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THE CONDENSATION OF DIETHYL

N-PROPYL CARBINOL AND DIETHYL

ESOPROPYL CARBENOL WITH PHEEVOL
EN THE PRESEN CE

CF ALUMINUM CHLORIDE

Thesis for the Degree of M. S.‘
MECHFGAN STATE COLLEGE
\"l’iiiiam K. Langdon
1940

V. b
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n‘
R .m.
m w
L m

THE!!!

 

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THE CONDENSATION 0P DIETHYL N-PROPYL CARBINOL
AND DIETHYL ISOPROPYL CARBINOL
WITH PHENOL
IN THE PRESENCE OF ALUMINUM CHLORIDE

by
Willian.Keith Langdon

A THESIS
Submitted to the Graduate School Of Michigan State College
of Agriculture and Applied Science in partial
fulfillment to the requirements for the
degree of

MASTER.OF SCIENCE

Department of Chemistry
1940

ACKNOWIEDGMENT

I wish to thank Dr. R. C. Huston for his assistance
and guidance which macle this work possible.

, cfa‘OJ .n. rm

.th‘il‘,

INTRODUCTION

In the year 1916 Huston ané Friedman (l) discovered
that aromatic alcohols condense with aromatic hydrocar-
bons in the presence or aluminum chloride as a catalyst.

In the year 1956 Huston and.Hsieh (3) discovered

that some simple tertiary aliphatic alcohols condense
tith phenol in the presence of aluminum.ehloride.
Since that time Huston one coworkers have condensed
a number of tertiary a1iphatic alcohols with.phenol.

In order to further this investigation, @iethyl
normalpropylcarbinol and diethylisopropylcarbinol were

condensed with.phenol.

HISTORICAL

There are e.number of methods by which.phenols
may be alkylated. Since this work is concerned only
with the condensations of phenol in the presence of
alminum chloride, only this type of condensation will
be discussed. However, it should be mentioned that in
1884 Auer (4) obtained alkyl phenols from simple aliphatic
alcohols and phenol, with a mixture of zinc chloride
and mine.

In 1897 Net (5) reported the formation of diphenyl
methane from benzyl alcohol and benzene with aluminum
chloride as a catalyst. Huston and Friedman (2) repeated
his work with a 30 % yield. They continued this work
and condensed mixed aliphatic aromatic secondary alcohols
and aromatic secondary alcohols with benzene.

In 1924 Huston (6) extended the reaction or benzyl
alcohol using phenol, anisole, and phenitole. 4:5, 45, and
50 percent yields respectively were obtained. In 1926
Huston and Sager (7) attempted to condense a number or
primary alcohols with benzene and were successful only
with allyl alcohol. Huston and Hermann (8) then condensed
allyl alcohol with phenol.

Later Huston (9) and co-workers reported the conden-
sation or benzhydrol, methylphenyl and ethylphenyl car-
binols with phenol giving good yields. Benzhydrol gave a
much higher yield of condensation product. Due to the fact

that benzhydrol has two alpha carbons which are on unsat-
urated benzene rings, this gave additional information

as to the effect of unsaturation or the alpha carbon atom
on condensations.

Huston and Iilsey (10), and Huston and Hradel (ll)
attempted to condense several diaryl-alkyl alcohols and
dialkyl-aryl alcohols with.benzene, with no success. Only
dehydration of the alcohol occurred.

Huston and Hsieh (3) opened a.new field, with.the
condensation of saturated aliphatic secondary and ter-
tiary alcohols with phenol and benzene or their homologs.
They obtained cumene by the condensation of isopropyl
alcohol with benzene in the presence of aluminum.chloride.
They discovered that under the conditions used, primary
alcohols do not condense either with benzene or’phenol,
secondary alcohols condense with benzene, and tertiary
alcohols condense with phenol. JHuston and.Fox (12) con-
densed the tertiary alcohols which had already been
condensed by Huston and Helen (3) with phenol, with benzene.
Tsukervanik (13) condensed simple secondary and tertiary
alcohols with benzene and tolulene, but explained the
condensations by a different mechanism. The condensation
reactions or the tertiary alcohols were extended to the
tertiary heptyl alcohols. These alcohols were condensed
with.phenol and benzene by Huston and Rodrick (l4), and
Boston and Binder (15) respectively.

very recently Huston and Guile (16) extended this
investigation to the tertiary octyl alcohols. They were

successful in condensing the eight dimethyl amyl carbinols
with phenol.

Huston and Breining (17) condensed diethyl isopropyl
earbinol and diethyl normalpropyl carbinol with benzene.
This present work deals with the condensation of these
two alcohols with phenol, with aluminum chloride as a
catalyst.

THEORETICAL

It has been.shown by Huston and co-workers that in
every case in which.there is condensation between an
alcohol and an aromatic hydrocarbon, the alpha carbon
atom of that alcohol.mnst be under strain. This strain
causes the bond between the carbon and oxygen of the hydroxyl
group to be relatively unstable. There are three main
types of alcohols which.fadllinto this classification:

1. Aromatic alcohols in which.the alpha carbon

atom is a member of a ring

2. Allyl alcohols

3. Tertiary alcohols
Secondary alcohols are under some strain and might belong
to the third group. In allyl and benzyl alcohols there
are two groups attached to the carbinol carbon, each of
which.has a strong attraction for the electron pair between
the carbon and oxygen. In tertiary and secondary aliphatic
alcohols, the alkyl groups have a relatively small attract-
ion for that electron pair allowing the pair to shift close
to the oxygen, thus giving the OH group a tendency to
split off.

Three mechanisms have been proposed for condensations
between tertiary aliphatic alcohols and aromatic hydro-
carbons:

l. Alkyl halide formation plus Friedel-Craft reaction.
2. Alkene formation plus condensation.

5. Ether fermation plus rearrangement.

‘me not result is that the hydroxyl group splits off of
the alcohol and a hydrogen splits off of the aromatic
compound with the formation of water. These mechanisms
attempt to explain how the net result is accomplished.
Alkyl Halide Formation Plus Friedel-Orafts Reaction:
his was the scheme outlined by Tzukervanik and Nazarova
(13). They observed that after the first phase of the
condensation, there were present all the components of the
Friedel-Craft reaction. They proposed that the reaction
proceeds in several steps:
1. Altminun chliride plus tertiary alcohol gives an
aluminate plus 301.
2. 1101203 splits from the alcohol giving an olefin.
3. Olefin plus 1101 gives an alkyl halide.
4. Alkyl halide plus aromatic canpound gives alkyl-
aryl coupound plus 301.
It seems unlikely that this is the proper mechanism. It
appears illogical that the hydrogen of a tertiary OH group
can be replaced by the aluminate radical. Hedrick (14)
proved that any 361 given off couldn't be used to form
an alkyl halide. He added a tertiary alcohol to some alum-
inum chloride in an inert solvent and there was instantan-
eous evolution of hydrogen chloride. If 301 were evolved,
it would not be available for alkyl halide formation.
Alkene Formation Plus condensation:
this idea was offered by McKenna and Sowa (18) for the
alkylation of benzene with boron trifluoride as a catalyst.
Ividence of this reaction is shown by the fact that normal

and secondary alcohols give identical products as do iso
and tertiary alcohols. McGreal (19) and Niederal suggested
a like mechanism for condensation with.the use of zinc
chloride. there is evidence against such.a mechanism in
the case of aluminum chloride. Hewever, it is true that
olefins do condense with aromatic hydrocarbons in the
presence of aluminum.chloride. A much higher temperature
was used with the hydrocarbon condensations as well as a
different catalyst. consequently, contrary to the work
of Huston and Sager (7), they were able to condense
primary alcohols and benzene.

Ether Formation Plus Rearrangement:
Smith (20) has shown that a.number of alkyl ethers will
rearrange into alkyl phenols. Rearrangement may be effected
by equal molecular amounts of aluminum chlhride. However,
there is a great deal of evidence which indicates that this
is not the mechanism of condensation. Tertiary alcohols
may be condensed with cmnpounds which have no possibility
of intermediate ether formation such as benzene, anisole,
and phenetole.

so mechaniss.yet reported has been very satisfactory.
It is possible that the reactions proceed through an inter-
mediate addition compound of aluminum chloride, alcohol,
and phenol, followed by rearrangement.

EXPERDENTAL

Material;

1.

2.

N-butyric acid. his was obtained from Eastman's.
(3.13. 161-1639 0)

Isobutyric acid. Eastman's (as. 153.5-1550 c)

e. lthyl bromide. lasman's (mp. ass-40° c)

4.

5.

6.

'7.

8.

10.

11a

12.

13.

14.

15.

Ghloracetic acid. Eastman Practical

Ethyl alcohol. Obtained from the stockroon, 95 %.
N-butyrlchloride was prepared fro. n-butyrie acid and
phosphorous trichloride. (B.P. 99-1010 c)
Iso-butyrylchloride was prepared from isobutyric acid
and phosphorous trichloride. (B.P. 90--92o C)
Phosphorous trichloride. Obtained from Eastnan.

m1: was redistilled, using a one-degree fraction.
Almninum Chloride. Merck's Reagent anhydrous resublimed.
Magnesium turnings. These were especially prepared for
Grignard reactions and were dried in a desiccator

over calcium chloride.

Benzene. Thisphene free c.P. This was dried over
freshly cut sodium.

Anhydrous ether for Grigiard reactions which was dried
over freshly cut sodium.

Petroleum ether. B. P. 30-650 c. Dried over freshly

cut sodium.

l6. Methyl n-propyl carbinol. This alcohol was prepared
in three ways:
1. Ethyl butyrate reacting with two moles of ethyl
magnesium bromide.
a. N-butyryl chliride reaction with two moles of
ethyl magnesium bromide.
3. Chlorscetyl chloride reacting with three moles
of ethyl magnesium. bromide.
17. Diethyl isopropyl carbinol. This was prepared fro-
isobutyryl chloride and two moles of ethyl magnesium
bromide.

The Preparation of the Alcohols

A. the Preparation of the Grignard Reagent.

The only Grignard reagent used was ethyl magnesium
bromide. The usual Ihitmore procedure (21 and 22) was
modified somewhat. Less ether was used and a faster rate
of addition employed.

In a three liter three-necked flask fitted with an
efficient glycerine sealed stirrer, reflux condenser, and
dropping funnel are placed four moles of magnesium turnings
(98 grams). Thirty cc. of a mixture of four moles of
ethyl bromide and two volumes of anhydrous ether are added
directly to the turnings. After thereac tion has started
and progressed for a few minutes, 200 cc. of ether is added
directly to the dry magnesium. me remaining halide other
solution is then added with stirring at such a rate that
the ether refluxes about one drop per second. After about
one-half If the halide solution has been added, the solution
in the flask may become warmer than the reflux tempera-
ture of ether due to the formation of the Grignsrd reagent.
Under these circmnstances, a little external cooling may
be used. After the halide-ether mixture has been added,
the solution is stirred for four more hours and let stand
overnight. ‘

After the solution has stood overnight, the proper
amount of the ester or acid halide is diluted with two vol-
mnes of anhydrous ether. This solution is added at the

rate of one drop per second until all of the solution
has been added. The formation of the addition complex is
instantaneous and therefore it may be hydrolyzed immediately.
It is decolposed by pouring on ice. The precipitated
mamasiun compounds are dissolved by adding 10 93 301 until
the solution is clear. Ilhe ether layer is separated and
the water layer is extracted several times with ether.
be other solutions are combined and are washed with dilute
sodium carbonate solution. They are then dried over
anhydrous sodium sulfate.

The other is evaporated off and the alcohol distilled

under vacuum.
B. The: Preparation of Diethyl H-Propyl carbinol

Diethyl n-propyl carbinol was first prepared by lesson
(25) frets: ethyl butyrate and ethyl magnesim bromide.
It was later prepared by-clarke and Riegel (23) from
diethyl Ice-tone and n-propyl magnesium brmnide. It was
prepared by Ihitmore (24) by the Grignard-ester synthesis,
and Breining prepared it from normal butyryl chliride and
ethyl magnesium bromide. The author prepared this alcohol
by both the ester and acid chloride synthesis with yields
between 62 and 70 percent in each case. Jackson ( Kedzie
menistry Laboratory ) suggested that an attempt be made
to make this alcohol using one mole of chloraeetyl chloride
and three moles of ethyl magnesium bromide.

Equations for this reaction:
/ MgBr

/0
(1) Cl“ -c\cl+ 0235Mgm‘ ’9 Cl-CHZ-bi-CZHS 13“ male.

(2) Cl WEB? H MERE-9 01 m E55533 and l
g . _ _ + V _ _ _ .
ngzns (:25 2 55+MEBmlm°°
(a) ei-mz- 3235+ 0235mm 9 cza5-caz-gggfignr1-Mgm01
2 5

3rd mole.

(40 6337- figm— HOB «.9 0337-3-ng + MgBron
235 0235

72 and 7'7 percent yields were obtained by this method.

he only modification or the above Grignard procedure was
that after the addition of the chldraeetyl chloride to the
Grignard reagent, the ether was evaporated off and the
reaction mixture was let stand on the steam bath for twenty-
four hours in order to insure the hydrocarbon type of
synthesis on the alpha carbon atom.

3. me Preparation of Diethyl Isopropyl Carbinel

Reining prepared this alcohol from isobutyryl chloride
and two moles of ethyl magnesium bromide. This was the method
by which this alcohol was prepared, and the procedure
used was the same as the above procedure for the preparation.
of diethyl n-propyl carbinol.

_ Diethyl n-prOpyl carbinol boiled at 55.56%: at 8 mm.
pressure, or 157-157.8°C at 744.5 m. pressure. Diethyl

isopropyl carbinol boiled at 55-3500 at 8 mm. pressure or
at 157-15800: at 742 mm.

condensation Vi th Phenol

The following procedure for the condensing of the
above alcohols with phenol has been found to be very sat-
isfactory for the past and present, workers in this labor-
story.

A 500 co. round-bottomed three-necked flask was fitted
with a condenser, mechanical glycerine sealed stirrer,
and stopper fitted with a thermometer. Thirty-two grams
(0.25 mole ) of octyl alcohol and 4'7 grams (0.5 mole) of
phenol, dissolved in 200 cc. of petroleum ether were placed
in the flask. Seventeen grams (0.125 mole) of aluminum
chloride were added to the flask over the course of an
hour. The temperature was controlled A between 25 and 30° 0
by immersing the flask in cold water. The condenser was
protected from the moisture of the air by a calcium chloride
tube. H01 was given off during the course of the reaction.
After standing overnight, the mixture was poured into ice
and concentrated H01. The two layers were separated. The
water layer was extracted three times with ether and this
extract combined with the other layer. The combined extract
was dried over anhydrous sodium sulfate and the ether
removed at ordinary pressure.

The residue was fractionated with a Claisen flask
having a 12 to 18 inch column. ‘Jhree main fractions were
obtained in this fractionation. he fractionation was
carried out with a pressure from 2 to 7 mm. me first

fraction below 65° C: consisted mainly of unreacted alcohol
and its decomposition products. The next fraction up to
100° 6 was chiefly phenol. The fraction loo-150° c was
mainly the octyl phenol and was refractionated several
times in order to obtain a product which distilled over

a narrow range.

Ellie average yield of the condensation product of
diethyl n-propyl carbinol and phenol was 36 %. The average
yield of the condensation product of isopropyl carbinol
and phenol was 54 %. ,,.

Derivatives

A. Benzoyl Esters

Benzoyl esters of both alkyl phenols were prepared.
The procedure used is that of Shriner and Fuson (26).
Three grams of the alkyl phenol were dissolwed in 4 cc.
of’pyridine and 3 cc. of benzoyl chloride were added.
After the initial reaction, the mixture was refluled over
a low flame for one hour and then poured on ice. The meter-
ial was extracted with ether. The pyridine was renewed
by washing with dilute sulfuric acid and than the excess
acid was removed by washing with sodiun.carbonate solution.
The ether was removed and the ester distilled under reduced
pressure. After standing in the refrigerator, the ester
crystallized out. The oil was removed on a.porons plate,
and the ester was recrystallized from petroleum.ether and
from ethyl alcohol until it had a.constant:melting point.
Data on these esters are found in table II.

B. Alpha-naphthylurethanes

These were prepared in the method described by wertel
(16). One gram of the tertiary octyl phenol was placed in
a test tube and 1.5 cc. of alpha-naphthyl isocyanate was
added, the reaction being catalyzed by two drops of dilute
anhydrous other solution of trimethylamine. The tube was
fitted with a calcium chloride tube. The reaction.was

heated on a steam bath for a half an hour and cooled. The
solidified contents were extracted with 60 cc. of boiling
ligroin (13.2. ao-120° c) and filtered. Upon cooling the
urethane crystallized out. It was recrystallized from
petroleum other until a constant melting point was obtained.
Data on these urethanes are given in Table III.

Proof of Structure

The proof of structure of these phenols was carried
out in a.manner similiar to that described by Guile (16)
and Rodrick (14). The first step in this procedure was
the preparation of the corresponding alkyl benzene. Both
of these alkyl benzenes were prepared by Breining (17).
Data on this are given in Table IV. The second step was
the preparation of the para nitro alkyl benzene. The third
step was the oxidation of the above nitro compound to para
nitro benzoic acid in order to prove that it was substituted
in the para.position. The fourth step was the reduction
of the nitro compound to the corresponding amino compound.
The fifth step was the diazotization of this amine and
hydrolysis to-the corresponding phenol.

A. Preparation of the Alkyl Benzenes

The procedure for the preparation of the alkyl benzenes
is very similiar to that for the preparation of the alkyl
ephenols. Both Breining and Guile (l7 and 16) give a detailed

procedure for these condensations.

B. Nitration of the Tertiary Octyl Benzenes

Malherbe's (27) procedure was used. The hydrocarbon
was treated with an equal weight of fuming nitric acid and
cooled during the addition. After the reaction had subsided,
the mixture was warmed to 90° c on a steam.bath for an

hour. It was then poured on ice and extracted with ether

three times. This extract was dried over calcium chloride
and after the removal of the ether, was fractionally distilled
under reduced pressure. Data on these compounds are given

in Table V.

G. Oxidation of the Para Nitro Tertiary Alkyl Benzenes
Mhlherbe's (27) method was used for this oxidation.
The purpose was to establish the position of the tertiary
alkyl group on the benzene ring. One gram of the nitro
compound and 20 cc. of 6 N nitric acid were placed in a
Darius tube, sealed and heated in a Carius furnace at
130° c until a large number of crystals had formed in the
tube. From three to eight days were required. The crystals
were removed from the tube. They were washed with hot
petroleum ether to remove oily materials and then recrystal-
lized several times from alcohol. In both cases the crystals
melted 238-2400 C and there was no lowering of the melting
point when mixed melting points were taken with para nitro
benzoic acid. This indicated that the alkyl group was para
to the hydroxyl group in the original compound.

D. Reduction of the Para Nitro Tertiary Alkyl Benzenes
Thirty grams of tin were placed ina liter Erlenmeyer
flask. About 15 grams of p-nitro tertiary alkyl benzene were

added and 100 cc. of concentratedIHCl. The mixture was
heated on the steam.bath. If there still was an oily layer
on top of the liquid after the tin had been digested, more
tin an.HCl were added. After addition of 200-300 cc. of

water, the mixture was made alkaline with 40 percent sodium
hydroxide. The alkaline solution was steam.distilled.

The distillate was extracted with ether and the ether
solution was dried with solid potassium hydroxide. After
removal of the ether, the solution was fractionally distilled
in a small modified Claisen flask. Data on these amines

are found in Table VI.

‘3. Phenols From the Para Amino Tertiary Alkyl Ebnzenes

The procedure used was that given by Guile (16). The
amine was treated with concentrated sulfuric acid, 5 co.
in 10 cc. of water, for each 2 grams of amine. The solid
amine salt was suspended in ten times the volume of'water.
The solution was cooled to 5° C and an equivalent amount
of 25 percent sodium nitrite solution calculated to react
with the amine, was added over a five hour period. Stirring
was continued for two hours and the solution was warmed on
the steam bath for an hour; The reaction mixture was steam.
distilled. The phenol was extracted from the distillate
with other, and the extract dried over anhydrous sodium
sulfate. The pure alkyl phenol was obtained by fractional
distillation under reduced pressure.

Ebnzoyl esters and alphanaphthyl urethanes were made
of the two above phenols. In each.oase the melting points
of the derivatives were the same as that of the correspond-
ing derivative of the phenol made by condensation of the
tertiary alcohol with phenol in the presence of aluminum

chlbride. There were no melting point depressions when
mixed melting points were taken. This indicated that
the alkyl phenols synthesized by the two different methods

were identical.

Tables of msical Conttants
Table I. Alkyl Phenols

Diethyl n-propyl Diethyl isopropyl
p-hydroxy phenyl p-hydroxy phenyl

 

 

methane methane

Melting Point °c (liquid) 88.5-84
Boiling Point: °c

Atmospheric Pres. 265, 741 mm. 260, 741 mm.

Reduced Pressure 154-137, 6 mm. 110-112, 2 mm.

4 5°0
Refractive Index Nfi ° 1.5212 (solid)
Surface Tension 27°C 56.62 (solid)
Specific Gravity-20° .9561 (solid)
'560

Percent Carbon’ 81.60 81.42
Igoreent Hydrogen“ 10.92 10.69

* calculated for 8148220, 0 = 81.49 H: 10.75

 

 

Table II. Alkyl Benzenee

gg1 Benzene Average Yielg 2111115 Point
Diethyl n-propyl o
phenyl methane 46 % 90-93 8, 6 mm.
Diethyl isopropyl a
phenyl methane 42 % 70-71 0, 5 mm.

W
Table III. Pare Nitro Alkyl Benzenes

mustang ailing Point °c 23131:: g 2*
D1 thyl n-propy]. .
p-nitro phenyl methane 125-150, '5- H. 6.07
Diethyl isopropyl
p-nitro phenyl methane 150-135, 6 mm. 5.97

* calculated tor 01432102N, N‘= 5.95

Table IV. Pare Amino Tertiary Octyl Benzenes

Substance Boiling Point °C Analzsis: g 11*
Diethyl, n-propyl
p-emino phenyl methane 120-125, 5 mm. 6.80

Diethyl isopropyl
p-amino phenyl methane 125-150, 6 mm. 6.75

* Calculated for 01432311, N = 6.82

 

Table V. Benzoyl Esters

my 1. Ester g; Melting Point °C a 818*
3 c 3 B
Diethy1 n-propyl
p-hydroxy phenyl methane (LO-40.5 81.18 8.42
Diethyl isopropyl
p~hydroxy phenyl methane 38.2-38.6 81.06 8.64
* Calculated for 02132602,, 381.24 s: 8. 44 i

 

 

 

 

 

 

Table VI. Alpha Nephthyl Urethanes

Alpha Naphtgzl Urethang or M, P. °C Analmla: g 11*

Diethyl n-propyl
p-hydroxy phenyl methane 106.7-10? 5.66

Diethyl isopropyl
p-hydroxy phenyl methane 1. 2.8-128 5 3.68

* Calculated for 32532902“: N s 3. 78

SUMMARY

1. me tertiary octyl alcohols, diethyl n-propyl
carbinol and diethyl isopropyl carbinol, have been condensed
with phenol in the presence of aluminum chloride to yield
p-tertiary octyl phenols.

2. he benzoyl esters and alpha naphthyl urethanes
of these two phenols have been prepared.

3. The structures have been established by synthesizing
them in a different. say.

1.
2.
5.
4.
5.
6.
'l.
8.
9.
10.
11.
12.
13.
14.
l5.
16.
1'7.
18.
19.
20.
21.
22.
25.
24.
25.

BIBLIOGRAPH!

Huston and Priedemann
Huston and l'riedemann
Huston and Hsieh

Auer

Net

Huston

Huston and Sager
Huston and Newman

Huston and Others

Huston and Uilsey
Huston and Hradel
Huston and Fox
Tzulervenik and others

Huston and Hedrick
Huston and Hinder
Huston and Guile

Huston and Reining
McKenna and Sore

MC Creel and Niederal
Smith

lhitmore and Mertscher

J. Am. Chem. Soc. 58 2527
40
58
l?
298
Soc. 46 2775

See. 48 1955

Glam. 7’85

439

J. Am. 8000

J. Am. Chem. Soc.
669

255

hr.
Ann.
I. Am.
J. Am.

Chem.
Chem.
master's Thesis

Michigan State College
J. Am. Chem. Soc. 55 2579
Chem. Soc. 5? 4484
Chem. Soc. 54 1506
Master's ‘nlesis

Michigan State College
Master's Thesis

Michigan State College
Master's Thesis

Michigan State College
J. Gen. ChemJISfl 7 652
J. Gen Chem. 0883 5 764
GlenJJSSH 5 117

Chem. 59 2001

I. Am.
J. Am.

J. Gen.
Jo Am. 3°C.
Master's Thesis

Michigan State College
J. Am. Chemo 800. 60
Master's lhesis

Michigan State College
J. Am. Chem. Soc. 59 470
Chem. Soc. 55 2625
Chem. 55 415

Chem. Soc. 1561 55

J. m.
J. m.
J. Am.

Soc.

(1916)
(1918)
(1956)
(1884)
(1897)
(1924)
(1926)
(1933)
(1951)
(1950)
(1932)
(1955)
(1954)
(1954)
(1957)
(1955)
(1955)
(1957)
(1955)
(1938)
(1958)
(1936)
(1935)
(1955)
(1955)

26. Edgar J. Am. Chem. Soc. 51 1485 (1929)
2?. Clarke and Riegel J. Am. Chem. Soc. 34 6779 (1912)
28. Whitmore and Coworkers J. Am. Chem. Soc. 56 180 (1954)
29. Masson Comptes Rendus 152 485 (1901)

50. Shriner and Pusan The Systematic Identification of
Organic compounds, Page 62.

51. Helherbe Her. 52 519 (1919)

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