Triazine, cellulose derivatives, preparation

In the case of quaternary derivatives made from the non-planar aliphatic amines 7.64, 7.65 and 7.66, steric strains further destabilise the C-N+ bond so that reaction with cellulose occurs under alkaline conditions at 30 °C, whereas temperatures of about 40-50 °C are required for the pyridinium derivatives 7.67. The quaternisation approach appeared to offer the opportunity to prepare dyes yielding reactivity levels intermediate between those of aminochloro- and dichlorotriazine dyes without loss of the desirable stability of the dye-fibre bond to acidic conditions that is characteristic of aminohalotriazine dyes. Unfortunately, this ideal was not attainable because of the objectionable odours of the tertiary amines liberated by the fixation reaction and the sensitivity of the reactivity behaviour of the quaternised derivatives to the nature of the chromogen attached to the triazine ring, making it difficult to select compatible combinations of dyes. 

The structure of Blue Dextran 2000, a water-soluble commercial derivative, involves a triazine type of dye covalently linked to dextran, and, in a way analogous to that used for other dyed polysaccharides, has been employed for the assay of dextranase. The ability of Blue Dextran 2000 to bind proteins cannot be attributed to formation of a covalent link, because no chloro groups remain on the triazinyl rings. The binding must involve an ionic bond between the protein and the sulfonic groups of the dye residue, and, in one case, the association could be reversed by using 0-(2-diethylaminoethyl) cellulose to abstract the dyed polysaccharide. Other chlorotriazinyl dyes have been used in the preparation of dyed derivatives of amylopectin, laminaran, dextrans, pectin, pelvetian, zosterine, and cellulose. As already mentioned, triazine-dyed polysaccharides are useful in enzyme insolubilization. 

Amylopectins. — The effects of acrylamide graft copolymerization on the solution properties of amylopectin have been discussed. Amylopectin has been dyed with DyAmyl-L and used in this form as a substrate for the assay of a-amylase. Amylopectin has been treated with isocyanate derivatives of 4-amino-( 1,1-dimethyl ethyl)-3-(methylthio)-l,2,4-triazin-5(4/f)-one ( metribuzin ) or acid chloride derivatives of 2,4-dichlorophenoxyacetic acid ( 2,4-D ) and 2,2-dichloropropionic acid ( dalapon ), to produce controlled-release polymeric pesticide systems. The solvent system utilized for these reactions, a lithium chloride or bromide salt in AW-dimethylacetamide, allows dissolution of the reactant salt and facilitates analysis of the polymer product by such techniques as i.r., U.V., and n.m.r. spectroscopies and gel permeation chromatography. Derivatives of other naturally occurring polysaccharides, including amylopectin, cellulose, chitin, and dextran, were also prepared. 

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