Methylcyclotetradec-5-en-1-ones

Details Methylcyclotetradec-5-en-1-ones Methylcyclotetradec-5-en-1-ones

1999-09-01

2001-12-04

Warden, Jill (Department: 1743)

Perfume compositions

Perfume compositions

Oxygen containing active ingredient

C512S008000, C512S025000, C512S027000, C568S375000

Reexamination Certificate

active

06326349

ABSTRACT:

FIELD OF THE INVENTION
The invention relates to methylcyclotetradec-5-en-1-ones and to scent compositions which include at least one methylcyclotetradec-5-en-1-one.
BACKGROUND OF THE INVENTION
G. Ohloff, Fortschritte der chemischen Forschung (Advances in Chemical Research, Vol. 12/2, 201) reportedly states that macrocyclic carbonyl compounds having more than 13, but fewer than 19, carbon atoms are involved in achieving a musk odor. However, all commercial musk scents have ring sizes of 15, 16 or 17 carbon atoms. Extremely little is known about the olfactory properties of fourteen-membered ring ketones, and only then in isolated cases.
For example, Mookherjee, et al., U.S. Pat. No. 4,183,965 reportedly discloses the use of a mixture of 2- and 3-cyclotetradecen-1-one for reducing the bitter taste of foods. The compounds may also be used in perfumery and have a sweet, musk-like, exaltone-like, waxy, rooty odor.
JP-A 55-66534 reportedly discloses the synthesis of 5-cis-cyclotetradecen-1-one having a musk-like character by heating 1-vinyl-3-cis-cyclododecen-1-ol with an alkali metal or alkali metal hydride. E. Yoshi and S. Kimoto: Chem. Pharm. Bull 17, 629, 1969 and, subsequently, M. Karpf and A. S. Dreiding: Helvetica Chimica Acta, Vol. 58(8), 2409, 1975, reportedly disclose the synthesis of a mixture of cis- and trans -3-methylcyclotetradec-2-en-1-ones and 3-methylcyclotetradec-3-en-1-ones. Olfactory properties of these compounds are not given.
R. W. Thies and K. P. Daruwala: J. Org. Chem. 1987, 52, 3798 reportedly disclose the preparation of 3-methyl-trans-cyclopentadec-5-enone by treatment of trans- or cis-1-(1-propenyl)-trans-cyclotridec-3-en-1-ol with potassium hydride in hexamethylphosphoramide.
Demole, et al., U.S. Pat. No. 5,354,735 reportedly discloses cis- and transisomers of 3-methylcyclopentadec-5-en-1-one as scent constituents having musk-like properties. The cis-isomer is stronger, more elegant, and has more of a musk odor and less of an animal odor than the trans-isomer, which has more of a nitromusk character and ambrette seed odor.
SUMMARY OF THE INVENTION
Accordingly, the present invention provides compounds of formula I:
wherein R
1
and R
2
are hydrogen or methyl, with the proviso that, when R
1
is methyl, R
2
is hydrogen, and when R
1
is hydrogen, R
2
is methyl.
The invention also provides scent compositions having at least one compound of formula I.
In addition, the present invention also provides processes for preparing organoleptic compositions. This process includes combining a compound according to formula I defined herein with a perfume or a consumer product.
DETAILED DESCRIPTION OF THE INVENTION
The present invention provides compounds of formula I:
wherein R
1
and R
2
are hydrogen or methyl, with the proviso that, when R
1
is methyl, R
2
is hydrogen, and when R
1
is hydrogen, R
2
is methyl. Unexpectedly, these compounds have a strong musk-like, i.e. nitromusk-like, powdery, fruity odor. These compounds also have a low threshold value and very good substantivity. The compounds of formula I may be in the Z- and/or in the E-form.
A preferred compound of formula I is E-3-methylcyclotetradec-5-en-1-one. Surprisingly, this compound has an odor which is more than ten times stronger than the corresponding Z-compound, Z-3-methylcyclotetradec-5-en-1-one. E-3-methylcyclotetradec-5-en-1-one has a gas-chromatographic threshold value of 0.2 ng/l while Z-3-methylcyclotetradec-5-en-1-one has one of 2.2 ng/l.
The compounds of formula I may, like other known musk scents, be used generally, i.e., they may be used to harmonize with a large number of natural and synthetic products which are frequently used in scent compositions. Particularly in the base note, compounds of formula I achieve interesting effects in combination with amber-like and woody accords, such as patchouli oil, cedarwood scent, and sandalwood scent. Floral body (middle) notes impart elegance and radiance to the compounds of formula I. Examples of different classes of substances that harmonize particularly well with the compounds of formula I include:
Natural products, such as oakmoss absolute, geranium oil, jasmine absolute, patchouli oil, rose oil, sandalwood oil, vetiverol, ylang ylang oil, and the like;
Alcohols, such as citronellol, EBANOL®, geraniol, linalool, phenyl ethyl alcohol, SANDALORE®, and the like;
Aldehydes and ketones, such as FLOROZONE® (3-(4-ethylphenyl)-2,2-dimethylpropional), HYDROXYCITRONELLAL ISO-E-SUPER®, ISORALDEIN®, maltol, methyl cedryl ketone, methylionone, vanillin, and the like;
Ethers and acetals, such as ambrox, geranyl methyl ether, rose oxide and SPIRAMBRENE® (2′,2′,3,7,7-pentamethyl-spiro[bicyclo[4. 1.0]heptan-2-5′-[1,3]dioxanel], and the like; and
Esters and lactones, such as BERRYFLOR®, &ggr;-decalactone, &ggr;-undecalactone, and the like.
The compounds of formula I may be used to prepare various compositions using a broad range of known scents and scent mixtures as indicated in the list set forth above.
The advantageous properties of the compounds of formula I permit broad and diverse use. For example, the compounds of formula I may be used in sweet oriental creations or in the fragrance trends “fougère,” “chypre” and “floral.”
Because of the low threshold values and good substantivity, the compounds of formula I may be used both in luxury perfumery, in compositions for cosmetic products, and for mass-produced products, such as detergents.
The compounds of formula I may be used within wide concentration limits, that may range, for example, from about 0.1% by weight in detergents to about 40% by weight in alcoholic solutions. Preferred concentrations of the compounds of formula I range between 3 and 20% by weight. Concentrations outside these limits, however, are also possible because the experienced perfumer may achieve novel effects using lower or higher concentrations.
In the present invention, compositions which include one or more of the compounds of formula I may be combined with all types of scent compositions including perfumes and perfumed consumer products, such as caux de cologne, eaux de toilette, extraits, lotions, creams, shampoos, soaps, ointments, powders, deodorants, detergents, other household products, and the like.
In the preparation of such compositions, the compounds of formula I may be used together with other scents or scent mixtures in a known manner, as described, for example, by W. A. Poucher, Perfumes, Cosmetics, Soaps, Vol. 2, 7th edition Chapman and Hall, London 1974.
The compounds of formula I may be prepared by various methods. For example, a compound of formula I in which R
1
is H and R
2
is CH
3
is prepared by the following method as a mixture with a compound of formula II:
i.e., a mixture of cis- and trans-4-methylcyclotetradec-6-en-1-one. In this method, (4-carboxy-3-methylbutyl)triphenylphosphonium bromide is subjected to a Wittig reaction, for example by treatment with potassium t-butoxide in tetrahydrofuran and subsequent addition of methyl 9-oxononanoate. The resulting product, dimethyl 3-methyltetradec-5-enedioate is subjected to an acyloin condensation and then treated with acetic anhydride/pyridine. The resulting mixture of mainly Z-4-methyl-2-oxocyclotetradec-6-enyl acetate and Z-3-methyl-14-oxocyclotetradec-5-enyl acetate is treated with calcium in ammonia at a low temperature (e.g., between about −30° C. to about −70° C.). The excess calcium is destroyed using bromobenzene.
This method produces a mixture of the following compounds:
E-3-methyl-cyclotetradec-5-enone 11%
Z-3-methyl-cyclotetradec-5-enone 35%
Z-4-methyl-cyclotetradec-6-enone 49%
These compounds have strongly musk-like (nitromusk), powder-like odors.
In the present invention, another example of a method for preparing a compound of formula I (R
1
═H, R
2
═CH
3
), preferably in the trans-form, begins with 2-chlorocyclododecanone or 2-bromocyclododecanone as starting materials. These compounds may be obtained in one stage from cyclododecanone (See, e.g., JP 491 093 39 and EP-A-0

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