Note: Descriptions are shown in the official language in which they were submitted.
8~178
.
This application is a divlsional of copending appliea-
tion Serial Number 268,768, filed Decem~er 24, lg76.
This invention relates to the art of ~ragranee eompo-
sitions and, more particularly, to a elass of compounds posses~
siny desirable aromas. More specifieally, this invention is~
direeted to a elass of compounds useful as fragrances or as com-
ponents in fragranee compositions.
The art of perfumery beyan, perhaps, in the aneient
eave dwellings of prehistorie man. From i~s inception, and until
eomparatively reeently, the perfumer has u~ilized natura~ perfume
ehemicals of animal and vegetable origin. Thus, natural perfume
ehemicals such as the essential oils, for example, oil of rose
and oil of eloves, and animal secretions such as musk, have been
manipulated by the perfumer to achieve a variety of fragrances.
In more reeent years, however, researeh perfume ehemists have
developed a large number of synthetie odoriferous ehemieals pos-
sessing aroma eharaeteristies particularly desired in the art.
These synthetie aroma chemicals have added a new dimension to
the aneient art of the perfumer, since the compounds prepared
are usually of a stable chemieal nature, are inexpensive as
eompared with the natural perfume ehemieals and lend themselves
more easily to manipulation than natural perfuma chemieals sinee
sueh natural perfume ehemieals are usually a complex mixture of
substances which defy chemieal analysis. In eontrast thereto,
the synthetic aroma chemicals possess a known chemical strueture
and may therefore be manipulated by the perfumer to suit speeifie
needs. Aecordingly, there is a great need in the art of fragrance
eompositions for compounds possessing speeiie eharaeteristie
aromas.
The prineipai objeet of the present invention is to
provide sueh a elass of aroma ehemieals. -~
Another objeet of the present invention is to provide
a speeifie elass of eompounds having eharacteristie aromas whieh
-2-
~ , - .
.. . . . .
, -:
: . . .. :, . , , . :
43-4283A
r--
&13
are useful in ~he preparation of fragrances and fragrance compo- `~
si.tions.,
These and other objects, aspects and advantages of this
invention wi~l beGome apparent from a consideration of the accom-
panying specification and claims~
In accordance with the above objects, there is provided
by the present invention a class of compounds represented by the
structural formulae
~ D
E- (I)
~(CH2)r E ~:
~ ~ H2)m (II) ~ ~;
and
h2) (III)
C m ~ :
wherein n is an integer 0 or 1; A, B and C each independently
represent hydrogen or alkyl having from 1 to 3 carbon atoms,
provided that when n is 0 at least one of A, B and C cannot be
hydrogen; D and E each independently represent hydrogen, alkyl
having from 1 to 6 carbon atoms, provided that the sum o~ the
carbon atoms in D and E does not exceed 6, alkoxy having from ~ ~:
1 to 5 carbon atoms or R-~-O- wherein R represents alkyl having
from 1 to 6 carb~O atoms or aryl, provided that if either D or
E is alkoxy or R-C-O- then the other substituent D or E must be
hydrogen; m is an integer 1 through 8; F and G represent hydro- ;~
gen or alkyl having from 1 to 3 carbon atoms; X represents ~ ~-
~CH2tp wherein p is an integer 0 through 2 and I and J each
independently represent hydrogen or methyl, provided that if p
.:
- ~ -3- ;~ :
,
,
,
-~43-4283A
1(~83~8
is 0 then m must be greater than 2; provided that the sum of the
carbon and oxygen atoms in the compound is no greater than 23
These compounds are useful as fragrances or as components in
fragrance compositions.
Synthesis of these compounds can proceed as illustrated
in the following equations:
For compounds of formula I:
A A O
_~ U V _~ [ 1 )
C CH2)n ~ E ~(CH2) ~ 3
In the above equation, n, A, B, C~ D and E have the same meanings
as set forth above. As shown in equation (1) a substituted or
unsubstituted cycloalkenone is reacted with an appropriate sub-
stituted or unsubstituted olefin to form the corresponding bi-
cyclo compound. This cycloaddition is readily accomplished by
conducting the reaction by irradiation of the reactants in an
- ' appropriate solvent through a glass filter which will not pass
light having a wave length of less than 2600A.
For compounds of formula II:
D~ light ~
~(CH2)~ E ~ CH2)m ~ ~ ~ CH2)m (2)
G C E G
In the above equation, n, A, B, C, D, E, F, G and m have the same
meanings as set forth above. As shown in equation (2), the com-
pounds of formula II are also formed by a photosynthesis reaction `
of an appropriate cycloalkenone with an appropriate olefin to
obtain the desired cycloaddition compounds.
For compounds of formula III:
~ ~ ~ C~2~ - > B ~ 2) (3)
.... . . .
.:
~43-4283A
33~
In the above equation, n, A, B, C, D, E, F, G, m and X have the
same meanings as set forth above. As in the procedures for the
preparation of compounds of formulae I and II, the compounds of
formula III can be prepared as shown in equation (3) by a photo-
synthesis reaction o an appropriate cycloalkenone with an
appropriate olefin to obtain the desired cycloaddition compound.
The reaction conditions are not critical but should be
such as to facilitate the preparation of the products. Thus,
the reaction of equations (1), (2) and (3) is normally conducted
at a temperature of from low temperatures up to about 150C.
Illustrative solvents useful in these reactions are the olefins
themselves, acetonitrile, benzene, acetone, ethyl acetate, hydro-
carbons, ethers and methylene chloride. Methylene chloride is a
preferred solvent. ~ -
More preferred embodiments are those compounds repre-
sented by the following stxuctural formula
A ~ F -
B ~ lCU2)m (IV)
wherein A, B, C, F, G and m have the same meanings as set forth
above.
Still more particularly preferred compounds are repre-
sented by the following structural formulae ~ ;
F
(CH2)m (V) ;'
\X ~
and
C~3~ 2)m ~VI~
wherein m, F and G have the same meanings as set forth above.
The compounds of for~ula VI are particularly preferred novel ~
.,~: ' ', ,, -.
~ -5-
43-~283A
,~
71~3
compounds.
Compounds which exemplify this inven~ion are
l-methyltricyclo[7.4Ø o2 '8]tridecane-10-one
1,12-dlmethyltricyclo[7.4Ø02'8]tridecane-10-one
1,12,12-trimethyltricyclo[7.4Ø02'8]tridecane-lO~one
l~methyltricyclo[8.4Ø02'9]tetradecan~-11-one
1,13-dimethyltricyclo[8.4Ø02'9]tetradecane-11-one
l-methyltricyclo[7.3Ø02'8]dodecane-10-one
1,12-dimethyltricyclo[7.3Ø02'8]dodecane-10-one
1,12,12-trimethyltricyclo[7.3Ø02'8]dodecane-10-one
7-methyltetracyclo[7.2.2.02'803'7]tridecane-4-one
6,7-dimethyltetracyclo[7.2.2.02'803'7]tridecane-4 one
`6,6,7-trimethyltetracyclo~7.2.2.02'803'7]tridecane-4-one
8-methyltetracyclo[8.2.2.02'903'8]tetradecane-4-one
6,8-dimethyltetracyclo[8.2.2.02'903'8]tetradecane-4-one
6,6,8-trimethyltetracyclo[8.2.2.02'903'8]tetradecane-4-one
7-methyltetracyclo[7.2.1.02'803'7]dodecane-4-one
6,7-dimethyltetracyclo[7.2.1.02'803'7]dodecane-4-one
6~6~7-trimèthyltetracyclo[7~2.l.o2~8o3~7]dodecane-4-one ;
8,11-(or 12-)dimethyltetracyclo[8.2.1.02'903'8Jtridecane-4-onc -
6,8,11-(or 12-)trimethyltetracyclo[8.2.1.02'903'8]tridecane-4-one
6,6,8,11-(or 12-)tetramethyltetracyclo[8.2.1.02'903'8]tridecane-
4-one
1,7,12,12-tetramethyltetracyclo[7.2.1.02'803'7]dodecane-4 one
7,9,12,12-tetramethyltetracyclo[7.2.1. o2 ~ 803'7]dodecane-4-one
1,6,7,12jl2-pentamethyltetracyclo[7.2.1. o2 ~ 803'7]dodecane-4-one
6,7,9,12,12-pentamethyltetracyclo[7.2.1.02'803'7]dodecane-4-one
1,6,6,7,12,12-hexamethyltetracyclo[7.2.1.02'803'7]dodecane-4-one ;.
6,6,7,9,12,12-hexamethyltetracyclo[7.2.1. o2 '~03'7]dodecane-4-one
1,13,13-trimethyltetracyclo[8.2.1.02'903'~]tridecane-4-one
10,13,13-trimethyltetracyclo[8.2.1.02'903'8]tridecane-4-one
1,8,13,13-tetramethyltetracyclo[8.2.1.02'903'8]tridecane-4-one
.'.' . ' . '
" ~ ' ' '
~-43-4283A
1~ 31~ ~
8,10,13,13-tetramethyltetracyclo~8.2.1. o2 ~ 903~3~tridecane-4-one
1,6,8,13;13-pentamethyltetracyclo[8.2~1~0~'903'3]tridecane-4-one
6,8,10,13,13,pentamethyltetracyclo[8.2~1.02'903'8]tridecane-4-one
1,6,6,8,13,13-hexamethyltetracyclo[8.2.1.o2'903'8]tridecane-4-one
6,6,8,10,13,13-hexamethyltetracyclo[8~2,1,o~903'8]tridecane-4-one
4-(or 5-)t-butyl-1-methyltricyclo[6.3Ø02'7]undecane-9-one
4-(or 5-)t-butyl-1,11-dimethyltricyclo[6.3.0~02'7]undecane-9-one
4-(or 5-)t-butyl-1,11,11-trimethyltricyclo[6.3Ø02'7]undecane-9-
one
10-(or 11-~t-butyltricyclo[6.4Ø0 '7]dodecane-3-one
10-(or 11-)t-butyl-7-methyltricyclo[6.4Ø02'7]dodecane-3-one
10-(or 11-)t-butyl-5,7-dimethyltricyclo[6.4Ø02'7]dodecane-3-one
10-(or 11-)t-butyl-5,5,7-trimethyltricyclo[6.4Ø02'7]dodecane-
~ ,
3-one
7-t-butyl-5-methylbicyclo[3.2.0]heptane-2-one
7-t-butyl-4,5-dimethylbicyclo[3.2.0]heptane-2-one -
7-t-butyl-4,4,5-trimethylbicyclo[3.2.0]heptane-2-one
l-methyltricyclo[9.3Ø02iI]tetradecane-12-one
1,14-dimethyltricyclo[9.3Ø02'1]tetradecane-12-one
1,14,14-trimethyltricyclo[9.3Ø02'1]tetradecane-12-one
l-methyltricyclo[10.3Ø02~11]pentadecane-13-one
1,15-dimethyltricyclo[10.3Ø02'11]pentadecane-13-one
1,15,15-trimethyltricyclo[10.3Ø o2 ~ pentadecane-13-one
tricyclol9.4Ø02'1]pentadecane-12-one -
l-methyltricyclol9.4Ø o2 ~10 ] pentadecane-12-one ;~
1,14-dimethyltricyclo[9.4Ø02'1]pentadecane-12-one
1,14,14-trimethyltricyclo[9.4Ø02'1]pentadecane-12-one
tricyclo[10.4Ø02'11]hexadecane-13-one
l-methyltricyclo[10.4Ø02'11]hexadecane-13-one ,~
1,15-dimethyltricyclo[10.4Ø0 ' ]hexadecane-13-one
1~15,15-trimethyltricyclo[10.4Ø02'1,1]hexadecaIIe-13-one
tricyclo[6.3Ø o2 ~ 7]undecane-3-one
::
~ , , , . ' ' , , .' , ' : , ,
~43-4283A
1~831~8
7-methyltricyclo[6.3Ø0 ~7]undecane-3-one
5,7-dimethyltricyclo[6.3Ø02~7]undecane-3-one
5,5,7-trimethyltricyclo[6.3Ø02'7]undecane-3-one
6-methyltricyclo[5.3Ø02'6]decane-3-one
5,6-dimethyltricyclo[5.3Ø02~6]decane-3-one
5,5,6-trimethyltricyclo[5.3Ø02'6]decane-3-one
l-methyltricyclo[6.3Ø02'7]undecane-9-one
1,11-dimethyltricyclo[6.3Ø02'7]undecane-9-one
1,11,11-trimethyltricyclo[6.3Ø02~7]undecane-9-one
6-ethoxy-5-methylbicyclo[3.2.0]heptane-2-one
6-ethoxy-4,5-dimethylbicyclo[3.2.0]heptane-2-one
6-ethoxy-4,4,5-trimethylbicyclo[3.2.0]heptane-2-one
7-ethoxy-6-methylbicyclo~4.2.0]octane-2-one
7-ethoxy~4,6-dimethylbicyclo[4.2.0]octane-2-one
7-ethoxy-4,4,6-trimethylbicyclo[4.2.0]octane-2-one
6-acetoxy-5-methylbicyclo[3.2.0]heptane-2-one
6-acetoxy-4,5-dimethylbicyclo[3.2.0]heptane-2-one
6-acetoxy-4,4,5-trimethylbicyclo[3.2.0]heptane-2-one
7-acetoxy-6-methylbicyclo[4.2.0]octane-2-one
7-acetoxy-4,6-dimethylbicyclo[4.2.0]octane-2-one
6-(or 7-)~-hexyl-5-methylbicyclo[3.2.0]heptane-2-one
6-(or 7-)1~-hexyl-4,5-dimethylbicyclo[3.2.0]heptane-2-one
6-(or 7-)~-hexyl-4,4,5-trimethylbicyclo[3.2.0]heptane-2-one
7-(or 8-)a-hexylbicyclo[4.2.0]oct~ne-2-one
7-(or 8-)n-hexyl-~-methylbicyclo[4.2.0]octane-2-one ~ `
7-(or 8-)n-hexyl-4,6-dimethylbicyclo[4.2.0]octane-2-one
7-(or 8-)n-hexyl-4,4,6-trimethylbicyclo[4.2.0]octane-2-one
The compounds of this invention are useful as fra-
grances in the preparation and formulation of fragrance composi-
tions such as perfumes and perfumed products due to their
pleasing, strong and long-lasting aroma. Perfume compositions
and the use thereof in cosmetic, detergent and bar soap ~ormu-
~ -8-
... . . ..
.
~3-4283A
~ 8~1~8
.
lations and the like are exemplary of the utility thereof. Like-
wise, these compounds can be utilized as the primary fragrance
in many such compositions.
It has been determined that the structural formulae of
the compounds of ~his invention form many different spatial con-
figurations, i.e., mixtures of stereo isome~s. These mixtures
of isomers all appear to exhibit fragrance characteristics that
are desired by perfumers in compounding fragrances.
The compounds of this invention are used in concentra-
tions of from trace amounts up to about 50 percent of the fragrancecomposition into which they are incorporated. As will be expec-
ted, the concentration of the compound will vary depending on the
particular fragrance desired in the composition and even within
. _ . ...
the same composition when compounded by different perfumers.
; ~ .
It has been found that the compounds of this invention
possess notes with good intensity and persistence. This fragrance
quality particularly adapts the compounds for incorporation into
fragrance compositions and fràgrance modifying compositions having
a desirable aroma. It will be appreciated by those skilled in the
art from the present invention that the fragrance character of
~ . .
the finished fragrance compositions can be tailored to specific
uses, as more fully described hereinafter. ~;
:,:
The compounds o~ this invention are olfactory agents -
and can be incorporated into a wide variety of compositions which ~`
. . ..
will be enhanced by their fragrance notes. The compounds can be
added to fragrance compositions in pure form or they can be added ;~
to mixtures of materials in fragrance-imparting compositions to
provide a desired fragrance character to a finished fragrance
material. The fragrance compositions obtained according to this
invention are suitable in a wide variety of perfumed articles and
can also be used to enhance, modify or reinforce natural fragrance
materials. It will thus be appreciated that the compounds of this
~" '.
.. . .
.: . . : . .
.
... .. .. . .
. .
43-4283
r^~
~Z~83~
invention are useful as olfactory agents and fragrances.
The term "fragrance composition" is used herein to
mean a mixture of compounds, including, for example, natural
oils, synthetic oils, alcohols, aldehydes, ketones, esters,
lactones, and frequently hydrocarbons which are admixed so that
the combined odors of the individual components produce a pleas-
ant or desired fragrance. Such fragrance compositions usually
contain (a) the main note or the "bouquet" or foundationstone of
the composition; (b) modifiers which round off and accompany
the main note; (c) fixatives which include odorous substances
which lend a particular note to the fragrance throughout all
stages of evaporation, and substances which retard evaporation;
and (d) top-notes which are usually low-boiling, fresh-smelling
materials. Such fragrance compositions of this invention can
be used in conjunction with carriers, vehicles, solvents, dis-
persants, emulsifiers, surface-active agents, aerosol propel-
lants, and the like.
In fragrance compositions the individual components
contribute their particular olfactory characteristics, but the -;
overall effect of the fragrance composition will be the sum of
the effect of each component.- Thus, the compounds of this in-
vention can be used to alter the aroma characteristics of a
fragrance composition, for example, by highlighting or moderating
the olfactory reaction contributed by another component of the
composition.
The amount of compounds of this invention which will
be effective in fragrance compositions depends on many factors,
including the other components, their amounts and the effects
which are desired. It has been found that fragrance compositions
containing as much as 50% by weight or as little as trace amounts
.
of mixtures of compounds of this invention, or even less can be
: : . .. ~
used to impart a desirable odor to soaps, cosmetics and other
-10- '
~t3-q283A
3L{~83~L~8
products. The amount employed will depend on considerations of
cost/ nature of the end product, the effect desired in the
finished product, and the particular fragrance sought.
The compounds disclosed herein can be used alone~ in
a fragrance-modifying composition, or in a ~ragrance composition
as an olfactory component in detergents and soaps; space deodor-
ants; perfumes; colognes; bath preparations such as bath oil,
bath salts; hair preparations such as lacquers, brilliantines,
pomades, and shampoos; cosmetic preparations such as creams,
deodorants, hand lotions, sun screens; powders such as talcs, ~;
dusting powders, face powder and the like. When the compounds
of this invention are used in perfumed articles such as the
foregoing, it can be used in amounts of 0.1% or lower. Generally,
it is preferred not to use more than about 10% in the finished
perfumed article, since the use of tco much will tend to unbal~
ance the total aroma and will needlessly raise the cost of the
article.
The following examples will serve to illustrate cer-
tain specific embodiments within the scope of this invention and
are not to be construed as limiting the scope thereof. ~ -
Example 1
7-(or 8-)acetoxy-4,4,6-trimeth~lbicyclo[4.2.0]octane-2-one
.
To a 5-liter, 3-necked flask equipped with a quartz
immersion well and nitrogen bubbler was added, under nitrogen,
138 g. (1.0 mol.) of isophorone, 950 g. (ll.OS mol.) of vinyl
acetate and enough ethyl acetate to fill the flask. The solution
.
was irradiated with an Hanovia 450 watt medium pressure mercury
arc through a Corning 9700 glass filter for 35 hours. The solu~
tion was concentrated n vacuo and the oily product was distilled
through a 25 cm. Vigreux-column to yield 164.5 g. (0.734 mol.,
73~ yield) of the desired product having b.p. 94-100C./0.46 mm.
Hg. IR analysis confirms the structure of the isomers of the
desired compound.
., ~ . .
: :
43-4283A
Example 2
1,13tl3-~rimethyltricyclo[8.4Ø02'9]tetradecane~ one
To a 5-liter flask equipped with a quartz immersion
well and nitrogen bubbler was added, under nitrogen, 138 g.
(1.0 mol.) of isophorone and 420 g. of freshly distilled cyclo-
octene. The flask was filled with dichloromethane and w~s
bubbled with nitrogen for 1 hour. The solution was irradiated
for 18.5 hours with an Hanovia 450 watt medium pressure mercury
arc through a Corning 9700 glass filter. After 7 hours, an
additional 82 g. of cyclooctene was added. The solution was
concentrated in vacuo to obtain an oil which was distilled
through a 45 cm. Vigreux-column to yield 218.4 g. (0.881 mol.,
88% yield) of product, b.p. 106-110C./0.3 mm.Hg. The product
~ . .
by glpc consisted of 3 isomers in the approximate ratio of
75:12.5:12.5. IR: 1692 cm 1 confirmed the production of the
desired product.
Example 3
tricyclo[8.4Ø02'9]tetradecane-11-one
A solution of 29.4 g. (0.3 mol.) of cyclohexenone and
200 ml. of cyclooctene in 2600 ml. of dichlorome~hane was ~ -
~ ~ .
irradiated at -65C. in the low temperature photolysis apparatus
described in Organic Prep. Proc. Int. 3, 61 (1971) with a 1000
watt G.E. mercury arc through a Corning 9700 glass filter for
4 hours. At the end of the photolysis the solution was concen- ;
trated in vacuo and the product was di~tilled through a short
Vigreux-column to yield 51.8 g. (0.249 mol., 83% yield) of a -
mixture of four isomers having b.p. 108-127C./0.4 mm.Hg. IR:
1695 cm 1 confirmed the structure.
Example 4
8-tertbutyl-4,4,6-trimethylbicyclo[4.2.0]octane-2-one
To a photoreactor fitted with a quartz immersion well
and nitrogen bubbler was added, under nitrogen, 27.6 g. (0.2 mol.)
-12-
43-4283A
of isophorone, 84 g~ (1.0 mol.) of 3!3-dimethyl-1-butene (t-
butyleth~lene) and enough dichloromethane to fill the 600 ml~
reactor. The solution was bubbled for 1 hour with nitrogen and
was then irradiated for 45.5 hour through a Corning 9700 glass
filter with an Hanovia 450 watt medium pressure mercury arc.
The solution was concentrated in vacuo and the oily product was
distilled on a 60 cm. stainless steel spinning band column to
yield 13.2 g. (0.059 mol., 30% yield) of the desired product,
b.p. 84-86C./0.65 mm.Hg. NMR: tCC14) 0.80~ ~S-9H); 0.87~ (S-3H);
1.03~ (S-3H); 1.16~ (S-3H); 1.23~-2.5~ ~multiplets, 8H); IR~
1697 cm 1. ;;
Example 5
5,5,7-trimethyltricyclo[6.4Ø02'7]dodecane-3-one -~
To a photoreactor fitted with a quartz immersion well -~
. .
and nitrogen bubbler was added, under nitrogen, 30.0 g. (0.217
,
mol.) of isophorone and 145 ml. of freshly distilled cyclohexene.
Enough dichloromethane was added to fill the 825 ml. internal ~-~
volume of the photoreactor. After the solution was bubbled with
nitro~en for 1 hour, it was irradiated through a Corning 9700
glass filter for 7-1j4 hours with an Hanovia 450 watt medium
pressure mercury arc. At the end of this period, the solution
was concentra'ced in vacuo to yield an oil which was distilled
through a short Vigreux-column. The product, which is a mixture -~
of two major isomers in approximately a 3:1 ratio had b.p.
93-106C./0.2 mm.Hg. Yield 39.2 g. (0.178 mol., 82% yield). The
two major isomers could be separated by distillation on a spinning
band coiumn. Isomer A: b.p. 85C./0.1 mm.Hg. m.p. 76.6-77.4C.,
IR: 1690 cm 1; NMR: (deuterochloroform) 1.20~ (S-3H); 1.07
(S-3H); 0.90~ (S-3H); 1.32~-2.70~ (complex multiplets-15H). Iso-
mer B: b.p. 95C./0.1 mm.Hg. IR: 1690 cm 1, NMR: ~deuterochloro-
form); 1.08~, 1.05~ ~2 singlets-6H); 0.90~ (S-3H) 1.18~2.82
(multiplets-15H).
~ , .. .. .. . . .
~43-~283~
3317~3
Example 6
6,6,8-trimethyltetracyclo[8~2.1.02'903'8]tridecane~4-one
_
To a Pyrex photoreactor èquipped with a quartz immer-
sion well and nitrogen bubbler was added, under nitrogen, 103.6
g. ~0.75 mol.) of isophorone and 400 g. (4.25 mol) of freshly
distilled bicyclo [2.2.1] hept-2-ene. The vessel was filled to
its internal volume of 1200 ml. with dichloromethane. The solu-
tion was bubbled with nitrogen for 1 hour and irradiated through
a Pyrex filter for 18.5 hours with an Hanovia 450 watt medium
pressure mercury arc. After the lamp was turned off, the solu-
tion was concentrated in vacuo to obtain an oil which was dis-
tilled through a 90 cm. Vigreux-column to yield 143.6 g. (0.62
mol., 82%~ of the desired product hav1ng b.p. 90-94C./0.5 mm.Hg.
Glpc showed the product to be a 1:1 mixture of two main isomers
(180 cm. x 0.3 cm. 1% OV-225 on Chrom G, 150C. initially for ~
3 min. and then programmed 10C./min. to 250C.) IR: 1692 cm 1 -i
NMR: (CC14) singlets at 1.35~, 1.10~, 1.006, 0.92~, 0.87~ with
the singlet at 1.00~ having an integral area of 6H whiie the
others integrated to 3H. The rest of the NMR spectrum was a set ;
of complicated multiplets.
Example 7
5,5,7-trimethyl-9-oxatricyclo~6.4~0.02'7]dodecane-3-one ~ -
; :
.~ , .. . .
To a 5-liter round bottomed flask equipped with a
quartz immersion well and nitrogen bubbler was added, under
nitrogen, 138 g. (1.0 mol.) of isophorone and 498 g. ~5.93 mol.)
of 3,4-dihydropyran. Enough dichloromethane was added to fill
the flask. The solution was bubbled with nitrogen for 1.5 hours
and was irradia*ed with a 450 watt Hanovia medium pressure mercury
arc through a Corning 9700 glass filter for 20.5 hours. When the
photolysis was completed, the solution was concentrated in_vacuo
to yield 107.9 g. (0.486 mol.) of a crystalline solid and 80.6 g.
of a liquid (0.363 mol.) (Total yield 0.849 mol., 85%). The
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~43-4283~
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solid after subli~ation and recrystallization had m.p~ 112.2
C. I~: 1690 cm 1 NMR: (CC14) 0.92~ (S-3H), 1.12~ (S-3H); 1.32
(S-3H);1.35-2.15~ (multiplets 8H); 2~35~ (triplet-2H, J=14Hz);
2.65-2.93~ (M-lH); 3.38-4.20~ (M-2H). The liquid, which had b.p.
101C./0.3 mm.Hg. was found by glpc to consist of a lower boiling
minor component, the solid and a higher boiling product. Re-
distillati.on of this fraction gave a fraction, b.p. 85-90C./
0.1 mm.Hg. which had a NMR (CC14) spectrum which had methyl
singlets at 0.92~, 1.03~, 1.10~ and 1.30~. The singlet at 1.30~
belonged to the solid component, which made up 34~ of the mixture.
IR: 1695cm 1.
.
Example 8
A fragrance composition illustrative of the instant
invention contains the following components:
Component Parts by Weight
Coumarin 7 0
Vanillin 1.0
Cedrenyl acetate 2.0
Cedarwood oil 3.0
Cinnamon leaf oil 0.5
Diphenylmethane 1.0
Eugenol, prime 1.0
Ethyl cinnamate 1.0
Hercolyn D 17.5
Compound of Example 5 (Isomer mixture) 20.0
Isopropyl quinolene (10% in
dipropylene glycol) 4.0
Linalool 1.0
Olibanum extract 14.0
- Sandela2 GD 1.0
Terpinyl acetate 6.0
Phenyl ethyl alcohol 20.0
A trademark of the Hercules Company
A trademark of the Givaudan Company
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43-4283A
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This fragrance composition imparts a pleasant woody-type aroma.
Example 9
The characteristic aromas of some of the compounds o~
the instant invention are as follows:
Compound of
Example Aroma
1 incense, myrrh, olibanum,
metallic
2 olibanum, incense, lasting
3 musty, floral
4 sweet, woody, sandalwood,
faintly lasting ;
woody, olibanum~ opoponax, ex-
tremely powerful after 12 hr. `'
6 bread dough, olibanum
7* weak to odorless, musty
*The compound of Example 7 is exemplary of compounds ;
of similar structure (heterocyclic) which are not~a5 useful as
the compounds of the instant invention.
20, While the invention has been described herein With ;-
regard to certain specific embodiments, it is not so limlted,
It is to be understood that variations and modifications thereof
may be made by those skilled in the art without departing from
the spirit and scope of the invention.
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