Structure and synthesis of bicalamenene

Tetrahedron Printed in

Letters,Vol.26,No.i2,np Great Britain

1535-1536,1985

Structure

and

Synthesis

of

0040-4039/85 $3.00 + .oo 01985 Pergamon Press Ltd.

Bicalamenene

Hidetoshi Yamada, Set i jat i Sastraprad.ja,’ and !-lug i 0 Nishizawa,* Department of Chemistry, Faculty of Science, Osaka City University, ku,

Osaka

558,

Summary:

The structure

lamenene

has

been

Recently, from A

“The

Japan,

we have of

dimer

the

to

synthesis

the

of

the

and

be formula

1.

isolation

of

plant

the

as

has

Indonesia

and

named

bica-

synthesis.

(+I-8-hydroxycalamenene

its

been

absolute

Bogor,

study

Hayashi

Sumivoshi-

sesquiterpene

spectral

alliaceum

same

2,2

Institute,

dimeric

on the

Dysoxslum

constituent

unsymmetrical

based

reported

plant

Biological

an unsymmetrical

established

a Meliaceous

minor

of

National

YUji

ma.jor

poisonous

characterized

structure

has

12) principle.’

t.o be been

nove 1

a

established

by

&I$ OH

3

A

1 Bicalamenene isooctane), ica

(11,

was

se1

isolated

column

a pale

chromatography

of

collected

estimated

by of

(6 0.60, 7 Hz in and From

these

calamenene the

the

following

high

Boqor,

0.99,

A pair

of

Aromatic

protons

spectral

evidence,

is

suggested

1.55,

the

CHC13);

syrup

hexane

in

UV A,,,

ca 0.04%

extract

of

the

284 nm (E yield

by the

dried

peel

2581, silof

D_

Indonesia.

The molecular formula C30H4202 was spectrum. IR spectrum indicated the (3600 and 3550 cm-‘). Six signals due to methyls 1.10, and 1.18) were observed as doublets with J = mass

singlets

due

appeared to

(c yellow

resolution

groups

0.85,

lH NMR.

1.84.

in

hvdroxvl

0.64,

t32.4”

as

alliaceum presence

f~lD2~

as

to

an unsymmetrical this

aromatic

a single

new natural

methyls broard

dimeric product,

appeared

peak

at

structure which

was

at

6 1.76

d 6.58.3 of

8-hydroxs-

conf irmed

by

synthesis.

Vhen an aqueous suspension of (+)-8-hydroxycalasenene (21, CcrlD15 t38.0” (c 1.37, CHC13), L!V A,,, 282 nm (c 1812, isooctane), was heated at reflux with two equiv. of ferric chloride for ‘1 h, a single unsymmetrical dimer and two

1535

1536

kinds

of

symmetrical

ct ively,

along

dimer

was

tion. of

the

between tion

the

of

of

the

natural

The symmet.r i cal

nm

(E

3b,

4130,

5D-QDS, two

compounds

0.11)

suggests

spectrum of

the

dered

the are

proper

1 (Rf

aromatic

each

0.01

to

be the

methyl

in

(5:l

C7-C7,

These

CHCIQl;

protons

are

by using

than

or

2 3b.

the

showed

Only

distinguishable;

(Rf IR

Thus,

both

more

hin-

quite

the

these

3a and

conclusion.

rather

UVI.

(Develosil of

system) in

iso-

UV hmax 284

HPLC

bond

and

4476,

polarity

solvent

dimers and

hexane

(c 0.35,

two compounds

‘3C NMR, IR,

of

284 nm (e

this

iso-

conf igura-

1.

Lower

supported

the

and

absolute mixture

hydrogen

the

on

overlapping

LX h,,,x

same

rota-

dimer

serious

formula

other

the

optical

molecule the

water).

intramolecular

structures. clH and

the

Thus,

CHC131;

and

dilution

more

of

1.

fa1D21+52.9”

high

assigned

t i es

half

respe-

The unsymmetrical

unsymmetrical

Rf 0.:35

0.40,

separated

of

the

by the

acetonitrile

with

under

dimeric

to

were

existence

isomers

(r

10% yields,

including

contains

of

10% yield;

Rf 0.37;

of

compared

C5-C5, due

3a,

23% yield;

determined

spectral values

di mers

mixture

one

that

was represented

isooctanel,

a 15:l

of

than

ccX1D21 +3.8”

and

of

and

material. product

la

bond,

group

14%, 23X,

natural

conformers

half

product

in

starting

the

C5-C7,

methyl other

dichloromethane); octane),

with

around

the

isolated

recovered

two possible

aromatic

group

the

identified

rotation

the

propyl

were

18% of

fully

Among

basis

dimers

with

chemical

similar shift

3a 6 1.94(6H,s);

3b

6 1.89(6H,sl.

la

1 The authors

Acknow:

(1984, nese

No.

5L104007)

of

the

thank

3a, 3b

Grant-in-Aid

Ministry

of

for

Education,

Special

Pro.ject

Science

and

Culture,

Research Japa-

Government.

1. M.

Nishizawa,

A.

Inoue,

2.

22, 2083 (1983). Symmetrical dimer

3.

Adams, T. A. Geissman, 13C NMR data of 1 are 22.2,

26.7,

126.2,

128.5,

(Received

in

27.0,

of

Japan

cadinane

REFERENCES SastrapradJa, and type

Y.

sessuiterpenoids

Phvtochemistrv,

Hayashi, are

well

and J. D. Edwards, Chem. Rew., 60, 555 as follows; (6, CDC13) 18.1, 19.6, 19.9,

27.3,

132.0,

S.

32.0,

136.4,

10 December

33.2, 139.3, 1984)

39.7, 142.5,

43.2, 150.5,

114.7, 153.1.

123.0,

known; (1960). 20.8, 123.6,

See

A.

31.7, 125.9,