Solvent triazines

In this solvent the reaction is catalyzed by small amounts of trimethyl-amine and especially pyridine (cf. 9). The same effect occurs in the reaction of iV -methylaniline with 2-iV -methylanilino-4,6-dichloro-s-triazine. In benzene solution, the amine hydrochloride is so insoluble that the reaction could be followed by recovery. of the salt. However, this precluded study mider Bitter and Zollinger s conditions of catalysis by strong mineral acids in the sense of Banks (acid-base pre-equilibrium in solution). Instead, a new catalytic effect was revealed when the influence of organic acids was tested. This was assumed to depend on the bifunctional character of these catalysts, which act as both a proton donor and an acceptor in the transition state. In striking agreement with this conclusion, a-pyridone is very reactive and o-nitrophenol is not. Furthermore, since neither y-pyridone nor -nitrophenol are active, the structure of the catalyst must meet the conformational requirements for a cyclic transition state. Probably a concerted process involving structure 10 in the rate-determining step... 

Line No. Triazine substituents Nucleophile + catalyst Solvent Rate constant (temp. °0) 106 liter mole i sec i Kin param Ex etic eters > JSt Ref. 

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. ... 

Trichloro-5-triazine is mono-aminated at temperatures of — 15° to 100°, depending on the nucleophilicity of the amine and on the solvent. With ammonia and alkylamines, one chloro group is replaced at —15 to 10°, a second at 10-50°, and a third at 20-100°. Unsymmetrical triamino derivatives can be pre-... 

Ring-chain tautomerism was observed in a series of l,2,3,6-tetrahydro-l,2, 4-triazine 4-oxides 5 in nonpolar solvents (e.g., CCI4) by NMR spectroscopy. Depending on the nature of substituents R and R, the ratios of the cyclic form of 1,2,4-triazine 5a to the open-chain form of hydrazone 5b were found to be up to 45 55 (77ZOR2617). 

The isomer lowest in energy is predicted to be the 2,5-dihydro-1,2,4-triazine 198g. The most stable structures always show two C=N double bonds. Moreover, in polar solvents, 198h should also be a dominant species [00PCCP2187]. The valence and Rydberg excited states of 1,2,3-triazine have been studied by multireference methods (MRD-CI) and the results are compared with experimental spectra [98CP39]. 

A gaseous stream of cyclopropene was passed through a stirred suspension of methyl 5,6-diphenyI-1,2,4-triazine-3-carboxylate (1.46 g, 5 mmol) in anhyd El20 (20 mL) for 15 min after which time an homogeneous solution was obtained. The solvent was removed to give an oil [yield 1.4 g (92%)] which solidified, and the solid was recrystallized (MeOH) mp 75- 79 C. 

Treatment of 1,2,4-triazines 91a-91e with the electron-deficient die-nophile dimethyl acetylenedicarboxylate gave products, depending on the substituents [77LA( 10) 1718]. Pyrrolo-[2, -/][ ,2,4]triazines 92 were obtained via [4 + 2]-cycloaddition [77LA(9)1413, 77LA( 10)1718] with 91, but interaction with 91b in the absence of solvent gave, in addition to 92, the pyrido[2,l-/][l,2,4]triazine 93 and [l,3]oxazino[2,3-/][l,2,4]-triazine 94. In case of 91a pyridine and benzene derivatives were also formed in addition to 92 (Scheme 23). 

Examples of this ring system were synthesized by nucleophillic addition of 613 to dimethyl acetylenedicarboxylate in moist solvents to afford the ylidene-substituted oxazolo[3,2-rf][l,2,4]triazine 614. Its X-ray crystal structure has been described [90JCR(S)354] (Scheme 126). 

Benzo-l,2,3-triazin-4-ones with the general structure 6.54 (X = O, S, or H2) are obtained by diazotization of the appropriate aniline derivatives 6.53 (Scheme 6-38). In polar aprotic solvents (e. g., nitrobenzene) the reverse reaction takes place to give the diazonium ion (for an example see Kullick, 1966). Diazotization of 1,8-diamino-naphthalene yields l-i/-naphthol[l,8-cfe]triazine (6.55 Tavs et al., 1967). In concentrated HC1 the triazine ring is opened again. 

Triazines have been prepared by microwave-assisted reaction of substituted benzonitriles 161 and cyanoguanidines 162 using the ionic hquid [bmim][PF6] as the solvent at 130°C for 10-15 min [106]. Nine differently... 

Ultrasonication was reported for the extraction of triazines from soil, previously sieved to 2 mm and stored at -18 °C, prior to analysis using CC/NPD and CC/lTD. A 5-g soil sample was placed in a polypropylene column and extracted for 15 min with 4 mL of ethyl acetate in an ultrasonic bath at room temperature. Subsequently, the solvent was filtered and collected in a graduated tube, and the extraction was repeated for another 15-min period using a second 4-mL portion of ethyl acetate. The two extracts... 

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