GB2357971A - Protection of plants against microorganism attack - Google Patents

Abstract

The present invention relates to a method for protecting and immunizing plants against attack by phytopathogenic microorganisms by applying a compound of formula I or compositions which comprise a compound of the formula I to the plants, to parts of the plants and/or to the locus of the plants. The compounds suitable to be applied according to the invention are of the general formula I <EMI ID=1.1 HE=36 WI=47 LX=393 LY=1128 TI=CF> <BR> <PC>wherein:<BR> X<SB>1</SB> is halogen<BR> Z is -C(=O)A, -C(=S)A, -CH(OR<SB>2</SB>)<SB>2</SB> or -C(OR<SB>2</SB>)<SB>3</SB> and in which<BR> A is OR<SB>3</SB>, SR<SB>3</SB>, NR<SB>4</SB>R<SB>5</SB>, NHOR<SB>6</SB>, -ON=CR<SB>7</SB>R<SB>8</SB> or NH-N(C)<SB>n</SB>(R<SB>9</SB>)R<SB>10</SB>;<BR> and the remaining substituents are according to claim 1. Certain of these compounds are novel.

Description

2357971 Organic Compounds The present invention relates to a method for

protecting and immunizing plants against attack by phytopathogenic microorganisms, for example fungi, bacteria and viruses, by applying a compound of formula 1 or compositions which comprise a compound of the formula 1 to the plants, to parts of the plants andlor to the locus of the plants. The invention also relates to new compounds of formula fla), their preparation and use.

Salicylic acid and derivatives having fungicidal and stress tolerance inducing activities are known, for example, from WO 99125191, H. Tsuzuki, et al., Shokuhin Eiseigaku Zasshi, 34(2), 1993, 142-7 and D. F. Klessig, et.al., Critical Reviews in Plant Sciences, 18(4), 1999, 547-575.

The compounds suitable to be applied according to the invention are those of the general formula 1 Z H OR1 F1::][: X, wherein X, is halogen Z is -C(=0)A, -C(=S)A, -CH(OR2)2or -C(OR2)3and in which A is hydrogen, OR3, SR3, NR4R5, NHOR6, -ON=CR7R8 or NI- 1^=C)n(R9)R10; R, is hydrogen; Cl-CAlkyl which can be unsubstituted or substituted by phenyl, -C(=0)0C1C2alkyl, -C(=0)0benzyI, Cl-C3alkoxy, phenoxy, -C(=0)-Cl-C3alkyl or -C(=0)phenyl, where the respective phenyl radicals of these substituents can be unsubstituted or substituted once or twice by halogen andlor methoxy;C3-C6alkenyl; -C(=0)-CI-CBalkyl which can be unsubstituted or substituted by phenyl, -C(=0)0Cl-C2a]kyl, Cl- CAlkoxy, phenoxy, benzyloxy or -OC(=0)-Cl-C3alkyl; -C(=0)phenyl, where the phenyl radical can be unsubstituted or substituted once or twice by halogen, hydroxy], methoxy, trifluoromethyl or trifluoromethoxy; C(=0)N(C1-CAlkyl)2; -C(=S)N(C1-C2alkyi)2; -SO2-Cl-C2alkyi; -S02-benzyl or- S02-phenyl, substituted once or twice by halogen, hydroxyl, methoxy, trifluoromethyl or trifluoromethoxy; or -S02-INIR15R16; R2 is Cl-C4alkyl which can be unsubstituted or substituted by phenyl, Cl- C2alkoxy, phenoxy or benzyloxy; -C(=0)-Cl-C4alkyi; or a cyclic 5 to 6- membered acetal which can be unsubstituted or substituted by Cl-C3alkyl, Cl-C3hydroxyalkyl, hydroxyl or benzy]; R3is hydrogen; a singly to triply charged metallic cation, or IN1H4+; Cl- C8alkyl which can be unsubstituted or substituted once to three times by halogen, C3-C6CYCloalky], Cl-C4alkoxy, phenoxy, benzyloxy, hydroxyl, carboxyl, C(=0)0C1-C4alkyl or C(=0)Obenzyi; C3-C6alikenyl;C3-C6a]kinyi; C3-C6CYCloalkyl; phenyl, benzy] or phenethyl, where the respective phenyl radicals of these substituents can be unsubstituted or substituted once to three times by halogen, Cl-CAlkyl, hydroxyl, Cl-C2alkoxy, trifluoromethyl or trifluorornethoxy; -C(=0)-ClC4alkyl; -C(=0)phenyl; or a 5- or 6-membered heterocycle having one to three heteroatoms selected from N, 0 and S; R4 is hydrogen; Cl-C8alkyl which can be unsubstituted or substituted once to three times by halogen,C3-CC,CYC]oalky], Cl-C4alkoxy, phenoxy, benzyloxy, hydroxyl, carboxyl, C(=0)0C1C4alkyl or C(=0)Obenzyi; C3- Cralkenyl; C3-C6alkinyl; C3-C6CYCloalkyl; phenyl, benzy] or phenethy], where the respective phenyl radicals of these substituents can be unsubstituted or substituted once to three times by halogen, Cl- C4alkyl, hydroxyl, Cl-C2a]koxy, trifluorornethyl or trifluoromethoxy; -C(=0)-Cl-C4alkyi; -C(=0)phenyl; or a 5- or 6-membered heterocycle having one to three heteroatoms selected from N, 0 and S; R5 is hydrogen, Cl-C6alkyl or benzy]; or R4and R5 form, together with the nitrogen atom, a cyclopentylarnine, cyclohexylamine, morpholine or dimethyimorpholine ring; R6, R7, R8, R9 and Rio are independently of one another hydrogen, Cl- C6alkyl, phenyl or pyridyl, where the phenyl radical or pyridyl radical can be unsubstituted or substituted once to three times by halogen,Cl-C4alky], hydroxyl, ClC2alkoxy, trifluoromethyl or trifluoromethoxy; n is 0 or 11; and R15and Rle, are independently of one another hydrogen,Cl-C4alkyl, phenyl or benzyi.

Halogen is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.

Alky], on its own or as a constituent of another substituent, is to be understood as meaning straight-chain or branched-chain alkyls. Depending on the number of carbon atoms indicated, they constitute the following groups, for example: methyl, ethyl and the isomers of propyl, butyl, pentyl or hexy], for example isopropyl, isobutyl, tert-butyl, sec-butyl or isopenty].

3 Alkenyl is, for example, 1-propenyl, allyl, 1-butenyl, 2-butenyl or 3butenyl.

Alkinyl is, for example, 1 -propynyl or 1 -butynyl.

Cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, preferably cyclopropyl, cyclopentyl or cyclohexy].

Examples of 5- or 6-membered heterocycles having nitrogen, oxygen andlor sulfur as heteroatoms are: thiophene, thiazole, furan and pyridine.

All the above mentioned radicals are given by way of example and do not represent any limitation.

The invention also relates to novel compounds of formula la and lb, to the preparation of those compounds and to agrochemical compositions comprising at least one of those compounds as active ingredient.

Thus, it is a further object of this invention to provide compounds of the general formulae]a and 1b 0 A S A H OR1 H ORI H:: (1a) and: i H H wherein A is OR3, SR3, NIR4R5, NHOR6, -ON=CR7R8 or NI-I-N(=C),,(R9)1R10; R, is hydrogen;C2-C4alkyl orCl-C4alkyl substituted by phenyl, -C(=0)0ClC2alkyi, C(=0)Obenzyi, Cl-C3alkoxy, phenoxy, -C(=0)-Cl-C3alkyl or C(=0)phenyl, where the respective phenyl radicals of these substituents can be unsubstituted or substituted once or twice by halogen and/or methoxy; C3-CAlkenyl; -C(=0)-Cl-C8alkyl which can be unsubstituted or substituted by phenyl, -C(=0)0Cl-C2a]kyi,Cl-C3a]koxy, phenoxy, benzyloxy or -OC(=0)-Cl-C3alkyl; -C(=0)phenyl, where the phenyl radical can be unsubstituted or substituted once or twice by halogen, hydroxy], methoxy, trifluoromethyl or trifluoromethoxy; - 4 C(=0)N(C1-CAlky%; -C(=S)N(Ci-C2alkyl)2; -S02-Cl-C2alkyl; -S02-benzyl or - S02-phenyl, where the respective phenyl radicals of these substituents can be unsubstituted or substituted once or twice by halogen, hydroxyl, methoxy, trifluoromethyl or trifluoromethoxy; or -S02-NR,5R,6; and R, is also methyl in formula lb; R3 is hydrogen; a singly to triply charged metallic cation, or NI-14+; Cl-C8alkyl which can be unsubstituted or substituted once to three times by halogen, C3-C6CYCloalkyl, Cl-C4alkoxy, phenoxy, benzyloxy, hydroxyl, carboxyl, C(=0PC1-C4alkyl or C(=0)Obenzyi; C3-Cr'alkenyl; C3-Cr,alkinyl; C3-Cr cycloalkyi; phenyl, benzyl or phenethyl, where the respective phenyl radicals of these substituents can be unsubstituted or substituted once to three times by halogen, Cl-CAlkyl, hydroxyl, Cl-C2alkoxy, trifluoromethyl or trifluoromethoxy; -C(=0)-ClC4alkyl; -C(=0)phenyl; or a 5- or 6-membered heterocycle having one to three heteroatoms selected from N, 0 and S; R4 is hydrogen; Cl-C8alkyl which can be unsubstituted or substituted once to three times by halogen, C3-C6CYCloalkyl, Cl-C4alkoxy, phenoxy, benzyloxy, hydroxyl, carboxy], C(=0)0C1C4alkyl or C(=0)Obenzyi; C3-Cralkenyl; C3-Cealkiny]; C3-C6cycloalkyl; phenyl, benzyl or phenethy], where the respective phenyl radicals of these substituents can be unsubstituted or substituted once to three times by halogen, Cl-C4alkyl, hydroxyl, Cl-C2alkoxy, trifluoromethyl or trifluoromethoxy; -C(=0)-Cl- C4alkyi; -C(=0)phenyl; or a 5- or 6-membered heterocycle having one to three heteroatoms selected from N, 0 and S; R5 is hydrogen, Cl-C6alkyl or benzyl; or R4 and R5 form, together with the nitrogen atom, a cyclopentylamine, cyclohexylamine, morpholine or dimethyimorpholine ring; R6, R7, R8, R9 and Rio are independently of one another hydrogen, Cl- C6alkyi, phenyl or pyridyl, where the phenyl radical or pyridyl radical can be unsubstituted or substituted once to three times by halogen, Cl- C4alky], hydroxy], Cl-C2alkoxy, trifluoromethyl or trifluoromethoxy; n is 0 or 1; and R15 and R1r. are independently of one another hydrogen, Cl- C4alkyl, phenyl or benzyi.

For reason of avoiding duplication, thoughout the description and unless otherwise stated, reference to compounds of formula 1 is to be understood to also be a reference to compounds of formulae la and lb.

The compounds of formula 1 and, where appropriate, their tautomers can be in the form of. salts. Compounds of formula 1 that have at least one basic center can form acid addition salts. Furthermore, compounds of the formula 1 having at least one acid group can form salts with bases. Preference is given to agrochemically advantageous salts.

Important compounds of the formula 1 are those in which Z is -C(=0)A or C(=S)^ and in particular those in which A is OR3, SR3 or NR4R5, whereby SR3 is preferred.

Compounds of formula 1 are preferred which possess the following substituents or combinations of these substituents amongst themselves:

X, is either fluorine, chlorine or bromine; Z is C(=0)A; A is hydrogen, OR3, SR3 or NR4R5, whereby SR3 is most preferred; R, is hydrogen, acetyl, methyl or allyl; R3 and R4 are hydrogen; Cl-QBalkyl which can be unsubstituted or substituted once to three times by halogen, C3C6CYcloalkyl, Cl-C4alkoxy, phenoxy, benzy[oxy, hydroxyl, carboxyl, C(=0)0C1-C4alkyl or C(=0)Obenzyi; C3-C6alkenyl; phenyl or benzyl, where the respective phenyl radicals of these substituents can be unsubstituted or substituted once to three times by halogen, hydroxyl, methoxy, trifluoromethyl andlor trifluoromethoxy; R5 is hydrogen.

Of these, those are preferred wherein X, is chlorine; Z is COOH, COSCH3 and COOCH3; R, is hydrogen, acety], methyl or allyl.

The compounds according to the invention have only a very weak direct activity against fungi and bacteria. However, these compounds effectively protect the plants from phytopathogehic microorganism by activation and stimulation of the plant's own defence system (immunisation). This mode of action is known by the name "Systemic Activated Resistance" (SAR). SAR compounds and methods are ecologically advantageous. It is therefore desirable to provide more compounds and methods for protecting plants by immunising them against attack by phytopathogenic microorganism.

The compounds of the formula 1, in which X, is halogen and Z is C(=0^ can be prepared as follows:

Synthesis of the compounds of formula 1 6 1. CH3WN, CH3S 0 OH 13C13,AlCI3 2. HCI OH axl a) 1 LiOH, xl OH H20-M HO 0 CHC131 b) OH e) NaOH xl Na0C10 N a 0 Meu' H 0 c) 0 A 0 H 0 H xl 0 A f,9) xl OR1 xl The reaction details may be found, for example, in the following references: a) EP0266849 (Al); b) M.Delmas, et. al., Synthetic Communications, 18(16&17), 1988, 2095-2101; c) JP Bayle, et. al., Bull. Soc. Chim. Fr., 27, 1990, 565; d) Houben-Weyl, Bd E5, 4. edition, 193ff; JP1 1302228; e) Houben-Weyl, Bd V116, 4. edition, 832; f) Houben-Weyl, Bd V116, 4. edition, 49ff, 85f1; g) F. Bosch, J.-IE. Banos, AINE 2(3), 1998, 108-117.

General overview: S. H. Erickson in Kirk-Othmer Encycl. Chem. Technol., Editor(s): Grayson, Martin; Eckroth, David, 3rd Ed., 20, Wiley, New York, N. Y 1982, 500-24.

Suitable bases, leaving groups, activating methods, coupling methods, reaction-inert solvents and catalysts are known to the skilled person. Additional methods for preparing the precursors, are familiar to the skilled person or are described in the literature.

7 The compounds of formula 1 can be used in the agricultural sector and related fields preventively andlor curratively as active ingredients in the control of plant pests. The compounds of formula 1 according to the invention are distinguished by excellent action even at low rates of concentration and by the fact that they are well tolerated by plants and are environmentally friendly. They have very advantageous, especially systemic, properties and can be used to protect numerous cultivated plants. The compounds of formula 1 can be used to inhibit or destroy the pests which occur on plants or on parts of plants (the fruit, blossoms, leaves, stems, tubers or roots), while at the same time parts of plants that grow later are also protected, for example against phytopathogenic microorganisms.

The compounds 1 can also be used as dressings in the treatment of seed (fruit, tubers, grains) and plant cuttings to provide protection against fungus infections as well as against phytopathogenic fungi which occur in the soil.

The compounds 1 are effective, for example against phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Botrytis, Pyricularia, Colletotrichum, Helm inthosporiu m, Fusarium, Septoria, Cercospora and Alternaria); Basidiomycetens (e.g. the genera Hemileia, Rhizocotonia and Puccinia); Ascomycetes (e.g. Venturia, Podosphaera, Erysiphe, Monilinia and Uncinula) and the Oomycetes which belong to the Phycomycetes (e.g. Phytophthora, Plasmopara, Pythium, Bremia etc.). In addition to this, the compounds according to the invention are effective against phytopathogenic bacteria and viruses (e.g. against Xanthomonas spp., Pseudomonas spp. and Erwinia amy[ovora, and also against tobacco mosaic virus).

The following plant species, for example, are regarded, within the scope of this invention, as being target crops for the plant-protective use which is disclosed herein: cereals (wheat, barley, rye, oats, rice, maize, sorghum and related species); beets (sugar beet and feeding beet); pip fruit, stone fruit and berry fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); legumes (beans, lentils, peas and soybean); oil crops (rape, mustard, poppy, olives, sunflowers, coconut, castor oil, cacao and peanuts); cucumber plants (pumpkin, cucumbers and melons); fiber plants (cotton, flax, hemp and jute); citrus fruits (oranges, lemons, shaddocks and mandarins); vegetable varieties (spinach, garden lettuce, asparagus, cabbage species, carrots, onions, tomatoes, potatoes and pepper); laurel plants (avocado, cinnamon and camphor), or plants such as tobacco, nuts, coffee, sugar cane, tea, pepper, grapevines, hops, banana plants, natural rubber plants and ornamental plants (Compositae).

8 The invention also relates to compositions which comprise the compounds of the formula 1 as an active compound component, in particular plantprotecting compositions, and also to their use in the agricultural sector or related areas.

Active compounds of the formula 1 are customarily used in the form of compositions and may be added, simultaneously or successively, to the surface or plant to be treated together with additional active compounds. These additional active compounds may be either fertilizers, trace element-supplying agents or other preparations which influence plant growth. It is also possible, in this context, to use selective herbicides, such as insecticides, fungicides, bactericides, nematicides or molluscicides, or mixtures of several of these preparations, additionally, where appropriate, together with excipients, surfactants or other administrationpromoting additives which are customary in formulation technology. Suitable excipients and additives may be solid or liquid and are those substances which are appropriate in formulation technology, for example natural or regenerated minerals, solvents, dispersants, wetting agents, adhesives, thickening agents, binding agents or fertilizers.

A preferred method for applying a compound of formula 1, or an agrochemical composition which comprises at least one of these compounds, is application to the leaves (foliar application). The frequency and rate of application depend upon the risk of infestation by the corresponding pathogen. The compounds 1 can, however, also penetrate the plant through the roots via the soil (systemic action). If the locus of the plant is impregnated with a liquid formulation or if the substances are introduced in solid form into the soil, e.g. in the form of granules (soil application). In paddy rice. crops, such granules can be applied in metered amounts to the flooded rice fields. In order to treat seeds, the compounds 1 can, however, also be applied to the seeds (coating), either by impregnating the grains or tubers with a liquid formulation of the active ingredient, or by coating them with a solid formulation.

Advantageous rates of application are in normally from 5 g to 2 kg of active ingredient (a.i.) per hectare (ha), preferably from 10 g to 1 kg of a. Uha, especially from 20 g to 600 g a. Uha. When the compound are used as seed dressings, dosages of from 10 mg to 1 g of active ingredient per kg seed are advantageous employed. The agrochemical compositions generally comprise 0. 1 to 99% by weight, preferably 0. 1 to 95% by weight, of a compound of formula 1, 99.9 to 1% by weight, preferably 99.8 to 5% by weight, of a solid or liquid adjuvant and 0 to 25% by weight, preferably 0. 1 to 25 % by weight, of a surfactant. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.

9 The compositions may also comprise further auxiliaries, such as stabilizers, antifoams, viscos ity regulators, binders or tackifiers, as well as fertilizers or other active ingredients for obtaining special effects.

A. Preparative examples Abbreviations: RT = room temperature; m.p. = melting point.

ExamDle Al. 3-Chloro-2-hvdroxy-thiobenzoic acid S.-methyl ester H 1. CH3SCN, 0 H OH BC13, AIC13 H OH 2. HCl c H H C, H To 280 mi of a solution of 1.0 M boron trichloride-dichloromethane are added a solution of 31.1 g (241 mol) of 2-chlorophenol in 220 mi 1,2- dichlorethane and 19.1 mi (278 mol) of methyl thiocyanate and 31.0 g (232 mol) of aluminum chloride under ice-cooling. After dissolving aluminum chloride with stirring at room temperature, the mixture is heated at 800C for 3 h while evaporating the dichloromethane. After ice-cooling, the reaction solution is mixed with 140 g of ice and 350 mi of 2 N HCl and heated at 11 O'C under stirring to evaporate 1,2-dichloroethane and further stirred for 64 h. After cooling, the mixture is extracted with toluene. The toluene layer is dried over magnesium suffate anhydrous and chromatographed on a column of silica gel using toluene as the eluent to yield 13.2 g (27%) of 3-chloro-2-hydroxy-thiobenzoic acid S.-methyl ester as pale yellow needles (m.p.: 889O.C).

Example A2. 3-Chloro-2-hvdroxy-benzaidehyde H 0 H H OH CHC13, NaOH- H OH H cl H cl H H g sodium hydroxide (powdered) (2 mol) are added to a mixture of 80 g (0. 62 mol) 2chlorophenol, 800 mi CI-IC13and 32 rril water maintaining the temperature of the reaction medium at 580C. The temperature is held for one hour before further 140 g sodium hydroxide (powdered) (3.5 mol) are added progressively over three hours, maintaining the temperature constant at 580C. After cooling to RT, the reaction mixture is diluted with water, acidified with 2 N HCI and extracted with ethyl acetate. The organic layer is then washed with brine, dried over sodium sulfate and concentrated in vacuo. The resulting 86 g crude brown oil is distilled through a 10 cm Vigreux column (55-580C10.2 mbar) to yield 45.7 g (47%) yellow crystals (m.p: 54-55OC).

Example A3. 3-Chloro-2-hvdroxy-benzoic acid by oxidation of its aldehyde 0 H 0 OH H OH Na0C10, NaOMe H OH H 1 ( IN 1 cl H cl H H Ill 1V g (0.255 mol) 3-chloro-2-hydroxy-benzaidehyde is dissolved in 500 mi dimethyl sulfoxide and cooled to WC before adding 65 mi (0.35 mol) sodium methoxide solution (5.4 M in methanol). The reaction mixture is stirred for 15 min., cooled to WC and 56.5 g (0.50 mol) sodium chlorite (80% purity) is added. The temperature is held for additional 2 h before the mixture is warmed up to RT and stirred for further 5 h. The reaction mixture is poured on 1.5 1 ice water, acidified with 2N HCI and extracted four times with ethyl acetate. The organic layer is then washed five times with saturated sodium bicarbonate solution. The collected water layer is adjusted to pH 1 with 6 N HCI, saturated with solid sodium chloride and extracted with ethyl acetate. The organic layer is dried over sodium sulfate and concentrated in vacuo to yield 40.1 g (90%) product as slightly brownish crystals (m.p.: 174-175%).

Example A4. 3-Chloro-2-hvdroxy-benzoic acid by solvolysis of its thioester 0 SCH3 0 OH H OH LiOH, H20/MeOH 1-1 OH H cl H cl H H 1V 12.9 g (0.064 mol) thioester is dissolved in a mixture of 50 mi methanol and 350 mi water and treated with 6.1 g (0. 15 mol) lithium hydroxide monohydrate. After stirring at RT for 24 h, the reaction solution was acidified with 2 N HCI, saturated with solid sodium chloride and extracted three times with ethyl acetate. The organic layer is dried over sodium sulfate and concentrated in vacuo. The crude product is recrystallized from toluene at OOC to yield 7.9 g (72%) product as yellow crystals.

Example A5. 3-Chloro-2-hvdroxy-benzoic acid methyl ester by solvolysis 0 SCH 3 0 OCH 3 H OH LiOH, Me0H/H20 H OH H cl H cl H H 11 v 9.8 g (0.049 mol) thioester is dissolved in a mixture of 240 m] methanol and 60 mi water and treated with 4.6 g (0. 11 mol) lithium hydroxide monohydrate. After stirring at RT for 24 h, the reaction solution is acidified with 1 N HIZI, saturated with solid sodium chloride and extracted three times with ethyl acetate. The organic layer is dried over sodium sulfate and concentrated in vacuo to yield 8.0 g (87%) pure product as a pale brown oil.

12 Example A6: 3-Chloro-2-hvdroxv-.N... N.-dimethvi-benzamide 0 OH 0 NMe 2 H OH HNW2, CD1 H OH H cl H cl H H 1V V1 8.0 g (46.3 mmol) 3-chlorosalicylic acid is dissolved in 80 m[ tetrahydrofurane, cooled in an ice-bath to OOC and treated with 8g (49 mmol) 1, 1'-carbonyidiimidazole. The reaction mixture is stirred and slowly heated up to RT over a period of 3 h. The addition of 25 m] (140 mmol) dimethylamine solution in ethanol (5.6 M) is slightly exothermic. The resulting mixture is stirred at RT over a period of 8 h before poured on ice water and acidified with 2 N HCL After saturation with solid sodium chloride and extraction with ethyl acetate, the combined organic layer is washed with saturated sodium bicarbonate solution, dried over sodium suffate and concentrated in vacuo to yield 3.72 g (63%) pale brown crystals (m.p.: 126-132OC) Example A7: 3-Chloro-2-methoxy-benzoic acid methyl ester 0 0Me 0 0Me H OH CH311 K2C03 H 0Me H cl H cl H H v V11 1.52 g (8.11 mmol) 3-chloro-2-hydroxy-benzoic acid methyl ester is dissolved in 35 mi acetone and subsequently treated with 1.2 g (8.9 mmol) anhydrous potassium carbonate and 1 ml methyl iodide. The reaction mixture is vigorously stirred at RT for 10 hr, filtered and concentrated under vacuo. Chromatography over silica gel affords 1.33 g (82%) of a colorless liquid.

13 Example AB: 2-Acetoxy-3-chloro-benzoic acid methyl ester 0 0Me 0 0Me H OH acidic anydrid, H Ov H Cl pyridine H cl 0 H H v Vill 1.46 g (7.8 mmol) 3-chloro-2-hydroxy-benzoic acid methyl ester is dissolved in 10 m 1 pyridine, treated with 4 m[ acidic anhydride and stirred at RT for 10 hr. The reaction mixture is diluted with 100 mi ethyl acetate, washed subsequently with saturated cupric sulfate solution, saturated sodium bicarbonate solution and brine. The organic layer is dried over sodium sulfate and evaporated under vacuo. Recrystallization from etherlpetrolether affords 1.72 g (97%) white needles (m.p.: 61-64OC).

The compounds listed below are obtained by applying the described methods of preparation to suitable starting materials and by varying alkylating and acylating reagents as well as the condensed nucleophiles. Table 1: compounds of the formula 1 z H OR1 H::]:: (1), wherein Z is -C(=0)A H CpdA R, X, Phys. data No.

1 H H F m.p.: 62-64'C 2 H H 1 m.p: 54-55'C 3 H H Br M.1p.: 49-50'C 4 H H 1 OH H F 93-96'C 14 6 OH H Cl m.p.: 174-175C 7 OH H Br m.p.: 178-18M 8 OH H 1 9 ONa+ H F ONa+ H Cl 11 ONa+ H Br 12 ONa+ H 1 13 ONI-14+ H F 14 ONI-14+ H Cl ONI-14+ H Br 16 ONI-14+ H 1 17 SCH3 H F m.p.: 62-65C 18 SCH3 H Cl m.p.: 88-90C 19 SCH3 H Br m.p.: 89-92% SCH3 H 1 21 SCH2CH3 H F 22 SCH2CH3 H Cl 23 SCH2CH3 H Br 24 SCH9CH3 H 1 S-benzyl H F 26 S-benzyl H Cl 27 S-benzyl H Br 28 S-benzyl H 1 29 OCH3 H F m.p.: 46-470C OCH3 H Cl m.p.: 29-37C 31 OCH3 H Br n D20: 1.5790 32 OCH3 H 1 33 OCH2CH3 H F 34 OCH2CH3 H Cl OCH2CH3 H Br 36 OCH2CH3 H 1 37 OCH2CH=CH2 H F 38 OCH2CH=CH2 H Cl 39 OCH2CH=CH2 H Br OCH2CH=CH2 H 1 41 0-n-propyl H F ---1 42 0-n-propyl H cl 43 0-n-propyl H Br 44 0-n-propyl H 1 04-propyl H F 46 04-propyl H cl 47 04-propyl H Br 48 04-propyl H 1 49 0-n-butyl H F 0-n-butyl H cl 51 0-n-butyl H Br 52 0-n-butyl H 1 53 04-butyl H F 54 04-butyl H Cl 04-butyl H Br 56 04-butyl H 1 57 0-phenyl H F 58 0-phenyl H cl 59 0-phenyl H Br 0henyl H 1 61 0-benzyi H F 62 0-benzyi H cl 63 0-benzyl H Br 64 0-benzyl H 1 0-(4-MeO-benzyl) H F 66 0-(4-MeO-benzyi) H cl 67 0-(4-MeO-benzyi) H Br 68 0-(4-MeO-benzyi) H 1 69 NH2 H F NH2 H cl 71 N112 H Br 72 NH2 H 1 73 NHCH3 H F 74 NHCH3 H cl NHCH3 H Br 76 NIACH3 H 1 77 N(CH3)2 H F m.p.: 150-1530C 16 78 N(CH3)2 H Cl m.p.: 126-1320C 79 N(CHI H Br m.p.: 117-1200C N(CH3)2 H 1 81 NH-phenyl H F 82 NH-phenyl H Cl 83 NH-phenyl H Br 84 INIH-phenyl H 1 NH-NH-phenyl H F 86 NH-NH-phenyl H Cl 87 NWINIH-phenyl H Br 88 NWNH-phenyl H 1 89 H CH3 F H CH3 Cl 91 H CH3 Br 92 H CH3 1 93 OH CH3 F 94 OH CH3 Cl OH CH3 Br 96 OH CH3 1 97 ONa+ CH3 F 98 ONa+ CH3 Cl 99 ONa+ CH3 Br ONa+ CH3 1 101 ONH4+ CH3 F 102 ONH4+ CH3 Cl 103 ONH4+ CH3 Br 104 ONJ-14+ CH3 1 SCH3 CH3 F nD 20: 1.5523; b.p.: 2590C 106 SCH3 CH3 Cl nD 20: 1.5850 107 SCH3 CH3 Br nD 20: 1.6047 108 SCH3 CH3 1 109 SCH2CH3 CH3 F SCH2CH3 CH3 Cl ill SCH2CH3 CH3 Br 112 SCH2CH3 CH3 1 113 S-benzy] CH3 F 17 114 S-benzyl CH3 cl S-Ibenzyl CH3 Br 116 S-benzy] CH3 1 117 OCH3 CH3 F nD 20: 1.4972 118 OCH3 CH3 Cl n D20: 1.5295 119 OCH3 CH3 Br nD 20: 1.5505 OCH3 CH3 1 121 OCH2CH3 CH3 F 122 OCH2CH3 CH3 cl 123 OCH2CH3 CH3 Br 124 OCH2CH3 CH3 1 OCH2CH=CH2 CH3 F 126 OCH2CH=CH2 CH3 cl 127 OCH2CH=CH2 CH3 Br 128 OCH2CH=CH2 CH3 1 129 0-n-propyl CH3 F 0-n-propyl CH3 cl 131 0-n-propyl CH3 Br 132 0-n-propyl CH3 1 133 04-propyl CH3 F 134 04-propyl CH3 cl 04-propyl CH3 Br 136 0-i-propyl CH3 1 137 0-n-butyl CH3 F 138 0-n-butyl CH3 cl 139 0-n-butyl CH3 Br 0-n-butyl CH3 1 141 04-1butyl CH3 F 142 04-butyl CH3 cl 143 04-butyl CH3 Br 144 0-i-butyl CH3 1 0-phenyl CH3 F 146 0-phenyl CH3 cl 147 0-phenyl CH3 Br 148 0-phenyl CH3 1 149 0-benzyi CH3 F 18 0-benzyl CH3 cl 151 0-benzyl CH3 Br 152 0-benzyl CH3 1 153 0-(4-MeO-benzyi) CH3 F 154 0-(4-MeO-benzyi) CH3 cl 0-(4-MeO-benzyi) CH3 Br 156 0-(4-MeO-benzyi) CH3 1 157 NH2 CH3 F 158 NH2 CH3 cl 159 NH2 CH3 13r NH2 CH3 1 161 NHCH3 CH3 F 162 NHCH3 CH3 cl 163 NHCH3 CH3 Br 164 NHCH3 CH3 1 N(CH3)2 CH3 F n J0: 1.5162 166 N(CH3)2 CH3 Cl nD 20: 1.5448 167 N(CH3)2 CH3 Br nD 20: 1.5632 168 N(CH3)2 CH3 1 169 NH-phenyl CH3 F NH-phenyl CH3 cl 171 NH-phenyl CH3 Br 172 NH-phenyl CH3 1 173 NWNH-phenyl CH3 F 174 NH-NH-phenyl CH3 cl NIHI-NH-phenyl CH3 Br 176 NH-NH-phenyl CH3 1 177 H COCH3 F 178 H COCH3 cl 179 H COCH3 Br H COCH3 1 181 OH COCH3 F 182 OH COCH3 cl 183 OH COCH3 Br 184 OH COCH3 1 ONa+ COCH3 F 19 186 ONa+ COCH3 cl 187 ONa+ COCH3 Br 188 ONa+ COCH3 1 189 ON1H14+ COCH3 F ON1H14+ COCH3 cl 191 ON1H14+ COCH3 Br 192 ON1H14+ COCH3 1 193 SCH3 COCH3 F nD 20: 1.5430 194 SCH3 COCH3 Cl nD 20: 1.5710 SCH3 COCH3 Br nD 20: 1.5872 196 SCH3 COCH3 1 197 SCH2CH3 COCH3 F 198 SCH2CH3 COCH3 cl 199 SCH2CH3 COCH3 Br SCH2CH3 COCH3 1 201 S-Ibenzyi COCH3 F 202 S-Ibenzyl COCH3 cl 203 S-Ibenzyl COCH3 Br 204 S-benzy] COCH3 1 205 OCH3 COCH3 F nD 20 A.4942 206 OCH3 COCH3 Cl m.p.: 611-64C 207 OCH3 COCH3 Br m.p.: 54-56C 208 OCH3 COCH3 1 209 OCH2CH3 COCH3 210 OCH2CH3 COCH3 cl 211 OCH2CH3 COCH3 Br 212 OCH2CH3 COCH3 1 213 OCH2CH=CH2 COCH3 F 214 OCH2CH=CH2 COCH3 cl 215 OCH2CH=CH2 COCH3 Br 216 OCH2CH=CH2 COCH3 1 217 0-n-propyl COCH3 F 218 0-n-propyl COCH3 cl 219 0-n-propyl COCH3 Br 220 0-n-propyl COCH3 1 221 04-propyl COCH3 F 222 0-i-propyl COCH3 cl 223 0-i-propyl COCH3 Br 224 04-propyl COCH3 1 225 0-n-butyl COCH3 F 226 0-n-butyl COCH3 cl 227 0-n-butyl COCH3 Br 228 0-n-butyl COCH3 1 229 0-i-butyl COCH3 F 230 0-i-butyl COCH3 cl 231 0-i-butyl COCH3 Br 232 04-butyl COCH3 1 233 0-phenyl COCH3 F 234 0-phenyl COCH3 cl 235 0-phenyl COCH3 Br 236 0-phenyl COCH3 237 0-benzyl COCH3 F 238 0-benzyl COCH3 cl 239 0-benzyi COCH3 Br 240 0-benzyl COCH3 1 241 0-(4-MeO-benzyl) COCH3 F 242 0-(4-MeO-benzyi) COCH3 cl 243 0-(4-MeO-benzyi) COCH3 Br 244 0-(4-MeO-benzyi) COCH3 1 245 NH2 COCH3 F 246NH2 COCH3 cl 247 NH2 COCH3 Br 248 NH2 COCH3 1 249 NHCH3 COCH3 F 250 NHCH3 COCH3 cl 251 NHCH3 COCH3 Br 252 NIHICH3 COCH3 1 253 N(CHI COCH3 F nD 20:1.5061 254 N(CH3)2 COCH3 Cl nD 211: 1.5305 255 N(CH3)2 COCH3 Br n D20: 1.5435 256 N(CH3)2 COCH3 1 257 NH-phenyl COCH3 F 21 258 NI-1-phenyl COCH3 cl 259 NH-phenyl COCH3 Br 260 NI-1-phenyl COCH3 1 261 NI-I-NI-1-phenyl COCH3 F 262 NI-I-NI-1-phenyl COCH3 cl 263 NI-I-NI-1-phenyl COCH3 Br 264 NI-I-NI-1-phenyl COCH3 1 265 H CH2CH=CH2 F 266 H CH2CH=CH2 cl 267 H CH2CH=CH2 Br 268 H CH2CH=CH2 1 269 OH CH2CH=CH2 F 270 OH CH2CH=CH2 cl 271 OH CH2CH=CH2 Br 272 OH CH2CH=CH2 1 273 ONa+ CH2CH=CH2 274 ONa CH2CH=CH2 cl 275 ONa+ CH2CH=CH2 Br 276 ONa' CH2CH=CH2 1 277 ONI-14+ CH2CH=CH2 F 278 ONI-14+ CH2CH=CH2 cl 279 ONI-14+ CH2CH=CH2 Br 280 ONI-14+ CH2CH=CH2 1 281 SCH3 CH2CH=CH2 F nD 20 A.5487 282 SCH3 CH2CH=CH2 Cl nD 21: 1.5780 283 SCH3 CH2CH=CH2 Br nD 21: 1.5950 284 SCH3 CH2CH=CH2 1 285 SCH2CH3 CH2CH=CH2 F 286 SCH2CH3 CH2CH=CH2 cl 287 SCH2CH3 CH2CH=CH2 Br 288 SCH2CH3 CH2CH=CH2 1 289 S-benzyl CH2CH=CH2 F 290 S-benzyl CH2CH=CH2 cl 291 S-benzyi CH2CH=CH2 Br 292 S-benzy] CH2CH=CH2 1 293 OCH3 CH2CH=CH2 F 20 A.5033 22 294 OCH3 CH2CH=CH2 Cl n J0: 1.5305 295 OCH3 CH2CH=CH2 Br nD 20: 1.5485 296 OCH3 CH2CH=CH2 1 297 OCH2CH3 CH2CH=CH2 F 298 OCH2CH3 CH2CH=CH2 Cl 299 OCH2CH3 CH2CH=CH2 Br 300 OCH2CH3 CH2CH=CH2 1 301 OCH2CH=CH2 CH2CH=CH2 F 302 OCH2CH=CH2 CH2CH=CH2 Cl 303 OCH2CH=CH2 CH2CH=CH2 Br 304 OCH2CH=CH2 CH2CH=CH2 1 305 0-n-propyl CH2CH=CH2 F 306 0-n-propyl CH2CH=CH2 Cl 307 0-n-propyl CH2CH=CH2 Br 308 0-n-propyl CH2CH=CH2 1 309 04-propyl CH2CH=CH2 F 310 04-propyl CH2CH=CH2 Cl 311 04-propyl CH2CH=CH2 Br 312 0-i-propyl CH2CH=CH2 1 313 0-n-butyl CH2CH=CH2 F 314 0-n-butyl CH2CH=CH2 Cl 315 0-n-butyl CH2CH=CH2 Br 316 0-n-butyl CH2CH=CH2 1 317 04-butyl CH2CH=CH2 F 318 04-butyl CH2CH=CH2 Cl 319 0-i-butyl CH2CH=CH2 Br 320 04-butyl CH2CH=CH2 1 321 0-phenyl CH2CH=CH2 F 322 0-phenyl CH2CH=CH2 Cl 323 0-phenyl CH2CH=CH2 Br 324 0-phenyl CH2CH=CH2 1 325 0-benzyi CH2CH=CH2 F 326 0-benzyi CH2CH=CH2 Cl 327 0-benzyi CH2CH=CH2 Br 328 0_benzy] CH2 H=CH2 1 329 0-(4-MeO-benzyi) CH2CH=CH2 F 330 0-(4-MeO-ben?-yi) CH2CH=CH2 cl 331 0-(4-MeO-benzyi) CH2CH=CH2 Br 332 0-(4-MeO-benzyi) CH2CH=CH2 1 333 NH2 CH2CH=CH2 334 NH2 CH2CH=CH2 cl 335 NH2 CH2CH=CH2 Br 336 NH2 CH2CH=CH2 1 337 NHCH3 CH2CH=CH2 F 338 NHCH3 CH2CH=CH2 cl 339 NHCH3 CH2CH=CH2 Br 340 NHCH3 CH2CH=CH2 1 341 N(CHA2 CH2CH=CH2 F n 1)20: 1.5185 342 N(CHA2 CH2CH=CH2 Cl nD 20: 1.5420 343 N(CH3)2 CH2CH=CH2 Br nD 20: 1.5583 344 N(CHA2 CH2CH=CH2 1 345 NI-1-phenyl CH2CH=CH2 F 346 NI-1-phenyl CH2CH=CH2 cl 347 NH-phenyl CH2CH=CH2 Br 348 NH-phenyl CH2CH=CH2 1 349 NI-I-NI-1-phenyl CH2CH=CH2 F 350 NWNI-1-phenyl CH2CH=CH2 cl 351 NI-I-NI-1-phenyl CH2CH=CH2 Br NWNI-1-phenyl CH2CH=CH2 1 B. Biological examples Example B1: Effect against Colletotrichurn lagenarium on Cucumis sativus L.

a) Residual protective effect After having been cultivated for 10 days, cucumber plants are sprayed with a spray liquor (concentration: 200 ppm) of the active compound.

After 4-7 days, the plants are infected with a spore suspension (approximately 1.2xl 05spores/mi) of the fungus and incubated at a temperature of 200C for 24hours at high 24 atmospheric humidity in the dark. The incubation is then continued at normal atmospheric humidity and at from 22C to 23%.

days after the infection, the protective effect is assessed on the basis of the fungal infestation.

b) Systemic effect After having been cultivated for 10 days, cucumber plants are treated, by means of application to the soil, with the active compound (concentration: 20ppm based on the soil volume).

After 4 to 7 days, the plants are infected with a spore suspension (approximately 1.2xl Osspores/mi) of the fungus and incubated at a temperature of 200C for 24 hours at high atmospheric humidity in the dark. The incubation is then continued at normal atmospheric humidity and at 220C.

days after the infection, the protective effect is assessed on the basis of the fungal infestation.

Untreated but infected control plants exhibited 50 to100% infestation with Colletotrichum.

Example B2: Effect against Phytophthora infestans on tomato plants a) Residual protective effect After having been cultivated for 3 weeks, tomato plants are sprayed with a spray liquor (0.02% active substance) which has been prepared from a formulation of the active compound. After 4 to 7 days, the treated plants are infected with a spore suspension of the fungus. The fungal infestation was assessed after incubating the infected plants for 6 days at 90-100% relative atmospheric humidity and at 118'C.

b) Systemic effect A spray liquor (0.002% active substance based on the soil volume) which has been prepared from a formulation of the active compound is supplied by pouring to tomato plants after they have been cultivated for 3 weeks. Care is taken, in this context, to ensure that the spray liquor does not come into contact with the parts of the plants which are above the soil. After 4 to 7 days, the treated plants are infected with a spore suspension of the fungus. The fungal infestation is assessed after incubating the infected plants for 6 days at 90-100% relative atmospheric humidity and at 180C, Untreated but infected control plants exhibited a 60 to 100% infestation with Phytophthora.

Example B3: Effect aciainst Piricularia orvzae on rice plants b) Systemic effect: A spray liquor (0.006% active substance based on the soil volume) which has been prepared from a formulation of the active compound is supplied by pouring to 18 day-old rice plants. After that, the pots are filled with water to such an extent that the lowest parts of the rice plant stems are standing in the water. After 4 to 10 days, the treated rice plants are infected with a conidial suspension of the fungus. The fungal infestation is assessed after the infected plants have been incubated for 5days at 100% relative atmospheric humidity and at approximately 24C.

In comparison with untreated control plants (100% infestation), rice plants which were treated with a spray liquor which contained a compound from Example B4: Effect against Pseudomonas lachrymans on Cucumis sativus L.

a) Residual protective effect After having been cultivated for 10 days, cucumber plants are sprayed with a spray liquor (concentration: 200 ppm) which has been prepared from a formulation of the active compound.

After 4 to 7 days, the plants are infected With a bacterial suspension (approximately 108cells/mi) and incubated for 7days at high atmospheric humidity and at a temperature of 230C.

days after the infection, the protective effect is assessed on the basis of the fungal infestation. Compounds of formula 1 show a good to very good protective effect.

b) Systemic effect After having been cultivated for 1 Odays, cucumber plants are treated, by means of application to the soil, with a spray liquor which has been prepared from a formulation of the active compound (concentration 20ppm based on the soil volume).

26 After 4 to 7 days, the plants are infected with a bacterial suspension (approximately 10'cells/mi) and incubated for 7 days at high atmospheric humidity and at a temperature of 230C.

days after the infection, the protective effect is assessed on the basis of the bacterial infestation. Compounds of formula 1 show a good to very good protective effect.

Untreated but infected control plants exhibited a 50 to 100% infestation with Pseudomonas.

Example B5: Immunizing effect against tobacco mosaic virus on tobacco 8 week-old tobacco plants are sprayed (concentration: 200 ppm) or injected (concentration: 200 ppm) with a formulated solution of the active compound. After 4 ays, the plants are inoculated mechanically with a suspension of tobacco mosaic virus + carborundum and incubated at a temperature of 20-22C.

7 days after the inoculation, the protective effect is assessed on the basis of the number and size of the local lesions.

Infected but untreated control plants exhibited 30 to 100% lesions.

Example B6: Effect against Xanthomonas ornae on rice (Oryza sativa) b) Systemic effect After having been cultivated in a greenhouse for 3 weeks, a suspension of the test substance is supplied to rice plants by pouring such that the rice plant itself is not wetted (0.006% active substance based on the soil volume). 4 to 10 days after this treatment, the plants are placed in a climate chamber at 240C and 90 -100% relative atmospheric humidity, and infected. The infection is achieved by cutting off the leaf tips with a pair of scissors which has previously been immersed in a suspension of Xanthomonas oryzae. After having been incubated for 10 days, the cut leaves, if infested, wilt, roll up and become necrotic. The extent of these disease symptoms is used to assess the systemic activity of the test substance.

Example B7: Effect against Cercospora nicotianae on tobacco 27 8 week-old tobacco plants are treated with a formulated solution of the active compound (concentration: 20Oppm). 4 days after treatment, the plants are sprayed with a spore suspension of Cercospora nicotianae (approximately 105spores/mi) and incubated for 5days at high atmospheric humidity and at a temperature of 22-250C. The incubation is then continued at normal atmospheric humidity and at 20-22'C. 12-14 days after the infection, the symptoms are then assessed on the basis of the fungal infestation.

28

Claims (10)

Claims:

1. A process for protecting and immunizing plants against attack by phytopathogenic microorganisms, comprises applying at least one of the compounds of formula (1) as the active ingredient to the plants, to part of the plants, to seeds andlor the locus of the plants Z H OR1 1 X, H wherein X, is halogen Z is -C(=0)^ -C(=S)^ -CH(OR2)2or -C(OR2)3and in which A is hydrogen, OR3, SR3, NIR4R5, NHOR6, ON=CR7R8 or NWN(=C), (R9)1R10; R, is hydrogen; Cl-C4alkyl which can be unsubstituted or substituted by phenyl, -C(=0)0C1C2alkyl, -C(=0)Obenzy], Cl-CAlkoxy, phenoxy, -C(=0)-Cl-C3alkyl or -C(=0)phenyl, where the respective phenyl radicals of these substituents can be unsubstituted or substituted once or twice by halogen andlor methoxy; C3-C6alkenyl; -C(=0)-Cl-C8alkyl which can be unsubstituted or substituted by phenyl, -C(=0PC1-C2alkyl, Cl- CAlkoxy, phenoxy, benzyloxy or -OC(=0)-Cl-C3alkyi; -C(=0)pheny], where the phenyl radical can be unsubstituted or substituted once or twice by halogen, hydroxyl, methoxy, trifluoromethyl or trifluoromethoxy; C(=0)N(C1-C2ailky02; -C(=S)N(C1-C2alkyi)2; -S02-Cl-C2alkyl; -S02-benzylorSO2-phenyl, where the respective phenyl radicals of these substituents can be unsubstituted or substituted once or twice by halogen, hydroxyl, methoxy, trifluoromethyl or trifluoromethoxy; or -S02-NR,,5R,6; R2 is ClC4alkyl which can be unsubstituted or substituted by phenyl, Cl-CAlkoxy, phenoxy or benzyloxy; -C(=0)-Cl-C4alkyl; or a cyclic 5 to 6-membered acetal which can be unsubstituted or substituted byCl-C3alky], ClC3hydroxyalkyl, hydroxyl or benzyi; R3 is hydrogen; a singly to triply charged metallic cation, or NH4+; Cl-C8alkyl which can be unsubstituted or substituted once to three times by halogen,C3-C6CYCloalky], Cl- C4alkoxy, phenoxy, benzyloxy, hydroxyl, carboxyl, C(=0PC1-C4alkyl or C(=0)01Jenzy]; C3-C6alkeny]; C3-C6alkinyl; C3-C6CYCloalky]; phenyl, benzy] or phenethyl, where the respective phenyl 29 radicals of these substituents can be unsubstituted or substituted once to three times by halogen, Cl-CAlkyl, hydroxyl, Cl-C2alkoxy, trifluoromethyl or trifluoromethoxy; -C(=0)-ClC4aiky]; -C(=0)pheny]; or a 5- or 6-membered heterocycle having one to three heteroatoms selected from N, 0 and S; R4 is hydrogen; Cl-C8alkyl which can be unsubstituted or substituted once to three times by halogen, C3-C6cycloalkyl, Cl-C4alkoxy, phenoxy, benzyloxy, hydroxyl, carboxyl, C(=0)0C1C4alkyl or C(=0)Obenzy]; C3-Cralkenyl; C3-C6alkiny]; C3-C6cycloalkyl; phenyl, benzy] or phenethyl, where the respective phenyl radicals of these substituents can be unsubstituted or substituted once to three times by halogen, Cl-C4alkyl, hydroxy], Cl-C2alkoxy, trifluoromethyl or trifluoromethoxy; -C(=0)-Cl- C4alky]; -C(=0)pheny]; or a 5- or 6-membered heterocycle having one to three heteroatoms selected from N, 0 and S; Rs is hydrogen, Cl-C6alkyl or benzyi; or R4 and Rs form, together with the nitrogen atom, a cyclopentylamine, cyclohexylamine, morpholine or dimethyimorpholine ring; Re, R7, R8, R9 and Rio are independently of one another hydrogen, Cl- C6alkyl, phenyl or pyridyl, where the phenyl radical or pyridyl radical can be unsubstituted or substituted once to three times by halogen, Cl- CAlkyl, hydroxyl, Cl-C2alkoxy, trifluoromethyl or trifluoromethoxy; n is 0 or 1; and R15 and R16 are independently of one another hydrogen, Cl- CAlkyl, phenyl or benzy].

2. A composition according to claim 1 in which the active ingredient is a compound of formula 1, wherein Z is -C(=0)A or -C(=S)^ and A is SR3.

3. A composition according to claim 1 in which the active ingredient is a compound of formula 1, wherein X, is fluorine, chlorine or bromine; Z is C(=0)A; A is SR3; R, is hydrogen, acetyl, methyl or allyl: and R3 and is hydrogen, Cl-C8alkyl which can be unsubstituted or substituted once to three times by halogen, C3-Crcycloalkyl, Cl-C4alkoxy, phenoxy, benzyloxy, hydroxyl, carboxyl, C(=0PC1-CAlkyl or C(=0)Obenzyi, C3-C6alkenyl, phenyl or benzyl, where the respective phenyl radicals of these substituents can be unsubstituted or substituted once to three times by halogen, hydroxyl, methoxy, trifluoromethyl andlor trifluoromethoxy.

4. A compound of the general formula (1a) or (Jb) 0 A S A H OR1 H OR1 1 (1a) 1 (1b) H z xl H z xl H H wherein A is OR3, SR3, NIR4R5, NHOR6, -ON=CR7R8 or NH-N(=C)n(Rg)R,(); R, is hydrogen; C2-C4alkyl or Cl-C4alkyl substituted by phenyl, -C(=0)0Cl- C2a]kyi, C(=0)Obenzyi, Cl-C3alkoxy, phenoxy, -C(=0)-CI-C3alkyl or - C(=0)phenyl, where the respective phenyl radicals of these substituents can be unsubstituted or substituted once or twice by halogen andlor methoxy; C3-C6alkenyl; -C(=0)-Cl-C8alkyl which can be unsubstituted or substituted by phenyl, -C(=0)0Cl-C2alkyi, Cl-C3alkoxy, phenoxy, benzyloxy or -OC(=0)-Cl-C3alkyl; -C(=0)phenyl, where the phenyl radical can be unsubstituted or substituted once or twice by halogen, hydroxyl, methoxy, trifluoromethyl or trifluoromethoxy; C(=0)N(C1-C2alkyl)2; -C(=S)N(C1- C2alkyl)2; -S02-Cl-C2a]kyl; -S02-benzyl or -S02-phenyl, where the respective phenyl radicals of these substituents can be unsubstituted or substituted once or twice by halogen, hydroxy], methoxy, trifluoromethyl or trifluoromethoxy; or -S02-NR,5R16; and R, is also methyl in formula lb; R3 is hydrogen; a singly to triply charged metallic cation, or IN1H4'; Cl-C8alkyl which can be unsubstituted or substituted once to three times by halogen, C3-C6cycloalkyl, Cl-C4alkoxy, phenoxy, benzyloxy, hydroxyl, carboxy], C(=0)OCI-C4alkyl or C(=0)0benzyi; C3-C6alkenyl; C3-C6alkinyl; C3-C6C00alky]; phenyl, benzyi or phenethyl, where the respective phenyl radicals of these substituents can be unsubstituted or substituted once to three times by halogen, Cl-C4alky], hydroxyl, Cl-C2alkoxy, trifluoromethyl or trifluoromethoxy; -C(=0)-ClC4alkyl; -C(=0)phenyl; or a 5- or 6-membered heterocycle having one to three heteroatoms selected from N, 0 and S; R4 is hydrogen; Cl-Cealkyl which can be unsubstituted or substituted once to three times by halogen, C3-C6CYCloalkyl, Cl-C4alkoxy, phenoxy, benzyioxy, hydroxyl, carboxyl, C(=0)0C1C4alkyl or C(=0)Obenzyi; C3-Cralkenyl; C3-C6alkinyl; C3-C6CYCloalkyl; phenyl, benzyl or phenethyl, where the respective phenyl radicals of these substituents can be unsubstituted or substituted once to three times by halogen, Cl-C4alkyl, hydroxyl, Cl-C2alkoxy, 31 trifluoromethyl or trifluoromethoxy; -C(=0)-Cl-C4a]ky]; -C(=0)phenyl; or a 5- or 6-membered heterocycle having one to three heteroatoms selected from N, 0 and S; R5 is hydrogen, Cl-C6alkyl or benzyl; or R4and R5form, together with the nitrogen atom, a cyclopentylamine, cyclohexylamine, morpholine or dimethyimorpholine ring; R6, R7, R8, R9 and Rio are independently of one another hydrogen, Cl-C6alkyl, phenyl or pyridyl, where the phenyl radical or pyridyl radical can be unsubstituted or substituted once to three times by halogen, Cl-CAlkyl, hydroxyl, ClC2alkoxy, trifluoromethyl or trifluoromethoxy; n isOorl; and R15and R16 are independently of one another hydrogen, Cl-CAlkyl, phenyl or benzyi.

5. A compound of the formula la or lb according to claim 4, wherein A is SR3.

6. A compound of the formula la according to claim 4, wherein X, is fluorine, chlorine or bromine; A is SR3; R, is hydrogen, acetyl, methyl or allyl: and R3and is hydrogen, Cl-C8alkyl which can be unsubstituted or substituted once to three times by halogen, C3-Cocycloalkyl, Cl-CAlkoxy, phenoxy, benzyloxy, hydroxyl, carboxyl, C(=0PC1-CAlkyl or C(=0)0benzy],C3C6alikenyl, phenyl or benzyl, where the respective phenyl radicals of these substituents can be unsubstituted or substituted once to three times by halogen, hydroxyl, methoxy, trifluoromethyl andlor trifluoromethoxy.

7. The use of a compound of the formula 1 according to claim 1 for protecting plants against infestation with phytopathogenic microorganisms.

8. A process according to claim 1, wherein the phytopathogenic organisms are fungal organisms.

9. A process according to claim 1, wherein the fungal organisms are from the Ascomycetes, Basidiomycetes, Oomycetes or Fungi imperfecti classes.

10. A process according to claim 1, wherein the phytopathogenic organisms are bacteria.

11 - A process according to claim 1, wherein the phytopathogenic oorganisms are viruses.

32 12. A process according to claim 1, wherein the phytopathogenic microorganisms are nematodes or insects 13. An agrochemical composition comprising a compound of formula 1 according to claim 1 and an inert carrier.