Nitromethane → 1-Methyl-4-nitro-2-[(E)-2-nitrovinyl]benzene

HRID 1053701Notes

Reaction equation

HRID 1053701 reaction equation
[CH3:1][C:2]1[CH:9]=[CH:8][C:7]([N+:10]([O-:12])=[O:11])=[CH:6][C:3]=1[CH:4]=O.C([O-])(=O)C.[NH4+].[N+:18]([CH3:21])([O-:20])=[O:19]>C(O)(=O)C>[CH3:1][C:2]1[CH:9]=[CH:8][C:7]([N+:10]([O-:12])=[O:11])=[CH:6][C:3]=1/[CH:4]=[CH:21]/[N+:18]([O-:20])=[O:19]

Participants

5

Reactant 3

HCID 6375NitromethaneHCID 517165Ammonium AcetateHCID 126541452-Methyl-5-nitrobenzaldehyde2×

Product 1

HCID 1182770521-Methyl-4-nitro-2-[(E)-2-nitrovinyl]benzene

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

Adapting literature known protocols (U.S. Pat. No. 8,344,028; and Kabalka and Varma, Org. Prep. Proced. Int., 1987, 19(4-5), 283-328), 1-methyl-4-nitro-2-[(E)-2-nitrovinyl]benzene (19a) is prepared by heating a solution of commercial 2-methyl-5-nitro-benzaldehyde (5j) (1.65 g, 10.0 mmol) (for a synthesis of (5j) see also Example 5, Method B), ammonium acetate (NH4OAc) (1.31 g, 17.0 mmol) in a mixture of nitromethane (MeNO2) (1.61 mL, 1.83 g, 30.0 mmol) and acetic acid (HOAc) (10.0 mL) to reflux for about 3 hours. Aqueous work-up and purification by silica gel column chromatography using ethyl acetate (EtOAc) and hexanes mixtures afford the title compound (19a).

Workup

  1. custom, 1987, 19(4-5), 283-328), 1-methyl-4-nitro-2-[(E)-2-nitrovinyl]benzene (19a) is prepared
  2. temperatureto reflux for about 3 hours
  3. customAqueous work-up and purification by silica gel column chromatography

Sources & evidence

ORD record
ord-4db38c0bcae44a11a54e79dae3ae887b
Source dataset
uspto-grants-2016_07
Patent number
US09394236B2

Reaction notes

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