Citral derivatives

Details Citral derivatives Citral derivatives

2007-12-18

2007-12-18

Dentz, Bernard (Department: 1625)

Organic compounds -- part of the class 532-570 series

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

Reexamination Certificate

active

10869626

ABSTRACT:
Improved citral derivatives, and fragrances and flavorings including the derivatives, that have a longer useful shelf life than citral and/or fragrances and flavorings including citral, are disclosed. In particular, the derivatives maintain the fragrance characteristics of citral, while lowering the allergic properties, and lemony flavors and fragrances with a longer shelf-life than citral, are disclosed. Also disclosed are methods of making the derivatives, and articles of manufacture including the derivatives. In one embodiment, the derivatives are prepared by replacing one or more double bonds in citral with a cyclopropyl group, which can be unsubstituted, or substituted with one or two lower alkyl, preferably methyl groups. The alkyl groups can optionally be substituted, for example, with electron donating groups, electron with drawing groups, groups which increase the hydrophilicity or hydrophobocity, and the like. In another embodiment, the derivatives are prepared by replacing the aldehyde group in citral with a nitrile, methyl ether or acetal group. The acetal groups can provide the compounds with a long lasting flavor or fragrance, where the acetals slowly hydrolyze to provide the aldehyde group in citral. In some embodiments, both the aldehyde and at least one of the double bond functional groups are both derivatized as described herein. Examples of suitable articles of manufacture include candles, air fresheners, perfumes, disinfectant compositions, hypochlorite (bleach) compositions, beverages such as beer and soda, denture cleanser tablets and flavored orally-delivered products such as lozenges, candies, and the like.

REFERENCES:
patent: 3549624 (1970-12-01), Conover et al.
patent: 3770836 (1973-11-01), Comes
patent: 3950429 (1976-04-01), Lamparsky et al.
patent: 4097531 (1978-06-01), Bledsoe, Jr. et al.
patent: 4151103 (1979-04-01), Evers et al.
patent: 4435428 (1984-03-01), Boden et al.
patent: 4521331 (1985-06-01), Martel et al.
patent: 4536583 (1985-08-01), Mookherjee et al.
patent: 4658067 (1987-04-01), Pittet et al.
patent: 6051548 (2000-04-01), Boden et al.
patent: 26 17 816 (1977-11-01), None
patent: 2617816 (1977-11-01), None
patent: 0 219 146 (1987-04-01), None
patent: 0 418 680 (1991-03-01), None
patent: 0 801 049 (1997-10-01), None
patent: 0 801 049 (1997-10-01), None
patent: 1.393.451 (1965-02-01), None
patent: 1 393 451 (1965-02-01), None
patent: 1393451 (1965-02-01), None
patent: 2 543 134 (1984-02-01), None
patent: 2 543 134 (1984-09-01), None
patent: 1061732 (1967-03-01), None
patent: 1 082 364 (1967-09-01), None
patent: 1082364 (1967-09-01), None
patent: 0 219 146 (1987-04-01), None
patent: 0 418 680 (1991-03-01), None
patent: 0 801 049 (1997-10-01), None
patent: WO 01/06853 (2001-02-01), None
patent: WO 01/06853 (2001-02-01), None
patent: WO 2001/006853 (2001-02-01), None
patent: WO 03/053901 (2003-07-01), None
patent: WO 03/053902 (2003-07-01), None
Masaki Y et al., “Substrate-specific rearrangement and acetonidation of epoxy-ethers catalyzed by tetracyanoethylene”, Chemistry Letters, No. 1, Jan. 1993, pp. 17-20, XP002224829.
Armstrong A et al., “Intramolecular Epoxidation in Unsaturated Ketones and Oxaziridines”, Journal of the Chemical Society, Perkin Transactions 1, No. 21, Nov. 1, 2001, pp. 2861-2873, XP002224830.
Schulte-Elte K H et al., “Photooxygenation of 3,3-dialkylsubstituted allyl alcohols, Occurrence of syn preference in the ene addition of1O2at E/Z isomeric allyl alcohols”, Helvetica Chimica Acta, vol. 62 No. 3, Apr. 20, 1979, pp. 816-829, XP002224831.
Scheller M E et al., “Syntheses of Cyclopropyl Silyl Ketones”, Helvetica Chimica Acta, vol. 68, No. 1, Feb. 5, 1986, pp. 44-52, XP002224832.
Rickards R W et al., “Synthesis of Four Stereoisomers of the Higher Dipteran Juvenile Hormone III Bisepoxide”, Tetrahedron Letters, vol. 33, No. 52, Dec. 22, 1992, pp. 8137-8140, XP002224833.
Calo V et al., “Enantiomeric Selection via 1,3-Elimination. A Simultaneous Kinetic Resolution of Halohydrins and Epoxides”, Tetrahedron Letters, vol. 49, 1978, pp. 4963-4966, XP002224834.
Ziegler F E et al., “Carbon-Carbon Bond Forming Reactions with Oxiranyl Radicals”, Tetrahedron Letters, vol. 37, No. 35, Aug. 26, 1996, pp. 6299-6302, XP004030674.
Mori N et al., “Synthesis of (2R, 3R)-Epoxyneral, a Sex Pheromone of the Acarid Mite, Caloglyphus sp. (Astigmata: Acaridae)”, Tetrahedron Letters, vol. 36, No. 9, Feb. 27, 1995, pp. 1477-1478, XP004028605.
Sakaguchi S et al., “Selective Oxidation of Monoterpenes with Hydrogen Peroxide Catalyzed by Peroxotungstophosphate (PCWP)”, Journal of Organic Chemistry, vol. 61, No. 16, Aug. 9, 1996, pp. 5307-5311, XP002224835.
R. Jorritsma et al., “The chemistry of small ring compounds. Part 441. Solvolysis of cyclopropyl sulfides and ethers”, Recueil, Journal of the Royal Netherlands Chemical Society, 100/5, May 1981, p. 194-200.
T. Shirafuji et al., “The Reduction ofgem-Dibromocyclopropanes by Means or Chromium (II) Acetate or Potassium Pentacycanocobaltate”, Bulletin of the Chemical Society of Japan, vol. 44, No. 1, Nov. 1971, p. 3161-3164.
P. Grieco et al., “Construction of thegem-Dimethylcyclopropane Unit Employing Triphenylphosphonoium Isopropylide”, Tetrahedron Letters No. 36, 1972, p. 3781-3783. Pergamon Press. Printed in Great Britain.
D. Seebach et al., “Ringöffnung von Cyclopropanon-bis-methylthio-acetalen Zu Ketonen und Dimethyldisulfid in Trifluoressigsäure . . . ”, Tetrahedron Letters No. 36, 1973, pp. 3509-3512. Perfamon Press. Printed in Great Britain.
M. Julia et al., “No. 309.—Transposition homoallylique avec participation . . . ”, Bulletin de la Société Chimique de France 1970 No. 5, p. 1805-1815.
M. Julia et al., “No. 311.—Transposition homoallylique avec participation . . . ”, Bulletin de la Société Chimique de France 1970 No. 5, p. 1822-1833.
Abstract: Beilstein Registry No. 2087248, Copyright 1988-2003 Beilstein Institut zue Foerderung der Chemischen Wissenschaften.
Abstract: Beilstein Registry No. 2085216, Copyright 1988-2003 Beilstein Institut zue Foerderung der Chemischen Wissenschaften.
Weyerstahl P et al.: “Olfactory properties and convenient synthesis of furans and thiophenes related to rose furan and perillene and their isomers” Liebigs Annalen: Organic and Bioorganic Chemistry, vol. 10, Oct. 1, 1995 pp. 1849-1853, XP000608611.
Database Crossfire Beilstein Beilstein Institut zur Forderung der Chemischen Wissenschaften, Frankfurt am Main, DE; XP002233853.
Gagniant P et al: “Recherche dans la serie thiophenique. -1.-Etude de quelques acides omega.2-thienylaliphatiques de formule generate: C4H3S.(CH2)n.COOH” Bulletin De La Societe Chimique De France, 1948, pp. 1083-1087, XP002233849.
Tamaru Y et al: “The palladium catalyzed thienylation of allylic alcohols with 2- and 3-bromothiophenes and their derivatives” TETRAHEDRON, vol. 35, No. 3, 1979, pp. 329-340, XP002233850.
Arena G et al.: “Thermodynamics of protonation of some five-membered herteroaryl-carboxylates, -Alkannoates and—Trans-Propenoates”, Journal of the Chemical Society, Perkin Transations 2, No. 10, Oct. 1993 pp. 1941-1945-XP002233851.
Garrigues B et al: “Synthese de 2-tert-butylthiophenes substitutes en position 5” Bulletin De La Societe Chimique De France, vol. 130, No. 1, 1993, pp. 58-63, XP002233852.
Rabinowitz M H et al: “Design of selective and soluble inhibitors of tumor necrosis factor—alpha converting enzyme (TACE)” Journal of Medicinal Chemistry, vol. 44, No. 24, Nov. 22, 2001, pp. 4252-4267, XP002266978.
Tashtoush H I et al: “Free radical coupling of alkyl and aryl halides with electron-deficient alkenes mediated by chromium(II) complexes” Chemische Berichte, vol. 126, No. 7, Jul. 2, 1993, pp. 1759-1761.
Masaki Y et al: “Substrate-specific rearrangement and a

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