Patent GB-1114327-A (GB)
Title: Aminocoumarin derivatives
IPC: C07D263/52
Filed: 1966-03-10
Abstract: High molecular hydrophobic organic material e.g polycondensation and polyaddition products, are brightened by the application thereto of a compound of formula <FORM:1114327/C3/1> where R1 represents alkyl, alkenyl, aryl cycloalkyl or aralkyl, optionally substituted by non-colouring substituents, R2 represents alkyl-s-, alkenyl-s-, cycloalkyl-s-, aralkyl-s-, aryl-s-, aryl-o-, aralkyl-o-, cycloalkyl-o-, or a said radical substituted by non-colouring substituents, hydroxyalkyl-o-, phenoxy-alkyl-o-, or hydroxyalkyloxyalkyl-o-, X represents oxygen or sulphur, R3 represents an isocyclic-aromatic or heterocyclic-aromatic radical optionally substituted by non-colouring substituents, and the benzene ring A can also contain non-colouring substituents.  The organic material can be brightened by incorporating the brighterner thereinto, optionally with plasticisers, stabilizers or pigments. Specified high molecular weight compounds are polyethylene, polypropylene, polyvinyl chloride, polyamides, polyesters, particularly polyesters of aromatic polycarboxylic acids with polyvalent alcohols such as polyterephthalic acid glycol esters, and cellulose esters, e.g. cellulose acetates.  In an example a composition comprising acetyl cellulose, titanium dioxide, diethyl phthalate and a brightener of the above formula is prepared as an opaque solution.ALSO:Novel 7-triazinyl amino-coumarins of the formula <FORM:1114327/C2/1> where R1 represents unsubstituted alkyl, alkenyl, cycloalkyl, aralkyl, or aryl, or a said radical substituted by non-colouring substituents, and R2 represents alkyl-S-, alkenyl-S-, cycloalkyl-S-, aralkyl-S-, aryl-S-, aryl-O-, aralkyl-O-, cycloalkyl-O-, or a said radical substituted by non-colouring substituents, hydroxyalkyl-O-, phenoxyalkyl-O-, or hydroxyalkyloxyalkyl-O-, X represents oxygen or sulphur, R3 represents an isocyclic-aromatic or heterocyclic-aromatic radical optionally substituted by non-colouring substituents, and the benzene ring A can also be substituted by non-colouring substituents, are prepared by reacting a 2,4,6-trihalogen-s-triazine in any order with an equimolar amount of a compound of formula R1-X-H, with an equimolar amount of a compound of formula R2-H, and with an equimolar amount of an appropriate 7-aminocoumarin compound, the reactions being effected in the presence of an acid binding agent, in the first case at about 0-10 DEG  C., in the second case at about 0-60 DEG  C. and in the third case at about 60-98 DEG  C.  Examples of non-colouring substituents are hydroxyl, alkoxy, hydroxyalkoxy, aryloxy, alkyl, or aryl groups, or F, Cl or Br. The halogen-s-triazine is preferably reacted in the first or also the second step with the aminocoumarin, while reaction with R1-X1-H and R2H may be performed in the first, second or third step. Starting materials which are hydroxyl compounds are preferably used in excess. Compounds which are mercaptan compounds are advantageously used as equivalent amounts of their alkali-metal salts in aqueous-organic solvent.  The compounds are useful in the optical brightening of high molecular organic material, including textile fibres.  3 - Phenyl - 7 - [41,61 - dichloro - S - triazinyl - (21)-amino]-coumarin is prepared by reacting 2,4,6 - trichloro - s - triazine with 3 - phenyl - 7 -aminocoumarin. Other 3-aryl-7-[41,61-dichloro-s-triazinyl - (21) - amino] - coumarins are prepared in an analogous fashion.  3 - Aryl - 7 - aminocoumarins are prepared by condensing appropriately substituted benzyl cyanides or 2-(cyanomethyl)-thiophene with 2 - methoxy - 4 - acetylaminobenzaldehyde or with 2 - methoxy - 5 - methyl - 4 - acetyl -aminobenzaldehyde, dealkylating the a -substituted o-methoxy cinnamic acid nitrile formed, closing the ring to form the coumarin and hydrolysing the acetylamino group.  3 - Phenyl - 7 - [41 - methoxy - 61 - chloro - s - triazinyl - (21) - amino] - coumarin is prepared by reacting 2,4,6-trichloro-s-triazine with methanol, and treating the so-formed 2-methoxy-4,6-dichloro - s - triazine with 3 - phenyl - 7 - aminocoumarin.  3 - (m - Sulphophenyl) - 7 - aminocoumarin is obtained by sulphonating 3-phenyl-7-aminocoumarin with sulphuric acid monohydrate.ALSO:Textile fibres such as cotton, wool, cellulose ester, polyester and nylon may be brightened by the application thereto of a compound of the formula <FORM:1114327/D1-D2/1> where R1 represents alkyl, alkenyl, cycloalkyl, oralkyl or aryl optionally substituted by non-colouring substitutes, R2 represents alkyl - S - alkenyl - S - cycloalkyl - S -, arakyl - S-, aryl - S -, aryl - O -, aralkyl - O -, cycyloalkyl - O -, or a said radical optionally substituted by non-colouring substitutes, hydroxyalkyl - O -, phenoxyalkyl - O -, or hydroxyalkyloxyalkyl - O -, X represents oxygen or sulphur. R3 represents an isocyclic - aromatic or heterocyclic - aromatic radical optionally substituted by non-colouring substituents, and the benzene ring A can also be substituted by non-colouring substituents.  The compounds are suitably applied as aqueous solutions of their alkali or ammonium salts.