A STUDY OF STEREC EFFECTS {N "E'HE REACTIONS OF
ARV: ESE‘ERS WW ARYL GREGNAEEDL R‘EAGENTS

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GAST LANSING, MICHIGAN

A STUDY OF STERIC EFFECTS IN THE REACTIONS OF ARYL ESTERS
WITH ARYL GRIGNARD REAGENTS

By

Arthur John Pastor

A THESIS

Submitted to the College of Science and Arts of Michigan
State University of Agriculture and Applied Science
in partial fulfillment of the requirements
for the degree of

MASTER OF SCIENCE

Department of Chemistry

1957

ACKNOWLEDGMENT

The writer wishes to express his
appreciation to Doctor w. T. Lippincott
for his guidance and assistance through-
out this investigation.

—-—-——~—*~~~_-—.—

ii

A STUDY OF STERIC EFFECTS IN THE REACTIONS OF ARYL ESTERS
WITH ARYL GRIGNARD REAGENTS

By

Arthur John Pastor

AN ABSTRACT

Submitted to the College of Science and Arts of Michigan
State University of Agriculture and Applied Science
in partial fulfillment of the requirements
for the degree of

MASTER OF SCIENCE
Department of Chemistry

Year 1957

Approved W W7,

ABSTRACT

A study of steric effects in the reactions of aryl esters with aryl
Grignard reagents has been made by conducting two series of block
experiments. In one series phenylmagnesium bromide, gfmethylphenyl-
magnesium bromide, gfethylphenylmagnesium bromide and gfisopropylphenyl-
magnesium bromide were each reacted with the phenyl esters of benzoic
acid, gfmethylbenzoic acid, Brethylbenzoic acid and gfisoprOpylbenzoic
acid. In the second series the same Grignard reagents were reacted with
the gfcresyl esters of the above benzoic acids.

Infrared absorption spectrophotometry was used to analyze the
reaction mixtures for ketones and tertiary alcohols. The infrared
method was checked by determination of ketones by oxime formation,
determination of tertiary alcohols by formation of the 3,5-dinitro-
benzoates, and by determination of unreacted ester by hydrolysis and
titration of the acid salts.

Results of this study indicate that alkyl groups in any of the
three steric areas, i.e., the acyl portion of the ester, the aryloxy
portion of the ester and the Grignard reagent, hinder the reaction of
Grignard reagent with ester. Substitution in the ortho position of the
Grignard.reagent was shown to cause the greatest hindrance. As would
be expected the degree of hindrance was shown to increase as the size
of the alkyl group increased. The formation of the initial complex
between Grignard reagent and ester was shown not to be appreciably

affected by steric factors of the order of magnitude employed in this

iv

study. The reaction by which alcohol is formed was shown to be markedly
influenced by steric factors in the aryloxy portion of the ester.
Evidence was obtained to show that the alcohol is formed by a direct

reaction of the initial complex formed with Grignard reagent.

TMEEOFCQWHWS

Page
INTRODUCTION .................................................... 1
Statement of Problem ................................. ........ 1
Historical ..................... ...... .................... .... 2
EXPERIMENTAL .................. ........... ....................... 6
Purification and Preparation of Reagents ................ ..... 7
Synthesis of Acid Chlorides ............. . .................... 9
Synthesis of Esters.. ........................................ 12
REACTION OF GRIGNARD REAGENTS WITH ESTERS........ ............... lS
METHODS OF ANALYSIS ..... . ........ . ....... . ................. . ..... 19
Determination of Alcohol Concentrations.. ...... ..... ......... 2h
RESULTS... ....... .... ..... . ........ ..... ...... . ....... .......... 31
DISCUSSION .............. . ..... . ....... ...... ............. ....... b0
CONCLUSIONS......................... ....... ........... 147
BIBLIOGRAPHY ........................... ... ...................... LB
APPENDIX....... ..... . ..... ............. ..... .. ................. N9
Infrared Absorption Spectrographs of Reaction Products of
Grignard Reagents with Esters ....................... . ..... h?

vi

 

II.

III.

IV.

VI.

VII.

VIII.

XI.

XII.

LIST OF TABLES

Page

. Comparison of Observed Physical Properties of Purified

Reagents to Accepted Literature Values ................... .... 8

Mole Fractions of Reagents and Volume of Toluene Employed in

Reactions of Grignard Reagents with Esters ................... 18

Infrared Molar Extinction Coefficients for Benzophenone in

Toluene at 6.0 Microns.............. ..... ...... ....... . ...... 21

Absorption of Triphenylcarbinol in Toluene at 2.80 Microns

with 0.05 Cm. NaCl Solution Cell............... ....... . ...... 2S
. Infrared Determinations of Diphenyl Ketones and Triphenyl

Tertiary Alcohols in Reactions of Grignard Reagents with

Esters..... ....... 0.0......OOIQOOO0.0.0.000...I.0.0.0.0000... 26

Extent of Ester Reaction with Aryl Grignard Reagents as
Determined by Hydrolysis and Amount of Ketone Formed......... 30

Percent Ketone Complex Formed, Percent Ketone Complex Con-
verted to Alcohol and Percent Grignard Reagent Reacting in
the Reactions of Phenylmagnesium Bromide with Aryl Esters.... 33

Percent Ketone Complex Formed, Percent Ketone Complex Cone
verted to Alcohol and Percent Grignard Reagent Reacting in
the Reactions of ngethylphenylmagnesium Bromide with Aryl
Esters....................................................... 35

. Percent Ketone Complex Formed, Percent Ketone Complex Con-

verted to Alcohol and Percent Grignard Reagent Reacting in
the Reactions of o-Ethylphenylmagnesium Bromide with Aryl
Esters. ...-...... 00.000.000.00. 00.0.0...OOOOOOOOOOOOOOOOOI. 37

Percent Ketone Complex Formed, Percent Ketone Complex Con-
verted to Alcohol and Percent Grignard Reagent Reacting in
the Reactions of gflsopropylbenzoate with Aryl Esters........ 39

Percent of Ketone Complex Formed with Phenyl Aryl Esters and
Aryl Grignard ReagentSOOOOOOD0.00.00.000.000.0IOOOOOOIOO0.000 bl

Percent of Ketone Complex Reacting to Form Alcohol in
Reactions of Aryl Grignard Reagents with Phenyl Aryl Esters.. N3

vii

ISIST OF TABLES - Continued

Page

JKCIII. Percent of Grignard Reagent Reacting in Reactions of Aryl
Grignard Reagents with Phenyl Aryl Esters .......... . ........ NS

)(IV. Percent of Grignard Reagent Reacting in Reactions of Aryl
Grignard Reagents with Phenyl and EfCresyl Esters ........... N6

viii

INTRODUCTION

Statement of Problem

The problem of steric effects of alkyl groups in the addition of
Grignard reagents to esters has been widely studied (1-8). However, a
review of the literature reveals no systematic comparison of effects of
alkyl substitution in the three possible steric areas, i.e. the acyl
portion of the ester, the alcohol portion of the ester, and the Grignard
reagent. The purpose of this investigation was to study the steric
effects of ortho substituted methyl, ethyl, and isopropyl groups in
the reactions of aryl Grignard reagents with a series of substituted
phenyl and g—cresyl benzoates. It was desired to establish in which of
the three possible positions mentioned alkyl substitution exhibited the
most pronounced steric hindrance. It was also desired to establish if
the greater decrease in reactivity took place in the intermediate ketone
form or in the parent ester, and if possible to establish more infor-
Nation concerning the mechanism of the reactions. A third purpose of
this work was to compare the relative effects of the methyl, ethyl, and
isOpropyl groups on reactivity and to establish if the steric effects
WEi‘Jr'e additive if the alkyl substituents were in more than one of the
Possible positions.

In order to study the steric effects of these alkyl groups in the
three positions, the phenyl and g—cresyl esters of benzoic acid,
2"‘"l'EEthylbenzoic acid, 2-ethylbenzoic, and 2-isopr0pylbenzoic acid were

prepared. These esters were chosen to avoid possible side reactions

due to enolization. The phenyl esters were each reacted with the
Grignard reagents from bromobenzene, l-bromo-2-methylbenzene, l—bromo-
2 -ethylbenzene, and l-bromo-2—isopropylbenzene. Each of the g—cresyl
esters were reacted with two Grignard reagents to correlate the results
obtained with the phenyl esters and to establish the effect of ortho
methyl substitution on the phenyl portion of the ester. The effects
of these groups were determined by comparing the relative yields of
diaryl ketones and triaryl tertiary alcohols in a series of reactions
performed under the same conditions. The diaryl ketones and triaryl
tertiary alcohols were determined quantitatively by infrared absorption
methods.

The reactions were all performed in refluxing toluene with constant
reaction times. The initial ratio of Grignard reagent to ester was 1:1
in all instances, and the initial concentration of reagents was main~
taimed approximately constant for all reactions studied. To avoid
possible undesirable side reactions, iodine and other activators were
not, employed in the preparation of the Grignard reagents; the Grignard
1"eagents were filtered prior to use to remove unreacted magnesium. The
Order of addition of reagents was in reverse to the accepted method,
1-8 . the Grignard reagents were added to the ester dissolved in toluene

to avoid favoring the formation of tertiary alcohol.

‘His‘borical
The effects of steric hindrance on Grignard reactions regarding
both normal addition and side reactions have been studied by several

luve‘Stigators. Fuson and co-workers (1) studied the reaction of alkyl

and aryl Grignard reagents with alkyl and aryl mesitoates; the reactions
did not produce any of the expected tertiary alcohol. The products of
the reactions of the Grignard reagents and the alkyl mesitoates were
mesitoic acid and the alkyl halide of the alkyl group of the ester.
The reactions with the aryl mesitoates and the alkyl Grignard reagents
produced a ketone and the phenol of the aryl group of the ester.

In the case of the reaction of aryl mesitoates with aryl Grignard
reagents the expected ketone was not obtained, but one in which ortho
substitution by a second mole of Grignard reagent had taken place.

R - T. Arnold, H. Bank, and R. Liggett (2) also investigated the effects
of substitution in the ortho position of the acyl portion of allyl
benzoates. These workers studied the reactions of phenylmagnesium
bromide with allyl benzoate, allyl _c_>_-toluate, and allyl mesitoate in
ethyl ether. They found that the yields of the expected triphenyl-
carbinol in the cases of allyl benzoate and allyl g—toluate were,
respectively, 86% and 68%, indicating that the single ortho group did
not greatly interfere with normal Grignard addition. However, with the
allyl mesitoate no ketone nor triphenyl alcohol were formed; but instead,
meSitoic acid and allyl benzene were the products. These same investi—
gators studied the effect of methyl substitution on the reactivity of
allyl alkyl esters. In the reaction of phenylmagnesium bromide with
allyl trimethyl acetate a high yield of t—butyldiphenyl carbinol was
ex'.[3€I‘ienced. The reaction of g-methylphenylmagnesium bromide with
ethyl o-toluate was studied by Boyd and Hatt ( 3). They found that no

tri ~'§>_---tolylcarbinol was produced. The diaryl ketone and the pinacol

of the diaryl ketone were isolated. The pinacol formation was attributed
to the presence of excess magnesium in the reaction mixture.

Kohler and Baltzly (h) studied the steric effects of methyl sub-
stitution upon the addition and enolization reactions of Grignard
reactions with ketones. In comparing the results obtained in reactions
of acetomesitylene, dimesityl ketone, and dimesityl diketone with
ethylmagnesium bromide, they concluded that the ortho groups affect only
those reactions which involve direct addition to the carbonyl and in
no way promote the competing enolization reaction. Their work was
confirmed in the studies of Smith and Guss (5) who found that the di-_o_-
alkyl substituted ketones underwent complete enolization in reacting
with methylmagnesium bromide .

The effect of steric hindrance as introduced by the reacting
Grignard was noted by Hauser and co-workers (6) in their study of
Competitive reactions of esters with alkyl Grignard reagents, and by
Whitmore and George in their study of Grignard reactions with alkyl
ketones. Hauser found that as the complexity of the Grignard reagent
increased from ethyl to isopropyl to tert-butyl to mesityl magnesium
bromide, the degree of normal addition decreased rapidly and condensa—
tion reactions were experienced. Whitmore and George found that the
degree of addition of the Grignard reagent to diisoprOpyl ketone was
greatly decreased as the Grignard reagent employed changed from methyl-
magnesium bromide to isobutylmagnesium bromide.

In discussing the problem of steric hindrance in Grignard reactions

with esters, Kharasch and Reinmuth (8) concluded that the ability to

form ketones when the intermediate is reasonably soluble is primarily
the function of the Grignard reagent, the branched chain alkylmagnesium
halides displaying a marked tendency toward ketone formation. They
also postulated that when the intermediate is of limited solubility in
the reaction media, the primary product in ester reactions is a ketone.

No literature references of the effects of methyl substitution in the

ortho position of the phenyl portion of the ester were encountered.

EXPERIMENTAL

Basic chemicals employed in this investigation were: bromobenzene,
1 -bromo -2 -me thylb enzene , l-bromo ~2 -ethylbenzene , l-bromo -2 -isopropyl ~
benzene, g—cresol, phenol, benzoyl chloride and g—toluic acid. Compounds
prepared and isolated were g-ethylbenzoic acid, g-ethylbenzoyl chloride,
2~tolyl chloride, g—isopropylbenzoic acid, g-isopropylbenzoyl chloride;
811d the phenyl and p_-cresyl esters of benzoic acid, _o_-toluic acid
g-ethylbenzoic acid, and g-isoprOpylbenzoic acid. The compounds synthe-
sized and not previously reported in the literature were the phenyl and
g—cresyl esters of g-ethylbenzoic acid and g-isoprOpylbenzoic acid and
the g-cresyl ester of _o_-toluic acid.

Each of the phenyl esters were reacted with the Grignard reagents
prepared from the above bromo substituted benzene compounds. Each
g—cresyl ester was only reacted with two Grignard reagents prepared
from the bromo substituted benzene compounds. The amount of ketone
and tertiary alcohol produced in each reaction was determined by
infrared analysis. In order to correlate infrared analysis, a portion
of the ketones were also determined by reaction with hydroxylamine
hSVdrochloride in pyridine. A portion of the reaction mixtures were
also treated with 3, S-dinitrobenzoyl chloride to' determine the tertiary
aLLcohol content. A determination of the unreacted ester was affected
by hydrolyzing the ester with sodium hydroxide and titrating the

bel'lzoic acid sodium salt.

PURIFICATION AND PREPARATION OF REAGENTS
Purification of Starting Reagents

The bromobenzene, 14bromo-2-ethy1benzene, and l~bromo-2-isopropyl-
benzene were supplied by The Dow Chemical Company as technical grade
Inaterials. The l-bromo-2-methylbenzene employed was obtained from
Eastman Kodak Company. These compounds were each purified by frac-
tional distillation. The bromobenzene and l—bromo-2-methylbenzene were
distilled at atmospheric pressure, while the l-bromo-2 ~ethylbenzene and
1-bromo-2~isopropyl-benzene were distilled at 30 mm Hg. pressure. In
each instance a two~foot adiabatic Vigreux column equipped with a Corad
Fractionating condenser was employed. All fractions were collected at
a reflux ratio of 30:1.

In the purification of these liquids, the fractionating column was
allowed to attain equilibrium at infinite reflux for a minimum of three
hours prior to collecting any distillate. In the case of bromobenzene,
l—bromo-Z -methylbenzene and l-bromo-2 -ethylbenzene the first condensate
representing approximately 10% of initial amount was collected at the

eJ-Cpected boiling point of the compounds. However, these first fractions
Were discarded and the desired product was collected at a reflux ratio
of 30:1 after the column again attained equilibrium.

In the purification of the l-bromo-2-isopropylbenzene, two initial
fFactions were discarded. The technical grade material was reported to
Contain 16% lebromo-h-ethylbenzene and 6% l—bromo-h-isopropylbenzene.

The first fraction was collected in the temperature range of 103.6 to

10600. The second fraction representing 10% of the total

TABLE I

COMPARISON OF OBSERVED PHYSICAL PROPERTIES OF PURIFIED REAGENTS
TO ACCEPTED LITERATURE VALUES"

T‘ :—-
1

 

 

 

 

 

Index of Refraction, 2500. Boiling Point, 20 mm Hg

 

 

Reagent
Observed Literature Observed Literature
IBromobenzene 1.5572 1.5571 620C 61.700
1 -Bromo-'2 -methyl- 1.5538 1.55141 82 5°C 82 .300
benzene
1 ~Bromo-2 -ethy1 - 1.51162 1.51462 96°C 97 .600
benzene
l-Bromo-2-isopropyl- 1.5390 , 1.5385 107°C 107.1330
benzene

*R. R. Dreisbach, Physical Properties of Chemical Compounds,
A.C.S., washington, D. C., 1955.

:L-bromo-2-isopropylbenzene was collected in the temperature range of

106 to 107%.

The observed boiling points and refractive indexes of the purified

rnaterials are compared to the literature values in Table I. Each of

11hese compounds was employed in the synthesis of its respective Grignard
Ioeagent, which in turn was reacted with the phenyl and gfcresyl esters.
'IWie l-bromo-2-ethylbenzene and the l-bromo-2-isopropylbenzene were also
employed in the synthesis of 2-ethylbenzoyl chloride and 2-isopropyl-
‘tnenzoyl chloride, respectively.

The aforesol was Eastman Kodak technical grade material. This was
jENArified by distillation at 30 mm Hg pressure employing a Claisen
ciistillation head on a 1 liter flask. Distillate boiling at 97-9800
‘hnas collected and retained. Literature value for boiling point of pure
52:-cresol is 97.hoC at 30 mm Hg pressure (9). Purified gfcresol was
fianmployed in the synthesis of the gfcresol esters of benzoic acid,

£25~methylbenzoic acid, gfethylbenzoic acid, and 2-isopropylbenzoic acid.

ES‘INTHESIS OF ACID CHLORIDES

Preparation of 2-methylpepgoy1__chloride -- One hundred grams of
2?-—methylbenzoic acid (0.73 mole), Eastman Kodak, was reacted with 139
Eilsams of thionyl chloride (1.1? moles), Eastman Kodak, according to the
IDIsocedure employed by Zuffanti (10). The 2-methy1benzoic acid was-
IDJMaced in a 500 ml round-bottomed, ground jointed flask equipped with
5i (Zlaisen distillation head. The side arm of the Claisen head was cork
stijpered and the flask inclined at approximately 30 degrees to avoid

Etrfiy” retention of condensate in the side arm. After addition of thionyl

IO

chloride, a condenser with drying tube was attached and the system
gently refluxed for 6.5 hours. The reaction was considered complete
when no further evolution of hydrogen chloride and sulfur dioxide was
evidenced.

The apparatus was then rearranged to permit normal distillation
and unreacted thionyl chloride distilled off at atmospheric pressure,
temperature range 75-8500. A second fraction which was collected at
108 to 113°C at 30 mm Hg pressure was discarded. Ninety-two and five-
tenths grams of product were collected at 11300 at 30 mm Hg pressure.

The yield was 81.9% of theoretical.

Preparation of 2-ethyl benzgyl chloride —- Seven grams of l-bromo-
2 ~ethylbenzene was added with 100 ml. of sodium dried ethyl ether to
16.03 gms (0.66 gm. atom) of 99.9% magnesium, Mallinckrodt Grignard
Reagent Grade, in a three neck, 1 liter, round bottomed flask, equipped
With stirring motor, condenser, am separatory funnel. A crystal of
iodine was added to initiate the reaction. After initiation, 115 gms
Of l-bromo-2—ethy1benzene dissolved in h50 ml of sodium dried ethyl
ether was added to the reaction drOpwise over a period of 1 hour. The
reaction mixture was gently refluxed for an additional hour to insure
C=C>mplete reaction of the magnesium, and then allowed to cool to room
temperature .

The prepared Grignard reagent was then transferred with dry nitro-
gen pressure onto 800 gms of finely divided solid carbon dioxide in a
5 liter beaker. The system was vigorously stirred during the addition.

Unl‘eacted carbon dioxide was allowed to evaporate and the mixture was

11

treated with 350 m1 of 10% hydrochloric acid solution containing crushed

ice. The mixture was then transferred to a 1 liter separatory funnel

sand the aqueous phase discarded. Four hundred ml of 10% sodium hydroxide

solution was added to the ether solution and the mixture was shaken for

3 minutes. Following separation, the aqueous phase was transferred to

a second separatory funnel containing 500 ml of C. P. chloroform and

200 ml of 1.5% hydrochloric acid in water solution. After separation

from the water phase, the chloroform solution was evaporated. The
yield of crude 2-ethylbenzoic acid melting at 62-6hOC was 8h.7%.
Literature value for melting point is 65°C (11).

The 2-ethylbenzoic acid was converted to 2-ethy1benzoy1 chloride
by the same procedure employed in the synthesis of l-methylbenzoyl

chloride. Seventy-six and four-tenths grams of the crude acid (0.5 mole)

Was reacted with 95 grams thionyl chloride (0.8 mole) for a period of
3 .5 hours. The reaction mixture was distilled at 300 mm Hg pressure.

Approximately 10% of the total product was discarded in the initial

fraction. The yield of acid chloride collected at a constant boiling

Point of 120°C at 30 mm Hg was 8h.6% based on the weight of acid

employed; 71.8% based on the initial starting material, 1-bromo-2 -ethy1-

b enzene .

Preparation of 2-isopropylbenzoyl chloride -- The acid chloride of

2"isoprOpylbenzoic acid was prepared in the exact manner employed in

the synthesis of 2-ethylbenzoyl chloride. One hundred and ten grams of

pr‘eviously purified l-bromo—2-isopr0pylbenzene (0.55 mole) was reacted

for 3 hours with 13.1; grams of 99 9% pure magnesium (055 gram atoms)

12

in a total of 550 ml anhydrous ethyl ether. In addition to employing a
crystal of iodine to initiate the reaction, two drops of l-bromo-2-
methylbenzene were added. The resulting Grignard reagent was transferred
by nitrogen pressure onto 1000 grams of finely divided solid carbon
dioxide. The yield of crude 2-isopropylbenzoic acid was 8h.2%. It was
initially a dark amber liquid which solidified after prolonged storage.
The observed melting point was 53 to 5500.

Sixty-four and nine-tenths grams of crude 2-isopropylbenzoic acid
( 0.14 mole) was reacted with 76 g thionyl chloride (0.61; mole) for 6.5
hours. After discarding the initial 10% fraction, 61.6 grams of
2-i30propylbenzoy1 chloride were collected over a boiling range of 127
to 128°C at 30 mm Hg pressure. The yield of acid chloride was 93.5%
based upon the amount of 2-iSopr0py1benzoic acid; 77.7% based upon the

initial amount of 1 -bromo -2 -isopropy1benz ene .

SYNTHESIS OF ESTERS

Phenol and g-cresol esters of benzoic, 2-methylbenzoic, 2-ethy1-
benzoic, and 2-isopr0py1benzoic acids were, prepared from the correspond-
ing acid chlorides according to the method recommended by Hickenbottom
( 12) . In each instance an equivalent molecular weight of the acid
Chloride was added to the phenol, Eastman Kodak Reagent Grade, or
purified p_-cresol dissolved in five times its weight of pyridine,
Merck & Company Reagent Grade, at 000. The reactions were performed
in 500 m1 Iodine flasks to facilitate vigorous agitation. After stand-
ing for 12 hours and attaining a temperature of approximately 250C,

100 ml of U.S.P. chloroform was added and the mixture was extracted

13

with four equivalent volumes of 1.5% hydrochloric acid, two volumes of
3% sodium carbonate, and two volumes of distilled water. Following
removal of the chloroform, the products were purified by deposition from
a methyl alcohol solution of 000. Precipitation from the methyl alcohol
solution was induced by the addition of a small amount of distilled
water. Samples of esters not listed previously in the literature were

submitted for carbon and hydrogen analysis.

Phenyl benzoate -- One—half mole phenol was caused to react with
O .5 mole benzoyl chloride, Eastman Kodak, melting point —0.50 to 0.500.
Yield of purified crystals melting at 69-700C was 914.11 gm., 95.2%

theoretical. The melting point of phenyl benzoate is 7000.

gCresyl benzoate -- One-half mole each of g-cresol and benzoyl

 

Chloride yielded 99.85 gm of ester, 911.1% yield. Refractive index of

Colorless liquid at 2500 was 1.5680.

Phenyl g-methylbenzoate -- Four-tenths mole each of phenol and

 

2~methy1benzoyl chloride yielded 69.6 gms, 8h.1% theoretical. Refractive

index of light yellow liquid at 25°C was 1.5695.

p_-Cresyl g-methylbenzoate -- Two-tenths mole each of _o_-cresol and

 

Q~methylbenzoyl chloride yielded 30.9 gms ester, 69.78% theoretical.
Refractive index at 2500 of light yellow liquid was 1.5657. Carbon-
h.Sfdrogen analysis revealed 79.h6% and 6.311%, respectively; theoretical

is C, 79.62% and H, 6.18%.

1h

Phenyl o-ethylbenzoate ~- Three-tenths mole each of phenol and
—-——-———-—~

 

‘gafethylbenzoyl chloride yielded 57.9 gms ester, 91.h% theoretical.
iEtefractive index at 25°C of amber liquid was 1.5678. Carbon-hydrogen

aLnalysis showed 0, 79.13% and H, 6.33%; theoretical is C, 79.62% and

H, 6.18%.

QfCresyl gfethylbenzoate -- Fifteen hundredths mole each of

 

 

52;—cresol and gfethylbenzoyl chloride yielded 30.5 gms. ester, 90.5%
islleoretical. Refractive index at 2500 of amber liquid was 1.5593.
C36lrbon—hydrogen analysis showed 0, 79.72% and H, 6.72%; theoretical is

C), 79.97% and H, 6.71%.

Phenyl geisoprOpylbenzoate -- Two-tenths mole each of phenol and

 

£35~isopropylbenzoyl chloride yielded h5.9 gms ester, 97.1% theoretical.

Iieefractive index at 2500 of dark amber liquid 1.5551. Carbon-hydrogen
Elrnalysis showed 0, 79.90% and H, 6.83%; theoretical is C, 79.97% and

11,. 6.71%.

 

o-Cresyl o-isoprOpylbenzoate -- One-tenth mole each of o-cresol
l—n—nu—ufl— —

Ellld gfisopropylbenzoyl chloride yielded 20.8 gms ester, 7h.2% theoretical.
Fieefractive index at 25°C of dark amber liquid was 1.551h. Carbon-

1’Zlardrogen analysis showed 0, 79.60% and H, 7.lh%; theoretical is C, 80.28%

and H, 7.13%.

15

REACTION OF GRIGNARD REAGENTS WITH ESTERS

The Grignard reagents prepared from the above bromobenzenes were

each reacted with all of the prepared phenyl esters. The effect of

the methyl-substituent in the ortho position of the phenyl portion of

the esters was studied in the reaction of phenylmagnesium bromide with
g—cresyl benzoate and g-cresyl g—isopropylbenzoate, g—methyl—phenyl-
magnesium bromide with g-cresyl g-methylbenzoate and g—cresyl g—ethyl—
benzoate, g-ethylphenylmagnesium bromide with g-cresyl g-methylbenzoate
arid g-cresyl q—ethylbenzoate, and g-isopropyl-pheny1magnesium bromide

With g—cresyl benzoate and g—cresyl g—isopropylbenzoate.

In each reaction studied, freshly prepared 25 ml of Grignard

reagent in ethyl ether was added to an equal molar amount of ester

dissolved in toluene. Grignard reagent concentrations were determined

by titration to a methyl orange end-point with 0.2N hydrochloric acid.
Initial ester concentrations were 0.025 mole per 100 ml in order to
provide nearly equal concentrations in all reactions. Each reaction

was allowed to proceed exactly 1 hour and was terminated by addition of

a hydrochloric acid solution. Following extraction with sodium

carbonate solutions and distilled water to insure complete removal of

the liberated phenol or _o_-cresol, the solutions were azeotropically

dried and diluted to standard volumes. Concentrations of ketones and

teI‘tiary alcohols were determined by infrared analysis. A typical
reaction is exemplified by the reaction of phenylmagnesium bromide with

pherlyl g-isopropylbenzoate given below.

16

Reaction of Phenylmagiesium Bromide with Pheny_l_o-Isopropylbenzoate --
Preparation and analysis of Grignard Reagent: Fifteen and seven-tenths
grams of purified bromobenzene (0.1 mole) was reacted with 2.143 gms of
99 .9% magnesium turnings (0.l gram atom) in 100 ml of sodium dried ethyl
ether. The bromobenzene in ethyl ether was added over a period of one
hour to the magnesium; heat was applied for an additional one hour to
maintain gentle reflux. No iodine was employed as an activator to avoid
Subsequent side reactions upon addition to the ester. The phenyl-
magnesium bromide solution was filtered through a 1 inch pad of Pyrex '
Wool to remove unreacted magnesium. Twenty-five milliliters was trans-
f erred into a 125 ml separatory funnel and 2 ml was pipetted into 25
m1 of distilled water. The water layer was then titrated with 0.2N
hydrochloric acid to the methyl orange end-point. Ten and eight-tenths
milliliters of acid were required to attain an end-point. Calculation
of mole fraction of phenyl magnesium bromide per 25 milliter was per-

formed by the following equation:

Moles of Grignard reagent 0.2 x ml of acid x 25

per 25 milliliter 2 x 1000

H

0.027 mole.

One hundred and eight milliliters of phenyl 2-isopropyl-benzoate in

toluene solutions at a concentration of 0.025 mole of ester per 100 ml
was placed in a 250 ml three neck flask. The flask was equipped with
a "lot or driven Teflon stirrer and a Dean-Stark condensation trap with

Cond enser. The separatory funnel containing the Grignard reagent was

17

attached to the third joint. The Grignard reagent was added in five
approximately equal portions over a period of five minutes. Agitation
was initiated prior to the addition of the phenylmagnesium bromide.
The temperature was raised to 1100C over the next 10 minute interval and
removal of ethyl ether was facilitated by means of the Dean-Stark
condensation trap. A deep red coloration was formed in the reaction
mixture as the ethyl ether was removed. After maintaining the tempera-
t‘Jre at 110°C for one additional hour, the reaction was quenched by
addition of 100 ml of 10% hydrochloric acid solution.

The mixture was transferred to a 250 ml separatory funnel and
extracted with two 100 m1 portions of 10% sodium carbonate solution
and two 100 m1 portions of distilled water. Seventy-five milliliters
Of toluene was added and the toluene solution placed in a 500 ml flask
equipped with a Claisen distillation head. The water in solution was
removed by azeotropic distillation with the excess toluene and the
SOlution concentrated to approximately 50 ml. After cooling to 20°C,
the solution was diluted to 125 ml with sodium dried toluene. The
resulting solution was a light amber color. Yield of ketone and percent

ketone converted to tertiary alcohol were determined in infrared analy-

.

Sis and were found to be 33.88% and 38-35%, PGSPeCtj-V91Y-

The concentrations of reagents employed in all reactions are

presented in Table II.

18

TABLE II

MOLE FRACTIONS OF REAGENTS AND VOLUME OF TOLUENE EMPLOYED
IN REACTIONS OF GRIGNARD REAGENTS WITH ESTERS

 

 

 

R . Mole Fraction Milliliters
eactlon
Reagents Toluene
Phenylmagnesium Bromide
1) Phenyl benzoate 0.0271 133.5
2) Phenyl E-methylbenzoate 0.0271 133.5
3) Phenyl E-ethylbenzoate 0.0299 1&5
h) Phenyl E—isopropylbenzoate 0.0271 133.5
5) E-Cresyl benzoate 0.0299 1h5
6) E-Cresyl 2-i30pr0py1benzoate 0.0299 1h5
2L¥Methylphenylmagnesium Bromide
1) Phenyl benzoate 0.031 1L9
2) Phenyl E-methylbenzoate 0.0265 131
3) Phenyl E—ethylbenzoate 0.0265 131
h) Phenyl E-isopropylbenzoate 0.0265 131
5) E-Cresyl E—methylbenzoate 0.023h 119
6) E-Cresyl E-ethylbenzoate 0.023h 119
23~Ethy1phenylmagnesium Bromide
1) Phenyl benzoate 0.025h 126.5
2) Phenyl E-methylbenzoate 0.025h 126.5
3) Phenyl E-ethylbenzoate 0.026 129
h) Phenyl E-isopropylbenzoate 0.0313 150
5) o-Cresy'i’ E-methylbenzoate 0.0313 150
6) E—Cresyl E—ethylbenzoate 0.0313 150
53:1sopropylphenylmagnesium Bromide
l) Phenyl benzoate 0.026h 130.5
2) Phenyl E—methylbenzoate 0.026h 130.5
3) Phenyl E-ethylbenzoate 0.0265 131
h) Phenyl E-isoprOpylbenzoate 0.027h 135
5) E-Cresylbenzoate 0.027h 135
6) E—Cresyl E-isopropylbenzoate 0.027h 135

 

19

METHODS OF ANALYSIS

Concentrations of diaryl ketone and triaryl tertiary alcohols
Ixroduced in the above reactions were determined by infrared analysis
llsing a Perkin-Elmer Model 21 Double Beam Infrared Spectrophotometer.
Efimploying benZOphenone as a standard, a molar extinction coefficient
(1f 360 was obtained. Since the maximum absorption of all diaryl ketones
cfiatained in this study appeared at 6 microns, this molar extinction
cnoefficient was employed for all ketone determinations. The validity
(if this treatment has been discussed by Bellamy (lb). The determination
cxf the triaryl tertiary alcohols required the use of a calibration
Egraph obtained with triphenylcarbinol. An attempt to correlate infrared
Etnalysis with precipitation methods of analysis was made employing
Trydroxylamine hydrochloride determinations of three ketones and 3,5-di-
Ilitrobenzoyl chloride determinations of three alcohols. Analysis of
Ilnreacted ester was affected by hydrolyzing the ester with sodium

Iiydroxide and titrating the acid salt.

lQetermination of Ketone Concentrations

Infrared Method -- The molar extinction coefficient of benzophenone
teas determined by measuring the absorptions of four solutions of the
lcetone in sodium dried C. P. toluene. .Solution concentrations in grams
IDer liter were 25, 12.5, 5, and 1. Absorptions were determined with a
IDouble Beam Perkin-Elmer Infrared Spectrophotometer Model 21. Sodium
<3h10ride solution cells of 0.05 cm thicknesses were employed in the

sample and in the reference positions of the instrument. Sodium dried

20
(3 . P. toluene was placed in the reference cell. Extinction coefficients
were calculated by the following equation:

e --‘EL- lo .l
I cd g IO

e = Molar extinction coefficient

M = Molecular weight of ketone

c = Concentration of ketone in grams per liter
d = Thickness of cell in centimeters

I = Intensity of light transmitted

IO Intensity of light at zero absorption.

The values of the molar extinction coefficients obtained with the
srtandard benzophenone solutions are presented in Table III. At concen-
11rations of 1 to 5 grams per liter, the molar extinction coefficient is
supproximately a constant 360 at 6.0 microns. This value differs from
1Jhe extinction coefficient of non found by Cross and Rolfe at 6.09
nnicrons (13). In subsequent analysis of ketones, it was found that the
Eirea of maximum absorption was constant for all diaryl ketones prepared
fiLn this study. Therefore, the experimentally determined extinction
czoefficient for benzophenone was employed in all calculations. This
(iecision was made on the basis of the findings of Bellamy (1b) which
Iindicated that the extinction coefficient of similar compounds remains
(zonstant provided there is no change in area of maximum absorption.

To determine the effect of the triaryl tertiary alcohols and aryl

esters upon the maximum absorption.peak of benzophenone, the infrared

TABLE III

INFRARED MOLAR EXTINCTION COEFFICIENTS FOR BENZOPHENONE
IN TOLUENE AT 6.0 MICRONS

21

 

 

Concentration Benzophenone Molar Extinction

 

1“ grams/liter Coefficient x 36'hh
25 1h.07
12.5 12.27
5 10.19
3 10.10
1 ' 10.07

22

signectrograph of a toluene solution containing 16.66 grams per liter
tseznzophenone, 8.33 grams per liter triphenylcarbinol, and 6.66 grams
Ipexr liter Efcresyl benzoate was studied. The spectrOgraphs of triphenyl-
<3axrbin01 and Efcresyl benzoate were also studied individually. Neither
“brie tertiary alcohol nor the ester exhibited absorptions in the 5.9 to
65.1 micron range. The Efcresyl benzoate exhibited a sharp absorption
eat; 5.75 microns, and the triphenylcarbinol absorbed at 2.80 microns.

A sample calculation of the ketone concentration is exemplified
Euuploying the data obtained in the analysis of the reaction mixture of
‘Er—ethylphenylmagnesium bromide with phenyl Efethylbenzoate diluted to
See m1.

Reaction: 0.026 mole ester
0.026 mole Grignard reagent

Infrared absorption: I = h7.8
M

I
Concentration of ketone in 4=~ 10g —-
grams per liter 36b x GIG; IO

 

_ log O.h78

__ 238. 1
1

13.2h x 0.321

b.25 grams per liter

Total number of grams per 500 ml is 2.13

Theoretical yield of ketone:

_ Molecular weight of ketone = 238.31
238.31 x 0.026 = 6.20 grams
Percent yield:
(2.13 9 6.2)100 = 3h.h%

23

The results of all infrared ketone determinations are incorporated with

infrared determinations of alcohol concentrations in Table V.

Hygroxylamine Hydrochloride Method -- In an effort to correlate
tfiie results obtained by infrared analysis the oximes of the ketones
Ixroduced in the reactions of Efethylphenylmagnesium bromide phenyl,
'vrith phenyl Efethylbenzoate, Efmethylphenylmagnesium bromide with phenyl
Elemethylbenzoate, and ErisoprOpylphenylmagnesium bromide with phenyl
garisopropylbenzoate were prepared by the method outlined by Byrant and
Smith (15). A 25 m1 aliquot of the reaction mixture in 125 m1 toluene
ssolution was placed in a Citrate of Magnesia bottle with 30 ml 0.5 N
Itydroxylamine hydrochloride in 80% ethanol and 100 m1 of a 20% pyridine
inn ethanol solution containing 0.2% bromOphenol blue indicator. The
£3amples and a blank containing only toluene with the reagents were
lieated in a water bath at 95°C for h hours. After cooling to room
“temperature, the samples were titrated with 0.36 N potassium hydroxide
:in methanol and 0.20 N hydrochloric acid in methanol to the color of
‘the blank sample. In addition to the unknown samples, one known to
toontain 1.05 gms of benzophenone was analyzed. An example of the method
<of calculation is shown with the known benzophenone sample.

16.77

Milliliters 0.36 N KOH
0.2 0.27

Milliliters O N HCl

II II

grams of benzophenone [(16.77 x 0.36) - (0.27 x 0.20)] 0.1822

1.09

Percent error:

[(1.09 - 1.05) f 1.0h] 100 = + 3.5%

214

Atnalysis indicated: 2.0 grams ketone, 32.3% yield, in reaction of
‘Elfethylphenylmagnesium bromide with phenyl Efethylbenzoate; 2.55 grams
bretone, h6.6% yield, in reaction of Efmethylphenylmagnesium bromide
twith phenyl Efmethylbenzoate; and 1.20 grams, 16.6% yield, in reaction
(if ErisoprOpylphenylmagnesium bromide with phenyl Erisopropylbenzoate.

CDhese results compare, respectively, to 3h.h%, h9.5%, and 21.8% obtained
13y infrared analysis.

IDETERMINATION OF ALCOHOL CONCENTRATIONS

Infrared Method -~ Infrared analysis of solutions of triphenyl
czarbinol of varying concentrations from 2.5 to 25 grams per liter indi-
<3ated that a constant molar extinction coefficient was not exhibited in
“this range. Therefore t29.ca1ibration graph, Figure—l, was made,
]plotting percent absorption against concentration of benzophenone. Data
employed in plotting this graph was obtained employing 0.05 centimeter
solution cells and is presented in Table IV.

The series of triaryl tertiary alcohols analyzed all exhibited
.absorption at 2.8 microns. Therefore it was assumed, as in the case of
‘the ketone determinations, that all alcohol concentrations could be

determined from the same graph. Results of these determinations are

'presented in Table V.

3,5-Dinitrobenzoy1 Chloride Method -- To correlate the infrared
analysis of alcohol concentrations, 3,5-dinitrobenzoy1 chloride deriva-
tives were prepared of the alcohols formed in the reactions of phenyl-

magnesium.bromide with phenyl benzoate, phenyl-Efmethylbenzoate, and

25

TABLE IV

ABSORPTION OF TRIPHENYLCARBINOL IN TOLUENE AT 2.80 MICRONS
WITH 0.05 CM. NaCl SOLUTION CELL

 

Triphenylcarbinol Concentration Percent Absorption
grams liter

18.75 33.57
12.50 . 22.1b
10.0 18.57
6.25 11.78
5.0 6.79

2.5 1.h3

26

TABLE V

INFRARED DETERMINATION OF DIPHENYL KETONES AND TRIPHENYL TERTIARY
ALCOHOLS IN REACTIONS OF GRIGNARD REA ...AGENTS WITH ESTERS

 

Reaction Ketone Tertiary Alcohol
(grams) . (grams)

 

I’henylmagnesium Bromide

1) Phenyl benzoate 0.21 2. 01
2) Phenyl E-methylbenzoate 0.98 1.38
3) Phenyl E-ethylbenzoate 1.28 1. b8
h) Phenyl E-iSOpropylbenzoate 1.27 1.07
5) E-Cresyl benzoate 0.22 3.05
6) E—Cresyl E—isopropylbenzoate 0.80 1.33
2 -Methy1pheny1magnesium Bromide
1) Phenyl benzoate 1.5h 0.72
2) Phenyl E-methylbenzoate 2.71 0.h7
3) Phenyl E-ethylbenzoate 2.68 0.50
h) Phenyl E—isopropylbenzoate ' 2.16 0.60
5) E-Cresyl 2-methy1benzoate 2.15 0.56
6) E—Cresyl 2-ethylbenzoate 1.82 0.66
2-Ethy1pheny1magnesium Bromide
1) Phenyl benzoate 1.79 0.60
2) Phenyl E-methylbenzoate 1.70 0.70
3) Phenyl E-ethylbenzoate 2.13 0.62
h) Phenyl E—isopropylbenzoate 2.90 0.62
5) E-Cresyl 2+methy1benzoate 2.71 0.6h
6) E-Cresyl 2-ethy1benzoate 2.65 0.78
2-ISOpropy1pheny1magnesium Bromide
1) Phenyl benzoate 1.99 0.52
2) Phenyl E-methylbenzoate 2.h7 0.56
3) Phenyl E—ethylbenzoate 1.67 0.h0
h) Phenyl E—isoprOpylbenzoate 1.59 0.57
5) E-Cresbeenzoate 1.50 0.66

6) E-Cresyl 2-130propy1benzoate 1.16 0.70

27

phenyl E—ethylbenzoate. As a control reaction, a solution known to
(nolitain 0.500 grams triphenylcarbinol in 25 m1 toluene was also analyzed
byr ‘this.method. For the unknown concentrations, a 25 m1 aliquot of
the reaction mixtures in 125 ml was dissolved in 25 m1 C. P. pyridine,
Eastman Kodak, and cooled to 0°C in 125 m1 Iodine flasks. One gram of
j3,fS-dinitrobenzoyl chloride was added to each sample and the mixtures
were allowed to stand for 6 days. Samples were then washed with four
Gecrual volumes of 5% hydrochloric acid, five equal volumes of 10% sodium
carbonate, and two volumes of distilled water. The samples were then
evaporated down to approximately 5 m1, and 50 ml of a 50% toluene 50%
rnerthyl alcohol solution added. This solution was cooled to 000. for

)4 hours and then filtered through weighed filter papers. The filtrate
Were evaporated to approximately 50% and chilled to 0°C for 1; hours.
In no instance was there evidence of crystallization in the filtrates.
The method of calculation of weight of alcohol is exemplified with the

known concentration of triphenylcarbinol.

Molecular weight of triphenyl carbinol = 260.32
Molecular weight of 3,5 dinitrobenzoic
acid ester of triphenyl carbinol = h5h.h2
Gravimetric factor = 260' g = 0-5729
'Weight of ester = 0.2h17 grams

0.2h17 x 0.5729

Weight of alcohol

0.1385 grams

100 [0.139 9 0.500]

ll

Percent yield
= 27 I 7%

28

Analysis of samples indicated 0.527 grams alcohol in reaction of phenyl-
magnesium bromide with phenyl benzoate, 0.373 grams alcohol in the
reaction with phenyl Efmethylbenzoate, and 0.387 grams alcohol in the
reaction with phenyl Efethylbenzoate. These results compare,
respectively, with 2.01 grams, 1.38 grams and 1.h8 grams alcohol as
determined by infrared analysis.

It is interesting to note that the gravimetric determination of the
known sample of triphenylcarbinol was approximately one-fourth of the
actual amount present. If the gravimetric determinations obtained
with the unknown samples are each multiplied by b, they are, respectively,
2.11 gm., 1.h9 gm., and 1.55 gm., closely correlating with the infrared

determinations.

Determination of Unreacted Ester

The amount of unreacted ester was determined by hydrolysis in six
of the reactions studied. Hydrolysis was accomplished by refluxing 20
m1 of the ester in toluene with 25 m1 of 0.22 N sodium hydroxide in 90%
ethylene glycol 10% water solution for 2h hours. Fifty milliliters of
ethanol was added and the mixture was titrated with 0.196 N hydrochloric
acid in ethanol to a pH of 9.75 employing a Beckman Model G pH Meter
equipped with glass and calomel electrodes. The equivalence point was
determined by plotting pH curves of the standard sodium hydroxide solu-
tion and the sodium hydroxide solution containing 1 milliequivalent of
phenol. In this manner the difference in titration of the blank and
unknown samples was a measure of the milliequivalents of aryl acid and

hence, the original ester.

29

The reactions in which the unreacted ester was determined are
presented in Table VI. The method of calculation is exemplified in the
analysis of the Escresyl benzoate in the toluene solution obtained in

the reaction of the ester with phenylmagnesium bromide.

Ml. of toluene solution of ester = 20
at 0.030 mole/250 ml.

Ml. of 0.22 N NaOH in Ethylene glycol = 25

M1. of 0.196 N HCl in Ethanol = 20.92

Meq. ester = (25 x 0.22) - (20.91 x 0.196)
present in solution

5.50 - b.09

1.81

Percent ester reacted.

2' g-fiéhl x 100 = h1.2% ester reacted

TABLE VI

30

EXTENT OF ESTER REACTION WITH ARYL GRIGNARD REAGENTS AS DETERMINED

BY HYDROLYSIS AND AMOUNT OF KETONE FORMED

 

 

Reaction

Percent Ester Reacted

 

Determined by

Determined by

 

Hydrolysis Ketone Formed

Phenyl Efethyl benzoate with

phenylmagnesium bromide 35.6 37.5
Phenyl Efethylbenzoate with

Efmethylphenylmagnesium bromide h9.5 51.0
Phenyl Efisopropylbenzoate with

Efmethylphenylmagnesium bromide 58.3 60.1
E:Cresy1 benzoate with

phenylmagnesium bromide 51.2 h3.l
E:Cresy1 Efmethylbenzoate with

Erethylphenylmagnesium bromide 52.h hh.7
EfCresyl Efisopropylbenzoate with

phenylmagnesium bromide 39.3 26.6 .

 

31

RESULTS

The results of this study are assembled in four tables according
to the Grignard reagent employed. The data are presented on the basis
of: 1) the total yield of ketone complex,* calculated from the actual
yield of ketone plus the weight of ketone or ketone complex consumed in
the formation of tertiary alcohol; 2) the percent of the total ketone
complex which was converted to alcohol during the reaction and 3) the
percent of Grignard reagent reacting to give ketone and alcohol. 0n
the basis of these comparisons, the results indicate that the over-all
reactivity of the esters, based on percent Grignard reagent reacted,
decreases with increased size of the alkyl substituent on the Grignard
reagent. The results also indicate that the ketone or ketone complex
is more reactive toward phenylmagnesium bromide than is the ester,
that the electron donating ability of the alkyl group is probably more
important in the Grignard reagent than in the ester, that steric
hindrance is slightly less important in the ester than in the Grignard
reagent. Finally, the results indicate that the Efcresyl esters are
less reactive than the corresponding phenyl esters and that the percent
of ketone complex reacting to give tertiary alcohol is higher with

the Efcresyl esters than with the phenyl esters.

 

 

"The ketone complex is considered to be the intermediate resulting when
one molecule of a Grignard reagent reacts with one molecule of an ester.
This complex may decompose to the ketone or it may react with more
Grignard reagent to form a tertiary alcohol.

32

The Phenylmagnesium Bromide Series

The results of the reactions of phenylmagnesium bromide with the
phenyl esters of the four benzoic acids, benzoic, methylbenzoic, ethyl-
benzoic and isoprOpyl-benzoic, and the Efcresyl esters of benzoic and
isoprOpylbenzoic acid are presented in Table VII. With both the phenyl
and Efcresyl esters the over-all reactivity, based upon the amount of
Grignard reagent reacted, decreased with the introduction of an alkyl
substituent on the acyl portion of the ester. ‘With the phenyl esters
of Efmethyl and Efethyl benzoic acid there was only a slight difference
in the over-all reactivity and in the amount of ketone converted to
alcohol. A more significant decrease was experienced with phenyl
2-i30pr0py1benzoate. These results indicate that the introduction of
an alkyl substituent in the acyl portion of the ester results in de-
creased reactivity of both the ester and the resulting ketone inter-
mediate. The results also indicate that the most marked decrease of
reactivity takes place in the ketone complex since the greatest decrease
in the amounts of complex converted to alcohol occurs in descending
from phenyl benzoate to phenyl 2-methy1benzoate and from phenyl 2-ethyl-
benzoate to phenyl 2-isopropy1benzoate. In the case of phenyl benzoate,
the resulting ketone complex was sufficiently more reactive than the
ester to result in a lower yield of total ketone as compared to the
other phenyl esters. Table VII indicates that Efcresyl benzoate is
considerably more reactive than.phenyl benzoate but that Efcresyl
grisopropylbenzoate is somewhat less reactive than the corresponding

phenyl ester. Significantly, however, the percents of ketone complex

33

TABLE VII

PERCENT KETONE COMPLEX FORMED, PERCENT KETONE COMPLEX CONVERTED TO
ALCOHOL AND PERCENT GRIGNARD REAGENT REACTING IN THE REACTIONS
OF PHENYLMAGNESIUM BROMIDE WITH ARYL ESTERS

W

 

Percent Ketone Percent Ketone Percent
Ester Complex Formed Complex Converted Grignard
to Alcohol Reacting
Phenyl benzoate 32.79 87.0h 62.96
Phenyl Efmethylbenzoate 37.01 50.05 55.55
Phenyl Efethylbenzoate 37.52 h5.72 5h.67
Phenyl Erisopropylbenzoate 33.88 38.35 h8.15
EfCresyl benzoate h3.12 90.85 80.27
EfCresyl isopropylbenzoate 26.6h 55.08 h0.23

 

3b

converted to alcohol is greater for both Efcresyl benzoate and Efcresyl
Erisopropylbenzoate than for the corresponding phenyl esters. This
indicates that the ketone complex somehow controls the reaction which

produces alcohol.

The EfMethylphenylmagnesium Bromide Series

 

Table VIII presents the results obtained in the reactions of
2-methy1phenylmagnesium bromide with the same four phenyl esters and
the Efcresyl esters of 2-methy1benzoic acid and 2-ethylbenzoic acid.

In this series the amount of Grignard reagent reacted and the total
amount of ketone formed both decreased as the size of the alkyl substit-
uent increased, the more significant change taking place between the
2-ethylbenzoate and 2-isopropylbenzoate. In contrast to the previous
series, the reactivity of the ketone complex increased.

These results suggest that decomposition of the ketone complex is
especially sensitive to steric hindrance but that, as the hindrance
increases, the complex becomes slightly more reactive. This is possibly
due to a loosening of the bonds of the complex which would enhance
reaction with any reagent which could break through the steric barrier.
In addition, the Efmethyl group of the Grignard reagent apparently
increases the ease with which the ketone complex forms. The total
ketone complex formed is increased from 8 to 17 percent in this series.

The over-all yield of ketone and percent Grignard reagent reacted
are less for the Efcresyl esters of this series than for the phenyl

esters. The percent of ketone complex converted to alcohol is

35

TABLE VIII

PERCENT KETONE COMPLEX FORMED, PERCENT KETONE COMPLEX CONVERTED TO
ALCOHOL AND PERCENT GRIGNARD REAGENT REACTING IN THE REACTIONS
OF EfMETHYLPHENYLMAGNESIUM BROMIDE WITH ARYL ESTERS

 

 

Percent Ketone Percent Ketone Percent

Ester Complex Formed Complex Converted Grignard

to Alcohol Reacting
Phenyl benzoate 33.38 21.1)1 10.911
Phenyl E-methylbenzoate 55.39 10.79 60.38
Phenyl Efethyl benzoate 51.01 11.68 56.60
Phenyl E-isopropylbenzoate hl.52 16.72 h9.06
E—Cresyl E—methylbenzoate 51.63 15.31 59.82
E-Cresyl E-ethylbenzoate 173 .62 201711 51.28

 

36

considerably greater for the Efcresyl compounds than for the correspond-
ing phenyl esters. Both of these observations confirm the trend noted

in the previous series, i.e. that the Efcresyl esters are less reactive
than their phenyl analogues but that the Efcresyl moiety is involved in

the reactions which produce alcohol.

The EfEthylphenylmagnesium Bromide Series

 

The results of the reactions of the four phenyl esters and the
Efcresyl esters of Efmethylbenzoic acid and Efethylbenzoic acid with
Efethylphenylmagnesium bromide are presented in Table IX. The over-all
reactivity and the total ketone complex formed increases slightly as
the size of the Efsubstituent in the acyl portion of the ester increases.
There is, however, a decrease in reactivity in this series compared to
the previous series. This decrease is greatest with the Efmethyl and
Efethylbenzoates. The percent of ketone complex reacting to form
alcohol is observed to decrease as the size of the Efsubstituent on the
acyl portion of the ester increases. This parallels the results
obtained with phenylmagnesium bromide.

The results obtained with the ortho-cresyl esters are similar to
those obtained in the previous series. The amount of ketone converted
to alcohol increases with increasing size of the alkyl substituent;
however, these values do not increase in comparison to the corresponding

phenyl esters of the series.

The E71sopropylphenylmagnesium Bromide Series

 

The results obtained in the reactions of the four phenyl esters and

37

TABLE IX

PERCENT KETONE COMPLEX FORMED, PERCENT KETONE COMPLEX CONVERTED T0
ALCOHOL AND PERCENT GRIGNARD REAGENT REACTING IN THE REACTIONS
OF EfETHYLPHENYLMAGNESIUM BROMIDE WITH ARYL ESTERS

 

Percent Ketone Percent Ketone Percent

 

Ester Complex Formed Complex Converted Grignard

to Alcohol Reacting
Phenyl benzoate h1.01 18.22 h8.b8
Phenyl Efmethylbenzoate 38.25 21.79 h6.5l
Phenyl Efethylbenzoate h1.13 16.86 h7.2h
Phenyl Efisopropylbenzoate h2.33 13.05 h7.85
EfCresyl Efmethylbenzoate hh.67 13.82 50.8h
E:Cresy1 Efethylbenzoate h2.h2 16.20 b9.29

 

38

the Efcresyl esters of benzoic acid and Efisopropylbenzoic acid with
Erisopropylphenylmagnesium bromide closely resemble those obtained in
the Efmethylphenylmagnesium bromide series. The results of this series
are presented in Table X. Both the percent Grignard reagent reacted
and the total ketone complex formed decrease with increasing size of
the alkyl substituent on the ester. This decrease is greatest between
the reactions of phenyl Efmethylbenzoate and phenyl Efethyl benzoate.
As the size of the alkyl substituent of the ester increases the
percent of ketone complex reacting to form alcohol also increases.
A similar trend appears when.Efmethylphenylmagnesium bromide is used.
The results with the Efcresyl esters indicate again the lower reactivity
of these esters compared with the corresponding phenyl esters. The
percent ketone complex reacting to form alcohol is much higher for
the Efcresyl esters than for the phenyl compounds supporting the trend

of the first and second series.

39

TABLE X

PERCENT KETONE COMPLEX FORMED, PERCENT KETONE COMPLEX CONVERTED T0
ALCOHOL AND PERCENT GRIGNARD REAGENT REACTING IN THE REACTIONS

OF EMROPMHENYLMAGNESIUM BROMIDE WITH ARYL ESTERS

 

Percent Ketone Percent Ketone Percent
Ester Complex Formed Complex Converted Grignard
to Alcohol Reacting

Phenyl benzoate 39.h9 1h.55 hh.23
Phenyl Efmethylbenzoate h5.29 13.10 51.21
Phenyl Efethylbenzoate 29.15 1h.26 33.30
Phenyl EfiSOPropylbenzoate 27.18 19.85 32.57
E:Cresyl benzoate 31.h6 22.28 38.39

EfCresyl Erisopropylbenzoate

22.51

29.39

29.25

 

b0

DISCUSSION

The results of this work may be conveniently summarized under three
headings, i.e. the effect of steric factors on 1) the formation of the
ketone complex, 2) the reaction of this complex to produce the alcohol
and 3) the total amount of Grignard reagent reacting.

The formation of the ketone complex, which can be simply represented

by the reaction:

OW * 0738-0 .... 0 {4-0-0

géX

is apparently only slightly affected by steric factors of the order of
magnitude employed in this work. This can be visualized clearly by
reference to Table XI which assembles the yields of ketone complex
obtained from the block of experiments reported in this study. Only
when.EfisoprOpylphenylmagnesium bromide is employed does the yield of
complex decrease appreciably. The activating effect of the Efmethyl
group of Eftolylmagnesium bromide is, however, quite apparent.

The stability of this complex, which has long been a topic of
speculation, is apparently great enough that the rate of formation of
alcohol is controlled by it. Until now, the question of alcohol
formation has centered about two questions: 1) does the complex decom-
pose to ketone and the ketone then react with more Grignard reagent to

give alcohol or 2) does the Grignard reagent react directly with the

111

TABLE XI

PERCENT OF KETONE COMPLEX FORMED WITH PHENYL ARYL ESTERS
AND ARYL GRIGNARD REAGENTS'

 

 

 

 

Grignarg %
Reagent" Ester”

Enydrogen EfMethyl EfEthyl EfIsopropyl
Enydrogen 32.79 37.01 37.52 33.88
E—Methyl 33.38 55.39 51.01 h1.52
EfEthyl h1.01 38.25 h1.13 h2.33
EfIsopropyl 39.h9 h5.29 29.15 27-18

 

*Yields are reported in percent 0f the theoretical quantity of
ketone complex.

h2
complex? The results of this work strongly suggest that the latter
interpretation is correct. This is based on the following reasoning:
A comparison of the yields of alcohol from reactions of Efcresyl or
phenyl esters indicates that the Efcresyl compounds give higher yields
than the corresponding phenyl esters. This can only mean that the
formation of alcohol is dependent on the aryloxy portion of the ester.
Since this group is not present in the ketone, it seems reasonable to
pr0pose that the ketone complex is sufficiently stable so that either
the Grignard must react with it or with the ketone which is formed only
after the slow decomposition of this complex. In either case the
complex will control the reaction.

The fact that the Efcresyl esters increase the alcohol yield is also
significant. If the Efmethyl group acts sterically it will tend to
loosen the complex and possibly hasten its decomposition to ketone.
This favors the picture of Grignard reaction with the ketone. If the
Efmethyl group acts electrically its election donating properties will
increase the basicity of oxygen atoms in the complex and will favor
the picture of Grignard reaction with the complex.

A possible clarification of this picture can be seen by examining
the values obtained for percent of ketone complex going to alcohol.
These values are arranged in block pattern in Table XII. Here the
striking steric effect produced by changing the Grignard reagent from
the phenyl to the Efalkyl compounds strongly suggests that the Grignard
reagent is reacting with the complex rather than with the ketone since
the latter type of reaction is not expected to be so profoundly affected

by such a change.

L3

TABLE XII

PERCENT OF KETONE COMPLEX REACTING TO FORM ALCOHOL IN REACTIONS OF
ARYL GRIGNARD REAGENTS WITH PHENYL ARYL ESTERS

 

 

 

 

Grignard - Ester

Reagent EnydrOgen EfMethyl EfEthyl EfIsopropyl
Enydrogen 87.0h 50.05 h5.72 38.35
EfMethyl .21.1h 10.79 11.68 16.72
E-Ethyl 18 .22 21.79 16.86 13 .05

Eflsopropyl 1h.55 13.10 1b.26 19.85

ht

An examination of the block pattern (Table XIII) of thexralues
obtained for the total Grignard reagent reacting with phenyl esters
presents some interesting correlations. The diagonal values extending
from upper right to lower left may be viewed as follows: the two values
at the ends of the diagonal illustrate the interaction of an thydrogen
and an Efisopropyl group. The greater reactivity is obtained when the
Erisopropyl group is in the ester rather than in the Grignard reagent.
The remaining two diagonal values illustrate the interactions of
Efmethyl and Efethyl groups. Here, the greater reactivity is obtained
when the ethyl group is in the ester rather than in the Grignard reagent.

Reading along the diagonal extending from upper left to lower
right indicates the relative magnitude of steric interaction between
two thydrogen atoms, two Efmethyl, two Efethyl and two Efisopropyl
groups respectively. The electrical properties of the Efmethyl group
are apparently not great enough to overcome its steric factor in this
reaction. This is shown by the fact that the Efmethyl interaction
gives slightly less reactivity than the thydrogen interaction. If
electrical factors predominate, a greater reactivity would be expected.

Finally a comparison of these diagonal relations with the corres-
ponding values obtained from the Efcresyl esters indicates the same
trends as those noted above but with lower reactivities for the Efcresyl '
compounds. This latter summary (Table XIV) best exemplifies the inter-
play among the three types of steric factors in the reaction under

study.

b5

TABLE XIII

PERCENT OF GRIGNARD REAGENT REACTING IN REACTIONS OF ARYL GRIGNARD
REAGENTS WITH PHENYL ARYL ESTERS

 

___

Grignard

 

 

R t Ester .:

eagen Enydrogen EfMethyl EfEthyl EfIsopropyl
Enydrogen 62.96 55.55 5h.67 h8.15
2 -Methyl 211.91; 60 . 38 56 .60 119 .06
E-Ethyl 88.118 1.6.51 117.214 £7.85

EfIsopropyl hh.23 51.21 33.30 32.59

TABLE XIV

b6

PERCENT OF GRIGNARD REAGENT REACTING IN REACTIONS OF ARYL GRIGNARD

 

REAGENTS WITH PHENYL AND E-CRESYL ESTERS
W

 

 

 

 

 

 

Grignard Ester
Reagent ErHydrogen EfMethyl BfEthyl Eflsopropyl
62.96 h8.15
E ~Hydro gen
80.27 h0'23
60.38 56.60
E -Me thyl
59.82 51.28
h6.51 u7.2h
_o_ -Ethy1
50.85 h9.29
Eflsopropyl
8.39 29°25

 

 

 

 

 

 

Note:

Values in the upper portion of the square refer to phenyl esters;

values in the lower portion refer to Efcresyl esters.

1:?

CONCLUSIONS

. Results of this work'indicate that bulky groups in any of the three
steric areas, i.e. the acyl portion of the ester, the aryloxy portion
of the ester and the Grignard reagent, hinder the reaction of the

Grignard reagent with ester.

. The degree of hindrance has been shown to increase with the increased

size of the Efsubstituent as anticipated.

. Substitution in the ortho position of the Grignard reagent has been

shown to cause the greatest hindrance.

. Formation of the initial complex between Grignard and ester has
been shown to be not appreciably affected by steric factors of the

order of magnitude employed in this study.

. The reaction by which alcohol is formed has been shown to be markedly

influenced by steric factors in the aryloxy portion of the ester.

. Evidence to show that the alcohol is formed by a direct reaction of

the initial complex with Grignard reagent is presented.

h8

B IBL I OGRAP HY
(l) R. C. Fuson, E. M. Bottorff, and S. B. Speck, J. Am. Chem. Soc.,
ég, 1&50-1h53 (19h?)-

(2) R. T. Arnold, H. Blank, R. Liggett, J. Am. Chem. Soc.,E23‘3hhh-3hh6
(19h1)o

(3) D. R. Boyd and H. H. Hatt, J. Chem. Soc.,EQJ 898-910 (1927).
(h) E. P. Kohler and R. Baltzly, J. Am. Chem. Soc.) 55, h015-26 (1932).
(5) L. Smith and C. Guss, J. Am. Chem. Soc.) 52, 80h-805 (1937).

(6) C. R. Hauser, P. Saperstein and J. C. Shivers, J. Am. Chem. Soc.)
79, 606-608 (19h8).

(7) [' E.)Whitmore and R. 3. George, J. Am. Chem. Soc., ég, 1239-12h0
19 2 .

(8) M. S. Kharasch and 0. Reinmuth, Grignard Reactions of Nonmetallic
Substances, New York, Prentice-Hall, 195b, pp. 5h9-688.

(9) R. R. Dreisbach, Physical Properties of Chemical Compounds, A.C.S.
June 1955, Washington, D. C.

(10) Saverio Zuffanti, J. Chem. Education, fig E81 (19h8).
(11) M. Crawford and F. H. C. Stewart, J. Chem. Soc.,hhh3-7 (1952).

(12) W. J. Hickinbottom, Reactions of Organic Compounds, Longmans,
Green and Co., New York, 19h8, pp. 258-261.

(13) J. Cross and‘Wfl Rolfe, Trans Faraday Soc.) El_35h (1951).

(lb) L. Bellamy, The InfraéRed Spectra of Complex Molecules, London
and New York, John Wiley & Sons, 195h, pp. 129-136,

(15) W. M. D. Bryant and D. M. Smith, J. Am. Chem. Soc.)_5__7_ 57-61 (1935).

APPENDIX

 

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CHEMISTRY LIBRARY

Date Due

 

 

Demco-293

 

 

M!CH|GAN SIAIL UNIVtRSHY

0F AGRICULTURE'AND APPUED SCIENCE

DEPARTMENT OF CHEM!STRY
EAST mas: .u. .mJ-HGAN

CHMBTBY LIBRARY
Thesis, c.2
Pastor,
A study of steric effects in the
reactions of aryl esters with
Grignard reagents.

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Thesis cfé

Pastor,
A study of steric effects in the

reactions of aryl esters with
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CHEMISTRY LIBRARY

Date Due

 

 

Demco-293

MICHIGAN Sl'Ait UNIVERSHY
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DEPARTMENT OF CHEMISTRY

EAST LAHSL uu. .WIVHKJ‘AN

(finnaBSBYIJBRABY
Thesis, c.2
Pastor,
A study of steric effects in the
reactions of aryl esters vdth
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CHEMISTRY mm m

Thesis c.%
Pastor,
A study of steric effects in the
reactions of aryl esters with
Grignard reagents.

 

 

 

 

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MICHIGAN STATE UNIVERSITY LIBRARIES

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