2-BROMO-5-METHOXYBENZYLAMINE synthesis
- Product Name:2-BROMO-5-METHOXYBENZYLAMINE
- CAS Number:887581-09-1
- Molecular formula:C8H10BrNO
- Molecular Weight:216.08
138642-47-4
887581-09-1
Step A: Synthesis of 1-(2-bromo-5-methoxyphenyl)methanamine 2-Bromo-5-methoxybenzonitrile (10.0 g, 47.2 mmol) was dissolved in dry tetrahydrofuran (100 mL) in a flame-dried flask and cooled in an ice bath. A solution of borane-tetrahydrofuran complex (75 mL, 75 mmol, 1.0 M) was added slowly and dropwise over 30 min. The reaction mixture was stirred overnight at room temperature and then the reaction was slowly quenched with ice water and saturated aqueous sodium carbonate solution. Tetrahydrofuran was removed by distillation under reduced pressure and the residue was extracted with ethyl acetate (EtOAc) several times (3 times). The organic layers were combined, washed with water, dried over anhydrous sodium sulfate and concentrated under reduced pressure to give the crude product. The crude product was purified by silica gel column chromatography to afford the target product 1-(2-bromo-5-methoxyphenyl)methanamine as a white powder (3.65 g, 36% yield). m/z = 216.9, 219.0 for C8H10BrNO ([M+H]+) by LCMS analysis.
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Yield:887581-09-1 95%
Reaction Conditions:
Stage #1: 2-bromo-5-methoxy-benzaldehydewith tert-butyldimethylsilane;methyl carbamate;trifluoroacetic acid in acetonitrile at 80; for 6 h;
Stage #2: with water;lithium hydroxide in tetrahydrofuran;methanol at 80; for 16 h;
Steps:
2-Bromo-5-methoxybenzylamine (3b).
To a stirred solution of bromobenzaldehyde 1b (1.0 g, 4.6 mmol) and methyl carbamate (524 mg, 7.0 mmol) in acetonitrile (12 mL), were added sequentially TFA (0.71 mL, 9.3 mmol) and tert-butyldiemthylsilane (TBDMSH) (1.53 mL, 9.3 mmol) and the resulting solution was stirred at 80 °C for 6 h. The reaction mixture was concentrated in vacuo and the residue dissolved in a mixture of THF, MeOH and aq. LiOH [1.95 g, 46.5 mmol in H2O (5 mL)] (1:1:1, total 15 mL) and heated at 80 °C for 16 h. The reaction mixture was cooled to RT and then treated with aqueous NaOH [700 mg in H2O (10 mL)] and the mixture was extracted with ethyl acetate (3 × 20 mL). The combined organic layers were washed with saturated NaCl solution, dried (Na2SO4), and filtered. Evaporation of the solvent and purification of the crude material by flash chromatography (short column, ethyl acetate/hexane, 1:1 to 100% ethyl acetate, then 5:95 methanol/ethyl acetate to 10:90 methanol/ethyl acetate) furnished the benzylamine 3b (960 mg, 95%) as pale yellowish viscous liquid. 1H NMR (400 MHz, CDCl3): = 7.40 (d, J = 8.6 Hz, 1H, Ar-H), 6.93 (d, J = 3.0 Hz, 1H, Ar-H), 6.67 (dd, J = 8.6, 3.0 Hz, 1H, Ar-H), 3.86 (s, 2H, CH2NH2), 3.78 (s, 3H, OCH3), 2.12 (br. s, 2H, CH2NH2); 13C NMR (100 MHz, CDCl3): = 159.3 (C), 142.5 (C), 133.4 (CH), 114.8 (CH), 114.1 (CH), 113.7 (C), 55.4 (OCH3), 46.8 (CH2NH2); HRMS (ESI) calcd for C8H11BrNO [M+H]+ 216.0018, found 216.0017.
References:
Satyanarayana, Gedu;Maier, Martin E. [Tetrahedron,2012,vol. 68,# 6,p. 1745 - 1749] Location in patent:supporting information; experimental part
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