1,1-Bis(methylthio)-2-nitroethylene → 1-(6-Chloro-3-pyridylmethyl)amino-1-methylthio-2-nitroethylene

HRID 1091063Notes

Reaction equation

HRID 1091063 reaction equation
[CH3:1][S:2][C:3](SC)=[CH:4][N+:5]([O-:7])=[O:6].[NH2:10][CH2:11][C:12]1[CH:13]=[CH:14][C:15]([Cl:18])=[N:16][CH:17]=1>C(#N)C>[Cl:18][C:15]1[N:16]=[CH:17][C:12]([CH2:11][NH:10][C:3]([S:2][CH3:1])=[CH:4][N+:5]([O-:7])=[O:6])=[CH:13][CH:14]=1

Participants

4

Reactant 2

HCID 836231,1-Bis(methylthio)-2-nitroethyleneHCID 70209275-(Aminomethyl)-2-chloropyridine

Product 1

HCID 855929321-(6-Chloro-3-pyridylmethyl)amino-1-methylthio-2-nitroethyleneYield 62%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent2×

Procedure

To a refluxing mixture of 6.61 g of 1,1-bis(methylthio)-2-nitroethylene and 100 ml of acetonitrile was added a solution of 4.28 g of 5-aminomethyl-2-chloropyridine in 10 ml of acetonitrile dropwise over a period of 3 hours and 30 minutes and the whole mixture was further refluxed for 2 hours. After cooling, the insolubles (by-product; 1,1-bis(6-chloro-3-pyridylmethylamino)-2-nitroethylene) were filtered off and the filtrate was concentrated and washed with ethyl acetate to give 4.83 g of 1-(6-chloro-3-pyridylmethylamino)-1-methylthio-2-nitroethylene. The ethyl acetate washings were concentrated and the residue was purified by column chromatography (eluent: dichloromethane-methanol (30:1)) to give a further crop (1.15 g) of the same compound.

Workup

  1. temperature30 minutes and the whole mixture was further refluxed for 2 hours
  2. temperatureAfter cooling
  3. filtrationthe insolubles (by-product; 1,1-bis(6-chloro-3-pyridylmethylamino)-2-nitroethylene) were filtered off
  4. concentrationthe filtrate was concentrated
  5. washwashed with ethyl acetate

Sources & evidence

ORD record
ord-bad9b04df2d04f1f8efda69ddae8d537
Source dataset
uspto-grants-1992_01
Patent number
US05084459

Reaction notes

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