2-Nitrobenzyl chloride → 1-[1-(Isopropylthio)methyl]-2-nitrobenzene

HRID 1176016Notes

Reaction equation

HRID 1176016 reaction equation
[N+:1]([C:4]1[CH:11]=[CH:10][CH:9]=[CH:8][C:5]=1[CH2:6]Cl)([O-:3])=[O:2].[CH3:12][CH:13]([S-:15])[CH3:14].[Na+]>C(#N)C>[CH:13]([S:15][CH2:6][C:5]1[CH:8]=[CH:9][CH:10]=[CH:11][C:4]=1[N+:1]([O-:3])=[O:2])([CH3:14])[CH3:12]

Participants

4

Reactant 2

HCID 119212-Nitrobenzyl chlorideHCID 3470666Sodium 2-propanethiolate2×

Product 1

HCID 595598261-[1-(Isopropylthio)methyl]-2-nitrobenzeneYield 55.8%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent2×

Conditions

Temperature
35 °C

Procedure

In a 250 ml three-necked flask equipped with a stirrer, dropping funnel and thermometer, 17.2 g (0.1 mol) 2-nitrobenzylchloride in 20 ml acetonitrile are added dropwise to 10.3 g (0.105 mol) sodium 2-propanethiolate in 75 ml acetonitrile, with cooling to maintain the temperature at 30-40° C. The suspension is stirred for another 16 hours at 40-50° C. To complete the reaction, another 6 g sodium 2-propanethiolate (0.061 mol) are added and stirring is continued another 24 hours at 40-50° C. The reaction is cooled and the solvent removed under vacuum. The residue is dissolved in methyl tert-butyl ether, washed and dried over sodium sulfate. The sodium sulfate is removed by filtration, and the solution is concentrated under vacuum. The crude product is purified by column chromatography (silica gel, 50:1 cyclohexane/ethyl acetate). 11.8 g (92% purity by HPLC, 51.2% theoretical yield) of 1-[1-(isopropylthio)methyl]-2-nitrobenzene are obtained as a brown oil [logP (pH 2.3)=3.28].

Workup

  1. customIn a 250 ml three-necked flask equipped with a stirrer
  2. temperaturewith cooling
  3. customthe reaction
  4. stirringstirring
  5. waitis continued another 24 hours at 40-50° C
  6. temperatureThe reaction is cooled
  7. customthe solvent removed under vacuum
  8. dissolutionThe residue is dissolved in methyl tert-butyl ether
  9. washwashed
  10. dry with materialdried over sodium sulfate
  11. customThe sodium sulfate is removed by filtration
  12. concentrationthe solution is concentrated under vacuum
  13. customThe crude product is purified by column chromatography (silica gel, 50:1 cyclohexane/ethyl acetate)

Sources & evidence

ORD record
ord-86271cc3f3f248f7802f4670ef38469f
Source dataset
uspto-grants-2010_11
Patent number
US07842710B2

Reaction notes

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