NL8203209A - 2-PHENYL-2H-1,2,3-TRIAZOLES, METHODS FOR PREPARING THEM AND USING THESE COMPOUNDS. - Google Patents

Description

N.O. 31 215-1-3-2-3-enyl-2H-1,2,3-triazoles, processes for their preparation and use of these compounds.

; The present invention relates to novel: 2-phenyl-4-alkanoyl- (or benzoyl-) 2H-1,2,3-triazoles, methods for their preparation, their use for the preparation of 2-phenyl-2Ξ-1 2,3-triazol-ylacetic acid and its derivatives, which are used as starting materials for the preparation of optical brighteners of the 3- (2, -phenyl-2, H-1 ', 2', 3, -triazole -4, -yl) -cuinark series can be used. The invention relates to a process for the preparation of the said triazolylacetic acids, as well as new intermediates, which are used in the mixing of the 2-phenyl-4-10 alkanoyl (or benzoyl) 2H-1,2,3-triazoles according to the invention.

2-Penyltriazoles, as well as methods for their preparation are known. See the overview article by E.R. Benson et al. In Chem. Rev. ^ 6, (1950) 1 and from T.L. Gilchrist et al.

15 in Adv. in Heterocyclic Chem. 1-6, 33 (1974), Academic Press,

Hew York and London; in addition, Chem. Abstr. 22 (1973), 66367η, CH-PS 485,014, DE-AS 1,168,437, DE-PS 1,226,591, E. Klingsberg, Synthesis 1972 (9) 475-7 and Chem. Ber. £ 8 (4), (1965) 1335-41, (= Chem. Abstr. 62 (1965), 16090 d).

The object of the present invention was now to provide new, specifically substituted 2-phenyl-2H-1,2,3-triazoles, which are particularly valuable intermediates, especially for the preparation of optical brighteners. Moreover, it was an object of the invention to find a new synthetic route for 2-phenyl-2H-1,2,3-triazol-4-ylacetic acids and derivatives thereof, which are used for the preparation of optical brighteners of the 3- (2 -phenyl-2, -11,21,3, -triazol-4, -yl) -umarin series have large betelsiis.

It has now been found that the new 2-phenyl-4-alkanoyl (or benzoyl) 2H-1,2,3-triazoles meet these requirements. Some of the new intermediates arising in the preparation of these valuable compounds are also subject of the present invention.

The 2-phenyl-2H-1,2,3-triazoles according to the invention correspond to 8203209-2 - with formal 1, wherein Eg C 1 -G 2 -alkyl, unsubstituted or substituted phenyl or benzyl and Z unsubstituted or substituted phenyl introduce.

As substituents for the phenyl ring Z resp. for Eg 5 as a phenyl or benzyl radical, the following may be considered, for example: halogen, alkyl, alkoxy, nitro, cyano, trifluoromethyl, alkenyl, cycloalkyl, substituted alkyl or. alkoxy such as alkoxyalkyl, alkoxyalkoxy, hydroxyalkyl, hydroxyalkoxy, haloalkyl, haloalkoxy, cyanoalkyl, carboxyalkyl, sulfoalkyl, phenylalkyl, phenoxyalkyl or carbalkoxyalkyl, carboxy and sulfo and derivatives, each of which are haloxyalkyl, alkoxy , carbalkoxy, alkylsulfonyl, cyano, nitro, trifluoromethyl, carboxy or sulfo and derivatives may be singly or multiply (e.g. 2-fold) substituted; 1 2 15 furthermore groups of the formulas -jj-HHgjIIY Y, -s (0) n-alkyl or

S

-S (0) n -substituted. alkyl, the substituted alkyl groups of which are those mentioned above and wherein n is the number 1 2 0, 1 or 2 and Y and Y are independently hydrogen, alkyl, 1 2 20 substituted alkyl (definitions as above) or Y and Y together with the nitrogen atom to which they are attached, a saturated 5- or 6-membered heterocyclic ring forms, optionally containing 1 or 2 nitrogen, oxygen and / or sulfur atoms as ring components and may optionally be substituted with alkyl groups.

Of the said substituents, the phenyl groups contain resp. benzyl groups Rg, when they are substituted 2, preferably 1 substituent. The phenyl radical Z in particular contains 3> preferably 2 substituents or such a substituent, wherein substituents of the 2-order or sterically hindering residues preferably occur at most twice, in particular only once in phenyl core.

Halogen is understood to mean chlorine, fluorine or bromine, preferably chlorine. Alkyl and alkoxy groups can contain 1 to 8, for example 1 to 6, especially 1 to 4, carbon atoms.

The equal numbers of carbon atoms apply to alkyl or alkoxy moieties in composite residues (eg, alkoxyalkyl, alkoxyalkoxy, carbalkoxy, etc.) as well as substituted alkyl or alkoxy groups. Alkenyl preferably contains 2 to 6, especially 3 or 4, carbon atoms.

Derivatives of sulfo or carboxyl groups are preferably 8203209e * - 3 -, salts, esters and amides. The amides lean with the formula

12 12 1 2 -SOgHT Y resp. COUY Y correspond (meaning of Y resp. Y

see above). Saturated heterocyclic nitrogen compounds 12 (Y + Y), insofar as they have other heteroatoms in the ring 5, have additional heteroatoms as such, preferably an N, O and / or S atom. Preferably, alkyl alkyl additives contain from 1 to 4 carbon atoms. Examples of such heterocyclic nitrogen compounds are, for example, the piperidine, piperazine, imidazolidine, pyrrolidine, morpholine, thiomorpholine or oxazolidine ring.

The salts of carboxy and sulfo groups ("carboxy" and "sulfo" in this application are always also understood to include their salts) are particularly suitable alkali metal, alkaline earth metal, ammonium or amine salt ions.

15 carboxyl groups then correspond to the formula -C00M resp.

-SOjM, in which M represents hydrogen or a salt-forming cation.

An alkali metal, ammonium or amine salt ion is suitable as a salt-forming cation. Among amine salt ions, those of the formula H®KR ° R ^ B! J are preferred, wherein R °, R ° and R ° independently represent hydrogen, alkyl, alkenyl, hydroxyalkyl, cyanoalkyl, haloalkyl or phenylalkyl and wherein R ° and Rg together represent the completion of a saturated heterocyclic nitrogen containing 5- or 6-ring, which may additionally contain a nitrogen or oxygen atom as a ring constituent, for example a piperidine, piperazine, pyrrolidine, imidazoline or morpholine ring while R 1 represents hydrogen.

Within the scope of formula 1, the 2-phenyl-2E-1,2,3-triazoles of formula 2 are emphasized, wherein R 1, C 1 -C 2 alkyl, unsubstituted phenyl or benzyl or with .1 or 2 substituents of the group halogen, C 1 -C 2 -alkyl, C 1 -C 2 -alkoxy, C 1 -C 2 -alkenyl, nitro, cyano, carboxy or sulfo and derivatives thereof, C 8 -C 1 -carbalkoxy or trifluoromethyl substituted phenyl or benzyl and R ^, R ^ and R, - independently of one another hydrogen, halogen, trifluoromethyl, cyano, nitro, C 1 -C 1 -alkyl, C 1 -C 1 -haloalkyl, C 1 -C 1 -hydroxyalkyl, Cg -C ^ -alkoxyalkyl, C ^ -G ^ -alkenyl, C ^ -C ^ -alkoxy, O ^ -C ^ -halo-alkoxy, C8 -C8 alkoxyalkoxy, unsubstituted or with halogen, C ^ -C ^ -alkyl , C 1 -G 2 -alkoxy, C 2 -C 2 -carbaloxy, C 1 -G 2 -alkylsulfonyl, cyano, nitro, trifluoromethyl or a group of formula -COOY ^ or 40 -SO ^ Y ^ mono- or poly-substituted phenyl or phenoxy, or an 8203209-4 group with formula -jj-BHg, -EY.jYg, -SO ^, -COOY ^, -8 (0 ^ - (0 ^ 0 ^ -

S

alkyl) or -S (O) n- (C 1 -C 1 -haloalkyl), wherein and Yg independently of one another is hydrogen or C 1 -O 2 -alkyl, Y 1 5 hydrogen, C 1 -C 2 -alkyl or a salt-forming cation and n represent the number 0, 1 or 2.

Because Eg represents a substituted phenyl or benzyl radical, it preferably contains biη of the indicated substituent and.

In particular, in formula 2, E7, R. and R. .. the 3 4 5 have the following meanings: R 1 hydrogen, halogen, trifluoromethyl, cyano, nitro, C 1 -C 2 alkyl, C 1 -C 2 haloalkyl C 1 -G 2 -hydroxyalkyl,

Og-Cg-alkoxyalkyl, C 1 -C 2 -alkenyl, C 1 -C 2 -alkoxy, C 1 -C 2 -halo-alkoxy, C 2 -C 8 -alkoxyalkoxy, unsubstituted or with halogen 15 C 1 -C 2 - alkyl, C 1 -C 2 -alkoxy, C 2 -C 2 -carbaloxy, C 1 -C 2 -alkylsulfonyl, cyano, nitro, trifluoromethyl or a group of formula -C00Y, or 3 -SO ^ Yj, singly or multiply substituted phenyl or phenoxy, or έέη of the groups of formula -C-m2, -HY ^ g, -SOjly -C00Y5, -s (0) n- (C r4 alkyl) or -S (0) n-

20 I

(C 1 -C 1 -haloalkyl), wherein Y 1 and Yg independently of each other is hydrogen or C 1 -C 1 -alkyl, Y 1 hydrogen, C 1 -C 1 -alkyl or a salt-forming cation and n is the number 0, 1 or 2, R ^ hydrogen, halogen, C ^ -C ^ -alkyl, C ^ -C ^ -alkoxy, nitro, cyano, C ^ -C ^ -halogen-25 alkyl, -NY ^ Yg, -SO ^ -COOY 2 or C 1 -G 2 alkylsulfonyl, R 2 hydrogen, halogen, G 1 -C 2 alkyl or G 1 -C 2 alkoxy.

Preferably the same as salt-forming cations Y-

^ JL

eligible, as noted above for M. Alkali metal and ammonium ions are preferred. The derivatives of sulfo and carboxyl groups are also preferred, which are exemplified above under formula 1.

Particularly mentioned are the 2-phenyl-1,2,3-triazoles of formula 3> wherein R 2J C 1 -C 2 -alkyl, benzyl, unsubstituted or with 1 or 2 substituents from the group chlorine, O 2 -C -alkyl, methoxy, nitro, cyano and / or trifluoromethyl substituted phenyl and R ^ and R ^ independently hydrogen, halogen, trifluoromethyl, cyano, nitro, C 1 -C 2 -alkyl, C 1 -C 2 -alkoxy C 1 -C 2 -alkylsulfonyl, unsubstituted or with halogen, C 1 -C 2 -alkyl, C 1 -C 2 -alkoxy, cyano, nitro, trifluoromethyl or a group of the formula -C00Y ^ or 40 - SO ^ Yj; substituted phenyl or phenoxy, or a group of the formula 8203209-5 - -SO ^ Y ^ i -COOYj or -NY ^ Yg, where Y ^, Y2 or Y ^ are as defined in formula 2 and Y 'is hydrogen, a alkali metal o or ammonium ion.

. *.

E 1 in formula 3 "preferably represents hydrogen, halogen, cyano, nitro, C 1 -C 2 -alkyl, C 1 -C 2 -alkoxy, C 1 -C 2 -alkyl] phenyl, -rCOOYj, -SO 2 Yj or .-BY ^ g for.

Of practical significance are in particular the 2-phenyl-2H-1,2,3-triazoles of formula IV wherein E 1 'C 1 -C 1 -C 2 alkyl, benzyl or unsubstituted or with 1 or 2 substituents from the 10 group chlorine, methoxy and / or methyl substituted phenyl, E 2 hydrogen, halogen, trifluoromethyl, cyano, nitro, C 1 -C 2 alkyl, O 2 -C 2 alkoxy, C 1 -C 2 alkylsulfonyl, unsubstituted or phenyl or phenoxy substituted by chlorine, methyl, msthoxy, cyano, nitro, sulfo or earboxy or its alkali or ammonium salts, or a group of the formula -SO ^ Y ^, -COOY ^ or -HY ^ Yg, where Y ,, Yg and Yj are as defined in formula 3 and E ^ represents hydrogen, halogen, C 1 -C 2 alkyl or C 1 -C 20 alkoxy.

Preferred 2-Enyl-2H-1,2,3-triazoles correspond to formula 5 wherein E 2 'is hydrogen, halogen, C 1 -C 2 -alkyl, C 1 -C 2 -alkoxy, cyano, nitro, sulfo or earboxy and their alkali metal or ammonium salts, C 1 -C alkylsulfonyl, phenoxy, phenyl, chlorophenyl, methylphenyl or carboxyphenyl and their alkali metal or ammonium salts and E 2 'hydrogen, halogen, methyl or methoxy.

Particular preference is also given to compounds of the formulas 1 to 4, in which Eg, E £, E £, respectively. E represents methyl.

The process described below for the preparation of compounds of the invention of formulas 1 to 5 are also subject of the invention.

A first process for the preparation of compounds of formula 1 and thus also the derived formulas 2 to 5 consists in that an oxime of formula 6, in which Z and Eg are defined as in formula 1, in the presence of a condensation agent until the corresponding triazole rings.

The compounds of formulas 2 to 5 are obtained in an analogous manner by using starting materials of formula 6, in which Eg, like the phenyl residue, has the meanings indicated in formulas 2 to 5. An oxime of formula 6 is preferably started from, in which Eg represents methyl.

8203209 - 6 -

As the condensing agent, an acid anhydride or an acid halide is preferably used in the process according to the invention, for example acetic anhydride, propionic anhydride, acetylochloride, benzoyl chloride, benzenesulfochloride, toluene-5-sulfochloride, methanesulfochloride, ethanesulfochloride, acetic acid chloride or thionyl chloride.

The process according to the invention produces the best results (high yields, purity of the products) when it is carried out with acetic anhydride as condensing agent in aqueous medium. The pH value is preferably kept between 10 and 13, in particular between 11-12, in the ring closure. The reaction temperature can be between 0 and 100 ° C, preferably at a reaction temperature between 0 and 50 ° C, in particular between 5 and 25 ° C. In the preferred variant of the process of the invention outlined, the reaction medium consists of acetic anhydride and water. However, a water-miscible organic solvent may additionally be present in the reaction medium. Instead of the water-miscible solvent, a water-immiscible organic solvent may also be used. This variant may, in particular, be recommended if a water-insoluble product of the formula 1 is obtained. The final product then dissolves in the organic phase, with which it can be separated from the reaction mixture and fed to the work-up.

Examples of suitable water-miscible organic solvents are low aliphatic alcohols such as methanol, ethanol, isopropanol, n-propanol, butanol and ethylene glycol, ethylene glycol monoalkyl ethers, tetrahydrofuran, dioxane, formamide, dimethylformamide and the like solvent.

As water immiscible solvents, for example, liquid aliphatic hydrocarbons and mixtures thereof, halogenated, preferably chlorinated, aliphatic hydrocarbons can be used, for example methylene chloride, chloroform, carbon tetrachloride, 1,1,1-trichloroethane, perchloro-ethylene, trichlorethylene and others, aromatic hydrocarbons such as benzene, toluene, xylene, chlorinated aromatic hydrocarbons such as chlorine, dichloro or trichlorobenzene, among others.

Another process according to the invention for the preparation of 2-phenyl-2H-1,2,3-triazoles of formula 1 and the derived formulas 2 to 5 consists in that a compound of formula 7 is 8203209

M

Converts to a dioxime of the formula 8 with hydroxylamine or a salt thereof, to ring-seal this dioxime into a triazole of the formula 9 in the presence of a condensing agent and to hydrolyze this to the corresponding ketone. In formulas 7 to 9, the general symbols have the meanings indicated in formula 1. The compounds of the formulas 2 to 5 are obtained in an analogous manner by using starting compounds of the formula 7 in which R 1 and the phenyl radical Z have the meanings given in formulas 2 to 5. It is preferred to start with compounds of the formula VII wherein R2 represents methyl.

The reaction of a compound of formula 7 with hydroxylamine or a salt thereof (first stage) is expediently carried out in an inert solvent, preferably in pyridine.

The reaction temperature can be between 0 and 100, in particular between 15 and 50, preferably between 5 and 25 ° C.

The resulting dioxime of formula 8 is ring-closed in the presence of a condensing agent to form the triazole of formula 9. This second stage can be carried out completely analogous to the cyclization of a compound of formula 6, as described above. Preferred condensing agent, reaction medium, pH value, reaction temperatures and solvent are exactly the same in this second stage of the second process according to the invention, as mentioned above in the cyclization of the compound of formula 6 .

A repetition can therefore be omitted.

The hydrolysis of the triazoles of formula 9 (third stage) obtained in the second stage can take place in the usual manner acidic or alkaline. Preferably, the hydrolysis is reacted in the presence of sodium bisulfite or formaldehyde.

50 paraformaldehyde performed. The hydrolysis is carried out in particular in water or in mixtures of water with a water-miscible organic solvent (examples of such solvents see above), preferably a small aliphatic alcohol, and preferably at an elevated temperature, in the 35 especially at the boiling point of the reaction medium.

The intermediates of formulas 6 and 8 obtained in the two processes just described for the preparation of the triazoles of formula 1 are new and are also subject of the present invention.

A verier aspect of the present invention are 8203209

* V

- 8 - half the oximes of formula 10, wherein C 1 -C 8 alkyl, unsubstituted or substituted phenyl or benzyl, Z represents unsubstituted or substituted phenyl and X represents O or ROH. Preferred substituent meanings have already been explained in formula 1.

Particularly to be mentioned are the oximes of formula 11, wherein X 0 or NOH, R 1 C 1 -C 2 -alkyl, unsubstituted phenyl or benzyl or with 1 or 2 substituents from the group halogen, C 1 -C 2 - alkyl, C 1 -C 2 -alkoxy, C 1 -C 2 -alkenyl, nitro, cyano, carboxy or sulfo and their derivatives, C 1 -C 20 carbaloxy or trifluoromethyl-substituted phenyl or benzyl and Ry R 1 and E 1 independently of each other hydrogen, halogen, trifluoromethyl, cyano, nitro, O 2 -C 1 -alkyl, C 1 -C 2 -haloalkyl, C 1 -C 2 -hydroxyalkyl, C 2 -C 8 -alkoxyalkyl, C 1 -C. -alkenyl, C-C, -alkoxy, C-C, -haloalkoxy, 3 4 14 I 4 15 C 8 -g-alkoxyalkoxy, unsubstituted or with halogen,

C 1 -C 4 -alkyl, C 1 -C 2 -alkoxy, C 3 -C 2 -carbaloxy, C 1 -Calkylsulfonyl, cyano, nitro, trifluoromethyl or a group of formula -COOY ^ or -SO ^ Yj substituted or multiply substituted phenyl or phenoxy, or one of the groups of formula -C-FHg, - FT ^ Yg »-SO ^ Y ^, -COOYj,

20 S

-S (o) - (C-C-alkyl) or -S (0) - (C-C, -haloalkyl) represent, * 1 * 4 * Ώ. where Y ^ and Y ^ independently of one another hydrogen or C 1 -C 2 alkyl, Y 1 hydrogen, C 1 -C 2 alkyl or a salt-forming cation and n represent the number 0, 1 or 2. Preferably, the substituents R 2> R 1, R 1, R 1 and R 1. the meanings indicated in formula 2.

Preferred are the oximes of formula 12, wherein X is O or UOH, RJJ, C 1 -O 2 alkyl, benzyl or unsubstituted or with 1 or 2 substituents from the group chlorine, methoxy and / or methyl substituted phenyl, R " hydrogen, halogen, trifluoromethyl, cyano, nitro, C 1 -C 2 -alkyl, C 1 -C 2 -alkoxy, C 1 -C 2 -alkylsulfonyl, unsubstituted or with chlorine, methyl, methoxy, cyano, nitro, sulfo or carboxy or their alkali metal or ammonium salts and substituted phenyl or phenoxy, or a group of the formula -S0, Yi, 3 3 -C00Y ^ or -FT ^ Yg »where Y ^, Y ^ and Y ^ as in the formula 3 are defined and R 1 represents hydrogen, halogen, C 1 -C 2 -alkyl or O 2 -O 2 -alkoxy, wherein R 1 is preferably hydrogen, halogen, C 1 -C 2 -alkyl, C 2 - C 1 -alkoxy, cyano, nitro, sulfo or carboxy or their alkali metal or ammonium salts, C 1 -alkyl sulfonyl, phenoxy, phenyl, chlorophenyl, methylphenyl or carboxyphenyl and their alkali metal 40 or ammonium salts and R 1 preferably hydrogen, halogen, 8203209-9 - methyl or methoxy prop ellen.

In formulas 10 to 12 Eg »R £ resp. prefer methyl and X 0.

The preparation of compounds of formulas 10 to 12 with X = * NOH has already been rewritten above (oximation of a compound of formula 7) · The preparation of compounds of formulas 10 to 12 with X = 0, ie also of compounds with formula 6, may be carried out in such a way that a compound of formula 7 with hydroxylamine or a salt thereof is converted into a lower alcohol, preferably ethanol, with the addition of sodium acetate to the corresponding mono-oxime of formula 6 (see also the example part ).

The starting compound of formula 7 is obtained, for example, by diazotization of a suitable aniline of formula Z-NH 9 and coupling of the resulting diazonium salt solution with a compound of formula 14 (see also D. Leuchs, Ch'em. Ber. (1965) 1335 »See also the example section.

The compounds of formula 14 are known or can be easily obtained by known methods.

The intermediates of formula 9 obtained in the above-described second process for the preparation of compounds of formula 1 are new and are also an object of the present invention. Preferred compounds of formula 9> correspond to those of formulas 2 to 5 except that the group -CR £, -CR £, -CR ^ ', 0 8 0 · reap . -C-CH, by the group -C-R ", -C-RJJ, -C-R ^", respectively. -C-CH, yy 3 H 2 II 2 II 2 II 5 Η0Η Ν0Η Ν0Ξ Ν0Η has been replaced. Also preferred here are the oxime compounds, wherein R 1, R 1, R 1, J, respectively. Ri} 'represent methyl.

The preferred 2-phenyl-2H-1,2,3-triazoles of formula 1, wherein R 9 represents methyl, are valuable starting materials for the preparation of 2-phenyl-2H-1,2,3 triazol-4-ylacetic acids and their derivatives, which in turn are intermediates for the preparation of optical brighteners. With the aid of the compounds according to the invention of the formula I, a novel, particularly favorable route for the preparation of these practically significant triazolyacetic acids is opened.

Heretofore, these acetic acids have been prepared by various routes, but all with certain drawbacks, respectively. difficulties have been kept 8203209-10. See, for example, DE-OS 2,329,991, NL-OS 74-07127, Chem. Abstr. 88, 170153η (1978), Chem. Abstr. £ 8 (1977) 201547.

The other 2-phenyl-2H-1,2,3-triazoles of the formula according to the invention, in which R1 of methyl differs, can also be used as starting materials for the preparation of the aforementioned 2-phenyl-2H-1,2 , 3-Triazol-4-ylazl] nztaHi and their derivatives are used. To this end, they may first be converted to compounds of formula 1, wherein R 1 represents methyl, according to known methods, the latter compounds being further convertible to the corresponding triazolylacetic acids as described below. For example, triazoles of Formula 1, wherein Eg of methyl differs, may first be oxidized to an acid of Formula 18, preferably using KMhQ 4. The acids of formula 18 can then be converted into the corresponding acid chlorides (for example by chlorination with PCl, PClcj, SOClg, SOgClg, among others) and the latter can be converted with a methyl magnesium halide (CH 2 MgX, X = C1, Br, j) using the Grignard reaction to convert to the corresponding triazoles of formula 1 wherein 20 Rg is methyl. The process steps described above are known from the textbooks of organic chemistry.

According to the invention, 2-phenyl-2H-1,2,3-triazol-4-ylacetic acids of formula 15 and their derivatives, wherein Z is unsubstituted or substituted phenyl and R 1 -hydroxy, C 1 -C, can be used in a particularly advantageous manner. ^ -alkoxy or a group of the formula -0 ^ ® or -HY ^ Ypj, wherein Y ^ and Y ^ independently of each other are hydrogen or C ^ -C ^ -alkyl or Y ^ and Y ^ together with the nitrogen atom to which they are attached a heterocyclic saturated 5- or β-ring, which optionally still contains an oxygen, sulfur-30 and / or nitrogen atom as ring component and which may optionally be substituted with 1 or 2 C 1 -Calkyl groups, a salt -shaped cation, prepare by converting a 2-phenyl-2H-1,2,3-triazole of the formula 16 with morpholine, piperidine or dimethylamine and sulfur to a 2-phenyl-2H-1,2,3- triazole-4-35 ylthiooetamide of formula 17, wherein X 2 represents a group of formula 13, 19 or -N (CH 2) 2, converts the latter without isolation to the corresponding 2-phenyl-2H-1,2,3-triazole- 4 -yl acetic acid hydrolyses and optionally converts an acid thus obtained by customary methods into a salt, an ester or an amide.

8203209 - 11 -

Preferred definitions for preferred (salt-forming cation) and preferred heterocyclic saturated 5- or 6-membered rings (Y, + Yj-) in formula 15 are given in conjunction with * 4 2 12 formula 1 (e.g., Y + Y) and similar preferred ranges also apply to the compounds of formula 15

Triazolylacetic acids which are preferred in the context of formula 15 are obtained as starting materials instead of compounds of formula 1 which are used with formulas 2 to 5 (each time with Rg = CH2). Optional conversions of obtained compounds of formula 15 with R 2 = 0 (free acid) to corresponding salts, esters and amides can be carried out by conventional salt formation, esterification and amidation processes.

To prepare the triazolylacetic acids of formula 15, a compound of formula 16 is preferably reacted with morpholine, piperidine or dimethylamine and sulfur powder (Villgerodt-Eindler reaction). It is also possible to use amines other than those mentioned, for example diethylamine, piperazine, thiomorpholine and other amines commonly used for the Willgerodt-Kindler reaction. The conversion generally takes place without a solvent. The temperature is about 50-150 ° C, preferably 80-120 ° C. The thioamide obtained, which is not isolated in the 3 parts, can then be converted into the corresponding acetic acid or acetic acid by means of a base in an aqueous medium. its salt hydrolyzed. As base, an alkali metal hydroxide, in particular NaOH, is preferably used. The hydrolysis is advantageous when operating at elevated temperature, preferably at reflux temperature.

Also, the conversion of the acetyl triazoles of formula 16 to 50 is corresponding triazolyacetic acids using ammonium polysulfide; and subsequent hydrolysis of the intermediate takes place (Willgerodt reaction). A solvent can also be used in this variant, for example dioxane.

The compounds of formula 15 are partly known, but many of them are new. The compounds of formula 15 are also subject of the present invention as far as they are new.

As already mentioned, the triazolylacetic acids and their derivatives of formula 15 for the preparation of optical bleaching agents of the 5- (2'-phenyl-2Ή-11,2 '' 3'-triazol-'4, -yl) coumarin 8203209-12 series. Methods for the preparation of such bleaching agents using 2-phenyl-2H-1,2,3-triazol-4-ylaczenes and their dexisrates are described in U.S. Patent 3,966,755 and British Patent 1,412,049.

As already mentioned above, the literature also discloses, inter alia, 2-phenyl-4-acetyltriazoles, which are substituted in the 5-position with a methyl group. See for example DE-PS 1,226,591 »E-Klingsberg, Synthesis 1972 (9), 475-7 and Chem. Ber. However, the triazoles of the formula II according to the invention, which are unsubstituted in the 5-position, are surprisingly insofar as valuable products are produced in that the emit can be prepared 3- (4) (1965) 1335-41. 2-phenyl-2, H-1 ', 2', 3'-triazol-4'-yl) margin bleaches (via the intermediate stage of the corresponding triazolylazines) have substantially more favorable bleach properties. For example, on textile materials, for example synthetic fibers, in particular polyester fibers, they achieve substantially higher degrees of whiteness than all bleaching agents, which nitrate in the 5-position with methyl-2-phenyl-4-acetyl-2Ξ-1,2-methyl , 3-triazoles can be prepared.

In the following examples, which further illustrate the various aspects of the present invention, without being limited thereto, parts and percentages are, unless otherwise indicated, parts by weight and parts by weight. Melting and boiling points are not corrected, unless stated otherwise.

Example I.

205 g of 2-phenylazoacetoaciesbaldehyde-1-oxime with formula 20 are dissolved in 1250 ml of water at 40 ° C, containing 44 S sodium hydroxide, and cooled with stirring at 15 ° C, partially precipitating the sodium salt of the oxime. . 112 g of acetic anhydride are added dropwise over vigorous stirring. The pH value is kept between 11.5 and 12 by simultaneous dripping of concentrated sodium hydroxide solution and the temperature is kept at 15-17 ° C by means of cooling at once. The reaction product separated after the reaction has ended is filtered off, washed with water and dried. 179 g (corresponding to 96% of theory) of 4-acetyl-2-phenyl-2H-1,2,3-triazole of formula 21 are obtained in this way as a beige product, which, after recrystallization, produces nit hexane at 95-96 ° C. C melts.

40 Analogously, using the appropriate 8203209 -15-

a

substituted 2-phenylazoacetoacetaldehyde-1-oximes of formulas 112-130 (see example 11) as starting products, also the 4-acetyl-2-phenyl-2H-1,2,3-triazoles of formula 22 listed in Table I.

5 Table. a

Compound No. R R "Melting point 42 4-CN" 154-157 43. 4-CH, Ξ 82-83 5 10. 44 ^ 3-CH5 1 60-61 45 2-CH, H 59-60 o 46 4-C1 H 110-111 47 .3-01 Ξ 113-114 48 2rCl H 70-72 15 49 4-OOH, H 112-113 y 50 3-ohh h 72-73 51 2-0CH, H 58-60 5 52 4-C00H H 261-262 53 4-NO2 H 123-125 20 54 4-0-CgH5 H 108-110 55 4-C1 2-C1 103-105 56 4-S02CH5 H 176-178 57 3-SO ^ Na H> 300 25 58 4 - / \ -C00H Ξ 268-269 4 / mm · 59 4-r H 114-118 60 4-Br H 114-116 30 ° P analogous manner also using the suitably substituted 2-phenylaBoacetoaetaldehyde-1-oximes of formulas 131-181 (see example If), as starting materials also the 4-acetyl-2-phenyl-2H-1,2,3-triazoles of formula 23, which are mentioned in the following table A1, are obtained.

8203209

Table_A1_.

- 14 -

Yerbinding No. R R "R"

61 4-C „H, H H

2 5 62 3-Br Η Ξ

63 2-1 I H

5 64 4-J Η H

65 3-J Η H

66 2-J Ξ Ξ

67 4-OF, Ξ H

3

68 2-CI-, Η H

3

10 69 4-1-Ο, Ε, Η H

3 (70 4-n (ch3) 2 η h

71 3-CH, 4-Br H

3 72 3-ra2 ξ h

73 3-MS02Ci-3 Ξ H

15 74 3-no2 4-oh5 i 75 3-m2 4-ch3 h

76 3-MSO 2 CR5 4-CH 3 H

77 3-01 4-CH, H

3

78 3-m2 4-01 H

20 79 3-MS02CR5 4-C1 Ξ

80 3-01 4-C1 H

81 3-00Ξ, 4-0CHz H

3 3 82 3-0CH, 5-0CH, Ξ 3 3 83 3-01 5-01 Ξ

25 84 2-Br 4-Br H

85 3-MSO2C: Fz 4-CH, 6-CH, 2 5 5 5 86 3-RHS0CI-2 4-CH, 5-CH, 2 5 5; 5 87 2-F 4-F | 3 88 3-0F, Μ Ξ 5 30. · "· 89 4-0- / * .- Cl Η Ξ \ = / • - · 90 2-01 6-01 Ξ 91 2-C1 3-01 4-01 55 92 2-C1 4-01 5-01 93 2 3-NO2 4-CH3 6-CH3 94 j 3-M2 4-0H3 6-CH3 8203205

Table A1 continued - 15 -

Connection No. R R »95 3-CR H e

96 2-CN H R

5 97 3-SCH5 H H

98 5-SOCH: · Η H

99 3-N02 Η 1

100 2-ro 2 H H

101 2-CH 4-Br H

10 102 2-CN 4-C1 H

103 3-CT ^ 4-C1 E

104 3-01 ^ 4-NOg H

105 4-01 ^ 2-R02 E

106 2-CH ^ 4-C1 H

15 107 3-no2 4-C1 E

108 3-001 ^ H i H

109 4-001 ^ 2 1 H

110 2-OCH3? 2 Η H

111 4 ~ 00P2CHF2 Ξ H

20 *) Be connection Rr. 93 has a melting point of 127-129 ° 0.

The other 2-phenyl-2H-1,2,3-triazoles of the formula 1 can also be obtained using the suitably substituted starting materials of the type of the formula. Image II.

2-phenylazoacetoacetaldehyde-1-oxime of formula 20 is prepared as follows:

A solution of 170 g of sodium acetate trihydrate in 300 ml of water is added to a suspension of 190 g of 2-phenylazoacetoacetaldehyde of formula 26 in 300 ml of ethanol, followed by a solution of 76.5 g of hydroxylamine hydrochloride in 100 ml of water. The suspension is stirred at 50 ° C for 5 hours and cooled to 20 ° C. The precipitate is filtered off with suction, washed with water and dried. In this way 190 g (92.5% of theory) of 2-phenylazoacetoacetaldehyde-1-oxime of formula 20 with a melting point of 152-153 ° C are obtained after crystallization from toluene.

In an analogous manner, using the substituted 8203209-16-substituted 2-phenylazoacetoacetaldehydes of formulas 182-200 (see example HI) as starting products, the 2-phenylazoacetoacetaldehyde-1-oximes of formula 24 shown in Table B are also prepared. .

5 label B.

Yerbinding R R 'Melting point ____ Co) _ * 112 4-CR H 183-185 113 3-CEj H 195-197 114 3-ch5 H 167-168 10 115 2-CHj H 175-176 116 4-C1 H 196-197 117 3-C1 H 171-172 118 2-01 H 174-175 119 4-OOHj H 163-165 15 120 3-OCH5 H 131-132 121 2-0CH5 H 190-192 122 4-C00H Ξ 243-147 123 4-eo2 h 222-224 124 4-0- f \ π 129-131 \ _ i • - * 20 125 4-01 2-C1 197-199 126 4-S020H5 H 203-204

127 3-S0-.Ha H

5 128 4 -f ^ .- 000H H 250-252 \ _ / • ·

129 4-R H

25 130 4-Br

Analogously, 2-phenylazoacetoacetaldehyde-1-oximes of formula 25, as well as the other oximes of formula 6, listed in Table 6 are obtained using the suitably substituted starting materials of the formula of the formula 26.

8203209 i - 17 -

Table B1 Λ Connection No. R R1 R "131 4-C2H5 h h 132 3-Br Η Ξ 5 133 2-P Η Ξ 134 4-J Ξ Ξ 135 3-J Ξ Ξ

136 2-J Ξ H

137 4-CR5 Π Ξ

10 138 2-GRj Η H

139 4-i-C5H7 Η Ξ 140 4 “R (ch5) 2 Η Ξ

141 3-CH 4-Br H

142 3-M2 Η Ξ 15 143 3-HHS02C: F3 Ξ j Ξ

144 5-NO2 4-CH5 I H

145 5-M2 4-CH5 j H

146 3-MSO2CF5 4-CHj | H

147 3-01 4-CH5 I Ξ

20 148 3-M2 4-C1 E

149 3-UHS02CP5 4-C1 j E

150 3-01 4-01 | H

151 3-OCH5 4-OOH5: H

152 3-OCH5 5-OCHj j Ξ

25 153 3-01 5-01 | E

154 2-Br 4-Br j H

155 3-MS02CP5 4-CH5 j 6-CH3 156 3-NHS02CP3 j 4-CH5 j 5-CH3

157 2-P 14-11 l E

30 158 3-cp3 ξ! H

i 159 4- -0-f * .- Cl H! Ξ \ / i j

160 2-C1 j 6-C1 j H

161 2-C1 3-01 4-01 162 2-C1 4-C1 5-01 8203209

Table B1 continued - 18 - ----

Yerbinding No. R R 'R "

165 5-N0p 4-CH, 6-GE

3 3 164 3-M2 4-CH5 6-CH2

5 165 3-CM Η H

166 2-CR Η H

167 3-sch5 Η Ξ

168 3-SOCH3 H H

169 3-no2 H H

10 170 2 -R02 E H

171 2-CH5 4-Br H

172 2-CR 4-C1 Ξ 173 3-01 ^ 4-C1 Ξ

174 3-01 ^ 4> H02 H

15 175 4-Ci ^ 2-H02 Ξ

176 2-CH 4-C1 H

177 3-U02 4-C1 Ξ

• 178 3-OCFj Η H

179 4-00 ^ I H

20 180 2-00ΗΡ2 Η H

181 4 “00F2CEP2 H H

Figure III.

2-phenylazoacetoacetaldehyde of formula 26 is prepared as follows: a diazonium salt solution prepared in a conventional manner from 1 mole of aniline is allowed to stir in an aqueous solution of 1.1 mole of 1-dimethylamino-butene-1-one under stirring at 5-6 ° C. 3 (cf. D. Leuchs, Chem. Ber. £ 8 (1965) 1335). The pH of the coupling solution is adjusted to 3> 8-4 by adding portions of sodium acetate. The mixture is stirred at 12-15 ° C until the coupling is finished and the yellow coupling product is then filtered off. This is washed with water and dried. In this way 175.8 (corresponding to $ 2% of theory) of 2-phenylazoacetoacetaldehyde of formula 26 is obtained as yellow-orange product, which melts at 117-118 ° C after recrystallization from ethanol.

8203209 - 19 -

In an analogous manner, using the diazonium salt solutions of the substituted substituted anilines as starting materials, the 2-phenylazoacetoacetaldehydes of formula 27 listed in Table C below were also obtained.

5 Table C

Yerbinding No. RR 'Melting point (0) 182 4-CI Ξ 156-158 183 4-CHj H 103-105 184 5-CH, S 76-77 5 10 185 2-CH, Ξ 91-92 j 186 4-CI H 122-123 187 3-01 H 114-115 188 2-01 H 117-118 189 4-0CHj H 107-109 15 190 3-0CH, H 94-96 7 191 2-00Ξ, H 119-121 7 192 4-COOH Ξ 234-236 195 4-H02 H 177-178 20 194 4-0 -. * ^ H 79-81 \ / • 5 · 195 4-01 2-01 121-122 196 4-S02CH5 H 167- 168 197 3-SOjNa H> 300 198 4- - (VcOOH H> 300 \ / «· 25 199 4-F Ξ 200 4-.Br 'Ξ

Similarly, using the appropriately substituted anilines and the appropriate 1-dimethylamino-but-1-one-3 compounds as starting products, 2-phenylazoacetoacetaldehydes containing the same substituents as the compounds 131 in the phenyl ring to 181 (Table B1), as well as the other 2-phenylazoacetoacet-8203209-20 aldehydes covered by formula 7.

Example 17.

a) 190 g of 2- $ tenylazoacetoacetaldehyde of formula 26 are suspended in 400 ml of 15 ° C pyridine and 146 g of hydroxyl-5-amine hydrochloride are added in portions, the temperature being raised to 15-20 ° C by external cooling. The now dark solution is then stirred at room temperature for 16 hours. 600 ml of water are now added to the reaction mixture, the mixture is stirred well and the separated reaction product is filtered off with suction, washed with water and dried. 107 g (corresponding to 94% of theory) of the 2-phenylazoacetoacetaldehyde-1,3-dioxime of the formula 28 are obtained in this manner, which after recrystallization from a mixture of equal parts of ethanol and water at 159-160 ° C melt.

B) 220 g of 2-3-enylazoacetoacetaldehyde-1,3-dioxime of formula 28 are dissolved in 2000 ml of water containing 80 g of sodium hydroxide. 205 g of acetic anhydride are added dropwise under stirring at 10-15 ° C over a period of 2 hours. By adding dropwise concentrated sodium hydroxide solution at the same time, the ρΞ value is raised between 11.5 and 12. After the reaction has ended, the slurry is brought to a pH of 6 by addition of diluted sun acid and the separated reaction product is filtered off, washed with water and dried. This gives 200 g (corresponding to 10090 of the theory) of 25 4-acetyl-2-phenyl-2H-1,2,3-triazoloxime of formula 29 as a beige product which, after recrystallization from chlorobenzene at 175 -176 ° C melts.

c) 20 g of 4-Acetyl-2-phenyl-2H-1,2,3-triazoleoxime of formula 29 and 36.4 S sodium bisulfite are mixed in a mixture of 100 ml of ethanol and 50 ml of water for 24 hours while stirring at r .flute temperature heated. After cooling, the mixture is diluted with 200 ml of water, brought to pH 3 with hydrochloric acid and the precipitated product is filtered off with suction, washed with water and dried. 17.5 g (corresponding to 93.5% of theory) of 4-acetyl-2-phenyl-2H-1,2,3-triazole of formula 21 are obtained in this way as a beige product, which is obtained at 95-96 ° C melts.

Step c) can be carried out in the following manner: 20 g of 4-acetyl-2-phenyl-2H-1,2,3-triazole oxime of formula 29 and 4.5 g of paraformaldehyde are added in a mixture of 100 ml of water and 40 10 ml 30% hydrochloric acid heated to reflux temperature for 24 hours.

8203209 - 21 -

After cooling, the mixture is diluted with 200 ml of water, the precipitated product is filtered off, washed with water and dried. This gives 17.9 (corresponding to 96% of the theory) 4- & cstyl-2-phenyl-2E-1,2,3-triazole with formula 21 as a beige product, which at 93-96 ° G melt.

According to the procedure of Example IV, using suitable 2-phenylazoacetoacetaldehydes of the formulas 182 to 200 ale starting products, the compounds of the formulas 42 to 60 listed in Table 1 are also obtained, with 10 00k the correspondingly substituted intermediates of the type having formulas 28 and 29 are obtained.

Example V.

250 g of 2- (4-nitrophenylazo) -acetoacetaldehyde-1-oxime of formula JO are suspended in 1000 ml of water containing 40 sodium hydroxide, stirred well for JO minutes at room temperature, mixed with 1000 ml of methylene chloride and the mixture is cooled to 15 ° C with stirring. 204 g of acetic anhydride are added dropwise with vigorous stirring over a period of time.

By simultaneously adding concentrated sodium hydroxide solution dropwise, the pE value is kept between 11.5 and 12 and the temperature is kept at 15-17 ° C by external cooling. After the completion of the reaction, the two-phase mixture is separated, the organic phase is washed with water, dried briefly over magnesium sulfate and evaporated. In this way, 161 g (corresponding to 69.5% of theory) of 4-alpha-ethyl-2- (4-nitrophenyl) -2E-1,2,3-triazole of formula 31 are obtained as a brown product, which , after recrystallization from alcohol, in light brown crystals with a melting point of 12 DEG-125 DEG C. are obtained.

Example VI.

93-5 5 3-Oxo-3-phenyl-2-phenylazopropionaldehyde-1-oxime of formula 32 are suspended in 500 ml of water containing 30 g of sodium hydroxide, stirred well for 30 minutes at room temperature, mixed with 300 ml of methylene chloride and the resulting mixture is cooled to 15 ° 0 with stirring. Acetic acid anhydride is then added dropwise with vigorous stirring in 2 hours over a period of 2 hours. By simultaneously adding concentrated sodium hydroxide solution dropwise, the pH value is kept between 11.5 and 12 and the temperature is kept at 15-17 ° 0 by external cooling.

After the completion of the reaction, the biphasic mixture is separated, the organic phase is washed with water, dried briefly over magnesium sulfate, evaporated and the residue is distilled under vacutim. 81.7 (94% of theory) of 4-benzoyl-2-phenyl-2H-1,2,3-triazole of formula 33 is thus obtained as a yellow-orange substance with a boiling point of 165-170 ° C / 1.7 kPa 5 and a melting point of 49-51 ° C.

Analogously, according to the foregoing method, using the compound of formula 34, which has a boiling point of 117-, is obtained by using 3-oxo-3- (p-methylphenyl) -2-phenylazopropion-aldehyde-1-oxime of formula 35 182 & C / 1.7 kPa JO and has a melting point of 63-64 ° C.

Example VII.

3-oxo-3-phenyl-2-phenylazopropionaldehyde-1-oxime of formula 32 is prepared as follows:

To a suspension of 126 g of 3-oxo-3-phenyl-2-phenylazopropionaldehyde 15 (known from Berichte der deutschen Ghem. Ges. _21_ (1888), 1697) in 500 ml of ethanol is added dropwise a solution of 85 g of sodium acetate trihydrate in 200 ml water, followed by a solution of 36.5 g of hydroxylamine hydrochloride in 100 ml of water. The suspension is stirred at room temperature for 20 hours, the precipitate formed is filtered off, washed with water and dried. 124 g (93% of theory) of 3-oxo-3-phenyl-2-phenylazopropionaldehyde-1-oxime of formula 32 having a melting point of 192-193 ° C after crystallization from ethanol are thus obtained.

In an analogous manner, according to the foregoing method, using 3-oxo-3- (p-methylphenyl) -2-phenylazopropion-aldehyde (known from Berichte der deutschen Chem. Ges. (1926), 108) as the starting product, the 3- oxo-3- (p-methylphenyl) -2-phenyl-azopropionaldehyde-1-oxime of formula 35 which, after crystallization from a mixture of ethanol and dimethylformamide, has a melting point of 206-107 ° C.

Example VIII.

To a solution of 93> 5 g of 4-acetyl-2-phenyl-2H-1,2,3-triazole of formula 21 in 56.5 S morpholine, 17.6 g of sulfur powder, piglet 70 ° C are added and the resulting dark brown melt 35 is stirred at 100-105 ° C for 4 hours. Now 250 ml of 17% NaOH are added dropwise and the reaction mixture is kept under reflux for another 4 hours. After cooling to 80 ° C, the mixture is brought to a pH of 7 with hydrochloric acid, the temperature is stirred for 30 minutes, diluted to 1000 ml with water and filtered with clarity. The clear solution is then adjusted with hydrochloric acid at a pH of 8203209-23 and the precipitated beige product is filtered off, washed with water and dried. In this way, 90 g (corresponding to 88.596 of the theory) of 2-phenyl-2H-1,2,3-triazol-4-ylacetic acid of formula 36 are obtained, which after church crystallization nit is a mixture of 1 part of toluene and Melt 2 parts of ligroine at 109-110 ° C.

Similarly, using the suitably substituted 4-acetyl-2-phenyl-2H-1,2,3-triazoles of formulas 43-52, 55, 56 and 59 as starting products, also the products listed in the following table substituted 2-phenyl-2H-1,2,3-triazol-4-ylacenes of formula 37 are obtained.

Table P.

j --------—--: - • Yerbinding No. RR * Melting point j __ (° o) 201 4-CH, H 116-117 o 15 202 3-CHj H 8.6-87 205 2- CH, Ξ 47-48 204 4-01 H 151-152 205 3-Cl H 139-140 206 2-C1 H 95-96 20 207 4-0CHj H 140-141 208 3-OCH ^ H 78-80 209 2 -0CH ^ Ξ 99-101 210 4-OOOH Ξ 264-265 211 4-S02CH3 H 197-198 25 212 4-C1 2-C1 107-109 213 4-F Ξ 136-140 _ I_

In an analogous manner, using the 2-phenyl-2H-1,2,3-triazoles with the formnles 53, 54, 57, 58, 60 and 61-111 as starting products, the correspondingly substituted 2-phenyl-30 2Ξ-1 2,3-tniazol-4-ylacetic acids. The aforementioned 2-phenyl-2H-1,2,3-triazol-4-ylacine enzymes can be converted into derivatives by conventional methods, for example in suns, esters, thioesters, amides or thioamides.

Example IX.

As already mentioned, the nit 2-phenyl-2H-1,2,3-8203209-24-triazoles of formula 1 according to the invention can be obtained 2-phenyl-2H-1,2,3-triazol-4-ylacetic acids and their derivatives (see formula 15) are used for the preparation of optical brighteners, in particular those of the 3 * triazole-4-ylcumarin series (see, for example, U.S. Patent 3 * 966,755 and British Patent 1,412,049 For example, such bleaches can be obtained as follows: a) In a mixture of 13.5 g of the sodium salt of the 2-phenyl-2H-1,2,3-triazol-4-ylacetic acid of formula 36 and 135 ml * 10 azic anhydride is charged with 10.3 g of 2-hydroxy-1-naphthaldehyde.

The reaction mixture is heated to boiling for 1 hour with stirring and refluxed for 5.5 hours. After the reaction mixture has cooled to about 80 ° C, it is brought to about 1700 ml of cold water and after a few hours the product is filtered off, washed with water and dried under vacuum at 60 to 70 ° C. A preliminary purification by recrystallization from 235 ml of chlorobenzene gives a pre-purified product. 1a recrystallized twice from chlorobenzene using bleaching earth, the compound of formula 38 is obtained in the form of yellow crystals with a melting point of 238 to 238.5 ° C. b) In a mixture of 14.6 g of the sodium salt of the 2-phenyl-2H-1,2,3-triazol-4-ylacetic acid of the formula 36 and 130 ml of acetic anhydride, 9.9 g of 2-hydroxy-4- methoxybenzaldehyde. The reaction mixture is heated to boiling in 1 hour and refluxed for 7.5 hours. After the reaction mixture has cooled to about 80 ° C, it is brought to about 1700 ml of water and after hydrolysis of the excess acetic anhydride has taken place, the reaction product is filtered off with suction, washed with water until neutral and then with a little alcohol to form a paste 30 and the crystalline product is filtered off and washed again with alcohol. After recrystallization from chlorobenzene by means of bleaching earth, the compound of formula 39 is obtained in the form of yellowish crystals with a melting point of 196 to 196.5 ° C.

Proceed as described in the preceding regulation b), but replace the sodium salt of the 2-phenyl-2H-1,2,3-triazol-4-ylacetic acid of the formula * 36 with equivalent amounts of the sodium salts of the 2- (m-chlorophenyl) -2H-1,2,3-triazol-4-yl-acetic acid of the formula 200, 2- (p-methylphenyl) -2H-1,2,3-triazol-40 4-ylacetic acid of the formula 201 or the 2- (p-methyl-m-chlorophenyl) -2H-8203209 4 - 25 - 1,2,3-triazol-4-ylacetic acid, the compounds 2- (m-chlorophenyl) usable as optical brighteners are obtained -4- (7. Metho2ycumarin-3'-yl) 2H-1,2,3-triazole (melting point: 202-203 C), 2- (p-methylphenyl) -4- (7'metho: xycumarin-3 ' -yl) 2H-1,2,3-triazole 5 (melting point 202.5-203 ° 0) reap. 2- (p-methyl-m-chlorophenyl) -4- (7'-methoxycoumarin-3'-yl) 211-1,2,3-triazole (mp: 241-24-24 ° C).

8203209

Claims (15)

20 represent -SO ^, -COOY ^, ”S (0) n- (C1-C ^ -alkyl) or -S (0) n- (C1-C4-haloalkyl), where Y ^ and Y ^ are independent of each other hydrogen or C 1 -C 2 -alkyl, Y 2 -hydrogen, C 1 -C 2 -alkyl or a salt-forming cation and n represent the number 0, 1 or 2. . 2-phenyl-2H-1,2,3-triazoles according to claim 2 of formula 3> wherein R 1, C 1 -C 2 -alkyl, benzyl, unsubstituted or with 1 or 2 substituents from the group chlorine, C -C 1 -alkyl, methoxy, nitro, cyano-4 and / or trifluoromethyl, substituted phenyl and R 2 and R 2 independently hydrogen, halogen, trifluoromethyl, cyano, nitro, C 1 -C 2 -alkyl, C 1 -C 2 -alkoxy, O 2 -C 2 -alkylsulfonyl, unsubstituted with halogen, C 1 -C 2 -alkyl, C 1 -C 2 -alkoxy, cyano, nitro, trifluoromethyl or a group of the formula -COOYi or -S0TYi substituted phenyl or phenoxyj or a group of the formula -S0, Ya, -C00Y * 00 0 or -NY.jY2, where Y ^, Y2 and Y ^ as defined in claim 35 and Y 'represents hydrogen, an alkali metal or ammonium ion. 2-Slenyl-2H-1,2,3-triazoles according to claim 3 of formula 4> wherein RJJ, C 1 -C 1 -C 2 alkyl, benzyl or unsubstituted or with 1 or 2 substituents of the chlorine group , methoxy and / or methyl substituted 8203209-27-phenyl, H ”hydrogen, halogen, trifluoromethyl, cyano, nitro, C 1 -C 2 -alkyl, G 2 -C 2 -alkozy, G 1 -C 2 -alkylsulfonyl, unsubstituted - doped chlorine, methyl, methoxy, cyano, nitro, sulfo or carboxy or their alkali metal or ammonium salts substituted phenyl or phenoxy; or a group of the formula -SO ^ Y ^, -COOY ^ or -irYjYg, wherein Yj, Yg and Y ^ are as defined in claim 3 and R 'is hydrogen, halogen, C 1 -C 2 -alkyl or C ^ -C ^ -alkoxy. 2-i'-enyl-2H-1,2,3-triazoles according to βέη or more of claims 1 to 4> wherein Rg, Rl, HJJ represents ^ y ^. 6. 2-phenyl-2H-1,2,3-triazoles according to conelusion 3 of formula 5 wherein R 2 'is hydrogen, halogen, C 1 -G 2 -alkyl, C 1 -C 2 -alkoxy, cyano, nitro, sulfo or carboxy and their alkali metal or ammonium salts, C 1 -Calkylsulfony1, phenoxy, phenyl, chloro-phenyl, methylphenyl or carboxyphenyl and their alkali metal or λ ammonium salts and R 2 'hydrogen, halogen, methyl or methoxy. 7. A process for preparing 2-phenyl-2H-1,2,3-triazoles of formula 1, wherein R 8 represents C 1 -C 8 alkyl, unsubstituted or substituted phenyl or benzyl and Z is unsubstituted or substituted phenyl, with characterized in that an oxime of formula 6, wherein Z and Rg are as defined above, is cyclized to form the corresponding triazole in the presence of a condensing agent. 8. Process according to claim 7 for the preparation of 2-phenyl-2H-1,2,3-triazes of formula 4> wherein R 1 V 2 -C 1 -C 2 alkyl, benzyl or unsubstituted or with 1 or 2 sub * · stituents from the group of chlorine, methoxy and / or methyl substituted phenyl, R 2 hydrogen, halogen, trifluoromethyl, cyano, nitro, C 1 -C 2 -alkyl, C 1 -C 2 -alkoxy, C 1 -C 2 -alkylsulfonyl, unsubstituted or substituted with chlorine, methyl, methoxy, cyano, nitro, sulfo or carboxy or their alkali metal or ammonium salts or phenoxy; or a group of the formula -SO ^ Y ^, -COOY ^ or -IJY ^ Yg, wherein Y ^, Yg and Y ^ are as defined in claim 3, and R ^ is hydrogen halogen, C ^ -C ^ -alkyl or G 1 -C 2 -alkoxy, characterized in that an oxime of formula AO, wherein R 1, R, and R 2 as defined above, is ring-closed in the presence of a condensing agent to the corresponding triazole. 9. Process according to claim J or 8, characterized in that an oxime is started from, in which Rg resp. R 8203209-28 - methyl. 10. Process according to one or more of claims 7 to 9, characterized in that the condensing agent used is an acid anhydride or an acid halide, for example acetic anhydride, propionic anhydride, acetyl chloride, benzoyl chloride, benzenesulfochloride, methanesulfochloride, ethanesulfoxychloride, ethanesulfoxychloride , preferably using acetic anhydrode. 11. Process according to claim 10, characterized in that the cyclization with acetic anhydride is carried out in the presence of water at a pH value between 10 and 13, the reaction medium optionally still containing a water-miscible organic solvent or, in the case of water-soluble final products, may contain a water-immiscible organic solvent. A process for preparing 2-phenyk-2H-1,2,3-triazoles of formula 1, wherein R 8 represents C 1 -C 8 alkyl, unsubstituted or substituted phenyl or benzyl and Z is unsubstituted or substituted phenyl, with the characterized in that a compound of formula 7 not hydroxylamine or a salt thereof is converted into a dioxime of formula 8, the latter is cyclized in the presence of a condensing agent to form a triazole of formula 9 and hydrolyzed to the corresponding ketone. Oximes of formula 10, wherein R 8 represents C 1 -C 8 alkyl, unsubstituted or substituted phenyl or benzyl, Z is unsubstituted or substituted phenyl and X represents 0 or Ε0Η. Oximen according to claim 13 of formula 11, wherein X 0 or R 0 H, R 8 C 1 -C 1 -alkyl, unsubstituted phenyl or benzyl 30 or with 1 or 2 substituents from the group halogen, C 1 -C 2 -alkyl, C 1 -C 2 -alkoxy, C 1 -C 2 -alkenyl, nitro, cyano, carboxy or sulfo and their derivatives, phenyl or benzyl and R 2, R 2 and R 2 independently substituted with C 2 -C 2 carbaloxy or trifluoromethyl from each other hydrogen, halogen, trifluoromethyl, cyano, nitro, C 1 -C 2 -alkyl, C 1 -C 2 -halo-35 alkyl, C 1 -C 2 -hydroxyalkyl, C 2 -C 8 -alkoxyalkyl, C 1 -C ^ -alkenyl, C ^ -C ^ -alkoxy, C ^ -C ^ -haloalkoxy, C8 -C8 alkoxyalkoxy, unsubstituted or with halogen, C ^ -C ^ -alkyo, C ^ -C ^ -alkoxy, Cg-Cpj -carbaloxy, C 1 -Calkylsulfonyl, cyano, nitro, trifluoromethyl or a group of the formula -COOY 2 or -SO 2 Y 2 single or multiply substituted phenyl or phenoxy; or έέη of the groups with the 8203209 -29 formula -C-HHg, -ΪΥ ^, -SO ^, -COOYy -3 (0 ^ - (0, - (3 4 «alkyl) or S -S (0 ) n- (C 1 -C 1 -haloalkyl), wherein Y 1, and Yg independently hydrogen or C 1 -C 2 -alkyl, Y 2 hydrogen, 5 C 1 -C 2 -alkyl or a salt-formed cation and n represent the number 0, 1 or 2. Oximes according to claim 14 of formula 12, wherein X 0 or UTOH, E ', O, - C 1 -alkyl, benzyl or unsubstituted or with 1 or 2 substituents from the group of chlorine, methoxy and / or methyl substituted Phenyl, R 2 hydrogen, halogen, triflormethyl, cyano, nitro, 0.-C 2 -alkyl, 0.-C 2 -alkoxy, 0.-C 2 -alkylsulfonyl, unsubstituted or with chlorine, methyl methoxy, cyano, nitro, sulfo or carboxy or their alkali metal or ammonium salts substituted phenyl or phenoxy; or a group of the formula -SO ^ Y ^ »-COOY ^ or -HY ^ Yg, where Y. ,, Yg and Y4 are as defined in claim 5 and R4 represents hydrogen, halogen, O4 -C1alkyl or C1-4 -C1alkoxy, wherein R 1 | preferably hydrogen, halogen, 0., -C 1 -alkyl, 0.-C 1 -alkoxy, cyano, nitro, sulfo or carboxy and their alkali metal or ammonium salts, C-C alkylsulfony1, phenoxy, phenyl, chlorophenyl, methylphenyl or carboxyphenyl and their alkali or ammonium salts and R "preferably represent hydrogen, halogen, methyl or methoxy. Oxime according to 6 and more of claims 15 to 15, wherein Rg, Rl or Rl represent methyl and X 0. Use of 2-phenyl-2H-1,2,5-triazoles of formula 16, wherein Z represents unsubstituted or substituted phenyl, as starting products for the preparation of 2-phenyl-2H-1,2 , 3-triazol-4-ylacetic acids of formula 41 and their functional derivatives and thus for the preparation of optical brighteners of the 3- (2ί-phenyl-2, Ξ-1, 2, 3, -triazole- 4-yl-coumarin series. 18. A process for preparing 2-phenyl-2H-1,2,3-triazol-4-ylacetic acids and their derivatives of formula 15 wherein Z is unsubstituted or substituted phenyl and R 1 -hydroxy, C 1 -C 6 -alkoxy or 35 represent a group of the formula -0 ~ M + or -ΚΥ / Ϊ ^, where Y ^ and Υ ^ independently of one another hydrogen or 0.-C ^ -alkyl or Y ^ and Y ^ together with the nitrogen atom to which they are bonded to form a saturated 5- or 6-membered heterocyclic ring, which may optionally contain an oxygen, sulfur and / or nitrogen atom as the ring component 40 and may optionally be substituted with 1 or 20 C 1 -alkyl groups. - 30 - and represent a salt-forming cation, characterized in that a 2-phenyl-2H-1,2,3-triazole of formula 16 with morpholine, piperidine or dimethylamine and sulfur to form a 2- phenyl-2H-1,2,3-triazol-4-ylthioacet-5 amide of formula 17 »wherein a group of formula 13, or a group of formula 19 or represents, converts and the latter without isolation to the corresponding 2-Phenyl-2H-1,2,3-triazol-4-ylacetic acid hydrolyses and optionally converts an acid thus obtained by customary methods to a salt, an ester or an amide. 19 · 2-Phenyl-2H-1,2,3-triazol-4-ylketoximes of formula 9, wherein C 1 -C 8 alkyl, unsubstituted or substituted phenyl or benzyl and Z represent unsubstituted or substituted phenyl. 15 8203209