Hydrochloric Acid → 2-(4-Chloro-2-nitro-phenylamino)-5-methyl-thiophene-3-carbonitrile

HRID 131308

Reaction equation

HRID 131308 reaction equation
[NH2:1][C:2]1[S:3][C:4]([CH3:9])=[CH:5][C:6]=1[C:7]#[N:8].Cl[C:11]1[CH:16]=[C:15](Cl)[CH:14]=[CH:13][C:12]=1[N+:18]([O-:20])=[O:19].O.[OH-].[Li+].[ClH:24]>CS(C)=O>[Cl:24][C:16]1[CH:15]=[CH:14][C:13]([NH:1][C:2]2[S:3][C:4]([CH3:9])=[CH:5][C:6]=2[C:7]#[N:8])=[C:12]([N+:18]([O-:20])=[O:19])[CH:11]=1

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 118992,4-DichloronitrobenzeneHCID 168937Lithium hydroxide, monohydrateHCID 6890562-Amino-5-methyl-3-thiophenecarbonitrile

Product 1

HCID 586259752-(4-Chloro-2-nitro-phenylamino)-5-methyl-thiophene-3-carbonitrileYield 33%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Procedure

Dissolve 2-amino-5-methyl-thiophene-3-carbonitrile (4.14 g, 30 mmol) and 2,4-dichloronitrobenzene (5.76 g, 30 mmol) in dimethylsulfoxide (70 ml) and stir under nitrogen. Add lithium hydroxide monohydrate (2.0 g, 47.7 mmol) and heat the mixture in an oil bath at room temperature for 18 hours. Pour the mixture into ice water, make acid with 2N HCl, extract into ethyl acetate, dry (MgSO4) and concentrate under reduced pressure. Crystallize from ethanol to give 2-(4-chloro-2-nitro-phenylamino)-5-methyl-thiophene-3-carbonitrile as a yellow solid (2.92 g, 33%): NMR (1H, 300 MHz, CDCl3): δ 9.5 (1H broad), 8.25 (1H,s), 7.45 (1H, d), 7.1 (1H,d), 6.25 (1H, s), 2.5 (3H,s).

Workup

  1. extractionextract into ethyl acetate
  2. dry with materialdry (MgSO4)
  3. concentrationconcentrate under reduced pressure
  4. customCrystallize from ethanol

Sources & evidence

ORD record
ord-086e4767ef7d4d3ca57bc77654685a55
Source dataset
uspto-grants-2008_06
Patent number
US07384934B2

Linked notes

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