Fused small ring compounds
by Shi-Kuang Yao
A THESIS Submitted to the Graduate Faculty in partial fulfillment of the requirements for the degree
of Doctor of Philosophy in Chemistry
Montana State University
© Copyright by Shi-Kuang Yao (1960)
Abstract:
Bicyclo(3.1.0)hexane-6-carboxylic acid [diagram not captured by OCR] has been synthesized by
reaction of cyclopentene with ethyl diazoacetate in the presence of copper powder followed by alkaline
hydrolysis. It has been observed that this compound does not undergo the Hell-Volhard-Zelinsky
reaction.
Rearrangement of 6,6-dichlorobicyclo(3.1.0)hexane was found to occur on heating. Both the original
dichloride and the rearrangement product gave the same l-chloro-6-acetoxy-l-cyclohexene when
refluxed with potassium acetate and acetic anhydride.
The structure of the rearrangement product, 1,6-dichloro-l-cyclohex-ene, was proved by degradation
and by preparing an authentic compound. The unknown and the authentic compound were found
identical by both infrared and vapor phase chromatography analyses.
The following mechanisms are proposed: 1. 6,6-DichlorobicycIo(3,1.0)hexane* is heated at 150°C.:
[diagrams not captured by OCR] 2. 6,6-Dichlorobicyclo(3.1.0)hexane reacts with potassium acetate in
acetic anhydride: [diagrams not captured by OCR] * The number of members in the ring to the right
exclusive of the members linking the two rings togethere are indicated by a number. Similarly the
members of the smaller ring are designated. Lastly the members of the link (bridge) exclusive of the
linking members are designated by number also. viz. bicyclo(3.1.0)hexane [diagram not captured by
OCR] For the numbering of the compound, start numbering 1 at one of the carbons in the bridge as
illustrated above. FUSED SMALL RING COMPOUNDS
by
Shi= K uang Yao
A THESIS
S u b m itte d t o t h e G r a d u a te F a c u l t y
in
p a r t i a l f u l f i l l m e n t o f t h e r e q u i r 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 i n C h e m is try
. at
M o n tan a S t a t e C o lle g e
A p p ro v e d :
H ead iI M a jo r D e p a rtm e n t
C h a irm a n » _ Jlx a m in in g C o n ttn itte e
D e a n , G ra d u a W D i v i s i o n
Bozem an, M ontana
A u g u s t , ,1 9 6 0
ACKNOWLEDGEMENT
I w is h a t t h i s - tim e t o a c k n o w le d g e my s i n c e r e a p p r e c i a t i o n and
th a n k s t o D r. L . 0 . B i n d e r , J r .
f o r h i s g u id a n c e , p a t i e n c e a n d c o n s i d e r a ­
t i o n d u r in g my y e a r s i n G r a d u a te S c h o o l.
T han ks a r e a l s o e x te n d e d t o my b o a r d member’s , D r s . E . W. A n a c k e r,
K. J . G o e r in g , B. L . J o h n s o n , G. H. Roehm, G. E. U h r ic h a n d e s p e c i a l l y
W, B. Cook f o r t h e i r p a t i e n c e a n d h e l p .
I w o u ld l i k e t o e x te n d my th a n k s t o t h e o t h e r s t a f f m em bers and
f e l l o w g r a d u a t e s i n t h e C h e m is try D e p a rtm e n t f o r t h e i r h e l p f u l s u g g e s t i o n s .
F i n a l l y , th a n k s t o my w i f e who h a s b e e n so p a t i e n t f o r t h e l a s t few
y e a rs.
TABLE OF CONTENTS
L i s t o f T a b le s ,
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Abstract, , , ,
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. o 18
0
P r e p a r a t i o n o f e t h y l b i c y c l o ( 3 e I . 0 ) h e x a n e = 6- c a r b o x y l a t e .
18
P r e p a r a t i o n o f b i c y c l o ( 3 e I . 0 ) h e x a n e = 6 - c a r b o x y l i c a c i d 0 9 0 , 0 0 0 18
P r e p a r a t i o n o f b i c y c l o ( 3 . 1 . 0 ) h e x a n e - 6 - c a r b o n y l b ro m id e
,
0
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19
9
P r e p a r a t i o n o f b i c y c I o ( 3 . 1. 0 ) h e x a n e - 6 - c a rb o x a m id e » . ,
19
P re p a ra tio n o f 6, 6 - d ic h lo ro b ic y c lo (3 » I . 0 )hexane
19
P r e p a r a t i o n o f l - c h l o r o - b - a c e t o x y - l - e y c l o h e x e n e fro m
6 36 'd i c h l o r o b i c y c l o ( 3 . 1 . 0 ) h e x a n e „
P r e p a r a t i o n o f l - c h l o r o - 6 - a c e t o x y - l - c y c l o h e x e n e from
,
1, 6- d i c h l o r o - l - c y c l o h e x e n e . , » . . .
0
9
0
P r e p a r a t i o n o f b i c y c I o ( S e l 1O)h e x a n e „ „ . . „
0
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The r e d u c t i o n o f I , 6 “ d i c h l o r o - 1 - c y c l o h e x e n e w i t h so d iu m
a n d m e th a n o l o a , , * * * * * * * * * * * * * * * * * * * * *
P r e p a r a tio n o f l-c h lo ro -6 -h y d ro x y -l-c y c lo h e x e n e .
,
P re p a ra tio n o f l-c h lo ro -c y c lo h e x -l-e n -6 -o n e . « ,
0
0
0
,
0
The r e a c t i o n o f l - c h l o r o - 6 - h y d r o x y - 1 - c y c lo h e x e n e w i t h
p o t a s s i u m p e rm a n g a n a te s o l u t i o n
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D e h y d r o g e n a tio n o f l - c h l o r o - 6 - a c e t o x y - l - c y c l o h e x e n e i n t h e
,
p resen ce of s u lf u r o r c h lo r a n il i , ,
I n f r a r e d d a ta
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» v 24
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The r e a c t i o n o f l- c h lo r o ^ G - h y d r o x y t- l- c y c lo h e x e n e w i t h
o o o o o o o o
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27
" 5D is c u s s io n .
30
T he P o s s i b i l i t i e s o f F u t u r e R e s e a r c h
38
Summary
40
L ite r a tu r e C ite d .
41
LIST OF TABLES
C o m p o s itio n o f e q u i l i b r i u m , m ix t u r e s o f jB , ^ d i a l k y l - C t
k e t o g l u t a r i c a c id and t h e i r c y c li c d e r i v a t i v e s . « .
-
7-
LIST OF FIGURES
I.
B i c y c l o ( 3 .1 .0 ) h e x a n e " 6 - c a r b o x y l i c a c i d (5% w/w i n C C I^) ........................ 27
2.
B ic y c l o ( 3 . 1 . 0 ) h e x a n e - 6 - c a rb o x a m id e ( N u jo l m u ll) . . . . .
3.
6 ,.S - D i c h lo r q b ic y c I o ( 3 . 1 . 0 ) h e x a n e ( c a p i l l a r y f i l m ) ....................................... . 2 8
4.
B i c y c l o ( 3 . 1 . 0 ) h e x a n e (20% v / v i n C C l^ ).
5.
1 , 6 - D i c h l o r 0 - 1 - c y c lo h e x e n e (20% v / v i n C S g ) .........................................................29
6.
A u t h e n t i c com pound o f I , 6 - d i c h l o r o - l - c y c l o h e x e n e
(20% v / v i n C S g ). . . . .
......................... . . . . . . . . . . . . . . .
. , i .
.......................
.............................
27
28
29
•m3 *
ABSTRACT
B i c y c l o ( 3 . 1 . 0 ) h e x a n e - 6 - c a r b o x y l i c a c i d ( Haoc ^ <T Z / > ) u a s b e e n s y n t h e ­
s i z e d by r e a c t i o n o f e y e l o p e n t e n e w i t h e t h y l d i a z o a c e t a t e .n th e p r e s e n c e
o f c o p p e r pow der f o llo w e d by a l k a l i n e h y d r o l y s i s .
I t n a s b e e n o b s e rv e d
t h a t t h i s compound d o e s n o t u n d e rg o t h e H e l l- V o l h a r d - Z e li n s k y r e a c t i o n .
R e a rra n g e m e n t o f 6 , 6 - d i c h l o r o b i c y c l o ( 3 . 1 . 0 ) h e x a n e was fo u n d t o o c c u r
on h e a t i n g .
B o th th e o r i g i n a l d i c h l o r i d e and t h e r e a r r a n g e m e n t p r o d u c t
g a v e t h e same l - c h l o r o - 6 - a c e t o x y - l - c y c l o h e x e n e when r e f l u x e d w i t h p o ta s s iu m
a c e t a te and a c e t i c a n h y d rid e .
The s t r u c t u r e o f t h e r e a r r a n g e m e n t p r o d u c t , I , 6 - d i c h l o r o - l - c y c l o h e x e n e , was p r o v e d by d e g r a d a t i o n an d by p r e p a r i n g a n a u t h e n t i c com pound. The
unknown a n d th e a u t h e n t i c compound w e re fo u n d i d e n t i c a l by b o t h i n f r a r e d
a n d v a p o r p h a s e c h ro m a to g ra p h y a n a l y s e s .
Cl
The f o ll o w i n g m echanism s a r e p r o p o s e d :
6 , 6 -D i c h l o r o b i c y c I o ( 3 . I . 0 ) h e x a n e * i s h e a te d a t 150°C . :
I.
Cl
Cl
Cl
Cl
\ +
I
y
+Tl ~
\ -C l
2 . 6 , 6 - D i c h l o r o b i c y c l o ( 3 . I . 0 ) h e x a n e r e a c t s w i t h p o ta s s iu m a c e t a t e i n
a c e t i c a n h y d r id e :
Cl
Cl
\
Cl
CH^COO"
Cl
Cl
/
Cl
Cl
I
"OOCCH,
Xx/
;
00 CCH3
/> / \ ^
-OOCCH 3
-C l
* The num ber o f m em bers i n t h e r i n g t o t h e r i g h t e x c l u s i v e o f t h e members
l i n k i n g t h e two r i n g s t o g e t h e r e a r e i n d i c a t e d by a n u m b er. S i m i l a r l y
t h e m em bers o f t h e s m a l l e r r i n g a r e d e s i g n a t e d . L a s t l y th e members o f
t h e l i n k ( b r i d g e ) e x c l u s i v e o f t h e l i n k i n g members a r e d e s i g n a t e d by num­
b er a ls o .
v i z . b i c y c l o ( 3 . 1. 0) h e x a n e
5
5
4
F o r t h e n u m b e rin g o f t h e com pound, s t a r t n u m b erin g I a t one o f t h e c a r ­
bo n s i n th e b r i d g e a s i l l u s t r a t e d a b o v e .
\
9INTRODUCTION
T h e re h a v e b e e n a t t e m p t s to s y n t h e s i z e e y e lo p ro p a n o n e f o r t h e p a s t
40 y e a r s ; h o w ever a l l t h e s e a t t e m p t s h a v e m et w ith f a i l u r e .
T h is i s u n ­
d o u b te d ly due t o t h e g r e a t s t r a i n on a th re e -m e m b e re d r i n g .
I n 1 9 2 2 , I n g o ld ( I ) r e p o r t e d t h e s y n t h e s i s o f e y e lo p r o p a n o n e by
t h e f o ll o w i n g m eth o d :
Demyanov an d F e o f i l a k t o v (2 ) a t t e m p t e d t o r e p e a t I n g o l d 's
( I ) w ork
v e r y c a r e f u l l y by t h e f o ll o w i n g schem e:
CH2Br
+
Z
Na-CH
CN
CN
COOC2 H5
OOC2H5
CH2Br
CO-NH
CONH
COOH
-CONH
COOH
-1 0 A c t u a l l y , h o w e v e r, t h e w ork was n o t c o m p le te d , and th e y s u g g e s t
t h a t t h e s t r u c t u r e o f t h e h y d ro x y a c i d , w h ic h was t h e l a s t s t e p th e y
r e a c h e d , w i l l b e a r m ore s tu d y .
Demyanov and F e o f i l a k t o v (2 ) s t a t e d t h a t w ith t h e e v id e n c e p r e s e n t e d
i t was q u i t e u n l i k e l y t h a t I n g o ld a c t u a l l y h ad e y e I o p r o p a n o n e .
They a l s o
c o n c lu d e d t h a t a l l t h e e v id e n c e p o i n t s t o th e n o n - e x i s t e n c e o f I n g o l d 's
e y e lo p r o p a n o n e , a n d p r o b a b l e g r e a t i n s t a b i l i t y o f t h e compound i f ,
in d e e d ,
i t e x is ts a t a l l .
L ip p (3 ) h a s a t t e m p t e d t o s y n t h e s i z e e y e lo p r o p a n o n e by t h e f o ll o w ­
in g m eth o d :
The f i n a l s t e p g a v e o n l y c y c lo p r o p a n e c a r b o x y l i c a c i d a n d o t h e r d e g r a d a ­
tio n p ro d u c ts .
L ip p th e n t r i e d
t h e f o l l o w i n g m ethod:
-1 1 The s y n t h e s i s was s u c c e s s f u l a s f a r a s d i p h e n y l m e th y le n e c y c lo p r o p a n e ,
b u t o n ly b e n z o p h e n o n e was o b t a i n e d on o z o n o l y s i s .
L ip p a l s o t r i e d d ia z o m e th a n e e x p a n s io n o f k e te n e ( 3 ) , b u t t h i s
y i e l d e d o n ly e y e lo b u ta n o n e w h ic h h a s b e e n known f o r y e a r s .
L ip p h a s c o n c lu d e d t h a t I n g o ld m is to o k I , 1 - d ih y d r o x y - c y c lo p r o p a n e
f o r e y e lo p r o p a n o n e .
F r a n c i s and W ils o n ( 4 ) o b t a i n e d a c y c l i c d e r i v a t i v e o f p h o ro n e f o r
w h ic h th e y a s s i g n e d t h e s t r u c t u r e shown b elo w :
I n g o ld a n d S h oppee ( 5 ) s u g g e s t e d t h a t th e compound p r e p a r e d by F r a n c i s an d
W ils o n was s t a b i l i z e d by ta u to m e r is m :
Guha a n d S e s h a d r i n g a r ( 6) h a v e r e p o r t e d o b t a i n i n g b i c y c l o ( 3 . 1 . 0 ) h e x a n - l - o n - 2 , 6 - d i e t h y l c a r b o x y l a t e , b u t th e y f a i l e d t o g i v e a n y d e f i n i t e
e v id e n c e .
I n a l l c a s e s , w h e re t h e th re e -m e m b e re d r i n g s a t u r a t e d k e to n e h a s
been c le a r ly id e n tif ie d ,
t h e r e h a v e b e e n g e m in a l o r l a r g e g ro u p s p r e s e n t
on t h e th re e -m e m b e re d r i n g o r a n a d j a c e n t r i n g o f t h e c o n d e n s e d o r s p i r a n e
ty p e .
Known com pounds i n c l u d e e y e l o p r o p a n - I - o n - 2 ,2 - d i m e t h y l c a r b o x y l a t e
( 7 ) , l-b r o m o - 2 ,2 ,3 ,3 - te tr a m e th y l- b ic y c lo ( 2 .1 .0 ) p e n ta n - 4 - o l- 5 o n e ( 4 ) ,
12b i c y c l o ( 3 . 1 . 0 ) h e x a n - l - o n - 2 , 6 - d i e t h y l c a r b o x y l a t e ( 6 ) , a n d c y c lo h e x a n e s p ir o - c y c l o p r o p a n o n e ( 8) .
The im p o r ta n c e o f s t e r i c e f f e c t s on th e s t a b i l i t y o f t h e f o llo w in g
com pounds
-COOH
R.
yCOCOOH
.C
-COOH
R'
CH2COOH
(H )
h a s b e e n d i s c u s s e d by T h o rp e e t a l (9 )
(1 0 ) i n
T a b le I .
The c o m p o s itio n
o f t h e e q u i l i b r i u m m ix t u r e i s d e f i n i t e l y d e p e n d e n t on t h e n a t u r e o f s u b ­
s t i t u e n t s , R a n d R ', a s shown by t h e d a t a i n T a b le I .
T h is t r a n s f o r m a t i o n ,
b e in g an e q u i l i b r i u m and c o n s e q u e n t ly d i r e c t l y r e l a t e d t o th e th erm o d y n am ic
s t a b i l i t i e s o f t h e r e a c t a n t and p r o d u c t , o f f e r s c o n v in c in g e v id e n c e t h a t
g e m - s u b s t i t u e n t s o r a c o n d e n s e d r i n g s y s te m may s t a b i l i z e a th re e -m e m b e re d
r i n g , p e r h a p s th r o u g h a n e f f e c t on bond a n g l e s .
The c o r r e c t e d s t r u c t u r e o f compound I h a s b e e n r e a s s i g n e d by W ib erg
a n d H o lm q u is t (1 1 ) a s f o ll o w s :
R
CH-COOH
R
^CKHCOOH
The a b o v e com pound s t i l l p o s s e s s e s t h e sam e e f f e c t (1 2 ) w i t h w h ic h T h o rp e
e t a l have o b se rv e d .
S t a b i l i z a t i o n by r e s o n a n c e i s a l s o p o s s i b l e a s h a s b e e n demon­
s t r a t e d by B r e s low , H a y n ie a n d M ir r a (1 3 ) who h a v e s y n t h e s i z e d d ip h e n y l
e y e lo p ro p e n o n e from p h e n y l k e te n e d im e th y l a c e t a l w i t h b e n z a l c h l o r i d e
ioI S o
TABLE I
C o m p o s itio n o f E q u i l i b r i u m M ix tu r e s o f I s r & I l
Rl
% o f I i n M ix tu r e s
h y d ro g e n
h y d ro g e n
0
m e th y l
m e th y l
0
m e th y l
e th y l
0
e th y l
e th y l
62
n -p ro p y l
n -p ro p y l
71
R
R a n d R 1 = -(C H 2) 5 -
100
“ 14a n d p o t a s s i u m t - b u t o x i d e f o llo w e d b y h y d r o l y s i s i n n e u t r a l a q u e o u s s o l u ­
tio n .
T h e rm a l d e c o m p o s itio n o f d i p h e n y l e y e lo p ro p e n o n e a t 130-40°Go
c a u s e s e v o l u t i o n o f c a r b o n m o n o x id e a n d d i p h e n y l a c e t y l e n e .
The r e l a t i v e ­
l y h i g h t e m p e r a t u r e a t w h ic h d e c o m p o s itio ri o c c u r s a n d t h e f a c t t h a t d i ­
p h e n y l e y e lo p r o p e n o n e c a n a l s o b e i s o l a t e d fro m h y d r o x y li c m edium , show
t h a t t h e c y c lo p r o p e n o n e s y s te m m u s t h a v e s t r o n g r e s o n a n c e s t a b i l i z a t i o n
i n d e e d t o c o m p e n s a te f o r i t s h i g h a n g le s t r a i n .
S e v e r a l o t h e r r e a c t i o n s w h ic h m ig h t h a v e some b e a r i n g on t h e s y n ­
t h e s i s o f e y e lo p ro p a n o n e h a v e b e e n r e p o r t e d .
I n t h e c o u r s e o f s t u d i e s on t h e f o r m a ti o n o f d i e h l o r o c a r b e n e a s a n
i n t e r m e d i a t e i n t h e a l k a l i n e ' h y d r o l y s i s o f c h lo r o f o r m . D o e rin g a n d :. .
H offm ann (1 4 ) t r e a t e d c h lo r o f o r m w i t h c y c lo h e x e n e i n t h e p r e s e n c e o f
p o t a s s i u m t - b u t o x i d e a n d o b t a i n e d 7 , 7 - d i c h l o r o b i c y c l o ( 4 . 1 , 0 ) h e p ta n e .
O th e r o l e f i n s w e re f o u n d b y t h e s e w o r k e rs t o r e a c t s i m i l a r l y w i t h c h l o r o ­
fo rm a n d b ro m o fo rm i n t h e p r e s e n c e o f s t r o n g b a s e s t o g i v e g e m - d ih a lo c y c lo p r o p a n e a n d f u r t h e r e x a m p le s o f t h i s r e a c t i o n h a v e b e e n r e p o r t e d by P arham
( 1 5 a , b , c,)*.. S ke 11 ( 1 6 a , b , , c ) , a n d t h e i r c o - w o r k e r s .
D a le a n d S w a r t z e n t r u b e r (1 7 ) t r i e d
t o h y d r o ly z e 2 , 2 - d i c h l o r o c y c l o -
p r o p y l b e n z e n e i n w a t e r i n a s e a l e d p y r e x tu b e h e a te d t o 2 0 0 -5 °C ,
b l a c k p o ly m e r ic m a t e r i a l was o b t a i n e d .
O nly a
U n d er l e s s d r a s t i c c o n d i t i o n s o n ly
t h e s t a r t i n g m a t e r i a l was o b s e r v e d ,
M c E lv a in a n d Weyna (1 8 ) h a v e d e s c r i b e d t h e r e a c t i o n o f k e te n e
a c e t a l s w i t h d i e h l o r o c a r b e n e t o fo rm 2 , 2 - d ic h l o r o c y c lo p r o p a n o n e a c e t a l s .
T h e s e p r o d u c t s c a n b e i s o l a t e d o n ly b y d i s t i l l a t i o n u n d e r low p r e s s u r e a s
-1 5 t h e y u n d e rg o p y r o l y s i s a b o v e IOO0C. Co a - c h l o r o a c r y l i c e s t e r s and an a l k y l
c h lo rid e .
A l l t h e p r o c e d u r e s w h ic h h a v e b e e n a tt e m p t e d ( I )
(2 )
p r e p a r a t i o n o f e y e lo p ro p a n o n e i n v o lv e d a q u e o u s s o l u t i o n s .
e y e lo p ro p a n o n e may e x i s t ,
(3 ) f o r th e
Even th o u g h
i t w o u ld b e e x p e c te d t h a t i t s h y d r a t e d form
w o u ld b e i s o l a t e d fro m t h e s e s o l u t i o n s b e c a u s e i n e y e lo p r o p a n o n e th e u s u a l
e q u i l i b r i u m b e tw e e n a k e to n e a n d i t s h y d r a t e s h o u ld be s t r o n g l y s h i f t e d t o
th e r i g h t as a r e s u l t o f th e I - s t r a i n e f f e c t (1 9 ).
Z
\
OH
OH
T h e r e f o r e , i t w o u ld seem w is e t o u s e n o n -a q u e o u s s o l v e n t s o r no s o l v e n t a t
a ll,
i n o r d e r t o a v o id t h e p o s s i b i l i t y o f h y d r a t i n g an y e y e lo p r o p a n o n e
t h a t m ig h t b e fo rm e d .
The p r o p o s i t i o n t h a t a n o n -a q u e o u s r e a c t i o n s e q u e n c e f o r t h e s y n ­
t h e s i s o f c y c lo p r o p a n o n e m ig h t be s u c c e s s f u l c a n b e e x te n d e d t o s im p le
s u b s t i t u t e d e y e lo p ro p a n o n e s w h ic h a r e n o t s t a b i l i z e d by r e s o n a n c e o r t h e
p r e s e n c e o f g e m in a l o r l a r g e g ro u p s on t h e th re e -m e m b e re d r i n g .
The r e ­
a c t i o n sch em es shown b e lo w w e re c h o s e n i n t h e ho p e o f o b t a i n i n g p r o d u c ts
w h ic h w o u ld b e o f i n t e r e s t f o r f u r t h e r s t u d i e s .
-1 6 SCHEME I
COOC0H:
Cu
+
o
N2CHCOOC2H5
n -h e p ta n e
OH**
H
COOH
HVZ r e a c t i o n
B r 2 , CCl 4 & P
KOH, S team
Na2CO0 o r
'r
Na0 i n l i q u i d NH0
J
OH
NH
Il
D ry HCl
i n C6H6
COOH
Il
/X
X
0
C one.
/
T*
H
X Z
17SCHEME I I
Cl
Cl
CH3COOK,
CH3COOH, 5«
Ac 0 (2 0 )
H3CCOO^ y D O C C H 3
0
+
Ac„0
"18=
EXPERIMENTAL
P r e p a r a t i o n o f e t h y l b i c y c l o ( 3 « 1 . 0 ) h e x a n e - 6 " c a r b o 3e y l a t e ,
C y c lo p e n te n e p r e p a r e d by d e h y d r a t i o n o f e y e l o p e n t a n o I i n t h e p r e ­
s e n c e o f 85% p h o s p h o r i c a c i d ( 2 1 ) , a n d t h e n p u r i f i e d t h r o u g h a Todd P r e ­
c i s e F r a c t i o n a t i o n A s s e m b ly , was c o l l e c t e d a t 3 9 -4 0 ° a t 641 mm.
A m i x t u r e o f e y e l o p e n t e n e ( 7 6 .4 g . , 1 .1 2 m o l e s ) , n - h e p t a n e (180 m l.)
a n d c o p p e r pow der c a t a l y s t ( 3 .0 g . ) w as h e a t e d a t 5 3 - 8 ° .
E th y l d ia s o -
a c e t a t e (1 2 8 g . , 1.12 m o le s ) w h ic h was p r e p a r e d from m e th y le n e a m in o a e e to n itrile
(2 2 )
(2 3 ) was a d d e d o v e r a p e r i o d o f 4 h o u r s w i t h r a p i d s t i r r i n g .
The m ix t u r e was c o o le d t o room t e m p e r a t u r e a n d t h e c a t a l y s t was rem oved
by f i l t r a t i o n .
The f i l t r a t e was w ash ed t w i c e w i t h 20 m l. p o r t i o n s o f 10%
s u l f u r i c a c i d , o n e 100 m l. p o r t i o n o f w a t e r , o n e 50 m l. p o r t i o n o f s a t ­
u r a t e d so d iu m b i c a r b o n a t e a n d f i n a l l y w i t h s a t u r a t e d so d iu m c h l o r i d e and
d r i e d o v e r so d iu m s u l f a t e .
r e s i d u e was d i s t i l l e d
The s o l v e n t was rem oved i n v a c u o , a n d t h e
th r o u g h a 6 " m i c r p f r a c t i o n a t i n g co lu m n p a c k e d w ith
s t a i n l e s s s t e e l h e l i c e s g i v i n g a m a in f r a c t i o n b o i l i n g a t 5 mm. : y i e l d
5 3 .3 g . (3 0 .8 % ).
P r e p a r a tio n o f b ic y c lo (3 .1 .0 ) h e x a n e - 6 -c a r b o x y lic a c id .
A m i x t u r e o f 25 g .
( 0 .1 6 2 m o le s ) o f e t h y l b i c y c I o ( 3 . I . 0 ) h e x a n e - 6 -
c a r b o x y l a t e a n d 250 m l. o f 2 Ne p o t a s s i u m h y d r o x id e was r e f l u x e d f o r 3
h o u rs.
The s o l u t i o n was f i l t e r e d ;
t h e f i l t r a t e was n e u t r a l i z e d w i t h 50%
s u l f u r i c a c id and r e p e a te d ly e x tr a c t e d w ith e t h e r .
The c o m b in e d e x t r a c t s
w e re e v a p o r a te d t o d r y n e s s a n d t h e r e s i d u e , r e c r y s t a l l i z e d fro m a l c o h o l
a s p r i s m s , m e l te d a t 6 1 .6 - 6 2 .6 ° C .
(c o rre c te d )
; y i e l d 15 g . (7 3 .4 % ).
-1 9 A n a l y s is : .
C a l c u l a t e d f o r CyH^QO2
:
N e u t r a l i z a t i o n E q u i v a l e n t 1 2 6 .1 6
F ound:
1 2 6 .0 4
P r e p a r a t i o n o f b i c y c l o Q . 1 . 0 ) h e x a n e - 6,- c a r b o n y l b ro m id e ;
Two gram s ( 0 .0 1 5 8 m o le ) o f b i c y c l o ( 3 . 1 . 0 ) h e x a n e - 6 - c a r b o x y l i c a c i d
was d i s s o l v e d i n 10 m l. o f c a r b o n t e t r a c h l o r i d e an d 0 .2 g . o f a n h y d ro u s
r e d p h o s p h o ru s w h ic h was f i r s t w ashed f r e e o f a l l a c i d an d c a r e f u l l y d r i e d
was a d d e d .
The m i x t u r e was h e a t e d t o b o i l i n g an d a f t e r t h e a d d i t i o n o f
1
2 .9 g . ( 0 .0 1 8 m ole), o f b ro m in e was r e f l u x e d f o r 1 5 m in u te s $ vacuum d i s t i l ­
l a t i o n , g a v e a m a in f r a c t i o n w h ic h b o i l e d a t 4 7 ° a t 1 .0 mm.
A n a ly s is :
C a l c u l a t e d f o r C^HgBrO
:
F ound;
B r , 42.26%
43.02%
P r e p a r a t i o n o f b i c y c l o ( 3 .1 .0 ) h e x a n e - 6 - c a r b o x a m i d e :
Two gram s o f b i c y c l o ( 3 . 1 . 0 ) h e x a n e - 6 - c a r b o n y l b ro m id e was a d d ed d ro p
w is e t o a n e x c e s s i c e - c o l d c o n c e n t r a t e d a q u e o u s ammonia s o l u t i o n w ith
v ig o ro u s a g i t a t i o n .
The p r e c i p i t a t e , a f t e r f i l t r a t i o n , w a s h in g w i t h w a t e r
a n d r e c r y s t a l l i z a t i o n fro m a l c o h o l a s n e e d l e s , m e lte d a t 1 9 3 -9 4 °C , ( u n c o r ­
re c te d ) .
A n a ly s is :
C a l c u l a t e d f o r CyH^NO
Found:
:
N, 11.19%
10.73%
P r e p a r a tio n o f 6 , 6 - d ic h lo r o b ic y c lo ( 3 .1 .0 ) h ex an e.
One h u n d re d a n d t h i r t y - s i x gram s (2 m o le s ) o f p u r i f i e d e y e lo p e n te n e
510 m l. o f n - p e n ta n e . a n d 2 8 4 .5 g . ( 2 .5 4 m o le s ) o f p o t a s s i u m t - b u t o x i d e
( 10% e x c e s s ) w e re a d d e d t o a 2 l i t e r 3 - n e c k e d f l a s k w h ic h was e q u ip p e d
w i t h m e rc u ry s e a l e d s t i r r e r , c o n d e n s e r a n d d r o p p in g f u n n e l .
The e n t i r e
*-20"
a p p a r a t u s was p l a c e d i n a n i c e - b a t h .
p a r e d fro m 9 0 .0 g .
The p o ta s s iu m t- b u to s e id e was p r e ­
( 2 .3 0 m o le s ) o f m e t a l l i c p o ta s s iu m by a d d in g e x c e s s o f
t - b u t y l a lc o h o l, and d i s t i l l i n g o f f th e e x c e s s a ld o h o l.
i n e v a c u a t e d o v e n a t 9 5 °C . f o r 16 h o u r s .
a n d s t i r r e d t h r o u g h o u t t h e w h o le r e a c t i o n .
I t was t h e n d r i e d
The s u s p e n s i o n was c o o le d t o 0 °C .
Two h u n d re d t h i r t y - e i g h t and
e i g h t - t e n t h s g ram s (2 m o le s ) o f c h lo r o f o r m w e re a d d e d d r o p w is e a t s u c h a
\
•
r a t e t h a t t h e t e m p e r a t u r e r e m a in e d b e tw e e n . 0 a n d 5°C .
F o llo w in g t h e a d d i ­
t i o n o f th e c h lo r o f o r m (w h ic h r e q u i r e d 4 h o u r s ) , t h e m ix t u r e was s t i r r e d
f o r an a d d it io n a l h o u r, and th e n p o u red i n to i c e w a te r.
T he 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 t h e a q u e o u s l a y e r was e x t r a c t e d w i t h tw o 250 m l. p o r t i o n s
o f n - p e n t a n e w h ic h w e re co m b in ed w i t h t h e o r g a n i c l a y e r , a f t e r d r y in g w i t h
a n h y d ro u s c a lc iu m c h l o r i d e , t h e s o l v e n t was e v a p o r a te d a n d t h e r e s i d u e d i s ­
tille d
in vacuo.
A a jia in f r a c t i o n (1 0 2 g . , 3 3 .8 % ), b . p . 5 7 -8 ° C . a t 13 mm.
p r e s s u r e was o b t a i n e d t h r o u g h t h e Todd P r e c i s e F r a c t i o n a t i o n A ssem bly a t
th e r e f lu x r a t i o o f 5 0 :I .
d|5
- 1 .1 6 0 5
A n a ly s is :
1
= 1 .4 9 4 2
C a l c u l a t e d f o r CgHgGlg
Found:
:
C l , 46,96%
47.17%
Exami n a t i o n o f t h i s m a t e r i a l b y v a p o r p h a s e c h ro m a to g ra p h y show ed
o n l y 6 , 6 - d i c h l o r o b i c y c l o ( 3 . 1 . 0 ) h e x a n e a n d I , 6 - d ic h l o r o e y c l o h e x e n e i n t h e
r a t i o 9 2 .3 : 7 . 7 .
The m a jo r co m ponent w as i s o l a t e d by v a p o r p h a s e chrom a­
t o g r a p h y a n d was show n by i n f r a r e d a n a l y s i s t o b e pure* S '^ - d i c h l o r o b i c y c l o ( 3 ,1 .0 ) hexane.
w e re em p lo y e d ;
I n t h e v a p o r p h a s e c h ro m a to g ra p h y a n a l y s e s , tw o colum ns
(I)
5 f t . x 0 .2 5 i n . Ucdn P o l a r colum n o p e r a t e d a t 96°C .
I
"<21>
w i t h h e liu m f lo w r a t e 9 ,5 c m ? , / s e c , , a n d (2 ) 5 f t , x 0 ,5 i n , C r a ig colum n
o p e r a t e d a t 114°C , w i t h h e liu m f lo w r a t e 8 ,5 cm-*, / s e c .
T he i n f r a r e d s p e c tr u m o f 6 , 6 - d i c h l o r o b i c y c l o ( 3 , I . 0 ) h e x a n e showed t h e
u s u a l c y c lo p r o p a n e a b s o r p t i o n a t 3 . 3 5 ^ ( 3 0 7 0 cm“ ^ . ) a n d 9 .8 X ^ ( 1 0 2 0 c m " * .) .
P r e p a r a t i o n o f 1 ,6 - d i c h l o r o - l ^ c y c l o h e x e n e .
(a)
F i f t y g ram s o f . 6 , 6 - d i c h l o r o b i c y c I o ( 3 , 1 , 0 ) h e x a n e w e re r e f l u x e d
a t 150°C . f o r o n e h o u r , a n d t h e n d i s t i l l e d
th r o u g h t h e Todd P r e c i s e F r a c -
t i o n a t i o n A ssem b ly g i v i n g a m a in f r a c t i o n b o i l i n g a t BS-A 0C. a t 15 mm, 5
y i e l d 4 7 .5 g , (95% ).
(c )
An a u t h e n t i c compound w as p r e p a r e d fro m c y c lo h e x a n o n e by
c h l o r i n a t i o n (2 4 ) a n d s u b s e q u e n t r e a c t i o n w i t h p h o s p h o ro u s p e n t a c h l o r i d e
a t O0Ce
e th e r.
The r e a c t i o n m i x t u r e was p o u r e d i n t o i c e - w a t e r a n d e x t r a c t e d w i t h
The s o l v e n t was e v a p o r a te d i n v a c u o a n d a m a in f r a c t i o n t h a t h a d
a b o i l i n g p o i n t o f 8 2 - 4 ° a t 15 mm. was o b t a i n e d .
T he a u t h e n t i c com pound was s e p a r a t e d by v a p o r p h a s e c h ro m a to g ra p h y
i n o r d e r to o b ta in a .p u r e p r o d u c t, and th e n ch eck ed w ith i n f r a r e d a n a ly ­
s is ,
t h e s p e c tr u m was s u p W im p o s a b le . w i t h t h e 1 , 6- d i c h l o r o - l - c y c l o h e x e n e
(2 5 ) p r i m a r i l y o b t a i n e d .
A n a ly s is :
T he r e s u l t s a r e p r e s e n t e d i n f i g u r e s 5 a n d 6,
C a l c u l a t e d f o r CgHgClg
Found:
:
C l , 46,96%
46,33%
P r e p a r a t i o n o f l - c h l o r o - 6 - a c e t o x y - l - c y c l o h e x e n e fro m 6 , 6 - d i c h l o r o b i c y c l o ( 3 ,1 ,0 ) hexane.
•
■
T h i r t y - e i g h t a n d o n e - h a l f gram s ( 0 ,2 5 5 m o le) o f 6 , 6 - d i c h l o r o b i e y c l o ( 3 , . 1 . 0 ) h e x a n e , 50 g , ( 0 .5 1 m o le ) o f a n h y d ro u s p o t a s s i u m a c e t a t e , 77 m l.
-2 2 o f g l a c i a l a c e t i c a c i d a n d 3 8 ,5 m l, o f a c e t i c a n h y d ti d e w e re r e f l u x e d a t
9 2 “ 5°G , f o r 72 h o u r s , a n d p o u r e d i n t o i c e - w a t e r .
The o r g a n i c l a y e r s was
s e p a r a t e d , t h e a q u e o u s l a y e r was e x t r a c t e d w i t h two 30 m l, p o r t i o n s o f
benzene,
, The c o m b in e d o r g a n i c s o l u t i o n s , w e re d i s t i l l e d u n t i l t h e b e n z e n e
was g o n e , a n d t h e r e s i d u e d i s t i l l e d i n v a c u o th r o u g h a Todd P r e c i s e F r a c ­
t i o n a t i o n A sse m b ly ,
A m a in f r a c t i o n , b . p , 8 3 -4 ° C , a t 5 mm,, was o b t a i n e d ;
y i e l d 3 0 . 7 g . (69% ).
M o u sse ro n e t a l (2 6 ) r e p o r t t h e f o ll o w i n g c o n s t a n t s , f o r t h i s com­
pound:
.
b .p .
A n a ly s is :
1 0 7 -8 °C . a t 15 mm. ; D |g = 1 ,1 6 8
C a l c u l a t e d f o r OgH^^ClOg
F ound:
:
;
^
= 1 .4 8 0 5
C l , 20,31%
20.3X7,
D e t a i l e d v a p o r p h a s e c h ro m a to g ra p h y s t u d i e s , s i m i l a r t o t h o s e men­
t i o n e d on p a g e 20. show ed t h a t t h e p r o d u c t was c o n ta m in a te d by 0 . 1% o f
6 , 6 - d ic h lo ro b ic y c lo (3 .1 .0 ) hexane.
P r e p a r a t i o n o f l - c h l o r o - 6 - a c e t o x y - l - c y e l o h e x e n e fro m 1 , 6 - d i c h l o r o - l - e y e l o ,h e x e n e .
The p r o c e d u r e d e s c r i b e d i n t h e p r e c e d in g s e c t i o n was f o llo w e d u s i n g
3 8 .5 g . ( 0 .2 5 5 m o le ) o f I , 6 - d i c h l o r o - 1 - c y c l o h e x e n e , 77 m l. o f g l a c i a l
a c e t i c a c i d an d 5 0 .0 g .
( 0 .5 1 m o le ) o f a n h y d ro u s p o ta s s iu m a c e t a t e .
f l u x t e m p e r a t u r e was 1 3 0 -3 2 °C .
Re­
The p r o d u c t b o i l e d a t 8 3 -4 ° C . a t 5 mm.,
a n d was show n b y i n f r a r e d a n a l y s i s a n d v a p o r p h a s e c h ro m a to g ra p h y t o b e
t h e sam e a s t h e o n e m e n tio n e d a b o v e .
P re p a ra tio n o f b ic y c lo ( 3 .1 .0 ) h exane.
The m eth o d d e s c r i b e d b y D o e r in g a n d H offm ann' (1 4 ). f o r .t h e r e d u c t i o n
-2 3 o£ 7 > 7 -d ib r o m o b ic y c I o ( 4 . 1 « 0 )h e p ta n e was e m p lo y e d .
F o llo w in g t h e c o m p le te
r e a c t i o n o f t h e so d iu m m e t a l (3 1 g , 3 2 ,0 g . a to m s) w i t h w e t m e th a n o l
(1 0 m l, o f w a t e r t o 300 m l, o f m e t h a n o l) , a n d 30 m l. o f e t h e r a s s o l v e n t ,
100 m l. o f w a t e r was a d d e d , t h e e t h e r l a y e r was s e p a r a t e d , a n d t h e a q u e o u s
l a y e r was e x t r a c t e d tw i c e w i t h 20 m l. p o r t i o n s o f e t h e r .
From 1 0 .2 g .
( 0 .0 6 7 5 m o le ) o f 6 , 6 - d i c h l o r o b i c y c l o ( 3 . 1 . 0 ) h e x a n e t h e y i e l d was 2 .8 5 g .
(51.7% ) o f b i c y c l o ( 3 . 1 . 0 ) h e x a n e a s a c o l o r l e s s l i q u i d , b . p . 74 0C , (6 4 1 m m .).
An i n f r a r e d a n a l y s i s show ed t h e u s u a l c y c lo p r o p a n e a b s o r p t i o n a t
3 . 3 5 / ^ ( 3 0 8 4 cm "^) a n d 9 . 7 7 / ^ ( 1 0 2 4 c m "!) a n d show ed no a b s o r p t i o n f o r u n ­
s a t u r a t i o n w h ic h w o u ld h a v e a p p e a r e d a t 6 - 6 . 5 ( 1 6 6 8 - 1 5 4 8 cm "^ ) .
V a p o r p h a s e c h ro m a to g ra p h y p r o v e d t h e h o m o g e n e ity o f t h e p r o d u c t .
T he r e d u c t i o n o f 1 , 6 - d i c h l o r o - l - c y c l o h e x e n e w i t h so d iu m a n d m e th a n o l.
I , 6 - D i c h l o r o - 1 - c y c l o h e x e n e ( 1 0 .2 g . , 0 ,0 6 7 5 m o le ) w as r e d u c e d w i t h
31 g . ( 2 .0 g . a to m s) o f so d iu m a n d 200 m l. o f w e t m e th a n o l i n t h e ab o v e
m a n n e r.
The p r o d u c t o b t a i n e d ( 3 , g . , 54,5% ) was i d e n t i f i e d w i t h known
c y c lo h e x a n e b y b o t h i n f r a r e d a n d v a p o r p h a s e c h ro m a to g ra p h y a n a l y s e s .
P r e p a r a t i o n o f l - c h l o r o - 6- h y d r o x y - l - e y c l o h e x e n e .
A s o l u t i o n o f 35 g .
( 0 .6 2 4 m o le ) o f p o ta s s iu m h y d r o x id e a n d 10 g .
( 0 .0 7 5 5 m o le ) o f l - c h l o r o - 6 - a c e t o x y - l - c y c l o h e x e n e i n 200 m l. o f 90% e t h y l
" a lc o h o l was r e f l u x e d f o r 3 h o u r s .
The s o l u t i o n was f i l t e r e d a n d t h e f i l ­
t r a t e was n e u t r a l i z e d w i t h 50% s u l f u r i c a c i d a n d t h e n r e f i l t e r e d .
T h is
f i l t r a t e was d i l u t e d w i t h 100 m l. o f w a t e r a n d e x t r a c t e d t w ic e w i t h b e n ­
zene.
The e x t r a c t s w e re d i s t i l l e d u n t i l t h e b e n z e n e was rem o v ed and t h e
r e s i d u e was d i s t i l l e d i n v a c u o .
A m ain f r a c t i o n , b . p . 8 6 -7 ° C . a t 15 mm..
=24”
was o b t a i n e d ; y i e l d 4 .7 4 g ,
(6 2 .5 % ).
M o u sse ro n e t a l (2 6 ) r e p o r t t h e f o l l o w i n g c o n s t a n t s :
b . p . 86= 7°C . a t 15 mm.
A n a ly s is :
C a l c u l a t e d f o r C^HgClO
;
= 1 .1 8 4
:
Found:
?
^ p5
1 .5 0 6 6
C l , 26.74%
26.49%
P o ta s s iu m d ic h r o m a te ( 1 .4 8 g . , 0 .0 0 5 0 'm o le ) was d i s s o l v e d i n 20 m l.
o f w a t e r a n d 4 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 was a d d e d .
The m ix tu r e
was a d d e d d r o p w is e t o 2 g . ( 0 .0 1 5 1 m o le ) o f l - c h l o r o - d - h y d r o x y - I a C yclo=
h e x e n e , k e e p in g t h e t e m p e r a t u r e b e tw e e n 25 a n d 30°C .
F o l lo w in g a d d i t i o n
o f t h e p o t a s s i u m d ic h r o m a te t h e r e a c t i o n m ix t u r e was h e a t e d i n a b e a k e r
o f w a t e r a t 60°C . f o r 20 m i n u t e s .
F i f t y m i l l i l i t e r s o f w a t e r was th e n
a d d e d a n d t h e s o l u t i o n c o o le d i n a c o o l i n g b a t h f o r 2 h o u r s .
A f t e r th e
p r e c i p i t a t e h a d b e e n s e p a r a t e d b y s u c t i o n , i t was w ash ed w i t h i c e - w a t e r
and d r ie d i n d e s ic c a t o r .
A f t e r r e c r y s t a l l i g a t i o n fro m a l c o h o l i t h a d a
m .p .o f 7 5 ,6 = 7 6 .4 ( c o r r e c t e d ) ; y i e l d 1 . 2 g . (61% ).
M o u sse ro n e t a I (2 7 )
r e p o r t a m .p . o f 70°C .
A n a ly s is :
C a l c u l a t e d f o r CgH^GlO
Found:
:
C l , 27,157.
27.11%
S e m ic a rb a z o n e ( r e c r y s t a l l i z e d fro m a l c o h o l ) m e l te d a t 195a97°C ,
r e p o r t e d a t 195=98°C . by M o u sse ro n e t a l ( 2 7 ) .
The m eth o d d e s c r i b e d b y C r o s s le y a n d H aas (2 8 ) w as em p lo y ed w i t h
-
25 -
o n l y a s l i g h t m o d i f i c a t i o n a s f o ll o w s :
Two gram s o f l - c h l o r o - 6 - h y d r o x y - 1 - c y c lo h e x e n e w e re s u s p e n d e d i n
30 m lo o f w a t e r find a c o l d , s a t u r a t e d s o l u t i o n o f p o ta s s iu m p e rm a n g a n a te
a d d e d u n t i l t h e c o l o r o f l a t t e r r e m a in e d p e rm a n e n t.
A fte r f i l t e r i n g
th e
s e p a r a t e d m an g a n e se d i o x i d e , a s m a ll am ount o f so d iu m b i s u l f i t e was a d d e d
i n o r d e r t o d e s t r o y t h e e x c e s s p e rm a n g a n a te a n d t h e l i q u i d was e v a p o r a te d
t o a v e r y s m a l l v o lu m e , a c i d i f i e d w i t h s u l f u r i c a c i d a n d r e p e a t e d l y e x ­
t r a c te d w ith e th e r .
A f t e r r e c r y s t a l l i z a t i o n fro m c h lo r o f o r m , t h e m .p , o f
t h e p r o d u c t was 9 6 , 5 - 7 . 3 ^ 0 . ; y i e l d 0 .5 g .
T h is m .p , w as i n d i c a t i v e o f
g l u t a r i c a c i d w h ic h was t h e p r o d u c t e x p e c t e d fro m t h i s r e a c t i o n .
T h is s u b s t a n c e was f u r t h e r i d e n t i f i e d a s g l u t a r i c ■a c i d , by &
m ix e d m .p . d e t e r m i n a t i o n w i t h known g l u t a r i c a c i d .
No m e l t i n g p o i n t d e ­
p r e s s i o n was o b s e r v e d .
The r e a c t i o n o f l - e h l o r o - 6 - h y d r o x y - l - c y e l o h e x e n e w i t h t h i o n y l c h l o r i d e .
A s o l u t i o n o f 1 .2 g . ( 0 .0 0 9 0 5 m o le ) o f l - c h l o r o - 6 - h y d r o x y l - l ? e y c l o h e x e n e a n d 1 .6 g . ( 0 .0 1 3 4 m o le ) o f t h i o n y l c h l o r i d e was r e f l u x e d on t h e
s t e a m - b a t h u n t i l h y d ro g e n c h l o r i d e g a s e v o l u t i o n h ad c e a s e d ( a b o u t 2
h o u rs).
T he e x c e s s t h i o n y l c h l o r i d e was rem oved u n d e r vacuum l e a v i n g a
, p r o d u p t w h ic h b o i l e d a t 6 8 -9 ° C . a t 7 .5 mm.
T h is m a t e r i a l was show n by i n f r a r e d a n d v a p o r p h a s e c h ro m a to g ra p h y
a n a l y s e s t o b e I , 6- d i c h l o r o - l - c y c l o h e x e n e .
j
D e h y d r o g e n a tio n o f l - c h l o r o - 6 - a g e t o x v - l - c y c lo h e x e n e i n t h e p r e s e n c e o f
s u lf u r o r c h lo ra n iI.
■------ 'r .......—----------'
T he m eth o d ^ d e s c r i b e d by C o c k e r (2 9 ) a n d A r n o ld (3 0 ) w e re f o llo w e d :
"26"
(a)
A s o lu tio n o f S g .
( 0 .0 2 8 6 m o le ) o f l " C h l o r o - 6 - a c e to % y " l-
c y c lo h e x e n e a n d 1 .8 4 g . ( 0 .0 5 7 2 m o le ) o f s u l f u r was r e f l u x e d a t 220*=40°C .
f o r 24 h o u r s .
The p r o d u c t was t h e n d i s t i l l e d .
A b o u t 70% o f u n r e a c t e d
m a t e r i a l was r e c o v e r e d , a n d a s m a ll am ount o f low b o i l i n g m a t e r i a l w h ic h
was n o t i n v e s t i g a t e d was a l s o o b t a i n e d .
(b )
A s o l u t i o n o f 5 g . ( 0 .0 2 8 6 m o le ) o f l - c h l o r o - b - a c e t o x y - l "
c y c lo h e x e n e a n d 1 3 .7 6 g . ( 0 . 1 2 6 , m o le ) o f c h l o r a n i l i n 30 m l. o f x y le n e
w as r e f l u x e d f o r 14 h o u r s , c o o l e d , a n d f i l t e r e d .
The f i l t r a t e was d i -
lultieid w i t h ,a h 'e q u a l q u a n t i t y o f e t h e r , w ash ed w i t h d i l u t e d s f l k a l i , d r i e d
o v e r so d iu m s u l f a t e a n d f r a c t i o n a t e d .
No 2 - c h l o r o - l - p h e n o x y a c e t a t e , . t h e e x p e c t e d p r o d u c t , c o u ld be
is o la te d .
27
WAVELENGTH
4COO
F ig u re I ,
3500
WAVENUMBER
F ig u re 2 .
IN KAYSERS
B i c y c l o ( 3 . 1 .0 ) h e x a n e - 6 - c a r b o x y l i c a c i d (5% w/w i n C C l^)
WAVELENGTH
5000
MICRONS
WAVENUMBER
IN MICRON
IN KAYSERS
B i c y c l o ( 3 . 1 . 0 ) h e x a n e - 6 -*carboxam ide ( N u jo l m u ll)
28
F ig u re
F ig u re 4 .
6,6-Dichlorobicyclo(3.1.0)h e x a n e (capillary film)
B i c y c l o ( 3 . I . 0 ) h e x a n e (20% v / v i n CCl^)
29
WAVELENGTH
—
70-
Figure 5 .
1,6-Dichloro-l-cyclohexene (20% v / v in CSg)
F ig u r e 6.
A u t h e n ti c compound o f I . 6 - d i c h l o r o - l - c y c l o h e x e n e
( 20% v / v i n CS 2 )
**30“
DISCUSSION
A lth o u g h n e i t h e r o f t h e r e a c t i o n sch em es o u t l i n e d i n t h e i n t r o d u c ­
t i o n f o r t h e s y n t h e s i z i n g o f b i c y c l o ( 3 .1 .0 ) h e x a n - 6 - o n e w as r e a l i z e d a num­
b e r o f i n t e r e s t i n g p o i n t s d e v e lo p e d i n t h e c o u r s e o f t h e i n v e s t i g a t i o n .
R e a c ti o n s e q u e n c e I w as c a r r i e d a s f a r a s b i c y c l o ( 3 . 1 . 0 ) h e x a n e - 6 c a r b o x y l i c a c i d , b u t t h e i n t r o d u c t i o n o f b ro m in e i n t o phe a c i d by t h e w e l l know n H e l l - V o l h a r d - Z e l i n s k y r e a c t i o n f a i l e d .
The H e l l - V o l h a r d - Z e l i n s k y r e a c t i o n n o r m a lly s u b s t i t u t e s b ro m in e on
t h e o r-c a rb o n .
R e p e a te d a t t e m p t s u n d e r m o st o f t h e known c o n d i t i o n s g a v e
o n ly s t a r t i n g m a t e r i a l.
E ven r e a c t i o n o f b ro m in e w i t h t h e a c i d c h l o r i d e ,
w h ic h i s p re su m e d t o b e a n i n t e r m e d i a t e i n t h e H e l l- V o l h a r d - Z e li n s k y r e ­
a c tio n , gave n e g a tiv e r e s u l t s .
The b ro m in e m o le c u le i n H e l l- V o l h a r d - Z e li n s k y r e a c t i o n a c t s a s a n
e le c tr o p h i li c re a g e n t.
I.
3 roh 2cgoh
2,
RCH2COBr
3.
RCHBrCOBr
The p r o p o s e d m ec h a n ism i s :
+
PB r 3 —» SRCHaCOBr
Br +B r " > RCHBrCOBr
+
+
RCH2COOH
(3 1 )
P(OH) 3
+
+
RCHBrCOOH
HBr
+
RCH2COBr
The c y c lo p r o p a n e r i n g h a s b e e n c l a s s i f i e d a s a n u c l e o p h i l i c g ro u p .
b e c a u s e t h e c a r b o n - c a r b o n b o n d s o f t h e c y c lo p r o p a n e r i n g a r e a b n o rm a lly
w eak a n d c y c lo p r o p a n e d e r i v a t i v e s m ig h t b e e x p e c te d t o b e r e a d i l y a t t a c k e d
by e l e c t r o p h i l i c r e a g e n ts .
H ow ever, t h e e l e c t r o n e g a t i v e g ro u p w h ic h i s
d i r e c t l y a t t a c h e d t o c y c lo p r o p a n e r i n g w o u ld d i m i n is h t h e a d d i t i v e a c t i v ­
i t y o f c y c lo p r o p a n e to w a rd b ro jn in e th r o u g h e x e r c i s e o f i n d u e to m e r ic o r
m e so m e ric e l e c t r o n a t t r a c t i o n ,away fro m t h e n u c l e o p h i l i c c e n t e r ( 3 2 ) .
-3 1 K osow er (3 3 ) h a s d e m o n s tr a te d e l e c t r o n d e l o c a l i z a t i o n i n a l k y l p r o p y l k e ­
to n e s :
A s i m i l a r d e l o c a l i z a t i o n c o u ld o c c u r i n b i c y c l o ( 3 . 1 . 0 ) h e x a n e - 6 - c a r b o x y l i c
T h is may b e t h e r e a s o n why t h e H e l l - V o l h a r d - Z e l i n s k y r e a c t i o n was
u n s u c c e s s fu l.
S k e l l a n d G a rn e r (1 6 b ) h a v e p r e p a r e d 6 ,6 - d i b r o m o b i c y c l o ( 3 .1 . 0 ) h e x a n e , b u t r e p o r t e d no c h e m ic a l p r o p e r t i e s .
R e a c ti o n s e q u e n c e I I was c a r r i e d a s f a r a s 6 , 6 - d i c h l o r o b i c y c l o ( 3 . 1 . 0 ) -h ex a n e (3 4 ).
6 , 6 - D i c h l o r o b i c y c I o ( 3 . I . 0 ) h e x a n e was fo u n d to b e i n ­
e r t t o b ro m in e i n c a r b o n t e t r a c h l o r i d e , b u t r e a c t e d r e a d i l y w i t h p o ta s s iu m
p e rm a n g a n a te s o l u t i o n .
The compound show ed no a b s o r p t i o n a t 6 - 6 .5 / 0 (1 6 6 8 -
1548 cm "^) w h ic h i s c o n s i s t e n t w i t h t h e a b s e n c e o f a d o u b le b o n d .
c h l o r i d e was r e m a r k a b ly a c t i v e i n d is p l a c e m e n t r e a c t i o n s .
The
T h e re was p r e ­
c i p i t a t i o n w i t h a l c o h o l i c s i l v e r n i t r a t e w i t h i n 3 m in u te s a t room tem p­
e ra tu re .
The r e a c t i o n o f t h e c h l o r i d e w i t h p o ta s s iu m a c e t a t e i n a c e t i c
a n h y d r i d e g a v e o n ly t h e r e a r r a n g e m e n t p r o d u c t , l - c h l c r o - 6 - a c e t o x y - l - c y c l o hexene.
The s t r u c t u r e o f t h i s compound was d e m o n s tr a te d by a s e r i e s o f
32r e a c t i o n s a s f o ll o w s :
Cl
Cl
Cl
Z
I
CH3COOK
i n Ac 2©
A
(I)
(3 4 )
iZ
X — OOCCH,
(ID
( 26 )
Cti3UH,
Na°
Cl
ZX
COOH
/
x X=O
(CH2) 3
COOH
(V I) (1 4 )
(V)
(IV ) (2 7 )
A num ber o f s i m i l a r r e a r r a n g e m e n t s h a v e b e e n r e p o r t e d i n t h e l i t e r a ­
tu re .
The r e a c t i o n o f p y r r o l e (3 5 )
c h lo r o f o r m a n d b a s e h a s g iv e n r i s e
(3 6 )
(3 7 ) a n d i n d o l e (3 8 )
(3 9 ) w ith
t o , r e s p e c t i v e l y , 3 - c h l o r o - p y r i d i n e an d
3 - c h l o r o - q u i n c l i n e , i n a d d i t i o n t o t h e e x p e c te d a ld e h y d e .
S h e l l a n d S a n d l e r (3 4 ) h a v e r e p o r t e d t h e r e a r r a n g e m e n t o f 6 , 6 - d i h a lo b i c y c l o ( 3 .1 .0 ) hexane w ith e l e c t r o p h i l i c r e a g e n ts .
T r e a tm e n t w ith
a l c o h o l i c s i l v e r n i t r a t e , y i e l d e d 6 - h y d r o x y - 1 - c y c lo h e x e n e .
th e s e a u th o rs th e s t r a i n
hanced r e a c t i v i t y ,
i n t h e 5 -3 r i n g s y s te m r e s u l t s
A c c o rd in g t o
in g r e a tly en­
6 , 6 - d i b r o m o b i c y c l o ( 3 .l ,0 ) h e x a n e b e in g 200 tim e s a s r e ­
a c t i v e a s t h e a n a lo g o u s 7 , 7 - d i h a i o b i c y c l o ( 4 . 1 . 0 ) h e p ta n e , W nich has a 6 -3
r i n g s y s te m .
P arh am , R e i f f a n d S w a r t z e n t r u b e r ( 1 5 a ) h av e r e p o r t e d t h e r e a c t i o n
o f in d e n y ls o d iu m w i t h c h lo r o f o r m i n e x c e s s i n d e n e .
2- C h l o r o n a p t h a l e n e
-3 3 was th e p r o d u c t when t h e r e a c t i o n m ix t u r e was s te a m d i s t i l l e d , b u t th e y
a l s o fo u n d I , 1 - d i c h l o r o - l a , 6 a - d i h y d r o c y c l o p r o p ( a ) in d e n e when n o n - p o la r
s o l v e n t s w e re em ployed i n p r o c e s s i n g t h e c r u d e r e a c t i o n m i x t u r e .
The p r o ­
p o s e d m ech an ism f o l l o w s ;
P arham a n d T w elv e s (1 5 b ) h a v e r e p o r t e d d ib ro m o c h lo ro m e th a n e , in d e n e
a n d b a s e s h o u ld l e a d p r e f e r e n t i a l l y t o t h e f o r m a tio n o f t h e f o ll o w i n g comp o u n d s;
Br
-3 4 The c r u d e c y c lo p r o p y l d e r i v a t i v e s o b t a i n e d fro m t h i s r e a c t i o n , p ro v e d t o
be t h e r m a l l y u n s t a b l e .
H ow ever, when t h e c r u d e p r o d u c t was d i s t i l l e d a
h i g h y i e l d o f a m ix t u r e o f t h e 2 - b ro m o n a p h th a le n e a n d 2 - c h l o r o n a p h t h a l e n e
was o b t a i n e d .
The com pound 6 , 6 - d i c h l o r o b i c y c l o ( 3 . 1 . 0 ) h e x a n e a p p e a r s t o u n d e rg o a
s i m i l a r th e r m a l r e a r r a n g e m e n t when h e a te d a t 150°C .
P r e s u m a b ly , t h e bond b e tw e e n c a r b o n atom s I a n d 5 i s t h e w e a k e s t
bond an d i t w i l l b r e a k d u r in g a r e a r r a n g e m e n t r e a c t i o n .
The w e a k n e ss o f
t h i s bond i s due t o t h e r i n g s t r a i n i n t h e 5 -3 r i n g s y s te m .
D u rin g t h e
r e a r r a n g e m e n t o f t h e 6 , 6 - d i c h l o r o b i c y c l o ( 3 . 1 . 0 ) h e x a n e , t h e re m o v a l o f one
o f t h e c h l o r i n e ato m s i s a s s i s t e d by t h e m eso m e ric e f f e c t o f t h e o t h e r
c h l o r i n e ato m a t t a c h e d t o t h e same c a r b o n a to m .
The m e so m e ric e f f e c t o f
t h e o t h e r c h l o r i n e atom w i l l te n d t o s t a b i l i z e t h e i n t e r m e d i a t e c y c lo p r o ­
p a n e c a rb o n iu m i o n .
The b o n d b e tw e e n c a r b o n atom s
I a n d 5 b r e a k s b e c a u s e o f th e i n ­
c r e a s e d r i n g s t r a i n on t h e c y c lo p r o p a n e r i n g w h ic h r e s u l t s
fro m t h e fo rm a ­
t i o n o f a c a rb o n iu m io n c e n t e r a t c a r b o n atom 6 .
The m ech an ism o f t h e r e a r r a n g e m e n t m o st l i k e l y i n e f f e c t f o llo w s
on th e n e x t page:
-3 5
B e c a u s e o f t h e i n c r e a s e d i n t e r n a l e n e r g y o f t h e m o le c u le a t 1 5 0 ° C .,
i t i s p o s s i b l e t h a t t h e r e a r r a n g e m e n t i s i n i t i a t e d by t h e c r e a t i n g o f t h e
bond b e tw e e n c a r b o n ato m s I a n d 5 .
The r e s u l t i n g i n t e r m e d i a t e c o u ld be
s t a b i l i z e d b y t h e p a r t i c i p a t i o n o f t h e n e ig h b o r i n g c h l o r i n e ato m t o fo rm
a c h lo r o n iu m i o n .
fo r th is re a c tio n :
An a l t e r n a t i v e c o n c e r t e d m echanism may b e p o s t u l a t e d
-3 6
I , 6 - d i c h l o r o - 1 - c y c l o h e x e n e h a s b e e n s y n t h e s i z e d by M o u sse ro n ( 2 5 ) .
T h is com pound a n d 1 , 3 - d i c h l o r o - l - c y c l o h e x e n e b o t h on o x i d a t i o n w i t h p o t a s ­
siu m p e rm a n g a n a te w o u ld g i v e g l u t a r i c a c i d .
T h e r e f o r e , t h e a u t h e n t i c com­
p o u n d was s y n t h e s i z e d by p a s s i n g c h l o r i n e g a s th r o u g h c y c lo h e x a n o n e (2 4 )
f o llo w e d by t h e r e a c t i o n o f p h o s p h o ro u s p e n t a c h l o r i d e a s f o ll o w s :
0
JL
IJ
0
ci2
LJ
/ zxX - C i
o"
A
A -.
V
P C is
The a u t h e n t i c compound was s e p a r a t e d fro m I , 2 - d i c h l o r o - 1 - c y c l o h e x e n e by
d is tilla tio n .
The a u t h e n t i c compound was f u r t h e r p u r i f i e d by v a p o r p h a s e
c h ro m a to g ra p h y a n a l y s i s an d was i d e n t i f i e d by i n f r a r e d a n a l y s i s .
1 ,2 - D i -
c h l o r o - 1 - c y c lo h e x e n e (4 0 ) was fo u n d t o b e m e l te d a t 2 6 -7 °C .
When 6 , 6 - d i c h l o r o b i c y c l o ( 3 . 1 . 0 ) h e x a n e a n d 1 , 6 - d i c h l o f o - l - c y c l o h e x e n e w e re r e a c t e d i n d i v i d u a l l y w i t h a n h y d ro u s p o ta s s iu m a c e t a t e i n a c e t i c
a n h y d r id e a n d r e f l u x e d a t 9 2 - 5 0C . , b o th g a v e l - c h l o r o - 6 - a c e t o x y - l - c y c l O "
h e x e n e , w h e re a s 6 , 6 - d i c h l o r o b i c y c l o ( 3 . 1 . 0 ) h e x a n e when h e a t e d a lo n e a t 95°C .
f o r a n h o u r g a v e no r e a r r a n g e m e n t p r o d u c t .
I n t h i s c a s e , t h e r e a r r a n g e m e n t was p r o b a b ly due t o t h e n u c l e o p h i l i c
a c t i v i t y o f th e a c e ta te io n .
T h is c a u s e s a f i s s i o n o f t h e r i n g g i v in g c y ­
c lo h e x e n e d e r i v a t i v e w h ic h was c h a r a c t e r i z e d t o be l - c h l o r o - 6 - a c e t o x y - l c y c lo h e x e n e .
Cl
The p r o p o s e d m echanism f o l l o w s ;
Cl
Cl
I
. OOCCHi
4 ------ X
J
CH3 COO
4 I
'y
L J
'
X-OOCCH3
L J
-C l"
-OOCCH1
”37,q
The i n f r a r e d s p e c t r a o f some r e p r e s e n t a t i v e s o f b i e y c l o ( 3 . I 0O )h e x a n e s a r e show n i n f i g u r e s I , 2 , 3 a n d 4 .
E ach o f t h e b i c y c l o ( 3 , 1 , 0 ) -
h e x a n e d e r i v a t i v e s h a s m edium t o s t r o n g a b s o r p t i o n p e a k s b e tw e e n 9 .7 7 =
9 .9 6
(1 0 2 4 a n d 1004 cm" ) .
A l l e n a n d c o - w o r k e r s (4 1 ) h a v e p o i n t e d o u t
t h a t i n a random s e l e c t i o n o f o r g a n i c com pounds 42% c o n t a i n e d one o r m ore
m o d e r a te o r s t r o n g a b s o r p t i o n p e a k s b e tw e e n 9 .7 - 1 0 . 0 5 ( 1 0 3 3 ~995 c m " .
The sam e a u f h p r s n o t e d t h a t a b s o r p t i o n a t 3 . 2 ^ ^ , r e g i o n w h ic h p r e v i o u s l y
h a d b e e n a s c r i b e d t o t h e m e th y le n e g ro u p o f t h e c y c lo p r o p a n e s t r u c t u r e i s
a ls o u n r e lia b le .
The s p e c t r a o f f i g u r e s I 9 2 , 3 , a n d 4 show no a b s o r p t i o n
a t 3 . 2 / ^ 9 b u t a s h o u l d e r a p p e a r s c o n s i s t e n t l y a t 3 .3 5 ^
e
-3 8
THE PO SSIBILITIES OF FUTURE RESEARCH
1.
A f u r t h e r i n v e s t i g a t i o n s h o u ld b e m ade o f t h e r e a c t i o n o f d i -
c h lo r o c a r b e n e w i t h c y c l o b u t e n e , c y c lo h e x e n e , e y e l o h e p t e n e , e y e l o o c t e n e
a n d o t h e r l i k e com pounds:
T h e o r e t i c a l l y , i t w o u ld b e h a r d t o p r e p a r e a se v en -m em b e red r i n g
a n a lo g o u s t o I , 6 - d i c h l o r o - l - c y c l o h e x e n e fro m 7 , 7 - d i c h l o r o b i c y c l o ( 4 . 1 . 0 ) h e p ta n e b e c a u s e o f t h e s t a b i l i t y o f t h e six -m e m b e red r i n g a n d t h e s t e r i c
i n f l u e n c e s e x i s t i n g p o s s i b l y i n se v en -m em b e re d r i n g s .
H ow ever, i t may be
f e a s i b l e t o p r e p a r e a h i g h e r m em bered r i n g th a n a se v en -m em b e re d o n e , w h ic h
t h e n m ig h t i n d e e d b e a n o v e l r i n g e x p a n s io n m e th o d .
2.
I t may be p o s s i b l e by t h e u s e o f l a b e l l e d c h l o r i n e (C l^ S ) to
d e te r m in e t h e m ech an ism o f t h e r e a r r a n g e m e n t o f 6 , 6 - d i c h l o r o b i c y c l o ( 3 . 1 . 0 ) h e x a n e by h e a t i n g .
The p r o c e d u r e o f R o b e r ts a n d M azur (4 2 ) c o u ld be m o d i­
f i e d by u s i n g N a I ^ l i n a c e t o n e o r H C l ^ i n b e n z e n e i n o r d e r t o c a r r y o u t
th e above r e a c tio n fo r la b e llin g p u rp o se s.
3.
The k i n e t i c s t u d i e s o f t h e f o ll o w i n g m echanism s m ig h t b e i n v e s ­
t i g a t e d . t o a d v a n ta g e i f i n t e r m e d i a t e com pounds c a n b e i s o l a t e d .
-3 9 The r a t e o f r e a r r a n g e m e n t o f schem e ( I ) c o u ld b e e x p e c t e d to be m ore r a p i d
t h a n t h e r a t e o f r e a r r a n g e m e n t o f schem e ( 2 ) .
T h is c a n b e d e te r m in e d o n ly
i f i n t e r m e d i a t e com pounds c a n b e i s o l a t e d .
4.
From t h e e v id e n c e p r e s e n t e d on p a g e s 30 a n d 3 1 , t h e b i c y c l o -
( 3 . 1 . 0) h e x a n e - 6 - c a r b o x y l i c a c i d c o u ld b e e x p e c t e d t o b e a t t a c k e d by n u c l e o ­
p h i l i c r e a g e n t s s u c h , a s p o ta s s iu m p e rm a n g a n a te .
T h e r e f o r e , i t may be
f e a s i b l e t o p r e p a r e b i c y c l o ( 3 . I . 0 ) h e x a n e - 6 -h y d ro x y ~ 6 - c a r b o x y l i e a c i d w i t h
p o t a s s i u m p e rm a n g a n a te .
The a - h y d r o x y a c i d c o u ld b e e x p e c t e d t o u n d e rg o
o x i d a t i o n w i t h c o n c e n t r a t e d s u l f u r i c a c i d r e s u l t i n g i n t h e f o r m a ti o n o f
b i c y c l o ( 3 . 1 .0 ) h e x a n - 6 - o n e .
T h is w o u ld b e i n k e e p in g w i t h M einw ald a n d
G assm an ( 4 3 ) .
M J1 t
I ,
SUMMARY
1.
B i c y c I o ( 3 . 1 , 0 ) lie x a n e - 6 ~ c a r b o x y l ie a c i d h a s b e e n s y n t h e s i z e d from cy~
c l o p e n t e n e w i t h e t h y l d i a z o a c e t a t e i n t h e p r e s e n c e o f c o p p e r pow der
a n d f o ll o w e d by t h e a l k a l i n e h y d r o l y s i s .
a ls o o b ta in e d .
2.
I t s am id e d e r i v a t i v e was
T h e s e a r e new com pounds.
The r e a c t i o n o f t h i s a c i d b y t h e H e l l - V o l h a r d - Z e l i n s k y m eth o d h a s b e e n
d is c u s s e d .
E v id e n c e i n d i c a t e s t h i s m eth o d c a n n o t b e a p p l i e d t o t h i s
com pound.
3.
6 j 6 - D i c h l o r o b i c y c l o ( 3 . 1 . 0 ) h e x a n e h a s b e e n s y n t h e s i z e d fro m e y e lo p e n ­
te n e w ith d ic h lo ro c a rb e n e in n -p e n ta n e .
T h is c o n f ir m s p r e v i o u s s y n ­
t h e s i s w ith d ic h lo r o c a r b e n e .
4.
R e a rra n g e m e n t o c c u r r e d when 6 , 6 - d i c h l o r o b i c y c l o ( 3 . 1 . 0 ) h e x a n e i s h e a t ­
e d a t 150°C . o r r e f l u x e d w i t h a c e t a t e i o n a t 92«*5°G.
fin d in g s .
5.
T h e s e a r e new
The m ech an ism s a r e p r o p o s e d .
B o th 6 » 6 ” d i c h l o r o b i c y c l o ( 3 . 1 . 0 ) h e x a n e a n d ! , b - d i e h l o r o - l - c y e l o h e x e n e
h a v e b e e n shown t o g i v e sam e l - c t i l o r o - b - a c e t o x y - l - c y c l o h e x e n e , t h e
f o rm e r a new f i n d i n g . >
6.
l s 6:- D ic h lo r o “ l “ c y c lo h e x e n e i s f u r t h e r p r o v e d by p r e p a r i n g a n a u t h e n t i c
com pound w h ic h c h e c k e d c o m p l e te l y by i n f r a r e d a n d v a p o r p h a s e ch ro m a­
t o g r a p h y a n a l y s e s a n d a l s o c h e c k e d b y t h e d e g r a d a t i o n o f l - c h l o r o - 6k e to -l-c y e lo h e x e n e to g l u t a r i c a c id .
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___ ^ nt-TTV I TBRARIES
I - I V M I O O f l 694 4
D378
YlBf
c o p .2
144883
Yao, Shi-K uang
F used s m a ll r i n g compounds
Z iL 'M isJ:
/(3 3 /
D 3 7 8
Y l f H
J .0 'f ■
144883