A new quinone from the heartwood of Mansonia Altissima chev: Mansonone L.

Tetrahedron

A NEW

Letters

QUINONE

FROM

C . Galeffi,

E.

Laboratori

di Chimica

Miranda

These

delle

(1,

quinones ‘A,B,

who have recently

Mans.1 Mans.E Mans.H isolated

from

reported

corresponding

(solvent

to the formula

and in the visible

at 555 nm,

F,

acetylated

from G,

modifies

the UV spectra

as above

in Great Britain.

ALTISSIMA

and G. B di Sanita,

Marini

Roma.

:

CHEV

Bettblo

Italy

4 August 1969)

publication

the isolation

the wood of Mansonia

B and D were

also

a new quinone,

described

Mansonone

of another

and the structure Altissimanamed

extract

of eight

respectively

and Imamura

(4)

Mansonone

L.

The quinone

was

Mans.C Mans. G

Mansonones

F,

-6: 2 ) (violet

shows

Yasue

I (5)

RcH R : OH

containing

spectrum

by Tanaka,

new quinone,

Mans.F Mans. L

G,

crystals

the molecular

R:H R : OH

and H by A1203 from

ethyl

(1V)column

acetate,

ion at m/e = 256 (base

melt-

peak),

C

a maximum

as in Mansonone consider

and acetic In effect,

of Mansonones

F.

L, This

which

The more

the introduction

C and E respectively

is closely 3583

contains

is confirmed

anhydride.

C) and H (6-hydroxy-Mansonone reported,

at 234 nm,

F (C 1 5Hl 203) which

Mansonone

Mansonone

6, can be excluded.

(B-hydroxy-Mansonone

for

Printed

and H

with pyridine

group,

L,

F,

as a hydroxy

hydroxy

Mansonone

accepted

15H1204’ of Mansonone L shows

We may therefore

than Mansonone

Superior-e

benzene-chloroform

The mass

The UV spectrum

L is easily

C .G . Casinovi,

Istituto

the isolation

the chloroform

165-7’).

structure.

L.

R : H ; R’: OH R : H ; R’: H R:OH;R’: H

chromatography ing point

MANSONONE

2, 3) we have reported

except

We are now reporting

Pergamon Press.

OF MANSONIA

Monache,

isolated

C, D, E,

Mansonones

1969.

HEARTWOOD

Biologica,

papers

sesquiterpene Mansonorms

THE

in UK 16 June 1969;

(Received

In previous

PP. 3583-3584,

No.40,

related

E).

with a shoulder suggests

one oxygen

atom more

by the fact that Mansonone probable

of an hydroxy as it appears

whereas

at 255 nm

an oxaphenalene

position group

in 6

in Mansonone

the spectrum

to that of Mansonone

of the

F (1)

of Spectra

G

No.40

3584

cannot be measured in alkaline solution because of the great sensitivity of the product. The NMB spectrum of Mansonone L was measured with less than 1 mg substance with the time averaging device on a Varian HA 100 instrument. after 30

scans

solvent,

shows

The spectrum in deuterated pyridine

between 1 and 3.5 ppm, in comparison to that of Mansonone F in the same a

singlet corresponding

to one methyl at 1.97 ppm (1.93 ppm for the CH3

group in the quinone ring of Mansonone F) and a doublet corresponding (J- 1.5

to a weakly coupled

methyl at 1.92 ppm which appears at 1.86 ppm in Maneonone F. The signal of

cps)

the methylm

to the carbonyl (which in Mansonone F is at 2.57 ppm) is absent in Mansonone

L. This fact

suggeststb

presence of an oxygen atom in the form of hydroxymethyl

group

CH20H. The NMH spectrum in deuterated acetone after 50

scans

between 6.20 and 8.70 ppm shows

a broad signal at 7.35 ppm compared to that of Mansonone F where a scarcely quartet

is

present at 7.10 ppm. These signals are assigned in both quinomto

resolved the olefinic

hydrogen coupled with the above mentioned methyl group which appears as a doublet (J= 1.5 cps)

at 1.92 and 1.86 ppm respectively.

The two aromatic ortho hydrogen6 which appeared

in Mansonone F as an AB quartet with chemical shift values very near (7.41 and 7.48 ppm) are in Mansonone L practically

coincident (7.84 ppm). Moreover

the

mass

spectrum shows

a peak at M+-17 (16% of the base peak). Therefore

the presence of a CH20H in @

position to the carbonyl,

is

strongly supported

by these facts. Moreover,

the observed increase of chemical shifts in aromatic protons of Mansonone L

respect to Mansonone F (7.84 respect to 7.41 and 7.48 ppm) is in agreement with the presence of a hydroxymethyl

instead of that of a methyl group (6).

References. 1. G.B. Marini Bettblo,

C.G.Casinovi

2. G.B. Marini Bettblo,

C.G.Casinovi,

AM.

and C.Galeffi. C.Galeffi,

Tetrahedron

Letters

52,4857 (1965)

and F. delle Monache.

1st. Super. Sanita 3 327 (1966)

3. C .Galeffi,

C .G . Caeinovi,

E . Miranda delle Monache,

and G. B. Marini Bettblo.

Ann. 1st. Super. Z&nit&?, 305 (1968) 4. N.Tanaka,

M.Yasue,

and M.Imamura.

5. K. Shimada, M.Yasue, 6. P.L.Corio,

B.P.Dailey.

and M.Imamura. J. Amer.

Tetrahedron

Letters 24, 2767 (1966)

Mokuzai Gakkaishi 13, 126 (1967)

Chem. Sot. 78, 3043 (1956)