Water → Methyl 4-(methylsulfanyl)-3-nitrobenzenecarboxylate

HRID 467335Notes

Reaction equation

HRID 467335 reaction equation
F[C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[N+:12]([O-:14])=[O:13].[CH3:15][S-:16].[Na+].O>CN1CCN(C)C1=O>[CH3:15][S:16][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[N+:12]([O-:14])=[O:13]

Participants

5

Reactant 3

HCID 962WaterHCID 4378561Sodium methanethiolateHCID 5219721Methyl 4-fluoro-3-nitrobenzoate

Product 1

HCID 21187831Methyl 4-(methylsulfanyl)-3-nitrobenzenecarboxylateYield 22.2%

Reagents, catalysts & solvents 1

HCID 66611,3-Dimethyl-2-imidazolidinoneSolvent

Procedure

Methyl 4-fluoro-3-nitrobenzoate (13.6 g) was added over 10 minutes to a stirred solution of sodium thiomethoxide (4.8 g) in 1,3-dimethyl-2-imidazolidinone (100 ml). The dark brown solution was stirred for 2 hours and was then heated on a steam bath for 2.5 hours. After cooling, the solution was poured into water (1.0 liter) and was extracted with diethyl ether (300 ml and then 2×200 ml). The ether solution was washed with water (2×250 ml), was dried over magnesium sulphate and was then concentrated in vacuo to leave an orange slurry. Crystallization from methanol provided methyl 4-methylthio-3-nitrobenzoate (3.45 g), m.p. 118°-120° C. [Elemental analysis: C,47.8; H,3.9; N,6.2; S,13.7%; calculated: C,47.58; H,3.96; N,6.17; S,14.1%].

Workup

  1. temperaturewas then heated on a steam bath for 2.5 hours
  2. temperatureAfter cooling
  3. extractionwas extracted with diethyl ether (300 ml
  4. washThe ether solution was washed with water (2×250 ml)
  5. dry with materialwas dried over magnesium sulphate
  6. concentrationwas then concentrated in vacuo
  7. customto leave an orange slurry
  8. customCrystallization from methanol

Sources & evidence

ORD record
ord-a1c20d827ce84a67895c402ff2c7ed16
Source dataset
uspto-grants-1992_10
Patent number
US05159114

Reaction notes

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