GB1580485A - Triazolidino pyridazine-diones - Google Patents

Description

(54) IMPROVEMENTS IN AND RELATING TO TRIAZOLIDINO-PYRIDAZINE-DIONES (71) We, HOECHST AKTIENGESELLSCHAFT, a body corporate organised according to the laws of the Federal Republic of Germany, of 6230 Frankfurt/Main 80, Postfach 80 03 20, Federal Republic of Germany, do hereby declare the invention for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement: The present invention relates to triazolidinotyridazinediones.

The present invention provides triazolidinopyridazine-diones of the general formula (I)

in which n is an integer, preferably the integer 1, 2 or 3, Rl represents an n-valent organic radical and R2 represents a hydrogen atom or a methyl group.

Where n is 1, 2 or 3 the following definitions of Rl are preferred.

1) If n is 1, R1 represents an optionally branched alkyl radical having from 1 to 18 carbon atoms, especially from 1 to 12 carbon atoms, which may also be sub stituted, an unsubstituted or substituted phenyl group or an optionally substituted cycloalkyl radical having from 5 to 8 carbon atoms in the carbon ring, eg. a cyclohexyl group. For example R1 may represent the norbornylmethyl radical, a hydroxyalkyl radical having, eg., from 1 to 4 carbon atoms, an alkoxyalkyl or alkylthioalkyl radical having, eg., a total of from 2 to 8 carbon atoms, especially 2 to 6 carbon atoms, an unsubstituted or substituted phenyl or benzyl radical, preferably substituted by one or more of the same or different substituents selec ted from halogen atoms, nitro and cyano groups, alkyl and alkoxy groups each having from 1 to 4 carbon atoms and halogen-substituted alkyl groups.

2) If n is 2, R1 represents a divalent aliphatic or cycloaliphatic hydrocarbon group, especially an alkylene or cycloalkylene group, having up to 36 carbon atoms, preferably up to 12, especially up to 6 carbon atoms, which may be saturated or unsaturated, preferably saturated, uninterrupted or interrupted by one or more oxygen, sulphur or nitrogen atoms, unsubstituted or substituted, preferably by one or more of the same or different substituents selected from halogen atoms and from alkyl groups having from 1 to 4 carbon atoms which are substituted by a hydroxy group, an alkoxy group preferably having from 1 to 4 carbon atoms or an alkylthio group preferably having from 1 to 4 carbon atoms. The substituted aliphatic hydrocarbon group may be an araliphatic group having up to 36 carbon atoms, preferably up to 24, especially up to 12 carbon atoms, which may also be unsubstituted or substituted, preferably by one or more of the same or different substituents selected from halogen atoms, nitro and cyano groups and alkyl groups having from 1 to 4 carbon atoms which themselves may be unsubstituted or sub stituted by one or more halogen atoms or by a hydroxy group or an alkoxy or alkylthio group, preferably having from 1 to 4 carbon atoms. If n is 2, R1 may also represent a divalent aromatic or heterocyclic radical having up to 36 carbon atoms, preferably up to 24, especially up to 12 carbon atoms, which may also be unsubstituted or substituted preferably by one or more of the same or dif ferent substituents selected from halogen atoms, nitro and cyano groups and alkyl groups having 1 to 4 carbon atoms which themselves may be unsubstituted or substituted by one or more halogen atoms or by a hydroxy group, an alkoxy group preferably having from 1 to 4 carbon atoms or an alkylthio group prefer ably having from 1 to 4 carbon atoms.

3) If n is 3, R1 represents a trivalent aliphatic or cycloaliphatic group having from 3 to 36 carbon atoms, especially 3 to 9 carbon atoms, which may be unsaturated or saturated, preferably saturated, uninterrupted or interrupted by one or more oxygen, sulphur or nitrogen atoms, unsubstituted or substituted, preferably by one or more of the same or different substituents selected from halogen atoms and alkyl groups having from 1 to 4 carbon atoms which are substituted by a hydroxy group, an alkoxy group preferably having from 1 to 4 carbon atoms or an alkylthio group preferably having from 1 to 4 carbon atoms. Preferably R1 is a saturated aliphatic Of cycloaliphatic hydrocarbon group, preferably having from 3-9 carbon atoms, which may be unsubstituted or substituted, preferably substituted by one or more of the same or different substituents listed immediately above. The substituted aliphatic hydrocarbon group may be an araliphatic group having up to 36 carbon atoms, preferably up to 24, especially up to 12 carbon atoms, which may also be unsubstituted or substituted, preferably by one or more of the same or different substituents selected from halogen atoms, nitro and cyano groups and alkyl groups having from 1 to 4 carbon atoms which themselves may be unsubstituted or substituted by one or more halogen atoms or by a hydroxy group, an alkoxy group preferably having from 1 to 4 carbon atoms or an alkylthio group preferably having from 1 to 4 carbon atoms, and have up to 36 carbon atoms, preferably up to 24, especially up to 12 carbon atoms therein.

If n is 3, R1 may also represent a trivalent aromatic or heterocyclic radical having up to 36 carbon atoms, preferably up to 24, especially up to 12 carbon atoms, which may be unsubstituted or substituted preferably by one or more of the same or different substituents selected from halogen atoms, nitro and cyano groups and alkyl groups having from 1 to 4 carbon atoms which may be unsub stituted or substituted by a hydroxy group, an alkoxy group preferably having from 1 to 4 carbon atoms or an alkylthio group preferably having from 1 to 4 carbon atoms.

For example, when n is 1, Rl may represent a (C1-C12)alkyl, a (C1-C4)- hydroxyalkyl, a (C2-C6)alkoxyalkyl, a (C2-Ce)alkyl-thioalkyl or a cydohexyl group; when n is 2, Rl may represent a (C112 ) alkylene group or a (C1-C6) alxylene group which may be unsubstituted or substituted by (C1-C4)hydroxyalkyl, (C1C4)- alkoxy-alkyl or (C1-C4)alkyyl-thio alkyl groups; when n is 3, R1 may represent a trivalent (C3-C9 ) -aliphatic or a 1,3,5-triazine group.

The invention also provides a salt of a compound of the general formula (I), especially an acid addition salt thereof.

The invention further provides a process for the preparation of compounds of the general formula (I), which comprises reacting a pyridazinediones of the general formula (II)

-with a primary amine of the general formula (III) (H2N)R, (III) and formaldehyde. n, R1 and R2 are as defined in general formula (I).

A preferred embodiment of the process comprises suspending or dissolving pyridazinedione of the general formula (II) in a solvent, adding the amine in a molar ratio in the range of from 1:1 to 2:1, based on the amount of pyridazinedione, preferably in the range of from 1.2:1 to 1.7:1, and, whilst stirring, adding thereafter at least twice, suitably twice to four times the molar amount, but preferably 2.5 to 3.5 times molar amount of formaldehyde based on the amount of pyridazinedione, pre ferably in the form of an aqueous formaldehyde solution. The reaction is advan tageously carried out at a temperature in the range of from 0 to 80" C, especially from 200 to 400 C; however the temperature range is not critical. Normally, the reaction product dissolves and may, in the solution formed, be separated from any undissolved pyridazinedione still present. By subsequently evaporating this solution and treating the residue with an inert solvent, for example benzine, or by repre cipitating the product, for example from a mixture of methylene chloride and benzine, the triazolidinopyridazinedione can be isolated in its pure form.

However, even in cases where an amount of formaldehyde is used which is less than the one specified above, the reaction yields the desired final product of the general formula (I).

For some purposes the compounds of the invention are used in an aqueous solution, so it may be advantageous in these cases to prepare such a solution directly by using water as the solvent in the process of the invention. For this purpose it is important, naturally, to use the pyridazinedione of the general formula (II), the amine and the formaldehyde in the appropriate molar ratios so that after the reaction has finished the reaction solution may be used directly without the need of to remove excess starting materials.

Besides the amines used in the Examples, the following amines, diamines and triamines are particularly suitable starting compounds for the process of the invention: ethylamine, propylamine, isopropylamine, isobutylamine, isoamylamine, hexylamine, isohexylamine, heptylamine, isoheptylamine, octylamine, isooctylamine, nonylamine, decylamine, undecylamine, tridecylamine, pentadecylamine, hexadecylamine, octa decylamine, cyclopentylamine, cycloheptylamine, cyclo-octylamine, cyclohexylamine, 2 amino-2-methylpropanol, 2-amino-2-ethylpropane-1,3-diol, 2-hydroxyethylamine, 2 hydroxypropylamine, 4-hydroxybutylamine, 5-hydroxypentylamine, 4-methoxybutyl amine, 5 -methoxypentylamine, 4-ethoxybutylamine, 5 -ethoxypentylamine, 3-propoxy propylamine, 4-propoxybutylamine, 5-propoxypentylamine, 3 -methylthiopropylamine, 4-methylthiobutylamine, 3-propylthiopropylamine, 4-propylthiobutylamine, ,to'-di- aminodiakyl ether, w,B'-diaminodialkyl thioether, methylcyclohexylamine, 1,1-di methylpropine-2-ylamine, 1,1 -diethylpropin-2-ylamine, halogenoaniline, nitroaniline, toluidine, anisole, aminobenzonitrile; methylenediamine, ethylenediamine, propylene diamine, butylenediamine, hexamethylenediamine, 1 -amino-2-aminomethyl-3,3,5-tri- methylcyclopentane; triaminoalkanes, triaminoisononane, triaminohexahydrotriazine, triaminotetrahydrotriazine, triaminodihydrotriazine, 2,4,6-triamino- 1,3,5-triazine (mela mine) and 1,2,3-triaminopropane.

Furthermore, all soluble primary amines, diamines, triamines, oligoamines or polyamines may advantagedusly be used.

As solvents for the reaction there may be used, for example, water or moderately to slightly polar solvents, preferably those having a low boiling point, for example methylene chloride, chloroform, carbon tetrachloride, benzene; ethers, such as diethyl ether, diisopropyl ether and tetrahydrofuran; esters, for example methyl acetate and ethyl acetate or ketone, for example acetone or methyl ethyl ketone. Preferably water, chloroform or methylene chloride is used.

The preparation of a pyridazinedione of the general formula (II) used as start ing compound, as well as the preparation of an amine of the general formula (III) required for the reaction, have already been described in literature.

The formaldehyde is used preferably as an aqueous formalin solution, but other products may also be used, for example paraldehyde and trioxan, which split the formaldehyde off under the reaction conditions thereby forming formaldehyde in situ.

The compounds of the general formula (I) show an excellent fungicidal and bactericidal action industrially as well as agriculturally. They are thus suitable for the preservation of lacquers, dyes, glues, paints, thickeners, sealing compounds and drill ing and cutting oils, for the protection of wood and paper products and textiles, and also for use as plant protective agents.

Therefore the present invention also provides a pesticidal composition which comprises a compound of the invention in admixture or conjunction with a suitable carrier and further provides a method of combating fungi or bacteria which comprises applying a compound of the invention or a pesticidal composition of the invention.

The compounds of the general formula (I) wherein Rl represents an alkyl radical having from 1 to 4 carbon atoms, have a generally good to limited water-solubility, with water-solubility decreasing with increase in chain length of the radical R1, and solubility in organic solvents generally increasing with increase in chain length. Substitutions in R1 of polar groups improve the water-solubility. The tristriazolidinopyridazinedione obtained with melamine, for example, is sparingly soluble in water and is therefore excellently suitable as fungicidal agent for paints, especially for paints which are exposed to weather conditions.

The compounds of the invention show a very good action against fungi, for example: Aureobasidium pullulans, Aspergillus flavus, Aspergillus niger, Aspergillus orycae, Alternaria consortiale, Chaetcnnium globosum, Coniophora puteana, Geotrichum candidum, Lenzites abietina, Merulius lacrimans, Penicillium funiculosum, Penicillium janthinellum, Penicillium vcrmiculatum, Penicillium wortmanni, Poria monticola, against genuine mildew types, Phytophthora iniestans, brown rust of wheat, Plasma para viticola, Cercospora betae, and Cladosporium fulvum as well as against Pytium ultimum, Ustilago avenae and Phoma betae; against Gram-positive and Gram-negative bacteria, for example: Aerobacter aerogenes, Bacillus subtilis, Escherichia coli, Proteus vulgaris and Pseudomonas aeruínosa; as well as against yeasts, for example Saccharomyces cerevisiae.

As bactericidal and fungicidal agents in industry the compounds of the invention may be used as such or in combination with other biocidal agents predominantly in the form of aqueous solutions or dispersions, or directly as additives to coating and painting substances.

As plant protective agents they may be formulated as dusts, wettable powders, dispersions, emulsion concentrates or granules. The content of total active ingredient is, in these cases, in the range of from 10 to 90% by weight. They may also contain common adhesive, wetting and dispersing agents, fillers and carriers or be mixed with, those other fungicidal agents with which they form compatible mixtures.

As carriers their mineral substances may be used, for example aluminum silicates, aluminas, kaolin, chalks, siliceous chalks, talc, kieselguhr or hydrated silicic acid; also preparations of these mineral substances with special additives, for example chalk greased with sodium stearate, may be used.

As carrier substances for liquid formulations all common and appropriate solvents, for example, toluene, zylene, diacetone alcohol, cyclohexanone, isophorone, benzines, paraffin oils, dioxan, dimethylformamide, dimethylsulphoxide, ethyl acetate, tetrahydrofuran and chlorobenzene as well as water may be used.

As adhesives glue-like cellulose products and polyvinyl alcohols are suitable.

As wetting agents all appropriate emulsifiers, for example ethoxylated alkyl phenols, salts of aryl or alkylaryl sulphonic acids, salts of oleoylmethyltaurine, salts of ethoxylated phenylsulphonic acids and soaps, may be used.

As dispersing agents cellulose pitch (salts of lignin sulphonic acid), salts of naphthalene sulphonic acid, and salts of oleoylmethyltaurine are suitable.

As grinding auxiliaries appropriate inorganic or organic salts, for example sodium sulphate, ammonium sulphate, sodium carbonate, sodium bicarbonate, sodium thiosulphate, sodium stearate and sodium acetate, may be used. The following Examples illustrate the invention.

A) Examples of preparation.

EXAMPLE 1.

22.4 Grams (0.2 moles) of pyridazinedione (maleic acid hydrazide) were suspended in 400 ml of methylene chloride, and 19.8 g (0.2 moles) of cyclohexylamine were added. 34.4 Millilitres (0.4 moles) of 35% aqueous formaldehyde solution were then added dropwise. During this process the temperature rose from 25 to 330 C; thereafter the reaction mixture was stirred at 33 C for 2 hours.

Then the mixture was allowed to cool, and magnesium sulphate added to dry the mixture. (Separation from the aqueous layer is not necessary as the reaction pro duct is water-soluble). After filtration the product was concentrated; the residue, an oil, was introduced, whilst stirring, into petroleum ether at a temperature in the range of from 80 to 1100 C. By cooling or partial concentration using a rotary evaporator, a crystalline solid was obtained, which was suction-filtered and dried. The yield was 37.9 g (80.5% of the theory) and the melting point 99" to 1010 C. The substance was found to be water-soluble.

C12H1N3O2 mol. wt. 235.0 Calculated: C 61.26%; H 7.24%; N 17.88% Found: C 60.9%; H 7.6%; N 17.8% In the NMR spectrum 2 olefinic protons, 4 CH2-protons, 10 aliphatic protons (cyclohexyl) and 1

proton were identified. The IR spectrum revealed an intensive carbonyl adsorption at 1620 cml.

EXAMPLE 2.

56.0 Grams (0.5 mole) of pyridazinedione were suspended in 1000 ml of methylene chloride, and 45.5 g (0.5 moles) of methylmercaptoethylamine were added.

85.5 Millilitres (1 mole) of 35% aqueous formaldehyde solution were added dropwise. During this process the temperature rose from 250 to 32 C. The mixture was then stirred at 320 C for 30 minutes, allowed to cool, dried over anhydrous magnesium sulphate and subsequently filtered and concentrated. In this manner an oil was obtained as a residue which crystallised upon trituration with benzine at a temperature in the range of from 300 to 850 C.

The solid matter was suction-filtered and dried. The yield was 83.0 g (73.5% of the theory) and the melting point 910 to 920 C.

C911 13N302S nol.wt. 227.0 Calculated: C 47.58%; H 5.730/c; N 18.5% Found: C 47.9%; H 6.0%; N 18.2% In the infrared spectrum the compound showed a strong CO adsorption at 1612 cool.

The substances of the general formula (I)

specified in the following Table were prepared in a analogous manner to that of Examples 1 and 2 above.

TABLE

Example Rl R2 n Melt. point (OC) 3 -CH3 H 1 160-162 . ~ 4 -C4H9n H 1 55-56 5 -(CH2)11-CH3 8082 6 -(CH2)34)H H 1 106-107 7 -(CH2)34)CH3 H 1 93-94 8 -CH19iso H 1 91-92 9 -C18H3, H 1 90-91 H H < 1 ll 1 137-138 1 11 -CH,-0 1 151 12 t H 1 206-208 13 -C4Hn CH3 1 non-distillable oil 14 -(CH2)11-CH3 CH3 1 46 15 -(CH2),-OH CH3 l 98-101 16 {fizz CH3 1 118-120 17 -CH2-CH2- H 2 157-158 EXAMPLE 18.

112 Grams (1 mole) of pyridazinedione and 75 g (2 moles) of 3-aminopropanol were dispersed in 345 g of water. Subsequently 171 g (2 moles) of a 35% formaldehyde solution was introduced over a period of 10 minutes. The mixture became clear and was then heated to about 40 C. It was maintained at this temperature for approximately an hour, whilst stirring, and was then allowed to cool.

A 30% solution of N - 3 - hydroxypropyltriazolidinopyridazinedione was obtained which was fast to storage at room temperature and also at 50 C and which, for example, may be used in this form as a technical preservative.

EXAMPLE 19.

336 Grams (3 moles) of pyridazinedione and 572 g (6 moles) of 35% aqueous formaldehyde were stirred at room temperature; then 126 g (1 mole) of melamine were added to this mixture, whilst heating to 600 C.

After about 30 minutes the suspension became clean at first and then the reaction product, tris (triazolidinopyridazinedione) -triazine, precipitated as a thick precipitate.

It was allowed to cool, was suction-filtered and dried at 800 C.

Yield: 526 Grams (98.5% of the theory).

Decomposition point: 2450 C.

The substance obtained was virtually insoluble in water and is particularly suitable, for example, as fungicidal agent for paints which are exposed to extreme humidity.

B) Examples of Application.

In the following biological Examples the following comparative substances were used: A = Benzimidazole carbamic acid methyl ester + tetramethylthiuram disulphide B = Tetrahydro-3,5 -dimethyl-2H- 1,3,5-thiadiazine-2'-thione C= 1-Butylcarbamoyl-2-methoxycarbonylaminobenzimidazole D = Manganese ethylene-1,2-bis-dithiocarbamate E = N-(trichloromethylthio) -phthalamide EXAMPLE I.

0.02 Millilitres of a spore suspension of Alternaria consortiale was applied drop wise to a nutrient medium (biomalt agar) in Petri dishes in which the compounds of the preparation Examples 5 and 14 had previously been added to the agar in the liquid state in the concentrations shown in Table I.

6 Days after the innoculation of the plates the diameter of the fungus colonies on the agar was mea.sured, and the growth inhibition caused by the preparation was expressed in per cent, calculated on a control (innoculated agar without the addition of the compounds of Examples 5 and 14 abovethis equalled 0% of inhibition).

As a comparative agent substance A was used in the same concentrations as the compounds to be tested.

TABLE I

Inhibition of Alternaria consortiale in % with mg of active ingredient per litre of agar Compound 50 10 5 1 5 100 90 70 14 100 100 80 A 100 30 0 EXAMPLE II.

Further tests were carried out and evaluated as described in Example I. As test organism Aspergillus niger was used.

TABLE Il

Inhibition of Aspergillus niger in % with mg of active ingredient per litre of agar Compound 50 10 5 1 5 100 0 80 60 14 100 90 70 A A 100 50 20 EXAMPLE III.

0.02 Millilitres of a bacteria suspension (comprising a mixture of E. coli, Bacterium prodigiosum, Bacterium pyocyaneum) were applied dropwise to a nutrient medium (standard-I-nutrient agar for bacteria) in Petri dishes, in which the compounds of the preparation Examples 3, 2, 12, 10, 7, 6, 11, 16, 14, 13 and 15 had previously been added to the agar in the liquid state in the concentrations shown in Table III.

The innoculated plates were evaluated after 4 days as for Examples I and II above.

As comparative agents commercial mercury-free products A and B were used in the same concentrations as the compounds to be tested.

TABLE III

Inhibition of a bacteria mixture in % with mg of active ingredient per litre of agar Compound 1000 500 100 50 3 - 100 90 50 2 ~ 100 40 - 12 - 100 70 - 10 - 100 50. 7 - 100 100 50 6 - 100 100 75 11 - 100 100 50 16 - 100 100 60 14 - 100 100 50 13 - 100 90 50 15 - 100 80 50 A 50 25 - - B 50 25 - Tables I, II and III show the superior fungicidal and/or bactericidal action of the compounds of the invention over the comparative agents.

EXAMPLE IV.

Sugar beet plants in their 6-leaf stage of development were strongly infected with conidia of the organism causing beet leaf spot (Cercospora beticola) and were placed, dripping wet, in a climatic chamber having a temperature of 25 C and a relative humidity of 100%. The plants remained there for 24 hours and were then taken to a green-house having a relative humidity in the range of from 85 to 90% and a temperature in the range of from 24 to 250 C. After 7 days the plants were treated until dripping wet with an aqueous suspension of the compound prepared in Example 14. The applied concentrations were 250, 120, 60 and 30 mg per litre of spraying liquid.

As comparative agent compound C was used in the same concentrations.

Upon drying the spraying liquid, the plants were taken back into a greenhouse. After an incubation period of 3 weeks the plants were examined for infestation with beet leaf spot, and the findings were evaluated. The degree of damage was expressed as a per cent of attacked leaf surface based on untreated infected control plants.

TABLE IV

% of infestation with Cercospora with mg of active ingredient 'l of spraying liquid Compound 250 120 60 30 14 0 0 3 5 C 0 3 5 10 untreated infected 100 plants EXAMPLE V.

Tomato plants of the type "Rheinlands Ruhm" in the 3-leaf stage of development were treated until dripping wet with aqueous suspensions of the compounds mentioned in Table V. The applied concentrations were 500, 250, 120 and 60 mg of active ingredient per litre of spraying liquid. As comparative agent compound D was used in the same concentrations. Upon drying the spraying liquid, the plants were innoculated with a zeosporangia suspension of Phytophthora infestans and were placed, dripping wet, for one day in a climatic chamber at a temperature of 15 C and a relative humidity of 100%. Subsequently they were taken to a cool greenhouse having a temperature of 15C C and a relative humidity of from 85 to 95 C.

After an incubation period of 7 days the plants were examined for infestation with Phytophthora. The degree of damage was expressed as a per cent of attacked leaf surface based on untreated infected control plants.

TABLE V

% of infestation with Phytophthora with mg of active ingredient/l of spraying liquid Compound 500 250 120 60 5 0 0 3 5 14 0 0 0 3 D 0 3 5 15 untreated infected 100 plants EXAMPLE VI.

Vine plants in the 4-leaf stage of development cultivated from cuttings of the Miiller-Thurgau type susceptible to Peronospora were treated until dripping wet with aqueous suspensions of the compounds of Examples 5 and 14. The applied concentrations were 500, 250, 120 and 60 mg of active ingredient per litre of spraying liquid. As comparative agent compound E was used in the same concentrations as the test preparations.

Upon drying the spraying liquid, the plants were innoculated with a zoosporangia suspension of Peronospora viticola and were placed dripping

TABLE VI

% of infestation with Peronospora with mg of active ingredient/l of spraying liquid Compound 500 250 120 60 5 0 0 0 5 14 0 0 0 3 E 0 3 5 10 untreated -infected 100 plants EXAMPLE VII.

Of the 30% aqueous solution of N-3-hydroxypropyltriazolidinopyridazinedione obtained according to Example 18, the following minimum inhibitor concentrations against the following microorganisms were ascertained by a test using nutrient medium plates: Aerobacter aerogenes 0.05% Bacillus subtilis 0.05% Pseudomonas aeruginosa 0.05% Saccharomyces cerevisiac 0.05% Alternaria consortiale 0.1 % Aspergillus niger 0.1 % Chaetomium globosum 0.05% Penicillium funiculosum 0.05% WHAT WE CLAIM IS: 1. A compound of the general formula

wherein n is an integer, Rl represents an n-valent organic group and R2 represents a hydrogen atom or a methyl group.

2. A compound as claimed in claim 1, wherein n is 1, 2 or 3.

3. A compound as claimed in claim 2, wherein n is 1 and R1 represents an alkyl group having from 1 to 18 carbon atoms or a cycloalkyl group having from 5 to 8 carbon atoms in the ring, which groups may be unsubstituted or substituted.

4. A compound as claimed in claim 3, wherein R, represents an alkyl group having from 1 to 12 carbon atoms, which may be unsubstituted or substituted, or a cyclohexyl group.

5. A compound as claimed in either claim 3 or claim 4, wherein R1 represents a norbornylmethyl, hydroxyalkyl, alkoxyalkyl or alkylthioalkyl group.

6. A compound as claimed in claim 5, wherein R1 represents an alkoxyalkyl or alkylthioalkyl group having a total of from 2 to 8 carbon atoms.

**WARNING** end of DESC field may overlap start of CLMS **.

Claims (51)

**WARNING** start of CLMS field may overlap end of DESC **. TABLE VI % of infestation with Peronospora with mg of active ingredient/l of spraying liquid Compound 500 250 120 60 5 0 0 0 5 14 0 0 0 3 E 0 3 5 10 untreated -infected 100 plants EXAMPLE VII. Of the 30% aqueous solution of N-3-hydroxypropyltriazolidinopyridazinedione obtained according to Example 18, the following minimum inhibitor concentrations against the following microorganisms were ascertained by a test using nutrient medium plates: Aerobacter aerogenes 0.05% Bacillus subtilis 0.05% Pseudomonas aeruginosa 0.05% Saccharomyces cerevisiac 0.05% Alternaria consortiale 0.1 % Aspergillus niger 0.1 % Chaetomium globosum 0.05% Penicillium funiculosum 0.05% WHAT WE CLAIM IS:

1. A compound of the general formula

wherein n is an integer, Rl represents an n-valent organic group and R2 represents a hydrogen atom or a methyl group.

2. A compound as claimed in claim 1, wherein n is 1, 2 or 3.

3. A compound as claimed in claim 2, wherein n is 1 and R1 represents an alkyl group having from 1 to 18 carbon atoms or a cycloalkyl group having from 5 to 8 carbon atoms in the ring, which groups may be unsubstituted or substituted.

4. A compound as claimed in claim 3, wherein R, represents an alkyl group having from 1 to 12 carbon atoms, which may be unsubstituted or substituted, or a cyclohexyl group.

5. A compound as claimed in either claim 3 or claim 4, wherein R1 represents a norbornylmethyl, hydroxyalkyl, alkoxyalkyl or alkylthioalkyl group.

6. A compound as claimed in claim 5, wherein R1 represents an alkoxyalkyl or alkylthioalkyl group having a total of from 2 to 8 carbon atoms.

7. A compound as claimed in claim 6, wherein R, represents an alkoxyalkyl or

alkylthioalkyl group having a total of from 2 to 6 carbon atoms.

8. A compound as claimed in claim 5, wherein R1 represents a hydroxyalkyl group having from 1 to 4 carbon atoms.

9. A compound as claimed in claim 2, wherein n is 1 and R1 represents an unsubstituted or substituted phenyl or benzyl group.

10. A compound as claimed in claim 9, wherein Rl represents a phenyl or benzyl group which is substituted by one or more of the same or different substituents selected from halogen atoms, nitro and cyano groups, alkyl and alkoxy groups each having from 1 to 4 carbon atoms and halogen-substituted alkyl groups.

11. A compound as claimed in claim 2, wherein n is 2 and R1 represents a divalent aliphatic or cycloaliphatic hydrocarbon group having up to 36 carbon atoms, which may be unsubstituted or substituted, saturated or unsaturated, and which may be uninterrupted or interrupted by one or more oxygen, sulphur or nitrogen atoms.

12. A compound as claimed in claim 11, wherein R1 represents a saturated aliphatic or cycloaliphatic hydrocarbon group which may be unsubstituted or substituted.

13. A compound as claimed in either claim 11 or claim 12, wherein the aliphatic or cycloaliphatic group represented by R1 has up to 12 carbon atoms.

14. A compound as claimed in claim 13, wherein the aliphatic or cycloaliphatic group represented by R1 has up to 6 carbon atoms.

15. A compound as claimed in any one of claims 11 to 14, wherein R1 represents an alkylene group which may be unsubstituted or substituted.

16. A compound as claimed in any one of claims 11 to 15, wherein the aliphatic or cycloaliphatic group represented by R1 is substituted by one or more of the same or different substituents selected from halogen atoms, and alkyl groups having from 1 to 4 carbon atoms which are substituted by a hydroxyl, alkoxy or alkylthio group.

17. A compound-as ctaimed m~clairn~16, wherein an alkoxy and/or alkylthio substituent has from 1 to 4 carbon atoms.

18. A compound as claimed in claim 2, wherein n is 2 and R1 represents a divalent aromatic, araliphatic or heterocyclic group having up to 36 carbon atoms which may be unsubstituted or substituted.

19. A compound as claimed in claim 18, wherein the aromatic, araliphatic or heterocyclic group represented by R1 has up to 24 carbon atoms.

20. A compound as claimed in claim 19, wherein the aromatic, araliphatic or heterocyclic group represented by Rl has up to 12 carbon atoms.

21. A compound as claimed in any one of daims 18 to 20, wherein R1 represents an aromatic, araliphatic or heterocyclic group which is substituted by one or more of the same or different substituents selected from halogen atoms, nitro and cyano groups, and alkyl groups having from 1 to 4 carbon atoms which may be unsubstituted or substituted by one or more halogen atoms or by a hydroxy, alkoxy or alkylthio group.

22. A compound as claimed in claim 21, wherein an alkoxy and/or alkylthio substituent has from 1 to 4 carbon atoms.

23. A compound as claimed in claim 2, wherein n is 3 and R1 represents a trivalent, aliphatic or cycloaliphatic group having from 3 to 36 carbon atoms, which may be unsubstituted or substituted, saturated or unsaturated, and which may be uninterrupted or interrupted by one or more oxygen, sulphur or nitrogen atoms.

24. A compound as claimed in claim 23, wherein R1 represents a saturated aliphatic or cycloaliphatic hydrocarbon group which may be unsubstituted or substituted.

25. A compound as claimed in either claim 23 or claim 24, wherein the aliphatic or cycloaliphatic group represented by R1 has from 3 to 9 carbon atoms.

26. A compound as claimed in any one of claims 23 to 25, wherein the aliphatic or cycloaliphatic group represented by R1 is substituted by one or more of the same or different substituents selected from halogen atoms and alkyl groups having from 1 to 4 carbon atoms which are substituted by a hydroxy, alkoxy or alkylthio group.

27. A compound as claimed in claim 26, wherein an alkoxy and/or alkylthio substituent has from 1 to 4 carbon atoms.

28. A compound as claimed in claim 2, wherein n is 3 and R1 represents a trivalent aromatic, araliphatic or heterocyclic group having up to 36 carbon atoms which may be unsubstituted or substituted.

29. A compound as claimed in claim 28, wherein the aromatic, araliphatic or heterocyclic group represented by R1 has up to 24 carbon atoms.

30. A compound as claimed in claim 29, wherein the aromatic, araliphatic or heterocyclic group represented by R, has up to 12 carbon atoms.

31. A compound as claimed in any one of claims 28 to 30, wherein the aromatic, araliphatic or heterocyclic group represented by R, is substituted by one or more of the same or different substituents selected from halogen atoms, nitro and cyano groups, and alkyl groups having from 1 to 4 carbon atoms which may be unsubstituted or substituted by a hydroxy, alkoxy or alkyl thio groups or by one or more halogen atoms.

32. A compound as claimed in claim 31, wherein an alkoxy and/or alkylmercapto substituent has from 1 to 4 carbon atoms.

33. A compound as claimed in claim 28, wherein R, represents a 1,3,5-triazine group.

34. A compound as claimed m claim 1, substantially as described in any one of the Examples herein.

35. A salt of a compound as claimed in any one of claims 1 to 34.

36. An acid addition salt of a compound as claimed in any one of claims 1 to 34.

37. A process for the preparation of a compound as claimed in claim 1 or a salt thereof, which comprises reacting a compound of the general formula

wherein R2 has the meaning given in claim 1, with a primary amine of the general formula (H2N)-R1 (III) wherein R1 and n have the meanings given in claim 1, and with formaldehyde.

38. A process as claimed in claim 37, wherein at least 2 moles of formaldehyde are used per mole of the compound of the general formula (II).

39. A process as claimed in claim 38, wherein in the range of from 2.5 to 3.5 moles of formaldehyde are used per mole of compound of the general formula (II).

40. A process as claimed in any one of claims 37 to 39, wherein the reaction is performed in the presence of a solvent.

41. A process as claimed in claim 40, wherein the solvent is water.

42. A process as claimed in iny one of claims 37 to 41, wherein the formaldehyde is generated in situ.

43. A process as claimed in any one of claims 37 to 42, wherein the reaction is carried out at 2 temperature in the range of from 0 to 80 C.

44. A process as claimed in any one of claims 37 to 43, wherein the amine of the general formula (II) is any one of these listed herein.

45. A process as claimed in claim 37, carried out substantially as described in any one of Examples 1 to 19 herein.

46. A compound as claimed in claim 1, whenever prepared by a process as claimed in any one of claims 37 to 45.

47. A pesticidal composition which comprises a compound as claimed in any one of claims 1 to 36 and 46, in admixture or conjunction with a suitable carrier.

48. A pesticidal composition as claimed in claim 47 in the form of a dispersion, dust, wettable powder, emulsion concentrate or granules.

49. A pesticidal composition as claimed in either claim 47 or claim 48, which contains from 10 to 90% by weight of the compound of the general formula (I) or salt thereof.

50. A pesticidal composition as claimed in claim 47, substantially as described in any one of Examples I to VII herein.

51. A method of combating fungi or bacteria, which comprises applying a compound as claimed in any one of claims 1 to 36 and 46 or a composition as claimed in any one of claims 47 to 50.