EP1656019A1 - Use of alcohol-oxyalkylates in the form of adjuvants for benzamidoxime gungicidal derivatives, appropriate agents and kits - Google Patents

Abstract

The invention relates to the use of alkoxylated alcohols (alcohol-oxyalkylates) in the form of adjuvants for improving fungicidal effect of benzamidoxime derivatives of formula (I) such as, for example N-phenylacetyl-2-difluoromethoxy-5,6-difluorobenzamide-(O-cyclopropylmethyl]-oxime or N-phenylacetyl-2-trifluoromethoxy-5,6-difluorobenzamide-(O-cyclopropylmethyl]-oxime. Appropriate agents and kits are also disclosed.

Description

 Use of alcohol alkoxylates as adjuvant for fungicidal benzamidoxi derivatives, corresponding agents and kits.

5 The present invention relates to the use of alcohol alkoxylates as adjuvants for fungicidal benzamidoxime derivatives, corresponding agents which contain at least one fungicidal benzamidoxime derivative and at least one alcohol alkoxylate, and kits which contain benzamidoxime derivative and alcohol alkoxylate in separate containers include.

In addition to optimizing the properties of the active ingredient, the development of an efficient agent is of particular importance with regard to industrial production and application of these active ingredients5. By properly formulating the active ingredient (s), it is necessary to find an optimal balance between partially opposing properties such as biological effectiveness, toxicology, possible environmental influences and costs. In addition, the formulation largely determines the durability and ease of use of an agent. This also applies to the fungicidal benzamide oxime derivatives known from EP-A-1017670 (WO 99/14187), EP-A 805 148 (WO 96/19442) and EP-A 1 077 028 (WO 99/56549). 5

It is generally known and agricultural practice to add certain auxiliaries to formulations for improved effectiveness. The amounts of active substance in the formulation can thereby advantageously be reduced while the activity remains the same, as a result of which costs are minimized and existing legal regulations can be complied with if necessary. In individual cases, it is also possible to enlarge the spectrum of active substances, in that plants which could only be treated inadequately with a certain active substance without addition are accessible for a corresponding treatment by adding certain auxiliary substances. Furthermore, the performance under unfavorable environmental conditions can be increased in individual cases by a suitable formulation. This means that incompatibilities of different active ingredients in one formulation can also be avoided.

Such auxiliary substances are sometimes referred to as adjuvants. They are often surface-active or salt-like compounds. Depending on the mode of action, modifiers, actuators, fertilizers and pH buffers can be differentiated. Modifiers influence wetting, liability and spreading of a formulation. Actuators break up the waxy plant cuticle and improve the penetration of the active ingredient into the cuticle both short-term (in the minute range) and long-term (in the hour range). Fertilizers such as ammonium sulfate, ammonium nitrate or urea improve the absorption and solubility of the active ingredient, and they can reduce the antagonistic behavior of active ingredients. pH buffers are conventionally used to optimally adjust the pH of the formulation.

With regard to the absorption of the active ingredient in the sheet, surface-active substances can act as modifiers and actuators. It is generally assumed that suitable surface-active substances can increase the effective contact area of liquids on leaves by reducing the surface tension. In addition, certain surfactants can dissolve or break up the epicuticular waxes, which facilitates absorption of the active ingredient. Furthermore, some surface-active substances can also improve the solubility of active substances in formulations and thus avoid crystal formation or at least delay it. Finally, in certain cases, they can also influence the absorption of active substances by retaining moisture.

Adjuvants of the surface-active type are used in a variety of ways for agrotechnical applications. These can be divided into anionic, cationic, non-ionic or amphoteric groups of substances.

Petroleum-based oils are traditionally used as activating adjuvants. In the recent past, seed extracts, natural oils and their derivatives, for example from soybeans, sunflowers and coconut, have also been used.

The synthetic surface-active substances that are usually used as actuators include polyoxyethylene condensates with alcohols, alkylphenols or alkylamines, which have HLB values in the range from 8 to 13. In this sense, WO 00/42847 mentions, for example, the use of certain linear alcohol alkoxylates in order to increase the effectiveness of agrotechnical biocide formulations. WO 02/15697 also describes the use of alcohol alkoxylates as adjuvants in the formulation of triazole pyrimidines. The task was to improve the effectiveness of said benzamidoxime derivatives when used.

It has been found that alkoxylated alcohols have a particularly good adjuvant effect when using the benzamide oxime derivatives.

The present invention therefore relates to the use of alkoxylated alcohols (alcohol alkoxylates) as adjuvants for improving the fungicidal activity of benzamide oxime derivatives of the formula (I)

where the substituents have the following meanings:

R ¹ difluoromethyl or trifluoromethyl;

R ^{2 is} hydrogen or fluorine;

R ³ _Cι-C4 alkyl which may be substituted by cyano, C ₄ haloalkyl, _{Cι-C4-alkoxy-Cι-C 4} alkyl, C ₃ -C ₆ -Alke- nyl, C ₃ - C ₆ haloalkenyl, C ₃ -C ₆ alkynyl or C ₃ -C ₈ cycloalkyl -CC-C ₄ alkyl;

R ⁴ is phenyl-Ci-Cg-alkyl which may carry from ₄ alkoxy and Cι-C ₄ haloalkoxy selected substituents on the phenyl ring one or more halo, Cι-C ₄ -alkyl, C ₄ haloalkyl, Cχ-C , or

Thienyl-C ₁ -C ₄ -alkyl, which can carry one or more substituents selected from halogen, Cχ-C _4- alkyl, Cι-C ₄ -haloalkyl, Cι-C ₄ -alkoxy and Cχ-C4-haloalkoxy on the thienyl ring, or

Pyrazolyl-Cι-C ₄ alkyl, which alkyl ₄ -Halogenal- pyrazolyl on one or more of halogen, Cι-C ₄ -alkyl, C wearing Cι-C ₄ alkoxy or Cι-C ₄ haloalkoxy substituents selected can.

At least some of the alcohol alkoxylates to be used are known per se. For example, WO 01/77276 and US 6,057,284 and EP 0 906 150 describe suitable alcohol alkoxylates. Reference is hereby expressly made to the description of these alcohol alkoxylates in these publications, with which the alcohol alkoxylates disclosed therein and the preparation thereof are part of the present disclosure.

The alcohol portion of the alcohol alkoxylates to be used according to the invention is generally based on alcohols or alcohol mixtures known per se having 5 to 30, preferably 8 to 20 and in particular 9 to 15 carbon atoms. Fatty alcohols with about 8 to 20 carbon atoms are particularly worth mentioning here. Many of these fatty alcohols are known to be used for the production of nonionic and anionic surfactants, for which purpose the alcohols have a corresponding functionalization, e.g. by alkoxylation or glycosidation. 5

The alcohol part of the alkoxylates to be used can be straight-chain, branched or cyclic. If it is linear, alcohols with 14 to 20, for example 16-18, carbon atoms should be mentioned in particular. If it is branched, according to a particular embodiment, the main chain of the alcohol part generally has 1 to 4 branches, and alcohols with a higher or lower degree of branching can also be used in a mixture with further alcohol alkoxylates, as long as the average number of 5 branches of the mixture is in the specified range.

The alcohol part of the alkoxylates to be used can be saturated or unsaturated. According to a special embodiment, if it is unsaturated, it has a double bond. 0

In general, the branches independently of one another have 1 to 10, preferably 1 to 6 and in particular 1 to 4 carbon atoms. Particular branches are methyl, ethyl, n-propyl or iso-propyl groups. 5

Suitable alcohols and especially fatty alcohols are both from native sources, for example by extraction and if necessary or desired by hydrolysis, transesterification and / or hydrogenation of glycerides and fatty acids, as well as by synthetic means, for. B. available by construction from starting materials with a smaller number of carbon atoms. So you get z. B. according to the SHOP process (Shell Higher Olefine Process) starting from ethene olefin fractions with a suitable number of carbon for further processing into surfactants. The functionalization of the olefins to the corresponding alcohols takes place, for. B. by hydrofor mylation and hydrogenation.

Olefins with a carbon number suitable for further processing into suitable alcohols can also be obtained by oligomerization of 5 C ₃ -C ₆ -alkenes, such as in particular propene or butene or mixtures thereof.

Furthermore, lower olefins can be produced using heterogeneous acid catalysts, e.g. B. supported phosphoric acid, oligomerized and * "then functionalized to alcohols.

A general synthetic possibility for the production of branched alcohols is e.g. the implementation of aldehydes or ketones with Grignard reagents (Grignard synthesis). Instead of Grignard

15 reagents can also be used aryl or alkyl lithium compounds, which are characterized by a higher reactivity. Furthermore, the branched alcohols can be obtained by aldol condensation, the reaction conditions

_{Λ ^ are known to} the expert. 20

The alkoxylation results from the reaction with suitable alkylene oxides, which generally have 2 to 15 and preferably 2 to 6 carbon atoms. 25 ethylene oxide (EO), propylene oxide (PO), butylene oxide (BO), pentylene oxide (PeO) and hexylene oxide (HO) should be mentioned here.

One type of alcohol alkoxylate to be used is based on one type of alkylene oxide.

30

Another type of alcohol alkoxylates to be used is based on at least two different types of alkylene oxide. It is preferred to arrange several alkylene oxide units of one type as a block, so that at least two different alkylene

35 oxide blocks result, which are each formed from several units of the same alkylene oxides. If block alkoxylates of this type are used, it is preferred that the alkylene oxide part is composed of 3 and in particular 2 blocks.

40

According to one aspect, it is preferred that the alcohol alkoxylates to be used according to the invention are ethoxylated or have at least one ethylene oxide block. According to a further aspect, ethylene oxide blocks are combined in particular with propylene oxide 5 or pentylene oxide blocks. Depending on the amounts of alkylene oxide (s) chosen for the reaction and the reaction conditions, the respective degree of alkoxation results. This is usually a statistical mean, since the number of alkylene-5 oxide units of the alcohol alkoxylates resulting from the reaction varies.

The degree of alkoxylation, i.e. the average chain length of the polyether chains of alcohol alkoxylates to be used according to the invention can be determined by the molar ratio of alcohol to alkylene oxide. Alcohol alkoxylates with about 1 to 100, preferably about 2 to 15, in particular 3 to 12, especially 4 to 12 and especially 5 to 12 alkylene oxide units are preferred. 5

The alcohols or alcohol mixtures are reacted with the alkylene oxide (s) by customary processes known to the person skilled in the art and in equipment customary for this. _Q The alkoxylation can be catalyzed by strong bases, such as alkali hydroxides and alkaline earth hydroxides, Brönsted acids or Lewis acids, such as AlCl ₃ , BF ₃ etc. For narrowly distributed alcohol alkoxylates, catalysts such as hydrotalcite or DMC can be used. 5

The alkoxylation is preferably carried out at temperatures in the range from approximately 80 to 250 ° C., preferably approximately 100 to 220 ° C. The pressure is preferably between ambient pressure and 600 bar. If desired, the alkylene oxide can be admixed with an inert gas, e.g. B. from about 5 to 60%.

Accordingly, the alkoxylated alcohols to be used are selected in particular from alcohol alkoxylates of the formula (II) 5

R ⁶ _θ- (C _m H _2m O) _x - (C _n H _2n 0) _y - (C _p H _2p O) _z -H (II)

wherein ⁰ R ^{β is} C ₅ -C ₃₀ alkyl or C ₅ -C ₃₀ alkenyl;

m, n, p independently of one another represent an integer from 2 to 16, preferably 2, 3, 4 or 5;

x, y, z independently represent a number from 0 to 100; and x + y + z corresponds to a value from 1 to 100,

and the configurations of these alcohol alkoxylates of the formula (II) which result from the above statements.

According to a particular embodiment, alcohol alkoxylates of the formula (II) are used, in which m = 2 and the value of x is greater than zero. These are alcohol alkoxylates of the EO type, which primarily include alcohol ethoxylates (m = 2; x> zero; y, z = zero) and alcohol alkoxylates with an EO block bonded to the alcohol part (m = 2; x> Zero; y and / or z> zero). Of the alcohol alkoxylates with an EO block attached to the alcohol part, EO-PO block alkoxylates (m = 2; x> zero; y> zero; n = 3; z = 0), EO-PeO block alkoxylates (m = 2; x> zero; y> zero; n = 5; z = 0) and EO-PO-EO block alkoxylates (m, p = 2; x, z> zero; y> zero; n = 3).

EO-PO block alkoxylates in which the ratio of EO to PO (x to y) is 1: 1 to 4: 1 and in particular 1.5: 1 to 3: 1 are preferred. The degree of ethoxylation (value of x) is generally 1 to 20, preferably 2 to 15 and in particular 4 to 10, the degree of propoxylation (value of y) is generally 1 to 20, preferably 1 to 8 and in particular 2 to 5. The total degree of alkoxylation, ie the sum of EO and PO units is generally 2 to 40, preferably 3 to 25 and in particular 6 to 15.

EO-PeO block alkoxylates in which the ratio of EO to PeO (x to y) is 2: 1 to 25: 1 and in particular 4: 1 to 15: 1 are further preferred. The degree of ethoxylation (value of x) is generally 1 to 50, preferably 4 to 25 and in particular 6 to 15, the degree of pentoxylation (value of y) is generally 0.5 to 20, preferably 0.5 to 4 and in particular 0.5 to 2. The total degree of alkoxylation, ie the sum of EO and PeO units is usually 1.5 to 70, preferably 4.5 to 29 and in particular 6.5 to 17.

According to a further particular embodiment, alcohol alkoxylates of the formula (II) are used, in which n = 2, the values of x and y are both greater than zero and z = 0. These are also alcohol alkoxylates of the EO type, in which the EO block is, however, terminally bound. These include above all PO-EO block alkoxylates (n = 2; x>zero;y>zero; m = 3; z = 0) and PeO-EO block alkoxylates (n = 2; x>zero;y>zero; m = 5; z = 0). PO-EO block alkoxylates in which the ratio of PO to EO (x to y) is 1:10 to 3: 1 and in particular 1.5: 1 to 1: 6 are preferred. The degree of ethoxylation (value of y) is generally 1 to 20, preferably 2 to 15 and in particular 4 to 10, the degree of propoxylation (value of x) is generally 0.5 to 10, preferably 0.5 to 6 and in particular 1 to 4. The total degree of alkoxylation, ie the sum of EO and PO units, is generally 1.5 to 30, preferably 2.5 to 21 and in particular 5 to 14.

Also preferred are PeO-EO block alkoxylates in which the ratio of PeO to EO (x to y) is 1:50 to 1: 3 and in particular 1:25 to 1: 5. The degree of pentoxylation (value of x) is generally 0.5 to 20, preferably 0.5 to 4 and in particular 0.5 to 2, the degree of ethoxylation (value of y) is generally 3 to 50, preferably 4 to 25 and especially 5 to 15. The total degree of alkoxylation, ie the sum of EO and PeO units is generally 3.5 to 70, preferably 4.5 to 45 and in particular 5.5 to 17.

According to a further particular embodiment, alcohol alkoxylates of the formula (II) are used, in which the values of x, y and z are all greater than zero. These include above all PeO-EO-PO block alkoxylates (m = 5; x> zero; n = 2; y> zero; m = 3; z> zero).

According to a preferred embodiment, the alcohol alkoxylates to be used according to the invention are based on primary, α-branched alcohols of the formula (III),

wherein

R ⁷ , R ^{8 are} independently hydrogen or -CC ₆ alkyl.

R ⁷ and R ⁸ are preferably independently of one another Cg-Cg-alkyl and in particular C ₂ -C ₄ -alkyl.

Alcohol alkoxylates based on 2-propylheptanol are very particularly preferred. These include in particular alcohol alkoxylates of the formula (II), in which R represents a 2-propylheptyl radical, ie R ⁷ and R ⁸ in formula (III) each represent n-propyl.

Such alcohols are also known as Guerbet alcohols. These can be obtained, for example, by dimerizing corresponding primary alcohols (for example R ⁷ ' ⁸ CH ₂ CH ₂ OH) at elevated temperature, for example 180 to 300 ° C., in the presence of an alkaline condensing agent, such as potassium hydroxide.

In the context of this preferred embodiment based on Guebert alcohols, alkoxylates of the EO type in particular are used. Particularly preferred are ethoxylates whose degree of ethoxylation is 1 to 50, preferably 2 to 20 and in particular approximately 3 to 10. Of these, the correspondingly ethoxylated 2-propylheptanols should be mentioned above all.

According to a further preferred embodiment, the alcohol alkoxylates to be used are based on C 1 -oxo alcohols.

The term "-C ₃ -oxoalcohol" generally refers to an alcohol mixture, the main component of which is formed from at least one branched Cχ alcohol (isotridecanol). Such C 1 -alcohols include in particular tetramethyl-nonanols, for example 2,4,6,8-tetramethyl-1-nonanol or 3,4,6,8-tetramethyl-1-nonanol as well as ethyldimethyl-nonanols such as 5-ethyl-4,7 -dimethyl-l-no-nanol.

Suitable C ₃ alcohol mixtures are generally available by hydrogenation of hydroformylated trimerbutene. In particular you can

a) bringing butenes into contact with a suitable catalyst for oligomerization,

b) isolate a C ₂ olefin fraction from the reaction mixture,

c) the Cι ₂ -01efinfraktion by reaction with carbon monoxide and hydrogen in the presence of a suitable catalyst and hydroformylation

d) hydrogenate.

Advantageous C ₃ alcohol mixture are essentially halogen-free, ie they contain less than 3 ppm by weight, in particular less than 1 ppm by weight, halogen, especially chlorine. Butene trimerization can be carried out by means of homogeneous or heterogeneous catalysis.

In the DIMERSOL process (see Revue de 1 'Institut Franςais du Petrole, Vol. 37, No. 5, Sept. / Oct. 1982, p. 639ff) butenes are formed in a homogeneous phase in the presence of a catalyst system consisting of a transition metal derivative and an organometallic compound oligomerized. Typical catalyst systems are Ni (0) complexes in connection with Lewis acids such as A1C1 ₃ , BF ₃ , Sb s etc. or Ni (II) complexes in connection with alkyl aluminum halides.

Alternatively, butenes can be oligomerized in a manner known per se on a heterogeneous catalyst containing Nikkei (process step a). Depending on the process conditions chosen, different relative amounts of butene dimers, trimers and higher oligomers are obtained. For the present purposes, the butene trimers, ie C ₂ olefins, are processed further. With regard to the desired degree of branching of the C ₃ -alcohol mixture obtained after hydroformylation / hydrogenation, the content of isobutene can be selected. Relatively low degrees of branching require a relatively low isobutene content and vice versa. For example, if the C _2-0 01efin fraction should have an ISO index of about 1.9 to 2.3, it is advisable to choose the butenes used predominantly linearly, ie the hydrocarbon stream generally used should be less than 5% by weight, based on the butene fraction, contain isobutene. The butenes can contain an admixture of saturated C ₄ hydrocarbons, which act as diluents in the oligomerization.

The heterogeneous, nickel-containing catalysts that can be used can have different structures, with nickel oxide-containing catalysts being preferred. Catalysts known per se can be used, as are described in C. T. O'Connor et al., Catalysis Today, Vol. 6 (1990), pp. 336-338.

The hydrocarbon stream (preferably C ₄ ) generally contains 50 to 100% by weight, preferably 60 to 90% by weight, butenes and 0 to 50% by weight, preferably 10 to 40% by weight, butanes. The butene fraction comprises less than 5% by weight, in particular less than 3% by weight, of isobutene, based on the butene fraction. The butene fraction generally has the following composition (in each case based on the butene fraction):

1-butene 1 to 50% by weight cis-2-butene 1 to 50% by weight trans-2-butene 1 to 99% by weight iso-butene 1 to 5% by weight

The so-called raffinate II is used as a particularly preferred feedstock, which is an isobutene-depleted C _{4 cut} from an FCC system or a steam cracker.

A C ₁₂ olefin fraction is isolated from the reaction discharge of the oligomerization reaction in one or more separation steps (process step b). Suitable separation devices are the usual apparatuses known to the person skilled in the art. These include e.g. B. distillation columns, such as plate columns, which can optionally be equipped with bells, sieve plates, sieve plates, valves, side draws, etc., evaporators, such as thin-film evaporators, falling film evaporators, wiper blade evaporators, Sambay evaporators etc. and combinations thereof. The Cχ -01efin fraction is preferably isolated by fractional distillation.

The ISO index of the _C12 -01efinfraktion, which indicates the mean number of branchings, is generally from 1 to 4, preferably 1.9 to 2.3, in particular 2.0 to 2.3. The ISO index can e.g. B. be determined by hydrogenating a sample of the Cχ -01efinfraktion to the dodecanes and in the ¹ H-NMR spectrum based on the signal area to be assigned to the methyl groups and the signal area to be assigned to the total protons the average number of methyl groups is determined. The ISO index is the average number of methyl groups minus two.

In order to prepare an alcohol mixture according to the invention, the isolated Cχ ₂ -01efin fraction is hydroformylated to Cχ ₃ -aldehydes (process step c) and then hydrogenated to Cχ ₃ -alcohols (process step d). The alcohol mixtures can be prepared in one step or in two separate reaction steps.

An overview of hydroformylation processes and suitable catalysts can be found in Beller et al., Journal of Molecular Catalysis A 104 (1995), pp. 17-85.

The hydroformylation is preferably carried out in the presence of a cobalt hydroformylation catalyst. The amount of the hydroformylation catalyst is generally 0.001 to 0.5% by weight, calculated as cobalt metal, based on the amount of the olefins to be hydroformylated. The reaction temperature is general

ll mean in the range of about 100 to 250 ° C, preferably 150 to 210 ° C. The reaction can be carried out at an elevated pressure of about 10 to 650 bar. It is preferred that the hydroformylation is carried out in the presence of water; however, it can also be carried out in the absence of water.

Carbon monoxide and hydrogen are usually used in the form of a mixture, the so-called synthesis gas. The composition of the synthesis gas used can vary within a wide range. The molar ratio of carbon monoxide to hydrogen is usually about 2.5: 1 to 1: 2.5. A preferred ratio is about 1: 1.5.

The cobalt catalyst homogeneously dissolved in the reaction medium can be suitably separated from the hydroformylation product by treating the reaction effluent from the hydroformylation with oxygen or air in the presence of an acidic aqueous solution. The cobalt catalyst is oxidatively destroyed to form cobalt (II) salts. The cobalt (II) salts are water-soluble and are extracted into the aqueous phase, which can be separated off and returned to the hydroformylation process.

The crude aldehydes or aldehyde / alcohol mixtures obtained in the hydroformylation can, if desired, be isolated and, if appropriate, purified by conventional methods known to those skilled in the art before the hydrogenation.

For the hydrogenation, the reaction mixtures obtained in the hydroformylation are reacted with hydrogen in the presence of a hydrogenation catalyst.

Suitable hydrogenation catalysts are generally transition metals, such as. B. Cr, Mo, W, Fe, Rh, Co, Ni, Pd, Pt, Ru etc. or mixtures thereof, which increase the activity and stability on supports such. B. activated carbon, aluminum oxide, diatomaceous earth, etc. can be applied. To increase the catalytic activity, Fe, Co and preferably Ni, also in the form of the Raney catalysts, can be used as a metal sponge with a very large surface area. A Co / Mo catalyst is preferably used for the preparation of the surfactant alcohols according to the invention. Depending on the activity of the catalyst, the hydrogenation of the oxo aldehydes is preferably carried out at elevated temperatures and elevated pressure. The hydrogenation temperature is preferably about 80 to 250 ° C., and the pressure is preferably about 50 to 350 bar. Other suitable Cχ ₃ alcohol mixtures are available in that

a) a C ₄ subjecting -01efin mixture to metathesis,) b from the metathesis olefins having 6 C atoms are separated individually c) the separated olefins or C atoms subjecting a mixture to dimerization to give olefin mixtures having from 12, and d) obtained olefin mixture, optionally after fractionation, the derivatization to a mixture of C13-oxo alcohols.

The basic principles of the metathesis used in process step a) have been described, for example, in Ullmann's Ecyclopedia of Industrial Chemistry, 5th edition, volume A18, p.235 / 236. Further information on the implementation of the method can, for example, K.J. Ivin, "Olefin Metathesis, Academic Press, London, (1983); Houben-Weyl, E18, 1163-1223; RL Banks, Discovery and Development of Olefin Disproportionation, CHEMTECH (1986), February, 112-117 ,

When applying metathesis to the information contained in the C ₄ -01efin streams main components butene-1 and butene-2 in the presence of suitable catalysts, olefins having 5 to 10 carbon atoms, preferably having 5 to 8 C atoms, in particular, however, Penten-2 and Hexen-3 were formed.

Suitable catalysts are preferably molybdenum, tungsten or rhenium compounds. It is particularly expedient to carry out the reaction heterogeneously catalyzed, the catalytically active metals being used in particular in conjunction with supports composed of Al ₂ O ₃ or SiO ₂ . Examples of such catalysts are Mo0 ₃ or W0 ₃ on Si0 ₂ , or Re0 ₇ on A1 ₂ 0 ₃ .

It is particularly expedient to carry out the metathesis in the presence of a rhenium catalyst, since in this case particularly mild reaction conditions are possible. In this case, the metathesis can be carried out at a temperature of 0 to 50 ° C and at low pressures of approx. 0.1 to 0.2 MPa.

In the dimerization of the olefins or olefin mixtures obtained in the metathesis step, dimerization products are obtained which, with regard to the further processing on surfactant alcohols, have particularly favorable components and a particularly advantageous composition if a dimerization catalyst is used which contains at least one element of subgroup VIII periodic system, and the catalyst composition and the reaction conditions are selected so that a dimer mixture is obtained which contains less than 10% by weight of compounds which have a structural element of the formula in (vinylidene 5 group)

wherein A ¹ and A ^{2 are} aliphatic hydrocarbon radicals. 5 The internal linear pentenes and hexenes contained in the metathesis product are preferably used for the dimerization. The use of 3-hexene is particularly preferred.

The dimerization can be carried out homogeneously catalyzed or heterogeneously catalyzed. The heterogeneous procedure is preferred, since on the one hand the catalyst separation is simplified and the process is therefore more economical, and on the other hand no environmentally harmful wastewater is generated, as is usually the case when separating dissolved catalysts, for example by hydrolysis. Another advantage of the heterogeneous process is that the dimerization product contains no halogens, especially chlorine or fluorine. Homogeneously soluble catalysts generally contain halide-containing ligands or they are used in combination with halogen-containing cocatalysts. Halogen from such catalyst systems can be incorporated into the dimerization products, which significantly affects both the product quality and the further processing, in particular the hydroformylation to surfactant alcohols. 5

Heterogeneous catalysis expediently combinations of oxides of metals of the VIII. Subgroup with aluminum oxide on support materials made of silicon and titanium oxides as examples _Q game, from DE-A-43 39 713 are known, are used. The heterogeneous catalyst can be used in a fixed bed - then preferably in coarse-grained form as 1 to 1.5 mm grit - or suspended (particle size 0.05 to 0.5 mm). In the case of heterogeneous implementation, the dimerization is expediently closed at temperatures of from 80 to 200.degree. C., preferably from 100 to 180.degree. C., under the pressure prevailing at the reaction temperature, optionally also under a protective gas pressure System executed. In order to achieve optimal sales, the reaction mixture is circulated several times, with a certain proportion of the circulating product being continuously discharged and replaced by starting material.

In the dimerization, mixtures of monounsaturated hydrocarbons are obtained, the components of which predominantly have twice the chain length as the starting olefins.

The dimerization catalysts and the reaction conditions are expediently chosen within the framework of the above information so that at least 80% of the components of the dimerization mixture branch out in the range from 1/4 to 3/4, preferably from 1/3 to 2/3, of the chain length of their main chain , or two branches on adjacent carbon atoms.

The high proportion - generally over 75%, in particular over 80% - of components with branching and the low proportion - generally below 25, in particular below 20% - of unbranched olefins is very characteristic of the oil mixtures produced in this way. Another characteristic is that predominantly groups with (y-4) and (y-5) carbon atoms are bound at the branching points of the main chain, where y is the number of carbon atoms of the monomer used for the dimerization. The value (y-5) = 0 means that there is no side chain.

In the Cχ-01efin mixtures prepared in this way, the main chain preferably carries methyl or ethyl groups at the branching points.

The position of the methyl and ethyl groups on the main chain is also characteristic: With mono substitution, the methyl or ethyl groups are in the position P = (n / 2) -m of the main chain, where n is the length of the main chain and m is the carbon number of the side groups , in the case of disubstitution products, one substituent is in the P position, the other on the neighboring C atom P + 1. The proportions of mono-substitution products (single branching) in the olefin mixture produced according to the invention are typically in the range from 40 to 75% by weight, the proportions of double-branched components in the range from 5 to 25% by weight.

It was also found that the dimerization mixtures can be derivatized particularly well if the position of the double bond meets certain requirements. In these advantageous In olefin mixtures, the position of the double bonds relative to the branches is characterized in that the ratio of the "aliphatic" hydrogen atoms to "olefinic" hydrogen atoms in the range H _a ii _Ph . ^: H ₀ ι _{ef n} . = (2 * n-0.5): 0.5 to (2 * nl, 9): 1.9, where n is the number of carbon atoms of the olefin obtained in the dimerization.

("Aliphatic" hydrogen atoms are those which are bound to carbon atoms which are not involved in a C = C double bond (Pi bond), and "olefinic" hydrogen atoms are those which are bound to a carbon atom which actuated a Pi binding.)

Dimerization mixtures in which the ratio is particularly preferred

Haiiph. : Hoißfi _n . = (2 * nl, 0): 1 to (2 * nl, 6): 1.6.

The olefin mixtures prepared in this way are first hydroformylated by reaction with carbon monoxide and hydrogen in the presence of suitable catalysts, preferably containing cobalt or rhodium, to form surfactant alcohols (oxo alcohols), branched primary alcohols.

A good overview of the hydroformylation process with numerous other references can be found, for example, in the extensive article by Beller et al. in Journal of Molecular Catalysis, A104 (1995) 17-85 or in Ullmanns Encyclopedia of Industrial Chemistry, Vol. A5 (1986), page 217 ff., page 333, as well as the relevant references.

The comprehensive information provided there enables the person skilled in the art to also hydroformylate the branched olefins according to the invention. In this reaction, CO and hydrogen are attached to olefinic double bonds, mixtures of aldehydes and alkanols being obtained according to the following reaction scheme: A ³ -CH = CH ₂

CO / H ₂ + catalyst

(n compounds) (iso compounds) 0 A ³ -CH ₂ -CH ₂ -CHO A ³ -CH (CHO) -CH ₃ (alkanal)

A ³ -CH ₂ -CH ₂ -CH ₂ OH A ³ -CH (CH ₂ OH) -CH ₃ (alkanol) 5

(A ³ = hydrocarbon residue)

The molar ratio of n- and iso-compounds in the reaction mixture is generally in the range from 1: 1 to 20: 1, depending on the process conditions chosen for the hydroformylation and the catalyst used. The hydroformylation is normally carried out in the temperature range from 90 to 200 ° C. and at a CO / H pressure of 2.5 to 35 MPa (25 to 350 bar). The mixing ratio of carbon monoxide to hydrogen depends on whether alkanals or alkanols should preferably be produced. It is expedient to work in the range CO: H from 10: 1 to 1:10, preferably 3: 1 to 1: 3, the range of low hydrogen partial pressures being used for the production of alkanals and the range of high hydrogen partial pressures being used for the production of alkanols , e.g. CO: H = 1: 2, choose.

Particularly suitable catalysts are metal compounds of the general formula HM (CO) ₄ or M (CO) g, where M is a metal atom, 5 is preferably a cobalt, rhodium or ruthenium atom.

In general, under hydroformylation conditions, catalytically active species of the general formula H _x M _y (C0) _z L _{g are} formed from the catalysts or catalyst precursors used in each case, where M is a metal from subgroup VIII, L is a ligand, which can be a phosphine, phosphite, amine, pyridine or any other donor compound, also in polymer form, and q, x, y and z are integers, depending on the valence and type of the metal and the binding force of the ligand L. , where q5 can also be 0. The metal M is preferably cobalt, ruthenium, rhodium, palladium, platinum, osmium or iridium and in particular cobalt, rhodium or ruthenium.

Suitable rhodium compounds or complexes are e.g. Rhodium (II) and rhodium (III) salts, such as rhodium (III) chloride, rhodium (III) nitrate, rhodium (III) sulfate, potassium rhodium sulfate, rhodium (II) and rhodium (III) caboxylate, rhodium (II) and rhodium (III) acetate, rhodium (III) oxide, salts of rhodium (III) acid, such as, for example Trisammonium hexachlororhodate (III). Rhodium complexes such as rhodium biscarbonyl acetylacetonate, acetylacetonato bisethylene rhodium (I) are also suitable. Rhodium biscarbonyl acetylacetonate or rhodium acetate are preferably used.

Suitable cobalt compounds are, for example, cobalt (II) chloride, cobalt (II) sulfate, cobalt (II) carbonate, cobalt (II) nitrate, their amine or hydrate complexes, cobalt carbocylates such as cobalt acetate, cobalt ethyl hexanoate, cobalt naphthanoate and the cobalt caprolactamate complex. Here too, the carbonyl complexes of cobalt such as dicobalt octocarbonyl, tetrakobalt dodecacarbonyl and hexacobalt hexadecacarbonyl can be used.

The compounds of cobalt, rhodium and ruthenium mentioned are known in principle and adequately described in the literature, or they can be prepared by a person skilled in the art analogously to the compounds already known.

The hydroformylation can be carried out with the addition of inert solvents or diluents or without such an addition. Suitable inert additives are, for example, acetone, methyl ethyl ketone, cyclohexanone, toluene, xylene, chlorobenzene, methylene chloride, hexane, petroleum ether, acetonitrile and the high-boiling fractions from the hydroformylation of the dimerization products.

If the hydroformylation product obtained has an excessively high aldehyde content, this can easily be achieved by hydrogenation, for example using hydrogen in the presence of Raney nickel or using other known hydrogenation reactions, in particular copper, zinc, cobalt, nickel, molybdenum, zirconium or Titanium-containing catalysts can be eliminated. The aldehyde components are largely hydrogenated to alkanols. A practically complete removal of aldehyde components in the reaction mixture can, if desired, be carried out by post-hydrogenation, for example under particularly gentle and economical conditions. with an alkali borohydride.

The Cχ ₃ -alcohol mixture according to the invention can be obtained in pure form from the reaction mixture obtained after the hydrogenation by customary purification processes known to the person skilled in the art, in particular by fractional distillation.

Cχ ₃ alcohol mixtures according to the invention generally have an average degree of branching from 1 to 4, preferably from 2.1 to 1 ° 2.5, in particular 2.2 to 2.4. The number of methyl groups in one molecule of the alcohol minus 1 is defined as the degree of branching. The mean degree of branching is the statistical mean of the degree of branching of the molecules of a sample. The average number of methyl groups in the molecules of a sample can be

15 easily ¹ H NMR spectroscopy. For this purpose, the signal area corresponding to the methyl protons in the ¹ H-NMR spectrum of a sample is divided by three and related to the signal area of the methylene protons in the CH ₂ -OH group divided by two.

20

In the context of this embodiment based on Cχ ₃ -oxoalcohols, those alcohol alkoxylates which are either ethoxylated or block alkoxylates of the EO / PO type are particularly preferred.

25

The degree of ethoxylation of the present invention to be used ethosulfate xylierten Cχ ₃ oxoalcohols is generally from 1 to 50, preferably 3 to 20 and especially 3 to 10, especially 4 to 10 and particularly 5 to 10. 30

The degree of alkoxylation of the EO / PO block alkoxylates to be used according to the invention depends on the arrangement of the blocks. If the PO blocks are arranged terminally, the ratio of EO units to PO units is generally at least 1, preferably 1: 1 to 4: 1 and in particular 1.5: 1 to 3: 1 The degree of ethoxylation is generally 1 to 20, preferably 2 to 15 and in particular 4 to 10, the degree of propoxylation is generally 1 to 20, preferably 1 to 8 and in particular 2 to 5. The total degree of alkoxylation, ie the sum of EO and PO -Units

40 is generally 2 to 40, preferably 3 to 25 and in particular 6 to 15. If, however, the EO blocks are arranged terminally, the ratio of PO blocks to EO blocks is less critical and is usually 1:10 to 3: 1, preferably 1: 1.5 to 1: 6. The degree of ethoxylation is usually

45 1 to 20, preferably 2 to 15 and in particular 4 to 10, the degree of propoxylation generally 0.5 to 10, preferably 0.5 to 6 and in particular 1 to 4. The total degree of alkoxylation is usually 1.5 to 30, preferably 2.5 to 21 and in particular 5 to 14.

According to a further preferred embodiment, alcohol alkoxylates based on C ₁₀ oxo alcohols are used.

The term "Cχo-oxo alcohol" stands in analogy to the previously explained term "Cχ _3- oxo alcohol" for Cχo-alcohol mixtures, the _Q main component of which is formed from at least one branched Cχo alcohol (isodecanol).

Suitable Cχo alcohol mixtures are generally available by hydrogenation of hydroformylated trimer propene. In particular, one can

a) propenes purpose of oligomerization with a suitable catalyst contacting, 0 b) from the reaction mixture a C ₉ -01efinfraktion isolate

c) hydroformylate the Cg olefin fraction by reaction with carbon monoxide and hydrogen in the presence of a suitable catalyst and 5 d) hydrogenate.

Special embodiments of this procedure result in analogy to the configurations described above for the hydrogenation of hydroformylated trimerbutene.

In the context of this embodiment based on Cχo-oxo alcohols, those alcohol alkoxylates which are either ethoxylated or block alkoxylates of the EO / PeO type are particularly preferred. 5

The degree of ethoxylation of the ethoxylated co-oxo alcohols to be used according to the invention is generally 1 to 50, preferably 2 to 20 and in particular 2 to 10, in particular 3 to 10 and particularly 3 to 10. 0

The degree of alkoxylation of the EO / PeO block alkoxylates to be used according to the invention depends on the arrangement of the blocks. If the PO blocks are arranged terminally, the ratio of EO units to PO units is generally at least 1, preferably 2: 1 to 25: 1 and in particular 4: 1 to 15: 1. The degree of ethoxylation is generally 1 to 50, preferably 4 to 25 and in particular 6 to 15, the degree of pentoxylation in the gel 0.5 to 20, preferably 0.5 to 4 and in particular 0.5 to 2. The total degree of alkoxylation, ie the sum of EO and PeO units, is generally 1.5 to 70, preferably 4.5 to 29 and in particular 6.5 to 17. If, however, the EO blocks are arranged terminally, the ratio of PeO blocks to EO blocks is less critical and is usually 1:50 to 1: 3, preferably 1: 25 to 1: 5. The degree of ethoxylation is generally 3 to 50, preferably 4 to 25 and in particular 5 to 15, the degree of pentoxylation is generally 0.5 to 20, preferably 0.5 to 4 and in particular 0.5 to 2. The The overall degree of alkoxylation is generally 3.5 to 70, preferably 4.5 to 45 and in particular 5.5 to 17.

It follows from the foregoing that, in particular die5 invention to be used Cχ _3-oxo alcohols or Cχ hole ₀ -Oxoalko- are based on olefins which are already branched. In other words, branches are not only due to the hydroformylation reaction as would be the case with straight chain olefins hydroformylation. The degree of branching of alkoxylates to be used according to the invention is therefore generally greater than 1.

The alkoxylates to be used according to the invention generally have a relatively small contact angle. Alkoxylates whose contact angle is less than 120 ° and preferably less than 100 ° are particularly preferred if this is determined in a manner known per se using an aqueous solution containing 2% by weight alkoxylate on a paraffin surface. 0

According to one aspect, the surface-active properties of the alcohol alkoxylates depend on the type and distribution of the alcohol alkoxylate grouping. The surface tension of alcohol alcohols to be used according to the invention, which can be determined by the pendant drop method, is preferably in a range from 25 to 70 mN / m and in particular 28 to 50 mN / m for a solution containing 0.1% by weight alcohol alkoxylate from 25 to 70 mN / m and in particular 28 to 45 mN / m for a solution containing 0.5% by weight of alcohol alkoxylate. Alcohol-0-alkoxylates which are preferably used according to the invention therefore qualify as amphiphilic substances.

The above alcohol alkoxylates are particularly suitable when using the benzamide oxime derivatives of the formula Ia 5 in which

R ^{1 is} as defined above;

R ^{5 represents} hydrogen, halogen, Cχ-C ₄ -alkyl, Cχ-C ₄ -haloalkyl, Cχ-C ₄ -alkoxy or Cχ-C ₄ -haloalkoxy; and

n is 1, 2 or 3.

Of these, benzamide oxime derivatives of the formula (I) or (Ia) are preferred, in which R ^{1 is} difluoromethyl or tri luormethyl and R ^{5 is} hydrogen, that is to say N-phenylacetyl-2-difluoromethoxy-5,6-di-fluorobenzamide (0 -cyclopropylmethyl] -oxime and N-phenylacetyl-2-trifluoromethoxy-5, 6-difluorobenzamide- (O-cyclopropylmethyl) -oxime.

The benzamide oxime derivatives can be used together with other active ingredients, e.g. with herbicides, insecticides, growth regulators, fungicides or also with fertilizers.

When mixed with fungicides, the fungicidal activity spectrum is enlarged in many cases.

The following list of fungicides with which the benzamidoxime derivatives can be used together is intended to explain the possible combinations, but not to limit them:

Aliphatic nitrogen fungicides, e.g. Butylamine, cymoxanil, didicin, dodine, guazatine and iminoctadine;

Amide fungicides, for example carpropamide, chloraniformethane, cyazofamide, cyflufenamid, diclocymet, ethaboxam, fenoxanil, flumetover, furametyr, prochloraz, quinazamide, silthiofam and triforine; in particular acylamino acid fungicides, for example benalaxyl, benalaxyl-M, furalaxyl, metalaxyl, metalaxyl-M, pefurazoate; Benzamide fungicide zide, for example benzohydroxamic acid, dioxymide, trichlamide, zarilamide and zoxamide; Furamide fungicides, for example cyclafuramide and furecyclox; Phenylsulfamide fungicides, for example dichlofluanide and tolylfluanide; Valina id fungicides, e.g. B. Benthiavalicarb and Iprovalicarb; and anilide fungicides, for example benalaxyl, benalaxyl-M, boscalid, carboxin, fenhexamide, metalaxyl, metalaxyl-M, metsulfovax, ofurac, oxadixyl, oxycarboxin, pyracarbolide, thifluzamide, tiadinil; in particular benzanilide fungicides, for example benodanil, flutolanil, meenil, mepronil, salicylanilide and tecloftalam; Furanilide fungicides, for example fenfuram, furalaxyl, furcarbanil and methfuroxam; and sulfonanilide fungicides, for example flusulfamide;

antibiotic fungicides, e.g. Aureofungin, blasticidin-S, cycloheximide, griseofulvin, kasugamycin, natamycin, polyoxins, polyoxorim, streptomycin and validamycin; especially strobilurin fungicides, e.g. Azoxystrobin, dimoxystrobin, ffluoxastrobin, cresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin and trifloxystrobin;

aromatic fungicides, e.g. Biphenyl, chlorodinitronaphthalene, chloroneb, chlorothalonil, cresol, diclorane, hexachlorobenzene, pentachlorophenol, quintozen, sodium pentachlorophenoxide and tecnazene;

Benzimidazole fungicides, e.g. Benomyl, carbendazim, chlorfenazole, cypendazole, debacarb, fuberidazole, mecarbinzid, rabenzazole and thiabendazole;

Benzimidazole precursor fungicides, e.g. Furophanate, thiophanate and thiophanate-methyl; Benzothiazole fungicides, e.g. Bentaluron, Chlobenthiazone and TCMTB;

bridged diphenyl fungicides, e.g. Bithionol, dichlorophen and diphenylamine;

Carbamate fungicides, e.g. Benthiavalicarb, Furophanat, Iprovalicarb, Propamocarb, Thiophanat and Thiophanat-methyl; especially benzidazolyl carbamate fungicides, e.g. Benomyl, carbendazim, cypendazole, debacarb, mecarbinzid; and carbanilate fungicides, e.g. diethofencarb;

Conazole fungicides, in particular imidazoles, for example climbazoles, clo-trimazoles, imazalil, oxpoconazoles, prochloraz and triflumizoles; and triazoles, for example azaconazole, bromuconazole, cyproconazole, diclobutrazole, difenoconazole, diniconazole, diniconazole-M, epoxy conazole, Etaconazole, Fenbuconazole, Fluquinconazole, Flusilazole, Flutriafol, Furconazole, Furconazole-cis, Hexaconazole, Imibenconazole, Ipconazole, Metconazole, Myclobutanil, Penconazazole, Propiconazole, Prothioconazole, Tothinoconazole, Quothinoconazole, Quothinoconazole, Triticona- zole, Uniconazole and Uniconazole-P;

Copper fungicides, e.g. Bordeaux mixture, Burgundy mixture, Cheshunt mixture, copper acetate, basic copper carbonate, copper hydroxide, copper naphthenate, copper oleate, copper oxychloride, copper sulfate, basic copper sulfate, zinc chromate, Cufraneb, Cuprobam, copper oxide, mancopper and oxine copper;

Dicarboximide fungicides, e.g. Famoxadone and fluoroimide; especially dichlorophenyl dicarboximide fungicides, e.g. Chlozolinates, dichlozolin, iprodione, isovaledione, myclozolin, procymidone and vinclozolin; and phthalimide fungicides, e.g. Captafol, Captan, Datalimfos, Folpet and Thiochlorfenphi;

Dinitrophenol fungicides, e.g. Binapacryl, Dinobuton, Dinocap, Dinocap-4, Dinocap-6, Dinocton, Dinopenton, Dinosulfon, Dinoterbon and DNOC; Dithiocarbamate fungicides, e.g. Azithiram, Carba orph, Cufraneb, Cuprobam, Disulfiram, Ferbam, Metam, Nabam, Tecoram, Thira and Ziram; especially cyclic

Dithiocarba at fungicides, e.g. Dazomet, Etem and Milneb; and polymeric dithiocarbamate fungicides, e.g. Mancopper, Mancozeb, Maneb,

Metiram, polycarbamate, propineb and zineb;

Imidazole fungicides, e.g. Cyazofamid, fenamidone, fenapanil, glyodin, iprodione, isovaledione, pefurazoate and triazoxide;

inorganic fungicides, e.g. Potassium azide, potassium thiocyanate, sodium azide and sulfur;

Mercury fungicides, in particular inorganic mercury fungicides, for example mercury chlorides such as mercury (II) chloride and mercury (I) chloride, mercury (II) oxide; Organomercury fungicides, eg (3-ethoxypropyl) mercury bromide, ethyl mercury acetate, ethyl mercury bromide, ethyl mercury chloride, ethyl mercury 2, 3-dihydroxypropyl mercaptide, ethyl mercury phosphate, methylene chloride, methylene chloride, n- (methylene chloride), n- (ethyl chloride) Methyl mercury benzoate, methyl mercury dicyandiamide, methyl mercury pentachlorophenoxide, 8-phenylmercurioxyquinoline, phenylmercurea, phenyl- mercury acetate, phenyl mercury chloride, phenyl mercury derivative of pyrocatechol, phenyl mercury nitrate, phenyl mercury salicylate, thiomersal and tolyl mercury acetate;

Morpholine fungicides, e.g. Aldimorph, benzamorf, carbamorph, dimethomorph, dodemorph, fenpropimorph, flumorph, and tride orph;

Organophosphorus fungicides, for example ampropylfos, ditalimfos, edifen- _1Q phos, fosetyl, hexylthiofos, iprobefos, phosdiphen, pyrazophos, tolclofos-methyl and triamiphos;

Organotin fungicides, e.g. Decafentin, fentin, tributyltin oxide;

Oxathiin fungicides, e.g. Carboxin and oxycarboxin;

Oxazole fungicides, e.g. Chlozolinates, dichlozolines, drazoxolone,

Famoxadone Hymexazole, Metazoxolone, Myclozolin, Oxadixyl and Vinc-

"_ Lozolin; 20

Polysulfide fungicides, e.g. Barium polysulfide, calcium polysulfide, potassium polysulfide and sodium polysulfide;

25 pyridine fungicides, e.g. Boscalid, buthiobate, dipyrithione, fluzzinam, pyridinitrile, pyrifenox, pyroxychlor and pyroxyfur;

Pyrimidine fungicides, e.g. Bupirimate, Cyprodinil, Diflumetorim, Dimethirimol, Ethirimol, Fenarimol, Ferimzone, Mepanipyrim, Nuurimol, Pyrimethanil and Triarimol;

Pyrrole fungicides, e.g. Fenpiclonil, fludioxonil and fluorimid;

35 quinoline fungicides, e.g. Ethoxyquin, halacrinate, 8-hydroxyquinoline sulfate, quinacetol and quinoxyfen;

Quinone fungicides, e.g. Benquinox, chloranil, dichlone and dithiaonon; 40

Quinoxaline fungicides, for example quinomethionate, chlorquinox and thioquinox; 5 thiazole fungicides, for example ethaboxam, etridiazole, metsulfovax, octhilinone, thiabendazole, thiadifluor and thifluzamide; Thiocarbamate fungicides, for example methasulfocarb and prothiocarb;

Thiophene fungicides, e.g. Ethaboxam and silthiofam;

Triazine fungicides, e.g. anilazine;

Triazole fungicides, e.g. Bitertanol, Fluotrimazole and Triazbutil;

Urea fungicides, e.g. Bentaluron, pencycuron and quinazamide;

and other fungicides, e.g. Acibenzolar, Acypetacs, Allyl Alcohol, Benzalkonium Chloride, Benzamacril, Bethoxazin, Carvone, Chloropicrine, DBCP, Dehydroacetic Acid, Diclomezine, Diethylpyrocarbonate, Fenaminosulf, Fenitropan, Fenpropidin, Formaldehyde, Hexachlorbututomidium, Methylphenolothidonidium, Isoprothothidone, Isoprothothidone, Isoprone, Isoprone, Isoprone, Isoprone Nitrothal-isopropyl, OCH, 2-phenylphenol, phthalide, piperalin, probenazole, proquinazide, pyroquilone, sodium orthophenylphenoxide, spiroxamine, sultropen, thicyofen, tricyclic azole and zinc naphthenate.

Fungicides with which the benzamidoxime derivatives can be used together include in particular:

Sulfur, dithiocarbamates and their derivatives, such as ferridimethyldithiocarbamate, zinc dimethyldithiocarbate, zinc ethylene bisdithiocarbate, manganese ethylene bisdithiocarbamate, manganese-zinc-ethylene-diamine-bis-dithiocarbamate, tetramethylthiylene-ammonium- bis-dithiocarbamate), ammonia complex of zinc (N, N'-propylene-bis-dithiocarbamate), zinc (N, N'-propylene-bis-dithiocarbamate), N, N'-polypropylene-bis- (thio - carbamoyl) disulfide;

Nitroderivatives, such as dinitro- (1-methylheptyl) phenylcrotonate, 2-sec. -Butyl-4, 6-dinitrophenyl-3, 3-dimethylacryla, 2-sec .- Butyl-4, 6-dinitrophenyl-iso-propyl carbonate, 5-nitro-iso-phthalic acid di-iso-propyl ester;

heterocyclic substances, such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, 0, O-diethyl-phthalimidophosphonothioate, 5-amino-1- [is - (dimethylamino) phosphinyl] - 3-phenyl-l, 2, 4-triazole, 2, 3-dicyano-l, 4-dithioanthraquinone, 2-thio-l, 3-dithiolo [4, 5-b] quinoxaline, Methyl 1- (butylcarbamoyl) -2-benzimidazole-carbamate, 2-methoxycarbonylamino-benzimidazole, 2- (furyl- (2)) -benzimidazole, 2- (thiazolyl- (4)) -benz- imidazole, N- (1, 1, 2, 2-tetrachloroethylthio) tetrahydrophthalimide, N-trichloromethylthio-tetrahydrophthalimide, N-trichloromethylthiophthalimide,

N-dichlorofluoromethylthio-N ', N' -dimethyl-N-phenyl-sulfuric acid diamide, 5-ethoxy-3-trichloromethyl-l, 2,3-thiadiazole, 2-rhodanomethylthiobenzothiazole, 1, 4-dichloro-2, 5-dimethoxybenzene, 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thione-l-oxide, 8-hydroxyquinoline or its copper salt, 2,3-di-hydro-5-carboxanilido 6-methyl-l, 4-oxathiin, 2,3-dihydro-5-carboxanilido-6-methyl-l, 4-oxathiin-4, 4-dioxide, 2-methyl-5, 6-dihydro-4H-pyran 3-carboxylic acid anilide, 2-methyl-furan-3-carboxylic acid anilide, 2, 5-dimethyl-furan-3-carboxylic acid anilide, 2,4, 5-trimethyl-furan-3-carboxylic acid anilide, 2, 5-dimethyl furan-3-carboxylic acid cyclohexylamide, N-cyclohexyl-N-methoxy-2, 5-dimethyl-furan-3-carboxamide, 2-methyl-benzoic acid anilide, 2-iodo-benzoic acid anilide, 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-tridecyl-morpholine or its salts, 2,6-dimethyl-N-cyclododecyl-morpholine or its salts, N- [3- (p-tert-butylphenyl) -2- methylpropyl] cis-2, 6-dimethylmorpholine, N- [3- (p-ter. -butylphenyl) -2-methylpropyl] piperidine, 1- [2- (2, 4-dichlorophenyl) -4-ethyl-l , 3-dioxolan-2-yl-ethyl] - 1H-1,2,4-triazole 1- [2- (2,4-dichlorophenyl) -4-n-propyl-1,3-di-oxolan-2- yl-ethyl] -1H-1,2,4-triazole, N- (n-propyl) -N- (2,4,6-tri-chlorophenoxyethyl) -N'-imidazol-yl-urea, 1- (4th -Chlorphenoxy) - 3, 3-dimethyl-l- (1H-1, 2, 4-triazol-l-yl) -2-butanone, (2-chlorophenyl) - (4-chlorophenyl) -5-pyrimidine- methanol, 5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine, bis- (p-chlorophenyl) -3-pyridine-methanol, 1,2-bis- (3-ethoxycarbonyl-2-thioureido ) -benzene, 1, 2-bis- (3-methoxycarbonyl-2-thioureido) -benzene, [2- (4-chlorophenyl) ethyl] - (1, 1-dimethylethyl) -1H-1, 2, 4 -triazole-1-ethanol, 1- [3- (2-chlorophenyl) -1- (4-fluorophenyl) oxira n-2-yl-methyl] - 1H-1, 2,4-triazole and

various fungicides, such as dodecylguanidine acetate, 3- [3- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] glutarimide, hexachlorobenzene, DL-methyl-N- (2,6-dimethyl-ρhenyl) -N-furoyl (2) -alaninate, DL-N- (2, 6-dimethyl-phenyl) -N- (2'-methoxyacetyl) -alanine-methyl ester, N- (2, 6-dimethylphenyl) -N -chloroacetyl-D, L-2-aminobutyrene-acton, DL-N- (2, 6-dimethylphenyl) -N- (phenylacetyl) -alanine methyl ester, 5-methyl-5-vinyl-3- (3, 5- dichlorophenyl) -2, 4-dioxo-l, 3-oxazolidine, 3- [(3, 5-dichlorophenyl) -5-methyl-5-methoxymethyl-l, 3-oxazolidin-2, 4-dione, 3- (3, 5-dichlorophenyl) -1-iso-propylcarbamoyl- hydantoin, N- (3, 5-dichlorophenyl) -1, 2-dimethylcyclopropane-1,2-dicarboximide, 2-cyano- [N- (ethylaminocarbonyl) -2-methoximino] acetamide, 1- [2- ( 2, 4-dichlorophenyl) pentyl] -1H-1, 2, 4-tri-azole, 2, 4-difluoro-α- (1H-1, 2, 4-triazolyl-l-methyl) -benzhydryl alcohol, N- (3-chloro-2, 6-dinitro-4-trifluoromethyl-phenyl) -5-trifluoromethyl-3-chloro-2-aminopyridine, l- ((bis- (4-fluorophenyl) methylsilyl) -methyl) -1H-1,2,4-triazole,

Strobilurins such as methyl-E-methoximino- [α- {o-tolyloxy) - o-toly1] acetate, methyl-E-2- {2- [6- (2-cyanophenoxy) pyridimin-4-yl-oxy] phenyl} -3-methoxyacrylate, methyl-E-methoximino- [α- (2,5-dimethyloxy) -o-toly1] acetamide.

Anilino-pyrimidines such as N- (4,6-dimethylpyrimidin-2-yl) aniline, N- [4-methyl-6- (l-propynyl) pyrimidin-2-yl] aniline, N- (4-methyl-6- cyclopropyl-pyrimidin-2-yl) aniline.

Phenylpyrroles such as 4- (2,2-difluoro-1,3-benzodioxol-4-yl) pyrrole-3-carbonitrile.

Cinnamic acid amides such as 3- (4-chlorophenyl) -3- (3,4-dimethoxyphenyl) acrylic acid morpholide.

Preferred combination partners are a) azoles, which are preferably selected from: bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, hexaconazole, metconazole, prochloraz, propiconazole, tebuconazole, trifluorobazazole, trifluorobazazole, trifluorobazazole , Penconazole, simeconazole, ipconazole, triticonazole and prothioconazole; b) benzophenones of the formula IV,

wherein

R ^{9 represents} chlorine, methyl, acetoxy, pivaloyloxy or hydroxy, preferably methoxy;

R ^{10 represents} chlorine or preferably methyl; R ^{11 represents} hydrogen, halogen, preferably bromine, or methyl; and

R ^{12 is} Cχ-C ₆ alkyl, preferably methyl, or benzyl, where the phenyl part of the benzyl radical can carry a halogen or methyl substituent;

c) oxime ether derivatives of the formula V

where the substituents X ¹ to X ⁵ and Y ¹ to Y ^{4 have the} following meaning:

X ¹ halogen, Cχ-C ₄ haloalkyl Cχ-C ₄ haloalkoxy;

X ² to X ⁵ independently of one another are hydrogen, halogen,

Cχ-C ₄ alkyl, Cχ-C ₄ haloalkyl, Cχ-C alkoxy or Cχ-C ₄ haloalkoxy;

Y ¹ Cχ-C ₄ alkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, Cχ-C ₄ alkyl-C ₃ -C ₇ cycloalkyl, these radicals being one or more under halogen , Cyano and Cχ-C ₄ alkoxy can carry selected substituents;

Y ^{2 is} a phenyl radical or a 5- or 6-membered saturated or unsaturated heterocyclic radical having at least one heteroatom selected from N, 0 and S, the cyclic radicals being one to three under halogen, Cχ-C ₄ -alkyl, Cχ-C ₄ -Alkoxy, Cχ-C ₄ -haloalkyl, Cχ-C-haloalkoxy, Cχ-C ₄ -alkoxy-C ₂ -C ₄ -alkenyl and Cχ-C ₄ -alkoxy- CC ₄ -alkynyl may have selected substituents; and

Y ³ , Y ⁴ independently of one another are hydrogen, Cχ-C ₄ -alkyl, Cχ-C ₄ -alkoxy, Cχ-C ₄ -alkylthio, N-Cχ-C ₄ -alkylamino, Cχ-C ₄ -haloalkyl or Cχ-C ₄ haloalkoxy; and

d) pyraclostrobin. Particularly noteworthy are combinations of benzamidoxime derivatives of the formula (I) and in particular the preferred representatives thereof with one, two or three of the following active compounds: metrafenone (a benzophenone of the formula (IV), where R ^{9 is} methoxy, R ¹⁰ represent methyl, R ^{11 represents} bromine and R ^{12 represents} methyl), epoxiconazole and pyraclostrobin.

The alcohol alkoxylates to be used according to the invention have adjuvant, in particular activity-demanding properties. Thus, when such alcohol alkoxylates are added to the benzamidoxime derivatives of the formula (I), a comparatively higher fungicidal action is observed when they are used. The following aspects, in particular, derive from the adjuvant effect when using one or more benzamide oxime derivatives of the formula (I), if appropriate in combination with one or more further active compounds:

comparatively higher effectiveness of the benzamide oxime derivatives at a given application rate; comparatively lower application rate of the benzamide oxime derivatives for a given effect; comparatively stronger absorption of the benzamidoxime derivatives by the organism to be treated, in particular a plant, especially via the leaf, and thus advantages in the post-emergence process, in particular in the spray treatment of plants.

The use according to the invention relates to a number of different possible uses, which are directed in particular to plant cultivation, agriculture and horticulture. The benzamide oxime derivatives of the formula (I) can be used in particular as fungicides and thus serve to control a broad spectrum of phytopathogenic fungi, in particular from the class of the Ascomycetes, Basidiomycetes, Phycomycetes and Deuteromycetes. Some of them are systemically active and can therefore also be used as foliar and / or soil fungicides. This applies in a corresponding manner to combinations of the benzamide oxime derivatives and other active ingredients, in particular fungicides.

Accordingly, the present invention also relates to methods corresponding to the above uses for the treatment of organisms which are infected by one or more harmful fungi, or for the preventive treatment of organisms in which there is a risk of infection with harmful fungi and therefore would like to avoid them. The procedure involves having an appropriate amount of active ingredient and adjuvant applied.

The organisms to be treated are primarily plants or parts of plants such as seeds. The treatment is such that a - in particular fungicidal - effective amount (application rate) of the combination of active ingredient and adjuvant acts on the harmful fungi, their habitat or the organisms to be kept free of them, in particular plants and seeds, soils, surfaces, materials or spaces leaves.

Advantages are particularly in the control of a variety of mushrooms on various crops such as cotton, vegetables (e.g. cucumber, beans, tomatoes, potatoes and squashes), barley, grass, oats, bananas, coffee, corn, fruit plants, rice, rye, soy, Wine, wheat, ornamental plants, sugar cane and a variety of seeds. The appropriate application is the responsibility of the expert.

Particular advantages are found in particular in the control of the following phytopathogenic fungi: Blumeria graminis (powdery mildew) on cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin plants, Podosphaera leucotricha on apples, Uncinula necator on vines, Puccinia species on cereals, Rhizo species on cotton, rice and lawn, Ustilago on cereals and sugar cane, Venturia inaequalis (scab) on apples, Helminthosporium species on cereals, Septoria nodorum on wheat, Botrytis cinera (gray mold) on strawberries, vegetables, ornamental plants and vines, Cercospora arachidicola on peanuts, Pseudocercosporella herpotrichoides on wheat and barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Plasmopara viticola on vines, Pseudoperonospora species in hops and cucumbers, Alternaria species on vegetables and fruit, Mycosphaerella species on bananas as well as Fusarium and Verticillium species.

In principle, the amount of active ingredient applied can be varied widely as a result of the high tolerance to plants. The application rates according to the invention for the benzamide oxime derivatives of the formula (I) are typically from 0.001 to 2.5 kg / ha, preferably 0.005 to 2 kg / ha, in particular 0.01 to 1.0 kg / ha and for the Alcohol alkoxylates generally at 0.001 to 25 kg / ha, preferably 0.05 to 2 kg / ha, in particular 0.1 to 1 kg / ha.

In the case of seed treatment, application rates for the benzamide oxime derivatives of the formula (I) are in general from 0.001 to 250 g / kg of seed, preferably from 0.01 to 100 g / kg, in particular from 0.01 to 50 g / kg and for the alcohol alkoxylates generally 0.001 to 250 g / kg, preferably 0.01 to 100 g / kg, in particular 0.01 to 50 g / kg.

The application rate ratio of alcohol alkoxylates to benzamido xime derivatives is generally in the range from 0.5: 1 to 100: 1, preferably 1: 1 to 50: 1, in particular 1: 1 to 20: 1. A special aspect According to the application rates of alcohol alkoxylates are greater than the application rates of benzamide oxime derivatives.

In the context of the use according to the invention, the active compounds are generally first formulated into an agent in accordance with agricultural practice and then applied as an agent. The adjuvant can already be added to the agent-containing agent; However, it can also be present separately, if appropriate also formulated as a further agent in accordance with agricultural practice, and can only be applied with the agent-containing agent at the same time as it is actually used, or at an appropriate time interval, so that the agent and adjuvant can act together.

The use according to the invention therefore also includes the use of the alcohol alkoxylates according to the invention as a "stand-alone" product. In this sense, the combination of active ingredient and adjuvant according to the invention can also be provided in the form of a kit. Such a kit contains at least two containers. A container comprises at least one benzamidoxime derivative of the formula (I), optionally formulated as an agent with suitable auxiliaries. Another container comprises at least one alcohol alkoxylate.

The present invention also relates to compositions with an active ingredient component (a) comprising (al) at least one benzamido xime derivative of the formula (I) and with an adjuvant component (b) comprising (bl) at least one alkoxylated alcohol, where that Weight ratio of component (bl) to (al) is at least 0.5.

Q _he makes proportion of component (a) in the total weight of the composition typically more than 1 wt .-%, preferably more than 2 wt .-% and especially more than 2.5 wt .-% of. On the other hand, the proportion of component (a) in the total weight of the composition generally makes up less than 75% by weight, preferably less than 60% by weight and in particular less than 50% by weight. The proportion of component (a1) in the total weight of the composition generally makes up more than 1% by weight, preferably more than 2% by weight and in particular more than 2.5% by weight. On the other hand, the proportion of component (a1) in the total weight of the composition generally makes up less than 50% by weight, preferably less than 40% by weight and in particular less than 35% by weight.

According to one embodiment of the present invention, the active ingredient component (a) consists essentially of (al), i.e.

(al) one or more benzamidoxime derivatives of the formula (I).

In addition to component (a1), the drug component (a) of agents according to the invention can have at least one further plant active ingredient.

According to a particular embodiment, agents according to the invention comprise as a further plant active ingredient

(a2) at least one or more of the combination partners described above, in particular one or more active substances which are selected from the azoles, benzophenones of the formula IV, oxime ether derivatives of the formula (V) and pyraclostrobin described above.

The relative proportions of active ingredient in such compositions containing an active ingredient combination are largely variable. According to one aspect, relatively larger proportions by weight of active ingredient (a2) than active ingredient (al) are used. This weight ratio of (a2) to (al) is typically in a range from 1.1: 1 to 20: 1, preferably from 1.5: 1 to 10: 1 and in particular from 2: 1 to 5: 1.

Components of component (b) in the total weight of the composition of more than 1% by weight, preferably more than 2% by weight and in particular more than 2.5% by weight are advantageous. On the other hand, components (b) in the total weight of the composition of less than 80% by weight, preferably less than 60% by weight and in particular less than 50% by weight, are generally expedient.

Components of component (b1) in the total weight of the composition are more than 5% by weight, preferably more than 8% by weight, in particular more than 10% by weight, especially more than 15% by weight and especially of more than 20% by weight are advantageous. On the other hand, components (bl) in the total weight of the agent are of less than 50% by weight, preferably less than 45% by weight and in particular less than 40% by weight, as a rule expedient.

According to one embodiment of the present invention, the active ingredient component (b) consists essentially of (bl), i.e. one or more alcohol alkoxylates.

In order to ensure a sufficient adjuvant effect, the weight ratio of component (bl) to component (al) is preferably more than 0.5, in particular more than 1 and advantageously more than 2.

The agents according to the invention can be formulated and used, for example, in the form of directly sprayable solutions, powders and suspensions or in the form of high-proof aqueous, oily or other suspensions, dispersions, emulsions, oil dispersions, pastes, dusts, sprinkling agents or granules. The form of application depends on the intended use; in any case, it should ensure as fine and uniform a distribution of the mixture according to the invention as possible.

Agents according to the invention preferably fall in the field of liquid formulations. These include in particular water-soluble concentrates (SL formulations), suspension concentrates (SC formulations), suspoemulsions (SE formulations) and microemulsions.

According to one embodiment, the present invention relates to agents with high active ingredient proportions (concentrates). In this case, the proportion of component (a) in the total weight of the composition generally amounts to more than 100 g / 1, preferably more than 200 g / 1 and in particular more than 250 g / 1. On the other hand, the proportion of component (a) in the total weight of the composition is expediently generally less than 700 g / 1, preferably less than 650 g / 1 and in particular less than 600 g / 1. Ranges from 200 to 600 g / l are therefore preferred. Here, the benzamide oxime derivative content usually amounts to up to 300 g / l.

According to a particular embodiment of the present invention, the agents comprise at least one auxiliary as component (c).

Component (c) can serve a variety of purposes. Suitable auxiliaries are selected according to the requirements. usually by a specialist.

For example, auxiliaries are selected from

5

(cl) surfactants;

(c2) anti-settling agents, anti-foaming agents, retention agents, pH buffers, anti-drift reagents; 0

(c3) minerals and trace elements that can be used by plants;

(c4) chelating agents;

(c5) solvents or diluents; 5

The proportion of component (c) in the total weight of the composition is, if present, generally 10 to 60% by weight, preferably 15 to 50% by weight and in particular 20 to 45% by weight. 0

The term “surface-active auxiliary” here denotes surface-active or surface-active agents, such as surfactants, dispersants, emulsifiers or wetting agents. 5 In principle, anionic, cationic, amphoteric and nonionic surfactants can be used.

The anionic surfactants include, for example, carboxylates, _Q in particular alkali metal, alkaline earth metal and ammonium salts of fatty acids, for example potassium stearate, which are usually also referred to as soaps; glutamates; Sarcosinates, for example sodium lauroyl sarcosinate; taurates; Methylcelluloses; Alkyl phosphates, especially alkyl mono- and diphosphoric acid esters; Sulfate; Sulfonates, especially alkyl and alkylarylsulfonates, especially alkali, alkaline earth and ammonium salts of arylsulfonic acids and alkyl-substituted arylsulfonic acids, alkylbenzenesulfonic acids, such as lignin and phenolsulfonic acids, naphthalene and dibutylnaphthalenesulfonic acids, or dodecylbenzenesulfonates, nodecylbenzenesulfonates Alkyl methyl ester sulfonates, condensation products of sulfonated naphthalene and derivatives thereof with formaldehyde, condensation products of naphthalene sulfonic acids, phenolic and / or phenolic sulfonic acids with formaldehyde or with formaldehyde and urea, mono- or dialkyl succinic acid ester sulfonates; 5 as well as protein hydrolyzates and lignin sulfate. The aforementioned sulfonic acids are advantageously used in the form of their new tralen or optionally basic salts used.

The cationic surfactants include, for example, quaternized ammonium salts, in particular alkyltrimethylammonium and dialkyldimethylammonium halides and alkylsulfates, and pyridine and imidazoline derivatives, in particular alkylpyridinium halides.

The nonionic surfactants include in particular

Alkylaryl alkoxylates, especially alkylphenol alkoxylates and especially their ethoxylates, such as, for example, ethoxylated iso-octyl, octyl or nonylphenol, tributylphenol polyoxyethylene ether; - Fatty alcohol polyoxyethylene alkyl esters, for example lauryl alcohol polyoxyethylene ether acetate; alkoxylated animal and / or vegetable fats and / or oils, for example corn oil ethoxylates, castor oil ethoxylates, tallow fat ethoxylates; Glycerol esters, such as glycerol monostearate,

Fatty amine alkoxylates, fatty acid amide and fatty acid diethanol amide alkoxylates, especially their ethoxylates; Sugar surfactants, in particular sorbitol esters, such as, for example, sorbitan fatty acid esters (sorbitan monooleate, sorbitan tristearate), and ethoxylated carboxylic acids and esters of mono- or polyfunctional alcohols such as polyoxyethylene sorbitan fatty acid esters, alkyl (poly) glycosides and N-alkylgluconamides;

- alkyl methyl sulfoxides;

- Alk ldimethylphosphinoxid, such as tetradecyldimethylphosphinoxid.

Di-, tri- and multiblock polymers of the type (AB) _X , ABA and BAB, eg polystyrene block polyethylene oxide, and AB comb polymers, eg polymethacrylate comb polyethylene oxide and in particular ethylene oxide-propylene oxide block copolymers or their end group sealed derivatives.

The amphoteric surfactants include, for example, sulfobetaines,

Carboxybetaines and alkyldimethylamine oxides, e.g. Tetradecyldimethylamine oxide.

Further surfactants, which can be mentioned here by way of example, are perfluorosurfactants, silicone surfactants, phospholipids, such as, for example, lecithin or chemically modified lecithins, amino acid surfactants, for example N-lauroylglutamate and surface-active homo- and copolymers, for example polyvinylpyrrolidone, polyacrylic acids in the form of their salts, polyvinyl alcohol , Polypropylene oxide, polyethylene oxide, Maleic anhydride-isobutene copolymers and vinylpyrrolidone-vinyl acetate copolymers.

The proportion of component (cl) in the total weight of the composition is - if present - generally up to 20% by weight, preferably up to 15% by weight, especially up to 10% by weight, and in particular up to 5% by weight .-%. _Q Anti-settling agents can be used in particular for suspension concentrates. These are primarily used for rheological stabilization. In this context, mineral products, such as bentonites, talcites and herctorites, should be mentioned in particular. 5 The anti-foaming agents include, in particular, those of the silicone type, for example the Silicon SL marketed by Wacker and the like.

The minerals and trace elements that can be used in plants include, in particular, inorganic ammonium salts, such as ammonium sulfate, ammonium nitrate, ammonium chloride, ammonium phosphate or other minerals or trace elements that can be used in plants, in particular ammonium nitrate fertilizer granules and / or urea. These can occur, for example, as aqueous and optionally mixed concentrates, such as. B. Ensol solutions, are introduced into the agents according to the invention.

If present, the proportion of component (c3) is the overall _Q samtgewicht of the agent is usually 0.1 to 35 wt .-%, and preferably 0.2 to 20 wt .-%.

Preferred chelating agents are heavy metal and especially transition metal complexing compounds e.g. EDTA and its 5 derivatives.

If present, the proportion of component (c4) in the total weight of the composition is generally 0.001 to 0.5% by weight, preferably 0.005 to 0.2% by weight and in particular 0.01 to 0.10% by weight. %.

The agents can contain solvents of soluble components or diluents of insoluble components of the agent. 5

In principle, for example, mineral oils, synthetic oils as well as vegetable and animal oils, as well as low-molecular lare hydrophilic solvents such as alcohols, ethers, ketones and the like.

On the one hand, aprotic or apolar solution or. To name diluents, such as mineral oil fractions of medium to high boiling point, for example kerosene and diesel oil, furthermore coal tar oils, hydrocarbons, paraffin oils, for example Cs to Co hydrocarbons of the n- or iso-alkane series or mixtures thereof, optionally hydrogenated or partially hydrogenated aromatics or Alkyl aromatics from the benzene or naphthalene series, for example aromatic or cycloaliphatic C ₇ to Cχβ hydrocarbon compounds, aliphatic or aromatic carboxylic acid or dicarboxylic acid esters, fats or oils of vegetable or animal origin, such as mono-, di- and triglycerides , in pure form or as a mixture, for example in the form of oily natural substance extracts, for example olive oil, soybean oil, sunflower oil, castor oil, sesame oil, corn oil, peanut oil, rapeseed oil, linseed oil, almond oil, castor oil, safflower oil, and their raffinates, for example hydrogenated or partially hydrogenated products thereof and / or their esters, especially methyl and ethyl esters.

Examples of Cs to Co hydrocarbons of the n- or iso-alkane series are n- and iso-octane, -decane, -hexadecane, -octadecane, -eicosane, and preferably hydrocarbon mixtures, such as paraffin oil (that of technical quality can contain up to about 5% aromatics) and a Cχ ₈ -C ₄ mixture, which is commercially available from Texaco under the name Spraytex oil.

The aromatic or cycloaliphatic C ₇ - to Cχs hydrocarbon compounds include in particular aromatic or cycloaliphatic solvents from the alkyl aromatic series. These compounds can be unhydrogenated, partially hydrogenated or fully hydrogenated. Such solvents include, in particular, mono-, di- or trialkylbenzenes, mono-, di-, trialkyl-substituted tetralines and / or mono-, di-, tri- or tetraalkyl-substituted naphthalenes (alkyl is preferably Cχ- C ₆ alkyl). Examples of such solvents are toluene, o-, m-, p-xylene, ethylbenzene, isopropylbenzene, tert-butylbenzene and mixtures, such as the Exxon products marketed under the name Shellsol and Solvesso, for example Solvesso 100, 150 and 200th

Examples of suitable monocarboxylic acid esters are oleic acid esters, in particular methyl oleate and ethyl oleate, lauric acid esters, in particular 2-ethylhexyl laurate, octyl laurate and isopropyl laurate, isopropyl myristate, palmitic acid esters, in particular 2-ethylhexyl palmitate and isopropyl palmitate, especially stearic acid esters Stearic acid n-butyl ester and 2-ethylhexanoic acid 2-ethylhexyl ester.

Examples of suitable dicarboxylic acid esters are adipic acid esters, in particular dimethyl adipate, di-n-butyl adipate, di-n-octyl adipate,

Di-iso-octyl adipate, also known as bis (2-ethylhexyl) adipate,

Di-n-nonyl adidipate, di-iso-nonyl adidipate and ditridecyl adipate;

Succinic acid esters, in particular di-n-octyl succinate and di-iso-octyl succinate, and di- (iso-nonyl) cyclohexane-1,2-dicarboxylate.

The proportion of the aprotic solvents or diluents described above in the total weight of the agent is generally less than 30% by weight, preferably less than 20% by weight and in particular less than 5% by weight.

On the other hand, protic or polar solvents or diluents may be mentioned, for example water, C ₂ -Cs-monoalcohols such as ethanol, propanol, isopropanol, butanol, isobutanol, tert-butanol, cyclohexanol and 2-ethylhexanol, C ₃ -Cs Ketones such as diethyl ketone, t-butyl methyl ketone and cyclohexanone, and aprotic amines such as N-methyl and N-octylpyrrolidone.

The proportion of the protic or polar solvents or diluents described above in the total weight of the agent is kept low according to the invention and is generally less than 20% by weight, preferably less than 15% by weight and in particular less than 10% by weight .-%.

According to a particular embodiment, the present invention relates to means comprising

(a) 2 to 35% by weight of at least one benzamidoxime derivative of the formula (I), preferably N-phenylacetyl-2-difluoromethoxy-5,6-difluorobenzamide- (0-cyclopropylmethyl] -oxime or N-phenylacetyl- 2-trifluoromthoxy-5,6-difluorobenzamide- (0-cyclopropylmethyl) oxime, and optionally 5 to 25% by weight of metrafenone, epoxiconazole or pyraclostrobin, or a mixture of 2 or 3 of these active ingredients; and

(b) 5 to 40% by weight of at least one alcohol alkoxylate, preferably an alkoxylated C10 or C13-0xo alcohol; as well as advantageously

(c) 15 to 45% by weight of one or more auxiliary substances. Agents according to the invention can be produced in a manner known per se. For this, at least parts of the components are put together. It should be noted here that products, in particular commercial products, can be used, the components of which can contribute to different components. For example, a certain surfactant can be dissolved in an aprotic solvent so that this product can contribute to components (cl) and (c5) according to the invention. As a mixture, the combined products are then generally to be mixed intensively with one another and, if necessary, to be ground, for example in the case of suspensions.

Mixing can be carried out in a manner known per se, e.g. by homogenizing with suitable devices such as KPG or magnetic stirrers.

The present invention also relates to the use of agents according to the invention in the application possibilities described above.

The agents can be applied in a manner known per se, e.g. by spraying, atomizing, dusting, scattering or pouring. To do this, it may be necessary to first prepare a 5 spray liquor, which is then e.g. with a drivable

Spraying machine is applied by means of finely distributing nozzles. The devices and working techniques used for this are known to the person skilled in the art. 0 Sprayable broths normally contain 0.0001 to 10, preferably 0.001 to 5, and in particular 0.002 to 2.0% by weight of active ingredient (a). To prepare a customary spray liquor, for example 0.2 to 5.0, preferably 0.3 to 3.0 and in particular 0.35 to 2.0 1 of an active ingredient concentrate according to the invention containing component (a) 5 to 10 to 2000 1, preferably with water 50 to 1500 1 and in particular 100 to 1000 1 are diluted. 0.1 to 5% by weight (based on the spray mixture) of further auxiliaries can optionally be added to the spray mixture. Exemplary substances for such auxiliary substances are starch and starch derivatives, for example a starch containing carboxyl and sulfonic acid groups (Nu-Film from Union Carbide Corp.) and spreading agents and extenders such as Vapor Guard from Miller Chemical & Fertilizer Corp. 5 In the context of the present description, quantities are generally based on the total weight of the composition, unless stated otherwise. The expression "essentially" means according to the invention generally draws a percentage ratio of at least 90%, preferably at least 95% and in particular at least 98%.

In the context of the present description, terms such as alkyl, alkoxy, etc. include straight-chain or branched hydrocarbon groups, preferably with - unless stated otherwise - 1 to 30 carbon atoms, the fatty residues generally 5 to 30, preferably 8 to 20 and in particular 9 to 16 carbon atoms, and the shorter residues, e.g. generally have 1 to 10, in particular 1 to 6 and particularly preferably 1 to 4, carbon atoms as substituents on aromatic groups.

The terms "alkenyl" and "alkynyl" stand for straight-chain or branched, 1-, 2-, 3-, 4-, 5- or 6-fold unsaturated hydrocarbon groups, preferably with - unless stated otherwise - 2 to 30 Carbon atoms, the fatty residues usually 5 to 30, preferably 8 to 20 and in particular 9 to 16 carbon atoms, and the shorter residues, for example generally have 2 to 10, in particular 2 to 6 and particularly preferably 1 to 4, carbon atoms as substituents on aromatic groups. In particular, the residues of mono- or polyunsaturated fatty acids should be mentioned here.

The term "halogen" preferably stands for fluorine, chlorine, bromine and iodine, in particular for fluorine and especially for chlorine.

For example:

Cχ-C ₄ alkyl for: methyl, ethyl, n-propyl, 1-methylethyl, n-butyl, 1-methylpropyl, 2-methylpropyl or 1, 1-dimethylethyl, especially for methyl or ethyl;

- C ₅ -C ₄ o-Al yl for: lauryl, steary or cetyl;

Cχ-C ₄ haloalkyl for: a Cχ-C ₄ alkyl radical as mentioned above, which is partially or completely substituted by fluorine, chlorine, bromine and / or iodine, for example trichloromethyl, trifluoromethyl, 2-fluoroethyl, 2-chloroethyl , 2-bromoethyl,

2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2,2,2-trichloroethyl, 2-fluoropropyl, 3-fluoropropyl, 2-chloropropyl or 3-chloropropyl, in particular for 2-fluoroethyl or 2-chloroethyl; Cyano-Cχ-C ₄ alkyl for: for example cyanomethyl, 1-cyanoeth-l-yl, 2-cyanoeth-l-yl, 1-cyanoprop-l-yl, 2-cyanoprop-l-yl, 3-cyano-prop -1-yl, l-cyanoprop-2-yl or 2-cyanoprop-2-yl, especially for cyanomethyl or 2-cyanoethyl; 5

Cχ-C ₄ alkoxy for: methoxy, ethoxy, n-propoxy, 1-methylethoxy, n-butoxy, 1-methylpropoxy, 2-methylpropoxy or 1, 1-dimethylethoxy, especially for methoxy or ethoxy; ° - Cχ-C ₄ -alkoxy-Cχ-C ₄ -alkyl for: Cχ-C ₄ -alkoxy as mentioned above substituted Cχ-C ₄ -alkyl, e.g. for methoxymethyl, ethoxymethyl, n-propoxymethyl, (1-methyl - ethoxy) methy1, n-butoxymethyl, (1-methylpropoxy) methyl, (2-methylpropoxy) methyl, (1, 1-dimethylethoxy) methyl1, 5 2- (methoxy) ethyl or 2- (ethoxy) ethyl, especially for methoxymethyl or 2-methoxyethyl;

C ₂ -C ₆ alkenyl for: e.g. ethenyl, prop-2-en-l-yl, n-buten-4-yl, l-methyl-prop-2-en-l-yl, 2-methyl-prop- 2-en-l-yl or 0 2-butene-l-yl, in particular for prop-2-en-l-yl;

C ₃ -C ₆ haloalkenyl for: C ₃ -C ₆ alkenyl as mentioned above, which is partially or completely substituted by fluorine, chlorine and / or bromine, for example 2-chloroallyl, 3-chloro-5-lyl, 2, 3 -Dichlorallyl or 3,3-dichlorallyl, especially for 2-chloroallyl;

C ₂ -Cg alkynyl for: for example ethynyl, prop-1-in-1-yl, prop-2-in-1-yl, n-but-1-in-1-yl, n-but-1-yl -3-yl, n-0 but-l-in-4-yl or n-but-2-in-l-yl, especially for prop-2-in-l-yl;

C ₃ -C ₈ cycloalkyl-Cχ-C-alkyl for: e.g. cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, (cyclo-5 propyl) ethyl, l- (cyclobutyl) ethyl, l- (cyclopentyl) ethyl, l- (Cyclohexyl) ethyl, 1- (cycloheptyl) ethyl, 1- (cyclo-octyl) ethyl, 2- (cyclopropyl) ethyl or 2- (cyclobutyl) ethyl, especially for cyclopentylmethyl; 0

Phenyl-Cχ-C ₆ -alkyl for: for example benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylprop-l-yl, 2-phenylprop-l-yl, 3-phenylprop-1-yl, in particular for benzyl or 2-phenylethyl; _ - Thienyl-Cχ-C ₄ alkyl for: eg 2-thienylmethyl, 3-thienylmethyl or 2-thienylethyl; Pyrazolyl-Cχ-C ₄ alkyl for: eg 1-pyrazolylmethyl, 2-pyrazolylmethyl, 3-pyrazolylmethyl or 2-pyrazolylylethyl.

The invention is illustrated by the following examples:

Examples 1: Biological effectiveness (curative control of

Wheat mildew) 10

Leaves of potted wheat seedlings of the "Kanzler" variety were grown in the two-leaf stage with spores of powdery mildew (Erysiphe [syn. Blumeria] graminis forma specialis. Tritici)

15 pollinated and cultivated in the greenhouse until the pre-infection averaged 20%. The plants were then sprayed with an aqueous suspension or emulsion which contained the active compounds and adjuvants given below. The suspension or emulsion was prepared from a stock solution with 10%

20 active ingredients in a mixture consisting of 85% cyclohexanone and 5% emulsifier. After the spray coating had dried on, the plants were pushed back into the greenhouse. The test plants were placed in a greenhouse at temperatures between 20 and 24 ° C and 60 to 90% relative humidity. 25 20 or 30 days after application, the extent of mildew development was determined visually in% infestation of the entire leaf area.

Table 1:% infestation of the leaves after application of the aqueous active substance formulation, which corresponded to an application rate of 7.5 g of active substance per ha

35

40

5

Active ingredient A: N-phenylacetyl-2-difluoromethoxy-5, 6-difluorobenz-a id- (O-cyclopropylmethyl] -oxime alkoxylate 1: ClO-oxo alcohol x 3 EO Alkoxylate 2: C13-0xoalcohol x 6 EO x 3 PO

It is clearly evident that the alcohol alkoxylates used strengthen the fungicidal activity of the active ingredients or active ingredient mixtures.

Claims

claims

1. Means comprising 5

(al) at least one benzamidoxime derivative of the formula (I)

where the substituents have the following meanings; 5

R ¹ difluoromethyl or trifluoromethyl;

R ^{2 is} hydrogen or fluorine; 0

R ³ Cχ-C ₄ -alkyl, which may be substituted by cyano, _{Cχ-C4-haloalkyl, Cχ-C4-alkoxy-Cχ-C 4} alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₆ -Halogenalkenyl, C ₃ -Ce alkynyl or C ₃ -C ₈ cycloalkyl-Cχ-C-alkyl; 5

R ⁴ phenyl-Cχ-C ₆ alkyl, which selected one or more of halogen, Cχ-C ₄ alkyl, Cχ-C ₄ haloalkyl, Cχ-C ₄ alkoxy and Cχ-C ₄ haloalkoxy on the phenyl ring Can carry substituents, or Q thienyl-Cχ-C ₄ alkyl, which on the thienyl ring one or more halogen, Cχ-C ₄ alkyl, Cχ-C ₄ haloalkyl, Cχ-C ₄ alkoxy and Cχ-C ₄ -Halogenalkoxy may carry selected substituents, or pyrazolyl-Cχ-C ₄ -alkyl, which has one or more halogen, Cχ-C ₄ -alkyl, Cχ-C ₄ -haloalkyl, Cχ-C ₄ -alkoxy or C on the pyrazolyl ring Cχ-C ₄ haloalkoxy can carry selected substituents.

(bl) at least one alkoxylated alcohol, 0 where the weight ratio of component (bl) to (al) is at least 0.5.

2. Composition according to claim 1, characterized in that the proportion of component (bl) to the total weight of the composition is greater than the proportion of component (al).

3. Composition according to claim 1 or 2, characterized in that the alcohol has 5 to 30, preferably 8 to 20 and in particular 9 to 15 carbon atoms.

4. Agent according to one of the preceding claims, characterized in that the degree of alkoxylation is 1 to 100, preferably 1 to 25, in particular 2 to 15 and particularly preferably 3 to 12.

10 5. Agent according to one of the preceding claims, characterized in that the alkoxylated alcohol is selected from alcohol alkoxylates of the formula (II)

R ⁶ -0- (C _ra H _2m 0) _x - (C _n H _2n O) _y - (C _p H ₂ pO) _!! -H (II)

15 where

R6 represents C ₅ -C ₃ o-alkyl or C ₅ -C ₃ o -alkenyl;

20 m, n, p independently of one another represent an integer from 2 to 16, preferably 2, 3, 4 or 5;

x, y, z independently represent a number from 0 to 100; and

25 x + y + z corresponds to a value from 1 to 100.

6. Means according to claim 5, characterized in that m = 2, the value of x is greater than zero and z = 0.

30

7. Means according to claim 6, characterized in that y is zero.

8. Means according to claim 6, characterized in that y is greater than zero.

9. Composition according to claim 8, characterized in that n = 3.

40

10. Composition according to claim 9, characterized in that the ratio of x to y is 1: 1 to 4: 1 and in particular 1.5: 1 to 3: 1.

₄₅ 11. Agent according to claim 8, characterized in that n = 5.

12. Composition according to claim 11, characterized in that the value of x is 1 to 50 and preferably 4 to 25 and the value of y is 0.5 to 20, preferably 0.5 to 4 and in particular 0.5 to 2.

5

13. Composition according to claim 5, characterized in that n == 2, the values of y and x are each greater than zero and z = 0.

10 14. Composition according to claim 13, characterized in that m = 3.

15. Composition according to claim 14, characterized in that the ratio of x to y 1:10 to 3: 1 and in particular 1.5: 1 to

^{15 is} 1: 6.

16. Composition according to claim 13, characterized in that m = 5.

²⁰ 17. Composition according to claim 16, characterized in that the

The value of x is 0.5 to 20, preferably 0.5 to 4 and in particular 0.5 to 2 and the value of y is 3 to 50 and preferably 4 to 25.

25

18. Composition according to one of claims 5 to 17, characterized in that the alcohol is 2-propylheptanol.

19. Composition according to one of claims 5 to 17, characterized in that the alcohol is a C13-oxo alcohol. 0

20. Composition according to claim 19, characterized in that the C13-oxo alcohol is obtainable by hydrogenation of hydroformylated trimerbutene. 5

21. Composition according to claim 19, characterized in that the C13-oxo alcohol is obtainable by hydrogenation of hydroformylated dimer hexene.

22. Agent according to one of claims 5 to 17, characterized gekenn0 characterized in that the alcohol is a ClO-oxo alcohol.

23. Composition according to claim 22, characterized in that the ClO-oxo alcohol is obtainable by hydrogenation of hydrofor- mylated trimer propene.

24. Agent according to one of the preceding claims, characterized in that the benzamidoxime derivative is a compound of formula la

R ^{1 is} as defined above;

20 R ^5, halogen, _{Cι-C4-alkyl,} halo-CC ₄ alkyl, Cχ-C ₄ alkoxy or Cι-C ₄ haloalkoxy is hydrogen; and

n is 1, 2 or 3.

25 25. Composition according to claim 24, characterized in that the

Benzamide oxime derivative N-phenylacetyl-2-difluoromethoxy-5, 6-di-fluorobenzamide (O-cyclopropylmethyl) oxime or N-phenylacetyl-2-trifluoromethoxy-5, 6-difluorobenzamide (O-cyclopropylmethyl) oxime is.

30

26. Composition according to one of the preceding claims, comprising

(a2) at least one other fungicide.

35 27. Composition according to claim 26, characterized in that the further fungicide is selected from metrafenone, epoxiconazole and pyraclostrobin.

28. Composition according to one of the preceding claims, comprising 40

(c) other tools.

29. Composition according to claim 1, comprising 5 (a) 2 to 35 wt .-% of at least one benzamidoxime derivative of the formula (I), preferably N-phenylacetyl-2-difluoromethoxy-5, 6-difluorobenzamide- (O- cyclopropylmethyl] oxime or N-phenylacetyl-2-trifluoromthoxy-5, 6-difluorobenzamide (O-cyclopropylmethyl) oxime, and optionally 5 to 25% by weight of metrafenone, epoxiconazole or pyraclostrobin, or a mixture of 2 or 3 of these 5 substances ; and

(b) 5 to 40% by weight of at least one alcohol alkoxylate, preferably an alkoxylated CIO or C13 oxo alcohol; as well as advantageously

10

(c) 15 to 45% by weight of one or more auxiliary substances.

30. Kit with at least two containers, whereby

15 (al) a first container contains at least one benzamidoxime derivative of the formula (I) and the benzamidoxime derivative is as defined in one of the preceding claims; and

^AW (bl) a second container of at least one alkoxylated

Includes alcohol and the alkoxylated alcohol is as defined in any one of the preceding claims.

31. Use of an alkoxylated alcohol to improve

25 fungicidal activity of a benzamidoxime derivative of the formula

(I), wherein the benzamidoxime derivative of formula (I) is as defined in any one of the preceding claims.

32. Use according to claim 31, characterized in that the application rate ratio of alcohol alkoxylate to benzamide oxime derivative is in the range from 0.5: 1 to 100: 1, preferably 1: 1 to 50: 1, in particular 1: 1 to 20 : 1 lies.

33. Use according to claim 31 or 32, characterized in that 35 the amount of alcohol alkoxylate is greater than that

Application rate of benzamide oxime derivative.

40

5