Perfume compositions – Perfume compositions – Oxygen containing active ingredient
Reexamination Certificate
2000-06-30
2002-07-16
Warden, Jill (Department: 1743)
Perfume compositions
Perfume compositions
Oxygen containing active ingredient
C512S008000, C512S009000, C512S011000, C512S013000, C512S026000, C512S027000, C549S330000, C549S331000, C549S356000, C549S381000, C549S385000, C549S386000, C549S396000, C549S397000, C549S398000, C549S414000
Reexamination Certificate
active
06420334
ABSTRACT:
FIELD OF THE INVENTION
Despite a large number of existing fragrances, there continues to be a need in the perfume industry for novel fragrances which as well as having their odoriferous properties additionally have positive secondary benefits, such as, for example, higher stability, better performance and effectiveness, better tenacity and long-lastingness.
SUMMARY OF THE INVENTION
We have found novel tetracyclic acetals of the two isomeric structures
in which
R is a lower alkyl.
DETAILED DESCRIPTION OF THE INVENTION
The acetals are particularly suitable as fragrances, which can be used in perfuming.
Lower alkyl generally represents methyl, ethyl, n-propyl, iso-propyl, n-butyl or isobutyl.
Particular preference is given to methyl and ethyl.
The novel tetracyclic acetals are prepared in a manner known per se starting from alpha-cedrene, which is reacted with acetic anhydride in the presence of titanium tetrachloride as a relatively strong Lewis acid. This forms, not as in the case of the reaction with acidic catalysts such as, for example, phosphoric acid, “acetylcedrene” (“methyl cedryl ketone”), a fragrance which has long been widely used in the prepa-ration of perfumes, but, with a structural rearrangement and the addition of water, the tricyclic hydroxyketone 1-(octahydro-8-hydroxy-3,6,7,7-tetramethyl-3 a,6-ethano-3aH-inden-5-yl)-ethanone which, upon heating and with the elimination of water, is gradually converted into the tetracyclic enol ether decahydro-2-methylene-3 a,4,4,7-tetramethyl-3,7a-methano-7aH-indeno[5,6-b]furan. By adding water to the enol ether, the hydroxy ketone readily reforms with ring opening (see also. J. Chem. Soc. Perkin Trans. I 1983, pp. 1373-78).
The hydroxy ketone is odorless in pure form; the enol ether has merely a weak odor reminiscent of the sesquiterpene hydrocarbon fraction of cedarwood oil (“Cedarwood oil terpenes”).
Surprisingly, we have now found that alcoholic solutions of both the hydroxy ketone and of the enol ether have a strong characteristic woody odor which is not a characteristic of the two pure compounds. We found that the reason for this lies in the formation of novel, as yet undescribed tetracyclic acetals. The formation of these acetals is described by the two equations below:
The acetals according to the present invention are generally in the form of the mixture of the two isomers.
Both isomers have a marked intensive and unusually long-lasting fresh woody odor.
Because of these particular organoleptic properties, these acetals are highly suitable for use as fragrance materials.
Details of how the preparation of the acetals according to the present invention are prepared are as follows:
The hydroxy ketone 1-(octahydro-8-hydroxy-3,6,7,7-tetramethyl-3a,6-ethano-3aH-inden-5-yl)-ethanone or the enol ether decahydro-2-methylene-3a,4,4,7-tetramethyl-3,7a-methano-7aH-indeno[5,6-b]furan or a mixture of the two is admixed with a lower alcohol, where, most preferably, the alcohol in question is used in excess and also serves as solvent. It is, however, also possible to add another inert solvent. The reaction can be carried out in a wide temperature range, e.g. between −25° and +150° C., optionally under pressure. Preference is given to a temperature range between 20° and 80° C.
After the excess alcohol, or other solvent, has been distilled off, the acetals according to the present invention are obtained as residues; where appropriate, the alcoholic solution can also be reused directly.
The acetals according to the present invention can be used as individual substances in a large number of products; it is particularly advantageous to combine them with other fragrance materials to give new types of perfume compositions.
By using the acetals according to the present invention it is generally possible to achieve, even at a low concentration, radiantly fresh, woody odor notes in the resulting perfume compositions, where the overall olfactory impression is harmonized to a striking degree, the radiance is perceptibly increased and the long-lastingness of the perfume oil is significantly increased.
Examples of fragrances with which the acetals according to the present invention can be advantageously combined can be found, for example, in S. Arctander, Perfume and Flavor Materials, Vols. I and II, Montclair, N.J., 1969, published privately or K. Bauer, D. Garbe and H. Surburg, Common Fragrance and Flavor Materials, 3
rd
Ed., Wiley-VCH, Weinheim 1997.
Individual examples which may be mentioned are:
Extracts from natural raw materials such as essential oils, concretes, absolutes, resins, resinoids, balsams, tinctures, such as, for example, ambergris tincture; amyris oil; angelica seed oil; angelica root oil; anise seed oil; valerian oil; basil oil; tree moss absolute; bay oil; armoise oil; benzoin resin; bergamot oil; beeswax absolute; birch tar oil; bitter almond oil; savoury oil; bucco leaf oil; cabreuva oil; cade oil; calmus oil; camphor oil; cananga oil; cardamom oil; cascarilla oil; cassia oil; cassie absolute; castoreum absolute; cedar leaf oil; cedarwood oil; cistus oil; citronella oil; lemon oil; copaiva balsam; copaiva balsam oil; coriander oil; costus root oil; cumin oil; cypress oil; Davana oil; dill herb oil; dill seed oil; eau de brouts absolute; oakmoss absolute; elemi oil; estragon oil; eucalyptus citriodora oil; eucalyptus oil; fennel oil; spruce needle oil; galbanum oil; galbanum resin; geranium oil; grapefruit oil; guaiacwood oil; gurjun balsam; gurjun balsam oil; helichrysum absolute; helichrysum oil; ginger oil; iris root absolute; iris root oil; jasmine absolute; calamus oil; camomile blue oil; camomile Roman oil; carrot seed oil; cascarilla oil; pine needle oil; spearmint oil; caraway oil; labdanum oil; labdanum absolute; labdanum resin; lavandin absolute; lavandin oil; lavender absolute; lavender oil; lemongrass oil; lovage oil; distilled lime oil; expressed lime oil; rosewood oil; litsea cubeba oil; laurel leaf oil; mace oil; marjoram oil; mandarin oil; massoi bark oil; mimosa absolute; ambrette seed oil; musk tincture; clary sage oil; nutmeg oil; myrrh absolute; myrrh oil; myrtle oil; clove leaf oil; clove bud oil; neroli oil; olibanum absolute; olibanum oil; opopanax oil; orange-flower absolute; orange oil; origanum oil; palmarosa oil; patchouli oil; perilla oil; peru balsam oil; parsley leaf oil; parsley seed oil; petitgrain oil; peppermint oil; pepper oil; pimento oil; pine oil; pennyroyal oil; rose absolute; rosewood oil; rose oil; rosemary oil; sage oil Dalmatian; sage oil Spanish; sandalwood oil; celery seed oil; spike lavender oil; star anise oil; styrax oil; tagetes oil; fir needle oil; teatree oil; turpentine oil; thyme oil; Tolu balsam; tonka absolute; tuberose absolute; vanilla extract; violet leaf absolute; verbena oil; vetyver oil; juniper oil; wine lees oil; wormwood oil; wintergreen oil; ylang oil; hyssop oil; civet absolute; cinnamon leaf oil; cinnamon bark oil; and fractions thereof, or ingredients isolated therefrom;
individual fragrances from the group of hydrocarbons, such as, for example, 3-carene; &agr;-pinene; &bgr;-pinene; &agr;-terpinene; &ggr;-terpinene; p-cymene; bisabolene; camphene; caryophyllene; cedrene; famesene; limonene; longifolene; myrcene; ocimene; valencene; (E,Z)-1,3,5-undecatriene; of aliphatic alcohols, such as, for example, hexanol; octanol; 3-octanol; 2,6-dimethylheptanol; 2-methyl-2-heptanol, 2-methyl-2-octanol; (E)-2-hexenol; (E)- and (Z)-3-hexenol; 1-octen-3-ol; mixture of 3,4,5,6,6-pentamethyl-3/4-hepten-2-ol and 3,5,6,6-tetramethyl-4-methyleneheptan-2-ol; (E,Z)-2,6-nonadienol; 3,7-dimethyl-7-methoxyoctan-2-ol; 9-decenol; 10-undecenol; 4-methyl-3-decen-5-ol; of aliphatic aldehydes and acetals thereof, such as, for example, hexanal; heptanal; octanal; nonanal; decanal; undecanal; dodecanal; tridecanal; 2-methyloctanal; 2-methylnonanal; (E)-2-hexenal; (Z)-4-heptenal; 2,6-dimethyl-5-heptenal; 10-undecenal; (E)-4-decenal; 2-dodecenal; 2,6,10-trimethyl-5,9-undecadienal; heptanal diethyl acetal; 1,1-dimethoxy-2,2,5-trimethyl-4-hexene; citronellyl
Surburg Horst
Wörner Peter
Cheung Noland J.
Cole Monique T.
Gil Joseph C.
Haarmann & Reimer GmbH
Warden Jill
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