ethyl 2-phenylsulfanylacetate

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: The procedure is as in Example 2 for the preparation of diethyl 2-dimethylamino-5-phenylthio-2,4-hexadienedioate, starting with N-(3-dimethylamino-3-benzoylpropenylidene)-N-methylmethanaminium tetrafluoroborate (5 g), a 2M ethanolic solution of sodium ethylate (7.4 cc) and ethyl (phenylthio)acetate (3.1 g) in ethanol (50 cc). After purification by chromatography on a silica column with a mixture of cyclohexane and ethyl acetate (80:20 by volume) as eluent, ethyl 5-dimethylamino-5-benzoyl-2-phenylthio-2,4-pentadienoate (4.1 g), m.p. 58° C., is obtained. After purification by chromatography on a silica column with a mixture of cyclohexane and ethyl acetate (80:20 by volume) as eluent

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

Procedure: The procedure is as in Example 2 for the preparation of ethyl (phenylthio)acetate, starting with n-butylmercaptan (10.7 cc), a 2M ethanolic solution of sodium ethylate (50 cc) and ethyl bromoacetate (16.7 g) in ethanol (100 cc). Ethyl (n-butylthio)acetate (15.4 g) is thereby obtained, and is used in the crude state in the subsequent syntheses.

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

Procedure: The procedure is as in Example 2 for the preparation of diethyl 2-dimethylamino-5-phenylthio-2,4-hexadienedioate, starting with N(3-dimethylamino-3-t-butyloxycarbonylpropenylidene)-N-methylmethanaminium tetrafluoroborate (4.05 g), a 1.6M solution (8.8 cc) of butyllithium in hexane and ethyl (phenylthio)acetate (2.8 g) in tetrahydrofuran (65 cc). After purification by chromatography on a silica column with a mixture of cyclohexane and ethyl acetate (70:30 by volume) as eluent, 6-ethyl 1-tert-butyl 2-dimethylamino-5-phenylthio-2,4-hexadienedioate (2.6 g), m.p. 85°-88° C., is obtained. After purification by chromatography on a silica column with a mixture of cyclohexane and ethyl acetate (70:30 by volume) as eluent

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

Procedure: The procedure is as in Example 2 for the preparation of diethyl 2-dimethylamino-5-phenylthio-2,4-hexadienedioate, starting with N-(3-dimethylamino-3-phenylpropenylidene)-N-methylmethanaminium tetrafluoroborate (15.4 g), a 2M solution of sodium ethylate (26.5 cc) and ethyl (phenylthio)acetate (10.4 g) in ethanol (150 cc). After purification by chromatography on a silica column with dichloromethane as eluent, ethyl 5-dimethylamino-5-phenyl-2-phenylthio-2,4-pentadienoate (9.7 g), m.p. 99° C., is obtained. After purification by chromatography on a silica column with dichloromethane as eluent

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

Procedure: The procedure is as in Example 2 for the preparation of diethyl 2-dimethylamino-5-phenylthio-2,4-hexadienedioate, starting with N-(3-dimethylamino-3-phenylpropenylidene)-N-methylmethanaminium tetrafluoroborate (15.4 g), a 2M solution of sodium ethylate (26.5 cc) and ethyl (phenylthio)acetate (10.4 g) in ethanol (150 cc). After purification by chromatography on a silica column with dichloromethane as eluent, ethyl 5-dimethylamino-5-phenyl-2-phenylthio-2,4-pentadienoate (9.7 g), m.p. 99° C., is obtained. After purification by chromatography on a silica column with dichloromethane as eluent

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

Procedure: The procedure is as in Example 2 for the preparation of ethyl (phenylthio)acetate starting with ethyl bromoacetate (16.7 g), a 2M ethanolic solution of sodium ethylate (50 cc) and benzylmercaptan (11.7 cc). Ethyl (benzylthio)acetate (19.4 g) is thereby obtained, and is used in the crude state in the subsequent phases.

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

Procedure: The procedure is as in Example 2 for the preparation of ethyl (phenylthio)acetate starting with ethyl bromoacetate (11.7 g), a 2M ethanolic solution of sodium ethylate (35 cc) and 4-methoxythiophenol (10 g). Ethyl (4-methoxyphenylthio)acetate (13.6 g) is thereby obtained, and is used in the crude state in the subsequent syntheses.

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

Procedure: The procedure is as in Example 2 for the preparation of ethyl (phenylthio)acetate starting with ethyl bromoacetate (11.7 g), a 2M ethanolic solution of sodium ethylate (35 cc) and 4-methoxythiophenol (10 g). Ethyl (4-methoxyphenylthio)acetate (13.6 g) is thereby obtained, and is used in the crude state in the subsequent syntheses.

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

Procedure: The procedure is as in Example 2 for the preparation of ethyl (phenylthio)acetate starting with ethyl bromoacetate (16.7 g), a 2M ethanolic solution of sodium ethylate (50 cc) and 4-chlorothiophenol (14.5 g). Ethyl (4-chlorophenylthio)acetate (20.7 g) is thereby obtained, and is used in the crude state in the subsequent phases.

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

Procedure: To a stirred suspension of 14 g (0.129 mol, 1.4 eq) of 3-hydroxy-1,1-dimethyl-guanidine in 300 mL dry THF at 0° C. was added portionwise 6.191 g (0.155 mol, 1.2 eq) of NaH (60% in oil). The resulting heavy suspension was stirred at RT for 1 hour 30 minutes. Then, 28.126 g (0.129 mol) phenylsulfanyl-acetic acid ethyl ester were slowly added. The reaction mixture was stirred at RT for 2 hours and then at 65° C. for 1 hour. The reaction was quenched by addition of a saturated aqueous solution of NH4Cl and the product extracted with EtOAc. The combined organic phase was dried on Na2SO4, filtered and evaporated. Column chromatography on silica gel (EtOAc/heptane, 1:9 to 1:2) yielded 19.370 g (64%) dimethyl-(5-phenylsulfanylmethyl-[1,2,4]oxadiazol-3-yl)-amine as a colorless oil, MS: 236 (MH+). The reaction mixture was stirred at RT for 2 hours at 65° C. for 1 hour The reaction was quenched by addition of a saturated aqueous solution of NH4Cl the product extracted with EtOAc The combined organic phase was dried on Na2SO4 filtered evaporated