DOCTORAL DISSERTATION SERIES
t i t l e The Q q n d e m s a 7/o n Of The Mefhvl diprojov) Ctrbrnoh

U M Fhfbol Ih The Presence Of /Uumimtn Chloride

Mo

AUTHOR U r

L

U N IV E R S IT Y

M k h i& ih J7*i c Q /k & e

DEGREE

DATE

M

m i

PUBLICATION NO $26
mim

i i i i i i i

num

'2

$

UNIVERSITY MICROFILMS

M

A N N ARBOR

-

MICHIGAN

THE C ON DE NSATION OF THE M E T H Y L D I P R O P Y L CARBINOLS
WITH PHE HO L IN THE P R E S E N C E OF A L U M I N U M CHLORIDE

"by
CA RL R I D G E K E L O Y

A THESIS
■ Submitted, to the G r a d ua te School of M i c h i g a n
State College of A g r i c u lt u re and A p p l i e d
Science in partial fulfilment of the
requirements for the degree of
D O C T O R OF P HI L O S O P H Y

D e p a r t m e n t of C he mi st ry
1942

ACKNOWLEDC-EMSNT
The writer wishes to express his

sincere s r a titude to

Dr. R. C. Huston for the kindly interest and helpful

sug­

gestions which have made possible the c om pletion of this
work.

T AB LE OF CONTENTS
I n t r o d u c t i o n ............................... page 1
Hi storical

................................

Th eo re ti ca l ................................
E x p er im e nt al Pr oc edures

..................

2
9
17

M a t e r i a l s ............................

17

P r e p a r a t i o n of Carblnols

18

.

.

.

.

C o n d e n s a t i o n s .....................
Derivatives
Proof of Struc tu re

23

................. 25
.

.

.

.

.

.

T a b l e s ................................

27
32

D i s c u s s i o n ...................................... 35
Summary
B ib li o g r a p h y

.....................
................................

38
39

1
INTRODUCTION
In previous papers from this laboratory (1) the con­
densations of tertiary butyl,

tertiary amyl,

tertiary hex-

y l , and tertiary heptyl alcohols wi th phenol in the p r e ­
sence of anhydrous aluminum chloride have bee n described.
Of the seventeen possible tertiary octyl alcohols,

all (2)

but the methyl dipropyl carbinols have been condensed with
phenol by us ing aluminum chloride as the condensing agent.
The purpose of this paper is to describe the condensation
of these remaining tertiary octyl alcohols.

I

2
HI b i On I oA h
G 0 nd.ens9.ti0 n may be d ef ined as the u n i o n of two or more
organic molecules or parts of the same molecule
without the elimination of component atoms)

(with or

in w hich the new

c om bi na ti on is effected b e tw ee n c a r b o n ‘'atoms.

It is a p r o ­

cess closely associated wit h the history of synthetic o r g a n ­
ic chemistry.

Internal condensation,

atoms within a molecule,
compounds,

the linking of carbon

leads to the f o r m a t i o n of cyclic

whereas external condensation is the u n io n of two

or more differ en t molecriles to p ro duce a molecule of greater
com pl ex it y and, generally,

of greater m ol ec ul ar weight.

The u n io n b e tw ee n molecules or parts of the same m o l e ­
cule is usually promoted by u ns at u r a t i o n and by the tendency
exhibited by unsaturated atoms to saturate themselves.
W h e t h e r the combining molecules are already u n s a t u r at ed or
are rendered unsaturated by the withdrawal of ce rtain e l e m ­
ents,

a catalyst is re quired to b ri ng about the condensation,

s erving/either as a d e h y d r at in g agent,

as an activator,

or

both.
Condensations

involving d e h y d r a t i o n are very numerous.

A mo ng the d eh yd ra ti on catalysts that have b e e n used may be
menti on ed the following:
phosphorus pentoxide,

sulfuric acid, phosphoric acid,

m ag ne si um chloride,

zinc chloride,

phosphorus p e n t a c h l o r i d e , aluminum chloride,

ferric c h l o r ­

ide, (both the anhydrous salt and in the form of the hexahydrate),

stannic chloride,

ac'etic acid,

sulfuric and acet-

3
ic acid mixture, b o r o n trifluoride, h y d r o g e n chloride, h y d r o ­
gen fluoride,
ide.

antimony trichloride,

and titanium t e t r a c h l o r ­

Of these condensation cataijrsts the ones listed below

have be en shown to be more efficient and of greater a p p l i c a ­
bility,

so an example of each is listed:
Zinc chloride was the catalyst used by Fi scher

and Roser

(3) in the preparation of aminotriphenylmethane

by condensing benzhydrol with aniline hydrochloride.
Sulfuric acid was employed as a catalyst by Be ck e r (4)
in 1882 when he condensed m-nitrobenzyl alcohol and benzene
to yield m - n i t r o d i p h e n y l m e t h a n e .
Mixtures of acetic and sulfuric acids were used by
Meyer and Munster (5)

in condensing benzyl alcohol and b e n ­

zene to give d i p h e n y l m e t h a n e .
Stannic chloride was the condensing agent used by
Michael and Jeanprstre

(5)

in preparing phenyltrirnethylphen-

y lacetonitrile from mesitylene and p h e n y l h y d r o x y a c e t o n i t r i l e .
Phosphorus pentoxide was employed by He mi l ia n (7) as a
catalyst in the condensation of benzhydrol with p-xylenje to
forrn diphenyl-p-xylylrnethane.
Magnesium chloride was the catalyst used by M a zz ar a (8 )
in condensing propyl alcohol with m-cresol to give propylm-cresol.
Hydrogen chloride was employed by Noelting (9)

in p r e ­

p ar in g p-nitrodimethyldiaminod iphenyltolylmethane from pnirtodimethylaminobenzhydrol and m-toluidine.
Zincke (10) announced the reaction of aromatic h y d r o ­

carbons with h a l o g e n compounds

in the pre se nc e of zinc dust:

Zn

V -

*

C 6 H 5H + C 1 C H 2 .06H5

I

C 6 H 5 C H 2 C 5H 5 +JHC1

S ince aluminum chloride catalyzes the same reaction,

zinc

chloride may be formed as an intermediate.
Because of its po we rf ul d e h y d r a t i n g ac t i o n al uminum
chloride has engaged the a tt e nt io n of workers

in this l a b o r ­

atory, both in studies of its uses and in attempts

to d e t e r ­

mine the possible me chanisms by w h ic h it acts.
Friedel and Grafts

(11)

first introduced aluminum

chloride as a catalyst in c on de n s a t i o n reactions among a l i ­
phatic compounds.

They at first observed that alum i nu m

chloride acts in the cold on amyl chloride to pr o duce h y d r o ­
gen chloride, hydrocarbons

of the c o m p o s it io n CnH 2 n + o* an{3-

h i g h l y condensed hydrocarbons.

L a te r they found that t r e a t ­

ment of mixtures of organic chlorides and aromatic h y d r o c a r ­
bons w it h . a l u m i n u m chloride led to the format io n of such alk y l a t i o n products as toluene,

etliylbenzene, or amylbenzene,

and acylation products like benzophenone.

A possible m e c h ­

anism for the Fried sl -C r af ts rea ct io n would be the c o m b i n a ­
tion of the catalyst with the benzene derivative:
II

CgR^H t A I C I 3
this intermediate would then react with the halide:

- R ’ci --- *
■lerz and W e it h

a i c i 3 - R ' c 6r 5 .

Ill

(1 2 ) condensed two molecules of phenol

to produce diphenyl ether b y u s i n g a l u mi nu m chloride, while
\Jass

(1 3 ) used this catalyst in cond en si n g d i c hl or oe th yl en e

oxide with benzene to give triphenylethane.

These reactions

indicated that the a l u m i n u m chloride may 3 erve as a d e h y ­
d ra ting agent as v/ell as a catalyst.
shown when draebe (l4)

This was still further

succeeded in pr od u c i n g small amounts

of aniline b y treating benz e ne w i t h h yd ro xy l am in e in the
presence of aluminum chloride.
The con de ns at io n of chloral,

chloral hydrate, bromal,

and trioxymethylene w i t h various organic compounds

in which

an el imination of w at er occurred was reported b y Fr ankforter and co-workers

(15) who showed that,

did not b ring about the same reactions

since sulfuric acid
in some cases,

the

aluminum chloride was acting not only as a d e h y d ra ti ng
agent but also as a catalyst.
The first reported c o n d e n s a t i o n of alcohols wi th a r o ­
matic compounds was the work of A u e r

(16) w ho ,' in 1884,

condensed ethyl alcohol with phenol u sing zinc c hloride as
a catalyst.
resulted..

A mixture of ethylphenol and e thylphenetole
Anisole was obtained w h e n methyl alcohol was

substituted for ethyl alcohol.
In 1897 Nef (17)

obtained di ph en y l m e t h a n e by the r e ­

a ction b et w e e n benzene and benzyl alcohol in the presence of
aluminum chloride.
F r i e d e m a n n (18)
cent.

In r ep ea t i n g this work Hu s t o n and

found that this r e a c t i o n gave a thirty p e r ­

yield of d i p h en y lm et ha ne as well as smaller amounts of

o- and p-d.ibenzylbenzene, a h y d r o c a r b o n h av i n g the f or mula

C 2 7 H 2 4 ' an<3- anthracene.

The yields were found to be a

f unction of the temperature and the amounts of reagents
used.

In continuing this work H u s t o n and F r i e d e m a n n

condensed methyl phenyl carbinol,

(19)

ethyl phenyl ca,rbinol,

and diphenyl carbinol wi th b en zene to obtain the c o r r e s p o n d ­
ing substituted benzenes.

It was found that bot h methyl and

ethyl groups had a retard in g effect up on the c o n de ns at io n
while a second phenyl group did not.
In 1924 Hus to n (20) found that benzyl alcohol would
also condense with phenol,

anisole,

and phene to le In the

p resence of aluminum chloride to give yields of 45, 45, and
57 percent,

respectively.

alcohols with benzene,

Hus to n and Sa ger

tive results for methyl,
isobutyl,

In trying to condense primary

ethyl, propyl,

isoarnyl, phenylethyl,

(21) reported n e g a ­
isopropyl,

n-butyl,

and phenylpropyl alcohols.

Allyl alcohol, however,

condensed to'give a 16 percent,

yield of a l l y l b e n z e n e .

This,

tained by Huston auid Bartlet
carbinol with phenol,
alcohols

together with the results o b ­
(22)

in co ndensing phenyl butyl

led to the hypothesis that only those

in which the alpha carbon atom was a mem be r of a

benzene ri ng or held a double bond would condense u nder the
, action of aluminum chloride.
jthe work of Huston,

Lewis,

sation of methyl phenyl,

This conclusion was favored by

and G-rotemut (23) on the c o n d e n ­

ethyl phenyl,

and dip he n yl carbinols

with phenol since the latter gave the highest yield of c o n ­
densate.

It is Interesting to note that the attempt by

Hu st on and Davis

(24)

to condense triphenyl ca,rbinol with

benzene gave triphenylmethane rather than tetraphenylmethane
as the product.
Other papers followed in which Huston and co-workers
(2 5 ) reported the condensations of benzyl or halogenated
benzyl alcohols with phenol or halogenated phenols,

cresols,

or halogenated cresols.
A study of the condensation of cyclohexyl,

cyclopentyl,

and cyclobutyl carbinols with benzene by Huston and G-oodemoot
(25)

showed an increasing activity with smaller rings.
Although earlier attempts by Huston and co-workers

(27)

showed dehydration rather than condensation of various d i ­
aryl alkyl and dialkyl aryl carbinols,

several of these c o m ­

pounds have recently bee n condensed with phenol by W e l s h and
D rake

(28), Huston and Hughes

(30).

(29), and Hu s t o n and Jack so n

They modified the usual condensation procedure by a d ­

ding a solution of the carbinol and phenol in petroleum
ether to anhydrous aluminum chloride suspended in petroleum
ether.

Considerable amounts of p —benzylpuenol were obtained

as a by-product.
It was the work of Huston and Hsieh

(1) which opened up

a new field of investigation wh en they found that It was
possible to condense saturated aliphatic alcohols with b e n ­
zene and with phenol by u sing anhydrous aluminum chloride.
The temperature of the condensations was controlled by r e ­
gulating the rate of addition of the alcohols to a stirred
mixture of aluminum chloride and benzene.

Although they

were unable to bring about the condensation of aliohatic

primary alcohols with benzene or with phenol,
in condensing isopropyl alcohol,
propyl carbinol,

they succeeded

sec-butyl alcohol, methyl n-

and methyl isopropyl carbinol with benzene

to give the mono-substituted derivatives in yields of from
25 to 28 percent.

The tertiary butyl,

tertiary amyl,

and

tertiary hexyl alcohols condensed with both benzene and
phenol to give good yields of mono-alkyl derivatives.

The

yields of the p-t-alkyl phenols were from 40 to 55 percent,
of the theoretical.

M a n y other investigations

(3 1 ) in which

the alkylation of aromatic nuclei was the object followed.
The condensation of the tertiary heptyl alcohols with phenol
was accomplished by Huston and Hedrick

(1), while Hus to n and

G-uile (2 ) accounted for the condensation of eight of the
seventeen tertiary octyl alcohols with phenol.
raaining nine,

Of the re-

only the methyl dipropyl carbinols have not

b ee n condensed with phenol in this laboratory,
w r i t e r ’s knowledge,

and, to the

the condensations described h e r e i n have

not b e e n previously reported in the literature.

9
THEORETICAL
In the course of investigations on the condensation r e ­
actions "between various alcohols and aromatic hydrocarbons
In the presence of aluminum chloride it has b e e n observed by
Hus to n and his co-workers that the alpha carbon atom of the
alcohol must be under strain in order to create an active
hydroxyl group.

This activation is due primarily to the

fact that the electron pair which holds the hydroxyl oxygen
to the alpha carbon is dr awn closer to the hydroxyl group,
r esulting in a relatively unstable carbon-oxygen bond.

The

progressively greater reactivity of the alcohols In passing
from the primary to the tertiary is accounted for on this
basis and may be represented as follows:
H
,R:C: ,.0:H
H '

R’
R :G : 0:H
H

R*
R :C
R"

:0:H

The. distance of the electron pair from the carbon atom in­
creases as the reactivity of the alcoholic hvdroxyl grout)
increases.

This greater reactivity of the tertiary alcohols

Is reflected in their greater tendency to condense.

The

fact that the primary alcohols have not bee n condensed by
the methods employed in this laboratory further emphasizes
the low reactivity of this class.

Ease of condensation p a r­

allels the ease with which the hydroxyl group is replaced by
the ha logen of h yd ro-halogen acids as well as £he ease with
which dehydration occurs.
The mechanisms which have been advanced for the conden­
sation of tertiary aliphatic alcohols with aromatic hyd.ro-

10
carbons

in the presence of anhydrous aluminum chloride may

be divided into three types:
1.

The for.ma.tion of an alkyl-halide by the action of
aluminum chloride on the alcohol,

followed b y al-

k ylation through a F riedel-Crafts reaction;
2.

Dehydration of the alcohol to form an a.lkene which,
then condenses with the aromatic compound;

3.

A preliminary action of the aluminum chloride to
form an ether-like substance which then rearranges
to produce the alkyl substituted aromatic compound.

Regardless of the path the reaction may take,

an atom of

h ydrogen must be split off the ring to combine with the a l ­
coholic hydroxyl group as follows:.
Aid 3
R-jCOH + H C 5 H 4 O H ---------- R 3 C - C 5H 4 OH + H 20

IV

M u c h evidence has accumulated to show that the above simple
representation cannot fully explain the condensation.

A

brief discussion of each of the three mechanisms suggested
above will be given.
The Alkyl Halide Intermediate Me ch anism
Perrier and Pouget

(32) and Mpetse

(33)

showed that the

action of anhydrous aluminum chloride on a primary alcohol
proceeds in two directions:

with an excess of the alcohol,

in the cold, are formed compounds of the type Al 2 d g ( R 0 H ) n ,
v/hile with an excess of aluminum chloride,

on heating, hydro'

gen chloride is liberated and there are formed addition pro-

11
ducts such as A l g C l ^ O F O g
A 1 C 1 2 0R + RO H
Tzukervanic

----»

together with simple ethers:
A 1 C 1 2 0H + R O R

V

(34) found that in the b e g i n n i n g of the r e action

b et we en a tertiary aliphatic alcohol and sufficient a luminum
chloride there are formed the above a d dition products, but
with the ad di ti on of an excess of aluminum chloride and heat
the c o rresponding olefins and alkyl halides are formed.

In

his suggested scheme of reac t io n it will be observed that
all the required components for a F ri ed el - C r a f t s synthesis
are present:

G 5'H 110H

+ A I C I 3 ----* A 1 C 1 2 (0C 5H 1]L.) + HG1

.A 1 C 1 2 (0C5H1]l)
C 5 H 10

+ HC1

VI

» G 5H 10 + A1C-12 0H

VII

* G 5H 1 1 C 1

VIII

A later study by Tzukervanic and N a z a r o v a

(35)

showed that

secondary alcohols and phenol in the presence of aluminum,
chloride give only insignificant amounts of alkyl phenols.
This has since b e e n dispro ve d b y the work of H u s t o n and C u r ­
tis

(3 6 ) on the c on densation of the secondary hexyl alcohols

w i t h phenol to give secondary hexyl phenols in good yields.
Tzukervanic and Nazarova, stated that in general,

the m e c h a n ­

ism of c o n d en sa ti on of secondary and tertiary alcohols with
phenol is different.

They found the m a i n product to be a

phenolic ether of the type R C 5 H 4 OR.
cohols,

Since the secondary a l ­

in d i s t i n c t i o n from the tertiary,

do not give c o n ­

siderable amounts of olefins and alkyl halides,

they proposed

a scheme of reaction w hi ch did not involve the Friedel-Crafts
mechanism:

ROH + AlClj

IX

----- A1G120R + HG1

G 6H 5OH + 2 A1C120 R

* RG6H40R + 2 A1G120H

X

One objection to the mechan is m suggested in steps VI-VIII
is the difficulty always encountered in replacing the hydroxyl
hyd ro ge n atom of a tertiary alcohol even w h e n a metal as a c ­
tive as sodium is employed.

The evolution of h y d ro ge n c h l o r ­

ide and heat was observed by H u s t o n and Hedrick (37)

on a dd ­

ing a solution of n-butyl dimethyl carbinol in petroleum
ether to a suspension of aluminum chloride in the same so l ­
vent.

Although hyd ro ge n chloride is evolved in step VI,

it

must be again introduced in step VIII if the alkyl halide Is
-.

i•

■^

to be an intermediate'in the.'reaction.

Further, up on adding

phenoi to this m i x t u r e .of "carbinol and a luminum chloride in
petroleum ether, a much smaller yield of alkyl phenol was
obtained than had been produced by the usual procedure.

The Dehydration Mechanism
M cK e n n a and Sowa (38) proposed that the alkene formed
by dehydr at io n of the alcohol was the intermediate in the
c ondensation of alcohols wit h benzene-, using b o r o n t rifluor­
ide as the catalyst:
XI
XII
This reaction was found to apply to primary,

secondary,

and

tertiary alcohols.

A similar mechanism has b e e n proposed by

McG-real and Niederl

(39) using zinc chloride as catalyst,

and by Welsh and Drake (28) for the condensation of aryl carbinols with phenol in the presence of aluminum chloride.
Where the elimination of water from the carbinol is impossi­
ble, as in the cases of benzyl alcohol, benzhydrol,

and tri­

phenyl carbinol, Welsh and Drake assumed the elimination of
the hydroxyl group along with a nuclear hydrogen.

This ex ­

planation was advanced to account for the r eaction b et ween
trlphenyl carbinol and phenol at hig h temperatures in the
absence of a catalyst.
It_#cannot be denied that olefins will condense with
aromatic hydrocarbons in the presence of aluminum chloride
as this has been shown by several papers

(40).

Nevertheless,

the fact that primary alcohols will not condense with b e n ­
zene under ordinary conditions

(2 1 ) leads to the conclusion

that this mechanism does not fully explain all c o n d e n s a ­
tions ,b e tw ee n alcohols and aromatic compounds.
The E t he r Intermediate Mechanism
In 1892 Hartmann and G-attermann (41) reported that pbutylphenol could be produced by treating iso-butyl phenyl
ether with aluminum chloride.

Other similar rearrangements

of alkyl-aryl ethers were reported from time to time, and
in 1933 Smith (42) discovered that tert-alkyl phenyl ethers
can rearrange into the corresponding p-tert-alkyl phenols
upon the application of heat.

He also reported the r e a r ­

rangement of some alkyl .phenyl ethers by means of aluminum

14
chloride.
That such ethers may be intermediates in the c o n d e n s a ­
tion reaction is indicated in the work of Hu st on and Eld-,
ridge

(43) who found a benzyl phenyl ether among the p r o ­

ducts obtained in the be nz yl at io n of 2 ,6 -dichlorophenol with
benzyl alcohol in the presence of aluminum chloride.
However,

it must be remembered that Huston has reported

good yields of the al kylation product resulting from the c o n ­
densation of tertiary alcohols and benzene,

anisole,

and m-

cresylmethyl ether (1 ) as well as in the condensation of
benzyl alcohol with anisole and phenetole

(20).

In all

these reactions ether format io n is an impossibility.

No

ethers have be en isolated from reactions b e tw ee n tertiary
a l i p h a t i c .alcohols and phenol as carried out in this l a b o r ­
atory

(1 ).
A n attempt has b e e n made by Hus to n and Hedrick (37) to

explain the color changes that always accompany the c o n d e n ­
sation of phenol with tertiary aliphatic alcohols.

It is

well known that ferric chloride forms colored compounds with
phenols.

It is conceivable that similar compounds may be

formed b et ween phenol and aluminum chloride.

An h y d r o - a l u m ­

inum phenolic acid of the type H ^ ( A 1 ( 0 w a s
This,

suggested.

then, would react with the alcohol to form an inter­

mediate addition complex which would rearrange to give the
alkyl phenol and aluminum phenolate*v the latter undergoing
hydrolysis to phenol and aluminum chloride.
In reviewing studies on the mechanism of the Friedel-

15
Crafts type of reaction, Price

(44) points out that Werty-

p oroch and Firla (45) have clearly demonstrated hy conduc­
tance studies-the formation of an ionic complex b e tw ee n a l ­
uminum chloride and ail alkyl halide:
£1

+

R:X:
+ A1:C1
" C l
U llch and Heyne

»R

(46),

.. G 1

(:X:A1:C1)
‘ Cl

,

XIII

in studying the equilibrium for the

formation of some catalyst-alkyl halide c o m p l e x e s , found
that the rate of alkylation of benzene was directly p r o p o r ­
tional to the concentration of the complex.

Price assumes

that the electron-deficient carbonium ion, R^, reacts,
as does the bromine cation B r + during bromination,

just

to c o m ­

plete Its octet by a ssociation with a pair of electrons from
a double bond of the aromatic nucleus:

Lj

4.

*

4*

C.
H

^

This is supported by evidence of the reversibility of the alk y l at i on reaction uncovered by Ipatieff and Co rs on (47)

in a

study of the reaction of p-di-tert-butylbenzene with benzene
in the presence of ferric chloride,

sulfuric acid,

or p h o s ­

phoric acid to yield tert-butylbenzene:
FeCl-z
(CH 3 )3 C - C 6 H 4 - C(CH 3 )3 4 C 6 H 6 ---^

2 C 6 H 5 - C ( C H j )3

XV

Perhaps the mechanism showing the most promise at the
present time is based u p o n the formation of addition products
of alcohol and phenol with aluminum chloride.

Such a theory

16
has also-been proposed for the catalytic action of several
other catalysts.

In the case of aluminum chloride, the c o m ­

plex or "polymolecule"

Is linked together by the outer el ec ­

trons of the aluminum or chlorine atoms.
rangement of atoms and electrons

Since the new a r ­

is unstable under the c o n ­

ditions of the reaction, rearrangement occurs, resulting in
the formation of a more stable system:
H
:Q:C

^
.. Cl
C :H-~:C1:A1— :0:R

* H O C 5 H 4 R -t- A l C l 3 *H 20

XVI

Such a mechanism is further suggested by the fact that a l u m ­
inum chloride is such a powerful electrophilic reagent.

The

aluminum atom exhibits s. great tendency to make up an octet
of shared electrons.

Also,

the chlorine atom exerts a

stronger pull upon the nuclear h y d r og en than does the less
electronegative ring carbon atom.
Two experimental observations

lead to the conclusion

that a different mechanism exists for the condensation of
tertiary aliphatic alcohols with phenol as compared to their
condensation with benzene.

First,

lowering the temperature

decreases the yield of alkylphenol but increases the yield
of a l k y l b e n z e n e .

Second,

no fragmentaion of the alcohol a p ­

pears during the phenol condensation;

whereas the degree of

fragmentation Is found to be very hi gh when benzene is c o n ­
densed.

17
EXPERIMENTAL PROCEDURES
Materials Used
M a gn es iu n turnings especially prepared for Grig na rd r e ­
actions were used after d ry i n g in an oven at 45° C. for sev­
eral days.
Benzene was thiophene-free,

C. P. grade.

Petroleum ether, B. p. 30-65° C., was dried over f r e s h ­
ly cut sodium.
Phenol was Mallinckrodt ’s (crystals)

and was r e d i s t i l ­

led before use.
Aluminum chloride was B a k e r 1s Analyzed,

special for

condensations, C. P. anhydrous.
Diethyl ether was C. P. anhydrous,

and was dried over

freshly cut sodium before use.
Diisopropyl ketone was obtained from E a s t m a n ’s.
Methyl iso-propyl ketone was prepared by brominating
tertiary amyl alcohol and hydrolyzing (43).
Ethyl acetate was B a k e r ’s U. S. P., redistilled before
using.
n-Propyl bromide was prepared by adding 48/i hydrobromic s.cid to n-propyl alcohol in the presence of concen tr a­
ted sulfuric acid and refluxing for several hours

(4 9 ).

18
Preparation of the Tertiary Octyl Alcohols
4-Methylheptanol-4
B y adding methyl iodide to di-n-propyl ketone in the
presence of zinc, G-ortalow and Saytzeff (50) first prepared
methyl di-n-propyl carbinol in 1386.
of 30 percent.

Halse

(51),

They reported a yield

in 1914, prepared the same a l ­

cohol by the reaction b e t w e e n n-propyl magnesium bromide and
ethyl acetate.

Stadnikow

(5 2 ) modified the procedure of

Raise by substituting benzhydryl acetate for the ethyl ester
to obtain a yield of 40 percent.
Preparation of n-Propyl M ag ne si um Bromide.
To a mixture of 50 grams
turnings and 100 ml.

(2.06 moles)

of dry magne si um

of anhydrous ethyl ether contained in a

three-liter,

three-necked,

of 246 grams

(2 moles)

round-bottomed flask, a solution

of n-propyl bromide in 500 ml.

of a n ­

hydrous ethyl ether was added dropwise through a dropping
funnel.

The mixture v/as stirred continuously during the ad­

d it i o n of the halide by means of a glycerine-sealed stirrer.
A long reflux condenser having a calcium chloride d ry i n g
tube at its upper end served to condense the ether vapors.
P reparation of the Carbinol.
To the Grignard reagent thus prepared was added 88
granrs (1 mole)

of freshly distilled ethyl acetate.

The rate

of addition was so regulated that the ether refluxed gently.

A f t e r the ester had all b e e n added the stirring was c o n t i n ­
ued for a period of at least two hours.
Hydrolysis of the mixture, after it had been allowed
to stand overnight, was brought about by p ouring the c o n ­
tents of the flask onto ice in a three-liter beaker.

The

cold mass was then treated with 1: 1 hydrochloric acid while
I
i
the whole was Rigorously stirred until the magnesium h y d r o x ­
ide was completely dissolved as shown by the clearing of the
water layer.

1

The ether layer was separated from the water layer by
i
means of a large separatorv/ f u n n e l . The water laver was
.

77

next extracted three times/ with fresh portions of ether.

The ether extracts were combined and drieb overnight by
standing over anhydrous sodium sulfate.

/

The ether was distilled off by use of a water b a t h and
the residual liquid subjected to a distillation under r e ­
duced pressure.

The methyl di-n-propyl carbinol was col l e c ­

ted b e t w e e n 58° and 60° C. under a pressure of 7 ram. of
mercury.

20
2 ,3-Dimethylhexanol-3

By adding 2-methylbutanone-3 to n-propyl magnesium b r o ­
mide, Clarke

(53),

in 1911, obtained a 45 percent, yield of

methyl n-propyl iso-propyl carbinol.

He prepared the ketone

by converting ethyl acetoacetate to ethyl dimethylacetoacetate and h y drolyzing with aqueous potassium hydroxide.
The methyl iso-propyl ketone was prepared (48) by the
action of bromine Ion tertiary amyl alcohol at 50-60° C.
forming triraethylethylene dibromide which was then h y d r o ­
lyzed to the ketone.

A 70 percent,

yield of ketone b o i l ­

ing ad 93-96° C. ?at 750 mm. pressure was obtained.
To a 2 m o l e :theoretical of n-propjrl magnesium bromide,
prepared as described under 4 - m e t h y l h e p t a n o l - 4 , was added
172 grams

(2 moles)

of methyl iso-propyl ketone.

The rate

o-f addition was such that the ether refluxed gently.

The

stirring was continued for two hours after the last of the
ketone/had b e e n added.

The resultant product was’ hydro-

lyzed in the usual manner with ice .'and 1:1 hydrochloric acid.
/
Methyl n-propyl iso-propyl carbinol was collected between
46° and 47° C. at a pressure of 3 mm. of mercury.

21
2,3#4-Trlmethylpentanol-3
A 7 6 percent,

yield of methyl di-iso-propyl carbinol

was reported by khitmore and Laughlin (54)

in 1932 from the

a ction of di-iso-propyl ketone on methyl magnesium chloride.
.

•

.

Prepar a t i o n of Me t hyl Magnesium Bromide.
The methyl bromide generator, by a modification of the
procedure given for methyl chloride
three-liter,

(5 5 )# consists of a

round-bottomed flask resting on a sand bath.

The flask is fitted with a reflux condenser which has a d e ­
livery tube running from its upper end to a train of w a s h ’
bottles.

This train is made up of three bottles containing

saturated sodium hydroxide solution,
centrated sulfuric acid,

three containing c o n ­

and three safety bottles,

one at

each end of the train and one between the alkali and the
acid bottles.

4

In the flask was placed 53 grans of water and 586
grams

(320 ml.)

of concentrated sulfuric acid.

tion of 370 grams

(470 ml.)

out, with cooling,

The addi­

of methyl alcohol v/as~carried

at such a rate that the temper qjture did

not rise above 70° C.

After adding 1130 grams of sodium

bromide the apparatus was tightly connected and the flask
heated on the sand bath so that the gas was evolved at a
fairly rapid rate.

The washed methyl bromide was passed

into a three-liter,

three-necked, round-bottomed flask

which contained ,75 grams

(3.09 moles)

of magnesium,

a few

i.

Iodine crystals and some ethyl bromide to start the reaction,

and 600 ml. of anhydrous ethyl ether.

The reaction was

'carried out under the hood because of the poisonous nature
of the methyl bromide fumes.

About two hours were required

to use up all the magnesium.
P reparation of the Carbinol.
1

To the methyl magnesium bromide was added 296 grams
I
(370 ml.) of di-iso-propyl ketone in/400 ml. of anhydrous
ethyl ether.

It was added at such a, rate that the ether

refluxed gently.

The resulting product,

after standing

overnight, was hydrolysed in the same manner as the 4methylheptanol-4.

Methyl di-iso-propyl carbinol was dis-

:tilled under diminished pressure.

The fraction boiling

'
O
O
’
b e t w e e n 53
and 54 C . at 13 mm. pressure was collected.

23
CONDENSATIONS
Each of the tertiary octyl alcohols whose preparation
has been described was condensed with phenol.
procedure was the same in every case,

Since the

only a typical run

will be described.
A 500 ml.

three-necked,

round-bottomed flask was fitted

with a short reflux condenser,
ine-sealed mechanical stirrer.

a thermometer,

and a g l y c e r ­

In the fls.sk was placed 32.5

grains (one-fourth mole) .of the carbinol and 3 5 grams
eighths mole)

of freshly distilled phenol.

(three-

The stirring

motor was started and stirring continued until the phenol
was completely dissolved to form a colorless solution in the
alcohol.

The addition of 17 grams

(one-eighth mole)

of a l ­

u minum chloride was carried out by introducing small portions
at frequeiit intervals during a two hour period.

The stir-

#

ring was continued vigorously for another hour and the m i x ­
ture was then allowed to stand overnight before hydrolysis
was carried out.

The temperature was not at a.ny time a llow­

ed to rise above 30° C. It was always observed that the
first addition of the aluminum chloride caused the mixture
of, carbinol and phenol to undergo a series of color changes
beginning with a yellow,

going through a purple,

and ending

with a final condensation product which was uniformly a deep
ma r o o n color.
The condensate was hydrolysed by oouring the thick
*
mixture onto ice in a three liter beaker.
While stirring
constantly,

1:1 hydrochloric

acid was added until the p l a s ­

24
tic mass rose to the top.
three times ether.

The hydrolysate was then extracted

The ether extracts were combined and the

ether removed on a water bath.

The residue was then subject­

ed to a distillation under reduced pressure.

The fraction

obtained between 45° and 60° C., at a pressure of 6 mm.
mercury,

consisted of uncombined carbinol.

C. the uncombined phenol distillled over.

of

From 60° to 90°
The octyl phenol

itself was obtained in the range b etween 140° and 160° C. at
the low pressure.

The octyl phenol fraction was then r e d i s ­

tilled and collected over a two degree range of temperature.
The product usually crystallized in the receiving flask,
if not,

or,

crystallization was induced by cooling the d i s t i l ­

late in the icebox overnight.
Purification of the product presented some difficulty
because of the extremely high solubility of the alkylated
phenol in all of the common solvents.

The slight color of

the product was removed b y pressing the crystals on an u n ­
glazed porcelain plate.

Further purification was attained

by recrystallization from petroleum ether.

25
DERIVATIVES
The a-naphthyl urethanes and the 3 ,5-dinitrobenzoyl
esters were prepared as derivatives of the p-tert-octyl
phenols.
g-Haphthyl Urethanes
The method of French and Virtel
the prepar a t i o n of the urethanes.

(56) was employed in

One gram of the c rystal­

line phenol was placed in a test tube and 0 . 5 ml.
thyl Isocyanate added.

It has been found that,

of a-naph­

If the r e a c ­

tion is not spontaneous, addition of a few drops of.a solu­
tion of trimethylamine in absolute ether will readily catalyze it.

During the re a ction the contents of the tube must

be protected against moisture by means of a calcium chloride
dr y i n g tube.

The solution was warmed on a steam bath for

thirty minutes,

cooled In a beaker of ice, and the sides of

the tube scratched with a stirring rod in order to induce
crystallization.

The urethane was purified by repeated r e ­

crystallizations from petroleum ether until a constant m e l t ­
ing point was obtained.

HC 8 H 17 C 6 H 4 -O-CO-NH-C10Hy

H
XVII

26
3 » 5-Dinltrobenzoyl Eaters
A modification of the method described by Shriner and
Fu son (57) was used in the preparation of the 3,5-dinitrobenzoyi esters of the three p - t e r t - o c t y l p h e n o l s .

In a 50

ml. Erlenmeyer flask were placed three grams of the phenol
and an equal weight of 3 ,5 -<iinitrobenzoyl chloride dissolved
in four ml. of pyridine.

After the initial reaction ha d sub­

sided the mixture was refluxed over a small flame for one
hour,

cooled, poured on ice,

with ether.

and the oily layer extracted

The ether extract was washed 'with cold dilute

sulfuric acid to remove the pyridine and then with cold
dilute sodium carbonate solution to remove excess acid.

The

ether was removed on a water bath and the ester then r e - ‘
crystallized from a water-alcohol mixture until a constant
m elting point was obtained.
C^H7

H

H

G-^Hy

H

H

H

NO g

G 8H 17"G 6H 4 " 0 -G°-G 6H 3^N 0 2)2 + ■HC1

XVIII

27
PROOF OF STRUCTURE
To prove the structure of the octyl phenols the co r ­
responding octyl benzenes were prepared,
nitro derivative,
tized,

nitrated to the p-

reduced to the p-amino compound,

diazo-

and the diazonium salt finally hydrolyzed to form

the octyl phenol.
The three methyl di-propyl phenyl methanes had b e e n
previously prepared in this laboratory (5 8 ) and their p h y ­
sical constants determined.

The method employed in the p r e ­

p a ration of these octyl benzenes was to condense the three
methyl di-propyl carbinols with benzene in the presence of
aluminum chloride.
The methyl di-n-propyl carbinol and the methyl n-propyl
iso-propyl carbinol were condensed with benzene in the same
manner so that a general d e s c r iption of the procedure will
suffice.

The condensation of the methyl di-iso-propyl car­

binol, however,

required special treatment because of its

great tendency to undergo fragmentation during the reaction.
Pr eparation of the Oc tylbenzenes
A.one-liter,

three-necked,

round-bottomed flask was pr o ­

vided with a glycerine-sealed mechanical stirrer,
condenser,

and a separatory funnel.

a reflux

A calcium chloride d r y ­

ing tube was inserted in the upper end of the reflux con d e n ­
ser to exclude moisture.
(two and one-half moles)
mole)

In the flask was placed 195 grams
of benzene and 33 grams

of anhydrous aluminum chloride.

(one-fourth

The mixture was then

stirred until the aluminum chloride was uniformly suspended
in the benzene.

Next,

65 grams

(one-half mole)

of carbinol

was added through the dropping funnel at the rate of one
drop per second.

The stirring was continued for four or

five hours after the last of the carbinol had b e e n added.
At no time during the a ddition of the carbinol was the te m ­
perature allowed to rise above 30° C., external cooling b e ­
ing applied if needed.

The evolution of considerable amounts

of h ydrogen chloride gas was noted as the reaction proceeded.
After standing overnight the mixture was hydrolyzed by p o u r ­
ing into ice and 1:1 hydrochloric acid.

The benzene layer

was separated and the water layer extracted three times with
ether.

The benzene-ether solution X'ras xvashed with sodium

carbonate solution in order to remove any excess acid and
then dried overnight over anhydrous sodium sulfate.

After

removing the ether and benzene on a water bath the residue
was distilled under reduced pressure.
All attempts which have b e e n made to condense methyl
di-iso-propyl carbinol with benzene at room temperature have
led to fragmentation of the carbinol resulting in the f o r m a ­
tion of alkyl benzenes of lower molecular weight.

This is

the subject of an investigation now under way in this l a b o r ­
atory b y Huston and Avmapara.
ting as much as possible,
erature of minus 30° C.

In order to avoid this split­

the condensation xvas run at a temp­
This temperature was maintained by

mixing ether and solid carbon dioxide
vent the freezing of the benzene,

("dry ice").

To p r e ­

an equal weight, of petro-

29
leum ether was added.
petroleum ether,
night,

The suspension of aluminum chloride,

and benzene was cooled in the icebox over­

then cooled d o w n to -30° C. and the carbinol added

over a period of five h o u r s .

The low temperature was m a i n ­

tained while stirring was continued for another five hours
after which the mixture was placed in the icebox overnight.
The material was allowed to come slowly to room temperature
and then treated in the usual manner.

E v e n with all these

precautions the yield of the desired product was low as
indicated in the table.
Nitration of the Qctylbenzenes
The nitration of the alkyl benzenes followed M a l h e r b e ’s
procedure (59).

The h y drocarbon was treated with an equal

weight of fuming nitric acid
the addition.

(sp. gr. 1 .5 2 ), cooling during

After the first violent reaction had subsided

the mixture was warmed to 90° C. in a water bath for one hour.
It was then poured on ice and the resulting solution extract­
ed three times with ether.
over calcium chloride,

The ether extracts were dried

the ether removed,

and the liquid

nitro compounds subjected to a distillation under reduced
pressure.
O xidation of the Nitrated Qctylbenzenes

In order to determine the position taken by the nitro
group, the octyl side chain was converted into a carboxyl
group and the nitrobenzoic acid identified by melting point.

30
The oxidation was adapted from a method proposed b y Anshiitz
and Beckerhoff

(60).

One gram of the nitro compound and 20

ml. of 6 N nitric acid were sealed up in a Carius tube 'and
he a t e d in a Carius furnace at 130° C. until crystals appe a r ­
ed on cooling.

The time required was from 10 to 20 hours.

The crystals were removed,
p etroleum ether, dried,

filtered by suction, washed with

and recrystallized from alcohol u n ­

til they melted at 238-240° C. and caused no d e p r e s s i o n of
the melting point of a k n own sample of p-nitrobenzoic acid.
R e d u c t i o n of the Nitrated Qctylbenzenes
C onversion of the nitro derivatives into the c o r respond­
ing amino compounds was accomplished by the method of Ipatieff
and Schmerling (61).

For each gram of the nitro compound,

conta.ined in a 500 ml. round-bottomed flask equipped with an
air condenser,

5 grams of granulated tin and 5 nil. of concen­

trated hydrochloric acid were added.

To this mixture was a d ­

ded sufficient ethyl alcohol to bring nearly all of the m a ­
terial into solution.

The f'lask was shaken until reduction

was complete as was shown by the absence of a marked turbid­
ity on pouring a test portion into water.

The flask was h e a t ­

ed on a steam bath if the reduction was slow.

Ten minutes was

all that was usually required- to complete the process.

The

aqueous-alcoholic s o lution was then decanted into about twice
Its volume of water and the amine extracted with ether after
the solution had be e n made alkaline with 40 percent,
hydro x i d e solution.

sodium

A purer product was obtained if the amine

31
was steam distilled before the ether extraction.

The ether

solution was washed with potassium carbonate solution,

the

ether evaporated, and the amine dried with solid potassium
hydroxide. ■

Replacement of the Amino G-roup by Hydroxyl
For each two grams of the amine,

a solution of 1.5 ml,

of concentrated sulfuric acid in 10 ml. of water was added.
The insoluble sulfate thus formed was suspended by vigorous
stirring in 10 volumes of water.
25 percent,

A fter cooling to 5° C. a

solution of sodium nitrite was added dropwise

until an excess was shown by a positive starch-potassium
iodide test.

The solution was tested from time to time with

Congo red paper to make sure that the acid concentration
did not drop too low.

W h e n the diazotizaticn was complete

the solution was brought to room temperature with continued
stirring and finally heated on the steam bath for an hour
to b ring about hydrolysis of the diazonium salt.

The phenol

was extracted with ether, dried with anhydrous sodium sulfate
and distilled in vacuo.

After isolation of the pure phenol

the cx-naphthyl urethane was prepared.

M elting point and m i x ­

ed melting point determinations indicated that the phenols
obtained by this method were identical with the others. „

32
TABLES
Table _I
Condensation of tert-Octyl Alcohols with Phenol
Product:

Yield:

4-Methyl-4-p2,3-Dimethyl-32,3;4-Trimethylhydroxyphenyl- p-hydroxyphenyl- 3 -p-hydroxyphenylheptane
hexane
pentane
65.0%

47.0%
72-73° C.

59.6%
57-58.5° C.

M. p.

63-63.5° C .

B. p.

151-152°/6 mm.

122-124°/2 mm.

1 1 6 - 1 1 7 ° / 2 mm.

282-284°/738

279-28l°/738

285-287°/738

Analyses:
%C *

81.17%

80.91%

80.96%

fall *

1 0 .68 %

1 0 .77 %

10.81%

* Calculated for

C = 81.50%, H= 10.75%
Table II

3 , 5-Dinitrobenzoyl Esters
Phenol Esterified

M. p.

4-Methyl~4-p-hydroxyphenylheptane

(°C.)

% N *

124.5-126.0 6.97%

2 ,3-Dimethyl-3-p-hydroxyphenylhexane

2.3.4-Tr im e thy 1 -3-p -hydrc xypho nyIp e ntane
** Calculated for C gpH2A-^6^2:

97.0-93.0

7 .01 %

103.0-103.5 6.98%.

N - 7.00% ,

Table III
oL-Naphthy lure thanes
ct-Naphthylurethane of:

M. p.

(°C.)

% N *

4 -Me thy1-4-p -hy dr oxyph eny lhep-t ane

1 0 5 .0 - 106.0 3.72%

2 ,3-Dimethyl-3-p-hydroxyphenylhexane

127.5-128.5 3.69%

2,3;4-Trimethy1-3-p-hydroxyphenyIpentane

1 0 6 .0 - 107.0 3.70%

* Calculated for C 25 H 2 9 O 2 B:

N= 3.73%

33
Table IV
Mlethyl Di-Propyl Carbinols
Compound:

b. p.
found:

4 -Methylh eptanol-4

2 ,3-Dimethylhexanol-3

54 56°/13 mm.

6 2 - 6 3 °/l 2 mm

155-5-7.5 ° / 7 4 8 .5

6 l- 6 3 °/l 2 mm

146-7°/740.5 mm
75-77°A O

36 %

54.5 %

80 %

Index of
refraction
(2 0 ° C . ):

1.4258

1.4517

1.4342

Surface
tension
(20° C.) :

26.675

27.500

28.325

0.8208

0.8344

0.8457

20

d:

Physical constants taken from the M
Kenneth D. Oline

mm.

158-58.2°/75S mm

159-6l°/755
% Yield:

53-54°/l3 rnm.

-

157-9°/748.5
reported:

2,3,4-Trimethylpentanol-3

S. thesis

of

(58)
Table IV-A

p-Nitro-tert-octylbenzen.es
Nitro Derivative of:

Boiling point:

4-Methyl-4-phenylheptane

137-139°/ 6 mm.

2 , 3-Dimethyl-3“Phenylhexane

140-141°/ 7 m m .

2,3# 4-Trlmethy1-3-phenylpentane

133-135 / 6 mm.

34
Table V
tert- Octylbenzenes *
Compound:
B. p.
found:

reported:
Yield:

4-Methyl-4phenylheptane

2,3-Dimethyl-3phenylhexane

2,3,4-Trlmethyl3-phenylpentane

109-111°/10 mm.

104.5-6.5/11 mm

104-106°/13 mm.

242-3°/T49 mm.

237-8°/748 mm.

234-6°/743 mm.

1 2 0 - 1°/ 1 2 mm.

31.8 %

18.4 %

6.0 %

Refractive
Index 20°

1.4930

1.4900

1.4968

Surface
tension

31.488

30.80

31.763

0.8700

0.8663

0.8808

Analyses
% c

88.34 %

88.43 fo

88.55 %

% H. **

11.64 %

11.68 %

11.51 %

Mol. Wt.
found:

190.88

189 . 9 2

189.72

Mol. Refr.
c a l c .:

63.25

63.25

63.25

found:

63.57

63.51

63.18

Paraciior
c a l c .:

522.4

519.4

516.4

found:

518.25

517'. 52

513.0

Physical constants determined by Cline
•k* Calculated for C ^ H ^ :

(5 8 )

^ ” 88.33 %, H = 11.67 %

35
DISCUSSION
The general procedure used to prepare the p-tert-octyl
phenols described consisted in the preparation of the three
isomeric methyl dipropyl carbinols, followed by their con­
densation with phenol using anhydrous aluminum chloride as
the catalyst:
C-%Hy
H H
I
AICI3
CH3-C-OH 4- HtV
^.COH
.— *
5 1
Nc = c x
C 3Hy
H H

C^Hv H
\
^.c—
CH-,-0-0:
3/
C3H7 H

The three carbinols, 4-methylheptanol-4,
hexanol-3i

H
c
■ >OOH

XIX

H
2,3-dimethyl-

and 2,3»4-trimethylpentanol-3^ have all b e e n p r e ­

viously prepared.

The methods involved in their preparation

are described in the experimental portion of this thesis,
while their physical constants,
tory by Kenneth D. Cline

as determined in this labora­

(5°), are listed in table IV.

At­

tempts by the writer to prepare 2 ,3 ,4-trimethylpentanol-3 by
using Iso-propyl magnesium bromide and methyl iso-propyl
ketone led only to failure.

It has been found that such

branched G-rignard reagents have a tendency to cause enolization and polymerization of the ketone.
In preparing the octylphenols„,

the phenol was dissolved

in the carbinol by rapid stirring and the aluminum chloride
added in small portions.

This "shaker method" was decided

u p o n following the observation of Curtis

(36) that higher

yields resulted from this method than when the alcohol was
added to phenol and catalyst in petroleum ether.

No Increase

36
in yield was observed when a temperature of 45 to 50° C.
was tried, whereas a temperature of 10° C. was found by
Huston and Guile (62) to cause a decrease in yield.

For

these reasons the temperature was held between 25 and 3 0 °
C.

After completion of the reaction the condensate appear­

ed as a gummy mass which stuck to the sides of the beaker
when water was added.

The addition of hydrochloric acid

thinned the mass and permitted it to rise to the surface.
A deep maroon color was always observed at the final stage
in the condensation.
The presence of unchanged phenol in the condensate was
shown by its crystallization as long white needles in the
receiving flask during the distillation of the products.
These needles slowly changed to a purple and finally to a
deep blue color,

suggesting the color reactions between

phenol and ferric chloride.
Separation of the octyl phenols from colored impurities
was difficult due to their great solubility in all common
organic solvents.

'The problem was solved by pressing them

out on porous porcelain plates which were kept for several
days in the icebox.

This method was necessary in the case

of 2,3“dimethyl-3-p-hydroxyphenylhexane because the impure
compound would not crystallize at room temperature.
After purification of the oetylphenols, their physical
constants were determined,
hydrogen,

they were analyzed for carbon and

and two solid d e r i v a t i v e s , the ct-naphthyl urethanes

and 3 ,S-dinitrobenzojrl esters, were prepared for identifica­
tion.

The latter were chosen in preference to benzoyl esters

37
because the melting points of the benzoyl esters were not
high enough to make them satisfactory derivatives.

The p e r ­

centages of nitrogen and the melting points of these d e r i ­
vatives are shown in tables II and III.
The proof of structure was the same as was used by
Huston and Hsieh (1) and by several subsequent investigators
in this laboratory.

The octyl benzenes were prepared by

condensing the same three carbinols with benzene in which
the catalyst,

aluminum chloride, was suspended.

The yields

(table V) were found to decrease as the branching of the al­
cohol increased.

Not only alkyl benzenes of lower molecular

weight, but also alkyl chlorides appeared In the lower f r a c ­
tions wh e n these condensates were distilled.

Although very

low temperatures increased the yield of oct.ylbenzene and d e ­
creased the yield of the lower alkyl benzenes,

it s imulta­

neously increased the amount of alkyl halide.
These t e r t - o c t y l b e nzenes, whose physical constants had
be e n previously determined in this laboratory
nitrated,

reduced, diazotized,

lyzed to the oetvlphenol.

(5 8 ), were

and the diazonium salt h y d r o ­

Oxidation of the side chain of the

nitrated octylbenzenes showed that the substitution of alkyl
group for hyd r o g e n in the phenol occurs in the para position
rather than in the ortho or rneta positions.

33
SUMMARY
1. The methyl di-propyl carbinols have b e e n condensed
with phenol in the presence of aluminum chloride to give
good yields of the corresponding p - t e r t - o c tylphenols.
2. The 3 , 5-dinitrobenzoyl esters and the a-naphthyl
urethanes of these p-tert-octylphenols have b e e n prepared.
3. The structures have been established by synthesis.

39
BIBLIOGRAPHY
1 Huston and Hsleh

Huston and Hedrick
2 Huston and Guile

Huston and Snyder

J. Am. Chem. S o c .

J58,

J . Am. Chem. Soc.

52

J. Ain. Chem. Soc.

61,

>

439

1936)

2001

1937)

69 • 1939)

Master's Thesis
Michigan State College
M a s t e r ’s Thesis
Michigan State College
Ber.
JL5,
674

1933)

3er.

2090

1882)

954

1873)

6 Michael and Jeanpretre Ber.

1 2 , 1615

1392)

Ber.

1 6 , 2360

1883)

505

1882)

553

1891)

*

137

1373)

2 -27,

530

1377)

Comp. Rend.

04,

1392

1-377)

12 Ilerz and Weith

Ber.

14,

189

1881)

13 Bass

Ber.

15,

1128

1382)

14 Graebe

Ber.

34, 1778

1901)

36, 1911

1914)

i'bi d .

37,

335

1915)

15 Auer

Ber.

17,

569

1884)

17 Kef

Ann.

293,

255

1897)

13 Huston and Friedeinann

J. Am. Chem. Soc.

38,

2527

19 Huston and Friedernann

J. Am. Chem.

40,

785

1918)

20 Huston

J. Am. Chem. Soc.

46

2775

1924)

21 Huston and Sager

J. Am. Chem.

48, 1955

Huston and Langdon
3 Fischer and Roser
Becker
5 ,Meyer and Burster

7 Hemilian
Q

±-i c x

Zi5 L c l jf*<3,

o H o e 1 ting

15,

Ber.

Gazz. Chim.

Ital.

Ber.
s-

10 Zincke

Ber.

n

Bull. Soc. Chim.

Friedel and Grafts

12,

15 Frankforter and others J. Am. Chem. Soc,

Soc.

Soc.

1938)

1880)

1916)

1926)

40
22 Huston and Bartlet

1926 )

23 Huston,

1927)

M a s t e r 1s Thesis
Michigan State College
Lev/is, G-rotemut J. Am. Chem. Soc.
49, 136 5
M a s t e r ’s Thesis
Michigan State College
J. Am. Chem. Soc.
33, 2379

1931)

ibid.

52, 4484

1930)

ibid.

j54, 1506

1932)

26 Huston and G-oodemoot

J. Am. Chem. Soc

5 6 , 2432

1934)

27 Huston and Wilsey

M a s t e r 's Thesis
Michigan State College
Master's Thesis
Michigan State College
M a s t e r ’s The s i s
Mi c higan State College
J. Am. Chem. Soc.
60,
58

1933)

24 Huston and Davis
25 Huston and others

H uston and Hradel
Huston and McComber
28 W e lsh and Drake
29 Huston and Hughes
30 Huston and Jackson
31 Huston and Fox

Doctor's Thesis-,
Michigan State College
J. Am. Chem. Soc.
6 3 , 541

1933)

1934)
1935)
1933)
1941)
1941)

32 Perrier and Pouget

M a s t e r ’s Thesis
Michigan State College
Master's Thesis
Michigan State College
M a s t e r ’s Thesis
Michigan State College
M a s t e r ’s Thesis
Michigan State College
Bull. Soc. Chim. 3-2B,
551

1901)

33 Mpetse

Praktika (Akad.Ath)

148

1931)

J.Gen.Chem. U.S.3.R
117
C. A.
29, 4746
Tzukervanic and Nazarova J.G-en.Chem.USSR
767
C. A.
.
30,
443
Huston and Curtis
Master* s Thesis
M i c higan State College
Huston and Hedrick
D o c t o r ’s Thesis
Michigan State College
McKenna and Sowa
J. Am. Chem. Soc.
59,
470

1935)
1935)
1935)
1936)
1941)

Huston and Binder
H uston and Sculatl
H uston and Breining

6

34 Tzukervanlc
35
36
37
38

1934)
1935)
1936)
1938)

1937)
1937)

39 McGreal and Nlederl

J. Am.

Chem. Soc.

5j7, 2625

1935)

40 Berry and Reid

J. Am.

Chem. Soc.

49, 3142

1927)

Compt.

rend.

164, 1375

1886)

Varet and Vienne

41
Cline and Reid

Bodroux

J. Am. Chem. Soc.

4§, 3150 (1927)

ibid

49, 3157 (1927)

Compt.

rend.

1 8 6 . 1 005

(1928)

41 Har t m a n n and G-attermann

Ber.

25, 3531 (1892)

42 Smith

J. Am. Chem. Soc

55,

ibid.

43 H u s t o n and Eldridge

849

(1933)

25,

3718

(1933)

ibid.

56,

1419

(1934)

ibid.

56,

1583

(1934)

Master* s Thesis
Michigan State College
J. Am. Chem. S oc.
2 26 0

(1930)

44 Price

Chem. Rev.

45 Wertyporoch and F i rla

Ann.

46 U l i c h and Heyne

Z. Electrochem.

47 Ipatieff and Corson

J. Am.

29,

Chem. Soc

.

48 Organic Syntheses

37 (1941)

500,

287

(1933)

41,

509

(1935)

52,

141? (1937)

XIII,

68

I,

5

49 Organic Syntheses

(1931)

50 G ortalow and Saytzeff

J. prakt. Chem.

31,

203

(1886)

51 Halse

J. prakt. Chem.

89,

453

(1914)

52 Stadnikow

Ber.

41, 2137

(1914)

53 Clarke

J. Am. Chem. Soc

31,

528

(1911)

54 Whitmore and La.ughlin

J. Am. Chem. Soc

54,

4392

(1932)

55 Organic Syntheses
56 French and Wirtel

35
J. Am. Chem. Soc.

48,

1736

(1926)

Shriner and Fuson

Ident.Org.

Compds.

173 (1940)

57 Shriner and Fuson

Ident.Org.

Comods.

138

(1940)

58 Huston and Cline

Master* s Thesis
M i c h i g a n State College
Ber.
52,
319

(1939)
(1919)

Ann.

(1903)

59 Malherbe
60 Anschutz and Beckerhoff

327,

219

42
61 Ipatieff and S c h m e r ling J. Am. Chem. Soc.
62 H u s t o n and G-uile

59,

1056

(1937)

D o c t o r ’s Thesis
(1938)
M i c h i g a n State College