Studies in carbonium ion chemistry
128
A by
Transcript of 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
