Drug – bio-affecting and body treating compositions – Baits – attractants – or lures
Reexamination Certificate
2000-03-15
2002-04-23
Pak, John (Department: 1616)
Drug, bio-affecting and body treating compositions
Baits, attractants, or lures
C514S529000, C560S125000
Reexamination Certificate
active
06375943
ABSTRACT:
BACKGROUND OF THE INVENTION
This invention relates to a method of attracting the Mediterranean fruit fly by subjecting the Mediterranean fruit fly to an attractant, wherein the attractant is ethyl (1R,2R,5R)-5-iodo-2-methylcyclohexane-1-carboxylate in an enantomeric excess of at least 70% and a regio and diastereo chemical purity of >5:1. The compound ethyl (1R,2R,5R)-5-iodo-2-methyl cyclohexane-1-carboxylate, in an enantomeric excess of at least 70% and a regio and diastereochemical purity of >5:1, may be prepared by reacting ethyl (1R,2R,5S)-5-hydroxy-2-methyl-1-carboxylate with Ph
3
P-imidazole-I
2
(or Ph
3
P-2,6-lutidine-I
2
) in a carbon tetrachloride/methlylene chloride mixture.
The Mediterranean fruit fly,
Ceratitas capitata
(Wiedemann) commonly known as the medfly, is a worldwide pest that feeds on 253 fruits and vegetables (Liquido, N. J., et al., Misc. Publ. Entomol. Soc. Am., 77:1 (1991)). The establishment of this exotic pest into the continental United States would significantly increase pesticide use and curtail fruit and vegetable exports, a multi-billion dollar industry (Jackson, D. S., et al., Entomol. Soc. Am., 31:2937 (1985)). For more than 30 years trimedlure (TML), a mixture of sixteen regio- and stereoisomers of tert-butyl esters of 4 (and 5)-chloro-2-methylcyclohexane-1-carboxylate (1), has been widely used as an attractant in traps used to monitor and detect male medfly (Beroza, M., et al., J. Agric. Food Chem., 9: 361-365 (1961)). The commercial trimedlure is formulated in a polymeric plug-type dispenser containing 2 g of trimedlure which acts as a controlled release dispenser for up to 8 weeks in Jackson traps (Leonhardt, B. A., et al., J. Econ. Entomol., 82: 860-867 (1989); Leonhardt, B. A., et al., Entomol. Exp. Appl., 44: 45-51 (1987)). HPLC separation of these sixteen regio- and stereoisomers of tert-butyl esters of 4 (and 5)-chloro-2-methylcyclohexane-1-carboxylate (1) made possible a field study of the relative attractiveness of these racemates toward the Mediterranean fruit fly (McGovern, T. P., et al., J. Econ. Entomol., 83:1350-1354 (1990)). Of these stereoisomers, TML-C (2) was shown to be most active. Particularly noteworthy is the ability of the medfly to discriminate among the two enantiomers of TML-C, with the (1S, 2S, 4R) configuration being most attractive (Sonnet, P. E., et al., J. Org. Chem., 49: 4639-4643 (1984); Doolittle, R. E., et al., J. Chem. Ecol., 17: 475-484 (1991)).
Recently, an iodo analog of trimedlure, ceralure (CER) (3), a mixture of 16 regio- and stereoisomers of ethyl 4 (and 5)-iodo-2-methylcyclohexane-1-carboxylate, has been found to be a more persistent and potent attractant than TML (U.S. Pat. No. 4,764,366). A field study designed to measure the relative attractiveness of these racemates, which were tediously separated by HPLC, demonstrated that ethyl cis-5-iodo-trans-2-methylcyclohexane-1-carboxylate (CER B
1
) (4) is most active (Warthen, J. D., J. Chem. Ecol, 20: 569-578 (1994)).
SUMMARY OF THE INVENTION
We have discovered that ethyl (1R,2R,5R)-5-iodo-2-methylcyclohexane-1-carboxylate, in an enantomeric excess of at least 70% and a regio- and diastereochemical purity of >5:1, may be prepared by reacting ethyl (1R,2R,5S)-5-hydroxy-2-methyl-1-carboxylate with Ph
3
P-imidazole-I
2
(or Ph
3
P-2,6-lutidine-I
2
) in a carbon tetrachloride/methlylene chloride mixture.
In accordance with this discovery, it is an object of the invention to provide ethyl (1R,2R,5R)-5-iodo-2-methylcyclohexane-1-carboxylate in an enantomeric excess of at least 70% and a regio- and diastereochemical purity of >5:1.
It is another object of the invention to provide a composition for attracting the Mediterranean fruit fly wherein the composition contains ethyl (1R,2R,5R)-5-iodo-2-methylcyclohexane-1-carboxylate in an enantomeric excess of at least 70% and a regio- and diastereochemical purity of >5:1.
It is also another object of the invention to provide a method of attracting the Mediterranean fruit fly by subjecting the Mediterranean fruit fly to an attractant, wherein the attractant is ethyl (1R,2R,5R)-5-iodo-2-methylcyclohexane-1-carboxylate in an enantomeric excess of at least 70% and a regio- and diastereochemical purity of >5:1.
REFERENCES:
patent: 3016329 (1962-01-01), Beroza et al.
patent: 4152422 (1979-05-01), Ohinata et al.
patent: 4764366 (1988-08-01), McGovern et al.
patent: 4891217 (1990-01-01), McGovern et al.
Avery, J.W., et al., “Use of Ceralure and Trimedlure in Mediterranean Fruit Fly (Diptera: Tephritidae) Mass-Trapping Tests”,J. Entomol. Sci., vol. 29(4), pp. 543-556, Oct., 1994.
Avery, J.W., et al., “Regioselective Synthesis of Ceralure B1and A, Ethyl cis-(and trans-) 5-Iodo-trans-2-Methylcyclohexane-1-Carboxylate”,Tetrahedron Letters, vol. 35(50), pp. 9337-9338, 1994.
Beroza, M., et al., “New Attractants for the Mediterranean Fruit Fly”,Agriculture and Food Chemistry, vol. 9(5), pp. 361-365, Sep.-Oct., 1961.
Clive, D.L.J., et al.,“Total Synthesis of Both(+)-Compactin and (+)-Mevinolin. General Strategy Based on the Use of a Special Titanium Reagent for Dicarbonyl Coupling”,J. Am. Chem. Soc., vol. 112(8), pp. 3018-3028, 1990.
Corey, E.J., et al., “Pyridinium Chlorochromate. An Efficient Reagent for Oxidation of Primary and Secondary Alcohols to Carbonyl Compounds”,Tetrahedron Letters, No. 31, pp. 2647-2650, Jun. 10, 1975.
DeMilo, A.B., et al. “Trimedlure: Effects of Structural Modifications on Its Attractiveness to Mediterranean Fruit Fly Males (Diptera: Tephritidae)”,J. Economic Entomology, vol. 87(6), 1494-1501, Dec., 1994.
DeMilo, A.B., et al., “Structure Confirmation of the Four trans Isomers of Ceralure, A Medfly Attractant, by NMR”,J. Agric. Food Chem., vol. 42(10), pp. 2089-2093, 1994.
DeMilo, A.B., et al., “Capillary Gas Chromatography Method for the Analysis of the trans isomers of Ceralure, a Medfly Attractant”,J. Chromatography A, vol. 673, pp. 295-298, 1994.
Doolittle, R.E., “Trimedlure Enantiomers: Differences in Attraction for Mediterranean Fruit Fly,Ceratitis capitata(WIED.) (Diptera: Tephritidae)”,J. Chemical Ecology, vol. 17(2), pp. 475-484, 1991.
Evans, D.A., et al., “Contrasteric Carboximide Hydrolysis with Lithium Hydroperoxide”,Tetrahedron Letters, vol. 28(49), pp. 6141-6144, 1987.
Evans, D.A., et al., “Asymmetric Diels-Alder Cycloaddition Reactions with Chiral &agr;,&bgr;-Unsaturated N-Acyloaxolidinones”,J. Am. Chem. Soc., vol. 110(4), pp. 1238-1256, 1988.
Garegg, J., et al., “Novel Reagent System for Converting a Hydroxy-group into an Iodo-group in Carbohydrates with Inversion of Configuraton”,J.C.S. Chem. Comm., pp. 978-980, 1979.
Harris, E.J., et al., “Sticky Traps for Detection and Survey of Three Tephritids”,J. Economic Entomology, vol. 64(1), pp. 62-65, Feb., 1971.
House, H.O., et al., “Enones with Strained Double Bonds. 8. The Bicyclo[3.2.1]octane Systems”,J. Org. Chem., vol. 48(10), pp. 1643-1654, 1983.
Jackson, D.S., et al., “Medfly in California 1980-1982”,Bulletin of the ESA, pp. 29-37, Winter, 1985.
Knapp, S., et al., “Synthesis and Reactions of Iodo Lactams”,J. Org. Chem., vol. 53(17), pp. 4006-4014, 1988.
Leonhardt, B.A., et al., “Comparison of Ceralure and Trimedlure Attractants for the Male Mediterranean Fruit Fly (Diptera:Tephritidae)”,J. Entomol. Sci., vol. 31(2), pp. 183-190, 1996.
Leonhardt, B.A., et al., “Design, Effectiveness, and Performance Criteria of Dispenser Formulations of Trimedlure, an Attractant of the Mediterranean Fruit Fly (Diptera: Tephritidae)”,J. Economic Entomology, vol. 82(3), pp. 860-867, Jun., 1989.
Leonhardt, B.A., et al., “Performance of Controlled-Release Formulations of Trimedlure to Attract the Mediterranean Fruit Fly,Ceratitis capitata”, Entomol. exp. Appl., vol. 44, pp. 45-51, 1987.
McGovern, T.P., et al., “Relative Attraction of the Mediterranean Fruit Fly (Diptera: Tephritidae) to the Eight Isomers of Trimedlure”,J. Economic Entomology, vol. 83(4), pp. 1350-1354, Aug., 1990.
McGovern, T.P., et al., “Attractiveness of trans-Trimedlure and its four Isomers in Field Tests with the Mediterranean Fruit Fly (D
Jang Eric B.
Raw Andre S.
Fado John D.
Pak John
Silverstein M. Howard
Stover G. Byron
The United States of America as represented by the Secretary of
LandOfFree
Attractant for the mediterranean fruit fly, the method of... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Attractant for the mediterranean fruit fly, the method of..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Attractant for the mediterranean fruit fly, the method of... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2822079