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A CONVENIENT PREPARATION OFα,α-DIPHENYLACETOPHENONEN. Sbarbati Nudelman a & A. A. Vitale aa Dept. de Quimica Organica, Facultad de Ciencias Exactas yNaturales, Universidad de Buenos Aires, 1428, Buenos Aires,ARGENTINAPublished online: 12 Feb 2009.

To cite this article: N. Sbarbati Nudelman & A. A. Vitale (1981) A CONVENIENT PREPARATIONOF α,α-DIPHENYLACETOPHENONE, Organic Preparations and Procedures International: TheNew Journal for Organic Synthesis, 13:2, 144-149

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!s, 3, C O C H j ) . -

6 . The cis a x i a l - e q u a t o r i a l r e l a t i o n s h i p f o r t h e hydrogens

a t t h e 1 and 6 p o s i t i o n s o f p u r i f i e d 1 w a s conf i rmed by

t h e magnitude of t h e i r c o u p l i n g c o n s t a n t (J = 4.03 Hz) a s

a s c e r t a i n e d by doub le resonance expe r imen t s . Composed of

1 3 .sharp l i n e s , t h e 13C NMR of - 1 is also i n harmony w i t h

t h e p r e s e n c e of a s i n g l e s t e r e o i s o m e r . W e a r e assuming

t h a t t h e bulky 3-buten-2-one s i d e c h a i n of 1 o c c u p i e s an

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

b i l i t y of a t r a n s e q u a t o r i a l - e q u a t o r i a l r e l a t i o n s h i p f o r

t h e 1 and 6 r i n g p o s i t i o n p r o t o n s o f A. 7. T h i s y i e l d of p u r e 1 r e p r e s e n t s a 57% recove ry o f t h e a-

v a i l a b l e 1 i n t h e mix tu re . W e have found t h a t a less con-

s e r v a t i v e c o l l e c t i o n of 1. by HPLC s e r i o u s l y compromises

i t s p u r i t y .

A CONVENIENT PREPARATION OF a.a-DIPHENYLACETOPHENONE

Submit ted b N . Sbarbati Nudelman" and A. A. V i t a l e 7 - i 7 i m r Y

Dept. de Quimica Organica F a c u l t a d de C i e n c i a s E x a c t a s y N a t u r a l e s Un ive r s idad de Buenos A i r e s 1428 Buenos A i r e s . ARGENTINA

Although s e v e r a l m e c h a n i s t i c s t u d i e s and s y n t h e t i c a p p l i -

c a t i o n s o f a l k a l i a r o m a t i c k e t y l ~ l - ~ have been r e c e n t l y pub-

l i s h e d , t h e r e have been n 3 f u r t h e r s t u d y of t h e r e a c t i o n o f

p h e n y l l i t h i u m w i t h ca rbon monoxide s i n c e t h e work of White-

144

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s i d e s , e t al.’

to be an i n t e r m e d i a t e b u t s e v e r a l mechan i s t i c q u e s t i o n s re-

mained unreso lved .

I n t h a t paper t h e benzophenone k e t y l w a s shown

As p a r t o f a d e t a i l e d i n v e s t i g a t i o n o f t h e mechanism of

t h e r e a c t i o n , w e have e s t a b l i s h e d c o n d i t i o n s which accoun t f o r

t h e t o t a l f a t e o f p h e n y l l i t h i u m and, s econd ly , minimize t h e

fo rma t ion o f by-products . Only f o u r p roduc t s were formed:

a,a-diphenylacetophenone ( I ) i s t h e major p roduc t , benzophe-

none (11) , benzoin (111) and a, a-diphenyl-a-hydroxyacetophenone

( I V ) . 0 OOH OOH

II I 0 II U II I

PhLi PhCCHPh2 + PhCPh + PhCCHPh + PhCCPh2

I I1 I11 I V

S o l v e n t and t empera tu re e f f e c t s , among o t h e r v a r i a b l e s ,

were s t u d i e d . The s o l v e n t s t e s t e d w e r e : d i e t h y l e t h e r , ~f-

hexane, t e t r a h y d r o f u r a n e and dimethoxyethane , b u t t h e b e s t

y i e l d s were o b t a i n e d u s i n g p h e n y l l i t h i u m as a f i n e powder,

w i t h no s o l v e n t . Some r e p r e s e n t a t i v e r e s u l t s are g a t h e r e d i n

t h e Table.

TABLE.- P roduc t Y i e l d ( % ) from S o l i d PhLi and COa

Temp. (OC) PhLi (mole) I I1 I11 I V

0 4 . 4 4 2 33 15 9 0 5.0 44 33 1 3 9

25 6 . 1 56 25 11 7 25 3 . 7 6 3 20 1 0 6 .5 60 4 . 2 70 19 7 3 60 4.9 78 14 5 2 - l lOb 5.0 94 1 .5 -

a) The y i e l d s r e p r e s e n t % conver s ion . b) 4.5% o f p h e n y l l i t h i - um w a s c o n v e r t e d t o t r i p h e n y l c a r b i n o l .

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A s it c a n be obse rved t h e conve r s ion to I i n c r e a s e s w i t h

t h e t empera tu re o f r e a c t i o n w h i l e t h e y i e l d o f 11 d e c r e a s e s ,

a s it h a s been observed i n d i e t h y l e t h e r s ~ l u t i o n . ~ The re-

a c t i o n s l e a d i n g to p r o d u c t s X I 1 and I V w e r e a l s o minimized a t

h i g h t empera tu res . All t h e r e p o r t e d y i e l d s w e r e o b t a i n e d by

g l p c ; f o r t h e r e a c t i o n s c a r r i e d o u t a t 60° and l l O o , I was a l -

so i s o l a t e d by s t a n d a r d t e c h n i q u e s .

I t i s wor th ment ioning t h a t t h e p r e v i o u s p r e p a r a t i o n s o f

I from benzoin6 ( y i e l d : 51%, 4 1 % o v e r - a l l s t a r t i n g from ben-

za ldehyde ) or from t r i p h e n y l e t h y l e n e 8 ( y i e l d : 59%, 35% ove r -

a l l from b e n z y l c h l o r i d e ) , are more l a b o r i o u s t h a n t h a t des -

c r i b e d h e r e . Fur thermore , t h e s y n t h e t i c c a p a b i l i t i e s o f t h e

a l k a l i a r o m a t i c k e t y l s are v e r y w e l l known;" t h e r e a c t i o n i s

now b e i n g examined i n an a t t e m p t t o i n t r o d u c e o r g a n i c g roups

b e f o r e t h e h y d r o l y t i c quenching. P r e l i m i n a r y r u n s w i t h b u t y l

are p romis ing b u t methyl i o d i d e t r e a t m e n t gave a m i x t u r e o f

p r o d u c t s as p r e v i o u s l y obse rved w i t h s imi l a r a n i o n s .

7a

9

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EXPERIMENTAL

Mel t ing p o i n t s are u n c o r r e c t e d . A l l compounds r e p o r t e d h e r e w e r e f u l l y c h a r a c t e r i z e d by m a s s spec t romet ry ( u s i n g a Var i an M a t CH7 s p e c t r o m e t e r ) , i n f r a r e d (de t e rmined on a P e r - k i n E l m e r 137 spec t ropho tomete r ) , u l t r a v i o l e t ( r e c o r d e d on a Beckman DK2A spec t ropho tomete r ) and n u c l e a r magnet ic reson- ance (de t e rmined on a Var i an A-60 s p e c t r o m e t e r ) s p e c t r o s c o p y and showed s p e c t r a l c h a r a c t e r i s t i c s c o n s i s t e n t w i t h t h e spec - t r a o f a u t h e n t i c samples . The g l p c a n a l y s e s w e r e c a r r i e d o u t on a 5830 Hewlet t -Packard G a s Chromatograph. Reac t ions invo lv - i n g p h e n y l l i t h i u m w e r e c a r r i e d o u t u s i n g s t a n d a r d t e c h n i q u e s f o r m a n i p u l a t i o n of oxygen and w a t e r - s e n s i t i v e compounds.

P h e n y l l i t h i u m was p r e p a r e d by a method adap ted from t h a t of S c h l o s s e r and Ladenberger ;12 no d i f f e r e n c e was obse rved by u s i n g f r e s h l y p r e p a r e d b u t y l l i t h i u m o r t h e commercial s o l u - t i o n i n E- exane. Carbon monoxide was g e n e r a t e d by s t a n d a r d proceduresSb and p u r i f i e d by p a s s i n g through a column o f po- t a s s i u m hydroxide and t h e n bubb l ing through a s o l u t i o n of ben- zophenone k e t y l i n t o l u e n e .

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Reaction of Phenyl l i thium with Carbon Monoxide.- The phenyl l i -

thium contained i n a tube capped with a No-air s topper w a s ex-

posed to carbon monoxide (1 atm p r e s s u r e ) . The white s o l i d

turned immediately t o pink, then to red and when t h e gas ab-

s o r p t i o n had ceased was a brownish purp le powder. n-Undecane

was added as i n t e r n a l g l p c s tandard , then g-hexane to form a h o -

mogeneous suspension (10 m l ) . A 1 . 0 m l a l i q u o t of t h e r e a c t i o n

mixture w a s quenched with w a t e r , e x t r a c t e d wi th e t h e r and t h e

d r i e d (MgS04) e t h e r l a y e r was analyzed by glpc.

I s o l a t i o n and Charac te r iza t ion of t h e Products.- The remaining

s o l u t i o n was worked up i n a s i m i l a r way and t h e e t h e r l a y e r

w a s d i s t i l l e d a t reduced pressure . The white r e s i d u e w a s

t r e a t e d with methanol and t h e c r y s t a l s c o l l e c t e d . A y i e l d of

60% of I , mp. 137' was obta ined from t h e r e a c t i o n mixture .car-

r i e d o u t a t 60°. The methanolic s o l u t i o n w a s passed through

a column of s i l i c a g e l with benzene-methanol mixture a s e l u e n t .

F r a c t i o n s conta in ing I1 and I11 were collected and charac te r -

i z e d by t h e i r mp., s p e c t r a and t l c behaviour. Comp. I V i s

produced only i n small amount and w a s i d e n t i f i e d by glpc-ms.

Product Balance by g1pc.- The r e a c t i o n mixture w a s analyzed

by g lpc on a 3% SE 30 on Chromosorb W column a t 50-250°.

t h i s column benzoin and b e n z i l have t h e same r e t e n t i o n t i m e

b u t only benzoin was i s o l a t e d by column chromatography and

f u l l y charac te r ized .

Standard Prepara t ion of I.- n-Butyll i thium ( 1 0 m l of a 1 . 2 N

hexane s o l u t i o n ) was t r a n s f e r r e d by a s y r i n g e to a 20 m l cen-

t r i f u g e tube ( n i t r o g e n atm) conta in ing s e v e r a l g l a s s p e a r l s ,

and capped wi th a No-air s topper . Iodobenzene (1.6 m l ) w a s

On

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added dropwise a n d PhLi p r e c i p i t a t e d as w h i t e c r y s t a l s , which

w e r e t h r i c e washed w i t h fi-hexane added by a s y r i n g e a n d dr ied

a t 60° and 1 0 mm Hg p r e s s u r e .

c a r b o n monoxide (1 a t m p r e s s u r e ) w a s p a s s e d t h r o u g h a l e n g t h o f

t y g o n t u b i n g and hypodermic n e e d l e . F a s t g a s a b s o r p t i o n o c u r r e d

i n t h e f i r s t 1 0 m i n t t h e n i t s lowed and c e a s e d c o m p l e t e l y ( 8

mmole of CO) i n 4 h r . The r e s u l t i n g r e a c t i o n m i x t u r e w a s a l -

lowed t o cool t o room t e m p e r a t u r e , n e x t i t w a s s u s p e n d e d i n ;-

hexane (10 m l ) , h y d r o l y z e d w i t h w a t e r ( 5 m l ) , e x t r a c t e d w i t h

d i e t h y l e t h e r a n d d r i ed over magnesium s u l f a t e . D i s t i l l a t i o n

o f t h e e t h e r a t 30° and r e d u c e d p r e s s u r e r e n d e r e d 1 . 0 3 g ( 9 4 %

y i e l d ) o f I , c r y s t a l l i z a t i o n f rom m e t h a n o l gave mp. 137O.

Acknowledgements.- The a u t h o r s are i n d e b t e d t o t h e C o n s e j o

N a c i o n a l d e I n v e s t i g a c i o n e s C i e n t i f i c a s y T e c n i c a s ( A r g e n t i n a ) ,

t o t h e SECYT ( A r g e n t i n a ) a n d t o t h e O r g a n i z a t i o n of American

S t a t e s f o r f i n a n c i a l s u p p o r t . UMYMFOR ( A r g e n t i n a ) is acknow-

l e d g e d f o r t h e g l p c a n d m a s s s p e c t r a .

The t u b e w a s h e a t e d a t llOo and

1.

2 .

3.

4 .

5.

6.

7.

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(1956): 0. Halpern and C. njerassi , J. Am. Chem. SOC. , - 81, 493 (1959).

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pounds", M c - G r a w H i l l , N e w York, N. Y . , 1969, C h . 7. 12. M. Sch losse r and V. Ladenberger, J. Orqanomet. Chem., 2,

193 (1967).

AN IMPROVED PREPARATION O F CORONENE

Submitted b A. G. HolDa and E. J. Eisenbraun* d Department of Chemistry Oklahoma S t a t e Un ive r s i ty S t i l l w a t e r , OK 74078

Syn thes i s of coronene i s g e n e r a l l y on a mg scale. Our

a t t e m p t s t o i n c r e a s e t h e scale w e r e f r u s t a t e d u n t i l w e developed

a h e a t e r and improved glassware' which enabled s u c c e s s f u l l y

c a r r y i n g o u t t h e , r e a c t i o n a t t h e r e q u i r e d temperature. Pre-

0 2 v ious ly r epor t ed y i e l d s of coronene were 66% (mp. 425-428 )

and 73% crude with 18% p u r i f i e d . We c o n s i s t e n t l y ob ta ined

pure coronene i n 80% y i e l d , mp. 434-438O (uncorr . ) on a gram

scale.

I1 EXPERIMENTAL I

Melting p o i n t s w e r e determined on Mel-temp c a p i l l a r y m e l t - i n g p o i n t appa ra tus w i t h a 90-510° thermometer from H-B i n s t r u -

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