Diethyl (cyanomethyl)phosphonate → 1-[(E)-2-Cyanovinyl]cyclopropanecarbonitrile
Reaction equation
CC(C)([O-])C.[K+].[C:7]([CH2:9]P(=O)(OCC)OCC)#[N:8].[CH:18]([C:20]1([C:23]#[N:24])[CH2:22][CH2:21]1)=O>C1COCC1>[C:7](/[CH:9]=[CH:18]/[C:20]1([C:23]#[N:24])[CH2:22][CH2:21]1)#[N:8]Participants
Procedure
To a solution of 1.0 M potassium tert-butoxide in THF (1.12 mL) at 0° C. was added slowly dropwise a solution of diethyl cyanomethylphosphonate (210 mg, 1.2 mmol) in THF (2 mL). The cold bath was removed and the reaction was warmed to ambient temperature. The solution was then re-cooled to 0° C. and a solution of 1-formylcyclopropanecarbonitrile (101 mg, 1.06 mmol) in THF (1.0 mL) was added dropwise. The cold bath was removed and the reaction was stirred for 3 hours at ambient temperature. The mixture was then diluted with ether and water, the ether solution was separated, washed with brine, dried over sodium sulfate, filtered and the solvent was removed in vacuo. Flash column chromatography (eluting with a gradient from 0-60% ethyl ether in hexanes) afforded the product (24 mg, 19%).
Workup
- customThe cold bath was removed
- temperatureThe solution was then re-cooled to 0° C.
- customThe cold bath was removed
- additionThe mixture was then diluted with ether and water
- customthe ether solution was separated
- washwashed with brine
- dry with materialdried over sodium sulfate
- filtrationfiltered
- customthe solvent was removed in vacuo
- washFlash column chromatography (eluting with a gradient from 0-60% ethyl ether in hexanes)
Sources & evidence
- ORD record
- ord-aced21954c17499da564fbd36a6f4d2b
- Source dataset
- uspto-grants-2015_12
- Patent number
- US09206187B2
Reaction notes
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