THE FRAGMENTATION OF 2,3, 4-TRIMETHYL- 2-PEN TAN OL WHEN
CONDENSED WITH BENZENE AND ALSO WITH PHENOL
IN THE PRESENCE OF ALUMINUM GHLORILE

by
REINHOLD JOHN HRANTZ

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

Department of Chemistry
1947

ProQuest Number: 10008357

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ACKNOWLEDGMENT
To Dean Ralph. C. Huston the author extends his appre­
ciation for the suggestions and inspiration which helped
bring about this work.

331648

INTRODUCTION
1h the study of the condensation, in the presence of
aluminum chloride# of each of the saturated aliphatic ter­
tiary alcohols through the eight-carbon earbiaols with
aromatic nuclei• chiefly benaene and phenol# it was ob­
served by Huston and coworker® (1) that smaller than ex­
pected yields were obtained in certain highly branched
alcohols*

This was attributed to the marked depressing

influence on the condensing capability of those carbinols
in which there was an accumulation of alkyl groups on the
carbon a t m adjacent to the hydroxyl carbon*
JPagmentatlon studies by Huston and Awuapara (2)#
Huston and Barrett (3)» and Huston and Van Vpkm (4) and
resulting isolation of tertiary butylbenssne have led to
the belief that low yields of expected condensates are
due to fragmentation rather than depressive influence on
the condensing capability of the alcohol*
In 1938 Guile (23) condensed 2 f3#4-trim©thyl-2pentanol with benaene in order to prove the structure of
his octylphenol obtained from condensing the same car bi­
n d with phenol*

He obtained none of the ootylbensene

since he used only 0*125 moles of earbinel*
The purpose of this investigation is to continue
the study of the fragmentation of 2#3#4-trimethyl-2pentamol when condensed with benssne and also with phenol
la the presence of aluminum chloride*

HISTORY
Because of the extensive work which has been done In
thie laboratory on alkylation of aromatic nuclei in the
presence of aluminum chloride or other catalysts many
excellent reviews (5,6) of the work have been given in
theses here*

In addition, more comprehensive reviews

such as those by Kranzlein (7) and Thomas

(8) or the re­

cent one by Price (9) are available on the subject of
aluminum chloride#s role in organic chemistry and the
theory of the Friedel-Craft reaction in general*
The purpose of this summary is to give a background
for the discussion of fragmentation and group migration
by especially calling attention to reactions in which
the alpha carbon to the hydroxyl carbon of a tertiary
alcohol contains an alkyl group (methyl)*
The preparation of alkyl benzenes and phenols has
been under investigation in this laboratory since Huston
and iViedeman (10) repeated the work of Nef (11) to obtaih a thirty per cent yield of diphenylmethane from the
condensation of benzyl alcohol with benzene in the pre­
sence of aluminum chloride*
That primary alcohols condensed with benzene gave no
yields was shown by Huston and Sager (12), or poor yields
with large amounts of aluminum chloride at elevated temper­
atures was portrayed by Norris and Sturgis (13),

The

latter showed that the reaction of alcohols and aromatic

nuclei wee & function of the quantity of aluminum chloride
and temperature ae Tzukervaaic and Nazarova (14) had
previously determined# especially in regard to condensa­
tion of secondary alcohols*

They (15) also obtained 60-

70# yields in the condensation of tertiary butyl and
tertiary amyl alcohols with phenol*
Secondary alcohols (5) give better yields of alkyl
benzene than the primary# and tertiary alcohols than the
secondary (I)*
primary

The tendency for rearrangements is
secondary — *

tertiary*

This was first ob­

served by Oustavson (16) only a year after the announcement
of the Vriedel-Crafts reaction*

He found that normal propyl

and Isopropyl bromides react with benzene in the presence
of aluminum chloride to form the same substance isopropylbensene (cumene)*
This was later corroborated by ether workers (17# 18#
19)*

Condensing normal butyl chloride with benzene gives

only the secondary product (20)*

it is of peculiar inter­

est that in 1899 Konovalov and Je&orov (21) Isolated
tertiary assy1 benzene in addition to the secondary product
when condensing 2-®ethy 1-3-chlorobutane with benzene in
the presence of aluminum chloride*
But mere significant than mere isomerization and rearrange­
ment to the more stable secondary and tertiary alkyl groups is
the degradation or fragmentation of various higher tertiary
alcohols when condensed with benzene under mild conditions*

This was observed in a paper by Huston, Guile, Sculati and
Cbsson (22) in 1941.

law yields were obtained when 2,4,4-

trimethyl-2-pentanol and 2,3,3-trimethyl-2-penta»ol were
condensed with benzene.

It was observed in the same paper

that the condensation of 2, 3,4-trimethyl~2-pentanol with
benzene gave no octylbenzene, but only lower molecular
weight products*

A condensation of the same carbinol with

phenol (23) gave a very low yield*

Since condensations

with phenol usually give larger yields than with benzene
under similar conditions this observation was of peculiar
interest*
At reduced temperatures (22) degradation was diminish­
ed and Increased yields of the expected alkylbenzenes were
obtained*

The yield of alkylbenzene and degradation is a

function of the amount of aluminum chloride used (24).
Ihen the alcohols subject to fragmentation are con­
densed with phenol there is less tendency to isomerise or
degrade (23) than when condensed with benzene*

However,

t-butylphenol was obtained by Breiter when he eondensed
2,3,3-trimethyl-2-pentanol and 2,2,3-trlmethyl-3-pentanol
with phenol*

Although it is not ‘reported, it is probable

that some t-butylphenol is formed when 2,4,4-trimethyl-2pentanol is eondensed with phenol,

smith and Hodden (26)

have shown that 2,4,4-trimethyl-2-p-hydroxyphenylpentane
rearranges in the presence of aluminum chloride to tbutylphenol under special conditions*

In the table below are listed some of the aleohols
ehieh have the greatest tendency to undergo fragmentation,
tertiary butylbenzene was reported as a product in each
ease when the alcohol was condensed with benzene in the
presence of aluminum chloride.
also reported in 1,2, and 3.

Tertiary amylbenzene was
Also there were various

other fragmentation produets such as methyl chloride in
4 and 6 and isopropyl chloride in 4.
In the fragmentations in each case some fractions
were almost infinitesimal so that perhaps some frag­
ments could have been overlooked in the final analysis.
c o h x m iS A iio ^ s

w ith

alcohol

mnzm^
fragments - reference

1. 2 f3*dimethy1-2-butanol

t-butyl & t-aaylbenaene

(4)

2. 2,3-dimethyl-2~pentanol

t-butyl & t-amylbensene

(4)

3. 2,3,3-trimethyl-S-butanol

t-butyl & t-amylbensene

$i)

4. 2 f3,3-trimetbyI-2~p©ntanol

t-butylbensene* isopropyl
chloride & methyl
chloride
(4)

5. 2,4,4*trimethyl-2~pentanol

t-butylbenzene

(1)

t-butylbenzene &
methyl chloride

(4)

t-butyl benzene

(2)

6. 2,2,3-trimethyl-3*pentanol
*
7. 2t3,4-trlmethyl*3-pentanol

To avoid this in working with alcohol number 3, Barrett
made his final fractionation In a 100-plate column.

In

the organic layer analysis he identified eleven fractions
including the two mentioned above plus a hexyl- and a

heptylbenzene.

Two styrene derivatives were also found

in small amounts*
Awuapara shewed that whereas he obtained nearly
fifty per cent yield of t~butlybenzene from alcohol
number 7 in which a methyl radical must migrate# with
2#4~di®ethyl-3-etbyX-3-pentanol# a very small yield of
t-butyl- and t-amylbenzene was obtained since their
formation necessitates the migration of an ethyl group*

The most successful alkylating agents are the alkyl
halides* olefins and alcohols*

She first two mentioned

need only catalytic amounts of aluminum chloride* while
a greater amount (13) is required with alcohols because

%
Htgs

+

£L
§t*C1

of the reaction between aluminum and the alcohol*

Smith

(24) has shown that larger amounts of aluminum chloride
increase the yield of al^latioa*
Using halides* alcohols* ethers and esters alkyla*
:tion procee&smo&t readily for- tertiary or bortryl types*
less readily for secondary types* still lees readily for
primary types* and least readily for methyl*

Thus*

reactive halides such as benny! chloride (9) will react
with benzene in the presence of traces of such a weak
catalyst as zinc chloride* whereas ass inert halide*
lilce methyl chloride requires a considerable quantify
of a powerful catalyst such as aluminum chloride*
In general there are three possible mechanisms for
explaining the reaction* although according to a review
(35) of the yriedel*Craft& synthesis by Calloway there
is no completely satisfactory explanation of the

alkylation of benzene by various alkylating agents*

The

three possible mechanisms are as follows?
1*

Alkyl halide formation plus Friedel-Crafts
reaction*

3*

Alkene formation plus condensation*

3*

Cationoid theory*

Tsukervanik (34) championed the first mechanism for
the alkylation of benzene with aliphatic alcohols in the
presence of aluminum chloride.

These are the steps h#

proposed?
1

*

ch3
HgC-OH

♦

A1C1 3

«*■»-»

ch*
EgO-DAlClg

CHj*

3*

HgC^CHg

*

HC1

*f

R^G^GHg

♦

HgGOHg
Cl

4

A1 (OH) Gig

Morris and Sturgis (13) have proposed a similar
mechanism with essentially the same steps showing
alkyl chloride formation as an intermediary step in
the alkylation of benzene with alcohols.
McKenna and Sows, (56t3¥) have suggested olefins as
Intermediates to help explain rearrangements during
alkylation.

CHgOHgCHgBr

A1CX»»

(C3H6 )

C!HjOHCHjj

(03H6 )

*

c6h6

>

ch3chch3
°6%

Whitmore’s (6it) theory of molecular rearrangements could
account for the came isomerization during alkylation by
the following steps

CHgCHgCB^Cl

*

3

AIC13

—

»

0HgCAgCH^ AlCl"

To exclude the theory of an olefin as an intermediate
is the fact that both benzyl alcohol (10) and benzhydrol
(38) are effective alkylating agents and Intermediate
olefin formation is impossible*
The most modern and generally accepted theory is the
one outlined by price (27)#

According to Price the substi­

tution in benzeneid compounds Involves the replacement of
a hydrogen atom by an electron deficient cationoid reagent*
B

That the above equation is reversible has been
shown by Ipatieff and Corson (28) by readily converting
p-di-'t*butylbenzene In benzene solution to t-butylbenzene
in the presence of a catalyst*

However the catalysts

will remove only tertiary alkyl groups unless vigorous
catalysis with aluminum chloride is effected (29,30*31).

The relative ease of the lees of the proton to form
the intermediate above Is dependent upon the tenacity
with whleh the group R will retain electrons it shares
with the substituent group* hydroxyl* chloride# etc*
i.

It has been already mentioned (32*33) that the order of
electronegativity is primary > secondary > tertiary.

Hf
BC t X
H
secondary

H
H0*X
B
primary

B*
BC
R f1

tertiary

The X group could be any substituent group* hydroxyl*
halogen* or benzenoid ring.

If benzenoid ring it explains

why the tertiary is the only group which will be removed
by catalysis above.
Thus according to the oationoid theory the steps
involved in the alkylation of the benzene ring by 2*3*4*
triaethyl* 2 *pentanol are theses

4H

4

CH3 CH3 CH3 H Cl
C%C~C~C
iJJiAl*Cl
H H CH3
Cl

AlCl*

CHS

CH^CH^CHrz
GH#C -C *C+
H H CH

4

B Cl
tOi&lsCl
" SI

The carbonium ion then reacts with the activated benzene

suel.ua.

H

CH. CH. CH.
C5£_**C - C - C+H
”

H
”

a

H CB* OS* GH^
-a * 0 * c-m*

ch3
H

t ai% H

H

0

H
C%

CH3

0%

C - C * C *GH3
QH3 H

h+

H

H
That the above reaction takes place only to a small
degree due to the instability of the ootyl ©arboniua ion
will be shoen under the experimental and discussion parts
of this thesis*

I.

Preparation of S,3*4*trtmethyI-3-pentanoI
The only reference to this alcohol in literature

arose from work in this laboratory by Huston and Guile
(25)*

They prepared the alcohol from 3,4-dimethyl-2-

pentanone*

This ketone was in turn obtained by treating

the Griguard reagent of 2-me thy1-3-bromobutane with aeetyl
chloride*

An overall yield of about

0

$ based on the alkyl

halide resulted*
In order to secure a larger percentage yield the
writer attempted other methods of preparation.

The first

of these made use of the malonie ester synthesis*

Two

starting-point material© were used, chloroacetic acid
and student preparation diethyl raalon&te*
The diethyl maleaate was redistilled from a modified
Claisen flask with a Vigreux column;
at S9-900/13 mm, was collected*

the portion boiling

The method of prepar­

ation of diethyl isopropylmalon&te was an adaption of
that in ’’Organic Syntheses* (39).
Preparation of diethyl ieopropylmalenat?
In a five liter 3-necked flask, fitted with reflux
condenser, separatory funnel and stirrer, was placed
2.8 liters of absolute alcohol.

This alcohol was made

especially absolute (99*9$) by drying ordinary absolute
alcohol (98*5*99.5$) obtained from the stockroom over

magnesium methylate*
The magnesium methylate m s

prepared by dissolving

24 g* of magnesium turnings in 200 ec* of absolute methanol
(a very vigorous reaction sets in)*
ms

To this eleohol&te

added three liters of absolute alcohol and the mixture

refluxed 4-5 hours*

Ihe alcohol m s

then distilled di­

rectly into the 3-neck©d flask mentioned above until it
reached a predetermined

2*8

llhlle the alcohol m s

liter mark*
distilling, 105 g* (5 gram

atoms) of freshly cut sodium m e added to the distillate
with ears and artificial cooling applied to the flask*
Ihen the sodium had all reacted 82b g» (780 ec.f 5*15
moles) of m&lox&ie ester was added through the separatory
funnel*

Hext the isopropyl bromide 515 g* (5*0 moles)

was added slowly ttoo ugh the separatory funnel and the
temperature of the mixture began to rise*

After the

initial rise in temperature the solution was refluxed
with stirring for 48 hours or until neutral to litmus*
After this time about two liters of alcohol was
distilled off and the residue was treated with two
liters of water*

the upper layer was distilled from

a 1-liter modified Claisen flask with a 24-inch vigreux
column*

She fraction boiling at 153-135°/44 mm*,

ng°-l*4208, was collected for the next step in the
eyntheois*

The yield m ®

745 g* (74*5>)*

Preparation of methy3^methyligopropylmalonate
The introduction of the methyl group as the second
alkyl group was first tried using methyl bromide as the
methyiating agent with no reaction taking place at all#
heart 540 g* (3*8 moles) of methyl iodide m s
cording to the above procedure (39)*

used ac­

After twelve hours*

r©fluxing, distillation of the alcohol, and washing with
water, the ester layer was distilled*
unalkylated ester came over first*

Some low boiling

The fraction boiling

at 116*11?°/1G nun., njj° 1.4242-1.4251, 563 g. (70£ of
theoretical) ^as collected for the next step*
The diethyl methyl!sopropyl malenate was also pre­
pared by first preparing diethyl methylmalonate (40)
in 35$ yield from malonic ester and methyl bromide*

The

i©©propyl bromide was added to the diethyl methylmalonate
and after refluxing for 72 hours only 48$ yield of
diethyl methylisopropylm&Ionate was obtained for this
step of the reaction*

Preparation of 2.3-dlaathyl^tanole * s M
The diethyl methylisopropylmalonate was treated (41)
with am equivalent weight (ill) of KJDH and saponified
with a reflux condenser for six hours*
was neutralized with

12

XJpom cooling this

B sulfuric acid and heated eight

hours for decarboxylation*

The product was distilled

under reduced pressure and the fraction boiling at

102

-

104°/ 40 an. was saved far the Grignard reaction*

The

yield was 52$*
yre p a r ationof 2*3*4-trimethyl-2-pentanol
A large excess (42) of methyl magnesium bromide was
prepared by passing methyl bromide through a potassium
hydroxide train into anhydrous ether containing magnesium
turnings*

After all the 2,3-dlmethyl butanoic acid was

added slowly, half of the ether was distilled off*
Sufficient benzene was then added to bring the reflux
temperature to 50-55° G.

The mixture was then refluxed

four to five hours and the cool solution hydrolysed upon
lee*

Bractionation of the dry ether solution yielded a

low boiling ketone 35-55°/ 19 am. and the alcohol at
67-68°/ 19 mm*

The outs with refraetive index values

of 1*4330 were used for the first condensation*
Because of the many steps in the synthesis, and
relatively overall low yields (15-18$) a more effective
preparation of the alcohol was sought#
Synthesis by the Beformatskv reaction
Huston and Goerner (43) had synthesised the alcohol
in 40-45$ overall yield based on ethyl

c<*bromo propionate*

81nee the steps were fewer and the yields much larger the
bulk of the earbinol was synthesized by this method*

Many

helpful suggestions were given by 2k* Goerner in regard to
techniques previously developed*

16.

A kilogram of propionic acid was brominated (44)
a n d ester if led (46} by procedures in "Organic Syntheses **.
She Reformat sky reaction (43} was then used in five-mole
runs in a k n o c k e d fire liter flask*
sine was C. P. Baker9e Analysed,

The thirty-mesh

The acetone was dried

several days ever anhydrous potassium carbonate*
benzene solution of the

The

(3 -hydroxy ester thus obtained

was dried over anhydrous sodium sulfate and dehydrated
by ref Inning with phosphorus pent oxide by the method of
fton and Bargund (46}.

After removal of the benzene the

umsatur&ted esters were fractionated under reduced
pressure in a 24-inch Penske column.
Reduction of the esters was accomplished 0.1 mole
at a time using Adams 9 platinum catalyst*

the lower boil­

ing unsaturated ester reduced in a few minutes while the
higher boiling ester required from one to two hours to
reduce

0.1

mole depending on the activity of the catalyst.

At one time POOl^ was used as the dehydrating agent
and because of the small amount of chloride present the
catalyst was poisoned and subsequent treatment with
alcoholic KGH was required before reduction could be
continued.
The yield of

2

»3-dimethy Ibutanoi c acid was 45-50>£

based on the bromo ester.
To prepare the alcohol from the ester a ratio of

2.76 moles of methyl magnesium bromide to one mole of
ester was used*

The Grignard reagent was prepared by

passing methyl bromide (99.5$ pure* frost a Bow cylinder)
through a EOH column into a five liter flask containing
ether and magnesium turnings*

After adding the ester

slowly about half of the ether was distilled off and
benzene was added to bring the boiling point of the mix­
ture to SQ-5S® and refluxing continued for eight hours*
The mixture was hydrolysed on ice and enough cold dilute
sulfuric acid added to dissolve the basic magnesium
salts*

The acid layer was extracted with ether and the

combined layers washed with
finally with cold water*

10

$ sodium carbonate and

The ether solution m s

then

dried all night over anhydrous potassium carbonate*
After removal of the ether the distillation was carried
out in a yeaske column*

The yield of alcohol based on

the ester was about 85$*
Physical constants of the alcohol
B.P.-15S0/ 733 m m . , S7.50/ 14 sou, 49.8°/ 7 m».
»*° -1*4380
-0.8432
4
%

-Gale* 40*67

Y*° -27.4 4yn«o/«m.

Cbs. 40*24

XI. COb BMSATIQH WITH
The apparatus (Pig.

1

) used was that devised by

Van Ifcrke (4), variations of which have been used con­
siderably in this laboratory*

At (H) there is a mod­

ification by Ur. Goerner not shown in (Fig* 1).

At

this point (H) an additional stopcock was added so that
the whole system oould be evacuated by water pump thus
diminishing the time required for sweeping out with
earbon dioxide*
The functions of the various parts of the apparatus
in (Fig# 1) are as follows«
A-

A 1- or

2-

liter three-necked flask for con­

taining the condensation mixture*
R*

Propping funnel in which the alcohol is placed*

G-

Glycerine-sealed stirrer*

D-

Carbon dioxide generator (dry ice bottle) con­
nected to a sulfuric acid bottle.

32-

Reflux condenser*

G-

Xce salt trap to collect benzene and vapor© of
the less volatile liquid© and gases#

I-

Ury ice-acetone trap (-?5°) to collect vapors
of more volatile liquid© and gases*

K-

Mercury for pressure regulation*

3>

Safety trap (replaced once by bromine in carbon
tetrachloride to test for unsaturated gases-

FI GURE

1

fa.

negative result© were obtained)*
M-

nitrometer filled with 50^ KOH*

-Altogether 6*7 moles of the alcohol were condensed
with benzene#

In addition two one-mole rune by Hr,

Goerner were added for analysis*

She condensation pro*

©edure followed was typical of that evolved from years
of experience in this laboratory by Huston and ouch workers
t

•

as Bay © ($)» Barrett (3), and Van X&rke (4),

She temper­

ature for the most part was kept at or just below 35° C*
(a range of 34*1°

0

* was maintained as far as possible)*

A typical condensation shall be described in detail*
Benzene

450

ml*

Alcohol

150

g*

Aluminum Chloride

44*5

g*

5 moles
1 mole
l^mole

The aluminum chloride was placed in the flask, dry
benzene added and the mixture stirred and heated to re­
flux while the system was evacuated with gentle suction*
large quantities of hydrogen chloride were evolved*

XJpon

cooling carbon dioxide was flushed through the system
until microbubbles were obtained in the nitrometer*

At

this point the Dewar flask© were placed at traps (G)
and (1 ) and the stopcocks (F) and (h) directed so that
the gases would flow through the traps*
The first on©~third of the alcohol was added very

•lowly In order to maintain a constant temperature*
Especially during the first addition of alcohol there was
considerable evolution of gases*

The color transitions

followed the usual aleohol-aluminum chloride condensation
pattern (yellow, orange, brown, dark brown).

During the

addition of the second one*third the evolution of gases
slackened and finally back pressure developed In the
mereury bottle (&)*

This back pressure was in part due

to the liquefying of gases evolved in the traps (G) and
(I)*

To oounteraet this the pinch clamp controlling the

carbon dioxide flow was slightly released until the
pressure within equaled that without*

The final one*

third portion of the alcohol could be added rapidly with­
out change in temperature*
The mixture was stirred for an additional hour and
carbon dioxide passed through until microbubbles were
obtained*

While sweeping out the system with carbon

dioxide stopcocks (F) and (H) were turned and the traps
(0 ) and (l) were removed and either analysed immediately
or sealed in a glass tube*
The gas collected In the nitrometer was passed back
and forth through a dry ice-acetone trap from one gas
pipette to another*

The gas pipettes were filled with

concentrated sulfuric acid to take out any unsaturated
gases*

After passing through the trap several minutes

only fifteen to twenty ml* of gas remained*

This did

not b u m and was evidently air which leaked in the system*
Into the separatory funnel (B) was placed 125 ml*
of ice water and while stirring it was added to flask
A which was immersed in iee water*

The stirring was

continued until all of the giasay m s s clinging tc the
walls of the flask had dissolved*
The water layer was drawn off arid washed three times
with benzene*
1 0

The combined extracts were washed with

$ BOgCOg and finally with water and dried over anhydrous

sodium sulfate.,

It u

OS* PAGDUKM*

S&AGtlQBU&lQU A m

While the condensation produets were drying* the
liquids i» traps (G) and (l) were analysed*

2h trap

(G)i two to five grams of ben&ane were usually collected*
Bo other gases were found present in this trap except
hydrogen chloride which saturated the whole system*
3*rap (l) contained as much as 10 gr&ias of condensed gas
when two moles of the e&rfeinol were condensed with
bensene*

She contents of this trap were usually analyse

ed first*, or else sealed in a glass tube for safe keep*
log*

Before sealing, a toluene thermometer was placed

in one hole of a rubber stopper with the bulb touching
the liquid in the trap*

Hie other hole contained a

delivery tube to another dry ice-acetone trap*

-After

passing the liquefied gases back and forth several times
by gradually exposing one trap to the air until it gently
boiled and keeping the other one in the aeeio»e~dry ice
Dewar, the hydrogen chloride m s

elminated from the

liquid*
The nitrometer usually contained only air*

if the

alcohol had been added too rapidly* and the evolution of
gaseous products was too great, some bensene would escape
from trap (G) to (I) and quantities of isebntime ordi«*
narily trapped in (I) would pass to the nitrometer*
Consequently the gas in the nitrometer was always passed

back and forth through a dry ice-acetone trap as proviously described until there m e
in volume*

no more diminution

At this point the remaining gas no longer

burned*
After having dried over night the liquid products
of the condensation were distilled from a ground-glassjointed

1-11

ter round bottomed flask connected to a

24-inch Fenske column containing l/lc inch helices#
the bemsene was removed at atmospheric pressure
and great care m e

taken to retrieve gases dissolved in

the hydrocarbon mixture*

Shis was accomplished by

connecting a piece of rubber tubing to the top of the
distilling head and extending into a test tube immersed
in dry ice-acetone.

Ihe amount of isobutane collected

at this time quite often was greater than that collected
in trap

(I)*

When nearly all of the bensene was removed

two different course© were followed*

On® was continued

removal of ben©one and heating of the mixture at about
100

° C* which caused the decomposition of a large amount

of the alkyl chloride© present due to the instability of
the tertiary alkyl chloride© at elevated temperatures*
It was more desirable to convert nil of the chlorides
to alkene© immediately by r©fluxing the solution with
an equal weight of alcoholic KOH (1 *1 ) for two to four
hours*

She layers were separated and the upper layer

washed several times with water#

ihe other emulsion was

washed with water several times and the combined organic
layers dried over anhydrous sodium sulfate.

This treat­

ment usually gave chloride free organic layers.
the treatment was repeated*

If not

Hie presence ©f chloride

made separation difficult and tedious*
Xdentifleation of Isohutane
There was no unsatur&ted gas present as was ascer­
tained by passing the gases collected through bromine
in carbon tetrachloride*

This was doubly checked by

using gas pipettes containing concentrated sulfuric acid
and by refractive index measurements.
The gas in trap (X) was fractionally distilled as
previously described until free from hydrogen chloride
and bensseae.

An Anschuia thermometer then measured the

boiling point at -11° to -10° C.

Since refractive index

readings are often better indications of purity than
boiling points, an adaptation of a method by Grosrc (47)
for determining refractive indices at low temperatures
was used*
The two lenses of the refract©meter were protected
from frosting over with the moisture of the room by
covering them with a glass plate sealed on the sides with
vaseline.

A thermometer was calibrated at -25° 0. and

acetone with some solid carbon dioxide was passed back
and forth through the system.

After becoming familiar

with the apparatus a temperature of -25° * 1° C. could

be maintained.

Three possible gases possessed the follow­

ing physical properties?
Compound

1. P * C .

n-butane
iaobutane
isobutylene

n£26°

- © #5

1*5621

-10*2

1*3514

-6 . 0

1.3814

The observed refractive indices varied from 1.3512
to 1.3518 in about ten readings, using different samples
from different condensations*

This left no doubt as to

the Identity of the gas in trap (i) as Isobutane.

In

contrast to the work of Van % k e and Barrett no methyl
chloride was found.
a

. fractionation without alcoholic KPH treatment.

i

.

•

■

In { M g . 2) is shown the plot of grams of product vs.
refractive index on condensation of three moles of the
alcohol.

An overall picture of the percentage yields and

variations in refractive index is thus obtained#

With

alkyl chlorides separation of products was exceedingly
difficult.

For example in separating

2

,3,44trim©thy 1 - 2 -

chloropentane from t-butylbenzene long r©fluxing and slow
removal of the alkyl chloride was required to keep the
refractive index of the cuts at the value for the chloride.
For this reason products shown in (Fig. 5) give a better
picture of the separation.
A list of fractions (3 mole basis) without alcoholic
KQH treatment is as follows?

<MQ

fyahS PrtJticf CF'tjS)

X. 2-methylpropane
Thin was identified as outlined above.
B.P.
n^O

<*1 1 ° to -10° C.
- 1.3815

Yield- 25 g. (7$)

2. 2,4,4-triiQethyl-2-ehloropentane

(?)

This fraction was not identified due to its presence
in such small amounts.;

However It must be present in

order for the refractive index in ( H g . 3) to drop as low
as it did to give

2

,^A-trimethyl-l-penten®, or else this

olefin was formed from the dimerising of the t-butyl
radical.

(51).

B.P*

«*

B*°
it
Yield 3.

2

S5°/28 mm.
1.4300
5 g. (1.0$)

*3 9 4***tri methy 1 * 2 -chloropentane

As far as the writer knows this compound is not re­
ported in literature*
like odor.

This octyl chloride had a camphor

Since there was not much evolution of heat

during the addition of the last half of oarbinol perhaps
most of it was converted directly to the chloride*

Hie

chloride was synthesised from the action of concentrated
hydrochloric acid on 2#3 >4-tri»»ethyl-2*-pentaaol and the
physical properties compared*

They were as followsj

SP.

-

60.5 - 61°/20,5 mm,

nSO
!>

-

1.4392

i48-149°/r'3t’ mm.

0*8939

f

-

%

-

Calc. 43*98

oho. 43*84

SUV*

-

Chic* 149*6

oho. 160*3
ehs# (DuNouy) 381*4
(Prop wt.) 382*6

Paraehor

-

Calc. 380*4

Yield

-

100

g. (23$)

4* 2-methyl-2-phenylpropane
Thia low energy-level fragment has been found in all
oases in which degradation has taken place*

It was the

major product and no difficulty was encountered in identi­
fying it by means of its p —scetaaimo derivative (48) .

ihe

physical constants eheek with those in Igloff (49)*
B.P.

-

60°/X4 mm.

nl°

-

1*4918

jf

-

0*8672

^
M*V*

*
-

Paraehor
M.P.

—

168*3/737*3 am*

Oslo. 44*78

ehe* 44.85

Calc. 134*0

ehs. 131*5

Chic * 339* 4

she* (BuHouy) 358. 6^23° C*
(Prop wt.)35?*l©g0°C*

p-acetamino
derivative

-

169-171° C.

115 g* (2Q%)

Yield -

(?)
Because of difficulties encountered in separating
these alkyl chlorides this fraction was worked with only
after alcoholic X 0 B treatment*
B®®

-

Yield -

1.48X3
8

g. (1 .2 /S)

6* 2-methyl-2-phenylbutane
Hie boiling point, molecular weight and refractive
index (50) checked with those of t-amylbenzene which led
to the preparation of the p-aeetamino derivative, confirm­
ing the presence of this fraction.

In order to raise the

refractive index to the value reported in literature the
fraction was refluxed with bromine in carbon tetra­
chloride and redistilled to eliminate traces of olefinic
impurities.
B.P.

-

189-190°/742 mm.

n|°

-

1.4928

D20
4
%

-

0.8716

-

Calc. 49.40

oba.

49.34

M.W.

-

Calc. 148

obs.

150.5

Paraehor -Calc. 399.4

71-72°/l2 mm.

obs. (Dullouy) 399.0
(Prop wt.) 397.8

M.P.

-

p-acetamino
derivative 139-141 C.

Yield

-

13 g. (Z%)

7. C ^ S

01

This is not found in literature and it was not
completely identified.

After alcoholic KOH treatment

the carbon and hydrogen analysis showed olefin forma­
tion.

The molecular weight measurement indicated the

presence of a compound comparable to thiss
B.P.

-

84-85°/4 mm.

n®°

-

1.4830

29.

M.W.
Yield
8

- Calc. 204.5
-

obs. 202.2

20 g. (3$)

. 2,3,4-trimethyl-2-phenylpentane
This fraction was the expected condensation product.

Because of such great fragmentation the yield was only
6.5$.

An attempt to prepare the p-acetamino derivative

gave no success.

The carbon and hydrogen analysis indi­

cated an octyl benzene.

It was necessary to reflux with

bromine In carbon tetrachloride for a short time and redis­
til in order to eliminate unsaturated impurities.

Subse­

quent nitration, reduction, and dlazotization gave a phenol
corresponding to the one obtained by direct treatment of
the carbinol with phenol.
B.P.

- 235°/758 mm.

92°/5 mm.

n-

. 1.4958

D2 0
4
%

- 0.8840
- Calc. 63.25

obs. 63.35

U.W.

- Calc. 190.3

obs. 192.5

Paraehor- Calc. 513.4

84°/2 mm.

obs. (Duilouy) 512 @ 24°C.
obs. (Strop w t . ) 509.6 @ 20°C*

C - H Analysis
C - Calc. 88.33$ obs. 88.27$
H - Calc. 11.67
obs. 11.50$
Yield

- 35 g. (6.0$)

9. Residue
This consisted of high boiling polymerized products.
15 g.

B, Fractionation after alcoholic KOH treatment.
A list of the fractions (3 mole basis) obtained after
alcoholic KOH treatment is as followst
1

*

2

-methylpropane

Identified with the same physical properties as in A*
2

. 2,4,4-trimethyl-l-pentene

(?)

This fraction was not identified, but there were indi­
cations that a trace might be present.

Removal of hydrogen

chloride from the octyl chloride with alcoholic iCOH gave a
refractive index for the lowest fraction of just slightly
below 1.410.

lahltmore (51), in separating the two diiso­

butylenes obtained a refractive index of 1.409 for the
lower boiling one and 1.415 for the higher boiling olefin.
The former was also present in much larger amounts (4.5si)
as shown by ©zonolysis (52).
from

2

Removal of hydrogen chloride

,3 ,4-trimetby 1 - 2 -chloropentane could give two

possible olefins.

The refractive index of 2,3,4-trimet hy 1-

1-pentene, the one with the lower value 9 is 1.4146 (53).
Therefore an index reading of 1.410 would indicate
that 2,4,4-trimethyl-X-pentene could be present.

This

results either from the dimerizing of isobutylene or from
hydrogen chloride removal after the octyl radical re­
arranges to form diisobutylene chloride.

The other olefin,

2 ,4 ,4 -trimethyl- 2 -pentene would be present only in the

ratio of 1 to 4.5 452) so that detection of such a small

£rah,s PtoJucf

amount would be impossible*
B*P*

* 10X-102°/73S mm*

XQl.5°/76Q nan. (53)

Bgv

- 1*4092

1*4089

(53)

B#°

- 0*7173

0.7164

(33)

%

- Calc* 33*37

obs. 33*75

field

- 4 I* (l$)

3* 2*3,4*trimethy1«*1*»pentone
Hb« physical constants of this fraction compared
f t W f i W y with those in l&lcft (53) leaving no doubt as
to lie identity*
B*P*

* 107~1OSV?38 mm*

107°/ 7 44 mm*

(33)

®§°

- 1*4145

1*4146

(33)

J&°

- 0*7242

0*723

(53)

~ Calc* 38*57

obs* 38*65

Paraehor- Calc. 330*0

field

- 45 g* (14$)

4* 2*3*4-trimeihyl~2-penteiie
This olefin is the ether olefin formed by removing
hydrogen chloride from

2

*3 *4 ~trimethyl- 2 -chl0 rop@nt&ne.

The physical constants agree with those found in
Bgloff (34)*
B.P.

- 114~115°/738 mm. 42°/58 mm. 115°/?50 mm
1*423
0*7370

M*W*

Calc* 38*67

Obs. 38.74

- Oslo* 112*1

Obs. 114*0

Iterachor- Calc. 330.0
XIaid

obs.

(DuHouy) 333.1
(nrop Wt.) 334.2

- 35 g. (16$)

5. 2-»ethyl-2»phenylp:ropane
Physical constants and 1dentIfIcatIon steps given

in A.
6 * C11H22
She sharp drop in refractive index (Jig* 3) is indic­
ative of a change from an aromatic compound to a complete­
ly aliphatic one*

She hand reading of the refractometer

Indicated this also*

Although complete identity of the

hydrocarbon fraction was not established, its carbon and
hydrogen analysis showed it to he olefinic* and its
molecular weight proved it to be an olefin or mixture of
olefins of eleven carbon atoms.

The most plausible eleven

carbon olefins will be suggested under the Discussion part
of the thesis*
B.P.

* 17?«*X80°/?33 mm.

n®°

- 1.449©

j^O

- 0.7915

l£g

- Calc* 02435

obs*

52*33

Iff.W.

* Calc. 154*3

obs.

153*5

paraehor- 450*0

obs* (DuHouy) 454*5

C - H Analysis
0 * Calc* ©5*71
H - Calc. 14*29

obs. 85*62
obs* 14*13

Yield

-

8

g. (2$)

7•

2

-methyl- 2 -phenylbutane

This fraction was Identified and has the physical
constants shown in A*
c 12H 24

A drop in refractive index# deeolorisation of bromine
in carbon tetrachloride and earbon-hydrogen analysis in­
dicated this fraction to be an olefin or mixture of
olefins*

Molecular weight determination shows it probab­

ly contains twelve carbon atoms*

under the Discussion

part of the thesis the possible structures will be
suggested*

Bydroxylation and oxidation with perchloric

acid yielded acetone in small amounts*

This would indi­

cate 2,4,4,5,6-pentaraethyl-2-heptene as one of the
probable olefins*
B.P.

- 189-197°/?33 mm*

57-S7.5°/4 mm.

n|°

- 1*4620

2j£°

- 0*8091

%

- Calc. 57.15

obs. 57.06

M.W.

- Calc* 168.3

obs. 170.8

Paraehor-Calc. 484

obs. (DuHouy) 474.0 @ 26°G.

C - H Analysis
C — Calc. 85.71
B - Calc. 14.29

obs* 85.89
obs. 14.05

Yield

- 25 g. (5.5$)

9. 2*3*4-trimethyl-2-phenylpentane
Physical constants and identification in part A*

34

1 0

. Residue
0

»e fraction of this residue with a refractive index

reading lower than the octylbenzene gave a molecular
weight of 230.

An olefin of sixteen carbons would have

a molecular weight of 224.

Thus there la evidently some

dimerizing of the octyl group and perhaps even further
polymerisation.
13 g.

iv.

a*’ t m qarbimqh with BHmox,
To aid in the proof of the structure of the octyl-

benzene the alcohol was also condensed with phenol.
Guile (23) had made this condensation in 1938 with 0.25
moles of the carbinol but due to the fragmentation of the
alcohol 9 small yield and varied products it was thought
advisable to cheek the physical constants of the octyl*
phenol and its derivatives.

Two condensations were made

using 0.55 moles and 1*1 moles of the alcohol.
The apparatus in (Jig. 1) was used in order that
escaping gases might be detected.

The procedure was

essentially the same as outlined by Guile.
Hie aluminum chloride (0.5 moles) and

200

ml. of

skelly solve were mixed together in a 3-necked flask*
The phenol (1*2 moles) was dissolved in 1 mole of carbi­
nol and the solution added slowly through a separatory
funnel*

The temperature was kept at 29*1°c*

After all

35

of the solution had been added# the mixture was allowed to
stand all night and hydrolysed the next morning with lee
water*
3he water layer was extracted three times with ether*
The combined extracts were dried over anhydrous sodium
sulfate*

tfpon distillation of the solvent at atmospheric

pressure about

1

gram of isobutane was collected in a dry

iee^aelltone hath*
After the solvent had been removed* fractionation
showed the two olefins resulting from the dehydration of
2 f3 t4~trlmethyl~2~pentanol» the octyl chloride* large
quantities of wnre&eted phenol# plus al&yl phenols*

There

were two w i n fractions of these ahlyl phenols as followst
PTom

1*1

moles of carbinol *

X. 110*125®/$
II* X30*14O°/5 mm.

3.0 grams
23 gram®

fraction I did not crystallise until redistilled
several times to free it from phenol.
(M.P. 95-96°) was obtained W

Tertiary butylphenol

crystallising from skelly

solve*
fraction II first started to melt at 78°*

Repeated

crystallizations from skelly solve* leept at - 1 0 ° f gradually
increased the melting point of the phenol separating out.
Redissolving in fresh solvent and reerystall!zat1on finally
gave a phenol melting at 88-89°,

This proved to be 2#3*4-

trlmethyl- 2 *p-hy dr oxypheny Ip entane*

There were several crystal fractions ranging in melt­
ing point from

68

° to the pwre octylphenol.

The lowering

of the melting point was undoubtedly due to some foreign
substance*

It was thought that the foreign substance might

be some t-butylphenol or perhaps some rearranged octylphenol 9 (2 9 4 #4*trim«thyl- 2 -p*hydroxyphenyIpentandu
Smith and Hodden (58) have shown that aluminum
chloride treatment of dlisobutylene phenol gives 75$
yields of tertiary butylphenol*
V, PROOF Q¥ BIBUCTUhS
Nitration of the octylbensen© by the IfeXberbe (59)
procedure, reduction of the amine# and subsequent diasotization to give the phenol was carried out as outlined
in detail by Guile (83)# Van Ifcrlce (4) and Kaye (5).
Mixed melting points of the converted octylbenzene
and the ootylphenol showed no depression.

Their

c*-naph-

thylurethanes when mixed also melted without depression.
The t-butylbenzene was also converted into the t-buiylphenol and its melting point and benzoate derivatives
were identical with those obtained from direct condensa­
tion of the alcohol with phenol.
The structure of

2

,3 ,4 -trimethyl- 2 -chloropentane

was proved by preparing it from the alcohol.

2,3,4-

trimetbyl- 2 -pentanol was treated with concentrated hydro­
chloric acid, refluxed and the product distilled under

reduced pressure.

The constants cheeked with those of

the alkyl chloride obtained*
The eleven- and twelve-carbon olefins were hydroxy leted by the method of Milas and Susbiaan (64)*

The glyeols

thus obtained were oxidised with *Cerie perchlorate * as
outlined by Smith and Duke (65).
Bvidently the double bond is next to the end carbon
in most of the

fraction as there were no aldehydes

or ketones obtained*

A small amount of acetone was found

upon oxidation of the glycol from the

VI*

mM&ABATXQM

1* The

m

zmav

a t

fraction*

ivm

o<^mphthy lure thanes were prepared by the

method of Jremeh and Wertel (57).
2

* the benzoates were prepared by the pyridine

method of Shriner and Puson (60) for the preparation of
3 #5~dinitr©benzoates.
3

« the preparation of the p-aeetamino derivatives

is described In detail by Van lyke*

It is the method

developed by Ipatieff and Scbaerllng (88,58)*

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sxacussxos
Vfam 2*3*4-trimethyl-2~pent&nol (23} was condensed
before with benzene* none of the octylbenzene was obtained
because of the small quantity condensed*

With low boil*

lag point products it was apparent that fragmentation had
taken place*

Shis led to the problem of this thesis*

observing the f ragmen tat ion of the alcohol by condensing
several moles with heasene and carefully fractionating
the products*
Hhttmore (61) has observed that catalysts such as
aluminum chloride cause molecules to rearrange by methyl
group migration* and In 191$ Boedtker and Balse noticed
rupture of the molecule with aluminum chloride as catalyst*
M

the study of this alcohol there is both rearrangement

end rupture of the molecule in more than one manner*
In all highly branched alcohols one of the products
of condensation with benzene is the resonating* low energy
level* tertiary butylbenzene.

It was the principal pro­

duct in this case*
As was deduced in the theoretical part of this thesis*
the best theory for the condensation mechanism is an
adaptation of that of Price (27)*

According to the cationoid

theory the condensation would proceed in the following steps s
**

C#) m f *

+

||t<a

a

—

— »

a*i*j!:ci

** a

(#) Xxt thin discussion the R group shall be Sfe2 CHCHUe&feg

**

.

)

R+

-f-

(Ha&XCljjJ**

#Wter the formation of this ear boniest ion there
o large number of p oee

retvc1 1 ono•

1

*

4£ae of those is eondeo-

cation with the benaeae «*aele£ which'sure present in excess
c r r c s s i b X y ©©Jbbiastlea with the chi or ihe ion also present
:lh large

Loss of & preton woulo gi#e an

olefin*

B

Cloer cf pretest}

,; .. In the casr-hepi**®? ton JUt'step: 2 -the nnaber
.is

carbon

fhia draw* the electron pair between c^rbone

three end fear closer to the number three carbotu

The

•,ha^ane® of. electrcma s*beut carbon two especially * &na alee
■at, BiaalNKr- three .causes split!lag of t-i*e molecule to- fora
the i soj?repyI ©a t io ^ end trteethyl ethylene*
It in significant that the laoprcpyl group la released
more readily than the methyl group:-#

Thi e is evidenced in the

fadt that no chlororaethane was detected upon careful
analysis of t h e g a s e o u B fraction#

Huston and Barrett (3)

la&feshown that condensation of 2,3, 3 -trimethyl~2-butanol
with hensene gave considerable ehlor ©methane*

Since

iione was obtained;tu this investigation, evidently the
electron pair I * ‘- ^ “er to the methyl group than to the
isepropyl groug
1

3d♦

the isoamylen© can either condense with beaten© as
the olefin, or as the tertiary acyl cation#

tee low yield of the expected product and high yield of
the t-butylhenaene is attributed to the tendency of the cation
to undergo rearrangement {61) with resulting rupture of the
chain •

Sitter on© of the fragments resulting from the chain
rupture la capable of condensing with benzene to give

2

-

methyl-S-phenylprcp&ne, or the olefin might add a proton
before the condensation.

-ft t-butylbenzene

the mechanism of the format Ion of Isobutane la biff ic u l t t o explain*

Although there are numerous references to

such reductions in the presence of alumintiai chloride in
literature, none.has offered a simple explanation*

In a

review by ^ l o f f (62), he state© l^bat alkene pely&eria&tioa
using aluminum ehloridemay involve eycliz&tion and die**
proportionation*

In the polymerization of ©thene with alumi­

num chloride* hydrogenation# dehydrbgeuation# and cyelization
occur to such an extent that the products consist of alkants
and cyclones {65}*
In the isomerization of alkanes in the presence of alumi­
num chloride# Kbm&rewsky (6

6

) always found large quantities of

isobutane as well a© olefin© of greater carbon content*
CV

£

CH2

+

Hg (di ©proportionation)

^

Mftiltmore (6?) has shown that dehydration of isopropyl
tertiary butyl carbinol gives none of the expected olefins
but does give a 5$ yield of 2#4#4-trimethyl~l-pentene*

It ia believed that in the present investigation the
eetyl nation adds te propene to give tiro isomeric el evencarbon olefins {a and B) after loss of a proton*

Although

less likely according to polymerisation studies, three
other possible olefins (C#D and E) could form by the addition of the isopropyl cation to 2*3*4-trimethyI~l~pentene*

B*

In the dehydration of an analogous alcohol* 4 ,4dime thy 1 ~ 2 -pen ta no 1 * m i t m o r e (6
ratio of

4

8

) has shown that the

*4 -dimethyl- 2 *pentene to 4*4«»dimethyl-l~pentene

Is 4,5 to 1*

this would indicate a preponderance of A

over B,
In a similar manner the oetyl cation can add to
Isobutene to give two isomeric twelve-carbon olefins*
theoretically possible* also, are three other olefins
(H, I* and J) formed by the addition of the tertiary butyl

cation to 2#3#4*trifflethyl~l*peateae*

Although all fire

©f the olefins may he present» the formation of F and 0
seeai moot plausible*
In the dehydration of

2

f4 1 4-tr imethy 1 - 2 -pentanol*

Whitmore (69) has shown that the ratio of 2 #4 f4~trimetfayl1-pen ten© to 2# 4 f4~trimsthy1-2-pentone ie four to one*
Analogously* one would expect a greater amount of

6

in

this fraetioa*

J.
mien

1^ e

twelve-carbon olefins were hydroxy la tod and

oxidised with perchloric acid, acetone was found present in
n a i l amounts*

m i s should indicate the presence of F*

46*

SUMMARY
1*

2,3,4*trimethy1-2-pentanol was condensed with benzene
In the presence of aluminum chloride*

Only

of the

expected 2,3*4-trimethyl-2-phenylpent&ne was obtained*
2*

Proof of the structure of 2,3,4*trimethyl-2-phenyl*
pentane was obtained by nitration of the oetylbenzene,
reduction and diazotization to giro an octylphenol
identical with one obtained by direct condensation of
the car b i n d with phenol*

3*

The gas, 2-methylpropane, was obtained and identified
by its b«p»» and refractive index at -*25°0*

4*

Chain rupture, both before and after rearrangement,
gave a small amount of t—assylbenzene, ano. a 2 8 yield of
t-butylbensene*

5*

Possible mechanisms are suggested*

Mixed eleven- and twelve-cor bon olefins were found
present and possible formulas presented*

6*

The alcohol was also condensed with phenol to give
two principal products*

The octylphenol thus obtained

was identical with the phenol obtained by conversion
of the oetylbenzene by nitration, reduction, and di&zotizatlcn*

47.

BIBLIOGRAPHY
1* Huston, ye* and Binder,

j* Org. Chem*, 3, 251

(1938)

2. Huston and Awuap&ra»

Ibid.,

9, 401

(1944)

3* Huston and Barrett,

Ibid*,

JI, 657

(1946)

4* Tan J^rke,

Doctor’s Thesis,
Mich. State College

(1944)

Doctor’s Thesis
Ml eh* State College

(1942)

Doctor's Thesis
Mich. State College

(1943)

5. Says,
6* Haley,
7. KTanslein,

'•Aluminehlorid In der Organisehen
Chernls*’, Verl&g Chemie GMBH, Berlin, (1930)

8* Thomas,

"Aluminum Chloride in Organic
Chemistry*, Beinhold, Hew York,

9* Adams,

’•Organic Reactions", Vol. Ill, Chap.l
By Price, John Wiley and Sons, Inc.,
Hew York,

10* Huston and ]£riedeman, I* Am* Ghem*
11* BOY,

Am**,

12* Huston and Sager,

W* Am* Ghem*

13* Harris and Sturgis,

Ibid*,

(1941)

1946)

See*, 40, 780

1918)

398* 285

1892)

Soc*, 48,1955

1926)

61,1413

1939)

14* Yaukerranlk and Has&rova, I* Gan* Chan*, (U.S.S.K*)
7, 632 (1937)
G* A.
|T,5778 (1937)
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J. Gen* Ghem*, (U.S.S.B*)
6 , 767 (1935)
C* A.
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16*

Gustavson,

Ber*,

Jl^lSSl

17* Meyer and Bernhauer,

Monatsh.,

18*

I* Am. Chem. Soc*, 60.,2953

Simons and Archer,

(1878)

53-»54§ 731 (1929)
(1938)

48

19.

I p a t i e f f * , P in e s
a n d ^ e h m e r lir ig ,

J*

SO,

S c h ra m m ,

M o n a ts h * ,

S I.

K o n o v a lo v

ss*

H a s te n , G u ile ,
S e u lc - tfi e n d W a s a o n ,

S 3,

24 *
25 .

end

O rg .

J e g o ro t,

G u ile ,

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Chem .

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Q rg .

Z e n tr* ,

and

Rod

© n,

(

1941 )

I *

621

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1888 )

i,

776

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1892 )

252

(

1941 )

Cueau,

D o c to r * s T h e s is
M ic h * S t a t e C o lle g e

(IS

Ms s t e r * s T he s i s
M i eh. S t at e

(

1947 )

(

1946 )

Ma a t e rf s T h e s i
M ie h * S t a t e

B re l te r ,

253

C h e m *,

C l ; 023.*

tr*

11 0£■*!0

28 )

&

C o lle g e

59 ,

2355

(

1957 )

29 ,

37

(

1941 )

59,

1417

(

1937 )

4 ) 19 *

44 4

(

1916 )

S o c*,

se.

S m ith

27 *

P r ic e ,

28 .

Ip a tie ff

and

O o r s o n ,<T *

29 *

B o o d tk a r

and

H s la e ,

B u ll* ,

30.

M illig a n

and

R e id ,

J

U J ..

W o o d w a rd , B o r e h a r d t
aad J a s o n ,

,
Ib id .* ,

56 ,

£103 {19 34 )

32 *

B ro m ,

I o i d.» ,

61 ,

1483

33*

W h i tm o re

34 *

T zuk e rr

C hem *

a m i .

m x i k

Am*

.

1*

C hem *
soc*

Am*

B e r n s t © in ,

,

R e v*,
S o c .,

o h im * {

C hem .

S o c .,

la id * ,
G en*

C ■i e n u

S

(.U *

B

3l *

35 *

A*

C hem *

C a lla w a y ,

36 *

M

r : n a

ea d

So ws ,

1*

r%IJ
%*£ f

M cK enna

and

S o we

I i: i d * ,

*

c K

q

38 .

H u a to n

fc/aJ *

O r g a n ic

and

F r ie d © m o n ,

S y n t h © .?■© s ,

MiFii 0

R a y .,
O.i'.i e m *

t 'b id * ,

S ,) c * ,

{

1939 )

2626 (19 56-)
*}

•

5,
C*

206 (19 22 )

J i*

117 { 1955 )
4746 (19 35 )

AZ*

527

(

1955)

59 ,

470

{

1957)

59.

1204 (19 3? )

J g ,

2527

{ . 1916 )

* 0 r g n . n l o S y n t n *•.r © s %
J o h n W:11 e y
and S o n s , I n c . , K* Y * , C o ll * T o
E n d E d . , 1941 . p .250

1.2

4W*

40* Organic Syntheses*

*0rg: ulc Synthes-os*, Joan Wi ley
and Sons, Inc., &.Y., 1943,
Coll* Vol*II, p. 279

41* Organic Syntheses,

Ibid*,

42* Bel ley,

Master* a Yhesia
Mich* St--to Coll-ge

43* Huston

p* 416
(19 44)

andGo erne? t$ * Am* Chem* Hoc* ,68, 2504 (19 46)

44* Organic Syntheses,

"Org*ale Syntheses*, Vol. XX,
John Wiley end Sons, N* Y * , 1940,
p. 106

45* Organic Syntheses,

•'Organic Syntheses*, Vol. 23,
John Wiley and Sons, 11. Y*, 1943,
p. 38

46* Con and Hetrgpnd,

J* Chs®. Soc*,

2461 (1952)

47. Gross©,

J. Am*

Chem. Soc*,59 ,2739 (1937)

48. Ipatieff and
Sohmerllng

Ihld*,

60,1478 (1938)

49* Eglaff,

••Physical Constants of Hyaracarbons*,
Vol. Ill, Reinhold Publishing Corp.
M* Y., 1946, >* 97

50* Egloff,

Ibid.,

51* Whitmore andWrenn, J* Am.

p. 115
Chem* Soc.,53,5136 (1931)

52. Whitmore and Church,! old.,
53. Egloff,

54* Egloff,

_54, 3710 (1932)

••PhysicalCourt ants of Hydro e? rbo ns*,
Vol. X, Reinhold Publishing Cory.,
H. Y . , 1939, p. 232
Ibid.,

p. 233

55. Whitmore end Souk,

J. Am. Chem*

56* Komerewsky,

Ibid,

69, 492 (1947)

57* Yrench and Wert el,

Ibid.,

48,1756 (19 26)

58. Ipatieff end Schmerling, Ibid.,

Soc*, ^54,3714 (19 32)

59,1056 (1937)

50.

59* Malherbe,

Ber.,

60. Shriner and Fuson,

*XdeniIfieation of Organic
Compounds", John Wiley and Sons,
H. Y, 2nd Ed,, 1940, p. 138

41. Whi trnor e»

J. Am* Chem, Soc.,

62. Oilman,

"Organic Ohemietry * § John Wiley
and Sons, Vol. 1, 2nd Ed*, 1942,
p. 13

63* Ipatieff and Grosse,J. Am* Chem* Soc.,

52, 319 (1919)

54,3274 (1932)

915 (1936)

64* Milan and Suesman,

Ibid.,

58,1302 (1936)

68. Smith and Duke,

2nd. Bog. Chem.,
Anal. Ed.»

13, 558 (1941)

86. Shmarewslcy and dicle,^* Am. Chem*

§9# 492 (1947)

67. Whitmore and Houk

Ibid.#

§4,5714 (1932)

68* Whitmore and HomeyersIbid*#

,4194 (1933)

69. Whitmore, Howland,
Urenn and Kilmer,
70. Kuykendall and
Board,

Ibid.,

§4,2970 (1942)

Ohio State t&iv*, Abe. Bteto***
M s sot*tat ion, lb. 17, 241*53, 1935