DE2932305C2 - - Google Patents

Description

The present invention relates to pyrazolo- [5,1-d] - [1,2,3,5] - tetrazin-4-one and process for its manufacture of azolo- [5,1-d] - [1,2,3,5] -tetrazin-4-ones.

Until recently, [1,2,3,5] tetrazines were considered to be unstable, connections difficult to access. The first time Representation of this heterocyclic ring system was successful only a few years ago: Bull. Chem. Soc. Japan 49, 1339, (1976). However, condensed [1,2,3,5] tetrazines remained an unknown connection class. This is in the summary publication by H. Neunhoeffer and F.G. Wiley, "Chemistry of 1,2,3-Triazines and 1,2,4-Triazines, Tetrazines and Pentazines "in" The Chemistry of Heterocyclic Compounds "Vol. 33, A. Weissberger and E. C. Taylor editors, John Wiley and Sons, New York, 1978 on p. 1296 confirmed by there for the monocyclic basic system, the 1,2,3,5- Tetrazine, it is found that there are no examples of this class of tetrazines are known.

It has now been found that the previously unknown azolo - [5,1-d] - [1,2,3,5] -tetrazin-4-ones of the formula I

obtained in a surprising manner and in high yield by aminoazoles of the formula III  

diazotized, optionally deprotonated with bases, and the obtained azole diazonium salts or diazo-azoles with a Isocyanate of the formula IV

R⁴-NCO (IV)

implements.

In formulas I and III
A for N or C-R¹,
M for N or C-R²,
Z for N or C-R³, but not simultaneously A, M and Z for nitrogen,
R¹ for H, straight-chain or branched alkyl, cycloalkyl, benzyl, aryl, SH, S-alkyl, phenoxyalkyl,
R² is H, straight-chain or branched C₁- to C₁₂-alkyl, C₃- to C₈-cycloalkyl, benzyl or phenyl optionally substituted by methyl, trifluoromethyl, halogen, methoxy, cyano or nitro,
R³ for H, straight-chain or branched C₁ to C₄ alkyl, chlorine, bromine, cyano, nitro, alkoxycarbonyl having up to 4 carbon atoms in the alkoxy radical, benzyl or phenyl optionally substituted by halogen, methyl, trifluoromethyl, methoxy, cyano or nitro , Thienyl-2, Thienyl-3, or Pyridyl-3 or
R² and R³ together for a tetramethine chain
-CH = CH-CH = CH-, form a trimethylene, tetramethylene, pentamethylene or hexamethylene chain and in the
R⁴ for straight-chain or branched C₁- to C₁₂-alkyl, which can optionally be substituted by C₁- to C₃-alkoxy or halogen, for C₃- to C₈-cycloalkyl, benzyl, α- phenylethyl, b -phenylethyl or for optionally one or phenyl, alkenyl, styryl substituted by C₁ to C₄ alkyl, C₁ to C₄ alkoxy, halogen, trifluoromethyl, cyano, nitro, C₁ to C₄ alkoxycarbonyl and by compounds of the formula II

in the A, M and Z the same meaning as to indicated the compounds of formula I, and X for - (CH₂) ₄-, - (CH₂) ₅- and - (CH₂) ₆-, for phenylene-1,3-, phenylene-1,4-, 2-methyl-phenylene-1,3-, 4-methyl-phenylene-1,3-, Naphthalene-1,5- or diphenylmethane-4,4'- is.

The reaction can be illustrated by the following reaction scheme will:  

Correspondingly, for example, 5-methyl-4-phenyl-3-aminopyrazole and phenyl isocyanate or 4-methoxyphenyl isocyanate as starting materials for the results:

For the production of the previously unknown bis-azolo [5,1-d] - [1,2,3,5] -tetrazin-4-ones of formula II are the Aminoazoles of the formula III diazotized, optionally with a base deprotonated, and with a diisocyanate of the formula V

OCN-X-NCO (V)

implemented in a molar ratio of 2: 1, where X is for tetramethylene, Pentamethylene, preferably hexamethylene, however for phenylene-1,3- or phenylene-1,4-, preferably 2-methyl- phenylene-1,3- or for 4-methylphenylene-1,3-, naphthylene- 1,5- or diphenylmethane-4,4'- is.

The raw materials for the production of new compounds are generally defined by formulas III, IV and V. In formula III, A stands for, for example Nitrogen atom or for the rest

where R1 is for example for hydrogen, straight-chain or branched alkyl, or for cycloalkyl, benzyl, aryl, SH, S-alkyl, phenoxyalkyl stands.

In formula III, M represents, for example, a nitrogen atom, if not A and Z for nitrogen at the same time stand or for the rest

where R² for example for hydrogen, straight-chain or branched C₁- bis C₁₂-, preferably C₁- to C₄-alkyl or for C₃- to C₈- Cycloalkyl, benzyl or optionally by fluorine, Chlorine, bromine, methyl, trifluoromethyl, methoxy, cyan or Nitro substituted phenyl, preferably for unsubstituted Phenyl stands.

In formula III, Z is, for example, nitrogen, if A and M are not nitrogen at the same time, or preferably for the rest = C-R³, where R³ is hydrogen,  straight-chain or branched C₁ to C₄ alkyl, Chlorine, bromine, cyan, nitro, alkoxycarbonyl with up to 4 carbon atoms in alkoxy, benzyl or preferably for optionally by fluorine, chlorine, bromine, methyl, trifluoromethyl, Methoxy, cyan or nitro substituted phenyl stands, especially for phenyl. R³ can for example also stand for thienyl-2, thienyl-3, or pyridyl-3.

R² and R³ can, for example, together for a tetramethine chain -CH = CH-CH = CH- or for a trimethylene, Tetramethylene, petamethylene or hexamethylene chain.

In the formula IV, the radical R⁴ is, for example, straight-chain or branched alkyl having 1 to 12 carbon atoms, which is optionally substituted by C₁- to C₃-alkoxy or by fluorine or chlorine, or by C₃- to C₈-cycloalkyl, or by allyl, Benzyl, α- phenylethyl, β- phenylethyl, preferably for phenyl, which may be substituted by C₁ to C₄ alkyl, C₁ to C₄ alkoxy, fluorine, chlorine, bromine, trifluoromethyl, cyano, nitro or alkoxycarbonyl with up to 4 C- Atoms in the alkoxy radical may be substituted, or for alkenyl, such as vinyl, substituted vinyl, e.g. B. styryl or allyl.

As an example for aminoazoles of the formula III are in detail called:

3-aminopyrazole
3-amino-5-methyl-pyrazole
3-amino-4,5-dimethylpyrazole
3-amino-4-phenyl-5-methylpyrazole
3-amino-4-methyl-5-phenylpyrazole
3-amino-4-phenylpyrazole
3-amino-5-phenylpyrazole
3-amino-4,5-diphenyl-pyrazole
3-amino-4-methoxycarbonyl-pyrazole
3-amino-4-methoxycarbonyl-5-methyl-pyrazole
3-amino-4-ethoxycarbonyl-5-methylpyrazole
3-amino-4-cyanopyrazole
3-amino-4-bromo-5-methylpyrazole
3-amino-4-phenyl-5-benzylpyrazole
3-amino-1,2,4-triazole
3-amino-4-bromo-pyrazole
3-amino-4-methyl-pyrazole
3-amino-4-nitro-pyrazole
3-amino-4- (2'-thienyl) pyrazole
3-amino-5-methyl-1,2,4-triazole
3-amino-5-phenyl-1,2,4-triazole
4-amino-5-phenyl-1,2,3-triazole
3-amino-indazole

Specific examples of isocyanates of the formula IV are called:

Methyl isocyanate
Ethyl isocyanate
Isopropyl isocyanate
n-butyl isocyanate
sec-butyl isocyanate
tert-butyl isocyanate
Cyclohexyl isocyanate
2-chloroethyl isocyanate
1-methoxy-2-propyl isocyanate
Dodecyl isocyanate
Benzyl isocyanate
Allyl isocyanate
α- phenylethyl isocyanate; β- phenylethyl isocyanate
Phenyl isocyanate
meta-trifluoromethyl-phenyl isocyanate
para-nitrophenyl isocyanate
para-methoxyphenyl isocyanate
para-methylphenyl isocyanate
para-chlorophenyl isocyanate
ortho-fluorophenyl isocyanate
2,4,6-trimethylphenyl isocyanate
2,4-dichlorophenyl isocyanate
3,4-dichlorophenyl isocyanate
3,4-difluorophenyl isocyanate
3-chloro-4-fluorophenyl isocyanate
meta-bromophenyl isocyanate
3-methoxycarbonyl phenyl isocyanate
4-ethoxycarbonyl phenyl isocyanate
Vinyl isocyanate and others

The following are examples of diisocyanates of the formula V. called:

Tetramethylene diisocyanate
Pentamethylene diisocyanate
Hexamethylene diisocyanate
meta-phenylene diisocyanate
2-methyl-meta-phenylene diisocyanate
4-methyl-meta-phenylene diisocyanate
Naphthalene-1,5-diisocyanate
Diphenylmethane-4,4'-diisocyanate

The aminoazoles and isocyanates used as starting materials are for the most part known or can be used in analogy be made to known processes.

For the preparation of compounds of formula I two starting materials, aminoazole and isocyanate, are preferred  used in a molar ratio of 1: 1. To achieve high However, it can be advantageous to yield an excess from 10 to 50% of mono-isocyanate. In the Preparation of compounds of formula II is the molar ratio from aminoazole to diisocyanate preferably 1: 0.5. The reaction temperature is generally between -50 and + 60 ° C, but preferably in the range of -5 up to + 15 ° C. In general, work is carried out under normal pressure.

For the implementation of the diazotized or the diazotized and deprotonated compound III with the isocyanates working in a two-phase aqueous-non-aqueous solvent system (acidic, buffered, neutral or basic Milieu) or in anhydrous diluents expedient.

For example, the following diluents or solvents come considered: methylene chloride, chloroform, diethyl ether, Methyl tert-butyl ether, tetrahydrofuran, toluene, Chlorobenzene, ethyl acetate, butyl acetate, Dimethylformamide.

Bases can be used:

• 1. bicarbonate or carbonates, such as. B. sodium bicarbonate or sodium carbonate.
• 2. Carboxylic acid salts, such as. B. sodium or ammonium acetate.
• 3. hydroxides, such as. B. sodium or potassium hydroxide.
• 4. Ammonia, alkylamines and glycine.

To isolate the compounds of the invention the end products obtained as a solid by filtration separated from the solvent and optionally by sublimation or recrystallization cleaned. Suitable solvents  this includes, for example, methanol, ethanol, Ethyl acetate, toluene or dichloroethane. If that End product is liquid, it is evaporated by the solvent won. When working up from the aqueous phase the end product can also first be extracted with methylene chloride and then isolated by evaporation.

The method according to the invention enables production completely new connections. The Azolo- [5,1-d] - [1,2,3,5] -tetrazine- 4-ones can be used as active ingredients in crop protection herbicidal or fungicidal properties or as growth regulators be used. They also offer prospects for use in medicine, especially as a diuretic, Sedatives, tranquillizers or to lower fever. With suitable substitution, the substances can also as dyes or as intermediates for dye production be used. The new connections are moreover extremely remarkable and valuable raw materials for scientific and commercial research.

The processes according to the invention are illustrated by the following examples illustrates:

Example 1

5.2 g of 5-methyl-4-phenyl-3-aminopyrazole are mixed from 15 ml conc. HCl and 15 ml water dissolved Chilled 5 ° C and with stirring at 0 to 5 ° C with a solution drop of 2.3 g of sodium nitrite in 10 ml of water transferred. After stirring for 30 minutes at 0 ° C and adding 150 ml of methylene chloride is cooled to 0 ° C saturated Na₂CO₃ solution added dropwise until the pH of the Reaction mixture is 7 to 8. Then the  orange-colored organic phase separated and over Na₂SO₄ dried. After separating the desiccant by filtration the solution becomes a solution of 5.0 g of 4-methoxyphenyl isocyanate in 100 ml of methylene chloride given, the temperature by cooling at 0 to 5 ° C. is held. After stirring for 16 hours at room temperature the precipitated crystals are suctioned off. To Evaporation of the filtrate gives crystals again. A total of 8.6 g (86%) of 3- (4-methoxyphenyl) - are obtained. 7-methyl-8-phenyl-pyrazolo- [5,1-d] - [1,2,3,5] -tetrazine- 4-one with mp. 182 to 184 ° C as a yellow solid.

The following compounds were obtained in the same way:  

In Examples Nos. 15 and 16, 3-amino-indazole hydrogen sulfate used as starting material.

Analogously, but using ½ mole of diisocyanate per mole of aminopyrazole, the following compounds of formula II:  

Example 20 Working in a two-phase solvent system

5.2 g of 5-methyl-4-phenyl-3-aminopyrazole are mixed from 15 ml conc. HCl and 15 ml water dissolved and 0 ° C with a solution of 2.3 g sodium nitrite in 10 ml water dissolved and at 0 ° C with a solution of 2.3 g of sodium nitrite added dropwise in 10 ml of water. Subsequently 150 ml of methylene chloride are added with cooling to 0 ° C. drips at 0 to 5 ° C saturated Na₂CO₃ solution until it is reached from pH 7 to 8 and then adds to the two-phase reaction mixture with good stirring at 0 ° C a solution of 6.1 g of 4-chlorophenyl isocyanate in 30 ml of methylene chloride drop by drop. After a total of 15 minutes Stirring is added as much methylene chloride as for complete dissolution of the crystalline product is required. After separation of the organic phase and drying over Na₂SO₄ the product is evaporated of methylene chloride isolated. 9.7 g (96% d. Th.) 3- (4-chlorophenyl) -7-methyl-8-phenylpyrazolo- [5,1-d] - [1,2,3,5] -tetrazin-4-one as pale yellow crystals, mp. 178 up to 182 ° C (identical to the substance of Example 5).  

Example 21

7.5 g of 5-benzyl-4-phenyl-3-aminopyrazole in 75 ml of glacial acetic acid dissolved and at 0 to 5 ° C with a solution of 2.3 g NaNO₂ in 10 ml of water as in Example 1 and after neutralization with saturated Na₂CO₃ solution in Dissolved 250 ml methylene chloride. The solution of the diazo compound then becomes a solution under ice cooling 3.9 g of phenyl isocyanate were added dropwise to 100 ml of methylene chloride. After 1 hour of stirring at 25 ° C, the solvent removed in vacuo and the oily residue with diethyl ether rubbed. 10 g (88% of theory) of 7-benzyl 3,8-diphenylpyrazolo- [5,1-d] - [1,2,3,5] -tetrazin-4-one as pale yellow crystals. After recrystallization from ethanol / Benzene (10: 1) showed a sample mp 120 to 121 ° C.

Example 22

4.0 g of 5-phenyl-4-aminol-1,2,3-triazole are mixed from 25 ml conc. Nitric acid and 25 ml of water dissolved. After cooling to 0 to 5 ° C at this temperature dropwise with a solution of 1.9 g NaNO₂ in 10 ml water transferred. After 30 minutes, 150 ml of methylene chloride added and with saturated Na₂CO₃ solution pH 7 to 8 adjusted. The yellow solution of the diazotriazole is dried over Na₂SO₄ and to a solution of 3.3 g of phenyl isocyanate added dropwise in 100 ml of methylene chloride. After stirring for 2 days at 25 ° C, the precipitated aspirated light yellow crystals, the filtrate is after filtration evaporated over silica gel. It is obtained after recrystallization from benzene-ethanol (6: 1) 3,8-diphenyl [1,2,3] -triazolo- [5,1-d] - [1,2,3,5] -tetrazin-4-one with Mp 140-142 ° C.  

Example 23

In the same way, 5-phenyl-4-amino-1,2,3-triazole and 4-nitrophenyl isocyanate the 3- (4-nitrophenyl) -8-phenyl [1,2,3] -triazolo- [5,1-d] - [1,2,3,5] -tetrazin-4-one.

The following compounds were prepared according to the procedure described in Example 1 or 20 method specified:  

Example 39

1.73 g of 5-benzyl-4-phenyl-3-amino-pyrazole are in one Mixture of 5 ml conc. HCl and 5 ml water dissolved Chilled 5 ° C and with stirring at 0 to 5 ° C with a solution dropwise of 0.76 g of sodium nitrite in 4 ml of water transferred. After 30 minutes of stirring at 0 ° C, 90 ml of cold Methylene chloride and 2 ml of phenyl isocyanate added and stir the two-phase mixture under ice cooling for one hour calmly. After stirring overnight at room temperature the organic phase is separated off, the aqueous phase extracted again with 50 ml of methylene chloride. The United Methylene chloride solutions are saturated with NaHCO₃ solution washed neutral and dried with Na₂SO₄. After filtering off the desiccant, the solution is evaporated, the residue rubbed with ether and the precipitated Aspirated crystals. 2.5 g (82% of the Theory) 7-methyl-3,8-diphenyl-pyrazolo- [5,1-d] - [1,2,3,5] - tetrazin-4-one as pale yellow crystals, mp. 143 to 144 ° C. (identical to the substance of Example 3).

Example 40

1.73 g of 5-methyl-4-phenyl-3-amino-pyrazole are in one Mixture of 5 ml conc. HCl and 5 ml water dissolved Chilled 5 ° C and with stirring at 0 to 5 ° C with a solution dropwise of 0.76 g of sodium nitrite in 4 ml of water transferred. After 30 minutes of stirring at 0 ° C, 90 ml of cold Methylene chloride added. By adding 10 g Sodium acetate and 10 ml of water are in the aqueous phase reached a pH of approx. 6. After dropping 2 ml Phenyl isocyanate is still an hour with ice cooling and then allowed to stir overnight at room temperature. To The organic phase is separated off again with 50 ml of methylene chloride extracted, the combined methylene chloride solutions  are washed neutral with saturated NaHCO₃ solution and dried with Na₂SO₄. After filtering off the desiccant the solution is evaporated, the residue with Ether rubbed in and the precipitated crystals are suction filtered. 2.6 g (85%) of 7-methyl-3,8-diphenyl- pyrazolo- [5,1-d] - [1,2,3,5] -tetrazin-4-one as beige crystals, Mp 142 to 144 ° C (identical to the substance of the Example 3 or 39).  

Efficacy against Phytophthora infestans on tomatoes

Leaves of potted plants of the "Large meat tomato" variety are watery Spray liquor containing 80% active ingredient and 20% emulsifier in the Contains dry substance, sprayed. After 24 hours the leaves are with a zoospore suspension of the fungus Phytophthora infestans infected. The plants are then placed in a steam-saturated chamber at temperatures set up between 16 and 18 ° C. After 6 days the Disease on the untreated but infected control plants like this strongly developed that assesses the fungicidal effectiveness of the substances can be.

The result of the experiment shows that the active ingredients Nos. 15 and 37 at application as a 0.025% spray liquor has a better fungicidal action show (90%) as the known comparison agent (60%).

Efficacy against Septoria nodorum

Leaves of "Jubilar" wheat seedlings grown in pots were sprayed with an aqueous spray liquor containing 80% active ingredient and 20% Emulsifier contained in the dry matter until dripping wet sprayed. The following day, the dried plants were treated with a infected aqueous spore suspension of Septoria nodorum and then for 7 days at 17 to 19 ° C and 95% relative humidity cultured. The extent of the fungal attack was then determined visually.

In this experiment, the infestation of the leaves after treatment with 0.05% active ingredient preparation for the compounds No. 37 according to the invention low, while at Comparative drug and severe infection occurred in untreated plants.  

Efficacy against powdery mildew

Leaves of "Early Gold" wheat seedlings grown in pots were with aqueous spray liquor, the 80% active ingredient and 20% emulsifier contained in the dry matter, sprayed and 24 hours after Dry the spray coating with oidia (spores) of the powdery mildew (Erysiphe graminis var. Tritici) pollinated. The test plants were then in the greenhouse at temperatures between 20 and 22 ° C and 75 up to 80% relative humidity. After 7 days it was Extent of mildew development determined.

In this experiment, 0.025% active ingredient preparation was the Compounds No. 15 largely prevent the development of harmful fungi while Comparative drug A not heavily infested with moderate leaf damage prevented (untreated total infestation).

Efficacy against cucumber mildew

Leaves of potted cucumber seedlings of the "Chinese variety Snake "were at the two-leaf stage with an aqueous conidia suspension of cucumber powdery mildew. After a day, these plants became with aqueous spray liquor containing 80% active ingredient and 20% emulsifier in the Dry matter contained, sprayed to drip and in the greenhouse at temperatures between 20 and 22 ° C and 70 to 80% humidity set up. 21 days after the inoculation, the extent of the fungal attack determined.

In this experiment, the infestation of the leaves after treatment with 0.025% active ingredient preparation for compound no. 15 low, during the Comparative active ingredient A does not cause severe infestation when leaf damage begins prevented (untreated total infestation).  

Antileukaemic efficacy of 41 against L 1210

Example 41: Compound No. 41 is prepared analogously to Examples 1 and 32 by combining the radicals R⁴ from Example No. 8 (with R⁴ = 2-chloroethyl) and Example No. 32 (with R² = methyl, R³ = methoxycarbonyl).

In the test for cytostatic activity in the leukemia test L 1210 (standard mouse test), the active ingredient no. 41 with a daily ip dose of 40 mg / kg for 5 days gave a survival time of 13 days as an average value in the range of 12-13 days . The survival time in the control experiment was 9.5 days in the range of 9-12 days. This results in a value of 36.8% ILS (T / C = 136.8%).

Claims (2)

1. Pyrazolo [5,1-d] -1,2,3,4-tetrazin-4-one of the formula Ia in the
M for C-R²,
Z stands for C-R³
and in what
R² is H, straight-chain or branched C₁- to C₁₂-alkyl, C₃- to C₈-cycloalkyl, benzyl or phenyl optionally substituted by methyl, trifluoromethyl, halogen, methoxy, cyano or nitro,
R³ for H, straight-chain or branched C₁ to C₄ alkyl, chlorine, bromine, cyano, nitro, alkoxycarbonyl having up to 4 carbon atoms in the alkoxy radical, benzyl or phenyl optionally substituted by halogen, methyl, trifluoromethyl, methoxy, cyano or nitro , Thienyl-2, thienyl-3, or pyridyl-3 or
R² and R³ together for a tetramethine chain -CH = CH-CH = CH-, form a trimethylene, tetramethylene, pentamethylene or hexamethylene chain and in the
R⁴ for straight-chain or branched C₁- to C₁₂-alkyl, which can optionally be substituted by C₁- to C₃-alkoxy or fluorine or chlorine, for C₃- to C₈-cycloalkyl, benzyl, α- phenylethyl, β- phenylethyl or for optionally by C₁ to C₄ alkyl, C₁ to C₄ alkoxy, halogen, trifluoromethyl, cyano, nitro, C₁ to C₄ alkoxycarbonyl substituted phenyl, vinyl, styryl or allyl. 2. Process for the preparation of Azolo [5,1-d] -1,2,3,5-tetrazin- 4-ones of the formula I. in the
A for N or C-R¹,
M for N or C-R²,
Z is N or C-R³, but not simultaneously A, M and Z is nitrogen
and in what
R¹ for H, straight-chain or branched alkyl, cycloalkyl, benzyl, aryl, SH, S-alkyl, phenoxyalkyl,
R² is H, straight-chain or branched C₁- to C₁₂-alkyl, C₃- to C₈-cycloalkyl, benzyl or phenyl optionally substituted by methyl, trifluoromethyl, halogen, methoxy, cyano or nitro,
R³ for H, straight-chain or branched C₁ to C₄ alkyl, chlorine, bromine, cyano, nitro, alkoxycarbonyl having up to 4 carbon atoms in the alkoxy radical, benzyl or phenyl optionally substituted by halogen, methyl, trifluoromethyl, methoxy, cyano or nitro , Thienyl-2, thienyl-3, or pyridyl-3 or
R² and R³ together for a tetramethine chain
-CH = CH-CH = CH-, form a trimethylene, tetramethylene, pentamethylene or hexamethylene chain and in the
R⁴ for straight-chain or branched C₁- to C₁₂-alkyl, which can optionally be substituted by C₁- to C₃-alkoxy or halogen, for C₃- to C₈-cycloalkyl, benzyl, α- phenylethyl, β- phenylethyl or for optionally by C₁- to C₄-alkyl, C₁- to C₄-alkoxy, halogen, trifluoromethyl, cyano, nitro, C₁- to C₄-alkoxycarbonyl substituted phenyl, alkenyl, styryl,
and of compounds of the formula II in which A, M and Z have the same meaning as given for the compounds of formula I, and X for - (CH₂) ₄-, - (CH₂) ₅- and - (CH₂) ₆-, for phenylene-1,3 -, phenylene-1,4-, 2-methylphenylene-1,3-, 4-methylphenylene-1,3-, naphthylene-1,5- or diphenylmethane-4,4'-,
characterized in that an aminoazole of the formula III in which A, M and Z have the meaning given above, diazotized, optionally deprotonated with bases and in a two-phase aqueous / non-aqueous solvent system or in anhydrous diluents either with an isocyanate of the formula IVR⁴NCO (IV) in a molar ratio of aminoazole to isocyanate of 1: 1 up to 1: 1.5 to the compounds of the formula I or with a diisocyanate of the formula VOCN-X-NCO (V) in a molar ratio of 2: 1 to the compounds of the formula II,
where R⁴ and X have the meanings given above.