Allyl chloroformate → tert-Butyl-[3-(2-chloro-pyrimidin-4-yl)-benzyl]-carbamic acid allyl ester

HRID 14908

Reaction equation

HRID 14908 reaction equation
[C:1]([NH:5][CH2:6][C:7]1[CH:12]=[CH:11][CH:10]=[C:9]([C:13]2[CH:18]=[CH:17][N:16]=[C:15]([Cl:19])[N:14]=2)[CH:8]=1)([CH3:4])([CH3:3])[CH3:2].Cl[C:21]([O:23][CH2:24][CH:25]=[CH2:26])=[O:22].C(N(C(C)C)CC)(C)C>C(Cl)Cl>[CH2:24]([O:23][C:21](=[O:22])[N:5]([C:1]([CH3:4])([CH3:2])[CH3:3])[CH2:6][C:7]1[CH:12]=[CH:11][CH:10]=[C:9]([C:13]2[CH:18]=[CH:17][N:16]=[C:15]([Cl:19])[N:14]=2)[CH:8]=1)[CH:25]=[CH2:26]

Participants

5

Reactant 3

HCID 18052Allyl chloroformateHCID 81531DiisopropylethylamineHCID 86603310tert-Butyl-[3-(2-chloro-pyrimidin-4-yl)-benzyl]-amine

Product 1

HCID 86603311tert-Butyl-[3-(2-chloro-pyrimidin-4-yl)-benzyl]-carbamic acid allyl esterYield 61%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

tert-Butyl-[3-(2-chloro-pyrimidin-4-yl)-benzyl]-amine from the above reaction (1.33 g, 4.84 mmol) was treated with allyl chloroformate (0.77 mL) in methylene chloride (15 mL) with diisopropyl ethylamine (1.7 mL) at room temperature for 3 hours. The mixture was diluted with methylene chloride (50 mL), washed with water (2×), brine, dried over Na2SO4, filtered. Removal of the solvent followed by chromatography on silica gel (1:4 ethyl acetate:hexane eluent) afforded product in 61% yield. LC-MS showed the product had the expected M+H+ of 360. 1H NMR (Varian 300 MHz, CDCl3, shifts relative to the solvent peak at 7.24 ppm) 8.6 (d, 1H) 7.9 (d, 2H) 7.6 (d, 1H) 7.4 (m, 2H) 5.9 (m, 1H) 5.2 (m, 2H) 4.7 (s, 2H) 4.6 (d, 2H) 1.4 (s, 9H).

Workup

  1. washwashed with water (2×), brine
  2. dry with materialdried over Na2SO4
  3. filtrationfiltered
  4. customRemoval of the solvent
  5. customafforded product in 61% yield

Sources & evidence

ORD record
ord-ed400203ca504787827ba29c97dbf2c5
Source dataset
uspto-grants-2010_06
Patent number
US07732444B2

Linked notes

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