Potassium Hydroxide → 4-[[(2,2-Dichloro-1-methylcyclopropyl)methyl]thio]-2-nitrobenzenamine

HRID 838997Notes

Reaction equation

HRID 838997 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+].[Cl:18][C:19]1([Cl:25])[CH2:21][C:20]1(CCl)[CH3:22]>C(O)C.C(Cl)(Cl)Cl.O>[N+:1]([C:4]1[CH:10]=[C:9]([S:11][CH2:12][C:20]2([CH3:22])[CH2:21][C:19]2([Cl:25])[Cl:18])[CH:8]=[CH:7][C:5]=1[NH2:6])([O-:3])=[O:2]

Participants

8

Reactant 4

HCID 14797Potassium HydroxideHCID 1046774-Amino-3-nitrophenyl thiocyanateHCID 3384531,1-Dichloro-2-(chloromethyl)-2-methylcyclopropaneHCID 4311764Sodium borohydride

Product 1

HCID 203255584-[[(2,2-Dichloro-1-methylcyclopropyl)methyl]thio]-2-nitrobenzenamineYield 62.5%

Reagents, catalysts & solvents 3

HCID 702EthanolSolvent3×HCID 962WaterSolventHCID 6212ChloroformSolvent

Procedure

To a stirred mixture 9.75 g (0.05 mole) of 2-nitro-4-thiocyanoaniline in 500 ml of absolute ethanol under N2, there is added 2.1 g of sodium borohydride in portions. The mixture is stirred at room temperature for 3 hours. 3.25 g (0.05 mole) of KOH in 30 ml of absolute ethanol is added. The mixture is stirred for 1 minute. A solution of 8.7 g (0.05 mole) of 1,1-dichloro-2-chloromethyl-2-methylcyclopropane in 15 ml of absolute ethanol is added and the mixture is refluxed for 3 hours. Equal amounts of H2O and CHCl3 are added until two layers are formed. The organic layer is separated, dried (MgSO4), and the solvent removed in vacuo to give a red oil which is triturated with 10 ml of absolute ethanol to yield 9.6 g of 2-nitro-4-[(2,2-dichloro-1-methylcyclopropyl)methyl]thioaniline as a solid, m.p. 76-78° C.

Workup

  1. stirringThe mixture is stirred for 1 minute
  2. temperaturethe mixture is refluxed for 3 hours
  3. customare formed
  4. customThe organic layer is separated
  5. dry with materialdried (MgSO4)
  6. customthe solvent removed in vacuo
  7. customto give a red oil which
  8. customis triturated with 10 ml of absolute ethanol

Sources & evidence

ORD record
ord-f9fad37a4c354aa289120c6d2f81b73e
Source dataset
uspto-grants-1978_06
Patent number
US04093732

Reaction notes

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