___—
#—
_____.
_‘—‘
__‘——-
__—_—
.—'_.—
_—'——

,_—_—
.____‘
’___4
__——_
____—

 

SOME DIARYL-ALKYL CARBINOLS

AND THEIR BEHAVIOR TO THE

. 11.233 10R OF ALUMINUM CHLORIDE

"33-333 5313 311 133:3 :3- 13 '
30.913.11.533 R Hradd
g 3’9 .

'1
31:3

.3 ., hi...v,3..v.,. ..

O. ' I‘Vlu .4 t 3| 0| 1 3 v r
31!. ..3...»1 .3 r33 4! . a of. 4 . 3 . u.\ 3.
' . 3 3 .‘ I . . 3 . I . a . .l ..Iol 3: a 3

3. 3 .. . . .3 ,: oulAn.nw3 . ,. 3.9:. . r I 43 . -...3 ....
01.1.! ..d. . r .lfluflufl.‘ . .... . . ..rxl. .. . .c . .I. .3.3 o 3.‘ . ..u... .. v . 3 . .. . . on {$1.333mearl,

 
 

 

 

 

SOAE DIARYL-ALflL CAuiBlfl'ULS AND TuEIR
BEHAVIOR TO THE
ACTION OF ALUmIliUJ CIEORIDE

A THESI S

SUBAITTED TO THE FACULTY OF THE
MICHIGAN STATE COLLEGE OF AGRICULTURE AND APPLIED SCIENCE
IN PART FJLFILMENT 0F TJE 1:333:11]:me FOd THE

DEW " OF
MASTER OF SCIEICE

BY
JOSEPH R. HRADEL

AUGUST. 1954

SOME DIARYLoALKYIa CARBINOLS AND THEIR
BEHAVIOR TO THE
ACTION OF ALUMINUM CHLORIDE

331. 335

-ACKHOWLEDGMENT-

To Dr. Ralph C. Huston the writer
11131142. to express hi: moat sincere
appreciation for the personal and
professional counsel without which

this work could. not have been con-

pl eted.

Joseph kt. Erode].

«FORENO RD-

Th: fact that the aluminum chloride
condensation was conceived by another
and, in past years, has been the sub.) ect
of many papers; also the possibility that,
through oversight, credit has not been
giVen where credit is one; the use of such
an ideal abstraction as the turn "1" has
been omitted.

Joseph R. Hrwiel

Introduction- ........ --------------------- ..... -1
Nomenclature---------------------------.--------2
Historical:
Dehydration.-------------------------------4
Condensation---------------------------—---4
Sulnarya-u-------------------------------.-6
Experimental:
.latcria1s---------------------------------.q
Preparation of Carbinols------------------.8
Tabulated data.--..-------------------11
Condensations-----—..-----------..--------12
Tabulated data:
Condensation and Heat effect--------16
Physical constants.---------.-------17
Analysis and.flolccular weights------18
Summary----------..-------------------19
Brominations.~---------------------------.20
Analysis and Constants.------..---.---21
Hitration of Cyclic Hydrocarbons~---------22
Tabulated data...-------------..------22
Discussion-------.----..----..-----------------z3

JNTROHJCTI’JN AND NOMENCLATURE-

.1-

III THO DUCTIOH

The sub: ect of this paper is an outgrowth of
the work of Wilsey (1), Erickson (2), and. Walters

(5) in this laboratory. Their attempts to prepare
1,1,1-triphenyl-alkyl hydrocarbons, the expected
compounds on condensation of uiphenyl-alkyl carbinols
with benzene in the presence of. aluminum chloride,
failed.

Wilsey proved that the reaction gave an un-
saturated diphenyl hydrocarbon which was identified
and a small quantity of a saturated hydrocarbon which
he failed to identify since it did not conform to
the constants of the expected compound.

It is the subject or this paper to check the
work; to further substantiate the results by condensation
of carbinols identical in type but containing methyl
substituted aryl substituent and carbincls containing
a branched chain elkyl substituent; and if possible.
to definately establish the course of tne reaction

since it does not fall in line with the expected.

.2.

THE.NOMENCLATURE

Throughout this paper the nan—sing;~ of compounds
will be in accord with the Definitive neport or the
Condission (4).

Carbinols:

HO-CoO¢C-C~
1 2 3 C

In the case of the presence of aryl groups. the name and
numbering will be as in the following example:
Ar H H H
HO-C-C.C-C-H
Ar H H H

1.1-diaryl-butanol-:.

Unsaturated hydrocarbons:

-c,_c.c-c-
1 a 5 4

hydrocarbons of this type with aryl groups will be named.
and numbered as follows:
E E Ar
H-C-C-Cgc-Ar
H H H

1,1.diaryl-butene-1.

Cyclic hydrocarbons:
Substituted cyclis hydrocarbons containing aryl and

alkyl groups, the numbering will start with the aryl as
shown: in the following example:

Pb H

1 l
Ph-C .“CJQ

1 1
MeoO-m-C 4h

4 ‘l 1
H Ph

1 2

3

1. 1, 3, )«tetraphenylaz, 44inethyl~cyclobutane

.‘LICAL-

J

m3...
on

«E11

-4...

Dehydration o i' Carbinol s

It is found, on looking through the literature.
that there are cases of intranwlecular dehydration of
carbinols by the use of heat and chemical agents. A
detailed discussion of these would be too lengthy, hence
they are only listed. Wagner (5), Sudborough (6),
Tiffeneau (7’s Sohorigin (8). lesson (9), Henllian (10).
and Michael and Jeanpretre (11 ).

Condensation

Intermolecular dehydration has been found to take
place mainly by the use or such dehydrating agents as
zinc chloride: Fisher and kisser (12 and 1)). Liebnsnn (14),
and Kippenberg (15): Hydrochloric acid: Susie (16);
Sulfuric acid: Bistrzycki and .‘E‘latesu (1')), Meyer and
Wurster (18). Becker (19), Hoelting (20). Gattemann and
Keppert (21), Fritsch (22). and Bistrzycxi and Sinonis (23).

The most important agent of dehydration and the one
most worked with is anhydrous aluminum chloride. It has
been in use since 1882 and still holds its place as
a dehydrating agent. Some or the earlier work that was
carried out was by: Wass (24). hers and Weith (25).
Graebe (26 and 27). anbert (23). Shell and Beer (29).
Frankfurter and Kritchevshy (30), Frankfurter and Kokatnur
()1). and Schaarschnidt, Honann, and Szemo (52). The
later and more extensive work of Huston and his (to-workers

is taken up in references (33-44 inclusive).

-5-

huston and Friedmann ( 53) condensed methyl
phenyl carbinol with benzene in the presence or aluminum
chloride to obtain 1,1-diphenylethane in a 3076 yield.
Aldo ethylphenyl carbinol was condensed to obtain
1.1-diphenylpropanc in yields of 40%.

Huston ()4) working with benzyl alcohol in an
aluminum chloride dehydration with phenol obtained
p-benzylphenol in yields of 45$. Similarly. condensation
of the alcohol with anisolc gave the methyl ether of.
p-benzylphenol and with phonetole a yield 0: 57gb of
ethyl ether of p-bensyl phenol was obtained.

Huston and Sager (55) obtained allyl-benzene in
quantities of 1636 in an aluminum chloride dehydration
reaction between allyl alcohol and benzene.

Huston, Lewis. and Grotemut (36) condensed methyl-
phenyl oarbinol with phenol to obtain a 3595 yield of
p—hydroxy-1,1-diphenylethane. Ethylphenyl carbinol
with phenol gave a 3096 yield of pahydroxydfl-diphenyl-
prepane. Benshydrol with phenol gave a 4075 yield of
p-hydroxy-triphenylmethane.

Huston. Swartout, and bardwell (37) condensed
o-cresol and. bensyl alcohol to obtain three products:
4-benxyl-o-cresol. 2-bcnzyluo~cresol. and 2, 4-bcnzyla

0-01‘0301.

-6-

Huston and Strickler (41) condensed phenylpropyl
carbinol with phenol to obtain a 20$ yield of 4-(e-phenyl-
butylL-phenol and a 656 yield of 2-(a.phenylbutyl).phenol.

Huston and Hon]: (4o) benzyleted macreeol to obtain
two mono benzylated and one dibenzyl-m-cresol.

Huston and Fox (44) condensed tertiary butyl alcohol
\itn benzene to obtain tertiary butyl-benzenc in yields
of 55-67%. Tertiary butyl-benzcne was condensed with
butyl alcohol to give 17-2276 yields of oflitertierybutyl-
benzene. Tertiary may). ale..hol wee then condensed to
give a yield of 6196 tertaryamylobcnzene. Dimethyl-n-
propyl carbinol mlt'n benzene gave a 44/: yield of dimethyl.
nap ro pyl ~phenylme thnne. Dime tug-1:1 so propyl onrbinol
with benzene gave 36¢ yield of dinethyl-ieopropyl-phenyl-

methane.

-Summary.

Tertiary aliphatic alcohols. aromatic alcoholl in
which the hydroxyl is on the carbon sdJecent to the phenyl
group, and unsaturated alcohols with the double bond
ad.) acent to the nydroxyl carbon are found to condense
in the presence of aluminum chloride with benzene or,

in my cases, with phenol.

-EXPEMM""1'M4-

.7-

«Materials.

Benzophenone used was E.K. practical grade.

Benzoyl chloride, E.K., n.P. o.5°.

Toluene, B.P. 109-110,5 dried over calcium
chloride for a period of a week.

Benzene, (thicphene free) M.P. 5° dried over
calcium.chlcride for one week.

Nitric acid, Red fuming, ep. gr. 1§8¢1.6e

Ethyl bromide. E.K.. practical grade but re-
distilled to traction BeP. 38.400 and.dried over
calcium chloride.

Propyl bromide, prepared from n-pmpyl alcohol
with sodium bromide and sulfuric acid. Fraction
B.P. 70-710 was used.

Isopropyl bromide, prepared from iaopropyl
alcohol with sodium bromide and sulfuric acid. Fraction
B.P. 59-»61o was used.

Other materials used were magnesium ribbon and
technical bromine.

All fractionatione were carried.out in a 250 3.20 am
modified Claieen column, used in standard as well no

vaouo distillatione.

.8-

-Carbinol s...

In the preparation of carbinols of this type,
considerable difficulty was eXperienced which made
essential the modifiaction or procedure. The
modification was found to work very well for all
the carbinols prepared, so it may be considered as

general.

Emanuel: OF 1,1-IDLPI1mYL-PROPMIOLa-I
Grignard reagent (8, 45. and 46);

A three liter three necked flask was fitted with a
sealed mechanical stirrer. a reflux condenser uitn a
drying tube of soda-lime. one. a dropping funnel. The
entire apparatus was then placed into a large cooling
receptacle. Into the above setup were placed 25 gr.

(1 mole) of cleaned magnesium ribbon, one liter of an-
hydrous ethyl ether, and a crystal of iodine. To the
above was added, through a dropping funnel, slow/1y

and with constant stirring, 110 gr. {1 mole) of anhydrous
ethyl bromide 37-390 fraction. After the reaction had
subsided, the mixture was allowed to stand for 2 to 4
hours.

Reaction with benzophehonc: (47)

To the above Grignard reagent, at 10.190. was
introduced, slowly and with constant stirring. technical
benzophenone dissolved in anhydrous ethyl other until

a colorless solution resulted (note 1). The mixture

~91»

was allowed to stand for a period of one hour and

then decomposed.by slowly pouring into a tour liter
Erlenmeyer flask containing one Kg. 0: cracked ice

and 100 cc of concentrated hydrochloric acid. The
other layer was then separated and allowed to evaporate
spontaniously. The resulting crystalline substance

was pressed tree of oil on a porous plate, recrystal.
lized three times from 95¢ ethyl alcohol, filtered.

washed with 20 cc of ethyl ether at 0°. and dried over
anhydrous magnesium sulfate in vacuo. The crystals of
1,1odiphenyl.pr09anol-1 were found to melt sharply at
9444.? and boil at 175-eo°/17 mm (45 and 46). 149-
151012 mm (note 2). 1

Notes
1. it the start or the addition of benzophenone.
a very intense red color developed. this Las lost after
the addition of 150 gr. of the ketone resulting in a
clear solution. The coloration is explained.by Gonberg
and others as due to Ketyl formation (47). It was
found that reactions that gave this coloration.gave good
yields of the cerbinol. Those that did not give it
resulted in precipitation. and on subsequent decomposition
gave 100% recovery or the ketone. The coloraticu and
increase in yield was found to be favored by a slight
excess or’magnesiun.in the arignard reagent.

-10.

Contamination of the carbinels with ketone was
found to be less if ketone addition was stopped on
the disappearance of the coloration.

2. The carbinol distilled as a colorless liquid.

1,1.diphenyl-butanolo1

Was prepared in the same manner as 1,1-diphenyl-
propanol-1 with the exception that 12} gr. (1 mole)
of n.propyl bromide was used. h.P. 70,710. in the
preparation or the reagent. The traction 160-6s°/10 m
was lie-ind to be the osrbinol (46). The carbinol
was purified oy crystallisation iron ligroin. Crystal-
lization iron alcohols r suited in the Iormaticn of
compounds as a result of interation or the carbinol
and the alcohol solvent, huston and Macomber (48).,
The carbinol distilled as a colorless liquid 162-639/10 mm
rnd crystallized in white needles melting at 65°.

1,1-diphenyl-2,2-dimcthyl-cthanol-1

1,1-dipheoyl-is0propyl curbinol was prepared in
an identical manner as the others except that 125 gr.
(1 mole) of isoproyyl bromide (49) fraction 59-610
was used. The reaction mixture after expulsion of the
other, was distilled resulting in the fraction 150-539]; mm
as the carbinol.
1.phenyl-tqp-tolyl-propanol-I

In this case the ketone was phenqup-tolyl ketonc
prepared by method or Ador and.Billket (50) McP. 57°.

slis

The carbinol prepared distilled as a brownish-yellow
liquid at 175-80°/2 mm, 210-15°/20 mm (51).

Yields
Compound Quant. used a yield
1, I-QLQQUHJ 1-94.0pr1-‘ j‘ull (I 2
1,1-uiphenyl-butanol.n Full 72
1.1-dipheny1-2,2-dinethyl- Full 30
‘ ethmlc‘
1-phenyl-1—p-tolyl- Half 70
prOptfllDl—d

gr. yield

150.0
163.0
180.0

79.0

The yield and per cent based on runs made by the

modified BBthOde

-1 2/ /
-conden cations-

1,1-diphenyl-propanol-1 uit'n benzene at 20°:
100 cc dry benzene was placed into a three necked
500 cc flask equipped with a mechanical stirrer and
dropping funnel. To this was then added 27 gr. (1/5 mole)
of aluminum chloride and allowed to stir for 15 minutes.
42.5 gr. (1/5 mole) of diphenyl ethyl carbinol were
then dissolved in dry petrolium ether and introduced
slowly and with constant stirring into the benzene-
aluminum chloride mixture with the temperature maintained
at 20°. The addition taking about an hour. stirring allowed
for a periou or five hours after the addition. During the
addition of the carbinol much hydrochloric acid was
given or: nun the reaction mixture was observed to change
to a reddish-brown color. The reaction mixture was then
poured slowly into a flask containing cracked ice and
hydrochloric acid, the ether-benzene layer was separated
of: and dried over calcium chloride. At this point the
mixture had a greenish color like that of cylinder oil.
After a day of drying the mixture was distilled tree at
other and benzene, the remainder fractionating into:
29 gr. -~-140-45°/} mm
5 er- mus-95°13 m
2 gr. ..--1.9540013 mm

1 gr. -“-~-naoucctu

-:3-

The first fraction was found to be unsaturated and
identified as I’l-diphenyl-propene-t. ’It crystallized
in five sided plates from 95$ ethyl alcohol and melted
at 48.5-49° sharp (45. 46. 52. 55. and 54).

The second and third fractions were combined and
crystallized from hot 95¢ ethyl alcohol and found to be
1,1,3,3—tetraphenyl-2,4-dinethyl-cyclobutane (by analysis
an molecular weight determination). The crystals are
rhombic, white with a shiny luster, insoluble in petroliun
and ethyl ether, slightly soluble in hot alcohol. when
dissolved in cold benzene a Very slight violet fluorescence

results.

1,1-diphenqupropanol-1 with benzene at 0°:
The technique of condensation was the same as used
in the first condensation. Fractions obtained:
20 gr. ---14o-45°/3 m
4 er. ---145-959/3 an
15 51‘. --.-195-2001; am
0 gr. --------—---tar
The first fraction again being the 1,1-diphenyl.propene-1
and the second and third fractions resolvinb into the cycle

butane derivative.

1,1-diphenJl-propanolét in petroliuu ether at 20°:

The condensation being the same as the others with
the exception that benzme was left out. desalted in
the following:

an"-

20 gr. 1,1-diphenyl.propene-1
4 gr. 1, 1, 5, 3.tetraphenyl-2, 4-oimetnyl acyclobutane
6 gr. Tar ’

1.1cdiphenyl-butanol-1 with benzene at 20°:
Procedure as used before. 45 gr. carbinol, 100 cc
benzene, and 27 gr. aluminum chloride. Fractions:
)3 gr. ---1 , 1 -diphenyl-butene-1---1 55 -63°/ 14 m
4 gr. —--1 , 1, 3, 3-tetraphenyl-2, 4.di ethyl-cycle butane
ace-550162 m
5 5r.---Tar
Condensation at 0°:
27 gr. ---155-6o°/14 m
1) gr. -«26o-65°/62 m

2 gr. -------------tar

1,1-diphenylae,2-dimethyl-ethan01-I at 20°
45 gr. carbinol, 100 cc benzene, and 2'1 or. of
aluniiun chloride. Fractions:
)1 gr. ---1,1ouphenyl-2.methyl-propene-1--170-7§°/§I1...
8 . 5 gr. ~--1,1, 3, 3-tetraphenyl-2, 2, 4, 4-tetrmethyl-
cyclobutane 215-1’l°/3m
2 5r. ----tar
Condensation at 0°:
2} 31'. ...-1704759} “In
17.5 sr.--215-17°/3 mm

9 .5 8r. -—--—----~tar

.154-

1,phenyl-1-p-tolyl~propanol-1 at 20°:
;5 gr. carbinol. 100 cc benzene. 27 Sr. of
aluminum chloride.‘ Fractions:
1—phenyl-1ap-tolyl-propene-1 38 gr. ---175—8J°/2 mm
1.3-d19henyl-1,3-di-p-tolyl-2,4~dimetnyl-cyclobutane
3.5 gr. ---210-159/2 as
Tar- -------- -~—-0.5'3r.

O
Condensation at 0 :

35.5 er. mus-80°12 m
5.8 gr. .--21o-15912 mm

0.0 gr. -------”-G-tar

The yields, constants and other information will
be found in the tabulated data.

-16.

Yi el ds

Condensations and Heat Effect

Unsaturated Hydrocarbons:

 

 

 

finpound gondwsati on god?
T313 0 1 31d
1,1.aiihen‘iiqropena-‘ 39"1.oss""’igjs.Loss 280 .129!"o' 50' o' T"

1.1-uphenr1-bntene-1 64.0, 79.011 295-505 95.0!
1,1-diphenyl-2-methyl- 5;,095 74.0% 295-505 95.0,

 

 

 

 

 

 

 

 

 

 

 

 

 

 

W1 Ll
1-ph0nyl-1-p-tolrl- 85.09!» 90 . 596 28 5-295 96.0!
l Edam-1
Cyclic Hydrocarbons:

Tielobutme Iondensatl on Heat
30 2913 W lield
371, '5, 3Retra15henyl-
J 2 . 4-0-1136th 40,99? 20 . 0% 289 2290 4.0%
1, 1 , 5, 3-te7trapheny .
2-4-dllet 1 32.0% 104396 295-105 3.0!

 

 

T, 1, 5, 3-tefrap deny ..

2|? 6| ftetrametml 42.0“ 20 .Qfi 29n-fl 11.0%
103 P any ‘193'd'1"

p-tolxl-g 5-dimeth11 13.095 Log 25 5-295 2.096

 

 

All unsaturated compounds soluble in (3th and
petrolium ether and cold methyl and ethyl alconols.

All cyclobutane derivatives insoluble in cold
ethyl and methyl alcohols. ethyl and petroliun ether,
end are soluble in cold benzene giving a very faint

violet fluorescence. Heat yield obtained by condition
of distillation.

-17-

Physical Constants

Unsaturated Hydrocarbons:

 

 

 

 

 

 

 

Conpcund KP. RF. D? 3 D25
1 , 1 -dipheny1-propene-1 48 . 5- 230 «-
‘90 28 ‘0 ...-C. ...-so.
1 , 1-dipheny12butencd ET-
----.. ° ' 149 1.5794
1 , 1-d1phenyY-TF-néthyf. 253- 't' ' ‘5

 

 

gropenc-A -....- 2%20 1.92% 1.1819
1-D any ~1-p-oy- 23 -
grams-L ----- W

The refractive index measured by the Abbs hefractomctcr.

 

 

Cyclic hydrocarbons:

 

 

 

 

 

 

Cyclofiitene 13. BI. Ffixfifi’tfi 59F
ethyl
1,1, 5, b-tetraphenyl— 10 4-0 :1298- w e
2 {-dimcth 1 405° g’o_o°12 um i'hombic
1,13,3-tetrapheny175- 260- final]; incite
2-4mm; 1 175.? 26 162 an needles
1,1,},5-tetrafiheny - 201- 21 w s

 

g,gaf,§-tetrameth¥l 591,53 217°!) n lates
1 )- eny -1 3 ..p- 0)— 10- figfli white""'""'"

'5ng -2_. Hilliethyl 294° 21£I2 mm needles

Distillation of cyclobutane derivatives at standard
pressure was inpossible because they were found to

de compo sc.

-13-

Analysis and holecular weights

 

 

Cyclobutahes
Analysis:
Cyclobutane Seraple dbg H 0 ¥Igdro§en Eififipn: :;
31'. gr. 3;. c c. and c c. ioun
Titraphenyl-di- s:-———
methyl (0301123) .2164 .7357 .1408 7.2096 7.2856 92.8016 92.4,.
fitraphenyl-di-

 

ethyl (cjzafl) .2049 .6911 .1406 7.157» 7.689‘ 92.25% 92.0%

1fe’traphenyl«tetra.»

fiphenyl-di-p-tolyl:
dimethyl (032.1”) .2004 .6767 .1591 7.7596 7.7711 92.2% 92.1?

 

 

 

Carbon and hydrogen analysis made according to the
method described by Fisher (55),

Molecular Weights:

 

 

 

ch‘fobutane Us a e e e 2
1
TetraphenyI-dfmethyl-
3158 £2 585.00 3941.00
fitraphenyl-di e thyf.
416416 W

 

Tetraphcnyl-t etrame thyl-
' “WM
Fiphenyl-dl -p 401111-111-

WNW—£1.39.—

moleoular weight determinations made by boiling

 

 

point method described in Findlay (56).

-19-

-Summary .1.

An increase in temperature shows a marked increase
in the formation of the unsaturated derivative in all
cases.

The carbinol when subjected to the normal distil-
lation temperature of its respective unsaturated
derivative, underwent dehydration without the presence
of aluminum chloride. The cyclobutane derivatives were
formed as well as the'unsatdrated hydrocarbons.

In condensations, a decrease in temperature resulted
in an increase in the formation of cyclic hydrocarbons.
Increase in temperature with the presence of aluminum
chloride favored the formation of tar.

The presence of branched chain alkyl group in the
carbincl favored the formation of cyclic hydrocarbons
on condensation, while the presence of methyl substituted

aryl groups had the reverse effect.

-20.
Brominaticn of Unsaturated Hydrocarbons

Into a small h.B. flask 250 cc fitted with a
mechanical stirrer and placed into an ice bath, were
placed 5 gr. 1,1-diphanyl-propene.1 fro» a constant
boiling fraction 200.250.59 in 20 cc of dry chloroform.
To the above mixture was added a 1.5 cc quantity of
bromine in 10 cc of chloroform. During the early part
of the addition, complete decolorization was observed
to take place. After allowing the mixture to stand for
12 hours, during which time HBr was given off in considerable
quantities. the chlorofomm was evaporated off on a steam
bath. The remainder, a dark brown liquid, was subjected
to many fractionatione and a month of cooling, and
resolved into crystals of the bromo derivative.

Table of constants and analysis will be found on
the.next page.

Crystallization of these compounds is very difficult
since they are found to decompose on standing in liquid
form. Two of the derivatives are known to be solid, the
diphenyl propane and the diphenylmethyl propane. It is
predicted they all are solid though only the diphenyl
propene derivative could be crystallized. Fractionation
and seeding with the lower bromo homolog failed.

All bromo derivatives were prepared in a simmlar
manner to the above, 1:1 molar proportions being used in

all cases.

-21-

Constants and Analysis

 

 

 

Constants:
fompound * IL?! 3.19. Dem
2-:bromoa1, 1-diphenyl.propcne-1 48- 1477- We

49° 17291143112 needles

 

 

 

 

2-bromo-‘l . IodiphanyfilficnO-1 1T5. T6110"
--- 178°“; mm liquid

firemen-1 , 1-diphe n;.1-2.uethyl.. 11f)- Yellow
preponeq ...... 18 /2_'.. mm li quid.

mromo -1 -pheny1-1 ...p utOIiI-t . ‘9 c “1110'

phonetic-1 --- 2300“me Liguid
Fractionation at standard pressure could not be

carried out due to decomposition.

Analy sis for bromine;

 

Foolpcuhd Formula Eula. w“found.
2-brozno-1,1.diphenyl.propene-1 (C 5H )Br)
1 1 22 1;! 23 IE!
2.5r0lfiti}1-diphcnyl.butonc.1 (C H 5Br7
. 16 1 ,.
__ A 27.8920 21. 5795__
3-bromo-1. t-Ephew1-2.metfif. (cfiswsrj

 

 

 

propane-1 27. 895$ 31!. 4296
mi‘omO-1-phenfl.1.potolyln (E16H153r7
propane-1 “2143055 21. 222

 

Bromine analysis made by Parr bomb according to the

procedure of Fisher (57).

-22-

litration of Cyclic Hydrocarbons

Nitrations were carried out according to the nethol
of Gonberg (58 and 59) who states that all phemrl groups
are nitrated in the pars position.

1 gr. of hydrocarbon is treated with 15 gr. of
tuning nitric acid (sp. gr. 1.58-1.61) at a temperature
of 0°. The hydrocarbon is added to the nitric acid very
slowly. After nitration is complete, (repeated nitrations
may be required) the nitro derivative is removed from the
acid by dilution sitn water at 0°, filtered, washed iris
or acid, and allowed to dry.

Goteborg designates that three nitrations be used, he
does not state the concentration of the acid he used.
These hydrocarbons were found to nitrate completely on
one nitration. Several nitrations were used to make

sure that complete nitration had taken place.

 

Mtane LIE'. Description
1,1,3, 3-tetraJp-nitro..phenle-Z, 4-
dimethyl- 94-850 Yellow powder
1, :1 ,,3 3-tetra-Tp-nitroiphenle-2, 4-
diethyl;135-pé° DkJel powder
1,1,,3 3-tetra-(p.nltro-pfienyTT.2 2
4:91:13“:th - ’joD lat 1e]. powuer
1, 3-di-(p-nitro-phenyl)-1, )- .p-
tglyl-z,§~dimetgyl- vec,ng° ht {algpgwder

Distillation in vacuc resulted in deconposition.

 

 

..DI SCU SSIOH -

-23-

As to an orplaination, why these carbinols
act the way they do as a result of the effects of
aluninun chloride and heat, may be shown by several
facts.

According to the literature, intramdlecular de-
hydration of carbinols of this type have been kncln for
some time. The fact that this dehydration will take
place shows that there must be a distorted condition
within the molecule. This distortion may be looked
upon as, the hydrogen of the beta and the hydroxyl of
the alpha carbon atoms being rendered highly mobile as
a result or the influence or the two aryl substituents.

The cyclobutane formation, however, can not be
conclusively explained from the standpoint of intra.
molecular dehydration. If such be the case, the only
explaination possible would be the formation of a
free radical with unsatiried bonds on two adJacent carbon
atoms: Ar E

“has,

which, if possible, on combination of two such free

radicals should give us two possible cyclobutanes:

Ar H CH3 er
‘1 1 , .2 1
and 8
Ar H A?

3

-24-

the possibility of the first case being very slight
since there are too many like charged and bulky groups
on one side of the molecule.

Another explaination of cyclobutane formation,
one which seems very possible since the yields are quite
low, would be:

*1 b:
H-M-CH3
rig”: 1.1%.".

' I
l : : i
Li: L0 -.:
H}C-?—%~Ar
H Ar

an intermolecular dehydration as shown. The position

of the aryl sustituents being favored by the fact that
there is a repulsion of the like charged aryl groups and
an attraction between positive hydrogen and negative

hydroxyl.

-SUWY-

-25-

The aryl-alkyl carbinols are found not to.
react to conditions of intermolecular dehydration
between oarbinol and benzene.

These carbinols are found to dehydrate intra-
molecularly to form'unsaturated diaryl hydrocarbons.
and intermolecularly to fomm aryl—alayl substituted
cyclobutanes.

The effect of heat is the same as the effect of
aluminum chloride but favors intramolecular dehydration.
The formation of cyclobutane derivatives as a result
of heat effect is very slight, though present.

Branched chain alkyl and methyl substituted aryl
substituents in carbinols of this type as well as the
diphenyl alkyl carbinols will not condense with benzene
in the presence of aluminum chloride.

Considerable difficulty was encountered in the
isolation of the compounds prepared. The fractions,
though well defined, required twenty to thirty
fractionations and repeated fractional crystallisation

before any state of purity could be attained.

oBIBLIO GRAPHY.

1.
2.

3.
4.

5.
6.

8.

9.
1o.
11.
12.
13.
14.

15.
16.

17.
18.

27.

.26-

Huston and Wilscy, Thesis H.S.. Unpublished. (1933).
nus... and Erickson, Thesis 3.5.. w . . (1933).
Huston and Walters, Thesis B.S.. " " . (1935).

gPatterson, J.A.C.S.. 53, 3905, (1935).

Wagner, Jour. ibis. Phy. Chem. Soc.. 16, 324.
Sudborough, $00.. 67, 604.

Tiffenean. 6.. 4, 143, 649.

Schorigin, Ber.. 41, 2115-11. (1908).

hasscn, Comp. rend.. 135. 53}.

Hemilian, ber.. 7, 1203. (1874).

.Michael and.Jeanpretre, Ibid., 25, 1615, (1892).
Fisher and Roser, Ibid.. 1}, 674, (1879).

Fisher and Roser, Ann.. 206, 113. 155. (1880).
Liebmann, Ber.. 15, 152. (1882).

Kippenberg, Ibid.. 30, 1140, (1997).

Susie, Bull.. 3, 11, 517. (1819).

Bistrzycki and Flateau, Ber.. 28, 889, (1895).
Meyer and Wurstsr, Ibid.. 6, 964, (1873).
Becker, Ibid.. 15, 2091, (1882).

Noelting, Icid., 24, 3121. (1891).

Gattenlann and.Koppert, Ibid.. 26, 2811, (1893).
Fritsch, 111111.. 29, 2300, (1896).

Bistrzycki and Simonis, Ibid.. 31, 2812, (1898).
Wass, Ibid.. 15. 1128, (1882).

Hers and Keith, Ibid.. 14, 189, (1881).

Graebe, Ibid., 34, 1118, (1901).

Graebe, Chas. Ztg.. 25, 628, (1901).

28.
29.
30.
31.
32.
35.
34.
35.
36.
37.
x 38.
39.
4o.
41.
1 42.
‘43.
44.
45.
46.

47.

49.
50.
51.
52.
53.
54.

-27-

Jaubert, Comp. rend.. 132, 841, (1901).

Shell and Seer, Ann.. 394, 119, (1912).

Frankfurter and Kritchevsky.. J.A.C.S.. 36, 1511, (1914).

Frankfurter and Kokatnur, Ibid.. 36, 1529, (1914).

Schaarsohsidt, Homsnn, and Seems, Ber.. 58, 1914, (1925).

Huston and Friedemann, J.A.C.S.. 38, 252'], (1916).

Huston, Ibid.. 46, 2775. (1924).

Huston and Sager, Ibid.. 48, 1955. (1926).

Huston and others. Ibid.. 49, 1365. (1927).

Huston, Swartout, and Wardwell, Ibid.. 52, 4484, (1930).

Huston and Eldridge, Ibid.. 53. 2260. (1931).

Huston and Lewis, lbid.. 53, 2379. (1931).

Huston and Honk, Ibid.. 54, 1506, (1932).

Huston and Strickler, Ibid.. 55, 4317, (1933).

Huston and.others, Ibid.. 53, 2146, (1933).

Huston and others, Ibid.. 55, 4639. (1933).

Huston and Fox, Thesis s.s.. Unpublished, (1934).

Hall and Bauer, Ber., 37, 231, (1904).

flages and Hellmann, Ibid.. 37, 1450, (1904).

Gomberg and others, Rec. Trev. Chim.. 48, 847-51. (1929).

Huston and.haoomber. Thesis B.S.. Unpublished, (1934),

Linnemann, Kekule, and Schrgtter, Ber.. 12, 2219. (1878).

Adar and Rilliet, Ibid.. 12, 2299. (1818).

Brsun, Many, and Reinsch, Ann.. 468-9. 295. (1929).

Emmart, Lucas, and Amagat, Bull.. 51, 108, (1932).

Auwers and Eisenlohr, .1'. pr.. (2),84, 50.

Sabstier and Murat. Comp. rend., 155. 337; A. Ch.. 9. 4.
288.

-28 ..

Fisher, Lab. henna]. Org. Chem. 3rd. Ed... 245, (1931).
Findlay, Practical Phys. Chem" 123, (1929).

Fisher, Lab. Manual Org. Chen». 3rd. Ed... 342, (1931).
Gomberg and. Gone, Bern 39, 2962, (1906).

Gomberg and Gone, 0., 2.14911, (1906).

 

'4’
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