1.2.4- Triazine, 3-methoxy

Bis(isopiopylamino)-2-methoxy-s-thazine BRN 0613574 Caswell No. 096 2,6-Diisopropylamino-4-methoxy-triazine N, N -Di-isoprapyl-6 nethoxy-1,3,5-triazine-2,4-diamine N,N -Diisopropyl-6-methoxy-1,3,5-triazine-2,4-diyldiamine N,N -Diisoprapyl-6-methoxy-1,3,5-tri-azine-2,4-diamine EINECS 216-548-0 EPA Pesticide Chemical Code 080804 G-31435 Gesafram Gesafram 50 HSDB 1519 2-Methoxy-4,6-bis(isopropylamino)-1,3,5-triazine 2-Methoxy-... 

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. 

The pyrimidine compounds are known to undergo a rearrangement of the 0-alkyl derivatives to the iV-alkyl ones. The methoxy derivatives of 1,3,5-triazine display a similar behavior. On applying methyl iodide to 2,4-dimethoxy-l,3,5-triazine one of the methyl groups is shifted giving rise to l-methyl-4-methoxy-derivative (22). This compound was also obtained by methylation of 4-methoxy-2-oxo-1,2-dihydro-1,3,5-triazine (18) with diazomethane. At higher temperature (100°C) in presence of methyl iodide a shift of both methyl groups takes place and methiodide is formed simultaneously (23). Similarly,... 

Because of the similarity of the substituent effects in s-triazine and quinoline derivatives, it seems probable that in the former sequence hydrogen falls between the chlorine atom and the methoxy group. 

Chloro-5,6-diphenyl-as-triazine readily undergoes methoxy-de-chlorination at 25° (< 12 hr) with methanolic methoxide and at 65° (4.5 hr) in non-basified methanol. The chloro group is also displaced by hydrazine (80°, 1 hr), ammonia (140°, 6 hr), and phenyl-magnesium bromide (70°, 12 hr), the latter forming the triphenyl compound 315.3-Chloro-6-phenyl-as-triazine is unstable to cold water or alkali and to hot alcohol or aqueous potassium carbonate. ... 

The presence of an TV-oxide group activates the 1,2,4-triazine ring toward electrophilic attack, for instance, in halogenation reactions. Thus, 3-methoxy- and 3-amino(alkylamino)-1,2,4-triazine 1-oxides 16 react easily with chlorine or bromine to form the corresponding 6-halo-1,2,4-triazine 1-oxides 17 (77JOC3498, 78JOC2514). 

The halogenation of 3-methoxy- or 3-methyl(dimethyl)amino-1,2,4-triazine 2-oxides 18 was found to proceed in a similar manner, resulting in 6-halo-1,2,4-triazine 2-oxides 19 (77JOC3498, 78JOC2514). 

Derivatives of 3-oxo-l,2,4-triazine 1-oxide undergo alkylation with various alkylating agents. Thus the reaction of 3-methoxy-l,2,4-triazine 1-oxide 20 with 2,3,5-tii-(9-benzoyl-/3-D-ribofuranosyl bromide, followed by the removal of the benzoyl protection with sodium methoxide, leads to an abnormal nucleoside 4-(/3-D-iibofuranosyl)-l,2,4-triazin-3(4//)-one 1-oxide 21 (73JOC3277). 

The methoxy group is replaced in the reaction of 3-methoxy-5-phenyl-1,2,4-triazine 1-oxide 46 with ammonia, resulting in 3-amino-5-phenyl-1,2,4-triazine 1-oxide 47. The treatment of 3-methoxy-1,2,4-triazine 1-oxide 20 with hydrazine leads to 3-hydrazino-1,2,4-triazine 1-oxide 48 (71JOC787). 

The reaction of 3-methoxy-1,2,4-triazine 1-oxide 20 with the carbanion generated from chloromethyl phenyl sulfone proceeds as the vicarious nucleophilic substitution (VNS) of hydrogen (Scheme 1, path B) via addition of the carbanion at position 5 of the heterocycle. Following base-induced elimination of HCl and protonation, 3-methoxy-5-phenylsulfonyl-1,2,4-triazine 4-oxides 65 result (88LA627). 

A similar migration of the methyl group was found in 3-methoxy-l,2,4-triazine 2-oxides 18 under the same conditions to afford the 2-methoxy-1,2,4-triazin-3(2/f)-one 125 (84TL1677). 

The reaction of 4-methoxy-3-nitropyridines 129 with guanidine under similar conditions results in 3-aminopyrido[3,4-e]-l,2,4-triazine 1-oxides 130 (76MI). 

OCH, BPA 2-methoxy-4,6- dichloro-S-triazine Cetyldimethyl ammonium choloride CHCI3 5 5 — 0.80 (CHC13) 80... 

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