Isolation of new isoprenyl alcohols from silkworm feces

Tetrahedron Letters N0.49, Printed in Great Britain.

IEOLATION

3F NEW

pp. 6209-6213,

ISOPRENYL

1966.

ALCOHOLS

Perwon

FROM

fieae

SILKWORM

Ltd.

FECES

Hideaki Fukawa, Yaeaehi Toyods Toru Shimisu. and Yaeao Yurohsehi Central Laboratory

of

Nisshin Flour Milling Co.,

Ohi, Irumagun. Saitama, Japan (Received 28 July 1966;

New pOlyieOpreny1

in revised

form 29 September 1966)

alcohola have beer, isolated from the unesponi-

fiable matter of silkworm (Bonbyx mori L.) feces. their eubetances ere in agreement with structure contain cl6 double bonde). undecaisoprenol-1 From the above unsaponifiable

Structural data on I

(n-11

and 12. which

and dodecaisoprenol-l.

matter. presence

Of

s01anes01(1-4)(n-9,

all trane form) is now evident, aleo. CH3

I HfCH+Z-CH-CH&OH structure

First fractionation

I

of the unsaponifiable matter obtained from

lipid extract of eilkaorm feces wee accomplished tion.

by molecular dietills-

The fraction, distilled out from 200 to 23Ot at 10“Torr..

6209

"LB

6210

then "LB

crpetsllieed

eeveral

ChrOmatOgraphed

a-hexsne

yielded

and infrared

The

from

n-hexane

gel.

Elution

two fractions

spectrum.

chromsto,grsphy

fiable

times

over silica

first

obtained

NDaa : 1.5112. (&s-o

jugat*d

Its

infrared

830 en-'.

Its nmr

(4-61,

r(in cDC13

Anal.

spectrum vya;

spectrum

followed acetone

showed

reference

and Rf

only

of the uneapOni-

primary

OH absorption

1660,

TYS. freq.

temperatUree

1450,

and uncon-

1380,

structural

1000. snd

InfOrmatiOn

60 9)

J-9.0 cps) and 4.8O(t.?)(-eCH-CH*-1. _

developed

cleavage

layer

in ultraviolet

The first

fraction

showed

in benzene-chloroform(4:l). From

a84 in chloroform-methanOl(4:l).

found

in

chromatography

one spot On thin

component

essential

with

and

12% ether

layer

absorption

c : saclog. Ii : ll.800.

by reductive 'were Only

by thin

oil at room

3000,

provided

a27 on s.tlica gel (3 plate8 in benzene

WZZLBa major

: 3300,

10 to

system.

~8 colorless

595(d.)(-CH-C&-OH,

found.

gave

and had no specific

,iouble bond,

7.95(-C&C&-),

fraction of solvent

which

fraction,

mlntter, W&S

regioo.

Each

in a variety

1)~ evidenced

at -5Ot

or acetone with

of the O?.Onide, levulin

on gas chromatography

and

Rf

RI

a48

oeonisation

aldehyde

and

88 2, 4-dinitrophenyl

hydraeones. Hydrogenation alcohol

derivative,

of the first NE:

Tte infrcrred spectrum

genated

~88 that aleo

alcohO1(5,7),

e::Cg*-CH..I-] * 645(t.)(CHr-C~*-oH). not 0bViOu.s and it may Horover,

result8

eaturated

product

due to "c-o had been

it" nmr spectrum

]>OlyieOprenyl

yielded

ieoprenyl

Rf a22 in benzene-chloroform

of the hydrogenated

rsductiorl the absOrption 1050 &_'(,I)snb

fraction

1.4630.

have moved

showed

shifted

that in the

from

expected

(4:l).

from

1000 to LL hydro-

r:P.lO(d.) (-CHz- r3 If-), 880(-C&But under

of reVereed-phase

the hydroxyl the larger paper

proton

signal

peaks.

chromatography

showed

w&e

No.49

that

6211

riret

the

fraction

contains

the fraction

wa8 effected

silica

Spectral

gel.

and result6

and At) were,

the described

mother

or proton

siqnal(r--B4) 1 :20

contain

cis-methyl

tie double

developed

oamometer H

b4W : 772.

apparatus ( 1:

in acetic preno1

A2

acid,

Adams

8354).Anal.

structure

was

alcohol.

tr0 which

it hae

catalyst

out

sod

NE:

prseesre

Found.

11.00 double

C :

0,usntitatLve bonds

for

in a microhydrogenation

ethanol-cyclOhexane-acetic

(5).

IS-1

6t.

Mw

rormamide

and RI

a28

: 037, 829 (Dodecaieo-

C : 86196, H : 12000, Calcd.

Catalytic

paper

acid,

by Vapor

7623). Anal.

Rf a34 in N. N'-dlmethyl

Found.

impregnated

C : Rt.09$, H : lc.82$.

carried

as solvent

experimental

on solanesol there

"Bre

these

hydrogenation

iOr C4~iiv40

: 12.17 double

bonde

iOr

I if n-12.

From our

(9).

Of

trane-methyl

spectra

that

Dolyiaoprenyl

determination

that

1.5095. m.p.

C : 86.2691 H : 11.82%.

shored

those

between

in the nmr

756(Undecaisoprenol

showed

NF:

ratios

and Rf R33 in acetic

weight

indicated

by vol.)

Substance

in relative

difference8

results

formamide

This

at 2Or with 1 : 1,

0Ver

isolated

minor

Rf a43 on pararrin

for CssHvoo

hydrogenation

.structure I if n-11.

for the irOn

of regular

9-IO'C. A molecular

gave

rechromatography

(l-P),

can be no doubt

results dolichol

and a consideration (5).

spadicol

that two 8Ubetancee

the unsaponifiable

matter

dodecaieoprenol-1,

respectively.

firmation

structurea.

Or these

Of

in the molecules.

: Il.935 Calcd.

catalytic

Above

eeparatlon

indlstinguiehsble

The are&

isubstance Al ahowed

in N, N'dimethyl

1.5094, m.p.

A611%.

bond

column

Further

or ozonization

signal(r -&34)

are both analogues

Isolated

work6

except

spectra.

for A, afid 1:1.7 for AZ.

Bubetances

acid

however.

fraction

in the nmr and

aubete.ncee.

by the precise

data

subetancee(Ar

area

two

of silkworm

feces

Further

of publiehed,

(8) and bstulaprenol

we hav5

fealrted

are undecaisbptenol-1

work

is in prOgrees

frOm and

On Con-

62lz

No.49

The

second

fraction, (4: 1).

ban&ens-chloroform chromatography obtained

any

eolrent

from

cryetsl

crystal

agreed

were

quite

fiable eole those

three

matter

diet

of leawe

those

fecea.

results

eolutlon,

the data

and

m.p.

paper

of authentic

epectral

"ee

39~4o'c.

chromatography

eoleneeol

and analytical

in

obtained data

Of the

Therefore,

of solaneeol.

II of eilkworm

alcohols

were

Of mulberry

feces originated

Detailed

with

according

01 silkworm,

(Rf I164 In acetone)

paper

feces

wee

conflrmed

to

found

in the UneapOni-

nonaieoprenol-1).

ieoprenyl

of silkworm

silkworm

rlth

in

spot on revereed-phase

981 acetone

fraction

be eolane8eol (all-trane

chromatography

and reversed-phase

identical

alcohol

layer

single

Of tobacco. In addition,

the ieoprenyl

Theee

only

from

of thin layer

eyeteme

leaves

gave

In any eolvent. eyetem

LB white

Ite Rf values

Rf a17 on thin

ala0

(Morue

bombycie

to the procedure

It ie Clear-that from

will

those

be publiehed

described

these

in leaves

It.). which

ieoprenyl

is the

above

for

alcohole

in

of mulberry.

elsewhere.

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