Nitromethane → Methyl 3-methyl-4-nitrobutanoate

HRID 27351

Reaction equation

HRID 27351 reaction equation
N12CCCCC1C=NCCC2.[N+:12]([CH3:15])([O-:14])=[O:13].[C:16]([O:21][CH3:22])(=[O:20])/[CH:17]=[CH:18]/[CH3:19]>CO>[CH3:19][CH:18]([CH2:15][N+:12]([O-:14])=[O:13])[CH2:17][C:16]([O:21][CH3:22])=[O:20]

Participants

5

Reactant 3

HCID 6375NitromethaneHCID 3141121,5-Diazabicyclo(5,4,0)undec-5-eneHCID 638132Methyl Crotonate

Product 1

HCID 13633418Methyl 3-methyl-4-nitrobutanoateYield 66.2%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent2×

Conditions

Temperature
60 °C

Procedure

1,5-Diazabicyclo[5,4,0]-undec-5-ene (6 ml) is added to a solution of nitromethane (91.5 g) in methanol (500 ml). The resulting mixture is heated to 60° C. and methyl crotonate (100 g, lm) is added under nitrogen. The mixture is then stirred for 6 days at 60° after which it is cooled to room temperature and most of the methanol is removed in vacuo. The residue is treated with ether (500 ml) and washed with 2 N hydrochloric acid (250 ml) and water (250 ml). The organic layer is dried (Na2SO4) and evaporated in vacuo to give crude product. The crude product is purified by column chromatography on silica gel (500 g, ethyl acetate/hexane 2:98) to give methyl 3-methyl-4-nitrobutanoate (106.6 g, 66%).

Workup

  1. customis removed in vacuo
  2. additionThe residue is treated with ether (500 ml)
  3. washwashed with 2 N hydrochloric acid (250 ml) and water (250 ml)
  4. dry with materialThe organic layer is dried (Na2SO4)
  5. customevaporated in vacuo
  6. customto give crude product
  7. customThe crude product is purified by column chromatography on silica gel (500 g, ethyl acetate/hexane 2:98)

Sources & evidence

ORD record
ord-dbc18eb3995d493ab393253e55b62903
Source dataset
uspto-grants-1980_09
Patent number
US04221717

Linked notes

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