(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT)
`(19) World Intellectual Property
`Organization
`International Bureau
`
`(43) International Publication Date
`24 April 2014 (24.04.2014)
`
`WIPOI PCT
`
`\9
`
`(10) International Publication Number
`
`WO 2014/060502 A1
`
`(51)
`
`International Patent Classification:
`A01N 43/56 (2006.01)
`A01N 43/80 (2006.01)
`A01N 57/20 (2006.01)
`A01N 41/06 (2006.01)
`
`(21)
`
`International Application Number:
`
`PCT/EP2013/071694
`
`(22)
`
`International Filing Date:
`
`17 October 2013 (17.10.2013)
`
`(25)
`
`(26)
`
`(30)
`
`(71)
`
`(72)
`
`(74)
`
`(81)
`
`Filing Language:
`
`Publication Language:
`
`Priority Data:
`1235 6025.2
`61/730,251
`
`19 October 2012 (19.10.2012)
`27 November 2012 (27.11.2012)
`
`English
`
`English
`
`EP
`US
`
`Applicant: BAYER CROPSCIENCE AG [DE/DE]; A1-
`fi'ed-Nobel-Strasse 50, 40789 Monheim (DE).
`
`Inventors: CRISTAU, Pierre; 4 rue Marietton, F-69009
`Lyon (FR). DAHMEN, Peter; Altebriickerstrasse 63,
`41470 Neuss (DE).
`
`Agent: GUITTON, Carole; Bayer S.A.S., Patents & Li-
`censing, 14 impasse Pierre Baizet, CS 99163, F-69263
`Lyon cedeX 09 (FR).
`
`Designated States (unless otherwise indicated, for every
`kind ofnational protection available): AE, AG, AL, AM,
`AO, AT, AU, AZ, BA, BB, BG, BH, RN, BR, BW, BY,
`BZ, CA, CH, CL, CN, CO, CR, CU, CZ, DE, DK, DM,
`
`DO, DZ, EC, EE, EG, ES, FI, GB, GD, GE, GH, GM, GT,
`IIN, IIR, IIU, ID, IL, IN, IR, IS, JP, KE, KG, KN, KP, KR,
`KZ, LA, LC, LK, LR, LS, LT, 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, R0, RS, RU, RW, SA,
`SC, 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 of regional protection available): ARIPO (BW, GH,
`GM, KE, LR, LS, MW, MZ, NA, RW, SD, SL, 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).
`Declarations under Rule 4.17:
`
`as to applicant’s entitlement to applvfor and be granted a
`patent (Rule 4.17(ii))
`Published:
`
`with international search report (Art. 21(3))
`
`before the expiration of the time limit for amending the
`claims and to be republished in the event of receipt of
`amendments (Rule 48.2(h))
`
`(54) Title: ACTIVE COMPOUND COMBINATION S COMPRISING CARBOXAMIDE DERIVATIVES
`
`(57) Abstract: The present invention relates to active compound combinations, in particular Within a composition, Which comprises
`(A) ) a N-cyclopropyl-N-[Subsliluled-benzyl]-3-(di11uoromelhyl)-5-11uoro-1-melhyl-1H-pyrazole-4-carboxamide or lhiocarboxamide
`derivative and (B) a further herbicidally active compound or (C) a plant growth regulator and/or (D) a safener for reducing phytotox —
`ic actions of agrochemicals. Moreover, the invention relates to a method for curatively or preventively controlling the phytopatho -
`genic fungi of plants or crops, to the use of a combination according to the invention for the treatment of seed, to a method for pro —
`tecting a seed and not at least to the treated seed.
`
`
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`WO 2014/060502
`Active compound combinations comprising carboxamide derivatives
`
`PCT/EP2013/071694
`
`The present invention relates to active compound combinations, in particular within a composition,
`
`which comprises (A) ) a N—cyclopropyl-N-[substituted—benzyl]—3 -(difluoromethyl)—5—fluoro-l-methyl-
`
`lH—pyrazole—4—carboxamide or thiocarboxamide derivative and (B) a fiirther herbicidally active com-
`
`pound or (C) a plant growth regulator and/or (D) a safener for reducing phytotoxie actions of agro—
`
`chemicals. Moreover, the invention relates to a method for curatively or preventively controlling the
`
`phytopathogenic fungi of plants or crops, to the use of a combination according to the invention for the
`
`treatment of seed, to a method for protecting a seed and not at least to the treated seed.
`
`N—cyclopropyl—N-[substituted-b enzyl]—3-(difluoromethyl)—5-fluoro- 1 -methyl- 1H—pyrazole—4—
`
`carboxamide or thiocarboxamide derivatives, their preparation from commercially available materials
`
`and their use as fungicides are disclosed in W02007/087906, W02009/Ol6220, WOZOlO/ 130767 and
`
`EP2251331. It is also known that these compounds can be used as fungicides and mixed with other
`
`fungicides or insecticides (cf. patent applications PCT/EP2012/001676 and PCT/EP2012/001674).
`
`Since the environmental and economic requirements imposed on modern-day crop protection composi-
`
`tions are continually increasing, with regard, for example, to the spectrum of action, toxicity, selectivi-
`
`ty, application rate, formation of residues, and favorable preparation ability, and since, furthermore,
`
`there may be problems, for example, with resistances, a constant task is to develop new compositions,
`
`in particular fungicidal agents, which in some areas at least help to fulfill the abovementioned require-
`
`ments. The present invention provides active compound combinations/compositions which in some as—
`
`pects at least achieve the stated objective.
`
`When controlling unwanted organisms in crops of plants which are usefiil for agriculture or forestry by
`
`using pesticides, the useful plants are sometimes also damaged to a greater or lesser extent by the pesti—
`
`cides employed. This unwanted phytotoxie effect is encountered in particular with the use of a consid-
`
`erable number of herbicides in crops of useful plants such as, for example, corn, rice or cereals- and
`
`there primarily in the post-emergence application. In some instances, the useful plants can be protected
`
`against the phytotoxie properties of the pesticides by employing safeners or antidotes, without dimin—
`
`ishing or substantially impairing the pesticidal activity against the harmful organisms. In some cases,
`
`even an improved pesticidal action against hannful organisms such as weeds was obseived.
`
`It has now been found, surprisingly, that the combinations according to the invention not only bring
`
`about the additive enhancement of the spectrum of action with respect to the phytopathogen to be con-
`
`trolled that was in principle to be expected but achieves a synergistic effect which extends the range of
`
`action of the component (A) and of the component (B) in two ways. Firstly, the rates of application of
`
`the component (A) and of the component (B) are lowered whilst the action remains equally good. See—
`
`ondly, the combination still achieves a high degree of phytopathogen control even where the two indi-
`
`vidual compounds have become totally ineffective in such a low application rate range. This allows, on
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`the one hand, a substantial broadening of the spectrum of phytopathogens that can be controlled and, on
`
`the other hand, increased safety in use.
`
`In addition to the fungicidal synergistic activity, the active compound combinations according to the
`
`invention have further surprising properties which, in a wider sense, may also be called synergistic,
`
`such as, for example: broadening of the activity spectrum to other phytopathogens, for example to re—
`
`sistant strains of plant diseases; lower application rates of the active compounds; sufficient control of
`
`pests with the aid of the active compound combinations according to the invention even at application
`
`rates where the individual compounds show no or virtually no activity; advantageous behavior during
`
`formulation or during use, for example during grinding, sieving, emulsifying, dissolving or dispensing;
`
`improved storage stability and light stability; advantageous residue formation; improved toxicological
`
`or ecotoxicological behavior; improved properties of the plant, for example better growth, increased
`
`harvest yields, a better developed root system, a larger leaf area, greener leaves, stronger shoots, less
`
`seed required, lower phytotoxicity, mobilization of the defense system of the plant, good compatibility
`
`with plants. Thus, the use of the active compound combinations or compositions according to the in-
`
`vention contributes considerably to keeping young cereal stands healthy, which increases, for example,
`
`the winter survival of the cereal seed treated, and also safeguards quality and yield. Moreover, the ac-
`
`tive compound combinations according to the invention may contribute to enhanced systemic action.
`
`Even if the individual compounds of the combination have no sufficient systemic properties, the active
`
`compound combinations according to the invention may still have this property. In a similar manner,
`
`the active compound combinations according to the invention may result in higher persistency of the
`
`fimgicidal action.
`
`Accordingly, the present invention provides a combination comprising:
`
`(A)
`
`at least one derivative of formula (I)
`
`X
`
`(1)
`
`wherein T represents an oxygen or a sulfur atom and X is selected from the list of 2—isopropyl, 2-
`
`eyclopropyl,
`
`2—tert-butyl,
`
`5-chloro—2—ethyl,
`
`5-ehloro—2—isopropyl, 2-ethyl-5-fluoro,
`
`S—fluoro-Z-
`
`isopropyl, 2—cyclopropyl-5-fluoro, 2-cyclopentyl—5—fluoro, 2—fluoro-6-isopropyl, 2-ethyl-5-methyl, 2-
`
`isopropyl—S—methyl, 2—cyelopropyl—5—methyl, 2—tert—butyl—5—methyl, 5—chloro—2—(trifluoromethyl), 5—
`
`methyl-2—(trifluoromethyl), 2-chloro—6—(trifluoromethyl), 3—chloro-2-fluoro-6-(trifluoromethyl) and
`
`2-ethyl-4,5-dimethyl, or an agrochemically acceptable salt thereof,
`
`and
`
`(B)
`
`at least one further herbicidally active compound
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`WO 2014/060502
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`or
`
`(C)
`
`at least one plant growth regulator
`
`and/or
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`PCT/EP2013/071694
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`(D)
`
`at least one safener for reducing phytotoxic actions of agrochemicals.
`
`Preference is given to combinations comprising at least one compound of the formula (I) selected
`
`from the group consisting of :
`
`\ -cyclopr0pyl—3 —(diflu oromethyl)—5 —flu oro -N— (2-is opropylb enzyl)- 1 -methyl- lH-pyrazole-4-
`
`carboxamidc (compound A1),
`
`\ -cyclopropyl—N—(2—cyclopropylb enzyl)-3 -(difluoromethyl)-5 -fluoro— 1 —methyl— 1H—pyrazole-4—
`
`carboxamide (compound A2),
`
`\ -(2—tert—butylbenzyl) —N-cyclopropyl—3 —(difluoromethyl)—5 —fluoro- 1 -methyl- 1 H-pyrazole-4-
`
`carboxamide (compound A3),
`
`
`
`
`
`\ -(5 —chloro-2— ethylbenzyl) -N—cyclopropyl-3 -(difluoromethyl)-5 -fluoro— 1 -methyl— 1H-pyrazole—4—
`
`carboxamide (compound A4),
`
`\ -(5—chloro-2-isopropylbcnzyl)—N -cyclopropyl-3-(difluoromethyl)-5 —fluoro- 1 -mcthyl- 1H-pyrazolc-4-
`
`carboxamide (compound A5),
`
`\ -cyclopropyl—3 —(difluoromethyl) —N— (2—ethyl—5 —fluorob enzyl)-5 -fluoro— 1 —methyl— 1H—pyrazole—4—
`
`carboxamide (compound A6),
`
`\ —cyclopropyl—3—(difluoromethyl)—5—fluoro—N—(5—fluoro—Z—isopropylbenzyl)—l —methy1— lH—pyrazole—4—
`
`carboxamide (compound A7),
`
`\ -cyclopropyl—N—(2—cyclopropyl-5 -fluorobenzyl)—3—(difluoromethyl)—5 —fluoro- 1 -methyl- 1 H-pyrazole-
`
`4-carboxamidc (compound A8),
`
`\ -(2—cyclopentyl-S-fluorobenzyl)—N-cyclopropyl-3 -(difluoromethyl)-5 —fluoro- 1 -methyl- lH-pyrazole-
`
`4-carboxamide (compound A9),
`
`\ -cyclopropyl—3—(difluoromethyl)—5—fluoro-N—(2—fluoro—6—isopropylbenzyl)-1 -methyl- lH-pyrazole—4-
`
`carboxamide (compound A10),
`
`\ -cyclopropyl—3 —(difluoromethyl) —N— (2—ethyl—5 —methylbenzyl)- 5 —fluoro- 1 -methyl- 1H-pyrazole-4-
`
`carboxamide (compound Al 1),
`
`\ -cyclopropyl—3—(difluoromethyl)—5—fluoro-N —(2—isopropyl-5—methylbenzyl)- 1 -methyl- ll-l-pyrazole-
`
`4-carboxamide (compound A12),
`
`\ -cyclopropyl—N-(2—cyclopropyl-5 -methylbenzyl)-3 -(difluoromethyl)-5 -fluoro— 1 —methyl— 1H—
`
`pyrazole—4—carboxamide (compound A13),
`
`\ —(2—tert—butyl—5 —methylb enzyl) —N—cyclopropyl—3 —(difluoromethyl)—5 —fluoro— 1 —methyl— lH—pyrazole—4—
`
`carboxamide (compound A14),
`
`\ - [5 —chlor0-2- (tri fluoromethyl)benzyl ] -N—cyclopropyl-3 -(difluoromethyl)-5 -fluoro- l -in ethyl - l H-
`
`pyrazolc—4—carboxamidc (compound A15),
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`N—cyclopropyl—3 —(difluoromethyl)—5 —fluoro- 1 -methyl-N— [5 -methyl-2-(trifluoromethyl)benzyl] - 1 H-
`
`pyrazole—4—carboxamide (compound A16),
`
`N— [2—chloro-6- (trifluoromethyl)benzyl] -N—cyc lopropyl-3 -(difluoromethyl)-5 -fluoro- 1 -methyl- 1 H-
`
`py1azole—4—carboxamide (compound A17),
`
`N— [3 —chloro—2— fluoro—6—(trifluoromethyl)benzyl] —N—cyclopropyl—3 —(difluoromethyl) —5 —fluoro— 1 —
`
`methyl—1H—pyrazole—4—carboxamide (compound A1 8).
`
`N—cyclopropyl—3—(difluoromethyl)—N—(2—ethyl—4,5—dimethylbenzyl)-5-fluoro- 1 -methyl-1H-pyrazole-4-
`
`earboxamide (compound A19),
`
`and
`
`N-cyclopropyl—3—(difluoromethyl)—5—fluoro-N—(2-isopropylbenzyl)— 1 -methyl- 1 H-pyrazole-4-
`
`earbothio-amide (compound A20).
`
`Suitable
`
`as
`
`combination
`
`partners
`
`for
`
`the
`
`active N—cyclopropyl-N—[substituted-benzyl]—3-
`
`(difluoromethyl)—5-fluoro-1-methyl-1H-pyrazole-4-carboxamide
`
`or thiocarboxamide derivatives of
`
`formula (I) in formulations of mixtures or in tank-mixes are, for example, known, preferably herbicidal-
`
`ly active compounds whose action is based on the inhibition of, for example, aeetolactate synthase, ace—
`
`tyl—coenzyme-A carboxylase, PS 1, PS 11, HPPDO, phytoene desaturase, protoporphyrinogen oxidase,
`
`glutamine synthetase, cellulose biosynthesis, 5-enolpy1uvylshikimate 3—phosphate synthetase. Such
`
`compounds and also other compounds which can be used, in some cases having an unknown or a dif—
`
`ferent mechanism of action, are described, for example, in Weed Research 26, 441-445 (1986), or in
`
`“The Pesticide Manual”, 12th edition 2000, or 13th edition 2003 or 14th edition 2006/2007, or in the
`
`corresponding “e-Pesticide Manual”, version 4 (2006), all published by the British Crop Protection
`
`Council, (hereinbelow also referred to in short as “PM”), and in the literature cited therein. Lists of
`
`1O
`
`15
`
`20
`
`“common names” are also available in “The Compendium of Pesticide Common Names” on the Inter-
`net.
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`
`Examples of herbicides known from the literature and also safeners, which may be combined with the
`
`N-cyclopropyl—N-[substituted-b enzyl]—3-(difluoromethyl)—5-fluoro- 1 -methyl- 1 H—pyrazole—4—
`
`earboxamide or thiocarboxamide derivatives of formula (I) are the active compounds indicated herein
`
`(note: the compounds are referred to either by the “common name” according to the lntemational Or-
`
`ganization for Standardization (ISO) or by the chemical name, if appropriate together with a customary
`
`code number):
`
`acetochlor; acibenzolar—S-methyl; acifluorfen(-sodium); aclonifen; AD—67; AKH 7088, i.e. [[[1-[5—[2-
`
`chloro—4—(trifluoromethyl)phenoxy]—2—nitrophenyl]—2—methoxyethylidene]amino]oxy]acetie
`
`acid and
`
`methyl
`
`[[[ 1 — [5 - [2—ehloro-4-(trifluoromethyl)phenoxy] -2-nitrophenyl] —2—methoxyethylidene] -
`
`amino]oxy]acetate; alachlor; alloxydim(—sodium); ametryn; amicarbazone, amidochlor, amidosulfuron;
`
`aminopyralid; amitrol; AMS,
`
`i.e. ammonium sulfamate; ancimidol; anilofos; asulam; atrazine; avi-
`
`glycine;
`
`azafenidin,
`
`azimsulfuron
`
`(DPX—A8947);
`
`aziprotryn;
`
`barban; BAS
`
`516 H,
`
`i.e.
`
`5-fluoro-2-phenyl-4H-3,1-benzoxazin-4-one; beflubutamid (UBH-509), benazolin(-ethyl); bencarba-
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`zone; benfluralin; benfuresate; benoxaeor; bensulfur0n(-methyl); bensulide; bentazone; benzfendizone;
`
`benzobieyclon, benzofenap; benzofluor; benzoylpr0p(—ethyl); benzthiazuron; bialaphos; bifenox;
`
`bispyribac(-s0dium) (KIH—2023); borax; bromacil; bromobutide; bromofenoxim; bromoxynil; bromu—
`
`r011; buminafos; busoxinone; butaehlor; butafenaeil, butamifos; butenachlor (KH-218); buthidazole; bu-
`
`tralin; butroxydim, butylate; eafenstrole (CH—900); earbetamide; earfentrazone(—ethyl); CDAA,
`
`i.e.
`
`2-ehlor0-N,N-di-2—pr0penylaeetamide; CDEC,
`
`i.e. 2—ehlorallyl diethyldithioearbamate; ehlomethox-
`
`yfen;
`
`ehloramben;
`
`ehlorazifop-butyl,
`
`ehlorbromuron;
`
`ehlorbufam;
`
`ehlorfenae;
`
`ehlorfenprop;
`
`chlorflureeol(-methyl);
`
`ehlorflurenol(-methyl);
`
`chloridazon;
`
`ehlorimuron
`
`(-ethyl);
`
`ehlormequat
`
`(—ehloride); ehlomitrofen; chlorophthalim (MK-616); chlorotoluron; ehloroxuron; ehlorpropham; ehlor-
`
`sulfuron; chlorthal-dimethyl; ehlorthiamid; chlortoluron, cinidon (-methyl and -ethyl), cinmethylin;
`
`einosulfiJron; clefoxydim, clethodim; elodinafop and its ester derivatives (for example clodinafop-
`
`propargyl); elofeneet; elomazone; elomeprop; eloprop; eloproxydim; elopyralid; clopyrasulfur0n(—
`
`methyl), cloquintoeet(—mexyl); eloransulam(-methyl), eumyluron (JC 940); cyanamide; cyanazine; ey-
`
`eloate; eyelosulfamuron (AC 104); eyeloxydim; eyeluron; eyhalofop and its ester derivatives (for ex-
`
`ample the butyl ester, DEH-112); eyperquat; eyprazine; cyprazole; eyprosulfamide; daimuron; 2,4-D,
`
`2,4—DB; dalapon; daminozide; dazomet; n—deeanol; desmedipham; desmetryn; di—allate; dieamba; di—
`
`chlobenil; dichlormid; dichlorprop(—P) salts; diclofop and its esters, such as diclofop-methyl; diclofop-
`
`P(-methyl); dielosulam,
`
`diethatyl(—ethyl); difenoxuron; difenzoquat( metilsulfate); diflufenican;
`
`diflufenzopyr(—s0dium); dimefuron; dimepiperate, dimethachlor; dimethametryn; dimethazone; dime—
`
`thenamid (SAN-582H); dimethenamide—P; dimethylarsinic acid; dimethipin; dimetrasulfuron, dinitra-
`
`mine; dinoseb; dinoterb; diphenamid; dipropetryn; diquat salts; dithiopyr; diuron; DNOC; eglinazine-
`
`ethyl; EL 77, i.e. 5-eyan0-1-(1,1—dimethylethyl)—N—methyl-1H-pyrazole—4—earb0xamide; endothal; epo-
`
`prodan, EPTC; esproearb; ethalfluralin; ethametsulfuron—methyl; ethephon; ethidimuron; ethiozin;
`
`ethofumesate; ethoxyfen and its esters (for example the ethyl ester, HN-252); ethoxysulfuron, etoben-
`
`zanid (HW 52); F5231,
`
`i.e. N-[2—ehlor0-4-fluoro-5-[4-(3-flu0r0pr0pyl)-4,5-dihydr0—5—0x0-1H-te-
`
`trazol—1—yl]phenyl]ethanesulfonamide; fenehlorazole(—ethyl); fenelorim; fenoprop; fenoxan, fenoxaprop
`
`and fenoxaprop—P and also their esters,
`
`for example fenoxaprop-P-ethyl and fenoxaprop-ethyl;
`
`fenoxydim; fentrazamide, fenuron; ferrous sulfate; flampr0p(-methyl 0r -is0pr0pyl 0r -is0pr0pyl—L);
`
`flamprop-M(—methyl 0r —is0pr0pyl); flazasulfuron; florasulam, fluazifop and fluazifop—P and their es-
`
`ters, for example fluazifop—butyl and fluazifop—P—butyl; fluazolate, fluearbazone(—s0dium), flueetosulfu—
`
`ron;
`
`fluchloralin; flufenacet; flufenpyr(-ethyl); flumetralin; flumetsulam; flumeturon;
`
`flumiclorac(—
`
`pentyl), flumioxazin (8—482);
`
`flumipropyn;
`
`fluometuron,
`
`fluoroehloridone, fluorodifen;
`
`fluorogly-
`
`eofen(—ethyl);
`
`flupoxam (KNW—739);
`
`flupropaeil
`
`(UBIC—4243);
`
`flupropanoate;
`
`flupyrsulfur0n(—
`
`methyl)(—s0dium);
`
`flurazole;
`
`flurenol(—butyl);
`
`fluridone;
`
`fluroehloridone;
`
`fluroxypyr(—meptyl);
`
`flur-
`
`primidol, flurtamone; fluthiaeet(—methyl) (KlH-9201); fluthiamide, fluxofenim; fomesafen; foramsulfu-
`
`ron,
`
`forchlorfenuron;
`
`fosamine;
`
`furilazole;
`
`furyloxyfen; gibberillie acid; glufosinate(—amm0nium);
`
`glyphosate(-is0pr0pylamm0nium); halosafen; halosulfur0n(-methyl); haloxyfop and its esters; halox-
`
`yfop—P (= R-haloxyfop) and its esters; HC—252; hexazinone;
`
`imazamethabenz(—methyl);
`
`imaza-
`
`1O
`
`15
`
`20
`
`25
`
`30
`
`35
`
`

`

`WO 2014/060502
`
`_ 6 _
`
`PCT/EP2013/071694
`
`mcthapyr, imazamox, imazapic, imazapyr; imazaquin and salts, such as the ammonium salt; imazctha—
`
`methapyr; imazethapyr; imazosulfuron; inabenfide; indanofan; indole—3—acetic acid; 4—indol—3 —ylbutyric
`
`acid; i0d0sulfi1r0n—methyl(-s0dium); ioxynil; isocarbamid; isopropalin; isoproturon; isouron; isoxaben;
`
`isoxachlmtole, isoxadifen(—ethyl); isoxaflutole, isoxapyrifop; karbutilate; lactofen; lenacil; linuron; ma-
`
`leic hydrazide (MH), MCPA; MCPB; mecopr0p(—P); mefenacet; mefenpyr(—diethyl); mefluidid; mepi—
`
`quat(—chloride); mesosulfilron(-methyl); mesotrione, metam; metamifop; metamitron; metazachlor;
`
`methabenzthiazuron; metham; methazole; methoxyphenone; methylarsonic acid; methylcyclopropene;
`
`methyldymron; methyl isothiocyanate; methabenzthiazuron; metobenzuron; metobromuron; (alpha-)-
`
`metolachlor; metosulam (XRD 511); metoxuron; metribuzin; metsulfuron-methyl; molinate; monalide;
`
`monocarbamide dihydrogensulfate; monolinuron; monuron; MT 128,
`
`i.e. 6-chlor0—N—(3—chlor0-2-
`
`p1‘0penyl)—5-methyl-N-phenyl-3 -py1idazi11a111i11e;
`
`MT 5950,
`
`i.e.
`
`N—[3 -chlor0—4—(l-
`
`methylethyl)phenyl]—2—methylpentanamide; naproanilide; napropamide; naptalam; NC 310, i.e. 4—(2,4—
`
`dichlorobenzoyl)-1-methyl-5-benzyloxypyrazole; neburon; nicosulfuron; nipyraclofen; nitralin; nitro-
`
`fen; nitrophenolate mixture; nitrofluorfen; nonanoic acid; norflurazon; orbencarb; orthasulfamuron; 0x-
`
`abctrinil; oryzalin; oxadiargyl (RP—020630); oxadiazon; oxasulfuron, oxaziclomcfonc, oxyfluorfcn;
`
`paclobutrazol; paraquat( dichloride); pebulate; pelargonic acid, pendimethalin; penoxsulam; pentachlo—
`
`rophenol; pentanochlor; pentoxazone, perfluidone; pethoxamid; phenisopham; phenmedipham; piclo-
`
`ram; picolinafen, pinoxaden, piperophos; piributicarb; pirifenop—butyl; pretilachlor; primisulfu—
`
`ron(—methyl); probenazole; procarbazone—(sodium), procyazine; prodiamine; profluralin; profoxydim;
`
`prohexadione(—calcium); prohydrojasmon; proglinazine(—ethyl); prometon; prometryn; propachlor; pro-
`
`panil; propaquizafop; propazine; propham; propisochlor; propoxycarbazone(—sodium) (MKH—656l); r1-
`
`propyl dihydrojasmonate; propyzamide; prosulfalin; prosulfocarb; prosulfuron (CGA—152005);
`
`prynachlor; pyraclonil; pyraflufen(-ethyl) (ET—75 1); pyrasulfotole; pyrazolynate; pyrazon; pyrazosulfu—
`
`r0n(-ethyl); pyrazoxyfen; pyribenzoxim, pyributicarb, pyridafol, pyridate; pyriftalid; pyriminobac(-
`
`methyl)
`
`(KIH—6l27); pyrimisulfan (KIH-5996); pyrithiobac(-s0dium)
`
`(KIH-203l); pyroxasulfone
`
`(KIH—485); pyroxofop and its esters (for example the propargyl ester); pyroxsulam; quinclorac; quin—
`
`merac; quinoclamine, quinofop and its ester derivatives, quizalofop and quizalofop—P and and their es-
`
`ter derivatives, for example quizalofop-ethyl; quizalofop-P-tefuryl and -ethyl; renriduron; rimsulfuron
`
`(DPX-E 9636); S 275,
`
`i.e. 2-[4-chlor0-2—flu0r0-5-(2—pr0pynyloxy)phcnyl]—4,5,6,7—tctrahydro-2H-
`
`indazole; saflufenacil, secbumeton; sethoxydim; siduron; simazine; simetryn; sintofen; SN 106279, i.e.
`
`2-[[7—[2-chlor0-4-(trifluor0methyl)phen0xy]—2—naphthalenyl]0xy]pr0pan0ic acid and methyl 2-[[7—[2-
`
`chlor0-4-(triflu01‘0methyl)phe110xy]-2-naphthalenyl]0xy]p1‘0panoate; sulcotrione, sulfent1azone (FMC—
`
`97285, F—6285); sulfazuron; sulfometur0n(—methyl); sulfosate (ICI—A0224); sulfosulfuron, TCA; tebu—
`
`tam (GCP-5544); tebuthiuron; tecnacene; tembotrione; tefuryltrione; tepraloxydim, terbacil; terbucarb;
`
`terbuchlor;
`
`terbumeton;
`
`terbuthylazine;
`
`terbutryn; TFH 450,
`
`i.e. N,N-diethyl-3-[(2-ethyl-6-
`
`mcthylphcnyl)sulf0nyl]—lH-1,2,4-triazolc-l-carboxamidc; thcnylchlor (NSK-850); thiafluamidc, thia-
`
`zafluron; thiazopyr (Mon— 13200); thidiazimin (SN-24085); thidiazuron; thiencarbazone—methyl; thifen—
`
`sulfur0n(-methyl); thiobencarb; Ti 35; tiocarbazil; topramezone; tralkoxydim; tri-allate; triasulfuron;
`
`1O
`
`15
`
`20
`
`25
`
`30
`
`35
`
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`

`WO 2014/060502
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`PCT/EP2013/071694
`
`triaziflam, triazofenamide; tribenuron(—methyl); triclopyr; tridiphane; trietazine; trifloxysulfuron; triflu—
`
`ralin; triflusulfuron and esters (for example the methyl ester, DPX—66037); trimeturon; trinexapac; trito—
`
`sulfilron, tsitodef; uniconazole; vernolate; WL 110547, i.e. 5-phenoxy-1-[3-(trifluoromethyl)phenyl]—
`
`lH—tetrazole; D-489; LS 82-556; KPP-300; NC—324; NC—330; DPX-N8189; SC—0774; DOWCO-535;
`
`DK—8910gV—53482; PP—600 and MBH—001.
`
`Herbicides of Group (B) which are suitable for combination with the N-cyclopropyl—N-[substituted-
`
`benzyl]—3 -(difluoromethyl)-5-flu oro— 1 —methyl—1H—pyrazole—4—carboxamide
`
`or thiocarboxamide de-
`
`rivatives of formula (I) are preferably selected from the group consisting of:
`
`(B- 1) Herbicides of the type of the phenoxyphenoxy- and heteroaryloxyphenoxycarboxylie acid de-
`
`rivatives selected from the group consisting of
`
`(3—1.1)
`
`phenoxyphenoxy- and benzyloxyphenoxycarboxylic acid derivatives, for example
`
`(B—1.1.1) methyl 2—(4—(2,4—dichlorophenoxy)phenoxy)propionate (diclofop—methyl),
`
`(B-1.1.2) methyl
`
`2-(4-(4-bromo—2—chlorophenoxy)phenoxy)propionate
`
`(DE-A
`
`26 01 548),
`
`(3—1.1.3) methyl 2-(4-(4-brom0-2-fluorophenoxy)phenoxy)propionate
`
`(US 4,808,750), (B—l.l.4) methyl 2—(4—(2—chloro—4—trifluoromethylphenoxy)phenoxy)—
`
`propionate (DE—A 24 33 067), (B—1.1.5) methyl 2-(4—(2-fluoro—4—trifluoromethylphen—
`
`oxy)phen0xy)propionate (US 4,808,750), (B—1.1.6) methyl 2-(4-(2,4-diehlorobenzyl)-
`
`phenoxy)propionate
`
`(DE-A 24 17 487),
`
`(B-1.1.7)
`
`ethyl
`
`4-(4—(4-trifluoromethyl-
`
`phenoxy)phenoxy)pent—2—enoate,
`
`(B—1.1.8) methyl 2—(4—(4—trifluoromethylphenoxy)—
`
`phenoxy)propionate
`
`(DE—A 24 33 067),
`
`(B-1.1.9)
`
`butyl
`
`(R)—2—[4-(4—cyano-2-
`
`fluorophenoxy)phenoxy]propionate (cyhalofop—butyl);
`
`(3—1.2)
`
`“monocyclic” heteroaryloxyphenoxyalkanecarboxylic acid derivatives, for example
`
`(B— 1 .2. 1 )
`
`ethyl
`
`2—(4-(3 , 5 - dichloropyridyl—2 -oxy)phenoxy)propionate
`
`(EP-
`
`A 0 002 925),
`
`(B-1.2.2)
`
`propargyl
`
`2-(4-(3,5-diehloropyridyl-2-
`
`oxy)phenoxy)propionate (EP—A 0 003 114), (B-1.2.3) methyl (RS)- or (R)-2-(4—(3-
`
`chloro—5—trifluoromethyl—2—pyridyloxy)phenoxy)propionate (haloxyfop—methyl or ha—
`
`loxyfop—P—methyl),
`
`(B—1.2.4) ethyl 2-(4-(3 -chloro—5—trifluoromethyl—2-pyridyloxy)—
`
`phenoxy)propionate (EP-A 0 003 890), (B-1.2.5) propargyl 2-(4-(5-chloro—3—fluoro-2-
`
`pyridyloxy)phenoxy)propionate (clodinafop—propargyl), (B—1.2.6) butyl (RS)— or (R)—2—
`
`(4—(5-trifluoromethyl-2-pyridyloxy)phenoxy)propionate (fluazifop-butyl or fluazifop-
`
`P-butyl),
`
`(B-1.2.7)
`
`(R)—2—[4-(3-chloro-S-trifluoromethyl-2-pyridyloxy)phenoxy]pro-
`
`pionie acid;
`
`(B—1.3)
`
`“bicyclic” hetero aryloxyphenoxyalkaneearboxylic acid derivatives,
`
`for example
`
`(3- 1 .3. 1) quizalofop—methyl,
`
`(B- 1 .3 .2) quizalofop-ethyl,
`
`(B- 1 .3.3) quizalofop-P-
`
`methyl,
`
`(B— 1 .3 .4)
`
`quizalofop-P-ethyl,
`
`(B— 1 .3 . 5) methyl
`
`2—(4-(6—fluoro-2-
`
`10
`
`15
`
`20
`
`25
`
`30
`
`35
`
`

`

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`
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`
`PCT/EP2013/071694
`
`quinoxalyloxy)phenoxy)propionate (see J. Pest. Sci. 1985, 10, 61),
`
`(B-1.3.6)
`
`propaquizafop,
`
`(B—l.3.7)
`
`ethyl
`
`fenoxaprop—ethyl,
`
`(3—138)
`
`fenoxaprop—P—ethyl,
`
`(B-1.3.9)
`
`ethyl
`
`2—(4-(6—chlorobenzthiazol-2-yloxy)phenoxy)propionate
`
`(DE-A-
`
`26 40 730), (3-13.10) tetrahydro-2-fi1rylmethyl (RS)- or (R)-2—(4—(6-chloroquinoxal-
`
`yloxy)phcnoxy) propionatc (EP-A 0 323 727),
`
`(3-13.11)
`
`(R)—2—[4-(6—chloro-1,3-
`
`benzoxazol-2-yloxy)phenoxy]-2'-fluoro—N—methylpropionanilide (metamifop);
`
`(13-2)
`
`Herbicides from the group of the sulfonylureas, such as pyrimidinyl— or triazinylaminocar-
`
`b0nyl[benzene-,
`
`-pyridine-,
`
`-pyrazole-,
`
`-thiophene—
`
`and
`
`-(alkyl-
`
`sulfonyl)alkylamino]sulfamides, with preferred substituents on the pyrimidine ring or the tria—
`
`zine ring selected from alkoxy, alkyl, haloalkoxy, haloalkyl, halogen or dimethylamino, it be-
`
`ing possible to combine all substituents independently of one another and with preferred sub-
`
`stituents in the benzene, pyridine, pyrazole, thiophene or (alkylsulfonyl)alkylamino moiety
`
`selected from alkyl, alkoxy, halogen, nitro, alkoxycarbonyl, aminocarbonyl, alkylaminocar—
`
`bonyl, dialkylaminocarbonyl, alkoxyaminocarbonyl, haloalkoxy, haloalkyl, alkylcarbonyl,
`
`alkoxyalkyl, (alkanesulfonyl)Alkylamino, which sulfonylureas are selected from the group
`
`consisting of
`
`(B—2.1) phenyl- and benzylsulfonylureas and related compounds, for example (B-2.1.1) chlor-
`
`sulfuron, (B-2.1.2) chlofimuron—ethyl, (B—2.1.3) metsulfin‘on—methyl, (B-2. 1.4) triasul-
`
`furon, (B—2.1.5) sulfometuron—methyl, (3-2.1.6) tribenuron—methyl, (B-2.1.7) bensul-
`
`furon-methyl, (B-2.1.8) primisulfuron-methyl, (B-2. 1.9) 3-(4-ethyl-6-methoxy- 1,3,5 -
`
`triazin—2-yl)—1—(2,3-dihydro—1,1—dioxo-2-methylbenzo[b]thiophene-7-sulfonyl)urea
`
`(EP—A 0 079 83),
`
`(B-2. 1 . 10)
`
`3—(4-cthoxy—6-cthyl-l,3,5-triazin—2—yl)-1-(2,3-dihydro-
`
`1,1—dioxo—2—methylbenzo[b]—thiophene—7—sulfonyl)urea (EP—A 0 079 683),
`
`(B—2.1.11)
`
`3-(4—methoxy—6—methyl— 1 ,3,5—triazin-2—yl)- 1 -(2—methoxycarbonyl-5 -iodophenyl-
`
`sulfonyl)urea (W0 92/ 13845), (B-2.1.12) tliflusulfin'on-methyl, (B-2.1.13) oxasulfu—
`
`ron,
`
`(B—2.1.14)
`
`iodosulfuron—methyl,
`
`(B—2. 1.15)
`
`iodosulfuron—methyl—sodium,
`
`(B—2.1.16) mesosulfuron, (B-2.1.17) mesosulfuron—methyl, (B—2.1.18) foramsulfuron,
`
`(B-2.1.19) cinosulfuron, (B-2.1.20) ethametsulfuron—methyl, (B-2.1.21) prosulfuron,
`
`(3-2122) tritosulfuron, (B—2.1.23) monosulfuron, (B-2.1.24) methyl 2—[({[methoxy-
`
`6—(methylthio)pyrimidin—2—yl] carb amoyl} amino) sulfonyl]benzoate;
`
`(B—2.2) thienylsulfonylureas, for example (B-2.2.1) thifensulfilron-methyl;
`
`(B—2.3) pyrazolylsulfonylureas, for example (B-2.3.1) pyrazosulfuron—ethyl, (B-2.3.2) methyl
`
`halo sulfuron—methyl,
`
`(B —2. 3 . 3)
`
`methyl
`
`5 —(4,6—dimethylpyrimidin—2—yl—
`
`carbamoylsulfamoyl)—1—(2-pyridyl)pyrazole-4-carboxylate
`
`(NC—330,
`
`see Brighton
`
`Crop Prot. Conference Weeds 1991, 1, 45ff.), (B—2.3.4) azimsulfuron, (B-2.3.5) N-
`
`1O
`
`15
`
`20
`
`25
`
`30
`
`35
`
`

`

`WO 2014/060502
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`
`[(4,6-dimcth0xypyrimidin—2-yl)carbamoyl] —4—(5 ,5 -dimcthyl-4,5 -dihydr0is0xazol-3 —
`
`yl)— 1,3 —dimethyl— lH—pyrazole—S —sulf0namide;
`
`(B—2.4) sulfonediamide derivatives, for example (B-2.4.1) amidosulfuron and (B-2.4.2) its
`
`structural analogs (EP-A 0 131 258 and Z. Pfl. Krankh. Pfl. Schutz, special issue XII,
`
`489—497 (1990));
`
`(B—2.5) pyridylsulfonylureas,
`
`for example (3-2.5 .1) nicosulfuron,
`
`(B-2.5 .2) rimsulfuron,
`
`(3-2.5.3) flupyrsulfiiron-methyl, (3—2.5.4) flupyrsulfiiron-methyl-s0dium, (3-255)
`
`3 -(4,6—dimcth0xypyrimidin—2—yl)— 1 —(3 -N —mcthylsulf0nyl—N -mcthylamin0pyridin-2-
`
`yl)sulf0nylurea or its salts (DE—A 40 00 503 and DE-A 40 30 577), (B-2.5.6) fla-
`
`zasulfuron, (3-2.5 .7) trifloxysulfuron—sodium, (B-2.5 .8) flucetosulfuron;
`
`(B—2.6) alkoxyphenoxysulfonylureas, for example (B-2.6.1) ethoxysulfuron or (B-2-6.2) its
`
`salts;
`
`(B—2.7) imidazolylsulfonylureas, for example (B-2.7.1) sulfosulfuron, (B—2.7.2) imazosulfu—
`
`1'011,
`
`(B—2.7.3)
`
`2—011101‘0-N—[(4,6-dimethoxypyfimidin—2-yl)ca1‘bamoyl]-6-
`
`propylimidazo [1 ,2—b]pyridazine—3 —sulf0namide;
`
`(B—2.8) phenylaminosulfonylureas, for example (B-2.8.1) cyclosulfamuron, (B—2.8.2) ortho-
`
`su lfamur011;
`
`(13-3)
`
`Chloroacetanilides,
`
`for example (B—3.1) acetochlor,
`
`(B—3.1) alachlor,
`
`(B-3.2) butachlor,
`
`(B—3.3) dimethachlor, (B—3.4) dimethenamid, (B-3.5) dimethanamid-P metazachlor, (B-3.6)
`
`metolachlor,
`
`(3-3.7) S-metolachlor,
`
`(3-3.8) pethoxamid,
`
`(B-3.9) pretilachlor,
`
`(B—3.10)
`
`propachlor, (B-3.1 1) propisochlor and (B—3.12)thenylchlor;
`
`(13-4)
`
`Thiocarbamates, for example (B—4.1) S—ethyl N,N—dipr0pylthiocarbamate (EPTC), (B—4.2) S—
`
`ethyl N,N—diisobutylthiocarbamate (butylate), (B—4.3) cycloate, (B—4.4) dimepiperate, (B-4.5)
`
`esprocarb,
`
`(3—4.6) molinate,
`
`(3-4.7) orbencarb,
`
`(3—4.8) pebulate,
`
`(B—4.9) prosulfocarb,
`
`(B—4.10) thiobencarb, (3—4.1 1) tiocarbazil, (B—4. 12) tIi—allate and (B—4.13) vemolate;
`
`(13-5)
`
`Cyclohexanedione oximes,
`
`for example (B-5.1) alloxydim,
`
`(B—5.2) butroxydim,
`
`(B-5.3)
`
`clethodim, (B—5.4) cloproxydim, (B-5.5) cycloxydim,
`
`(B—5.6) profoxydim, (B-5.7) sethox-
`
`ydim, (B-5.8) tepraloxydim and (B-5 .9) tralkoxydim;
`
`(3-6)
`
`Imidazolinones, for example (B-6.1) imazamethabenz-methyl, (B-6.2) imazapic, (B—6.3) ima-
`
`zamox, (B—6.4) imazapyr, (B-6.5) imazaquin and (3-6.6) imazethapyr;
`
`10
`
`15
`
`20
`
`25
`
`30
`
`

`

`WO 2014/060502
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`
`PCT/EP2013/071694
`
`(3-7)
`
`Triazolopyrimidincsulfonamidc derivatives,
`
`for example
`
`(B-7.1)
`
`chloransulam-mcthyl,
`
`(B—7.2) diclosulam, (B—7.3) florasulam, (B—7.4) flumetsulam, (B—7.5) metosulam, (B—7.6) pe—
`
`noxsulam (3-7.7) and pyroxsulam;
`
`(3-8)
`
`Benzoylcyelohexanediones, for example (B—8. 1) sulcotrione, (B—8 .2) 2-(2—nit1‘0benzoyl)-4,4-di-
`
`methylcyclohexane— 1,3—dione (EP—A 0 274 63 4), (3—8 .3) 2—(2—nitr0—3—methylsulf0nylbenzoyl)—
`
`4,4-dimethylcyclohexane-1,3-dione (WO 91/13548), (B—8.4) mesotrione, (B—8 .5) 2-[2—chlor0-
`
`3-(5—cya110methyl—4,5—dihydr0isoxazol-3-yl)—4-(ethylsulfonyl)benzoyl]—1,3-cyclohexanedi0ne,
`
`(B—8.6) 2- [2-chlor0-3-(5-cyan0mcthyl-4,5-dihydroisoxazol-3-yl) -4-(methylsulfonyl)bcnzoyl]-
`
`1,3-cyclohexanedi0ne,
`
`(B— 8.7)
`
`2— [2-chlor0-3 -(5 -eth0xymethyl—4,5—dihydroisoxazol-3 -yl)-4-
`
`(ethylsulfonyl)benzoyl]—1,3-cyclohexanedione,
`
`(B-8 . 8)
`
`2-[2—chlor0-3 -(5 -ethoxymethyl-4,5-
`
`dihydroisoxazol—3 —yl)—4—(methylsulfonyl)benzoyl] - 1 ,3 -cyclohexanedi0ne,
`
`(B— 8. 9) 2- [2 —chlor0-
`
`3 — [(2,2,2—triflu0r0eth0xy)methyl] —4—(ethylsulfonyl)b enzoyl] — 1,3 —cyclohexanedione,
`
`(B—8. 10)
`
`tembotrione,
`
`(B-8.1 1) 2—[2-chlor0—3—[(2,2—diflu0roeth0xy)methyl]-4-(ethylsulf0nyl)benzoyl]-
`
`1,3-cyclohexanedione,
`
`(B—8. 12)
`
`2-[2-chloro-3-[(2,2-difluoroethoxy)methyl]-4-
`
`(methylsulfonyl)bcnzoyl]— 1,3-cyclohcxancdi0nc,
`
`(3-8. 13)
`
`2- [2—ch10r0-3—[(2,2,3,3-
`
`tetrafluoropropoxy)methyl] -4-(ethylsulfonyl)benzoyl] —