Triethyl phosphonoacetate → 3,5-Dimethyl-1-(carbethoxymethylene)cyclohexane

HRID 1461952Notes

Reaction equation

[Na].C(OP([CH2:10][C:11]([O:13][CH2:14][CH3:15])=[O:12])(OCC)=O)C.[CH3:16][CH:17]1[CH2:22][CH:21]([CH3:23])[CH2:20][C:19](=O)[CH2:18]1>C1(C)C=CC=CC=1>[CH3:16][CH:17]1[CH2:22][CH:21]([CH3:23])[CH2:20][C:19](=[CH:10][C:11]([O:13][CH2:14][CH3:15])=[O:12])[CH2:18]1

Participants

Conditions

Temperature: 20 °C

Procedure

85 g of dry toluene are added to a round flask which is fitted with a stirrer, thermometer, dropping funnel and reflux condenser. Under a nitrogen atmosphere there are now introduced 17.2 g of sodium in small portions and the mixture is heated to boiling. After dissolution of the sodium (after about 3 hours), the mixture is cooled to 20° C. and there is slowly added dropwise thereto (during about 11/2 hours) a mixture of 219 g of ethyl diethylphosphonoacetate, 95 g of 3,5-dimethyl-cyclohexanone and 220 g of dry toluene. The temperature is held between 25° and 30° C. The mixture is stirred at this temperature for a further 2 days and thereupon poured on to 400 g of ice, extracted with toluene, washed neutral and concentrated. The residue is distilled over a Widmer column and thus yields 110 g of ethyl 3,5-dimethyl-cyclohexylideneacetate.

Workup

customis fitted with a stirrer
temperaturereflux condenser
temperaturethe mixture is heated to boiling
additionthere is slowly added dropwise
customis held between 25° and 30° C
extractionextracted with toluene
washwashed neutral
concentrationconcentrated
distillationThe residue is distilled over a Widmer column and thus yields 110 g of ethyl 3,5-dimethyl-cyclohexylideneacetate

Sources & evidence

ORD record: ord-f0f658d9eed243439cefe46c4cfb9e93
Source dataset: uspto-grants-1984_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US04457862

Reaction notes

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