JP2007534652A - 3-Trifluoromethylpicolinic acid anilide and its use as a fungicide - Google Patents

Abstract

The present invention relates to 3-trifluoromethylpicolinic acid anilide of the general formula (I), wherein X represents oxygen, sulfur or a direct bond, W represents oxygen or sulfur, and n represents 0, 1, 2, 3 Or the substituents have the meanings given in the claims) and the agriculturally useful salts of (I). The invention further relates to the use of said 3-trifluoromethylpicolinic acid anilides of general formula (I) and their agriculturally acceptable salts as fungicides, and to plant protection agents containing them.

Description

  The present invention relates to 3-trifluoromethylpicolinic acid anilide having bactericidal activity and its use as a bactericidal agent, ie for controlling harmful bacteria.

  Hetaryl anilide with bactericidal activity is the subject of many patent applications (eg WO 86/02641, JP 01313402, US 4,877,441, EP 371950, WO 93/11117, EP 545099, DE 4204766, DE 4204768, EP 591699). , EP 589301, JP 07145156, JP 08092223, WO 97/08148, WO 98/03500, EP 824099, EP 846416, WO 00/09482, WO 01/42223, EP 1110454, EP 1110956, WO 01/49664, JP 2001- 302605, WO 02/08195, WO 02/08197, WO 02/38542, WO 02/59086, WO 02/064562, WO 03/010149, WO 03/66609, WO 03/66610, WO 03/69995, WO 03 / 74491 and WO 03/70705). However, especially at low application rates, the hetaryl anilides described in these publications are not entirely satisfactory.

JP 58096069 is the formula

(Where R is CH ³ or CF ₃ )
Disclosed are picolinic acid anilides effective for sterilization. However, the bactericidal activity of these compounds is insufficient.

  The object of the present invention is to provide further fungicidal active compounds which have an improved action, in particular at low application rates, overcoming the disadvantages of the compounds known from the prior art. In addition, these compounds must have good compatibility with useful plants and, if possible, cause little if any harm to useful animals. .

  We have found that this object is achieved by the 3-trifluoromethylpicolinic acid anilides of formula I and their agriculturally acceptable salts described below.

Accordingly, the present invention provides compounds of formula I

(Where n is 0, 1, 2, 3 or 4 and the substituents are defined as follows:
X is O, S or a direct bond;
W is O or S;
R ₁ , R ² and R ³ are independently of each other hydrogen, halogen, nitro, CN, C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkyl, C ₂ -C ₄ -alkenyl, C _2- C ₄ -alkynyl, C ₁ -C ₄ -alkoxy, and some or all of the hydrogen atoms in the four last listed groups can be substituted with halogen;
R ⁴ is hydrogen, OH, C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkyl C ₁ -C ₄ -alkoxy, and some of the hydrogen atoms in the three last listed groups or All can be substituted with halogen;
R ⁵ is unsubstituted C ₄ -C ₁₂ -alkyl, C ₃ -C ₁₂ -cycloalkyl, C ₃ -C ₁₂ -alkenyl, C ₅ -C ₁₂ -cycloalkenyl, C ₃ -C ₁₂ -alkynyl, C ₃ -C ₁₂ -Cycloalkyl-C ₁ -C ₄ -alkyl [5 last listed groups can in each case have 1, 2 or 3 substituents R ⁹ Some or all of the hydrogen atoms in the last listed group can be substituted with halogen]; C ₁ -C ₁₂ -haloalkyl, C ₁ -C ₁₂ -alkyl [1, 2 or 3 substitutions] Group R ¹¹ ]; group —C (R ¹⁰ ) ═NOR ⁸ , group —C (O) NR ¹³ R ¹⁴ ; phenyl; phenyl-C ₁ -C ₆ -alkyl, phenyl-C ₂ -C ₆ -alkenyl , Phenyl-C ₂ -C ₆ -alkynyl, phenyloxy-C ₁ -C ₆ -alkyl, phenyloxy-C ₂ -C ₆ -alkenyl, phenyloxy-C ₂ -C ₆ -alkynyl [6 last listed Alkyl, alkenyl and a The alkynyl moiety can have 1, 2, 3 or 4 substituents R ^11, and the phenyl ring in the 7 last listed groups can have 1, 2, 3 or 4 groups R ⁷ . Can have];
R ⁶ has the meaning given for R ¹ which is different from hydrogen;
R ⁷ is C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkyl, C ₁ -C ₄ -alkoxy, C ₂ -C ₄ -alkenyl, C ₂ -C ₄ -alkenyloxy, C ₂ -C ₄ -alkynyl, C ₂ -C ₄ -alkynyloxy [some or all of the hydrogen atoms in these seven groups can be replaced by halogen], OH, halogen, nitro, CN, C _1- C ₄ -alkylthio, C ₁ -C ₄ -alkylsulfonyl, -C (O) R ¹² , NR ¹³ R ¹⁴ , -C (O) NR ¹³ R ¹⁴ , -C (S) NR ¹³ R ¹⁴ , -C ( R ¹⁰⁾ = NOR ^8, phenyl [may have 1, 2, 3 or 4 radicals mentioned under R ^6], phenoxy [1, 2, 3 or 4 mentioned under R ⁶ C ₁ -C ₆ -alkyl-phenyl [some or all of the hydrogen atoms of the alkyl moiety can be substituted with halogens, and the phenyl ring is listed under R ⁶ Can have 1, 2, 3 or 4 groups] In, also two radicals R ⁷ attached to adjacent carbon atoms, CH = CH-CH = CH or can be an alkylene chain having 3-5 carbon atoms, wherein one or two non-adjacent CH ₂ groups can also be replaced by oxygen or sulfur, and some or all of the hydrogen atoms can be replaced by halogens;
R ⁸ is C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkyl, C ₂ -C ₄ -alkenyl, C ₂ -C ₄ -alkynyl [some of hydrogen atoms in these four groups or All can be substituted with halogen], phenyl or phenyl-C ₁ -C ₆ -alkyl [phenyl in the two last listed groups is 1, 2, 3 listed under R ⁶ Or can have 4 groups];
R ⁹ is C ₁ -C ₄ -alkyl, C ₁ -C ₈ -alkoxy, C ₂ -C ₈ -alkenyloxy, C ₂ -C ₈ -alkynyloxy, C ₁ -C ₄ -alkoxy-C ₁ -C ₈ -alkoxy and some or all of the hydrogen atoms in these groups can be substituted with halogens;
R ¹⁰ is hydrogen, halogen, C ₁ -C ₈ -alkoxy, C ₂ -C ₈ -alkenyloxy, C ₂ -C ₈ -alkynyloxy, C ₁ -C ₄ -alkoxy-C ₁ -C ₈ -alkoxy, C ₁ -C ₁₂ -alkyl, C ₃ -C ₁₂ -cycloalkyl, C ₂ -C ₁₂ -alkenyl, C ₅ -C ₁₂ -cycloalkenyl, C ₃ -C ₁₂ -cycloalkyl-C ₁ -C ₄ -alkyl [Some or all of the hydrogen atoms in the 9 last listed groups can be substituted with halogen], phenyl [1, 2, 3 or 4 groups listed under R ⁷ Can have];
R ¹¹ is halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₈ -alkoxy, C ₁ -C ₈ -alkoxy-C ₁ -C ₈ -alkoxy, C ₂ -C ₈ -alkenyloxy, C _2- C ₈ -alkynyloxy, C ₁ -C ₄ -alkoxy-C ₁ -C ₈ -alkoxy, some or all of the hydrogen atoms in these groups can be substituted with halogens;
R ¹² is hydrogen, OH, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₂ -C ₄ -alkenyl, C ₂ -C ₄ -alkynyl, C ₂ -C ₄ -alkenyloxy, C _2- C ₄ -alkynyloxy, C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkoxy, some or all of the hydrogen atoms in the seven last listed groups being substituted with halogens It is possible;
R ¹³ and R ¹⁴ are independently of each other hydrogen, C ₁ -C ₄ -alkyl, C ₂ -C ₄ -alkenyl, C ₂ -C ₄ -alkynyl, and some of the hydrogen atoms in these groups Or all can be substituted with halogen)
Of 3-trifluoromethylpicolinic acid anilide and the agriculturally useful salt of I.

  The invention further relates to the use of 3-trifluoromethylpicolinic acid anilides of formula I and their agriculturally acceptable salts as fungicides and to crop protection compositions comprising these compounds.

  Furthermore, the present invention relates to a method for controlling phytopathogenic fungi (harmful fungi), which sterilizes harmful fungi, their habitats or plants, areas, materials or spaces that should be kept free of them. Treatment with an effective amount of 3-trifluoromethylpicolinic acid anilide of formula I and / or an agriculturally acceptable salt of I.

  Depending on the nature of the substituent, the 3-trifluoromethylpicolinic acid anilide of formula I can have one or more chiral centers, in which case they exist as enantiomers or a mixture of diastereomers. . The present invention provides both pure enantiomers or diastereomers and mixtures thereof. Suitable compounds of formula I also include all possible stereoisomers (cis / trans isomers) and mixtures thereof.

Suitable agriculturally useful salts are in particular the salts of their cations or their acid addition salts whose cations and anions respectively do not adversely affect the bactericidal action of compound I. Thus, suitable cations are in particular alkali metals, preferably sodium and potassium, alkaline earth metals, preferably calcium, magnesium and barium and transition metals, preferably manganese, copper, zinc and iron ions, and also if desired. Ammonium ions, preferably diisopropylammonium, tetramethylammonium, tetrabutylammonium, trimethylbenzylammonium, which can have _{1 to 4} C1-C4-alkyl substituents and / or one phenyl or benzyl substituent; Furthermore, phosphonium ions, sulfonium ions, preferably tri (C ₁ -C ₄ -alkyl) sulfonium, and sulfoxonium ions, preferably tri (C ₁ -C ₄ -alkyl) sulfoxonium.

Useful acid addition salt anions are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate and , C ₁ -C ₄ -alkanoic acid anions, preferably formate, acetate, propionate and butyrate. They can be formed by reacting I with the corresponding anionic acid, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.

In defining the variables given in the above formula, collective terms that are generally typical for the substituent are used. The term C _n -C _m indicates the number of possible carbon atoms in each case in the substituent or substituent. All hydrocarbon chains, ie all alkyl, haloalkyl, phenylalkyl, alkenyl, haloalkenyl, phenylalkenyl, alkynyl, haloalkynyl and phenylalkynyl moieties can be straight or branched. The halogenated substituent preferably has 1 to 5 identical or different halogen atoms. The term halogen represents in each case fluorine, chlorine, bromine or iodine.

Examples of other meanings are:
-C ₁ -C ₄ -alkyl and the alkyl moiety in alkoxyalkyl, alkylsulfonyl and alkylthio: CH ₃ , C ₂ H ₅ , CH ₂ -C ₂ H ₅ , CH (CH ₃ ) ₂ , n-butyl, CH (CH ₃ ) —C ₂ H ₅ , CH ₂ —CH (CH ₃ ) ₂ or C (CH ₃ ) ₃ ;
-C ₁ -C ₄ -haloalkyl: some, for example 1, 2 or 3 or all of the hydrogen atoms are halogen, such as fluorine, chlorine, bromine and / or iodine, in particular chlorine and / or fluorine, in particular fluorine Substituted C ₁ -C ₄ -alkyl groups such as CH ₂ F, CHF ₂ , CF ₃ , CH ₂ Cl, CH (Cl) ₂ , C (Cl) ₃ , chlorofluoromethyl, dichlorofluoromethyl, Chlorodifluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro -2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, C ₂ F ₅ , 2-fluoropropyl, 3-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 2-chloropropyl, 3-chloropro Le, 2,3-dichloro propyl, 2-bromopropyl, 3-bromopropyl, 3,3,3-trifluoropropyl, 3,3,3-trichloro _{propyl, CH 2 -C 2 F 5,} CF 2 -C ₂ F ₅ , 1- (fluoromethyl) -2-fluoroethyl, 1- (chloromethyl) -2-chloroethyl, 1- (bromomethyl) -2-bromoethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or Nonafluorobutyl;
-C ₁ -C ₁₂ -alkyl: a saturated hydrocarbon group having 1 to 12 carbon atoms, such as the C ₁ -C ₄ -alkyl group described above or, for example, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3 -Methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4- Methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2 -Ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl or 1-ethyl-2-methylpropyl, preferably CH ₃ , C ₂ H ₅ , CH _{2 -C 2 H 5, CH (} CH 3) 2, n- _{butyl, C (CH 3) 3,} n- -pentyl, n- hexyl, n--heptyl or n- Corruptible;
- C ₁ -C ₁₂ - haloalkyl: C ₁ -C ₁₂ described above some of the hydrogen atoms, for example, two or three or all halogen, in particular substituted by chlorine and / or fluorine, especially fluorine -Alkyl groups, ie one of the groups listed under C ₁ -C ₄ -haloalkyl, for example, or 5-fluoro-1-pentyl, 5-chloro-1-pentyl, 5-bromo-1 -Pentyl, 5-iodo-1-pentyl, 5,5,5-trichloro-1-pentyl, undecafluoropentyl, 6-fluoro-1-hexyl, 6-chloro-1-hexyl, 6-bromo-1- Hexyl, 6-iodo-1-hexyl, 6,6,6-trichloro-1-hexyl or tridecafluorohexyl;
- C ₂ -C ₄ - alkenyl moiety in alkenyl and alkenyloxy: to 4 carbon atoms and any position with double bonds, unsaturated straight or branched hydrocarbon group, such as ethenyl, 1- Propenyl, 2-propenyl, 1-methylethenyl, 1-buten-1-yl, 1-buten-2-yl, 1-buten-3-yl, 2 buten-1-yl, 1-methylprop-1-ene-1 -Yl, 2-methylprop-1-en-1-yl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl;
- C ₂ -C ₁₂ - alkenyl: a 2 to 12 carbon atoms and any position with double bonds, unsaturated straight or branched hydrocarbon group, for example C ₂ -C ₄ above - alkenyl and also For example, n-penten-1-yl, n-penten-2-yl, n-penten-3-yl, n-penten-4-yl, 1-methylbut-1-en-1-yl, 2-methylbuta- 1-en-1-yl, 3-methylbut-1-en-1-yl, 1-methylbut-2-en-1-yl, 2-methylbut-2-en-1-yl, 3-methylbut-2- En-1-yl, 1-methylbut-3-en-1-yl, 2-methylbut-3-en-1-yl, 3-methylbut-3-en-1-yl, 1,1-dimethylprop-2 -En-1-yl, 1,2-dimethylprop-1-en-1-yl, 1,2-dimethylprop-2-en-1-yl, 1-ethylprop-1-en-2-yl, 1 -Ethylprop-2-en-1-yl, n-hex-1-en-1-yl, n-hex-2-en-1-yl, n-hex-3-en-1-yl, n -Hex-4-en-1-yl, n-hexa-5-en-1-yl, 1-methylpent-1-en-1-yl, 2-methylpent-1-en-1-yl, 3-methylpenta -1-en-1-yl, 4-methylpent-1-en-1-yl, 1-methylpent-2-en-1-yl, 2-methylpent-2-en-1-yl, 3-methylpenta-2 -En-1-yl, 4-methylpent-2-en-1-yl, 1-methylpent-3-en-1-yl, 2-methylpent-3-en-1-yl, 3-methylpent-3-ene -1-yl, 4-methylpent-3-en-1-yl, 1-methylpent-4-en-1-yl, 2-methylpent-4-en-1-yl, 3-methylpent-4-ene-1 -Yl, 4-methylpent-4-en-1-yl, 1,1-dimethylbut-2-en-1-yl, 1,1-dimethylbut-3-en-1-yl, 1,2-dimethyl But-1-en-1-yl, 1,2-dimethylbut-2-en-1-yl, 1,2-dimethylbut-3-en-1-yl, 1,3-dimethylbut-1-ene -1-yl, 1,3-dimethylbuta- 2-en-1-yl, 1,3-dimethylbut-3-en-1-yl, 2,2-dimethylbut-3-en-1-yl, 2,3-dimethylbut-1-ene-1 -Yl, 2,3-dimethylbut-2-en-1-yl, 2,3-dimethylbut-3-en-1-yl, 3,3-dimethylbut-1-en-1-yl, 3, 3-dimethylbut-2-en-1-yl, 1-ethylbut-1-en-1-yl, 1-ethylbut-2-en-1-yl, 1-ethylbut-3-en-1-yl, 2 -Ethylbut-1-en-1-yl, 2-ethylbut-2-en-1-yl, 2-ethylbut-3-en-1-yl, 1,1,2-trimethylprop-2-en-1- Yl, 1-ethyl-1-methylprop-2-en-1-yl, 1-ethyl-2-methylprop-1-en-1-yl or 1-ethyl-2-methylprop-2-en-1-yl;
Alkynyl moiety in -C ₂ -C ₄ -alkynyl and alkynyloxy: a straight or branched hydrocarbon group having 2 to 4 carbon atoms and a triple bond at any position, eg ethynyl, 1-propynyl, 2 -Propynyl (= propargyl), 1-butynyl, 2-butynyl, 3-butynyl and 1-methyl-2-propynyl;
-C ₂ -C ₁₂ -alkynyl: a straight or branched hydrocarbon group having 2 to 12 carbon atoms and a triple bond at any position, such as ethynyl, prop-1-in-1-yl, prop- 2-in-1-yl, n-but-1-in-1-yl, n-but-1-in-3-yl, n-but-1-in-4-yl, n-but-2- In-1-yl, n-pent-1-in-1-yl, n-pent-1-in-3-yl, n-pent-1-in-4-yl, n-pent-1-in- 5-yl, n-pent-2-yn-1-yl, n-pent-2-yn-4-yl, n-pent-2-yn-5-yl, 3-methylbut-1-in-3- Yl, 3-methylbut-1-in-4-yl, n-hex-1-in-1-yl, n-hex-1-in-3-yl, n-hex-1-in-4-yl, n-hex-1-yn-5-yl, n-hex-1-yn-6-yl, n-hex-2-yn-1-yl, n-hex-2-yn-4-yl, n- Hex-2-yn-5-yl, n-hex-2-yn-6-yl, n-hex-3-yn-1-yl, n-hex-3-yn-2-yl 3-methylpent-1-in-1-yl, 3-methylpent-1-in-3-yl, 3-methylpent-1-in-4-yl, 3-methylpent-1-in-5-yl, 4-methylpent-1-in-1-yl, 4-methylpent-2-in-4-yl and 4-methylpent-2-yn-5-yl;
-C ₁ -C ₄ -alkoxy: OCH ₃ , OC ₂ H ₅ , OCH ₂ -C ₂ H ₅ , OCH (CH ₃ ) ₂ , n-butoxy, OCH (CH ₃ ) -C ₂ H ₅ , OCH _2- CH (CH ₃ ) ₂ or OC (CH ₃ ) ₃ ;
-C ₁ -C ₄ -haloalkoxy: C ₁ -C _{4 as} described above, wherein some, for example 1, 2 or 3 or all hydrogen atoms are replaced by halogen atoms, in particular chlorine and / or fluorine, in particular fluorine - an alkoxy group, i.e., for example, _{OCH 2 F, OCHF 2, OCF} 3, OCH 2 Cl, OCH (Cl) 2, OC (Cl) 3, chloro, trifluoromethoxy, dichloro trifluoromethoxy, chlorodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2-bromoethoxy, 2-iodoethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoro Ethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy, OC ₂ F ₅ , 2-fluoropropoxy, 3-fluoropropoxy, 2,2-difluoropropoxy, 2,3-difluoropropoxy , 2-chloropropoxy, 3-chloro Propoxy, 2,3-dichloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 3,3,3-trifluoropropoxy, 3,3,3-trichloropropoxy, OCH ₂ -C ₂ F ₅ , OCF ₂ -C ₂ F ₅ , 1- (CH ₂ F) -2-fluoroethoxy, 1- (CH ₂ Cl) -2-chloroethoxy, 1- (CH ₂ Br) -2-bromoethoxy, 4-fluorobutoxy, 4- chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy, preferably OCHF _2, OCF _3, dichlorofluoromethane methoxide, chlorodifluoromethoxy or 2,2,2-trifluoroethoxy;
- C ₃ -C ₆ - cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;
-C ₃ -C ₁₂ -cycloalkyl: monocyclic, bicyclic or tricyclic hydrocarbon group, for example C ₃ -C ₆ -cycloalkyl group as described above or cycloheptyl, cyclooctyl, bicyclo [2.2.1] heptyl Bicyclo [2.2.2] octyl, bicyclo [3.2.1] octyl, bicyclo [3.3.0] octyl, bicyclo [4.3.0] nonyl, bicyclo [4.4.0] decyl or adamantyl;
- C ₃ -C ₁₂ - cycloalkyl - C ₁ -C ₄ - _{alkyl: C 3 -C 12 - C 1} -C substituted cycloalkyl ₄ - alkyl, for example cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, Cyclohexylmethyl, cycloheptylmethyl, cyclooctylmethyl, 2- (cyclopropyl) ethyl, 2- (cyclobutyl) ethyl, 2- (cyclopentyl) ethyl, 2- (cyclohexyl) ethyl, 2- (cycloheptyl) ethyl, 2- (Cyclooctyl) ethyl, 3- (cyclopropyl) propyl, 3- (cyclobutyl) propyl, 3- (cyclopentyl) propyl, 3- (cyclohexyl) propyl, 3- (cycloheptyl) propyl, 3- (cyclooctyl) propyl , 4- (cyclopropyl) butyl, 4- (cyclobutyl) butyl, 4- (cyclopentyl) butyl, 4- (cyclohexyl) butyl, 4- (cycloheptyl) butyl, 4- (cyclo Corruptible) butyl;
- C ₁ -C ₄ - alkoxy -C ₁ -C ₄ - _{alkyl: C 1 -C 4 - C 1} -C 4 substituted with an alkoxy - alkyl, such as methoxymethyl, ethoxymethyl, 1- or 2-methoxyethyl 1- or 2-ethoxyethyl, 1-, 2- or 3-methoxypropyl;
- C ₁ -C ₄ - alkoxy -C ₁ -C ₄ - _{alkoxy: C 1 -C 4 - C 1} -C 4 substituted with alkoxy - alkoxy, such as methoxy, methoxy, ethoxy-methoxy, 1- or 2-methoxyethoxy 1- or 2-exoxyethoxy, 1-, 2- or 3-methoxypropoxy;
Phenyl-C ₁ -C ₆ -alkyl: C ₁ -C ₆ -alkyl substituted with phenyl, such as benzyl, 1- or 2-phenylethyl, 1-, 2- or 3-phenylpropyl;
Phenyloxy-C ₁ -C ₆ -alkyl: C ₁ -C ₆ -alkyl substituted with phenoxy, such as phenoxymethyl, 1- or 2-phenoxyethyl, 1-, 2- or 3-phenoxypropyl;
Phenyl-C ₂ -C ₆ -alkenyl: C ₂ -C ₆ -alkenyl substituted with phenyl, such as 1- or 2-phenylethenyl, 1-phenylprop-2-en-1-yl, 3-phenyl- 1-propen-1-yl, 3-phenyl-2-propen-1-yl, 4-phenyl-1-buten-1-yl or 4-phenyl-2-buten-1-yl;
-Phenyloxy-C ₂ -C ₆ -alkenyl: C ₂ -C ₆ -alkenyl substituted with phenoxy, such as 1- or 2-phenyloxyethenyl, 1-phenyloxyprop-2-en-1-yl, 3-phenyloxy-1-propen-1-yl, 3-phenyloxy-2-propen-1-yl, 4-phenyloxy-1-buten-1-yl or 4-phenyloxy-2-buten-1- Ill;
-Phenyl-C ₂ -C ₆ -alkynyl: C ₂ -C ₆ -alkynyl substituted with phenyl, such as 1-phenylprop-2-in-1-yl, 3-phenyl-1-propyn-1-yl, 3-phenyl-2-propyn-1-yl, 4-phenyl-1-butyn-1-yl or 4-phenyl-2-butyn-1-yl;
-Phenyloxy-C ₂ -C ₆ -alkynyl: C ₂ -C ₆ -alkynyl substituted with phenoxy, for example 1-phenyloxyprop-2-yn-1-yl, 3-phenyloxy-1-propyne-1 -Yl, 3-phenyloxy-2-propyn-1-yl, 4-phenyloxy-1-butyn-1-yl or 4-phenyloxy-2-butyn-1-yl.

With regard to bactericidal activity, anilides of the formula I are preferred, in which the variables R ^{1 to} R ⁶ are independent of one another and in particular in combination with the following meaning:
R ¹ , R ² , R ³ independently of one another are hydrogen, halogen, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -haloalkyl. In particular, one, two or preferably all groups R ¹ , R ² and R ³ are hydrogen;
R ⁴ is hydrogen, methyl, OH or methoxy, especially hydrogen;
R ⁵ has one of the following meanings:
-Unsubstituted C ₄ -C ₁₂ -alkyl, C ₃ -C ₁₂ -cycloalkyl, C ₂ -C ₁₂ -alkenyl, C ₅ -C ₁₂ -cycloalkenyl, C ₂ -C ₁₂ -alkynyl, where 4 Some or all of the hydrogen atoms in one of the last listed groups can be substituted with halogen, and some or all of the hydrogen atoms in C ₃ -C ₁₂ -cycloalkyl are C ₁ -C ₄ Can be substituted with -alkyl;
- C ₁ -C ₁₂ - haloalkyl, in particular C ₁ -C ₄ - fluoroalkyl, C ₁ -C ₄ - alkoxy - C ₁ -C ₄ - alkyl, C ₁ -C ₄ - haloalkoxy - C ₁ -C ₄ - Alkyl, in particular C ₁ -C ₄ -fluoroalkoxy-C ₁ -C ₄ -alkyl;
-Phenyl, phenyl-C ₁ -C ₆ -alkyl, wherein the phenyl ring can be substituted by 1, 2, 3 or 4 groups R ⁷ , in particular 0, 1, 2 or 3 groups Having R ⁷ ; or
--C (C ₁ -C ₄ -alkyl) = NO-R ⁸ , wherein some of the hydrogen atoms of the C ₁ -C ₄ -alkyl group, for example 1, 2 or 3 or all, are replaced by halogens Can be done; and
R ⁶ is independently of each other C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -haloalkoxy or halogen, in particular fluorine, chlorine, methyl, Trifluoromethyl, methoxy, trifluoromethoxy or difluoromethyl.

The variable R ⁷ is in particular C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₁ -C ₄ -haloalkyl, C ₁ -C ₄ -haloalkoxy, nitro, CN and halogen, in particular fluorine, chlorine, Selected from the group consisting of methyl, trifluoromethyl, methoxy, trifluoromethoxy or difluoromethyl.

The variable R ⁸ is preferably C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkyl, C ₁ -C ₄ -alkoxy, C ₂ -C ₄ -alkenyl, C ₂ -C ₄ -alkynyl (these 5 Some or all of the hydrogen atoms in one group can be substituted with halogen), halogen, nitro, CN, phenyl (having 1, 2, 3 or 4 groups listed under R ⁶ ), Phenoxy (can have 1, 2, 3 or 4 groups listed under R ⁶ ), C ₁ -C ₆ -alkyl-phenyl (some or all of the hydrogen atoms of the alkyl group) Can be substituted with halogen, and the phenyl ring can be selected from the group consisting of 1, 2, 3 or 4 groups listed under R ⁶ , in particular C ₁ -C ₄ - alkyl, C ₃ -C ₆ - cycloalkyl, C ₂ -C ₄ - alkenyl, C ₂ -C ₄ - alkynyl (some of the hydrogen atoms in these four groups or All can be substituted with halogen) and phenyl and benzyl (phenyl in the two last listed groups can have 1, 2, or 3 groups listed under R ⁶ ) Selected from the group consisting of

  For bactericidal activity, anilides of the formula I where n = 0 are preferred.

  The variable W is in particular oxygen.

Regarding the bactericidal activity of anilide I, X in formula I is a direct bond or oxygen. In a first particularly preferred embodiment of the invention, X is oxygen. In another particularly preferred embodiment, X is a direct bond. If R ⁵ is unsubstituted alkyl, X is in particular a direct bond.

With regard to their bactericidal activity, anilides of the formula I in which the group XR ⁵ is attached to the amide nitrogen in the ortho or meta position, in particular in the ortho position are preferred. Of these, anilides of the formula I in which R ¹ , R ² and R ³ are each hydrogen, in particular anilides of the formula I in which n = 0, are particularly preferred. Of these, anilides in which R ⁵ has one of the following meanings are particularly preferred:
-Unsubstituted C ₄ -C ₁₂ -alkyl, C ₃ -C ₁₂ -cycloalkyl, C ₂ -C ₁₂ -alkenyl, C ₅ -C ₁₂ -cycloalkenyl, C ₂ -C ₁₂ -alkynyl, where 4 Some or all of the hydrogen atoms in one of the last listed groups can be substituted with halogen, and some or all of the hydrogen atoms in C ₃ -C ₁₂ -cycloalkyl are C ₁ -C ₄ Can be substituted with -alkyl;
- C ₁ -C ₁₂ - haloalkyl, in particular C ₁ -C ₄ - fluoroalkyl, C ₁ -C ₄ - alkoxy - C ₁ -C ₄ - alkyl, C ₁ -C ₄ - haloalkoxy - C ₁ -C ₄ - Alkyl, in particular C ₁ -C ₄ -fluoroalkoxy-C ₁ -C ₄ -alkyl;
-Phenyl, phenyl-C ₁ -C ₆ -alkyl, wherein the phenyl ring can be substituted by 1, 2, 3 or 4 groups R ⁷ , in particular 0, 1, 2 or 3 groups Having R ⁷ ; or
--C (C ₁ -C ₄ -alkyl) = NO-R ⁸ , wherein some or all of the hydrogen atoms of the C ₁ -C ₄ -alkyl group can be substituted with halogen.

Here, R ⁷ and R ⁸ have the meanings given as particularly preferred; W is in particular oxygen.

In particular for the fungicides and their use as active compounds for controlling pests, the individual compounds collected in the following Tables 1 to 6 are preferred, these compounds being encompassed by the formulas Ia, Ib and Ic Especially preferred are compounds of formula Ia.

Table 1:
Compound of formula Ia:

(Where X is a direct bond and R ⁵ has one of the meanings given in Table A)
Table 2:
A compound of formula Ia wherein X is O and R ⁵ has one of the meanings given in Table A.

Table 3:
Compound of formula Ib:

(Where X is a direct bond and R ⁵ has one of the meanings given in Table A)
Table 4:
A compound of formula Ib wherein X is O and R ⁵ has one of the meanings given in Table A.

Table 5:
Compounds of formula Ic:

(Where X is a direct bond and R ⁵ has one of the meanings given in Table A)
Table 6:
A compound of formula Ic wherein X is O and R ⁵ has one of the meanings given in Table A.

The 3-trifluoromethylpicolinic acid anilide of formula I with W = O and R ⁴ = H is prepared according to the synthesis shown in the following process of scheme 1 known from the literature according to the activated 3-3- Can be prepared by reacting trifluoromethylpicoline derivatives with aniline III [Houben-Weyl: “Methoden der organ. Chemie” [Methods of organic chemistry], Georg-Thieme-Verlag, Stuttgart , New York 1985, Volume E5, pp. 941-1045.]. Activated carboxylic acid derivatives include, for example, halides, activated esters, anhydrides, azides such as chloride, fluoride, bromide, para-nitrophenyl ester, pentafluorophenyl ester, N-hydroxysuccinimidate and hydroxybenzotriazole. 1-yl ester.

Scheme 1:

  In Scheme 1, L is a suitable nucleophilic exchangeable leaving group such as halide, activated ester group, anhydride group, azide such as chloride, fluoride, bromide, para-nitrophenyloxy, pentafluoro. A group derived from phenyloxy, N-hydroxysuccinimide or hydroxybenzotriazol-1-yl.

  Furthermore, 3-trifluoromethylpicolinic acid anilide of formula I can be prepared by reacting free acid IIa with unsubstituted or N-substituted aniline IIIa in the presence of a coupling agent ( Scheme 2).

Scheme 2:

Suitable coupling agents are, for example:
-Coupling agents based on carbodiimide, such as N, N'-dicyclohexylcarbodiimide [JC Sheehan, GP Hess, J. Am. Chem. Soc. 1955, 77, 1067], N- (3-dimethylaminopropyl) -N '-Ethylcarbodiimide;
-Coupling agents that form mixed anhydrides with carbonates such as 2-ethoxy-1-ethoxycarbonyl-1,2-dihydroquinoline [B. Belleau, G. Malek, J. Amer. Chem. Soc. 1968, 90 , 1651.], 2-isobutyloxy-1-isobutyloxycarbonyl-1,2-dihydroquinoline [Y. Kiso, H. Yajima, J. Chem. Soc., Chem. Commun. 1972, 942.];
-Coupling agents based on phosphonium, for example (benzotriazol-1-yloxy) tris (dimethylamino) phosphonium hexafluorophosphate [B. Castro, JR Domoy, G. Evin, C. Selve, Tetrahedron Lett. 1975, 14, 1219 .], (Benzotriazol-1-yloxy) tripyrrolidinophosphonium hexafluorophosphate [J. Coste et.al., Tetrahedron Lett. 1990, 31, 205.];
-Coupling agents based on uronium or guanidinium N-oxide structures, such as N, N, N ', N'-tetramethyl-O- (1H-benzotriazol-1-yl) uronium hexafluorophosphate [R. Knorr, A. Trzeciak, W. Bannwarth, D. Gillessen, Tetrahedron Lett. 1989, 30, 1927.], N, N, N ', N'-tetramethyl-O- (benzotriazol-1-yl ) Uronium tetrafluoroborate, (benzotriazol-1-yloxy) dipiperidinocarbenium hexafluorophosphate [S. Chen, J. Xu, Tetrahedron Lett. 1992, 33, 647];
-Coupling agents that form acid chlorides, for example bis- (2-oxooxazolidinyl) phosphinic chloride [J. Diago-Mesequer, Synthesis 1980, 547.].

R ⁴ = unsubstituted or halogen - substituted alkyl or unsubstituted or halogen - substituted cycloalkyl, 3-trifluoromethyl picolinic acid anilide of the formula I, the amide I (where be R ⁴ = hydrogen Can be obtained according to Scheme 1 or 2) by alkylation with a suitable alkylating agent in the presence of a base. For example, J. Am. Chem. Soc. 1952, 74, p. 3121, Helv. Chim. Acta, 1974, 57, p. 281, Synth. Commun. 1988, 18, p. Known from 2011.

  3-trifluoromethylpicolinic acid IIa is obtained from the corresponding pyridine-2,3-dicarboxylic acid by methods known from the literature, for example from J. Fluorine Chem. 1993, 60, p. 233-237; JP 1980-5059135; US 4803205; or Khim. Geterotsikl. Soedin 1994, pp. 657-659 by reaction with sulfur tetrafluoride or according to Eur. J. Org. Chem. 2002, pp. 327-330 It can manufacture by introducing.

  These are activated by processes known from the literature [Houben-Weyl: “Methoden der organ. Chemie”, Georg-Thieme-Verlag, Stuttgart, New York 1985, Volume E5, pp. 587-614, 633-772]. The synthesized thiophene carboxylic acid derivative II can be used.

  Anilines III and IIIa were synthesized by known methods from the literature [Houben-Weyl: “Methoden der organ. Chemie”, Georg-Thieme-Verlag, Stuttgart, New York, Volume XI, Part 1, pp. 9-1005.] can do.

3-trifluoromethylpicolinethioanilide of formula I where W = S is generally obtained from the corresponding anilide of formula I where X = O by, for example, J. Am. Chem. Soc. 1951, 73 , p. 4988, or sulfurized with P ₂ S ₅ or by reaction with Lawessons reagent according to Heterocycles 2002, 58, pp. 203-212; or Pharmazie 1999, 54 (9), pp. 645-650, Can be manufactured.

  The 3-trifluoromethylpicolinic acid anilides of formula I and their agriculturally acceptable, ie useful salts, are suitable for use as fungicides. They are characterized by being highly effective against a broad spectrum of phytopathogenic fungi, especially those from the types Ascomycetes, Deuteromycetes, Phycomycetes and Basidiomycetes. Some are effective overall and can be used for plant protection as foliar and soil fungicides.

  They are various cultivated plants such as wheat, rye, barley, oats, rice, corn, grass, banana, cotton, soybeans, coffee, sugarcane, vines, fruits and ornamental plants and vegetables such as cucumbers, beans, Of particular importance for the control of numerous fungi on tomatoes, potatoes and cucumbers and the seeds of these plants.

They are particularly suitable for controlling the following plant diseases:
Alternaria species for fruits and vegetables,
・ Botrytis cinerea (gray mold disease) for strawberries, vegetables, ornamental plants and vines,
Cercospora arachidicola for tuberous plants,
Erysiphe cichoracearum and Sphaerotheca fuliginea against cucumber,
・ Erysiphe graminis (powdery mildew) for cereals,
Fusarium and Verticillium species for various plants,
-Helminthosporium species for cereals,
-Mycosphaerella species for banana and tuberous plants-Phytophthora infestans for potatoes and tomatoes,
・ Plasmopara viticola against vines,
・ Podosphaera leucotricha against apples,
Pseudocercosporella herpotrichoides against wheat and barley,
Pseudoperonospora species for hops and cucumbers,
・ Puccinia species for cereals,
・ Pyricularia oryzae against rice,
Rhizoctonia species for cotton, rice and turf,
・ Septoria nodorum against wheat,
・ Sphaerotheca fuliginea for cucumber, powdery mildew of cucumber,
・ Uncinula necator against vines,
• Ustilago species for cereals and sugarcane,
・ Venturia species (black scab) for apples and pears,
・ Septoria tritici,
・ Pyrenophora species,
・ Leptosphaeria nodorum,
・ Rhynchosporium species,
・ Typhula species.

  Compound I is also suitable for controlling harmful fungi such as Paecilomyces variotii in the protection of materials (eg wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products.

  Compound I is used by treating a fungus or a plant, seed, material or soil to be protected from fungal attack with an active compound in an amount effective for sterilization. Application can be made both before and after infection by the material, plant or seed fungus.

  Bactericidal compositions generally contain from 0.1 to 95% by weight of active compound, preferably from 0.5 to 90%.

  When used in plant protection, the amount applied is 0.01 to 2.0 kg of active compound per hectare, depending on the type of effect desired.

  In the treatment of seeds, an amount of active compound of 0.001 to 0.1 g, preferably 0.01 to 0.05 g, per kg of seed is generally necessary.

  When used to protect materials or stored products, the amount of active compound applied depends on the type of application area and the desired effect. The amount customarily applied in the protection of the material is, for example, 0.001 g to 2 kg, preferably 0.005 g to 1 kg of active compound per cubic meter of material to be treated.

  Compound I can be converted into conventional formulations such as solutions, emulsions, suspensions, powders, powders, pastes and granules. The application form depends on the respective intended use and in each case a fine and homogeneous distribution of the compounds according to the invention should be ensured.

  The formulations are prepared in a known manner, for example by diluting the active compound with solvents and / or carriers, if desired with emulsifiers and dispersants, and when water is the diluent, other organic solvents can be dissolved. It is also possible to use it as a co-solvent. Adjuncts suitable for this purpose are essentially solvents such as aromatics (eg xylene), chlorinated aromatics (eg chlorobenzene), paraffins (eg petroleum fraction), alcohols (eg methanol, butanol), ketones. (Eg cyclohexanone), amines (eg ethanolamine, dimethylformamide) and water; carriers such as soil natural minerals (eg kaolin, clay, talc, chalk) and soil synthetic minerals (eg highly dispersed silicic acid, silicates); Emulsifiers such as nonionic and anionic emulsifiers (eg polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates) and dispersants such as lignosulfite effluent and methylcellulose.

  Suitable surfactants include lignosulfonic acid, naphthalene sulfonic acid, phenol sulfonic acid and dibutyl naphthalene sulfonic acid alkali metal, alkaline earth metal and ammonium salts, alkylaryl sulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates and fatty acids. And alkali metal and alkaline earth metal salts thereof, sulfated fatty alcohol glycol ether salts, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acid with phenol and formaldehyde, Polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol and nonylphenol, Killphenol polyglycol ether, tributylphenyl polyglycol ether, alkylaryl polyether alcohol, isotridecyl alcohol, fatty alcohol ethylene oxide condensate, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether Acetals, sorbitol esters, lignosulfite waste liquors and methylcellulose.

  Petroleum fractions with medium to high boiling points, such as kerosene or diesel oil, as well as coal tar oils and oils of vegetable and animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffins, Tetrahydronaphthalene, alkylated naphthalene or derivatives thereof, methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene or isophorone, or highly polar solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone or Water is suitable for the production of directly sprayable solutions, emulsions, pastes or oily dispersions.

  Powders, compositions for dusting and dusting can be prepared by mixing the active substance with a solid carrier or by mutual grinding.

  Granules such as coated granules, impregnated granules and homogeneous granules can be produced by binding the active compound to a solid carrier. Solid carriers are for example mineral soils such as silica gel, silicates, talc, kaolin, attaclay, limestone, lime, chalk, balls, ocher, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, soil synthetic substances Fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate or urea, and plant products such as cereal flour, bark flour, wood flour and nutshell powder, cellulose powder and other solid carriers.

  The formulations generally comprise between 0.01 and 95% by weight of active compound, preferably between 0.1 and 90%. The active compound is used (in accordance with the NMR spectrum) in a purity of 90-100%, preferably 95-100%.

An example for a formulation is as follows:
I. 5 parts by weight of a compound of the invention are well mixed with 95 parts by weight of finely divided kaolin. In this way, a powder containing 5% by weight of active compound is obtained.

II. 30 parts by weight of a compound of the invention are well mixed with a mixture of 92 parts by weight finely divided silica gel and 8 parts by weight liquid paraffin (sprayed on the surface of the silica gel). In this way, an active compound preparation (active compound content 23% by weight) with good adhesive properties is obtained.

III. 10 parts by weight of a compound of the invention are 90 parts by weight of xylene, 6 parts by weight of an addition product of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid N-monoethanolamide, 2 parts by weight It is dissolved in a mixture consisting of the calcium salt of dodecylbenzenesulfonic acid and 2 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil (active compound content 9% by weight).

IV. 20 parts by weight of a compound according to the invention are 60 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight of an addition product of 7 moles of ethylene oxide and 1 mole of isooctylphenol and 5 parts by weight. , Dissolved in a mixture consisting of an addition product of 40 mol of ethylene oxide and 1 mol of castor oil (active compound content 16% by weight).

V. 80 parts by weight of a compound of the invention comprising 3 parts by weight of diisobutylnaphthalene-α-sulfonic acid sodium salt, 10 parts by weight of sodium salt of lignosulfonic acid from sulfite waste liquor and 7 parts by weight of finely divided silica gel And mixed with a hammer mill (active compound content 80% by weight).

VI. 90 parts by weight of a compound according to the invention are mixed with 10 parts by weight of N-methyl-α-pyrrolidone to obtain a solution suitable for use in the form of very small drops (active compound content 90 weight%).

VII. 20 parts by weight of a compound of the invention are 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of an addition product of 7 moles of ethylene oxide and 1 mole of isooctylphenol and 10 parts by weight. , Dissolved in a mixture consisting of an addition product of 40 moles of ethylene oxide and 1 mole of castor oil. An aqueous dispersion containing 0.02% by weight of active compound is obtained by pouring the solution into 100,000 parts by weight of water and finely dispersing therein.

VIII. 20 parts by weight of a compound of the invention comprising 3 parts by weight of diisobutylnaphthalene-α-sulfonic acid sodium salt, 17 parts by weight of sodium salt of lignosulfonic acid from sulfite waste liquor and 60 parts by weight of finely divided silica gel Well mixed and crushed with a hammer mill. By finely dispersing the mixture in 20,000 parts by weight of water, a spray emulsion containing 0.1% by weight of active compound is obtained.

IX. 10 parts by weight of a compound of the invention is 63 parts by weight of cyclohexanone, 27 parts by weight of a dispersant (eg 50 parts by weight of an adduct of 7 moles of ethylene oxide and 1 mole of isooctylphenol and 50 parts by weight of IX. , A mixture of 40 moles of ethylene oxide and 1 mole of castor oil). The stock solution is then diluted by dispensing in water to the desired concentration, for example in the range of 1-100 ppm.

  The active compounds can be used as such, in the form of a formulation or in the form of application made therefrom, for example directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, sprays. Can be used by spraying, atomizing, aerating, spraying or sprinkling in the form of a composition or granule. The application form depends exclusively on the intended use; in each case, the finest possible dispersion of the active compounds according to the invention should be ensured.

  Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (spray powders, oil dispersions) by adding water. To produce an emulsion, paste or oily dispersion, the material can be homogenized in water, as it is or dissolved in an oil or solvent, with a wetting agent, tackifier, dispersant or emulsifier. However, concentrates containing active substances, wetting agents, tackifiers, dispersants or emulsifiers and possibly solvents or oils can also be prepared, which concentrates are suitable for dilution with water .

  The concentration of the active compound in the ready-to-use preparation can vary within a relatively wide range. Generally, it is 0.0001 to 10%. Often, even small amounts of active compound I, for example 2 to 200 ppm, are sufficient in ready-to-use preparations. Also preferred are ready-to-use preparations having a concentration of active compound in the range of 0.01 to 1%.

  The active compounds can also be used very successfully in ultra low volume (ULV) processes, formulations with more than 95% by weight of active compounds or even with active compounds without additives. It is possible to apply.

  Various types of oils, herbicides, fungicides, other pesticides and fungicides can be added to the active compounds, if necessary not again until just before use (tank mix). These agents can be added to the composition of the present invention in a weight ratio of 1:10 to 10: 1.

  The compositions according to the invention are also present in application forms as fungicides and together with other active compounds, for example with herbicides, insecticides, growth regulators, fungicides or also with fertilizers. Can do. When compound I or a composition comprising it as a fungicide in the application form is mixed with other fungicides, an extension of the active germicidal spectrum is often obtained.

The following list of fungicides with which the compounds of the invention can be used is intended to illustrate possible combinations and is not limiting:
Sulfur, dithiocarbamate and its derivatives, such as iron (III) dimethyldithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylenebisdithiocarbamate, manganese ethylenebisdithiocarbamate, manganese zinc ethylenediaminebisdithiocarbamate, tetramethylthiuram disulfide, (N , N'-ethylenebisdithiocarbamate) zinc ammonia complex, (N, N'-propylenebisdithiocarbamate) zinc ammonia complex, (N, N'-propylenebisdithiocarbamate) zinc or N, N'-polypropylenebis (Thiocarbamoyl) disulfide;
Nitro derivatives such as dinitro (1-methylheptyl) phenyl crotonic acid, 2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate, 2-sec-butyl-4,6-dinitrophenylisopropyl carbonate Or diisopropyl 5-nitroisophthalate;
Heterocyclic materials such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, O, O-diethyl phthalimidophosphonothioate, 5-amino-1- [Bis (dimethylamino) phosphinyl] -3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithio [4,5-b] Quinoxaline, methyl 1- (butylcarbamoyl) -2-benzimidazole, 2- (methoxycarbonylamino) benzimidazole, 2- (2-furyl) benzimidazole, 2- (4-thiazolyl) benzimidazole, N- ( 1,1,2,2-tetrachloroethylthio) tetrahydrophthalimide, N- (trichloromethylthio) tetrahydrophthalimide or N- (trichloromethylthio) phthalimide;
N-dichlorofluoromethylthio-N ', N'-dimethyl-N-phenylsulfuric acid diamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-thiocyanatomethylthiobenzothiazole, 1,4 -Dichloro-2,5-dimethoxybenzene, 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, 2-thiopyridine 1-oxide, 8-hydroxyquinoline or its copper salt, 2,3-dihydro- 5-carboxyanilide-6-methyl-1,4-oxathiin, 2,3-dihydro-5-carboxyanilide-6-methyl-1,4-oxathiain 4,4-dioxide, 2-methyl-5,6-dihydro -4H-pyran-3-carboxyanilide, 2-methylfuran-3-carboxyanilide, 2,5-dimethylfuran-3-carboxyanilide, 2,4,5-trimethylfuran-3-carboxyanilide, N-cyclohexyl- 2,5-dimethylfuran-3-carboxamide, N-cyclohexyl -N-methoxy-2,5-dimethylfuran-3-carboxamide, 2-methylbenzanilide, 2-iodobenzanilide, N-formyl-N-morpholine 2,2,2-trichloroethyl acetal, piperazine-1, 4-diylbis-1- (2,2,2-trichloroethyl) formamide, 1- (3,4-dichloroanilino) -1-formylamino-2,2,2-trichloroethane, 2,6-dimethyl-N -Tridecylmorpholine or a salt thereof, 2,6-dimethyl-N-cyclododecylmorpholine or a salt thereof, N- [3- (p- (tert-butyl) phenyl) -2-methylpropyl] -cis-2,6 -Dimethylmorpholine, N- [3- (p- (tert-butyl) phenyl) -2-methylpropyl] piperidine, 1- [2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxolane- 2-ylethyl] -1H-1,2,4-triazole, 1- [2- (2,4-dichlorophenyl) -4- (n-propyl) -1,3-dioxolan-2-ylethyl] -1H-1 , 2,4-Triazole, N- (n-Propylene ) -N- (2,4,6-trichlorophenoxyethyl) -N'-imidazolylurea, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazole- 1-yl) -2-butanone, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanol, (2RS, 3RS ) -1- [3- (2-chlorophenyl) -2- (4-fluorophenyl) oxiran-2-ylmethyl] -1H-1,2,4-triazole, α- (2-chlorophenyl) -α- (4 -Chlorophenyl) -5-pyrimidinemethanol, 5-butyl-2-dimethylamino-4-hydroxy-6-methylpyrimidine, bis (p-chlorophenyl) -3-pyridinemethanol, 1,2-bis (3-ethoxycarbonyl- 2-thioureido) benzene or 1,2-bis (3-methoxycarbonyl-2-thioureido) benzene;
Strobilurin, such as methyl E-methoxyimino [α- (o-tolyloxy) -o-tolyl] acetate, E-2- {2- [6- (2-cyanophenoxy) pyrimidin-4-yloxy] phenyl} -3 -Methyl methoxyacrylate, methyl E-methoxyimino- [α- (2-phenoxyphenyl)] acetamide, methyl E-methoxyimino- [α- (2,5-dimethylphenoxy) -o-tolyl] acetamide;
Anilinopyrimidines such as N- (4,6-dimethylpyrimidin-2-yl) aniline, N- [4-methyl-6- (1-propynyl) pyrimidin-2-yl] aniline or N- [4-methyl -6-cyclopropylpyrimidin-2-yl] aniline;
Phenyl pyrrole, for example 4- (2,2-difluoro-1,3-benzodioxol-4-yl) pyrrole-3-carbonitrile;
Cyanamide, such as 3- (4-chlorophenyl) -3- (3,4-dimethoxyphenyl) acryloylmorpholine; and various fungicides, such as dodecylguanidine acetate, 3- [3- (3,5-dimethyl-2- Oxycyclohexyl) -2-hydroxyethyl] glutarimide, hexachlorobenzene, methyl N- (2,6-dimethylphenyl) -N- (2-furoyl) -DL-alaninate, N- (2,6-dimethylphenyl)- N- (2'-methoxyacetyl) -DL-alanine methyl ester, N- (2,6-dimethylphenyl) -N-chloroacetyl-D, L-aminobutyrolactone, N- (2,6-dimethylphenyl)- N- (phenylacetyl) -DL-alanine methyl ester, 5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2,4-dioxo-1,3-oxazolidine, 3- (3,5- (Dichlorophenyl) -5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione, 3- (3,5-dichlorophenyl) -1-isopropyl Pyrcarbamoylhydantoin, N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide, 2-cyano-N- (ethylaminocarbonyl) -2- [methoxyimino] acetamide, 1- [2- (2,4-dichlorophenyl) pentyl] -1H-1,2,4-triazole, 2,4-difluoro-α- (1H-1,2,4-triazolyl-1-methyl) benzhi Drill alcohol, N- (3-chloro-2,6-dinitro-4-trifluoromethylphenyl) -5-trifluoromethyl-3-chloro-2-aminopyridine, 1-((bis (4-fluorophenyl) Methylsilyl) methyl) -1H-1,2,4-triazole.

Production example:
Example 1: 3-trifluoromethylpicolinic acid (ortho-cyclohexyl) anilide:
1.1 Methyl 3-trifluoromethylpyridine-2-carboxylate:
66.8 g (0.4 mol) of pyridine-2,3-dicarboxylic acid was initially charged into a 0.5 liter autoclave. 120 g (6 mol) of anhydrous hydrogen fluoride was then condensed and 138.4 g (1.28 mol) of sulfur tetrafluoride was added under pressure. The mixture was stirred at 60 ° C. for 24 hours. The autoclave was vented and then 150 ml of methanol was added, after which the mixture was stirred at 80 ° C. under autogenous pressure for 3 hours. Vent the autoclave, then pour the contents into 1000 g of ice water, make the mixture alkaline with 40% strength by weight aqueous potassium hydroxide solution, wash 3 times with 350 ml of methylene chloride, the methylene chloride phase Were separated and washed once with 300 ml of water, and then the organic phase was dried over magnesium sulfate. This rate of solvent removal under reduced pressure gave a residue that was distilled under reduced pressure on a 15 cm Vigreux column. 61.9 g of the title compound were obtained as a fraction at 98-99 ° C. (10 mbar) with a purity of 88.7% according to GC.

1H-NMR (DMSO-d6): 3.05 ppm (s, 3H, OMe); 7.85 ppm (m, 1H, pyridine-H); 8.40 ppm (d, 1H, pyridine-H); 8.95 ppm (d, 1H, Pyridine-H).

1.2 Potassium salt of 3-trifluoromethylpyridine-2-carboxylic acid:
20 g (0.086 mol) of 88.7% pure methyl 3-trifluoromethylpyridine-2-carboxylate and 300 ml of 20% strength by weight aqueous potassium hydroxide solution were heated to reflux for 6 hours. The mixture was then adjusted to pH = 5 with aqueous hydrochloric acid and concentrated to dryness. The residue was treated twice with 400 ml boiling methanol. The methanol extracts were combined and evaporated to dryness under reduced pressure. 20.2 g of the title compound were obtained as potassium salt.

1H-NMR (DMSO-d6): 7.3 ppm (m, 1H, pyridine-H); 7,95 ppm (d, 1H, pyridine-H); 8.6 ppm (d, 1H, pyridine-H).

1.3 3-Trifluoromethylpicolinic acid (ortho-cyclohexyl) anilide:
600 mg ortho-cyclohexylaniline and 1.04 g triethylamine were dissolved in 20 ml dichloromethane. 0.72 g of 3-trifluoromethylpicolinoyl chloride was added and the mixture was stirred at room temperature for 14 hours. The reaction mixture was then washed once in each case with aqueous sodium bicarbonate and dilute hydrochloric acid and twice with water. The organic phase was dried over sodium sulfate and concentrated under reduced pressure. The residue was chromatographed on silica gel using a mixture of cyclohexane and methyl tert-butyl ether to obtain 740 mg of the target compound having a melting point of 111 to 116 ° C.

  The compounds of Examples 2-22 (compound of formula I ') were prepared in a similar manner. The physicochemical data are shown in Table 7.

Table 7:

Example of use:
The active compound was prepared as a stock solution containing 0.25% by weight of active compound in acetone or dimethyl sulfoxide (DMSO). 1% by weight of the emulsifier Uniperol ™ EL (wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) was added to this solution and the mixture was diluted with water to the desired concentration.

Activity against powdery mildew of cucumber leaves caused by Sphaerotheca fuliginea, aqueous suspensions having the concentrations of active compounds described below at the cotyledon stage in the leaves of potted cucumber seedlings of the protective application variety “Chinese Snake” The turbidity was sprayed to the runoff point. The coating dried after 20 hours of spraying and the plants were inoculated with an aqueous suspension of cucumber powdery mildew spores (Sphaerotheca fuliginea). The test plants were then cultivated in a greenhouse for 7 days at a temperature of 20-24 ° C. and 60-80% relative atmospheric humidity. Next, the spread of powdery mildew was visually determined by% infection in the cotyledon area. The results are shown in Table 8.

Table 8:

An aqueous suspension having the concentration of the active compound described below was sprinkled on the leaves of potted wheat seedlings of the protective active variety “Kanzler” against Puccinia recondita (wheat rust) . The next day, the treated plants were sprinkled with wheat spore fungus (Puccinia recondita) spores. The plants were then placed in a room with high atmospheric humidity (90-95%) and 20-22 ° C. for 24 hours. During this time, the spores germinated and the germ tube penetrated into the leaf tissue. The next day, the test plants were returned to the greenhouse and cultivated for an additional 7 days at 20-22 ° C. and 65-70% relative atmospheric humidity. Subsequently, the spread of rust fungi on the leaves was visually determined. The results are shown in Table 9.

Table 9:

Claims (14)

Formula I

(Where n is 0, 1, 2, 3 or 4 and the substituents are defined as follows:
X is O, S or a direct bond;
W is O or S;
R ₁ , R ² and R ³ are independently of each other hydrogen, halogen, nitro, CN, C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkyl, C ₂ -C ₄ -alkenyl, C _2- C ₄ -alkynyl, C ₁ -C ₄ -alkoxy, and some or all of the hydrogen atoms in the four last listed groups can be substituted with halogen;
R ⁴ is hydrogen, OH, C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkyl C ₁ -C ₄ -alkoxy, and some of the hydrogen atoms in the three last listed groups or All can be substituted with halogen;
R ⁵ is unsubstituted C ₄ -C ₁₂ -alkyl, C ₃ -C ₁₂ -cycloalkyl, C ₃ -C ₁₂ -alkenyl, C ₅ -C ₁₂ -cycloalkenyl, C ₃ -C ₁₂ -alkynyl, C ₃ -C ₁₂ -Cycloalkyl-C ₁ -C ₄ -alkyl [5 last listed groups can in each case have 1, 2 or 3 substituents R ⁹ Some or all of the hydrogen atoms in the last listed group can be substituted with halogen]; C ₁ -C ₁₂ -haloalkyl, C ₁ -C ₁₂ -alkyl [1, 2 or 3 substitutions] Group R ¹¹ ]; group —C (R ¹⁰ ) ═NOR ⁸ , group —C (O) NR ¹³ R ¹⁴ ; phenyl; phenyl-C ₁ -C ₆ -alkyl, phenyl-C ₂ -C ₆ -alkenyl , Phenyl-C ₂ -C ₆ -alkynyl, phenyloxy-C ₁ -C ₆ -alkyl, phenyloxy-C ₂ -C ₆ -alkenyl, phenyloxy-C ₂ -C ₆ -alkynyl [6 last listed Alkyl, alkenyl and a The alkynyl moiety can have 1, 2, 3 or 4 substituents R ^11, and the phenyl ring in the 7 last listed groups can have 1, 2, 3 or 4 groups R ⁷ . Can have];
R ⁶ has the meaning given for R ¹ which is different from hydrogen;
R ⁷ is C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkyl, C ₁ -C ₄ -alkoxy, C ₂ -C ₄ -alkenyl, C ₂ -C ₄ -alkenyloxy, C ₂ -C ₄ -alkynyl, C ₂ -C ₄ -alkynyloxy [some or all of the hydrogen atoms in these seven groups can be replaced by halogen], OH, halogen, nitro, CN, C _1- C ₄ -alkylthio, C ₁ -C ₄ -alkylsulfonyl, -C (O) R ¹² , NR ¹³ R ¹⁴ , -C (O) NR ¹³ R ¹⁴ , -C (S) NR ¹³ R ¹⁴ , -C ( R ¹⁰⁾ = NOR ^8, phenyl [may have 1, 2, 3 or 4 radicals mentioned under R ^6], phenoxy [1, 2, 3 or 4 mentioned under R ⁶ C ₁ -C ₆ -alkyl-phenyl [some or all of the hydrogen atoms of the alkyl moiety can be substituted with halogens, and the phenyl ring is listed under R ⁶ Can have 1, 2, 3 or 4 groups] In, also two radicals R ⁷ attached to adjacent carbon atoms, CH = CH-CH = CH or can be an alkylene chain having 3-5 carbon atoms, wherein one or two non-adjacent CH ₂ groups can also be replaced by oxygen or sulfur, and some or all of the hydrogen atoms can be replaced by halogens;
R ⁸ is C ₁ -C ₄ -alkyl, C ₃ -C ₆ -cycloalkyl, C ₂ -C ₄ -alkenyl, C ₂ -C ₄ -alkynyl [some of hydrogen atoms in these four groups or All can be substituted with halogen], phenyl or phenyl-C ₁ -C ₆ -alkyl [phenyl in the two last listed groups is 1, 2, 3 listed under R ⁶ Or can have 4 groups];
R ⁹ is C ₁ -C ₄ -alkyl, C ₁ -C ₈ -alkoxy, C ₂ -C ₈ -alkenyloxy, C ₂ -C ₈ -alkynyloxy, C ₁ -C ₄ -alkoxy-C ₁ -C ₈ -alkoxy and some or all of the hydrogen atoms in these groups can be substituted with halogens;
R ¹⁰ is hydrogen, halogen, C ₁ -C ₈ -alkoxy, C ₂ -C ₈ -alkenyloxy, C ₂ -C ₈ -alkynyloxy, C ₁ -C ₄ -alkoxy-C ₁ -C ₈ -alkoxy, C ₁ -C ₁₂ -alkyl, C ₃ -C ₁₂ -cycloalkyl, C ₂ -C ₁₂ -alkenyl, C ₅ -C ₁₂ -cycloalkenyl, C ₃ -C ₁₂ -cycloalkyl-C ₁ -C ₄ -alkyl [Some or all of the hydrogen atoms in the 9 last listed groups can be substituted with halogen], phenyl [1, 2, 3 or 4 groups listed under R ⁷ Can have];
R ¹¹ is halogen, C ₁ -C ₄ -alkyl, C ₁ -C ₈ -alkoxy, C ₁ -C ₈ -alkoxy-C ₁ -C ₈ -alkoxy, C ₂ -C ₈ -alkenyloxy, C _2- C ₈ -alkynyloxy, C ₁ -C ₄ -alkoxy-C ₁ -C ₈ -alkoxy, some or all of the hydrogen atoms in these groups can be substituted with halogens;
R ¹² is hydrogen, OH, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, C ₂ -C ₄ -alkenyl, C ₂ -C ₄ -alkynyl, C ₂ -C ₄ -alkenyloxy, C _2- C ₄ -alkynyloxy, C ₁ -C ₄ -alkoxy-C ₁ -C ₄ -alkoxy, some or all of the hydrogen atoms in the seven last listed groups being substituted with halogens It is possible;
R ¹³ and R ¹⁴ are independently of each other hydrogen, C ₁ -C ₄ -alkyl, C ₂ -C ₄ -alkenyl, C ₂ -C ₄ -alkynyl, and some of the hydrogen atoms in these groups Or all can be substituted with halogen)
3-trifluoromethylpicolinic acid anilide or an agriculturally useful salt of I. The anilide of formula I according to claim 1, wherein R ¹ , R ² and R ³ independently of one another are hydrogen, halogen, C ₁ -C ₄ -alkyl or C ₁ -C ₄ -haloalkyl. The anilide of formula I according to claim ¹ , wherein R ¹ , R ² and R ³ are each hydrogen. ^4. An anilide of formula I according to any one of claims 1 to 3, wherein R4 is selected from the group consisting of hydrogen, methyl, OH and methoxy. The anilide of formula I according to claim ⁴ , wherein R ⁴ is hydrogen. R ⁵ has one of the following meanings:
-Unsubstituted C ₄ -C ₁₂ -alkyl, C ₃ -C ₁₂ -cycloalkyl, C ₂ -C ₁₂ -alkenyl, C ₅ -C ₁₂ -cycloalkenyl, C ₂ -C ₁₂ -alkynyl, where 4 Some or all of the hydrogen atoms in one of the last listed groups can be substituted with halogen, and some or all of the hydrogen atoms in C ₃ -C ₁₂ -cycloalkyl are C ₁ -C ₄ Can be substituted with -alkyl;
- C ₁ -C ₁₂ - haloalkyl, C ₁ -C ₄ - alkoxy - C ₁ -C ₄ - alkyl, C ₁ -C ₄ - haloalkoxy - C ₁ -C ₄ - alkyl;
Phenyl, phenyl-C ₁ -C ₆ -alkyl, wherein the phenyl ring can be substituted by 1, 2, 3 or 4 groups R ⁷ ; or
-C (C ₁ -C ₄ -alkyl) = NO-R ⁸ , wherein some or all of the hydrogen atoms of the C ₁ -C ₄ -alkyl group can be substituted with halogen Item 6. The anilide of formula I according to any one of items 1 to 5. R ⁶ has the following meanings: C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy (these groups can be substituted with halogen) or halogen. An anilide of the formula I as described. 8. Anilide of formula I according to any one of claims 1 to 7, wherein n = 0. R ^1, R ² and R ³ represent each hydrogen, a group XR ⁵ is the amide nitrogen, ortho or anilides of the formula I according to claim 9, wherein the coupled in the meta position. 10. An anilide of formula I according to any one of claims 1 to 9, wherein X is a direct bond or oxygen. X is oxygen or a direct bond and R ⁵ has one of the following meanings:
-Unsubstituted C ₄ -C ₁₂ -alkyl, C ₃ -C ₁₂ -cycloalkyl, C ₂ -C ₁₂ -alkenyl, C ₅ -C ₁₂ -cycloalkenyl, C ₂ -C ₁₂ -alkynyl, where 4 Some or all of the hydrogen atoms in one of the last listed groups can be substituted with halogen, and some or all of the hydrogen atoms in C ₃ -C ₁₂ -cycloalkyl are C ₁ -C ₄ Can be substituted with -alkyl;
- C ₁ -C ₁₂ - haloalkyl, C ₁ -C ₄ - alkoxy - C ₁ -C ₄ - alkyl, C ₁ -C ₄ - haloalkoxy - C ₁ -C ₄ - alkyl;
Phenyl, phenyl-C ₁ -C ₆ -alkyl, wherein the phenyl ring can be substituted by 1, 2, 3 or 4 groups R ⁷ ; or
-C (C ₁ -C ₄ -alkyl) = NO-R ⁸ , wherein some or all of the hydrogen atoms of the C ₁ -C ₄ -alkyl group can be substituted with halogen Item 10. Anilide of Formula I according to Item 10. A method of using 3-trifluoromethylpicolinic acid anilide of formula I and agriculturally acceptable salts thereof according to any one of claims 1 to 11 for controlling harmful bacteria. 12. A bactericidal composition comprising a bactericidal effective amount of at least one 3-trifluoromethylpicolinic acid anilide of formula I or an agriculturally acceptable salt of I according to any one of claims 1-11. A method for controlling harmful fungi, wherein the harmful fungi, their habitat or plants, areas, materials or spaces to be kept free of them are in an amount effective for sterilization of at least one species, 12. A process comprising treating with 3-trifluoromethylpicolinic acid anilide of formula I according to any one of claims 1 to 11 or an agriculturally acceptable salt of I.