Bromine → Tert-butyl ((5-bromothiazol-2-yl)methyl)carbamate

HRID 230028Notes

Reaction equation

HRID 230028 reaction equation
[C:1]([O:5][C:6]([NH:8][CH2:9][C:10]1[S:11][CH:12]=[CH:13][N:14]=1)=[O:7])([CH3:4])([CH3:3])[CH3:2].C([O-])(=O)C.[Na+].[Br:20]Br.O.O.O.O.O.S([O-])([O-])=O.[Na+].[Na+]>C(OCC)(=O)C>[Br:20][C:12]1[S:11][C:10]([CH2:9][NH:8][C:6]([O:5][C:1]([CH3:4])([CH3:2])[CH3:3])=[O:7])=[N:14][CH:13]=1

Participants

6

Reactant 4

HCID 24408BromineHCID 517045Sodium AcetateHCID 19790054Sodium sulfite pentahydrateHCID 23088785tert-Butyl N-(1,3-thiazol-2-ylmethyl)carbamate

Product 1

HCID 23088769Tert-butyl ((5-bromothiazol-2-yl)methyl)carbamate

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

A solution (2 L) of 1.33 kg of 2-t-butoxy carbonylaminomethylthiazole in ethyl acetate was added to an aqueous solution (20 L) of 8.6 kg of sodium acetate, and the mixture was stirred. Bromine (1.35 L) was added dropwise to this solution (internal temperature: 19 to 24° C.) over a period of 3.5 hr, and the mixture was stirred at an internal temperature of 25.5±5° C. for 14 hr. Sodium sulfite pentahydrate (180 g) was added thereto, the mixture was then extracted with 3 L of ethyl acetate, and the organic layer was washed with 1 L of water and 1.53 L of a 6 M aqueous sodium hydroxide solution. The aqueous layer was then extracted with 3 L of ethyl acetate. The organic layers were combined, were dried over anhydrous magnesium sulfate, and were filtered. The solvent was removed from the filtrate by evaporation under the reduced pressure, followed by substitution concentration twice with 2 L of ethanol to give 944 g of 5-bromo-2-t-butoxy carbonylaminomethylthiazole.

Workup

  1. stirringthe mixture was stirred at an internal temperature of 25.5±5° C. for 14 hr
  2. extractionthe mixture was then extracted with 3 L of ethyl acetate
  3. washthe organic layer was washed with 1 L of water and 1.53 L of a 6 M aqueous sodium hydroxide solution
  4. extractionThe aqueous layer was then extracted with 3 L of ethyl acetate
  5. dry with materialwere dried over anhydrous magnesium sulfate
  6. filtrationwere filtered
  7. customThe solvent was removed from the filtrate by evaporation under the reduced pressure
  8. concentrationfollowed by substitution concentration twice with 2 L of ethanol

Sources & evidence

ORD record
ord-0ccb3666dc3e4b789d61c75b2db9323b
Source dataset
uspto-grants-2009_07
Patent number
US07563901B2

Reaction notes

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