Dimethyl Sulfide → 2-[(Methylsulfanyl)methyl]-4-nitroaniline

HRID 2398557Notes

Reaction equation

HRID 2398557 reaction equation
C(OCl)(C)(C)C.[N+:7]([C:10]1[CH:16]=[CH:15][C:13]([NH2:14])=[CH:12][CH:11]=1)([O-:9])=[O:8].[CH3:17][S:18][CH3:19].C[O-].[Na+]>C(Cl)Cl.C(#N)C.CO>[N+:7]([C:10]1[CH:16]=[CH:15][C:13]([NH2:14])=[C:12]([CH2:17][S:18][CH3:19])[CH:11]=1)([O-:9])=[O:8]

Participants

8

Reactant 4

HCID 1068Dimethyl SulfideHCID 74754-NitroanilineHCID 521297Tert-Butyl hypochloriteHCID 10942334Sodium Methoxide

Product 1

HCID 3267072-[(Methylsulfanyl)methyl]-4-nitroaniline

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 6342AcetonitrileSolventHCID 6344DichloromethaneSolvent2×

Procedure

The starting materials are prepared as follows: The solution of 23.4 g of t-butylhypochlorite in 20 ml of methylene chloride is added to that of 30.0 g of 4-nitroaniline and 27.0 g of dimethyl thioether in 650 ml of acetonitrile and 200 ml of methylene chloride while stirring at -40° under nitrogen. After 4 hours the temperature is raised to -20° and maintained there for three hours. After the addition of 30 g of sodium methoxide in 100 ml of methanol the mixture is refluxed for 15 hours, cooled, filtered and evaporated. The residue is dissolved in diethyl ether and filtered through a silica gel column to remove any unreacted 4-nitroaniline as its benzenesulfonate following addition of 17.4 g of benzenesulfonic acid. The filtrate is evaporated and the residue recrystallized from ethanol, to yield the 4-nitro-2-methylmercaptomethylaniline melting at 72°-77°.

Workup

  1. customThe starting materials are prepared
  2. temperatureAfter 4 hours the temperature is raised to -20°
  3. temperaturemaintained there for three hours
  4. temperatureis refluxed for 15 hours
  5. temperaturecooled
  6. filtrationfiltered
  7. customevaporated
  8. dissolutionThe residue is dissolved in diethyl ether
  9. filtrationfiltered through a silica gel column
  10. customto remove any unreacted 4-nitroaniline
  11. additionas its benzenesulfonate following addition of 17.4 g of benzenesulfonic acid
  12. customThe filtrate is evaporated
  13. customthe residue recrystallized from ethanol

Sources & evidence

ORD record
ord-eac37064f4ba432b89296ece5d44b470
Source dataset
uspto-grants-1977_05
Patent number
US04025505

Reaction notes

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