Part IV

PREPARATIONS
Exercise No.1. Preparation of Acetanilide from Aniline by acetyiation.
Requirements. Anline- 2.5 ml
Acetylating Acetic anydride -2!5 ml
"ixture #lacial acetic acid-2.5 ml
PRINCIPLE:
Chemical reaction.
Amines can readily be acetylated to solid acetyl deri$ati$es using acetylating
mixture. %Acetic acid is mixed due to te ig cost of acetic anydride&. 'is reaction
is an eg for Nucleopilic substitution resetin Aniline acts as nucleopile and te lone
pair elecrons on te nitrogen atom attac(s te caronyl group of aceticanydride and
te resuiting product i.s Acetanilide.
Procedure: 'a(e 2.5 ml. of te aniline. 2.5 ml. of acetic anydride and 2.5 ml.
of glacial acetic acid in a 25)ml. conical flas(! *a(e te reaction mixture torougly
and ten reflex it gently for 15 minutes using air condenser. Pour te ot mixture +it
constant stirring to 2)) ml. of ice cold +ater in a bea(er. ,ilter te product and +as
+it +ater. Recrystalise te curde acetanilide eiter from boiling +ater or dilute
acetic acid 2) ml. of acid -) ml. of +ater&.
Appearance . /ite sining 0a(es
1ield . -.5gms.
".P. . 1152c
1
QUESTIONS
1. Explain te mecanism in$ol$ed in actylatum.
2. /ic is te nucleopile in tis reaction
3. 0o+ aniline is. Nucleopilic4
-. 5ndicate te anilide lin(age.
5. /y is aniline is aromatic4
Exerchcic. !: To "re"are A"irin #acet$l alic$lic acid% &rom Salic$lic acid '$
ace&$lation.
Re(uirement: *alicylic acid 5 gms.
Acetic anydride 6 ml.
7onc. *ulpuric acid 3-5 drops.
Chemical reaction:
PRINCIPLE: *alicylic acid is a penolic acid. 'e penolic group can easily
be acetylated using acetic anydride. 'is is an eg of Nucleopilic substitution
reaction. Penolic ydroxyl group of salicylic acid acts as nucleopile and te lone
pair of electrons on te oxygen atom attac(s te carbonyl group of acetic anydride to
form Aspirin.
Procedure: 'a(e all te tree cemical compounds in te gi$en proportions in
a 25) ml. flas(. *a(e te mixture torougly and +arm te reaction mixture at 5) -
8)2c on a +ater - bat +it continuous stirring. Allo+ te reaction mixture to cool
and add nearly 125 ml. of-+ater! stir torougly and filter te product. Recrystallise
te product from 5)9 alcool or 5)9 acetic acid or ot +ater.
2
Appearance 7olourless needles
1ield 5 gms.
".P 138-13627
QUESTIONS
1. Explain te mecanism4
2. /ic is te nucleopile4
3. :se of Aspirin
-. 5dentification tests for aspirin
Exercie No.). To "re"are !*+*, - Tri'romoaniline &rom Aniline '$ 'romination.
Re(uirement
Aniline 2ml.
#lacial acetic acid 15 ml.
;romine in glacial acetic acid 3 ml in 1) ml of
5ce glacial acetic acid
3
Chemical reaction:
PRINCIPLE: ;en<ene does not react appreciably +it ;( but te presence of
acti$ating groups li(e N0
2
on te ring can acti$ate te substitution! can easily form
bromo drri$ati$es! +en treated +it a solution of ;r
2
in acetic acid. 'is is an eg of
Electropilic substitution reaction. *ince- N0
2
is an orto! para director te incoming
bromonium ion %clceopele& is directed to form symmetrical tribromo aniline
Procedure. 'a(e 2 ml. of aniline and 1.5 ml. of glacial acetic acid in a conical flas(.
Place te ;as( in ice bat and add to it =.- ml. of bromine +ater in 1) ml. of glacial
acetic acid drop+ise +it constant stirring troug a burette or separating funnel.
Pour te reaction mixture to a bea(er a$ing excess %1))ml& of +ater. ,ilter te
product +as +it +ater and reerystallise from alcool or rectified spirit.
Appearance 7olourless sining 1ong needles
1ield 5 gm.
". P. 12)27
QUESTIONS
1. Explain te mecanism of reaction
2. /ic is te electropile4
3. /at type of group is-N024
-. Explain o+ ben<ene is more stalte4
-
Exercie No.+ To "re"are "-.romoaeetanilide &rom Aeetanilide '$ tromination.
Re(uirement:
Aeetanilide 2 gm.
#lacial acetic acid 15 ml.
;romine in glacial acetic acid 3 ml. of bromine in 1) ml. of glacial
acetic acid.
Chemical Reaction:
PRINCIPLE: 'e anilide group present in aeetanilide. is a moderate
acti$ating group +ic directs te incoming bromonium ion to orto and para
positions. Practically only a little amount of orto product is formed because of steric
indrance of te bul(y functional group. 'e formed orto product is remo$ed during
recrystallisation because it is completely soluble in alcool or rectified spirit. 'is
reaction is also an eg-for Electropilic substitution.
Procedure: >issol$e 2 gm. ?f te aeetanilide in 15 ml. of glacial actic acid in
25)ml. flas(. Add 31 ml. of bromine dissol$ed in 1) ml. glacial acetic acid from a
burette @A a separating funnel to te aeetanilide solution drop by drop +it continuous
stirring. Allo+ te reaction mixture to stand for alf an our. Pour te contents to a
bea(er a$ing 25) ml. cold +ater. ,ilter te product! +as +it cold +ater! dry and
recrystallise from alcool or rectified spirit.
Appearance /ite crystalline compound
1ield 2.5 gm.
5
".P. 18627
QUESTIONS
1. Explain te mecanism of reaction.
2. /ic is te electropile4
Exercie No./ To "re"are Phen$la0o - "1 - na"tho2&rom Aniline '$ dia0oti0ation
&ollo3ed '$ cou"lin4 reaction.
Re(uirement:
Aniline 2ml
7one. 0ydrocloric acid - ml
*odium nitrite 1g
B-Naptol 1.C5 g
*odium ydroxide 1)9 11ml
5ce
PRINCIPLE: Aniline is an aromatic primary amine +ic can undergo dia<otisation
to form ben<ene dia<onium cloride in presence of sodium nitrite and con 07l. 'is
in turn undergoes coupling reaction +it 2-napittrftelefm penyl a<o2-naptol.
PROCE5URE: >issol$e 1.2ml of aniline in -ml of con 07l and =ml of +ater in a
conical flas( >ia<otise by addition of solution of 1g of sodium nitrite in 5ml of +ater.
Prepare te solution of 1.C5g of 2-naptol in 11ml of 1)9 NA?0 in a 25)ml bea(er
cool te solution to 527 immersion in ice bat or by direct addition of 1) -15g of
crused ice. *tir te naptol solution $igorously and add te cooled >ia<onium
cloride solution $ery slo+ly. Red colour de$elops and red crystals of penyl a<o 2-
naptol separates out. /en all te solution as been added allo+ mixture to stand
in ice bat for 1)mts +it stirring. ,ilter te solution +as +ell +it +ater and drain
torougly. Recrystalli<e te product from glacialacetic acid.
8
Appearance >eep sining red crystals
1ield 3.5 g
".P 131 c
QUESTIONS
1. Explain >ia<otisation.
2. 0o+ does nitrous acid is generated4
3. /y nitrous acid sould be generated in situ4
Exercie No: , 5etermination o& 6ixed 6eltin4 Point
Aim. 'o determine te mixed melting point of te follo+ing mixtures and to report on
te purity of %5& and to report +eter te product is formed in% 2&
1. ;en<oic acid A 2-Naptol
2. Aspirin and Anilide of Aspirin
PRINCIPLE. Presence of impurity generally decreases te melting point so if
t+o compounds a$ing $ery close melting points are mixed te melting point of te
mixture +ill considerably be lo+er tan tat of eiter of te t+o compouns. *o te
melting point determination elps to ascertain +eter te compound is pure or not.
5n some cases te melting point of te compound is $ery close to its deri$ati$e
so it becomes $ery difficult to ascertain by means of melting point tat +eter te
product is formed or not. 5n suc cases! te deri$ati$e sould be mixed +it te
original compound and te mixture sould be sub@ected to melting point
determination. 5f te melting point of te mixture is $ery lo+ tan tat of eiter of te
components it is ascertained tat te deri$ati$e is formed! because if te deri$ati$e
+ere not been formed te mixture +ill a$e te same melting point as te original
compound.
PROCE5URE: 7lose one end of te capillary tube! by olding it in te edge
of a flame continuously rotating till it is sealed. 5ntroduce nearly ).5g of te
completely dried and finely po+dered compound by trusting te open end of te
6
capillary tube into a small eap of te compound and tapping +it te sealed end of
te tube on te benc. Place te capillary tube inside te electrically eated melting
point apparatus and note do+n te melting point. >etermine te melting point of pure
;en<oic acid A 2-Naplol and mixture of te t+o by placing te tubes beside eac
oter inside te apparatus. >etermine te melting point of Aspirin and te product
expected to be Anilide of aspirin and for te mixture of te t+o compounds. Report
"elting point of ;en<oic acid D
"elting point of 2-Naptol D
"elting point of ;en<oic acid A 2-Naptol D
0ence te gi$en sample is P:REE5"P:RE D
"elting point of Aspirin D
"elting point of Anilide of Aspirin D
"elting point of mixture D
Exercie No 7: Stereo 6odel o& Or4anic Com"ound
Aim: 'o construct te bail and stic( stereo models of "etane! Etane! conylene
Acetylene! Acetone and ;en<ene and comment on te sape! structure! bond angle!
bond lengt etc.
PRINCIPLE: 7arbon atom can exist in tree ybridi<ed states depending on te
number of atoms attaced to it.
Car'on atom i SP
)
h$'ridi0ed i& attached to + atom or 4rou".
Car'on atom i SP
!
h$'ridi0ed i& it i attached to ) atom or 4rou".
Car'on atom i SP h$'ridi0ed i& it i attached to ! atom or 4rou".
*P
3
ybridi<ed carbon is tetraedral in sape *P
2
ybridi<ed carbon is trigonal
in sape and *P ybridi<ed carbon is planar. *o depending on te number of atoms
attaced to te carbon atom te stereo model can be build for better understanding of
=
te molecular geometry.
PROCE5URE: 7arbon atom is blac( colored and ydrogen atom is +ite
coloured. /ite stic(s are used to represent te bonds bet+een te atoms. 'ree
different carbon atoms are a$ailable to pro$ide tetraedral! trigonal and planar
arrangement. *elect te carbon atom according to te number of atoms attaced to it.
;uild te model by inserting te stic(s into te oles pro$ided in te corresponding
atom. ,inally report te sape! "olecular orbital picture of te molecule! type of
ybridi<ation of carbon! Number of sigma bonds and pi bonds! bond lengt and bond
angle.
QUESTIONS
1. "olecular formula for "etane! Etane
2. *tate of ybridi<ation of carbon in "etane Etane and Acetylene.
3. /at is te $alency of carbon! oxygen! nitrogen! ydrogen4
-. >efine $alency.
5. >efine bond angle! bond lengt.
8. >efine orbital! molecular orbital.
6. /y acetylene is more reacti$e4
=. /y bond lengt in al(enes! al(ynes is! less tan al(anes4
C. >efine atomic +eigt! molecular +eigt. Equi$alent +eigt and atomic
number.
1). 5:PA7 name for Acetylene.
5i'en0al acetone '$ Claien8 - Schmidt condenation
AI6
'o prepare diben<al acetone by claisenFs - *cmidt condensation
PRINCIPLE
Aromatic aldeydes condense +it alipatic (etones or +it mixed al(yl- aryl
(etones in te presence of aqueous al(ali to form a! B- unsaturated (etones.
C
5n te preparation of diben<alacetone 2 molecules of ben<aldeyde condenses
+it 1 molecule of diben<al acetone. 'is reaction is called claisenFs condensation.
PROCE5URE
1. 5n a 15)ml conical flas place a cold solo of 5.)g of Na?0 pellets in 5)ml
of 0
2
? and -)ml of alcool.
2. /ilst s+irling te contents of te flas! add a mixture of 5.1ml of pure!
redistilled 7
8
0
5
70? and 1.Cml of A.R. acetone. *a(e frequently and
maintain te temperature at 2)-25c for 15min by immersion of te flas( in
a bat of cold 0
2
).
3. ,ilter off te precipitated diben<al acetone at te pump and +as it in cold
+ater to eliminate te al(ali as completely as possible.
-. 7rude precipitate is recrystalli<ed for etyl acetate or Rectified spirit. Pure
diben<al acetone GA yello+ crystal solidH
NOTE
*ufficient alcool is employed to dissol$e te ben<aldeyde and to retain te
initially formed ben<al acetone in solution until it as ad time to react +it te
second molecule of ben<aldeyde.
Pre"aration o& .en0anilide
Aim
'o prepare and submit ;en<anilide
Princi"le
Acylation of an Aromatic 1E2 amine may be readily acie$ed by using an acid
cloride.
5n general! ;en<oyiation of aromatic!amines finds less application tan
acetylation in preparati$e +or(! but te process is often employed for te
identification A caracteri<ation of amines. 5n te scoyen - ;aumen "etod of
;en<oylation! te amine! or its salt is dissol$ed %or& suspended in a sligt excess of = -
1)
15 9 Na?0 A soln a small excess of ben<oyl cloride is ten added A te mixture
$igorously sa(en in a stoppered $essel G;en<oylation proceeds smootly A te
sparingly soluable ben<oyl deri$ati$e separates as a sold.
Procedure
*uspend 1 g %1ml& te substance in 2) ml of 59 Na?0 soln in a /ell - cor(ed
boiling tube %or& small concial flas(! A add 2 ml of ;en<oyl cloride ).5 ml at a time
+it constant sa(ing! and cooling in +ater if necessary sa(e $igorously for 5-1)
min until te odor of ben<oyl cloride as disappeared. "a(e sure tat te mixture
as an Al(aline Reaxn. ,ilter off te solid ben<oyl deri$ati$e& +as it +it a little
cold +ater A Recrystallise it from etanol %or& dil
S9NT:ESIS O; .EN<PP:ENON O=I6E
Aim
'o prepare and submit ;en<openone ?xime.
Princi"le
;en<ppenone condenses +it 0ydroxylamine in te presence of excess of
Na?0 soln to yield te oxime.
%7
8
0
5
&
2
7? I 0
2
N?0
%7
8
0
5
&
2
7DN-?0 I 0
2
?.
Procedure
5n a 1))ml R; ,las( filed c a Reflux condenser place 5 gm of ;en<openone!
3 gm of 0yproxylamine 07l! 1)ml of etanol A 2 ml of 0
2
?! 'o te resulting
mixture no+ add +it sa(ing A.in portions 5.8 gm of solid Na?0 ta(ing care tat
te reaxn does not become too $igorous Jn so cool te flas( under tap +ater. After te
addition of Na?0 is complete eat te flas( under Reflux-for 1) min. cool and pour
te contents of te flas( in a bea(er containing a soln of 15 ml of cone. 07l in 5) ml
0
2
?. ,ilter te precipted ?xime A +as +it cold +ater. Recrystalli<erte product
11
from metanol.
".PDK1-) - 1-227
1ield D 5 gms.
12