Tosylmethyl isocyanide → 3-(3,4-Dichlorophenyl)-4-nitro-1H-pyrrole

HRID 1651702Notes

Reaction equation

HRID 1651702 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:10]=[CH:11][C:12]=1[Cl:13])[CH:5]=[CH:6][N+:7]([O-:9])=[O:8].C1(C)C=CC(S([CH2:23][N+:24]#[C-:25])(=O)=O)=CC=1>CS(C)=O.CCOCC.O>[Cl:1][C:2]1[CH:3]=[C:4]([C:5]2[C:6]([N+:7]([O-:9])=[O:8])=[CH:25][NH:24][CH:23]=2)[CH:10]=[CH:11][C:12]=1[Cl:13]

Participants

6

Reactant 2

HCID 161915Tosylmethyl isocyanideHCID 23629018984-16-2

Product 1

HCID 4704323-(3,4-Dichlorophenyl)-4-nitro-1H-pyrroleYield 212.2%

Reagents, catalysts & solvents 3

HCID 679Dimethyl SulfoxideSolventHCID 962WaterSolventHCID 3283Diethyl EtherSolvent2×

Procedure

Sodium hydride (2.66 g of a 60% suspension in oil is rinsed with dry ether; 66 mmol) and suspended in 150 mL of dry ether. To this mixture is added over 15 minutes a mixture of 12.0 g (5.5 mmol) of 3,4-dichloro-β-nitrostyrene and 10.8 g (5.5 mmol) of (p-tolylsulfonyl)methyl isocyanide in 50 mL of DMSO and 150 mL of ether. The mixture is stirred for 1.5 hours and then diluted with 150-200 mL of water and additional ether. The ether layer is separated, dried over magnesium sulfate, and concentrated in vacuo. The resulting 10.6 g of crude product is purified by chromatography on silica gel using a 4:1 mixture of chloroform and ethyl acetate. A 7.2 g solid fraction is recrystallized from chloroform-ethyl acetate-hexane to give 3.0 g of yellow solid, m.p. 187°-188° C. (dec.).

Workup

  1. washSodium hydride (2.66 g of a 60% suspension in oil is rinsed with dry ether
  2. additionTo this mixture is added over 15 minutes
  3. customThe ether layer is separated
  4. dry with materialdried over magnesium sulfate
  5. concentrationconcentrated in vacuo
  6. customThe resulting 10.6 g of crude product is purified by chromatography on silica gel using
  7. additiona 4:1 mixture of chloroform and ethyl acetate
  8. customA 7.2 g solid fraction is recrystallized from chloroform-ethyl acetate-hexane

Sources & evidence

ORD record
ord-89b99f7885d44e40b8541c728b1d0a1b
Source dataset
uspto-grants-1990_05
Patent number
US04929634

Reaction notes

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