Methanol → 2-(4-Chloro-3-fluorophenyl)ethylamine

HRID 19777Notes

Reaction equation

HRID 19777 reaction equation
[BH4-].[Li+].C[Si](C)(C)Cl.[Cl:8][C:9]1[CH:14]=[CH:13][C:12]([CH:15]=[CH:16][N+:17]([O-])=O)=[CH:11][C:10]=1[F:20].CO>C1COCC1>[Cl:8][C:9]1[CH:14]=[CH:13][C:12]([CH2:15][CH2:16][NH2:17])=[CH:11][C:10]=1[F:20]

Participants

6

Reactant 4

HCID 887MethanolHCID 6397ChlorotrimethylsilaneHCID 4148881Lithium borohydrideHCID 668017121-Chloro-2-fluoro-4-(2-nitro-vinyl)-benzene

Product 1

HCID 193623072-(4-Chloro-3-fluorophenyl)ethylamineYield 73%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

Lithium borohydride (2.16 g, 99 mmol) was suspended in THF (50 ml). Trimethylchlorosilane (21.6 g, 198 mmol) was added dropwise. A solution of 1-chloro-2-fluoro-4-(2-nitro-vinyl)-benzene (5.0 g, 24.8 mmol) in THF (20 ml) was added dropwise. Strong gas evolution and foam formation was observed. The white suspension was stirred at RT for 3 days. Carefully MeOH (80 ml) was added. The solvents were removed in vacuo and the residue was purified by flash column chromatography (CH2Cl2/MeOH+5% aq. NH4OH 4:1) to yield 2-(4-chloro-3-fluoro-phenyl)-ethylamine (3.1 g, 73%) as a white solid. MS (ISP) 174.1 (M+H)+. 1HNMR (DMSO-d, 300 MHz): δ 2.92 (t, J=4.8 Hz, 2H), 3.02 (t, J=6.3 Hz, 2H), 7.15 (dd, J=6.0 and 1.2 Hz, 1H), 7.38 (dd, J=1.2 and 7.8 Hz), 7.53 (t, J=6.3 Hz, 1H), 7.93 (br, 2H).

Workup

  1. customThe solvents were removed in vacuo
  2. customthe residue was purified by flash column chromatography (CH2Cl2/MeOH+5% aq. NH4OH 4:1)

Sources & evidence

ORD record
ord-4366979928964a23976331540d5aa8a5
Source dataset
uspto-grants-2010_06
Patent number
US07745477B2

Reaction notes

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