Cyanuric chloride, reactions with alcohols

Another sequence of reactions starting with DAS is needed for weakly basic amines, such as aniline sulfonic acids, and also for alcohols. These are initially treated with cyanuric chloride, then with DAS in an aqueous medium at 40-50 °C. In this way the number of side reactions is substantially reduced. 

It is possible to make the chlorine atoms in cyanuric chloride combine with one, two, or three compounds containing hydroxyl or amino groups attached to coloured dye molecules. The reactions with water, alcohols, and amines are summarized below (Coffey, Chem. Ind., 1960, 136). 

CHLORCYAN (506-77-4) CNCl C-N-CL Noncombustible gas. Violent polymerization can be caused by chlorine or moisture. Violent reaction with alcohols, alkenes, and alkynes (violent exothermic reaction) acids, acid salts, amines, strong alkalis, olefins, strong oxidizers. Contact with acid forms toxic hydrogen cyanide gas. Mixtures with benzene or cyanogen halides yield hydrogen chloride. In cmde form, this chemical trimerizes violently if catalyzed by traces of hydrogen chloride or ammonium chloride, forming cyanuric chloride. Alkaline conditions will convert this chemical to... 

Even polyalkoxy-s-triazines are quite prone to nucleophilic substitution. For example, 2,4,6-trimethoxy-s-triazine (320) is rapidly hydrolyzed (20°, dilute aqueous alkali) to the anion of 4,6-dimethoxy-s-triazin-2(l )-one (331). This reaction is undoubtedly an /S jvr-4r2 reaction and not an aliphatic dealkylation. The latter type occurs with anilines at much higher temperatures (150-200°) and with chloride ion in the reaction of non-basified alcohols with cyanuric chloride at reflux temperatures. The reported dealkylation with methoxide has been shown to be hydrolysis by traces of water present. Several analogous dealkylations by alkoxide ion, reported without evidence for the formation of the dialkyl ether, are all associated with the high reactivity of the alkoxy compounds which ai e, in fact, hydrolyzed by usually tolerable traces of water. Brown ... 

By suitable choice of reaction conditions the chloro substituents of cyanuric chloride (11.10) can be replaced in a stepwise fashion. In the first step DAS reacts with cyanuric chloride at a temperature in the 0-20 °C range, ideally at pH 5-6. In the second step an amine or alcohol (R, 11) reacts within the range 20-50 °C under neutral or slightly alkaline... 

Cyanuric chloride has been used for the preparation of acyl chlorides, amides, and peptides. Conversion of cyanuric chloride into 2-chloro-4,6-dimethoxy-l,3,5-triazine (CDMT, 6) leads to a reagent that upon reaction with carboxylic acids produces the highly reactive 2-acyloxy-4,6-dimethoxy-l,3,5-triazines.P l The resulting active ester is a powerful acylating agent for alcohols and amines. The activation is performed in presence of a base, preferentially NMM, which leads to intermediate formation of 4-(4,6-dimethoxy-l,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMTMM, 7)P l (Scheme 5). This addition product is readily prepared from the commercially available CDMT (6) and NMM in THF and can be stored as solid compound in the cold.P P l It offers the advantage that it can be used in a one-... 

CYANURIC ACID CHLORIDE (108-77-0) Reacts with moist air, forming fumes of hydrogen chloride fumes. Violent exothermic reaction with water above 86°F/30°C or steam, forming hydrogen chloride and cyanic acid. Violent reaction with ethanol, dimethylfor-mamide, dimethylsulfoxide, methanol. Isolate from alcohols and caustic materials. 

Cyanuric chloride (TCT) has been found to promote the Ferrier rearrangement of D-glycal 41 in the presence of alcohols, in CH2CI2 at room temperature (8cheme 27a). The catalyst role in this process vras assigned to HCl, which is formed along with cyanuric acid in the reaction of TCT with adventitious moisture. 

For this reason, only di- and triallyl monomers have achieved commercial significance, and then only the esters. Since the cross-linked polymer occurring in this polymerization involves the side chains containing ester groups, they are also sometimes referred to industrially as polyesters. The di- and triallyl ester monomers are produced by the reaction of allyl alcohol with acids, acid anhydrides, or acid chlorides. Examples of monomers are diallyl phthalate (1) from phthallic anhydride, and triallyl cyanurate (II) from trichloro-5-triazine ... 

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