3047-38-9Relevant academic research and scientific papers
Alkylation of Nitrile Anions by Tertiary α-Halo Ketones and Nitriles
Ros, Francisco,Rosa, Jose de la,Enfedaque, Juan
, p. 5419 - 5424 (2007/10/02)
Potassium salts of nitriles bearing carbethoxy, cyano, or phenyl groups at the α carbon react with tertiary α-halo ketones and nitriles (1-5) in DMSO or HMPA to provide the alkylated β-keto- or β-cyano-β,β-dialkyl nitriles 6-10 in useful yields. (PhCHCN)(-) undergoes cyclization with p-XC6H4COCCl(CH3)2 to produce 2(5H)-furanone 11.Reaction of (Ph2CCN)(-) with PhCOCCl(CH3)2 affords the hydrolyzed ketone 12a and recovered carbon acid, while the anion undergoes oxidative dimerization to NCCPh2CPh2CN with p-O2NC6H4COCCl(CH3)2 with concomitant formation of the reduced ketone p-O2NC6H4COCH(CH3)2 and the hydrolyzed ketone 12b.The alkylations of (-) and (-) with p-O2NC6H4COCX(CH3)2 take place by the SRN1 process.
New Methods for the Syntheses of α,β-Unsaturated Ketones, Aldehydes, and Nitriles by the Palladium-Catalyzed Reactions of Allyl β-Oxo Esters, Allyl 1-Alkenyl Carbonates, and Allyl α-Cyano Esters
Minami, Ichiro,Nisar, Mohammad,Yuhara, Masami,Shimizu, Isao,Tsuji, Jiro
, p. 992 - 998 (2007/10/02)
Allyl β-oxo esters, allyl 1-alkenyl carbonates, and allyl α-cyano esters are converted into α,β-unsaturated ketones, aldehydes, and nitriles by palladium-catalyzed intramolecular decarboxylation-dehydrogenation.Palladium-phosphine complexes such as Pd(OAc)2-PPh3, Pd(OAc)2-dppe, or Pd2(dba)3*CHCl3-PPh3, are effective catalysts.Yields depend on solvents and on the mole ratio of palladium to phosphine.The optimum Pd/P ratio for each substrate was determined.Use of nitriles as solvents is essential for the dehydrogenation.
