1.3.5- Triazines, from nitriles

Extreme pressure (above 1000 atm) and high temperatures are required for the preparation of trisubstituted 1,3,5-triazines from nitriles. Strong acids or bases can be used as an alternative. 

Cyclization, hexahydro-l,3,5-triacyl-y-triazines from nitriles and formaldehyde, 51... 

Probably the cyclotrimerization of nitriles is the best known route to 1,3,5-triazines. The reaction has the obvious limitation that it is of value for preparing the symmetrical derivatives only. Nevertheless, many important triazines, such as cyanuric chloride, are made in this way. There are a number of other cyclotrimerization reactions which are also useful, in particular the trimerization of imidates. An easy route to 1,3,5-triazine from ammonium acetate has been developed. 

Synthesis of 4(6)-amino-l,3,5-triazine-2-ones and 2-thiones starting from benzotriazole derivatives has been reported <01JOC6797>. The first template photochemical synthesis of a 1,3,5-triazine derivative as a receptor capable of differentiating between thymine and uracil has been described <01CC1446>. A new solid phase synthesis of trisubslituted 6-amino(substituted)-2,4-dioxo-3,4-dihydro-l,3,5-triazines from a resin-bound amine component has been reported <01JCO278>. The synthesis of thirteen lris(azol-l-yl)-13,5-triazines, as a new class of multidentatc ligands, has been described <01H(55)905>. Tris(pyrazolyl-13,5-triazincs) 14 have been prepared by cyclotrimerization of aromatic nitriles, in piperidine and in solvent-free conditions <01T4397>. 

Hydrogen chloride Chloro-l,3,5-triazines from 3 nitrile molecules... 

Di(pentafluorocyclopropanyl)-substituted triazine 76 was prepared from nitrile 75 by reaction with armnonia followed by acylation-cyclization with trifluoroacetic anhydride (Scheme 32) [64],... 

Another example of the remarkable reactivity of Mg actuated by our procedure is its reaction with nitriles. In this respect, the Mg resembles an alkali metal more than an alkaline earth. Benzonitrile reacts with Mg overnight, in refluxing DME, to give 2,4,6-triphenyl-l,3,5-triazine and 2,4,5-triphenylimidazole in 26 and 27% yield, respectively, based on magnesium. Jhe imidazole was shown to arise, at least in part, from the action of Mg on the triazine. The trimerization of aromatic nitriles to give symmetrical triazines is not unknown, but generally the reactions are... 

Benzo-flw-triazine tri-N-oxides 384 (R = H, Me R1 = mesityl, 2,6-ClC6H3) are formed from the reaction of nitrile oxides R CNO with benzofuroxans 385. The structure of 384 (R = Me, R1 = mesityl) has been confirmed by X-ray crystal structure analysis (431). 

Reactions involving the [4 + 1 + 1] principle, an example of which is shown in equation (136), are rather uncommon and of strictly limited utility [3 + 2 + 1] and [2 + 2 + 2] processes, on th,e other hand, are well known. Representative [3 + 2+1] three-bond formation processes are given in equations (137)—(141), from which it can be seen that the common situation is where ammonia, a substituted amine or formamide constitutes the one-atom fragment. Many [2 + 2 + 2] atom fragment syntheses are known and some are familiar reactions. Thus, the cobalt(I)-catalyzed condensation of nitriles and isocyanates with alkynes gives pyridines and 2-pyridones, often in excellent yield (e.g. equation 142), while the cyclotrimerizations of nitriles, imidates, isocyanates, etc., are well established procedures for the synthesis of 1,3,5-triazine derivatives (e.g. equation 143). Further representative examples are given in equations (144)-(147), and the reader is referred to the monograph chapters for full discussion of these and other [2 + 2 + 2] processes. Examination of the... 

---