Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Patent
1992-08-27
1995-11-21
Ivy, C. Warren
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
549326, C07D30702
Patent
active
054688817
DESCRIPTION:
BRIEF SUMMARY
TECHNICAL FIELD
The present invention relates to a method of producing natural type cis-whiskey lactone contained in whiskey, wine, etc.
PRIOR ART
Whiskey lactone (3-methyl-4-octanolide) is one of the perfume components of whiskey and wine.
There are stereomers of the natural whiskey lactone, which are of the trans-type or cis-type in accordance with the configuration of the methyl group at the 3-position thereof and butyl group at 4-position thereof. As compared to trans-whiskey lactone [(3S,4R)-3-methyl-4-octanolide] (D), generally, a lower amount of cis-whiskey lactone [(3S,4S)-3-methyl-4-octanolide] (A) is contained, for example, in whiskey and wine. However, cis-whiskey lactone (A) is superior in perfume characteristics. ##STR2##
However, a means for selectively synthesizing natural type cis-whiskey lactone (A) having superior properties to those of the trans-type isomer (D) as described above has not been known.
DISCLOSURE OF THE INVENTION
It is the object of an present invention to provide a method of producing cis-whiskey lactone which is able to selectively and easily synthesize natural type cis-whiskey lactone.
In order to solve the above problem, the inventor carefully reviewed and paid attention to the fact that trans-whiskey lactone and cis-whiskey lactone differ only in the absolute configuration of the butyl group at the 4-position thereof, and determined that the trans-whiskey lactone can be converted to the cis-whiskey lactone by reversing the solid configuration of the butyl group at the 4-position, thereby completing the present invention.
The present invention comprises: A method of producing cis-whiskey lactone, comprising, [(3S,4R)-3-methyl-4-octanolide] represented by general formula (D) and adding an alkyl group to the hydrolyzed portion, thereby obtaining the 3,4-trans compound represented by general formula (C), compound in the presence of triphenylphosphine and azodicarboxylate, thereby obtaining 3,4-cis compound (B) presented by general formula (B), and the hydrolyzed compound, thereby obtaining 3,4-cis-whiskey lactone [(3S, 4S)-3-methyl-4-octanolide] (A) represented by general formula (A): ##STR3## wherein R represents a general alkyl group and R' represents a general acyl group.
The method of producing cis-whiskey lactone of the present invention will be described below in detail.
Trans-whiskey lactone (D) used as a starting substance in the present invention can be produced, for example, by a well-known producing method described in "Heterocycles No. 31, pp. 1585-1588 (1990)".
Hydrolysis of the lactone portion in step (a) can be achieved, for example, by using a solution of an alkali such as sodium hydroxide, or potassium hydroxide. As a result, the lactone ring of the trans-whiskey lactone is broken between the carbon at the 1-position of the lactone and oxygen, and trans compound (D.sub.2) as indicated in the following formula can be obtained. ##STR4##
In this formula, M represents an alkali metal.
Then, trans compound (D.sub.2) is made to react with, for example, an alkyl halide such as isopropyl bromide or butyl bromide in an appropriate solvent, thereby adding an alkyl group to the carbonyl group at the 1-position of compound (D.sub.2) and obtaining trans compound (C). The appropriate solvent to be used in this step is, for example, an organic solvent such as dimethyl formamide or dimethyl sulfoxide, but it is not particularly limited.
In the reverse reaction, i.e., Mitunobu reaction of the butyl group at the 4-position of trans compound (C) in the step (b), trans compound (C) obtained in step (a) is made to react with, for example, acetic acid, benzoic acid, or an acyl derivative thereof in the presence of triphenylphosphine and azodicarboxylate, in an appropriate solvent, thereby reversing the configuration of the butyl group at the 4-position of trans compound (C). As a result, cis compound (B) in which the butyl group at the 4-position thereof and the methyl group at the 3-position thereof mutually configured in the cis-type can be obtained. The appropriate so
REFERENCES:
patent: 3926947 (1975-12-01), Lipska
patent: 4994585 (1991-02-01), Koseki et al.
patent: 5112994 (1992-05-01), Koseki et al.
Mitsunobu (1981) Synthesis, vol. No. 1, pp. 1-28.
Gunther, et al. (1986) Liebigs Ann. Chem, pp. 2112-2122.
Salaun, et al. (1989) Tetrahedron vol. 45, No. 10, pp. 3151-3162.
Derwent Publications Ltd., Abstract of JP 63-068578 Mar. 1988.
Helvetica Chimica Acta--vol. 72 (1989) pp. 1362-1370.
Tetrahedron, vol. 30, pp. 3547-3552, Pergamon Press 1974.
Carbohydrate Research, 167 (1987) pp. 187-196.
Tetrahedron vol. 46, No. 1, pp. 231-243, 1990.
"Formal Total Synthesis of 1.beta.-Methylcarbapanem Via a Novel Route to Deoxylamino Sugars" J. Org. Chem. 1989, 54, pp. 2103-2212.
"Nature", No. 4192 Mar. 4, 1950, p. 369.
Liebigs Ann. Chem. 1986, pp. 2112-2122.
"Synthesis" (1986), pp. 1052-1054.
"Tetrahedron Letters", vol. 28, No. 20, pp. 2299-2300, 1987.
"Chemical Abstract" vol. 89, 1978, pp. 690, 43996j.
"Synthesis of the Dideoxynucleosides DDC and CNT from Clutamic Acid, Ribonolactone, and Pyrimidine Bases" J. Org. Chem. 1988, 53, pp. 4780-4786.
"Heterocycles", vol. 31, No. 9, 1990, pp. 1585-1588.
"Advanced Organic Chemistry" p. 400 1977.
"Tetrahedron" vol. 43, No. 19, pp. 4497-4506, 1987.
"Carbohydrate Research" 129 (1984) pp. 73-86.
"Synthetic Studies on Cembranolides Stereoselective Synthesis of Epoxy Ester Intermediates" J. Org. Chem. 1984, 49, pp. 747-753.
Angew. Chem. Int. Ed. Engl. 28 (1989) No. 1, pp. 69-71.
Chemistry Letters, pp. 307-310, 1990.
"Tetrahedron" vol. 38, No. 15, pp. 2395-2402, 1982.
Ebata Takashi
Kawakami Hiroshi
Koseki Koshi
Matsumoto Katsuya
Matsushita Hajime
Ivy C. Warren
Japan Tobacco Inc.
Owens A. A.
Yuji Gosei Kogyo Co., Ltd.
LandOfFree
Method of producing cis-whiskey lactone does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Method of producing cis-whiskey lactone, we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Method of producing cis-whiskey lactone will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-1138503