II. Two new flavones from tephrosia polystachyoides bak.f.

Tatmhedron Letters No.8, pp 703 - 704, 1972. II.

TWO NEW FLAMNES

FROM TEPHFIOSIA PU_YSTAUiYOIDES

R. Vleggaar,T.M. Dept.

of

Organic

(Seoeired

in

Tachmsin, shown to yoidin

have

(2)

a novel

structure

and

C23H2006,

1140

(from

gives

and 4.23

elementary

evident

from

as a singlet

(3H)

is is

the

the

revealed to

and

7 8.79

with

the

*

ForpartIseeref.

*

NMR spectra (7

-

(3H)

at

and

T 6.68. thus

G6

appears

are

assigned

Africa

proton proton

at

at

upon

C-3”.

of

(c I

is

4

1.00, 1646

cm-l to

of

at

in

spectrum

IR

nm (log

group.

one mole

7 2.64

solvent

of

methanol,

shift

the

at field

recorded

lO.DO) in cDC13.

on a Varian

is

pmton of

the

at

7 6.11

methoxyl

CDC13 to shows

The high

nature A singlet

of

from

as

The C-3

(3H).

be substituted

T 3.62.

group

benzene-d6,

that

the

methoxyl

GS.5 singlets

at

r 8.63

groups.

as a doublet

The two methylene

HA-100 instrument

1

B 4.52,

at

7 5.74

(Jl

pmtons

appear

with

TMS as

= 7.5

Hz)

as a pair

due to of

internal

coup-

doublets

1. were

113-

Stachyoidin the

exchangeable).

upfield to

formula m-p.

a 3-furanone

(shoulder)

The chemical shift

pronounced

CH,DH).

The unsubstituted

and ~a.

of

staGI-+

f1avone.l

presence

change

been

a molecular

C23H2DD6.CH3DH,

assigned

(lH, D2D

(2H)

has

components,

indicates

and 308

a flavone.

two C-methyl

appears

268

stachyoidin

as a singlet

C-4”

cm-’

mk.f.

Ssk.f.

formula 330.00

the

1972)

two minor

shows a band at

pmup.

This

to

stachyoidin

218,

7 2.04

proves

of

7 8.13

of

~a.

of

di-oxygenated

and

methoxyl

at

methine

South

polystachyoidas

polystachyoides

1770

reveals

indicative

(3H)

The benzylic ling

at

at

a 5,7

solvent dependence

now appearing

The pmton (3H)

T 6.66

ammatic

has an ortho-proton

and

A band at

stachyoidin

7 3.34,

the

Pretoria,

1.

In.1 r-

absorption

by rmltiplets

assigned

singlet

at

at

de Wsal

structures

a molecular

a flavone 3

suggesting of

M--ion

gives 40-6@),

for

exhibits

singlets

shows a characteristic

gmup

ether

respectively),

appears

H.L.

Pretoria,

Tephrosia the

fmm

on the

a flavone.

(CH3DH)

from

isolated

analysis

test’

The NMR spectrum#

S-ring

isolated

also

methanol-petmleum

The l_lV spectrum

of

We now report

(z),

characteristicof

4.55

flavone

Shinoda

Smalbergerand

University

S&F.*

5 Janu~'y 1972;aooepkdforplbllatim19 JV

msss determination

while

a positive

(KSr)

Chemistry,

(i).l

taphrodin

Accurate of

Tilt

Printed in Great&ikia.

prrlgmonPram.

standard

704

at

lo.

7 5.62

J2 = 12.0

(lH,

Hz)

and

further

splitting

as a result

at

(J3

Hz and J4 = 2.0

C-3”

pair

of

= 3.1

double

doublets

From the fusion

is

stachyoidin

-viz.

of

at

coupling

(5)

the

J2 = 12.0

coupling

(Jl

constant

and

(lH,

of

= 7.5

for

this

the

the

J3 = 3.1

protons

Hz and

C-3”

at

and

are

there

From the

tion,

it

follows

at

ton

at

G4”

7 5.74 3.1

with

and the

Hz,

C-4”

pound,

to

C25H220S, CH30H),

the

is

deuterium6

for

the

coupling

constants

Hz,

J4 = 2.0

Hz)

the

the

pair

is

appears

as a

Hz). = 7.5

Hz)

a cis

conformations

double

ring-

for

in

methylene

the

of

by exchanging

disappearance

at

the

protons Karplus

and equa-

stachyoidin.

proven

doublets

the

by application of

further

resulting

of

between

and

conformation

pmtons

R = 0),

the

stachyoidin

236-237’

m.p.

identical

with

(from

of

acetate

The rest

gmup. -

The authors respectively, to

7 5.15

of

to

the the

methine

doublet

a double

doublet

proat

(J3

=

in

glacial

ether

acetic

40-600),

acid

[o]

r

gives

-

22.5’

a con+ (c =

(3). (3)

of

the

thank

them

shows a singlet spectrum

Ors.

and

one of

lead-IV-acetate

benzene-petroleum

tephrodin

NMR and mass spectra support

with

tephrodin

The NMR spectrum

financial

preferred

(4,

of

of

Acknowledgements

for

C3”

Hz).

Acetoxylation

0.98,

(Jl

two possible

= 3.1

between

collapse

J4 = 2.0

(J3

(6)

The relationship

at

(S)

values

C-3”

that

proton

exhibit

themethinepmton

(6).

observed

pmton

doublets with

J4 = 2.0

(21

themethine

these

protons

The methine

Hz,

assumption

Both

Hz). methylene

Hz respectively).

7 5.15

Following

assumed.

7 5.91

the

K.

at

Pachler

Council

7 7.94

similar to

is

and

for

(3H)

that

S.H.

which

of

Eggers

Scientific

is

compound for

the

and Industrial

assigned &).

recording Research

(R.V.).

References 1.

T.M.

Smalberger,

2.

K.

3.

G.E.

Inglett,

4.

T.J.

Batterham

5.

R.G.

Wilson,

6.

D.J.

Adam,

R.

Venkataraman,

Prog. J.

Org.

and J.H.

L.

Vleggaar in

23,

Highet,

Bowie

Cmmbie

Chem.

Chem.,

R.J.

and H.L.

and

D.H.

and D.A.

de Waal,

Org.

Nat.

93

(1958).

Aust.

J.

Pmds.,

Chem.,

Williams, Whiting,

J.S.

Afr. l7,

l7,

Chem.

Inst.,

24,

1 (1959).

428

Tetrahedron, J.

Chem.

Sac.

(1964). 24,

(c),

1407 1966,

(1968). 542.

1 (1971).

of

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