SYNTHESB AND PRELIMINARY
SOLVOLYTTC STUDIES OF DERWATIVES
0F BICYCLOI3.2. 1}OCT-6-EN-3-0L

Thesis for the Degree of M. S.
MICHTGAN STATE UNIVERSITY
ROBERT E. BOTTO
1970

L I B R A R Y
Michigan Stats
sity

Univcr

  
   

  
 
 

   
 
   
 

9' “ ‘=
BINDTNG BY ‘

nuns & suns! ‘

SYNTHESIS AND PRELIMINARY SOLVOLYTIC STUDIES
OF DERIVATIVES 0F BICYCLO[3.2.I]0CT-6-EN-3-OL

by

Robert E. Botto

A THESIS

Submitted to:
Michigan State University
in partiaT fuTTfiTTment of the requirements

fer the degree of

MASTER OF SCIENCE

Department of Chemistry
1970

ABSTRACT

SYNTHESIS AND PRELIMINARY SOLVOLYTIC STUDIES
OF DERIVATIVES OF BICYCLO[3.2.T]0CT-6-EN-3-0L

By
Robert E. Botto

The synthesis and characterization of gi§;endo-2,4-diphenyl-
bicyclo[3.2.l]oct-6-en-endo-3-ol (XVIII) and giérendo-2,4-diphenyl-
bicyclo[3.2.l]oct-6-en-g§9:3-ol (XXII), and derivatives thereof

are reported.

/ Ph Ph

Ph Ph OH

(XVIII) (XXII)

These alcohols are obtained via bicyclic ketone (XVI). Lithium
aluminum hydride reduction of the ketone produces the gnggfalcohol
(XVIII) as the only reduction product, whereas Bouveault-Blanc
reduction results in the isolation of the g§Q:alcohol (XXII) along
with its epimer, 3523532,4-diphenylbicyclo[3.2.l]oct-6-en-g§g:3-ol
(XXIII).

./ ’h Ph
Ph 15"

. Ph

(xv1) 0”

(XXIII)

Solvolyses of the endo and g§g_methanesulfonates (compounds (X) and
(XI) respectively) show that the reaction mixtures contain predominately

elimination product, diene (XXVII).

/' Ph /’ .h
Ph
P osozcu
cn3ozso
00 (XI)

3

Ph

'h
(XXVII)

ACKNOWLEDGMENT

The author would like to express both his thanks and appreciation
to:

... Dr. Donald G. Farnum for his guidance and understanding
throughout the course of this project - whose friendship is
cherished - whose excellence as a chemist is surpassed only by his
idealism - and whose ping-pong playing is atrocious.

... my fellow graduate students: Glennie, Raghu, Rog, Big Al,
Bill, and last, but least, Gabone ( and Myrn).

. a nobleman second class, Lord Eric.
... Local Board #4 without whose undying effort this thesis would

never have been written.

to my parents,

this is more
theirs
than it is

mine

TABLE OF CONTENTS

Page
INTRODUCTION. . . . . . .................. 1
RESULTS AND DISCUSSION ................... 13
EXPERIMENTAL. . . . . . . . . ..... . ......... 31
Part 1: Synthesis ......... . . . . . . . . . 32
Cis-endo- 2 ,4-diphenylbicyclo[3. 2. l]oct-6-en-3-one
TXVI) ........ . . . . ...... . 32
Cis-endo- 2 ,4- diphenylbicyclo[3. 2. l]oct- 6-en-endo-
S-ol (XVIII). Lithium Aluminum Hydride
Reduction . . . . . ..... . . . . . . . . 32

2331:3223.°;-e—:::;¢1;:?:I.5:2{e Jig-23%:

(XIX). Method A - Acetic Acid. . . . . . . . . . 33
Method B - Toluenesulfonic Acid ......... 33
Method C - 30% Sulfuric Acid. . ......... 34
Sodium-Alcohol Reduction of Ketone (XVI). . . . . 34

Preparation of the p:Nitrobenzoates (XX) and
(XXI) . . . ...... . ......... 35

Qig;endo-2,4-diphenyloct-G-en-55933-ol (XXII) . . 37

Chromium Trioxide-Di yridinium Complex Oxidation

of exo-Alcohol (XXII . . . . .......... 37
Trans- 2 ,4 diphenylbicyclo[3. 2. l]oct-6- -en-exo- -3-
0| (XXIII). o o o o o o o o oooooooooo 38

Chromium Trioxide - Dipyridinium Complex
Oxidation of trans-Diphen l-exo-Alcohol. Trans-
2 ,4 Diphenylbicyclo[3. 2. lfiocE331en-3-one (XXIV) . 39

Part

TABLE OF CONTENTS (Continued)

Sulfuric Acid Treatment of Alcohols (XXII)
and (XXIII) ................ . . .

Cis-endo-2,4-diphenylbic clo[3.2.l]oct-6-en-g§9;
3:;1 methanesulfonate(x). . . .........

Cis-endo-Z,4-diphenylbicyclo[3.2.l]oct-6-en-endo-
3-yl methanesulfonate (XI) ...........

Epimerization of Bicyclic Ketone (XVI) with
Sodium Methoxide ................

Diimide Reduction. Cis-endo-2,4-diphenylbicyclo-

[3.2.l]octan-3-one (XXVII) ...........
Cis-endo-Z,4-diphenylbicyclo[3.2.l]octan-endo-
3-ol (XVIII) ....... . ....... . . .

Attempted Mesylation of Saturated-endo Alcohol
(XXVIII) ....................

Cis-endo-Z,4-diphenylbicyclo[3.2.l]octane-endo-
3-yl methanesulfonate (XV) ...........

Cis-endo-2,4-diphenylbic clo[3.2.l]oct-25273-
yT-metfianesulfonate (XIV) ............

Lithium Aluminum Hydride Reduction of Endo-
mesylate (XI). 2-Phenyl-endo-4-phenylBicyclo-
[3.2.l]octa-2,6-diene (XXVII) ..........
Catalytic Hydrogenation of Diene (XXVII).
Cis-endo-2,4-diphenylbicyclo[3.2.l]octane
TXXVIII') . . . . . .............

II: Solvolysis ....... . .........
Acetic Acid ...................

Formic Acid ............ . ......

ii

Page

39

39

4O

4T

4T

42

43

43

44

44

46
47
47
47

TABLE OF CONTENTS (Continued)

Page

Trifluoroacetic Acid ............... 48

Ethanol: Hater ................. 48

Dioxane: Hater ................. 49
Dimethylformamide (IMF) ............. 49
REFERENCES ......................... Sl
APPENDIX - NMR Spectra ................... 53

iii

LIST OF TABLES

TABLE Page
I Ultraviolet Absorptions (Carbonyl Chromophore)
of Ketones (XVI) and (XXIV). . . .......... 22
II Results of NMR Decoupling on Diene (XXVII) ..... 27

iv

FIGURE

10

ll

LIST OF FIGURES

Energy Profile For a Diels-Alder Reaction. . . . .

Symmetric Approach of Butadiene and Ethylene

in the Diels-Alder Reaction. . .........

Correlation Diagram for the Diels-Alder

Reaction of Butadiene with Ethylene .......

Symmetric Approach of Cyclopropanone and

Cyclopentadiene. . . . . . . . . . . .....

Classical Fragmentation Pathway (Thermally

Allowed) ..... . . . . . ..... . . .

Transition State fer Concerted Fragmentation of

Exg Mesylate (X) (X = OSOZCH3) . . . . . . . . .

Energy Diagram for Solvolysis of Compounds

(X) and (XI). With Concerted Fragmentation. . . .
Reaction Path Without Fragmentation .......
Energy Profile Without Fragmentation ......

Approach of Metal Hydride in the Reduction

of Ketone (XVI). . . . . . . . . . . . . . . . .

Distorted Conformation of Epimerized

prNitrobenzoate (XXI). . . ...........

. 5

10
. lO
. ll

. l6

. 20

INTRODUCTION

Cycloadditions of conjugated dienes have claimed the interest of
synthetic and mechanistic chemists for nearly forty years. However,
isolated examples of diene additions have been found as early as
the turn of the century.

In l893 Zincke correctly explained the formation of perchloro-
indenone (II) in the pyrolysis of l-hydroxyperchlorocyclapent-B-ene
carboxylic acid (I) suggesting perchlorocyclopentadienone as an

intermediatel.
C1 C12

A5
0 .H
‘3 CDH

12
(I) <11)

 

In the years following, controversy arose as to the actual structures of
the adducts formed. Staudinger and Albrecht proposed structures involving
cyclobutane rings, but these later proved to require revision. It was not
until some thirty years later, when Diels and Alder elucidated the
structure of the l:l adduct (III) of p;benzoquinone and cyclopentadienez,

that the nature of the reaction became evident.
I

This introduced the fruitful preparative and mechanistic investigations
of these authors. The structure of the l:l addition compound (TV) from
cyclopentadiene and diethyl azodicarboxylate3 illustrated the diversity

of this reaction type.

N/COZEt N/C02Et
- u -—e T
EtOZC/ \COZEt
(IV)

Indeed, the literature contains a wealth of examples concerning this one
step reaction, and the wide variation in reactants allows access to many
important classes of compounds“. A

The history of the retro-diene reaction is as old and diversified
as the cycloaddition itself. In 1929 Diels and Alder demonstrated that
an adduct of furan and maleic anhydride (V) decomposed into its addends
at its melting 0point of 125°5.

1. __.__> 9 +041.

\
(v) ‘

Many examples have been reported in the literature since this discovery5.
It is also important to note that the reverse process most often
occurs at similar or higher temperatures than the forward process. This
is a direct consequence of enhanced thermodynamic stability of the adduct
over that of the starting materials since forward and reverse processes

have identical transition states (Figure I).

Energy (E )

ar

VI!

(5,),

 

 

 

 

———-—reaction coordinate———{;>

FIGURE I. Energy Profile For a Diels-Alder Reaction

where (Ea)f 8 activation energy for forward
process
(Ea)n = activation energy for reverse
process
[T.S.]* a transition state

The theory of concerted transformations has been refined and extended
by the contributions of Woodward and Hoffmann’. Their molecular orbital
approach has helped inmenely in understanding the structure-selectivity
of the Diels-Alder and related addition reactions. It is from them
that we learn that conservation of orbital symmetry dictates a reaction
pathway.

If we consider the [4 + 2] cycloaddition of butadiene to ethylene,
then a reasonable approach is characterized by a single plane of symmetry
bisecting the two components. This can be justified for the following

reasons. First it is the most sterically accessible approach for the

 

FIGURE 2. Symmetric Approach of Butadiene and Ethylene
in the Diels-Alder Reaction.

two molecules. And second, it allows maximum u-overlap of the
approaching orbitals leading to the transition state. There are six
essential levels involved in the reaction which can be illustrated in the
the following correlation diagram (Figure 3). Delocalized a-bond
combinations and u-bond combinations must be constructed for both

product and reactants, respectively. Every bonding level of reactants
correlates with a bonding product level; there is no correlation between
bonding and antibonding orbitals. The transformation is a symmetry

allowed ground state process and, therefore, thermally allowed.

As already noted, there have been many examples of [4 + 2] cyclo-
additions, but none so intriguing as those involving ionic components.
The first example of this novel transformation has been observed by

Fort, gt,gl,°.

r
0 2,6 lutidin
X\ l? " ./[[)/\ DMF ;

 

 

 

 

FIGURE 3. Correlation Diagram for the Diels-Alder
Reaction of Butadiene with Ethylene.

It has been suggested that the reaction actually involves the isomeric
dipolar form of cyclopropanone (VI), although there is some question

as to whether cyclopropanone itself reacts9.

P Ph G) G)
__> / \
‘:_—- P h <%"_—T> P h
a m °®

{Since orbital symmetry dictates the number of electrons, not the total
number of orbitals,the ionic component in the above reaction is treated
as though it were a simple Zu-electron moiety. Here again, a reasonable

approach is a plane bisecting the two components (Figure 4).

 

 

 

FIGURE 4: Symmetric Approach of Cyclopropanone
and Cyclopentadiene.

However, substituent n-interaction with the conjugated diene may
help to lower the transition state energy and must therefore be

considered. This would account for the stereOSpecificity of the

product.
More recently, Hoffman reported the first direct combination of

a simple allyl cation with cyclopentadiene10.

A2 C1 3cco 2A9 > @ @
liq SO2
2CC(Cl)3

(mixture of egg.

and endo)

 

Retrodiene cleavage concerted with ionization is possible during
solvolysis provided orbital symmetry is conserved and bond reorganization
is not accompanied by excessive strain energy. Electrocyclic trans-
formations during solvolysis are well established. Cristol, 35,31,11,
have demonstrated that gyg;7-chlorocarane (VII) undergoes solvolysis
readily at 125°, whereas its epimer (VIII) remains unchanged after

prolonged treatment with acetic acid at 2l0°.

C
Wk

H CI N20“
2\°°

(VIII)

These results can be interpreted in terms of a concerted disrotatory
opening of the 1,6 bond which becomes available for backside displacement
of the leaving group. When the leaving group is ag51_to the ring system,
rotation would lead to a trans, trag§;allyl cation which is severly
strained. Whitham has shown that the solvolysis of 359:8-bromobicyclo-
[5.l.0]octane12 gives the expected tggg§;cyclooctenol (Ix) clearly

establishing the concertedness of the reaction.
H ,Br

I

A
/

(IX)

It seems likely, therefore, that a concerted ionic [4 + 2]
fragmentation is plausible. We have chosen to study the solvolysis
of g§9_and gngg_bicyclo[3.2.l]octenyl mesylates (compounds (X) and
(XI), respectively) to investigate this possibility.

/ Ph / Ph
Ph P
(x) "5 (x1) "5

These particular systems have two distinct advantages: the steric
influence of the phenyl substituents hinders nucleophilic attack at
the cationic center, and fragmentation would lead to an energetically

favorable species, namely the l,3-diphenylpropenyl cation (XII) shown

 

 

 

below (Figure 5). __' “‘
Ph
69 a Q
L__ h .._L T
products <: solvent pn/g2\é79\\xph

 

(XII)

FIGURE 5. Classical Fragmentation Pathway (Thermally Allowed)

Fragmentation could be concerted with ionization if there is a
traggyagtlrparallel relationship of the two neighboring carbon-carbon
bonds and the carbon-oxygen bond. In the transition state of (X) the
leaving group (designated by Y) does attain this anti_relationship

(Figure 6). As X leaves, the developing positive charge could become

stabilized by the developing p-orbitals in the alpha-positions, i.e.,
the p-orbitals produced from the concerted fragmentation of the 1,2 and
4,5 aébonds become available for backside displacement of the leaving

group. There might also be a bonding contribution from the u-orbitals

at carbons 6 and 7.

 

FIGURE 6. Transition State for Concerted Fragmentation
of §§Q_Mesylate (X) (Y = 0502CH3)

note: substituents omitted for simplicity

However, this mode of ionization is impossible for the eggg_isomer
(XI) which must ionize without such participation. Thus, one might
predict a lower transition state energy fOr the gxg_compound (X).
The implications for the energetics of the reaction are depicted
below (Figure 7).

Fragmentation need not occur in order to observe rate acceleration.
Thus ionization of the gxgrisomer (X) might proceed to delocalized
non-classical cation (XIII), which could react with solvent without

fragmentation to give bicyclic products. This would lead to a

TO

[1.s]*

Energy [T-S]*
bicyclic cation

 

“959.

 

 

——reaction coordinate—9

FIGURE 7. Energy Diagram for Solvolysis of Compounds
(X) and (XI). With Concerted Fragmentation.

transition state in which the developing positive charge is delocalized
(aver a much larger precentage of the molecule and should be stabilized

try such a charge distribution (Figure 8). 1
"T.S

h "——‘€3’ Afiiighi’ Ph
P 5- (D
(X)

r— fi T.52 fl (XIII)
/ Ph 35 - s 1\/

 

 

 

 

 

 

 

P Ph
MsO L.. P" Products
6" ’5'? _
(XI) "50”

Figure 8. Reaction Path Without Fragmentation

ll

 

 

1: etc.

[T.S]*2

T [1.5]"‘1
cation (XIII)

Energy

 

endo
exo

 

 

 

-————-reaction coordinate———+>

Figure 9. Energy Profile Without Fragmentation

The cations resulting from ionization of (X) and (XI) are subject to

the same nonclassical resonance, hence, these intermediates are identical
in energy. The difference occurs in the transition state - the
delocalization inherent in the intermediate is reflected in the transition
state of the gxg_species only. Assuming that the ground state energy
difference between compounds (X) and (X1) is negligible, delocalization
should lower the energy of the gxg_transition state and, consequently,

must lower the energy of activation (Figure 9) necessary to achieve it.

12

Steric acceleration to ionization in compound (X1)is an important
factor which should not be overlooked. The eggg_leaving group is not
only situated under the ring system but gi§_to both phenyl moieties.
This should appreciably enhance the rate of (XI) relative to (X). Since
two opposing factors are in operation a kinetic study would prove
meaningless. Only by comparing the rates of the saturated analogues,
(XIV) and (XV), can we estimate steric rate acceleration in the absence

of delocalization. Furthermore, comparing the rates of (X) and (XIV)

(x1v) 0M5 "50 (XV)

should establish the rate enhancement due to participation since it
seems very unlikely that the transition state resulting from
ionization of (XIV) is subject to the same delocalization as its
unsaturated analogue - ionization of (XIV) should lead to a classical
secondary cation. Thus, compound (X) should solvolyze faster than
(XIV).
This thesis describes the synthesis and preliminary solvolytic

study of (X), (XI), (XIV), and (XV).

RESULTS AND DISCUSSION

A reasonable synthetic approach to compounds (X) and (XI) seemed
to be via bicyclic ketone (XVI) which had previously been prepared by
two different methods. Fort and coworkers treated benzyl-a-chlorobenzyl
ketone with 2,6-lutidine in the presence of cyclopentadienee. Although

the specific reaction conditions were not given Cookson's preparation

// Ph // PM
P Ph
OMS OMS
0‘) (X1)

Br Br

Ph h

 

(XVI) (XVII)
of the same adduct involved reduction of dibromide (XVII) with sodium

iodide in acetone9. The later method seemed the more attractive in

view of the milder conditions required.

13

14

Using the procedure outlined in the experimental section (ngg_
infra) we were able to obtain optimum yields of 73% on large quantities
of material following Cookson's suggestions. The spectral properties
of our compound were in complete agreement with those reported in the
literature. The simplicity of the nmr spectrum suggested that a plane
of symmetry existed through the carbonyl moiety. The very weak n + n*
absorption for the carbon-oxygen double bond demonstrated that the two
phenyl substituents assume an equatorial positon13. Since the orientation
of the benzylic hydrogens had been established, we could determine the
conformation of the six-membered ring system on the basis of coupling
(observed: J - 4 cps) between the benzylic hydrogen atoms (Hc) and the
bridgehead hydrogens (Hb). If the six-membered ring assumes a boat
configuration the dihedral angle between HD and Hc would be 93, 90°;

' consequently, the coupling constant between them should be zero. On
the other hand, if configuration (XVI) is assumed the dihedral angle
becomes approximately 45°, and the estimated coupling is in accord with
that observed experimentally. The spectroscopic evidence agreed with
the conviction that the adduct (XVI) arises from eggg_addition of the
cyclopropanone - like intermediate to cyclopentadiene.

Treatment of ketone (XVI) with lithium aluminum hydride in refluxing
ethyl ether afforded gigfgnggrdiphenylbicyclo[3.2.l]oct-6-en-gngg;3-ol
(XVIII) as the only reduction product in 65% yield. The unreacted
starting material was mechanically separated from the alcohol since
recrystallization from hexane afforded two distinct crystal forms which

were quite easily recognized.

15

 

(XVIII)

Compound (XVIII) exhibited only free hydroxyl absorption in the
infrared at 2.8l u (sharp) which is characteristic of a sterically
hindered alcohol. That a plane of symmetry still existed was verified
by the simplicity of both the phenyl and olefinic regions of the nmr
spectrum. The retention of the chair confbrmation during reduction
was born out by the coupling between Ha and Hb in the product (J = 1.8
cps). If the six-membered ring assumed a boat conformation the dihedral
angle between the two protons should be nearly 0°, hence the coupling
between them would be large. The rather small coupling constant
showed that, in fact, the dihedral angle increased over that of ketone
(XVI) due to changes in hybridization at C-3. The coupling (J - 4.5 cps)
between the methine proton (He) and the benzylic hydrogens (Hb) was
consistent with £1§;coupling in similar systemsl“. Consequently, the
hydroxyl moiety must be gyg_to the two-carbon bridge. Shaking the sample
with deuterium oxide resulted in the disappearance of the signal located
at T 8.55.

The mass spectrum of alcohol (XVIII) exhibited a parent peak at m/e

276 (calcd: 276). Analysis confirmed the molecular fermula C20H200°

16

The fOrmation of only the endo-isomer is quite easily rationalized.
The attack of the metal hydride must occur approximately perpendicular
to the plane of the carbonyl double bond (Figure 9) designated by

axis C15.

 

Figure 1). Approach of Metal Hydride in the
Reduction of Ketone (XVI).

By far the less sterically favorable approach of the large metal hydride
is from the underside of the molecule. Here the reducing agent
encounters steric repulsion from both the two-carbon bridge and the
large equatorial phenyl substituents. Attack from the top involves

only two alphafhydrogen repulsions.

Internal cyclization can occur only if the hydroxyl moiety is §y2_
to the double bond and the six-membered ring assumes a chair conformation.
It is reasonable that protonation of the double bond would lead directly
to oxonium ion (XIXa), that is, concerted oxygen participation would
occur during protonation (Scheme 1). Subsequent loss of a proton would

result in the fOrmation of (XIX). Such neighboring group participation

I7

is well established in the literature especially if it occurs via a

favorable 5-membered transition state15.

Scheme I

 

 

 

 

 

 

 

[— fins *
h H”
—-->
Ph
Ho L /°,, _
H
(XVIII)
V/
H __
Ph
~H+
'h <E"""‘ Ph
P
o T‘ [09 J
(XIX) H
(XIXa)

Refluxing endo-alcohol (XVIII) in 30% sulfuric acid led to the
isolation of tricyclic ether (XIX), syn:§yg;4,9-diphenyl-2-oxatricyclo-
[3.2.l.l3s7]nonane, which exhibited infrared absorption at 9.89 u. The

structural assignment was based mostly on the nmr data. There was no

18

olefinic resonance present. Two signals located at r 5.32 and 5.62
were characteristic of two methine protons adjacent to an ether linkage.
The absence of any coupling to the lower field benzylic hydrogen (T 6.79)
reflected the severe distortion present in the cyclohexane ring
system. Both the adjacent bridgehead proton and the methine hydrogen
at carbon-3 do become perpendicular to this low-field-axial-benzylic
proton by such distortion in molecular models.

The mass spectrum of the tricyclic ether exhibited a parent peak
at m/e 276 (calcd. 276), but its fragmentation pattern was quite
different from that of the starting alcohol. The compound analyzed
correctly fer CZOHZOO‘ The data presented confirmed our suspicion that
acid catalysis mediates structural isomerization of alcohol (XVIII).

Lithium aluminum hydride reduction of ketone (XVI) made us aware
of the large steric factors inherent in such a ring system. Thus the
relatively convenient Bouveault-Blanc reduction of the ketone should
produce the more thermodynamically stable reduction product, namely
the g§g7alcohol (XXII) (vide infra). Reduction of ketone (XVI) with
sodium and ethanol in refluxing toluene did yield a red oil whose
spectral properties suggested the presence of a mixture of products.
Since crystallization of the crude material was extremely difficult,
it was thought that separation of the p:nitrobenzoate derivities of
these isomers could be more easily accomplished.

The crude mixture was treated with prnitrobenzoyl chloride and an
equivalent amount of pyridine in ethyl ether. Fractional recrystallization
from 95% ethanol afforded long-yellowish needles, m.p. l8l.5-184.5°,

which were purified further. Eventually a colorless solid, gigfendo-

19

2,4-diphenylbicyclo[3.2.l]oct-6-ene-gxg;3-p:nitrobenzoate (XX), was
obtained whose infrared spectrum possessed characteristic ester absorption
at 5.75 p. The A282 quartet centered at 1 2.l9 in the nmr further
established the presence of the Ernitrobenzoyl moiety. The unusually
low-field methine resonance (Hb) (r 4.08, t, J a 9.8) could only be
explained by the anisotropic effect of the three phenyl rings and the

ester function which encompass it.

 
 

(XX) b 0‘ flT©~Noz

The assignment of the g§g_ester function was based on the large coupling
(9.8 cps) observed between Hb and the axial-benzylic protons (H‘), and
is typical of trggsydiaxial coupling found in similar rigid cyclohexane
ring systemsl“. Analysis for the compound was consistent with a
molecular formula of C27H23NO4 while the highest peak in the mass
spectrum was m/e 258 (calcd. 425) due to quantitative elimination of
prnitrobenzoic acid (P-l67).~

Concentration of the remaining ethanol solution afforded another
solid, trag§:2,4-diphenylbicyclo[3.2.l]oct-6-ene-g§g;3-p-nitrobenzoate
(XXI), m.p. l39°, whose infrared absorption at 5.78 u was also
characteristic of an ester carbonyl group. The rather complex nmr
spectrum reflected the annihilation of the symmetry. This was confirmed
by the two distinct chemical shifts of the benzylic protons, Ha and Rb,
and their different coupling to the methine hydrogen (HG). Perhaps the

20
most convincing evidence as to the gxgrnature of the prnitrobenzoyl
moiety was the large coupling (J 8 11.5 cps), typical of trgg§;diaxial
coupling in such systems, between the methine proton and the axial-
benzylic proton (Ha)’ The surprisingly large coupling (J = 7.6 cps)
Ph

(xxx) "c 0 —fl @4102

between Hb and Hc can be rationalized in terms of ring distortion

created by repulsions of the axial phenyl moiety (Figure l0).

Ph b

Figure ll. Distorted Conformation of Epimerized
pritrobenzoate (XXI).

As the phenyl substituent assumes a pseudo-equatorial position the
hydrogen (Hb) must attain some axial character; consequently, the
dihedral angle between Hb and Hc approaches 0° and the coupling between
them increases. Confirmation of the molecular formula, C27H23N04,
was obtained from analysis.

Hydrolysis of the two prnitrobenzoates with 8% alcoholic potassium
hydroxide led to the isolation of their respective alcohols, gxg_alcohol

(XXII) and gxgrepimerized alcohol (XXIII).

21

Ph

/ P" /
Ph Ph
OH OH

(XXII) (XXIII)

The infrared spectrum of gxg7alcohol (XXII) exhibited both free and
intermolecularly bonded hydroxyl absorption (2.83 and 2.88 v) while
that of (XXIII) only showed absorption at 2.82 n. The nmr spectra
(Appendix) for these compounds parallel those of their respective
precursors and will not be discussed. Both compounds analyzed
correctly for CZOHZOO and their mass spectral analyses were consistent
with a molecular weight of 276.

Refluxing compounds (XXII) and (XXIII) in 30% H2504 yielded only
starting material. There was no evidence for tricyclic-ether formation.

A more comprehensive structure analysis was undertaken by
reoxidation of the two alcohols. Acidic and basic conditions were
avoided to prevent epimerization of the ketone formed during the
reaction. Oxidation of the gngalcohol (XXII) with Collins reagent
(see Experimental) led to the isolation of ketone (XVI) which was
identified by comparison with a sample prepared in the reaction of the
cyclopropanone with cyc10pentadiene (gjgg_§uprg). When alcohol (XXIII)
was subjected to the same conditions a different ketone was isolated,
trag§:2,4-diphenylbicyclo[3.2.l]oct—6-en-3-one (XXIV). The absorption
at 5.84 in the infrared spectrum was characteristic of a cyclic (six-
membered ring) ketone. The prominent feature of the nmr spectrum

seemed to be the different chemical shifts of the two bridgehead protons

22

and reflected the dissymetry of the molecule. The ultraviolet Spectrum
of this ketone~was quite informative. An axial-phenyl interaction

with the carbonyl chromophore is known to shift the n + n* transition
to longer wavelengths and increase the extinction coefficient13. This,

in fact, does occur (Table l). The compound analyzed correctly fir'C20H18O.

TABLE I: Ultraviolet Absorptions (Carbonyl Chromophore)
of Ketones (XVI) and (XXIV).

 

 

n + n* transition extinction
Compound (nm)_ coefficient
(XVI) 290 29
(XXIV) 300 115

 

 

 

 

 

Treatment of ketone (XVI) with sodium methoxide and methanol in
toluene for 6 days gave epimerized ketone (XXIV) in 68.8 t 1.1% yield.
This established that the two ketones were indeed epimers. Interestingly,
the ketone which contained an axial phenyl substituent was the
thermodynamically predominant product. The only explanation that
can be given requires that the energy involved in axial:repulsions
(consider the six-membered ring) is less than those encountered through
interaction with the bridgehead hydrogens and the two-carbon bridge
when the phenyl moiety is equatorial. On the other hand, diepimerization
would lead to a higher energy state because of the 1,3 diaxial diphenyl
interaction produced.

Epimerization during the sodium-alcohol reduction can be understood
in terms of the above equilibration experiment. Integration of the

two methine resonances centered at r 5.80 revealed that the gngtrans

23

diphenyl alcohol (XXIII) comprised 48.1 2 .4% of the total reduction
product. This means epimerization (which is favored over reduction by
the presence of protic Sflvent) occurs at a rate more slowly than
reduction under these reaction conditions. However, it is still quite
competitive. Longer reaction times would favor epimerization until
thermodynamic equilibrium is ultimately reached. Accordingly,

optimum yields of the desired alcohol (XXII) were obtained employing
short reaction lifetimes and low concentration of ethanol.

Every attempt to prepare the p:toluenesulfonate of the endo:
alcohol (XVIII) failed, probably due to the enormous steric repulsions
implicated for attack by such a large molecule. However, treatment
of the gndg:alcohol with methanesulfonyl chloride in pyridine at 0°
led to the isolation of gj§;gggg;2,4-diphenylbicyclo[3.2.lJoct-6-en-
egg9;3-methanesulfonate (XI)in 65% yield. The infrared Spectrum of this
compound exhibited characteristic covalent sulfonate absorptions at
7.39 and 8.54 n. The nmr displayed a sharp three proton singlet at
r 8.26 (sulfonate methyl); the rest of this spectrum was similar to
that of its parent alcohol (Appendix). §j§:gggg;2,4-diphenylbicyclo-
[3.2.1]oct-6-en-gxg;3-methanesulfonate (X) was prepared in the same

fashion (72% yield).

Ph so CH '
2 3 CH 0250
0‘) (X1)

24

Infrared absorptions of this sulfonate appeared at 7.39 and 8.52 p.
The methyl singlet in the nmr now appeared at r 8.57. Both compounds
analyzed correctly for C21H22503. Their mass spectra exhibited parent
peaks at m/e 354 (calcd. 354). The fragmentation patterns for the two
compounds were remarkably similar except fer slight differences in
relative intensities of the fragments.

The preparation of the saturated analogues of compounds (X) and
(XI) was first attempted following the reaction sequence described
above on saturated ketone (XXV). The saturated ketone was prepared by

diimide reduction of ketone (XVI).

(XXV)

 

The infrared spectrum of (XXV) exhibited absorption at 5.83 v; nmr:
r 2.86 (10H, phenyl), 6.22 (2H, benzylic), 7.35 (2H, bridgehead), 7.60-
8.55 (6H, methylene). The n + n* transition in the ultraviolet was
found at 290 nm (e = 30). The compound analyzed for CZOHZOO’

Lithium aluminum hydride reduction of ketone (XXV) gave §j§;gggg;
2,4-diphenylbicyclo[3.2.l]octan-ggggy3-ol (XXVI) in 90% yield.
Hydroxyl absorptions at 2.81 and 2.89 u in the infrared were characteristic

of free and intermolecularly bonded interactions. The small coupling

Ph
H0 b
(XXVI)

25

(J = 3.8 cps) between the methine proton (Hb) and the benzylic hydrogens
(Ha) in the nmr established the axial nature of the hydroxyl moiety.
Confirmation of the molecular weight was obtained from mass spectrometry
with a parent peak of m/e 278 (calcd. 278). The molecular formula
CZOHZOO was verified by analysis. All attempts to prepare the methane-
sulfonate derivative of this alcohol met with defeat, probably as a
direct consequence of the greater (to its unsaturated analogue) steric
hindrance created by the eggg_hydrogens on the now saturated two-carbon
bridge. The alternative which remained was reduction of the unsaturated
mesylates (x) and (XI) themselves.

Diimide reduction of gigg-Inesylate (XI) produced gym-2,4-
diphenylbicyclo[3.2.1]octane-gnggf3 methanesulfonate (XV) in 88% yield.
The infrared spectrum showed absorption at 7.43 and 8.57 u; nmr: r 4.33
(1H, t, J a 3.9 cps) methine proton, 8.41 (3H, s) sulfbnate methyl.

The parent peak in the mass spectrum was in complete accord for the
addition of one mole of hydrogen, m/e 356. Analysis was consistent

for a molecular formula 0f C21H24503. Reduction of the gngmesylate

Ph 'h

P P
0250 VSOZCH3

(xv) (XIV)

CH3

(X) led to the isolation of its saturated analogue, gj§;gggg;2,4-
diphenylbicyclo[3.2.l ]octane-_exo_-3-methanesulfonate (XIV); infrared:
7.41 and 8.52 n; nmr: r 4.31 (1H, t, 10.4 cps) methine proton, 8.14
(3H, s) sulfonate methyl; mass spect: m/e 356. This compound also

analyzed correctly for C21H24SO3.

26

Since the four methanesulfonates (vigg_§upgg) had been isolated
and their structures elucidated it was possible to commence with our
solvolytic investigation. It should be realized that the results
discussed here evolve from a very primitive study of only compounds
(X) and (XI). The primary purpose for such an investigation was the
discovery of the proper solvolytic conditions necessary to initiate
ionization, and characterization of the major products; the kinetic
rates of reaction were not determined and will not be discussed.

Acetolysis of either the gndg_or gxg_mesylate (X or XI) at 35°
resulted in the recovery of starting material. Formolysis at 50° or
80° also proved insufficient to promote ionization of the egggfisomer.
When the gnggycompound was subjected to more vigorous conditions,
i.e. heated to 140° in the presence of acetic acid buffered with 5%
sodium acetate, only an intractable polymeric tar could be isolated.

Treatment of the gngg;mesylate with trifluoroacetic acid (also a
run containing 5% sodium trifluoroacetate) resulted in the isolation
of a yellow polymer. It was not determined whether this polymeric
material had its origin from the parent system or the 1,3 diphenyl
allyl cation which would be formed via our proposed fragmentation
pathway (Scheme II).

Scheme II

"Pig @+ pm... J

Npolymer

27

Subsequent runs were conducted with the exclusion of acid which seemed
to catalyze polymerization.

When either mesylate was heated to 140° in a 1:1 ethanol-water
solvent system, with or without added triethylamine, the major solvolysis
product isolated was diene (XXVII), 2-phenyl-gngg;4-phenylbicyclo[3.2.1}
octa-2,6-diene. Similar results were obtained in dioxane-water. It
should be noted that other products (5-15%) were formed, but they were
neither isolated nor characterized. Solvolysis at 140° in a slurry
of sodium carbonate and dimethylformamide containing lithium chloride
produced diene (XXVII) in quantitative yield. Attempted reduction of
the egggrmesylate with lithium aluminum hydride again resulted in
isolation of the diene. Its ir spectrum showed characteristic olefinic
and aromatic absorptions at 3.32 (doublet). The absorption at 255 nm
(e = 13,000) in the ultraviolet was typical of a styrenyl chromophore.
The nmr spectrum was as follows: 1 2.53-3.10 (10H, phenyl), 3.61 (sym.
quartet, Hd), 4.34 (quintet, Hb), 4.74 (sym. quartet, Hc), 6.23 (doublet
of doublet's, Ha)’ 6.83 (multiplet, Hf), 7.02 (multiplet, He)’ 7.78
(complex, methylene-bridge protons). The coupling between the protons

was verified by irradiation experiments (Table II).

 

(XXVII)

28

TABLE II: Results of NMR Decoupling on Diene (XXVII).

 

 

 

 

 

 

 

 

 

 

Signal Signals I Coupling
Irradiated Altered Multiplicity (cps)
H Hc doublet 2.8
d Hf pattern change -——-
Ha doublet 4.8
Hb He pattern change -——-
Hf pattern change
H H doublet 2.8
c H: pattern change -—-
H Hb unsym. quartet ~1.5
a Hf pattern change -—-—
H Hb sym. quartet 1.5
f Hd doublet 5.8
Hb unsym. quartet él.5
He H doublet 5.8
H: broad doublet ~3.0
Hd doublet 5.8
He & Hf Hc doublet 5.8
Hb doublet 3.0
H doublet 5.8
Hf & Hb H: broad singlet -—

 

 

 

 

 

29

Confirmation of the molecular weight was obtained from mass spectrometry
with a parent peak of m/e 258 (calcd 258). Diene (XXVII) was isolated
as a colorless oil which was fairly sensitive to air and heat on
standing and was stored under nitrogen at 0°.

In lieu of purification and analysis because of its tendencies
toward decomposition the diene was catalytically hydrogenated (5%
palladium on charcoal) to give a bicyclic octane skeleton. Hydrogenation
should and did occur from the less hindered side of the styrene moiety
to produce the symmetrical octane, §j§;ggg9;2,4-diphenylbicyclo[3.2.l]-
octane (XXVIII). The ir spectrum of this compound was rather

Ph
(XXVIII)

uninformative; however, the simplicity of the nmr spectrum did reflect
its symmetry: 1 2.83 (10H, 5) phenyl, 7.08 (2H, broad triplet) benzylic,
7.61 (2H, m) bridgehead, 7.82-8.60 (8H, complex) methylene. The mass
spectrum was consistent for the addition of two moles of hydrogen:
parent peak m/e 262. The analysis confirmed the molecular formula
Czo"22°

In conclusion elimination and not fragmentation seems to be the
major solvolytic pathway. Perhaps the driving force for elimination is
the formation of the stable diene system (XVII) and may be a direct
consequence of the phenyl interaction which is relieved by the formation

of the double bond, thus swinging the phenyl moiety away from the ring

30

system. The possible existence of fragmentation products can not be
eliminated since the minor constituents have not yet been identified.
Finally, the author would like to suggest the preparation of the

a,a' dimethyl methanesulfonate analogues ((XXIX) to (XXXII)) of the

mesylates discussed in this thesis on the grounds that elimination

CODHO‘C OCCUV‘ .

 

1M5

(XXIX) and (XXX) (XXXI) and (XXXII)

EXPERIMENTAL

Melting points were taken on a Thomas Hoover capillary melting
point apparatus and are uncorrected. Infrared spectra were recorded
by a Perkin-Elmer Grating Infrared Spectrophotometer, Model 237 8.
They were calibrated with the 6.23 V band of a polystyrene film
reference. A Unicam SP 800 was used for recording ultraviolet spectra.
Mass spectra analysis were performed by Mrs. R. L. Guile at Michigan
State University on a Hitachi, Model RMU-6, Mass Spectrometer.

Nuclear Magnetic Resonance (nmr) spectra were obtained using a
Varian A-60 Spectrometer. The decoupling experiments were performed
by Eric Roach on a Varian HA-lOO Spectrometer. The nmr dataare presented
in the fOllowing manner: 1 6.00 (2H, d of d's, J I 4). All spectra are
recorded in tau (1) units relative to tetramethylsilane (TMS). The first
symbols in the parenthesis refer to the integrated band intensity (number
of hydrogens), the second letter(s) indicate band multiplicity and the
last symbol (J) is the observed coupling constant in cycles per second.
The multiplicities are: 5 = singlet, d = doublet, t = triplet, q =
quartet and m - multiplet. Others will be stated explicitly.

Elemental analyses were carried out by Spang Microanalytical

Laboratory, Ann Arbor, Michigan.

31

32

Part I: Synthesis
gigyendo-2,4-diphenylbicyclo[3.2.1]oct-6-en-3-one (XVI). u,o'-

 

Dibromodibenzyl ketone (240 g, 0.652 mole) in 900 ml of reagent grade
acetone was added dropwise to a mechanically stirred solution of sodium
iodide (240 g, 0.652 mole) in 3250 ml of acetone. An excess of cyclo-
pentadiene (ca, 75 ml) was distilled into the reaction mixture
concurrent with the addition of the dibromoketone. The mixture was
maintained between -7 and -12°C throughout the course of the reaction.
The solution first turned a bright yellow, then climaxed in the
appearance of golden needles aimlessly drifting in a dark brown nectar.
The mixture was allowed to warm to room temperature and then poured
into 4 liters of water. Sodium bisulfite was added until the solution
became colorless. The yellowish needles were filtered, dissolved in
boiling 95% ethanol and treated with Norit A. Hot filtration and
subsequent cooling afforded long colorless needles, m.p. 150.2-150.8°

(total yield: 129 g, 73%), which exhibited identical spectral properties,

gigyendo-Z,4-dipheny1bicyclo[3.2.l]oct-6-en-endo-3-ol (XVIII).

 

Lithium Aluminum Hydride Reduction20, The bicyclic ketone (XVI) (20 g,

 

73 mmoles) dissolved in tetrahydrofuran (150 ml) was added dropwise
to a slurry of lithium aluminum hydride (LAH) (4.5 g, 122 mmoles) in
anhydrous ethyl ether. After addition was completed the mixture was
refluxed overnight. The remaining LAH was destroyed by adding 2 m1
of 5% sodium hydroxide solution followed by 2 ml of water for each

initial gram of LAH. The fluffy white precipitate was filtered and

33

washed with ethyl ether. The combined organic solvents were removed
j_r_1_ 11913. Recrystallization twice from hexane afforded colorless prisms,
m.p. 80-81.5° (12.9 g, 47 mmoles, 65% yield); infrared: Amax (KBr) 2.81,
6.23, 10.00, 10.86, 10.99; nmr: r (CDC13) 2.86 (10H, 5), 3.62 (2H,
broads), 5.73 (1H, d of t's, J1 = 8.4, J2 = 4.5), 6.78 (2H, d of d's,
J1 . 1.7, J2 = 4.5), 7.14 (2H, broad d, J = 5.2), 7.60 (1H, quintet,
J1 = 5.2, J2 = 10.2), 8.25 (1H, d, J = 10.2), 8.55 (1H, d, J = 8.4);
trace of acid: signal at 8.55 collapsed to a sharp singlet and signal
at 5.73 collapsed to a triplet; in 020: signal at 8.55 disappeared;
mass spect: m/e 276

Anal, Calcd. for CZOHZOO: C, 86.92; H, 7.29. Found: C, 87.09;
H, 7.40.

Cyclization of endo-Alcohol (XVIII). Sygrgyg:4,9-diphenyl-2-

 

oxatricyclo[3.2.l.1317]nonane (XIX). Method A - Acetic Acid. The endo;
alcohol (0.5 g, 1.8 mmoles) was dissolved in 20 m1 acetic acid. The
mixture was heated on a steam bath for 24 hrs. Neutralization with
Na2C03 solution, extraction with ethyl ether, drying over M9504 and
finally concentration of the organic phase by flash evaporation afforded
an off white solid (430 mg) which was spectroscopically identical to
starting material.

Method B - Toluenesulfonic Acid. The eggg_- alcohol (0.7 g, 2.5
mmoles) was placed in 25 m1 l:l ethanol - water containing toluenesulfonic
acid (2 g, 11.6 mmoles). The mixture was refluxed overnight.
Neutralization with Na2C03 and subsequent workup afforded only starting

material .

34

Method C - 30% Sulfuric Acid. The gngg_alcohol (l g, 3.6 mmoles)
was placed in a 100 ml one-neck flask containing 60 ml of 30% H2S04.
The mixture was refluxed for three hours. It was then allowed to cool,
diluted to 200 ml, and extracted with ethyl ether. The organic layer
was washed with water, 5% Na2C03 solution and then more water. The
organic phase was concentrated ig_vggug_and the solid recrystallized
twice from hexane and then sublimed, m.p. 101-101.5° (0.7 g, 2.5 mmoles,
70% yield); infrared: Amax (Nujol) 6.23, 9.8, 9.89, 9.96, 11.23; nmr:
T (C0013) 2.47-3.04 (10H, complex), 5.32 (1H, broad t, J = 4), 5.62
(1H, broad s), 6.79 (1H, s), 6.91-8.46 (6H, complex), 8.39 (1H, d of t's,
J1 = 4.2, J2 s 11.8); mass spect: m/e 276.

Anal, Calcd. for CZOHZOO: C, 86.92; H, 7.29.

Found: C, 87.05; H, 7.29.

Sodium-Alcohol Reduction of Ketone (XVI). The bicyclic ketone
(17.5 g, 63 mmoles) in 210 ml absolute ethanol and 50 m1 of dry toluene
(warmed until ketone dissolved) was syringed into a refluxing solution
of 400 m1 toluene and molten sodium (14 g, 0.61 mole). The reaction
mixture was refluxed until all the sodium dissolved. The remaining
cooled solution was then poured into one liter of water and extracted
with ethyl ether. The organic portion was washed twice with 2% H01,
once with 10% sodium carbonate solution and finally washed twice with
water. Drying over MgSO4 and concentration of the organic layer in_
vgggg.gave a reddish oil. Recrystallization from hexane afforded 6.6 g
of an off-white solid. Further concentration of the hexane afforded no
additional crystalline material. Continuous shaking of the remaining

oil with cold petroleum ether yielded an additional 4.9 g of impure solid

35

material. .The infrared spectrum of the crude material possessed
characteristic hydroxyl absorption; no starting ketone was present. The
nmr spectrum did suggest that more than one compound was present.

At this point further purification of this alcoholic mixture seemed
fruitless. Preparation of the pfnitrobenzoates was undertaken in hope
that separation could be achieved. (Spectral properties of the pure
alcohols will be given in a later section.)

A portion of the crude product mixture was purified further for
nmr studies. The red oil obtained originally was dissolved in 15 m1
of acetonitrile. Continuous solvent-solvent extraction with pentane for
five days afforded an off-white solid upon evaporation. The remaining
acetonitrile solution was concentrated jn_gaggg_to give a red residue,
the infrared of which indicated that no alcohol was present and
extraction was complete. The composition of each alcohol was determined
by integrating the two characteristic methine resonances centered at
r 5.8. Comparison of the integrated intensity bands showed that
traggyz,4-dipheny1bicyclo[3.2.l]oct-6-en-exg;3-ol (XXIII) composed 48.1
t .4% of the total reduction product. The remaining portion was cisrenggf
2,4-diphenylbicyclo[3.2.1]oct-6-en-gxg:3-ol (XXII).

Preparation of the p-Nitrobenzoates (XX) and (XXI). The crude
alcoholic mixture from the previous experiment (11.5 9, ca. 42 mmoles)
was placed in a round bottom flask containing pyridine (6 ml, 75 mmole)
and 340 m1 of anhydrous ethyl ether. .p-Nitrobenzoyl chloride (11.5 g,
62 mmoles) dissolved in a minimum amount of anhydrous ether was added
dropwise to the stirred solution maintained at 0°C during the period

of addition. A white precipitate resulted immediately. The reaction

36

was continued for three hours at room temperature,,and the mixture poured
into a separatory funnel containing 200 m1 H20, shaken, and the water
layer discarded. The organic portion was washed twice with 1 1/2% HCl
(100 ml), once with 10% sodium bicarbonate solution, and twice more
with water. It was then dried with MgSO4; concentration by flash
evaporation gave a yellowish solid. Recrystallization from 95% ethanol
afforded long-yellowish needles, m.p. 181.5-184.5°. Recrystallizat1on
a second time from a hexane-benzene mixture gave slightly yellowish
needles, m.p. 185-186°. It seemed that the fractional crystallization
process was complete. Further purification from acetone-water afforded
colorless needles, m.p. 186-186.5° (4.9 g); infrared: Xmax (cc14) 5.75,
6.20, 9.07, 11.58; nmr: r (CDC13) 2.l9 (4Jl, A282 quartet, J = 9.2),
2.60-3.10 (10H, m), 3.75 (2H, broad s), 4.08 (1H, t, J = 9.8), 6.93
(2H, d of d's, J1 = 9.8, J2 = 2.4), 7.14 (2H, m), 7.79 (1H, d of t's,
J1 = 10.3, 02 = 4.9), 8.06 (1H, d, J = 10.3); mass spect: m/e 258.

A221: Calcd. for C27H23NO4: C, 76.22; H, 5.45; N, 3.29.

Found: C, 76.13; H, 5.50; N, 3.13.

Concentration of the ethanol solution and subsequent cooling gave
another yellowish solid material, m.p. 139°. Recrystallization from
acetone-water afforded long colorless needles, m.p. 139° (2.45 g);
infrared: Amax (CC14) 5.78, 6.20, 9.07, 11.59; nmr, r (C0013) 2.35 (4H,
A282 quartet, J = 8.8), 2.58-3.05 (10H, complex), AB system: 3.75 (1H)
and 3.97 (1H) (d of d's, J1 = 4.2, J2,3 = 2.6), 4.08 (1H, d of d's,

J1 = 7.6, J2 = 9.5), 6.24 (1H, d of d's, J1 = 2.6, J2 = 7.6), 6.39
(1H, d of d‘s, J1 = 2.2, J2 ==1L5), 7.19 (2H, m), 7.83 (1H, d, J = 11.0),

8.30 (1H, d of t's, J1 . 4.7, J2 = 11.0); mass spect: m/e 258.

37

Anal. Calcd. for C27H23N04: C, 76.22; H, 5.45; N, 3.29.

Found: C, 76.28; H, 5.49; N, 3.21.

The remainder of the ethanol solution was concentrated ig_vacuo
yielding 0.80 g of solid which was an impure mixture of the two p-
nitrobenzoates. The total quantity of product isolated was 8.10 g

(93, 70% yield).

§j§;endo-2,4-diphenyloct-6-en-gng3-ol (XXII). The gxg;p-nitro-

 

benzoate (XX) (650 mg, 1.5 mmoles) was added to a solution of potassium
hydroxide (8 g, 140 mmoles) in 42 ml of methanol (ca, 8% alcoholic KOH).
The mixture was refluxed overnight, poured into 300 m1 of ice-water, and
extracted twice with ethyl ether (200 ml). The combined ether extracts
were washed with 2% hydrochloric acid and then water. Recrystallization
from hexane afforded colorless superfine needles, m.p. 148-149° (295 mg,
1.1 mmoles, 71% yield); infrared: Amax (Nujol) 3.83 (shoulder), 3.88,
6.21, 9.07, 9.47, 10.21; nmr: r (coc13) 2.79 (10H, 5), 3.87 (2H, broad s).
5.85 (1H, t, J = 9.2), 7.28 (4H, complex, d, J = 9.2), 7.90 (1H, quintet,
J1 - 4.9, J2 = 10.3), 8.21 (1H, d, J = 10.3), 8.56 (1H, s); in 020:
resonance at 8.56 disappeared; mass spect: m/e 276.

Anal. Calcd. for CZOHZOO: C, 86.92; H, 7.29.

Found: C, 87.05; H, 7.31.

Chromium Trioxide-Dipyridinium Complex Oxidation of gngAlcohol

 

(XXII). (The procedure for the preparation and use of the complex is
outlined by J. C. Collins)rz The alcohol (0.41 g, 1.5 mmoles) was dissolved

in 20 ml of methylene chloride. To this stirred solution a six-fold excess

38

of the complex (2.4 g, 9.3 mmoles) was added. The reaction proceeded

to completion within 10 minutes (at room temperature) with decomposition
of the complex to brownish-black polymeric chromium reduction products.

The organic layer was then poured into 100 m1 of water and extracted

with ethyl ether. The remaining polymeric residue was washed three

times with ether (25 m1), combined with the other organic portion and

dried over magnesium sulfate. The solvent was stripped in_vaggg_and
recrystallization from methanol afforded colorless needles, m.p. 150-
150.5° (290 mg, 1.1 mmoles, 71% yield); the spectral properties of this
compound were identical to those of the bicyclic ketone (XVI) (vide supra).

Trans-2,4-diphenylbicyclo[3.2.1]oct-6-en-gxg;3-ol (XXIII). The

 

trag§3diphenyl-gxg-p-nitrobenzoate (XXI) (2.09 g, 4.9 mmoles) was added

to a solution of potassium hydroxide (24 g, 0.42 mole) in 120 ml of
methanol (53, 8% alcoholic KOH). The mixture was refluxed overnight.

The work-up of the reaction mixture was identical to that in the hydrolysis
of exo-p-nitrobenzoate (XX) (vide supra). Recrystallization from hexane
afforded colorless superfine needles, m.p. 108.5-110.5° (1.10 g, 4.0
mmoles, 82% yield); infrared: Amax (Nujol) 2.82, 6.21, 9.31, 10.21; nmr:
T (CDC13) 2.54-2.94 (10H, complex), AB system: 3.85 (1H) and 4.01 (1H)
(d, of d's, J] 8 6, J2’3 8 2.5), 5.62 (1H, d of d's, J] 8 10.9, J2 = 7.2),
6.70 (1H, d of d's, J] 8 2.6, J2 8 7.2), 6.87 (1H, d of d's, 018 2.4,

J2 8 10.9), 8.01 (1H, d, J 8 10.3), 8.37 (1H, d of t's, J1 8 10.3, J2 =
4.9), 8.6 (1H, 5); mass spect: m/e 276.

Anal. Calcd. for CZOHZOO: C, 86.92; H, 7.29.

Found: C, 86.73; H, 7.30.

39

Chromium Trioxide - Dipyridinium Complex Oxidation of trans-Diphenyl-

 

exo-Alcohol. Trans-2,4-Diphenylbicyclo[3.2.l]oct-6-en-3-one (XXIV). The

 

tragg-diphenyl-gxg-alcohol (270 mg, 0.98 mmole) was dissolved in 12.5 ml

of methylene chloride. The complex (1.5 g, 6.7 mmoles) was added to the
stirred solution at room temperature. The reaction proceeded to completion
within 10 minutes as evidenced by the formationcfaibrownish-black polymeric
residue. The work-up of the reaction mixture was identical to that in the

oxidation of the exo-alcohol (XXII) (vide supra). Recrystallization from

 

methanol afforded colorless shimmering needles, m.p. 131-132.5° (170 mg,
0.62 mmole, 63%); infrared: Amax (CHC13) 5.84, 6.23, 7.42, 9.08; uv: Amax
(cyclohexane) 300 rm1 (e 8 115); nmr: r (CDC13) 2.50-2.97 (10H, complex),

3.63 (2H, m), 6.07 (2H, m), 6.57 (1H, m), 6.93 (1H, m), 7.68 (2H, m).

Anal. Calcd. for C20H180: C, 87.56; H, 6.61.

Found: C, 87.37; H, 6.66.

Sulfuric Acid Treatment of Alcohols (XXII) and (XXIII). In separate
experiments the two gxg;alcohols (100 mg, 0.36 mmole) were placed in 6 ml
of 30% H2S04. Their mixtures were refluxed for three hours, cooled, diluted
to 50 m1 and extracted with ethyl ether. The ether portions were washed
with 10% NaHCO3 solution and twice with water; the solvent was removed in
32239, Spectral data taken of the crude products were consistent with those
of the starting materials. There was no evidence that cyclic-ether

formation had occured.

gig-endo-Z ,4-di phenyl bi cycl o[3 . 2 .1]oct-6-en-§§9_-3-yl methanesul fonate

 

9:). The exo-alcohol (XXII) (1.05 g, 3.86 mmoles) was dissolved in 40

40

m1 pyridine. An equimolar amount of methanesulfonyl chloride (0.45 g,
I 3.90 mmoles) was added. The mixture was allowed to react at approximately
0°C overnight and then warmed to room temperature for 24 hrs. The mixture
was diluted with 500 ml of water and the precipitate filtered.
Recrystallization from ethyl ether-hexane gave yellowish needles. Further
purification by cold recrystallization from acetone-water afforded
colorless needles, m.p. 166.5° (dec.) (0.92 g, 2.77 mmoles, 72% yieid);
infrared: Amax (Nujol) 6.20, 7.39, 8.52, 10.57, 10.98; nmr: r (CDC13)
2.73 (10H, 5), 3.73 (2H, broad s), 4.70 (1H, t, J = 9.8), 6.98 (2H, d of
d's, J1 . 9.8, J2 = 2.4), 7.21 (2H, broad d, J = 4.9), 7.86 (1H, d of t's,
J1 . 10.3, 02 = 4.9), 8.17 (1H, d, J = 10.3), 8.26 (3H, s); mass spect:
m/e 354.

Anal. Calcd. for C21H22503: C, 71.16; H, 6.26; S, 9.05.

Found: C, 71.17; H, 6.35; S, 9.11.

§!§;endo-2,4-diphenylbicyclo[3.2.lJoct-6-en-endo-3-yl methanesulfonate

 

(XI) . The endg-nesyiate was obtained in 55% yield following the

procedure for the preparation of the exo-mesylate ( X ) (vide supra).

The compound had the fo1lowing properties: m.p. 144.5° (dec.); infrared:
Amax (Nujol) 6.19, 7.39, 8.54, 10.87; nmr: r (CDC13) 2.78 (10H, 5),

3.57 (2H, broad s), 4.61 (1H, t, J 8 4.4); 6.53 (2H, d of d of d's, J1 = 4.4,
J2 8 1.4), 7.11 (2H, broad d, J 8 5.2), 7.55 (1H, d of t's, J1 = 5.2,

J2 . 10.4), 8.20 (1H, d, J . 10.4), 8.57 (3H, 5); mass spect: m/e 354.

Anal. Calcd. for C21H22503: C, 71.16; H, 6.26; S, 9.05.

Found: C, 71.30; H, 6.17; S, 9.13.

41

Epimerization of Bicyclic Ketone_(XVI) with Sodium Methoxide.
The gisfdiphenyl ketone (XVI) (2.55 g, 9.25 mmoles) was treated with
sodium methoxide (770 mg, 14.3 mmoles) in 52 m1 of dry methanol and
122 m1 toluene. The mixture was refluxed for 6 days, poured into
200 ml water, and extracted with ethyl ether. The ether portion was
washed with water, twice with 1 1/2% hydrochloric acid (100 ml), again
with water, and finally dried over M9504. The solvent was removed 12_
gggug_leaving a slightly yellowish solid. The amount of epimerization
was determined from nmr by integrating the resonances assigned to the

bridgehead protons and applying the following formula,

 

2 A]
x 100
A2 + A1
where A] = integrated band intensity located at T 6.57 for one
proton of (XXIV); A2 = " " " " " T 6.93 for two

Protons of (XVI) and one proton of (XXIV).

Using the above method, it was found that 68.8 t 1.1% of the starting
ketone epimerized at one center alpha to the carbonyl moiety yielding
trans-2,4-diphenylbicyclo[3.2.l]oct-6-en-3-one (XXIV).

Diimide Reduction. Cis-endo-2,4-diphenylbicyclo[3.2.l]octan-3-one

 

(XXVII). (Potassium Azodicarboxylate (PADA) was used as the diimide
precursor and was prepared according to Thielele. Generation of diimide
j__§jtg_was outlined in a procedure by Warren, 23391319). The unsaturated
ketone (XVI) (8.0 g, 29 mmoles) was dissolved in a slurry of 150 m1
pyridine and PADA (15 g, 80 mmoles). Acetic acid (4.0 g, 67 mmoles)

dissolved in 5 m1 pyridine was added drapwise to the vigorously stirred

42

slurry. After 9 hrs. an equal amount of acid was slowly added. The
absence of yellow solid indicated that the reaction was complete. Upon
completion the mixture was poured into 500 ml of water and the precipitate
filtered. Recrystallization from 95% ethanol afforded colorless needles,
m.p. 114.5-115° (6.6 g, 24 mmoles, 83% yield); infrared: Amax (mujol)
5.83, 6.19, 9.33; u v : Amax (cyclohexane) 290 nm (e = 30); nmr:
T (CDC13) 2.86 (10H, 5), 6.22 (2H, d, J = 2.5), 7.35 (2H, m), 7.60-8.55
(6H, complex).

Anal, Calcd. for CZOHZOO: C, 86.92; H, 7.29.

Found: C, 87.00; H, 7.43.

glarendo-Z,4-dipheny1bicyclo[3.2.l]octan-endo-3-ol (XVIII). The

 

saturated ketone (3.6 g, 13 mmoles) was added dropwise to a refluxing
slurry of lithium aluminum hydride (1.5 g, 39 mmoles) in anhydrous ethyl
ether. The mixture was allowed to reflux overnight and followed by
work-up in the usual manner (vide supra). Recrystallization from

hexane afforded colorless prisms, m.p. 102.5-103.5° (3.23 g, 11.6 mmoles,
90% yield); infrared 1m“ (Nujol) 2.81, 2.89, 6.21, 9.33, 10.22; nmr:

T (CDC13) 2.54-3.1O (10H, complex), 5.46 (1H, t, J = 3.8), 6.92 (2H, m),
7.21-8.55 (8H, complex), 8.98 (1H, s); mass spect: m/e 278.

Anal. Calcd. for CZOHZZO: C, 86.28; H, 7.97.

Found: C, 86.19; H, 8.05.

43

Attempted Mesylation of Saturated-endo Alcohol (XXVIII). The

 

alcohol (XXVIII) (2.0 g, 7.2 mmoles) was dissolved in 80 m1 pyridine.
An equimolar amount of methanesulfonyl chloride (0.90 g, 7.3 mmoles)
was added. It was allowed to react for 48 hrs, the first day at 0°C
and the second at room temperature. Workup in the usual manner

(vide supra) gave a solid whose spectral properties were identical

 

with those of the starting alcohol.

Ala-endo-2,4-dipheny1bicyclo[3.2.lJoctane-endo-S-yl methanesulfonate

 

(XV). The anda-mesylate (X1) (407 mg, .96 mmoles) was dissolved in
10 ml of pyridine containing potassium azodicarboxylate (800 mg, 5.3
mmoles). Acetic acid was added dropwise to the stirred solution in
two equivalent portions, at the beginning and 9 hrs later (total of
.5 g acetic acid in 5 m1 pyridine). After a total of 48 hrs the mixture
was poured into 300 ml water and the precipitate filtered.
Recrystallization from acetone-water afforded white needles, m.p.
103° (dec.) (360 mg, 0.84 mmoles, 88% yield); infrared; Amax (Nujol)
7.43, 8.57, 10.53, 10.90, 11.02, 11.50; nmr: 1 (CDC13) 2.52-2.92
(10H, complex), 4.33 (1H, t, J = 3.9), 6.63 (2H, m), 7.25 (2H, m),
7.91-8.27 (6H, complex), 8.41 (3H, s); mass spec.: m/e 356.

Anal. Ca1cd. for C21H24SO3: C, 70.75; H, 6.79; S, 9.00.

Found: C, 70.78; H, 6.77; S, 9.14.

44

Ala-endo-2,4-diphenylbicyclo[3.2.l]oct-aan;3-yl methanesulfonate

 

(XIV). The saturated gag-mesylate (XIV)(140 mg, 0.33 mmoles) was prepared
following the same procedure for the reduction of endo-compound (XI)

(vide snpra). Recrystallization from acetone-water afforded colorless

 

platelets, m.p. 154.5° (dec.) (80 mg, 0.19 mmoles, 57% yield); infrared;
Xmax (Nujol) 7.41, 8.52, 10.77, 11.79; nmr: T (CDC13) 2.45-2.88 (10H,
complex), 4.31 (1H, t, J = 10.4), 6.33 (2H, d of d's, J1 8 10.4, J2 8
1.8), 7.64 (2H, m), 7.84-8.83 (6H, complex), 8.14 (3H, 5); mass Spect:
m/e 356.

SD

Anal. Calcd. for C C, 70.75; H, 6.79; S, 9.00.

21H24 3‘
Found: C, 70.72; H, 6.77; S, 9.07.

Lithium Aluminum Hydride Reduction of Endo-mesylate (XI) 2-Pheny1-

 

endo-4-phenylbicyclo[3.2.l]octa-2,6-diene (XXVII). The endo-mesylate

 

(l g., 2.4 mmoles) was treated with excess lithium aluminum hydride

(1 g.) in refluxing ether. The mixture was refluxed overnight and
worked up in the usual manner. A colorless oil was obtained in
quantitative yield; infrared: Amax (Nujol) 3.32 doublet, 7.45, 9.73,
10.73, 11.21, 11.52; uv: Amax (cyclohexane) 255 nm (e 8 13,000);

nmr: 1 (001113) 2.53-3.10 (10H, complex), 3.61 (1H, d of d's, J1 8

2.8, J2 8 5.8), 4.34 (1H, quintet, J1 8 1.5, J2 8 3.0), 4.74 (1H, d of
d's, J1 8 2.8, J2 8 5.8), 6.23 (1H, d of d's, J1 8 3.0, J2 8 4.8), 6.83
(1H, m), 7.02 (1H, m), 7.78 (2H, complex); mass spect: m/e 258. This

compound decomposed on standing at room temperature and was stored under

a nitrogen atmosphere in the refrigerator.

45

Catalytic Hydrogenation of Diene (XXVII). §l§;endo-2,4-diphenyl-

 

bicyclo[3.2.lJoctane (XXVIII). The crude diene was dissolved in 50 ml
of methanol containing Norit A (250 mg.) and stored in the refrigerator
with occasional mixing. The solution was filtered, diluted to 250 m1,
and 5% palladium on charcoal (0.5 g.) was added. Concentration in_
gannn_gave a colorless oil which on cold recrystallization from
acetonitrile and subsequent sublimation afforded 130 mg. of colorless
needles, m.p. 92°; infrared: Amax (KBr) 3.42, 3.50, 8.54, 9.90, 11.01,
11.40; nmr: r (CDC13) 2.83 (10H, s), 7.08 (2H, broad distorted t,

J 5 7-8), 7.61 (2H, m), 7.82-8.50 (8H, complex); mass spect: m/e 262.

Anal. Calcd. for CZOHZZ: C, 91.55; H, 8.45.

Found: C, 91.63; H, 8.39.

46

Part II: Solvolysis

Acetic Acid. A) The endo-mesylate (20 mg.) was placed in an nmr

 

tube containing 1 m1 of acetic acid. A spectrum of the sample was taken
every 15 min. The probe temperature (22; 34.5°) was calculated using

a methanol standard. There appeared to be no reaction after one and a
half hours.

B) The gag-mesylate (20 mg.) was subjected to the same conditions
as in Part A. There was no change after 1 1/2 hrs.

C) A 5% sodium acetate-acetic acid solution was prepared. The
anaa-mesylate (50 mg.) and 5 m1 of the buffered solution were placed
into a sealed tube. The solution was degassed with nitrogen for 5
minutes. Subsequent heating to 140° for 1 hr. followed by quenching
in 100 ml 10% NaHCO3 afforded an intractable polymeric residue.

Formic Acid. A) The angn-mesylate (50 mg.) was placed into 5 ml

 

90% formic acid. Heating to 50° for 1 hr. and subsequent quenching in
NaHCO3 yielded only starting material.

8) The aaa isomer (50 mg) was subjected to the same conditions
as in part A. Quenching resulted in the precipitation of a brownish
material which had identical spectral prOperties to that of starting
material.

C) The material recovered in part B was dissolved in 5 ml 50%
formic acid and heated to 80° for 2 hrs. Again only starting material

could be isolated.

47

Trifluoroacetic Acid. A) The endo mesylate (50 mg.) was dissolved

 

in 5 m1 trifluoroacetic acid and warmed to 45° for three-quarters of an
hour. The solution turned a dark red which culminated with the appearance
of a yellow precipitate. A similar experiment was conducted on 300 mg.
of the anna_compound dissolved in 7 ml trifluoroacetic acid in order to
characterize the precipitate. The reaction mixture was filtered and the
precipitate dissolved in d-chloroform. The resultant n m r spectrum was
characteristic of polymeric material: 2.32-3.21 r (broad multiplet),
8.2-9.4 r (broad multiplet).

B) The anna-mesylate (50 mg.) was placed in 5 m1 trifluoroacetic
acid containing 5% sodium trifluoroacetate. Only polymeric material

could be obtained.

Ethanol: Water. A) The endo-mesylate (100 mg.) was placed in a

 

sealed tube containing 9 ml of 1:1 ethanol-water solution. Six drops
of triethylamine was added. The solution was degassed with nitrogen
for 5 minutes and heated to 145° for 1 hr. The mixture was cooled,
diluted with 100 ml water, and the product extracted with pentane. The
pentane was removed ln_gaana_leaving an oily residue which could not
be purified further; infrared: Amax (film) 3.32 doublet, 6.25, 6.70,
6.91, 7. 5, 9.73, 10.73, 11.21, l..52, 13.14, 14.34; n.m r : r (CDC13)
2.53-3.10 (10H, complex), 3.61 (1H, d of d's, J1 8 2.8, J2 8 5.8, 4.34
(1H, quintet, J1 8 1.5, J2 8 3.0), 4.74 (1H, d of d's, J1 8 2.8, J2 8 4.8),
6.93 (2H, m), 7.78 (2H, complex).

B) The gag-mesylate (110 mg.) was placed in 10 m1 1:1 ethanol-water

solution in a sealed tube. Six drops of triethylamine was added, the

48

solution degassed for 5 minutes with nitrogen, and heated to 145° for
1 hr. When the solution was cooled to room temperature a white solid
precipitated (53 mg.) which was recovered starting material. The
remaining solution was diluted with 100 m1 of water and extracted
with pentane. The organic layer was dried over M9504 and concentrated
ln_!aann_leaving a thick oil whose n m r spectrum (C0013) could only
be characterized in the lower field region::-2.53-3.10 (m), 3.64 (sextet,
peak intensity: l:l:2:2:l:1), 3.97 (broad, s), 4.34 (quintet), 4.74
(d of d's), 6.23 (d of d's).

C) Heating the anaa:mesylate to 145° in ethanolzwater without adding

triethylamine gave results identical to those obtained in part A.

Dioxane:Water. The endo-mesylate (50 mg.) was dissolved in 3 m1

 

of dioxane and syringed into a sealed tube containing 3 m1 H20. The
solution was degassed with nitrogen and heated to 140° for 1 hr. The
mixture was cooled, diluted to 100 ml with water and extracted with
pentane. The organic portion was dried with M9804 and concentrated in-
naana_giving an oily substance which exibited identical spectral
properties to that obtained from the solvolysis of the anaa;mesylate

in ethanol-water (vide supra).

Dimethylformamide (DMF). A) The endo-mesylate (792 mg.) was placed

 

in 80 m1 of DMF containing 320 mg of lithium chloride and 170 mg

Na2C03. The mixture was heated to 140° for 1 hr. It was then cooled,
diluted with water and extracted with pentane. Concentration ln_!aann.
afforded a single compound (510 mg.) which was a slightly colored oil;

infrared: Amax (film) 3.32 doub1et, 6.25, 9.73, 10.73, 11.21, 11.52;

49

nmr: r (CDC13) 2.53-3.lO (10H, complex), 3.61 (1H, d of d's, J1 8 2.8,

J2 8 5.8), 4.34 (1H, quintet, JI 8 1.5, J2 8 3.0), 4.74 (1H, d of d's,

J18 2.8, J2 = 5.8), 6.23 (1H, d of d's, J18 3.0, J2 = 4.8), 6.93 (2H, m),
7.78 (2H, complex); mass spect: m/e 258.

(A) N -'
o o o

10.

11.

12.
13.
14.
15.

REFERENCES

T. Zincke and H. Gfinther, Ann. Chem., 212, 243 (1893).
0. Diels and K. Alder, ibid., 460, 98 (1928).
0. Diels, K. Alder, G. Stein, P. Pries, and H. Winckler,

Chem. Ber., 62, 2337 (1929).
———'—’\/\7

. Sauer, Angew. Chem. internat. Edit., 5, 211 (1966).

 

J
O. Diels and K. Alder, Chem. Ber., 62, 554 (1929).
H. Kwart and K. King, Chem. Rev., 68, 415 (1968).
R

. B. Woodward and R. Hoffmann, Angew. Chem. internat. Edit.,
8, 781 (1969).

 

A. Fort, J. Amer. Chem. Soc., 8%, 4979 (1962).

 

R. C. Cookson and M. J. Nye, Prod. Chem. Soc., 129 (1963).

 

H. R. M. Hoffmann, D. R. Joy, and A. K. Suter, J. Chem. Soc. (B),

 

57 (1968).
S. F. Cristol, R. M. Segueria, and C. H. DePuy, J. Amer. Chem.
§ag,, 81, 4007 (1965).

 

G. H. Whitham and M. Wright, Chem. Commun., 294 (1967).

 

Cookson and Wariyar, J. Chem. Soc., 2302 (1956).

 

B. Waegnell and C. W. Jefford, Bull. Soc. chim. France, 844 (1964).
W. G. Dauben, G. J. Fonken, and D. S. Noyce, J. Amer. Chem. Soc.,
18, 2579 (1956).

50

16.

17.
18.
19.

20.

51

P. 0. Bartlett, Nonclassical Ions, Benjamin, New York, 1965,
and references therein.

J. C. Collins, Tetrahedron Letters, 3363 (1968).

 

J. Thiele. Ann. Chem., (2’7), 127 (1892).
J. W. Hamersma and E. I. Snyder, J. Org, Chem., 30, 3985 (1965).

 

D. G. Farnum and L. Sprinkle, private communication.

APPENDIX

NMR SPECTRA

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