CZCJINDENSATION OF TERTIARY
ALiPHATlC CARBENOLS \X‘ITH
AROMATIC COMPOUNDS IN THE
azzazasazxzca OF ALUMINUM CHLORIDE
1:. HEPTYL ALCOHOLS
AND BENZENE
TREES 1131+: THE DEG’EE OF M, S.

.u

I‘v’ianin Ncr'man Binder

1935

 

 

COIIDEI‘ISATION OF TERTIARY ALIE'HATIC
CARBII‘IC'LS WITH AROMATIC COMPOUNDS II
THE 1" TESSNCE OF ALUEINUM CHLORIDE
II. HEPTYL ALCOHOLS AND WIN" £3413

CCNDEKSATION OF TERTIARY ALIPHATIC
CARBIROLS WITH AROL'EATIC COMPOUIEDS IN
THE PRESEEECE OF ALUEEINUIA CHLORIDE
II. HEPTYL ALCOHOLS AED DSLZ’ZIE

A Thesis

Submitted to the Faculty of Michigan
State College of Agriculture and Applied
Science in partial fulfillment of the re-

quirements for the master of Science Degree

BY

marvin Norman Binder

ACKKOWLEDGEEENT

The author takes this cpgortunity to
acknowledge his indebtedness to Dr.
R.O.Hustcn for his friendly advube
and helpful suggestions during the

performance of this work.

331608

‘1‘ (fifth'fl'sq
\ih ‘ ’.\n :5 D

HISTCTLI ’3.:'.L

Surgery

ether tethede for Preparing the
tert—Alkyl benzenes

EXPE“ 133?

AL

Eeterials

Prefieration of Cerbinols

Condensatione

A. 3

methyl npbutyl carbinol, benzene,
and A1013

Table of Results

Dimethyl iso-butyl cerbinol, benzene,

Table of Results

Dimethyl sec-butyl carbinol, benzene,
end A1313

Be 16 of Results

Eimethyl tert-butyl carbinol, benzene,
and A1613

yethyl ethyl n—uropyl carbincl,
benzene, and £10 J13

Table of Results
Triethyl oarbinol, benze ene, and A1013
Teble of Results

ilet thyl ethyl lee-RIO pyl carbinol,
ben qzene, endA A1013

*3
C3"

ble of Results

Page

03

13

14
16

17
19

'19

80
23
23
25

h)
6)

THEGRETICAL
Determination of Physical Constanta

Index of Refraction end molecular
Refractione

Belling Points, Density, and Holeculer
Volama

Surface Tension and Parachors
Structure of Alkyl Benzenee

HISTORICAL

A history of condensation reactions, brought about by
such catalysts as H3804, P305, 35304, MgClg, ZnClg, P015,
A1013, etc. has been amply covered by former workers in
this laboratory. This material is already available in
good form, however, it was felt necessary to include a
brief resume of research carried out in this laboratory
involving the reactions of alcohols with benzene in the
presence of aluminum chloride as a catalyst. The alcohols
include aromatics, aliphatios, and mixed aromatic aliphatice.

The first work in this field was started by Huston and
Friedmann (,1. La. m. m” .18.. 2527, 1916). They found
that primary aromatic alcohols react with benzene in the
presence of aluminum chloride. henzyl alcohol and benzene

react to give diphenylmethane as the principal product.
c a nu.oq 0.: 3101 c p-3q.c u 3.0
some“. + e16 ——3-> 6-5 on as + .2

Later work by Huston and Friedmann (1,Ԥa, Chem. 890.,
29, 785, 1918), shows that secondary aromatic alcohols con-

dense eith benzene according to the reaction:

0 a-\ can \
6 3/0393 + 06136 A1013; 0 5/CHC6H5 4- H20
R R

 

B may be methyl, ethyl, or phenyl. A better yield is ob-
tained when R. is phenyl.
Reactions with tertiary aromatic alcohols and benzene:
Huston‘ found that triphenyl carbinol will not condense
with benzene to form tetraphenyl methane as eXpected, In-

‘ unpublished

stead, the product is triphenyl methane,
(06a5)3ccn + cask,5 “-01 (0335);;03 4. ___

Apparently, the oxygen is removed from the carbinol.
Where this oxygen goes to, has yet to be determined.

Huston, Eilsey, and Hradel (master's Theses)‘ found
that diaryl-alkyl carbinols do not condense with benzene;

instead, dehydration occurs.

(Ceiislzyoa + case ——3—>A1°1 cfiHS‘c-cz-IC' 3 + ago
0235 0635’

Huston and haoomber’, in working with dialkyl-aryl
carbinols, observed no condensation but dehydration in-
stead.

ceiispg 03135 + cat-‘5 Macsflsp-caeas 4» H30
ages on 031-25

Condensation of aliphatic carbinols with benzene in
the presence of aluminum chloride:

iuston and Sager (,1. .1323. 91393.2. Egg" is. 1955, 1926)
report that saturated aliphatic alcohols do not condense
with benzene. among these are methyl, ethyl, prepyl, iso-
propyl, butyl, iso-butyl, and iso-amyl. However, they
found that the unsaturated alcohol, allyl alcohol, will

condense with benzene.
Gaza-casinos + 06216 M3.) CHfCHCHBCGHE, + ago

Huston and Hsieh (Doctor's Thesis)‘, with slight
‘ unpublished

modifications in procedure, were able to condense alipha-
tic alcohols with benzene and benzene derivatives. Pri-
mary alcohols do not react at all; secondary alcohols re-
act very slightly; tertiary alcohols react very readily

to form the corresponding alkyl benzene.

CF~3\ :13
ens—0.03 + Gena ———1-'i, c..3\c—c~ 5 + no
0313/ Ciis/

Huston and Fox (master's Thesis)’ condensed tert-
butyl alcohol, tert—amyl alcohol, dimethyl nppropyl and
dimethyl iso-prOpyl carbinol with benzene to obtain.tert-
butyl benzene, tert—amyl benzene, dimethyl nppropyl phenyl
methane,w .d din ethyl iso-prooyl phenyl methane in good
yields.

 

l.’Primary and secondary aromatic alcohols condense
with benzene in the presence of aluminum chloride to form
the corresponding benzene derivative.

2. mixed tertiary aliphatic-aromatic alcohols do not
condense with benzene. Dehydration of the carbinol occurs
to form the corres;')onding unsaturated hydrocarbon. ‘

3. Unsaturated aliphatic (priznary) alcohols, with
the double bond adjacent to the hydroxyl carbon, condense
with benzene.

4. Tertiary aliphatic alcohols condense readily with
benzene, secondary alcohols react only slightly, while pri-
mary alcohols do not react at all.

‘ ungublished

Other methods for Preparing the tert—Alkyl Benzenes

Digethz} i§Q=b§tzl phony; methane~
From auchlor-3,4-dimethyl pentane and benzene in the
presence of aluminum chloride (genreiner,g, 2;, [2], 83,

294). 3.9. 218°; dli - 0.8741; nfi5-5 - 1.4938.

detail sisal sznrnnrl, h a
From 3-chlor-3—methyl hexane and benzene in the pre—

 

sence of aluminum chloride (Helge,‘g,12;, [a], 89, 452).
3.9. 110-112°/15 mm.; egg - 0.9319; n§5 -‘1.4995.

mm gheny; gr ethane-
From triethyl chloromethane and benzene in the pre-
sence of aluminum chloride (Schreinsr, g, 2;, [2], 82,

296). B.P. see—222°; dag - 0.8858; n35 - 1.4921.

EXPERInE’l-I TAL

MATERIALS

The butyl bromides were obtained from Eastman Kodak
Laboratories. It was also necessary to prepare some of the
bromides from the corresponding alcohol because the supgly
on.hand was not sufficient to carry on satisfactory re—
search. The alcohols were also obtained from Eastman.

Tertabutyl chloride was prepared from tert—butyl
alcohol.

Methyl ethyl ketone and ethyl carbonate were obtained
iron Eastman. ’

Ethyl bromide was prepared from commercial (95%) ethyl
alcohol.

Acetone was C.P. grade.

n~frogyl bromide and iso-proyyl bromide were Prepared
from the correSponding alcohols.

hagncsium (turnings), especially prepared for Grignard
reactions, was used.

0.9. thicyhene—free benzene was used in all condensa-
tions.

Aluminum chloride was a high grade commercial product.

(11

Preparation of Carbinols

Dimethzllgnggzl’carbinol gg_2-methyl hexnnol-Q,
From.n~buty1 magnesium bromide and acetone (?hit§g;e

a. Church, ,1. £33. Shen- m., 55., 1113-24, 193:3).
B.P. 139-1430

 

Aggroximate yield obtained - so;

Dimgthz; iggzbutzl — bin 9; 2.4-dimeth1; gentgggl-z,
From iso—butyl magnesium bromide and acetone (gagggb
Qagngeegt, and larger, ,1. g. 933;. $339., §_3_._, 1483-91, 1939)
‘ 3.9. 137-1390
50—530 (30 mm)
n§°.. 1.4173

Approximate yield obtained - 30%

Dimgthg; sec—bgtx;._;;§;gglqgg 2,3—dimethyl gentnn —3
From sesabutyl magnesium bromide and ecetoue (Edgar,
Culinfeert, & Earlier, ,1. 51m. $93., §:_]_.,, 1485.91, 1939)
3.9. lee-150.50
53-53.5° (30 mm)
n30 - 1.4370

Approximate yield obtained - 25$

Dimgthgl tertabutyl cerbin 1 or 2,2.3-trimethyl butenol-S,

From tertubutyl magnesium chloride and acetone (this,

   

'_.__
_1 ,.

M, ,1. £33.. Chem. Soc... £53., 1559-67, 1935; cigar, Celin-

gaert, & barker, ibid., é}, 1485-91, 1929). Letter yields

0)

are obtained when tert—butyl chloride is used instead of
tert-butyl bromide. '
B.P. 130° n.P.. 17°

The cerbinol is Very hyngSCOQiO and forms a hydrate
with melting point around BQ~83°. When it is distilled
in small amounts and without special precautions, only the
hydrate is obtained. then larger quantities are handled,
the distillate is a mixture of the liquid carbinol and aci-
cular crystals of its hydrate. The hydrate loses its water
readily when kept in a dessicntor over bdrium oxide (32., 9.,
a: 1. ) .
Approximate yield obtained - 15 to 20%

‘hethzl ethyl Q-grogzl cerbingl,
From nppropyl magnesium bromide and methyl ethyl ke-
tone (whitmgrg & finder-teacher, 1. fig. £13334. £593., §_5_, 1559-
67, 1933).
B.P. 139-141o
56° (30 mm)
n30 - 1.4331

Approximate yield obtained - 61%

‘gggh1;_ethyl'i§o-2rgeyl cerbingl,
From isOaprcpyl magnesium bromide and methyl ethyl ke-

tone (ehitm re & Everg, g; in. Chem. 333., 55 812-15, 1933).

—,

         

3.2. 138—14o° (750 mm)
49~5o° (20 mm)
n30 - 1.4287, 1.4280

Approximate yield obtained - 26%

21.21211 aarhiesl.
From ethyl magnesium bromide and diethyl carbonate
(we; 8: harvgl, Qrgnnig Synthesis 35;, 98-100, 1931).
3.9. 140-1420
72—730 (53 mm)
Approximate yield obtained .- 823:3

CONDBRSATIORS

 

A. Dimethyl n—but l carbinol, benzene, and A1C13,
Trial 1.
Carbinol - 1 eq. - 20 g.
Benzene - 5 ' — 67 g.
A1613 - § ' - 11.5 g.

A 500 m1. three-necked round-bottom flask was provi-
ded with a mercury sealed mechanical stirrer, a tube to re-
mcve H01 fumes, a thermometer, and a separatory funnel.
Benzene was placed in the flask and the stirrer started.
The entire amount of A1313 was then added to the benzene.
The A1C13 is thus uniformly suspended in the benzene. By
this procedure, the temperature may easily be controlled
by the rate of addition of the carbinol. The carbinol was
then added drop by drop (about a drop every five seconds).
Three hours elapsed during the addition. Considerable 301
was evolved during the reaction. The temperature was easi—
ly maintained between 25 and 30° C. and not allowed to go
above 30°. 50 external cooling was necessary. The entire
mixture was stirred for an additional two hours. During
the addition of the carbinol, the mixture changes from a
yellow to a dark red color, forming a coagulate which breaks
up after more of the carbinol is added and later turning a
dark red-brown. Mixture was allowed to stand overnight
(about 18-30 hours); then decomposed with ice and hydro—
chloric acid. The benzene layer was segarated and the a-

queous portion extracted several times with ether. In the

10

other extraction, it was necessary to add H31 to destroy the
ether—water emulsion which formed. The other and benzene
extracts should be washed with dilute sodium carbonate to
remove any remaining 331. It is then dried over anhydrous
calcium chloride. The other and benzene are distilled off
and the residue distilled in a fractionating column at re—
duced pressure. The following fractions were obtained at
80 mm.
1. (so - 106°) - a g.
II. (103 ~11090) - 13 g.
III. above 109° 4- 6 g.
The fraction boiling at IDS-109° is dimethyl n—butyl
phenyl methane.

Equation of Reaction:

C: CH .
CH3CHgCHgCHgg-8H + C635-él§;3*CHaCchflzcEQQ-gefis-+ 330
CBS CH3

Trial II.
The same quantities, procedure, and conditions were
arsed as in trial I. Fractions at 20 ms.:
1. (so -.1oe°) -: 2 g.
II. (108 - 109°) - 12 g.

0)

III. Asove 103° - g.
Trial III.
Ihe same procedure was followed as in trial I & II.
Carbinol ~ 1 eq.1~ 80 g.
benzene - 4 “ - 54 g.

— " — 11.5 g.

H

0

N.

£31313 -

11

The following fractions were obtained at 30 mm.:
I. (so -- 106°) - 1-}; g.
II. (106 - 109°) - 11 g.
III. Above 1090 - 6 g.
An increase in the amount of A1013 seems to lower the
yield of alkyl benzene.
Trial IV.
Cureinol - 1 eq. - 20 g.
Benzene —I6 ' - 81 g.
1102!.3 -. g- ' — 11.5 g.
The following fractions were obtained at 20 mm.:
I. (30 - 106°) - 3 g.
II. (106 - 100°) - 12 g.
III. Above 100° ~ 5 g.
Trial V. _
Carbinol -1 eq. - 80 g.
Benzene — 7 ” - 94 g.
A1013 - é ' - 11.5 g.
The following fractions were obtained at 20 mm.:
I. (so - 105°) -. 1-}; g.
II. (108 - 109°) - 13 g.
III. Above 109° - 5 g.

So far, in all trial runs only one-sixth of a mole of
the carbinol was used. It was thought that it larger quan-

tities are used a better yield of alkyl benzene is obtained.

In.the next trial one—half mole of the carbinol is used.

13

Trial VI.
Carbinol ..1 eq. - 58 g.
Benzene - 5 ” - 195 g.
A1013 - fi ” - 33.4 3.
Upon fractionation at 30 mm. obtained

I. (106 - 109°) - 39 g.

Analysis of Fractions

Fraction (SO-106°) contains a small amount of z-chlor-'
3—methyl hexane, n.9, 132°; 39—4o°/2o mm.; n30 - 1.4310.

As a check, the chloride was prepared from the corres-
ponding carbinol by saturating with dry H31 gas. The pro-
duct boiled at 39-40°/20 1mm; 113° - 1.4308.

The boiling point of the chloride, as recorded in the
literature, is 130—1350.

Fraction (106-1090) is the condensation product. di—
methyl npbutyl phenyl methane. After several fractiona-
tions, it boiled at lO?~lO7,6°/30 mm. This compound is

.59: recorded in the literature.

Carbonpflydrogen Determination:

Wt. sample wt. coa % 0 wt. H30 % H3
.2003 .6504 88.61 .2047 11.44
.3149 .6963 88.35 .2203 11.47
Calculated for °1sfleo 88.63 11.36
.Moleculer Weight Determination:
Wt. sample Temp. diff. Wt. benzene hol. wt.
1.0136 .335 43.4442 169

Calculated for 013820 176

13

The following table shows the yields of dimethyl
upbutyl phenyl nethene obtained from the veriOus trials.

Table of Results

- Eeaotnnts Products
Cnrbinol Benzene A131. not.Yld. Theo. Yld.
g. eq. g. on. 3. e.. g. g. p
20 1 6? 5 11.5 e 13 30.3 39
20 1 e7 5 11.5 e 12 30.3 39
so 1 54' 4 11.5 5 11 30.3 as
20 '1 81 6 11.5 t 12 30.3 ee
20 1 94 7 11.5 e 13 30.3 43
58 1 195 5 33.4 e 39 88.0 44

Only a light increase in yield is observed when lar-
ger quantities are used.

Fr ction boiling above 1090/20 mm. was fractionated
to yield a heavy yellow-colored oil boiling at 135-1600/
30 mm. 9robnbly a polymer; it may also contain some di-
‘alkyl benzene. It was allowed to stand in the ice-box

for several months but no crystallization was noted.

14

B. W igo—butv; carbin l benzene, and 2.3.313,
Trial I.

Carbinol - 1 eq. - 10 g.

Benzene _- 5 “ 1- 34 g.

£1013 -»§ “ - 6 g.

The same procedure used in previous condensatione was
followed. The carbincl was added, drop by droo, to a sus-
pension of 111013 in benzene. 501 was evolved. The temp
parature was kept between 25 and 30°. After about half ~
of the carbinol had been added, a'black coagulate formed
which broke up as more carbincl was added. The mixture
turned dark red-brown. Three hours elapsed during the
addition of the carbinol. Stirring was continued for two
more hours. Allowed to stand overnight. Decomposed with
HCl and ice-water, etc. Distilled and fractiotnted.

Recovered benzene - 24 g.

Fractions at 30 mm.:

I. (3:5 - 40°) - 4 g.
11. (40‘- 99°) -1% g.
III. (99 - 103°) - 3 g.
IV. Above 103° - 4 g.

Equation of Reaction:

CH H 3 (33 H CH
H-g—E-Q—SE—OH + CSHS fla-DWGHf‘; + H80
33 H CH3 C33 H CH3

The fraction boiling at 99-103° is the condensation
product, dimethyl iso-butyl phenyl methane.

Trial II.

Carbincl - 1 eq. — 80 g.

Benzene — C ” - 67 g.

The Iclloring fractions were othined at 80 m:.:

5’.

U

E.
g.-w

H
H
A
.5
I
D
(-J
' O
v
I
O) M!" (II

it
?‘
L)
A
0
U
3

3'.

Analysis of Fractions

Brie tion (33-4LJO) alien fractio ted yi elded a liquid
boiling at 33—340/20 mm. It is saturated and contains ha- ‘
lide. irehahly the chi are com;cund of the carbinol, Z-chlor-“
2,4-di.m M2231 pentane. n50 - 1.4239.

This coniound is recorded in the lite ratuze with th
folio i'v yrs erties: 3.P.1LL-13"°- mi? - 1.4202
as a check, the chlcrc congound was pragared by satura-
ting dizet li"l iso-bntyl carbinol with drya I’Cl g: . The pro-
duct had the following progerties:

B.P. 33—c "30/30 mL. ngg - 1.4235

Det Lr'inntion of ii a hoilin 15 point at atmoegheric pres-
sure rte difficult. The substanc a deer; mosses, liberating
H01.

The craie fr:10tion (33.4; 01’0 n3) alas coz‘. taine some

unsaturate d praduete as 31 mrn by the bromine te st.

16

The fraction (40-99 ) is a mixture of the chloride and
condensation product.

Fraction (99-1030) is the condensation product, dimethp
yl ieo~buty1 phenyl methane. When fractionated several times
it yielded a fraction with the properties:

2.2. 216—2170 (745.6 mm)
100~103° (20 mm)
. n$6~54- 1.4340
This corresponds to the properties of dimethyl ieo-butyl
phenyl methane as recorded in the literature.

2.2. 212° né5-5 - 1.422

The following table shows the yields obtained from the
various condensatione, dimethyi iao»butyl phenyl methane be—
ing the product.

Table of Results

Reectenta Product

Carbinol Benzene A1313 Act.Y1d. Theo. ggd.
89 39' 80 eq. 8- 6%. 8- 8- P

10 1 84 5 6 § 3 15.5 19.4
20 1 ' 67 5 11.5 § 6 30.3 12.2
20 1 81 6 11.5 § 5 30.3 16.5
22.2 1 103 7 13.7 g 5 35.2 14.2
30 1 98 5 16.? g 8 44.0 18.4

17

G. Dimethfl. gee-mtg. gm penggne, and M,
rr1a1 I. '-
Carbinol —.1 eq. ..23.2 g.
Benzene ..5 ' - 73 g.
11101;5 .- § .. - 13.7 g.

The same procedure used in previous condensations was
followed. The carbinol was added to a suspension of A1013
in benzene with constant stirring. The temperature was
kept at 25°. Addition of the carbinol required three hours.
301 was evolved freely. Stirring was continued for two
more hours and the mixture allowed to stand overnight.

It was decomposed, extracted, etc. The extracts were
distilled and fractionated.
.Recovered benzene —r65 g.
The following fractions were obtained at 201mm.:
I. (331-.43°)«- 3 g.‘.
'11. (43 - 102°) ..1 g.
III. (103 -].08°) -- 5 g. {/0}. .flM)
IV. Above 108° .. 8 g.

The fraction boiling at 102-1080 contains the conden-

sation product, dimethyl sec-butyl phenyl methane.

Equation of Reaction:

03 0235 CH
H::g..¢-8H-+ 05H6._él§l§€,. 3.2c..c. 635 4_ 320
033 CH3/ CF :13

Analysis of Fractions

Fraction (33-43°) contains halogen and is unsaturated.

18

i traction was isolated boiling at 38—39°/80 mm. This frac-
tion contains halogen but shows no unsaturation.
ngo - 1.4264

This ccrresoonds very closely to the chloro compound, ’
2-chlor-2,3-dimethyl pentane. It has been previously shown
that the fraction obtained in the diaethyl iso-butyl conden—
sation is the chloro compound. Since these conyounds are
isomeric, their boiling points are closely related.

Fraction (43-108°) is a mixture of the chloride, con— y”
densation eroduct, and unsaturated products.

Fraction (ICE-108°) was repeatedly fractionated to yield
a liquid boiling at 105-1070/20 mm. It is saturated and does
not contain halide. It was assumed to be the alkyl benzene.

Dimethyl sec butyl phenyl methane is ngtNrecorded in the

literature.

Carbonphydrogen.Determination:

Wt. sample st. 003 etc rt. H30 % 33
.2063 .6359 83.03 .2089 11.33

molecular height Determination:

ht.sample. Temp. diff. Wt. benzene Eel. It.
1.0623 .351 44.000 167
Calculated for Clgflgo 176

The following table shows the yields obtained from

various condensation trials, the product being dimethyl

19

iso—butyl phcfnl methane.

Table of Results

Reactants Products
Carbinol Benzene A101Q Aot.Yld. Theo. Yld.
8. 8Q. go eq. 8- 85. g. g. %
23.2 1 78 5 13.7 % 5 35.2 14.2
‘ ' l ' 5 ' § 4% ' 13.8
' l ' 5 ' § 5 ' 14.3
30 1 es 5 17 e 6% 44.0 15.0

D. Dimethyl tert-butyl carbingl, bcngene, agghélgl3,
Trial I.’

Carbinol «'1 eq. — 23.2 g.

Benzene - 5 “ — 78 g.

n1013 - § “ -13.7 g.

The carbinol was mixed with clout oneohalf of the quan-
tity of benzene and then added from a.dr0pping funnel to the
benzene-aluminum chloride suspension. Since the carbinol is
very hygroscopic and crystallizes, it was necessary to mix
it with some benzene to prevent crystallization. A calcium
chloride tube was attached to the funnel to exclude all
moisture. The reaction proceeded in the usual manner. Upon
distillation and fractionation, obtained the following:

Recovered benzens'u 70 g.
Recovered carbinol - 13 g.

.r. _ ‘, : " , ' ‘1".
1 ' 4‘ $451!" . f} L]; I} l .‘K . \. I" H.) .

Fractionation at 30 mm. yielded.

C Cr --"‘ If}

I. (104 - 109°) - lgto 1% g. (a? ~»»wahe
II. AbOVG 109° ‘ 2 g. (9Q.

The fraction boiling at 104—1090 has the characteris-
tic odor of the other butyl hydrocarbons, does not contain
halogen, but shows unsaturation. The boiling point cor-
responds to the boiling point of the other hydrocarbons.
Probably it is the hydrocarbon with a little of unsatura-
ted material.

Due to the difficulty involved in working with the
carbinol, that is, purification and dehydration, work was

discontinued.

E. mgghzl MW carbingl, “men and £1,913,
Trial 1.
Carbinol —>l eq. - 23.2 g.
Benzene — 5 ' -78 g.
A1C13 - § " - 13.7 g.
The same procedure used in previous condensations was
followed. Distillation and fractionation yielded:
Recovered benzene - 63 g.
Fractions at 15 mm.:
I. (as - 98°) - 1% g.
11. (as - 101°) ~ 13.5 g.
III. Above 101° - 4 g.

Equation of Reaction:

T1

..-._ 633
c Saga-0.021 + Cefie “”5 4> CgE-Zg-EO-C‘H‘. + H30

 

C 357 C 3117

The fraction boiling at ss-101°/15 mm. is methyl ethyl

appropyl phenyl methane.
Trial II.
Carbinol - 1 eq. - 39 g. ‘
Benzene - 5 ' - 130 g.
A1013 - § ' - 22 g.
Distillation and fractionation yielded the following
fractions.
Recovered benzene - 107 g.
Fractions at 15 mm.
1. (35 - 99°) -. 3 g.
II. (99 - 102°) - 24 g.
111. Above 102° — s g.

Analysis of Fractions
Fraction (es—99°) when fractionated, yielded a liquid

boiling at 40-43°/20 mm. This fraction is saturated and
contains halogen. It corresponds to the ohloro compound,
methyl ethyl n-prcpyl chloromethane. The chloro compound
was prepared from the corresponding carbincl by saturating
with dry H01 gas. Its properties are

B.P. 410/20 mm. n50 -.1.4ess
is recorded in the literature, its properties are

3.9. 39-40°/15 mm. n§51~ 1.4271
Only a very small amount of the chloride Was obtained from
the condensation reaction; about two to three grams from \

both condensations.

Fraction (QB-102°) when fractionated several times

yielded a liquid boiling at 1000/15 mm. and lOB.5~lO7°/
30 mm. It is assumed to be the condensation product,

methyl ethyl nppropyl phenyl methane. Its properties are
I n30 -y1.4ee4 n§5 ->1.4235

It is recorded in the literature sith the following pro-
perties: I

B.P. 110-1120/15 mm. n%5 - 1.4235
The boiling points do not check very closely.

Carbon—Hydrogen Determination:

Fit. sample wt. 003 '35: G at. H30 % 33
.3030 .6535 88.33 .3065 11.44
Calculated for Clgflgo 88.63 11.36

The following table shows the yields of methyl ethyl
appropyl phenyl methane obtained from.various trials.

Table of Results

Reactants Products‘
Carbinol Benzene A1013 Act.Yld. Theo. Yld.
E. 6Q. go 6C1. go eq. 3. g. I

39 1 130 5 23

23.2 1 78 5 13.7 s 12.5 35.2 35
e 24 59 4o

F. Irigthy; carbingl, penzene, and A1317,
Trial 1.

Carbinol - 1 eq.‘- 25.3 g.
Benzene - 5 "' - 78 g.
A1013 - % ' - 13.7 g.
The same procedure used in previous condensations was
followed.
‘Recovered benzene - 64 g.
Fractions at 30 mm.:
1. (33 - 105°) - 1 g.
II. (105 - 108°) - 13 g.
III. Above 108° - 5% 3.

Th fraction boiling at 105-108° is triethyl phenyl

C3

moths-me 0

Equation of Reaction:

A161

 

(03H5)30-CH 4- 06216 3e.(ozn5)30.cea5 + n30

Trial II.
Carbinol - 1 eq.‘- 39 g.

'7

Benzene — 5 ” — loO a.

A1013 - d 9 ~ 33 g.
Fractions at 20 mm.:

1. (33 - 105°) - 3 g.

II. (105 - 103°) - 24 E.

III. Above 108° - 7 g.

. 24

Analysis of Fractions
I Fraction (33-1050) when fractionated yielded a liquid
boiling at 43-43°/30 mm. It is assumed to be the chloride \
of the carbinol. As a check, triethyl chloromethane was i
made from triethyl carbinol and dry HCl gas.
3.9. 43°/20 mm. ago ~’1.4320
It is recorded in the literature with the following proger—
ties:
3.9. 143-144° n35 ~11.4828
Very little of the chloro compound was obtainoc; about one
gram from both trials.
Fraction (105-108°) was fractionated several times to
yield a fraction boiling at 107-108°/30 mm. It is assumed
to be the condensation product, triethyl phenyl methane. ’

8.9. 107.s°/20 mm.
225.2es°/745.8 ..

3° - 1.4975 n35 -L1.4ess

no
The following properties are recorded in the literature:

B.P. 230~2ee° n55 .11.4331

Carbonpfiydrogen Determination:

Wt. sample _wt. C03 % 0 Tot. ago e H3
.2031 .6581 88.37 .2071 11.41
Calculated for 013330 88.63 11.36

The following table shows the yields of triethyl

phenyl methane obtained from various trials.

 

 

D.)
(.51

Table of Results

Reactants Products
Carbincl Benzene A1613 Act.Yld. Theo. Yld.
g. eq. g. eq. g. on. g. g, %
25.2 1 7e 5 15.7 § 15 55.2 as
59 1 130 5 22 t as 59 40

G. Methyl ethyl isgzgrggxl carbinol, benzene, and A1013,
Trial I o

Carbinol - 1 eq.- 33.2 g.
Benzene — 5 ” a 78 g.
A1013 - § " ~ 13.? g.
The same procedure used in previous condensations was
follonel. Distilled and fractionated, at 20 mm.
Recovered benzene - 64 g.
I. (55 - 45°) ; 4 g.
11. (45 - 105°) - 5 g.
In. (105 -1oe°) - 5 g. “2.; MM)
Iv. Above 108° - 5 3.

Four more trials were made using the some quantities

as above. The same results were obtained in each case.

Analysis of Fractions
Fraction (35-450) was fractionated to yield a liquid
boiling at 41-430/30 mm. This was found to be the chloro ‘:
comgound, S-chlor-3,4-dimethyl pentene.
Fraction (45—1030) probably is a mixture of the chloro

compound, unsaturated products, and some rearrangement pro—

ducts. No definite boiling fractions could be separated.
Fraction(lOS-108°) when fractionated several times

yielded a liquid boiling at 105-1070/20 ma. This must be

the condensation product, methyl ethyl iso-propyl phenyl

methane which is not recorded in the literature.

Carbonpfiydrogen Determination:

fit. sample wt. 002 %.0 wt. H30 % H3
.2113 .6838 88.26 .2153 11.42
Calculated for 915320 88.63 11.36

Molecular Weight Determination:

ht. sample Tenn. diff. wt. benzene H01. wt.
1.0623 .352 44.00 166
CfilOUlfited for 013H20 176

The following table shows the yield of methyl ethyl

iso—proyyl phenyl methane obtained.

Table of Results

Reactants Products
Carbinol Benzene A1013 Act.Yld Theo. Yld.
g. eq. g. eq. g. eq. g. g. %
23.2 1 78 5 13.7 § 4 85.2 11.4

The higher boiling fractions of each group of conden-
sations have not been separated. no definite boiling frac-

tions could be isolated.

2?

Determination of Physical Constants

Density determinations were made by means of a small
picncmeter devised by the author. All determinations were
made at 30° 0. compared to water at 4° 0.

Index of refraction measurements were made with the
Abbe' refractometer.

Surface tension measurements were made by scans of
the Harkins' Drap-height method and by the Duflouy Tensio-
meter method. '

For the drop-weight method, surface tension.was cal-

culated by the formula,

Flu-9%?

.. surface tension in dynes/om.

‘5‘
j
(J

mass of drop in grams

- volume of droop 0%)

m 4 B ‘3’
I

- pull of gravity (981)
radius of tip (.27158 cm)

a: w
I

— a constant, obtained from
table corresponding to fig
The Dufiouy Tensionetor is a direct reading instrument,
that is, values for surface tension are read directly on a
dial.
The observed molecular volume was calculated by divi-

ding the molecular weight of the comgound by its density.

38

The observed parachor was calculated by the formula,
Pug-M

where P - parachor of comgound
M - molecular weight
d — density

3'- surface tension

molecular refractions were calculated by the formula,

. hula—.21
L” - n. + 2
where ED - molecular refraction

h — molecular weight
- density

n - index of refraction

Theoretical molecular volumes were calculated by the

formula,
n - number of carbon atoms
or Vm‘ a 16.3? n + 16.03 ‘+ 74.5?

n.~ number of carbon atoms in
aliphatic side chain
16.03 - effect of one hydrogen
74.5?- effect of phenyl ring

Index of Refraction and holecular Refractions

Substance n50 Ego
Cale. Found
cs,
n-césg-crg5a5 : 1.4943 58.55 58.68
£113
055 55
ape—c-d $5525 1 1.4928»' 58.65 58.67
033/ H 0:13 .
Cg}15\ (33.3.3 .
5.3-5-0515 v 1.4966 58.55 58.48
055’ sea
Size .
055575-8555 5 1.4864 58.55 58.53
02H5/
053
nee-c.8rn5 . 1.4974 58.65 58.54
GB; 021.5

From this table, the conclusion may be made that heap-
ing of eurogens on adjacent carbon atoms increases the in-
dex of refraction. Index of refraction is lowest when eu-

rogens are heaped, but not on adjacent carbon atoms.

Boiling Points, Density, and Molecular Volumes

Substance

CH3 H C. isU

CH .3 0.13
E~C’C-be}15
C2115, 0333

03.3.3

0 911.: “-0-ng 115

0“ 2:10;).

C3113 C 23;.

BQP.

285.5-224.5°
745.6 mm.

107-107.5°
20 mm.

216-2170
745.? mm.
101-1020

20 mm.

[i
218-8210
740 F1122}.
105 ~107°
20 {£181.

15 mm .

835-2880
745.8 mm.
107.50
20 55:1 .

221.8880
740.1 mm.

20 mm._
(:1 11"“‘1'1

f

7 4 1.3-.- \,\V\

o
.15.: p.
o

.8737

.8724

.8801

.8786

.8803

Gale.

204.49

204.49

204.49

204.49

204.48

204.49

V

111

Found

201.44

201.74

200.3. 3

199.83

188.83

30

molecular volumes as determined experimentally are
lower than the calculated value. The formulae develoyed
for calculation of molecular volumes only hold for straight
~chain compounds. Therefore, the calculated molecular vol-
ume would be the value for npheptyl benzene. The difference
between the calculated and the observed molecular volume
must be the effect due to chain branching.

According to Kauffmann, a decrease in molecular vol-
ume is due to hanging of eurogens on adjacent carbon atoms.
As shown in the table, dimethyl cec—butyl phenyl methane
and methyl ethyl iso—nropyl phenyl methane have a low mo-
lecular volume.

According to Kauffmann, the carbon atom in the benzene
ring, to which is attached an aliphatic side chain, may
act as a heaping center. In compounds 3%.. heaping or
groups in on a carbon atom adjacent to a carbon in a hen—
zene ring, the difference in molecular volume must be due
to the groups present. or the three isomers having
straight chain branching, dimethyl upbutyl phenyl methane
has the highest molecular volume; methyl ethyl n-propyl
phenyl methane is slightly lower, while triethyl phenyl
methane is still lower. It becomes apparent that heaping lyf
of like groups on an adjacent carbon atom causes a grea-
ter lowering of molecular volume than do unlike groups.

In triethyl phenyl methane, the three groups are exact-
ly alike and the molecular volume is lowest. When the

three groups are slightly different, as in methyl ethyl

32

appropyl phenyl methane, molecular volume should be some-
what higher and it is. Dimethyl n-butyl phenyl methane
when considered as the normal compound in the series should
have the highest molecular volume and it has.

Dimethyl iso-butyl phenyl methane has the greatest
molecular volume in the series. This increase in molecu—
lar volume occurs when eurogens are heaped on carbons not
adjacent to each other. Kauffmann states that heaping of
eurogens‘ng§,on adjacent carbon atoms increases the mol-
ecular volume and decreases the boiling point.

It seems peculiar that dimethyl sec-butyl phenyl me-
thane and methyl ethyl iso~propyl phenyl methane have such
low boiling points. Reaping of eurogens on adjacent car-
bon atoms ordinarily increases the boiling point, however,
this was not found to be the case. Maybe the ethyl group
in the molecule has some influence on the boiling point.
Also, there may be some doubt as to the purity of these com-

pounds. --l. r

0'!
OJ

Surface Tension and harachors

Substance Surface Tension Parachors

Drop-Wt. Duhouy Cale. Urey-Wt. Duxouy

on.
n.64eg.c-58s5 29.45 51.52 476.4 469.4 476.5
or.
*3

can a sa-

Hés.¢-c- Gas 28.63 30.80 473.4 466.6 “_473.6
or a 664 ~ _ .-
66/
63335\ C1:
2-6.6-t5a5 29.26 31.52 473.4 465.2 476.2

I a
CH3 0413

cu?
cgaggc.c535 29.60 31.93 476.4 436.6 476.1
03H? -1-

)

0335\ a . .
Cgh5;C-b6h5 29.66 62.13 476.4 464.0 475.8

236

CH3\ on

Mfg-c- 5H5 29.47 31.83 476.4 465.8 474.8
CH3 0335 .1 1

Sugden (g, Chen. 809., ;BS, 1177, 1834) states that
"for isomerides of different structure only, parachors are
identical within the limits of esperimental error. Also,

position isomerism seems to cause no change in the parachor.”

34

In calculating atomic and structural constants, he did not
consider chain branching. For this reason, Sugden‘s con—
stants were not considered in this work.

In calculating parachors, the atomic and structural
constants of iiur‘ni'ord and. Phillips (l. 99.33- 5312., £5, 211.3,

1939) were used. These constants are as follows:

H 3 .15.4 Double bond I- 19.0
0 3 9.2 Somemb. ring a 0.8
0 3 30.0 CH3 . 40.0

The parachor, when calculated from these constants is lar-
ger than the observed parachor. This difference may be due
to chain branching.

Mumford and Phillips state that “chain branching in
aliphatic hydrocarbons and their derivatives is accompanied
by a slight, but definite diminution of the parachor. The
decrement varies somewhat according to the position and
length of the side chain, but within the limits of eXperi-
mental error a mean value of -3.0 would appear to be ageli;
'cable to all branched groups of the type 03330 and double
this value for CR30 radicals and doubly-branched compounds

 

CHRB' 'Cflfig.'

when these decrements are used, the calculated para-
chor checks more closely. If, however, a decrement of ~3.0
is used for branching on a phenyl ring, a still closer
check is obtained. It is shown in the table that the cal-
culated parachcr now checks very closely with the observed

paraehor calculated from surface tension values determined

35

by the Duhouy method.

Surface tension values determined by the Drop—Weight
method are lower than those determined by the Duhouy me-
thod. Consequently, the parachors calculated from Drop-
height surface tension values will be lower than those cal—
culated from surface tension values determined by the
Duhouy method. Sugden determined surface tension_by the
Bubble-Pressure method; also, Eumford and Phillips used
the same method. Parachore calculated from.DuNouy values
check very closely with parachors calculated from the hum-
ford and Phillips constants. Asparently, the DuRouy me-
thod agyroximates very closely the Bubble-Pressure method.
It appears, therefore, that a new set of constants must be
introduced for the Drop-Weight method for this series of

compounds.

56

Structure of Alkyl Benzenes
In these condensation reactions, there may be a pos-
sibility of rearrangement products to be formed. To de-
termine whether the condensation products have the struc-
tures as expected, several reactions were carried in an
attempt to prepare these products.

To prepare Dimethyl upbutyl phenyl methane:
I. g; Warts—Fittig Synthesis:

on ' on
. z , _
1 3

This reaction is very reliaole, in preparing hydro—
carbons from alkyl halides. However, no dimethyl n-butyl
phenyl methane was obtained. Some diphenyl is formed.

The formation of diphenyl may be due to the reactivi-
ty of the two reactants, bromobenzene being more reactive
than dimethyl n—butyl chloromethane. In place of bromo-
benzene, chlorobenzene was used. Unfortunately, the same
results were observed. It appears, therefore, that the
aromatic halides are more reactive than aliphatic halides,

because in each case diphenyl is formed.

II.Ԥy, he Grignard Reaction:
061E153: + big ————>- 05H5thr

CH CH3
CBH5HQBI-+ Cl-C-g4flg-————%>CBH5-Q—C4H9 + -—---

37

The reaction did not proceed in this manner. The
original chloride was recovered and diphenyl was formed.
Chlorohenzene would not react with magnesium to form the

Grignard reagent.

m. mussel-2mm .1...____s.s hthesi :

CH

CH” . ,
n-C H -C—8l + C I! —“1—013—>n-c 1" “0.8631" 4. ..
a 3 "3

A fraction boiling at 08—1090/30 mm. was isolated.
It is 123x_unsaturated but does not contain halogen. It
is not the expected product, dimethvl n-butyl phenyl me-
thane.

Ho other reaction was found by which these condensa-
tion products could be prepared.

It is shown that the physical constants for each com-
pound is different. If rearrangement takes place, two of
these compounds should be exactly alike. Since each com—
pound has decidedly different physical constants, it is
safe to say that the hydrocarbons have the structure as

eXpected.

38

SUEXARY-
l. Tertiary heptyl aliphatic alcohols condense with
benzene in the presence of aluminum chloride according to

the reaction:

3' R'
sac-4:11 + cans 31°]- s.c—06s5 4- H30
R: R.

where R' is methyl and R is n-butyl, iso—butyl, or secon-
dary butyl. then the groups are all different, the reac-

tion is as follows:

Bil I
n-c-os 4» cans $423+ RFC-cans + 2130
Pa a.

2. The straight chain carbinols, as dimethyl n-butyl
oarbinol, methyl ethyl nppropyl carbinol, and triethyl
carbinol condense very readily with benzene to give good
yields of the corresponding hydrocarbon.

3. The branched chain earbinols, as dimethyl'iso~bup
tyl carbinol, dimethyl secvbutyl carbinol, and methyl ethyl
iso~pr09yl carbinol do not condense so readily with ban»
zene as do the straight chain carbinols. The yields of hy-
drocarbons is small. Considerable amounts of the halogen
derivative of the carbincl are formed.

4. Physical constants, as boiling points, densities,
index of refraction, molecular refractions, molecular vol~
umes, surface tension, parachors, were determined‘for each
compound.

5. The relationship between structure and physical pro-

perties is shown.