Studies in carbonium ion chemistry

A

by

1

( )

( ) ..

oyolio

mass

(46-51; ) ..

ABSTRACT

me~o-hydrobenzoin sulphites (94-96) have been

pr'3pared an(l in eaoh case the stereo-isomers separated ..

Pyrolysis these cyclic sulphites gave mixtures of

aldehyde and ketone.. For any pair of sulphites product

ratio been shmffl to be dependent on the stereochemistry

of the 3-0 bond. a. greater yield of ketone being produced

when the 3-0 is syn to a hydrogen on the heterocyclic ring ..

This is thought to due abstraction of hydrogen by

the syn to form the enol of a ketone. The differenoes

between the aldehyde to ketone ratios for a series of 8-0

isomers. where the aryl substituent changes, has

rationalized in terms of the migratory .aptitude of the

aryl group"

The product ratios obtained when the unsubstituted ()l),

I-methyl (33), 2-methyl (42) and l,2-dimethyl (45) alkenes

are oxidized by Kllln04, performic acid and iodine-silver

acetate-water are discussed. Ifhe products from these

oxidations are the substituted cyelohexane-I,2-diols (46-57;

60-63).. The cyclicsulphites of these diols have been

prepared and the isomers separated. Pyrolysis of the

cyclic sulphites produced aldehyde and(or) ketones. The

products result from a 1.2-hydride. methyl or methylene shift.

1

1 ..

<II

(

OCC1.1r~

x ( R occurs

(

are t.U.-"._

an~~e,me~nt.s .. 1 t 5

O(1;6Ur (1" 1

(

(i)

1",) are

(2)

(

:»

( )

lO~

(

)

) 1

to 11

)

)

7

)

( ( 1)

a 1 or

(8 1;1

)

)

) (

)

)( )

(

)

)

.. a.~iOt 1)

) X. 6 ,. 6. 5.

) Xt 6 !h

) I, 6. 6.

(

)

oourse

)

..

) "

-H( )

-( ) -

)

on

(

) ..

1

2

(29)

)

).

( to

)

)

)

)

.. (

)

or

) ..

)

) .

(

(

J)

( )

..

{

( ).

)

H

3", )

:h

J~ ) :; S)

3~ 7} 1"

j,. ) 1.

Jll' ) 1

3.6'1(7) 1

3.50(6) 1 5

J .. ) 1'111

J .. 6) 1.

) 1.25

(

)

)

1 9

1

an

..

)

( )

)

(42)

( ,2p ).p, 20{ t ,SO} (4?51

S cO 5!h61

4 1

1

LH) 1

S 1

1

1 4

4 1

1 1

1

0):1

)

) .. ) p

)

A 1

)

-Bllm9" )

)

)

..

,

)

( ).

1

4",

49 , . ..

1\1> fiX)

1. ) 1. L~.

) l. 4"

, ,:.,. 1 ax)

4 ) 1. ) 4. 1

I'i

('3 1. ) 1 1 ..

h2 ) 1. ) 1.57

(

(2 i9)

the

(

) . ·try( "l6) by

the

to

) ,,,ere

(3tl) w~s

)

by

:3

1

j .

1

J. 11) 1.o~H24iS) 7')

). 7) o. ,7)

,'),. 16) 1.2.5)

• (6) J,1)

·,

1. ~r,6)

1 .. 15( fIn

( )

or

A

1f3

) to

were

All

be

an

(i)

by 1.

a:n

are

) ..

100

8 76

8)

,

the

no

a)

A

B

1

,76, )

.'76) HX~

( )

70

80)

) )

( )~

1:1

(

un

( )

formation·

) ,

( :;I) ..

9)"

• 9)

(

(

(

(

(

(

)

) ..

).

).

) 4,1-

)

) ( )

(1) ()!' ( )

).

(

41.,

) .,4 .,8

) 97.8

) 0 -4101(108) 0 ....

(a)

(0)

(

to uncover

..

ev

more

(

Ion 143b (

( )

on

J+l~.

The losses can

occur either from an open chain parent or from a parent

where the relative stereochemistry of the diol is maintained.

fhe latter must be the case for many of the fragmentation

processes !..!J!,.. the loss of 18(H20) and 55(C4H7).

~oss of water from cyolohexanols oocurs largely by

1,J-or l,4-abstractions, abstraction of a tertiary hydrogen

being preferred.55.65-68. It has been found that for an

extensive series of tert-butylcyclohexanols elimination of

water occurs most readily from the trans-isomer. In

4-tert-blltYl cyclohexanol the process occurs ~ a 1,4-abstraction

in the boat conformation, and in 3-tert-blltylcyclohexanol

by a 1,3-trans-diaxial process66(i and ii, Fig .. 32).

In the unsubstituted dials the greatest loss of water

occurs from diol(49) where both hydroxyl groups are positioned

to undergo the most favourable abstraction of a. hydrogen

(iii. Fig .. J2) .. T-his is reflected in the overa,ll pattern by

the base peak at m/e 80, which arises by the loss of two

molecules of ,.,a.ter and the tert-butyl group.

Loss of 55(C4Hi) only occurs to a. significant extent

from that diol( 48) where the stereochemistry a110\,18 the

tert-butyl and the hydroxyl groups to be in close proximity

in a boat conformation.

1

0.6 o

7

0",

on

on

The silica gel used for colw1ID chromato~:raphy vIas Crosfield

quality :8 .. 3 .. S. Sorbsil. All solvents column

chromatography '\Il€Jre techni Benzene was distilled

of P205lr

Merck silica gel G with 'binder li'luka. alumina type H

were used for ~LC .. plates iIIara dElaetivated

by being left open to the atmosphere for 2-3 da.ys" BenZene,

CRel] and CHCl)-acetone mixtures '>I'lere the solvents most

commonly used for developing the chromatog:rams.. The

visualizing agents used )vere iodine or phosphomolybdic acid

in EtOH.

4-tert-Butyleyclohexanol(28,lOOg) was dissolved in

acetone(250ml) and Jon€E Reagent (CrQ3,lO.J:112S04,8.7:H20,30)

was added dropwise until the reaction mixture rem.ained a

brown colour .. After stirring for a further 30 minutes the

until a permanent gTeen colour resulted .. The product was

isolated by extraction with EtzO. Distillation afforded

G1£ pu.re (Carbowax 20M) 4-tert ... butylcyclohexanone(29t85e,80%}

m Lr8-.500(Lit"J449-500); ~max: 1715,1220" 1165, 945cm-1 ;

NMR b O.9)(S,9H; tart-butyl); 1.5-) .. 4p]'Jl'l\(methylene groups) ..

)

) fl,

(

( :;

h V ~ ; li1;O*,

; .. O. ; h , 1

.. ' ).

over.

°20

905

(

(1 1) of

; 1,,20(s, ; ); 0 .. 8;(8,

one mole of

oooli:ng

{ {

(Lit. J7b11 , 1560, IJ1}Q?

( ,s_,,~_,u); 1.62 . 11

, ,,0

).

..

solu"tion of ketona( f 49.. )

7,,4g)

100ml) • 12

)

(

( f h );

()<i\ if< :5 ). Ii iii

( 2 ..

J 1) )

( ,

(11)

ot

);

(4Gg) was

th~

" "

(

(

"

) ~ v ~'i(. )400,

h ( h 1

, ;

1. \h o. , J

( )~

)

} as a

).

(

1

)

) J

0 • h o. It h .0 , , ,

(

(

the

(

in

~XCefJ~)

a

)

)

• , 1000 ,

1,,00

(

~~$X

o

(

( )

),

\,1"'",""""&:1,,..) ,

)11

40(0)

1

(c)

)

(

(

II ,

, J h 2 I

-, h

: Of 7() O.

,

(

1)

m. ), .J .m8X , 1.

• 1 1. .. , 1 h h

,

(0)

(a)

{

A

( )

V£'l .... U.H,C;;); )f 1.8(

h 0.8,( 1\

tto;_?::a""",:-

~mtlx , t

(

1

h e,

""'~ie~""'U;;Jc'" ) •

""""".",,,,1 , 0 t

10.6,

~

l!it

lIt 12,,0.

If J

.. , h ).

II (J~ "!Q.9; II, ..

"SO, "",U-,.uu); 2. j( 2ft,

(

(

l

h

., , , J

" , 0

'" 1:2)

), 1 .. rl( ; f

h

I

,.·.·n~"'H.: C, 10 •

•

" It

0

.. 9; II'

0, 71 7 • 11.9.

(b) (lJg)

~, __ ..... -·u ..... ,C>"" ~ .... diol

(60 121 Q -12i1 .. V max )4,0. , 114;, 1120, 1055, 960,

950, 912, 827 I ~ 1.23( "

tert .... buty1); 1.2 .... 1.7

!ll. solution d101(48,4 .. 0g)

produot by m.eane of

( 6t",5.

1125, 1210, 1100. 10)0 em"":1 ;

; Ar .... !l.); 7.Lt7(Wh/2 II )Il,

, ; ;

2.,O{lH, 0-1.); o. (f.\ t tart-butyl); 1. •. o(

I Ot '13 .. 6; ti, 8.8. C11Ha40J =

Ot TJ

, Ii

; .H, 8 7 '.. II

).

b 8 .. 06( Whiz llH~. 5.47(Wh/2 ,;

A

was hea.ted

1)1 meane EtzO.

on alumina( ).

)

(by )

(8.)

,2.

t 112!5, , 1125_ OlD-I;

Ar .... l) J 7 .4'?( Wh/2 , ;

"hU-""z.Jii»/, ,.67(

_~nt'lI"_). t 0, 74.6;tl, 8., .. 8.

traotionllJ

!Ii

tirne

produot

( ) in

pro pan-2-o1 ( lOOml) W~I'!I ''''Y'''''''''''',

reflux one

64.

by

removal the £I01ver'1't was chromatographed on al'llmina

(S%,250g). Et20 eluted amixture(O~ ,1;1) of

4o<-tert-butyloyclohexane-10lt2ol-diol(48) 1 Pt2~-diol( 49) ..

Further elution with yielded 4o< ... ttiJrt .... butyloyclohexane-

1~t2o(-d101(47,O. )m.104-106o(Lit.l2l0~1070); ~ max 3250,

1110, lO?5, 1060, 985 om-l, ~ ).50(W11/2 16H~t ,Oli-Oli); -2.6( ; 0-1>- 0.87(8, 9H; tert-bu,tyl), 0.9 ... 2.2 ppm(methyiane

) . (b) SOdium{ 5g) was add,ed a solution of

4~tert-trut11-oyclohexalY -2o(-benzoloxy-l-one (2g) in

iaopropanol(lOOml) II' When the addl tion was cOInplete the

reaotionmixture was re!lttxeo. tor one hour.. !'he produot

isolated by means of ]lit20 ohromatographed on

alumina(51b,lOOg). eluted a mixture(l:l) of 0.1018(48)

and (lt9}(O. ) followed by <11101(47)(0_81$).

waB heated under reflux in. acetone for 8 hours. product

was isolated by meEtnS of EtzO and chromatographed on

(5",2.5017;). EtzO-pel1tane(Ja7) 4o(-tert-butyl-lp ....

methylcyolohexan -2-one-lct-ol( 68,2 .2g.451')

b

h 1

on

1,50g).

, f

Ii t ); t!

o. 11/ I ). ,

(1

a stirred eolution of

one hour.

1~t2o(-lttereooh0mistry,.

l~tert-llutyl-l<x.2~

m. 111°-119°; ~ max

Nf"IR b 1.8(211; O-!!)a 1.

0.85(s. 9H, tart-butyl); O.

Fo~nd: Ot 71.8, .0.

)

then

the

, om-I;

• f coa....Q!!j) ,

I. s c. 71.9. 11,

in diglyme(20ml)

3ml). Th~ diborane

of tllke:ne(6g) in

wali') oomplete the

.1 ..

to one

a solution

(

procluct(5

6' .... 64; max 3400, 1060, , 990,

).6S(wh/2 7H~.; h 1.,!HlHJ

, JH;

~ max JltOO; , lOB!h

, ; ""Uo-1JU).' 1.7( ;

() h 0

for one

).

by

70.

)

(?O.l.Og) OID .... I ;

; 0.96

Elll

), 1.0-1.9

l:l~O )

~ ... (14)( ,l.lg)

S )\t06(

je,80(Wh!Z h o_ Il J7Hz. " , II • it ) .

-01(12 ~ 3.01 ( , 2.5, I );

o.

)

,

( )

)

O.9G(

(c)

.. , , * ""l,,-'vn ... ) ,

).

( )

) ~ nlwc171S, 1210 It

~ 1.15(d, J , Oft-Ci) I

1 .1 cppm.( ) ..

71 waH

on

) 5c(-tert-bl:rtjrl.,~~p-

) ~ mfiLX 1715, • , 1155 I

; ); o. h

) 1

11)0,

o

: 0,

0.90(s; ii''''11~A: C,

l:3(s f

)

) ~

1.05(s ) ;

diol(O.

mnd

on

or

C>I.. (48)

( • #

; 0, .5; ·1·· t\'" ,,1 17·· " It ... . \1. V ; !,.! Ii . .. V fI

.5; ti, 9 " fit ,

(JUB,l'2. (

110 S. (Wh/2

(Wh/2

0 ..

)

orUtxane .... .Lr t 2 f

• 10)0,

vU" .. v.,;'v); 1 .. '55(s.

"

, 170.

)

s,

(

,

_~',L_"' .... ( )

, 1100, ,,715

A)~3.

(B) 4.J1(

t '''''j;;j.-v~v); 1.5)( )

1 )

(Al S 4.20('Wb/2 , ), 1.4S(

( 4.65( , • ,.nl.-"',,",...,); 1.

$I 2~ .... d101(57)

A: 1 ; ~ max 1200, 950, 940,

)~ 4.13(t, J 6Hz" ; h 1.70( at . , H'n"t'!,nl"tl C, 66 ; 11,10.4; S, .. 7.

c. .9; H. 10.1; 8, .0.

p ,,2o<-d101( )

l~, 1:1); ~ max , , ) ~ .. ); 1 ) It ,

; ( l.

1:1) ; ~ m,e:),~ • 710 ;

).

)

cyc1io

left to

4,

~ max )400,

1. Sf h (B) ,7 iit 10

10.

\,ii"''''''',U::J.I.f;lW;.l'~'''A. P' t 2 f -eli 01 ( 6:3 )

; 910, a'5. 810. 190

h (B) 1.30 1.20~ II

be:fJt~o~Ln a4)m.86°-81°( )

, l580, 10"10,

74.

4,

Jmax ,490.

~ 7.90-6.85(

:;,

t 1000.

"-,u-,,,,.<·,,h 4. S

(Lit~

. 0 4o( 112 -11

• 10)0,

h ~ mp"x

,7.31( ,

•

);

)

rD", ), ~ mu " t , 8 t ; • •

~ , t

6 • t fJ J , h 6 I .,

( St

.); H, 4.11

0" I f

(

J , Oli ..

was <ll>tA\"U1.1U.

_10°.

)

.,

( h ~ max: , , "I t ,

• ; iii, ).

( ( II

..

{

)

I ,

m,

J , );

II ).

• c. }.~, " , , 0,

)

)

;

~ ~ f , (4, J t , h :h ). " f , l!I,

<;. •

17:30,

1

4,

1130 t cm-1 ,

, Ar-l); ? ~27( ;

h .J max

(102.

b 9,

• .,

(106;

(

by

, 990,

, 4.2'1

, 2750 11

... jl:: ..... ~t:n.J h

SEJO) • ~ max

• ?2?(d •

.. <if 2.. ,. .,

S, ,

J ) J ~ ~U:l.X t 2740 t

I ~ 9tiS(d. " );

1.14(88J J 4.80(tl,

_r'-.. .• "_) ..

eli .?; H, 7,,2.

,. Da:rJ!~0~Ln 101; h ;) max

.. , , ; 4.22( 8~

0, 03.); :fI, , ° 14lilOO(1l2 e, .4, H. 3.8; , .8.

J.

~ max 2720, 2

4.80 tI,

vU • ...ul'l,4) );

).

t 940,

( lB, h J h 87( h 1.0-2 ion

II a

•

( I , ) malt S 2.15( )

() ) iii

~

•

82; J

11~ , t t $ 2.13

( II. I , h ; h 1. ).

at oj ~16?O56 4' •

( ).

A

),

)

( )

was

pura ( ~1l'>"'hrn;'fft:!

) loa).

was

meaQ .... Uu:nnfi!I."S

1

..

(

(

1

(

(

(b) (

) ..

(

)

(

"1tf.f;re!'lS ( b ) i

) was ).

(

( , (

)

(

) )

1 ..

2",

,(II

J

J

J

).

D

l.

111

•

1/1

).

J.

III

).

.J

• J.

.H

)Jr

•

•

O,,"R. Johnson. J .A .. C 1020(1963).

16. II.F .. Van \1oerden and E. Havinga. .. Rec.Trav .. Chim .. ,

17. C. Altona, R.J .. Geise and C. Ramel's. Ree.Trav.Chim.,

!i. 1197(1966}.

H.M"H .. Shearer .. J .. 0.8 .. , 1394(1959).·

20.

C.B. Johnson and D ... McCants. J.A.C .. S •• Mf 2935(1964)"

J .. G .. Pritchard and P.O. Lauterbur. J .A .. C"S .. , .§.l

2105(1961) ..

21. F. liaake, P.J. McNeal and E.J. Goldsmith. J • .A.C.S.,

22.. llil.D. Brice, J .M. Coxon, E. Dansted, M .. P. Hartshorn and

T .. Robinson .. Chern ... Com.m:s. 356(1969) ..

23.. A.J. Lewis .. Ph.D. !hesis. University of Canterbury.

24 .. Yu Tu. Samitov .. Aminova .. 2*11. Strukt •. Kb.im •

25. Yu Yu. Samitov and 10M .. Aminova .. Zh .. Strukt"Khim ..

(Eng .. transl .. ). 2., 497(1964).

26.. K..W., Buck, A.B. Foster, 111 eD. Pardoe, M.H ... Qadir and

J .. M .. Webber .. Chem .. Comms .. , 759(1966).

27. iL.B .. Foster, Q .. li.Hasan, D .. Ha"lklns and J .. M. ~vebber

Chem .. Comms, 1084(1968).

28. K .. W .. Buck, T .. A .. Hamor and D .. J .. Watlr:;in.. Chem.Comma",

758(1966).

c , ~T • • R ,1 ).

e ).

J~ 1> Ii<

C .. ;li( ).

• ) . )"

~<' ). l!J .. , ).

<::t ). ., .. '1\ i.? !II, .. l!' 'If " '" "

).

54. f ( ).

.. Hit '" D ...

,.

).

)

).,

J ).

(il,0i)

Enerf'-V 1

Reaction

(0)

"­+c-/2

Coordinate

R I

-c -I 2

,D

Fig.2

• products

'- .R. /'" " c <-:t...: . c /2 1~

Oi)

(e)

R R

•

R

Fig.3

t-Bu t-8u

N2 H

OH

OH t-8u

----------. t- Bu -o-C HO

R' I \

-~ -~-X ~ . products

Fig.S

ROH + CLSCL t ROSOL + HCL I \ '

0 0

ROS-CIL + R10H ., ROSOQ,R1 + HCl I

0

FigS

X~H X~H x.q,H4 H 0 Xq,~ HO

O __ ~ ___ O 0" / 0- 5

sy n- ant i -

I Fig.7

Ar :\ 6+

·Ar 0 H

aldehyde Ar o H )

Ar / I : H

05 ___ I ,

07, ... H

H 1\

~ 1\&'"

o 0 Ar \/ ketone Ar • sO I

: /50 &-'0

Fig.S

Ar H ~-H ~r Ar , : Ar r H 0 ,"H°ici ketone

- • )

0"":""/ __ 0 l) I ~ .. ' 0 6~S~

H OS~H 116

Fig.9

t-8u t-Bu

A-isomer B~isomer

Fig.10

R H R

t- Bu l'~rl-N-.CAr Bu-t

+ e' + Are + MeOH r MeO

R H

R

t"Bu H Bu-t

Fig.11

0 o· .. e No" II I No 0" H

RoO'" II" C\ CE>~ H.LQR

. / l C R"IIII \ R'IIIII \

R' R' ! R'

( i)

oe No·

I ~I RJlIIIIIC~C

I H RIIIIII \

R' R'

" ..

(i j)

Fi g.12

N NH-S02G6 H5

y~ 0 CH3

' 56 57

)

.~ 54 )55 t-Bu t-8u

t-Bu CH3

CH KMn04 . 62 63

OH ~ /

It

OH ~ 60 t -Bu t -Bu 0

a

t-Bu aGOR

II' 47

: t-8l! ---'"""'-'I>. 61

t"Bu

Fig.13 t -Bu

t -Bu

t-BU~---

t -Bu

complex I) X· , ~l 126

> CH3---<{:t 127

0\ MnO )

/ 2 o t-Bu

124

0

/ )

Mn02

125 0/

Fig.14

CHJ

C021 + AgI

CHJ

C02I. CHJ

C0 2Ag+

(Simonini Complex)

CHfOOe> ~ CH:3-C-O~ ~

' t' we » CH3COO I

HO

Fi g.15

OH

OH

OH

x ~o HCOOH ) 'f-OH

HCOO+

Fig.16

I

H taBu

~ ;:::----t-Bu

II 132 ~

33

133 139

Fi~

----t

~ t-Bu _~SO

Ii~

2

Fig

11.5

10

6.5

5 5

0

. ii iii iv v VI

1 ). 0.4 1 3 0.02 1.3

2J. tG 5.S O. 8 0.02 5.8

3). 0.09 0.2 0.2

% Relative population when

1). a:::e=H

2). a = CH J ; e:::: H

3). a::: H;

Fig.20

Fi9. 22 ·

CH3 C~ 'c"""""" ''3

C~ H H

106 ·0 BF3

CH3 CH3

HO )

0" / 115 /C""

CH3 CH3 (i) Fig.23

CH3~ ');;CH3

111~ OH

109

(i i)

rotation followed

by ring closure

115

ring closure

114

BFj OBf3

~ 0

I C Ct-( 'CH3 /C"

CH3 CH3

(i) OH

110 OH

{ii)

(i i i)

Fig.25

. C~

0'-../ C

~ 0/\ . CH3

112

rotation ------.. followed by:riilg

closure

112

ring closure

11 3

Fig. 26

OH

OH ••

t- Bu

+OH

+OH

OHCH

t- Bu

1 +OH

3 OH +

+ OH .

OH

Fig.27

2-Me. ,

OH ~ +OH

~

OH

Inl \#'

+.

H3 HO CH3

CH3 • OH +

200 +

t- Bu t- Bu t- Bu

+OH +OH 143 )

OH OH 8. b.

Fig. 28.

100 Diol - 48.

GO

20

I I .1 I I I 50 70 90 110 130 . 150 170 190

100 49,

60

20

I II II I 70 110 150 190

Fig. 29

100 Diol - 47.

60

20

I I :1 I I I I

50 70 90 110 130 150 170 190

100 46.

60

20 I . I lilt I I

70 110 150 .190

F'i g. 30

100 1-Me. (50-53)

60

20

I I II I I I

50 70 90 110 130 150 170 190

2 -Me.( 54- 57) 100

60

20

70 110 150 190

100 Di -MGJ 60- 63)

60

20

70 110 150 190

Fig. 31

OH t-Bu t-Bu

, .

( j )

H OH

( i l>

t-Bu OH t- Bu

( i jj)

Fig. 32

RO-S-OR co, 0 11 5=0 ( \=0 0 d 0/

1 2 3

0 CH0H CH3 I t1)-; ~/S ~,/S-O ,-

\\\''OH \".0 ~I 0/ i 0 0

4

CH i 3, ~

i/O 'CH \ i I 50

CH / " Q

8

5 6

CH3 CH3 C~

0 ~S

o/b 70 7b

H H R

~~R Ry{-R R\d;H HO

~/ ' 0, / , 0, / 5,

0 0 ,...-5 .....-S o '

80 8b

20 R' = CH3 I R= H (80 ,8b)

8e

. 23 (80 ,8c 18d)

7 (80 ,8d)

7

R

ad

H

H

CH:20H \£0 S~ I H6 1 o OCH3

90

CH20H

~O O-S~

H6' 1 OC~

9b

C~H3 0, / .

CH3

C~~H 0_ /

SO ........50

100 10b 11

14

16

10

12

15

C . /'" ~CH

CH3 2

18

'13

9Z

S2

H

t"JZ EZ ZZ

05 /\ o 0 OH8

HZOSO SH9~ OS \ /\ H8 HF.:\ ' ~O H , I 4 Z (SH9~) H 9H~ H

+\ I SH98 \I

SH98

LZ OZ 6~

OS /\

SH9,)ZH8 .------05 o 0

HZOSO / H ra~ \'

'. SHr~9:J HH O~%' 0=8 , H SH9:J H

OH NNHSOf6r1s

CH3CH= CHCH3 t-Bu t-Bu t-Bu t-Bu

27 28 29 30 31

OH CH3 a a a CH3 CH3

COC~~H5 COnHs

t-Bu ,

t-Bu t-Bu t-Bu t-Bu

32 . 33 34 35 36

----N-C6t-t,2 a OH OH NNHS02CoHs CH3 CH3 CH3 CH3 CH3

t-Bu t-Bu t-Bu t-8u t-Bu

37 38 39 40 41 "

OH CH3 yCH3 VC~ CH3

CH3

t-Bu t-Bu t-Bu t-Bu

42 43 44 45

OH 0 0

OCOC6HS

t-Bu 64 65 66

OH

OH C~ 01

.-'

67 68 69 OH CH3 1; 1/ .t,fJj CI-

OH 71 72

o

73 74 CH3

75

0 CH3 CHO CH3 9

t-Bu t-Bu t-Bu 76 77 78 79

cfCHO yCO-CH3

CH .

ct:O- CH3

t-Bu t-Bu t-Bu 80 81 82

XC6H4-CHOH-CHOH-C6H4X

XC 6H4- CH- CH- C6HL0 / \ I ° /0 : "SO '

XC6H4-CH2-C-C6H4X -'II

° (XC6H4)2--CH-CHO

83.X,H

84.X,CHj

87.X ,H '

88.X,N02

89.X,H

90•X,CH3

94.X,H

9S.X,CH3

99.X,H

100.X,CH3

102.X,H

lO3.X,CH3

8S.X,CH30

86.X,Cl

91 •X,CH3O 93.X , ,NO 2

92.X,Cl

96.X,Cl 0

97. X,N02

101.X,Cl

104.X,Cl

c~ I

~c~ W:H

C~CH3 C~~ CH3 C 3 C H3C HO H - CHClCH3

H HOH 3 H , . OH

'0 '0 OH OH ~05 106 107 108 109

OH "

~OH ~O,,/H3 OH OH O-C,

CH3 110 111 112

. H 0", I CH3 H C~CH3

C HO . HO

/ 'CH o 3 0" / 0" / /C" /C,

CH3 CH3 CH3 CH.3 113 114 11 5

o I

116 R~S

( Fig.9)

117

CH3 0

0-51 , 0/

H C6HS

o

% 119

124-125 (Fi g. 14)

126-127 (Fig.15)

120

CH3

121

128-131 ( Fi g.17)

132 -139 (Fig.1S)

t -Bu

123

Ra

·H

H

t-Bu

0 Re 0,,- I .

5 1'0

0

CH 2

H

H t-Bu

140

yO t-Bu ·142

H CH2

CH2 H

145

147 (Fi g. 22)

H Ra t"'Bu CH2 0, /0.

5

H CH2 /\ o 0

H Ra

141

R t-Bu COR'

COR' R 143 144

H H

0 H I t-Bu

0--50

146