Posted by
hongjin on Monday, November 08, 2010 1:38:51 AM
Compounds represented by the structural formulae ##STR1## 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; R represents hydrogen or an alkyl having from 1 to 6 carbon atoms; D and E each independently represent hydrogen or alkyl having from 1 to 6 carbon atoms, provided that the sum of the carbon atoms in D and E does not exceed 6, provided that, in the bicyclo compounds, at least one of A, B, C, D or E must be an alkyl; m is an integer 1 through 8; aroma chemicals F and G represent hydrogen or alkyl having from 1 to 3 carbon atoms; X represents ##STR2## WHEREIN P IS AN INTEGER 0 THROUGH 2 AND I and J each independently represent hydrogen or methyl, provided that if p 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, are useful as fragrances or as components in fragrance compositions. These compounds have very pleasant, strong and long-lasting aromas. Novel compounds are also disclosed.
Claims
The embodiments of this invention in which a particular property or privilege is claimed are defined as follows:
1. A compound represented by the structural formula ##STR10## wherein m is aninteger from 1 through 8; F and G represent hydrogen or alkyl having from 1 to 3 carbon atoms; and R represents hydrogen or an alkyl having from 1 to 6 carbon atoms.
2. A compound according to claim 1 wherein m is 2.
3. A compound according to claim 2 which is 3,5,5,7-tetramethyltricyclo[6.4.0.02,7 ]dodecane-3-ol.
4. A compound according to claim 3 which is 5,5,7-trimethyltricylco[6.4.0.02,7 ]dodecane-3-ol.
Description
This invention relates to the art of fragrance compositions and, more particularly,to a class of compounds possessing desirable aromas. More specifically, this invention is directed to a class of compounds useful as fragrances or as components in fragrance compositions.
The art of perfumery began, perhaps, in the ancient cave dwellings, of prehistoric man. From its inception, and until comparatively recently, the perfumer has utilized natural perfume chemicals of animal and vegetable origin. Thus, naturalperfume chemicals such as the essential oils, for example, oil of rose and oil of cloves, and animal secretions such as musk, have been manipulated by the perfumer to achieve a variety of fragrances. In more recent years, however, research perfumechemists have developed a large number for synthetic odoriferous chemicals possessing aroma characteristics particularly desired in the art. These synthetic aroma chemicals have added a new dimension to the ancient art of the perfumer, since thecompounds prepared are usually of a stable chemical nature, are inexpensive as compared with the natural perfume chemicals and lend themselves more easily to manipulation than natural perfume chemicals since such natural perfume chemicals are usually acomplex mixture of substances which defy chemical analysis. In contrast thereto, the synthetic aroma chemicals manufacturer possess a known chemical structure and may therefore be manipulated by the perfumer to suit specific needs. Accordingly, there is a greatneed in the art of fragrance compositions for compounds possessing specific characteristic aromas.
The principal object of the present invention is to provide such a class of aroma chemicals.
Another object of the present invention is to provide a specific class of compounds having characteristic aromas which are useful in the preparation of fragrances and fragrance compositions.
These and other objects, aspects and advantages of this invention will become apparent from a consideration of the accompanying 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 ##STR3## wherein n is an integer 0 or 1; A, B and C each independently represent hydrogen or alkyl havingfrom 1 to 3 carbon atoms, provided that when n is 0 at least one of A, B or C cannot be hydrogen; R represents hydrogen or alkyl having from 1 to 6 carbon atoms; D and E each independently represent hydrogen or alkyl having from 1 to 6 carbon atoms,provided that the sum of the carbon atoms in D and E does not exceed 6, provided that, in the bicyclo compounds, at least one of A, B, C, D or E must be an alkyl; m is an integer 1 through 8; F and G represent hydrogen or alkyl having from 1 to 3 carbonatoms; X represents ##STR4## wherein p is an integer 0 through 2 and I and J each independently represent hydrogen or methyl, provided that if p is 0 then m must be greater than 2; provided that the sum of the carbon and oxygen atoms in the compound isno 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: ##STR5## In the above equations, n, A, B, C, D and E have the same meanings as set forth above. As shown in equation (1), a substituted or unsubstitutedcycloalkenone is reacted with an appropriate substituted or unsubstituted olefin to form the corresponding bicyclo compound. This cycloaddition is readily accomplished by conducting the reaction by irradiation of the reactants in an appropriate solventthrough a glass filter which will not pass light having a wave length of less than 2600 A.
As shown in equation (2), the ketone can be reduced to the secondary alcohol (where R is hydrogen) in the presence of a suitable reducing agent such as sodium borohydride, aluminum isopropoxide, or lithium aluminum hydride. As shown in equation(3), the tertiary alcohol (where R is alkyl) can be prepared from the ketone by reaction with a Grignard reagent or an alkyl lithium reagent. ##STR6## In the above equations, n, A, B, C, D, E, F, G and m have the same meanings as set forth above. Asshown in equation (4), the ketone precursors are also formed by a photosynthesis reaction of an appropriate cycloalkenone with an appropriate olefin to obtain the desired cycloaddition compound. aroma chemicals
As shown in equation (5), the ketone can be reduced to the secondary alcohol (where R is hydrogen) in the presence of a suitable reducing agent such as sodium borohydride, aluminum isopropoxide, or lithium aluminum hydride. As shown in equation(6), the tertiary alcohol (where R is alkyl) can be prepared from the ketone by reaction with a Grignard reagent or an alkyl lithium reagent. ##STR7## In the above equations, n, A, B, C, D, E, F, G, m and X have the same meanings as set forth above. The ketone precursors of the compounds of Formula III can be prepared as shown in equation (7) by a photosynthesis reaction of an appropriate cycloalkenone with an appropriate olefin to obtain the desired cycloaddition compound.
As shown in equation (8), the ketone can be reduced to the secondary alcohol (where R is hydrogen) in the presence of a suitable reducing agent such as sodium borohydride, aluminum isopropoxide, or lithium aluminum hydride. As shown in equation(9), the tertiary alcohol (where R is alkyl) can be prepared from the ketone by reaction with a Grignard reagent or an alkyl lithium reagent.
The reaction conditions for the cycloaddition reaction are not critical but should be such as to facilitate the preparation of the ketones. Thus, the reaction of equations (1), (4) and (7) is normally conducted at a temperature of from lowtemperatures up to about 150° C. Illustrative solvents useful in these reactions are the olefins themselves, acetonitrile, benzene, acetone, ethyl acetate, hydrocarbons, ethers and methylene chloride. Methylene chloride is a preferred solvent.
aroma chemicals manufacturer
The reaction conditions for the formation of the secondary alcohols from the corresponding ketones are not critical but should be such as to facilitate the preparation of the desired alcohols. Thus, the reaction of equations (2), (5) and (8) isnormally conducted at a temperature of from ambient up to about 70° C.
Illustrative solvents useful in these reactions are methanol, ethanol and isopropyl alcohol for reactions using sodium borohydride as the reducing agent. For reactions using aluminum isopropoxide as the reducing agent, isopropyl alcohol is thepreferred solvent. For reactions using lithium aluminum hydride as the reducing agent, the solvents can be ether or tetrahydrofuran. Tetrahydrofuran is the preferred solvent with this latter reducing agent.
The reaction conditions for the formation of the tertiary alcohols from the corresponding ketones should be carried out at lower temperatures, preferably at or below ambient and in the absence of oxygen and moisture.
Illustrative solvents useful in the reactions of equations (3), (6) and (9) are ether or tetrahydrofuran for the Grignard reagent and ether or hydrocarbon solvents for the alkyl lithium reagent.
More specific details of the procedures for preparation of the ketone precursors of the compounds of the instant invention can be found in copending U.S. patent application Ser. No. 645,188, filed 12-29-75 which is incorporated herein byreference.
More preferred embodiments are those compounds represented by the following structural formula ##STR8## wherein A, B, C, F, G, m and R have the same meanings as set forth above.
aroma chemicals manufacturer
Still more particularly preferred compounds are represented by the following structural formulae ##STR9## wherein m, F, G and R have the same meanings as set forth above. The compounds of Formula VI are particularly preferred novel compounds.