3,4,4-trifluorobut-3-en-1-ol

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The first method involves hydrolysis of 4-bromo-1,1,2-trifluoro- 1-butene (II) with water in the presence of N-methyl pyrrolidinone to give 3,4,4-trifluor-3-buten-1-ol (III), followed by Jones oxidation under conditions not previously known. These conditions are at a temperature of about 51°-54° C. In addition, the 3,4,4-trifluoro-3-buten-1-ol in acetone solvent and the Jones reagent are added to the reaction vessel simultaneously to afford 3,4,4-trifluoro-3-butenoic (IV) acid in 52% overall yield. ##STR4## are at a temperature of about 51°-54° C

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 8.2 g (40 mmol) of 2-methyl-4-(4-fluorobenzylidene)-oxazol-5-one of Example (II-1) in 100 ml of toluene are heated overnight under reflux with 6.3 g (50 mmol) of 3,4,4-trifluorobut-3-enol, with the addition of 200 mg of 4-dimethylaminopyridine. After cooling, the solution is washed with water and concentrated under reduced pressure and the brown solid is chromatographed over silica gel using the system chloroform/ethyl acetate (4:1). 6.5 g (Yield 49% of theory) of 3,4,4-trifluorobut-3-enyl 3-(4-fluorophenyl)-2-acetylamino-prop-2-enoate of mp.: 116° are obtained. are heated overnight After cooling the solution is washed with water concentrated under reduced pressure the brown solid is chromatographed over silica gel using the system chloroform/ethyl acetate (4:1)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 8.2 g (40 mmol) of 2-methyl-4-(4-fluorobenzylidene)-oxazol-5-one of Example (II-1) in 100 ml of toluene are heated overnight under reflux with 6.3 g (50 mmol) of 3,4,4-trifluorobut-3-enol, with the addition of 200 mg of 4-dimethylaminopyridine. After cooling, the solution is washed with water and concentrated under reduced pressure and the brown solid is chromatographed over silica gel using the system chloroform/ethyl acetate (4:1). 6.5 g (Yield 49% of theory) of 3,4,4-trifluorobut-3-enyl 3-(4-fluorophenyl)-2-acetylamino-prop-2-enoate of mp.: 116° are obtained. are heated overnight After cooling the solution is washed with water concentrated under reduced pressure the brown solid is chromatographed over silica gel using the system chloroform/ethyl acetate (4:1)

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mechanically stirred 12 L glass reactor clad with a jacket cooled with tap water was charged with 100 mL of acetone and 100 mL of Jones reagent. A solution of 3,4,4-trifluoro-3-buten-1-ol (850 g, 6.75 mol) diluted to a total volume of 5.0 L in acetone was added simultaneously with 5.0 L of Jones reagent via a twin head peristaltic pump capable of of a pump rate ca. 120 mL/min. A reaction temperature of 51°-54° C. was maintained by adjusting the pump rate and the tap water cooling flow. Following the addition (45 min), the mixture was allowed to cool to 35°-40° C. over 30-60 min. The reaction mixture was transferred to a separatory funnel and layers separated. The upper layer was washed once with brine and concentrated. The lower layer was diluted with water (500 mL) and extracted with dichloromethane (3 L). The dichloromethane extract was combined with the above residue, washed with brine and dried over magnesium sulfate. Evaporation of the solvent gave 613 g (65%) of the desired product as a green oil. A reaction temperature of 51°-54° C. was maintained the addition (45 min) to cool to 35°-40° C. over 30-60 min The reaction mixture was transferred to a separatory funnel layers separated The upper layer was washed once with brine concentrated The lower layer was diluted with water (500 mL) extracted with dichloromethane (3 L) The dichloromethane extract washed with brine dried over magnesium sulfate Evaporation of the solvent

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The first method involves hydrolysis of 4-bromo-1,1,2-trifluoro-1-butene (II) with water in the presence of N-methyl pyrrolidinone to give 3,4,4-trifluoro-3-buten-1-ol (III), followed by Jones oxidation under conditions not previously known. These conditions are at a temperature of about 51°-54° C. In addition, the 3,4,4-trifluoro-3-buten-1-ol in acetone solvent and the Jones reagent are added to the reaction vessel simultaneously to afford 3,4,4-trifluoro-3-butenoic (IV) add in 52% overall yield. ##STR4## are at a temperature of about 51°-54° C

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The first method involves hydrolysis of 4-bromo-1,1,2-trifluoro-1-butene (II) with water in the presence of N-methyl pyrrolidinone to give 3,4,4-trifluoro-3-buten-1-ol (III), followed by Jones oxidation under conditions not previously known. These conditions are at a temperature of about 51°-54° C. In addition, the 3,4,4-trifluoro-3-buten-1-ol in acetone solvent and the Jones reagent are added to the reaction vessel simultaneously to afford 3,4,4-trifluoro-3-butenoic (IV) add in 52% overall yield. ##STR4## are at a temperature of about 51°-54° C

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The first method involves hydrolysis of 4-bromo-1,1,2-trifluoro-1-butene (II) with water in the presence of N-methyl pyrrolidinone to give 3,4,4-trifiuoro-3-buten-1-ol (III), followed by Jones oxidation under conditions not previously known. These conditions are at a temperature of about 51°-54° C. In addition, the 3,4,4-trifluoro-3-buten-1-ol in acetone solvent and the Jones reagent are added to the reaction vessel simultaneously to afford 3,4,4-trifluoro-3-butenoic (IV) acid in 52% overall yield. ##STR4## are at a temperature of about 51°-54° C

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The first method involves hydrolysis of 4-bromo-1,1,2-trifluoro-1-butene (II) with water in the presence of N-methyl pyrrolidinone to give 3,4,4-trifiuoro-3-buten-1-ol (III), followed by Jones oxidation under conditions not previously known. These conditions are at a temperature of about 51°-54° C. In addition, the 3,4,4-trifluoro-3-buten-1-ol in acetone solvent and the Jones reagent are added to the reaction vessel simultaneously to afford 3,4,4-trifluoro-3-butenoic (IV) acid in 52% overall yield. ##STR4## are at a temperature of about 51°-54° C

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A mechanically stirred 12 L glass reactor clad with a jacket cooled with tap water was charged with 100 mL of acetone and 100 mL of Jones reagent. A solution of 3,4,4-trifluoro-3-buten-1-ol (850 g, 6.75 mol) diluted to a total volume of 5.0 L in acetone was added simultaneously with 5.0 L of Jones reagent via a twin head peristaltic pump capable of a pump rate ca. 120 mL/min. A reaction temperature of 51°-54° C. was maintained by adjusting the pump rate and the tap water cooling flow. Following the addition (45 min), the mixture was allowed to cool to 35°-40° C. over 30-60 min. The reaction mixture was transferred to a separatory funnel and layers separated. The upper layer was washed once with brine and concentrated. The lower layer was diluted with water (500 mL) and extracted with dichloromethane (3L). The dichloromethane extract was combined with the above residue, washed with brine and dried over magnesium sulfate. Evaporation of the solvent gave 613g (65%) of the desired product as a green oil. A reaction temperature of 51°-54° C. was maintained the addition (45 min) to cool to 35°-40° C. over 30-60 min The reaction mixture was transferred to a separatory funnel layers separated The upper layer was washed once with brine concentrated The lower layer was diluted with water (500 mL) extracted with dichloromethane (3L) The dichloromethane extract washed with brine dried over magnesium sulfate Evaporation of the solvent

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The first method involves hydrolysis of 4-bromo-1,1,2-trifluoro-1butene (II) with water in the presence of N-methyl pyrrolidinone to give 3,4,4-trifluoro-3-buten-1-ol (III), followed by Jones oxidation under conditions not previously known. These conditions are at a temperature of about 51°-54° C. In addition, the 3,4,4-trifluoro-3-buten-1-ol in acetone solvent and the Jones reagent are added to the reaction vessel simultaneously to afford 3,4,4-trifluoro-3-butenoic (IV) acid in 52% overall yield. ##STR3## are at a temperature of about 51°-54° C

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: The first method involves hydrolysis of 4-bromo-1,1,2-trifluoro-1-butene (II) with water in the presence of N-methyl pyrrolidinone to give 3,4,4-trifiuoro-3-buten-1-ol (III), followed by Jones oxidation under conditions not previously known. These conditions are at a temperature of about 51°-54° C. In addition, the 3,4,4-trifluoro-3-buten-1-ol in acetone solvent and the Jones reagent are added to the reaction vessel simultaneously to afford 3,4,4-trifluoro-3-butenoic (IV) acid in 52% overall yield. ##STR4## are at a temperature of about 51°-54° C