3,839,351 United States Patent Office Patented Oct. 1, 1974 2 and their quaternisation products of the formula 3,839,351 TRAZOLYL-COUMARNS Rs R4 Alfons Dorlars, Leverkusen, and Heinrich Gold, Cologne, Germany, assignors to Bayer Aktiengesellschaft, Lever kusen, Germany 5 No Drawing. Filed Aug. 13, 1971, Ser. No. 171,758 Claims priority, application Germany, Aug. 13, 1970, P 20 40 1892 nt. C. C07d 55/02 (II) U.S. C. 260-308 A 3 Claims 0. in which R1 to R4 and X have the same meaning as above; R5 stands for an alkyl radical; and Y represents a ABSTRACT OF THE DISCLOSURE colourless anion, k Coumarin compounds of the formula as well as their production and their use as brightening agents. R 5 The alkyl radicals R-R5 comprise straight-chain, branched or cyclic, saturated or unsaturated alkyl groups X with 1-12 carbon atoms, which may contain substituents, for example, halogen atoms, e.g. fluorine, chlorine and R-17 N.N OO NN/ 20 bromine; hydroxyl groups; alkoxy groups with 1-4 car Ri-N / No So bon atoms; alkyl-carbonyloxy groups with 1-4 carbon N atoms in the alkyl radical; cyano; carboxylic acid groups; alkoxycarbonyl groups with 1-4 carbon atoms in the al in which kyl group; as well as phenyl radicals which may contain R, R2, Ra and Ra mean hydrogen, alkyl or aryl radicals; 25 halogen atoms, C1-C4-alkyl and alkoxy groups. R and R as well as Rs and R4, together with the two Suitable alkyl radicals are, for example: methyl, hy carbon atoms of the respective heterocycle, may form droxymethyl, methoxymethyl, cyanomethyl, ethoxycar a non-aromatic ring system; bonylmethyl, ethyl, B-hydroxyethyl, 6-acetoxyethyl, 6 R may also stand for a cyano, carboxyl, carboxylic acid chloroethyl, B-cyanoethyl, carboxyethyl, ethoxycarbonyl ester or carboxylic acid amide group; 30 ethyl, methoxyethyl, ethoxyethyl, m- and iso-propyl, n X stands for a nitrogen atom or a methine group (CH); iso-, sec.- and tert-butyl, iso-butenyl, pentyl, hexyl, octyl, and the coumarin ring as well as the alkyl and aryl decyl, dodecyl, benzyl, p-chlorobenzyl, 3-phenylethyl, B radicals may contain further substituents, methoxyethenyl and cyclohexyl radicals. and their quaternisation products of the formula The optionally substituted aryl radicals primarily com 35 prise phenyl radicals which may carry one or more sub R3 R stituents, for example, fluorine, chlorine, bromine, cyano, lower alkyl and alkoxy groups with 1-4 carbon atoms 69 ye (which, in turn, may be further substituted, e.g. by phenyl X N N-Rs radicals), the carboxyl group, alkoxy-carbonyl groups 40 with 2-5 carbon atoms, sulphonic acid groups, sulphonic R^ N C. acid ester groups, optionally alkyl-substituted sulphona RI-N - No N O mide groups, alkylsuphone groups with 1-4 carbon N atoms, phenyl and phenoxy radicals. The following are examples of such radicals: phenyl, in which R1 to R and X have the same meaning as above, 45 o-, m- and p-fluorophenyl, o-, m- and p-chlorophenyl, R stands for an alkyl radical; and Y represents a o-, m- and p-bromophenyl, o-, m- and p-tolyl, o-, m- and colourless anion - p-anisyl, m- and p-cyanophenyl, m- and p-ethoxycarbonyl as well as their preparation and their use as optical bright phenyl, Suphophenyl-, amidosulphonylphenyl, phenoxy eICS. sulphonylphenyl, m- and p-methylsulphonylphenyl, m 50 and p-ethylsulphonylphenyl, p-benzylphenyl, p-benzyl The subject-matter of the present invention comprises oxyphenyl radicals, p-biphenyl and p-phenoxyphenyl coumarin compounds of the formula radicals. Non-aromatic ring systems which are fused with the R4 v-triazole ring and may also be symbolised by R and 55 R together with the two carbon atoms of the v-triazole ring, are, in particular, cyclopentane and cyclohexane X N N rings which, in turn, may be fused with a benzene ring. R % N NN/ Examples of such fused systems are the following: - No O R-N 60 N (I) in which R, R2, R and R4 mean hydrogen, alkyl or aryl radicals; ?N.\/\s/ (O-N/ anNN/ R and Ra as well as R3 and R4, together with the two carbon atoms of the respective heterocycle, may form 65 a non-aromatic ring system; R may also stand for a cyano, carboxyl, carboxylic acid ester or carboxylic acid amide group; 7 O X stands for a nitrogen atom or a methine group (CH); {X4- N/ and the coumarin ring as well as the alkyl and aryl 70 Suitable carboxylic acid ester groups R2 are, for exam radicals may contain further substituents, ple, alkoxy-carbonyl groups with 1-4 carbon atoms in the 3,839,351 3. 4. alkoxy group, such as methoxy-carbonyl, ethoxy-carbonyl or butoxy-carbonyl radicals. pH R An optionally substituted carboxylic acid imide group is, N for example, a carboxylic acid amide group which may be R-6 N mono- or disubstituted by alkyl radicals with 1-4 carbon 2 NN/ atoms. Examples are the groups -CONH2, -CONHCH3, -CONHCH, -CON(CH3)2 and -CON (C2H5)2. N (V) Suitable substituents in the coumarin ring are primarily C1-C4-alkyl radicals. in which R1 to R4 have the same meaning as above, The anion Y is preferably a colourless anion which O either originates from the quaternising agent used, or are either directly triazolised by treatment with dehydrat has been introduced by exchange of the anion initially ing agents, or are first converted by reaction with de present. Suitable anions are, for example, Cl, Br, I; sul hydrating agents into the corresponding triazole-N-oxides phonate groups such as CHO-SO3, C2H5O-SO3; benzene of the formula sulphonate, toluene-sulphonate, phosphate, formate, ace R3 R tate, chlorozincate, perchlorate, nitrate, sulphate and oxa late radicals. Preferred coumarin compounds with the scope of the O N N formula (I) are those of the formula /S/NN/ 20 R2 2 N R's N No O Riv/ (VI) R2-1 N N 25 in which R1 to R4 have the same meaning as above, R’i-S and the latter are subsequently reduced. IOl.N The dehydration of the coumarin compounds (V) is (III) in which carried out in known manner by heating with dehydrating 30 agents such as acid anhydrides and acid halides. R" and R' means hydrogen; C1-Co-alkyl groups which Examples are: acetic anhydride, propionic acid anhy may be substituted by chlorine, fluorine, bromine, hy dride, acetyl chloride, thionyl chloride, sulphuryl chloride droxyl, C-C4-alkoxy, Ca-C5-alkyl-carbonyloxy, Ca-C5 and phosphorus pentoxide; the acetic anhydride is particul alkoxy-carbonyl, cyano, carboxyl and phenyl radicals; larly suitable and is used either in ample excess or in com a cyclohexyl radical; or phenyl groups which may be bination with solvents. substituted by fluorine, chlorine, bromine, cyano, Suitable solvents are dimethyl sulphoxide, dimethyl C1-C4-alkyl, C1-C4-alkoxy, benzyl or C-C-alkoxy formamide, N-methyl-pyrrolidone, tetramethyl urea, acetic carbonyl groups; acid, propionic acid, and others. In most cases, an addition of bases is expedient, such as lithium, sodium or potassium R1 and R2 together may stand for -(CH2)4 or acetate, trimethylamine, triethyl amine, dimethyl-benzyl 40 amine, pyridine and higher pyridine homologues. The temperatures at which the dehydration is carried out may be varied within a fairly wide range. In general, the process is carried out at temperatures of between 40 and and 160° C., preferably at between 60 and 140 C. R's and R', stand for hydrogen, C1-C4-alkyl, methoxy 45 The cyclisation of the compounds (V) in the presence methyl, phenyl, or together stand for -(CH2)4-, of dehydrating agents to form the triazole-N-oxides of the formula (VI) is expediently carried out in solvents which as well as their quaternisation products of the formula are inert under the reaction conditions applied and towards 50 the chosen oxidising agents, such as e.g. pyridine, higher Ra R' pyridine bases, dimethyl formamide, N-methyl-pyrroli done, dimethyl sulphoxide, acetic acid and their mixtures e with water. N N -R's Suitable dehydrating agents are, inter alia, mercury(II) R-17 N 3. Yve 55 oxide, copper(II) salts such as copper acetate and copper N No/N sulphate, complex copper(II) salts, lead dioxide, lead R" N / O tetra-acetate, sodium and potassium bichromate, potassium N (IV) ferricyanide, hydrogen peroxide, aceto peracid and potas in which sium peroxy-disulphate. 60 A technically preferred method of carrying out the proc R" and R4 have the same meaning as above; ess consists in dehydrating compounds of the formula (V) R's stands for a C1-C4-alkyl group which may be sub in the presence of pyridine or technical pyridine bases with stituted by hydroxyl, halogen, C1-C4-alkoxy, Ca-C5. copper(II) salts, such as copper acetate or copper sulphate, alkoxy-carbonyl, cyano or by phenyl radicals; and which may be used in solid form or in aqueous solution; Y' represents a colourless anion. 65 the blowing in of air may be expedient. This oxidative cyclisation is generally carried out at The new coumarin compounds of the formula (I) and temperatures of about 0° C. to 100° C., preferably of their quaternary salts of the formula (II) can be pre 20 to 80 C. pared according ot various processes. The subsequent reduction of the triazole-N-oxides (VI) Those compounds of the formula (I) in which X rep can be carried out, for example, with the aid of zinc dust resents a nitrogen atom; R1, R2, R3 and R4 mean hydrogen, and Zinc amalgam in an acetic acid or mineral acid solu alkyl or aryl radicals; and R1 and R2 as well as Ra and tion or suspension, or by means of tin granulate or tin(II) Ra, together with the two carbon atoms of the respective chloride in mineral acids. v-triazole ring, may form a non-aromatic ring system, are The coumarin compounds of the formula (V) required obtained in that compounds of the formula as starting substances can be prepared in known manner 3,839,351 5 6 by condensing 4-acetamino-2-hydroxybenzaldehyde or its 1-oximino-1-e-, -m-, and -p-anisylacetone, anil with triazolyl-acetic acids of the formula 1-oximino-1-o-, -m- and p-chlorophenylacetone, 1-oximino-1-m- and -p-cyanophenylacetone, R3 Rs 1-oximino-1-m- and -p-carbethoxy- and -p-carbethoxy phenyl-acetone, HOOC-CH-N N 1-oximino-1-m- and p-methylsulphonylphenyl-acetone, NN/ (VII) 1-oximino-1,3-diphenyl-acetone, in which R3 and R4 have the same meaning as above, to oXimino-butyrophenone, form 7-acetamino-3-1,2,3-triazolyl-(1)-coumarins; sub ty-benzoyl-y-oximino-butyric acid methyl- and ethyl ester, sequently hydrolysing the acetamino group to form the O Oximino-valerophenone, amino group; converting the resultant 7-amino-coumarins oximino-1- and -2-propionaphthone, by diazotisation and subsequent reduction into the corre benzil-monoxime, sponding 7-hydrazino-coumarins; and, finally, condensing tolil-monoxime, anisil-monoxime, the latter, again in known manner, with ox-oximino-ketones 5 oXimino-cyclopentanone, of the formula oXimino-cyclohexanone, R-C-NOE 2-oximino-indanone-(1), (VIII) 2-oximino-tetralone-(1). to form the oximino-hydrazones of the formula (V). 20 Those coumarin compounds of the formula (I) in which Some of the triazolyl-acetic acids (VII) are known. R2 may stand for a cyano, carboxyl, carboxylic acid ester They are obtained in known manner by reacting azido or carboxylic acid amide group, and R1, R and R4 have acetic esters wtih acetylenes and subsequent alkaline hy the same meaning as above, are advantageously prepared drolysis of the ester group. by triazolising compounds of the formula Suitable triazolyl-acetic acids of the formula (VII) are, for example, a. 1,2,3-triazolyl-(1)-acetic acid, R3 R4 4-phenyl-v-triazolyl-(1)-acetic acid, 4-phenyl-5-methyl-v-triazolyl-(1)-acetic acid, 4,5-bis-hydroxymethyl-v-triazolyl-(1)-acetic acid, 30 /N-N 4,5-bis-methoxymethyl-v-triazolyl-(1)-acetic acid, N 4-methoxymethyl-v-triazolyl-(1)-acetic acid, 2 =O 4-methyl-v-triazolyl-(1)-acetic acid, Ro1 N^\ No 4-methoxyvinyl-v-triazolyl-(1)-acetic acid, R-5 3 5 N 4,5,6,7-tetrahydrobenzotriazolyl-(1)-acetic acid. NH Suitable a-oximino-ketones of the formula (VIII) are R3 R inter alia, 1-oximino-3,3-dimethylbutanone-2, 40 oximino-acetone, N. N. diacetyl-monoxime, NN/ 1-oximino-butanone-(2), a's2 N O 2-oximino-1-phenyl-butanone-(3), R- SN O 1,3-diphenyl-1-oximino-propanone-(2), 45 R-c. oximino-benzyl-cyclohexyl-ketone, N (IX) 1-oximino-4-phenyl-buten-(3)-one-(2), 2-oximino-pentanone-(3), 3-oximino-4-methyl-pentanone-(2), 1-oximino-4-methylpenten-(3)-one-(2), 50 in which R1, R2 and Rs have the same meaning as above, 3-oximino-pentanol-(5)-one-(2), by treatment with dehydrating agents. 3-oximinohexanone-(2), A preferred method of carrying out this dehydration 2-oximino-5-methyl-hexanone-(3), is characterised in that the compounds (IX) are first con 2-oximinoheptanone-(3), verted with the aid of copper(II) salts into the copper 3-oximinoheptanone-(4), complexes, and these are then converted into the corre 3-oximino-octanone-(2), sponding 7-triazolyl-coumarin compounds by heating in 4-oximino-nonanome-(5), the presence of an excess of a solution of a complex 3-oximino-undecanone-(2), copper(II) salt. 3-oximinotridecanone-(2), Furthermore, lead tetraacetate is also suitable as de oXiminoacetophenone, 60 hydrating agent, for example. p-fluoro-, p-chloro- and p-bromo-oximino-acetophenone, p-methyl- and p-methoxy-oximino-acetophenone, The coumarin compounds of the formula (IX) required 2,4- and 3,4-dimethyl-oximino-acetophenone, as starting compounds can be obtained, for example, by oximino-propiophenone, diazotising 7-amino-coumarin derivatives of the formula p-fluoro-, p-chloro- and p-bromo-oximino-propiophenone, p-methyl-, p-benzyl-, p-dimethylbenzyl-, p-ethyl- and p-tert-butyl-oximino-propiophenone, p-methoxy-, p-ethoxy- and p-phenoxy- oximino-propio phenone, p-benzyloxy-oximino-propiophenone, 2,5-dimethyl-oximino-propiophenone, HN p-phenyl-oximino-propiophenone 2-oximino-1,3-diphenyls (X) propanone-(1), 1-oximino-1-phenylacetone, 1-oximino-1-o-, -m-, and -p-tolylacetone, 75 in which R3 and R4 have the same meaning as above, 3,839,351 7 8 and coupling the diazo compound with enamines of the Suitable hydrazino-coumarins of the formula (XII), formula besides the free 7-hydrazino-aquarines, are for example, R2-CI the formyl, acetyl and propionyl derivatives as well as R-- N (XI) the N-sulphonic acids of 3-1,2,3-triazinyl-(1))-7-hydrazino-coumarin, in which R1 and R2 have the same meaning as above. 3-(4-phenyl-v-triazinyl-(1)-7-hydrazino-coumarin, Those coumarin compounds of the formula (I) in which 3-4-ethyl-v-triazinyl-(1)-7-hydrazino-coumarin, X stands for a methine group, are preferably obtained by 3-4-methoxy-v-triazinyl-(1)-7-hydrazino-coumarin and condensing 7-hydrazino-coumarins of the formula O 3-(4,5,6,7-tetrahydrobenzotriazolyl-(1)-7-hydrazino 'counarin. is . Those coumarin compounds of the formula (I) in N. N. which X stands for CH; R1 stands for hydrogen; and R2, R3 and R4 have the same meaning as above, are advan A-HIN-EN rN%o/ tageously prepared by reacting the free 7-hydrazino com (XII) pounds of the formula (XII) in which A stands for H, or their mineral acid salts, with malon-dialdehydes of in which R and R4 have the same meaning as in formula the formula (I), and A stands for hydrogen, an acyl radical or a 20 R-CeCH-Z Sulphonic acid group, H--0 (XIV) with vinyl-ketones of the formula in which Z stands for a hydroxyl, alkoxy, acyloxy or dialkylamino group, and R2 has the same meaning as 25 above, R-–o (XIII) or with their functional derivatives. This reaction is carried out, for example, by heating in which R1 and R have the same meaning as in formula in glacial acetic acid to about 80-110° C. (I), and Z stands for halogen, a hydroxyl, alkoxy, 30 The functional derivatives of malon-dialdehyde (XIV) acyloxy or dialkyl-amino group, and their functional derivatives include, for example, while maintaining the radical A, and subsequent cyclisa malon-dialdehyde, 1,1,3,3-tetramethoxy-propane, chloro-, tion with the elimination of A-OH. and bromo-malon-dialdehyde and their bisulphite com The condensation of 6-halovinyl-ketones of the formula 35 pounds, phenyl-malon-dialdehyde, ox-phenyl-6-dimethyl (XIII) (Z=halogen, e.g. Cl, Br) is preferably carried amino-acrolein, ox-tolyl-6-dimethylamino-acrolein, cyano out with free 7-hydrazino-coumarin compounds (XII); malon-dialdehyde. A=H), whereas (3-hydroxy-, -alkoxy-, -acyloxy- or -di Cobviously, the substituents of the new coumarin com alkylamino-vinyl-ketones (XIII) are preferably condensed pounds of the formula (I) obtained according to one of with 7-acyl-hydrazino-coumarin compounds (XII); 40 the processes described above can be converted in known A=acyl. manner, Subsequent to the full synthesis. For example, sulphonic acid groups can be introduced The condensation of the hydrazino-coumarins of the into aryl radicals R1 to R4 by subsequent sulphonation, formula (XII) with the vinyl-ketones of the formula and any sulphonic acid groups present can be converted (XIII) is expediently carried out in a neutral to weakly in known manner into sulphonamide and sulphonic acid acidic organic medium at temperatures of about 40-100' 45 ester groups. C. The elimination of A-OH from the resultant reaction Furthermore, cyano groups can be converted, for ex product is carried out by the reaction with strong acids, ample, into carboxyl, carboxamide or carboxylic acid for example, mineral acids such as hydrochloric acid, ester groups, and carboxyl groups can be esterified or at temperatures of about 80-120° C. amidised, Suitable vinyl-ketones of the formula (XIII) are for 50 The quaternisation of the compounds of the formula example, (I) to form compounds of the formula (II) is carried out phenyl-6-hydroxyvinyl-ketone, in known manner, for example, in an inert organic sol hydroxymethylene-pinacoline, i vent. Suitable quaternising agents are, for example, the p-tolyl- and p-anisyl-6-hydroxyvinyl-ketone, esters of strong mineral acids and organic sulphonic acids p-fluoro-6-hydroxyvinyl-ketone, 55 With preferably low-molecular alcohols, such as alkyl phenyl-3-methoxyvinyl-ketone, chlorides, alkyl bromides, alkyl iodides, aralkyl halides, phenyl-(o-methyl-6-hydroxyvinyl)-ketone, alkylene halides, dialkylsulphates; and esters of Sulphonic phenyl-(o-ethyl- and -propyl-6-hydroxyvinyl)-ketone, acids of the benzene series, such as the methyl, ethyl, phenyl-(o-isopropyl- and -benzyl-6-hydroxyvinyl)-ketone, 60 F-methoxyethyl, p-chloroethyl, propyl, n-butyl esters of phenyl-(o-phenyl- and -tolyl-6-hydroxyvinyl-ketone, benzenesulphonic acid, P-methylbenzene-sulphonic acid, p-biphenyl-6-hydroxyvinyl-ketone, Pichlorobenzene-sulphonic acid and p-nitrobenzene-sul methyl-(o-methyl- and -ethyl-6-hydroxyvinyl)-ketone, Erie acid; as well as acrylonitrile in the presence of methyl-(o-phenyl- and -benzyl-3-hydroxyvinyl)-ketone, CS ethyl-(o-methyl- and -phenyl-6-hydroxyvinyl)-ketone, Suitable inert organic solvents are, for example, high cyclohexyl-(o-phenyl-o-hydroxyvinyl)-ketone, 65. boiling aliphatic, cycloaliphatic or aromatic hydrocar cyclohexyl-(6-phenyl-o-hydroxyvinyl)-ketone bons; furthermore, stable aliphatic or cyclic halogen benzyl-(o-phenyl-3-hydroxyvinyl)-ketone, compounds, such as carbon tetrachloride, trichloroethyl 1,4-diphenyl-2-hydroxymethylene-butanone-(1), tene, tetrachloroethylene, di-, tri- and tetrachloroethane, 2-hydroxy-methylene-cyclopentanone-(1) and -cyclohex mono- or dichlorobenzene, nitrobenzene; as well as alco. anone-(1), hols. It is also possible to work in an excess of liquid 2-hydroxymethylene-indanone-(1), quaternising agent to obviate over-energetic reaction con 2-hydroxymethylene tetralone-(1), ditions. 1-hydroxymethylene-tetralone-(2), The new triazolyl-coumarins of the formula (I) or and their methyl ethers. 5 (II) are valuable brightening agents. They are suitable 3,839,351 10 for brightening fibres, filaments, fabrics, knitted fabrics, hydride at 145-150° C. for 15 hours. The mixture is foils and plastic materials of synthetic origin, primarily subsequently allowed to cool down to 90° C., 450 ml. for brightening materials of polyacrylonitrile, polyesters, of concentrated hydrochloric acid are added dropwise at polyamides, polyurethanes and cellulose esters. Com: 90-100° C., and stirring is continued at 85° C. for 4 pounds of the formula (I) which contain sulphonic acid hours. The mixture is poured into 4 litres of water and groups can be used for brightening synthetic and natural neutralised with ammonia. The precipitated yellow crys polyamides. s talline 7-amino-3-4-phenyl-y-triazolyl-(1) J-coumarin is The brightening agents of the present invention can be filtered off with suction, washed with water until free applied in the usual way, for example, in the form of from salt, and dried; melting point 302-304° C. (decom solutions in water or organic solvents or in the form of O position). 271 g. (89% of theory) are obtained. The ami aqueous dispersions. Polyester materials can also be no-phenyl-triazolyl-coumarin so obtained is diazotised in treated with the brightening agents by impregnating them concentrated hydrochloric acid in analogy with the amino with solutions or dispersions of the brightening agents, triazolyl-coumarin, as described under (A), and the diazo followed by squeezing, drying and briefly heating at tem compound is reduced with a sodium hydrogen sulphite peratures above 150° C. Furthermore, the brightening 5 Solution to form 7-hydrazino-3-(4-phenyl-y-triazolyl agents can be added to casting or spinning solutions sery (1)-coumarin, which is obtained in the form of yellow ing for the production of synthetic fibres, filaments, foils Crystals which decompose at about 273-277 C. Yield 201 and other shaped articles. The necessary amounts can g. (71% of theory), referred to amino-phenyl-triazolyl easily be determined for every case; in general, amounts coumarin. of 0.05 to 0.6%, referred to the material to be brightened, 20 In an analogous way there is obtained from 4-phenyl have proved sufficient. 5-methyl-v-triazolyl-(1)-acetic acid, 4-acetylamino-2-hy The brightening agents according to the invention are droxy-benzaldehyde-anil, sodium acetate and acetic anhy extremely productive and are characterised by a high de dride, the 7-amino-3-4-phenyl-5-methyl-v-triazolyl-(1)- gree of whiteness; the resultant brightening effects are coumarin pale, almost colourless crystals; melting point very fast to light and chlorine. 271-272 C. (decomposition) the diazo compound of Coumarin compounds of the general formula (I) which is reduced with sodium hydrogen sulphite, as de which contain one or more alkyl radicals with 4-12 car Scribed, to form 7-hydrazino-3-(4-phenyl-5-methyl-y-tri bon atoms are, in many cases, suitable for the optical azolyl-(1)-coumarin; pale-yellow crystal powder, melting brightening of synthetic fibre materials form organic point 237-239 C. (decomposition). solvents. The process is characterised in that the fibre 30 The 7-amino-3-(4-methoxymethyl-, 4,5-dimethoxymeth materials are impregnated with dyeing liquors containing yl, 4-methoxyvinyl- and 4,5-tetramethylene-y-triazolyl these brightening agents, and are subsequently subjected (1)l-coumarins obtainable according to the methods de to a heat treatment. Scribed above from 4-methoxymethyl-y-triazolyl-(1)-ace EXAMPLE 1. tonitrile, 4,5-dimethoxymethyl-y-triazolyl-(1)-acetonitrile, 35 4-(6-methoxyvinyl)-v-triazolyl-(1)-acetonitrile or 4,5,6,7- (A) Preparation of 7-hydrazino-3-v-triazolyl-(1)- tetrahydrobenzo-triazolyl - (1) - acetonitrile and 4-acetyl coumarin amino-2-hydroxybenzaldehyde-anil can likewise be con 228 g. 7-amino-3-Iv-triazolyl-(1) J-coumarin (French Verted into the corresponding hydrazines by reduction of Patent Specification No. 1,336,427) are stirred in 900 ml. their 7-diazo compounds. of concentrated hydrochloric acid at 65° C. for 1 hour, 40 (C) Preparation of 7-4-ethyl-5-methyl-y-triazolyl-(2)- and the resultant light-coloured crystal suspension is sub 3-Iv-triazolyl-(1)-coumarin (1c) sequently diazotised, after cooling to 0-5 C., with good stirring with a solution of 70 g. sodium nitrite in 250 ml. 127 g. 7-hydrazino-3-v-triazolyl-(1)-coumarin are of Water. The clear brown-red diazo solution so obtained stirred with 63 g. 2-oximino-pentanone-(3) and 40 ml. is Subsequently added dropwise with stirring to 1.4 litres 45 of 50% acetic acid in 500 ml, glycol monomethyl ether of a concentrated technical sodium bisulphite solution, at 92-95 C. for 4 hours. The reaction mixture is allowed the temperature being kept within a range of 0-5° C. by to Cool down to room temperature while stirring is con external cooling with ice. The resultant yellow suspension tinued 250 ml. of water are added dropwise, and the is further stirred for 12 hours, first at 0° C., then at room precipitated yellow oximino-hydrazone is filtered off with temperature; the diazo reaction of a sample with H-acid 50 Suction. It is washed with a little cold methanol and dried is then negative. The precipitated yellow 7-hydrazino-3- at 80 C. under reduced pressure. 167 g. oximino-hydra triazolyl-coumarin-as-Sulphonic acid is filtered off with Zone are obtained in the form of an Orange-yellow crystal Suction and the filter paste is stirred in 1 litre of concen powder of melting point 260-262° C. (decomposition). trated hydrochloric acid at 65° C. for 3 hours. The com 167 g. of dry oximino-pentanone-triazolyl-coumarin plete elimination of the sulphonic acid group is tested by 55 hydrazone are stirred with 55 g. acetic anhydride and 14 means of a thin layer chromatogram. After the addition g. of anhydrous sodium acetate in 300 ml. dimethyl form of 1 litre of Water and cooling to room temperature, the amide. The mixture is heated to 100-105° C. within one light-coloured crystal suspension is filtered off with suc hour, the same temperature is maintained for 3 hours, tion and the resultant moist filter paste is again Suspended and stirring is continued at 120-125° C. for one hour. in 1 litre of water. This suspension is mixed dropwise 60 About 100-150 ml. are subsequently distilled off from With stirring at room temperature with an aqueous am the reaction mixture under reduced preSSure, the mixture monia Solution until the pH value of 8 no longer changes. is allowed to cool down to room temperature, and the The resultant pale-yellow finely crystalline precipitate is precipitated crystalline material is filtered off with Suction. filtered off with Suction, washed with cold water until It is purified by reprecipitation from aqueous dimethyl free from salt, and dried. There are obtained 196 g. of 65 formamide and subsequently from chlorobenzene, and yellow 7-hydrazino-3-(y-triazolyl-(1) J-coumarin with a there are thus obtained 115 g. of the desired triazolyl coumarin in the form of white needles of melting point Content of 94% (76% of theory); melting point 270 207-208 C., which dissolve in dimethyl formamide to 275 C. (decomposition). give a colourless solution of intense violet-blue fluores. (B) Preparation of 7-hydrazino-3-(4-phenyl-v- O CCC. triazolyl-(1) J-coumarin The 3-v - triazolyl-( 1)l-7-IV-triazolyl-(2) J-coumarins listed in the following table can be prepared in an analo 220 g. 4-phenyl-y-triazolyl-(1)-acetic acid are stirred gous way from 7-hydrazino-3-Iy-triazolyl-( 1)-coumarin with 254 g. 4-acetylamino-2-hydroxy-benzaldehyde-anil, or its derivatives substituted on the y-triazolyl-(1) ring 100 g. of anhydrous Sodium acetate and 550 g. acetican 75 and the specified oximino-ketones, 3,839,351 11. 2 TABLE R3 R

NeN - No =O R1- N SOC N Shade of fluorescence in DME R 3 R Oximino-ketone (350 m) C H Oximino-acetone.------Wiolet-blue. CH H Diacetyl-monoxime. ---- Do. CH 2-oximino-pentanone-(3). Do. CH3 H -phenyl-2-oximino- Somewhat butanone-(3). reddish blue. -e--- iso-CaFF CE H 3-oximino-4-methyl- Violet-blue. pentanone-(2). H 3-oximino-heptanone-(4)- Do. H 3-pimino-tridecanone- Do. H 2-oximino-cyclohexa- Do. none-(1). H 1-oximino-3,3-dimethyl- Do. propanone-(2). E. Oximino-acetophenone. Somewhat reddish blue. 1-l.--. CFIIs E. -Oximino-1-phenyls Do. {D- acetOne. !--- (- Chs H Oximino-propiophenole- Do.

1-n--- Same as above.------a w w Cs Oximino-butyrophenone. Do. 1-0------do------iso-C3H Oximino- Do. isovalerophenone. lip------do------H Cyclohexyl-oximino- Reddish benzylketone. blue. ld------do------BenZil-monoxime------Do.

4-methyl-oximino-pro- Do. piophelone.

4-fluoro-oximino-aceto- Do. F phenone.

1-t---- Ca H. 4-chloro-oximino-pro- Do. piophenone. i-ti--- CH 4-methoxy-oximino-pro- Bluie. piophenone. i-W--- C H 4-benzyl-oximino-pro- Somewhat -CE piophenone. reddish blue.

CE H 1-oximino-1-m-cyano- Do. 1.-W.--- 3 phenylacetone.

NC

1-x.--- CH3 1-oximino-1-p-carbeth- Blue. oxyphenylacetone. l-y--- C H 2-oximino-indanone-(1).-- Do.

-Z-...-- C2H5 CH3 2-oximino-pentanone- Do. aar (3). a-1---- C3H5 CH CE Same as above.------do------Wiolet-Blue. b---- CE5 CH3 B -CH=CH-O C3 ----do- Do. c----- C2Es C3 COC CH2OCH3 Do. d-1--- C2H5 CH3 CH2OCH Do. e----- C2His -(CH2)4- Do. 8,839,351 14 EXAMPLE 2. perature are filtered off with suction, washed with metha nol and recrystallized from chlorobenzene with the addi Preparation of 7-4-methyl-5-carbethoxy-y-triazolyl-(2)- tion of bleaching earth. 116 g. 7-methylpyrazolyl-3-tri 3-y-triazolyl-(1)-coumarin (2a) azolyl-coumarin are so obtained in the form of greenish white needles which dissolve in dimethyl formamide with 23 g. of 7 - amino-3-y-triazolyl - (1)-coumarin are a violet-blue fluorescence (melting point 260 C.). stirred in the hot with 50 ml, of concentrated hydrochloric acid and 25 ml. of water. After cooling to --5 C, the (B) Preparation of 7-3-methyl-4-phenylpyrazolyl-(1)- light-coloured suspension is diazotised by the addition of 3-y-triazolyl-(1)-coumarin (2i) a solution of 7 g. sodium nitrite in 30 ml. of water. The resultant diazo solution is poured into 500 ml. of ice O 25 g. 7 - hydrazino-3 - Iy-triazolyl-(1)-coumarin are water and the excess of hydrochloric acid is buffered with stirred with 200 ml. glycol methyl ether, and 11 g. acetic sodium carbonate. The diazo suspension is then poured anhydride are added at 40° C. The resultant solution is into a solution of 15 g. 6-amino-crotonic acid ethyl ester mixed with 17 g. a-phenyl-acetoacetoaldehyde (=hydroxy in 200 ml, of alcohol, the pH value being kept at 5-6. methylene-benzy-methylketone) and stirred at 50° C. When the coupling is completed, a dilute sodium chloride 15 for 3 hours and at 70° C. for 1 hour. 15 ml. of concen solution is added to the mixture, the precipitated orange trated hydrochloric acid are subsequently added drop brown azo compound is filtered off with suction and dis wise, and the mixture is stirred at 65-70° C. for 1 hour solved in 250 ml. pyridine. 45 g. copper acetate are and at 100-105 C. for 1 hour. After cooling, the pre gradually added with stirring, and the mixture is heated cipitated pyrazolyl-coumarin is filtered off with suction, at 75-80 C. As soon as the cyclisation is completed 20 washed with methanol, and purified by recrystallisation (about 3 hours), the pyridine is driven off with steam and from chlorobenzene. 12 g. methyl-phenyl-pyrazolyl-tri the residue is purified by reprecipitation from toluene and azolyl-coumarin are so obtained in the form of greenish dimethyl formamide. 14 g. of the coumarin derivative pale-yellow crystals which dissolve in dimethyl forma mentioned above are obtained in the form of pale yell 25 mide with a somewhat reddish blue fluorescence. lowish needles which dissolve in dimethyl formamide with (C) (Preparation of 7-3-methyl-4-chloropyrazolyl-(1)- a violettish blue fluorescence. 3-Iv-triazolyl-(1)-coumarin (3t) The coumarin derivatives listed in the following table are obtained in an analogous way with the use of the 15 g. 7 - 3-methylpyrazolyl-(1)-3-Iv-triazolyl-(1)- specified coupling components. 30 coumarin (3a) are dissolved in 400 ml. tetrachloroethane;

ABLE R R N N LN=NN R N / No N AgenceShade of No. R. R R. R. Coupling component (350 mps) 2-a-- CHs COOCs H E f-Amino-crotonic acid ethyl ester.... Violet-blue. 2-bl. CH COOH E 3-Amino-crotonic acid E. ester Do. (Subsequently hydrolysed). 2-c.---- Ca CN H H 6-Aminocrotonitrile.------Do. 2-d--- CN H H A-Amino-cinnamic acid nitrile------Blue.

2-e---- Sane as above CON E H 6-Amino-cinnamic amide...------. Do. 2-f------do------COOCs H H 3-Amino-cinnamic acid ester. Do.

EXAMPLE 3 the solution is mixed at 50° C. with 9 g. sulphuryl chlo 65 ride. Stirring is continued at 50° C. for 2 hour and at (A) Preparation of 7-3-methylpyrazolyl-(1)-3- 75 C. for 72 hour, the mixture is then allowed to cool v-triazolyl-(1)-coumarin (3a) down, and the precipitated crystalline product is filtered 127 g. 7-hydrazino-3 - Iv-triazolyl-(1)-coumarin are off with Suction. It is purified by recrystallisation from heated in 900 ml. glycol monomethyl ether with 75 g. 3 dimethyl formamide and is then present in the form of ketobutyr-aldehyde-dimethylacetal at 100° C. for 4 hours greenish white crystals which dissolve in dimethyl forma while stirring. After cooling to 60° C., 40 ml. of con mide with a strong violet-blue fluorescence. centrated hydrochloric acid are added to the mixture and The compounds obtained according to this process with stirring is continued at 90-100° C. for 2 hours. The the specified carbonyl compounds are listed in the follow crystals which are precipitated after cooling to room tem- 75 ing table. 3,839,351

TABLE Rs

N -R ? N N R^\ No/ - Y, Ri- N /

Shade of fluorescence in DME No. R R R3 R Carbonyl compound (350 mi) 3-a-...- CH3 B. H H B-Estabutyraldehyde dimethyl- Violet blue. 8Cetal. 3-b--- H H H H 1,1,3,3-tetramethoxypropane (or Do. malonic aldehyde). 3-C---- H H H Phenyl-3-chlorovinyl-ketone.------Somewhat reddish blue. 3-d--- H H a-Phenyl-6-dimethyl-amino- Reddish acrolein. blue.

3-e---- CH3 H Hydroxymethylene-propio- Somewhat phanone. reddish blue. 3-f.--- Same as above.------C2H H Hydroxymethylene-butyro- Do. phenone. 3-g------do------iso-C3H H H Hydroxymethylene-isowalero- Do, phenone. 3-h.--- E. H Hydroxymethylene-benzylcyclo- Do. - hexyl-ketone.

3-i---- CHs Same as above.------H H Hydroxymethylene-benzyl- Do. methyl-ketone

3-ki--- CH3 H Methyl-(a-benzyl-3-hydroxy- Violet-blue. CF- vinyl)-ketone.

3-I---- B Hydroxymethylene-benzyl- Somewhat CH- - benzyl-ketone. reddish blue. 3-m--- Same as above.------H H Hydroxymethylene-desoxy- Blue. benzoin.

3-n------(CH2)4- H E. 2-hydroxymethylene-cyclo- Wiolet-blue. hexanone-(1). 3-O---- Cas E. Hydroxymethylene-benzy- Somewhat ethyl-ketone. reddis blue. 3-p--- H Same as above.------H Phenylmalone-dialdehyde.------Rish le. 3-q--- H -----do------CHs -----do------Somewhat reddish blue. 3-r---. CFs H -(CH2)4- Kabutyraldehyde-dimethyl- Violet-blue. 3Ce3. 3-S.-- CH H H CHOCH ----- do------Do. 3-t.--- C3 C H H Ketobutyraldehyde-dimethyl- Do. acetal; subsequently chlorinated.

3-1 - H. Br H H Bronomalone-dialdehyde- D0. 3-v--- H Cl H H Chloromalone-dialdehyde- Do. 3-wl. CH E. CH Ketobutyraldehyde-dimethyl- Somewhat acetal. reddish blue.

EXAMPLE 4 uum drying cabinet. In this way it is obtained in the form of yellowish white crystals which readily dissolve in water Preparation of 7-4-ethyl-5-methyl-y-triazolyl-(2) J-3-3- with a greenish blue fluorescence. methyl-v-triazolium-(1) - coumarin methosulphate or 6 The 7-4-ethyl-5-methyl-y-triazolyl-(2)-3-3 - methyl bromide y-triazolium-(1)]-coumarin bromide can easily be precipi 32 g. 7-4-ethyl-5-methyl-v-triazolyl-(2) - 3 - Iv - tri tated from an aqueous solution of the methoSulphate with azolyl-(1)-coumarin are boiled under a weak reflux in the aid of potassium bromide; white crystals whose 150 ml. toluene with 13.5 g. dimethyl sulphate for 1 hour. colourless aqueous solution has a greenish blue fluores The solvent is subsequently distilled off on a water bath 70 CCCC. under reduced pressure, and the light-coloured oily resi From the 3-triazolyl-coumarins mentioned in Examples due is mixed in the cold with a little petroleum ether. 1-3, the corresponding 3-triazolium-coumarin salts can After standing, there crystallises the triazolium-coumarin easily be prepared in an analogous way with alkylating methosulphate which is filtered off with suction, washed agents; the most important compounds are listed in the with a little petroleum ether, and dried at 50° C. in a vac-7 following table.

3,839,351 19 20 EXAMPLE 5 ratio of 1:40 in an aqueous bath at 95 C., which con Fibres of polyethylene glycol terephthalate are intro tains, per litre, 1 g. sodium chlorite and 1 g, oxalic acid. duced in a liquor ratio of 1:40 into a bath containing, per The fibres so obtained are pure white. litre, 1 g, oley sulphonate, 0.75 g. formic acid and 0.1 g. EXAMPLE 11 of one of the compounds mentioned in Examples 1a-1f and 3a-d. The bath is subsequently heated to boiling A yarn of polyamide 6 is treated in a liquor ratio of temperature and the same temperature is maintained for 1:40 at 80-90° C. for 30 minutes in an aqueous bath 30-60 minutes. After rinsing and drying, the polyester containing, per litre, 0.15 g. of the brightening agent of fibres exhibit a very good brightening effect of high fast the formula ness to washing, chlorine and light. I) EXAMPLE 6 A yarn of polyethylene glycol terephthalate is agitated in a liquor ratio of 1:40 in a roller bath at 125° C. for 45 minutes in a liquor containing, per litre, 1 g oleyl sulphonate, 0.75 g. formic acid and 0.1 g of one of the compounds mentioned in Examples 1 to 3. After rinsing and 2 g. sodium chlorite. After rinsing and drying, the and drying, the polyester yarn exhibits a good degree of yarn exhibits a very clear brightening effect. whiteness of high fastness to washing, chlorine and light. The brightening agent used above was prepared as fol EXAMPLE 7 lows: 10 g. 3-y-triazolyl-(1)]-7-4-phenyl-5-methyl-v- triazolyl-(2)-coumarin (Example 1 m) are heated in 70 A fabric of polyester fibres is padded with an aqueous ml. of concentrated sulphuric acid at 115 C. for 2 hours liquor containing, per litre, 1 g of a commercial dispers while stirring. After cooling, the mixture is poured into ing agent based on fatty alcohol polyglycol ethers, 1 g. 400 ml. of cold water, sodium chloride is added until the of a commercial wetting agent based on alkyl-naphthalene precipitation is complete, and the precipitated sulphonic sulphonic acids, 4 g. of an alginate thickening agent, as acid is filtered off with suction. The filter residue is stirred well as a solution of 1 g. of one of the compounds men in 500 ml. of hot water and neutralised with a sodium tioned in Examples 1 to 3, in 20 g. triethanolamine. The hydroxide solution. The hot solution is clarified with the fabric is then squeezed to a weight increase of 100%, 30 use of adsorption charcoal, and the sulphonic acid salt is then dried, heated at 190° C. for 1 minute, and subse salted out by the addition of sodium chloride. The pre quently washed hot. Compared with untreated fabric, it cipitated product is filtered off with suction, washed with exhibits a very strong and clear brightening effect of ex a 5% sodium chloride solution, and dried. The sodium cellent fastness to light, washing and chlorite. salt of 3-v-triazolyl-(1)-7-3-sulphophenyl-5-methyl-v- EXAMPLE 8 triazolyl-(2)-coumarin is obtained in the form of a light coloured greenish crystal powder whose colourless solu 6 kg. terephthalic acid dimethyl ester and 5 litres ethyl tion in dimethyl formamide has a strong blue (reddish) ene glycol are mixed in a stirrer autoclave with 0.05% fluorescence in ultraviolet light. zinc acetate and 0.03% (referred to terephthalic acid methyl ester) of one of the compounds described in Ex EXAMPLE 12 amples 1d, q, w, y and Z. The autoclave is heated to 180 A fabric of cellulose acetate fibres is introduced in a C. while stirring; transesterification starts at about 150 liquor ratio of 1:40 into a bath containing, per litre, 1 C. The eliminated methanol is distilled off. The tempera g. oleyl sulphonate, 0.75 g. formic acid, and 0.08 g. of one ture is raised to 200 C. after one hour and to 220 C. of the brightening agents mentioned in Example 1 under after a further 45 minutes. The transesterification is then 45 c to i. The bath is then heated to 60° C. within 20 minutes completed. For precondensation, the product so obtained and the same temperature is maintained for 30-60 min is pressed under nitrogen into an autoclave heated to utes. After rinsing and drying, the fabric exhibits a bril 275 C. During precondensation, the excess of glycol is liant brightening effect. distilled off. After 45 minutes, a vacuum is applied, which We claim: is weak at first and is increased to below 1 mm. Hg in 1. Coumarin compound of the formula the course of a further 45 minutes. After about 2% 50 hours, the polycondensation is completed and the resultant R3 R melt is subsequently extruded to produce filaments with a final titre of 50-25. The filaments so obtained exhibit an N -N N. outstanding brightening effect of high fastness to light and 55 R-(4. N r NN/ wet processing. N aO EXAMPLE 9 Ri-N / No/T Polyacrylonitrile fibres are introduced in a liquor N ratio of 1:40 into an aqueous bath containing, per litre, wherein 1 g. oxalic acid, 1 g. sodium chlorite, as well as 0.05 g. of 60 R1 and R2 ae H; CH: C2H5; CH; C4Hg; C5H11; COOH; one of the compounds mentioned in Example 4. The bath CONH2, CH, CH21; CH=CH-; CHCOOC2H5; is heated to boiling temperature within 20 minutes and C2H4COOCH3; C2H4OH; benzyl; CN, COOCHs; cy the same temperature is maintained for 45-60 minutes. clohexyl; styryl; naphthyl; phenyl; phenyl substituted The polyacrylonitrile fibres are subsequently rinsed and by Cl, Br, F, CH3, C2H5, C4H9, OCH3, OCH5, benzyl, E. The fibres then exhibit an outstanding brightening 65 benzyloxy, dimethylbenzyl, phenyl, phenyloxy, cyano, effect. SO2CH3, COOCH5, SOH; or R1 and R2 together form EXAMPLE 10 a radical-(CH2)3-, -(CH2)4-, One of the compounds mentioned in Example 4 is CH added to a conventional polyacrylonitrile spinning so 70 lution in such a quantity that the concentration of this - 0 compound in the polyacrylonitrile component of the ex truded fibre amounts to 0.1 percent by weight. The spin and wherein ning Solution is spun in the usual way and the fibre mate R3 and R4 are H, CH, CHOH, CHOCH, phenyl, or rial so produced is agitated for 45 minutes in a liquor -CH=CH-OCH3 and R3 and R together are a rad 3,839,351 21 22 ical -(CH2)-4, and their quaternization products of 3. the formula R3 R

e N -CH, Bre N N-Rs xe 5 CH-1N NN/ R^N. I’ CHCH N-A1-0 R NN/ \/=0 N/ wherein R5 is C-4 alkyl, chloroethyl, methoxy ethyl O References Cited carbomethoxy methyl, ethoxyethyl, cyanoethyl, cyano UNITED STATES PATENTS methyl hydroxyethyl, or benzyl; and Y is a colorless 3,646,052 2/1972 Neuner et al. ------260-308 A anion. 3,521,187 7/1970 Snavely et al. ------260-308 R 2. Coumarin compounds of the formula 5 3,663,560 5/1972 Schellhammer et al. - 260-308 R 3,271,412 9/1966 Raue et al. ------260-308 B JOSEPH A. NARCAVAGE, Primary Examiner N N N U.S. C. X.R. CH-1 Y N 20 260-308 B, 37 R; 8-57 CHCH-l/ o/So N