Y-Cyanoketones

Monocyanoethylation of deoxybenzoin and phenylacetone.int-butyl alcohol gives y-cyanoketones (XU-76 Rs = CgHs, Rg = CH3, CgHs), which are cyclized by potassium hydroxide in t-butyl alcohol/methanol to 3,4-dihydro-S-phenyl-6 substituted-2-pyridones (Xn-77), which can be dehydrogenated to 5-phenyl-6-substituted-2-pyridones (XII-78). When y-benzoylbutyronitrile is passed over AljOa at 400" or over Cr203/Al203 at 300 to 310°, 6-phenyl-2-pyridone (W-79)is formed. Mixtures of products can be formed in these reactions for... 

Triethylaluminum (s. a. under TiCl ) y -Cyanoketones from a, -ethyleneketones... 

Acetone cyanohydrin as a source of hydrogen cyanide s. U, 773 y -Cyanoketones from chalcones GO G G GO GHG GN... 

Ketoesters, synthesis of 608, 615 Ketones - see also a-Cyanoketones, Hydroxyketones, Sulphinylketones synthesis of 811-814 y-Ketonitriles, synthesis of 322 /3-Ketosulphones... 

Shono and Kise have investigated the electroreductive coupling reaction of y- and -cyanoketones, yielding bicyclic a-hydroxy ketones 218 and their dehyd-roxylated equivalents 221 [198], Optimized yields are obtained when the electroreduction is carried out in i-propanol at a controlled potential of — 2.8 V using a divided cell equipped with a ceramic diaphragm and an Sn or Ag cathode. The product ratio is controlled by the reaction temperature. When the reaction is carried out at 25°C, almost exclusively the a-hydroxy ketone 218 is obtained, whereas at 65°C the obviously thermally dehydroxylated ketone 221 is the predominant product (Scheme 42). Furthermore, this methodology has been... 

An aq.-alc. soln. of the startg. cyanoketone warmed in pH 10 NaaCOg/NaHCOg buffer 7-hydroxy-a,a,y-trimethylbutyrolactam. Y 84%. - This reaction involves an unusually mild basic hydrolysis of a nitrile. F. e. s. R. V. Stevens and M. Kaplan, Chem. Commun. 1970, 822. 

A soln. of diethylaluminum cyanide in benzene added to a soln. of 3,3 -17,17- bisethylenedioxyandrosta -5,8-dien-ll-one in benzene-toluene, and the product isolated after 10 min. at 0° cyanoketone. Y 73.3% with repeated hydrocyanation of recovered startg. m. 91.6%. 

Gyanogen chloride in dioxane added in a slow stream with stirring and ice-saltcooling at 3-8° to a soln. of l-(N-pyrrolidyl)cyclononene and a little more than 1 mole triethylamine in the same solvent, kept at 3-6° for an additional 2 hrs. and at room temp, overnight 2-cyanocyclononanone. Y 77%, F. cyclic -cyanoketones s. M. E. Kuehne, Am. Soc. 81, 5400 (1959). 

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