DE4304010A1 - Use of pyrimidylhydrazones in the protection of materials - Google Patents

Abstract

Pyrimidylhydrazones of the formula <IMAGE> in which R<1> represents hydrogen, halogen, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy or haloalkythio, R<2> represents hydrogen, halogen, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy or haloalkylthio, or, if R<1> and R<2> are in the ortho position relative to each other, together represent an alkylene chain having 3 to 6 carbon atoms or a fused benzene ring, R<3> represents hydrogen, alkyl, cycloalkyl, cycloalkenyl, optionally substituted aryl, optionally substituted aralkyl, optionally substituted heteroaryl, or optionally substituted heteroarylalkyl, R<4> represents hydrogen or alkyl, R<5> represents hydrogen, alkyl, alkynyl, alkoxy, alkylthio or cycloalkyl, R<6> represents hydrogen, halogen, alkyl, alkoxy, alkylthio or cycloalkyl, and R<7> represents hydrogen, halogen, alkyl, alkoxy, alkylthio or cycloalkyl, and their acid addition salts and metal salt complexes are highly suitable for the protection of industrial materials against attack by microorganisms and/or animal pests.

Description

The present invention relates to the use of partially known pyrimidyl hydrazone in the material protection.

It has already become known that certain Pyrimidylhydrazones have fungicidal properties (see J. Pestic. Sci. 14, 295-300 (1989), BE-PS 561 091 and EP-PS 0 019 450). Use of these substances in Material protection has not yet been described ben.

It has now been found that pyrimidyl hydrazones of formula

in which
R ^{1 represents} hydrogen, halogen, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy or haloalkylthio,
R ^{2 represents} hydrogen, halogen, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy or haloalkylthio, or if
R ¹ and R ^{2 are} in the ortho position to one another, together represent an alkylene chain having 3 to 6 carbon atoms or represent a fused benzene ring,
R ^{3 represents} hydrogen, alkyl, cycloalkyl, cycloalkenyl, optionally substituted aryl, optionally substituted aralkyl, optionally substituted heteroaryl or optionally substituted heteroarylalkyl,
R ^{4 represents} hydrogen or alkyl,
R ^{5 represents} hydrogen, halogen, alkyl, alkynyl, alkoxy, alkylthio or cycloalkyl,
R ^{6 represents} hydrogen, halogen, alkyl, alkoxy, alkylthio or cycloalkyl and
R ^{7 represents} hydrogen, halogen, alkyl, alkoxy, alkylthio or cycloalkyl,
and their acid addition salts and metal salt complexes can be used very well to protect technical materials against attack by microorganisms or animal pests.

The compounds of formula (I) can, depending on the Position of the substituents on the C = N double bond in Form of geometric isomers (syn / anti) arise. The present invention relates both to the use of the pure isomers as well as the isomer mixtures.

Surprisingly, the ver reversible substances better to fight unwanted Microorganisms and animal pests in the material protection as the most constitutionally similar, known Active substances with the same direction of action.

Formula (I) provides a general definition of the pyrimidyl hydrazones which can be used according to the invention.
R ¹ preferably represents hydrogen, fluorine, chlorine, bromine, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, haloalkoxy 1 to 4 carbon atoms and 1 to 5 halogen atoms or for haloalkylthio with 1 to 4 carbon atoms and 1 to 5 halogen atoms.
R ² preferably represents hydrogen, fluorine, chlorine, bromine, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, haloalkoxy 1 to 4 carbon atoms and 1 to 5 halogen atoms or for haloalkylthio with 1 to 4 carbon atoms and 1 to 5 halogen atoms.
R ¹ and R ² are also preferably, if they are arranged in the ortho position to each other, together for an alkylene chain with 3 to 5 carbon atoms or for a fused benzene ring.
R ³ preferably represents hydrogen, straight-chain or branched alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, cycloalkyl having 3 to 8 carbon atoms, cyclo alkenyl having 3 to 8 carbon atoms, if appropriate simple to triple, similar or different phenyl or naphthyl substituted by halogen, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, alkylthio having 1 to 6 carbon atoms and / or haloalkyl having 1 to 6 carbon atoms and 1 to 7 halogen atoms, for optionally single to triple, similar or differently substituted by halogen, alkyl with 1 to 6 carbon atoms, alkoxy with 1 to 6 carbon atoms, alkylthio with 1 to 6 carbon atoms and / or haloalkyl with 1 to 6 carbon atoms and 1 to 7 halogen atoms substituted phenylalkyl with 1 to 4 carbon atoms Alkyl part, or for an optionally benz fused five- or six-membered heteroaromatic tables Residue with 1 to 3 heteroatoms, such as nitrogen, oxygen and / or sulfur, where each of these residues can be monosubstituted to triple, identical or differently substituted by halogen and / or alkyl having 1 to 4 carbon atoms, or for an optionally benzanellated hetero arylalkyl -Rest, where the heteroaryl part can be five or six-membered and can contain 1 to 3 heteroatoms, such as nitrogen, oxygen and / or sulfur, and the alkyl part can contain 1 to 4 carbon atoms and each of these hetero arylalkyl residues simply to can be triple, identical or differently substituted by halogen and / or alkyl having 1 to 4 carbon atoms.
R ⁴ preferably represents hydrogen or straight-chain or branched alkyl having 1 to 4 carbon atoms.
R ⁵ preferably represents hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, alkynyl having 2 to 6 carbon atoms, straight-chain or branched alkoxy having 1 to 6 carbon atoms, straight-chain or branched alkylthio having 1 to 4 carbon atoms, cycloalkyl having 3 to 7 Carbon atoms, fluorine, chlorine or bromine.
R ⁶ preferably represents hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkoxy having 1 to 6 carbon atoms, straight-chain or branched alkylthio having 1 to 4 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, fluorine, chlorine or Bromine.
R ⁷ preferably represents hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, alkynyl having 2 to 6 carbon atoms, straight-chain or branched alkoxy having 1 to 6 carbon atoms, straight-chain or branched alkylthio having 1 to 4 carbon atoms, cycloalkyl having 3 to 7 Carbon atoms, fluorine, chlorine or bromine.
R ¹ particularly preferably represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, tert-butyl, methoxy, ethoxy, methylthio, ethyl thio, haloalkyl having 1 or 2 carbon atoms and 1 to 3 fluorine , Chlorine and / or bromine atoms, haloalkoxy with 1 or 2 carbon atoms and 1 to 3 fluorine, chlorine and / or bromine atoms or for haloalkylthio with 1 or 2 carbon atoms and 1 to 3 fluorine, chlorine and / or bromine atoms.
R ² particularly preferably represents hydrogen, fluorine, chlorine, bromine, methyl, ethyl, n-propyl, isopropyl, tert-butyl, methoxy, ethoxy, methylthio, ethyl thio, haloalkyl having 1 or 2 carbon atoms and 1 to 3 fluorine , Chlorine and / or bromine atoms, haloalkoxy with 1 or 2 carbon atoms and 1 to 3 fluorine, chlorine and / or bromine atoms or for haloalkylthio with 1 or 2 carbon atoms and 1 to 3 fluorine, chlorine and / or bromine atoms.
If they are arranged in the ortho position to one another, R ¹ and R ² also particularly preferably together represent an alkylene chain having 3 to 5 carbon atoms or a fused benzene ring.
R ³ particularly preferably represents hydrogen, straight-chain or branched alkyl having 1 to 18 carbon atoms, alkenyl having 2 to 18 carbon atoms, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclopentenyl, cyclohexenyl, if appropriate simple to triple, identical or different by Fluorine, chlorine, bromine, alkyl with 1 to 4 carbon atoms, alkoxy with 1 to 4 carbon atoms, alkylthio with 1 to 4 carbon atoms, haloalkyl with 1 or 2 carbon atoms and 1 to 3 fluorine, chlorine and / or bromine atoms substituted phenyl or naphthyl, or for optionally single to triple, identical or different by fluorine, chlorine, bromine, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, haloalkyl having 1 or 2 carbon atoms and 1 to 3 fluorine, chlorine and / or bromine atoms substituted phenylalkyl with 1 or 2 carbon atoms in the alkyl part, or for pyrazolyl, imidazolyl, 1,2,4 -Triazolyl, pyrrolyl, furanyl, thienyl, thiazolyl, oxazolyl, pyridinyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, quinazolinyl, indolyl, benzothienyl, benzofuranyl, benzothiazolyl or benzimidazolyl, each of these radicals can be monosubstituted or trisubstituted, in the same way, or substituted by three, the same Fluorine, chlorine, bromine, methyl, ethyl and / or tert-butyl, or for pyrazolylmethyl, imidazolylmethyl, 1,2,4-triazolylmethyl, pyrrolylmethyl, furfuryl, thienylmethyl, thiazolylmethyl, oxazolylmethyl, pyridinylmethyl, pyrimidinylmethyl, triazinylmethyl, quinolinyl , Isoquinolinylmethyl, Quinazolinylmethyl, Indolylmethyl, Benzothienyl methyl, Benzofurfuryl, Benzothiazolylmethyl or Benzimidazolylmethyl, whereby each of these residues can be substituted one to three times, identically or differently by fluorine, chlorine, bromine, methyl, ethyl and / or tert.-butyl.
R ⁴ particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl.
R ⁵ particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, propargyl, methoxy, ethoxy, methylthio, ethylthio, cyclopropyl, cyclohexyl, cyclopentyl, fluorine, chlorine or bromine.
R ⁶ particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, methoxy, ethoxy, methylthio, ethylthio, cyclopropyl, cyclopentyl, cyclohexyl, fluorine, chlorine or bromine.
R ⁷ particularly preferably represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, propargyl, methoxy, ethoxy, methylthio, ethylthio, cyclopropyl, cyclopentyl, cyclohexyl, fluorine, chlorine or bromine.

Preferred substances which can be used according to the invention are also addition products of acids and those pyrimidyl hydrazones of the formula (I) in which R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 have} the meanings indicated as preferred.

Acids that can be added include: preferably hydrohalic acids, such as. B. the chlorine hydrochloric acid and hydrobromic acid, esp especially hydrochloric acid, also phosphoric acid, Nitric acid, sulfuric acid, mono- or bifunctional Carboxylic acids and hydroxycarboxylic acids, such as. B. Vinegar acid, maleic acid, succinic acid, fumaric acid, wine acid, citric acid, salicylic acid, sorbic acid and Lactic acid and sulfonic acids, such as. B. p-toluenesulfone acid, 1,5-naphthalenedisulfonic acid or camphorsulfone acid, saccharin and thiosaccharin.

In addition, preferred compounds which can be used according to the invention are addition products from salts of metals of the II. To IV. Main group and of I. and II. And IV. To VIII. Subgroup of the Periodic Table of the Elements and those pyrimidylhydrazones of the formula (I) in which R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and R ^{7 have} the meanings given as being preferred.

Here are salts of copper, zinc, manganese, magne sium, tin, iron and nickel especially before moves. Anions of these salts are those in Be that derive from such acids that to lead physiologically compatible addition products. Particularly preferred such acids are in this Connection the hydrohalic acids, such as. B. the Hydrochloric acid and hydrobromic acid, also phosphoric acid, nitric acid and sulfuric acid.

As examples of pyrimidyl hydrazones of the formula (I) are the substances listed in Table 1 below called.

The pyrimidyl hydrazones which can be used according to the invention Some formulas (I) are known (cf. J. Pestic. Sci. 14, 295-300 (1989), BE-PS 561 091 and EP-PS 0 019 450). The pyrimidyl hydrazones of the formula (I) and their acid addition salts and metal salt complexes can be produce by using 2-pyridyl ketones of the formula

in which
R ¹ , R ² and R ^{3 have} the meanings given above,
with pyrimidylhydrazines of the formula

in which
R ⁴ , R ⁵ , R ⁶ and R ^{7 have} the meanings given above,
in the presence of a diluent and, if appropriate, in the presence of a catalyst, and if appropriate adding an acid or a metal salt to the compounds of the formula (I) thus obtained.

If (pyrid-2-yl) propyl ketone and (pyrimid-2- yl) hydrazine as starting materials, the course of the Process for producing usable according to the invention Substances illustrated by the following formula scheme become:

The 2-pyridyl ketones required as starting materials in the above process are generally defined by the formula (II). The radicals R ¹ , R ² and R ³ preferably have those meanings which have already been mentioned as preferred for these substituents in connection with the description of the pyrimidylhydrazones of the formula (I) which can be used according to the invention.

The 2-pyridyl ketones of the formula (II) are known or can be manufactured according to known methods len (see BE-PS 561 091 and DE-OS 27 44 385). So get you get 2-pyridyl-ketones of formula (II), if you have 2-cyano pyridines of the formula

in which
R ¹ and R ^{2 have} the meanings given above,
with organometallic compounds of the formula

R³-Me (V)

in which
R ^{3 has} the meaning given above and
Me stands for lithium or MgX, where
X represents chlorine, bromine or iodine,
in the presence of an inert, organic diluent, such as, for example, diethyl ether, at temperatures between -20 ° C. and + 25 ° C. and the intermediate 2-pyridyl-ketimines of the formula

in which
R ¹ , R ² , R ³ and Me have the meanings given above,
in the presence of an inert, organic diluent, such as, for example, diethyl ether, successively with an aqueous buffer system, such as, for example, an aqueous ammonium chloride solution, and with acid, such as, for example, aqueous hydrochloric acid, at temperatures between -10 ° C. and + 20 ° C implements. The 2-pyridyl-ketones of the formula (II) can be isolated from the resulting mixture by customary methods. In general, the procedure is such that the reaction mixture is extracted with an organic solvent which is not very miscible with water and the solution obtained is distilled, if necessary after drying.

The in the preparation of the 2-pyridyl ketones of the formula (II) according to the above method as reaction components required substances of the formulas (IV) and (V) are known or can be produced using generally known methods put.

Formula (III) provides a general definition of the pyrimidylhydrazines which are furthermore required as starting materials in the process for the preparation of pyrimidylhydrazones which can be used according to the invention. The radicals R ⁴ , R ⁵ , R ⁶ and R ⁷ preferably have those meanings which have already been mentioned as preferred for these substituents in connection with the description of the pyrimidyl hydrazones of the formula (I) which can be used according to the invention.

The pyrimidylhydrazines of the formula (III) are known or can be done according to generally known methods produce.

As a diluent when performing the Process for producing usable according to the invention Pyrimidylhydrazone all usual inert, organic Solvents into consideration. Are preferably usable Alcohols, such as methanol, ethanol, n-propanol, iso propanol, n-butanol and tert-butanol, also nitriles, such as acetonitrile, also aromatic hydrocarbons, such as benzene, toluene and xylene and also halo generated aliphatic hydrocarbons such as methylene chloride, chloroform and carbon tetrachloride.

As catalysts come when performing the Ver driving to manufacture usable according to the invention Pyrimidylhydrazone all for such reactions reaction accelerator in question. Preferably Acids such as acetic acid and aqueous salt can be used acid.

The reaction temperatures can be carried out of the method for producing used according to the invention barer Pyrimidylhydrazone in a larger area can be varied. Generally one works at Tem temperatures between 0 ° C and 140 ° C, preferably between 20 ° C and 120 ° C.

When performing the manufacturing process he Pyrimidylhydrazone usable according to the invention works  one generally under normal pressure. It is also possible to increase or decrease pressure work.

When performing the manufacturing process he Pyrimidylhydrazones which can be used according to the invention are used to 1 mole of 2-pyridyl ketone of the formula (II) in general mean 0.8 to 1.2 moles of pyrimidylhydrazine of the formula (III) and optionally a small amount of one Reaction accelerator. The processing takes place according to usual methods. Generally one goes in the Way, that one concentrates the reaction mixture, the remaining residue with a little with water miscible organic solvent takes up the resulting Clean solution by filtration, then concentrate and den Residue recrystallized or distilled.

The pyrimidyl hydrazones which can be used according to the invention Formula (I) can be in acid addition salts or metal salt complexes are transferred.

For the production of acid addition salts of the compounds Those acids are preferred for the formula (I) in question already in connection with the description Exercise of acid addition usable according to the invention Salts have been mentioned as preferred acids.

The acid addition salts of the compounds of formula (I) can in a simple manner according to usual salt formation methods, e.g. B. by dissolving a compound of formula (I) in a suitable inert solvent and adding  the acid, e.g. B. hydrochloric acid can be obtained and in a known manner, e.g. B. by filtering, iso liert and optionally by washing with an inert organic solvents can be cleaned.

For the production of metal salt complexes of the compounds The salts of the formula (I) are preferably those of metals in question that are already related the description of those which can be used according to the invention Metal salt complexes mentioned as preferred metal salts were.

The metal salt complexes of the compounds of the formula (I) can be done in a simple manner using customary procedures will hold so z. B. by dissolving the metal salt in Alcohol, e.g. B. ethanol and adding to compounds of Formula (I). One can know metal salt complexes in known Way, e.g. B. by filtering, isolating and given if clean by recrystallization.

The active substances which can be used according to the invention have a strong microbicidal action and an action against animal pests and can protect against technical materials against infestation and destruction due to unwanted microorganisms and animal damage linge be used.

Under technical materials in the present Zu context to understand non-living materials that prepared for use in engineering are. For example, technical materials that  by active substances according to the invention before microbial ver change or destruction should be protected, adhesive fabrics, glues, paper and cardboard, textiles, leather, Wood, paints and plastic articles, cooling lubricant fabrics and other materials made by Mikroorga nisms can be attacked or decomposed. As part of the materials to be protected are also parts of Production plants, for example cooling water circuits, called, which affect by multiplication of microorganisms can be pregnant. As part of the present Er are preferred as technical materials Adhesives, glues, papers and cartons, leather, wood, an coating agents, cooling lubricants and heat transfer called liquids, particularly preferably wood.

As microorganisms that break down or change tion of the technical materials can be for example bacteria, fungi, yeast, algae and Called slime organisms. Preferably he act active substances against fungi which can be used according to the invention, in particular molds, wood staining and wood-destroying fungi (Basidiomycetes) and against Slime organisms and algae.

For example, microorganisms of the following genera may be mentioned:
Alternaria, such as Alternaria tenuis,
Aspergillus, such as Aspergillus niger,
Chaetomium, like Chaetomium globosum,
Coniophora, such as Coniophora puetana,
Lentinus, such as Lentinus tigrinus,
Penicillium, such as Penicillium glaucum,
Polyporus, such as Polyporus versicolor,
Aureobasidium, such as Aureobasidium pullulans,
Sclerophoma, such as Sclerophoma pityophila,
Trichoderma, like Trichoderma viride,
Escherichia, such as Escherichia coli,
Pseudomonas, such as Pseudomonas aeruginosa,
Staphylococcus, such as Staphylococcus aureus.

As animal pests, the destruction techni shear materials can be preferred Called insects. Examples include:

• A: Hymenoptera:
  Sirex jevencus
  Urocerus augur
  Urocerus gigas
  Urocerus gigas taignus
• B: Beetle:
  Anobicum punctatum
  Apate monachus
  Bostrychus capucins
  Chlorophores pilosus
  Dendrobium pertinex
  Dinoderus minutus
  Ernobius mollis
  Heterobostrychus brunneus
  Hylotrupes bajulus
  Lyctus africanus
  Lyctus brunneus
  Linear lctus
  Planicollis Lyctus
  Lyctus pubescens
  Minthea rugicollis
  Priobium carpini
  Ptilinus pecticornis
  Sinoxylon spec.
  Trypto dendron spec.
  Xestobium rufovillosum
  Xyleborus spec.
• C: Termites:
  Coptotermes formosanus
  Cryptotermes brevis
  Heterotermes indicola
  Kalotermes flavicollis
  Mastotermes darwiniensis
  Reticulitermes flavipes
  Reticulitermes lucifugus
  Reticulitermes santonensis
  Zootermopsis nevadensis

Depending on the field of application, the invention can active ingredients in the usual formulations are transferred, such as solutions, emulsions, suspensions sions, powders, pastes and granules.

These can be made in a manner known per se the, e.g. B. by mixing the active ingredients with a Extender that consists of liquid solvent and / or solid carriers exist, optionally using of surfactants such as emulsifiers and / or dispersants, where appropriate in If water is used as an extender organic Solvents such as alcohols are used as auxiliaries can be.

Liquid solvents for the active ingredients can, for example Water, alcohols, such as lower aliphatic Alcohols, preferably ethanol or isopropanol, or Benzyl alcohol, ketones such as acetone or methyl ethyl ketone, liquid hydrocarbons such as gasoline fractions, halogenated Be hydrocarbons such as 1,2-dichloroethane.

The used to protect technical materials Agents generally contain the active ingredients in one Amount from 1 to 95 wt .-%, preferably from 10 to 75 wt .-%.

The application concentrations of the invention too Active ingredients depend on the type and the occurrence of the microorganisms to be controlled and animal pests and according to the composition of the  material to be protected. The optimal amount can be used can be determined by test series. Generally lie the application concentrations in the range from 0.001 to 5% by weight, preferably from 0.05 to 1.0% by weight on the material to be protected.

The effectiveness and range of effects of the Invention according to the active substances that can be used, funds, concentrates or more generally form stakes can be increased if necessary antimicrobial compounds, fungicides, bacteria ricides, herbicides, insecticides or other active ingredients to enlarge the range of effects or to achieve special effects such. B. additional protection be added before insects. These blends can have a broader spectrum of activity than the inventions connections according to the invention.

In many cases, synergistic effects are obtained, ie the effectiveness of the mixture is greater than that of the individual components. Particularly favorable mixture partners are z. B. the following connections:
Sulfenamides such as dichlorfluanid (Euparen), tolylfluanid (Methyleuparen), Folpet, Fluorfolpet;
Benzimidazoles such as Carbendazim (MBC), Benomyl, Fuberid azole, Thiabendazole or their salts;
Thiocyanates such as thiocyanatomethylthiobenzothiazole (TCMTB), methylene bisthiocyanate (MBT);
quaternary ammonium compounds such as benzyldimethyltetra decylammonium chloride, benzyldimethyldodecylammonium chloride, dodecyldimethylammonium chloride; Morpholine derivatives such as C ₁₁ -C ₁₄ -4-alkyl-2,6-dimethyl-morpholine homologous (tridemorph), (±) -cis-4- (3-tert-butylphenyl) -2-methylpropyl) -2,6 -dimethylmorpholine (fenpropimorph), falimorph;
Phenols such as o-phenylphenol, tribromophenol, tetrachlorophenol, pentachlorophenol, 3-methyl-4-chlorophenol, dichlorophen, chlorophen or their salts;
Azoles such as triadimefon, triadimenol, bitertanol, tebu conazole, propiconazole, azaconazole, hexaconazole, prochloraz, cyproconazole, 1- (2-chlorophenyl) -2- (1-chlorocyclopropyl) -3- (1,2,4-triazol-1-) yl) propan-2-ol, 1- (2-chlorophenyl) -2- (1,2,4-triazol-1-yl-methyl) -3,3-dimethyl-butan-2-ol.

Iodopropargyl derivatives such as iodopropargyl butyl carbamate (IPBC), chlorophenyl formal, phenyl carbamate, hexyl carbamate, cyclohexyl carbamate, iodopropargyloxyethyl phenyl carbamate;
Iodine derivatives such as diiodomethyl-p-arylsulfones e.g. B. Diiod methyl p-tolyl sulfone;
Bromine derivatives such as bromopol;
Isothiazolines such as N-methylisothiazolin-3-one, 5-chloro-N-methylisothiazolin-3-one, 4,5-dichloro-N-octyl isothiazo lin-3-one, N-octylisothiazolin-3-one (octilinones);
Benzisothiazolinones, cyclopentene isothiazolines;
Pyridines such as 1-hydroxy-2-pyridinthione (and their Na, Fe, Mn, Zn salts), tetrachloro-4-methylsulphonyl pyridine;
Metal soaps such as tin, copper, zinc naphthenate, ocateate, -2-ethylhexanoate, oleate, phosphate, benzoate, oxides such as TBTO, Cu ₂ O, CuO, ZnO;
Organic tin compounds such as tributyltin naphthenate and tributyltin oxide;
Dialkyldithiocarbamates such as Na and Zn salts of dialkyldithiocarbamates, tetramethyltiuramide disulfide (TMTD);
Nitriles such as 2,4,5,6-tetrachloroisophthalonitrile (chlorothalonil), inter alia, microbicides with activated halogen group such as Cl-Ac, MCA, tectamer, bromopol, bromidox;
Benzothiazoles such as 2-mercaptobenzothiazoles; says Dazomet;
Quinolines such as 8-hydroxyquinoline;
Formaldehyde-releasing compounds such as benzyl alcohol mono (poly) hemiformal, oxazolidines, hexahydro-s-triazine, N-methylolchloroacetamide;
Tris-N- (cyclohexyldiazeniumdioxy) aluminum, N- (cyclohexyldiazeniumdioxy) -tributyltin or K. salts, bis- (N-cyclohexyl) diazinium (-dioxy- copper or aluminum).

The following are preferably added as insecticides:

Phosphoric acid esters such as azinphos-ethyl, azinphos-methyl, 1- (4-chlorophenyl) -4- (O-ethyl, S-propyl) phosphoryloxy pyrazole (TIA-230), chlorpyrifos, coumaphos, demeton, Demeton-S-methyl, diazinon, dichlorvos, dimethoate, Ethoprophos, Etrimfos, Fenitrothion, Fention, Hepteno phos, parathion, parathion-methyl, phosalone, phoxion, Pirimiphos-ethyl, Pirimiphos-methyl, Profenofos, Pro thiofos, sulprofos, triazophos and trichlorphone.

Carbamates such as aldicarb, bendiocarb, BPMC (2- (1-methyl propyl) phenylmethyl carbamate), butocarboxime, butoxycar boxim, carbaryl, carbofuran, carbosulfan, cloethocarb, Isoprocarb, methomyl, oxamyl, pirimicarb, promecarb, Propoxur and thiodicarb.

Pyrethroids such as allethrin, alphamethrin, bioresmethrin, Byfenthrin (FMC 54 800), cycloprothrin, cyfluthrin, Decamethrione, cyhalothrin, cypermethrin, deltamethrin, Alpha-cyano-3-phenyl-2-methylbenzyl-2,2-dimethyl-3- (2- Chloro-2-trifluoromethylvinyl) cyclopropane carboxylate, Fenpropathrin, fenfluthrin, fenvalerate, flucythrinate,  Flumethrin, fluvalinate, permethrin and resmethrin; Nitroimino and nitroimides such as 1 - [(6-chloro-3-pyridinyl) methyl] -4,5-dihydro-N-nitro-1H-imidazol-2-amine (Imida cloprid).

Organosilicon compounds, preferably dimethyl (phe nyl) silylmethyl-3-phenoxy-benzyl ether such as B. dimethyl (4-ethoxyphenyl) silylmethyl-3-phenoxybenzyl ether or Dimethyl (phenyl) silylmethyl-2-phenoxy-6-pyridylmethyl ethers such as B. Dimethyl (9-ethoxyphenyl) silylmethyl-2- phenoxy-6-pyridylmethyl ether or (phenyl) [3- (3-phenoxy phenyl) propyl] (dimethyl) silanes such as e.g. B. (4-ethoxyphe nyl) - [3 (4-fluoro-3-phenoxyphenyl) propyl] dimethyl silane.

Algicides are considered as other active substances, Molluscicides, active substances against "sea animals", which are on z. B. Settling floor paints.

The production of active ingredients and their erfindungsge Moderate use is demonstrated by the following examples illustrated.  

Manufacturing examples example 1

Under a nitrogen atmosphere, a mixture of 2.54 g (0.017 mol) (pyrid-2-yl) -n-propyl-ketone, 80 ml of ethanol, 1.87 g (0.017 mol) of (pyrimid-2-yl) hydrazine and 2 drops Glacial acetic acid heated under reflux for 60 hours. After that the reaction mixture is cooled to room temperature and by stripping off the solvent under reduced pressure Pressure reduced. You take the remaining residue in chloroform, filtered through a mixture of active coal and silica gel and concentrated again. The residue is recrystallized from petroleum ether. You get on this way 3.61 g (88% of theory) of (pyrid-2-yl) -n- propyl-keto- (pyrimid-2-yl) hydrazone in the form of a solid substance from melting point 82 to 89 ° C.

Preparation of the starting substance of the formula

Under a nitrogen atmosphere and with stirring Mixture of 61.7 g (0.6 mol) of n-propyl magnesium chloride in 100 ml of diethyl ether at 0 ° C dropwise with a Solution of 59.44 g (0.57 mol) of 2-cyano-pyridine in 100 ml Diethyl ether added. After the exothermic has subsided The reaction is stirred for a further 3 hours at 25 ° C., then Chilled to 0 ° C and dropwise with 142 ml of one 30% aqueous ammonium chloride solution added. On finally, while stirring, 223 ml of 6 N hydrochloric acid dripped in. After standing at room temperature for 12 hours The reaction mixture is ratur by adding ver thinner, aqueous sodium hydroxide solution made slightly basic and then extracted six times with 200 ml of diethyl ether. The combined organic solutions are over potassium carbonate dried and concentrated under reduced pressure tight. The remaining residue is distilled. Man receives 71.5 g (84% of theory) in this way (Pyrid-2-yl) -n-propyl-ketone in the form of a colorless Oil. 39 to 44 ° C / 0.06 Torr.

According to the previously specified method, the in the following table 2 substances specified in formulas produced.

According to the method given in Example 1 the substances listed in Table 3 below Formula (II) prepared.

Table 3

Examples of use Example A

To demonstrate the effectiveness against fungi, the minimal inhibitory concentrations (MIC) of fiction according to the active ingredients:

An agar made from wort and peptone is in concentration with active ingredients according to the invention from 0.1 mg / l to 5000 mg / l. After freezing contamination of the agar with pure cultures of the in test organisms listed in the table. After two weeks Storage at 28 ° C and 60 to 70% relative air moisture is determined the MIC. MIC is the lowest highest concentration of active ingredient at which none Overgrowth occurs due to the type of microbe used.

Active substances and MIC values are in the following table specified.

The abbreviations given in Table A have the following meanings
SCPLBR = Penicillium rebicaule
CHATGL = Chaetomium globosum
ASPENI = Aspergillus niger
BACISU / STAPAU = Bacillus subtilis
PSDMAE = Pseudomonas aeruginosa
SYDOPO = Selerophoma pityophila
TRCDVI = Trichoderma viride
MYCOTA = Chladosporium herbarum
ALTEAL = Alternaria tenuis
AURERU = Aureobasidium pullulans

Claims (3)

1. Use of pyrimidylhydrazone of the formula in which
R ^{1 represents} hydrogen, halogen, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy or haloalkylthio,
R ^{2 represents} hydrogen, halogen, alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy or haloalkylthio, or if
R ¹ and R ^{2 are} in the ortho position to one another, together represent an alkylene chain having 3 to 6 carbon atoms or represent a fused benzene ring,
R ^{3 represents} hydrogen, alkyl, cycloalkyl, cyclo alkenyl, optionally substituted aryl, optionally substituted aralkyl, optionally substituted heteroaryl or optionally substituted heteroarylalkyl,
R ^{4 represents} hydrogen or alkyl,
R ^{5 represents} hydrogen, halogen, alkyl, alkynyl, alkoxy, alkylthio or cycloalkyl,
R ^{6 represents} hydrogen, halogen, alkyl, alkoxy, alkylthio or cycloalkyl and
R ^{7 represents} hydrogen, halogen, alkyl, alkynyl, alkoxy, alkylthio or cycloalkyl,
as well as their acid addition salts and metal salt complexes for protecting technical materials against attack by microorganisms or animal pests. 2. Use according to claim 1, characterized in that substances of formula (I) are used in which
R ^{1 represents} hydrogen, fluorine, chlorine, bromine, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, haloalkoxy having 1 to 4 carbon atoms and 1 to 5 halogen atoms or represents halogen alkylthio having 1 to 4 carbon atoms and 1 to 5 halogen atoms, and
R ^{2 represents} hydrogen, fluorine, chlorine, bromine, alkyl having 1 to 4 carbon atoms, alkoxy having 1 to 4 carbon atoms, alkylthio having 1 to 4 carbon atoms, haloalkyl having 1 to 4 carbon atoms and 1 to 5 halogen atoms, haloalkoxy having 1 to 4 carbon atoms and 1 to 5 halogen atoms or represents halogen alkylthio having 1 to 4 carbon atoms and 1 to 5 halogen atoms and
R ¹ and R ² furthermore, when they are arranged in the ortho position to one another, together represent an alkylene chain having 3 to 5 carbon atoms or a fused benzene ring,
R ^{3 represents} hydrogen, straight-chain or branched alkyl having 1 to 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, cycloalkyl having 3 to 8 carbon atoms, cycloalkenyl having 3 to 8 carbon atoms, optionally one to three times, in the same way or differently by halogen, alkyl phenyl or naphthyl substituted with 1 to 6 carbon atoms, alkoxy with 1 to 6 carbon atoms, alkylthio with 1 to 6 carbon atoms and / or haloalkyl with 1 to 6 carbon atoms and 1 to 7 halogen atoms, optionally optionally up to three times, identical or different by halogen, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, alkyl thio having 1 to 6 carbon atoms and / or haloalkyl having 1 to 6 carbon atoms and 1 to 7 halogen atoms substituted phenyl alkyl having 1 to 4 carbon atoms in the alkyl part , or for an optionally benzanellated five- or six-membered heteroaromatic radical 1 to 3 hetero atoms, where each of these radicals can be mono- to triple, identical or differently substituted by halogen and / or alkyl having 1 to 4 carbon atoms, or represents an optionally benzanellated hetero arylalkyl radical, the heteroaryl part being five or can be six-membered and can contain 1 to 3 heteroatoms and the alkyl part can contain 1 to 4 carbon atoms and each of these heteroarylalkyl radicals can be substituted once to three times, in the same way or differently, by halogen and / or alkyl having 1 to 4 carbon atoms,
R ^{4 represents} hydrogen or straight-chain or branched alkyl having 1 to 4 carbon atoms,
R ^{5 represents} hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, alkynyl having 2 to 6 carbon atoms, straight-chain or branched alkoxy having 1 to 6 carbon atoms, straight-chain or branched alkylthio having 1 to 4 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, fluorine, chlorine or bromine,
R ^{6 represents} hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, straight-chain or branched alkoxy having 1 to 6 carbon atoms, straight-chain or branched alkylthio having 1 to 4 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, fluorine, chlorine or bromine stands and
R ^{7 represents} hydrogen, straight-chain or branched alkyl having 1 to 6 carbon atoms, alkynyl having 2 to 6 carbon atoms, straight-chain or branched alkoxy having 1 to 6 carbon atoms, straight-chain or branched alkylthio having 1 to 4 carbon atoms, cycloalkyl having 3 to 7 carbon atoms, fluorine, chlorine or bromine. 3. Procedures to combat unwanted micro organisms and / or animal pests in the Material protection, characterized in that one Pyrimidylhydrazones of the formula (I) according to Claim 1 or their acid addition salts or metal salt Complexes on the microorganisms or animal Pests and / or their habitat.