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THE PREPARATION AND IDENTIFICATION
OF TIE Acmm "IO DERIVATIVES
OF TERTIARY ALKYL DEEZEEES

by
John Hamilton Coleman

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

MASTER OF SCIEHCE

Department of Chemistry
1941

,4’ll"§“

ACKIé GULF. WERE T

To Dr. R. C. Huston, the writer expresses
his sincere appreciation for the helpful
suggestions made during the performance

of this work.

33162-1

Introduction - -

History ~ _ - -

Exzerimental
Katerials -

Carbinols -

Contents

Condensation; - - - - - - -

Preparation
Tables - ..
Discussion - - _
Sunmery - - - -

Bibliograpfiy - ‘

of Derivatives

Iage

12
15—19

Introduction

In the course of a study of aromatic hydrocarbons
Ipatieff (1) found need of a simple method of the identi-
fication of alkylbenzenes. Boiling points and other physical
constants would have been satisfactory for distinguishing
between homolOgous compounds but inadequate in the case of
isomers, oxidation could have been used to distinguish between
mono~ and dialkylbenzenes, but of course, would have failed
to determine the configuration of the alkyl groupings.

Ipatieff and Schmerling (2) in an attempt to establish
a.suitable means of identification of several alkyl benzenes,
studied the mono- and di-acetamino derivatives. No previous
study of the nitration, reduction, and acylation of a series
of alkylbenzencs under a single set of conditions had been
attempted.

A procedure for the quick and easy identification of
mono-alkyl benzenes was deveIOped. Under the prescribed
conditions pure L-nitroalkylbensenes may be obtained by use
of a nitrating mixture of equal volumes of concentrated
sulfuric and nitric acids. Ortho isomers are present in
only small amounts and do not interfere; and the dinitro
derivatives which may be present may be readily separated by
an ether extraction of the solution obtained on reducing
with tin and hydrochloric acid. The mono-amino complex forms
an ether soluble salt with tin chloride in the presence of
acid; the dianino salt is ether-insoluble.

Ipatieff and Schmerling prepared both mono- and di-

acotamino derivatives of toluene, ethyl benzene, the propyl
benzenes, the butyl benzenes and the amyl benzenes. All
were white crystals, possessed sharp melting points, and
were easily identified.

In this laboratory since 1934 higher alkyl benzenes
have been prepared by condensation of tertiary alcohols with
benzene in the presence of aluminum chloride. A fairly
satisfactory method of identification of these hydrocarbons
has been effected in the preparation of the correSponding
alkyl phenols (and subsequent preparation of urethane
derivatives) by nitration, reduction, diazotization, and
hydrolysis. however, the method is long, and not entirely
gratifying with small amounts.

Since it was necessary, for a complete study of the
mechanics of condensation reactions, to establish the identi-
fication of mixed fractions and split alkyl benzene products,
and since the acetamino derivatives of some alkyl benzenes
had been prepared, the preparation and identification of the
mono-acetamino derivatives of all the condensation products

(tertiary alkyl benzenes) was highly desirable.

History

Huston and Fox (3) in 1934 successfully condezsod
tertiary butyl alcohol, tertiary any aleahel, dimethvl
n-propyl carbinol, and dimsthyl iso-prooyl carbirol with
benzene to give the empected products, tertiary tutyl
benzene, tertiary amyl benzene, dincthyl n-¢ropyl pheny
methane, and dimethyl iso—prolyl methane, in good yields.

Huston and hinder (L) in 1935 COHSBESGG dinethyl D-
butyl carbinol, dimethyl iso—butyl carbinol, dimethyl sec-
butyl carbinol, methyl ethyl n-prOpyl carbirol, methyl
ethyl ice-prepyl carbinol, and trimethyl carbinol to obtain
in good yields the products, dimethyl n—butyl phenyl methane,
dimethyl iso-butyl phenyl methane, dimethyl sec-butyl phenyl
methane, methyl ethyl nuprOpyl phenyl methane, methyl ethyl
iso—prOpyl phenyl methane, and triethyl pheryl methane. A
condensation with dimethyl tertiary butyl carbinel gave a
product in the expected range, but it was not identified
with certainty.

Huston and Sculati (5) in 1936 condensed dimethyl amyl
carbinols (n-anyl, active amyl, iso-amyl, sec-amyl) with
benzene to form the alkyl benzenes dimethyl n—amyl phenyl
methane, dimethyl active amyl phenyl methane, di-methyl iso-
amyl phenyl methane, and dimethyl sec-amyl shenyl methane
in yields which decreased with the approach of tee branching
to the carbinol grouping.

Huston and Ireining (6) in 1938 by condensation with

benzene prepared diethyl n-prOpyl phenyl methane and di-

ethyl iso-prOpyl phenyl math Hi approximately 25$ yields
from diethyl n-prOpyl carbinol and diethyl iso IOpyl carbinol
respectively.

Huston and Cline (7) in 1939 were able to isolate methyl
diah-propyl phe.n"l methane and methvl h-Jro yl-iso-propyl
phenyl methane in 37% and 18} yields respectively; and also
small amounts (7%) of methyl di-iso~pr0pyl hsnyl methane
from the respective carbinols.

Huston and .Jnter (8) in 1939 in tr» ir proof of structure
were successful in isolating and identifying the normal pro-
ducts of con<ens ation of n-butyl netth ethyl carbinol, sec-
butyl methyl ethyl carbinol, and iso—butyl T~thyl eths 1 car-
binol, nith benzene.

Huston and lesson (9) in 1940 by reactions of 2,4,L-tri-
methyl pentanol-Z, 2,3,3-trimethyl pentanol-Z, and 2~methy1~
3-ethyl-pentanol-2 with benzene, prepared the correSponding
alkyl benzenes, 2,A,A-trimethyl-Z-phenyl-pentane, 2,3,3-tri-
methyl~2~phenyl~pentane, and 2—methyl~3~cthyl~2~1wh nyl-pentane
(the later which.huston and Guile (10) had earlier reported)

althouizh in small yields.

ExPerimental

Haterials
1. H-amyl, sec-amyl, iso-amyl, active amyl, n-propyl,
iso-prOpyl, and n-butyl bromides were prepared from the
corresponding alcohols (Eastman technical) by the action
of sulfuric acid and hydrobromic acid (11).
2. Tertiary amyl bromide was prepared by shaking the
alcohol with 48% hydrobromic acid in the cold and
salting out with calcium chloride (12). Two degree
ranges were taken on all bromides.
3. Benzene was thicphene free, C. P. and was dried
over sodium before use.
4. Diethyl ether was C. P. anhydrous, and was dried
over sodium before use. During the last of the work it
was necessary to use U. 3. P. ether which.was first
washed with water to remove the alcohol, chloroform,
etc., dried over calcium chloride, distilled from
sodium, and dried over sodium.
5. Petroleum ether was dried.over sodium (B.P.30-65°).
6. Acetone was C.P. and was first dried over sodium
sulfate.
7. magnesium turnings sepecially prepared for Grignard
reactions were used after being dried in an oven at
50°.
8. Aluminum.chloride was Bah r's Analyzed, special
for condensations.

9. Acetic anhydride was Eastman.

10. Iso-butyryl chloride was prepared for use by the
action of phosphorous trichloride on iso—butyric acid.
B.P. 90~9l°at atmospheric pressure. (13)

11. Dimethyl iso-butyl carbinol was prepared by Binder.
(1.)

12. Dimethyl sec-butyl carbinol was prepared by Binder.
(L)

13. Triethyl carbinol was prepared by Binder. (4)

14. Diethyl n-prcpyl carbinol was prepared by Langdon.
(11.)

15. Methyl di-iso-prOpyl carbinol was prepared by
Meloy. (15)

16. 2,4,4-trimethyl—pentanol-2 was prepared by Guile.
(10)

Carbinols

1. Dimethyl iso-propyl carbinol

This was prepared by the action of acetone on the
Grignard reagent, iso-prOpyl magnesium bromide. Yield-
35%.
2. Dimethyl n-butyl carbinol

This alcohol was prepared from n-butyl magnesium
bromide and acetone (16). Yield - 575.
3. methyl ethyl iso-propyl carbinol

Prepared from methyl iso-prOpyl ketone and an
ethyl Grignard reagent. Yield - 63$.
4. methyl ethyl n-prOpyl carbinol

This was prepared by the method of Shitmore and
Badertsoher, (17) from methyl ethyl ketone and n-prOpyl
magnesium'bromide. Yield - 60$.
5. Dimethyl n-amyl carbinol

Prepared from n-amyl bromide and acetone.
Grignard's reaction (18). Yield - 40%.
6. Dimethyl sec-amyl carbinol

This was prepared by the above method, substituting
sec-amyl bromide. Yield - 12$.
7. Dimethyi iso-amyl carbinol

This alcohol was also prepared by the same method
using iso-amyl bromide. Yield ~ 41$.
8. Dimethyl active-amyl carbinol

This was prepared from active-amyl bromide and

acetone by the above method. Yield - 135.

 

3

9. Dimethyl tert-anyl carbinol
2,3,B-trimethyl-pentanol-Z was prepared from
directions given by Uhitmore and Badertscher (18),
and consisted of the preparation of the ketone, 3,3-
dimethyl-pentanone-Z and reacting this With methyl
magnesium.iodide. Yield - 12$.
10. Diethyl iso-prOpyl carbinol
This was prepared from the interaction of one
mole of iso-butyryl chloride and two moles of ethyl

magnesium bromide. B. P. 64-660 at 20mm. Yield - 25$.

Condensations

1. Dimethyl iso-prOpyl phenyl methane

Run in an ice water bath, by the method of Fox
(3). Yield - 20,15.
2. Dimethyl n-butyl phenyl methane

Run according to that method used by Binder (4).
Yield - 1,0373.
3. Dimethyl iso-butyl phenyl methane

Run by Binder's technique (L). Yield - 19$.
4. Dimethyl secobutyl phenyl methane

From benzene and dimethyl sec-butyl carbinol (4).
Yield - 28$.
5. Methyl ethyl n-prOpyl phenyl methane

From.methyl ethyl n-prOpyl carbinol by condensation
with benzene (A1013) (2.). Yield - 31.315.
6. Hethyl ethyl iso-prOpyl phenyl methane

Run by the Shaker method, the aluminum chloride
being slowly added to the stirred mixture of carbinol
and benzene. The reaction mixture was cooled in a
salt-ice bath, which.was allowed to warm to room
temperature upon completion or the addition. Yield -
23%. (A)
7. Triethyl phenyl methane

From triethyl carbinol by the method of Binder
(4). Yield - 50%.
8. Dimethyl nnamyl phenyl methane

Run in a cold water bath by the Shaker method,

using dimethyl n-amyl carbinol and benzene in the

10

presence of A1013 (5). Yield - 23%.
9. Dimethyl iso-amyl phenyl methane

Run by Sculati's technique (5). Yield - 24d.
10. Dinethyl sec-anyl phenyl methane

Run as above (5). Yield - 8.4;.
11. Dimethyl act—anyl phenyl methane

From.dimethy1 active-amyl carbinol using the
method of Sculati (5). Yield - 14%.
12. Diethyl n-propyl phenyl methane

Run according to the technique of Breining (6).
Yield - 19:3.
13. Diethyl iso-propyl phenyl methane

Run as above (6). Yield ~ 20%.
14. methyl di-iso-propyl phenyl methane

This was prepared using a slightly modified
technique. Cline (8) prepared this product in small
amounts by first suspending the benzene and aluminum
chloride in petroleum.cther, cooling to a minus 30°
and slowly adding the carbinol. In this condensation,
the suspended benzene, aluminum chloride, and petroleum
ether, were stirred for twenty-four hours at room.
,temperature, cooled over-night in a refrigerator, and
then cooled to about a minus 24°. The carbinol was
then slowly added so that there was no appreciable
change in temperature. This treatment gave a higher
yield of the desired product. Yield - 5%.
15. 2,3,3-trimethyl-2-phenyl pentane

From.2,3,3-trimethyl pentanol-Z by the technique

11

evolved by Wesson (9). Yield - 6.23.
16. 2,4,A-trimethyl-2—phenyl pentane

Run by the Shaker method, the aluminum chloride
being slowly added to a stirred mixture of benzene,
petroleum ether, and carbinol, which was cooled in a

Salt-ioe bath. Yield "' 7.1.53.

12

Preparation of derivatives

In the technique evolved by Ipatieff and Schmerling (2)
either the mono- or the di-acetamino derivatives may be pre-
pared as the worker desires. By varying the nitrating mixture
either one may be successfully isolated as the principal
product, or both may be obtained from the same small amount
of starting‘material required. The derivatives chosen here
are the mono-acetamino alkyl benzenes.

The directions given are as follows:

"Procedure~- A:mixture of 0.5 to 1.0 0.0. of the
aromatic hydrocarbon and 5 c.c. of a nitrating mixture was
shaken for three to five minutes. The nitrating mixture con-
sisted of equal volumes of sulfuric acid (d-l.84) and nitric
acid (d-1.42), when the mononitro compound was desired as the
chief product, or of two volumes of the sulfuric acid to one
of the nitric acid when it was the disubstituted derivative
which was to be obtained. Ho attempt was made to cool the
reaction mixture. when the evolution of heat had ceased, the
mixture was poured upon a small amount of cracked ice, the
oily nitro layer was taken up in ether, washed twice with
water, and the ether was evaporated on a water-bath. To the
residue was added five grams of granulated tin, 5 0.0. of
concentrated hydrochloric acid, and sufficient ethyl alcohol
to bring all of nearly all of the nitro compound into
solution. The mixture was shaken until reduction was com-
,plete as was shown by the absence of marked turbidity on
ixouring a test portion into water. This usually required

less than ten minutes. In those cases in which the reduction

13

took place more slowly, the reaction was hastened by heating
the mixture on the water-bath; usually, however, the re-
duction was very exothermic end did not require the appli-
cation of external heat. when reduction was complete, the
aqueous alcoholic solution was decanted from the excess tin
into about 20 c.c. of water. The solution was extracted with
ether and sufficient concentrated alkali was added to the
aqueous solution to dissolve nest of the precipitate of tin
hydroxide which formed at first. The amino compound was
extracted with ether, washed with water, dried by shaking for
a few minutes with potassium carbonate, and the ether removed
by evaporation. To the residue was added one c.c. of acetic
anhydride. The derivative usually crystallized almost imme-
diately. The material was warmed with 5 c.c. of water to
hydrolyze the excess anhydride. Since some of the acetamino
derivatives are quite soluble in dilute acetic acid it was
occasionally necessary to evaporate almost to dryness the
solution containing the hydrolyzed acetic anhydride. The
crude derivative was filtered and then recrystallized from
hot water or dilute alcohol, yield 40-70%.”

This was found in general to be satisfactory, but a few
modifications were made. As the mono-derivatives were the
only ones desired, the nitrating mixture consisted of equal
parts of sulfuric and nitric acids. The ether extract of
the reduced product was evaporated, the complex broken by
neutralization with sodium hydroxide, the pure amine ex-
tracted with ether, and the ether evaporated. It was also

found necessary with most of the amines, to reflux them with

 

lnI.Il'
lull

14

acetic anhydride for five or ten minutes. The resultant
solution.was then cooled, hydrolyzed with 25 c.c. of water,
and then carefully neutralized with 10$ sodium hydroxide.
The oily liquid was freed of water by filtration and washed
with water several times.

With the exception of the octyl derivatives, recrystal-
lization from.dilute alcohol was convenient. Hexane and iso-
prOpyl alcohol diluted with water also worked very well.

Those derivatives which the author was unable to
crystallize as indicated in Table.A refused to come down from
a great variety of solvents. All the common solvents known —
water, alcohols, hexane, Shellysolve, acids, dioxane,
nitrobenzene, benzene and others, were tried with no success.

Some of the derivatives crystallised from.the oils on
.long standing (a year), but attempts to recrystallize them

from any solvents were of no avail.

15

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20

Discussion

The general procedure for the preparation of the acet-
amino derivatives of the alkyl benzenes described in this
'worh consisted of nitration by means of a mixture of equal
parts of c ncentrated sulfuric and nitric acids; reduction
of the product with tin and hydrochloric acid; and acylation

of the pure none-amine with acetic anhydride.

1: a
m- m n so __;-,
n ED + n.03—s—ea n' {{QNOVF H20

nu§Q1~202+ H figi—e nuggnnz-i— H20

g R
~‘- 4’ - -’ - th<“i H
n RDI‘LZ + (mambo —————-> 12' SD c3t13+ 20

In a few cases, pure amines (para), which had been pree
viously prepared in the laboratory, were acylated. Helting
points of these derivatives checked with those made by the
above method.

Fairly good yields resulted with all the products,
averaging about 40%.

Evidently those derivatives which the author was unable
to crystallize possess a latent lattice formation which
makes recrystallisation impossible. This is the only method

of explaining the resultant crystallization from the oils on

long standing. The forces necessary to form.the lattice work
are not sufficiently strong to permit latticing in solvents.
Ho generalizations on the melting points can be made
aside from the fact that lengthening the chain lowers the
melting point, and breaching (heaping of eurogens) raises it

to a certain extent.

‘3’)

“I-

8113:; vary

1. Some tertiary alcohols were synthesiro and condensed
with berzene in the presence of aluminum chloride to form
the elk l benzenes.

2. Identification of tertiary alkyl benzenes has been made
through the preparation f the mono-acetamino derivatives.
The tectnique consists of nitration, reduction, and ecylatiOn,
and may be applied quickly to small amounts of the hydro-
carbon.

3. Fifteen of these derivatives have been successfully re-
crystallized. Kelting points and crystal forms have been
recorded.

4. Various solvents, scratching, seeding, cooling, and
other accepted methods of inducing crystallization (20) were
utilized on the remaining derivatives which were those of
the tertiary octyl benzenes. These were not successful.

5. Some of these on long standing crystallized from.the
oils. however, attempts to recrystallize fron.solvents

failed.

-_._ VDP‘qi‘a‘Jib '.‘

 

Bibliosrephy

1. Iputieff, Carson, Fines J. in. Clo . :00. 58 919 1936
I etieff ens Pines Ibid 58 1056 1936
Grosse enfl Ipatieff Itid 57 2415 1935

Ipetieff, Ionnrcusky, Pines Ibid 918 1936

\D
0.1

2. Ipetieff one Schnerling J. in. Chen. Soc. 59 1056 1937
3. H eton and Fox Lester's Tnnsis 1934
L. Euston and binder unster's ThuSlS 1935
5. Huston and Boulati master's Thesis 1936
6. Eueton and areining Hester'e Tb sis 1933
7. Huston and Cline Easter's Thesis 1939
8. fiuston and Synder Keeter's Thesis 1939
9. Huston and Wesson Iastcr's Thesis 1940
10. Huston and Guile . J. Am. hem. Soc. 61 69 1339
11. Organic Synthesis Coll. Vol I, Page 23
12. Organic Synthesis Coll. Vol I, Page 138

13. Bercker Am. Chin. Fnye. {5) 26 468 1.s2

14. E ston and Lnngdon Master's Thesis 1939
15. Huston and Leloy Doctor's Thesis Unpublished 1941
16. Whitmore and Cerch J. Am. Che . Soc. 55 1119-

1124 1933
17. Whitmore and Badertecher J. in. Cher. Soc. 55 1559-

67 1933
18. Unitnore enfl Endertscner J. Am. Chen- Soc. 59 1561 1933

19. Shoesnitn and fiackie J. Am. Chem. too. 51 2335 1923
Beiletein, 14th Edition,

Volume III, Page 1167

20. horton Laboratory flecdnique in
Organic Onenistry, Pages 147-165

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