‘5‘:

LIBRARY

Michigan State
University

 

This is to certify that the
thesis entitled
STUDIES TOWARD

THE TOTAL SYNTHESIS
OF SEYSCHELLENE

presented by

KENNETH BRUCE WHITE

has been accepted towards fulfillment
of the requirements for

Ph.D. degree in Organic Chemistry

 

 

 

Major professor

Date /0 /J:§’/jf/
/ 7

0-7 639

 

 

 

STUDIES TOWARD THE TOTAL SYNTHESIS

OF SEYSCHELLENE

BY

Kenneth Bruce White

A DISSERTATION

Submitted to
Michigan State University
in partial fulfillment of the requirements
for the degree of

DOCTOR OF PHILOSOPHY

Department of Chemistry

1977

ABSTRACT

STUDIES TOWARD THE TOTAL SYNTHESIS
OF SEYSCHELLENE

BY

Kenneth Bruce White

An approach to the synthesis of seyschellene 5%) via

bicyclol2.2.2]octanone intermediates has been investigated.

CH
'“3‘\\H

CH
1

N

The reactions of cross-conjugated dienolate anions
derived from substituted cyclohexenones with methyl acrylate
and vinyl ketones form bicyclo[2.2.ZJoctan-Z—ones by a
sequential Michael mechanism; however, the reaction of vinyl
ketones must be conducted under amine-free conditions.
Unexpectedly, the conjugate base from 2,3-dimethylcyclohexv
2-enone gives only a single Michael adduct £3) with methyl

vinyl ketone and if forced to react further undergoes an

 

o‘p.‘
gnu.

'9‘

Kenneth Bruce White

intramolecular aldol condensation to give dienone 3.

O

2

N

 

Keto-ester‘é’was transformed into vinyl ketonelé’in
four steps. The same route was applied to keto-ester’g'to
give hydroxy-ketonelz; The corresponding hydroxy acid of
’E’formed lactone’g, thus demonstrating that the C-5 carbo-

methoxy group is syn to the carbonyl at C-2 in’g.

CCD2CH3 0
J5- COZCHa
o

 

Kenneth Bruce White

Reaction of dienol silyl ether with various dieno-

,2;

philes afforded Dials-Alder adducts fig.

053}: z
/
OSi—E
9
N z = CHO $39
= COCH3 10b
N
= CN 10c

Aldehyde 10a was converted in two steps to vinyl
ketone 11. Vinyl ketone 11 could be a possible precursor
~ N

of seyschellene.

DEDICATION

This diaaentation is dedicated to my
patents, who have pnovided a continu-
ing bounce 06 Love, undenbtanding and
inspihaxion.

To my Aibtenb, who have been a bounce
06 joy and love.

ii

ACKNOWLEDGMENT S

The author is deeply grateful to Professor
William H. Reusch for his guidance, enthusiasm
and encouragement during the course of this work.

Appreciation is also extended to my col-
leagues for stimulating and informative discus-
sions and to my friends for their friendship,
humor, and unending concern for my wellbeing.

Special thanks are extended to Beth Decker
for her friendship and moral support.

The author acknowledges the financial sup-
port from the National Institutes of Health and
the Department of Chemistry at Michigan State
University.

 

iii

TABLE OF CONTENTS

Page
INTRODUCTION. 0 O I O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O C O O O O 1
“SULTS AND DISCUSSION. 0 O O O O O O O O O O O O O O O O O O O O O O O O O O O O O 9
EXPERIMENTAL. O O O .......... O O O O O O C ....... O O O O O O O O O O O O O 35
General-O... ......... OOOOCOOOOOOOOOOOOOO00...... 35
2'-Carbomethoxy-6-viny1-3,5,S-trimethylcyclo-
hex-2-en-l-one( )nooooooooooooooooooooooooo 36
S-Carbomethoxy-B,4-dimethylbicycloIZ.2.2]octan~
z-One (24) OOOOOOOOOOOOOOOOIOOOOOOO0.0.0.0.... 37

5-Carboxy-§74-dimethy1bicyclo[2.2.2Joctan-2—
01 (2g)...................................... 38
2-Hydroxy-3,4-dimethy1bicyclo[2.2.2]octan-5-
carboxylic acid G-Lactone ( 7)............... 39
5-Acetyl-4,7,7-trimethylbicyclo 2.2.2Joctan-2e

one ( )..................................... 39

3'-Oxo-6- utyl-Z,3-dimethylcyclohex-2-enone (33) 41
9,10-Dimethylbicyclo[4.4.0]deca-2,9-diene-3-
one (1)OOOOOOOOCOOOOOOIOOOOOOOOCOOOOCCOOOOOO 42

5-Carboxy-4,7,7-trimethylbicyclo[2.2.2]octan-
2-one( )OOOOOOOIOOOOOOOOOOOOOO0.0.0.00.0... 43
5-Chloroformyl-4,7,7-trimethylbicyclo[2.2.2]-

octan-Z-one (33)............................. 43
Preparation of Dione From Acid Chloride fig... 44
5-Carboxy-3,4-dimethy icyclol2.2.2]octan-2-

one (3g)..................................... 45

S-Chloroformyl-3,4-dimethylbicyclo[2.2.2]octan-

2-one ( 7)................................... 45
S-Acetyl-B, -dimethylbicyclo[2.2.2]octan-2-

one (3 )..................................... 46

Treatmen of Dione 8 with Base................. 47
Treatment of Dione 2’ with Base................. 47
3-Methylcyclohex-2-enone........................ 48
3-Ethoxy-2-methylcyclohex-2-enone............... 49
2-Methylcyclohex-2-enone........................ 50

iv

TABLE OF CONTENTS--continued Page

5-Carbomethoxy-4-methylbicyclo[2.2.2]octan—2-
one (9)0...000000000000.0 ..... 00.00.000.00. 50

S-Acetyl- -methylbicyclo[2.2.2]octan-2-one (49) 51
5-Carbomethoxy-3-methy1bicyclo[2.2.2]octan-2-
one (41)..... ......... ...................... 53
5-Acety123-methylbicyclo[2.2.2]octan-2-one (4 ) 54
5-Hydroxymethyl-4,7,7-trimethy1bicyclo[2.2.2 -
octan-Z-ol (4 )............................. 55

5-F0rmyl-4,7,7-trimethylbicyclo[2.2.2]octan-2-
one (47)0.0.0.00000000000000.000.000.0000... 56
S—(1'-Hydroxya11yl)-4,7,7-trimethy1bicyclo-

[2.2.2]octan-2-one ( 8)..................... 57
8-Acryloyl-4,7,7-trimet ylbicyclo[2.2.2]octan-

2-one (49).................................. 57
5-Hydroxymgthyl-3,4-dimethy1bicyclo[2.2.2]-

octan-Z-ol (50)............................. 58

5-Pormyl-3,4-difiéthylbicyclo[2.2.2]octan-2-
one (1)... ....... 0.0.0...0000000...00.....0 59
5-(l'-Hydroxyallyl)-3,4,4-dimethy1-2-vinyl-

bicyclo[2.2.2]octan-2-ol ( 3)............... 60
S-Acryloyl-3,4-dimethyl-2-viny bicyclo[2.2.2]-
octan-Z-ol ( 4)............................. 61
3-t-Butyldimethy silyloxy-l,2-dimethylcyclo-
hexa-l,3-diene (55)......................... 61
l,Z-Dimethyl-3-trim3thylsilyloxycyclohexa-
1,3-diene (56).............................. 62
5-Acetyl-2—t-bfityldimethylsilyloxy-3,4-
dimethylbicyclo[2.2.2]oct-2-ene ( 7)........ 63
2-t-Buty1dimethylsilyloxy-3,4-dimethy -5-
formylbicyclo[2.2.2]oct-2-ene (fig).......... 64
2-t-Butyldimethylsi1yloxy-5-cyano-3,4-dimethy1-
bicyclo[2.2.2]oct-2-ene (53)................ 65
2-t-Butyldimethylsi1yloxy-5-carbomethoxy-3,4-
dimethylbicyclol2.2.2]oct-2-ene (60)........ 65
5-Acetyl-3,4-dimethy1-2-trimethylsilyioxybi-
cyclo[2.2.2]oct-2-ene (61).................. 66
3,4-Dimethy1-5-formyl-2-trimethylsilyloxybi-
cyclo[2.2.2]oct-2-ene ( 2).................. 67
5-Cyano-3,4-dimethyl-2-trimethylsilyloxy-
bicyclo[2.2.2]oct-2-ene (63)................ 67
3,4-Dimethyl-S-(1'-hydroxyetޤl)bicyclo[2.2.2]-
octan-Z-ene ( 4)............................ 68
Oxidation of Alco ol ........................ 69
5-(3'-Hydroxy-3'-but- '-enyl)-3,4-dimethyl-
bicyclo[2.2.2]octan-2-one (63).............. 69

TABLE OF CONTENTS-~continued Page

5-(2'-Buta-l',3'-diene)-3,4-dimethy1bicyclo-

[2.2.2]0Ctan‘2-One (fi)ooooooooooooooooooooo 70
Preparation of Diene fig via Allyl Chloride §§.. 71
3,4-Dimethyl-5-(l'-hydroxyallyl)bicyclo[2.2.2]-

OCtan-z-One (6~9)0.000.00.0.0000...0000.00000 72
5-Acryloyl-3,4-dimethylbicyclo[2.2.2]octan-2-

one (45)0....0.000.0000.000.000.000000000000 73

~
REFERENCES..000 ......... 00.00.00.000000000000000.000 74
APPENDIX0000000.000.00.000000.000.000....00000.00000 76

vi

FIGURE

1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
13.
14.

15.
16.
17.
18.
19.
20.

Infrared
Infrared
Infrared
Infrared
Infrared
Infrared
Infrared
Infrared
Infrared
Infrared
Infrared
Infrared
Infrared

Infrared
hexenone.

Infrared
Infrared
Infrared
Infrared
Infrared

Infrared

LIST OF FIGURES

Page
spectrum of 23....... ........ ........ 76
speCtrum0f 24.00.00.000.00.000000000 77
N
spectrmn Of 260.00.000.00...00......0 78
N
spectrum of 27....................... 79
N
spectrum of 29....................... 80
N
spectrum of 30....................... 81
N
spectrum of 31....................... 82
~
SpectrumOf 340.00....00.00000...00.0 83
N
spectruH‘Of 35.0.0000.000......00OOO. 84
N
spectrum of 36....................... 85
~
spectrWOf 3700.......0....000..00.0 86
N
spectrum of 38....................... 87
N
spectrum of 3-methy1cyclohex-2-enone. 88
spectrum of 3-ethoxy-2-methy1cyclo-
.000.00.00.00.000.0..00.0.0000.00..0. 89
spectrum of 2-methylcyclohex-2-enone. 90
speCtrumOf 3900000000000.000.000.00. 91
N
spectrum of 40....................... 92
N
BPeCtrumOf 410.00....0...0..00...00. 93
IV
SPeCtr‘HnOf 420.0..0...00000.0000..0. 94
~
speCtrumOf 46000.00.00.....00000000. 95
N

LIST OF FIGURES--C0ntinued

FIGURE

21.
22.
23.
24.
25.
26.
27.
28.
29.
30.
31.
32.
33.
34.
35.
36.
37.
38.
39.
40.
41.
42.
43.

Infrared
Infrared
Infrared
Infrared
Infrared
Infrared
Infrared
Infrared
Infrared
Infrared
Infrared
Infrared
Infrared
Infrared
Infrared
Infrared
Infrared
Infrared
Infrared

Infrared

Pmr spectrum of

Pmr spectrum of 24.............
rv

spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum

spectrum

2

Pmr spectrum of 2

of

of
of

of

of
of

550.000.000000000000000.0

N
S 000.00.000.00000000000.
N
7

61.00000000000000000000.0

6200.0...00000000.00.000.

63.0.00....0000000.00..00

N
6 0.00.0.00.00.0..000.000
N
6

700.00.00.00000000.00.00

uh

80.000.00.00000.0000.00.
500000.000...0....0....0
22.....00000..0000.00.00.00...

viii

Page

96

97

98

99
100
101
102
103
104
105
106
107
108
109
110
111
112
113
114
115
116
116
117

LIST OF FIGURES--continued

FIGURE

44.
45.
46.
47.
48.
49.
50.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
61.
62.
63.
64.
65.
66.

Pmr

Pmr

Pmr

Pmr

Pmr

Pmr

Pmr

Pmr

§§§§§§§§§€§§§

spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum

spectrum

of
of
of
of
of
of
of
of
of
of
of
of
of
of
of
of
of
of
of
of
of
of
of

28 28 2:: 28 2: as as 28

3-methylcyclohex-2-enone......

3-ethoxy-2-methylcyclohexenone

2-methylcyclohex-2-enone......

23 22 33 2‘3 23 233 23 )3 23 2“ 2‘8 2%

ix

Page

117
118
118
119
119
120
120
121
121
122
122
123
123
124
124
125
125
126
128
127
127
128
128

LIST OF FIGURES--continued

FIGURE

67.
68.
69.
70.
71.
72.
73.
74.
75.
76.
77.
78.
79.
80.
81.
82.
83.
84.
85.
86.
87.
88.
89.

Pmr
Pmr
Pmr

Pmr

Pmr
Pmr
Pmr
Pmr

Pmr

Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass

Mass

spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
spectrum

spectrum

spectrum
spectrum
spectrum
spectrum
spectrum
Spectrum
spectrum
spectrum
spectrum

spectrum

of
of
of
of
of
of
of
of
of
of
of
of
of

of
of
of
of
of
of
of
of
of

Page

56000000000000000000000.000000 129

N
5000000000 ..... 00000000000000 129
N
58 ....... 0000 ........ 000000000 130
N
50000000000000000000.00000000 130
N
60000000000000000000.000000000 131
N
61000000000000.000000000000000 131
N
62000000000000.000000000000000 132
N

630000 ..... 00000000000000.0000 132

N
64.000.000.000.0.0000000000000 133
N
67000000000000.0000.0.0000000. 133
N
68000000000000.000.000.000.000 134
N
6 .0000000000000000000.0000... 134
N
45.000.000.000000.000.0000.... 135
N

22000000000000000000000000000 135

400000000000000000000000000. 136

0.0000000000000000.00000... 136

270 00 000 000 00. 0.00 0. 000. 0000 0 137
2900. 000 0 0 000 0 0.. 000000000 00 0 137
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 138

31.00000000000000000000000000 138

400000.0000000000000000.0000 139

000000000000...000000.00... 140

3
N
35.-co...oooooooooooooooooooo 139
IV
3
N

LIST OF FIGURES--continued

FIGURE

90.
91.
92.
93.

94.
95.
96.
97.
98.
99.
100.
101.
102.
103.
104.
105.
106.
107.
108.
109.
110.
111.
112.

Mass spectrmn Of £00....OOOOOOOO

Mass spectrum of 38...........................
N

Mass spectrum of 3-methy1cyclohex-2-enone.....

Mass spectrum of 3-ethoxy-2-methylcyclo-
hexenone..................... ..... ............

Mass spectrum of 2-methy1cyclohex-2-enone.....

Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass
Mass

Mass

spectrum of
spectrum of
spectrum of
spectrum of
spectrum of
spectrum of
spectrum of
spectrum of
spectrum of
spectrum of~
spectrum of
spectrum of
spectrum of
spectrum of
spectrum of
spectrum of
spectrum of

spectrum of

39....

23 23 23 2

A
0‘

{S 2% IS 23 2“ 2“ )2 )3 PE 13 )3 23 k: 2

xi

Page

140
141

141

142
142
143
143
144
144
145
145
146
146
147
147
148
148
149
149
150
150
151
151

.ohn A“

...‘.L U!

lel !
L14. 1
:15. I

117.

1.

.1.

11
.3 o

LIST OF FIGURES--continued

FIGURE

113.
114.
115.
116.
117.
118.
119.
120.
121.

Mass

Mass

M388

Mass

Mass

Mass

Mass

Mass

Mass

spectrum
spectrum
spectrum
spectrum
spectrum
spectrum
Spectrum
spectrum

spectrum

of
of
of
of
of
of
of
of

of

ox
O

23 2% )3 23 21‘ 233 2‘“ 23?

xii

Page

152
152
153
153
154
154
155
155
156

 

 

.
"A:
coy}

a.
In.

*I
0.36

3.:
‘4'.“

P
‘V'A
5.“

INTRODUCTION

Since the dawn of man, fragrant substances extracted
from plants have played an important role in everyday life.
One of the better known Eastern perfumes is Patchouli.
According to Genders,l "Its odour is the most powerful of
all scents derived from the botanical kingdom, and in its
unadulterated form smells extremely unpleasantly of goats."
The oil of Patchouli has an odor that is "sweet, powerful

2 One sesquiterpene isolated

and persistent of old wood."
from Patchouli oil obtained from the Seyschelles Islands is
Seyschellene Sl).3 Another sesquiterpene isolated from

Patchouli oil is Patchouli alcohol 9;).4

'\“\H ['5
\\\\\ H
H
C82
.13 3..
Seyschellene Patchouli Alcohol

'.'§|l
:vo ‘\

.45.

9.11,
in“

‘

I o
7““!
O4.“

RD":
'5 V.

)1

Three different pathways have been employed in the con-
struction of the tricyclic carbon skeleton of seyschellene
8;). In the approach devised by Piers,5 Wieland-Miescher
ketone £2) was transformed into the tosylate‘g’in sixteen
steps (eq. 1). Treatment of the tosylate g'with sodium
hydride afforded norseyschellanone’g, this being the key
step in the formation of the tricyclic skeleton of seyschel-
lene. Norseyschellanone 92) was treated first with methyl-
lithium and next with a solution of pyridine and thionyl
chloride to yield seyschellene’l. It is important to note

that as a result of Pier's synthesis, a synthesis of nor-

 

seyschellanone constitutes a synthesis of seyschellene.

O

16 STEPS ' NaI-I
->

 

(l)

 

 

 

 

 

 

C82
1 Seyschellene
av

(100% from’a

2’ Norseyschellanone

 

Another synthesis of seyschellene, devised by Prater,6
employs the Diels-Alder reaction (eq. 2). Alkylation of the
phenolate l'with cis and trans-S-bromo-B—methyl-l,3—penta-
diene yielded ketone‘g. This mixture of ketones was heated
in benzene to form the tricyclic ketoneslg and £3. Hydro-
genation of‘g’and 10 afforded ketones 11 and 12. Ketone 11

N IV IV ~
was then treated with methyllithium to afford the alcohol
13. It should be noted that the tricyclic compounds 10, 11
N N N
and 13 do not have the carbon skeleton of seyschellene.

In a very interesting rearrangement reaction, the alcohol
13,was heated with sodium acetate in acetic acid to yield
seyschellene (’1').

Prater suggests that this reaction proceeds via a

wagner Meerwein rearrangement.

 

(2)

 

 

 

 

 

 

 

 

 

0 V o W
H /Pd0
0 +
/
9 10 ll 12
N ~ N N
MeLi ,Et20
V
V
HOAc
NaOAc
l3

 

A second total synthesis of seyschellene, using the
Dials-Alder reaction to generate the tricyclic skeleton was
reported by Yoskikose7 (eq. 3). In six steps, 2,3-dimethy1-2-
cyclohexenone was converted into the N-oxide 13; Pyrolysis
of the N-oxide 13 afforded a number (unreported) of products,
one of which was the ketone lg. The yield of l§ was not
reported; thus, it is unknown whether or not this was the

major product. Hydrogenation of the ketone 13 gave norsey-

schellanone (5).

O
6 STEPS
(3) —* -> —>

 

 

 

 

CH

 

 

'0'.

.
...I'
.-

-V'Oll
‘

79"!

v.'-

a.
x .1

The seyschellene synthesis effected by Mirrington8
(eq. 4), is based on the following strategy. First, a suit-
ably functionalized bicyclo[2.2.2]octane was synthesized.
Next, the six membered ring in the tricyclic carbon skeleton
of seyschellene was annealed to form norseyschellone. The
Diels-Alder reaction of 1,3—dimethyl—1,3—cyclohexadiene with
methyl vinyl ketone affords the ketone 19,9 which was con-
verted into the tosylate 11 in seven steps. Cyclization of
the tosylate 23 was accomplished by treatment with trityl
potassium to yield norseyschellanone £2). One major dis-
advantage of Mirrington's synthesis is the difficulty
associated with the stereoselective construction of the non-
rigid 4-carbon side chain in 13. Because of this difficulty,
it was necessary at one stage in the synthetic sequence to

separate a pair of epimeric compounds.5

(4)

 

 

 

 

17 (ZaTaO or Br)

CH 16 ~ 0

3 CH
V ' 3 '

w” “.3

¢3CK
4",' 4-——- .._J
Z
0 i— 6 J
5 09K

 

Every successful synthetic strategy has as its founda-
tion at least one specific transformation of a versatile
intermediate. In this study, the availability of the cross»
conjugated enolate anion 1§,and its reactions prompted con-
sideration of the total synthesis of seyschellene (eq. 5).
Treatment of a cyclic a,8 unsaturated ketone (13) with a
lithium amide yields the cross conjugated enolate anion lg
(to be discussed later). This enolate can be alkylated to
give a' aklyl a,B unsaturated ketones 1&3)'10 A most unusual
reaction is observed when a cross conjugated enolate anion
is treated with methyl acrylate. A bicyclo[2.2.2]octanone
£;}) is formed in very high yield.11

The formation of a suitable bicyclo[2.2.2]octanone would
be a very useful intermediate in a synthetic pathway which
follows a strategy similar to the approach used by Mirrington.
This dissertation describes experiments which explore this
type of synthetic pathway to the total synthesis of seyschel-

lene.

 

 

 

 

 

 

 

 

 

 

o P 0 Li '7
LDA
(S) THF 0°
R R ' R B
R 19 LR “J
N 18
N
a) R = H
b) R = CH3
0
R2
18 “2" a
‘ R
R R
20
~
ozcn3
R R
1) We CH3R
2) 32°
0

 

 

 

 

o
LDA
(5) R THF, 0°
R
19
N
a) R = H
b) R = CH
2
R x
18 ,
I
R
L11 W0 CH3R
2) H2

 

 

R R B
b J
18
N
0

R2
R
R R
20
~
ozca3
R
o

1
l- 3.!
.0...\

(I.
l "
I

RESULTS AND DISCUSSION

The addition of methyl acrylate to the cross conjugated
dienolate anion derived from iSOphorone gave keto ester 21
(eq. 5). There are two probable mechanisms by which this 1;
reaction might proceed. One consists of a sequence of two
Michael reactions (eq. 6) and the other involves a Diels- ~a
Alder cycloaddition (eq. 7) in which the dienolate anion
serves as the diene reactant. In view of the very high
yields observed under exceptionally mild conditions with
substrates of varying steric hindrance (to be discussed
later), the sequential Michael mechanism was favored by
Ross Lee in his initial investigation of this reaction.11
In a study of the Michael reaction conducted by House
et al.,12 the reaction of an enolate anion with B-chloro-
methyl acrylate (eq. 8) gave unsaturated adduct via an
addition-elimination mechanism. The same strategy was used
here to study the mechanism of reaction eq. 5. Thus, addi-
tion of cis-B—chloro-methyl acrylate at -23° to the cross-
conjugated dienolate anion derived from isophorone afforded
the keto-ester 33 and starting material (eq. 9). A similar

13

result was noted by Boeckman (eq. 10). These results

clearly point to a double Michael reaction sequence, since

 

10

the bicyclo[2.2.2]octanone product (g3) expected from the
Dials-Alder pathway should have been sufficiently stable to

be isolated or otherwise observed.

 

OLi o
LDA COZCHB Li
(—’.--- ¢-.....' — ocn3
(6) O CH :
2 3 I
H 0 02¢ I
"——z—' - --J
OLi
21
N
Li
/\ l fcozcn3
(7)
(:02 CH3

OLi

 

 

 

11

(k) e K9
CHI Cl H
3 / H
(8) + ‘\C=C +0K 3
H/ IIOZCH3 —__.§

+03
c1 H
§C=
H cozca3

3
co CH _

C=C 2 3 <‘—_.[::f:7fi_::o C\\ Cg/OCH3

H H

(9)
1) LDA,-23° ’ CH=CHco2 CH3
2) (c1 + s. 2M.

c

 

 

0 CH 5 M
2 3 22

N

CO2 CH3
2)
Not observed
OZCH3
N

 

(10) . 1) LDA,-28°
/ 2)

CO CH

 

 

 

 

 

 

12

In order to use the sequential Michael synthesis to
form the tricyclic carbon skeleton of seyschellene, it is
necessary to begin with 2,3-dimethylcyclohexenone. This
enone was prepared in two steps from cyclohexane—l,3-dione

as shown in eq. 11.

 

 

(ll) 0 o o
NaOH(aQ) > 1)‘ NaH,Et30 ’
MeI,A 2) MeLi
3) H306

Reaction of methyl acrylate with the cross-conjugated
dienolate anion derived from 2,3-dimethylcyclohexenone

afforded the keto-ester‘gé,in high yield (eq. 21).

(12)
0 CH

1) LDA,-78°
2) /\c02cn3

3) H20

“i’

 

 

13

The configuration of the carbomethoxyfunction at C-5
in 4 was demonstrated by the following chemical approach.
Keto-ester 23 was saponified to keto-carboxylate 2; (eq. 13)
which was then reduced by catalytic hydrogenation to give
hydroxy-acid 33, Lactonization of hydroxy acid £9 was

accomplished in refluxing toluene containing para-toluene-

sulfonic acid (eq. 14).

 

 

 

co CH 0 Na 02H
2 3 2
(13) NaOH H PtO ‘—’
‘5 2' 2
820
on
o o H
24 25 26
~ ~ N
O2H TSOH,¢CH3
(14) ..
on
H
26
(v

 

It should be noted, however, that, because of its easy
accessibility, isophorone was used many times throughout
this research project as a model compound for reactions to

be applied to 2,3-dimethylcyclohexenone.

 

 

14

The success of double Michael reactions involving methyl
acrylate suggested that a reaction between the cross-
conjugated dienolate anion of 2,3-dimethylcyclohexenone and

divinyl ketone might lead directly to a bis—nor-seyschellene

derivative (33) as shown in eq. 15.

Li H08 0-
l I
7.7:! /

   

The synthesis of pure divinyl ketone turned out to be
a difficult task. Oxidation of divinyl carbinol with

manganese dioxide afforded divinyl ketone ("'508) and start-

ing material (eq. 16). Attempts to purify divinyl ketone

by spinning band column distillation failed to completely

remove divinyl carbinol and a similar result was noted by

Reed.14 It was, of course, unacceptable to use contaminated

diVinyl ketone as a Michael acceptor, since the alcholic
imPurity would serve as a proton source which would destroy

or isomerize the cross-conjugated dienolate anion.

15

Another approach to prepare divinyl ketone is the
aluminum chloride catalyzed reaction of ethylene with
B-chloro-acetyl chloride to yield 1,5-dichloro-3-pentanone
(eq. 17), followed by bis-dehydrochlorination. Attempts to
dehydrochlorinate 1,5-dichloro-3-pentanone using sodium
carbonate by the procedure of Jones and Taylor failed.15
However, formation of divinyl ketone from 1,5-dichloro-3-
pentanone was accomplished by using the method of dehydro-
chlorination developed by DeJongh and Wynberg.16 Thus,
reaction of 1,5-dichloro-3-pentanone with ethyl dicyclo-

hexyl amine at 100°C under vacuum yielded divinyl ketone

which could be further purified by vacuum distillation

 

 

 

(eq. 17).
(16) O
HO ii
MnO
2
| I v | I
(17 =
) o HZC CH2 ‘) 0
c1 A1C13,CH2C12 Na,co1
C ' A' ’Polymer
1
1

(®)2NEtfi I |
100°

 

 

 

 

16

Reaction of divinyl ketone with the cross-conjugated
dienolate anion derived from isophorone led only to starting
material and polymer (eq. 18). This disappointing result
was matched by the reaction of methyl vinyl ketone with
the same dienolate anion, which yielded mostly starting
material and ~10% of the corresponding double Michael
adduct (33, eq. 18). Thus, under reaction conditions that
gave a successful double Michael reaction with methyl

acrylate, methyl vinyl ketone was surprisingly unreactive.

 

(18) 0 F on " o
LDA
THF -786 LL'D¥K*' + Polymer
’ 2) H o
2
L.

 

.J
o o
1, 6*
+ 5.11.
2) H20
29
N

The question that now had to be answered was: What
factors are responsible for this difference in behavior
between vinyl ketones and vinyl esters? Since the conjugated
double bond of a vinyl ketone is more polar than the corre-

17

sponding bond of a vinyl ester, vinyl ketones should in

fact be more reactive in Michael reactions. In order to

 

 

17

reconcile these facts, it must be recognized that two nucleo-
philes are present in the reaction mixture: the dienolate
anion and a 2° amine (eq. 19). If the amine reacts with

the vinyl ketone by a 1,4 addition (eq. 20), the resulting
adduct might initiate vinyl ketone polymerization, and in

any event would hinder the desired reaction.

0 P OLi W

 

THF, -78° , + (>_)2NH
(19) (>- ) 2NLi

 

 

 

R NH O a
W
(20) _....
b

 

 

This argument suggests that removal of the amine after
formation of the dienolate anion would facilitate subsequent
double Michael reaction using vinyl ketones as Michael
acceptors.

To test this premise, isophorone was treated with
lithium diisopropyl amide (LDA). The resulting amine and
solvent were removed by vacuum distillation from the reac-

tion vessel. The remaining crystalline dienolate anion was

18

redissolved in THF under an argon atmosphere and then
cooled to -78°. Addition of methyl vinyl ketone to this
amine-free dienolate anion solution led to the desired
bicyclo[2.2.2]octanedione 23 (eq. 21) in 75% yield.
Surprisingly, reaction of the amine-free conjugate
base derived from 2,3-dimethyl-cyclohexenone with methyl
vinyl ketone or ethyl vinyl ketone did not proceed to a
bicyclo[2.2.2]octane product. Only the mono Michael
product 39 was obtained under mild conditions, and more
vigorous treatment (longer reaction time at a higher
temperature)gave the decalone 21 (eq. 22). This same
decalone was also obtained by stirring dione 29 in a THF

solution of‘FOK for 2 days at room temperature (eq. 22).

 

 

 

 

 

O F OLi '-
l) LDA
(21) b
2) Remove
Amine "1
O
1) |
‘:~
121 2) H20
0 29

 

 

 

19

 

 

(22) o " OLi 1 o I. 7
/
‘ 1) LDA I O i)____,’: O
2) Remove 2) 320
Amine
1.. d 30 +OK,+OH

’V ’ 48 hrs

0
L)”: a
2) A, 4 weeks
3)HO 0
2.1,

 

2

The formation of dienone 21 is not difficult to
rationalize. Formation of the dione intermediate undoubtedly
proceeds by an initial Michael reaction (eq. 23). Under more
drastic reaction conditions interconversion of the enolate
anions 23 and 33 (eq. 23) occurs and, the latter then suf-

fers an adol condensation to form decalone 2; by a

Robinson annelation.

20

 

 

 

 

 

 

 

 

 

 

 

OLi 6) O
/ L -"1
(23) e— ------
OLi
h- d
32
r- T — N —
_ ‘—
.§ -9
.n—l)
O 71/ / __J,
OLi
L OH 4 L. —
33
N
L- 31
n.
O

In the course of studying these reactions, it was
necessary to prepare authentic samples of the diones gg,and
23,by an alternative route. To this end, saponification
of keto-ester 21 afforded keto acid ;3 in 80% yield (eq. 24).
Treatment of 33 with a methylene chloride solution of
thionyl chloride and lithium chloride afforded keto-acid
Chloride g; in 89% yield (eq. 24). Finally, reaction of 1;
with dimethyl lithium cuprate gave dioneizg in 85% yield
(eq. 24).18 Dione 38 was synthesized in the same way,
Starting with keto-ester‘35 (eq. 25). As expected, the
sPGCtral properties (IR, NMR, MS) of dione 23,0btained by
the double Michael reaction (eq. 21) and the aforementioned

rOUte were identical.

 

 

 

21

 

 

 

 

 

 

co CH co H cool
2 3 2 soc1
(24) 9
l) NaOH(aq) LiCl,CH Cl
0 2 2
2) H30
0 34 35 O
as, "’ ~ .
(CH3)2CuL1
Et20,-78°
‘»
o
29
N'
co CH 0 H
(25) 2 31)NaOH(ag) . 2
2)330°
soc1iLic1
H CHZC 2
o
24 . 33 °
"’ coc1
(CH3) CuLi ._
Et20,-78°
H H
38 ‘3 37 o
N

22

In an important experiment.;g, on treatment with
potassium t-butoxide at 25° for 2 days, was completely con-
verted to the Robinson annelation product 3; (eq. 26).
Similar treatment of 23 gave only slight epimerization to
the exo isomer, over 90% of the diketone being recovered

unchanged (eq. 27).

 

 

0
+rOK/+OH A
(25) THF, 48 h .
3
38 0 A]}
«\u 0
O
H
(27)
J'OKIFOH , + S.M.
THF, 48 h
0 0

29
N

The effect of methyl groups on the course of the
Sequential Michael reactions of cyclohexenone dienolate
anions with methyl vinyl ketone is indeed striking. It is
also puzzling that this effect does not appear when the
Michael acceptor is methyl acrylate. In order to explore
this feature more fully a series of comparative cyclizations
were conducted in which methyl groups were positioned at

different sites on the cyclohexenone ring. For this purpose,

23

3-methylcyclohexenone was prepared in two steps from cyclo-
hexan-l,3-dione (eq. 28) and 2-methy1cyclohexenone was
obtained in three steps from the same starting material

(eq. 28).19

 

 

 

o OEt O
(28)
TSOH,¢H i
EtOH,A . 2) H300 ’
0 o
o
c1131 0 O
N
aZH'HZOJ . 3501mm! 1) LAH
. E-tOH,A 2) H305

OEt

Reaction of the cross—conjugated dienolate anion derived
from 3-methy1cyclohexenone with methyl acrylate gave the
keto-ester 33,(eq. 29). Likewise reaction of the cross-

Conjugated dienolate anion from 2-methylcyclohexenone with

methyl acrylate afforded the epimeric keto—esters 41'(eq. 30).

The reaction of the amine-free cross-conjugated dienolate
anions of these methylcyclohexenones with methyl vinyl
ketone also afforded the expected bicyclo[2.2.2]octane

diOnes (eq. 29 and 30). Thus, the reaction of the conjugate

24

base derived from 2,3-dimethylcyclohexenone with methyl
vinyl ketone is unique in not yielding the expected

bicyclo[2.2.2]octane dione (eq. 22).

O

(29) 1) LDAL-Z 3° ’ CC’2CH3
2) CO2CH3
3

 

 

 

9
14’ o
1) LDA,-23° ’
2) Remove Amine
3) MVK
4o 0
N

 

(30) cozca3
1) LDA.-g;° ’
2) cozcn3
H
41 o
N
1) LDA,-23° a
2) Remove Amine
3) va H
42 o
N

 

 

25

The variability of the enolate reactions described
above can be rationalized in terms of steric and electronic

factors influencing the second Michael addition (eq. 31).

 

 

(31)

 

O

44
N

 

Since ester enolate bases are less stable and more
reactive than ketone enolate anions (esters are over 10,000
times weaker as Bronsted acids than are ketoneszo), there
is a thermodynamic driving force favoring cyclization
(ga,+ 5g) of the intermediate formed from acrylate ester
addition (z = OCH3 in equation 31). Vinyl ketone reactions,
on the other hand, proceed through a series of ketone enolate
anions among which this driving force is missing. In the
absence of strong steric hindrance, the cyclization should
Still be favored because of the increase in bond energy
‘that normally accompanys the conversion of w-bonds to
(Fibonds, Indeed, this is observed for all cases in which at
least one of the R substituents (R:L or R2) is a hydrogen

atom. However, when both R1 and R2 are methyl, non-bonded

repulsions destabilize the bicyclic product (33) relative

tC> the monocyclic precursor and the latter ($3) predominates.

‘4

26

As a consequence of the model experiments with vinyl
ketones, the triple Michael reaction approach to seyschellene
was abandoned. Nevertheless, approaches involving sequential
Michael reactions still looked promising. This new strategy
would require synthesis of the vinyl ketone 35 from the

keto-ester 23, followed by intramolecular cyclization (eq.

32).
O O
CO CH
(32) 2 3
—§-'—v —+
J H
O o O
24 45 28
(V N N

The easily accessible keto-ester 2;,was used as a model
compound for the proposed reactions of 23. To this end,
reduction of El with lithium aluminum hydride afforded the
diol 39 (eq. 33). This diol (25,) was oxidized to keto-
aldehyde 2; with pyridinium chlorochromate (eq. 33), and
treatment of 3.7, with vinyl magnesium bromide afforded keto-
alcohol 33. As expected, attack of the Grignard reagent
(Macurred only at the less hindered carbonyl function of the

alxiehyde. Oxidation of fig with manganese dioxide afforded

the vinyl ketone 23.

 

27

 

cozcn3 CHZOH H0
LAI-I I [o] ’

(33) 21 o 47 o
N

46 OH
MgBr
' (M)
4.52.]—
l. E
49 ° 48 c)
N N

With the promising results of model compound in hand,

 

 

this synthesis was applied to keto-ester 23; Reduction of
£5 with lithium aluminum hydride afforded the expected diol
(23) in high yield (eq. 34) and oxidation with pyridinium
chlorochromate gave the desired keto-aldehyde‘zl (rq. 34).
Unfortunately treatment Of.;$ with excess vinyl magnesium
bromide proceeded with double addition, resulting in diol
23, rather than keto-alcohol ’53 (eq. 35) . The structure of
£23 was based on mass spectral evidence. Attempts to obtain
hydroxy ketone ’53 using other reaction conditions (lower
(Hancentration of the Grignard reagent and lower temperature)
also failed. Oxidation of $53 with maganese dioxide afforded
Vinyl ketone (5:; (eq. 35) . Thus it appears that the gem-

dimethyl group in the model keto-aldehyde 4“; blocked attack

 

 

28

of the Grignard reagent at the ketone. In keto-aldehyde
31, the gem-dimethyl group is no longer present and the

Grignard reagent attacks both carbonyl functions with very

little chemioselectivity.22

(34) 0020113 ___'H\ECHZOH:1 5:15:10
~
CH/\Mglsr (XS)
(35) 4g
11
51
v"’ 0

4”\\'MgBr

(XS)

  

 

 

 

  

 

At this point, it appeared doubtful whether any pathway
tKD seyschellene could be achieved using Michael reactions
<Jf conjugated dienolate anions. Consequently, a new approach

Was devised. Earlier considerations of a Dials-Alder

'0'

'-

D¢

29

umchanism for the cross-conjugated dienolate anions sug-
gested the possibility of using a Diels-Alder reaction to
construct the bicyclic carbon skeleton of seyschellene.

In order to use the Diels—Alder reaction in this way,
it was necessary to begin with a cross-conjugated dienol
ether derived from 2,3-dimethylcyclohexenone. This diene
was readily prepared by silylation of the corresponding
dienolate anion.23 Thus, treatment of the cross-conjugated
dienolate anion derived from 2,3-dimethylcyclohexenone with
a THF:HMPA solution of t-butyl dimethyl silyl chlorosilane
afforded t-butyl dimethyl dienol ether 23 (eq. 36). An
equivalent reaction of the same dienolate anion with tri-
methyl chlorosilane afforded trimethyl silyloxy diene ether
,5‘5’ (eq. 36). Diels-Alder cycloaddition of ’53 with methyl
Vinyl ketone afforded the ketone 21 in 94% yield (eq. 37).
Other dienophiles also reacted with this siloxy diene
(eq. 37) to give corresponding Dials-Alder adducts.

.As expected, trimethyl silyl dienol ether 23 also re-
aCted with dienophiles to give Diels-Alder adducts (eq. 38).
While this work was in progress, Rubottom and Krueger
reported similar results for the Dials-Alder reactions be-
tWeen silyl dienol ethers derived from cyclohexenones with
mfileic anhydride or dimethyl acetylene-dicarboxylate

(eq. 39).24

30

0 OLi 0 Si +

 

 

 

 

LDA +SiCl
1_}
1, O
55
N

 

 

 

 

OSiE
)5... , a
H
081+ ’53
i/Z Z
1 I 1,
(37) ‘ ¢Me, reflux
OSi+
z = c0033 3],
= C30 58
N
= CN 59
N
=- COZCH3 '63
051?:
"/2 Z
(38’ a m '
e, reflux
/
0812
Z = COCH3 61
IV
= CHO 62
"3’
= CH 6
OSiEE IN!

 

(39) am A O —) fl’ 0
' 25510

P‘

31

One question that had to be answered was: What is the
configuration of the Diels-Alder adducts? Since there are
four possible isomers, it is imperative to know which isomer
(if any) was favored in the Diels-Alder reaction. To this
end, treatment of aldehyde 6; with excess methyl lithium
afforded keto-alcohol 63'(eq. 40) and oxidation of £3,with
pyridinium chlorochromate gave dione 3g, The spectral
properties of dione gg obtained in this fashion were identi-
cal to the spectral pr0perties of dione 3g prepared by an
alternate route (eq. 25). Thus, the Diels-Alder adducts
appear to obey Alder's endo rule, and they have the con-

figuration required for use in a seyschellene synthesis.

cao
( MeLifxs) ’
40)
J
051;;
C
[0]
‘———J.
H
38 0

N

 

62

N

 

32

With the stereochemistry of the Diels—Alder adducts
known, approaches involving the Diels-Alder adducts looked
promising. One strategy would require synthesis of allyl
chloride 65 from ketone 21, followed by intramolecular
cyclization (eq. 41). To this end, treatment of ketone 63
with excess vinyllithium afforded allyl alcohol’gl (eq. 42).
Treatment 0f,22 with thionyl chloride using the method of

Morrow et 21.,25 gave the allyl chloride 6; (eq. 43). In an

 

attempt to isolate 65 by preparative glpc, 65 underwent

dehydrochlorination to form diene fig; Thus, treatment of
crude allyl chloride §§,with sodium hydride gave the diene
Jig and not the expected ketone‘gg (eq. 44). Diene §§,was
cflotained by an alternate route. Treatment of allyl alcohol
fizz,with page toluenesulfonic acid in refluxing toluene gave
SE; (eq. 45). Since the stereochemistry of the double bond
Of 93 was not determined, the possibility that the major
isomer obtained was the ; isomer existed. This might explain

the failure of 65 to cyclize.

000113

(41) \\
-+1—»«—¢ -———’
A C1
0 0 I

05152

61 65 66
IV! r»! /\I

33

 

 

OH
H
coca3 3
/\Li
, .
(XS)
(42) H
61 051 57 °
N IV
HO
CH3
SOC12,PX '
' C
(43) 00 I 1
H
I
65 O
67 O nu
~
NaH 1,
ll
(44) 65 —"""""
N
NaH

 

 

 

O
T OH
(45 “§""—"
)
¢Me,A
H
O

 

34

Another strategy which utilized a Dials-Alder adduct
involved synthesis of dione :43 (eq. 46 and eq. 32) from
aldehyde ’63. Thus, treatment of aldehyde ’63 with excess
vinyllithium afforded allyl alcohol 69/ (eq. 47). Oxidation
of 63 with manganese dioxide afforded vinyl ketone :13 (eq.
47).

The synthesis of vinyl ketone if; accomplishes the
primary goal of this dissertation since this compound is a

possible precursor of norseyschellanone (’5‘) .

94$

 

OSi: —
N N
0
HWM’D l \
(x8)
0

OSi: -— N

 

EXPERIMENTAL
General

Infrared spectra (ir) were recorded on a Perkin-Elmer
237B grating spectrophotometer. Proton magnetic resonance
spectra (pmr) were taken in deuterochloroform or CCl4 solu-
tions with a Varian T-60 spectrometer and are calibrated in
parts per million (6) downfield from tetramethylsilane as
an internal standard. Ultraviolet spectra (UV) were re-
corded on a Unicam SP-800 spectrophotometer. Mass spectra
(ms) were obtained with a Hitachi RMU 6 mass spectrometer.

Melting points were taken on either the Hoover-Thomas
apparatus (capillary tubes) or on a hot-stage microscope
and are uncorrected.

Gas—liquid phase chromatographic analyses (glpc) were
conducted with either a Varian 1200 flame ionization gas
chromatograph or an Aerograph A-9OP3 thermal conductivity
instrument.

Micro-analyses were performed by Spang Microanalytical

Labs, Ann Arbor, Michigan.

35

even
uvw
. b

'-
:O A

‘34-'04

lI Q
t.“
5..”

3531'
.1.
:45

'I'EI

36

2'-Carbomethoxy-6-viny1-3,5L§7trimethyl-
cyclohex-Z-en-l-one (22)

To a stirred solution of .340 mL (2.4 mmoles) of diiso-
prOpyl amine (DIA) in 80 mL of THF at -23° under an argon
atmosphere was added 1.0 mL (2.2 mmoles) of 2.2 M n-butyl-
lithium in hexane. After 20 min, a solution of .300 mL
(2.0 mmoles) of isophorone in 5 m1 of THF was then added
drapwise to this mixture over a ten minute period. The reac-
tion mixture was stirred for 1 hr, following which a solution
of .264 g (2.2 mmoles) of cis-B-chloromethyl acrylate in 5
mL of THF was added dropwise over a five minute period.

The reaction mixture was stirred for 2 hr at -23°. After
warming to 25°, water and ether were added and the aqueous
phase was extracted with ether. The combined ether extracts
were washed three times with a 1M HCl solution, once each
with water and a saturated sodium sulfate solution and
finally dried over M9804. Removal of solvent gave .404 g
(910) of a reddish oil. Analysis by glpc showed a mixture

of isophorone and keto-ester‘23,(ratio 1:1). An analytical

sample of’23,obtained by preparative glpc the following

properties: Uv (95% EtOH) 242 nm (e . 13,400); ir (00013)
1725 cm‘z, 1670 cm'l; pmr (00013) 6 6.3-6.1 (vinyl,3H), 3.6
(8:3H), 2.4-1.2 (m,6H), 1.05 (s,3H), 0.95 (s,3H); mass spec-

trum (70 eV) m/e (rel intensity) 222(3)P, 190(27), 175(100).

 

37

Anal. Calcd. for C13H1803: C, 70.24; H, 8.16.

Found: C, 70.33; H, 8.25.

S-Carbomethoxyf3,4-dimethy1bicyclo-
12.2.2Toctan-2-one (2E)

 

To a stirred solution of 2.2 mmoles of lithium diiso-
propyl amide (LDA) in 80 mL of THF prepared in the usual
manner, at -78° under an argon atmosphere was added a solu-
tion of .248 g (2.0 mmoles) of 2,3-dimethylcyclohexenone in
5 mL of THF over a 5 min period. The reaction mixture was
stirred for 1 hr, following which a solution of .200 mL
(2.2 mmoles) of methyl acrylate in 5 mL of THF was added
dropwise over a 5 min period. The reaction mixture was
stirred, first for 2 hr at -78° and then for 12 hr at 25°.
Water and ether were added to the reaction mixture and the
aqueous phase was extracted with ether. The combined ether
extracts were washed three times with a 1 M_HC1 solution,
once each with water and a saturated sodium sulfate solution
and finally dried over M9504. Removal of solvent gave .390
g (910) of keto-ester 4 as a pale yellow oil, which was
homogeneous by glpc (4% QF-l, 120°). An analytical sample
obtained by preparative glpc (4% QF-l, 190°) exhibited the

1 l

fOllowing properties: ir (c014) 1730 cm- , 1190 cm" , 1160

-1
cm 3 pmr (CC14) 6 3.6 (3.38), 2.9-1.3 (m,9H), 1.1 (3,3H)
0'9 (d,3H); mass spectrum (70 eV) m/e (rel intensity)

210(5)p, 124(100).

 

 

 

 

38

Anal. Calcd. for C12H1803: C, 68.55; H, 8.63.

Found: C, 68.68; H, 8.66.

5-Carboxy-3,4-dimethylbicyclo-
[2.272joctan-2-ol (26)

The keto-ester‘gg (.784 g, 4 mmoles) was added to a
solution of 10% aqueous sodium hydroxide and stirred at rm
temp for 5 hr (until homogeneous). Platinum oxide (170 mg)
was then added and the solution was hydrogenated at 25° and
atmospheric pressure for 2 days with theoretical uptake of
hydrogen. After filtering off the catalyst through a celite
mat, the solution was acidified with 6 M hydrochloric acid
and extracted with ether. The combined ether extracts were
washed once each with water and a saturated sodium sulfate
solution and finally dried over M9504. Removal of solvent
gave .740 g (92%) of hydroxy acid‘gg,and starting material
(8:2) as a white solid, mp 103-104°. An analytical sample

obtained by preparative glpc (4% QF-l, 190°) exhibited the

1 1

following properties: ir (CDC13) 3500 cm- , 3250-3000 cm- ,
1720 an“; pmr (c0013) 0 8.2 (63,23) 2.9-1.5 canon) 1,2...9
(m.6H); mass spectrum (70 eV) m/e (rel intensity) 198(2)P,

196(11)impurity, 124(100).

react

Her
e

 

39

Z-Hydroxyr3,4-dimethylbigyclo[2.2.2]octan-5-
carboxylic acid 0-Lactone (£3)

 

To a solution of 50 mL of toluene containing a small
amount of pargftoluenesulfonic acid was added .198 g (1
mmole) of hydroxy-acid‘gg and the resulting mixture was
refluxed 1 hr through a Dean-Stark water trap containing
molecular sieves (4A). Ether was added to the cooled solu-
tion and the organic mixture was washed with cold (3°) five
percent sodium bicarbonate and saturated sodium sulfate
solutions and finally dried over MgSO4. Removal of solvent
gave .092 g (51%) of lactone 22 as an oil. An analytical
sample obtained by preparative glpc (4% QF-l, 190°) exhibi-
ted the following properties: ir (CDC13) 1755 cm-1, 1270

cm ; mass spectrum (70 eV) m/e (rel intensity) 180(2)P,

152(10), 94(100).

5-Acetyl-4,7,7-trimethylbicyclo-
[2.2.2]octan-2-one’(agf

To a stirred solution of 2.2 mmoles of LDA in 40 mL of
THF, prepared by the usual manner, at -78° under an argon
atmosphere was added a solution of .300 mL (2.0 mmoles) of
isophorone in 5 mL of THF dropwise over a 5 min period, and
the resulting solution was stirred at -78° for 1 hr. The
reaction mixture was warmed to 25° and the solvent and amine

Were removed under vacuum being careful to avoid exposure

40

to the air. The resulting solid was dissolved in 80 mL of
THF under an argon atmosphere and the solution was cooled
to -78°. To this solution was added .178 mL (2.2 mmoles) of
methyl vinyl ketone in 5 mL of THF over a 5 min period.
The reaction mixture was stirred 2 hr at -78° and 12 hr at
25°. Water and ether were then added to the reaction mix-
ture and the aqueous solution was extracted with ether.
The combined ether extracts were washed three times with a
l M_HC1 solution, once each with a water and a saturated
sodium sulfate solution and finally dried over MgSO4.
Removal of the solvent yielded .364 g of a yellow oil.
Dione'23 (.310 g, 75%) was obtained as a white solid, mp
51-53°, by Kugelrohr’ distillation (110°, 5 microns). An
analytical sample obtained by preparative glpc (4% QF-l,
190°) exhibited the following properties: ir (CC14) 1725
cm’l: pmr (c0c13) a 2.0-2.25 (m.2n), 2.15 (3,33). 1.959130
(m,63) 1.15 (s,3H), 1.0 (s,3H), 0.9 (s,3H); mass spectrum
(70 eV) m/e (rel intensity) 208(15)P, 193(18), 138(28),
123(100).

5231. legg, for C H O : C, 74.96; H, 9.68.

13 20 2
Found: C, 74.91; H, 9.75.

(D

(“f

5.4

 

41

3'-Oxo-6-butyl-2,3—dimethylgyclohex-
2-enone (33)—

 

To a stirred solution of 22 mmoles of LDA in 200 mL of
THF, prepared by the usual manner, at -78° under an argon
atmosphere was added a solution of 2.48 g (20 mmoles) of
2,3-dimethylcyclohexenone in 50 mL of THF dropwise over a
10 min period and the resulting solution was stirred at -78°
for 1 hr. The reaction mixture was warmed to 25°, and the
solvent and amine were removed under vacuum being careful to
avoid exposure to the air. The resulting solid was dis-
solved in 400 ml of THF under an argon atmosphere and the
solution was cooled to -78°. To this solution was added
1.80 mL (22 mmoles) of freshly distilled methyl vinyl ketone
in 100 mL of THF over a 10 min period. The resulting mix-
ture was stirred 3 hr at -78° and 12 hr at rm temperature.
Water and ether were then added to the reaction mixture and
the aqueous solution was extracted with ether. The combined
ether extracts were washed three times with a 1 M HCl solu-
tion, once each with a water and a saturated sodium sulfate
solution and finally dried over M9804. Removal of the sol-
vent yielded 2.8 g of a yellow oil. Kugelrohr distillation
(100°, 5 microns) of the oil afforded 2.41 g (60%) of dione
30 as a colorless oil which exhibited the following proper-
ties: Uv (95% EtOH) 245 nm (e = 8,200); ir (0014) 1720 cm'l,

1660 cm’l: pmr (cc14) 0 2.7—2.2 (m,GH), 2.1 (s,3H), 1.85

42

(bs,4H), 1.70 (d,4H) 0.9 (m,1H); mass spectrum (70 eV) m/e
(rel intensity) 194(3)P, 137(41), 124(19), 96(100).
Anal. Calcd. for C12H1802: C, 74.19; H, 9.34.
Found: C, 74.19; H, 9.20.

9,lO-Dimethylbicyclo[4.4.0]deca-
2,9-diene-3-one (31)

 

To a stirred solution of .560 g (5 mmoles) of potas—
sium t-butoxide and 5 mL of t-butyl alcohol in 80 mL of THF
at 25° was added a solution of .388 g (2 mmoles) of dione 39
in 5 mL of THF. After stirring for 2 days at 25°, water
and ether were added and the aqueous phase was extracted
with ether. The combined ether extracts were washed twice
with a l M HCl solution, once each with water and a satur-
ated sodium sulfate solution and finally dried over M9804.
Removal of the solvent afforded .323 g (91%) of dienone 31’

as an oil. An analytical sample obtained by preparative

glpc (4% QF-l, 190°) exhibited the following prOperties:
_ . - “-1
Uv (EtOH)1max 291 nm (e - 19,600, 1r (CHC13) 1650 cm ,
1620 cm-1; pmr (0014) 6 5.5 (bs,lH), 2.4-2.0 (m,7H) 1.8
(m,8H); mass spectrum (70 eV) m/e (rel intensity) 177(7)P+1,
l76(56)P, 133(30), 105(100).
Anal. Calcd. for C12H16O : C, 81.77; H, 9.00
Found: C, 81.77; H, 9.00

 

 

‘5

Z

43

S-Carboxyf4,7,7-trimethy1bigyclo-
[2.2.2]octan-2-one (23)

To 2.98 g (13.19 mmoles) of keto-ester 21 was added
100 mL of ten percent aqueous sodium hydroxide, and this
solution was stirred for 5 hr at 25° (until homogeneous).
After acidification with 6 M HCl solution, the solution was
extracted three times with ether, and the combined extracts
were washed with water and saturated sodium sulfate solution
and finally dried over M9804. Removal of the solvent gave
2.26 g (82%) of a solid. Recrystallization from hexane and
ethyl acetate afforded keto acid 33 which exhibited the
following prOperties: mp 148-150°; ir (CDC13) 3300-3000
cm’l, 1720 cm-1; pmr (00013) 6 9.6 (bs,1H), 2.9-1.3 (m,8H),
1.1 (s,3H),1.05 (s,3H),0.90 (s,3H); mass spectrum (70 eV)

m/e (rel intensity) 210(7)P, 138(35), 123(100).

5-Chloroformy1-4,7,7-trimeth lbicyclo-
T2 . 2. 2Ectan-2-one (2%)

 

To a stirred solution of 2.0 g (8.77 mmoles) of keto-

acid 25,and 10 g of lithium chloride in 200 mL of CHCl was

3
added 20 mL of thionyl chloride. After stirring for 3 days
at 25° under an argon atmosphere, the reaction was filtered,
and removal of solvent from the filtrate afforded 1.78 g
(89%) of acid chloride 23 as a solid. Recrystallization

from CHCl afforded gé'as a white solid which exhibited the

3

44

following properties: mp 63-65°; ir (CDC13) 1795 cm-1,

1725 cm-1; pmr (CDC13) 6 2.5-1.2 (m,8H) 1.10 (s,3H), 1.05
(s,3H), 0.90 (s,3H); mass spectrum (70 eV) m/e (rel inten-

sity) 230(4)P+2, (228)P, 165(20), 138(28), 123(100).

Preparation of Dione 29 From Acid Chloride 35
N 6"

To a stirred solution of 1.17 g (6 mmoles) of cuprous

 

iodide in 80 mL of ether at -78° under an argon atmosphere
was added 7.05 mL (12 mmoles) of a 1.7 M_methy11ithium in
ether solution. The resulting reaction mixture was stirred
for 20 min, following which a solution of .448 g (2 mmoles)
of acid chloride 23,in 5 mL of ether was added. The reac-
tion mixture was then stirred for 4 hr, followed by the
addition of 1 ml of acetic acid.

After warming to 25°, water and ether were added and
the aqueous phase was extracted three times with ether.
The combined ether extracts were washed three times with a
buffered ammonium hydroxide solution (pH 9), once each with
water and a saturated sodium sulfate solution and finally
dried over MgSO4. Removal of solvent afforded 1.70 g (85%)
of an oil which was homogeneous by glpc (4% QF-l, 160°).
An analytical sample obtained by glpc (4% QF-l, 190°)
exhibited the identical gas chromatographic and spectral

properties as dione 29.
N

iriec'

H

'-«V(

 

 

45

5—Carboxy—3,4-dimethylbicyc10e
T2.2)2]octan-2-one (33)

 

To 1.71 g (8.14 mmoles) of keto-ester 23 was added 100
nd.of ten percent aqueous sodium hydroxide, and this solu-
tion was stirred for 6 hr at 25° (until homogeneous). After
acidification with 6 M hydrochloric acid, the solution was
extracted three times with ether, and the combined extracts
were washed with water and saturated sodium sulfate and
dried over M9804. Removal of the solvent gave 1.30 g (82%)
of a solid. Recrystallization from hexane and ethyl acetate
afforded keto-acid 39 which exhibited the following proper-

1, 1720 cm—1;

ties: mp 112-115°, ir (c0c13) 3300-3000 cm"
pmr (00013) 6 8.0 (bs,1H), 2.9-1.5 (m,8H), 1.2-1.0 (m,7H);

mass spectrum (70 eV) m/e (rel intensity), l96(9)P, 124 (100).

5-Chloroformrl-3,4-dimethylbicyclo-
[2}2.2,octan-2-one (23)

 

To a stirred solution of 1.58 g (8.5 mmoles) of keto-
acid 33 and 5 gm of lithium chloride was added 25 mL of
thionyl chloride. After stirring for 4 days at 25° under
an argon atmosphere, the reaction mixture was filtered, and
removal of solvent from the filtrate afforded 1.69 g (89%)
of acid chloride 23 as an oil which was homogeneous by gplc
_(4% QF-l, 160°). An analytical sample obtained by prepara-

tive glpc (4% QF-l, 190°) exhibited the following properties:

46

ir (00013) 1795 cm‘1

—1
. 1725 cm ; pmr (CDC13) 6 3.1-1.3
(m,9H), 1.1 (s,3H), 1.0 (d,3H); mass spectrum (70 eV) m/e
(rel intensity) 216(1)P+2, 214(2)P, 178(46), 124(37),

79(100).

5-Acetyl-3,4-dimethylbicyclo-
[2.2.2]octan-2-one (28)

 

 

To a stirred solution of 11.76 g (60 mmoles) of cuprous
iodide in 400 mL ether at —78° under an argon atmosphere
was added 70.5 mL (120 mmoles) of a 1.7 M_methy11ithium in
ether solution. The resulting reaction mixture was stirred
for 20 min, following which a solution of 4.28 g (20 mmoles)
of acid chloride 33 in 50 mL of ether was added. The reac-
tion mixture was then stirred for 4 hr, following which 2 mL
of acetic acid was added. After warming to 25°, water and
ether were added and the aqueous phase was extracted three
times with ether. The combined ether extracts were washed
three times with a buffered ammonium hydroxide solution
(pH 9), once each with water and saturated sodium sulfate

solution and finally dried over MgSO Removal of the

4.
solvent afforded 2.00 g (52%) of dione gg'as an oil which
was homogeneous by glpc (4% QF-l, 160°). An analytical

sample obtained by preparative glpc (4% QF-l, 190°) exhi-
bited the following properties: ir (c014) 1720 om‘l: pmr

(CC14) 5 2.8-2.1 (m,2H), 2.05(S,3H), 2.0-1.1 (m,7H),

47

1.00 (s,lH), 0.90 (s,3H), 0.80 (d,3H); mass spectrum
(70 eV) m/e (rel intensity) 194(20)P, 124(100).
Anal. Calcd. for C12H1802: C, 74.19; H, 9.34.
Found: C, 74.17; H, 9.21.

 

Treatment of Dione 23 with Base

 

 

To a stirred solution of .560 g (5 mmoles) of potas-
sium t-butoxide and 5 mL of t-butyl alcohol in 80 mL of THF
at 25° was added a solution of .776 g (4 mmoles) of dione
_38 in 5 mL of THF. After stirring at 25° for 2 days, water
and ether were added and the aqueous phase was extracted
with ether. The combined ether extracts were washed twice
with a l M_HC1 solution, once each with water and a satur—
ated sodium sulfate solution and finally dried over MgSO4.
Removal of the solvent afforded .437 g (62%) of an oil.

An analytical sample collected by preparative glpc exhibited
the identical spectral and gas chromatographic properties

of dione 31.
N

Treatment of Dione gg'with Base

 

 

To a stirred solution of .560 g (5 mmoles) of potassium
t-butoxide and 5 mL of t-butyl alcohol in 80 mL of THF at
25° was added a solution of .194 g (l mmole) of dione 23 in

5 mL of THF. After stirring at 25° for 2 days, water and

48

ether were added and the aqueous phase was extracted with
ether. The combined ether extracts were washed twice with
a 1 M HCl solution, once each with water and a saturated
sodium sulfate solution and finally dried over M9804.
Removal of the solvent gave .139 g (77%) of an oil which
showed two products, dione 23 and the epimer of dione 29
(ratio 9:1). An analytical sample of the major product
obtained by preparative glpc (4% QF-l, 190°) exhibited the

identical spectral and gas chromatographic properties as

dione 29.
N

3—Methy1cyclohex—2-enone

 

To a stirred solution of 4.90 g (35 mmoles) of 3-ethoxy-
2-cyclohexenone in 100 mL of ether under an argon atmos-
phere at 25° was added 25 mL (40 mmoles) of 1.6 M_methy1-
lithium in ether. After 24 hr, the reaction mixture was
poured into an ice and water mixture. The aqueous phase
was extracted with ether and the combined ether extracts
were washed three times with a l M HCl solution, once each
with water and a saturated sodium sulfate solution and
finally dried over M9804. Removal of the solvent afforded
2.69 g (70%) of crude 2-methy1cyclohexenone. Distillation
through a short-path still gave 2.11 g of colorless
3-methylcyclohexenone which exhibited the following

properties: bp 98-100° (7 mm)(lit. bp 99.5-98(8.0:mm)]26;

49

ir (liquid film) 1675 cm"1

, 1640 cm—1; pmr (CDC13) 6 5.7
(m,1H), 2.4-2.0 (m,6H), 1.9 (s,lH); mass spectrum (70 eV)

m/e (rel intensity) 110(37)P, 82(100).

3—Ethoxy—2-methylcyclohexenone

 

To a solution of 400 mL of toluene and 200 mL of
absolute ethanol containing 3.0 gm of pagaftoluenesulfonic
acid was added 37.8 g (0.3 moles) of 2-methylcyclohexane—
1,3-dione, and the resulting mixture was refluxed for 18 hr
through a Dean-Stark water trap. After cooling, the reac-
tion mixture was washed with four 100 mL portions of ten
percent aqueous sodium hydroxide which had been saturated
with sodium chloride. The resulting organic solution was
washed with successive 50 m1 portions of water until the
aqueous washings were neutral. Removal of the solvent
afforded an oil which was purified by vacuum distillation
to yield 14.4 g (31%) of a clear oil which exhibited the
following properties: bp 80°, .300 mm; ir (CC14) 1665 cm-1,
1630 cm'l; pmr (cc14) 6 4.0 (q,2H), 2.7-1.6 (m,6H), 1.45
(3,33), 1.35 (t,3H): mass spectrum (70 eV) m/e (rel inten-

sity) 155(6)P+l, 154(53)P, 110(42), 98(100).

50

2-Methy1cyclohex-2-enone

J

To a stirred solution of .910 c (24 mmoles) of lithium
aluminum hydride (LAH) in 300 mL of dry ether was added
dr0pwise a solution of 14 g (92.5 moles) of 3-ethoxy-2-

me thylcyclohexenone in 100 mL of ether. The reaction mix-
ture was refluxed for 24 hr, cooled and then carefully
poured into a water and ice mixture which was acidified to
a pH of two with 1 IL! HCl solution. The aqueous phase was
extracted with ether, and the combined ether were washed
three times with 1 lg HCl solution and once each with water
and a saturated sodium sulfate solution and finally dried

over M9804. Removal of the solvent gave 8.5 g (82%) of an

Oil. Distillation through a short-path still afforded 7.4
gm of colorless 2-methylcyclohexenone which exhibited the
f<:b2l.lowing properties: bp. 57-60 (10 mm) (Lit. bp. 56

( 9 mm)]27: ir (liquid film) 1680 cm‘l; pmr (cc14) 6 6.7
(b8,1H), 2.5-1.8 (m,6H), 1.65 (s,3H); mass spectrum (70 eV)

m/e (rel intensity) 110(37)P, 82(100).

5—Carbomethoxy:4-methy1bicyclo—
12.2.2Joctan-23one (397'
N
To a stirred solution of 5.5 mmoles of LDA in 80 mL of
'rEUF, prepared by the usual manner, at ~23° under an argon

a“T-mcsphere was added a solution of .550 g (5.0 moles) of

51

3-methylcyclohex-2-enone in 5 mL of THF dropwise to the

reaction mixture over a 10 min period. The resulting mix-

ture was stirred at ~23° for 1 hr, following which a solu-

tion of .550 mL (6.0 moles) of methyl arcylate in 5 mL of

THE was added dropwise over a 5 min period. After stirring

for 2 hr at —23°, water and ether were added to the reac-

tion mixture and the aqueous phase was extracted with ether.

The combined ether extracts were washed three times with a

l h_’1 HCl solution, once each with water and a saturated

 

sodium sulfate solution and finally dried over M9804. ‘
Removal of the solvent gave .879 g (98%) of keto-ester ’33

as a yellow oil which was homogeneous by glpc (4% QF-l, 130°).

An analytical sample obtained by preparative glpc (4% QF-l,

190°) exhibited the following properties:

1725 cm‘l, 117s cm‘l; pmr (CDc13) 6 3.6 (8,311), 2.9-1.3

ir (CDC13)

(m,10H), 0.95 (s,3H); mass spectrum (70 eV) m/e (rel inten-
sity) 196(11)P, 110(100).

Anal. Calcd. for C11H1603: C, 67.32; H, 8.22.

Found: C, 67.44; H, 8.31.

5-Acety1-4-methylbicyclo[2.2.2]-
octan-2-one 75$)

To a stirred solution of 2.2 mmoles of LDA in 40 mL of
THE, prepared by the usual manner, at -78° under argon was
added a solution of .220 gm (2.0 moles) of 3-methylcyclo-

helvc-Z—enone in 5 mL of THF over a 10 min period and the

52

resulting solution was stirred at -78° for 1 hr. The reac-
tion mixture was warmed to 25° and the solvent and amine
were removed under vacuum being careful to avoid exposure
to air. The resulting solid was dissolved in 80 mL of THF
under an argon atmosphere and was cooled to -78°. To this
reaction mixture was added .180 mL (2.2 moles) of methyl
vinyl ketones in 10 mL of THF over a 10 min period. The
resulting mixture was stirred 3 hr at -78° and 12 hr at 25°.

Water and ether were then added to the reaction mixture and

 

the aqueous solution was extracted with ether. The com-
bined ether extracts were washed three times with a l 11 HCl
Selution, once each with a water and a saturated sodium
Sulfate solution and finally dried over M9804. Removal of
the solvent gave .262 g (73%) of dione 43 as a pale yellow
Oil which was homogeneous by glpc (4% QF-l, 160°). An ana-
1Ytica1 sample obtained by preparative glpc (4% QF-l, 190°)
exhibited the following characteristics: ir (CC14) 1735
cm‘l; pmr (cc14) 6 2.8-2.2 (m,3H), 2.1 (s,3H), 2.0-1.2
(m, 7H), 0.95 (9,311); mass spectrum (70 eV) m/e (rel intens-
ity} . 180 (49)P, 110(100) .

Anal. Calcd. for C H O C, 73.30; H, 8.95.

11 16 2‘
Found: C, 73.33; H, 8.93.

 

53

5-Carbomethoxy-3-methylbicyclo-
[2 . 2.2]octan-2-one (11;)

 

 

To a stirred solution of 2.2 mmoles of LDA in 80 mL of
THE, prepared by the usual manner, at -78° under an argon
atmosphere was added a solution of .220 g (2.0 moles) of
2-methylcyclo-hex-2-enone in 5 mL of THF dropwise to the
reaction mixture over a 10 min period. The resulting mix—

ture was stirred at -23° for 1 hr, following which a solu-

 

txion of .210 mL (2.4 mmoles) of methyl acrylate in 5 mL of
THF was added dropwise over a 5 min period. The reaction
nxixture was stirred for 2 hr at -23°. Water and ether were
added to the reaction mixture and the aqueous phase was
extracted with ether. The combined ether extracts were
vmashed three times with a l §_HC1 solution, once each with
Water and a saturated sodium sulfate solution and finally
Cilried over MgSO4. Removal of the solvent gave .315 g (81%)
(>15 keto-ester 41 as a pale yellow oil which was a mixture of
C3-3 epimers by glpc (4% QF-l, 160°). An analytical sample
C>1>tained by preparative glpc (4% QF-l, 190°) exhibited the

1, 1250 cm'l,

fellowing properties: ir (CDC13) 1730 cm-

1150 an“; pmr (00013) 6 3.65 (s,3H), 2.3-0.90 (m,13H):

mass spectrum (70 eV) m/e (rel intensity) 196(20)P, 110(100).
Anal. Calcd. for C11H1603: C, 67.32: H, 8.22.

Found: C, 67.34; H, 8.18.

 

54

S-Acetyl-B-methylbicyclo[2.2.2]-
octanTZ -one (1.2,)

 

To a stirred solution of 2.2 mmoles of LDA in 40 mL of
THE, prepared by the usual manner, at -78° under an argon
atmosphere was added a solution of .220 g (2.0 moles) of
Z-mthylcyclohexenone in 5 mL of THF dropwise to the reac-
tion mixture over a 10 min period. After stirring for 1 hr
at -78°, the reaction was warmed to 25° and the solvent and
amine were removed under vacuum being careful to avoid
exposure to air. The resulting solid was dissolved in 80
mL of THF under an argon atmosphere and the solution was
cooled to ~78°. To this solution was added .180 mL (2.2
moles) of methyl vinyl ketone in 10 mL of THF over a 10
min period. The resulting mixture was stirred 2 hr at -78°
and 12 hr at 25°. Water and ether were then added to the
reaction mixture and the aqueous solution was extracted with
ether. The combined ether extracts were washed three times
with a 1 g HCl solution, once each with a water and a
Saturated sodium sulfate solution and finally dried over
M9804. Removal of the solvent gave .308 g (81%) of dione
3‘3, as a pale yellow oil. Glpc analysis (4% QF-l, 160°)
Showed a mixture of epimers and starting material (9:1) . An
aIlalytical sample obtained by preparative glpc (4% QF-l,
1-9O") exhibited the following properties: ir (CC14) 1730

curl, pmr (cc14) 6 2.3-2.2 (m,3H), 2.15 (s,3H), 2.0-1.0

 

55

(m,10H); mass spectrum (70 eV) m/e (rel intensity)

181(6)P+1: 180(44)P, 110 (100) .

Anal. Calcd. for C11H1602: C, 73.30; H, 8.95.

Found: C, 73.12; H, 8.97.

 

S-Hydroxrmethy1-4,7,7-trimethy1bicyclo-
2.2.2]octan-2-ol (fig)

 

To a stirred solution of .228 g (6 mmoles) of LAH in
300 mL of ether at 25° was added drOpwise a solution of
J..212 g (5 mmoles) of keto-ester 21,in 15 mL of ether. The
reaction mixture was refluxed for 24 hr, cooled and then
carefully poured into a water and ice mixture which was
acidified to a pH of two with 1 g HCl solution, the aqueous
Phase was extracted with ether and the combined ether ex-
tracts were washed twice with water, once with a saturated
Sodium sulfate solution and finally dried over MgS04.
Removal of the solvent afforded .894 g (89%) of a white
SOlid, mp 135°. Recrystallization from acetone gave diol
jifi which exhibited the following properties: mp 137°;

1 1 l

, 1025 cm-

, 1170 cm- ; pmr (D6-acetone)

ir (nujoil) 3240 cm-
5 3.45 (d,2H), 3.14 (m,1H), 2.78 (s,2H, dissappears with
D20), 1.4-1.0 (m,7H), 0.9 (s,3H), 0.8(s,3H): mass spectrum
(70 eV) m/e (rel intensity) 198(3)P, 180(35), 180(30),
93(100).

Anal. Calcd. for C12H2202: C, 72.68: H, 11.13.

 

Found: C, 72.80; H, 11.13.

56

5-Formyl-4,7,7-trimethylbicyclo-
[2. 2 . 2‘ octan-Y-one (‘EZY

 

 

 

To a mechanically stirred solution of .537 g (2.5

moles) of pyridinium chlorochromate in 100 mL of CH2C12 at

25° was added a solution of .198 g (1 mole) of diol ’48 in

20 mL of CH2C12. After 3 hr,

the superatant was decanted from the black gum.

50 mL of ether was added and

The insol-
uble residue was washed three times throughly with 50 mL

portions of ether whereupon it became a black granular

solid. The combined organic solution was passed through a

short pad of florisel and was washed with 30 mL portions of
a solution of 5 mL of acetyl acetone in 300 mL of a 20%
Sodium hydroxide solution and twice with water, once with

Saturated sodium sulfate solution and finally dried over

M9804. Removal of the solvent gave .165 g (84%) of keto-

aldehyde 5:; as an oil which was homogeneous by glpc

(4 % QF-l, 160°). An analytical sample collected by glpc

(4% QF-l, 190° ) exhibited the following properties: ir
(Cc14) 2855 cm’l, 2700 cm'l, 1730 cm‘l; pm: (0014) 6 9.5

(8,111), 2.5(bs,2H), 1.9-1.5 (m,5H), 1.1 (s,4H), 0.9 (s,4H):

mass spectrum (70 eV) m/e (rel intensity) 194(4)P, 180(10)
impurity, 179(17), 138(38), 123(100).

57

5-(1'-hydroxya11y1)-4,7,7-trimethy1bicyglo-
T2.2izloctan-2-one (43)

 

To a stirred solution of .194 g (1.0 mmole) of keto-

aldehyde 43 in 100 mL of THF at 25° was added dropwise 1.25
mL (3 moles) of 2.4 b_4 vinyl magnesium bromide in THF.

After 3 hr, the reaction mixture was poured into an ice and

water mixture. The aqueous phase was extracted with ether

and the combined ether extracts were washed twice with

water, once with a saturated sodium sulfate solution and

finally dried over M9804. Removal of the solvent gave

- 200 g (90%) of hydroxyketone 43 as a yellow oil, which was

homogeneous by glpc (4% QF-l, 190°). An analytical sample

Obtained by preparative glpc (4% QF-l, 190°) exhibited the

following properties: ir (CHCL3) 3600 cm-1, 3460 cm-1,

.1720 cm'l- pmr (c0013) 6 6.1-5.5 (vinyl,3H), 4.5 (bs,1H),

I

2-0-1.5 (m,6H), 1.3 (m,3H), 1.1 (s,6H), 0.9 (8,311): mass

Spectrum (70 eV) m/e (rel intensity) 222(2)P, 204(4),

1 38 (30) , 123 (100) .

Anal. Calcd. for C14H2202: C, 75.63; H, 9.97.

Found: C, 75.75: H, 9.89.

 

8-Acrrloy1-4i],7-trimethylbicyclo-
2.2.2Toctan-2-one (£3)

 

To a mechanically stirred solution of 30 g of manganese

Ciioxide in 400 mL of CH2C12 at 25° was added 3.0 g (13.6

mmoles) of hydroxyketone L6, in 30 mL of CH2C12. After 24 hr,

58

1130 mL of ether was added and the superatant was decanted
from the brown residue. The insoluble residue was then
washed three times with ether and the combined organic solu-
tion was passed through a short pad of celite and finally
dried over MgSO4. Removal of the solvent yielded 2.31 g
('7£3%) of dione 43 as a yellow oil which was homogeneous by
glpc (4% QF-l, 190°). An analytical sample obtained by
preparative glpc (4% QF-l, 190°) exhibited the following

Properties: ir (CC14) 1725 cm-1

, 1675 cm'l; pmr (c014) 6
6.3-5.5 (vinyl,3H), 2.8-1.2 (m,10H), 1.1 (s,3H), 0.95 (s,3H);
mass spectrum (70 eV) m/e (rel intensity) 221(5)P+1,
220(34)P, 138(59), 55(100).

Anal. Calcd. for C14H2002: C, 76.33; H, 9.15.

Found: C, 76.22; H, 9.09.

S-H drox eth l—3,4-dimeth lbic clo-
l2.;.2loctan-2-OI (5%)

N

To a stirred solution of .36 g (9.5 mmoles) of LAH in
53(30 mL of ether at 25° was added dropwise a solution of 1.79
E! (8.5 mmoles) of keto-ester 23 in 50 mL of ether. The
I1‘Gaaction mixture was refluxed for 24 hr under an argon
El1:mosphere, cooled and then carefully poured into a water
Eilld ice mixture which was acidified to a pH of two with 1.!
H<21 solution. The aqueous phase was extracted with ether

a~1'1d the combined ether extracts were washed twice with

59

water, once with a saturated sodium sulfate solution and

finally dried over M9804. Removal of the solvent gave 1.35

g; (86%) of diol 53 as a white solid, mp 183-186°. An ana-
L13g1:ica1 sample obtained by preparative glpc (4% QF-l, 190°)

1

exhibited the following prOperties: ir (CHC13) 3600 cm- ,

3400 cm'l; pmr (D6-acetone) 6 3.6 (m,3H), 2.8 (s,2H), 1.9-

1- 2 (m,7H), 1.05-0.9 (m,6H); mass spectrum (70 eV) m/e

(rel intensity): 184(1)P, 108(100).

Anal. Calcd. for C11H2002: C, 70.92; H, 11.90.

Found: C, 71.61; H, 11.01.

S-Formyl-B,4-dimethy1bicyclo-
[2.2.2]octan-2-one (51)
~
To a mechanically stirred solution of 14.8 g (69
Innuoles) of pyridinium chlorochromate in 300 mL of CH2C12 at

25° was added a solution of 3.18 g (17.3 moles) of diol 23
After 5 hr, 50 mL of ether was added
The

in 30 mL of CH2C12.
and the superatant was decanted from the black gum.

insoluble residue was washed three times throughly with

100 ml portions of ether whereupon it became a black granu-

1a.: solid. The combined organic solution was passed through

a short pad of florisel and was washed with a solution of
5 ml. of acetyl acetone in 300 mL of a 20% sodium hydroxide

S<31ution and twice with water, once with saturated sodium

SWillfate and finally dried over MgSO4. Removal of the

60

solvent gave 2.08 g (67%) of a yellow oil. Further purifi-
cation by Keigelrohr distillation (85°, 5 microns) afforded
51 as a clear liquid, ir (cc1 ) 2930 cm-1, 1720 cm'l, 1690
N 4

cm’l- pmr (c0013) 6 9.85 (d,lH), 2.8-1.6 (m,9H), 1.4-0.9

l

(m,6H); mass spectrum (70 eV) m/e (rel intensity) 180(35)P,

124 (100).
Anal. Calcd. for C11H1602: C, 73.30; H, 8.95.
Found: C, 73.29; H, 8.97.

5-(1'-Hydroxya11 1)-3,4-dimethy1-2-viny1-
bicycToIf. . Joctan32-FI (’53)

To a stirred solution of 2.08 g (11.55 mmoles) of keto-
aldehyde ’51 in 100 mL of THF at 25° was added 9.2 mL (22
mmoles) of 2.4 b_d_ vinyl magnesium bromide in THF. After 5 hr,
the reaction was poured into an ice-water mixture. The
aqueous phase was extracted with ether and the combined
ether extracts were washed twice with water and once with a
Saturated sodium sulfate solution and finally dried over

54980 Removal of solvent gave 2.41 g (88%) of diol ’53; as

4.
€111 oil which was homogeneous by glpc (4% QF-l, 160°). An
Elrialytical sample obtained by preparative glpc (4% QF-l,
J—S?0°) exhibited the following property: mass spectrum
('70 eV) m/e (rel intensity) 236(1)P, 218(1), 124(23),

85(100).

61

5-Acryloyl-3,4-dimethyl-2-viny1bigyclo-
[2.2.2Toctan-2Fol (23)

To a stirred solution of 25 g of manganese dioxide in

4C)() mL of CH2C12 at 25° was added 2.36 g (10 mmoles) of

(1101 ’53 in 30 mL of CHZClZ. After 24 hr, 100 mL of ether

VVELES added and the superatant was decanted from.the brown

residue. The insoluble residue was then washed three times

VVi;th ether and the combined organic solution was passed

‘tlirough a short pad of celite and finally dried over M9804.
Removal of the solvent yielded 2.12 g (91%) of an oil which

contained hydroxy ketone ’5‘4’ and ~5% starting material as

shown by glpc (4% QF-l, 160°) . An analytical sample obtain-

<ad by preparative glpc (4% QF—l, 190°) exhibited the follow-

ling properties: ir (CC14) 3220 cm-1, 1725 cm-1: pmr (CC14)

6 604-404 (m,6H), 401 (111,13), 2.8-109 (111,911) 1.0-008 (111,611);

Inass spectrum (70 eV) m/e (rel intensity) 234(1)P, 219(4),
.206(10), 124(22), 41(100).

3-t-Buty1dimethylsilyloxy:1 2-dimethy1-
cyclbhexa:l}31diene (25)

To a stirred solution of 55.5 mmoles of LDA, prepared
.in the usual manner, in 300 mL of THF at -78° under an argon
atmosphere was added a solution of 6.2 g (50 mmoles) of

2,3-dimethylcyclohexenone in 100 mL of THF dropwise over a

10 min period. The reaction mixture was stirred for 1 hr

and then 5 mL of HMPA was added. After the reaction mixture

62

warmed to 0°, a solution of 10.5 g (70 moles) of t-butyldi-

methylchlorosilane in 100 mL of THF was added over a 10 min

period- The reaction mixture was stirred for 18 hr at 25°,

water and ether were then added and the aqueous phase was

extracted with ether. The combined ether extracts were

washed three times with water and once with a saturated

sodium sulfate solution and finally dried over M9804.
Removal of the solvent gave a clear oil. Purification by
vacuum distillation (123°,6mm) yielded 10.0 g (88%) of

dienol ether ’53 as a clear oil with the following properties:
ir (neat) 1645 cm-1, 1620 cm-1; pmr (CC14) 6 4.6 (bs,1H),
2-1-1.6 (m,10H), 0.95 (5,911), 0.20 (s,6H); mass spectrum
(70 eV) m/e (rel intensity) 238(5)P, 236(5), 75(100).

Anal. Calcd. for C14H2608i: C, 70.52; H, 10.99

Found: C, 70.47; H, 10.84.

1 , 2-Dimethyl-3-trimethylsilyloxy-
gclcfiiexa-IA-diene (:6)

To a stirred solution of 55.5 moles of LDA, prepared
in the usual manner, in 300 mL of THF at -78° under an
argon atmosphere, was added a solution of 6.2 g (50 moles)
0f 2pIS—dimethylcyclohexenone in 100 mL of THF dropwise over

a 10 min period. The reaction mixture was stirred for 1 hr

and then 5 mL of HMPA was added. After the reaction mixture

warmed to 0°, a solution of 12.6 mL (100 moles) of tri-

methylchlorosilane in 100 mL of THF was added over a 10 min

63

period- The reaction mixture was stirred for 18 hr at 25°,

water and ether were then added and the aqueous phase was

extracted with ether. The combined ether extracts were

washed three times with water and once with a saturated

sodium sulfate solution and finally dried over M9804.

Removal of the solvent gave a clear oil. Purification by

vacuum distillation (104°, 7 mm) yielded 8.58 g (87%) of

ether ’53 as a clear oil with the following properties:

ir (neat) 1640 cm'l, 1620 cm-1; pmr (cc14) 6 4.75 (bs,1H),

2.05 (m,4H), 1.7 (m,6H), 0.20 (s,9H); mass spectrum (70 eV)

m/e (rel intensity) 198(5)P, 196(59), 73(100).

Anal. Calcd. for CllHZOOSi: C, 67.28; H, 10.26.

Found: C, 67.17; H, 10.07.

5-Acetyl-2-t-but zldimethylsilyloxy-3 , 4-dimethyl-
Bicyclo 2 . T. 2Toct-Fene (’53)

 

To a stirred solution of 2.38 g (10 moles) of dienol
ether §3 in 200 mL of toluene containing ~10 mg of hydro-
QUinone was added 1.62 mL (20 moles) of methyl vinyl ketone.
This reaction mixture was refluxed for 24 hr under an argon
atmOSphere. Removal of the solvent afforded 2.84 g (92%)
0f ketone ’53) as an oil which was homogeneous by glpc
(4% QF-l, 100°). An analytical sample obtained by prepara-
tiVe glpc (4% QF-l, 190°) exhibited the following properties:

ir (CC14) 1700 cm-1, 1650 cm-1; pmr (CC14) 6 2.5-2.0 (m,3H),

64

1.95 (s,3H), 1.8-1.2 (m,8H), 1.1 (s,3H), 0.9 (s,9H), 0.2
(bs,6H)

‘0

mass spectrum (70 eV) m/e (rel intensity) 308(8)P,
238(15) , 75(100).

Anal. Calcd. for C18H3202S1: C, 70.07,

Found: C, 70.07; H, 10.38.

H, 10.45.

From a pmr experiment using EuFOD, ’53 was found to be

epimeric at C-5 (ratio; syn:anti, 80:20).

2_—t-Butyldimethjlsilyloxy-3 , 4-dimethyl-5-formy1-

bicyclo [2 . 2 .2] oct-T-ene (’53)
To a stirred solution of 2.38 g (10 moles) of dienol

ether 55 in 200 ml of toluene containing ~10 mg of hydro-

Quj-none was added 1.34 mL (20 moles) of acrolein. This

reaction was refluxed for 23 hr under an argon atmosphere.
Removal of solvent afforded 2.90 g (98%) of aldehyde 53 as
an Oil which was homogeneous by glpc (4% QF-l, 100°). An
analytical sample obtained by preparative glpc (4% QF-l,

190°) exhibited the following properties: ir (neat) 1730
1

cm 1, 1690 cm‘ , pmr (00013) 6 9.1 (d,1H), 2.4-1.3 (m,11H),

1.2 (111,311), .9 (bs,9H): 0.2 (m,6H); mass spectrum (70 eV)
m/e (rel intensity) 294(6). 239(31). 75(100).

From a pmr experiment using EuFOD, 5‘8) was found to be

epimeric at C—5 (ratio; syn:anti, 80:20).

65

2-t-Buty1dimethylsilyloxtS-cyano-3 , 4-dimethy1-
biEyc 1012 . 2. 2Rct-Fene (:33)

To a stirred solution of 2.38 g (10 moles) of dienol
ether 55 in 200 mL of toluene containing ~10 mg of hydro—
guinone was added 1.30 mL (20 moles) of acrylonitrile.

This reaction mixture was refluxed for 24 hr under an argon

atmOSphere. Removal of the solvent afforded 2.36 g (81%)

of nitrile ’53 as an oil which was homogeneous by glpc (4%

QF'lo 100°) . An analytical sample obtained by preparative

glpc (4% QF-l, 190°) exhibited the following properties:

is (neat) 2225 cm-1, 1670 cm-1; pmr (CC14) 6 2.5-l.5 (m,10H),

1-3 (m,6H), 0.9 (d,9H), 0.1 (d,6H); mass spectrum (70 eV)
m/e (rel intensity) 291(30)P, 238(44), 182(100), 75(85).

Anal. Calcd. for C H OSiN: C,

1.7 29 70.04; H, 10.02

Found: C, 70.03; H, 10.03.

From a pmr experiment ’53, was found to be epimeric at

2-t-Buty1dimethylsi1

rloxy-S-carbomethoxyf3,4-
dimethylbicyclo

2.2.2]oct-2-ene (60)
N

 

To a stirred solution of 2.38 g (10 moles) of dienol
ether ’5‘; in 200 mL of toluene containing ~10 mg of hydro-
quinone was added 1.80 mL (20 moles) of methyl acrylate.
This reaction mixture was refluxed for 24 hr under an argon

atmosPhere. Removal of the solvent afforded 3.20 g (95%)

66

of 63 as an oil which was homogeneous by glpc (4% QF-l,100°)

An analytical sample obtained by preparative glpc (4% QF-l,

190°) exhibited the following properties: ir (CC14) 1735
cm-1, 1660 cm'l; pmr (cc14) 6 3.5 (d,3H), 2.3-1.0 (m,14H),
0.9 (s,9H), 0.1 (d,3H); mass spectrum (70 eV) m/e (rel
intensity) 325(8)P+l, 324(28)P, 238(59), 182(100).

From a pmr experiment using EuFOD, 69 was found to be

epimeric at C-5 (ratio; syn:anti, 70:30).

5-Acety1-3,4-dimethyl-2-trimethylsilyloxybicyclo-
(2.2.2loct—2-ene (61)
N

To a stirred solution of .880 g (5 mmoles) of dienol
etherlgg in 200 mL of toluene containing'~10 mg of hydro-
quinone was added 1.22 mL (15 mmoles) of methyl vinyl ketone.
This reaction mixture was refluxed for 24 hr under an argon
atmosphere. Removal of the solvent afforded 1.31 g (97%)
of ketone 21 as an oil which was homogeneous by glpc (4%
QF-l, 100°). An analytical sample obtained by preparative
glpc (4% QF—l, 190°) exhibited the following properties:

ir (neat) 1725 cm“1

, 1680 cm-1; pmr (c0013) 6 2.5-1.3 (m,
14H), 1.1 (s,3H), 0.2 (d,9H); mass spectrum (70 eV) m/e
(rel intensity) 266(12)P, 196(100).

Anal. Calcd. for ClSHZGOZSl: C, 67.61; H, 9.83.

Found: C, 67.61; H, 9.78.

 

l)
9
. 1‘
(I)
H

quino
react
ethos
cf all

QF-l,

67

3,4-Dimethyl-5fiformyl-2-trimethylsi1yloxy-
biCycloT2.2.2Toct-2:ene (62)

To a stirred solution of 1.98 g (10 mmoles) of dienol
ether 26 in 200 mL of toluene containing-10 mg of hydro-
quinone was added 1.35 mL (20 mmoles) of acrolein. This
reaction mixture was refluxed for 24 hr under an argon
atmosphere. Removal of the solvent afforded 2.30 g (92%)
of aldehyde 6; as an oil which was homogeneous by glpc (4%
QF-l, 100°). An analytical sample obtained by preparative
glpc (4% QF-l, 190°) exhibited the following properties:
ir (neat) 1680 cm’l, 1635 cm-1; pmr (c0c13) 9.15 (d,1H),
2.5-0.9 (m,14H), 0.1 (s,9H); mass spectrum (70 eV) m/e
(rel intensity) 2526(6)P, 196(100).

Anal. Calcd. for C14H240281: C, 66.61; H, 9.58.

Found: C, 66.41; H, 9.61.

°°1°°°g1§gig121915:;ss2211gai—11 11°-
To a stirred solution of .588 g (3 mmoles) of dienol
ether 26 in 200 mL of toluene containing'vlo mg of hydro-
quinone was added .795 mL (12 mmoles) of acrylonitrile.
This reaction mixture was refluxed for 24 hr under an argon
atmosphere. Removal of the solvent afforded .689 g (92%)
Of'nitrile‘gg as an oil which was homogeneous by glpc

(4% QF-l, 100°). An analytical sample obtained by

68

preparative glpc (4% QF-l, 190°) exhibited the following

properties: ir (CHC13) 2230 cm”1‘

, 1670 cm’l; pmr (coc13) 6
2.5-1.0 (m,14H), 0.2 (d,9H); mass spectrum (70 eV) m/e
(rel intensity) 249(13)P, 196(100).

Anal. Calcd. for C11H23O Si N: C, 67.41; H, 9.29.

Found: C, 67.53; H, 9.32.

3,4—Dimethyl-5-(1'-hydroxyethyl)bicyclo-
[2.2}2]octan-2-onew(§3)

To a stirred solution of 2.66 g (10 mmoles) of alde-
hyde 63 in 100 mL of ether was added 18.6 mL (30 mmoles) of
1.6 §_methyllithium in ether at 25° under an argon atmos-
phere. After 4 days, the reaction mixture was poured into
an ice-water mixture. The aqueous phase was extracted with
ether and the combined ether extracts were washed twice
with water and once with a saturated sodium sulfate solution
and finally dried over MgSO4. Removal of the solvent gave
1.59 g (81%) of hydroxy ketone gé’as an oil, which was
homogeneous by glpc (4% QF-l, 160°). An analytical sample
obtained by preparative glpc (4% QF-l, 190°) exhibited the

1, 3430 cm'l,

following properties: ir (CHC13) 3600 cm-
1720 cm-1; pmr (CDC13) ratio methyl to nonmethyl protons
(1:1); mass spectrum (70 eV) m/e (rel intensity) 196(8)P,

178(55), 124(100).

69

Oxidation of Alcohol 64
Au

 

To a stirred solution of 1.07 g (5 mmoles) of pyridin-
ium chlorochromate in 100 mL CH2C12 at 25° was added a solu-
tion of .364 g (2 mmoles) of hydroxy ketone 63 in 30 mL
CH2C12. After 3 hr, 100 mL of ether was added and the
superatant was decanted from the black gum. The insoluble
residue was washed three times throughly with 50 mL portions
of ether whereupon it became a black granular solid. The
combined organic solution was passed through a short pad of
florisel and was washed three times with 40 mL portions of
a solution of 5 mL of acetyl acetone in 300 mL of a 20%
sodium hydroxide solution and once each with water and a
saturated sodium sulfate solution and finally dried over

MgSO Removal of the solvent gave .300 g (83%) of an oil

4.
which was homogeneous by glpc. An analytical sample ob-
tained by preparative glpc (4% QF-l, 190°) exhibited identi-

cal spectral properties as dione 38.

5-(3'-Hydrox7-3'—but-1'-eny1)-3,4-dimethy1bicyclo-
2.2.2]octan-2-one(§3)

 

 

 

To a stirred solution of 2.66 g (10 mmoles) of ketone
61 in 100 mL of THF at 25° under an argon atmosphere was
added 9.8 mL (22 mmoles) of 2.25 §_viny11ithium in THF.
After 4 days, the reaction mixture was poured into an ice-

water mixture. The aqueous phase was extracted with ether

70

and the combined ether extracts were washed twice with water
and once with a saturated sodium sulfate solution and

finally dried over MgSO Removal of the solvent gave 1.86

4.
g (83%) of hydroxy ketone 61 as an oil, which was homogene-

ous by glpc (4% QF-l, 160°). An analytical sample obtained

by preparative glpc (4% QF-l, 190°) exhibited the following

1 l l

prOperties: ir (CHC13) 3590 cm- , 3450 cm- , 1720 cm- ;

pmr (CDC13) 6 6.2-5.5 (m,4H), 2.4-1.4 (m,10H), l.3(s,3H),

1.1-0.9 (m,6H); mass spectrum (70 eV) m/e (rel intensity) 4
218(25)impurity, 204(6)m-H20, 123(100).
Anal. Calcd. for C14H2202: C, 75.63; H, 9.97.

 

Found: C, 76.45; H, 9.99.

5—(2'-Buta-1',3'-diene)-3,4-dimethy1bicyclo-
[2}2.2Ioctan:2-one (63)

 

 

To a solution of 200 mL of toluene containing 50 mg of
pgggftoluene-sulfonic acid was added .654 g (3 mmoles)
of hydroxy ketone 63, and the resulting mixture was refluxed
for 24 hr through a Dean-Stark water trap. Ether was added
to the cooled solution and the organic mixture was washed
with saturated sodium carbonate and saturated sodium sulfate
solutions and finally, dried over M9804. Removal of the
solvent under reduced pressure gave .404 g (65%) of diene
68 as an oil which was homogeneous by glpc (4% QF-l, 160°).
An analytical sample obtained by preparative glpc (4% QF-l,

190°) exhibited the following properties: ir (CC14):

71

1 l

3090 cm- , 1730 cm- ; pmr (c014) 6 6.6-4.8 (m,5H), 3.0-1.6
(m,10H), 1.2-0.9 (m,7H); mass spectrum (70 eV) m/e (rel
intensity) 204(31)P, 124(42), 55(100).

Anal. Calcd. for C14H200 : C, 82.30; H, 9.87.

Found: C, 82.16; H, 9.87.

 

Preparation of Diene 68 via Allyl Chloride 65
N N

 

To a stirred solution of .654 g (3 mmoles) Of.23 and
.241 mL (3 mmoles) of pyridine in 40 ml of ether at 0° was
added .238 mL (3.3 mmoles) of thionyl chloride. The reac-
tion mixture was stirred for 10 min at 0° and then concen-
trated to dryness under reduced pressure. The resulting oil
was dissolved in toluene and concentrated to dryness three
times. The residue was dissolved in water and ether, and
the ether layer was washed with cold (3°) sodium bicarbonate
and water and finally dried over M9804. Removal of the
solvent gave .4218 g (58%) of a dark oil which was homogene-
ous by glpc (4% QF-l, 160°). A sample obtained by prepara-
tive glpc (4% QF-l, 190°) had the identical pmr as diene 63.
The crude pmr was different from the pmr of diene 23.

To a stirred solution of .500 g (2.08 mmoles) of the
crude product in 50 m1 of glyme under an argon atmosphere
at 25° was added .170 gm (3 mmoles) of sodium hydride.

After stirring for 24 hrs at room temperature, water and

72

ether were added and the aqueous solution was extracted
with ether. The combined ether extracts were washed once
each with water and a saturated sodium sulfate solution

and finally dried over MgSO Removal of solvent gave .302

4.
g (70%) of an oil which exhibited the identical gas chroma-

tographic and pmr prOperties as diene 63.

3,4-Dimethy1-5-(1'-hydroxyallyl)bicyclo-
(2.2.210ctan-2-one (£3)—

 

 

To a stirred solution of 1.4 g (5.55 mmoles) of alde-
hyde 63 in 100 mL of THF at 25° was added 6.7 mL (15 mmoles)
of 2.25 M vinyllithium in THF under an argon atmosphere at
25°. After 4 days, the reaction mixture was poured into an
ice-water mixture. The aqueous phase was extracted with
ether and the combined ether extracts were washed twice
with water and once with a saturated sodium sulfate solution

and finally dried over MgSO Removal of the solvent gave

4.
.920 g (84%) of hydroxy ketone 45 as an oil, which was homo-

geneous by glpc (4% QF-l, 160°). An analytical sample

obtained by preparative glpc (4% QF-l, 190°) exhibited the

1, 3400 cm_1; pmr

following properties: ir (CC14) 3600 cm-
(CDC13) 6 6.2-4.8 (m,3H), 3.0-1.3 (m,10H), 1.0-0.9 (m,6H);
mass spectrum (70 eV) m/e (rel intensity) 208(6)P, 190(23),
124(31), 123(100).

Anal. Calcd. for C O C, 74.96; H, 9.68.

13H20 2‘
Found: C, 74.92; H, 9.68.

73

S-Acrylgyl-B,4-dimethylbicyclo-
[2.2.2Toctan-2-one (43)

 

 

To a stirred solution of 5 g of manganese dioxide in

200 mL of CH2C12 at 25° was added .500 g (2.4 mmoles) of

keto-alcohol 63 in 10 mL CH2C12. After 24 hr, 100 m1 of

ether was added and the superatant was decanted from the
brown residue. The insoluble residue was then washed three
times with ether and the combined organic solution was
passed through a short pad of celite and finally dried over

MgSO Removal of the solvent afforded .400 g (81%) of

4.
dione 43 as a yellow oil which contained 10% impurities by
glpc (4% QF-l, 160°). An analytical sample obtained by
preparative glpc (4% QF-l, 190°) exhibited the following

1, 1615 cm-1, pmr: (CDC13)

properties: ir (CC14) 1725 cm-
ratio vinyl: nonvinyl protons, 3:17; mass spectrum (70 eV)

m/e (rel intensity) 206(9)P, 156(10), 56(100).

REFERENCES

 

 

011.

H.‘

12

REFERENCES

1. Roy Genders, "A History of Scent", Hamish Hamilton Ltd.,
London, England 1972, p. 112.

2. M. Billot and F. V. Wells, "Perfumery Technology; Art:
Science:Industry", Halsted Press, New York, 1975, p. 87.

3. G. Wolff and G. Davisson, Tetrahedron, 25, 4903 (1969).

 

4. G. Buchi, W. D. MacLeod Jr. and J. Podella, J. Amer.
Chem. Soc., 83, 4438 (1964).

 

5. E. Piers, W. DeWaals, and R. Britton, J. Amer. Chem.
Soc., 23, 5113 (1971).

 

6. G. Prater, Helv. Chim. Acta, 23, 172 (1974).

 

7. N. Fukamiya, M. Kato and A. Yoskikoshi, J. C. S. Chem.
Comm., 1120 (1971). ’—

 

8. K. Schmalzl and R. Minington, J. Org. Chem., 37, 2877
(1972) . ’V

 

 

9. K. Schmalzl and R. Minington, J. Org. Chem., 34, 2358
(1969) . N

10. R. Lee, C. McAndrews, K. Patel, and W. Reusch,
Tetrahedron Lett., 965 (1973).

 

11. R. Lee, Ph.D. Thesis, Michigan State University, 1973;
Ross Lee, Tetrahedron Lett., 3333 (1973).

 

12. H. 0. House, W. L. Roelofs and B. M. Trost, J. Org. Chem.,
21, 646 (1966).

 

13. B. Boeckman, Private Communication.

14. S. Reed, J. Org. Chem., 23, 4116 (1962).

 

15. N. Jones and H. T. Taylor, J. Chem. Soc., 1345 (1961).

 

74

 

”1
id:

21.

22.

24,

25.

26.

27.

16.

17.

18.

19.

20.

21.

22.

23.

24.

25.

26.

27.

75

H. A. P. DeJongh and H. Wynberg, Rec. Trav. Chim. 82,
202 (1963). ”“

 

E. D. Bergmann, D. Ginsburg, and R. Pappo, Organic Reac-
tions, 18, 205 (1959).

 

G. H. Posner, C. E. Whitten, and P. E. McFarland,
J. Am. Chem. Soc., 23, 5107 (1972).

W. F. Gannon and H. 0. House, Org. Synth., Coll. Vol. V,
539 (1973).

 

H. 0. House, "Modern Synthetic Reactions", Second Edi-
tion, New York, 1972, p. 494.

E. J. Corey and J. W. Suggs, Tetrahedron Lett., 31,
2647 (1975). ’V

 

B. M. Trost, H. C. Arndt, P. E. Strege, and T. R.
Verhoeven, Tetrahedron Lett., 32, 3477 (1976).

 

K. M. Patel, Ph.D. Thesis, Michigan State University,
(1974).

G. M. Rubottom and D. S. Krueger, Tetrahedron Lett.,

 

7, 611 (1977).
IV

D. F. Morrow, T. P. Culbertson, and R. M. Hofer,
J. Org. Chem., 33, 361 (1967).

Beil, 7(2), 56.

H. Born, R. Pappo, and J. Szmuszkovicz, J. Chem. Soc.,
1779 (1953).

 

M

APPENDIX

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

33324523243

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I .. I

I 3

I o

A.

 

 

....-- - -—-I

 

 

 

 

L A A IA AL A A [A L A _A IAL A A A I A A _A A I A A A _A I A A A A J A A A A 1 J
... u. . an p. U .0 )0 20 h .

Figure 49. Pmr spectrum of fig.

 

. ' J l
1 l 1 fl 1 .
v v w w J V v v Jr 1 —v v ' v v w v ' V v 1 ‘ n.
L CID I” M .W
00..

« COCI

 

l

v.-

A .. .. ~-m.—...---- -....-

   
 

 

...o' ...”--c- >0.

 

 

b
......_. ...—......— -—- -..

 

- A A l A L A A I A L A A L A A A A I 1 L4 A A l A A J_l LA A A L__A J LL_A J
no to .0 so .... I“ .0 Jo to .. .

Figure 50. Pmr spectrum of 33.

 

 

 

 

 

 

.—-—————-—d

 

 

 

 

 

vfi~~+—v +~ fiv v vfivfiv , -AA- I AA-A i
I; bra III] III) “a! n.
‘0'.
\l
O i
4
!
H 3
O 1
LA A AAA“. . AA AAA- A AA “-... “AAAAA- ”AAAA
I
A A A A 1 A A A x A AA A A 1 A A A A L A A A A .Jl
AAA 1 A AA A I A AA A I: A A A A I A A A A I A At A A I j A A A A A A A I A A If
u re .0 so NW‘ 40 10 u no A #
Flgure 51. Pmr spectrum of 38.
N
1 1 1 1 1 J I l - 1
I "*'* ' T * ‘ 'ir ' 'r' * 1 ' "‘ r*1" " 1
‘4) an AM I‘D MI: “I.

 

 

 

 

 

 

 

 

 

AA A r4 A .A _A r A A l A A A LA I A A A A I A A A A I L A A A I A_ A A A I A A A I A
.0 To u so he WT u u u -o u

Figure 52.

Pmr spectrum of 3—methy1cyclohex-2-enone.

 

H.—

II

 

 

 

 

 

 

, A
1 l A r l A I . l 1
A l A A A J A A A A A T A A A A I . . I A I A I
u 70 u m p.7TT no .u N la a
Figure 53. Pmr spectrum of 3-ethoxy-2—methy1cyclohexenone.
T I ‘ “I” ‘ ‘

 

 

 

 

 

A A l l ' J A_L
Al . A1 A I A T . l A A i .
In In au I

! A_ L;
r“ i
1

Figure 54. Pmr spectrum of 2-methylcyclohex—2—enone.

 

‘d
g-t

c0205

 

 

. A I
m '0‘ 4.

Figure 55. Pmr spectrum of 23.

 

 

 

 

 

 

 

 

 

 

 

1 l I
If L 1 I 1
“ w m
0
O
. A- - AMAAA ..l A— A- AA . A. AA.A.A.-A A
. v—nnwwuv- lv-‘W'V vn . 7 .
J A I l l . . I l
A I I I I A I A I I A A 1AA l
n In 50 :o p. ‘ no )0 70

Figure 56. Pmr spectrum of fi3°

 

 

 

 

v is. T A- vvlvvffirf"1 ‘*'**' I ' "'fi'

L .‘ll :- I. NI! vi.
1....

t

‘.

c02013 a.

H
Irv“ "
i i
‘ I, I
r’.‘

A; A; A l A A A J A A14 A i . A; A 1 r A A l

A..__AAA [A4 A A LLAAA {#A A A I A AAAlAAA A_I l A AAIAA A A [A A A AJ

no to u so mm on so u w o

 

Figure 57. Pm: spectrum of 335°

 

 

 

 

 

 

 

 

 

 

F—AA J I 4 A J A J A A A A I A A L A J L A A A I A .1 A J I l A _A A l A A A A I A A A L l
u n u to "AT" u so n I. 0

Figure 58. Pmr spectrum of A2,.

 

A
“Y

.0

1
v v— V j r v v v I v v

CfiFM

OH

 

 

1b-

no

 

 

 

 

 

 

AL A A I A A r l . r r L J r A . A l I - :4 A . l - . 1
AA A I A A A .A 1 A A A A l_A A A A I J A A j A A I l A A A I A A A A 1 A A A l A
if n u u m I" u u u no c
Figure 57. Pmr spectrum of 46.
A 1 'I
I V W r ' ' ‘ ' '7 ‘ T‘V r v—Tfi rf1 f r v v T r t v v I v 1 v v ‘ v—r—v 'lfi
it'll «'0 I.» no M. uh

 

 

 

I

 

 

 

 

 

 

 

 

 

A A A A A A A A_ A l A A _L A A L A L A A A l A A A A '
AA I A A A A I A A A _A I A L A A I l A A A I A I A A I A A A A J A L A A_ I A AA A I A
no 70 no so p... "I co )0 u to 0

Figure 60.

of 47.
Pmr spectrum /v

 

125

\O' W all :0 no - n.

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

A A 1 A I
AA A [A A A. A r A A _A A7 A A A A r A A A I A A AA A l L A A A I A A A A 1 AA A A I
no to so so m. H‘ u w )0 n Io a
Figure 61. Pmr spectrum of 48.
N
A j - 5 V v A j - ; w v fvg v 1 v r v ' f ' 4'" V ‘ I 1
)TN 10 Do In In "N!
0. |
O .c
I
i
O ‘-
l-
.l
J A A A A A L A A A A l A A A 1 A A. A A 1 A A A 1
AA A I A A A. A I A A A A I A A A A I A L A A A A A A I A A A A L A A A _A 1 A L A A I
no I0 co so m "' no )9 to '0 .

Figure 62. Pmr spectrum of £3.

.122 .

 

 

 

 

 

 

 

. '1
r‘ v ‘ 1. ‘v 1. .1 ~' 2..
ill.
I
CHZOH .
-1 H I
H
H0 l
__////,n l
L A l 1 l 1. l 1 . l I
-1 1- . r 1 I - 1 I. 1 1 . 11 . -1 1 FT
u to u w "fit .0 u n no a
Figure 63. Pmr spectrum of 23'
L 1 1 L nj i r1 $ ‘ 1 L ‘ u-
g"
1

V

 

I —n W v-v ' v- V

:Z] CHO
. H‘éz’fi"
H 1
o l
i
\

.. ..A_u i1A_. A...‘ L ... . ...J
m.

 

 

L1 1 1 1 1 l 1
4-j— AI 11 111 .I1_.1.I.11.I . I
u u .o u on?" u u n In
Figure 64. Pmr spectrum of 51.

s—— ~w ..

 

 

 

 

 

 

 

 

 

1 1 1 ' 1 1 I” 17* - 11‘
‘f VrVVIV—V'V'V V vvfi' I‘j’ fTV—V‘V I W fififififi
In «To an a» m: w
M
1"“.
r
l
I
I
I,
H ,;
-1 on I
I
I"
I.
'I
‘1 L _._AA A l A A'- L 1 AL AlJ A l 4 IALA l A _4 Agl
LALIAA AJIALL_AIAA_A A+l LA A A1414LI 14A A AAA ALLJAA [J
u n u 19 min a so u u o
O
Plgure 65. Pmr spectrum of 54.
a vvv ‘f f V1 VVVVV lijv—Trvw—Vr r Liv—vrv—vfiftvvjrfivv ‘v‘
hr» ll 8'. M MAI um

_—_: ~"_*”M

_-
...:

 

 

 

 

 

 

 

. A L I 1 1 4 - r . I A 1 1 LA I . A I 1 1 A J 1 L 1 _ I
L4 A l A A A A r A A AA A r A A A A I l A J L I A J A A A A‘A A I A A A A I A A A A I A
co )0 on so u... “r .0 so u I. o

 

Figure 66. Pmr spectrum of g3.

 

 

 

 

 

 

 

 

l A A LA A L A A A A l A ' A A J A
LA. AL A A A A 1 A A A A I A__ A A L I AA A A I A l A A I I A L A I A A A A LL A A A I A
no in on H. ... ”j u )0 H I. o

 

Figure 67. Pmr spectrum of ’53.

11—
b
_

 

4

1

4
cu“-
l

_—

 

 

 

_.L—erc.—r ....-."r
—“ '

\

 

 

 

 

 

 

 

—A_ L _ _ A A _ .-. AA ..L- -AL A .-__ A- A... AAA. ‘A A L L I A A...-
v V— w— ‘
WV .— v—vv v— v v w v r VT V"
A A A A l L A A l _A L J. l A L A A A l A A LA
LL 4 r I r I
A A A A A A A A A A__ A- A A A A

 

 

‘
*‘3 fill

 

 

 

   

 

 

' A
I A ALA—A L l A A A A A A A1 A A 1 A A l A AA AA A

. A A 1
L Li A A A A I A A A _A r A A A A l l L A A J L l A AI L A A A 1 A L A A I A A A A F‘
u u oo :o p... "T u _u u u o

 

Figure 69. Pmr spectrum of 23.

 

CN

O:Si+

 

 

 

 

 

 

 

A L I _A A A A_ 1 A AA A A I A L A A 1 LA A_-A_ A A A A A l I A A A r A AAA_ A A A A L LA
I. n u u on 'W _u u n M

Figure 70. Pmr spectrum of 23.

 

 

 

 

 

 

 

   

 

 

 

o ‘ I L
l *— r v 1v: v * v f l V f—V v 1 V' V V ' ! i T V Y *1 v v V W I
VL'fw'jfl» "I 77 L ' i m a.
U”
H
C02CH3 .
b
' I
OSI+
l
v V—v w—v—A A w— “ WAV fi 1 , A:_r__ ‘_ V #V A
.l _A A A A l A A l A _A l A A 1 A A I A A l L A l A .A 1 AA A
. A A rA A A A LA L A A I A“A A A l A A A A l A l A A I A A AA A I A A A A l A A A A
a 05 u u up. 7" u u u

 

Figure 71. Pmr spectrum of £9.

 

‘»

 

l J
v— v v I v v v rvf V fi— w I
in! Cu .0

 

 

 

 

 

A_ r A A A Ll A A A A I A. A L A I A A A A A A A A [—1 A A A I A A A A I A A A A A
u n u so In W n so u u 0

Figure 72. Pmr spectrum of §$°

I“

 

CHO

OSiE

rv—w— WV— vv w v

 

1

"owfio .—-..O ‘- ..--q

I .

i

.o-‘o

“I. l 'fil-I

 

 

 

 

 

A L A [A A L A I A L A A I A A A A I L A A A I A l A A I l__ A A A LA A A A l A A 1 A
no lo .0 so ".7” u )0 u I. 0

Figure 73. Pmr spectrum of Q5;

 

 

 

 

 

 

 

 

a fi— v f L r V f 5 V fi' V § * v V y 5 W v f ‘ v ‘ 7’1 v f 5 V ' V V 5 T V :
bu *0 u u no V.
mo
4 CN i
!
I
i
OSiE ~
2 i
I
r v V A‘ k f L
l - A A A A A I A A A l A ' l l
L A A FA A A —A L A A A A I__A A A L I J A A A A J A A J A A A l A A A A r A A1 _A
no to 00 90 m n1 4. )0 10 N 0

Figure 74. Pmr spectrum of 23.

"""'" _._ —

 

1311

 

}.

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

1'
o
l A _A L A A I A A ' l A A 1A_ A A l _A A AAA 1 A A 1.
AA A I A A A A I _A A A I A A A A I AAA AL A L A A I A A A AA A A A A I L A A A I A
u to u w an. “1 00 u u u u
Flgure 7S. Pmr spectrum.o£ 64.
l l
Ivvvw s -5j. - I r-‘.fi£-vvi , .,.<.rr, - ,vr - ,
I v 0‘” I'- 1 Mb ...u
0..
CH OH ,
_ t
C
H 3
o 1
i.
I
LAAAAA - 1A- AAAA l AAALAAA 1A A A l
A AA A r A AA AAI J A A A A LA A I A A A A I A AA A I A A AA] A
u n u so mm a u u u u

Figure 76. Pmr spectrum.of £3.

_""""" —

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

J 1 L l
I“ vvvvvv I f vwiffifl""1' '
a! an M
q
LAJoAA14.A--1 - -A- -_L.A1-A‘1A. -L
AAAIAAAA‘VAAAAIAAAALAAAAA]AAAArAAALIAAAAIAAAAIA
u n u so m'“ u u u u 0
Figure 77. Pmr spectrum of 68.
L l l l A VIT ivv¢7rvf'—V‘fi
. Viv . . Vi vvvvvvrr~vv1v vvaw l
I. L in no no on.
u.

 

 

 

 

 

1 A - A . l- - .4 - A J A A1; - 1 - - 14 A 1A A - 1 - - J
L4 [ A A A. A I A A ‘A L I A A .AAA l 44 A A L A A T A A A A I A A A A I A A A A I A
u n u u a. W n u to co 0

 

Figure 78. Pmr spectrum of 93.

 

 

 

 

 

 

 

 

 

 

' L L ' f I i '0“
I o
I
I
I
l O
I
I
I
I
‘I

J L A a l I ‘i | I l.i. I 1 Ir '

Figure 79. Pm: spectrum of £3.

H
COgma
H

[U

‘?

e .

\st

.5

34

k I

‘ , I I ‘

“1° I ,I ”I ~’ i l

M“ “i ii” 'I' ; III. ,I. "I I. i.
do u- to I.“ _LIJ’H' “MAM“ ll ’0 U H n
M/{ I v-n ’y‘ IUI‘

Figure 80. Mass spectrum of £3.

136

cozcus

m 36 , .

( 0
O! (I U1
..nibxm‘iumk‘iu How? v

J-ut

Jar

III‘

”e

mi.

Ami)
la
la

Mass spectrum of 24

 

Figure 81.

~

I\"

 

a. .u u .u h

N‘QVXKme‘UK‘iIN‘ .Ja\L.\NWN—_\

II Illixllll .IIIL.

Figure 82.

~

Mass spectrum of 26.

...-— iii-'—

 

137

 

1
ll‘fl

.l 0"

l4”

u n [#0
"/c,

 

W”

St‘

 

[N

a...

. 5030.}.

z. w

\uuAN m. a c 3mm

 

Figure 83.

Mass spectrum of 27.
N

 

 

ab

:40

220

MD

130

6::

 

 

 

“’1

3.

b w u x

.. xxx “KHAN .mxtxqu

a.)

Mass spectrum of zv.

Figure 84.

138

 

 

 

 

 

 

 

 

O
O
I
I I p
lid :00 220

Figure 85. Mass spectrum of 23.

I00
:3 I I
b 8” I I
2% I 1
)- I I
Ix be I
I I I
h I z I
:: “° I I I
Q:

I I I I I I I
no I. II I II I I I' I :
II I II I . I; I II
“I IIII éoII JIIO II M! IIOI . "OI-I “I. w 2” m 7” “o

m/e

Figure 86. Mass spectrum of gi.

139

 

 

1"

m w v m A
“finxns... ‘NKiIIN. Vicmtlm‘

Jim

2w

Jay

1‘5

lb

‘0

 

Mass spectrum of 36.

Figure 87.

COCI

360

I.

2:-

(to

 

 

 

NI m a wfi MI

N

Mass 8PGCtrum.of 35.

Figure 88.

C02“

140

 

1“ 4‘9

3J0

COCI
I
A

 

Ibo

 

 

 

III 6 W
I. I. a I
e ,fl
#7 m
A. IIII IHIHIWIIIHIA M
I III; I
/

Mass spectrum of ;§.

III;
III. . -
IIIII .
l. I III II I III. I.. .
' | I
'I III I
I III 'I'IQI I \llllll- II- ... I III. I I'm"
I ||IIIIIII III | ..Il.
.IIII I|||Ilv I .
IIIIIIIIII IIIII
III.‘
-IIIIBII C.I
'III II.

 

I
I
I
I
HI
Figure 89.

uII .w u k.

W n. 0 W ..c
'8 6 A I ”
«v5» \kGKthN harstxumo/x \s¢\\«x..m.oQI..<.N Hike..-

 

A!

Mass spectrum of 37.

Figure 90.

141

...-

I IIIIII III I”

.l IIHHHUHH

Jan 440 :6.

20.3

Lo '60

no

‘0

 

.‘l Il‘l’ III .Illl.
III'C .-I’I‘Il’!

w w . u u
3X \xuulwtnN wacimcz

'IIl‘-

“Mass speCtrum of 33,

Figure 91.

III‘III'I."

 

 

8|

5.:

 

m I n w w - m
«\$\\A.M.Vwk\<.N WAC‘VM‘

Mass spectrum of 3~methy1cyclohex-2—enone.

Figure 92.

142

#0

£4" : ’7
d
v

IN

§
Q

[5" ’17.“? fat
'3

 

 

 

).
Q5
cg
'3 “fin—......
L._ -..... ..

 

 

 

 

 

I I

Iv ‘3 a
”/2 I” If M

 

Figure 93. Mass spectrum of 3-ethoxy—Z-methylcyclohexenone.

 

mandarlbnwohxzfi)
C‘
0

 

 

 

,w (if
«I ‘
2WIIIIII

 

 

,«m n O we

Figure 94. Mass spectrum of 2~methylcyclohex—2—enone.

 

143

 

 

 

 

 

cqcn,
O
E
f.
i?
‘3. a.
3.
§.
I I II
" ' I I II I
I I" Ii a"
.‘IIII‘IIIIIIIIII "..I... ‘
a In mans/L420 I Ibo I :0 44. :4;
Figure 95. Mass spectrum 01 ‘33.
O

1354: m: I.-1u«..ym;
° a.
o e E

~§
e

u
D

 

 

 

III

4 I in In, I) a" I? r /b o
nYfi,

 

 

 

[[0

Figure 96. Mass spectrum of :13.

 

3
a.
O
c

330

JOJ
H

Ito

 

~

loo

Ho

 

 

 

 

I.I..M 9
4 I u~
4 [Ill-I'll...
l
f
m 0 II
III e
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m
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I c I
III I III IIIIWLIM e
I II I I I I I I-. p
I..“ I
I ”URI 8
.thfl m I I II III.1

 

I

 

LI—
(no

 

 

 

 

 

 

 

 

 

O
7
9
.MHIMMM e III
.II m. IIII
II .« I90 II
m e u m N n M w w ...I a

«aebgflwfiw uxc§mms Tee \u..9.muih Insc3wp<

lao

/¢'0
Mass spectrum of 42.

 

Figure'98.

145

CH20H

OH

 

 

 

 

 

 

 

 

.u
/

O
0 IV

4
Sr x XL 533..“ fist

W
3.4

110

A."

 

   

 

 

 

 

 

 

 

 

 

0
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Ilium
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I 0
Ah a
IJ
M. .w
I-II..fl /
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t -. m
c
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P II- III.
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8 IhI
8
a
M III w
9 I
9 0
I I I.
e I.”
r
m II .
I I a.
P m w w. W n

I l
3 t9 3?“ $3 ‘3‘

Figure 100.

N

Mass spectrum of 47.

 

145

CH20H
no

OH

 

 

[‘0

Ho

      

t
Mass spectrum qt 5"

 

I

 

I10

 

IN

 

 

 

 

I o o
M 4 6 W.
sue \ \L 5th ....H $42.33*

‘9

Figure ‘99 .

 

 

I

 

 

 

I'll-I'll.

.0 O 0 O
M on lo 0: .4

I ~&\\k..w.auth lax 3m%

220

I!"

[to

 

Figure 100.

N

M335 Spectrum of 47.

146

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

OH
0
[c0
3
2w
93
S
c:
”I I I
5"". I 3
(K I I
II ' I
2a I I I ',I III. I I
I II 'II: II I II
I I I I II' ' I
' IIII III I I I
‘ 60 IL- 'f” /0l.’I l.“- V" L loo lb’O 1149'} .2):- “0
‘7‘ ' m/e’
Figure 101. Mass spectrum of :33.
O
/0‘9 I
I I
3‘ I
5.9" I
‘3 ow I
5‘:
é II
.24» I
II
.10 II I '
I I
- | fr lofl I u- LAH—'7‘.” [no LI am- 220 175
‘l« m I”'/(

Figure 102. Mass spectrum of 53.

 

 

 

147

CH20H

\
a
0 3

LA fipé Iv'a's ”7 ”-J
"s %

,.
*E

U
h

 

 

 

 

 

 

 

IIJIIIIIII IIII

_1
(I o (I
t v: ”a “/K [A ”a /40 I!

Figure 103. Mass spectrum of. ’58.

CHO

§

m
V.

 

“fl/E IMvSJy (fin)
a
§

pfi’

‘3
U

E

 

 

--...—

B

 

 

 

 

9C, ‘0 9" I00 “/2, [20 Ala [$0

I
. I I
I“. . I: I II I II III] I I [Ila

loo 2.10

Figure 104. Mass spectrum of (5%.

 

 

148

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

OH
III

.1

I I

.. II I I I I I

III I
,0 II II III I I II I
III II , - A ‘

4. to In ”We.” Mo 10 duo .120 we 2o
Figure 105. Mass spectrum of 23-

I
go
‘3 I
Ii“ I I
I II I I
5””I I II .
a II III III III III I III I I
. I III II I '

.II III II IIIIIII IIIII III II I I I III II

ya,- so y" me a No / a no 2w 23a .u

 

 

Figure 106. Mass spectrum of ’53.

149

 

/¢‘(’ I
'> I
i“ l
>~ I
‘5 I
I4
Q
Em= I
E I
g 1 I
m ' I I
’~< I r I
I I ‘ I
A’ ' I
I
II II" I
‘LIJIIILLILLLILII I I II I III II II
to d. u r u p ”.1 M [UI‘ J u “a ,7 y('

m/(
Figure 107. Mass Spectrum of g3.

 

 

 

 

 

 

 

 

I

I

‘\’..‘_’I

I
, .

J‘ I I I
IIILLILIIIIIJIJ II I II I

 

mfiaII

Figure 108. Mass spectrum of 23.

 

 

E

.0
O

(2‘07": frm’ 50'” $2
‘3

 

...:
Q

 

 

 

 

 

Figure 109.

 

 

 

 

 

150

III/“III I J I

“" N" /¢o

Mass spectrum of £3.

 

 

 

 

 

J
1" #110 “(yo

 

['0
I? .
t I
‘50. I
“ I
E I
3 ‘lo I
\u I
°‘ I

)0 I

IHJII “MI IU m 1 I L Aifl I Ii_I L
b0 C" I” In In {‘6 no 2» .ua M In a to
Vin/c
Figure 110. ”Mass speCtrum of 58.

~

 

cu
oss+

151

 

 

III II I lilfl NH

2‘0

 

J)?

 

 

W
J
m. H3
C
m r. Ian
0
H
m
m
IIMR

.I' III!

.%¢
Mass spectrum of 19’.

~

f 60.

Mass spectrum 0

 

 

 

 

 

 

I 1 I
II I II I II I,II-L 1
IHHI II IIIIIIIII- IiJ v _.I.—
I
m
I I IL We
IIIIw--III.IIII..II I III M m ... II I I Is I.

Q to.) .mI. 4H m:3.u.x 3 {arches ficfimw

JO

Figure 112.

 

152

cozc H3

05I+

 

Figure 113.

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