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6-1-1947
The action of bromine on 1-PNitrophenyl-4-Phenylbutadiene 1,3
Leonidas Brown Barron
Atlanta University
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Recommended Citation
Barron, Leonidas Brown, "The action of bromine on 1-P- Nitrophenyl-4-Phenylbutadiene 1,3" (1947). ETD Collection for AUC Robert
W. Woodruff Library. Paper 183.
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PREFACE
The author is indebted to Dr. K.A. Huggins
Head of Department of C~iemistry, Atlanta University,
for guidance and assistance in the prejaration of
this thesis since its begix~ning in 1946.
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Ofl~ICAL
This paper deals with the addition of bromine to lwP~
RffEU
iii tropheny1~4 phenylbutadiene i~ (02N-06114— (~=C-Ce~C~H5).
~he results obtained are compared with those obtained by
other workers in related fields,
Some of the important
theories which have been formulated to ezplain additions
to oon~ugated systems are discussed in this paper.
Zn 1889 Thiel? developed his theory of partial valence,
which has been
to useful
explaining addition to oom~
pounde containing conjugated double bonde
theory0 in nml
According to the
pie lin)agee the valence beyond the first do
not utilize as much of the atomic affinity as a single bond
leaving free a lar
partial valence.
*
thoug2i variable amount of affinity
In the case of butadiene l,~ each of the
f~i]r carbon atoms would have a partial valence, represented
as
ollo~s:
~Cr.I—CC~
¶i~he two carbon atoms in the
oentçz are pictured as having free affinity yet are bound
together by a single bond; this affinity saturates itself
acroae the single bond.
According to this theory
reaction takes place on the first
addition
fourth carbon atom
the so-called 1,4 addition to the conjugated
~tem.
12!hiele1 Ann. 306, 8? (1099); 308, 3~3 (1899).
1
—
2
Ingold’ gives a different view on the mode of addition
in his studies of butadiene
1,3. )(ixtures of the 1,4 and 1,2
dibromides are formed when butadiene is treated with bromine.
The 1,2 dibromids when heated at 1000 yields some of the 1,4
dibromide.
~C-CCK2
4O~~
B~g-cK=CK-CR2
Ingo34 states that 1,4 addition is always a product of its 1,2
jnsomer.
He assumes that during the initial addition process
ions are formed and that
fl8j~~
the see and bromine atom is
liberated (as an ion) only during the addition of the first,
the in~tia1 product of addition consists of the ions of the
1,2 dibromide~~
g—~cHz.
What happens after the initial
stage of the reaction process depends upon the conditions of
the ex~eriment~
In a non~.ionizing medium, association takes
place aM a 1,2 addition product is formed.
tTnder these con
dition.e the production of any 1,4 additIon product results
from rearrangement of the 1,2 dibromide,
Foz’ ox~uzple, when
bromine is add~d to 1,4 diphenylbutadiene, according to Ingold,
the 1,2 product is formed first
The bracket izidieat~s an ~n~notropic system and Ph CHBr and.
Ph are activatirzg~ groups.
The Ph group is represented by
Xngo1~ to be rapid and complete promoting a change from the
~,4 to the 1,2 product, whereas the Ph CHBr is slow and in
complete promoting a change from the 1,2 to the 1,4 addition
product.
In such a system Irigold concludes that the result
½urton and Ingold, J. Chorn. Soc., 904 (1928).
r
3
is always a 1,2 or 3,4 ad.dition product..
Among the groups
favorable to anionotropic change are alkyl, phenyl, carboxy,
and eyano substitutierits and neutral groups containing
wishared electrons in association with the atome to which
it is attached.1
!ngold and Smith2 made studies of the addition of
iodine monochloride to conjugated systems and ethylenic
linkages.
They were interested in determining~ for unsymmet~~
neal products1, such as the 1,2 dibromide of butadiene and
3,4 dibromide of sorbic acid, which is the point of initia
tion of ~.ttack and which is the point of its completion.
They reported that the addition of iodine monoebloride to
propylene gave predominately CE~.CECl.CE21, styrene gave
95~$ C6E5 CECI CE2!, crotonie acid gave 92
and ethylene suiphonic acid gave 90
0fl~~CIK~l.CHI COOR,
CE2C1.CHI.303L
These
results were in line with the theory that iodine adds pre-.
dominately to the o&carbon atom in the double bond.
These
results are in harmony with results reported by other
workers..
Ingle3 reported making c6E50EC1.aR2! when etryene
was treated with Wi~)s’s and Rubi’s solution.
Erlenmeyer4showed
that ~6R5 CKC1 CE! COOH is the principal product of the
action of iodine monochionide on cinnamic acid.
1Burton and Ingold, J. Chem. Soc., 904 (1928).
2lngold arid Smith, J. Chem.. Soc., 2742 (1931).
3Ingle, 3. Chew. Soc. Irid., 21
4Enlenmeyer, Ann., 289
591 (1902).
270 (1896).
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5
Theland’ attempted to explain the addition of bromine
to olefins or congugated compounds on the basis of resonance.
when bromine adds to propylene in a non—ionizing solvent the
product can only be propylene Dibrornide (I).
After the
addition of one bromine atom to (carbon atom 1 or 2 ~ the only
ion left in solution would be a bromide ion (Br-) to add to
carbon atom 1 or 2.
~r
Br
- CE — CH~
3
2
1
I
H~C
~
—
0B
Br
CE - CH~
2
XI
IY~C
3
-
Br
CE
2
UI
-
(XE
CE2
1
If the reaction is carried out in water two possible isomers,
U or III would result after the addition of one bromide atom,
The addition of bromine to butadiene is explained by Wheiand.
on the same mechanism as f or the addition of bromine to prow—
1ene~
The active reagent is a positive bromide ion which is of
course electrophilio.~
The point of attack in butadiene would
where an unshared pair of electrons could be provided
OCCU?
uwst easily.
The structures I and U indicate the ways in which
~ unshared pair can be brought to the terminal, or to one of
aE2: Cli
-
I
CE
CE2
CE2
-
CE
CE
CE2
U
the central carbon atoms respectively, as the molecule is
polartzqd in the reaction. Structure I has two ways to permit
the s~hift of electrons, whereas structure XI has only one.
It
is easier for the reaction to commence at the terminal carbon
atom producing a product pictured as a resonance hybird of III
or IV.
1G. W. Wheland, “The Theory of ~esonanee an~ its Appli
cation to Organic Chemistry, ~m.J~ohn Wiley and Sons, New York,
1945, p. 245.
6
According to the theory bromine (Br—) will add to carbon atom
3 in structure lIT to produce a 1,2 or 3,4 dibromide,
In
structure IV bromine (Br-b) will add to carbon 1 to produce
Br
Br
12
34
1
2~
itT
lv
3
4
the 1,4 dibromide. Wheland does not believe that it is possible
to predict whether the 1,2 or 1,4 isomer will, predominate over
the Other, but be concludes that the di~cnssion has been of
value in that it provides a simple and logical explanation of
the two possible isomers.
~n treating 1-p nitrophe~yj
4 - phenylbutadjene 1,3
REEK
C
C
- 06R5) with bromine in equlmolar
qu&~itities, It is readily seen that two different ethenoid
groups are competing f,r a limited amoimt of bromIne~
lugold
made a limited study of the additIon of bromine
to co~n~~eting ethylenlo groups4
Li~ñ~tod quantities of bromine
werO added to mixtures of ethylene and substItuted ethylenes
in an inert solvent.
liz this method all re~u1t~ are compared
with the activity of ethylene, ethylene being taken as uiiity.
Baner2 has provided several qualitative comparIso~~ and the
results recorded by Reicho van Wyok and Waele3 may be con
sidered as roughly comparable among themselves.
The former
concluded that alkyl, phenyl, bromine, oarboxy and cyano
3ingold and Ingold, J. Chem. Soc., 2354
2Bauer, ~ 37
3317
(1931).
(19Q4).
3V~ck and Waele, Rely. Chem~ Acta.
4
242
(1921).
-
‘7
subs tituents d.e-activate the etI~aoid nucleus, whereas the
latter investigators reported a small and wnbi~uous effect
for alkyl groups but supported Bauer’s deduction re arding
the de-~aetivating influence of phenyl and oarboxyl substituents.
Similar investigations have also been reported by Hertz and
Eofman and Kirmrenther,2 Su~db ourough and Thomas ,3
WilUame and ,]~ames,4 and Davis.~
Ti~resu1ts reported by
these investigators seem to be too varied to draw any valua~Z~,
conelus ions,
~Phe work of Bergmann6 pertaining to the synthesis of
substituted stilbenes and diphenylbutadiene; and the work
of Bachman,7 who stxulied ois-trans isomerism of substituted
di
-
and tn
-
phenylbutadienes, were of considerable interest.
~Bergmazm in his synthe~es prepared 1—p nitrophenyl
—
4 phenyl-.
butad~ene 1,3.
1,3
1
—
Ba.clunan prepared 1—0 nitrophenyl -4- phenyi.
OCORR H
H
earbo~rlio acid (02Nc6H4
~
:~ C :
C~H5) and
-
decarboxylated it giving 1—0 nitrophenyl
1,3.
-
4 phenylbutadione
Our attempts to deearboxylate the corresponding p
3~ertz and Mylius, Ber., 39~
38)~6
—
U906).
~Hofman and Xirmrenthen, Ben., 42
4481
(1909 ).~.
3Sudbourotigh and Thomas, J~. (Yhem. Soc., 715, 2450 (1910).
4Williams and ‘ames, 3’, Chem. Soc.,, 34~, (l9~8).
5Da’ris, 3’. Am. c~hem. Soe., 50
6Bergmann, 3’.
7Baehman, J
2~•
~.
Chema.,
Chern., 8
6
2769
134
311
(1928).
(1941).
(1943).
8
nitro acid were unsuccessful.
Three compounds are possible when bromine adds to 1-p
nItrophenyl -4— phenylbutadiene 1,~.
H~HK
02N-.a6R4- C~O-O~~C~
rBr
RKKB
O2N-.C~K4— C~-C:C-a6K5 + Br2
—‘
2N_c6H4-q-e~c-~frc~5
II
Br
o 2N- C5R4—C—C- C:C—C6K5
In
BrBr
O’zonization of a compound represented by- structure I followed
by hy~d~olysis would yield p—nitro benzoic acid (m.p~ 238°),
and 1,2 dibromo.phenyl propionic acid (m..p
2O6~)4
0~oni—
cation of a compound represented by. structure II followed by
hydroZysis would yield c~c.bromo phenyl acetic acid (m.p. 84°),
aM c(bromo p-nitrophenyl acetic acid (m.p. unknown)~. Ozoni
zation of a compound represented by structure Ifl followed by
hydrolysis would yield 1,2 dibromo p-nitropbenyl propionic
acid
(Sep.
217—218°), and benzoic acid (m.p. 122°).
Oxidation
of these compounds (represented by structw.es I, II., and III)
to glycols followed, by cleavage with lead tetraacetate would
yield the same products as indicated in the process of ozo—
nolysie.
Products pictured as def.iving’ from structures U and.
XXI were not isolated in any- of the experiments.
P nitro
be~nzoic acid and derivatives of 1,2 dibronia propion~c~ acid
were isolated in experiments carried
OUt
bYt~e above prooesses~.
CRA?2~R U
R~N~
~~ZL0N
~TRQP~1Y~
-
j
BUTA1)~k)~ ~
In a 500cc KJeldabl flask, fitted with a. condenser con
taming a calcium chloride tube, was placed a mixture of
p
-
ziitro~heny1 acetic acid (36 g), cinnm&4ehyd.e (2~ g),
and lead monoxide (22 g). To this mixture was added acetic
a!4~xiride (40 g).
The entire mixture was zefl.~wced f~ five
bourn at a temperature of 1800. After coo1ing~ the crude
product was filtered
ith sucUofl to remove the lead acetate.
The precipitate was extracted twice with boiling acetic
ac~d~ which on i~recipitation gave an impure product~ that
melted at 177
-
78~. The impure product w~e dissolved in
ehloreform and washed several times with a 5% solution o~
sodium 1~drexidei Concentration of the ehlorofoz’ui yielded
5 grams of yellow crystals (mop
retiv~a1 based on p
-
1729, or 10~ of the thee”
nitrophenyl acetic acid. This melting
point was the same as that reported b~r ]3er~rmRrm’ who had
previously prepared this compound.
1Dergioann,
~.
~
Cham.
~ 134
9
(1941).
•.~
In a large ~ley~n2yer flask l~. grains of l-p~ riitro~
phenyl
~ phenylbutadiené ~ was dissolved in ~OO cc
of metby~ene ch1orid~e., The flask was fitted with a three
hole stepper contaiz4ng a mecb.anical stirrer, a separa~
toi~r funnel~, ancL the solution was coo!i~ed to ~ Through
the eeparatory funuel~. with stirrer in moUon,~as sdded~
4ropwise 9~6 ~ (3.1 eel of bro~nine dissolved in ~OO cc
of me~1~y1ene c~g~ric~e
~urir~g the addition the temperature
was not allowed, to 7i8e above 5°o After all of the b~ouzine
ha~ been adde~ stir~ing we~ continued for on~ hour~. The
stirrer was etop~p~ and. the temperature of the aolu~tion
was allowed. to rise to roorn~ temperature. The meth~lene
chloride was removed by distillation uncLer reduced pr
aad the
~ijg
was recrys~t
.i.aed from ethyl acetate.
~rield. of iight brown crystals was 93~32 grams (ni~p
l~
380) or ~7O% of the tIzeoretical~
~yi~
c
o
F~uniit
d~ for
~
8~9~
~ 38 ~6; 38~8l
~
~IB~O~L(~ ~
AT~ ~
~
~
________
The fiItbrorni4~e of lap
DIJ~ThRQX~
-
nitrophez~rl
-
-
_________
4
phenylbutadiene
1~3 (3 g) was d4~ss ived. in. 6O~ cc of chloroform an~ added. to
~0 cc of chloroform containing 10 ~aas of perben~oie acid.
pu~ au~w~,toa
(ewr)
~
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12
~filE PREPARATION OF 1,2 DIa~DROXY
BROMO
(~!!
-
1-~
-
~
4
-
-
~,i DI
PRENYLBV~!M~1E
USE OF PER ACE?!C~ ACID)1
A mixture Of 120 cc of acetic acid and 48 cc of hydrogen
peroxide (~0~$) was placed in an Erlenmeyer flask and heated
for one hour at a temperature of
The solution was
750~
allowed to cool to 25°., and to the cooled solution was added
5 grams of the dibromide of 1-p
butadiene 1,3.
-
nitrophenyl
—
4
-
phenyl
The reaction started immediately, and was
allowed toreact until the solution reached room temperature;
after which the solution was extracted with ether and washed
with a 5
acid.
eolution of sodium hydroxide to remove the acetic
The ether was dried over calcium chloride and removed
by distillation under reduced pressure.
The yield of light
yellow crystalline glycol was 4.6 grams (m.p
85
58.600), ~zi
of the theoretical.
~na1. Calod.. for C16H15O4NBr2;
Found.:
Br~ 36.07;
Br, ~5 95.
~5.97.
A~T$MPTED CLEAVAGE OF 1,2 D!HYD~ROXY 3,4
BROMO
-
~ -
NI?RQ?E~EYL
-
4
-
DI
PHENLBU’J~AKE
(THE 23~ i?!. PERIODIC ACID)2
A solution of 2 grams of Potassium periodate in 100 cc
of N
sulphuric acid at 200 was rapidly added to a solution
~can1an and Swern, 1. Am
Chem. Soc., 62
2Eeinke and T~uce, J~. md, ~ Chom., 18
King, J. Chem. Soc., 1~26Tl9 :
2305
(1940).
244 (1946);
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the solution was made alkaline eizd extracted with ethers
The
ethereal extract, which gave a negative test with Fizohein
aldehyde reagent was distilled under reduced pressure,
The
solid, when purified, yielded one gram of the original glyool.
The alkaline solution was boiled for a period of one hour
and the solution was extracted with ether which ~rielded, when
concentrated, a product containing bromine (m.p.
The
80).
melting point did not change when mixed with authentic bromo
styrene which melts at 8~.
The aqueous solution was a~cidif led with dilute sulphuric
acid and extracted with petro eum ether,
~oneeutratjon of
the petroleum ether gave a bromine containing product which
melted at 1300 (the melting point reported in the literature
f or oc-bromo elrtnamio acid).
The melting point did not change
when a sample of this compound was mixed with authentic
.<-
bromo einnamio acid.
Concentration of the water solution yielded 1.32 grams
of a product (m.p. 238°) containing no bromine,
The melting
poiut of a mixture of this product with authentic p
-
nitro
benzo~e acid was also 2380.
QZ0NTZATIO~ ~ ~ DThROMThE 0? 1~p~
-
Zn 100 cc of methylene chloride was dissolved 3 grams of
the dibromide..
The solution was cooled to 0~ and a stream of
ozone was passed through the solution for a period of twelve
hours~
The methylene chloride was distilled under reduced
pressure •
After the ad~dition of water and hydrogen peroxide,
15
the mass was a11ow~d to stand. for twenty four hours.
The
solution was made alkaline and extracted with chloroform.
The chloroform layer yielded 0.52 gram of tue original
dibromide.
The alkaline solution was boiled for a period of one
hour and the solution was extracted with ether which yielded.,
when concentrated, a product containing bromine (m.p, 80).
The melting point did not change when mixed with authentic
bromo styrene which melts at 80.
The aqueous solution was acidified with dilute sulphuric
acid and extracted with petroleum ether.
Concentration of
the petroleum ether gave a bromine eontaining product which
melted at lZ0~ (the me ting point reported in the literature
for c’<-bromo cinnamic acid).
The meI~tiiig point did. not change
when a sample of this compound. wae mixed with authentic
0<
-
bromo cinnamic acid.
Concentration of the water solution yielded one gram
of a product (m.p. 238°) containing no bromine.
The melting
point of a mixtare of this produot~ with authentic p
nitro
benZOie acid was also 2380.
I
CHAPTER III
SUMMARY
I.
The dibromide of ~ 1,3 was
prepared.
II.
Attempts were made to prepare 1,2 dihydrcxxy 3,4 dibromo
l—p—njtroraierwmutane by the use of (1) potassium pernanganate, and
(2) by the use of perbenzoic acid.
III.
1,2 dihydroxy 3,4 dibromo 1-p—nitrophenylbutarie was prepared
by the use of peracetic acid.
IV.
Cleavage of 1,2 dihydroxy 3 ,4 dibromo 1—p-nitrophenyThutane
and ozono~rsis of the dibromide of l-p-itroj~ieny1—4—phex~-1butadi.ene
1,3 yielded the same products.
1J• All products isolated were derived from a 3,4 addition
product
According to most theories, it would be expected that bromine would
add 1,4. to ~
Ezperimental results
proved the structure to be a 3,4 derivo~4ye, which is somewhat in
accord with Ingold ‘s theory of addition to conjugated systems.
16
CRAP~R IV
BI~IOGaAPHY
4~TICLFA8
~4kins, Homer and. CQnner) Balp]3. ~The Catalytic Rydro
gefla~ion of Organic Com~ound.a over Copper Chromite
~ ~m~ic~ Chemic~
ele , ~, 1091
Bac~nan, G~ B. aria Hoagli
B. I. “An Attenxptei Syntheais
of a Cyc1oocta~etraene. Cis - ~ra.ne Iaom~rism of
~Ribet~ituted Di and ~i ph
1butad~ienee~° Journ~,
of ~ Cheniietry~ -8, 311, (1943).
Bauer, ~igo~ °Zur Keuritnios- der ~I~1enstoff4o~pe1biBdTmg.
J~4itiou von &‘om,” 33eriçhte ~ deuts~cb ghen$aeh
Gc~~ha~t 3
331’l, (190i).
Ber ~:
.~
Burton
~‘eJ.iz~ ~n~i Weinherg, Zi~orah
“~marke on the
S.ynthesi~ of 5ubetituted~ tilbeneE and Diphenyl
but gjezie~,” ~ourziaj ~ ()rgar~ Chemistry, ~,
J34~ 41941).
Harold and tzigol~ Cd~ato~pher. ~1cbile.~Axiion
term~riam, part I~ A preli.miliar7 Study of the
Conditione of ActivatiOn of the Thzee.a.Carbon
Sy~
and a DiecUeeio~i of the
ulta in Relation
t~ the Modes of Aaditiou to Conj~gatad Systems, ~‘
~ ~. ~ ~ Societ~y, 904, ~1928)
Davia~ Harold S. “The Relative Bates of B~omoflatiofl of
the Olefins,” ~ of ~ ~ Chemie~
ocie
~ 2769 (19~).
Hocke~t
Rô C and ~cC1e
W. S. “The Qg~idation of
Certain Glycoeides by Lead Tetraacetate~ jq1~fla~
~ ~ic~axi ~ ~pc~.otiii ~ 1~7~ ~1939~,t
ingold
Cbz~istopher and Ingol~ ~d.ith B. “Influence of
Su1~sUtuentS on the Additive Reactivity of tliylene
Derivatives Part I. I~e1iZajZ1a~Y Observations Ofl
the A4.dit-ion of ~omine in olutiofle, ‘~ rournaZ, ~
~ çj~endea1 Soc ie~, 2354~ (1931).
1?
18
IngoLd
Chrie to~pher aM Smi.th, Hex~xy G. ~e node of
~d4ition to Conjugated Uneaturated Syeteuie Part
II1o~ Fuz~ther R~max~ko and Ob~ervatione Bearing e1~
~eehanien~ of Addition of 1~a1ogens and. J~t1xog~n
HalideS ~ Journe3~ ~ ~ cheice~1.
i t
2742,
~jayo1 ?~Lm_k R~ and e11ieg~ Cheve$~ DTh~ 2eroxid.e ~ffect
in th~ ~dtUtion of Re~geuts to Uneaturated. Cornpounds and in Rearrar3~emeUt Reactions “~m~c~1
~ 351,
(1940)
kusicat, Irving and Nèrt~rup, He~bart ~
“5tudies of Con.
3 ted. Syetems V. The prepa~ration and Cblorona
ti~n of Buta4tiene,” ~n?i~ of ~ ~te~i~can
~ Spcie
5
4O~43 ~T93O)
Sean1an~, John T and Sweria David., ~Action of Lead
Teti~acetate u!pon I~draxy1ated. Fat Acids and Re
lated Cornpounds. Uydro~zy21.ated Oleic Acid, ~tby1
01sate and Oleyl .Alcohcl., ~‘ JpiLrna~ of ~ ~erican
~J~~emic~ ~ag~z, ~, 23~)5~ 23O9~~ (~4OT
SuLibouro
:‘. John T,• and Thov~aa John,
~The Addition of
~romine to Unsaturated Com~oun4.~, ‘~ Journ~ ~
~ S. is
715, (1910).
Williams, David M and. J~ie
Thomas C. “The Addition of
Bromine to ~tk~rlenio Compound.~’ in a. No l~r&rox.y.~
lated ~o1vente’ ~ of ~ hemic~ S is
~4~s (1928)
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