WO1997012883A1

WO1997012883A1 - Intermediates and process for the preparation of substituted salicylic acid derivatives as plant protective agents

Info

Publication number: WO1997012883A1
Application number: PCT/EP1996/004201
Authority: WO
Inventors: Joachim Rheinheimer; Uwe Josef Vogelbacher; Ernst Baumann; Ulf Misslitz; Karl-Otto Westphalen; Helmut Walter
Original assignee: Basf Aktiengesellschaft
Priority date: 1995-10-02
Filing date: 1996-09-26
Publication date: 1997-04-10
Also published as: DE19536811A1

Abstract

The invention relates to organic tin compounds of formula (I), wherein the rests have the following meaning: R1 is optionally substituted benzyl, alkyl, dihydropyranyl, trialkyl silyl, alkoxy alkyl and dialkoxy alkyl; and R2 is alkyl, cycloalkyl. It also relates to a process for preparing said compounds, a biocidal agent and their use as biocides.

Description

Intermediates and processes for the production of substituted salicylic acid derivatives as crop protection agents

description

The present invention relates to organic tin compounds of the formula I.

where the residues have the following meaning:

R ¹ optionally substituted benzyl, alkyl, dihydropyranyl, trialkylsilyl, alkoxyalkyl and dialkoxyalkyl;

R ² alkyl, cycloalkyl.

The above-mentioned compounds serve in particular as intermediates for the production of crop protection agents, e.g. of substituted salicylic acid derivatives. Substituted salicylic acid derivatives with good herbicidal and / or bioregulatory activity are known from EP-A 652 216, EP-A 346 789, WO 93/03017 and EP-A 402 751.

The object of the invention was to provide new intermediates for the preparation of substituted salicylic acid derivatives and to provide an advantageous process for the preparation of these compounds.

We have found that this object is achieved by the novel organic tin compounds of the formula I mentioned at the outset. Furthermore, an advantageous process for the preparation of substituted salicylic acid derivatives of the formula IV was found. The latter can then be converted, for example, into the active substances described in the publications mentioned above using known processes.

In the description, the substituents mentioned preferably have the following meaning:

Optionally substituted alkyl, optionally substituted alkylthio and optionally substituted alkoxy: the alkyl group can be represented by one to the maximum possible number

Be substituted halogen atoms and / or carry one to three of the radicals folgen¬: ₄ haloalkoxy nitro, cyano, C ₄ -alkoxy, C C 1 -C ₄ alkylthio, C 1 -C ₄ alkylamino, di-C 1 -C ₄ alkylamino, Cχ-C ₄ alkylcarbonyl, C 1 -C ₄ alkoxycarbonyl, phenyl, substituted with one to three halogen atoms or one to three methyl groups Phenyl, phenoxy, phenoxy substituted with one to three halogen atoms or one to three methyl groups.

Optionally substituted phenyl and optionally substituted benzyi: the phenyl ring can carry one to five halogen atoms, one to three C 1 -C ₄ alkyl or C ₄ -C ₄ alkoxy groups and / or one to three of the following radicals: nitro, cyano, Cι ~ _C4 halo-alkyl, _{Cι-C4-haloalkoxy,} Cι-C ₄ alkylthio, Cι ~ C ₄ alkylamino, di-Cι-C ₄ alkylamino, Cι-C ₄ alkylcarbonyl, Cι ~ C ₄ -Alkoxycarbonyl, phenyl, with one to three halogen atoms or one to three methyl groups substituted phenyl, phenoxy, with one to three halogen atoms or one to three methyl groups substituted phenoxy.

-C-C ₄ alkyl: methyl, ethyl, i-propyl, 2-propyl, 1-butyl, 2-butyl, 2-methyl-propy1, 1, 1-dimethyl-ethyl.

C ₁ -C ₆ -alkyl: C 1 -C ₄ -alkyl and 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-butyl, 3-methyl-butyl, 2-methyl-2-butyl, 3-methyl- 2-butyl, 1,1-dimethyl-propyl, 1,2-dimethyl-propyl, 2,2-dimethyl-propyl, 1-hexyl, 2-hexyl, 3-hexyl, 2-methyl-pentyl, 3-methyl- pentyl, 4-methyl-pentyl, 2-methyl-2-pentyl, 3-methyl-2-pentyl, 4-methyl-2-pentyl, 2-methyl-3-pentyl, 3-methyl-3-pentyl, 2, 2-dimethyl-butyl, 2,3-dimethyl-butyl, 3,3-dimethyl-butyl, 3, 3-dimethyl-1-butyl, 2-ethyl-butyl, 1,1,2-trimethyl-propyl, 1, 2,2-trimethyl-propyl, especially methyl, ethyl, propyl, 2-propyl, butyl, 2-butyl, 1,1-dimethyl-ethyl, pentyl, 2,2-dimethyl-propyl, hexyl.

-C-C ₄ haloalkyl: chloromethyl, difluoromethyl, dichloromethyl, trifluoromethyl, trichloromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 1,1,2,2-tetrafluoroethyl, 2,2,2-trifluoroethyl , 2-chloro-l, 1,2-trifluoroethyl and pentafluoroethyl, decafluorobutyl, 1,1-bis-trifluoromethyl-2,2,2-trifluoroethyl, preferably difluoromethyl, trifluoromethyl, trichloromethyl and chlorodifluoromethyl.

C ₃ -C ₈ cycloalkyl: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, particularly preferably cyclopropyl, cyclopentyl and cyclohexyl.

C 1 -C ₄ -alkylcarbonyl: acetyl, propionyl, 1-propylcarbonyl, 2-propylcarbonyl, 1-butylcarbonyl, 2-butylcarbony1, 2-methylpropylcarbonyl, 1, 1-dimethy1-ethylcarbonyl. Cι-C ₄ alkoxycarbonyl: ethoxycarbonyl, propoxycarbonyl, 1-propyloxycarbonyl, 2-propyloxycarbonyl, 1-butyloxycarbonyl, 2-butyloxycarbonyl, 2-methyl-propyloxycarbonyl, 1, 1-dimethy1-ethoxycarbonyl.

C 1 -C ₄ alkoxy: methoxy, ethoxy, propoxy, 1-methylethoxy, butoxy, 2-butoxy, 1-methylpropoxy, 2-methylpropoxy, 1, 1-dimethylethoxy, especially methoxy, ethoxy, 1-methylethoxy.

Ci-Cε-alkoxy: -C-C ₄ alkoxy and pentoxy, 2-pentoxy, 3-pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy, 2-methyl1-2-butoxy, 3-methyl-2-butoxy , 1, 1-Dimethy1-propoxy, 1,2-dimethyl-propoxy, 2,2-dimethyl-propoxy, 1-hexoxy, 2-hexoxy, 3-hexoxy, 2-methyl-pentoxy, 3-methyl-pentoxy, 4th -Methyl-pentoxy, 2-methyl-2-pentoxy, 3-methyl-1-2-pentoxy, 4-methyl-2-pentoxy, 2-methyl-3-pentoxy, 3-methyl-3-pentoxy, 2,2-dimethyl -butoxy, 2,3-dimethylbutoxy, 3,3-dimethylbutoxy, 2,3-dimethy1-2-butoxy, 3, 3-dimethyl-2-butoxy, especially methoxy, ethoxy, 1-methylethoxy.

C 1 -C ₄ haloalkoxy: difluoromethoxy, trifluoromethoxy, chloro-difluoromethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 1, 1,2,2-tetrafluoroethoxy, 2,2,2-trifluoroethoxy, 2-chlorine -l, 1,2-trifluoroethoxy and pentafluoroethoxy, 1, 1,2, 3, 3, 3-hexafluoropropoxy, heptafluoropropoxy, decafluorobutoxy, 1, 1-bis-trifluoromethyl-2,2,2-trifluoroethoxy , preferably difluoromethoxy, trifluoromethoxy and chlorodifluoromethoxy.

C ₃ -Cχ ₂ -cycloalkoxy: cyclopropoxy, cyclobutoxy, cyclopentoxy, cyclohexyloxy, cycloheptyloxy, cyclooctyloxy, cyclononyloxy, cyclodecyloxy, cycloundecyloxy and cyclododecyloxy, particularly preferably cyclopropoxy, cyclopentoxy and cyclohexyloxy.

Cι-C ₄ -Alkylcarbonyloxy: acetoxy, propionyloxy, 1-propylcarbony1-oxy, 2-propylcarbonyloxy, 1-butylcarbonyloxy, 2-butylcarbonyloxy, 2-methyl-propylcarbonyloxy, 1,1-dimethyl-ethylcarbonyloxy.

C 1 -C ₄ -Alkylthio: methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 2-butylthio, 1-methyl-propylthio, 2-methylpropylthio, 1, 1-dimethylethylthio, especially methylthio, ethylthio, 1- Methyl ethylthio.

C 1 -C ₄ alkylsulfonyl: methylsulfonyl, ethylsulfonyl, propylsulfonyl, 1-methylethylsulfonyl, butylsulfonyl, 2-butylisulfonyl, 1-methylisulfonyl, 2-methylpropylsulfonyl, 1,1-dimethylethylsulfonyl, in particular methylsulfonyl, in particular methylsulfonyl, in particular methylsulfonyl, in particular methylsulfonyl, in particular methylsulfonyl, in particular methylsulfonyl, in particular methylsulfonyl, in particular methylsulfonyl, in particular methylsulfonyl, in particular methylsulfonyl, in particular methylsulfonyl, in particular methylsulfonyl, in particular methylsulfonyl, in particular methylsulfonyl, especially methylsulfonyl, especially methylsulfonyl, especially methylsulfonyl, especially methylsulfonyl, C 1 -C ₄ alkylamino: methylamino, ethylamino, propylamino, 1-methylethylamino, butylamino, 2-butylamino, 1-methylpropylamino, 2-methylpropylamino, 1,1-dimethylethylamino, in particular methylamino, ethylamino, 1-methylethylamino.

Di-Cι-C ₄ alkylamino: dimethylamino, N-methyl-N-ethylamino, diethylamino, N-methyl-N-propylamino, N-Ethy1-N-propylamino, dipropylamino, diisopropylamino, N-isopropyl-N-methylamino, N -Ethy1-N-isopropylamino, N-isopropyl-N-propylamino, dibutylamino, di-2-methylpropylamino, di-1-methylpropylamino, N-butyl-N-methylamino and isomers, N-butyl-N-ethylamino and isomers , N-butyl-N-propylamino and isomers.

With a view to the intended use of the end products, such as, for example, the active substances described in the publications mentioned above, compounds of the formula I are preferred as intermediates in which the substituents have the following meaning:

R ¹ optionally substituted benzyl, C ₁ -C ₆ -alkyl, dihydro pyranyl, tri-C ₆ -alkylsilyl, C ₄ -alkoxy-C ₄ -alkyl and di-C ₄ -alkoxy-C 1 -C C ₄ alkyl;

R ² -C ₆ alkyl, C ₃ -C ₆ cycloalkyl.

Compounds of the formula I in which the substituents have the following meaning are particularly preferred:

R ¹ -C ₄ alkyl;

R ² Ci-Ce alkyl, C ₃ -C ₆ cycloalkyl.

The organic tin compounds of the formula I are prepared by metalating the underlying benzoic acid with a suitable base at low temperatures and then reacting it with a trialkyltin compound of the formula III to give the tin compound I:

V

II I wherein the substituents R ¹ and R ^{2 have} the meaning given above. Cycloalkyl or alkyl-lithium compounds are particularly suitable as bases, and the commercially available isomers of butyl and hexyllithium are particularly suitable. It is often expedient to add an auxiliary to promote the metallization. For this purpose ethers, alcoholates such as potassium tert-butoxide or amines such as tetramethylethylenediamine are suitable. The metalation can take place at temperatures from 0 to 130 ° C., preferably between -50 and -100 ° C. All solvents commonly used in metallizations are also suitable for this reaction; diethyl ether, methyl tert-butyl ether, tetrahydrofuran and simple hydrocarbons are particularly suitable, and it may be advantageous to use mixtures of these substances. The reaction times for the metalation can range from a few minutes to a few hours. The trialkyltin compound is then added, where X is the usual leaving groups, preferably chlorine or bromine. The above applies to the temperature during the addition and the subsequent reaction time. An aqueous or non-aqueous workup can then be carried out, it being useful in the first case to keep the pH of the aqueous phase constant with a buffer. If necessary, it increases the yield considerably if, before working up, a substance is added at low temperatures that is suitable for destroying excess base. For example, carbon dioxide, water, alkyl or benzyl halides are suitable. If necessary, the organic tin compounds of the formula I can be further purified, for example by chromatography on silica gel. They also prove to be stable against water at various pH values during processing and can be stored at room temperature.

The organic tin compounds of formula I have biocidal properties. The herbicidal properties are particularly pronounced.

The compounds I and their agriculturally useful salts are suitable - both as isomer mixtures and in the form of the pure isomers - as herbicides. The herbicidal compositions containing I control vegetation very well on non-cultivated areas, particularly when high amounts are applied. In crops such as wheat, rice, corn, soybeans and cotton, they act against weeds and harmful grasses without significantly damaging the crop plants. This effect occurs especially at low application rates. Depending on the particular application method, the compounds I or compositions containing them can also be used in a further number of crop plants for eliminating undesired plants. The following crops are considered, for example:

Alliuπ. cepa, pineapple comosus, Arachis hypogaea, Asparagus officinalis, Beta vulgaris ssp. altissima, Beta vulgaris ssp. rapa, Brassica napus var. napus, Brassica napus var. napobrassica, Brassica rapa var. silvestris, Camellia sinensis, Carthamus tinctorius, Carya illinoinensis, Citrus limon, Citrus sinensis, Coffea arabica (Coffea canephora, Coffea libericaus), Cucumodison , Daucus carota, Elaeis guineensis, Fragaria vesca, Glycine max, Gossypium hirsutum, (Gossypium arboreum, Gossypium herbaceum, Gossypium vitifolium), Helianthus annuus, Hevea brasiliensis, Hordeum vulgare, Humulus lupulus, Ipomoealumisisumisum , Lycopersicon lycopersicum, Malus ssp., Manihot esculenta, Medicago sativa, Musa ssp., Nicotiana tabacum (N.rustica), Olea europaea, Oryza sativa, Phaseolus lunatus, Phaseolus vulgaris, Picea abies, Pinus ssp., Pisum sativum, Prunus , Prunus persica, Pyrus communis, Ribes sylvestre, RjLcinus communis, Saccharum officinarum, Seeale cereale, Solanum, tuberosum, Sorghum bicolor (see vulgar), Theobroma cacao, Trifolium pr atense, Triticum aestivum, Triticum durum, Vicia faba, Vitis vinifera, Zea mays.

In addition, the compounds I can also be used in crops which are tolerant to the action of herbicides by breeding, including genetic engineering methods.

The herbicidal compositions or the active compounds can be applied pre- or post-emergence. If the active ingredients are less compatible for certain crop plants, application techniques can be used in which the herbicidal compositions are sprayed with the aid of sprayers in such a way that the leaves of the sensitive crop plants are not hit wherever possible, while the active ingredients are applied to the leaves of undesirable plants growing below them or the uncovered floor area (post-directed, lay-by).

The compounds I or the herbicidal compositions comprising them can be sprayed, for example, in the form of directly sprayable aqueous solutions, powders, suspensions, and also high-strength aqueous, oily or other suspensions or dispersions, emulsions, oil dispersions, pastes, dusts, spreading agents or granules , Fogging, dusting, scattering or pouring can be used. The application forms depend on the uses; in any case, they should ensure the finest possible distribution of the active compounds according to the invention.

The following are essentially considered as inert additives:

Mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, also coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. Paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, alkylated benzenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol, cyclohexanol, ketones such as cyclohexanone or strongly polar solvents, e.g. Amines such as N-methylpyrrolidone or water.

Aqueous use forms can be prepared from emulsion concentrates, suspensions, pastes, wettable powders or water-dispersible granules by adding water. To prepare emulsions, pastes or oil dispersions, the substrates as such or dissolved in an oil or solvent can be homogenized in water by means of wetting agents, adhesives, dispersants or emulsifiers. However, it is also possible to prepare concentrates consisting of an active substance, Metz, adhesive, dispersant or emulsifier and possibly solvent or oil, which are suitable for dilution with water.

The surface-active substances (adjuvants) are the alkali, alkaline earth, ammonium salts of aromatic sulfonic acids, for example lignin, phenol, naphthalene and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylarylsulfonates, alkyl, lauryl ether and fatty alcohol sulfates, and salts sulfated hexa-, hepta- and octadecanols as well as fatty alcohol glycol ether, condensation products of sulfonated naphthalene and its derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl, octyl, phenyl or nonyl phenyl Tributylphenyl polyglycol ether, alkyl aryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ether or polyoxypropylene alkyl ether, lauryl alcohol polyglycol ether acetate, sorbitol ester, lignin sulfite waste liquor or methyl cellulose. Powders, materials for broadcasting and dusts can be prepared by mixing or grinding the active substances together with a solid carrier.

Granules, e.g. Coated, impregnated and homogeneous granules can be produced by binding the active ingredients to solid carriers. Solid carriers are mineral soils such as silica, silica gels, silicates, talc, kaolin, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, Ammonium phosphate, ammonium nitrate, ureas and vegetable products such as cereal flour, tree bark, wood and nutshell flour, cellulose powder or other solid carriers.

The concentrations of the active ingredients I in the ready-to-use preparations can be varied within a wide range. The formulations generally contain 0.001 to 98% by weight, preferably between 0.01 to 95% by weight, of active ingredient. The active ingredients are used in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).

The compounds I according to the invention can be formulated, for example, as follows:

I 20 parts by weight of compound No. 1 are dissolved in a mixture which alkylated from 80 parts by weight. Benzene, 10 parts by weight of the adduct of

8 to 10 mol of ethylene oxide in 1 mol of oleic acid-N-monoethanolamide, 5 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 5 parts by weight of the adduct of 40 mol of ethylene oxide and 1 mol of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained which contains 0.02% by weight of the active ingredient.

II 20 parts by weight of compound no. 1 are dissolved in a mixture consisting of 40 parts by weight of cyclohexanone,

30 parts by weight of isobutanol, 20 parts by weight of the adduct of 407 mol of isooctylphenol-ethylene oxide and 1 mol of isooctylphenol and 10 parts by weight of the add-on product consist of 40 mol of ethylene oxide and 1 mol of castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient. III 20 parts by weight of active ingredient No. 1 are in a

Dissolved mixture, which consists of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction from the boiling point 210 to 280 ° C and 10 parts by weight of the adduct of 40 mol ethylene oxide with 1 mol castor oil. Pouring the solution into 100,000 parts by weight of water and finely distributing it therein gives an aqueous dispersion which comprises 0.02% by weight of the active ingredient.

IV 20 parts by weight of active ingredient No. 1 are with

3 parts by weight of the sodium salt of diisobutylnaphthalenesulfonic acid, 17 parts by weight of the sodium salt of a lignosulfonic acid from a sulfite waste liquor and 60 parts by weight of powdered silica gel are mixed well and ground in a hammer mill. A spray liquor containing 0.1% by weight of the active ingredient is obtained by finely distributing the mixture in 20,000 parts by weight of water.

V 3 parts by weight of active ingredient No. 1 are with

97 parts by weight of finely divided kaolin mixed. In this way, a dust is obtained which contains 3% by weight of the active ingredient.

VI 20 parts by weight of active ingredient No. 1 are with

2 parts by weight of calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of fatty alcohol polyglycol ether, 2 parts by weight of sodium salt of a phenol-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.

VII 1 part by weight of compound I is dissolved in a mixture consisting of 70 parts by weight of cyclohexanone, 20 parts by weight of ethoxylated isooctylphenol and 10 parts by weight of ethoxylated castor oil. A stable emulsion concentrate is obtained.

VIII 1 part by weight of compound I is dissolved in a mixture consisting of 80 parts by weight of cyclohexanone and

20 parts by weight of Wettol ^® EM31 (non-ionic emulsifier based on ethoxylated castor oil). A stable emulsion concentrate is obtained.

In order to broaden the spectrum of activity and to achieve synergistic effects, the substituted salicylic acid derivatives I can be used with numerous representatives of other herbicidal or growth-regulating groups of active ingredients are mixed and applied together. For example, 1,2, 4-thiadiazoles, 1,3,4-thiadiazoles, amides, aminophosphoric acid and their derivatives, aminotriazoles, anilides, (het) -aryloxyalkanoic acid and their derivatives, benzoic acid and their derivatives, benzothiadiazione come as mixing partners , 2-aroyl-l, 3-cyclohexanediones, hetaryl aryl ketones, benzylisoxazolidinones, meta-CF3-phenyl derivatives, carbamates, quinolinecarboxylic acid and their derivatives, chloroacetanilides, cyclohexane-1,3-dione derivatives, diazines, dichloropropionic acid and their derivatives , Dihydrobenzofurans, dihydrofuran-3-ones, dinitroanilines, dinitrophenols, diphenyiether, dipyridyls, halocarboxylic acids and their derivatives, ureas, 3-phenyluracils, imidazoles, imidazolinones, N-phenyl-3, 4, 5,6-tetrahydronapholeimide, oxir Phenols, aryloxy or heteroaryloxyphenoxy propionic acid esters, phenylacetic acid and its derivatives, phenyl propionic acid and its derivatives, pyrazoles, phenylpyrazoles, pyridazme, pyridinecarboxylic acid and its derivatives, pyrimidyl ether, Sulfonamides, sulfonylureas, triazines, triazinones, triazolmones, triazolecarboxamides, uraciles.

It may also be useful to apply the compounds I alone or in combination with other herbicides or growth regulators, mixed with other crop protection agents, for example with agents for controlling pests or phytopathogenic fungi or bacteria. Also of interest is the miscibility with mineral salt solutions, which are used to remedy nutritional and trace element deficiencies. Non-phytotoxic oils and oil concentrates can also be added.

The amount of active ingredient applied is 0.001 to 3.0, preferably 0.01 to 1.0 kg / ha of active substance depending on the control target, the season, the target plants and the growth stage.

Examples of use

The herbicidal activity of the substituted salicylic acid derivatives of the formula I was demonstrated by greenhouse tests:

Plastic flower pots with loamy sand with about 3.0% humus as a substrate served as culture vessels. The seeds of the test plants were sown separately according to species.

In pre-emergence treatment, the active ingredients suspended or emulsified in water were applied directly after sowing by means of finely distributing nozzles. The vessels were sprinkled lightly to encourage germination and growth, and then clear plastic covers until the plants had grown. This cover causes the test plants to germinate evenly, provided that this has not been impaired by the active ingredients.

For the purpose of post-emergence treatment, the test plants, depending on the growth habit, are first grown to a height of 3 to 15 cm and only then treated with the active ingredients suspended or emulsified in water. For this purpose, the test plants are either sown directly and grown in the same containers or they are first grown separately as seedlings and transplanted into the test containers a few days before the treatment. The application rate for post-emergence treatment is 3.0 kg / ha a.S.

The plants were kept in a species-specific manner at temperatures of 10 to 25 ° C and 20 to 35 ° C. The trial period lasted 2 to 4 weeks. During this time, the plants were cared for and their response to the individual treatments was evaluated.

Evaluation was carried out on a scale from 0 to 100. 100 means no emergence of the plants or complete destruction of at least the aerial parts and 0 means no damage or normal growth.

The plants used in the greenhouse experiments are composed of the following types:

Table 1 - Post-emergence herbicidal activity in the greenhouse

We have also found processes for preparing the salicylic acid derivatives of the formula IV by reacting the tin compounds of the formula I with aromatic or heteroaromatic compounds of the formula V in the presence of a transition metal complex as catalyst:

IV wherein R ¹ and R ^{2 have} the meanings described above and

R ^{3 is} chlorine, bromine, iodine, fluorosulfonyl or fluoroalkyl sulfonyl;

A is a 5-membered heteroaromatic linked via a carbon atom and having an oxygen, nitrogen or sulfur atom or having one to four nitrogen atoms or having one or two nitrogen atoms and additionally a sulfur or oxygen atom in the ring, which may be substituted one or more times can be; a 6-membered heteroaromatic with one to four nitrogen atoms in the ring, which can optionally be substituted one or more times; optionally mono- or polysubstituted phenyl

mean. The following heterocycles are particularly preferred as 5-membered heteroaromatics: 2-thienyl, 3-thienyl, 2-furyl, 3-furyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl , 5-pyrazolyl, 1-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 2-0xazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isoxazolyl, 4 -Isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 1,2, 3-triazol-l-yl, 1,2,3-triazol-4-yl, l, 2,3-triazole -5-yl, (IH) 1,2,4-triazol-l-yl, (IH) 1,2,4-triazol-3-yl, (IH) 1,2,4-triazol-5- yl, (4H) 1,2,4-triazol-2 (5) -yl, (4H) l, 2,4-triazol-4-yl, 1-tetrazolyl, 5-tetrazolyl, 2-oxazolyl, 4-oxazolyl , 5-oxazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 1,2,3-oxadiazole -4-yl, 1, 2,3-oxadiazol-5- yl, l, 2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 3 (4) furazanyl, 1,3,4-oxadiazol-2 (5) -yl, 1,2,3-thiadiazol-4-yl, 1,2,3-thiadiazol-5-yl, l , 2,5-thiadiazol-3-yl, 1,3, 4-thiadiazol-2-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl.

The following heterocycles are particularly preferred as β-membered heteroaromatics: 2-pyridyl, 4-pyridyl, 3-pyridyl, 2 ₇ pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, pyrazin-2-yl, pyridazin-3-yl, pyridazin-4 -yl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl, 1,2,4-triazin-5-yl, 1,2,4-triazin-6 -yl, l, 2,4,5-tetrazin-3-yl.

The following are preferably considered as substituents: fluorine, chlorine, bromine, iodine, optionally substituted alkyl, optionally substituted alkoxy, optionally substituted alkylthio, optionally substituted alkylsulfoxy, optionally substituted C ₃ -C ₆ cycloalkyl, C ₃ -Ce -Cycloalkoxy, cyano, nitro, formyl, -C-C ₄ -alkoxycarbonyl, Di-Cι-C ₄ -alkylamino, Cι ~ C ₄ - alkylamino.

A catalytically active palladium compound is used in this process. Any palladium salts or complexes which are at least partially soluble in the reaction mixture are suitable. The oxidation state of the palladium can be 0 or 2. The following counterions are suitable for the palladium salts: chloride, bromide, iodide, sulfate, acetate, trifluoroacetate, acetylacetonate or hexafluoro-2,4-pentadionate. Many different palladium complexes can be used. The only requirement is that the ligands on the palladium can be displaced from the substrate under the reaction conditions. Phosphine ligands such as aryl-alkyl phosphines such as methyldiphenylphosphine, isopropyldiphenylphosphine, triarylphosphines such as triphenylphosphine, tritolyl- phosphine, trixylylphosphine, trihetarylphosphines such as trifurylphosphine or dimeric phosphines. Olefinic ligands such as, inter alia, dibenzylidene acetone or its salts, cycloocta-1,5-diene or amines such as trialkylamines (for example triethylamine, tetramethylethylene diamine, N-methylmorpholine) or pyridine are also very suitable.

The complex used can be used directly in the reaction. So you can e.g. with tetrakistriphenylphosphine palladium (O), bistriphenylphosphine palladium dichloride, bistriphenylphosphine palladium diacetate, a dibenzylideneacetone palladium (O) complex, tetrakismethyldiphenylphosphine palladium (O) or bis (1,2-diphenylphosphino dichloride) palladium dichloride. A palladium salt and additionally a suitable ligand can also be used, which then only form the catalytically active complex in situ. This procedure is available e.g. with the above-mentioned salts and phosphine ligands such as e.g. Trifuryl phosphine or tritolyl phosphine. Palladium complexes such as e.g. Tris (dibenzylidene acetone) dipalladium, bis (dibenzylidene acetone) palladium or 1,5-cyclooctadiene palladium dichloride by the addition of ligands such as e.g. Trifurylphosphine or Tritolyl¬ phosphine can be activated further.

Usually 0.001 to 10 mol%, in particular 0.005 to 5 mol%, of the palladium compound (salt or complex), based on the compound I, is used. Higher quantities are possible but rather uneconomical. The amount of V, based on the starting material I, is generally from 0.8 to 3, preferably from 0.95 to 1.5, molar equivalents. All solvents which do not themselves react with the substrates used are suitable for the reaction. Polar solvents accelerate the reaction. Ethers such as diethyl ether, methyl tert-butyl ether, dimethoxyethane, tetrahydrofuran, dioxane, amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylpropyleneurea or amines such as triethylamine are particularly suitable. The use of mixtures, for example of ethers with amides, is often advantageous. Alkyl alcohols and water can also be considered as mixing partners, especially if the radical B contains a boron atom. The addition of tetraalkylammonium halides or alkali metal halides such as lithium chloride is often helpful and is particularly advisable if Z stands for a sulfonyloxy radical. Especially if the radical B contains a boron atom, it is often useful to add an organic or inorganic base such as potassium carbonate, sodium carbonate, calcium carbonate, calcium hydroxide, sodium hydroxide, potassium hydroxide, potassium phosphate, sodium phosphate, pyridine or an amine such as triethylamine. The reaction temperature is between -20 and 200 ° C, preferably between 50 and 160 ° C. The reaction times are usually between a few minutes and 50 hours, usually 0.5 to 10 hours. When using low-boiling solvents, it is sometimes useful to carry out the reaction under autogenous pressure in the autoclave.

The invention furthermore comprises, as intermediates, the substituted salicylic acid derivatives of the formula IV

wherein the substituents R ¹ and A have the meaning described above, with the proviso that the radical A is not optionally substituted phenyl. The preferred substituents are also the same as those described above.

The compounds of formula IV serve as intermediates in the synthesis of new and known heterocyclically substituted salicylic acid derivatives, the herbicidal activity of which is reported, for example, in the patent applications cited above. For this purpose, the radical R ¹ is first removed using known methods such as hydrolysis or hydrogenolysis in order to release the hydroxyl group. The heterocyclically substituted salicylic acids, which are easily accessible in this way, can then be reacted by known processes, for example with a suitable pyrimidine derivative, to give the desired crop protection active compounds.

example 1

2-methoxy-6-tributylstannylbenzoic acid (Verb. No. 1):

option A

30.0 g (0.26 mol) of N, N, N ', N'-tetramethylethylenediamine in 250 ml of tetrahydrofuran were cooled to -90 ° C. and 208 ml (0.27 mol) of 1.3 m sec-butyllithium Solution in hexane and then a solution of 18.0 g (0.117 mol) of 2-methoxybenzoic acid dissolved in 100 ml of tetrahydrofuran were added dropwise. The mixture was stirred for 1 h at -90 ° C. and then 47.4 g (0.140 mol) of chlortributylstannane dissolved in 20 ml of tetrahydrofuran were added dropwise. The mixture was allowed to warm to -76 ° C., the mixture was stirred at this temperature for 40 min and 54.9 g (0.351 mol) of benzyl bromide were added dropwise. It was allowed to warm to -20 ° C., poured onto a mixture of 400 ml of water, 100 g of potassium dihydrogenphosphate and 100 g of disodium hydrogenphosphate dihydrate, extracted three times with methyl tert-butyl ether, over sodium dried sulfate and concentrated in vacuo. For purification, chromatography was carried out on silica gel using cyclohexane / ethyl acetate (99: 1). Yield: 19.7 g (38%) ¹ H-NMR (CDC1 ₃ ): δ = 0.84 (t); 1.03 (m); 1.30 (m); 1.45 (m); 4.07 (s); 7.03 (d); 7.38 (d); 7.52 (t); 11.30 (widened).

Variant B

7.66 g (66 mmol) of N, N, N ', N'-tetramethylethylenediamine in 60 ml of tetrahydrofuran were cooled to -90 ° C. and 53 ml (69 mmol) of 1.3 m sec-butyllithium solution in hexane and then a solution of 4.6 g (30 mmol) of 2-methoxybenzoic acid dissolved in 30 ml of tetrahydrofuran was added dropwise. The mixture was stirred at -90 ° C. for 1 h and then 12.2 g (36 mol) of chlortributylstannane were added dropwise. The mixture was allowed to warm to -70 ° C., stirred at this temperature for 45 min and some ice was added. The mixture was stirred at this temperature for 10 min and poured directly onto a mixture of 150 ml of water, 35 g of potassium dihydrogenphosphate and 35 g of disodium hydrogenphosphate dihydrate, extracted three times with methyl tert-butyl ether, dried over sodium sulfate and concentrated in vacuo. For purification you can chromatograph on silica gel with cyclohexane / ethyl acetate (99: 1). The product can be used in the same way as that prepared according to variant A.

2-methoxy-6-trimethylstannylbenzoic acid can be obtained analogously to the example above if chlorotrimethylstannane is used instead of chlortributylstannane.

Example 2

2-methoxy-6- (6-trifluoromethylpyridin-2-yl) benzoic acid (No.

1,430):

In 150 ml of anhydrous dioxane, 9.2 g (21 mmol) of 2-methoxy-6-tributylstannylbenzoic acid, 0.36 g of tetrakis (triphenylphosphine) palladium (O), 68 mg of 2, 6-bis-tert-butyl-4 methylphenol and 5.8 g (25.6 mmol) of 2-bromo-6-trifluoromethylpyridine dissolved and stirred in an autoclave at 130 ° C. for 3 h. After concentration in vacuo, the mixture was transferred into 20% sodium hydroxide solution, washed twice with methylene chloride and acidified with concentrated hydrochloric acid while cooling with ice. The precipitated product was filtered off, washed with water and dried in vacuo at 45 ° C. Yield: 2.6 g (42%). Mp 201 to 203 ° C. ¹ H NMR (DMSO-d ₆ ): δ = 3.81 (s); 7.22 (d); 7.30 (d); 7.53 (t); 7.87 (d); 7.95 (d); 8.15 (t); 12.80 (widened). Example 3

2- (4,6-Dimethoxypyrimidin-2-yl) -6- (6-trifluoromethylpyridin-2-yl) benzoic acid (Compound No. 2):

a) To 2.1 g (7.1 mmol) of 2-methoxy-6- (6-trifluoromethylpyridine-

2-yl) -benzoic acid dissolved in 100 ml dichloromethane, 7.1 ml (8.1 mmol) of a 1 M boron tribromide solution were added dropwise and the mixture was stirred overnight. Then 7.1 ml of methanol were added dropwise, poured onto 150 ml of 10% sodium hydroxide solution and the organic phase was separated off. The aqueous phase was concentrated to ice with ice. Acidified with hydrochloric acid, extracted with ethyl acetate, dried over sodium sulfate and concentrated in vacuo. Yield: 1.7 g (85%). The product was used directly for the following experiment.

b) A mixture of 1.6 g (5.7 mmol) of 2-hydroxy-6- (6-trifluoromethylpyridin-2-yl) benzoic acid and 80 ml of water was mixed with 0.36 g (5.5 mmol) 85% potassium hydroxide adjusted to a pH of 9, stirred for 1 h and concentrated in vacuo. The mixture was then boiled six times with toluene in a rotary vacuum at 80 to 90 ° C. to dry in a rotary evaporator. The salt thus obtained was added to 120 ml of dimethyl sulfoxide, 0.143 g (5.7 mmol) of 95% sodium hydride was added and the mixture was stirred at room temperature for 2.5 h. 1.23 g (5.7 mmol) of 4, 6-dimethoxy-2-methylsulfonylpyrimidine were added and the mixture was stirred at room temperature for 5 h. The reaction mixture was poured onto 200 ml of phosphoric acid ice water and extracted five times with ethyl acetate. The organic phase was washed four times with 100 ml of phosphoric acid water, dried over sodium sulfate and concentrated in vacuo. The

If necessary, the crude product could also be chromatographed on silica gel

Cyclohexane / ethyl acetate are cleaned.

Yield: 1.5 g (65%). 109 to 111 ° C.

* H NMR (DMSO-d ₆ ): δ = 3.78 (s); 6.02 (s); 7.46 (m); 7.66 (m); 7.89 (d); 8.02 (d); 8.20 (t); 13.0 (widened).

Example 4

2-methoxy-6- (2-fluoropyridin-5-yl) benzoic acid (No. 1,384):

In 150 ml of anhydrous dioxane, 12.2 g (27.7 mmol)

2-methoxy-6-tributylstannylbenzoic acid, 0.47 g tetrakis (triphenylphosphine) palladium (O), 89 mg 2,6-bis-tert-butyl-4-methylphenol and 7.5 g (33.8 mmol) dissolved 2-fluoro-5-iodopyridine and stirred in an autoclave at 130 ° C. for 3.5 h. After concentration in vacuo, the mixture was transferred to 200 ml of 15% sodium hydroxide solution, washed twice with methylene chloride and acidified with concentrated hydrochloric acid while cooling with ice. The mixture was extracted with ethyl acetate and dried over sodium sulfate and concentrate in vacuo. Further purification was carried out by chromatography on silica gel with cyclohexane / ethyl acetate. Yield: 3.1 g (46%). 143 to 145 ° C. ⁱ H-NMR (DMSO-d ₆ ): δ = 3.81 (s); 7.04 (d); 7.19 (d); 7.29 (d); 7.50 (t); 7.98 (mc); 8.21 (s); 13.10 (broadened).

Example 5

2- (4, 6-Dimethoxypyrimidin-2-yl) -6- (2-f luorpyridin-5-yl) -benzoic acid (compound no. 3:

a) To 2.0 g (8.1 mmol) of 2-methoxy-6- (2-fluoropyridin-5-yl) -benzoic acid dissolved in 100 ml of dichloromethane were added 8.1 ml (8.1 mmol) of a 1 M boron tribromide solution and stirred overnight. Then 9 ml of methanol were added dropwise, poured onto 200 ml of 15% sodium hydroxide solution and extracted with dichloromethane. The aqueous phase was concentrated under ice with conc. Acidified with hydrochloric acid, whereby the product failed. After filtering off, the mixture was washed with water, dissolved in ethyl acetate, dried over sodium sulfate and concentrated in vacuo. Yield: 1.8 g (96%). Melting point: 187 to 188 ° C. The product was used directly for the following experiment.

b) A mixture of 1.3 g (5.6 mmol) of 2- (2-fluoropyridin-5-yl) - 6-hydroxybenzoic acid and 80 ml of water was mixed with 0.31 g

(5.6 mmol) of potassium hydroxide adjusted to a pH of 9 and concentrated in vacuo. The mixture was then boiled out six times with toluene in a rotary vacuum at 80 to 90 ° C. to dry in a rotary evaporator. 1.3 g (5.1 mmol) of the salt thus obtained were stirred with a little molecular sieve (4 Angstrόm) in 80 ml of dimethyl sulfoxide for 1 h, 0.13 g (5.1 mmol) of 95% sodium hydride and added for 1 h Room temperature stirred. 1.1 g (5.1 mmol) of 4, 6-dimethoxy-2-methylsulfonylpyrimidine were added and the mixture was stirred overnight at room temperature. The reaction mixture was poured onto 200 ml of phosphoric acid ice water and extracted four times with ethyl acetate. The organic phase was washed five times with phosphoric acid water, dried over sodium sulfate and concentrated in vacuo. Yield: 1.5 g (75%). Mp 159 to 160 ° C. ⁱ H NMR (DMSO-d ₆ ): δ = 3.78 (s); 6.01 (s); 7.29 (dd); 7.40 (m); 7.60 (t); 8.02 (m); 8.25 (s). Example 6

2-Methoxy-6- (5-trifluoromethylpyridin-2-yl) benzoic acid (No. 1,429) can be prepared largely analogously to 2-methoxy-6- (2-fluoropyridin-5-yl) benzoic acid: Yield (after Cleaning) 47%. ⁱ H-NMR (DMSO-de): δ = 3.81 (s); 7.24 (d); 7.33 (d); 7.51 (t); 7.87 (d); 8.29 (d); 8.97 (s); 12.80 (widened).

2-methoxy-6- (3-methoxypyridazin-6-yl) benzoic acid (No. 1.470):

7.1 g (16.1 mmol) of 2-methoxy-6-tributylstannylbenzoic acid, 0.25 g of tetrakis (triphenylphosphine) palladium (O), 48 mg of 2, 6-bis-tert-butyl were placed in 180 ml of anhydrous dioxane -4-methylphenol and 3.0 g (16.1 mmol) of 3-bromo-6-methoxypyridazine dissolved and stirred in an autoclave at 130 ° C for 2 h. After concentration in vacuo, the mixture was chromatographed on silica gel using cyclohexane / ethyl acetate / acetic acid (24: 1: 0.05). Mp (sublimation at over 200 ° C). ⁱ H-NMR (DMSO-d ₆ ): δ = 3.81 (s); 4.03 (s); 7.24 (m); 7.30 (d); 7.49 (t); 7.85 (d); 12.90 (widened).

The compounds in Table 1 can be prepared analogously to the examples given.

Table 1: Intermediates of formula IVa (R ¹ = methyl)

Claims

claims

1. Organic tin compounds of formula I.

where the residues have the following meaning:

R ² alkyl, cycloalkyl.

2. Organic tin compounds of formula I according to claim 1, wherein the radicals have the following meaning:

R ¹ optionally substituted benzyi, Ci-C _δ- alkyl, dihydropyranyl, tri-Ci-C _δ -alkylsilyl, -C ~ C ₄ -alkoxy- Cι-C ₄ -alkyl and di-Cι-C ₄ -alkoxy-Cι-C ₄ alkyl;

R ² Ci-Ce alkyl, C ₃ -C ₆ cycloalkyl.

3. Organic tin compounds of formula I according to claim 1 or 2, wherein the radicals have the following meaning:

R ¹ -C ₄ alkyl;

R ² alkyl, cycloalkyl.

4. A process for the preparation of the organic tin compounds of the formula I according to claim 1, characterized in that a salicylic acid derivative of the formula II is metalated with a base and then reacted with a tin compound of the formula III.

II I wherein the radicals R ¹ and R ^{2 have} the meaning given in claim 1. 5. A process for the preparation of the organic tin compound of the formula I as claimed in claim 4, characterized in that an alkyl or cycloalkyl-lithium compound is used as the base.

6. A process for the preparation of the salicylic acid derivatives of the formula IV, characterized in that tin compounds of the formula I are reacted with compounds of the formula V in the presence of a catalyst

I IV where the substituents have the following meaning:

R ^ R ^{2 has} the meaning given in claim 1;

R ^{3 is} chlorine, bromine, iodine, fluorosulfonyl or fluoroalkylsulfonyl;

A is a 5-membered heteroaromatic linked via a carbon atom with an oxygen, nitrogen or

Sulfur atom or with one to four nitrogen atoms or with one or two nitrogen atoms and additionally one sulfur or oxygen atom in the ring, which can optionally be substituted one or more times;

a 6-membered heteroaromatic with one to four nitrogen atoms in the ring, which can optionally be substituted one or more times; optionally mono- or polysubstituted

Phenyl.

Salicylic acid derivatives of the formula IV

in which the substituents have the following meaning: R ¹ optionally substituted benzyl, alkyl, dihydropyranyl, trialkylsilyl, alkoxyalkyl and dialkoxyalkyl;

A is a S-membered heteroaromatic linked via a carbon atom and having an oxygen, nitrogen or sulfur atom or having one to four nitrogen atoms or having one or two nitrogen atoms and additionally a sulfur or oxygen atom in the ring, which may optionally be mono- or polysubstituted; a 6-membered heteroaromatic with one to four nitrogen atoms in the ring, which can optionally be substituted one or more times.

Use of the organic tin compounds of formula I according to claim 1 as biocides.

9. Use of the organic tin compounds of formula I according to claim I as herbicides.

10. A biocidal agent containing a biocidally effective amount of at least one organic tin compound of the formula I according to claim 1 and at least one inert liquid and / or solid carrier and, if desired, at least one adjuvant.

11. A herbicidal composition comprising a herbicidally effective amount of at least one organic tin compound of the formula I according to claim 1 and at least one inert liquid and / or solid carrier and, if desired, at least one adjuvant.

12. A process for the preparation of biocidally active agents, characterized in that a biocidally effective amount of at least one organic tin compound of the formula I according to claim 1, and at least one inert liquid and / or solid carrier and, if desired, at least one adjuvant are mixed.

13. A process for the preparation of herbicidally active agents, characterized in that a herbicidally effective amount of at least one organic tin compound of the formula I according to Claim 1, and at least one inert liquid and / or solid carrier and, if desired, at least one adjuvant are mixed. 14. A method for controlling undesirable plant growth, characterized in that a herbicidally effective amount of at least one organic tin compound of the formula I according to claim 1 is allowed to act on plants, their habitat or on seeds.