Water → Carbamic acid, N-(2-bromo-4-methyl-5-thiazolyl)-N-methyl-, 1,1-dimethylethyl ester

HRID 533306Notes

Reaction equation

HRID 533306 reaction equation
[C:1]([O:5][C:6](=[O:15])[NH:7][C:8]1[S:12][C:11]([Br:13])=[N:10][C:9]=1[CH3:14])([CH3:4])([CH3:3])[CH3:2].[H-].[Na+].I[CH3:19].O>CN(C=O)C.C(OCC)(=O)C>[C:1]([O:5][C:6](=[O:15])[N:7]([C:8]1[S:12][C:11]([Br:13])=[N:10][C:9]=1[CH3:14])[CH3:19])([CH3:4])([CH3:3])[CH3:2]

Participants

7

Reactant 4

HCID 962WaterHCID 6328Methyl iodideHCID 24758Sodium hydrideHCID 59580681HCID 59580681, compound

Product 1

HCID 59580796Carbamic acid, N-(2-bromo-4-methyl-5-thiazolyl)-N-methyl-, 1,1-dimethylethyl esterYield 54%

Reagents, catalysts & solvents 2

HCID 6228DimethylformamideSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of (2-bromo-4-methyl-thiazol-5-yl)-carbamic acid tert-butyl ester (2.93 g, 10 mmol) in DMF (50 mL) at 0° C. was added NaH (480 mg, 12 mmol, 60% dispersion in mineral oil) in one portion and the suspension was stirred for 1 h. Iodomethane (0.65 mL, 10.5 mmol) was added in one portion, and after 5 min the reaction mixture was warmed to ambient temperature and stirred for 5 h. Water and ethyl acetate were added and the resulting biphasic mixture was separated. The aqueous layer was extracted one time with ethyl acetate. The combined organic extracts were washed twice with brine, dried over Na2SO4, filtered and concentrated to dryness under reduced pressure. The crude product was purified by silica gel chromatography (0-100% ethyl acetate/hexanes) to give the desired product as a clear oil (1.66 g, 54%): IR (KBr) 1688 cm−1; 1H NMR (300 MHz, CDCl3) δ 2.98 (s, 3H), 2.29 (s, 3H), 1.54 (s, 9H); ESIMS m/z 309 (M+2).

Workup

  1. stirringstirred for 5 h
  2. customthe resulting biphasic mixture was separated
  3. extractionThe aqueous layer was extracted one time with ethyl acetate
  4. washThe combined organic extracts were washed twice with brine
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated to dryness under reduced pressure
  8. customThe crude product was purified by silica gel chromatography (0-100% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-b526913f032d40e6b67b871045d479fb
Source dataset
uspto-grants-2014_10
Patent number
US08853246B2

Reaction notes

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