N-Formyl-2-methoxy-2-methyl-propylamine

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

实验步骤: A suspension of MIBAHCl (220.00 g, 99.0% (GC), 1.56 mol) in methyl formate (767.32 g, 12.73 mol) was heated to reflux, and triethylamine (175.39 g, 1.73 mol) was added dropwise. The reaction mixture was heated to reflux. The reaction was monitored by TLC until disappearance of MIBAHCl. After 68 hours, the resulting white suspension was cooled to room temperature the solution was filtered and the residue rinsed with diethyl ether (2862 mL). The filtrate was concentrated by rotary evaporation under reduced pressure and the product, a yellow oil, was distilled under reduced pressure (1.5 mmHg). MIBF was yielded as a colorless liquid (201.34 g, 98% yield, 99.8% (GC), b.p.: 120.0-120.5° C./1.50 mmHg); TLC Rf 0.2 (4:1 ethyl acetate/hexanes, detection with p-anisaldehyde spray); FTIR(neat): v 3300, 3061, 2977, 2938, 2831, 2751, 1671, 1534, 1469, 1385, 1368, 1287, 1238, 1183, 1164, 1079, 1034, 1004, 957, 858, 721, 666 cm−1; 1H-NMR(600 MHz, CDCl3): δ 1.13 (s, 6H, 2 CH3), 3.16 (s, 3H, OCH3), 3.28 (d, J=5.9 Hz, 2H, CH2 ), 6.12 (br s, 1H, NH), 8.19 (s, 1H, CHO); 13C-NMR (151 MHz, CDCl3): δ 22.5 (2 CH3), 46.0 (CH2), 49.4 (OCH3), 74.1 (C), 161.4 (CHO); MS (EI): m/z=132[M+H]+; MS (CI): m/z=132[M+H]+. was heated to reflux The reaction mixture was heated to reflux was filtered the residue rinsed with diethyl ether (2862 mL) The filtrate was concentrated by rotary evaporation under reduced pressure the product, a yellow oil, was distilled under reduced pressure (1.5 mmHg) MIBF was yielded as a colorless liquid (201.34 g, 98% yield, 99.8% (GC), b.p.: 120.0-120.5° C./1.50 mmHg)

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

实验步骤: A suspension of MIBAHCl (220.00 g, 99.0% (GC), 1.56 mol) in methyl formate (767.32 g, 12.73 mol) was heated to reflux, and triethylamine (175.39 g, 1.73 mol) was added dropwise. The reaction mixture was heated to reflux. The reaction was monitored by TLC until disappearance of MIBAHCl. After 68 hours, the resulting white suspension was cooled to room temperature the solution was filtered and the residue rinsed with diethyl ether (2862 mL). The filtrate was concentrated by rotary evaporation under reduced pressure and the product, a yellow oil, was distilled under reduced pressure (1.5 mmHg). MIBF was yielded as a colorless liquid (201.34 g, 98% yield, 99.8% (GC), b.p.: 120.0-120.5° C./1.50 mmHg); TLC Rf 0.2 (4:1 ethyl acetate/hexanes, detection with p-anisaldehyde spray); FTIR(neat): v 3300, 3061, 2977, 2938, 2831, 2751, 1671, 1534, 1469, 1385, 1368, 1287, 1238, 1183, 1164, 1079, 1034, 1004, 957, 858, 721, 666 cm−1; 1H-NMR(600 MHz, CDCl3): δ 1.13 (s, 6H, 2 CH3), 3.16 (s, 3H, OCH3), 3.28 (d, J=5.9 Hz, 2H, CH2 ), 6.12 (br s, 1H, NH), 8.19 (s, 1H, CHO); 13C-NMR (151 MHz, CDCl3): δ 22.5 (2 CH3), 46.0 (CH2), 49.4 (OCH3), 74.1 (C), 161.4 (CHO); MS (EI): m/z=132[M+H]+; MS (CI): m/z=132[M+H]+. was heated to reflux The reaction mixture was heated to reflux was filtered the residue rinsed with diethyl ether (2862 mL) The filtrate was concentrated by rotary evaporation under reduced pressure the product, a yellow oil, was distilled under reduced pressure (1.5 mmHg) MIBF was yielded as a colorless liquid (201.34 g, 98% yield, 99.8% (GC), b.p.: 120.0-120.5° C./1.50 mmHg)

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

实验步骤: To a stirred solution of 2-methoxyisobutylamine (16.4 g, 0.16 mol) and a catalytic amount of p-toluenesulphonic acid (75 mg) at 0° C. was added slowly ethylformate (11.79 g, 12.92 ml, 0.16 mol). After the slightly exothermic reaction ceased, the solution was refluxed for 16 hours, and distilled through a Vigreux column to give 19.36 g (93%) of N-formyl-2-methoxyisobutylamine, bp 74° C./15 mm. After the slightly exothermic reaction the solution was refluxed for 16 hours distilled through a Vigreux column

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

实验步骤: A suspension of MIBAHCl (220.00 g, 99.0% (GC), 1.56 mol) in methyl formate (767.32 g, 12.73 mol) was heated to reflux, and triethylamine (175.39 g, 1.73 mol) was added dropwise. The reaction mixture was heated to reflux. The reaction was monitored by TLC until disappearance of MIBAHCl. After 68 hours, the resulting white suspension was cooled to room temperature the solution was filtered and the residue rinsed with diethyl ether (2862 mL). The filtrate was concentrated by rotary evaporation under reduced pressure and the product, a yellow oil, was distilled under reduced pressure (1.5 mmHg). MIBF was yielded as a colorless liquid (201.34 g, 98% yield, 99.8% (GC), b.p.: 120.0-120.5° C./1.50 mmHg); TLC Rf 0.2 (4:1 ethyl acetate/hexanes, detection with p-anisaldehyde spray); FTIR(neat): ν 3300, 3061, 2977, 2938, 2831, 2751, 1671, 1534, 1469, 1385, 1368, 1287, 1238, 1183, 1164, 1079, 1034, 1004, 957, 858, 721, 666 cm−1; 1H-NMR (600 MHz, CDCl3): δ 1.13 (s, 6H, 2 CH3), 3.16 (s, 3H, OCH3), 3.28 (d, J=5.9 Hz, 2H, CH2), 6.12 (br s, 1H, NH), 8.19 (s, 1H, CHO); 13C-NMR (151 MHz, CDCl3): δ 22.5 (2 CH3), 46.0 (CH2), 49.4 (OCH3), 74.1 (C), 161.4 (CHO); MS (EI): m/z=132[M+H]+; MS (Cl): m/z=132[M+H]−. was heated to reflux The reaction mixture was heated to reflux was filtered the residue rinsed with diethyl ether (2862 mL) The filtrate was concentrated by rotary evaporation under reduced pressure the product, a yellow oil, was distilled under reduced pressure (1.5 mmHg) MIBF was yielded as a colorless liquid (201.34 g, 98% yield, 99.8% (GC), b.p.: 120.0-120.5° C./1.50 mmHg)

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

实验步骤: A suspension of MIBAHCl (220.00 g, 99.0% (GC), 1.56 mol) in methyl formate (767.32 g, 12.73 mol) was heated to reflux, and triethylamine (175.39 g, 1.73 mol) was added dropwise. The reaction mixture was heated to reflux. The reaction was monitored by TLC until disappearance of MIBAHCl. After 68 hours, the resulting white suspension was cooled to room temperature the solution was filtered and the residue rinsed with diethyl ether (2862 mL). The filtrate was concentrated by rotary evaporation under reduced pressure and the product, a yellow oil, was distilled under reduced pressure (1.5 mmHg). MIBF was yielded as a colorless liquid (201.34 g, 98% yield, 99.8% (GC), b.p.: 120.0-120.5° C./1.50 mmHg); TLC Rf 0.2 (4:1 ethyl acetate/hexanes, detection with p-anisaldehyde spray); FTIR(neat): v 3300, 3061, 2977, 2938, 2831, 2751, 1671, 1534, 1469, 1385, 1368, 1287, 1238, 1183, 1164, 1079, 1034, 1004, 957, 858, 721, 666 cm−1; 1H-NMR(600 MHz, CDCl3): δ 1.13 (s, 6H, 2 CH3), 3.16 (s, 3H, OCH3), 3.28 (d, J=5.9 Hz, 2H, CH2 ), 6.12 (br s, 1H, NH), 8.19 (s, 1H, CHO); 13C-NMR (151 MHz, CDCl3): δ 22.5 (2 CH3), 46.0 (CH2), 49.4 (OCH3), 74.1 (C), 161.4 (CHO); MS (EI): m/z=132[M+H]+; MS (CI): m/z=132[M+H]+. was heated to reflux The reaction mixture was heated to reflux was filtered the residue rinsed with diethyl ether (2862 mL) The filtrate was concentrated by rotary evaporation under reduced pressure the product, a yellow oil, was distilled under reduced pressure (1.5 mmHg) MIBF was yielded as a colorless liquid (201.34 g, 98% yield, 99.8% (GC), b.p.: 120.0-120.5° C./1.50 mmHg)