Some Micro-Chemical Tests For Alkaloids

S O M E T E S T S
M I C R O - C H E M I C A L F O E A L K A L O I D S
CHAELES H. STEPHENSON SCIENTIFIC A SS A T SIT N BFEEAU OF CHBMISTEY, UNITED STATES D P R M N O AGEXOUtTURH, EA T E T F W S I G O , D. O. A HN T N INCLUDING C H E M I C A L TESTS O F U S E D T H E
A L K A L O I D S
C. E . P A R K E R ASSISTANT CHEMIST B B A OF CHEMI3TBY, T NT D S A E D P B M N O AQRICULTXJEB, UEU 7 I B T T S BA T S T F W S I G O , D. O. A HN T N
With Tv/enty-seven Plates (162 Photomicrographs) and a Folding Table of Reactions.
L O N D O N CHARLES GRIFFIN & COMPANY, LIMITED W.C.2
12 E X E T E R STREET, STRAND, 1921
CONTENTS PG AE
INTRODUCTION MLCROCHEMICAL T E S T S FOR ALKALOIDS DESCRIBED BY OTHERS CONCENTRATIONS OF ALKALOIDAL SOLUTIONS REAGENTS U S E D METHOD U S E D IN MAKING T E S T S SCHEME FOR IDENTIFICATION OF ALKALOIDS TABLE SHOWING B E S T TESTS FOR EACH ALKALOID DETAILED DESCRIPTION OF T E S T S CHEMICAL EXAMINATIONS INDEX TO PLATES PLATES TABLE OF REACTIONS 1 3 7 8 11 13 15 16 84 107 Ill FOLLOWS PLATES
S O M E T E S T S
M I C R O C H E M I C A L F O R A L K A L O I D S
INTRODUCTION T H I S work on microchemical tests for alkaloids was begun in December, 1907, in order t o obtain microchemical tests for the detection of cocaine. F r o m this b e g i n n i n g work was done on other alkaloids u n t i l a total of sixty-four had been tested. Thirteen of these alkaloids w e r e of doubtful purity, a n d therefore the results obtained o n these are not recorded here. T w o preliminary papers h a v e been p r e s e n t e d o n this work before the Association of Official A g r i c u l t u r a l Chemists, the first i n 1908, published i n B u l l e t i n N o . 122, B u r e a u of Chemistry, p . 9 7 , 1 9 0 9 , a n d the s e c o n d i n 1910, published in B u l l e t i n N o . 137, B u r e a u of C h e m i s t r y , p. 189,1911. I n this work no claim at all is m a d e for originality in a p p l y i n g the microchemical t e s t s for alkaloids, as the methods have been in use for m a n y years. M a s t of the tests were worked out between t h e years 1907 a n d 1910, and since that time several of the m o r e important contributions on the subject b y other authors have b e e n made. References t o color reactions o n l y have, i n the m a i n , been purposely omitted, since they w e r e considered of m i n o r importance for this work. W e have endeavored to g i v e due credit for a l l micro*chemical tests which have been previously p u b l i s h e d and
SOME MICROCHEMICAL TESTS FOR ALKALOIDS
w h i c h are described i n this work, by referring in the t e x t t o t e s t s a l r e a d y described b y others. W h i l e t h e results in some cases are n o t all that m i g h t b e d e s i r e d , y e t some v e r y sensitive and characteristic tests h a v e b e e n w o r k e d out. N o tests whatever were obtained o n t h r e e o f t h e fifty-one alkaloids described. Tests on the o t h e r f o r t y - e i g h t alkaloids were, in m o s t cases, quite satisfactory. P h o t o m i c r o g r a p h s of all the more important c r y s t a l l i n e precipitates obtained were made, and the most c h a r a c t e r i s t i c ones are g i v e n on plates. F u n g o u s g r o w t h takes place in m a n y solutions of alkal o i d s a f t e r a time, a n especially heavy g r o w t h occurring in b r u c i n e solutions. A l l of our work, however, was carried o u t o n f r e s h l y prepared solutions. T h e alkaloids w i t h which the greatest number of cryst a l l i n e p r e c i p i t a t e s w e r e obtained, u s i n g the standard alkal o i d a l r e a g e n t s , w e r e strychnine, berberine, tropacocaine and brucine. T h e a l k a l o i d s w i t h which no crystalline precipitates w e r e o b t a i n e d were apocodeine, colchicine and solanine. T h e f o l l o w i n g thirteen alkaloids w e r e discarded bec a u s e t h e r e w a s a serious doubt as t o their p u r i t y : B e b e e r i n e , cephaline, coroutine, delphinine, duboisine, emet i n e , g e l s e m i n i n e , Iupinidine, pelletierine, sabadine, sabad i n i n e , s a n g u i n a r i n e and veratrine. T h e a u t h o r desires f u l l y to acknowledge the assistance r e c e i v e d f r o m M r . B . J . H o w a r d , Microscopist in charge of t h e M i c r o c h e m i c a l Laboratory, not o n l y for the m a n y v a l u a b l e s u g g e s t i o n s m a d e , but also for the taking of m a n y of t h e p h o t o m i c r o g r a p h s herewith published.
MICROCHEMICAL TESTS FOR ALKALOIDS DESCRIBED BY O T H E R S T h e f o l l o w i n g authors describe crystalline p r e c i p i t a t e s w i t h alkaloids, which precipitates have also been investig a t e d in this w o r k : 1. T . G . W o r m l e y , " M i c r o - c h e m i s t r y of P o i s o n s / ' 1869. S e c o n d edition 1885. This is t h e most e x h a u s t i v e work in E n g l i s h which w e have f o u n d o n t h e subject* I t gives microchemical tests for a g r e a t number of p o i s o n s other than alkaloids and deals with t w e l v e alkaloids, describing crystalline precipitates for n i n e of them. I t c o n tains m a n y fine p l a t e s showing the f o r m s of the v a r i o u s crystalline precipitates. I n the 1 8 8 5 edition microchemical tests f o r g e l s e m i n e are given in addition to t h o s e d e scribed i n t h e first edition. 2. J . W . Griffin and A r t h u r H e n f r e y , " T h e M i c r o graphic D i c t i o n a r y , a guide t o the e x a m i n a t i o n of t h e structure a n d nature of microscopic o b j e c t s , " 1 8 8 3 , vol. i, p . 30. D e s c r i b e s five crystalline precipitates w h i c h w e have w o r k e d o n . 3. A . W . B l y t h , " P o i s o n s : Their E f f e c t a n d D e t e c tion," 1885. T h e following crystalline precipitates are d e scribed: S t r y c h n i n e with potassium chromate; w i t h p o t a s sium t h i o c y a n a t e ; w i t h platinum chloride; with p a l l a d o u s chloride; a n d w i t h g o l d chloride. 4. A . IB. L y o n s , " N o t e s on t h e A l k a l o i d s o f C o c a L e a v e s , " The Am. Journ. Pharm., Oct., 1885, p . 3 0 . D e scribes the crystalline precipitates with cocaine a n d t h e following r e a g e n t s : P i c r i c acid; g o l d chloride; p l a t i n u m chloride; p o t a s s i u m h y d r o x i d e ; and sodium carbonate. G i v e s
sketches of the g o l d chloride a n d p l a t i n u m chloride reactions. 5. F . Giesel, " Ubermangansaures Kali zur P r i i f u n g des Cocains," Pharm. Zeit., F e b . 2 7 , 1 8 8 6 . Describes the crystalline precipitate with cocaine and potassium permanganate. 6. Popoff, " E m p l o i de l'acide Picrique pour la determination des alcaloides v e g e t a u x en toxicologie," Annales d'Hygiene publique et de mddecine Ugole, 3e Serie 26, 1 8 9 1 , p . 81. The author describes crystalline precipitates w i t h picric acid and gives sketches of the crystals produced. E i g h t of the crystalline precipitates described by him are f o r m e d in solutions of greater concentration than 1 : 5 0 , a n d hence we do not describe them. 7. T . G. W o r m l e y , " N o t e s o n S o m e of the Chemical P r o p e r t i e s of the Mydriatic Alkaloids," Amer. Jowrn. Pharm.j Nov., 1894, p. 513. Crystalline precipitates with t h e following reagents are described: H y o s c i n e and g o l d chloride; atropine and hyoscyamine a n d also hyoscine with picric acid. W e did not obtain any crystalline precipitates w i t h the two latter except in very concentrated solutions, a n d w e have avoided, as a rule, describing the crystals f o r m e d in solutions more concentrated than 1: 50. 8. H . Behrens, " A n l e i t u n g zur Mikrochemischen A n a l y s e , " vol. iii, 1st Edition, 1896. Three editions of this w o r k have appeared. This is the m o s t extensive work on microchemical analysis which has been published. 9. W . R. D u n s t a n and F . H . Carr, " Contributions t o O u r Knowledge of the A c o n i t e Alkaloids," The Pharm. Journ., F e b . 15, 1896, p . 1 2 2 . T h e authors describe the crystalline precipitate w i t h aconitine and p o t a s s i u m permanganate a n d that with cocaine and p o t a s s i u m permanganate.
TESTS FOR ALKALOIDS DESCEIBED B Y OTHERS
10. M . V a d a m , " Differenciation d e s alcaloides a u m o y e n de leurs precipites microcristallins," Journ. de Pharm. et de chimie, 6 serie, 1897, ii, p . 1 0 0 . D e s c r i b e s t w e n t y - t h r e e different crystalline precipitates w h i c h w e have studied. 11. B . Zenetti, " D e n mikrochemischen N a c h w e i s d e r A l k a l o i d e mittelst Pikrinsaure ( F e s t s c h r i f t z u r S t r a s s burger V e r s a m m l u n g des D . A p . - V . ) . " R e f e r e n c e t o above in Pharm. Zeit.j N o v . 3 , 1897, vol. xlii, p . 7 5 2 . D e s c r i b e s c r y s t a l s formed with picric acid a n d t h e f o l l o w i n g alkaloids: A t r o p i n e , cocaine, n i c o t i n e , brucine, a n d strychnine. 12. W . H . W a r r e n and R. S. W e i s s , " T h e P i c r o l o n a t e s of Certain A l k a l o i d s / ' Journ. of Biol. Chem., 3 , p . 3 2 7 , 1 9 0 7 . D e s c r i b e s crystals formed w i t h picric acid a n d alcoholic solutions of nicotine, strychnine a n d brucine. 13. W a l t e r J . D i l l i n g , " Coniine, C o n h y d r i n e , P s e u d o conhydrine, Coniceine, and a N e w Coniine I s o m e r . A S u m m a r y o f T h e i r Cjhemicajl R e a c t i o n s , " The Pharm. Journ. and Pharmacist, J u l y 17, 1909, p . 1 0 2 . D e s c r i p tion of five crystalline precipitates w i t h coniine, w h i c h w e describe. 14. E . A b d e r h a l d e n , " H a n d b u c h des biochemischen A r b e i t s m e t h o d e n , " 1910, vol. ii, p . 9 0 4 . 15. A l i d e Grutterink, " Beitrage zur mikrodhemischen A n a l y s e E i n i g e r A l k a l o i d e und D r o g e n m i t b e s o n d e r e r B e r i i c k s i c h t i g u n g der M e t h o d e n v o n H . B e h r e n s , " 1 9 1 0 . T h e author gives a table showing reactions of f o r t y - t w o alkaloids a n d bases w i t h sixty-nine r e a g e n t s , a n d describes m o r e fully reactions for sixteen alkaloids. I n n o other w o r k which w e have been able to locate h a v e microchemical tests for so g r e a t a number of different alkaloids b e e n
given, a l t h o u g h t h e r e a r e o n l y sixteen of t h e t o t a l f o r t y t w o alkaloids for w h i c h t h e r e a r e sketches a n d m o r e comp l e t e descriptions of t h e p r e c i p i t a t e s . 16. L . R o s e n t h a l e r a n d P . G o e r n e r , " A r o m a t i c N i t r o D e r i v a t i v e s , E s p e c i a l l y N i t r o p h e n o l s , as A l k a l o i d a l P r e c i p i t a n t s , " Z . Anal. Chem., 4 9 , 1910, p . 340. D e s c r i b e s t h r e e crystalline p r e c i p i t a t e s w i t h p i c r i c acid which w e h a v e described. 17. A . B o l l a n d , " M i k r o c h e m i s c h e S t u d i e n , " M o n a t shefte fiir Chemie 2 9 , 1 9 0 8 , p . 9 9 1 ; 32, 1 9 1 1 , p . 117. D e scribes m a n y c r y s t a l l i n e p r e c i p i t a t e s . 18. E . B . P u t t , " M i c r o c h e m i c a l T e s t s for t h e I d e n t i fication of Some of t h e A l k a l o i d s , " J. Ind. Eng. Chem., vol. iv, p . 5 0 8 - 5 1 2 , 1 9 1 2 . D e s c r i b e s seven crystalline p r e cipitates t h a t w e h a v e w o r k e d o n . F o u r t e e n p h o t o m i c r o g r a p h s a r e given.
CONCENTRATIONS OF ALKALOIDAL
SOLUTIONS
I N t e s t i n g the alkaloids, aqueous solutions of from 1 : 1 0 0 0 to 1: 5 0 were used. I n one ease, however, a more concentrated solution than 1 : 5 0 w a s used, a n d that w a s with the alkaloid quinine, in which case a concentration of 1 : 3 5 was unetL T h i s m o r e concentrated solution w a s used on account of the lack of .satisfactory crystal formation in more dilute solutions. W h e n the alkaloid or alkaloidal salt w a s not c o m p l e t e l y soluble in water, j u s t sufficient 10 per cent, hydrochloric a d d wan a d d e d t o dissolve it. I n one or t w o cases o n l y wits an alcoholic solution of the alkaloid used, because the alkaloid w a s not soluble in w a t e r or in the 10 per cent, hydrochloric acid. T h e s e solutions of alkaloids w e r e tested with different reagents a n d t h e character of the precipitates, w h e n formed, w a s noted under the microscope. A f t e r s o m e time those r e a g e n t s which were f o u n d t o be u n s a t i s f a c t o r y as alkaloiclaf precipitates were abandoned, a n d d u r i n g the remainder of the work o n l y those r e a g e n t s which a p p e a r e d of value were retained. T h e final revised list of reagents which w e r e f o u n d o f value for tents n u m b e r s about forty.
REAGENTS USED T h e following reagents were used in 5 per cent, aqueous solutions: sodium carbonate; sodium nitroprusside; sodium phosphate; sodium benzoate; sodium phosphomolybdate; potassium hydroxide; potassium acetate; potassium iodide; potassium iodate; potassium chromate; potassium ferrocyanide and ferricyanide; potassium cyanide; potassium permanganate; saccharin; silver nitrate; ammonium molybdate; chromic acid; the chlorides of gold, platinum, palladium,* mercury, iron and zinc; a 10 per cent, solution of barium nitrate; a saturated, aqueous solution of picric acid and the following reagents for which w e give the formula: Marine's r e a g e n t C a d m i u m iodide P o t a s s i u m iodide D i s t i l l e d water 30 g m s . 60 g m s . 180 c.c.
Mayer's reagents1:100 mercuric chloride in water and add j u s t sufficient potassium iodide t o redissolve the scarlet precipitate first produced. Millon's reagentdissolve metallic mercury in an equal weight of concentrated nitric acid and dilute with an equal volume of water. Zinc-chlor-iodideZinc chloride 100 g m s . Water 60 c.c. P o t a s s i u m iodide 20 g m s . Iodine crystals 6 gms. Mr. E. B. Putt of this Bureau informs me that it is difficult to obtain a 5 peT cent, aqueous solution of palladous chloride in a soluble form. What is ordinarily supplied as palladous chloride is either palladous-ammonium chloride or is a brown partially soluble powder that acts very much as if it contained considerable basic salt. If such a salt is encountered, it can be used only after being subjected to treatment with chlorine.
REAGENTS USED Wagner's reagentIodine P o t a s s i u m iodide Water
5(ty 1 0 0 0 c.c.
P h o s p h o m o l y b d i c acidsodium p h o s p h o m o l y b d a t e i n 10 times its w e i g h t of a m i x t u r e of 1 p a r t of s t r o n g nitric acid t o 10. p a r t s of water* P h o s p h o t u n g s t i c aciddissolve 1 0 0 p a r t s of sodium t u n g s t a t e and 60 t o 80 p a r t s of sodium p h o s p h a t e in 500 parts of w a t e r a n d a d d nitric acid u n t i l t h e reaction is acid. Silicotungstic a c i d a 5 per cent, aqueous solution. K r a u t ' s r e a g e n t e i g h t y g r a m m e s bismuth nitrate i n 2 0 0 c.c. nitric acid of 1.18 sp. g r . D i s s o l v e 272 g r a m m e s p o t a s s i u m iodide i n a little w a t e r a n d add t o above. A m m o n i u m t h i o c y a n a t e a 10 per cent, aqueous solution. A saturated aqueous solution of s o d i u m nitroprusside w a s u s e d in addition t o the 10 per cent, solution, but reactions with both solutions appear to b e similar. A 10 p e r cent, solution of picric acid i n alcohol w a s u s e d i n addition t o t h e saturated aqueous solution. T h e g r e a t e s t difference n o t e d w a s w i t h atropine, in which case t h e alcoholic solution w a s m u c h m o r e sensitive in f o r m i n g crystals t h a n the aqueous solution. T h e f o l l o w i n g r e a g e n t s w e r e u s e d t o t e s t at least a p a r t of t h e alkaloidal solutions, but t h e y w e r e n o t retained either because t h e y r e a c t e d similarly t o s o m e r e a g e n t already on t h e list or because t h e y did n o t f o r m crystalline precipit a t e s w i t h t h e alkaloids u n d e r the conditions u s e d i n this w o r k : A m m o n i u m h y d r o x i d e ; barium carbonate; barium chloride; bismuth n i t r a t e ; bromine w a t e r ; c a d m i u m chlo-
10 SOME MICROCHEMICAL TESTS FOR ALKALOIDS ride; chloral hydrate; citric acid; ferric sulphate; phenol; phosphoric acid; potassium bromate; potassium bromide; potassium chloride; potassium fluoride; picrolonic acid; pyrogallic acid; sodium bicarbonate; sodium citrate; sodium hydroxide; sodium hypochlorite; sodium nitrate; sodium salicylate; sodium sulphite; sodium t u n g s t a t e ; stannous chloride; strontium arsenate; strontium chromate; strontium nitrate; tannic acid; tartaric acid; uranium acetate; uranium nitrate; zinc sulphide.
M E T H O D USED IN MAKING TESTS T o prepare the residue for testing it is usually essential that the alkaloid be separated from the product in as pure a form as possible by the usual chemical methods. E x p e r i e n c e s with t h e tests have amply demonstrated the importance of this operation preliminary to a p p l y i n g the tests, and a considerable degree of purity is usually requisite to the successful operation of the test. T h e alkaloid or alkaloidal residue to be tested is dissolved in water, and if not completely soluble sufficient 10 per cent, hydrochloric acid is added drop by drop until it is in solution. Care should be taken t o keep all solutions to be tested as nearly neutral as possible, since t h e influence of free acid on the formation of crystalline alkaloidal compounds tends t o break up or dissolve the crystals first formed. P l a c e one drop of the alkaloidal solution on a microscopic slide and add, b y means of a glass rod, one small drop of the reagent. E x a m i n e for crystals under the microscope. Crystals are generally formed at once, though at times the slide must stand for a few minutes. I n the latter case do not place cover glass on the solution, as crystallization is often due to concentration b y evaporation. B y rubbing the slide with a glass rod crystallization is hastened, though t h e crystals are more likely to be abnorm a l when the solution is stirred. Precipitates which crystallize at all crystallize very quickly, as a rule, w h e n stirred with a glass rod. I n a few cases, however, crystals are not formed at all unless the solution be stirred. W h e n stirred, the crystals are likely to be smaller and not so characteristic as when the crystals form more slowly. W e recommend.
IS SOME MICROCHEMICAL TESTS FOR ALKALOIDS that stirring with a glass rod be avoided as far as possible on account of the abnormal crystal forms likely to be thus obtained. H o w e v e r , stirring serves a useful purpose in many cases a n d is often a desirable procedure. Care should be taken that the glass rod used in m a k i n g the test is properly cleaned between each test, otherwise it serves t o carry at least a trace of crystalline matter from one test over into the n e x t . I t is desirable to make u p the alkaloid to be tested to known strength, as the crystals formed show such variation in many cases dependent u p o n concentration. T h e amount of reagent used has usually great effect upon the formation of crystals. Sometimes a very small amount of reagent gives the best crystals, then again a considerable amount is needed in order to g e t crystal formation at all. N o r m a l l y an amorphous precipitate is formed which soon crystallizes, though at times the crystals are formed directly without the amorphous precipitate being first thrown down. W i t h some alkaloids, notably berberine and narcotine, similar crystals are formed with a great number of different reagents, and it appears that the alkaloid is thrown out of the solution by the addition of the reagent rather than that a salt is formed. L I M I T o r R E A C T I O N . I n * every case where w e g e t crystal formation in the 1 : 1 0 0 0 solution of the alkaloid, a more dilute solution was used in order to report the approximate greatest dilution with which crystals are formed. I t will be noted that i n some reactions, cocaine with gold-chloride, for example, crystals are produced at dilutions of as great as 1: 20,000. S u c h a reaction is a very sensitive one and with it w e can identify mere traces of alkaloid.
S C H E M E FOR IDENTIFICATION OF ALKALOIDS T h e following outline m a y be of service i n i d e n t i f y i n g t h e alkaloids, t h o u g h it h a s t h u s f a r been f o u n d impossible t o m a k e o u t w h a t is considered a s a t i s f a c t o r y k e y for u s e i n t h e i r identification. I f a n y alkaloid is suspected, find it o n t h e list a n d u s e t h e r e a g e n t u n d e r which it is placed. F o r e x a m p l e , i n testi n g for a t r o p i n e , u s e W a g n e r ' s r e a g e n t for cocaine, g o l d chloride, e t c . T h e a l k a l o i d s i n t h e following lists a r e n o t t h e o n l y ones which f o r m c r y s t a l s w i t h t h e r e a g e n t s i n question, b u t each alkaloid is listed u n d e r t h a t r e a g e n t w i t h which i t f o r m s t h e m o s t s a t i s f a c t o r y c r y s t a l s for identification. Characteristic crystalline precipitates are formed with each r e a g e n t a n d alkaloids in the list following it.
WITH GOLD CHXOMDB SOLTJTIOX WITH POTASSIUM HXDBOXIDE SOLUTION
1. Cocaine 2. Tropacocaine 3. Benzoyl-ecgonine 4. Strychnine 5. Caffeine 6. Quinidine 7. Quinoline 8. Apomorphine 9. Nicotine 10. Sparteine 11. Scopolamine
WITH KBATTT'S REAGEOT
1. Thebaine 2. Papaverine 3. Narcotine 4. Hydrastine 5. Aspidospermine 6. Corydaline 7. Chelidonine

WITH WAGNEE'S REAGEOT
1. Homatropine 2. Hyoscyamine 8. Berberine 4. Atropine 5. ColcMdne

WITH PLATHHTM CHXORJDE SOLUTION
1. Theobromine 2. Narceine 8. Anhalonine 4. Coniine 5. Arecoline
1. Calycanthine 2. Pilocarpine 3. Brucine 4. Cinchonidine
14. SOME MICROCHEMICAL TESTS FOR ALKALOIDS WITH Yuotmunvvomc Acx 1. Baaine 2. Pilocarpidinc 3. Pelleterine
WITH PII0*I!0*OT.TWUT*
WITH Mnrn ( Vnumtm */ Ilrrnffie J - >ifnlnf

liyflm.tJnJfir
X Choline . 2. Ecgoninc
WITH MAEnr/i* RA}TT
W
Wrrii Mam' 1 i * *% C= * r t >tl4nr

*M Snwr* l*itfriiATii
t Moiphlne 2. Codeine
WITH SODIUM CAOJ*ATIS
W m t
1. CInchoninc 2. Acoaltlne
TABLE S H O W I N G BEST T E S T S FOR ALKALOID

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DETAILED DESCRIPTION O F T E S T S I t will be noted that t h e alkaloids are treated i n alphabetical order. T h e descriptions are kept short, and m a n y of t h e crystal forms produced can, at least, be b u t poorly described. Reference is made i n the t e x t to all crystal forms reproduced in the plates. M a n y of the precipitates photograph very poorly, and for this reason some sensitive tests have not been reproduced i n t h e plates.
ACONITINE.
F o u r crystalline a n d twenty-two non-crystalline p r e cipitates were obtained.

S O D I U M C A R B O N A T E . T h i s is the m o s t sensitive test
for aconitine. Characteristic rosettes are usually slowly formed i n great numbers! even in the 1 : 1 0 0 0 solution. T h e y are usually formed more quickly i n the 1 : 5 0 0 solution than in the 1 : 2 0 0 solution. A m o r p h o u s precipitates form in the t w o more concentrated solutions o n l y ( P l a t e X I I I , Fig. 6).
POTASSIUM PERMANGANATE.The precipitates are
rather dense. T h e crystals are small, spherical, a n d form very slowly in the t w o more dilute solutions. I n the 1 : 2 0 0 solution the crystals are rosettes and polarize; brightly. T h e y are characteristic a n d of good size. N o t m a n y a r e formed and they form slowly ( 9 ) .
POTASSIUM H Y D R O X I D E . I n the 1 : 2 0 0 solution t h e
amorphous precipitate crystallizes in rosettes of shortpointed rods. Crystals are often formed i n f e w numbers only and very slowly.
DETAILED DESCRIPTION OF TESTS
17
P o t a s s i u m c y a n i d e gives results similar t o the above. A m m o n i u m thiocyanate gives a v e r y slight precipitate in the 1 : 50 solution only.
ANHALONINE (MESCALINE)
T h e microchemical reactions of t w o samples, one labeled " M e s c a l i n " a n d the other " A n h a l o n i n e , " were identical. A t t e n t i o n is called to the m e l t i n g point obtained, by Parker, 1 8 1 - 2 a s compared with Schmidt's figure recorded as 2 5 4 - 5 . F o u r aqueous solutions of the alkaloid were used, viz.: 1 : 1 0 0 0 ; 1 : 5 0 0 ; 1 : 2 0 0 ; 1: 50. N o n - c r y s t a l l i n e precipitates f o r m e d o n l y withzinc-chloriodide, phosphomolybdate, and silico-tungstic acid. W i t h this alkaloid eleven crystalline precipitates were obtained as f o l l o w s :
K R A U T ' S R E A G E N T . T h i s i s the m o s t sensitive test,
great numbers o f v e r y small crystals b e i n g formed even i n a 1 : 3 0 0 0 solution. T h e y are too small, however, t o b e of service as a test. T h e best concentration for crystal formation is about 1 : 2 0 0 . A t this concentration they are often very l a r g e a n d moss-like i n appearance a n d polarize only slightly. A n amorphous precipitate is thrown d o w n first from w h i c h t h e crystals form quickly. G O L D C H L O R I D E . T h i s reagent does n o t form crystals in the 1 : 1 0 0 0 solution, b u t small crystals, quickly g r o w i n g to a g o o d size, are formed upon stirring t h e 1 : 5 0 0 solution. V e r y l a r g e rods, i n a dense mass, f o r m in the 1 : 5 0 solution, a n d of g o o d size i n the 1 : 2 0 0 solution ( P l a t e I,Fig.l) (17).
PLATINUM CHLORIDE.This reagent forms a few
small crystals o n stirring the 1 : 5 0 0 solution.
A dense
18 SOME MICROCHEMICAL TESTS FOR ALKALOIDS mass of large, fine needle rosettes w a s instantly formed in the 1: 50 and 1: 200 solutions ( P l a t e I V , F i g . 1 ) ( 1 7 ) . P i c n i c A C I D . A n amorphous precipitate formed in the 1 : 5 0 solution only, and this crystallizes very rapidly into large, rough-appearing rods. L a r g e rods are also formed in the 1: 200 solution, b u t without a first amorphous precipitate. U p o n stirring the t w o more dilute solutions we g e t a great number of small rods ( 1 7 ) .
WAGNER'S REAGENT.This reagent forms heavy
amorphous precipitates i n the t w o more concentrated solutions which crystallize slowly into large, rough-appearing rods of a bluish-black to black color. Their polarization is slight T h e slight amorphous precipitate in t h e 1 : 5 0 0 solution does not crystallize, but upon stirring with a glass rod great numbers of small rods are formed even i n the 1 : 1 0 0 0 solution if sufficient reagent be added ( 1 7 ) .
M E R C U R I C C H L O R I D E . U p o n stirring the 1 : 50 solu-
tion great numbers of large, highly polarizing rosettes either of plates or of rods are formed ( 1 7 ) .
POTASSIUM PERMANGANATE.This reagent forms
very short rods in the 1 : 50 solution only on stirring.

PALLADOUS C H L O R I D E . C l e a r - c u t , h i g h l y polarizing
crystals are formed i n the 1 : 5 0 solution o n stirring a n d a very few in the 1 : 2 0 0 solution. T h e y axe normally fouror six-sided.
M A Y E R ' S R E A G E N T . T h i s reagent forms amorphous
precipitates in the t w o more concentrated solutions only. Crystals form quickly and are rosettes o f rods or plates.
M A R M E ' S R E A G E N T . L a r g e plates or rosettes of rods
formed in the 1 : 50 solution.

P H O S P H O T U N G S T I C A C I D . T h i s r e a g e n t forms crys-
tals slowly in all solutions from t h e amorphous precipitate.
19
T h e y are rosettes of short rods a n d i n t h e 1 : 5 0 solution often v e r y l a r g e rods ( P l a t e X X I V , F i g , 3 ) . Froehde's reagent gives a y e l l o w color.
APOCODEINE
ISTo crystalline precipitates were obtained whatever with this alkaloid. A l l of t h e c o m m o n alkaloidal reagents form heavy n o n crystalline precipitates.
APOMORPHINE
T h e solutions of this alkaloid take on a light, greenish color within a f e w m i n u t e s and turn t o a dark blue after a few hours. T e n crystalline a n d twenty-five non-crystalline precipitates were obtained.
G O L D C H L O R I D E . T h i s is t h e best t e s t for apomorphine.
H e a v y amorphous precipitates appear in all the solutions a t once a n d t h e y are of a deep, red-brown color. T h e crystals are f o r m e d i n dense masses a n d do n o t polarize. T h e y are small a n d very fine needles in all the solutions, being somewhat larger in t h e more concentrated solutions a n d are occasionally rosettes. This test is v e r y sensitive, as w e are able t o obtain fine needles i n a 1 : 1 0 , 0 0 0 solution ( P l a t e I , F i g . 2 ) .
P L A T I N U M CHLORIDE.Crystals formed from amor-
phous precipitate i n all solutions e x c e p t the 1 : 5 0 . T h e y are characteristic, rather small rosettes, of a deep rose color. C H R O M I C A C I D . V e r y faint rose color in the 1 : 1 0 0 0 solution a n d precipitates i n t h e 1 : 5 0 0 a n d more concentrated solutions which are reddish-brown turning t o g r e e n around t h e e d g e s .
0 SOME MICROCHEMICA1 TESTS FOE ALKALOIDS Crystals are small and formed in all solutions. T h e y do not polarize. N o r m a l l y rosettes of short rods. The crystals in the 1: 50 are considerably larger.
POTASSIUM IODIDE.Amorphous precipitate in the
1:50 solution only, and this crystallizes into small, highly polarizing crystals which have sharp, clear-cut angles like those of a diamond. T h e 1: 200 solution does not form & precipitate. Potassium iodide gives reactions similar to above. Z I N C CHLOBJDE.Small rods in rosettes instantly formed in the 1: 50 solution only. KRAUT'S R E A G E N T . L a r g e rosettes of rods are formed at once in the 1: 50 solution in addition t o the heavy brown precipitate which does not crystallize. PHOSPHOMOLYBDIC A C I D . A dense mass of rod-like crystals instantly formed in the 1 : 5 0 solution only. HILXON'S REAGENT.Rose-red precipitate forming rods in the 1 : 5 0 solution and these are often i n rosettes. N o crystals formed in the more dilute solutions. Barium nitrate and silver nitrate give crystals similar to those formed with this reagent and in the 1 : 5 0 solution only. The following color reactions were noted: Rose-red color with ferric sulphate and also with silver nitrate and ammonium vanadate. R e d precipitate turning to deep green with potassium chroniate and ferric chloride. HlTDROBBOMIDE F o u r crystalline and t e n non-crystalline precipitates were obtained. O n l y one satisfactory test w a s worked out for this alkaloid, KJUTTT'S REAGENT.Crystals are formed slowly from
21
the amorphous precipitates i n t h e t w o more concentrated solutions, b u t are formed more quickly in t h e t w o dilute solutions. T h e y are good-sized plates often i n rosettesT h e t e s t is sensitive, as great numbers of crystals are formed i n t h e 1 : 1 0 0 0 solution ( P l a t e X I I I , F i g . 1 ) .
P I C R I C A C I D . N o t a sensitive test and n o amorphous
precipitates a r e formed. A s the 1: 50 solution evaporates, spherical crystals o r rosettes of short rods o f good size are formed.
PALLADOXJS CHXOBIDE.After t h e . 1 : 50 solution
stands f o r s o m e t i m e large irregular plates which polarize well are f o r m e d . T h e s e plates are often i n rosettes ( P l a t e VI, Fig. 1 ) .
MILLO^T'S S O L U T I O N . I n t h e 1 : 50 solution only, small
needle-shaped crystals, often i n rosettes, are formed from. the amorphous precipitate. ASPIDOSPERMINE E i g h t crystalline and twenty-four non-crystalline p r e cipitates w e r e obtained.
POTASSIUM HYDEOXIDE.A fine a n d sensitive test.
F i n e l a r g e crystals a r e quickly formed from the amorphous precipitate. T h e y are a l o u t the same in appearance in all solutions, though much larger i n t h e more concentrated solutions. T h e y form a dense mass of rosettes in the 1 : 5 0 solution. Their appearance is similar t o that of some forms o f seaweed ( P l a t e X V , Tig. 1 ) . S m a l l rods formed in a 1: 3000 solution, which i s about the limit o f reaction. Potassium chrornate, sodium carbonate, and potassium cyanide give crystals similar to above, t h o u g h t h e y are not so sensitive.
WAGNER'S REAGENT.Yery short, pointed rods in
22 SOME MICROCHEMICAL TESTS FOR ALKALOIDS rosettes are formed i n the two more concentrated solutions only. They are formed around the edges of the heavy amorphous precipitates (Plate X , F i g . 1 ) . Potassium iodide,' Mayer's reagent, and Marine's reagent all give results similar to the above. The following color reactions were noted: With ferric chloride a deep rose color i s developed in addition to the amorphous precipitate. With potassium iodate a faint pink color develops in the 1: 50 solution on standing. The amorphous precipitate with gold chloride takes on a hlack color. With chromic acid the amorphous precipitate takes on a pink color.
ATKOPINE S U L P H A T E
Four crystalline and thirteen non-crjrstalline precipitates were obtained.

W A G N E R ' S R E A G E N T . T h i s is a sensitive test and the
best one that we have for atropine. T h e crystals are normally small rods or triangular plates and are formed in great numbers from the amorphous precipitate first thrown down. They hare sharp angles and polarize poorly. A 1: 8000 solution forms great numbers of very small crystals. T h e crystals in the 1 : 5 0 solution are of good size. This is a satisfactory test, and though the crystals are never large, they are characteristic ( P l a t e X , F i g s . 2 and 3) ( 1 8 ) . Zinc-chlor-iodide or Kraut's reagent forms similar to the above. crystals
P I C R I C A C E D . W e have a n amorphous precipitate but
n o crystals in solutions above 1 : 50. Crystals are obtained with difficulty and only in the 1: 50 solution. T h e y are
23
normally large, plate-like and polarize brilliantly. Crystal formation is so uncertain as t o make this reaction of n o value as a test. This test is described b y W o r m l e y , he, however, using an alcoholic solution of picric acid rather than an aqueous solution ( 1 ) . T h e alcohoKc solution of picric acid makes a very satisfactory reagent for this alkaloid, as u p o n stirring the 1 : 1 0 0 0 solution small plates are formed and from the amorphous precipitates i n the other solutions rosettes of plates are formed ( P l a t e X I X , F i g . 1) (6) ( 1 0 ) ( 1 1 ) . P o t a s s i u m hydroxide forms a n amorphous precipitate in the 1 : 5 0 solution but not in the 1 : 200 solution. W o r m l e y describes a crystalline precipitate with potassium hydroxide, but w e have been unable t o confirm this ( 1 ) .
BENZOYL-ECGONINE
F i v e crystalline and nine non-crystalline precipitates were obtained. G O L D C H L O E I D E . A m o r p h o u s precipitates are formed in all solutions. This is the only sensitive test. Crystals form from the amorphous precipitates rather quickly. T h e y g r o w t o large size, are light greenish-yellow in color and polarize brightly. T h e y are normally rosettes of l o n g and rather narrow irregular plates. T h e y f o r m a dense mass in t h e 1 : 50 solution. T h e photograph reproduced was taken j u s t after t h e crystallization h a d started. Crystals of g o o d size are formed in a 1 : 3 0 0 0 solution after it stands for some time ( P l a t e I , F i g . 3 ) .
W A G N E R ' S R E A G E N T . H e a v y , amorphous precipitates
in all solutions, but crystals are formed only i n the t w o more concentrated solutions. These crystals are large a n d dense rosettes appearing like some form of seaweed. O n l y
a few crystals are formed in the 1 : 2 0 0 solution. T h e s e crystals are of a light greenish color a n d polarize fairly well. Kraut's reagent reacts as above.
MAYER'S R E A G E N T . V e r y l o n g , needle-like crystals
are formed in the t w o more concentrated solutions only and around the edges of the drops. Palladous chloride forms a n amorphous precipitate in the 1 : 5 0 solution only. The amorphous precipitate with potassium permanganate and with mercuric chloride is very slight,
BEEBEBINE
A saturated aqueous solution, this being about 1 : 1 0 0 , also solutions of 1 : 5 0 0 and 1 : 1 0 0 0 were used. T h e solutions of this alkaloid are yellow. U p o n addition of the following reagents t o a saturated aqueous solution i n addition to a heavy amorphous precipitate, crystals are formed. T h e crystals show u p t o better advantage if but little of the reagent be used. The crystals are similar, if n o t identical, with all of t h e reagents in the following list: Chromic acid; sodium nitroprusside; platinum chloride; palladous chloride; mercuric chloride; zinc-chlor-iodide; W a g n e r ' s reagent; potassium iodide; Kraut's reagent; Marine's reagent; jphosphomolybdic acid; saccharin; ammonium thiocyanate; potassium permanganate ( 2 ) ; picric acid; sulphuric acid; hydrochloric acid; ferric chloride; zinc chloride; Millon's reagent; barium and silver nitrate. T h e y are i n all cases moss-like or fine needles, often in rosettes, and the greater part of the h e a v y amorphous precipitate does n o t crystallize ( P l a t e X , F i g . 4, and P l a t e X X , F i g s . 5 and 6 ) ( 8 ) .
25
T h e r e a g e n t s with which no crystals were obtained are: P o t a s s i u m cyanide; ammonium molybdate; g o l d chloride; Mayer's r e a g e n t ; potassium ferrocyanide; potassium ferricyanide; silico-tungstic acid and phosphotungstic acid. Berberine, u p o n evaporation of t h e aqueous solution, crystallizes into yellow needles, often in rosettes.
B E T A I N E HYDROCHLORIDE
E i g h t crystalline and three non-crystalline precipitates were obtained. P H O S P H O T U N G S T I C A C I D . T h i s is a fine, sensitive and characteristic test. Crystals are formed at once in all solutions, a n d t h e y form a very dense mass in the t w o more concentrated solutions. T h e crystals are of t w o kinds, l o n g needles in rosettes and very short rods i n rosettes. T h e limit of reaction is about 1 : 2 0 0 0 ( P l a t e X X I V , Fig. 4).
K R A U T ' S R E A G E N T . A f e w needles are formed in the
1 : 1 0 0 0 solution. A m o r p h o u s precipitates in the three more concentrated solutions o n l y a n d crystals are slowly formed f r o m this unless the solutions are stirred, but if stirred, t h e crystals are formed quickly, being needles usually in rosettes, though often six-sided crystals are formed.
P H O S P H O M O L Y B D I C A C I D . T h e r e is n o precipitate in
the 1 : 1 0 0 0 solution. Great numbers of small spherical crystals are formed and also needles and often rods in the 1 : 5 0 0 solution. R e actions are best a t this dilution. L a r g e rosettes of needles or rods are formed slowly i n t h e t w o more concentrated solutions, the needles w i t h pointed ends a n d rods irregular in outline. T h e amorphous precipitates are heavy in the more concentrated solution ( P l a t e X X I V , F i g . 1 ) .
26
PICRIC ACID.Crystals of rods and needles are formed on stirring the 1: 50 solution only. This is not a t all sensitive as a test. W i t h the alcoholic solution of picric acid they are formed in the t w o more concentrated solutions.
W A G N E R ' S R E A G E N T . O n l y in the 1 : 50 solution are
crystals formed on stirring. in rosettes.
T h e y are characteristic plates
GOLD CHLORIDE.Crystals are formed only o n stirring
the 1 : 5 0 solution. T h e y are usually regular rods a n d sometimes there are a few plate-like forms. They polarize well.
SILICO-TUNGSTIC A C I D . T h e amorphous precipitates
formed in the t w o more concentrated solutions o n l y crystallize. Crystals are very small and polarize b u t slightly. They are normally short rods.
S O D I U M B E N Z O A T E . C r y s t a l s are formed i n the 1 : 50
solution only and they are rosettes of plates and are exactly like those formed when hydrochloric acid is added t o a sodium benzoate solution. The following color reaction was n o t e d : Ammonium vanadate when added t o a little of the alkaloid gives a red color which fades quickly.
BRTJCINE
Twenty crystalline and nine non-crystalline precipitates were obtained.

POTASSIUM H Y D R O X I D E . T u f t s of needle-shaped crys-
tals are formed in the 1 : 200 solution. This is t h e greatest dilution that forms crystals at once and then only on stirring. V e r y large rosettes of needles are quickly formed from the heavy amorphous precipitate in the 1 : 50 solu-
27
tion. These crystals g r o w t o large size a n d m a y easily be seen without t h e aid of the microscope. I n t h e more dilute solutions t u f t s of needle crystals are formed from the amorphous precipitate only after some time and as the solutions evaporate ( P l a t e X V , F i g . 2 ) (1) ( 8 ) . Sodium carbonate gives results similar t o t h e above ( 8 ) .
SODIUM NITRO-PRUSSIDE.Spherical crystals are
formed in the 1: 2 0 0 solution on standing. T h e y are small and show distinct polarization crosses. R o s e t t e s formed from the amorphous precipitate in t h e 1 : 50 solution. N o precipitate is formed i n the more dilute solutions ( P l a t e I X , F i g .6 ) .
CHROMIC ACID.Great numbers of rods, often in
rosettes, are formed i n a 1 : 1 0 0 0 solution. T h e crystals are large a n d i n a dense mass in t h e more concentrated solutions. A great number of small crystals were formed i n a 1: 4000 solution ( P l a t e X X I I , F i g . 1 ) . Chrom-acetic acid gives crystals similar t o above, but they are formed without an amorphous precipitate being first thrown down.
P O T A S S I U M C H R O M A T E . I n t h e three more concen-
trated solutions rods often in rosettes are formed. Often the rods have a twisted or spiral appearance ( 8 ) ( 1 0 ) .
P L A T I N U M C H L O R I D E . T h i s is a v e r y sensitive test.
T h e 1 : 1 0 0 0 solution crystallizes o u t into a dense mass of rods which are sometimes in rosettes. T h e crystals in the 1 : 5 0 solution are small, as it is t o o concentrated for best results. A considerable number of small crystals are formed i n a 1 : 2 0 , 0 0 0 solution ( P l a t e I V , F i g . 2 ) ( 1 ) (8) ( 1 0 ) .
P A L L A D O U S C H L O R I D E . R o d s f o r m e d in all solutions
28 SOME MICEOCHEMICAL TESTS FOR ALEALOIDS up to 1: 4000. A t the latter dilution w e g e t very few small crystals. These rods are normally i n rosettes and formed from an amorphous precipitate. I n the 1: 500 solution an amorphous precipitate is first formed and the crystals are not large and polarize poorly. The 1 : 5 0 solution is too concentrated for best results and the crystals vary greatly in size (Plate V I , F i g . 2 ) . MERCXJEIC C H L O E I D E . A light precipitate is obtained in the 1:500 and 1 : 1 0 0 0 solution from which spherical or rosette crystals are formed. T h e crystals are fine rosettes of plates in the more concentrated solutions. T h e addition of too great an amount of reagent hinders the formation of crystals greatly ( 8 ) . ZLNTC CHLOEIDE.The crystals are clear-cut rods or plates with sharp angles in rosettes, and the limit of reaction is about 1: 500 ( P l a t e X X V I , F i g . 5 ) . ZDJC-CHLOR-IODIDE.Limit of reaction is about 1:200. Crystals are spherical or rosettes and like those obtained in the zinc chloride reaction.
AMMONIUM THIOCYANTATE.The slight amorphous
precipitate in the 1 : 5 0 solution crystallizes quickly into moss-like rosettes (Plate X X V , T i g . 1) ( 2 ) .

WAGDOB'S R E A G E N T . H e a v y precipitates form in all
the solutions. Crystallization is slow a n d t h e crystals are small rosettes except in more concentrated solutions, when they are large rosettes or rods. T h e limit of reaction is about 1: 2000 (Plate X , F i g . 5 ) .
POTASSIUM I O D I D E . N o amorphous precipitates are
obtained with this reagent. Large, brightly polarizing masses of plates, often i n rosettes, are forihed i n t h e t w o more concentrated solutions i n great numbers. Crystals are formed yery slowly in the 1: 500 solution. These crys-
DETAILED DESCRIPTION OF TESTS tals have a characteristic appearance Fig. 2 ) . Plafe
K K A U T ' S R E A G E N T . A dense precipitate but n o crys-
tals are formed in the 1 : 1 0 0 0 solution. A f e w good-sized rosettes are formed in the 1 : 500 solution. T h e y appear t o float at the surface. I n the more concentrated solutions w e have another f o r m of crystals also present. T h e y are smaller a n d darker a n d rosettes are formed slowly.
M A R M E ' S R E A G E N T . V e r y dense, a m o r p h o u s precipi-
tates are obtained only in the three more dilute solutions. Crystals form only i n the 1 : 5 0 solution. T h e y are the same as those formed with potassium iodide; that is, rosettes composed of rods.
POTASSIUM FERRICYANIDE.Crystals quickly f o r m i n
the 1: 50 solution o n l y from the dense, amorphous precipitate. T h e y are large rosettes of plates a n d polarize brightly. M a n y of the crystals are needles a n d sometimes a combination of needles and plates is obtained. T h e y are very brilliant under polarized light ( 1 ) .
P O T A S S I U M C Y A N I D E . C r y s t a l s f o r m in the t w o more
concentrated solutions only and in general outline look like some form of grass in the 1 : 200 solution, a n d large rosettes in the 1 : 5 0 solution. A dense, amorphous precipitate is first formed i n t h e 1 : 5 0 solution ( P l a t e X X I , F i g . 1 ) . S A C C H A R I N . G r e a t numbers of small needles are formed o n stirring the 1 : 2 0 0 solution a n d are slowly formed in the 1 : 5 0 solution, i n which case w e have rosettes of needles, or often of plates. N o crystals or precipitates are obtained i n the t w o more dilute solutions ( P l a t e V , Fig. 6 ) . P I C R I C A C I D . T h i s is a poor test, as crystals form slowly a n d often n o t at all, and then in concentrated solu-
30 SOME MICROCHEMICAL TESTS FOR ALKALOIDS tions only. (11) ( 1 2 ) .

M I I X O N ' S R E A G E N T . A slight precipitate is formed in
They are rosettes of needles ( 1 ) ( 6 ) ( 1 0 )
the 1 : 2 0 0 solution and it redissolves. There is a faint rose-red color which forms rather slowly a n d starts around the edge of the drop. O n standing, brilliant crystals are formed. T h e crystals are rosettes of small plates and polarize well (Plate X X V I , F i g . 1 ) . U p o n addition of water to some brucine crystals, they change from irregular plates t o fine rosettes of needles a n d these i n turn dissolve as more water is added. The brucine solutions upon standing several weeks become a faint pink color. The following color reaction was noted: A d d one drop of chromic acid and then one drop of concentrated hydrochloric acid. A deep blood-red is then developed. Crystals are formed similar to those formed with a chromic acid alone.
CAFFEINE
Six crystalline and t w o non-crystalline precipitates were obtained. KRAUT'S R E A G E N T T h i s is the best test for caffeine. I n t h e 1:1000 solution a heavy, amorphous precipitate is formed which crystallizes quickly in dark, reddish-brown rosettes of small size. T h e 1 : 5 0 0 and 1 : 200 solutions give similar results. These crystals do n o t polarize. The precipitate is so dense i n the 1 : 5 0 solution that it hinders crystallization somewhat. M a n y of the crystals are small rods. A 1 : 5000 solution forms some very small crystals (Plate X I I I , F i g . 2 ) .
MERCURIC CHLORIDE.A considerable number of
D E T A I L E D DESCRIPTION OF TESTS
31
needle-shaped crystals a r e formed i n all solutions. T h e y f o r m a d e n s e m a s s i n t h e 1 : 50 s o l u t i o n a n d p o l a r i z e b r i l l i a n t l y . T h e l i m i t of r e a c t i o n is a b o u t 1 : 1 0 0 0 ( P l a t e vin,Fig.i).

P A L L A D O U S C H L O R I D E . T h e l i m i t of r e a c t i o n is a b o u t
1 : 200. T h e c r y s t a l s a r e s m a l l n e e d l e s a n d f o r m a dense m a s s i n t h e 1 : 5 0 s o l u t i o n . T h e y p o l a r i z e b u t slightly.

GOLD CHLORIDE.This is n o t a s e n s i t i v e t e s t . The
c r y s t a l s a r e n o r m a l l y n e e d l e s o r t u f t s of needles a n d f o r m v e r y slowly. I n t h e 1 : 5 0 solution t u f t s o r r o s e t t e s of fairly l a r g e r o d s o r n e e d l e s a r e f o r m e d o n s t a n d i n g ( P l a t e I , F i g .4 ) ( 1 0 ) .

PHOSPHOMOLYBDIC ACID.Heavy, amorphous pre-
cipitates f o r m . C r y s t a l s a r e s m a l l r o d s u s u a l l y f o r m e d around t h e edges. I n t h e 1 : 200 solution t h e crystals a r e small a n d i n g r e a t n u m b e r s . T h e y d o n o t s t a n d o u t c l e a r l y on a c c o u n t of b e i n g m a s s e d a n d o f t e n s u r r o u n d e d b y t h e a m o r p h o u s p r e c i p i t a t e . I n t h e 1 : 5 0 solution t h e p r e c i p i t a t e is so d e n s e t h a t t h e c r y s t a l s f o r m slowly. T h e y a r e normally rods.
SILICO-TUNGSTIC A C I D . I n the two more concentrated
solutions t h e c r y s t a l s a r e v e r y s m a l l a n d t h e a m o r p h o u s p r e cipitates a r e d e n s e . T h e c r y s t a l s d o n o t p o l a r i z e b r i g h t l y .
CALYCANTHINE SULPHATE
T h i r t e e n c r y s t a l l i n e a n d fifteen n o n - c r y s t a l l i n e p r e cipitates w e r e o b t a i n e d .
PLATINUM CHLORIDE.This is a s e n s i t i v e t e s t . An
a m o r p h o u s p r e c i p i t a t e is f o r m e d which crystallizes a l m o s t i n s t a n t l y i n t o cross-like c r y s t a l s i n all solutions. They a p p e a r especially well in t h e 1 : 5 0 solution ( P l a t e I V , Fig. 3 ) .
32 SOME MICEOCHEMICAL TESTS FOR ALKALOIDS

CHROMIC A C I D . A m o r p h o u s p r e c i p i t a t e s appear in
the three more concentrated solutions only. These precipitates crystallize on standing, forming fine, large rosettes of needles or rods, especially large i n the 1 : 50 solution (Plate X X I I , F i g . 2 ) .
PALLADOUS C H L O R I D E . T h i s is a sensitive test. Crys-
tals are quickly formed in all the solutions. T h e y are very large and even in the 1 : 1 0 0 0 solution t h e y are of g o o d size. Great numbers of small rods are formed o n stirring the 1 : 2 0 0 0 solution (Plate V I , F i g . 3 ) . ZINC-CHLOR-IODIDE.Amorphous precipitates appear in all the solutions. V e r y small crystals were noticed only in the 1: 500 solution after it had stood for some time, but most of the precipitate does not crystallize,
W A G N E R ' S R E A G E N T . A m o r p h o u s precipitates formed
in all the solutions and crystals i n all but t h e 1 : 1 0 0 0 solution. Crystals are irregular plates often occurring in rosettes. T h e y are very small in the 1 : 5 0 0 solution, but form quickly a n d are of large size in the 1 : 5 0 solution.
A M M O N I U M T H I O C Y A N A T E . A dense m a s s of rods is
formed in the 1 : 50 solution. quick crystallization.
Stir the 1 : 5 0 0 solution for
P O T A S S I U M C Y A N I D E . T h e crystals are small a n d tri-
angular in outline. T h e y are quickly formed in the t w o more dilute solutions on stirring. T h e y are large and form quickly from the precipitate in the 1 : 5 0 solution. Potassium hydroxide or sodium carbonate gives results similar to those aboveKRAUT'S R E A G E N T . V e r y large, d e e p , yellow, irregular plates are formed in the t w o more concentrated solutions only from the dense, amorphous precipitates.
P O T A S S I U M I O D I D E . L a r g e rosettes of rods are formed
3S
instantly u p o n stirring the 1: 50 solution a n d in t h e 1 : 200 solution o n standing.

S O D I U M P H O S P H A T E . C r y s t a l s are o n l y f o r m e d i n the
1: 50 solution. T h e y form slowly. T h e y are rather small, clear-cut rosettes g r o w i n g t o g o o d size. T h e following color reaction w a s n o t e d : A m m o n i u m vanadate gives a blood-red color, which quickly fades, i n the 1 : 50 solution.
SODIUM NITROPRUSSIDE.A concentrated aqueous
solution of the reagent w a s used. T h e dense, amorphous precipitate quickly crystallizes in the 1 : 5 0 solution only i n fine large rosettes of plates. O n stirring the 1 : 5 0 0 solution small six-sided plates are formed.
CHELIDONINE
T w e l v e crystalline a n d t w e n t y non-crystalline precipitates were obtained.

POTASSIUM HYDROXIDE.This is the best test for
chelidonine. T h e amorphous precipitate crystallizes quickly in all solutions. T h e crystals i n the 1 : 1 0 0 0 solution are goodsized, irregular rods a n d polarize well. A 1 : 4 0 0 0 solution forms numerous small crystals. Other reagents which give crystals as above are sodium carbonate; potassium chromate; potassium cyanide; sodium phosphate a n d potassium acetate.
POTASSIUM FERROCYANIDE.The light amorphous
precipitates crystallize rather slowly i n small, highly p o l arizing crystals. M a n y are formed even i n t h e 1 : 1 0 0 0 solution.
K R A U T ' S R E A G E N T . C r y s t a l s f o r m e d in t h e t w o m o r e 3
34 SOME MICROCHEMICAL TESTS FOR ALKALOIDS dilute solutions from t h e amorphous precipitate are small and black six-sided plates.
FERRIC CHLORIDE.The amorphous precipitate is
slight. Small, highly polarizing crystals are formed in the two more dilute solutions. T h e y appear like those formed with zinc chloride.
Z I N C C H L O R I D E . S m a l l , h i g h l y polarizing crystals are
formed i n the t w o more dilute solutions ( P l a t e X X V I I , Fig.l).

S O D I U M P H O S P H O M O L Y B D A T E . P l a t e s of g o o d size are
formed in the t w o more dilute solutions. SACCHARIN.IsTo amorphous precipitate formed. A few small crystals are formed i n the t w o more dilute solutions. T h e y polarize well. Color reaction: W i t h a m monium vanadate added to d r y material a green color is formed, gradually fading t o p i n k ; Froehde's reagent g a v e a blue color.
CHOLINE
E i g h t crystalline a n d seven non-crystalline precipitates were obtained.

P H O S P H O M O L Y B D I C A C I D . T h i s is a sensitive t e s t for
choline. Amorphous precipitates a n d crystals are formed in all the solutions. T h e y are small, as a rule. T h e best concentration is 1 : 200, i n which solution great numbers of needles, often in rosettes, axe formed. These crystals are often in dense masses ( P l a t e X X I V , F i g . 2 ) .
SILICO-TUNGSTIC A C I D . H e a v y precipitates f o r m in
all the solutions and the best crystals are formed i n the 1 : 5 0 0 solution. T h e crystals are rods or needles, often curved, and normally have a peculiar granular appearance on the surface.
35
PHOSPHOTXJNGSTIC A C I D . H e a v y , amorphous precipi-
tates are f o r m e d w i t h this reagent a n d small crystals are formed only i n t h e 1 : 5 0 solution. This is n o t a satisfactory reagent t o u s e as a test for choline. B A R I U M N I T R A T E . G r e a t numbers of very small crystals are f o r m e d i n all solutions. T h e y appear t o be very small rosettes.
MERCURIC CHLORIDE.Heavy, amorphous precipitate
formed in the 1 : 50 solution only. Crystals are formed i n all the solutions, t h o u g h o n l y around edges i n t h e 1 : 1 0 0 0 solution. T h e y are small and polarize slightly a n d are normally spherical.
KRAUT'S REAGENT.Heavy, amorphous precipitates
appeared i n the three more concentrated solutions. I n the 1: 200 solution, a f e w l o n g and rather narrow, irregular plates are formed around the edge of the drop only Rosettes of small plates are formed a t once i n the 1 : 5 0 solution. T h e y are n o r m a l l y six-sided.
G O L D C H L O R I D E . T h e limit of reaction is about 1 : 2 0 0 .
Rosettes of plate-like crystals in 1 : 5 0 solution are formed from the amorphous precipitate. T h e y polarize fairly well.
MAYER'S R E A G E N T . A n amorphous precipitate ap-
pears in t h e 1 : 5 0 solution only, and this crystallizes rapidly into plates which are rather small a n d often triangular in outline.
CINCHONINE SULPHATE
S i x crystalline precipitates and twenty-three non-crystalline precipitates were obtained.

S O D I U M C A R B O N A T E . T h i s is a v e r y delicate a n d char-
acteristic test. T h e crystals are small rosettes a n d are quickly formed i n g r e a t numbers in all the solutions. T h e y
36
are especially g o o d in the 1 : 1 0 0 0 solution. T h e y form such a dense mass i n t h e more concentrated solutions that they do not show u p so well as they d o i n t h e 1 : 1 0 0 0 solution. T h e y are dark i n appearance a n d d o n o t polarize brightly ( P l a t e X I V , F i g s . 1 ( X 150) a n d 2 ( X 300) ( 8 ) . Numbers of small needles are formed i n a 1 : 20,000 solution. Other reagents forming crystals a s above alt h o u g h the tests are n o t so sensitive i n all cases, are as follows: Potassium hydroxide; potassium chromate, a n d potassium cyanide.
POTASSIUM P E R M A N G A N A T E . N o t a s a t i s f a c t o r y test,
as the amorphous precipitate frequently does n o t crystallize. T h e amorphous precipitate is v e r y dense in all t h e solutions. T h e crystals form slowly a n d best i n t h e 1 : 2 0 0 solution. T h e y are small plates, usually p o i n t e d and often in rosettes. T h e rosettes are often v e r y dense and are found in great numbers as t h e solution stands.
P O T A S S I U M F E I I R O C Y A N I D E . G r e a t n u m b e r s of small
rods in rosettes formed i n the 1 : 1 0 0 0 solution. M o s t of the crystals in the 1 : 2 0 0 solution are spherical and show distinct polarization crosses; others a r e rosettes of plates. I n the 1 : 5 0 solution t h e amorphous precipitate is very dense and the f e w crystals which form at first are like those i n the 1: 2 0 0 solution. T h e precipitate does n o t crystallize rapidly, however ( 8 ) ( 1 5 ) ,
CINCHONIDINE SULPHATE
N i n e crystalline a n d twenty-four non-crystalline p r e cipitates were obtained.

PLATINUM CHLORIDE,The test is sensitive. A
1 : 20,000 solution forms a number of small crystals. T h e
37
crystals are u s u a l l y rosettes of plates, sometimes of rods. T h e y are clear-cut, but do n o t polarize highly. T h e 1 : 5 0 solution is t o o concentrated for best results ( P l a t e I V , Fig. 4) ( 8 ) .
SODIUM PHOSPHATE.Dense rosettes of n e e d l e s are
quickly f o r m e d i n the t w o more concentrated solutions only. T h e y show distinct polarization crosses ( P l a t e V I I , Fig. 5 ) .
POTASSIUM CYANIDE.On standing crystallization
takes place s l o w l y from t h e amorphous precipitate first formed i n t h e three more concentrated solutions. T h e crystals are dark, appearing in rosettes of needles o r spherical a g g r e g a t e s .
S O D I U M B E N Z O A T E . T h e very dense, amorphous p r e -
cipitate in t h e t w o more concentrated solutions crystallizes out into large a n d dense rosettes of needles. T h e s e rosettes grow t o a l a r g e size and can be plainly seen w i t h the n a k e d eye. Stir t h e solution for quick results. P I C R I C A C I D . T h e crystals are very slowly formed from the amorphous precipitate. T h e y are good-sized rods in masses.
POTASSIUM HYDROXIDE.Spherical crystals are
quickly formed i n the 1 : 5 0 0 solution u p o n stirring* A m o r p h o u s precipitates form in the 1 : 5 0 0 a n d more c o n centrated solutions. There is n o precipitate i n the 1 : 1 0 0 0 solution ( P l a t e X V , F i g . 3 ) .
P O T A S S I U M F E R R O C Y A N I D E . T h i s is n o t so sensitive
as the above, b u t the crystals, when formed, are similar. A n amorphous precipitate and crystals form in the 1 : 5 0 solution only. Sodium carbonate reacts like t h e above ( 8 ) .
POTASSIUM C H R O M A T E . T h e light, a m o r p h o u s pre-
38
cipitate first formed crystallizes into great numbers of rodshaped rosettes i n the 1 : 1 0 0 0 solution. There is no precipitate at greater dilutions. COCAINE HYDROCHLORIDE T e n crystalline a n d fourteen non-crystalline precipitates were formed. T h e following observations w e r e n o t e d concerning the various reactions with cocaine i n which crystals were produced.
G O L D C H L O R I D E . T h i s is t h e m o s t sensitive reaction
for cocaine. A n amorphous precipitate is first produced in all solutions. T h e crystals are characteristic a n d a few small ones are produced i n a dilution of 1 : 2 0 , 0 0 0 . T h e crystals can best be described b y photograph. T h e y are normally delicate a n d characteristic rosettes. When formed slowly they are l o n g rods w i t h m a n y short arms running out at nearly right angles from t h e m a i n axis. Their shape varies greatly according t o t h e concentration (Plate I , Figs. 5 and 6) (4) (8) ( 1 0 ) .
P L A T I N U M C H L O R I D E . T h i s is also a v e r y sensitive
test for cocaine and a characteristic one. F e a t h e r y crystals are formed u p to a dilution of about 1 : 4 0 0 0 ( P l a t e I V , Fig. 5) (8) (4) (10) ( 1 8 ) .
P I C R I C A C I D . T h i s is a c o m p a r a t i v e l y p o o r reagent, as
the heavy, amorphous precipitates crystallize with difficulty a n d usually very slowly. Crystals formed in solutions u p t o about 1: 800, b u t t h e y are n o t very characteristic. T h e y are rosettes or sheaves of needles ( P l a t e X I X , Fig. 2) (4) (6) (10) ( 1 1 ) .
P O T A S S I U M P E R M A N G A N A T E . S o l u t i o n s u p to about
1: 700 give purple-colored plates or a g g r e g a t e s of plates.
39
Vigorous stirring of t h e solution is often necessary t o start crystallization, which then proceeds rapidly. T o obtain this test readily, add only a very small amount of the reagent ( P l a t e X X I I I , F i g , 4 ) ( 5 ) ( 7 ) ( 1 5 ) .
P A L L A D O U S C H L O R I D E . T h e crystals f o r m e d are char-
acteristic, but this reagent is not so sensitive as some of the others mentioned above. T h e crystals v a r y much i n form according t o the conditions of precipitation. O n e of the most common forms is that obtained with a 1 : 1 0 0 solution, when feathery crystals are produced; 1 : 5 0 0 is about the limit of reaction. F o r quick crystallization, a d d a drop of chlorine water or a drop of dilute hydrochloric acid t o the solution a n d then a d d the palladous chloride a n d stir with a glass rod. This reaction is of interest, as it w a s the first one w e used a n d w a s the starting-point of this investigation ( P l a t e V I , F i g . 4 ) . C H R O M I C A C I D * T h i s test is made b y adding a small drop of chromic acid solution t o t h e test drop. A precipitate is formed which o n stirring disappears. A small drop of strong hydrochloric acid is added a n d a yellowish deposit is produced, which after stirring o n t h e slide should in a f e w minutes be transformed into loose, spherical clusters of a n acicular crystal. This test appears t o be one of the most uncertain because of t h e difficulty with which crystals are produced ( P l a t e X X I I , F i g . 3 ) . P o t a s s i u m dichromate m a y be substituted for the chromic acid i n the above. I n this test it w a s found that after once h a v i n g obtained crystals n o difficulty w a s experienced thereafter, n o matter how m a n y times the test w a s tried. There is always considerable difficulty in first obtaining crystals. A f t e r some time the conclusion w a s arrived at that the glass rod used
40 SOME MICROCHEMICAL TESTS FOR ALKALOIDS in making the tests serves t o carry at least a trace of crystalline matter from one test t o the other, and that this trace causes the whole drop t o crystallize out very quickly. This fact is mentioned here t o call attention t o the necessity of washing the stirring r o d thoroughly, since simply drying on a towel will not clean it perfectly.
FERRIC C H L O R I D E . T h e crystals are a g g r e g a t e s of
rather coarse, blade-like forms with chisel-shaped ends. This is n o t a very sensitive test. Stir t o obtain quick results ( P l a t e I I I , F i g . 6 ) .
POTASSIUM HYDROXIDE.In concentrated solutions
this reagent produces a white, amorphous precipitate which changes into crystals o n standing, or b y stirring with a glass rod. T h e crystals are rod-shaped ( 4 ) . Sodium carbonate gives results similar t o t h e above (4) ( 8 ) . ^ Potassium cyanide forms l a r g e rods from t h e amorphous precipitate in t h e 1 : 5 0 solution slowly. I n practical work the g o l d chloride a n d the platinum chloride tests have been u s e d almost entirely, as they are the most satisfactory. Tests were performed t o determine the effect on the gold chloride test of t h e presence of another alkaloid with the following results: A s a rule, w h e n there is present one-fifth as much of t h e other alkaloid as of cocaine, it has no effect on the test; one-half t h e a m o u n t affects the crystals in more than half t h e combinations tried and twice the amount destroys the test i n nearly every case. Other alkaloids i n equal a m o u n t have a slight effect only on the picric acid test, b u t change t h e form of crystals with platinum chloride i n most cases.
41
T h e potassium permanganate test is destroyed in about one-half of the cases, w h e n an equal amount of another alkaloid is present. T h e potassium hydroxide test is spoiled in only eight out of forty cases when another alkaloid is present in equal amount. T h e effect of glycerine u p o n the different tests w a s tried and it w a s found that glycerine, when present in o n e hundred times the amount of t h e alkaloid, d i d n o t interfere w i t h the test i n a n y case. Likewise granulated sugar present o n e hundred or more times the amount of t h e cocaine does n o t interfere with the tests. Tannic acid, w h e n present in equal amount with t h e cocaine, affects the test in all cases. G u m arabic or lactose solutions do n o t affect the tests for cocaine i n a n y case.
CODEINE
Solutions of codeine sulphate were used. T h e crystalline precipitates number nine; the non-crystalline eleven.
M A R M E ' S R E A G E N T . T h i s , t h e best t e s t for morphine,
is also the best test for codeine. F i r s t w e have a n amorphous precipitate a n d from this great numbers of small, silvery-appearing masses are formed at once, even in solutions as dilute as 1 : 2000. I n the more concentrated solutions, such as the 1 : 2 0 0 solution, for example, these masses soon start t o crystallize a n d crystallization spreads rapidly over the field a n d the crystals appear as small rods i n masses. F i g . 1 shows first stages of crystallization, while F i g . 2 shows very little of t h e precipitate which has n o t
42 SOME MICROCHEMICAL TESTS FOR ALKALOIDS crystallized. O n still f u r t h e r s t a n d i n g , r o s e t t e s of g o o d sized p l a t e s , n o r m a l l y v e r y i r r e g u l a r i n o u t l i n e , a r e f o r m e d , a l t h o u g h we often h a v e r o d s i n r o s e t t e s i n s t e a d of p l a t e s . T h e s e changes a r e well s h o w n b y p h o t o g r a p h s ( P l a t e X V I I , Figs. 1,2 and 3 ) . R e a c t i o n s w i t h M a y e r ' s r e a g e n t a r e similar t o above (10).
MILLON'S R E A G E N T . T h i s reagent forms a precipitate
in t h e 1 : 1 0 0 0 solution, b u t n o c r y s t a l s w e r e n o t e d . I n t h e 1: 50 solution a p r e c i p i t a t e is f o r m e d first a n d it c r y s t a l lizes i n small, spherical c r y s t a l s . I n t h e 1 : 2 0 0 a n d m o r e c o n c e n t r a t e d solutions t h e p r e c i p i t a t e t a k e s o n a yellow color a n d t h e c r y s t a l s a r e still s m a l l a n d spherical. T h i s reaction is of n o v a l u e a s a t e s t , t h e c r y s t a l s b e i n g t o o small (Plate X X V I , F i g . 2 ) . CHROMIC A C I D . T h e amorphous precipitate first f o r m e d quickly c h a n g e s i n t o oil-like d r o p s . C r y s t a l s a r e f o r m e d only i n t h e 1 : 5 0 solution. T h e y a r e characteristic, d a r k i n a p p e a r a n c e , a n d a r e n o r m a l l y s p h e r i c a l , o r rosettes of p l a t e s . S o m e t i m e s t h e y a r e m u c h l a r g e r a n d b u s h y i n a p p e a r a n c e . F o r m a t i o n of c r y s t a l s t a k e s p l a c e slowly u n less t h e d r o p be s t i r r e d ( P l a t e X X I I , F i g . 4 ) .
P O T A S S I U M C H R O M A T E . T h i s r e a g e n t is n o t sensitive
as a test. T h e 1 : 5 0 s o l u t i o n crystallizes o u t i n s t a n t l y i n t o beautiful, l a r g e r o s e t t e s . T h e b r a n c h e s a r e b r o a d , p l a t e like, o r r o d s , a n d h a v e p o i n t e d e n d s ( P l a t e X X I , F i g . 4) ( 1 ) . Z I N C - C H L O R - I O D I D E . T h e l i m i t of r e a c t i o n for c r y s t a l s is a b o u t 1 : 500, b u t t h e s o l u t i o n is t o o d i l u t e f o r good-sized crystals. G r e a t n u m b e r s of r o s e t t e s a r e f o r m e d in t h e 1 : 5 0 solution, some b e i n g coarse, o t h e r s m a d e u p of needle-like forms ( P l a t e X X V I I , F i g s . 2 a n d 3 ) .
43
P O T A S S I U M I O D I D E . T h i s reagent forms long, needlelike crystals, often i n masses, in the 1 : 5 0 solution only. Crystals are formed without a first amorphous precipitate ( P l a t e X V I I I , F i g .3 ) ( 1 ) .
W A G N E R ' S R E A G E N T . T h i s r e a g e n t f o r m s precipitates
in all solutions, b u t crystals are formed o n l y i n t h e 1 : 5 0 and 1 : 2 0 0 solutions. T h e y are rosettes of plates, light brown in color and usually of large size ( P l a t e X , Fig* 6 ) (8) (18) ( 1 ) .
A M M O N I U M T H I O C Y A N A T E . L i m i t of reaction about
1 : 1 0 0 . L a r g e rosettes consisting of rods are formed in the 1 : 5 0 solution. T h e s e rods are pointed at t h e ends. T h e y polarize brightly ( P l a t e X X V , F i g . 2 ) . COLCHICINE T h e aqueous solutions are yellow. N o crystalline precipitates were obtained. U p o n adding W a g n e r ' s reagent t o the 1 : 50 solution of the alkaloid, a n amorphous precipitate is formed. S o m e very fine needles are formed from this after it stands for some time, but their formation is n o t always certain.
CONIINE
Seven crystalline a n d nine non-crystalline precipitates were obtained.

P H O S P H O T U N G S T I C A C I D . T h i s is a g o o d a n d sensitive
test. Short rods are instantly formed even in a 1 : 1 0 , 0 0 0 solution ( P l a t e X X I V , F i g . 5 ) ( 1 3 ) .

KRAUT'S REAGENT.Heavy, amorphous precipitates
are first formed. T h e crystals are small, clear-cut plates of a deep, reddish-brown color, and are often six-sided, but
44
are not all of the same shape. G r e a t numbers are formed from the precipitate i n t h e 1 : 5 0 0 solution a n d all of the 1 : 1 0 0 0 solution crystallizes. Crystals were also obtained in a 1: 3000 solution ( 8 ) ( 1 3 ) .
MARME'S REAGENT.The amorphous precipitate is
heavy in all cases. O n standing it takes o n a n appearance similar to oil globules, a n d after some time crystals are formed. T h e y are large a n d coarse in appearance a n d form very slowly. T h e y are n o r m a l l y a bundle of rods or plates. T h e growth of the crystals m a y be v e r y clearly seen under the microscope as the drops come i n contact with the crystal. T h e 1: 200 and 1 : 5 0 0 solutions are best for crystal formation ( P l a t e X V I I , F i g . 4 ) ( 1 3 ) .
MAYER'S R E A G E N T . A m o r p h o u s precipitates formed
in all the solutions. Crystals are of good-sized rosettes of irregular rods. Crystallization is slow a n d n o crystals are formed in the 1 : 1 0 0 0 solution.
PHOSPHOMOLYBDIC ACID.Many of the crystals
formed are small and spherical, others are plate-like, sharply cut, and deep y e l l o w in color. T h e crystals are formed rather quickly from t h e amorphous precipitate a n d are best seen around the edges of t h e h e a v y amorphous precipitate and in the more concentrated solutions ( 1 3 ) .
PALLADOTJS C H L O R I D E . O n l y o n stirring do w e get
crystals. These are small a n d f o r m o n l y as t h e solutions become concentrated. T h e y are short rods, often i n rosettes.
B A R I U M N I T R A T E . R o s e t t e s of small rods are formed
in all the solutions o n stirring ( 1 3 ) . T h e heavy, amorphous precipitate w i t h g o l d chloride takes on a violet color at once in t h e 1 : 5 0 solution.
DETAILED DESCRIPTION OF TESTS CORYDALINE
45
S i x crystalline a n d twenty-seven non-crystalline p r e cipitates were obtained.

POTASSIUM H Y D R O X I D E . A m o r p h o u s precipitates ap-
pear in all the solutions. Crystallization is slow. T h e crystals are rosettes of rods i n the 1 : 50 solution. I n t h e more dilute solutions, plates or rosettes of plates are formed. A m m o n i u m hydroxide gives results similar t o the above.
SILVER N I T R A T E . S h o r t rods are f o r m e d from the
amorphous precipitate in t h e 1: 50 solution only.

AMMONIUM THIOCYANATE.Small rosettes are
formed in all the solutions quickly from t h e amorphous precipitates.

P O T A S S I U M C H R O M A T E . V e r y fine rods or needles i n
rosettes are formed solutions only.

MERCURIC
in t h e t w o more
concentrated
ap-
CHLORIDE.Amorphous
precipitates
pear i n all t h e solutions and t h e y all crystallize, t h o u g h n o t rapidly. Rosettes of rods, polarizing fairly well, is t h e normal form ( P l a t e V I I I , F i g . 2 ) .
M I L L O N ' S R E A G E N T . I n the 1 : 50 solution, crystals in
rosettes of rods are formed from the amorphous precipitate. The following color reactions were n o t e d : L i g h t blue quickly changing to dark blue color with F r o e h d e ' s reagent in the 1 : 50 and 1: 200 solutions, and this color gradually fades out. A slight reddish or pink coloration formed with ammonium vanadate i n all the solutions u p t o t h e 1 : 1 0 0 0 . I t is very faint in the 1 : 1 0 0 0 solution.
46 SOME MICEOCHEMICAL TESTS FOR ALKALOIDS

CYTISINE HYDROCHLORIDE
Nine crystalline and seven non-crystalline precipitates were obtained.

MAYER'S R E A G E N T . T h i s is the best t e s t for cytisine.
This is a very sensitive test, as good-sized rosettes of rods are soon formed in a 1: 6000 solution. A very dense crystalline precipitate is formed a t once i n all solutions. They are moss-like, often turning to rods o n standing.
M A R M E ' S R E A G E N T . T h e r e are n o precipitates in the
two more dilute solutions. A n exceedingly dense mass of rods formed very quickly from the amorphous precipitate i n t h e 1 : 50 solution. Stir the 1 : 2 0 0 solution for quick crystallization.
P L A T I N U M C H L O R I D E . T h i s reagent f o r m s crystals
only on stirring the 1 : 5 0 solution. T h e y are large and dense rosettes of needles and do not polarize ( 8 ) .
PHOSPHOTUNGSTIC A C I D . T h i s r e a g e n t forms heavy,
amorphous precipitates in all the solutions, a n d crystals i n all except the 1: 50 solution are formed slowly* T h e y are rosettes of plates and polarize but slightly.
WAGNER'S R E A G E N T . T h i s is a sensitive test. The
amorphous precipitate crystallizes in all the solutions used. The crystals are normally l o n g rods, o f t e n in rosettes. They do not polarize. T h e y are often leaf-like rosettes in the 1 : 5 0 solution, and crystallization t a k e s place more slowly in this solution than in the more dilute ones. T h e crystals grow to a good size i n the 1 : 1 0 0 0 solution ( P l a t e X I , Fig. 1 ) . PICRIC A C I D . N o crystals appear i n a n y solution more dilute than 1: 200. O n stirring the 1: 2 0 0 solution w e g e t great numbers of needles or often plates. T h e 1 : 50 solu-
DETAILED DESCRIPTION OF TESTS tion crystallizes o u t slowly, forming very large, rosettes of rods ( P l a t e X I X , F i g . 3 ) .
MERCURIC CHLORIDE.Fine rosettes of
47 dense
are
plates
formed in the t w o more concentrated solutions. They polarize well. O n l y a f e w small ones form o n stirring the 1: 5 0 0 solution ( P l a t e V I I I , F i g . 3 ) . G O L D C H L O R I D E . T h e best crystals with this reagent are at a concentration of about 1 : 2 0 0 . T h e crystals are t h e n large, somewhat leaf-like a n d characteristic. They do n o t polarize. A great n u m b e r of very small crystals are formed o n stirring the 1 : 1 0 0 0 solution ( P l a t e I I , F i g . 1) ( 8 ) . T h e following color reaction w a s n o t e d : T h e 1 : 50 solution takes on a deep reddish-brown color w i t h ferric chloride.
DIONINE (ETHYL-MORPHINE)
E i g h t crystalline a n d fourteen non-crystalline precipitates were obtained. N o very sensitive tests for dionine were obtained.
WAGNER'S REAGENT,The dense precipitate in the
1 : 5 0 and 1 : 2 0 0 solutions crystallize rather rapidly into l a r g e rosettes of rods. Crystals were n o t obtained i n the m o r e dilute solutions. T h e s e crystals are characteristic (Plate X I , F i g . 2) ( 1 8 ) . Kraut's reagent forms crystals similar t o t h e above, b u t t h e reagent does n o t appear t o be so sensitive.
M A Y E R ' S R E A G E N T . T h e crystals, f o r m e d in the t w o
m o r e concentrated solutions, are small. T h e y are silvery in appearance a n d do n o t polarize. T h e y form slowly, as a rule, and m o s t of t h e heavy, amorphous precipitate does n o t crystallize.
48 SOME MICROCHEMICAL TESTS FOR ALKALOIDS Marine's reagent gives results as above. ZINC-CHLOR-IODIDE.This reagent forms a heavy p r e cipitate and in the 1 : 50 solution a f e w small crystals f o r m around the edge. T h e y d o n o t polarize a n d might easily be overlooked.
S O D I U M C A R B O N A T E . S h o r t rods or rosettes of r o d s
are formed in the 1: 50 solution only and are formed s l o w l y unless the drop be stirred. N o precipitate formed ( P l a t e X I V , Fig. 3 ) . Potassium hydroxide gives results as above.
MERCURIC C H L O R I D E . N o precipitate appeared in t h e
two more dilute solutions. A n amorphous precipitate formed i n the 1: 50 solution only. I n the 1 : 2 0 0 and m o r e concentrated solutions, large rosettes of plates are the n o r mal form. Stir the 1: 200 solution i n order t o g e t quick crystallization (Plate V I I I , F i g . 4 ) . ECGONINE HYDROCHLORIDE Three crystalline and four non-crystalline precipitates were obtained.
PHOSPHOMOLYBDIC A C I D . T h i s is a delicate and c h a r -
acteristic test. Crystalline precipitates are formed i n a l l solutions up t o 1 : 4 0 0 0 . T h e y are best at a dilution o f 1:500. A l l of the amorphous precipitate i n the 1: 5 0 0 solution does not crystallize until it stands for some t i m e . The crystals are dense rosettes of needles often of l a r g e size. They do not polarize highly.
PHOSPHOTUNGSTIC A C I D . T h e crystals are v e r y s m a l l
and indistinct rosettes and are best seen in the 1 : 1 0 0 0 solution. The amorphous precipitates in t h e more concentrated solutions do not crystallize.
K R A U T ' S R E A G E N T . H e a v y , amorphous precipitates
49
are formed. Crystals are formed i n t h e 1 : 2 0 0 a n d in the 1 : 5 0 0 solutions only. T h e y are six-sided a n d n o t very large and are clear-cut plates ( P l a t e X I I I , F i g . 3 ) .
HEROINE (DIACETYL MORPHINE)
Seven crystalline a n d nineteen non-crystalline precipitates were obtained. N o very sensitive tests were obtained o n heroine.
S O D I U M C A R B O N A T E . A rather light, a m o r p h o u s pre-
cipitate is formed i n t h e 1 : 2 0 0 solution a n d it crystallizes slowly. Crystals polarize very highly a n d are often fine rosettes of p o i n t e d plates. There w a s n o precipitate i n t h e dilute solution.
SODIUM PHOSPHATE.This reagent forms rather
coarse rosettes of rods i n the 1 : 5 0 solution only, a n d n o first amorphous precipitate appeared.
POTASSIUM HYDROXIDE.No precipitate a p p e a r s e x -
cept i n the 1 : 5 0 solution, a n d this soon crystallizes. T h e crystals are rosettes of rods, often n o t well formed.
P L A T I N U M C H L O R I D E . C r y s t a l s are formed o n l y f r o m
the heavy precipitate i n t h e t w o more concentrated solutions after some time. T h e y are spherical or often fine rosettes of needles a n d do n o t polarize ( 1 8 ) .
M E R C U R I C C H L O R I D E . N o precipitate a p p e a r s in the
dilute solutions. I n the 1 : 2 0 0 solution a f e w crystals are slowly formed from the slight precipitate. T h e y do not polarize brightly. I n t h e 1 : 5 0 solution w e have a dense precipitate. Crystals are rather slowly formed, but they g r o w into good-sized rosettes, sometimes of blade-like forms. T h e reaction resembles that of morphine with this reagent; hence, if it is obtained, a p p l y t h e tests for morphine, especially with Mayer's and Marine's reagents. T h e
4
50
amorphous precipitate appears like oil g l o b u l e s before it crystallizes ( P l a t e V I I I , F i g . 5 ) .

POTASSIUM C Y A N I D E . I n the 1 : 5 0 solution, a rather
dense precipitate crystallizes s l o w l y i n t o solid, j a g g e d appearing crystals, o f t e n rods or cubes. B e a u t i f u l rosettes are often formed. B y stirring t h e 1 : 2 0 0 solution w e g e t great numbers of p l a t e s polarizing v e r y brightly ( P l a t e X X I , Fig. 2).
P I C R I C A C I D . C r y s t a l s a p p e a r in t h e t w o m o r e c o n -
centrated solutions from the h e a v y a m o r p h o u s precipitates. T h e y are spherical or often small rosettes, a n d d o n o t polarize brightly ( P l a t e X I X , F i g . 4 ) . HOMATROPINE F o u r crystalline a n d fourteen non-crystalline precipitates were obtained.
G O L D C H L O R I D E . T h e limit of r e a c t i o n is a b o u t 1 : 5 0 0 ,
as the 1 : 1 0 0 0 solution forms neither crystals n o r amorphous precipitate. I n t h e 1 : 5 0 0 solution a slight amorphous precipitate is first formed. T h i s , o n standing, turns into oil-like drops a n d from these crystals a r e formed. T h e y form slowly, are of a greenish color, a n d polarize brightly. T h e y are rosettes of plates. I n t h e 1 : 2 0 0 solution the amorphous precipitate is considerably heavier than before a n d crystallization is slow. T h e crystals sometimes appear t o be of a n orange color. E v e n in the 1 : 5 0 solution crystallization is very slow ( P l a t e I I , F i g . 2 ) ( 1 7 )
WAGNER'S REAGENT.This is a s e n s i t i v e t e s t , as a
number of very small crystals form i n a 1 : 4 0 0 0 solution on standing, t h o u g h t h e y are t o o small t o be o f service as a test.
DETAILED DESCRIFflON OF TESTS
51
T h e a m o r p h o u s precipitate in t h e 1 : 1 0 0 0 solution is dense. T h e crystals form slowly. T h e y are n e a r l y all small a n d dark-brown i n color a n d are m a i n l y six-sided. A f e w are larger a n d consist of several r a d i a t i n g branches. T h e y vary in color, b e i n g black, light or dark-brown, y e l l o w , and often o f a g r e e n color. T h e p h o t o g r a p h s s h o w t h e d e cided difference in the appearance of these crystals ( P l a t e X I , Figs. 3 and 4) ( 1 7 ) . K r a u t ' s r e a g e n t forms crystals quite similar t o above.
MILLON'S REAGENT.Small spherical crystals are
formed in the 1 : 5 0 solution o n l y ( P l a t e X X V I , F i g . 3 ) .

HYDRASTINE
Thirty-three a m o r p h o u s precipitates w e r e obtained with this alkaloid a n d o n l y o n e crystalline precipitate.

P O T A S S I U M H Y D R O X I D E . U p o n a d d i n g a 25 per cent,
solution o f this r e a g e n t t o t h e 1 : 1 0 0 0 solution o f t h e alkaloid a n d stirring, crystals are produced from t h e amorphous precipitate. T h e y are clear-cut rosettes. Crystal formation is much slower if t h e solution is n o t stirred. T h e crystals are similar but larger in more concentrated solutions. N o crystals were obtained with a 5 per cent, solution o f potassium hydroxide, a n d it is often difficult t o obtain a n y crystals a t all even with the 2 5 p e r cent, solution ( P l a t e X V , F i g .4 ) . T h e f o l l o w i n g color reaction w a s n o t e d : A m m o n i u m vanadate g i v e s a pink color which is n o t p e r m a n e n t in t h e 1 : 5 0 solution. A m m o n i u m thiocyanate g i v e s a n a m o r p h o u s precipitate in t h e 1 : 5 0 solution only.
5% SOME MICROCHEMICAL TESTS FOR ALKALOIDS

HYDRASTININE
A l l t h e solutions showed fluorescence, especially the more dilute ones. E i g h t non-crystalline a n d eleven crystalline precipitates were obtained.
POTASSIUM PERMANGANATE.The crystals formed
with this reagent are large a n d characteristic. T h e amorphous precipitate which is first formed does n o t ordinarily crystallize i n t h e 1 : 1 0 0 0 solution. S o m e t i m e s w e g e t a f e w rods and plates. I n the three m o r e concentrated solutions, however, w e g e t great numbers of large plates often in rosettes. T h e y have saw-tooth edges or often appear like some very deeply cut leaves ( P l a t e X X I I I , F i g . 5) ( 1 5 ) .
G O L D C H L O R I D E . T h i s r e a g e n t f o r m s a m o r p h o u s pre-
cipitates i n all the solutions, a n d the t w o more concentrated solutions crystallize o n l y o n stirring. T h e crystals formed are rods, often pointed or notched at t h e ends a n d sometimes occurring in rosettes.
MERCURIC CHLORIDE.On stirring the 1 : 1 0 0 0 solu-
tion w e g e t a f e w small rods. R o d s , often pointed, a n d in rosettes quickly formed o n stirring the 1 : 5 0 0 solution. A dense mass of large rods instantly formed in t h e 1 : 2 0 0 solution. T h e 1 : 5 0 solution crystallizes o u t into one dense mass of crystals ( 1 5 ) . C H R O M I C A C I D . T h i s test is characteristic but not very sensitive, as no crystals are formed at greater dilutions than 1: 200. I n the more concentrated solutions w e g e t great numbers of crystals. T h e y are normally dense rosettes of rods of peculiar shape, often pointed. Variations i n the appearance of t h e crystals are shown i n t h e photographs.
53
I n the 1 : 5 0 solution g r e a t numbers of large moss-like rosettes are f o r m e d a t once from the amorphous precipitate ( P l a t e X X I I , F i g s . 5 a n d 6 ) .
P I C R I C A C I D . P i c r i c acid f o r m s crystals in t h e t w o
more concentrated solutions only. T h e y are plates or rosettes of p l a t e s . I n the 1 : 5 0 0 solution they are often eight-sided; some a r e irregular in outline. T h e y are norm a l l y rosettes of l a r g e size i n the more concentrated solutions and polarize b r i g h t l y ( P l a t e X I X , F i g . 5 ) ( 1 6 ) .
ZINC-CHLOK-IODIDE.Amorphous precipitates are
heavy a n d numbers of crystals are formed quickly, especially in t h e 1 : 1 0 0 0 solution if stirred. T h e crystals are needles or rods u s u a l l y p o i n t e d a n d often i n rosettes.
PALLADOTJS C H L O R I D E . N o precipitate appears i n the
1 : 1 0 0 0 solution. N u m b e r s of rosettes are formed in the 1 : 5 0 0 solution. T h e y are composed of sharp-pointed needles resembling thorns. I n t h e 1 : 2 0 0 solution w e have large crystals in t w o forms, needles i n rosettes a n d rosettes of plates. I n the 1: 5 0 solution w e g e t a dense mass of needle-shaped crystals. R o s e t t e s of plates are n o t so c o m m o n ( P l a t e V I , Fig. 5 ) .
P L A T I N U M C H L O B I D E . C r y s t a l s f o r m o n l y o n stirring
in the 1 : 1 0 0 0 a n d 1 : 5 0 0 solutions, a n d t h e y are rosettes of rods, as a rule. T h e dense precipitates in the other t w o solutions crystallize quickly into large, bushy crystals (Plate I V , F i g . 6 ) .
M A Y E R ' S R E A G E N T . T h e precipitates are all heavy
with this r e a g e n t a n d crystals are formed o n l y o n stirring. T h e y are v e r y small i n all e x c e p t t h e 1 : 1 0 0 0 solution, and in this solution t h e y are o f t e n good-sized rosettes of rods.
54

M A R M E ' S R E A G E N T . A m o r p h o u s precipitates appear
which crystallize without stirring in all solutions- A dense mass of crystals are obtained in the t w o more concentrated solutions. T h e crystals in the 1 : 1 0 0 0 solution are large and polarize highly. T h e y normally have cross arms a n d j a g g e d edges.
A M M O N I U M M O L Y B D A T E . H e a v y , a m o r p h o u s precipi-
tates a n d great numbers o f small needle-shaped crystals are formed in all the solutions.
HYOSCYAMINE HYDROBROMIDE
A n alkaloidal salt labeled " D a t u r i n e S u l f a t e " g a v e same results as t h e o n e labeled hyoscyamine hydrobromide, and the chemical determinations were m a d e o n the former. S i x crystalline a n d fifteen non-crystalline precipitates were obtained.
KRAUT'S R E A G E N T . T h e heavy, amorphous precipi-
tate crystallizes s l o w l y into irregular rods in t h e 1 : 5 0 0 a n d 1 : 1 0 0 0 solutions. Crystals are larger a n d more quickly formed in the more concentrated solutions. T h e y are often in rosettes.
G O L D C H L O R I D E . T h i s is n o t a sensitive test. Amor-
p h o u s precipitates appear in all t h e solutions. C r y s t a l s of pointed rods or irregular plates, often in rosettes, are f o r m e d in t h e 1 : 5 0 solution after some time a n d o n stirring {Plate I I , F i g . 3 ) .
MERCURIC CHLORIDE.An amorphous precipitate
forms in t h e 1 : 5 0 solution only. Crystals appear only in the t w o more concentrated solutions. T h e y are large rosettes of rods polarizing brightly. S t i r the 1 : 2 0 0 solution for quick results.
P I C R I C A C I D . D e n s e r o s e t t e s o f n e e d l e s are formed
DETAILED DESCRIPTION OF TESTS slowly upon solutions o n l y .

WAGNER'S
65
stirring
the
two
more
concentrated
precipi-
REAGENT.Heavy,
amorphous
t a t e s in all t h e solutions a n d small crystals a r e q u i c k l y formed. S o m e look like those formed w i t h atropine a n d this reagent. T h e y are, as a rule, l a r g e r t h a n those f o r m e d with atropine. I n t h e 1 : 5 0 solution, besides this form, w e have l a r g e crystals of a l i g h t - g r e e n color a n d which a r e dense rosettes u s u a l l y moss-like in g e n e r a l a p p e a r a n c e ( P l a t e X I , F i g . 5 ) . S m a l l crystals a r e f o r m e d in a 1 : 2 0 0 0 solution. Z I N C - C H L O R - I O D I D E - A g e l a t i n o u s precipitate f o r m e d in a l l t h e solutions. T h e crystals are small p l a t e s a n d similar t o those formed w i t h atropine. THE OPIUM ALKALOIDS
T h e f o l l o w i n g o p i u m alkaloids w e r e s t u d i e d : M o r phine, codeine, apomorphine, apocodeine, n a r c o t i n e , n a r ceine, papaverine, thebaine, peronine, dionine a n d heroine. Several o f these alkaloids have already been discussed* MOBPHINE F o u r aqueous solutions of m o r p h i n e hydrochloride w e r e used, t h e alkaloid* being p r e s e n t o n e p a r t t o 1000, 5 0 0 , 2 0 0 , a n d 5 0 , respectively. E l e v e n n o n - c r y s talline a n d e l e v e n crystalline precipitates w e r e obtained with these solutions.
M A B M E ' S R E A G E N T . T h i s is t h e b e s t t e s t f o r m o r p h i n e .
I n all t h e solutions e x c e p t the 1 : 1 0 0 0 a g e l a t i n o u s precipitate is formed which crystallizes o u t quickly. T h i s precipi-
56
SOME MICROCHEMICAL TESTS, FOR ALKALOIDS
tate has a silvery appearance under the microscope. These crystals are rosettes of v e r y fine needles a n d are characteristic. T h e y form a dense m a s s , especially so in the more concentrated solutions. I n t h e 1 : 1 0 0 0 solution w e g e t n o precipitate, but b y a d d i n g a drop of the reagent and allowi n g t o stand for a short time, l o n g needles form aroimd the edge of the drop ( P l a t e X V I I , F i g . 5 ) .
WAGNER'S REAGENT.A very characteristic test,
though n o t so sensitive as t h e one with Marine's reagent. A heavy, amorphous precipitate i s formed in all solutions. This precipitate forms reddish-brown drops before crystallization takes place, a n d from t h e precipitate crystallization takes place very slowly. I t is often necessary t o allow t h e solution t o stand several minutes before crystals are formed. T h e crystals are large plates, reddish-brown i n color, a n d irregular in outline. O p t i m u m concentration is about 1 : 2 0 0 . W h i l e the crystals are normally as described, y e t w e o f t e n obtain rosettes of fine needles in t h e 1 : 5 0 solution, or sometimes rods. These crystals are n o t dark-brown in color, b u t are light in appearance a n d similar t o those formed b y the potassium iodide solution. S t i r w i t h a g l a s s r o d about thirty strokes as soon as reagent is added t o 1 : 50 solution if quick crystallization be desired. T h e s e crystals are n o t so large and are usually more regular in outline than when they form more slowly ( P l a t e X I , F i g . 6 ) ( 1 8 ) .
SODIUM CARBONATE.Great n u m b e r s of s m a l l crys-
tals formed in the 1 : 2 0 0 solution, without t h e formation of an amorphous precipitate. T h e s e crystals are characteristic, being sharply defined rods often i n rosettes. Crystals formed in more concentrated solutions t h a n this are fine, clear-cut, a n d characteristic, t h o u g h n o t large. T h e
D E T A I L E D DESCRIPTION O F TESTS
57
solutions m u s t be stirred for quick crystallization. N o p r e c i p i t a t e o c c u r s in s o l u t i o n s m o r e d i l u t e t h a n t h e 1 : 2 0 0 ( P l a t e X I V ,F i g .4 ) ( 8 ) .

MAYER'S R E A G E N T , A gelatinous precipitate, with a
s i l v e r y a p p e a r a n c e u n d e r t h e m i c r o s c o p e , is f o r m e d , b u t since w e h a v e n o t b e e n a b l e t o p r o v e t h a t c r y s t a l s a r c f o r m e d , t h e a p p e a r a n c e is b e s t d e s c r i b e d b y t h e p h o t o graph (Plate X V I , F i g . 3 ) . Barium-mercuric-iodide gives r e s u l t s s i m i l a r t o a b o v e . A s t h e reactions with codeine a r e q u i t e s i m i l a r t o t h i s , t h e s e r e a g e n t s a r e o n l y of v a l u e i n d i s t i n g u i s h i n g m o r p h i n e a n d c o d e i n e f r o m other alkaloids.
O T H E R T E S T S . T h e other tests for m o r p h i n e a r e n o t
sensitive a n d h a v e n o t b e e n f o u n d o f p r a c t i c a l v a l u e . T h e y a r e briefly a s f o l l o w s : P o t a s s i u m c h r o m a t e f o r m s r o d s o r r o s e t t e s of r o d s o n l y on stirring t h e 1 : 2 0 0 a n d more concentrated solutions. T h i s r e a c t i o n is n o t a t a l l sensitive, a s it is o f t e n difficult to obtain crystals on stirring t h e 1 : 2 0 0 solution ( P l a t e X X I , Fig. 5) ( 4 ) . Zinc-chlor-iodide forms a slight gelatinous precipitate, but n o crystals in t h e 1 : 2 0 0solution, a n d a dense precipit a t e w h i c h c r y s t a l l i z e s i n s t a n t l y in t w o f o r m s of c r y s t a l s i n the 1 : 50 solution. Yellow-brown, shiny crystals a r e u s u a l l y c o m m o n a n d t h e s e d o n o t p o l a r i s e . A d e n s e m a s s of needle-like c r y s t a l s is a l s o f o r m e d a r o u n d t h e e d g e o f t h e drop. These latter, j u d g i n g from their a p p e a r a n c e , a r e f o r m e d b y t h e p o t a s s i u m iodide in t h e r e a g e n t . Mercuric chloride forms large rosette-like crystals in the 1 : 5 0 solution only a n d very quickly when stirred. These crystals a r e formed without a n amorphous preeipi-
58
tate being thrown down first and are n o r m a l l y dense rosettes of rods ( P l a t e V I I I , F i g . 6 ) ( 8 ) . P o t a s s i u m iodide forms needles i n t h e 1 : 5 0 solution only and slowly. These needles are normally l o n g a n d in rosettes, and m a y often be easily seen without t h e aid of t h e microscope ( P l a t e X V I I I , F i g . 4 ) . Kraut's reagent forms very heavy, amorphous, brickred precipitates i n all solutions. Crystals are f o r m e d in the 1 : 50 solution only, and a r e f e w a n d small a n d formed from the precipitate, but only a very small part o f the p r e cipitate crystallizes. T h e crystals are very small rods a n d so infrequently formed that this reagent is worthless a s a test for morphine. P o t a s s i u m permanganate. A dense mass of v e r y s m a l l crystals noted i n more concentrated solutions o n l y a r o u n d the edges of t h e heavy precipitate which is f o r m e d . T h e s e crystals are irregular in outline and t o o small t o be of s e r vice as a test.
NABCEINE
Three solutions of narceine hydrochloride w e r e used i n dilutions of 1 : 1 0 0 0 , 1 : 500, a n d 1 : 200. N i n e crystalline and nineteen non-crystalline precipitates were obtained.
K R A U T ' S R E A G E N T . V e r y dense, a m o r p h o u s precipi-
tates are first formed. T h e crystals are beautiful l a r g e rosettes of needles a n d are v e r y characteristic, a s t h e y a r e deep-blue i n color. T h e test is n o t v e r y sensitive, a s t h e 1 : 5 0 0 solution forms crystals o n l y o n s t a n d i n g f o r s o m e time. N o crystals were formed i n the 1 : 1 0 0 0 solution. W a g n e r ' s r e a g e n t gives results similar t o t h e a b o v e ( P l a t e X I I , F i g . 1) ( 1 ) .
DETAILED DESCRIPTION OP TESTS

POTASSIUM IODIDE.The crystals are rosettes
59
of
needles o f g o o d size, blue i n color a n d f o r m e d i n small numbers i n the 1 : 5 0 0 solution, b u t m a n y are formed in the m o r e concentrated solutions. T h e crystals are like those f o r m e d w i t h K r a u t ' s solution o r w i t h W a g n e r ' s reagent ( 8 ) . Z I N C - C H L O R - I O D I D E . H e a v y , a m o r p h o u s precipitates a n d g r e a t n u m b e r s of fine, blue rosettes of needles are formed i n a l l b u t t h e 1 : 1 0 0 0 solution.
PALLADOUS CHLORIDE.Amorphous precipitates
formed i n t h e 1 : 2 0 0 solution o n l y . S m a l l rosettes or sheaves o f needles are s l o w l y f o r m e d i n all t h e solutions (Plate V I , F i g -6 ) .

P L A T I N U M C H L O R I D E . B e a u t i f u l f e a t h e r y r o s e t t e s are
formed f r o m t h e a m o r p h o u s precipitates in all solutions. T h i s is a sensitive test ( P l a t e V , F i g , 1 ) ( 1 ) ( 1 0 ) .

POTASSIUM C H R O M A T E . N o amorphous precipitates
appeared. R o s e t t e s o f needles are f o r m e d in t h e more concentrated solutions only. S t i r w i t h a g l a s s r o d for quick crystallization ( 1 ) ( 1 0 ) . P I C R I C A C I D . T h e 10 p e r cent, alcoholic solution g a v e heavy, a m o r p h o u s precipitates i n a l l t h e solutions a n d rosettes o f small plates f o r m e d o n l y in t h e 1 : 5 0 solution.
GOLD CHLORIDE.While w e h a v e a p r e c i p i t a t e i n all
solutions, c r y s t a l s were o n l y obtained i n t h e 1 : 5 0 solution after s t a n d i n g . T h e y are dense rosettes of needles. T h e p h o t o g r a p h shows v e r y clearly t h e d r o p s i n process of crystallization ( P l a t e I I , F i g . 4 ) .
POTASSIUM HYDROXIDE.There were no amorphous
precipitates, but rosettes of needles f o r m e d i n t h e 1 : 5 0 solution ( P l a t e X V , F i g . 6 ) .
60 SOME MICROCHEMICAL TESTS FOR ALKALOIDS

NABCOTINE
Solutions of narcotine hydrochloride were usedE i g h t crystalline a n d t w e n t y - s i x non-crystalline p r e cipitates were obtained.
POTASSIUM H Y D R O X I D E . I n the 1 : 1 0 0 0 solution an
amorphous precipitate which is fairly h e a v y is formed and crystals are slowly formed from this. T h e y are needles. I n the 1: 5 0 0 solution the precipitate is dense and great numbers of crystals are quickly formed. T h e y are normally rosettes of needles of g o o d size a n d d o n o t polarize brightly. I n the 1 : 2 0 0 solution t h e precipitate is very dense a n d needles in rosettes, or m o r e often in sheaf-like bundles, are formed- T h e whole precipitate crystallizes out o n standing. I n the 1 : 5 0 solution t h e precipitate crystallizes t o a dense mass of rosettes of needles o n standing. The following reagents g i v e results practically the same as the above, although there is some variation in sensitiveness of the reactions; potassium acetate ( P l a t e X I I , F i g . 5 ) ; potassium chromate; potassium cyanide; sodium carbonate ( P l a t e X I V , F i g . 5 ) ; sodium phosphate, a n d sodium phosphomolybdate ( 8 ) ( 2 ) . T h e sodium carbonate a d d e d t o t h e alkaloid in a solution of 1 : 20,000 forms a number of very fine needle crystals. W o r m l e y describes t h e crystals formed with potassium hydroxide with potassium chromate a n d those formed with potassium acetate, a n d g i v e s plates illustrating their normal form.
NICOTINE
Seven crystalline a n d eleven non-crystalline precipitates were obtained.
61
G O L D C H L O R I D E . A very h e a v y precipitate is formed
in the 1 : 1 0 0 0 solution, and this crystallizes quickly into small spherical or sheaf-like crystals. T h e y polarize poorly. I n t h e 1 : 5 0 0 solution t h e precipitate a n d crystals are as above. T h e crystals do n o t form as readily in the 1: 50 solution as they do at greater dilutions. This test is sensitive, as a n aqueous solution of about 1 : 1 5 , 0 0 0 g i v e s considerable numbers of small and characteristic crystals ( P l a t e I I , F i g . 5 ) ( 8 ) .
M E R C U R I C C H L O R I D E . T h e amorphous precipitate is
very slight in the 1 : 1000 solution a n d crystallization is slow unless the solution be stirred, w h e n crystals are formed at once. T h e y are small, clear-cut rosettes of plates and polarize but slightly. I n the more concentrated solutions the crystals are larger and form more rapidly. A 1 : 4000 solution gives a number of small crystals on stirring ( P l a t e I X , F i g . 1 ) ( 1 ) ( 8 ) .
K R A U T ' S R E A G E N T . T h e amorphous precipitate crys-
tallizes at once i n needles, often i n rosettes, u p o n stirring the 1 : 5 0 0 solution. N o crystals were obtained in the 1 : 1 0 0 0 solution. I n the t w o more concentrated solutions, the crystals are large rods, light-yellow in color a n d polarize brightly ( 8 ) .
W A G N E R ' S R E A G E N T . C r y s t a l s are obtained with diffi-
culty from t h e heavy, amorphous precipitates, especially if much of the reagent be used. N o crystals were obtained in the 1 : 1 0 0 0 solution. U s e b u t a small amount of the reagent for satisfactory results.
M A Y E R ' S R E A G E N T . G r e a t n u m b e r s of small, spheri-
cal crystals are formed from the amorphous precipitate in the t w o more concentrated solutions only. A light, amor-
62 SOME MICROCHEMICAL TESTS FOR ALKALOIDS plious precipitate is formed i n the 1 : 5 0 0 solution, but n o crystals are formed at this dilution ( 1 0 ) .
P I C R I C A C I D . T h i s is a sensitive test. T h e crystals
are large and form instantly f r o m t h e heavy, amorphous precipitate in all solutions. T h e precipitate first formed immediately dissolves unless sufficient of t h e reagent be used. S o m e crystals were obtained in the 1 : 4 0 0 0 solution and this is about the limit of reaction ( 1 ) ( 6 ) ( 1 0 ) ( 1 1 ) (12) ( 1 6 ) .
B A R I U M N I T R A T E . G r e a t n u m b e r s of small crystals
are formed at once and they polarize brightly. dumb-bell shaped.

PAPAYERINE
T h e y are
Thirteen crystalline a n d t w e n t y - t w o precipitates were obtained.
non-crystalline
P O T A S S I U M H Y D R O X I D E . A m o r p h o u s precipitates a p -
pear in all the solutions a n d these precipitates all crystallize o n standing and crystallization takes place more slowly i n the more concentrated solutions. T h e crystals are small rods or rosettes of rods often arranged i n the shape of a fan. U p o n adding this r e a g e n t t o a 1 : 1 0 , 0 0 0 solution a n d stirring, a considerable n u m b e r of small rods are formed at once. P o t a s s i u m chromate a n d also p o t a s s i u m acetate give results similar t o the above ( P l a t e X V , F i g . 5 ) .
SODIUM CARBONATE.The amorphous precipitate
crystallizes slowly unless stirred. O n standing, large rosettes of rods are formed, while o n stirring the crystals are i n small rods only. S o d i u m phosphate gives crystals similar to the above.
63
Z I N C C H L O R I D E . A l l the solutions crystallize at once.
T h e crystals are normally small rosettes of irregular plates. This appears t o be a good test, a f e w small crystals b e i n g formed in a 1 : 2 0 0 0 solution. A n amorphous precipitate first formed i n the 1 : 5 0 solution only ( P l a t e X X V I , Fig. 6).
M E R C U R I C CHLORIDE.Characteristic crystals, t h o u g h
not large ones, are formed with this reagent. T h e y a p p e a r to be cubical with rounded edges, o r often rosettes of p l a t e s in layers. A m o r p h o u s precipitates are f o r m e d i n all t h e solutions a n d these crystallize o n stirring ( P l a t e I X , F i g . 2) ( 8 ) . Other crystalline precipitates are briefly as f o l l o w s : ZINC-CHLOR-IODIDE.Crystals formed s l o w l y f r o m t h e amorphous precipitate. T h e y are normally like c r y s t a l s formed with zinc chloride.
P A L L A D O U S C H L O R I D E . S m a l l , irregular crystals are
formed from the amorphous precipitate i n t h e 1 : 2 0 0 a n d 1: 50 solutions on standing ( P l a t e V I I , F i g . 1 ) .

MAYER'S REAGENT.The amorphous precipitate is
very dense. T h e crystals are formed s l o w l y around t h e edges of the drops and are not characteristic. T h e y are small plates often i n dense masses.
M A R M E ' S R E A G E N T . T h e amorphous precipitates are
all very dense a n d the crystals are small rosettes of p l a t e s and do not form quickly. These crystals appear t o better advantage after standing some time, as t h e y g r o w larger.
F E R R I C C H L O R I D E . C r y s t a l s appear o n l y i n t h e t w o
more concentrated solutions. T h e y are rather quickly formed i n great numbers from the amorphous precipitates and appear almost square.
64

M I L L O N ' S R E A G E N T . T h e crystals formed are identi-
cal with those formed b y t h e mercuric chloride solution, but Millon's reagent is less sensitive.
P E R O N I N E ( B E N Z Y L M O R P H I N E HYDROCHLORIDE)
Three solutions o n l y w e r e used a n d they were aqueous solutions of t h e f o l l o w i n g strengths: 1 : 1 0 0 0 , 1 : 5 0 0 , and 1 : 200.
POTASSIUM IODIDE.This is a sensitive a n d satisfac-
t o r y test. L a r g e , dense rosettes of rods or needles are formed from t h e amorphous precipitates at once. M a n y goodsized crystals are formed i n t h e 1 : 1 0 0 0 solution; a n o n crystalline precipitate is n o t formed first ( P l a t e X V I I I , F i g . 5).
HYDROCHLORIC ACID.Upon adding dilute hydro-
chloric acid solution t o t h e 1 : 200 solution a n d stirring, crystals of rods, often in rosettes, are formed. T h e rods are usually notched a t t h e ends. Ferric chloride gives crystals in the 1 : 2 0 0 solution only, a n d t h e y appear like those above.
B A R I U M N I T R A T E . A m o r p h o u s precipitates a n d then
crystals are formed in t h e 1 : 2 0 0 solution only, a n d they are rods or needles, t h e rods o f t e n being notched at the ends. Silver nitrate reacts in the same manner as this reagent.
MAYER'S R E A G E N T . H e a v y , amorphous precipitates
appear in all the solutions, b u t crystals are formed from the precipitate o n l y i n t h e 1 : 2 0 0 solution. T h e y are rosettes of rods, f o r m i n g slowly b u t g r o w i n g t o a large size.
AMMONIUM THIOCYANATE.Rosettes of rods are
rather quickly formed from t h e heavy, amorphous precipitate in the 1 : 2 0 0 solution and o n stirring the 1 : 5 0 0 solution.

PHYSOSTIGMINE SULPHATE (ESERHSTE)
65
T w o crystalline a n d sixteen non-crystalline precipitates were obtained. N o sensitive test for this alkaloid w a s obtained. G O L D C H L O R I D E . A m o r p h o u s precipitates a p p e a r in all the solutions, but crystals o n l y in t h e 1: 5 0 solution. The crystals are very small and dark in a p p e a r a n c e . T h e y are formed i n great numbers from the heavy, dark-brown precipitate first produced. T h e f o l l o w i n g color reactions w e r e n o t e d : P o t a s s i u m hydroxide g i v e s a d e e p - p i n k color i n all the solutions. A m m o n i u m vanadate g i v e s a red color i n the 1 : 50 solution and this fades o u t quickly. A p i n k color is obtained i n t h e 1 : 200 solution. P o t a s s i u m cyanide gives a pink color in t h e solutions on standing. PlLOCARPIDINE Three crystalline precipitates were obtained. P H O S P H O T U N G S T I C A C I D . T h i s is the best test for this alkaloid. H e a v y , amorphous precipitates a n d o n stirring great numbers of small rosettes or needle-like crystals are formed. I f n o t stirred the crystals are f o r m e d o n l y around the edges of the drops ( P l a t e X X I V , F i g . 6 ) . P H O S P H O M O L Y B D I C A C I D . V e r y h e a v y , amorphous precipitates are formed i n all solutions. O n standing, small spherical crystals are formed. E s p e c i a l l y g r e a t numbers formed in the 1: 50 solution. T h e y do n o t polarize. P L A T I N U M C H L O R I D E . R o s e t t e s of l a r g e p l a t e s are quickly formed i n the 1: 50 solution only. N o amorphous precipitate or crystals formed in the 1 : 2 0 0 s o l u t i o n ( 1 7 ) . 5
66
SOME MICROCHEMICAL TESTS FOR ALKALOIDS PlLOCARPESTE HYDROCHLOUIDE
T w o crystalline a n d fourteen non-crystalline precipitates were obtained.

P L A T I N U M C H L O R I D E . T h e m o s t characteristic crys-
tals were obtained w i t h this reagent. T h i s is not a very sensitive test, as n o crystals were obtained i n more dilute solutions than 1 : 2 0 0 . U p o n stirring t h e 1 : 2 0 0 solution, w e g e t some crystals around t h e edges. T h e y are rosettes of irregular plates. I n the 1 : 5 0 solution great numbers of clear-cut plates are formed instantly ( P l a t e V , F i g . 2 ) ( 8 ) .
GOLD CHLORIDE.Heavy, amorphous precipitates
formed in all but t h e 1 : 1 0 0 0 solution, a n d these crystallize u p o n stirring in plates or often in rosettes ( 1 0 ) .
PIPEEIJSTE
Solutions in 90 p e r cent, alcohol were used. M a n y reagents are precipitated i n crystalline form when added t o alcohol, a n d for this reason alcoholic solutions are not as satisfactory t o work with a s aqueous or acid solutions. T h e crystals formed were i n m o s t cases similar, being rods of needles. T h e y were formed with all t h e following reagents: Mercuric chloride; platinum chloride; sodium nitro-prusside; potassium acetate; potassium ferricyanide; saccharin; potassium iodide; Marine's reagent, a n d ammonium molybdate. THE CINCHONA ALKALOIDS
Microchenrical tests were worked o u t for t h e following cinchona alkaloids: Q u i n i n e ; quinidine; cinchonine; cinchonidine, a n d quinoline. Cinchonine a n d cinchonidine have already been discussed; see p p . 3 5 a n d 3 6 .

QUININE SULPHATE
67
F i v e crystalline precipitates a n d twenty-seven n o n crystalline precipitates were obtained. N o sensitive tests f o r this alkaloid found.
S O D I U M P H O S P H A T E . T h e r e w a s n o precipitate in the
two more dilute solutions. G r e a t numbers of large, sheaf-like crystals are quickly formed in t h e 1 : 2 0 0 solution. I n t h e 1 : 50 solution w e have besides t h e sheaf-like crystals, another form. These particles are rather small, silvery i n appearance, and are present in great numbers. T h e y d o n o t polarize and are probably non-crystalline, their appearance being similar t o the particles formed w h e n M a y e r ' s reagent is added t o morphine or t o codeine ( P l a t e V I I , F i g . 6 )
POTASSIUM ACETATE.Dense masses of very fine
needle crystals or rosettes of these are formed only in t h e 1: 50 solution ( P l a t e X I I , F i g . 6 ) .

P O T A S S I U M C H R O M A T E . N o reaction in the two more
dilute solutions. B y a d d i n g sufficient of this r e a g e n t a n d stirring, w e g e t rosettes of needles at once i n t h e 1 : 2 0 0 solution. I n the 1: 50 solution t h e dense precipitate first formed crystallizes rapidly into large rosettes of rods o n stirring ( P l a t e X X I , Fig. 6 ) .
WAGNER'S REAGENT.While d e n s e precipitates are
formed in all t h e solutions, n o crystals were obtained i n any but t h e 1 : 5 0 solution. I n this solution crystallization is slow. T h e crystals are, as a rule, n o t large and do n o t polarize brightly. T h e y are n o t sharp i n outline. M u c h of t h e precipitate takes o n a deep rose-red color, this color b e i n g different from that obtained with any other alkaloid tested w i t h this reagent ( P l a t e X I I , F i g . 2 ) .
68
SOME MICROCHEMICAL TESTS FOR ALKALOIDS Kraut's reagent gives reactions similar t o t h e above.
AMMONIUM THIOCYANATE.The amorphous precipi-
tate in the 1 : 50 solution crystallizes quickly i n large, dense, moss-like crystals. T h e slight precipitate in the 1 : 2 0 0 solution forms small crystals o n stirring. T h e t w o photographs ( P l a t e X X V , F i g s . 4 and 5 ) show h o w widely the crystals m a y vary in appearance.
QUINTDINE SULPHATE
S i x crystalline a n d t w e n t y - s i x non-crystalline precipitates were obtained.

P O T A S S I U M C H R O M A T E . N o p r e c i p i t a t e s appeared in
the dilute solutions. I n t h e 1 : 50 solution a very dense, amorphous precipitate is first thrown d o w n and crystals are slowly formed. T h e y often exhibit a braided appearance.
GOLD CHLORIDE.In the 1: 500 solution, a heavy,
amorphous precipitate crystallizes at once o n stirring or slowly when n o t stirred into needles or rosettes of these. These crystals are formed i n great numbers. N o crystals appear in the 1 : 1 0 0 0 solution. Crystals do not form quickly in the more concentrated solutions ( P l a t e I I , F i g . 6) ( 8 ) .
M E R C U R I C C H L O R I D E . N o crystals are formed in a n y
solution more dilute than t h e 1 : 200. I n this solution fairsized rosettes are formed from the rather dense, amorphous precipitate. These crystals polarize brightly around the edges, but n o t in the centre ( P l a t e I X , F i g . 3 ) .
POTASSIUM I O D I D E . N o amorphous precipitate a p -
pears in the more dilute solutions. Crystals i n great n u m bers are formed at once o n stirring t h e 1 : 1 0 0 0 solution. T h e y are normally triangular i n outline. A f e w crystals were formed i n a 1 : 2 0 0 0 solution. I n
69
the more concentrated solutions the crystals are large and form quickly. T h i s reagent does not form crystals with any other of the cinchona alkaloids studied ( P l a t e X V I I I , F i g . 6) ( 8 ) .
P O T A S S I U M F E R R O C Y A N I D E . G r e a t numbers of rods
are formed quickly i n the more concentrated solutions. Their appearance is best described b y the photograph. N o precipitate appears i n t h e 1 : 1 0 0 0 solution ( P l a t e X X , Fig. 3) ( 8 ) .
A M M O N I U M T H I O C Y A N A T E . S m a l l rosettes form on
stirring a 1 : 1 0 0 0 solution. V e r y large rosettes appear in all the more concentrated solutions ( P l a t e X X V , F i g . 3 ) .
QUINOLISTE
E l e v e n crystalline a n d seventeen non-crystalline precipitates w e r e obtained.

C H R O M I C A C I D . T h i s is n o t a sensitive test, as crystals
were obtained o n l y in t h e 1 : 5 0 solution. T h e y are rosettes of leaf-like forms a n d polarize brightly. T h e amorphous precipitate is light a n d crystallizes slowly ( P l a t e X X I I I , Fig. 1 ) .
G O L D C H L O R I D E . T h i s is a sensitive test. The 1:1000
solution crystallizes out quickly into a dense mass of crystals of a g r e e n color, appearing like some form of sea-weed. T h e 1 : 5 0 0 solution is t o o concentrated t o give the best results. S o m e fair-sized needles are formed in a 1 : 5000 solution ( P l a t e I I I , F i g . 1 ) .
P L A T I N U M C H L O R I D E . N e e d l e - l i k e crystals, often in
rosettes, are obtained o n stirring t h e 1 : 1 0 0 0 solution. I n the 1 : 5 0 solution t h e crystals are i n a dense mass and small (Plate V , F i g . 3) ( 8 ) .
M E R C U R I C C H L O R I D E . T h e crystals are dense rosettes
70
in all solutions e x c e p t t h e 1 : 1 0 0 0 , in which solution there is no precipitate ( P l a t e I X , F i g . 4 ) ( 8 ) .

WAGNER'S REAGENT.Heavy, amorphous precipi-
tates and crystals are s l o w l y formed i n a l l t h e solutions. T h e y are rods a n d v a r y f r o m brown or light yellowishbrown to a dark-bluish color ( P l a t e X I I , F i g . 3 ) .
K R A U T ' S R E A G E N T . I n t h e 1 : 1 0 0 0 solution the amor-
phous precipitate crystallizes o u t quickly i n beautiful reddish-brown rosettes of needles. A 1 : 8000 solution g a v e a few very small crystals. T h e more concentrated solutions do n o t give a n y more satisfactory results t h a n the 1 : 1 0 0 0 solution ( P l a t e X I I I , F i g . 4 ) ( 8 ) .
P I C R I C A C I D . T h i s is a sensitive t e s t for quinoline.
L a r g e crystals are formed instantly i n the 1 : 1000 solution, and a very dense mass of crystals in t h e more concentrated solutions. A f e w small crystals are formed i n a 1: 3000 solution ( P l a t e X I X , F i g . 6 ) .
MAYER'S R E A G E N T . T h e p r e c i p i t a t e i n the 1:1000
or 1 : 5 0 solution does n o t crystallize. T h e crystals are normally large rods in t h e other t w o solutions.
P O T A S S I U M F E R R O C Y A N I D E . T h e c r y s t a l s are small
rods or four-sided plates with sharp angles a n d formed only in the t w o more concentrated solutions. T h e amorphous precipitate is very slight in the 1 : 5 0 0 solution ( P l a t e X X , F i g .4) ( 8 ) . P o t a s s i u m f errocyanide reacts like t h e above.
MILLON'S REAGENT.The crystals are small, dark
rosettes and formed in the t w o more concentrated solutions only. T h e y have a light-pink color w h e n in masses and this color is especially t o be seen i n the 1 : 5 0 solution ( P l a t e X X V I , Fig. 4).
DETAILED DESCRIPTION OF TESTS SCOPOLAMINE HYDROBROMIDE ( H Y O S C I N E H YDROBROMIDE )
71
S a m p l e s marked either " H y o s c i n e " or " Scopolamin " g i v e identical microchemical reactions. O n l y three crystalline precipitates were obtained. Thirteen non-crystalline precipitates were obtained. G O L D C H L O R I D E . T h i s is a sensitive test and the only one, apparently, of practical value. T h e crystals are instantly formed o n stirring the solutions, otherwise they f o r m slowly. N u m b e r s of small crystals are formed in a 1 : 4000 solution on stirring. T h e y are triangular in outline. T h e crystals g r o w t o a large size, especially i n the 1 : 2 0 0 solution. T h e y polarize brightly and are yellow i n color and n o r m a l l y are rosettes of plates with coarse, sawtooth e d g e s . T h e y are characteristic. A m o r p h o u s precipitates a p p e a r i n all t h e solutions u p t o 1 : 5 0 0 ( P l a t e III, Fig. 2) (7).
K R A U T ' S R E A G E N T . T h e precipitates are all dense.
O n s t a n d i n g t h e y all crystallize. T h e y are noticed especially around t h e e d g e s a n d are usually rosettes of rods. W A G N E R ' S R E A G E N T . C r y s t a l s are very slowly formed from the heavy, amorphous precipitates. O n stirring a sticky m a s s is formed from the amorphous precipitate and this on further stirring crystallizes rapidly into short rods, sometimes i n rosettes ( P l a t e X I I , F i g . 4 ) .
SOLANINE
N o satisfactory test w a s obtained o n this substance. T w e n t y - s e v e n amorphous precipitates were obtained.

SPARTEINE SULPHATE
S e v e n crystalline a n d fifteen non-crystalline precipitates were obtained.
G O L D C H L O R I D E . T h e o n l y very sensitive test is that with gold chloride. A great number of small, blade-like crystals which polarize fairly w e l l are formed i n t h e 1 : 1 0 0 0 solution. T h e crystals are larger b u t similar in shape in the 1: 500 solution. I n the t w o more concentrated solutions the crystals vary greatly in shape a n d size a n d are often in masses ( P l a t e I I I , F i g . 3 ) ( 1 0 ) . Z I N O C H L O R - I O D I D E . V e r y small crystals were formed in all the solutions, but the greater part of t h e precipitate does n o t crystallize. O n standing, the crystals i n t h e 1 : 1 0 0 0 solution g r o w t o a fair size. T h e y are v e r y irregular in outline.
PALLADOUS CHLORIDE.No amorphous precipitates
appear. O n standing, fine, large, spherical crystals or rosettes are formed i n t h e 1 : 5 0 solution a n d a f e w in the 1 : 2 0 0 solution. T h e y are of a deep, reddish-brown color (Plate V I I , F i g .2 ) .
P O T A S S I U M F E R R I C Y A N I D E . T h i s is n o t sensitive as a
reagent for sparteine. L a r g e plates a n d m a n y square ones are formed in the 1 : 50 solution only.
MARME'S R E A G E N T . T h e dense, a m o r p h o u s
small
precipi-
tates crystallize slowly o n standing, great numbers of crystals being formed. T h e y are rather slender rods a n d of good length.
FERRIC CHLORIDE.Great numbers of crystals are
formed around the e d g e of t h e drop in the 1 : 50 solution and a few in the 1 : 2 0 0 solution. T h e y float o n t h e liquid.
SILVER N I T R A T E . C r y s t a l s are f o r m e d i n g r e a t n u m -
bers on stirring the 1 : 5 0 solution only. small rods a n d polarize brightly.
T h e y are normally

STRYCHNINE SULPHATE
73
T w e n t y - s e v e n crystalline and five non-crystalline p r e cipitates were obtained with this alkaloid. M a n y sensitive a n d characteristic tests were worked out.
POTASSIUM HYDROXIDE.Rods n o r m a l l y with a V-
shaped recess i n each e n d are formed i n all the solutions. A few small crystals are formed i n a 1 : 20,000 solution. T h e crystals are large a n d rough i n appearance in the t w o more concentrated solutions a n d are formed from the amorphous precipitates first thrown down. Stir the more dilute solutions for quick crystallization ( P l a t e X V I , F i g . 1) ( 8 ) ( 1 ) ; Crystals similar t o t h e above are formed with ammonia and also w i t h sodium carbonate ( P l a t e X I V , F i g . 6) ( 8 ) .
SODIUM N I T R O - P R U S S I D E . N o precipitates were o b -
tained i n t h e t w o more dilute solutions. A v e r y slight precipitate appeared in the 1 : 200 solution a n d this crystallized slowly. T h e crystals are spherical and show distinct polarization crosses. I n the 1: 50 solution t h e dense, amorphous precipitate crystallizes quickly. M a n y of the crystals are spherical a n d others are rosettes of p l a t e s ( 1 0 ) .
SODIUM PHOSPHATE.Small rods formed in the
1 : 1 0 0 0 solution o n stirring. I n t h e 1 : 2 0 0 solution cubical or six-sided forms predominate. I n the 1 : 5 0 solution there are m a n y sharp, clear-cut crystals formed at once. T h e y are normally l o n g needles. L i m i t of reaction is about 1 : 2 0 0 0 , b u t a t this dilution the crystals are not characteristic.
AMMONIUM T H I O C Y A N A T E . S m a l l rods are formed
on stirring t h e 1 : 1 0 0 0 solution a n d a very dense mass of
74
crystals appear in t h e more concentrated solution ( P L X X V , F i g . 6) ( 2 ) ( 3 ) ( 8 ) . C H R O M I C A C I D . C r y s t a l s are quickly formed i n solutions from the amorphous precipitates which i thrown down in all but the 1 : 1 0 0 0 solution. T h e y a r e two kinds, the m o s t c o m m o n being rectangular, h a v i lines j o i n i n g the opposite corners. T h e y do not p o l a r i T h e other crystalline f o r m is branching a n d does not pol; ize. A t the 1: 200 dilution the last is the most comrn form of crystals. A f e w small crystals are formed ir 1 : 5 0 0 0 solution. T h e reaction of potassium dichrom* is similar to the above and w a s described by W o r m ] (Plate X X I I I , F i g . 2) (8) ( 1 ) .
POTASSIUM C H R O M A T E . R o d s sometimes in r o s e t
are formed in solutions u p t o 1 : 500 ( 3 ) ( 1 0 ) . G O L D C H L O B I D E . A dense, amorphous p r e c i p i t a t e thrown down u p o n a d d i n g the reagent. T h i s crystalli: out rapidly. T h e crystals are dense rosettes. T h e y i light-brown in color and do n o t polarize brilliantly. These crystals g r o w t o a large size e v e n in a 1 : 1 0 solution. T h e w e i g h t of the cover g l a s s is sufficient break the crystals. T h e 1: 50 solution is t o o concentrated for satisfactc results, as crystals are formed in a dense mass. Some fairly large and characteristic crystals are f o r m at a dilution of 1 : 2 0 , 0 0 0 ( P l a t e I I I , F i g . 4 ) ( 1 ) ( (8) (10). P L A T I N U M C H L O E I D E . C l e a r - c u t crystals are q u i d formed from the amorphous precipitate i n all the solutioi There is considerable variation in their appearance, t h o u all are of the same general t y p e . T h e rosette clusters fii formed break d o w n a n d assume i n m a n y instances t
75
form s h o w n i n p l a t e after three t o five m i n u t e s . I n a 1 : 1 5 , 0 0 0 solution g r e a t numbers of v e r y small crystals are formed, b u t t h e y are n o t characteristic ( P l a t e V , F i g . 4 ) (1) (8) (10) ( 1 8 ) . T h e above test, u s i n g dichloride of p l a t i n u m , w a s described b y W o r m l e y ( 4 ) .
P A I X A D O U S C H L O R I D E . T h e c r y s t a l s are l a r g e rosettes,
the arms h a v i n g a m u c h curved a n d irregular shape. T h e r e are also a n u m b e r of v e r y small crystals which float at the surface of t h e drop. A f e w small crystals are formed in a 1 : 1 2 , 0 0 0 solution. W o r m l e y states t h a t these crystals are similar t o those f o r m e d with p l a t i n u m chloride ( P l a t e V I I , Fig. 3) (1) ( 3 ) .
M E R C U R I C C H L O R I D E . T h e c r y s t a l s are f a i r l y large
a n d g r a c e f u l l y curved i n the 1 : 1 0 0 0 solution. T h e y polarize but slightly. I n t h e more concentrated solutions they are dense rosettes. A f e w crystals are f o r m e d i n a 1 : 3 0 0 0 solution ( P l a t e I X , F i g . 5 ) ( 4 ) ( 8 ) .
F E R R I C C H L O R I D E . C r y s t a l s are f o r m e d s l o w l y i n the
1 : 2 0 0 solution. T h e y are small a n d spherical. I n t h e 1 : 50 solution a dense m a s s of l a r g e needles are formed a t once. T h e r e are also g r e a t n u m b e r s of small, spherical crystals formed. T h e test is n o t sensitive.
Z I N C C H L O R I D E . G o o d - s i z e d , sheaf-like c r y s t a l s are
formed quickly i n t h e 1 : 2 0 0 solution. T h e y polarize brilliantly. N e e d l e s are formed b u t s l o w l y in t h e more dilute solutions unless t h e solution be stirred. Z I N C - C H L O R - I O D I D E . G r e a t n u m b e r s of small, dark crystals are formed in the 1 : 1 0 0 0 solution. T h e r e are t w o forms o f crystals i n t h e 1 : 2 0 0 solution, o n e like that formed with zinc chloride a n d t h e other spherical in appearance, which does n o t polarize. I n t h e 1 : 5 0 solution these crys-
76 SOME MICROCHEMICAL TESTS FOR ALKALOIDS tals are fine rosettes. T h e limit of reaction is 1 : 1 0 , 0 0 0 (Plate X X V I I , Figs. 4 and 5 ) .
WAGNER'S REAGENT.Dense precipitates appear in
all the solutions. There are t w o forms of crystals, o n e is light in color a n d appears t o float a t t h e surface; t h e other appears as large needles or rods i n masses i n the more concentrated solutions. T h e crystals formed i n a 1 : 2000 solution are small and n o t characteristic ( 1 ) . Kraut's reagent gives reaction like ahove.
POTASSIUM IODIDE.No amorphous precipitates are
formed. N e e d l e - s h a p e d crystals, often i n rosettes, are formed i n the more dilute solutions, a n d these m u s t he stirred for quick results. D e n s e rosettes of plates are formed i n t h e 1 : 5 0 solution ( 1 ) .
M A R M E ' S R E A G E N T . I n t h e 1 : 1 0 0 0 solution w e h a v e
first an amorphous precipitate which is n o t very dense, a n d from this small, silvery-looking masses, possibly crystals, are formed rather slowly. W e also have a crystal formation w h e n the solution stands for a short time. T h e s e crystals are quite different from the other forms a n d are sharp-cut rosettes of small plates. T h e y polarize brilliantly. A 1 : 25,000 solution g i v e s a f e w small crystals, but t h e y are not a t all characteristic. T h e 1 : 1 0 0 0 crystals are quite normal i n appearance ( P l a t e X V I I , F i g . 6 ) .
M A Y E R ' S R E A G E N T . A dense, amorphous precipitate
and t w o forms of crystals are formed. T h e first f o r m o f crystals floats o n the surface. T h e y are light in color, d o not polarize, a n d are n o t clear-cut. T h e other f o r m is darker, polarizes slightly a n d forms more slowly t h a n t h e first. T h e y are rosettes of needles or rods in t h e more con-
77
centrated solutions. A good number of small crystals was formed in a 1 : 2 0 , 0 0 0 solution ( P l a t e X V I , F i g s . 4 and 5) (1) ( 1 0 ) .
POTASSIUM FERRICYANIDE.Rosettes of rods or plates
appeared i n t h e t w o more concentrated solutions only (10) ( 1 5 ) ; P o t a s s i u m ferrocyanide forms crystals similar t o above, but the reaction is more sensitive ( 8 ) ( 1 0 ) . P O T A S S I U M C Y A N I D E , G r e a t numbers of rods often in rosettes f o r m e d i n all the solutions. A f e w small crystals were formed i n a 1 : 3000 solution. Stir the solutions for quick results. P H O S P H O M O L Y B D I C A C I D . C r y s t a l s formed only in the 1 : 5 0 solution. T h e y are large rods of dense masses a n d m u c h of the heavy, amorphous precipitate does not crystallize. S o d i u m phosphomolybdate gives results like the above. S A C C H A R I N . A f e w small crystals are formed on stirring a 1 : 2 0 0 solution. A very dense, amorphous precipitate is f o r m e d i n t h e 1 : 50 solution. T h i s turns into oillike drops which soon crystallize into plates in rosettes. T h e y are f o r m e d slowly unless the solution be stirred. P I C R I C A C I D . T h e crystals are large, g r e e n rosettes gracefully curved and are formed in all the solutions from the amorphous precipitates. Crystals are formed on stirr i n g a 1 : 1 0 , 0 0 0 solution ( P l a t e X X , F i g . 1) ( 1 ) ( 6 ) (10) (11) ( 1 2 ) . M I L L O N ' S R E A G E N T . R o s e t t e s of needles appear in the 1 : 5 0 solution only. A few small crystals normally sixsided are sometimes formed in the 1 : 5 0 0 solution. T h e f o l l o w i n g color reaction w a s noted. A m m o n i u m vanadate p r o d u c e d a pink coloration in all the solutions.
78 SOME MICROCHEMICAL TESTS FOR ALKALOIDS

THEBAISTE
F o u r crystalline and t w e n t y - s i x non-crystalline precipitates were obtained.

P O T A S S I U M H Y D R O X I D E . G r e a t n u m b e r s of small rods
are formed i n the 1 : 1000 solution. T h e y polarize brightly. I n the more concentrated solutions t h e crystals are rosettes of plates or rods formed from t h e amorphous precipitate. T h e same crystal forms as above are g i v e n with sodium carbonate or potassium cyanide ( P l a t e X V I , F i g . 2 ) ( 8 ) .
P L A T I N U M C H L O R I D E . T h e best crystals are obtained
by using a very small amount of this reagent and in the 1 : 5 0 solution only. T h e y are fine needles i n rosettes or sheaves. I n more dilute solutions crystallization is poor and the crystals are small a n d spherical ( 1 0 ) .
THEOBROMINE
N o satisfactory microchemical tests were obtained. N o t being soluble i n water or i n dilute hydrochloric acid, a dilute solution i n 10 p e r cent, potassium hydroxide was used, but i n order to obtain the f o l l o w i n g crystals t h e drop of the solution m u s t be allowed t o d r y d o w n and thus become more concentrated before a p p l y i n g t h e reagent.
G O L D C H L O R I D E . A d e n s e m a s s of l i g h t - g r e e n , n e e d l e -
like crystals are formed.

KRAUT'S R E A G E N T . A dense m a s s of dark, reddish-
brown needles or small p l a t e s is formed. Sometimes t h e crystals are small and spherical. A pink color is developed around the edge of t h e drop.
P I C R I C A C I D . W i t h alcoholic s o l u t i o n r o d crystals are
formed at once on stirring all solutions. precipitates formed.
N o amorphous
DETAILED DESCRIPTION OP TESTS

TROPACOCAINE HYDROCHLORIDE
79
T w e n t y crystalline and only four non-crystalline precipitates were obtained. C H R O M I C A C I D . T h e limit of reaction is about 1: 2000. A t this dilution a f e w small crystals are formed on stirring. Small, diamond-shaped crystals are formed o n stirring the 1 : 1 0 0 0 solution. T h e y are very brilliant under polarized light. T h e t w o more concentrated solutions give beautiful large rosettes of plate-like forms. Amorphous precipitate formed i n the 1 : 5 0 solution only ( P l a t e X X I I I , Fig. 3).
G O L D C H L O R I D E . T h i s is a v e r y sensitive t e s t , as a con-
siderable number of small crystals are formed i n a 1: 30,000 solution o n stirring. Crystals form at once in t h e 1 : 1 0 0 0 solution. T h e y are fairly large and clear-cut. A f e w crystals float at the t o p of the drop. T h e y all have a rather rough-appearing surface. T h e crystals are of the same general form, but they are much larger w h e n the drop is not stirred. T h e more concentrated solutions form dense masses of crystals at once from the amorphous precipitate (Plate I I I ,Fig. 5 ) ( 1 5 ) .
P L A T I N U M C H L O R I D E . T h i s is a sensitive test. Beau-
tiful large crystals are formed i n the more dilute solutions. These crystals normally have cross-arms f o r m i n g an acute angle one with another. T h e crystals are produced in such masses that their form is n o t perfect i n more concentrated solutions. A f e w very small crystals are formed i n a 1 : 2 0 , 0 0 0 solution ( P l a t e V , F i g . 5 ) ( 1 5 ) .
P A L L A D O U S C H L O R I D E . T h i s is another sensitive test
for tropacocaine. Crystals formed in all t h e solutions vary in shape. N o r m a l crystals have a very short cross-arm at
80
SOME MICROCHEMICAL TESTS FOE ALKALOIDS
an acute angle t o the m a i n axis. Solutions of 1 : 1 0 0 and under are t o o concentrated f o r best results. N u m b e r s of small crystals are f o r m e d i n a 1 : 4 0 0 0 solution ( P l a t e VII, Fig.4).
MERCURIC CHLORIDE.Small, jagged crystals are
formed o n stirring a 1 : 5000 solution. Solutions under 1: 100 are too concentrated a n d over 1 : 1 0 0 0 too dilute for satisfactory crystal formation. I n t h e 1: 200 solution the crystals are normally v e r y large a n d j a g g e d plates in rosettes ( 5 ) .
F E R R I C C H L O R I D E . C r y s t a l s a p p e a r in the t w o more
concentrated solutions only. I n a 1 : 100 solution an amorphous precipitate is formed which is at once redissolved, but b y adding sufficient of the reagent the precipitate finally does n o t dissolve b u t crystallizes out in moss-like forms. T h e crystals are of the same general type, but somewhat smaller o n stirring the solution.
Z I N C C H L O R I D E . C r y s t a l s are f o r m e d in the more con-
centrated solutions only. T h e y are rods or are diamondshaped and formed in g r e a t numbers on stirring; 1 : 2 0 0 is about the limit of reaction. Z I N C - C H L O R - I O D I D E . T h i s test is sensitive, crystals being formed i n a 1 : 5 0 0 0 solution. T h e crystals are similar to those formed with zinc chloride ( P l a t e X X V I I , Fig. 6 ) .
W A G N E R ' S R E A G E N T . T h i s is another sensitive test for
this alkaloid. I n the 1 : 1 0 0 0 solution, a n amorphous precipitate is formed which settles d o w n u p o n the slide and after a time beautiful, clear-cut crystals of a light-yellow color are formed. T h e y d o n o t f o r m rapidly i n all cases and vary considerably i n shape. I n the 1 : 5 0 0 solution the crystals
DETAILED DESCBIPTTON OF TESTS
81
which form first float o n t o p of t h e drop, then darker crystals form which are usually a cluster of needles; 1 : 5 0 is too concentrated for t h e best results. Great numbers of crystals are formed in a 1 : 5000 solution. Kraut's reagent gives results like the above ( P l a t e X I I I , Fig. 5).
P O T A S S I U M I O D I D E . M a n y p l a t e s are formed i n all t h e
solutions, but t h e y are small i n t h e 1 : 1 0 0 0 solution a n d form slowly o n stirring.

M A R M E ' S R E A G E N T , T h e c r y s t a l s are moss-like i n a p -
pearance. T h e test is sensitive, crystals being formed o n stirring a 1 : 20,000 solution. I n t h e 1 : 1 0 0 0 solution the dense, amorphous precipitate forms crystals slowly unless the drop be stirred ( P l a t e X V I I I , F i g . 1 ) .
M A Y E R ' S R E A G E N T . O n s t i r r i n g t h e 1 : 1 0 0 0 solution,
small crystals are formed in g r e a t numbers. T h e y are of t w o kinds, t h e lighter colored ones float o n the surface; t h e others are dark a n d appear as i n t h e photograph. T h e limit of reaction is about 1 : 2 0 , 0 0 0 ( P l a t e X V I , F i g . 6 ) .
P O T A S S I U M F E R R I C Y A N I D E . T h e limit of reaction is
about 1 : 2 0 0 . L a r g e plates are f o r m e d from the amorphous precipitate in this solution, b u t n o t quickly unless stirred. T h e s e crystals are v e r y brilliant under polarized light.
P O T A S S I U M F E R R O C Y A N I D E . C r y s t a l s are formed o n l y
in the concentrated solutions. T h e y are normally clear-cut rods or plates a n d polarize brilliantly.
POTASSIUM PERMANGANATE.Crystals are formed
quickly from the amorphous precipitate i n the 1 : 1 0 0 0 solution. T h e y are purple in color a n d appear t o be made u p of a number of thin plates o n e u p o n t h e other ( P l a t e X X I I I , F i g . 6 ) ( 1 5 ) . T h e crystals normally have a v e r y
82
graceful, wing-like appearance. T h e crystals that are formed when t h e solution is stirred are usually rectangular in form, often with a V - s h a p e d recess in either or both ends; 1: 4000 appears t o be near t h e limit of reaction. P I C R I C A C I D . C r y s t a l s are quickly formed from the amorphous precipitate i n the 1 : 1 0 0 0 solution. T h e y are normally rosettes, but variations from the normal form occur according t o t h e a m o u n t of r e a g e n t used,. T h e weight of the cover-glass is sufficient t o break the crystals. Crystals in the t w o more concentrated solutions form more slowly. A f e w small crystals are f o r m e d i n a 1 : 8000 solution. W i t h a n alcoholic solution of this reagent a f e w small needles are formed in a 1 : 2 0 , 0 0 0 solution ( P l a t e X X , Fig. 2) ( 1 5 ) . M I L L O N ' S R E A G E N T . A dense, crystalline precipitate is formed in a 1 : 5 0 solution. T h e y show m a n y colors and polarize brightly. B l a d e - l i k e rosettes are the normal forms. N o crystals or precipitates form in the more dilute solutions.
S O D I U M N I T R O - P R U S S I D E . N o reaction i n the more
dilute solutions. L a r g e crystals are formed in a 1 : 1 0 0 solution. T h e s e crystals have a very rough-appearing surface and m a n y fine needles p r o j e c t i n g f r o m this give the crystals a cactus-like appearance.
A M M O N I U M T H I O C Y A N A T E . T h e slight, amorphous
precipitate in the 1 : 50 solution crystallizes o n stirring at once into fine plates often i n rosettes. T w e n t y different tests for tropacocaine were tried on a mixture of this alkaloid and some other alkaloid in equal amounts. I n this w a y forty different alkaloids were tested with tropacocaine. T h i s makes a total of eight hundred tests. T h e results obtained were as follows: T h e test for
83
tropacocaine w a s n o t affected in 450, or 56 p e r cent., of the cases; w a s slightly affected i n 84, or 15 p e r cent., and w a s spoiled i n 266, or 2 9 p e r cent., of the total tests made. S o m e reactions are n o t affected h y the presence of another alkaloid and others are v e r y easily spoiled. I f both alkaloids i n a m i x t u r e precipitate with the reagent used, the test is m o s t likely t o be spoiled. I t appears that often the a m o u n t of r e a g e n t used has more effect on the shape of the crystal t h a n the presence of another alkaloid.
YOHIMBINE H Y D B O C H L O B I D E
One crystalline precipitate o n l y a n d twenty-eight amorphous precipitates were obtained. P O T A S S I U M C Y A N I D E . R o s e t t e s of crystals of good size are formed f r o m the amorphous precipitates, but they form very slowly and in the 1 : 2 0 0 solution only. T h e y show distinct polarization crosses ( P l a t e X X I , F i g . 3 ) . T h e f o l l o w i n g color reactions were n o t e d : Froehde's reagent g i v e s a deep-blue color i n the 1: 200 solution which, on standing, changes to green. Millon's reagent gives a y e l l o w color on standing.
CHEMICAL EXAMINATIONS
D I V I S I O N OF D R U G S
T h e following tests a n d observations bearing u p o n the question of the authenticity a n d p u r i t y of the alkaloids used in this work were m a d e . T h e authorities cited are : A L L E N : " Commercial Organic A n a l y s i s " (fourth edition), 1909-14.
BRUHL, HJELT and A S C H A N : "Die Pflanzen-Alka-
loide," 1900. H E N R Y : " T h e P l a n t Alkaloids," 1 9 1 3 . P I C T E T - B I D D L E : " V e g e t a b l e Alkaloids," 1904. R O S E N T H A L E R : " D e r N a c h w e i s Organischer V e r bindungen," 1 9 1 4 . S C H M I D T : " Pharmaceutische Chemie " (fifth edition), 1911. " U n i t e d S t a t e s P h a r m a c o p o e i a " (eighth edition, rev i s e d ) , 1905.
W I N T E R S T E I N A N D T R I E R : " D i e A l k a l o i d e , " 1910.
Reference is m a d e t o these works for the details of pharmacopoeial tests a n d other w e l l - k n o w n tests a n d reagents. I t m a y be mentioned, however, that b y Mecke's (Lafon's) reagent is understood a 0.5 p e r cent, solution of selenious acid i n sulphuric acid. T h e centigrade thermometer w a s u s e d in reading all temperatures. Aconitine, potent. Merck, crystals. Crystalline powder presenting some rhomboidal and prismatic fragments. M . P . , 1 9 0 , heated rapidly t o 185, t h e n 1 p e r minute.
84
85
( U . S . P . states M . P . 195 if rapidly heated, but 182 with decomposition if slowly heated. H e n r y , 1 9 7 - 8 . W i n t e r s t e i n a n d Trier, 1 9 7 - 8 . P i c t e t quotes D u n s t a n , 1 8 9 - 1 9 0 and F r e u n d and Beck, 1 9 7 - 8 ; Briihl, when rapidly heated, 1 9 7 - 8 ; Rosenthaler, 1 9 7 - 8 ; Schmidt quotes E h r e n b e r g and P u r f u r s t , 1 9 4 . ) W i t h sulphuric acid and a m m o n i u m vanadate gave an orange color. O n w a r m i n g with sulphuric acid the solution w a s at first colorless, carbonizing o n prolonged heating. G a v e n o Vitali reaction. W a s dextrorotatory; the hydrochloride w a s lsevorotatory. T h e 1 : 1 0 0 0 solution of the sulphate g a v e with N / 1 0 potassium p e r m a n g a n a t e a precipitate barely perceptible under t h e microscope. A n h a l o n i n e H y d r o c h l o r i d e , Merck. M . P . 181-2. (Schmidt, 2 5 4 - 5 . ) T h e nearly colorless solution i n sulphuric acid did not become colored o n w a r m i n g . Sulphuric acid with a trace of nitric acid produced a violet-red color f a d i n g t o brown. N i t r i c acid produced a reddish-purple color fading out and not becoming blood-red, as stated b y Schmidt. Apocodeine Hydrochloride, Merck. M . b e t w e e n 150 a n d 1 6 0 ; not sharp. ( S c h m i d t states that its properties are similar to those of apomorphine.) I t s solution did not turn blue or black with ferrous sulphate solution. U p o n shaking its acetic acid solution with potassium
86 SOME MICROCHEMICAL TESTS FOR ALKALOIDS iodate and ether and diluting with water, the ether f o r m e d a greenish layer. On adding 10 per cent, solution of ferric chloride t o the water solution it turned brown. The substance with Marquis' reagent produced n o color; Mecke's reagent produced a dirty-green color t u r n ing black; Froehde's reagent produced a dark-blue, becoming greenish-black. Apomorphine Hydrochloride, Merck, Crystals. M . 205-210, decomposing with a dark color. ( U . S . P . decomposes between 200 and 210.) U . S . P . tests: W h e n shaken with 100 parts of water, the latter acquired no green color. Conformed to the color tests of the U . S . P . except t h a t with sulphuric acid and paraldehyde, the color was g r e e n ish-yellow rather than green. A l s o , dilute ferric chloride solution gave not a red color, but violet, changing t o purple. Ferric chloride, T . S . U . S . P . 8 , g a v e first a p u r p l e and, as more was added, a deep-red color. Arecoline Hydrobromide, Merck. M . P . , 168-170. (Henry, 1 6 7 - 8 . Crystallized from alcohol. Schmidt, 1 6 7 - 8 ; crystallized from alcohol. Briihl, 1 6 7 - 8 ; crystallized from alcohol. Rosenthaler, 170.) Water solution g a v e no precipitate with tannic acid. Aspidospermine, Merck. Crystals according to Fraude. M.P., 205-6. (Schmidt, 2 0 5 - 6 ; Pictet, 2 0 5 - 6 ; H e n r y , 2 0 5 - 6 ; Briihl, 2 0 5 - 6 ; Winterstein, 2 0 5 - 6 ; Rosenthaler, 2 0 5 - 6 . ) The solution in dilute sulphuric acid being boiled w i t h
87
a small a m o u n t of potassium chlorate assumed a fuchsin red color. O n evaporating with platinic chloride and hydrochloric acid, a violet-purple residue w a s left. O n triturating w i t h sulphuric acid and a little lead peroxide, the mixture t u r n e d brown, then red. A t r o p i n e Sulphate, Merck. M.P., 189-190. D r i e d first at 1 2 0 , then over sulphuric acid. ( U . S . P . , M . P . , about 189.9. I f free f r o m hyoscyamine about 1 8 8 . H e n r y , about 189.9. Schmidt, about 183. Rosenthaler, about 180 dry.) U . S . P . tests: G a v e Vitali's reaction. T h e solution in water gave no precipitate w i t h either platinic chloride or g o l d chloride, but w h e n the alkaloid w a s extracted and converted into the hydrochloride, its solution g a v e n o precipitate with platinic chloride, but a copious one with g o l d chloride. T h e chloraurate melted at 1 3 7 . B e n z o y l E c g o n i n e , Merck. Crystals appeared efflorescent. M . P . , not sharp, about 1 7 5 . A f t e r drying, M . P . , 1 9 1 - 2 , fairly sharp. (Schmidt, 8 6 - 7 ; anhydrous, 1 9 5 ; H e n r y , 8 6 ; anhydrous, 1 9 5 ; B r u h l , 8 6 - 7 ; anhydrous, 1 9 5 ; Pictet, 9 2 ; anhydrous, 1 9 5 ; W i n t e r s t e i n , anhydrous, 195.) Chloraurate, air-dry, m e l t e d 2 0 7 - 8 . Berberine, K a h l b a u m . G r a d u a l l y darkened above 150 to black, melting above 2 0 0 . ( S c h m i d t about 1 4 0 ; B r u h l , 1 4 5 , decomposing above 150. W i n t e r s t e i n , about 150, dry. H e n r y , M . P . , indefinite, d e c o m p o s i n g above 1 1 0 , liquid o n l y at 160 with
88 SOME MICEOCHEMICAL TESTS FOR ALKALOIDS decomposition. Pictet, melts at 120, anhydrous. R o s e n thaler states that the base known in the solid form is not berberine (hydroxide) but berberinal, M . P . , 144.) W a t e r solution neutral to litmus. Formed with sulphuric acid a yellow solution becoming olive-green, then brown. Formed with nitric acid an orange solution immediately becoming brown. U p o n adding bromine water drop by drop to the water solution of the alkaloid the precipitate first formed dissolved, on shaking, to a reddish-brown solution; further addition of bromine water produced a brown precipitate, dissolving on warming to a red solution. The acetic and sulphuric acid solution of the alkaloid on treatment with zinc was nearly decolorized. O n making this solution alkaline with ammonia and shaking out with ether or chloroform the evaporation residue was brownish-yellow, amorphous, and partly soluble in water. Betaine Hydrochloride, Merck. M . P . , about 235-6 with decomposition. (Schmidt, with decomposition, 2 1 3 - 1 5 ; Rosenthaler, with decomposition, 2 2 7 - 8 . ) The chloraurate, recrystallized with hot water, began to soften about 190, melted entirely with sudden evolution of gas at 2 4 5 - 8 . (Schmidt, vol. ii, P a r t I , p . 450 [ 1 9 1 0 ] , states that the chloraurate recrystallized from hot 1 per cent, hydrochloric acid, melts at 248, from hot water, 209.) Brucine, Merck, R e a g e n t . Softened at 173. MJP., 1 7 6 - 7 . D r i e d at 110. (Henry, M . P . , anhydrous, 1 7 8 ; Pictet, M . P . , anhydrous, 178; Schmidt, M . P . , anhydrous, 1 7 8 ; Briihl, M . P . , anhydrous, 178; Rosenthaler, M . P . , anhydrous, 178.)
89
W i t h nitric acid a blood-red color w a s p r o d u c e d gradually f a d i n g t o y e l l o w . O n a d d i n g stannous chloride it became p u r p l e . Caffeine. M.P., 231-2. ( U . S . P . , sublimes about 1 7 8 ; dried at 100 to constant weight, m e l t s at 2 3 6 - 8 . Schmidt, begins to sublime a little about 1 0 0 , melts at 2 3 0 - 5 . W i n t e r s t e i n , sublimes at 2 2 1 , m e l t s d r y at 2 3 4 . H e n r y , sublimes at 176, m e l t s d r y at 2 3 4 - 5 . P i c t e t , m e l t s dry 2 3 4 - 5 . Rosenthaler, m e l t s dry 2 3 4 - 5 . ) D i s s o l v e d in sulphuric acid a n d in nitric acid without production of a n y color. M u r e x i d e test positive. Sulphuric acid with potassium dichromate produced a yellowish-green color, becoming green. I t s solution w a s not precipitated b y M a y e r ' s reagent. Calycanthine Sulphate. M.P., 223-4. T h e substance w i t h nitric acid g a v e a g r e e n color. Sulphovanadic acid g a v e a blood-red color. Sulphuric acid containing a little potassium dichromate g a v e a blood-red color, finally b e c o m i n g greenish. Froehde's reagent g a v e a yellow color, finally becoming red. Chelidonine, Merck. M . P - , 1 4 5 - 1 5 0 , not sharp. (Henry, 135-6. Pictet, 1 3 5 - 6 . Schmidt, 136. W i n t e r s t e i n , 1 3 6 . Rosenthaler, 1 3 5 - 6 . ) T h e solution i n w a r m alcohol, slightly acidified with H C 1 , w a s precipitated w i t h gold chloride. B r o w n precipitate of microscopic prisms or needles. M . P . , 1 9 2 - 3 .
90 SOME MICROCHEMICAL TESTS FOR ALKALOIDS Sulphuric acid turned t h e p o w d e r black and the liquid finally became faint violet. Sulphuric acid with a trace of nitric acid g a v e a brown color fading to yellow. T h e mixture with sugar and water, to which, after a few minutes, sulphuric acid was added, turned purplish-brown. Froehde's reagent g a v e a dirty-green color, becoming grass-green, then dirty-green- Sulphovanadic acid g a v e a light-green color, becoming dark-green, then dirty-green. Cinchonidine Sulphate, Bullock and Crenshaw. M.P., 205-6. ( U . S . P . , loses water of crystallization at 1 0 0 , darkens at 203, melts 205.3.) U . S . P . tests: T h e 1 : 1 0 0 0 solution in dilute sulphuric acid was very slightly fluorescent. T h e substance treated with sulphuric acid gave no color; on a d d i n g potassium chromate turned yellowish-green, then green. O n treating 0.5 g r a m with water and Rochelle salt and filtering, the filtrate g a v e no precipitate with one drop of ammonia water. ( N o excess of cinchonine or quinidine sulphate.) T h e aqueous solution w a s slightly alkaline to litmus, lsevorotatory. I n the solution barium chloride produced a precipitate insoluble in hydrochloric acid. T h e base precipitated b y ammonia was o n l y slightly soluble in ammonia, but quite so in ether. Cinchonine Sulphate, F e i d t . M.P., 198-9. U . S . P . M . P . , 198.5. T h e 1 : 1 0 0 0 aqueous solution w a s slightly alkaline to litmus, dextrorotatory, not perceptibly fluorescent, but be-
91
came so on addition of a f e w drops of sulphuric acid. T h e aqueous solution w i t h barium chloride g a v e a white precipitate insoluble in hydrochloric acid. T h e substance was nearly soluble i n 80 parts of chloroform a n d was not discolored by sulphuric acid. Cocaine Hydrochloride. M . R , 1 8 8 - 9 . ( U . S . P . , about 1 8 9 . 9 ; Briihl, 181.5; when quite pure, 2 0 1 - 2 ; H e n r y , 1 8 6 ; Rosenthaler, 1 8 3 ; Schmidt, 1 8 6 , anhydrous.) U . S . P . tests: T h e aqueous solution g a v e with silver nitrate white precipitate insoluble in nitric acid. O n a p p l y i n g the U . S . P . test for excess of isatropyl cocaine, a crystalline precipitate was obtained, the supernatant liquid not appearing opalescent, but still not perfectly clear, o w i n g to some precipitate remaining in suspension. O n a p p l y i n g the test with potassium p e r m a n g a n a t e , the color did n o t fade in one-half hour. O n heating with sulphuric acid, vapors of benzoic acid escaped. Codeine S u l p h a t e Crystals, U . S . P . , Mallinckrodt. B e g a n to t u r n brown about 2 1 5 - 2 2 0 . M . P . , 2 7 7 . ( U . S . P . , loses water of crystallization at 100, decomposes above 2 0 0 , residue melts 2 7 8 ; H e n r y , M . P . , 278 dec.) U . S . P . tests: T h e aqueous solution was neutral to l i t m u s ; with barium chloride formed a white precipitate insoluble in H C 1 . W i t h p o t a s s i u m ferricyanide and ferric chloride no blue color a p p e a r e d at once. O n a d d i n g t o the substance sulphuric acid, no color
92
appeared in the cold, on w a r m i n g the solution became violet, and on further a d d i n g nitric acid, red. Mecke's reagent produced a g r e e n color, turning blue and then green. Marquis 5 reagent produced a violet color, turning blue. Colchicine. D r i e d over sulphuric acid, n o sharp M . P . Softened at 135, but was not in clear fusion at 160. ( U . S . P . , dried over sulphuric acid, M . P . , 1 4 2 . 5 ; Winterstein, no sharp M . P . , 1 4 3 - 7 ; P i c t e t , 1 4 5 ; Schmidt, 1 4 5 ; Briihl, quite dry, 1 4 3 - 7 ; H e n r y , dry, 1 4 3 - 7 ; Rosenthaler, about 145.) U . S . P . tests: T h e aqueous solution w a s yellow, neutral to litmus and laevorotatory. T h e substance with sulphuric acid g a v e a yellow solution which nitric acid turned greenish-blue, then red, then yellow. O n adding excess of potassium hydroxide it became red. T h e substance on boiling with hydrochloric acid and ferric chloride formed a y e l l o w solution, becoming green, which imparted a reddish color t o chloroform when shaken with same. Coniine, Merck, P u r e . Light-brown, mobile liquid. Dextrorotatory in alcoholic solution. T u r n e d litmus paper blue, leaving n o f a t t y stain. T o the alcoholic solution a little carbon bisulphide w a s added and the mixture w a s w a r m e d . I n one portion of this, copper sulphate 0.1 t o 0.2 per cent, solution produced a brown precipitate, soluble in ether; in another portion ferric chloride solution produced a brown color soluble in ether; in another, uranium nitrate solution produced a red color soluble in toluene.
93
A w a t e r solution of the hydrochloride on evaporation left a residue of rush-like crystals. O n a d d i n g to a solution of the same sodium hydroxide solution a n d distilling with steam, an alkaline distillate, with an odor of coniine, was obtained. Corydaline Alkaloid, Merck. M.P., 127. ( S c h m i d t , 1 3 4 - 5 ; Pictet, Briihl, 1 3 4 - 5 ; Winterstein, 1 3 4 - 5 ; H e n r y , 135.) T h e alcohol solution was dextrorotatory. Froehde's reagent g a v e a dark-blue color, becoming dirty-green. Sulphovanadic acid g a v e a blue color, becomi n g bluish-gray. Cytisine Hydrochloride, Merck. M . P . n o t below 2 8 0 . T h e aqueous solution was laevorotatory. O n m a k i n g the solution alkaline with ammonia, shaking out with chloroform and evaporating the chloroform in several portions, the residue on adding ferric chloride turned brown, becoming a dirty-blue on adding a few drops of h y d r o g e n peroxide. O n warming on the water bath this became yellow. On w a r m i n g another portion of the residue with 2 c.c. nitric acid, it turned yellow, and on dilution with water no precipitate appeared. D a t u r i n e Sulphate, Merck. D r i e d at 100, M . P . 2 0 0 ; dried at 120, M . P . 2 0 4 - 5 . ( H e n r y states that the alkaloid from stramonium fruits is identical with atropine; likewise Schmidt and W i n t e r s t e i n . Briihl states that the identity, though questioned, is n o w admitted.) G a v e Vitali's reaction. T h e aqueous solution was
94
laevorotatory. T h e solution with barium chloride g a v e a white precipitate insoluble in hydrochloric acid. T h e properties indicate that this is hyoscyamine sulphate rather than atropine sulphate. Dionine, Merck. M . P . , 1 2 3 - 5 . ( H e n r y , M . P . , 1 2 3 - 5 ; Rosenthaler, begins to melt 110, transparent 120,) G a v e Pellagri's reaction. W i t h Froehde's reagent, yellowish-green color, becoming blue. Marquis' reagent, bluish-purple. T h e aqueous solution u p o n addition of silver nitrate gave a white precipitate, insoluble in nitric acid. E c g o n i n e A c i d Hydrochloride, R h o m b s . M.P., 245-250. H e n r y , E c g o n i n e hydrochloride, rhombs, 2 4 6 ; (d) E c g o n i n e hydrochloride, rhombs, monoclinic prisms, 2 3 6 ; (dl) E c g o n i n e hydrochloride, rhombs, slender needles; dry, 149 with dec.; Bruhl, rhombic tables, 2 4 6 ; (d) E c g o n i n e hydrochloride, rhombs, 2 3 6 . ) A portion was dissolved in a m i n i m u m amount of water, platinic chloride added and t h e n absolute alcohol and allowed to stand. T h e s c a n t y precipitate w a s washed three times b y decantation with absolute alcohol and dried at 1 4 0 - 1 4 5 , and then over sulphuric acid in a desiccator for several days. M . P . , 2 0 9 - 2 1 0 . A l l e n , " Commercial O r g a n i c A n a l y s i s , " 1912, 6, 338, states that B 2 H 2 P t C l 6 melts at 2 2 6 . H e r o i n e ( D i a c e t y l m o r p h i n e H y d r o c h l o r i d e ) Mallinckrodt. M . P . , 2 2 5 - 6 . ( S e e Schmidt , P a r t 2, 1716.) T h e substance with Froehde's reagent g a v e a purple color; with Marquis' r e a g e n t a p u r p l e color; with Mecke's re-
95
agent a g r e e n color like morphine; w i t h nitric acid a yellow color turning green. O n w a r m i n g with sulphuric acid and alcohol the odor of ethyl acetate w a s perceptible. T h e aqueous solution with ferric chloride g a v e no blue color; with silver nitrate a white precipitate insoluble in nitric acid; barium chloride, n o precipitate. H o m a t r o p i n e Hydrobromide, Powers-WeightmanRosengarten. M . P . , 2 0 9 - 2 1 0 . A sample of Mallinckrodt's, M . P . , 2 0 8 - 9 . ( U . S . P . , 2 1 3 - 8 ; H e n r y , 213.8.) U . S . P . tests: T h e aqueous solution was neutral to l i t m u s ; not precipitated b y tannic acid or platinic chloride. I n it iodine solution produced a brown precipitate, silver nitrate a white precipitate, insoluble in nitric acid. O n adding to it chlorine water and shaking with chloroform, the latter was colored brown b y free bromine. T h e substance g a v e n o Vitali reaction. O n treating it with sulphuric acid containing a trace of potassium dichromate a transient pink color appeared which w a s slowly replaced by green. O n m a k i n g the aqueous solution alkaline w i t h potassium hydroxide, shaking out with ether and evaporating the latter, the residue was not crystalline, but rather semiliquid and sticky. KTo M . P . of the free alkaloid was obtainable. T h e alkaloid turned yellow and then red on warming with mercuric chloride solution, as stated by U . S . P . Hydrastine Merck-Alkaloid-Highest Purity. M . P . , 131. ( U . S . P . , 131; Winterstein, 132;
96
Pictet, 1 3 2 ; Briihl, 1 3 2 ; Schmidt, 1 3 2 ; H e n r y , 1 3 2 ; Rosenthaler, 132.) U . S . P . tests: A l k a l i n e t o litmus. T h e chloroform solution was laevorotatory. Sulphuric acid produced a y e l l o w color, becomi n g purple on heating. Froehde's r e a g e n t produced a green color, c h a n g i n g to b r o w n ; nitric acid produced a reddish-yellow color; M e c k e ' s r e a g e n t produced a red, changing to b r o w n ; sulphuric acid with potassium dichromate, a red color c h a n g i n g to brown. T h e sulphuric acid solution on addition of potassium permanganate acquired a blue fluorescence. H y d r a s t i n i n e Hydrochloride, M e r c k . M . P . , not sharp; softens about 1 9 3 ; M . P . , about 198. (Schmidt, 2 1 2 ; H e n r y , 2 1 2 ; Rosenthaler, 210.) U . S . P . tests: T h e aqueous solution g a v e a blue fluorescence and was slightly alkaline to l i t m u s ; w i t h bromine water g a v e a yellow precipitate soluble in ammonia. P o t a s s i u m dichromate solution produced a precipitate soluble on heating and crystallizing o u t a g a i n o n cooling. A m m o n i a water produced no precipitate. Sodium hydroxide produced a transient turbidity followed by a precipitate on standing. T h e substance with sulphuric acid g a v e o n l y a faintyellow color; with nitric acid a yellowish color; with sulphuric and nitric acids a red color. Sulphuric acid a n d a m m o n i u m vanadate produced an orange color turning a dark-brown a n d then fading. H y o s c i n e (see S c o p o l a m i n e ) . H y o s c y a m i n e H y d r o b r o m i d e , M e r c k f r o m Belladonna-Cryst.
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M . P . , 1 4 7 - 8 . ( U . S . P . , 1 5 1 . 8 ; H e n r y , 151.8.) U . S . P . tests: T h e chloraurate melted 1 5 9 - 1 6 0 . T h e aqueous solution w a s neutral t o litmus, laevorotatory; with silver nitrate g a v e a precipitate insoluble in nitric acid, soluble in ammonia; with platinic chloride, no precipitate. T h e solid substance g a v e Vitali's reaction; w i t h sulphuric acid n o color was produced, and the further addition of nitric acid produced no color. Morphine A l k a l o i d . M . P . , 2 5 3 - 4 . ( U . S . P . , w h e n rapidly heated, 2 5 4 ; Briihl, with decomposition, about 2 3 0 ; Schmidt, cautiously heated, about 230, without decomposition; above 230 or u p o n rapid heating it decomposes; P i c t e t , about 247 with decomposition; H e n r y , 254, with decomposition; Rosenthaler, 230.) U . S . P . tests: T h e aqueous solution was alkaline t o l i t m u s ; M a y e r ' s reagent g a v e a gelatinous precipitate; sodium phosphomolybdate g a v e a yellow precipitate forming a blue solution u p o n addition of ammonia. U p o n w a r m i n g with solutions of ferric chloride and potassium ferricyanide, it turned blue. T h e neutral solution g a v e a blue color with ferric chloride and the acidified solution g a v e no color. Solid substance: with sulphuric acid, cold, g a v e no color, but on heating a brownish-purple. W i t h sulphuric acid and potassium iodate dark-brown color; with Mecke's reagent, blue color becoming green and then b r o w n ; with Froehde's reagent, reddish-purple color becoming blue; with Marquis' reagent, purple color; with sulphuric acid
98 SOME MICROCHEMICAL TESTS FOR ALKALOIDS and potassium dichromate, colorless, then g r e e n ; with nitric acid, orange color becoming yellow. Narceine, Eimer and A m e n d . M . P . , 1 6 5 - 6 ; dried at 1 0 5 - 1 1 0 , b e g a n to m e l t at 1 6 5 - 6 ; not entirely melted at 2 2 0 . ( H e n r y , 1 7 0 , or 140-145 dry; Pictet, 1 7 0 - 1 , or 145 d r y ; Schmidt, 162-5 air-dry; Briihl, 170, dry at 100, m e l t s 1 4 0 - 5 ; Winterstein, with 3 H 2 O melts 170, a n h y d r o u s 1 4 0 - 5 ; Rosenthaler, 170.) Substance (see Schmidt, 2,1742). W i t h F r o e h d e ' s reagent brown-green color not becoming r e d ; evaporated with dilute sulphuric acid, red colorno v i o l e t streaks on adding a trace of nitric acid; with s u l p h o v a n a d i c acid brown color becoming yellow and then p a l e - r e d d i s h ; with Marquis' reagent, brown color fading o u t ; w i t h Mecke's reagent, brown to reddish color fading out. Chlorine water and subsequent a d d i t i o n of ammonia produced an evanescent red color not t u r n i n g blue u p o n the addition of iodine solution. Narcotine, E i m e r and A m e n d . M . P . , 1 7 2 - 4 . ( H e n r y , 176; Pictet, 1 7 6 ; Schmidt, 176; Briihl, 176; Rosenthaler, 176.) W i t h Froehde's reagent a green color; w i t h M e c k e ' s reagent, pale-bluish; sulphovanadic acid, r e d ; Marquis' reagent, reddish color becoming yellow; s u l p h u r i c acid, y e l low color turning red on warming. Nicotine, Merck, H i g h e s t Purity. A brown liquid apparently s o m e w h a t decomposed. T h e microchemical tests were, however, m a d e on a fresh sample. Turned litmus paper blue and left a f a t t y - a p p e a r ing spot. T h e alcoholic solution was lsevorotatory; after acidifying with H C 1 was dextrorotatory.
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T h e above acid solution was m a d e alkaline hydroxide and distilled with steam. The shaken out with chloroform and the latter " blasted off " cold in the presence of dilute H C 1 . T h e residue g a v e precipitates with Meyer's, Kraut's, a n d Sonnenschein's reagents, and silicotungstic acid. T h e distillate was alkaline to litmus. T o an ethereal solution of the alkaloid an ether solution of iodine w a s added a n d the mixture allowed t o stand in a corked tube. R e d needles formed but on inspection with reflected light n o blue iridescence w a s apparent. U p o n digesting one or t w o drops of the alkaloid with formaldehyde for some hours and then a d d i n g one or t w o drops of nitric acid a red color was produced. T h e hydrochloride solution u p o n evaporation left a non-crystalline residue. Papaverine, Merck. M . P . , 1 4 4 - 5 (softens 1 4 3 ) . (Winterstein, 147; Pictet, 1 4 7 ; Schmidt, 1 4 7 ; H e n r y , 1 4 7 ; Briihl, 1 4 7 ; Rosenthaler, 147.) Substance ( S c h m i d t 2, 1 7 3 1 ) . W i t h F r o e h d e ' s reagent g a v e violet-blue color t u r n i n g green, t h e n blue, then g r e e n ; Marquis' reagent, reddish-violet color f a d i n g out. Sulphovanadic acid, bluish-green color t u r n i n g blue; Mecke's reagent a bluish-green color becoming blue and then fading. Chlorine water g a v e a brownish-gray (not green) solution. Precipitate produced b y ammonia had about the same color; no reddish color. Peronine, Merck. M e l t e d above 2 6 0 . T h e substance g a v e Pellagri's reaction. W i t h Froehde's reagent a bluish-purple color becoming maroon, purplish-gray, then olive, c h a n g i n g rapidly at
100 SOME MICROCHEMICAL TESTS FOR ALKALOIDS first; Marquis' r e a g e n t , pink, becoming cherry color; Mecke's reagent, light-green color becoming olive, then greenish-brown; sulphovanadic acid, brownish color; sulphuric acid, cold, produced no color; on warming, a reddish color; addition of a t r a c e of nitric acid turned the solution dark brownish-red. P h y s o s t i g m i n e Sulphate, Merck. Melting-point, indeterminate; softened about 115. ( U . S . P . , M . P . , about 1 4 0 ; softening at 1 3 0 ; H e n r y , deliquescent, m e l t s 1 4 0 . ) U . S . P . tests: A q u e o u s solution faintly acid to litmus. W i t h barium chloride gives a precipitate insoluble in hydrochloric acid. W i t h ammonia an evanescent precipitate which redissolved, the solution t u r n i n g p i n k ; with g o l d chloride a purple color and turbidity; w i t h platinic chloride (in concentrated solution o n l y ) , yellowish precipitate. T h e substance w i t h sulphuric acid g a v e a faint-yellow color; with sulphuric acid and potassium iodate, lightpurple to reddish color. F i v e m g . treated w i t h nitric acid g a v e a yellow color, becoming red on w a r m i n g , and on evaporating the residue became slightly greenish. T h e latter was not turned violet by fumes of nitric a c i d ; addition of a drop of nitric acid g a v e a red solution t u r n i n g greenish on dilution. Pilocarpidine N i t r a t e , H a r n a c k - M e r c k . M . P . , 132 ( S c h m i d t , 1 3 6 ; H e n r y , 1 3 3 ) . A p p l i e d U . S . P . test for pilocarpine to 10 m g . with hydrogen peroxide, benzol, a n d potassium dichromate; result negative. Violet color at first, but disappeared on shaking. Pilocarpine Hydrochloride. D r i e d in oven at 1 0 3 . M . P . , 1 9 6 - 7 . ( U . S . P . , dried
101
several hours at 1 0 0 ; melts 1 9 5 . 9 ; Schmidt, about 2 0 0 ; Briihl, 2 0 0 ; Rosenthaler, about 2 0 0 ; H e n r y , 2 0 4 - 5 . ) U . S . P . tests: H y d r o g e n peroxide, potassium dichromate and benzol gave a violet color described as characteristic of pilocarpine. T h e aqueous solution was faintly acid to litmus and gave a white precipitate with silver nitrate insoluble in dilute nitric acid. T h e substance triturated with calomel turned black; on addition of sulphuric acid evolved g a s ; addition of a particle of potassium dichromate produced a green color. Piperine, Merck. M.P., 128-130. ( U . S . P . , 1 3 0 ; H e n r y , 1 2 8 - 9 . 5 ; Pictet, 1 2 8 - 9 ; Winterstein, 1 2 8 ; Briihl, 1 2 8 - 9 . 5 ; Schmidt, 1 2 8 - 9 ; Rosenthaler, 128.) Substance with sulphuric acid produced at first brownish-red color, later becoming greenish; with nitric acid an orange color. Quinidine Sulphate, F e i d t & Co. M . P . , 195. Tests (see Schmidt 2y 1 7 8 7 ) . W a r m e d 0.5 g. with 10 c.c. of water to 60, added 0.5 g. potassium iodide, stirred and let cool one hour, then filtered. I n filtrate one drop 10 per cent, ammonia water produced n o precipitate. Five-tenth g m . and 10 c.c. water acidified with sulphuric acid and 10 c.c. of ether were made alkaline with ammonia and shaken. A l l the alkaloid was dissolved. T h e solution acidified with sulphuric acid w a s fluorescent; gave the Thalleioquin test. T h e alcoholic solution of the alkaloid was dextrorotatory. Quinine Sulphate.
10 SOME MICROCHEMICAL TESTS FOR ALKALOIDS Dried at 115-120. Melting-point about 2 1 8 - 9 w i t h decomposition. D r i e d over sulphuric acid, M . P . , 2 0 9 - 2 1 0 with decompositionN o t sharp. ( U . S . P . , dried over sulphuric acid, 2 0 5 ; Schmidt, dried above 150 w i t h decomposition; H e n r y , dried over sulphuric acid, becomes anhydrous at 115% melts at 205.) U . S . P . tests: T h e aqueous solution w a s neutral t o l i t m u s ; w i t h barium chloride gave a white precipitate insoluble in h y d r o chloric acid; gave the Thalleioquin t e s t ; w h e n acidified w i t h sulphuric acid gave a blue fluorescence. The ammonia test for other alkaloid g a v e a d e c i d e d turbidity. T h e substance with sulphuric acid acquired n o c o l o r ; with nitric acid a faint-yellow color. Quinoline, Merck, Pure. Yellow, oily liquid having a slightly alkaline reaction t o litmus paper and leaving a f a t t y stain thereon. Boiling-point, 236 (determined in a capillary t u b e containing a Scudder anti-bumping capillary a n d read on. falling temperature at cessation of e b u l l i t i o n ) . D i f f i c u l t l y soluble in water, readily soluble i n alcohol. Scopolainine Hydrobromide, M e r c k . T r u e . M . P . , 191. (Dried t w o d a y s over sulphuric acid.) U . S . P . , hyoscine hydrobromide. Softens at 100, melts a n d loses water of crystallization, at 110. D r i e d over sulphuric acid, M . P . , 1 9 1 - 2 . (Schmidt, i-scopolamin-hydrobromid dried, 180; H e n r y , i-scopolamin-hydrobromid dried, 1 8 0 ; Briihl, t h e salt official in Germany dried a t 1 0 0 , M . P . , 1 8 7 - 1 9 1 ; RosenthaJer, 1 9 0 - 2 . )
103
T h e chloraurate, M . P . , 1 9 7 ; the aqueous solution w a s neutral to litmus, lasvorotatory, silver nitrate produced a precipitate insoluble in nitric acid, b u t soluble in ammonia. Chlorine water liberated bromine, i m p a r t i n g a brown color to chloroform. Mayer's reagent w i t h hydrochloric acid gave a precipitate; mercuric chloride, precipitate; phosphotungstic acid, precipitate; picric acid, precipitate; platinic chloride, precipitate. T h e substance g a v e Vitali's reactions. Solanine, Merck. Softened at 250 with decomposition, n o t entirely melted at 2 7 0 . ( H e n r y , 235 or 244 or 2 5 0 ; W i n t e r stein, 2 6 2 ; P i c t e t , 2 3 5 ; Bruhl, 2 4 4 ; Schmidt, 2 4 5 ; Rosenthaler, 2 5 0 - 2 6 0 . ) ( S e e Schmidt 2, 1662.) T h e substance with sulphuric acid g a v e an orange color becoming violet; Froehde's reagent g a v e a y e l l o w color becoming brown with purple streaks, purple and then greenish; Mecke's reagent g a v e a brown color, then p u r p l e streaks becoming greenish and then b r o w n ; sulphovanadic acid, yellow color becoming brown, purple-violet a n d then olive. Sparteine Sulphate Crystals, E i m e r and A m e n d . D r i e d at 110 in oven; melted in its water of crystallization a n d then solidified; was powdered and dried until n o longer coherent; color became slightly yellowish-orange when m e l t e d ; softened at 153. M . P . , not sharp, 155-7* ( U . S . P . , loses all water of crystallization at 110, anhydrous, M . P . , 1 3 6 ; Rosenthaler, H e n r y and W i n t e r stein give lupinidine as a synonym of sparteine.) U . S . P . tests: T h e aqueous solution was acid to litmus. N o precipi-
104 SOME MICROCHEMICAL TESTS FOR ALKALOIDS tate in any dilution by p o t a s s i u m ferrocyanide 5 per cent, solution. Barium chloride gave a white precipitate insoluble in H C L The ether-ammonia-iodine t e s t was positive. The test for volatile alkaloid with potassium hydroxide and litmus paper was positive. The substance treated with sulphuric acid did not carbonize. Strychnine Hydrochloride, P o w e r s and W e i g h t m a n . M . P . not below 260. T h e aqueous solution with silver nitrate g a v e a white precipitate insoluble in nitric acid. T h e substance treated with sulphuric acid containing a trace of potassium dichromate g a v e the characteristic blueviolet color becoming purple, cherry and orange. Sulphuric acid with ammonium vanadate g a v e a violet color becoming purple, then cherry. Sulphuric acid gave no color. On adding potassium iodate a violet color becoming reddish-purple appeared. Nitric acid gave no color. O n evaporating and treating with ammonia became dark-yellow, and if treated with alcoholic potassium hydroxide solution, orange-red color changing to brown. Thebaine, Eimer and A m e n d . M.P., 191-2. ( H e n r y , 193; Pictet, 1 9 3 ; Briihl, 1 9 3 ; Schmidt, 193; Rosenthaler, 193.) The substance with sulphuric acid g a v e a red color; with Froehde's reagent a red color; with sulphovanadic acid a red color. Theobromine. M . P . about 340.
105
( S c h m i d t and Rosenthaler, suhlimes 290 without melting; Winterstein, sublimes 2 9 0 - 5 without m e l t i n g ; Pictet, sublimes 2 9 0 - 5 without m e l t i n g ; enclosed in a tube melts 3 2 9 - 3 3 0 ; H e n r y , same as P i c t e t . ) Substance evaporated with chlorine water and the residue exposed to the fumes of ammonia assumed a purple color (murexide test p o s i t i v e ) . Tropacocaine Hydrochloride, Merck. (Benzoylpseudotropeine Hydrochloride.) M . P . about 277 with decomposition. (Briihl, 2 7 1 ; Rosenthaler, 2 7 1 ; H e n r y , 283 with decomposition; Schmidt (see Schmidt 2,1691). One-tenth g m . dissolved in 5 c.c. of water and m i x e d with three drops dilute sulphuric acid a n d five drops of 1 : 1 0 0 0 potassium permanganate solution g a v e violet color, not diminishing much in one-half hour. Yohimbine Hydrochloride, M e r c k (Quebrachine). M . P . not sharp, 3 0 0 - 3 1 5 with decomposition. ( H e n r y , 2 9 5 - 3 0 0 with decomposition; Briihl, 2 8 7 ; Rosenthaler, 2 8 5 - 2 9 0 ; Schmidt 2, 1845, about 300.) T h e aqueous solution was made alkaline with ammonia and shaken out with chloroform and the chloroform evaporated. T h e alkaloidal residue dissolved in sulphuric acid formed a colorless solution. I n this particles of potassium dichromate produced grayish streaks not resembling those characteristic of strychnine. A portion of the alkaloidal residue was warmed in a test-tube with ammoniacal silver nitrate solution. R e d u c tion indicated b y formation of a slight mirror. T h e substance with sulphovanadic acid g a v e a blue, turning wine color; with Froehde's reagent slowly developed a blue color turning green.
INDEX TO PLATES Aconite with Sodium Carbonate Ammonium Thiocyanate Anhalonine with Gold Chloride with Phosphotungstic Acid with Platinum Chloride Apomorphine with Gold Chloride Arecoline with Kraut's Reagent with Palladous Chloride Aspidospermine with Potassium Hydroxide with Wagner's Reagent Atropine with Picric Acid with Wagner's Reagent Benzoyl-ecgonine with Gold Chloride Berberine with Hydrochloric Acid with Sulphuric Acid with Wagner's Reagent Betaine with Phosphomolybdic Acid with Phosphotungstic Acid Brucine with Ammonium Thiocyanate with Chromic Acid with Millon's Reagent with Palladous Chloride with Platinum Chloride with Potassium Cyanide with Potassium Hydroxide with Potassium Iodide With Saccharin with Sodium Nitropmsside with Wagner's Reagent with Zinc Chloride Caffeine with Gold Chloride with Kraut's Reagent with Mercuric Chloride Calycanthine with Chromic Acid with Palladous Chloride with Platinum Chloride Chelidonine with Zinc Chloride Choline with Phosphomolybdic Acid Chromic Acid Cinchonine with Sodium Carbonate Cinchonidine with Platinum Chloride with Potassium Hydroxide with Sodium Phosphate Cocaine with Chromic Acid with Ferric Chloride with Gold Chloride with Palladous Chloride with Picric Acid with Platinum Chloride with Potassium Permanganate PI. XIII, Fig. 6 PI. XXV PL I, Fig. 1 PL XXIV, Fig. 3 PI. IV, Fig. 1 PL I, Fig. 2 PL XIII, Fig. 1 PL VI, Fig. 1 PL XV, Fig. 1 PL X, Fig. 1 PL XIX, Fig. 1 PL X, Figs. 2, 3 PL I, Fig. 3 PL XX, Fig. 5 PL XX, Fig. 6 PL X, Fig. 4 PL XXIV, Fig. 1 PL XXIV, Fig. 4 PL XXV, Fig. 1 PL XXII, Fig. 1 PL XXVI, Fig. 1 PL VI, Fig. 2 PL IV, Fig. 2 PL XXI, Fig. 1 PL XV, Fig. 2 PI. XVIII, Fig. 2 PL V, Fig. 6 PL IX, Fig. 6 PL X, Fig. 5 PL XXVI, Fig. 5 PL I, Fig. 4 . PL XIII, Fig. 2 PL VIII, Fig. 1 PL XXII, Fig. 2 PL VI, Fig. 3 PL IV, Fig. 3 PL XXVII, Fig. 1 PL XXIV, Fig. 2 Pis. XXII and XXIII PL XIV, Figs. 1, 2 PL IV, Fig. 4 PL XV, Fig. 3 .PL VII, Fig. 5 PL XXII, Fig. 3 PL III, Fig. 6 PL I, Figs. 5, 6 PL VI, Fig. 4 PL XIX, Fig. 2 PL IV, Fig. 5 PL XXIII, Fig. 4 107
108 SOME MICROCHEMICAL TESTS FOR ALKALOIDS Codeine with Ammonium Thiocyanate with Chromic Acid with Marine's Reagent with Millon's Reagent with Potassium Chromate with Potassium Iodide with Wagner's Reagent with Zinc-Chlor-Iodide Coniine with Marine's Reagent with Phosphotungstic Acid Corydalin with Mercuric Chloride Cytisine with Gold Chloride with Mercuric Chloride with Picric Acid with Wagner's Reagent Dionine with Mercuric Chloride with Sodium Carbonate with Wagner's Reagent Ecgonine with Kraut's Reagent Ferric Chloride Gold Chloride Heroine with Mercuric Chloride with Picric Acid with Potassium Cyanide Homatropine with Gold Chloride with Millon's Reagent with Wagner's Reagent Hydrastine with Potassium Hydroxide Hydrastinine with Chromic Acid with Palladous Chloride with Picric Acid with Platinum Chloride with Potassium Permanganate Hydrochloric Acid Hyoscyamine with Gold Chloride with Wagner's Reagent Kraut's Reagent Marine's Reagent Mayer's Reagent Mercuric Chloride Millon's Reagent Morphine with Marine's Reagent with MayeT's Reagent with Mercuric Chloride with Potassium Chromate with Potassium Iodide with Sodium Carbonate with Wagner's Reagent Narceine with Gold Chloride with Palladous Chloride with Platinum Chloride with Potassium Hydroxide with Wagner's Reagent Narcotine with Potassium Acetate with Sodium Carbonate PI. XXV, Fig. 2 PL XXII, Fig. 4 PL XVII, Figs. 1, 2, 3 PI. XXVI, Fig. 2 PL XXI, Fig. 4 PL XVIII, Fig. 3 PL X, Fig. 6 PL XXVII, Figs. 2, 3 PL XVII, Fig. 4 PL XXIV, Fig. 5 * PL VIII, Fig. 2 PL II, Fig. 1 PL VIII, Fig. 3 PL XIX, Fig. 3 PL XI, Fig. 1 PL VIII, Fig. 4 PL XIV, Fig. 3 ., PL XI, Fig. 2 PL XIII, Fig. 3 PL III Pis. I, II, III PL VIII, Fig. 5 PL XIX, Fig. 4 ....PL XXI, Fig. 2 PL II, Fig. 2 PL XXVI, Fig. 3 JP1. XI, Figs. 3, 4 PL XV, Fig. 4 PL XXII, Figs. 5, 6 PL VI, Fig. 5 .PL XIX, Fig. 5 PL IV, Fig. 6 PL XIII, Fig. 5 ..PL XX PL II, Fig. 3 PL XI, Fig. 5 PL XIII Pis. XVII, XVIII PL XVI Pis. VIII, IX PL XXVI PL XVII, Fig. 5 PL XVI, Fig. 3 PL VIII, Fig. 6 PL XXI, Fig. 5 PL XVIII, Fig. 4 PL XIV, Fig. 4 PL XI, Fig. 6 PL II, Fig. 4 PL VI, Fig. 6 PI. V, Fig. 1 PL XV, Fig. 6 PL XII, Fig. 1 PL XII, Fig. 5 PL XIV, Fig. 5
INDEX TO PLATES Nicotine with Gold Chloride with Mercuric Chloride Palladous Chloride Papaverine with Mercuric Chloride with Palladous Chloride with Potassium Hydroxide with Zinc Chloride Peronine with Potassium Iodide Phosphomolybdic Acid Phosphotungstic Add Picric Acid Pilocarpidine with Phosphotungstic Add Pilocarpine with Platinum Chloride Platinum Chloride Potassium Acetate Potassium Chromate Potassium Cyanide Potassium Ferrocyanide Potassium Hydroxide Potassium Iodide Potassium Permanganate Quinine with Ammonium Thiocyanate with Potassium Acetate with Potassium Chromate with Sodium Phosphate with Wagner's Reagent Quinidine with Ammonium Thiocyanate with Gold Chloride with Mercuric Chloride with Potassium Ferrocyanide with Potassium Iodide Quinoline with Chromic Acid with Gold Chloride with Kraut's Reagent with Mercuric Chloride with Millon's Reagent with Picric Add with Platinum Chloride with Potassium Ferrocyanide with Wagner's Reagent Saccharin Scopolamine with Gold Chloride with Wagner's Reagent Sodium CaTbonate Sodium Nitroprusside Sodium Phosphate Sparteine with Gold Chloride with Palladous Chloride Strychnine with Ammonium Thiocyanate with Chromic Add with Gold Chloride with Marine's Reagent with Mayer's Reagent with Palladous Chloride with Platinum Chloride with Picric Add
109 PL n, Fig. 5 PL IX, Fig. 1 Pis. VI, VII PL IX, Fig. 2 PL VII, Fig. 1 PL XV, Fig. 5 PI. XXVI, Fig. 6 PL XVIII, Fig. 5 PL XXIV PL XXIV Pis. XIX, XX PL XXIV, Kg. 6 PL V, Fig. 2 Pis. IV, V PL XII PL XXI PL XXI n PL XX Pis. XV, XVI PL XVIII PL XXIII PL XXV, Jigs. 4, 5 PL XII, Fig. 6 PL XXI, Fig. 6 PL VII, Fig. 6 PL XII, Fig. 2 PL XXV, Fig. 8 PL II, Fig. 6 PL IX, Fig. 8 PL XX, Fig. 8 PL XVIII, Fig. 6 PL XXIII, Fig. 1 PL III, Fig. 1 PL XIII, Fig. 4 PL IX, Fig. 4 PL XXVI, Fig. 4 PL XIX, Fig. 6 PL V, Fig. 8 PL XX, Fig. 4 PL XII, Fig. 3 PL V PI. Ill, Fig. 2 PL XII, Fig. 4 Pis. XIII, XIV PL IX PL VII PL III, Fig. 3 PL VII, Fig. 2 PL XXV, Fig. 6 PL XXIII, Fig. 2 PL III, Fig. 4 PL XVII, Fig. 6 PL XVI, Figs. 4, 5 PL VII, Fig. 3 Pi. V, Fig. 4 PL XX, Fig. 1
110 SOME MICROCHEMICAL TESTS FOR ALKALOIDS Strychnine with Potassium Hydroxide with Mercuric Chloride .. with Sodium Carbonate with Zinc-Chlor-Iodide Sulphuric Acid Thebaine with Potassium Hydroxide Tropacocaine with Chromic Acid with Gold Chloride with Kraut's Reagent with Marine's Reagent with Mayer's Reagent with Palladous Chloride with Picric Acid with Platinum Chloride with Potassium Permanganate with Zinc-Chlor-Iodide Wagner's Reagent Yohimbine with Potassium Cyanide Zinc Chloride Zinc-Chlor-Iodide PL XVI, Fig. 1 PL IX, Fig. 5 .... PL XIV, Fig. 6 PL XXVII, Figs. 4, 5 PL XX PL XVI, Fig. 2 PL XXIII, Fig. 3 PL III, Fig. 5 PL XIII, Fig. 5 PL XVIII, Fig. 1 PL XVI, Fig. 6 PL VII, Fig. 4 PL XX, Fig. 2 PL V, Fig. 5 PL XXIII, Fig. 6 .PL XXVII, Fig. 6 Pis. X, XI, XII PL XXI, Fig. 8 Pis. XXVI, XXVII PL XXVII
PLATE I.
FIG. 1 A halo nine 1 : 200. . n
u F. pri 1 : I 2 Anf G . op oe in a
F . 3 Bzcn 1 : 5. F. n i : 5. I eooie 0 I 4 C 0 G . ne y l g G. a e f i e 4r
F . osl1 : 50t g coI. ieXn 1 : 1 0 I 5 Ciao e 0.h o hiGôi. 0 . G . ct f d w d lre -i 1e O ns r i l F .Cc0 a m e r y d - a) 5
PLATE II.
*>/*
Fn.. 1.Cytisim.1 1 : 2u<).
\ "V "-,
FIG. 3.Hyoscyanune 1 : 50.
Fi. 5.N'icotinc 1 : 100O. Fu;. ii.Quinitiine 1 : 2txi. Crystals formed with cold chloride i Xlol!'.
ATE III.
Fie. 2.Scopolaniine I :
FIG. 3.Sparteine 1 : 20O. FIG. 4.Strychnine 1 : 500. Crystals fcrmexi with gold chloride K X150 * .
4*
FIG. 5.Tropacooiine 1 : l()O0, with gold Fit;, ti.Cocaine 1 : 50. with ferric chloride chloride (XI50). t XI">*)).
PLATE IV.
-*/
-A"
,.' \
Fiu. 1.Anhaloiiine 1 : 20U.
FIG. I1.Braciae 1 :
Fio. 3.Calycanthine 1 : 1000.
FIG. 4.Cinchonidine 1 : 1000.
FIG. 5.Cocaine 1 : 5O0. FIG. t>.Hydrastinine 1 : 5 . ) <. K Crystals formed with platinum chloride ( X150/.
PLATE V.
chnine FIG. 3.Quinoline 1 : 50O. FIG. 4.Strychnine 1 : 500. Crystals formed with platinum chloride i X15(Ji. #
.FIG. 5.Tropaeocaine 1 : 500, with platinum FIG. 6.Brucine 1 : o<), with saccharine chloride ( X150). (X150.
PLATE VI.
FIG. 1.Arecolino 1 : .50.
FIG. 2.Brucinc- 1 : ,) 0 "O .
FIG. o.Hydrastininp 1 : W>. FIG.ft.Calyeanttdne1 : 1 0 . OO Crystals formed with palladcms chloride ( XloO).
PLATE VII.
FIG. 1.Papaverine 1 : ~ 0 >.
FIG. 2.Sparteine 1 : ~ a .>
&;fct.
FIG. 3.Strychnine 1 : ,>> . "(0 FIG. 4.Tropaeocaine 1 : 100. Crystals formed with palladous chloride ( X150>.
FIG. O.Cinchonidine 1 : 2(X). Fir,. 6.Quinine 1 : 200. Crystals formed with sodium phosphate 1 : 200.
PLATE VIII.
F.a : o G1nf1 ) I .C l e . if J>,

F . 3 Cie 1 : 5. I y G. n s t 0
F. 1 : 5 G4D 0 I .n . o a e i
1 : 50.
#
* > Fi. 5 . H e r o i n e 1 : 2O0. Crystals formed with TIG. 6.Morphine mercuric chloride ( X 150).
PLATE IX.
FIG. S.ûinidine 1 : 200. FIG. 4.Quinuline 1 : 2uu. Crystals formed with mercaric chloride ( X150).
FIG. O.Strychnine 1 : 500, with mercuric FIG. 6.Bruciae 1 : 30, vrith sodiuai nitrochioride ( X150). prusside.
PLATE X.
Pio. 1.Aspidospcrrnine 1 : ~>0.
FIG. 2.Atropine 1 : 500.
. .'i.Atropine 1 : 500 {X'<i00)
FIG. 5.Brueine 1 : 500. FIG. 0.Codeine 1 : 50. Crystals formed with Wagner's reagent (X150}.
I'LATi: XI
FIG. 1.Cytisiui' 1 : UI.
FIG. 3.Homatropine 1 : ~A\)
FIG. 5.ffyosevarciiii> 1 : 50. FKJ.fi.MorphineI : 2C 0L Crystals foriuei with Wagner's reajgent ( XlJi
i':..wi. MI.
Tic. 3.Quinoline 1 : 2iN). Fiu. 4.Scopolarrui'e J : 50. Crystals formed with ^'agner's reagen
Fro. 5.Nareotine 1 : 2K () Fir, r,.Qmrune 1 "15. Crystals formed with potassium acetate Xl5
i'-LATL
FIG. 1.ArtM'olinr 1 : 4 ) . H %
Crystals fnrmed with Kraut's rva*rf nt Xl.V;
* F. raiI 1C10w Ksi FTn 1 * w G5rgtn XU0, h rf U. Ai > h I . eece 1:. 0 t a" .n-6 i To 5 i u i. f ' oa p i n t anc J
e j
FIG. 3.Dionine 1 :
u. 4. M'..rpr;:n* 1 : "*'
Pio. 5.Narcotine 1 : 1000. Fie . Strychnin* 1 : > Crystals formed with sixiiuni carboaite H:1*H)
Fit;. 1.Asjtu.ltjs'|>tiri!uiu' 1 : lt*tt
FIG. T>.Papavenuo 1 : 2X . t> ^ i</ ' -V-'* Crystals formed with potassium hydr->*nit s . <
%*
V 4 Via l.Stryfhnm' 1 : .* "it Crystals i'urim-if with p <
PLAiL XWL
FIG. 5.Morphine I : 200. Fi. 6. >tryrhmne 1 Crystals formed with Marine's reagent X !> ! .< *
Fin. i.Tropaci -.unv I : lin>,\nth Mar
FIG. :i.Codeine 1 : 50.
FIG. 5.Peronine 1 : 200. Fir? tf Crystals formed -with potassiuni n.Mi.ir- '
\;v.
FIG. 3.Cvtisine 1 : 50.
Fir,. 6. ) n .line 1 : 1O\ <w Fio. 5.Hydrastinine 1 : 200. 1f 3V Crystals formed with picric acid
r. \ . .;. V\
-K
X
% * * *
4i
%l*
Fe 3 Qna o : 5w ptsui4fr. > ;;*' i. uss fr e 0t n srr er * itr . Cytl 1 d .h aFi .. > r. iin i rde m i i
i'LA 1L XM .
Fio. li.Vohimbine I : 2(K), with potassium cyanid* ( X15W.
Fin. 1.C--*it'izit ] -n K
FIQ. 5.Morphine 1 : 50. Crystals formed with
PLATE XXII.
m m - : FIG. 1.Brucine 1 : 500.
FIG. 2.Calycanthine 1 : 50.
FIG. 3.Cocaine ] : 200.
FIG. 4.Codeine 1 : 50.
FIG. 5.Hydrastinine 1 : 200. FIG. 6.Hydrastinine 1 : 200. Crystals formed with chromic acid ( X150>.
PLATE XXIII.
FIG.
l.
.. y t c h I wFrn 15. 5. h Gc nit X: 0 t cmSe I* 0 i Io2 d 0 hi r i

-8
* . S -Tropacocaine 1 : 100, with chromic FIG. 3.Tropa
FtG
4 -Cocaine 1 : 200, with potassium t w. 4.-C perman2anate .
t e o n a F.lyte wl5u Tma : 11. G5r dd h0t. rc.an ( X> I Cao 1 :Fp >*ne 00 . y n tG0 ocgt 0 His i o pe. 0 r v a t 1 5 a .m ri a . e i6 a sm s tf
PLATE XXIV.
.*' n*
FIG. 1.Betaine 1 :: 200. 1 200. FIG. 2.Choline 1 : 200. FIG. Ctl f bdie id { XlOi Crystals formed with phosphomolybdie acid { XloOi. ***
V
"Hf..
s? :.
. * *r
*fc
PIG. 3.Anhalonine 1 : 200.
FIG. 4.~Betaine 1 : 1000.
FIG. 5.Coniine 1 : 200. FIG. 6.Piloearpidine 1 : 60 Crystals formed with phosphotungstic acid ( XI50).
PLATE XXV.
FIG. 1.Brucine 1 : 50.
FIG. 2.Codtine 1 : "U >.
Fie. 3.Ouinidine 1 : 2M. ( )
FIG. 4.Quinine 1 : 35.
FIG. 5.Quinine 1 : 35. FIG. 6.Strychnine 1 : 500, Crystals formed with ammonium thiocyanate ( X150^.
PLATE XXVI.
FIG. 1.Bnicine 1 : 1 U . U0
FIG. 2.Codeine 1 : 5O.
>
FIG. 3.Homatropine 1 : 50. Fio. 4.Quinolme 1: 50. Crystals formed with ZStillon's reagent ( X150).
m.~ FIG. 6.Papaverine 1 : 500. FIG. 5.Brucine 1 : 50. cine 1 : 50. p id (XlO) C l f Crystals formed with zinc chloride (XloO).
PLATE XXVII.
FIG. 1.Chelidonine 1 : 500, with zinc chloride (X150).
FIG. 2.Codeine 1 : 50.
c;.'6.Codeine1 : 50.
V Fio. 5.Strychnine 1 : 50. Fio. (J.Tropacocy,Irio 1': ^ Q Crystals formed with zinc-chlor-iodide (X150),

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S O M E T E S T S

C. E . P A R K E R ASSISTANT CHEMIST B B A OF CHEMI3TBY, T NT D S A E D P B M N O AQRICULTXJEB, UEU 7 I B T T S BA T S T F W S I G O , D. O. A HN T N

With Tv/enty-seven Plates (162 Photomicrographs) and a Folding Table of Reactions.

L O N D O N CHARLES GRIFFIN & COMPANY, LIMITED W.C.2

12 E X E T E R STREET, STRAND, 1921

SOME MICROCHEMICAL TESTS FOR ALKALOIDS

SOME MICROCHEMICAL TESTS FOR ALKALOIDS

TESTS FOR ALKALOIDS DESCEIBED B Y OTHERS

SOME MICROCHEMICAL TESTS FOR ALKALOIDS

REAGENTS USED Wagner's reagentIodine P o t a s s i u m iodide Water

1. Thebaine 2. Papaverine 3. Narcotine 4. Hydrastine 5. Aspidospermine 6. Corydaline 7. Chelidonine

1. Homatropine 2. Hyoscyamine 8. Berberine 4. Atropine 5. ColcMdne

1. Theobromine 2. Narceine 8. Anhalonine 4. Coniine 5. Arecoline

1. Calycanthine 2. Pilocarpine 3. Brucine 4. Cinchonidine

WITH Mnrn ( Vnumtm */ Ilrrnffie J - >ifnlnf

Wrrii Mam' 1 i * *% C= * r t >tl4nr

TABLE S H O W I N G BEST T E S T S FOR ALKALOID

nni < liiiri! r ^ ^ l k

Afifl {XXIV\ fl)

(IV, X Wtfvtit (XVH, 4) Win#f $U*ifnl (XL h U Ummtk HMmttki CVHi. 4)

(V I) ujm Amliil (.XJI. 0) mr ChUmdr fix, U : M l (XXVl,0)

F o u r crystalline a n d twenty-two non-crystalline p r e cipitates were obtained.

DETAILED DESCRIPTION OF TESTS

small crystals o n stirring the 1 : 5 0 0 solution.

very short rods in the 1 : 50 solution only on stirring.

formed in the 1 : 50 solution.

tals slowly in all solutions from t h e amorphous precipitate.

DETAILED DESCRIPTION OF TESTS

DETAILED DESCRIPTION OF TESTS

Four crystalline and thirteen non-crjrstalline precipitates were obtained.

P I C R I C A C E D . W e have a n amorphous precipitate but

DETAILED DESCRIPTION OF TESTS

SOME MICROCHEMICAL TESTS FOR ALKALOIDS

DETAILED DESCRIPTION OF TESTS

SOME MICROCHEMICAL TESTS FOR ALKALOIDS

crystals formed on stirring. in rosettes.

T h e y are characteristic plates

GOLD CHLORIDE.Crystals are formed only o n stirring

Twenty crystalline and nine non-crystalline precipitates were obtained.

DETAILED DESCRIPTION OF TESTS

precipitate in the 1 : 5 0 solution crystallizes quickly into moss-like rosettes (Plate X X V , T i g . 1) ( 2 ) .

DETAILED DESCRIPTION OF TESTS tals have a characteristic appearance Fig. 2 ) . Plafe

K K A U T ' S R E A G E N T . A dense precipitate but n o crys-

30 SOME MICROCHEMICAL TESTS FOR ALKALOIDS tions only. (11) ( 1 2 ) .

They are rosettes of needles ( 1 ) ( 6 ) ( 1 0 )

needle-shaped crystals a r e formed i n all solutions. T h e y f o r m a d e n s e m a s s i n t h e 1 : 50 s o l u t i o n a n d p o l a r i z e b r i l l i a n t l y . T h e l i m i t of r e a c t i o n is a b o u t 1 : 1 0 0 0 ( P l a t e vin,Fig.i).

1 : 200. T h e c r y s t a l s a r e s m a l l n e e d l e s a n d f o r m a dense m a s s i n t h e 1 : 5 0 s o l u t i o n . T h e y p o l a r i z e b u t slightly.

c r y s t a l s a r e n o r m a l l y n e e d l e s o r t u f t s of needles a n d f o r m v e r y slowly. I n t h e 1 : 5 0 solution t u f t s o r r o s e t t e s of fairly l a r g e r o d s o r n e e d l e s a r e f o r m e d o n s t a n d i n g ( P l a t e I , F i g .4 ) ( 1 0 ) .

32 SOME MICEOCHEMICAL TESTS FOR ALKALOIDS

formed in the 1 : 50 solution. quick crystallization.

Stir the 1 : 5 0 0 solution for

P O T A S S I U M C Y A N I D E . T h e crystals are small a n d tri-

DETAILED DESCRIPTION OF TESTS

instantly u p o n stirring the 1: 50 solution a n d in t h e 1 : 200 solution o n standing.

T w e l v e crystalline a n d t w e n t y non-crystalline precipitates were obtained.

formed i n the t w o more dilute solutions ( P l a t e X X V I I , Fig.l).

E i g h t crystalline a n d seven non-crystalline precipitates were obtained.

DETAILED DESCRIPTION OF TESTS

PHOSPHOTXJNGSTIC A C I D . H e a v y , amorphous precipi-

S i x crystalline precipitates and twenty-three non-crystalline precipitates were obtained.

SOME MICROCHEMICAL TESTS FOR ALKALOIDS

N i n e crystalline a n d twenty-four non-crystalline p r e cipitates were obtained.

Wrrii Mam' 1 i * % C= r t >tl4nr