CA1083178A - Bicyclo- and tricyclo-alkanones aroma chemicals - Google Patents
Bicyclo- and tricyclo-alkanones aroma chemicalsInfo
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- CA1083178A CA1083178A CA336,215A CA336215A CA1083178A CA 1083178 A CA1083178 A CA 1083178A CA 336215 A CA336215 A CA 336215A CA 1083178 A CA1083178 A CA 1083178A
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Abstract
Abstract of the Disclosure Compounds represented by the structural formulae (I) (II) (III) 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 or C cannot be hydrogen; D and E each independently represent hydrogen, alkyl having from 1 to 6 carbon atoms, provided that the sum of 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 carbon atoms or aryl, provided that if either D or E is alkoxy or R-?-O- then the other substituent D or E must be hydrogen; m is an integer 1 through 8; E and G represent hydro-gen or alkyl having from 1 to 3 carbon atoms; X represents
Description
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
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-~ , - .
.. . . . .
, -:
: . . .. :, . , , . :
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-~ ,
.. . . . .
, -:
: . . .. :, . , , . :
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 ~" '.
.. . .
.: . . : . .
.
... .. .. . .
. .
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.
., ~ . .
: :
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
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 ~" '.
.. . .
.: . . : . .
.
... .. .. . .
. .
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.
., ~ . .
: :
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.) 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
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.) 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
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 ~ ' .' ~ ': :, .
. :, .~,' , , .
~43-4283~
10~33~7~
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 :,.
" ' , :
:
.
~ 83~
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
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 ~ ' .' ~ ': :, .
. :, .~,' , , .
~43-4283~
10~33~7~
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 :,.
" ' , :
:
.
~ 83~
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.
' . ' :~- ., ': . ': ' ~ ' `
,: ~
- :
., , :,
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.
' . ' :~- ., ': . ': ' ~ ' `
,: ~
- :
., , :,
Claims (8)
1. A compound represented by the structural formula wherein m is an integer from 1 through 8 and F and G represent hydrogen or alkyl having from 1 to 3 carbon atoms.
2. A compound according to claim 1 wherein m is 2.
3. A compound according to claim 2 which is 5,5,7-trimethyltricyclo[6.4Ø02,7] dodecane-3-one.
4. A compound according to claim 1 which is 1,13,13-trimethyltricyclo[8.4Ø02,9]tetradecane-11-one.
5. A process of preparing a compound of the formula comprising subjecting a compound of the formula and a compound of the formula to a photosynthesis reaction, wherein, in the above formulae, m is an integer from 1 through 8 and F and G represent hydrogen or alkyl having from 1 to 3 carbon atoms.
6. A process as defined in claim 5, wherein the reaction is conducted at a temperature of up to about 150°C.
7. A process as defined in claims 5 and 6 wherein the reaction is carried out in the presence of a solvent selected from the group consisting of acetonitrile, benzene, acetone, ethyl acetate, hydrocarbons, ethers and methylene chloride.
8. A method of imparting a fragrance or aroma to a fragance composition or a substrate, or altering the aromic characteristics of a fragrance composition, comprising incorporating into the composition or substrate an odiferous amount of a compound represented by the formula wherein m is an integer from 1 through 8 and F and G represent hydrogen or alkyl having from 1 to 3 carbon atoms.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA336,215A CA1083178A (en) | 1975-12-29 | 1979-09-24 | Bicyclo- and tricyclo-alkanones aroma chemicals |
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/645,188 US4051076A (en) | 1975-12-29 | 1975-12-29 | Aroma chemicals |
| US645,188 | 1975-12-29 | ||
| CA268,768A CA1087100A (en) | 1975-12-29 | 1976-12-24 | Bicyclo-and tricyclo-alkanones aroma chemicals |
| CA336,215A CA1083178A (en) | 1975-12-29 | 1979-09-24 | Bicyclo- and tricyclo-alkanones aroma chemicals |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1083178A true CA1083178A (en) | 1980-08-05 |
Family
ID=27164844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA336,215A Expired CA1083178A (en) | 1975-12-29 | 1979-09-24 | Bicyclo- and tricyclo-alkanones aroma chemicals |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1083178A (en) |
-
1979
- 1979-09-24 CA CA336,215A patent/CA1083178A/en not_active Expired
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