2-chlorobutanoyl chloride

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:

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: Following the procedure of Kem K. M.; Nguyen N. V.; Cross D. J. J. Org. Chem. 1981;46:5188 for the preparation of chloroacetamides, a solution of 2-chlorobutyryl chloride (61.91 mmol, 8.73 g, Lancaster) in 28 mL of CH2Cl2 was added to diethylamine (56.28 mol, 4.12 g, Aldrich) in a mixture of CH2Cl2 (56 mL) and NaOH (56 mL, 20% aqueous) at −25° C. to furnish 2-chloro-N,N-diethyl-butyramide (7.23 g, 72%). 1HNMR (400 MHz, CDCl3) δ 0.98 (t, J=7.33 Hz, 3H, CH2CH3), 1.12 (t, J=7.08 Hz, 3H, CH2CH3), 1.19-1.23 (m, 3H, CH2CH3), 1.89-2.00 (m, 1H, CH2CH3), 2.03-2.14 (m, 1H, CH2CH3), 3.22-3.38 (m, 2H, NCH2CH3), 3.41-3.52 (m, 2H, NCH2CH3), 4.26 (t, J=7.08 Hz, 1H, CHCl); MS(APCI+): m/z 177.9 (M+1), 179.9 (M+3).

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

実験手順: A suspension of 20.3 g of 2-chloro-butyryl chloride and 12.3 g of 2-amino-3-trifluoromethyl-benzoic acid in toluene was refluxed under reduced pressure for one hour and was then evaporated to dryness under reduced pressure. The oil residue was added to 100 ml of iced water and the mixture was stirred for one hour and was vacuum filtered. The product was washed with water and dried under reduced pressure at 50° C. to obtain 17 g of 2-(1-chloropropyl)-8-trifluoromethyl-4H-3,1-benzoxazine-4-one melting at 65°-70° C. was refluxed under reduced pressure for one hour was then evaporated to dryness under reduced pressure The oil residue was added to 100 ml of iced water filtered The product was washed with water dried under reduced pressure at 50° C.

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

実験手順: To a mixture of 7.39 g (0.015 mole) of triphenylsulfonium 2-hydroxy-1,1,3,3,3-pentafluoropropane-1-sulfonate, 2.33 g (0.017 mole) of chlorobutyric chloride, and 37 g of acetonitrile, 1.42 g (0.018 mole) of pyridine was added dropwise, followed by stirring at room temperature for 3 hours. Then 18 g of 5% dilute hydrochloric acid was added to the reaction solution whereupon acetonitrile was distilled off under vacuum. The residue was combined with 40 g of dichloromethane whereupon the organic layer was separated. The organic layer was washed with 30 g of water, from which dichloromethane was distilled off under vacuum. To the residue was added 40 g of methyl isobutyl ketone. This was washed with 30 g of water, with 30 g of dilute aqueous ammonia, and three times with 30 g of water whereupon methyl isobutyl ketone was distilled off under vacuum. Ether was added to the residue, followed by decantation and vacuum drying. The target compound was obtained as brown oil (7.94 g, yield 87%). was added dropwise was distilled off under vacuum was separated The organic layer was washed with 30 g of water, from which dichloromethane was distilled off under vacuum To the residue was added 40 g of methyl isobutyl ketone This was washed with 30 g of water, with 30 g of dilute aqueous ammonia, and three times with 30 g of water whereupon methyl isobutyl ketone was distilled off under vacuum Ether was added to the residue drying

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

実験手順: To a mixture of 7.39 g (0.015 mole) of triphenylsulfonium 2-hydroxy-1,1,3,3,3-pentafluoropropane-1-sulfonate, 2.33 g (0.017 mole) of chlorobutyric chloride, and 37 g of acetonitrile, 1.42 g (0.018 mole) of pyridine was added dropwise, followed by stirring at room temperature for 3 hours. Then 18 g of 5% dilute hydrochloric acid was added to the reaction solution whereupon acetonitrile was distilled off under vacuum. The residue was combined with 40 g of dichloromethane whereupon the organic layer was separated. The organic layer was washed with 30 g of water, from which dichloromethane was distilled off under vacuum. To the residue was added 40 g of methyl isobutyl ketone. This was washed with 30 g of water, with 30 g of dilute aqueous ammonia, and three times with 30 g of water whereupon methyl isobutyl ketone was distilled off under vacuum. Ether was added to the residue, followed by decantation and vacuum drying. The target compound was obtained as brown oil (7.94 g, yield 87%). was added dropwise was distilled off under vacuum was separated The organic layer was washed with 30 g of water, from which dichloromethane was distilled off under vacuum To the residue was added 40 g of methyl isobutyl ketone This was washed with 30 g of water, with 30 g of dilute aqueous ammonia, and three times with 30 g of water whereupon methyl isobutyl ketone was distilled off under vacuum Ether was added to the residue drying

反応条件: temp:-2.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To 6.4 g. (0.06 moles) anhydrous sodium carbonate in 60 cc. H2O was added 10.2 g. (0.05 moles) of m-chloroperbenzoic acid of 84.35% purity. The stirred mixture was chilled to -2° C. and 8.5 g. (0.06 moles) 2-chlorobutyryl chloride in 30 cc. chloroform was added over 17 minutes. After a total reaction time of 60 minutes, the reaction was worked up as in Example I and gave 15.2 g. product. Product A.O. analysis: theory, 5.77; found, 5.15; 89.30% pure; 97.7% yield. After a total reaction time of 60 minutes gave 15.2 g

反応条件: temp:-3.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To 9.5 g. (0.05 moles) of 40% peracetic acid in 20 cc. H2O was added 3.2 g. (0.03 moles) of anhydrous sodium carbonate. The mixture was chilled to -3° C. with stirring and 7.1 g. (0.05 moles) of 2-chlorobutyryl chloride in 30 cc. chloroform added over a period of 8 minutes. After a total of 40 minutes at -3° to -6° C., ether and water were added. The organic phase was separated, washed once with cold 1% KOH solution, once with ice water, and once with cold saturated salt water. The concentrated material weighed 8.2 g., including 2.0 g. of dimethyl phthlate. Product A.O. analysis: theory, 8.14 found, 4.81; 59.1% pure; 49.5% yield. The organic phase was separated washed once with cold 1% KOH solution, once with ice water

反応条件: temp:-3.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To 9.5 g. (0.05 moles) of 40% peracetic acid in 20 cc. H2O was added 3.2 g. (0.03 moles) of anhydrous sodium carbonate. The mixture was chilled to -3° C. with stirring and 7.1 g. (0.05 moles) of 2-chlorobutyryl chloride in 30 cc. chloroform added over a period of 8 minutes. After a total of 40 minutes at -3° to -6° C., ether and water were added. The organic phase was separated, washed once with cold 1% KOH solution, once with ice water, and once with cold saturated salt water. The concentrated material weighed 8.2 g., including 2.0 g. of dimethyl phthlate. Product A.O. analysis: theory, 8.14 found, 4.81; 59.1% pure; 49.5% yield. The organic phase was separated washed once with cold 1% KOH solution, once with ice water

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir: