Fungicidal combinations of active substances

The present invention relates to new combinations of active ingredients which consist of a known fluorobenzothiazole derivative on the one hand and other known active ingredients on the other hand and are very well suited for combating phytopathogenic fungi.

It is already known that isopropyl 1 - ({[1- (6-fluoro-1,3-benzothiazol-2-yl) ethyl] amino} carbonyl) -2-methylpropylcarbamate has fungicidal properties (cf. EP-A1- 775 696). The effectiveness of this substance is good, but leaves something to be desired at low application rates in some cases.

Furthermore, it is already known that numerous triazole derivatives, aniline derivatives, dicarboximides and other heterocycles can be used to combat fungi (cf. EP-A 0 040 345, DE-A 22 01 063, DE-A 23 24 010, Pesticide Manual, 9th Edition (1991), pages 249 and 827, EP-A 0 382 375 and EP-A 0 515 901). However, the effect of these substances is not always sufficient at low application rates.

Finally, it is also known that 1 - [(6-chloro-3-pyridinyl) methyl] -N-nitro-2-imidazolidinimine can be used to control animal pests, such as insects (cf. Pesticide Manual, 9th Edition (1991 ), Page 491). Fungicidal properties of this substance have not yet been described.

Furthermore, it is already known that 1- (3,5-dimethyl-isoxazole-4-sulfonyl) -2-chloro-6,6-difluoro- [1,3] dioxolo- [4,5f] -benzimidazole has fungicidal properties (see WO 97-06171).

Furthermore, it is already known that substituted azadioxacycloalkenes have a fungicidal action (cf. EP-B-712 396).

Finally, it is also known that substituted halopyrimidines have fungicidal properties (cf. DE-A1-196 46 407, EP-B-712 396).

It has now been found that the new drug combinations of a fluorobenzothiazole derivative of the formula<chemistry id="chem0001" num="0001"><img file="EP1239733B1_D0001.tif" /></chemistry> and<ul id="ul0001" list-style="none"><li>(1) a triazole derivative of the formula<chemistry id="chem0002" num="0002"><img file="EP1239733B1_D0002.tif" /></chemistry>    in which<dl id="dl0001"><dt>X</dt><dd>represents chlorine or phenyl, and</dd><dt>Y</dt><dd>For<chemistry id="chem0003" num="0003"><img file="EP1239733B1_D0003.tif" /></chemistry> or<chemistry id="chem0004" num="0004"><img file="EP1239733B1_D0004.tif" /></chemistry> stands,</dd></dl> and or</li><li>(2) the triazole derivative of the formula<chemistry id="chem0005" num="0005"><img file="EP1239733B1_D0005.tif" /></chemistry> and or</li><li>(3) an aniline derivative of the formula<chemistry id="chem0006" num="0006"><img file="EP1239733B1_D0006.tif" /></chemistry>    in which<dl id="dl0002"><dt>R¹</dt><dd>represents hydrogen or methyl,</dd></dl> and or</li><li>(4) N- [1- (4-chlorophenyl) ethyl] -2,2-dichloro-1-ethyl-3-methylcyclopropane carboxamide of the formula<chemistry id="chem0007" num="0007"><img file="EP1239733B1_D0007.tif" /></chemistry> and or</li><li>(5) the zinc propylene 1,2-bis (dithiocarbamidate) of the formula<chemistry id="chem0008" num="0008"><img file="EP1239733B1_D0008.tif" /></chemistry> and or</li><li>(6) at least one thiocarbamate of the formula<chemistry id="chem0009" num="0009"><img file="EP1239733B1_D0009.tif" /></chemistry>    Me = Zn or Mn or mixture of Zn and Mn and or</li><li>(7) the aniline derivative of the formula<chemistry id="chem0010" num="0010"><img file="EP1239733B1_D0010.tif" /></chemistry> and or</li><li>(8) the compound of formula<chemistry id="chem0011" num="0011"><img file="EP1239733B1_D0011.tif" /></chemistry> and or</li><li>(9) the benzothiadiazole derivative of the formula<chemistry id="chem0012" num="0012"><img file="EP1239733B1_D0012.tif" /></chemistry> and or</li><li>(10) the 8-t-butyl-2- (N-ethyl-Nn-propylamino) methyl-1,4-dioxaspiro [5,4] decane of the formula<chemistry id="chem0013" num="0013"><img file="EP1239733B1_D0013.tif" /></chemistry> and or</li><li>(11) the compound of formula<chemistry id="chem0014" num="0014"><img file="EP1239733B1_D0014.tif" /></chemistry> and or</li><li>(12) the compound of formula<chemistry id="chem0015" num="0015"><img file="EP1239733B1_D0015.tif" /></chemistry> and or</li><li>(13) the compound of the formula<chemistry id="chem0016" num="0016"><img file="EP1239733B1_D0016.tif" /></chemistry> and or</li><li>(14) the cyanoxime derivative of the formula<chemistry id="chem0017" num="0017"><img file="EP1239733B1_D0017.tif" /></chemistry> and or</li><li>(15) a pyrimidine derivative of the formula<chemistry id="chem0018" num="0018"><img file="EP1239733B1_D0018.tif" /></chemistry>    in which<dl id="dl0003"><dt>R²</dt><dd>for methyl, ―C≡C ― CH₃ (Mepanipyrim) or cyclopropyl (cyprodinyl),</dd></dl> and or</li><li>(16) an aniline derivative of the formula<chemistry id="chem0019" num="0019"><img file="EP1239733B1_D0019.tif" /></chemistry> and or</li><li>(17) the morpholine derivative of the formula<img file="EP1239733B1_D0020.tif" /> and or</li><li>(18) the phthalimide derivative of the formula<chemistry id="chem0020" num="0020"><img file="EP1239733B1_D0021.tif" /></chemistry> and or</li><li>(19) the phosphorus compound of the formula<chemistry id="chem0021" num="0021"><img file="EP1239733B1_D0022.tif" /></chemistry> and or</li><li>(20) the hydroxyethyl triazole derivative of the formula<chemistry id="chem0022" num="0022"><img file="EP1239733B1_D0023.tif" /></chemistry> and or</li><li>(21) the 1 - [(6-chloro-3-pyridinyl) methyl] -N-nitro-2-imidazolidinimine of the formula<chemistry id="chem0023" num="0023"><img file="EP1239733B1_D0024.tif" /></chemistry> and or</li><li>(22) the oxazolidinedione of the formula<chemistry id="chem0024" num="0024"><img file="EP1239733B1_D0025.tif" /></chemistry> and or</li><li>(23) the benzamide derivative of the formula<chemistry id="chem0025" num="0025"><img file="EP1239733B1_D0026.tif" /></chemistry> and or</li><li>(24) a guanidine derivative of the formula<chemistry id="chem0026" num="0026"><img file="EP1239733B1_D0027.tif" /></chemistry>    in which<dl id="dl0004"><dt>m</dt><dd>stands for integers from 0 to 5 and</dd><dt>R³</dt><dd>for hydrogen (17 to 23%) or the rest of the formula</dd></dl><chemistry id="chem0027" num="0027"><img file="EP1239733B1_D0028.tif" /></chemistry> stands, and or</li><li>(25) the triazole derivative of the formula<chemistry id="chem0028" num="0028"><img file="EP1239733B1_D0029.tif" /></chemistry> and or</li><li>(26) the halogenobenzimidazole of the formula<chemistry id="chem0029" num="0029"><img file="EP1239733B1_D0030.tif" /></chemistry> and or</li><li>(27) the halopyrimidine of the formula<chemistry id="chem0030" num="0030"><img file="EP1239733B1_D0031.tif" /></chemistry> and or</li><li>(28) the tetrachloroisophthalodinitrile of the formula<chemistry id="chem0031" num="0031"><img file="EP1239733B1_D0032.tif" /></chemistry> and or</li><li>(29) the compound of formula<chemistry id="chem0032" num="0032"><img file="EP1239733B1_D0033.tif" /></chemistry> and or</li><li>(30) the pyridinamine of the formula<chemistry id="chem0033" num="0033"><img file="EP1239733B1_D0034.tif" /></chemistry> and or</li><li>(31) the thiazole carboxamide of the formula<chemistry id="chem0034" num="0034"><img file="EP1239733B1_D0035.tif" /></chemistry> and or</li><li>(32) the sulfonamide of the formula<chemistry id="chem0035" num="0035"><img file="EP1239733B1_D0036.tif" /></chemistry> and or</li><li>(33) the compound of formula<chemistry id="chem0036" num="0036"><img file="EP1239733B1_D0037.tif" /></chemistry> and or</li><li>(34) the compound of formula<chemistry id="chem0037" num="0037"><img file="EP1239733B1_D0038.tif" /></chemistry> and or</li><li>(35) the compound of formula<chemistry id="chem0038" num="0038"><img file="EP1239733B1_D0039.tif" /></chemistry> and or</li><li>(36) the diamide of the formula<chemistry id="chem0039" num="0039"><img file="EP1239733B1_D0040.tif" /></chemistry> and or</li><li>(37) the methoxyacrylate derivative of the formula<chemistry id="chem0040" num="0040"><img file="EP1239733B1_D0041.tif" /></chemistry> and or</li><li>(38) the quinoline derivative of the formula<chemistry id="chem0041" num="0041"><img file="EP1239733B1_D0042.tif" /></chemistry> and or</li><li>(39) the phenylamide derivative of the formula<chemistry id="chem0042" num="0042"><img file="EP1239733B1_D0043.tif" /></chemistry> and or</li><li>(40) the phenylamide derivative of the formula<chemistry id="chem0043" num="0043"><img file="EP1239733B1_D0044.tif" /></chemistry> and or</li><li>(41) the dicarboxime derivative of the formula<chemistry id="chem0044" num="0044"><img file="EP1239733B1_D0045.tif" /></chemistry> and or</li><li>(42) the phosphonic acid of the formula<chemistry id="chem0045" num="0045"><img file="EP1239733B1_D0046.tif" /></chemistry> and or</li><li>(43) the pyrrole derivative of the formula<chemistry id="chem0046" num="0046"><img file="EP1239733B1_D0047.tif" /></chemistry> and or</li><li>(44) the phenyl carbonate of the formula<chemistry id="chem0047" num="0047"><img file="EP1239733B1_D0048.tif" /></chemistry> and or</li><li>(45) the copper compounds<ul id="ul0002" list-style="none" compact="compact"><li>a)         Copper oxychloride (XXXXVIa) </li><li>b)         Copper hydroxide (XXXXVIb)</li></ul> and or</li><li>(46) the imidazole derivative of the formula<chemistry id="chem0048" num="0048"><img file="EP1239733B1_D0049.tif" /></chemistry> and or</li><li>(47) a triazole derivative of the formula<chemistry id="chem0049" num="0049"><img file="EP1239733B1_D0050.tif" /></chemistry> and or<chemistry id="chem0050" num="0050"><img file="EP1239733B1_D0051.tif" /></chemistry> and or<chemistry id="chem0051" num="0051"><img file="EP1239733B1_D0052.tif" /></chemistry> and or<chemistry id="chem0052" num="0052"><img file="EP1239733B1_D0053.tif" /></chemistry> and or<chemistry id="chem0053" num="0053"><img file="EP1239733B1_D0054.tif" /></chemistry> and or<chemistry id="chem0054" num="0054"><img file="EP1239733B1_D0055.tif" /></chemistry> and or<chemistry id="chem0055" num="0055"><img file="EP1239733B1_D0056.tif" /></chemistry> and or<chemistry id="chem0056" num="0056"><img file="EP1239733B1_D0057.tif" /></chemistry> and or</li><li>(48) a compound of the general formula<chemistry id="chem0057" num="0057"><img file="EP1239733B1_D0058.tif" /></chemistry>    in which<dl id="dl0005"><dt>R¹</dt><dd>represents phenyl, 2-naphthyl, 1,2,3,4-tetrahydronaphthyl or indanyl which is unsubstituted or substituted by fluorine, chlorine, bromine, methyl or ethyl,</dd></dl> and or</li><li>(49) N-Methyl-2- (methoxyimino) -2- [2 - ([1- (3-tri-fluoro-methylphenyl) ethoxy] iminomethyl) phenyl] acetamide of the formula<chemistry id="chem0058" num="0058"><img file="EP1239733B1_D0059.tif" /></chemistry> and or</li><li>(50) 2,4-dihydro-5-methoxy-2-methyl-4- [2 - ([([1- (3-tri-fluoromethylphenyl) ethylidene] amino) oxy] methyl) phenyl] -3H-1, 2,4-triazol-3-one of the formula<chemistry id="chem0059" num="0059"><img file="EP1239733B1_D0060.tif" /></chemistry> and or</li><li>(51) the compound of formula<chemistry id="chem0060" num="0060"><img file="EP1239733B1_D0061.tif" /></chemistry></li></ul> have very good fungicidal properties.

Surprisingly, the fungicidal action of the active compound combinations according to the invention is considerably higher than the sum of the actions of the individual active compounds. So there is an unforeseeable, real synergistic effect and not just an addition.

It can be seen from the structural formula for the active ingredient of the formula (I) that the compound has two asymmetrically substituted carbon atoms. The product can therefore be present as a mixture of different isomers or in the form of a single isomer.

Preferred compounds of the formula (I) are compounds in which the amino acid part is formed from i-propyloxycarbonyl-L-valine and the fluorobenzothiazolethylamine part is racemic, but in particular has the (R) configuration.

Formula (II) includes the compounds

1- (4-chlorophenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) butan-2-one of the formula<chemistry id="chem0061" num="0061"><img file="EP1239733B1_D0062.tif" /></chemistry>

1- (4-chlorophenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) butan-2-ol of the formula<chemistry id="chem0062" num="0062"><img file="EP1239733B1_D0063.tif" /></chemistry> and

1- (4-phenylphenoxy) -3,3-dimethyl-1- (1,2,4-triazol-1-yl) butan-2-ol of the formula<chemistry id="chem0063" num="0063"><img file="EP1239733B1_D0064.tif" /></chemistry>

Formula (IV) comprises the aniline derivatives of the formulas

<chemistry id="chem0064" num="0064"><img file="EP1239733B1_D0065.tif" /></chemistry> and<chemistry id="chem0065" num="0065"><img file="EP1239733B1_D0066.tif" /></chemistry>

It can be seen from the structural formula for the active ingredient of the formula (V) that the compound has three asymmetrically substituted carbon atoms. The product can therefore be present as a mixture of different isomers or in the form of a single component. The compounds N- (R) - [1- (4-chlorophenyl) ethyl] - (1S) -2,2-dichloro-1-ethyl-3t-methyl-1R-cyclopropanecarboxamide of the formula are particularly preferred<chemistry id="chem0066" num="0066"><img file="EP1239733B1_D0067.tif" /></chemistry> and N- (R) - [1- (4-chlorophenyl) ethyl] - (1R) -2,2-dichloro-1-ethyl-3t-methyl-1R-cyclopropanecarboxamide of the formula<img file="EP1239733B1_D0068.tif" />

Formula (VII) includes the compounds

(VIIa) Me = Zn (Zineb),         (VIIb) Me = Mn (Maneb) and         (VIIc) mixture of (VIIa) and (VIIb) (Mancozeb).

Formula (XVI) includes the compounds

(XVIa) R² = CH₃ (Pyrimethanil) and<chemistry id="chem0067" num="0067"><img file="EP1239733B1_D0069.tif" /></chemistry>         (XVIc) R²= -C≡C-CH₃ (Mepanipyrim)

The compound of formula (XVII) can be methyl N- (2,6-dimethylphenyl) -N- (methoxyacetyl) -DL-alaninate (metalaxyl, XVIIa) or methyl N- (2,6-dimethylphenyl) -N- ( methoxyacetyl) -D-alaninate (Metalaxyl-M, XVIIb) are present.

The hydroxyethyl-triazole derivative of the formula (XXI) can be in the "thiono" form of the formula<chemistry id="chem0068" num="0068"><img file="EP1239733B1_D0070.tif" /></chemistry> or in the tautomeric "mercapto" form of the formula<chemistry id="chem0069" num="0069"><img file="EP1239733B1_D0071.tif" /></chemistry> are available. For the sake of simplicity, only the "Thiono" form is listed.

The guanidine derivative of the formula (XXV) is a mixture of substances with the common name guazatine.

It can be seen from the structural formula for the active compounds of the formula (XXXXIX) that the compounds can be present as E or Z isomers. The product can therefore be present as a mixture of different isomers or in the form of a single isomer. Compounds of the formula (XXXXIX) in which the compounds of the formula (XXXXIX) are present as E isomers are preferred. The compounds of the formulas are particularly preferred<chemistry id="chem0070" num="0070"><img file="EP1239733B1_D0072.tif" /></chemistry> and<chemistry id="chem0071" num="0071"><img file="EP1239733B1_D0073.tif" /></chemistry> and<chemistry id="chem0072" num="0072"><img file="EP1239733B1_D0074.tif" /></chemistry> and<chemistry id="chem0073" num="0073"><img file="EP1239733B1_D0075.tif" /></chemistry> and<chemistry id="chem0074" num="0074"><img file="EP1239733B1_D0076.tif" /></chemistry> and<chemistry id="chem0075" num="0075"><img file="EP1239733B1_D0077.tif" /></chemistry> and their isomers.

The following active ingredients are particularly preferred as mixing partners of the compounds of the formula (I):<ul id="ul0003" list-style="none" compact="compact"><li>(3) tolylfluanide (IVb),</li><li>(5) Propineb (VI),</li><li>(6) Mancozeb (VIIc),</li><li>(7) fenhexamide (VIII),</li><li>(8) iprovalicarb (VIII),</li><li>(11) azoxystrobin (XII),</li><li>(12) trifloxystrobin (XIII),</li><li>(13) compound of the formula (XIV),</li><li>(18) Folpet (XIX),</li><li>(20) compound of the formula (XXI),</li><li>(26) compound of the formula (XXVII),</li><li>(27) compound of the formula (XXVIII),</li><li>(28) chlorothalonil (XXIX),</li><li>(30) fluazinam (XXXI), and</li><li>(45) Copper compounds<ul id="ul0004" list-style="none" compact="compact"><li>a)         Copper oxychloride (XXXXVIa)</li><li>b)         Copper hydroxide (XXXXVIb).</li></ul></li></ul>

The components present in the active compound combinations according to the invention in addition to a halogenobenzimidazole of the formula (XXVII) are also known.

The active substances are described in detail in the following publications:<ul id="ul0005" list-style="none"><li>(1) compounds of the formula (II)    DE-A 22 01 063    DE-A 23 24 010</li><li>(2) compound of formula (III)    EP-A 0 040 345</li><li>(3) compounds of the formula (IV)    Pesticide Manual, 9th. Ed. (1991), pages 249 and 827</li><li>(4) Compound of formula (V) and its individual derivatives    EP-A 0 341 475</li><li>(5) Compound of Formula (VI)    Pesticide Manual, 9th. Ed. (1991), page 726</li><li>(6) compounds of the formula (VII)    Pesticide Manual, 9th. Ed. (1991), pages 529, 531 and 866</li><li>(7) compound of formula (VIII)    EP-A 0 339 418</li><li>(8) Compound of Formula (IX)    EP-A 0 472 996</li><li>(9) compound of formula (X)    EP-A 0 313 512</li><li>(10) compound of formula (XI)    EP-A 0 281 842</li><li>(11) compound of formula (XII)    EP-A 0 382 375</li><li>(12) compound of formula (XIII)    EP-A-460 575</li><li>(13) compound of formula (XIV)    DE-A 196 02 095</li><li>(14) compound of formula (XV)    Pesticide Manual, 9th. Ed. (1991), page 206</li><li>(15) compounds of the formula (XVI)    EP-A 0 270 111    EP-A 0 310 550</li><li>(16) compound of formula (XVII)    Pesticide Manual, 9th. Ed. (1991), page 554</li><li>(17) Compound of Formula (XVIII)    EP-A 0 219 756</li><li>(18) compound of the formula (XIX)    Pesticide Manual, 9th. Ed. (1991), page 431</li><li>(19) compound of the formula (XX)    Pesticide Manual, 9th. Ed. (1991), page 443</li><li>(20) compound of the formula (XXI)    WO 96-16048</li><li>(21) Compound of Formula (XXII)    Pesticide Manual, 9th. Ed. (1991), page 491</li><li>(22) Compound of Formula (XXIII)    EP-A 0 393 911</li><li>(23) compound of the formula (XXIV)    EP-A 0 600 629</li><li>(24) Substance of the formula (XXV)    Pesticide Manual, 9th. Ed. (1991), page 461</li><li>(25) compound of the formula (XXVI)    Pesticide Manual, 9th. Ed. (1991), page 654</li><li>(26) compound of the formula (XXVII)    WO 97-06171</li><li>(27) compound of the formula (XXVIII)    DE-A1-196 46 407, EP-B-0 712 396</li><li>(28) compound of the formula (XXIX)    US 3,290,353</li><li>(29) compound of the formula (XXX)    DE-A-156 7169</li><li>(30) compound of formula (XXXI)    EP-A-0 031 257</li><li>(31) compound of formula (XXXII)    EP-A-0 639 547</li><li>(32) compound of formula (XXXIII)    EP-A-0 298 196</li><li>(33) compound of the formula (XXXIV)    EP-A-600 629</li><li>(34) compound of the formula (XXXV)    DE-A-2 149 923</li><li>(35) compound of the formula (XXXVI)    DE-A-2 012 656</li><li>(36) compound of formula (XXXVII)    US 1 972 961</li><li>(37) compound of the formula (XXXVIII)    EP-A-326 330</li><li>(38) compound of the formula (XXXIX)    EP-A 278 595</li><li>(39) compound of the formula (XXXX)    DE-A-3 030 026</li><li>(40) compound of the formula (XXXXI)    DE-A-2 903 612</li><li>(41) compound of formula (XXXXII)    U.S. 2,553,770</li><li>(42) compound of the formula (XXXXIII)    known and available for purchase</li><li>(43) compound of the formula (XXXXIV)    EP-A-206 999</li><li>(44) compound of formula (XXXXV)    EP-A-78 663</li><li>(45) <ul id="ul0006" list-style="none" compact="compact"><li>a) compound of the formula (XXXXVIa) known and available for purchase</li><li>b) compound of the formula (XXXXVIb) known and available for purchase</li></ul></li><li>(46) compound of the formula (XXXXVII)    DE-A-2 429 523</li><li>(47) <ul id="ul0007" list-style="none"><li>a) Compound of the formula (XXXXVIIIa) EP-A-112 284</li><li>b) compound of the formula (XXXXVIIIb) DE-A-3 042 303</li><li>c) compound of the formula (XXXXVIIIc)    DE-A-3 406 993</li><li>d) compound of the formula (XXXXVIIId)    EP-A-68 813</li><li>e) compound of the formula (XXXXVIIIe)    DE-A-2551560</li><li>f) Compound of the formula (XXXXVIIIf) EP-A-145 294</li><li>g) Compound of the formula (XXXXVIIIg) DE-A-3 721 786</li><li>h) compound of the formula (XXXXVIIIh)    EP-A-234 242</li></ul></li><li>(48) compound of the formula (XXXXIX)    WO 96/23763</li><li>(49) compound of the formula (XXXXX)    EP-A-596 254</li><li>(50) compound of the formula (XXXXXI)    WO 98/23155</li><li>(51) compound of the formula (XXXXXII)    EP-A-569 384.</li></ul>

In addition to an active ingredient of the formula (I), the active compound combinations according to the invention contain at least one active ingredient from the compounds of groups (1) to (51). They can also contain other fungicidally active admixing components.

If the active ingredients are present in the active ingredient combinations according to the invention in certain weight ratios, the synergistic effect is particularly evident. However, the weight ratios of the active ingredients in the active ingredient combinations can be varied within a relatively wide range. In general, 1 part by weight of active compound of the formula (I)<ul id="ul0008" list-style="none"><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight of active ingredient from group (1),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight of active ingredient from group (2),</li><li>1 up to 150 parts by weight, preferably 1 to 100 parts by weight, of active ingredient from group (3),</li><li>0.1 to 10 parts by weight, preferably 0.2 to 5 parts by weight of active ingredient from group (4),</li><li>1 up to 150 parts by weight, preferably 5 to 100 parts by weight of active ingredient from group (5),</li><li>1 up to 150 parts by weight, preferably 5 to 100 parts by weight, of active ingredient from group (6),</li><li>0.1 to 50 parts by weight, preferably 1 to 20 parts by weight, of active ingredient from group (7),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight of active ingredient from group (8),</li><li>0.02 to 50 parts by weight, preferably 0.1 to 10 parts by weight of active ingredient from group (9),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight of active ingredient from group (10),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight of active ingredient from group (11),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight of active ingredient from group (12).</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight of active ingredient from group (13),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight, of active ingredient from group (14),</li><li>0.2 to 50 parts by weight, preferably 1 to 20 parts by weight, of active ingredient from group (15),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight, of active ingredient from group (16),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight, of active ingredient from group (17),</li><li>1 up to 150 parts by weight, preferably 5 to 100 parts by weight of active ingredient from the group (18),</li><li>0.1 to 150 parts by weight, preferably 1 to 100 parts by weight, of active ingredient from group (19),</li><li>0.02 to 50 parts by weight, preferably 0.2 to 10 parts by weight, of active ingredient from group (20),</li><li>0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight of active ingredient from group (21),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight of active ingredient from group (22),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight of active ingredient from the group (23),</li><li>0.01 to 150 parts by weight, preferably 1 to 100 parts by weight, of active ingredient from group (24),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight of active ingredient from group (25),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight of active ingredient from group (26),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight of active ingredient from group (27),</li><li>1 up to 150 parts by weight, preferably 5 to 100 parts by weight, of active ingredient from group (28),</li><li>1 up to 150 parts by weight, preferably 5 to 100 parts by weight, of active ingredient from group (29),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight of active ingredient from group (30),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight, of active ingredient from group (31),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight, of active ingredient from group (32),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight, of active ingredient from group (33),</li><li>0.1 to 50 parts by weight, preferably 1 to 20 parts by weight of active ingredient from the group (34),</li><li>0.1 to 50 parts by weight, preferably 1 to 10 parts by weight, of active ingredient from group (35),</li><li>1 up to 150 parts by weight, preferably 5 to 100 parts by weight, of active ingredient from group (36),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight of active ingredient from group (37).</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight of active ingredient from the group (38),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight of active ingredient from the group (39),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight, of active ingredient from group (40),</li><li>1 up to 150 parts by weight, preferably 5 to 100 parts by weight, of active ingredient from group (41),</li><li>1 up to 150 parts by weight, preferably 5 to 100 parts by weight, of active ingredient from group (42),</li><li>0.1 to 50 parts by weight, preferably 1 to 20 parts by weight, of active ingredient from group (43),</li><li>0.1 to 50 parts by weight, preferably 1 to 20 parts by weight of active ingredient from the group (44),</li><li>1 up to 150 parts by weight, preferably 5 to 100 parts by weight, of active ingredient from the group (45a),</li><li>1 up to 150 parts by weight, preferably 5 to 100 parts by weight, of active ingredient from the group (45b),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight of active ingredient from group (46),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight, of active ingredient from group (47a),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight, of active ingredient from group (47b),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight of active ingredient from group (47c),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight of active ingredient from the group (47d),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight, of active ingredient from the group (47e),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight of active ingredient from the group (47f),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight of active ingredient from the group (47 g),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight of active ingredient from the group (47 h),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight of active ingredient from the group (48),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight of active ingredient from the group (49),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight of active ingredient from group (50),</li><li>0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight of active ingredient from group (51).</li></ul>

The active compound combinations according to the invention have very good fungicidal properties and can be used to control phytopathogenic fungi, such as Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes, etc.

The active compound combinations according to the invention are particularly suitable for combating Phytophthora infestans and Plasmopara viticola.

The fact that the active ingredient combinations are well tolerated by plants in the concentrations required to combat plant diseases allows treatment of above-ground parts of plants, of propagation stock and seeds, and of the soil. The active compound combinations according to the invention can be used for leaf application or as a mordant.

The active compound combinations according to the invention are also suitable for increasing the crop yield. They are also less toxic and have good plant tolerance.

According to the invention, all plants and parts of plants can be treated. Plants are understood here to mean all plants and plant populations, such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Cultivated plants can be plants which can be obtained by conventional breeding and optimization methods or by biotechnological and genetic engineering methods or combinations of these methods, including the transgenic plants and including the plant cultivars which can or cannot be protected by plant breeders' rights. Plant parts are to be understood to mean all above-ground and underground parts and organs of plants, such as shoots, leaves, flowers and roots, examples being leaves, needles, stems, stems, flowers, fruiting bodies, fruits and seeds as well as roots, tubers and rhizomes. The plant parts also include crops and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, offshoots and seeds.

The treatment of the plants and parts of plants with the active compounds according to the invention is carried out directly or by acting on their surroundings, living space or storage space according to the customary treatment methods, for example by dipping, spraying, evaporating, atomizing, scattering, spreading and in the case of propagation material, in particular seeds single or multi-layer wrapping.

The active compound combinations according to the invention can be converted into the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols, very fine encapsulations in polymeric substances and in coating compositions for seeds, and ULV formulations.

These formulations are prepared in a known manner, for example by mixing the active ingredients or combinations of active ingredients with extenders, that is to say liquid solvents, pressurized liquefied gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or dispersants and / or foam-generating agents. In the case of the use of water as an extender, for example organic solvents can also be used as auxiliary solvents. The following are essentially suitable as liquid solvents: aromatics, such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example Petroleum fractions, alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents such as dimethylformamide and dimethyl sulfoxide, and water. Liquefied gaseous extenders or carriers mean liquids which are gaseous at normal temperature and under normal pressure, for example aerosol propellants such as butane, propane, nitrogen and carbon dioxide. The following are suitable as solid carriers: for example natural rock powders such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powders such as highly disperse silica, aluminum oxide and silicates. Possible solid carriers for granules are: eg broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules from inorganic and organic flours as well as granules from organic material such as sawdust, coconut shells, corn cobs and tobacco stems. Suitable emulsifying and / or foam-generating agents are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example Alkylaryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates. Possible dispersing agents are, for example, lignin sulfite waste liquor and methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and also natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, for example iron oxide, titanium oxide, ferrocyan blue and organic dyes, such as alizarin, azo and metal phthalocyanine dyes and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc, can be used.

The formulations generally contain between 0.1 and 95% by weight of active ingredients, preferably between 0.5 and 90%.

The active compound combinations according to the invention, as such or in their formulations, can also be used in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, in order, for example, to broaden the spectrum of action or to prevent the development of resistance. In many cases, synergistic effects are obtained, ie the effectiveness of the mixture is greater than the effectiveness of the individual components.

A mixture with other known active ingredients, such as herbicides or with fertilizers and growth regulators, is also possible.

The active substance combinations can be used as such, in the form of their formulations or the use forms prepared therefrom, such as ready-to-use solutions, emulsifiable concentrates, emulsions, suspensions, wettable powders, soluble powders and granules. They are used in the customary manner, for example by pouring, spraying, atomizing, scattering, spreading, dry pickling, wet pickling, wet pickling, slurry pickling or incrusting.

When using the active compound combinations according to the invention, the application rates can be varied within a substantial range, depending on the type of application. In the treatment of parts of plants, the application rates of active compound combination are generally between 0.1 and 10,000 g / ha, preferably between 10 and 1,000 g / ha. In the case of seed treatment, the application rates of the active compound combination are generally between 0.001 and 50 g per kg of seed, preferably between 0.01 and 10 g per kg of seed. In the treatment of the soil, the active compound combination application rates are generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.

The good fungicidal activity of the active compound combinations according to the invention can be seen from the examples below. While the individual active ingredients have weaknesses in their fungicidal action, the combinations show an action that goes beyond a simple summation of action.

Fungicides always have a synergistic effect if the fungicidal activity of the active ingredient combinations is greater than the sum of the effects of the individually applied active ingredients.

The expected effect for a given combination of two active ingredients can be according to SR Colby ("Calculating Synergistic and Antagonistic Responses of Herbicide Combinations", Weeds <u>15</u> (1967), 20-22) can be calculated as follows: If<dl id="dl0006"><dt>X</dt><dd>the efficiency when using the active ingredient A in an application rate of <u>m</u> g / ha means</dd><dt>Y</dt><dd>the efficiency when using the active ingredient B in an application rate of <u>n</u> g / ha means and</dd><dt>E</dt><dd>the efficiency when using the active ingredients A and B in application rates of <u>m</u> and <u>n</u> g / ha means</dd></dl> then<maths id="math0001" num=""><math display="block"><mrow><mtext>E = X + Y - </mtext><mfrac><mrow><mtext>XY </mtext></mrow><mrow><mtext>100</mtext></mrow></mfrac></mrow></math><img file="EP1239733B1_D0078.tif" /></maths>

The efficiency is determined in%. It means 0% an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

If the actual fungicidal activity is greater than calculated, the combination of the combination is superadditive, ie there is a synergistic effect. In this case, the actually observed efficiency must be greater than the value for the expected efficiency (E) calculated from the above formula.

The invention is illustrated by the following examples. However, the invention is not limited to the examples.

<u>example 1</u>

Phytophthora test (tomato) / protective

<tables id="tabl0001" num="0001"><table frame="all"><tgroup cols="2" colsep="1" rowsep="0"><colspec colnum="1" colname="col1" colwidth="78.75mm" /><colspec colnum="2" colname="col2" colwidth="78.75mm" /><tbody valign="top"><row><entry namest="col1" nameend="col1" align="left">solvent</entry><entry namest="col2" nameend="col2" align="left">47 Parts by weight of acetone</entry></row><row rowsep="1"><entry namest="col1" nameend="col1" align="left">Emulsifier</entry><entry namest="col2" nameend="col2" align="left">3rd Parts by weight of alkylaryl polyglycol ether</entry></row></tbody></tgroup></table></tables>

To produce a suitable preparation of active compound, 1 part by weight of active compound or combination of active compounds is mixed with the stated amounts of solvent and emulsifier and the concentrate is diluted with water to the desired concentration or a commercially available formulation of active compound or combination of active compounds with water is diluted to the desired concentration.

To test for protective activity, young plants are sprayed with the active compound preparation in the stated application rate. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Phytophthora infestans. The plants are then placed in an incubation cabin at approx. 20 ° C and 100% relative humidity.

3rd Evaluation is carried out days after the inoculation. 0% means an efficiency that corresponds to that of the control, while an efficiency of 100% means that no infection is observed.

The activity found of the active compound combination according to the invention is greater than the calculated activity, ie there is a synergistic effect. The combination of the compound of the formula (I) and the halogenobenzimidazole of the formula No. XXVII has an actual efficiency of 73% at a mixing ratio of 1: 1 and an application rate of 0.1 g / ha. The expected value calculated using the Colby formula is significantly lower at 63%.

Active substances, application rates and test results are shown in the following tables.<tables id="tabl0002" num="0002"><img file="EP1239733B1_D0079.tif" /></tables><tables id="tabl0003" num="0003"><img file="EP1239733B1_D0080.tif" /></tables><tables id="tabl0004" num="0004"><img file="EP1239733B1_D0081.tif" /></tables><tables id="tabl0005" num="0005"><img file="EP1239733B1_D0082.tif" /></tables><tables id="tabl0006" num="0006"><img file="EP1239733B1_D0083.tif" /></tables><tables id="tabl0007" num="0007"><img file="EP1239733B1_D0084.tif" /></tables><tables id="tabl0008" num="0008"><img file="EP1239733B1_D0085.tif" /></tables><tables id="tabl0009" num="0009"><img file="EP1239733B1_D0086.tif" /></tables><tables id="tabl0010" num="0010"><img file="EP1239733B1_D0087.tif" /></tables><tables id="tabl0011" num="0011"><img file="EP1239733B1_D0088.tif" /></tables><tables id="tabl0012" num="0012"><img file="EP1239733B1_D0089.tif" /></tables><tables id="tabl0013" num="0013"><img file="EP1239733B1_D0090.tif" /></tables><tables id="tabl0014" num="0014"><img file="EP1239733B1_D0091.tif" /></tables><tables id="tabl0015" num="0015"><img file="EP1239733B1_D0092.tif" /></tables><tables id="tabl0016" num="0016"><img file="EP1239733B1_D0093.tif" /></tables><tables id="tabl0017" num="0017"><img file="EP1239733B1_D0094.tif" /></tables><tables id="tabl0018" num="0018"><img file="EP1239733B1_D0095.tif" /></tables><tables id="tabl0019" num="0019"><img file="EP1239733B1_D0096.tif" /></tables><tables id="tabl0020" num="0020"><img file="EP1239733B1_D0097.tif" /></tables><tables id="tabl0021" num="0021"><img file="EP1239733B1_D0098.tif" /></tables><tables id="tabl0022" num="0022"><img file="EP1239733B1_D0099.tif" /></tables><tables id="tabl0023" num="0023"><img file="EP1239733B1_D0100.tif" /></tables><tables id="tabl0024" num="0024"><img file="EP1239733B1_D0101.tif" /></tables><tables id="tabl0025" num="0025"><img file="EP1239733B1_D0102.tif" /></tables><tables id="tabl0026" num="0026"><img file="EP1239733B1_D0103.tif" /></tables><tables id="tabl0027" num="0027"><img file="EP1239733B1_D0104.tif" /></tables><tables id="tabl0028" num="0028"><img file="EP1239733B1_D0105.tif" /></tables><tables id="tabl0029" num="0029"><img file="EP1239733B1_D0106.tif" /></tables><tables id="tabl0030" num="0030"><img file="EP1239733B1_D0107.tif" /></tables><tables id="tabl0031" num="0031"><img file="EP1239733B1_D0108.tif" /></tables><tables id="tabl0032" num="0032"><img file="EP1239733B1_D0109.tif" /></tables><tables id="tabl0033" num="0033"><img file="EP1239733B1_D0110.tif" /></tables><tables id="tabl0034" num="0034"><img file="EP1239733B1_D0111.tif" /></tables><tables id="tabl0035" num="0035"><img file="EP1239733B1_D0112.tif" /></tables><tables id="tabl0036" num="0036"><img file="EP1239733B1_D0113.tif" /></tables><tables id="tabl0037" num="0037"><img file="EP1239733B1_D0114.tif" /></tables><tables id="tabl0038" num="0038"><img file="EP1239733B1_D0115.tif" /></tables><tables id="tabl0039" num="0039"><img file="EP1239733B1_D0116.tif" /></tables><tables id="tabl0040" num="0040"><img file="EP1239733B1_D0117.tif" /></tables><tables id="tabl0041" num="0041"><img file="EP1239733B1_D0118.tif" /></tables><tables id="tabl0042" num="0042"><img file="EP1239733B1_D0119.tif" /></tables><tables id="tabl0043" num="0043"><img file="EP1239733B1_D0120.tif" /></tables>