Formamide and derivs

Amino-pyridazines and -pyridazinones react with monomethyl- or iV,A-dimethyl-formamide and other aliphatic amides in the presence of phosphorus trichloride, thionyl chloride, phosgene or benzenesuUonyl chloride to give mono- or di-alkylaminomethyl-eneamino derivatives. The same compounds can be prepared conveniently with A,iV-dimethylformamide dimethyl acetal in high yield (Scheme 50). 

These include hydrazine, dimethylsulfoxide (DMSO), formamide and some derivatives (N-methylformamide and dimethylformamide), acetamide and some derivatives, and pyridine N-oxide. Some salts such as potassium acetate also intercalate kaolinites. Once intercalated by one of these small molecules or salts, other molecules which normally do not directly intercalate kaolins can be introduced by replacement. Further, the exposure of the inner surfaces by intercalation gives one the opportunity to alter the interlayer bonding of the kaolin layers by chemical modification of the inner surfaces. 

In a Vilsmeier-Haack-Amold reaction, A/,Ar-disubstituted amino-methylenemalonates (329) were prepared in good yields from the sodium derivative of diethyl malonate or from diethyl malonate in the presence of triethylamine in benzene or toluene at a temperature below 20°C with imidoyl chlorides, which were prepared in situ from N./V-disubstituted formamides and phosphoryl chloride (63BRP917436). Instead of diethyl malonate, diethyl ethoxymagnesiummalonate could also be used (63 BRP917436). 

Kennedy GL, Jr Biological effects on acetamide, formamide, and their monomethyl and dimethyl derivatives. CRC CritRev Toxicol 17 129-182, 1986... 

Ready formation of pyrazolo[3,4-4 pyrimidines from reaction of 5-aminopyrazole -carboxylic acid derivatives is a well-established route to derivatives of this ring system. A recent application is the conversion of 286 into 288 by reaction with formamide and NIS 287 (Equation 40) <2002BML1687>. 

Azodicarboxamidine. See Azobisformamidine under Azobisformic Acid and Derivatives, Azodicorboxyethylamide. See Azobisethyl-formamide under Azobisformic Acid and Derivatives, p A653... 

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