June 20, 1962 FREEENERGYIN TRIARYLMETHANE

LINEAR REACTIONS 2349

[CONTRIBUTION
FROM THE DEPARTMENTS TEE C,EORGEWASHINGTON
OF CHEMISTRY, UNIVERSITY,
WASHINGTON,
D. c . , AND
THEWILLIAMM. RICE UNIVERSITY, HOUSTON,TEX.]

Application of Linear Free Energy Relationships to Some Reactions of

Triarylmethane Derivatives
BY CALVIND. RITCHIE,~W.F. SAGERAND E. S. LEWIS
RECEIVEDDECEMBER16, 1961

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.

Introduction with those obtained by oxidizing a known amount

A series of 3"- and 4"-substituted derivatives of of the leuco base with an excess of chloranil and
malachite green (4,4'-bis (dimethylamino)-tri- adding several lambda of the resulting solution to
phenylmethyl chloride) provide the opportunity an aqueous solution buffered at pH 4.0.
to study a number of add-base and oxidation-
reduction reactions in which the basic skeletal
structure of the substrate is unchanged from one
reaction series to another. Thus, these reaction
series furnish an interesting set in which to investi-
gate the applicability of structure-reactivity cor-
relatias.
The base strengths of a wide series of substituted
triarylmethanols have been previously investi-
gated,2 and the data can be combined to provide 1T It
a test of multiple variations in structure-reactivity
correlations.'
In this paper, we shall be concerned with the
various transformations indicated in Scheme I,
with R = H or CH3.
Methods and Results
A series of 3"- and 4"-substituted leuco bases of
malacbite green (I) were prepared by the condensa-
tion of the appropriately substituted benzaldehyde
It 1T
with dimethylaniline in aqueous sulfuric acid.
The carbinol bases I11 were prepared by oxidation
of the leuco bases with excess chloranil (tetra-
chloro-$-benzoquinone). Fluoborate salts of the
dyes I1 were prepared by dissolving the carbinol
bases in dilute aqueous acid and adding sodium
fluoborate to precipitate the salts.
The carbinol bases proved to be exceedingly dif- SCHEME
1.-R is H or CH,.
ficult to purify. The final compounds used in this A rather disturbing feature of the carbinol
study showed extinction coefficients which were bases is that we have been unable to observe an
generally higher than any previously reported. OH stretching band in the infrared spectra. That
The melting points of the carbinol bases were also the absence of the OH band in the infrared is not
generally higher than those which have been due to hydrogen bonding is indicated by the fact
reported in the literature. that a band fails to appear when a dilute solution
Physical data and elemental analyses of these of the carbinol base in carbon tetrachloride is
compounds are shown in Table I. The elemental examined in a 1- cm. path length cell. An exami-
analyses are poorest for those compounds which nation of the n.m.r. s ectrum of the carbinol base
we have found hardest to purify. The extinction of crystal violet, 811, X = p-dimethylamino),
coefficients obtained by dissolving tlhe carbinol also failed to show a band corresponding to a
bases in aqueous solution buffered at pH 4.0 agree proton of an OH group. The presence of oxygen
(1) To whom correspondence regarding this paper should be ad-
dressed a t Department of Chemistry, T h e University of Buffalo,
is shown, however, by the results of the elemental
Buffalo 14, N. Y. analyses, and by a qualitative test for oxygen de-
(2) (a) N. C. Deno, ct ai., J. Org. Chcm., 19, 155 (1954); J . Am. scribed in the Experimental section. Molecular
Chcm. SOL, 77, 3044 (1955); 7'7, 3051 (1955); 79, 6805 (1957). (b) weight determinations, both by depression of the
0. F. Ginsberg and N. S. Mel'nkova, J . Gcn. Chem., U. S. S. R.,I6,
1109 (1955); C. A . , 61, 16368 (1957). (e) M. Gillois and P. Rumpf,
melting point of camphor and by the isopiestic
Compf. rend., 238, 591 (1954). method for benzene solution, show that the carbinol
(3) S. I. Miller, J . Am. Chem. SOL,81, 101 (1959). bases are monomeric. There can be little doubt,
2350 CALVIN ll‘. F.SAGER
D. RITCHIE, AND E. s. LEWIS 1701. 84

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
bases (111,R = H).
Because of the solubility limitations of the car-
binol bases and leuco bases in water, we have
examined all of the reactions in methanol solution.
Buffer solutions were prepared by partial neutrali-
zation of various tertiary amines with p-toluene-
sulfonic acid. The inertness of the amine toward
the dyes was established in each case by the use
of different buffer concentrations.
Spectrophotometric measurements have been
employed throughout, and the procedures are
described in detail in the Experimental section.
Conversion of Dyes to Methyl Ethers (I1 F! 111,
R = CH,) .-The relative equilibrium constants
for the transformation of the methyl ethers to the
dyes were measured in anhydrous methanol using
tribenzylamine-tribenzylammonium p-toluenesulfo-
nate buffers. The results are reported in Table I1
as P K a - p K t r i b e n z y l a m i n e .
The relative rates of reaction of the dyes with
methoxide were measured in triethylamine-tri-
ethylammonium p-toluenesulfonate buffers. The
rates, in each case, were measured a t two different
buffer ratios The ratio of pseudo-first-order rate
constants obtained agreed with those calculated
assuming that the rate of reaction of the dye with
methanol was negligible. The results are reported
in Table I1 as the log of the pseudo-first-order rate
+
constants, log kl = log kz log K b (triethylamine)
Conversion of Dyes to Protonated Methyl Ethers
(IX (R=CHQ) + 11) -&’hen acid is added to a
solution of one of the dyes, there is an immediate
change in the color of the solution, followed by a
slow fading of the color. When equilibrium is
reached, the visible spectrum of the solution is
identical to the original spectrum except for dimin-
ished intensity. No absorbance corresponding to
that expected of the monoprotonated dye is ob-
servable except in the case of crystal violet.
From the changes observed it may be deduced
that the monoprotonated dye reacts with solvent
to form the diprotonated methyl ether. The same
behavior is noted in water, and Hantzsch4was able
to isolate the triprotonated carbinol base in the case
of crystal violet.
The equilibrium constants for the conversion
(I1 & IX, R=CH3) were measured by adding
known amounts of p-toluenesulfonic acid to ca.
molar solutions of the dyes in methanol. The
results are shown in Table 11.
Basicity of Leuco Bases (IV Ft I) .-The basicities
of the leuco bases were measured in dichloroacetic
acid-dichloroacetate buffers in which the extent of
protonation of the leuco bases is small. The second
ionization of the leuco bases has, therefore, been
neglected. The values of the first ionization con-
stant are reported in Table 11, and are calculated
using the value of pKa = 6.4 for the ionization of
dichloroacetic acid.5
The Reaction of the Leuco Base of Malachite
Green (I, X = H) with Chloranil (I + II).-The
stoichiometry of the reaction of the leuco base of
(4) A. Hantzsch, Bcr., 33, 752 (1900).
( 3 ) I< P Bell, “The Proton in Chemistry,” Cornell University
Press, lthacs. 6 .Y..1959. p. 44,
June 20, 1962 IN TRIARYLMETHANE
LINEARFREEENERGY REACTIONS 2351

malachite green with chloraniP to produce the cor- TABLE

I11
responding dye in methanol solution degassed with EQUATION
HAMMETT CORRELATIONS
nitrogen was found to be accurately represented Reaction P -log KO
by eq. 1 to about 50% completion. After this IV I equil. MeOH, 25’ 0.466 6.05
Ar3CH -I- Q + H+ Ar3C+ + H2Q (1) 11 is 111( R = CHI) equil. MeOH,
25’ 2.64 2.37
point, the amount of dihydrochloranil present I1 -t 111 ( R = CHI) rate, MeOH,
became progressively greater than the amount of 25’ 0.940 2.93
dye. Since the concentration of dye plus unre- IX F? I1 ( R = CHa) equil. MeOH,
acted leuco base was always equal to the initial 25” -1.33 0.824
concentration of leuco base, i t appears that the I -P 11, rate MeOH, 25” -0.81 -0.66
complication is caused by a slow reaction of chlor- I1 + I11 ( R = H)“ equil. H20,20” 1.83 i.01
ani1 with solvent. vrnax, of dyes H20, 2 5 “ , crn.-l - 559 16,040
The rate of oxidation of the leuco base followed 0 Data taken from ref. 2b.

second-order kinetics accurately to about 50%

completion. If air was not removed from the Also shown in Table I11 are the results of the
solutions, the kinetics were second order to only application of the Hammett equation to the cor-
about 25y0 completion, and the rate constant de- relation of the wave lengths of maximum absorb-
termined was about 20% higher than that de- ance of the dyes, and to the data for the basicity
termined in degassed solutions. of the carbinol bases in water. Plots of the data
A tenfold change in the hydrogen ion concentra- are shown in Figs. 1-7.
tion of the reaction solution caused no change in
the rate constant.
If the reaction was carried out in solution buffered
a t a pH where the carbinol was the stable species,
the concentration of dye initially rose, and then
declined as the reaction proceeded. Although no
quantitative measurements were made, this ob-
servation indicates that the dye is the initially
produced species in the reaction.
The second-order rate constants, calculated from
initial rates of reaction in 0.1 M acetic acid in
methanol, are reported in Table 11.
Evidence for the Existence of Monoprotonated
Carbinol Base in Aqueous Solution.-It was noted
that the extinction coefficient of malachite green is
considerably greater in methanol than in water
(cu. 25Y0). The integrated intensities of the visible 0:
bands differ by only 7%. When a solution of the Fig. 1.-Hammett plot of basicities of leuco bases.
dye in methanol is rapidly diluted with water,
buffered a t FH 4.0, the absorbance of the dye is
cu. 7% greater than that normally measured.
The absorbance of the solution slowly decreases
to the normal value.
These observations are simply explained if one
assumes that the dye is in equilibrium with the
monoprotonated carbinol base (I1a VI) in aqueous
solution.’ The position of this equilibrium is
independent of $and €wouldI be exceedingly dif-
ficult to determine in studies with aqueous solutions
alone.
The integrated intensities of solutions of the dyes
in acetonitrile are the same as those in methanol,
and we take this as evidence that practically no
monoprotonated methyl ether exists in the meth- 05t
anol solutions. 0 02 04 06 oe
Discussion 0
Application of the Hammett equations to the Fig. 2.-Hammett plot of basicities of methyl ethers
data of Table 11, using only m”- and “+R” 9”-
substituted compounds in the correlationg gives the One other p-value may be determined from the
results shown in Table 111. present data by noting that p for the reaction of
(6) J. H . Jones, et al., J . Assoc. Of. Agric. Chcm., 88, 977 (1955). the dyes to form the diprotonated methyl ethers
(7) The possibility of monoprotonated carbinol base in certain (I1 F? IX, R=CH,) must be the sum of p for the
cases has been suggested by: C. C . Barker, G. Hallas and A . Stamp, diprotonation of the methyl ethers (I11 F? IX,
J . Chem. SOL.,3791 (1960).
( 8 ) L. P. Hammett, “Physical Organic Chemistry,” McGraw-Hill (9) Procedure recommended by: R . W. Taft, Jr., and I. C. Lewis,
Book Ca., Inc.,S e w Ycrk, N . Y.,1840, Chap. V I I . J. A m . Chcm. Soc., 81, 5343 (1959).
2352 CALVIND. RITCHIE,w.F.SAGER AND E. s. LEWIS Vol. 84

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

G Fig. 6.-Hammett plot of basicities of carbinol bases in

Fig. 3.-Hammett plot of rate constants for reaction of dyes aqueous solution.
with methoxide.

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

Fig. 8.-Hammett plot of basicities of triarylmethanols in f (4.

water. Fig. 9.-Plot of basicities of triarylmethanols according to
eq. 4.
carbon atom (0.35814). Thus one predicts p =
-0.33 (i.e., -3.02 X 0.303 X 0.358). where D is the dielectric constant of the solvent,
Rho for the reaction I11 $ VI, R = CH3, and Aur is the difference in the u constant of the
may be estimated as one-half that for reaction I11 reaction site in the reactants and products.
IX, R = CHa, if we assume that the protonated If one assumes that the effect of an OH group
amino group of VI does not appreciably change the is very nearly that of an OCH3 group, this value
effect of the X group on the second amino group. may be compared with that found for the basicity
The value estimated in this manner (-0.655) of the carbinol bases in water (-1.83). The
is higher than expected by a significant amount agreement is excellent.
when compared with p for the reaction I $ IV Multiple Variations in Structure-Reactivity Cor-
of the leuco bases. relation.-Deno2a has determined the basicity of a
Since the only change from the leuco base situa- large number of mono-, di- and trisubstituted
tion is that a hydrogen has been replaced by a triphenylmethanols in aqueous solution, and has
methoxyl on the central carbon, we must ascribe calculated a p for this series of -4.0. A plot of
the differences in p values to an increased transmis- Deno's pK values and the values for the malachite
sion by the central carbon when H is replaced by green series versus the sum of the u values of the
OCH3. substituents is shown in Fig. 8. The plot is cer-
Qualitatively, this observation is in agreement tainly not linear.
with the prediction that the transmission properties Plotting only the monosubstituted derivatives
of groups are changed by substitution.l6 versus u gives a p of -4.0. If one then examines
It should be noted that this change is in the op- the eq. 4 for multiple variations in structure,'j
posite direction to that found in the aliphatic it is seen that the difference between this value
series,16 however. In the aliphatic system, an
electron-withdrawing substituent attached to log K = ( V I uz C I ) , ~ O (UIUZ + + 0143 4 + +
carbon diminishes the transmission properties of UZ'J3)q log KO (4) +
the carbon, while in the present system, the substi- and that for the malachite green series is due
tution of OCHs, an electron - withdrawing substit- to the term q (h., p - pa = (az a&). + +
Assign-
uent, for hydrogen has increased the transmission ing a u value of -2.00 to the dimethylamino
properties of the carbon. group,18wethenfindq = -0.55.l9
From the arguments presented in the earlier The sign of q is the same as that of p as required
paper,16 this result requires a value of q16 which is from the previous section.
of the same sign as p , rather than of opposite sign Figure 9 shows a plot of the first two terms on the
as in the aliphatic series. We shall proceed to right of eq. 4 versus the experimental pK values
show that this result is consistent with other proper- for all of the experimental data available. The
ties of the system. line drawn is the line of unit slope predicted by the
Basicity of the Methyl Ethers.-From the equation.
value of p for the basicity of the methyl ethers We feel that this correlation, involving a range in
found in this work, we predict a p of -1.95 in K of over twenty powers of ten, is a striking con-
aqueous solution, using the equation (17) W. F. Sager end C. D. Ritchie, J . A m . Chem. SOC.,83, 3498
(1.8 + 67/D)Aur = p" (3) (1961).
118) H. C. Brown and Y. Okamoto, ibid., 80, 4979 (1958); the
(14) R. W. Taft, Jr., and I. C. Lewis, J . A m . Chcm. Soc., 80, 2436
(1958).
extreme value of u was chosen because of the nature of the present
(15) C. D. Ritchie, J . Phys. Chrm., 66, 2091 (1961).
(16) Q is the constant in the equation: log K
log
-
Zuipo
K O ,which was derived by Miller (cy. ref. 3).
i
+ z'uiu,g +
1.i
system.
(19) This treatment implicitly assumes the propeller model for the
triarylcarbonium ions. Cf.N. N. Lichtin and M. J. Vignoli, J , A m .
Chrm. Soc., 19, 679 (1957).
2354 AND E. S.LEWIS
CALVIND. RITCHIE,W. F. SAGER Vol. 84

firmation of the utility of multiple variations in PKt. - f'Ktribensylsmina = lOg[A/(Amax - A ) ] +

structure-reactivity correlations. log[(Rali)/(RaNH')] (5)
Experimental where A is the absorbance of a solution with buffer ratio
(R+)/(RaNH+), A,, is t h e absorbance of a solution con-
Materials.-Eastman Kodak Co. p-toluenesulfonic acid taining the same amount of added dye, but buffered a t
was recrystallized from methanol and dried a t 100" for pH = pKamine- 1.00, and K, is the equilibrium constant
several hours. for the reaction
Dichloroacetic acid was distilled a t atmospheric pressure
through a 50-cm. Vigreux column. The fraction boiling
between 193.5 and 194.5' was collected and used for the
Ar3C+ + CH30H Ar30CH3 + Hf
preparation of buffers. Table 11. shows a series of typical experimental data.
Practical grade chloranil was recrystallized from ben-
zene to constant melting point. Dihyorochloranil was re- TABLE IV
crystallized from ethanol. DETERMINATION O F EQUILIBRIUM COXSTANTS
Reagent grade anhydrous methanol was used without
further purification.
Tribenzylamine and triethylamine were Eastman Kodak
ArC+ 4- C H 3 0 H ArJCOCH3 H+; +
p"-NOz derivative
Co. white label reagents. Buger Ab- pK - Buffer Ab- pK -
Temperature Control.-The Cary model 14 spectropho- ratioa sorbance pK.,i,, ratioa sorbance pK.,i..
tometer was equipped with a thermostated cell compartment
which was kept a t 25 & 0.5' by means of water circulated O.lOb 1.220 ... 2.00b 0.707 0.397
from a constant temperature bath. All solutions were .30b 1.138 0.403 4.00b ,486 ,392
thermostated in the bath prior to mixing or measuring. .50b 1.057 ,388 9.00b ,280 .405
Preparation of Leuco Bases.-The leuco bases used in this l.OOb 0.891 .368 9.00c ,281 ,405
study were prepared by condensation of the appropriately
a Buffer ratio = (R3N)/[R3NH+). * (R3?jH+) = 1.08
substituted benzaldehyde with dimethylaniline using stand-
ard procedures.'j The melting points of these compounds x 10-3 AI. c (K~P\;H+) = 2.02 x 1 0 - 4 M.
agree well with previously reported values as shown in Table
I. Basicity of Leuco Bases.-The basicities of the leuco
Preparation of Carbinol Bases.-The carbinol bases bases were measured by an analogous method using the
were prepared by the oxidation of the corresponding leuco absorbance a t about 260 mp.
bases with excess chloranil. The buffer solutions were prepared by adding known
The leuco base (2 g.) was dissolved in 150 ml. of ethanol concentrations of dichloroacetic acid to a methanolic solu-
and 4 g. of chloranil was added in one portion. The result- tion 3.78 X 10-8 M in sodium methoxide which had been
ing mixture was refluxed for 1 hour. At this time, 200 ml. standardized against standard hydrochloric acid.
of hot 10% sodium hydroxicle solution was added. The The buffers were such that only a small extent of proto-
solution was immediately extracted with several 100 ml. nation occurred, so that it was possible to neglect the second
portions of hot n-heptane. The n-heptane extract was ionization of the leuco bases.
washed with hot 10% sodium hydroxide, dried with sodium In order to calculate equilibrium constants from the ob-
sulfate, and set aside to cool slowly. The sides of the flask served absorbances, it was necessary to know the absorb-
were scratched vigorously to initiate crystallization. ance of the monoprotonated leuco bases. It was found
The precipitate thus obtained was repeatedly recrystal- that for those leuco bases which did not have chromophoric
lized from n-heptane until constant melting point and molar groups on the third ring, the diprotonated leuco base had
absorbance in the visible spectrum of the derived dyes were a negligible absorbance a t 260 r n p . I t was also noted that
obtained. the absorbance of leuco crystal violet was three-halves that
The absorbances of the compounds in the visible range for leuco malachite green. From these observations it
were obtained by adding several lambda of an acetone appeared reasonable to assume that the absorbance of the
solution of the carbinol bases to an aqueous solution buf- leuco bases was the sum of the absorbances of the individual
fered a t pH 4.0. Spectra were obtained with a Cary model chromophore groups present. Thus, the molar absorbances
14 spectrophotometer. may be expressed

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

Acknowledgments.-We gratefully acknowledge Robert A. Welch Foundation for a Post-doctoral

the use of the laboratory facilities of the Cosmetics fellowship under which much of the present work
Division of the U. S. Food and Drug Administra- was carried out, and to the Department of Chemis-
tion for the early phases of this work. C. D. R. try, University of Buffalo, for clerical assistance in
also wishes to express his appreciation to the preparing the manuscript.

[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).