Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Patent
1992-10-21
1994-12-20
Ivy, C. Warren
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
549314, C07D30728
Patent
active
053747445
DESCRIPTION:
BRIEF SUMMARY
TECHNICAL FIELD
The present invention relates to a method of manufacturing a 4-substituted-.gamma.-lactone and a novel substance as a useful intermediate product thereof. The 4-substituted-.gamma.-lactone include sex pheromones of vermin. More specifically, examples are (R,Z)-5-tetradecene-4-olide known as the sex pheromone of mamekogane (common name: Japanese beetle, scientific name: Popillia japonica) [J. H. Tumlinson et al, Science, 789, 197 (1977)] and (R,Z)-5-dodecene-4-olide known as the sex pheromone of a cupreous chafer. Therefore, the present invention is suitable in the verminous extermination of the mamekogane and the cupreous chafer in accordance with a pheromone trap (catching and killing by attraction).
BACKGROUND ART
The mamekogane and the cupreous chafer are vermin on fruit trees such as grape trees, and lawns. In recent years, damage to lawn by the mamekogane and the cupreous chafers in golf courses poses a serious problem.
Conventionally, these mamekogane and cupreous chafers are exterminated by pesticide applications. However, since a large amount of pesticide is used, the environmental pollution caused by contamination with pesticides in the vicinity of a golf course is a serious problem.
On the other hand, catching and killing by attraction using the sex pheromone of a vermin has an advantage in that a large number of vermin can be exterminated with a small amount of pheromone. This method is applied to some vermin in practice. Therefore, catching and killing by attraction of the mamekogane and cupreous chafers is assumed to be an extremely effective means to solve the above problem.
The following methods are known as methods of synthesizing the pheromone of the mamekogane, i.e., (R,Z)-5-tetradecene-4-olide (18).
1) A method in which, as indicated by reaction formula (I) below, (4R,5S,6S)-5,6-dihydroxytetradecane-4-olide (40) as an optically active intermediate is derived from arabinose, an intermediate (41) is then derived from the intermediate (40), and diols at the 5- and 6-positions of the intermediate (41) are eliminated to obtain a compound (18) [Y. Nishida, M. Konno, H. Hori, H. Ohrui, H. Meguro, Agric. Biol. Chem., 51, 635 (1987)]: ##STR1## (wherein R.sub.1 represents C.sub.8 H.sub.17).
2) A method in which, as indicated by reaction formula (II) below, an acetylenic ketoester (52) synthesized from a 1-decyne derivative (51) is asymmetrically reduced (53) in the presence of (2S,3R)-(+)-4-dimethylamino-1,2-diphenyl-3-methyl-2-but anol [Chirald available from Aldrich Chemical Co., Inc.] and LiAlH.sub.4, and the reduction product is subjected to fractional crystallization as an (R)-(+)-.alpha.-naphthylethylamine salt, thereby obtaining a compound (18) having high optical purity [S. Senda and K. Mori, Agric. Biol. Chem., 47, 2595 (1983)]. ##STR2## (wherein R.sub.1 represents C.sub.8 H.sub.17)
3) A method in which, as indicated by reaction formula (III), a compound (18) is obtained from (R)-glutamic acid, through butyrolactone, by using a Wittig reaction [R. E. Doolitle, et al, J. Chem. Ecol., 6,473 (1980)]. ##STR3## (wherein R.sub.1 represents C.sub.8 H.sub.17)
The conventional methods of manufacturing the compound (18) described above pose the following problems. Thus, in the method (1), a total of 12 steps are required from arabinose as the starting material, and the yield of the final compound (18) against arabinose is very low.
In the method (2), (2S,3R)-(+)-4-dimethylamino-1,2-diphenyl-3-methyl-2-butanol and (R)-(+) -.alpha.-naphthylethylamine which are required to obtain the optically active compound (18) are very expensive reagents, resulting in high manufacturing costs. In addition, in order to finally obtain the compound (18) having high optical purity, the (R)-(+) -.alpha.-naphthylethylamine salt must be subjected to fractional crystallization, thus complicating the process.
In the method (3), when nitric acid is reacted with (R)-glutamic acid to close the lactone ring, tetrahydro-5-oxy-2-furanonecarboxylic acid which is partially racemized is obtained. The racemic pro
REFERENCES:
Farbond et al. CA 113(22):197669f 1990.
M. Midland et al. (1980) Tetrahedron Letters 21:3549-3552.
Nishida, Yoshihiro et al., Agric. Biol. Chem., 51(3), pp. 635-640, 1987.
Senda, Shuji et al., Agric. Biol. Chem., 47(11), pp. 2595-2598, 1983.
Doolittle, R. E. et al., J. Chem. Ecol., 6, pp. 473-485, 1979.
Levene, P. A. et al., J. Biol. Chem., vol. 102, No. 1, pp. 187-201, 1933.
Chattopadhyay, S. et al., Synthetic Communications, 20(9), pp. 1299-1303, 1990.
Fukusaki, Eiichiro et al., Tetrahedron vol. 47, No. 32, pp. 6223-6230, 1991.
Leal, W. S., Naturwissenschaften 78, pp. 521-523, 1991.
Sugai, Takeshi et al. Synthesis pp. 1112-1114, Sep. 1990.
Nemoto Hideo et al., Heterocycles, vol. 31 No. 2, 1990.
Fukusaki, Eiichiro et al., Biosci. Biotech. Biochem., 56(7), pp. 1160-1161, 1992.
Ebata, Takashi et al., Biosci. Biotech. Biochem., 56(5), pp. 818-819, 1992.
Novel Lactone of Octanoic Acid Japanese 56-120678 Sep. 1981 Abstract.
The Merck Index (1983) Tenth Edition, Rahway, N.J., p. 987, entry 6758.
Ebata Takashi
Kawakami Hiroshi
Koseki Koshi
Matsushita Hajime
Ono Mikio
Fuji Flavor Co., Ltd.
Ivy C. Warren
Japan Tobacco Inc.
Owens A. A.
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