Potassium lespedezate and potassium isolespedezate, bioactive substances concerned with the circadian rhythm in nyctinastic plants

Tetrahedron Letters,Vo1.30,No.30,pp Printed in Great Britain

POTASSIUM

LESPEDEZATE

Hideyuki

Shigemori,

Department

Naomi

Maxwell

AND POTASSIUM

CONCERNED

Sakai.

Eiichi

of

Hiyoshi,

Summary:

an effort

In

nyctinastic

plants,

potassium

bioactive

substances

have

proved

been

The well for

plant

known

some

chemical

the

thigmonastic isolated

and

occidentalis

as

factors

the

from

of

the

plant

water

bioassay.

All

in the

test

quite

and the

leaves

opened

varied whole

9.8Hz), Hz),

1 week,

spectral UV

(H20)

but

with

3.84(1H,

dd.

the

again

13000); 3.46(1H,

at

(around

(3 and

(c 0.65. [D20,

J = 7.8.

12.7Hz).

d, J = 8.8Hz),

H20): internal

9.3Hz).

3.89(1H, 7.18(2H,

3991

4)

dd,

as

the

J = 2.0.

and

leaves

used

were These

in for

contained

Cassia

minimum

tests active

was

extracted

with

procedure

cited

powder

(negative)

m),

379

dioxane 3.54(1H,

12.7Hz),

d, J = 8.8Hz).

the

immersed

isolation

reference: 3.50(1H,

have Cassia

others).

colourless

FAB-MS

we

in Japanese).

the

Don

G. to

both

leaf-opening

used

hours,

and

movement that

and

been

10 p.m.).

L.

leaf

the

principles

humidity

by

L.

have

because

Plant

for

In 1987,

have

several

carefully,

according

we

the

to search

the

of

been made

controlled

reported

(Medohagi

tested

for

cuneata

separated

Don.

of

were

attempted

and

have been

have

mimosoides

bioactive

night

Lespedeza

1~ NMR

G.

plants

movements

isolation

be

the

L.

plant

leaf-opening, to

salts

mimosoides

(1).1*3)

Cassia

L.

potassium

Cassia

isolated

by KPLM-1

temperature

substances

dd.

have others,

as

These

efforts

have

d.

herein

the

out

the

and

(temperature,

3 [o]2513 - 57.4'

J = 5.9,

6.79(2H,

plant

report

When

carried

carefully

bioactive

nm(E,

9.8Hz),

s).

of

be

conditions

then

two

data: 268

must

the

harb and

J = 7.8,

6.12(1H,

at room

the

1, affording

dd,

stand

to

at evening.

in Fig.

(IH,

allowed

of

several

in

isolated

were

nyctinastic great

nyctinastic

plants

leaves

plant

scientists

cuneata

young

closed

for

(M-K)-;

The

L.

and

c

control

leaves

methanol

following

Lespedeza which

mimosoides

solution,

fresh

plant

Yamamura

rhythm

circadian

Don.

the

related

controlled

We

G. of

and

of

the

the

clock,

pudica

were

factor. 4)

L.

movements

Schildknecht

from

Shosuke

University,

isolespedezate

and

the

a number

Mimosa

(2)

stimulants

reproducible,

concentration The

nyctinastic

internal

that

then,

movements

a leaf-closing

Cassia

thigmonastic

the

plant

chelidonate

cuneata

of

reported

with

leaf-opening

an

and

Keio

JAPAN

in Japanese)

So

PLANTS

Shizuri,*

Technology,

potassium

having

Since

the

and

for

Recently,

nyctinastic

to detect

distilled

are

2)

(1) from

potassium

In order

Ricca

and

concerned

Lespezeza

(Ojigi

compounds.

(KPLM-1)

plant

mechanism

substances.

stimulants

effective

organismus

In 1916,

bioactive

factor

the

pudica

their

for

SUBSTANCES

IN NYCTINASTIC

Yoshikazu

Science Yokohama,

lespedezate

be quite

Mimosa

for

pudica.1)

these

from

to

understanding

Mimosa

to search

RHYTHM

Miyoshi,

Faculty

BIOACTIVE

ISOLESPEDEZATE,

WITH THE CIRCADIAN

of Chemistry,

0040-4039/89 $3.00 + .oo Pergamon Macmillan plc

3991-3994,1989

having

the

(M-H)-,

341

(6 3.71)] dd.

4.88(1H,

J

6 3.41 =

9.3,

d, J = 7.8

3993

7.69(ZH,

d. J = 8.8Hz);

74.8(d), (br.s),

76.9(d),

'3C

77.4(d).

156.9(s),

NMR

internal

[020,

102.2(d),

116.5(d

reference; x Z),

dioxane

121.4(d),

(667.6)]

127.0(s),

61.5(t),

132.8(d

70.4(d),

x 2).

146.2

172.6(br,s).

COOK OOH KPLMF-1

(1)

Potassium

chelidonate

(2) OH

HoHa-,

HO

’ Potasrlum

lespedezate

&OOK

OH

(3)

1 Potassium

Isolespedezate

(4)

kOOMe

5

6 PH

Br

COOMe COOK

7 The 3.42,

3.52,

benzene 6.73, the

'H and

these

two

each

Finally, and

and

3.64,

aromatic

5.01,

7.69,

on

Thus, the

a

same

standing the

70.4,

127.0,

(3. 6 6.79

room

76.9. and

of

7.18:

both

4, 6

and

102.2),

The

lespedezate

(C15H170gK), suggesting

potassium of

5-D-glucopyranoside(d

olefinic

6.73

and

and

that

3 and

are

protons

(3)

the 4

mixture

were

represented

(3. 6 6.12; it

is

bond also

potassium

afforded

salts

7.69)

double

isomer (3)

3.33,

1,4-disubstituted

a trisubstituted

172.6).

potassium

formula

shifts

of

77.4

146.2),

temperature,

chemical and

presence

group(d

both

molecular

structures of

74.8.

carboxylate

at

the

132.8,

Furthermore,

the

comparison

protons

61.5.

and

WI

of 4 indicate

116.5,

signals. having

compounds

from

spectra

156.9)

(4).

other.

NMR

6.87.

corresponding

lespedezate

to

3.55,

ring(6 121.4

'3C

8

obvious

4,

( 6 has isoof

isomeric by 6 that

[A]. 6.73) the

3994

carboxylate To

confirm

were

group the

compound (7)

into

The

methyl

CH2Cl2;

2,

acetates

Two

the

located

in &

lespedezate

and

(6)5),

stereostructure

and

(6)

were

(3)

in all

synthesized

of potassium L.

wish

of

to

these

thank

of FAB mass

Ministry

of

of

same

are

This

Science

further

(JEOL)

of

O-acetobromoglucose Sieves

of

the

and

/

synthetic

obtained

from

rotation.

isolespedezate 10m7

4A

opened

mol/l).

their

the

Synthetic

analogues

as well

in progress.

and

research

and

2,

- Molecular

optical

-

isolespedezate(4)

Kusai

spectra.

Education,

potassium

(4)

experiments

compounds

including

in 4.

IR-120B/H20;

by NOE

properties

the

one

isolespedezate

from

AgOTf

of

trans

Amberlite

confirmed

concentration(l0-6

compounds A.

and

(I,

physical

data

and

potassium

(1,

those

spectral

potassium

Or.

The

with

in 3,

starting

(8)

lespedezate

at the

lespedezate(3).

activities

authors

identical

respects

and

of 4 was

temperature).

completely

position

respectively

The

at refluxing

samples

for measurements from

are

(5)5)

(5)

mimosoides

potassium

as biological The

potassium

acetates

salts

natural

on

both

acetates

(6) were

of Cassia

studies

the

/ toluene

and

bioactive

leaves

ring

3-p-methoxyphenyl-2-hydroxy-propionate

ODQ

(5)

natural

benzene

3, Ac20/Pyr.).

(6).

and

the

structures,

converted

CH2N2/MeOH;

and

Dr.

has

Culture,

T.

been

Kinoshita

supported

to which

(Sankyo in

grateful

part

Co.

Ltd..)

by

grants

acknowledgment

is

made.

References

1)

H.

Schildknecht,

Angew.

Chem.

Int.

Ed.

and --

notes

22. 695 (1983)

Engl.,

and

many

cited

references

therein. 2) U. Ricca. 3) H.

Nuov

G.

Schildknecht

cited

Ital.

(Nuova

23.

51 (1916).

Appl.

Chem..

Y. Shizuri

a colourless

oil:

and S. Yamamura,

Chem.

Lett.,

C25H30013[m/r

1570, and 1515 cm- '; 6 (C6D6) (1H. ddd, J = 2.2, 4.17(lH,

54, 2501 (1982)

dd,

s).

and

7.30(2H,

6 as a colourless

and many

references

5.55(1H,

oil: C25H3D013[m/z

dd,

J = 4.4.

(IH, d, J = 7.8Hz). and 7.79(2H. (q). 55.3(q),

(Received

in

5.69(1H,

d, J = 9.3Hz);

(s), 126.9(d). and 170.5(s);

12.2Hz).

61.6(t), 132.6(d

Japan

s),

J = 9.8Hz).

13C NMR (6, CDC13) 71.6(d),

71.9(d).

160.6(s),

(c 1.0, CHC13).

April

igag)

20.5(q),

d,

1605,

s),

dd.

3.13

12.2Hz),

3 = 9.3. 9.8Hz), J = 8.8Hz),

6.88

CHC13). 1760,

1720,

1640.

s), 1.80(3H,

'1605, 3.08

s),

3.82(1H,

dd, J = 2.5, 12,2Hz),

5.48(1H.

t,

20.6(q),

72.8(d),

164.2(s).

1.91(3H.

5.25(1H.

s), l.70(3H, s),

1640.

dd, J = 2.2,

6.69(2H.

0.70,

1720,

4.01(1H,

IR (film)

s), 3.45(3H. t,

1755,

dd, J = 7.8, 9.8H.z). 6.75(211, d, J =

68.4(d),

17

(C

s). 1.62(3H,

5.29(1H,

x 2). 138.1(s)

[al26D -10.0'

9.8Hz).

-35.1'

538.1666(Mt)];

3.22(3H,

s),

J = 7.8Hz),

J = 7.8,

[ol25~

1.59(3H,

(IH, ddd, J = 2.5, 4.4, 9.8Hz). 4.04(1H,

dd,

d,

511.

s), 1.71(3H,

s), 3.28(3H.

4.80(1H.

d. J = 8.8Hz);

1575, and 1515 cm-l: S (C606)

s), 1.68(3H,

3.23(3H,

J = 5.4, 12.2H.z).

1987,

IR (film)

538.1673(M+)];

1.65(3H.

5.4. 9.3Hz).

5.45 (IH. t, J = 9.3Hz). (1H.

Seria). Pure

K. Schumacher,

therein.

4) E. Miyoshi, 5) 5 as

Bot.

and

J = 9.8Hz),

9.3Hz). 20.6(q),

99.3(d), 169.5(s).

113.8(d

5.59

7.20(1H, 20.7(q), x 2).

170.0(s),

s), 52.2

125.3

170.2(s).