Synthesis and odor properties of carene and carane derivatives


Sadowska, H.; Gora, J.

Perfumer and Flavorist 7(1): 52-54

1982


The purpose of this report is to detail the syntheses of novel 4-substituted derivatives of carene and carane, and studies of their sensory (odorous) properties. The compounds were prepared from (+)-car-3-ene in a series of processes.

Synthesis
and
odor
properties
of
carene
and
carane
derivatives
By
Halina
Sadowska
and
Jozef
Gora,
Institute
of
General
Food
Chemistry,
Technical
University,
Lodz,
Poland
n
addition
to
a-pinene,
(+)-car-3-ene
I
is
the
I
main
component
of
turpentine
obtained
from
the
Pinus
silvestris
pine.
Its
content
in
Polish,
German,
and
Russian
turpentines
is
15-41%.
1
Until
now,
(+)-car-3-ene
has
been
insufficiently
used
for
the
syntheses
of
odor
compounds.
Only
two
such
compounds
are
manufactured
on
a
commercial
scale:
4-hydroxymethyl-2-carene
2,
having
a
fl
ower
odor
with
a
fruit
note,
and
its
acetate
with
a
herb
-flower
odor,
the
"turiol"
and
turiol
acetate
of
Dragoco.
2
The
syntheses
of
sev-
eral
nitriles,
derivatives
of
carene
and
carane,
patented
recently
in
Germany,
also
deserve
at-
tention.
3
Interesting
prospects
are
seen
using
(+)-car-3-ene
for
the
synthesis
of
1
-menthol
by
the
series
of
reactions
worked
out
by
Sukh
Dev
and
coworkers.
4
An
extensive
review
of
the
possible
uses
of
car-3-ene
for
the
syntheses
of
odor
compounds
has
recently
been
published
by
Verghese.
5
The
purpose
of
this
report
is
to
detail
the
syntheses
of
novel
4
-substituted
derivatives
of
carene
and
carane,
and
studies
of
their
sensory
(odorous)
properties.
The
compounds
were
prepared
from
(+)-car-3-ene
in
a
series
of
processes
shown
in
figure
1.
In
the
first
stage
of
the
synthesis,
(+)-car-3-
ene
1
separated
from
Polish
balsamic
turpentine
was
changed,
in
the
Prins
reaction,
to
a
mixture
of
acetates
of
4-hydroxymethyl-2-carene
3
and
4-hydroxymethy1-3(10)-carene
4.
Hydrolysis
of
this
mixture
resulted
in
a
mixture
of
4-hy-
droxymethyl-2-carene
2
and
4-hydroxy-
52/Perfumer
&
Flavorist
methyl-3(10)-carene
5
in
a
ratio
of
94:6.
6
From
alcohols
2
and
5,
the
respective
alkoxynitriles
6
and
7
were
prepared
by
reaction
with
acrylonit-
rile
in
an
alkaline
medium.?
On
the
other
hand,
by
the
oxidation
of
alcohols
2
and
5,
an
83:17
mixture
of
4-formy1-2-carene
8
and
4-formy1-
3(10)-carene
9
was
obtained.
From
the
mixture
of
these
aldehydes,
their
acetals
with
ethanedio1-1,2
10
and
11
were
prepared.
4-Formyl-3-carene
13
was
prepared
by
the
de-
composition
of
the
semicarbazone
of
4-formyl-
2-carene
12
in
a
3%
boiling
aqueous
solution
of
oxalic
acid.
In
the
second
stage,
the
mixture
of
homocarenols
2
and
5
was
hydrogenated
cata-
lytically
with
Raney
Ni
to
4-hydroxymethylca-
rane
14,
This
compound
was
further
used
to
synthesize
the
following
compounds
in
a
series
of
reactions
analogous
to
those
described
above:
alkoxynitrile
15,
4-hydroxymethylcarane
acetate
16,
4-hydroxymethylcarane
propionate
17,
and
4-formylcarane
18
and
its
acetals
with
ethyl
ortoformate
19,
ethanediol-1,2
20,
and
propane-
diol-1,2
21.
The
purity
of
the
compounds
was
checked
by
GC
and
their
structure
was
determined
by
spectral
methods:
IR,
NMR,
and
MS.
The
odor
characteristics
of
the
compounds
are
given
in
Table
I.
Results
obtained
by
the
comparison
of
odors
of
the
carene
and
carane
derivatives
show
that
the
decisive
effect
on
the
odor
nature
seems
to
come
from
functional
groups.
The
derivatives
of
4
-substituted
carane
show
0272-2666/82/0001-5201$02.00/00-0
1982
Allured
Publishing
Corp.
Vol.
7,
February/March
1982
Table
L
Odor
Characteristics
of
the
Prepared
Compounds
Compound
formula
Boiling
point
c/Imlig
cH2ococH
3
0
13
8
20
0
2
m=
208,29
Odor
dharaoterietioe
I
91-93/1,5
herb
-flower
odor
[2]
y
H20/1
86-87/0,8
fiower
odor
with
a
fruit
note
[2]
C
11
H
18
0
M=166,24
5
0
01
27
H2OCH20-12cN
.
.....r
c
1
0
21
mo
M=219,33
1 i
7
pCHO
0
1
0
16
0
16o64,23
Ali
oy
4
7
ac
H2
0
13
H
20
0
2
10i IL
M=208,29
102-103/0,2
weak
odor
54-56/0,7
82-8
4
/
1
,3
verbena
odor
with
balsamic
-
woody
note
intensivo,froah
croon-kumine
odor
with
flowery
note
HO
84-8
6
/
3
freeh,etrong
kumlne
like
odor
H20H
92-9
3
/
1
,5
terpinolene
like
odor
H
li
20
0
M=168,26
14
Table
I
continues
on
page
54
Vol.
7,
February/March
1982
Perfumer
&
Flavorist/53
Carene
and
carane
derivatives
Table
I
Continued
( L i
-
CH20042CH2CN
110-112/0,4
...../r
>
.'/)0
14
H
23
NO
M=221,32
::12.21C
142000CH3
C
11
H
22
0
2
M=210,31
1;
1:
21
CH2OCOC2
H5
C
ih
H
2
0 2
...'
17
M=224,31
:
11
H
18
0
M=166,24
j:IbirC
..--°L2145
ki
80-81/0,4
fresh,green,woody„
''OC:2/45
fruit
-pear
odor
weak,woody
"molly"
odor
0
899/2
intensive
belsomie-
woody
odor
88-89/0,4
dolleate,woody,pat-
choule-cedren,odor,
with
fresh
croon
note
HO
100/10
balsamic
odor
with
pepper
shade
C
H
28
0
2
Mc
240,38
ii
CH
°
1
'142
".•
0-CH2
C
11
11
22
0
2
2.0
M=210,11
k
-.g
0-
c H 2
643
C
141
12
4
0
2
a
M=224,32
91-9
4
/
1
,3
102-104/0,2
woody,
fresh
odor
balsa-
mic
with
very
light
anise
note
light
coomarin
odor
with
menthols
note,
fresh,
green,
woody
54/Perfumer
&
Flavorist
Vol.
7,
February/March
1982
Carene
and
carane
derivatives
Figure
1
0
CH3
H
2
oc
9
cH
3
HO
Cr03
14
*
H
CHOP
2
Cl-i
"-
acH
2
1_12
c
H
-
OH
br2
-01-,
11
CHO
HO
t
H2NNHCOAlH2
2.Hydrolysis
OH
H20H
+
H2OH
C
142=C
HCN
tri
ton
B
14
H
2
OH
CH
2
-
-
CHCN
triton
B
(R
—00)20
CH(OC2H5)3
r l
f.
If
;
1C
2
H
5
CH
'NOC2
H5
91
CH
2
-014
t
CH
2
-0H
20
4
1
0-CH2
f14
2
-QH
CH
-OH
bH3
CH
0
-CH
64
3
13
CH20C1-1
2
CH
2
CN
H2OCH
2
CH2CN
H2OCH2CH2CN
15
1
Q
•-"
CH
?
OCR
P
16
R=
-CH
3
17
R=
-C21-15
an
odor
which
is
milder
and
finer
than
that
of
the
respective
derivatives
of
carene.
It
can
be
generally
stated
that
the
introduction
of
a
side
rlain
containing
1
carhon
at^rns
an‘l
a
func-
tional
group
(alcohol,
carbonyl,
ester
or
acetal)
into
position
4
of
the
carene
or
carane
system
makes
it
possible
to
synthesize
several
new
compounds
possessing
interesting
odor
prop-
erties.
Some
of
them
may
advantageously
enrich
the
range
of
perfume
materials
manufactured
from
car-3-ene.
56/Perfumer
&
Flavorist
References
1.
M.
CieSlak
and
B.
Zakrzewski,
Przemysl
Chemiczny
9,
475
(1980);
K.
Bruns,
Parf.
Kosmet.
61
(12),
457
(1980)
2.
Dragoco
Report
(1969)
3.
F.
Redies,
B.
Redies,
D.
Tark,
and
Ch
Gille,
German
Pat-
ent
2812288
(1978)
4.
Sukh
Dev,
11
International
Symposium
on
Chemistry
of
Natural
Products,
Golden
Sands,
Bulgaria,
1978
5.
J.
Verghese,
Perf.
Flay.
4
(4),
23
(1979)
6.
H.
Sadowska,
Doctoral
Thesis,
Technical
University
of
LOc1/,
1980
7.
J.
Kulesza,
J.
Podlejski,
and
J.
Wilczyflska,
Cosm.
Perf.
90
(8),
50
(1975)
Vol.
7,
February/March
1982