Ketones, cyclic => dinitriles

The insertion reaction chemistry of the well-known germylene Ge [CH(Si M03)3)2 50 is very diverse.154 323-328 This species inserts readily into the C-H bonds of mono- and dinitrile substrates (Scheme 47),154 the C-H bonds of ethers and alkanes in the presence of Phi (Scheme 48),323 the C-H bonds of ketones in the presence of MgCE (Scheme 49) and the O-H bonds of the tautomer enols in the absence of MgCl2 (Scheme 50),324 and the C-H bonds of diketones resulting in cyclic products (Scheme 51). 

Thorpe reaction org chem The reaction by which, in presence of lithium amides, a,(rt-dinitriles undergo base-catalyzed condensation to cyclic iminonitriles, which can be hydrolyzed and decarboxylated to cyclic ketones. thorp re,ak-shan TMPC See tetrakis(hydroxymethyl)phosphonium chloride, thulia See thulium oxide. thu-le-a ... 

Ziegler method. Cyclization of dinitriles at high dilution in dialkyl ether in the presence of ether-soluble metal alkylanilide and hydrolysis of the resultant imino-nitrile with formation of macro-cyclic ketones in good yields. 

The ethylbenzene formed does not interference with subsequent reactions. The condensing agent is sensitive to air, so that all operations must be conducted with an atmosphere of pure nitrogen. For each 0.1 mole of the dinitrile, 1.5 1 of a 0.60-0.67 molar solution of sodio-Y-methylaniline containing a 25% excess of TV-methylaniline is used 246 the solution is heated and stirred under reflux in a nitrogen atmosphere while the dinitrile is run in continuously during 72 h. The subsequent hydrolysis to the cyclic ketone is carried out as indicated in the scheme above. 

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