Methylenediamines activated

Reactant 7.123 can be prepared by reacting acrylonitrile with s-trioxane (Scheme 7.74) using an acid catalyst in carbon tetrachloride as solvent [147]. Two commercially available bifunctional reactants, N,N -bis(acryloyl)methylenediamine (7.133) and its water-soluble bis-quaternary precursor (7.134), have been evaluated to achieve dyeings of similar quality at lower cost. The precursor is readily converted to the active reactant at about pH 8 during... 

Equilibrium studies have shown that the first formation constant of the chromium(iii)-ethylenediamine system is < 10, over 10 -fold smaller than the value (10 ) previously reported. [Cr(en)3 (tn) ] (x = 0—3 and tn = tri-methylenediamine) complexes have been prepared and resolved using nitro-(-f )D-camphor. These mixed complexes have the same absolute configuration, A, as the pure [Cr(en)3] and [Cr(tn)3] species. Selective intervention of an optically active counterion in the relaxation processes of excited enantiomeric complexes can lead to partial resolution. This has been achieved for [Cr(phen)3] using D-tartrate. ... 

In Mannich reactions performed in basic media, the active aminomethylating species is less well defined. It may be a methylenediamine (9), a hydroxymethylamine (8), or an alkoxymethylamine (ROCH2NR2 ) (in alcoholic solvents). Aminomethylation in base-catalyzed Mannich reactions, as shown for cyclohexanone, is believed to occur by an 5n2 mechanism in which the enolate (13) displaces either NR2", 0H , or OR from one of the intermediates above (Scheme 2). 

Physiologically active nitrogen-containing heterocycles have been obtained reacting heterocycles 1 with methylenediamines and H-phosphonate diesters [67]. In the first stage of the reaction, diamine reacts with dialkyl H-phosphonate to give dialkyl... 

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