Potassium Hydroxide → 4-{[(2,2-Dichlorocyclopropyl)methyl]sulfanyl}-2-nitroaniline

HRID 838993Notes

Reaction equation

HRID 838993 reaction equation
[N+:1]([C:4]1[CH:10]=[C:9]([S:11][C:12]#N)[CH:8]=[CH:7][C:5]=1[NH2:6])([O-:3])=[O:2].[BH4-].[Na+].[OH-].[K+].BrC[CH:20]1[CH2:22][C:21]1([Cl:24])[Cl:23]>C(O)C.C(Cl)(Cl)Cl.O>[Cl:23][C:21]1([Cl:24])[CH2:22][CH:20]1[CH2:12][S:11][C:9]1[CH:8]=[CH:7][C:5]([NH2:6])=[C:4]([N+:1]([O-:3])=[O:2])[CH:10]=1

Participants

8

Reactant 4

HCID 14797Potassium HydroxideHCID 1046774-Amino-3-nitrophenyl thiocyanateHCID 4311764Sodium borohydrideHCID 47395822-BROMOMETHYL-1 1-DICHLOROCYCLOPROPANE

Product 1

HCID 205328394-{[(2,2-Dichlorocyclopropyl)methyl]sulfanyl}-2-nitroanilineYield 54.6%

Reagents, catalysts & solvents 3

HCID 702EthanolSolvent3×HCID 962WaterSolventHCID 6212ChloroformSolvent

Procedure

To a stirred mixture of 11.75 g (0.06 mole) of 2-nitro-4-thiocyanoaniline in 500 ml of absolute ethanol under N2 there is added 2.5 g (0.06 mole) of sodium borohydride in portions. The mixture is stirred at room temperature for 15 minutes and then refluxed for 15 minutes. The heating mantle is removed and 3.9 g (0.06 mole) of KOH in 30 ml of absolute ethanol is added. The mixture is stirred for 1 minute. A solution of 12.25 g (0.06 mole) of 1-bromomethyl-2,2-dichlorocyclopropane in 30 ml of absolute ethanol is added and the mixture is stirred at room temperature for 15 minutes and then refluxed for 2 hours. Equal amounts of H2O and CHCl3 are added until 2 layers are formed. The organic layer is separated, dried (MgSO4), and the solvent removed in vacuo to give a red oil which is chromatographed on silica gel. Elution with ethyl ether gives 9.6 g of red oil.

Workup

  1. temperaturerefluxed for 15 minutes
  2. customThe heating mantle is removed
  3. stirringThe mixture is stirred for 1 minute
  4. stirringthe mixture is stirred at room temperature for 15 minutes
  5. temperaturerefluxed for 2 hours
  6. customare formed
  7. customThe organic layer is separated
  8. dry with materialdried (MgSO4)
  9. customthe solvent removed in vacuo
  10. customto give a red oil which
  11. customis chromatographed on silica gel
  12. washElution with ethyl ether

Sources & evidence

ORD record
ord-cba037499cf64fc2a329aaaa220dee3b
Source dataset
uspto-grants-1978_06
Patent number
US04093732

Reaction notes

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