Transamidation

Other interesting regioselective reactions are carried out within the synthesis of nitrofurantoin. Benzaidehyde semicarbazone substitutes chlorine in chloroacetic ester with the most nucleophilic hydrazone nitrogen atom. Transamidation of the ester occurs with the di-protic outer nitrogen atom. Only one nucleophilic nitrogen atom remains in the cyclization product and reacts exclusively with carbonyl compounds. 

Transamidation. Polyacrylamide reacts with primary amines such as hydrazine [302-01-2], N2H4, (54) and hydroxjlamine [7803-49-8]. NH O, (55—57) to form substituted amides with loss of ammonia. 

MPD-1 fibers may be obtained by the polymeriza tion of isophthaloyl chloride and y -phenylenediamine in dimethyl acetamide with 5% lithium chloride. The reactants must be very carefully dried since the presence of water would upset the stoichiometry and lead to low molecular weight products. Temperatures in the range of 0 to —40° C are desirable to avoid such side reactions as transamidation by the amide solvent and acylation of y -phenylenediamine by the amide solvent. Both reactions would lead to an imbalance in the stoichiometry and result in forming low molecular weight polymer. Fibers are dry spun direcdy from solution. 

Transamidation and Transesteramidation. Transamidation is the mutual exchange of chain fragments in a polyamide, shown as follows where R, R" and R, R" represent polymer chain fragments of any length. 

It is generally accepted that transamidation is not a concerted reaction, but occurs through the attack of a free end on the amide group via aminolysis (eg, eq. 4) or acidolysis (eg, eq. 3) (65). Besides those ends always present, new ends are formed by degradation processes, especially hydrolysis (eq. 5), through which the amide groups are in dynamic equiUbrium with the acid and amine ends. 

The step in which the free acid and amine ends recombine (eq. 6) is only accompHshed statistically, since it is unlikely that any two particular ends formed in the acidolysis or aminolysis steps would find each other in the melt. Transamidation is cataly2ed by both acidic and basic ends, but in general acids appear to be much more effective than bases (59,65). 

Transamidation is an important process in the melt phase for polyamides because it is usually the process by which an equiUbrium molecular weight distribution is reestabUshed and, in the case of the melt blending of two or more polyamides to form a copolymer, it is the process by which randomi2ation of the individual monomers along the chain is effected. In the soHd phase, chain mobiUty is restricted and equiUbrium in either case often is not achieved. 

Transesteramidation is a process similar to transamidation, except that a polyamide is mixed with a polyester rather than another polyamide (67). 

A related antiinflammatory agent prepared via a more traditional route is fluproquazone (65). Heating with urea in acetic acid results in transamidation by synthon 64 and... 

Important solvolysis reactions for nylons are hydrolysis, methanolysis, glycolysis, aminolysis, ammonolysis, transamidation, and acidolysis.17 Hydrolysis of nylon-6 with steam in the presence of an acid catalyst to form caprolactam is tlie preferred depolymerization approach. However, when recycling carpet face fibers, file fillers in the polymer may react with file acid catalyst and lower the efficiency of the catalyst. 

Transamidation, polyamide, 158 Transesterification, 529-530 Transesterification polymerizations, 69-74 Transimidization, 302-303 Transition metal coupling, 10, 467-523 applications for, 472-476 chemistry and analytic techniques for, 483-490... 

H3PO4 is being used for transamidation in such a case XRF determines higher phosphorous concentrations than justified on the basis of the phosphite additives. Ion chromatography may then be required. 

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