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[CONTRIBUTION
FROM THE DEPARTMENTS TEE C,EORGEWASHINGTON
OF CHEMISTRY, UNIVERSITY,
WASHINGTON,
D. c . , AND
THEWILLIAMM. RICE UNIVERSITY, HOUSTON,TEX.]
Several acid-base and oxidation-reduction reactions of a series of 3"- and 4"- substituted derivatives of malachite green
(4,4'-bis-(dimethylamino)-triphenylmethyl chloride) have been studied. The various rate and equilibrium constants are
correlated by the Hammett equation, and the p-values obtained are compared with those calculated by the methods proposed
in several recent theoretical studies. Reasonable agreement is found. The constants obtained for this series are combined
with data for a broader series of triarylmethane derivatives in order to investigate the effects of multiple variations in struc-
ture. It is found that Miller's equation for multiple variation in structure-reactivity correlations gives excellent agreement
with the data.
TABLE 1
PHYSICAL
CONSTANTS
OF MALACHITE
GREENDERIVATIVES
r----------leuco bases---- -Carbinol bases--
M p., a c . Amu, Amu, €mar.” fma.,~ M . P . , OC. Carbon, % Hydrogen, %
Subst. Obsd Lit. rnw emaxa mp H20 MeOH Obsd. Lit. Calcd. Found Calcd. Found
H 99 94 263 3.24 623 8.36 10.7 163 117 79.7 78.1 7.52 7.85
nt”-Cl 110 112 265 3.24 632 8.13 11.1 140 ,. 72.5 70.9 6.58 6.21
p”-a 97 98 264 8.29 627 8.17 ... 160 .. 72.5 72.7 6.58 6.62
m”-CH3 86 85 264 3.24 622 ... 11.5 .. .. .. .. ..
p”-CH3 100 94 262 3.30 620 9.39 ... 151 .. 80.0 79.7 7.78 7.44
m”-NO, I52 152 266 4.12 639 7.51 9.17 165 .. 70.7 69.9 6.40 6.10
P”-N02 179 177 267 4.10 648 5.59 8.20 190 .. i0.7 71.3 6.40 6.61
m”-OCH3 124 123 263 3.27 626 8.65 151 140 76.7 77.0 7.45 7.37
p”-OCH, 105 105 268 3.36 615 9.21 11.5 154 .. 76.7 76.6 7.45 7.52
p”-DMA& 175 173 265 4.86 592 11 0 11.5 190 180 ii 2 77.2 7.98 7.92
l-cm.-l-mole-l X lo-*. Dimethylamino.
TABLE 11
AND RATECONSTASTS
EQUILIBRIUM FOR MALACHITE
GREENDERIVATIVES’
Subst.
H 0 0 6.06 2.40 0.761 2.94 0.67 6.84
m ’’-C1 0.373 0.399 5.80 1.35 1.44 2.58 0.34 6.23
WZ”-CH~ - ,069 - ,066 , . .. .. .. .. 7.21
p”-CH, - ,170 - ,311 .. .. .. .. .. 7.27
m”-NOz ,710 ,710 5.73 0.442 1.80 2.17 0.10 5.84
p’ ‘-NO* .778 ,778 .. 0.392 1.77 2.28 0.03 5.50
WZ”-OCH~ ,115 ,047 .. .. .. .. .. 6.95
p”-OCH3 - ,268 - ,778 .. .. .. .. .. 7.18
p”-DMAy - .83 -2.00 .. .. .. .. , . 9.36
p’’-Br ,232 0.150 .. .. .. .. .. 6.38
H. C. Brown and D. McDaniel, J.Oug. Chem., 23, 420 (1958). b H. C. Brown and Y . Okamoto, J.Anz. Chem. SOC.,80,
4978 (1958). Ref. 2 ; aqueous solution, d Relative values, see text, methanol solution. e k , set.-'. k , l.-mole-’-
min. -I. 0 Dimethylamino. Temperature 25’.
then, that we have indeed obtained the carbinol change in the color of the solution, followed by a
bases (111,R = H). slow fading of the color. When equilibrium is
Because of the solubility limitations of the car- reached, the visible spectrum of the solution is
binol bases and leuco bases in water, we have identical to the original spectrum except for dimin-
examined all of the reactions in methanol solution. ished intensity. No absorbance corresponding to
Buffer solutions were prepared by partial neutrali- that expected of the monoprotonated dye is ob-
zation of various tertiary amines with p-toluene- servable except in the case of crystal violet.
sulfonic acid. The inertness of the amine toward From the changes observed it may be deduced
the dyes was established in each case by the use that the monoprotonated dye reacts with solvent
of different buffer concentrations. to form the diprotonated methyl ether. The same
Spectrophotometric measurements have been behavior is noted in water, and Hantzsch4was able
employed throughout, and the procedures are to isolate the triprotonated carbinol base in the case
described in detail in the Experimental section. of crystal violet.
Conversion of Dyes to Methyl Ethers (I1 F! 111, The equilibrium constants for the conversion
R = CH,) .-The relative equilibrium constants (I1 & IX, R=CH3) were measured by adding
for the transformation of the methyl ethers to the known amounts of p-toluenesulfonic acid to ca.
dyes were measured in anhydrous methanol using molar solutions of the dyes in methanol. The
tribenzylamine-tribenzylammonium p-toluenesulfo- results are shown in Table 11.
nate buffers. The results are reported in Table I1 Basicity of Leuco Bases (IV Ft I) .-The basicities
as P K a - p K t r i b e n z y l a m i n e . of the leuco bases were measured in dichloroacetic
The relative rates of reaction of the dyes with acid-dichloroacetate buffers in which the extent of
methoxide were measured in triethylamine-tri- protonation of the leuco bases is small. The second
ethylammonium p-toluenesulfonate buffers. The ionization of the leuco bases has, therefore, been
rates, in each case, were measured a t two different neglected. The values of the first ionization con-
buffer ratios The ratio of pseudo-first-order rate stant are reported in Table 11, and are calculated
constants obtained agreed with those calculated using the value of pKa = 6.4 for the ionization of
assuming that the rate of reaction of the dye with dichloroacetic acid.5
methanol was negligible. The results are reported The Reaction of the Leuco Base of Malachite
in Table I1 as the log of the pseudo-first-order rate Green (I, X = H) with Chloranil (I + II).-The
+
constants, log kl = log kz log K b (triethylamine) stoichiometry of the reaction of the leuco base of
Conversion of Dyes to Protonated Methyl Ethers
(IX (R=CHQ) + 11) -&’hen acid is added to a (4) A. Hantzsch, Bcr., 33, 752 (1900).
( 3 ) I< P Bell, “The Proton in Chemistry,” Cornell University
solution of one of the dyes, there is an immediate Press, lthacs. 6 .Y..1959. p. 44,
June 20, 1962 IN TRIARYLMETHANE
LINEARFREEENERGY REACTIONS 2351
r
2.5 -
0
\\\
-I
I
2.3- '
55
I ,
I..........
02 04 06
o \
08
0 02 0.4
4
0.6 0.8
160-
um.x10-4
158-
1.56 -
0
.O 0.2 0.4 0.6 08
02 0.4 06 08 0:
a: Fig. 7.-Hammett plot of frequencies of absorption of dyes.
Fig. 4.-Hammett plot of equilibrium constants for conver- and which appears reasonable from the mechanism
sion of dyes to diprotonated methyl ethers. of other triphenylmethane oxidations,"' is a hy-
dride transfer
r.d.
ArpCH +Q ---f Ar&+ + HQ-
fast (2)
HQ- + H + --+- HzQ
Obviously, however, our data do not rule out
other mechanisms in which a slow second-order
reaction is followed by a fast step producing the
dye. Nor can we rule out a mechanism similar to
that proposed by Swain and Hedberg" for the oxi-
dation of leuco malachite green by ceric sulfate.
Assuming mechanism 2, if the charge on the
carbonium ion were fully developed in the transi-
I . 02
04
06 08
tion state of the rate-determining step, we should
expect a p of nearly the same magnitude as that
cr: for the equilibrium conversion of the methyl ether
Fig. 5.-Hammett plot of rate constants for reaction of to the dye (-2.6). Since the observed p is only
leucos with chloranil. -0.81, very little charge has developed in the
transition state.
R=CHI) and that for the formation of the methyl Basicity of the Amino Groups in the Leucos and
ether from the dyes (I1 a 111, R=CHa). Thus, Methyl Ethers.-The p for the basicity of the amino
p for the diprotonation of the methyl ethers is group in the leuco bases (-0.47) is very close to
-1.31. that which one would predict from the basicity
The Reaction of Chloranil with the Leuco Bases. of anilines in methanol (-3.0212), and the fall-off
-Any mechnnism proposed for the oxidation must factor for a benzene ring (0.30318)and a saturated
be in accord with the observed second-order (10) R. Stewart, Con. J . Chem., 35, 766 (1957).
kinetics, and the observation that the dye is the (11) C. G. Swain and R. Hedberg, J . A m . Chem. Soc., 7 2 , 3375
(1950).
initially produced species. T h e simplest mech- (12) H. H. Jaffe, Chcm. Reus., 58, 191 (1953).
anism that is in accord with these observations, (13) € HI Jaff.5, J . Chrm. Phys., It, 415 (1953).
..
June 20, 1962 LINEARFREEENERGY
IN TRIARYLMETHANE
REACTIONS 2353
/ 2 0 -2 -4 -6
0
IC? -8 0 8 16
I.
Physical constants for the compounds are shown in Table El = '/z(Eo Ez) +
where E L is the molar absorbance of the monoprotonated
Fluoroborate salts of the dyes were prepared by adding leuco base, Eo that for the free base and E2 that for the
sodium fluorobordte to aqueous solutions of the dyes buffered diprotonated leuco base.
;it PH 4.0. The fluoroborates were recrystallized from water. E2 was determined by measuring the absorbance of the
Basicity of Methyl Ethers in Methanol.-Buffers pre- leuco base in a methanolic solution 10-1 M in p-toluenesul-
pared by adding p-toluenesulfonic acid to methanol solu- fonic acid, and Eo by measuring the absorbance of the leuco
tions of tribenzylamine were found to be in the proper range base in pure methanol.
for measurement of the equilibria between the dyes and the The equilibrium constants were then calculated using an
methyl ethers. equation analogous to 5. Typical experimental data are
A typical experiment was performed by adding an aliquot shown in Table V.
portion of a solution of the dye, or carbinol, in methanol to
a buffered portion of methanol, waiting for establishment V
TABLE
of the equilibrium, and measuring the absorbance of the
resulting solution in the visible range with a Cary model DETERMINATION
OF EQUILIBRIUM CONSTANTS
14 spectrophotometer.
A second aliquot of the dye solution was added to nietli-
IV I +
H + ; nz"-C1 Substituent
ariol buffered a t p H = P K t r i b e n ~ y l a m i n e - 1.00 in order to HuBer'L
ratio Absorbance fiK - PKuch
determine the absorbance of the dye. It was found that
:tt this PH the dissociation of the methyl ethers was com- ... 1 .874b .....
plete. 0.291 1.799 -0,525
The various buffers were prepared by adding knowii 0.962 1.670 - ,538
amounts of tribenzylamine to a methanolic solution 1.08 X
lO-.a M in p-toluenesulfonic acid, which had been stand- 1.625 1.580 - .542
ardized against standard sodium hydroxide. 2.23 1.519 - ,564
The inertness of the amine toward the dye was estab- "Buffer ratio = (HA)/(A-). b Absorbance in pure
lished by repeating the measurement using a solution having methanol.
a different buffer concentration but the same ratio as pre-
viously used. Conversion of Dyes to Diprotonated Methyl Ethers .-
The final concentration of dye plus ether was in each case Carefully measured volumes of standardized -toluenesul-
ahout l O - ' M . fonic acid in methanol were added to d s o l u t i o n s of
The cquilit)riulll constant. \\ere calcrllatatl f r t ) l n (he the dyes in methanol (prepared bl- adding the fluorobordte
equation salt to methanol). After equilibrium had been established,
June 20, 1962 LINEARFREEENERGY REACTIONS
IN TRIARYLMETHANE 2355
‘g
‘9
-0.61
-0.8
I TIME (mins.),
100 300 700 Fig. 11.-Second-order rate plot for reaction of leuco
TIME (SECS.). nialachite green with chloranil; (Ar3CH)o = ( Q ) o = 2.39 X
Fig. 10.-Pseudo-first-order rate plot for reaction of niala- .lf; absorbance measured in 1-mm. path length cell.
cliite green with mctlioxide: I, buffer ratio = 1.64; 11,
buffer ratio = 5.57; 0, (R3A7HC) = 5.41 X 10-3M; 0 , trations (ca. 5 X 31) in lY0 acetic acid in methanol
( R ~ x H + )= 1.08 x 10-3.1’1. (the amount of acid determined to give complete conversion
of the methyl ether to the dye, and only a small extent of
the absorbances of the solutions in the visible region \vcre protonation of the leuco base), and then mixing equal
ineasured . Calculations were analogous to those described volumes of the solutions.
above. Complete ultraviolet and visible spectra were obtained a t
Some typical data are shown in Table V I . 18 and 24 hours reaction time.
The absorbance of the solution a t 620 mp was used t o
TABLE VI calculate the amount of dye present. Assuming 1:l
stoichiometry, and using the spectra of the pure com-
OF EQUILIBRIUM
DETERMINATION CONSTANTS ponents, a theoretical spectrum was calculated and com-
pared with the experimental. Xearly perfect agreement
IX, ( R = CH3) I1 f CH8OHp’; X = H(A,,,, was obtained in both cases.
= 1.502) After 48 hours reaction time, the experimental and
Concn. of p-toluene- theoretical spectra did not agree. Analysis of the experi-
sulfonic acid Absorbance 8K mental spectrum revealed that more dihydrochloranil than
1.67 X 1.370 0.761 dye was present. The spectrum of the master solution of
3.34 x 10-2 1.314 ,631 chloranil also revealed the presence of dihydrochloranil
6.68 X 1.131 ,691 after 48 hours.
Second-order plots of absorbance data for more concen-
1.34 X 10-1 0.860 .747 trated reaction mixtures were accurately linear to about
1.67 X 10-1 ,760 772 5070 completion. The presence of air resulted in deviations
3.34 x 10-1 ,491 . i90 from linearity much sooner, and the calculated rate con-
stants were higher than those obtained from degassed solu-
Reaction of Dyes with Methoxide.-Buffer solutions pre- tions by about 20%.
pared by adding p-toluenesulfonic acid to solutions of tri- Because of the complicating factors, initial rates werc
cthylainine in methanol were found to give a range of used t o calculate rate constants for the reaction. The
PH in which the dyes are completely converted to the methyl constants obtained in this manner agreed reasonably well
ethers. with those obtained from second-order plots of degassed
The reactions were followed by adding an aliquot portion solutions, and were more reproducible.
of a solutiori of the dye fluoroborate in methanol to a quantity -4 typical second-order plot is shown in Fig. 11.
o f the buffer, placing the resulting solution in a 1-cni. path Runs using various concentrations of acetic acid wcrc
leiigth cell and measuring the absorbance 51s. time by placiiig made to establish the independence of rate constant 011
(tie cell in the therrnostated conipartmciit o f a Cary inodcl acid concentration over a tenfold raiige of liydrogen io11
1.1 spectrophotometer set t o record absorbari concentration, (i.e., 100-fold range of concentrations of
length oi maximum absorbance of the dye, a t a ktinwii acetic acid ) .
(.hart speed. When the reactions were carried o u t in the absence o I
First-order plots of the data gave the pseudo-first-order acetic acid, the color of the solution increased in intensity.
rate constants, kl. Runs at two different buffer ratios and then decreased until no color remained after severdl
cstablished that the reactions are first order with respect hours. Addition of acid to the solution resulted in the ini-
to triethoxide, and that the rate of reaction with methanol mediate appearance of color.
is iiegligible. Runs a t different buffer concentrations estab- Infrared Spectra.-Infrared spectra of the carbinol
lished the inertness of triethylamine toward the dye. bases were measured in C S and CC1, solutions with a Per-
Some typical first-order plots are shown in Fig. 10. kin-Elmer model 21 spectrophotometer.
Reaction of Leuco Bases with Chloranil .-In order to Molecular weight determinations were performed oii
cstablisli the stoichioiiietry of the reaction of chloranil with crystal violet carbinol using standard techniques.
lllc leuco bases, tlic complete ultraviolet and visible spectra QualitativeTestfor OxygeninMalachiteGreen Carbinol.-
o f chloratiil, dihydrochloranil, leuco malachite grcrn and Anhydrous hydrochloric acid was passed through a solutiori
irialachite green fluoroborate were measured on carefully of 75 mg. of malachite green carbinol i u 20 ml. nf carboii
purified materials in methanol solution. Solutions con- tetrachloride until precipitation was complete.
taining mixtures of any two of the above components were The lightly colored solvent was carefully decanted, and
observed to give spectra exactly corresponding to the sum the gummy precipitate was dissolved in 0.10 ml. of absolute
of the spectra of the individual components. ethanol. The resulting ethanol solution was then analyzed
The spectra obtained were used to analyze the spectra for water by gas chromatography o n an 8’ polyethylene
of reaction mixtures prepared from known amounts of glycol column. The presence of water was clearly shon.ri
chlordnil and leuco base a t various reaction times. by the chromatogram.
X typical experiment was performed by preparing master A blank of the alcohol, treated in the same tiiaiiiier, did
solutions uf the leuco base and of chloranil of equal concen- iiot show the presence of water.
2356 MARKN. RERICKAND ERNESTL. ELIEL VOl. 84
[CONTRIBUTION
FROM THE DEPARTMENTOF CHEMISTRYAND RADIATION
LABORATORY’ OF SOTRE
OF THE UNIVERSITY DAME,
NOTREDAME,IND.,AND THE DEPARTMENTOF CHEMISTRYOF PROVIDENCE
COLLEGE,PROVIDENCE, R. I.]
Reduction with Metal Hydrides. IX. Reaction Paths in the Reduction of Epoxides
with Lithium Aluminum Hydride and Aluminum Chloride’
BY MARKN. RERICKAND ERNESTL. ELIEL
JANUARY 3, 1962
RECEIVED
The nature of the reduction products of triphenylethylene oxide with “mixed hydride” (lithium aluminum hydride-
aluminum chloride) has been found to depend on the proportions of LiAlHl and AlCll in the reagent. With a 1:3 (AlCla:
LiAlH4) reagent, presumably containing AlHa as the active reducing agent, the product is the previously observed phenyl-
benzhydrylcarbinol, PhzCHCHOHPh, probably formed by direct, electrophilically assisted reductive ring opening of t h e
epoxide. With a 4: 1 reagent, presumably AlHClz and excess AlCla, the main product is PhaCCH*OH, accompanied by hy-
drogenolysis products of PhtCHCHOHPh. With this reagent, reduction seems to be preceded by rearrangement of t h e
ep.oxide to the aldehyde PhsCCHO (phepyl shift) as the major product and the ketone PhzCHCOPh (hydride shift) as t h e
minor product. Treatment of the epoxide with AlCh gave the aldehyde and ketone in a 3 : l ratlo, as distinct from treat-
ment with BFa which gives almost entirely the aldehyde. The reaction of the epoxide with AlCla seems to involve a com-
plex of the chlorohydrin PhzCClCHOHPh as the first intermediate. This unstable chlorohydrin was prepared by treat-
ment of the epoxide with hydrogen chloride. Upon treatment with a limited amount of LiAIHI (C0.25 mole) it also gave
a mixture of PhsCCHO and PhzCHCOPh with the aldehyde predominating, and upon reduction with mixed (4: 1) hydride
it gave PhsCCHrOH, whereas with excess LiAlH, alone it gave mainly PhZCHCHOHPh. I n this latter reduction, the ketone
PhzCHCOPh is not an intermediate, since deuteride reduction gave PhZCDCHOHPh, as shown by n.m.r. spectrum, rather
than PhzCHCDOHPh. Similar results are obtained with p-diisobutylene oxide which gives mainly MeaCCMeZCHzOH
with the 4:l reagent but mainly MeaCCHOHCHMet with the 1:3 reagent.
I n previous p u b l i ~ a t i o n sfrom
~ ~ ~this Laboratory, latter to 2,2,3,3-tetramethylbutanol-1(IV). I t
the reduction of epoxides with lithium aluminum was postulated that the reduction of I to I11 in-
hydride-aluminum halide mixtures (“mixed hy- volved a hydride shift in the acidic reaction medium
drides”6) has been described. Of particular in- producing phenyl benzhydryl ketone (VI) as an
terest in connection with the present investigation intermediate. This postulate was based on the
is the reduction of triphenylethylene oxide (I) and demonstrationa that reduction of styrene oxide with
of @-diisobutylene oxide (11). The former gave lithium aluminum deuteride-aluminum chloride
rise to phenylbenzhydrylcarbinol (111) and the
B Fa /O\
(CeHa)tCCHO t ( C ~ H ~ ) ~ C - C H C S H ~
V I
- “m.h.”
(CsW6)zCHCHOHCsH
gave 2-phenylethanol-1-d, evidently v i a phenyl-
acetaldehyde, and that similar reduction of iso-
butylene oxide gave isobutyl-1-d alcohol v i a iso-
butyraldehyde. The mechanism of reduction of
I to I11 was inferred by analogy, passing over the
- 111
fact that in this reduction lithium aluminum hy-
dride pre-treated with allyl bromide was used
AlClr /o\ rather than lithium aluminum chloride-aluminum
-
(CHa)dWCHa)zCHO ( CH,)2CH-C~( C H , ) ~ halide. At the time, this did not seem to matter,
VI1 I1 since allyl bromide (believed to be a generator of
“m.h.” inorganic bromide in situ) had been employed inter-
( CHt )lCC( CHa)2CH20H changeably with aluminum halides in other reduc-
IV tions.: The reduction of I1 to IV was similarly
( C O H ~ Z C H C O C J L (C & ) ~ C C H ~ O H postulated to involve shift of a t-butyl group to
VI VI11 give tetramethylbutyraldehyde (VII) as an inter-
(CH&CCHOHCH( CH& mediate.4 In this case the reality of the inter-
IX mediate was demonstrated by isolating i t from the
reaction of IT with aluminum chloride in the ab-
( 1 ) The Radiation Laboratory is operated under contract with the sence of hydride.‘
Atomic Energy Commission. Enquiries regarding this paper should The postulated rearrangement of I to VI became
be directed to E. L. E., University of Notre Dame. Presented before a matter of concern in the light of a recent surveys
the Division of Organic Chemistry at the meeting of the American
Chemical Soaety at New York, N. Y., September 12, 1960.
which suggests that phenyl usually migrates in pref-
(2) Paper VIII, E. L. Eliel and M. N . Rerick. J . Am. Chem. Soc., erence to hydrogen and especially in view of the
83, 1367 (1960). demonstration’ that treatment of triphenylethylene
(3) E. L. Elid and D. W. Delmonte, ibid., 80, 1744 (1958). oxide (I) with boron trifluoride etherate gives tri-
(4) E.L. Eliel and M. N . Rerick, ibjd., 81, 1362 (1960).
(5) For a review of mixed hydride reductions cf. M. N . Rerick,
phenylacetaldehyde (V) by a phenyl shift rather
“Selective Reduction of Organic Compounds with Complex Metal (6) R. E. Parker and N. 5. Isaacs, Ckm. Revs., 69, 737 (1959).
Hydrides,” Metal Hydrides, Inc., 33 Congress Street, Beverly, Mass., (7) A. C. Cope, P. A. Trumbull and E.R. Trumbull. J , Am. Chcm.
1959, snd E. L. Eliel, Roc. Chem. Progr., I S , 129 (1961). Soc., 80, 2844 (1968).