2-氯-1,3-二甲苯

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: According to the general procedure B, 2-Chloro-m-xylene (70 mg, 0.50 mmol) reacted with n-hexylamine (80 μl, 0.60 mmol) using 2 mol % of Pd(OAc)2, 4 mol % of Ph5FcP(t-Bu)2, and sodium tert-butoxide (58 mg, 0.60 mmol) in toluene (1.5 ml) at 100° C. to give the title compound (100 mg, 97%) as a colorless oil: 1H-NMR (400 MHz, CDCl3): δ 7.02 (d, 2H, J=7.2 Hz), 6.83 (t, 1H, J=7.2 Hz), 3.00 (t, 2H, J=7.2 and 7.6 Hz), 3.0 (bs, 1H), 2.32 (s, 6H), 1.61 (m, 2H), 1.45-1.31 (m, 6H), 0.93 (t, 3H, J=5.6 and 7.2 Hz). 13C{1H}-NMR (100 MHz, CDCl3): δ 146.37, 129.05, 128.75, 121.52, 48.69, 31.73, 31.14, 26.83, 22.62, 18.54, 14.03. GC/MS(EI): m/z 205 (M+). at 100° C.

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: A solution of 2-chloro-m-xylene (5.00 g, 35.60 mmol), NBS (5.70 g, 32.03 mmol), and a catalytic amount of benzoyl peroxide (100 mg) in CCl4 was refluxed for 1 hour. After cooling to room temperature the resulting mixture was filtered and the filtrate was distilled off. Purification by column chromatography using pentane as the eluant followed by distillation afforded the title compound. Spectroscopic data: 1H NMR (300 MHz, CDCl3.) δ 2.39 (s, 3H), 4.61 (s, 2H), 7.08-7.23 (m, 2H), 7.25-7.30 (m, 1H). was filtered the filtrate was distilled off Purification by column chromatography followed by distillation

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Nitration of 2-chloro-m-xylene. Nitric acid (90%, 50 mL) was cooled to −35° C. (ethanol-dry ice bath). 2-Chloro-m-xylene (10 mL) was added dropwise over 1 h keeping the temperature between −30° C. and −35° C. The reaction mixture was poured onto ice, stirred for 10 min, precipitate formed was collected by filtration, washed with water, dried. The crude product was purified on SiO2 (50 g), hexane-EtOAc (0 to 2% v/v). The product—yellow solid, 12.8 g, as a mixture of 2-chloro-1,3-dimethyl-4-nitro-benzene and chloro-1,3-dimethyl-5-nitro-benzene (4:1). the temperature between −30° C. and −35° C The reaction mixture was poured onto ice precipitate formed was collected by filtration washed with water dried The crude product was purified on SiO2 (50 g), hexane-EtOAc (0 to 2% v/v) The product—yellow solid, 12.8 g, as a mixture of 2-chloro-1,3-dimethyl-4-nitro-benzene and chloro-1,3-dimethyl-5-nitro-benzene (4:1)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: This reaction is carried out in the same manner as the reaction in example 3. The difference is that, the reactants are 2,6-dimethylphenyl chloride (142.4 mg, 1.0 mmol), palladium cinnamyl chloride (7.8 mg, 0.015 mmol), 2-Methoxy-6-(N-methyl-N-phenyl-amino)phenyldicyclohexyl)phosphine (24.4 mg, 0.060 mmol), Cs2CO3 (651.9 mg, 2.0 mmol) in 4.0 mL acetone at 90° C. for 22 h. 1-(2′,6′-Dimethylphenyl)-2-propanone (138.4 mg) was obtained with a yield of 84% as liquid. 1H NMR (300 MHz, CDCl3) δ 7.15-7.03 (m, 3H, ArH), 3.79 (s, 2H, CH2), 2.27 (s, 6H, 2×ArCH3), 2.17 (s, 3H, COCH3); 13C NMR (75 MHz, CDCl3) δ 206.2, 136.7, 132.1, 128.1, 126.9, 45.0, 29.2, 20.2; IR (neat) v (cm−1) 3021, 2922, 2867, 1715, 1589, 1470, 1446, 1415, 1379, 1357, 1317, 1223, 1158, 1095, 1053, 1031; MS (70 eV, EI) m/z (%): 163 (M++1, 3.30), 162 (M+, 27.85), 119 (100); HRMS calcd for C11H14O (M+): 162.1045. Found: 162.1046. This reaction is carried out in the same manner as the reaction in example 3 at 90° C. for 22 h

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: This reaction is carried out in the same manner as the reaction in example 3. The difference is that, the reactants are 2,6-dimethylphenyl chloride (142.4 mg, 1.0 mmol), palladium cinnamyl chloride (7.8 mg, 0.015 mmol), 2-Methoxy-6-(N-methyl-N-phenyl-amino)phenyldicyclohexyl)phosphine (24.4 mg, 0.060 mmol), Cs2CO3 (651.9 mg, 2.0 mmol) in 4.0 mL acetone at 90° C. for 22 h. 1-(2′,6′-Dimethylphenyl)-2-propanone (138.4 mg) was obtained with a yield of 84% as liquid. 1H NMR (300 MHz, CDCl3) δ 7.15-7.03 (m, 3H, ArH), 3.79 (s, 2H, CH2), 2.27 (s, 6H, 2×ArCH3), 2.17 (s, 3H, COCH3); 13C NMR (75 MHz, CDCl3) δ 206.2, 136.7, 132.1, 128.1, 126.9, 45.0, 29.2, 20.2; IR (neat) v (cm−1) 3021, 2922, 2867, 1715, 1589, 1470, 1446, 1415, 1379, 1357, 1317, 1223, 1158, 1095, 1053, 1031; MS (70 eV, EI) m/z (%): 163 (M++1, 3.30), 162 (M+, 27.85), 119 (100); HRMS calcd for C11H14O (M+): 162.1045. Found: 162.1046. This reaction is carried out in the same manner as the reaction in example 3 at 90° C. for 22 h

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Nitration of 2-chloro-m-xylene. Nitric acid (90%, 50 mL) was cooled to −35° C. (ethanol-dry ice bath). 2-Chloro-m-xylene (10 mL) was added dropwise over 1 h keeping the temperature between −30° C. and −35° C. The reaction mixture was poured onto ice, stirred for 10 min, precipitate formed was collected by filtration, washed with water, dried. The crude product was purified on SiO2 (50 g), hexane-EtOAc (0 to 2% v/v). The product—yellow solid, 12.8 g, as a mixture of 2-chloro-1,3-dimethyl-4-nitro-benzene and chloro-1,3-dimethyl-5-nitro-benzene (4:1). the temperature between −30° C. and −35° C The reaction mixture was poured onto ice precipitate formed was collected by filtration washed with water dried The crude product was purified on SiO2 (50 g), hexane-EtOAc (0 to 2% v/v) The product—yellow solid, 12.8 g, as a mixture of 2-chloro-1,3-dimethyl-4-nitro-benzene and chloro-1,3-dimethyl-5-nitro-benzene (4:1)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Nitration of 2-chloro-m-xylene. Nitric acid (90%, 50 mL) was cooled to −35° C. (ethanol-dry ice bath). 2-Chloro-m-xylene (10 mL) was added dropwise over 1 h keeping the temperature between −30° C. and −35° C. The reaction mixture was poured onto ice, stirred for 10 min, precipitate formed was collected by filtration, washed with water, dried. The crude product was purified on SiO2 (50 g), hexane-EtOAc (0 to 2% v/v). The product—yellow solid, 12.8 g, as a mixture of 2-chloro-1,3-dimethyl-4-nitro-benzene and chloro-1,3-dimethyl-5-nitro-benzene (4:1). the temperature between −30° C. and −35° C The reaction mixture was poured onto ice precipitate formed was collected by filtration washed with water dried The crude product was purified on SiO2 (50 g), hexane-EtOAc (0 to 2% v/v) The product—yellow solid, 12.8 g, as a mixture of 2-chloro-1,3-dimethyl-4-nitro-benzene and chloro-1,3-dimethyl-5-nitro-benzene (4:1)