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-,

1871 (196S).1
lRcpriated lroo thc tournrl ol the Aqcriceo Cbeoicd Society,91,
lg0g by thc Aoericao Cheoicd Socicty rnd reprintcd by perrnirsioo ol thc copyright ottlc(.
Copyright

Reactionof Lithium Dialkyl'and


Diarylcuprateswith OrganicHalides

SanFilipPo,Jr.,
WilliaryF. Fischer,Jr.,Joseph
GeorgeM. Whitesides,
RobertW. Bashe,ild HerbertO. House
Reactionof Lithium Dialkyl- and Diarylcupratesw'ith
OreanicHalides''
Filippo. Jr.,3
George NI. Whitesides, lVilliam F. Fischer, Jr.,3 Joseph San
Robert W. Bashe, and Herbert O' House

ContributionfromtheDepartmen|ofChemistr-I.'
02 I 39'
MassacltttsettsInstitute of Technolog'" Cambridge' Massachusetts
Receiced Februurv 7, 1969

(R,,CuLi)react with aryl iodides in ether solution by competing


Abstract: Lithium diaikyl- or diarylcuprates product
meral-halogen e x c h a n g e a n d c o u p i i n g r e a c t i o n s . U s i n g a p p r o p r i a t e r e i l g e n t s .h i g h y i e l d s o f t h e c o u p l e d
e x c h a n g e t o p r o c i e d t o c o m p l e t i o n i n t h e p r e s e n c eo f a n
R-Ar can be obtained by allowing tt. m e r a l - h a l o g e n
s p e c i e sp r e s e n t . i ns o l u t i o n w i t h n i t r o b e n -
e x c e s so f R , : C u L i , a n d o x i d i z i n g t h e r e s u l t i n gm i x t r . r r eo f o r g a n o m e t a l l i c
z e n c o r o x y g e n . T h i s r e a c t i o ns e q u e n c e w o r k s w ' e l l w i r h l i t h i u m d i - n - a l k y ' l -a n d d i a r y l t ' t l p r a t e s ; i t f a i l s w i t h d i -
r e a c t w i t h a r . " - li o d i d e s o n l y b y m e t a l -
s e c - a l k y l -a n d d i - l - a l k y l c u p r a t e s . A l t h o u g h m o s t a l k y t l i t h i u m r e a g e n t s
w i r h c o p p e r . s m o o t h l y converts aryl iodides to ar-vlmethanes'
halogen exch.nge, methyllithium. uncompiexed
o l i r h i u m d i a l k y l - a n d c t i a r y , l . u p r " , . w
s i r h r r l , ( r i h a l i d e s a p p c a r s t o t a k e p l a c e w i t h o u t s i g n i f i c a n tm e t a l -
Coupling
d i p h c n y l c u p r a t e w i t h ( - ) - ( R ) - 2 - b r o m o b l t t l t n e o c c t t r sw i t h t h e p r e -
h a l o g e ne x c h a n g e . T h e r e a c r i o no f l i t h i u m
< j o m i n a n ti n c e r s i r no f c o n f i g u r a r i o n( 8 4 - 9 2 ' T ,s r e r e o s e l e c i i u i r e y lx p e c t e do f u n S r 2 - l i k e d i s p l a c e n r e n t ' ,c. o u p l i n g
halides
r c a c t i o n si n l . o l v i n ga n r r - a l k y l h a l i d ei i s o n c r e u c t i o n p a r t n e r iroceed in high yielcl: thost invohing r-alkyl
d i - n - a l k y l - ,r 3 i - s e c - a l k y .al n
- ,d d i - r - a l k y l c o p p e r
r e i l g e n t su l t c o i p l e with n-alkyl halides' A number of
fail. Lithium
couplingreactions
p r e p a r a t i o n sf o r r c p r e s e n t a r i v e c o p p e r ( l ) a r e c o m p l e x e sa r e d e s J r i b e d .a n d t h e s e n s i t i l i t y o f t h e
o [ p r e p a r a t i o n o f t h e a t e c o m p l e x .t o t h e n a r u r e o f t h e s o l v e n t .a n d t o t h e p r e s e n c eo f l i t h i u m h a l i d e s '
to the merhod
t r i a l k y l p h o s p h i n e sa. n d d i a i k y l s u l f i < j e isn s o l u t i o na r e d i s c u s s e d '

or- s i u m r e a g e n t sa r e r e l a t i v e l y u n r e a c t i v et o w a r d s i m p l c
A b r o a d l y a p p l i c a b l ep r o c e d u r ef o r c o u p l i n g t h e
ll g a n i c m o i e t y o f a n o r g a n o m e t a l l i cr e a g e n tw i t h e l k y l a n d a r y l h a l i d e s : t h c i r r e a c t i o nw i t h a c t i v a t e dh a -
t h a t o i a n o r - q a n i ch a l i d e w o u l d b e a u s e f u lm e m b e ro f l i d e s a g a i n i e a c l st o n r i x t u r e so f p r o d u c t s . T ' EO r g a n o -
t h e c l a s s o f r e a c t i o n s a v a i l a b l e f o r t h e s y n t h e s i so [ z i n c a n c lo r g a n o a l u m i n u mc o m p o u n d se x h i b i t l o w r e a c -
carbon-carbonc bonds. Un[ortunaiely'the com- t i v i t y t o w a r d, € . 8 . , n - a l k y l h a l i d e s ' A t p r e s e n t ' t h c
(l) s t r u c t u r a lf a c t o r sr e s p o n s i b l ef o r l o w n u c l e o p h i l i c i t yo f
R M + R , X _ > R _ R ,+ V I X
t h e s e o r g a n o m e t a l l i cr e u g e n t st o w a r d c a r b o n a r e n o t
m o n l y e n c o u n t e r e do r g a n o m e t a l l i cd e r i v a t i v e so [ t h e e n t i r e l ye v i d e n t .
ma i n gr oup m et al s a p p e a r to b e u n s i i ti s fa c to r yas rea- I n c o n t r a s t . o r g a n o m e t a l l i cc o m p o u n d s c o n t a i n i n g
g e n t s lor ef f ec t in g th e fo rm a ti o n o f c a rb o n -carbon carbon-copper(l)bonds provide a class of reagents
b o n d s b y n u c l e o p h i l i c d i s p l a c e m e n ta t a c a r b o n - w h o s eu s e i u l n e s isn c o u p l i n g r e a c t i o n sw i t h o r g a n i c h a -
h a l o g e nb o n d . A l t h o u g h o r g a n o l i t h i u m r e a g e n t sa r e l i des has beenampl y demonstrl ted i n certai nspecialized
s t r o n g l y b a s i c ,t h e y a p p e a r t o b e o n l y w e a k l y n u c l e o - ci rcumstances. i trut reacti on of copper(l ) acet ylides
philic ioward carbon: reaction of an organolithium w i t h a c e t y l e n i c , ea r o m a t i c . r 0v i n y l , [ a ' b a n d a c y F r " h a -
i o * p o u n d w i t h a n a l k y l o r a r y l h a l i d ei n h y d r o c a r b o n . , G r i g n a r dR e a c t i o n so f N o r r -
o r..i h. r s olut ions u s u a l l y l e a d sto m i x tu re so f products ( 7 ) N I . S ' K h a r a s c l ra n d O . R e i n m u t h '
I n c ', Nerv York' N' Y" 19)l'
metallic S u b s t i t n c c s , "P r e n t i c e - H a t t ,
d e ri v ed t ' r om c om p e ti n g m e ta l -h a l o g e n e x c h ange.ta C h a p t e r1 6 .
m e t a l a t i o n , si 3 e l i m i n a t i o n ,a n d c o u p l i n g ,w i t h t h e l a s t ( 8 ) N o r m a n t h a s r e p o r t e d t h a t u s e o f h e x a m e t h y l p h o s p h o r a m i d 'ct s
to
r e a c t i o na p p a r e n t l yp r o c e e d i n ga, t l e a s ti n p a r t , t h r o u g h s o i v e n rf o r t h e r e a c t i o no f a l k y l h a l i d e sw i t h G r i g n a r d r e a g e n t sl e a d s
generalin'
s y n t h e t i c a t l yu s c f u I y i e t d so f c o u p l e d p r o d u c t s ; h o w e v e r ' t h e
a complex free-radicalmechanism'6Organomagne- o [ t h i s s o l v c n te f f e c ih a s n o t y e t b e e nd c m o n s t r a t e d : c f ' H ' N o r m a n t '
A n g e wC. h e n t . l n t .E t t E . n g ! . , - 6 , 1 0 ' 1( 16 9 6 7 ) ;J ' F ' N o r m a n t ' B u l l ' S o c
( l ) s u p p o r t e db y c r a n t s c P - 2 0 1 8 a n d G P - i 2 6 6 f l r o m t h c N a t i o n a l
C h i m .F r . , 1 8 8 8( 1 9 6 3 ) .
S c i c n c cF o u n d a t i o n . (1961);
( 9 ) ( a ) G . E g l i n t o na n d W ' N l c C r a c ,A c ! c a nO' r g ' C h e m " 4 ' 2 2 5
( 2 ) S u p p o r t e c bi y R c s c a r c hG r a n t N o . A F O S R - 6 8 ' 1 5 1 8l r o m t h e
S c i e n c e s ,A i r F o r c e O f f i c eo t ' s c i e n t i f i c R e s e a r c h ' ( b ) F . B o h l m a n n , H ' S c h d n o l o s k v ,E ' I n h o f f e n ' a n d G ' G r a u ' C h e n t '
D i i c c t o r a i eo f C h e m i c a t
( 3 ) N a t i o n a l I n s t i t u t e so f H e a l t h P r e t j o c t o r r lF c l l o w , 1 9 6 6 _ 1 9 6 9 . \ir.,91,794 (1961); (c) R. F' Curtis and J' A' Tavlor' Tetrahedrort
G i l m a n , O r g . R e a c t t o n s , 6 , 3 (
3 1 9 9 5 t ) ; D . E . L ett.,29l9(1968).
i , f i n . G . J o n e sa n d H . (1961); ( t t i l f a ) C . E " C a s t r o , E . J ' G ' r u g h a n ,a n d D ' C ' O r v s l e y 'J ' o r z
A p p i c q u i s ta n d D . F . O ' B r i c n , J . A r n e r . C h e n t .S o c . , 8 5 . 7 4 3 ibid"28'
W i n k l e r , i b i d . , E E ,9 U ' 9 6 9 ( 1 9 6 6 ) ' C h e m . , 3 l ,- t 0 7 1( 1 t 6 6 ) ; ( b ) C . E . C a s t r oa n d R ' D ' S t e p h e n s ' ( 1 9 6 - < ) ;
H. L S. Winklcr and H. ( 1 9 6 3 ) :( c ) R . E . D e i s y a n d s . A . K a n d i l , i b i d . , 3 0 . 3 8 5 7
(5) W. l(irmse, " C a r b c n e C h e m i s t r y , " A c a d c m i c P r e s s N
' e w Y o r k ' 2 1 6 3
(d) R. E. Atkinson, R. F. iurtis, and J' A' Taytor'J' Chem'Soc" C"
N.Y.,1964;G.l(iibrich,Angew'Chem'Int.Ed'Engl',6,'ll(1967)'and J' A'
i ; ' s ( t s o z l : ( e ) R . E . A t k i n s o n , R ' F ' C u r t i s ' D ' M ' J o n e s 'a n d
r e f e r e n c e si n e a c h . 718(1967)'
( 1 9 6 7 ) ; H ' R ' W a r d T a y l o r , C h e m . C o m m u n . '
( 6 ) H . R . W a r d , J . A m e r . C h e m 'S o c ' , 8 9 , 5 5 1 7
( t t l t o l J . B u r d o n ,P . L ' C o c ' C . R ' M a r s h ' a n d J ' C ' T a t l o w ' C h e n t '
and'R.G.Lawler,ibi(t.,89,5518(1967);C.G'screttrsandJ'F' V' I'
C o m n t u n . ,r z s s t l 9 6 i l ; ( b ) L . Y u U k h i n , A ' M ' S l a d k o v ' a n d
E a s t h r m ,i b i d . ,8 8 , 5 6 6 8( 1 9 6 6 ) .

lVltitesitles. et ttl. I Lirhiunt Diulk-t'l- untl Diurylcuprute Reuctiltns


4872
l i d e sh a s b e e nu s e ds u c c e s s f u i li yn f o r m a t i o n o f a b o n d s . t h e s i g n i f i c a n ti n c r e a s ei n t h c -y i e l d o f a r y m e t h a n e
a n d a n u m b e r o f t h e r m a l l y s t a b l e a r y l c o p p e r ( l )r e a - .h-
s e r ' e d o n o r i d a t i o n o f t h e r e a c t i o nm i x i u r e i n d i c a t c s
g e n t sh a v e b e e no b s e r v e dt o c o u p l e w i t h a r y l . ' a l k y l .a n d
t h a t a t l e a s tt w o r e a c t i o n sa r e t a k i n g p l a c ei n s o l u t i o ' :
a c y l h a l i d e sr.' rr' r u n f o r t u n a t e l y t. h e u s e f u i n e sosf m o s t a r e a c t i o n l e a d i n g t o c o u p r i n g( . q 2 o r 4 ) , a n d
u n c o m p l e x e da l k y l c o p p e r ( l )r e a g e n t si n c o u p l i n g r e e c - anothcr
r e a c t i o ni n v o l v i n g m e t a l - h a l o g e ne x c h a n g eb e t w e e n
tions is limited, since these compounds decompose thc
a r y l i o d i d e a n d r h e c u p r a t eI w h i c h c o m l e t e s w i r h ( r r r
t h e r m a l l ym o r e r a p i d l y t h a n t h e y r e a c tw i t h o r g a n i ch a - p r e c e d e s t) h e c o u p r i n g r e a c r i o n( e q 3 ) . T h e
l i d e s . H o w e v e r , p r e v i o u sw o r k w i t h o r g a n o J o p p e r ( t ) oxici:rrirc
c o n v e r s i o no f a " m i x e c i " l i t h i u r p h " n y l m e t h y l c u p * r c
c o n r p o u n d s h a s d e m o n s t r a t e dt h a t f o r m a t i o n o f I : I ( r e p r e s e n t e sd c h e m a t i c a l l yb y 2 ) t o t o l u e n e
" a t e " c o m p l e . r e s ro{ f t h e s er e a g e n t sw i t h on oxidation
organolithium
a n d o r g a n o m a g n e s i u nrre a g e n t ss i m u l t a n e o u s l yr e s u l t s P h l + ( C H ' ) , C u L i- - > PhCHr * (CH,Cu) * Lit rlr
i n a s t a b i l i z a t i o no f t h e c a r b o n - c o p p e r ( l )b o n i t o w a r d I
t h e r m a ld e c o n r p o s i t i o a n n d i n a n i n c r e a s ei n t h e n u c l e o - P h l + ( C H , I : C u L i= - l P h ) ( C H r ) C u L *i C H r l (-rr
p h i i i c r e a c t i v i t yt o w a r d c a r b o n o f t h e o r g a n i c m o i e t y I 2
b o n d e d t o c o p p e r .r . i1, 6 T h u s , l i t h i u m O i i t t y t - o r d i - 2 + CHII --+ phCHr * (CHrCu) {rr
a r y lc upr at esap p e a re dto b e o f i n te re s t , .og.nts for
2 * O: --> PhCH3 (_i)
c a r r y i n g o u r t h e d i s p l a c e m e not f h a l o g e" tna t c i r b o n b y
o r g a n i cg r o u p s . ( e q 5 ) i s i n a c c o r d w i t h t h e r e s u l t so f p r e v i o u s
studics.r,
T h i s p a p e r r e p o r t s t h e r e s u r t so f o u r e x a m i n a t i o no f l n a n e f f o r t t o e s t a b r i s ht h e m o s t s a t i s f a c t o r ye x p c . -
t h c ' r e a c t i v i t yo f l i t h i u m d i o r g a n o c u p r a r etso w a r d o r - m e n t a l c o n d i t i o n s f o . r c o u p _ r i nogr g a n o c o p p e r e ' g e
r[:
g a n i c h a l i d e s . T h e r e s u l t so f s i m i l a r ,i rn d e p e n d e n t w i r h a r y ' lh a l i d e s .a n d t o d e f i n et h e i f f e c t o i t t . r e r m i n u i
in-
' e s t i q a t i o n sh a v e r e c e n t l yb e e nd e s c r i b e db y C o r e y a n d o x i d a t i o n o n t h e y ' i e l do f c o u p l e c p l r o d u c t ,w e h a v c e r -
P o s n e r , 1a7n d s e v e r a al p p r i c a t i o n o s f t h e s ec b u p r i n gp r o - a m i n e dt h e r e a c t i o n so f l i t h i u r ' d i m e t h y l c u p r a taen d
rc_
c c d u r e sh a v e b e e n r e p o r t e d s i n c e t h e o r i g i n . i a . i i r i p - l a t e d s u b s t a n c e sw i t h i o c l o b e n z e n ea n d l - i o d o n ' p r r -
t i o n s r. , t h a l e n ei n d e t a i l .
T h r e e p r e p a r a t i o n sf o r s o l u t i o n sc o n t a i n i n g, . l i t h i u n r
Ii esults ..
d i n r e t h y l c u p r a t e " a r e a v a i l a b l e ( e q 6 - g ; .r i : , , T h c s e
I leac t ion of i \Ie th y tc o p p e r(I) D e ri v a ti v e srvi th A ryl
:C H rLi * C uX -_> (C H ,r):C uLi + L iX (r,r
I o d i d e s . P u r e l i r h i u m d i m e t h y l c u p r a r e( l ) c a n
be I
pr epar ed b, v di s s o l v i n g h a l i d e -ti e e n re th y l copper(I)
in C H ,Li + C H ,,C ->
u
halide-free m e r h y l l i t h i u ms o l u r i o n . r ; R e a c t i o no f t h i s (C H ,r)rC u Li (-/t
n u r t e r i a lw i t h a r y l i o d i d e s s u c h a s i o d o b e n z e n eo r l - I
r o d o n a p h t h a l e nien e t h e r s o l u t i o n a t r o o n r t e m p e r a t u r e l C H 3 L i* L . C u X- _ _ +( C H , ) : C u L i .+L t i X (s)
t' or per iodsof 8 to 2 -t h r, fo l ro w e d b y h y d ro r ysi s,yi el ds p r e p a r a t i o n sd i f f e r i n c o n v e n i e n c ae n d i n t h e p r o p e r t i es
t h c 'c o r f € s p o n d i n g a r y l m e t h a n ew i t h a m a x i m u m c o n - o f t h e r e s u l t i n g o r g a n o m e t a l l i cr e a g e n t s . T h e r n ( ) s r
r e r s i o n o i 3 0 - 5 0 1 [ b a s e do n r h e a r y l i o d i d e . a m e n a b l e t o l a r g e i c a l e s y n r h e t i ci p p l i c a t i o n i s t h c
If the
o r g a n o m e t a l l i cc o m p o n e n t s o t ' t h e r e a c t i o n m i x t u r e s d i r e c t r e a c t i o n b e t w e e n n r e t h y l l i t h i u m a n d c o p p e r (I l
; 1 r c o x i d i z e d r r p r i o r t o h y d r o l y s i s ,t h e y i e i d o f a r y r - b r o m i d e o r i o d i d e s u s p e n d e di n e t h e r( e q 6 ) . T h e c o n r -
n r e r h r n e i s i n c r c a s e dr o 6 0 - 7 0 % ( T a b l t s I a n d r i l . p o s i t i o n o f t h e s e o r g a n o m e t a l l i sc o l u t i o n si s n o t w c l l
T h e s eo b s e r v ' a t i o nssu g g e stth a t l i t h i u m d i m e t h y l c u p r a t e d e f i n e d o n t w o c o u n t s : f o r o n e . t h e , vc o n t a i n v a r i u b r e
r s r e l c t i v e t o w a r d c a r b o n - i o d i n eb o n d s i n a s e n s e a m o u n r so f l i t h i u m h a l i d e :f o r a s e c o n d t, h e y a p p e a r[ ( )
that
leeds to carbon-carbon bond formation. However, b e s i g n i f i c a n t l ym o r e a c t i v ci n c e r t a i nr e a c t i o n st h a n s o -
CorshkovZ , h . O r g . K ! i y . r O , ? t t l 9 6 g ) ; C h e m .A b s n . , 6 g , 7 S 6 2 1 l 9 6 g ) ; l u t i o n s c o n r a i n i n gp u r e l i t h i u m d i m e t h y l c u p r a t e (ttd,,
rcrA. It. Sladkov i nfra). P reparati on of pure ri thi um di methyr cupr at eb, ,
C h e m .A b s r r . ,6 7 , 91317<6{1, l.9. _ 6R 7 ).._ G o l . d iZn hg ., O r g . K t i m . . f , ' t j t S ( 1 9 6 7 ) ;
( l : ) ( a ) H . C r l m a n . a r r tJJ. M _ S r e a c t i o n o f m e t h y l l i t h i u n rw i t h a s l i g h t . * i . r s - o f p u r . ,
. t r a l c y , R e c . T r a cC . hirn.pa1,s_Bas,55,
s l l ( 1 9 1 6 ) ;( b ) A . E . J u k c s ,S . s . D u a , a n c rH . c i r n ' * ,
l . d r "gSainr e o .^pepraorrd. ,
m e t h y l c o p p e r( e q 7 ) l e a d s t o l i t h i u m h a l i d e f r e e s o r u -
C h e m . .1 2 , P l . l . P . l . l ( 1 9 6 g ) ; ( c ) A . C a i r n c r o s sa n d t i o n s c o n t a i n i n g a n o r g a n o c o p p e rr e a g e n to f w e l l - c l c -
W. n.
J ' ' l r n e r ' C h e m .s o c . , 9 0 , 2 r g 6 ( r 9 6 g ) ; ( d ) M . N i l s s o n
ando. wenner- f i n e d s t o i c h i o m e t r y ,b u t i s r e l a l i v e l yi n c o n v e n i e n itn i r s
s t r o m . T e t r a h e d r o nL e t t _ 3 3 0 7 0 9 6 3 ) ; ( e ) f o r a r e c e n t . * i " r u ,
\ r l s s o n , S r e n s k .K e t n . T i t l s k i . ,9 0 , l 9 Z s e e N I.
i t S O a t ; C h e m .. l b s r r . . , 6 9g, l 4 5 r e q u i r e m e n rt h a t m e t h y l c o p p e r ( rb) e p r e p a r e di n a s e p -
rI963).
( l l ) E v i d c n c ef o r c o u p r i . g b e r r v e eanr y r c o p p e r ( r ) a r a t e s t e p . R e a c t i o n o l ' m e t h y l l i t h i u mw i t h a n e t h c r -
c o m p o u n d sa n d a r v r
h ' r l i d e sh ; r s b c e n f o u u d i r r s t u c i i e so f t t r e u r i - a n
,.".iion, i;;';r."i:
s o l u b l ec o p p e r ( l ) h a l i d et r i a l k y l p h o s p h i n eo r b i s ( d i a l k lI
F . r n r r . C h e m . R e c . , 6 4 , - 6jl t 1 9 6 4 ) ; ( b ) C . B j d r k l u n c l s u l f i d e ) c o m p l e x r e s u l t si n a s o l u t i o n c o n t a i n i n g t i . , .
,rnJ.vt Nilsson,
Tetrahedron L e t t e r s , 6 7 5( t 9 6 6 ) ; M . N i i s s on , i b i d . , 6 7 9( 1 9 6 6 ) ,( c )
L c n i n a n d T . C o h c n , i b i d . , 1 5 3 1( 1 9 6 5 ) ; ( d ) M . A. H. p h o s p h i n eo r s u l f i d el i g a n d a n d l i t h i u m h a l i d e i n i a c i -
Nilsson. Aua Chem.
S c a n < l .l Z , , 5 3 7( 1 9 5 8 ) ;2 0 . . l 2 j ( 1 9 6 6 ) . t i o n t o a l i t h i u m d i n r e t h y l c o p p ea r te complex (eq E)
(l.l) W. Tochrcrmann
l A n z e w . C h e m . I n t . E c t .E n g l . , S , 3 5 t ( 1 9 6 6 ) l
rnd C. Wittig [euarr. Rec.(London),20, tgt
f l S e " 6 ) l ' h a v pe r o v i d e d (20) No firm evidcrrcc is availablc co'cerning
r e \ l c _ \ ' vosI t h e p r o p e r t i c sa n d r c . a c t i o n so f a t e t h e s t r u c r u r c (s ) o r
aoaptr*ar.---' extenr(s) of aggrc-gation ot' thc species reprcscntcd
(l-i) H. O. Housc.rndW. F. i n t h i s p a p c r . rr
F i s c h e r ,I r . , J . O r g . i h e m . , 3 3 , 9 . 1 9 R , : c u L i a n d R : C u L i ' p R r .
t t 9 6 8 ) ; H . O . H o u s c .W . L . R c s p e s sa, n d C . V B y a n a l o g y r v i r i r t h e n r . . o . p r " * c s f o r n r ec
f V i r i , " r i J . r , ' i a i . f .l ,t , b c n v e e n m e t h . ' - l l i t h i u m a n d
lllS (1966)a , n d r e l ' c r e n c ei sn e a c h . either dimcthylmagncsium or dimethri-
( 1 6 ) H . G i l m a n . R . C . J o n c s .a n c l zinc,:t the "lithium dimcthl lcuprarcs" probably consisr
L. A. Woods, ibid., li, 1630 or ,.i.,iri.Jr.,,
( I951). m c r a l c l u s r e r s r v i r h l i r c c - c c . t c rcd bridgirrg alkyl groups. prclimi.:rr,.
low-tempcraturc nmr studics of coppcr . o , r r p l e x c s a r e c o r l s l s t c ril
(1. !9! i6) 7 )E; , J . C o r e ; -r l d G . H . p o s n e r ,J . A n t e r . C h e m .S o c . ,E 9 , 3 9 i l w r t h s u : h a p i c r u r e a n d a l s o s u g g c s r t h c e" xt "i s t c n c c o f
9 0 . 5 6 1 5( 1 9 6 8 ) . higher complcrc:
( 1 8 ) G . B i j c h ia n d J . A . C a r t s o n , h a v i n g c o m p o s i r i o n , e.g.. ( R C u ) . ( R L i ) 1 . : : Both chcmical and spcctro-
i b i c t . , 9 05, l l 6 i l 9 6 g ) ; E . J . C o r e y , s c o p i c e v i d c n c c indicate q u a l i t a r r v c l y
J . A . K a r z e n e l l c n b o g c rar ,n d C . H . p o s n e r ,i b i ( I . , g g , . t 2 4 5( rhat trialkylphosphines in solurio.
1967);E. J. o('copper are complexcs are associatcd rvith thc mctal clusters,
C o r e y ,J . A . l ( a r z e n e l l c n b o g eN n ,. W . G i i m a n , S . A . R o m a n ,a n d but ag;rrr..
E r i c k s o n ,i b i d . , 9 0 , 5 6 t8 ( t S O S l . B . W . n o s t r u c t u r a l i n f o r m a t i o n c o n c c r n i n g t h e d e t a i l s o f t h i s a s s o c r a r i o n. r r c
( 1 9 ) G . M . \ \ ' h i t c s i d c sJ, . _ S a nF i l i p p o , a t h a n d . : r
J r . , C . p . C a s e y ,a n d E . J . (21) T. L. Brown, Accounts Chent. Res., l,2j (196g).
P r r n e kJ, . A m e r . C h e m .S o c . ,g 9 , S I O : i i S O Z t .
(22) l. SanFilippo, Jr., unpublishcd studies.

Josynr,l ol' t/re .lrtrari<'uttChentiutl Strcietv 9l ; t7 Augusr I J, 1 9 6 9


Table I. Reactionof Lithium Dialkylcuprateswith lodobenzene"
Recovered
- iodo-
Other solution Reaction benzene, - Y i e l d , 7 o '-
RrCuLi components(concn,/v/) time, hr 7l Product Hy drolysisOxidation"

l. (CHr}CuLid I 95 Toluene 3
4 75 6 l6
1{
l5 36 AA 48
42 <l 16 70
cHrl-i (0.1) I .l 4
2. (CHr)zCuLid
4 ll 35
l5 25 65
A'l
+z .18 7L
3. (CHrhCuLid LiBr (1.0) I -l -[
l5 29 60
4. (CHrlCuLid L i r( r . 0 ) I <l <l
34 l6
5. (CHr)rCuLid ( r r - C r H g ) r P( 0 . 5 ) I 20 9l
4 l8 92
6. (CHr}CuLi' Lit (0.5)+ I <l <l
( r r - C r H c ) z S( 1 . 0 ) ,1 1
l9
72 JI 37
7. (CHr!CuLii L i r (0 .5 )+ 025 l2 60
L i B r( 1 . 0 ) t2 l: 60
8. (CHr)zCuLid "residue" o I 55 52
2 99 98
9. (CHr)rCuLid c H 3 L i(0 .1 )+ I J 7
"residue" 4 A 80 80
l5 95 95
10. (rr-C.Ho):CuLiP(rr-Buh^ Lir(0.s) 0.7 rl-CrH rC,;H; <l 50
I l. (sec-CrH,r)zCuLiP(rr-Buh^ Lit (0.5) o.7i sec-CrHgCoHs <l 20
12. "(rt-C.Hc):CuLi"i Lir(0.s) 1.0, rt-C.rHgCoH: <l 55
13. "(sec-C1H,,)rCuLi"i L i r( 0 . s ) I .0, sec-CrH,rCoH; <l <t
. Reactionswcre carncd ou! in erhersolutionat 25', with [RrCuLi] = 0.5 11, and [C.Hill - 0.1 I/, unlessotherwiseno(ed. ' Yiclds
were dcterminedby glpc, and sre basedon iodobenzenc. " Oxidationswere carried out by diluting the reaction mixlure to -0.1 M in Cu(l)
d Pteparedby dissolving hal idc-freem€thylcopper(I)
followed by addition ofan excessof moleculff oxygenat -78', unlessnoted olherwise.
in hatide-fiee methytlithium solurion (eq ?). , Preparedby reaction of 2 equiv of melhyllithium wirh I cquiv of (r'-C.H')rslrcul (eq 8)
/ prepar€dby reactionof 2 equiv of alkyllilhium reagentwith a suspensionof I equiv of Cul (eq 6), , "Residue".refersto the materialspres-
I Pr€paredby re-
enr in commircial copper(l) iodide which are insoluble in di-r-butyl sul6de. See the text lbr a disctrssionof this poin!.
I Relction carriedout a( -10'. )THFsolurion-
acrionof 2 equivof aikyllirhium.eagentwirh I equivof lCuP(r-Bu)r(eq 8).

Th e pr es enc e of t he s el i g a n d sa n d th e i r re a c ti o nproducts taken to avoi d contact betw een the reacti on solut ion
during the w o r k - u p o f r e a c t i o n sc a r r i e d o u t o n a s y n - a n d o x y g e n ( f r o m t h e a i r ) i n t h e r e a c t i o n si n v o l v i n g a
t h e t i cs c a l eh a sc o n s i s t e n t l yp r o v e dt o b e a m a j o r i n c o n - n o n o x i d a t i v e w o r k - u p , t h e p o s s i b i l i t yt h a t s o m e p o r -
venience. t i o n o [ t h e t o l u e n e o r l - m e t h y l n a p h t h a l e n feo r m e d i n
L i t h i u m d i a l k y l c u p r a t e sc o n t a i n i n g p r i m a r y a l k y l t h e s e e x p e r i n t e n t sa r o s e f r o m u n i n t e n t i o n a l r e a c t i o n
g r o u p so t h e r t h a n n r e t h y lc a n i n g e n e r a b l e p r e p a r e db y w i t h a n o x i d a n t c a n n o t b e r i g o r o u s l ye , r c l u d e d . T h e
p r o c e d u r e sa n a l o g o u st o t h o s e o f e q 6 , 7 , a n d 8 , a l - i ncreasei n yi el d of unsymmetri caldi mer on o xidat ion
t h o u g h t h e s o l u t i o n so b t a i n e db y t h e p r o c e d u r eo f e q 6 provi des a qual i tati ve measureof the quanti t y of ar yl-
m a y c o n t a i n a l k y l l i t h i u m r e a g e n ti n a p p r e c i a b l e x c e s s metallic reagent presentin the solution. Additional
o f t h e s t o i c h i o m e t r yr e q u i r e d b y t h e f o r m u l a t i o n R : - evi dencefor the presenceof an aryl metal l i c int er m e-
C u L i . G r i g n a r d r e a g e n t sc a n n o t i n g e n e r a l b e s u b - d i a t e i s d i s c u s s e dl a t e r i n t h i s m a n u s c r i p t . S i n c ea n e x -
sti tu t ed f or or gano l i th i u m re a g e n tsi n th e p ro c edureof cessof l i thi um di methyl cupratew as used i n all st udies,
e q 6 . W e hav e on l r' b e e n s u c c e s s fuiln p re p a ri ngw el l - a n d s i n c eo x i d a t i v ec o u p l i n g o f m i x e d l i t h i u m d i o r g a n -
ch ar ac t er iz eds ec - a n d t-a l k y l c o p p e r(l )re a g e n tsby the ocupratesseemsto gi ve approxi matel ystati sticalyields
p ro c edur eof eq 8. T h e p ro c e d u re se x e mp l i fi e dby eq 6 o f s y m m e t r i c a la n d u n s y m m e t r i c a dl i m e r s , r et h e p r o b -
[wi th c opper ( l) br o m i d e ],7 , a n d 8 w e re a l s o s a tisfactory a b i l i t y o f s y m m e t r i c a lc o u p l i n g o f t h e a r y l m o i e t i e so f
f o r p r o d u c i n ge t h e r s o l u t i o n s o f l i t h i u m d i p h e n y l c u - t w o a r y l m e t a l l i cr e a g e n t su n d e r o x i d a t i v ec o n d i t i o n si s
prate. much l ow er than the probabi l i tv of unsymmetr icalcou-
The pr oduc t s of re a c ti o n o f l i th i u m d i me th yl cuprate pling.
w i t h i o d o b e n z e n ea n d w i t h i o d o n a p h t h a l e n ew e r e i n - The data of Tabl e I summari ze observat ionscon-
t e r r e df r o m a c o m p a r i s o no f t h e g l p c t r a c e so f t w o a l i - c e r n i n gt h e r e s p o n s eo f t h e y i e l d o f t o l u e n ei n c o u p l i n g
q u o t s : o n e a l i q u o t w a s h y d r o l y z e dd i r e c t l y ;t h e s e c o n d of l i thi um di methyl cuprate w i th i odobenzene t o i. I
w a s f ir s t ox idiz edu s i n g a n e x c e s so f mo l e c u l a ro xygenor n u m b e r o f t y p e s o f c h a n g e si n r e a c t i o n c o n d i t i o n s .
n i t r o b e n z e n ea. n d t h e n h y d r o l y z e d . U s i n g t h i s a n a - T h e r e a c t i o no I p u r e l i t h i u m d i m e t h y l c u p r a t w e ith iodo-
l y t i c a l p r o c e d u r et,h c y i e l d o f t o l u e n eo r l - m e t h y l n a p h - benzenei n hal i de-fi reeether appearsto be com plet e in
t h a l e n e o b t a i n e d f o l l o w i n g t h e n o r t o x i d a t i v ew o r k - u p 2 4 h r o r l e s sa t 2 5 o . T h e y i e l d o f t o l u e n ei n t h e n o n -
p r e s u m a b l yp r o v i d e sa m e a s u r eo f c o u p l i n gt a k i n g p l a c e oxi dati ve w ork-up, and the i ncreasei n yi el d o f t oluene
b y s onr ec om binati o n o f re a c ti o n sre p re s e n te db y eq 2, o n o x i d a t i o n .d e m o n s t r a t et h a t t h e p r o d u c t so f c a r b o n -
3 , a n d - 1 . A l t h o u g h i t n u m b e r o f p r e c a u t i o n sw e r e carbon bond formati on and metal -hal ogen exchange

lVhiresitles,et al. I ! ithium Dialky'l- unclDiarylcuprareReactions


II. Reactionof MethylcopperDerivativeswirh r-rodonaohthalene
l-lodonaph- Other solution Reactron _yields. oto ---.
Copperreagent thalene componen(s tlme. l-Methyl- l-Iodo-
(concn. /V/) Concn, rVf (concn, ,l/) hr Naphthalene naphthalene _naphthalene
(CHr)zCuLi(0.38)b 0.l3 0.5 25 l0 67
2.O 5l 29 t7
4.0 58 3l 6
8.0 62 JJ
(CH'):CuLi (0.38)" 0.l3 LiI (0.3e) 05 72 ll 7
1.0 73 l3 3
2.0 77 t4
23 69 20
( C H ' ) ' C u L i( 0 . 3 2 X 0.ll Lir (0.32) 2.5 59-70 26-28 3-10
ti (2 62 l0;a
)< (2 57 l6)"
2.5 (4 70 4)l
(0.38)
CHTCUP(rr-Buh 0 .r 3 0.5 8
I 9l
2.0 I
3l 68
4.0q 5 75 J
CH.rCuP(rr-Bu)r (0:38) 0.l3 2.0 2 JJ 65
C H , C U P ( r r - B u(h0 . 3 8 ) 0.13 LiI (0.38) 2.0 20 29 5l
" Bas€don l_iodonaphlhalene. Reactionswere carried out in ether solution a! 25' unlessotherwiseindicated. ! prepared by dtssolvrng
halide-freemerhylcopper(I)inhalide'freernethyllithiumsolution(eq7)..Preparedbyreacrionof2equivoimiilyttithiumwittrisuspensioi
oi I equiv of Cul (eq 6). d Yields obtained on oxidalion with o. a! 0'. If all the oxygen added had dissolvedin the reaction
solurion. its
equrlalcn!concentrationwould have been 1.4,L/. . Oxidation wilh 01 at -78": equivalentconcentration1.4 M, /Oxidation wilh
PhNO! at 0"; equivalent concentration0.67 rll. , The reaction was stirred at 25-27' for 2 h. ano *ten treareJiotO-io" ror
z tr.

f o r m a t c o m p a r a b l er a t e s . S i m i l a r d a t a f o r r e a c t i o n s m e t h y l l i t h i u mw i t h a r y l i o d i d e si n t h e a b s e n c eo f c o p p e r
w i t h l - i o d o n a p h t h a l e na e r e p r e s e n t e di n T a b l e I I ; i n s a l t so f t e n g i v e sy i e l d so f c o u p l e dp r o d u c t sc o m p a r a b l c
t h i s c a s ec o n s u m p t i o nb y t h e a r y l i o d i d e i s c o m p l e t ei n o r s u p e r i o r r o t h o s e o b t a i n e du s i n g l i t h i u m d i m e t h y , l -
less than 8 hr. The addition of lithium bromide, cuprate. However, comparison of entries I and l
lithium iodide, or di-n-butyl sulfide to solutions ot of rabl e I establ i shes thar the presenceof me t hyilit hiur '
lithiumdimethylcuprare ( t ) p r e p a r e df r o m p u r e m e t h y l - i n excessof the stoi chi omerryrequi red by the f or m ula-
c o p p e rh a s r e l a t i v e l yl i t t l e e f r e c to n t h e r a t e e i t h e ro f t h e t i o n " ( C H r ) , C u L i " d o e s n o r a p p r e c i a b l ye n h a n c e t h e
m e t a l - h a l o g e ne , \ c h a n g er e a c t i o n o r o f t h e c o u p l i n g r e a c t i v i r yo f t h e c o p p e r a r e c o m p l e x i n t h e c o u p l i n g
reacrion. Addition of I equiv of tri-n-burylphosphine reaction.
t o a r e a c t i n gs o l u t i o n o f l i t h i u n r d i m e t h y l c u p r a t ea n d A possi bl ecl ue to the di fferencei n reactivit y of pur c
i odobenz enehas tw o e ffe c ts : i t i n c re a s e sthe rate of lithium dimethylcuprare a n d m a t e r i a lp r e p a r e dd i r e c t l y
m et al- halogene ,rc h a n g ea s j u d g e d b y th e y i e l d of tol - from methyllithium and commercial copper iodidc
u e n eo b t a i n e do n o x i d a t i o n ,a n c li t i n c r e a s etsh e r a t e o f a p p e a r si n c o m p a r i s o no f e n t r i e s2 , 7 , 8 , a n d 9 o f T a b l c
t o l u e n ef o r m a t i o n p r i o r t o o x i d a t i o n . I. The ether-soluble c o m p l e xo f d i - n - b u t y ls u l f i d ea n c l
C o m p a r i s o no f e n t r i e s l , 3 , 4 . a n d 7 o f T a b l e I a n d c o p p e r ( l )i o d i d e u s e di n t h e p r e p a r a t i o no f p u r e m e t h y l -
s i n r i l a rd a t a i n T a b l e I I e s t a b l i s h etsh a t t h e r e a c t i o nb e - c o p p e r ( t ) ( e q 7 ) i s o b t a i n e d b y d i s s o l v i n gc o p p e r ( l)
tween aryl iodidesand pure lithium dimethylcuprate. iodide in the sulfide. Commercial "copper iodide"
p r e p a r e df r o m m e t h y l l i t h i u m a n d m e t h y l c o p p e r ( l ) i, s ordi nari l y contai nsapproxi matel y5 ft i mpur it ieswhich
a p p r e c i a b l ys l o w e r t h a n t h a t w i r h l i t h i u m d i m e t h y l - are insoluble in di-n-butyl sulfide. Entries 8 and 9
cu pr at e pr epar e d b y re a c ti o n o f m e th y l l i t hi um and summari zeexperi mentsi n w hi ch thesedi -n-but yl sulf ide
c o p p e r ( l )i o d i d e : t h e l a t t e r r e a c t i o na p p e a r st o b e c o m - i nsol ubl e resi duesw ere col l ectedand added t o copper
p l e t e i n l 5 - 3 0 m i n . w h i l e t h e f o r m e r p r o c e s sr e q u i r e s ate compl exespreparedfrom pure methyl co pper . Sur -
8 -2- l hr . F ur t he r, a l th o u g h th e y i e l d o f to l uene ob- pri si ngl y, i t appearsthat addi ti on of these r esiduest t r
tained on oxidation of the latter reactionmixture is the organocoppersol uti onssi gni fi cantl yenh ancest heir
c o m p a r a b l et o t h a t o b t a i n e d o n o x i d a t i o n o [ r e a c t i o n reacti vi ty i n the nono,ri dati vecoupl i ng react ion. Wor k
mixturesincorporatingpure lithium dimethylcuprate, i n progress i s desi gnedto expl ore the si gnif icanceot -
t h e y i e l d o f t o l u e n ep r o d u c e di n t h e d i r e c tc o u p l i n gr e a c - t h e s eo b s e r v a t i o n sa.n d a n y d i s c u s s i o n of themechanism
ti o n is s ignif ic an tl yl o w e r. T h u s . i t a p p e a rsth at metal - by w hi ch the di -n-butyl sul fi dei nsol ubl eresiduesm ighr
h alogenex c hang ei s s i g n i fi c a n tl ,vmo re ra p i d usi ng the i n f l u e n c et h e c o u r s eo f t h e c o u p l i n g r e a c t i o ni s c l e a r l y '
re a gent pr epar e d b y re a c ti o n o f m e th y l l i th i um and specul ati on. N onethel ess.these resul ts ra ise t he in-
c o p p e r ( l )i o d i d e r h a n u s i n g p u r e l i t h i u m d i m e t h y l c u - triguing possibility that metals,other than copper,
prate. p r e s e n ti n t h e r e s i d u e sm a y b e c a p a b l eo f c a t a l y z i n gt h c
The r eas on f or th e o b s e rv e dd i ffe re n c e si n reacti vi ty c o u p l i n gr e a c t i o n . : {
o f t he or ganom e ta l l i cre a g e n tsp re p a re d b y th e proce-
d u r es r epr es ent e db y e q 6 a n d 7 i s n o t p re s entl ycl ear. yielded 86% l-methylnaphthalene. Consequently, the direcr reection
with methyllithium appears to bc the merhod of choice for synthcrrc
Methyllithium itself reacts readily with iodobenzene mcthylation reactions involving aryl iodides when other function.rl
to y ield t oluene .!3 In fa c t, th e d i re c t re acti on of groups in the organic iodide are compatibte with this organometallic
reagent. Comparison of these yieids and reacrion times with those in
( 2 3 ) ( a ) H . G i l m a n a n d F . W . M o o r e , J . A m e r . C h e m .S o c . ,6 2 , l g 4 j Table I provides chemical evidence that solutions of lithium dimethl,l-
( 1 9 4 0 ) ; ( b ) W . L a n g h a m ,R . Q . B r e w s r e ra, n c lH . G i l m a n , i b i d . , 6 3 , S 4 S cuprate do not contain appreciable concentrations of free methyllithium.
( l 9 , l l ) . I n o u r h a n d s , r e a c r i o n o f I e q u i v o f m e t h y l l i r h i u mw i t h I (24) Nore Apoeo rx PRoor. Semiquantitative flame spectropho-
e q u i v o f i o d o b e n z e n ei n e t h c r y i e l d e d9 l f t o l u e n ei n 3 0 m i n a t r o o m tometric anal-vsis of a representative sample of the di-n-butyl sulfidc
tempcraturc. Under similar reaction conditions, l-iodonaphthalcne insoluble "residue" in commercial copper(I) iodide has established thar

Journul o/'tlrc Americun Chemical srrcierl' I 9l:t7 I August Ij, 1969


T a b l eI I I . l u p r a t ew i t h A r y l a n d V i n y l H a l i d e s
R e a c r i o no f L i t h i u m D i p h e n y C
(CeHr)rCuLi Organic halide Additiv(s) Reaction
(concn. r!/) (concn, ,l/) (concn,M) time, hr Product y,ields,
l - l o d o - I P h e n y l -l , l ' - B i -
Iodo- Naph- naph- naph- naph-
benzene thalene thalene thalene thyl

0.16 l -lodonaphthalene LiBr (ca.0.48)" I 53 60 ?5 l3


(0 032) ,I
6,i 22
t9 J9 28
0.16 LiBr (ca.0.48)" .t
h 525
Oz (excess)"
0.16 LiBr (ca.0.48)," I
b 51 )
O: (excess)d
0.16 LiBr (ca.0.48)," A
b t0 90
PhNOr (0.40)"
0.16 LiBr (ca.0.48)," ,| 6 :-i 70
MeNOr (0.59f
0.16 LiBr (ca.0.48)," t1
b l5 8l
CuClr (0.32Y
0.18 Lrl (ca.0.02) I :5 59 t2
4 .18 ,i6 J
a1
JI
)) l9 r1
45
0.2t L i B r ( c a .1 . 7 ) I
bJl J+ 25
(0 042) 35 b5e 2 39
, r r u r s - Sitl b e n e
't5 crs-Stilbene
0.2-l I rar ts- 13-Bromostyrene LiBr (ca.0.72)" 2.O <2
(0.04e) 4 .0
'tn
90 <2
0.:0 c i s - d -B r o m o s t y r e n e LiBr (cn.0.60)' <l 73
( 0.0 4 2 )
1,8-Diphenl'l-
naphthalene l- Phenylnaphthalene
0.60 1 , 8 -D i i o d o n a p h t h a l e n e L i B r ( c a .1 . 8 ) " 2.1(reflux) 5 56
(0.10)
060 O.:(excess)" 41
2
. This salt was formed in the reactionsolutionduring the preparationof phenyllithiumand during the subscquent lbrmationof lithium
diphenylcuprarefrom phenyllithium and copper(t) bromide. ' In theseruns the yield of iodobenzenewas not determined. "After the re-
acrion solulion had been srirred for the speciliedtrrne it was cooled to 0' before the oxidant was added. d Aftcr the reaclion solution had
beenstirred for lhe specifiedtime it was cooled to - 78' before the oxidant wds added.

R e a c t i o n o f l i t h i u n r d i - r r - b u t y l -a n d d i - s e c - b u t y l ' for successfulcoupl i ng. Methyl (tri -rr-butyl phosphine) -


(tri-n-butylphosphine)cuprates:w 0 ith iodobenzene c o p p e r ( l ) r e a c t s w i t h l - i o d o n a p h t h a l e n et o g i v e
y i e l d s a p p r e c i a b l eq u a n t i t i e so f n - b u t y l - a n d s e c - b u t y l - l - m e t h y l n a p h t h a l e n e .T h i s r e a c r i o n s e e m s t o b e
b e n z e n e .r e s p e c t i v e l y o, n o x i d a t i v e c o u p l i n g , b u t n o accompani ed by appreci abl y l ess metal -hal o gen ex-
b u t y l b e n z e n e so n n o n o x i d a t i v e h y d r o l y t i c w o r k - u p c h a n g e t h a n t h e c o r r e s p o n d i n gr e a c t i o n i n v o l v i n g
( T a b l e I ) . A p p a r e n t l y m e t a l - h a l o g e ne x c h a n g ec a n m e t h y l c o p p e ra t e c o m p l e x e s . U n f o r t u n a t e l yt h e p r e s -
t a k e p l a c ew i t h t h e s e r e a g e n t s b, u t t h e d i r e c t c o u p l i n g e n c e o f t r i - n - b u t y l p h o s p h i nien t h e s er e a c t i o nm i x t u r e s .
r e a c t i o ni s s l o w . a n d t h e t h e r m a l i n s t a b i l i t y o f a l k y l c o p p e r ( l )r e a g e n r s
H y d r o l y s i so f a l i q u o t s o f a r e a c t i o nm i x t u r e c o n t a i n - other than methyl , severel yl i mi t the practi calusef ulness
i n g p u r e l i t h i u m d i m e t h y l c u p r a t ea n d i o d o n a p h t h a l e n e of coupl i ng reacti ons i nvol vi ng the al kyl (tri- n- but yl-
d e m o n s t r a t e st h a t t h e d e c r e a s e i n t h e c o n c e n t r a - phosphi ne)copper([) reagents.
t i o n o f i o d o n a p h t h a l e n ei s a c c o m p a n i e d b y ^ c o r - For reacti on systems i n w hi ch metal -halogen ex-
responding increase in concentration of both l- change i s faster than di rect coupl i ng, there m ay be
m e t h y l n a p h t h a l e na e n d n a p h t h a l e n e t, h e l a t t e r c o m - p r a c t i c a l a d v a n t a g e si n c e r t a i n c a s e s t o a c o u p l i n g
pound presumably arising from protonation of a schemeinvolving direct formation of the mixed are
l - n a p h t h y l o r g a n o m e t a l l i cr e a g e n t . T h e d a t a i n T a b l e c o m p l e x e sr e q u i r e df o r o x i d a t i v ec o u p l i n gf r o m o r g a n o -
II sugges t hat nit ro b e n z e n ei s a s l i g h tl y m o re e ftrci ent l i thi um reagents. Thi s scheme i s most attra ct ive f or
r e a g e n tf o r t h e o x i d a t i v e c o u p l i n g t h a n i s m o l e c u l a r c o u p l i n g si n v o l v i n g . r e c -o r l - a l k y l c o p p e rc o m p o u n d s .
o xyg en. T he las t th re e e n tri e s i n T a b l e II e stabl i sh The thermal stabi l i ty of these reagentsi s suf f icient l, '-
that formation of an ate complexis not a prerequisite l ow that extensi vethermal decomposi ti onoccu r s under
the reaction conditions required for coupling and
irs principal mctallic constituents are: Cu (> l0%), Fe (>10%), m e t a l - h a l o g e ne x c h a n g et o t a k e p l a c e . I n c o n t r a s t .
N a ( l - 1 0 ; ) , N i ( 0 . 1 - 1 . 0 ' l l ) ,a n d C r ( 0 . 1 - 1 . 0 T ) . A m i x t u r e o f " p u r c "
lirhium dimethylcuprate, prcpilred using the procedure rcpresented bt'
b o t h t h e f o r m a t i o n o f m i x e d a t e c o m p l e x e sb y r e a c t i o n
eq 7. and iron(II) chloridc 1<20T, based on coppcr) shorvs lhe same o f o r g a n o l i t h i u mr e a g e n t sw i t h c o p p e r ( l )s a l t s( e q 6 a n d
rcactivity'toward iodobenzcnc as material preparcd drrectly from 8 ) , a n d t h e i r s u b s e q u e n to . r i d a t i v ec o u p l i n g , c a n b e
methrtlithium and commcrcial copper iodide. Nickel(tl) bromide
signiticantly cnhanccs both thc yield and rate of formation of toluene carri ed out at -78o. Thus. for exampl e, sec- but yl-
i n t h c d i r e c t c o u p l i n g r ea c t i o n o l ' " p u r e " l i t h i u m d i m c t h y l c u p r a t e w i t h benzenei s formed i n hi gher yi el d by oxi dati on of pr e-
iodobenzene. Thus, both nickel and iron catalyze the coupling of
formed ate compl exesthan by di rect reacti onof lit hium
lithium dimcthylcuprate rvith iodobenzene. Studies of applications
a n d m e c h a n i s m o t ' t h i s c a t a l r - s i sa r c c o n t i n u i n g . di -sec-butyl cuprate w i th i odobenzene(Tabl e I).

l,l,'lritesides,
et al. I Litltium Diulk-t'l-und DiarT'lcuprctte
Reuctions
876
I. 2.; CuBr.T IIF. - ;3.
sec-C1H,Li* 4CnH;Li ec-CrHnCrH; s o i u t i o n s : i n m o s t o f t h e s e r e a c t i o n sw e h a v e e x -
G, -;30 amined.the yields of couplcd product obtained after
(76/"1
l . 2 . 5 C t r l l r ,T I I I ' . - 7go e i t h e r o x i d a t i o n o r h y d r o l y s i so f t h e r e a c t i o nm i x t u r c s
t-C.{HJLi * 4CrHrLr --+ l-C{HcCeHi a r e v e r y s i m i l a r . S i n c e r h e o . r i d a t i o nq f l i t h i u m d i -
2. O:, - 78"
(737'1 a l k y l c u p r a t e sg i v e s g o o d y i e l d s o f d i m e r i c p r o d u c t s . r l
R e a c t i o no f L i t h i u m D i p h e n y l c u p r a t e with Aryl and t h i s o b s e r v a t i o ni n d i c a t e st h a t t h e s er e a c t i o ns o l u t i o n s
Viny'l Halides. The reacrion of lithium diphenyl- d i d n o t c o n t a i n s i g n i f i c a n tc o n c e n t r a t i o n so f o r g a n o -
c u p r a t ew i t h l - i b d o n a p h t h a l e n(eT a b l e t I I ) a p p e a r st o m e t a l l i c c o m p o u n d s c o r r e s p o n d i n gt o t h e s t a r t i n g o r -
f o l l o w a p p r o x i m a t e l yt h e s a m e p a t t e r n t h a t a p p e a r e d g a n i c h a l i d e s .a r t h e p o i n t a t w h i c h t h e o x i d a n t w a s
i n r e a c t i o n so f t h e m e t h y l r e a g e n tI w i t h l - i o d o n a p h - added. Although this fact does not by itself exclude
t h a l e n ea n d i o d o b e n z e n e . T h e o p e r a t i o n o f m e t a l - t h e p r o d u c t s o f m e t a l - h a l o g e ne x c h a n g ea s t r a n s i t o r l .
h a l o g e n i n t e r c h a n g ei n t h i s r e a c t i o n s y s t e mi s u n a m - i n t e r m e d i a t e si n t h e c o u p l i n g r e a c t i o n , t h e o b s e r r . e j
b i g u o u s l . cv o n f i r m e d b y t h e o b s e r v a t i o nt h a t h y d r o r y s i s s t e r e o c h e m i s t roy I t h e r e a c r i o no f l i t h i u m d i p h e n , v - l c u -
o f a r e a c t i o na l i q u o t w i t h D : O a f t e r t h e m e t a l - h o l o g . n prate w i th (-)-(n)-2-bromoburane (ui de i nf r a) r encler s
e x c h a n g eh a s t a k e n p l a c e l e a d s t o n a p h t h a l e n eh a v i n g t h i s r e a c t i o nc o u r s eu n l i k e l y . T h i r d , c o u p l i n g si n v o l v -
i s o t o p i cc o m p o s i t i o n 8 0 7 4 d r , 2 0 % d o , & n d b y t h e s i - i n g a l k y l h a l i d e sa r e s i g n i f i c a n r l yi m p r o v e d b y u s i n g a
nruitaneoua sppearance o f i o d o b e n z e naen d n a p h t h a r e n e p o l a r s o l v e n t s u c h a s t e t r a h y d r o f u r a na s t h e r e a c t l o n
i n a o p r o r i m a t e l y e q u a l y i e l d s f r o m h y d r o l y s i so f a l i - medium.
q u o t s t a k e n e a r l y i n t h e r e a c t i o n . M e t a l - h a l o g e ne x - S e v e r a ls p e c i f i cp o i n t s c o n c e r n i n gt h e d a t a i n T a b l e
c h : r n g ei s c o m p l e t ei n a p p r o x i m a t e l y4 h r a t r o o m t e m - I V d e s e r v eb r i e f c o m n r e n t . F i r s t , l i t h i u m d i m e t h v l c u -
p c r r t u r e : t h e c o u p l i n g r e a c t i o n ,w h i c h m a y r e f l e c e p r a t e ( 1 ) p r e p a r e df r o n t m e r h y l l i r h i u ma n d c o p p e r ( l )
t ither
d i r e c r r c a c r i o n o I l i t h i u m p h e n y l l(- n a p h t h y l ) c u p r a t e o d i d e a p p e a r st o h a v ' et h e s a m e r e a c t i v i t yt o w a r d a l k , , l
i
* ' i t h t h e i o d o b e n z e n e f o r m e d i n t h e e x c h a n g e ,o r h a l i d e sa s d o e s p u r e l . S i n c e t h e d i f f e r e n c eb e t w , e e n
thr'rntad l e c o m p o s i t i o no l a l - n a p h t h y l c o p p eorr g a n o - t h e r e a c t i v i t y o f t h e s e r e a g e n t st o w a r d a r y l h a l i d e s
n l e t a l l i cr e a g e n ti n t h e p r e s e n c e o f a p h e n y l c o p p ecr o m - s e e n r e dt o b e r e l e t e dt o a d i f l e r e n c ei n t h e i r a c t i v i t l , i n
p o u n d . c o n t i n u e s n t o r e s l o w l y . R e g a r d l e s so f t h e m e t a l - h a l o g e ne x c h a n g e t. h e i r s i m i l a r i t yi n a r e a c t r o n
n r e c h a n i s nt r f t h e t h e r m a lc o u p l i n gr e a c t i o n o. x i d a t i o n s y s t e m i n w h i c h m e t a l - h a l o g e ne x c h a n g ea p p a r e n r l v
c r it h e m i x t u r e o t ' o r g u n o n r e t a l l irce r g e n t so b t a i n e da f t e r d o e s n o t t a k e p l a c e i s n o t s u r p r i s i n g . S e c o n d ,i t a p -
t h e i n i r i a lm e t a l - h a l o g e ne x c h a n g er c u c t i o ni s c o m p l e t e p e c r s t h e t i t m a v b e p o s s i b l ei n c e r t a i n c o u p l i n g r e i t c -
r c s u l t si n e f t i c i e n ct o n v ' e r s i o o n f l - n a p h t h y l m e t asl p e c i e s t i o n s t o u s c a m i x t u r e o f t t r g a n o l i t h i u mr e a g e n t a n t i
p r c s e n t i n s o l u t i o n t o l - p h e n y l n a p h t h y l e n eO . nce c a t a l . r ' t i cq u a n t i t i e s o f c o p p c r ( l ) i t t n i n p l a c e o f p r c -
a g l i n . n i t r o b e n z c n ea p p e a r st o p r o d u c e t h e h i g h e s t f o r m e d d i i t l k y l c u p r a t e st o e f l ' c . ctth e c o u p l i n g r e a c t i o n .
v i e l d s o f I - p h e n y l n a p h t h a l e nien t h e o x i d a t i v ec o u - a l b e i t a t a p p r e c i a b l ed e t r i r n c n r t o r e a c t i o n r a t e a n t i
p l i n g : o r i d a t i o nw i t h o x y g e ne i t h e rr r r0 o o r a t - 7 8 o , p r o d u c t y i c l d . T h e r e a c r i o no f t h r e e f o l dm o l a r e x c c s s
n r t r o m e t h a n eo, r c o p p e r ( l l ) c h l o r i d eg i v e sa p p r e c i a b l y o f I w i t h r r - o c t y li o d i d e t t t v i c l d / r - n o n a n et a k e s p l a c e
l c r w €yf i e l d s . q u a n t i t a t i v e l iyn l e s st h a n 3 h r . R e a c t i o no f a s i m i l a r
S i m i l a r l y ,r e a c t i o no f a n e x c e s so f l i t h i u m d i p h e n y l - q u a n t i t yo I m e t h y l l i t h i u mw i t h r r - o c t y il o d i d e f o r l 2 h r
c u D r a t ew i t h 1 , 8 - d i i o d o n a p h t h a l einner e f l u x i n gd i e t h y l yields only 6% n-nonane. Howcver, addition oi 5
e t h e r s o l u t i o n f o r e x t e n d e dp e r i o d so f t i m e a p p e a r st o m o l I c o p p e r i o d i d e ( b a s e do n l - o c r y l i o d i d e ) t o r h e
r c s u l t i n a p p r o x i n r a t c l y 5 0 , | o c o n v e r s i o no f t h e a r y l m e t h y l l i t h i u n r e s u l t si n a 6 l ' ' l y i e l d o I r r - n o n a n ei n l ]
i o d i d e t o l - p h e n y l - 8 - c o p p e r ( l ) n a p h t h a l eansej.u d g e d h r . T h i r d . l i t h i u m d i - i r - b u r y ' l c u p r ar e t ea c t sw i t h a l n l o s r
b . r t h e d i f f e r e n c ei n y i e l d o f l - p h e n y l -a n d 1 . 8 - d i p h e n y l - e q u a l i a c i l i t y w i t h r r - p e n r y li o d i d e . b r o m i d e , c h l o r i d c .
naphthalene b e f o r ea n d a f t e r o x i d a t i o n . a n d t o s y l a t et o y i e l d / r - n o n a n e p. r o c i d e dt h a t t e t r a h v -
R e a c t i o n o f l i t h i u m d i p h e n y l c u p r a t cw i t h c , . r - o r d r o f u r a n i s u s e da s s o l v e n t . T h e u s eo f d i e t h y l e t h e r a s
tra t t . s ' $- br om osty re nre e s u l tsi n h i g h c o n v e rs ionsto crs- s o l v e n tr e s u l t si n l o w e r y i e l d so f c o u p l e d p r o d u c t sw i t h
a n d t r c n . r - s t i l b e n e sr e, s p e c t i v e l y ;o x i d a t i o n i s n o t r e - n - p e n t yb l r o m i d ea n d c h l o r i d e ; t h eu s eo f p e n t a n ea s s o l -
q u i r e d i n t h i s r e a c r i o ns y s r e mt o o b t a i n h i g h y i e l d s o f v e n t a p p e a r st o c o m p l e r e l yi n h i b i t t h e d i r e c t c o u p l i n g
c o u p l e dp r o d u c t s . L e s st h a n 2 \ o f t h e s t i l b e n ei s o m e r r e a c t i o n . T h e s eo b s e r v a t i o n sa r e i n q u a l i t a t i v ea c c o r c i
h a v ' i n gi n v e r t e dc o n f i g u r a t i o na r o u n d t h e d o u b l e b o n d w i t h t h e p r o p o s i t i o nt h a t t h e r e s p o n s eo f t h e c o u p l i n g
i s t o r m e d i n e a c h c a s e . F o r r e a s o n sd i s c u s s e dp r e - r e a c t i o n st o c h a n g e si n s o l v e n t a n d l e a v i n g g r o u p a r e
v i o u s l y 2 tsh e o b s e r v a t i o n o f r e t e n t i o n o f s t e r e o c h e m - h o s e e x p e c t e df o r a n S v 2 r e a c t i o n . F o u r t h , a l t h o u g h
t
r s t r y i n t h e s ec o u p l i n g r e a c t i o n ss t r o n g l ya r g u e sa g a i n s t 2 - b r o m o b u t a n ec o u p l e s i n h i g h y i e l d w i t h l i t h i u m d i -
f r e ed - s t y r v lr a d i c a l sa s r e a c t i o ni n t e r m e c i i a t e s . p h e n y l c u p r a t et h. e y i e l d so f c o u p l e d p r o d u c t so b t a i n e d
Reac t ionof Lith i u m D i a l k l ' l - a n d D i a ryl c u pratesw i th o n r e a c t i o no f s e c o n d a r ya l k y ' l h a l i d e sw i t h l i t h i u m c i i -
A l k l ' l H a l i d e s . T h e r e a c r i o no f t y p i c a l l i t h i u m d i o r - a l k v l c u p r a t e sa r e m u c h l o w e r t h a n t h o s eo b t a i n e dw ' i t t r
g a n o c u p r a t e sw i t h a t k y l h a l i d e s( T a b l e I V ) d i f f e r s i n p rimarv halides. The yieldsof coupled productsob-
s e v e r a li m p o r t a n t p r a c t i c a l a s p e c t sf r o m t h e r e a c t i o n s t a i n e d u s i n g t - a l k y l h a l i d e s a r e s o l o w t h a t t h e r c -
w i t h a r , v l h a l i d e s d i s c u s s e dp r e v i o u s l y . F i r s t . t h e s e a c t i o n a p p e a r st o b e o f n o p r a c t i c a l u t i l i t y . I n c o n -
c o u p l i n g r e o c t i o n s u s u a l l v p r o c e e d m ( ) r e r a p i c l t ya n d t r a s t .l i t h i u m d i - . s e c - a l k yal -n d d i - r - a l k y l ( t r i - n - b u t y l p h o s -
i n h i g h e r y i e l d t h a n d o t h e c o r r e s p o n d i n gc o u p l i n g st o p h i n e ) c u p r a t e sg: 0i v eg o o d y i ei d s o f c o u p l e dp r o d u c t so n
a r . v l m o i e t i e s . S e c o n d , t h e r e i s n o e v i c l e n c ef o r i m - r e a c t i o nw i t h p r i m a r y a l k y l h a l i d e s . T h u s , c o u p l i n g o t '
p o r t a n t i n v o l v e m c n t o f m e t a l - h a l o g e ne x c h a n g e i n a p r i m a r y w i t h a s e c - a l k y lg r o u p i s b e s t a c c o m p l i s h e d
coupling reactions involving alkyl halides in ether either by reactionof a primary alkyl chloride with a
( 2 - s )G . l V I . W h i t e s i d e sa n d C . P . C a s e y ,J . A n t e r . C h e m . , S o c .E "di-sec-alkylcuprate,o " r by reaction of a primaritl'
, g.
. t 5 - Il ( 1 9 6 6 ) . alkyl bromide with a di-scc-alkyl(tri-n-butylphosphine)-

Jourrutl ol rlte Antt'ricun Chemiculsocier.t' t gt;t7 1 August lJ, t969


Table IV. Reactionsof Lithium Dialkyl- and Diarylcuprateswith Alkyl Halides"
R-R' yield, /o"
Copperreagent.RrCuLi Alkyl halide,R'X LiX Time. Hydrol- Oxida-
(concn. rV) (concn,M) (concn,M) hr Solvent ysis tionb
-
(CH,LCuLi (0.5)" n - C r H r r (l 0 . 1 ) 025 EtrO l8 l8
05 30 30
35 98 98
(CHr)rCuLi(0.5)'r (0.1)
rr-CsHrrI Lir (0.5) 025 56 56
05 75 75
35 98 98
(CH')zCuLi(0.33)d I t ' C a H r z( 0
I .1l) Li r (0.5) 2.7 97
CH3Li (0.66) * 5 mol 7. CUI'
ta
IL 64
(rr-CrHr):CuLi(0.4)' r r - C s H r r( l0 . 1 ) I 68 72
2 69 75
26 70
(rr-CnHc):CuLi
(0.4)" (0.I )
rr-CsHrrI t
I THF 98 98
2 98
(0.4)"
(rr-CrHg)2CuLi r r ' C i H r r B(r0 . 1 ) I n-CsH': <2 67
2 <2 70
26 <2
(0.4)"
(rr-CnHr):CuLi r r - C i H r r B(r0 . 1 ) I Et,O 68 72
2 69 75
)6 70
(0.4)"
(rr-CrH,r):CuLi n - C i H r r B (r 0 . 1 ) I
I THF 98 98
26 98
EtrO l0 1)
(0.4)"
(rr-CrH,).rCuLi r r - C ; H r r C( l0 . 1 ) I
9 1)
2
26 l0
(0.4)'
(rr-CrHr):CuLi r r - C i H r r C( l0 . 1 ) I THF 80 86
80 86
io 8l
(0.4)"
(rr-CrH,.,):CuLi r r - C i H r r O T(s0 . 1 ) I THF 98
(rr-CrH,):CuLi(0.4)" C'H,;CHBTCH'(0.I ) I THF l2 l2
2 l) l2
26 l2
(r-CrH,).:Cu
Li (0.4)" C , H i C B r ( C H r )(,0 . 1 ) I THF <t0 <10
2 <10 <10
( r r - C 1 H r ) r C u. LPiB u r( 0 . S ) r r r - C r H r r(l0 . 1 ) Lir (0.5) THF-CcHu 9l 9l
( r r - C r H c ) z C uP L iB' u r( 0 . S ) r r r - C s H u B(r0 . 1 ) (0.5) 93 93
(.sec-CrHr)zCuLi' PBU''(0.5)' r r - C i H r r B(r0 . 1 ) (0.5) 94 94
( / - c . r H , ) : c u L iP' B u r( 0 . s 1 r r r - C i H r r B(r0 . 1 ) (0.s1 THF-CsH'r 92 92
"(rr-C,rH,')rCuLi" 10.5;a r r - C r H r (r 0
l .1) (0.s; EtrO-CcHrr 53 t)

"(rr-CrHu)zCuLi" 10.5;a r r - C r H r r(l0 . 1 ) (0.s1 THF-CoHu 39 55


"(scc-CrHr):CuLi"(0.5)'r r r - C ; H r r(l0 . 1 ) (0.5) 7 7
"( /-CrHq):CuLi"(0.5)r r r - C ; H r r([0 . I) (0's) THF-C;H <l <t
"(rr-CrHn).rCuLi" (0.5)a r r - C ; H r r C( l0 . 1 ) (0.5) 79 80
"(sec'-CrH,r)zCuLi" (0.5)'r r r - C ; H r r C( 0
l .1) (0.s1 64 60
60 60
"(l-CoHu):CuLi"(0.5)d r r - C ; H r r C( 0 l .1) (0.5) <l <l
( n - C r H r ) z C u LPi .B u r( 0 . 5 1 r c - C r H r r B( r0 . 1 ) (0.5) T H F - C t H rr o 25 25
(CoH;)rCuLi(0.21'l r r - C r H n(l 0 . 1 ) Li B r(0.2) 2 EtrO 99
(C'H'hCuLi (0.39)'r C r H ' C H B T C H(T0 . 1 2 ) (0.3e) 7Z THF-Et:OO 87
( C r H r ) : C u L(i 0 . 3 ) d c - C o H r r B( r0 . 1 ) (0.3) 96 g l0 l0
(C'H')rCuLi (0.39)'j AdamantylBr (0.12) (0.3e) 72 c <l
(CeHr)rCuLi(0.2)'t ( C H , h C B r( 0 . 1 ) (0.21 A
c <l
(CH.::CHhCuLi' P(l- Buh (0.S)r r r - C ' H u l( 0 . 1 ) Li t (0.5) 0.75 95 9l
(CH':6gCHz):CuLi (0.3)n r r - C ; H r r( l0 . 1 ) (0.6) 0.75 98d
(CoHrC:C)rCuLis (0.3)'r I t - C ' H ' r [( 0 . 1 5 ) (0.3) J EtrO <l
xidation with Or al
- 78', unlessotherwise nored. . Preparedby dissolvingalkylcopperin alkyllithium solution (eq 7). d Prepared by -reactiono[ slkyllithium
'
reagentwirh copper(I) iodide or bromirJe{eq 6). The iomposition of thesereagentsis uncerta-in. The amount of CuI added isi based on
qua-nrityofa-C"i,,I piesenr. r Preparetiby reactionofalkillithium reagentwith lCuPBur (eq 81. o p"u"r;on temperature52" hepared
i
by reaciion of 2 equiv of allyllithium solution wirh I equiv of t0rC.H,)rS]zCuI (eq 8). The same yield was obtained from reaction ol
CH,:CHCHrLi.

cuprate. Coupling of a primary with a t-alkyl group The mi l d condi ti ons and hi gh yi el ds associ a t edwit h
c a n b e a c c o m p l i s h e db y r e a c t i o no f a p r i m a r y a l k y l h a - thesecoupl i ng reacti onsaffordedan opportuni ty t o ex-
lide with a lithium di-r-alkyl(tri-rr-butylphosphine)cu- ami ne the stereochemi stryof carbon-carbon bond f or -
prate; this coupling fails u s i n g " d i - t - a l k y l c u p r a t e . " m a t ion during a coupling reaction. Optically active
F i n a l l y , a l t h o u g h t h e c o u p l i n g o f l i t h i u m d i a l l y l c u p r a t e (+ )-(S )-2-butanol (opti cal puri ty 77-79% ) w as pr e'
a n d l - pent y l iodide w a s a ra p i d a n d h i g h -y i e l d reac- pared by oxi dati on of the hydroborati on product f r om
t i o n . c o m p a r a b l ey i e l d s o I l - o c t e n ec o u l d b e o b t a i n e d crs-2-buteneand opti cal l y acti ve di i sopi noca m pheyl-
by direct reaction between allyllithiurn and n-pentyl borane.26 Thi s al cohol w as converted to 2-br om o-
iodide. T hus , in t hi s p a rti c u l a r c a s e ,fo rma ti o n of the ( 2 6 ) ( a ) P r e p a r e df r o m d i b o r a n e a n d ( - ) - a - p i n e n e b y t h e m e t h o d
co p p e rat e c om plexo ffe rsn o s y n th e ti ca d v a n ta g e . o f H . C . B r o w n , N . R . A y y a n g a r , a n d C ' Z w e i f e l ,J . A m e r . C h e m ' S o c "

lVhitesitles, et al. I Lithium Dialkyl- und Diury'lcuprate Reactions


4878
CTH; CrH' CzH; f o r t u n a t e l y ,t h e a v a i l a b l ed a t a a r e n o t s u m c i e n t l yd e -
I Ph,PIl.. I , ( - - rllr r : C r rL i t
HrrrClllOH - -> BrlllGlilH H ; i i c l l l C 6 H r( 9 ) tai l ed to permi t a preci se descri pti on of t he bond-
1 DIIII I EIr()-TIIF formi ng step. The reacti on may i nvol ve sim ply dis-
I
CHr CHl CHr
p l a c e m e n to f h a l i d e i o n a t c a r b o n b y a n a l k y l g r o u p
s (eq l 0), or some more compl e.\pathw aypFoceeding, f or
[ o ] t t o+ 1 0 . 4 3 - 1 0 . 6 9 '[ o ] " o - 2 l . O l ' [o]'"o+18.70'
b u t a n e b y t r e a t m e n t w i t h t r i p h e n y l p h o s p h i naen d b r o -
m i n e i n d i m e t h y f o r m a m i d e . T h i s p r o c e d u r ei s a m o d i -
?\_). -I
R,/
-) CuI + R-CL
\
+ I- ( t0)

f i c a t i o no f a p r e v i o u s l yp u b l i s h e dm e t h o d : 7w h i c h m i n -
i m i z e sr a c e m i z a t i o nb y d i s t i l l i n g t h e b r o m i d e f r o m t h e e x a m p l e ,b y n u c l e o p h i l i cd i s p l a c e m e nwt i t h i n v e r s i o no f
reac t ionm ix t ure a s i t i s fo rme d .2 r By a n a l o gyw i th the confi gurati on on the al kyl hal i de by the copper at om
w or k of S c hae fe rs aTn d re l a te d s tu d i e s b y Snyder2ew e (eq I I ), followed by collapse of the resulting forrnol
a s s um e t his ha l o g e n a ti o n p ro c e e d sw i th i nversi on of I
c o n f i g u r a t i o nt o p r o d u c e b r o m i d e o f t h e ( - ) - R c o n - R,Cu---\C-l !
f i e u r a t i o nh a v i n g [ o ] " o - 2 7 . 0 1 o ( n e a t ) ,c o r r e s p o n d i n g
t o a n o p t i c a l p u r i t y o f 7 6 t o 8 l [ , d e p e n d i n go n t h e
v alue ac c ept edfo r th e ro ta ti o n o f o p ti c a l l y p ure 2-bro- 1,, +
R . , C u ( l )l l- C \ --( + RCuu)(r )
mobutane.s0Reaction of this bromide with lithium
diphenylcuprate in refluxing ether-tetrahydrofuran c o p p e r ( l [ [ ) 3 5o r g a n o m e t a l l i cc o m p o u n d w i t h r e t e n t i o n
f i e l d e d( + ) - ( S ) - 2 - p h e n y l b u t a nhea ' , ' i n g
[cv]*-
r 7 o* 1 8 . 2 0 o f c o n f i g u r a t i o ns. 6 U n t i l m o r e i n f o r m a t i o nc o n c e r n i n g
t o + 1 8 . 7 0 " ( n e a t ) , 3 rc o r r e s p o n d i n gt o 6 7 - 6 8 % o p - both the state of aggregati onand structureof t he coppc. r
t i c a l l y 'p u r e m a t e r i a l . 3 { T h u s t h e c o u p l i n g o f l i t h i u m a t e c o m p l e x e sa n d t h e i n f l u e n c eo i a l k y l h a l i d es t r u c t u r c
d i p h e n , v l c u p r a t ew i t h 2 - b r o m o b u t a n e p r o c e e d s w i t h on the rateand stereochenlisto r yf t h e c o u p l i n gr e a c t i o n
p r e d o m i n a n ti n v e r s i o no f c o n f i g u r a t i o n . C o m p a r i s o n are avai l abl e, further specul ati on on det ailed m ech-
o i t h c o p t i c a l p u r i t i e so f t h e s t a r t i n gb r o m i d ea n d c o u - a n i s mi s p o i n t l e s s .
p l c d p r o d u c t e s t a b l i s h e st h a t t h c r e a c r i o nt a k e s p l a c e R e a c t i o no f l i t h i u m d i a l k y l c u p r a t ew s i t h a r _ r 'hl a l i d c s
w i t h 8 - l - 9 2T ; s t e r e o s e l e c t i v i tdye, p e n d i n go n t h e v a l u e d i f l e r s f r o m r e a c t i o nw i t h a l k y l h a l i d e s i, n t h a t m e t a l
a c c e p t e df o r t h e o p t i c a l r o t a t i o no f t h e e n a n t i o m e r i c a l l y h a l o g e ne x c h a n g ei s i m p o r t a n t . T h e r o l e o f t h i s n r e t a l -
p u r e2 - b r o m o b u t a n e . h a l o g e n e x c h a n g ei n n o n o x i d a t i v ec o u p l i n g o f c o p p e r
a t e c o m p l e x e sw i t h a r y l h a l i d e si s p r e s e n t l yu n c l e a r .
Discussion
I n i t i a l g e n e r a t i o no f a n a r y l c o p p e rc o m p o u n d a n d a n
T h e e x p e r i m e n t a ld a t a p r e s e n t e di n t h i s p a p e r i n d i - a l k y l h a l i d e b y m e t a l - h a l o g e ne x c h a n g em i g h t b e f i r l -
c a t e t h a t t h e r e a c t i o n o f ' l i t h i u m d i a l k y l c u p r a t e sw i t h l o w e d b y n u c l e o p h i l i cd i s p l a c e m e not f h a l i d e i o n t ' r o n r
a l k y ' lh a l i d e sp r o c e e d sw i t h o u t s i g n i f i c a nm
t etal-halogen t h e a l k y l h a l i d e b y t h e a r y l m e t a l l i cr e a g e n(t e q l 2 ) . A l -
e x c h a n g e ,b y a m e c h a n i s mw h i c h r e q u i r e s ,i n a t l e a s t . R : C u L i* A r l . - R I * A r R C u L-i - - > R A r (lll
o n e i n s t a n c ep , r e d o m i n a n ti n v e r s i o no f c o n f i g u r a t i o na t
the carbon atom originallybonded to halogen. Fur- t e r n a t i v e l y ,t h e m e t a l - h a l o g e ne x c h a n g em i g h t s i m p l ; '
ther. the structureot' the alkyl group bonded to the c o n s t i t u t e a s i d e r e a c t i o n c o m p e t i n gw i t h d i r e c t c o u -
n r e t a l a n d t o t h e h a l o g e n .t h e n a t u r e o f t h e l e a v i n g p l i n g o f t h e c o m p o n e n t s( e q l 3 ) . O u r d a t a d o n o t
g r o u p . a n d t h e p o l a r i t y o f t h e s o l v e n ta l l e x e r t a n i n - R I + A r R C u L= i - R : C u L *i A r l - > R A r (tll
f l u e n c eo n t h e c o u r s eo f t h e r e a c r i o nw h i c h i s c o n s i s t e n t
w i t h a m e c h a n i s mf o r c a r b o n - c a r b o nb o n d f o r m a t i o n p e r m i t a n u n a m b i g u o u sd i s t i n c t i o nb e t w e e nt h e s e a l -
w h i c h i n v o l v e sa n S x 2 d i s p l a c e m e nat t c a r b o n . U n - t e r n a t i v e sa t p r e s e n t . H o w e v e r , t h e o b s e r v a t i o nt h a t
d i c r _ r ' l c u p r a t easr e c a p a b l e o f n o n o x i d a t i v ec o u p l i n g
8 6 . 3 9 7 ( 1 9 6 l ) . ( b ) T h e a b s o l u t e s t e r c o c h e m i s t r yo f 2 - b u t a n o l h a s b e e n w i t h a r y l i o d i d e s e s t a b l i s h e st h a t a m e c h a n i s mf o r
cstrblishcd by rclation to lactic acid. Sce K. Wiberg, J. Amer. Chem.
S o c . , 7 4 , 3 8 9 1 ( 1 9 5 2 ) , a n d r e f c r e n c c sc i t e d t h e r e i n .
c a r b o n - c a r b o nb o n d f o r m a t i o n d o e s e x i s t w h i c h d o c s
(17) (a) J. P. Schaelcr and D, S. Wcinburg, J. Org. Chem..30, 2635 n o t i n v o l v e a n S x 2 d i s p l a c e m e not f t h e t y p e i m p l i c a t e d
( 1 9 6 5 ) ; ( b ) C . A . W i l c y , R . L . H e r s h o r v i t z .B . M . R e i n , a n d B . C .
by eq l0 and I l.
Chung, J. Amer. Chem. Soc.. 86, 9fl (196.l).
(28) The procedurc used hcrc is similar to that developed in the F r o m t h e p o i n t o f v i e w o f p o t e n t i a la p p l i c a t i o n o t '
unpublished work of F. R. Jcnsen and V. Krimsley, University of c o p p e r" a t e " c o m p l e x e si n c a r b o n - c a r b o nb o n d f o r m i n g
C u l i l o r n i a a t B e r k c l ey .
( 1 9 ) R . G . W e i s s a n d E . I . S r r v d e r .C h e m . C o m m u n . , l 3 5 8 ( 1 9 6 8 ) .
reacti ons, several practi cal l eatures of this wor k ilr e
(30) (a) P. S. Skcll, R. G. Allen, and G. Helmkamp, J. Amer. Chem. w o r t h e m p h a s i z i n g . F i r s t , t h e m o s t c o n v e n i e n tp r e p -
. S o c . .8 2 , ' l l 0 ( 1 9 6 0 ) , o b s c n ' e d [ a ] : s o 3 t . O n " l b r ( * ) - 2 - b r o m o b u t a n e a n d a r a t i o n o f t h e p r e r e q u i s i t ea t e c o m p l e x e sf r o m a s ) ' n -
calculate that the maximum value should be 39.3': (b) from the data of
R . L . L e t s i n g e r , L . G . N { a u r y , a n d R . L . B u r r v e l l ,i b i d . , 7 3 , 2 3 7 3 ( 1 9 5 1 ) , a
t h e t i cp o i n t o f v i e w i s t h a t i n v o l v i n gr e a c t i o no f 2 e q u i v
maximum valuc for [a]r,o of 34.3'ma."'be calculated; (c) F. R. Jensen of organolithium reagent with I equiv of the ap-
and D. D. Davis bclicvc thc maximum value is within the range 33.1- p r o p r i a t e c o p p e r ( l ) h a l i d e . T h i s p r e p a r a t i o ni s a p -
3-s.J". Scc D. D. Davis, Ph.D. Dissertarion. University of California
at Bcrkeley, Aug 1966: (d) P. Salvadori, L. Lardicci, and M. Stagi, p l i c a b l et o a r y l . v i n y l . a n d p r i m a r y a l k y l r e a g e n t s i. t s
R i c e r c a S c i . , 3 7 . 9 9 0 ( 1 9 6 7 ) , s h o r v t h a t S k el l ' s v a l u c s " o l 3 9 . 3 o i s t o o s u c c e s sw i t h s e c o n d a r vr e a g e n t si s m a r g i n a l , a n d i t
high. From thcir data a mlximum valuc for [.lr]lioof 35.7o may be
f a i l s w i t h t e r t i a r y r e a g e n t s . F o r c o u p l i n g r e a c t i o ns
c a l c u l a t e d ; ( c ) D . G . C o o d w i n a n d H . R . [ - l u c i s o n ,J . C h e m . S o c . ,B ,
l l 3 3 ( I 9 6 8 ) , o b s e r rc d [ a ] : : o - J 3 . ' t o t b r ( - ) - l - b r o m o b u t a n e a n d c a l - r e q u i r i n g r - a l k y l c o p p e r ( l )r e a g e n t s l. i t h i u m d i - l - a l k y ' l -
c u l a t c d e m a x i r n u n r v a l u e o t -3 { 8 c . F r o m t h c s c r c s u l t s i t a p p e a r s t h a t ( t r i - n - b u t y l p h o s p h i n e ) c o p p e r ( lc)o m p o u n d s a r e t h ' :
t h c a c t u a l v a l u c l i e s b e t r v c c n3 1 . 4 o a n d 3 - s . 7 o .
( l l ) T h c a b s o l u r c c o n t i g u r a t i o n o t ' ( * ) - ( S ) - 2 - p h e n y l b u t a n e h a s b e en (15) Cf. A. Lcvitzki and NI. Anbar. Chent. Commun.,40l (l96tl).
a s s i g n c db y 'r e l r r t i o n t o 2 - b u t a n o l , r : a n d b y r e l a t i o n t o a - p h c n y l e t h a n o l . r 3 (J6) Forrnally sirnilar oxidative addition reec!ions have becrt ttlr-
( 3 2 ) D . J . C r a m , J . A m e r . C h e n r , S o c . ,7 4 , : 1 . 1 9( 1 9 5 2 ) . servcd for a widc variety ol' dt-dt0 transition mctal complexes. Urt'
( l l ) D . J . C r a m , i b i d . , 7 4 , 2 1 3 7( 1 9 5 1 ) . fortunrtcly' thc s(ereochemistry of thcse reactions is not prescntlv
( 3 . 1 ) J . K c r r y ' o n , P . W . B . H a r r i s o n , a n d J . R . S h c ' p p a r d ,J . C h e m . S o c . , knorrrr. Cf. l. P. Collman, Accounrs Chem. Res., l, 136 (196E):
658, 661 ( 1926),reportcd [c]::o - l7.l' tbr ( - )-l-phenylbutane. L. Vaska, ibid., l,135 ( 1968).

Journul rtl tlre.^ltrtaricunChcnticul Strciet.t'I 9l:17 I August 13, 1969


4879
o n l y p r a c t i c a lc h o i c e . d e s p i t et h e p r o b l e m s f r e q u e n t l y A n a l y s e s o f l i t h i u m r e a g e n t sw e r e c a r n e d o u t u s i n g t h e G i l m a n
d o u b l e - t i t r a t i o n p r o c e d u r e . $ o r b y t i t r a t r o n w r t h a s t a n d a r ds o l u -
e n c o u n t e r e dd u r i n g w o r k - u p p r o c e d u r e s . S e c o n d ,t h e
t i o n o f 2 - b u t a n o l i n x y l e n e w i t h b i p y r i d yI a s a n i n d i c a t o r . { r
h i g h r e a c t i v i t yo f m e t h y l l i t h i u m t o w a r d a r y l i o d i d e s T h e b i s ( d i - r r - b u t y l s u l f i d e ) a n d t h e t n - r r - b u t y l p h o s p h i n ec o m -
i n d i c a t e st h a t t h i s m a t e r i a l . r a t h e r t h a n l i t h i u m d i - p l e x e s o f c o p p e r ( l ) i o d i d e w e r e p r e p a r e d a s d e s c r r b e dp r e v i o u s l y . t s
m e t h y l c u p r a t e i,s p r o b a b l y t h e r e a g e n to f c h o i c e f o r C o p p e r ( l ) i o d i d e w a s p u r i f i e d u s i n g a l r t e r a t u r ep r o c e d u r e , { ta n d
m e t h y l a t i o no f a r o m a t i c h a l i d e s . T h i r d , t h e r e l a t i v e an analogous procedure employ'rng saturated aqueous potassium
b r o m i d e w a s u s e d t o p u r i f y ' c o m m e r c i a l c o p p e r ( l )b r o m i d e .
r a t e s o f c o u p l i n g a n d m e t a l - h a l o g e ne x c h a n g ei n t h e S o l u t i o n s o [ p u r e . h a l i d e - f r e el i t h i u m d r m e t h y l c u p r a t ew e r e o b -
r e a c t i o no f l i t h i u m d i a l k y l c u p r a t e so t h e r t h a n m e t h y l t a i n e d b y d i s s o l v i n g a s u s p e n s r o no f h a l i d e - f r e em e t h y l c o p p e ri n a n
d e r i v a t i v e sw i t h a r y l h a l i d e s i s s u c h t h a t t h e y i e l d o t ether solution containing slightly less than I equiv of halide-free
u n s y m m e t r i c a ld i m e r o b t a i n a b l e b y d i r e c t c o u p l i n g m e t h y l l i t h i u m . r s H a l i d e - c o n t a i n i n gs o l u t i o n s o f l i t h i u m d i m e t h y l -
c u p r a t e sw e r e o b t a i n e d e i t h e r b y ' a d d i n g a s o l u t i o n o f l i t h i u m i o d i d e
re a cti onappear st o b e l e s sth a n th a t o b ta i n a b l efr om a
o r l i t h i u m b r o m i d e i n e t h e r t o a s o l u t i o n o f h a l i d e - f r e el i t h i u m
co mb inat ion of m et a l -h a l o g e n e x c h a n g e fo l l o w ed by dimethylcuprate. or by direct reaction ol' 2 equiv of methyllithium
oxidative coupling. In certain casesit may prove i n e t h e r w i t h a s u s p e n s i o no f I e q u i v o t ' c o p p e r ( l ) i o d i d e i n d i e t h y l
a d va n t ageoust o at te mp t to c o n v e rt th e a ry l c opper ether at 0". Solutions of lithium dialk_,-lcuprate co sntainingtri-rr-
re a g e nt s f or m ed du ri n g me ta l -h a l o g e n e x c h a nge to b u t y l p h o s p h i n e ( r e p r e s e n t e di n t h i s p a p e r a s R r C u L i . P B u r ) w e r e
prepared by adding 2 equiv (typrcatly8.10 mmol,5.00 ml of 1.62
c o u p l e dp r o d u c t sb y a d d i t i o n o f a l a r g e e x c e s so f a l k y l N s o l u t i o n ) o f m e t h y l l i t h i u m ( a s h a l i d e - f r e eo r h a l i d e - c o n t a i n i n g
h a l i d e t o t h e s o l u t i o n s. T A l t e r n a t i v e l y ,f o r m a t i o n o f e t h e r s o l u t i o n ) , v i n y l l i t h i u m , r r - b u t y l - . s e c - b u t y l - .o r t - b u t y l l i t h i u m
t h e l i t h i u m r e a g e n t so f b o t h o f t h e o r g a n i cg r o u p st o b e t o I e q u i v o f t e t r a k i s i o d o t( r i - r r - b u t y l p h o s p h i n e ) c o p p e r ((lt)y p i c a l l y
coupled. followed by oxidative coupling of the ap- 3 . 1 8 g , 8 . 1 0 m m o l . i n 1 . 5 m l o f T H F o r e t h e r )a t - 7 8 o . R e a c t i o n
p r o x i m a t e l ys t a t i s t i c a m between the organolithium rcagent and thc copper(l) halide was
l i x t u r e o f " a t e " c o m p l e x e so b -
essentiallyinstantaneousunder these conditions. The resulting
t a i n e d w h e n t h e s er e a g e n t sa r e m i . r e di n s o l u t i o n w i t h solutions ranged in color ltom colorlessto pale pink or yellow, and
a n a p p r o p r i a t ec o p p e r s a l t , n r a v p r o v i d e a u s e f u lr o u t e r v e r e s t a b l e i n d e f i n i t e l y 'a t - 7 8 ' ' . The thermal stability of these
t o a n u n s y m m e t r i c adl i m e r . p r o v i d e dt h a t t h i s m a t e r i a l m i x t u r e s v a r i e d c o n s i d e r a b l y: l i t h i u m d i - t - b u t y l ( t r i - r r - b u t y l p h o s -
i s e a s i l y s e p a r a t e df r o m t h e t w o s y m m e t r i c a ld i m e r s phinetcuprate was the least stable. its decomposition being essen-
t r a l l y c o m p l e t e a l t e r ] 0 m r n a t 0 ' ; t h e a n a l o g o u sm e r h y l a t e c o m p l e x
n e ccss ar ilyf or nr ed at th e s a m e ti n re . s h o r v e d t h e g r e a t e s t s t a b i l i t y ' ,d i s p l a y ' i n gl i t t l c e v i d e n c eo f t h e r m a l
d e c o m p o s i t i o na l t e r 1 . 5h r a t t h e s a m e t e m p c r a t u r c .
S l i g h t l y c l o u d y s o l r : t i o n s o l ' l i t h i u n r d i p h e n y l c u p r a t er a n g i n g i n
E x p e r i m e n t aSl e c t i o n s ' c o n c e n t r a r i o nl ' r o m 0 . 1 6 t o ( ) . - i 0O / w c r c p r e p a r e db y a d d i n g 2 e q u i v
o f e t h e r e a l p h e n y ' l l i t h i u m t o a c o l c l ( 0 ) s u s p e n s i o no f p u r i f i e d
Preparation of the Organometallic Reagents. All reactions in- c o p p e r (l ) b r o m r d e . T h e s es o l u t i o n sr a n g c d i n c o l o r t r o m p a l ey e l l o w
v o l v i n g o r g a n o r n c t a l l i cr e a g e n t s w c r e c a r r i e d o u t u n d e r a n i n e r t t o a p a l e g r e e n i s hy e l l o w w i t h t h e l c a s tc o l o r a n d t u r b i d i r y b e i n g o b -
atmosphere of prepurified nitrogen. Ether and tetrahydrofuran served when thc solutions wcre prcpareri liom purified phenyl-
r v c r ed i s t i l l e dl t o m l i t h i u m a l u m i n u m h y d r i d c i m m e d i a t e l y b e t b r e l i t h i u m . W e r v e r e c o n s i s t e n t l yu n a b l e t o p r c p a r e t h e s es o l u t i o n
u s e .a n d w e r e t r a n s l e r r e d u n d e r n i t r o g e n u s i n g h y p o d e r m i c s y r i n g e s by the addition ol' ethcreal phenyllithium solutions to cold (0 to
- 7 8 " ) s u s p e n s i o n so f p u r i f i e d c o p p e r ( l ) i o d i d e . I n a l l c a s e s a
o r s t a i n l e s s t e e lc a n n u [ a s .
S o l u t i o n s o f m e t h y l l i t h i u m ( p r e p a r e d f r o m m e t h y l c h l o r i d e , ti n black suspensiorr esultedrather than the solutions obtained wirh
e t h e r , r - b u t y l l i t h i u m i n h e x a n e . s e c - b u t y l l i t h i u mi n h e x a n e .a n d l - c o p p e r ( l ) b r o m r d e . t 3 S o l u t i o n s o t ' l i t h i u r n d i p h e n y l c u p r a t ec o u l d
butyllithium in pentane,obtained ltom the Foote Mineral Corp., a l s o b e o b t a i n e d b y t h e a d d i t i o n o l ' 2 e q u i v o l ' e t h e r e a lp h e n y l l i t h i u m
c o n t a i n e dl e s st h a n 0 . 0 l e q u i v o f l i t h i u m h a l i d e / e q u i v o f a l k y l l i t h i u m to an ethereal solution of bistdi-rr-butyl sulfide)copper(l) iodide.
reagent. Solutionsof methyllithium (prepared from methyl bro- T h e s e o b s e r v a t i o n s s u g g c s tt h a t t h e d e c o m p o s i t i o n o b s e r v e dd u r i n g
m r d e ) i n e t h e r . o b t a i n e d f r o m A l f a I n o r g a n i c s .I n c . , w e r e s a t u r a t e d a t t e m p t s t o p r e p a r e p h e n y l c o p p e r d e r i v a t i v e s l t o m s u s p e n s i o n so f
wrth lithium bromrde. Solutions oi vinyllithium (THF solution) copper(t) iodide should be attributed to impurities in the iodide
obtarned from Alfa contained 5 [ lithium chloride by weight. w h i c h w e r e n o t r e m o v e d b y t h e p u r i f i c a t r o np r o c e s s r 2 we employed.
Halide-lteesolutions of phenyllithium were obtained by the pre- Puritied solutions ol' lithium diphenylcuprate were prepared
v r o u s l y d e s c r i b e d s er e a c t i o n o f i o d o b e n z e n e w i t h r r - b u t y l l i t h i u m by the general procedure describedpreviouslytsin which the ether-
i n a b e n z e n e - h e x a n em r x t u r e . T h e s o l i d p h e n y l l i t h i u m w a s c o l - insoluble phenylcopper was collected and washed with cold (0')
lected. washed with hexane. and redissolved in ether. After the ether under an inert atmosphere. Although the methylcopper
e t h e r s o l u t i o n w a s c o o l e d t o - 7 8 " , t h e c r y s t a l l i n el i t h i u m r e a g e n t r e a g e n t p r e p a r e d b y a n a n a l o g o u s p r o c e d u r e 1 5w a s e s s e n t i a l l yf r e e
w h i c h s e p a r a t e dw a s c o l l e c t e d . r e d i s s o l v e di n e t h e r , f i l t e r e d t h r o u g h of halide containing impurities. the correspondingphenylcopper
a Celite pad. and stored under nitrogen. Ether solutions of phenyl- r e a g e n t c o n t a i n e d l 0 - 2 0 m o l I o [ h a l i d e s a l t s . T h e w a s h e dp h e n y l -
lithium containing lithium bromide were prepared from bromoben- c o p p e r w a s r e d i s s o l v e d i n a n e t h e r e a l s o l u t i o n o f h a l i d e - f r e ep h e n y l -
zene in the usual way. Ethereal solutions of the purified, halide- lithium.
tiee phenyllithium were relatively stable when stored in the re- Allylcopper(l) and lithium diallylcuprate were prepared fronr
frigerator. For example, an ether solution which was initially 3.05 allyllithium. Following a previously described procedure.{r
rl1 rn phenyllithium was found to be 3.00 iVI after 2-months storage 1 . 9 5 5 g ( 6 . 9 0 m m o l ) o f t e t r a a l l y l t i n w a s a l l o r v e dt o r e a c t w i t h 2 7 . 3
at l-2'. mmol of phenyllithium in 29 ml oI ether tor I hr. After centrifu-
g a t i o n t o r e m o v e t h e t e t r a p h e n y l t i n . t h e s u p e r n a t a n te t h e r s o l u t i o n
w a s s e p a r a t e d a n d f o u n d t o b e 0 . 9 7 . 1, & / i n a l l y l l i t h i u m . T h e a d d i -
(37) The usefulncss of this technique has been demonstrated by tion of I equiv of an etherealsolution ol' allyllithium to a cold
C o r e y a n d c o r v o r k c r s . 1 7l,B ( - 7 8 " ) e t h e r e a Is o l u t i o n c o n t a i n i n g I e q u i v o f t h e b i s ( d i - n - b u t y ' l
(38) All mclting points are corrected and all boiling points are sulfide) complex of copper(l) iodide produced a bright red pre-
uncorrected. Unlcss otherwise stated magnesium sulfiatewas employed cipitate of allylcopper. Addition of a second equivalent of allyl-
as a drying agenr. The infrarcd spectra were dctermined with a Perkin-
lithium converted the mixture to a pale yellorv solution of diallyl-
Elmcr, Model 237, grating spectrophotomerer. The ultraviolet spectra
were dctcrmined with a Cary recording specrrophotometer, Model 14.
cuprate.
The nmr spectra were determined at 60 MHz with a Varian Model A-60
"Lithium di-n-butylcuprate" was prepared by reaction of n-
spectrometcr. The chemical-shift valucs are expressed either in hertz butyllithium with copper(l) iodide usrng the lollowing proce-
or rl (ppm) relativc to a tetramethylsilane internal standard. The mass
spcctra rvercobtained with a CEC Model 2l-130 or a Hitachi (Perkin-
Elmcr) mass spcctrometer. Analytical glpc analyses were performed
on F & iVl !Iodel 810 flame ionization and iVlodel 720 thermal conduc- ( 4 0 ) H . C i l m a n , F . K . C a r t l e d g ea, n d S . Y . S i m , i b i d . , l , 8 ( 1 9 6 3 ) .
tivity instruments. Absolute yields of producrs were calculated from ( 4 1 ) S . C . W a t s o na n d J . F . E a s t h a m i,b i d . , 9 ,1 6 5( 1 9 6 7 ) .
peak areas using internal standard techniques, with response factors ( 4 2 ) C . B . K a u f f m a n a n d L . A . T e t e r ,I n o r g . S ) ' n . , 7 , 9 ( 1 9 6 3 ) .
obtaincd with authentic samplcs. ( 4 3 ) t h i s d e c o m p o s i t i o nm a y r e s u l t f r o m t h e p r c s e n c eo f t r a c e so f
(39) lvt. Schlosser and V. Ladenbcrger, J. Organometal. Chem., E, 193 o t h e r t r a n s i t i o nm c t a l s i n t h e c o p p e r ( l )i o d i d e . r s "
( t 9 6 7) . ( 4 - l ) D . S e y f e r t ha n d M . A . W e i n e r ,J . O r g . C h e m . , 2 6 , 4 7 9 7( 1 9 6 1 ) .

Llthiresides, et ul. I Lithium Diulkv'l- and Diur"v'lcuprute Reactions


dure. Copper(t) iodide t0.677 g. j.5.1 mmol) was placed in a a l k y ' l b o r a n ea n d t h e n a l l o w e d t o r e a c t w i t h c i s - 2 - b u t e n ei n d i g l y m e
4o-ml centrifuge tube. The tube was capped wrth a serum stopper. s o l u r r o n a s p r e v i o u s l y d e s c r i b e d1. 6 " A f t e r o x i d a t i o n o f t h e r e s u l t r n g
and flamed dry under a stream of nitrogen. Ether (20 ml) was trralkylborane. the fraction containing 2-butanol, bp 60- 120
a d d e d t o t h e t u b e . a n d t h e r e s u l t i n gs u s p e n s r o nw a s c o o l e d t o - 5 0 , . .
was separated. dried by distillation from calcium lrydride, and then
A t t h i s t e m p e r a t u r e 4 . 0 m l ( 7 . 0 8 m m o l ) o f h a r i d e - f r e er r - b u t y l - fractronally drstilled in a spinning-bandcolumn. The purrlied
lithium solution was added. The tube was shaken vigorously for (+)-(S)-2-butanol was obtained in 55
5 min while holding the temperature between -50 and -2O". T, yield; bp 99_100, (76o
m m ) , r r : s D 1 . 3 9 5 8 ,d 2 5 r0 . 8 0 0 ,[ . r ] t t o + 1 0 . 6 9 . ( n e a t ) ( o p t i c a l p u n r ] ,
ccntrrfugation at - 78' separated the resulting suspension into a 79';1.st In a second run where the purification scheme di<i nor
smallquantity of black solid and a red solurion. This solutionwas i n c l u d e a d i s t i l l a t i o n l r o m c a l c i u m h y ' d r i d e ,t h e 2 - b u t a n o l r v a s o b -
t r a n s f i e r r e dt o a n o t h e r c e n t r i f u g e t u b e a n d h y d r o l y z e d . A n a l y s i s { s t a i n e d i n . 1 8 [ y i e l d ; 9 8 - 9 9 " ( 7 6 0 m m ) , n : 5 o 1 . 3 9 6 3 ,d 2 s t O . 7 g g .
r n d r c a t e dt h a t t h e h y d r o l y z e d m i x t u r e c o n t a i n e c l b u t a n e a n d c o p p e r
[ o ] t t o + 1 0 . 4 3 ' ' ( n e a r ) ( o p t i c a l p u r i t y , 7 7 ' 2 ' , 1 s[ rt i t . * b p 9 9 . 5 , , r r r 5 o
i n t h e r a r r o 1 . 8 9 : 1 . 0 o . o x i d a t i o n o f t h e o r g a n o m e t a l l i cs o l u t i o n 1.39501. In both runs the final product exhibited a single peak <;n
b e f o r e h y d r o l y s i s u s r n g m o l e c u l a r o x y g e n p r o d u c e d , r - o c t a n e( 4 o r , ) glpc.tt
and rr-butyl alcohol (2571, calculated on the basis of initial rr- The conversionof (+)-(s)-2-butanol ro (-)-(R)-2-bromobutane
butvllithium. similar trearment of n-burylrithium produced rr- was effected by an adaptatlon'n of a general procedure descrrbetl
b u t y ' l a l c o h o l e x c l u s i v e l y ; p u r e l i t h i u m d i - r r - b u t y r c u p r a t e ( l )y i e l d s p r e v i o u s l y . r T o a s o l u t i o n i l G - 1 5 , ) o f 1 5 . 0g ( 0 . 2 0 2m o l ) o f ( * . 1 _
8 0 ! r r - o c t a n ea n d 5 [ l - b u t y l a l c o h o l o n o x i d a r i o n . r e ( S ) - 2 - b u t a n o l 1 J 4 1 t s e+ 1 0 . 6 9 " , o p r i c a l p u r i t y 7 9 7 2 ) a n d 5 6 . g g
The exact nature o[ the mixtures produced by the reaction of (0.218 mol) of triphenylphosphinein 250 ml of dimethylfornramide
rr-butyllithium rvith copper( I) iodide in ether remains unclear. How- was added, droprvise and with stirring, sulhcient bromine so rnar
e'er, b'oth the approximate analysesoutlined above and the chem- t h e r e a c t i o n m i x t u r e m a i n t a i n e d a y e l r o w - o r a n g ec o l o r . T h e r e a c -
r c a l r e a c t r v i t y o f t h e m i x t u r e s i n d i c a t e t h a t t h e y c a n b e c o n s i d e r e da s tion mi.rture was slowly warmed to 45 " while volatile materialsrvere
m r x t u r e so f r r - b u t y l l i t h ui m and lithium di-rr-burylcuprate. allowed to distil lrom rhe reaction mixture under reduced pressurc
P r e p a r a t i o n so f " l i t h i u m d i - s e c - b u t y l c u p r a t e "a n d " r i t h i u m d i - / - (0.5 mml inro a cold trap. The crucre distiilate was parritionctl
burylcuprate"by direct reaction of 2 equiv oi arkyilithium reagent between pentane and water and the organic layer was washed wrth
wrrh I equiv of copper iodide followed an analogous procedure. aqueous NaHCOr, dried, and concentrated. Distillation of thc
S o l u t r o n s o f d i l i t h i u m t r i s {p h e n y l e t h y n y l ; c u p r a r ew e r e p r e p a r e d r e s i d u a l l i q u i d i n a T e f l o n s p i n n i n g - b a n dc o r u m n a f f o r d e d l { . 1 g
by permrrtrng 18.2 mmol of phenylethynyllithium (obtained by ( 5 I i ; o f ( - ) - (R ) - 2 - b r o m o b u r a n e .b p 9 0 ' ( 7 6 { )m m ) , l r 5 DI . . l l . t I
m r x i n g 1 . 8 5g ( 1 8 . 2 m m o l ) o f p h e n y l a c e r y l e n e . r/,r-,
a n d 1 0 . 7m l ( 1 g . 2 1 . 2 3 6 .[ . r ] , ' o - 2 6 . 0 2 ' ( n e a r )( o p r i c a lp u r i t y 7 i t o 7 g
m m o l ) o f m e r h y l l i t h i u m i n 2 0 m l o f e t h e r ) r o r e a c rw i t h l . l 5 g ( 6 . 0 6 \ for maximurn
r o t a t i o n s o f 3 5 . 7 a n d 3 3 . - l ' , r e s p e c t i v e l y ) . 3 0[ n a s e c o n d r e a c t i o n .
m m o l ) o f c o p p e r (I ) i o d i d e a r 2 5 " t o y i e l d a p a l e y e l l o w h o m o g e n e o u s (+)-(S)-2-butanol ([a]15o+ I0..ll", 77\ optically pure) was con-
s o l u t i o n . I f o n l y 2 e q u i v o f p h e n y t e t h y n y l l i t h i u mw a s u s e d / e q u i v verted in 63! yield to (-)-(R)-2-brornoburane,bp 9G-9t, r760
o i c o p p e r i o d i d e , a h e r e r o g e n e o u s y e l l o r v s u s p e n - s i o nw a s f o r m e d . m m ) , / r : r o l . - 1 3 5 Jd, 2 s t 1 . 2 . 1 6[ o , ] 5 o - 2 7 . 1 O , ( n e a t )( o p t i c a l p u n r !
A d d r t r o n o f o n e I ' u r r h e re q u i v a l e n t o l ' p h e n y l c t h y n y l l i t h i u mt o t h i s 7 6 t o 8 l ' ' l l b r m a x i m u m r o t a r i o n so t ' 3 5 . 7 a n d 3 3 . 4 " , r e s p e c t i v e l )y: ,
s u s p e n s r o nr e s u l t e d r n i m m e d r a t e t b r m a t i o n o l ' a p a l e y e l l o w s o l u - ' , s e a
9 0 - 9 1 . 51 , 5 67r ;, : rDs 1 . . 1 3 5 0 5 6 r ,I]n. e a c hc a s eo u r p r o t i _
I t i t . b p Q1 . 1
tlon. u c t e x h i b i t e da s i n g l c p e a k o n g l p c a n a l y s i s{.7 o u r e x p e r i m e n r ss u g -
Preparation of the Flulides and the I I1'drocarbon products. g c s t t h a t t h e m i n i m u m v a l u el b r t h e r o t a r i o no f ( - ) - ( R ) - 2 - b r o m o b u -
C o m m c r c i a l s a m p l e so l ' r r a r r s - s t i l b e n cI ,- p h e n y l n a p h t h a l e n en, o n a n e . t a n e s h o u l d b e - 3 3 . 0t o - 3 5 .I ' ' .
rr-hcxane. toluene. l-butylbenzene. sec-butylbenzene,l-octene.
R e a c t i o n o f m c t h y l l i t h i u m w i t h i o c i o b e n z e n ew a s c a r r i e c j o u t b - , .
1 . 1 - d r m e t h y l h c p t a n e1. - m e t h y l o c t a n e ,r - b u t y l b e n z e n e ,p h e n y l c y c l o - a c l d i n g - 1 . 6 2 m m o l o f m e r h y l l i r h i u mb y s y r i n g et o 1 . 6 2m m r l o l '
h c x a n e . l - m e r h y l n a p h t h a l e n e . a n d r r - o c t y l b e n z e n ew e r e u s e d f o r i o d o b e n z e n e d i s s o l v ' c di n - ' 1 . 5m l o l ' e t h e r a t 2 5 ' . T h e r c a c r r o r s
r d c ' n r r f i c a t i oann d g l p c c a l i b r a t i o n . l - l o d o o c r a n e ( E a s t m a n w h i t e w c r e a l l o r v e d t o s t a n d l b r l 5 - 1 0 m r n . h y d r o l y z e d .a n d a n a l y z c d b _ r
L a b e i l , i o d o b e n z e n e .a n d l - i o d o p e n t a n e w e r e u s c d w i t h o u t f u r t h e r grpc.
p u r r f i c a t r o n . C o m m e r c i a l l - i o d o n a p h t h a l e n ew a s r e d i s t i l t e db e f o r e
R e a c t i o n o f L i t h i u m D i m e t h l ' l c u p r a t ew i t h l o d o b e n z e n e . ( T y p i c e l
u s e ; b p I 5 l - 1 5 2 ' ( l 0 m m ) . r r : r D1 . 7 0 1 0 [ l r t .b{ p6 l 6 l - 1 6 2 " ( 1 5m m t . P r o c e d u r c ) . I o d o b e n z e n c ( 0 . 1 ( ) Jg , I m m o l ) a n d a w e i g h e d q u a r -
rrrrD 1.70541. Crude trans-$-bromostyrene lcu. l0% crs (first
t i t y ' o f a n i n t c r n a l s t a n d a r d( r r - o c t a n ew ) e r e p r a c e di n a l 5 - m l c c n -
c i u t e d ) a n d 9 0 ' . ' ; I r a t t s ( e l u t e d s e c o n d ) . , 7E a s t m a n O r g a n i c C h e m - trifuge tube capped with a scrum stopper. Trre tube was lrushcd
r c a l s lw a s p u r i f i e d b y t r e a t m e n t w i t h N a o H i n i s o p r o p y l a l c o h o l a s w i t h n i t r o g e n a n d i r s c o n r c n t sd i l u t c d w i t h e t h e r .t h e n t r a n s l c r r c d
p r e v r o u s l yd e s c r i b e d : ' { b p 5 9 - 6 1 . 5 ' ( 1 . 5 m m ) . r r r s D 1 . 6 0 6 0
[lit.ra t o a . 1 0 - m lc e n r r r l ' u g ct u b e c o n r a i n i n g5 m l ( 5 . 0 m m o l ) o f l i t h i u r n
b p J 5 - - ; 0 ' ( 1 . 1 5 m r n ) . r r r s D 1 . 6 0 . 1 8 1 i;r ( l i q u i d f i l m ) . 9 4 0 c m - r d i m c t h - v l c u p r a t es o i u t r o n a t - 7 s r h c t u b e w a s a l r o w e dt o l v a r n
u r u t t sC H : C H ) : nmr (CClr) 6 7.19(5 H aryl CH) and an AB t o r o o m t e m p c r a r u r c . A l i q u o t s ( - 0 . 5 m l ) w e r e r e m o v e c lp e r i o d -
pattern. : l4 Hz and esrimatedchemical shifts 6.60 and 7.00
"/ i c a l l l ' . a n d e i t h e r h - r ' d r o l v z c db - v a d r l i t i o n o i 0 . r 0 m l o f w a r e r o r
tl H. vrnyl CH). cir-rj-Bromostyrene was prepared from lrans- d i l u t e d b y c a . a l a c r o r o f 5 , ; ; o x i d i z e d b y e x p o s u r et o o x y g e n a r
crnnamrc acrd dibromide as previously described:{e bp 39-40, -78'', and analyzed by glpc. A collected
sampleof toluene rvas
t ( 1 . 5m m ) , r : 5 D 1 . 5 9 8 . 1 f l i t . b p 5 5 - 5 6 " ( 2 m m ) . r e 5 5 - 5 8 o( 2 m m ) , r s identified b-v comparison ol' ir spectrum and glpc retention tirnes
r i 5 D 1 . 5 9 8 0 ' 8 , r e ln; m r ( C C l { ) 6 7 . 1 - 7 . 7 ( 5 H m u l t i p l e t , a r y l C H ) , w i t h a n a u t h e n t i cs a m p l e .
6 . 8 7 ( l H d o u b l e t . : 8 H z . v i n y ' lC H ) . a n c l 6 . 2 3 ( l H d o u b l e t . . f control experimenrs indicated that the source of the lithrurn
"f
: 8 Hz. vinyl CH). Previously described procedureswere used to halides present in these reaction mi.rtures was not imporranr:
p r e p a r e c r s - s t i l b e n e . r " I . 8 - d i p h e n y l n a p h t h a l e n e . : rabn d 1 , 8 - d i i o d o -
r e a c t i o n sc o n t a i n i n g l i r h i u m h a l i d e p r e p a r e d f r o m 1 . 2 - d i h a l o e r n a n c
n a p h t h a l e n em . p 1 0 7 - 1 0 9 ' ( l i t . s t m p 1 0 9' ; . r , a n d a d d e d t o r h e p r e l b r m e d l i t h i u m d i m e t h y ' l c u p r a t es o l u r i o n s
( - ) - a - P i n e n e .[ a ] : 5 D - - 1 7 . 5 ' ( n e a t ) , i r r v a s c o n v e r t e d t o t h e d i - p r o d u c e d t h e s a m e y ' i e l d so f t o l u e n e a s d i d r e a c t i o n s c o n r a l n l n g
l i t h i u m h a l i d e o r i g i n a l l y p r e s e n ri n r h e m e t h y l l i t h i u ms o l u t i o n .
( - l - 5 )G l p c a n a l y s c so t ' n - b u t a n e w c r e o c c o m p l i s h c do n a c o l u m n P r e p a r a t i o n o f " . \ [ i . x e d " , \ t e C o m p l e x e s . U n s . v - m m e t r i c aOIx i d a -
c o m p o s c do t ' 3 X A p i e z o n L o n a l u m i r r a . E D T A r v a se m p l o y e df o r t i v e C o u p l i n g . C o p p e r (I ) b r o m i d e ( 1 . 4 2 6g , I 0 . 0 m m o l ) w a s p r a c e ( r
c o p p e ra n a l y s i s : c J ' .C . W . E l r v e l la n d L S c h o l c s .. . A n e l y s i so f C o p p c r i n a . l f ) - m [ c e n t r i l ' u g et u b e . T h e t u b e w a s c a p p e d w i t h a s e r u r ] r
a n d I t s A l l o y s , " P c r g a m o n P r c s s ,L t d . , L o n d o n . 1 9 6 7 . s t o p p e r a n d g e n t l y l l a r n e d d r y u n d e r a s r r e a m o f n i t r o g e n . T I - {F
( { 6 ) F . K r o l l p t t i f f c r , . 4 n nC. h e n r . . 4 3 0l,6 l ( l 9 l l ) . ( 5 m l ) a n d a n e t h c r s o l u r i o n o f p h e n y l l i t h i u m( 9 . 0 m l . I 8 m m o r )
( - 1 7 )A g l p c c o l u n r n p a c k c d , , v i r ha n i t r i l c s i l i c o n e g u m , X E - 6 0 ,
w e r e a d d e d t o t h e t u b e a t 2 5 . T h i s m i x t u r e r v a ss h a k e nv i g o r o u s i r
s u s p e n d e od n C h r o m o s o r b P w a s e m p l o y c dt o r t h i s a n a l y s i s .
( . 1 8 )L . J . D o l b y , C . W i l k i n s . f o r 5 m i n . I t r v a sr h e n c o o l e dt o - 7 8 ' a n d l . l 5 m l ( 2 . 0 m m o l ) o t ' a
" r n dT . C . F r e r , J, . O r q . C h e m . , 3 l ,l l l 0
(1966).
( - 1 9 )S . J . C r i s t o l a n d W . P . N o r r i s , J . . l m e r . C h e m .S o c . , 7 5 , f 6 l 5
rl95l). l0l0 (l9ll). Thcret'orc, thc roration of our samplc indicated.rrr
t 5 0 ) t a t L . F i c s c r ," E r p c r i m e n r si n O r g a n i cC h c n r i s t r y , l"r d c d , D . optrcal purirv of 93 '',.
C . H c a t ha n d C o . , B o s r o n ,\ l a s s . , 1 9 5 j ,p 1 8 6 ; ( b ) H . O . H o u s e R . . W. ( - s - l )P . J . L e r o u x a r r d H . J . L u c a s
lJ. ..lmer. Chem. Soc., 7J, .ll
\ t . r g i n , . r n dH . W T l r o m p s o r tJ. . O r g . C h e m . , 2 l tl,- l 0 l f l 9 6 j ) ; ( b ) H . t l95l)l rcport [a]:;o - lJ.-s' for (- )-l-buranor.
O . H o u s ea n d R . \ \ ' . B r r s h c l' ,l . i b i d . , 3 0 .l 9 4 l i l 9 6 5 ) ; 3 2 , 7 8 . 1( t 9 6 7 ) . ( 5 5 ) R . F . B r u n e l , J . L . C r c n s h e w ,a n d E . T o b i n , i b i ( t . , 4 3 , 5 7 . 1 ( l 9 l l ) .
( 5 1 ) R . S c h o l l ,C . S e c r ,a n d R . W c i t z c n b o c kB , er.,43,22OZ 0910). t56) (a) J. Timmcrnran and Y. Delcourt, J. Chim. ph.r's.,Jl, ,lo
( 5 1 ) T h i s c x p e r i m c n tr v a s p e r f o r m e di n o u r l a b o r a t o r i e sb y R o b c r t (l9l1l: (b) N. J. Leonlrd and E. W. Nommcnscn,./. Amer. Chern. Soc.,
W . B a s h c ,P h . D . D i s s c r ! a t i o r rA , u g 1 9 6 6 , i V l a s s a c h u s c tItnss t i t u r e o f 71. 1808 ( 19,19).
T c c hn o l o g y . (57) Thc yicld of couplcd producr obtairred on oxidation of diatkrl-
( 5 3 ) T h r ' r o t u r i o n r c p o r r c d f o r p u r c ( - ) - a - p i n c n ci s [ a ] : r o p- 5 1 . 1 8 , or ary'lalkylcuprates dccreascson incrcasing thc concertration ot' rlre
( n c : r ! ) : F . H . T h u r l ' r c ra n d R . C , T h i c l k c , . / . A n t e r . C h e m . S o c . , 5 3 . organocoppcr(I)rcagent to \ulues grcttcr !han ca.0.1 .t/.

J r u t r n u l , t l t l t e . . 1 n t t ' r i c r t t rC / t e n r i t ' u l S t t c ' i e t v q | . l7 ,


Auqu.tr lJ, /q4g
488I
p e n t a n es o l u t i o n o f t - b u t y ' l l i t h i u mw a s a d d e d . T h e r e s u l t i n g m i x - m l o f e t h e r w a s a d d e d a s o l u t i o n o f - 1 2 2m C ( 1 . 5 0m m o l ) o f l - b r o m o -
t u r e w a s s h a k e n t h o r o u g h l - v ,l o r l 0 s c c . I h e n o x i d i z e d b y a d d i t i o n adamantane in 1.0 ml o[ tetrahvdrofuran. After the resulting
of 60 ml of molecular oxygen by syringe at - 78 '. Hydrolysis and solution had been retluxed for 75 hr wirh no visible evidence
g l p c a n a l y s i s i n d i c a t e d t h e p r e s e n c eo f l - b u t y l b e n z e n e ( 7 3 7 4 , b a s e d of reaction. the solution rvas htdrolyzed and worked tp in the
on r-butyllithium). usualway. The crude liquid product contatnedsthe starting bro-
Coupling Reactionsof Lithium Diphcnl'lcuprate with .\lkyl and mide (retention time 23..1mrnt and a number of minor lower
!'iny'l FIafides. ,\. trurrs-p-Bromostyrene. To 20.7 ml of a cold b o i l i n g c o m p o n e n t s : n o p e a k c o r r e s p o n d i n gt o l - p h e n y l a d a m a n -
( 0 ' ) e t h e r s o l u t i o n o f l i t h i u m d i p h e n y l c u p r a t c ,p r e p a r e d f r o m 7 2 8 t a n e ( r e t e n t i o n l i m s - 1 - 1 .m 4 i n ) w a s d e t e c t e d . A n a u t h e n t i cs a m p l e
mg (5.0 mmol) of coppei(l) bromide and 10.0 mmol of phenyl- o f l - p h e n y ' l a d a m a n t a n e . m p8 6 - 8 7 : ( l i t . s e tmr p 8 8 - 8 9 o ) ,w a s p r e p a r e d
lithium. was added -l ml of an ether solution containing l.0l mmol a s p r e v i o u s l y d c s c r r b c d . 5 e " T h e s p e c t r a l p r o p e r t r e so f t h e p r o d u c r
o f t r a r r s - i 3 - b r o m o s t y r e naen d a k n o w n w e i g h t o f h e x a m e t h y l b e n z e n e correspond to those previously described.5et,,"
(an internalstandard). The resulting mixture. from which a yellow- Reaction of Lithium Dimethrlcuprate with l-Iodooctane. Ether
green precipitate slowly separated, was stirred at room tempera- s o l u t i o n s ( 6 . 0 m l ) c o n t a i n i n c 2 . 0 Om m o l o f i o d o o c t a n e ,a w e i g h e d
ture under a nitrogen atmosphere. An aliquot removed after 2 hr a m o u n t o f l - d e c a n e ( i n t e r n a l . s t a n d a r d ) a, n d t h e v a r i o u s o r g a n o -
rvasquenched in saturated aqueous NHrCI (adjusted to pH 9 with m e t a l l i c r e a g e n t ss p e c i f i e d b c l o r v r v e r es t i r r e ( l a t r o o m t e m p e r a t u r e
added NHr) and then e,\tracted with benzene. After the benzene and aliquots were periodically removed. hydrolyzed, and ana-
solution had been rvashedwith aqueous NaCl, it was dried, con- lyzegl.t;'s, In the reaction rvrrh 2.00 mmol of lithium dimethyl-
c e n t r a t e d ,a n d a n a l y z e d b y g l p c . s t T h e c a l c u l a t e d y i e l d s w e r e 7 5 \ c u p r a t e . a l i e r 2 . 6 7 h r t h e c a l c u l a t e d y i e l d o f , r - n o n a n ew a s 9 7 / , a n d
o f t r a r r s - s t i l b e n ea n d 1 9 i i o f u n c h a n g e d s t a r t i n g b r o m i d e . A f t e r o n l y 3 [ o f t h e r r - o c t y ' li o d i d e r e m a i n e d . I n a s i m i l a r r e a c t i o n w h e r e
a total reaction period of .l hr, the remaining reaction mixture was 2 1 . 0 0m m o l o f m e t h y l l i t h i u m w a s r r e a r e d r v i t h o n l y 0 . 1 0 m m o l ( j
quenched, worked up, and analyzed.s6 The components detected mol %) of copper(l) iodide, the calculatedyields after a l2-hr
( i n o r d e r o f e l u t i o n ) 5 8w e r e : s t a r t i n g b r o m i d e ( 4 % r e c o v e r y ) , b i - r e a c t r o n p e r i o d w e r e l 9 [ r r - o c t a n e .6 . 5 9 " l - o c t e n e . 6 4 2 , n - n o n a n e ,
p h e n y l , h e x a m e t h y ' l b e n z e n e( i n t e r n a l s t a n d a r d ) . a n d / r a r r s - s t i l b e n e and 2 i ot'the starting rodide. When 4.00 mmol of methyllithiun-,
(90% yield). Comparable results (511 bromo olefin and 90gl w a s u s e d r v i t h n o a d d e d c o p p e r s a l t t h e y i e l d s a l ' r e ra l 2 - h r r e a c t i o n
I r a r r s - s t i l b e n ew
) ere obtained in a secondreaction. In each casethe w e r e 2 7 9 1 r r - o c t a n e .l 8 : ; l - o c t e n e . 6 [ r r - n o n a n e .a n d 4 2 \ o f t h e
y ' i e l d o f c r s - s t i l b e n e( e l u t e d b e t o r e l h e I r u t t s i s o m e r ) w a s l e s s t h a n u n c h a n g e d i o d o o c t a n e . C o l l e c t e d s a m p l e s o f r r - n o n a n e ./ t - o c t a n e .
2 - o . A c o l l e c t e d s ds a m p l e o f t h e / r r u r s - s t i l b e n ew a s i d e n t i f i e d w i t h and l-octene rvere identified wrrh authentic samplesby comparison
an authentic sample by comparison of inirared spectra and glpc of infrared spectra and glpc rerention times. Two glpc columns
retcntion tirnes. were required for anal;sis. On one columni8the order of elution
B . r ' i . r - d - B r o m o s t ] - r e n e .T h c c o r r e s p o n d i n g r e a c t i o n o f 5 . 0 0 w a s / r - o c t a n e a n d l - o c t e n e ( u n r e s o l v e d ) ,n o n a n e , d e c a n e , a n d l -
m m o l o f l i t h i u n r d i p h e n y ' l c u p r a r ea n d 1 . 0 2 n r r n o l o f c i s - p - b r o n r o - iodooctane. A second columnri was used to resolve /,-octanc
. s t y r e n e i n 2 - 1 . 5m l o l ' c t h c r w a s r u n l b r 2 h r a t r o o m t e m p e r a t u r e . ( e l u t e d f i r s t ) t i o m l - t l c t e n e( e l u r e ds e c o n d ) .
The crude product colltained (in order ol' clution:58 biphenyl, Reaction of Lithium Dimethr'lcupriltc with l-[odonaphthalene.
hexamethylbenzcnc, arrd ci.r-stilbene (cak ula:ed yields 72 and E t h e r e a l s o l u t i o n s c o n t a i n i n g h e x a m c r h y l b c n z e n e( i n t e r n a l s t a n -
73i in two reacrions). In each case, tltc yrcld ot' Irarrs-stilbene d a r d ) a n d t h e m o l l r c o n c e n r r a r i o n so l ' l - i o d o n a p h t h a l e n ea n d I i t h -
rvas less than I'1. A c o l l e c r e d 5 ss a m p l e o t ' r h e c i s - s t i l b e n e w a s i u m d i m e t h l , l c u p r a t e i n d i c a t e c li n T a b l c l l r v c r e s t i r r e d a t r o o m
identified with an aurhentic sample by comparison of infrared spec- t c m p e r a t u r e ( 2 5 - 2 7 ' ) a n d a l i q u o r s r v e r er e m o v e d a t t h e i n d i c a t e d
t r a a n d g l p c r e t c n t i o nt i r n e s . t i m e s a n d h y ' d r o l y z e da n d a n a l . v z e di n t h e u s u a l w a y . W i t h t h e
C. Iodooctane. The reacrion of 5.00 mmol of lirhium diphenyl- g l p c c o l u m n u s e d . 5 t h e c o m p o n e n t sw e r e e l u t e d i n t h e o r d e r n a p h -
cuprate with l.0l mmol of l-iodoocrane in 2J.7 ml of ether con- t h a l e n e . l - m e t h y l n a p h t h a l c n e . h e . r a m e t h y l b e n z e n ea. n d l - i o d o -
t a r n i n g a w e i g h e d a m o u n t o f l - m e t h , " ' l n a p h r h a l e n e( a n i n t e r n a l n a p h t h a l e n e . C o l l e c t e d ; Es a m p l e so l ' n a p h t h a l e n ea n d i t s l - m e t h y , l
s t a n d a r d )w a s r u n a t r o o m t c m p c r a r u r el b r 2 h r . T h e c r u d e n e u t r a l d e r i v a t i v e w e r e i d c n t r t i e dw i t h a u t h c n t i c s a m p l e sb y c o m p a r i s o n o l '
p r o d u c t c o n t a i n e d( l i s t e d i n o r d e r o [ e l u t i o n ) : $ l - m e t h y l n a p h t h a - i n l r a r e d s p e c t r a a n d g l p c r e t e n t i o n t i m e s . I n c e r t a i n c a s e sh a l i d e -
l e n e ,b i p h e n y l .a n d r - o c t y l b e n z e n e( c a l c u l a t e dy i e l d s9 9 a n d l 0 0 f i n l ' r e el i t h i u m d i m e t h y l c u p r a r ew a s e m p l o y e d : i n o t h e r s t h e r e a c t i o n
t w o r e a c t l o n s ) . A c o l l e c t e d 5 Es a m p l e o f t h e n - o c t y l b e n z e n e w a s s o l u t i o n c o n t a i n c d L i l i n a c o n c e n t r a t i o ne q u i v a l e n tt o t h e c o p p e r
rdentitiedwith an aurhenric sample by comparison of infrared r e a g e n t . T h e p r e s e n c eo t ' L i l i s r n d i c a t e di n T a b l e I I . I n c e r r a i n
s p e c t r aa n d g l p c r e t e n t i o n t i m e s . of the runs an oxidant rvas added to one aliquot of the reaction
D . ( - ) - ( R ) - 2 - B r o m o b u t e n e .A m i x t u r e o l ' 1 2 0 m m o t o f l i t h i u m m i x t u r e a t t h e e n d o l ' t l r e s t a t e d r e a c t i o np e r i o d b e l b r e t h e r e a c t i o n
d i p h e n r ' l c u p r a r ca n c l 5 . 0 0 g ( i 6 . 5 m m o l ) o i f - ) - ( R ) - 2 - b r o m o b u r a n c m l x t u r e w a s h ; , d r o l v z e d a n d a n a l l ' z e d . N r t r o b e n z e n ew a s a d d e d
( [ c r ] : s o- 2 6 . 0 2 . , o p t i c a l p u r i t y 7 3 - 7 8 i ) i n a m i x t u r e o f 1 2 9 m l o t ' t o t h e r e a c t i o n s o l u t r o n r l r a k n o r ' , ' nv o l u n r e o t ' o x y ' g e nw a s a d d e d t o
cther and 180 ml of tetrahydrofuranwas relluxed (51-52,) for 72 t h e n i t r o g e n a t m o s p h e r ea b o v e t h e r e a c t i o nm i x t u r e a n d t h e m i . r t u r e
h r a n d t h e n q u e n c h e di n a q u e o u s N H r C I a n d e x t r a c t e d w i t h e t h e r . was thoroughly mrxed by shaking. Addition of oxygen resulrs
A l ' t e r t h e e t h e r e a ls o l u t i o n h a d b e e n w a s h e d w i t h a q u e o u s N a C l . in immedratelbrmation of a black precipitate; addition of nitro-
d r i e d . a n d c o n c c n t r a r e d .d i s t i l l a t i o n o t ' t h e r e s i d u a l l i q u i d t h r o u g h a b e n z e n ep r o d u c e s a d e e p r e d c o l o r i n s o l u t r o n .
T e f l o n s p i n n i n g - b a n dc o l u m n s e p a r a r e d. 1 . 3 3g ( 8 7 i o ) o f ( + ) - ( $ - I n r e a c t i o n s o t ' l - i o d o n a p h t h a l e n ew i t h t h e t r i - n - b u t y l p h o s p h i n e
2 - p h e n y l b u t a n eb. p 1 7 0 ' . r r ! 5 o 1 . 4 8 7 9 ,r / : 5 r0 . 8 5 6 . [ o ] t o + 1 8 . 2 0 . complex of methylcopper. the rnrtial reacrion mixtures were hy'-
(neat) (optical purity 67'':).se [n a second run employing (-)- d r o l y z e d w i t h a q u e o u s l . . l , t / H C I r a t h e r t h a n t h e a q u e o u sN H , C I
( R ) - 2 - b r o m o b u t a n e( [ a ] t t o - 2 7 . 0 1 . , o p r i c a l p u r i t y 7 6 - 8 l to facilitateseparationof the trr-l-butylphosphine. [n certain of
%) rhe
( * ) - { S ) - 2 - p h e n y l b u t a nw e a s o b t a i n e di n 6 7 \ , ; - i e l d ; b p 1 6 9 - 1 7 0 " , t h e s e r e a c t i o n s r v i t h t h e p h o s p h i n e c o m p l e . \ .t h e i n i t i a l e t h e r s o l u -
r r r 5 D1 . 4 8 7 7 r. / : 5 r0 . 8 5 5 .[ o ] . u o + 1 8 . 7 0 ,( n e a t ) ( o p t i c a l p u r i t y 6 g 7 1 t , , t i o n r v a s c o n c e n t r a t e d u n d e r r e d u c e d p r e s s u r ea n d t h e r e s i d u e w a s
( l r t . 5 eb p 1 7 2 ' , r t 2 3 o1 . 4 8 8 3 ) . I n e a c h c a s e t h e d i s t i l l e d p r o d u c t e i t h e r d i s s o l v e d i r r r e t l L r x r n gt e t r a h y d r o f u r a n o r h e a t e d t o 6 0 - 7 0 '
e x h i b i t e d a s i n g l e p e a k o n g l p c . " p r e l i m i n a r y e x p e r i m e n t ss t u d y ' - r v i t h o u t a d d e d s o l v e n t . t b r l - 2 h r p r i o r t o a n a l y s i s . o6E0 , 6 r T h e
i n g t h e r e a c r i o n o t ' l i t h i u m d i p h e n y l c u p r a t ew i t h r a c e m i c 2 - b r o m o - c a l c u l a t e d 6 0. " " i e l d so f p r o d u c t s v v ' e r el 5 - 1 3 " ; n a p h t h a l e n e a n d 6 G -
butane were perlbrmed wirh an internal standard (rr-butylbenzene) 85T l-methtlnaphthalene. Although no oxidant was deliberatell
p r e s e n t t o p e r m i t g l p c a n a l y s i s . { 7 T h e l b l l o w i n g c a l c u l a t e dy i e l d s a d d e d t o t h e s e l a t t e r r e a c t i o n m r x t u r e s . t h e p o s s r b i l i t yt h a t s o m e
of 2-phenylbutane were obtained afrer a 2{hr reaction period oxygen (ltom the air) nray have reached the reaction mixtures can
u n d e r t h e s p e c i f i cc o n d i t i o n s : g ' i i n e t h e r a r 2 5 . : 5 1 % i n e t h e r - not be excluded. in spite of our eflorts to maintain an oxygen-free
I . l - d i m e t h o x y e r h a n e ( 3 : . 1v / v ) a t 6 0 - 6 - l ; 7 2 \ i n e r h e r - r e t r a h y d r o - atmosphere.
f u r a n ( 3 : J v , v ) a t 5 2 - 5 4 ' . U n d e r t h e s a m e c o n d i t i o n sr e a c r i o n A s a c o n t r o I e x p e r i m e n t . a n er h e r s o l u t i o n o l ' n a p h t h a l e n e( 2 . 9 6
of l-bromobutane wrrh phcnyllirhium in boiling ether for 2l hr m m o l ) a n d t h e t r i - r r - b u t y l p h o s p h r nceo m p l e x o f m e r h y l c o p p e (r 1 0
lbrmed 2-phenylbutanc in -l'T yield. when rhe time lbr the reac-
tion rvith lithium diphenylcuprate in the erher-tetrahydroluran
mrxture was exrcndedto 72 hr. rhe calculatedyield of 2-phenyl- (59) (a) H. Stcttcr. \l . Schrvartz. arrd A. Hcrschhorn, Chem. Ber..
b u t a n e r v a s 8 . 1' 1 . 9 2 . l 6 1 9 ( 1 9 5 9 ) ; ( b ) R . C . F o r r , J r . , a n d P . r o n R . S c h l e y e r ,J . O r g .
E. l-Bromoadamcntane. To a solution ot' -1.50mmol of di- Chenr.,30, 789 (1965): tc) Z. Dolel:uk, S. Hula, V. Hanus, and S.
p h e n y l c u p r a t ei n a m i x r u r e o f 6 . 8 m l o t ' t e t r a h y d r o f u r a n a n d 5 . 0 Landa, Collect. C:ech. Chern. Comrnun., 31, -ll5 ( 1966).
( 6 0 ) A g l p c c o l u m n p a c k c d * i t h C a r b o r v a x l 0 \ 1 s u s p e n d e do n C h r o -
m o s o r b P r v u s em p l o y c d f o r t h i s a n a l ys i s .
( 6 1 ) A n a l y s c s d o n c u i t h a C u r b o r " ' a x c o l u m n 6 ' ru s c d b i p h e n y l a s a n
( 5 8 ) A g l p c c o l u m r r p a c k c d r v i t h s i l i c o n cg u m , S E - 5 1 , suspcnded
on itrternal standurd. On this column the ordcr ot' clution was: naph-
C h r o r n o s o r b P w ' u se m p l o y c d t b r t h i s a r r l l l ' s i s . t h a l c r r c ,l - r n c t h v l n l p h t h a l c r r c ,b i p n c n r l , a n d l - i o d o n a p h t h a l e n e .

Litltitttrt Diulk y l- ttnd Diury'lc'trDrute Reaclion.s


.1882

m m o l ) w ' a sc c n c e n t r a t e d a n d t h e n h e a t e d t o 5 0 ' - 6 0 of o r 2 h r . A f t e r l-phentlnaphthalene (567]' yield), and 1,8-diphenylnaphthalene


h y d r o l l s r s . n o l - m e t h v l n a p h t h a l e n e w a s d e t e c t e d mi n t h e c r u d e (5T yreldt. The second aliquot was cooled to 0'', oxidized wrrh
reactron producr. A lso an ethereal solution containing hexa- g a s e o u so x y g e n . a n d t h e n h y d r o l y z e d t o p r o d u c e a m i x t u r e c o n -
m e r h v l b e n z e n e-. 1 . f ) 0m r n o l o f h a l i d e - f r e e m e t h y l l i t h i u m . a n d l ' 0 0 t a r n r n g : 1 . 2 - d i p h e n y l e t h a n e l. - p h e n y l n a p h t h a l e n e( 2 % y i e l d r .
m m o l o f l - i o d o n a p h t h a l e n ew a s s t i r r e d f o r 2 h r a t r o o m t e m p e r a - a n d 1 , 8 - d i p h e n y l n a p h t h a l e nG e 7 7 ' , y i e l d ) . C o l l e c t e d s s a m p l e so i
t u r e a n d t h e n h v d r o l y z e d a n d a n a l y z e d . 5 8 T h e c a l c u l a t e dy i e l d s naphthalene. l-phenylnaphthalene.and 1,8-diphenylnaphthalene
r v e r el l i n a p h t h a l e n ea n d 8 6 7 " l - r n e t h y l n a p h t h a l e n e . w e r e i d e n t i f i e d w i t h a u t h e n t i c s a m p l e s b y -c o m p a r i s o n o f i n f r a r e d
Reaction of Lithium Diphenylcuprate with ,\ryl Halides. '\. spectra and gas chromatographic retention times. Prelimrnarv
l - l o d o n a p h t h a l e n e . E t h e r s o l u t i o n sc o n t a i n i n g 1 . 2 - d i p h e n y l e t h a n e experiments had demonstrated that a 2{-hr reaction period pre-
(an inrernal standard) and the molar concentrationsof lithium c e d i n g o . r i d a t i o n w a s n e c e s s a r yi n t h i s c a s e t o c o m p l e t e t h e i n i t r a l
t J r p h c n lrc u p r a t e a n d l - i o d o n a p h t h a l e n e i n d i c a t e d i n T a b l e I I I metal-halogen exchange.
r r c r e s t i r r e d a t r o o m t e m p e r a t u r eQ 5 - 2 7 " ) . A t t h e t i m e s i n d i c a t e d R e a c t i o n o f L i t h i u m D i a l k y ' l - a n d D i a r y l c u p r a t e s w i t h . - \ l k yl
r T a b l e I I I ) a l i q u o t s l v e r c r e m o v e d , h y d r o l y z e d . a n d a n a l y z e di n t h e Halides. The data of Table IV were obtained using a common
u s u a l r v ' a y ' . O n t h e g l p c c o l u m n s u s e d . s ' 6 2t h e o r d e r o f e l u t i o n o f procedure. illustrated here by the coupling of lithium di-rr-but1'l-
c o m p o n e n r s w a s: i o d o b e n z e n e , n a p h t h a l e n e . b i p h e n y l , 1 , 2 - d i - cuprate rvith l-chloropentane. One milliliter of a THF solutron
p h e n y l e t h a n e . l - r o d o n a p h t h a l e n e ,l - p h e n y l n a p h t h a l e n e ,a n d l , l ' - c o n t a i n i n g 1 . 0 m m o l o f l - c h l o r o p e n t a n ew a s a d d e d i n o n e p o r t i o n
binaphthyl. Collectedt8 samples of naphthalene and 1-phenyl- to a solution ot 5.0 mmol of lithium di-rr-butylcuprate in 5 ml ot'
n a p h r h a l e n ew ' e r e i d e n t i f i e d w i t h a u t h e n t i c s a m p l e s b y c o m p a r i s o n THFat -78'. T h i s m i x t u r e w a s a l l o r v e dt o s t a n d f o r I h r a t : 5 '
o l ' i n f r a r e d s p e c t r a a n d g a s c h r o m a t o g r a p h i cr e t e n t i o n t i m e s . A l l w i t h o c c a s i o n a ls w i r l i n g , t h e n c a u t i o u s l yh y d r o l y z e d a n d a n a l y z e d
o t ' r h e d a r a p r e s e n r e di n T a b l e I I I r v e r e o b t a i n e d w i t h l i t h i u m d i - by glpc directly.
p h e n y l c u p r a t er v h i c h c o n t a i n e d s o m e l i t h i u m h a l i d e . W h e n t h e Preparative Scale Reaction of Lithium Di-rr-butyl(tri-r-butr'l-
c u p r a t e r e a g e n tw a s p r c p a r e d f r o m w a s h e d 5 h e n ul c o p p e r p r e c i p i t a t e p h o sp h i n e ) c up r a t e u ' i t h l - I o d o p e n t a n e . T e t r a k i s [ i o d o (t r i - n - b u rv l -
: , r n dr e c r y ' s t a t l i z epdh e n y l l i t h i u m s o t h a t o n l ) 0 . 1 - 0 . 2 e q u i v o f h a l i d e p l r o s p h i n e ; c o p p e r ( l ) l( 7 6 . 6 g , 0 . 1 9 5 m o l ) w a s p l a c e d i n a t l a m c -
salts rvas present.the irrrtial exchangereaction benveen the cuprate d r i e d . t h r e e - n e c k e d . l - 1 . f l a . s ke q u i p p e d r v i t h a n i t r o g e n i n l e t a n d
a n d l - i o d o n a p h t h a l e n ew a s s l i g h t l y s l o w e r t h a n t h e c o r r e s p o n d i n g m e c h a n i c a l s t i r r e r . E t h e r ( 5 0 0 m l t r v a sa d d e d a f t e r t h e f l a s k h a u
rerctron rvnerc cxcess lithiunt bromide was present. Certain b e e ne v a c u a t e da n d f i l l c d r v i t h n i t r o g e ns e v e r a tl i m e s . T h e r e s u i t i n g
r e r c t i o n a l i c l u o t sw e r e t r e a t e d r v r t h v a r i o u s o x i d a n t s p r i o r t o h y - solution rvascooled to -78'and 210 ml (0.39mol) of rr-bunl-
drolvsis and analysrs. With the solid and liquid oxidants. the lithium in hexane rvas edded wrth stirring over a 20-min penod.
re3ctlonmixtures rverc stirred for l5 min after addition to ensure l - [ o d o p e n t a n e( 1 0 . 0 g , 0 . 0 3 9 1 m o l ) m i x e d r v i t h l 0 m l o f e t h e r w u s
compicte oxiclation. [:or reaction rvith oxygen gas, the solutions translerredby cannula into the reaction mixture and stirring corr-
w c r e s t r r r e d r v ' h i l ca l a r g c e x c e s so t ' g a s w a s ; l a s s c d o v e r t h e s u r f ' a c e tinued tbr 30 min at - 78'. The mixture was allowed to warm t()
o t ' t h es o l u t i o n . r o o m t e m p c r r r t u r ea n d s t i r r e d i o r 6 h r . t h e n c o o l e d t o - 2 0 ' l r r r r l
. { s a c o n t r o l e x p e r i n t c t r t .I l . 7 m l o f a n e t l ' l c r e s sl o l u t i o n c o n t a i n - c a r . r t i o u s l l h' y d r o l y z e d r , v r t h 1 0 0 m i o f 5 . V / h y d r o c h l o r i c a c i d . T h c
r n g 1 . 5 0 m m o I o t ' p h c r r v l l i t h i u ma n d 0 . 5 0 m m o l o f l ' i o d o n a p h t h a - trvo layers were separated. and the aclueous layer rvas rva.shcrj
l e n e r v a s s t i r r e d a t r o ( ) r l l t c m p e r a t u r e .a n d a l i q u o t s w e r e r e m o v e d , w i t h t r v o 1 0 0 - m l p o r t i o n s o f p e n t a n e . T h e c o m b i n e do r g a n i c p l t a s c
h r d r o l y z e d . a n d l n a l y z c d 5 sp c r i o d i c a l l y . A l t h o u g h 9 6 % o f t h e was treatcd wrth decolorizing charcoal. tiltered through Cclrtc.
l - i t t d o n a p h t h a l c n eh a c l l r c e n c o n v e r t e d t o l - n a p h t h l , l l i t h i u m( n a p h - a n d d r i e d . S h o r t - p a t hd i s t i l l a t r o n( b p l - 1 5 - 1 6 0 ' )y i e l d e d5 . 1 0 g o t '
t h a l e n e a t ' t e r h y c i r o i y s r s )a l ' t e r I h r . n o l - p h e n y l n a p h t h a l e n ew a s c r u d e p r o d u c t w h i c h g l p c a n a l y s r si n d i c a t e dt o b e 8 G ' 8 2 [ r - n o n a n c
d c t c ' c t e di n t h e r e a c t i o n t t r i x t u r ee v e n a f t e r a l { . h r r e a c t i o np e r i o d . ( t h e o r e t i c a ly i e l d 5 . t \ ) g , t . T h e i m p u r i t i e si n t h i s m a t e r i a l a p p e a r c t l
A n e t h e r e a ls o l u t r o n p r c p a r e d f r o m 1 . 0 m m o l o t ' t h e t r i - r r ' b u t y l - t o b e p r o d u c e d b . " -t h e r m a l d c c o m p o s i t i o n o [ t r i - r r - b u t y l p h o s p h i r r c -
phosphrne c o m p l e x o t ' c o p p e r ( l )i o d i d c . 1 . 0m m o l o i p h e n y l l i t h i u m . c o p p c r ( l ) c o m p l e x e si n t h e d r s t r l l a t i o np o t . A l r a c t i o n ( b p l 5 l -
( ) . 1 - 1m m o l o f l - i o d o n l p h t h a l e n e , a n d a n i n t e r n a l s t a n d a r d r v a s 1 5 4 . 5 ' ) t a k e n d u r i n g r e d i s t r l l a t r o nt h r o u g h a g o l d s p i n n i n g - b a n d
c ( ) n c e n t r a t e du n d c r a n t t r o g e n a t m o s p h e r ea n d t h e n h e a t e d t o 9 G - c o l u m n h a d r r : 5 o l . - 1 0 7 0a n d a n r r s p e c t r u m a n d g l p c r e t e n t l o n
95' tbr 2 hr. The resulting mixture was treated rvith 2.0 ml of time icienticaw l i t h t h o s c o f a u t h e n t t cf l - n o n a n c .
dcuterrum oxide solutron containing DCI (10"; by weight) and R e a c t i o n o f . \ l l - vI ' O r q a n o m e t aI l i c D e r i v a t iv e s w i t h l - I o d o p e n t a n e .
t h r n s u b j e c t e dt o t h e u s u a I i s o l a t t o na n d a n a l y s i s . 5 s T h e c a l c u l a t e d T o a c o l c l ( - 7 8 ' ) s o l u t r o no f l r t h i u m d i a l l y l c u p r a t ep r e p a r e dl . r o m
y r c i d s r v e r e : 5 ' l i o d o l r e n z e n e2. J ' [ n a p h t h a l e n e .5 2 % l - p h e n y l - l . - 1 5g ( 3 . [ X )m m o l ) o f t h e b i s t r r - l r L r st yul l f i d e c) o m p l e xo f c o p p c r t l t
'- i o d i d e a n d 6 0 0 m m o l o f ' a l l - v l l i t h r u r ni n 1 0 . 2m l o f e t h e r w a s a t l d c t i
n a p h t h a l e n ea . n d 6 " , ; | . I [ ; i n a p l r t h v ' 1 .A c o l l e c t e d s s a m p l e o f t h e
n t p h r h a l e n ec o n t a i n e t i ( r n a s s. s p e c t r o m e t r i ca n a l y s i s) 8 3 % c / rs p e c i e s 1 . 0 m i o l ' a n e t h e r s o l u t i o n c o n t a i n i n g1 . 0 0m m o l o f l - i o d o p e n t a r l u
and l7''i r/, species. Various attempts to improve the yield of l- a n d a k n o r v n w e i g h t o l ' r - n o n a n e ( a n i n t e r n a ls t a n d a r d ) . A f t e r t l r c
p h e n y t n a p h t h a l e n ew i t l t o u t u s e o f a n o x r d a n t s u c h a s t h e u s e o [ m i x t u r e h a d b e e n s t r r r e df o r I h r a t - 7 8 ' i t w a s a l l o w e d t o w a r n t t t l
q u r n o l i n ea s a s o l v e n t o r t h e u s e o f n o s o l v e n t g a v e c r u d e p r o d u c t 0 " ( t h e c o p p e r r e a g e n t d e c o m p o s e dw i t h s e p a r a t i o n o f m e t a l l i c
m r \ t u r e s i n r v h i c h t h e c a l c u l a t e d 5 dy i e l d o f l - p h e n y l n a p h t h a l e n e c o p p e r ) a n d t h e n q u e n c h e d i n a n a q u e o u ss o l u t i o n o f N H r C I a n d
r a n g e df r o m 0 t o 5 0 " , i . N H r a n d e x t r a c t e dw i t h e t h e r . A f t e r t h e e t h e r e a ls o l u t i o n h a d b e e n
B . 1 . 8 - D i i o d o n a p h t h n l e n e .A s o l u t i o n o f 1 . 2 - d i p h e n y l e t h a n e . w a s h e d w i t h w a t e r . d r i e d . a n d c o n c e n t r a t e d .a n a l y s i s b y g l p c d t
6 . 0 m m o l o f l i t h i u m d i r r h e n y l c u p r a t ea. n d 3 8 0 m g ( 1 . f f ) m m o l ) o f i n d i c a t e d t h e p r e s e n c eo f l - o c t e n e( y i e l d s i n t w o r u n s 9 8 a n d l [ I ) " , ; .
I . S - d i i o d o n a p h t h a l e n rcr r I 0 m l o l ' e t h e r w a s r e f l u x e d f o r 2 ' l h r a n d f i r s t e l u t e d ) a n d / r - n o n a n e ( e l u t e d s e c o n d ) . A c o l l e c t e d o rs a m p l e
then two aliquots rverc rentoved. One aliquot was hydrolyzed of the l-octene was identifiedwith an authenticsample by'cont-
w i t h o u t a d c l i t i o no t ' a r r o x i d a n t t o g i v e a m i x t u r e c o n t a r n i n g( i n p a r i s o n o f i n f r a r e d s p e c t r aa n d g l p c r e t e n t i o nt i m e s . A c o m p a r a L r l c
order o[ elution):;8 nlphthalene (35[ yield), 1,2-diphenylethane. r e a c t r o n w a s r u n w i t h - 1 . 0 0m m o l o f a l l y l l i t h i u m a n d 1 . 0 0 m m o I o l '
l - i o d o p e n t a n ei n 9 . 0 m l o f e t h e ra t 1 5 " f o r I h r . A f t e r t h e m i x t u r c s
from trvo identical runs had been hydrolyzed, dried, and concen-
r6l) A glpc column prrckedwith silicone gum. No. SE-10' suspended t r a t e d . a n a l y - s i s 6i tn d i c a t e d t h e p r e s e n c eo f l - o c t e n e ( y i e l d s 9 8 a n d
o n C h r o m o s o r b P r v a ser r r p l o y c d l o r t h i s a n a l y s i s .
gg'I,).