tert-Butyl mercaptan → 2-tert-Butylsulfanylmethyl-4-nitro-benzoic acid ethyl ester

HRID 390411Notes

Reaction equation

HRID 390411 reaction equation
[CH2:1]([O:3][C:4](=[O:16])[C:5]1[CH:10]=[CH:9][C:8]([N+:11]([O-:13])=[O:12])=[CH:7][C:6]=1[CH2:14]Br)[CH3:2].[CH3:17][C:18]([SH:21])([CH3:20])[CH3:19].[H-].[Na+]>CC#N>[CH2:1]([O:3][C:4](=[O:16])[C:5]1[CH:10]=[CH:9][C:8]([N+:11]([O-:13])=[O:12])=[CH:7][C:6]=1[CH2:14][S:21][C:18]([CH3:20])([CH3:19])[CH3:17])[CH3:2]

Participants

5

Reactant 3

HCID 6387tert-Butyl mercaptanHCID 24758Sodium hydrideHCID 58066683Ethyl 2-(bromomethyl)-4-nitrobenzoate

Product 1

HCID 580666792-tert-Butylsulfanylmethyl-4-nitro-benzoic acid ethyl ester

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
0 °C

Procedure

2-Bromomethyl-4-nitro-benzoic acid ethyl ester (8.0 g, 27.8 mmol) and 2-methyl-2-propanethiol (3.74 mL, 33.3 mmol) were combined in MeCN (100 mL) at 0° C. Sodium hydride (60% in mineral oil; 1.39 g, 34.8 mmol) was added, and the reaction was stirred for 5 minutes at 0° C., and then at room temperature until no starting material was seen by analytical tlc. The mixture was quenched by adding ice chips and diluted with H2O (100 mL) and 1N aqueous HCl (30 mL), and then extracted with EtOAc. The combined organic layers were washed with H2O, dried, filtered, and concentrated, and the residue was purified by silica gel chromatography to give the title compound.

Workup

  1. customat room temperature
  2. customThe mixture was quenched
  3. additionby adding ice chips
  4. additiondiluted with H2O (100 mL) and 1N aqueous HCl (30 mL)
  5. extractionextracted with EtOAc
  6. washThe combined organic layers were washed with H2O
  7. customdried
  8. filtrationfiltered
  9. concentrationconcentrated
  10. customthe residue was purified by silica gel chromatography

Sources & evidence

ORD record
ord-91d8d28dc8144ad793f8cc65f37778e0
Source dataset
uspto-grants-2013_02
Patent number
US08383654B2

Reaction notes

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