With cyanoamides

Mercaptoquinolinic acid 175 reacts with cyanoamide and with cyano-thioureas to give imines 176 and 177, respectively (73KGS644) (Scheme 61). 

The scope of conditions of the ketone-nitrile reaction is very broad. For instance, the polyfluorinated ketones 156 and 158 react with nitriles in the presence of concentrated sulfuric acid99 and with cyanoamides 159 by reaction mixtures at room temperature in the absence of acid catalyst100,101 (equations 52 and 53). 

Potassium cyanate, carbonic and chlorocarbonic esters, phosgene, or urea are used as cyclizing agents in the synthesis of perimidine-2-one 430 (X = X = NR, Y = O) and its derivatives from 1,8-naphthylene-diamines. Naphtho[substituted amino group in position 2 (X = Y = NH or Y = NR) are obtained on interaction of 1,8-naphthylenediamines with bromocyanogen, cyanoamide, 5-methylisothiourea, arylisothiocyanates, or dimethyltri-chloromethylamine. 

IJ-Thiazine derivatives. The cyanoamide (I)- condenses with an aromatic acid and PPE to form 5-carbamoyl-6-methyllhio-1.3-thiazine-4-oncs (2) in 27 90% yield. The reaction with aliphatic acids gives 5-cyano-6-methylthio-l-keto-l,3-thiazine-4-ones (3) in low yields. ... 

The ready reaction of conjugated azoalkenes with a molar excess of nitriles containing activated methylene groups (e.g. malononitrile, p-cyanoamides, p-phosphononitriles or remotely activated nitriles) has been examined. 

Another interesting example of hydroxyl group participation occurs upon treatment of the hydroxyferrocene cyanide (251) with potassium cyanide in ethanol. The cyanoamide (252) is said to form by cyanide attack on the cyclic intermediate. Alternatively, it seems to us that Ph2C—O bond cleavage to the amide and the highly stabilized carbonium ion may precede CN" attack since the process as shown involves attack at a highly hindered carbon. 

A number of other syntheses of coniine have been effected, of which that of Diels and Alder is of speeial interest. The initial adduct of pyridine and methyl acetylenedicarboxylate, viz., tetramethylquinoIizine-1 2 3 4-tetracarboxylate (IX) on oxidation with dilute nitric acid is converted into methyl indolizinetricarboxylate (X). This, on hydrolysis and decarboxylation, furnishes indolizine, the octahydro-derivative (XI) of which, also known as octahydropyrrocoline, is converted by the cyanogen bromide method (as applied by Winterfeld and Holschneider to lupinane, p. 128) successively into the bromocyanoaraide (XII), cyanoamide (XIII) and dZ-coniine (XIV). A synthesis of the alkaloid, starting from indolizine (pyrrocoline) is described by Ochiai and Tsuda. ... 

A related type b cyanoamidation leading to 3-pyrrohn-2-ones was reported by the Takemoto group (Scheme 19 20060L2711). Treatment of the alkyne 116 with catalytic Pd(PPh3)4 in xylene gives an equal mixture of 3-pyrrolin-2-one 117 and alkyhdene lactam 118. The mechanism presumably involves a 5-cxo-trig oxidative addition of cyanide and the amide carbonyl across the alkyne isomerization of 118 under the reaction conditions then leads to the formation 117. 

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