Nitromethane → methyl [5-chloro-3-(nitromethyl)-2-oxo-2,3-dihydro-1H-indol-3-yl](cyano)acetate

HRID 883651Notes

Reaction equation

HRID 883651 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][CH:10]=1)[NH:7][C:6](=[O:11])/[C:5]/2=[C:12](/[C:17]#[N:18])\[C:13]([O:15][CH3:16])=[O:14].[N+:19]([CH3:22])([O-:21])=[O:20].N1CCCCC1>C(OCC)(=O)C>[Cl:1][C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][CH:10]=1)[NH:7][C:6](=[O:11])[C:5]2([CH:12]([C:17]#[N:18])[C:13]([O:15][CH3:16])=[O:14])[CH2:22][N+:19]([O-:21])=[O:20]

Participants

5

Reactant 3

HCID 6375NitromethaneHCID 8082PiperidineHCID 24828581methyl (2Z)-(5-chloro-2-oxo-1,2-dihydro-3H-indol-3-ylidene)(cyano)acetate

Product 1

HCID 24827441methyl [5-chloro-3-(nitromethyl)-2-oxo-2,3-dihydro-1H-indol-3-yl](cyano)acetateYield 73.8%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Procedure

A suspension of methyl (2Z)-(5-chloro-2-oxo-1,2-dihydro-3H-indol-3-ylidene)(cyano)acetate, intermediate 1 (10.000 g; 38.1 mmol) in dry nitromethane (61 ml; 1.14 mol) was treated with piperidine (189 μl; 1.90 mmol). After stirring for 3 hours, the mixture was diluted with ethyl acetate and filtered through silica. Evaporation of the solvent gave methyl [5-chloro-3-(nitromethyl)-2-oxo-2,3-dihydro-1H-indol-3-yl](cyano)acetate as an oil (9.1 g, 73.8%). This was a mixture of diastereomers which was sufficiently pure for subsequent reaction (HPLC purity 97%). MS (ESI+): 324.2; MS (ESI−): 322.2

Workup

  1. filtrationfiltered through silica
  2. customEvaporation of the solvent

Sources & evidence

ORD record
ord-1559b5d87dcb447e8358f8ad26f5b6c3
Source dataset
uspto-grants-2012_08
Patent number
US08236963B2

Reaction notes

Loading…