C([O-])(=O)C.[K+].[C:6]([CH2:8][C:9]([O:11][CH2:12][CH3:13])=[O:10])#[N:7].[Cl:14]C(C#N)(Cl)C(OCC)=O.[CH:24]([C:26]([CH3:28])=O)=[CH2:25].CN(C=O)C.P(Cl)(Cl)Cl>C(N(CC)CC)C.C1(C)C=CC=CC=1>[Cl:14][C:6]1[C:8]([C:9]([O:11][CH2:12][CH3:13])=[O:10])=[CH:25][CH:24]=[C:26]([CH3:28])[N:7]=1To a mixture of 20 mL of toluene, 0.5 g of potassium acetate, 0.7 ml of triethylamine, and 4.25 g (40 mmol) of ethyl cyanoacetate at 5° C. were added dropwise 7.28 g (40 mmol) of ethyl 2,2-dichlorocyanoacetate. The resulting mixture was stirred at 5° C. for 30 min., and methyl vinyl ketone (4.2 g, 60 mmol) was added via a syringe pump in 1 h. After stirring at room temperature for 6 hours, 6.2 mL (80 mmol) of DMF was added, followed by slow addition of PCl3 (11 g, 80 mmol). Anhydrous HCl gas was bubbled in for 10 min., while keeping the reaction temperature around 65° C. After being heated at 80° C. for 1 hour, the reaction mixture was cooled, quenched with aqueous ammonium hydroxide, extracted with toluene, washed with 5% NaHCO3, and dried over MgSO4. Distillation afforded 5.83 g of the title compound. (36% yield, 112°-15° C./0.2 mm Hg).
読み込み中…
