Carbon tetrabromide → tert-Butyl N-[3-(bromomethyl)benzyl]-N-methylcarbamate

HRID 567804ノート

反応式

HRID 567804 の反応式
[C:1]([O:5][C:6](=[O:18])[N:7]([CH2:9][C:10]1[CH:15]=[CH:14][CH:13]=[C:12]([CH2:16]O)[CH:11]=1)[CH3:8])([CH3:4])([CH3:3])[CH3:2].C(Br)(Br)(Br)[Br:20].C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C(Cl)Cl>[Br:20][CH2:16][C:12]1[CH:11]=[C:10]([CH:15]=[CH:14][CH:13]=1)[CH2:9][N:7]([CH3:8])[C:6](=[O:18])[O:5][C:1]([CH3:4])([CH3:3])[CH3:2]

参加物

5

反応物 3

HCID 11205Carbon tetrabromideHCID 11776TriphenylphosphineHCID 18470938tert-Butyl 3-(hydroxymethyl)benzyl(methyl)carbamate

生成物 1

HCID 18470889tert-Butyl N-[3-(bromomethyl)benzyl]-N-methylcarbamate収率 63.3%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒

実験手順

A milky suspension of 3-[(methylamino)methyl]phenylmethanol (preparation 12) (2.7 g, 17.9 mmol) in THF (60 ml) and water (60 ml) was treated with di-t-butylpyrocarbonate (5.4 g,24.7 mmol) and the mixture stirred at room temperature overnight. The THF was evaporated and the aqueous residue treated with ethyl acetate (250 ml). The organic layer was washed with sat aq brine (100 ml) a and dried over MgSO4. Filtration away from the drying agent followed by evaporation of the solvent gave the crude product which was purified by chromatography (SiO2, eluting with 95:5CH2Cl2:MeOH) to give the intermediate tert-butyl N-[3-(hydroxymethyl)benzyl]-N-methylcarbamate(4.2 g) which was used directly in the next step. A stirred solution of tert-butyl-N-[3-(hydroxymethyl)benzyl]-N-methylcarbamate (4.2 g, 16.7 mmol) in CH2Cl2 (150 ml) at 0° C., was treated with carbon tetrabromide (8.0 g, 24.1 mmol) and triphenyl phosphine (6.35 g, 24.21 mmol). The resultant solution was warmed to room temperature and stirred for 4 days. The resultant mixture was evaporated to dryness and the residue purified by chromatography (SiO2, gradient elution with 100% hexane; 99:1 hexane:ethyl acetate; 95:5 hexane:ethyl acetate) to give the desired product (3.32 g, 60%). 1H NMR (CDCl3) δ 1.50 (s, 9H), 2.80 (s, br, 3H), 4.20 (s, 2H), 4.30 (s, 2H), 7.15 (m, 1H), 7.25 (m, 1H), 7.30 (m, 2H). LRMS m/z=333.2 (M+18)+.

後処理

  1. customThe resultant mixture was evaporated to dryness
  2. customthe residue purified by chromatography (SiO2, gradient elution with 100% hexane; 99:1 hexane:ethyl acetate; 95:5 hexane:ethyl acetate)

出典と根拠

ORDレコード
ord-8167a43eeaf744c5acb4ed2c591719f0
出典データセット
uspto-grants-2001_01
特許番号
US06180627B2

反応ノート

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