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A review o f couplin,q m e c h a i i s n s i s g i v e n and n o t e b l e exeiiples of Lon? r,u.lr,.e cou?linz in t h e literature w e ~ ~ s c u ~ s F ? ~ . ::ethyl p r o t o n s c a n underco Lon!: r n m E e c o u > l i n ~ rri-th p r o t o n s vinic11 me ^l+cr bonl3s strrny, aiid the mcchmi3m of' t h i s :-recess as r e h t e d to t h e h o n n e x m p l e s is d i s c u s s e d . J.p:)lic-tion of t h e phenomenon i n solvin<; s t e r e o c h e m i c a l problems is a l s o discils sed. T h e e f f e c t s of e l e c t r o n e i y a t i v e s u ' o s t i t u e n t s on

ions

range c o u ~ 2 l i n g i s a l s o o u t l i n e d .

i ) i s c u s s i o n of the p r e s e n t nor;: f o l l o n s , ~ ! l i c r e i n t h e d e s c r i p t i o n of' the p r e p w s t i o l i of ;rimy b o r n m e d e r i v n t i v e s

,

inclurling sevzral

cieuterated d s r i v a t j - v e s , i.s presented. The l i n e w i d t h s

i:'~

^{) of t:?e}

h/2

n e t h y l ,yrou?s w e r e measureii. i t wns f o i ~ ~ d that t h e nitith of t h e methyl

g r o u p s decreased j.n the _order i g > C g > C,

o,

^{m d the} Z and C m e t h ~ r l signals

3 9

were d r a . ~ i s a 2 p r e c i ~ ' ~ l y b r o a c e r t h a n t h e G 0 . Long rmse c o u p l i n s beliveen the p r o t o n s of t h e C and C metlij-1 Zroups is p o s t u l e t e d a s

8

7

beins r e s p o n s i b l e for these tvo bein,: b r o a d e r t h a Z

I 0 , ^Lon,? range coupling between t h e C n e t i q l p r o t o n s snd t h e C, end C endo p r o t o n s ,

8

3

5 -

md between t h e C,, met:qrl end the C endo ~ r o t o i i i s t e n t s t i v e l y

,

3

^----

ascribed to the clifferences in th? widths of the G

a

a n ~ C 9 rnetkjl g m u p s . N t h o u , ~ h the lins ~ ~ 6 6 t h ~ of t h e tertiary i~~et:>;,r,.ls were found to

v?ry :.I-it!~ s o l v e n t , t h e r e l a t i v e vriaths o f t h e t h r e e rilethy1 signals of t h e b o r n m e derivatives we$ f o u . ~ d to be t h e saqe. Thus r ~ e ~ s u r e n e n t of line wiilths is a neChod of c o r r e l a t i n g t h e methyl siglals i n s ~ e c t r a run in d i f f e r e n t solvents.

The e f f e c t s o n the c h e n i c d s h i y t s of the t e r t i a r y methyl groups of borna?nes tdlen v a r i o u s s u l s s t i t t l e n t s a r e p l a c e d t h e basic s!:releton, i s d s o d e s c r i b e d . The 2resence of m e t h y l e n e d i o ~ ~ grou3 at C or C,

2 3

r e s u l t s i n a d e s h i e l d i n g of C and a s h i e l d i n g of C w h i l e i n t r o d u c t i o n

8 9'

of hydroqyl groups has no uniform effect becmse oi" different orientstions of t h e hydroxyl group f r o m compound t o compoud.

An i n t r o 5 u c t i o n t o -the mechanism o f benzene induced s o l v e n t shifts i s given. Benzene a??ears t o f ors a stereosgecif i c complex 1~6th ketones, end o t h e r n o l e c u l e s , xilich c e i undergo a d i p o l e

-

induced d i p o l e i n t e r - a c t i o n . The e f f e c t s oi' t h i s intnrection on the n.2.r. s d p c t r n of v a r i o u s ketone s , p i n o n e s and aromet i c compounds i s d e s c r i b e d .

The p r e s e n t work d e s c r i b e s the ~ e a s u r e m e n t or" solvent s h i f t s a t v = i o u s c o n c e n t r ~ t ions o f k e t o n e s end ketal-s i n benzene. Previous

sLnilw r ~ o r k is discl~ssed in t h e l i ~ h t of t h e r e s u l t s o'atained, ail it has been shown t h ~ t some assuzlptions p r e v i o u s l j r used in correlat-ing the d a t a w i t h t h e in% e r a c t i o n s

,

hzve been L~I just i f i e d . Tne s o l v e n t s h i f t s versus the c o n c e n t r a t i o n have been plo5ted t o give c u r v e s v;hich h ~ v e bee2 i n t e r 9 r e t e d as i n 8 i c c.t ing s i x c i f i c s o l v e a t

-

s o l u t e i n t e r a c t i o n s ,

i.e. I : 1 , 1 : 2, etc., an3 n o t rpndom a s s o c i e k i o n s . T i i s hes been s!lom

---

by c o n p s r i n s c a l c u l a t e d curves ai'ih t l e x p e r i g e n t e l r e s u l t s , v i t h v!lich ~ agreement i s 2006.

! b e t h i r d p a r t of t h i s s e c t i o ~ of t h e work d e ~ l s ~ 5 t h t h e

s g e c t r a of some hydro~,rnethylel?e :ret ones, and commences w i t h i n t r o - d u c t i o n g e n e r a l -l ,3-d*.et one s s o l u t i o n . The r a t e s of exchmge o f e a o l i z ~ b l e protons i s discussed, and t h e i r use in d e t e ~ n i n i n g the r e l ~ t i v e proportions of' en01 f o r n s i s o u t l i n e d .

The ? r e s e n t work 6 e s c r i b s s t h e behaviour of 3-i'omylbornan-2-one i n c~rbontetrachloride

-

^{D 0} s o l u t i o n , ,uzd e x p l a n ~ t i o n f o r t h e pref-

2

erence f o r one en01 form i s given. ~ U s o d i s c u s s e d i s t h e couplin? b e t m e e n 'formyl' and hydmxyl protons i n hydroxnnethylene ketonss, and i t is s h o m

1' cn3.t the cou2ling depends s t r o n g l y on t h e ? I - 0 4 - H s n g l e , which can b e a l t e r e d by s ? ! i ~ h t cl~anges i n n o l e c u l ~ z ,geonet~y, t h u s IseSing to changes

observed, exc h r n g e

Froeesses do not the v a l u e of the couplin:: c o n s t ~ a t , but o n l y

whet h e r occurs.

A C D

---

C.'"i:ihLyS3D ,NiLj3&4

--

---- GZ! -- 3:

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ilS

---

_{Il'r C'lCLIC}

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ST" .La " ^1-24 -- -'

A camp-e'lensive review of the dienoxe

-

^phenol rearren,.:ene,rt is _p;iven d it is s h o m t h a t any cross-conjugate2 c y c l o h e x a d i s ~ o n e will r e a r r a n r e to 2.3 arorllat i c ? r o d u c t , the s ~ b s t i t u t ion of which depends

strongly on (i) tile s u b s t i t u t i o n p n t t p r n of the o r i g i n d dienone,

(ii) p e e i l l - i e r i t i e s i n t h e molecular s t r u c t u r e , and (iii) t h e rearrangegent conditions. R e ~ r ~ ~ e a e x t s o r sene d i e ~ o l s m5 s o w cross-conjugated r - n e t h ~ ~ l ~ n e c ~ ~ c l o h e x n , d i e ~ i ~ ! s or 'sernibenzenes' m e d e s c r i b d , end in general

v i i

these f ' o l l o ~ ? the pa- tern of the dienone

-

~ h 2 n o l r e n r r m , ~ e z e n t . Besrrcnge- rnent of some s t e r o i d a l ot-suSstitutsd k e t o n e s is a l s o m e n t i m e 3 b r i e f l y .

TO c r o s s - c ~ n j u , . ~ : a t e d netizylenecyclohex~dienes v e r e sjmtiie sised by r e a c t i o n of ::let !~yl!!lagnesiun i o d i d e on t h e corresponding dienones

-

t h i s r e s c t i o i l liad p r e v i o u s l y been r e 2 o r t e d t o g i v e o n l y the p ~ r > d u c t s of re~xr~n:,.einent of the i n t e r n e d i a t e semibenzenes. Tne semibenzenes were r e a , r r m , . ~ d u s i n c p e r c h l o r i c acid in m e t i c 2drljrGri?.e

-

e t h y l a c e t a t e t o give t h e

,

I+-2-isubst i t u t e ? a3..oxct;ic p r o d u c t . The a t t 2cki.n~: s p e c i e s ves shown t o b e r y o t o n , and t h e reaction, u n L 2 c ~ t h e c?-ienor~e

-

^phenol

rearran,.;.ement, showed a c l e w preference " o r m t l ~ y l e n e r s t i ~ e r thm ethyl m i g r a t i o n .

S e v e r s 1 m e t h y l sub s t i t u t ed s t eroic3.e.l 2a~-117cko177-t,c-en-3-one s were p r e g e r e d by ^{t h e} re,?,rr~+r1ge1:1ent of' t h e c o r r e s ~ o n r ' , i n ~ L, j-epo,r,l-3-ones ~ i t h s u l ~ ~ h u r i c acid i n a?-ueous ~ c e t o n e , h e r e i n sbonm t o b e e g e n e r d method.

Fie !iy4&-orjenones vere r t ? a r r m ~ e c i u s i n g t l l r c e s e t s of c o n S i t i o n s : Toluene- psul-qhonic ecir? in rnethenol, t o l u e n e - 2 - s u 1 : ~ h o n i c

zcia

ⁱⁿ benzene, a d pcrc.~d.oric acid _{i n} a c e t i c m-iiydrirle

-

e t h y l e c e t 2t e

.

^{Only one} compou.nd, 2 6 h y d r o q ; ~ c h o l e s t - 4 - e n - j-one : ; m e ^,zn eromztic p o ? u c t ; t h e other s u b s t r r b s unl2~2rneut resrrp;y;exent ";lrlroul;!i t i l e v p r i o ~ ~ s e ~ o l . ~ , t o ;;ivc ~ t t ^P,c~: i l s v 1 . d l ~ r

~t Cg of t i l e cxrm50n s::eleton. -4 n z c h m i s x iz g i v e n m3. d i s c u s s e d f o r each rewr,o:cl~c';~e:;t. o I - ,c A i . : ; e r n seelxFt< to _emerge.

ii revier: oi' ths x e c h s ~ i s n o f th2 Ile!,lrqensen r e d u c t i o n i s given

17it.r:h s A x c i f i c r a f e r e n o e ^!;P r c 3 - u c t i n ~ oi' cIi,funstionel c o ~ ~ p o u n i l s , ?$leye

viii

r e m r e - r g e m e n t s rney occur.

T:?e > r e s e n t ~ : o r k ssho.rvs t h z t in t h e Clemr-nensm reduction of I ,3-d*-et rnes

,

^{t i ~ e} i n t e m e d i ~ t e cyclopropanec?-iol vrhicll j.s f i r s t formed, unCert;aes aciaolysis t o g i v e an a-wiror-~ k e t o r ~ e znd e Fb4~d-roq7 ketone,

P % C ~ of P T Z I ~ C ~ rncj t h e n tln4erl;o rurther C l e n : . e n s e n rerj.l_zc:;ion to ~ i v e t h e

0?> 3erV9fi re! a r r m g e d 2,nfi I J W ~ ~ . r r , ~ n ; e ( monol;et one s

.

^{T h e} btcrZl.le6-i P..c:~ of

E , ~ - ~ v , ~ c L T o ~ ketogp, ~ ~ 8 s :;rcved jy 07assrvir:s t h e r ~ ~ k ; t e o? forrm2tion o:r the proZ.uct;s, ,?lid. : ~ ; r i:ep.zur:'Lng <;!IT rrfve of re?.ucticln oZ ^2'1i ~ ~ c t e ~ m - d e n t l ~

+ r v r r T ? - - m

,

^{1 C.} -

I:':T4i.:CI~.LC5wfiL

? ~ ~

- ~ - ~ ~ ' i ? ? - ~ - C ~ ' ~ ~ l ? ~

~ < ~

x-AibA-L-,a

c ~

y-:

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^{- -} >i?,c:y-Tz$

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F?clps

I - - - . _ I _ _ -

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-4 s?iort r-suL-,6 o f i1itrz--101ccu131z ilyl!ro,yen c . j s t r ~ c t i o n r e c c t i o m u s i n s 1-d tetr:is.cctzte o r 1 ; ~ ~ e 1 ; r ~ o i o i i i t e f l r c c e s s is =iven, ~ i i . t h some d e t a i l being sspl-iefi to the coc-~?j-t-ions, t k z stcreocbl~cis:ry neefie&

for t l ~ c r e a c t i c n , ~1.2 tc 2 r ~ ~ p ~ " n ' i ~ t . i o n processes ~ i 2 i c h rcc?j- occur. S r i e f r ~ e n t i o n is d s c ! made o f t h e new r e e c t i o n ; ~ I ~ ~ J - o ~ F , I ! a b s t r n c t i o n u s i n s decornpos ition o h lq~iyl>mnli t e r.4-Z;h silver ions.

The l e d " i e t r r z c e t - t e rr-.cc-t;lon xas ~ t p p l i e d 7;i4~hout success t o aSstrcc"iiorr o f '-y2ror_:er? :'ro.: cli w o n a t ^{l c} ? ~ c t l l y l grouin, u t i l i z i n y an

.=

^{r 3}

.

T r y r f i e n t ct i o n r w c t ion s were ,yener n l l y a-hen z y l i c hyCro-rdl

o i ~ t a i n e d . *plic?L.icn of t 3 e b r o x i n e

-

^silvqr i n n ?et:lo3. p r ~ e ?cod y i e l d s of cyclic e t h e r s in _t7;o c r s e s , iqdi.cstinf: t h t a S s t r 2 c t F c n r e a c t i o n had

I t 4 ~ k e 3 :ILF,c~. I?-lkc? conrlLtio_rls l'or s u c h a r e c c t i o n seen ",be c r i t i c a l :

11 t e r t i a : ~ h y 2 r o q - 1 r r o u p I s rl::euired, and ti:e abstr-c-kion s e e m on*

A LO t&e p1acc ^:'_r0.:1 2 ?sinlw,t. celltre.