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

HRID 2228727Notes

Reaction equation

HRID 2228727 reaction equation
[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]

Participants

5

Reactant 3

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

Product 1

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

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

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)+.

Workup

  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)

Sources & evidence

ORD record
ord-9a4e936f7c0449d38173b48ba81da370
Source dataset
uspto-grants-2002_07
Patent number
US06417203B1

Reaction notes

Loading…