3-(dimethylamino)-1-phenylprop-2-en-1-one

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

Procedure: By using a method similar to that described in Example 35, but starting from 3-dimethylaminoacrylophenone (5 g), phosphorus oxychloride (2.47 cc), 4-methylthiophenol (3.55 g) and sodium cyanoborohydride (1 g), and after evaporating the organic phase to dryness under reduced pressure (2.7 kPa) at 40° C., an orange oil is obtained which is dissolved in isopropanol (40 cc). A 5.6N solution (7 cc) of hydrochloric acid gas in ethyl ether is added to this solution. The precipitate formed is separated off by filtration and then recrystallised from isopropanol (40 cc). In this way 1-dimethylamino-3-(4-methylphenylthio)-3-phenyl-2-propene (Z) hydrochloride (3.3 g) is obtained in the form of a white solid melting at 197°-198° C. after evaporating the organic phase to dryness under reduced pressure (2.7 kPa) at 40° C. an orange oil is obtained which The precipitate formed is separated off by filtration recrystallised from isopropanol (40 cc)

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

Procedure: By using a method similar to that described in Example 35, but starting from 3-dimethylaminoacrylophenone (5 g), phosphorus oxychloride (2.47 cc), 4-methylthiophenol (3.55 g) and sodium cyanoborohydride (1 g), and after evaporating the organic phase to dryness under reduced pressure (2.7 kPa) at 40° C., an orange oil is obtained which is dissolved in isopropanol (40 cc). A 5.6N solution (7 cc) of hydrochloric acid gas in ethyl ether is added to this solution. The precipitate formed is separated off by filtration and then recrystallised from isopropanol (40 cc). In this way 1-dimethylamino-3-(4-methylphenylthio)-3-phenyl-2-propene (Z) hydrochloride (3.3 g) is obtained in the form of a white solid melting at 197°-198° C. after evaporating the organic phase to dryness under reduced pressure (2.7 kPa) at 40° C. an orange oil is obtained which The precipitate formed is separated off by filtration recrystallised from isopropanol (40 cc)

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

Procedure: By using a method similar to that described in Example 35, but starting from 3-dimethylaminoacrylophenone (5 g), phosphorus oxychloride (2.5 cc), 3-chlorothiophenol (4.13 g) and sodium cyanoborohydride (1 g), and after evaporating the organic phase to dryness under reduced pressure (2.7 kPa) at 40° C., a residue is obtained which is dissolved in a mixture (20 cc) of acetone and ethyl ether (50/50 by volume). A 5.6N solution (6 cc) of hydrochloric acid gas in ethyl ether is added to this solution. The precipitate formed is separated off by filtration and then recrystallised from isopropanol (30 cc). In this way 3-(3-chlorophenylthio)-1-dimethylamino-3-phenyl-2-propene (Z) hydrochloride (2.6 g) is obtained in the form of a white solid melting at 156°-157° C. after evaporating the organic phase to dryness under reduced pressure (2.7 kPa) at 40° C. a residue is obtained which The precipitate formed is separated off by filtration recrystallised from isopropanol (30 cc)

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

Procedure: By using a method similar to that described in Example 35, but starting from 3-dimethylaminoacrylophenone (6.1 g), phosphorus oxychloride (3 cc), 2-chlorothiophenol (5 g) and sodium cyanoborohydride (1.3 g), and after evaporating the organic phase to dryness under reduced pressure (2.7 kPa) at 40° C., a yellow oil is obtained which is dissolved in isopropanol (20 cc). A 5.6N solution (7.8 cc) of hydrochloric acid gas in ethyl ether is added to this solution. The precipitate formed is separated off by filtration and then recrystallised from isopropanol (20 cc). In this way 3-(2-chlorophenylthio)-1-dimethylamino-3-phenyl-2-propene (Z) hydrochloride (2.5 g) is obtained in the form of a white solid melting at 162° C. after evaporating the organic phase to dryness under reduced pressure (2.7 kPa) at 40° C. a yellow oil is obtained which The precipitate formed is separated off by filtration recrystallised from isopropanol (20 cc)

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

Procedure: By using a method similar to that described in Example 35, but starting from 3-dimethylaminoacrylophenone (6.1 g), phosphorus oxychloride (3 cc), 2-chlorothiophenol (5 g) and sodium cyanoborohydride (1.3 g), and after evaporating the organic phase to dryness under reduced pressure (2.7 kPa) at 40° C., a yellow oil is obtained which is dissolved in isopropanol (20 cc). A 5.6N solution (7.8 cc) of hydrochloric acid gas in ethyl ether is added to this solution. The precipitate formed is separated off by filtration and then recrystallised from isopropanol (20 cc). In this way 3-(2-chlorophenylthio)-1-dimethylamino-3-phenyl-2-propene (Z) hydrochloride (2.5 g) is obtained in the form of a white solid melting at 162° C. after evaporating the organic phase to dryness under reduced pressure (2.7 kPa) at 40° C. a yellow oil is obtained which The precipitate formed is separated off by filtration recrystallised from isopropanol (20 cc)

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

Procedure: By using a method similar to that described in Example 35, but starting from 3-dimethylaminoacrylophenone (5 g), phosphorus oxychloride (2.47 cc), 4-bromothiophenol (5.39 g) and sodium cyanoborohydride (1 g), a chestnut-coloured residue is obtained which is taken up in chloroform. The solution is made alkaline to pH 10 with an aqueous solution of sodium hydroxide. After separation of the chloroform phase, the aqueous phase is extracted with methylene chloride. The organic phases are collected, dried over sodium sulphate, filtered and then evaporated to dryness under reduced pressure (2.7 kPa) at 30° C. A residue is obtained which is dissolved in ethanol (60 cc). A 3N ether solution (7.7 cc) of hydrochloric acid gas is added to this solution. The white solid which precipitates is separated off by filtration and recrystallised from a mixture of isopropanol and methanol (60/40 by volume). In this way 3-(4-bromophenylthio)-1-dimethylamino-3-phenyl-2-propene (Z) hydrochloride (1.8 g) is obtained in the form of a white solid melting at 252° C. a chestnut-coloured residue is obtained which After separation of the chloroform phase the aqueous phase is extracted with methylene chloride The organic phases are collected dried over sodium sulphate filtered evaporated to dryness under reduced pressure (2.7 kPa) at 30° C A residue is obtained which The white solid which precipitates is separated off by filtration recrystallised from a mixture of isopropanol and methanol (60/40 by volume)

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

Procedure: By using a method similar to that described in Example 35, but starting from 3-dimethylaminoacrylophenone (5 g), phosphorus oxychloride (2.47 cc), 4-bromothiophenol (5.39 g) and sodium cyanoborohydride (1 g), a chestnut-coloured residue is obtained which is taken up in chloroform. The solution is made alkaline to pH 10 with an aqueous solution of sodium hydroxide. After separation of the chloroform phase, the aqueous phase is extracted with methylene chloride. The organic phases are collected, dried over sodium sulphate, filtered and then evaporated to dryness under reduced pressure (2.7 kPa) at 30° C. A residue is obtained which is dissolved in ethanol (60 cc). A 3N ether solution (7.7 cc) of hydrochloric acid gas is added to this solution. The white solid which precipitates is separated off by filtration and recrystallised from a mixture of isopropanol and methanol (60/40 by volume). In this way 3-(4-bromophenylthio)-1-dimethylamino-3-phenyl-2-propene (Z) hydrochloride (1.8 g) is obtained in the form of a white solid melting at 252° C. a chestnut-coloured residue is obtained which After separation of the chloroform phase the aqueous phase is extracted with methylene chloride The organic phases are collected dried over sodium sulphate filtered evaporated to dryness under reduced pressure (2.7 kPa) at 30° C A residue is obtained which The white solid which precipitates is separated off by filtration recrystallised from a mixture of isopropanol and methanol (60/40 by volume)

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

Procedure: By using a method similar to that described in Example 35, but starting from 3-dimethylaminoacrylophenone (10 g), phosphorus oxychloride (5 cc), 4-mercaptopyridine (6.35 g) and sodium cyanoborohydride (2 g), a chestnut-coloured residue is obtained which is taken up in water (100 cc). The solution is acidified to pH 2 by adding an aqueous solution of concentrated hydrochloric acid and then washed with ethyl ether (2×50 cc). The aqueous phase is adjusted to pH 10 by adding a concentrated aqueous solution of sodium hydroxide and then extracted with methylene chloride. The resultant organic phase is dried over sodium sulphate, filtered and then concentrated to dryness under reduced pressure (2.7 kPa) at 30° C. to give a red residue which is chromatographed on silica gel [eluent: methylene chloride/methanol (95/5 by volume)], 200 cc fractions being collected. Fractions 13 to 25 are concentrated under reduced pressure (2.7 kPa) at 30° C. A residue is obtained which is dissolved in ethanol (15 cc). A 1.2N ethanolic solution (20 cc) of oxalic acid is added to this solution; the solid which precipitates is separated off by filtration and recrystallised from a mixture (110 cc) of acetonitrile and ethanol (20/80 by volume). In this way 1-dimethylamino-3-phenyl-3-(4-pyridylthio)-2-propene (Z) sesquioxalate (3 g) is obtained in the form of white crystals melting at 173° C. a chestnut-coloured residue is obtained which washed with ethyl ether (2×50 cc) by adding a concentrated aqueous solution of sodium hydroxide extracted with methylene chloride The resultant organic phase is dried over sodium sulphate filtered concentrated to dryness under reduced pressure (2.7 kPa) at 30° C. to give a red residue which is chromatographed on silica gel [eluent: methylene chloride/methanol (95/5 by volume)], 200 cc fractions being collected Fractions 13 to 25 are concentrated under reduced pressure (2.7 kPa) at 30° C A residue is obtained which the solid which precipitates is separated off by filtration recrystallised from a mixture (110 cc) of acetonitrile and ethanol (20/80 by volume)

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

Procedure: By using a method similar to that described in Example 35, but starting from 3-dimethylaminoacrylophenone (5 g), phosphorus oxychloride (2.5 cc), p-chlorothiophenol (4.13 g) and sodium cyanoborohydride (1 g), and after evaporating the reaction mixture under reduced pressure (2.7 kPa) at 40° C., a residue is obtained, which is dissolved in ethanol (50 cc). A 3N solution (12 cc) of hydrochloric acid gas in ethyl ether is added to this solution. The precipitate formed is separated off by filtration and then recrystallised from ethanol (70 cc). In this way 3-(4-chlorophenylthio)-1-dimethylamino-3-phenylthio-2-propene (Z) hydrochloride (3.4 g) is obtained in the form of a white powder melting at 226° C. after evaporating the reaction mixture under reduced pressure (2.7 kPa) at 40° C. a residue is obtained The precipitate formed is separated off by filtration recrystallised from ethanol (70 cc)

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

Procedure: By using a method similar to that described in Example 35, but starting from 3-dimethylaminoacrylophenone (5 g), phosphorus oxychloride (2.5 cc), p-chlorothiophenol (4.13 g) and sodium cyanoborohydride (1 g), and after evaporating the reaction mixture under reduced pressure (2.7 kPa) at 40° C., a residue is obtained, which is dissolved in ethanol (50 cc). A 3N solution (12 cc) of hydrochloric acid gas in ethyl ether is added to this solution. The precipitate formed is separated off by filtration and then recrystallised from ethanol (70 cc). In this way 3-(4-chlorophenylthio)-1-dimethylamino-3-phenylthio-2-propene (Z) hydrochloride (3.4 g) is obtained in the form of a white powder melting at 226° C. after evaporating the reaction mixture under reduced pressure (2.7 kPa) at 40° C. a residue is obtained The precipitate formed is separated off by filtration recrystallised from ethanol (70 cc)

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

Procedure: By using a method similar to that described in Example 35, but starting from 3-dimethylaminoacrylophenone (80 g), phosphorus oxychloride (40 cc), thiophenol (50.3 cc) and sodium cyanoborohydride (16 g), and crystallising the (Z)-isomer, a yellow solid is isolated after evaporation of the mother liquors under reduced pressure (2.7 kPa) at 30° C. followed by crystallisation of the residue obtained from a mixture of acetone and ethyl ether (25/75 by volume); the solid is recrystallised from methyl ethyl ketone (230 cc). 1-Dimethylamino-3-phenyl-3-phenylthio-2-propene (E) hydrochloride (14.3 g) is thus obtained in the form of a white solid melting at 146°-147° C. crystallising the (Z)-isomer a yellow solid is isolated after evaporation of the mother liquors under reduced pressure (2.7 kPa) at 30° C. followed by crystallisation of the residue obtained from a mixture of acetone and ethyl ether (25/75 by volume) the solid is recrystallised from methyl ethyl ketone (230 cc)

Conditions: temp:20.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Phosphorus oxychloride (2.5 cc) dissolved in methylene chloride (6 cc) is added dropwise at 0° C. to a solution of 3-dimethylaminoacrylophenone (5 g) in methylene chloride (16 cc). After starting for 15 minutes at 0° C. and then 30 minutes at 20° C., the temperature is again brought down to 0° C. The precipitate formed is dissolved by adding methanol (5 cc). Triethylamine (8 cc) and thiophenol (3.15 cc) dissolved in methylene chloride (10 cc) are added dropwise. After 2 hours 30 minutes' stirring at 20° C., methanol (30 cc) is added followed by sodium cyanoborohydride (1 g) at 0° C. and stirring is continued for 3 hours at 20° C. The mixture is then concentrated under reduced pressure (2.7 kPa) at 40° C. The solid obtained is taken up in chloroform and the solution is filtered. The organic phase is evaporated under reduced pressure (2.7 kPa) at 40° C. The residue obtained is taken up in water and the solution is made alkaline to pH 10 by adding a 35% strength aqueous solution of sodium hydroxide, and then extracted with methylene chloride. The organic phase is dried over sodium sulphate, filtered and then evaporated to dryness under reduced pressure (2.7 kPa) at 40° C. The residue obtained is dissolved in ethyl ether (10 cc). A 3N solution (10 cc) of hydrochloric acid gas in ethyl ether is added to the solution obtained. The precipitate formed is separated off by filtration and then recrystallised from a mixture of ethanol (15 cc) and ethyl ether (20 cc). In this way 1-dimethylamino-3-phenyl-3-phenylthio-2-propene (Z) hydrochloride (3 g) is obtained in the form of white crystals melting at 176° C. 30 minutes at 20° C. is again brought down to 0° C The precipitate formed is dissolved are added dropwise stirring is continued for 3 hours at 20° C The mixture is then concentrated under reduced pressure (2.7 kPa) at 40° C The solid obtained the solution is filtered The organic phase is evaporated under reduced pressure (2.7 kPa) at 40° C The residue obtained extracted with methylene chloride The organic phase is dried over sodium sulphate filtered evaporated to dryness under reduced pressure (2.7 kPa) at 40° C The residue obtained obtained The precipitate formed is separated off by filtration recrystallised from a mixture of ethanol (15 cc) and ethyl ether (20 cc)