Non-heterocyclic nitrogen centres

The kinetics and mechanism of the phosphorus-catalysed dimerization of acrylonitrile to give 1,4-dicyanobut-l-ene and 2,4-dicyanobut-l-ene have been studied.114 The reactions of aryliminodimagnesium (138) with //-substituted p-ey nobcnzophcnones, l-cyano-9-fluorenenone, o-, m-, and /-dicyanobenzenes, and o-, m-, and p-nitrobenzonitriles have been examined.115 The effect of pressure on the reaction of 3-methyl-l-(4-tolyl)triazene (139) and benzoic acid in chloroform and acetonitrile has been studied.116 The effect of acids on the rate of urethane formation from alcohols and isocyanates in the presence of alkyltin carboxylates has been examined.117 A Hammett a value has been reported for the amidine group N=CHNMe2 and used for the prediction of the basicity of sites in bifunctional amidines.118 

Aryl carbazates (140) containing a methyl group in the 2-position hydrolyse by a /J ( 2 mechanism but the others hydrolyse by an ElcB mechanism.119 This conclusion was reached from a study of a wide range of ring-substituted compounds. 

Kinetic evidence for the involvement of a-hydroxydialkylnitrosamines (142) in the pH-independent solvolysis of the a-(acyloxy)dialkylnitrosamines (141) has been obtained.120 The aminolysis in benzene of 0-(2,4-dinitrophenyl)-/ ,/ -disubstituted benzophenone oximes (143) with pyrrolidine and piperidine are third order in amine.121 Hirst s mechanism involving electrophilic catalysis operates and can explain the various effects observed. The bis(pcntamcthylphcnyl)-/V-isopropylketenimine (144) undergoes pre-equilibrium A-protonation in aqueous acetonitrile followed by water attack. An inverse solvent isotope effect and the observation of the diol (145) confirm this.122 

The effect of high pressure (128-2600 bar) and high temperature (330°C) on the hydrolysis of butyronitrile (156) has been reported.  

A theoretical study of the reaction of water and methanol with HNCO has led to a prediction of a four-centred transition state for both reactions. The interactions of water and of alcohols with alkyl isocyanates have been the subject of both experimental and theoretical study. In the case of hydration, evidence for initial interaction of water and water clusters (n = 1-3) across the N=C bond of the alkyl isocyanate 

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