(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)
`
`(10) International Publication Number
`
`WO 2017/207444 A1
`
`h a
`
`WIPOI PCT
`
`(19) World Intellectual Property
`Organization
`International Bureau
`
`(43) International Publication Date
`07 December 2017 (07.12.2017)
`
`(51) International Patent Classification:
`A01N 43/56 (2006.01)
`A01P 3/00 (2006.01)
`A01N 43/58 (2006.01)
`
`(21) International Application Number:
`
`PCT/EP2017/062795
`
`(22) International Filing Date:
`
`(25) Filing Language:
`
`(26) Publication Language:
`
`26 May 2017 (26.05.2017)
`
`English
`
`English
`
`SD, SE, SG, SK, SL, SM, ST, SV, SY, TH, TJ, TM, TN, TR,
`TT, TZ, UA, UG, US, UZ, vc, VN, ZA, ZM, ZW.
`
`(84) Designated States (unless otherwise indicated, for every
`kind ofregional protection available): ARIPO (BW, GH,
`GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, ST, SZ, TZ,
`UG, ZM, ZW), Eurasian (AM, AZ, BY, KG, KZ, RU, TJ,
`TM), European (AL, AT, BE, BG, CH, CY, CZ, DE, DK,
`EE, ES, FI, FR, GB, GR, HR, HU, IE, IS, IT, LT, LU, LV,
`MC, MK, MT, NL, NO, PL, PT, RO, RS, SE, SI, SK, SM,
`TR), OAPI (BF, BJ, CF, CG, CI, CM, GA, GN, GQ, GW,
`KM, ML, MR, NE, SN, TD, TG).
`
`(30) Priority Data:
`16095747
`
`01 June 2016 (01.06.2016)
`
`GB
`
`Declarations under Rule 4.17:
`
`as to applicant’s entitlement to applyfor and be granted a
`patent (Rule 4.17(ii))
`ofinventorship (Rule 4.1 7(iv))
`Published:
`
`with international search report (Art. 21(3))
`
`SYNGENTA PARTICIPATIONS AG
`(71) Applicant:
`[CH/CH]; Schwarzwaldallee 215, 4058 Basel (CH).
`
`(72) Inventors: FORSTER, Birgit; Syngenla Crop Protection
`AG Schwarzwaldallee 215, 4058 Basel (CH). GRASSO,
`Valeria; Syngenta Crop Protection AG Schaffhauser-
`slrasse, 4332 Stein (CH).
`
`(74)
`
`Agent: SYNGENTA INTERNATIONAL AG; Sch-
`warzwaldallee 215 (WRO B8-Zl -30), 4058 Basel (CI I).
`
`(81) Designated States (unless otherwise indicated, for every
`kind ofnational protection available): AE, AG, AL, AM,
`AO, AT, AU, AZ, BA, BB, BG, BH, BN, BR, BW, BY, BZ,
`CA, CH, CL, CN, CO, CR, CU, CZ, DE, DJ, DK, DM, DO,
`DZ, EC, EE, EG, ES, Fl, GB, GD, GE, GH, GM, GT, HN,
`HR, HU, ID, IL, IN, IR, IS, JP, KE, KG, KH, KN, KP, KR,
`KW, KZ, LA, LC, LK, LR, LS, LU, LY, MA, MD, ME, MG,
`MK, MN, MW, MX, MY, MZ, NA, NG, NI, NO, NZ, OM,
`PA, PE, PG, PH, PL, PT, QA, RO, RS, RU, RW, SA, SC,
`
`(54) Title: FUNGICIDAL COMPOSITIONS
`
`(57) Abstract: The present invention relates to novel fungicidal compositions for the treatment
`of phytopathogenic diseases of useful plants, especially phytopathogenic fungi, and to a method
`of controlling such phytopathogenic diseases on useful plants. In particular compositions suitable
`for control of diseases caused by phytopathogens comprise a mixture of a compound of formula
`(I) with a compound of formula (II) and a method of controlling diseases 0n useful plants using
`such compositions.
`
`F
`
`\
`
`I
`N\N
`
`R8
`
`N\
`
`R
`
`(I)
`
`
`
`
`
`wo2017/207444A1|||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||||
`
`

`

`WO 2017/207444
`
`PCT/EP2017/062795
`
`FUNGICIDAL COMPOSITIONS
`
`The present invention relates to novel fungicidal compositions for the treatment of
`
`phytopathogenic diseases of useful plants, especially phytopathogenic fungi, and to a
`
`method of controlling such diseases, and/or fungi, on useful plants.
`
`It is known from W02008/148570, WO 2010/063700, WO 2010/084078 and WO
`
`2008/151828 that certain pyrazonI-carboxamide derivatives have biological activity against
`
`phytopathogenic fungi. On the other hand various fungicidal compounds of different
`
`chemical classes are widely known as plant fungicides for application in various crops of
`
`cultivated plants. However, crop tolerance and activity against phytopathogenic plant fungi
`
`do not always satisfy the needs of agricultural practice in many incidents and aspects. In
`
`order to overcome this problem, some binary mixtures of pyrazonI-carboxamides with
`
`certain fungicides have been provided in WO 2012/041874, and WO 2015/049178.
`
`Fungicidal pyridazine derivatives are disclosed in EP1767529A1, and binary mixtures
`
`of such compounds with Qol inhibitors are disclosed in EP2604116A1.
`
`1O
`
`15
`
`The present invention provides a composition suitable for control of diseases caused
`
`by phytopathogens comprising, as component (A), a compound of formula (I)
`
`H ,4ng
`0
`
`f,
`m N“
`
`R
`
`F
`dimw M
`F w
`
`5:”:
`M,
`
`i
`”7:57"
`
`(f; H 25%
`
`20
`
`wherein
`
`R is hydrogen or methoxy;
`
`Q is
`
`M
`w. L~~~~~ ‘3’
`I
`
`mg,
`
`(I).
`
`R,
`
`fix. «it
`
`1
`
`R2 W .5:
`(Q1) or
`f?““""”:3
`
`(Qz);
`
`

`

`WO 2017/207444
`
`PCT/EP2017/062795
`
`wherein
`
`R1 is hydrogen, halogen or C1-Csalkyl;
`
`R2 is hydrogen, halogen, C1-Cealkyl, Cz-Cealkenyl, Ca-Cealkinyl, Ca-Cecycloalkyl-Ca-
`
`Csalkinyl, halophenoxy, halophenyl-Cs-Cealkinyl, C(C1-C4alkyl)=NO-C1-C4alkyl, C1-
`
`Cshaloalkyl,
`
`C1—Cehaloalkoxy, C2—Cehaloalkenyl, or Cz—Cshaloalkenyloxy;
`
`R3 is hydrogen, halogen or C1-Csalkyl; with the proviso that at least one of R1, R2 and
`
`R3 is different from hydrogen;
`
`R4, R5 and R5, independently from each other, are hydrogen, halogen or -E-R7; with
`
`the proviso that at least one of R4, R5 and R6 is different from hydrogen;
`
`R7 is hydrogen, C1-Csalkyl, C1-Cshaloalkyl or C1-C4alkoxyalkyl; and
`
`R3 is hydrogen or methoxy;
`
`and agrochemically acceptable salts, stereoisomers, diastereoisomers, enantiomers
`
`and tautomers of those compounds;
`
`and as component (B), a compound of formula (II)
`
`R2)“;
`
`
`
`(II) or an agrochemically acceptable salt thereof, wherein,
`
`R21 is hydrogen or halogen;
`
`R22, R23 and R24 are each independently hydrogen or halogen; and,
`
`R25 is halogen or cyano.
`
`In a further aspect, the invention provides a method of controlling phytopathogenic
`
`diseases on useful plants or on propagation material thereof, which comprises applying to
`
`the useful plants, the locus thereof or propagation material thereof a combination of
`
`components (A) and (B) as described herein.
`
`The compounds of formula (I) wherein R3 is hydrogen can occur in the two
`
`enantiomeric forms of formula (la) and (lb):
`
`10
`
`15
`
`20
`
`25
`
`

`

`WO 2017/207444
`
`PCT/EP2017/062795
`
`_ 3 _
`
`H3C
`
`\H
`3:
`
`Q
`
`H30,
`
`H
`
`H
`
`N\R
`
`R8
`
`F
`
`and
`
`Ia
`
`(
`
`)
`
`F
`
`F O\
`
`H
`
`/
`
`N\
`
`\
`
`l”
`CH3
`
`1 Z éQ
`N\
`R8
`
`R
`
`H
`
`|b .
`
`)
`
`(
`
`o
`
`F
`
`H
`
`\
`
`N,
`‘,N
`CH3
`
`The invention encompasses both enantiomeric forms of the compounds of formula (I).
`
`The compounds of formula (I) and their preparation are described in WO 2010/063700,
`
`WO 2010/084078 and WO 2008/151828.
`
`Compounds of formula (II) and their preparation are described in EP1767529A, and
`
`EP2604116A1.
`
`It has been found that the use of a compound of formula (II) in combination with a
`
`compound of formula (I) surprisingly and substantially may enhance the effectiveness of the
`
`latter against fungi, and vice versa. Additionally, the method of the invention is effective
`
`against a wider spectrum of such fungi than can be combated with the individual active
`
`ingredients, when used solely.
`
`In general, the weight ratio of component (A) to component (B) is from 1000:1 to
`
`1:1000, especially from 80:1 to 1:80, more especially in a ratio from 40:1 to 1:40, even more
`
`especially in a ratio of from 20:1 to 1:20, even more especially still from 10:1 to 1:10, very
`
`especially from 5:1 and 1:5, and in particular from 5:2 to 2:5. Special preference is given to
`
`a ratio of from 1:80 to 2:5. Specific individual ratios that are preferred include the ratio of
`
`1:1, 5:1, 5:2, 5:3, 5:4, 4:1, 4:2, 4:3, 3:1, 3:2, 2:1, 1:5, 2:5, 3:5, 4:5, 1:4, 2:4, 3:4, 1:3, 2:3,
`
`1:2, 1:600, 1:300, 1:150, 1:100, 1:50, 1;40, 1:35, 1:20, 2:35, 4:35, 1:10 1:75, 2:75, 4:75,
`
`1:6000, 1:3000, 1:1500, 1:350, 2:350, 4:350, 1:750, 2:750, and 4:750. Out of these, 1:80,
`
`1:40, 1:20, 1:10, 1:5 and 2:5 are particularly preferred.
`
`It has been found, surprisingly, that certain weight ratios of component (A) to
`
`component (B) are able to give rise to synergistic activity. Therefore, a further aspect of the
`
`invention are compositions, wherein component (A) and component (B) are present in the
`
`composition in amounts producing a synergistic effect. This synergistic activity is apparent
`
`from the fact that the fungicidal activity of the composition comprising component (A) and
`
`component (B) is greater than the sum of the fungicidal activities of component (A) and
`
`component (B). This synergistic activity extends the range of action of component (A) and
`
`component (B) in two ways. Firstly, the rates of application of component (A) and
`
`1O
`
`15
`
`2O
`
`25
`
`

`

`WO 2017/207444
`
`PCT/EP2017/062795
`
`component (B) are lowered whilst the action remains equally good, meaning that the active
`
`ingredient mixture still achieves a high degree of phytopathogen control even where the two
`
`individual components have become totally ineffective in such a low application rate range.
`
`Secondly, there is a substantial broadening of the spectrum of phytopathogens that can be
`
`controlled.
`
`A synergistic effect exists whenever the action of an active ingredient combination is
`
`greater than the sum of the actions of the individual components. The action to be expected
`
`E for a given active ingredient combination obeys the so-called COLBY formula and can be
`
`calculated as follows (COLBY, SR. "Calculating synergistic and antagonistic responses of
`
`1O
`
`herbicide combination", Weeds, Vol. 15, pages 20-22; 1967):
`
`ppm = milligrams of active ingredient (= a.i.) per liter of spray mixture
`
`X = % action by active ingredient (A) using p ppm of active ingredient
`
`Y = % action by active ingredient (B) using q ppm of active ingredient.
`
`According to COLBY, the expected (additive) action of active ingredients (A)+(B) using
`
`15
`
`p+q ppm of active ingredient is
`
`E = X + Y - %
`
`If the action actually observed (0) is greater than the expected action (E), then the action of
`
`the combination is super-additive, i.e. there is a synergistic effect. In mathematical terms,
`
`synergism corresponds to a positive value for the difference of (O-E). In the case of purely
`
`complementary addition of activities (expected activity), said difference (O—E) is zero. A
`
`negative value of said difference (O-E) signals a loss of activity compared to the expected
`
`activity.
`
`However, besides the actual synergistic action with respect to fungicidal activity, the
`
`compositions according to the invention can also have further surprising advantageous
`
`properties. Examples of such advantageous properties that may be mentioned are: more
`
`advantageuos degradability; improved toxicological and/or ecotoxicological behaviour; or
`
`improved characteristics of the useful plants including: emergence, crop yields, more
`
`developed root system, tillering increase, increase in plant height, bigger leaf blade, less
`
`dead basal leaves, stronger tillers, greener leaf colour, less fertilizers needed, less seeds
`
`needed, more productive tillers, earlier flowering, early grain maturity, less plant verse
`
`(lodging), increased shoot growth, improved plant vigor, and early germination.
`
`Some compositions according to the invention have a systemic action and can be
`
`used as foliar, soil and seed treatment fungicides.
`
`20
`
`25
`
`30
`
`

`

`WO 2017/207444
`
`PCT/EP2017/062795
`
`With the compositions according to the invention it is possible to inhibit or destroy the
`
`phytopathogenic microorganisms which occur in plants or in parts of plants (fruit, blossoms,
`
`leaves, stems, tubers, roots) in different useful plants, while at the same time the parts of
`
`plants which grow later are also protected from attack by phytopathogenic microorganisms.
`
`The compositions according to the invention can be applied to the phytopathogenic
`
`microorganisms, the useful plants, the locus thereof, the propagation material thereof,
`
`storage goods or technical materials threatened by microorganism attack.
`
`The compositions according to the invention may be applied before or after infection
`
`of the useful plants, the propagation material thereof, storage goods or technical materials
`
`1O
`
`by the microorganisms.
`
`A further aspect of the present invention is a method of controlling diseases on useful
`
`plants or on propagation material thereof caused by phytopathogens, which comprises
`
`applying to the useful plants, the locus thereof or propagation material thereof a
`
`composition according to the invention. Preferred is a method, which comprises applying to
`
`the useful plants or to the locus thereof a composition according to the invention, more
`
`preferably to the useful plants. Further preferred is a method, which comprises applying to
`
`the propagation material of the useful plants a composition according to the invention.
`
`Throughout this document the expression “composition” means the various mixtures
`
`or combinations of components (A) and (B), for example in a single “ready-mix” form, in a
`
`combined spray mixture composed from separate formulations of the single active
`
`ingredient components, such as a “tank—mix”, and in a combined use of the single active
`
`ingredients when applied in a sequential manner, i.e. one after the other with a reasonably
`
`short period, such as a few hours or days. The order of applying the components (A) and
`
`(B) is not essential for working the present invention.
`
`Compounds of formula (I) wherein Q is Q1, are preferred as component A. In
`
`particular, compounds of formula (I) wherein Q is Q1, R1, R2 and R3 are halogen (more
`
`especially chloro), R is methoxy and R8 is hydrogen are particularly preferred as component
`
`A.
`
`Preferred components (A) are listed in Tables 1 & 2 below.
`
`15
`
`20
`
`25
`
`30
`
`Table 1:
`
`Compounds of formula (lc):
`
`

`

`WO 2017/207444
`
`PCT/EP2017/062795
`
`_ 6 _
`
`H
`
`,
`
`wherein
`
`Q is
`
`F H RQ
`0"
`H Rs
`OCH3
`
`N
`
`\N
`I
`
`(Ic)
`
`R1
`
`R3
`
`R
`
`2
`
`(Q1) or
`
`R
`
`\
`\ S
`
`R6
`
`(Q2);
`
`
`
`Compound No.
`R1
`R2
`R3
`Q
`R4
`R5
`R6
`R3
`
`1.001
`CI
`CI
`CI
`Q1
`-
`-
`-
`H
`
`1.002
`CI
`H
`CI
`Q1
`-
`-
`-
`H
`
`1.003
`CI
`CI
`H
`Q1
`-
`-
`-
`H
`
`1.004
`Cl
`Br
`CI
`Q1
`-
`-
`-
`H
`
`1.005
`Br
`Br
`Br
`Q1
`-
`-
`-
`H
`
`1.006
`H
`CI
`H
`Q1
`-
`-
`-
`H
`
`1.007
`H
`Br
`H
`Q1
`-
`-
`-
`H
`
`1.008
`H
`CF3
`H
`Q1
`-
`-
`-
`H
`
`1-009
`-
`-
`-
`02
`CI
`c1
`CI
`H
`
`
`1-010
`-
`-
`-
`02
`CI
`H
`CI
`H
`
`
`1-011
`-
`-
`-
`02
`H
`CI
`CI
`H
`
`
`1-012
`-
`'
`-
`02
`CI
`Cl
`Br
`H
`
`
`1-013
`-
`'
`-
`02
`CI
`H
`Br
`H
`
`
`1.014
`-
`-
`-
`Q2
`H
`Cl
`Br
`H
`
`
`1.015
`-
`-
`-
`Q2
`H
`CI
`H
`H
`
`
`1.016
`-
`-
`-
`Q2
`CI
`H
`H
`H
`
`1.017
`CI
`CI
`CI
`Q1
`-
`-
`-
`OCH3
`
`1.018
`CI
`H
`CI
`Q1
`-
`-
`-
`OCH3
`
`1.019
`CI
`CI
`H
`Q1
`-
`-
`-
`OCH3
`
`1.020
`Cl
`Br
`CI
`Q1
`-
`-
`-
`OCH3
`
`1.021
`Br
`Br
`Br
`Q1
`-
`-
`-
`OCH3
`
`1.022
`H
`CI
`H
`Q1
`-
`-
`-
`OCH3
`
`1.023
`H
`Br
`H
`Q1
`-
`-
`-
`OCH3
`
`1.024
`H
`CF3
`H
`Q1
`-
`-
`-
`OCH3
`
`1-025
`-
`-
`-
`02
`CI
`CI
`CI
`OCH3
`
`
`1026
`-
`-
`-
`02
`c1
`H
`c1
`OCH3
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`

`

`WO 2017/207444
`
`PCT/EP2017/062795
`
`_ 7 _
`
`
`
`Compound No.
`R1
`R2
`R3
`Q
`R4
`R5
`R5
`R3
`
`1-027
`-
`-
`-
`02
`H
`CI
`CI
`OCHs
`
`
`1-028
`-
`-
`-
`02
`CI
`Cl
`Br
`OCH3
`
`
`
`
`
`
`
`
`
`CI
`
`H
`
`H
`
`H
`
`OCH3
`
`OCHs
`
`
`
`
`
`
`
`
`1-029
`-
`-
`-
`02
`CI
`H
`Br
`OCHs
`
`
`1-030
`-
`-
`-
`02
`H
`Cl
`Br
`OCHs
`
`1-031
`
`1-032
`
`-
`
`-
`
`-
`
`-
`
`-
`
`-
`
`02
`
`02
`
`H
`
`CI
`
`
`
`
`
`Table 2: Comgounds of formula (Id):
`
`wherein
`Q is
`
`5
`
`H
`
`F
`
`FH O RQ
`I
`N H R8
`N\
`\N
`I
`
`(Id),
`
`R1
`
`R4
`
`\ R5
`\ 8
`
`(Q2),
`
`R2
`
`(Q1) or
`
`R3
`R6
`
`
`Compound No.
`R1
`R2
`R3
`Q
`R4
`R5
`R5
`Rs
`
`2001
`CI
`CI
`CI
`Q1
`-
`-
`-
`H
`
`2.002
`CI
`H
`CI
`Q1
`-
`-
`-
`H
`
`2.003
`CI
`CI
`H
`Q1
`-
`-
`-
`H
`
`2.004
`Cl
`Br
`CI
`Q1
`-
`-
`-
`H
`
`2.005
`Br
`Br
`Br
`Q1
`-
`-
`-
`H
`
`2.006
`H
`CI
`H
`Q1
`-
`-
`-
`H
`
`2.007
`H
`Br
`H
`Q1
`-
`-
`-
`H
`
`2.008
`H
`CF3
`H
`Q1
`-
`-
`-
`H
`
`
`2-009
`-
`-
`-
`02
`CI
`CI
`CI
`H
`
`
`2-010
`-
`'
`-
`02
`CI
`H
`CI
`H
`
`
`2-011
`-
`-
`-
`02
`H
`CI
`CI
`H
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`2012
`-
`-
`-
`02
`CI
`Cl
`Br
`H
`
`
`2-013
`-
`'
`-
`02
`CI
`H
`Br
`H
`
`
`2-014
`-
`-
`-
`02
`H
`Cl
`Br
`H
`
`
`2.015
`-
`-
`-
`Q2
`H
`CI
`H
`H
`
`2.016
`
`-
`
`-
`
`-
`
`Q2
`
`CI
`
`H
`
`H
`
`H
`
`
`
`
`
`
`
`

`

`WO 2017/207444
`
`PCT/EP2017/062795
`
`_ 8 _
`
`
`
`Compound N0.
`R1
`R2
`R3
`Q
`R4
`R5
`Re
`Rs
`
`2017
`CI
`CI
`CI
`Q1
`-
`-
`-
`OCHs
`
`2.018
`CI
`H
`CI
`Q1
`OCHs
`
`2.019
`CI
`CI
`H
`Q1
`OCHs
`
`2.020
`Cl
`Br
`CI
`Q1
`OCH3
`
`2.021
`Br
`Br
`Br
`Q1
`OCH3
`
`2.022
`H
`CI
`H
`Q1
`OCH3
`
`2.023
`H
`Br
`H
`01
`OCH3
`
`2.024
`H
`CF3
`H
`Q1
`OCH3
`
`
`2-025
`-
`-
`-
`02
`CI
`CI
`CI
`OCH3
`
`
`2-026
`-
`-
`02
`CI
`H
`CI
`OCHs
`
`
`2-027
`-
`-
`02
`H
`CI
`CI
`OCH3
`
`
`2-028
`-
`-
`02
`CI
`Cl
`Br
`OCH3
`
`
`2-029
`-
`-
`02
`CI
`H
`Br
`OCHs
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`2.030
`-
`-
`02
`H
`Cl
`Br
`OCHs
`
`
`2-031
`-
`-
`02
`H
`CI
`H
`OCHs
`
`2-032
`
`-
`
`-
`
`02
`
`CI
`
`H
`
`H
`
`OCHs
`
`A particular preferred component (A) is the compound No. 1.001 (3-(difluoromethyl)—
`
`N-methoxy-1-methyl-N-[1-methyl-2—(2,4,6-trichlorophenyl)ethyl]pyrazole-4-carboxamide).
`
`Thus, particularly preferred mixtures comprise as component (A) 3-(difluoromethyl)—N-
`
`methoxy—1—methyl—N—[1—methyl—2—(2,4,6—trichlorophenyl)ethyl]pyrazole—4—carboxamide and a
`
`compound of formula (II).
`
`Particularly preferred components (B) are listed below in Table 3.
`
`TABLE 3
`Compounds of formula (II)
`1O
`
`Compound
`R21
`R22
`R23
`R24
`R25
`
`(Ila)
`CI
`F
`F
`F
`CI
`
`(IIb)
`H
`F
`F
`F
`CI
`
`(IIc)
`H
`F
`H
`F
`CI
`
`(IId)
`H
`F
`H
`F
`CN
`(Ile)
`H
`F
`F
`F
`Br
`
`
`
`
`
`
`
`
`
`
`
`Thus disclosed herein are compositions comprising any one of components (A) from
`
`Table 1
`
`in combination with compound (Ila); compositions comprising any one of
`
`components (A) from Table 2 in combination with compound (Ila); compositions comprising
`
`any one of components (A) from Table 1 in combination with compound (llb); compositions
`
`comprising any one of components (A) from Table 2 in combination with compound (llb);
`
`compositions comprising any one of components (A) from Table 1 in combination with
`
`

`

`WO 2017/207444
`
`PCT/EP2017/062795
`
`compound (llc); compositions comprising any one of components (A) from Table 2 in
`
`combination with compound (llc); compositions comprising any one of components (A) from
`
`Table 1
`
`in combination with compound (lid); compositions comprising any one of
`
`components (A) from Table 2 in combination with compound (lid); and compositions
`
`comprising any one of components (A) from Table 1
`
`in combination with compound (lle);
`
`compositions comprising any one of components (A) from Table 2 in combination with
`
`compound (||e).
`
`Particularly preferred mixtures comprise as component (A), a compound of formula (I)
`
`(in particular 3-(difluoromethyl)—N-methoxy-1-methyl-N-[1-methy|—2-(2,4,6-
`
`trichlorophenyl)ethyl]pyrazole-4-carboxamide) and as component B, any one of the
`
`compounds of formula (II) as listed in Table 3, and in particular any one of compounds (Ila),
`
`(llb), (llc) and (lid).
`
`In one embodiment component A is 3-(difluoromethyl)—N-methoxy-1-methyl-N-[1-
`
`methyl-2-(2,4,6-trichlorophenyl)ethyl]pyrazole-4-carboxamide, and component B is 3-chloro-
`
`5-(4-chlorophenyl)-6-methyl-4-(2,4,6-trifluorophenyl)pyridazine.
`
`In another embodiment component A is 3—(difluoromethyl)—N—methoxy—1—methy|—N—[1—
`
`methyl-2-(2,4,6-trichlorophenyl)ethyl]pyrazoIe-4-carboxamide, and component B is 3-chloro-
`
`6-methyl-5-phenyl-4-(2,4,6-trifluorophenyl)pyridazine.
`
`In a further embodiment component A is 3-(difluoromethyl)—N-methoxy-1-methyl-N-[1-
`
`methyl-2-(2,4,6-trichlorophenyl)ethyl]pyrazole-4-carboxamide, and component B is 4-(2,6-
`
`difluorophenyl)—3—chloro—6—methyl—5—phenyl—pyridazine.
`
`In yet a further embodiment component A is 3—(difluoromethyl)—N—methoxy—1—methyl—N—
`
`[1-methyl-2-(2,4,6-trichlorophenyl)ethyl]pyrazole-4-carboxamide, and component B is 4-(2,6-
`
`difluorophenyl)-6-methyl-5-phenyl-pyridazine-3-carbonitrile.
`
`The active ingredient combinations are effective against harmful microorganisms,
`
`such as microorganisms, that cause phytopathogenic diseases, in particular against
`
`phytopathogenic fungi and bacteria.
`
`The active ingredient combinations are effective especially against phytopathogenic
`
`fungi belonging to the following classes: Ascomycetes (e.g. Venturia, Podosphaera,
`
`Erysiphe, Monilinia, Mycosphaerella, Uncinula); Basidiomycetes (e.g. the genus Hemileia,
`
`Rhizoctonia, Phakopsora, Puccinia, Ustilago, Tilletia); Fungi imperfecti (also known as
`
`Deuteromycetes; e.g. Botrytis, Helminthosporium, Rhynchosporium, Fusarium, Septoria,
`
`Cercospora, Alternaria, Pyricularia and Pseudocercosporella); Oomycetes (e.g.
`
`1O
`
`15
`
`20
`
`25
`
`30
`
`

`

`WO 2017/207444
`
`PCT/EP2017/062795
`
`-10-
`
`Phytophthora, Peronospora, Pseudoperonospora, Albugo, Bremia, Pythium,
`
`Pseudosclerospora, Plasmopara).
`
`According to the invention “useful plants” typically comprise the following species of
`
`plants: grape vines; cereals, such as wheat, barley, rye or oats; beet, such as sugar beet or
`
`fodder beet; fruits, such as pomes, stone fruits or soft fruits, for example apples, pears,
`
`plums, peaches, almonds, cherries, strawberries, raspberries or blackberries; leguminous
`
`plants, such as beans, lentils, peas or soybeans; oil plants, such as rape, mustard, poppy,
`
`olives, sunflowers, coconut, castor oil plants, cocoa beans or groundnuts; cucumber plants,
`
`such as marrows, cucumbers or melons; fibre plants, such as cotton, flax, hemp orjute;
`
`1O
`
`citrus fruit, such as oranges, lemons, grapefruit or mandarins; vegetables, such as spinach,
`
`lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika;
`
`lauraceae, such as avocados, cinnamon or camphor; maize; tobacco; nuts; coffee; sugar
`
`cane; tea; vines; hops; durian; bananas; natural rubber plants; turf or ornamentals, such as
`
`flowers, shrubs, broad-leaved trees or evergreens, for example conifers. This list does not
`
`15
`
`represent any limitation.
`
`20
`
`25
`
`30
`
`The term "useful plants" is to be understood as including also useful plants that have
`
`been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for
`
`example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and
`
`trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS
`
`(glutamine synthetase) inhibitors) as a result of conventional methods of breeding or
`
`genetic engineering. An example of a crop that has been rendered tolerant to
`
`imidazolinones, e.g. imazamox, by conventional methods of breeding (mutagenesis) is
`
`Clearfield® summer rape (Canola). Examples of crops that have been rendered tolerant to
`
`herbicides or classes of herbicides by genetic engineering methods include glyphosate- and
`
`glufosinate-resistant maize varieties commercially available under the trade names
`
`RoundupReady® , Herculex l® and LibertyLink®.
`
`The term "useful plants" is to be understood as including also useful plants which
`
`have been so transformed by the use of recombinant DNA techniques that they are capable
`
`of synthesising one or more selectively acting toxins, such as are known, for example, from
`
`toxin-producing bacteria, especially those of the genus Bacillus.
`
`Toxins that can be expressed by such transgenic plants include, for example,
`
`insecticidal proteins, for example insecticidal proteins from Bacillus cereus or Bacillus
`
`popliae; or insecticidal proteins from Bacillus thuringiensis, such as S-endotoxins, e.g.
`
`CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(b1) or Cry90, or vegetative
`
`

`

`WO 2017/207444
`
`PCT/EP2017/062795
`
`-11-
`
`insecticidal proteins (VIP), e.g. VIP1, VIP2, VIP3 or VIP3A; or insecticidal proteins of
`
`bacteria colonising nematodes, for example Photorhabdus spp. or Xenorhabdus spp., such
`
`as Photorhabdus luminescens, Xenorhabdus nematophilus; toxins produced by animals,
`
`such as scorpion toxins, arachnid toxins, wasp toxins and other insect-specific neurotoxins;
`
`toxins produced by fungi, such as Streptomycetes toxins, plant lectins, such as pea lectins,
`
`barley lectins or snowdrop lectins; agglutinins; proteinase inhibitors, such as trypsine
`
`inhibitors, serine protease inhibitors, patatin, cystatin, papain inhibitors; ribosome-
`
`inactivating proteins (RIP), such as ricin, maize-RIP, abrin, qufin, saporin or bryodin; steroid
`
`metabolism enzymes, such as 3-hydroxysteroidoxidase, ecdysteroid-UDP-glycosyl-
`
`transferase, cholesterol oxidases, ecdysone inhibitors, HMG-COA—reductase, ion channel
`
`blockers, such as blockers of sodium or calcium channels, juvenile hormone esterase,
`
`diuretic hormone receptors, stilbene synthase, bibenzyl synthase, chitinases and
`
`glucanases.
`
`In the context of the present invention there are to be understood by 8—endotoxins, for
`
`example CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(b1) or Cry90, or
`
`vegetative insecticidal proteins (VIP), for example VIP1, VIP2, VIP3 or VIP3A, expressly
`
`also hybrid toxins, truncated toxins and modified toxins. Hybrid toxins are produced
`
`recombinantly by a new combination of different domains of those proteins (see, for
`
`example, WO 02/15701). An example for a truncated toxin is a truncated CrylA(b), which is
`
`expressed in the Bt11 maize from Syngenta Seed SAS, as described below. In the case of
`
`modified toxins, one or more amino acids of the naturally occurring toxin are replaced. In
`
`such amino acid replacements, preferably non-naturally present protease recognition
`
`sequences are inserted into the toxin, such as, for example, in the case of Cry|||A055, a
`
`cathepsin-D-recognition sequence is inserted into a CryIIIA toxin (see WO 03/018810)
`
`Examples of such toxins or transgenic plants capable of synthesising such toxins are
`
`disclosed, for example, in EP-A—0 374 753, WO 93/07278, WO 95/34656, EP-A—0 427 529,
`
`EP-A—451 878 and WO 03/052073.
`
`The processes for the preparation of such transgenic plants are generally known to
`
`the person skilled in the art and are described, for example, in the publications mentioned
`
`above. CryI-type deoxyribonucleic acids and their preparation are known, for example, from
`
`WO 95/34656, EP-A—0 367 474, EP-A-0 401 979 and WO 90/13651.
`
`The toxin contained in the transgenic plants imparts to the plants tolerance to harmful
`
`insects. Such insects can occur in any taxonomic group of insects, but are especially
`
`1O
`
`15
`
`20
`
`25
`
`30
`
`

`

`WO 2017/207444
`
`PCT/EP2017/062795
`
`-12-
`
`commonly found in the beetles (Coleoptera), two—winged insects (Diptera) and butterflies
`
`(Lepidoptera).
`
`Transgenic plants containing one or more genes that code for an insecticidal
`
`resistance and express one or more toxins are known and some of them are commercially
`
`available. Examples of such plants are: YieldGard® (maize variety that expresses a
`
`CrylA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CrylllB(b1) toxin);
`
`YieldGard Plus® (maize variety that expresses a CrylA(b) and a CrylllB(b1) toxin); Starlink®
`
`(maize variety that expresses a Cry9(c) toxin); Herculex l® (maize variety that expresses a
`
`CrylF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve
`
`tolerance to the herbicide glufosinate ammonium); NuCOTN 3BB® (cotton variety that
`
`expresses a CrylA(c) toxin); Bollgard l® (cotton variety that expresses a CrylA(c) toxin);
`
`Bollgard ll® (cotton variety that expresses a CrylA(c) and a CryllA(b) toxin); VIPCOT®
`
`(cotton variety that expresses a VIP toxin); NewLeaf® (potato variety that expresses a
`
`CrylllA toxin); NatureGard® and Protecta®.
`
`Further examples of such transgenic crops are:
`
`1. Bt11 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St.
`
`Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which
`
`has been rendered resistant to attack by the European corn borer (Ostrinia nubila/is and
`
`Sesamia nonagrioides) by transgenic expression of a truncated CrylA(b) toxin. Bt1 1 maize
`
`also transgenically expresses the enzyme PAT to achieve tolerance to the herbicide
`
`glufosinate ammonium.
`
`2. Bt176 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St.
`
`Sauveur, France, registration number C/FR/96/05/10. Genetically modified Zea mays which
`
`has been rendered resistant to attack by the European corn borer (Ostrinia nubila/is and
`
`Sesamia nonagrioides) by transgenic expression of a CrylA(b) toxin. Bt176 maize also
`
`transgenically expresses the enzyme PAT to achieve tolerance to the herbicide glufosinate
`
`ammonium.
`
`3. MIR604 Maize from Syngenta Seeds SAS, Chemin de l'Hobit 27, F-31 790 St.
`
`Sauveur, France, registration number C/FR/96/05/10. Maize which has been rendered
`
`insect-resistant by transgenic expression of a modified CrylllA toxin. This toxin is Cry3A055
`
`modified by insertion of a cathepsin—D—protease recognition sequence. The preparation of
`
`such transgenic maize plants is described in WC 03/018810.
`
`10
`
`15
`
`20
`
`25
`
`30
`
`

`

`WO 2017/207444
`
`PCT/EP2017/062795
`
`-13-
`
`4. MON 863 Maize from Monsanto Europe S.A. 270—272 Avenue de Tervuren, B—1150
`
`Brussels, Belgium, registration number C/DE/02/9. MON 863 expresses a CrylllB(b1) toxin
`
`and has resistance to certain Coleoptera insects.
`
`5. IPC 531 Cotton from Monsanto Europe S.A. 270-272 Avenue de Tervuren, B-1150
`
`Brussels, Belgium, registration number C/ES/96/02.
`
`6. 1507 Maize from Pioneer Overseas Corporation, Avenue Tedesco, 7 B-1160
`
`Brussels, Belgium, registration number C/NL/00/10. Genetically modified maize for the
`
`expression of the protein Cry1 F for achieving resistance to certain Lepidoptera insects and
`
`of the PAT protein for achieving tolerance to the herbicide glufosinate ammonium.
`
`7. NK603 x MON 810 Maize from Monsanto Europe S.A. 270—272 Avenue de
`
`Tervuren, B—1150 Brussels, Belgium, registration number C/GB/02/M3/03. Consists of
`
`conventionally bred hybrid maize varieties by crossing the genetically modified varieties
`
`NK603 and MON 810. NK603 X MON 810 Maize transgenically expresses the protein CP4
`
`EPSPS, obtained from Agrobacterium sp. strain CP4, which imparts tolerance to the
`
`herbicide Roundup® (contains glyphosate), and also a CrylA(b) toxin obtained from Bacillus
`
`thuringiensis subsp. kurstaki which brings about tolerance to certain Lepidoptera, include
`
`10
`
`15
`
`the European corn borer.
`
`Transgenic crops of insect-resistant plants are also described in BATS (Zentrum fiir
`
`Biosicherheit und Nachhaltigkeit, Zentrum BATS, Clarastrasse 13, 4058 Basel, Switzerland)
`
`20
`
`Report 2003, (http://bats.ch).
`
`The term "useful plants" is to be understood as including also useful plants which
`
`have been so transformed by the use of recombinant DNA techniques that they are capable
`
`of synthesising antipathogenic substances having a selective action, such as, for example,
`
`the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A—0 392 225). Examples
`
`of such antipathogenic substances and transgenic plants capable of synthesising such
`
`antipathogenic substances are known, for example, from EP-A—0 392 225, WO 95/33818,
`
`and EP—A—0 353 191. The methods of producing such transgenic plants are generally
`
`known to the person skilled in the art and are described, for example, in the publications
`
`mentioned above.
`
`Antipathogenic substances which can be expressed by such transgenic plants
`
`include, for example, ion channel blockers, such as blockers for sodium and calcium
`
`channels, for example the viral KP1, KP4 or KP6 toxins; stilbene synthases; bibenzyl
`
`synthases; chitinases; glucanases; the so—called "pathogenesis—related proteins" (PRPs;
`
`25
`
`30
`
`

`

`WO 2017/207444
`
`PCT/EP2017/062795
`
`-14-
`
`see e.g. EP—A—0 392 225); antipathogenic substances produced by microorganisms, for
`
`example peptide antibiotics or heterocyclic antibiotics (see e.g. WO 95/33818) or protein or
`
`polypeptide factors involved in plant pathogen defence (so-called "plant disease resistance
`
`genes", as described in WC 03/000906).
`
`Useful plants of elevated interest in connection with present invention are cereals;
`
`soybean; rice; oil seed rape; pome fruits; stone fruits; peanuts; coffee; tea; strawberries;
`
`turf; vines and vegetables, such as tomatoes, potatoes, cucurbits and lettuce.
`
`The term “locus” of a useful plant as used herein is intended to embrace the place on
`
`which the useful plants are growing, where the plant propagation materials of the useful
`
`plants are sown or where the plant propagation materials of the useful plants will be placed
`
`into the soil. An example for such a locus is a field, on which crop plants are growing.
`
`The term “plant propagation material” is understood to denote generative parts of a
`
`plant, such as seeds, which can be used for the multiplication of the latter, and vegetative
`
`material, such as cuttings or tubers, for example potatoes. There may be mentioned for
`
`example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants.
`
`Germinated plants and young plants which are to be transplanted after germination or after
`
`emergence from the soil, may also be mentioned. These young plants may be protected
`
`before transplantation by a total or partial treatment by immersion. Preferably “plant
`
`propagation material” is understood to denote seeds.
`
`A futher aspect of the instant invention is a method of protecting natural substances
`
`of plant and/or animal origin, which have been taken from the natural life cycle, and/or their
`
`processed forms against attack of fungi, which comprises applying to said natural
`
`substances of plant and/or animal origin or their processed forms a combination of
`
`components (A) and (8)..
`
`According to the instant invention, the term “natural substances of plant origin, which
`
`have been taken from the natural life cycle” denotes plants or parts