IE39574L - 1, 2, 4- triazinediones. - Google Patents

Abstract

1448696 2 - Phenyl - as - triazine - 3,5(2H, 4H)diones PFIZER Inc 21 Sept 1973 [29 May 1973] 44509/73 Heading C2C [Also in Division A5] Novel compounds of the formula wherein R 2 and R 6 are each hydrogen, fluoro, chloro, cyano or methyl, providing at least one of R 2 and R 6 is hydrogen or fluoro; R 3 and R 5 are each hydrogen, cyano, trifluoromethyl, halo, C 1-6 alkyl, alkoxy or alkylthio or nitro; R 4 is or -CH 2 NR 13 R 14 , wherein Z is hydrogen, C 1-6 alkylthio or halo; Y, Y<SP>1</SP>, Y<SP>11</SP> are each hydrogen, halo, C 1-6 alkyl or trifluoromethyl; X is oxygen, sulphur or -O-CH 2 -; X<SP>1</SP> is -OCH 2 -, -S-CH 2 -, -SOCH 2 -SO 2 CH 2 - -CH 2 -, -OCH 2 CO- or -NHCH 2 -; X and X<SP>1</SP>, when they are unsymmetrical, being attached to the phenyl triazine ring system by the oxygen, sulphur or nitrogen atom; X<SP>11</SP> is oxygen, sulphur, SO, SO 2 , CO or CHOH; R 10 is hydrogen; R 11 is hydrogen, halo, C 1-6 alkylthio, alkylsulphinyl, alkylsulphonyl or alkoxy, trifluoromethyl or nitro; R 12 is C 1-6 -alkylthio, alkylsulphinyl, alkylsulphonyl or C 2-6 alkanoyl, trifluoromethyl or SO 2 NRR 1 <SP>1</SP> wherein R is H, C 1-6 alkyl, allyl, propargyl, phenyl, benzyl, pchlorophenyl, #-hydroxyethyl, #-acetoxyethyl, #-methoxy ethyl, #-methylthioethyl, #-methylsulphonylethyl, cyclopropyl; R 1 <SP>1</SP> is hydrogen, C 1-6 alkyl, allyl, propargyl, #-hydroxyethyl, #- acetoxyethyl, #-methoxyethyl, #-methylthioethyl, #-methylsulphonylethyl, γ-(#-methoxyethoxy)propyl, cyclopropyl or cyclopentyl; or R and R 1 <SP>1</SP> together with the nitrogen to which they are attached are morpholino or pyrrolidino and R 13 and R 14 together with the nitrogen to which they are attached are morpholino, thiomorpholino or thiazolindino, and alkali metal, alkaline earth metal and amino salts thereof may be prepared by (1) decarboxylation of a corresponding 6-carboxy-triazine compound. (2) Oxidizing a C 1-6 alkyl thioether at R 12 to a C 1-6 alkylsulphonyl; or (3) introducing a chlorosulphonyl group at R 12 followed by reaction with a free amine to form a sulphonamide group at R 12 . 2 - [3,5 - Dimethyl - 4 - (3 - methyl - 4 - thiomethyl - phenoxy)phenyl] - 6 - carboxy - as - Triazine - 3,5 - (2H,4H) - dione is prepared by reacting 3 - methyl - 4 - thiomethylphenol with 3,5 - dimethyl - 4 - chloronitrobenzene to form 2,6 - dimethyl - 4 - nitro - 31 - methyl - 41 - thiomethyl-diphenylether which is reduced to the 4- amino compound followed by reaction with nitrous acid and then cyanoacetyl-urethane to yield ethyl N - [cyano - 3,5 - dimethyl - 4 - (3- methyl - 4 - thiomethylphenoxy) - phenyl - hydrazinylidine)methylcarbonyl]carbamate which is cyclized to the required compound. 2 - [3,5 - Dimethyl - 4 - (4 - bromobenzyloxy)- phenyl] - as - triazine - 3,5(2H,4H) - dione - 6- carboxylic acid is prepared by reacting the potassium salt of 3,5-dimethyl-4-nitrophenol with p-bromobenzylbromide to yield 3,5-dimethyl - 4 - (4 - bromobenzyloxy) - nitrobenzene which is reduced to the corresponding aniline which on reaction with nitrous acid followed by cyanoacetylurethane yields 3,5-dimethyl-4-(4- bromobenzyloxy) - phenylhydrazonocyano acetylurethane which is cyclized to 2-[3,5-dimethyl-4- (4 - bromobenzyloxy)phenyl]- as - triazine - 3,5- (2H,4H)-dione-6-carbonitrile which is hydrolysed to the required 6-carboxy compound required. [GB1448696A]