Diethyl Ether → Dimethyl-thiocarbamic acid S-(4-bromo-2-hydroxymethyl-6-nitro-phenyl)ester

HRID 1747486Notes

Reaction equation

HRID 1747486 reaction equation
C([O:3][C:4](=O)[C:5]1[CH:10]=[C:9]([Br:11])[CH:8]=[C:7]([N+:12]([O-:14])=[O:13])[C:6]=1[S:15][C:16](=[O:20])[N:17]([CH3:19])[CH3:18])C.C(OCC)C.B>C1COCC1>[Br:11][C:9]1[CH:8]=[C:7]([N+:12]([O-:14])=[O:13])[C:6]([S:15][C:16](=[O:20])[N:17]([CH3:19])[CH3:18])=[C:5]([CH2:4][OH:3])[CH:10]=1

Participants

5

Reactant 3

HCID 3283Diethyl EtherHCID 6331Borane2×HCID 594976075-Bromo-2-dimethylcarbamoylsulfanyl-3-nitro-benzoic acid ethyl ester

Product 1

HCID 59497682Dimethyl-thiocarbamic acid S-(4-bromo-2-hydroxymethyl-6-nitro-phenyl)esterYield 91%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

5-Bromo-2-dimethylcarbamoylsulfanyl-3-nitro-benzoic acid ethyl ester (3.0 g, 9.4 mmol) is taken up in THF (40 mL)/diethyl ether (10 mL) and cooled to zero with an ice bath. Borane in THF (1M, 20 mL, 2.1 mmol) is added dropwise to the reaction and then the reaction warmed to room temperature. An additional equivalent of borane is added, and the reaction warmed to 45° C. The reaction is stirred at 45° C. for 4 hours and then the reaction cooled to zero and quenched by the slow addition of saturated NH4Cl. The reaction is poured into water and then extracted with ethyl acetate. The combined organic layers were dried filtered and evaporated. The residue is purified on silica gel with DCM/MeOH as the eluent to afford 2.5 g (91%) of the title product. LCMS (ESMS): m/z 336.9 (M+H+).

Workup

  1. temperaturecooled to zero with an ice bath
  2. temperaturethe reaction warmed to 45° C
  3. temperaturethe reaction cooled to zero
  4. customquenched by the slow addition of saturated NH4Cl
  5. additionThe reaction is poured into water
  6. extractionextracted with ethyl acetate
  7. customThe combined organic layers were dried
  8. filtrationfiltered
  9. customevaporated
  10. customThe residue is purified on silica gel with DCM/MeOH as the eluent

Sources & evidence

ORD record
ord-5bbd51f808c34fc3986367ee0ea77503
Source dataset
uspto-grants-2015_10
Patent number
US09150556B2

Reaction notes

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