Carbonfunctional Organosilicon Compounds: Synthesis of...

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Carbonfunctional Organosilicon Compounds: Synthesis of Some Silylcoumarins

B . N . G h o s e *

Department of Chemistry, University of Ife, Ile-ife, Nigeria

Z. Naturforsch. 34b, 1140-1144 (1979); received April 10, 1979

Silylcoumarins The syntheses of some silylcoumarins of the formulae 7-H0C9H402-4-(CH2)nSiMe2(F)

[n = 3 and 4], and 7-H0C9H402-4-C6H4(CH2)nSiMe2(F)-4' [ n = 1, 2 and 3] are reported.

Introduction C a r b o n f u n c t i o n a l s i l a n e s b e a r i n g c o u m a r i n t y p e

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

t i a l i m p o r t a n c e as p r e c u r s o r s i n c o s m e t i c i n d u s t r i e s .

W e r e p o r t t h e s y n t h e s i s o f s o m e 4 - o r g a n o s i l i c o n

d e r i v a t i v e s o f 7 - h y d r o x y c o u m a r i n , i n w h i c h w e

c h e c k e d t h e p o s s i b i l i t y o f i n t r o d u c i n g f u n c t i o n a l i t y

a t t h e s i l i c o n a t o m i n t h e c o u m a r i n c o m p o u n d s t o

m a k e i t p o s s i b l e t o l i n k t h e s e o r g a n o s i l a n e s t o o t h e r

o r g a n o m e t a l l i c c o m p o u n d s .

Results and Discussion W e h a v e p r e v i o u s l y r e p o r t e d [1] t h a t s i l i c o n

s u b s t i t u t e d /?-ketoesters r e a c t w i t h r e s o r c i n o l , i n t h e

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

e x p e c t e d 7 - h y d r o x y c o u m a r i n s b e a r i n g o r g a n o s i l i c o n

s u b s t i t u e n t s i n t h e 4 - p o s i t i o n . I t is w e l l e s t a b l i s h e d

t h a t a r o m a t i c g r o u p s s u c h a s p h e n y l , p - c h l o r o p h e n y l

e t c . a t t a c h e d t o s i l i c o n a r e l a b i l e t o a c i d c l e a v a g e [2],

W e , t h e r e f o r e , e x p l o i t e d t h i s r o u t e t o s y n t h e s i z e

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

7 - H 0 C 9 H 4 0 2 - 4 - ( C H 2 ) n S i M e 2 ( F ) , (n = 3 a n d 4), a n d

7 - H 0 C 9 H 4 0 2 - 4 - C 6 H 4 ( C H 2 ) n S i M e 2 ( F ) - 4 ' , (n = 1 , 2

a n d 3), u s i n g t h e /3-ketoesters o f t h e t y p e

M e 2 P h S i ( C H 2 ) « C 0 C H 2 C 0 2 E t a n d

M e 2 ( p - C l C 6 H 4 ) S i ( C H 2 ) „ C 6 H 4 C 0 C H 2 C 0 2 E t . I n t h e

p r e s e n t c a s e d i m e t h y l p h e n y l s i l y l a c e t i c e s t e r s a n d

d i m e t h y l ( p - c h l o r o p h e n y l ) s i l y l a r o y l e s t e r s w e r e

c h o s e n . F o r t h e a r y l ser ies , p - c h l o r o p h e n y l g r o u p

w a s c h o s e n t o p r e v e n t a c y l a t i o n t a k i n g p l a c e i n t h e

p h e n y l r i n g a t t a c h e d t o s i l i c o n d u r i n g F r i e d e l - C r a f t

a c y l a t i o n .

T h e s i l y l k e t o n e s ( V I I I - X I I ) w e r e p r e p a r e d i n

g o o d y i e l d s b y t h e f o l l o w i n g r o u t e s :

* Reprint requests to Dr. M. Z. A. Badr. 0340-5087/79/0800-1140/$ 01.00/0

M ^ 0 . / n T T . v 1) M g / E t 2 0 M e 2 P h S i ( C H 2 ) „ X — — >•

2) C d C l 2

3) M e C O C l

M e 2 P h S i ( C H 2 ) „ C O M e

w h e r e X = Cl or B r

V I I I : n = 3

I X : n = 4

a n d

M e C O C l / A l C l 3 ( p - C l C 6 H 4 ) M e 2 S i ( C H 2 ) n P h >

C H 2 C l 2 / 0 °

( y - C l C 6 H 4 ) M e 2 S i ( C H 2 ) r e C 6 H 4 C O M e - ^

X : n = 1 X I : n = 2 X I I : n = 3

w h i c h w e r e t h e n c o n v e n i e n t l y c o n v e r t e d t o cor-

r e s p o n d i n g ^ - k e t o e s t e r s ( X I I I - X V I I ) b y t h e f o l l o w -

i n g r o u t e :

( E t O ) 2 C O X - C O M e X - C 0 C H 2 C 0 2 E t

N a H / E t 2 0

X I I I : X = M e 2 P h S i ( C H 2 ) 3 -

X I V : X = M e 2 P h S i ( C H 2 ) 4 -

X V : X = M e 2 ( p - C l C 6 H 4 ) S i C H 2 C 6 H 4 -

X V I : X = M e 2 ( p - C l C 6 H 4 ) S i ( C H 2 ) 2 C 6 H 4 -

X V I I : X = M e 2 ( p - C l C 6 H 4 ) S i ( C H 2 ) 3 C 6 H 4 -

T h e ^ - k e t o e s t e r s w e r e r e a c t e d w i t h r e s o r c i n o l i n

p r e s e n c e of c o l d c o n c e n t r a t e d s u l p h u r i c a c i d , a n d

t h e n t r e a t e d w i t h p o w d e r e d a m m o n i u m fluoride t o

g i v e t h e d e s i r e d p r o d u c t . T h e a c i d l a b i l e p h e n y l -

a n d p - c h l o r o p h e n y l - g r o u p s w e r e c l e a v e d f r o m s i l i c o n

a t o m as e x p e c t e d , a n d t h e s i l y l c o u m a r i n s ( X V I I I t o

X X I I ) w e r e o b t a i n e d i n a b o u t 6 0 % y i e l d :

B. N. Ghose • Carbonfunctional Organosilicon Compounds 1141

1) H2SO4 X - C 0 C H 2 C 0 2 E t + m - ( H 0 ) 2 C 6 H 4 —

2) NH4F 7 - H 0 C 9 H 4 0 2 - 4 - Y

X V I I I : Y = - ( C H 2 ) 3 S i M e 2 ( F )

X I X : Y = - ( C H 2 ) 4 S i M e 2 ( F )

X X : Y = - C 6 H 4 C H 2 S i M e 2 ( F ) - 4 '

X X I : Y = - C 6 H 4 ( C H 2 ) 2 S i M e 2 ( F ) - 4 '

X X I I : Y = - C 6 H 4 ( C H 2 ) 3 S i M e 2 ( F ) - 4 '

Experimental T h e d i s t i l l a t i o n s w e r e c a r r i e d o u t w i t h p r e c i s i o n

m a d e V i g r e u x c o l u m n s , e q u i v a l e n t t o c a . 1 2 t h e o -r e t i c a l p l a t e s . M o i s t u r e s e n s i t i v e c o m p o u n d s ( n o t a b l y c h l o r o s i l a n e s , G r i g n a r d r e a g e n t s a n d o r g a n o l i t h i u m c o m p o u n d s ) w e r e m a n i p u l a t e d u n d e r d r y n i t r o g e n .

N M R s p e c t r a w e r e r e c o r d e d o n a V a r i a n A 60 o r T 60 i n s t r u m e n t , w i t h t e t r a m e t h y l s i l a n e a s i n t e r n a l s t a n d a r d . T h e r e s u l t s a r e g i v e n a s v a l u e s i n p p m . T h e I R s p e c t r a w e r e r e c o r d e d o n a P e r k i n - E l m e r 2 3 7 s p e c t r o p h o t o m e t e r , b y u s i n g f i l m s f o r l i q u i d s a n d n u j o l m u l l s f o r s o l i d s . T h e r e p o r t e d m o l e c u l a r w e i g h t s r e f e r t o t h e p a r e n t p e a k a s r e c o r d e d o n a n A E 1 M S 9 s p e c t r o m e t e r .

(A) Preparation of silyl precursors I) (y-Chloropropyl)dimethylphenylsilane [Me2PhSi(CH2)3Cl]

( y - C h l o r o p r o p y l ) d i m e t h y l c h l o r o s i l a n e [3], o n t r e a t -m e n t w i t h 1 0 % e x c e s s p h e n y l m a g n e s i u m b r o m i d e i n e t h e r , y i e l d e d t h e t i t l e c o m p o u n d ( 8 0 % ) b . p . 6 4 ° / 0 . 0 2 m m H g , 1 . 5 0 8 0 (l it . [4], b . p . 1 1 0 ° / 2 m m H g , n2£ 1 . 5 1 5 0 ) . I R ( f i lm) v ( M e - S i ) 1 2 5 0 (s), 830 (s) c m - 1 . N M R ( n e a t ) M e 2 S i 6 0 . 1 8 (s), C H 2

0 . 6 7 ( m ) , 1 . 5 5 (m) , 3 . 2 2 (t), P h 7 . 3 2 ( m ) p p m .

II) (4-Hydroxybutyl)dimethylphenylsilane [Me2PhSi(CH2)4OH]

( C h l o r o ) d i m e t h y l p h e n y l s i l a n e [5] ( 6 8 . 2 g ; 0 . 4 m o l e ) w a s a d d e d t o t h e G r i g n a r d r e a g e n t , p r e p a r e d f r o m ( 4 - c h l o r o b u t o x y ) t r i m e t h y l s i l a n e [6] ( 7 2 . 2 g ; 0 . 4 m o l e ) a n d m a g n e s i u m t u r n i n g s (9.6 g ; 0 .4 g - a t o m ) i n e t h e r (400 c m 3 ) . U s u a l w o r k i n g u p o f t h e r e a c t i o n m i x t u r e g a v e t h e p r o d u c t ( 7 0 % ) b . p . 92°/0.002 m m H g , n™ 1 . 5 1 1 2 .

C i 2 H 2 o O S i

F o u n d C 69 .4 H 9 . 6 m o l . w t . 208,0, C a l c d C 6 9 . 2 H 9 .6 m o l . w t . 2 0 8 . 3 7 .

I R ( f i l m ) y ( 0 H ) 3 3 3 7 (s, b) , r ( M e S i ) 1 2 4 8 (s, sh) , 830 (s) c m - i . N M R ( n e a t ) O H <54.23 (s), P h 7 . 2 6 ( m ) , C H 2 0 . 6 6 ( m ) , 1 . 4 2 (m) , 3 . 4 3 (t), M e 2 S i 0 . 1 6 (s) p p m .

III) (4-Bromobutyl)dimethylphenylsilane [Me2PhSi(CH2)4Br]

P h o s p h o r u s t r i b r o m i d e (32.5 g ; 0 . 1 2 m o l e ) w a s a d d e d d r o p w i s e t o ( 4 - h y d r o x y b u t y l ) d i m e t h v l p h e n y l -s i l a n e ( I I ) (49.4 g ; 0 .24 m o l e ) s t i r r e d a t Ö °C. T h e

m i x t u r e w a s t h e n h e a t e d t o 80 °C f o r 1 h . T h e u s u a l w o r p u p p r o c e d u r e g a v e t h e t i t l e c o m p o u n d ( 6 0 % ) b . p . 94 o /0.001 m m H g , n 2 1 1 . 5 1 8 4 .

C i 2 H i 9 B r S i

F o u n d C 5 3 . 1 H 7 . 0 B r 2 9 . 5 m o l . w t . 2 7 1 . 0 , C a l c d C 5 3 . 1 H 7 . 0 B r 2 9 . 5 m o l . w t . 2 7 1 . 2 8 .

I R ( f i lm) v ( M e S i ) 1 2 5 0 (s, sh) , 8 3 5 (s, b ) c m - i . N M R ( n e a t ) M e 2 S i <5 0 . 1 2 (s), C H 2 0 . 5 0 (m), 1 . 3 3 ( m ) , 3 . 0 0 (t), P h 7 . 1 6 ( m ) p p m .

(IV) p-Chlorophenyl(chloro)dimethylsilane [p-ClC6HiSi(Cl)Me2J

p - C h l o r o p h e n y l m a g n e s i u m b r o m i d e [ p r e p a r e d f r o m p - b r o m o c h l o r o b e n z e n e ( 1 9 1 . 5 g ; 1 m o l e ) a n d m a g n e t i u m t u r n i n g s (26.4 g ; 1 . 1 g - a t o m ) i n e t h e r ( 7 5 0 c m 3 ) ] w a s a d d e d t o d i c h l o r o d i m e t h y l s i l a n e ( 1 9 3 g ; 1 . 5 m o l e ) i n e t h e r (200 c m 3 ) a t 0 °C. T h e m i x t u r e w a s s u b s e q u e n t l y a l l o w e d t o w a r m u p t o r o o m t e m p e r a t u r e a n d w a s t h e n r e f l u x e d f o r 4 h . T h e r e a c t i o n m i x t u r e w a s filtered, f o l l o w e d b y t h e e x t r a c t i o n o f t h e p r e c i p i t a t e d s a l t s w i t h a m i x t u r e o f p e t r o l e t h e r a n d e t h e r ( 1 : 1 ) . F r a c t i o n a t i o n o f t h e c o m b i n e d filtrate a n d e x t r a c t s g a v e t h e p r o d u c t ( 6 7 % ) b . p . 62 o /0.9 m m H g , riQ 1 . 5 2 7 8 .

C g H i o C ^ S i

F o u n d C 4 6 . 3 H 5 . 0 C 1 3 3 . 9 m o l . w t . 2 0 5 . 0 , C a l c d C 4 6 . 8 H 4 . 9 C 1 3 4 . 6 m o l . w t . 2 0 5 . 1 6 .

I R ( f i lm) v ( a r o m a t i c ) 1 5 8 5 (s), r ( M e S i ) 1 2 6 5 (s), 840 (s) c m - 1 . N M R ( n e a t ) M e 2 S i d 0 .69 (s), P h 7 . 4 3 (m) p p m .

V) Benzyl(dimethyl)p-chlorophenylsilane [PhCH2SiMe2(C6H4Cl-p) ]

p - c h l o r o p h e n y l ( c h l o r o ) d i m e t h y l s i l a n e ( I V ) ( 5 1 . 2 g ; 0 . 2 5 m o l e ) w a s a d d e d t o b e n z y l m a g n e s i u m c h l o r i d e (0.3 m o l e ) i n e t h e r (300 c m 3 ) . U s u a l w o r k i n g u p o f t h e r e a c t i o n m i x t u r e g a v e t h e t i t l e c o m p o u n d ( 9 3 % ) b . p . 1 0 2 7 0 . 0 2 m m H g , n % 1 . 5 6 6 2 , w h i c h s o l i d i f i e d o n s t a n d i n g ( m . p . 3 1 - 3 2 °C) .

C i a H i v C l S i

F o u n d C 6 9 . 1 H 6 . 5 C 1 1 3 . 5 m o l . w t . 2 6 1 . 0 , C a l c d C 6 9 . 1 H 6 . 5 C U 3 . 6 m o l . w t . 2 6 0 . 8 4 .

I R ( f i lm) v ( a r o m a t i c ) 1 6 1 0 (s), 1 5 8 5 (s), r ( M e S i ) 1 2 6 0 (s), 8 3 5 (s) v ( p - s u b s t . ) 8 1 0 c m - i . N M R ( C C 1 4 ) M e 2 S i d 0 . 1 5 (s), C H 2 2 . 1 3 (s), P h 6 . 9 5 (m) p p m .

VI) ß-Phenylethyldimethyl(p-chlorophenyl)silane [Ph(CH2)2SiMe2(C6IhCl-p ) J

C o u p l i n g o f / 3 - p h e n y l e t h y l m a g n e s i u m b r o m i d e w i t h p - c h l o r o p h e n y l ( c h l o r o ) d i m e t h y l s i l a n e ( I V ) a f -f o r d e d t h e t i t l e c o m p o u n d ( 6 2 % ) b . p . 1 0 5 7 0 . 0 1 m m H g , 1 . 5 5 7 0 .

C 1 6 H 1 9 C l S i

F o u n d C 7 0 . 0 H 6 . 9 C 1 1 2 . 9 m o l . w t . 2 7 5 . 0 , C a l c d C 7 0 . 0 H 6 . 9 C 1 1 2 . 9 m o l . w t . 2 7 4 . 8 6 .

1142 B. N. Ghose • Carbonfunctional Organosilicon Compounds 1142

I R (f i lm) v ( a r o m a t i c ) 1580 (s), 1605 (s), v ( M e S i ) 1260 (s), 845 (s) v (p-subst . ) 8 1 0 c m - 1 . N M R ( C C 1 4 ) M e 2 S i 6 0.06 (s), C H 2 0 .91 (m), 2 .40 (m), P h 7 . 0 0 (m) p p m .

VII) y-Phenylpropyldimethyl(p-chlorophenyl) -silane [Ph(CH2)zSiMe2(C6H4Cl-p)]

y - P h e n y l p r o p y l m a g n e s i u m b r o m i d e a n d p - c h l o r o -p h e n y l ( c h l o r o ) d i m e t h y l s i l a n e ( I V ) g a v e t h e t i t l e c o m p o u n d (81 % ) b . p . 108°/0.001 m m H g , n™ 1 . 5 5 1 5 .

C i 7 H 2 i C l S i

F o u n d C 7 1 . 1 H 7 . 5 C 1 1 2 . 2 m o l . w t . 2 8 9 . 0 , C a l c d C 7 0 . 7 H 7 . 3 C 1 1 2 . 3 m o l . w t . 2 8 8 . 8 9 .

I R (f i lm) v ( a r o m a t i c ) 1 6 0 5 (s), 1 5 7 5 (s), v ( M e S i ) 1 2 5 0 (s), 830 (s), v (p-subst . ) 805 c m ' 1 . N M R (CC14) M e 2 S i d 0.02 (s), C H 2 0.50 (m), 1 . 4 1 (m), 2 . 3 8 (t), P h 7 .00 (m) p p m .

(B) Preparation of silyl ketones VIII) 5-(Dimethylphenylsilyl)pentan-2-one [Me2PhSi(CH2)zCOMe ]

T o y - d i m e t h y l p h e n y l s i l y l p r o p y l m a g n e s i u m c h l o -r i d e [ p r e p a r e d f r o m m a g n e s i u m a n d ( y - c h l o r o -p r o p y l ) d i m e t h y l p h e n y l s i l a n e ( I ) i n e t h e r ] c a d m i u m c h l o r i d e ( d r i e d a t I O " 3 m m H g a t 120 °C f o r 4 h) w a s a d d e d i n p o r t i o n s a t 0 °C. T h e v o l u m e o f t h e r e a c t i o n m i x t u r e w a s r e d u c e d b y d i s t i l l i n g o f f e t h e r a n d b e n z e n e w a s a d d e d a n d t h e m i x t u r e w a s re-f l u x e d f o r 3 h . T h e r e s u l t i n g g r e y c o l o u r e d s o l u t i o n w a s c o o l e d t o 0 °C a n d a c e t y l c h l o r i d e w a s a d d e d t o i t . T h e m i x t u r e w a s r e f l u x e d f o r 2 h f o l l o w e d b y h y d r o l y s i s w i t h 1 0 % H C l . U s u a l w o r k u p g a v e t h e p r o d u c t ( 6 2 % ) b . p . 94°/0.01 m m H g , wj 8 1 . 4 9 8 5 .

C i 3 H 2 0 O S i

F o u n d C 70.6 H 9 . 1 m o l . w t . 220.0, C a l c d C 70.9 H 9 . 1 m o l . w t . 220.38.

I R (f i lm) v ( C = 0 ) 1 7 1 5 (s), v ( a r o m a t i c ) 1 6 0 5 (s), v (MeSi) 1 2 5 0 (s), 830 (s) c m - i . N M R ( n e a t ) M e 2 S i 8 — 0 . 2 0 (s), C H 2 0 .34 (m), 1 .00 (m), 1 . 7 4 (t), C H 3

1 . 3 7 (s), P h 6.84 (m) p p m .

IX) 6- (Dimethylphenylsilyl)hexan-2-one [Me2PhSi(CH2)4COMe ]

I n a n i d e n t i c a l r e a c t i o n a s i n ( V I I I ) ( 4 - b r o m o -b u t y l ) d i m e t h y l p h e n y l s i l a n e ( I I I ) g a v e t h e t i t l e c o m -p o u n d ( 6 0 % ) b . p . 95-98°/0.001 m m H g , n l £ 1 . 4 7 6 5 .

C i 4 H 2 2 O S i

F o u n d C 7 1 . 6 H 9.2 m o l . w t . 234.0, C a l c d C 7 1 . 8 H 9.4 m o l . w t . 2 3 4 . 4 1 .

I R (f i lm) v ( C = 0 ) 1 7 1 8 (s) v ( a r o m a t i c ) , 1 6 0 5 (s), v (MeSi) 1 2 5 2 (s), 835 (s) c m - » . N M R ( n e a t ) M e 2 S i Ö — 0 . 1 0 (s), C H 2 0.66 (m), 1 .83 (t), C H 3 1 . 5 0 (s), P h 7.00 (m) p p m .

X) p-[(p-Chlorophenyl)dimethylsilylmethyl]-acetophenone [(p-ClCeH4)Me2SiCH2C6H4COMe-p]

T o a s o l u t i o n o f b e n z y l ( d i m e t h y l ) - p - c h l o r o p h e n y l -s i l a n e ( V ) (26.05 g ; 0 .1 m o l e ) i n d i c h l o r o m e t h a n e ( 1 0 0 c m 3 ) a t 0 °C w a s a d d e d s l o w l y a p r e p r e p a r e d c o m p l e x o f a l u m i n i u m c h l o r i d e ( a n h y d r o u s ) (20.0 g ; 0 . 1 5 m o l e ) a n d a c e t y l c h l o r i d e (7.9 g ; 0.1 m o l e ) i n d i c h l o r o m e t h a n e ( 1 0 0 m 3 ) , m a i n t a i n e d a t 0 °C. T h e r e a c t i o n m i x t u r e w a s s u b s e q u e n t l y w a r m e d u p t o r o o m t e m p e r a t u r e a n d w a s k e p t s t i r r e d a t t h i s t e m p e r a t u r e f o r 3 h . F i n a l l y i t w a s p o u r e d o v e r c r u s h e d ice . U s u a l w o r k u p g a v e t h e t i t l e c o m p o u n d ( 5 5 % ) . m . p . 5 5 - 5 7 °C ( p e t r o l e t h e r ) .

C i 7 H 1 9 C 1 0 S i

F o u n d C 6 7 . 6 H 6 . 2 C 1 1 1 . 7 m o l . w t . 3 0 3 . 3 0 3 , C a l c d C 6 7 . 4 H 6 . 3 C 1 1 1 . 7 m o l . w t . 3 0 2 . 8 7 .

I R ( n u j o l ) v ( C = 0 ) 1680 (s) v ( a r o m a t i c ) , 1 6 1 0 (s) v ( M e S i ) , 1 2 5 5 (s, sh) , 850 (s) v (p-subst . ) , 8 1 5 (s) c m - 1 . N M R (CDCla) M e 2 S i «5 0.33 (s), C H 2 2 .38 (s), C H 3

2 . 5 2 (s), P h 7 .30 (m) p p m .

XI) p-[p-Chlorophenyl(dimethyl jsilylethyl]aceto-phenone [p-(p-ClC6H4)Me2Si(CH2)2CeH4COMe-p]

T r e a t m e n t o f / ? - p h e n y l e t h y l ( d i m e t h y l ) - p - c h l o r o -p h e n y l s i l a n e ( V I ) w i t h a l u m i n i u m c h l o r i d e a n d a c e t y l c h l o r i d e c o m p l e x as i n ( X ) g a v e t h e d e s i r e d p r o d u c t ( 6 4 % ) b . p . 124°/0.001 m m H g , rig 1 . 5 3 3 5 .

C i g H a i C l O S i

F o u n d C 6 8 . 4 H 6 . 8 C l l l . l m o l . w t . 3 1 7 . 0 , C a l c d C 6 8 . 3 H 6 . 6 C 1 1 1 . 2 m o l . w t . 3 1 6 . 0 .

I R (f i lm) v ( C = 0 ) 1 6 8 0 (s) v ( a r o m a t i c ) , 1 6 0 5 (s) v ( M e S i ) , 1 2 5 5 (s), 840 (s), v (p-subst . ) 7 9 5 (s) c m - 1 . N M R ( n e a t ) M e 2 S i <5 — 0 . 1 6 (s), C H 2 0.67 (m), 2 . 3 3 (m), C H 3 2 .08 (s), P h 7.00 (m) p p m .

XII) p-[p-Chlorophenyl(dimethyl)silylpropyl]-acetophenone f(p-ClC6H4)Me2Si(CH2)3CeHACOMe-pJ

T h e t i t l e c o m p o u n d w a s o b t a i n e d ( 6 1 % ) , as a h e a v y o i l b y a s i m i l a r r e a c t i o n as i n ( X ) w i t h y - p h e n y l p r o p y l ( d i m e t h y l ) - p - c h l o r o p h e n y l s i l a n e -( V I I ) . w^8 1 . 5 2 6 6 .

C i 9 H 2 3 C 1 0 S i

F o u n d C 6 8 . 9 H 6 . 6 C 1 1 0 . 5 m o l . w t . 3 3 1 . 0 , C a l c d C 6 9 . 0 H 6 . 9 C 1 1 0 . 7 m o l . w t . 3 3 0 . 9 2 .

I R (f i lm) v ( C = 0 ) 1 6 8 0 (s), v ( a r o m a t i c ) 1605 (s), f ( M e S i ) 1 2 6 8 (s), 830 (s), v (p-subst . ) 7 9 5 (s) c m " 1 . , N M R ( n e a t ) M e S i < 5 — 0 . 1 2 (s), C H 2 0 .33 (m), 1 .46 (m), 2 .43 (t), C H 3 2 . 3 3 (s), P h 7 .26 (m) p p m .

(C) Preparation of silyl-ß-ketoesters XIII) Ethyl- [ß-(dimethyl)phenylsilylethylJaceto-acetate [Me2PhSi(CH2)zC0CH2C02Et]

S o d i u m h y d r i d e (9.6 g o f 5 0 % s u s p e n s i o n i n p a r a f f i n o i l ; 0.2 m o l e ) w a s f r e e d f r o m oi l b y w a s h i n g w i t h p e t r o l e t h e r a n d finally k e p t s t i r r e d i n e t h e r

B. N. Ghose • Carbonfunctional Organosilicon Compounds 1143

(150 c m 3 ) a t r o o m t e m p e r a t u r e . D i e t h y l c a r b o n a t e ( 1 1 . 8 g , 0.1 mole) a n d 5 - [ ( d i m e t h y l ) p h e n y l s i l y l ] -p e n t a n - 2 - o n e ( V I I I ) ( 1 1 . 0 g ; 0.05 m o l e ) in e t h e r (50 c m 3 ) w e r e a d d e d t o i t . T h e m i x t u r e w a s r e f l u x e d f o r 24 h, s u b s e q u e n t l y p o u r e d o n t o c r u s h e d ice a n d k e p t n e u t r a l b y a d d i n g 2 N h y d r o c h l o r i c a c i d . U s u a l w o r k u p g a v e t h e t i t le c o m p o u n d as h e a v y oi l ( 7 0 % ) w h i c h res i s ted a l l a t t e m p t s a t c r y s t a l l i z a t i o n . n™ 1.5056.

C i 6 H 2 4 0 3 S i

F o u n d C 65.8 H 8.4 m o l . w t . 292.0, C a l c d C 65.7 H 8.3 m o l . w t . 292.44.

I R (film) v ( C = 0 ) (ester) 1 7 4 5 (s) (keto) , 1 7 1 5 (s) v(MeSi), 1250 (s, sh), 830 (s) c m - ' . N M R (CC14) M e 2 S i <5 0 .16 (s), C H 2 0.90 (m), 1 . 7 6 (m), 2 .70 (t),

0 = 6 - C H 2 - C = 0 3.81 (s), C H s O 2.62 (q), C H 3 1 . 3 4 (t), P h 7 .46 (m) p p m .

XIV) Ethyl-[y-(dimethyl)phenylsilylpropyl]-acetoacetate [Me2PhSi(CH2)4C0CH2C02Et]

6 - [ ( D i m e t h y l ) p h e n y l s i l y l ] h e x a n - 2 - o n e ( I X ) w a s t r e a t e d in a s imi lar w a y as in ( X I I I ) t o g i v e t h e t i t l e c o m p o u n d as a h e a v y oi l ( 7 5 % ) , w h i c h r e s i s t e d a l l a t t e m p t s a t c r y s t a l l i z a t i o n , n ^ 1 .5038.

C 1 7 H 2 6 0 3 S i

F o u n d C 66.7 H 8.5 m o l . w t . 306.0, C a l c d C 66.6 H 8.5 m o l . w t . 306.47.

I R (film) v ( C = 0 ) (ester) 1740 (s) (keto) , 1 7 1 5 (s) v(MeSi) , 1250 (s, sh), 830 (s) c m - 1 . N M R (CC14) M e 2 S i d — 0 . 0 4 (s), C H 2 0.70 (m), 1 . 7 8 (m), 2.83 (m),

0 = C - C H 2 - C = 0 3.69 (s), C H 2 0 3.89 (q), C H 3

1 .58 (t), P h 7.50 (m) p p m .

XV) Ethyl-[p-(p-chlorophenyl)dimethylsilyl-methyl Jbenzoylacetate [p-(p-ClC6H4)Me2SiCH2C6H4C0CH2C02Et ]

A s i m i l a r r e a c t i o n as in ( X I I I ) w i t h p- [p-chloro-p h e n y l ) d i m e t h y l s i l y l m e t h y l ] a c e t o p h e n o n e ( X ) g a v e t h e des i red c o m p o u n d as h e a v y oi l ( 6 0 % ) b . p . 180°/0.001 m m H g , n™ 1 .5635.

C 2 o H 2 3 C 1 0 3 S i

F o u n d C 6 4 . 1 H 6 . 3 C 1 9 . 5 m o l . w t . 3 7 5 . 0 , C a l c d C 6 4 . 1 H 6 . 1 C 1 9 . 5 m o l . w t . 3 7 4 . 9 3 .

I R (film) v ( C = 0 ) (ester) 1 7 5 0 (s) (keto) , 1690 (s) v ( a r o m a t i c ) , 1 6 1 0 (s) v(MeSi), 1 2 6 5 (s), 840 (s) v (p-subst . ) , 8 1 5 (s) c m - 1 . N M R (CCl 4 )Me 2 Si<50.13(s) ,

C H 2 2 .21 (m), 0 = C - C H 2 - C = 0 3 .91 (s), C H a O 4.23 (q), C H 3 1 .31 (t), P h 7 .50 (m) p p m .

XVI) Ethyl-[p-(p-chlorophenyl)dimethylsilyl-ethyl Jbenzoylacetate [p- ( p-ClCeHi )Me2Si( CH2 )2CeH4C0CH2C02Et J

T h e t i t l e c o m p o u n d w a s o b t a i n e d ( 6 2 % ) a s a h e a v y oil b y a s imi lar r e a c t i o n t o t h a t in ( X I I I ) w i t h [ p - ( p - c h l o r o p h e n y l ) d i m e t h y l s i l y l e t h y l ] a c e t o -p h e n o n e ( X I ) . n™ 1.5460.

C 2 i H 2 5 C 1 0 3 S i

F o u n d C 6 4 . 6 H 6 . 2 C19.0 m o l . w t . 3 8 9 . 0 , C a l c d C 6 4 . 9 H 6 . 4 C19.1 m o l . w t . 388.9.

I R (film) v ( C = 0 ) (ester), 1750 (s) (keto) , 1690 (s) v ( a r o m a t i c ) , 1605 (s) v(MeSi), 1 2 5 5 (s), 840 (s) v(p-subst . ) , 800 (s) c m - 1 . N M R (CC14) M e 2 S i <5

— 0 . 1 6 (s), C H 2 0.83 (m), 2.66 (m), 0 = C - C H 2 - 6 = 0 3.82 (s), C H 2 0 4.00 (q), C H 3 1 . 1 5 (t), P h 7 .50 (m) p p m .

X VII) Ethyl-[p- (p-chlorophenyl)dimethylsilyl-propyl Jbenzoylacetate [p- (p-ClC6H4)Me2Si(CH2)3C6H4C0CH2C02Et ]

[ p - ( p - C h l o r o p h e n y l ) d i m e t h y l s i l y l p r o p y l ] a c e t o p h e n o n e ( X I I ) g a v e t h e t i t l e c o m p o u n d in a r e a c t i o n s i m i l a r t o ( X I I I ) as a h e a v y oi l ( 6 5 % ) . n $ 1 .5305.

C 2 2 H 2 7 C 1 0 3 S i

F o u n d C 6 5 . 6 H 6 . 9 C18.7 m o l . w t . 403.0, C a l c d C 6 5 . 6 H 6 . 7 C18.8 m o l . w t . 4 0 2 . 9 9 .

I R (film) i / ( C = 0 ) (ester) 1740 (s) (keto) , 1682 (s) v ( a r o m a t i c ) , 1605 (s) v(MeSi), 1250 (s, sh), 830 (s) v (p-subst . ) , 790 (s) c m - 1 . N M R (CC14) M e 2 S i <5 — 0 . 1 7 (s), C H 2 0.34 (m), 1 .40 (m), 2 .34 (t), 0 = C - C H 2 - C = 0 3.43 (s), C H 2 0 3.70 (q), C H 3

0.83 (t), P h 7 .24 (m) p p m .

(D) Preparation of silylcoumarins X VIII) 7-Hydroxy-4-[y-dimethyl(fluoro)silyl]-propylcoumarin [7-H0C9HA02-4-(CH2)3SiMe2(F)]

C o n c e n t r a t e d s u l p h u r i c a c i d (5 c m 3 ) a t — 1 0 °C w a s a d d e d s l o w l y t o a coo led m i x t u r e o f r e s o r c i n o l (2.8 g ; 0.025 m o l e ) a n d e t h y l - [ y - ( d i m e t h y l ) p h e n y l -s i l y l e t h y l ] a c e t o a c e t ä t e ( X I I I ) (7.3 g ; 0.025 m o l e ) . T h e d e e p r e d c o l o u r e d m i x t u r e w a s k e p t a t — 1 0 °C f o r 24 h , a n d t h e n p o w d e r e d a m m o n i u m fluoride (5 g) w a s a d d e d t o i t . T h e r e s u l t i n g h e a v y oi l w a s w a s h e d s e v e r a l t i m e s w i t h c o l d d i o x a n b y d e c a n t a -t i o n a n d t h e n s t i rred a t r o o m t e m p e r a t u r e w i t h m i n i m u m a m o u n t o f p e t r o l e t h e r f o r ca. 3 h . T h e u n d i s s o l v e d m a t e r i a l w a s f i l tered off , a n d w a s re-c r y s t a l l i z e d f r o m b e n z e n e - h e x a n e . T h e t i t l e c o m -p o u n d w a s o b t a i n e d as c r e a m c o l o u r e d sol id ( 5 0 % ) m . p . 1 7 3 - 1 7 4 °C.

C i 4 H i 7 F 0 3 S i

F o u n d C 5 9 . 9 H 6 . 0 F 6 . 7 m o l . w t . 280.0, C a l c d C 5 9 . 9 H 6 . 1 F 6 . 7 m o l . w t . 280.0.

I R (nujo l ) »(OH) 3240 (m, b) v ( C = 0 ) , 1700 (s) v ( a r o m a t i c ) , 1605 (s) v(MeSi), 1260 (s), 850 (s) c m - 1 . N M R ( D M S O ) M e 2 S i Ö — 0 . 2 0 (s), C H 2 0.41 (m), 1 . 4 1 (m), 2.50 (m), C H 5.83 (s), P h 6.98 (m), O H 10.30 (s) p p m .

XIX) 7-Hydroxy-4-[d-dimethyl(fluoro)silylJbutyl-coumarin [7-H0C\H,02-4-(CH2)4SiMe2(F)]

I n a s imi lar r e a c t i o n as in ( X V I I I ) w i t h e t h y l -[ y - ( d i m e t h y l ) p h e n y l s i l y l p r o p y l ] a c e t o a c e t a t e ( X I V )

1144 B. N. Ghose • Carbonfunctional Organosilicon Compounds 1144

g a v e t h e d e s i r e d p r o d u c t ( 4 8 % ) m . p . 1 1 9 - 1 2 0 °C ( b e n z e n e - p e t r o l e t h e r ) .

C i s H i g F O s S i

F o u n d C 6 1 . 1 H 6 . 4 F 6 . 3 m o l . w t . 294.0, C a l c d C 6 1 . 2 H 6 . 5 F 6 . 4 m o l . w t . 294.34.

I R ( n u j o l ) v ( O H ) , 3 1 8 0 (m, b) v(C=0), 1 7 0 5 (s) v ( a r o m a t i c ) , 1 6 0 5 (s) v(MeSi) , 1268 (s), 850 (s) c m - 1 . N M R ( D M S O ) M e 2 S i <5 — 0 . 2 0 (s), C H 2 0.38 (m), 1 . 3 8 (m), 2 .48 (m), C H 5 .81 (s), P h 7.00 (m), O H 10.30 (s) p p m .

XX) 7-Hydroxy-4-[4'-dimethyl(fluorojsilylmethyl]-phenylcoumarin [7-H0C9H402-4-C6H4CH2SiMe2(F)-4']

A s i m i l a r r e a c t i o n t o t h a t i n ( X V I I I ) w i t h e t h y l -[ p - ( p - c h l o r o p h e n y l ) d i m e t h y l s i l y l m e t h y l ] b e n z o y l -a c e t a t e ( X V ) , g a v e a v i s c o u s oi l , w h i c h s o l i d i f i e d u p o n s t a n d i n g a t 0 °C. R e c r y s t a l l i z a t i o n f r o m b e n z e n e - h e x a n e g a v e t h e t i t l e c o m p o u n d ( 5 5 % ) m . p . 2 0 0 - 2 0 2 °C.

C i s H i 7 F 0 3 S i

F o u n d C 6 5 . 7 H 5 . 2 F 5 . 7 m o l . w t . 328.0, C a l c d C 6 5 . 8 H 5 . 2 F 5 . 8 m o l . w t . 3 2 8 . 4 1 .

I R ( n u j o l ) v ( O H ) , 3 1 4 5 (m, b) v ( C = 0 ) , 1 6 9 5 (s) v ( a r o m a t i c ) , 1 6 1 5 (s), 1600 (s) v(MeSi) , 1 2 5 0 (s), 8 5 5 (s) c m - 1 . N M R ( D M S O ) M e S i 6 — 0 . 1 0 (s), C H 2

2.00 (s), C H 5 .90 (s), P h 7.00 (m), O H 1 0 . 3 5 (s, b) p p m .

XXI) 7-Hydroxy-4-[4'-dimethyl(fluoro)silylethyl]-phenylcoumarin [ 7-ROC o>H\02-4-C a ( CH2) 2S iM e2(F)-4'j

E t h y l - [ p - ( p - c h l o r o p h e n y l ) d i m e t h y l s i l y l e t h y l J -b e n z o y l a c e t a t e ( X V I ) g a v e t h e t i t l e c o m p o u n d ( 5 8 % )

a s a h e a v y oi l , w h i c h s o l i d i f i e d a f t e r s o m e t i m e a t 0 °C, f r o m a n i d e n t i c a l r e a c t i o n a s i n ( X V I I I ) . m . p . 2 0 0 - 2 0 2 °C ( b e n z e n e - p e t r o l e t h e r ) .

C 1 9 H 1 9 F 0 3 S i

F o u n d C 6 6 . 6 H 5 . 5 F 5 . 4 m o l . w t . 342.0, C a l c d C 6 6 . 7 H 5 . 6 F 5 . 5 m o l . w t . 3 4 2 . 4 3 .

I R ( n u j o l ) » ( O H ) , 3090 (m, b) v ( C = 0 ) , 1700 (s) v ( a r o m a t i c ) , 1 6 1 0 (s), 1600 (s) v ( M e S i ) , 1 2 5 5 (s), 8 5 0 (s) c m - i . N M R ( D M S O ) M e 2 S i d — 0 . 1 8 (s), C H 2

0.63 (m), 2 .47 (m), C H 5 . 9 0 (s), P h 6 .95 (m), O H 10.38 (s, b) p p m .

XXII) 7-Hydroxy-4-[4'-dimethyl(fluoro)silyl-propyl) phenylcoumarin [7-H0Cc,H402-4-C<sHi(CH2)zSiMe2(F)-4']

A n i d e n t i c a l r e a c t i o n a s i n ( X V I I I ) w i t h e t h y l -[ p - ( p - c h l o r o p h e n y l ) d i m e t h y l s i l y l p r o p y l ] b e n z o y l -a c e t a t e ( X V I I ) g a v e t h e p r o d u c t ( 5 8 % ) m . p . 1 9 2 t o 1 9 4 °C ( b e n z e n e - p e t r o l e t h e r ) .

C 2 o H 2 i F O s S i

F o u n d C 6 7 . 3 H 5 . 8 F 5 . 1 m o l . w t . 356.0, C a l c d C 6 7 . 4 H 5 . 9 F 5 . 3 m o l . w t . 3 5 6 . 4 5 .

I R ( n u j o l ) v ( O H ) , 3 1 5 0 (m, b) v ( C = 0 ) , 1700 (s) v (aromatic), 1610 (s), 1600 (s) v(MeSi), 1260 (s), 8 5 5 (s) c m - i . N M R ( D M S O ) M e 2 S i d — 0 . 2 0 (s), C H 2

0.43 (m), 1 . 4 4 (m), 2 . 4 6 (m), C H 5 . 8 5 (s), P h 6 .95 (m), O H 1 0 . 3 7 (s, b) p p m .

P a r t o f t h i s w o r k w a s c a r r i e d o u t a t t h e U n i -v e r s i t y o f S u s s e x , E n g l a n d . I t h a n k P r o f . C. E a b o r n a n d D r . D . R . M . W a l t o n o f t h a t u n i v e r s i t y f o r u s e f u l d i s c u s s i o n d u r i n g t h e c o u r s e o f t h i s w o r k a n d l a b o r a t o r y f a c i l i t i e s .

[ 1 ] C . E a b o r n , B . N . G h o s e , a n d D . R . M . W a l t o n , J . O r g a n o m e t . C h e m . 6 5 , 1 6 9 ( 1 9 7 4 ) .

[ 2 ] C . E a b o r n a n d R . W . B o t t , i n A . G . M a c D i a r m i d ( e d . ) : O r g a n o m e t a l l i c C o m p o u n d s o f t h e G r o u p I V E l e m e n t s , V o l . 1 ; P a r t i , p . 4 0 9 , M a r c e l D e k k e r I n c . , N e w Y o r k 1 9 6 8 .

[3] J. W. Rayan, G. K. Menzie, and J. L. Speier, J. Am. Chem. Soc. 82, 3601 (1960).

[ 4 ] Z . V . B e l y a k o v a , M . G . P o m e r a n t s e v a , a n d S . A . G o l u b t s o v , J . G e n . C h e m . U S S R . 1 9 6 5 , 1 0 5 3 .

[ 5 ] K . A . A n d r i a n o v a n d N . V . D e l a z a r i , D o k l a d y A k a d . N a u k . S S S R . 1 2 2 , 3 9 3 ( 1 9 5 8 ) ; C . A . 5 3 , 2 1 3 3 ( 1 9 5 9 ) .

[ 6 ] J . L . S p e i e r , J . A m . C h e m . S o c . 7 4 , 1 0 0 3 ( 1 9 5 2 ) .