Ring isomerization of isoflavone glycosides. Synthesis of tectoridin-4′-methyl ether and other iso flavone glucosides.

Tetrahedron Letters No.40, Printed in Great Britain,

Institute

of

PP, 4277-4279,

Cr,ganic

Chemistry,

1965.

Pergamon Pies8 Ltd.

Technical

University,

Budapest. (Received In

a preliminary

communication

suitable

for

the

flavones

and

their

this

method

30 September 1965)

has

ri.ng

isomer

O-methyl

been

extended

R1=R2=H

b:

;!l=!I’

c:

,Xl=tetroacetyl+-D-clucosyl,

d :

Sl=tetraacetyl-@-Dqlucosyl,

to

3

X2=11

f:

R 2=OCU3

4277

of

both

0-benzyl

e : Al+-D-Clucosyl, .il+-D-(:l’lcosyl,

we have

ization and

a :

it2=OCil

[1]

the

group

described

a method

polyhydroxy-iso-

.

derivatives. of

flovones

-

Later [2].

4278

No.48

We now wish

report

substituted

des, sising

-isof

7 by of

to

our

in

kivone

method

that, positions

~luco of

-ieoflavone coupled tion to

substituted

fkvonoid

/Ia/

presence

of

mp. 182 Co/

Isomerizatior. the

and

yielded

/IIe,

mp.

the

of

pressznce

ons

of

pectivcly

the

first

215-6

Co/

et!ler,

Ib/

bromide

yieided

IIb

[4,5],

in

aqueous

[4]

have

acetonic

potassium

tectoridin the

already

solucarbonate -

by

mp.

194-5

ref1uxi.q

Co/,

in

ccrbot;ute

rcepectivelg.

alcoholic

under

soiution

ankcdrous

conditi-

5-hydroxy-6,4’-dimcthoxy-?-/fl-D-gluco-

/IIf,

the

been

mp.

h;drolyois

229-230

01

t!lc

corresponding

Co,

lit.

[ 51:

elucoeides

aglycones

Ic,

Ia,

Id,

Ib,

res-

230°C/, Ile

and

IIa

/3/

and

to

be

ider:ti-

of

natural

respectively.

Synthetic

in

/Id,

lalter

and

case

5,7-Ilihydroxy-

‘j-hydro~-G-r.~et!loxy-7-/~-D-glucos~lo~/-isoPlitvone

. %cid

IIf

also

being

and

5-hydroxy-8,4~-dimcthoxy-7-/tetraaci;tyl-

potassium

syloyi/-is::Tlt,vone -

0:’

5.6

positions

s;rnt!le-

5,7-dihgdroxy-8,4’-dimethoxy-

conaentrnted

*AD-~~;uco~:!lo:~yy/-ieofJ.:~vorie -

cal

in

5-tiydro~r-8-methoxy-7-/tetroacetyl-~-D-;:lucosylox;r/-iroflavo-

na /Ic,

in

in

glycosides.

[ 31 and

;;lucosi-

we succeeded

thie

tetroacetyl+(-D-glucosyl

the

*fl::vone

8,

/iso-tectorigenin-4’-methyl with

in

and

isomcrization, of

-8-methoxy-jsflnvone

from

5,7

sides

ring

isomerization

r-in)5

starting

tectoridin-~-rnctl~~l :?li

respects [ 51,

,ql;cosidic prcv:o~~el;;

with

this

t!ie

being

linlcage by

t!le fi -cT)r,Sigur::tion

ether

/IIf/

product

of

the of

tectoridin

dcqradetion o!‘

synthetic

the

[5,6]. gluc~ol

;,roYied mcthylation proof i:hich Our c’ic

of has

the been

synthesis

Sour?.

;)oeition proved proves

No.48

Refer 1.

J.

VCredy

2.

J.

‘VBr:ldy:

3,

I:!.i.

4.

L.

Dhar r’arkzs,

exes

: Tetrahedron

Letters.

Submitted

for

publication.

Tetrahedron

Letters,

Submitted

for

publication.

and J.

T.it. V&ady

Seshadri: und

i.

Tetrahedron Gottsecen:

1, Acta 449

5.

c.

Xannich,

P.

Schumann

und

i'i.3.

Lin:

Arch.

77

/1959/.

Chim.

Hun&. 12,

/1962/. Pharm.

a,

/1937/. 6.

;.:.

Krishnzmurti

and

T.R.

leshxdri:

J.

Sci.

/India/

Ind.

Rasearch

G,

1 j1954/.

317