STUDiES TOWARD THE TOTAL "SYNTHESIS 0F * f *

TETRACYCLlC TRITERPENES

Dissertation for the Degree of Ph. D.
MICHIGAN STATE UNIVERSITY
V JERROLD LEROY MARTIN, JR.
' 1976 '

 

‘31:, arse-13mm
'. t -
7

This is to certify that the
thesis entitled
Studies Toward the Total Synthesis

of Tetracycllc Trlterpenes

presented by

Jerrold Leroy Martin, Jr.

has been accepted towards fulfillment
of the requirements for

Ph.D. degree in Organic Chemistry

 

 

741.

Major professor

Date g1] ZB/ 7‘

0-7 639

ABSTRACT

STUDIES TOWARD THE TOTAL SYNTHESIS
OF TETRACYCLIC TRITERPENES

BY

Jerrold Leroy Martin, Jr.

Perhydroindenedione l is a potentially useful start-
ing material for the total synthesis of lanostane and
euphane triterpenes.

The carbonyl function in the six-membered ring of l
was reduced to an axial alcohol and formed adducts with
Grignard reagents and ylides in the presence of the
unprotected carbonyl group in the five-membered ring.

By making use of this selective reactivity, derivative é

was synthesized.

llnBuLi
2)CH3I

 

 

 

CH3O

 

Treatment of 3 with diisobutyl aluminum hydride yielded

alcohols 3 and §.

Jerrold Leroy Martin, Jr.

(iBU)2A|H

 

{w

 

CH3O

 

Epimer 5 showed an eight-fold preference for water
loss (M-l8) in its 15eV mass spectrum, relative to §;
however, mass spectral analysis of several deuterium
labeled analogs of 5 and E failed to explain this phe-
nomenon. The configurations of 3 and § were assigned by
a comparison of the methyl shifts in their proton mag-
netic reSonance spectra with known angular methyl shifts
for the 5a,l4a-androstane series.

Approaches to building a terpene side chain onto §
were explored. Although the carbonyl function in § resisted
the addition of a wide variety of nucleOphilic reagents,
it did form an adduct with sodium acetylide. This adduct
was completely resistant to all efforts to transform it
into useful intermediates. Treatment of § with lithium
ethoxyacetylene resulted in an unprecedented condensation

product:

LiCECOEt _

 

,3.

 

Jerrold Leroy Martin, Jr.
Allyl magnesium bromide and crotyl magnesium bromide
both formed adducts with §. The adduct resulting from
the crotyl Grignard reagent was transformed into a
B-hydroxy ester side chain similar to that employed by

other workers to elaborate a terpene side chain:

 

STUDIES TOWARD THE TOTAL SYNTHESIS
OF TETRACYCLIC TRITERPENES

By

Jerrold Leroy Martin, Jr.

A DISSERTATION

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

DOCTOR OF PHILOSOPHY

Department of Chemistry

1976

39 Copyright by
Jerrold Leroy Martin, Jr.

1976

This dissertation is dedicated to my
parents, who have provided a continuing
source of love and inspiration, and to
my future with Sally.

ii

ACKNOWLEDGEMENTS

The author is indebted to Professor William H.
Reusch for his instruction, for his vigorous intellectual
example, and for his sincere counsel.

To friends in the lab and elsewhere, past and
present, the author extends his gratitude.

The National Institutes of Health and the Department
of Chemistry at Michigan State University generously

supported the author during the course of this work.

iii

TABLE OF CONTENTS

Page
INTRODUCTION. . . . . . . . . . . . . . . . . . . . 1
RESULTS AND DISCUSSION. . . . . . . . . . . . . . . 9
A.. Survey of Carbonyl Reactivity in l . . . 9
B. Approaches to Side Chain Synthesis . . . 19
EXPERIMENTAL. . . . . . . . . . . . . . . . . . . . 33
General. . . 33
Preparation of 2- -Methylcyclohexan- l, 3- Dione. 34
Preparation of 6- -Methy1bicyclo[4. 4. 0]dec-
1- -ene- 3, 7- Dione. . . . . 35
Preparation of (IR*, ,SaGBf-S -Hydroxy- ~6-
Methyltricyclo[4.4 5]decan.9 One. . . 36
Preparation of 1 . . . . . . 37
Preparation of Z . . . . . 38
Preparation of 3 via n-Butyl Lithium and
Methyl Iodide. . . . . . . . . . . . . . . 39
Preparation of 3 via Dimsyl Sodium and
Methyl Iodide. . . . . . . . . . . . . . . 40
Preparation of 4 . . . . . . . . . . . . . . 41
Preparation of 3 . 41
Preparation of 6. . . . . . . . . . . . . . 42
Preparation of Z and 3 . . . . . . . . . . . 43
Preparation of 9. . . . . . . . . . . . . . 44
Preparation of IQ. 45
Preparation of 11. 47
Preparation of 13. 47
Preparation of 14. 49
Preparation of 15. . . . . . . . . . . . . . 49
Preparation of 16 and 12 . . . . . . . . . . 50
Preparation of 13. . . . . . . . . . . 52
Preparation of 12.52

Preparation of ZQ and 21 : I : : I I I : : . 53

Preparation of Z- . . . . . . . . . . 54
Preparation of 23 and Z6. . . 56
Treatment of 3 with Isopropenyl Lithium. . . 58
Treatment of 3 with Vinyl Lithium. . . 58
Treatment of 3 with Vinyl Magnesium Chloride 59
Treatment of 3 with Methyl Lithium . . . . . 59
Preparation of 22. . . . . . . . . . . . . . 60

iv

Page

Preparation of 29 from 27.. . . . . . . . . 61
Preparation of 29 and 39 from 3.. . . . . . 62
Treatment of 29 with Pyridine--Si1ver

Nitrate. . . . . . 63
Treatment of 29 with Ethanolic Potassium

Hydroxide. . . . . . . 63
Treatment of 29 with Potassium Tert-

Butoxide . . . . . . . . . . . . . . . . 63
Preparation of 32. . . . . . . . . . . . 64
Attempted Thermolysis of 32. . . . . . 65
Attempted Conversion of 3 to a Homologous

Unsaturated Ester Using a Wittig Reagent . 65

Attempted Conversion of 3 to a Homologous
Unsaturated Aldehyde Using a Wittig

Reagent. . . . . . . 66
Attempted Conversion of 3 to a Spiro

Epoxide. . . . . . . 66
Treatment of 3 with the Lithium Bnolate

Anion of Tert- Butyl Acetate. . . . . 67
Treatment of 3 with the Lithium Bnolate

Anion of Tert- -Butyl Trimethylsilylacetate. 68
Treatment of 3 with the Lithium Bnolate

of Ethyl Acetate . . . 68
Treatment of 3 with a Reformatsky Reagent. . 69
Preparation of 33. . . . 69
Recovery of 34 from the Treatment .of 33

with Formic Acid . . . . . . . . . . . 70
Regeneration of 33 from 34 . . . . 71
Recovery of 33 from Treatment of 33 with

Sulfuric Acid-~Acetic Acid . . . . . . . . 72
Preparation of 33 from 33 in Pyridine--

Acetic Anhydride . . . . . 72
Treatment of 33 with Mercuric Oxide and.

Aqueous Acid . . . 73
Treatment of 33 with Mercuric Sulfate and

Acetic Acid. . . . . . . . . . . . . . . . 73
Treatment of 33 with Mercuric Acetate. . . . 74
Treatment of 33 with Mercuric Oxide and

Aqueous Acid . . . . . 74
Attempted Reduction of the Ethynyl Group

f33 using Lithium Aluminum Hydride . . . 74

Attempted Reduction of the Ethynyl Group

of 33 using Diisobutyl Aluminum Hydride. . 75
Summary of the Attempted Catalytic Hydro-

genation of the Ethynyl Group of 33

under Several Conditions . . . . . 7S
Attempted Claisen- Cope Rearrangement of 34 . 76
Attempted Claisen- Cope Rearrangement of 33

by Flow Pyrolysis. . . . . . 76
Attempted Ag(I) Catalyzed Claisen- Cope
Rearrangement of 33. . . . . . . . . . . . . 76

Page

Conversion of 33 to a Phosphite Ester
(3g) and Attempted Thermal Claisen-

Cope Rearrangement of the Derivative . . . 77
Attempted Conversion of 33 to a Chloro-
Allene with Thionyl Chloride--Pyridine . . 77

Attempted Conversion of 33 to an Allene
using Lithium Aluminum Hydride--

Aluminum Trichloride . . . . 78
Attempted Conversion of 33 to a Methyl-
Substituted Allene . . . . . . . . . . . 78
Preparation of 32. . . . . . . . . . . . . . 79
Preparation of 33. . . . 80
Treatment of 3 with Allyl Magnesium Bromide
in THF . . . . . . . . . . . . . . . . . 81
Preparation of 39. . . . . . . . 81
Preparation of 49. 82
Preparation of 43. 83
APPENDIX. . . . . . . . . . . . . . . . . . . . . . 86
BIBLIOGRAPHY. . . . . . . . . . . . . . . . . . . . 200

vi

LIST OF TABLES

Table Page
1 Assignment of chemical shifts (ppm). . . . . 18

2 Calculated and observed A (61-66) values
(ppm). . . . . . . . . . . . . . . . . 18
3 Reagents which failed to form adducts to 3 . 23

vii

11
12
13
14
15
16
17
18
19
20
21
22

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

Infrared

LIST OF FIGURES

spectrum
spectrum
spectrum
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viii

Page
86
87
88
89
90
91
92
93
94
95
96
97
98
99

100
101
102
103
104
105
106
107

Figure Page
23 Infrared spectrum of 23. 108
24 Infrared spectrum of 26. 109
25 Infrared spectrum of 27. 110
26 Infrared spectrum of 29. 111
27 Infrared spectrum of 30. 112
28 Infrared spectrum of 32 (CDC13). 113
29 Infrared spectrum of 33. 114
30 Infrared spectrum of 34. 115
31 Infrared spectrum of 33. 116
32 Infrared spectrum of 36. 117
33 Infrared spectrum of 37. 118
34 Infrared spectrum of 38. 119
35 Infrared spectrum of 39. 120
36 Infrared spectrum of 40. 121
37 Infrared spectrum of 43. 122
38 Pmr spectrum of 1. 123
39 Pmr spectrum of 2. 124
40 Pmr spectrum of 3. 125
41 Pmr spectrum of 4. . 126
42 Pmr spectrum of 3. 127
43 Pmr spectrum of 6. 128
44 Pmr spectrum of Z. 129
45 Pmr spectrum of 8. 130
46 Pmr spectrum of 10 131
47 Pmr spectrum of 11 132
48 Pmr spectrum of 13 . 133
49 Pmr spectrum of 14 . . . . . . . . . . . . . 134

ix

Figure Page
50 Pmr spectrum of 15 . . . . . . . . . . . . . 135
51 Pmr spectrum of 16 . . . . . . . . . . . . . 136
52 Pmr spectrum of 17 . . . . . . . . . . . . . 137
53 Pmr spectrum of 18 . . . . . . . . . . . . . 138
54 Pmr spectrum of 19 . . . . . . . . . . . . . 139
55 Pmr spectrum of 29 . . . . . . . . . . . . . 140
56 Pmr spectrum of 21 . . . . . . . . . . . . . 141
57 Pmr spectrum of 22 . . . . . . . . . . . . . 142
58 Pmr spectrum of 23 . . . . . . . . . . . . . 143
59 Pmr spectrum of 24 . . . . . . . . . . . . . 144
60 Pmr spectrum of 25 . . . . . . . . . . . . . 145
61 Pmr spectrum of 26 . . . . . . . . . . . . . 146
62 Pmr spectrum of 27 . . . . . . . . . . . . . 147
63 Pmr spectrum of 29 . . . . . . . . . . . . . 148
64 Pmr spectrum of 39 . . . . . . . . . . . . . 149
65 Pmr spectrum of 32 . . . . . . . . . . . . . 150
66 Pmr spectrum of 33 . . . . . . . . . . . . . 151
67 Pmr spectrum of 34 . . . . . . . . . . . . . 152
68 Pmr spectrum of 35 . . . . . . . . . . . . . 153
69 Pmr spectrum of 36 . . . . . . . . . . . . . 154
70 Pmr spectrum of 37 . . . . . . . . . . . . . 155
71 Pmr spectrum of 38 . . . . . . . . . . . . . 156
72 Pmr spectrum of 39 . . . . . . . . . . . . . 157
73 Pmr spectrum of 49 . . . . . . . . . . . . . 158
74 Pmr spectrum of 43 . . . . . . . . . . . . . 159
75 Mass spectrum of 1 (70 eV) . . . . . . . . . 160
76 Mass spectrum of 2 (70 eV) . . . . . . . . . 161

X

Figure

77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
102
103

Mass
Mass
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Mass
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163
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172
173
174
175
176
177
178
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182
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104
105
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Page
189
190
191
192
193
194
195
196
197
198
199

INTRODUCTION

The tetracyclic triterpenes and steroids constitute
an area of vital interest to synthetic chemists. Their
synthesis and modification pose a challenge which has not
only tested and refined synthetic strategies, but also
has led to the development of novel reagents or reaction
conditions. The marked physiological properties1 of some
members of this group is an additional enticement in
capturing the interest of the researcher.

Every successful synthetic strategy has as its founda-
tion at least one specific transformation or versatile
intermediate. In this study, the availability of trans-
1,6-dimethy1bicyclo[4.3.0]nonan-2,7-dione2 (equation 1)
prompted consideration of the total synthesis of the

lanostane and euphane/tirucallane triterpenes.

O I) NaOH '

2)CH31 base
(I) 4r "'—"""'*
IMVK
C) C)

 

KO+|

AL

   

2
The tetracyclic triterpenes and steroids3 are formed in
nature by enzymatic cyclizations of squalene,4 followed
by rearrangement and loss of methyl groups. A chair-boat-
chair-boat folding of squalene leads to the lanostane
system, whereas a chair-chair-chair-boat arrangement leads

to euphol and/or tirucallol derivatives.

lonosterol tirucallol

 

Treatment of squalene 2,3-oxide with an appropriate enzyme
in the laboratory has in fact produced a mixture of lano-
sterol and cholesterol.5
Non-enzymatic, acid-catalyzed cyclization of appro-
priate polyene intermediates has also generated the lano-
stane skeleton. Thus, a polyene monoepoxide with a pre-
formed D ring was cyclized to parkeol while the correspond-

ing epimeric epoxide was cyclized to isotirucallol:6

  

porkeol isotirucollol

Cyclization of another polyene monoepoxide with a preformed

CD moiety led to a dihydrolanosterol precursor:7

(3)

 

 

J dihydrolonosterol

The euphane/tirucallane skeleton probably cannot be

obtained by such polyene cyclizations, because of the ease

4
with which compounds of this family undergo acid-catalyzed

8
rearrangement:

(4)

   

AwC)

euphenol acetate isoeuphenol acetate

Another successful approach to the synthesis of 14a-
methyl steroids and triterpenes involves the methylation
of lS-keto intermediates. This strategy was used in the
first synthesis of lanosterol (from cholesterol)9 and was
also used for the preparation of l4a-methy1testosterone

and 14a-methylprogesterone analogs.10

  
  

(5) CBHV

  

I) PhCOCI, Py
2) t -BuOK_
3) Me! 7

 

The use of 1 as the basis for a total synthesis of

the lanostane and euphane triterpenes is particularly

5
attractive since it would avoid a l4a-methylation step.
Such a total synthesis would necessarily be conducted in
two parts. First, the A and B rings must be joined to
'appropriate sites on the six-membered ring of 1. Second,
a side chain must be attached to the carbonyl function of

the five-membered ring:

(i/attoch side chain

  
 

attach
ringsA and B\ O

A literature search disclosed three general strate-
gies which have been used for building the eight-carbon
cholestane side chain. The first strategy, utilized in
Woodward's cholesterol synthesis,11 proceeds by a conden-
sation to form the D ring, elaboration to a pregnane
side chain, and addition of an isohexyl unit as the alkyl
magnesium bromide (equation 6). The isohexyl unit has also

been added as a Wittig reagent.12

 

base ’8

)several steps

1

several C)

steps
+_+_ .

 

 

cholesterol

The second strategy results from a combination of two
independent studies. It proceeds by addition of an iso-

13 followed by a Wittig

hexyl unit to a carboxylic acid,
reaction, and a stereoselective hydroboration14 (equa-

tion 7):

 

2)H202

l)TsCLFN
4* 2)LiAlH4

 

\\ G>95%S

 

7
The third route, used in the synthesis of the

17

curcurbitacin I,15 ecdysone,16 desmosterol, and vitamin

US18 side chains, proceeds through a C-22 carbonyl func-

tion and concludes with the addition of an isohexyl unit

as illustrated below:

MgBr
In

OTHP

   

l) LiCllH-CH2—-<-OTHP
SOPh¥

  

2M: /ng N

 

an - ecdysone

(DCH3
|)LiA|H4

2)TsCI,PT
3)Nal \

   

 

 

 

desmosterol

 

   

I) WMgBr

2) 0504

3) Pb(OAC)4

4) H3PO4 _

5) Ac2O,NaOAc {:1

Ac @

1)¢3PJ'<3C2MeLi
2)Ac20. NaOAc

i) PiO2IH2IHOAC

 

2) KOH

   

a vitamin D3 precursor

This dissertation describes experiments which
explore the reactivity of the perhydroindenedione l and
offer the possibility of attaching a side chain to the

five-membered ring of l with the natural configuration.

RESULTS AND DISCUSSION

A. Survey of Carbonyl Reactivity in l_

 

As well as being the potential basis of a total syn-
thesis of several tetracyclic triterpenes, the perhydro-
indenedione, l, offered a unique opportunity to study the
comparative reactivity of five- and six-membered ring
ketones with similar steric environments.

Some idea of the difference in reactivity between
the five-membered ketone and the six-membered ketone can

be gained by considering the selective transformations

outlined in equations 12, 13, and 14:

l)base
2)CH31

 

02)

 

  
 

12, xylene

 

03)

reflux

U4)

 

 

10

Thus, a very high degree of selectivity, favoring
addition to the six-membered carbonyl group, was observed
for sodium borohydride reduction, vinyl magnesium chloride
addition and sulfoxonium ylide combination with 1. Sub-
sequent transformations of these products have implica-
tions for future work to introduce fused rings A and B
or a C-17 side chain. For example, protection of the
hydroxyl group in 2 as an ester or ether derivative should
permit chemical transformations of the relatively unreac-
tive five-membered carbonyl function. To this end,
compound 2 was methylated and yielded the expected methyl
ether 3. Compound 3 was accompanied by small amounts of
side products, presumably resulting from alkylation of the
carbon atom alpha to the carbonyl function. The vinyl
carbinol 4 proved to be difficult to dehydrate, but
finally yielded to treatment with iodine in refluxing

xylene19

to form the diene 5. The diene 5 did not form
Diels-Alder adducts with maleic anhydride or tetracyano-
ethylene in refluxing xylene, or with benzoquinone in

20

refluxing chlorobenzene. Epoxide 6 was formed in

excellent yield by reaction with dimethyloxosulfonium

21 in DMSO solution for more than one week at

methylide
ambient temperature. Epoxide 6 was fairly resistant to
boron trifluoride etherate at room temperature, yielding
only small amounts of isomerized material which was not

isolated. Treatment of 6 with lithium di-n-propyl amine

11

22

in refluxing ether failed to give the expected 8-

elimination product (equation 15):

 

(nPr)2 N Li
// _
(15) g // ,

 

However, treatment of 6 with potassium tert-butoxide in
hot DMSO23 gave a product, the mass spectrum of which

suggested a condensation product of two units of 6

(equation 16):

 

 

In retrospect, the greater reactivity of the six-

membered ketone of 1 compared with the five-membered

ketone is a good illustration of a general principle

summarized over twenty years ago by Professor H. C. Brown:
"It follows that in the 5-membered ring

the trigonal structure for one of the ring

atoms is strongly favored over the tetrahedral
arrangement, whereas the reverse is true in

12

the 6-membered ring. Let us assume that this
result will be generally true for all deriva-
tives of 5- and 6-membered rings. In other
words let us assume that an exo double bond

in all S-membered ring systems will be more
stable toward changes involving loss of the
exocyclic double bond than will the correspond-
ing exo double bonds in 6-membered ring
systems."24

The methoxy ketone 3 was used as the starting material
for all subsequent efforts directed toward a side chain
synthesis. To this end, the widely studied l7-keto

steroids25

served as excellent models for many of the
reactions that were investigated.

Although 3 can be reduced with excess lithium
aluminum hydride, this reduction is best accomplished
by treatment with diisobutyl aluminum hydride. A pair of

epimeric alcohols were produced (equation 17), isolated,

and analyzed spectroscopically.

 

 

The mass spectra of Z and 8 were studied because of

the possible parallel fragmentation to the D ring cleavage

26

in lanostane, illustrated in part below:

 

13

 

 

lanostane m/e 399
m/e 414(45% at tsev) (5% at 15eV)

 

o
.4. my“: m/e 274 (74/. at 15eV)
to ‘

m/e 259 (100% at 15eV)

    

 

 

 

Scheme I

Indeed, the mass spectra of 7 and 8 were similar to that
of lanostane with respect to the formation of an m/e 154

fragment by loss of C2H40, and the lack of substantial

methyl loss (M-lS):

14

   

 

 

 

 

CH30
— d
m/e 198 m/e 198 m/e 154
(Z, 8% at 15 eV) (7, 24% at 15 eV)
(25, 10: at 15 eV) 442° (3, 25% at 15 eV)
l-CHSOH m/e 180 l—CHSOH
(7, 34% at 15 eV)
m/e 166 (8, 4% at 15 eV) m/e 122
(z, 34% at 15 eV) ‘ (z, 100% at 15 eV)
(8, 35% at 15 eV) (8, 100% at 15 eV)

Scheme 2

An eight-fold preference for the loss of water
(M-18) from 2 relative to 8 in the 15 eV mass spectra
of these epimers must be related in some way to their
different configurations. In an effort to determine the
nature of this potentially useful stereochemical discrimi-
nation, three deuterium labeled analogs of Z and 8 were

prepared, as outlined in equations 18, 19, and 20.

15

(l8)

(l9)

 

2H

 

 

16

(20)

   

   

c030 3}, CD3 29.

The formation of 22, 23, and 24 in nearly equal amounts
is a dramatic example of the difference between methyl
iodide and its d3 analog, the latter being smaller and
more able to "invade" the crowded environment of the
five-membered ring.

Compounds Z, 16, 20, and 25 all have lower melting
points and more abundant M-l8 ions than their correspond-
ing epimers (8, 17, 21, and 26). More importantly, no
M-19 ion was observed in any of the deuterium labeled
compounds. The mass spectra of z and 8 were therefore
not helpful in assigning configurations to these isomers.
Compound 2 moves faster than 8 on TLC and GLPC, as
expected for that isomer having a pseudo-equatorial
hydroxyl function. However, this difference is not

sufficient to anchor an iron clad structure assignment.

17
Fortunately, the angular methyl resonance signals
in Z and g (with the aid of the selectively deuterated
analogs 19 and 12) can be interpreted in a fashion that

leads to a clear configuration and assignment.

   

27 have tabulated the incremented

Bhacca and Williams
effects of substituents on the chemical shift of C-18
and C-19 protons for the Sa,14a-androstane series. After
assigning the chemical shifts of the angular methyl
groups bonded to C-1 and C-6 of the perhydroindenes l,
3, E, Z, and 9 (Table 1), the chemical shift difference
for each compound was calculated from the appropriate
steroid methyl increments and compared with the observed
value (Table 2). Hydroxyl increments were used as an
estimate for the methoxyl function in §, 2, and §. The
good correlation of the observed and calculated chemical

shift differences (A) for 7 and 8 seems to justify their

assigned structures.

18

Table 1. Assignment of chemical shifts (ppm)

 

 

C-6 C-1 C-6
Compound methyl methyl methyl (d3 analog)
1 0.85 1.15 0.95 (l5)
g 1.25 0.90 1.25 (13)
§ 1.15 0.85 1.10 (25)
Z 0.90 1.00 0.95 (19)
g 1.00 0.80 1.05 (22)

 

Table 2. Calculated and observed A (61-66) values (ppm)

 

Compound A obs A calc steroid increments used

 

1 0.30 0.32 C-6: l7-oxo(C-18) + 4-oxo(C-19)
” C-l: 12-oxo(C-18) + lS-oxo(C-18)
2 -0.35 -0.32 C-6: 17-oxo(C-l8) + 4B-OH(C-19)
” C-l: lS-oxo(C-18) + IZa-OH(C-18)
3 -0.30 -0.32 same as for 2

7 0.10 0.05 C-6: l7a-OH(C-18) + 48 OH(C-19)
~ C-l: 158-OH(C-18) + lZa-OH(C-18)
8 -0.20 -0.23 C-6: 17B-0H(C-18) + 4B-OH(C-19)
” C-l: 150-0H(C-18) + lZa-OH(C-18)

 

 

l, X = Y = 0

E, X = B-OH,a-H; Y = 0

5, X = fi-OCH3,a-H; Y = 0

Z, X = B-OCH3,a-H; Y = B-H,o-OH
0, X = s-OCH3,a-H; Y = B‘OH,a'h

19

B. Approaches to Side Chain Synthesis

 

Treatment of 3 with isopropenyl lithium, vinyl
lithium, vinyl magnesium chloride, and methyl lithium
failed to yield a carbonyl adduct. However, when 3 was
treated with isopropenyl lithium, followed by acetic
anhydride, the enol acetate 22 was isolated (equation
21). This illustrated the propensity of 3 to form an
enolate anion, rather than an adduct, in the presence of

organometallic reagents.

1)>—- Li
(2” §' ~;

 

 

In order to avoid enolization of 3, under such reaction
conditions, an attempt was made to synthesize the 0,8-

unsaturated compound 28, which is incapable of

20
enolization, but should still be subject to attack by

carbon nucleophiles.

 

(22) 3 7‘

 

The bromide 29 was synthesized from both 3 and the

enol acetate 27;28

however, 29 proved to be resistant to
dehydrobromination by pyridine-silver nitrate, potassium

hydroxide, and potassium tert-butoxide.

Bra, HOAc
(23) 27 at
- pyridine, dork

 

 

 

HOAc,Br2
,3,
HBr

 

(24)

V

 

CH30 3,9,

Likewise, the sulfone 32 failed to eliminate thermally,29

in refluxing xylene, to give 28.

21

(25)
|)LDA

g 2) (cages;

 

Examination of a Dreiding model of 3 indicates that
its trans-configuration induces a puckering of the five-
membered ring, analogous to the configuration of the 17-

keto steroids:

 

It has been noted30 in the case of the 16-bromo-l7-keto
steroids, that introduction of a double bond in the D
ring would cause additional ring strain by flattening
the ring, and this would in fact oppose dehydrohalogena-

tion. Indeed, attempted dehydrohalogenation of such a

31

steroid has led to extensive decomposition. Successful

dehydrohalogenation of the 16-bromo-17-keto steroids can

be effected, however, by protection of the l7-keto function

22

as an ethylene ketal during the dehydrohalogenation.32

O o/W
/_\ 0
(26) . mIBr H0 0H4 . ImBr
stOH

tBuOK

xylene. heat
0 O/\OI
o stOH 0
‘ acetone

68% 75%

 

 

This approach is precluded in the present case because
an ethylene ketal derivative of the keto function in 3
cannot be made.33

A variety of ylides and ester enolates also failed
to form an adduct with the carbonyl function in 3

(Table 3). The addition of Wittig reagents,34’35

21 39 to the l7-keto

ylides, and Reformatsky reagents
function of steroids has been successfully effected in
the past.

The prospect for successful side-chain introduction
improved temporarily with the discovery that freshly pre-
pared sodium acetylide in THF solution gave an adduct
with 3 (equation 27). In the context of previous failures,
this success was not unexpected, since the acetylide

nucleophile is smaller and less basic than the alkyl

23

Table 3. Reagents which failed to form adducts to 3

 

REAGENT REFERENCE
(C6H5)3P =CH — C025? 34'
0
(510)2P-CH-1CH-NHC6H”, NOH 35
9
(C+E92$‘=C+ha 2'
0L'
CH2=C<O,'BU 36
.__ .= ,ICHJ
(CH3)3S| CH C‘DtBu 37
OLi
__ .’
CH2 C\OEt 38
Br-CHz‘COZEf, Zn 39

 

 

 

 

lithium reagents used earlier. Although the yield of
adduct 33 was modest (41% isolated yield), it appeared
as though elaboration of the ethynyl carbinol group to a
terpene side chain would be a simple exercise in apply-

ing known procedures to an unexceptional substrate.
H

C
”I
C

    

NoCECH
THF,ref|ux ,

(2?)

2w

 

CPiC)

33

A!”

24
Unfortunately, adduct 33 proved to be completely
resistant to all efforts to transform it into useful
intermediates. The Rupe rearrangement,4O for example,
failed to proceed in either formic or acetic acid and

yielded only the corresponding esters (equation 28).

0 expected

.3 Rupe product

CH30
(28) g; RCOZH H

I];
C R-H 3:4.

.0 17:0 3:2

CH30

Attempts to effect hydrolysis of the triple bond
by mercury catalyzed addition of water41 failed under a
variety of conditions, some of which successfully trans-

form l7-ethyny1carbinol derivatives of steroids42

(equation 29).

 
  
   

Hg - Dowex 5O
H20, reflux

*
V

 

HC>

25

The ethynyl function of 33 also resisted reduction

to a vinyl group by lithium aluminum hydride,43 diiso-

44

butyl aluminum hydride, and catalytic hydrogenation.

Several hydrogenation conditions were explored, the least
active of which has been used to reduce an ethynyl

45 (equation 30).

steroid

H2.pyridine
Pd/COCCQ

   

Experiments were then conducted with the objective
of turning 33 or a derivative into an allene, but this
effort proved to be equally frustrating. One series of
experiments failed in the attempt to force a Claisen-Cope
rearrangement of 35 and 35 by thermolysis, or by treat-
ment of 35 with silver perchlorate in refluxing acetone,46

a procedure successfully used with steroid analogs

(equation 31).

26

 

H‘CutOAC H
)5 —-—-»OH' ‘33
(
AmC)
42%

Even the normally facile rearrangement of propargylic

47

phosphites to phosphonate esters failed to proceed

(equation 32).

(32) g”

 

The ethynyl groups of 33 and 35 were also impervious to

allene formation in the presence of thionyl chloride-

48 49

pyridine, lithium aluminum hydride-~aluminum trichloride,

49

and dimethyl copper lithium, the precedents for which

are outlined below:

 

27

{SDCI
(.3, . .2 a . + O
OH pyndrne
C ,/Cl

 

 

 

<> CECH

$0 C

CH 0 J, o

60 /o 19 A
CH2
I
CI
LiAlH4 -AICI3
\ 53%
(34) H
\C -—CH3

ll

 

 

C
LiCq(C H3)2¥ ..

Some of the reaction conditions to which 3 was
subjected, yielded unexpected results. Treatment of
3 with lithium ethoxyacetylene50 gave a one-to-one
adduct (32), as confirmed by its mass spectrum and
elemental analysis. The infrared spectrum of 32 dis-

played a strong carbonyl band, and its C13

magnetic
resonance spectrum displayed resonances which suggested
a carbonyl (6 113) and a double bond (6 163 and 183).
The above information implied that adduct 32 had under-

gone the known isomerization to an a,B-unsaturated ester

28

. . . . . . Sl
1n the same fashion as the steroid isomerization shown

in equation 35.

1%;,,CC§Et

 

However, the lack of a resonance signal in the vinyl

region of the proton magnetic resonance spectrum of 37

~~

ruled out such a structure for this compound. Accord-

ingly, an X-ray crystal structure determination52

of
the yellow, crystalline solid was completed. The results

of this analysis were surprising and are displayed in

equation 36.

(36)

LiCECOEt ——->

 

29
There is no precedent for an enolate condensing with ethoxy-
acetylene in this manner. However, amines, alcohols, and

thiols do add in this fashion.53

54 that certain acetylenes

Since it has been shown
will add to ketones in a [2+2] manner upon photolysis,
3 was irradiated in the presence of ethoxyacetylene.
The result of the eXperiment was to isomerize 3 into its

cie~isomer 38:

C)

    

lw

(37)

 

CH30 CH30

 

{no

It may be noted that 38, or a modified version of it, is
a potential starting material for the synthesis of 143-
methyl steroids.

The ability of allyl and crotyl Grignard reagents55
to form addition products with hindered ketones such as

56 seemed worth explor-

di-tert-butyl ketone in high yield
ing. Accordingly, 3 was reacted with allyl magnesium
bromide in THF solution for two days, and recovered
unchanged. However, a parallel experiment in ether
solution proved successful, yielding 39 as the only
product. One epimer of undetermined stereochemistry

greatly predominated, as evidenced by the pmr spectrum

of the product.

30

Br
Mg/
C1, ‘
‘\/ ”ether

2) H30+

(38)

 

 

CH30

 

20)

As shown in equation 38, the success of this addition
reaction results from the ability of the magnesium, an
electron deficient species, to coordinate with the ketone

oxygen, thereby facilitating the known55

cyclic mechanism
by which allyl Grignards add to ketones. Apparently,
THF complexes more strongly with the Grignard reagent
than the ketone oxygen does, and the reaction is retarded
in this solvent.57
This reaction was extended to the case of crotyl
magnesium bromide with excellent results. Reaction of 3
with this Grignard reagent produced the a-methyl alkyl
adduct 50 after one hour's reaction time. Compound 3
had been totally consumed, and no trace of 51 was
detected. However, longer reaction times (ca. one week)
yield 31 as the only product, in accord with previous

work.55

31

 

 

Compound 40 was subjected to conditions which

58 The

effected oxidative cleavage of the olefin bond.
crude acid 32 was treated with excess diazomethane to
form the B—hydroxy ester 53, which was obtained as a
low melting solid after purification by high pressure

liquid chromatography (HPLC), in 36% yield from 40.

(40)

 

Even though GLPC of 30 and 53 discloses a single peak in
each case, analysis by HPLC shows that they are each a
mixture of two compounds. These are presumably epimers
at the position corresponding to C-20 on the steroid

nucleus.

32
The synthesis of fé accomplishes the primary goal
of this dissertation, since this compound is closely
related to other precursors to successful side chain

SYntheses .15’16’17,18

EXPERIMENTAL

General

Except as indicated, all reactions were conducted
under dry nitrogen or argon, using solvent purified
by distillation from suitable drying agents. Magnetic
stirring devices were used for most small scale reactions;
larger reactions were agitated by paddle stirrers.

Organic extracts were always dried over anhydrous sodium
sulfate before being concentrated or distilled under
reduced pressure. The progress of most reactions was
followed by thin layer chromatography (TLC) and/or gas
liquid phase chromatography (GLPC). Visualization of

the thin layer chromatograms was effected by spray reagents
such as 5% p-anisaldehyde in ethanol and 30% sulfuric

acid with subsequent heating.

Analysis by GLPC was conducted with A-90-P3 or 1200
Varian-Aerograph instruments. Preparative layer chroma-
tography was carried out on 2 mm silica gel F-254 adsorbent
on 20 x 20 cm glass plates. Visualization of the prepara-
tive plates was effected by ultraviolet light and/or
charring with a hot wire. Melting points were determined
on either a Hoover-Thomas apparatus (capillary tube) or

on a Reichert hot-stage microscope and are uncorrected.

33

34

Infrared Spectra (ir) were recorded on a Perkin-Elmer
237B grating spectrophotometer. Proton magnetic resonance
spectra (pmr) were taken in deuterochloroform or CCl4
solutions with a Varian T-60 spectrometer and are cali-
brated in parts per million (6) downfield from tetra-
methylsilane as an internal standard. Ultraviolet
spectra (UV) were recorded on a Unicam SP-800 spectro-
photometer. Mass spectra (ms) were obtained with a
Hitachi RMU 6 mass spectrometer. Carbon magnetic
resonance spectra (cmr) were taken in deuterochloroform
solution with a Varian CFT-ZO spectrometer and are cali-
brated in parts per million (6) downfield from tetra-
methylsilane as an internal standard.

Microanalyses were performed by Spang Microanalytical

Labs, Ann Arbor, Michigan.

Preparation of Z-Methylcyclohexan-l,3-Dione

A solution of 80.0 g (2.0M) of sodium hydroxide in
500 ml of water was added to 224 g (2.0M) of cyclohexan-
l,3-dione. The solid quickly dissolved to form a red
solution which was cooled to 0°; then 312 g (2.2M/138 ml)
of methyl iodide was added in one portion, and the mixture
was refluxed for 12 hr. The reaction was cooled to 0°
and the precipitated 2-methylcyclohexan-1,3-dione was
filtered and rinsed with cold water to remove all traces
of sodium iodide. The filtrate and washings were combined
and placed in a reaction flask along with 40 ml of methyl

iodide and refluxed 12 hr. The product was isolated in

35
the same manner described previously. The combined solid
product was air dried for 24 hr, and then dried in a vacuum
oven (40°/l torr) for 12 hr. The product thus obtained
(194 g, 77%) was suitable for use without further puri-
fication. It may be recrystallized (20 ml ethanol/5 g
substrate) to give material with mp 209--le° (lit59
mp 208--210°).

Preparation of 6-Methylbicyclo[4.4.01dec-
l-ene-3,7-dione

 

 

A solution of 0.5 g (about 6 pellets) of potassium
hydroxide in 500 ml of absolute methanol was added to
126 g (1.0M) of Z-methylcyclohexan-l,3-dione, followed by
77 g (1.1M) of methyl vinyl ketone (Aldrich). The mixture
was refluxed for 3 hr, then cooled to room temperature,
and the unreacted methyl vinyl ketone and methanol were
removed under vacuum. The residual oil was dissolved in
500 ml of benzene in a one liter round bottom flask,
equipped with a Dean-Stark trap and condenser, treated
with 6 ml of pyrrolidine, and then refluxed for 90 min.
At this point, 18 ml of water had collected in the Dean-
Stark trap. Prior to cooling it to room temperature,
100 ml of benzene was then distilled from the reaction
mixture. The dark solution was diluted with 300 ml of
ether, washed with 4N hydrochloric acid until no more
red colored material was removed, washed sequentially
with water and brine, and dried. Removal of the solvents

yielded 175 g of light brown oil which was diluted with

36
90 ml of ether and placed in the refrigerator. Crystal-

lization yielded 113 g (63%) of slightly yellow, crystal-

60

line product which had mp 50--53° (ether) (lit mp 47--SO°).

 

Preparation of_(IR*,Sa,6§)—Sjfiydroxy-6-Methyl-
Trityclo[4.4.0.0 :STdecan-Q-Une

 

It should be noted that all reaction apparatus was
scrupulously clean and was flame dried under nitrogen.
The reaction was conducted when the relative humidity in
the laboratory was rather low (e.g., the last two weeks
in January).

In a one liter, three neck, round bottom flask which
contained a small lump of sodium metal, was consensed
500 ml of ammonia. The ammonia was then distilled through
Tygon tubing into a two liter, three neck, round bottom
flask containing 1.39 g (0.2M) of lithium ribbon. The
reaction flask was equipped with a paddle stirrer, a dry
ice condenser, a dry ice--isopr0panol bath, and an addi-
tion funnel to which a nitrogen gas line was attached.

A solution of 17.8 g (0.1M) of the enone dissolved in 250
ml of THF was placed in the addition funnel and added
drOpwise over a one hr period, during which an additional
centimeter of lithium ribbon was added to the reaction.
The blue color of the reaction was discharged by the
dropwise addition of ethylene dibromide, following which
10 g of finely ground ammonium carbonate was added in

one portion. The cooling bath was removed and the

ammonia was evaporated into the hood under a stream of

37
nitrogen. The residue was taken up in 300 ml of water
and this mixture was extracted four times with 200 m1 of
ether. The extracts were washed sequentially with water
and brine, and then dried. After removal of the solvent,
17.2 g of light yellow oil was obtained, which was
triturated with 10 ml of ether and placed in the refrigera-
tor. Crystallization yielded 12.8 g (71%) of the white,
crystalline cyclopropanol. An analytical sample had mp

98--100° (ether).

Preparation of l_

 

A solution of 1.57 g (0.028M) of potassium hydroxide
in 30 ml of 50% v/v methanol—-water was deoxygenated by
bubbling nitrogen gas into it for 15 min. The solution
was cooled to 0° and 4.5 g (0.025M) of the solid tricyclic
cyclopropanol was added in one portion. The deep green
solution was stirred at 0° for 24 hr, and the reaction
was then neutralized with concentrated hydrochloric
acid, whereupon it became yellow and a precipitate formed.
The methanol was removed and the aqueous residue was
dissolved in ether and water. This mixture was extracted
with ether and the ether extracts were washed sequen-
tially with water, 200 ml of 10% aqueous sodium bisulfite
(in four portions), and brine. After drying and removal
of the solvent, 3.27 g (72.5%) of solid 1 was obtained.

An analytical sample displayed the following properties:
mp l68--169° (ether); ir (cc14) 1705, 1735 cm'l; pmr
(CC14) 6 0.85 (5,3H), 1.15 (5,3H), l.30--Z.90 (m,lOH);

38

ms (70 eV) m/e (rel intensity) 180(85), 165(66), 154(10),
137(34), 125(252), 110(100), 95(72), 81(62), 67(63),
55(45), 41(81); cmr (rel intensity ) 6 l7.85(73), 20.59(97),
21.51(77), 24.34(100), 25.21(89), 32.74(98), 36.08(88),
S4.45(25), 55.25(37), l76.25(18), l79.50(l3).

Anal Calcd for C11H1602: C, 73.33; H, 8.88

Found: C, 73.05; H, 8.91

The sodium bisulfite extract was acidified with con-
centrated hydrochloric acid and extracted with chloroform.
The chloroform extract was washed sequentially with water
and brine. After drying and removal of the solvent,

0.69 g (15.3%) of cis-l-methylbicyclo[4.4.0]decan-2,8-

dione was obtained (mp 65--67° [ether]).

Preparation of 2_

 

To a solution of 27.0 g (0.15M) of l in 1350 ml of
ethanol (cooled to 0°) was added drOpwise a solution of
23.2 g (0.58M) of sodium hydroxide and 6.45 g (0.17M) of
sodium borohydride (Ventron) in 100 ml of ethanol and 50
ml of water. This addition was effected over a 30 min
period with vigorous stirring. After 3-1/2 hr at 0°,
GLPC (130°, 4% SE-30) showed that 1 had been totally
consumed. The ethanol was removed from the reaction
mixture and the residue was dissolved in water and ether.
The aqueous phase was extracted with ether and the com-
bined ether extracts were washed sequentially with water
and brine. After drying and removal of the solvent,

26.57 g (97.5%) of essentially pure 2 was obtained. An

39

analytical sample displayed the following properties:
mp 170--l80° (sealed tube); ir (CDClS) 3590, 3450, 1735
cm'l; pmr (ch13) a 0.9 (s,3H), 1.25 (s,3H), 1.3--2.7
(m,llH), 3.8 (m,lH); ms (70 eV) m/e (rel intensity)
182(41), 167(15), 154(5), 149(8), 138(10), 122(40),
111(100), 109(85), 96(64), 81(58), 67(45), 55(62),
41(80).

Anal Calcd for C H 0 ° C, 72.49; H, 9.95

11 18 2'
Found: C, 72.47; H, 9.97

Preparation of 3 via n-Butyl Lithium and Methyl Iodide
A solution of 9.1 g (0.05M) of 2 in 500 ml of THF

was cooled to 0° and stirred vigorously while 27.0 ml of
1.85M n-butyl lithium in hexane (Ventron) was added.
The resulting yellow suspension was stirred 15 min at
0°; then 7.8 g (0.055M) of methyl iodide was added. The
reaction mixture was allowed to warm to room temperature,
stirred for 12 hr, and then washed with brine and dried.
After removal of the solvent, 10.08 g of brown oil was
recovered. Analysis by GLPC (160°, 4% QF-l) showed that
the oil was approximately 79% 3 and 21% 2. This oil was
distilled at 70°/0.05 torr and yielded 6.62 g (67.5%)
of 3 as a colorless oil. The residue weighed 3.1 g and
consisted mainly of 2 which was recrystallized from ether
and recycled in subsequent preparations. An analytical
sample of 3 displayed the following properties: ir (neat)
1735 cm’l; pmr (cc14) a 0.85 (s,3H), 1.15 (s,3H), 1.20--
2.70 (m,lOH), 3.25 (m,lH), 3.3 (s,3H); ms (70 eV) m/e

40

(rel intensity) 196(5), 164(2), 148(5), 125(8), 120(9),
112(7), 109(8), 105(11), 97(8), 91(9), 85(9), 78(93),
71(13), 63(100), 61(15), 55(11), 45(14), 41(19); cmr
(rel intensity) 6 l6.89(86), 18.85(66), 22.84(59),
23.39(100), 25.98(87), 27.09(83), 32.98(74), 44.43(44),
51.l7(35), 57.54(43), 83.69(72), l74.76(16).

Anal_Calcd for C H 0 ' C, 73.43; H, 10.27

12 20 2'
Found: C, 73.37; H, 10.17

Preparation of 3 via Dimsyl Sodium and Methyl Iodide
To 250 m1 of dry DMSO was added 2.16 g (0.09M) of

sodium hydride and the resulting suspension was heated
at 70° for one hr to form a clear yellow solution. This
dimsyl sodium solution was cooled to room temperature
and 8.20 g (0.045M) of 2 was added in one portion. The
solid quickly dissolved and the resulting solution was
stirred one hr at room temperature, followed by the addi-
tion of 9.58 g (0.0675M) by methyl iodide in one portion.
After this reaction mixture was stirred 19 hr at room
temperature, it was poured into 250 ml of water, and the
resulting aqueous mixture was extracted with benzene.
The benzene extract was washed sequentially with water
and brine, and then dried. After removal of the solvent,
8.54 g of yellow oil was recovered. This oil was distilled
at 0.005 torr, and 6.50 g (73.7%) of 3 was collected

between 51--53°.

41

Preparation of 4_

 

To a solution of 1.80 g (0.001M) of l in 100 ml of
THF at room temperature was added 10 ml of 2.5M vinyl
magnesium chloride in TMF (Ventron) in one portion, and
the resulting solution was stirred three days. The reac-
tion was poured into saturated ammonium chloride and
extracted with ether. The ether extracts were washed
sequentially with water and brine, and then dried, to
yield 2.81 g of light yellow amorphous solid after removal
of the solvent. This solid was recrystallized from
ethyl acetate--petroleum ether to yield 1.18 g (56.7%)
of A, which displayed the following prOperties: mp 111--
112°; ir 3410, 1725, 1630, 990, 930 cm'l; pmr (00013)
6 0.85 (s,3H), 1.3 (s,3H), 1.35--3.7 (m,llH), 5.1 (m,2H),
5.9 (m,lH); ms (70 eV) m/e (rel intensity) 208(8), 193(20),
190(11), 175(9), 133(25), 111(100), 96(36), 82(27),
67(25), 55(48), 41(43).

Anal Calcd for C H 0 ' C, 74.96; H, 9.68

13 20 2'
Found: C, 74.84; H, 9.77

Preparation of 5_

A catalytic amount of iodine was added to a solution
of 0.520 g (0.0025M) of A in 25 ml of xylene and the solu-
tion was refluxed for 12 hr. The reaction was cooled to
room temperature and washed sequentially with 0.5M sodium
thiosulfate and brine, and then dried. Analysis by GLPC
(160°, 4% QF-l) and TLC (silica gel, 20% v/v ethyl

42

acetate--cyclohexane) showed that 5 had been totally con-
sumed. The xylene solution was diluted with ether and
filtered through silica gel. The solvents were removed to
yield 0.436 g (91.8%) of 5 as a light yellow oily solid.
An analytical sample of 5 displayed the following
properties: UV (95% ethanol) 235 nm (e 1.5[104]); ir
(neat) 3010, 1730, 1675, 990, 910 cm’l; pmr (C014) 6 0.75
(s,3H), 0.85 (s,3H), 1.0--3.0 (m,8H), 5.0--7.0 (m,4H);
ms (70 eV) m/e (rel intensity) 190(43), 175(16), 157(8),
147(10), 133(37), 119(100), 105(28), 91(14), 77(16),
65(9), 55(12), 41(12).

Anal Calcd for C H

0 C, 82.06; H, 9.53

18 2‘
Found: C, 82.22; H, 9.70

13

Preparation of 6_

 

To 300 ml of DMSO (dried over molecular sieves) was
added 2.66 g (0.111M) of sodium hydride which had been
rinsed with petroleum ether and weighed out as a dry
solid. The mixture was heated with stirring at 70° for
one hr, until a yellow solution had formed. The solution
was cooled to 15° and 24.40 (0.111M) of solid trimethyl-
oxosulfonium iodide was added in one portion. The mixture
was stirred 30 min at room temperature until a solution
had formed. Then a solution of 8.00 g (0.0455M) of l in
100 ml of DMSO was added in one portion and the resulting
solution was stirred seven days at room temperature.

The reaction was poured into 400 ml of ice water and the

resulting mixture was extracted with five, 200 m1 portions

43

of ether. The ether solution was washed sequentially with
water and brine, and then dried. After removal of the
solvent 7.33 g (83%) of Q,was recovered as a white solid.
An analytical sample of §,displayed the following properties:
mp 159--161° (petroleum ether); ir 1735 cm'l; pmr (CC14)
1.0 (s,3H), l.l (s,3H), 1.15--2.2 (m,lOH), 2.3 (m,2H);
ms (70 eV) m/e (rel intensity) 194(28), 179(13), 166(17),
151(17), 136(44), 122(46), 107(100), 93(58), 79(45),
67(37), 55(42), 41(72).

Anal Calcd for ClZH 0 ° C, 74.19; H, 9.34

18 2'
Found: C, 74.16; H, 9.27

Preparation of Z and §_

To a solution of 3.92 g (0.02M) of‘; in 100 ml of
THF at 0° was added in one portion 43 ml of a 20% solu-
tion of diisobutyl aluminum hydride in hexane (Ventron).
The reaction was placed in a refrigerator at 5° for two
days, and was then poured into cold 4N hydrochloric acid
and extracted with ether. The ether extracts were
washed sequentially with 4N hydrochloric acid, water,
and brine, and then dried. After removal of the solvent,
3.91 g (98.7%) of a clear oil was obtained which proved
to be a mixture of the epimeric alcohols, Z and 8.
Analysis by GLPC (160°, 4% QF-l) showed that 3 had been
completely consumed and that the two epimeric alcohols
were present in the ratio of 1.4:1 (shorter retention
alcoholzlonger retention alcohol). Analytical samples

of each of the alcohols were obtained by preparative

 

44
layer chromatography (20% v/v ethyl acetate--cyclohexane,
double elution) of 0.1583 g of the epimeric mixture.
The higher band on the plate yielded 0.0665 g of one epimer
which corresponded to the shorter retention component on
the GLPC. It was assigned configuration 7, and displayed
the following properties: mp 84--85°; ir (CC14) 3610,
3480 cm‘l; pmr (0014) 6 0.9 (s,3H), 1.0 (s,3H), 1.1--2.6
(m,llH), 3.05 (m,lH), 3.20 (s,3H), 3.6 (m,lH); ms (15 eV,
ion source 100°) m/e (rel intensity) 198(8), 180(34),
166(34), 154(24), 148(63), 133(19), 122(100), 112(12),
93(16), 84(50), 71(20).

Anal Calcd for C M O C, 72.68; M, 11.18

22 2‘
Found: C, 72.71; M, 11.16

12

The lower band on the plate yielded 0.0533 g of the

other epimer which corresponded to the longer retention
component on the GLPC. It was assigned configuration 8
and displayed the following properties: mp 106--108°;
ir (0014) 3615, 3500 cm'l; pmr (00013) 8 0.8 (s,3H),
1.0(s,3H), l.l--2.6 (m,llH), 3.0 (m,lH), 3.2 (s,3H),
3.8 (m,lH); ms (15 eV, source 100°) m/e (rel intensity)
198(10), 180(4), 166(35), 154(25), 148(39), 133(8),
122(100), 112(38), 93(8), 84(33), 71(16).

Anal Calcd for C12M2202: C, 72.68; M, 11.18

Found: C, 72.61; M, 11.18

Preparation of 9_

 

A solution of 2.76 g (0.069M) of sodium hydroxide
in 25 ml of water was added to 7.72 g (0.069M) of

45
cyclohexan-l,3-dione. The solid quickly dissolved to
give an orange solution which was cooled to 0°, and heated
with 10 g (0.069M) of CD31 (Aldrich). The reaction was
refluxed for two days, then cooled to room temperature,
and placed in the refrigerator at 5° for 12 hr. The
resulting solid was recovered by vacuum filtration,
washed with water, and dried in a vacuum oven at 45°/
one torr, to yield 6.00 g (67.5%) of 9, a light yellow
solid which displayed the following properties: mp
184-~188°; ms (70 eV) m/e (rel intensity) 130(5),
129(50), 101(62), 83(36), 73(35), 59(45), 55(100),
42(64), 32(77). The ir and pmr were not taken due to
the low solubility of this compound in most common

spectral solvents.

Preparation of 10

~ ~,‘

A mixture of 6.00 g (0.0465M) of 9, 30 m1 of ethyl

 

acetate, 10 m1 of triethylamine, and 6.0 m1 of methyl
vinyl ketone was stirred 12 hr at room temperature.

At this point, some of the starting material still had
not dissolved, so an additional 2 ml of methyl vinyl
ketone was added and the reaction was refluxed for 6 hr.
The solution was cooled to room temperature and filtered.
After removal of the solvent from the filtrate, 10.18 g
of light brown gum was recovered which contained the
desired Michael-adduct and some decomposed methyl vinyl
ketone. A solution of the crude Michael-adduct, which

was pure by GLPC (180°, 4% QF-l) in 200 ml of toluene, was

46
treated with 0.167 ml (0.142 g/0.002M) of pyrrolidine and
0.114 ml (0.120 g/0.002M) of glacial acetic acid and was
refluxed for 12 hr. Analysis by GLPC indicated that the
Michael-adduct had been consumed and that l0 was the only
product. The reaction was diluted with 200 ml of ether
and washed with 200 ml of 4N hydrochloric acid. The
aqueous wash was treated with 15 m1 of concentrated sul-
furic acid and was extracted with ten, 100 m1 portions
of ether. The combined organic solutions were washed
sequentially with water and brine, and then dried. After
removal of the solvent, 6.95 g of brown oil was recovered.
Continuous liquid-liquid extraction of the acid wash with
chloroform gave 1.80 g of semi-solid material after
removal of the solvent. This material was dissolved in
ether and the resulting brown precipitate was removed by
filtration. A further 0.32 g of crude product was
obtained after removal of the solvent. The combined
yield of crude product was 7.27 g. An ir of the crude
product showed the presence of acidic material, so a
solution of the crude product in ether was washed with
saturated sodium bicarbonate. After removal of the
solvent, 5.84 g (69.4%) of l9 was obtained which displayed
the following properties: ir (neat) 2200, 1735, 1715,
1640 cm‘l; pmr (cc14) 6 1.0--3.1 (m,lOH), 5.6 (5,1H);
ms (70 eV) m/e (rel intensity) 182(11), 181(58), 163(52),
139(80), 125(79), 121(100), 111(77), 93(75), 79(68),
69(80), 67(81), 41(75), 39(82).

47

Preparation of 11_

~~

 

Into a one liter, three neck, round bottom flask
equipped with a dry ice--isopropanol cooling bath, paddle
stirrer, dry ice--isopropanol condenser, pressure equalized
addition funnel, and nitrogen line, containing 45 m1 of
THF and 0.452 g (0.065M) of lithium ribbon, was condensed
250 ml of dry ammonia (from sodium). A solution of 5.75
g (0.0318M) of l0 in 80 m1 of THF was placed in the addi-
tion funnel and added to the reaction over 30 min. When
the addition was complete, the blue color of the ammonia
was discharged with a few drOps of ethylene dibromide,
then 6.7 g (0.07M) of ammonium carbonate was added in
one portion. The ammonia was evaporated into the hood
under a stream of nitrogen and the remaining material was
taken up with 400 m1 of water and then extracted with four,
100 m1 portions of ether. The ether extracts were washed
sequentially with water and brine, and then dried. After
removal of the solvent, 5.18 g (89%) of ll was recovered
as a light brown solid which displayed the following

properties: ir (cc14) 3375, 2200, 1700 cm—1

; pmr (CC14)
6 0.9--2.8 (m,llH), 3.55 (m,2H); ms (70 eV) (rel intensity)
184(16), 183(100), 165(28), 155(13), 140(26), 127(57),

113(70), 99(49), 84(53), 71(45), 55(33), 41(63).

Preparation of 13_
To a deoxygenated solution of 1.72 g (0.0306M) of
potassium hydroxide in 60 m1 of 50% v/v methanol-~water

was added 5.10 g (0.0278M) of ll'and the resulting

 

 

48
solution was stirred six hr at room temperature. This
solution was blue-green initially and gradually became
brown. The reaction was neutralized with concentrated
hydrochloric acid, and the resulting yellow, heterogeneous
mixture was extracted with five, 100 m1 portions of ether.
The ethereal extract was analyzed by GLPC (160°, 4% QF-l)
and the ratio of l3 to l2 was found to be 4:1. The ether
extract was washed sequentially with three 25 ml portions
of 10% sodium bisulfite, 4N hydrochloric acid, water,
and brine, and then dried. After removal of the solvent,
2.65 g of yellow solid was recovered. This solid was
recrystallized from ether--petroleum ether to give 1.29 g
(25.3%) of l3 which displayed the following properties:
mp 158--160°; ir (c014) 2200, 1720, 1700 cm'l; pmr
(CDC13) 6 0.95 (s,3H), l.4--2.7 (m,lZH); ms (70 eV)
m/e (rel intensity) 184(9), 183(64), 168(9), 165(56),
155(4), 141(21), 137(23), 128(50), 113(100), 99(63),
85(60), 69(30), 55(31), 41(49).

The combined aqueous washes were acidified with
concentrated sulfuric acid and extracted continuously
with chloroform in a liquid-liquid extractor. After
isolation of the chloroform phase and removal of the
solvent, 2.12 g of brown oil was recovered. Analysis
by GLPC showed that the oil was a mixture of l2 and l3.

The combined yield of 12 and 13 was 4.77 g (93.5%).

49

 

Preparation of l4_

A solution of 1.25 g (0.0312M) of sodium hydroxide
and 0.266 g (0.007M) of sodium borohydride in 3 ml of
water was added to a solution of 1.00 g (0.00546M) of
l3 in 50 ml of ethanol at 0°. The reaction was stirred
4-1/2 hr at 0°, then neutralized by the dropwise addi-
tion of concentrated hydrochloric acid. The ethanol was
then removed and the residue was dissolved in ether and
water. The mixture was extracted with ether and the
extracts were washed sequentially with water and brine,
and then dried. After removal of the solvent, 1.07 g
of crude 14 was isolated as a solid, which was recrystal-
lized from ether to yield 0.687 g (68.0%) of l4 as white
crystals which displayed the following properties:
mp l76--l77° (sealed tube); ir (CDClS) 3600, 3450, 2200,

1730 cm'1

; pmr (CDC13) 6 1.25 (s,3H), 1.3--2.6 (m,llH),

3.8 (m,lH); ms (70 eV) m/e (rel intensity) 186(7), 185(55),
170(10), 167(10), 157(4), 152(4), 149(7), 143(6), 141(7),
139(8), 125(42), 114(78), 112(100), 99(80), 81(57),

69(53), 55(28), 43(33), 41(45).

Ppaparation of l5_
To a solution of 0.617 g (0.003M) of l4 in 60 ml of
THF at 0° was added dropwise 1.35 ml of 2.45M n-butyl
lithium in hexane (Ventron), whereupon the lithium
alkoxide of l4 formed a precipitate. The reaction mixture
was stirred 15 min at 0°, then 0.206 ml (0.468 g/0.0033M)

of iodomethane was added in one portion. The reaction was

50
warmed to room temperature and stirred for 12 hr, during
which the alkoxide went into solution. This solution was
poured into brine and the resulting mixture was extracted
with ether. The ether extract was washed sequentially with
50% v/v water--brine and brine, and then dried. After
removal of the solvent, 0.650 g of yellow oil was recovered,
which was placed on 65 g of silica gel and eluted with
20% v/v ethyl acetate--cyclohexane, to yield 0.421 g
(70.6%) of l5 as an oil, as well as 0.183 g of l4. Com-
pound l5 displayed the following prOperties: ir (neat)
2215, 2200, 2050, 1735 cm-1; pmr (cc14) 6 1.1 (s,3H),
l.2--2.6 (m,lOH), 3.15 (m,lH), 3.25 (s,3H); ms (70 eV)
m/e (rel intensity) 200(8), 199(44), 184(4), 181(4),
171(5), 167(9), 157(2), 149(8), 143(11), 139(12), 128(40),
125(54), 115(59), 112(54), 97(51), 85(55), 71(100),
58(35), 41(43).

Preparation of l6 and 12—
To a solution of 0.352 g (0.00177M) of l5 in 20 m1

of THF at 0° was added in one portion 4.3 m1 of a 20%
solution of diisobutyl aluminum hydride in hexane
(Ventron). The reaction was placed in a refrigerator
at 5° for two days, and was then poured into cold 4N
hydrochloric acid and extracted with ether. The ether
extracts were washed sequentially with 4N hydrochloric
acid, water, and brine, then dried. After removal of
the solvent, 0.380 g of a clear oil was obtained which

proved to be a mixture of the epimeric alcohols, 16 and 17.

51
Analysis by GLPC (160°, 4% QF-l) showed that l5 had been
completely consumed and that the two epimeric alcohols
were present in the ratio of 1.4:1 (shorter retention
alcohol:1onger retention alcohol).

Analytical samples of each of the alcohols were
obtained by preparative layer chromatography (20% v/v
ethyl acetate--cyclohexane, double elution) of the
epimeric mixture. The higher band on the plate yielded
0.162 g of one epimer which corresponded to the shorter
retention component on the GLPC. It was assigned con-
figuration l6, and displayed the following properties:
mp 76--78°; ir (CHClS) 3590, 3415, 2220, 2205, 2120,
2030 cm'l; pmr (c0013) 6 0.95 (s,3H), 1.1--2.6 (m,llH),
3.15 (m,lH), 3.25 (s,3H), 3.75 (m,lH); ms (15 eV, ion
source 100°) m/e (rel intensity) 201(11), 186(1), 184(1),
183(12), 169(38), 157(35), 151(37), 125(100), 115(9),
112(9), 108(10), 84(49), 71(8).

The lower band on the plate yielded 0.124 g of the
other epimer which corresponded to the longer retention
component on the GLPC. It was assigned configuration l7,
and displayed the following properties: mp 107--109°;

ir (CHClS) 3580, 3410, 2215, 2205 cm'1

; pmr (CDC13) 6

. 1.05 (s,3H), l.l--2.6 (m,llH), 3.05 (m,lH), 3.25 (s,3H),
3.9 (m,lH); ms (15 eV, ion source 100°) m/e (rel intensity)
201(12), 186(1), 184(1), 183(3), 170(6), 169(42), 157(32),
151(38), 125(100), 115(34), 112(8), 108(12), 84(14),

71(10).

52

 

Prpparation of l§_

To a solution of 0.42 g (0.01M) of sodium tetra-
deuteridoborate (ICN) in 150 ml of absolute ethanol at
0°, was added in one portion 1.00 g (0.00556M) of l.
The reaction was stirred 3 hr at 0°, then the excess
reducing agent was destroyed by the dr0pwise addition of
concentrated hydrochloric acid. The ethanol was removed
and the residue was dissolved in water and ether. The
mixture was extracted with ether, and the extracts were
washed with brine and dried. All of diketone l had been
consumed by the reaction to form one product according to
analysis by TLC (silica gel, ether) and GLPC (160°, 4%
QF-l). The solvent was removed to yield 1.03 g (100%)
of l8 as a white solid that displayed the following pro-
perties: mp 168--17l°; ir (CHCls) 3600, 3450, 2400, 2090,
1735 cm'l; pmr (00013) 8 0.82 (s,3H), 1.15 (s,3H),
120--2.6 (m,llH); ms (70 eV) m/e (rel intensity) 184(7),
183(53), 168(18), 150(9), 141(6), 138(16), 123(45),
112(81), 110(100), 96(90), 82(52), 67(33), 55(46), 41(61).

Praparation of l9_

~~

To a solution of 0.732 g (0.004M) of 18 in 75 m1 of

 

THF at 0° was added dropwise 1.80 ml of 2.45M n-butyl
lithium in hexane (Ventron). The suspension which formed
was stirred 15 min at 0°, then 0.275 ml (0.625 g/0.0044M)
of iodomethane was added, and the reaction was stirred

1 hr at 0°, then warmed to room temperature, and stirred

12 hr. The reaction was diluted with 100 m1 of ether,

53

and the solution was washed sequentially with 50% v/v
water--brine and brine, and then dried. After removal
of the solvent, 0.801 g of yellow oil was obtained which
analysis by GLPC (160°, 4% QF-l) showed was a mixture of
l9 and l8. This oil was placed on 80 g of silica gel
and eluted with 20% v/v ethyl acetate--cyclohexane, to
yield 0.550 g (69.9%) of l9, as well as 0.250 g of l8.
The labeled methoxy ketone 1g displayed the following

properties: ir (neat) 2175, 1740 cm"1

; pmr (CC14) 6
0.82 (s,3H), 1.1 (s,3H), 1.2--2.6 (m,lOH), 3.25 (s,3H);
ms (70 eV) m/e (rel intensity) 198(7), 197(42), 182(5),
166(3), 165(8), 150(8), 141(10), 126(53), 123(41),
112(66), 110(55), 97(45), 86(57), 72(100), 59(30),

55(36), 41(51).

 

Praparation of 20 and 2l_

To a solution of 0.404 g (0.00205M) of l9 in 20 m1
of THF at 0° was added in one portion 4.3 m1 of a 20%
solution of diisobutyl aluminum hydride in hexane
(Ventron). The reaction was placed in a refrigerator at
5° for two days, after which it was poured into cold 4N
hydrochloric acid and the resulting mixture was extracted
with ether. The ether extracts were washed sequentially
with 4N hydrochloric acid, water, and brine, and then
dried. After removal of the solvent, 0.448 g of a clear
oil was obtained which proved to be a mixture of the
epimeric alcohols, 20 and 2l. Analysis by GLPC (160°,
4% QF-l) showed that l9 had been completely consumed and

54
that the two epimeric alcohols were present in the ratio
of 1.4:1 (shorter retention alcohol:1onger retention
alcohol). Pure samples of each of the alcohols were
obtained by preparative layer chromatography (20% v/v
ethyl acetate--cyclohexane, double elution) of the epi-
meric mixture. The higher band on the plate yielded
0.184 g of one epimer which corresponded to the shorter
retention component on the GLPC. It was assigned con-
figuration 20, and displayed the following properties:

mp 7o--72°; ir (CHC13) 3590, 3440, 2080 cm"1

; pmr (CDC13)

6 0.95 (s,3H), 1.05 (s,3H), l.l--2.6 (m,llH), 3.2 (s,3H),
3.6 (m,lH); ms (15 eV, ion source 100°) m/e (rel intensity)
199(12), 181(17), 167(51), 155(39), 149(55), 134(11),
123(100), 112(15), 109(20), 108(15), 95(10), 85(70),
72(11).

The lower band on the plate yielded 0.153 g of the
other epimer which corresponded to the longer retention
component on the GLPC. It was assigned configuration El,
and displayed the following properties: mp 106--109°;

ir (CHCls) 3590, 3440, 2075 cm'1

; pmr (CDC13) 6 0.82
(s,3H), 1.02 (s,3H), 1.1--2.6 (m,llH), 3.2 (s,3H),

3.8 (m,lH); ms (15 eV, ion source 90°) m/e (rel intensity)
199(7), 181(3), 167(36), 155(27), 149(35), 134(6),

123(100), 112(37), 109(17), 108(12), 95(6), 85(22), 72(9).

Praparation of 22_

 

To a solution of 0.690 g (0.00379M) of 2 in 75 ml of
THF at 0° was added 2.0 m1 of 2.5M n-butyl lithium in

55

hexane (Ventron) in one portion, and the resulting suspen-
sion was stirred 15 min at 0°. The reaction was then
treated with 0.322 ml (0.005M) of iodotrideuteridomethane
(Aldrich) and stirred six hr at 0°. The reaction was
then warmed to room temperature and stirred 12 hr. The
reaction was diluted with 100 ml of ether and washed
sequentially with 50% v/v water--brine and brine, and
then dried. After removal of the solvent, 0.908 g of
brown oil was recovered, which was filtered through
silica gel in ether solution to give 0.732 g of light
brown oil. This oil was chromatographed on an HPLC
column (500 x 15 mm, silica gel, 5% v/v methanol--
chloroform at 1 ml/min) to yield 0.524 g of deuterium
labeled product as a clear oil and 0.145 g of 2. The
deuterium labeled fraction was a mixture of three major
components, present in roughly equal amounts. Pure
samples of these components were isolated by preparative
GLPC (200°, 10 ft 20% SE-30).

Collection of the component with the shortest reten-
tion yielded 0.142 g of 22 as an oil which displayed the
following properties: ir (neat) 2210, 2175, 2100, 2045,

1735 cm'1

; pmr (CC14) 6 0.82 (s,3H), 1.1 (s,3H), 1.Z--2.6
(m,lOH), 3.15 (m,lH); ms (70 eV) m/e (rel intensity)
200(4), 199(27), 184(3), 181(2), 171(3), 165(2), 164(6),
157(2), 156(3), 128(79), 121(34), 107(52), 93(56), 74(87),

67(50), 55(55), 41(100).

56
Collection of the component with the middle retention
yielded 0.113 g of 33 as an epimeric mixture which dis-
played the following properties: ir (neat) 2205, 2175,

2105, 2045, 1735 cm“1

; pmr (€C14) one epimer (63%) had

6 0.85 (s,3H), 1.05 (s,3H), the other epimer (37%) had

6 0.75 (s,3H), 1.15 (s,3H), the other peaks were 6
1.2--2.8 (m, 9H), 3.1 (m,lH); ms (70 eV) m/e (rel inten-
sity) 217(3), 216(22), 201(2), 182(1), 181(4), 171(10),
153(6), 148(10), 143(13), 140(4), 138(19), 128(100),
114(34), 109(33), 107(28), 93(35), 81(43), 74(64), 67(33),
55(38), 41(75).

Collection of the component with the longest reten-
tion yielded 0.041 g of 33 as an oil which displayed the
following properties: ir (neat) 2210, 2175, 2105, 2050,
1730 cm‘l; pmr (cc14) 8 0.9 (s,3H), 1.15 (s,3H), 1.3--2.6
(m,8H), 3.15 (m,lH); ms (70 eV) m/e (rel intensity)
234(2), 233(14), 218(3), 215(1), 198(1), 171(9), 155(14),
146(25), 128(100), 119(30), 93(29), 81(35), 74(45),
67(28), 55(28), 41(63).

Preparation of 33 and 26_

 

To a solution of 0.137 g (0.000690M) of 33 in 20 m1
of THF at 0° was added in one portion 2.26 ml of a 20%
solution of diisobutyl aluminum hydride in hexane
(Ventron). The reaction was placed in a refrigerator at
5° for two days, then poured into cold 4N hydrochloric
acid and extracted with ether. The ether extracts were

washed sequentially with 4N hydrochloric acid, water,

57
and brine, and then dried. After removal of the solvent,
0.141 g of a clear oil was obtained. Analysis by GLPC
(160°, 4% QF-l) showed that the oil was a mixture of
33, 33, and 33 and that the two epimeric alcohols were
present in the ratio of 1:2.5 (shorter retention alcohol:
longer retention alcohol). Pure samples of each of the
alcohols were obtained by preparative layer chromatography
(20% v/v ethyl acetate--cyclohexane, double elution) of
the mixture. The higher band on the plate yielded
0.057 g of one epimer which corresponded to the shorter
retention component on the GLPC. It was assigned con-
figuration 33, and displayed the following properties:
mp 83--85°; ir (CHClS) 3590, 2210, 2175, 2100, 2045 cm’l;
pmr (CDC13) 6 0.95 (s,3H), 1.05 (s,3H), 1.1--2.6 (m,llH),
3.1 (m,lH), 3.65 (m,lH); ms (15 eV, ion source 110°) m/e
(rel intensity) 202(2), 201(10), 184(3), 183(19), 166(36),
157(25), 148(46), 133(8), 122(100), 112(10), 108(14),
95(4), 94(4), 87(51), 74(11).

The lower band on the plate yielded 0.042 g of the
other epimer which corresponded to the longer retention
component on the GLPC. It was assigned configuration
39, and displayed the following properties: mp 109-~111°;
ir (CHC13) 3590, 2210, 2170, 2045 cm'l; pmr (c0013) 8
0.8 (s,3H), 1.02 (s,3H), l.1--2.6 (m,llH), 3.02 (m,lH),
3.82 (m,lH); ms (15 eV, ion source 110') m/e (rel inten-
sity) 202(2), 201(11), 183(5), 166(38), 157(25), 148(36),
133(6), 122(100), 112(37), 108(13), 95(4), 94(5), 87(13),
74(9).

58

Treatment of 3 with Isopropenyl Lithium

 

To a solution of 3.33 ml of a 0.15M stock solution
of isopropenyl lithium (from isopropenyl bromide) in
ether and 5 m1 of tetramethylethylenediamine in 12.5 ml
of THF at -78°, was added dropwise a solution of 0.098 g
(0.0005M) of 3 in 12.5 ml of THF. On completion of the
addition, the reaction was stirred a further hour at
-78°, then warmed to room temperature and stirred 24 hr.
The reaction was then cooled to -78°, a second 3.33 ml of
0.15M iSOpropenyl lithium added, stirring continued one
hr at -78°, and then warmed to room temperature and
stirred 24 hr. The reaction was quenched by the addition
of saturated aqueous ammonium chloride and extracted
with ether. The extracts were washed sequentially with
water and brine, and then dried. After removal of the
solvent, 1.15 g of brown oil was recovered. The crude
product was placed on 100 g of silica gel and eluted with
30% v/v ether--pentane, to yield 0.83 g of material
which displayed spectral properties identical to those

of the starting material.

 

 

Treatment of 3 with Vinyl Lithium
To a solution of 0.196 g (0.001M) of 3 in 20 m1 of
THF at -78° was added 0.6 m1 of 2.5M vinyl lithium in
THF (Ventron) in one portion. The reaction was stirred
at -78° for one hr, then at 0° for one hr, and at room
temperature for 12 hr. The reaction was poured into

water and extracted with ether. The extracts were washed

59
sequentially with water and brine, and then dried. After
removal of the solvents, 0.190 g of yellow oil was
recovered which had spectral properties and GLPC reten-

tion (160°, 4% QF-l) identical with those of 3.

Treatment of 3 with Vinyl Magnesium Chloride

 

To a solution of 0.204 g (0.00104M) of 3 in 20 m1
of THF and 0.42 ml (0.003M) of HMPA, was added 1.3 ml
of 2.3M vinyl magnesium chloride in THF (Ventron) in one
portion, and the resulting solution was refluxed for two
days. The reaction was poured into 4N hydrochloric acid
and extracted with ether. The ether extracts were washed
sequentially with water and brine, and then dried. After.
removal of the solvent, 0.174 g of brown oil was obtained
which displayed spectral properties and GLPC retention

(160°, 4% QF-l) identical with those of 3.

Treatment of 3 with Methyl Lithium

 

To a solution of 0.196 g (0.001M) of 3 in 10 m1 of
THF and 0.3 ml of tetramethylethylenediamine, was added
1.21 ml of 1.65M methyl lithium in ether (Ventron) in one
portion, and the resulting solution was stirred at room
temperature for five days. The reaction was poured into
cold 4N hydrochloric acid and then extracted with ether.
The ether extract was washed sequentially with 4N hydro-
chloric acid, water, and brine, and then dried. After

removal of the solvent, 0.225 g of brown oil was recovered

60
which displayed spectral properties and GLPC retention

(160°, 4% QF-l) identical with those of 3.

Preparation of 27

 

To a solution of 3.33 ml of a 0.15M stock solution
of iSOpropenyl lithium (from 2-bromopropene) in ether,
2.5 ml of tetramethylethylenediamine, and 6.5 ml of THF
was added dropwise a solution of 0.049 g (0.00025M) of
3 in 6.5 ml of THF at room temperature. The resulting
'solution was refluxed for 24 hr. The reaction was cooled
to room temperature, and then quenched by the addition
of 1.08 g (0.0106M) of acetic anhydride in one portion.
The cloudy, brown reaction became translucent at this
point. The reaction mixture was poured into water and
extracted with ether. The ether extracts were washed
sequentially with water and brine, and then dried. The
solvent was removed to yield 0.89 g of brown oil, which
was placed on 80 g of silica gel and eluted with 30%

v/v ether--pentane and later 50% v/v ether--pentane, to
yield 0.140 g of hydrocarbon grease, 0.210 g (35.3%) of
32, and 0.326 g of 3. The enol-acetate 32 displayed the
following properties: ir (neat) 1760, 1640, 895, 805
cm'l; pmr (c014) 8 1.1 (s,3H), 1.15 (s,3H), l.2--2.8
(m,8H), 2.05 (s,3H), 3.15 (m,lH), 3.2 (s,3H), 5.2 (m,lH);
ms (70 eV) m/e (rel intensity) 238(1), 196(22), 181(10),
178(9), 164(33), 149(100), 135(23), 131(14), 121(30),
119(19), 117(30), 107(25), 93(24), 91(24), 79(25), 73(25),
71(52), 67(23), 55(39), 45(34), 43(86), 41(62).

61
Anal Calcd for C14H2203: C, 70.56; H, 9.30

Found: C, 70.64; H, 9.18

Preparation of 29 from 27_

 

To a solution of 0.129 g (0.000543M) of 33 in 60 ml
of 10% v/v pyridine--acetic acid was added a solution of
1.04 g (0.0065M) of bromine in 3 m1 of acetic acid. The
reaction was stirred in the dark at room temperature for

24 hr, after which 25 m1 of 10% Na SO was added. The

2 3

mixture was extracted with ether. Analysis by TLC (silica
gel, 30% v/v ether--pentane) of the ether solution showed
that 33 had been consumed in the reaction. After drying
and removal of most of the solvent, 1.27 g of oil was
recovered which contained acetic acid. Th1s oil was
placed on 100 g of silica gel and eluted with 30% v/v
ether--pentane. The products obtained from the chroma-
tography were assumed to comprise both epimeric bromo
ketones, since their TLC retentions were different from
33 and 3. Early fractions yielded 0.0205 g of a mixture
of both epimers. The later fractions yielded 0.0648 g
(43.5%) of one epimer of 33 as yellow crystals which dis-
played the following properties: mp 69--79° (decomposi-

tion); ir (cc14) 1755 cm’1

; pmr (CC14) 6 0.89 (s,3H),

1.42 (s,3H), 1.3--2.9 (m,8H), 3.25 (m,lH), 3.35 (s,3H),
4.15 (t,1H); ms (70 eV) m/e (rel intensity) 276(9),

274(9), 196(8), 194(2), 168(5), 163(11), 140(65), 125(100),

109(44), 93(38), 84(95), 71(94), 55(45), 41(71).

62

Preparation of 29 and 30 from 3_

 

To a solution of 0.613 g (0.00313M) of 3 in 55 ml
of acetic acid was added a solution of 0.550 g (0.0034M)
of bromine in 5 m1 of acetic acid, followed by one drop
of fuming hydrobromic acid. The reaction was stirred at
55° for eight hr. After cooling to room temperature,
50 m1 of 10% sodium sulfite was added to the reaction
mixture which was then poured into 200 m1 of water. This
aqueous mixture was extracted with ether and the ether
extracts were washed sequentially with water and brine,
and then dried. After removal of the solvent, 0.982 g
of oil was recovered. Analysis by GLPC (150°, 4% SE-30)
of the oil showed the presence of 3, 33, and a third com-
ponent subsequently identified as 39. The oil was placed
on 100 g of neutral alumina (act 1) and eluted with 5%
v/v ether--benzene. Early fractions yielded 0.196 g of
39 as a solid which displayed the following properties:

mp 100--105°; ir (nujol) 1765 cm.1

; pmr (CC14) 6 1.20
(s,3H), 1.55 (s,3H), 1.5--2.8 (m,8H), 3.1 (m,lH) 3.35
(s,3H); ms (70 eV) m/e (rel intensity) 3S6(0.3), 354(0.4),
352(0.3), 296(0.2), Z94(0.4), 292(0.2), 276(l.5),
274(l.6), 215(1.5), 213(1.5), l63(3.0), 140(95), 125(100),
109(24), 108(26), 93(26), 91(23), 84(22), 71(79), 55(26),
41(55).

Later fractions yielded 0.229 g (26.8% yield from 3)

of 29, identical in all its spectral properties to the

bromide isolated in the previous preparation.

63
Treatment of 33 with Pyridine--Silver Nitrate

To a solution of 0.0475 g (0.000173M) of 39 in 1.5
m1 of pyridine was added 0.0295 g (0.000173M) of solid
silver nitrate and the mixture was refluxed for 48 hr.
The reaction was cooled to room temperature, diluted with
benzene, and then filtered through alumina. The benzene
solution was then washed sequentially with 4N hydro-
chloric acid and brine, and then dried. After removal
of the solvent, 0.0452 g of oil was recovered whose
spectral properties and GLPC retention were identical to

those of 29.

Treatment of 29 with Ethanolic Potassium Hydroxide

 

A solution of 0.065 g of 33 and 0.7 g of potassium
hydroxide in 5 m1 of absolute ethanol was refluxed for
24 hr. Analysis of the reaction by GLPC and TLC (neut
alumina, act 1, 5% v/v ether--benzene) showed that 33

had remained unchanged.

 

Treatment of 33 with Potassium Tart-Butoxide

A solution of 0.100 g (0.000365M) of 39, and 0.045 g
(0.0004M) of potassium tert-butoxide in 1.5 ml of DMSO
was heated at 100° for 24 hr. The reaction was cooled
to room temperature and dissolved in water and ether.
The ether phase was isolated and dried. After removal of
the solvent, 0.0633 g of oil was recovered which later
crystallized. The product was identical to 33 by its

spectral and chromatographic properties.

64

Preparation of 32

 

To a solution of 0.506 g (0.005M) of diisopropyl-
amine in 90 m1 of THF was added 2.32 ml of 2.15M n-butyl
lithium in hexane (Ventron) in one portion, and the mix-
ture was stirred 10 min at room temperature. After this
solution was cooled to -78°, a solution of 0.410 g (0.0021M)
of 3 in 5 ml of THF was added in one portion and the
resulting solution was stirred 10 min at -78°. A solution
of 1.09 g (0.005M) of diphenyldisulfide and 0.87 ml
(0.895 g/0.005M) of HMPA in 5 m1 of THF was then added in
one portion and the reaction was stirred two hr at -78°,
followed by 12 hr at room temperature. The reaction mix-
ture was washed sequentially with acidified brine and.
neutral brine, and then dried. After removal of the
solvent, 1.78 g of brown oil was recovered. An ethyl
acetate solution of this material was filtered through
silica gel and the solvent was removed from the filtrate
to yield 1.28 g of crude 33 as a yellow oil. This oil
was dissolved in 10 ml of acetic acid, treated with 5%
aqueous potassium permanganate until the purple color
persisted, and stirred a further 15 min at room tempera-
ture. The color was discharged by the addition of 0.5M
sodium bisulfite. The mixture was extracted with chloro-
form and the extracts were washed sequentially with water
and brine, and then dried. After removal of the solvent,
1.08 g of yellow oil was recovered. The oil was dissolved

in a minimum of hot 50% v/v ethyl acetate--petroleum ether

65
and placed in the refrigerator. A precipitate was
recovered and found to be 0.341 g of diphenyldisulfide.
After removal of the solvent from the mother liquor,
0.617 g of brown oil was recovered. Preparative layer
chromatography (20% v/v ethyl acetate--hexane) of this
oil yielded 0.090 g (13.3% from 3) of 33 as an oil which
displayed the following properties: ir (CDC13) 3025,
1745, 1575 cm-1; pmr (CDC13) (approx 3 1:2.67 mixture of
epimers from comparison of the peaks in the methyl region)
6 0.85 (s,3H), 1.35 (s,3H), 1.4--2.0 (m,8H), 3.2 (m,lH),
3.3 (s,3H), 3.85 (m,lH), 7.5 (m,5H); ms (70 eV) m/e
(rel intensity) 304(1), 292(2), 276(2), 252(9), 194(14),
179(10), 163(10), 151(10), 140(27), 135(28), 125(71),
111(80), 108(65), 95(45), 83(67), 77(100), 71(99), 55(76),
43(50).

 

Attempted Thermolysis of 33_

A solution of 0.0585 g of 33 in 10 m1 of xylene was
refluxed for 18 days. The reaction was cooled to room
temperature and the solvent was removed to yield 0.113 g
of residue. Preparative layer chromatography (20% v/v
ethyl acetate--cyclohexane) of the crude product yielded

0.0494 g of unchanged 32.

Attempted Conversion of 3 to a Homologous Unsaturated

A

Ester Using a Wittig Reagpnt

 

To a solution of 0.098 g (0.0005M) of 3 in 10 m1 of
DMSO was added 0.348 g (0.001M) of the solid Wittig

66
reagent isolated from sodium hydroxide treatment of an
aqueous solution of the salt prepared from triphenyl
phosphine and ethyl bromoacetate. The mixture was heated
at 110° for 12 hr, then cooled to room temperature, poured
into water, and extracted with ether. The extracts were
washed sequentially with water and brine, and then dried.
The orange solution was filtered through silica gel and
the solvent was removed to yield 0.120 g of brown oil,
the major component of which was unreacted 3.

Attempted Conversion of 3 to a Homologous
UnsaturatediAldehyde Using a Wittig Reagent

 

 

To a stirred suspension of 0.0254 g (0.0011M) of
sodium hydride in 10 ml of THF at 0° was added a solution
of 0.288 g (0.0011M) of diethyl 2-(cyclohexylamino)vinyl-
phosphonate in 10 m1 of THF in one portion. The resulting
solution was stirred 15 min at 0°, then a solution of
0.196 g (0.001M) of 3 in 10 m1 of THF was added in one
portion. The reaction was stirred at 0° and monitored
at intervals by GLPC (160°, 4% QF-l) over a 24 hr period.
The ketone 3 remained unchanged. The expected imine
would have yielded a homologous aldehyde derivative of

3 upon acid hydrolysis.

Attempted Conversion of 3 to a Spiro Epoxide

 

To 10 ml of DMSO was added 0.024 g (0.001M) of sodium
hydride and the mixture was heated at 70° for one hr. The

resulting yellow solution was cooled to 0°. To this was

67
added a solution of 0.220 g (0.001M) of trimethyloxosul-
fonium iodide in 10 m1 of THF in one portion, and the
solution was stirred 15 min at 0°. Then a solution of
0.196 g (0.001M) of 3 in 10 m1 of THF was added in one
portion and the reaction was stirred two hr at 0°. The
reaction was warmed to room temperature, stirred two
days, then poured into brine, and extracted with ether.
The extracts were washed sequentially with water and
brine and then dried. After removal of the solvent,
0.154 g of clear oil was recovered whose spectral proper-
ties and GLPC retention were identical to 3.

Treatment of 3 with the Lithium Bnolate
AnIOn of Tart-Butyl Acetate

 

 

To a solution of 0.002M of lithium diisopropyl amine
in 2 m1 of THF at -78° was added 0.232 g (0.002M/0.168
m1) of tart-butyl acetate in one portion. The solution
was stirred 15 min at ~78°, then a solution of 0.196 g
(0.001M) of 3 in 2 ml of THF was added dropwise. The
solution was stirred at -78° for four hr, then 4 m1 of
0.03N hydrochloric acid was added, and the reaction was
warmed to room temperature. The mixture was extracted
with ether and the extracts were washed sequentially with
water and brine, and then dried. After removal of the
solvent, 0.181 g of unreacted 3 was recovered.

In another trial of this experiment, the reaction
was quenched with acetic anhydride at -78°, then warmed

to room temperature. The isolated product was 3.

68

Treatment of 3 with the Lithium Bnolate Anion
of Tart-Butyl Trimethylsilylacetate

 

 

To a solution of 0.0005M of lithium isoprophyl cyclo-
hexyl amine in 10 ml of THF at -78° was added 0.094 g
(0.0005M) of tart-butyl trimethylsilylacetate in one
portion. The solution was stirred five min at -78°, then
a solution of 0.098 g (0.0005M) of 3 in one m1 of THF was
added dropwise. The reaction was stirred 10 min at -78°,
warmed to room temperature, poured into 4N hydrochloric
acid, and then extracted with ether. The ether extract
was washed sequentially with 4N hydrochloric acid and
brine, and then dried. After removal of the solvent,
0.134 g of yellow oil was recovered whose spectral proper-
ties, GLPC behavior (130°, 4% SE-30), and TLC retention
(silica gel, 20% v/v ethyl acetate--hexane) were identical
to those of 3.

Treatment of 3 with the Lithium
Bnolate of Ethyl Acetate

 

 

To a solution of 0.002M of lithium diisopropyl amine
in 10 ml of THF at -78° was added 0.22 g (0.0025M) of
ethyl acetate in one portion. The solution was stirred
15 min at -78°, then a solution of 0.196 g (0.001M) of
3 in one m1 of THF was added dropwise. The reaction was
stirred four hr at -78°, then quenched by the addition of
0.15 ml of glacial acetic acid. The reaction was warmed
to room temperature, poured into water, and extracted
with ether. The ether extracts were washed with brine

and dried. After removal of the solvent, 0.208 g of

69
light yellow oil was recovered whose spectral properties,
GLPC behavior, and TLC retention were identical to those

of 3.

Treatment of 3 with a Reformatsky Reagent

 

To a solution of 0.196 g (0.001M) of 3 in 15 ml of
benzene and one m1 of dimethyoxyethane was added 0.196 g
(0.003M) of zinc dust and 0.501 g (0.003M) of ethyl
bromoacetate. The mixture was brought to reflux. After
30 min most of the zinc was consumed. Refluxing was con-
tinued for a total of 24 hr, then the reaction was cooled
to room temperature and a further 0.003M of zinc dust
and 0.003M of ethyl bromoacetate were added. The reflux
was resumed for another 24 hr, then the reaction was
cooled to room temperature and poured into 2N sulfuric
acid. The mixture was extracted with ether and the
extracts were washed sequentially with water and brine,
and then dried. After removal of the solvent, 0.370 g
of orange oil was recovered. Preparative layer chroma-
tography (20% v/v ethylacetate--cyc1ohexane, double
elution) of the oil yielded 0.160 g of oil whose spectral
properties, GLPC behavior, and TLC retention were iden-

tical to those of 3.

 

Preparation of 33_
Acetylene gas, scrubbed by concentrated sulfuric
acid, was bubbled over a six hr period into a stirred

slurry of 1.15 g (0.05M) of sodium sand in 200 ml of THF

70
which was maintained at 50°. The acid in the scrubber
was changed when it began to darken and turn yellow.
A solution of 1.78 g (0.00908M) of 3 in 10 m1 of THF was
added in one portion to the sodium acetylide-~THF slurry
and the mixture was refluxed for 2 days under argon. The
reaction was cooled to room temperature and poured slowly
into ice water. The aqueous mixture was extracted with
ether and the extracts were washed sequentially with
water and brine, and then dried. After removal of the
solvent, 1.87 g of yellow oil was recovered which later
solidified. Recrystallization from ethyl acetate yielded
0.831 g (41.1%) of 33. An analytical sample of 33 dis-
played the following properties: mp 104--107°; ir (CC14)

3590, 3350 cm‘1

; pmr (CC14) 6 0.8 (s,3H), 0.95 (s,3H),
l.2--2.4 (m,lZH), 3.05 (m,lH), 3.3 (s,3H); ms (70 eV)
m/e (rel intensity) 222(1), 207(1), 198(2), 188(3),
166(10), 154(14), 148(29), 133(28), 122(100), 112(30),
107(65), 93(30), 81(29), 71(90), 55(39), 41(58). ‘
Anal Calcd for C14H2202: C, 75.63; H, 9.97
Found: C, 75.58; H, 10.00

Recovery of 34 from the Treatment
of33 with Formic AEid

 

 

 

A solution of 0.350 g (0.00158M) of 33 in 1.65 ml
of 88% formic acid was heated at 85--90° for 12 hr. The
reaction was cooled to room temperature and made alkaline
by the addition of 5% aqueous sodium hydroxide. The

aqueous mixture was extracted with ether and the extracts

71
were washed sequentially with water and brine, and then
dried. After removal of the solvents, 0.400 g of light
brown oil was recovered. This oil was placed on 40 g of
silica gel and eluted with 50% v/v ether--pentane, to
yield 0.256 g (64.8%) of 33 as a crystalline white solid,
as well as 0.057 g of 33. An analytical sample of 33
displayed the following properties: mp 37--39°; ir
(cc14) 1725 cm‘l; pmr (c014) 8 0.95 (s,3H), 1.1 (s,3H),
l.2--2.6 (m,llH), 3.15 (m,lH), 3.35 (s,3H), 8.05 (s,lH);
ms (70 eV) m/e (rel intensity) 250(1), 226(1), 211(1),
194(3), 180(18), 165(19), 148(34), 133(59), 122(100),
107(96), 93(59), 84(95), 79(54), 71(42), 59(30), 53(35).

Rpgeneration of 33 from 34_

 

To a solution of 0.060 g (0.000240M) of 33 in 3 m1
of methanol was added 0.1 m1 of 30% w/w potassium
hydroxide--methanol. The reaction was stirred at room
temperature for 20 min. The methanol was then removed
and the residue was dissolved in ether and water. The
ether phase was isolated and dried. After removal of
the solvent, 0.0552 g (96.3%) of 33 was recovered, as
evidenced by spectra, TLC retention (silica gel, 50%
v/v ether--pentane), and GLPC behavior (150°, 4% SE-30)

of the product.

72

Recoveryof3§ from Treatment of 33_
with Sulfuric Acid-—Acet1c’Acid'

 

 

 

To a solution of 0.0550 g (0.000248M) of 33 in one
m1 of glacial acetic acid was added one drop of concen-
trated sulfuric acid and the resulting solution was
heated at 50° for 30 min. The reaction was cooled to
0°, neutralized with 30% aqueous sodium hydroxide, and
extracted with ether. The ether extract was dried and
analyzed by GLPC (150°, 4% SE-30) and TLC (silica gel,
50% v/v ether--pentane). A single product had formed
from 33. After removal of the solvent, 0.038 g (58%) of
crude 33 was obtained, whose spectral properties and
GLPC retention were identical to the acetate derivative
of 33 which was subsequently prepared from a pyridine--
acetic anhydride medium.

Preparation of 35 from 33 in
‘Pyridine--Acetic Anhydride

 

A solution of 1.00 g (0.0045M) of 33 in 30 ml of
pyridine and 1.38 ml of acetic anhydride was refluxed
for 12 hr, then cooled to room temperature. The pyridine
was removed and the residue was dissolved in ether. The
ether solution was washed sequentially with 4N hydro-
chloric acid, water, and brine, and then dried. After
removal of the solvent, 1.11 g of brown oil was obtained.
Analysis by GLPC (160°, 4% QF-l) indicated that this was
nearly pure 33. The oil was distilled at 0.15 torr and
the desired acetate was collected at 67°, to yield 1.02 g

(85.7%) of 33, which displayed the following properties:

73

ir (neat) 1735 cm-1

; pmr (CC14) 6 0.92 (s,3H), 1.05 (s,3H),
1.95 (s,3H), 1.2--2.6 (m,llH), 3.1 (m,lH), 3.30 (s,3H).
A satisfactory mass spectrum could not be obtained.

Treatment of 33 with Mercuric
Oxide and’Aqueous Acid

 

 

A mixture of 0.109 g (0.0005M) of red mercuric oxide
and 10 ml of 5% aqueous sulfuric acid was heated at 60°
until a solution had formed. Then 0.111 g (0.0005M) of
solid 33 was added and the resulting mixture was heated
at 60° for 24 hr. The reaction was cooled to room tem-
perature, extracted with ether, the extracts were dried,
and the solvent was removed to yield 0.055 g of unreacted
33.

Treatment of 33 with Mercuric
Sfilfate and Acetic ACid

 

To a solution of 0.055 g (0.00025M) of 33 in one ml
of glacial acetic acid was added 0.075 g (0.00025M) of
mercuric sulfate and the resulting mixture was heated at
60° for 12 hr. The reaction was cooled to room tempera-
ture, diluted with water, and extracted with ether. The
ether extract was washed sequentially with water and
brine, and then dried. After removal of the solvent,
«0.0585 g (87.9%) of the acetate 33 was isolated. Analysis
of the crude product by TLC (silica gel, 50% v/v ether--
pentane) and GLPC (150°, 4% SE-30) disclosed that it was

essentially pure.

74

Treatment of 35 with Mercuric Acetate

 

A solution of 0.257 g of 33 and 0.5 g of mercuric
acetate in 20 m1 of ethyl acetate was stirred 24 hr at
room temperature. Then hydrogen sulfide gas (generated
from A1253 and water) was bubbled into the reaction for
10 min. The black precipitate which formed was removed
by filtration through celite. After removal of the
solvent from the filtrate, 0.257 g of unreacted 33 was
recovered.

Treatment of 33 with Mercuric
Oxide and Aqueous Acid—7

 

 

 

A mixture of 0.109 g (0.0005M) of red mercuric oxide
and 10 m1 of 5% aqueous sulfuric acid was heated at
55--60° until a solution had formed. To this was added
in one portion a solution of 0.132 g (0.0005M) of 33 in
5 ml of THF. The homogeneous reaction mixture was heated
at 55--60° for 24 hr, then cooled to room temperature,
diluted with water, and extracted with ether. The ether
extracts were washed with brine and dried. After removal
of the solvent, 0.110 g of crude 33 was obtained.

Attempted Reduction of the Ethynyl Grogp
of 33 using_Lithium Aluminum‘Hydride

To a solution of 0.111 g (0.0005M) of 33 in 10 m1 of
diglyme was added 0.0378 g (0.001M) of solid lithium
aluminum hydride in one portion. The heterogeneous mix-
ture was refluxed for 18 hr. The reaction was cooled to

room temperature, poured into ice water, neutralized with

75
4N hydrochloric acid, and extracted with chloroform. The
chloroform extracts were washed sequentially with water
and brine, and then dried. The solution was filtered
through silica gel and the solvent was removed from the
filtrate to yield 0.117 g of unreacted 33 as a white
amorphous solid.
Attempted Reduction of the Ethynyl Group
of 33 using Diisobutyl Aluminum Hydride

To a solution of 0.222 g (0.001M) of 33 in 5 ml of
benzene at 0° was added 7 ml of a 20% solution of diiso-
butyl aluminum hydride in hexane (Ventron) and the
resulting solution was stirred five min at 0°. The
reaction was heated at 60° for 3-1/2 days. After cool-
ing to room temperature, five m1 of 50% v/v methanol--
benzene was added to the reaction followed by 10 m1 of
50% v/v methanol--water. The resulting precipitate was
filtered off, then most of the methanol was removed from
the filtrate. The residue was diluted with water and
extracted with ether. The ether extract was washed
sequentially with water and brine, and then dried. After
removal of the solvent, 0.198 g of unreacted, solid 33
was recovered.

Summary of the Attempted Catalytic

Hydrogenation of theiEthynyICCroup
of 3 undEr Several Conditions

 

 

 

 

Ethynyl carbinol 33 was subjected to each of the

following hydrogenation media under one atmosphere of

76
hydrogen and at room temperature: pyridine, 2% palladium
on calcium carbonate, 24 hr; dioxane, 2% palladium on
calcium carbonate, 1 hr; methanol, palladium on carbon,
6 hr; acetic acid, palladium on carbon, 24 hr; methanol,
platinum oxide, 24 hr. In each case, 33 was recovered

unchanged.

Attempted Claisen-Cope Rearrangement of 33_
Formate 34 (0.119 g) was heated at 250° for 19-1/2

hr in an evacuated, sealed tube and recovered unchanged.

Attempted Claisen-Cppe Rearrangement of
_35by Flow Pyrolysis

 

 

A solution of 0.359 g of 33 in 50 ml of cyclohexane
was introduced dropwise (one drop/s) into the top of a
Vigreux column packed with Pyrex beads which was main-
tained at 300°. The system was flushed by a stream of
nitrogen (40 bubbles/min through a U-tube charged with
mineral oil) during the course of the pyrolysis. The
effluent was collected in two cold traps connected in
series which were maintained at -78°. After removal of
the solvent, 0.157 g of unchanged 33 was recovered.

Attempted Ag(I) Catalyzed Claisen-Cope
Rearrangement of 35_

 

 

To a solution of 0.395 g of 35 in 20 m1 of acetone
was added one drop of silver perchlorate monohydrate and
the resulting solution was refluxed for five days. The

reaction was cooled to room temperature, diluted with

77
five m1 of saturated ammonium chloride, and stirred for
15 min. The mixture was diluted with ether and filtered
through silica gel. After removal of the solvent, 0.340 g
of brown oil was recovered, which was a mixture of 33 and
32':-
Conversion of 33 to a Phosphite Ester

(36) and Attempted Thermal Claisen-
Cope Rearrangement of the Derivative

 

 

 

 

To a solution of 0.204 g (0.00092M) of 33 in 20 ml
of triethylamine at room temperature was added 0.15 ml
of diethyl chlorophosphite (Aldrich) in one portion and
the reaction was stirred for 24 hr. The reaction was
diluted with water and washed sequentially with water and
brine, and then dried. After removal of the solvent,
0.269 g of yellow oil was recovered. Preparative layer
chromatography (50% v/v ethyl acetate--cyclohexane) of
the oil yielded 0.140 g of 33 and 0.078 g of 33. The
phosphite ester 33 displayed the following properties:

ir (neat) 1265, 1070, 1025, 970 cm"1

; pmr (CC14) 6 0.9
(s,3H), 1.05 (s,3H), 1.3 (t,6H), l.4--2.6 (m,llH), 3.0
(m,lH), 3.2 (s,3H), 3.9 (m,4H).

A sample of 33 was heated at 100° for 24 hr in an
evacuated, sealed tube and later recovered unchanged.

Attempted Conversion of 33 to a Chloro- Allene
with Thionyl Chloride--Pyridine

 

To a solution of 0.111 g of 33 in 10 m1 of pyridine

was added 2.5 ml of thionyl chloride in one portion. The

78
dark brown solution was stirred at room temperature for
24 hr and the product isolated in_the usual way. Analysis
by TLC (silica gel, 40% v/v ether--pentane) and spectra
of the product showed that it was unreacted 33.
Attempted Conversion of 33 to an Allene

using Lithium Aluminum
Hydride-~A1uminum Trichloride

 

 

 

A solution of 0.222 g (0.001M) of 33 in seven m1 of
THF was added in one portion to a stirred slurry of 0.0756
g (0.002M) of lithium aluminum hydride and 0.200 g
(0.0015M) of aluminum trichloride in eight ml of THF at
room temperature. The mixture was then refluxed for 24
hr. The reaction was cooled to room temperature, poured
into ice water, and the aqueous mixture was extracted with
ether. The ether extracts were washed sequentially with
water and brine, and then dried. After removal of the
solvent, 0.220 g of 33 was recovered.

Attempted Conversion of 33 to a
Methyl-SUEstituted Allene

 

 

To a stirred suspension of 1.90 g (0.01M) of cuprous
iodide in 25 m1 of ether at 0° was added 10.9 ml of 2.3M
methyl lithium in ether solution (Ventron) in one portion.
The mixture was stirred 2.5 hr at 0° at which point a
clear solution was obtained. The solution was cooled to
-78° and a solution of 0.528 g (0.002M) of 33 in 10 m1
of ether was added dropwise. The reaction was stirred

15 min at -78°, then warmed to room temperature and

79
stirred six hr. The reaction was diluted with ether and
washed with pH 8 ammonium hydroxide (saturated ammonium
chloride whose pH was adjusted with concentrated ammonium
hydroxide) until most of the blue Cu(II) was removed.
After drying and removal of the solvent, 0.563 g of light
green oil was recovered. This oil was placed on 50 g of
silica gel and eluted with 20% v/v ethyl acetate--petroleum

ether to yield 0.214 g of 35 and 0.287 g of 33.

Preparation of 37

 

To a solution of 0.280 g (0.004M) of ethoxyacetylene
(Farchan) in 10 ml of ether was added 1.93 ml of 2.08M
n-butyl lithium in hexane (Ventron) and the resulting
cloudy solution was stirred 10 min at room temperature.

A solution of 0.434 g (0.00221M) of 3 in 10 ml of ether
was then added in one portion, followed by 0.70 ml

(0.72 g/0.004M) of HMPA. The reaction was stirred 12

hr, and then poured into cold 4N hydrochloric acid, and
extracted with ether. The ether extracts were washed
sequentially with 4N hydrochloric acid, water, and brine,
and then dried. After removal of the ether, the residue
was dissolved in methanol, norit was added, and the mix-
ture was heated on a steam bath for five min.» After fil-
tration of the hot mixture, the methanol was removed to
yield 0.579 g (98.3%) of light yellow, crystalline 32.

An analytical sample of 37 displayed the following pro-

perties: mp l32--134° (petroleum ether-~ethyl acetate);

80
ir (cc14) 1700, 1630, 1265 cm'l; pmr (cc14) a 0.9 (s,3H),
1.05 (s,3H), 1.25 (t,3H), 1.4--Z.9 (m,llH), 3.15 (m,lH),
3.25 (s,3H), 3.9 (q,2H); UV (95% ethanol) 272 nm
(a 992); ms (70 eV) m/e (rel intensity) 267(13), 266(53),
251(4), 237(4), 234(60), 219(26), 205(50), 196(65),
177(35), 163(45), 157(45), 129(55), 109(58), 97(100),
71(60), 55(86), 43(95), 41(87); cmr (CDC13) 5 (rel
intensity) 13.s7(77), 15.32(82), 17.08(91), 20.08(75),
23.67(100), 24.08(68), ZS.73(97), 33.10(92), 42.03(53),
SZ.44(33), 57.70(58), 62.26(68), 83.58(87), 113.03(21),
163.46(15), 182.69(13).
Anal Calcd for C O

H C, 72.14; H, 9.84

26 3‘
Found: C, 72.13; H, 9.84

16

Preparation of 38_

 

A solution of 0.098 g of 3 and 0.1 m1 of ethoxy-
acetylene in five m1 of benzene was irradiated for 3-1/2
hr with a Hanovia lamp using a Corex filter. After
removal of the solvent, 0.112 g of yellow oil was recovered.
The pmr spectrum of the crude product indicated that no
adduct had formed and that 3 had isomerized to its cis-
isomer as evidenced by the methyl shifts.

Accordingly, a solution of 0.105 g of 3 in five m1
of benzene was irradiated as before. After removal of
the solvent, 0.102 g of clear oil was recovered. The
GLPC retention (160°, 4% QF-l) of the product was nearly

coincident with that of the starting material but the pmr

81

spectrum of the product indicated that 3 had completely
isomerized to 38. The cis-fused perhydroindene, 38,
displayed the following prOperties: ir (neat) 1735 cm'l;
pmr (CC14) 6 0.85 (s,3H), 0.92 (s,3H), 1.0--2.4 (m,lOH),
3.2 (m,lH), 3.25 (s,3H); ms (70 eV) m/e (rel intensity)
197(5), 196(26), 181(8), 164(19), 149(19), 136(21),
122(35), 109(100), 97(65), 81(39), 71(45), 58(43),
41(68).

Anal Calcd for C H 0 ° C, 73.43; H, 10.27

12 20 2'
Found: C, 73.24; H, 10.34

Treatment of 3 with Allyl Magnesium Bromide in THF

A solution of 0.242 g (0.002M) of allyl bromide in
20 m1 of THF was stirred with 0.048 g (0.002M) of magnesium
turnings for three hr at room temperature, at which point
all the magnesium had dissolved to form a clear solution.
Then a solution of 0.196 g (0.001M) of 3 in one m1 of
THF was added to the Grignard solution. The reaction was
stirred two days at room temperature, then poured into
water, extracted with ether, and the extracts were washed
sequentially with water and brine, and then dried. After
removal of the solvent, 0.199 g of clear oil was recovered,

the pmr spectrum of which indicated it to be unreacted 3.

 

Preparation of 39
A solution of 0.484 g (0.004M) of allyl bromide 1n
15 m1 of ether was stirred with 0.096 g (0.004M) of mag-

nesium turnings for three hr at room temperature, at

82

which point all the magnesium had dissolved to form a
clear solution. Then a solution of 0.196 g (0.001M) of
3 in five ml of ether was added to the Grignard solution.
The reaction was stirred for 12 hr at room temperature,
then refluxed for two hr. The reaction was cooled to
room temperature, poured into saturated aqueous ammonium
chloride, and extracted with ether. The ether extracts
were washed sequentially with water and brine, and then
dried. After removal of the solvent, 0.212 g (89.1%) of
39 was obtained as a colorless oil. Analysis by GLPC
(160°, 4% QF-l) of the product indicated that 3 had been
completely consumed. An analytical sample of 39 dis-
played the following properties: ir (neat) 3520, 3025,
1630, 985, 905 cm‘l; pmr (0014) 6 1.0 (s,3H), 1.1 (s,3H),
1.2--2.4 (m,l3H), 3.0 (m,lH), 3.15 (s,3H), 5.0 (m,2H),
5.7 (m,lH); ms (70 eV) m/e (rel intensity) 238(0.1),
220(0.6), 206(0.8), 197(0.6), 188(0.5), 179(2), 165(3),
147(8), 122(9), 107(6), 93(4), 91(4), 81(5), 71(9),
58(30), 43(100).

Anal Calcd for C H 0 ° C, 75.58; H, 10.99

15 26 2'
Found: C, 75.51; H, 11.05

 

Preparation of 40_

A mixture of 7.2 g (0.3M) of magnesium turnings, a
small crystal of iodine, and 30 ml of ether was stirred
until the iodine color had lightened appreciably (about
15 min). Then a solution of 13.5 g (0.1M) of crotyl

bromide (Aldrich) in 70 m1 of ether was added dropwise

83

to the magnesium turnings over five hr at room tempera-
ture. After the addition was complete, the metallic gray
solution was stirred a further 30 min. Then a solution
of 10 g (0.051M) of 3 in 100 ml of ether was added to
the Grignard solution over one hr. The reaction was
stirred for another hour after the addition was complete,
then poured into cold, saturated ammonium chloride. The
aqueous mixture was extracted with ether and the extracts
were washed sequentially with water and brine, and then
dried. Analysis by GLPC (160°, 4% QF-l) of the ether
solution indicated that 3 had been totally consumed.
After removal of the solvent, 12.40 g (96.5%) of 49 was
recovered as a clear oil. An analytical sample of 40
displayed the following prOperties: ir (neat) 3520,
3025, 1630, 990, 905 cm'l; pmr (c014) 6 0.95 (d,3H),
1.1 (bs,6H), 1.15--2.6 (m,lZH), 3.0 (m,lH), 3.15 (s,3H),
4.9 (m,2H), 5.8 (m,lH); ms (70 eV) m/e (rel intensity)
252(0.3), 240(0.2), 237(0.2), 234(2), 224(6), 220(3),
210(2), 202(2), 197(7), 179(19), 165(30), 147(100),
125(32), 122(37), 105(35), 91(25), 81(31), 71(52),
55(51), 41(56).

Anal Calcd for C H 0 ° C, 76.14; H, 11.18

16 28 2'
Found: C, 76.00; H, 11.15

Preparation of 43

 

A solution of 57.7 g (0.27M) of sodium metaperiodate

and 0.30 g of potassium permanganate in 1000 m1 of water

84

was added to a solution of 11.3 g (0.045M) of 49 in 250
m1 of tert-butanol and 100 ml of 5% aqueous potassium
carbonate, over 30 min at room temperature. The reaction
was maintained at pH 8 during the addition by adding two
further 100 m1 portions of 5% aqueous potassium carbonate,
at equally spaced intervals, to the reaction. The reaction
was stirred four hr at room temperature after the addi-
tion was complete, then acidified with concentrated
sulfuric acid. The reaction was extracted with four,
200 m1 portions of chloroform, and the extracts were
washed sequentially with water and brine, and then dried.
After removal of the solvent, 12.27 g of the crude acid,
42, was recovered. Analysis of 42 by TLC (silica gel,
20% v/v ethyl acetate--cyclohexane) indicated the absence
of 40. The neat ir spectrum of 42 displayed: 3600~-2300
(broad), 1700 (strong) cm'l.

The crude acid, 42, was dissolved in 100 m1 of ether
and treated with an ether solution of diazomethane
(approx 0.05M in 500 m1) at 0°. The excess diazomethane
and most of the ether were boiled off on a steam bath.
The remainder of the ether was removed under reduced
pressure to yield 11.72 g of clear viscous oil. Analysis
of the oil by TLC indicated an absence of 42. Analysis
by GLPC (160°, 4% QF-l) indicated one major peak at long
retention and some volatile impurities. This material
was purified by HPLC (15 x 500 mm silica gel, 20% v/v

ethyl acetate--hexane, one ml/min) in 20 portions to

85
yield 4.64 g (36.2%) of 43 as a colorless oily solid which
displayed the following properties: ir (neat) 3480,
1710 cm'l; pmr (c014) 6 0.9--2.0 (m,21H), 3.05 (m,lH),
3.2 (s,3H), 3.6 (s,3H); ms (70 eV) m/e (rel intensity)
284(0), 266(1), 252(0.6), 234(1.3), 219(0.8), 208(13),
196(46), 164(11), 147(17), 125(62), 121(69), 112(61),
97(54), 85(60), 71(100), 57(75), 41(84).

APPENDIX

86
2.5 3.0 3.5 4.0 M'CRONS 5.0 6.0 30
10° - . . z ' . 1 . . ' .

IRANSMITTANCEI‘Vo)

M
O

 

o , . p 1 ; . . . .
4000 3500 3000 2500 2000 1500
8.0 M'CRONS 10.0 11.01

    
 
 

100

TRANSMITTANCE(%)

20

1800 1600 1400 1200 1000 800

FFIQUENLV 1( M

Figure 1. Infrared spectrum of 1.

87

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Infrared spectrum of 2 (CDCl

Figure 2.

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88
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; f i . ' 1 .. .. i U .
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2500 2000 1500
1,0 WCRONS 10.0 11.0120 16.0

1oc:-- — ~ -~ ~ « , ._ - - —— '~———--.~——-«~.1co
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4000 3500

 

 

 

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Figure 3. Infrared spectrum of 3.

TRANSMITTANCE(%)

IRANSMIT 1 A. 151

89
4.0
1

MICRONS 5_o

6.0

 

 

 

 

 

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Figure 4.

Infrared spectrum of 4.

90

30

2.5
100 »r

4.0 M‘CRONS 5.0 6.0

3.5

 

 

 

 

 

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FFZ‘N ~11: r '--'

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1400

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Figure 5.

25

91
3.0 . 315 4.0 M'CRONS 5.0 6.0 8.0

 

 

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TRANSMHTANCE(%)
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Figure 6. Infrared spectrum of 6.

92

 
     

2.5 3.0 , 3.5 4.0 MICRONS 5.0 6.0 8.0

100
30

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80
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Figure 9. Infrared spectrum of IQ.

95 .
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Figure 10. Infrared spectrum of 11.

MICRONS 5.0 6.0

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