3-hydroxybenzenecarbothioamide

反応条件: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 1,3 dichloroacetone (0.42 g, 3.26 mmol) in toluene (5 mL) was added 3-hydroxythiobenzamide (0.25 g, 1.63 mmol) and the reaction mixture was heated at 120° C. for 1 h. After completion of the reaction mixture (TLC monitoring), the reaction mixture was evaporated to dryness, added water and extracted with EtOAc (×3). The combined organics was washed with water, brine, dried (Na2SO4), filtered and concentrated. The crude residue was purified over silica gel (230-400 M, 10% EtOAc-Hexane) to get the desired product (0.14 g, 38%). After completion of the reaction mixture (TLC monitoring), the reaction mixture was evaporated to dryness added water extracted with EtOAc (×3) The combined organics was washed with water, brine dried (Na2SO4) filtered concentrated The crude residue was purified over silica gel (230-400 M, 10% EtOAc-Hexane)

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

実験手順: The procedure used for the preparation of 4a was repeated with 3-hydroxybenzenecarbothioamide 3d (1.53 g, 10.0 mmol) and ethyl 4-chloroacetoacetate (1.65 g, 10.0 mmol) in dry THF (20 mL) to give 4d (2.04 g, 78%) as a white solid after chromatographic purification on silica gel (gradient EtOAc/hexane: 30-40%) and recrystallization from EtOAc/hexane. mp 95.5°-97.2° C.; IR (KBr) 3112, 1727, 1278 cm-1 ; 1H NMR (DMSO-d6) δ 1.15 (3H, t, J=7.0 Hz, CH3), 3.81 (2H, s, CH2), 4.07 (2H, q, J=7.0 Hz, CH2), 6.81 (1H, d, J=7.3 Hz, Ar), 7.22-7.30 (3H, m, Ar), 7.46 (1H, s), 9.68 (1H, s, OH); FDMS m/z 263 (M+); Anal. Calcd for C13H13NO3S: C, 59.30; H, 4.98; N, 5.32. Found: C, 59.41; H, 4.91; N, 5.30.

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

実験手順: The procedure used for the preparation of 4a was repeated with 3-hydroxybenzenecarbothioamide 3d (1.53 g, 10.0 mmol) and ethyl 4-chloroacetoacetate (1.65 g, 10.0 mmol) in dry THF (20 mL) to give 4d (2.04 g, 78%) as a white solid after chromatographic purification on silica gel (gradient EtOAc/hexane: 30-40%) and recrystallization from EtOAc/hexane. mp 95.5°-97.2° C.; IR (KBr) 3112, 1727, 1278 cm-1 ; 1H NMR (DMSO-d6) δ 1.15 (3H, t, J=7.0 Hz, CH3), 3.81 (2H, s, CH2), 4.07 (2H, q, J=7.0 Hz, CH2), 6.81 (1H, d, J=7.3 Hz, Ar), 7.22-7.30 (3H, m, Ar), 7.46 (1H, s), 9.68 (1H, s, OH); FDMS m/z 263 (M+); Anal. Calcd for C13H13NO3S: C, 59.30; H, 4.98; N, 5.32. Found: C, 59.41; H, 4.91; N, 5.30.

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

実験手順: The procedure used for the preparation of 3a was repeated with 3-hydroxybenzonitrile (5.48 g, 46.1 mmol), (EtO)2P(S)SH (7.72 mL, 46.1 mmol) and water (9.2 mL) at 80° C. for 36 hr to give 3d (4.04 g, 57%) as a yellow solid after chromatographic purification on silica gel (gradient EtOAc/CH2Cl2 : 6-12%) and crystallization from EtOAc/hexane. mp 139.0°-140.0° C.; IR (KBr) 3340, 3280, 3165, 1629, 1590, 1462 cm-1 ; 1H NMR (DMSO-d6) δ 6.83 (1H, br d, J=7.0 Hz, Ar), 7.10-7.25 (2H, m, Ar), 7.27 (1H, s, Ar), 9.33 (1H, br s, NH), 9.58 (1H, s, OH), 9.72 (1H, br s, NH); FDMS m/z 153 (M+); Anal. Calcd for C7H7NOS: C, 54.88; H, 4.60; N, 9.14. Found: C, 55.01; H, 4.53; N, 9.02.

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

実験手順: The procedure used for the preparation of 3a was repeated with 3-hydroxybenzonitrile (5.48 g, 46.1 mmol), (EtO)2P(S)SH (7.72 mL, 46.1 mmol) and water (9.2 mL) at 80° C. for 36 hr to give 3d (4.04 g, 57%) as a yellow solid after chromatographic purification on silica gel (gradient EtOAc/CH2Cl2 : 6-12%) and crystallization from EtOAc/hexane. mp 139.0°-140.0° C.; IR (KBr) 3340, 3280, 3165, 1629, 1590, 1462 cm-1 ; 1H NMR (DMSO-d6) δ 6.83 (1H, br d, J=7.0 Hz, Ar), 7.10-7.25 (2H, m, Ar), 7.27 (1H, s, Ar), 9.33 (1H, br s, NH), 9.58 (1H, s, OH), 9.72 (1H, br s, NH); FDMS m/z 153 (M+); Anal. Calcd for C7H7NOS: C, 54.88; H, 4.60; N, 9.14. Found: C, 55.01; H, 4.53; N, 9.02.

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

実験手順: The procedure used for the preparation of 4a was repeated with 3-hydroxybenzenecarbothioamide 3d (1.53 g, 10.0 mmol ) and ethyl 4 -chloroacetoacetate (1.65 g, 10.0 mmol) in dry THF (20 mL) to give 4d (2.04 g, 78%) as a white solid after chromatographic purification on silica gel (gradient EtOAc/hexane: 30-40%) and recrystallization from EtOAc/hexane. mp 95.5°-97.2° C.; IR (KBr) 3112, 1727, 1278 cm-1 ; 1H NMR (DMSO-d6) δ1.15 (3H, t, J=7.0 Hz, CH3), 3.81 (2H, s, CH2), 4.07 (2H, g, J=7.0 Hz, CH2), 6.81 (1H, d, J=7.3 Hz, Ar), 7.22-7.30 (3H, m, Ar), 7.46 (1H, s), 9.68 (1H, s, OH); FDMS m/z 263 (M+); Anal. Calcd for C13H13NO3S: C, 59.30; H, 4.98; N, 5.32. Found: C, 59.41; H, 4.91; N, 5.30.

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

実験手順: The procedure used for the preparation of 4a was repeated with 3-hydroxybenzenecarbothioamide 3d (1.53 g, 10.0 mmol ) and ethyl 4 -chloroacetoacetate (1.65 g, 10.0 mmol) in dry THF (20 mL) to give 4d (2.04 g, 78%) as a white solid after chromatographic purification on silica gel (gradient EtOAc/hexane: 30-40%) and recrystallization from EtOAc/hexane. mp 95.5°-97.2° C.; IR (KBr) 3112, 1727, 1278 cm-1 ; 1H NMR (DMSO-d6) δ1.15 (3H, t, J=7.0 Hz, CH3), 3.81 (2H, s, CH2), 4.07 (2H, g, J=7.0 Hz, CH2), 6.81 (1H, d, J=7.3 Hz, Ar), 7.22-7.30 (3H, m, Ar), 7.46 (1H, s), 9.68 (1H, s, OH); FDMS m/z 263 (M+); Anal. Calcd for C13H13NO3S: C, 59.30; H, 4.98; N, 5.32. Found: C, 59.41; H, 4.91; N, 5.30.

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

実験手順: The procedure used for the preparation of 3a was repeated with 3-hydroxybenzonitrile (5.48 g, 46.1 mmol), (EtO)2P(S)SH (7.72 mL, 46.1 mmol) and water (9.2 mL) at 80° C. for 36 hr to give 3d (4.04 g, 57%) as a yellow solid after chromatographic purification on silica gel (gradient EtOAc/CH2Cl2 : 6-12%) and crystallization from EtOAc/hexane. mp 139.0°-140.0° C.; IR (KBr) 3340, 3280, 3165, 1629, 1590, 1462 cm-1 ; 1H NMR (DMSO-d6) δ6.83 (1H, br d, J=7.0 Hz, Ar), 7.10-7.25 (2H, m, Ar), 7.27 (1H, s, Ar), 9.33 (1H, br s, NH), 9.58 (1H, s, OH), 9.72 (1H, br s, NH); FDMS m/z 153 (M+); Anal. Calcd for C7H7NOS: C, 54.88; H, 4.60; N, 9.14. Found: C, 55.01; H, 4.53; N, 9.02.

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

実験手順: The procedure used for the preparation of 3a was repeated with 3-hydroxybenzonitrile (5.48 g, 46.1 mmol), (EtO)2P(S)SH (7.72 mL, 46.1 mmol) and water (9.2 mL) at 80° C. for 36 hr to give 3d (4.04 g, 57%) as a yellow solid after chromatographic purification on silica gel (gradient EtOAc/CH2Cl2 : 6-12%) and crystallization from EtOAc/hexane. mp 139.0°-140.0° C.; IR (KBr) 3340, 3280, 3165, 1629, 1590, 1462 cm-1 ; 1H NMR (DMSO-d6) δ6.83 (1H, br d, J=7.0 Hz, Ar), 7.10-7.25 (2H, m, Ar), 7.27 (1H, s, Ar), 9.33 (1H, br s, NH), 9.58 (1H, s, OH), 9.72 (1H, br s, NH); FDMS m/z 153 (M+); Anal. Calcd for C7H7NOS: C, 54.88; H, 4.60; N, 9.14. Found: C, 55.01; H, 4.53; N, 9.02.

反応条件: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 1,3 dichloroacetone (0.42 g, 3.26 mmol) in toluene (5 mL) was added 3-hydroxythiobenzamide (0.25 g, 1.63 mmol) and the reaction mixture was heated at 120° C. for 1 h. After completion of the reaction mixture (TLC monitoring), the reaction mixture was evaporated to dryness, added water and extracted with EtOAc (×3). The combined organics was washed with water, brine, dried (Na2SO4), filtered and concentrated. The crude residue was purified over silica gel (230-400 M, 10% EtOAc-Hexane) to get the desired product (0.14 g, 38%). After completion of the reaction mixture (TLC monitoring), the reaction mixture was evaporated to dryness added water extracted with EtOAc (×3) The combined organics was washed with water, brine dried (Na2SO4) filtered concentrated The crude residue was purified over silica gel (230-400 M, 10% EtOAc-Hexane)

反応条件: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 1,3 dichloroacetone (0.42 g, 3.26 mmol) in toluene (5 mL) was added 3-hydroxythiobenzamide (0.25 g, 1.63 mmol) and the reaction mixture was heated at 120° C. for 1 h. After completion of the reaction mixture (TLC monitoring), the reaction mixture was evaporated to dryness, added water and extracted with EtOAc (×3). The combined organics was washed with water, brine, dried (Na2SO4), filtered and concentrated. The crude residue was purified over silica gel (230-400 M, 10% EtOAc-Hexane) to get the desired product (0.14 g, 38%). After completion of the reaction mixture (TLC monitoring), the reaction mixture was evaporated to dryness added water extracted with EtOAc (×3) The combined organics was washed with water, brine dried (Na2SO4) filtered concentrated The crude residue was purified over silica gel (230-400 M, 10% EtOAc-Hexane)

反応条件: temp:120.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a solution of 1,3 dichloroacetone (0.42 g, 3.26 mmol) in toluene (5 mL) was added 3-hydroxythiobenzamide (0.25 g, 1.63 mmol) and the reaction mixture was heated at 120° C. for 1 h. After completion of the reaction mixture (TLC monitoring), the reaction mixture was evaporated to dryness, added water and extracted with EtOAc (×3). The combined organics was washed with water, brine, dried (Na2SO4), filtered and concentrated. The crude residue was purified over silica gel (230-400 M, 10% EtOAc-Hexane) to get the desired product (0.14 g, 38%). After completion of the reaction mixture (TLC monitoring), the reaction mixture was evaporated to dryness added water extracted with EtOAc (×3) The combined organics was washed with water, brine dried (Na2SO4) filtered concentrated The crude residue was purified over silica gel (230-400 M, 10% EtOAc-Hexane)