# Patent

## Title
Fungicidal combinations of active substances

## Abstract

The present invention relates to active compound combinations of a fluorobenzo-thiazole of the formula (I)




and at least one of the compounds listed herein. The active compound combinations of the present invention are useful as fungicides.

## Background
The present patent application is a division of U.S. application Ser. No. 10/149,353, filed Jun. 7, 2002, now U.S. Pat. No. 6,624,183, which was filed under 35 U.S.C. 371 as a national stage application of International Application PCT/EP00/11989, filed Nov. 30, 2000, which was published in German as International Patent Publication WO 01/44215 on Jun. 21, 2001, which is entitled to the right of priority of German Patent Applications 199 59 947.5, filed Dec. 13, 1999, and 100 21 412.6, filed May 3, 2000.


The present invention relates to novel active compound combinations which consist of a known fluoro-benzothiazole derivative and further known fungicidally active compounds, and which are highly suitable for controlling 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 activity of this compound is good; however, at low application rates it is in some cases not satisfactory.
Furthermore, it is already known that a large number of triazole derivatives, aniline derivatives, dicarboximides and other heterocycles can be employed for controlling 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). Likewise, the activity of these compounds is not always satisfactory at low application rates.
Finally, it is also known that 1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazo-lidineimine can be used for controlling animal pests such as insects (cf. Pesticide Manual, 9th Edition (1991), page 491). However, fungicidal properties have hitherto not been described for this compound.
Furthermore, it is already known that 1-(3,5-dimethyl-isoxazol-4-sulphonyl)-2-chloro-6,6-difluoro-[1,3]-dioxolo-[4,5f]-benzimidazole has fungicidal properties (cf. WO 97-06171).
Furthermore, it is already known that substituted azodioxacycloalkenes have fungicidal properties (cf. EP-B-712 396).
Finally, it is also known that substituted halogenopyrimidines have fungicidal properties (cf. DE-A1-196 46 407, EP-B-712 396).
It has now been found that the novel active compound combinations comprising a fluorobenzothiazole derivative of the formula




and

    
    
        (1) a triazole derivative of the formula
    
    






    
    
         in which
        
             X represents chlorine or phenyl and
        
        
    
    






    
    
        
        
             Y represents

and/or

        
        
        (2) the triazole derivative of the formula
    
    






and/or

    
    
        (3) an aniline derivative of the formula
    
    






    
    
         in which
        
             R1 represents hydrogen or methyl,

and/or

        
        
        (4) N-[1-(4-chloro-phenyl)-ethyl]-2,2-dichloro-1-ethyl-3-methyl-cyclopropane-carboxamide of the formula
    
    






and/or

    
    
        (5) the zinc propylene-1,2-bis-(dithiocarbamidate) of the formula
    
    






and/or

    
    
        (6) at least one thiocarbamate of the formula
    
    






    
    
         Me=Zn or Mn or a mixture of Zn and Mn

and/or

        (7) the aniline derivative of the formula
    
    






and/or

    
    
        (8) the compound of the formula
    
    






and/or

    
    
        (9) the benzothiadiazole derivative of the formula
    
    






and/or

    
    
        (10) the 8-t-butyl-2-(N-ethyl-N-n-propyl-amino)-methyl-1,4-dioxaspiro[5,4]-decane of the formula
    
    






and/or

    
    
        (11) the compound of the formula
    
    






and/or

    
    
        (12) the compound of the formula
    
    






and/or

    
    
        (13) the compound of the formula
    
    






and/or

    
    
        (14) the cyanoxime derivative of the formula
    
    






and/or

    
    
        (15) a pyrimidine derivative of the formula
    
    






    
    
         in which
        
             R2 represents methyl, —C≡C—CH3 (mepanipyrim) or cyclopropyl (cyprodinyl),

and/or

        
        
        (16) an aniline derivative of the formula
    
    






and/or

    
    
        (17) the morpholine derivative of the formula
    
    






and/or

    
    
        (18) the phthalimide derivative of the formula
    
    






and/or

    
    
        (19) the phosphorus compound of the formula
    
    






and/or

    
    
        (20) the hydroxyethyl-triazole derivative of the formula
    
    






and/or

    
    
        (21) the 1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidinimine of the formula
    
    






and/or

    
    
        (22) the oxazolidinedione of the formula
    
    






and/or

    
    
        (23) the benzamide derivative of the formula
    
    






and/or

    
    
        (24) a guanidine derivative of the formula
    
    






    
    
         in which
        
             m represents integers from 0 to 5 and
             R3 represents hydrogen (17 to 23%) or the radical of the formula
        
        
    
    






and/or

    
    
        (25) the triazole derivative of the formula
    
    






and/or

    
    
        (26) the halogeno-benzimidazole of the formula
    
    






and/or

    
    
        (27) the halogenopyrimidine of the formula
    
    






and/or

    
    
        (28) the tetrachloro-isophthalo-dinitrile of the formula
    
    






and/or

    
    
        (29) the compound of the formula
    
    






and/or

    
    
        (30) the pyridineamine of the formula
    
    






and/or

    
    
        (31) the thiazolecarboxamide of the formula
    
    






and/or

    
    
        (32) the sulphonamide of the formula
    
    






and/or

    
    
        (33) the compound of the formula
    
    






and/or

    
    
        (34) the compound of the formula
    
    






and/or

    
    
        (35) the compound of the formula
    
    






and/or

    
    
        (36) the diamide of the formula
    
    






and/or

    
    
        (37) the methoxyacrylate derivative of the formula
    
    






and/or

    
    
        (38) the quinoline derivative of the formula
    
    






and/or

    
    
        (39) the phenylamide derivative of the formula
    
    






and/or

    
    
        (40) the phenylamide derivative of the formula
    
    






and/or

    
    
        (41) the dicarboxime derivative of the formula
    
    






and/or

    
    
        (42) the phosphonic acid of the formula
    
    






and/or

    
    
        (43) the pyrrole derivative of the formula
    
    






and/or

    
    
        (44) the phenyl carbonate of the formula
    
    






and/or

    
    
        (45) the copper compounds
        a) copper oxychloride (XXXXVIa)
        b) copper hydroxid (XXXXVIb)

and/or

        (46) the imidazole derivative of the formula
    
    






and/or

    
    
        (47) the triazole derivative of the formula
        a)
    
    






and/or

    
    
        b)
    
    






and/or

    
    
        c)
    
    






and/or

    
    
        d)
    
    






and/or

    
    
        e)
    
    






and/or

    
    
        f)
    
    






and/or

    
    
        g)
    
    






and/or

    
    
        h)
    
    






and/or

    
    
        (48) a compound of the general formula
    
    






    
    
         in which
        
             R1 represents unsubstituted or fluorine-, chlorine-, bromine-, methyl- or ethyl-substituted phenyl, 2-naphthyl, 1,2,3,4-tetrahydronaphthyl or indanyl,

and/or

        
        
        (49) N-methyl-2-(methoxyimino)-2-[2-([1-(3-tri-fluoro-methyl-phenyl)ethoxy]iminomethyl)phenyl]acetamide of the formula
    
    






and/or

    
    
        (50) 2,4-dihydro-5-methoxy-2-methyl-4-[2-([([1-(3-tri-fluoro-methylphenyl)ethylidene]amino)oxy]methyl)phenyl]-3H-1,2,4-triazol-3-one of the formula
    
    






and/or

    
    
        (51) the compound of the formula
    
    






have very good fungicidal properties.

Surprisingly, the fungicidal activity of the active compound combinations according to the invention is considerably higher than the sum of the activities of the individual active compounds. Thus, an unforeseeable, true synergistic effect is present, and not just an addition of activities.
From the structural formula of the active compound of the formula (I), it can be seen that the compound has two asymmetrically substituted carbon atoms. Accordingly, the product can be present as a mixture of different isomers or else in the form of a single isomer.
Preferred compounds of the formula (I) are compounds in which the amino acid moiety is formed from i-propyloxycarbonyl-L-valine and the fluoro-benzothiazoleethylamine moiety is racemic, but has, in particular, the (R) configuration.
The formula (II) includes the compounds
1-(4-chloro-phenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-one of the formula




1-(4-chloro-phenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-ol of the formula




and

1-(4-phenyl-phenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-ol of the formula




The formula (IV) includes the aniline derivatives of the formulae




and





It is evident from the structural formula for the active compound of the formula (V) that the compound has three asymmetrically substituted carbon atoms. The product may therefore be present as a mixture of different isomers, or else in the form of a single component. Particular preference is given to the compounds
N-(R)-[1-(4-chloro-phenyl)-ethyl]-(1S)-2,2-dichloro-1-ethyl-3t-methyl-1R-cyclopropanecarboxamide of the formula




and

N-(R)-[1-(4-chloro-phenyl)-ethyl]-(1R)-2,2-dichloro-1-ethyl-3t-methyl-1R-cyclopropanecarboxamide of the formula




The formula (VII) includes the compounds

















(VIIa)
Me = Zn
(zineb),



(VIIb)
Me = Mn
(maneb) and



(VIIc)
mixture of (VIIa) and (VIIb)
(mancozeb).










The formula (XVI) includes the compounds

















(XVIa)
R2 = CH3
(pyrimethanil) and



 



(XVIb)




(cyprodinyl)



 



(XVIc)
R2 = —C≡C—CH3
(mepanipyrim)










The compound of the formula (XVII) can be present as methyl N-(2,6-dimethylphenyl)-N-(methoxyacetyl)-DL-alaninate (metalaxyl, XVIIa) or as methyl N-(2,6-dimethylphenyl)-N-(methoxyacetyl)-D-alaninate (metalaxyl-M, XVIIb).
The hydroxyethyl-triazole derivative of the formula (XXI) can be present in the “thiono” form of the formula




or in the tautomeric “mercapto” form of the formula





For simplicity's sake, only the “thiono” form is given in each case.
The guanidine derivative of the formula (XXV) is a substance mixture with the common name guazatine.
From the structural formula for the active compouds of the formula (XXXXIX), it can be seen that the compounds can be present as E or Z isomers. Accordingly, the product can be present as a mixture of different isomers or else in the form of a single isomer. Preference is given to compounds of the formula (XXXXIX) in which the compounds of the formula (XXXXIX) are present as E isomer. Particular preference is given to the compounds of the formulae




and their isomers.

The following active compounds are particularly preferred mixing partners of the compounds of the formula (I):

    
    
        (3) tolylfluanid (IVb),
        (5) propineb (VI),
        (6) mancozeb (VIIc),
        (7) fenhexamid (VIII),
        (8) iprovalicarb (VIII),
        (11) azoxystrobin (XII),
        (12) trifloxystrobin (XIII),
        (13) compound of the formula (XIV),
        (18) folpet (XIX),
        (20) compound of the formula (XXI),
        (26) compound of the formula (XXVII),
        (27) compound of the formula (XXVIII),
        (28) chlorothalonil (XXIX),
        (30) fluazinam (XXXI), and
        (45) copper compounds
        
            a) copper oxychloride (XXXXVIa)
            b) copper hydroxide (XXXXVIb).
        
        
    
    


The components which are present in the active combinations according to the invention in addition to a halogeno-benzimidazole of the formula (XXVII) are also known.
Specifically, the active compounds are described in the following publications:

    
    
        (1) compounds of the formula (II)
        
            DE-A 22 01 063
            DE-A 23 24 010
        
        
        (2) compound of the formula (III)
        
            EP-A 0 040 345
        
        
        (3) compounds of the formula (IV)
        
            Pesticide Manual, 9th Ed. (1991), pages 249 and 827
        
        
        (4) compound of the formula (V) and individual derivatives thereof
        
            EP-A 0 341 475
        
        
        (5) compound of the formula (VI)
        
            Pesticide Manual, 9th Ed. (1991), page 726
        
        
        (6) compounds of the formula (VII)
        
            Pesticide Manual, 9th Ed. (1991), pages 529, 531 and 866
        
        
        (7) compound of the formula (VII)
        
            EP-A 0 339 418
        
        
        (8) compound of the formula (IX)
        
            EP-A 0 472 996
        
        
        (9) compound of the formula (X)
        
            EP-A 0 313 512
        
        
        (10) compound of the formula (XI)
        
            EP-A 0 281 842
        
        
        (11) compound of the formula (XII)
        
            EP-A 0 382 375
        
        
        (12) compound of the formula (XIII)
        
            EP-A-460 575
        
        
        (13) compound of the formula (XIV)
        
            DE-A 196 02 095
        
        
        (14) compound of the formula (XV)
        
            Pesticide Manual, 9th Ed. (1991), page 206
        
        
        (15) compounds of the formula (XVI)
        
            EP-A 0 270 111
            EP-A 0 310 550
        
        
        (16) compound of the formula (XVII)
        Pesticide Manual, 9th Ed. (1991), page 554
        (17) compound of the formula (XVI)
        
            EP-A 0 219 756
        
        
        (18) compound of the formula (XIX)
        
            Pesticide Manual, 9th Ed. (1991), page 431
        
        
        (19) compound of the formula (XX)
        
            Pesticide Manual, 9th Ed. (1991), page 443
        
        
        (20) compound of the formula (XXI)
        
            WO 96-16048
        
        
        (21) compound of the formula (XXII)
        
            Pesticide Manual, 9th Ed. (1991), page 491
        
        
        (22) compound of the formula (XXII)
        
            EP-A 0 393 911
        
        
        (23) compound of the formula (XXIV)
        
            EP-A 0 600 629
        
        
        (24) substance of the formula (XXV)
        
            Pesticide Manual, 9th Ed. (1991), page 461
        
        
        (25) compound of the formula (XXVI)
        
            Pesticide Manual, 9th Ed. (1991), page 654
        
        
        (26) compound of the formula (XXVII)
        
            WO 97-06171
        
        
        (27) compound of the formula (XXVIII)
        
            DE-A1-196 46 407, EP-B-0 712 396
        
        
        (28) compound of the formula (XXIX)
        
            U.S. Pat. No. 3,290,353
        
        
        (29) compound of the formula (XXX)
        
            DE-A-156 7169
        
        
        (30) compound of the formula (XXXI)
        
            EP-A-0 031 257
        
        
        (31) compound of the formula (XXXI)
        
            EP-A-0 639 547
        
        
        (32) compound of the formula (XXXXI)
        
            EP-A-0 298 196
        
        
        (33) compound of the formula (XXXIV)
        
            EP-A-600 629
        
        
        (34) compound of the formula (XXXV)
        
            DE-A-2 149 923
        
        
        (35) compound of the formula (XXXVI)
        
            DE-A-2 012 656
        
        
        (36) compound of the formula (XXXVII)
        
            U.S. Pat. No. 1,972,961
        
        
        (37) compound of the formula (XXXVII)
        
            EP-A-326 330
        
        
        (38) compound of the formula (XXXIX)
        
            EP-A 278 595
        
        
        (39) compound of the formula (XXXX)
        
            DE-A-3 030 026
        
        
        (40) compound of the formula (XXXXI)
        
            DE-A-2 903 612
        
        
        (41) compound of the formula (XXXXII)
        
            U.S. Pat. No. 2,553,770
        
        
        (42) compound of the formula (XXXXIII)
        
            known and commercially available
        
        
        (43) compound of the formula (XXXXIV)
        
            EP-A-206 999
        
        
        (44) compound of the formula (XXXXV)
        
            EP-A-78 663
        
        
        (45) a) compound of the formula (XXXXVIa) known and commercially available
        b) compound of the formula (XXXXVIb) known and commercially available
        (46) compound of the formula (XXXXVII)
        
            DE-A-2 429 523
        
        
        (47) a) compound of the formula (XXXXVIIIa)
        
            EP-A-112 284
        
        
        b) compound of the formula (XXXXVIIIb)
        
            DE-A-3 042 303
        
        
        c) compound of the formula (XXXXVIIIc)
        
            DE-A-3 406 993
        
        
        d) compound of the formula (XXXXVIIId)
        
            EP-A-68 813
        
        
        e) compound of the formula (XXXXVIIIe)
        
            DE-A-2551560
        
        
        f) compound of the formula (XXXXVIII)
        
            EP-A-145 294
        
        
        g) compound of the formula (XXXXVIIIg)
        
            DE-A-3 721 786
        
        
        h) compound of the formula (XXXXVIIIh)
        
            EP-A-234 242
        
        
        (48) compound of the formula (XXXXIX)
        
            WO 96/23763
        
        
        (49) compound of the formula (XXXXX)
        
            EP-A-596 254
        
        
        (50) compound of the formula (XXXXXI)
        
            WO 98/23155
        
        
        (50) compound of the formula (XXXXXII)
        
            EP-A-569 384.
        
        
    
    


In addition to an active compound of the formula (I), the active compound combinations according to the invention comprise at least one active compound of the compounds of groups (1) to (51). Additionally, they may comprise further fungicidally active additives.
The synergistic effect is particularly pronounced when the active compounds in the active compound combinations according to the invention are present in certain weight ratios. However, the weight ratios of the active compounds in the active compound combinations can be varied within a relatively wide range. In general,

    
    
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (1),
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (2),
        from 1 to 150 parts by weight, preferably from 1 to 100 parts by weight, of active compound of group (3),
        from 0.1 to 10 parts by weight, preferably from 0.2 to 5 parts by weight, of active compound of group (4),
        from 1 to 150 parts by weight, preferably from 5 to 100 parts by weight, of active compound of group (5),
        from 1 to 150 parts by weight, preferably from 5 to 100 parts by weight, of active compound of group (6),
        from 0.1 to 50 parts by weight, preferably from 1 to 20 parts by weight, of active compound of group (7),
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (8),
        from 0.02 to 50 parts by weight, preferably from 0.1 to 10 parts by weight, of active compound of group (9),
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (10),
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (11),
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (12),
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (13),
        from 0,1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (14),
        from 0.2 to 50 parts by weight, preferably from 1 to 20 parts by weight, of active compound of group (15),
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (16),
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (17),
        from 1 to 150 parts by weight, preferably from 5 to 100 parts by weight, of active compound of group (18),
        from 0.1 to 150 parts by weight, preferably from 1 to 100 parts by weight, of active compound of group (19),
        from 0.02 to 50 parts by weight, preferably from 0.2 to 10 parts by weight, of active compound of group (20),
        from 0.05 to 20 parts by weight, preferably from 0.1 to 10 parts by weight, of active compound of group (21),
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (22),
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (23),
        from 0.01 to 150 parts by weight, preferably from 1 to 100 parts by weight, of active compound of group (24),
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (25),
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (26),
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (27),
        from 1 to 150 parts by weight, preferably from 5 to 100 parts by weight, of active compound of group (28),
        from 1 to 150 parts by weight, preferably from 5 to 100 parts by weight, of active compound of group (29),
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (30),
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (31),
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (32),
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (33),
        from 0.1 to 50 parts by weight, preferably 1 to 20 parts by weight, of active compound of group (34), from 0.1 to 50 parts by weight, preferably from 1 to 10 parts by weight, of active compound of group (35),
        from 1 to 150 parts by weight, preferably from 5 to 100 parts by weight, of active compound of group (36),
        from 0.1 to 50 parts by weight, preferably from 0,2 to 20 parts by weight, of active compound of group (37).
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (38),
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (39),
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (40),
        from 1 to 150 parts by weight, preferably from 5 to 100 parts by weight, of active compound of group (41),
        from 1 to 150 parts by weight, preferably from 5 to 100 parts by weight, of active compound of group (42),
        from 0.1 to 50 parts by weight, preferably from 1 to 20 parts by weight, of active compound of group (43),
        from 0.1 to 50 parts by weight, preferably from 1 to 20 parts by weight, of active compound of group (44),
        from 1 to 150 parts by weight, preferably from 5 to 100 parts by weight, of active compound of group (45a),
        from 1 to 150 parts by weight, preferably from 5 to 100 parts by weight, of active compound of group (45b),
        from 0.1 to 50 parts by weight, preferably from 0,2 to 20 parts by weight, of active compound of group (46),
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (47a),
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (47b),
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (47c),
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (47d),
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (47e),
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (47f),
        from 0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight, of active compound of group (47g),
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (47h),
        from 0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight, of active compound of group (48),
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (49),
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (50),
        from 0.1 to 50 parts by weight, preferably from 0.2 to 20 parts by weight, of active compound of group (51)
        are present per part by weight of active compound of the formula (I).
    
    


The active compound combinations according to the invention have very good fungicidal properties and can be employed for controlling phytopathogenic fungi, such as Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes, etc.
The active compound combinations according to the invention are particularly suitable for controlling Phytophthora infestans and Plasmopara viticola. 
The fact that the active compound combinations are well tolerated by plants at the concentrations required for controlling plant diseases permits the 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 employed for foliar application or else as seed dressings.
The active compound combinations according to the invention may also be employed to increase the yield of crops. However, they have reduced toxicity and are tolerated well by plants.
According to the invention, it is possible to treat all plants and parts of plants. Plants are to be understood here as meaning all plants and plant populations such as desired and undesired wild plants or crop plants (including naturally occurring crop plants). Crop 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 plant cultivars which can or cannot be protected by plant breeders certificates. Parts of plants are to be understood as meaning all above-ground and below-ground parts and organs of plants, such as shoot, leaf, flower and root, examples which may be mentioned being leaves, needles, stems, trunks, flowers, fruit-bodies, fruits and seeds and also roots, tubers and rhizomes. Parts of plants also include harvested plants and vegetative and generative propagation material, for example seedlings, tubers, rhizomes, cuttings and seeds.
The treatment of the plants and parts of plants according to the invention with the active compounds is carried out directly or by action on their environment, habitat or storage area according to customary treatment methods, for example by dipping, spraying, evaporating, atomizing, broadcasting, brushing-on and, in the case of propagation material, in particular in the case of seeds, furthermore by one- or multi-layer coating.
The active compound combinations according to the invention can be converted to the customary formulations, such as solutions, emulsions, suspensions, powders, foams, pastes, granules, aerosols and microencapsulations in polymeric substances and in coating compositions for seeds, and ULV formulations.
These formulations are produced in a known manner, for example by mixing the active compounds or active compound combinations with extenders, that is liquid solvents, liquefied gases under pressure, and/or solid carriers, optionally with the use of surfactants, that is emulsifiers and/or dispersants, and/or foam formers. If the extender used is water, it is also possible to use, for example, organic solvents as auxiliary solvents. Essentially, suitable liquid solvents include: aromatics such as xylene, toluene or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic hydrocarbons such as chlorobenzenes, chloroethylenes 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 sulphoxide, or else water. Liquefied gaseous extenders or carriers are to be understood as meaning liquids which are gaseous at ambient temperature and under atmospheric pressure, for example aerosol propellants such as butane, propane, nitrogen and carbon dioxide. Suitable solid carriers are: for example ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals such as finely divided silica, alumina and silicates. Suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, or else synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks. Suitable emulsifiers and/or foam formers are: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates, or else protein hydrolysates. Suitable dispersants are: for example lignin-sulphite waste liquors and methylcellulose.
Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, or else natural phospholipids such as cephalins and lecithins and synthetic phospholipids can be used in the formulations. Other additives can be mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations generally comprise between 0.1 and 95% by weight of active compounds, preferably between 0.5 and 90%.
The active compound combinations according to the invention, as such or in their formulations, can also be applied in a mixture with known fungicides, bactericides, acaricides, nematicides or insecticides, to broaden the activity spectrum or to prevent the development of resistance, for example. In many cases, synergistic effects are obtained, i.e. the activity of the mixture is greater than the activity of the individual components.
A mixture with other known active compounds such as herbicides or with fertilizers and growth regulators is also possible.
The active compound combinations can be used as such, in the form of their formulations or as 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 watering, spraying, atomizing, scattering, spreading, and as a powder for dry seed treatment, a solution for seed treatment, a water-soluble powder for seed treatment, a water-soluble powder for slurry treatment, or by encrusting.
When using the active compound combinations according to the invention, the application rates can be varied within a relatively wide range, depending on the kind of application. In the treatment of parts of plants, the application rates of the active compound combination are generally between 0.1 and 10,000 g/ha, preferably between 10 and 1000 g/ha. In the treatment of seeds, the application rates of the active compound combination are generally between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. In the treatment of the soil, the application rates of the active compound combination are generally between 0.1 and 10,000 g/ha, preferably between 1 and 5000 g/ha.
The good fungicidal activity of the active compound combinations according to the invention is evident from the examples below. While the individual active compounds exhibit weaknesses with regard to the fungicidal activity, the combinations have an activity which exceeds the sum of individual activities.
A synergistic effect of fungicides is always present when the fungicidal activity of the active compound combinations exceeds the total of the activities of the active compounds when applied individually.
The expected activity for a given combination of two active compounds can be calculated as follows (cf. Colby, S. R., “Calculating Synergistic and Antagonistic Responses of Herbicide Combinations”, Weeds 15, (1967), 20–22):

    
    
        If
        X is the efficacy when applying active compound A at an application rate of m g/ha,
        Y is the efficacy when applying active compound B at an application rate of n g/ha and
        E is the efficacy when applying the active compounds A and B at an application rate of m and n g/ha,
        then
    
    






  E
  =
  
    X
    +
    Y
    -
    
      
        X
        ·
        Y
      
      100
    
  




The efficacy is calculated in %. 0% is an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.
If the actual fungicidal activity exceeds the calculated value, then the activity of the combination is superadditive, i.e. a synergistic effect exists. In this case, the efficacy which was actually observed must be greater than the value for the expected efficacy (E) calculated from the abovementioned formula.
The examples that follow illustrate the invention. However, the invention is not limited to the examples.


EXAMPLE 1
Phytophthora Test (Tomato)/Protective
















Solvent:
47 parts by weight of acetone



Emulsifier:
 3 parts by weight of alkylaryl polyglycol ether










To produce a suitable preparation of active compound, 1 part by weight of active compound or active compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration, or a commercial formulation of active compound or active compound combination is diluted with water to the desired concentration.
To test for protective activity, young plants are sprayed with the active compound preparation at 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 about 20° C. and 100% relative atmospheric humidity.
Evaluation is carried out 3 days after the inoculation. 0% means an efficacy which corresponds to that of the control, whereas an efficacy of 100% means that no infection is observed.
The activity found for the active compound combination according to the invention is greater than the calculated activity, i.e. there is a synergistic effect. At a mixing ratio of 1:1 and an application rate of 0.1 g/ha, the combination of the compound of the formula (I) and the halogeno-benzimidazole of the formula No. XXVII has an actual efficacy of 73%. At 63%, the expected value, calculated using Colby's formula, is considerably lower.
Active compounds, application rates and test results are shown in the tables below.







TABLE 1





Phytophthora test (tomato)/protective


















Active compound



Active compound
application rate


known:
in g/ha
Efficacy in %





compound of the formula (XXVII)
0.1
30


 








 


compound of the formula (I)
0.1
47


 











 


Mixture according to the invention:













Active






compound

Expected value,




application
Actual
calculated using


Active compound
Mixing ratio
rate in g/ha
efficacy
Colby's formula
















XXVII


0.1





+
 {close oversize brace} 
1:1
+
 {close oversize brace} 
73
63


I


0.1
















TABLE 2





Phytophthora test (tomato)/protective


















Active compound



Active compound
application rate


known:
in g/ha
Efficacy in %





compound of the formula (I)
 1
47


 








 


propineb (VI)
20
19


 
















Mixture according to the invention













Active






compound

Expected value




application
Actual
calculated using



Mixing ratio
rate in g/ha
efficacy
Colby's formula
















(I)


 1





+
 {close oversize brace} 
1:20
+
 {close oversize brace} 
94
57


propineb (VI)


20
















TABLE 3





Phytophthora test (tomato)/protective


















Active compound



Active compound
application rate
Efficacy


known:
in g/ha
in %












compound of the formula (I)
 1
47


 








 


chlorothalonil (XXIX)
20
12


 
















Mixture according to the invention:













Active compound

Expected value,




application
Actual
calculated using



Mixing ratio
rate in g/ha
efficacy
Colby's formula
















(I)


 1





+
 {close oversize brace} 
1:20
+
 {close oversize brace} 
84
53


chlorothalonil (XXIX)


20
















TABLE 4





Phytophthora test (tomato)/protective


















Active compound




application rate
Efficacy


Active compound known:
in g/ha
in %





compound of the formula (I)
 1
47


 








 


dichlofluanid (IVa)
20
 5


 
















Mixture according to the invention:













Active compound

Expected value,




application
Actual
calculated using



Mixing ratio
rate in g/ha
efficacy
Colby's formula
















(I)


 1





+
 {close oversize brace} 
01:20
+
 {close oversize brace} 
87
50


dichlofluanid (IVa)


20
















TABLE 5





Phytophthora test (tomato)/protective


















Active compound




application rate
Efficacy


Active compound known:
in g/ha
in %





compound of the formula (I)
 1
47


 








 


tolylfluanid (IVb)
20
21


 
















Mixture according to the invention:













Active compound

Expected value,




application
Actual
calculated using



Mixing ratio
rate in g/ha
efficacy
Colby's formula
















(I)


 1





+
 {close oversize brace} 
1:20
+
 {close oversize brace} 
95
58


tolylfluanid (IVa)


20
















TABLE 6





Phytophthora test (tomato)/protective


















Active compound



Active compound
application rate in



known:
g/ha
Efficacy in %





compound of the formula (I)
1
47


 








 


folpet (XIX)
20
0


 

























Active








compound


Expected value





application

Actual
calculated using


Mixture according to the invention:

Mixing ratio
rate in g/ha

efficacy
Colby's formula





(I)


1


+
 {close oversize brace} 
1:20
+
 {close oversize brace} 
95
47


folpet (XIX)


20
















TABLE 7







Phytophthora test (tomato)/protective










Active compound



Active compound
application rate in


known:
g/ha
Efficacy in %





compound of the formula (I)
 1
39








 


mancozeb (VIIc)
20
28










Mixture according to the invention:













Active






compound

Expected value




application
Actual
calculated using



Mixing ratio
rate in g/ha
efficacy
Colby's formula

















(I)


 1





+
 {close oversize brace} 
1:20
+
 {close oversize brace} 
68
56


mancozeb (VIIc)


20
















TABLE 8







Phytophthora test (tomato)/protective










Active compound



Active compound
application rate in


known:
g/ha
Efficacy in %





compound of the formula (I)
 1
47








 


bitertanol (IIc)
10
 4










Mixture according to the invention:













Active






compound

Expected value




application
Actual
calculated using



Mixing ratio
rate in g/ha
efficacy
Colby's formula

















(I)


 1





+
 {close oversize brace} 
1:10
+
 {close oversize brace} 
73
49


bitertanol (IIc)


10
















TABLE 9







Phytophthora test (tomato)/protective










Active compound



Active compound
application rate in


known:
g/ha
Efficacy in %





compound of the formula (I)
 1
47








 


tebuconazole (III)
10
 5
















Mixture according to the invention:













Active






compound

Expected value




application
Actual
calculated using



Mixing ratio
rate in g/ha
efficacy
Colby's formula

















(I)


 1





+
 {close oversize brace} 
1:10
+
 {close oversize brace} 
73
50


tebuconazole


10


(III)
















TABLE 10







Phytophthora test (tomato)/protective










Active compound



Active compound
application rate in


known:
g/ha
Efficacy in %





compound of the formula (I)
 1
47








 


triadimenol (IIb)
10
 0
















Mixture according to the invention:













Active






compound

Expected value




application
Actual
calculated using



Mixing ratio
rate in g/ha
efficacy
Colby's formula

















(I)


 1





+
 {close oversize brace} 
1:10
+
 {close oversize brace} 
88
47


triadimenol (IIb)


10
















TABLE 11







Phytophthora test (tomato)/protective










Active compound



Active compound
application rate in


known:
g/ha
Efficacy in %





compound of the formula (I)
 1
47








 


imidacloprid (XXII)
10
 0
















Mixture according to the invention:













Active






compound

Expected value




application
Actual
calculated using



Mixing ratio
rate in g/ha
efficacy
Colby's formula

















(I)


 1





+
 {close oversize brace} 
1:10
+
 {close oversize brace} 
71
47


imidacloprid (XXII)


10
















TABLE 12







Phytophthora test (tomato)/protective










Active compound



Active compound
application rate in


known:
g/ha
Efficacy in %





compound of the formula (I)
 1
47








 


compound of the formula (XXI) (20)
10
 2
















Mixture according to the invention:













Active






compound

Expected value




application
Actual
calculated using



Mixing ratio
rate in g/ha
efficacy
Colby's formula

















(I)


 1





+
 {close oversize brace} 
1:10
+
 {close oversize brace} 
62
48


(XXI) (20)


10
















TABLE 13







Phytophthora test (tomato)/protective










Active compound



Active compound
application rate in


known:
g/ha
Efficacy in %





compound of the formula (I)
 1
47








 


fenhexamid (VIII)
10
13
















Mixture according to the invention:













Active






compound

Expected value




application
Actual
calculated using



Mixing ratio
rate in g/ha
efficacy
Colby's formula

















(I)


 1





+
 {close oversize brace} 
1:10
+
 {close oversize brace} 
70
54


fenhexamid (VIII)


10
















TABLE 14







Phytophthora test (tomato)/protective










Active compound



Active compound
application rate in


known:
g/ha
Efficacy in %





compound of the formula (I)
 1
47








 


carpropamid (V)
10
 0
















Mixture according to the invention:













Active






compound

Expected value




application
Actual
calculated using



Mixing ratio
rate in g/ha
efficacy
Colby's formula

















(I)


 1





+
 {close oversize brace} 
1:10
+
 {close oversize brace} 
90
47


carpropamid (V)


10
















TABLE 15







Phytophthora test (tomato)/protective










Active compound



Active compound
application rate in


known:
g/ha
Efficacy in %





compound of the formula (I)
 1
47








 


spiroxamine (XI)
10
 0
















Mixture according to the invention:













Active






compound

Expected value




application
Actual
calculated using



Mixing ratio
rate in g/ha
efficacy
Colby's formula

















(I)


 1





+
 {close oversize brace} 
1:10
+
 {close oversize brace} 
86
47


spiroxamine (XI)


10
















TABLE 16







Phytophthora test (tomato)/protective










Active compound



Active compound
application rate in


known:
g/ha
Efficacy in %





compound of the formula (I)
 1
39








 


fluazinam (XXXI)
10
56
















Mixture according to the invention:













Active






compound

Expected value




application
Actual
calculated using



Mixing ratio
rate in g/ha
efficacy
Colby's formula

















(I)


 1





+
 {close oversize brace} 
1:10
+
 {close oversize brace} 
87
73


fluazinam (XXXI)


10
















TABLE 17







Phytophthora test (tomato)/protective










Active compound



Active compound
application rate in


known:
g/ha
Efficacy in %





compound of the formula (I)
1
47








 


compound of the formula (XXVIII) (27)
1
 9
















Mixture according to the invention:













Active






compound

Expected value




application
Actual
calculated using



Mixing ratio
rate in g/ha
efficacy
Colby's formula

















(I)


1





+
 {close oversize brace} 
1:1
+
 {close oversize brace} 
72
52


(XXVIII) (27)


1
















TABLE 18







Phytophthora test (tomato)/protective










Active compound



Active compound
application rate in


known:
g/ha
Efficacy in %





compound of the formula (I)
1
47


 








 


compound of the formula (XIV) (13)
1
 8


 
















Mixture according to the invention:















Expected




Active

value




compound

calculated




application
Actual
using Colby's



Mixing ratio
rate in g/ha
efficacy
formula

















(I)


1





+
 {close oversize brace} 
1:1
+
 {close oversize brace} 
62
51


(XIV) (13)


1
















TABLE 19







Phytophthora test (tomato)/protective










Active




compound


Active compound
application rate


known:
in g/ha
Efficacy in %





formula (I)
 1
56








 


compound of the formula (XXXXVIa) (40)
50
 0


copper oxychloride










Mixture according to the invention:













Active






compound

Expected value




application
Actual
calculated using



Mixing ratio
rate in g/ha
efficacy
Colby's formula

















formula (I)


 1





+
 {close oversize brace} 
1:50
+
 {close oversize brace} 
82
56


copper oxychloride (XXXXVIa)


50
















TABLE 20







Phytophthora test (tomato)/protective










Active




compound


Active compound
application rate


known:
in g/ha
Efficacy in %





formula (I)
1
56








 


compound of the formula (XII) (11)
1
55


azoxystrobin
















Mixture according to the invention:













Active






compound

Expected value




application

calculated using



Mixing ratio
rate in g/ha
Actual efficacy
Colby's formula

















formula (I)


1





+
 {close oversize brace} 
1:1
+
 {close oversize brace} 
95
80


azoxystrobin (XXI)


1
















TABLE 21







Phytophthora test (tomato)/protective










Active




compound


Active compound
application rate


known:
in g/ha
Efficacy in %





formula (I)
1
56








 


compound of the formula (XIII) (12)
1
 0


trifloxystrobin
















Mixture according to the invention:













Active






compound

Expected value



Mixing
application
Actual
calculated using



ratio
rate in g/ha
efficacy
Colby's formula

















formel (I)


1





+
 {close oversize brace} 
1:1
+
 {close oversize brace} 
68
56


trifloxystrobin (XIII)


1

## Claims

1. A synergistic active compound combination comprising at least one compound of formula (I)




and the phosphorus compound of formula (XX), and wherein the weight ratio of the compound of the formula (I) to the compound of formula (XX) is from 1:0.1 to 1:150