Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2001-03-23
2003-06-17
Owens, Amelia (Department: 1625)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C562S512000, C424S195110
Reexamination Certificate
active
06579992
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to a novel method for converting dihydrotagetone, a bifunctional acyclic monoterpene ketone, isolated from plant species of Tagetes species into coconut flavoured 5-isobutyl-3-methyl-4,5-dihydro-2(3H)-furanone with two chiral centres of formula (1). Interestingly, the compound (1) is found as a novel analogue of whisky lactone (also named as Querecus lactone or oak lactone) of formula (1a), which is contained, for example, in high quality alcoholic beverages (Napolean whisky, Jamaica and cognac etc), as fragrance ingredient, in insect pheromones and several natural products containing this structural moiety. Moreover coconut flavoured compound (1) is also an analogue of coconut aldehyde (&ggr;-nonalactone or aldehyde C-18, F.E.M.A. No. 2751) of formula (1b) which is responsible for flavouring a wide range of food stuffs including baked goods and confectionery.
The present invention also relates to 2,6-dimethyl-4-oxo-heptanoic acid of formula (3) not only as a precursor for the synthesis of whisky lactone of formula (1a) but also as a novel analogue of 2,6-dimethyl-5-oxo-heptanoic acid (a constituent of well known essential oil of
Mentha x piperita
) which has wide applications in flavouring food stuffs, soft and alcoholic beverages, perfumery and pharmaceutical industries.
BACKGROUND OF THE INVENTION
A wide-spread class of &ggr;-butyrolactones (also known as dihydro-2(3H)-furanone or 4-butanolide or tetrahydro-2-furanone) were first synthesized in 1884 via internal esterification of 4-hydroxybutyric acid. These important lactones exhibit very intensive and pleasant fruity aroma and can be easily transformed into other useful products e.g. furans, cyclopentenones, butenolides and pyrrolidones (Freudenberger, D., Wunder, F. and Fernholz, H., U.S. Pat. No. 4,096,156 (1978)). The butyrolactone moieties are found in many natural products (Gunatilaka, A. A. L., Surendra, K. S. and Thomson, R. H., Phytochemistry, 23(4) 929-931 (1984) and Drioli, S., Felluga, F., Forzato, C., Nitti, P., Pitacco, G. and Valentin, E., J. Org. Chem., 63, 2385-2388 (1998)), insect pheromones (Naoshima, Y., Ozawa, H., Kondo, H. and Hayashi, S., Agric. Biol. Chem., 47(7) 1431-1434 (1983); Kim, C. S., Datta, P. K., Hara, T., Itoh, E. and Horiike, M., Bioscience Biotechnology and Biochemistry, 63(1) 152-154 (1999)), antifungal substances and flavor components (Shinohara, T. and Watanabe, M., J. Agri. Chem. Soc. Jap., 53 (7) 219-225 (1979) and Buttery, R. G. and Ling, L. C., J Agric Food Chem., 46(7) 2764-2769 (1998)) and also occur in the essential oil bearing plants.
Although several methods are available for the synthesis of simple &ggr;-butyrolactone derivatives, however, synthesis of chiral centered biologically active &ggr;-butyrolactone (Hullot, P., Cuvigny, T., Larcheveque, M. and Normant, H., Can. J. Chem., 55, 266-273 (1977); Tamaru, Y., Hojo, M. and Yoshida, Z., J. Org. Chem., 56, 1099-1105 (1991); Daugan, A. and Brown, E., J. Nat. Prod., 54(1) 110-118 (1991); Hartmann, B., Kanazama, A. M., Depres, J. P. and Greene, A. E., Tetrahedron Lett. 34(24) 3875-3876 (1993); Ishibashi, F.; Taniguchi, E., Phytochemistry, 49(2) 613-622 (1998) and Noyori, R., Kitamura, M., Ohkuma, T., Saya, N. and Kumobayashi, H., U.S. Pat. No. 5,420,306 (1995)) and their analogues (Mangnus, E. M., Vliet, L. A.-van, Vandenput, D. A. L. and Zwanenburg, B., J. Agri. Food Chem., 40(7) 1222-1229 (1992); Belletire, J. L., Mahmoodi, N. O., J Nat. Prod., 55(2) 194-206 (1992) are tedious but even then the preparation of chiral &ggr;-butyrolactones are the subject of many synthetic schemes (Carretero, J. C., Rojo, J., Tetrahedron Lett., 33, 7407-7410 (992); Casey, M., Manage, A. C. and Murphy, P. J., Tetrahedron, 33, 965-968 (1992); Zschage, O. and Hoppe, D., Tetrahedron, 48, 5657-5666 (1992); Paulsen, H. and Hoppe, D., Tetrahedron, 48, 5667-5670 (1992); Chong, J. M. and Mar, E. K., Tetrahedron Lett., 31, 1981-1984 (1990) and Bachi, M. D. and Bosch, E. J., J. Org. Chem., 57, 4696-4705 (1992).
In particular, two chiral centered &ggr;-butyrolactones having substituents such as an alkyl or alkenyl group are in more demand and they exist as either cis and/or trans isomer in nature (Bryan, V. and Chan, T. H., Tetrahedron Lett., 37(30), 5341-5342 (1996)). For example, whisky lactone, chemically known as 5-butyl-4-methyl-dihydro-2(3H)-furanone (also known as 3-methyl-4-octanolide or 4-hydroxy-3-methyloctanoic acid lactone) (1a) is a natural optically active disubstituted butyrolactone which is widely recognized and it has been identified as the most valuable additive responsible for the flavor of high quality whisky, wine, cognac and scotch etc (Nishimura, K. and Masuda, M., J. Food Sci. 36, 819 (1971); Kepner, R. E., Webb, A. D. and Muller, C. J., Am. J. Enol. Viticult, 23, 144 (1972); Etienne, M. and Manfred, S., Tetrahedron Lett., 25(40), 4491-4494 (1984) and Pérez-coello, M. S., Sánchez, M. A., García, E., González-viñas, M. A., Sanz, J. and Cabezudo, M. D., J. Agri. Food Chem., 48, 885-889 (2000)). Whisky lactone (1a) (also known as oak lactone or Querecus lactone) is a diastereomer of 3-methyl-4-octanolides(5-butyl-4-methyl-dihydro-2(3H)-furanone) which is found in whisky, wine, brandy and in extract of oak barrels. This lactone is important constituent of aging flavour and have so far been considered to be formed during aging from unknown precursors in wood barrels (Chem Abstr. 114, 181996v, 1991) which finally contributes to the flavour impact of the oak. The effect of oak barrels on the quality of wines are also influenced by several factors such as tree age, growth rate of tree and barrel size etc (Towey, J. P. and Waterhouse, A. L., Am. J. Enol. Viticult, 47(1), 17-20 (1996)).
In particular, the quality of the alcoholic beverages is affected largely by the presence of whisky lactone which is produced during the aging process. A wine aged for a longer period of time is realized to be of higher quality and is further influenced by several factors such as climatological conditions, fermentation, distillation, maturation and blending (Plaza, E. G., Munoz, R. G., Roca, J. M. L. and Martinez, A., J. Agric., Food Chem., 48, 736-741 (2000)). One of the isomers of this interesting whisky lactone (1a) is identified for the first time in whisky by Soumalainen and Nykanen in 1969 (Soumalainen, H. and Nykänen, L., Nährungsmiddelindustrien, 23, 1-15 (1970), however, later on cis and trans isomers have been determined by several workers in matured cognac, Jamiaca rum and whiskies and found that the aroma threshold for the cis isomer is 92 ppb while for the trans-isomer is 460 ppb (Masuda, M. and Nishimura, K., Phytochemistry, 10, 1401-1402 (1971); Gunther, C. and Mosandl, A., Liebigs Ann. Chem. 2112-2122, (1986); Gunther, C. and Mosandl, A., Z. Lebensm. Unters. Forsch., 185, 1-4 (1987) and Maarse, H. and Berg F. V. D. In Understanding Natural flavours, edited by Piggott, J. R. and Paterson, A.; Blackie Academic & Professional, New York, pp. 243-267 (1994)). In fact, four stereoisomers of whisky lactone (1b) are known with the following taste and odor such as (3R,4R)-5-butyl-4-methyl-dihydro-2(3H)-furanone with sweet, fresh, bright coconut smell (in 10% ethanol) and creamy, soft, coconut taste (10 ppm in aqueous saccharin); (3S,4S)-5-butyl-4-methyl-dihydro-2(3H)-furanone with weak coconut note earthy, mouldy afterodor, hay note odor and herbaceous, reminiscent of coconut taste; (3S,4R)-furanone derivative with spicy clelery note, weak coconut, distinct green walnut note odor and sweet creamy fatty, reminiscent of coconut; (3R,4S)-furanone derivative with intensive coconut note, afterodor, reminiscent of celery odor and weak spicy, herbaceous taste (Schreier, P., In: Bioflavour '87, Analysis. Biochemistry Biotechnology, Proceedings of the International Conference, Würzburg, Federal Republic of Germany, Sep. 29-30, 1987, Walter de Gruyter, New York, 55-74, (1988) and Eric, M., Raymond, B., Christine, L. G. and Jean-Louis, P., J. Agric. Food Chem., 48, 4306-4309, (2000)). A mixture of cis- and trans
Dogra Ruchi
Joshi Bhupendra Prasad
Sinha Arun Kumar
Council of Scientific & Industrial Research
Owens Amelia
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