Europaisches P a t e n t a m t

U9)

European Patent Office

Publ ication number:

Office europeen des brevets

EUROPEAN

PATENT

@ Date of filing: 18.11.85

Priority: 20.11.84 JP 246764/84

Date of publication of application:
02.07.86 Bulletin 86/27
Designated Contracting States:
CH DE FR GB IT LI NL

(3) Fragrance and flavor compositions.

There is described a fragrance and flavor compositions
containing 1,5,8,8-tetramethylbicyclo[8.1.0]undec-5-en-2one. This sesquiterpene ketone has an odor reminiscent of a
variety of odors based on the strong powdery, woody note
and furthermore has high diffusivity and retentivity and
accords well with a number of perfume, fragrance and flavor
materials.

CM
in
00

185

921

A2

@ Application number: 85114631.6

CM
<

APPLICATION

Int CI 4: C 11 B 9 / 0 0
A 61 K 7/46,

A 23

L 1/226

Applicant: KURARAY CO., LTD.

1621 Sakazu
Kurashiki-City Okayama Prefecture(JP)
^2) Inventor: Asakawa, Yoshinori
189-2, lyashiki Okinohama-cho
Tokushima City Tokushima Pref .(JP)
@ Representative: Vossius Vossius Tauchner Heunemann
Rauh
Siebertstrasse 4 P.O. Box 86 07 67
D-8000 Munchen 86(DE)

OF THE

BACKGROUND
Field

of

sitions
ketone.

Invention:

the

This

Description
a

is

there

from
trees.

on oak

the

oak

a. f r a g r a n c e

contain

material
oil,

moss

Evernia

prunanastri,

The

oil

is

of

the

chypre

fragrances

and f l a v o r

a specific

compo-

sesquiterpene

Art:

raw

fragrance

to

which

Prior

the

of

known

example,

and

relates

invention

(aroma c o m p o s i t i o n s )

As

INVENTION

isolable

from

which

obtained,

a kind

. used
or

is

as

of

fougere

for

lichen rowing

fixer

lichens,

for

perfume
for

type,

instance.
is

It

that

reported

[8.1.0]undec-5-en-2-one

[This
cf.

H.

Nozaki

et

is

of

species

japonica.

subsp.

called
Chem.

J.C.S.

al.,

from

acanthophylla

ketone

sesquiterpene

isolated

was

Plagiochila

liverworts,

1,5,8,8-tetramethylbicyclo-

"bicyclohumulenone";
Comm.,

1979,

pages

174-175.]
it

Furthermore,

is

and

cyclopentadecanone-1)
musk-like

odor

-9-one-l)

has

ketones

are

used

as

fixers

in

have

(cycloheptadecen-

odor.

civet-like

(3-methyl-

muscone

cyclopentadecanone

civetone

that

and

that

known

These

perfume

macrocyclic

and

fragrance

formulations.
An
as

a perfume

certain

of

object
or

the

invention

to

provide

or

flavor

material,

ketone

having

fragrance

sesquiterpene

is

the
of

use,
a

characteristic

distinct

odor

the

odors

of

object

of

the

invention

in

the

art

well

as
will

from

other

as

become

(arma

the

provides

DETAILED

which

japonica,
the

to

belongs

rock

and

bed

can

be

collected

and

Peninsula

in

possible

to

as

material

raw

Formosa,
it

secure

in

Bicyclohumulenone
extracting
subsp.

dried

and

diethyl

ether,

hydrocarbon

dichloroethane)

or

alcohol).

conducted

at

days.

others,

of

quantity

for

the

as

chloride,

of

about

solvent

for

use

by

example,

acanthophvlla

a halogenated

extraction

is

scale.

ether),

The

it

that

so

obtained,

(e.g.

is

Korean

such

temperature

Removal

the

a moist

on

liverwort

solvent

alcohol

an

in

order

growing

Plaaiochila

methylene

isopropyl

2-14

dibutyl

(e.g.

be

the

Said

sufficient

ground

with

japonica

of

easily.

among

can

acanthophylla

bicyclohumulenone,

a commercial

on

compition

INVENTION

Plagiochila

Japan,

and f l a v o r

liverwort

all over

skilled

description.

OF THE

Plagiochilaceae
a cormus

distributed

widely

liverwort

is

Jungermanniales,

those

bicyclohumulenone.

contains

family

advantages

INVENTION

DESCRIPTION

above-mentioned

and

to

a fragrance

which c o n t a i n s

composition)

subsp.

known

objects

detailed

following

invention

The

so-far

apparent

SUMMARY OF THE
This

the

ketones.

macrocyclic
This

from

an

ether

(e.g.

chloroform,
methanol,
is

generally

10-40C
from

ethanol,

the

over

about

extract

by

distillation
Plagiochila

essential

the

gives

acanthophylla

bicyclohumulenone.

isolated

in
oil

essential

by

extraction

supercritical
carried
oil
as

the

in

out

essential

steam

a perfume

or

fragrance

based

the

on

of

odors

and

diffusivity
of

number

perfume

etc.

fragrance
added

to

mixtures

finished

to

of

perfume

compositions

invention

are

reinforce

and

suitable
can

natural

also

be
its

pure
in

material.

be

it

fragrance

has

directly

of

a variety
such

note,

orris,

high
with

well

to

to

and

perfume

form

it

or

can

be

fragrance-imparting
character

fragrance
perfume
to

according

a wide
used

used

woody

The

obtained
in

essential

cedarwood,

added

desired

is

materials.

materials

provide

fragrance

articles

in

compositions

compositions
to

can

be

or

which

The

accords

fragrance

Bicyclohumulenone

obtained

reminiscent

aroma

and

be

material.

Furthermore,

and

chromatography.

can

vetiver,

retentivity

said

subjecting

manner.

powdery,

strong

patchouli,

carnation,

moss,

an

be

can

dioxide,

flavor

or

has

the

which

distillation

carbon

distillation

by

liverwort

also

can
steam

conventional

Bicyclohumulenone

as

with

obtained

of .odors

oil
to

by

column

or

liverwort

said

subjecting

manner

distillation

above-mentioned

The

the

Bicyclohumulenone

conventional

to

of

japonica

subsp.

contains

the

oil

variety

of

enhance,

materials.

It

and
this
perfumed

modify

or

will

thus

be

that

appreciated
olfactory
The

term

used

herein

for

example,

of

or

(c)
lend
all

fixatives

which

of

stages

low-boiling

with

olfactory

and

effect

and
of

each

note

the

are

main

vehicles,

note,

which

throughout
which

retard

usually

Such

invention

this

(b)

substances

which

the

or

composition,

substances

and

perfume
be

can

used

solvents,
agents,

like.
compositions,

contribute

fragrance

fragrance

surface-active

characteristics,

a pleasant

main

materials.

the

combined

composition

fragrance

components

perfume
the

and

perfume

individual

of

of

the

accompany

and

carriers,

propellants

the

notes

top

emulsifiers,

dispersants,

In

the

fresh-smelling

conjunction

the

(d)

frequently

and

odorous

include

compositions

fragrance

and

to

and

produce

the

(a)
of

evaporation,
and

evaporation,

off

note

a particular

aerosol

contain

round

alcohols,

that

perfume

foundation-stone
which

modifiers

Such

usually

oils,

lactones,
so

is

including,

compounds,

components

fragrance.

or

bouquet

an

composition"

synthetic

admixed

are

individual

compositions

of

esters,

which

the

fragrance

oils,

ketones,

desired

and

a mixture

mean

natural

hydrocarbons

as

fragrance.

"perfume

to

aldehydes,

odors

and

agent

useful

is

bicyclohumulenone

but

their
the

ingredient.

particular

overall

composition

the

will

Thus,

effect
be

the

bicyclo-

of
sum

in

humulenone

be

can

used

alter

to

characteristics

of

for

highlighting

example,

and

perfume

an

the
ingredient

of

according

to

the

may

in

the

intended

the

about

0.005

percent.

The

perfume

and

invention

can

be

in

example,

it

such

preparations
liquids,

as

as

bath

such

as

and

perfume
scenting

products

additives

de

so

for

95

of

soaps;

of

salts,

bath
hair

etc.;

hair

shampoos,
In

composition

can

textile

For

ways.

cosmetic

pomades,

etc.

this

space

etc.;

creams,

it

weight

composition

pomades,

as

example,

to

percent

tonics,

according

vary

cologne;

bath

stick

substrates

preparation
in

in

or

eau

hair

rinses,
the

addition,
also

be

fibers

and

used

for

fabrics,

on.

Bicyclohumulenone
the

as

amount

bicyclo-

variety

large

detergents,

and

may

fragrance

oil,

fragrance

such

weight

lotions,

creams,

cleansers;

etc.;

paper

hair

such

of

composition;

and

perfumes

preparations
supplies

used

be

can

deodorants;

used

sensible

proportion

composition

of

use

from

range

total

composition

olfactorily

The

bicyclohumulenone.

humulenone

for

composition,

another

by

fragrance

contains

invention

this

to

fragrance
moderating

or

contributed

aroma

composition.
The

of

and

a perfume

reaction

olfactory
the

by

the

of

foodstuffs,

is

also

useful

artificial
animal

as

flavors
feeds,

an

ingredient

and

as

beverages,

flavor

is

"foodstuff"

term

broadest
such

of

properties

for

based

these

ppm

up

effects.

flavoring

compositions
aromatics,
in

of

give

the

above-mentioned

the

has
best

following

means

invention.

this
be

as

the

organoleptic

feeds,

beverages,

tobacco

in

flavoring

products,

the

products

can

be

to

be

can
to

special
flavoring

1 to

about

for

15%

composition.
10%

other

to

used,

about

to

10

beyond

achieve
of

0.1

flavored.

be

to

increased

preparation

0.1%

from

proportions

example,
total

of the

In

many

by

weight

cases
will

results.

The

illustrate
no

of

desired

making

its

products

bicyclohumulenone

about

the

The

by

admixing

of

order

the

flavoring

invention

this

in

ppm
In

proportions

average

of

bicyclohumulenone

proportions

weight

is

by

used

and

used

be

weight

100

also

animal

proportions

about

to

include

modifying

can

the

on

However,

is

preparations

bicyclohumulenone

in

specification

to

The

products.

cocoa.

foodstuffs,

pharmaceutical

ppm

meant

and

tobacco

this

in

bicyclohumulenone
additive

or

agent

is

tea

coffee,

When

used

and

sense

as

and

preparations

pharmaceutical

a modern
use

and

the

of

invention
construed

in
as

high-quality

aroma

are

examples

provided

composition

aroma

of

given

further
limiting

by
which

note

bicyclohumulenone.
to

merely

detail
the

and

scope

should
of

the

10

Production
A 450

of

portion

gram

Example
the

liverwort

collected

acanthophylla

subsp.

Kamiyama-cho,

Myozai-gun,

Tokushima

Prefecture,

a mixer

extracted

with

was

in

ground
of

portions

methanol

subjected

was

concentrated

one

150

with
ml

(13.45

g)

200

g of

the

ethyl

of

under

silica

acetate.

The

fraction

of

30

was

15%

g of

Sephadex

This

attained

solvent

using

system

centration

of

while
ethyl

to

LH-20.

volumes

g of

the

while

eluate
and

chromatography
with

of

on

the
a

a mixed

chloroform

and

a bicyclohumulenone-containing
was

100

using

pressure

Development

equal

using

ethyl

n-hexane

reduced

and

residue

system
of

was

was

attained

concentration

subjected

fraction
using

chromatography
was

of

3.182

gave

fraction.

was

the

solvent

under

ether

layer

filtrate

residue

diethyl

was

acetate-85%

ethyl

g)

solvent composed
methanol

the

mixed

obtained

The

and

extract

chromatography

Development

concentrated

(5.105

column

Japan

The

the

ether

pressure

acetate-n-hexane
increasing

of

in

5 liter

hours.

pressure.

The

to

two

and

portions

reduced

gradually

residue

ml

water.

gel.

72

filtration

subjected

was

freshly

over

reduced

300

two

as

20C

at

under

portion

concentrated

and

suction

to

was

extracted

japonica

Plagiochila

subjected

g of

silica

column

gel.

Development

acetate-benzene

ethyl

gradually
acetate

to

and,

mixed

increasing

the

con-

the

30%

ethyl

from

column

g of

0.717

eluate

benzene

acetate-70%

bicyclohumulenone

instrumental

as

this

obtained

was
The

crystals.

for

data

analysis

there

fraction,

compound

are

given

below:

Melting
Specific
IR

75-77C

point:
rotation

[@]pD22:

(cm-1):

spectrum

+68.5

(c

0.99,

CHC13)

2950,

1680,

1445,

1385,

1360,

1328,

1305,

1165,

1122,

1088,

1065
[nm

UV s p e c t r u m
Mass

spectrum

1 H-NMR

spectrum

(log

(m/z):

(400

0.26

(dd,

0.97

(s,

1.47

(dd,

3.13

(ddd,

5.20

(d,

)]:

207

(3.70)

220

[M+],

205,

107,

95,

MHz)

CDCl3:

J =
3H);
J =
J
J

81,

3.2

1.17

1.07,

= 12.2

Hz,

Hz,

0.5

6.37
1H)

41

55,

1H);

Hz,
s,

6H);

Hz,

1H);

(each

and

12.4 Hz

109,

121,

67,

69,

and

7.1 Hz

= 10.7

136,

Hz

and

4.88

Hz,

1H);

13C-NMR

spectrum
16.70,

(100

MHz)

17.21

CDCl3:

(C-14,

25.52

(C-9);

33.88

(C-13);

34.34,

C-8);

39.41,

(C-12);

(C-11,

C-7,

(C-6);

130.18

39.47,
C-4,

C-15);
32.38
34.56
39.51,

C-3);

(C-5);

24.97
(C-10);
(C-1,
40.89

125.33
215.60

(C-2)

Example
Perfume

and

fragrance

composition

of

the

powdery

floral

type
A powdery
the

following

floral
formula:

base

was

prepared

according

to

Example
Perfume

and

bouquet

type

fragrance

A perfume
oriental
following

bouquet

and

formula:

composition

fragrance

type

was

of

the

composition

prepared

oriental

of

according

the
to

the

Example
Perfume

and

A chypre
following

fragrance
base

formula:

was

composition
prepared

of

the

according

chypre
to

the

type

1.
sition)

A fragrance
which

and

contains

flavor

an

composition

olfactorily

(aroma

sensible

compo-

amount

of

1,5,8,8-tetramethylbicyclo[8.1.0]undec-5-en-2-one.
2.
an

A perfume

olfactorily

or

sensible

fragrance
amount

composition
of

which

contains

1,5,8,8-tetramethyl-

bicyclo[8.1.0]undec-5-en-2-one.
3.

The

5-en-2-one
flavor

as

use

of

1,5,8,8-tetramethylbicyclo[8.10]undec-

fragrance

compositions.

material

in

perfume,

fragrance

and