2,5-dimethylhexa-2,4-diene

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: Ethyl diazoacetate (5.0 g) in methylene chloride (50 mL) was added dropwise to a slurry of the Cu,K-PFIEP[SO3H] catalyst described above (2.0 g) in methylene chloride (100 mL) and 2,5-dimethyl-2,4-hexadiene (8.33 g). After stirring for about 18 h at ambient temperature, the reaction product was isolated by filtering off the catalyst, evaporating the solvent and chromatographing the resulting residue on silica with 10% ethyl acetate and 90% hexane as eluant. The isolated chrysanthemumate had an identical 1H nmr spectrum to a commercial sample. Anal. Calcd. for C12H20O2 : C, 73.43; H, 10.27; Found: C, 74.08; H, 10.58. the reaction product was isolated by filtering off the catalyst evaporating the solvent and chromatographing the resulting residue on silica with 10% ethyl acetate and 90% hexane as eluant

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

Procedure: Ethyl diazoacetate (5.0 g) in methylene chloride (50 mL) was added dropwise to a slurry of the Cu,K-PFIEP[SO3H] catalyst described above (2.0 g) in methylene chloride (100 mL) and 2,5-dimethyl-2,4-hexadiene (8.33 g). After stirring for about 18 h at ambient temperature, the reaction product was isolated by filtering off the catalyst, evaporating the solvent and chromatographing the resulting residue on silica with 10% ethyl acetate and 90% hexane as eluant. The isolated chrysanthemumate had an identical 1H nmr spectrum to a commercial sample. Anal. Calcd. for C12H20O2 : C, 73.43; H, 10.27; Found: C, 74.08; H, 10.58. the reaction product was isolated by filtering off the catalyst evaporating the solvent and chromatographing the resulting residue on silica with 10% ethyl acetate and 90% hexane as eluant

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

Procedure: A flask was charged with CH2Cl2 (25 mL), 2,5-dimethyl-2,4-hexadiene (25 mL) and 0.45 g of the Cu,K-PFIEP[SO3H] catalyst, prepared as described above. A solution of ethyl diazoacetate (2.5 g) in CH2Cl2 (25 mL) was added slowly dropwise and the resulting reaction mixture was stirred for 24 hours at ambient temperature. Gas chromatography analysis showed that the resulting product contained cis- and trans-ethyl chrysanthemumates in a 1:1.66 isomer ratio and a combined yield of 89.6%. prepared the resulting reaction mixture

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

Procedure: A flask was charged with CH2Cl2 (25 mL), 2,5-dimethyl-2,4-hexadiene (25 mL) and 0.45 g of the Cu,K-PFIEP[SO3H] catalyst, prepared as described above. A solution of ethyl diazoacetate (2.5 g) in CH2Cl2 (25 mL) was added slowly dropwise and the resulting reaction mixture was stirred for 24 hours at ambient temperature. Gas chromatography analysis showed that the resulting product contained cis- and trans-ethyl chrysanthemumates in a 1:1.66 isomer ratio and a combined yield of 89.6%. prepared the resulting reaction mixture

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

Procedure: Ethyl diazoacetate (5.0 g) in methylene chloride (50 mL) was added dropwise to a slurry of the Cu,K-PFIEP[SO3H] catalyst described above (2.0 g) in methylene chloride (100 mL) and 2,5-dimethyl-2,4-hexadiene (8.33 g). After stirring for about 18 h at ambient temperature, the reaction product was isolated by filtering off the catalyst, evaporating the solvent and chromatographing the resulting residue on silica with 10% ethyl acetate and 90% hexane as eluant. The isolated chrysanthemumate had an identical 1H nmr spectrum to a commercial sample. Anal. Calcd. for C12H20O2 : C, 73.43; H, 10.27; Found: C, 74.08; H, 10.58. the reaction product was isolated by filtering off the catalyst evaporating the solvent and chromatographing the resulting residue on silica with 10% ethyl acetate and 90% hexane as eluant

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

Procedure: A flask was charged with CH2Cl2 (25 mL), 2,5-dimethyl-2,4-hexadiene (25 mL) and 0.45 g of the Cu,K-PFIEP[SO3H] catalyst, prepared as described above. A solution of ethyl diazoacetate (2.5 g) in CH2Cl2 (25 mL) was added slowly dropwise and the resulting reaction mixture was stirred for 24 hours at ambient temperature. Gas chromatography analysis showed that the resulting product contained cis- and trans-ethyl chrysanthemumates in a 1:1.66 isomer ratio and a combined yield of 89.6%. prepared the resulting reaction mixture

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

Procedure: A portion of the effluent from Example 6 was taken, containing 800 m mole trichloroethylene, 35 m mole 2,5-dimethylhexa-1,5-diene and 91 m mole 1,1-dichloro-4-methylpenta-1,4-diene. This mixture was subjected to fractional distillation, and about 600 m mole of trichloroethylene were removed slowly at ≯ 87° C. The residue was treated with p-toluene sulphonic acid (1% by weight) in an autoclave at 150° for 4 hours under autogeneous pressure. Essentially complete isomerisation of the dienes to their conjugated isomers was effected by this treatment. The mixture was fractionally distilled to yield 2,5-dimethylhexa-2,4-diene (28 m mole) and 1,1-dichloro-4-methylpenta-1,3-diene (80 m mole). This mixture was subjected to fractional distillation, and about 600 m mole of trichloroethylene were removed slowly at ≯ 87° C The residue was treated with p-toluene sulphonic acid (1% by weight) in an autoclave at 150° for 4 hours under autogeneous pressure The mixture was fractionally distilled

Conditions: temp:0.00; pressure:0.00; stir:

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

Procedure: A portion of the effluent from Example 6 was taken, containing 800 m mole trichloroethylene, 35 m mole 2,5-dimethylhexa-1,5-diene and 91 m mole 1,1-dichloro-4-methylpenta-1,4-diene. This mixture was subjected to fractional distillation, and about 600 m mole of trichloroethylene were removed slowly at ≯ 87° C. The residue was treated with p-toluene sulphonic acid (1% by weight) in an autoclave at 150° for 4 hours under autogeneous pressure. Essentially complete isomerisation of the dienes to their conjugated isomers was effected by this treatment. The mixture was fractionally distilled to yield 2,5-dimethylhexa-2,4-diene (28 m mole) and 1,1-dichloro-4-methylpenta-1,3-diene (80 m mole). This mixture was subjected to fractional distillation, and about 600 m mole of trichloroethylene were removed slowly at ≯ 87° C The residue was treated with p-toluene sulphonic acid (1% by weight) in an autoclave at 150° for 4 hours under autogeneous pressure The mixture was fractionally distilled

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

Procedure: In a 50 mL Schlenk tube purged with nitrogen, 22 mg of 2,2-bis[2-[(4S)-1-naphthyloxazoline]]propane was added to a white suspension containing 18 mg of cuprous trifluoromethanesulfonate and 5 mL of dichloroethane and stirred at a room temperature for 10 minutes to prepare a blue color homogeneous solution of an asymmetric copper complex. After that, 7.8 g of 2,5-dimethyl-2,4-hexadiene was added thereto and the inner temperature was adjusted to 40° C. and 1.4 g of tert-butyl diazoacetate was dropwise added for 2 hours and the resulting mixture was stirred at the same time further for 30 minutes to effect reaction and tert-butyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate was obtained in a yield of 89% (based on tert-butyl diazoacetate). Trans-isomer/cis-isomer ratio=81/19. The optical purity of the trans-isomer was 86% e.e. and that of the cis-isomer was 60% e.e. In a 50 mL Schlenk tube purged with nitrogen, 22 mg of 2,2-bis[2-[(4S)-1-naphthyloxazoline]]propane was added to a white suspension containing 18 mg of cuprous trifluoromethanesulfonate and 5 mL of dichloroethane to prepare a blue color homogeneous solution of an asymmetric copper complex was adjusted to 40° C. the resulting mixture was stirred at the same time further for 30 minutes reaction

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

Procedure: In a 50 mL Schlenk tube purged with nitrogen, 22 mg of 2,2-bis[2-[(4S)-1-naphthyloxazoline]]propane was added to a white suspension containing 18 mg of cuprous trifluoromethanesulfonate and 5 mL of dichloroethane and stirred at a room temperature for 10 minutes to prepare a blue color homogeneous solution of an asymmetric copper complex. After that, 7.8 g of 2,5-dimethyl-2,4-hexadiene was added thereto and the inner temperature was adjusted to 40° C. and 1.4 g of tert-butyl diazoacetate was dropwise added for 2 hours and the resulting mixture was stirred at the same time further for 30 minutes to effect reaction and tert-butyl 2,2-dimethyl-3-(2-methyl-1-propenyl)cyclopropanecarboxylate was obtained in a yield of 89% (based on tert-butyl diazoacetate). Trans-isomer/cis-isomer ratio=81/19. The optical purity of the trans-isomer was 86% e.e. and that of the cis-isomer was 60% e.e. In a 50 mL Schlenk tube purged with nitrogen, 22 mg of 2,2-bis[2-[(4S)-1-naphthyloxazoline]]propane was added to a white suspension containing 18 mg of cuprous trifluoromethanesulfonate and 5 mL of dichloroethane to prepare a blue color homogeneous solution of an asymmetric copper complex was adjusted to 40° C. the resulting mixture was stirred at the same time further for 30 minutes reaction