Sodium methanethiolate → Methyl 2-(methylthio)-4-(trifluoromethyl)benzoate

HRID 1250314Notes

Reaction equation

HRID 1250314 reaction equation
[CH3:1][S-:2].[Na+].[N+]([C:7]1[CH:16]=[C:15]([C:17]([F:20])([F:19])[F:18])[CH:14]=[CH:13][C:8]=1[C:9]([O:11][CH3:12])=[O:10])([O-])=O>O.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.C1(C)C=CC=CC=1>[CH3:1][S:2][C:7]1[CH:16]=[C:15]([C:17]([F:20])([F:19])[F:18])[CH:14]=[CH:13][C:8]=1[C:9]([O:11][CH3:12])=[O:10]

Participants

6

Reactant 2

HCID 4378561Sodium methanethiolateHCID 11276727Methyl 2-nitro-4-(trifluoromethyl)benzoate

Product 1

HCID 10944828Methyl 2-(methylthio)-4-(trifluoromethyl)benzoateYield 103.9%

Reagents, catalysts & solvents 3

HCID 74236Tetrabutylammonium BromideCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Procedure

Sodium thiomethoxide (91 mg; 1.3 mmol; 1.3 equiv) was dissolved in water (0.34 mL). Tetrabutylammonium bromide (48 mg; 0.15 mmol; 0.15 equiv) was added. Methyl 2-nitro-4-trifluoromethylbenzoate (5a; 249 mg; 1.0 mmol) was dissolved in toluene and added to the mixture. The reaction mixture was stirred at ambient temperature for 1 h to completely consume 5a according to gas chromatography (GC) analysis. The reaction mixture was diluted with ethyl acetate and water and the layers were thoroughly mixed and then separated. The organic layer was dried over Na2SO4 and concentrated to afford 0.26 g of 6a which contained a small amount of tetrabutylammonium bromide. The crude product was filtered through a pad of flash silica gel to afford 226 mg (90%) of 6a.

Workup

  1. additionadded to the mixture
  2. customto completely consume 5a
  3. additionThe reaction mixture was diluted with ethyl acetate and water
  4. additionthe layers were thoroughly mixed
  5. customseparated
  6. dry with materialThe organic layer was dried over Na2SO4
  7. concentrationconcentrated

Sources & evidence

ORD record
ord-281289f343e34407ba59bf16f463a8bd
Source dataset
uspto-grants-2002_01
Patent number
US06337418B1

Reaction notes

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