(1R,3S)-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropane-1-carbonyl chloride

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 625 mg of (1R)-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid chloride was added under ice-water cooling to a mixed solution of 400 mg of (RS)-2-methyl-4-methylidene-3-ethylcyclopent-2-en-1-ol, 5 mg of 2,6-di-t-butyl-4-methylphenol and 274 mg of pyridine in 6 ml of toluene. The reaction was continued at an ambient temperature for eight hours. The reaction solution was added to a 5% citric acid solution under ice-water cooling, and extracted three times with diethyl ether. The combined ether layer was washed successively with a saturated sodium hydrogencarbonate solution and a saturated sodium chloride solution, and dried over anhydrous magnesium sulfate. After removal of the solvent under reduced pressure, the residue was subjected to silica gel column chromatography to yield 781 mg of (RS)-2-methyl-4-methylidene-3-ethyl-2-cyclopenten-1-yl (1R)-trans-3-(2,2-dichloro-vinyl)-2,2-dimethylcyclopropanecarboxylate (Compound No.5). Yield 82%. extracted three times with diethyl ether The combined ether layer was washed successively with a saturated sodium hydrogencarbonate solution a saturated sodium chloride solution, and dried over anhydrous magnesium sulfate After removal of the solvent under reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of (RS)-3-(2-propenyl)-3-cyclopenten-1-ol (100 mg), 2,6-di-tert-butyl-4-methylphenol (5 mg), pyridine (82 mg) and toluene (5 ml), (1R)-trans-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarbonyl chloride (181 mg) was added under ice-cooling. The resulting reaction mixture was further allowed to react for 8 hours at room temperature. Then the reaction mixture was subjected to the same post-treatment as in Example 1 to afford 145 mg of (RS)-3-(2-propenyl)-3-cyclopenten-1-yl (1R)-trans-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate (Compound No. 29). Yield 57% nD25 1.5100 was added under ice- cooling The resulting reaction mixture to react for 8 hours at room temperature

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of (RS)-3-(2-propenyl)-4-methyl-3-cyclopenten-1-ol (190 mg), 2,6-di-tert-butyl-4-methylphenol (5 mg), pyridine (140 mg) and toluene (10 ml), (1R)-trans-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarbonyl chloride (310 mg) was added under ice-cooling. The resulting reaction mixture was further allowed to react for 8 hours at room temperature. Then the reaction mixture was subjected to the same post-treatment as in Example 1 to afford 379 mg of (RS)-3-(2-propenyl)-4-methyl-3-cyclopenten-1-yl (1R)-trans-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate (Compound No. 18). Yield 77% nD24 1.5112 was added under ice- cooling The resulting reaction mixture to react for 8 hours at room temperature

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 3.4 Grams of pyridine was added to a mixture of 5.0 g of (S)-2-methyl-4-oxo-3-(2-propynyl)-cyclopent-2-enyl alcohol, 8.0 g of (1R)-trans-3-(2, 2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid chloride and 50 ml of toluene under ice-cooling. The resulting mixture was allowed to react at room temperature for 12 hours. Thereafter, about 50 ml of a saturated aqueous ammonium chloride solution was added to the resultant reaction solution, which was then extracted with three 50-ml portions of diethyl ether. The combined diethyl ether layer was washed with a saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The residue was subjected to a silica gel column chromatography followed by recrystallization from a mixed solvent of hexane and ethyl acetate to obtain 8.9 g (yield: 78%) of (S)-2-methyl-4-oxo-3-(2-propynyl)-cyclopent-2-enyl (1R)-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate (the present compound). cooling to react at room temperature for 12 hours reaction solution, which was then extracted with three 50-ml portions of diethyl ether The combined diethyl ether layer was washed with a saturated aqueous sodium chloride solution dried over anhydrous sodium sulfate concentrated under reduced pressure followed by recrystallization from a mixed solvent of hexane and ethyl acetate

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 3.4 Grams of pyridine was added to a mixture of 5.0 g of (S)-2-methyl-4-oxo-3-(2-propynyl)-cyclopent-2-enyl alcohol, 8.0 g of (1R)-trans-3-(2, 2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid chloride and 50 ml of toluene under ice-cooling. The resulting mixture was allowed to react at room temperature for 12 hours. Thereafter, about 50 ml of a saturated aqueous ammonium chloride solution was added to the resultant reaction solution, which was then extracted with three 50-ml portions of diethyl ether. The combined diethyl ether layer was washed with a saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The residue was subjected to a silica gel column chromatography followed by recrystallization from a mixed solvent of hexane and ethyl acetate to obtain 8.9 g (yield: 78%) of (S)-2-methyl-4-oxo-3-(2-propynyl)-cyclopent-2-enyl (1R)-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate (the present compound). cooling to react at room temperature for 12 hours reaction solution, which was then extracted with three 50-ml portions of diethyl ether The combined diethyl ether layer was washed with a saturated aqueous sodium chloride solution dried over anhydrous sodium sulfate concentrated under reduced pressure followed by recrystallization from a mixed solvent of hexane and ethyl acetate

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 3.4 Grams of pyridine was added to a mixture of 5.0 g of (S)-2-methyl-4-oxo-3-(2-propynyl)-cyclopent-2-enyl alcohol, 8.0 g of (1R)-trans-3-(2, 2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid chloride and 50 ml of toluene under ice-cooling. The resulting mixture was allowed to react at room temperature for 12 hours. Thereafter, about 50 ml of a saturated aqueous ammonium chloride solution was added to the resultant reaction solution, which was then extracted with three 50-ml portions of diethyl ether. The combined diethyl ether layer was washed with a saturated aqueous sodium chloride solution, dried over anhydrous sodium sulfate and then concentrated under reduced pressure. The residue was subjected to a silica gel column chromatography followed by recrystallization from a mixed solvent of hexane and ethyl acetate to obtain 8.9 g (yield: 78%) of (S)-2-methyl-4-oxo-3-(2-propynyl)-cyclopent-2-enyl (1R)-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate (the present compound). cooling to react at room temperature for 12 hours reaction solution, which was then extracted with three 50-ml portions of diethyl ether The combined diethyl ether layer was washed with a saturated aqueous sodium chloride solution dried over anhydrous sodium sulfate concentrated under reduced pressure followed by recrystallization from a mixed solvent of hexane and ethyl acetate

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 625 mg of (1R)-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid chloride was added under ice-water cooling to a mixed solution of 400 mg of (RS)-2-methyl-4-methylidene-3-ethylcyclopent-2-en-1-ol, 5 mg of 2,6-di-t-butyl-4-methylphenol and 274 mg of pyridine in 6 ml of toluene. The reaction was continued at an ambient temperature for eight hours. The reaction solution was added to a 5% citric acid solution under ice-water cooling, and extracted three times with diethyl ether. The combined ether layer was washed successively with a saturated sodium hydrogencarbonate solution and a saturated sodium chloride solution, and dried over anhydrous magnesium sulfate. After removal of the solvent under reduced pressure, the residue was subjected to silica gel column chromatography to yield 781 mg of (RS)-2-methyl-4-methylidene-3-ethyl-2-cyclopenten-1-yl (1R)-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate (Compound No.5). Yield 82%. (Eluent: n-hexane/ethyl acetate=30/1, 2,6-di-t-butyl-4-methylphenol 0.1%) nD23 1.5251 extracted three times with diethyl ether The combined ether layer was washed successively with a saturated sodium hydrogencarbonate solution a saturated sodium chloride solution, and dried over anhydrous magnesium sulfate After removal of the solvent under reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 625 mg of (1R)-trans-3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid chloride was added under ice-water cooling to a mixed solution of 400 mg of (RS)-2-methyl-4-methylidene-3-ethylcyclopent-2-en-1-ol, 5 mg of 2,6-di-t-butyl-4-methylphenol and 274 mg of pyridine in 6 ml of toluene. The reaction was continued at an ambient temperature for eight hours. The reaction solution was added to a 5% citric acid solution under ice-water cooling, and extracted three times with diethyl ether. The combined ether layer was washed successively with a saturated sodium hydrogencarbonate solution and a saturated sodium chloride solution, and dried over anhydrous magnesium sulfate. After removal of the solvent under reduced pressure, the residue was subjected to silica gel column chromatography to yield 781 mg of (RS)-2-methyl-4-methylidene-3-ethyl-2-cyclopenten-1-yl (1R)-trans-3-(2,2-dichloro-vinyl)-2,2-dimethylcyclopropanecarboxylate (Compound No.5). Yield 82%. extracted three times with diethyl ether The combined ether layer was washed successively with a saturated sodium hydrogencarbonate solution a saturated sodium chloride solution, and dried over anhydrous magnesium sulfate After removal of the solvent under reduced pressure

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of (RS)-3-(2-propenyl)-3-cyclopenten-1-ol (100 mg), 2,6-di-tert-butyl-4-methylphenol (5 mg), pyridine (82 mg) and toluene (5 ml), (1R)-trans-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarbonyl chloride (181 mg) was added under ice-cooling. The resulting reaction mixture was further allowed to react for 8 hours at room temperature. Then the reaction mixture was subjected to the same post-treatment as in Example 1 to afford 145 mg of (RS)-3-(2-propenyl)-3-cyclopenten-1-yl (1R)-trans-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate (Compound No. 29). Yield 57% nD25 1.5100 was added under ice- cooling The resulting reaction mixture to react for 8 hours at room temperature

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: To a mixture of (RS)-3-(2-propenyl)-4-methyl-3-cyclopenten-1-ol (190 mg), 2,6-di-tert-butyl-4-methylphenol (5 mg), pyridine (140 mg) and toluene (10 ml), (1R)-trans-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarbonyl chloride (310 mg) was added under ice-cooling. The resulting reaction mixture was further allowed to react for 8 hours at room temperature. Then the reaction mixture was subjected to the same post-treatment as in Example 1 to afford 379 mg of (RS)-3-(2-propenyl)-4-methyl-3-cyclopenten-1-yl (1R)-trans-2,2-dimethyl-3-(2,2-dichlorovinyl)cyclopropanecarboxylate (Compound No. 18). Yield 77% nD24 1.5112 was added under ice- cooling The resulting reaction mixture to react for 8 hours at room temperature