Organic compounds -- part of the class 532-570 series – Organic compounds – Oxygen containing
Patent
1987-08-07
1988-07-05
Lone, Werren B.
Organic compounds -- part of the class 532-570 series
Organic compounds
Oxygen containing
568700, 568715, 568828, C07C 35205
Patent
active
047556269
DESCRIPTION:
BRIEF SUMMARY
TECHNICAL FIELD
The present invention relates to 4-isopropyl-7-methylene-5-cyclodecen-1-ol, which is useful as an intermediate for synthesizing periplanone-B which is a sex pheromone of American cockroaches.
BACKGROUND ART
Periplanone-B is the main component of the sex pheromone of female American cockroaches (Periplaneta americana) which are a type of harmful insect distributed worldwide. C. J. Persoons et al. were the first to isolate this component and determine its plane structure, and they reported that this component had a specific germacrene-type sesquiterpenoid structure (C. J. Persoons et al., Tetrahedron Letters, 24, 2055 (1976)). According to Persoons et al., periplanone-B produces a very strong physiological effect; 1 picogram (1/100,000,000,000 gram) of this component attracts and sexually excites male American cockroaches. W. C. Still et al. synthesized a racemic material of periplanone-B and determined its relative configuration (W. C. Still, J. Am. Chem. Soc., 101, 2495 (1979)). K. Nakanishi et al optically resolved the racemic material synthesized by Still et al. and determined the absolute configuration of periplanone-B by a spectroscopic method (K. Nakanishi et al., J. Am. Chem. Soc., 101, 2495 (1979)). S. N. Schreiber reported another method of synthesizing periplanone-B in J. Am. Chem. Soc., 106, 4038 (1984).
As has been described above, periplanone-B is a sex pheromone of American cockroaches and can be used to attract or trap male American cockroaches in a specific location. However, insects including American cockroaches produce only a small amount of sex pheromone, and extraction thereof is not practical. Therefore, development of a method which allows synthesis of periplanone-B on an industrial scale is desirable.
In the synthetic methods of Still et al. and Schreiber et al., the starting material is a racemic material (ethoxyethyl ether of (+)-5-(hydroxymethyl)cyclohexenone in the former, and (+)-4-isopropyl-2-cyclohexen-1-one) in the latter). Therefore, periplanone-B obtained as a final product in either method is only a racemic material. A starting material racemic material used in either method is very difficult to optically resolve, and requires a complex process therefor. In addition, these methods use oxy-Cope rearrangement, which cannot be performed on a large scale, in the formation of a 10-membered ring, which is a key reaction in the synthesis of periplanone-B. These methods are not, therefore, efficient. Moreover, these methods include many steps which require fine adjustment of reaction conditions, such as organometallic reactions or stereoselective reactions.
DISCLOSURE OF INVENTION
It is, therefore, an object of the present invention to provide an optically active intermediate which allows synthesis of optically active periplanone-B on an industrial scale.
There is provided according to the present invention 4-isopropyl-7-methylene-5-cyclodecen-1-ol.
BEST MODE OF CARRYING OUT THE INVENTION
The compound according to the present invention, i.e., 4-isopropyl-7-methylene-5-cyclodecen-1-ol is represented by the following formula: ##STR1## This compound can be manufactured using, as a starting material, optically active d-dihydrolimonene, which is known per se and is readily available, following the reaction routs below: ##STR2##
A method of manufacturing the compound of the invention will be described below, along the above routs.
(i) In step 1, d-dihydrolimonene, represented by formula A, is subjected to ozonolysis, and resulting ozonolysed product is reduced with dimethylsulfide. The ozonolysis can be performed by suspending d-dihydrolimonene in an alcohol solvent, and passing ozone through the suspension at a temperature of 0.degree. C. or lower, and preferably -30.degree. C. or lower. The alcohol solvent can be an alcohol such as methanol, ethanol, or ethylene glycol, or a mixture thereof with methylene chloride or chloroform. A preferred solvent is a mixture of methanol with methylene chloride. Ozone is contained in oxygen or air at a concentration of 1 to
REFERENCES:
patent: 3184432 (1965-05-01), Wilkes et al.
patent: 3217041 (1965-11-01), Houlihan
patent: 3914315 (1975-10-01), Miyake et al.
Persoons et al, Tetrahedron Letters, "Sex Pheromons of the American Cockroach, Periplanet Americana: A Tentative Structure of Periplanone-B", 2055-2058, 1976.
Still, W. Clark, Journal of the American Chemical Society, "Periplanone-B, Total Synthesis and Structure of the Sex Excitant Pheromone of the American Cockroach", vol. 101, 2493-2495, Apr. 25, 1979.
Kitahara Takeshi
Koseki Koshi
Mori Kenji
Mori Masataka
Japan Tobacco Inc.
Lone Werren B.
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