[Reprinted from the Journal of the American Chemical Society, 96,2829 (1974).

] Copyright 1974by the American Chemical Soeiety and reprinted by permission of the copyright owner.

Reactions,and Copper(I) Alkoxides. Synthesis, Thermal Decompositionl

George M. Whitesides,* John S. Sadowskioand Jennifer Lilburn C o n tri b u ti o n fro mtheD epartmentofC herni stryl .| 14,,' sochuse| tsl nsti tuteo. f Nouember17, 1973 Massachusetts 02139. Receiued Technology,Cambriclge,

reaction betweenalcohols Abstract: Alkoxides and phenoxides of copper(I) can be prepared by the heterogencous for the formation of and phenols and methylcopper(I). These organocopper(I) compounds are useful reagents organic halides. The reaction of copper(l) alkoxidcswith aryl halidesyields of ethersby displacement haiide from reagcnts alkyl aryl ethersunder particularly mild ionditions. Thermal decompositionof primary alkorycopper(l) Thermal clecomposition of secondary alkoxycopper(l) reagents generates intermediate alkoxy radicals. to involve apparently can take place either by a free-radicalmechanismor by a mechanismtentatively suggested factors determining which mechanismwill predominatefor copper(I)-hydrideas an intermediate. The structural a given compound have not been established'

tTth. utitity of alkyl- and arylcopper(l) reagents in I or ganic s y nt h e s i si s b a s e d o n th e i r h i g h nucl eop h i l ic it y t owar d c a rb o n , a n d o n th e i r a b i l i ty to take reactions.2-a They also show part in electron-transfer low basicity toward protons, an afffinity for carbonca rbon double bon d s , a n d a n a b i l i ty to c o o rd i n atew i th soft Lewis bases. Since the mechanisms by which copper(I) influences the reactivity of carbanions are not clearly understood, it is difficult to predict the beh a v ior of new t y p e s o f o rg a n o c o p p e r(I)c o mpounds. Nevertheless,there is obvious reason to hope that organic derivatives of copper(I) other than those bec l o nging t o t he we l l -e x p l o re d l a s s o f c o mp o u nds containing carbon-copper bonds might also show useful
( 1 ) S u p p o r t e d b y t h e N a t i o n a l S c i e n c eF o u n d a t i o r l , G r a n t s G P 28586X ancl GP-14247, ancl by the International coppcr Rcsearch Association. O (2) J. F. Normant, S)'nthesis,2,6(1972); G' H. Posner, rg' React', 3 19, | (1972), ( 3 ) G . B r i h r a n c l P . B u r b a i n " M e t h o d e n d e r o r g a n i s c h e nc h e m i e " ( H o u b e n - W e y l ) ,V o l . X I I I / 1 , E ' M i , i l l e r , E d . , G e o r g T h i c m e V c r l a g , S t u t t g a r t ,1 9 7 0 ,p 7 3 1 f f . R ( 4 ) O . A . C h a l t y k i a n , " C o p p e r - C a t a l y t i c e a c t i o n s , "A . E . S t u b b s , t r a n s . , C o n s u l t a n t sB u r e a u , N e w Y o r k , N ' Y . , 1 9 6 6 ; P . F . F a n t a , C h e m . R e c , , 6 4 , 6 1 3( 1 9 6 4 ) ; R . G . R . B a c o n a n d H . A . O . H i l l ' Q u a r t ' , R e c . ,C h e m .S o c . ,1 9 , 9 5 ( 1 9 6 5 ) ; J . P e i s a c h P . A i s e n , a n d W . E ' B l u r n berg, Ed., "The Biochemistry of Copper," Academic Press,New York, N. Y.. 1966.

reacti vi ty. Thi s paper descri besstudi es of o ne such cl ass: al koxi desof copper(l ). Thesestudi eshad t hr ee of and characteri zati on alkoxides obj ecti i es: synthesi s p h e n o x i d e so f c o p p e r ( l ) ; d e t e r m i n a t i o no f t h e und i beharl i orof thescsubstancesn reacti onsw hose usef ulness w i th al kyl copper reagentshas al ready b een esof tabl i shed: and exami nati onof the mechani sms t heir thermaldecomposi ti on. C opper(l ) al koxi des and phenoxi deshave been im pl i cated previ ousl y as i ntermedi atesi n a var iet y of reacti ons,a'and poorl y chara ct er ized 5 copper-catal yzed have been prepa r ed'6 A exampl esof thesesubstances is useful synthesisof copper([) tert-butoxideT not appl i cabl e to the preparati on of the thermal l y u nst able copper(I) pri mary and secondaryal koxi des th at wer e ^central i nterest i n our w ork. The prepar at ion of of copper(I) phenoxi deby a procedureanal ogou st o t hat here has beenreported.s C opper(I)a lkoxides descri bed
(5) J. K. I(ochi, Proc. Ittt. Congr.Pure Appl' Chem', 23rd,4' 377 (1971),and referenccs citcd therein, ( ( 6 ) b . E . H . B a w r ra n d F . J . W h i t b v , J . C h e m . 9 o c . , 3 9 2 61 9 6 0 ) ; G ' C o s t a . A . C a m u s , a n d N . M a r s i c h , J . I n o r g ' l ' ' l u c l 'C h e m ' , 2 7 ' 2 8 1 (Ie6s). J ( 7 ) T . S a e g u s aT . T s u c l a ,a n d T . H a s h i r n o t o , ' A m e r ' C h e m ' S o c " , 9 4 , 6 5 8( 1 9 7 2 ) . 45, 1499 iSl f. I(awaki and H. Hashimoto, Bull. Chem. Soc' Jap', (r972).

ttf Whitesides,et al, I St'nthesis Cttpper(l) Alkoxides

2830 h a v e been s ugge s te da s " h o l d i n g g ro u p s " i n mi xed , co pperat e c om ple x e sH e t(R )C u L i .' $ Results of and S1'nthesis Characterization Copper(I) Alkoxides and Phenoxides. Copper(t) alkoxides were obtainecl by heterogeneousreaction between dry, oxygen-free me a a l co holsand halid e -fre e th y l c o p p e r(I) t 0 o u nder a (eq l). With the exception of nitrogen atr-nosphere
(CH3Li)r * 4"(Bu.zS).zCu["---->

(c H :,c u ),t *h

" R o C u " + c Hl t

(l )

co p per ( l) m et hoxi d e , th e c o p p e r(l ) a l k o x i d e s w ere so l uble in et her a t 0 o ; m o s t w e re a l s o s o l u b l e i n hyd ro c ar bon s olv en ts .a l th o u g h c o p p e r(I) c y c l o h exoxi de a n d c y c lopent oxi d ep ro v i d e n o ta b l e e x c e p ti ons(ci de infra). Copper(l) alkoxides were precipitated from e th er s olut ions as l i g h t y e l l o w s o l i d s o n c o o l i ng to -7 8" , and wer e p u ri fi e d b y w a s h i n g w i th c o l d ether. Co p per ( l) m et hox i d e a n d c o p p e r(l ) p h e n o x i d esw ere o b tainedus inga si m i l a r re a c ti o n ; h o w e v e r,s i n cethese ar su b s t anc es e inso l u b l e i n e th e r. th e i r fo rm a t i on w as t h e ter ogeneous hro u g h o u t. T h i s p ro c e d u re for the p re par at ion of c o p p e r(l ) a l k o x i d e s i s a re asonabl y g e ner alone. alt ho u g h h i g h mo l e c u l a r w e i g h t a l cohol s so met im esr eac t s l o w l y o r i n c o mp l e te l yw i th methyl co p per ( I ) . F ur t h e r, th e i s o l a te d y i e l d s o f c o pper(l ) a l ko x idesar e m ore v a ri a b l eth a n o n e w o u l d l i k e (ui de o i n .fr u) . V igor ous a g i ta ti o n o f th e s u s p e n s i o n f methyl co p per ( l) in t he s o l u ti o n o f e x c e s sa l c o h o l i n ether i s re quir ed t o ac hie v eh i g h y i e l d s o f c o p p e r(l ) a l k oxi des. Si m ilar pr oc edure s h a v e b e e n a p p l i e d to th e synth es is of c opper ( l ) c a rb o x y l a te s ,a n d s e e m to w ork smoot hly . Copper ( I ) alk ox i d e sa re h y d ro l y z e d o n c o n tact w i th w a ter and r apid l y o x i d i z e d b y a i r. T h e i r thermal sta bilit y dependso n th e i r s tru c tu re : c o p p e r(l ) deri vati ves of t er t iar y a l c o h o l s a re s ta b l e fo r h o u rs at temp e r at ur esles s t ha n 1 7 0 o , w h i l e th o s e o f p ri m ary al co hols dec om pos era p i d l y a t ro o m te mp e ra ture. The comse ns it iv it y m any o f th e s ec o m p o u n d sp re c l u d ed of e b u s t ion analy s isa s a me th o d o f e s ta b l i s h i n g m pi ri cal co mpos it ion. I nste a d ,s a m p l e sw e re h y d ro l y zed.and th e r at io of alk ox y to c o p p e r m o i e ti e s(R : R O/C u) i n n wasd e te rmi n e d . T h e s ea n a l y s e is di cated th es e am ples s valuesof R in satisfactoryagreementwith the expected v a l u e R : 1 . 0 : f o r c o p p e r ( l ) m e t h o x i d e ,R : 1 . 0 6 : fo r c opper ( l) n- bu to x i d e ,R : 0 .9 8 : fo r c o p p er(I)rertR b u tox ide,R : 1. 0 4 ; fo r c o p p e r(l ) c y c l o h e x o x i de, : R 1.04; for copper(l)isopropoxide, : 1.01. These re s ult sleav eno do u b t th a t th e m a te ri a l so b ta i n edusi ng th e pr oc edur e li n e di n e q I a re c o p p e r(l )a l k o xi des. out For c er t ain s y n th e ti c a p p l i c a ti o n s ,i t p ro vecl confo ve nientt o us e an a l te rn a ti v ep ro c e d u re r th e preparation of copper(l) alkoxides. Reaction of lithium a l kox ide wit h a su s p e n s i o no f c o p p e r(l ) c h l ori de i n d i m et hox y et hanea t 0 o re s u l te d i n fo rm a ti on of a h o mogeneous s o l u ti o n c o n ta i n i n g o rg a n o metal l i c i sp ec ieswhos e r ea c ti v i ty w a s e s s e n ti a l l y n d i s ti ngui sha b le f r om t hat of p u re c o p p e r(I) a l k o x i d e s . The obse r v at ion t hat c o o l i n g th e s e s o l u ti o n s d i d n o t resul t that i n pr ec ipit at ion o f c o p p e r(l ) a l k o x i d e s s u g g e sted
( 9 ) G . H . P o s r r c r C . E . W h i t t c n , a t r d J . J . S t c r l i n g ,J . A m c r . C h e n t . , c S o c . ,9 5 , 7 7 8 8( 1 9 7 3 ) ; s e ea l s o W . H . M a r - r d e v i l la n c lG . M . W h i t c s i d c s , 0 J . O r g . C h e n r . , 3 9 , 4 0( 1 9 7 4 ) . Journol o/'tlte Antericun Clrcnticol Societt' I 96.9 I Mu.r I, 1971

l i thi um chl ori de w as compl exed w i th organ ocopper presenti n sol uti on. and no seri ouseffo r t s wer e speci es to i sol atc pure copper(l ) al koxi des fron r t hese made si sol uti ons. N everthel ess. nce al kal i metal alkoxides a r e f r e q u e n t l ym o r c r e a d i l y o b t a i n e di n l a r g e q u a n t i t y w t, than is methylcopper(l)his procedure ill bethe more conveni entfor the preparati onof w hat are presum ed. on the basi sof reacti vi ty,to be copper(l ) sal ts of t hese al koxi des,at l east for practi cal appl i cati onsi nvolving l arge quanti ti esof these materi al s. Oxidation of Copper(I) Alkoxides. The dimerizatiort of organi c groups by oxi dati vecoupl i ng of the or ganic seem s moi eti esof copper(l )al kyl s, aryl s,and acetyl en es to have no anal ogy i n the chemi stry of copper ( l) al koxi des: reacti on w i th rnol ecul ar oxygen occur s s m o o t h l y , b u t i r i e l d so n l y c o p p e r ( l l ) a l k o x i d e s : r e a c y t i o n o f c o p p e r ( l ) n - b u t o x i d ew i t h n i t r o b e n z e n e i e l d s y r i - b u t a n ailn 2 2 1 , ; i e l d . with of Reactions Copper(I) Alkoxides and Phenoxides Organi c H al i des. C oupl i ng of organi c groups by of di nucl eophi l i c spl acement hal i dei on from an or ganic hal i de by the al kyl moi ety oi a l i thi unr cl i al ky lct r pr at c i s one of the most useful rcacti ttnsof orgi ttto copper ( l) c o m p o u n d s . : A n a l o g o u s n u c l e o p h i l i cr e i t c t i o t l sb c . t w e e n a l k y l h a l i d c sa n d c o p p e r ( l ) a l k o x i c l e sp r c p r r r e t l I a c c o r d i n gt o e q l . g i v e m o d e r a t e y i e l d s o f t l i r r l k r \ e t h e r s( T a b l c I ) . r " T h c s ey i e l d sr e s p o n ctl o c h l r l g e i n
Table I. R e a c t i o n so f C o D n e r ( l ) A l k o x i d e s w i t h A l k r l H a l i d c r

ROM
rr-CrHlOCu

R'X
l-C,HrBr

Solvent
Et:O EtJO-H M PA Digli,me

T e n r p .R O R (

l(x)
P;,ridine n-CrHlCl rl-CrHll l-CrH,,OTs .ter'-CrHlBr lcrl-C rHrrBr Bromocyclohexarre (cH,,)rccHzBr n-CrHrBr rl-C+Hr,l rl-CrHlBr l-5 ll5 l-5

,scc-CrH,,OCu lerl-CrHlOCu CoHiOCr-r n-C+HgOLi

--.1 5-5 55 53 100

6)t'

rl-CrHlBr

P1'ridine EtIO_H M PA

75"

" T h e s t a r t i t i g c o r r c e n t r a t i o no f R O C u w a s a p p r o x i m a t c l l 0 ' 2 N " R ' X w a s p r e s e n t i n 5 0 ' 1 , ,e x c e s s . A l l r e a c t i o n s w e r e a l l o w e c i t o proceeclfor 1.1lrr at tlre temperature indicated. Ytelds were determ i n e < l b y ' g l p c . a n c l a r e b a s e d o n t h e a s s u m p t i o r tt h a t t h e f i e l c l o f c o p p e r ( l ) a l k o x i d e i s o l a t e c ll ' r o m r e a c t i o n o f r l e t h y l c o p p e r ( l ) w i t h n a l c o h o l w a s 6 4 . 5 0 ' ), , . T h e t e x t c o n t a i n sa c l i s c u s s i o o l t h i s p o i n t . / ' I s o l a t e c ly i e l d L r a s e d n m e t h y ' l l i t h i u m . ' Y i e l c l s w e r e d e t e r m i n e d o w by glpc. ancl. to make contl-rarison ith the corresponding yields f r o m t h e c o p p e r ( l ) a l k o x i c i e sp o s s i b l e .a r e r e p o r t e d o n t h e a s s u m p t i o n t h a t t h e I i e l c l o [ l i t h i r - r ma l k o x i c l e f r o m r e a c t i o n o f m e t h y l w l i t h i u m r v i t h a l c o l . r o l a s c r r . 5 0 1 i . I n r c a l i t y . t h i s y ' i e l di s p r o b a b l y o quantitative. sclthat the true yield of ROR' l'rased n ROLi is [alI of that given. ( l 0 ) C o n v c u t i o n a ln r c t h o c l so r t h c p r c p a r a t i o no f a l k y l a r l d a r y l f , c t h c r s a r c s l r r v c y c ctl r y C . A . B c u h l c r a n d D . E . P c a r s o l t " S u r v c y o f c O r g n n i c S l n t h c s c s , "W i l c l ' - l r t t c r s c i c t r cN,c w Y o r k , N . Y . , 1 9 7 0 ,C h a l l l t c r 6 , a p c l l t 1 H . \ { c c r u c i r t i r t " M c t l . r o c l c tc l c r O r g a r r i s c h c lC l . r c r . r r i c " V E ( H o u b c n - W c : l ) , V I 3 , E . \ ' t i . r l l c r , c l . ,G c o r g T l . r i c r u c c r l a g , S t t r t t g a r t , 1 9 6 5 ,p I l l ' .

2831 re a c t ionc ondit ion sa n d re a c ta n ts tru c tu re i n a fashi on the th a t is qualit at iv e l y s i m i l a r to th a t c h a ra c te ri zi ng Wi l l iam s on et her s y n th e s i s : p ro d u c ti o n o f e thers i s fa vo r ed by t he us e o f p y ri d i n e l t o r p o l a r a p roti c sol v e n t s : 1 1e l i m i n a t i o ni s a s e r i o u ss i d e r e a c t i o n i n d i s p l a c em ent s s ec o n d a ryc e n te rs . T h e y i e l d s o f ethcrs at fo rm ed by r eac t io n o f c o p p e r(I) a l k o x i d e sa n d a l kyl -X d e cr eas ed t he ord e r X : O T s > B r - t > Cl l the in or co rres ponding de r fo r a ry l -X w a s X : I ) B r )) OTs > C l. T he r eac t i o n o f c o p p e r(l ) a l k o x i d e sw i th al kyl s h a l i d es of f er s c er t a i n a d v ' a n ta g e o v e r th e Wi l l iamson syn t hes isof et her s i n th a t re a c ti o n c o n d i ti o n s i n the fo rm er ar e m ilder th a n th o s e u s u a l l y e mp l o y e d i n thc t a l a t t e r ,a n d e l i m i n a t i o n p p e a r s o b e a s m a l l e rp r o b l e m : th h o w ev er ,it s uf f er sf ro m th e d i s a d v a n ta g e a t c o pper(l ) a a l k o x i d e s r e o r d i n a r i l yl e s sr e a d i l ya v a i l a b l e n d m o r e a s e n s i t i v et o t e m p e r a t u r ea n d o x y g e n t h a n a r e a l k a l i l n e tal alk ox ides . The r eac t ion of c o p p e r(l ) a l k o x i d c sw i th a ry l hal i des p ro d uc es alk y l ar yl e th e rs i n g o o d y i e l d s (T a b l e l l ). Alkoxides Aryl and with of Table II. Reaction Copper(l) VinylicHalides'
ROM/,
ll-C+HoOCu

ArX.
Phenyl p-toluenesulfonate Iodobenzene

Solvent
Pyridine Diglyme Pyridine

Temp. ArOR, oC 7"1

25

12 I 29 64 90 <t 6-s 98 96 75 70 55,, 65', 45,, 85 86 96t, 94 85

a 1 ^

100 25 ll5

l-CrHsOCu"

Chlorobenzene Bromobenzene Iodobenzene Dimethoxy'ethaneHMI'A/ 85

n-CrHrOLi (10i.; CuCl) n-C,rHoOCu" sec-CrHgOCu lerl-C.rHlOCu CtH;OCu rl-C.HrOCu

Iodobenzene 3-lodotoluene 4-lodotoluene Bromobenzene Iodobenzene

Pyridine

25 I l5

(or obtai ned by react ion the speci es mi xture of speci es) o f l i t h i u m a l k o x i d e sw i t h c u p r o u s c h l o r i d c ,a n d f r o m o l i t h i u m a l k o x i d c i n t h e p r e s e n c e f a p p r o x i m a t e l yl 0 mol 7,:, cuprousr2 chloride. Again. pyridine or e t h e r e a ls o l v c n t sc o n t a i n i n g H M P A p r o v i d e t h c b e s t o reaction media. Higher temperatures r longer reacti on ti mes ure requi red for these reacti onsth an f or t h e r e a c t i o n so f c o p p e r a l k o x i d e sw i t h a l k y l - h a l i d e s , s a l t h o u g ht h e s ed i s p l a c c m e n td o t a k e p l a c ea t a s e r ri c e able rate even at room temperature. One important to functi on of pyri di ne i n thesereacti onsseems be t hat o f s t a b i l i z i n gt h e c o p p e r a l k o x i d e s a g a i n s t t h e r m a l t t d e c o m p o s i t i o n : 1 'i r m a y a l s o c h a n g e h e r e a c t i v i t yo r extent of aggregati onof the copper al koxi des by coordination. These reacti onsprovi de the bcst avai l abl epro cedur e i o for the conversion f aryl halldesnto aryl alkyl ethers. A l ternati vc prepai ati ons based on reacti ons bet ween p o t a s s i u ma l k o x i d e sa n d a r y l h a l i d e s r e q u i r e m o r e vi gorouscondi ti onsand produce l ow er yi el ds of pr oducts, and i n addi ti on suffer from the possi bi lit y t hat i n t e r v e n t i o no f a n a r y n e m e c h a n i s mi n a n y n e w e x a m p l e m a y l e a d e i t h e rt o a m i x t u r e o f p r o d u c t so r t o a s i n g l ep r o d u c ti n w h i c h t h e p o s i t i o no f t h e e t h e rl i n k a g c isambiguous.ra Thermal Decomposition of Copper(l) Alkoxides. T h e t h e r n r a l s t a b i l i t y o f c o p p e r ( l ) a l k o r i c l e si s a p p r e c i a b l yh i g h e r t h a n t h a t o f c o p p e r ( l ) a l k y l s : f o r exampl e. on w armi ng tt-t roont temperattr r e f r ont - 7 8 o . c o p p e r ( l ) n - b u t o x i d ei s s t a b l e f o r 1 2 h r . w h i l e n i r - b u t y l c o p p e r ( ld e c o m p o s e is 2 0 m i n . N o n e t h e l e s s . ) o thermal cleconrposition f copper alkoxides is an o w i m p o r t a n tc o m p e t i n gp r o c e s s h e n r e a c t i o n s f c e r t a i n a of thesesubstances re carried out at temperatures a b o v e a m b i e n t . a n c l i n f o r m a t i o n c o n c c r n i t t gt h e s c s t h e r m a l d e c o n r p o s i t i o nis p e r t i n e n tt o t h e i r s y n t h e t i c application. e M a n y p a t h w ' a y s r i s t f o r t h e t h e r m a ld e c o m p o s i t i o n o f t r a n s i t i o n n i e t a l o r g a n o n t e t a l l i cc o m p o t t n d s i n c g e n c r a l . l i - : r a n d o f o r g a n o c o p p e r ( l ) o m p o t t n d si n t particular.r\-r: Although it has been possible o dei. f i n e c e r t a i n d e t a i l s o f t h e s ed e c o m p o s i t i o n s t i s s t i l l r,' ery {Ii cul t to predi ct the processthat w i l l dom inat e di for a parti cul ar organometal l i crcagent. C om par ison
( 1 2 ) R . G . R . B a c o n a n d S . C . R o r n i s o t ' J ,. C h e m . . S o cC , 3 1 2 r . ( 1 9 6 9 )h a v c n o t c d t h a t t h c n u c l c o y t l ' r i l i c ioy ' s o c l i u r ra l k o r i c l c st o l v a r c l r tf o i b l r r y l h a l i c l c ss i n c r c r t s c c ly t l i c p r c s c n c c f c o p l l c r s l l t s . ( 1 3 ) A s i m i l a r f t r n c t i o r ri s s c r v c db y t r i l r r y l l l h o s p h i r r c sh o r v c v c ' rt,h c : o p r c s c n c c l ' s t o i c h i o r r t c t r iq u a t t t i t i c s f p h o s p h i l c s i n o r g a r l i cr c a c t i o n o c h m i x t u r c s o n r p l i c a t cts c i r r v o r k - u p . c 1 ( 1 4 ) M . R . V . S a h y u ta t r c D . . 1 . C r a r l , O r g . S - r ' r r . , 4 5 , 8(9 9 6 5 ) l l r , . J . S . B r a c l s h a wE . Y . C h c n , R . H . H a l c s ,a r r t lJ . A . S o u t h ,. 1 O r s . C l t e t r t . , , G 3 ' 7 . 2 0 5 1( 1 9 7 2 ) : D . J . C r a n r , B . R i c k t r o r r r r t t . t c l . R . I ( r r o x , J . ' 4 m e r . 2 Chent.Soc.,82. 641 (l 960\. ( 1 - 5 )P . S . B r a t c r n r a r a n c lR . J . C r o s s ,J . C h e m . S o c . , D a l t o r tT r a t t s ' , t 6 , \ 7( 9 7 2 ) . ( 1 6 ) G . M . W h i t c s i d c s , . l . . G a a s c h a n c lE . R . S t c c l r o r l s k y., .A n t e r . l F , ( , C h c r n .S o c . , 9 4 , 5 2 - 5 8 1 9 7 2 ) ; G . M . W h i t c s i c i e sD . B c r g b r c i t c r ,l r t c l P . E . I ( c r r c l a l li,b i d . , 9 6 ,2 8 0 6( 1 9 7 1 ) . t. l. ( 1 7 ) G . W . P a r s h a l la n d J . . 1 . M r o r v c a , A c l L ' a rO r g c u t o m e t aC h e m ' , 7 , 1 s 7( 1 9 6 8 ) . ( 1 8 ) G . M . W h i t c s i d c sC . P . C a s c y , n d J . I ( . I ( r i c g c r , J . A m e r . C h e m . a , S o c . ,9 3 , 1 3 7 9( 1 9 7 1 ) . ( 1 9 ) A . C a i r n c r o s sa r t c lW . A . S h e p l r a r t l',1 . A n t e r . C h e m . S o c . , 9 0 , H 2 1 8 6 ( l c ) 6 8 ) ; 9 3 , 2 4 7 ( 1 9 7 1 ) : A . C a i r r r c r o s s , . O t r r u r a ,a n c l W . A . S h c l r p a r di ,b i d . ,9 3 . 2 4 8( 1 9 7 1 . ) ( 2 0 ) M . T a t r u n t a r r c l. 1 . l ( . I ( o c h i , J . O r g a t r c m e t a lC h e m , ,4 2 ' 2 0 5 . (1e72). ( 2 1 ) G . M . W h i t c s i c l c sE . J . P a n e k ,a n c lE . R . S t c c l r o n s k yJ . A m e r . , , 2 Che m . S o c . ,9 4 , 2 3 2( 1 9 7 \ . ( 2 2 ) C . M . W h i t c s i d c s , . R . S t e c l r o n s k yC . P . C a s c y ,a n d J ' S a n , E ( F i l i p p o , J r . , . A m a r . C h e m .9 o c . , 9 2 , 1 4 2 6 1 9 7 0 ) ' J

1-Bromocyclohexene

" The starting concentration of copper alkoxide was approxirnately 0.1 l/. Reactions were carried out for l2 hr. r Copper(l) alkoxides were prepared by the reaction of methy'lcopper(l)with the alcohol. unless otherwise noted. " A 501.. exce:is of the aryl halide was employed. d Yields are determined by glpc based on the copper(l) alkoxide. unless otherwise noted. " The copper(l) alkoxide was prepared by the reaction of the lithium alkoxide with cuprous chloride. / The DMF contained 4 equiv of HMPA/equiv of lithium. o Isolated yield based on methyllithium. The ethers produced in these reactions were isomericalll,' pure within the limits I Copper(l) lerl-tlutoxide was o f d e t e c t i o n o f t h e a n a l y s i s( + 5 % ) . prepared by the reaction of potassium /e/'l-blltoxide with cuprous chloride.

Wi th in t he lim it ed ra n g e o f re a c ti o n se x a m i n ed,comp a ra ble y ields of a l k y l a ry l e th e rs a re o b ta i n e d from co p p er ( l) alk ox ide s p re p a re d a c c o rd i n gto e q 1, from

(11) Reaction of copper(I) carboxylates with alkyl halidcs occurs best in pyridine: A. H. Lervin and N. L. Golclberg, Tetrahedrort Lctt.,491 (1972). Magncsiurn nlkoxicles rcact with alkyl halides in hcxarncthylp h o s p h o r a r n i d c t o g i v e c t h c r s i n g o o c l y i c l c l; Y . L c r o u x , M . L a r c h e v e q u e ,a n d J . - C . C o m b r c t , B u l l . S o c . C h i m . F r . , 3 2 5 8 ( 1 9 7 1 ) .

of Whitcsides,et al. I St'nthesis Copper(l) Alkoxides

2832 of the mechanism(s)of thermal decomposition of corre spondingc oppe r(I) a l k y l s a n d a l k o x i d e ss h o ul d hel p to define the factors that determine the dominant decompositionpathways. The major products of the thermal decomposition o f pr im ar y and s e c o n d a ry c o p p e r(l ) a l k o x i d es are co p per m et al, alc o h o l , a n d th e k e to n e o r a l dehyde formally derived from oxidation of the alcohol (eq 2). (2) RCH:OCu----> RCH:OH 1 RCH-O a Cu(O) were Two fundamentally different types of mechanisms considered in trying to account for these products. b On e , r epr es ent ed y e q 3 a n d 4 , i n v o l v e sa n i n i tial el i m----> RCH:O 1 CuH (3) RCHTOCu RCHTOCu CuH ----> RCHzOH 2Cu(O) 1 f (4) i n a t ion of c opp e r(t) h y d ri d e fro m o n e c o pper(l ) alkoxide moiety, followed by reduction of a second co pper ( l) alk ox id e b y th i s c o p p e r(l ) h y d ri d e . Thi s fo me c hanis mhas be e n e s ta b l i s h e d r th e d e c o m posi ti on n- but y l( t r i- n -b u ty l p h o s p h i n e )c o p p e,2 0 - 22 but r(l ) of cl e ar ly c annot be i mp o rta n t i n th e th e rma l decomp o sit ion of , . g., c o p p e r(l ) l c rl -b u to x i d e , fo r w hi ch vi cinal c opper ( t ) h y d ri d e e l i m i n a ti o n i s i m p ossi bl e. (e Th e s ec ondm ec ha n i s m q 5 a n d 6 ) re q u i re sh o mol yti c ----> RCH:O' * Cu(O) (5) RCHTOCu ---> products (6) RCHTO. scission of a copper-oxygen bond, followed by gene ra t ion of pr oduc ts fro m th e i n i ti a l l y fo rme d al koxy ra dic als : t his m e c h a n i s m w o u l d a l s o b e a ppl i cabl e to t he dec om po s i ti o n o f l c rl -a l k o x y c o p p e r (l ) comth p o unds . B y way o f p re c e d e n t, e rma l d e c o mposi ti on i u i a f r ee alk y l r adi c a l s i s o f e s ta b l i s h e dm p o rta ncefor co pper ( t )alk y ls c o n ta i n i n gn o h y d ro g e na to m s p to the ca r bon- c opper bo n d .2 1 T h u s , a p ro b l e m o f central c o n c e r n i n d e t e r m i n i n gt h e m e c h a n i s mo f t h e r m a l d e c om pos it ionof a c o p p e r(l ) a l k o x i d e i s th a t of dete rm ining whet he r c o p p e r(l ) h y d ri d e o r fre e al koxy i ra dic alsar e int er me d i a te sn th e d e c o mp o s i ti o n .2' r Our f ir s t appr o a c h to th i s p ro b l e m c e n te red on i l stu dy of t he inf lue n c eo f s o l v e n t o n th e d i s tri b uti on of o p roduc t sf r om t he th e rma l d e c o m p o s i ti o n f re p resentati ve c opper ( l) alk o x i d e s (T a b l e III). If fre e al koxy ra d ic als ar e int e rm e d i a te si n th e s e th e rma l decomp o sit ions ,t hen t h e y i e l d o f a l c o h o l p ro d u c e d rel ati ve p to t hat of t he c a rb o n y l -c o n ta i n i n g ro d u c t s h oul d be th in s olv ent s a t a re m o re a c ti v eh y d ro g endonors h i g her to war d alk ox y r a d i c a l s th a n i n th o s e th a t are l ess a ctiv e. 2a T he c o p p e r(l ) a l k o x i d e s e x a m i n e d f el l i nto tw o c at egor ies : th o s e (u .g ., c o p p e r(l ) rl -h eptoxi de, for which the ratio cyclohexoxide,and cyclopentoxide)
(23) A numbcr of variants are conccivable for a free-radical cleconlposition. At orrc cxtrcmc, initial clccomposition of the copper(l) alkoxidc could yield a clialkyl pcroxide, which woulcl clecorrposc' in a subsequent stcp to frcc alkoxy radicals. As prcccdent, dccompositiorr of vinylic and aronratic orgauocoppcr(l) cotlpouncls producc orgltrtic d i m e r s i n a r e a c t i o n t h a t c l o c sn o t i n v o l v e f r c e - r a d i c a l i u t e r m c c l i a t e s . t r ' i g Alternativcly, nlkoxy radicals gcncrated by hornolytic scission of a carbon-coppcr bond might attack copper(I) alkoxidc to incluce radical Regarcllcss, the most irlrr.recliate rlcchatristic clistinctiorr forrnation. to bc made is that betrveen thosc rcaction schemcs that involvc ittterrnediate frcc alkoxy radicals, and those that do not. ( 2 4 ) T h e h y d r o g c n a t o r n c l o n o r a b i l i t i e s l i s t e d f o r t h c s o l v c n t s u s e c li n Table III are those estin.ratccl olt a per molecule basis fror.r.rclata for r e a c t i o n s o f / e r l - b u t o x y r a c l i c a l sr v i t h t h c s c s u b s t a n c e s : c / . W . A . P r y o r , "Free Radicals," McGraw-Hill, Ncw York, N. Y., 1966: C. Walling, Pure Appl. Chem.,l5. 69 (1961): A. L. Willianrs, E. A. Obcrright, and J. W. Brooks, J. Amer. Chem. Soc., 78, 1190 (1956); J. A. Hor.varcl, Adcan. Free Rqclicctl Chem., 4, 49 (1972).

Solvent Effects on the Distribution of Products from Table III. tl.reThermal Decomposition of Copper(i) Alkoxides" Solvent (H donor ability)b

ROCU
rr-CzHr;,OCu

Product Alcoholi balance, carbonyl' % 3.1 2.9 r0 1 04 2 7t, 2.32 873 l. lB 768 o74 0.89 0.96 0.79 r.83 l.r9 0.12 I .39 0.80 0.80 92 79 88 100 9r 86 84 72 89 83 90 r00 86 80 72 72

Toluene( I .0) I ) e n t a n( 2 . 6 ) e THF (23) (0.0004) Copper( I) cyclohexoxic'le Benzene ( C u m e n e 2 .5 ) P e n t a n( 2 . 6 ) e THF (23) e Copper(l) cyclopentoxide P e n t a n( 2 . 6 ) THF (23) Pentan(2.6) e CH3CH(OCu)C;Hz THF (23) (0.0C[4)" Benzene CTHiCH(OCu)CzH; ( Tetralin 4.3)" Ether(23)i Toluene(l .0) C6H,rCH(OCr-r)CoH; Pentan(2.6) e THF (2]) e C o p p e r (I ) c y c l o b u t o x i d e P e n t a n ( 2 . 6 ) THF (23)

,, The decompositions were carried out by heating solutions o r i g i n a l l y0 . 3 + O . l M i n c o p p e r ( l ) a l k o x i d e f o r 2 0 h r a t I 1 5 " . u n l e s s n o t e d o t h e r w i s e . ' T h e m e t h o d L r s e dt o e s t i m a t e t h e s e n u m l r e r s is the ratio of the is described in ref 24. "'Alcohol/carbonyl" p alcoftol- and carbonll-cor-rtainipg roducts derived from the alkoxy moiety of the copper(l) alkoxide. 'r Decompositiort temperaturc 85'. " Decomposition temperature 100". / Decomposition temp e r a t u r e1 6 0 " .

products i ncr eased of al cohol i cto carbonyl -contai ni ng as the sol ventw as changedfrom r elat ively si gni fi cantl y i neffecti vehydrogen atom donors stl ch as pe nt ane or tol uene tcl an efl i ci ent donor, tetrahydrofur an, and . , r h o s e ( c . g . , c o p p e r ( l ) 2 - p e n t o x i d e 3 - p e n t o x i d ec y c l o f) b u t o x i d e . a n c l 1 , 1 - d i p h e n y l m e t h o x i d eo r w h i c h i r o t c h a n g ci n s o l v c n t h a c l n o s i g n i f i c a n i n f l u e n c e n t h i s r r a t i o . T h c s ey i e l d sa r e r e a s o n a b l ye p r o d u c i b l e :s m a l l v a r i a t i o n s r n a y b c d u e t o a d v e n t i t i o u sh y d r o l y s i si n of some of the sampl es. The physi calappearance all w d e c o m p o s i t i o n a s s i m i l a r ,w i t h d of thc santples trring a two exceptions:copper(l) cyclohexoxide ncl cyclope-ntoxi dew erc ntttch l ess sol ubl e than the ot hcr , c o p p e r ( l )a l k o r i d e se x a m i n e da n d t h e i r d e c o n r p o s i t i o n s w ereat l easti n part hcterogeneol l s. The hi gh yi el ds of al cohol s observed i n decom posi ti onsof the fi rst group of al koxi desi n so lr 'ent sof hi gh hydrogen atonl donor capabi l i ty. and th e var iati on i n thi s yi el d on changi ngthe sol vent.are qualit ati vel y compati bl ervi th the i ntermedi acyof free alkoxy radi cal s i n the decomposi ti ons. It i s di fl i cu lt t o esthe changei n the rati o of alcoholti mate quanti tati vel y products expectedon changing to carbonyl -contai ni ng sol vent i n these reacti ons, assumi ng an alkoxy radi cal to be an i ntermedi ate. si nce a nu m ber of reacti ons (radi cal combi nati on and di spropor t ionati on. attack on sol vent. reacti on w i th undecom p o s e d c o p p e r ( l ) a l k o x i d e ) a r e c o n c e i v a b l yo p e n t o such a racl i cal . Ftrrther qLl al i tati vesupport f or t he i ntermedi acyof free al koxy radi cal si n these r eact ions and of w as provi ded by the obsern' ati on fragmenta t ions of characteri sti c al koxy radi cal si n cer t ain ri ng cl osurcs . t h e r m a ld e c o m p o s i t i o n s T h u s . t h e r m a ld e c o m p o s i t i o n a o f c o p p e r ( t )n - h e p t o x i d e t 7 0 ' i n t o l u e n e y i e l d e d 1 and dodecane. Th e f or m aheptanol , n-heptal dehyde, can best be expl ai nedas the r esult of ti on of dodecane

Journal o/'the Anterican Chemical Society I 96:9 I May l, 1974

2833
n-CzHr;OCu-*
700

rr-CzHrrOH* I-CoFITaCHO + rt-Cr,:Hro

PhCHs

6t%

207;

127;

the fragmentation of an intermediateheptoxyl radical to an n-hexyl radical, and subsequentcombination of tw o of t hes e r ad i c a l s .2 5 S i mi l a rl y , th e rma l decoml p o sit ion of t he c op p e r(l ) s a l t o f 4 -p e n te n -1 -oa t 90' i n 26 toluene yielded 3-4% of 2-methyltetrahydrofuran, The behav ior o f p ri m a ry a l k o x y c o p p e r(l ) compounds on thermal decomposition,and of cyclohexoxyth ), a n d c y c lopent ox y c o p p e r(l i n d i c a te s a t th e d o mi nant mechanism for decomposition of these substances generatesfree alkoxy radicals. Establishing a mecha n is m f or t he r e m a i n i n g s e c o n d a ry a l k o x y c opper(l ) compounds examined is less straightforward, although se v er allines of ev i d e n c ea re c o m p a ti b l ew i th a mecha n is m inv olv ing e l i m i n a ti o n a n d s u b s e q u e n treacti on of o f c opper ( I ) hy dr i d e . F i rs t, th e re l a ti v ei n s e n si ti vi ty p ro duc t dis t r ibut i o n s fro m d e c o mp o s i ti o n o f these t su b s t anc eso t he h y d ro g e nd o n o r a b i l i ty o f th e sol vent i s ex pec t edf or a m e c h a n i s mi n v o l v i n g g e n e rati onand co ns um pt ion of a n i n te rme d i a te c o p p e r(l ) h ydri de. Second,an effort to detect fragmentation of the cycloo b u ty l r ing dur ing th e th e rm a l d e c o mp o s i ti o n f copper(l) cyclobutoxide was unsuccessful: the only products observed were cyclobutanol and cyclobutanone. The oxidation of cyclobutanol has been the object of careful stu dy :27 it s t wo-e l e c tro n o x i d a ti o n l e a d s to cycl ob u tanone, while i ts o n e -e l e c tro no x i d a ti o n l e ads al mo s t ex c lus iv elyto ri n g -o p e n e dp ro d u c ts . Al though th e r eac t ion c ond i ti o n s u s e d to e ffe c t th e th e r mal dea co m pos it ionof c op p e r(l )c y c l o b u to x i d e re s i g n i fi cantl y that no d i ffer entt han t hos e o f R o d e k , th e o b s e rv a ti o n s ri n g- openedpr odu c ts w e re c b ta i n e d ,2 s n d th e yi el ds a o f ring- c los edpr o d u c ts w e re g o o d (T a b l e III ), both p ro v ide s t r ong s u p p o rt fo r th e c o n te n ti o n that the cyc lobut ox y r adic a l i s n o t a n i n te rm e d i a tei n t hi s dea co m pos it ion. B oth o b s e rv a ti o n s re a l s o c o m pati bl e m w i th a dec om posi ti o n e c h a n i s mi n v o l v i n g e l i mi nati on o f c opper ( I ) hy dr i d e . T h i rd , i f c o p p e r(l ) h y dri de i s g e n er at ed in t hese d e c o mp o s i ti o n s ,i t m u s t conrert co p per ( I )alk ox ide sto a l c o h o l s(e q 4 ) a t a ra te that i s at l e a st c om par ableto i ts ra te o f fo rm a ti o n : th e r ati o of th e y ields of alc o h o l s a n d k e to n e s p ro d u c e d i n the th e r m al dec om po s i ti o nn e v e r fa l l s mu c h b e l o w uni ty, a s i t m us t if t he el i m i n a ti o no f c o p p e r(I)h y d ri d e (eq 3) w e re t o be r apid c o mp a re d w i th i ts s u b s e q u ent reacti o n . E x per im en ta l l y ,re a c ti o n o f c o p p e r(l ) h ydri de' :e wi th equim olar q u a n ti ti e s o f e i th e r c o p p e r(l) cycl oh e x ox ide in t oluen e o r c o p p e r(I) 3 -p e n to x i d ein ether a t 1 00o r es ult s in c o n v e rs i o no f a l k o x v m o i eti es en( 2 5 ) F o r c o m p a r i s o n , r r - b u t o x yr a c l i c a l s ,g e n c r a t e da t 1 9 5 " i n t h c v a p o r p h a s c , c l c c o n r p o s eo p r o p y l r a d i c a l s t o t h c c x t c n t o f 2 9 1 i , : t E . R . B e l l , J . H . R a l c y , F . F . R u s t , F . H . S e u b o l d ,a n d W . E . V a u g h a r . r , D i s c a s sF a r a d a yS o c . ,N o . 1 0 , 2 4 2 ( 1 9 5 1 ) . . ( 2 6 ) I r r a d i a t i o n o f t h c n i t r i t e c s t c r o f 4 - p c n t e n - l - o lr e s u l t si n y i c l c l s o f c y c l i z c dp r o c l u c t s p t o 6 8 7 J : R . D . R i e k e a n d N . A . M o o r c , T e t r a u h e c l r o n e t t . , 2 5 , 2 0 3 5( 19 6 9 ) . L ( 2 7 ) l < . M c y c r a n c l J . R o i . e k ,J . A r t t e r .C h e n t .| o c . , 9 4 , 1 2 0 9( 1 9 1 2 ) : J . R o 6 e k a n c lA . E . R a d k o w s k y ,J . O r g . C h e n t . , 3 8 .8 9 ( 1 9 7 3 ) ; J . A m e r . Cltent.Soc.,95, 7123(1973). ( 2 8 ) T h c o b s e r v a t i o nt h a t n o b u t y r a l c l c h y d c r s u b e r a l c l e l . r y r v c r e o de i r c l c t c c t c crl - t h i s r e a c t i o ni s n o t n c c e s s a r i lv c r y s i g n i f i c a n ts i n c cc o p p c r ( l ) y , a l k o x i d e s a r c s u f f i c i c n t l ys t r o n g l y b a s i c t o d e s t r o y s c u s i t i v ec a r b o n y l c o n r l r o u n c lu n d e r t h e c o n d i t i o n so f t h c s cr c a c t i o n s . s ( 2 9 ) G . M . W h i t e s i d e s , . S a n F i l i p p o , J r . , E . R . S t c c l r o n s k ya n c l J , C . P . C a s e y , J A t n e r .C h e r t r . o c . , 9 1 , 6 5 4 2 1 1 c 1 6J .1 t . D i l t s a n d D . F . . S 9A ( 1 9 6 8 ) ; 9 1 , 4 0 8 8( 1 9 6 9 ) t G . M . W h i t c s i c l ca n c l Slrrivcr,bid.,90.5769 i s J . S a r rF i l i p p o , J r . ,i b i d . , 9 2 . 6 6 lI ( 1 9 7 0 ) .

tirely to alcohol; no ketones were detected in either reducti on. Thus the transformati on of c opper ( I ) al koxi des to al cohol s by copper(l ) hydri de is r apid. Fourth, i f copper(l) hydri de w ere produced dur ing thermal decomposi ti on of copper(l ) al koxi des, som e quantity of molecular hydrogen might be found among si the products of the decomposi ti on, nce therm al dei composi ti onof copper(l )hydri deto hydrog' ens a r apid reacti on under the condi ti ons encounteredin t hese reacti ons. E xami nati on of the thermal decomposit ion products of pentane sol uti ons of copper(l ) cyclobuof toxi de and 2-pentoxi dei ndi cated the presence approxi matel y 1[ mol ecul ar hydrogen based on copper al koxi de; those from copper(t) n-butoxi de an d cycloyi el d s. The hexoxi deal so show ed smal l (-0.l -0.2[) hydrogen detected from decomposition quantities of of copper(l ) cycl obutoxi deand 2-pentoxi dear e only 4-6% of that requi redto accountful l y for the dif f er ence in i n the yi el ds of ketone and al cohol generated t hese they are agai n com pat ible reacti ons; neverthel css, of w i th the presence copper(l ) hydri de i n the decom posi ti on. Fi nal l y, bri ef exami nati onof the ki net icsof reveal edbehavior ver y these thermal decomposi ti ons and by si mi l ar to that observed both by K ochi 2(' ' 30 for S tedronsky;rr the thermal decomposi ti onof alkylcopper(l) compounds in which the elimination of i c o p p e r ( l ) h y d r i d e i s o f e s t a b l i s h e dm p o r t a n c e : d e i composi ti onof copper(l ) 2-pentoxi de n pentaneshows an i nducti on peri od of vari abl edurati on, fol l owed by a decomposi ti onw hose ti me course vari es from sam ple to sampl e. The i nducti on peri od can be el i mi nat edby the addition of 5 mol % copper(l) hydride. Curiousl y, the ki neti cs of the thermal decomposit ion of b e n e c o p p e r ( l ) - h e p t o x i d s h o w ss i m i l a r , r r a t i c , e h a v i o r . Discussion The reacti on of methyl copper(l )(and presum ably other thernral l y stabl e, basi c, organocopp er ( l) r ew a g e n t s ) 3 2 - 3 4 i t h a l c o h o l sa n d p h e n o l sp r o v i d e so n e E l c o n v e n i e n tr o u t c t o c o p p e r () a l k o x i d e s a n d p h e n o x i d e s : m a t e r i a l so f s i m i l a r r e a c t i v i t y m a y a l s o b e obtai ned by reacti on betw een l i thi um al koxides and . chl cuproLrs ori de The tw o types of reacti onsi n which secmto hav' ei mmedi atesyntheticpot enthesereagents ti al are thcl sei nvol vi ngthe formati on of ether l inkages, parti cul arl y by di spl acementof hal i de i on fr om an aromati c nucl eus, and those requi ri ng the t her m al ' generati on pri mary al koxy radi cal s.:ri In the f or m er of reacti on, copper(l ) al koxi des seem cl earl y super ior t o
( 3 0 ) K . W a d a , M . T a r l u r a , a r - r dJ . I ( o c h i , J . A m e r . C h e m . S o c . , 9 2 6656(re70). (31) E. R. Stcdronsky, Ph.D. Thcsis, Massachusctts Irlstitutc of Technology, Carrbriclgc, Mass., I 970. (32) T. Cohcn and A. H. Lcwin, J. Amer. Chent. Soc., 88, 4521 ( 19 6 6 ) . ( 3 3 ) A . C a i r n c r o s s , J . R . R o l a n d , R . M . H e n c l e r s o r . t ,i l t t d W . A . S h c p p a r c l ,J . A r t r e r . C h e m . 5 o c . , 9 2 , 3 l 8 7 ( 1 9 7 0 ) . (34) T. L. Cohcn and R. A. Scharnbach, J. Amer. Chem. Soc., 92, 3189( r970). ( 3 5 ) A b r i c f c r a n r i n a t i o n o f t h c t h e r r t r a l c l c c o r t t ; r o s i t i o r lo f c o p l l c r ( [ ) phcnoriclcs was carriccl out in thc hope thtt this rcaction rnight gcltcratc l r h c n o x y r a c l i c a l s ,a n c l n r i g h t a c c o r c l i n g l y l t r o v i c l e a r r r c t h o d o f o x i d a t i v c l y couplirrg phcnols. Thc rcstrlts of this study rvcrc clisappoir-rting: als though digll'111g olutions of coppcr(I) 2,6-clinrethylphcrroriclcyieldccl , 1 , 4 ' - c l i h y c l r o x y - 1 , 3 ' , 5 , 5 ' - t c t r a r r r c t h y l t r i p h c n y li r t y i c l c l s L r p t o 6 0 l l o r l were also rapicl clccorlpositiort at >100o, r'ttuch lorvcr yiclcls (.'20'l;) obtainccl unclcr apparcntly sirnilar conclitions. Thcrrnal dcconrposition of copper(l) phcnoriclc l"icldccl r.nirturcs of clihydrorybiphenyls irl no m o r c t h a n 5 i ' , ,y i c l c l . D c t i r i l s o f t h c s c c x t l c r i m c r t t s r n a y b e f o u n d i n t h e Ph.D. Thcsis of .J S. Sadon'ski, Massachusctts Institute of Tcchnology, Carnbridgc, Mass., 1972,

o.l-Copper(l)Alkoxides Whitcsitles,et al. I S.r'ntlrcsis

2834 o th e r pr es ent ly a v a i l a b l e re a g e n ts . T h e a b i l i ty of co p per ( l) t o f ac i l i ta te re a g e n ts th a t i n v o l v e formal n u c leophilic dis pl a c e me n ts t s p 2 c a rb o n c e n ters i s a w e l l k nown, aand e v i d e n c e a s b e e np re s e n te d a t these h th re ac t ions m ay in s o m e i n s ta n c e si n v o l v e fre e -radi cal i n ter m ediat es . 3: W e h a v e n o c o n c re tee v i d e n ceconce rn ing t he m ec h a n i s mo f th e d i s p l a c e m e n t f hal i de o i o n f r om ar om at ic n u c l e i b y c o p p e r a l k o x i d c s , S mal l q u a nt it ies( - l , " A o f b i p h e n y la re o b s e r' e d i n re acti ons w i t h p h e n y li o d i d e : t h i s o b s e r v a t i o ns c o n s i s t e nw i t h , i t b u t does not dema n d , e i th e r a fre e ra d i c a l o r a n aryl co p per int er m edia tei n th e re a c ti o n . T h e p ro nounced e ffec tof s olv ent s ,p a rti c u l a rl yH MP A, o n th e reacti on. th e s ugges t ionof ra d i c a l c h a ra c te r. a n d th e faci l i ty w i th whic h alk ox id e so f c o p p e r(t)(a s o p p o s e dto other m e t a l s ) p a r t i c i p a t ea r e c o m p a t i b l e w i t h m e c h a n i s m s o f t h e S n u l t y p e , 3 2 ' 3b u t o x i d a t i v ea d d i t i o n t o C u ( l ) 6 m i g h t a l s o b e i n v o l v e d , 3 a n d a d d i t i o n a lw o r k i s r e T q u i r ed t o def inea m e c h a n i s mc o n v i n c i n g l y . As a methodof generating rimary alkoxy radicals. p th e t her m oly s is of c o p p e r(l ) a l k o x i d e s o ffe rs at the sa m e t im e t he ad v a n ta g e sth a t th e s e s u b s ta n ces are m u c h e a s i e rt o o b t a i n . a n d s a f e r t o m a n i p u l a t e , h a n t a re p r im ar y alk y l p e ro x i d e s a n d th e d i s a d v a n tage , that th e y ar e m or e s en s i ti v eto a i r a n d w a te r th a n these peroxides. T h e e x a m i n a t i o no f t h e m e c h a n i s m s f t h e r m a l d e o c o m p o s i t i o n s f c o p p e r ( l )a l k o x i d e s r o i ' i d e s w o c o n o p t v i n c i n g ,i f q u a l i t a t i v ep i e c e s f e v i d e n c en d i c a t i n _ e a t , o i th fre e alk ox y r adic a l s a re i n rp o rta n t i n te rme d i a tesbct w e e n p r i m a r y c o p p e r ( l )a l k o x i d e sa n d p r o d u c t s : t h r : r e s p o n s e f p r o d u c t y i e l d st o c h a n g e s n t h e h y d r o g e n o i a t o m d o n o r a b i l i t y o f t h e s o l v e n t .a n d t l r e p r o d u c t i o n o f fragm ent at ion d c y c l i z a ti o np ro d u c tsc h a ra c teri sti c an o f a l k o x y r a d i c a l s . T h e s ed a t a d o n o t r e q u i r ee i t h e r th a t a f r ee- r adic a lme c h a n i s mb e fo l l o w e d e x cl usi rel y ( a l t h o u g h i t z i p p e a r so b e a d o n r i n a n t p a t h w a y f o r t p r i m a r yc o p p e r ( l ) l k o x i d e s )o r t h a t t h e a l k o x y r a d i c a l s a . n e ce s s ar ily gen e ra te db y h o n to l y s i so f a n o xygen be c o p p e r b o n d ( a l t h o u g h t h i s p a t h w a y s e e n t su p r i o r i t h e m o s t l i k e l y ) . R e g a r d l c s st i s e r i d e n tt h a t a t l c a s t i. o n e addit ional m e c h a n i s m -m o s t p ro b a b l l , i n v ol vi ng th e gener at ionand re a c ti o n o f c o p p e r(l ) h y d ri dc-i s o p e rat iv e in t he t h e rma l d e c o m p o s i ti o no f s e condary a l k o x y c o p p e r ( lc o m p o u n d s . T h e e v i d e n c e u p p o r t i n g ) s th e inv olv em ent o f c o p p e r(l ) h y d ri d e i n th i s second me chanis mis nr or e c o mp a ti b l e th a n o b l i g a to ry: the n a tu r e and r elat iv e y i e l d s o f d e c o mp o s i ti o np roducts a re relat iv elyins en s i ti v e s o l v e n t: m o re k e to ne than to a l co hol is pr oduc e d i n c e rta i n o f th e d e c o mp osi ti ons: tra ces of hy dr ogen a re d e te c te da m o n g th e p ro ducts: co p p er ( l) hy dr ide r a p i d l y re d u c e sc o p p e r(l ) a l koxi de.s to a lc ohols . T heseo b s e rv a ti o n s re a l l v e ry s i mi l ar to a those made in establishing opper(l) hydride as an c i n te r m ediat ein t he th e rm a l d e c o mp o s i ti o no f n -butyl (tri -n - but y lphos ph i n e )c o p p e r(l ), d m a k e a n a n al ogous an me chanis m f or t he d e c o m p o s i ti o n o f c o p p e r( l ) al ko xi d esat t r ac t iv e. Th e ident if ic at io no f th e s etw o me c h a n i s m s oes not d clarify the structural factors that control the path
( 3 6 ) J . F . B u n n c t t ,, 4 c c o u r t tC h e r n R e s . . 5 ,1 3 9( 1 9 7 2 ) : J . A . Z o l r e r v i c z s . a r r dT . M . O e s t r e i c h , J A r t r e r . h e m .S o c . , 9 5 , 6 8 6 3 1 9 7 3 ) a n c lr c f c r c u c e s ( , . C c i t e di n c a c h . ( 3 7 ) N u c l e o p h i l i cc o u p l i n go f g o l d ( I ) a t e c o m p l e x e s i t h a l k y l h a l i d e w s i n v o l v e so x i d a t i v e a d d i t i o n o f t h c a l k y l r n o i e t y t o t h c g o l c l a t o m : A . T a m a k i a r r cJ . I ( o c h i , J . O r g a n o m e t a lC h e m . , 5 l , C 3 9 ( 1 9 7 3 ) . l . Journctl of the American Cltemical Societl' I 96:9 I Muy l, 1974

fol l ou' ed bv a parti cul arorganocopper(f) contpound in i t s t h c r m a l d c c o m p o s i t i o n . I n c l e e dt.h e e l i n t i n a t i o n f o copper(l) hycl ri cl from a copper(l) al koxi dew ould seenl c' energeti cal l y more attracti vethan i ts el i mi nati on f r om a c o p p e r ( l )a l k y l , b o t h b e c a u s eh e e n e r g yc h a n g ea s t soci atcdw i th the conversi onof a carbon-oxyge nsingle b o n d t o a c a r b o n y lg r o u p i s m o r e f a v o r a b l et h a n t h a t o f a c a r b o n - c a r b o n i n g l eb o n d t o a d o u b l e b o n d , a n d s because coppcr( )-orygen bond i s expected b e m or c a l to p o l a r ,a n d l e s ss u s c e p t i b lte h o m o l y t i cs c i s s i o nt,h a n a o c o p p e r ( l )c a r b o n b o n d . T h e f a i l u r e o f t h i s r e a s o n i n g suggests that othcr factorsenti rel y-the structureof t he organometal l i c aggregates, presence trac er net al the o1' c a t i i l y s t s t h c a r a i l u b i l i t y o f v a c a n t c o o r d i n a t i o l rs i t e s . on the metal may ul ti ntate' l yci eterni i ne the deconr p o s i t i o n m e c h a n i s n r a n d t h c r r l a l s t a b i l i t i c so f t h e s e s and other orgrrrl rr11r.tl rrcagcnts. I Ii c r' ExperimentalSection'
Iodofbis(di-n-but1'l sulfido)]copper(I). Commercial coppcr(l) iod i d e ( 1 9 5 g , 1 . 0 - 5n r o l ) i v a i s s t i r r e d w i t h d i - l - b u t y l s u l f i d e ( 2 9 0 g , 2 . 0 0 ntol) in a 500-nrl erlenrncl'er 11ask. Thc reaction nrixturc was *,arnrecl to.3() lirr l0 nrin and thc rcsulting amber licluicl filtered tltroLrgh a Buchncr furrnel and stored at room temperature. (1.4 g, \Ieth1'lcopper(I). Iodo[tris(di-ri-buty,l sulfido)]copper(l) 2.8 mmol) and 30 rll of ether u'ere added to a flame-dried. serunlstoprpered, -10-ml ccntrifuge tubc containing a Teflon-coated stirring bar aud six to eight 3-nrnr glass beads to aicl in subsec;ucltl ltctcrogeneous reactious tlrc alcohols. Thc solLrtioll wil\ coolecl to - 7 8 i n a [ ) r 1 l c e" r ii t h p r o l - r r l a l c o h o l b a t h a n d n r e t l r 1 , l l i 1 1 1 l l ' r(r1 . - 5 so n n r l o f a 1 . 6 . V s o l u t i o n i n c l i e t h y , le t h c r . 2 . 4 m r n o l ) r v a s a d d e d . p r o ducing an inrnrcdiatc precilritate of bright lellow methylcopper(l). The solicl wa\ corrpacted b1 centril'Lrgati()n at roont tcmperatLlre ancl the \Llllcrnatant liquid rcrlovecl b1' cannula. Fresh etlrcr (30 r r l ) w a s a c l c l e c lu ' l r i l e k e e p r n g t h e n r e t h l , l c o l - r p e r ( l ) c o l c i i n a D r - v l c e isolrrolrl'l alcohol batlt. ancl the tLrbe w:rs shaken arrd ccntriluged. The etlter was agarin renrovcd and tlte washing prrlcerlure rcpeated an additiorral two times. Copper(l) alkorides \\cre prcparccl b1 a contntol't proccdurc. i l l u s t r a t e d h c r c l r y t h c 1 ' r 1 e 1 ] n r s t i o no f c o p p e r ( l ) n - b u t o x i c l c . To a suslrension of 2.-l nrnrol of ntetlrvlcopper(l). preparcd as descritrcd above. was acldecl rr-but1l alcohol (0.22 ml. 2.-1mntol). l-he reaction nrixture \ras stirred at 0 for 3 hr under nitrogen. Thc resulting hontogcr-lcolrssolution uas cooled to -78' ; copper(l) rr-but o r i d e p r e c i p i t a t e d a s a l i g h t l e l l o w ' p o i . r ' d c r . T h e s o l i d \ , \ ' a sc o m -

( 3 8 ) A l l r l c l t i n g p o i l r t s a n c l b o i l i n g l . r o i n t sl r r c u r l c o r r c c t e d . I n f r a r c c l spcctril rvcrc rictcrurinccl u ith a Pcrkin-Elnrcr, Modcl 237, grating s 1 : r c c t r o l r l - r o t o n r c t c r .N n r r s l - r c c t r a\ \ ' c r c c l c t c r n r i n c c li v i t h a V a r i l r n T - 6 0 nnrr spcctronlctcr. Mass spcctra wcre clctcrrninccl on a HitachiPcrkin-Elrncr R M U-6 nlass sl)cctronrctcr. Con.rttustion analy'scsu'crc M ' 1 1 r , 1 ' g s 1[ i c r p l t r b s ,L t c l . , . l ' l r l c l i i t r l t t l - r t l l i s ,I ' d . N' A.irly.tillcrfclrtnctl 111' cal glpc analyses u'crc pcrforrlccl on F&M Moclcl 810 anci PcrkinElrner Moclcl 990 llurnr' ionizltion iustrun.rcr.rts. Hyclrogcn analyses r,l'crccarriccl out Lry glpc using nitrogcn carricr gas, a thermal concluctivitl, clctcctor, anrl rncthlnc lls intenlll stirnclurcl. Absolr.rtc yiclcls o f l r r o c l u c t s r v c r c c a l c u l a t c c l f r o r . r . r1 ' r c a kl r r c l r s u s i n g i n t c r n a l s t a n c l a r c l t ec h r r i q u c s , w i t h r c s p o n s c f i r c t o r s o b t a i n c r l f r o n r u u t h c n t i c s a r . n p l c s . Dicthyl cthcr rncl tctrahydrofuriill wcrc clistillcclfronr lithiur.rr ultrnrir u i - r n ih y c l r i c l c o r c a l c i u n r h y c l r i t l c b c f o r c u s c . D i r r r c t h o r y c t l r a r t c a r t c l llcntanc rvcrc clistillccl fronr clisocliunr [rcuzolrhcrrouc ciianion unclcr n i t r o g e n : p y r i c l i n c u n c l l . r c n z e r r cw c r c c l i s t i l l c c l f r o m c a l c i u n r h y d r i c l c u n d e r n i t r o g e n ; h c x r r r n e t h y l p h o s p h o r a n r i c l er v a s d i s t i l l c c l f r o r r r s o d i u n r a t r c c l u c c d l r r c s s u r c . A l c o h o l s r v c r c d i s t i l l c c l , c l r i e c lo l ' c r 3 A r . n o l c c u l a r s i c v c s , a n c l c l c o r y ' g c r r a t c cu s i n g a s t r c a r l l o f n i t r o g c n . O r g u u i c h a l i c l c s l r v c r c p a s s c d t h r o u g h a c o l u n r r . ro f u l u m i r r a , a n d c l c o r y g c n a t c c l u s i t r g a strcanl of nitrogcn. H a l i c l c - f r e c n r c t h l , l l i t h i u m ( 1 . 6 . ' 1 1i n c t l . r c r ) w a s purchascd frorn Footc Mincral Corp. , C y , ' c l o p c n t y l - , r r - b r . r t - ' * l -a r t c l t c r l - b r - r t y l l i t l ' r i r . r r nc a g c n t s \ \ ' c r c s u p p l i c d b l ' F o o t e M i n c r a l C o r p . r Alfa Irtorgunics, Inc. Lithiunt s c c - B u t _ n - l l i t h i u n r\ \ ' l s s u l r p l i e c l b l jrrt All r e a g c n t s * , c r c a n u l v z c c l b 1 , t h c G i l r l a n c l o L r b l et i t r a t i o n n r c t l t o c l . reactior.rsinvolving organoluctallic rcagcnts werc carriccl out utrdcr p r c p r , r r i f i c r ln i t r o g c n , u s i n g s t ur r c l a r d i n c r t a t m o s p h c r c t c c h n i q u e s , l { t ( 3 9 ) H . G i l n r i r n . F . l ( . C a r t l c c l g c , a n d S . - Y . S i n r , , l. O r g c r t r o n t e t a l . C h e m . , l . 8 ( 1 9 ( r - j . t 6 . M . W h i t e s i c l e s ,C . P . C a s c y , a n c l J . I ( . I { r i e g c r , ; , J . A n t e r . C h c t r t . ^ S o c .9 3 . 1 3 1 9 ( 1 9 1 1 ) . (10) D. F. Shrivcr, "Thc Manipulation of Air-Scnsitivc Cor.r.rpouuds," M c G r a u , - H i l l , N c r r Y o r k , N . Y . , 1 9 6 9 ,C h a p t c r 7 .

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pacted br ccntrifugation at - 78" and the supernatant licluid r e m o v e c lb y c a n n u l a . F r e s h e t h e r w a s a d d e d w h i l e k e c p i n g t h c c o p p r e r ( l ) r : - b L r t o r i ccl o l c l i n a D r 1 ' I c e i s o l t r o l r l l a l c o h o l b a t l - ra r r c l e . the tLrbc was shaken ancl centril'ugecl. The ether was again rer m o v e c la n c l t h e w ' a s h i n gp r o c e c l u r e e p e a t e c l . T h e l i e l c l s ( r i t l c i t r l r u ) t o f c o l r p e r ( l ) a l k o r i d e s o l r t a i n e c lL r s i n g h i s p r o c e c l u r ew e r c r . l o t p a r t i c u l a r l y r e p r o c l u c i [ ' r l el.' o r t w o r e a s o n s : t h e h e t e r o g e n e i t . v f t h e o r e a c t i o n i n e t l r e r a n c l t h e r e s t r i c t i o n s i r n p o s e c lb , l t h e m e t h o c l o f anall'sis. W h e n t h e a l k o r i d e w a s g c n e r a t e da s a r r i n t e r m e d i a t e .t h e r e a c t t o n ( d m w a s h o m o g e n e o u s p y ' r i d i r r e i s s o l v e s e t h y l c o p p e r ( l ) ) . n c la t w ' c t a f o l c l e r c e s so f a l c o h o l r v a s u s e d . W h e n t h e a l k o x i c l ew a s t o b e i s o l a t e c l . t h c r e a c t i o n r v a s h e t e r o g e n e o u s( d i e t h y l e t h e r d o e s n o t c l i s . s o l v e r n e t h y l c o l - r p e r ( l ) ) . n d I e q u i v o f a l c o l r o l r , r ' a su s e c l . T h e a w a s h i n g a n c i c e r r t r i f u g i n gh a d t o b e c l o n e a t - 7 8 . a s t h e a l k o x i c l e s a r e v e r ) e t h e r s o l u b l ea t h i g h e r t e n i p e r a t l l r e s . T l r e s en t a n i p u l a t i o n s were technically clifiicult. l}ecause the acid cluench regeneratecl t h e s t a r t i n g a l c o h o l . c a r e h a d t o b e t a k e n t o r e n t o v e e x c e s sa l c o h o l before quenching the alkoxicle. ancl onl,l I ecluiv of alcohol rvas u s e d . T h e i s o l a t e c lf i e l d o f ' a l k o x i c l e l r r o b a b l y v a r i e c l o v e r a r v i c l e r range tharr did the nonisolated l,ielcl of alkoxide internrecliate. A v e r a g e f i e l c l s( p e r c e n t s a n c l r a n g e s ) o b s e r v e c ll - o r v a r i o u s c o p p e r a l k o x i d e sr v e r e : m e t h o r i c l e - 7 0 : r r - i r u t o x i c l e. - 5 5( 4 8 - 6 6 ) : / c r t p h e n o x i d e . - - 1 - i( : - s butoride -65 (52 83): cyclohexoride-80; 5 7 ) : a n c li s o p r o p o x i c l e - 5 0 . , , \ n : r l y s i so f C o p p e r ( I ) . \ l k o x i d e s . T o a s o l L r t i o n o f c o 1 - r p e r ( l ) a l k o x i d e ( I : 1 m m o l ) i n e t l r e r a t 0 l v a s a c l d e d 0 . - 5n t l o f c o n c e n t r a t e d h 1 ' d r o c h l o r i ca c i c l . A d d i t i o n o f i n t e r n a l s t a n c l a r dp e r n t i t t c d g l p c a n a l l ' s i so f t l r e r c s u l t i n g h o n r o g e n e o u s o l u t i o n f o r a l c o h o l o n a s l5i'l Carbowax 20M on Chromosorb W coluntn. The col)pcr content of the solution was then cieternrined l,adding to it 10 b l ml of concentratecrritric aciri. clilLrtingo 200 rll u,ith distilled t water. ancl anallzing follou.irrg the procctlure o1' Flasclrka anci A l r d i n e . II Small Scale Reactions of Copper(I) .\lkoxides with Orsanic H a l i d e s . T h e p r o c c c l u r e su s e d f o r n t o s t o f t l r c s c r c a c t i o n \ \ \ r r e s i m i l a r . a n d a r c i l l u s t r a t e c lh e r e [ ' r _trl - r c c t l t o d u s e c lf o r r h c r c u c r r o n m o f c o p l t e r ( l ) n - b u t o x i c l e* ' i t h n - t r u t l l b r o m i c i c . A 2 . - l - n t n r o ls a r l g r l e o f n T e t h y l c o p p e r ( l )r v a s p r e p a r e d . T h e b u l k o f t h c c t h c r u s e d i n t h e f i n a l w a s h i n g w a s r e m o v e d .p y r i d i n e ( 2 0 m l ) a n c ln - b u t 1 l a l c o h o l ( 0 . 2 2 n t l . 2 . : l m r n o l ) r v e r ea c l c l e c a n c l t h e c e n t r i t ' L r g t u b e w a s c a l r p e r l i. c w i t h t l v o s e r L l l l s t o l l l l e r s . ( - l h c s c c o n c ls e r r e c l t o \ l o \ \ l l t c r a t c c l f ' l e a k a g eo f o x r g e n i n t o t h e 1 l a s k . ) T h e s o l L r t i o l \ ! a s s l i r r c t l l o r . r t h r a t 0 " : t h e n n - b L r t 1 'b r o m i c l e ( 0 . 3 2 n r l . J . 6 m m o l ) r ' , a s a r k l r r l l a n c l t h e r e a c t i o n m i x t u r e w a s s t i r r e d f o r a n a r l c l i t i o n a lf J h r a r r o o r r r b t e m p e r a t u r e . A n a l 1 , ' s i s 1 g l l t c o n a n 8 - [ ' 1 .1 0 " ; i T C E I , o n C h r o n r o s o r b W c o l u m n i n c l i c a t e d y i c l c lo l ' c l i - i r - b L rl t e t h c r o l ' 6 - 1 " , , . a l Purification of Ciuprous Chloride.tr (-uprorr' chloride (-50 g) w a s g r o u n d i n a m o r t a r w i t l r c r r . l 0 n t l o f | \ ' L r l l i r r i ca c i c l . T I t c r e s u l t i n g p a s t e w a s a d d e d t o 7 ( ) 0 n r l o f ( r " , , s r r l l ' u r t ) L lrtrc i t l . I h e r s u s p e n s i o n v a ss t i r r e df o r l 0 m i n ; t h c s u s p c n d e ts o l i t l u n r l t l r r | 1 1 1 g l b l u e s u p e r n a t a n t l i q u i d w e r e s e p a r a l c d b _ rf i l t r a r i o n . T l r c t i l t c r c c l s o l i d w a s r v a s h e d w i t h 3 0 0 n r l o f g l a c i a l a c e r i c a c i c l . 2 - 5 0n t l o f ethanol, and 250 rnl of ether. The oll-'uvhite olid rvasdried under s v a c u u m a n c ls t o r e d a t 5 ' . Reaction of lodobenzene with Copper(I) l-Butoxide b5' the Rcaction of Lithium n-Butoxide with Cuprous C'hloride. Cuprous c h l o r i d e ( 0 . 2 0 g . 2 . 0 n t n r o l ) n , a sa d d e d t o a s c r u n t - s t o p p c r e c l . a n t c l d r i e d , : 1 0 - m l c e n t r i f u g e 1 u t - r e o n t a i n i n g a T ' e f l o n - c o a t c c ls t i r r i r r g c bar. and thc tube was llLrsheciith nilrogen. A solLrtion f lithiLrnt u o n - b u t o x i d e .p r e p a r c d t r 1 r e a c t i o n o f 0 . 1 . 1 8 ( 2 . 0 m n r o l ) o f i r - l r L r t ] l g a l c o h o l w i t h 2 . 0 n r n r o l o f m e t h i l l i t l t i u n r i n - 5m l o f D M t : . w a s a c l d c d a n d t h e m i x t u r e s t i r r e d f o r 3 0 m i r r . P . r r i d i n e( 2 0 n r l ) w , a sa d d e d t o t h e r e s u l t i n g l e l l o w s o l L r t i o n .a n c l t h i s n t i x t u r e a l l o l v e c lt o r e a c t w ' i t l r ( iodobenzene0.61c.3.0 ntmol) for l2lrr al rcllux. Glpc anallsis i n d i c a t e dt l r a t r i - b u t l l l t h e n l l e t h e r l r a s p r e s e n ti n 9 8 ' ' . , t i c l d . b a s c d o n c o p p e r ( l ) a l k o x i d e1 i e l d . Reaction of lithium n-butoxide with iodobenzenein the prcsenceof 1 0 9 ; c u p r o u sc h l o r i d e r , v a s a r r i e d o u t i n a n a n a l o g o u s m a n n e r , r v i t l - t c the exception that only 0.02 g (0.2 ntntol) of cuprous chloride u.as used. Analysis on a 6-ft. 3:; OV-17 on ChronrosorbQ colrlmn s h o w e d a 7 0 o , i y ' i e l do f n - b u t 1I p h e n l ' l e t h e r . Prep:rrative Scale Reaction of Copper(I) .rtc-Butoxide with Bromobenzene. Dimethoxlethanc (30 nrl) and 2-butanol (,5.6 g.75 ( 4 1 ) H . F l a s c h k a r r cH . A b c l i n c , V i k r o c h i mA c t u , 7 7 0 1 9 5 6 ) . ( a l . ( . 1 : ) R . N . I ( c l l e r a n c lH . D . W y ' c o f i 'I,t t o r g . S y t t . , 2 ,1 ( 1 9 4 6 ) . m m o l ) w c r c a d d c - dt o a s e r u m - s t o p l r e r e df.l a m c - d r i e d . 1 0 0 - m le r l e n m e ) , c rl l a s k c o r r t a i n i n g T c l l o n - c o a t e ds t i r r i n g b a r . T h e r e s u l t i n g a ( s o l L r t i o nu ' a s c o o l e d i r r a r r i c e b a t h a n c l n r e t h l ' l l i t h i L r n r . 1 7n r l o f a 1.6 ,\r solution in ctlrer. 75 rnmol) u,as added slowl-r,. Cuprous ll c h l o r i c i e ( 7 . - 5g . 7 . 5 r n n r o l ) r v a s p l a c e d i n a s e r u n r - s t o p l l e r e c f . a n r e d r i e d . 5 0 0 - n r l .r o l r n c l - b o t l o m e df l a s k e q u i p p e d r v i t l r a T e f l o n - c o a t e d s t i r r i n g t r a r a n d a s c r u l ' n - s t o p p c r e dr e l l u x c o n d e n s e r . T l r e a 1 r p a r a t u \ a n d i t s c o n t e n t s r e r e f ' l u s h e dw i t h n i t r o g e n . t h c l i t h i u m . s c r ' - b u t o r i c i s o l u t i o n w a s a c l d e c la n d t h e m i x t u r e w a s s t i r r c d f o r 3 0 e . 2 P 1 ' r i c l i n(e 0 0 n r l ) a n d b r o m o b c n z e n c | l . f r g . 7 5 m m o l ) min at 25 { tl w e r e a c ' l c l e co t h e r e s u l t i n g s o l u t i o n a n c i t h e r e a c t i o n m i x t u r e w a s r e t l u r c d f o r l l l r r . S o h c n t \ \ ' a s r e n l o v e c lb y c l i s t i l l a t i o n t h r o u g h a 3 0 - c n i H o l z n r a n n c o l u n r n . a n c l t l - t cr e s i c l u er v a s c l i s t i l l e ctlh r o r - r g h h c t ) l s a m e c o l u r n n a t r e c l u c c cp r c s s u r c . i e l d i n g 5 . 1 g ( - 1 , 5 9 ;o f . r c c - b u t 1 l l p h e n l ' le t h e r l r a v i n gb p 9 l ( l - 5 m m ) : n m r ( C C l ' ) 6 6 . 8 ( s . 5 . a r o m a t i c C H ) . . 1 . 0 ( m .l " O C H ) . 2 . 0 0 . 8 ( r n . 8 . C H r a r r c lC H , r ) . Preparation Scale Reaction of l-Bromobutane with Copper(I) r P h e n o x i d e . A n r a g n e t i c s t i r r i n g b a r a n d 1 5 . 3 - r n n -g l a s s b e a d s ( t o i n c r c a s et h c r a t e o f s o l i d s o l u t i o n r e a c t i o r r sb 1 'g r i n c l i n g )r v c r e p l a c e d i n e a c h o f t r v o 2 f f 1 - n r lc e n t r i f i r g e b o t t l e s . T h e b o t t l e s w e r e s t o [ ) l r e r c d . a n d l l a n r e c l r - r n d c rr t i t r o g e n . M e t h l , l c o l r l r e r ( I ) ( 5 0 m m o l ) w a s p r e p a r e c li n e a c l r 1 u b c . T o t l r e w ' a s h c cs u s l - r c n s i o no f m c t h y l l s ( c o p p e r ( l ) i n c t l r c r ( - 5 0n r m o l ) r v a s a c l d e d8 . 8 m l o f l r h e r r o l 0 . 1 m o l ) a n c l 1 0 0 m l o f p y r i c l i n c . T h e m i x t u r e w a s s t i r r e c lf o r 3 h r a t 0 ' . B u t . v lb r o n r i c l e( 8 . { l - 5 l . 0 . 0 7 5 m o l ) w a s a d c l e dt o e a c h b o t t l e a n d t h e m t m i x t u r e s r v e r c s l i r r e c la t r o o r 1 1 e m p e r a t u r e u n c l e rn i t r o g e r r I ' o r . 1 8h r . TIre rcactiorr mirturcs werc poured or.lto ice ancl tlre corlbineci organic prorlucts ertractecl into ether. Ammoniunr Irlclroride ( - 1 0 m l ) u ' a s u r l d c r l t o c o n r p l c r c o l l l l e r a s w a t e r - s o l u b l eC L r ( l l ) -fhc sltecies. c r t r a c t \ \ \ c r c w a s h e d * i t h a c l u e o u sK O H a n d r . l ' i t l t ice watcr: tlre ethcr'\\a\ rcmorecl on a rotar) evalrorator. On . d i s t i l l a t i o n u r r t l e r r c c l u c c t l p r e s s L l r c 9 . 3 g ( ( r 2" , , l r a s e d o t r t n e t l - t 1 l lithir-rrl)of l-[rittrI plten1[ ether *as cltrtained: nntr (C'Clr) o 6 . 7 7 . 2 ( n r . 5 . a r o n . r a t i C H ) . . 1 . 81 . 0 ( t . l . O C H : r ) . 0 . 8 2 . 0 ( r l . 7 . c c H : a n r l ( - F { r : i r r c ( ' 1 , ) l 9 ( r 0 . 2 9 J 0 " 2 8 8 0 . l 6 ( x ) . l 5 ( x ) . 1 2 9 0c m 1 : /ll c 1-50. l)reparative Sc:rleReaction of I -Bromocl'clohexene rvith Copper(I) T h c r e a c t i o n u a s c a r r i e c lo l l t o n a 7 0 - n r n r o l s c a l c i t r l-Butoridc. d t a m a n u c r a n a l o g o u r t o t h a l c l e s c r i t r ca b o v e : t h e r e a t c t i o ni n r e w a s 2 J h r . A r ec l u c c r l p r e \ \ u r e c l i s t i l l a t i o n l i e l c l e d 3 . ( r g ( 3 3 1 , , ) o f l - b r r t o r y ' c l c l o l r e r e n c : t r 2 ' D 1 . 1 1 6 3 5 :n m r ( C C l 1 ) 6 - 1 . 1 5 ( m . l . . C H ) . 1 . , s 5t . l . O C H : ) . 0 . 9 - 52 . 0 ( m . l - 5 .C H : a n c lC H , ' ) : i r ( C C l r ) ( 1 1 0 7 - 52 9 ( X ) .I ( r ( r , 5l . i , 5 0 .l - + 3 - i . 3 7 . 5 .I 1 9 0c n r 1: r r " t , I 5 - 1 . . Reactionof Copper(l) Phenoxide with lodobenzene. A solution n o f l r a l i d c - f r c c r e l h l l c o l - r p c r ( l()2 . 0 n r n r o l ) i n l 0 n r l o l ' p l r i c l i n c w a s transfcrrccl to a flarlc-c'lried.-10-ml ccntrifuge tutre contairriug p h e n o l ( 0 . 8 7 g . I 0 n r r n o l ) . a r t c l s t i r r c c la t 2 5 f o r 3 0 r n i n . T h c s l r e s u l t i n ga r n [ ' r e r o l u l i o n \ \ a \ t r a n s f c r r e ct o a f l a r n e - c l r i e c l . , 5 0 - n t l . u l r o u n t l - l - r o t t o n r c r l l a s k e c l L r i p p e c l . ' i t h a T e f l o n - c o z r t e cs t i r r i n g b a r 0 r I r r r r l ' c l r r n t - \ i ( r l r l ) c l e ( lc t l L r rc o n r l e n s e r . l o c l o b e r r z e n(c . 6 1 g . 3 . 0 r l r . n o ) u l r ' l r r l r l c t la r t t l t l r c r e a c t i o n t n i x t u r e r c l l u r e c l l - c l r l 2 h r . l a A n u l r : i : t r l 't h t r c u et i ( ) n r r r i r t u r el r y g l l r c r . r s i n g u S - f t . l - 5" , , C a r b o r v a r 2 0 \ { c o l r r n . r ri.n t l i c a t c t l a 9 - l " , , l i e l c lo f c l r p h e n y le t h c r . r C 1 ' c l o b u t : r n t l l\ \ i t \ p r c l - r a r c d u s i n g t l t e l l r o c e d l t r c o f C a s e r i o . I G r a h a n t .a n c lR r t b c r t s . Thermoll'sis of Copper(l) ,\lkoxides. Approxinralell 2-nrl a l i c l u o t s o f c o p l r e r (I ) a l k o x i d e s o l u t i o l r \ \ c r c t r a n s f e r r c c l u n d e r t n i t r o g e n i n t o d r r S - n t n t P 1r c r t u [ ' r c s . h c c o n t e n t s o f t h c t u b e s u ' e r c f r o z e n i n l i q L r i dn i l r o g c n . a n c l t l r c t u b e s n e r e s c a l e du n c i e rv a c L l u m . o T h e t u b e s r v e r el t e a t c c i n a b o n r t ' r v e n f o r t h e r e c l u r s i t ei m e . c o o l e c l . t s . a n i l o p e n c c l . l n t c r r t a l g l p c s t a r r c l a r c lw e r e a d c l e c la r r c lt l r c n r i r t u r e s r.r'ere nallzetl lrr glpc. Thc colrlrercontent ol'these solutions was a o b c l e t c r n r i n e c l r t h e l r r o c e c l u r e f F l a s c h k aa n c l A b d i n e . { t Thermal Decomposition of Copper(I) \lkoxides in the Presenceof C o p p e r ( I ) H v d r i d e . S o l u t i o r r s o f . c . , q ' . .c o p p e r ( l ) c y c l o l r e x o r i c l c ( - 5 . 0 m r - n o l ) i r r l 0 n r l o f l o l u e n e a n d c o i - r 1 r e r ( l ) 1 - p e n t o x i d e( 3 . 1 l m m o l ) r n 1 0 n r l o f c t h e r \ ! e r e t r a n s f e r r e c lt o - 1 0 - r n c e n t r i f u g c t L r b e s o c o n t a i n i r r gJ . 0 - m n r o ls a n r p l c s f c o p p e r ( l ) h y d r i d e . 2 e T h e r e s u l t i n g n m i r t u r c s u ' e r c c l e c o n r n o s eic l s e a l e dt u b e s a t I l 5 a n c l a n a l v z e da s clescribed L-rove. a

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(43) \l . C. Clscrio, \\', I{. Grrrhunr, and.1. I). Robcrts, l-ctrutttdrort, lr. l7l il960).

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