Patent GB-1379785-A (GB)
Title: Triazolylethenyl-phenylene derivatives
IPC: D06L3/12
Filed: 1972-03-14
Abstract: 1379785 1,2,3-Triazole derivatives and intermediates therefor SANDOZ Ltd 14 March 1972 [18 March 1971] 11832/72 Headings C2C and C2P [Also in Division C3] Novel 1,2,3-triazole derivatives of the Formula I wherein R is an optionally substituted mono- or bi-nuclear aryl radical or a radical of the Formula II, R 1  and R 3  are optionally substituted C 1-6  alkyl radicals or optionally substituted mono- or bi-nuclear aryl radicals, R 2  and R 4  are hydrogen or chlorine atoms, optionally substituted C 1-6  alkyl, -C#N, -CONH 2 , -COOR 5  or -NHOOR 6  groups R 5  and R 6  being optionally substituted C 1-6  alkyl groups or R 5  being a hydrogen atom, n is 1 to 6 and the ring(s) B may be substituted or unsubstituted, provided that n is other than 1 when R has the Formula II above, are obtained by a number of synthetic methods. These are (a) a compound of the formula X 1 -[B] n -X 2  is reacted with a triazole of the Formula IV and a compound Y 2 -R, one of X 1  and Y 1  and X 2  and Y 2  being a -CHO group or a functional derivative thereof and the other being a radical of the formula -CH 2 -Z 1 , wherein Z is a hydrogen atom, a carboxy or an optionally substituted carboxylic ester or amide group or one of certain phosphorus-containing groups and, where required, any product containing a group Z 1  which is other than hydrogen is converted into a compound in which it is hydrogen; (b) a compound of the formula R 9 -CH = CH-[B] n X 1  is reacted with a compound of the formula R 10 -Y 1 , one of R 9  and R 10  being R and the other being a radical of the Formula XIV and where required, any product containing a group Z 1  which is other than hydrogen is converted into a compound in which it is hydrogen; (c) (where n is from 2 to 6), a compound of the Formula XV with a compound of the formula Hal being a chlorine, bromine or iodine atom, x and y being from 1 to 5 provided that x + y is six or less, in the presence of copper powder; (d) a diazo derivative of a compound of the formula R 9 -CH = CH-[B] n NH 2  is reacted, in the presence of a catalyst, with a compound of the formula R 10 -CH = CH-Z 2 , Z 2  being a carboxyl or an optionally substituted carboxylic acid amide or ester group, and where required, Z 2  in the product is split off; or compounds of the formula XIX R 11  being an optionally substituted mono- or bi-nuclear aryl radical or a radical of the Formula XX -CO-CR 4  = NOH, is reacted with a compound of formula R 1 -NH-NH 2  and, when R 11  is a radical XX, with a compound of the formula R 3 -NH-NH 2 , and the resulting product is-cyclized. The compound of the Formula XLVIII may also be produced by dehydrating the corresponding amide. The compounds of Formula I have opticalbrightening properties and may be used for the brightening of textile and non-textile organic materials and plastics. The dipotassium salts of 4,4<SP>1</SP>-di-, ter- and quater-phenylene diacetic acids are obtained from the corresponding p,p<SP>1</SP> -diacetyl derivatives by the Willgerodt-Kindler reaction, the reaction with sulphur being carried out in excess morpholine and the thiomorpholides produced being saponified with 40 to 50% potassium hydroxide solution. 4 - Iodo - 2 - cyano - # - (2<SP>1</SP> - phenyltriazol - 4<SP>1</SP>- yl)styrene is produced by diazotization of 4- amino - 2 - cyano - # - (2<SP>1 </SP>- phenyltriazol - 4<SP>1</SP>- yl)styrene followed by reaction with potassium iodide. 2 - (4<SP>1 </SP>- cyanophenyl) - 1,2,3 - triazole - 4- aldehyde is obtained from di-iso-nitroso-acetone and 4-cyanophenyl-hydrazine. 2 - Phenyl - 4 - methyl - 5 - formyl - 1,2,3- triazole is produced from 2-phenyl-4-methyl- 1,2,3-triazole-5-carboxylic acid via the hydrazide and subsequent oxidation with lead tetraacetate. The preparation of 2-phenyl-4-formyl- 1,2,3-triazole is also referred to. The bis-phenylhydrazone oxime of the formula is produced by reacting an alkaline solution of isonitrosoacetone with 4,4<SP>1</SP>-bisformylbisphenyl to produce a bis-(#-keto)oxime of the formula and reacting this with phenyl hydrazine. The bis-triazole-N-oxide of the Formula (LVI) is obtained as an intermediate in process (e) above when the bisphenyl hydrazone of the Formula (LIV) is cyclized with copper sulphate pentahydrate.  4,4<SP>11</SP> - Bis - (diethoxyphosphonomethyl)terphenyl, 4,4<SP>111</SP> - bis - (diethoxyphosphonomethyl) quaterphenyl, 2 - phenyl - 4 - (diethoxyphosphonomethyl) - 1,2,3 - triazole, 4 - cyano -4<SP>1</SP>- diethoxyphosphonomethyl stilbene and 2-cyano-4<SP>1</SP>- diethoxyphosphonomethyl stilbene are obtained by reacting triethyl phosphite with the appropriate bromomethyl compounds.