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

HRID 567804노트

반응식

HRID 567804 반응식
[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]

참가 물질

5

반응물 3

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

생성물 1

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

시약·촉매·용매 1

HCID 6344Dichloromethane용매

실험 절차

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)+.

후처리

  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)

출처 및 근거

ORD 기록
ord-8167a43eeaf744c5acb4ed2c591719f0
출처 데이터셋
uspto-grants-2001_01
특허 번호
US06180627B2

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