TREA

Alkyl indane aldehyde compounds

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  • Patent Grant
  • 5403823
  • Patent Number
    5,403,823
  • Date Filed
    Friday, January 21, 1994
    30 years ago
  • Date Issued
    Tuesday, April 4, 1995
    29 years ago
Information
Abstract
The present invention relates, inter alia, to novel alkyl indane aldehyde compounds having fragrant musk-like aroma.
Description

BACKGROUND OF THE INVENTION
The present invention relates, inter alia, to novel alkyl indane aldehyde compounds having fragrant musk-like aroma.
Musk has been a highly valued fragrance for decades, finding use in numerous products such as in perfumes, colognes, soaps, cosmetics, as well as others. Natural musk is obtained from the glands of the endangered tiny musk deer of Central Asia, Moschus moschiferous, commonly referred to as the Asian musk deer. Such natural musk, however, is extremely scarce and expensive. Accordingly, fragrance chemists around the world have spent considerable time and effort searching for synthetic products which duplicate or closely simulate the natural musk scent.
As a result of such research efforts, a number of different synthetic musks have been discovered. Among such synthetic compounds are the acetyl indanes described by Sprecker et al., U.S. Pat. No. 4,466,908, compounds of the formulas ##STR1## Similarly, Fehr et al., Helvetica Chimica Acta, Vol. 72, pp. 1537-1553 (1989) discusses such synthetic musks as those of the formula ##STR2## wherein R is either H or CH.sub.3.
Traas et al., U.S. Pat. No. 4,352,748 discloses formylated and acetylated indane musks, including those of the formulas ##STR3##
Other acetyl indanes, such as 6-acetyl-1,1,3,3,5-pentamethylindane, 5-acetyl-1,1,2,3,3-pentamethylindane and 6-acetyl-5-ethyl-1,1,2,3,3-pentamethylindane, are disclosed in French Patent No. 1,392,804 (as reported in Chemical Abstracts, Vol. 63, p. 1681d (1965)).
Cobb et al., U.S. Pat. No. 4,551,573, also discusses various indane compounds.
New and or better musk aroma compounds are needed to meet the demands of the fragrance industries. The present invention is directed to these, as well as other, important ends.
SUMMARY OF THE INVENTION
The present invention provides novel compounds of the formula [I]: ##STR4## wherein R.sup.1 is H, CH.sub.3, CH.sub.2 CH.sub.3, OCH.sub.3 or OH,
R.sup.2 and R.sup.3 are, independently, H, CH.sub.3, CH.sub.2 CH.sub.3, OCH.sub.3, OH or C(O)H,
R.sup.4 and R.sup.7 are, independently, H, CH.sub.3, CH.sub.2 CH.sub.3 or CH(CH.sub.3).sub.2,
R.sup.5 and R.sup.8 are, independently H or CH.sub.3, and
R.sup.6 is H, CH.sub.3 or CH.sub.2 CH.sub.3, provided that
(i) one of R.sup.2 and R.sup.3 is C(O)H, and one of R.sup.2 and R.sup.3 is other than C(O)H,
(ii) when R.sup.1 is H, then R.sup.2 and R.sup.3 are other than OCH.sub.3 or OH,
(iii) when R.sup.1 is other than H, then R.sup.7 is CH.sub.3 or CH.sub.2 CH.sub.3,
(iv) no more than one of R.sup.4, R.sup.6 and R.sup.7 is CH.sub.2 CH.sub.3 or CH(CH.sub.3).sub.2,
(v) no more than one of R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 is H,
(vi) when each of R.sup.1, R.sup.3, R.sup.4 and R.sup.5 are CH.sub.3, then R.sup.8 is H,
(vii) when R.sup.4 is CH(CH.sub.3).sub.2, then at least one of R.sup.5 or R.sup.6 is H,
(viii) when R.sup.7 is CH(CH.sub.3).sub.2, then at least one of R.sup.6 or R.sup.8 is H,
(ix) when R.sup.1 is OCH.sub.3, then R.sup.2 and R.sup.3 are other than OH,
(x) when R.sup.1 is OH, then R.sup.2 and R.sup.3 are other than OH or OCH.sub.3,
(xi) when R.sup.1 is H, R.sup.4 is CH(CH.sub.3).sub.2 and R.sup.5 is CH.sub.3, then one of R.sup.2 and R.sup.3 is CH.sub.2 CH.sub.3,
(xii) when R.sup.1 is H, R.sup.7 is CH(CH.sub.3).sub.2 and R.sup.8 is CH.sub.3, then one of R.sup.2 and R.sup.3 is CH.sub.2 CH.sub.3,
(xiii) when R.sup.1 is H, R.sup.7 is CH(CH.sub.3).sub.2 and R.sup.8 is H, then R.sup.3 is C(O)H,
(xiv) when R.sup.1 is H, R.sup.4 is CH(CH.sub.3).sub.2 and R.sup.5 is H, then R.sup.2 is C(O)H,
(xv) when R.sup.1 is H, R.sup.7 is CH.sub.2 CH.sub.3 and R.sup.4, R.sup.5 and R.sup.8 are CH.sub.3, then both of R.sup.2 and R.sup.3 are other than CH.sub.3,
when R.sup.1 is H, R.sup.4 is CH.sub.2 CH.sub.3 and R.sup.5, R.sup.7 and R.sup.8 are CH.sub.3, then both of R.sup.2 and R.sup.3 are other than CH.sub.3, and
(xvii) when one of R.sup.2 and R.sup.3 is CH.sub.3, and each of R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are CH.sub.3, then R.sup.1 is other than H.
The foregoing compounds possess an active musk aroma having utility in the fragrance industry. The compounds of the invention may be used alone, or in combination with carriers, additional perfumery materials, and/or other ingredients, to provide various products, such as perfumes, colognes, soaps, and cosmetics.
DETAILED DESCRIPTION OF THE INVENTION
As noted above, the present invention is directed to novel musk compounds of the formula [I]: ##STR5##
In the above formula [I], the R substituents may be selected as follows: R.sup.1 may be selected from the group consisting of H, CH.sub.3, CH.sub.2 CH.sub.3, OCH.sub.3 and OH; R.sup.2 may be selected from the group consisting of H, CH.sub.3, CH.sub.2 CH.sub.3, OCH.sub.3, OH and C(O)H; R.sup.3 may be selected from the group consisting of H, CH.sub.3, CH.sub.2 CH.sub.3, OCH.sub.3, OH and C(O)H; R.sup.4 may be selected from the group consisting of H, CH.sub.3, CH.sub.2 CH.sub.3 and CH(CH.sub.3).sub.2 ; R.sup.5 may be selected from the group consisting of H and CH.sub.3 ; R.sup.6 may be selected from the group consisting of H, CH.sub.3 and CH.sub.2 CH.sub.3 ; R.sup.7 may be selected from the group consisting of H, CH.sub.3, CH.sub.2 CH.sub.3 and CH(CH.sub.3).sub.2 ; and R.sup.8 may be selected from the group consisting of H and CH.sub.3.
The foregoing selection of R substituents should, however, be made with the following qualifications in mind: that one of R.sup.2 and R.sup.3 is C(O)H, and the other of R.sup.2 and R.sup.3 is other than C(O)H; that when R.sup.1 is H, then R.sup.2 and R.sup.3 are both other than OCH.sub.3 or OH; that when R.sup.1 is other than H, then R.sup.7 is either CH.sub.3 or CH.sub.2 CH.sub.3 ; that no more than one of R.sup.4, R.sup.6 and R.sup.7 is either CH.sub.2 CH.sub.3 or CH(CH.sub.3).sub.2 ; that no more than one of R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 is H; that when all of R.sup.1, R.sup.3, R.sup.4 and R.sup.5 are CH.sub.3, then R.sup.8 is H; that when R.sup.4 is CH(CH.sub.3).sub.2, then one or both of R.sup.5 or R.sup.6 is H; that when R.sup. 7 is CH(CH.sub.3).sub.2, then one or both of R.sup.6 or R.sup.8 is H; that when R.sup.1 is OCH.sub.3, then R.sup.2 and R.sup.3 are both other than OH; that when R.sup.1 is OH, then R.sup.2 and R.sup.3 are both other than either OH or OCH.sub.3 ; that when all of the following is true--R.sup.1 is H, R.sup.4 is CH(CH.sub.3).sub.2 and R.sup.5 is CH.sub.3 --then one of R.sup.2 and R.sup.3 is CH.sub.2 CH.sub.3 ; that when all of the following is true--R.sup.1 is H, R.sup.7 is CH(CH.sub.3).sub.2 and R.sup.8 is CH.sub.3 --then one of R.sup.2 and R.sup.3 is CH.sub.2 CH.sub.3 ; that when all of the following is true--R.sup.1 is H, R.sup.7 is CH(CH.sub.3).sub.2 and R.sup.8 is H--then R.sup.3 is C(O)H; that when all of the following is true--R.sup.1 is H, R.sup.4 is CH(CH.sub.3).sub.2 and R.sup.5 is H--then R.sup.2 is C(O)H; that when all of the following is true--R.sup.1 is H, R.sup.7 is CH.sub.2 CH.sub.3 and R.sup.4, R.sup.5 and R.sup.8 are CH.sub.3 --then both of R.sup.2 and R.sup.3 are other than CH.sub.3 ; that when all of the following is true--when R.sup.1 is H, R.sup.4 is CH.sub.2 CH.sub.3 and R.sup.5, R.sup.7 and R.sup.8 are CH.sub.3 --then both of R.sup.2 and R.sup.3 are other than CH.sub.3 ; and that when all of the following is true--one of R.sup.2 and R.sup.3 is CH.sub.3, and each of R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are CH.sub.3 --then R.sup.1 is other than H.
For reasons of their fragrance characteristics, synthesis advantages, formulation benefits, and/or other values, the following are preferable classes of compounds within the scope of Formula [I]:
Compounds of Formula [I] wherein R.sup.2 is C(O)H.
Compounds of Formula [I] wherein at least one (that is, one or more) of R.sup.1, R.sup.2 and R.sup.3 are, independently OCH.sub.3 or OH.
Compounds of Formula [I] wherein at least one (that is, one or more) of R.sup.1, R.sup.2 and R.sup.3 are OCH.sub.3.
Compounds of Formula [I] wherein R.sup.1 is H, CH.sub.3, CH.sub.2 CH.sub.3 or OCH.sub.3, and R.sup.2 and R.sup.3 are, independently, H, CH.sub.3, CH.sub.2 CH.sub.3, OCH.sub.3 or C(O)H.
Compounds of Formula [I] wherein R.sup.1 is H, CH.sub.3 or OCH.sub.3, and R.sup.2 and R.sup.3, independently, are H, CH.sub.3, OCH.sub.3 or C(O)H.
Compounds of Formula [I] wherein at least one (that is, one or more) of R.sup.4 or R.sup.7 are H, CH.sub.3 or CH.sub.2 CH.sub.3.
Compounds of Formula [I] wherein R.sup.4 and R.sup.7 are, independently, CH.sub.3, CH.sub.2 CH.sub.3 or CH(CH.sub.3).sub.2, and R.sup.5 and R.sup.8 are CH.sub.3.
Compounds of Formula [I] wherein R.sup.4 and R.sup.7 are, independently, CH.sub.3, CH.sub.2 CH.sub.3 or CH(CH.sub.3).sub.2, R.sup.5 and R.sup.8 are CH.sub.3 and R.sup.6 is CH.sub.3 or CH.sub.2 CH.sub.3.
Compounds of Formula [I] wherein R.sup.4 is CH(CH.sub.3).sub.2.
Specific compounds of Formula [I] which are most preferred, for reasons of fragrance characteristics, synthesis advantages, formulation benefits, and/or other values are as follows:
The compound of Formula [I] wherein compound of Claim 1 wherein R.sup.1 is CH.sub.3, R.sup.2 is C(O)H, R.sup.3 is OCH.sub.3, R.sup.4 is CH.sub.3, R.sup.5 is CH.sub.3, R.sup.6 is CH.sub.3, R.sup.7 is CH.sub.3 and R.sup.8 is CH.sub.3.
The compound of Formula [I] wherein R.sup.1 is OCH.sub.3, R.sup.2 is C(O)H, R.sup.3 is CH.sub.3, R.sup.4 is CH.sub.3, R.sup.5 is CH.sub.3, R.sup.6 is CH.sub.3, R.sup.7 is CH.sub.3 and R.sup.8 is CH.sub.3.
The compound of Formula [I] wherein R.sup.1 is CH.sub.3, R.sup.2 is C(O)H, R.sup.3 is CH.sub.3, R.sup.4 is CH.sub.2 CH.sub.3, R.sup.5 is CH.sub.3, R.sup.6 is H, R.sup.7 is CH.sub.3 and R.sup.8 is CH.sub.3.
The compound of Formula [I] wherein R.sup.1 is CH.sub.3, R.sup.2 is C(O)H, R.sup.3 is OCH.sub.3, R.sup.4 is CH.sub.2 CH.sub.3, R.sup.5 is CH.sub.3, R.sup.6 is H, R.sup.7 is CH.sub.3 and R.sup.8 is CH.sub.3.
The compound of Formula [I] wherein R.sup.1 is CH.sub.3, R.sup.2 is C(O)H, R.sup.3 is OCH.sub.3, R.sup.4 is CH.sub.3, R.sup.5 is CH.sub.3, R.sup.6 is H, R.sup.7 is CH.sub.2 CH.sub.3 and R.sup.8 is CH.sub.3.
The compound of Formula [I] wherein R.sup.1 is OCH.sub.3, R.sup.2 is C(O)H, R.sup.3 is CH.sub.3, R.sup.4 is CH.sub.2 CH.sub.3, R.sup.5 is CH.sub.3, R.sup.6 is H, R.sup.7 is CH.sub.3 and R.sup.8 is CH.sub.3.
The compound of Formula [I] wherein R.sup.1 is OCH.sub.3, R.sup.2 is C(O)H, R.sup.3 is CH.sub.3, R.sup.4 is CH.sub.3, R.sup.5 is CH.sub.3, R.sup.6 is H, R.sup.7 is CH.sub.2 CH.sub.3 and R.sup.8 is CH.sub.3.
The compound of Formula [I] wherein R.sup.1 is CH.sub.3, R.sup.2 is C(O)H, R.sup.3 is CH.sub.3, R.sup.4 is CH(CH.sub.3).sub.2, R.sup.5 is H, R.sup.6 is CH.sub.3, R.sup.7 is CH.sub.3 and R.sup.8 is CH.sub.3.
The compound of Formula [I] wherein R.sup.1 is CH.sub.3, R.sup.2 is C(O)H, R.sup.3 is OCH.sub.3, R.sup.4 is CH(CH.sub.3).sub.2, R.sup.5 is H, R.sup.6 is CH.sub.3, R.sup.7 is CH.sub.3 and R.sup.8 is CH.sub.3.
The compound of Formula [I] wherein R.sup.1 is OCH.sub.3, R.sup.2 is C(O)H, R.sup.3 is CH.sub.3, R.sup.4 is CH(CH.sub.3).sub.2, R.sup.5 is H, R.sup.6 is CH.sub.3, R.sup.7 is CH.sub.3 and R.sup.8 is CH.sub.3.
The compound of Formula [I] wherein R.sup.1 is OCH.sub.3, R.sup.2 is C(O)H, R.sup.3 is OCH.sub.3, R.sup.4 is CH(CH.sub.3).sub.2, R.sup.5 is H, R.sup.6 is CH.sub.3, R.sup.7 is CH.sub.3 and R.sup.8 is CH.sub.3.
The compound of Formula [I] wherein R.sup.1 is H, R.sup.2 is C(O)H, R.sup.3 is CH.sub.3, R.sup.4 is CH(CH.sub.3).sub.2, R.sup.5 is H, R.sup.6 is CH.sub.3, R.sup.7 is CH.sub.3 and R.sup.8 is CH.sub.3.
The novel alkyl indane aldehyde compounds of the present invention may be prepared in various fashions. In the preferable protocol, alkyl indanes are first prepared. Then the alkyl indanes are formylated (that is, the radical --C(O)H is added to the benzene ring of the indane structure, to form an alkylated indane aldehyde), or oxidized (that is, a --CH.sub.3 substituent on the benzene ring of the indane structure is oxidized to --C(O)H, to form an alkyl indane aldehyde), yielding the alkyl indane aldehyde compounds of Formula [I]. Examples 1-6 illustrate specific methodology which may be utilized for the preparation of compounds of the present invention.
In general, alkyl indane compounds or alkyl indane aldehyde compounds may be prepared by numerous synthetic routes which will be readily apparent to those skilled in the art, once armed with the present disclosure. Examples of suitable methodology which may be employed or modified in accordance with the present invention to prepare such compounds include Fehr et al., U.S. Pat. Nos. 5,162,588, Cobb et al., 4,551,573, Gozenbach et al., 4,406,828, Traas et al., 4,352,748, Sprecker et al, 4,162,256, 4,466,908 and 4,652,400, Wood et al., 3,509,215, Stofberg et al., 3,278,622, Frank, 5,095,152, 5,087,770, 5,087,785, and 5,206,217, DeSimone, 4,018,719, Fehr et al., Helvetica Chimica Acta, Vol. 72, pp. 1537-1553 (1989), European Patent Application Publication No. 0,393,742, Great Britain Patent No. 1,459,036, Japanese Patent No. SHO 50-40761, and French Patent No. 1,392,804 (also reported in Chemical Abstracts, Vol. 63, p. 1681d (1965), the disclosures of each of which are hereby incorporated herein by reference, in their entirety. Modifications of such methodology sufficient to enable preparation of the specific novel compounds of the present invention will be readily apparent to those skilled in the art once placed in possession of the present invention.
In accordance with Frank, U.S. Pat. Nos. 5,087,785 and 5,087,770, for example, alkyl indanes may be prepared by isomerizing an alkylated tetrahydronaphthalene in the presence of (i) a Lewis acid (the Lewis acid being present in an amount of less than about 50 mole percent based on the amount of the alkylated tetrahydronaphthalene), and (ii) a solvent which can be a halogenated or unhalogenated solvent and, optionally, (iii) a phase transfer agent. Exemplary Lewis acids include titanium chloride, aluminum chloride and aluminum bromide. Exemplary halogenated solvents include dichloromethane, trichloromethane and 1,2-dichloroethane, and exemplary unhalogenated solvents include cyclohexane. Exemplary phase transfer agents include methyltrioctylammonium chloride and a mixture of methyltrioctylammonium chloride and methyltridecylammonium chloride (marketed under the trademark ADOGEN-464.TM., by Sherex Co., Dublin, Ohio).
In the foregoing process, the molar proportions of the reagents can be varied over a relatively wide range, provided that the Lewis acid is present in an amount of less than about 50 mole percent based on the amount of the alkylated tetrahydronaphthalene starting material, the precise amounts of the reagents being dependent upon such factors as the particular solvent employed, the presence or absence of a phase transfer agent, and the specific tetrahydronaphthalene starting material and other reaction conditions such as time, temperature, pressure, etc. Suitable reagent amounts will be well within the ambit of those skilled in the art, once armed with the present disclosures.
Although, in general, the molar proportions of the reagents employed in the process may be relatively widely varied, for best results, however, it is important to maintain a ratio of less than one mole of phase transfer agent per mole of Lewis acid. Preferably, the molar ratio is about 0.8 to 1.0, more preferably about 0.5 to 1.0, phase transfer agent to Lewis acid.
The subject isomerization reaction may be carried out in any suitable vessel which provides sufficient contacting between the Lewis acid, the phase transfer agent and the other reactants. For simplicity, a stirred batch reactor can be employed. The reaction vessel used should be resistant to the possible corrosive nature of the Lewis acid, such as a glass-lined vessel. The reagents of the present process may be added to the vessel in any order, although generally the solvent, the alkylated tetrahydronaphthalene, and any phase transfer agent are added first, followed by Lewis acid addition. The reaction may be carried out over a wide temperature range, but is preferably carried out at temperatures from about 0.degree. C. to about 20.degree. C. The pressure at which the reaction is carried out and the type of atmosphere are not critical. Generally, the isomerization reaction proceeds to equilibrium in about 1 to about 8 hours.
Product can be recovered from the reaction mixture by first quenching the reaction mixture in cold water or on crushed ice, preferably on ice, and then processing the mixture in the usual manner for Friedel-Crafts reactions to extract the indane compounds. Suitable extraction protocol is described, for example, in George A. Olah, Friedel-Crafts And Related Reactions, Vols. 1 and 2 (Interscience Publishers, John Wiley and Sons, New York, N.Y. 1964), the disclosures of which are hereby incorporated by reference in their entirety. Typically, following quenching and the resultant phase separation, the organic layer is washed an additional time with water to aid in removal of the Lewis acid. One or more additional washings can be carried out with dilute alkali solution to further aid Lewis acid removal. The resultant product is generally a mixture of the alkylated tetrahydronaphthalene starting material and the desired secondary alkyl indane isomerates. A more purified product may be obtained by subjecting the washed reaction mixture to reduced pressure fractional distillation, commercial chromatographic separation or other separation means known to those skilled in the art.
Alkylated tetrahydronaphthalene starting materials may be obtained commercially, or prepared using numerous well known procedures including those disclosed in Frank, U.S. Pat. Nos. 4,877,911, 4,877,914, 4,877,910, 4,877,916, 4,877,915, 4,877,913 and 4,877,912, Cobb et al., 4,551,573, Japanese Patent No. SHO 57-40420, Wood, U.S. Pat. Nos. 3,246,044, Wood et al., 3,856,875, Sato et al., 4,284,818, Kahn, 3,379,785, Suzukamo et al., 4,767,882, the disclosures of each of which are hereby incorporated herein by reference, in their entirety.
Alkyl indane compounds may then be formylated or oxidized to form alkyl indane aldehydes using conventional formylation or oxidation technology, as will be readily apparent to those skilled in the art, once armed with the present disclosure.
For example, alkyl indane compounds may be formylated using the following formylation process. Specifically, to prepare alkyl indane aldehyde compounds of the present invention, the alkyl indanes may be preferably reacted with .alpha.,.alpha.-dichloromethyl methyl ether, in a solvent such as an organic solvent (preferably a halogenated organic solvent such as, for example, anhydrous dichloromethane), in the presence of a Lewis acid (preferably titanium chloride; TiCl.sub.4). Other suitable halogenated solvents and Lewis acids are discussed above, and will be readily apparent to those skilled in the art, once armed with the present disclosures. In general, formylation methods are well known in the art and are described, for example, in Organic Syntheses, Collective Vol. 5, pp. 49-50, by A. Rieche, H. Gross, and E. Hoft, edited by H. E. Baumgarten, John Wiley and Sons (New York, N.Y. 1973), Rahm, Synthetic Communications, Vol. 12, No. 6, pp. 485-487 (1982), Effenberger, Angewandte Chemie International Edition (English), Vol. 19, No. 3, pp. 151-230 (1980), Olah et al., Chemical Reviews, Vol. 87, No. 4, pp. 671-686 (1987), and Hauser et al., Synthesis, pp. 723-724 (August 1987), the disclosures of each of which are hereby incorporated herein by reference, in their entirety.
Alternatively, to prepare alkyl indane aldehydes from alkyl indanes using oxidation techniques, the alkyl indanes are preferably reacted with ceric ammonium nitrate (Ce(NO.sub.3).sub.4. NH.sub.4 NO.sub.3), a strong oxidant for organic compounds, in the presence of acetic acid. In general, these and other suitable oxidation methods are well known in the art, and are described, for example, in Syper, Tetrahedron Letters, No. 37, pp. 4493-4498 (1966), Laing et al., J. Chem. Soc. (C), pp. 2915-2918 (1968), Imamoto et al., Chemistry Letters, pp. 1445-1446 (1990), Kreh et al., Tetrahedron Letters, Vol. 28, No. 10, pp. 1067-1068 (1987), Hauser et al., Communications, pp. 72-73 (August 1987), and Syper, Tetrahedron Letters, No. 42, pp. 4193-4198 (1967).
Further purification of the alkyl indane aldehyde compounds of Formula [I] may be carried out, if desired, using, for example, standard fractional distillation techniques, as well as other conventional extraction, distillation, crystallization and chromatography techniques, and the like.
Exemplary alkyl indane aldehyde compounds are shown in Table I below.
TABLE I__________________________________________________________________________Compound R.sup.1 R.sup.2 R.sup.3 R.sup.4 R.sup.5 R.sup.6 R.sup.7 R.sup.8__________________________________________________________________________ 1 H H C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 2 H H C(O)H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 3 H H C(O)H H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 4 H H C(O)H CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3 5 H H C(O)H CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3 6 H H C(O)H CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.3 7 H H C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H CH.sub.3 8 H H C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H 9 H H C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH(CH.sub.3).sub.2 H10 H H C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H11 H H C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.312 H H C(O)H CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.313 H H C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.314 H H C(O)H CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.315 H CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.316 H CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.317 H CH.sub.3 C(O)H H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.318 H CH.sub.3 C(O)H CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.319 H CH.sub.3 C(O)H CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.320 H CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.321 H CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H CH.sub.322 H CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H23 H CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH(CH.sub.3).sub.2 H24 H CH.sub.3 C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.325 H CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.326 H CH.sub.3 C(O)H CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.327 H CH.sub.2 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.328 H CH.sub.2 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.329 H CH.sub.2 CH.sub.3 C(O)H H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.330 H CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.331 H CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.332 H CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 H CH(CH.sub.3).sub.2 CH.sub.333 H CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.334 H CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H CH.sub.335 H CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H36 H CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH(CH.sub.3).sub.2 H37 H CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.338 H CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.339 H CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.340 H CH.sub.2 CH.sub.3 C(O)H CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.341 H CH.sub.2 CH.sub.3 C(O)H CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.342 CH.sub.3 H C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.343 CH.sub.3 H C(O)H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.344 CH.sub.3 H C(O)H H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.345 CH.sub.3 H C(O)H CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.346 CH.sub.3 H C(O)H CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.347 CH.sub.3 H C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H48 CH.sub.3 H C(O)H CH.sub.3 CH.sub. 3 CH.sub.3 CH.sub.2 CH.sub.3 H49 CH.sub.3 H C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H50 CH.sub.3 H C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.351 CH.sub.3 H C(O)H CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.352 CH.sub.3 H C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H53 CH.sub.3 H C(O)H CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.354 CH.sub.3 H C(O)H CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.355 CH.sub.3 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.356 CH.sub.3 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.357 CH.sub.3 CH.sub.3 C(O)H H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.358 CH.sub.3 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.359 CH.sub.3 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.360 CH.sub.3 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H61 CH.sub.3 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H62 CH.sub.3 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H63 CH.sub.3 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.364 CH.sub.3 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.365 CH.sub.3 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H66 CH.sub.3 CH.sub.3 C(O)H CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.367 CH.sub.3 CH.sub.3 C(O)H CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.368 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.369 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.370 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.371 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.372 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub. 3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.373 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H74 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H75 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H76 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.377 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.378 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H79 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.380 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.381 CH.sub.3 C(O)H H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.382 CH.sub.3 C(O)H H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.383 CH.sub.3 C(O)H H H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.384 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.385 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.386 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H87 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H88 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H89 CH.sub.3 C(O)H H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.390 CH.sub.3 C(O)H H CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.391 CH.sub.3 C(O)H H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H92 CH.sub.3 C(O)H H CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.393 CH.sub.3 C(O)H H CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.394 CH.sub.3 C(O)H CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.395 CH.sub.3 C(O)H CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.396 CH.sub.3 C(O)H CH.sub.3 H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.397 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H98 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H99 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H100 CH.sub.3 C(O)H CH.sub.3 CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3101 CH.sub.3 C(O)H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3102 CH.sub.3 C(O)H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H103 CH.sub.3 C(O)H CH.sub.3 CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.3104 CH.sub.3 C(O)H CH.sub.3 CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.3105 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3106 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3107 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3108 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3109 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3110 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H111 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H112 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H113 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3114 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3115 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H116 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.3117 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.3118 CH.sub.2 CH.sub.3 H C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3119 CH.sub.2 CH.sub.3 H C(O)H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3120 CH.sub.2 CH.sub.3 H C(O)H H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3121 CH.sub.2 CH.sub.3 H C(O)H CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3122 CH.sub.2 CH.sub.3 H C(O)H CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3123 CH.sub.2 CH.sub.3 H C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H124 CH.sub.2 CH.sub.3 H C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H125 CH.sub.2 CH.sub.3 H C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H126 CH.sub.2 CH.sub.3 H C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3127 CH.sub.2 CH.sub.3 H C(O)H CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3128 CH.sub.2 CH.sub.3 H C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H129 CH.sub.2 CH.sub.3 H C(O)H CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.3130 CH.sub.2 CH.sub. 3 H C(O)H CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.3131 CH.sub.2 CH.sub.3 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3132 CH.sub.2 CH.sub.3 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3133 CH.sub.2 CH.sub.3 CH.sub.3 C(O)H H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3134 CH.sub.2 CH.sub.3 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3135 CH.sub.2 CH.sub.3 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3136 CH.sub.2 CH.sub.3 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H137 CH.sub.2 CH.sub.3 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H138 CH.sub.2 CH.sub.3 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H139 CH.sub.2 CH.sub.3 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3140 CH.sub.2 CH.sub.3 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3141 CH.sub. 2 CH.sub.3 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H142 CH.sub.2 CH.sub.3 CH.sub.3 C(O)H CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.3143 CH.sub.2 CH.sub.3 CH.sub.3 C(O)H CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH3144 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3145 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3146 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3147 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3148 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3149 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H150 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H151 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H152 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3153 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3154 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H155 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.3156 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.3157 CH.sub.2 CH.sub.3 C(O)H H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3158 CH.sub.2 CH.sub.3 C(O)H H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3159 CH.sub.2 CH.sub.3 C(O)H H H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3160 CH.sub.2 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3161 CH.sub.2 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3162 CH.sub.2 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H163 CH.sub.2 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H164 CH.sub.2 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H165 CH.sub.2 CH.sub.3 C(O)H H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3166 CH.sub.2 CH.sub.3 C(O)H H CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3167 CH.sub.2 CH.sub.3 C(O)H H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H168 CH.sub.2 CH.sub.3 C(O)H H CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.3169 CH.sub.2 CH.sub.3 C(O)H H CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.3170 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3171 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3172 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3173 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3174 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3175 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H176 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H177 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H178 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3179 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3180 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H181 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.3182 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.3183 CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3184 CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3185 CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3186 CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3187 CH.sub.2 CH.sub.3 OC(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3188 CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H189 CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H190 CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H191 CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3192 CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3193 CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H194 CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.3195 CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.3196 OCH.sub.3 H C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3197 OCH.sub.3 H C(O)H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3198 OCH.sub.3 H C(O)H H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3199 OCH.sub.3 H C(O)H CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3200 OCH.sub.3 H C(O)H CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3201 OCH.sub.3 H C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H202 OCH.sub.3 H C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H203 OCH.sub.3 H C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H204 OCH.sub.3 H C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3205 OCH.sub.3 H C(O)H CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3206 OCH.sub.3 H C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H207 OCH.sub.3 H C(O)H CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.3208 OCH.sub.3 H C(O)H CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.3209 OCH.sub.3 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3210 OCH.sub.3 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3211 OCH.sub.3 CH.sub.3 C(O)H H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3212 OCH.sub.3 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3213 OCH.sub.3 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3214 OCH.sub.3 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H215 OCH.sub.3 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H216 OCH.sub.3 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H217 OCH.sub.3 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3218 OCH.sub.3 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3219 OCH.sub.3 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H220 OCH.sub.3 CH.sub.3 C(O)H CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.3221 OCH.sub.3 CH.sub.3 C(O)H CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.3222 OCH.sub.3 CH.sub.2 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3223 OCH.sub.3 CH.sub.2 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3224 OCH.sub.3 CH.sub.2 CH.sub.3 C(O)H H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3225 OCH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3226 OCH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3227 OCH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H228 OCH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H229 OCH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H230 OCH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3231 OCH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3232 OCH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H233 OCH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.3234 OCH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.3235 OCH.sub.3 C(O)H H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3236 OCH.sub.3 C(O)H H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3237 OCH.sub.3 C(O)H H H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3238 OCH.sub.3 C(O)H H CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3239 OCH.sub.3 C(O)H H CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3240 OCH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H241 OCH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H242 OCH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H243 OCH.sub.3 C(O)H H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3244 OCH.sub.3 C(O)H H CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3245 OCH.sub.3 C(O)H H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H246 OCH.sub.3 C(O)H H CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.3247 OCH.sub.3 C(O)H H CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.3248 OCH.sub.3 C(O)H CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3249 OCH.sub.3 C(O)H CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3250 OCH.sub.3 C(O)H CH.sub.3 H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3251 OCH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3252 OCH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3253 OCH.sub. 3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H254 OCH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H255 OCH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H256 OCH.sub.3 C(O)H CH.sub.3 CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3257 OCH.sub.3 C(O)H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3258 OCH.sub.3 C(O)H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H259 OCH.sub.3 C(O)H CH.sub.3 CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.3260 OCH.sub.3 C(O)H CH.sub.3 CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.3261 OCH.sub.3 C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3262 OCH.sub.3 C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3263 OCH.sub.3 C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3264 OCH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3265 OCH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3266 OCH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H267 OCH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H268 OCH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H269 OCH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3270 OCH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3271 OCH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H272 OCH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.3273 OCH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.3274 OH H C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3275 OH H C(O)H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub. 3276 OH H C(O)H H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3277 OH H C(O)H CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3278 OH H C(O)H CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3279 OH H C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H280 OH H C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H281 OH H C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H282 OH H C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3283 OH H C(O)H CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3284 OH H C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H285 OH H C(O)H CH(CH.sub.3) H CH.sub.3 CH.sub.3 CH.sub.3286 OH H C(O)H CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.3287 OH CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3288 OH CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3289 OH CH.sub.3 C(O)H H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3290 OH CH.sub.3 C(O)H CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3291 OH CH.sub.3 C(O)H CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3292 OH CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H293 OH CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H294 OH CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H295 OH CH.sub.3 C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3296 OH CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3297 OH CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H298 OH CH.sub.3 C(O)H CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.3299 OH CH.sub.3 C(O)H CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.3300 OH CH.sub.2 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3301 OH CH.sub.2 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3302 OH CH.sub.2 CH.sub.3 C(O)H H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3303 OH CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3304 OH CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3305 OH CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H306 OH CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H307 OH CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H308 OH CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3309 OH CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3310 OH CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H311 OH CH.sub.2 CH.sub.3 C(O)H CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.3312 OH CH.sub.2 CH.sub.3 C(O)H CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.3313 OH C(O)H H H CH.sub.3 CH.sub.3 CH.sub. 3 CH.sub.3314 OH C(O)H H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3315 OH C(O)H H H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3316 OH C(O)H H CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3317 OH C(O)H H CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3318 OH C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H319 OH C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H320 OH C(O)H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H321 OH C(O)H H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3322 OH C(O)H H CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3323 OH C(O)H H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H324 OH C(O)H H CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.3325 OH C(O)H H CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.3326 OH C(O)H CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3327 OH C(O)H CH.sub.3 H CH.sub. 3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3328 OH C(O)H CH.sub.3 H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3329 OH C(O)H CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3330 OH C(O)H CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3331 OH C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H332 OH C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H333 OH C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H334 OH C(O)H CH.sub.3 CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3335 OH C(O)H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3336 OH C(O)H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H337 OH C(O)H CH.sub.3 CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.3338 OH C(O)H CH.sub.3 CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.3339 OH C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3340 OH C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3341 OH C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3342 OH C(O)H CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3343 OH C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3344 OH C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3345 OH C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H346 OH C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H347 OH C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H348 OH C(O)H CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3349 OH C(O)H CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3350 OH C(O)H CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H351 OH C(O)H CH.sub.2 CH.sub.3 CH(CH.sub.3 ).sub.2 H CH.sub.3 CH.sub.3 CH.sub.3352 OH C(O)H CH.sub.2 CH.sub.3 CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.3353 CH.sub.3 OCH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3354 CH.sub.3 OCH.sub.3 C(O)H H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3355 CH.sub.3 OCH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3356 CH.sub.3 OCH.sub.3 C(O)H CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3357 CH.sub.3 OCH.sub.3 C(O)H CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3358 CH.sub.3 OCH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H359 CH.sub.3 OCH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H360 CH.sub.3 OCH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H361 CH.sub.3 OCH.sub.3 C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3362 CH.sub.3 OCH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3363 CH.sub.3 OCH.sub.3 C(O)H CH.sub.2 CH.sub. 3 CH.sub.3 CH.sub.3 CH.sub.3 H364 CH.sub.3 OCH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3365 CH.sub.3 OCH.sub.3 C(O)H CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.3366 CH.sub.3 OCH.sub.3 C(O)H CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.3367 CH.sub.3 OH C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3368 CH.sub.3 OH C(O)H H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3369 CH.sub.3 OH C(O)H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3370 CH.sub.3 OH C(O)H CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3371 CH.sub.3 OH C(O)H CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3372 CH.sub.3 OH C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H373 CH.sub.3 OH C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H374 CH.sub.3 OH C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H375 CH.sub.3 OH C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3376 CH.sub. 3 OH C(O)H CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 H377 CH.sub.3 OH C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H378 CH.sub.3 OH C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3379 CH.sub.3 OH C(O)H CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.3380 CH.sub.3 OH C(O)H CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.3381 CH.sub.3 C(O)H OCH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3382 CH.sub.3 C(O)H OCH.sub.3 H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3383 CH.sub.3 C(O)H OCH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3384 CH.sub.3 C(O)H OCH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3385 CH.sub.3 C(O)H OCH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3386 CH.sub.3 C(O)H OCH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H387 CH.sub.3 C(O)H OCH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H388 CH.sub.3 C(O)H OCH.sub.3 CH.sub.3 CH.sub. 3 CH.sub.2 CH.sub.3 CH.sub.3 H389 CH.sub.3 C(O)H OCH.sub.3 CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3390 CH.sub.3 C(O)H OCH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3391 CH.sub.3 C(O)H OCH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H392 CH.sub.3 C(O)H OCH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3393 CH.sub.3 C(O)H OCH.sub.3 CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.3394 CH.sub.3 C(O)H OCH.sub.3 CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.3395 CH.sub.3 C(O)H OH H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3396 CH.sub.3 C(O)H OH H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3397 CH.sub.3 C(O)H OH H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3398 CH.sub.3 C(O)H OH CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3399 CH.sub.3 C(O)H OH CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3400 CH.sub.3 C(O)H OH CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H401 CH.sub.3 C(O)H OH CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H402 CH.sub.3 C(O)H OH CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H403 CH.sub.3 C(O)H OH CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3404 CH.sub.3 C(O)H OH CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3405 CH.sub.3 C(O)H OH CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H406 CH.sub.3 C(O)H OH CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3407 CH.sub.3 C(O)H OH CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.3408 CH.sub.3 C(O)H OH CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.3409 CH.sub.2 CH.sub.3 OCH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3410 CH.sub.2 CH.sub.3 OCH.sub.3 C(O)H H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3411 CH.sub.2 CH.sub.3 OCH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3412 CH.sub.2 CH.sub.3 OCH.sub.3 C(O)H CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3413 CH.sub.2 CH.sub.3 OCH.sub.3 C(O)H CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3414 CH.sub.2 CH.sub.3 OCH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H415 CH.sub.2 CH.sub.3 OCH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H416 CH.sub.2 CH.sub.3 OCH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H417 CH.sub.2 CH.sub.3 OCH.sub.3 C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3418 CH.sub.2 CH.sub.3 OCH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3419 CH.sub.2 CH.sub.3 OCH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H420 CH.sub.2 CH.sub.3 OCH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3421 CH.sub.2 CH.sub.3 OCH.sub.3 C(O)H CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.3422 CH.sub.2 CH.sub.3 OCH.sub.3 C(O)H CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.3423 CH.sub.2 CH.sub.3 OH C(O)H H CH.sub. 3 CH.sub.3 CH.sub.3 CH.sub.3424 CH.sub.2 CH.sub.3 OH C(O)H H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3425 CH.sub.2 CH.sub.3 OH C(O)H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3426 CH.sub.2 CH.sub.3 OH C(O)H CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3427 CH.sub.2 CH.sub.3 OH C(O)H CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3428 CH.sub.2 CH.sub.3 OH C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H429 OH C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H430 CH.sub.2 CH.sub.3 OH C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H431 CH.sub.2 CH.sub.3 OH C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3432 CH.sub.2 CH.sub.3 OH C(O)H CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3433 CH.sub.2 CH.sub.3 OH C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H434 CH.sub.2 CH.sub.3 OH C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3435 CH.sub. 2 CH.sub.3 OH C(O)H CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.3436 CH.sub.2 CH.sub.3 OH C(O)H CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.3437 CH.sub.2 CH.sub.3 C(O)H OCH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3438 CH.sub.2 CH.sub.3 C(O)H OCH.sub.3 H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3439 CH.sub.2 CH.sub.3 C(O)H OCH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3440 CH.sub.2 CH.sub.3 C(O)H OCH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3441 CH.sub.2 CH.sub.3 C(O)H OCH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3442 CH.sub.2 CH.sub.3 C(O)H OCH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H443 CH.sub.2 CH.sub.3 C(O)H OCH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H444 CH.sub.2 CH.sub.3 C(O)H OCH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H445 CH.sub.2 CH.sub.3 C(O)H OCH.sub.3 CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3446 CH.sub.2 CH.sub.3 C(O)H OCH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3447 CH.sub.2 CH.sub.3 C(O)H OCH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H448 CH.sub.2 CH.sub.3 C(O)H OCH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3449 CH.sub.2 CH.sub.3 C(O)H OCH.sub.3 CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.3450 CH.sub.2 CH.sub.3 C(O)H OCH.sub.3 CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.3451 CH.sub.2 CH.sub.3 C(O)H OH H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3452 CH.sub.2 CH.sub.3 C(O)H OH H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3453 CH.sub.2 CH.sub.3 C(O)H OH H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3454 CH.sub.2 CH.sub.3 C(O)H OH CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3455 CH.sub.2 CH.sub.3 C(O)H OH CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3456 CH.sub.2 CH.sub.3 C(O)H OH CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H457 CH.sub.2 CH.sub.3 C(O)H OH CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H458 CH.sub.2 CH.sub.3 C(O)H OH CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H459 CH.sub.2 CH.sub.3 C(O)H OH CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3460 CH.sub.2 CH.sub.3 C(O)H OH CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3461 CH.sub.2 CH.sub.3 C(O)H OH CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H462 CH.sub.2 CH.sub.3 C(O)H OH CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3463 CH.sub.2 CH.sub.3 C(O)H OH CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.3464 CH.sub.2 CH.sub.3 C(O)H OH CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.3465 OCH.sub.3 OCH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3466 OCH.sub.3 OCH.sub.3 C(O)H H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3467 OCH.sub.3 OCH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3468 OCH.sub.3 OCH.sub.3 C(O)H CH.sub.3 CH.sub. 3 H CH.sub.3 CH.sub.3469 OCH.sub.3 OCH.sub.3 C(O)H CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3470 OCH.sub.3 OCH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H471 OCH.sub.3 OCH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H472 OCH.sub.3 OCH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H473 OCH.sub.3 OCH.sub.3 C(O)H CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3474 OCH.sub.3 OCH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3475 OCH.sub.3 OCH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H476 OCH.sub.3 OCH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3477 OCH.sub.3 OCH.sub.3 C(O)H CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.3478 OCH.sub.3 OCH.sub.3 C(O)H CH(CH.sub.3).sub.2 CH.sub.3 H CH.sub.3 CH.sub.3479 OCH.sub.3 C(O)H OCH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3480 OCH.sub.3 C(O)H OCH.sub.3 H CH.sub.3 CH.sub. 2 CH.sub.3 CH.sub.3 CH.sub.3481 OCH.sub.3 C(O)H OCH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3482 OCH.sub.3 C(O)H OCH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3483 OCH.sub.3 C(O)H OCH.sub.3 CH.sub.3 CH.sub.3 H CH.sub.2 CH.sub.3 CH.sub.3484 OCH.sub.3 C(O)H OCH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H485 OCH.sub.3 C(O)H OCH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 H486 OCH.sub.3 C(O)H OCH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H487 OCH.sub.3 OC(O)H OCH.sub.3 CH.sub.2 CH.sub.3 H CH.sub.3 CH.sub.3 CH.sub.3488 OCH.sub.3 C(O)H OCH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 H CH.sub.3 CH.sub.3489 OCH.sub.3 C(O)H OCH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 H490 OCH.sub.3 C(O)H OCH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3491 OCH.sub.3 C(O)H OCH.sub.3 CH(CH.sub.3).sub.2 H CH.sub.3 CH.sub.3 CH.sub.3492 OCH.sub.3 C(O)H OCH.sub.3 CH(CH.sub.3).sub. 2 CH.sub.3 H CH.sub.3 CH.sub.3493 H H C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3494 H H C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3495 H H C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3496 H H C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3497 H CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3498 H CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3499 H CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3500 H CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3501 H CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3502 H CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3503 CH.sub.3 H C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3504 CH.sub.3 H C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3505 CH.sub.3 H C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3506 CH.sub.3 H C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3507 CH.sub.3 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3508 CH.sub.3 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3509 CH.sub.3 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3510 CH.sub.3 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3511 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3512 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3513 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3514 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3515 CH.sub.3 OCH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3516 CH.sub.3 OCH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3517 CH.sub.3 OCH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3518 CH.sub.3 OH C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3519 CH.sub.3 OH C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3520 CH.sub.3 OH C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3521 CH.sub.2 CH.sub.3 H C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3522 CH.sub.2 CH.sub.3 H C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3523 CH.sub.2 CH.sub.3 H C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3524 CH.sub.2 CH.sub.3 H C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3525 CH.sub.2 CH.sub.3 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3526 CH.sub.2 CH.sub.3 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub. 3 CH.sub.3 CH.sub.3527 CH.sub.2 CH.sub.3 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3528 CH.sub.2 CH.sub.3 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3529 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3530 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3531 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3532 CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3533 CH.sub.2 CH.sub.3 OCH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3534 CH.sub.2 CH.sub.3 OCH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3535 CH.sub.2 CH.sub.3 OCH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3536 CH.sub.2 CH.sub.3 OH C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3537 CH.sub.2 CH.sub.3 OH C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3538 CH.sub.2 CH.sub.3 OH C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3539 OCH.sub.3 H C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3540 OCH.sub.3 H C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3541 OCH.sub.3 H C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3542 OCH.sub.3 H C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3543 OCH.sub.3 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3544 OCH.sub.3 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3545 OCH.sub.3 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3546 OCH.sub.3 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3547 OCH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3548 OCH.sub. 3 CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3549 OCH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3550 OCH.sub.3 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3551 OCH.sub.3 OCH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3552 OCH.sub.3 OCH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3553 OCH.sub.3 OCH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3554 OH H C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3555 OH H C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3556 OH H C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3557 OH H C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3558 OH CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3559 OH CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3560 OH CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3561 OH CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3562 OH CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3563 OH CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3564 OH CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3565 OH CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3566 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3567 CH.sub.3 C(O)H H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3568 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3569 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3570 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3571 CH.sub.3 C(O)H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3572 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3573 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3574 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3575 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3576 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3577 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3578 CH.sub.2 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3579 CH.sub.2 CH.sub.3 C(O)H H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3580 CH.sub.2 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3581 CH.sub.2 CH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3582 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3583 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3584 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3585 CH.sub.2 CH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3586 CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3587 CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3588 CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3589 CH.sub.2 CH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3590 CH.sub.2 CH.sub.3 C(O)H OCH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3591 CH.sub.2 CH.sub.3 C(O)H OCH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3592 CH.sub.2 CH.sub.3 C(O)H OCH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3593 CH.sub.2 CH.sub.3 C(O)H OH CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3594 CH.sub.2 CH.sub.3 C(O)H OH CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3595 CH.sub.2 CH.sub.3 C(O)H OH CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3596 OCH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3597 OCH.sub.3 C(O)H H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3598 OCH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3599 OCH.sub.3 C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3600 OCH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3601 OCH.sub.3 C(O)H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3602 OCH.sub.3 C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3603 OCH.sub.3 C(O)H CH.sub. 3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3604 OCH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3605 OCH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3606 OCH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3607 OCH.sub.3 C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3608 OCH.sub.3 C(O)H OCH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3609 OCH.sub.3 C(O)H OCH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3610 OCH.sub.3 C(O)H OCH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3611 OH C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3612 OH C(O)H H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3613 OH C(O)H H CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3614 OH C(O)H H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub. 2 CH.sub.3 CH.sub.3615 OH C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3616 OH C(O)H CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3617 OH C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3618 OH C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3619 OH C(O)H CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH(CH.sub.3).sub.2 CH.sub.3620 OH C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3621 OH C(O)H CH.sub.2 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3622 OH C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3623 OH C(O)H CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3624 CH.sub.3 C(O)H OCH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3625 CH.sub.3 C(O)H OCH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3626 CH.sub.3 C(O)H OCH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3627 CH.sub.3 C(O)H OH CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.3628 CH.sub.3 C(O)H OH CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3 CH.sub.3629 CH.sub.3 C(O)H OH CH.sub.3 CH.sub.3 CH.sub.3 CH.sub.2 CH.sub.3 CH.sub.3__________________________________________________________________________
The novel alkyl indane aldehyde compounds of the present invention, with their musk aroma properties, have high utility in the fragrance industry. These compounds can be employed alone, in combination with one another, and/or in combination with one or more ingredients to provide excellent musk fragrance compositions. The compounds of the invention are particularly useful in rounding off compositions, and blend particularly well with aldehydes of various fragrance types.
For example, the compounds of Formula [I] may be used as olfactory components in anionic, cationic, nonionic and zwitterionic detergents, soaps, fabric softener compositions, fabric softener articles for use in clothes dryers, space odorants and deodorants, perfumes, colognes, toilet water, toiletries, bath preparations, deodorants, cosmetics, hand lotions, sunscreens, powders, as well as in other ways. The amount of the subject compounds to be used in modifying the olfactory or fragrance properties of a composition (that is, modifying, augmenting, enhancing, or improving the aroma of such compositions), will vary depending upon the particular use intended, as will be readily apparent to those skilled in the art. Although they may be present in major or minor amounts, preferably, because of the strength of their odor, the compounds of the invention are generally employed as a minor ingredient, that is, in an amount of about 0.1 percent by weight of the fragrance composition up to about 50 percent by weight of the fragrance composition, preferably about 0.1 percent by weight up to about 30 percent by weight of the fragrance composition, and most preferably about 0.1 percent by weight up to about 5.0 percent by weight of the fragrance composition. Within these basic parameters, the olfactorily effective amount (that is, the amount of the compounds of Formula [I] effective to modify, augment, enhance or improve the aroma properties of a composition) will be well within the ambit of one skilled in the art, once armed with the present disclosures.
The fragrance compositions of the invention may, if desired, contain a carrier or vehicle (as used herein, the term "carrier" shall be considered synonymous with the term "vehicle"). Such carriers include liquids such as a non-toxic alcohol, a non-toxic glycol, or the like. An example of a non-toxic alcohol is ethyl alcohol. An example of a non-toxic glycol is 1,2-propylene glycol. Alternatively, the carrier can be an absorbent solid such as a gum, e.g., gum arabic, xantham gum or guar gum, or components for encapsulating a composition such as gelatin, by means of coacervation or such as a urea formaldehyde polymer whereby a polymeric shell is formed around a liquid perfume oil center. The amount of the vehicle or carrier will vary depending upon the particular vehicle or carrier employed and use intended, as will be readily apparent to those skilled in the art. However, the vehicle or carrier can generally be employed in an amount of about 5 percent by weight up to about 95 percent by weight of the fragrance composition.
The fragrance composition may alternatively or additionally contain other perfumery materials. Typical additional perfumery materials which may form part of compositions of the invention include: natural essential oils such as lemon oil, mandarin oil, clove leaf oil, petitgrain oil, cedar wood oil, patchouli oil, lavandin oil, neroli oil, ylang oil, rose absolute or jasmine absolute; natural resins such as labdanum resin or olibanum resin; single perfumery chemicals which may be isolated from natural sources or manufactures synthetically, as for example, alcohols such as geraniol, nerol, citronellol, linalol, tetrahydrogeraniol, .beta.-phenylethyl alcohol, methyl phenyl carbinol, dimethyl benzyl carbinol, menthol or cedrol; acetates and other esters derived from such alcohols; aldehydes such as citral, citronellal, hydroxycitronellal, lauric aldehyde, undecylenic aldehyde, cinnamaldehyde, amyl cinnamic aldehyde, vanillin or heliotropin; acetals derived from such aldehydes; ketones such as methyl hexyl ketone, the ionones and the methylionones; phenolic compounds such as eugenol and isoeugenol; other synthetic musks such as musk xylene, musk ketone, hexamethylisochroman, 5-acetyl-isopropyltetramethylindane, 6-acetyl-hexamethyltetralin (TETRALIDE.RTM., a registered trademark of Bush Boake Allen Limited), 5-acetyl-hexamethylindane and ethylene brassylate; and other materials commonly employed in the art of perfumery. Typically at least five, and usually at least ten, of such materials will be present as components of the active ingredient. The amount of the additional perfumery material will vary depending upon the particular perfumery material employed and use intended, as will be apparent to those skilled in the art.
Fragrance compositions and preparatory techniques are well known in the art, and are disclosed, for example, in "Soap, Perfumery and Cosmetics", by W. A. Poucher, 7th edition, published by Chapman & Hall (London) (1959); "Perfume and Flavour Chemicals", by S. Arctander, published by the author (Montclair) (1959); and "Perfume and Flavour Materials of Natural Origin", also by S. Arctander, self-published (Elizabeth, N.J.) (1960), the disclosures of each of which are incorporated herein by reference, in their entirety.





The invention is further described in the following Examples 1-6, which are prophetic examples illustrating methods of preparation for compounds of the present invention.
Example 1 describes the preparation of 5-formyl-1-isopropyl-2,3,3,4,6-pentamethylindane, a compound of Formula [I] wherein R.sub.1 is CH.sub.3, R.sub.2 is C(O)H, R.sub.3 is CH.sub.3, R.sub.4 is CH(CH.sub.3).sub.2, R.sub.5 is H, R.sub.6 is CH.sub.3, R.sub.7 is CH.sub.3, and R.sub.8 is CH.sub.3.
Example 2 describes the preparation of 5-formyl-1-isopropyl-2,3,3,6-tetramethylindane, a compound of Formula [I] wherein R.sub.1 is H, R.sub.2 is C(O)H, R.sub.3 is CH.sub.3, R.sub.4 is CH(CH.sub.3).sub.2, R.sub.5 is H, R.sub.6 is CH.sub.3, R.sub.7 is CH.sub.3, and R.sub.8 is CH.sub.3.
Example 3 describes the preparation of 5-formyl-1-isopropyl-2,3,3,6-tetramethyl-4-methoxyindane, a compound of Formula [I] wherein R.sub.1 is OCH.sub.3, R.sub.2 is C(O)H, R.sub.3 is CH.sub.3, R.sub.4 is CH(CH.sub.3).sub.2, R.sub.5 is H, R.sub.6 is CH.sub.3, R.sub.7 is CH.sub.3, and R.sub.8 is CH.sub.3.
Example 4 describes the preparation of 5-formyl-1-isopropyl-2,3,3,4-tetramethyl-6-methoxyindane, a compound of Formula [I] wherein R.sub.1 is CH.sub.3, R.sub.2 is C(O)H, R.sub.3 is OCH.sub.3, R.sub.4 is CH(CH.sub.3).sub.2, R.sub.5 is H, R.sub.6 is CH.sub.3, R.sub.7 is CH.sub.3, and R.sub.8 is CH.sub.3.
Example 5 describes the preparation of 5-formyl-1,1,2,3,3,4-hexamethyl-6-methoxyindane, a compound of Formula [I] wherein R.sub.1 is CH.sub.3, R.sub.2 is C(O)H, R.sub.3 is OCH.sub.3, R.sub.4 is CH.sub.3, R.sub.5 is CH.sub.3, R.sub.6 is CH.sub.3, R.sub.7 is CH.sub.3, and R.sub.8 is CH.sub.3.
Example 6 describes the preparation of 5-formyl-1,1,2,3,3,6-hexamethyl-4-methoxyindane, a compound of Formula [I] wherein R.sub.1 is OCH.sub.3, R.sub.2 is C(O)H, R.sub.3 is CH.sub.3, R.sub.4 is CH.sub.3, R.sub.5 is CH.sub.3, R.sub.6 is CH.sub.3, R.sub.7 is CH.sub.3, and R.sub.8 is CH.sub.3.
These examples are intended to be illustrative only, and are not to be construed as limiting the scope of the appended claims.
EXAMPLE 1
Preparation of 5-Formyl-1-Isopropyl-2,3,3,4,6-Pentamethylindane
Isopropylmagnesium chloride (2.0M, 100 ml, 0.2 moles) (which may be obtained from Aldrich Chemical Company, Inc., Milwaukee, Wis.) in ether is added at room temperature to a 250 ml four-necked round bottom flask equipped with an air stirrer, septum, Claisen adapter (thermocouple and dry ice condenser attached) and nitrogen inlet tube. To this is then slowly added 3,5-dimethylbenzaldehyde (24.46 g) (which may be obtained from Lancaster Synthesis, Inc., Windham, N.H.). After about 2 hours, an aliquot of additional Grignard (20 ml) is added. The solution is then heated at 60.degree. C. for about one hour, and quenched with aqueous NH.sub.4 Cl. The aqueous layer is then washed several times with methyl tert-butyl ether and rotoevaporated to yield a crude product mixture containing 2-methyl-1-[3',5'-dimethylphenyl]-1-propanol. The product mixture is then fractionated under reduced pressure to further purify the 2-methyl-1-[3',5'-dimethylphenyl-1-propanol compound.
Next, 2-methyl-1-[3',5'-dimethylphenyl-1-propanol is converted to 1-isopropyl-2,3,3,4,6-pentamethylindane by following procedures similar to those described in European Patent Application Publication No. 0 393 742. Specifically, to a stirred solution of 10 ml TiCl.sub.4, in 120 ml dichloromethane which has been cooled to -5.degree. C. under nitrogen, is added a mixture of 17.8 g 2-methyl-1-[3',5'-dimethylphenyl-1-propanol, and 14.0 g 2-methyl-2-butene over a two hour period. The reaction mixture is stirred for a further 30 min at -5.degree. C. Thereafter, it is poured into a mixture of 200 ml water and 100 ml concentrated hydrochloric acid and stirred for 15 min. The organic phase is separated and the aqueous phase washed with brine with 50 ml dichloromethane. The combined organic phase is washed twice with 100 ml 10% hydrochloric acid solution, once with 100 ml water, twice with 100 ml 5% sodium carbonate solution, and finally, once again, with water. Solvent is then removed, yielding 1-isopropyl-2,3,3,4,6-pentamethylindane, which is further purified using reduced pressure fractional distillation techniques.
The compound 1-isopropyl-2,3,3,4,6-pentamethylindane is then treated as follows to yield 5-formyl-1-isopropyl-2,3,3,4,6-pentamethylindane. Specifically, 1-isopropyl-2,3,3,5,6-pentamethylindane (12.96 g) is placed in a 1 liter three-necked round bottom flask equipped with a reflux condenser, a stirrer and a dropping funnel. In accordance with the general procedures described in Organic Syntheses, Collective Vol. 5, pp. 49-50, by A. Rieche, H. Gross, and E. Hoft, edited by H. E. Baumgarten, John Wiley and Sons (New York, N.Y. 1973), methylene chloride (37.5 ml) is added to the flask. The solution is then cooled in an ice bath, and titanium tetrachloride (19.0 g) is added over a period of about 3 minutes. While the solution is stirred and cooled, .alpha.,.alpha.-dichloromethyl methyl ether (5.75 g) is added dropwise over a 25 minute period. After the addition is complete, the mixture is stirred for about 5 minutes in the ice bath, for about 30 minutes without cooling, and for about 15 minutes at about 35.degree. C. The reaction mixture is then poured into a separatory funnel containing about 50 g of crushed ice and is shaken thoroughly. The organic layer is separated, and the aqueous solution is extracted with two 10 ml portions of methylene chloride. The combined organic solution is washed three times with 10 ml portions of water. A crystal of hydroquinone is added to the methylene chloride solution, which is then dried over anhydrous sodium sulfate. After evaporation of the solvent, the residue is distilled to yield, as a crude product, 5-formyl-1-isopropyl-2,3,3,4,6-pentamethylindane. The 5-formyl-1-isopropyl-2,3,3,4,6-pentamethylindane is then further purified using standard fractional distillation techniques.
EXAMPLE 2
Preparation of 5-Formyl-1-Isopropyl-2,3,3,6-Tetramethylindane
Isopropylmagnesium chloride (2.0M, 100 ml, 0.2 moles) (which may be obtained from Aldrich Chemical Company, Inc., Milwaukee, Wis.) in ether is added at room temperature to a 250 ml four-necked round bottom flask equipped with an air stirrer, septum, Claisen adapter (thermocouple and dry ice condenser attached) and nitrogen inlet tube. To this is then slowly added meta-tolualdehyde (24.46 g). After about 2 hours, an aliquot of Grignard (20 ml) is added. The reaction is then heated at 60.degree. C. for about one hour, and quenched with aqueous NH.sub.4 Cl. The aqueous layer is then washed several times with methyl tert-butyl ether and rotoevaporated to yield a crude product mixture containing 2-methyl-1-[3'-methylphenyl]-1-propanol. The product mixture is then fractionated under reduced pressure further purify 2-methyl-1-[3'-methylphenyl]-1-propanol. The compound 2-methyl-1-[3'-methylphenyl]-1-propanol is then converted to 1-isopropyl-2,3,3,6-tetramethylindane by following the procedures of Example 1.
The compound 1-isopropyl-2,3,3,6-tetramethylindane is then treated as described in Example 1 to yield 5-formyl-1-isopropyl-2,3,3,6-tetramethylindane.
EXAMPLE 3
Preparation of 5-Formyl-1-Isopropyl-2,3,3,6-Tetramethyl-4-Methoxyindane
Isopropylmagnesium chloride (2.0M, 100 ml, 0.2 moles) (which may be obtained from Aldrich Chemical Company, Inc., Milwaukee, Wis.) in ether is added at room temperature to a 250 ml four-necked round bottom flask equipped with an air stirrer, septum, Claisen adapter (thermocouple and dry ice condenser attached) and nitrogen inlet tube. To this is then slowly added 3-methoxy-5-methyl benzaldehyde (24.46 g), which may be prepared in accordance with the procedures of Syper, Tetrahedron Letters, No. 37, pp. 4493-4498 (1966). After about 2 hours, an aliquot of Grignard (20 ml) is added. The solution is then heated at 60.degree. C. for about one hour, and quenched with aqueous NH.sub.4 Cl. The aqueous layer is then washed several times with methyl tert-butyl ether and rotoevaporated to yield a crude product mixture containing 2-methyl-1-[3'-methoxy-5'-methylphenyl]-1-propanol. The product mixture is then fractionated under reduced pressure to further purify 2-methyl-1-[3'-methoxy-5'-methylphenyl]-1-propanol.
The compound 2-methyl-1-[3'-methoxy-5'-methylphenyl]-1-propanol is then converted to a mixture of 1-isopropyl-2,3,3,6-tetramethyl-4-methoxyindane and 1-isopropyl-2,3,3,4-tetramethyl-6-methoxyindane by following the procedures of Example 1. The mixture of indanes is then subjected to vacuum spinning band distillation techniques to separate out the 1-isopropyl-2,3,3,6-tetramethyl-4-methoxyindane compound.
The 1-isopropyl-2,3,3,6-tetramethyl-4-methoxyindane compound is then treated as described in Example 1 to yield 5-formyl-1-isopropyl-2,3,3,6-tetramethyl-4-methoxyindane.
EXAMPLE 4
Preparation of 6-Formyl-1-Isopropyl-2,3,3,4-Tetramethyl-5-Methoxyindane
The procedures of Example 3 are substantially carried out, except that the compound 1-isopropyl-2,3,3,4-tetramethyl-6-methoxyindane is isolated from the indane mixture using vacuum spinning band distillation techniques for further use.
The compound 1-isopropyl-2,3,3,4-tetramethyl-6-methoxyindane is then treated as described in Example 1 to yield 6-formyl-1-isopropyl-2,3,3,4-tetramethyl-5-methoxyindane.
EXAMPLE 5
Preparation of 5-Formyl-1,1,2,3,3,4-Hexamethyl-6-Methoxyindane
Methylmagnesium bromide (3.0M, 100 ml) (which may be obtained from Aldrich Chemical Company, Inc., Milwaukee, Wis.) in ether is added at room temperature to a 250 ml four-necked round bottom flask equipped with an air stirrer, septum, Claisen adapter (thermocouple and dry ice condenser attached) and nitrogen inlet tube. To this is then slowly added a mixture of 2,3-dimethyl-4-methoxyacetophenone and 3,4-dimethyl-2-methoxyacetophenone (24.46 g). The mixture of acetophenones may be prepared using the Perrier modification (CH.sub.3 C(O)Cl, aluminum chloride and methylene chloride) in accordance with the procedures of Perrier, Chem. Ber., Vol. 33, pp. 819 et seq. (1900), and Perrier, Bull. Soc. Chim. France, pp. 859 et seq. (1904). After about 2 hours, an aliquot of additional Grignard (20 ml) is added. The solution is then heated at 60.degree. C. for about one hour, and quenched with aqueous NH.sub.4 Cl. The aqueous layer is then washed several times with methyl tert-butyl ether and rotoevaporated to yield a crude product mixture containing 1-methyl-1-[2'-methoxy-3',4'-dimethylphenyl]-ethanol or 1-methyl-1-[4'-methoxy-2',3'-dimethylphenyl]-ethanol. The product mixture is then subjected to spinning band distillation procedures to separate out the 1-methyl-1-[4'-methoxy-2',3'-dimethylphenyl]-ethanol compound. The compound 1-methyl-1-[4'-methoxy-2',3'-dimethylphenyl]-ethanol is then converted to 1,1,2,3,3,4-hexamethyl-6-methoxyindane by following the procedures of Example 1.
The 1,1,2,3,3,4-hexamethyl-6-methoxyindane (10.8 g) is then heated with copper(II) sulfate pentahydrate (18.04 g) and potassium peroxydisulfate (60.55 g) in acetonitrile and water (1:1, 500 ml) at reflux for about 15 to 20 minutes, following procedures similar to those described in Hauser et al., Synthesis, pp. 723-724 (1987). The mixture is then cooled to room temperature and methylene chloride (150 ml) is added. The layers are separated and the aqueous phase is further extracted with additional methylene chloride (2.times.70 ml). The combined organic solutions are dried with anhydrous sodium sulfate, filtered, and evaporated at reduced pressure to yield 5-formyl-1,1,2,3,3,4-hexamethyl-6-methoxyindane.
EXAMPLE 6
Preparation of 5-Formyl-1,1,2,3,3,6-Hexamethyl-4-Methoxyindane
The procedures of Example 5 are substantially carried out, except that the compound 1-methyl-1-[2'-methoxy-3',4'-dimethylphenyl]-ethanol is isolated from the indane mixture using standard fractional distillation techniques, and used to prepare 1,1,2,3,3,6-hexamethyl-4-methoxyindane.
The compound 1,1,2,3,3,6-hexamethyl-4-methoxyindane is then treated as described in Example 5 to yield 5-formyl-1,1,2,3,3,6-hexamethyl-4-methoxyindane.
The disclosures of each patent and publication cited or described herein are hereby incorporated herein by reference, in their entirety.
Various modifications of the invention, in addition to those shown and described herein, will be readily apparent to those skilled in the art from the foregoing description. Such modifications are also intended to fall within the scope of the appended claims.
Claims
  • 1. A compound of the formula: ##STR6## wherein R.sup.1 is H, CH.sub.3, CH.sub.2 CH.sub.3, OCH.sub.3 or OH,
  • R.sup.2 and R.sup.3 are, independently, H, CH.sub.3, CH.sub.2 CH.sub.3, OCH.sub.3, OH or C(O)H,
  • R.sup.4 and R.sup.7 are, independently, H, CH.sub.3, CH.sub.2 CH.sub.3 or CH(CH.sub.3).sub.2,
  • R.sup.5 and R.sup.8 are, independently H or CH.sub.3, and
  • R.sup.6 is H, CH.sub.3 or CH.sub.2 CH.sub.3, provided that
  • (i) one of R.sup.2 and R.sup.3 is C(O)H, and one of R.sup.2 and R.sup.3 is other than C(O)H,
  • (ii) when R.sup.1 is H, then R.sup.2 and R.sup.3 are other than OCH.sub.3 or OH,
  • (iii) when R.sup.1 is other than H, then R.sup.7 is CH.sub.3 or CH.sub.2 CH.sub.3,
  • (iv) no more than one of R.sup.4, R.sup.6 and R.sup.7 is CH.sub.2 CH.sub.3 or CH(CH.sub.3).sub.2,
  • (v) no more than one of R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 is H,
  • (vi) when each of R.sup.1, R.sup.3, R.sup.4 and R.sup.5 are CH.sub.3, then R.sup.8 is H,
  • (vii) when R.sup.4 is CH(CH.sub.3).sub.2, then at least one of R.sup.5 or R.sup.6 is H,
  • (viii) when R.sup.7 is CH(CH.sub.3).sub.2, then at least one of R.sup.6 or R.sup.8 is H,
  • (ix) when R.sup.1 is OCH.sub.3, then R.sup.2 and R.sup.3 are other than OH,
  • (x) when R.sup.1 is OH, then R.sup.2 and R.sup.3 are other than OH or OCH.sub.3,
  • (xi) when R.sup.1 is H, R.sup.4 is CH(CH.sub.3).sub.2 and R.sup.5 is CH.sub.3, then one of R.sup.2 and R.sup.3 is CH.sub.2 CH.sub.3,
  • (xii) when R.sup.1 is H, R.sup.7 is CH(CH.sub.3).sub.2 and R.sup.8 is CH.sub.3, then one of R.sup.2 and R.sup.3 is CH.sub.2 CH.sub.3,
  • (xiii) when R.sup.1 is H, R.sup.7 is CH(CH.sub.3).sub.2 and R.sup.8 is H, then R.sup.3 is C(O)H,
  • (xiv) when R.sup.1 is H, R.sup.4 is CH(CH.sub.3).sub.2 and R.sup.5 is H, then R.sup.2 is C(O)H,
  • (xv) when R.sup.1 is H, R.sup.7 is CH.sub.2 CH.sub.3 and R.sup.4, R.sup.5 and R.sup.8 is CH.sub.3, then both of R.sup.2 and R.sup.3 are other than CH.sub.3,
  • (xvi) when R.sup.1 is H, R.sup.4 is CH.sub.2 CH.sub.3 and R.sup.5, R.sup.7 and R.sup.8 is CH.sub.3, then both of R.sup.2 and R.sup.3 are other than CH.sub.3, and
  • (xvii) when one of R.sup.2 and R.sup.3 is CH.sub.3, and each of R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are CH.sub.3, then R.sup.1 is other than H.
  • 2. A compound of claim 1 wherein R.sup.2 is C(O)H.
  • 3. A compound of claim 1 wherein at least one of R.sup.1, R.sup.2 and R.sup.3 are independently OCH.sub.3 or OH.
  • 4. A compound of claim 3 wherein at least one of R.sup.1, R.sup.2 and R.sup.3 are OCH.sub.3.
  • 5. A compound of claim 1 wherein R.sup.1 is H, CH.sub.3, CH.sub.2 CH.sub.3 or OCH.sub.3, and R.sup.2 and R.sup.3 are, independently, H, CH.sub.3, CH.sub.2 CH.sub.3, OCH.sub.3 or C(O)H.
  • 6. A compound of claim 5 wherein R.sup.1 is H, CH.sub.3 or OCH.sub.3, and R.sup.2 and R.sup.3 independently are H, CH.sub.3, OCH.sub.3 or OC(O)H.
  • 7. A compound of claim 1 wherein at least one of R.sup.4 or R.sup.7 are H, CH.sub.3 or CH.sub.2 CH.sub.3.
  • 8. A compound of claim 1 wherein R.sup.4 and R.sup.7 are, independently, CH.sub.3, CH.sub.2 CH.sub.3 or CH(CH.sub.3).sub.2, and R.sup.5 and R.sup.8 are CH.sub.3.
  • 9. A compound of claim 8 wherein R.sup.6 is CH.sub.3 or CH.sub.2 CH.sub.3.
  • 10. A compound of claim 1 wherein R.sup.4 is CH(CH.sub.3).sub.2.
  • 11. A compound of claim 1 wherein R.sup.1 is CH.sub.3, R.sup.2 is C(O)H, R.sup.3 is OCH.sub.3, R.sup.4 is CH.sub.3, R.sup.5 is CH.sub.3, R.sup.6 is CH.sub.3, R.sup.7 is CH.sub.3 and R.sup.8 is CH.sub.3.
  • 12. A compound of claim 1 wherein R.sup.1 is OCH.sub.3, R.sup.2 is C(O)H, R.sup.3 is CH.sub.3, R.sup.4 is CH.sub.3, R.sup.5 is CH.sub.3, R.sup.6 is CH.sub.3, R.sup.7 is CH.sub.3 and R.sup.8 is CH.sub.3.
  • 13. A compound of claim 1 wherein R.sup.1 is CH.sub.3, R.sup.2 is C(O)H, R.sup.3 is CH.sub.3, R.sup.4 is CH.sub.2 CH.sub.3, R.sup.5 is CH.sub.3, R.sup.6 is H, R.sup.7 is CH.sub.3 and R.sup.8 is CH.sub.3.
  • 14. A compound of claim 1 wherein R.sup.1 is CH.sub.3, R.sup.2 is C(O)H, R.sup.3 is OCH.sub.3, R.sup.4 is CH.sub.2 CH.sub.3, R.sup.5 is CH.sub.3, R.sup.6 is H, R.sup.7 is CH.sub.3 and R.sup.8 is CH.sub.3.
  • 15. A compound of claim 1 wherein R.sup.1 is CH.sub.3, R.sup.2 is C(O)H, R.sup.3 is OCH.sub.3, R.sup.4 is CH.sub.3, R.sup.5 is CH.sub.3, R.sup.6 is H, R.sup.7 is CH.sub.2 CH.sub.3 and R.sup.8 is CH.sub.3.
  • 16. A compound of claim 1 wherein R.sup.1 is OCH.sub.3, R.sup.2 is C(O)H, R.sup.3 is CH.sub.3, R.sup.4 is CH.sub.2 CH.sub.3, R.sup.5 is CH.sub.3, R.sup.6 is H, R.sup.7 is CH.sub.3 and R.sup.8 is CH.sub.3.
  • 17. A compound of claim 1 wherein R.sup.1 is OCH.sub.3, R.sup.2 is C(O)H, R.sup.3 is CH.sub.3, R.sup.4 is CH.sub.3, R.sup.5 is CH.sub.3, R.sup.6 is H, R.sup.7 is CH.sub.2 CH.sub.3 and R.sup.8 is CH.sub.3.
  • 18. A compound of claim 1 wherein R.sup.1 is CH.sub.3, R.sup.2 is C(O)H, R.sup.3 is CH.sub.3, R.sup.4 is CH(CH.sub.3).sub.2, R.sup.5 is H, R.sup.6 is CH.sub.3, R.sup.7 is CH.sub.3 and R.sup.8 is CH.sub.3.
  • 19. A compound of claim 1 wherein R.sup.1 is CH.sub.3, R.sup.2 is C(O)H, R.sup.3 is OCH.sub.3, R.sup.4 is CH(CH.sub.3).sub.2, R.sup.5 is H, R.sup.6 is CH.sub.3, R.sup.7 is CH.sub.3 and R.sup.8 is CH.sub.3.
  • 20. A compound of claim 1 wherein R.sup.1 is OCH.sub.3, R.sup.2 is C(O)H, R.sup.3 is CH.sub.3, R.sup.4 is CH(CH.sub.3).sub.2, R.sup.5 is H, R.sup.6 is CH.sub.3, R.sup.7 is CH.sub.3 and R.sup.8 is CH.sub.3.
  • 21. A compound of claim 1 wherein R.sup.1 is OCH.sub.3, R.sup.2 is C(O)H, R.sup.3 is OCH.sub.3, R.sup.4 is CH(CH.sub.3).sub.2, R.sup.5 is H, R.sup.6 is CH.sub.3, R.sup.7 is CH.sub.3 and R.sup.8 is CH.sub.3.
  • 22. A compound of claim 1 wherein R.sup.1 is H, R.sup.2 is C(O)H, R.sup.3 is CH.sub.3, R.sup.4 is CH(CH.sub.3).sub.2, R.sup.5 is H, R.sup.6 is CH.sub.3, R.sup.7 is CH.sub.3 and R.sup.8 is CH.sub.3.
  • 23. A fragrance composition comprising a compound of claim 1 in combination with at least one of a carrier and additional perfumery material.
  • 24. A fragrance composition comprising a compound of claim 21 in combination with at least one of a carrier and additional perfumery material.
  • 25. A method of modifying the olfactory properties of a composition comprising adding thereto an olfactorily effective amount of a compound of claim 1.
  • 26. A method of modifying the olfactory properties of a composition comprising adding thereto an olfactorily effective amount of a compound of claim 21.
  • 27. A product produced by the method of claim 25.
  • 28. A product produced by the method of claim 26.
RELATED APPLICATION

This application is a continuation-in-part of patent application U.S. Ser. No. 079,008, filed Jun. 18, 1993, now U.S. Pat. No. 5,292,720, the disclosures of which are hereby incorporated herein by reference in their entirety.

US Referenced Citations (35)
Number Name Date Kind
2800511 Carpenter Jul 1959
2897237 Carpenter Jul 1959
3244751 Theimer et al. Apr 1966
3246044 Wood et al. Apr 1966
3278622 Stofberg et al. Oct 1966
3379785 Kahn Apr 1968
3400159 Theimer et al. Sep 1968
3442640 Wood et al. May 1969
3509215 Wood et al. Apr 1970
3856875 Wood et al. Dec 1974
4018719 De Simone Apr 1977
4162256 Sprecker et al. Jul 1979
4284818 Sato et al. Aug 1981
4352748 Traas et al. Oct 1982
4406828 Gozenbach Sep 1983
4466908 Sprecker et al. Aug 1984
4551573 Cobb Nov 1985
4605778 Willis et al. Aug 1986
4652400 Sprecker Mar 1987
4767882 Suzukamo et al. Aug 1988
4877910 Frank Oct 1989
4877911 Frank Oct 1989
4877912 Frank Oct 1989
4877913 Frank Oct 1989
4877914 Frank Oct 1989
4877915 Frank Oct 1989
4877916 Frank Oct 1989
4880775 Christenson et al. Nov 1989
4908349 Gozenbach Mar 1990
5087770 Frank Feb 1992
5087785 Frank Feb 1992
5095152 Frank Mar 1992
5162588 Fehr et al. Nov 1992
5185318 Fehr et al. Feb 1993
5206217 Frank Apr 1993
Foreign Referenced Citations (7)
Number Date Country
0301375 Feb 1989 EPX
0393742 Oct 1990 EPX
0405427A2 Jan 1991 EPX
50-40761 Apr 1975 JPX
57-40420 Mar 1982 JPX
7802038 Aug 1978 NLX
1459036 Dec 1976 GBX
Non-Patent Literature Citations (29)
Entry
Muller and D. Lamparksy, Perfumes, Art, Science and Technology, Elsevier Science Publishing Co., Inc., New York, N.Y., pp. 254-310 (1991).
Bedoukian, Paul Z., Perfumery and Flavoring Synthetics, 3rd Revised Ed., pp. 334-336 (Allured Publishing Corp., Illinois 1986).
Bedoukian, Paul Z., Perfumery and Flavoring Synthetics, 2nd Revised Ed., pp. 248-292 (Elsevier Publishing Co., 1967).
Beets, Structure-Activity Relationships in Human Chemoreception, pp. 161-381 (Applied Science Publishers Ltd., London) (1973).
Carey et al., Advanced Organic Chemistry, Part B: Reactions and Sythesis, pp. 383-386 (Plenum Press, N.Y. 1977).
Effenberger, Electrophilic Reagents, Angewandte Chemie (Int. Ed. in English), vol. 19, No. 3, pp. 151-230 (1980).
Fehr et al., New Aromatic Musk Odorants: Design and Synthesis, Helvetica Chimica Acta, vol. 72, pp. 1537-1553 (1989).
Godfrey et al., Preparation of Methoxyphenols by Baeyer-Villiger Oxidation of Methoxybenzaldehydes, J. C. S. Perkin I, pp. 1353-1354 (1974).
Hannan et al., Synthesis of Bromonaphthoquinones from 1,5-Dimethoxynaphthalene, J. Org. Chem., vol. 44, No. 13, pp. 2153-2158 (1979).
Harrison et al., Compendium of Organic Synthetic Methods, pp. 84-85 (Wiley-Interscience, N.Y. 1971).
Hauser et al., Regiospecific Oxidation of Methyl Groups in Dimethylanisoles, Synthesis, pp. 723-724 (1987).
Huang et al., A Convenient Synthesis of Aryl Formatest, J. Chem. Research (Synop), pp. 292-293 (1991).
Imatoto et al., Cerium(IV) Trifluoromethanesulfonate as a Strong Oxidizing Agent, Chemistry Letters, pp. 1445-1446 (1990).
Kreh et al., Selective Oxidations With Ceric Methane-sulfonate and Ceric Trifluoromethanesulfonate, Tetrahedron Ltrs, vol. 28, No. 10, pp. 1067-1068 (1987).
Laing et al., Synthetic Steroids. Part IX. A New Route to 19-Nor-steroids, J. Chem. Soc. (C), pp. 2915-2918 (1968).
March, J., Advanced Organic Chemistry: Reactions, Mechanisms and Structure, 4th Ed., pp. 1098-1099, 1184-1185 (John Wiley & Sons, N.Y. 1992).
Nikaido et al., Acid-Catalyzed Oxidation of Benzaldehydes to Phenols by Hydrogen Peroxide, J. Org. Chem., vol. 49, pp. 4740-4741 (1984).
Olah et al., Formylating Agents, Chemical Reviews, vol. 87, No. 4, pp. 671-686 (1987).
Ohloff et al., Chemical Classification and Structure-Odour Relationships, Perfumes: Art, Science and Technology, pp. 287-330 (Amsterdam 1991).
Rahm et al., Acetone Cyanohydrin, A Convenient Formylation Reagent For Arenes, Synthetic Communications, vol. 12, No. 6,. pp. 485-487 (1982).
Rieche et al., Aromatic Aldehydes. Mesitaldehyde, Organic Syntheses, Collective vol. 5, pp. 49-50 (1973).
Syper, The Baeyer-Villiger Oxidation of Aromatic Aldehydes and Ketones with Hydrogen Peroxide Catalyzed by Selenium Compounds, Synthesis, pp. 167-172 (1989).
Syper, Partial Oxidation of Aliphatic Side Chains With Oerium (IV), Tetrahedron Letters, No. 37, pp. 4493-4498 (1966).
Syper, Silver (II) As An Oxidant For Organic Compounds, Tetrahedron Letters, No. 42, pp. 4193-4198 (1967).
Theimer, Fragrance Chemistry: The Science of the Sense of Smell, pp. 509-534 (Academic Press 1982).
French Patent No. 1,392,804 (as reported in Chemical Abstracts, 29-Essential Oils and Cosmetics, vol. 63, p. 6781 (1965)).
Chastrette, Importance of Hydrogen Bonding in the Recognition of Musky Odours, ECRO VIII: Abstracts, pp. 176-177 (1987).
Perrier, Chem. Ber., vol. 33, p. 815 et seq. (1990).
Perrier, Bull. Soc. Chim. France, p. 859 et seq. (1904).
Continuation in Parts (1)
Number Date Country
Parent 79008 Jun 1993