The Synthesis of Butadiene Derivatives

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P U R D U E UNIVERSITY

T H IS I S TO C E R T IF Y T H A T T H E T H E S IS P R E P A R E D U N D E R MY S U P E R V IS IO N

BY _________________________ S i d n e y

E N T IT L E D

THE S Y N T H E S I S

M.

F o x ___________________________

O F H J T A C IE N E D E R IV A T IV E S

C O M P L IE S W IT H T H E U N IV E R S IT Y R E G U L A T IO N S O N G R A D U A T IO N T H E S E S

A N D I S A P P R O V E D B Y M E A S F U L F IL L IN G T H IS P A R T O F T H E R E Q U IR E M E N T S

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Table 5 1-SUBSÏITUTED- 1 , 3-BUTADIENES CH2t»CH-CH»GH R Substituent-R

Y ield , 1o on Dehydration

B .P.° C. (mm.)

20

x

IvI.P.0 C, M.A,D.a

Phenyl*3

62

79-81 (7)

1.5943

120

p-T olyl

60

95-96 (2)

-

117

p-Chlorophenyl

58

85-87 (15)

1.6189

107

p-Fluorophenyl

55

68-69 (12)

1.5794

113

3 ,4-D ic hlorophenyl

55

85 (2)

1.6374

137-138

p-Eethoxyphenyl

53

122-124 (6)

-

144

cS^Thenyl

48

79-81 (11)

-

112

cSçFuryl

52

72-73 (10)

-

103

< ^ a p h th y lc

51

130-132 (4)

1.6347

160-161

%.A.D. = maleic anhydride d e riv a tiv e . “Reported by Braude, Jones, and S te rn , J . Chem. S o c ., 1947, 1087. ^Reported by Arnold and Coyner, lo c . c i t .

XV

T able 6 P0L*ÏM3RS PREPARED FROM 1-3UBSTITUTED-1, 3-BUTADISrIES

Monomer (1 -su b stitu e n t)

Y ield , % (20 h rs ,)

D escrip tio n of Polymer

Phenyl

40

gummy, g ra n u la r

p-T olyl

45

gummy, g ran u lar

p-Chlorophenyl

55

b rittle

p-Fluorophenyl

48

b rittle

3 ,4-Dichloro

60

b rittle

cR-Thenyl

42

gummy, g ran u lar

c^-Furyl

44

gummy, g ran u lar

POLYMERS PREPARED FROM 2-3UBSTITUTED- 1 , 3-BUTADIENES Phenyl

77

rubbery, s o ft

p-T olyl

76

rubbery, s o ft

p-Chlo rophenyl

80

rubbery, s o ft

p-Fluorophenyl

82

rubbery, s o ft

3 ,4-D ic hlorophenyl

78

ru bbery, hard

p-Methoxyphenyl

72

rubbery, hard

d^-Thenyl

65

rubbery, b r i t t l e

^-N aphthyl

51

rubbery. b r i t t l e

xvi

SmBIARY A number of 1- and 2 -s u b s titu te d a ry l-1 ,3 -b u ta d ie n e s has been prepared by re a c tio n of butadiene monoxide w ith organom etallic compounds. stu d ied .

The polym erization behavior of th ese dienes has been

PART I I

xvü

(C ontribution from th e Purdue Research Foundation and Department of Chemistry, Purdue U n iv e rsity , L a fa y e tte, In d .) PREPARATION OF ANALOGUES OF POLYAMIDES* by G. Bryant Bachman and Sidney H, Fox AN ABSTRACT The search fo r a method of preparing polyamides, which would have th e p ro p e rtie s of p ro te in s , has been proceeding fo r a number o f y e ars.

The most s ig n if ic a n t re c en t advance along th is lin e was the

work rep o rted by Woodward. ^ He described the p re p a ratio n of high mole1 Woodward, J . Am. Chem. S o c., 69, 1551 (1947). c u lar weight polyamides (1,000,000 to 15,000,000 u n its ) from anhydrides of N-carboxy- X-amino a c id s . I t was o f in t e r e s t to tr y the methods used by Woodward to p re­ pare analogous types of polymers.

The types of polymers d esired were

p o ly e sters ( -0-CHR-C0-)n , polysulfonates ( -OCHR-SOg-}^ and p o ly su l­ fonamides ( -NHCHR-SOg-) n . Many attem pts were made to prepare the above compounds. most cases polymers were obtain ed .

In

However, the pure monomers, necessary

fo r the c o n tro lle d p rep aratio n of these polymers, were never is o la te d . The d u p lic a tio n of r e s u lts in polymer form ation was dependent on th e is o la tio n o f the monomer.

Therefore th e polymers were of l i t t l e in te r e s t .

* From the Ph.D. th e s is o f Sidney M. Fox, Purdue U n iv e rsity , Feb. 1950.

PART I

THE SYNTHESIS OF BUTADIENE DERIVATIVES

INTRODUCTION S u b stitu te d 1,3-butadiene molecules vary g re a tly in t h e i r ease of polym erization and in the p h y sical p ro p e rtie s of th e ir polym ers.

The

importance of com pletely exploring the re la tio n between s tru c tu re and p ro p e rtie s of diene polymers is shown by the f a c t th a t polymers o f ch lo ro prene and bromoprene a re v a s tly su p erio r to those of isoprene as sy n th e tic rubbers.

C arothers and Berchet®»7 obtained d ata which showed th a t the

b e st rubbers were obtained from 2 -s u b stitu te d d ien es.

In Carothers* work

th re e types of s u b stitu e n t groups were stu d ied - a lk y l, phenyl and h alo ­ gen.

I t was found th a t a l l o f these groups in the 2 -p o sitio n have an

a c c e le ra tin g e ffe c t upon the ra te of polym erization.

The e ffe c t in ­

creases from methyl to h epty l among the a lk y l groups and i s even stro n g er fo r the phenyl group.

Halogens show an even g re a te r e ffe c t on the ra te

of polym erization in th e o rd er ch lo rin e ^bromine ^ io d in e .

C arothers also

reported th a t s u b s titu tio n on the 1 -p o sitio n of dienes depresses the a c tiv a tin g e ffe c t of a group on the 2 -p o sitio n .

S u b s titu tio n a t the

3 -p o sitio n g en erally re in fo rc e s the e ffe c t o f a group alread y p resen t a t the 2 -p o sitio n . Although 2 -p h e n y l-l, 3-butadiene polymerizes ra p id ly the polymer is s o ft and has a r e la tiv e ly lower m olecular weight than the o th er poly­ mers.

0. S. Marvel and coworkers*^- in a s e rie s of over twenty papers

reported the p re p a ratio n and polym erization o f a s e rie s o f s u b s titu te d sty re n e s. compounds.

These workers ch arac te riz ed the polymers obtained from these They were able to show th a t s u b s titu tio n on the benzene rin g

2

produces polymers with, higher so fte n in g p o in ts than o rd in ary styrene polymers*

I t was b elieved by the p resen t author th a t s u b s titu tio n o f

the arom atic rin g in 2 -a ry l-l,3 -b u ta d ie n e s might a lso ra is e the so fte n ­ ing p o in t of the polymers obtained from these dienes* A study o f the l i t e r a t u r e in d icated th a t a s u ita b le method fo r the p rep aratio n of 2 -a ry l-l,3 -b u ta d ie n e was not av ailab le*

A new

method of sy n th esis fo r t h i s type of compound was th e re fo re devised* The method depended upon the re a c tio n o f arom atic Grignard reagents w ith butadiene monoxide (3 ,4 -ep o x y -l-b u ten e).

Upon h y d ro ly sis o f the

Grignard re a c tio n m ixture an alco h o l was obtained which could be de­ hydrated to the d esired s u b s titu te d butadiene. I t was p o ssib le to o b tain e ith e r the 1- o r 2 -s u b stitu te d a ry l butadienes by th is method according to th e o rd er in which the r e ­ agents were added.

The products o f the re a c tio n were id e n tifie d by p re­

paring the 1 -a ry l compounds by an unequivocal and independent s y n th e sis. This synthesis involved the re a c tio n o f allylmagnesium h a lid e w ith sub­ s titu te d aromatic aldehydes.

An alcohol was obtained from these r e ­

actio n s which on dehydration gave 1 -a ry l-1 ,3 -b u ta d ie n e s,

Maleic anhy­

d ride d e riv a tiv e s of these dienes were prepared fo r c h a ra c te riz a tio n and th e ir m elting p o in ts observed. The butadiene compounds obtained from the butadiene monoxide sy n th esis were also reacted with maleic anhydride to o b tain d e riv a tiv e s . These d e riv a tiv e s had m elting p o in ts which d iffe re d from those of the 1-arylbutadiene a d d itio n pro d u cts.

This d ifferen c e in d ic a ted th a t the

compounds obtained from the butadiene monoxide were 2 -a ry l-l,3 -b u ta d ie n e s . An extensive study was made to determine the b e st methods of

3

dehydration of the interm ediate a lc o h o ls.

I t was found th a t the secon­

dary alco h o ls were dehydrated b e st in the vapor phase over an alumina c a ta ly s t.

The prim ary a lc o h o ls, obtained from the butadiene monoxide

re a c tio n s , gave the b e st y ie ld s by h e atin g w ith powdered sodium hydroxide under reduced p re ssu re . The 1 -a ry l- and 2 - a r y l - l , 3-butadienes were polymerized by means o f an emulsion polym erization technique.

The polymers obtained

from the 1 -a ry l dienes were b r i t t l e , non-rubbery su b stan ces.

The

2 -a ry l dienes gave polymers which were tough and rubbery when adequately d rie d .

Copolymers w ith styrene produced g ra n u la r polym ers.

w ith butadiene produced strong ru b b e r-lik e m a te ria ls .

Copolymers

4

DISCUSSION The s u b s titu tio n o f the 1 ,3-butadiene molecule by a lip h a tic , aromatic o r halogen groups in flu en ces the ra te of polym erization of these compounds.

This vjas shown by C arothers6 *7 and UJhitby17 who used

a large v a rie ty of s u b s titu te d b u tad ien es.

These workers were not able

to study adequately the ^ -s u b s titu te d compounds since these compounds were not re a d ily a v a ila b le . 6 7 C arothers * prepared and studied the polym erization of 2-phenyl-l,3-butadiene (phenoprene).

The method o f sy n th esis used in ­

volved the re a c tio n of phenyl magnesium bromide w ith 4 -c h lo ro -1 ,2 -b u ta ­ diene . ^ -MgBr + C1-CH2-CH=C=CH2

►

CH2— CH=C=CH.2 + C=^—C=C [T j]

( 24#)

The y ie ld s from t h i s re a c tio n a re low, the in term ed iates are d i f f i c u l t to prepare, and the f i n a l products are not e a s ily sep arated . Another sy n th esis of 2 -p h en y l-l,3 -b u tad ien e is rep o rted by Backer and S tra tin g ^ .

This sy n th esis is longer and more involved than

the one reported by C arothers.

I t is i ll u s t r a t e d in the follow ing

equations: OH rag-^-CHgCHg

0

-H2° ,

Br Br CHg-C-CH-CH3 Bra in CC14 ^ ch3. 0 _ 6 hCH3

0

a lco h o lic

-r

A

M ixture o ► Bromo-2-phenyl-butenes

o 380° w ith BaClp(anhyd.)

—►CH2=C-CH=CHq

This method is a lso undesirable fo r the p re p a ratio n of a number of

*

l

Ù

^

5

2 - a r y l - l , 3-butadienes because of the number o f step s in the procedure and the o v e ra ll y ie ld s a re low. Recently P rice 1 ,3 -b u tad ien es.

1 5

published a method of sy n th esis fo r 2 -a ry l-

This method involves th e re a c tio n of (&.-methylstyrene

w ith formaldehyde in g la c ia l a c e tic acid using .17$ s u lfu ric acid as a c a ta ly s t.

A m ixture i s obtained from th is re a c tio n c o n sistin g m ostly

of 4 -p h e n y l-l, 3-dioxane (I) and 2-phenyl-4-acetoxy-l-butene ( I I ) .

The

2-ph enyl-l,3-butadiene was obtained from the acetoxybutene (II) by py ro ly sis a t 530°.

The diene was a lso obtained by the p y ro ly sis of the

dioxane (I) a t 150° in the presence of sodium b is u lf a te . + ECHO

(I)

•CHo-CHoOCOCH.

(ID

This method of sy n th esis i s troublesome and cannot be used e a s ily fo r the p rep aratio n o f a la rg e number of d if f e r e n tly s u b s titu te d compounds. The y ie ld s are low and the products a re d i f f i c u l t to se p a ra te . A new method of sy n th esis fo r the p re p a ra tio n of the 2-aryl. 1,3-butadienes was developed in the p re sen t in v e s tig a tio n .

This method

was the re a c tio n of butadiene monoxide (3,4-epoxy-l-butene) w ith aromatic

6

Grignard re a g e n ts.

The alco h o ls obtained upon h y d ro ly sis were dehy­

d rated to 1,3-butadiene d e riv a tiv e s . The re a ctio n of a Grignard reagent w ith an unsymmetrieal epoxide may give a prim ary o r a secondary alco h o l o r a m ixture o f both compounds.

I t i s th e re fo re p o ssib le to o b ta in from butadiene monoxide

the 1 -a ry l (I) or 2 -a ry l alco h o l (II) according to the follow ing equation, AiMgBr + CH2=CH-GH-CH2 _h y d ro ly s is ^

CH2=CH-gH-CHgAr (I)

or ch2=ch- ch- ch2oh At

(II)

I t was conjectured th a t conditions could be c o n tro lle d to give e ith e r one o f the above two a lc o h o ls.

This supp o sitio n was the

r e s u lt of an analogy drawn from a paper by Kharasch.

9

He showed th a t

the a d d itio n o f styrene oxide to a Grignard so lu tio n gave th e prim ary a lco h o l, but th a t the secondary alco h o l was obtained by rev ersin g the procedure and adding the Grignard reagent to the oxide, Ar f^VCH-CHpOH

jV^CHpCHs

added to AiMgX — >

AilîgX

added to

-^ï— CHo >0/

>

z^^Y^H-OHpAr L H

Since the v in y l group i s o fte n analogous in i t s behavior to a phenyl group, s im ila r re a c tio n s were expected w ith butadiene

7

monoxide.

The re s u ltin g alco h o ls might then be dehydrated to give the

d e sired 1- or 3 -a ry l s u b s titu te d 1 ,3 -b u tad ien es. I t was decided to prepare 1 -a ry l arom atic butadienes a lso by an unequivocal and independent sy n th e sis.

These dienes were then com­

pared w ith the compounds obtained from the butadiene monoxide re a c tio n to determine whether the prim ary o r secondary alco h o l had been o b tain ed . The p rep aratio n o f 1 -su b st1tu te d 1,5-butadienes The re a c tio n of allylmagnesium h a lid e s with arom atic a ld e­ hydes^ was the re a c tio n used to prepare 1 -ary 1 -1 ,3 -butadienes. CH^GH-CHgMgX + ArCHO

ÇMgX — > CH2=CH-CHg-CHAr

s a t'd NH4CI Qg — ---------- > GHg^GH-CHg-ifiAr

^ 8 ° —» CH2=CH-CH=CHAr

There i s one case in the re c en t lit e r a t u r e where th is re a c tio n is re ­ ported^.

This i s fo r the re a c tio n o f

magnesium c h lo rid e . rep o rted .

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