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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