ME @r'asmmvzw Am
FHQTQQ-fiEWSTRY as mm
{tfigfigé‘aé‘flefit‘éé-
DECAHYDmAWHMCENE.
TQeQNE-@, 1' .CYCLQPEHmE;

Thosta {m- t’E—m Dogma wit M. Sc
IifiCHEGRN STATE UNR’EESETY

David C. Lamkizt
we?

LIBRARY

T H F S t S .
chhlgan State
University

 

 

ABSTRACT
THE PREPARATION AND PHOTOCHEMISTRY OF
SPIRO[1,2,3,4,5,6,7.8,9,10-DECAHYDROANTHRACENE-
10-ONE-9.1'-CYCLOPENTANE]

by David C. Lankin

The purpose of this study was to investigate the struc-
ture of the product or products from the oxidation of s-do—
decahydrotriphenylene 3% with peroxytrifluoroacetic acid—
boron fluoride etherate and further, to study the photo—
chemistry of the dienone products derived from such an
oxidation.

When s-dodecahydrotriphenylene gg'was oxidized with a
miXture of peroxytrifiluoroacetic acid—boron fluoride ether-
ate in methylene chloride at -3 to +10, spiro[1,2,3,4,5,6,
7,8,9,10-decahydroanthrace—10-one—9,1'-cyclopentane]lgg
was produced in 45% yield. When the oxidation was carried
out at -67 to -65°, unoxidized hydrocarbon 33, dienone fig,
and Spiro[1,2,3,4,5,6,7,8,9,10-decahydrophenanthrene-10-

one-9,1'-cyclopentane] 33 were formed. It was shown that

 

33 34 35

David C. Lankin
dienone 33 could be converted into dienone 3Q by treatment
with either trifluoroacetic acid or boron fluoride etherate
in methylene chloride at room temperature. A proposed re-
action mechanism accounts for the formation of the dienones.

Irradiation of dienone fig in ether solution provided
dienone 333 Irradiation of dienone 3g in methanol solution
produced spiro[tetracyclo[7.4.1.01I903'3]tetradec-3-ene-2—
one—14,1'-cyclopentane], §§J shown to be the primary photo-
product of 3E, Further irradiation of §§ in ether afforded
dienone 333 The intermediacy of QQ, in the production of
33 from photolysis of dienone fig in ether has been shown
and the proposed mechanisms for the various photochemical

transformations are consistent with these results.

 

58

m

Irradiation of dienone 33 in ether provided ring fis—
sion products, but no ketone §§ was formed.

Control experiments showed that none of the irradiated
compounds Wfifii reactive in the dark in the solvents used

for the irradiations.

THE PREPARATION AND PHOTOCHEMISTRY OF
SPIRO[1,2,3,4,5,6 7,8,9,10-DECAHYDROANTHRACENE-
10-ONE-9,1'-CYCLOPENTANE]

BY

David C. Lankin

A THESIS

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

MASTER OF SCIENCE
Department of Chemistry

1967

ACKNOWLEDGMENT

The author wishes to express his sincere apprGCiation
to Professor Harold Hart for his encouragement and en-
thusiasm during the course of this study.

Appreciation is also extended to Mr. Michael Gross
for his assistance in operating the HA—lOO spectrometer.

Appreciation is also extended to Mr. Roger Murray
for many helpful discussions.

Appreciation is extended to Michigan State University
for a Graduate Teaching Assistantship from September, 1964

to Spring, 1967.

ii

TABLE OF CONTENTS

PAGE
INTRODUCTION . . . . . . . . . . . . . . . . . . . . . 1
RESULTS AND DISCUSSION . . . . . . . . . . . . . . . . 11
A. The Oxidation of s-Dodecahydrotriphenylene. . 11
B. The Photochemistry of Spiro[1,2,3,4,5,6,7,8,
9,10-decahydroanthracene—10-one—9,1'-cyclo—
pentane] . . . . . . . . . . . . . . . . . . 20
C. The Photochemistry of Spiro[tetracyclo
[7.4.1.019038]tetradec-3-ene-2-one-14,1'-
cyclopentane] . . . . . . . . . . . . . . . 30
D. The Photochemistry of Spiro[l, 2, 3, 4, 5, 6, 7,8,
9, 10-decahydr0phenanthrene-10-one-9, 1'-
cyclopentane] . . . . . . . . . . . . . . 37
EXPERIMENTAL . . . . . . . . . . . . . . . . . . . . . 40
A. General Procedures . . . . . . . . . . . . . 40
B. Preparation of s-Dodecahydrotriphenylene . . 41
C. The Oxidation of s-Dodecahydrotriphenylene. . 42
1. The Reaction with 110% Excess Oxidant at
-3 to +10 . . . . . . . . . . . . . . . 42
2. The Reaction with 110% Excess Oxidant at
—67 to -650 . . . . . . . . . . . . . 43
D. The Rearrangement of Spiro[1,2,3,4,5,6,7,8,9,
10-decahydrOphenanthrene-lo—one—9,1'—cyclo—
pentane] with Boron Fluoride Etherate. . . . 45
E. The Rearrangement of Spiro[1,2,3,4,5,6,7,8,9,
10-decahydrophenanthrene-lo-one-9,1‘-cyclo-
pentane] with Trifluoroacetic Acid . . . . . 46
F. General Photolysis Procedures . . . . . . . . 46

iii

TABLE OF CONTENTS (Cont.)

G. Irradiation of Spiro]1,2,3,4,5,6,7,8,9,10-
decahydroanthracene—10-one-9,1'-cyclo—
pentane] in Anhydrous Ether . . . .

H. The Dark Reaction of Spiro[1,2,3,4,5,6,7,8,9,
10-decahydroanthracene-lO-one-9,1'-cyclo-
pentane] in Anhydrous Ether . . . .

I. Irradiation of Spiro[1,2,3,4,5,6,7,8,9,10-
decahydroanthracene-lO-one-9,1'-cyclo—
pentane] in Methanol . . . . . . . . . . .

J. The Dark Reaction of Spiro[1,2,3,4,5,6,7,8,9,
10-decahydroanthracene-lO-one-9,1'-cyclo-
pentane] in Methanol . . . . . . . . . . .

K. Irradiation of Spiro[tetracyclo[7.4.1.01'903'3]
tetradec—3—ene-2-one—14,1'-cyclopentane] in
Anhydrous Ether . . . . . . . . . . . . . .

L. The Dark Reaction of Spiro[tetracyclo
[7.4.1.01I903'3]tetradec-3—ene-2—one-14,1'—
cyclopentane] in Anhydrous Ether . . . . . .

M. Irradiation of Spiro[1,2,3,4,5,6,7,8,9,10-
deCahydrOphenanthrene—10—one—9,1'-cyclo-
pentane] in Anhydrous Ether . . .

N. The Dark Reaction of Spiro[1,2,3,4,5,6,7,8,9,

10-decahydrophenanthrene-10-one-9,1'-cyclo-
pentane] in Anhydrous Ether . . . . . . . .

SUMMARY . . . . . . . . . . . . .
LITERATURE CITED
APPENDIX . . . . . . . . . . . . . . . . . . . . . .
1. a) IR Spectrum of Spiro[1,2,3,4,5,6,7,8,9,10-
decahydroanthracene-lo—one-9,1'-cyclo-
pentane] . . . . . . . . . . . . .
b) UV Spectrum of Spiro[1,2,3,4,5,6,7,8,9,10—

decahydroanthracene-lO—one—9,1'-cyclo-
pentane] . . . . .

iv

PAGE

47

48

49

49

50

50

51

51

52

54

57

58

58

TABLE OF CONTENTS (Cont.)

PAGE
2. a) IR Spectrum of Spiro[1,2,3,4,5,6,7,8,9,10—
decahydrOphenanthrene—lo-one—9,1'-cyclo-
pentane] . . . . . . . . . . . . . . . . 59
b) UV Spectrum of Spiro[1,2,3,4,5,6,7,8,9,10-
decahydrophenanthrene-10-one—9,1‘—cyclo-
pentane] . . . . . . . . . . . . . . . . 59

3. a) IR Spectrum of Spiro[tetracyclo[7.4.1.01'903'8]
tetradec-3—ene-2-one-14,1'-cyclopentane]. 60

b) UV Spectrum ofSpiro[tetracyclo[7.4.1.01'903'8]
tetradec-3-3n3-2-one-14,1‘-cyclopentane]. 60

4. NMR Spectrum of Spiro[1,2,3,4,5,6,7,8,9,10-
decahydroanthracene-10—one-9,1'-cyclo-
pentane] . . . . . . . . . . . . . . . . . . 61

5. NMR Spectrum of Spiro[1,2,3,4,5,6,7,8,9,10-
decahydrophenanthrene-10-one-9,1'—cyclo-
pentane]‘. . . . . . . . . . . . . . . . . . 62

6. NMR Spectrum of Spiro[tetracyclo[7.4.1.01'903'3]
tetradec-B-ene-Z-one—14,1'-cyclopentane] . . 63

LIST OF FIGURES

FIGURE

1. General mode of photochemical reaction of
6,6-disubstituted-2,4-cyclohexadienones

2. A mechanism for the oxidation of s-dodeca-
hydrotriphenylene . . . . . . . . . . . .

3. A mechanistic scheme depicting principle modes
of rearrangement of 2,5-cyclohexadienones

4. The photolysis of spiro[1,2,3,4,5,6,7,8,9,10-
decahydroanthracene-lO-one-9,1'-cyclopentane]
in ether as monitored by uv spectroscopy .

5. The photolysis of spiro[1,2,3,4,5,6,7,8,9,10-
decahydroanthracene-10—one-9,1'-cyclopentane]
in methanol as monitored by uv spectroscopy

6. A mechanistic scheme depicting principle modes
of photorearrangement of bicyclo[3. 1.0]
hexenones . . . . . . . . . . . . . .

7. The photolysis of spiro[tetracyclo[7.4.1.01'903'3]

tetradec-3-ene-2-one—14,1'-cyclopentane] in
ether as monitored by uv Spectroscopy .

vi

PAGE

18

21

25

26

31

34

INTRODUCTION

It has been established that organic peracids are
very good sources of electrophilic hydroxyl, particularly
in their reaction with aromatic hydrocarbons(1). Peroxy-
trifluoroacetic acid provides a very efficient source of
positive hydroxyl, as trifluoroacetate ion is a good
leaving group(2). However, while peroxytrifluoroacetic
acid hydroxylations of aromatic compounds result in good
yields, the conversions are generally low. It was there—
fore considered that oxidation efficiency could be greatly
enhanced by the presence of a Lewis acid, such as boron
fluoride, which could coordinate with one of the oxygens
of the trifluoroacetate group, thus facilitating hetero—

lytic cleavage of the peroxide oxygen-oxygen bond(3).

 

(103-BF3 O
47 47 - +
CF30\,‘ or CF3C\g\ > CF3C02 + OH
O-O\ ,O'—O\
l.
H BF3 H

When mesitylene 1 was oxidized with a mixture of peroxy—
trifluoroacetic acid and boron fluoride in methylene chlor-
ide at 00(3,4), mesitol 2 was formed in 88% yield. When
the oxidation was carried out at —40°, the yield was quanti—

tative.

 

OH
O we... BF, >
CH2C12. 00
l, 2,

The peroxytrifluoroacetic acid—boron fluoride oxidation of
prehnitene 3 proceeded equally well producing the expected
prehnitol, plus other products, one of which was identified

as 4,5,6,6—tetramethyl-2,4—cyclohexadienone 4(3,4,5).

O

Dienone 4 is presumed to arise from attack of electrophilic

O

,9: :1,

hydroxyl at a substituted carbon atom followed by a Wagner—
Meerwein methyl shift and loss of a proton. This was a
particularly important observation, since the direct syn-
thesis of alkyl substituted 2,4-cyclohexadienones might
be achieved from the corresponding alkyl substituted benzene.
It seemed likely that if the benzene were totally sub-
stituted with alkyl groups, peroxytrifluoroacetic acid-
boron fluoride oxidation might render only dienone products.
This was shown to be the case when hexamethylbenzene 5 was
oxidized with peroxytrifluoroacetic acid-boron fluoride
etherate in methylene chloride at 0°; 2,3,4,5,6,6-hexa—

methyl—2,4-cyclohexadienone 6 was formed in greater than 90%

3
yield (6,7). Oxidation of hexaethylbenzene 1 results in the

formation of the corresponding hexaethyldienone 8 in 82%

 

yield (6).
R
(3 R
R R R
CF3C020H, BF3°Et20 R
>
CH2C12, 00
R R R
R R
‘5 R = CH3 IQ R = CH3
1, R = C2H5 g, R = C2H5

Oxidation of durene 9 gave 3,4,6,6—tetramethy1-2,4—cyclo-

hexadienone 12 in over 50% yield (8).

 

O
CF3COZOH, BF3'Et20
>
CH2C12, 0°
2 12.

Oxidation of pentamethylbenzene gives predominantly dienone
products (9).

Recently, the oxidation of 1,2,3,4-tetramethylnaphtha—
lene 11 has provided naphthaleneones(benzocyclohexa-

dienones) 12 and 13, as the major products (10).

 

CF3COZOH,-12°
> +
O BF3 'Etzo Q
CH2C12

13

«VU

The photochemistry of 6,6—disubstituted-2,4—cyclo-
hexadienones was first studied by Barton and Quinkert (14)
and has been extensively reviewed (11,12,13). Figure 1
depicts the reaction alternatives of 2,4-cyclohexadienones.

In general, three primary processes of 2,4-cyclohexa-
dienones have been elucidated: a) ring fission of 14 to
give a gis'ketene 15 which can undergo 1,2 addition of a
nucleophile H-X to give the Byzée unsaturated diene acid
derivative 16, having the gig geometry, which can be sub-
sequently photoisomerized to the trans 57:66 unsaturated
diene acid derivative 11' or the gig ketene can undergo
1,6 addition of H-X to give the diene acid derivative 18,
which is much rarer; b) loss of a group Y from C6, either
by homolytic cleavage of the C-Y bond or by migration of Y
to C5, provided it is unsubstituted (R2 = H) followed by
aromatization to the phenols 12 or 20; c) rearrangement to
a bicyclo[3.1.0]hexenone 21, Which pathway the cyclohexa-

dienone takes depends on the number and position of the

substituents on the cyclohexadienone ring.

5
Pathways a_ and b_were first elucidated by Barton and
Quinkert (14). Route 3” however, is considerably different
than as first proposed by Barton (11). It was first sug-
gested that the gi§_ketene 15 isomerized to a trans ketene
15a which added the nucleophilic species H-X 1,2 or 1,4 to
give 5y:Oe and cfizée diene acid derivatives respectively.
Whether H—X added 1,2 or 1,4 was presumed to be determined

by the 1,3—steric interactions in the trans ketene 15a.

R5
R3
O:C_
R1(Y)
R4
Y(R1)
R2
15a

IW

However, Hart and Collins (9) have shown that cyclo-
hexadienones which undergo ring fission do so to give a
gi§_ketene which reacts with H-X to give a 67:56 gig diene
acid derivative (1,2 addition) which can be photoisomerized
Eb the Byzée trans diene acid derivative. For example, ir—
radiation of a methanol solution of 22 through Pyrex gave
dienoate gg’having the gi§_geometry. Irradiation of 22
through vycor gave the isomerized dienoate 24 having the
trans geometry, as well as 23, Only in one case was a small
amount of a6:75 unsaturated dienoate detected. Irradiation

of a methanol solution of dienone 10 gave, in addition to

.mwcocmflvmxmnoHowo

Iv.NIUmu5uHquDmHUI®.® mo COHuommH HMOHEOSOOponm mo OUOE Hmumcmm one .H wusmflm

S
5

2m; 3 >2
memv «mm ma

5H «m
//ll\\ vm , ‘ .m X mm mm
\\II/rIL\ x .IkHWhv _/rI\\ umrll

nu

 

 

 

E E All H
m >n vaflm o A mv
m \ /
mm Av m ¢ H
m m va mam mm
ON ma M
mm mm , . -
GOHDHUUOIN.H GOHDHUUOI®.H
am am w «m
H mm—— m
. m a n xlm
. a m
mo mo
«m , .ww ma
>3 i— mm mm

mm
v «m vm
vaam m O m .l/
.III I
nm-H >3 M >3 M
m
m H _ n
mm 0 mm Hm O m 0 m

_ hv
D M m ‘—
————> H hV
MeOH H Vycor C02Me

22 23 24

AN [W m

the major product Byzée unsaturated dienoate 26, about 15%
of 21, arising from 1,6 addition of the methanol to the
cis ketene 25 (8,9). No diene acid derivatives arising from

1,4 addition of the nucleophile were observed.

hv

 

—~ /] 2.9,
MeOH \\
Pyrex
‘—-.' CO Me
1,6 \ 2
10 25 27

Reaction alternative 9, recently elucidated by Hart,
Collins and Waring (6,15), involves rearrangement to a
bicyclo[3.1.0]hexenone. Irradiations of 1% ether solutions
of 2,3,4,5,6,6-hexamethyl-2,4-cyclohexadienone, fi’or the
hexaethyl analog, 2 through Pyrex, resulted in the formation
of the corresponding bicyclo[3.1.0]hexenones, 22 and 22”

The mechanism has been shown, by suitable labelling experi-

ments, to involve "bond crossing" rather than alkyl

 

O
R O R
R R
R hv/ether/Pyrex R
‘\
R R R
R R
g R=CH3 2,52, R=CH3
2 R = C2H5 22 R = C2H5
migration (6). This is a radical departure from the more

familiar ring fission reaction which had previously been ob-
served. There is however, a relationship between ring fis—
sion and bicyclic ketone formation, in that they are compet-
ing reactions. Evidence to support this idea has been
presented by Hart and Collins (9). Irradiation of a methanol
solution of 2,4,5,6,6-pentamethyl-2,4—cyclohexadienone 22'

provided both bicyclic ketone 22 and diene ester 22 (9).

O
+ \_/
MeOH/ Pyrex ' \

30 31 32

(W NV w

 

 

The course of the reaction seems to be controlled by the
position of the hydrogen on the ring. In the pentamethyl
series, if the hydrogen is at C2, photolysis gives ex—

clusively the ring fission product. When the hydrogen is

at C5, photolysis gives exclusively the bicyclic ketone.
Since the photochemistry of 2,4—cyclohexadienones de—
pends on the number and position of substituents and as has
been shown, photolysis of hexaalkylsubstituted—2,4-cyclo-
hexadienones results in the formation of bicyclic ketones,
it seemed that a subtle structural modification in dienones
2 or 2'might alter the photochemical behavior of the di-
enone. An investigation into the photochemistry of Spiro-
[1,2,3,4,5,6,7,8,9,10—decahydrophenanthrene-10-one—9,1'—
cyclopentane] 22,(16) was undertaken, since it is struc-
turally similar to dienone 2. The ethyl groups have ef—
fectively been prevented from rotating, by incorporating

them into rings.

‘0

. o
.0.

33 g

I'W

It was visualized that the synthesis of dienone 22
could be accomplished by peroxytrifluoroacetic acid-boron
fluoride etherate oxidation of s-dodecahydrotriphenylene 22'
(17). Attack of electrophilic peroxytrifluoroacetic acid
on 22 followed by a 1,2-Wagner-Meerwein alkyl shift and loss
of a proton should provide a reasonable synthetic route to

dienone 22,

00.

34

m

The oxidation of hydrocarbon 2g and the photochemistry of

the products will be the subject of this thesis.

1o

RESULTS AND DISCUSS ION
A. The Oxidation of s-Dodecahydrotriphenylene

The preparation of s~dodecahydrotriphenylene 2g'was
carried out according to the procedure by Mannich (17).
Cyclohexanone, dissolved in methanol, was condensed with
itself in the presence of concentrated sulfuric acid. After
refluxing and stirring for 24-36 hrs, work-up afforded the
literature yield of 223

s-Dodecahydrotriphenylene was oxidized at —3 to +10
with 110% excess peroxytrifluoroacetic acid in methylene
chloride and distilled 47% boron fluoride etherate, both Of
which were added at equal rates over a 1.5 hr period. Under
these conditions, a 100% conversion of the starting material
resulted, as determined by tlc analysis of the reaction
mixture before hydrolysis and after work—up, and the product,
formed in 45% yield after recrystallization from methanol,
mp 115-1170, was shown by analysis on tlc to consist of a
single compound, free of starting material. The compound
was assigned the structure spiro[1,2,3,4,5,6,7,8,9,10-deca-
hydroanthracene—lO-one-9,1'-cyclopentane], 22 (16), on

spectroscopic evidence and mode of formation.

11

12

 

I'll o
>
. CH2C12, -3 to 10

34 35

M“ m

Compound 22, a colorless crystalline solid, analyzed
well for C18H24O. The mass Spectrum indicated a parent peak
at m/e 256, showing this to be the molecular formula. The
ir spectrum of 22 in CCl4 solution showed principle absorp-
tions at 1655 and 1627 cm"1 (c=O and c=c, conjugated). Di-
enone 22 had a uv absorption maximum at 253 mu(e 18,300)
with a shoulder at 280 mu(e 6800). The nmr spectrum of 22
consisted of three broad absorptions, centered at 7.791,
8.171 and 8.401, with areas in the ratio of 1:1:1. The three
absorptions are assigned to the allylic methylene protons
(8H), the spirocyclopentane protons (8H), and the non-allylic
protons in the six-membered rings (8H).

The Spectroscopic evidence supports the structure for
22. The ir and uv data are typical for 2,5-cyclohexadien-
ones (18). Garbisch (19) has reported the uv absorption
maximum for dienone 22'to be 234.5 mu(e 14,500). Hart and
Swatton (20) have reported the uv absorption maximum for the
completely methylated dienone 21 at 246 mu(e 14,800). The
uv absorption maximum for spiro dienone 22, reported by

Winstein and Baird (21), appears at 242 mu(e 16,000). These

13
uv data compare very favorably with that obtained for 22,
From the spectra of these three dienones, 22, 21 and 22” it
is possible to arrive at a predicted uv absorption maximum
for a dienone of the general formula 22, where R is alkyl.
Enchancement of the uv absorption maximum due to the presence
of the five membered spiro ring is about 7.5 mu (the differ-

ence between the absorption maxima of dienones 22 and 22).

O O O

O O
O

.32 .12. 38

m

If this difference is added to the absorption maximum of
dienone 21” a predicted value of 253.5 mu, for the absorp-

tion maximum of 22, is obtained. This agrees very nicely

with the value of 253 mu observed for dienone 22,

The ir values obtained for 22 are also in good agree—
ment with the values reported for dienone 21 (20). Dienone
21 has absorptions in its ir spectrum at 1653 and 1624 cm-1

(C=O and C=C, conjugated).

14

The proton assignments in the nmr are also consistent
with structure 22. The low field abSorption at 7.791'is
typical of allylic methylene protons in a six membered ring
(35). The absorption at 8.171 was assigned to the spiro
cyclopentane ring protons on the basis of the spiro cyclo—
pentane ring proton assignment in dienone 22. These protons
appear at 8.171 as a slightly Split singlet (60 Mc) (21a).
These exact absorption characteristics are observed in the
nmr Spectrum of 22 at 60 Mc. The remaining absorption at
8.401 is assigned to the non—allylic protons in the six mem—
bered ring by process of elimination.

Since the oxidations of hexamethyl- and hexaethylbenzene
yielded only linearly conjugated dienones, it seemed rather
strange that a cross-conjugated dienone should be formed in
the present case. In the oxidation of penta-
methyl benzene (9), dienone 22a, formed in 7% yield, was
presumed to arise from rearrangement of the 2,4—cyclohexa—

dienone 22” also formed in the reaction.

0 O
H H III
40 40a

(W M

Oxidation of s—dodecahydrotriphyenylene 22 using the
same conditions aS already described, but lowering the re—

action temperature to -67 to —650 and immediately hydrolyzing

15
with Saturated sodium bicarbonate solution gave, after work-up
and subsequent separation of the reaction mixture by prepara-
tive thin layer chromatography, three products: a) unreacted
S-dodecahydrotriphenylene 22; b) cross-conjugated dienone 22;
and c) a new compound assigned the structure Spiro[1,2,3,
4,5,6,7,8,9,10-decahydrophenanthrene-10—one-9,1'~cyclopen-
tane] 22,(16), on Spectroscopic evidence, mode of formation

and chemical reactivity.

 

 

O
o
CF3COZOH, CH2C12 .
> .+ 000
2g 33 35

The identity of the first two products was demonstrated
by comparison of their ir spectra and their Rf's on tlc with

pure samples.

Compound, 22, a pale yellow solid, mp 69-710, analyzed
well for C18H24O. The mass Spectrum showed a parent peak
at m/e 256, indicating this to be the molecular formula;
thus 22'was an isomer of dienone 22, The ir Spectrum of 22'
in CC14 solution Showed principle bands at 1644 and 1580 cm-1
(C=O and C=C, conjugated). The uv spectrum of 22,had an
absorption maximum in methanol at 332 mu(e 5100). The nmr
Spectrum in CC14 Showed two broad complex, absorptions cen—

tered at 7.781 and 8.371, which integrated with an approximate

16
relative ratio of 1:2. It was tentatively preSumed that
the low field absorption was due to the allylic methylene
protons (8H) and that the rest of the nmr spectrum accounted
for the remaining protons (16H). Further Spectrum—struc-
ture correlation, using nmr, was not possible.

The ir and uv Spectral data are typical for a 2,4-
cyclohexadienone (18) and compare very favorably with other
hexaalkyl—substituted-2,4-cyclohexadienones obtained by
this synthetic route (6,7). The uv absorption maximum of
dienones 2 and 2 occur at 330 mu(e 4500) and 339 mu(€ 11,000),
respectively, which is in good agreement with that obtained
for 22, The principle absorptions in the ir spectra of
dienones 2 and 2 occur at 1647 and 1567 cm_1(C=O and c-C
conjugated) and 1635 and 1560 cm”1 (c=O and c=c conjugated),
respectively, which compare favorably with the values ob-
tained for 22,

Treatment of 22 with either trifluoroacetic acid or
boron fluoride etherate in methylene chloride at room
temperature converts it into dienone 22, The structure of
the rearrangement product follows from comparison of its ir
Spectrum and Rf on tlc with that of pure dienone 22, The
rearrangement carried out with trifluoroacetic acid was
observed to be about 9 times faster than when carried out
with boron fluoride etherate under the same conditions.

This same type of rearrangement has been Shown to occur with

dienone 2, but requires more vigorous conditions (20).

17

. CF3C02H
. CH2C12

33 35

[W (“w

 

Treatment of 2 with fuming sulfuric acid converts it quan-

titatively to dienone, 21. The mechanism is presumed to
O O

fuming H2804

 

>

g 37

involve a series of methyl migrations.

With the facts that have been presented, a mechanism
which is consistent with the results may be formulated.
The course of oxidation is depicted in Figure 2. The ox-
idizing species is written OH+, although it is recognized
that this is probably not the true oxidant and that it may
be complexed to trifluoroacetate ions or other ligands in
solution. Evidence for the cationic nature of the oxidant,
however, has been presented (2).

The oxidation presumably involves initial attack of
electrophilic peroxytrifluoroacetic acid on 22,to give

carbonium 222, which undergoes a 1,24Wagner-Meerwein Shift

8
1

.mamamsmzmflHuoupmnmomooolm mo coapmoflxo on“ mcflnfluommo mamnom UprHamaomE d .N onsmflm

 

 

 

 

19
of an alkyl group, to give carbonium ion Egb. Carbonium ion
§gb undergoes another 1,2-shift, through its resonance
hybrid g2; to give carbonium ion géd. The carbonium ion géd
then undergoes a subsequent 1,2-shift, through its resonance
hybrid géefollowed by loss of a proton. The last two pro-
cesses can probably be written in either a stepwiSe or
concerted fashion. It is written in a stepwise fashion here
for clarity.

It is interesting to note that in formulating the
mechanism, dienone Qg’is not involved. However the pro—
tonated form of §§J carbonium ion ggb, is involved. It has
been observed, qualitatively, that the reaction leading to
the formation of gg is facile even at —67°. It is therefore
felt that any equilibrium between protonated and unproton-
ated dienone favors the protonated form. When the alkyl

substitutents are methyl or ethyl, the equilibrium is

 

 

34b 33

M w

shifted toward the unprotonated form, as is evidenced from
the formation of the corresponding linearly conjugated di-
enones from such oxidations. The fact that dienone §§ is

obtained from the hydrolysis of the low temperature oxidation

20

probably involves hydrolysis of the protonated form of

the dienone.

B. The Photochemistry of Spir011L2,3,4,5,6,7,8,9,1O-

decahydroanthracene-IO—one-9,1‘-cyclopentane1

The photochemistry of 2,5-cyclohexadienones has been
extensively investigated (12,13,22,23,24,25) In general,
2,5-cyclohexadienones undergo two primary photochemical
processes: a) loss of a substituent from C4 carbon fol-
lowed by aromatization and b) rearrangement to a bicyclo-
[3.1.0]hexenone (lumiproduct). Figure 3 depicts the pos-
sible reaction routes.

The principle steps involved in the photolysis of
2,5-cyclohexadienones are: a) excitation followed by inter-
system crossion to n,w* triplet (31,-) 32); b) bond altera-
tion, 3,5—bonding ($2 -> 3;) and d) skeletal rearrangement
(33 -> fig). The competition of rearrangements of type
(31,-) ii) in suitably 4—substituted 2,5-cyclohexadienones
by a radical fragmentation has been explained with homolytic
cleavage in the excited state of 32 and expulsion of a sub-
stituent (e.g., R) in radical form. The resulting phenoxy
radical 22' would then abstract a hydrogen from the solvent
to give phenol g1.

Recently, Schuster (26) has demonstrated that radical
fragmentation does compete with bicyclic ketone formation.
Irradiation of dienone fig in benzene solution provides a

mixture of pfcresol, £29 and the corresponding bicyclic ketone.

1
2

28¢: mm A“

.muumHEmLUOponm CH mmocm>©< .Hmcmmmsom .M Sony voodoonmmmu .mmcocmflpmxmLOHumo
Im.N mo ucmfimmsmnummuou03m mo me08 mHmHUCHHm mafiuoflmmp mEmSUm Uflumflcmnumz
mm

)2

mv

 

: Nv

mw
.m

mo

.m mudmflm

.:m

22

hV } +
benzene

 

cc13

48 49 50

m (W ('W

However, irradiation of spirodienone g; in ether solution
gives only radical fragmentation products, pfethylphenol Qg'

being the major one (27).

 

O OH
hv .
+
ether minor
CH2CH3 products
21, :22,

The most interesting photoreaction of 2,5-cyclohexa-
dienones is the formation of bicyclo[3.1.0]hexenones. Zim—
merman has studied the photochemistry of 4,4-diphenyl-2,5-
cyclohexadienone Qg'in great detail (23,28). Irradiation
of Qg’in aqueous dioxane solution afforded bicyclic ketone
ég’as the major product. Side products, shown to arise from
subsequent photolysis of the bicyclic ketone, were also

observed.

hV \
. > H
aqueous dioxane

53 54

m m

Kropp has investigated the photochemistry of 2,5-cyclo-
hexadienones (24,25), one of which was spirodienone fig.
Irradiation of a methanolic solution of 22 gave the cor-

responding bicyclic ketone gg (25).

0 a O

hv {ff
MeOH fi> _ \

55 56

NV m

 

Recently, it has been shown that irradiation of dienone,

Qz,in ether provided the expected bicyclic ketone gg (20).

o
O
hv ,
:QC Etzo ’ \

2.2, 28

(w

 

Irradiation of spiro[1,2,3,4,5,6,7,8,9,10-decahydro-

antracene—lO—one-Q,1'-cyclopentane] ii in anhydrous ether

24
through Vycor with a ZOO-watt Hanovia Type S lamp resulted
in formation of dienone 33, The reaction, followed by uv
spectroscopy (Figure 4), was completed when the absorption
intensity at 332 mu due to 33 reached a maximum, in about
4.9 hr.

The photoproduct of dienone 35, a pale yellow solid,
mp 69-710 from methanol, was shown to be identical to di-
enone 33 by comparison of its ir and uv spectrum with
that of 33 obtained from the low temperature oxidation of
s-dodecahydrotriphenylene 34, Also comparison of the R of

f

the photoproduct with the R of a pure sample of 33 on tlc

f
showed them to be identical. The photoproduct could also
be converted back to gé'by treatment with trifluoroacetic
acid in methylene chloride at room temperature, which is

consistent with the chemical reactivity of 33 under these

conditions.

0 O

hv/EtzO/Vycor > .

g2 33

rw

 

 

Irradiation of spiro dienone gé'in methanol solution,
through vycor provided a very smooth conversion to a new
compound. The reaction, followed by uv spectroscopy

(Figure 5), was completed in 50 minutes when no further

25

.mmoomonuommm >5 an Umuouficoa mm Hmzum CH Hmcmusmmoaumu
I.H.mlmaonoalmcmomugucmoupmnmomonoa.m.m.b.®.n.v.m.m.aaouflmm mo mammaouonm one .v musmflm

h .
2.33.558 553.022.»

§

0
o

0
v

transmittance
aauchosqe

O
N

 

 

.:./.._/ _// v_/_

 

26

.mmoumonpommm >5 hp Umuouflaoe mm Hocmnume :H.~mqmusomoao>o
u.H.mnmcoucanmcmomuanamouvmzmomwnoa.m.w.s.m.n.¢.m.m.aiouflmm mo mflmsaouoam mse .m mucosa

 

. . 2.9.365? $5.32:

OO—
00 .

e W B
C 00 H W.
n 1;.»(..

t .

.H O? m.-
m u
S 3
n a
a
r
t 0m

0,

 

 

 

::x;_/ _// V_/ _

 

27
change in the uv was observed. Evaporation of the solvent
produced a slightly colored transparent oil in quantitative
yield. It was shown to be Spiro[tetracyclo[7.4.1.01:9O3I3]-
tetradec-3-ene-2-one-14,1'-cyclopentane], 58 (16), based on
Spectroscopic evidence and mode of formation.

Compound 58 analyzed for C13H24O, the carbon content,
however, being slightly low. The mass spectrum indicated a
parent peak at m/e 256, showing this to be the molecular
formula. The compound was therefore isomeric with dienone
ii. The ir spectrum (liquid film) had absorptions at 1685
and 1639 cm_1 (c=o and c=C, conjugated). The uv Spectrum in
methanol had an absorption maximum at 240 mu (6 6440), a
shoulder at 275 mu (e 2735) and another maximum at 325-

340 mu (6 580). The nmr spectrum (CCl4 solution) consisted
of broad complex absorptions between 7—91, with principle
peaks centered at 8.021, 8.431 (with a shoulder at 8.381)
and 8.721. Accurate integration of the nmr spectrum was not
possible as the peaks overlapped too much to obtain any use-
ful information. Any kind of spectrum structure correlation

using the nmr data was not possible.

hv >
.0. MeOH / Vycor

 

 

28
The ir and uv data are consistent with the structural
assignment to 55, by comparison with the spectral data of

compounds having similar structural features.

 

56 28 29

I‘W m m

The uv spectrum of 55 (25) showed absorption maxima at
233 mu (6 4200) and 265 mu (£3290). The uv spectra of bi-
cyclic ketones £5 and 22 (6,15) in 95% ethanol have absorp—
tion maxima at 235 mu (e 6270), 274 mu (e 3240), shoulder at
320 mu (e 605) and 239 mu (6 5300), 270 mu (6 2660), 332 mu
(6 850), respectively. The uv data for 55, gg'and gg,com—
pare very favorably with that obtained for 55. The ir spec-

,. -1
trum of 55'has absorptions at 1689 and 1608 cm (c=o and

c=C, conjugated). Bicyclic ketones £5 and gg’have similar
absorptions in their ir spectra at 1690 and 1640 cm-1 and

1680 and 1638 cm—1, respectively. These data also give very
favorable support to structure 55,

The photoproduct of 55 in methanol, assigned structure
55, is the primary photoproduct of dienone 55, The structure
of the photoproduct is consistent with the spectral data
and its mode of formation is consistent with the general
mechanistic scheme described in Figure 3. The proposed

mechanism for the formation of ketone 55 from dienone 55 may

29

therefore be formukfled as below. The ionic intermediate

 

35 35a 58

M W rw

555 is used for convenience and clarity.

If ketone 55 is the primary photoproduct from dienone
55, then how does dienone 55'arise when 55 is photolyzed in
ether? A tentative answer can be obtained by examining the
uv spectra obtained from following the photolyses in ether
and methanol, Figures 4 and 5, respectively. Figure 4
shows a steady decrease in the absorption of the uv spectrum
due to dienone 55. It appears to decay to a uv spectrum
which is very similar to the uv spectrum for ketone 55, This
intermediate uv spectrum then appears to decay to the uv
spectrum of dienone 55. The same sort of decrease in ab-
sorption is observed in Figure 5, except that further photol-
ysis either does not occur or is so slow that a significant
change in the uv spectrum is not detectable and the photolysis
stops at the intermediate uv spectrum. This therefore sug-
gests that ketone 55 is the probable intermediate in the

formation of dienone 55 from the photolysis of dienone 55’in

ether.

30
C. The Photochemistry of Spiro[tetracyclo[7.4.1.01r903r3]

tetradec-3-ene-2-one-14,1'—cyclopentane]

 

The photochemistry of bicyclo[3.1.0]hexenones has re-
ceived much attention (22). In general, the photolysis of
bicyclo[3.1.0]hexenones can proceed to give three kinds of
products: a) phenols; b) 2,4-cyclohexadienones and c)
2,5-cyclohexadienones. Figure 6 describes the reaction
alternatives.

The photolysis of 55 may be described in the following
way: a) excitation followed by intersystem crossing to n,fi*
triplet (22.-9 55); b) 1,5-bond fission (55,—v 55); c)
intersystem crossing to the dipolar ground state singlet
(55,-9 55) and skeletal rearrangements leading to 55, 5g
and 55, The nature of the substituents directs the route of
rearrangement. For example, irradiation of bicyclic ketone

55'in methanol leads to a 2,4—cyclohexadienone, 55 (24,25).

hv
MeOH

 

g 66

Irradiation of umbellone, 51 (29), affords thymol as the

photoproduct,.55.

31

T 88: mm .w .332an
Iouonm CH mmocm>©¢ .HmGMMMSUm .& Eoum UmODUOHmmm_ .mmcocmxm£_o.fi.m_0aumofln

 

mo ucmEomcmuummHouonm mo mmUoE mHmHUCflHm mcfluoflmmp mfimnum Uflumflcmnomz .m musmflm
mm .m
.:m
mo
E n 25 22 22 22
Amumv Hm om mm
V® :m WM m :m :m :m
m
.m COHuHmOm
Q .MII .NHII .MHII mull G
‘1' III! III: IIIII.
m )x
\\ Cum .3m :— .2“ N
-.m o I0 o u .0“
coauflmomlv .. ..
m1

)2

mm =A m

z
.m

:cm

32

OH

 

67 68

m I'W

Recently, Hart and Swatton (20) have shown that the
intermediate corresponding to 55 can be trapped. Irradia-
tion of the hexamethyl bicyclic ketone 55 in acid-free
methanol produced photoproduct 55, resulting from addition

of the solvent to 55a.

 

 

0 OH
0 “)
hv . Me
\ MeOH ' "
_ J
3% 3% £52,

Several years ago, Matsuura (30) and more recently
Miller (31,32) have shown another alternative in the photol-
ysis of bicyclo[3.1.0]hexenones. As depicted in Figure 6,
1,5-bond cleavage of the bicyclic ketone is most common.
However, cleavage of the 5,6-bond can also occur. Irradia-
tion of bicyclic ketone 22,1“ cyclohexane solution (32)
produced dienone 15, The mechanism is presumed to involve
cleavage of the C5-C6 bond, giving 15a as an intermediate,
which can then undergo acyl migration and double bond form—

ation to give 25, The mechanism has many characteristics of

33

 

 

O‘R CH3 C) R. * H: O Ii
7“ -——4- ._,. CH3
*
2.9. 22.: ll
19. 2.9,: 11,
R = n—pr or allyl R = n-pr or allyl

carbonium ion reactions and the acyl migration has a close
analogy in carbonium ion chemistry. However, the fine
points to the mechanism have not been elucidated.

Irradiation of an ether solution of Spiro[tetracyclo
[7.4.1.011903:3]tetradec-3-ene-2-one-14,1'-cyclopentane], 55,
through vycor with a 200 watt Hanovia lamp provided a smooth
conversion to dienone 55,as the only product. The photoly—
sis, followed by uv spectroscopy (Figure 7), showed a steady
decay of the band at 240 mu due to 55, and a gradual increase
in the band at 332 mu due to dienone 55, The reaction was
completed in about 2 hr when the band at 332 mu had reached
maximum intensity. Evaporation of the solvent and crystal—
lization from methanol provided dienone 55, The structure
of the photoproduct follows from its ir spectrum and compari-
son of Rf's on tlc with a pure sample of dienone 55,

This result tends to substantiate the tentative sug—
gestion that ketone 55'is the intermediate in the production
of dienone 55,from the photolysis of dienone 55 in ether.
Therefore, the sequence of photoreactions to describe this

system may be written as follows:

34

.mmoomouuommm >5 an Umuouflcoa mm 50355 CA Hmcmucwmoaomo
I.H.vHImGOINIwchmIUmomuuwuHm.m0m.ao.a.v.5HoaohomuumuHouflmm mo mHmmHouonm wfle .b mu5mwm

 

3238...? 593.953

unnooo 02 03.0.0.0u

 

 

00w .. 0.0
00 v
e I .. N.o e
M 8 .- »H m-
.nov . + cemw
m i u
s .I n
n
a 0.0
r
tom .
0.0
or v 0.9
T
o t
T
0 r N;
V V...
0.—
N x
O.—
p r O.“

..:/._/ _// v_/

 

35

 

35 58 33

(W rw I'w

A tentative mechanism for the conversion of ketone 55
to 55'may be prOposed which is totally consistent with
Miller's mechanism (32). Also, the notation used by Miller,
depicting 5,6-bond cleavage and subsequent acyl migration
and double bond formation, will be used here since the exact

nature of the excited state is not known.

   

33

(w

The question now arises, why should this process occur
at all in this particular system? ,Miller (32) has postulated
the following explanation to account for the 5,6-bond cleav-
age in his Efbutyl bicyclic ketones. In the ground state,

25,.there is severe steric interaction between the Efbutyl

36

   

72 73

group at C1 and the g§9_substituent at C6. Weakening the
C5-C6 bond to allow the 2&2 substituent at C5 to rotate
slightly toward the carbonyl, as in Z5, would markedly re-
lieve the crowding while at the same time bring the geometry
at C6 into a more favorable arrangement for migration of

the carbonyl group.

Therefore, a tentative explanation accounting for the
formation of dienone 55’from the photolysis can be proposed.
An examination of models of structure 55'shows some steric
interaction between the protons on the 252 side of the
spiro cyclopentane ring and the protons of the bridging
cyclohexane ring. These interactions may be minimized in
two ways: a) the bridging cyclohexane ring can assume a
particular conformation so as to minimize interactions and,
applying Miller's argument, b) the C5-C6 bond can weaken
slightly, rotating the spiro cyclopentane ring so that the
2&2 protons are pointed toward the carbonyl. The degree of
importance of the steric effect is probably less than in the
case of the Efbutyl bicyclic ketones. However, an over-

riding factor greatly magnifies the steric importance in the

37
photolysis of 55. Examination of the excited state of ketone

55, corresponding to the ground state singlet 55iin Figure 6,

   

58b 58c

WV

shows the presence of double bonds and positive charges at
bridgehead carbons, which violates the Bredt rule (33).
Therefore, photolysis by the 'normal' route becomes less
important and the alternative route, cleavage of the C5-C6

bond becomes more important.

D. The Photochemistry of Spiro[1,2,3,4,5,6,7,8,9,10-

decahydrophenanthrene-10-one—9,1'—cyclopentaneL

The photochemistry of 2,4-cyclohexadienones has been
previously described (See introduction). The two important
photoreactions of 2,4-cyclohexadienones are: a) ring
fission to give a g$§_ketene; and b) rearrangement to a
bicyclo[3.1.0]hexenone. As has been described (11), the
pathway taken by the cyclohexadienone depends onrthe size,
number and position of the substituents on the cyclohexa-
dienone ring as well as the nucleophilic character of the

solvent.

38

Subtle structural changes in 2,4-cyclohexadienones are

known to influence the photochemical course of the reaction.
Such a structural change was made in dienone 5, The ethyl
groups were effectively pinned back into a ring system, re-

sulting in dienone 55,

O O

o
00
0

g 33

m

Irradiation of an ether solution of 55 through Pyrex
using a Hanovia 200—watt Type S lamp was followed by uv
spectroscopy and resulted in a gradual decay of the band at
332 mu due to dienone 55, The only band that remained ap-
peared at an absorption maximum of 205 mu. Upon completion
of the reaction, in about 6.2 hr, evaporation of the solvent
afforded a slightly colored oil having a mildly pungent odor.
The ir spectrum of the oil in CCl4 solution showed principle
absorptions at 3500, 1720 and 1705 cm-1. Comparison of the
R

of the oil with the Rf of a sample of ketone 55, also an

f
oil, on tlc showed them to be different.

The ir data strongly suggest that the photoproduct has
a carboxylic acid function (34). This fact alone suggests
that dienone 55 has undergone ring fission to the ketene,

which has reacted with the small quantity of water, (about

.01%) present in commercially available anhydrous ether.

39
This is purely supposition, however, and requires further
proof. It is clear that dienone 55 did not react to give
ketone 55, The structure of the photoproduct and an explana-

tion to account for this photochemical behavior are subjects

for further research.

EXPERIMENTAL
A. General Procedures

Unless otherwise stated, all ultraviolet spectra were
measured in methanol solution with a Unicam Model SP-800
untraviolet spectrophotometer. Infrared spectra were meas-
ured in carbon tetrachloride with a Unicam Model SP—200
infrared spectrophotometer and were calibrated against poly-
styrene. All nmr Spectra were measured in carbon tetra-
chloride with a Varian Associates HA-100 spectrometer. Chemi-
cal shifts are in T values, measured from tetramethylsilane
as an internal reference. Mass spectra were carried out by
Dr. L. B. Sims and Mr. John Wettaw of this department with
a Consolidated Electrodynamics Corporation 21-103C instru-
ment, operating at an ionizing potential of 70 v. Analyses
by thin layer chromatorgraphy were carried out using 1" x 4"
microscope slides coated with Brinkmann Silica Gel-H as the
adsorbent, eluted with chloroform and developed with iodine
vapor. Separations by preparative thin layer chromatography
were carried out using 8" x 8" glass plates coated with
Brinkmann Silica Gel-PF254, of 2 mm thickness, as the ad~
sorbent and eluted with chloroform. Elemental analyses were
performed by Spang Microanalytical Laboratories, Ann Arbor,

Michigan. All melting points are uncorrected.

4O

41

B. Preparation of s-Dodecahydrotriphegylene (17)

To a stirred solution of cyclohexanone (100 g, 94 ml,
1.02 mole) in 300 ml of methanol was added concentrated
sulfuric acid (100 g, 55.5 ml, 1.02 mole) in a dropwise
fashion. When addition of the sulfuric acid was completed,
the solution was stirred and refluxed for 24-36 hours. After
about 5 hours of refluxing, a tan colored oil began to sep—
arate.

When the reflux period was completed, the reaction
mixture was allowed to cool to room temperature for 24 hours
while still being stirred. ‘The dark green reaction mixture
was decanted, leaving the tan oil. The oil was dissolved
in 400 ml of benzene and the benzene layer extracted with
water (3 x 250 ml) which turned the benzene layer yellow.
After drying the organic layer over anhydrous sodium sulfate,
the benzene was concentrated to 150 ml and cooled for 24—36
hours, which induced crystallization. The crystals were
filtered and gently rinsed with cold benzene and then cold
methanol. The crystals were suction dried on a Bfichner

funnel and provided 5.9 g (2.5 x 10‘2 mole) of s-dodeca-

 

hydrotriphenylene'5g, mp 232-2330 (lit. value (17) 232-2330),

 

as colorless needles. The yield was 7.4% (lit. yield 6.0 g,
7.5%). The nmr spectrum Showed two broad singlets centered
at 7.551 and 8.31, corresponding to the benzylic and ali-

cyclic methylenes respectively. The areas were in the ratio

of 1:1.

42

C. The Oxidation of s-Dodecahydrotriphenylene
1. The Reaction with 110% Excess Oxidant at —3 to +10

To a cooled, vigorously stirred solution of s-dodeca-
hydrotriphenylene (4.59g, 1.9 x 10‘2 mole) in 200 ml of
methylene chloride was simultaneously added: 1) a solution
of peroxytrifluoroacetic acid, made by dissolving trifluoro—
acetic anhydride (9.0 g, 4.3 x 10-2 mole) in 15 ml of
methylene chloride, cooling to 0°, and with vigorous stir—
ring adding 98% hydrogen peroxide (1.1 ml, 4.3 x 10—2 mole)
until a homogeneous solution was obtained; 2) distilled 47%
boron fluoride etherate (20 ml). The temperature was main—
tained at -3 to +10. Slow addition of the oxidant and acid
catalyst (found to be important in oxidizing this compound)
was completed after 1.5 hr. After an additional 1.5 hr of
stirring, during which time the temperature was allowed to
rise to 20°, the reaction mixture was analyzed by thin layer
chromatography and it was determined that all of the starting
hydrocarbon had reacted. The reaction mixture was then
hydrolyzed with 200 ml of water and the organic layer was
successively extracted with water (2 x 200 ml), saturated
sodium bicarbonate solution (2 x 300 ml), water (2 x 200 ml)
and dried over anhydrous sodium sulfate. The methylene
chloride was evaporated and the residue dissolved in 20 ml
of methanol. The methanol was concentrated to 5-10 ml and
Cooled overnight. Crystallization afforded 2.21 g (8.65 x

10—3 mole) of colorless crystals which\mme shown to be

43
gpiro[1,2,3,4,5,6,7,8,9,10—decahydroanthracene-10-one-9,1'—
cyclgpentane]’55qmp 114—1170. Recrystallization from meth-
anol provided 1.75 g, mp 115-117°. The yield of the dienone
before recrystallization was 45%, based on the hydrocarbon
consumed. The colorless crystalline dienone had major bands
in its ir spectrum (CC14 solution) at 1655 and 1627 cm-1
(C=O and c-c, conjugated). The uv spectrum showed bands
at Afing 253 mu (6 18,300) and 280 mu (shoulder on main
band) (6 6800). The mass spectrum indicated a parent peak
at m/e 256. The nmr spectrum consisted of three broad
peaks centered at 7.79m, 8.171, 8.401 with relative areas
in the approximate ratio of 1:1:1. The three peaks were
assigned to the 8 allylic methylene protons, 8 methylene
protons in the 5-membered spiro ring, and the remaining 8

methylene protons in the two 6-membered rings.

Anal. Calcd for C13H24O: C, 84.32; H, 9.43.

 

Found: C, 84.26; H, 9.26.
2. The Reaction With 110% Excess Oxidant at —67 to —65°

To a cooled, vigorously stirred solution of s-dodeca-
hydrotriphenylene (4.74 g, 1.97 x 10..2 mole) in 175 ml of
methylene chloride was simultaneously added: 1) a solution
of peroxytrifluoroacetic acid, made by dissolving trifluoro-
acetic anhydride (8.7 g, 4.15 x 10.2 mole) in 15 ml of
methylene chloride, cooling to 0°, and with vigorous stir-
ring adding 98% hydrogen peroxide (2.9 g, 8.3 x 10.2 mole)

until a homogeneous solution was obtained; 2) distilled 47%

44
boron fluoride etherate (15 ml). The temperature was main—
tained at -67 to -65° using a dry ice—acetone bath. Addi-
tion of the oxidant and acid catalyst was completed in 35
minutes and the reaction was hydrolyzed by pouring the re-
action mixture into 750 ml of ice cold saturated sodium bi-
carbonate solution. The organic layer was washed with water
(2 x 300 ml), saturated sodium bicarbonate (2 x 200 ml),
water (2 x 200 ml) and dried over anhydrous sodium sulfate.
The reaction mixture was analyzed by thin layer chromatography
and shown to contain 3 components. The reaction mixture was
then separated by preparative thin layer chromatography and
the 3 components were identified.

The least polar material was identified as unreacted
s-dodecahydrotripheny1ene by its ir and nmr spectra and by
comparison of its Rf with that of a pure sample of the hydro—
carbon on tlc. The most polar component was identified as
Spiro[1,2,3,4,5,6,7,8,9,10-decahydroanthracene-lO—one-9,1'-
cyclopentane] by its ir and nmr spectra and by comparison

of its R value with that of a pure sample on tlc. The

f
third component, whose Rf was slightly greater than the Rf
of Spiro[1,2,3,4,5,6,7,8,9,10-decahydroanthracene-lO-one—

9,1'-cyclopentane], was shown to be spiroL1,2,3,4,5,6,7,8,

9,10-decahydrophenanthrene-lO-one—9,1'-cyclopentane]’55,mp
69-71°. The pale yellow solid displayed major bands in the
ir (CC14 solution) at 1644 and 1580 cm"1 (c=o and c-c, con—

jugated). The uv spectrum consisted of a broad band

hfing 332 mu (e 5100). The mass spectrum indicated a parent

45
peak at m/e 256. The nmr spectrum (CCl4 solution) showed
2 broad peaks centered at 7.781 and 8.371 with an approxi-
mate relative area ratio of 1:2, corresponding to 8 allylic
methylene protons and 16 alicyclic protons (the 5-membered
Spiro ring and the 6-membered rings combined).

1315;. Calcd for C18H24O: c, 84.32; H, 9.43.

Found: C, 84.35; H, 9.44.

D. The Rearraggement of Spiro[1,2,3,4,5,6,7,8,9,10-deca-
hydrgphenanthrene—lO-one—9,1‘—cyplopentane] with Boron

Fluoride.Etherate

To a solution of spiro[1,2,3,4,5,6,7,8,9,10-decahydro-
phenanthrene-lO-one—9,1'-cyclopentane]'55’(100 mg, 3.9 x 10-4
mole) in 30 ml of methylene chloride was added 3 ml of 47%
boron fluoride etherate and the mixture was allowed to
stir at room temperature. The reaction was monitored by
thin layer chromatography and after 3 hours, there was no
detectable amount of the starting conjugated dienone. The
reaction mixture was then hydrolyzed with 150 ml of ice water
and further extracted with water (2 x 50 ml) and the organic
layer dried over anhydrous sodium sulfate. The methylene
chloride was evaporated and the residue dissolved in meth—
anol. Crystallization from methanol afforded 56.9 mg of
§piroL1,2,3,4,5,6,7,8,9,10—decahydroanthracene-10-one-9,1‘-
gyclopentane],55'as the only product formed (tlc), mp 114-
117°. Comparison with a pure sample (tlc and ir) of the cross-

conjugated dienone 55 showed the two to be identical.

46
E. The Rearrangement of Spiro[1,2,3,4,5,6,7,8,9,10-decahydro-
phenanthrene—lO-one-Q,1'—cycl0pentanelywith Trifluoro—

acetic Acid

To a stirred solution of Spiro[1,2,3,4,5,6,7,8,9,10-
decahydrophenanthrene-10—one-9,1'—cyclopentane],55’(100 mg,
3.9 x 10“4 mole) in 30 ml of methylene chloride was added
2 ml of trifluoroacetic acid. The reaction mixture was al-
lowed to stir at room temperature for 45 minutes. The re—
action was monitored by tlc, by sampling the reaction mix—
ture after 5, 10 and 20 minutes. It was determined that
after 20 minutes, all of the starting dienone had reacted.
The reaction mixture was then hydrolyzed with 150 ml of
water, extracted with saturated sodium bicarbonate solution
(2 x 50 ml), water (2 x 50 ml) and dried over anhydrous
sodium sulfate. The methylene chloride was evaporated and
the residue dissolved in methanol. Analysis of the methanol
solution by tlc indicated that only one product had been

4 mole)

formed. Crystallization provided 71.4 mg (2.8 x 10-
or spiroL1,2,3,4,5,6,7,8,9,10-decahydroanthracene-lO—one—

9,1'—cyclopentane]’554mp 114-117°. Comparison of the re-

 

arrangement product (tlc, ir) withzapure sample of the cross—

conjugated dienone 55’showed them to be the same.

F. General Photolysis Procedures

Unless otherwise stated, all irradiations were conducted

using a Hanovia Type 8200 watt Mercury vapor lamp. This was

47
placed in a quartz water jacket which was fitted into a
Pyrex well of slightly larger diameter. The effective vol—
ume of the Pyrex well could hold up to 450 ml of solution
which could be agitated with a flow of nitrogen gas. Also
unless otherwise stated, irradiations were carried out
using a Vycor filter, which was fitted between the lamp and
the quartz water jacket. The entire flask assembly was
immersed in a Dewar flask filled with cold water, which was

used as a cooling bath.

G. Irradiation of Spiro[1,2,3,4,5,6,7,8,9,10-decahydro-

anthracene—lO—one-Q,1'—cycl9pentane] in Anhydrous Ether

A solution of spiro[1,2,3,4,5,6,7,8,9,10-decahydro-
anthracene-lO-one-9,1'-cyclopentane],55,(770.7 mg, 3.0 x
10.—3 mole) in 400 ml of anhydrous ether was irradiated.

The photolysis, followed by disappearance of the ultra-
violet band at 253 mu and appearance of an ultraviolet band
at 332 mu, was completed in 4.9 hours (at which time the
band at 331 mu reached a maximum). The ether was evaporated
and the yellow residue dissolved in 15 ml of methanol.
Analysis (tlc) of the methanol solution showed that no
starting material was present and that only one component
was present. It was therefore concluded that a quantitative
conversion occurred. The methanol solution was concentrated
to 5 ml or less and cooled. Crystallization afforded 438.4

mg, 1.71 x 10.3 mole (57% yield) of spiro[1,2,3,4,5,6,7,8,—

 

 

9,10—decahydrophenanthrene—10-one—9,1'-cyc10pentaneld55,

48
mp 69—71°. This was shown to be the same conjugated dienone
as that obtained from the oxidation of s—dodecahydrotri—
phenylene at —67 to —65°, by comparison of their Rf's on

tlc and infrared and nmr spectra.

H. The Dark Reaction of Spiro[1,2,3,4,5,6,7,8,9,10-deca-
hyfiroanthracene-lO—one-9,1'-cyclopentane] in Anhydrous

Ether

A solution of Spiro[1,2,3,4,5,6,7,8,9,10-decahydro-
anthracene-lO-one-9,1'—cyclopentane]'55,(13.9 mg, 5.3 x 10-5
mole) in 3 ml of anhydrous ether in a Pyrex test tube was
sealed with a cork and placed in the dark. Analysis of the
solution after 36 days by thin layer chromatography and
infrared Spectroscopy showed that no reaction had taken

place. Evaporation of the ether afforded a quantitative

recovery of the starting dienone.

 

I. Irradiation of Spiro[1,2,3,4,5,6,7,8,9,10-decahydro—

anthracene—lO-one-Q,1'-cyclopentane] in Methanol

A solution of Spiro[1,2,3,4,5,6,7,8,9,10-decahydro-
antracene—lO—one-9,1'-cyclopentane],55,(691.6 mg, 2.7 x

10‘3

mole) in 400 ml of methanol was irradiated. The photol-
ysis, followed by the disappearance of the ultraviolet band
at 253 mu, was completed after 50 minutes. The methanol was

evaporated affording 672 mg (2.62 x 10—3 mole) of a slightly

colored transparent oil which was shown to be

49
spiroLgetracyclo[7.4.1.01'903'8]tetradec-3-ene—2-one,14,1'-

gyclopentane], 55, The oil was analyzed by tlc and compared

 

to the starting dienone and was found to be free of starting
dienone and consist of a single component.
The oil had predominent bands in the ir spectrum

(liquid film) at 1685 and 1639 cm‘1

(C=O and c-c, conjugated).
The uv Spectrum consisted of bands at AE§2H 240 mu (e 6440),
275 mu (shoulder) (e 2735) and 325-340 mu (6 580). The mass
spectrum indicated a parent peak at m/e 256. The nmr spectrum
(CCl4 solution) consisted of broad complex peaks between
7-91,'with principle peaks centered at 7.71, 8.021, 8.431
(shoulder at 8.381), and 8.721. Accurate integrations of

the peaks were virtually impossible, due to their complexity.

Anal. CalCd for C13H240: C, 84.32; H: 9.43.

Found: C, 82.35; H, 9.34.

J. The Dark Reaction of Spiro[1,2,3,4,5,6,7,8,9,10-deca—

hydroanthracene-lO-one-Q,1'—cyclopentane] in Methanol

A solution of spiro[1,2,3,4,5,6,7,8,9,10—decahydro-
anthracene-lO—one-9,1'—cyclopentane],55l(14.0 mg, 5.6 x 10—5
mole) in 5 ml of methanol was placed in a Pyrex test tube,
sealed with a cork and placed in the dark. Analysis of the
solution after 27 days by tlc and infrared spectroscopy
showed that no reaction had taken place. Evaporation of

methanol gave a quantitative recovery of the starting di-

enone.

50
K. ggradiation of Spiro[tetracycloi7.4.1.01I903:3]tetradec-

3-ene-2-one-14,1'-cyclopentane] in Anhydrous Ether

A solution of spiro[tetracyclo[7.4.l.01I903r3]tetradec-
3-ene-2-one-14,1'—cyc10pentane],55l(448.9 mg, 1.78 x 10-3
mole) in 350 ml of ether was irradiated. The photolysis,
followed by the appearance of an untraviolet band at 332 mu,
was completed after about 2 hours (at which time the band
at 332 mu had reached a maximum). The ether was evaporated

and the residue dissolved in methanol. -Crystallization pro—

vided 347 mg of §piroi1,2,3,4,5,6,7,8,9,10-decahydrgphen—

 

anthrene—lO—one—9,1'-cyclopentane]’55, Analysis by tlc
and infrared spectroscopy showed the photoproduct to be
identical to the conjugated dienone obtained from the oxi—

dation of S—dodecahydrotriphenylene at -67 to -65°.

L. The Dark Reaction of Spiro[tetracycloL7.4.1.011903'Qj

tetradec-3-ene-2-one-14,1'-cyclopentanel in Anhydrous

 

Ether

A solution of spiro[tetracyclo[7.4.1.011903'8]tetradec-
3-ene-2-one-14,1'-cyclopentane]’554(15 mg, 5.85 x 10-5
mole) in.3 ml of anhydrous ether was placed in a Pyrex test
tube, sealed with a cork and placed in the dark. No reaction
could be detected after 15 days by analysis of the solution

by tlc and by infrared specroscopy. Evaporation of the

ether gave a quantitative recovery of starting material.

51
M. Irradiation of Spiro[1,2,3,4,5,6,7,8,9,10-decahydrophen-

anthrene-lO-one-9,1'-cyclopentane1 in Anhydrous Ether

A solution of spiro[1,2,3,4,5,6,7,8,9,10-decahydro—
phenanthrene-lO-one-Q,1'—cyclopentane] 55 (107 mg, 4.2 x
10.4 mole) in 300 ml of anhydrous ether was irradiated
through a Pyrex filter using a 200 watt Hanovia Type S mer—
cury lamp. The photolysis, followed by the disappearance
of the ultraviolet band at 332 mu, was completed in 6.2 hours.
The ether was evaporated yielding 110 mg of a slightly
colored oil. Comparison of this oil with Spiro[tetracyclo
[7.4.1.01'903'3]tetradec-3—ene—2-one-14,1'-cyclopentane] 55
by infrared and uv spectroscopy and tlc showed them to be
different. The oil had characteristic bands in the ir at
3500, 1720, 1705 and 1452 cm-1. The uv Spectrum had a

MeOH

band at kmax 205 (6 12,300). The photoproduct was not

further investigated at this time.

N. The Dark Reaction of Spiroi1,2,3,4,5,6,7,8,9,10—decahydro-

phenanthrene-lO-one-9,1'-cyclopentane] in Anhydrous Ether

A solution of spiro[1,2,3,4,5,6,7,8,9,10-decahydro-
phenanthrene-lO-one-9,1‘-cyclopentane] 55 (13.9 mg, 5.3 x
10"5 mole) in 3 ml of anhydrous ether in a Pyrex test tube
was sealed with a cork and placed in the dark. Analysis of
the solution after 39 days by ir and tlc indicated that no
reaction had taken place. Evaporation of the ether afforded

a quantitative recovery of the starting dienone.

S UMMARY

1. The oxidation product of s—dodecahydrotriphenylene
with 110% excess peroxytrifluoroacetic acid-boron fluoride
etherate at —3 to +1° was spiro[1,2,3,4,5,6,7,8,9,10—deca-
hydroanthracene—lO-one-9,1'-cycl0pentane] in 45% yield
after recrystallization from methanol based on a 100% con-
version of the hydrocarbon.

2. Oxidation of s—dodecahydrotriphenylene under the
same conditions but at —67 to -65° followed by immediate
hydrolysis gave unreacted s-dodecahydrotriphenylene, Spiro-
[1,2,3,4,5,6,7,8,9,10-decahydroanthracene-lO-one-9,1'-
cyclopentane] and spiro[1,2,3,4,5,6,7,8,9,10—decahydro-
phenanthrene-lO-one-9,1'—cyclopentane].

3. Treatment of spiro[1,2,3,4,5,6,7,8,9,10—decahydro-
phenanthrene-lO-one-9,1'—cyclopentane] with either tri—
fluoroacetic acid or boron fluoride etherate in methylene
chloride rearranged it to spiro[1,2,3,4,5,6,7,8,9,10—deca—
hydroanthracene—lO-one-9,1‘—cyclopentane]. The reaction
with trifluoroacetic acid was about nine times faster than
with boron fluoride etherate.

4. Irradiation of spiro[1,2,3,4,5,6,7,8,9,10—deca-
hydroanthracene-lO—one—9,1'-cyclopentane] in ether through
Vycor gave spiro[1,2,3,4,5,6,7,8,9,10~decahydrophenanthrene-

10-one-9,1'—cyc10pentane].

52

53

5. Irradiation of spiro[1,2,3,4,5,6,7,8,9,10—deca-
hydroanthracene-1O-one—9,1‘-cyc10pentane] in methanol
through Vycor gave spiro[tetracyclo[7.4.1.01I903'8]tetradec-
3—ene-2—one-14,1'-cyclopentane] as the primary photoproduct.

6. Irradiation of spiro[tetracyclo[7.4.1.01'903'8]-
tetradec—3-ene-2-one—l4,1'-cyclopentane] in ether through
Vycor gave spiro[1,2,3,4,5,6,7,8,9,10-decahydrophenanthrene-
10-one-9,1'—cyclopentane].

7. Irradiation of Spiro[1,2,3,4,5,6,7,8,9,10-decahydro-
phenanthrene-lO-one—Q,1'-cyclopentane] in ether through
Pyrex gave a product which is presumed to be a ring fission
product. No spiro[tetracyclo[7.4.1.01'903'8]tetradec-3—
ene-2-one-14,1'-cyclopentane] was formed.

8. Control experiments showed that none of the ir-
radiated compounds were reactive in the dark in the solvents

used for the irradiations.

L ITERATURE C I TED
Waters, W. S. and D. H. Derbyshire, Nature, 165, 401
(1950). --

Norman, R. O. C. and A. J. Davidson, J. Chem. Soc.,
5404 (1964).

Hart, H. and C. A. Buehler, J. Org. Chem., 55, 2397
(1964). "‘

 

Hart, H., C. A. Buehler and A. J. Waring in "Selective
Oxidation Processes", Advances in Chemistry Series,
American Chemical Society, Washington, D.C., 1965, p. 1.

Hart, H. and C. A. Buehler, J. Am. Chem. Soc., 55, 2177
(1963). "‘

Hart, H., P. M. Collins and A. J. Waring, J. Am. Chem.
Soc., §§, 1005 (1966).

Hart, H. and A. J. Waring, J. Am. Chem. Soc., 55,

 

 

1454 (1964). ‘—'
Hart, H. and R. M. Lange, J. Org. Chem., =5, 3776
(1966).

Collins, P. M. and H. Hart, J. Chem. Soc., in press.
Hart, H. and R. K. Murray, Jr., J. Org. Chem., in press.

Quinkert, G., Angew. Chem., Intern. Ed. Engl., g, 211
(1965). "

deMayo, P. and S. T. Reid, Quart. Rev. (London), 55,
393 (1961). ‘—

Chapman, 0. L. in "Advances in Photochemistry", edited
by W. A. Noyes, Jr., G. S. Hammond and J. N. Pitts, Jr.,
Interscience Publishers, New York, Vol. 1, 1963, pp.
330-351.

Barton, D. H. R. and G. Quinkert, J. Chem. Soc., 1
(1960).

Hart, H. and A. J. Waring, Tetrahedron Letters, 325
(1965).

54

16.

17.

18.

19.

20.

21.

22.

23.

24.
25.

26.

27.

28.

29.

30.
31.

32.

33.

55

"Definitive Rules for Nomenclature of Organic Chemistry",
J. Am. Chem. Soc., 55, 5545 (1960).

Mannich, C., Ber., 25, 153 (1906).

Waring, A. J. in "Advances in Alicyclic Chemistry",
edited by H. Hart and G. J. Karabatsos, Academic Press,
New York, Vol. 1, 1966, pp. 184—193.

Garbisch, E. w., J. Org. Chem., fl, 2109 (1963).

 

Hart, H. and D. W. Swatton, J. Am. Chem. Soc., 55,
1874 (1967). “‘

a) Winstein, S. and R. Baird, J. Am. Chem. Soc., 52,
788 (1962); b) Winstein, 8., private communicatiofiT

Schaffner, K. in "Advances in Photochemistry", edited
by W. A. Noyes, Jr., G. S. Hammond and J. N. Pitts,
Jr., Interscience Publishers, New York, Vol. 4, 1966,
pp. 81-112.

Zimmerman, H. E. and D. I. Schuster, J. Am. Chem. Soc.,
52, 4527 (1962).

Kropp, P. J., J. Am. Chem. Soc., 55, 4053 (1964).
Kr0pp, P. J., Tetrahedron, 55, 2183 (1965).

Schuster, D. I. and D. J. Patel, J. Am. Chem. Soc.,
1.3.8., 1825 (1966) .

Schuster, D. I. and C. J. Polowczyk, J. Am. Chem. Soc.,
§§, 1722 (1966).

Zimmerman, H. E. and J. S. Swenton, J. Am. Chem. Soc.,
52, 906 (1967).

Wheeler, J. W. and R. H. Eastman, J. Am. Chem. Soc.,
51. 236 (1959).

Matsuura, T., Bull. Chem. Soc. Japan, 51, 564 (1964).
Miller, B. and H. Margulies, Chem. Comm., 314 (1965).

Miller, B. and H. Margulies, J. Am. Chem. Soc., 55,
1678 (1967. "'

Eliel, E., "Stereochemistry of Carbon Compounds", McGraw—
Hill, New York, 1962, p. 300.

34.

35.

56

Nakanishi, K., "Practical Infrared Absorption Spectros-
copy", Holden-Day, San Francisco, 1964, p. 43.

Mathieson, D. W., "Interpretation of Organic Spectra",
Academic Press, New York, 1965, pp. 51-58.

APPENDIX

57

58

O
coo coo no
“a.

 

1. a) IR Spectrum of Spiro[1,2,3,4,5,6,7,8,9,10—decahydrc—
anthracene-lO-one-9,1'-cyclopentane].

1-0

 

C
1-0 ‘0
as
a"
on 3
" a
g a
So. i
s ‘03
° 9
" a
A . n
a o 2 ‘00
so
00 )oo

 

m .
wavelet: h millimicrons .. ..

1. b) UV Spectrum of Spiro[1,2,3,4,5,6,7,8,9,10-decahydro-
anthracene-lO—one-9,1'-cyclopentane].

59

  

l\l( \\I \I' I'm

  

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

  

transmittance

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

O

 

2. a) IR Spectrum of Spiro[1,2,3,4,5,6,7,8,9,10-decahydro-
phenanthrene-lO-one-9,1'-cyclopentane].

|\|( \\| \|’\Hlv

2'0

 

0
1-0 ’0
08
20,.
3
00° 3
U 0'
3 a
£04 40:
3 u
,,. 5
«02
so
100

 

wavelength millimicrons

2. b) UV Spectrum of Spiro[1,2,3,4,5,6,7,8,9,10-decahydro-
phenanthrene-lO-one-9,1'—cyc10pentane].

 

60

  
 

\|'_ 2m.

  
   

\|( \\l

   
     

91155
; - >’--‘m

i

 

 

      
 

 
 

oo , . ---<>-- 90

M .0

K .

 

 

 

   

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

    

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

' \
70-11 7O
60 60
so so T 1 .
-' i . €:. 1.3 .i'
r - - - . ;' r x:
.: t .I: ..; . ’1:
f.; . .'z‘ '2! ‘:
: ‘ 1- :2. 2:: 1
3) 1‘:; 3° ' ‘ ; Y.
-- ’wsr ;n
30 1;. ‘ 20 i? . .. 1“
'2 "' H 3 ‘. :’
4 ‘ -vo 0.9 at. -.:
c ' ‘t H‘::. 2':
“'0 7 D 1 3 .5} .z’l.‘
j z z: :::
"' ;‘ H; ?
IIOIIII'IOO" I: 3..
o . ..... . . ..,,‘§;1;§‘) ,
5000 4000 W0 2000 m .00 ”00

wavenumber

3. a) IR Spectrum of Spiro[tetracyclo[7.4.1.01'903'8]tetra-
dec—3-ene-2-one-14,1'-cyclopentane].

.\|‘ \\l \"\'I)‘

 

 

 

2-0 ‘
v0
2
1-6
1-4 4
1'2 ' G
a
1-0 10
0-8
a"
- -I
o o 6 u
u :1
C 4 a
a
.5 0-4 ‘_ 1 405
3 < '5'
y 1 so
00 j 100

as
Wink". h millimicrons

3. b) UV Spectrum of Spiro[tetracyclo[7.4.1.01'903I8]tetra-
dec-3-ene-2-one-14,1'—cyclopentane].

61

.HmGM5GmmoHoho
o E5Huommm mzz .w

I.H.mImCOIOHImaOMHSHCMOvaflmumUIOH.m.m.b.®.m.v.m.N.HHOHflmm m
3 a Q h o
.._...-.-- .....a¢+-fi-..-q.-.-h ..-...-..--4_J.-..--.._..-...--.F..-......H.q-4.-..<
4 d ..... 1-1I1<(1 1)“ 44444444 “.144 4211411411444. 44444 14).- q 4 1._ 4 4‘1 1

‘I‘IH‘qtil-{J‘
< 1

1 - . _
I:

 

 

1)d< q
‘

 

 

 

8‘

hi I .- I). I) > I— I I I — I I 5). P I, I b r I I I
I—Itph un—>L()-P>)>—III. urtb—Iprrhfibbn—

I I I D I I I (P P
I I F b — L D D b D b i D b .— F r h h h F P I
-

P [I

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by)’ b b b y p I

 

II-II.I—IIII-

I-Ip

62

.Hmcmucwmoaumu
I.H.mumsouoalmcmuzucmcmzmonpmsmomploasm.m.b.m.m.v.m.m.a_ouflmm mo E5H5Ummm mzz .m

)‘IHITQJ‘1115—1I11delie ll‘I‘l‘l—ll1‘qll41+‘)‘l“1I‘l_‘1l1-ll‘1H|11|‘J‘.fii11‘_4I11-1111—111l-1l41_11ldq“11
‘11! 4 . a «144.111.1111 111111111 -Id)4ld1141l42-) 11111111 4‘111‘41141- 111111111 d<<<dne<l._<¢<-4<4<d\A-) 444444444

 

 

 

 

8 o 8. 8n RX 81

 

A
I

)

{—%4F4—a

pp ..P. IIIII»P>I.I>I>I.— I). PIP?

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