Nitromethane → Nitromethyl 3-methyl-2-thienyl ketone
Reaction equation
[CH3:1][C:2]1[CH:6]=[CH:5][S:4][C:3]=1[C:7]([OH:9])=O.[N+:10]([CH3:13])([O-:12])=[O:11].C(P(=O)(OCC)OCC)#N.C(N(CC)CC)C>CN(C=O)C.C1(C)C=CC=CC=1.C(OCC)(=O)C>[CH3:1][C:2]1[CH:6]=[CH:5][S:4][C:3]=1[C:7]([CH2:13][N+:10]([O-:12])=[O:11])=[O:9]Participants
Conditions
- Temperature
- 0 °C
Procedure
A solution composed of 10 g (70 mmol) of 3-methyl-2-thiophenecarboxylic acid, 3.4 g (56 mmol) of nitromethane and 115 ml of DMF is cooled to 0° C. 11.9 g (72.8 mmol) of diethyl cyanophosphonate in 56 ml of DMF, and then 18.2 g (180 mmol) of triethylamine in 56 ml of DMF are added thereto successively. The medium is then stirred for 2 hours at 0° C. and for 21 hours at room temperature. The reaction medium is poured over 1 litre of a toluene/ethyl acetate (1:1) mixture, and extracted with water. This aqueous phase, acidified with 40 ml of acetic acid, is extracted with a toluene/ethyl acetate (1:1) mixture. The organic extracts are washed with water and then with a saturated NaCl solution in water, before being dried over Na2SO4 and concentrated. The residue, purified by chromatography on a silica column in dichloromethane and then by recrystallization from an ethyl acetate-hexane mixture, gives 2 g of a pale yellow solid (Yield=19%).
Workup
- extractionextracted with water
- extractionis extracted with a toluene/ethyl acetate (1:1) mixture
- washThe organic extracts are washed with water
- dry with materialwith a saturated NaCl solution in water, before being dried over Na2SO4
- concentrationconcentrated
- customThe residue, purified by chromatography on a silica column in dichloromethane
- customby recrystallization from an ethyl acetate-hexane mixture
Sources & evidence
- ORD record
- ord-2f67b0a9ffa94a979ffc1339ed168dfc
- Source dataset
- uspto-grants-1999_08
- Patent number
- US05932765
Reaction notes
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