1-chloro-4-(diethoxyphosphorylmethyl)benzene

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

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

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

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

Procedure: Under a nitrogen atmosphere, 0.12 gram (0.0050 mole) of sodium hydride was added to a stirred solution of 1.2 gram (0.0057 mole) of 5-formyl-5'-methyl[2,2'-bithienyl] and 1.7 gram (0.0064 mole) of diethyl 4-chlorobenzylposphonate in 20 mL of N,N-dimethylformamide. The reaction mixture was stirred at room temperature for about three huurs. Analysis of the reaction mixture by thin layer chromatography indicated starting materials remained. Additional sodium hydride was added, and the mixture was stirred at room temperature for several hours. The reaction mixture was quenched with an aqueous solution saturated with ammonium chloride. This mixture was extracted several times with diethyl ether. The extracts were combined and washed with an aqueous solution saturated with sodium chloride. The washed extract was dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure leaving a residue. This residue was purified by column chromatography on silica gel to yield 2-(4-chlorophenyl)-1-(5'-methyl[2,2'-bithienyl]-5-yl)ethene as a solid, m.p. 157°-162° C. the mixture was stirred at room temperature for several hours The reaction mixture was quenched with an aqueous solution saturated with ammonium chloride This mixture was extracted several times with diethyl ether washed with an aqueous solution saturated with sodium chloride The washed extract was dried over anhydrous magnesium sulfate filtered The filtrate was evaporated under reduced pressure leaving a residue This residue was purified by column chromatography on silica gel

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

Conditions: temp:-70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 26.3 g (0.1 mol) of 4-chlorobenzyl-phosphonic acid diethyl ester were dissolved in 400 ml of absolute tetrahydrofuran and the solution was cooled to -70° C. 0.11 mol of n-butyl-lithium (15% strength solution in hexane) were added dropwise, in counter-current with nitrogen and while stirring thoroughly, and the reaction mixture was then subsequently stirred at -70° C. for a further 15 minutes. 15.4 g (0.1 mol) of carbon tetrachloride were then added dropwise at -70° C., also under nitrogen, and the reaction mixture thereby became red-brown in color. After stirring for a further 15 minutes, 18.6 g (0.1 mol) of 2,2-dimethyl-3-formyl-cyclopropanecarboxylic acid ethyl ester were added at -65° C. The reaction mixture was then allowed to come to room temperature and was subsequently stirred at 25° C. for a further 3 hours. The reaction mixture was then poured into 2 liters of water and extracted with 600 ml of ether. The ether phase was dried over sodium sulphate, the solvent was stripped off in vacuo and the oily residue was distilled at 150°-155° C./2 mm Hg. 2,2-Dimethyl-3-(2-chloro-2-p-chlorophenyl-vinyl)-cyclopropanecarboxylic acid ethyl ester was obtained in 54.3% yield. the reaction mixture was then subsequently stirred at -70° C. for a further 15 minutes After stirring for a further 15 minutes to come to room temperature was subsequently stirred at 25° C. for a further 3 hours extracted with 600 ml of ether The ether phase was dried over sodium sulphate the oily residue was distilled at 150°-155° C./2 mm Hg

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

Procedure: The captioned compound was synthesized from diethyl 4-chlorobenzylphosphonate and methyl 3-formyl-4-bromobenzoate in accordance with the same procedure as in the manufacturing method described in step A of Example 2-2-1.

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

Procedure: The captioned compound was synthesized from diethyl (4-chlorobenzyl)phosphonate and ethyl 3-formyl-4-methoxybenzoate obtained in step C of Example 1-2-1 in accordance with the same procedure as in the methods described in step A of Example 2-2-1.

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

Procedure: The captioned compound was synthesized from diethyl 4-chlorobenzylphosphonate and methyl 3-formyl-4-bromobenzoate in accordance with the same procedure as in the manufacturing method described in step A of Example 2-2-1.

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

Procedure: The captioned compound was synthesized from diethyl 4-chlorobenzylphosphonate and methyl 3-formyl-4-bromobenzoate in accordance with the same procedure as in the manufacturing method described in step A of Example 2-2-1.

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

Procedure: The captioned compound was synthesized from diethyl (4-chlorobenzyl)phosphonate and ethyl 3-formyl-4-methoxybenzoate obtained in step C of Example 1-2-1 in accordance with the same procedure as in the methods described in step A of Example 2-2-1.

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

Procedure: Under a nitrogen atmosphere, 0.12 gram (0.0050 mole) of sodium hydride was added to a stirred solution of 1.2 gram (0.0057 mole) of 5-formyl-5'-methyl[2,2'-bithienyl] and 1.7 gram (0.0064 mole) of diethyl 4-chlorobenzylposphonate in 20 mL of N,N-dimethylformamide. The reaction mixture was stirred at room temperature for about three huurs. Analysis of the reaction mixture by thin layer chromatography indicated starting materials remained. Additional sodium hydride was added, and the mixture was stirred at room temperature for several hours. The reaction mixture was quenched with an aqueous solution saturated with ammonium chloride. This mixture was extracted several times with diethyl ether. The extracts were combined and washed with an aqueous solution saturated with sodium chloride. The washed extract was dried over anhydrous magnesium sulfate and filtered. The filtrate was evaporated under reduced pressure leaving a residue. This residue was purified by column chromatography on silica gel to yield 2-(4-chlorophenyl)-1-(5'-methyl[2,2'-bithienyl]-5-yl)ethene as a solid, m.p. 157°-162° C. the mixture was stirred at room temperature for several hours The reaction mixture was quenched with an aqueous solution saturated with ammonium chloride This mixture was extracted several times with diethyl ether washed with an aqueous solution saturated with sodium chloride The washed extract was dried over anhydrous magnesium sulfate filtered The filtrate was evaporated under reduced pressure leaving a residue This residue was purified by column chromatography on silica gel