Triazines methoxylation

Flament et al made use of the partial replacement of two chlorine atoms in cyanuric chloride (12) with methoxyl groups, the 2,4-di-methoxy-6-chloro-l,3,5-triazine (13) formed was dehalogenated to 2,4-dimethoxy-1,3,5-triazine (14) and this yielded the product (2) on gentle hydrolysis. 

Mono-substitution occurs most readily in the stepwise replacement of the halogen substituents of 2,4,6-trichloro-s-triazine with aqueous methanol and sodium bicarbonate (30°, 30 min), the monomethoxy derivative (324) is obtained on heating (65°, 30 min), the disubstitu-ted derivative is formed and on brief heating (65°) with the more basic sodium carbonate or methanolic sodium hydroxide (25°, 3 hr) complete methoxylation (320) occurs. Ethanolic ethoxide (25°, 1 hr) or sodium carbonate (35°) is sufficient to give complete ethoxy-dechlorination. The corresponding phenoxy derivatives are obtained on treatment with one (0°), two (15°, 1 hr), or three equivalents (25-70°, 3 hr) of various sodium phenoxides in aqueous acetone. The stepwise reaction with phenols, alcohols, or thiols proceeds in better yield in organic solvents (acetone or chloroform) with collidine or 2,6-lutidine as acid acceptors than in aqueous sodium bicarbonate. ... 

The sole representative of this class is l-(4,6-dimethoxy-l,3,5-triazin-2-yl)pyrene (67), [3271-22-5], which gives a bluish white brightening effect on polyester substrates it is employed chiefly in combination with other polyester brighteners such as 38. Compound 67 is obtained by the Fricdel-Crafts reaction of cyanuric chloride with pyrene with subsequent replacement of the remaining chlorines with methoxyl groups [117],... 

TV.7V-Dimethylbenzylamine [64,65], 2,4.6-tris(dialkylamino)-l,3,5-triazines [66], N-(2,2,2-trifluoroethyl)amines [67,68], and TV-(2,2-difluoroethyl)amines [68] exhibit similar behavior. Methoxylation of enamines results in substitution at both the vinylic and the allylic positions [61]. 

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