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m-DIAEYLBENZENES:
SYNTHESES AND U LT RA VI OL ET SPECTRA
By F re d Thornton Reed
Thesis
submitted to the F a c u l t y of the Graduate School of the Un iv e r s i t y of Maryl an d in partial fulfillment of the requirements for the degree of Doctor of Philosophy 1950
UMI Number: DP70538
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A-CKNOWLEDGEM ENT
The author wishes to express his deep appreciation and sincere gratitude to Dr.
G. F or rest Woods for his
m a n y suggestions and his u n t i r i n g guidance and assistance throughout the entire course of this investigation. out his counsel and direction,
With
this thesis would not have
been possible.
±57899
TABLE OF CONTENTS I NTRO DU CT I ON H ISTORICAL
.................................................
1
...................................................
3
m -Ter ph en yl derivatives 0-Terphenyl d er ivatives DISCUSSION
• ..............................
..............
Synthesis
EXPERI MEN T AL
spectra
64
.................
65 65
.............................
3 -Carboxybi phenyl
4-Xenyl bromide
64
..................
Monoethyl ether of dihydroresorcinol
2-Xenyl iodide
40
......................................
Silver Salt of di hy dr or es or c in ol
3-Xenyl bromide
15
...............................
...................................................
Di hy dr or es or ci no l
8
15
.............. ... . ............................
U lt raviolet
3
.......................................
69
..........................................
69
.........................................
70
3 -P he ny l -z^^-Cyclohexenone
............................
70
3-( 4-Xenyl )-Z^. ^-cyclohexenone
.....................
3-( 3-Xenyl )-.£s ^-cyclohexenone
.........................
71
3-( 2 - X e n y l )
.........................
73
2 _Cy C io}ieX 0non Q
1-Fhenyl-3-( 3 - x e n y l )-benzene (B) 1 - P h e n y l - 3 - ( 3 - x e n y l )-benzene
(A)
l-Pheny l- 3- ( 2- xe ny l) -b e nz en e (B) l - P h e n y i - 3 - (2 - x e n y l )-benzene
....................
(A)
71
75 76
....................
77
78
ii l-( 3 - X e n y l )- 3 -( 4 - x e n y l )-benzene
(A)
l-( 3 - X e n y l )-3-( 4 - x e n y l )-benzene
........
1 . 3 - D i - ( 3 - x e n y l )-benzene
................
..................
79 80 81
l - ( 4 - X e n y l ) - 3 - (2 - x e n y l )-benzene
(A)
............. ..
83
1 - ( 4 - X e n y l )-3-(2 - x e n y l )-benzene
(B)
................
84
l - ( 3 - Xenyl)-3-(2-xenyl)-benzene
(B)
85
1 - ( 3 - X e n y l )- 3 - ( 2 - x e n y l )-benzene
(A)
86
1 . 3 - D i - (2-xenyl)-benzene m-Cliloroiodobenzene m-Nitroiodobenzene
.............................
87
...................................
87
.............
89
3-Nitro-3 f-ch.lorobiphenyl
............................
89
3-Ch.loro-3 f-ami no biphenyl
............................
91
.............................
92
3-Iodo-3 T-chlorobiphenyl
3-( 3-Chloroph.enyl)- A ^ - c yc 1 ohexenone 3 , 3 f r- Dichloro-m-terphenyl
...............
.................
3-(3-(3 f- C h l o r o ) - x e n y l y l ^ - c y c l o b e x e n o n e 3, 3 T 1 ! T-Dichloro-m-quinqueph.enyl
....................
93 94 95 96
Wurtz reaction of 3,3 *ffT- d i c h l o r o - m - q u i n q u e p h e n y l .
97
U ltraviolet absorption
99
L I T E R A T U R E CITED
spectra
......................
101
INTRODUCTION A method ha d been d ev eloped earlier
In this laboratory
by T u c k e r 1 for the prep ar at io n of m e ta substituted d i a r y l benzenes f r o m the monoethyl ether of d i h y d r o r e s o r c i n o l . seemed pertinent that this synthetic route
It
should be extended
and the u t i li ty of this enol ether as a starting material for pre pa ri ng m et a di su bstituted benzenoid hy drocarbons be e x ploited.
Therefore,
a series of polyphenyls was prepared by
the general reaction scheme shown below.
00 2s 5 R1MgX
substituents,
Pd-C
and R^, was varied to include all the p o s s i
ble combinations of phenyl, groups
In the final compound
Since the groups tion,
The nature of the
2-xenyl,
3-xenyl,
and 4-xenyl
(IV).
and B.£ possessed conjugate u n s a t u r a
it was' also a purpose of this research to Investigate
the ultraviolet light absorption of these substances In which the meta substituents cannot hybrid.
jointly enter into a resonant
This was done by d et er mi ni ng the a bsorption curves
in the ultraviolet region of the spectrum for each compound prepared.
These absorption curves not o n l y demonstrated the
prohibited resonance between m e t a substituents, but also brought out certain other fundamental facts applicable to
the theory of absorption of ultraviolet light by organic molecules.
These are discussed in a later section.
While this work was in progress,
it became apparent
that certain other avenues of approach were worthy of inves tigation.
To confirm further the interpretation of the
ultraviolet
spectra,
a series of compounds was prepared in
whi ch
was the tolyl group
(there b e i n g three possible
isomers)
and R 2 was the methyl
group,
three isomeric d i m e t h y l b i p h e n y l s .
thus resulting in
A still further extension
of the problem resulted in the p re paration of the three iso meric compounds of type II, in which R-j_ was a chlorophenyl group,
and also compounds of type
groups were the
and
II and IV in which the R
naphthyls.
HISTORICAL As has been stated In the Introduction,
earlier work in
this laboratory^- has shown the p o t e n t i a l i t y of d i h y d r o resorc inol as a starting reagent for the pr ep ar at io n of m et a substituted aromatic hydrocarbons.
The thesis of Dr. Erwin
W. Tucker^- very thoroughly encompasses the hi storical b a c k ground of the efforts of early workers to prepare the few polyphenyls which are known.
This histor ic al
search will not
be repe at ed here and the reader is r eferred to Dr. T u c k e r fs thesis. It should be of Interest, however,
to rev ie w the work
w h ic h has b een done on substituted polyphenyls.
Since this
thesis concerns itself w ith m e t a disubstituted benzenoid compounds, xenyl
w he rein the
substituents are either phenyl or
(the accepted nomencl at ur e for the biphenyl radical
w it h one free valence), primarily, recent
this histor ic al
compounds of this type.
and v e r y i nt eresting work
terphenyl,
this c ompound will be
summary will cover,
However,
in vi ew of some
on the chemistry of oincluded
in this portion of
the thesis. Schmidt and S c h u l t z ^ appear have reported the p r e p a r a t i o n of terphenyl.
to be the first workers to any derivatives of m-
A trinitro compound resulted from the treatment
of m-ter ph en yl with f u m i n g nitric acid. to prove Its structure. zinc and h ydrochloric
Ho attempt was made
This compound on reduction with
acid afforded a "288° m e l t i n g base".
A raonobromo and tetrabromo derivative h ave been r e ported by Olgiati^;
the former substance was pr epared from
equimolar amounts of m-terphenyl and bromine
in carbon
d isulfide and the latter f ro m either m -terphenyl or f r om m on ob ro mo -m -t er ph en yl b y treating with excess bromine. Ox id at io n of the monobromo compound with chromic
oxide gave
either 4- or 6 - b r o m o - 3 - carboxydiphenyl which led Olgiati to conclude that the m on ob ro mo derivative would be 4 f-bromo-mterphenyl#.
Oxidation of the tetrabromo compound gave both
COOH
COOH
This nomenclature and that used throughout this thesis is in accordance with that recommended by Chemical Abstracts. s' 3"
3
3 3
m -Terphenyl
o-Terphenyl
4 -bromobenzoic
acid and 3 ,4 -dibromobenzoic
to conclude an original compound,
acid which seemed
3 " , 4 , 4 f,4"-tetrabromo-m-
terphenyl.
COOH
COOH
Br France, H e i l b o r n and H ey ^ have also studied the nitro derivatives of m- te rphenyl a tri-nitro-m-terphenyl.
by preparing a mono-,
a di-,
The mononitro compound was
and
shown
to be 4 1-nitro-m-terphenyl since on oxi da ti on it gave 2 nitro-5-carboxydiphenyl,
the structure of whic h was pr ov en
by an independent synthesis.
F o r the dinitro
compound they
COOH
proposed the structure
4, 6 f-dinitro-m-t©rphenyl since this
compound on oxidation gave 4-nitrobenzoic
acid,
indicating
the second nitro group was in the para p os it io n of the termi nal ring.
T hey p roposed the structure 4 , 4 " , 6 r-trinitro-m-
terphenyl for the trinitro derivative, b a s i n g this on anology but on no chemical evidence. f i rm ed by Wardner,
This work was e s s e n t ia ll y c o n
and L o w r y ^ who synthesized, the same nitro
d er ivatives and came to the same conclusions as to structure. T hey fu rther reported that the trinitro compound was r e s i s tant to oxidation.
By catalytic
reduction of the mononitro
derivative these workers p repared the c o r r e s p on di ng monoamine (m.p.
64°).
F r o m this they prepared the hyd ro c hl or id e salt,
the acetyl derivative (m.p. 152°).
(m.p. 117°) and the benzoyl derivative
Dia zo ti za ti on of the amine fo llowed by c ou pl in g
w it h various naphthyl residues
gave colored compounds p o s s e s
sing dying properties. The mo no ch l or o and mon ob ro mo derivatives of m-terphenyl h av e b e e n synthesized b y Cook and Cook^ through the treatment of m-terp he ny l with the corres po nd in g h a l o g e n in the presence of iron.
In both cases the h a l o g e n was
4 f-position. the acid,
shown to be
In the
The 4 f-chloro-m-terphenyl was oxidized to yield
2 - c h l o r o - 5 - c a r b o x y b i p h e n y l , whose structure was
p r o v e n by synthesis f r o m 3 - n i t r o - 4 - a m i n o t o l u e n e .
This same
oxidative procedure was also employed to prove the structure of 4 1- b r o m o - m - t e r p h e n y l .
In an attempt to account for the
absence of any 4 - br o m o - 3 - c arboxybiphenyl products,
in the oxidation
they prepared 3-methyl-4-bromobipheny l and carried
out the same oxidative procedure on it.
All attempts failed;
the desired product was a pparently destroyed dur in g the oxi-
Cook and Cook^ have also prepared the 4 T-anino-mterphenyl and 4 f- i o d o - m - t e r p h e n y l .
The former was obtained
by treating 4 ^ c h l o r o - m - t e r p h e n y l with an excess of 28/£ hyd ro xy la mi ne
solution,
cuprous chloride,
calcium oxide,
and
copper for a period of thirty hours at 190° C. and 800 to 850 p.s.i. chloride,
The product was
isolated as the amine h y d r o
The free amine was liberated with pota ss i um
hydroxide.
Transf or ma t io n of this to the d ia z onium compound
and addition of po ta s s i u m iodide afforded the 4 T-iodo-mterphenyl The reaction of cyclohexene oxide with phenol in the presence of boron trifluoride has b e e n shown by Price and Mueller
8
to result In a small amount
terphenyl,
of 4,4 n-dihydroxy-m-
although the principle products of the reaction
were p -c yc lohexylanisole and 1,3-dianisyl cyclohexane. Similarly some 4 , 4"-dimethoxy-m-terpheny l Is obtained w hen cyclohexene oxide chloride.
is treated with anisolo and aluminum
Substitution of 1 ,2 -dichlorocyclohexane for
cyclohexene oxide
results In similar reaction products.
The
4 , 4 "-dihydroxy-m-terphenyl was reacted at 300° C. with zinc dust to give m-terphenyl. At the time of this writing,
Bradsher and Swerlick^ are
apparently In the process of a more comprehensive i n v e s t i g a tion of certain reactions of m-terphenyl.
A pr el i mi na ry
report has indicated some Interesting results.
Bradsher
implied that hi s earlier work had shown that mo no ha logenation and n it ration resulted in substitution of the 4 f-position
while the F r i e d e l and Grafts reaction resulted in substitu tion on the 4-position.
In preparing the 4 1-cyano-m-ter-
phenyl by the reaction of crude monobromo compound with cuprous cyanide,
these workers obtained not only the expected
4 ’- c y a n o - m - t e r p h e n y l , but also a small nitrile fr ac ti on which yielded 4-carboxy-m-terphenyl on hydrolysis.
Also,
in study
ing the benz oy la ti on of m-terphenyl by the Friedel and Crafts method,
they found that their product contained some 4 ’-
be nz oy l-m-terphenyl as well as the expected 4-benzoyl However,
wh en using the Perrier complex of benzoyl chloride-
a luminum chloride, tained,
isomer.
only the 4 ’benzoyl-m- te r ph en yl was o b
and this in 69% yield.
a i 2 c i 6 .2 G 6h 5coci
+
Perrier complexes w it h p-tolyl
sr CO
and m-tolyl chlorides also brought about 4 ’-position.
substitution in the
These workers also report the p re pa ra ti o n of
several n e w m-terphenyl derivatives,
but details have not yet
been published. o-Terphenyl Derivatives An extensive
investigation into the chemistry of o-ter-
phenyl has been initiated by Allen and co-workers with the result that a number of its fundamental reactions have been elucidated.
As Allen and Pingert-^-0 have pointed out,
the
few known derivatives of o-terphenyl prior to their i n v es ti gation were compounds r es u lt in g from degradative
studies on
large and complex molecules.
after
A l len and Pingert,
re vi ew in g the earlier attempts to prepare o-terphenyl, found that the most
satisfactory m e t h o d involved a W u r t z - F u t t i g
re ac t i o n of chlorobenzene with sodium.
F r o m 2.5 kg.
of
chlorobenzene and 230 g. of sodium they were able to obtain 70 g. of o-terphenyl
(m.p.
58°).
The general r e a ct iv it y of the molecule
is des cr ib ed by
A l l e n and Pingert as being" along two m a i n chemical axes:
The 4- and 4 n-positions have been shown to be the most r e active, while the 3 ’- and 4 '-positions are reactivity”.
"secondary in
This situation was borne out in such reactions
as h a l o g e n a t i o n and nitration. For
some reason it had b ee n speculated that such a m o l e
cule as o-terphenyl might permit the Kekule
structures of the m id d l e rang.
any such property, lysis fragments
isolation of one of the In an attempt to find
the mole cu l e was ozonized and the h y d r o
studied.
As seen below,
a preferred Kekule
structure would result in different products.
CHO a ~ H sCOCHO -h{ ° CHO
C 5H 5 C = 0 I C 6 H 5C = O
-h
CHO I CHO
It is not difficult to appreciate the problems involved in such a study when one sees that either or b o t h terminal rings m a y be attacked by the ozone also.
That this did occur was
quite obvious to Allen and Pingert since they were unable to i de nt if y In appreciable amounts any fragments other than glyoxal.
N o r were they able to reproduce these ozonolysis
experiments to any satisfaction. These
same workers have
shown that o-terphenyl Is c a p a
ble of rearrangement to various isomers under certain c o n d i tions.
In anhydrous benzene with al uminum chloride,
o-
terphenyl first rearranges to m- te rphenyl and finally to p-terphenyl. is used,
If an equivalent amount of aluminum chloride
the results are more drastic;
among the products
formed are p-terphenyl and t r i p h e n y l e n e .
As the temperature
and c o nc en tr at io n of aluminum chloride are Increased,
con
densation products predominate. Allen and P i n g e r t ^ have reported the acetyl, benzoyl, bromo,
and nitro derivatives of o-terphenyl.
workers expected,
acetyl chloride or acetic
As these anhydride c o m
bined w ith o-terphenyl In the presence of aluminum chloride
11. to give 4 -ac e t y l - o - t e r p h e n y l .
The structure was verified by
showing that this compound was identical with substance obtained f ro m a Wurtz reaction of o-iodobiphenyl with pbromoacetophenone.
Usin g sodium hypochlorite the acetyl COCH