Derivatives of Hexachlorocyclopentadiene and 1,2,3,4-Tetrachlorocyclopentadiene

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PURDUE UNIVERSITY

THIS IS TO CERTIFY THAT THE THESIS PREPARED UNDER MY SUPERVISION

BY

R ich ard K ayton M eyers

ENTITLED

DERIVATIVES OF HEXACHLOROCYCLOPENTADIENE AND

1 ) 2 , 3 , 4-TETRACHL0R0CYCL0PENTADIENE

COMPLIES WITH THE UNIVERSITY REGULATIONS ON GRADUATION THESES

AND IS APPROVED BY ME AS FULFILLING THIS PART OF THE REQUIREMENTS

FOR THE DEGREE OF

D o c to r o f P h ilo s o p h y

P r o f e s s o r in C h a r g e o f T h e s is

H ead o f S ch o o l or D epa r tm en t

TO THE LIBRARIAN:;--IS THIS THESIS I6bSfi£T TO BE REGARDED AS CONFIDENTIAL.

P R O F E S S OB n r CHARGE

G R A D . S C H O O L F O R M 9 —3 - 4 9 —1 M

DERIVATIVES Of HEXAOHLOEOGYOIOEBKTADIERE AID 1 , 2 , 3 , 4-TETRA0HLOROOYOLOPEÏÏTADIEEE A T h e sis S u b m itte d to th e F a c u lty of Purdue Ü n l v e r s i ty

R i c h a r d K. M ey ers in P a r t i a l F u lfillm e n t of th e R e q u i r e m e n t s f o r t h e D e g re e of D o c to r o f P h ilo so p h y F e b r u a r y , 1950

ProQuest N um ber: 27714103

All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is d e p e n d e n t upon the quality of the copy subm itted. In the unlikely e v e n t that the a u thor did not send a c o m p le te m anuscript and there are missing pages, these will be noted. Also, if m aterial had to be rem oved, a n o te will ind ica te the deletion.

uest ProQuest 27714103 Published by ProQuest LLC (2019). C opyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States C o d e M icroform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106 - 1346

•AGKIOELEDGMEIT The a u t h o r e x p r e s s e s h i s t h a n k s t o P r o f e s s o r E . T. MoBee f o r h i s g u id a n c e and a i d th ro u g h o u t t h i s i n v e s t i g a t i o n . a d v i c e o f D r . 2 . D. W elch i s g r e a t l y a p p r e c i a t e d .

The

The

a u t h o r i s a l s o g r a t e f u l t o h i s l a b o r a t o r y p a r t n e r , H. B a k o f f , an d t o t h e many o t h e r r e s e a r c h f e l l o w s w i t h whom h e h a s b e e n a s s o c ia te d , f o r t h e i r in v a lu a b le su g g e stio n s and c r itic is m s . T h is r e s e a r c h p r o j e c t was f i n a n c e d by t h e H ooker E l e c t r o c h e m i c a l Company t h r o u g h t h e P u rd u e R e s e a r c h F o u n d a tio n .

TABLE OF OOITBITS Page ABSTRACT P a rt 1.

P art 2.

P art 3.

P a rt 4.

PREFACE . PART I

P r e p a r a t i o n o f F u l v e n e s from 1 , 2 , 3 , 4 T e t r a o h l o r o c y e l o p e n t a d i e n e an d A ro m a tic A l d e h y d e s . ....................... .

.

1

The A c t i o n o f . S u l f u r i c A c id on 1 . 2 . 3 . 4 -T e tra c h lo ro e y c lo * * p e n ta d ie n e . . . . . . . . .........................

v ii

The A d d i t i o n o f B rom ine a n d C h l o r i n e to 1 , 2 , 3 , 4 - T e tr a c h lo r o o y c lo pen t a d i e n e . . . . . . . . . . . . . .

xvi

S e le c te d D ie Is -A ld e r R e a c tio n s o f H e x a c h lo ro o y c lo p e n ta d ie n e and 1 .2 . 3 .4 -T e tra c h lo ro c y c lo .................... p e n ta d ie n e ....................................................................................................

1

THE COMDMSATIOI OF 1 , 2 , 3 , 4-TETRACHL0R0CYCLOPEITADIEIE WITH AROMATIC ALDEHYDES

In tro d u c tio n .

. . . . . . . . . . . . . . . . .

L i t e r a t u r e B a c k g ro u n d • • • D isc u ssio n .

. . . . . .

E x p erim e n tal.

.................................................

......................... . . . . . . .

. . . . . . . . . . . .

.........................

2 2 8 14

P re p a ra tio n of l,2 ,3 ,4 - T e tr a c h lo r o - 6 p h e n y l-fu lv e n e . . . . . . . . . . . . . .

14

P re p a ra tio n o f l,2 ,3 ,4 - T e tr a c h lo r o - 6 (p -c h lo ro p h e n y l)-fu lv e n e . . . . . . . . .

14

P re p a ra tio n of 1 ,2 ,3 ,4 -T e tra c h lo ro -6 ( p -m e th o x y p h e n y l) - f u l v e n e . • .........................

15

P r e p a r a tio n o f 1 , 2 , 3 , 4 -T © tra o h lo ro -6 (p -d im e th y la m in o p h e n y l) - f u l v e n e . . . . . .

15

P re p a ra tio n o f 1 , 2 , 3 , 4 -T e tra c h lo ro -6 ( 3 ,4 -d im e th o x y p h e n y l)-fu lv e n e . . . . . . .

16

P age P re p a r a tio n of 1 , 2 , 3 , 4 -T e tra c h lo ro -6 ~ ( 3 , 4 -m e th y le n e d io x y p h e n y l)-fu lv e n e . . • .

16

P re p a ra tio n o f l,2 ,3 ,4 -P e tra c h lo ro -6 ^ ( 4 -h y d ro x y -3 -m e th o x y p h e n y l)-fu lv e n e . . . .

17

P re p a ra tio n o f l ,2 ,3 ,4 - îe tr a o h l o r o - 6 (m -n itro p h e n y l)-fu lv e n e . . . . . . . . . .

17

P re p a ra tio n of 1 ,2 ,3 ,4 -T e tra o h lo ro -6 ( p - h y d r oxy p h e n y l ) - f u l v e n e ............................................. 18 P re p a ra tio n o f 1 ,2 , 3 ,4 -T e tra o h lo ro -6 (o -h y d ro x y p h e n y l)-fu lv e n e . . . . . . . . .

18

P re p a ra tio n o f 1 ,2 ,3 ,4 -T e tra o h lo ro -6 .............................................................. 19 sty ry lfu lv e n e . P re p a ra tio n o f 1 ,2 ,3 ,4 -T e tra o h lo ro -6 (2 -fu ry l)-fu lv e n e . . . . . . . . . . . . .

19

O x id a tio n of 1 , 2 , S ^ - T e t r a c h l o r o - ô fp -m eth o x y p h en ÿ l)- f u l v e n e . . . . . . . . .

19

P re p a ra tio n o f 1 , 2 , 3 ,4 -T e tra e h lo ro o y o lo p en tad ie n e. . .......................................................20 PART I I

THE A0TI01 OF SULFURIC ACID OU 1 , 2 , 3 , 4 TETRACELOROCYCLOPEUTADIEUE

In tro d u c tio n

.............................................22

D i s c u s s i o n ............................. E x p erim e n tal.

.

. . . .

22

.............................

29

P re p a ra tio n of 2 ,3 ,4 -T ric h lo ro -2 o y c l o p e n t e n o n e ......................... . . . . . . . .

29

P re p a ra tio n o f T e tra c h lo ro -3 a ,4 , 7 ,7 a t e t r a h y d r o - 4 , 7 i-me t h a n o i n d e n e - 1 , 8 d io n e . • • .................................

29

P y r o l y s i s of T e t r a o h l o r o - 3 a ,4 ,7 ,7 a t e t r a h y d r o - 4 , 7- m e t h a n o i n d e n e - 1 , 8 d io n e . . . . . . . . . . . .

.

.

.

P r e p a r a t i o n o f 5 - B r o m o - 2 ,3 , 4 - t r i c h lo ro -2 -c y c lo p e n te n o n e . . . . . . . . . .

30 31

P age

PART I I I

D e h y d r o h a l o g e n a t i o n o f 5 -B ro m o - 2 , 3 , 4 t r i c h l o r o - 2 - o y o l o p e n t e n o n e ..............................

31

P re p a ra tio n o f P ro m o tetrac h lo ro -1 in d o n e . . . . . . . . . . . .........................

32

D itn o m in a tio n o f 2 , 3 , 4 - T r i e h lo r o - 2 o y c lo p e n te n o n © . . . . . . . . . . . . .

33

THE ADDITION OF BROMINE AND CHLORINE TO 1 , 2 , 3 , 4-TETRACHLOROOYCLOPENTADIENE

In tro d u c tio n D isc u ssio n .

. . .

. . . . . . . . . .

. . . . . . . . . . .

....................

34

. .

34

E x p e r i m e n t a l .............................

41

B ro m in a tio n o f 1 , 2 , 3 , 4 - T e t r a e h l o r o c y c l o p e n t a d i e n e .....................................................

.

41

P r e p a r a t i o n o f 4 -B ro m o -2 , 3 , 4 - t r i o h lo ro -2 -c y c lo p e n te n o n e ♦ . . . ....................

41

H y d r o l y s i s o f 4 - B r o m o - 2 ,3 , 4 - t r i o h l o r o - 2 - c y c l o p e n t e n o n e . . . .........................

42

P r e p a r a t i o n o f O i o % ^ 6 ^ 2 * .............................

43

•

P r e p a r a t i o n o f CgHClgO . . . . . . . . . .

43

B r o m i n a t i o n o f 4 - B r o m o - 2 ,3 , 4 - t r i c h l o r o - 2 - c y c l o p e n t e n o n s . . ..............................

44

C h lo rin a tio n of 1 ,2 ,3 ,4 -T e tra c h lo ro ­ cy c l open t a d i e n e . . . . . . . . .

45

S u l f u r i c A c id H y d r o l y s i s o f CgHgClg.

.

. . .

47

P re p a ra tio n of 1 , 2 , 3 , (or 4 ) ,5 ,5 P e n t a c h l o r o c y o l o p e n t a d i e n e . .........................

47

P re p a ra tio n of 1 , (o r 2 ) ,3 ,4 ,7 ,7 P e n t a o h l o r o M c y c l o - ( 2 .2 .1 ) - 2 h e p te n e - 5 ,ô - d ic a r h o x y lic A cid . . . . . .

48

P re p a ra tio n of 1 , (o r 2 ) , 3 , 4 -T ric h l o r o - 5 , 5 - d im e th o x y c y c l o p e n t a d i e n e • .................... . . . . . . . . .

48

P age P re p a ra tio n of 1 , (o r 2 ) ,3 ,4 - T r ic h l o r o - 7 , 7 -d in B t h o x y l î i e y o l o (2*2*1) --2- k e p t e n e - 5 , 6 —d i — o a r b o x y l i c A o id . . * ........................* *

PART IV

*

50

P r e p a r a t i o n o f Q1o H2G16 ° 2 ........................• • •

50

P r e p a r a t i o n o f O ^ H O lg O ........................................

51

SELECTED DIELS-ALDER REACTIONS OP HEZAOELOROCYCLOPENTADIEBE ADD 1 , 2 , 3 , 4 TBTRACHLOROGYCLOPED TADIEDB ..............................

52

............................................

53

In tro d u c tio n * * * * * * * * * * D isc u ss io n *

*

*

*

*

E x p e r i m e n t a l * ....................

*

* * * * * * * * *

59

P re p a ra tio n of 1 ,2 ,3 ,4 ,7 ,7 -H e x a c h lo ro -5 -h y d ro x y m e th y lb ic y o lo (2 .2 .1 ) -2 -h e p te n e * .......................................

59

P r e p a ra tio n o f th e A c e ta te E s t e r o f 1 . 2 . 3 . 4 . 7 . 7 -H e x a e h lo ro -5 -h y d ro x y m e th y lb ie y c lo -(2 * 2 .1 ) -2 -h e p te n e * * * *

59

P re p a ra tio n of th e P ro p io n a te E s te r of l,2 ,3 ,4 ,7 ,7 -H e x a c h lo ro -5 h y d ro x y m e th y lb ic y c lo -(2 .2 .1 )-2 h e p te n e * * * * * * * * * ....................

60

P re p a ra tio n of 1 ,2 ,3 ,4 ,7 ,7 -H e x a c h lo r o -5 -ch lo ro m eth y lb i c y c l o - ( 2 . 2 . 1 ) 2 -h ep te n e . . . . . . . . . . .

60

P r e p a r a t i o n o f 5-B rom om ethy1 - 1 , 2 , 3 , 4 , 7 .7 -h e x a o h lo ro b ic y c lo -(2 .2 * 1 )-2 h e p te n e . . . . . . . . . . . . . . . .

61

P r e p a r a t i o n o f 1 , 2 , 3 , 4 , 7 , 7-H exac h lo ro -5 -is o th io c y a n o m e th y lb ic y o lo -(2 * 2 .1 )-2 -h e p te n e . . . . . * .

62

R e a c t i o n o f 1 , 2 , 3 , 4 , 7 , 7 -H e x a c h lo ro -6 -iso th io c y a n o m e th y lb i c y c l o - ( 2 . 2 . 1 ) - 2 - h e p t e n e W ith A n ilin e . .......................

63

P age D im e riz a tio n of 1 ,2 ,3 ,4 - T e t r a e h lo ro c y o lo p e n ta d ie n e . . . . . . . . .

64

A d d itio n of O y c lo p e n ta d ie n e to 1 , 2 , 3 , 4 -T e tra o h lo ro o y e lo p e n ta d ie n e . . .

64

C h lo r in a tio n o f th e 1 , 2 , 3 , 4 - f e t r a o h lo ro o y o lo p e n ta d ie n e -o y o lo p e n t a d i e n e Add n o t ......................... • • • •

64

SUHEBEY BIBLIOGRAPHY VITA

.........................................................................

67 69

LIST OP TABLES AMD FIGURES T ab les I XI III

P ag e F u l v e n e s P r e p a r e d fro m 1 , 2 , 3 , 4 - T e t r a ­ c h l o r o c y c l o p e n t a d i e ne . . . . . . . . . . . .

11

D ie I s - A l d e r A d d u c ts o f H e x a o h l o r o ................................... 57 ey clo p en tad ie n e D i e ls - A l d e r A d d u c ts o f 1 , 2 , 3 , 4 - T e t r a ­ c h l o r o c y c l open t a d i e n e . .......................................

58

F ig u re s I II

B ro m in a tio n o f 1 , 2 , 3 , 4 - T e t r a e h lo r o c y c lo p e n ta d ie n e . . . . . . . ..................................... C h lo rin a tio n o f 1 , 2 , 3 , 4 -T e tra o h lo ro c y o lo p e n ta d ie n e . . . . . . ......................... • • •

36 40

( C o n t r i b u t i o n fro m t h e D e p a r t m e n t o f C h e m i s t r y and P urdue R e s e a rc h F o u n d a tio n ) P u rd u e U n i v e r s i t y D a fa y e tte , In d ian a PREPARATION OF FULVENES FROM 1 , 2 , 3 , 4-TETRAOEÙOHOOY0105BHTADIEHB AÎTD AROMATIC AMBHYDBS1 By E a r l 'T. MoBee a n d R i c h a r d K. M ey ers

1.

Taken i n p a r t fro m a t h e s i s s u b m i t t e d b y R. K. M e y ers to t h e f a c u l t y o f P u rd u e U n i v e r s i t y i n p a r t i a l f u l f i l l m e n t o f th e r e q u ir e m e n ts f o r th e d e g re e o f D o c to r o f P h ilo s o p h y in F e b ru a ry , 1950. ABSTRACT In tro d u c tio n I n t h e c o u r s e o f i n v e s t i g a t i o n s i n t h i s l a b o r a t o r y on

t h e p r e p a r a t i o n o f c h l o r i n a t e d compounds h a v i n g i n s e c t i c i d a l v a l u e , i t seem ed a d v i s a b l e

to p re p a re a s e r i e s of t e t r a -

c h l o r o f u l v e n e s fro m 1 , 2 , 3 , 4 - t e t r a c h l o r o c y c l o p e n t a d i e n e and a ro m a tic a ld e h y d e s . F u l v e n e s a r e g e n e r a l l y p r e p a r e d by th e c o n d e n s a t i o n o f c a r b o n y l com pounds w i t h c yc l o p e n t a d i ene i n t h e p r e s e n c e o f stro n g a lk a lin e re a g e n ts 2 ,3 ,4 .

33,

A s e c o n d m eth o d i n v o l v e s t h e

2.

T h ie le , B e r. ,

666 ( 1 9 0 0 ) .

3.

T h i e l e , A n n ., 3 4 8 , 1 ( 1 9 0 6 ) .

4.

B o o rd , Renne and C r a n e , J . Am. Chem. S o c . , 67 , 1237 ( 1 9 4 5 ) .

a d d i t i o n o f a o y o l o p e n t a d i e n y l G r i g n a r d r e a g e n t to a c a r b o n y l compound f o l l o w e d by d e h y d r a t i o n 3 .

The o n l y t e t r a h a l o f u l v e n e

11

5.

C o u r t o t , Ann, G h im ., IV (9 ) , 58 ( 1 9 1 5 ) .

r e p o r t e d p r i o r t o t h i s i n v e s t i g a t i o n was p r e p a r e d by th e b ro m in a tio n of 6 , 6 -d ip h e n y lfu lv e n e ^ ,

6.

Bergmann and von C h r i s t i a n i , B e r . , 63B, 2559 ( 1 9 3 0 ) . A t t e m p t s w ere made t o c o n d e n s e c a r b o n y l compounds w i t h

1 . 2 . 3 . 4 - te tr a c h lo r o c y c lo p e n ta d ie n e in th e p re se n c e o f s tro n g b a s e s s u c h a s so d iu m h y d r o x i d e a n d sodium e t h o x i d e , b u t o n ly c o m p le x c o n d e n s a t i o n m i x t u r e s w e re o b t a i n e d . a s p y r i d i n e a n d sodium a c e t a t e

Weak b a s e s , s u c h

in a c e t i c a c i d , a l s o y i e l d e d

t h e same r e s u l t s . H ow ever, i t was f o u n d t h a t t h e c o n d e n s a t i o n c o u ld b e e f ­ f e c t e d q u i t e r e a d i l y by s t i r r i n g a s o l u t i o n o f an a r o m a t i c a l d e h y d e a n d 1 , 2 , 3 , 4 - t e t r a c h l o r o c y c l o p e n t a d i e n e i n 95$ e th a n o l.

S i n c e t h e a d d i t i o n o f s m a l l a m o u n ts o f a c i d do n o t

seem t o a f f e c t th e c o u r s e o f t h e r e a c t i o n ,

th e s o lv e n t, a

m i x t u r e o f e t h a n o l and w a t e r , p r o b a b l y a c t s a s a b a s i c c o n d e n s i n g a g e n t i n th e r e a c t i o n .

T e t r a e h l o r o f u l v e n e s w h ic h

h a v e b e e n p r e p a r e d by t h i s m e th o d a r e l i s t e d i n T a b le I . The f u l v e n e s p r e p a r e d fro m a r o m a t i c a l d e h y d e s a n d 1 . 2 . 3 . 4 - te tr a e h lo r o o y c lo p e n ta d ie n e a re h ig h ly c o lo re d c r y s t a l l i n e com pounds.

The p h e n y l - s u b s t i t u t e d d e r i v a t i v e s

a r e r e d - o r a n g e , w h i l e t h o s e p r e p a r e d fro m c in n a m a ld é h y d e an d f u r f u r a l a r e b ro w n .

The t e t r a c h l o r o f u l v e n e s a r e n o t r e a d i l y

ill

TABLE I F u l v e n e s P r e p a r e d fro m 1 , 2 , 3 , 4 - T e t r a c h l o r o c y e lo p e n ta d ie n e 01

01 H R

^ > =c" 01 R 1. phenyl 2.

M .P . 2 °C . 8 1 -2

( 4 - e h lo r o p h e n y l) 140-4

01

Y ie ld

F o r m u la

4 48 57

0 Cl g H50 1 4 C ,o H - C l^

3.

(4 -h y d ro x y p h e n y l)

4.

d ark en s 140° dec. 1 6 3 -7

0

0

O a lo 'd . H

Found3 O H

4 8 . 61

-

4 8 .2

5 4 . 41

-

5 4 .9 , 5 4 . 61

-

45.7'*"

16

C1PHK0 1 . 0

4 6 .1

(4 -d im e th y l1 2 6 -7 a m in o p h e n y l)

51

0 ,/R ,,0 l^

5 0 .1

3 .2 8 5 0 .3

3 .1 6

5.

( 4 - m e th o x y p h e n y l)

127-8

50

C , , H oC 1 .0 13 8 4

4 8 .4

2 .5 4 4 8 .4

2 .4 8

6.

(3 -n itro p h e n y l)

144

24

0 , pH cCl.H 0o 12 5 4 2

4 2 .2

7.

( 4 -h y d ro x y -3 - 178-9 me th o x y p h e n y l)

32

0 . „Hfl0 1 . 0 P

4 6 .2

2 . 5 5 4 6 .2

2 .5 3

8.

(3 ,4 -m e th y le n e - 153-4 d io x y p h en y l)

45

G1(~HAC1A0 9

4 6 .4

1 .7 8 4 6 .4

1 .7 3

9.

( 3 , 4 - d i m e th y o x y - 1 3 8 - 9 phenyl

47

O i4 Hi o C14°B

4 7 .8

2 . 6 0 4 7 .7

2 .8 4

10.

(2-hy droxypbenyl) d e c . 1 4 0 -5 0

G19HAC1A0 xc b 4

4 6 .2

2 . 5 3 4 6 .2

2 .5 5

11.

sty ry l

1 4 4 -5

41

5 2 .8

2 . 5 2 5 2 .5

2 .4 8

12.

fu ry l

1 0 9 -1 0

50

4 2 .6

1 . 4 2 4 2 .6

1 .4 3

O ^ E g O l^

-

4 2 . 61

(1) ' 01 a n a l y s i s (2) M . P . u n c o r r e c t e d (3 ) C a rb o n and h y d ro g e n a n a l y s i s p e r f o r m e d by H. G a l b r a i t h

iv

o x i d i z e d i n a i r , b u t c h ro m ic o x i d e c o n v e r t s them t o s u b s t i t u t e d b e n zo ic a c id s* F u l v e n e s p r e p a r e d fro m c y c l o p e n t a d i e n e u n d e r g o D i e l s - A l d e r r e a c t i o n s 7 ’ 8 , 9 , 1 ^*

A t t e m p t s w e re made t o r e a c t m a l e i c a n h y d r i d e

7.

D i e l s , A l d e r a n d P r i e s , B e r . , 62B, 2081 ( 1 9 2 9 ) .

8.

K o h le r and K a b le,

9.

Woodward a n d B a e r , J , Am. Chem. S o c . ,

6 6 , 645 ( 1 9 4 4 ) .

1 0 . B l o m q u i s t a n d W inslow , J . O r g . Chem. ,

1 0 , 149 (1 % 5 ) .

J . Am. Chem. S o c . , 5 7 , 917 (1 9 5 5 ) .

w i t h a few o f t h e 1 , 2 , 3 , 4 - t e t r a c h l o r o - 6 - p h e n y l s u b s t i t u t e d f u l v e n e s u n d e r r e l a t i v e l y m i l d c o n d i t i o n s , b u t i n no c a s e was th e ad d u ct i s o l a t e d . The 1 , 2 , 3 , 4 - t e t r a c h l o r o c y c l o p e n t a d i e n e u s e d i n t h i s work was p r e p a r e d by a m o d i f i c a t i o n o f t h e m eth o d d e s c r i b e d by B aranauckus^.

11.

The p r o c e d u r e i n v o l v e s t h e r e d u c t i o n o f h e x a -

B a r a n a u c k u s , P h . D. T h e s i s , p . 31 ( 1 9 4 7 ) .

e h lo r o c y o lo p e n ta d ie n e w ith z in c and h y d r o c h lo r ic a c i d . B xperim e n t a l The h e x a c h l o r o o y c l o p e n t a d i e n e was g e n e r o u s l y s u p p l i e d b y t h e H o oker E l e c t r o c h e m i c a l Company. P re p a ra tio n of 1 ,2 ,3 ,4 -T e tra c h lo ro c y c lo p e n ta d ie n e .

A

s o l u t i o n o f 825 g . o f h e x a c h l o r o o y c l o p e n t a d i e n e i n an e q u a l volum e o f p e t r o l e u m e t h e r ( 5 0 o- 6 0 ° ) w as p o u r e d i n t o a 5 l i t e r t h r e e - n e c k e d f l a s k , e q u ip p e d w i t h a d ro p p in g f u n n e l , a r e f l u x

V

c o n d e n s e r , a n d a HershTaerg s t i r r e r a t t a c h e d t o a h i g h s p e e d m o to r.

The r e a c t i o n f l a s k w as s u r r o u n d e d by a l a r g e s te a m co n e

t h r o u g h w h ic h c o l d w a t e r w as c i r c u l a t e d .

A s l u r r y o f 520 g .

o f z i n c , w h ic h h a d b e e n p r e v i o u s l y t r e a t e d w i t h a c o l d s o l u t i o n o f 50 g . o f c o p p e r s u l f a t e , w as a d d e d w i t h s t i r r i n g so lu tio n .

to th e

A s o l u t i o n o f 625 m l . o f c o n c e n t r a t e d h y d r o c h l o r i c

a c id (te c h .)

d i l u t e d w i t h an e q u a l volum e o f w a t e r was a d d e d

d ro p w ise to th e r e a c t i o n m ix tu r e o v e r a p e r i o d o f 3 .5 h o u r s . The r e a c t i o n m i x t u r e w as t h e n

filte re d

th ro u g h a l a r g e Buchner

fu n n e l to se p a ra te th e l iq u i d

fro m t h e r e m a i n i n g c o p p e r a n d

z in c .

The p e t r o l e u m e t h e r s o l u t i o n w as s e p a r a t e d from t h e a c i d

la y e r,

c o o l e d i n an i c e b a t h ,

and th e l a r g e ,

w h ic h fo r m e d w e re c o l l e c t e d on a f i l t e r .

l i g h t ta n c r y s t a l s

The m a j o r p o r t i o n o f

t h e p e t r o l e u m e t h e r w as e v a p o r a t e d a n d t h e o r g a n i c l i q u i d w h ic h r e m a i n e d was c o o l e d t o y i e l d a s e c o n d b a t c h o f d a r k e r c r y s t a l s . The t o t a l q u a n t i t y o f c r u d e t e t r a o h l o r o o y c l o p e n t a d i e n e a m o u n ted t o 366 g . (59% ), m e l t i n g fro m

56 0 ~ 6 2 ° .

o b ta in in g a w h ite c r y s t a l l i n e

p r o d u c t ( m .p . 6 2 ° - 6 3 0 ) i s t o

d is till

The b e s t m eth o d o f

th e cru d e m a t e r i a l u n d e r re d u c e d p r e s s u r e .

G e n e ra l P ro c ed u re f o r th e P r e p a r a t io n of 1 , 2 , 3 , 4 -T e tra ^ o h lp ro fu lv e n e s .

A s o l u t i o n o f 0 . 1 m o le o f 1 , 2 , 3 , 4 - t e t r a c h l o r o -

c y c l o p e n t a d i e n e and 0 . 1 m o le o f t h e a r o m a t i c a l d e h y d e i n 60 m l . o f e t h a n o l was r e f l u x e d g e n t l y on a s t e a m b a t h .

The m i x t u r e

g r a d u a l l y t u r n e d d a r k , and s o l i d p r o d u c t s e p a r a t e d .

A fte r

s i x t e e n t o e i g h t e e n h o u r s t h e r e a c t i o n c o n t a i n e r w as c o o l e d a n d t h e p r e c i p i t a t e c o l l e c t e d by f i l t r a t i o n .

The p r o d u c t was

r e c r y s t a l l i z e d from t h e a p p r o p r i a t e s o l v e n t ( e t h a n o l i n m o s t c a s e s ) .

vi

O x id a tio n o f 1 , 2 , 3 t 4 ~ T e tra c h lo ro ~ 6 -(p -m e th o x ÿ p h e n y l)fu lv en e «

Ten m i l l i l i t e r s o f s u l f u r i c a c i d was a d d e d w i t h

stirrin g

to a m ix tu re o f 2 g . of 1 , 2 , 5 , 4 - t e t r a e h l o r o - 6 - ( p -

m e t h o x y p h e n y l ) - f u l v e n e , 10 m l. o f a c e t i c a c i d , 10 m l. o f w a t e r a n d 6 g . o f chrom ium t r i o x i d e c o n t a i n e d i n a 250 m l . t h r e e ­ n e ck e d f l a s k e q u ip p e d w i t h a s t i r r e r and a c o n d e n s e r.

The

m i x t u r e b o i l e d v i g o r o u s l y a n d e x t e r n a l c o o l i n g w as r e q u i r e d . When t h e r e a c t i o n h a d s u b s i d e d , i t was h e a t e d on a s te a m b a t h f o r an h o u r.

The r e a c t i o n was c o o l e d a n d d i l u t e d w i t h 10 m l.

o f w a fe r and th e n p o u re d th ro u g h a s i n t e r e d g l a s s f i l t e r g i v e a s m a l l am ount o f t a n a n d r e d s o l i d . so lv e d in b a s e ,

to

The s o l i d w as d i s ­

th e s o l u t io n f i l t e r e d , and th e f i l t r a t e

a c i d if i e d w ith s u l f u r i c a c id .

A w h ite s o lid p r e c i p i t a t e d

i m m e d i a t e l y a n d w as c o l l e c t e d on a f i l t e r a n d d r i e d . m e l t i n g p o i n t w as 1820 - 1 8 3 ° .

The

A m ix e d m e l t i n g p o i n t w i t h an

a u t h e n t i c s a m p le o f a n i s i c a c i d show ed no l o w e r i n g , i n d i c a t i n g t h a t t h e p r o d u c t o f o x i d a t i o n was a n i s i c a c i d . A c k n o w led g m e n t.

The a u t h o r s e x p r e s s t h e i r t h a n k s t o t h e

H o o k e r E l e o t r o c h e m i c a l Company a n d t h e P u rd u e R e s e a r c h F o u n d a tio n f o r f i n a n c in g t h i s i n v e s t i g a t i o n . Summary A s e r i e s o f 1 , 2 , 3 , 4 - t e t r a c h lo r o f u lv e n e s have been p re p a re d fro m 1 , 2 , 3 , 4 - t e t r a c h l o r o c y c l o p e n t a d i e n e a n d a r o m a t i c a l d e h y d e s .

v ii

( C o n t r i b u t i o n f ro m t h e D e p a r t m e n t o f C h e m i s t r y and P u rd u e R e se arch F o u n d a tio n ) B urdue U n i v e r s i t y L a fa y e tte , In d ian a ÏHB AC H O I OF SULFURIC ACID 01 1 , 2 , 3 , 4-IBTRACHLOROOYOLOPEJITADIEUB1 By E a r l

1.

MoBee a n d R i c h a r d K« M e y e rs

T aken i n p a r t fro m a t h e s i s s u b m i t t e d by R. E» M e y ers to t h e f a c u l t y o f B u rd u e U n i v e r s i t y i n p a r t i a l f u l f i l l m e n t o f th e re q u ire m e n ts f o r th e d e g re e o f D o c to r o f P h ilo so p h y in F e b ru ary , 1950. ABSTRACT In tro d u c tio n H y d ro ly sis of h e x a c h lo ro o y c lo p e n ta d ie n e w ith s u l f u r i c

a c i d y i e l d s e i t h e r a m o n o k e to n e o r a d i k e t o n e d e p e n d i n g upon 2 th e c o n d itio n s o f th e r e a c t i o n . B rin s r e p o r t s t h a t th e d i -

2.

B r i n s , R e c . t r a v . c h i m . , £ 5 , 455 ( 1 9 4 6 ) .

k e to n e , 1 , 2 , 5 , 5 - t e tr a o h lo r o - l- c y e lo p e n te n e ? 3 ,4 -â io n e i s

th e

m a j o r p r o d u c t when t h e h y d r o l y s i s i s p e r f o r m e d a t 1 0 5 o* 1 2 0 o . le w c o m e r a n d McBee

3.

w e re a b l e t o o b t a i n 2 , 3 , 4 , 4 , 5 - p e n t a c h l o r o -

le w c o m e r a n d McBee, J . Am. Chem. S o c . ,

TIL, 946 ( 1 9 4 9 ) .

2 - c y .o l o p e n te n o n e i n h i g h y i e l d by m a i n t a i n i n g t h e r e a c t i o n te m p e ra tu re a t 8 0 °.

S i n c e no i n f o r m a t i o n w as a v a i l a b l e c o n ­

c e r n i n g t h e a c t i o n o f s u l f u r i c a c i d on 1 , 2 , 3 , 4 - t e t r a c h l o r o -

v iil

o y o l o p e n t a d i e n e , t h i s r e a c t i o n w as i n v e s t i g a t e d . H y d ro ly sis of 1 , 2 , 3 , 4 - te tr a e h lo r o o y e lo p e n ta d ie n e w ith s u l f u r i c a c i d a t room t e m p e r a t u r e p r o d u c e d a p p r o x i m a t e l y a n 80% y i e l d o f a k e t o n e h a v i n g t h e f o r m u l a OgH^OlgO.

T h is

compound i s one o f t h e f o l l o w i n g t h r e e i s o m e r s .

01 01

H-i I i f hJ — I c i

I

II

Y

N

O lL =rIII

Compound I w o u ld r e s u l t f ro m t h e 1 , 4 - a d d i t i o n o f s u l f u r i c a c i d t o t h e d i e n e , w h e r e a s I I a n d I I I w o u ld h e o b t a i n e d fro m 1 , 2 -a d d itio n s# B ro m in a tio n s t u d i e s o f th e s u l f u r i c a c i d h y d r o ly s is p r o d u c t of 1 , 2 , 3 , 4 - t e t r a c h l o r o c y c l o p e n t a d i e n e l e a d to th e c o n c l u s i o n t h a t CgHgClgO i s

2

, 3 , 4 -trie h lo ro -2 » c y c lo p e n te n o n e .

S i n c e e a c h o f t h e t h r e e i s o m e r s h a v e h y d r o g e n a to m s a l p h a t o a c a r b o n y l g r o u p , e a c h w ould be e x p e c t e d t o b r o m i n a t e .

The mono-

b r o m i n a t i o n p r o d u c t s w h i c h s h o u l d r e s u l t fro m com pounds I ,

II

and I I I a r e : 0 01k Br ■H E—< ^4 —

01 IT (d e riv e d fro m I )

T (d e riv e d fro m I I )

01

TI T Ia ( d e r i v e d fro m I I I )

C o n s id e r a tio n o f th e d e h y d ro h a lo g © n a tio n p r o d u c ts o f th e b r o m o k e to n e s i n d i c a t e a m e th o d by w h ic h compound I c a n b e

ix

d i s t i n g u i s h e d fro m compounds I I a n d I I I .

A l l o f t h e brom o­

k e t o n e s s h o u l d d e h y d r o h a l o g e n a t e t o fo rm c y o l o p e n t a d i e n o n e s . H ow ever, o y e lo p a sfc ad ien o n e s a r e r e a c t i v e a n d g e n e r a l l y d i m e r i z e ^ ;

4.

A l l e n , Chem. R e v . ,

th e re fo re ,

3 7 , 209 ( 1 9 4 5 ) .

t h e p r o d u c t s o f t h e d e h y d r o h a l o g e n a t i o n w o u ld be

t r i c y c l i c d ik e to n e s.

S i n c e ^ r h a l o c a r b o n y l com pounds d e h y d r o ­

h a l o g e n a t e r e a d i l y . Compound 1 7 , d e r i v e d fro m I , w o u ld l o s e h y d ro g e n c h l o r i d e on t r e a t m e n t w i t h b a s e t o p r o d u c e a m e th a n o in d e n e d io n e c o n ta in i n g b ro m in e . H Br

r

Br

Br H

rO

01

Ole 01

01

01

01

01

01

J

Br 01

(* T h is compound r e p r e s e n t s one o f s e v e r a l p o s s i b l e i s o m e r s . ) On t h e o t h e r h a n d ,

t h e c h l o r i n e a to m s a n d b r o m in e a to m s o f

compounds 7 , 71 a n d 7 1 a d e r i v e d fro m com pounds I I a n d I I I ,

are

s t r u c t u r a l l y e q u i v a l e n t a n d t h u s sh o u ld e lim in a te hydrogen b r o m id e u pon t r e a t m e n t w i t h b a s e t o y i e l d t r i c y c l i c d i k e t o n e s w h ic h do n o t c o n t a i n b r o m i n e .

I h is l a t t e r p re d ic tio n

is based

on t h e f a c t t h a t b r o m i d e s fo rm o l e f i n s m ore r e a d i l y t h a n c h lo rid e s5.

5.

T a y l o r , J . Chem. S o c . , 1 9 3 7 , 1 9 6 2 . The com pound, OgHgOlgO, w as b r o m i n a t e d t o g i v e a mono-

s u b s t i t u t i o n p r o d u c t , OgHgBrOlgO.

D e h y d ro h a lo g e n a tio n o f t h i s

/

X

compound p r o d u c e d a t r i c y c l i c d i k e t o n e , G ^ S g B r^ O l^ O , w h ic h deco m p o sed w i t h t h e a p p l i c a t i o n o f h e a t t o an i n d o n e , CgEBrOl^O. S i n c e t h e d e h y d r o h a l o g e n a t io n p r o d u c t o f t h e b ro m o k e to ne c o n ­ t a i n e d b r o m i n e , i t c a n be c o n c l u d e d t h a t t h e s u l f u r i c a c i d h y d ro ly sis p ro d u ct of 1 , 2 , 3 , 4 -te tra c h lo ro c y c lo p e n ta d ie n e i s 2 , 3 , 4 - t r i o h l o r o - 2 - c y c l o p e n t e n o n e , compound I . The r e a c t i o n o f C^HgGlgO w i t h e x c e s s b ro m in e c o n t r i b u t e s a d d i t i o n a l e v id e n c e to th e p ro o f o f th e s t r u c t u r e

o f th e s u l f u r i c

a c id h y d ro ly sis p ro d u ct of 1 , 2 , 3 , 4 -te tra c h lo ro c y c lo p e n ta d ie n e . Compound I , h a v i n g two e n o l i e h y d r o g e n a to m s s h o u l d d i b n o m i n a t e ; compound I I ,

h a v i n g one e n o l i c h y d r o g e n ato m s h o u l d m ono-

b n o m in a te ; a n d compound I I I ,

h a v i n g t h r e e a c t i v e h y d ro g e n a to m s

s h o u l d form a t r i b r o m o d e r i v a t i v e .

E x c e s s b r o m i n a t i on o f

OgHgOlgO g av e a d ib ro m o d e r i v a t i v e , CgHBrgClgO, i n d i c a t i n g more c o n c lu s iv e ly t h a t th e s u l f u r i c a c id h y d ro ly s is p ro d u c t o f th e te tra c h lo ro d ie n e i s 2 , 3 , 4 -tric h lo ro -2 -o y c lo p e n te n o n e . T re a tm e n t o f 2 , 3 , 4 - t r io h l o r o - 2 - c y e lo p e n t e n o n e w i t h b a s e gave a t e t r a c h l o r o t e t r a h y d r o - 4 ,7 - m e t h a n o i n d e n e - l ,8 - d i o n e , C10H4G14^2* a rG & o tio n t y p i c a l o f h a l o e y o l o p e n t e n o n e s .

H ow ever,

p y r o l y s i s o f t h i s c a r b o n y l b r i d g e compound y i e l d e d a p r o d u c t h a v i n g th e f o r m u la C^gHyCl^Og, i n s t e a d o f f o r m in g t h e e x p e c t e d d i h y d r o i n d p n e , OgH^Ql^O.

I t i s c o n c e i v a b l e t h a t t h e compound

CigH^Ol^Og c o u l d f o rm by a D i e l s - A l d e r t y p e d i m e r i z a t i o n o f t h e i n t e r m e d i a t e d i h y d r o i n d o n e w h ic h h a s a 1 , 3 - d i e n e s y s te m a n d a d o u b l e b o n d a c t i v a t e d by a c a r b o n y l g r o u p .

Dihydro**

^

(* T h i s compound r e p r e s e n t s one o f s e v e r a l p o s s i b l e

is o m e rs .)

i n d o n e s a r e known t o u n d e rg o D i e l s - A l d e r r e a c t i o n s ^ .

6.

A l l e n a n d S p a n i e l , J , Am. Ghem. S o c . ,

5 5 , 3773 ( 1 9 3 3 ) .

E x p erim e n tal P r e p a r a tio n o f 2 .3 ,4 -T rlc h lo ro -2 -G y c lo p e n te n o n e . m i x t u r e o f 306 g .

A

( 1 . 5 m o le s ) o f 1 , 2 , 3 , 4 - t e t r a e h l o r o e y o l o

p e n t a d i e n e w as s t i r r e d a t room t e m p e r a t u r e f o r f i v e h o u r s . H y d ro g en c h l o r i d e w as e v o l v e d t h r o u g h o u t t h e r e a c t i o n . end of th e r e a c t i o n

t im e ,

At th e

t h e m i x t u r e a p p e a r e d to b e one p h a s e .

I t w as t h e n p o u r e d on ch o p p ed i c e ,

t h e o r g a n i c l a y e r was

s e p a r a t e d a n d th e a q u e o u s l a y e r e x t r a c t e d w i t h 250 m l . o f c h lo ro fo rm .

The c h l o r o f o r m s o l u t i o n w as a d d e d t o t h e o r g a n i c

m a t e r i a l , w a sh e d f i v e

t i m e s w i t h 100 m l . p o r t i o n s o f w a t e r ,

and d r i e d o v e r so d iu m s u l f a t e a n d D r i e r i t e .

The s o l v e n t was

rem o ved by d i s t i l l a t i o n ,

a n d t h e r e m a i n i n g l i q u i d vacuum

d i s t i l l e d t o g i v e 10 g .

o f p r e - r u n a n d 213 g .

d e s ire d p ro d u ct b o ilin g

a t 8 4 0 - 8 5 ° / l . 5 mm. E g.

(81.4% )

of

The p r o d u c t

c a n be r e c r y s t a l l i s e d fro m p e t r o l e u m e t h e r ( 3 5 0- 3 7 ° )

to g iv e a

w h ite s o l i d m e ltin g a t 2 7 °-2 8 0 . A n a ly sis:

th e

G a l c ' d . f o r O^EgOlgO:

G, 3 2 . 3 ; H, 1 . 6 2

Found:

0 , 3 2 . 4 ; H, 1 . 6 2

x il

P re p a ra tio n of ffe tra o h lo ro -g a ,4 t 4 a ,7 - te tr a h y a r o - 4 ,7m eth an o in d e n e - 1 , 8 » d io n e .

F o r t y gram s ( 0 . 2 2 m o le)

of 2 ,5 ,4 -

t r i o h l o r o * 2 - o y o l o p e n t e n o n e w as d i s s o l T e d i n 100 ml# o f g l a o i a l a o e t i o a c i d , a n d 30 g . o f sodium a o e t a t e w as a d d e d t o t h e s t i r r e d so lu tio n * h e a t.

fThe m i x t u r e i m m e d i a t e l y t u r n e d d a r k and g a v e o f f

A f t e r one h o u r o f s t i r r i n g ,

t h e r e a c t i o n m i x t u r e w as

d i l u t e d w i t h w a t e r , a n d a brow n p r e c i p i t a t e fo rm e d w h ic h w a s c o l l e c t e d on a f i l t e r .

A s m a l l am ount o f o r g a n i c l i q u i d s t i l l

re m a in e d in th e f i l t r a t e .

T h is l i q u i d w as s e p a r a t e d fro m t h e

a q u e o u s l a y e r , d i s s o l v e d i n 25 m l . o f a c e t i c a o i d a n d 10 g . o f so d iu m a c e t a t e a d d e d .

$he m i x t u r e w as t r e a t e d i n t h e

m anner a s th e o r i g i n a l r e a c t i o n . added to th e f i r s t f r a c t i o n . m a t e r i a l y i e l d e d 13 g . w i t h d e c o m p o sitio n .

same

She p r o d u c t o b t a i n e d w a s

R e c r y s t a l l i z a t i o n o f th e cru d e

(40%) o f p r o d u c t m e l t i n g a t 1 8 0 0- 1 8 2 °

Two r e c r y s t a l l i z a t i o n s gave f l u f f y w h i t e

c r y s t a l s m e l t i n g a t 1 8 4 ° - 1 8 5 0 w i t h t h e e v o l u t i o n o f g a s to a y e llo w l i q u i d . A n a ly sis:

G a l c ’ d . f o r ^ i o E4C14 ° 2 : Found:

M. W. ( H a s t )

O a l o ’d . :

40•2 ; 0 , 4 0 . 0 ; H, 1 . 3 4 .

298; Found, 270.

P y ro ly s is of T e tra c h lo ro -3 a ,4 . 7 , 7 a -te tr a h y d r o - 4 ,7m e th an o in d e n e-1 . 8 - d io n e .

T h r e e gram s o f t e t r a e h l o r o - 3 a , 4 , 7 , 7 a -

t e t r a h y d r o - 4 , 7 - m e t h a n o i n d e n e - l , 8 - d i o n e w as d i s s o l v e d i n 30 m l. o f x y len e and re f lu x e d f o r f o u r h o u rs . e v o lv e d th ro u g h o u t th e h e a t i n g . d istilla tio n ,

H ydrogen c h l o r i d e w as

The x y l e n e was rem oved b y

t h e l a s t t r a c e s b e i n g rem oved by a i r e v a p o r a t i o n .

x iii

The r e m a i n i n g t a n s o l i d w as r e o r y s t a l l i z e d fro m p e t r o l e u m e t h e r ( 9 0 ° - 1 0 0 ° ) and b e n z e n e t o g i v e a w h i t e p o w d e r m e l t i n g a t 262°-2640 . A n a ly sis:

O a l o ’ d . f o r O^gB^Gl^Og:

0 , 4 2 . 9 ; H, 1 .3 8

Found:

0 , 4 3 .0 , 4 3 .3 ; H, 1 . 2 5 , 1 . 3 0 .

M. W. ( B a s t ) O a l o ’d . ;

503.

Found :

520.

P r e p a r a t io n o f 5 ~ 8 ro m o ~ 2 ,3 ,4 ~ trio h lo ro ~ 2 ~ o y o lo p e n te n o n e . A s o l u t i o n o f 30 g .

( 0 .1 9 m ole)

o f b ro m in e i n 50 m l . o f c a r b o n

t e t r a c h l o r i d e was a d d e d d r o p w is e t o a r e f l u x i n g s o l u t i o n o f 35 g .

( 0 . 1 9 m ole)

o f 2 , 3 , 4 - t r i c h l o r o - 2 - c y o l o p e n t e n o n e i n 50 m l .

o f carbon t e t r a c h l o r i d e .

T hroughout th e 2 .5 h o u r a d d i t i o n ,

h y d r o g e n b ro m id e w as e v o l v e d .

The s o l u t i o n w a s d r i e d o v e r

D r i e r i t e a n d t h e n t h e s o l v e n t re m o v e d . y ie ld e d 2 g.

42 g .

(91$) o f

of h ig h e r b o ilin g

Vacuum d i s t i l l a t i o n

p ro d u ct b o ilin g a t

9 3 ° - 1 0 0 O/ 3 mm. H g . ,

m a te ria l,

of

and 4 g .

d a rk p o tr e s i d u e .

R e d i s t i l l a t i o n th ro u g h a O la is e n f l a s k e q u ip p e d w ith a V ig reu x colum n g a v e p r a c t i c a l l y a l l o f t h e p r o d u c t b o i l i n g a t 8 9 ° - 9 1 0 / 2 mm. Hg.

n ? ° , 1 .5 8 4 8 .

A n a ly sis:

G a l e ’d . f o r CgHgBrGlgO:

C, 2 2 . 7 ; H,

0 .7 6

Found:

G, 2 2 . 7 ; H,

0 .7 5

P r e p a r a t i o n o f Cxoïï2^1 4S r 20 2*

A m i x t u r e o f 10 g . o f

5 - b r o m o ~ 2 , 3 , 4 ~ t r i c h l o r o ~ 2 ~ c y c l o p e n t e n o n e , 7 . 5 g . o f so d iu m a c e t a t e a n d 10 m l.

o f g l a c i a l a c e t i c a c i d w as s h a k e n .

was e v o l v e d a n d t h e m i x t u r e t u r n e d g r e e n .

H eat

A f t e r one h o u r t h e

m i x t u r e w as d i l u t e d w i t h a n e q u a l volum e o f w a t e r a n d a w h i t e s o lid se p a ra te d .

R e c r y s t a l l i z a t i o n fro m p e t r o l e u m e t h e r gave

2 . 1 g . o f p r o d u c t m e l t i n g a t 1 7 0 o- 1 7 1 ° w i t h d e c o m p o s i t i o n . A n a ly sis;

C a lc ’d.

f o r QiO H2 Q14 B r 2 ° 2 :

°» 2 6 . 3 ; H, 0 . 4 4

Found:

0, 2 5 .8 , 2 6 .0 ; H, 0 . 5 4 , 0 . 5 9

An a c i d h a v i n g a n e u t r a l i z a t i o n e q u i v a l e n t o f 167 w as i s o l a t e d fro m t h e m o th e r l i q u o r o f t h e r e a c t i o n m i x t u r e .

T h is

compound a m o u n ted t o 0 . 7 g . o f o r a n g e n e e d l e s , m e l t i n g a t 2 1 6 0- 2 1 8 ° . P r e p a r a t i o n o f OgKBrOl^O, a P o l y h a l o i n d o n e .

A m ix tu re o f

1 . 2 g . o f O^QHgOl^BrgOg i n 5 m l. o f x y l e n e w as h e a t e d t o r e f l u x , a n d h y d r o g e n h a l i d e was n o t e d b e i n g e v o l v e d .

The s o l u t i o n w as

r e f l u x e d f o r a p p r o x i m a t e l y two h o u r s an d t h e n t h e s o l v e n t was rem oved.

T h r e e r e c r y s t a l l i z a t i o n s fro m a m i x t u r e o f p e t r o l e u m

e t h e r and b en zen e gave 0 .3 g . A n a ly sis:

C a l e ’d .

of a p ro d u c t m e ltin g a t 156°-1570 .

f o r OgHBrOl^O: Found:

0 , 3 1 . 2 ; H, 0 . 2 9 0 , 3 1 .0 , 3 1 .1 ; H, 0 . 2 9 , 0 . 3 2 .

M. W. ( B a s t ) O a l o ’ d . :

347.

Found:

356.

The D i b r o m l n a t l o n o f 2 , 3 , 4 ~ T r i c h l o r o - 2 ~ c y c l o p e n t e n o n e . A s o l u t i o n o f 25 g .

( 0 . 1 3 m o le ) o f 2 , 3 , 4 ~ t r i c h l o r o ~ 2 ~ c y c l o p e n t e n o n e

i n 50 m l . o f c a r b o n t e t r a c h l o r i d e w a s b r o u g h t t o r e f l u x a n d 50 g . ( 0 . 3 1 m o le )

o f b ro m in e i n 50 m l. o f c a r b o n t e t r a c h l o r i d e

w as a d d e d d r o p w i s e .

The f i r s t h a l f o f t h e a d d i t i o n p r o c e e d e d

r a p i d l y w i t h t h e e v o l u t i o n o f h y d r o g e n b r o m id e , a n d t h e n t h e r e a c t i o n becam e s l u g g i s h .

The c a r b o n t e t r a c h l o r i d e w as

rem oved b y d i s t i l l a t i o n a n d 50 m l . o f a c e t i c a c i d w as a d d e d . The r e m a i n d e r o f t h e b ro m in e w as d r o p p e d i n a n d t h e m i x t u r e

XV

w as h e a t e d on a s te a m b a t h o v e r n i g h t .

The u n r e a o t e d b r o m in e

and c a r b o n t e t r a c h l o r i d e w as rem o ved by d i s t i l l a t i o n a n d t h e a c e tic a c id so lu tio n d ilu te d w ith w a te r. was e x t r a c t e d w i t h c h l o r o f o r m .

The l i q u i d m i x t u r e

The c h l o r o f o r m s o l u t i o n w as

w a sh e d w i t h w a t e r an d d r i e d o v e r so dium s u l f a t e . g a v e 32 g .

(

D istilla tio n

70 %) o f p r o d u c t b o i l i n g a t 1 0 9 ° - 1 1 3 o/ 2 mm. E g.

n ^ ° , 1 .6 2 2 7 . A n a ly sis:

C a l c ' d . f o r OgHClgBrgO:

0 , 1 7 . 5 ; H, 0 . 2 9

Found:

C, 1 7 . 3 ; H, 0 . 2 8

A c k n o w led g m e n t.

The a u t h o r s w i s h t o e x p r e s s t h e i r th a n k s ,

t o t h e H o o k er E l e c t r o c h e m i c a l Company a n d t h e P u rd u e R e s e a r c h F o u n d a tio n f o r t h e i r f i n a n c i a l a s s i s t a n c e . Summary B ro m in a tio n an d d eh y d ro h a lo g é n a tio n s t u d i e s i n d i c a t e t h a t t h e m ain p r o d u c t o f h y d r o l y s i s o f 1 , 2 , 3 , 4 - t e t r a c h l o r o c y o lo p e n ta d ie n e w ith s u l f u r i c a c id i s 2 ,3 ,4 ~ tric h lo r o ~ 2 - c y c lo ~ p e n te n o n e .

D e h y d ro h a lo g e n a tio n o f 2 , 3 , 4 - t r i c h l o r o - 2 - c y e l o -

p e n te n o n e y i e l d s a t e t r a c h l o r o t e t r a h y d r o - 4 , 7 - m e t h a n o i n d e n e - l , 8 d i o n e , w h ic h d e c o m p o se s a t i t s m e l t i n g p o i n t i n t o C ^ E y C ly O g .

xv i

( C o n t r i b u t i o n fro m t h e D e p a r tm e n t o f C h e m is tr y and P urdue K e se a rc h F o u n d a tio n ) P urdue U n i v e r s i ty > L a fa y e tte , In d ian a TEB ADDITION OF BBOMIBE AMD CELOBIFS TO 1 , 2 , 3 , 4 EElRAOmOEOCYCIOMillADXESS By l a r i T. McBee a n d R i c h a r d K, M e y ers

1.

Taken i n p a r t from a t h e s i s s u b m i t t e d by R. K« M ey ers t o th e f a c u l t y o f Purdue U n iv e r s ity i n p a r t i a l f u l f i l l m e n t o f th e r e q u ir e m e n ts f o r th e d e g re e of D o c to r o f P h ilo so p h y in F e b ru ary , 1950. ABSTRACT In tro d u c tio n The a d d i t i o n o f h a l o g e n t o 1 , 2 , 3 , 4 - t e t r a c h l o r o c y c l o -

p e n t a d i e n e was u n d e r t a k e n w i t h t h e i d e a i n m ind o f p r e p a r i n g some compounds w h ic h m i g h t p r o v e o f v a l u e a s i n s e c t i c i d e s . B ro m in a tio n g T h ie le

2.

r e p o r t e d t h a t t h e a d d i t i o n o f b ro m in e t o c y c l o -

T h i e l e , A n n ., 3 1 4 . 3 0 0 - 2 ( 1 9 0 0 ) .

p e n ta d ie n e g iv e s a m ix tu re o f th e e i s - t r a n s 1 ,4 - a d d i t i o n p ro d u c ts.

F a r m e r a n d S c o tt® f o u n d t h a t some 1 , 2 - a d d i t l o n 7

-

3,

-

F a r m e r and S c o t t , J . Chem. S o c . , 1 9 2 9 , 1 7 2 - 8 0 .

p ro d u c t a ls o form ed. B r o m i n a t i o n o f 1 , 2 , 3 , 4 - t e t r a c h l o r o c y e l o p e n t a d i e n e gave an

x v ii

8 5 $ y i e l d o f an a d d i t i o n p r o d u c t , CgHgBrgCl^ m e l t i n g a t 70 o- 7 1 ° «

The compound w as h y d r o l y z e d a t room t e m p e r a t u r e w i t h

s u l f u r i c a c i d t o a m o n o k e to n e , GgHgBrQlgO.

H y d ro ly sis of t h i s

k e t o n e a t 6 0 ° y i e l d e d a compound h a v i n g p r o p e r t i e s i d e n t i c a l to 2 , 3 - d i c h l o r o -c y c lo p e n te n e - 1 , 3 -d io n e p re p a re d p re v io u s ly 4 b y Z in o k e . S i n c e t h e 1 , 3 - d i k e t o n e c a n c o n c e i v a b l y r e s u l t

4.

Z in o k e a n d R o h d e , A n n ., 2 9 9 , 377 ( 1 8 9 8 ) .

fro m b o t h t h e 1 , 2 - an d 1 , 4 - a d d i t i o n p r o d u c t s o f b r o m in e t o 1 , 2 , 3 , 4 - te tr a c h lo r o c y c lo p e n ta d ie n e , i t can n o t be s t a t e d w h e t h e r GgHgBrgGl^ i s

th e 1 ,2 » o r 1 , 4 - a d d i t i o n p r o d u c t.

The com pound, CgHgBrOl^O, o b t a i n e d by h y d r o l y s i s o f OgHgBrgCl^, i s b e l i e v e d t o b e 4 -b ro m o - 2 , 3 , 4 - t r i c h l o r o - 2 cy clo p en ten o n e .

The a s s i g n m e n t o f t h i s s t r u c t u r e i s b a s e d

upon t h e f o l l o w i n g e v i d e n c e .

The com pound, when r e a c t e d w i t h

so d iu m a c e t a t e i n a c e t i c a c i d , g a v e a h e x a c h l o r o - 3 a , 4 , 7 , 7 a te tra h y d ro -4 ,7 -m e th a n o in d e n e -l,8 -d io n e , a carb o n y l b rid g e compound, w h ic h r e a d i l y decom posed a t i t s m e l t i n g p o i n t i n t o an in d o n e .

fo rm a tio n o f th e t r i c y c l i c

d i k e t o n e by d e h y d r o -

b r o m i n a t i o n i n d i c a t e s t h a t CgHgBrClgO i s a c y c l o p e n t e n o n s . S i n c e t h e m o n o k eto n e w as h y d r o l y z e d t o 2 , 3 - d i c h l o r o - 2 - c y c l o p e n t e n e - 1 , 4 - d i o n e , i t c a n b e a ssu m e d t h a t a b r o m in e ato m and a c h l o r i n e a to m a r e a t t a c h e d t o a c a r b o n a to m a l l y l i o a d o u b le bond and b e t a to a c a rb o n y l g ro u p .

to

The k e t o n e

b ro m in a te d i n an a c id s o l u t i o n w i t h t h e e v o l u t i o n o f hy d ro g en b ro m id e .

T h is r e a c t i o n i n d i c a t e s t h a t t h e compound h a s

h y d r o g e n a to m s t h a t a r e a l p h a t o t h e c a r b o n y l g r o u p .

The

x v lii

r e s u l t s o f th e s e ex p erim e n ts le a d to th e c o n c lu sio n t h a t OgHgBrClgO i s 4 - h r o m o ^ 2 , 3 , 4 - t r i c h l o r o - E - e y c l o p e n t e n o n e . Ohio r i n a t i o n fh e c h lo r i n a t i o n of 1 , 2 , 3 , 4 - te tr a c h lo r o c y c lo p e n ta d ie n e in c arb o n t e t r a c h l o r i d e y i e l d e d a m ix tu re o f p r o d u c t s . A p p r o x i m a t e l y 30% o f th e t e t r a c h l o r o c y c l o p e n t a d i e n e was c o n v e r t e d t o a s o l i d a d d i t i o n p r o d u c t , OgHgCl^ ( m . p . , 4 4 ° - 4 5 0 ) . A p e n t a c h l o r o c y c l o p e n t a d i e n e was a l s o d e t e c t e d i n t h e c h l o r i n a t i o n m i x t u r e by i t s r e a c t i o n w i t h m a l e i c a n h y d r i d e . A s e r i e s o f r e a c t i o n s w e r e p e r f o r m e d on t h e compound G5 ÏÏ2 G I 6 ( m . p . , 4 4 ° - 4 5 0 ) .

S u lf u r ic a c id h y d ro ly ze d i t to

2 , 3 -d io h lo ro -2 -c y c lo p e n te n o n e .

D e h y d ro h a lo g e n a tio n pro d u ced

a p e n t a c h l o r o c y c l o p e n t a d i e n e w h ic h u n d e r w e n t a D i e l s - A l d e r r e a c t i o n w ith m aleic a n h y d rid e . When GgHgOlg w as r e a c t e d w i t h e x c e s s m e th a n 0 l i e b a s e , a t r i o h l o r o d i m e t h o x y o y e l o p e n t a d i e n e was o b t a i n e d .

The l a t t e r

compound c a n a l s o be p r e p a r e d fro m t h e p e n t a c h l o r o c y c l o ­ p e n ta d ie n e . by i t s

The 1 , 3 - d i e n e s t r u c t u r e o f t h e k e t a l w as shown

r e a c t i o n w ith m aleic a n h y d rid e .

A h e x a c h lo ro -

m e t h a n o i n d e n e - 1 , 8 - d i o n e w as i s o l a t e d fro m t h e r e a c t i o n o f th e k e ta l w ith s u l f u r i c a c id . w as h e a t e d ,

When t h i s

t r i c y c l i c d ik e to n e

i t d ecom p osed i n t o a p e n t a c h l o r o i n d o n e .

The

r e a c tio n s of th e tric h lo ro d im e th o x y c y c lo p e n ta d ie n e a re a n a lo g o u s to th e r e a c t i o n s o f te tr a c h lo r o d im e th o x y c y c lo p e n t a d i e n e o u t l i n e d by le w c o m e r a n d MoBee^.

xlx

5.

lew o o m e r a n d McBee, £ • Am. Ghem. S o c . ,

7 1 , 946 ( 1 9 4 9 ) .

The s e r i e s o f r e a c t i o n s d i s c u s s e d a r e r e p r e s e n t e d i n F ig u re I . E x p e rim e n ta l B ro m in a tio n o f 1 , 2 , 5 , 4 - T e tr a o h lo r o o y c lo p e n ta d ie n e . s o l u t i o n o f 220 g .

( 1 . 3 8 m o le s )

A

o f b r o m in e i n 110 m l . o f

c a r b o n t e t r a c h l o r i d e w as ad d ed d r o p w i s e o v e r a p e r i o d o f two h o u r s t o a r e f l u x i n g s o l u t i o n o f 276 g . ( 1 . 3 5 m o le s ) o f 1 , 2 , 3 , 4 - t e t r a c h l o r o c y c l o p e n t a d i e n e i n 250 m l. o f c a r b o n te tra c h lo rid e .

The m i x t u r e was s t i r r e d o v e r n i g h t .

A m ajo r

p o r t i o n o f t h e c a r b o n t e t r a c h l o r i d e w as rem oved by d i s t i l l a t i o n a n d t h e n t h e r e m a i n i n g l i q u i d w as c o o l e d .

A t o t a l o f 426 g .

(86.9% ) o f p r o d u c t c r y s t a l l i z e d , m e l t i n g fro m 6 6 ° - 7 0 o . B e e r y s t a l l i z a t i o n fro m m e t h a n o l gave w h i t e p l a t e l e t s o f C5HgBr2C l 4 m e l t i n g a t 70o - 7 1 ° . A n a ly sis: 01, 5 8 .5 .

C a l c ’ d . f o r G^H^Br^Gl^:

Found:

T o ta l h a lo g e n a s

T o ta l h a lo g e n a s G l, 5 8 .9 .

P r e p a r a t i o n o f 4 -B ro m o ~ 2 , 3 , 4 ~ t r i c h l o r o - 2 - c y c l o p e n t e n o n e . A m i x t u r e o f 60 g .

( 0 . 1 7 m o le ) o f CgHgBrgCl^ and 150 m l. o f

c o n c e n t r a t e d s u l f u r i c a c i d w as s t i r r e d a t room t e m p e r a t u r e i n a t h r e e - n e c k e d f l a s k open t o t h e a i r .

B ro m in e , fro m t h e

o x i d a t i o n o f h y d r o g e n b r o m id e by s u l f u r i c a c i d , w as e v o l v e d d u rin g th e r e a c t i o n .

A t t h e e n d o f a b o u t tw e n ty h o u r s ,

m i x t u r e was p o u r e d o n t o c h o p p e d i c e .

th e

The o r g a n i c l a y e r was

s e p a r a te d and th e aqueous l a y e r e x tr a c te d s e v e r a l tim e s w ith

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o cd * _X 4f

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