Sodium Bicarbonate → 4-(Methoxymethylene)cyclohexanecarbonitrile

温度

25 °C

9.6 g of triphenyl(methoxymethyl)phosphonium chloride were suspended in 50 ml of t-butyl methyl ether while gassing with argon and treated portionwise at -10° C. with 3.39 g of solid potassium t-butylate. After completion of the addition, the mixture was stirred at 0° to 5° C. for a further 30 minutes and then the deep orange, partially heterogeneous mixture was treated dropwise within 10 minutes with a solution of 2.30 g of 4-cyanocyclohexanone in 20 ml of t-butyl methyl ether. In so doing, the internal temperature should not exceed 5° C. After completion of the addition, the now yellow-orange mixture was warmed to 25° C. and stirred for a further 2 hours. 50 ml of a 2% sodium hydrogen carbonate solution were subsequently added and the separated, aqueous phase was extracted twice with 50 ml of diethyl ether each time. The organic phases were washed with 50 ml of saturated sodium chloride solution, dried over potassium carbonate and concentrated. The residual, semi-crystalline, orange oil was triturated with 400 ml of hexane, cooled to -20° C. and freed from precipitated triphenylphosphine oxide by filtration (rinsing with cold hexane). Low-pressure chromatography (0.4 bar) of the concentrated residue on silica gel using 10% ethyl acetate/petroleum ether as the eluant gave 1.60 g (56%) of 4-(methoxymethylene)cyclohexanecarbonitrile as a colourless oil (purity 97%).

1. additionAfter completion of the addition
2. customexceed 5° C
3. additionAfter completion of the addition
4. stirringstirred for a further 2 hours
5. extractionthe separated, aqueous phase was extracted twice with 50 ml of diethyl ether each time
6. washThe organic phases were washed with 50 ml of saturated sodium chloride solution
7. dry with materialdried over potassium carbonate
8. concentrationconcentrated
9. customThe residual, semi-crystalline, orange oil was triturated with 400 ml of hexane
10. temperaturecooled to -20° C.
11. customfrom precipitated triphenylphosphine oxide
12. filtrationby filtration (rinsing with cold hexane)

ORDレコード

ord-8d828eb6cb764e8080c073066756b89a

出典データセット

uspto-grants-1988_11

DOI

10.6084/m9.figshare.5104873.v1

特許番号

US04783280