WO2015104699A2 - Combination of novel nitrification inhibitors and fungicides as well as combination of (thio)phosphoric acid triamides and fungicides - Google Patents

Combination of novel nitrification inhibitors and fungicides as well as combination of (thio)phosphoric acid triamides and fungicides Download PDF

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WO2015104699A2
WO2015104699A2 PCT/IB2015/052773 IB2015052773W WO2015104699A2 WO 2015104699 A2 WO2015104699 A2 WO 2015104699A2 IB 2015052773 W IB2015052773 W IB 2015052773W WO 2015104699 A2 WO2015104699 A2 WO 2015104699A2
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phenyl
methyl
inhibitors
alkyl
fluoro
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PCT/IB2015/052773
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French (fr)
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WO2015104699A3 (en
Inventor
Barbara Nave
Joachim Dickhaut
Mihiret Tekeste SISAY
Alexander Wissemeier
Wolfram Zerulla
Gregor Pasda
Markus Schmid
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Basf Se
Basf (China) Company Limited
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Publication of WO2015104699A2 publication Critical patent/WO2015104699A2/en
Publication of WO2015104699A3 publication Critical patent/WO2015104699A3/en

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
    • A01N31/14—Ethers
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/26—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-nitrogen bonds
    • A01N57/28—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-nitrogen bonds containing acyclic or cycloaliphatic radicals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
    • Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
    • Y02P60/21—Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures

Definitions

  • the present invention relates to the combination of novel nitrification inhibitors of formula I and fungicides as well as to the combination of (thio)phosphoric acid triamides and fungicides. Moreover, the invention relates to the use of this combination of novel nitrification inhibitors and fungicides for increasing the health of a plant, and to the use of the combination of
  • compositions comprising the nitrification inhibitor and a fungicide for increasing the health of a plant, as well as compositions comprising the nitrification inhibitor and a fungicide, and compositions comprising the (thio)phosphoric acid triamide and a fungicide.
  • methods for increasing the health of a plant comprising the treatment of plants, soil and/or loci with said combination of the novel nitrification inhibitor and a fungicide or with said combination of (thio)phosphoric acid triamides and a fungicide.
  • Nitrogen is an essential element for plant growth, plant health and reproduction. About 25% of the plant available nitrogen in soils (ammonium and nitrate) originate from decomposition processes (mineralization) of organic nitrogen compounds such as humus, plant and animal resi- dues and organic fertilizers. Approximately 5% derive from rainfall. On a global basis, the biggest part (70%), however, are supplied to the plant by inorganic nitrogen fertilizers.
  • the mainly used nitrogen fertilizers comprise ammonium compounds or derivatives thereof, i.e. nearly 90% of the nitrogen fertilizers applied worldwide is in the Nh form (Subbarao et al., 2012, Advances in Agronomy, 1 14, 249-302). This is, inter alia, due to the fact that Nh assimilation is energeti- cally more efficient than assimilation of other nitrogen sources such as NO3 " .
  • N h is held electrostatically by the negatively charged clay surfaces and functional groups of soil organic matter. This binding is strong enough to limit NhV-loss by leaching to groundwater.
  • NO3 " being negatively charged, does not bind to the soil and is liable to be leached out of the plants' root zone.
  • nitrate may be lost by denitri- fication which is the microbiological conversion of nitrate and nitrite (NO2 ) to gaseous forms of nitrogen such as nitrous oxide (N2O) and molecular nitrogen (N2).
  • ammonium (N hV) compounds are converted by soil microorganisms to nitrates (NO3 " ) in a relatively short time in a process known as nitrification.
  • the nitrification is carried out primarily by two groups of chemolithotrophic bacteria, ammonia-oxidizing bacteria (AOB) of the genus Nitrosomonas and Nitrobacter, which are ubiquitous component of soil bacteria populations.
  • AOB ammonia-oxidizing bacteria
  • Nitrobacter which are ubiquitous component of soil bacteria populations.
  • the enzyme, which is essentially responsible for nitrification is ammonia monooxygenase (AMO), which was also found in ammonia-oxidizing archaea (Subbarao et al., 2012, Advances in Agronomy, 1 14, 249-302).
  • Suitable nitrification inhibitors include biological nitrification inhibitors (BNIs) such as linoleic acid, alpha-linolenic acid, methyl p-coumarate, methyl ferulate, MHPP, Karanjin, brachi- alacton or the p-benzoquinone sorgoleone (Subbarao et al., 2012, Advances in Agronomy, 1 14, 249-302).
  • BNIs biological nitrification inhibitors
  • nitrification inhibitors are synthetic chemical inhibitors such as Nitra- pyrin, dicyandiamide (DCD), 3,4-dimethyl pyrazole phosphate (DMPP), 4-amino-1 ,2,4-triazole hydrochloride (ATC), 1 -amido-2-thiourea (ASU), 2-amino-4-chloro-6-methylpyrimidine (AM), 5- ethoxy-3-trichloromethyl-1 ,2,4-thiodiazole (terrazole), or 2-sulfanilamidothiazole (ST) (S GmbH and Kerkhoff, 1984, Fertilizer research, 5(1 ), 1-76).
  • DCD 3,4-dimethyl pyrazole phosphate
  • ATC 4-amino-1 ,2,4-triazole hydrochloride
  • ASU 1 -amido-2-thiourea
  • AM 2-amino-4-chloro-6-methylpyrimidine
  • ST 2-sulfanilamidothiazo
  • EP 0 917 526 further mentions the use of polyacids to treat mineral fertilizers containing a nitrifi- cation inhibitor in order to improve the fixation of the nitrification inhibitors in the inorganic fertilizer. Moreover, the volatility of the nitrification inhibitor can be reduced.
  • Healthier plants are desirable since they result among other in better crop yields and/or a better quality of the plants or crops. Healthier plants also better resist to biotic and abiotic stress. A better resistance to stress in turn allows reducing the quantity of pesticides, which also helps avoiding the development of resistances against the respective pesti- cides.
  • One object of the present invention is to provide a composition containing a nitrification inhibitor which increases the health of plants, and/or provides better crop yields and/or a better quality of the plants or crops, and/or shows a better resistance to stress, and/or allows the reduction of the quantity of pesticides used, and/or helps avoiding the development of resistances against the respective pesticides
  • Another object of the present invention is to provide a composition containing the
  • ⁇ v reduces the emission of nitrous oxide from soils
  • (vii) is toxicologically unobjectionable, and/or (viii) does not adversely affect the urease-inhibiting effect and/or activity of the (thio)phosphoric acid triamide, and/or
  • (xxiii) enable earlier seed germination and/or blooming.
  • the objects (xiii), (xiv), (xv), (xvi), (xvii) and (xxi) particularly pertains to such plants or seedlings wherein such plants or seedlings were, or the soil in which the such plants or seedlings were placed was subject to the application of compositon of the present invention.
  • the preferred objects of the present invention are (i), (ii), (v), (vi), (vii), (xi), (xii), (xiii), (xiv), (xv), (xvi), (xvii), (xviii), (xix), (xx), the more preferred objects of the present invention are (ii), (vi), (xii), (xiii), (xv), (xvi), (xix), and/or (xx), the most preferred objects of the present invention are (ii), (vi), (xvi), and/or (xix), the particularly preferred objects of the present invention are (xvi) and/or (xix).
  • composition comprising the (thio)phosphoric acid triamide (T) and a further compound can fulfil the one or more of the objects (i) to (xxvii) significantly better than the individual compounds - i.e. the (thio)phosphoric acid triamide (T) or said further compound - alone can do, and preferably, this better fulfilment of the objects by said composition compared to the individual compounds is evidenced by calculations according to Colby' s formula, see Colby, S. R. (Calculating synergistic and antagonistic responses of herbicide Combinations", Weeds, 15, pp. 20-22, 1967)
  • the present invention addresses this need and relates to a combination of a novel nitrification inhibitor of formula I or a stereoisomer, salt, tautomer or N-oxide thereof, wherein
  • A is aryl or hetaryl, wherein the aromatic ring may in each case be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from R A ;
  • R 1 and R 2 are independently of each other selected from H and Ci-C2-alkyl
  • R 3 is H, Ci-C4-haloalkyl, Ci-C4-hydroxyalkyl, ethynylhydroxym ethyl, phenylhydroxymethyl, or aryl, wherein the aromatic ring may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from R B ; and wherein
  • a 3- to 14-membered saturated or unsaturated carbocycle or heterocycle which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from NR 1b , O, and S, wherein S may be oxidized and/or wherein the carbocycle or het- erocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R 1b is H, C1-C4- alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6-cycloalkylmethyl, or ORa; or
  • B is aryl or hetaryl, wherein the aromatic ring of the ary or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from R h ;
  • a 3- to 14-membered saturated or unsaturated carbocycle or heterocycle which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from N R 1b , O, and S, wherein S may be oxidized and/or wherein the carbocycle or heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R 1b is H, Ci-C4-alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6-cycloalkylmethyl, or OR9; or
  • two substituents R A together represent a carbocyclic or heterocyclic ring, which is fused to A and may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from NR 1c , O, and S, wherein S may be oxidized and/or wherein the carbocycle or heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R 1c is H, d-C 4 -alkyl, C 2 -C 4 -alkenyl, C3-C 6 -cycloalkyl, C 3 -C 6 - cycloalkylmethyl, C3-C6-heterocyclyl, C3-C6-heterocyclylmethyl or OR9; and wherein
  • Y 1 , Y 2 and Y 3 are independently of each other selected from O, S and NR 1a , wherein R 1a is in each case independently H, Ci-C4-alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6- cycloalkylmethyl, ORa, SRa or NR m R n ;
  • R a and R b are independently of each other selected from
  • aryl or hetaryl wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from R h ; or
  • R a and R b together with the nitrogen atom to which they are bound form (iii) a hetaryl group which may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from R h ; or
  • a 3- to 10-membered, saturated or unsaturated heterocycle which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from NR 1b , O, and S, wherein S may be oxidized and/or wherein the heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R 1b is H , Ci-C4-alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C 6 -cycloalkylmethyl, or ORa; R c is
  • R is Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, NRR k , OR, SR, aryl or hetaryl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from R h ;
  • R9 is H or Ci-C 4 -alkyl
  • R 1d is H, Ci-C 4 -alkyl, C 2 -C 4 -alkenyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 - cycloalkylmethyl, or OR9;
  • R m and R n are independently selected from H and Ci-C 4 -alkyl
  • the present invention relates in another aspect to the composition (Q) comprising a fungicide and a (thio)phosphoric acid triamide according to the general formula (la)
  • X is oxygen or sulfur
  • R a1 is a Ci to C20 alkyl, C3 to C20 cycloalkyl, C& to C20 aryl, or dialkylaminocarbonyl group
  • R a2 is H , or
  • R a1 and R a2 together with the nitrogen atom linking them define a 5- or 6-membered saturated or unsaturated heterocyclic radical, which optionally comprises 1 or 2 further heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur, and the present invention preferably relates to a composition (Q) comprising a fungicide and a (thio)phosphoric acid triamide according to the general formula (la) and not comprising any nitrification inhibitor of the compound of formula I.
  • the composition (Q) also includes kit-of-parts comprising a fungicide and (T).
  • kit-of-parts is to be understood to denote a kit comprising at least two separate parts wherein each of the parts can be independently removed from the kit.
  • a kit includes a box, a tool, a vessel, a container, a bag or any kit-like equipment. Also a kit whose separate parts are only to- gether in this one kit for a extremely short period of time are regarded as kit-of-parts. Kit-of-parts are useful for the combined application (of the contents) of the separate parts of the kit.
  • the present invention relates in another aspect to the use of a composition (Q) comprising a fungicide and a (thio)phosphoric acid triamide (T) for increasing the health of a plant, and the present invention preferably relates to the use of a composition (Q) comprising a fungicide and a (thio)phosphoric acid triamide (T) and not comprising any nitrification inhibitor of the compound of formula I for increasing the health of a plant.
  • X in the general formula (la) is preferably sulfur.
  • R a1 in the general formula (la) is preferably Ci-C2o-alkyl, more preferably Ci-Cio-alkyl, most preferably C2-C7 alkyl, for example C3-C4 alkyl.
  • alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hex- yl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl and isodecyl.
  • Examples of cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclooctyl, examples of aryl groups are phenyl or naphthyl.
  • Examples of heterocyclic radicals R a1 R a2 N- are piperazinyl, morpholinyl, pyrrolyl, pyrazolyl, triazolyl, oxazolyl, thiazolyl or imidazolyl groups.
  • the (thio)phosphoric acid triamide (T) is preferably N-n- butylthiophosphoric acid triamide (NBPT) and/or N-n-propylthiophosphoric acid triamide (NPPT), more preferably NBPT.
  • (T) is preferably NPPT.
  • (T) is preferably LIM US, i.e. a mixture of NBPT and NPPT with about NBPT at 63% and NPPT at 22%, secondary compounds at 10%, further secondary compounds such as amines below 4% and dimerease derivatives below 1 %.
  • the composition (Q) comprises a fungicide and at least two different (thio)phosphoric acid triamides (T) having structures of the general formula (la) and wherein said at least two different (thio)phosphoric acid triamides differ in a of radicals R a1 or R a2 , and preferably, one of said at least two different (thio)phosphoric acid triamides is N-n- butylthiophosphoric acid triamide (NBPT), and more preferably, the other of said at least two different (thio)phosphoric acid triamides is selected from the group consisting of N-cyclohexyl-, N-pentyl-, N-isobutyl- and N-n-propylphosphoric acid triamide and -thiophosphoric acid triamide.
  • T at least two different (thio)phosphoric acid triamides having structures of the general formula (la) and wherein said at least two different (thio)phosphoric acid triamides differ in a of radicals R a1 or R a
  • (Q) comprises a fungicide, NBPT and NPPT.
  • (Q) comprises a fungicide, NBPT and NPPT, wherein NBPT is present in amounts of from 1 to 99.99 wt.%, more preferably from 10 to 99.9 wt.%, most preferably from 20 to 99 wt.%, particularly preferably from 30 to 98 wt.%, more particularly preferably from 40 to 95 wt.%, most particularly preferably from 50 to 90 wt.%, especially from 60 to 85 wt.%, especially preferably from 72 to 80 wt.%, for example from 74 to 77 wt.%, in each case based on the total weight of the (thio)phosphoric acid triamides (T) contained in the composition (Q).
  • the (thio)phosphoric acid triamides (T) can be contained in varying amounts in the composition (Q).
  • the amount of (T) is not more than 95 wt.% (wt.% stands for "percent by weight"), more preferably not more than 90 wt.%, most preferably not more than 85 wt.%, more particularly preferably not more than 75 wt.%, most particularly preferably not more than 65 wt.%, particularly not more than 55 wt.%, especially not more than 45 wt.% for example not more than 35 wt.%, based on the total weight of the composition (Q).
  • the amount of (T) is at least 1 wt.%, more preferably at least 4 wt.%, most preferably at least 14 wt.%, more particularly preferably at least 24 wt.%, most particularly preferably at least 34 wt.%, particularly at least 44 wt.%, especially at least 54 wt.%, for example at least 64 wt.%, based on the total weight of the composition (Q).
  • the composition (Q) preferably does not comprise any nitrification inhibitor of the compound of formula I.
  • the present invention relates to the use of combination of a fungicide and a nitrification inhibitor for increasing the health of a plant, wherein said nitrification inhibitor is a compound of formula I as defined herein above.
  • A is phenyl or a 5- or 6- membered hetaryl, wherein the aromatic ring may in each case be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from R A .
  • R 1 and R 2 both represent hydrogen.
  • R 3 is hydrogen, Ci-C4-haloalkyl or ethinylhydroxym ethyl, and preferably R 3 is hydrogen.
  • R A in said compound of formula I, is
  • a 3- to 14-membered saturated or unsaturated heterocycle which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from NR 1b , O, and S, wherein S may be oxidized and/or wherein the heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R 1b is H , Ci-C 4 -alkyl, C2-C 4 -alkenyl, C3-C6-cycloalkyl,
  • the fungicide is at least one fungicide selected from the group of fungicides comprising:
  • Respiration inhibitors such as:
  • Inhibitors of complex III at Q 0 site e.g. strobilurines selected from, azoxystrobin (A.1 .1 ), coumethoxystrobin (A.1.2), coumoxystrobin (A.1.3), dimoxystrobin (A.1 .4), enestroburin (A.1.5), fenaminstrobin (A.1.6), fenoxystrobin/flufenoxystrobin (A.1 .7), fluoxastrobin (A.1 .8), kresoxim-m ethyl (A.1.9), mandestrobin (A.1 .10), meto- minostrobin (A.1 .1 1 ), orysastrobin (A.1 .12), picoxystrobin (A.1 .13), pyraclostrobin (A.1 .14), pyrametostrobin (A.1 .15), pyraoxystrobin (A.1.16), trifloxystrobin
  • inhibitors of complex III at Q, site selected from cyazofamid (A.2.1 ), amisulbrom (A.2.2), [(3S,6S,7R,8R)-8-benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2- carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate (A.2.3), [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)-4-methoxy-pyridine- 2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate
  • inhibitors of complex II selected from benodanil (A.3.1 ), ben- zovindiflupyr (A.3.2), bixafen (A.3.3), boscalid (A.3.4), carboxin (A.3.5), fenfuram (A.3.6), fluopyram (A.3.7), flutolanil (A.3.8), fluxapyroxad (A.3.9), furametpyr (A.3.10), isofetamid (A.3.1 1 ), isopyrazam (A.3.12), mepronil (A.3.13), oxycarboxin (A.3.14), penflufen (A.3.14), penthiopyrad (A.3.15), sedaxane (A.3.16), tecloftalam (A.3.17), thifluzamide (A.3.18), N-(4'-trifluoromethylthiobiphenyl-2-yl)- 3-difluoromethyl
  • terol biosynthesis inhibitors such as:
  • phenylamides or acyl amino acid fungicides selected from benalaxyl (C.1 .1 ), ben- alaxyl-M (C.1.2), kiralaxyl (C.1.3), metalaxyl (C.1 .4), metalaxyl-M (mefenoxam, C.1.5), ofurace (C.1.6), oxadixyl (C.1.7);
  • tubulin inhibitors selected from benzimidazoles, thiophanates: benomyl (D1 .1 ), carbendazim (D1 .2), fuberidazole (D1.3), thiabendazole (D1.4), thiophanate- methyl (D1.5); triazolopyrimidines: 5-chloro-7-(4-methylpiperidin-1 -yl)-6-(2,4,6- trifluorophenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine (D1.6);
  • MAP / histidine kinase inhibitors selected from fluoroimid (F.1.1 ), iprodione (F.1 .2), procymidone (F.1 .3), vinclozolin (F.1.4), fenpiclonil (F.1.5), fludioxonil (F.1.6);
  • G protein inhibitors selected from quinoxyfen (F.2.1 );
  • Lipid and membrane synthesis inhibitors such as:
  • Phospholipid biosynthesis inhibitors selected from edifenphos (G.1.1 ), iprobenfos (G.1 .2), pyrazophos (G.1.3), isoprothiolane (G.1.4);
  • lipid peroxidation inhibitors selected from dicloran (G.2.1 ), quintozene (G.2.2), tec- soloene (G.2.3), tolclofos-methyl (G.2.4), biphenyl (G.2.5), chloroneb (G.2.6), etridiazole (G.2.7);
  • phospholipid biosynthesis and cell wall deposition inhibitors selected from dime- thomorph (G.3.1 ), flumorph (G.3.2), mandipropamid (G.3.3), pyrimorph (G.3.4), benthiavalicarb (G.3.5), iprovalicarb (G.3.6), valifenalate (G.3.7) and N-(1 -(1 -(4- cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester (G.3.8);
  • (xx) fatty acid amide hydrolase inhibitors selected from oxathiapiprolin (G.5.1 ), 2- ⁇ 3-[2- (1 - ⁇ [3,5-bis(difluoromethyl-1 H-pyrazol-1 -yl]acetyl ⁇ piperidin-4-yl)-1 ,3-thiazol-4-yl]- 4,5-dihydro-1 ,2-oxazol-5-yl ⁇ phenyl methanesulfonate (G.5.2), 2- ⁇ 3-[2-(1 - ⁇ [3,5- bis(difluoromethyl)-1 H-pyrazol-1 -yl]acetyl ⁇ piperidin-4-yl) 1 ,3-thiazol-4-yl]-4,5- dihydro-1 ,2-oxazol-5-yl ⁇ -3-chlorophenyl methanesulfonate (G.5.3);
  • inorganic active substances selected from Bordeaux mixture (H .1 .1 ), copper acetate (H.1 .2), copper hydroxide (H.1.3), copper oxychloride (H.1 .4), basic copper sulfate (H.1.5), sulfur (H.1.6);
  • organochlorine compounds e.g. phthalimides, sulfamides, chloronitriles
  • organochlorine compounds selected from anilazine (H .3.1 ), chlorothalonil (H .3.2), captafol (H.3.3), captan (H.3.4), folpet (H.3.5), dichlofluanid (H.3.6), dichlorophen (H.3.7), hexachlorobenzene (H.3.8), pentachlorphenole (H.3.9) and its salts, phthalide (H.3.10), tolylfluanid (H.3.1 1 ), N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl-benzenesulfonamide (H .3.12);
  • organochlorine compounds e.g. phthalimides, sulfamides, chloronitriles
  • inhibitors of glucan synthesis selected from validamycin (1.1 .1 ), polyoxin B (1.1 .2); melanin synthesis inhibitors: pyroquilon (1.2.1 ), tricyclazole (1.2.2), carpropamid
  • Plant defence inducers selected from:
  • acibenzolar-S-methyl J.1 .1
  • probenazole J.1.2
  • isotianil J.1.3
  • tiadinil J.1.4
  • prohexadione-calcium J.1 .5
  • phosphonates fosetyl (J.1 .6), fosetyl-aluminum (J.1.7), phosphorous acid and its salts (J.1 .8), potassium or sodium bicarbonate
  • K Compounds with unknown mode of action selected from: (xxvii) bronopol (K.1 .1 ), chinomethionat (K.1.2), cyflufenamid (K.1.3), cymoxanil (K.1 .4), dazomet (K.1 .5), debacarb (K.1 .6), diclomezine (K.1.7), difenzoquat (K.1 .8), difenzoquat-methylsulfate (K.1.9), diphenylamin (K.1.10), fenpyrazamine (K.1 .1 1 ), flumetover (K.1 .12), flusulfamide (K.1 .13), flutianil (K.1.14), methasul- focarb (K.1 .15), nitrapyrin (K.1.16), nitrothal-isopropyl (K.1.18), oxathiapiprolin (K.1 .19),
  • said fungicide is azoxystrobin (A.1 .1 ), pyraclostrobin (A.1 .14), thfloxystrobin (A.1 .17), boscalid (A.3.4), fluopyram (A.3.7), fluxapyroxad (A.3.9), pen- flufen (A.3.14), penthiopyrad (A.3.15), sedaxane (A.3.16), difenoconazole (B.1.5), ipconazole (B.1 .15), prothioconazole (B.1 .23), triticonazole (B.1.29), metalaxyl (C.1 .4), metalaxyl-M
  • said combination of a nitrification inhibitor or (T) and a fungicide further comprises a fertilizer.
  • the present invention relates to a composition for increasing the health of a plant comprising at least one nitrification inhibitor as defined herein above or (T) and at least one fungicide as defined herein above.
  • said agricultural compositon additionally comprises at least one carrier.
  • the present invention relates to a method for increasing the health of a plant, comprising treating a plant growing on soil or soil substituents and/or the locus or soil or soil substituents where the plant is growing or is intended to grow with a combination of at least one nitrification inhibitor or (T) and at least one fungicide as defined herein above, or a composition as defined herein above.
  • T nitrification inhibitor or
  • the plant and/or the locus or soil or soil substituents where the plant is growing or is intended to grow is additionally provided with a fertilizer.
  • the application of said nitrification inhibitor (A) and of said fungicide (B), and optionally of said fertilizer (C) is carried out simultaneously or with a time lag.
  • the application of (thio)phosphoric acid tri- amide (T) and of said fungicide (B), and optionally of said fertilizer (C) is carried out simultaneously or with a time lag.
  • said time lag is an interval of 1 day, 2 days, 3 days, 1 week, 2 weeks or 3 weeks.
  • composition or method of the invention as mentioned herein above, said increase of the health of a plant is reflected by an increase in growth of root and shoot, an overall increase in productivity and/or a faster and more efficient development of the plant.
  • said plant is an agricultural plant such as wheat, barley, oat, rye, soybean, corn, oilseed rape, canola, sunflower, cotton, sugar cane, sugar beet, rice or a vegetable such as spinach, lettuce, asparagus, or cabbages; or sorghum; a silvicultural plant; an ornamental plant; or a horticultural plant, each in its natural or in a genetically modified form.
  • agricultural plant such as wheat, barley, oat, rye, soybean, corn, oilseed rape, canola, sunflower, cotton, sugar cane, sugar beet, rice or a vegetable such as spinach, lettuce, asparagus, or cabbages; or sorghum; a silvicultural plant; an ornamental plant; or a horticultural plant, each in its natural or in a genetically modified form.
  • the present invention relates in one aspect to the use of a fungicide and a nitrification inhibitor for increasing the health of a plant, wherein said nitrification inhibitor is a compound of formula I as defined herein.
  • the present invention relates in another aspect to the use of a fungicide and a (thio)phosphoric acid triamide (T) for increasing the health of a plant.
  • the term “consisting of” is considered to be a preferred embodiment of the term “comprising of. If hereinafter a group is defined to comprise at least a certain number of embodiments, this is meant to also encompass a group which preferably consists of these embodiments only. Furthermore, the terms “first”, “second”, “third” or “(a)”, “(b)”, “(c)”, “(d)” etc. and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of oper- ation in other sequences than described or illustrated herein.
  • first”, “second”, “third” or “(a)”, “(b)”, “(c)”, “(d)”, “i”, “ii” etc. relate to steps of a method or use or assay there is no time or time interval coherence between the steps, i.e. the steps may be carried out simultaneously or there may be time intervals of seconds, minutes, hours, days, weeks, months or even years between such steps, unless otherwise indicated in the application as set forth herein above or below. It is to be understood that this invention is not limited to the particular methodology, protocols, reagents etc. described herein as these may vary.
  • Nitrification inhibitor is to be understood in this context as a chemical substance which slows down or stops the nitrification process. Nitrification inhibitors accordingly retard the natural transformation of ammonium into nitrate, by inhibiting the activity of bacteria such as Nitrosomonas spp.
  • the term "nitrification” as used herein is to be understood as the biological oxidation of ammonia (N H3) or ammonium (NhV) with oxygen into nitrite (NO2 ) followed by the oxidation of these nitrites into nitrates (NO3 ) by microorganisms. Besides nitrate (NO3 ) nitrous oxide is also produced though nitrification. Nitrification is an important step in the nitrogen cycle in soil. The inhibition of nitrification may thus also reduce NO2 losses.
  • compound(s) according to the invention comprises the compound(s) as defined herein as well as a stereoisomer, salt, tautomer or N-oxide thereof.
  • compound(s) of the present invention is to be understood as equivalent to the term “compound(s) according to the invention", therefore also comprising a stereoisomer, salt, tautomer or N-oxide thereof.
  • the compounds of formula I may be amorphous or may exist in one or more different crystalline states (polymorphs) which may have different macroscopic properties such as stability or show different biological properties such as activities.
  • the present invention relates to amorphous and crystalline compounds of formula I, mixtures of different crystalline states of the respective compound I, as well as amorphous or crystalline salts thereof.
  • Salts of the compounds of the formula I are preferably agriculturally acceptable salts. They can be formed in a customary manner, e.g. by reacting the compound with an acid of the anion in question if the compound of formula I has a basic functionality. Agriculturally useful salts of the compounds of formula I encompass especially the acid addition salts of those acids whose cati- ons and anions, respectively, have no adverse effect on the mode of action of the compounds of formula I.
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydro- gensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting compounds of formula I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • N-oxide includes any compound of formula I which has at least one tertiary nitrogen atom that is oxidized to an N-oxide moiety.
  • the organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members.
  • the prefix C n -C m indicates in each case the possible number of carbon atoms in the group.
  • halogen denotes in each case fluorine, bromine, chlorine or iodine, in particular fluorine, chlorine or bromine.
  • alkyl denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably from 1 to 3 carbon atoms.
  • Examples of an alkyl group are methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl, iso-butyl, tert-butyl, n-pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-di methyl propyl, 1-ethylpropyl, n-hexyl, 1 ,1 -dimethylpropyl, 1 ,2- di methyl propyl, 1 -methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1 -dimethyl- butyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethyl- butyl, 1 -ethylbutyl, 2-ethylbutyl,
  • haloalkyl denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms.
  • Preferred haloalkyl moieties are selected from Ci-C4-haloalkyl, more preferably from Ci-C3-haloalkyl or Ci-C2-haloalkyl, in particular from Ci-C2-fluoroalkyl such as fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, and the like.
  • cyanoalkyl denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, wherein the hydrogen atoms of this group are partially or totally replaced with cyano groups.
  • Preferred cyanoalkyl moieties are selected from Ci-C4-cyanoalkyl, more preferably from Ci-C3-cyanooalkyl or Ci-C2-cyanoalkyl.
  • hydroxyalkyl denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, wherein the hydrogen atoms of this group are partially or totally replaced with hydroxy groups.
  • Preferred hydroxyalkyl moieties are selected from Ci-C4-hydroxy- alkyl, more preferably from Ci-C-hydroxyalkyl or Ci-C2-hydroxyalkyl.
  • Preferred hydroxyalkyl moieties are selected from hydroxy methyl, dihydroxymethyl, trihydroxymethyl,1 -hydroxyethyl and 2-hydroxyethyl.
  • alkoxy denotes in each case a straight-chain or branched alkyl group which is bound via an oxygen atom and has usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.
  • alkoxy group examples are methoxy, ethoxy, n-propoxy, iso-propoxy, n-butyloxy, 2-butyloxy, iso-butyloxy, tert-butyloxy, and the like.
  • alkoxyalkyl refers to alkyl usually comprising 1 to 10, frequently 1 to 4, preferably 1 to 2 carbon atoms, wherein 1 carbon atom carries an alkoxy radical usually comprising 1 to 4, preferably 1 or 2 carbon atoms as defined above. Examples are CH2OCH3, CH2-OC2H5, 2-(methoxy)ethyl, and 2-(ethoxy)ethyl.
  • alkenyl denotes in each case an at least singly unsaturated hydrocarbon radical, i.e. a hydrocarbon radical having at least one carbon-carbon double bond, having usually 2 to 10, frequently 2 to 6, preferably 2 to 4 carbon atoms, e.g.
  • haloalkenyl refers to an alkenyl group as defined above, wherein the hydrogen atoms are partially or totally replaced with halogen atoms.
  • alkynyl denotes in each case a hydrocarbon radical having at least one carbon-carbon triple bond and having usually 2 to 10, frequently 2 to 6, preferably 2 to 4 carbon atoms, e.g.
  • ethynyl propargyl (2-propyn-1 -yl), 1 -propyn-1 -yl, 1 -methylprop-2-yn-1 -yl), 2- butyn-1 -yl, 3-butyn-1 -yl, 1 -pentyn-1 -yl, 3-pentyn-1 -yl, 4-pentyn-1 -yl, 1 -methylbut-2-yn-1 -yl, 1 - ethylprop-2-yn-1 -yl and the like.
  • haloalkynyl refers to an alkynyl group as defined above, wherein the hydrogen atoms are partially or totally replaced with halogen atoms.
  • alkynylalkyl refers to alkyl usually comprising 1 to 10, frequently 1 to 4, preferably 1 to 2 carbon atoms, wherein 1 carbon atom carries an alkynyl radical usually comprising 2 to 4, preferably 2 or 3 carbon atoms as defined above.
  • alkynylhydroxyalkyi refers to an hydroxyalkyi as defined above usual- ly comprising 1 to 10, frequently 1 to 4, preferably 1 to 2 carbon atoms, wherein 1 carbon atom carries an alkynyl radical usually comprising 2 to 4, preferably 2 or 3 carbon atoms as defined above.
  • An exemplary alkynylhydroxyalkyl is ethynylhydroxym ethyl.
  • alkynyloxy denotes in each case an alkynyl group which is bound to the remainder of the molecule via an oxygen atom and has usually from 2 to 6 carbon atoms, frequently from 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms.
  • cycloalkyl as used herein and in the cycloalkyl moieties of cycloalkoxy and cycloal- kylmethyl denotes in each case a monocyclic cycloaliphatic radical having usually from 3 to 10 or from 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohep- tyl, cyclooctyl, cyclononyl and cyclodecyl or cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
  • cycloalkenyl denotes in each case a monocyclic singly unsaturated non-aromatic radical having usually from 5 to 10 or from 3 to 8 carbon atoms, including e.g. cy- cloheptenyl or cyclooctenyl.
  • heterocyclyl or “heterocycle” includes in general 3- to 14-membered, preferably 3- to 10-membered, more preferably 5-, or 6-membered non-aromatic radicals with at least one het- eroatom.
  • heterocyclyl or “heterocycle” refers to monocyclic, bicyclic or tricyclic het- erocyclic non-aromatic radicals.
  • heterocyclyl or “heterocycle” also includes bicyclic or tricyclic radicals, which comprise a non-aromatic ring and a fused aryl or hetaryl ring.
  • heterocyclic radicals usually comprise 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where S-atoms as ring members may be present as S, SO or SO2.
  • Examples of 5- or 6-membered heterocyclic radicals comprise saturated or unsaturated, non-aromatic heterocyclic rings, such as oxiranyl, oxetanyl, thietanyl, thietanyl-S-oxid (S- oxothietanyl), thietanyl-S-dioxid (S-dioxothiethanyl), pyrrolidinyl, pyrrolinyl, pyrazolinyl, tetrahy- drofuranyl, dihydrofuranyl, 1 ,3-dioxolanyl, thiolanyl, S-oxothiolanyl, S-dioxothiolanyl, dihy- drothienyl, S-oxodihydrothienyl, S-dioxodihydrothienyl, oxazolidinyl, oxazolinyl,
  • heterocyclic rings also com- prising 1 or 2 carbonyl groups as ring members comprise pyrrolidin-2-onyl, pyrrolidin-2,5-dionyl, imidazolidin-2-onyl, oxazolidin-2-onyl, thiazolidin-2-onyl and the like.
  • Particularly preferred are also bicyclic 8- to 10-membered heterocyclic radicals comprising as ring members 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3 heteroatoms selected from N, O and S members, where S-atoms as ring members may be present as S, SO or SO2.
  • said bicyclic 8- to 10-membered heterocyclic radicals comprise a 5- or 6-membered non-aromatic ring as defined above, which is fused to an aryl or hetaryl ring or to another heterocyclic ring.
  • fused heterocyclyl radicals may be bound to the remainder of the molecule via any ring atom of the 5- or 6-membered ring or the fused ring.
  • carbocyclyl or “carbocycle” includes in general 3- to 14-membered, preferably 3- to 10-membered, more preferably 5- or 6-membered non-aromatic radicals.
  • the term “carbocyclyl” or “carbocycle” may refer to monocyclic, bicyclic or tricyclic carbocyclic non-aromatic radicals.
  • Preferred carbocycles are cycloalkyl and cycloalkenyl groups having from 3 to 10, preferably 5 or 6 carbon atoms.
  • bicyclic 8- to 10-membered carbocyclic radicals wherein a 5- or 6-membered non-aromatic ring is fused to an aryl ring or another carbocyclic ring.
  • fused carbocyclyl radicals may be bonded to the remainder of the molecule via any ring atom of the 5- or 6-membered ring or the fused ring.
  • heteroaryl includes monocyclic 5- or 6-membered heteroaromatic radicals comprising as ring members 1 , 2, 3 or 4 heteroatoms selected from N, O and S. Examples of 5- or
  • 6-membered heteroaromatic radicals include pyridyl, i.e. 2-, 3-, or 4-pyridyl, pyrimidinyl, i.e. 2-, 4- or 5-pyrimidinyl, pyrazinyl, pyridazinyl, i.e. 3- or 4-pyridazinyl, thienyl, i.e. 2- or 3-thienyl, furyl, i.e. 2-or 3-furyl, pyrrolyl, i.e. 2- or 3-pyrrolyl, oxazolyl, i.e. 2-, 3- or 5-oxazolyl, isoxazolyl, i.e. 3-, 4- or 5-isoxazolyl, thiazolyl, i.e. 2-, 3- or 5-thiazolyl, isothiazolyl, i.e. 3-, 4- or
  • 5-isothiazolyl pyrazolyl, i.e. 1 -, 3-, 4- or 5-pyrazolyl, i.e. 1 -, 2-, 4- or 5-imidazolyl, oxadiazolyl, e.g. 2- or 5-[1 ,3,4]oxadiazolyl, 4- or 5-(1 ,2,3-oxadiazol)yl, 3- or 5-(1 ,2,4-oxadiazol)yl, 2- or 5-(1 ,3,4-thiadiazol)yl, thiadiazolyl, e.g.
  • heteroaryl also includes bicyclic 8 to 13-membered, preferably 8- to 10 membered heteroaromatic radicals comprising as ring members 1 , 2 or 3 heteroatoms selected from N, O and S, wherein a 5- or 6-membered heteroaromatic ring is fused to a phenyl ring or to a 5- or 6-membered heteroaromatic radical.
  • Examples of a 5- or 6-membered heteroaromatic ring fused to a phenyl ring or to a 5- or 6- membered heteroaromatic radical include benzofuranyl, benzothienyl, indolyl, indazolyl, ben- zimidazolyl, benzoxathiazolyl, benzoxadiazolyl, benzothiadiazolyl, benzoxazinyl, chinolinyl, iso- chinolinyl, purinyl, 1 ,8-naphthyridyl, pteridyl, pyrido[3,2-d]pyrimidyl or pyridoimidazolyl and the like.
  • These fused hetaryl radicals may be bonded to the remainder of the molecule via any ring atom of 5- or 6-membered heteroaromatic ring or via a carbon atom of the fused phenyl moiety.
  • heteroaryloxy refers to heteraryl as defined above, which is bound via an oxygen atom to the remainder of the molecule.
  • aryl includes monocyclic, bicyclic or tricyclic aromatic radicals comprising 6 to 14 carbon atoms, preferably 6 or 10 carbon atoms, more preferably 6 carbon atoms.
  • exemplary aryl radicals include anthracenyl, naphthalenyl and phenyl.
  • a preferred aryl radical is phenyl.
  • a preferred arylalkyl group is phenylmethyl, i.e. benzyl.
  • aryloxy refers to aryl as defined above, which is bound via an oxygen atom to the remainder of the molecule.
  • a preferred aryloxy group is e.g. benzyloxy.
  • the present invention concerns in one aspect the use of a nitrification inhibitor for reducing nitrification, wherein said nitrification inhibitor is a compound of formula I or a stereoisomer, salt, tautomer or N-oxide thereof, wherein
  • A is aryl or hetaryl, wherein the aromatic ring may in each case be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from R A ;
  • R 1 and R 2 are independently of each other selected from H and Ci-C2-alkyl
  • R 3 is H, Ci-C4-haloalkyl, Ci-C4-hydroxyalkyl, ethynylhydroxym ethyl, phenylhydroxymethyl, or aryl, wherein the aromatic ring may be unsubstituted or may be partially or fully substi- tuted by substituents, which are independently of each other selected from R B ; and wherein is
  • a 3- to 14-membered saturated or unsaturated carbocycle or heterocycle which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from NR 1b , O, and S, wherein S may be oxidized and/or wherein the carbocycle or heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R 1b is H, C1-C4- alkyl, C 2 -C4-alkenyl, C3-C6-cycloalkyl, C3-C6-cycloalkylmethyl, or ORa; or
  • B is aryl or hetaryl, wherein the aromatic ring of the ary or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from R h ;
  • a 3- to 14-membered saturated or unsaturated carbocycle or heterocycle which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from N R 1b , O, and S, wherein S may be oxidized and/or wherein the carbocycle or heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R 1b is H, Ci-C4-alkyl, C 2 -C4-alkenyl, C3-C6-cycloalkyl, C3-C6-cycloalkylmethyl, or OR9; or
  • two substituents R A together represent a carbocyclic or heterocyclic ring, which is fused to A and may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from NR 1c , O, and S, wherein S may be oxidized and/or wherein the carbocycle or heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R 1c is H, d-C 4 -alkyl, C 2 -C 4 -alkenyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 - cycloalkylmethyl, C3-C6-heterocyclyl, C3-C6-heterocyclylmethyl or OR9; and wherein
  • Y 2 and Y 3 are independently of each other selected from O, S and NR 1a , wherein R 1a is each case independently H, Ci-C 4 -alkyl, C 2 -C 4 -alkenyl, C3-C6-cycloalkyl, C3-( cycloalkylmethyl, ORa, SRa or NR m R n ;
  • R a and R b are independently of each other selected from
  • aryl or hetaryl wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from R h ; or
  • a 3- to 10-membered, saturated or unsaturated heterocycle which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from NR 1b , O, and S, wherein S may be oxidized and/or wherein the heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R 1b is H , Ci-C 4 -alkyl, C 2 -C 4 -alkenyl, C3-C6-cycloalkyl, C3-C 6 -cycloalkylmethyl, or ORa; is
  • Ci-C 4 -alkylene chain may in each case be unsubstituted or may be partially or fully substituted by ORa, CN, halogen, or phenyl;
  • a 3- to 10-membered saturated or unsaturated carbocycle or heterocycle which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from NR 1b , O, and S, wherein S may be oxidized and/or wherein the carbocycle or heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R 1b is H, C1-C4- alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6-cycloalkylmethyl, or ORa;
  • R f is Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, NRR k , OR, SR, aryl or hetaryl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from R h ;
  • R9 is H or Ci-C 4 -alkyl
  • R 1d is H, Ci-C 4 -alkyl, C 2 -C 4 -alkenyl, C 3 -C 6 -cycloalkyl, C 3 -C 6 - cycloalkylmethyl, or OR9;
  • aryl, aryl-Ci-C 2 -alkyl, hetaryl, or hetaryl-Ci-C 2 -alkyl wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from halogen, CN, C1-C4- alkyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy, C 2 -C 4 -alkynyloxy, ORa, and SRa; or
  • A is phenyl or a 5- or 6-membered hetaryl, wherein the aromatic ring may in each case be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from R A .
  • R A represents phenyl or a 5- or 6- membered hetaryl, wherein the aromatic ring may in each case be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from R A .
  • R 1 and R 2 both represent hydrogen.
  • R 3 is hydrogen, Ci-C4-haloalkyl or ethynylhydroxymethyl. It is even more preferred that R 3 is hydrogen.
  • A is A', i.e. phenyl or a 5- or 6-membered hetaryl, wherein the aromatic ring may in each case be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from R A , and R 1 and R 2 are both hydrogen.
  • substituents which are independently of each other selected from R A , and R 1 and R 2 are both hydrogen.
  • A is A', i.e. phenyl or a 5- or 6-membered hetaryl, wherein the aromatic ring may in each case be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from
  • R A , and R 3 is hydrogen.
  • R 1 and R 2 are both hy- drogen, and R 3 is hydrogen.
  • nds correspond to compounds of formula I.A.X. I.A.X
  • A is A', i.e. phenyl or a 5- or 6-membered hetaryl, wherein the aromatic ring may in each case be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from R A , R 1 and R 2 are both hydrogen, and R 3 is hydrogen.
  • R A if present, is
  • a 3- to 14-membered saturated or unsaturated heterocycle which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from N R 1b , O , and S, wherein S may be oxidized and/or wherein the heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R 1b is H , Ci-C 4 -alkyl, C2-C 4 -alkenyl, C3-C6-cycloalkyl, C3-C 6 -cycloalkylmethyl, or ORa.
  • the compound of formula I is a compound of formula 1.1 , I.A, I.X, 1.1. A, 1.1.X, I.A.X or I.1.A.X, wherein R A , if present, is
  • a 3- to 14-membered saturated or unsaturated heterocycle which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from N R 1b , O , and S, wherein S may be oxidized and/or wherein the heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R 1b is H , Ci-C4-alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C 6 -cycloalkylmethyl, or ORa.
  • R A is present in the compounds of formula I or a compound of any one of formulae 1.1 , I.A, I.X, 1.1 .A, 1.1 .X, I.A.X or I.1.A.X, and preferably if R A is selected as indicated above, the following substituent definitions are particularly preferred according to the present invention.
  • Y 1 , Y 2 and Y 3 are independently of each other selected from O, S and N R 1a , wherein preferably R 1a is in each case independently H, d-C 4 -alkyl, ORa, or NR m R n .
  • R a and R b are independently of each other selected from
  • heteroatoms which, independently of each other, are selected from NR 1b , O, and S, wherein S may be oxidized and/or wherein the heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R 1b is preferably H , Ci-C 4 -alkyl, or ORa.
  • R c is
  • a 3- to 10-membered saturated or unsaturated carbocycle or heterocycle which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from NR 1b , O, and S, wherein S may be oxidized and/or wherein the carbocycle or heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R 1b is preferably H, Ci-C 4 -alkyl, or ORa.
  • R f is Ci-C 4 -alkyl.
  • Ra is H.
  • R h is halogen or Ci-C 4 -alkoxy.
  • R is N
  • Ci-C 4 -alkyl Ci-C 4 -haloalkyl, C2-C 4 -haloalkenyl
  • R and R k are both H .
  • R 1 is H.
  • R m and R n are both H .
  • the present invention thus relates to the use of a combination of a nitrification inhibitor or (T) and a fungicide as defined herein above, or of a composition comprising said combination of a nitrification inhibitor or (T) and a fungicide as defined herein for increasing the health of a plant.
  • the nitrification inhibitor or derivatives or salts thereof as defined herein above in combination with a fungicide, in particular compounds of formula I and/or salts or suitable derivatives thereof in combination with a fungicide, as well as compositions comprising said nitrification inhibitor or (T) and a fungicide as defined herein may be used for increasing the health of a plant.
  • the use may be based on an application of the combination of the nitrification inhibitor or (T) and a fungicide, or the composition as defined herein to a plant growing on soil and/or the locus where the plant is growing or is intended to grow, or the application of the combination of the nitrification inhibitor or (T) and a fungicide, or the composition as defined herein to soil where a plant is growing or is intended to grow or to soil substituents.
  • the com- bination of the nitrification inhibitor or (T) and a fungicide may be used in the absence of plants, e.g. as preparatory activity for subsequent agricultural activity.
  • the use may further include the application of a combination of a fungicide and (T) or the nitrification inhibitor or derivatives or salts thereof as defined herein above, in particular compounds of formula I and/or salts or suitable derivatives thereof, as well as compositions comprising said combination of a fungicide and (T) or the nitrification inhibitor, or agrochemical mixtures comprising (T) or said nitrification inhibitor as defined herein above to environments, areas or zones, where nitrification takes place or is assumed or expected to take place.
  • environments, areas or zones may, in specific embodiments, not comprise plants or soil, but be planned for subsequent growth of plants. Examples of such environments are laboratory envirnonments or green houses or similar indoor facilities.
  • plant health as used herein is intended to mean a condition of the plant which is determined by several aspects alone or in combination with each other.
  • One indicator (indicator 1 ) for the condition of the plant is the crop yield.
  • “Crop” and “fruit” are to be understood as any plant product which is further utilized after harvesting, e.g. fruits in the proper sense, vegeta- bles, nuts, grains, seeds, wood (e.g. in the case of silviculture plants), flowers (e.g. in the case of gardening plants, ornamentals) etc., that is anything of economic value that is produced by the plant.
  • Another indicator (indicator 2) for the condition of the plant is the plant vigor.
  • the plant vigor becomes manifest in several aspects, too, some of which are visual appearance, e.g. leaf color, fruit color and aspect, amount of dead basal leaves and/or extent of leaf blades, plant weight, plant height, extent of plant verse (lodging), number, strong ness and productivity of tillers, panicles' length, extent of root system, strongness of roots, extent of nodulation, in particular of rhizobial nodulation, point of time of germination, emergence, flowering, grain maturity and/or senescence, protein content, sugar content and the like.
  • Another indicator (indicator 3) for an increase of a plant's health is the reduction of biotic or abiotic stress factors.
  • the three above mentioned indicators for the health condition of a plant may be interdependent and may result from each other. For example, a reduction of biotic stress may lead to a better plant vigor, e.g. to better and bigger crops, and thus to an increased yield. Biotic stress, especially over longer terms, can have harmful effects on plants.
  • the term "biotic stress” as used in the context of the present invention refers in particular to stress caused by living organisms, such as fungi, especially phythopathogenic fungi. As a result, the quantity and the quality of the stressed plants, their crops and fruits decrease. As far as quality is concerned, reproductive development is usually severely affected with consequences on the crops which are important for fruits or seeds.
  • Growth may be slowed by the stresses; polysaccharide synthesis, both structural and storage, may be reduced or modified: these effects may lead to a decrease in biomass and to changes in the nutritional value of the product.
  • a reduction of biotic stress factors may, for example, be due to a fungicidal effect to fungi, especially phythopathogenic fungi of a fungicide as defined herein.
  • Abiotic stress includes drought, cold, increased UV, increased heat, or other changes in the environment of the plant, that leads to sub-optimal growth conditions.
  • a reduction of abiotic stress factors may, for example, be due to a reduction of nitrification and a corresponding improvement of uptake of nitrogen nutrients.
  • the term "increased yield" of a plant as used herein means that the yield of a product of the respective plant is increased by a measurable amount over the yield of the same product of the plant produced under the same conditions, but without the application of the composition of the invention. According to the present invention, it is preferred that the yield be increased by at least 0,5 %, more preferred at least 1 %, even more preferred at least 2 %, still more preferred at least 4 %.
  • An increased yield may, for example, be due to a reduction of nitrification and a corresponding improvement of uptake of nitrogen nutrients, as well as a fungicidal effect to fungi, especially phythopathogenic fungi of a fungicide as defined herein.
  • improved plant vigor means that certain crop characteristics are increased or improved by a measurable or noticeable amount over the same factor of the plant produced under the same conditions, but without the application of the composition of the pre- sent invention. Improved plant vigor can be characterized, among others, by following improved properties of a plant:
  • the improvement of the plant vigor according to the present invention particularly means that the improvement of anyone or several or all of the above mentioned plant characteristics are improved. It further means that if not all of the above characteristics are improved, those which are not improved are not worsened as compared to plants which were not treated according to the invention or are at least not worsened to such an extent that the negative effect exceeds the positive effect of the improved characteristic (i.e. there is always an overall positive effect which preferably results in an improved crop yield).
  • An improved plant vigor may, for example, be due to a reduction of nitrification and a corresponding improvement of uptake of nitrogen nutrients, as well as a fungicidal effect to fungi, especially phythopathogenic fungi of a fungicide as defined herein.
  • said increase of the health of a plant is reflected by an increase in growth of root and shoot and/or an overall increase in productivity and/or a faster and more efficient development of the plant.
  • reducing nitrification or “reduction of nitrification” as used herein refers to a slowing down or stopping of nitrification processes, e.g. by retarding or eliminating the natural transformation of ammonium into nitrate. Such reduction may be a complete or partial elimination of nitrification at the plant or locus where the inhibitor or composition comprising said inhibitor is applied.
  • a partial elimination may result in a residual nitrification on or in the plant, or in or on the soil or soil substituents where a plant grows or is intended to grow of about 90% to 1 %, e.g. 90%, 85%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10% or less than 10%, e.g. 5% or less than 5% in comparison to a control situation where the nitrification inhibitor is not used.
  • a partial elimination may result in a residual nitrification on or in the plant or in or on the soil or soil substituents where a plant grows or is intended to grow of below 1 %, e.g.
  • a "fungicide” as mentioned herein above may be any fungicide known to the skilled person.
  • a fungicide typically shows an outstanding effectiveness against biotic stresses caused by a broad spectrum of phytopathogenic fungi, including soil-borne fungi, which derive especially from the classes of the Plasmodiophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti).
  • Some are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants.
  • the fungicides and compositions comprising them according to the invention are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e. g.
  • Fungicides and compositions comprising them respectively may preferably be used for controlling a multitude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
  • field crops such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
  • Fungicides and compositions comprising them according to the present invention are particularly suitable for reducing biotic stresses caused by one or more of the following plant diseases: Albugo spp. (white rust) on ornamentals, vegetables (e. g. A Candida) and sunflowers (e. g. A. tragopogonis); Alternaria spp. (Alternaria leaf spot) on vegetables, rape (A. brassicola or brassi- cae), sugar beets (A tenuis), fruits, rice, soybeans, potatoes (e. g. A. solani or A alternata), tomatoes (e. g. A solani or A alternata) and wheat; Aphanomyces spp.
  • Albugo spp. white rust
  • vegetables e. g. A Candida
  • sunflowers e. g. A. tragopogonis
  • Alternaria spp. Alternaria leaf spot
  • rape A. brassicola or brassi- cae
  • Ascochyta spp. on cereals and vegetables e. g. A. tritici (anthracnose) on wheat and A hordei on barley; Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e. g. Southern leaf blight (D. maydis) or Northern leaf blight (B. zeicola) on corn, e. g. spot blotch (B. sorokiniana) on cereals and e. g. B. oryzae on rice and turfs; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e.
  • Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad- leaved trees and evergreens, e. g. C. ulmi (Dutch elm disease) on elms; Cercospora spp. (Cer- cospora leaf spots) on corn (e.
  • Botrytis cinerea teleomorph: Botryotinia fuckeliana: grey mold
  • fruits and berries e. g. strawberries
  • vegetables e. g. lettuce, carrots, celery and cabbages
  • rape flowers, vines, forestry plants and wheat
  • spp. (anthracnose) on cotton (e. g. C. gossypii), corn (e. g. C. gramini- cola: Anthracnose stalk rot), soft fruits, potatoes (e. g. C. coccodes: black dot), beans (e. g. C. lindemuthianum) and soybeans (e. g. C. truncatum or C. gloeosporioides); Corticium spp., e. g. C.
  • Cycloconium spp. e. g. C. oleaginum on olive trees
  • Cylindrocarpon spp. e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.
  • liriodendri Neonectria liriodendri: Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e. g. D. phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleo- morph: Pyrenophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. D.
  • tritici-repentis tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa; Elsinoe spp. on pome fruits (£. pyri), soft fruits (£. veneta: anthracnose) and vines (£.
  • ampelina anthracnose
  • Entyloma oryzae leaf smut
  • Epicoccum spp. black mold
  • Erysiphe spp. potowdery mildew
  • sugar beets £. betae
  • vegetables e. g. £. pisi
  • cucurbits e. g. £. cichoracearum
  • cabbages rape (e. g. £. cruciferarum)
  • Eutypa lata Eutypa canker or dieback, anamorph: Cytosporina lata, syn.
  • Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e. g. M. laxa, M. fructicola and M. fructigena (bloom and twig blight, brown rot) on stone fruits and other rosaceous plants; Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M. graminicola (anamorph: Septoria tritici, Septoria blotch) on wheat or M. fijiensis (black Sigatoka disease) on bananas; Peronospora spp. (downy mildew) on cabbage (e. g. P. brassicae), rape (e. g. P. parasitica), onions (e. g. P. destructor), tobacco (P. tabacina) and soybeans (e. g. P. manshurica);
  • Monilinia spp. e. g. la
  • Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp. e. g. on vines (e. g. P. tracheiphila and P. tetraspora) and soybeans (e. g. P. gregata: stem rot); Phoma lingam (root and stem rot) on rape and cabbage and P. betae (root rot, leaf spot and damping-off) on sugar beets; Phomopsis spp. on sunflowers, vines (e. g. P. viticola: can and leaf spot) and soybeans (e. g. stem rot: P.
  • phaseoli, teleomorph Diaporthe phaseolorum
  • Phy- soderma maydis brown spots
  • Phytophthora spp. wilt, root, leaf, fruit and stem root
  • paprika and cucurbits e. g. P. capsici
  • soybeans e. g. P.
  • Plasmodiophora brassicae club root
  • Plasmopara spp. e. g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers
  • Podosphaera spp. powdery mildew
  • Puccinia spp. rusts on various plants, e. g. P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, P. kuehnii (orange rust) on sugar cane and P.
  • Pyrenophora anamorph: Drechslera
  • tritici-repentis tan spot
  • P. teres net blotch
  • Pyricularia spp. e. g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals
  • Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphanidermatum);
  • Ramularia spp. e. g. R.
  • collo-cygni Roso-cygni (Ramularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables and various other plants, e. g. R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice or R.
  • S. reiliana head smut
  • Sphaerotheca fuliginea powdery mildew
  • Spongospora subterranea powdery scab
  • Stagonospora spp. on cereals, e. g. S. nodorum (Stagonospora blotch, teleomorph: Lepto- sphaeria [syn. Phaeosphaeria] nodorum) on wheat
  • Synchytrium endobioticum on potatoes potato wart disease
  • Taphrina spp. e. g. T.
  • deformans leaf curl disease
  • T. pruni plum pocket
  • plums Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e. g. T. basicola (syn. Chalara elegans); Tilletia spp. (common bunt or stinking smut) on cereals, such as e. g. T. tritici (syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat; Typhula incarnata (grey snow mold) on barley or wheat; Urocystis spp., e. g. U.
  • occulta stem smut
  • Uromyces spp. rust
  • vegetables such as beans (e. g. U. appendiculatus, syn. U. phaseoli) and sugar beets (e. g. U. betae)
  • Ustilago spp. loose smut) on cereals (e. g. U. nuda and U. avaenae), corn (e. g. U. maydis: corn smut) and sugar cane
  • Venturia spp. scab
  • apples e. g. V. inaequalis
  • pears Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. V. dahliae on strawberries, rape, potatoes and tomatoes.
  • the fungicide a respiration inhibitor.
  • respiration inhibitor fungicides to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are inhibitors of complex III at Q 0 site, inhibitors of complex III at Q, site, inhibitors of complex II, or other respiration inhibitors or complex I uncouplers.
  • respiration inhibitor fungicides of the class of inhibitors of complex III at Q 0 site to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are strobilurines.
  • Envisaged examples of stro- bilurine and similar compounds to be used in the context of the present invention include azoxystrobin (A.1.1 ), coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxystrobin/flufenoxystrobin, fluoxastrobin, kresoxim-methyl, mandestrobine, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin (A.1 .14), pyrametostrobin, pyrao- xystrobin, trifloxystrobin (A.1 .17) and 2-(2-(3-(2,6-dichlorophenyl)-1 -methyl-allylideneaminooxy- methyl)-phenyl)-2-methoxyimino-N-methyl-acetamide, pyribencarb, triclopyricarb/chlorodincarb,
  • respiration inhibitor fungicides of the class of inhibitors of complex III at Q, site to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are cyazofamid, amisulbrom, [(3S,6S,7R,8R)-8- benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7- yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)-4-methoxy-pyridine- 2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8
  • respiration inhibitor fungicides of the class of inhibitors of complex II to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are benodanil, benzovindiflupyr, bixafen, boscalid (A.3.4), carboxin, fenfuram, fluopyram (A.3.7), flutolanil, fluxapyroxad (A.3.9), furametpyr, isofetamid, isopyrazam, mepronil, oxycarboxin, penflufen (A.3.14), penthiopyrad (A.3.15), sedaxane (A.3.16), tecloftalam, thifluzamide, N-(4'-trifluoromethylthiobiphenyl-2-yl)-3-difluoromethyl-1 - methyl-1 H-pyrazole-4-carboxamide, N-(2-(1 ,3,3-trimethyl-
  • respiration inhibitor fungicides of the class of other respiration inhibitors or complex I uncouplers to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are diflumetorim, (5,8-difluoro- quinazolin-4-yl)- ⁇ 2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl ⁇ -amine; nitrophenyl derivates: binapacryl, dinobuton, dinocap, fluazinam; ferimzone; organometal compounds: fen- tin salts, such as fentin-acetate, fentin chloride or fentin hydroxide; ametoctradin, silthiofam
  • the fungicide is a sterol biosynthesis inhibitor (SBI fungicide).
  • SBI fungicide sterol biosynthesis inhibitor
  • Suitable examples of amino acid derivative herbicides to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are C14 demethylase inhibitors (DMI fungicides), delta14-reductase inhibitors, inhibitors of 3-keto reductase or 1 -[re/-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thio- cyanato-1 H-[1 ,2,4]triazole, 2-[re/-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranyl- methyl]-2H-[1 ,2,4]triazole-3-
  • respiration inhibitor fungicides of the class of C14 demethylase inhibitors to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are triazoles, azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole (B.1 .5), diniconazole, diniconazole-M, epoxi- conazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole (B.1 .15), metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole (B.1 .23), simeconazole,
  • respiration inhibitor fungicides of the class of delta 14-reductase inhibitors to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph, fenpropidin, piperalin, or spiroxamine.
  • a suitable example of a respiration inhibitor fungicide of the class of inhibitors of 3-keto reductase to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention is fenhexamid.
  • the fungicide is a nucleic acid synthesis inhibitor.
  • Suitable examples of nucleic acid synthesis inhibitor fungicides to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are phenyl- amides or acyl amino acid fungicides, hymexazole, octhilinone, oxolinic acid, bupirimate, 5- fluorocytosine, 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine, or 5-fluoro-2-(4- fluorophenylmethoxy)pyrimidin-4-amine.
  • nucleic acid synthesis inhibitor fungicides of the class of phenylamides or acyl amino acid fungicides to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are benalaxyl, benalaxyl- M, kiralaxyl, metalaxyl (C.1.4), metalaxyl-M (mefenoxam) (C.1.5), ofurace, or oxadixyl.
  • the fungicide is an inhibitors of cell division and cytoskeleton.
  • Suitable examples of inhibitor of cell division and cytoskeleton fungicides to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are tubulin inhibitors and other cell division inhibitors.
  • Suitable examples of inhibitors of cell division and cytoskeleton fungicides of the class of tubulin inhibitors to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are benzimidazoles, thiophanates: beno- myl, carbendazim, fuberidazole, thiabendazole (D.1.4), thiophanate-methyl; or triazolopyrim- idines.
  • triazolopyrimidines is 5-chloro-7-(4-methylpiperidin-1 -yl)-6-(2,4,6- trifluorophenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine.
  • Suitable examples of inhibitors of cell division and cytoskeleton fungicides of the class of other cell division inhibitors to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are diethofencarb, ethaboxam (D.2.2), pencycuron, fluopicolide, zoxamide, metrafenone and pyriofenone.
  • the fungicide is an inhibitor of amino acid and protein synthe- sis.
  • Suitable examples of inhibitor of amino acid and protein synthesis fungicides to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are methionine synthesis inhibitors and protein synthesis inhibitors.
  • Suitable examples of inhibitor of amino acid and protein synthesis fungicides of the class of me- thionine synthesis inhibitors to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are cyprodinil, mepa- nipyrim, and pyrimethanil.
  • Suitable examples of inhibitor of amino acid and protein synthesis fungicides of the class of pro- tein synthesis inhibitors to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are blasticidin-S, kasugamy- cin, kasugamycin hydrochloride-hydrate, mildiomycin, streptomycin, oxytetracyclin, polyoxine and validamycin A.
  • the fungicide is a signal transduction inhibitors.
  • Suitable examples of signal transduction inhibitor fungicides to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are MAP / histidine kinase inhibitors or G protein inhibitors.
  • Suitable examples of signal transduction inhibitor fungicides of the class of MAP / histidine kinase inhibitors to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are fluoroimid, iprodione, pro- cymidone, vinclozolin, fenpiclonil, and fludioxonil.
  • a suitable example of an inhibitor of signal transduction inhibitor fungicides of the class of G protein inhibitors to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention is quinoxyfen.
  • the fungicide is a lipid and membrane synthesis inhibitor.
  • Suitable ex- amples of lipid and membrane synthesis inhibitor fungicides to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are phospholipid biosynthesis inhibitors, phospholipid biosynthesis inhibitors, lipid peroxidation inhibitors, phospholipid biosynthesis and cell wall deposition inhibitors, compounds affecting cell membrane permeability and fatty acids or fatty acid amide hydrolase inhibitors.
  • lipid and membrane synthesis inhibitor fungicides of the class of phospholipid biosynthesis inhibitors to be used in combination with a nitrification inhibitor or (T) - prefer- ably used in combination with (T) - according to the present invention are edifenphos, iproben- fos, pyrazophos, or isoprothiolane.
  • lipid and membrane synthesis inhibitor fungicides of the class of lipid pe- roxidation inhibitors to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are dicloran, quintozene, tec- clawene, tolclofos-methyl, biphenyl, chloroneb, or etridiazole.
  • lipid and membrane synthesis inhibitor fungicides of the class of phospho- lipid biosynthesis and cell wall deposition inhibitors to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are dimethomorph, flumorph, mandipropamid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate (G.3.7) or N-(1 -(1 -(4-cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester.
  • lipid and membrane synthesis inhibitor fungicides of the class of compounds affecting cell membrane permeability and fatty acids to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are propamocarb or propamocarb-hydrochlorid.
  • lipid and membrane synthesis inhibitor fungicides of the class of fatty acid amide hydrolase inhibitors to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are oxathiapiprolin (G.5.1 ), 2- ⁇ 3-[2-(1 - ⁇ [3,5-bis(difluoromethyl-1 H-pyrazol-1 -yl]acetyl ⁇ piperidin-4-yl)-1 ,3-thiazol-4-yl]- 4,5-dihydro-1 ,2-oxazol-5-yl ⁇ phenyl methanesulfonate, 2- ⁇ 3-[2-(1 - ⁇ [3,5-bis(difluoromethyl)-1 H- pyrazol-1 -yl]acetyl ⁇ piperidin-4-yl) or 1 ,3-thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol-5-
  • the fungicide is an inhibitors with Multi Site Action.
  • Suitable examples of inhibitor with Multi Site Action fungicides to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are inorganic active substances, thio- and dithiocarbamates, organochlorine compounds, or guanidines and others.
  • Suitable examples of inhibitors with Multi Site Action fungicides of the class of inorganic active substances to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, or sulfur.
  • Suitable examples of inhibitors with Multi Site Action fungicides of the class of thio- and dithiocarbamates to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are ferbam, mancozeb (H .2.2), maneb, metam, metiram, propineb, thiram, zineb, or ziram
  • Suitable examples of inhibitors with Multi Site Action fungicides of the class of organochlorine compounds to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are phthalimides, sulfamides, chloroni- triles, anilazine, chlorothalonil (H.3.2), captafol, captan, folpet, dichlofluanid, dichlorophen, hex- achlorobenzene, pentachlorphenole and its salts
  • Suitable examples of inhibitors with Multi Site Action fungicides of the class of guanidines and others to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are guanidine, dodine, dodine free base, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine- tris(albesilate), dithianon, or 2,6-dimethyl-1 H,5H-[1 ,4]dithiino[2,3-c:5,6-c']dipyrrole- 1 ,3,5,7(2H,6H)-tetraone.
  • the fungicide is a cell wall synthesis inhibitor.
  • Suitable examples of cell wall synthesis inhibitor fungicides to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are inhibitors of glucan synthesis.
  • Suitable examples of cell wall synthesis inhibitor fungicides of the class of inhibitors of glucan synthesis to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are validamycin, polyoxin B; melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamid, dicyclomet, or fenoxanil.
  • the fungicide is a plant defence inducer.
  • Suitable examples of plant defence inducer fungicides to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are acibenzolar-S-methyl, probenazole, isotianil, tiadinil, prohexadione-calcium; phosphonates: fosetyl, fosetyl-aluminum, phosphorous acid or its salts.
  • the fungicide is a compounds with unknown mode of action.
  • Suitable examples of such fungicides to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are bronopol, chinome- thionat, cyflufenamid, cymoxanil, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat- methylsulfate, diphenylamin, fenpyrazamine, flumetover, flusulfamide, flutianil, methasulfocarb nitrothal-isopropyl, picarbutrazox, tolprocarb, 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4- ⁇ 5-[2-(prop-2-yn-1 -yloxy)phenyl]-4,5-d
  • the fungicide may be selected from the following group of fungicides: A) Respiration inhibitors
  • Inhibitors of complex III at Q 0 site e. g. strobilurins: azoxystrobin, picoxystrobin, pyra- clostrobin, trifloxystrobin
  • inhibitors of complex II e. g. carboxamides: boscalid, fluopyram, fluxapyroxad, pen- flufen, penthiopyrad, sedaxane,
  • C14 demethylase inhibitors (DM I fungicides): cyproconazole, difenoconazole, flutriafol, ipconazole, prothioconazole, tebuconazole, triticonazole,
  • Delta14-reductase inhibitors fenpropimorph
  • phenylamides or acyl amino acid fungicides metalaxyl, metalaxyl-M (mefenoxam), ofu- race, oxadixyl;
  • tubulin inhibitors such as benzimidazoles, thiophanates: carbendazim, thiabendazole, other cell division inhibitors: diethofencarb, ethaboxam, fluopicolide, zoxamide, met- rafenone,
  • MAP / histidine kinase inhibitors fludioxonil
  • G protein inhibitors quinoxyfen
  • Lipid and membrane synthesis inhibitors phospholipid biosynthesis and cell wall deposition: dimethomorph, mandipropamid, fatty acid amide hydrolase inhibitors: oxathiapiprolin,
  • organochlorine compounds e. g. phthalimides, sulfamides, chloronitriles: anilazine, chlorothalonil,
  • the fungicide is azoxystrobin (A.1.1 ), pyraclostrobin (A.1.14), trifloxystrobin (A.1 .17), boscalid (A.3.4), fluopyram (A.3.7), fluxapyroxad (A.3.9), pen- flufen (A.3.14), penthiopyrad (A.3.15), sedaxane (A.3.16), difenoconazole (B.1.5), ipconazole (B.1.15), prothioconazole (B.1 .23), triticonazole (B.1 .29), metalaxyl (C.1 .4), metalaxyl-M (mefenoxam) (C.1.5), thiabendazole (D.1.4), ethaboxam (D.2.2), valifenalate (G.3.7), oxathiapiprolin (G.5.1 ), mancozeb (H.2.2), or
  • compositions comprising as compound I (component A) a nitrification inhibitor as defined herein above and as compound II (component B) a fungicide as defined herein, i.e. a combination of component A and B.
  • such compositions may be selected from the component A of Table 2 in column 2 (Com. A) and from component B of Table 2 in column 3 (Com. B).
  • the number of component A of Table 2 corresponds to the number of component A as shown in Table 1 , supra ("Entry").
  • Preferred embodiments thus include the specified combinations or compositions comprising component A and B as defined in Cb-1 to Cb-4515 of the following Table 2:
  • Cb-1390 100 A.3.14 Cb-1605 100 A.3.15 Cb-1820 100 A.3.16

Abstract

A composition comprising a)at least one(thio)phosphoric acid triamide (T) according to the general formula (Ia) Ra1 Ra2 N–P(X)(NH2)2 (Ia) wherein X is oxygen or sulfur; Ra1 is a C1 to C20 alkyl, C3 to C20 cycloalkyl, C6 to C20 aryl, or dialkylaminocarbonyl group;Ra2 is H, or Ra1 and Ra2 together with the nitrogen atom linking them define a 5-or 6-membered saturated or unsaturated heterocyclic radical, which optionally comprises 1 or 2 further heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur, and b) at least one specific fungicide.

Description

Combination of novel nitrification inhibitors and fungicides as well as combination of (thio)phosphoric acid triamides and fungicides
Description
The present invention relates to the combination of novel nitrification inhibitors of formula I and fungicides as well as to the combination of (thio)phosphoric acid triamides and fungicides. Moreover, the invention relates to the use of this combination of novel nitrification inhibitors and fungicides for increasing the health of a plant, and to the use of the combination of
(thio)phosphoric acid triamides and fungicides for increasing the health of a plant, as well as compositions comprising the nitrification inhibitor and a fungicide, and compositions comprising the (thio)phosphoric acid triamide and a fungicide. Further encompassed by the present invention are methods for increasing the health of a plant comprising the treatment of plants, soil and/or loci with said combination of the novel nitrification inhibitor and a fungicide or with said combination of (thio)phosphoric acid triamides and a fungicide.
Nitrogen is an essential element for plant growth, plant health and reproduction. About 25% of the plant available nitrogen in soils (ammonium and nitrate) originate from decomposition processes (mineralization) of organic nitrogen compounds such as humus, plant and animal resi- dues and organic fertilizers. Approximately 5% derive from rainfall. On a global basis, the biggest part (70%), however, are supplied to the plant by inorganic nitrogen fertilizers. The mainly used nitrogen fertilizers comprise ammonium compounds or derivatives thereof, i.e. nearly 90% of the nitrogen fertilizers applied worldwide is in the Nh form (Subbarao et al., 2012, Advances in Agronomy, 1 14, 249-302). This is, inter alia, due to the fact that Nh assimilation is energeti- cally more efficient than assimilation of other nitrogen sources such as NO3".
Moreover, being a cation, N h is held electrostatically by the negatively charged clay surfaces and functional groups of soil organic matter. This binding is strong enough to limit NhV-loss by leaching to groundwater. By contrast, NO3", being negatively charged, does not bind to the soil and is liable to be leached out of the plants' root zone. In addition, nitrate may be lost by denitri- fication which is the microbiological conversion of nitrate and nitrite (NO2 ) to gaseous forms of nitrogen such as nitrous oxide (N2O) and molecular nitrogen (N2).
However, ammonium (N hV) compounds are converted by soil microorganisms to nitrates (NO3" ) in a relatively short time in a process known as nitrification. The nitrification is carried out primarily by two groups of chemolithotrophic bacteria, ammonia-oxidizing bacteria (AOB) of the genus Nitrosomonas and Nitrobacter, which are ubiquitous component of soil bacteria populations. The enzyme, which is essentially responsible for nitrification is ammonia monooxygenase (AMO), which was also found in ammonia-oxidizing archaea (Subbarao et al., 2012, Advances in Agronomy, 1 14, 249-302).
The nitrification process typically leads to nitrogen leakage and environmental pollution. As a result of the various losses, approximately 50% of the applied nitrogen fertilizers is lost during the year following fertilizer addition (see Nelson and Huber; Nitrification inhibitors for corn production (2001 ), National Corn Handbook, Iowa State University).
As countermeasures the use of nitrification inhibitors, mostly together with fertilizers, was sug- gested. Suitable nitrification inhibitors include biological nitrification inhibitors (BNIs) such as linoleic acid, alpha-linolenic acid, methyl p-coumarate, methyl ferulate, MHPP, Karanjin, brachi- alacton or the p-benzoquinone sorgoleone (Subbarao et al., 2012, Advances in Agronomy, 1 14, 249-302). Further suitable nitrification inhibitors are synthetic chemical inhibitors such as Nitra- pyrin, dicyandiamide (DCD), 3,4-dimethyl pyrazole phosphate (DMPP), 4-amino-1 ,2,4-triazole hydrochloride (ATC), 1 -amido-2-thiourea (ASU), 2-amino-4-chloro-6-methylpyrimidine (AM), 5- ethoxy-3-trichloromethyl-1 ,2,4-thiodiazole (terrazole), or 2-sulfanilamidothiazole (ST) (Slangen and Kerkhoff, 1984, Fertilizer research, 5(1 ), 1-76).
EP 0 917 526 further mentions the use of polyacids to treat mineral fertilizers containing a nitrifi- cation inhibitor in order to improve the fixation of the nitrification inhibitors in the inorganic fertilizer. Moreover, the volatility of the nitrification inhibitor can be reduced.
However, many of these inhibitors only work sub-optimal or have undesirable side effects. In view of this situation there is hence a continuous need for compositions that increase the health of plants. Healthier plants are desirable since they result among other in better crop yields and/or a better quality of the plants or crops. Healthier plants also better resist to biotic and abiotic stress. A better resistance to stress in turn allows reducing the quantity of pesticides, which also helps avoiding the development of resistances against the respective pesti- cides.
One object of the present invention is to provide a composition containing a nitrification inhibitor which increases the health of plants, and/or provides better crop yields and/or a better quality of the plants or crops, and/or shows a better resistance to stress, and/or allows the reduction of the quantity of pesticides used, and/or helps avoiding the development of resistances against the respective pesticides
Another object of the present invention is to provide a composition containing the
(thio)phosphoric acid triamide(s) (T) which - each preferably through a synergistic action - (i) enhances the stability of the (thio)phosphoric acid triamide(s), and/or
(ii) enhances the urease inhibiting effect of the (thio)phosphoric acid triamide(s), and/or
(iii) enhances the yield increase effect of the (thio)phosphoric acid triamide(s), and/or
(iv) has a relatively long storage life, particularly before being applied to or coated on nitrogen- containing fertilizers, and/or
{v reduces the emission of nitrous oxide from soils, and/or
(vi) reduces the ammonia emission from soils, particularly when applied with urea-containing fertilizer on the same locus,
(vii) is toxicologically unobjectionable, and/or (viii) does not adversely affect the urease-inhibiting effect and/or activity of the (thio)phosphoric acid triamide, and/or
(ix) can be easily and safely packaged, transported and shipped, even in large quantities, and/or
(x) can be easily and safely handled and applied for soil treatment, even in large quantities, and/or
(xi) improves the nutrient use efficiency, and/or
(xii) improves the delivery of the fungicide to the plant, and/or
(xiii) improves the plant growth (e.g. biomass, yield, root branching and length; compact growth in case of ornamental plants), and/or
(xiv) enables a better developed root system, a larger leaf area, greener leaves, stronger shoots and/or
(xv) improves the plant defense of the plants, and/or
(xvi) improves the plant health of the plants, and/or
(xvii) improves the quality of the plants, and/or
(xviii) improves the storage or survivability of the fungicide and/or prolong the availability of fungicides to the plants, and/or
(xix) enhances the fungicidal effect of the fungicide, and/or
(xx) allows the reduction of the quantity of fungicides used, and/or
(xxi) increase the survivability rate of seedlings, for example transplanted seedlings, and/or
(xxii) reduce or avoid unfavorable environmental or toxicological effects whilst still allowing effective pest control, and/or
(xxiii) enable earlier seed germination and/or blooming. The objects (xiii), (xiv), (xv), (xvi), (xvii) and (xxi) particularly pertains to such plants or seedlings wherein such plants or seedlings were, or the soil in which the such plants or seedlings were placed was subject to the application of compositon of the present invention.
The preferred objects of the present invention are (i), (ii), (v), (vi), (vii), (xi), (xii), (xiii), (xiv), (xv), (xvi), (xvii), (xviii), (xix), (xx), the more preferred objects of the present invention are (ii), (vi), (xii), (xiii), (xv), (xvi), (xix), and/or (xx), the most preferred objects of the present invention are (ii), (vi), (xvi), and/or (xix), the particularly preferred objects of the present invention are (xvi) and/or (xix). The term "in a synergistic way" means that the composition comprising the (thio)phosphoric acid triamide (T) and a further compound can fulfil the one or more of the objects (i) to (xxvii) significantly better than the individual compounds - i.e. the (thio)phosphoric acid triamide (T) or said further compound - alone can do, and preferably, this better fulfilment of the objects by said composition compared to the individual compounds is evidenced by calculations according to Colby' s formula, see Colby, S. R. (Calculating synergistic and antagonistic responses of herbicide Combinations", Weeds, 15, pp. 20-22, 1967) The present invention addresses this need and relates to a combination of a novel nitrification inhibitor of formula I
Figure imgf000005_0001
or a stereoisomer, salt, tautomer or N-oxide thereof, wherein
A is aryl or hetaryl, wherein the aromatic ring may in each case be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from RA;
R1 and R2 are independently of each other selected from H and Ci-C2-alkyl; and
R3 is H, Ci-C4-haloalkyl, Ci-C4-hydroxyalkyl, ethynylhydroxym ethyl, phenylhydroxymethyl, or aryl, wherein the aromatic ring may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from RB; and wherein
RA is
(i) halogen, CN, NRaRb, ORc, SRC, C(=Y1)RC, C(=Y1)ORc, C(=Y1)SRC, C(=Y1)NRaRb, Y2C(=Y1)RC, Y2C(=Y1)ORc, Y2C(=Y1)SRC, Y2C(=Y1)NRaRb, Y3Y2C(=Y1)RC,
Figure imgf000005_0002
S(=0)2Y2C(=Y1)NRaRb, N02, NON-CN, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C4- haloalkyl, Ci-C4-cyanoalkyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, C2-C4-alkynyl-Ci-C2- hydroxyalkyl, C2-C4-alkynyloxy;
Figure imgf000005_0003
C2-C4-alkenylene-C(=Y1)ORc,
Figure imgf000005_0004
C2-C4-alkenylene-C(=Y1)SRc,
Figure imgf000005_0005
Ci-C4-alkylene-Y2- C(=Y1)RC, C2-C4-alkenylene-Y2-C(=Y1)Rc, Ci-C4-alkylene-NRaRb, C2-C4-alkenylene- NRaRb, Ci-C4-alkylene-ORc, C2-C4-alkenylene-ORc, Ci-C4-alkylene-SRc, C2-C4- alkenylene-SRc, wherein the Ci-C4-alkylene or C2-C4-alkenylene chain may in each case be unsubstituted or may be partially or fully substituted by ORa, CN, halogen or phenyl; (iii) aryl, aryl-Ci-C2-alkyl, hetaryl or hetaryl-Ci-C2-alkyl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from Rh;
(iv) a 3- to 14-membered saturated or unsaturated carbocycle or heterocycle, which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from NR1b, O, and S, wherein S may be oxidized and/or wherein the carbocycle or het- erocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R1b is H, C1-C4- alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6-cycloalkylmethyl, or ORa; or
(v) L-B, wherein
L is -CH2-, -CH=CH-, -C≡C-, -C(=0)- or -CH=, and
B is aryl or hetaryl, wherein the aromatic ring of the ary or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from Rh;
or
a 3- to 14-membered saturated or unsaturated carbocycle or heterocycle, which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from N R1b, O, and S, wherein S may be oxidized and/or wherein the carbocycle or heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R1b is H, Ci-C4-alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6-cycloalkylmethyl, or OR9; or
(vi) two substituents RA together represent a carbocyclic or heterocyclic ring, which is fused to A and may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from NR1c, O, and S, wherein S may be oxidized and/or wherein the carbocycle or heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R1c is H, d-C4-alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6- cycloalkylmethyl, C3-C6-heterocyclyl, C3-C6-heterocyclylmethyl or OR9; and wherein
RB is NH-C(=0)-(Ci-C4-alkyl), NH-C(=0)-(C2-C4-alkenyl),
Figure imgf000006_0001
alkyl), NH-C(=0)-(C3-C6-cycloalkyl), NH-S(=0)2-(Ci-C4-alkyl), or N02; and wherein
Y1, Y2 and Y3 are independently of each other selected from O, S and NR1a, wherein R1a is in each case independently H, Ci-C4-alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6- cycloalkylmethyl, ORa, SRa or NRmRn;
Ra and Rb are independently of each other selected from
(i) H, NRRk, OR, SR, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, C(=Y1)R, C(=Y1)OR, C(=Y1)SR, C(=Y1)NRRk, C(=Y1)C(=Y2)R, S(=0)2R;
(ii) aryl or hetaryl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from Rh; or
Ra and Rb together with the nitrogen atom to which they are bound form (iii) a hetaryl group which may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from Rh; or
(iv) a 3- to 10-membered, saturated or unsaturated heterocycle, which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from NR1b, O, and S, wherein S may be oxidized and/or wherein the heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R1b is H , Ci-C4-alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6-cycloalkylmethyl, or ORa; Rc is
(i) H, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C(=0)OR, C(=0)SR, C(=0)NRRk;
(ii) Ci-C4-alkylene-C(=0)R, Ci-C4-alkylene-C(=0)OR, wherein the Ci-C4-alkylene chain may in each case be unsubstituted or may be partially or fully substituted by ORa, CN, halogen, or phenyl;
(iii) aryl, aryl-Ci-C2-alkyl, hetaryl, or hetaryl-Ci-C2-alkyl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from Rh; or
(iv) a 3- to 10-membered saturated or unsaturated carbocycle or heterocycle, which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from NR1b, O, and S, wherein S may be oxidized and/or wherein the carbocycle or heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R1b is H, Ci-C4- alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6-cycloalkylmethyl, or ORa; Rd and Re are independently selected from Ci-C4-alkyl, Ci-C4-haloalkyl, NRRk, OR, SR, CN, C(=Y1)R, C(=Y1)OR, C(=Y1)SR, or C(=Y1)NRRk;
R is Ci-C4-alkyl, Ci-C4-haloalkyl, NRRk, OR, SR, aryl or hetaryl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from Rh;
R9 is H or Ci-C4-alkyl;
Rh is halogen, CN, N02, NRRk, OR, SR, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4- haloalkyl, Ci-C4-alkoxy, C2-C4-alkynyloxy, C(=Y1)R, C(=Y1)OR, C(=Y1)SR, C(=Y1)NRRk, aryl, aryloxy, hetaryl and hetaryloxy; is
(i) halogen, CN, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-haloalkyl, C2-C4- haloalkenyl;
(ii) =NR1d, wherein R1d is H, Ci-C4-alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6- cycloalkylmethyl, or OR9;
(iii) =0, =S, N RRk, OR, SR, C(=Y1)R, C(=Y1)OR, C(=Y1)SR, C(=Y1)NRRk; (iv) aryl, aryl-Ci-C2-alkyl, hetaryl, or hetaryl-Ci-C2-alkyl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from halogen, CN, C1-C4- alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, C2-C4-alkynyloxy, ORa, and SRa; or
(v) C3-C6-cycloalkyl, or 3- to 6-membered heterocyclyl, wherein the cycloalkyl ring or the heterocyclyl ring may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from halogen, CN , Ci-C4-alkyl,
Figure imgf000008_0001
R and Rk are independently selected from H , ORa, SRa, C(=Y1)Ra, C(=Y1)ORa, C(=Y1)SRa, C(=Y1)N RmRn, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-haloalkyl, aryl or hetaryl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently selected from halogen, CN , Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, C2-C4-alkynyloxy, ORa, and SRa;
R is H , Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-haloalkyl, C(=Y1)Ra, C(=Y1)ORa,
C(=Y1)N RmRn, aryl or hetaryl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently selected from halogen, CN , Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, C2-C4-alkynyloxy, ORa, and SRa; and
Rm and Rn are independently selected from H and Ci-C4-alkyl;
and a fungicide. The inventors surprisingly found that by applying the compound of formula I as defined herein above and of a fungicide the nitrification of ammonium to nitrate could significantly be reduced, biotic stress could be reduced and in consequence the health of a plant could be increased.
The inventors surprisingly found that by applying the (thio)phosphoric acid triamide (T) as de- fined herein above and of a fungicide the urease inhibiting effect of the (thio)phosphoric acid triamide(s) could be enhanced, biotic stress could be reduced and in consequence the health of a plant could be increased, also the fungicidal activity of the fungicide could be enhanced, and other objects as mentioned above under the list (i) to (xxviii) could be fulfilled preferably in a synergistic way.
The present invention relates in another aspect to the composition (Q) comprising a fungicide and a (thio)phosphoric acid triamide according to the general formula (la)
Ra1 Ra2N-P(X)(N H2)2 (la) wherein
X is oxygen or sulfur; Ra1 is a Ci to C20 alkyl, C3 to C20 cycloalkyl, C& to C20 aryl, or dialkylaminocarbonyl group;
Ra2 is H , or
Ra1 and Ra2 together with the nitrogen atom linking them define a 5- or 6-membered saturated or unsaturated heterocyclic radical, which optionally comprises 1 or 2 further heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur, and the present invention preferably relates to a composition (Q) comprising a fungicide and a (thio)phosphoric acid triamide according to the general formula (la) and not comprising any nitrification inhibitor of the compound of formula I.
The "(thio)phosphoric acid triamide according to the general formula (la)" is also referred to as "(thio)phosphoric acid triamide (T)" or "(T)" in the present patent application, "wt.%" refers to "percent by weight".
The composition (Q) also includes kit-of-parts comprising a fungicide and (T). Here, the term "kit-of-parts" is to be understood to denote a kit comprising at least two separate parts wherein each of the parts can be independently removed from the kit. A kit includes a box, a tool, a vessel, a container, a bag or any kit-like equipment. Also a kit whose separate parts are only to- gether in this one kit for a extremely short period of time are regarded as kit-of-parts. Kit-of-parts are useful for the combined application (of the contents) of the separate parts of the kit.
The present invention relates in another aspect to the use of a composition (Q) comprising a fungicide and a (thio)phosphoric acid triamide (T) for increasing the health of a plant, and the present invention preferably relates to the use of a composition (Q) comprising a fungicide and a (thio)phosphoric acid triamide (T) and not comprising any nitrification inhibitor of the compound of formula I for increasing the health of a plant.
X in the general formula (la) is preferably sulfur. Ra1 in the general formula (la) is preferably Ci-C2o-alkyl, more preferably Ci-Cio-alkyl, most preferably C2-C7 alkyl, for example C3-C4 alkyl. Examples of alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, hex- yl, 2-methylpentyl, heptyl, octyl, 2-ethylhexyl, isooctyl, nonyl, isononyl, decyl and isodecyl. Examples of cycloalkyl groups are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and cyclooctyl, examples of aryl groups are phenyl or naphthyl. Examples of heterocyclic radicals Ra1Ra2N- are piperazinyl, morpholinyl, pyrrolyl, pyrazolyl, triazolyl, oxazolyl, thiazolyl or imidazolyl groups.
According to one embodiment, the (thio)phosphoric acid triamide (T) is preferably N-n- butylthiophosphoric acid triamide (NBPT) and/or N-n-propylthiophosphoric acid triamide (NPPT), more preferably NBPT. According to another embodiment, (T) is preferably NPPT. Ac- cording to another embodiment, (T) is preferably LIM US, i.e. a mixture of NBPT and NPPT with about NBPT at 63% and NPPT at 22%, secondary compounds at 10%, further secondary compounds such as amines below 4% and dimerease derivatives below 1 %.
According to another embodiment, the composition (Q) comprises a fungicide and at least two different (thio)phosphoric acid triamides (T) having structures of the general formula (la) and wherein said at least two different (thio)phosphoric acid triamides differ in a of radicals Ra1 or Ra2, and preferably, one of said at least two different (thio)phosphoric acid triamides is N-n- butylthiophosphoric acid triamide (NBPT), and more preferably, the other of said at least two different (thio)phosphoric acid triamides is selected from the group consisting of N-cyclohexyl-, N-pentyl-, N-isobutyl- and N-n-propylphosphoric acid triamide and -thiophosphoric acid triamide. More preferably, (Q) comprises a fungicide, NBPT and NPPT. Particularly preferably, (Q) comprises a fungicide, NBPT and NPPT, wherein NBPT is present in amounts of from 1 to 99.99 wt.%, more preferably from 10 to 99.9 wt.%, most preferably from 20 to 99 wt.%, particularly preferably from 30 to 98 wt.%, more particularly preferably from 40 to 95 wt.%, most particularly preferably from 50 to 90 wt.%, especially from 60 to 85 wt.%, especially preferably from 72 to 80 wt.%, for example from 74 to 77 wt.%, in each case based on the total weight of the (thio)phosphoric acid triamides (T) contained in the composition (Q).
Generally, the (thio)phosphoric acid triamides (T) can be contained in varying amounts in the composition (Q). Preferably, the amount of (T) is not more than 95 wt.% (wt.% stands for "percent by weight"), more preferably not more than 90 wt.%, most preferably not more than 85 wt.%, more particularly preferably not more than 75 wt.%, most particularly preferably not more than 65 wt.%, particularly not more than 55 wt.%, especially not more than 45 wt.% for example not more than 35 wt.%, based on the total weight of the composition (Q). Preferably, the amount of (T) is at least 1 wt.%, more preferably at least 4 wt.%, most preferably at least 14 wt.%, more particularly preferably at least 24 wt.%, most particularly preferably at least 34 wt.%, particularly at least 44 wt.%, especially at least 54 wt.%, for example at least 64 wt.%, based on the total weight of the composition (Q).
According to another embodiment, the composition (Q) preferably does not comprise any nitrification inhibitor of the compound of formula I. Thus, in another aspect the present invention relates to the use of combination of a fungicide and a nitrification inhibitor for increasing the health of a plant, wherein said nitrification inhibitor is a compound of formula I as defined herein above.
In a preferred embodiment of said use, in said compound of formula I, A is phenyl or a 5- or 6- membered hetaryl, wherein the aromatic ring may in each case be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from RA.
In another preferred embodiment of said use, in said compound of formula I, R1 and R2 both represent hydrogen. In yet another preferred embodiment of said use, in said compound of formula I, R3 is hydrogen, Ci-C4-haloalkyl or ethinylhydroxym ethyl, and preferably R3 is hydrogen.
In still another preferred embodiment of said use, in said compound of formula I, RA, if present, is
(i) halogen, CN, NRaRb, ORc, C(=Y1)RC, C(=Y1)ORc, C(=Y1)SRC, C(=Y1)NRaRb, Y2C(=Y1)RC, Y2C(=Y1)NRaRb, N RaN=C(Rd)(Re), S(=0)2Rf, N02, Ci-C6-alkyl, C2-C6- C1-C4- haloalkyl, Ci-C4-alkoxy, C2-C4-alkynyl-Ci-C2-hydroxyalkyl, C2-C4-alkynyloxy;
(ii) C2-C4-alkenylene-C(=Y1)Rc, C2-C4-alkenylene-Y2-C(=Y1)Rc, wherein the C1-C4- alkylene or C2-C4-alkenylene chain may in each case be unsubstituted or may be partially or fully substituted by CN or halogen;
(iii) aryl, wherein the aromatic ring of the aryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other se- lected from Rh; or
(iv) a 3- to 14-membered saturated or unsaturated heterocycle, which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from NR1b, O, and S, wherein S may be oxidized and/or wherein the heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R1b is H , Ci-C4-alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl,
C3-C6-cycloalkylmethyl, or ORa.
In a further preferred embodiment of said use - either in combination with a (thio)phosphoric acid triamide (T) or in combination with a nitrification inhibitor of fornula I -, the fungicide is at least one fungicide selected from the group of fungicides comprising:
A) Respiration inhibitors such as:
(i) Inhibitors of complex III at Q0 site (e.g. strobilurines) selected from, azoxystrobin (A.1 .1 ), coumethoxystrobin (A.1.2), coumoxystrobin (A.1.3), dimoxystrobin (A.1 .4), enestroburin (A.1.5), fenaminstrobin (A.1.6), fenoxystrobin/flufenoxystrobin (A.1 .7), fluoxastrobin (A.1 .8), kresoxim-m ethyl (A.1.9), mandestrobin (A.1 .10), meto- minostrobin (A.1 .1 1 ), orysastrobin (A.1 .12), picoxystrobin (A.1 .13), pyraclostrobin (A.1 .14), pyrametostrobin (A.1 .15), pyraoxystrobin (A.1.16), trifloxystrobin (A.1.17) and 2-(2-(3-(2,6-dichlorophenyl)-1 -methyl-allylideneaminooxymethyl)-phenyl)-2- methoxyimino-N-methyl-acetamide (A.1 .18), pyribencarb (A.1 .19), triclopy- ricarb/chlorodincarb (A.1.20), famoxadone (A.1 .21 ), fenamidone (A.1.21 );
(ii) inhibitors of complex III at Q, site selected from cyazofamid (A.2.1 ), amisulbrom (A.2.2), [(3S,6S,7R,8R)-8-benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2- carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate (A.2.3), [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)-4-methoxy-pyridine- 2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate
(A.2.4), [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxy-pyridine- 2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate (A.2.5), [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1 ,3-benzodioxol-5-ylmethoxy)-4-methoxy- pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methyl- propanoate (A.2.6); (3S,6S,7R,8R)-3-[[(3-hydroxy-4-methoxy-2- pyridinyl)carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1 ,5-dioxonan-7-yl 2- methylpropanoate (A.2.7)
(iii) inhibitors of complex II (e. g. carboxamides) selected from benodanil (A.3.1 ), ben- zovindiflupyr (A.3.2), bixafen (A.3.3), boscalid (A.3.4), carboxin (A.3.5), fenfuram (A.3.6), fluopyram (A.3.7), flutolanil (A.3.8), fluxapyroxad (A.3.9), furametpyr (A.3.10), isofetamid (A.3.1 1 ), isopyrazam (A.3.12), mepronil (A.3.13), oxycarboxin (A.3.14), penflufen (A.3.14), penthiopyrad (A.3.15), sedaxane (A.3.16), tecloftalam (A.3.17), thifluzamide (A.3.18), N-(4'-trifluoromethylthiobiphenyl-2-yl)- 3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide (A.3.19), N-(2-(1 ,3,3- trimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxamide (A.3.20), 3-(difluoromethyl)-1 -methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide (A.3.21 ), 3-(trifluoromethyl)-1 -methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4- carboxamide (A.3.22), 1 ,3-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4- carboxamide (A.3.23), 3-(trifluoromethyl)-1 ,5-dimethyl-N-(1 ,1 ,3-trimethylindan-4- yl)pyrazole-4-carboxamide (A.3.24), 1 ,3,5-trimethyl-N-(1 ,1 ,3-trimethylindan-4- yl)pyrazole-4-carboxamide (A.3.25), N-(7-fluoro-1 ,1 ,3-trimethyl-indan-4-yl)-1 ,3- dimethyl-pyrazole-4-carboxamide (A.3.26), N-[2-(2,4-dichlorophenyl)-2-methoxy-1 - methyl-ethyl]-3-(difluoromethyl)-1 -methyl-pyrazole-4-carboxamide (A.3.27);
(iv) other respiration inhibitors or complex I uncouplers selected from diflumetorim
(A.4.1 ), (5,8-difluoroquinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2- yloxy)-phenyl]-ethyl}-amine (A.4.2); nitrophenyl derivates: binapacryl (A.4.3), dino- buton (A.4.4), dinocap (A.4.5), fluazinam (A.4.6); ferimzone (A.4.7); organometal compounds: fentin salts, such as fentin-acetate (A.4.8), fentin chloride (A.4.9) or fentin hydroxide (A.4.10); ametoctradin (A.4.1 1 ); and silthiofam (A.4.12);
terol biosynthesis inhibitors (SBI fungicides) such as:
(v) ): triazoles: azaconazole (B.1 .1 ), bitertanol (B.1 .2), bromuconazole (B.1 .3), cypro- conazole (B.1.4), difenoconazole (B.1.5), diniconazole (B.1 .6), diniconazole-M (B.1 .7), epoxiconazole (B.1 .8), fenbuconazole (B.1.9), fluquinconazole (B.1.10), flusilazole (B.1 .1 1 ), flutriafol (B.1.12), hexaconazole (B.1.13), imibenconazole (B.1 .14), ipconazole (B.1.15), metconazole (B.1.17), myclobutanil (B.1.18), oxpoconazole (B.1 .19), paclobutrazole (B.1.20), penconazole (B.1.21 ), propicona- zole (B.1 .22), prothioconazole (B.1 .23), simeconazole (B.1 .24), tebuconazole (B.1 .25), tetraconazole (B.1.26), triadimefon (B.1.27), triadimenol (B.1 .28), triticon- azole (B.1.29), uniconazole (B.1 .30),
(vi) 1 -[re/-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thio- cyanato-1 H-[1 ,2,4]triazole (B.1 .31 ), 2-[re/-(2S;3fi)-3-(2-chlorophenyl)-2-(2,4- difluorophenyl)-oxiranylmethyl]-2H-[1 ,2,4]triazole-3-thiol (B.1 .32), 2-[2-chloro-4-(4- chlorophenoxy)phenyl]-1 -(1 ,2,4-triazol-1 -yl)pentan-2-ol (B.1.33), 1 -[4-(4- chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -cyclopropyl-2-(1 ,2,4-triazol-1 - yl)ethanol (B.1 .34), 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4- triazol-1 -yl)butan-2-ol (B.1.35), 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1 -(1 ,2,4- triazol-1 -yl)butan-2-ol (B.1.36), 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-3- methyl-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol (B.1 .37), 2-[4-(4-chlorophenoxy)-2- (trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)propan-2-ol (B.1.38), 2-[2-chloro-4-(4- chlorophenoxy)phenyl]-3-methyl-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol (B.1.39), 2-[4-(4- chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)pentan-2-ol (B.1.40),
2-[4-(4-fluorophenoxy)-2-(trifluoromethyl)phenyl]-1-(1 ,2,4-triazol-1 -yl)propan-2-ol (B.1 .41 ), 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1-(1 ,2,4-triazol-1 -yl)pent-3-yn-2-ol (B.1 .51 ); imidazoles: imazalil (B.1 .42), pefurazoate (B.1.43), prochloraz (B.1.44), triflumizol (B.1.45); pyrimidines, pyridines and piperazines: fenarimol (B.1 .46), nuarimol (B.1 .47), pyrifenox (B.1 .48), triforine (B.1.49), [3-(4-chloro-2-fluoro- phenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]-(3-pyridyl)methanol (B.1 .50; (vii) Delta14-reductase inhibitors selected from aldimorph (B.2.1 ), dodemorph (B.2.2), dodemorph-acetate (B.2.3), fenpropimorph (B.2.4), tridemorph (B.2.5), fenpropidin (B.2.6), piperalin (B.2.7), spiroxamine (B.2.8);
(viii) Inhibitors of 3-keto reductase selected from fenhexamid (B.3.1 );
C) Nucleic acid synthesis inhibitors such as:
(ix) phenylamides or acyl amino acid fungicides selected from benalaxyl (C.1 .1 ), ben- alaxyl-M (C.1.2), kiralaxyl (C.1.3), metalaxyl (C.1 .4), metalaxyl-M (mefenoxam, C.1.5), ofurace (C.1.6), oxadixyl (C.1.7);
(x) hymexazole (C.2.1 ), octhilinone (C.2.2), oxolinic acid (C.2.3), bupirimate (C.2.4), 5- fluorocytosine (C.2.5), 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine (C.2.6), 5- fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4-amine (C.2.7);
D) Inhibitors of cell division and cytoskeleton such as:
(xi) tubulin inhibitors selected from benzimidazoles, thiophanates: benomyl (D1 .1 ), carbendazim (D1 .2), fuberidazole (D1.3), thiabendazole (D1.4), thiophanate- methyl (D1.5); triazolopyrimidines: 5-chloro-7-(4-methylpiperidin-1 -yl)-6-(2,4,6- trifluorophenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine (D1.6);
(xii) other cell division inhibitors selected from diethofencarb (D2.1 ), ethaboxam (D2.2), pencycuron (D2.3), fluopicolide (D2.4), zoxamide (D2.5), metrafenone (D2.6), pyri- ofenone (D2.7);
E) Inhibitors of amino acid and protein synthesis such as:
(xiii) methionine synthesis inhibitors (anilino-pyrimidines) selected from cyprodinil
(E.1 .1 ), mepanipyrim (E.1 .2), pyrimethanil (E.1.3);
(xiv) protein synthesis inhibitors selected from blasticidin-S (E.2.1 ), kasugamycin
(E.2.2), kasugamycin hydrochloride-hydrate (E.2.3), mildiomycin (E.2.4), streptomycin (E.2.5), oxytetracyclin (E.2.6), polyoxine (E.2.7), validamycin A (E.2.8);
F) Signal transduction inhibitors such as:
(i) MAP / histidine kinase inhibitors selected from fluoroimid (F.1.1 ), iprodione (F.1 .2), procymidone (F.1 .3), vinclozolin (F.1.4), fenpiclonil (F.1.5), fludioxonil (F.1.6); (xv) G protein inhibitors selected from quinoxyfen (F.2.1 );
G) Lipid and membrane synthesis inhibitors such as:
(xvi) Phospholipid biosynthesis inhibitors selected from edifenphos (G.1.1 ), iprobenfos (G.1 .2), pyrazophos (G.1.3), isoprothiolane (G.1.4); (xvii) lipid peroxidation inhibitors selected from dicloran (G.2.1 ), quintozene (G.2.2), tec- nazene (G.2.3), tolclofos-methyl (G.2.4), biphenyl (G.2.5), chloroneb (G.2.6), etridiazole (G.2.7);
(xviii) phospholipid biosynthesis and cell wall deposition inhibitors selected from dime- thomorph (G.3.1 ), flumorph (G.3.2), mandipropamid (G.3.3), pyrimorph (G.3.4), benthiavalicarb (G.3.5), iprovalicarb (G.3.6), valifenalate (G.3.7) and N-(1 -(1 -(4- cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester (G.3.8);
(xix) compounds affecting cell membrane permeability and fatty acides selected from propamocarb (G.4.1 ), propamocarb-hydrochlorid
(xx) fatty acid amide hydrolase inhibitors selected from oxathiapiprolin (G.5.1 ), 2-{3-[2- (1 -{[3,5-bis(difluoromethyl-1 H-pyrazol-1 -yl]acetyl}piperidin-4-yl)-1 ,3-thiazol-4-yl]- 4,5-dihydro-1 ,2-oxazol-5-yl}phenyl methanesulfonate (G.5.2), 2-{3-[2-(1 -{[3,5- bis(difluoromethyl)-1 H-pyrazol-1 -yl]acetyl}piperidin-4-yl) 1 ,3-thiazol-4-yl]-4,5- dihydro-1 ,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate (G.5.3);
H) Inhibitors with Multi Site Action such as:
(xxi) inorganic active substances selected from Bordeaux mixture (H .1 .1 ), copper acetate (H.1 .2), copper hydroxide (H.1.3), copper oxychloride (H.1 .4), basic copper sulfate (H.1.5), sulfur (H.1.6);
(xxii) thio- and dithiocarbamates selected from ferbam (H.2.1 ), mancozeb (H.2.2),
maneb (H.2.3), metam (H.2.4), metiram (H.2.5), propineb (H.2.6), thiram (H.2.7), zineb (H .2.8), ziram (H.2.9);
(xxiii) organochlorine compounds (e.g. phthalimides, sulfamides, chloronitriles) selected from anilazine (H .3.1 ), chlorothalonil (H .3.2), captafol (H.3.3), captan (H.3.4), folpet (H.3.5), dichlofluanid (H.3.6), dichlorophen (H.3.7), hexachlorobenzene (H.3.8), pentachlorphenole (H.3.9) and its salts, phthalide (H.3.10), tolylfluanid (H.3.1 1 ), N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl-benzenesulfonamide (H .3.12);
(xxiv) guanidines and others selected from guanidine (H.4.1 ), dodine (H.4.2), dodine free base (H.4.3), guazatine (H.4.4), guazatine-acetate (H.4.5), iminoctadine (H .4.6), iminoctadine-triacetate (H.4.7), iminoctadine-tris(albesilate) (H.4.8), dithianon
(H.4.9), 2,6-dimethyl-1 H,5H-[1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H ,6H)- tetraone (H.4.10);
I) Cell wall synthesis inhibitors such as:
(xxv) inhibitors of glucan synthesis selected from validamycin (1.1 .1 ), polyoxin B (1.1 .2); melanin synthesis inhibitors: pyroquilon (1.2.1 ), tricyclazole (1.2.2), carpropamid
(I.2.3), dicyclomet (I.2.4), fenoxanil (I.2.5);
J) Plant defence inducers selected from:
(xxvi) acibenzolar-S-methyl (J.1 .1 ), probenazole (J.1.2), isotianil (J.1.3), tiadinil (J.1.4), prohexadione-calcium (J.1 .5); phosphonates: fosetyl (J.1 .6), fosetyl-aluminum (J.1.7), phosphorous acid and its salts (J.1 .8), potassium or sodium bicarbonate
(J.1.9);
K) Compounds with unknown mode of action selected from: (xxvii) bronopol (K.1 .1 ), chinomethionat (K.1.2), cyflufenamid (K.1.3), cymoxanil (K.1 .4), dazomet (K.1 .5), debacarb (K.1 .6), diclomezine (K.1.7), difenzoquat (K.1 .8), difenzoquat-methylsulfate (K.1.9), diphenylamin (K.1.10), fenpyrazamine (K.1 .1 1 ), flumetover (K.1 .12), flusulfamide (K.1 .13), flutianil (K.1.14), methasul- focarb (K.1 .15), nitrapyrin (K.1.16), nitrothal-isopropyl (K.1.18), oxathiapiprolin (K.1 .19), tolprocarb (K.1.20), oxin-copper (K.1.21 ), proquinazid (K.1 .22), tebuflo- quin (K.1.23), tecloftalam (K.1 .24), triazoxide (K.1 .25), 2-butoxy-6-iodo- 3-propylchromen-4-one (K.1.26), 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4- (4-{5-[2-(prop-2-yn-1 -yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2- yl)piperidin-1 -yl]ethanone (K.1 .27), 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4- (4-{5-[2-fluoro-6-(prop-2-yn-1 -yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thi- azol-2-yl)piperidin-1 -yl]ethanone (K.1 .28), 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 - yl]-1 -[4-(4-{5-[2-chloro-6-(prop-2-yn-1 -yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}- 1 ,3-thiazol-2-yl)piperidin-1 -yl]ethanone (K.1 .29), N-(cyclopropylmethoxyimino-(6- difluoro-methoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide (K.1 .30), N'-(4- (4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimeth^^
formamidine (K.1 .31 ), N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl- phenyl)-N-ethyl-N-methyl formamidine (K.1 .32), N'-(2-methyl-5-trifluoromethyl-4-(3- trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine (K.1.33), N'-(5- difluoromethyl-2-methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine (K.1.34), methoxy-acetic acid 6-tert-butyl-8-fluoro-2,3-dimethyl- quinolin-4-yl ester (K.1.35), 3-[5-(4-methylphenyl)-2,3-dimethyl-isoxazolidin-3-yl]- pyridine (K.1.36), 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine (pyrisoxazole) (K.1.37), N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide (K.1 .38), 5-chloro-1 -(4,6-dimethoxy-pyrimidin-2-yl)-2-methyl-1 H-ben- zoimidazole (K.1 .39), 2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5- yl]-2-prop-2-ynyloxy-acetamide, ethyl (Z)-3-amino-2-cyano-3-phenyl-prop-2-enoate (K.1 .40), picarbutrazox (K.1 .41 ), pentyl N-[6-[[(Z)-[(1 -methyltetrazol-5-yl)-phenyl- methylene]amino]oxymethyl]-2-pyridyl]carbamate (K.1 .42), 2-[2-[(7,8-difluoro-2- methyl-3-quinolyl)oxy]-6-fluoro-phenyl]propan-2-ol (K.1 .43), 2-[2-fluoro-6-[(8-fluoro- 2-methyl-3-quinolyl)oxy]phen-yl]propan-2-ol (K.1 .44), 3-(5-fluoro-3,3,4,4- tetramethyl-3,4-dihydroisoquinolin-1 -yl)quinoline (K.1.45), 3-(4,4-difluoro-3,3- dimethyl-3,4-dihydroisoquinolin-1 -yl)quinoline (K.1.46), 3-(4,4,5-trifluoro-3,3- dimethyl-3,4-dihydroisoquinolin-1 -yl)quinoline (K.1 .47), 9-fluoro-2,2-dimethyl-5-(3- quinolyl)-3H-1 ,4-benzoxazepine (K.1 .48).
In a particularly preferred embodiment, said fungicide is azoxystrobin (A.1 .1 ), pyraclostrobin (A.1 .14), thfloxystrobin (A.1 .17), boscalid (A.3.4), fluopyram (A.3.7), fluxapyroxad (A.3.9), pen- flufen (A.3.14), penthiopyrad (A.3.15), sedaxane (A.3.16), difenoconazole (B.1.5), ipconazole (B.1 .15), prothioconazole (B.1 .23), triticonazole (B.1.29), metalaxyl (C.1 .4), metalaxyl-M
(mefenoxam) (C.1.5), thiabendazole (D.1 .4), ethaboxam (D.2.2), valifenalate (G.3.7), oxathiapiprolin (G.5.1 ), mancozeb (H.2.2), or chlorothalonil (H.3.2). In a further preferred embodiment, said combination of a nitrification inhibitor or (T) and a fungicide further comprises a fertilizer.
In a further aspect the present invention relates to a composition for increasing the health of a plant comprising at least one nitrification inhibitor as defined herein above or (T) and at least one fungicide as defined herein above.
In a preferred embodiment said agricultural compositon additionally comprises at least one carrier.
In another aspect the present invention relates to a method for increasing the health of a plant, comprising treating a plant growing on soil or soil substituents and/or the locus or soil or soil substituents where the plant is growing or is intended to grow with a combination of at least one nitrification inhibitor or (T) and at least one fungicide as defined herein above, or a composition as defined herein above.
In a preferred embodiment of the method the plant and/or the locus or soil or soil substituents where the plant is growing or is intended to grow is additionally provided with a fertilizer. In a further preferred embodiment of the method, the application of said nitrification inhibitor (A) and of said fungicide (B), and optionally of said fertilizer (C) is carried out simultaneously or with a time lag.
In a further preferred embodiment of the method, the application of (thio)phosphoric acid tri- amide (T) and of said fungicide (B), and optionally of said fertilizer (C) is carried out simultaneously or with a time lag.
In a particularly preferred embodiment, said time lag is an interval of 1 day, 2 days, 3 days, 1 week, 2 weeks or 3 weeks.
In a further preferred embodiment of a use, composition or method of the invention as mentioned herein above, said increase of the health of a plant is reflected by an increase in growth of root and shoot, an overall increase in productivity and/or a faster and more efficient development of the plant.
In a further preferred embodiment of the use, composition or method of the invention as mentioned herein above, said plant is an agricultural plant such as wheat, barley, oat, rye, soybean, corn, oilseed rape, canola, sunflower, cotton, sugar cane, sugar beet, rice or a vegetable such as spinach, lettuce, asparagus, or cabbages; or sorghum; a silvicultural plant; an ornamental plant; or a horticultural plant, each in its natural or in a genetically modified form.
In addition, a process for treating the soil comprising applying the compositions of the invention into the soil in-furrow and/or as side dress and/or as broadcast was found. The present invention relates in one aspect to the use of a fungicide and a nitrification inhibitor for increasing the health of a plant, wherein said nitrification inhibitor is a compound of formula I as defined herein. The present invention relates in another aspect to the use of a fungicide and a (thio)phosphoric acid triamide (T) for increasing the health of a plant.
Although the present invention will be described with respect to particular embodiments, this description is not to be construed in a limiting sense.
Before describing in detail exemplary embodiments of the present invention, definitions im- portant for understanding the present invention are given. As used in this specification and in the appended claims, the singular forms of "a" and "an" also include the respective plurals unless the context clearly dictates otherwise. In the context of the present invention, the terms "about" and "approximately" denote an interval of accuracy that a person skilled in the art will understand to still ensure the technical effect of the feature in question. The term typically indi- cates a deviation from the indicated numerical value of ±20 %, preferably ±15 %, more preferably ±10 %, and even more preferably ±5 %. It is to be understood that the term "comprising" is not limiting. For the purposes of the present invention the term "consisting of is considered to be a preferred embodiment of the term "comprising of. If hereinafter a group is defined to comprise at least a certain number of embodiments, this is meant to also encompass a group which preferably consists of these embodiments only. Furthermore, the terms "first", "second", "third" or "(a)", "(b)", "(c)", "(d)" etc. and the like in the description and in the claims, are used for distinguishing between similar elements and not necessarily for describing a sequential or chronological order. It is to be understood that the terms so used are interchangeable under appropriate circumstances and that the embodiments of the invention described herein are capable of oper- ation in other sequences than described or illustrated herein. In case the terms "first", "second", "third" or "(a)", "(b)", "(c)", "(d)", "i", "ii" etc. relate to steps of a method or use or assay there is no time or time interval coherence between the steps, i.e. the steps may be carried out simultaneously or there may be time intervals of seconds, minutes, hours, days, weeks, months or even years between such steps, unless otherwise indicated in the application as set forth herein above or below. It is to be understood that this invention is not limited to the particular methodology, protocols, reagents etc. described herein as these may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present invention that will be limited only by the appended claims. Unless defined otherwise, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art.
The term "nitrification inhibitor" is to be understood in this context as a chemical substance which slows down or stops the nitrification process. Nitrification inhibitors accordingly retard the natural transformation of ammonium into nitrate, by inhibiting the activity of bacteria such as Nitrosomonas spp. The term "nitrification" as used herein is to be understood as the biological oxidation of ammonia (N H3) or ammonium (NhV) with oxygen into nitrite (NO2 ) followed by the oxidation of these nitrites into nitrates (NO3 ) by microorganisms. Besides nitrate (NO3 ) nitrous oxide is also produced though nitrification. Nitrification is an important step in the nitrogen cycle in soil. The inhibition of nitrification may thus also reduce NO2 losses.
The term "compound(s) according to the invention", or "compounds of formula I" comprises the compound(s) as defined herein as well as a stereoisomer, salt, tautomer or N-oxide thereof. The term "compound(s) of the present invention" is to be understood as equivalent to the term "compound(s) according to the invention", therefore also comprising a stereoisomer, salt, tautomer or N-oxide thereof. The compounds of formula I may be amorphous or may exist in one or more different crystalline states (polymorphs) which may have different macroscopic properties such as stability or show different biological properties such as activities. The present invention relates to amorphous and crystalline compounds of formula I, mixtures of different crystalline states of the respective compound I, as well as amorphous or crystalline salts thereof.
Salts of the compounds of the formula I are preferably agriculturally acceptable salts. They can be formed in a customary manner, e.g. by reacting the compound with an acid of the anion in question if the compound of formula I has a basic functionality. Agriculturally useful salts of the compounds of formula I encompass especially the acid addition salts of those acids whose cati- ons and anions, respectively, have no adverse effect on the mode of action of the compounds of formula I. Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydro- gensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting compounds of formula I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
The term "N-oxide" includes any compound of formula I which has at least one tertiary nitrogen atom that is oxidized to an N-oxide moiety.
The organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members. The prefix Cn-Cm indicates in each case the possible number of carbon atoms in the group. The term "halogen" denotes in each case fluorine, bromine, chlorine or iodine, in particular fluorine, chlorine or bromine.
The term "alkyl" as used herein denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably from 1 to 3 carbon atoms. Examples of an alkyl group are methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl, iso-butyl, tert-butyl, n-pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-di methyl propyl, 1-ethylpropyl, n-hexyl, 1 ,1 -dimethylpropyl, 1 ,2- di methyl propyl, 1 -methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1 -dimethyl- butyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethyl- butyl, 1 -ethylbutyl, 2-ethylbutyl, 1 ,1 ,2-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1 -ethyl-1 -methyl- propyl, and 1 -ethyl-2-methylpropyl. The term "haloalkyl" as used herein denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms. Preferred haloalkyl moieties are selected from Ci-C4-haloalkyl, more preferably from Ci-C3-haloalkyl or Ci-C2-haloalkyl, in particular from Ci-C2-fluoroalkyl such as fluoromethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, and the like.
The term "cyanoalkyl" as used herein denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, wherein the hydrogen atoms of this group are partially or totally replaced with cyano groups. Preferred cyanoalkyl moieties are selected from Ci-C4-cyanoalkyl, more preferably from Ci-C3-cyanooalkyl or Ci-C2-cyanoalkyl.
The term "hydroxyalkyl" as used herein denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, wherein the hydrogen atoms of this group are partially or totally replaced with hydroxy groups. Preferred hydroxyalkyl moieties are selected from Ci-C4-hydroxy- alkyl, more preferably from Ci-C-hydroxyalkyl or Ci-C2-hydroxyalkyl. Preferred hydroxyalkyl moieties are selected from hydroxy methyl, dihydroxymethyl, trihydroxymethyl,1 -hydroxyethyl and 2-hydroxyethyl.
The term "ethynylhydroxymethyl" as used herein refers to the following substituent.
Figure imgf000019_0001
The term "phenylhydroxymethyl" as used herein refers to the following substituent.
Figure imgf000019_0002
The term "alkoxy" as used herein denotes in each case a straight-chain or branched alkyl group which is bound via an oxygen atom and has usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Examples of an alkoxy group are methoxy, ethoxy, n-propoxy, iso-propoxy, n-butyloxy, 2-butyloxy, iso-butyloxy, tert-butyloxy, and the like.
The term "alkoxyalkyl" as used herein refers to alkyl usually comprising 1 to 10, frequently 1 to 4, preferably 1 to 2 carbon atoms, wherein 1 carbon atom carries an alkoxy radical usually comprising 1 to 4, preferably 1 or 2 carbon atoms as defined above. Examples are CH2OCH3, CH2-OC2H5, 2-(methoxy)ethyl, and 2-(ethoxy)ethyl.
The term "alkylene" as used herein and in the moieties of e.g.
Figure imgf000020_0001
C1-C4-
Figure imgf000020_0002
Ci-C4-alkylene- Y2-C(=Y1)RC, Ci-C4-alkylene-NRaRb, Ci-C4-alkylene-ORc, and Ci-C4-alkylene-SRc refers to a straight-chain or branched alkylene group having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, more preferably from 1 to 3 carbon atoms. Preferably, said alkenylene group connects a substituent, such as C(=Y1)RC, C(=Y1)ORc, C(=Y1)SRC, C(=Y1)NRaNRb, Y2-C(=Y1)RC, NRaRb, ORc,SRc, with the remainder of the molecule.
The term "alkenyl" as used herein denotes in each case an at least singly unsaturated hydrocarbon radical, i.e. a hydrocarbon radical having at least one carbon-carbon double bond, having usually 2 to 10, frequently 2 to 6, preferably 2 to 4 carbon atoms, e.g. vinyl, allyl (2-propen- 1 -yl), 1 -propen-1 -yl, 2-propen-2-yl, methallyl (2-methylprop-2-en-1 -yl), 2-buten-1 -yl, 3-buten-1 - yl, 2-penten-1 -yl, 3-penten-1 -yl, 4-penten-1 -yl, 1 -methylbut-2-en-1 -yl, 2-ethylprop-2-en-1 -yl and the like.
The term "haloalkenyl" as used herein refers to an alkenyl group as defined above, wherein the hydrogen atoms are partially or totally replaced with halogen atoms.
The term "alkenylene" as used herein and in the moieties of e.g. C2-C4-alkenylene-C(=Y1)Rc, C2-C4-alkenylene-C(=Y1)ORc, C2-C4-alkenylene-C(=Y1)SRc, C2-C4-alkenylene-C(=Y1)NRaNRb, C2-C4-alkenylene-Y2-C(=Y1)Rc, C2-C4-alkenylene-NRaRb, C2-C4-alkenylene-ORc, and C2-C4- alkenylene-SRc refers to a straight-chain or branched alkenylene group, which is at least singly unsaturated, and has usually from 2 to 10 carbon atoms, frequently from 2 to 6 carbon atoms, preferably 2 to 4 carbon atoms, more preferably from 2 to 3 carbon atoms. Preferably, said alkenylene group connects a substituent, such as C(=Y1)RC, C(=Y1)ORc, C(=Y1)SRC,
C(=Y1)NRaNRb, Y2-C(=Y1)RC, N RaRb, ORc,SRc, with the remainder of the molecule. The term "alkynyl" as used herein denotes in each case a hydrocarbon radical having at least one carbon-carbon triple bond and having usually 2 to 10, frequently 2 to 6, preferably 2 to 4 carbon atoms, e.g. ethynyl, propargyl (2-propyn-1 -yl), 1 -propyn-1 -yl, 1 -methylprop-2-yn-1 -yl), 2- butyn-1 -yl, 3-butyn-1 -yl, 1 -pentyn-1 -yl, 3-pentyn-1 -yl, 4-pentyn-1 -yl, 1 -methylbut-2-yn-1 -yl, 1 - ethylprop-2-yn-1 -yl and the like.
The term "haloalkynyl" as used herein refers to an alkynyl group as defined above, wherein the hydrogen atoms are partially or totally replaced with halogen atoms.
The term "alkynylalkyl" as used herein refers to alkyl usually comprising 1 to 10, frequently 1 to 4, preferably 1 to 2 carbon atoms, wherein 1 carbon atom carries an alkynyl radical usually comprising 2 to 4, preferably 2 or 3 carbon atoms as defined above.
The term "alkynylhydroxyalkyi" as used herein refers to an hydroxyalkyi as defined above usual- ly comprising 1 to 10, frequently 1 to 4, preferably 1 to 2 carbon atoms, wherein 1 carbon atom carries an alkynyl radical usually comprising 2 to 4, preferably 2 or 3 carbon atoms as defined above. An exemplary alkynylhydroxyalkyl is ethynylhydroxym ethyl. The term "alkynyloxy" as used herein denotes in each case an alkynyl group which is bound to the remainder of the molecule via an oxygen atom and has usually from 2 to 6 carbon atoms, frequently from 2 to 4 carbon atoms, preferably 2 to 3 carbon atoms.
The term "cycloalkyl" as used herein and in the cycloalkyl moieties of cycloalkoxy and cycloal- kylmethyl denotes in each case a monocyclic cycloaliphatic radical having usually from 3 to 10 or from 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohep- tyl, cyclooctyl, cyclononyl and cyclodecyl or cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
The term "cycloalkylalkyl" refers to a cycloalkyl group as defined above which is bound via an alkyl group, such as a Ci-Cs-alkyl group or a Ci-C4-alkyl group, in particular a methyl group (= cycloalkylmethyl), to the remainder of the molecule.
The term "cycloalkenyl" as used herein denotes in each case a monocyclic singly unsaturated non-aromatic radical having usually from 5 to 10 or from 3 to 8 carbon atoms, including e.g. cy- cloheptenyl or cyclooctenyl.
The term "heterocyclyl" or "heterocycle" includes in general 3- to 14-membered, preferably 3- to 10-membered, more preferably 5-, or 6-membered non-aromatic radicals with at least one het- eroatom. The term "heterocyclyl" or "heterocycle" refers to monocyclic, bicyclic or tricyclic het- erocyclic non-aromatic radicals. The term "heterocyclyl" or "heterocycle" also includes bicyclic or tricyclic radicals, which comprise a non-aromatic ring and a fused aryl or hetaryl ring. Particularly preferred are 5- and 6-membered monocyclic heterocyclic non-aromatic radicals. The heterocyclic radicals usually comprise 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3 heteroatoms selected from N, O and S as ring members, where S-atoms as ring members may be present as S, SO or SO2. Examples of 5- or 6-membered heterocyclic radicals comprise saturated or unsaturated, non-aromatic heterocyclic rings, such as oxiranyl, oxetanyl, thietanyl, thietanyl-S-oxid (S- oxothietanyl), thietanyl-S-dioxid (S-dioxothiethanyl), pyrrolidinyl, pyrrolinyl, pyrazolinyl, tetrahy- drofuranyl, dihydrofuranyl, 1 ,3-dioxolanyl, thiolanyl, S-oxothiolanyl, S-dioxothiolanyl, dihy- drothienyl, S-oxodihydrothienyl, S-dioxodihydrothienyl, oxazolidinyl, oxazolinyl, thiazolinyl, ox- athiolanyl, piperidinyl, piperazinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, 1 ,3- and 1 ,4- dioxanyl, thiopyranyl, S.oxothiopyranyl, S-dioxothiopyranyl, dihydrothiopyranyl, S- oxodihydrothiopyranyl, S-dioxodihydrothiopyranyl, tetrahydrothiopyranyl, S-oxotetra- hydrothiopyranyl, S-dioxotetrahydrothiopyranyl, morpholinyl, thiomorpholinyl, S-oxothiomorpho- linyl, S-dioxothiomorpholinyl, thiazinyl and the like. Examples for heterocyclic rings also com- prising 1 or 2 carbonyl groups as ring members comprise pyrrolidin-2-onyl, pyrrolidin-2,5-dionyl, imidazolidin-2-onyl, oxazolidin-2-onyl, thiazolidin-2-onyl and the like. Particularly preferred are also bicyclic 8- to 10-membered heterocyclic radicals comprising as ring members 1 , 2, 3, 4 or 5, preferably 1 , 2 or 3 heteroatoms selected from N, O and S members, where S-atoms as ring members may be present as S, SO or SO2. Preferably, said bicyclic 8- to 10-membered heterocyclic radicals comprise a 5- or 6-membered non-aromatic ring as defined above, which is fused to an aryl or hetaryl ring or to another heterocyclic ring. These fused heterocyclyl radicals may be bound to the remainder of the molecule via any ring atom of the 5- or 6-membered ring or the fused ring.
The term "heterocyclylalkyl" refers to heterocyclyl as defined above, which is bound via a C1-C5- alkyl group or a Ci-C4-alkyl group, in particular a methyl group (= heterocyclylmethyl), to the remainder of the molecule.
The term "carbocyclyl" or "carbocycle" includes in general 3- to 14-membered, preferably 3- to 10-membered, more preferably 5- or 6-membered non-aromatic radicals. The term "carbocyclyl" or "carbocycle" may refer to monocyclic, bicyclic or tricyclic carbocyclic non-aromatic radicals. Preferred carbocycles are cycloalkyl and cycloalkenyl groups having from 3 to 10, preferably 5 or 6 carbon atoms.
Particularly preferred are also bicyclic 8- to 10-membered carbocyclic radicals, wherein a 5- or 6-membered non-aromatic ring is fused to an aryl ring or another carbocyclic ring. These fused carbocyclyl radicals may be bonded to the remainder of the molecule via any ring atom of the 5- or 6-membered ring or the fused ring.
The term "carbocyclylalkyl" refers to carbocyclyl as defined above which is bound via a C1-C5- alkyl group or a Ci-C4-alkyl group, in particular a methyl group (= carbocyclylmethyl), to the remainder of the molecule. The term "hetaryl" includes monocyclic 5- or 6-membered heteroaromatic radicals comprising as ring members 1 , 2, 3 or 4 heteroatoms selected from N, O and S. Examples of 5- or
6-membered heteroaromatic radicals include pyridyl, i.e. 2-, 3-, or 4-pyridyl, pyrimidinyl, i.e. 2-, 4- or 5-pyrimidinyl, pyrazinyl, pyridazinyl, i.e. 3- or 4-pyridazinyl, thienyl, i.e. 2- or 3-thienyl, furyl, i.e. 2-or 3-furyl, pyrrolyl, i.e. 2- or 3-pyrrolyl, oxazolyl, i.e. 2-, 3- or 5-oxazolyl, isoxazolyl, i.e. 3-, 4- or 5-isoxazolyl, thiazolyl, i.e. 2-, 3- or 5-thiazolyl, isothiazolyl, i.e. 3-, 4- or
5-isothiazolyl, pyrazolyl, i.e. 1 -, 3-, 4- or 5-pyrazolyl, i.e. 1 -, 2-, 4- or 5-imidazolyl, oxadiazolyl, e.g. 2- or 5-[1 ,3,4]oxadiazolyl, 4- or 5-(1 ,2,3-oxadiazol)yl, 3- or 5-(1 ,2,4-oxadiazol)yl, 2- or 5-(1 ,3,4-thiadiazol)yl, thiadiazolyl, e.g. 2- or 5-(1 ,3,4-thiadiazol)yl, 4- or 5-(1 ,2,3-thiadiazol)yl, 3- or 5-(1 ,2,4-thiadiazol)yl, triazolyl, e.g. 1 H-, 2H- or 3H-1 ,2,3-triazol-4-yl, 2H-triazol-3-yl, 1 H-, 2H-, or 4H-1 ,2,4-triazolyl and tetrazolyl, i.e. 1 H- or 2H-tetrazolyl. The term "hetaryl" also includes bicyclic 8 to 13-membered, preferably 8- to 10 membered heteroaromatic radicals comprising as ring members 1 , 2 or 3 heteroatoms selected from N, O and S, wherein a 5- or 6-membered heteroaromatic ring is fused to a phenyl ring or to a 5- or 6-membered heteroaromatic radical. Examples of a 5- or 6-membered heteroaromatic ring fused to a phenyl ring or to a 5- or 6- membered heteroaromatic radical include benzofuranyl, benzothienyl, indolyl, indazolyl, ben- zimidazolyl, benzoxathiazolyl, benzoxadiazolyl, benzothiadiazolyl, benzoxazinyl, chinolinyl, iso- chinolinyl, purinyl, 1 ,8-naphthyridyl, pteridyl, pyrido[3,2-d]pyrimidyl or pyridoimidazolyl and the like. These fused hetaryl radicals may be bonded to the remainder of the molecule via any ring atom of 5- or 6-membered heteroaromatic ring or via a carbon atom of the fused phenyl moiety.
The term "hetarylalkyi" refers to hetaryl as defined above which is bound via a Ci-Cs-alkyl group or a Ci-C4-alkyl group, in particular a methyl group (= hetarylmethyl), to the remainder of the molecule.
The term "heteraryloxy" refers to heteraryl as defined above, which is bound via an oxygen atom to the remainder of the molecule.
The term "aryl" includes monocyclic, bicyclic or tricyclic aromatic radicals comprising 6 to 14 carbon atoms, preferably 6 or 10 carbon atoms, more preferably 6 carbon atoms. Exemplary aryl radicals include anthracenyl, naphthalenyl and phenyl. A preferred aryl radical is phenyl. The term "arylalkyl" refers to aryl as defined above which is bound via a Ci-Cs-alkyl group or a Ci-C4-alkyl group, in particular a methyl group (=arylmethyl), to the remainder of the molecule. A preferred arylalkyl group is phenylmethyl, i.e. benzyl.
The term "aryloxy" refers to aryl as defined above, which is bound via an oxygen atom to the remainder of the molecule. A preferred aryloxy group is e.g. benzyloxy.
As has been set out above, the present invention concerns in one aspect the use of a nitrification inhibitor for reducing nitrification, wherein said nitrification inhibitor is a compound of formula I
Figure imgf000023_0001
or a stereoisomer, salt, tautomer or N-oxide thereof, wherein
A is aryl or hetaryl, wherein the aromatic ring may in each case be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from RA;
R1 and R2 are independently of each other selected from H and Ci-C2-alkyl; and
R3 is H, Ci-C4-haloalkyl, Ci-C4-hydroxyalkyl, ethynylhydroxym ethyl, phenylhydroxymethyl, or aryl, wherein the aromatic ring may be unsubstituted or may be partially or fully substi- tuted by substituents, which are independently of each other selected from RB; and wherein is
(i) halogen, CN, NRaRb, ORc, SRC, C(=Y1)RC, C(=Y1)ORc, C(=Y1)SRC, C(=Y1)NRaRb, Y2C(=Y1)RC, Y2C(=Y1)ORc, Y2C(=Y1)SRC, Y2C(=Y1)NRaRb, Y3Y2C(=Y1)RC,
Figure imgf000024_0001
S(=0)2Y2C(=Y1)NRaRb, N02, NON-CN, Ci-C6-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, C1-C4- haloalkyl, Ci-C4-cyanoalkyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, C2-C4-alkynyl-Ci-C2- hydroxyalkyl, C2-C4-alkynyloxy;
Figure imgf000024_0002
C2-C4-alkenylene-C(=Y1)ORc,
Figure imgf000024_0003
C2-C4-alkenylene-C(=Y1)SRc,
Figure imgf000024_0004
Ci-C4-alkylene-Y2- C(=Y1)RC, C2-C4-alkenylene-Y2-C(=Y1)Rc, Ci-C4-alkylene-NRaRb, C2-C4-alkenylene- NRaRb, Ci-C4-alkylene-ORc, C2-C4-alkenylene-ORc, Ci-C4-alkylene-SRc, C2-C4- alkenylene-SRc, wherein the Ci-C4-alkylene or C2-C4-alkenylene chain may in each case be unsubstituted or may be partially or fully substituted by ORa, CN, halogen or phenyl;
(iii) aryl, aryl-Ci-C2-alkyl, hetaryl or hetaryl-Ci-C2-alkyl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from Rh;
(iv) a 3- to 14-membered saturated or unsaturated carbocycle or heterocycle, which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from NR1b, O, and S, wherein S may be oxidized and/or wherein the carbocycle or heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R1b is H, C1-C4- alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6-cycloalkylmethyl, or ORa; or
(v) L-B, wherein
L is -CH2-, -CH=CH-, -C≡C-, -C(=0)- or -CH=, and
B is aryl or hetaryl, wherein the aromatic ring of the ary or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from Rh;
or
a 3- to 14-membered saturated or unsaturated carbocycle or heterocycle, which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from N R1b, O, and S, wherein S may be oxidized and/or wherein the carbocycle or heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R1b is H, Ci-C4-alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6-cycloalkylmethyl, or OR9; or
(vi) two substituents RA together represent a carbocyclic or heterocyclic ring, which is fused to A and may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from NR1c, O, and S, wherein S may be oxidized and/or wherein the carbocycle or heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R1c is H, d-C4-alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6- cycloalkylmethyl, C3-C6-heterocyclyl, C3-C6-heterocyclylmethyl or OR9; and wherein
RB is NH-C(=0)-(Ci-C4-alkyl), NH-C(=0)-(C2-C4-alkenyl),
Figure imgf000025_0001
alkyl), NH-C(=0)-(C3-C6-cycloalkyl), NH-S(=0)2-(Ci-C4-alkyl), or N02; and wherein
Y2 and Y3 are independently of each other selected from O, S and NR1a, wherein R1a is each case independently H, Ci-C4-alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-( cycloalkylmethyl, ORa, SRa or NRmRn;
Ra and Rb are independently of each other selected from
(i) H, NRRk, OR, SR, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, C(=Y1)R, C(=Y1)OR, C(=Y1)SR, C(=Y1)NRRk, C(=Y1)C(=Y2)R, S(=0)2Rf;
(ii) aryl or hetaryl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from Rh; or
Ra and Rb together with the nitrogen atom to which they are bound form
(iii) a hetaryl group which may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from Rh; or
(iv) a 3- to 10-membered, saturated or unsaturated heterocycle, which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from NR1b, O, and S, wherein S may be oxidized and/or wherein the heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R1b is H , Ci-C4-alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6-cycloalkylmethyl, or ORa; is
(i) H, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C(=0)OR, C(=0)SR, C(=0)NRRk;
(ii)
Figure imgf000025_0002
wherein the Ci-C4-alkylene chain may in each case be unsubstituted or may be partially or fully substituted by ORa, CN, halogen, or phenyl;
(iii) aryl, aryl-Ci-C2-alkyl, hetaryl, or hetaryl-Ci-C2-alkyl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from Rh; or
(iv) a 3- to 10-membered saturated or unsaturated carbocycle or heterocycle, which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from NR1b, O, and S, wherein S may be oxidized and/or wherein the carbocycle or heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R1b is H, C1-C4- alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6-cycloalkylmethyl, or ORa;
Rd and Re are independently selected from Ci-C4-alkyl, Ci-C4-haloalkyl, NRRk, OR, SR, CN, C(=Y1)R, C(=Y1)OR, C(=Y1)SR, or C(=Y1)NRRk;
Rf is Ci-C4-alkyl, Ci-C4-haloalkyl, NRRk, OR, SR, aryl or hetaryl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from Rh;
R9 is H or Ci-C4-alkyl;
Rh is halogen, CN, N02, NRRk, OR, SR, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4- haloalkyl, Ci-C4-alkoxy, C2-C4-alkynyloxy, C(=Y1)R, C(=Y1)OR, C(=Y1)SR, C(=Y1)NRRk, aryl, aryloxy, hetaryl and hetaryloxy;
R is
(i) halogen, CN, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-haloalkyl, C2-C4- haloalkenyl;
(ii) =NR1d, wherein R1d is H, Ci-C4-alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6- cycloalkylmethyl, or OR9;
(iii) =0, =S, N RRk, OR, SR, C(=Y1)R, C(=Y1)OR, C(=Y1)SR, C(=Y1)NRRk;
(iv) aryl, aryl-Ci-C2-alkyl, hetaryl, or hetaryl-Ci-C2-alkyl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from halogen, CN, C1-C4- alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, C2-C4-alkynyloxy, ORa, and SRa; or
(v) C3-C6-cycloalkyl, or 3- to 6-membered heterocyclyl, wherein the cycloalkyl ring or the heterocyclyl ring may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from halogen, CN, Ci-C4-alkyl,
Figure imgf000026_0001
R and Rk are independently selected from H, ORa, SRa, C(=Y1)Ra, C(=Y1)ORa, C(=Y1)SRa, C(=Y1)NRmRn, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-haloalkyl, aryl or hetaryl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently selected from halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, C2-C4-alkynyloxy, ORa, and SRa;
R is H, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-haloalkyl, C(=Y1)Ra, C(=Y1)ORa,
C(=Y1)NRmRn, aryl or hetaryl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently selected from halogen, CN , Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, C2-C4-alkynyloxy, ORa, and SRa; and Rm and Rn are independently selected from H and Ci-C4-alkyl.
In a preferred embodiment of said compound of formula I, A is phenyl or a 5- or 6-membered hetaryl, wherein the aromatic ring may in each case be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from RA. These compounds correspond to compounds of formula 1.1 , wherein A' represents phenyl or a 5- or 6- membered hetaryl, wherein the aromatic ring may in each case be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from RA.
Figure imgf000027_0001
In a further preferred embodiment of said compound of formula I , R1 and R2 both represent hydrogen. These compounds corresp ds of formula I.A.
Figure imgf000027_0002
I.A
In another preferred embodiment of said compound of formula I, R3 is hydrogen, Ci-C4-haloalkyl or ethynylhydroxymethyl. It is even more preferred that R3 is hydrogen. These compounds correspond to compounds of formula I.X.
Figure imgf000027_0003
I.X
In a particularly preferred embodiment of said compound of formula I, A is A', i.e. phenyl or a 5- or 6-membered hetaryl, wherein the aromatic ring may in each case be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from RA, and R1 and R2 are both hydrogen. These compounds correspond to compounds of formula I.1.A.
Figure imgf000027_0004
In another more preferred embodiment of said compound of formula I, A is A', i.e. phenyl or a 5- or 6-membered hetaryl, wherein the aromatic ring may in each case be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from
RA, and R3 is hydrogen. These comp mpounds of formula I.1 .X.
Figure imgf000027_0005
In another more preferred embodiment of said compound of formula I, R1 and R2 are both hy- drogen, and R3 is hydrogen. nds correspond to compounds of formula I.A.X.
Figure imgf000027_0006
I.A.X In the most preferred embodiment of said compound of formula I, A is A', i.e. phenyl or a 5- or 6-membered hetaryl, wherein the aromatic ring may in each case be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from RA, R1 and R2 are both hydrogen, and R3 is hydrogen.
Figure imgf000028_0001
Further preferred embodiments of said compound of formula I relate to the substituents RA, with which A may be partially or fully substituted.
In a preferred embodiment of the compound of formula I, RA, if present, is
(i) halogen, CN , N RaRb, ORc, C(=Y1)RC, C(=Y1)ORc, C(=Y1)SRC, C(=Y1)N RaRb, Y2C(=Y1)RC, Y2C(=Y1)N RaRb, N RaN =C(Rd)(Re), S(=0)2Rf, N02, Ci-C6-alkyl, C2-C6- C1-C4- haloalkyl, Ci-C4-alkoxy, C2-C4-alkynyl-Ci-C2-hydroxyalkyl, C2-C4-alkynyloxy;
(ii) C2-C4-alkenylene-C(=Y1)Rc, C2-C4-alkenylene-Y2-C(=Y1)Rc, wherein the C1-C4- alkylene or C2-C4-alkenylene chain may in each case be unsubstituted or may be partially or fully substituted by CN or halogen;
(iii) aryl, wherein the aromatic ring of the aryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from Rh; or
(iv) a 3- to 14-membered saturated or unsaturated heterocycle, which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from N R1b, O , and S, wherein S may be oxidized and/or wherein the heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R1b is H , Ci-C4-alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6-cycloalkylmethyl, or ORa.
In a particularly preferred embodiment of the present invention, the compound of formula I, is a compound of formula 1.1 , I.A, I.X, 1.1. A, 1.1.X, I.A.X or I.1.A.X, wherein RA, if present, is
(i) halogen, CN , N RaRb, ORc, C(=Y1)RC, C(=Y1)ORc, C(=Y1)SRC, C(=Y1)N RaRb, Y2C(=Y1)RC, Y2C(=Y1)N RaRb, N RaN =C(Rd)(Re), S(=0)2Rf, N02, Ci-C6-alkyl, C2-C6- C1-C4- haloalkyl, Ci-C4-alkoxy, C2-C4-alkynyl-Ci-C2-hydroxyalkyl, C2-C4-alkynyloxy;
(ii) C2-C4-alkenylene-C(=Y1)Rc, C2-C4-alkenylene-Y2-C(=Y1)Rc, wherein the C1-C4- alkylene or C2-C4-alkenylene chain may in each case be unsubstituted or may be partially or fully substituted by CN or halogen;
(iii) aryl, wherein the aromatic ring of the aryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from Rh; or
(iv) a 3- to 14-membered saturated or unsaturated heterocycle, which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from N R1b, O , and S, wherein S may be oxidized and/or wherein the heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R1b is H , Ci-C4-alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6-cycloalkylmethyl, or ORa. If RA is present in the compounds of formula I or a compound of any one of formulae 1.1 , I.A, I.X, 1.1 .A, 1.1 .X, I.A.X or I.1.A.X, and preferably if RA is selected as indicated above, the following substituent definitions are particularly preferred according to the present invention.
Preferably, Y1, Y2 and Y3 are independently of each other selected from O, S and N R1a, wherein preferably R1a is in each case independently H, d-C4-alkyl, ORa, or NRmRn.
Preferably, Ra and Rb are independently of each other selected from
(i) H, NRRk, Ci-C4-alkyl, Ci-C4-hydroxyalkyl, C(=Y1)R; or
Ra and Rb together with the nitrogen atom to which they are bound form
(iv) a 3- to 10-membered, saturated or unsaturated heterocycle, which may contain 1 ,
2, or 3 heteroatoms which, independently of each other, are selected from NR1b, O, and S, wherein S may be oxidized and/or wherein the heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R1b is preferably H , Ci-C4-alkyl, or ORa.
Preferably, Rc is
(i) H, Ci-C4-alkyl; or
(iv) a 3- to 10-membered saturated or unsaturated carbocycle or heterocycle, which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from NR1b, O, and S, wherein S may be oxidized and/or wherein the carbocycle or heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R1b is preferably H, Ci-C4-alkyl, or ORa. Preferably, Rd and Re are independently selected from N Rk and C(=Y1)OR;
Preferably, Rf is Ci-C4-alkyl.
Preferably, Ra is H.
Preferably, Rh is halogen or Ci-C4-alkoxy.
Preferably, R is
(i) Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-haloalkenyl; or
(iii) =0.
Preferably, R and Rk are both H . Preferably, R1 is H.
Preferably, Rm and Rn are both H .
Preferred compounds of formula I of the present invention are listed in the following Table 1 :
Figure imgf000030_0001
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Figure imgf000039_0001
Figure imgf000040_0001
Figure imgf000041_0001
In a central aspect the present invention thus relates to the use of a combination of a nitrification inhibitor or (T) and a fungicide as defined herein above, or of a composition comprising said combination of a nitrification inhibitor or (T) and a fungicide as defined herein for increasing the health of a plant. The nitrification inhibitor or derivatives or salts thereof as defined herein above in combination with a fungicide, in particular compounds of formula I and/or salts or suitable derivatives thereof in combination with a fungicide, as well as compositions comprising said nitrification inhibitor or (T) and a fungicide as defined herein may be used for increasing the health of a plant.
The use may be based on an application of the combination of the nitrification inhibitor or (T) and a fungicide, or the composition as defined herein to a plant growing on soil and/or the locus where the plant is growing or is intended to grow, or the application of the combination of the nitrification inhibitor or (T) and a fungicide, or the composition as defined herein to soil where a plant is growing or is intended to grow or to soil substituents. In specific embodiments, the com- bination of the nitrification inhibitor or (T) and a fungicide may be used in the absence of plants, e.g. as preparatory activity for subsequent agricultural activity.
The use may further include the application of a combination of a fungicide and (T) or the nitrification inhibitor or derivatives or salts thereof as defined herein above, in particular compounds of formula I and/or salts or suitable derivatives thereof, as well as compositions comprising said combination of a fungicide and (T) or the nitrification inhibitor, or agrochemical mixtures comprising (T) or said nitrification inhibitor as defined herein above to environments, areas or zones, where nitrification takes place or is assumed or expected to take place. Such environments, areas or zones may, in specific embodiments, not comprise plants or soil, but be planned for subsequent growth of plants. Examples of such environments are laboratory envirnonments or green houses or similar indoor facilities. The term "plant health" as used herein is intended to mean a condition of the plant which is determined by several aspects alone or in combination with each other. One indicator (indicator 1 ) for the condition of the plant is the crop yield. "Crop" and "fruit" are to be understood as any plant product which is further utilized after harvesting, e.g. fruits in the proper sense, vegeta- bles, nuts, grains, seeds, wood (e.g. in the case of silviculture plants), flowers (e.g. in the case of gardening plants, ornamentals) etc., that is anything of economic value that is produced by the plant. Another indicator (indicator 2) for the condition of the plant is the plant vigor. The plant vigor becomes manifest in several aspects, too, some of which are visual appearance, e.g. leaf color, fruit color and aspect, amount of dead basal leaves and/or extent of leaf blades, plant weight, plant height, extent of plant verse (lodging), number, strong ness and productivity of tillers, panicles' length, extent of root system, strongness of roots, extent of nodulation, in particular of rhizobial nodulation, point of time of germination, emergence, flowering, grain maturity and/or senescence, protein content, sugar content and the like. Another indicator (indicator 3) for an increase of a plant's health is the reduction of biotic or abiotic stress factors.
The three above mentioned indicators for the health condition of a plant may be interdependent and may result from each other. For example, a reduction of biotic stress may lead to a better plant vigor, e.g. to better and bigger crops, and thus to an increased yield. Biotic stress, especially over longer terms, can have harmful effects on plants. The term "biotic stress" as used in the context of the present invention refers in particular to stress caused by living organisms, such as fungi, especially phythopathogenic fungi. As a result, the quantity and the quality of the stressed plants, their crops and fruits decrease. As far as quality is concerned, reproductive development is usually severely affected with consequences on the crops which are important for fruits or seeds. Growth may be slowed by the stresses; polysaccharide synthesis, both structural and storage, may be reduced or modified: these effects may lead to a decrease in biomass and to changes in the nutritional value of the product. A reduction of biotic stress factors may, for example, be due to a fungicidal effect to fungi, especially phythopathogenic fungi of a fungicide as defined herein.
Abiotic stress includes drought, cold, increased UV, increased heat, or other changes in the environment of the plant, that leads to sub-optimal growth conditions. A reduction of abiotic stress factors may, for example, be due to a reduction of nitrification and a corresponding improvement of uptake of nitrogen nutrients.
The term "increased yield" of a plant as used herein means that the yield of a product of the respective plant is increased by a measurable amount over the yield of the same product of the plant produced under the same conditions, but without the application of the composition of the invention. According to the present invention, it is preferred that the yield be increased by at least 0,5 %, more preferred at least 1 %, even more preferred at least 2 %, still more preferred at least 4 %. An increased yield may, for example, be due to a reduction of nitrification and a corresponding improvement of uptake of nitrogen nutrients, as well as a fungicidal effect to fungi, especially phythopathogenic fungi of a fungicide as defined herein. The term "improved plant vigor" as used herein means that certain crop characteristics are increased or improved by a measurable or noticeable amount over the same factor of the plant produced under the same conditions, but without the application of the composition of the pre- sent invention. Improved plant vigor can be characterized, among others, by following improved properties of a plant:
(a) improved vitality of the plant,
(b) improved quality of the plant and/or of the plant products, e.g.
(b) enhanced protein content,
(c) improved visual appearance,
(d) delay of senescence,
(e) enhanced root growth and/or more developed root system (e.g. determined by the dry mass of the root),
(f) enhanced nodulation, in particular rhizobial nodulation,
(g) longer panicles,
(h) bigger leaf blade,
(i) less dead basal leaves,
(j) increased chlorophyll content
(k) prolonged photosynthetically active period
The improvement of the plant vigor according to the present invention particularly means that the improvement of anyone or several or all of the above mentioned plant characteristics are improved. It further means that if not all of the above characteristics are improved, those which are not improved are not worsened as compared to plants which were not treated according to the invention or are at least not worsened to such an extent that the negative effect exceeds the positive effect of the improved characteristic (i.e. there is always an overall positive effect which preferably results in an improved crop yield). An improved plant vigor may, for example, be due to a reduction of nitrification and a corresponding improvement of uptake of nitrogen nutrients, as well as a fungicidal effect to fungi, especially phythopathogenic fungi of a fungicide as defined herein.
It is particularly preferred that said increase of the health of a plant is reflected by an increase in growth of root and shoot and/or an overall increase in productivity and/or a faster and more efficient development of the plant. The term "reducing nitrification" or "reduction of nitrification" as used herein refers to a slowing down or stopping of nitrification processes, e.g. by retarding or eliminating the natural transformation of ammonium into nitrate. Such reduction may be a complete or partial elimination of nitrification at the plant or locus where the inhibitor or composition comprising said inhibitor is applied. For example, a partial elimination may result in a residual nitrification on or in the plant, or in or on the soil or soil substituents where a plant grows or is intended to grow of about 90% to 1 %, e.g. 90%, 85%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10% or less than 10%, e.g. 5% or less than 5% in comparison to a control situation where the nitrification inhibitor is not used. In certain embodiments, a partial elimination may result in a residual nitrification on or in the plant or in or on the soil or soil substituents where a plant grows or is intended to grow of below 1 %, e.g. at 0.5%, 0.1 % or less in comparison to a control situation where the nitrification inhibitor is not used. A "fungicide" as mentioned herein above may be any fungicide known to the skilled person. A fungicide typically shows an outstanding effectiveness against biotic stresses caused by a broad spectrum of phytopathogenic fungi, including soil-borne fungi, which derive especially from the classes of the Plasmodiophoromycetes, Peronosporomycetes (syn. Oomycetes), Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes and Deuteromycetes (syn. Fungi imperfecti). Some are systemically effective and they can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Moreover, they are suitable for controlling harmful fungi, which inter alia occur in wood or roots of plants. The fungicides and compositions comprising them according to the invention are particularly important in the control of a multitude of phytopathogenic fungi on various cultivated plants, such as cereals, e. g.
wheat, rye, barley, triticale, oats or rice; beet, e. g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e. g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rape, sugar cane or oil palm; corn; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; sweet leaf (also called Stevia); natural rubber plants or ornamental and forestry plants, such as flowers, shrubs, broad-leaved trees or evergreens, e. g. conifers; and on the plant propagation material, such as seeds, and the crop material of these plants. Fungicides and compositions comprising them, respectively may preferably be used for controlling a multitude of fungi on field crops, such as potatoes sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybeans, rape, legumes, sunflowers, coffee or sugar cane; fruits; vines; ornamentals; or vegetables, such as cucumbers, tomatoes, beans or squashes.
Fungicides and compositions comprising them according to the present invention are particularly suitable for reducing biotic stresses caused by one or more of the following plant diseases: Albugo spp. (white rust) on ornamentals, vegetables (e. g. A Candida) and sunflowers (e. g. A. tragopogonis); Alternaria spp. (Alternaria leaf spot) on vegetables, rape (A. brassicola or brassi- cae), sugar beets (A tenuis), fruits, rice, soybeans, potatoes (e. g. A. solani or A alternata), tomatoes (e. g. A solani or A alternata) and wheat; Aphanomyces spp. on sugar beets and vegetables; Ascochyta spp. on cereals and vegetables, e. g. A. tritici (anthracnose) on wheat and A hordei on barley; Bipolaris and Drechslera spp. (teleomorph: Cochliobolus spp.), e. g. Southern leaf blight (D. maydis) or Northern leaf blight (B. zeicola) on corn, e. g. spot blotch (B. sorokiniana) on cereals and e. g. B. oryzae on rice and turfs; Blumeria (formerly Erysiphe) graminis (powdery mildew) on cereals (e. g. on wheat or barley); Botrytis cinerea (teleomorph: Botryotinia fuckeliana: grey mold) on fruits and berries (e. g. strawberries), vegetables (e. g. lettuce, carrots, celery and cabbages), rape, flowers, vines, forestry plants and wheat; Bremia lactucae (downy mildew) on lettuce; Ceratocystis (syn. Ophiostoma) spp. (rot or wilt) on broad- leaved trees and evergreens, e. g. C. ulmi (Dutch elm disease) on elms; Cercospora spp. (Cer- cospora leaf spots) on corn (e. g. Gray leaf spot: C. zeae-maydis), rice, sugar beets (e. g. C. beticola), sugar cane, vegetables, coffee, soybeans (e. g. C. sojina or C. kikuchii) and rice; Cladosporium spp. on tomatoes (e. g. C. fulvum: leaf mold) and cereals, e. g. C. herbarum (black ear) on wheat; Claviceps purpurea (ergot) on cereals; Cochliobolus (anamorph: Helmin- thosporium of Bipolaris) spp. (leaf spots) on corn (C. carbonum), cereals (e. g. C. sativus, ana- morph: B. sorokiniana) and rice (e. g. C. miyabeanus, anamorph: H. oryzae); Colletotrichum
(teleomorph: Glomerella) spp. (anthracnose) on cotton (e. g. C. gossypii), corn (e. g. C. gramini- cola: Anthracnose stalk rot), soft fruits, potatoes (e. g. C. coccodes: black dot), beans (e. g. C. lindemuthianum) and soybeans (e. g. C. truncatum or C. gloeosporioides); Corticium spp., e. g. C. sasakii (sheath blight) on rice; Corynespora cassiicola (leaf spots) on soybeans and orna- mentals; Cycloconium spp., e. g. C. oleaginum on olive trees; Cylindrocarpon spp. (e. g. fruit tree canker or young vine decline, teleomorph: Nectria or Neonectria spp.) on fruit trees, vines (e. g. C. liriodendri, teleomorph: Neonectria liriodendri: Black Foot Disease) and ornamentals; Dematophora (teleomorph: Rosellinia) necatrix (root and stem rot) on soybeans; Diaporthe spp., e. g. D. phaseolorum (damping off) on soybeans; Drechslera (syn. Helminthosporium, teleo- morph: Pyrenophora) spp. on corn, cereals, such as barley (e. g. D. teres, net blotch) and wheat (e. g. D. tritici-repentis: tan spot), rice and turf; Esca (dieback, apoplexy) on vines, caused by Formitiporia (syn. Phellinus) punctata, F. mediterranea, Phaeomoniella chlamydospora (earlier Phaeoacremonium chlamydosporum), Phaeoacremonium aleophilum and/or Botryosphaeria obtusa; Elsinoe spp. on pome fruits (£. pyri), soft fruits (£. veneta: anthracnose) and vines (£. ampelina: anthracnose); Entyloma oryzae (leaf smut) on rice; Epicoccum spp. (black mold) on wheat; Erysiphe spp. (powdery mildew) on sugar beets (£. betae), vegetables (e. g. £. pisi), such as cucurbits (e. g. £. cichoracearum), cabbages, rape (e. g. £. cruciferarum); Eutypa lata (Eutypa canker or dieback, anamorph: Cytosporina lata, syn. Libertella blepharis) on fruit trees, vines and ornamental woods; Exserohilum (syn. Helminthosporium) spp. on corn (e. g. £. turci- cum); Fusarium (teleomorph: Gibberella) spp. (wilt, root or stem rot) on various plants, such as F. graminearum or F. culmorum (root rot, scab or head blight) on cereals (e. g. wheat or barley), F. oxysporum on tomatoes, F. solani (f. sp. glycines now syn. F. virguliforme ) and F. tucumani- ae and F. brasiliense each causing sudden death syndrome on soybeans, and F. verticillioides on corn; Gaeumannomyces graminis (take-all) on cereals (e. g. wheat or barley) and corn; Gib- berella spp. on cereals (e. g. G. zeae) and rice (e. g. G. fujikuroi: Bakanae disease); Glomerella cingulata on vines, pome fruits and other plants and G. gossypii on cotton; Grainstaining complex on rice; Guignardia bidwellii (black rot) on vines; Gymnosporangium spp. on rosaceous plants and junipers, e. g. G. sabinae (rust) on pears; Helminthosporium spp. (syn. Drechslera, teleomorph: Cochliobolus) on corn, cereals and rice; Hemileia spp., e. g. H. vastatrix (coffee leaf rust) on coffee; Isariopsis clavispora (syn. Cladosporium vitis) on vines; Macrophomina phaseolina (syn. phaseoli) (root and stem rot) on soybeans and cotton; Microdochium (syn. Fusarium) nivale (pink snow mold) on cereals (e. g. wheat or barley); Microsphaera diffusa (powdery mildew) on soybeans; Monilinia spp., e. g. M. laxa, M. fructicola and M. fructigena (bloom and twig blight, brown rot) on stone fruits and other rosaceous plants; Mycosphaerella spp. on cereals, bananas, soft fruits and ground nuts, such as e. g. M. graminicola (anamorph: Septoria tritici, Septoria blotch) on wheat or M. fijiensis (black Sigatoka disease) on bananas; Peronospora spp. (downy mildew) on cabbage (e. g. P. brassicae), rape (e. g. P. parasitica), onions (e. g. P. destructor), tobacco (P. tabacina) and soybeans (e. g. P. manshurica);
Phakopsora pachyrhizi and P. meibomiae (soybean rust) on soybeans; Phialophora spp. e. g. on vines (e. g. P. tracheiphila and P. tetraspora) and soybeans (e. g. P. gregata: stem rot); Phoma lingam (root and stem rot) on rape and cabbage and P. betae (root rot, leaf spot and damping-off) on sugar beets; Phomopsis spp. on sunflowers, vines (e. g. P. viticola: can and leaf spot) and soybeans (e. g. stem rot: P. phaseoli, teleomorph: Diaporthe phaseolorum); Phy- soderma maydis (brown spots) on corn; Phytophthora spp. (wilt, root, leaf, fruit and stem root) on various plants, such as paprika and cucurbits (e. g. P. capsici), soybeans (e. g. P.
megasperma, syn. P. sojae), potatoes and tomatoes (e. g. P. infestans: late blight) and broad- leaved trees (e. g. P. ramorum: sudden oak death); Plasmodiophora brassicae (club root) on cabbage, rape, radish and other plants; Plasmopara spp., e. g. P. viticola (grapevine downy mildew) on vines and P. halstedii on sunflowers; Podosphaera spp. (powdery mildew) on rosaceous plants, hop, pome and soft fruits, e. g. P. leucotricha on apples; Polymyxa spp., e. g. on cereals, such as barley and wheat (P. graminis) and sugar beets (P. betae) and thereby transmitted viral diseases; Pseudocercosporella herpotrichoides (eyespot, teleomorph: Tapesia yal- lundae) on cereals, e. g. wheat or barley; Pseudoperonospora (downy mildew) on various plants, e. g. P. cubensis on cucurbits or P. humili on hop; Pseudopezicula tracheiphila (red fire disease or ,rotbrenner', anamorph: Phialophora) on vines; Puccinia spp. (rusts) on various plants, e. g. P. triticina (brown or leaf rust), P. striiformis (stripe or yellow rust), P. hordei (dwarf rust), P. graminis (stem or black rust) or P. recondita (brown or leaf rust) on cereals, such as e. g. wheat, barley or rye, P. kuehnii (orange rust) on sugar cane and P. asparagi on asparagus; Pyrenophora (anamorph: Drechslera) tritici-repentis (tan spot) on wheat or P. teres (net blotch) on barley; Pyricularia spp., e. g. P. oryzae (teleomorph: Magnaporthe grisea, rice blast) on rice and P. grisea on turf and cereals; Pythium spp. (damping-off) on turf, rice, corn, wheat, cotton, rape, sunflowers, soybeans, sugar beets, vegetables and various other plants (e. g. P. ultimum or P. aphanidermatum); Ramularia spp., e. g. R. collo-cygni (Ramularia leaf spots, Physiological leaf spots) on barley and R. beticola on sugar beets; Rhizoctonia spp. on cotton, rice, potatoes, turf, corn, rape, potatoes, sugar beets, vegetables and various other plants, e. g. R. solani (root and stem rot) on soybeans, R. solani (sheath blight) on rice or R. cerealis (Rhizoctonia spring blight) on wheat or barley; Rhizopus stolonifer (black mold, soft rot) on strawberries, carrots, cabbage, vines and tomatoes; Rhynchosporium secalis (scald) on barley, rye and triticale; Sa- rocladium oryzae and S. attenuatum (sheath rot) on rice; Sclerotinia spp. (stem rot or white mold) on vegetables and field crops, such as rape, sunflowers (e. g. S. sclerotiorum) and soybeans (e. g. S. rolfsii or S. sclerotiorum); Septoria spp. on various plants, e. g. S. glycines (brown spot) on soybeans, S. tritici (Septoria blotch) on wheat and S. (syn. Stagonospora) no- dorum (Stagonospora blotch) on cereals; Uncinula (syn. Erysiphe) necator (powdery mildew, anamorph: Oidium tuckeri) on vines; Setospaeria spp. (leaf blight) on corn (e. g. S. turcicum, syn. Helminthosporium turcicum) and turf; Sphacelotheca spp. (smut) on corn, (e. g. S. reiliana: head smut), sorghum und sugar cane; Sphaerotheca fuliginea (powdery mildew) on cucurbits; Spongospora subterranea (powdery scab) on potatoes and thereby transmitted viral diseases; Stagonospora spp. on cereals, e. g. S. nodorum (Stagonospora blotch, teleomorph: Lepto- sphaeria [syn. Phaeosphaeria] nodorum) on wheat; Synchytrium endobioticum on potatoes (potato wart disease); Taphrina spp., e. g. T. deformans (leaf curl disease) on peaches and T. pruni (plum pocket) on plums; Thielaviopsis spp. (black root rot) on tobacco, pome fruits, vegetables, soybeans and cotton, e. g. T. basicola (syn. Chalara elegans); Tilletia spp. (common bunt or stinking smut) on cereals, such as e. g. T. tritici (syn. T. caries, wheat bunt) and T. controversa (dwarf bunt) on wheat; Typhula incarnata (grey snow mold) on barley or wheat; Urocystis spp., e. g. U. occulta (stem smut) on rye; Uromyces spp. (rust) on vegetables, such as beans (e. g. U. appendiculatus, syn. U. phaseoli) and sugar beets (e. g. U. betae); Ustilago spp. (loose smut) on cereals (e. g. U. nuda and U. avaenae), corn (e. g. U. maydis: corn smut) and sugar cane; Venturia spp. (scab) on apples (e. g. V. inaequalis) and pears; and Verticillium spp. (wilt) on various plants, such as fruits and ornamentals, vines, soft fruits, vegetables and field crops, e. g. V. dahliae on strawberries, rape, potatoes and tomatoes.
In one embodiment, the fungicide a respiration inhibitor.
Suitable examples of respiration inhibitor fungicides to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are inhibitors of complex III at Q0 site, inhibitors of complex III at Q, site, inhibitors of complex II, or other respiration inhibitors or complex I uncouplers.
Suitable examples of respiration inhibitor fungicides of the class of inhibitors of complex III at Q0 site to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are strobilurines. Envisaged examples of stro- bilurine and similar compounds to be used in the context of the present invention include azoxystrobin (A.1.1 ), coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxystrobin/flufenoxystrobin, fluoxastrobin, kresoxim-methyl, mandestrobine, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin (A.1 .14), pyrametostrobin, pyrao- xystrobin, trifloxystrobin (A.1 .17) and 2-(2-(3-(2,6-dichlorophenyl)-1 -methyl-allylideneaminooxy- methyl)-phenyl)-2-methoxyimino-N-methyl-acetamide, pyribencarb, triclopyricarb/chlorodincarb, famoxadone, and fenamidone.
Suitable examples of respiration inhibitor fungicides of the class of inhibitors of complex III at Q, site to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are cyazofamid, amisulbrom, [(3S,6S,7R,8R)-8- benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7- yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acetoxymethoxy)-4-methoxy-pyridine- 2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)- 8-benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo- 1 ,5-dioxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1 ,3-benzodioxol-5- ylmethoxy)-4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2- methylpropanoate; and (3S,6S,7R,8R)-3-[[(3-hydroxy-4-methoxy-2-pyridinyl)carbonyl]amino]- 6-methyl-4,9-dioxo-8-(phenylmethyl)-1 ,5-dioxonan-7-yl 2-methylpropanoate. Suitable examples of respiration inhibitor fungicides of the class of inhibitors of complex II to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are benodanil, benzovindiflupyr, bixafen, boscalid (A.3.4), carboxin, fenfuram, fluopyram (A.3.7), flutolanil, fluxapyroxad (A.3.9), furametpyr, isofetamid, isopyrazam, mepronil, oxycarboxin, penflufen (A.3.14), penthiopyrad (A.3.15), sedaxane (A.3.16), tecloftalam, thifluzamide, N-(4'-trifluoromethylthiobiphenyl-2-yl)-3-difluoromethyl-1 - methyl-1 H-pyrazole-4-carboxamide, N-(2-(1 ,3,3-trimethyl-butyl)-phenyl)-1 ,3-dimethyl-5-fluoro- 1 H-pyrazole-4-carboxamide, 3-(difluoromethyl)-1 -methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole- 4-carboxamide, 3-(trifluoromethyl)-1 -methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4- carboxamide, 1 ,3-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3- (trifluoromethyl)-l ,5-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 1 ,3,5-tri- methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, N-(7-fluoro-1 ,1 ,3-trimethyl-indan-4- yl)-1 ,3-dimethyl-pyrazole-4-carboxamide, and N-[2-(2,4-dichlorophenyl)-2-methoxy-1 -methyl- ethyl]-3-(difluoromethyl)-1 -methyl-pyrazole-4-carboxamide.
Suitable examples of respiration inhibitor fungicides of the class of other respiration inhibitors or complex I uncouplers to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are diflumetorim, (5,8-difluoro- quinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl}-amine; nitrophenyl derivates: binapacryl, dinobuton, dinocap, fluazinam; ferimzone; organometal compounds: fen- tin salts, such as fentin-acetate, fentin chloride or fentin hydroxide; ametoctradin, silthiofam
In a further embodiment, the fungicide is a sterol biosynthesis inhibitor (SBI fungicide). Suitable examples of amino acid derivative herbicides to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are C14 demethylase inhibitors (DMI fungicides), delta14-reductase inhibitors, inhibitors of 3-keto reductase or 1 -[re/-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thio- cyanato-1 H-[1 ,2,4]triazole, 2-[re/-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranyl- methyl]-2H-[1 ,2,4]triazole-3-thiol, 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1 -(1 ,2,4-triazoM - yl)pentan-2-ol, 1 -[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -cyclopropyl-2-(1 ,2,4-triazol-1 - yl)ethanol, 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol, 2- [2-chloro-4-(4-chlorophenoxy)phenyl]-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol, 2-[4-(4-chlorophenoxy)-2- (trifluoromethyl)phenyl]-3-methyl-1 -(1 ,2,4-triazol-1-yl)butan-2-ol, 2-[4-(4-chlorophenoxy)-2- (trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1-yl)propan-2-ol, 2-[2-chloro-4-(4-chlorophenoxy)phenyl]- 3-methyl-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol, 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 - (1 ,2,4-triazol-1 -yl)pentan-2-ol, 2-[4-(4-fluorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol- 1 -yl)propan-2-ol, 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1 -(1 ,2,4-triazol-1 -yl)pent-3-yn-2-ol; or imidazoles such as imazalil, pefurazoate, prochloraz, triflumizol; pyrimidines, pyridines or piper- azines such as fenarimol, nuarimol, pyrifenox, triforine, and [3-(4-chloro-2-fluoro-phenyl)-5-(2,4- difluorophenyl)isoxazol-4-yl]-(3-pyridyl)methanol. Suitable examples of respiration inhibitor fungicides of the class of C14 demethylase inhibitors (DM I fungicides) to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are triazoles, azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole (B.1 .5), diniconazole, diniconazole-M, epoxi- conazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole (B.1 .15), metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole (B.1 .23), simeconazole, tebuconazole, tetraconazole, triadime- fon, triadimenol, triticonazole (B.1 .29), or uniconazole. Suitable examples of respiration inhibitor fungicides of the class of delta 14-reductase inhibitors to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph, fenpropidin, piperalin, or spiroxamine. A suitable example of a respiration inhibitor fungicide of the class of inhibitors of 3-keto reductase to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention is fenhexamid.
In a further embodiment, the fungicide is a nucleic acid synthesis inhibitor. Suitable examples of nucleic acid synthesis inhibitor fungicides to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are phenyl- amides or acyl amino acid fungicides, hymexazole, octhilinone, oxolinic acid, bupirimate, 5- fluorocytosine, 5-fluoro-2-(p-tolylmethoxy)pyrimidin-4-amine, or 5-fluoro-2-(4- fluorophenylmethoxy)pyrimidin-4-amine.
Suitable examples of nucleic acid synthesis inhibitor fungicides of the class of phenylamides or acyl amino acid fungicides to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are benalaxyl, benalaxyl- M, kiralaxyl, metalaxyl (C.1.4), metalaxyl-M (mefenoxam) (C.1.5), ofurace, or oxadixyl. In a further embodiment, the fungicide is an inhibitors of cell division and cytoskeleton. Suitable examples of inhibitor of cell division and cytoskeleton fungicides to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are tubulin inhibitors and other cell division inhibitors. Suitable examples of inhibitors of cell division and cytoskeleton fungicides of the class of tubulin inhibitors to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are benzimidazoles, thiophanates: beno- myl, carbendazim, fuberidazole, thiabendazole (D.1.4), thiophanate-methyl; or triazolopyrim- idines. A suitable example of triazolopyrimidines is 5-chloro-7-(4-methylpiperidin-1 -yl)-6-(2,4,6- trifluorophenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine.
Suitable examples of inhibitors of cell division and cytoskeleton fungicides of the class of other cell division inhibitors to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are diethofencarb, ethaboxam (D.2.2), pencycuron, fluopicolide, zoxamide, metrafenone and pyriofenone.
In a further embodiment, the fungicide is an inhibitor of amino acid and protein synthe- sis. Suitable examples of inhibitor of amino acid and protein synthesis fungicides to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are methionine synthesis inhibitors and protein synthesis inhibitors.
Suitable examples of inhibitor of amino acid and protein synthesis fungicides of the class of me- thionine synthesis inhibitors to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are cyprodinil, mepa- nipyrim, and pyrimethanil.
Suitable examples of inhibitor of amino acid and protein synthesis fungicides of the class of pro- tein synthesis inhibitors to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are blasticidin-S, kasugamy- cin, kasugamycin hydrochloride-hydrate, mildiomycin, streptomycin, oxytetracyclin, polyoxine and validamycin A. In a further embodiment, the fungicide is a signal transduction inhibitors. Suitable examples of signal transduction inhibitor fungicides to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are MAP / histidine kinase inhibitors or G protein inhibitors. Suitable examples of signal transduction inhibitor fungicides of the class of MAP / histidine kinase inhibitors to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are fluoroimid, iprodione, pro- cymidone, vinclozolin, fenpiclonil, and fludioxonil. A suitable example of an inhibitor of signal transduction inhibitor fungicides of the class of G protein inhibitors to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention is quinoxyfen.
In a further embodiment, the fungicide is a lipid and membrane synthesis inhibitor. Suitable ex- amples of lipid and membrane synthesis inhibitor fungicides to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are phospholipid biosynthesis inhibitors, phospholipid biosynthesis inhibitors, lipid peroxidation inhibitors, phospholipid biosynthesis and cell wall deposition inhibitors, compounds affecting cell membrane permeability and fatty acids or fatty acid amide hydrolase inhibitors.
Suitable examples of lipid and membrane synthesis inhibitor fungicides of the class of phospholipid biosynthesis inhibitors to be used in combination with a nitrification inhibitor or (T) - prefer- ably used in combination with (T) - according to the present invention are edifenphos, iproben- fos, pyrazophos, or isoprothiolane.
Suitable examples of lipid and membrane synthesis inhibitor fungicides of the class of lipid pe- roxidation inhibitors to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are dicloran, quintozene, tec- nazene, tolclofos-methyl, biphenyl, chloroneb, or etridiazole.
Suitable examples of lipid and membrane synthesis inhibitor fungicides of the class of phospho- lipid biosynthesis and cell wall deposition inhibitors to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are dimethomorph, flumorph, mandipropamid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate (G.3.7) or N-(1 -(1 -(4-cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester.
Suitable examples of lipid and membrane synthesis inhibitor fungicides of the class of compounds affecting cell membrane permeability and fatty acids to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are propamocarb or propamocarb-hydrochlorid.
Suitable examples of lipid and membrane synthesis inhibitor fungicides of the class of fatty acid amide hydrolase inhibitors to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are oxathiapiprolin (G.5.1 ), 2-{3-[2-(1 -{[3,5-bis(difluoromethyl-1 H-pyrazol-1 -yl]acetyl}piperidin-4-yl)-1 ,3-thiazol-4-yl]- 4,5-dihydro-1 ,2-oxazol-5-yl}phenyl methanesulfonate, 2-{3-[2-(1 -{[3,5-bis(difluoromethyl)-1 H- pyrazol-1 -yl]acetyl}piperidin-4-yl) or 1 ,3-thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol-5-yl}-3-chlorophenyl methanesulfonate.
In a further embodiment, the fungicide is an inhibitors with Multi Site Action. Suitable examples of inhibitor with Multi Site Action fungicides to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are inorganic active substances, thio- and dithiocarbamates, organochlorine compounds, or guanidines and others. Suitable examples of inhibitors with Multi Site Action fungicides of the class of inorganic active substances to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, or sulfur. Suitable examples of inhibitors with Multi Site Action fungicides of the class of thio- and dithiocarbamates to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are ferbam, mancozeb (H .2.2), maneb, metam, metiram, propineb, thiram, zineb, or ziram Suitable examples of inhibitors with Multi Site Action fungicides of the class of organochlorine compounds to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are phthalimides, sulfamides, chloroni- triles, anilazine, chlorothalonil (H.3.2), captafol, captan, folpet, dichlofluanid, dichlorophen, hex- achlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid, or N-(4-chloro-2-nitro- phenyl)-N-ethyl-4-methyl-benzenesulfonamide.
Suitable examples of inhibitors with Multi Site Action fungicides of the class of guanidines and others to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are guanidine, dodine, dodine free base, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine- tris(albesilate), dithianon, or 2,6-dimethyl-1 H,5H-[1 ,4]dithiino[2,3-c:5,6-c']dipyrrole- 1 ,3,5,7(2H,6H)-tetraone.
In a further embodiment, the fungicide is a cell wall synthesis inhibitor. Suitable examples of cell wall synthesis inhibitor fungicides to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are inhibitors of glucan synthesis.
Suitable examples of cell wall synthesis inhibitor fungicides of the class of inhibitors of glucan synthesis to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are validamycin, polyoxin B; melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamid, dicyclomet, or fenoxanil.
In a further embodiment, the fungicide is a plant defence inducer. Suitable examples of plant defence inducer fungicides to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are acibenzolar-S-methyl, probenazole, isotianil, tiadinil, prohexadione-calcium; phosphonates: fosetyl, fosetyl-aluminum, phosphorous acid or its salts.
In a further embodiment, the fungicide is a compounds with unknown mode of action. Suitable examples of such fungicides to be used in combination with a nitrification inhibitor or (T) - preferably used in combination with (T) - according to the present invention are bronopol, chinome- thionat, cyflufenamid, cymoxanil, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat- methylsulfate, diphenylamin, fenpyrazamine, flumetover, flusulfamide, flutianil, methasulfocarb nitrothal-isopropyl, picarbutrazox, tolprocarb, 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4- {5-[2-(prop-2-yn-1 -yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 - yl]ethanone, 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4-{5-[2-fluoro-6-(prop-2-yn-1 -yl- oxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 -yl]ethanone, 2-[3,5- bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4-{5-[2-chloro-6-(prop-2-yn-1 -yloxy)phenyl]-4,5- dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 -yl]ethanone, oxin-copper, proquinazid, tebufloquin, tecloftalam, triazoxide, 2-butoxy-6-iodo-3-propylchromen-4-one, N-(cyclo- propylmethoxyimino-(6-difluoro-methoxy-2,3-difluoro acetamide, N'-(4-
(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(4- (4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(2- methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine, N'-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine, methoxy-acetic acid 6-tert-butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester, 3-[5-(4- methylphenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine, 3-[5-(4-chloro-phenyl)-2,3-dimethyl- isoxazolidin-3-yl]-pyridine (pyrisoxazole),
N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide, 5-chloro-1 -(4,6-dimethoxy- pyrimidin-2-yl)-2-methyl-1 H-benzoimidazole, 2-(4-chloro-phenyl)- N-[4-(3,4-dimethoxy-phenyl)- isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide, ethyl (Z)-3-amino-2-cyano-3-phenyl-prop-2-enoate, pentyl N-[6-[[(Z)-[(1 -methyltetrazol-5-yl)-phenyl-methylene]amino]oxymethyl]-2- pyridyl]carbamate, 2-[2-[(7,8-difluoro-2-methyl-3-quinolyl)oxy]-6-fluoro-phenyl]propan-2-ol, 2-[2- fluoro-6-[(8-fluoro-2-methyl-3-quinolyl)oxy]phenyl]propan-2-ol, 3-(5-fluoro-3,3,4,4-tetramethyl- 3,4-dihydroisoquinolin-1 -yl)quinoline, 3-(4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1 -yl)- quinoline, 3-(4,4,5-trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1 -yl)quinolone, or 9-fluoro-2,2- dimethyl-5-(3-quinolyl)-3H-1 ,4-benzoxazepine.
In preferred embodiments, the fungicide may be selected from the following group of fungicides: A) Respiration inhibitors
Inhibitors of complex III at Q0 site (e. g. strobilurins): azoxystrobin, picoxystrobin, pyra- clostrobin, trifloxystrobin
inhibitors of complex III at Q, site: cyazofamid,
inhibitors of complex II (e. g. carboxamides): boscalid, fluopyram, fluxapyroxad, pen- flufen, penthiopyrad, sedaxane,
other respiration inhibitors: fluazinam;
B) Sterol biosynthesis inhibitors (SBI fungicides)
C14 demethylase inhibitors (DM I fungicides): cyproconazole, difenoconazole, flutriafol, ipconazole, prothioconazole, tebuconazole, triticonazole,
prochloraz,
Delta14-reductase inhibitors: fenpropimorph,
C) Nucleic acid synthesis inhibitors
phenylamides or acyl amino acid fungicides: metalaxyl, metalaxyl-M (mefenoxam), ofu- race, oxadixyl;
- 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4-amine;
D) Inhibitors of cell division and cytoskeleton
tubulin inhibitors, such as benzimidazoles, thiophanates: carbendazim, thiabendazole, other cell division inhibitors: diethofencarb, ethaboxam, fluopicolide, zoxamide, met- rafenone,
F) Signal transduction inhibitors
MAP / histidine kinase inhibitors: fludioxonil;
G protein inhibitors: quinoxyfen;
G) Lipid and membrane synthesis inhibitors phospholipid biosynthesis and cell wall deposition: dimethomorph, mandipropamid, fatty acid amide hydrolase inhibitors: oxathiapiprolin,
valifenalate
H) Inhibitors with Multi Site Action
- thio- and dithiocarbamates:, mancozeb, maneb, metam, metiram, thiram, ziram;
organochlorine compounds (e. g. phthalimides, sulfamides, chloronitriles): anilazine, chlorothalonil,
K) Unknown mode of action
cyflufenamid, dazomet,
In a particularly preferred embodiment, the fungicide is azoxystrobin (A.1.1 ), pyraclostrobin (A.1.14), trifloxystrobin (A.1 .17), boscalid (A.3.4), fluopyram (A.3.7), fluxapyroxad (A.3.9), pen- flufen (A.3.14), penthiopyrad (A.3.15), sedaxane (A.3.16), difenoconazole (B.1.5), ipconazole (B.1.15), prothioconazole (B.1 .23), triticonazole (B.1 .29), metalaxyl (C.1 .4), metalaxyl-M (mefenoxam) (C.1.5), thiabendazole (D.1.4), ethaboxam (D.2.2), valifenalate (G.3.7), oxathiapiprolin (G.5.1 ), mancozeb (H.2.2), or chlorothalonil (H.3.2).
Accordingly, the present invention furthermore relates to compositions comprising as compound I (component A) a nitrification inhibitor as defined herein above and as compound II (component B) a fungicide as defined herein, i.e. a combination of component A and B. In preferred embodiments, such compositions may be selected from the component A of Table 2 in column 2 (Com. A) and from component B of Table 2 in column 3 (Com. B). The number of component A of Table 2 corresponds to the number of component A as shown in Table 1 , supra ("Entry"). Preferred embodiments thus include the specified combinations or compositions comprising component A and B as defined in Cb-1 to Cb-4515 of the following Table 2:
Com. Com. Com. Com. Com. Com.
Comb. Comb. Comb.
A B A B A B
Cb-1 1 A.1 .1 Cb-216 1 A.1.14 Cb-431 1 A.1 .17
Cb-2 2 A.1 .1 Cb-217 2 A.1.14 Cb-432 2 A.1 .17
Cb-3 3 A.1 .1 Cb-218 3 A.1.14 Cb-433 3 A.1 .17
Cb-4 4 A.1 .1 Cb-219 4 A.1.14 Cb-434 4 A.1 .17
Cb-5 5 A.1 .1 Cb-220 5 A.1.14 Cb-435 5 A.1 .17
Cb-6 6 A.1 .1 Cb-221 6 A.1.14 Cb-436 6 A.1 .17
Cb-7 7 A.1 .1 Cb-222 7 A.1.14 Cb-437 7 A.1 .17
Cb-8 8 A.1 .1 Cb-223 8 A.1.14 Cb-438 8 A.1 .17
Cb-9 9 A.1 .1 Cb-224 9 A.1.14 Cb-439 9 A.1 .17
Cb-10 10 A.1 .1 Cb-225 10 A.1.14 Cb-440 10 A.1 .17
Cb-1 1 1 1 A.1 .1 Cb-226 1 1 A.1.14 Cb-441 1 1 A.1 .17
Cb-12 12 A.1 .1 Cb-227 12 A.1.14 Cb-442 12 A.1 .17
Cb-13 13 A.1 .1 Cb-228 13 A.1.14 Cb-443 13 A.1 .17
Cb-14 14 A.1 .1 Cb-229 14 A.1.14 Cb-444 14 A.1 .17
Cb-15 15 A.1 .1 Cb-230 15 A.1.14 Cb-445 15 A.1 .17 Cb-16 16 A.1.1 Cb-231 16 A.1.14 Cb-446 16 A.1.17
Cb-17 17 A.1.1 Cb-232 17 A.1.14 Cb-447 17 A.1.17
Cb-18 18 A.1.1 Cb-233 18 A.1.14 Cb-448 18 A.1.17
Cb-19 19 A.1.1 Cb-234 19 A.1.14 Cb-449 19 A.1.17
Cb-20 20 A.1.1 Cb-235 20 A.1.14 Cb-450 20 A.1.17
Cb-21 21 A.1.1 Cb-236 21 A.1.14 Cb-451 21 A.1.17
Cb-22 22 A.1.1 Cb-237 22 A.1.14 Cb-452 22 A.1.17
Cb-23 23 A.1.1 Cb-238 23 A.1.14 Cb-453 23 A.1.17
Cb-24 24 A.1.1 Cb-239 24 A.1.14 Cb-454 24 A.1.17
Cb-25 25 A.1.1 Cb-240 25 A.1.14 Cb-455 25 A.1.17
Cb-26 26 A.1.1 Cb-241 26 A.1.14 Cb-456 26 A.1.17
Cb-27 27 A.1.1 Cb-242 27 A.1.14 Cb-457 27 A.1.17
Cb-28 28 A.1.1 Cb-243 28 A.1.14 Cb-458 28 A.1.17
Cb-29 29 A.1.1 Cb-244 29 A.1.14 Cb-459 29 A.1.17
Cb-30 30 A.1.1 Cb-245 30 A.1.14 Cb-460 30 A.1.17
Cb-31 31 A.1.1 Cb-246 31 A.1.14 Cb-461 31 A.1.17
Cb-32 32 A.1.1 Cb-247 32 A.1.14 Cb-462 32 A.1.17
Cb-33 33 A.1.1 Cb-248 33 A.1.14 Cb-463 33 A.1.17
Cb-34 34 A.1.1 Cb-249 34 A.1.14 Cb-464 34 A.1.17
Cb-35 35 A.1.1 Cb-250 35 A.1.14 Cb-465 35 A.1.17
Cb-36 36 A.1.1 Cb-251 36 A.1.14 Cb-466 36 A.1.17
Cb-37 37 A.1.1 Cb-252 37 A.1.14 Cb-467 37 A.1.17
Cb-38 38 A.1.1 Cb-253 38 A.1.14 Cb-468 38 A.1.17
Cb-39 39 A.1.1 Cb-254 39 A.1.14 Cb-469 39 A.1.17
Cb-40 40 A.1.1 Cb-255 40 A.1.14 Cb-470 40 A.1.17
Cb-41 41 A.1.1 Cb-256 41 A.1.14 Cb-471 41 A.1.17
Cb-42 42 A.1.1 Cb-257 42 A.1.14 Cb-472 42 A.1.17
Cb-43 43 A.1.1 Cb-258 43 A.1.14 Cb-473 43 A.1.17
Cb-44 44 A.1.1 Cb-259 44 A.1.14 Cb-474 44 A.1.17
Cb-45 45 A.1.1 Cb-260 45 A.1.14 Cb-475 45 A.1.17
Cb-46 46 A.1.1 Cb-261 46 A.1.14 Cb-476 46 A.1.17
Cb-47 47 A.1.1 Cb-262 47 A.1.14 Cb-477 47 A.1.17
Cb-48 48 A.1.1 Cb-263 48 A.1.14 Cb-478 48 A.1.17
Cb-49 49 A.1.1 Cb-264 49 A.1.14 Cb-479 49 A.1.17
Cb-50 50 A.1.1 Cb-265 50 A.1.14 Cb-480 50 A.1.17
Cb-51 51 A.1.1 Cb-266 51 A.1.14 Cb-481 51 A.1.17
Cb-52 52 A.1.1 Cb-267 52 A.1.14 Cb-482 52 A.1.17
Cb-53 53 A.1.1 Cb-268 53 A.1.14 Cb-483 53 A.1.17
Cb-54 54 A.1.1 Cb-269 54 A.1.14 Cb-484 54 A.1.17
Cb-55 55 A.1.1 Cb-270 55 A.1.14 Cb-485 55 A.1.17
Cb-56 56 A.1.1 Cb-271 56 A.1.14 Cb-486 56 A.1.17 Cb-57 57 A.1.1 Cb-272 57 A.1.14 Cb-487 57 A.1.17
Cb-58 58 A.1.1 Cb-273 58 A.1.14 Cb-488 58 A.1.17
Cb-59 59 A.1.1 Cb-274 59 A.1.14 Cb-489 59 A.1.17
Cb-60 60 A.1.1 Cb-275 60 A.1.14 Cb-490 60 A.1.17
Cb-61 61 A.1.1 Cb-276 61 A.1.14 Cb-491 61 A.1.17
Cb-62 62 A.1.1 Cb-277 62 A.1.14 Cb-492 62 A.1.17
Cb-63 63 A.1.1 Cb-278 63 A.1.14 Cb-493 63 A.1.17
Cb-64 64 A.1.1 Cb-279 64 A.1.14 Cb-494 64 A.1.17
Cb-65 65 A.1.1 Cb-280 65 A.1.14 Cb-495 65 A.1.17
Cb-66 66 A.1.1 Cb-281 66 A.1.14 Cb-496 66 A.1.17
Cb-67 67 A.1.1 Cb-282 67 A.1.14 Cb-497 67 A.1.17
Cb-68 68 A.1.1 Cb-283 68 A.1.14 Cb-498 68 A.1.17
Cb-69 69 A.1.1 Cb-284 69 A.1.14 Cb-499 69 A.1.17
Cb-70 70 A.1.1 Cb-285 70 A.1.14 Cb-500 70 A.1.17
Cb-71 71 A.1.1 Cb-286 71 A.1.14 Cb-501 71 A.1.17
Cb-72 72 A.1.1 Cb-287 72 A.1.14 Cb-502 72 A.1.17
Cb-73 73 A.1.1 Cb-288 73 A.1.14 Cb-503 73 A.1.17
Cb-74 74 A.1.1 Cb-289 74 A.1.14 Cb-504 74 A.1.17
Cb-75 75 A.1.1 Cb-290 75 A.1.14 Cb-505 75 A.1.17
Cb-76 76 A.1.1 Cb-291 76 A.1.14 Cb-506 76 A.1.17
Cb-77 77 A.1.1 Cb-292 77 A.1.14 Cb-507 77 A.1.17
Cb-78 78 A.1.1 Cb-293 78 A.1.14 Cb-508 78 A.1.17
Cb-79 79 A.1.1 Cb-294 79 A.1.14 Cb-509 79 A.1.17
Cb-80 80 A.1.1 Cb-295 80 A.1.14 Cb-510 80 A.1.17
Cb-81 81 A.1.1 Cb-296 81 A.1.14 Cb-511 81 A.1.17
Cb-82 82 A.1.1 Cb-297 82 A.1.14 Cb-512 82 A.1.17
Cb-83 83 A.1.1 Cb-298 83 A.1.14 Cb-513 83 A.1.17
Cb-84 84 A.1.1 Cb-299 84 A.1.14 Cb-514 84 A.1.17
Cb-85 85 A.1.1 Cb-300 85 A.1.14 Cb-515 85 A.1.17
Cb-86 86 A.1.1 Cb-301 86 A.1.14 Cb-516 86 A.1.17
Cb-87 87 A.1.1 Cb-302 87 A.1.14 Cb-517 87 A.1.17
Cb-88 88 A.1.1 Cb-303 88 A.1.14 Cb-518 88 A.1.17
Cb-89 89 A.1.1 Cb-304 89 A.1.14 Cb-519 89 A.1.17
Cb-90 90 A.1.1 Cb-305 90 A.1.14 Cb-520 90 A.1.17
Cb-91 91 A.1.1 Cb-306 91 A.1.14 Cb-521 91 A.1.17
Cb-92 92 A.1.1 Cb-307 92 A.1.14 Cb-522 92 A.1.17
Cb-93 93 A.1.1 Cb-308 93 A.1.14 Cb-523 93 A.1.17
Cb-94 94 A.1.1 Cb-309 94 A.1.14 Cb-524 94 A.1.17
Cb-95 95 A.1.1 Cb-310 95 A.1.14 Cb-525 95 A.1.17
Cb-96 96 A.1.1 Cb-311 96 A.1.14 Cb-526 96 A.1.17
Cb-97 97 A.1.1 Cb-312 97 A.1.14 Cb-527 97 A.1.17 Cb-98 98 A.1.1 Cb-313 98 A.1.14 Cb-528 98 A.1.17
Cb-99 99 A.1.1 Cb-314 99 A.1.14 Cb-529 99 A.1.17
Cb-100 100 A.1.1 Cb-315 100 A.1.14 Cb-530 100 A.1.17
Cb-101 101 A.1.1 Cb-316 101 A.1.14 Cb-531 101 A.1.17
Cb-102 102 A.1.1 Cb-317 102 A.1.14 Cb-532 102 A.1.17
Cb-103 103 A.1.1 Cb-318 103 A.1.14 Cb-533 103 A.1.17
Cb-104 104 A.1.1 Cb-319 104 A.1.14 Cb-534 104 A.1.17
Cb-105 105 A.1.1 Cb-320 105 A.1.14 Cb-535 105 A.1.17
Cb-106 106 A.1.1 Cb-321 106 A.1.14 Cb-536 106 A.1.17
Cb-107 107 A.1.1 Cb-322 107 A.1.14 Cb-537 107 A.1.17
Cb-108 108 A.1.1 Cb-323 108 A.1.14 Cb-538 108 A.1.17
Cb-109 109 A.1.1 Cb-324 109 A.1.14 Cb-539 109 A.1.17
Cb-110 110 A.1.1 Cb-325 110 A.1.14 Cb-540 110 A.1.17
Cb-111 111 A.1.1 Cb-326 111 A.1.14 Cb-541 111 A.1.17
Cb-112 112 A.1.1 Cb-327 112 A.1.14 Cb-542 112 A.1.17
Cb-113 113 A.1.1 Cb-328 113 A.1.14 Cb-543 113 A.1.17
Cb-114 114 A.1.1 Cb-329 114 A.1.14 Cb-544 114 A.1.17
Cb-115 115 A.1.1 Cb-330 115 A.1.14 Cb-545 115 A.1.17
Cb-116 116 A.1.1 Cb-331 116 A.1.14 Cb-546 116 A.1.17
Cb-117 117 A.1.1 Cb-332 117 A.1.14 Cb-547 117 A.1.17
Cb-118 118 A.1.1 Cb-333 118 A.1.14 Cb-548 118 A.1.17
Cb-119 119 A.1.1 Cb-334 119 A.1.14 Cb-549 119 A.1.17
Cb-120 120 A.1.1 Cb-335 120 A.1.14 Cb-550 120 A.1.17
Cb-121 121 A.1.1 Cb-336 121 A.1.14 Cb-551 121 A.1.17
Cb-122 122 A.1.1 Cb-337 122 A.1.14 Cb-552 122 A.1.17
Cb-123 123 A.1.1 Cb-338 123 A.1.14 Cb-553 123 A.1.17
Cb-124 124 A.1.1 Cb-339 124 A.1.14 Cb-554 124 A.1.17
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Cb-1462 172 A.3.14 Cb-1677 172 A.3.15 Cb-1892 172 A.3.16
Cb-1463 173 A.3.14 Cb-1678 173 A.3.15 Cb-1893 173 A.3.16
Cb-1464 174 A.3.14 Cb-1679 174 A.3.15 Cb-1894 174 A.3.16
Cb-1465 175 A.3.14 Cb-1680 175 A.3.15 Cb-1895 175 A.3.16
Cb-1466 176 A.3.14 Cb-1681 176 A.3.15 Cb-1896 176 A.3.16
Cb-1467 177 A.3.14 Cb-1682 177 A.3.15 Cb-1897 177 A.3.16
Cb-1468 178 A.3.14 Cb-1683 178 A.3.15 Cb-1898 178 A.3.16
Cb-1469 179 A.3.14 Cb-1684 179 A.3.15 Cb-1899 179 A.3.16
Cb-1470 180 A.3.14 Cb-1685 180 A.3.15 Cb-1900 180 A.3.16
Cb-1471 181 A.3.14 Cb-1686 181 A.3.15 Cb-1901 181 A.3.16
Cb-1472 182 A.3.14 Cb-1687 182 A.3.15 Cb-1902 182 A.3.16
Cb-1473 183 A.3.14 Cb-1688 183 A.3.15 Cb-1903 183 A.3.16
Cb-1474 184 A.3.14 Cb-1689 184 A.3.15 Cb-1904 184 A.3.16
Cb-1475 185 A.3.14 Cb-1690 185 A.3.15 Cb-1905 185 A.3.16
Cb-1476 186 A.3.14 Cb-1691 186 A.3.15 Cb-1906 186 A.3.16
Cb-1477 187 A.3.14 Cb-1692 187 A.3.15 Cb-1907 187 A.3.16
Cb-1478 188 A.3.14 Cb-1693 188 A.3.15 Cb-1908 188 A.3.16
Cb-1479 189 A.3.14 Cb-1694 189 A.3.15 Cb-1909 189 A.3.16
Cb-1480 190 A.3.14 Cb-1695 190 A.3.15 Cb-1910 190 A.3.16
Cb-1481 191 A.3.14 Cb-1696 191 A.3.15 Cb-191 1 191 A.3.16
Cb-1482 192 A.3.14 Cb-1697 192 A.3.15 Cb-1912 192 A.3.16
Cb-1483 193 A.3.14 Cb-1698 193 A.3.15 Cb-1913 193 A.3.16
Cb-1484 194 A.3.14 Cb-1699 194 A.3.15 Cb-1914 194 A.3.16
Cb-1485 195 A.3.14 Cb-1700 195 A.3.15 Cb-1915 195 A.3.16
Cb-1486 196 A.3.14 Cb-1701 196 A.3.15 Cb-1916 196 A.3.16
Cb-1487 197 A.3.14 Cb-1702 197 A.3.15 Cb-1917 197 A.3.16
Cb-1488 198 A.3.14 Cb-1703 198 A.3.15 Cb-1918 198 A.3.16
Cb-1489 199 A.3.14 Cb-1704 199 A.3.15 Cb-1919 199 A.3.16
Cb-1490 200 A.3.14 Cb-1705 200 A.3.15 Cb-1920 200 A.3.16 Cb-1491 201 A.3.14 Cb-1706 201 A.3.15 Cb-1921 201 A.3.16
Cb-1492 202 A.3.14 Cb-1707 202 A.3.15 Cb-1922 202 A.3.16
Cb-1493 203 A.3.14 Cb-1708 203 A.3.15 Cb-1923 203 A.3.16
Cb-1494 204 A.3.14 Cb-1709 204 A.3.15 Cb-1924 204 A.3.16
Cb-1495 205 A.3.14 Cb-1710 205 A.3.15 Cb-1925 205 A.3.16
Cb-1496 206 A.3.14 Cb-1711 206 A.3.15 Cb-1926 206 A.3.16
Cb-1497 207 A.3.14 Cb-1712 207 A.3.15 Cb-1927 207 A.3.16
Cb-1498 208 A.3.14 Cb-1713 208 A.3.15 Cb-1928 208 A.3.16
Cb-1499 209 A.3.14 Cb-1714 209 A.3.15 Cb-1929 209 A.3.16
Cb-1500 210 A.3.14 Cb-1715 210 A.3.15 Cb-1930 210 A.3.16
Cb-1501 211 A.3.14 Cb-1716 211 A.3.15 Cb-1931 211 A.3.16
Cb-1502 212 A.3.14 Cb-1717 212 A.3.15 Cb-1932 212 A.3.16
Cb-1503 213 A.3.14 Cb-1718 213 A.3.15 Cb-1933 213 A.3.16
Cb-1504 214 A.3.14 Cb-1719 214 A.3.15 Cb-1934 214 A.3.16
Cb-1505 215 A.3.14 Cb-1720 215 A.3.15 Cb-1935 215 A.3.16
Cb-1936 1 B.1.5 Cb-2151 1 B.1.15 Cb-2366 1 B.1.23
Cb-1937 2 B.1.5 Cb-2152 2 B.1.15 Cb-2367 2 B.1.23
Cb-1938 3 B.1.5 Cb-2153 3 B.1.15 Cb-2368 3 B.1.23
Cb-1939 4 B.1.5 Cb-2154 4 B.1.15 Cb-2369 4 B.1.23
Cb-1940 5 B.1.5 Cb-2155 5 B.1.15 Cb-2370 5 B.1.23
Cb-1941 6 B.1.5 Cb-2156 6 B.1.15 Cb-2371 6 B.1.23
Cb-1942 7 B.1.5 Cb-2157 7 B.1.15 Cb-2372 7 B.1.23
Cb-1943 8 B.1.5 Cb-2158 8 B.1.15 Cb-2373 8 B.1.23
Cb-1944 9 B.1.5 Cb-2159 9 B.1.15 Cb-2374 9 B.1.23
Cb-1945 10 B.1.5 Cb-2160 10 B.1.15 Cb-2375 10 B.1.23
Cb-1946 11 B.1.5 Cb-2161 11 B.1.15 Cb-2376 11 B.1.23
Cb-1947 12 B.1.5 Cb-2162 12 B.1.15 Cb-2377 12 B.1.23
Cb-1948 13 B.1.5 Cb-2163 13 B.1.15 Cb-2378 13 B.1.23
Cb-1949 14 B.1.5 Cb-2164 14 B.1.15 Cb-2379 14 B.1.23
Cb-1950 15 B.1.5 Cb-2165 15 B.1.15 Cb-2380 15 B.1.23
Cb-1951 16 B.1.5 Cb-2166 16 B.1.15 Cb-2381 16 B.1.23
Cb-1952 17 B.1.5 Cb-2167 17 B.1.15 Cb-2382 17 B.1.23
Cb-1953 18 B.1.5 Cb-2168 18 B.1.15 Cb-2383 18 B.1.23
Cb-1954 19 B.1.5 Cb-2169 19 B.1.15 Cb-2384 19 B.1.23
Cb-1955 20 B.1.5 Cb-2170 20 B.1.15 Cb-2385 20 B.1.23
Cb-1956 21 B.1.5 Cb-2171 21 B.1.15 Cb-2386 21 B.1.23
Cb-1957 22 B.1.5 Cb-2172 22 B.1.15 Cb-2387 22 B.1.23
Cb-1958 23 B.1.5 Cb-2173 23 B.1.15 Cb-2388 23 B.1.23
Cb-1959 24 B.1.5 Cb-2174 24 B.1.15 Cb-2389 24 B.1.23
Cb-1960 25 B.1.5 Cb-2175 25 B.1.15 Cb-2390 25 B.1.23
Cb-1961 26 B.1.5 Cb-2176 26 B.1.15 Cb-2391 26 B.1.23 Cb-1962 27 B.1.5 Cb-2177 27 B.1.15 Cb-2392 27 B.1.23
Cb-1963 28 B.1.5 Cb-2178 28 B.1.15 Cb-2393 28 B.1.23
Cb-1964 29 B.1.5 Cb-2179 29 B.1.15 Cb-2394 29 B.1.23
Cb-1965 30 B.1.5 Cb-2180 30 B.1.15 Cb-2395 30 B.1.23
Cb-1966 31 B.1.5 Cb-2181 31 B.1.15 Cb-2396 31 B.1.23
Cb-1967 32 B.1.5 Cb-2182 32 B.1.15 Cb-2397 32 B.1.23
Cb-1968 33 B.1.5 Cb-2183 33 B.1.15 Cb-2398 33 B.1.23
Cb-1969 34 B.1.5 Cb-2184 34 B.1.15 Cb-2399 34 B.1.23
Cb-1970 35 B.1.5 Cb-2185 35 B.1.15 Cb-2400 35 B.1.23
Cb-1971 36 B.1.5 Cb-2186 36 B.1.15 Cb-2401 36 B.1.23
Cb-1972 37 B.1.5 Cb-2187 37 B.1.15 Cb-2402 37 B.1.23
Cb-1973 38 B.1.5 Cb-2188 38 B.1.15 Cb-2403 38 B.1.23
Cb-1974 39 B.1.5 Cb-2189 39 B.1.15 Cb-2404 39 B.1.23
Cb-1975 40 B.1.5 Cb-2190 40 B.1.15 Cb-2405 40 B.1.23
Cb-1976 41 B.1.5 Cb-2191 41 B.1.15 Cb-2406 41 B.1.23
Cb-1977 42 B.1.5 Cb-2192 42 B.1.15 Cb-2407 42 B.1.23
Cb-1978 43 B.1.5 Cb-2193 43 B.1.15 Cb-2408 43 B.1.23
Cb-1979 44 B.1.5 Cb-2194 44 B.1.15 Cb-2409 44 B.1.23
Cb-1980 45 B.1.5 Cb-2195 45 B.1.15 Cb-2410 45 B.1.23
Cb-1981 46 B.1.5 Cb-2196 46 B.1.15 Cb-2411 46 B.1.23
Cb-1982 47 B.1.5 Cb-2197 47 B.1.15 Cb-2412 47 B.1.23
Cb-1983 48 B.1.5 Cb-2198 48 B.1.15 Cb-2413 48 B.1.23
Cb-1984 49 B.1.5 Cb-2199 49 B.1.15 Cb-2414 49 B.1.23
Cb-1985 50 B.1.5 Cb-2200 50 B.1.15 Cb-2415 50 B.1.23
Cb-1986 51 B.1.5 Cb-2201 51 B.1.15 Cb-2416 51 B.1.23
Cb-1987 52 B.1.5 Cb-2202 52 B.1.15 Cb-2417 52 B.1.23
Cb-1988 53 B.1.5 Cb-2203 53 B.1.15 Cb-2418 53 B.1.23
Cb-1989 54 B.1.5 Cb-2204 54 B.1.15 Cb-2419 54 B.1.23
Cb-1990 55 B.1.5 Cb-2205 55 B.1.15 Cb-2420 55 B.1.23
Cb-1991 56 B.1.5 Cb-2206 56 B.1.15 Cb-2421 56 B.1.23
Cb-1992 57 B.1.5 Cb-2207 57 B.1.15 Cb-2422 57 B.1.23
Cb-1993 58 B.1.5 Cb-2208 58 B.1.15 Cb-2423 58 B.1.23
Cb-1994 59 B.1.5 Cb-2209 59 B.1.15 Cb-2424 59 B.1.23
Cb-1995 60 B.1.5 Cb-2210 60 B.1.15 Cb-2425 60 B.1.23
Cb-1996 61 B.1.5 Cb-2211 61 B.1.15 Cb-2426 61 B.1.23
Cb-1997 62 B.1.5 Cb-2212 62 B.1.15 Cb-2427 62 B.1.23
Cb-1998 63 B.1.5 Cb-2213 63 B.1.15 Cb-2428 63 B.1.23
Cb-1999 64 B.1.5 Cb-2214 64 B.1.15 Cb-2429 64 B.1.23
Cb-2000 65 B.1.5 Cb-2215 65 B.1.15 Cb-2430 65 B.1.23
Cb-2001 66 B.1.5 Cb-2216 66 B.1.15 Cb-2431 66 B.1.23
Cb-2002 67 B.1.5 Cb-2217 67 B.1.15 Cb-2432 67 B.1.23 Cb-2003 68 B.1.5 Cb-2218 68 B.1.15 Cb-2433 68 B.1.23
Cb-2004 69 B.1.5 Cb-2219 69 B.1.15 Cb-2434 69 B.1.23
Cb-2005 70 B.1.5 Cb-2220 70 B.1.15 Cb-2435 70 B.1.23
Cb-2006 71 B.1.5 Cb-2221 71 B.1.15 Cb-2436 71 B.1.23
Cb-2007 72 B.1.5 Cb-2222 72 B.1.15 Cb-2437 72 B.1.23
Cb-2008 73 B.1.5 Cb-2223 73 B.1.15 Cb-2438 73 B.1.23
Cb-2009 74 B.1.5 Cb-2224 74 B.1.15 Cb-2439 74 B.1.23
Cb-2010 75 B.1.5 Cb-2225 75 B.1.15 Cb-2440 75 B.1.23
Cb-201 1 76 B.1.5 Cb-2226 76 B.1.15 Cb-2441 76 B.1.23
Cb-2012 77 B.1.5 Cb-2227 77 B.1.15 Cb-2442 77 B.1.23
Cb-2013 78 B.1.5 Cb-2228 78 B.1.15 Cb-2443 78 B.1.23
Cb-2014 79 B.1.5 Cb-2229 79 B.1.15 Cb-2444 79 B.1.23
Cb-2015 80 B.1.5 Cb-2230 80 B.1.15 Cb-2445 80 B.1.23
Cb-2016 81 B.1.5 Cb-2231 81 B.1.15 Cb-2446 81 B.1.23
Cb-2017 82 B.1.5 Cb-2232 82 B.1.15 Cb-2447 82 B.1.23
Cb-2018 83 B.1.5 Cb-2233 83 B.1.15 Cb-2448 83 B.1.23
Cb-2019 84 B.1.5 Cb-2234 84 B.1.15 Cb-2449 84 B.1.23
Cb-2020 85 B.1.5 Cb-2235 85 B.1.15 Cb-2450 85 B.1.23
Cb-2021 86 B.1.5 Cb-2236 86 B.1.15 Cb-2451 86 B.1.23
Cb-2022 87 B.1.5 Cb-2237 87 B.1.15 Cb-2452 87 B.1.23
Cb-2023 88 B.1.5 Cb-2238 88 B.1.15 Cb-2453 88 B.1.23
Cb-2024 89 B.1.5 Cb-2239 89 B.1.15 Cb-2454 89 B.1.23
Cb-2025 90 B.1.5 Cb-2240 90 B.1.15 Cb-2455 90 B.1.23
Cb-2026 91 B.1.5 Cb-2241 91 B.1.15 Cb-2456 91 B.1.23
Cb-2027 92 B.1.5 Cb-2242 92 B.1.15 Cb-2457 92 B.1.23
Cb-2028 93 B.1.5 Cb-2243 93 B.1.15 Cb-2458 93 B.1.23
Cb-2029 94 B.1.5 Cb-2244 94 B.1.15 Cb-2459 94 B.1.23
Cb-2030 95 B.1.5 Cb-2245 95 B.1.15 Cb-2460 95 B.1.23
Cb-2031 96 B.1.5 Cb-2246 96 B.1.15 Cb-2461 96 B.1.23
Cb-2032 97 B.1.5 Cb-2247 97 B.1.15 Cb-2462 97 B.1.23
Cb-2033 98 B.1.5 Cb-2248 98 B.1.15 Cb-2463 98 B.1.23
Cb-2034 99 B.1.5 Cb-2249 99 B.1.15 Cb-2464 99 B.1.23
Cb-2035 100 B.1.5 Cb-2250 100 B.1.15 Cb-2465 100 B.1.23
Cb-2036 101 B.1.5 Cb-2251 101 B.1.15 Cb-2466 101 B.1.23
Cb-2037 102 B.1.5 Cb-2252 102 B.1.15 Cb-2467 102 B.1.23
Cb-2038 103 B.1.5 Cb-2253 103 B.1.15 Cb-2468 103 B.1.23
Cb-2039 104 B.1.5 Cb-2254 104 B.1.15 Cb-2469 104 B.1.23
Cb-2040 105 B.1.5 Cb-2255 105 B.1.15 Cb-2470 105 B.1.23
Cb-2041 106 B.1.5 Cb-2256 106 B.1.15 Cb-2471 106 B.1.23
Cb-2042 107 B.1.5 Cb-2257 107 B.1.15 Cb-2472 107 B.1.23
Cb-2043 108 B.1.5 Cb-2258 108 B.1.15 Cb-2473 108 B.1.23 Cb-2044 109 B.1.5 Cb-2259 109 B.1.15 Cb-2474 109 B.1.23
Cb-2045 110 B.1.5 Cb-2260 110 B.1.15 Cb-2475 110 B.1.23
Cb-2046 111 B.1.5 Cb-2261 111 B.1.15 Cb-2476 111 B.1.23
Cb-2047 112 B.1.5 Cb-2262 112 B.1.15 Cb-2477 112 B.1.23
Cb-2048 113 B.1.5 Cb-2263 113 B.1.15 Cb-2478 113 B.1.23
Cb-2049 114 B.1.5 Cb-2264 114 B.1.15 Cb-2479 114 B.1.23
Cb-2050 115 B.1.5 Cb-2265 115 B.1.15 Cb-2480 115 B.1.23
Cb-2051 116 B.1.5 Cb-2266 116 B.1.15 Cb-2481 116 B.1.23
Cb-2052 117 B.1.5 Cb-2267 117 B.1.15 Cb-2482 117 B.1.23
Cb-2053 118 B.1.5 Cb-2268 118 B.1.15 Cb-2483 118 B.1.23
Cb-2054 119 B.1.5 Cb-2269 119 B.1.15 Cb-2484 119 B.1.23
Cb-2055 120 B.1.5 Cb-2270 120 B.1.15 Cb-2485 120 B.1.23
Cb-2056 121 B.1.5 Cb-2271 121 B.1.15 Cb-2486 121 B.1.23
Cb-2057 122 B.1.5 Cb-2272 122 B.1.15 Cb-2487 122 B.1.23
Cb-2058 123 B.1.5 Cb-2273 123 B.1.15 Cb-2488 123 B.1.23
Cb-2059 124 B.1.5 Cb-2274 124 B.1.15 Cb-2489 124 B.1.23
Cb-2060 125 B.1.5 Cb-2275 125 B.1.15 Cb-2490 125 B.1.23
Cb-2061 126 B.1.5 Cb-2276 126 B.1.15 Cb-2491 126 B.1.23
Cb-2062 127 B.1.5 Cb-2277 127 B.1.15 Cb-2492 127 B.1.23
Cb-2063 128 B.1.5 Cb-2278 128 B.1.15 Cb-2493 128 B.1.23
Cb-2064 129 B.1.5 Cb-2279 129 B.1.15 Cb-2494 129 B.1.23
Cb-2065 130 B.1.5 Cb-2280 130 B.1.15 Cb-2495 130 B.1.23
Cb-2066 131 B.1.5 Cb-2281 131 B.1.15 Cb-2496 131 B.1.23
Cb-2067 132 B.1.5 Cb-2282 132 B.1.15 Cb-2497 132 B.1.23
Cb-2068 133 B.1.5 Cb-2283 133 B.1.15 Cb-2498 133 B.1.23
Cb-2069 134 B.1.5 Cb-2284 134 B.1.15 Cb-2499 134 B.1.23
Cb-2070 135 B.1.5 Cb-2285 135 B.1.15 Cb-2500 135 B.1.23
Cb-2071 136 B.1.5 Cb-2286 136 B.1.15 Cb-2501 136 B.1.23
Cb-2072 137 B.1.5 Cb-2287 137 B.1.15 Cb-2502 137 B.1.23
Cb-2073 138 B.1.5 Cb-2288 138 B.1.15 Cb-2503 138 B.1.23
Cb-2074 139 B.1.5 Cb-2289 139 B.1.15 Cb-2504 139 B.1.23
Cb-2075 140 B.1.5 Cb-2290 140 B.1.15 Cb-2505 140 B.1.23
Cb-2076 141 B.1.5 Cb-2291 141 B.1.15 Cb-2506 141 B.1.23
Cb-2077 142 B.1.5 Cb-2292 142 B.1.15 Cb-2507 142 B.1.23
Cb-2078 143 B.1.5 Cb-2293 143 B.1.15 Cb-2508 143 B.1.23
Cb-2079 144 B.1.5 Cb-2294 144 B.1.15 Cb-2509 144 B.1.23
Cb-2080 145 B.1.5 Cb-2295 145 B.1.15 Cb-2510 145 B.1.23
Cb-2081 146 B.1.5 Cb-2296 146 B.1.15 Cb-2511 146 B.1.23
Cb-2082 147 B.1.5 Cb-2297 147 B.1.15 Cb-2512 147 B.1.23
Cb-2083 148 B.1.5 Cb-2298 148 B.1.15 Cb-2513 148 B.1.23
Cb-2084 149 B.1.5 Cb-2299 149 B.1.15 Cb-2514 149 B.1.23 Cb-2085 150 B.1.5 Cb-2300 150 B.1.15 Cb-2515 150 B.1.23
Cb-2086 151 B.1.5 Cb-2301 151 B.1.15 Cb-2516 151 B.1.23
Cb-2087 152 B.1.5 Cb-2302 152 B.1.15 Cb-2517 152 B.1.23
Cb-2088 153 B.1.5 Cb-2303 153 B.1.15 Cb-2518 153 B.1.23
Cb-2089 154 B.1.5 Cb-2304 154 B.1.15 Cb-2519 154 B.1.23
Cb-2090 155 B.1.5 Cb-2305 155 B.1.15 Cb-2520 155 B.1.23
Cb-2091 156 B.1.5 Cb-2306 156 B.1.15 Cb-2521 156 B.1.23
Cb-2092 157 B.1.5 Cb-2307 157 B.1.15 Cb-2522 157 B.1.23
Cb-2093 158 B.1.5 Cb-2308 158 B.1.15 Cb-2523 158 B.1.23
Cb-2094 159 B.1.5 Cb-2309 159 B.1.15 Cb-2524 159 B.1.23
Cb-2095 160 B.1.5 Cb-2310 160 B.1.15 Cb-2525 160 B.1.23
Cb-2096 161 B.1.5 Cb-2311 161 B.1.15 Cb-2526 161 B.1.23
Cb-2097 162 B.1.5 Cb-2312 162 B.1.15 Cb-2527 162 B.1.23
Cb-2098 163 B.1.5 Cb-2313 163 B.1.15 Cb-2528 163 B.1.23
Cb-2099 164 B.1.5 Cb-2314 164 B.1.15 Cb-2529 164 B.1.23
Cb-2100 165 B.1.5 Cb-2315 165 B.1.15 Cb-2530 165 B.1.23
Cb-2101 166 B.1.5 Cb-2316 166 B.1.15 Cb-2531 166 B.1.23
Cb-2102 167 B.1.5 Cb-2317 167 B.1.15 Cb-2532 167 B.1.23
Cb-2103 168 B.1.5 Cb-2318 168 B.1.15 Cb-2533 168 B.1.23
Cb-2104 169 B.1.5 Cb-2319 169 B.1.15 Cb-2534 169 B.1.23
Cb-2105 170 B.1.5 Cb-2320 170 B.1.15 Cb-2535 170 B.1.23
Cb-2106 171 B.1.5 Cb-2321 171 B.1.15 Cb-2536 171 B.1.23
Cb-2107 172 B.1.5 Cb-2322 172 B.1.15 Cb-2537 172 B.1.23
Cb-2108 173 B.1.5 Cb-2323 173 B.1.15 Cb-2538 173 B.1.23
Cb-2109 174 B.1.5 Cb-2324 174 B.1.15 Cb-2539 174 B.1.23
Cb-2110 175 B.1.5 Cb-2325 175 B.1.15 Cb-2540 175 B.1.23
Cb-2111 176 B.1.5 Cb-2326 176 B.1.15 Cb-2541 176 B.1.23
Cb-2112 177 B.1.5 Cb-2327 177 B.1.15 Cb-2542 177 B.1.23
Cb-2113 178 B.1.5 Cb-2328 178 B.1.15 Cb-2543 178 B.1.23
Cb-2114 179 B.1.5 Cb-2329 179 B.1.15 Cb-2544 179 B.1.23
Cb-2115 180 B.1.5 Cb-2330 180 B.1.15 Cb-2545 180 B.1.23
Cb-2116 181 B.1.5 Cb-2331 181 B.1.15 Cb-2546 181 B.1.23
Cb-2117 182 B.1.5 Cb-2332 182 B.1.15 Cb-2547 182 B.1.23
Cb-2118 183 B.1.5 Cb-2333 183 B.1.15 Cb-2548 183 B.1.23
Cb-2119 184 B.1.5 Cb-2334 184 B.1.15 Cb-2549 184 B.1.23
Cb-2120 185 B.1.5 Cb-2335 185 B.1.15 Cb-2550 185 B.1.23
Cb-2121 186 B.1.5 Cb-2336 186 B.1.15 Cb-2551 186 B.1.23
Cb-2122 187 B.1.5 Cb-2337 187 B.1.15 Cb-2552 187 B.1.23
Cb-2123 188 B.1.5 Cb-2338 188 B.1.15 Cb-2553 188 B.1.23
Cb-2124 189 B.1.5 Cb-2339 189 B.1.15 Cb-2554 189 B.1.23
Cb-2125 190 B.1.5 Cb-2340 190 B.1.15 Cb-2555 190 B.1.23 Cb-2126 191 B.1.5 Cb-2341 191 B.1.15 Cb-2556 191 B.1.23
Cb-2127 192 B.1.5 Cb-2342 192 B.1.15 Cb-2557 192 B.1.23
Cb-2128 193 B.1.5 Cb-2343 193 B.1.15 Cb-2558 193 B.1.23
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Cb-2789 209 B.1.29 Cb-3004 209 C.1.4 Cb-3219 209 C.1.5
Cb-2790 210 B.1.29 Cb-3005 210 C.1.4 Cb-3220 210 C.1.5
Cb-2791 21 1 B.1.29 Cb-3006 211 C.1.4 Cb-3221 211 C.1.5
Cb-2792 212 B.1.29 Cb-3007 212 C.1.4 Cb-3222 212 C.1.5
Cb-2793 213 B.1.29 Cb-3008 213 C.1.4 Cb-3223 213 C.1.5
Cb-2794 214 B.1.29 Cb-3009 214 C.1.4 Cb-3224 214 C.1.5
Cb-2795 215 B.1.29 Cb-3010 215 C.1.4 Cb-3225 215 C.1.5
Cb-3226 1 D.1.4 Cb-3441 1 D.2.2 Cb-3656 1 G.5.1
Cb-3227 2 D.1.4 Cb-3442 2 D.2.2 Cb-3657 2 G.5.1
Cb-3228 3 D.1.4 Cb-3443 3 D.2.2 Cb-3658 3 G.5.1
Cb-3229 4 D.1.4 Cb-3444 4 D.2.2 Cb-3659 4 G.5.1
Cb-3230 5 D.1.4 Cb-3445 5 D.2.2 Cb-3660 5 G.5.1
Cb-3231 6 D.1.4 Cb-3446 6 D.2.2 Cb-3661 6 G.5.1 Cb-3232 7 D.1.4 Cb-3447 7 D.2.2 Cb-3662 7 G.5.1
Cb-3233 8 D.1.4 Cb-3448 8 D.2.2 Cb-3663 8 G.5.1
Cb-3234 9 D.1.4 Cb-3449 9 D.2.2 Cb-3664 9 G.5.1
Cb-3235 10 D.1.4 Cb-3450 10 D.2.2 Cb-3665 10 G.5.1
Cb-3236 11 D.1.4 Cb-3451 11 D.2.2 Cb-3666 11 G.5.1
Cb-3237 12 D.1.4 Cb-3452 12 D.2.2 Cb-3667 12 G.5.1
Cb-3238 13 D.1.4 Cb-3453 13 D.2.2 Cb-3668 13 G.5.1
Cb-3239 14 D.1.4 Cb-3454 14 D.2.2 Cb-3669 14 G.5.1
Cb-3240 15 D.1.4 Cb-3455 15 D.2.2 Cb-3670 15 G.5.1
Cb-3241 16 D.1.4 Cb-3456 16 D.2.2 Cb-3671 16 G.5.1
Cb-3242 17 D.1.4 Cb-3457 17 D.2.2 Cb-3672 17 G.5.1
Cb-3243 18 D.1.4 Cb-3458 18 D.2.2 Cb-3673 18 G.5.1
Cb-3244 19 D.1.4 Cb-3459 19 D.2.2 Cb-3674 19 G.5.1
Cb-3245 20 D.1.4 Cb-3460 20 D.2.2 Cb-3675 20 G.5.1
Cb-3246 21 D.1.4 Cb-3461 21 D.2.2 Cb-3676 21 G.5.1
Cb-3247 22 D.1.4 Cb-3462 22 D.2.2 Cb-3677 22 G.5.1
Cb-3248 23 D.1.4 Cb-3463 23 D.2.2 Cb-3678 23 G.5.1
Cb-3249 24 D.1.4 Cb-3464 24 D.2.2 Cb-3679 24 G.5.1
Cb-3250 25 D.1.4 Cb-3465 25 D.2.2 Cb-3680 25 G.5.1
Cb-3251 26 D.1.4 Cb-3466 26 D.2.2 Cb-3681 26 G.5.1
Cb-3252 27 D.1.4 Cb-3467 27 D.2.2 Cb-3682 27 G.5.1
Cb-3253 28 D.1.4 Cb-3468 28 D.2.2 Cb-3683 28 G.5.1
Cb-3254 29 D.1.4 Cb-3469 29 D.2.2 Cb-3684 29 G.5.1
Cb-3255 30 D.1.4 Cb-3470 30 D.2.2 Cb-3685 30 G.5.1
Cb-3256 31 D.1.4 Cb-3471 31 D.2.2 Cb-3686 31 G.5.1
Cb-3257 32 D.1.4 Cb-3472 32 D.2.2 Cb-3687 32 G.5.1
Cb-3258 33 D.1.4 Cb-3473 33 D.2.2 Cb-3688 33 G.5.1
Cb-3259 34 D.1.4 Cb-3474 34 D.2.2 Cb-3689 34 G.5.1
Cb-3260 35 D.1.4 Cb-3475 35 D.2.2 Cb-3690 35 G.5.1
Cb-3261 36 D.1.4 Cb-3476 36 D.2.2 Cb-3691 36 G.5.1
Cb-3262 37 D.1.4 Cb-3477 37 D.2.2 Cb-3692 37 G.5.1
Cb-3263 38 D.1.4 Cb-3478 38 D.2.2 Cb-3693 38 G.5.1
Cb-3264 39 D.1.4 Cb-3479 39 D.2.2 Cb-3694 39 G.5.1
Cb-3265 40 D.1.4 Cb-3480 40 D.2.2 Cb-3695 40 G.5.1
Cb-3266 41 D.1.4 Cb-3481 41 D.2.2 Cb-3696 41 G.5.1
Cb-3267 42 D.1.4 Cb-3482 42 D.2.2 Cb-3697 42 G.5.1
Cb-3268 43 D.1.4 Cb-3483 43 D.2.2 Cb-3698 43 G.5.1
Cb-3269 44 D.1.4 Cb-3484 44 D.2.2 Cb-3699 44 G.5.1
Cb-3270 45 D.1.4 Cb-3485 45 D.2.2 Cb-3700 45 G.5.1
Cb-3271 46 D.1.4 Cb-3486 46 D.2.2 Cb-3701 46 G.5.1
Cb-3272 47 D.1.4 Cb-3487 47 D.2.2 Cb-3702 47 G.5.1 Cb-3273 48 D.1.4 Cb-3488 48 D.2.2 Cb-3703 48 G.5.1
Cb-3274 49 D.1.4 Cb-3489 49 D.2.2 Cb-3704 49 G.5.1
Cb-3275 50 D.1.4 Cb-3490 50 D.2.2 Cb-3705 50 G.5.1
Cb-3276 51 D.1.4 Cb-3491 51 D.2.2 Cb-3706 51 G.5.1
Cb-3277 52 D.1.4 Cb-3492 52 D.2.2 Cb-3707 52 G.5.1
Cb-3278 53 D.1.4 Cb-3493 53 D.2.2 Cb-3708 53 G.5.1
Cb-3279 54 D.1.4 Cb-3494 54 D.2.2 Cb-3709 54 G.5.1
Cb-3280 55 D.1.4 Cb-3495 55 D.2.2 Cb-3710 55 G.5.1
Cb-3281 56 D.1.4 Cb-3496 56 D.2.2 Cb-3711 56 G.5.1
Cb-3282 57 D.1.4 Cb-3497 57 D.2.2 Cb-3712 57 G.5.1
Cb-3283 58 D.1.4 Cb-3498 58 D.2.2 Cb-3713 58 G.5.1
Cb-3284 59 D.1.4 Cb-3499 59 D.2.2 Cb-3714 59 G.5.1
Cb-3285 60 D.1.4 Cb-3500 60 D.2.2 Cb-3715 60 G.5.1
Cb-3286 61 D.1.4 Cb-3501 61 D.2.2 Cb-3716 61 G.5.1
Cb-3287 62 D.1.4 Cb-3502 62 D.2.2 Cb-3717 62 G.5.1
Cb-3288 63 D.1.4 Cb-3503 63 D.2.2 Cb-3718 63 G.5.1
Cb-3289 64 D.1.4 Cb-3504 64 D.2.2 Cb-3719 64 G.5.1
Cb-3290 65 D.1.4 Cb-3505 65 D.2.2 Cb-3720 65 G.5.1
Cb-3291 66 D.1.4 Cb-3506 66 D.2.2 Cb-3721 66 G.5.1
Cb-3292 67 D.1.4 Cb-3507 67 D.2.2 Cb-3722 67 G.5.1
Cb-3293 68 D.1.4 Cb-3508 68 D.2.2 Cb-3723 68 G.5.1
Cb-3294 69 D.1.4 Cb-3509 69 D.2.2 Cb-3724 69 G.5.1
Cb-3295 70 D.1.4 Cb-3510 70 D.2.2 Cb-3725 70 G.5.1
Cb-3296 71 D.1.4 Cb-3511 71 D.2.2 Cb-3726 71 G.5.1
Cb-3297 72 D.1.4 Cb-3512 72 D.2.2 Cb-3727 72 G.5.1
Cb-3298 73 D.1.4 Cb-3513 73 D.2.2 Cb-3728 73 G.5.1
Cb-3299 74 D.1.4 Cb-3514 74 D.2.2 Cb-3729 74 G.5.1
Cb-3300 75 D.1.4 Cb-3515 75 D.2.2 Cb-3730 75 G.5.1
Cb-3301 76 D.1.4 Cb-3516 76 D.2.2 Cb-3731 76 G.5.1
Cb-3302 77 D.1.4 Cb-3517 77 D.2.2 Cb-3732 77 G.5.1
Cb-3303 78 D.1.4 Cb-3518 78 D.2.2 Cb-3733 78 G.5.1
Cb-3304 79 D.1.4 Cb-3519 79 D.2.2 Cb-3734 79 G.5.1
Cb-3305 80 D.1.4 Cb-3520 80 D.2.2 Cb-3735 80 G.5.1
Cb-3306 81 D.1.4 Cb-3521 81 D.2.2 Cb-3736 81 G.5.1
Cb-3307 82 D.1.4 Cb-3522 82 D.2.2 Cb-3737 82 G.5.1
Cb-3308 83 D.1.4 Cb-3523 83 D.2.2 Cb-3738 83 G.5.1
Cb-3309 84 D.1.4 Cb-3524 84 D.2.2 Cb-3739 84 G.5.1
Cb-3310 85 D.1.4 Cb-3525 85 D.2.2 Cb-3740 85 G.5.1
Cb-331 1 86 D.1.4 Cb-3526 86 D.2.2 Cb-3741 86 G.5.1
Cb-3312 87 D.1.4 Cb-3527 87 D.2.2 Cb-3742 87 G.5.1
Cb-3313 88 D.1.4 Cb-3528 88 D.2.2 Cb-3743 88 G.5.1 Cb-3314 89 D.1.4 Cb-3529 89 D.2.2 Cb-3744 89 G.5.1
Cb-3315 90 D.1.4 Cb-3530 90 D.2.2 Cb-3745 90 G.5.1
Cb-3316 91 D.1.4 Cb-3531 91 D.2.2 Cb-3746 91 G.5.1
Cb-3317 92 D.1.4 Cb-3532 92 D.2.2 Cb-3747 92 G.5.1
Cb-3318 93 D.1.4 Cb-3533 93 D.2.2 Cb-3748 93 G.5.1
Cb-3319 94 D.1.4 Cb-3534 94 D.2.2 Cb-3749 94 G.5.1
Cb-3320 95 D.1.4 Cb-3535 95 D.2.2 Cb-3750 95 G.5.1
Cb-3321 96 D.1.4 Cb-3536 96 D.2.2 Cb-3751 96 G.5.1
Cb-3322 97 D.1.4 Cb-3537 97 D.2.2 Cb-3752 97 G.5.1
Cb-3323 98 D.1.4 Cb-3538 98 D.2.2 Cb-3753 98 G.5.1
Cb-3324 99 D.1.4 Cb-3539 99 D.2.2 Cb-3754 99 G.5.1
Cb-3325 100 D.1.4 Cb-3540 100 D.2.2 Cb-3755 100 G.5.1
Cb-3326 101 D.1.4 Cb-3541 101 D.2.2 Cb-3756 101 G.5.1
Cb-3327 102 D.1.4 Cb-3542 102 D.2.2 Cb-3757 102 G.5.1
Cb-3328 103 D.1.4 Cb-3543 103 D.2.2 Cb-3758 103 G.5.1
Cb-3329 104 D.1.4 Cb-3544 104 D.2.2 Cb-3759 104 G.5.1
Cb-3330 105 D.1.4 Cb-3545 105 D.2.2 Cb-3760 105 G.5.1
Cb-3331 106 D.1.4 Cb-3546 106 D.2.2 Cb-3761 106 G.5.1
Cb-3332 107 D.1.4 Cb-3547 107 D.2.2 Cb-3762 107 G.5.1
Cb-3333 108 D.1.4 Cb-3548 108 D.2.2 Cb-3763 108 G.5.1
Cb-3334 109 D.1.4 Cb-3549 109 D.2.2 Cb-3764 109 G.5.1
Cb-3335 110 D.1.4 Cb-3550 110 D.2.2 Cb-3765 110 G.5.1
Cb-3336 111 D.1.4 Cb-3551 111 D.2.2 Cb-3766 111 G.5.1
Cb-3337 112 D.1.4 Cb-3552 112 D.2.2 Cb-3767 112 G.5.1
Cb-3338 113 D.1.4 Cb-3553 113 D.2.2 Cb-3768 113 G.5.1
Cb-3339 114 D.1.4 Cb-3554 114 D.2.2 Cb-3769 114 G.5.1
Cb-3340 115 D.1.4 Cb-3555 115 D.2.2 Cb-3770 115 G.5.1
Cb-3341 116 D.1.4 Cb-3556 116 D.2.2 Cb-3771 116 G.5.1
Cb-3342 117 D.1.4 Cb-3557 117 D.2.2 Cb-3772 117 G.5.1
Cb-3343 118 D.1.4 Cb-3558 118 D.2.2 Cb-3773 118 G.5.1
Cb-3344 119 D.1.4 Cb-3559 119 D.2.2 Cb-3774 119 G.5.1
Cb-3345 120 D.1.4 Cb-3560 120 D.2.2 Cb-3775 120 G.5.1
Cb-3346 121 D.1.4 Cb-3561 121 D.2.2 Cb-3776 121 G.5.1
Cb-3347 122 D.1.4 Cb-3562 122 D.2.2 Cb-3777 122 G.5.1
Cb-3348 123 D.1.4 Cb-3563 123 D.2.2 Cb-3778 123 G.5.1
Cb-3349 124 D.1.4 Cb-3564 124 D.2.2 Cb-3779 124 G.5.1
Cb-3350 125 D.1.4 Cb-3565 125 D.2.2 Cb-3780 125 G.5.1
Cb-3351 126 D.1.4 Cb-3566 126 D.2.2 Cb-3781 126 G.5.1
Cb-3352 127 D.1.4 Cb-3567 127 D.2.2 Cb-3782 127 G.5.1
Cb-3353 128 D.1.4 Cb-3568 128 D.2.2 Cb-3783 128 G.5.1
Cb-3354 129 D.1.4 Cb-3569 129 D.2.2 Cb-3784 129 G.5.1 Cb-3355 130 D.1 .4 Cb-3570 130 D.2.2 Cb-3785 130 G.5.1
Cb-3356 131 D.1 .4 Cb-3571 131 D.2.2 Cb-3786 131 G.5.1
Cb-3357 132 D.1 .4 Cb-3572 132 D.2.2 Cb-3787 132 G.5.1
Cb-3358 133 D.1 .4 Cb-3573 133 D.2.2 Cb-3788 133 G.5.1
Cb-3359 134 D.1 .4 Cb-3574 134 D.2.2 Cb-3789 134 G.5.1
Cb-3360 135 D.1 .4 Cb-3575 135 D.2.2 Cb-3790 135 G.5.1
Cb-3361 136 D.1 .4 Cb-3576 136 D.2.2 Cb-3791 136 G.5.1
Cb-3362 137 D.1 .4 Cb-3577 137 D.2.2 Cb-3792 137 G.5.1
Cb-3363 138 D.1 .4 Cb-3578 138 D.2.2 Cb-3793 138 G.5.1
Cb-3364 139 D.1 .4 Cb-3579 139 D.2.2 Cb-3794 139 G.5.1
Cb-3365 140 D.1 .4 Cb-3580 140 D.2.2 Cb-3795 140 G.5.1
Cb-3366 141 D.1 .4 Cb-3581 141 D.2.2 Cb-3796 141 G.5.1
Cb-3367 142 D.1 .4 Cb-3582 142 D.2.2 Cb-3797 142 G.5.1
Cb-3368 143 D.1 .4 Cb-3583 143 D.2.2 Cb-3798 143 G.5.1
Cb-3369 144 D.1 .4 Cb-3584 144 D.2.2 Cb-3799 144 G.5.1
Cb-3370 145 D.1 .4 Cb-3585 145 D.2.2 Cb-3800 145 G.5.1
Cb-3371 146 D.1 .4 Cb-3586 146 D.2.2 Cb-3801 146 G.5.1
Cb-3372 147 D.1 .4 Cb-3587 147 D.2.2 Cb-3802 147 G.5.1
Cb-3373 148 D.1 .4 Cb-3588 148 D.2.2 Cb-3803 148 G.5.1
Cb-3374 149 D.1 .4 Cb-3589 149 D.2.2 Cb-3804 149 G.5.1
Cb-3375 150 D.1 .4 Cb-3590 150 D.2.2 Cb-3805 150 G.5.1
Cb-3376 151 D.1 .4 Cb-3591 151 D.2.2 Cb-3806 151 G.5.1
Cb-3377 152 D.1 .4 Cb-3592 152 D.2.2 Cb-3807 152 G.5.1
Cb-3378 153 D.1 .4 Cb-3593 153 D.2.2 Cb-3808 153 G.5.1
Cb-3379 154 D.1 .4 Cb-3594 154 D.2.2 Cb-3809 154 G.5.1
Cb-3380 155 D.1 .4 Cb-3595 155 D.2.2 Cb-3810 155 G.5.1
Cb-3381 156 D.1 .4 Cb-3596 156 D.2.2 Cb-381 1 156 G.5.1
Cb-3382 157 D.1 .4 Cb-3597 157 D.2.2 Cb-3812 157 G.5.1
Cb-3383 158 D.1 .4 Cb-3598 158 D.2.2 Cb-3813 158 G.5.1
Cb-3384 159 D.1 .4 Cb-3599 159 D.2.2 Cb-3814 159 G.5.1
Cb-3385 160 D.1 .4 Cb-3600 160 D.2.2 Cb-3815 160 G.5.1
Cb-3386 161 D.1 .4 Cb-3601 161 D.2.2 Cb-3816 161 G.5.1
Cb-3387 162 D.1 .4 Cb-3602 162 D.2.2 Cb-3817 162 G.5.1
Cb-3388 163 D.1 .4 Cb-3603 163 D.2.2 Cb-3818 163 G.5.1
Cb-3389 164 D.1 .4 Cb-3604 164 D.2.2 Cb-3819 164 G.5.1
Cb-3390 165 D.1 .4 Cb-3605 165 D.2.2 Cb-3820 165 G.5.1
Cb-3391 166 D.1 .4 Cb-3606 166 D.2.2 Cb-3821 166 G.5.1
Cb-3392 167 D.1 .4 Cb-3607 167 D.2.2 Cb-3822 167 G.5.1
Cb-3393 168 D.1 .4 Cb-3608 168 D.2.2 Cb-3823 168 G.5.1
Cb-3394 169 D.1 .4 Cb-3609 169 D.2.2 Cb-3824 169 G.5.1
Cb-3395 170 D.1 .4 Cb-3610 170 D.2.2 Cb-3825 170 G.5.1 Cb-3396 171 D.1 .4 Cb-361 1 171 D.2.2 Cb-3826 171 G.5.1
Cb-3397 172 D.1 .4 Cb-3612 172 D.2.2 Cb-3827 172 G.5.1
Cb-3398 173 D.1 .4 Cb-3613 173 D.2.2 Cb-3828 173 G.5.1
Cb-3399 174 D.1 .4 Cb-3614 174 D.2.2 Cb-3829 174 G.5.1
Cb-3400 175 D.1 .4 Cb-3615 175 D.2.2 Cb-3830 175 G.5.1
Cb-3401 176 D.1 .4 Cb-3616 176 D.2.2 Cb-3831 176 G.5.1
Cb-3402 177 D.1 .4 Cb-3617 177 D.2.2 Cb-3832 177 G.5.1
Cb-3403 178 D.1 .4 Cb-3618 178 D.2.2 Cb-3833 178 G.5.1
Cb-3404 179 D.1 .4 Cb-3619 179 D.2.2 Cb-3834 179 G.5.1
Cb-3405 180 D.1 .4 Cb-3620 180 D.2.2 Cb-3835 180 G.5.1
Cb-3406 181 D.1 .4 Cb-3621 181 D.2.2 Cb-3836 181 G.5.1
Cb-3407 182 D.1 .4 Cb-3622 182 D.2.2 Cb-3837 182 G.5.1
Cb-3408 183 D.1 .4 Cb-3623 183 D.2.2 Cb-3838 183 G.5.1
Cb-3409 184 D.1 .4 Cb-3624 184 D.2.2 Cb-3839 184 G.5.1
Cb-3410 185 D.1 .4 Cb-3625 185 D.2.2 Cb-3840 185 G.5.1
Cb-341 1 186 D.1 .4 Cb-3626 186 D.2.2 Cb-3841 186 G.5.1
Cb-3412 187 D.1 .4 Cb-3627 187 D.2.2 Cb-3842 187 G.5.1
Cb-3413 188 D.1 .4 Cb-3628 188 D.2.2 Cb-3843 188 G.5.1
Cb-3414 189 D.1 .4 Cb-3629 189 D.2.2 Cb-3844 189 G.5.1
Cb-3415 190 D.1 .4 Cb-3630 190 D.2.2 Cb-3845 190 G.5.1
Cb-3416 191 D.1 .4 Cb-3631 191 D.2.2 Cb-3846 191 G.5.1
Cb-3417 192 D.1 .4 Cb-3632 192 D.2.2 Cb-3847 192 G.5.1
Cb-3418 193 D.1 .4 Cb-3633 193 D.2.2 Cb-3848 193 G.5.1
Cb-3419 194 D.1 .4 Cb-3634 194 D.2.2 Cb-3849 194 G.5.1
Cb-3420 195 D.1 .4 Cb-3635 195 D.2.2 Cb-3850 195 G.5.1
Cb-3421 196 D.1 .4 Cb-3636 196 D.2.2 Cb-3851 196 G.5.1
Cb-3422 197 D.1 .4 Cb-3637 197 D.2.2 Cb-3852 197 G.5.1
Cb-3423 198 D.1 .4 Cb-3638 198 D.2.2 Cb-3853 198 G.5.1
Cb-3424 199 D.1 .4 Cb-3639 199 D.2.2 Cb-3854 199 G.5.1
Cb-3425 200 D.1 .4 Cb-3640 200 D.2.2 Cb-3855 200 G.5.1
Cb-3426 201 D.1 .4 Cb-3641 201 D.2.2 Cb-3856 201 G.5.1
Cb-3427 202 D.1 .4 Cb-3642 202 D.2.2 Cb-3857 202 G.5.1
Cb-3428 203 D.1 .4 Cb-3643 203 D.2.2 Cb-3858 203 G.5.1
Cb-3429 204 D.1 .4 Cb-3644 204 D.2.2 Cb-3859 204 G.5.1
Cb-3430 205 D.1 .4 Cb-3645 205 D.2.2 Cb-3860 205 G.5.1
Cb-3431 206 D.1 .4 Cb-3646 206 D.2.2 Cb-3861 206 G.5.1
Cb-3432 207 D.1 .4 Cb-3647 207 D.2.2 Cb-3862 207 G.5.1
Cb-3433 208 D.1 .4 Cb-3648 208 D.2.2 Cb-3863 208 G.5.1
Cb-3434 209 D.1 .4 Cb-3649 209 D.2.2 Cb-3864 209 G.5.1
Cb-3435 210 D.1 .4 Cb-3650 210 D.2.2 Cb-3865 210 G.5.1
Cb-3436 21 1 D.1 .4 Cb-3651 21 1 D.2.2 Cb-3866 21 1 G.5.1 Cb-3437 212 D.1.4 Cb-3652 212 D.2.2 Cb-3867 212 G.5.1
Cb-3438 213 D.1.4 Cb-3653 213 D.2.2 Cb-3868 213 G.5.1
Cb-3439 214 D.1.4 Cb-3654 214 D.2.2 Cb-3869 214 G.5.1
Cb-3440 215 D.1.4 Cb-3655 215 D.2.2 Cb-3870 215 G.5.1
Cb-3871 1 H.2.2 Cb-4086 1 H.3.2 Cb-4301 1 G.3.7
Cb-3872 2 H.2.2 Cb-4087 2 H.3.2 Cb-4302 2 G.3.7
Cb-3873 3 H.2.2 Cb-4088 3 H.3.2 Cb-4303 3 G.3.7
Cb-3874 4 H.2.2 Cb-4089 4 H.3.2 Cb-4304 4 G.3.7
Cb-3875 5 H.2.2 Cb-4090 5 H.3.2 Cb-4305 5 G.3.7
Cb-3876 6 H.2.2 Cb-4091 6 H.3.2 Cb-4306 6 G.3.7
Cb-3877 7 H.2.2 Cb-4092 7 H.3.2 Cb-4307 7 G.3.7
Cb-3878 8 H.2.2 Cb-4093 8 H.3.2 Cb-4308 8 G.3.7
Cb-3879 9 H.2.2 Cb-4094 9 H.3.2 Cb-4309 9 G.3.7
Cb-3880 10 H.2.2 Cb-4095 10 H.3.2 Cb-4310 10 G.3.7
Cb-3881 1 1 H.2.2 Cb-4096 1 1 H.3.2 Cb-4311 1 1 G.3.7
Cb-3882 12 H.2.2 Cb-4097 12 H.3.2 Cb-4312 12 G.3.7
Cb-3883 13 H.2.2 Cb-4098 13 H.3.2 Cb-4313 13 G.3.7
Cb-3884 14 H.2.2 Cb-4099 14 H.3.2 Cb-4314 14 G.3.7
Cb-3885 15 H.2.2 Cb-4100 15 H.3.2 Cb-4315 15 G.3.7
Cb-3886 16 H.2.2 Cb-4101 16 H.3.2 Cb-4316 16 G.3.7
Cb-3887 17 H.2.2 Cb-4102 17 H.3.2 Cb-4317 17 G.3.7
Cb-3888 18 H.2.2 Cb-4103 18 H.3.2 Cb-4318 18 G.3.7
Cb-3889 19 H.2.2 Cb-4104 19 H.3.2 Cb-4319 19 G.3.7
Cb-3890 20 H.2.2 Cb-4105 20 H.3.2 Cb-4320 20 G.3.7
Cb-3891 21 H.2.2 Cb-4106 21 H.3.2 Cb-4321 21 G.3.7
Cb-3892 22 H.2.2 Cb-4107 22 H.3.2 Cb-4322 22 G.3.7
Cb-3893 23 H.2.2 Cb-4108 23 H.3.2 Cb-4323 23 G.3.7
Cb-3894 24 H.2.2 Cb-4109 24 H.3.2 Cb-4324 24 G.3.7
Cb-3895 25 H.2.2 Cb-41 10 25 H.3.2 Cb-4325 25 G.3.7
Cb-3896 26 H.2.2 Cb-41 11 26 H.3.2 Cb-4326 26 G.3.7
Cb-3897 27 H.2.2 Cb-41 12 27 H.3.2 Cb-4327 27 G.3.7
Cb-3898 28 H.2.2 Cb-41 13 28 H.3.2 Cb-4328 28 G.3.7
Cb-3899 29 H.2.2 Cb-41 14 29 H.3.2 Cb-4329 29 G.3.7
Cb-3900 30 H.2.2 Cb-41 15 30 H.3.2 Cb-4330 30 G.3.7
Cb-3901 31 H.2.2 Cb-41 16 31 H.3.2 Cb-4331 31 G.3.7
Cb-3902 32 H.2.2 Cb-41 17 32 H.3.2 Cb-4332 32 G.3.7
Cb-3903 33 H.2.2 Cb-41 18 33 H.3.2 Cb-4333 33 G.3.7
Cb-3904 34 H.2.2 Cb-41 19 34 H.3.2 Cb-4334 34 G.3.7
Cb-3905 35 H.2.2 Cb-4120 35 H.3.2 Cb-4335 35 G.3.7
Cb-3906 36 H.2.2 Cb-4121 36 H.3.2 Cb-4336 36 G.3.7
Cb-3907 37 H.2.2 Cb-4122 37 H.3.2 Cb-4337 37 G.3.7 Cb-3908 38 H.2.2 Cb-4123 38 H .3.2 Cb-4338 38 G.3.7
Cb-3909 39 H.2.2 Cb-4124 39 H .3.2 Cb-4339 39 G.3.7
Cb-3910 40 H.2.2 Cb-4125 40 H .3.2 Cb-4340 40 G.3.7
Cb-391 1 41 H.2.2 Cb-4126 41 H .3.2 Cb-4341 41 G.3.7
Cb-3912 42 H.2.2 Cb-4127 42 H .3.2 Cb-4342 42 G.3.7
Cb-3913 43 H.2.2 Cb-4128 43 H .3.2 Cb-4343 43 G.3.7
Cb-3914 44 H.2.2 Cb-4129 44 H .3.2 Cb-4344 44 G.3.7
Cb-3915 45 H.2.2 Cb-4130 45 H .3.2 Cb-4345 45 G.3.7
Cb-3916 46 H.2.2 Cb-4131 46 H .3.2 Cb-4346 46 G.3.7
Cb-3917 47 H.2.2 Cb-4132 47 H .3.2 Cb-4347 47 G.3.7
Cb-3918 48 H.2.2 Cb-4133 48 H .3.2 Cb-4348 48 G.3.7
Cb-3919 49 H.2.2 Cb-4134 49 H .3.2 Cb-4349 49 G.3.7
Cb-3920 50 H.2.2 Cb-4135 50 H .3.2 Cb-4350 50 G.3.7
Cb-3921 51 H.2.2 Cb-4136 51 H .3.2 Cb-4351 51 G.3.7
Cb-3922 52 H.2.2 Cb-4137 52 H .3.2 Cb-4352 52 G.3.7
Cb-3923 53 H.2.2 Cb-4138 53 H .3.2 Cb-4353 53 G.3.7
Cb-3924 54 H.2.2 Cb-4139 54 H .3.2 Cb-4354 54 G.3.7
Cb-3925 55 H.2.2 Cb-4140 55 H .3.2 Cb-4355 55 G.3.7
Cb-3926 56 H.2.2 Cb-4141 56 H .3.2 Cb-4356 56 G.3.7
Cb-3927 57 H.2.2 Cb-4142 57 H .3.2 Cb-4357 57 G.3.7
Cb-3928 58 H.2.2 Cb-4143 58 H .3.2 Cb-4358 58 G.3.7
Cb-3929 59 H.2.2 Cb-4144 59 H .3.2 Cb-4359 59 G.3.7
Cb-3930 60 H.2.2 Cb-4145 60 H .3.2 Cb-4360 60 G.3.7
Cb-3931 61 H.2.2 Cb-4146 61 H .3.2 Cb-4361 61 G.3.7
Cb-3932 62 H.2.2 Cb-4147 62 H .3.2 Cb-4362 62 G.3.7
Cb-3933 63 H.2.2 Cb-4148 63 H .3.2 Cb-4363 63 G.3.7
Cb-3934 64 H.2.2 Cb-4149 64 H .3.2 Cb-4364 64 G.3.7
Cb-3935 65 H.2.2 Cb-4150 65 H .3.2 Cb-4365 65 G.3.7
Cb-3936 66 H.2.2 Cb-4151 66 H .3.2 Cb-4366 66 G.3.7
Cb-3937 67 H.2.2 Cb-4152 67 H .3.2 Cb-4367 67 G.3.7
Cb-3938 68 H.2.2 Cb-4153 68 H .3.2 Cb-4368 68 G.3.7
Cb-3939 69 H.2.2 Cb-4154 69 H .3.2 Cb-4369 69 G.3.7
Cb-3940 70 H.2.2 Cb-4155 70 H .3.2 Cb-4370 70 G.3.7
Cb-3941 71 H.2.2 Cb-4156 71 H .3.2 Cb-4371 71 G.3.7
Cb-3942 72 H.2.2 Cb-4157 72 H .3.2 Cb-4372 72 G.3.7
Cb-3943 73 H.2.2 Cb-4158 73 H .3.2 Cb-4373 73 G.3.7
Cb-3944 74 H.2.2 Cb-4159 74 H .3.2 Cb-4374 74 G.3.7
Cb-3945 75 H.2.2 Cb-4160 75 H .3.2 Cb-4375 75 G.3.7
Cb-3946 76 H.2.2 Cb-4161 76 H .3.2 Cb-4376 76 G.3.7
Cb-3947 77 H.2.2 Cb-4162 77 H .3.2 Cb-4377 77 G.3.7
Cb-3948 78 H.2.2 Cb-4163 78 H .3.2 Cb-4378 78 G.3.7 Cb-3949 79 H.2.2 Cb-4164 79 H.3.2 Cb-4379 79 G.3.7
Cb-3950 80 H.2.2 Cb-4165 80 H.3.2 Cb-4380 80 G.3.7
Cb-3951 81 H.2.2 Cb-4166 81 H.3.2 Cb-4381 81 G.3.7
Cb-3952 82 H.2.2 Cb-4167 82 H.3.2 Cb-4382 82 G.3.7
Cb-3953 83 H.2.2 Cb-4168 83 H.3.2 Cb-4383 83 G.3.7
Cb-3954 84 H.2.2 Cb-4169 84 H.3.2 Cb-4384 84 G.3.7
Cb-3955 85 H.2.2 Cb-4170 85 H.3.2 Cb-4385 85 G.3.7
Cb-3956 86 H.2.2 Cb-4171 86 H.3.2 Cb-4386 86 G.3.7
Cb-3957 87 H.2.2 Cb-4172 87 H.3.2 Cb-4387 87 G.3.7
Cb-3958 88 H.2.2 Cb-4173 88 H.3.2 Cb-4388 88 G.3.7
Cb-3959 89 H.2.2 Cb-4174 89 H.3.2 Cb-4389 89 G.3.7
Cb-3960 90 H.2.2 Cb-4175 90 H.3.2 Cb-4390 90 G.3.7
Cb-3961 91 H.2.2 Cb-4176 91 H.3.2 Cb-4391 91 G.3.7
Cb-3962 92 H.2.2 Cb-4177 92 H.3.2 Cb-4392 92 G.3.7
Cb-3963 93 H.2.2 Cb-4178 93 H.3.2 Cb-4393 93 G.3.7
Cb-3964 94 H.2.2 Cb-4179 94 H.3.2 Cb-4394 94 G.3.7
Cb-3965 95 H.2.2 Cb-4180 95 H.3.2 Cb-4395 95 G.3.7
Cb-3966 96 H.2.2 Cb-4181 96 H.3.2 Cb-4396 96 G.3.7
Cb-3967 97 H.2.2 Cb-4182 97 H.3.2 Cb-4397 97 G.3.7
Cb-3968 98 H.2.2 Cb-4183 98 H.3.2 Cb-4398 98 G.3.7
Cb-3969 99 H.2.2 Cb-4184 99 H.3.2 Cb-4399 99 G.3.7
Cb-3970 100 H.2.2 Cb-4185 100 H.3.2 Cb-4400 100 G.3.7
Cb-3971 101 H.2.2 Cb-4186 101 H.3.2 Cb-4401 101 G.3.7
Cb-3972 102 H.2.2 Cb-4187 102 H.3.2 Cb-4402 102 G.3.7
Cb-3973 103 H.2.2 Cb-4188 103 H.3.2 Cb-4403 103 G.3.7
Cb-3974 104 H.2.2 Cb-4189 104 H.3.2 Cb-4404 104 G.3.7
Cb-3975 105 H.2.2 Cb-4190 105 H.3.2 Cb-4405 105 G.3.7
Cb-3976 106 H.2.2 Cb-4191 106 H.3.2 Cb-4406 106 G.3.7
Cb-3977 107 H.2.2 Cb-4192 107 H.3.2 Cb-4407 107 G.3.7
Cb-3978 108 H.2.2 Cb-4193 108 H.3.2 Cb-4408 108 G.3.7
Cb-3979 109 H.2.2 Cb-4194 109 H.3.2 Cb-4409 109 G.3.7
Cb-3980 110 H.2.2 Cb-4195 110 H.3.2 Cb-4410 110 G.3.7
Cb-3981 111 H.2.2 Cb-4196 111 H.3.2 Cb-4411 111 G.3.7
Cb-3982 112 H.2.2 Cb-4197 112 H.3.2 Cb-4412 112 G.3.7
Cb-3983 113 H.2.2 Cb-4198 113 H.3.2 Cb-4413 113 G.3.7
Cb-3984 114 H.2.2 Cb-4199 114 H.3.2 Cb-4414 114 G.3.7
Cb-3985 115 H.2.2 Cb-4200 115 H.3.2 Cb-4415 115 G.3.7
Cb-3986 116 H.2.2 Cb-4201 116 H.3.2 Cb-4416 116 G.3.7
Cb-3987 117 H.2.2 Cb-4202 117 H.3.2 Cb-4417 117 G.3.7
Cb-3988 118 H.2.2 Cb-4203 118 H.3.2 Cb-4418 118 G.3.7
Cb-3989 119 H.2.2 Cb-4204 119 H.3.2 Cb-4419 119 G.3.7 Cb-3990 120 H.2.2 Cb-4205 120 H .3.2 Cb-4420 120 G.3.7
Cb-3991 121 H.2.2 Cb-4206 121 H .3.2 Cb-4421 121 G.3.7
Cb-3992 122 H.2.2 Cb-4207 122 H .3.2 Cb-4422 122 G.3.7
Cb-3993 123 H.2.2 Cb-4208 123 H .3.2 Cb-4423 123 G.3.7
Cb-3994 124 H.2.2 Cb-4209 124 H .3.2 Cb-4424 124 G.3.7
Cb-3995 125 H.2.2 Cb-4210 125 H .3.2 Cb-4425 125 G.3.7
Cb-3996 126 H.2.2 Cb-421 1 126 H .3.2 Cb-4426 126 G.3.7
Cb-3997 127 H.2.2 Cb-4212 127 H .3.2 Cb-4427 127 G.3.7
Cb-3998 128 H.2.2 Cb-4213 128 H .3.2 Cb-4428 128 G.3.7
Cb-3999 129 H.2.2 Cb-4214 129 H .3.2 Cb-4429 129 G.3.7
Cb-4000 130 H.2.2 Cb-4215 130 H .3.2 Cb-4430 130 G.3.7
Cb-4001 131 H.2.2 Cb-4216 131 H .3.2 Cb-4431 131 G.3.7
Cb-4002 132 H.2.2 Cb-4217 132 H .3.2 Cb-4432 132 G.3.7
Cb-4003 133 H.2.2 Cb-4218 133 H .3.2 Cb-4433 133 G.3.7
Cb-4004 134 H.2.2 Cb-4219 134 H .3.2 Cb-4434 134 G.3.7
Cb-4005 135 H.2.2 Cb-4220 135 H .3.2 Cb-4435 135 G.3.7
Cb-4006 136 H.2.2 Cb-4221 136 H .3.2 Cb-4436 136 G.3.7
Cb-4007 137 H.2.2 Cb-4222 137 H .3.2 Cb-4437 137 G.3.7
Cb-4008 138 H.2.2 Cb-4223 138 H .3.2 Cb-4438 138 G.3.7
Cb-4009 139 H.2.2 Cb-4224 139 H .3.2 Cb-4439 139 G.3.7
Cb-4010 140 H.2.2 Cb-4225 140 H .3.2 Cb-4440 140 G.3.7
Cb-401 1 141 H.2.2 Cb-4226 141 H .3.2 Cb-4441 141 G.3.7
Cb-4012 142 H.2.2 Cb-4227 142 H .3.2 Cb-4442 142 G.3.7
Cb-4013 143 H.2.2 Cb-4228 143 H .3.2 Cb-4443 143 G.3.7
Cb-4014 144 H.2.2 Cb-4229 144 H .3.2 Cb-4444 144 G.3.7
Cb-4015 145 H.2.2 Cb-4230 145 H .3.2 Cb-4445 145 G.3.7
Cb-4016 146 H.2.2 Cb-4231 146 H .3.2 Cb-4446 146 G.3.7
Cb-4017 147 H.2.2 Cb-4232 147 H .3.2 Cb-4447 147 G.3.7
Cb-4018 148 H.2.2 Cb-4233 148 H .3.2 Cb-4448 148 G.3.7
Cb-4019 149 H.2.2 Cb-4234 149 H .3.2 Cb-4449 149 G.3.7
Cb-4020 150 H.2.2 Cb-4235 150 H .3.2 Cb-4450 150 G.3.7
Cb-4021 151 H.2.2 Cb-4236 151 H .3.2 Cb-4451 151 G.3.7
Cb-4022 152 H.2.2 Cb-4237 152 H .3.2 Cb-4452 152 G.3.7
Cb-4023 153 H.2.2 Cb-4238 153 H .3.2 Cb-4453 153 G.3.7
Cb-4024 154 H.2.2 Cb-4239 154 H .3.2 Cb-4454 154 G.3.7
Cb-4025 155 H.2.2 Cb-4240 155 H .3.2 Cb-4455 155 G.3.7
Cb-4026 156 H.2.2 Cb-4241 156 H .3.2 Cb-4456 156 G.3.7
Cb-4027 157 H.2.2 Cb-4242 157 H .3.2 Cb-4457 157 G.3.7
Cb-4028 158 H.2.2 Cb-4243 158 H .3.2 Cb-4458 158 G.3.7
Cb-4029 159 H.2.2 Cb-4244 159 H .3.2 Cb-4459 159 G.3.7
Cb-4030 160 H.2.2 Cb-4245 160 H .3.2 Cb-4460 160 G.3.7 Cb-4031 161 H.2.2 Cb-4246 161 H .3.2 Cb-4461 161 G.3.7
Cb-4032 162 H.2.2 Cb-4247 162 H .3.2 Cb-4462 162 G.3.7
Cb-4033 163 H.2.2 Cb-4248 163 H .3.2 Cb-4463 163 G.3.7
Cb-4034 164 H.2.2 Cb-4249 164 H .3.2 Cb-4464 164 G.3.7
Cb-4035 165 H.2.2 Cb-4250 165 H .3.2 Cb-4465 165 G.3.7
Cb-4036 166 H.2.2 Cb-4251 166 H .3.2 Cb-4466 166 G.3.7
Cb-4037 167 H.2.2 Cb-4252 167 H .3.2 Cb-4467 167 G.3.7
Cb-4038 168 H.2.2 Cb-4253 168 H .3.2 Cb-4468 168 G.3.7
Cb-4039 169 H.2.2 Cb-4254 169 H .3.2 Cb-4469 169 G.3.7
Cb-4040 170 H.2.2 Cb-4255 170 H .3.2 Cb-4470 170 G.3.7
Cb-4041 171 H.2.2 Cb-4256 171 H .3.2 Cb-4471 171 G.3.7
Cb-4042 172 H.2.2 Cb-4257 172 H .3.2 Cb-4472 172 G.3.7
Cb-4043 173 H.2.2 Cb-4258 173 H .3.2 Cb-4473 173 G.3.7
Cb-4044 174 H.2.2 Cb-4259 174 H .3.2 Cb-4474 174 G.3.7
Cb-4045 175 H.2.2 Cb-4260 175 H .3.2 Cb-4475 175 G.3.7
Cb-4046 176 H.2.2 Cb-4261 176 H .3.2 Cb-4476 176 G.3.7
Cb-4047 177 H.2.2 Cb-4262 177 H .3.2 Cb-4477 177 G.3.7
Cb-4048 178 H.2.2 Cb-4263 178 H .3.2 Cb-4478 178 G.3.7
Cb-4049 179 H.2.2 Cb-4264 179 H .3.2 Cb-4479 179 G.3.7
Cb-4050 180 H.2.2 Cb-4265 180 H .3.2 Cb-4480 180 G.3.7
Cb-4051 181 H.2.2 Cb-4266 181 H .3.2 Cb-4481 181 G.3.7
Cb-4052 182 H.2.2 Cb-4267 182 H .3.2 Cb-4482 182 G.3.7
Cb-4053 183 H.2.2 Cb-4268 183 H .3.2 Cb-4483 183 G.3.7
Cb-4054 184 H.2.2 Cb-4269 184 H .3.2 Cb-4484 184 G.3.7
Cb-4055 185 H.2.2 Cb-4270 185 H .3.2 Cb-4485 185 G.3.7
Cb-4056 186 H.2.2 Cb-4271 186 H .3.2 Cb-4486 186 G.3.7
Cb-4057 187 H.2.2 Cb-4272 187 H .3.2 Cb-4487 187 G.3.7
Cb-4058 188 H.2.2 Cb-4273 188 H .3.2 Cb-4488 188 G.3.7
Cb-4059 189 H.2.2 Cb-4274 189 H .3.2 Cb-4489 189 G.3.7
Cb-4060 190 H.2.2 Cb-4275 190 H .3.2 Cb-4490 190 G.3.7
Cb-4061 191 H.2.2 Cb-4276 191 H .3.2 Cb-4491 191 G.3.7
Cb-4062 192 H.2.2 Cb-4277 192 H .3.2 Cb-4492 192 G.3.7
Cb-4063 193 H.2.2 Cb-4278 193 H .3.2 Cb-4493 193 G.3.7
Cb-4064 194 H.2.2 Cb-4279 194 H .3.2 Cb-4494 194 G.3.7
Cb-4065 195 H.2.2 Cb-4280 195 H .3.2 Cb-4495 195 G.3.7
Cb-4066 196 H.2.2 Cb-4281 196 H .3.2 Cb-4496 196 G.3.7
Cb-4067 197 H.2.2 Cb-4282 197 H .3.2 Cb-4497 197 G.3.7
Cb-4068 198 H.2.2 Cb-4283 198 H .3.2 Cb-4498 198 G.3.7
Cb-4069 199 H.2.2 Cb-4284 199 H .3.2 Cb-4499 199 G.3.7
Cb-4070 200 H.2.2 Cb-4285 200 H .3.2 Cb-4500 200 G.3.7
Cb-4071 201 H.2.2 Cb-4286 201 H .3.2 Cb-4501 201 G.3.7 Cb-4072 202 H.2.2 Cb-4287 202 H .3.2 Cb-4502 202 G.3.7
Cb-4073 203 H.2.2 Cb-4288 203 H .3.2 Cb-4503 203 G.3.7
Cb-4074 204 H.2.2 Cb-4289 204 H .3.2 Cb-4504 204 G.3.7
Cb-4075 205 H.2.2 Cb-4290 205 H .3.2 Cb-4505 205 G.3.7
Cb-4076 206 H.2.2 Cb-4291 206 H .3.2 Cb-4506 206 G.3.7
Cb-4077 207 H.2.2 Cb-4292 207 H .3.2 Cb-4507 207 G.3.7
Cb-4078 208 H.2.2 Cb-4293 208 H .3.2 Cb-4508 208 G.3.7
Cb-4079 209 H.2.2 Cb-4294 209 H .3.2 Cb-4509 209 G.3.7
Cb-4080 210 H.2.2 Cb-4295 210 H .3.2 Cb-4510 210 G.3.7
Cb-4081 21 1 H.2.2 Cb-4296 21 1 H .3.2 Cb-451 1 21 1 G.3.7
Cb-4082 212 H.2.2 Cb-4297 212 H .3.2 Cb-4512 212 G.3.7
Cb-4083 213 H.2.2 Cb-4298 213 H .3.2 Cb-4513 213 G.3.7
Cb-4084 214 H.2.2 Cb-4299 214 H .3.2 Cb-4514 214 G.3.7
Cb-4085 215 H.2.2 Cb-4300 215 H .3.2 Cb-4515 215 G.3.7
Accordingly, the present invention furthermore relates to compositions comprising as compound I (component 1 , referrred to as "Co.1 ") a (thio)phosphoric acid triamide (T) as defined herein above and as compound II (component 2, referred to as "Co. 2") a fungicide as defined herein, i.e. a combination of component 1 and 2. In preferred embodiments, such compositions may be selected from the component 1 of Table 3 in the column titled "Co. 1 " and from component 2 of Table 3 in the column titled "Co. 2". N-n-butylthiophosphoric acid triamide (NBPT) is referred to as "(W)". N-(n-propyl) thiophosphoric acid triamide (NPPT) or any mixtures comprising NBPT and NPPT, wherein NBPT is present in amounts of from 1 to 99.99 wt.%, more preferably from 10 to 99.9 wt.%, most preferably from 20 to 99 wt.%, particularly preferably from 30 to 98 wt.%, more particularly preferably from 40 to 95 wt.%, most particularly preferably from 50 to 90 wt.%, especially from 60 to 85 wt.%, especially preferably from 72 to 80 wt.%, for example from 74 to 77 wt.%, in each case based on the total weight of the (thio)phosphoric acid triamides (T) contained in the composition (Q), is referred to as (Y). N-n-butylthiophosphoric acid triamide (NBPT) but not comprising any nitrification inhibitor of the compound of formula I is referred to as (Z), thus, all compositions or mixtures i 1 133 to i1698 do not comprise any nitrification inhibitor of the compound of formula I. NBPT and/or NPPT and additionally comprising a urea- containing fertilizer is referred to as (U), wherein such urea-containing fertilizer is preferably urea, formaldehyde urea, UAN, urea sulfur, stabilized urea, urea based NPK-fertilizers, or urea ammonium sulfate and is most preferably UAN. The application of the compositions or mixtures i1 to Ϊ2264 can be carried out in a way that its individual components (for example Co. 1 and Co. 2, in case of i1699 to Ϊ2264 NBPT/NPPT and the urea-containing fertilizer and Co. 2) are applied either simultaneously or with a time lag as further specified below. Preferred embodiments thus include the specified combinations or compositions comprising component 1 and 2 as defined in the compositions or mixtures i1 to i2264 of the following Table 3: Mixt. Co.1 Co.2 Mixt. Co.1 Co.2 Mixt. Co.1 Co.2 Mixt. Co.1 Co.2 i1 (W) (A.1.1) Ϊ567 (Y) (A.1.1) i1133 (Z) (A.1.1) Ϊ1699 (U) (A.1.1) i2 (W) (A.1.2) Ϊ568 (Y) (A.1.2) i1134 (Z) (A.1.2) i1700 (U) (A.1.2) i3 (W) (A.1.3) Ϊ569 (Y) (A.1.3) i1135 (Z) (A.1.3) i1 01 (U) (A.1.3) i4 (W) (A.1.4) Ϊ570 (Y) (A.1.4) i1136 (Z) (A.1.4) i1702 (U) (A.1.4) i5 (W) (A.1.5) i571 (Y) (A.1.5) i1137 (Z) (A.1.5) i1703 (U) (A.1.5) i6 (W) (A.1.6) Ϊ572 (Y) (A.1.6) i1138 (Z) (A.1.6) i1704 (U) (A.1.6) i7 (W) (A.1.7) Ϊ573 (Y) (A.1.7) i1139 (Z) (A.1.7) i1705 (U) (A.1.7) i8 (W) (A.1.8) Ϊ574 (Y) (A.1.8) i1140 (Z) (A.1.8) i1706 (U) (A.1.8) i9 (W) (A.1.9) Ϊ575 (Y) (A.1.9) i1141 (Z) (A.1.9) i1707 (U) (A.1.9) i10 (W) (A.1.10) Ϊ576 (Y) (A.1.10) i1142 (Z) (A.1.10) i1708 (U) (A.1.10) i11 (W) (A.1.11) Ϊ577 (Y) (A.1.11) i1143 (Z) (A.1.11) i1709 (U) (A.1.11) i12 (W) (A.1.12) Ϊ578 (Y) (A.1.12) i1144 (Z) (A.1.12) Ϊ171Ο (U) (A.1.12) i13 (W) (A.1.13) Ϊ579 (Y) (A.1.13) i1145 (Z) (A.1.13) i1711 (U) (A.1.13) i14 (W) (A.1.14) Ϊ580 (Y) (A.1.14) i1146 (Z) (A.1.14) i1712 (U) (A.1.14) i15 (W) (A.1.15) i581 (Y) (A.1.15) i1147 (Z) (A.1.15) Ϊ1713 (U) (A.1.15) i16 (W) (A.1.16) Ϊ582 (Y) (A.1.16) i1148 (Z) (A.1.16) i1714 (U) (A.1.16) i17 (W) (A.1.17) Ϊ583 (Y) (A.1.17) i1149 (Z) (A.1.17) i1715 (U) (A.1.17) i18 (W) (A.1.18) Ϊ584 (Y) (A.1.18) i1150 (Z) (A.1.18) Ϊ1716 (U) (A.1.18) i19 (W) (A.1.19) Ϊ585 (Y) (A.1.19) i1151 (Z) (A.1.19) Ϊ1717 (U) (A.1.19) i20 (W) (A.1.20) Ϊ586 (Y) (A.1.20) i1152 (Z) (A.1.20) Ϊ1718 (U) (A.1.20) i21 (W) (A.1.21) Ϊ587 (Y) (A.1.21) i1153 (Z) (A.1.21) Ϊ1719 (U) (A.1.21) i22 (W) (A.2.1) Ϊ588 (Y) (A.2.1) i1154 (Z) (A.2.1) i1720 (U) (A.2.1) i23 (W) (A.2.2) Ϊ589 (Y) (A.2.2) i1155 (Z) (A.2.2) i1721 (U) (A.2.2) i24 (W) (A.2.3) Ϊ590 (Y) (A.2.3) i1156 (Z) (A.2.3) i1722 (U) (A.2.3) i25 (W) (A.2.4) i591 (Y) (A.2.4) i1157 (Z) (A.2.4) i1723 (U) (A.2.4) i26 (W) (A.2.5) Ϊ592 (Y) (A.2.5) i1158 (Z) (A.2.5) i1724 (U) (A.2.5) i27 (W) (A.2.6) Ϊ593 (Y) (A.2.6) i1159 (Z) (A.2.6) i1725 (U) (A.2.6) i28 (W) (A.2.7) Ϊ594 (Y) (A.2.7) i1160 (Z) (A.2.7) i1726 (U) (A.2.7) i29 (W) (A.3.1) Ϊ595 (Y) (A.3.1) i1161 (Z) (A.3.1) i1727 (U) (A.3.1) i30 (W) (A.3.2) Ϊ596 (Y) (A.3.2) i1162 (Z) (A.3.2) i1728 (U) (A.3.2) i31 (W) (A.3.3) Ϊ597 (Y) (A.3.3) i1163 (Z) (A.3.3) i1729 (U) (A.3.3) i32 (W) (A.3.4) Ϊ598 (Y) (A.3.4) i1164 (Z) (A.3.4) i1730 (U) (A.3.4) i33 (W) (A.3.5) Ϊ599 (Y) (A.3.5) i1165 (Z) (A.3.5) i1731 (U) (A.3.5) i34 (W) (A.3.6) Ϊ600 (Y) (A.3.6) Ϊ1166 (Z) (A.3.6) i1732 (U) (A.3.6) i35 (W) (A.3.7) i601 (Y) (A.3.7) Ϊ1167 (Z) (A.3.7) i1733 (U) (A.3.7) i36 (W) (A.3.8) Ϊ602 (Y) (A.3.8) Ϊ1168 (Z) (A.3.8) i1734 (U) (A.3.8) i37 (W) (A.3.9) Ϊ603 (Y) (A.3.9) Ϊ1169 (Z) (A.3.9) i1735 (U) (A.3.9) i38 (W) (A.3.10) Ϊ604 (Y) (A.3.10) Ϊ1170 (Z) (A.3.10) i1736 (U) (A.3.10) i39 (W) (A.3.11) Ϊ605 (Y) (A.3.11) Ϊ1171 (Z) (A.3.11) i1737 (U) (A.3.11) i40 (W) (A.3.12) Ϊ606 (Y) (A.3.12) Ϊ1172 (Z) (A.3.12) i1738 (U) (A.3.12) i41 (W) (A.3.13) Ϊ607 (Y) (A.3.13) Ϊ1173 (Z) (A.3.13) i1739 (U) (A.3.13) i42 (W) (A.3.14) Ϊ608 (Y) (A.3.14) Ϊ1174 (Z) (A.3.14) i1740 (U) (A.3.14) i43 (W) (A.3.15) Ϊ609 (Y) (A.3.15) Ϊ1175 (Z) (A.3.15) Ϊ1741 (U) (A.3.15) i44 (W) (A.3.16) i610 (Y) (A.3.16) Ϊ1176 (Z) (A.3.16) i1742 (U) (A.3.16) i45 (W) (A.3.17) i611 (Y) (A.3.17) Ϊ1177 (Z) (A.3.17) i1743 (U) (A.3.17) i46 (W) (A.3.18) i612 (Y) (A.3.18) Ϊ1178 (Z) (A.3.18) i1744 (U) (A.3.18) i47 (W) (A.3.19) i613 (Y) (A.3.19) Ϊ1179 (Z) (A.3.19) i1745 (U) (A.3.19) i48 (W) (A.3.20) i614 (Y) (A.3.20) Ϊ1180 (Z) (A.3.20) i1746 (U) (A.3.20) i49 (W) (A.3.21) i615 (Y) (A.3.21) Ϊ1181 (Z) (A.3.21) i1747 (U) (A.3.21) i50 (W) (A.3.22) i616 (Y) (A.3.22) Ϊ1182 (Z) (A.3.22) i1748 (U) (A.3.22) i51 (W) (A.3.23) i617 (Y) (A.3.23) Ϊ1183 (Z) (A.3.23) i1749 (U) (A.3.23) i52 (W) (A.3.24) i618 (Y) (A.3.24) Ϊ1184 (Z) (A.3.24) i1750 (U) (A.3.24) i53 (W) (A.3.25) i619 (Y) (A.3.25) Ϊ1185 (Z) (A.3.25) Ϊ1751 (U) (A.3.25) i54 (W) (A.3.26) Ϊ620 (Y) (A.3.26) Ϊ1186 (Z) (A.3.26) i1752 (U) (A.3.26) i55 (W) (A.3.27) i621 (Y) (A.3.27) Ϊ1187 (Z) (A.3.27) i1753 (U) (A.3.27) i56 (W) (A.4.1) Ϊ622 (Y) (A.4.1) Ϊ1188 (Z) (A.4.1) i1754 (U) (A.4.1) i57 (W) (A.4.2) Ϊ623 (Y) (A.4.2) Ϊ1189 (Z) (A.4.2) i1755 (U) (A.4.2) i58 (W) (A.4.3) Ϊ624 (Y) (A.4.3) Ϊ1190 (Z) (A.4.3) i1756 (U) (A.4.3) i59 (W) (A.4.4) Ϊ625 (Y) (A.4.4) Ϊ1191 (Z) (A.4.4) i1757 (U) (A.4.4) i60 (W) (A.4.5) Ϊ626 (Y) (A.4.5) Ϊ1192 (Z) (A.4.5) i1758 (U) (A.4.5) i61 (W) (A.4.6) Ϊ627 (Y) (A.4.6) Ϊ1193 (Z) (A.4.6) i1759 (U) (A.4.6) i62 (W) (A.4.7) Ϊ628 (Y) (A.4.7) Ϊ1194 (Z) (A.4.7) i1760 (U) (A.4.7) i63 (W) (A.4.8) Ϊ629 (Y) (A.4.8) Ϊ1195 (Z) (A.4.8) Ϊ1761 (U) (A.4.8) i64 (W) (A.4.9) Ϊ630 (Y) (A.4.9) Ϊ1196 (Z) (A.4.9) i1762 (U) (A.4.9) i65 (W) (A.4.10) i631 (Y) (A.4.10) Ϊ1197 (Z) (A.4.10) i1763 (U) (A.4.10) i66 (W) (A.4.11) Ϊ632 (Y) (A.4.11) Ϊ1198 (Z) (A.4.11) i1764 (U) (A.4.11) i67 (W) (A.4.12) Ϊ633 (Y) (A.4.12) Ϊ1199 (Z) (A.4.12) i1765 (U) (A.4.12) i68 (W) (B.1.1) Ϊ634 (Y) (B.1.1) Ϊ1200 (Z) (B.1.1) i1766 (U) (B.1.1) i69 (W) (B.1.2) Ϊ635 (Y) (B.1.2) Ϊ1201 (Z) (B.1.2) i1767 (U) (B.1.2) i70 (W) (B.1.3) Ϊ636 (Y) (B.1.3) Ϊ1202 (Z) (B.1.3) i1768 (U) (B.1.3) i71 (W) (B.1.4) Ϊ637 (Y) (B.1.4) Ϊ1203 (Z) (B.1.4) i1769 (U) (B.1.4) i72 (W) (B.1.5) Ϊ638 (Y) (B.1.5) Ϊ1204 (Z) (B.1.5) i1770 (U) (B.1.5) i73 (W) (B.1.6) Ϊ639 (Y) (B.1.6) Ϊ1205 (Z) (B.1.6) Ϊ1771 (U) (B.1.6) i74 (W) (B.1.7) Ϊ640 (Y) (B.1.7) Ϊ1206 (Z) (B.1.7) i1772 (U) (B.1.7) i75 (W) (B.1.8) i641 (Y) (B.1.8) i1207 (Z) (B.1.8) i1773 (U) (B.1.8) i76 (W) (B.1.9) Ϊ642 (Y) (B.1.9) Ϊ1208 (Z) (B.1.9) i1774 (U) (B.1.9) i77 (W) (B.1.10) Ϊ643 (Y) (B.1.10) Ϊ1209 (Z) (B.1.10) i1775 (U) (B.1.10) i78 (W) (B.1.11) Ϊ644 (Y) (B.1.11) Ϊ1210 (Z) (B.1.11) i1776 (U) (B.1.11) i79 (W) (B.1.12) Ϊ645 (Y) (B.1.12) Ϊ1211 (Z) (B.1.12) i1777 (U) (B.1.12) i80 (W) (B.1.13) Ϊ646 (Y) (B.1.13) Ϊ1212 (Z) (B.1.13) i1778 (U) (B.1.13) i81 (W) (B.1.14) Ϊ647 (Y) (B.1.14) Ϊ1213 (Z) (B.1.14) i1779 (U) (B.1.14) i82 (W) (B.1.15) Ϊ648 (Y) (B.1.15) Ϊ1214 (Z) (B.1.15) i1780 (U) (B.1.15) i83 (W) (B.1.16) Ϊ649 (Y) (B.1.16) Ϊ1215 (Z) (B.1.16) Ϊ1781 (U) (B.1.16) i84 (W) (B.1.17) i650 (Y) (B.1.17) Ϊ1216 (Z) (B.1.17) i1782 (U) (B.1.17) i85 (W) (B.1.18) i651 (Y) (B.1.18) Ϊ1217 (Z) (B.1.18) i1783 (U) (B.1.18) i86 (W) (B.1.19) i652 (Y) (B.1.19) Ϊ1218 (Z) (B.1.19) i1784 (U) (B.1.19) i87 (W) (B.1.20) Ϊ653 (Y) (B.1.20) Ϊ1219 (Z) (B.1.20) i1785 (U) (B.1.20) i88 (W) (B.1.21) Ϊ654 (Y) (B.1.21) Ϊ1220 (Z) (B.1.21) i1786 (U) (B.1.21) i89 (W) (B.1.22) Ϊ655 (Y) (B.1.22) Ϊ1221 (Z) (B.1.22) i1787 (U) (B.1.22) i90 (W) (B.1.23) Ϊ656 (Y) (B.1.23) Ϊ1222 (Z) (B.1.23) i1788 (U) (B.1.23) i91 (W) (B.1.24) Ϊ657 (Y) (B.1.24) Ϊ1223 (Z) (B.1.24) i1789 (U) (B.1.24) i92 (W) (B.1.25) Ϊ658 (Y) (B.1.25) Ϊ1224 (Z) (B.1.25) i1790 (U) (B.1.25) i93 (W) (B.1.26) Ϊ659 (Y) (B.1.26) Ϊ1225 (Z) (B.1.26) Ϊ1791 (U) (B.1.26) i94 (W) (B.1.27) Ϊ660 (Y) (B.1.27) Ϊ1226 (Z) (B.1.27) i1792 (U) (B.1.27) i95 (W) (B.1.28) i661 (Y) (B.1.28) i1227 (Z) (B.1.28) i1793 (U) (B.1.28) i96 (W) (B.1.29) Ϊ662 (Y) (B.1.29) Ϊ1228 (Z) (B.1.29) i1794 (U) (B.1.29) i97 (W) (B.1.30) Ϊ663 (Y) (B.1.30) Ϊ1229 (Z) (B.1.30) i1795 (U) (B.1.30) i98 (W) (B.1.31) Ϊ664 (Y) (B.1.31) Ϊ1230 (Z) (B.1.31) i1796 (U) (B.1.31) i99 (W) (B.1.32) Ϊ665 (Y) (B.1.32) Ϊ1231 (Z) (B.1.32) i1797 (U) (B.1.32) i100 (W) (B.1.33) Ϊ666 (Y) (B.1.33) Ϊ1232 (Z) (B.1.33) i1798 (U) (B.1.33) i 01 (W) (B.1.34) Ϊ667 (Y) (B.1.34) Ϊ1233 (Z) (B.1.34) i1799 (U) (B.1.34) M02 (W) (B.1.35) Ϊ668 (Y) (B.1.35) Ϊ1234 (Z) (B.1.35) Ϊ1800 (U) (B.1.35) i103 (W) (B.1.36) Ϊ669 (Y) (B.1.36) Ϊ1235 (Z) (B.1.36) Ϊ1801 (U) (B.1.36) i104 (W) (B.1.37) Ϊ670 (Y) (B.1.37) Ϊ1236 (Z) (B.1.37) Ϊ1802 (U) (B.1.37) i105 (W) (B.1.38) i671 (Y) (B.1.38) i1237 (Z) (B.1.38) Ϊ1803 (U) (B.1.38) i106 (W) (B.1.39) Ϊ672 (Y) (B.1.39) Ϊ1238 (Z) (B.1.39) Ϊ1804 (U) (B.1.39) i107 (W) (B.1.40) Ϊ673 (Y) (B.1.40) Ϊ1239 (Z) (B.1.40) Ϊ1805 (U) (B.1.40)
M08 (W) (B.1.41) Ϊ674 (Y) (B.1.41) Ϊ1240 (Z) (B.1.41) Ϊ1806 (U) (B.1.41) i109 (W) (B.1.42) Ϊ675 (Y) (B.1.42) Ϊ1241 (Z) (B.1.42) Ϊ1807 (U) (B.1.42) i110 (W) (B.1.43) Ϊ676 (Y) (B.1.43) Ϊ1242 (Z) (B.1.43) Ϊ1808 (U) (B.1.43) i111 (W) (B.1.44) Ϊ677 (Y) (B.1.44) Ϊ1243 (Z) (B.1.44) Ϊ1809 (U) (B.1.44) i112 (W) (B.1.45) Ϊ678 (Y) (B.1.45) Ϊ1244 (Z) (B.1.45) Ϊ1810 (U) (B.1.45) i113 (W) (B.1.46) Ϊ679 (Y) (B.1.46) Ϊ1245 (Z) (B.1.46) Ϊ1811 (U) (B.1.46) i114 (W) (B.1.47) Ϊ680 (Y) (B.1.47) Ϊ1246 (Z) (B.1.47) Ϊ1812 (U) (B.1.47) i115 (W) (B.1.48) i681 (Y) (B.1.48) i1247 (Z) (B.1.48) Ϊ1813 (U) (B.1.48) i116 (W) (B.1.49) Ϊ682 (Y) (B.1.49) Ϊ1248 (Z) (B.1.49) Ϊ1814 (U) (B.1.49) i117 (W) (B.1.50) Ϊ683 (Y) (B.1.50) Ϊ1249 (Z) (B.1.50) Ϊ1815 (U) (B.1.50) i118 (W) (B.1.51) Ϊ684 (Y) (B.1.51) Ϊ1250 (Z) (B.1.51) Ϊ1816 (U) (B.1.51) i119 (W) (B.2.1) Ϊ685 (Y) (B.2.1) Ϊ1251 (Z) (B.2.1) Ϊ1817 (U) (B.2.1) i120 (W) (B.2.2) Ϊ686 (Y) (B.2.2) Ϊ1252 (Z) (B.2.2) Ϊ1818 (U) (B.2.2) i121 (W) (B.2.3) Ϊ687 (Y) (B.2.3) Ϊ1253 (Z) (B.2.3) Ϊ1819 (U) (B.2.3) i122 (W) (B.2.4) Ϊ688 (Y) (B.2.4) Ϊ1254 (Z) (B.2.4) Ϊ1820 (U) (B.2.4) i123 (W) (B.2.5) Ϊ689 (Y) (B.2.5) Ϊ1255 (Z) (B.2.5) Ϊ1821 (U) (B.2.5) i124 (W) (B.2.6) Ϊ690 (Y) (B.2.6) Ϊ1256 (Z) (B.2.6) Ϊ1822 (U) (B.2.6) i125 (W) (B.2.7) i691 (Y) (B.2.7) i1257 (Z) (B.2.7) Ϊ1823 (U) (B.2.7) i126 (W) (B.2.8) Ϊ692 (Y) (B.2.8) Ϊ1258 (Z) (B.2.8) Ϊ1824 (U) (B.2.8) i127 (W) (B.3.1) Ϊ693 (Y) (B.3.1) Ϊ1259 (Z) (B.3.1) Ϊ1825 (U) (B.3.1) i128 (W) (C.1.1) Ϊ694 (Y) (C.1.1) Ϊ1260 (Z) (C.1.1) Ϊ1826 (U) (C.1.1) i129 (W) (C.1.2) Ϊ695 (Y) (C.1.2) Ϊ1261 (Z) (C.1.2) Ϊ1827 (U) (C.1.2) i130 (W) (C.1.3) Ϊ696 (Y) (C.1.3) Ϊ1262 (Z) (C.1.3) Ϊ1828 (U) (C.1.3) i131 (W) (C.1.4) Ϊ697 (Y) (C.1.4) Ϊ1263 (Z) (C.1.4) Ϊ1829 (U) (C.1.4) i132 (W) (C.1.5) Ϊ698 (Y) (C.1.5) Ϊ1264 (Z) (C.1.5) Ϊ1830 (U) (C.1.5) i133 (W) (C.1.6) Ϊ699 (Y) (C.1.6) Ϊ1265 (Z) (C.1.6) Ϊ1831 (U) (C.1.6) i134 (W) (C.1.7) Ϊ700 (Y) (C.1.7) Ϊ1266 (Z) (C.1.7) Ϊ1832 (U) (C.1.7) i135 (W) (C.2.1) Ϊ701 (Y) (C.2.1) i1267 (Z) (C.2.1) Ϊ1833 (U) (C.2.1) i136 (W) (C.2.2) Ϊ702 (Y) (C.2.2) Ϊ1268 (Z) (C.2.2) Ϊ1834 (U) (C.2.2) i137 (W) (C.2.3) Ϊ703 (Y) (C.2.3) Ϊ1269 (Z) (C.2.3) Ϊ1835 (U) (C.2.3) i138 (W) (C.2.4) Ϊ704 (Y) (C.2.4) Ϊ1270 (Z) (C.2.4) Ϊ1836 (U) (C.2.4) i139 (W) (C.2.5) Ϊ705 (Y) (C.2.5) Ϊ1271 (Z) (C.2.5) Ϊ1837 (U) (C.2.5) i140 (W) (C.2.6) Ϊ706 (Y) (C.2.6) i1272 (Z) (C.2.6) Ϊ1838 (U) (C.2.6) i141 (W) (C.2.7) Ϊ707 (Y) (C.2.7) Ϊ1273 (Z) (C.2.7) Ϊ1839 (U) (C.2.7) i142 (W) (D.1.1) Ϊ708 (Y) (D.1.1) Ϊ1274 (Z) (D.1.1) Ϊ1840 (U) (D.1.1) i143 (W) (D.1.2) Ϊ709 (Y) (D.1.2) Ϊ1275 (Z) (D.1.2) Ϊ1841 (U) (D.1.2) i144 (W) (D.1.3) Ϊ710 (Y) (D.1.3) Ϊ1276 (Z) (D.1.3) Ϊ1842 (U) (D.1.3) i145 (W) (D.1.4) Ϊ711 (Y) (D.1.4) i1277 (Z) (D.1.4) Ϊ1843 (U) (D.1.4) i146 (W) (D.1.5) Ϊ712 (Y) (D.1.5) Ϊ1278 (Z) (D.1.5) Ϊ1844 (U) (D.1.5) i147 (W) (D.1.6) Ϊ713 (Y) (D.1.6) Ϊ1279 (Z) (D.1.6) Ϊ1845 (U) (D.1.6) i148 (W) (D.2.1) Ϊ714 (Y) (D.2.1) Ϊ1280 (Z) (D.2.1) Ϊ1846 (U) (D.2.1) i149 (W) (D.2.2) Ϊ715 (Y) (D.2.2) Ϊ1281 (Z) (D.2.2) Ϊ1847 (U) (D.2.2) i150 (W) (D.2.3) Ϊ716 (Y) (D.2.3) i1282 (Z) (D.2.3) Ϊ1848 (U) (D.2.3) i151 (W) (D.2.4) Ϊ717 (Y) (D.2.4) Ϊ1283 (Z) (D.2.4) Ϊ1849 (U) (D.2.4) i152 (W) (D.2.5) Ϊ718 (Y) (D.2.5) Ϊ1284 (Z) (D.2.5) Ϊ1850 (U) (D.2.5) i153 (W) (D.2.6) Ϊ719 (Y) (D.2.6) Ϊ1285 (Z) (D.2.6) Ϊ1851 (U) (D.2.6) i154 (W) (D.2.7) Ϊ720 (Y) (D.2.7) Ϊ1286 (Z) (D.2.7) Ϊ1852 (U) (D.2.7) i155 (W) (E.1.1) Ϊ721 (Y) (E.1.1) i1287 (Z) (E.1.1) Ϊ1853 (U) (E.1.1) i156 (W) (E.1.2) Ϊ722 (Y) (E.1.2) Ϊ1288 (Z) (E.1.2) Ϊ1854 (U) (E.1.2) i157 (W) (E.1.3) Ϊ723 (Y) (E.1.3) Ϊ1289 (Z) (E.1.3) i1855 (U) (E.1.3) i158 (W) (E.2.1) Ϊ724 (Y) (E.2.1) Ϊ1290 (Z) (E.2.1) Ϊ1856 (U) (E.2.1) i159 (W) (E.2.2) Ϊ725 (Y) (E.2.2) Ϊ1291 (Z) (E.2.2) Ϊ1857 (U) (E.2.2) i160 (W) (E.2.3) Ϊ726 (Y) (E.2.3) i1292 (Z) (E.2.3) Ϊ1858 (U) (E.2.3) i161 (W) (E.2.4) Ϊ727 (Y) (E.2.4) Ϊ1293 (Z) (E.2.4) Ϊ1859 (U) (E.2.4) i162 (W) (E.2.5) Ϊ728 (Y) (E.2.5) Ϊ1294 (Z) (E.2.5) Ϊ1860 (U) (E.2.5) i163 (W) (E.2.6) Ϊ729 (Y) (E.2.6) Ϊ1295 (Z) (E.2.6) Ϊ1861 (U) (E.2.6) i164 (W) (E.2.7) Ϊ730 (Y) (E.2.7) Ϊ1296 (Z) (E.2.7) Ϊ1862 (U) (E.2.7) i165 (W) (E.2.8) Ϊ731 (Y) (E.2.8) i1297 (Z) (E.2.8) Ϊ1863 (U) (E.2.8) i166 (W) (F.1.1) Ϊ732 (Y) (F.1.1) Ϊ1298 (Z) (F.1.1) Ϊ1864 (U) (F.1.1) i167 (W) (F.1.2) Ϊ733 (Y) (F.1.2) Ϊ1299 (Z) (F.1.2) Ϊ1865 (U) (F.1.2) i168 (W) (F.1.3) Ϊ734 (Y) (F.1.3) Ϊ1300 (Z) (F.1.3) Ϊ1866 (U) (F.1.3) i169 (W) (F.1.4) Ϊ735 (Y) (F.1.4) Ϊ1301 (Z) (F.1.4) Ϊ1867 (U) (F.1.4) M70 (W) (F.1.5) Ϊ736 (Y) (F.1.5) Ϊ1302 (Z) (F.1.5) Ϊ1868 (U) (F.1.5) i171 (W) (F.1.6) Ϊ737 (Y) (F.1.6) Ϊ1303 (Z) (F.1.6) Ϊ1869 (U) (F.1.6) i172 (W) (F.2.1) Ϊ738 (Y) (F.2.1) Ϊ1304 (Z) (F.2.1) Ϊ1870 (U) (F.2.1) i173 (W) (G.1.1) Ϊ739 (Y) (G.1.1) Ϊ1305 (Z) (G.1.1) Ϊ1871 (U) (G.1.1) i174 (W) (G.1.2) Ϊ740 (Y) (G.1.2) Ϊ1306 (Z) (G.1.2) Ϊ1872 (U) (G.1.2) i175 (W) (G.1.3) Ϊ741 (Y) (G.1.3) i1307 (Z) (G.1.3) Ϊ1873 (U) (G.1.3) i176 (W) (G.1.4) Ϊ742 (Y) (G.1.4) Ϊ1308 (Z) (G.1.4) Ϊ1874 (U) (G.1.4) i177 (W) (G.2.1) Ϊ743 (Y) (G.2.1) Ϊ1309 (Z) (G.2.1) Ϊ1875 (U) (G.2.1) i178 (W) (G.2.2) Ϊ744 (Y) (G.2.2) Ϊ1310 (Z) (G.2.2) Ϊ1876 (U) (G.2.2) i179 (W) (G.2.3) Ϊ745 (Y) (G.2.3) Ϊ1311 (Z) (G.2.3) Ϊ1877 (U) (G.2.3) i180 (W) (G.2.4) Ϊ746 (Y) (G.2.4) Ϊ1312 (Z) (G.2.4) Ϊ1878 (U) (G.2.4) i181 (W) (G.2.5) Ϊ747 (Y) (G.2.5) Ϊ1313 (Z) (G.2.5) Ϊ1879 (U) (G.2.5) i182 (W) (G.2.6) Ϊ748 (Y) (G.2.6) Ϊ1314 (Z) (G.2.6) Ϊ1880 (U) (G.2.6) i183 (W) (G.2.7) Ϊ749 (Y) (G.2.7) Ϊ1315 (Z) (G.2.7) Ϊ1881 (U) (G.2.7) i184 (W) (G.3.1) Ϊ750 (Y) (G.3.1) Ϊ1316 (Z) (G.3.1) Ϊ1882 (U) (G.3.1) i185 (W) (G.3.2) Ϊ751 (Y) (G.3.2) 11317 (Z) (G.3.2) Ϊ1883 (U) (G.3.2) i186 (W) (G.3.3) Ϊ752 (Y) (G.3.3) Ϊ1318 (Z) (G.3.3) Ϊ1884 (U) (G.3.3) i187 (W) (G.3.4) Ϊ753 (Y) (G.3.4) Ϊ1319 (Z) (G.3.4) Ϊ1885 (U) (G.3.4) i188 (W) (G.3.5) Ϊ754 (Y) (G.3.5) Ϊ1320 (Z) (G.3.5) Ϊ1886 (U) (G.3.5) i189 (W) (G.3.6) Ϊ755 (Y) (G.3.6) Ϊ1321 (Z) (G.3.6) Ϊ1887 (U) (G.3.6) i190 (W) (G.3.7) Ϊ756 (Y) (G.3.7) i1322 (Z) (G.3.7) Ϊ1888 (U) (G.3.7) i191 (W) (G.3.8) Ϊ757 (Y) (G.3.8) Ϊ1323 (Z) (G.3.8) Ϊ1889 (U) (G.3.8) i192 (W) (G.4.1) Ϊ758 (Y) (G.4.1) Ϊ1324 (Z) (G.4.1) Ϊ1890 (U) (G.4.1) i193 (W) (G.5.1) Ϊ759 (Y) (G.5.1) Ϊ1325 (Z) (G.5.1) Ϊ1891 (U) (G.5.1) i194 (W) (G.5.2) Ϊ760 (Y) (G.5.2) Ϊ1326 (Z) (G.5.2) Ϊ1892 (U) (G.5.2) i195 (W) (G.5.3) Ϊ761 (Y) (G.5.3) i1327 (Z) (G.5.3) Ϊ1893 (U) (G.5.3) i196 (W) (H.1.1) Ϊ762 (Y) (H.1.1) Ϊ1328 (Z) (H.1.1) Ϊ1894 (U) (H.1.1) i197 (W) (H.1.2) Ϊ763 (Y) (H.1.2) Ϊ1329 (Z) (H.1.2) Ϊ1895 (U) (H.1.2) i198 (W) (H.1.3) Ϊ764 (Y) (H.1.3) Ϊ1330 (Z) (H.1.3) Ϊ1896 (U) (H.1.3) i199 (W) (H.1.4) Ϊ765 (Y) (H.1.4) Ϊ1331 (Z) (H.1.4) Ϊ1897 (U) (H.1.4) i200 (W) (H.1.5) Ϊ766 (Y) (H.1.5) Ϊ1332 (Z) (H.1.5) Ϊ1898 (U) (H.1.5) i201 (W) (H.1.6) Ϊ767 (Y) (H.1.6) Ϊ1333 (Z) (H.1.6) Ϊ1899 (U) (H.1.6)
Ϊ202 (W) (H.2.1) Ϊ768 (Y) (H.2.1) Ϊ1334 (Z) (H.2.1) Ϊ1900 (U) (H.2.1)
Ϊ203 (W) (H.2.2) Ϊ769 (Y) (H.2.2) Ϊ1335 (Z) (H.2.2) Ϊ1901 (U) (H.2.2) Ϊ204 (W) (H.2.3) Ϊ770 (Y) (H.2.3) Ϊ1336 (Z) (H.2.3) Ϊ1902 (U) (H.2.3) i205 (W) (H.2.4) Ϊ771 (Y) (H.2.4) i1337 (Z) (H.2.4) Ϊ1903 (U) (H.2.4)
Ϊ206 (W) (H.2.5) Ϊ772 (Y) (H.2.5) Ϊ1338 (Z) (H.2.5) Ϊ1904 (U) (H.2.5)
Ϊ207 (W) (H.2.6) Ϊ773 (Y) (H.2.6) Ϊ1339 (Z) (H.2.6) Ϊ1905 (U) (H.2.6)
Ϊ208 (W) (H.2.7) Ϊ774 (Y) (H.2.7) Ϊ1340 (Z) (H.2.7) Ϊ1906 (U) (H.2.7)
Ϊ209 (W) (H.2.8) Ϊ775 (Y) (H.2.8) Ϊ1341 (Z) (H.2.8) Ϊ1907 (U) (H.2.8) i210 (W) (H.2.9) Ϊ776 (Y) (H.2.9) Ϊ1342 (Z) (H.2.9) Ϊ1908 (U) (H.2.9) i211 (W) (H.3.1) Ϊ777 (Y) (H.3.1) Ϊ1343 (Z) (H.3.1) Ϊ1909 (U) (H.3.1) i212 (W) (H.3.2) Ϊ778 (Y) (H.3.2) Ϊ1344 (Z) (H.3.2) Ϊ1910 (U) (H.3.2) i213 (W) (H.3.3) Ϊ779 (Y) (H.3.3) Ϊ1345 (Z) (H.3.3) Ϊ1911 (U) (H.3.3) i214 (W) (H.3.4) Ϊ780 (Y) (H.3.4) Ϊ1346 (Z) (H.3.4) Ϊ1912 (U) (H.3.4) i215 (W) (H.3.5) Ϊ781 (Y) (H.3.5) i1347 (Z) (H.3.5) Ϊ1913 (U) (H.3.5) i216 (W) (H.3.6) Ϊ782 (Y) (H.3.6) Ϊ1348 (Z) (H.3.6) Ϊ1914 (U) (H.3.6) i217 (W) (H.3.7) Ϊ783 (Y) (H.3.7) Ϊ1349 (Z) (H.3.7) Ϊ1915 (U) (H.3.7) i218 (W) (H.3.8) Ϊ784 (Y) (H.3.8) Ϊ1350 (Z) (H.3.8) Ϊ1916 (U) (H.3.8) i219 (W) (H.3.9) Ϊ785 (Y) (H.3.9) Ϊ1351 (Z) (H.3.9) Ϊ1917 (U) (H.3.9)
Ϊ220 (W) (H.3.10) Ϊ786 (Y) (H.3.10) Ϊ1352 (Z) (H.3.10) Ϊ1918 (U) (H.3.10) i221 (W) (H.3.11) Ϊ787 (Y) (H.3.11) Ϊ1353 (Z) (H.3.11) Ϊ1919 (U) (H.3.11)
Ϊ222 (W) (H.4.1) Ϊ788 (Y) (H.4.1) Ϊ1354 (Z) (H.4.1) Ϊ1920 (U) (H.4.1)
Ϊ223 (W) (H.4.2) Ϊ789 (Y) (H.4.2) Ϊ1355 (Z) (H.4.2) Ϊ1921 (U) (H.4.2)
Ϊ224 (W) (H.4.3) Ϊ790 (Y) (H.4.3) Ϊ1356 (Z) (H.4.3) Ϊ1922 (U) (H.4.3) i225 (W) (H.4.4) Ϊ791 (Y) (H.4.4) i1357 (Z) (H.4.4) Ϊ1923 (U) (H.4.4)
Ϊ226 (W) (H.4.5) Ϊ792 (Y) (H.4.5) Ϊ1358 (Z) (H.4.5) Ϊ1924 (U) (H.4.5)
Ϊ227 (W) (H.4.6) Ϊ793 (Y) (H.4.6) Ϊ1359 (Z) (H.4.6) Ϊ1925 (U) (H.4.6)
Ϊ228 (W) (H.4.7) Ϊ794 (Y) (H.4.7) Ϊ1360 (Z) (H.4.7) Ϊ1926 (U) (H.4.7)
Ϊ229 (W) (H.4.8) Ϊ795 (Y) (H.4.8) Ϊ1361 (Z) (H.4.8) Ϊ1927 (U) (H.4.8)
Ϊ230 (W) (H.4.9) Ϊ796 (Y) (H.4.9) Ϊ1362 (Z) (H.4.9) Ϊ1928 (U) (H.4.9) i231 (W) (H.4.10) Ϊ797 (Y) (H.4.10) Ϊ1363 (Z) (H.4.10) Ϊ1929 (U) (H.4.10)
Ϊ232 (W) (1.1.1) Ϊ798 (Y) (1.1.1) Ϊ1364 (Z) (1.1.1) Ϊ1930 (U) (1.1.1)
Ϊ233 (W) (1.1.2) Ϊ799 (Y) (1.1.2) Ϊ1365 (Z) (1.1.2) Ϊ1931 (U) (1.1.2)
Ϊ234 (W) (1.2.1) Ϊ800 (Y) (1.2.1) Ϊ1366 (Z) (1.2.1) Ϊ1932 (U) (1.2.1) i235 (W) (I.2.2) i801 (Y) (I.2.2) i1367 (Z) (I.2.2) Ϊ1933 (U) (I.2.2)
Ϊ236 (W) (I.2.3) Ϊ802 (Y) (I.2.3) Ϊ1368 (Z) (I.2.3) Ϊ1934 (U) (I.2.3)
Ϊ237 (W) (I.2.4) Ϊ803 (Y) (I.2.4) Ϊ1369 (Z) (I.2.4) Ϊ1935 (U) (I.2.4) Ϊ238 (W) (I.2.5) Ϊ804 (Y) (I.2.5) Ϊ1370 (Z) (I.2.5) Ϊ1936 (U) (I.2.5)
Ϊ239 (W) (J.1.1) Ϊ805 (Y) (J.1.1) Ϊ1371 (Z) (J.1.1) Ϊ1937 (U) (J.1.1)
Ϊ240 (W) (J.1.2) Ϊ806 (Y) (J.1.2) Ϊ1372 (Z) (J.1.2) Ϊ1938 (U) (J.1.2) i241 (W) (J.1.3) Ϊ807 (Y) (J.1.3) Ϊ1373 (Z) (J.1.3) Ϊ1939 (U) (J.1.3)
Ϊ242 (W) (J.1.4) Ϊ808 (Y) (J.1.4) Ϊ1374 (Z) (J.1.4) Ϊ1940 (U) (J.1.4)
Ϊ243 (W) (J.1.5) Ϊ809 (Y) (J.1.5) Ϊ1375 (Z) (J.1.5) Ϊ1941 (U) (J.1.5)
Ϊ244 (W) (J.1.6) i810 (Y) (J.1.6) Ϊ1376 (Z) (J.1.6) Ϊ1942 (U) (J.1.6) i245 (W) (J.1.7) i811 (Y) (J.1.7) i1377 (Z) (J.1.7) Ϊ1943 (U) (J.1.7)
Ϊ246 (W) (J.1.8) i812 (Y) (J.1.8) Ϊ1378 (Z) (J.1.8) Ϊ1944 (U) (J.1.8)
Ϊ247 (W) (J.1.9) i813 (Y) (J.1.9) Ϊ1379 (Z) (J.1.9) Ϊ1945 (U) (J.1.9)
Ϊ248 (W) (K.1.1) i814 (Y) (K.1.1) Ϊ1380 (Z) (K.1.1) Ϊ1946 (U) (K.1.1)
Ϊ249 (W) (K.1.2) i815 (Y) (K.1.2) Ϊ1381 (Z) (K.1.2) Ϊ1947 (U) (K.1.2)
Ϊ250 (W) (K.1.3) i816 (Y) (K.1.3) Ϊ1382 (Z) (K.1.3) Ϊ1948 (U) (K.1.3) i251 (W) (K.1.4) i817 (Y) (K.1.4) Ϊ1383 (Z) (K.1.4) Ϊ1949 (U) (K.1.4)
Ϊ252 (W) (K.1.5) i818 (Y) (K.1.5) Ϊ1384 (Z) (K.1.5) Ϊ1950 (U) (K.1.5)
Ϊ253 (W) (K.1.6) i819 (Y) (K.1.6) Ϊ1385 (Z) (K.1.6) Ϊ1951 (U) (K.1.6)
Ϊ254 (W) (K.1.7) Ϊ820 (Y) (K.1.7) Ϊ1386 (Z) (K.1.7) Ϊ1952 (U) (K.1.7) i255 (W) (K.1.8) i821 (Y) (K.1.8) i1387 (Z) (K.1.8) Ϊ1953 (U) (K.1.8)
Ϊ256 (W) (K.1.9) Ϊ822 (Y) (K.1.9) Ϊ1388 (Z) (K.1.9) Ϊ1954 (U) (K.1.9)
Ϊ257 (W) (K.1.10) Ϊ823 (Y) (K.1.10) Ϊ1389 (Z) (K.1.10) i1955 (U) (K.1.10)
Ϊ258 (W) (K.1.11) Ϊ824 (Y) (K.1.11) Ϊ1390 (Z) (K.1.11) Ϊ1956 (U) (K.1.11)
Ϊ259 (W) (K.1.12) Ϊ825 (Y) (K.1.12) Ϊ1391 (Z) (K.1.12) Ϊ1957 (U) (K.1.12)
Ϊ260 (W) (K.1.13) Ϊ826 (Y) (K.1.13) Ϊ1392 (Z) (K.1.13) Ϊ1958 (U) (K.1.13) i261 (W) (K.1.14) Ϊ827 (Y) (K.1.14) Ϊ1393 (Z) (K.1.14) Ϊ1959 (U) (K.1.14)
Ϊ262 (W) (K.1.15) Ϊ828 (Y) (K.1.15) Ϊ1394 (Z) (K.1.15) Ϊ1960 (U) (K.1.15)
Ϊ263 (W) (K.1.16) Ϊ829 (Y) (K.1.16) Ϊ1395 (Z) (K.1.16) Ϊ1961 (U) (K.1.16)
Ϊ264 (W) (K.1.17) Ϊ830 (Y) (K.1.17) Ϊ1396 (Z) (K.1.17) Ϊ1962 (U) (K.1.17) i265 (W) (K.1.18) i831 (Y) (K.1.18) i1397 (Z) (K.1.18) Ϊ1963 (U) (K.1.18)
Ϊ266 (W) (K.1.19) Ϊ832 (Y) (K.1.19) Ϊ1398 (Z) (K.1.19) Ϊ1964 (U) (K.1.19)
Ϊ267 (W) (K.1.20) Ϊ833 (Y) (K.1.20) Ϊ1399 (Z) (K.1.20) Ϊ1965 (U) (K.1.20)
Ϊ268 (W) (K.1.21) Ϊ834 (Y) (K.1.21) Ϊ1400 (Z) (K.1.21) Ϊ1966 (U) (K.1.21)
Ϊ269 (W) (K.1.22) Ϊ835 (Y) (K.1.22) Ϊ1401 (Z) (K.1.22) Ϊ1967 (U) (K.1.22)
Ϊ270 (W) (K.1.23) Ϊ836 (Y) (K.1.23) Ϊ1402 (Z) (K.1.23) Ϊ1968 (U) (K.1.23) i271 (W) (K.1.24) Ϊ837 (Y) (K.1.24) Ϊ1403 (Z) (K.1.24) Ϊ1969 (U) (K.1.24) Ϊ272 (W) (K.1.25) Ϊ838 (Y) (K.1.25) Ϊ1404 (Z) (K.1.25) Ϊ1970 (U) (K.1.25)
Ϊ273 (W) (K.1.26) Ϊ839 (Y) (K.1.26) Ϊ1405 (Z) (K.1.26) Ϊ1971 (U) (K.1.26)
Ϊ274 (W) (K.1.27) Ϊ840 (Y) (K.1.27) Ϊ1406 (Z) (K.1.27) Ϊ1972 (U) (K.1.27) i275 (W) (K.1.28) i841 (Y) (K.1.28) i1407 (Z) (K.1.28) Ϊ1973 (U) (K.1.28)
Ϊ276 (W) (K.1.29) Ϊ842 (Y) (K.1.29) Ϊ1408 (Z) (K.1.29) Ϊ1974 (U) (K.1.29)
Ϊ277 (W) (K.1.30) Ϊ843 (Y) (K.1.30) Ϊ1409 (Z) (K.1.30) Ϊ1975 (U) (K.1.30)
Ϊ278 (W) (K.1.31) Ϊ844 (Y) (K.1.31) Ϊ1410 (Z) (K.1.31) Ϊ1976 (U) (K.1.31)
Ϊ279 (W) (K.1.32) Ϊ845 (Y) (K.1.32) Ϊ1411 (Z) (K.1.32) Ϊ1977 (U) (K.1.32)
Ϊ280 (W) (K.1.33) Ϊ846 (Y) (K.1.33) Ϊ1412 (Z) (K.1.33) Ϊ1978 (U) (K.1.33) i281 (W) (K.1.34) Ϊ847 (Y) (K.1.34) Ϊ1413 (Z) (K.1.34) Ϊ1979 (U) (K.1.34)
Ϊ282 (W) (K.1.35) Ϊ848 (Y) (K.1.35) Ϊ1414 (Z) (K.1.35) Ϊ1980 (U) (K.1.35)
Ϊ283 (W) (K.1.36) Ϊ849 (Y) (K.1.36) Ϊ1415 (Z) (K.1.36) Ϊ1981 (U) (K.1.36)
Ϊ284 (W) (K.1.37) i850 (Y) (K.1.37) Ϊ1416 (Z) (K.1.37) Ϊ1982 (U) (K.1.37) i285 (W) (K.1.38) i851 (Y) (K.1.38) Ϊ1417 (Z) (K.1.38) Ϊ1983 (U) (K.1.38)
Ϊ286 (W) (K.1.39) i852 (Y) (K.1.39) Ϊ1418 (Z) (K.1.39) Ϊ1984 (U) (K.1.39)
Ϊ287 (W) (K.1.40) Ϊ853 (Y) (K.1.40) Ϊ1419 (Z) (K.1.40) Ϊ1985 (U) (K.1.40)
Ϊ288 (W) (K.1.41) Ϊ854 (Y) (K.1.41) Ϊ1420 (Z) (K.1.41) Ϊ1986 (U) (K.1.41)
Ϊ289 (W) (K.1.42) Ϊ855 (Y) (K.1.42) Ϊ1421 (Z) (K.1.42) Ϊ1987 (U) (K.1.42)
Ϊ290 (W) (K.1.43) Ϊ856 (Y) (K.1.43) i1422 (Z) (K.1.43) Ϊ1988 (U) (K.1.43) i291 (W) (K.1.44) Ϊ857 (Y) (K.1.44) Ϊ1423 (Z) (K.1.44) Ϊ1989 (U) (K.1.44)
Ϊ292 (W) (K.1.45) Ϊ858 (Y) (K.1.45) Ϊ1424 (Z) (K.1.45) Ϊ1990 (U) (K.1.45)
Ϊ293 (W) (K.1.46) Ϊ859 (Y) (K.1.46) Ϊ1425 (Z) (K.1.46) Ϊ1991 (U) (K.1.46)
Ϊ294 (W) (K.1.47) i860 (Y) (K.1.47) Ϊ1426 (Z) (K.1.47) Ϊ1992 (U) (K.1.47) i295 (W) (K.1.48) i861 (Y) (K.1.48) i1427 (Z) (K.1.48) Ϊ1993 (U) (K.1.48)
Ϊ296 (W) (M.1.1) Ϊ862 (Y) (M.1.1) Ϊ1428 (Z) (M.1.1) Ϊ1994 (U) (M.1.1)
Ϊ297 (W) (M.1.2) Ϊ863 (Y) (M.1.2) Ϊ1429 (Z) (M.1.2) Ϊ1995 (U) (M.1.2)
Ϊ298 (W) (M.1.3) Ϊ864 (Y) (M.1.3) Ϊ1430 (Z) (M.1.3) Ϊ1996 (U) (M.1.3)
Ϊ299 (W) (M.1.4) Ϊ865 (Y) (M.1.4) Ϊ1431 (Z) (M.1.4) Ϊ1997 (U) (M.1.4)
Ϊ300 (W) (M.1.5) Ϊ866 (Y) (M.1.5) Ϊ1432 (Z) (M.1.5) Ϊ1998 (U) (M.1.5) i301 (W) (M.1.6) Ϊ867 (Y) (M.1.6) Ϊ1433 (Z) (M.1.6) Ϊ1999 (U) (M.1.6)
Ϊ302 (W) (M.1.7) Ϊ868 (Y) (M.1.7) Ϊ1434 (Z) (M.1.7) i2000 (U) (M.1.7)
Ϊ303 (W) (M.1.8) Ϊ869 (Y) (M.1.8) Ϊ1435 (Z) (M.1.8) i2001 (U) (M.1.8)
Ϊ304 (W) (M.1.9) Ϊ870 (Y) (M.1.9) Ϊ1436 (Z) (M.1.9) i2002 (U) (M.1.9) i305 (W) (M.1.10) i871 (Y) (M.1.10) i1437 (Z) (M.1.10) i2003 (U) (M.1.10) Ϊ306 (W) (M.1.11) Ϊ872 (Y) (M.1.11) Ϊ1438 (Z) (M.1.11) i2004 (U) (M.1.11)
Ϊ307 (W) (M.1.12) Ϊ873 (Y) (M.1.12) Ϊ1439 (Z) (M.1.12) i2005 (U) (M.1.12)
Ϊ308 (W) (M.1.13) Ϊ874 (Y) (M.1.13) Ϊ1440 (Z) (M.1.13) i2006 (U) (M.1.13)
Ϊ309 (W) (M.1.14) Ϊ875 (Y) (M.1.14) Ϊ1441 (Z) (M.1.14) i2007 (U) (M.1.14) i310 (W) (M.1.15) Ϊ876 (Y) (M.1.15) Ϊ1442 (Z) (M.1.15) i2008 (U) (M.1.15) i311 (W) (M.1.16) Ϊ877 (Y) (M.1.16) Ϊ1443 (Z) (M.1.16) i2009 (U) (M.1.16) i312 (W) (M.1.17) Ϊ878 (Y) (M.1.17) Ϊ1444 (Z) (M.1.17) i2010 (U) (M.1.17) i313 (W) (M.1.18) Ϊ879 (Y) (M.1.18) Ϊ1445 (Z) (M.1.18) Ϊ2011 (U) (M.1.18) i314 (W) (M.1.19) Ϊ880 (Y) (M.1.19) Ϊ1446 (Z) (M.1.19) i2012 (U) (M.1.19) i315 (W) (M.1.20) i881 (Y) (M.1.20) i1447 (Z) (M.1.20) i2013 (U) (M.1.20) i316 (W) (M.1.21) Ϊ882 (Y) (M.1.21) Ϊ1448 (Z) (M.1.21) Ϊ2014 (U) (M.1.21) i317 (W) (M.1.22) Ϊ883 (Y) (M.1.22) Ϊ1449 (Z) (M.1.22) Ϊ2015 (U) (M.1.22) i318 (W) (M.1.23) Ϊ884 (Y) (M.1.23) Ϊ1450 (Z) (M.1.23) i2016 (U) (M.1.23) i319 (W) (M.1.24) Ϊ885 (Y) (M.1.24) Ϊ1451 (Z) (M.1.24) Ϊ2017 (U) (M.1.24)
Ϊ320 (W) (M.1.25) Ϊ886 (Y) (M.1.25) Ϊ1452 (Z) (M.1.25) i2018 (U) (M.1.25) i321 (W) (M.1.26) Ϊ887 (Y) (M.1.26) Ϊ1453 (Z) (M.1.26) i2019 (U) (M.1.26)
Ϊ322 (W) (M.1.27) Ϊ888 (Y) (M.1.27) Ϊ1454 (Z) (M.1.27) i2020 (U) (M.1.27)
Ϊ323 (W) (M.1.28) Ϊ889 (Y) (M.1.28) Ϊ1455 (Z) (M.1.28) i2021 (U) (M.1.28)
Ϊ324 (W) (M.1.29) Ϊ890 (Y) (M.1.29) Ϊ1456 (Z) (M.1.29) i2022 (U) (M.1.29) i325 (W) (M.1.30) i891 (Y) (M.1.30) i1457 (Z) (M.1.30) i2023 (U) (M.1.30)
Ϊ326 (W) (M.1.31) Ϊ892 (Y) (M.1.31) Ϊ1458 (Z) (M.1.31) i2024 (U) (M.1.31)
Ϊ327 (W) (M.1.32) Ϊ893 (Y) (M.1.32) Ϊ1459 (Z) (M.1.32) i2025 (U) (M.1.32)
Ϊ328 (W) (M.1.33) Ϊ894 (Y) (M.1.33) Ϊ1460 (Z) (M.1.33) i2026 (U) (M.1.33)
Ϊ329 (W) (M.1.34) Ϊ895 (Y) (M.1.34) Ϊ1461 (Z) (M.1.34) i2027 (U) (M.1.34)
Ϊ330 (W) (M.1.35) Ϊ896 (Y) (M.1.35) Ϊ1462 (Z) (M.1.35) i2028 (U) (M.1.35) i331 (W) (M.1.36) Ϊ897 (Y) (M.1.36) Ϊ1463 (Z) (M.1.36) i2029 (U) (M.1.36)
Ϊ332 (W) (M.1.37) Ϊ898 (Y) (M.1.37) Ϊ1464 (Z) (M.1.37) i2030 (U) (M.1.37)
Ϊ333 (W) (M.1.38) Ϊ899 (Y) (M.1.38) Ϊ1465 (Z) (M.1.38) i2031 (U) (M.1.38)
Ϊ334 (W) (M.1.39) Ϊ900 (Y) (M.1.39) Ϊ1466 (Z) (M.1.39) i2032 (U) (M.1.39) i335 (W) (M.1.40) i901 (Y) (M.1.40) i1467 (Z) (M.1.40) Ϊ2033 (U) (M.1.40)
Ϊ336 (W) (M.1.41) Ϊ902 (Y) (M.1.41) Ϊ1468 (Z) (M.1.41) Ϊ2034 (U) (M.1.41)
Ϊ337 (W) (M.1.42) Ϊ903 (Y) (M.1.42) Ϊ1469 (Z) (M.1.42) Ϊ2035 (U) (M.1.42)
Ϊ338 (W) (M.1.43) Ϊ904 (Y) (M.1.43) Ϊ1470 (Z) (M.1.43) Ϊ2036 (U) (M.1.43)
Ϊ339 (W) (M.1.44) Ϊ905 (Y) (M.1.44) Ϊ1471 (Z) (M.1.44) Ϊ2037 (U) (M.1.44) Ϊ340 (W) (M.1.45) Ϊ906 (Y) (M.1.45) Ϊ1472 (Z) (M.1.45) Ϊ2038 (U) (M.1.45) i341 (W) (M.1.46) Ϊ907 (Y) (M.1.46) Ϊ1473 (Z) (M.1.46) Ϊ2039 (U) (M.1.46)
Ϊ342 (W) (M.1.47) Ϊ908 (Y) (M.1.47) Ϊ1474 (Z) (M.1.47) i2040 (U) (M.1.47)
Ϊ343 (W) (M.1.48) Ϊ909 (Y) (M.1.48) Ϊ1475 (Z) (M.1.48) Ϊ2041 (U) (M.1.48)
Ϊ344 (W) (M.1.49) i910 (Y) (M.1.49) Ϊ1476 (Z) (M.1.49) i2042 (U) (M.1.49) i345 (W) (M.1.50) i911 (Y) (M.1.50) i1477 (Z) (M.1.50) Ϊ2043 (U) (M.1.50)
Ϊ346 (W) (N.1.1) i912 (Y) (N.1.1) Ϊ1478 (Z) (N.1.1) i2044 (U) (N.1.1)
Ϊ347 (W) (N.1.2) i913 (Y) (N.1.2) Ϊ1479 (Z) (N.1.2) i2045 (U) (N.1.2)
Ϊ348 (W) (N.1.3) i914 (Y) (N.1.3) Ϊ1480 (Z) (N.1.3) Ϊ2046 (U) (N.1.3)
Ϊ349 (W) (N.1.4) i915 (Y) (N.1.4) Ϊ1481 (Z) (N.1.4) i2047 (U) (N.1.4)
Ϊ350 (W) (N.1.5) i916 (Y) (N.1.5) Ϊ1482 (Z) (N.1.5) Ϊ2048 (U) (N.1.5) i351 (W) (N.2.1) i917 (Y) (N.2.1) Ϊ1483 (Z) (N.2.1) Ϊ2049 (U) (N.2.1)
Ϊ352 (W) (N.2.2) i918 (Y) (N.2.2) Ϊ1484 (Z) (N.2.2) i2050 (U) (N.2.2)
Ϊ353 (W) (N.2.3) i919 (Y) (N.2.3) Ϊ1485 (Z) (N.2.3) Ϊ2051 (U) (N.2.3)
Ϊ354 (W) (N.3.1) Ϊ920 (Y) (N.3.1) Ϊ1486 (Z) (N.3.1) i2052 (U) (N.3.1) i355 (W) (N.3.2) i921 (Y) (N.3.2) i1487 (Z) (N.3.2) Ϊ2053 (U) (N.3.2)
Ϊ356 (W) (N.3.3) Ϊ922 (Y) (N.3.3) Ϊ1488 (Z) (N.3.3) i2054 (U) (N.3.3)
Ϊ357 (W) (N.3.4) Ϊ923 (Y) (N.3.4) Ϊ1489 (Z) (N.3.4) i2055 (U) (N.3.4)
Ϊ358 (W) (N.4.1) Ϊ924 (Y) (N.4.1) Ϊ1490 (Z) (N.4.1) Ϊ2056 (U) (N.4.1)
Ϊ359 (W) (N.5.1) Ϊ925 (Y) (N.5.1) Ϊ1491 (Z) (N.5.1) i2057 (U) (N.5.1)
Ϊ360 (W) (N.6.1) Ϊ926 (Y) (N.6.1) Ϊ1492 (Z) (N.6.1) Ϊ2058 (U) (N.6.1) i361 (W) (N.6.2) Ϊ927 (Y) (N.6.2) Ϊ1493 (Z) (N.6.2) Ϊ2059 (U) (N.6.2)
Ϊ362 (W) (N.6.3) Ϊ928 (Y) (N.6.3) Ϊ1494 (Z) (N.6.3) i2060 (U) (N.6.3)
Ϊ363 (W) (N.6.4) Ϊ929 (Y) (N.6.4) Ϊ1495 (Z) (N.6.4) i2061 (U) (N.6.4)
Ϊ364 (W) (N.6.5) Ϊ930 (Y) (N.6.5) Ϊ1496 (Z) (N.6.5) i2062 (U) (N.6.5) i365 (W) (N.7.1) i931 (Y) (N.7.1) i1497 (Z) (N.7.1) Ϊ2063 (U) (N.7.1)
Ϊ366 (W) (N.7.2) Ϊ932 (Y) (N.7.2) Ϊ1498 (Z) (N.7.2) Ϊ2064 (U) (N.7.2)
Ϊ367 (W) (N.7.3) Ϊ933 (Y) (N.7.3) Ϊ1499 (Z) (N.7.3) Ϊ2065 (U) (N.7.3)
Ϊ368 (W) (N.8.1) Ϊ934 (Y) (N.8.1) Ϊ1500 (Z) (N.8.1) Ϊ2066 (U) (N.8.1)
Ϊ369 (W) (N.9.1) Ϊ935 (Y) (N.9.1) Ϊ1501 (Z) (N.9.1) Ϊ2067 (U) (N.9.1)
Ϊ370 (W) (N.10.1) Ϊ936 (Y) (N.10.1) Ϊ1502 (Z) (N.10.1) Ϊ2068 (U) (N.10.1) i371 (W) (N.10.2) Ϊ937 (Y) (N.10.2) Ϊ1503 (Z) (N.10.2) Ϊ2069 (U) (N.10.2)
Ϊ372 (W) (N.10.3) Ϊ938 (Y) (N.10.3) Ϊ1504 (Z) (N.10.3) i2070 (U) (N.10.3)
Ϊ373 (W) (N.10.4) Ϊ939 (Y) (N.10.4) Ϊ1505 (Z) (N.10.4) Ϊ2071 (U) (N.10.4) Ϊ374 (W) (N.10.5) Ϊ940 (Y) (N.10.5) Ϊ1506 (Z) (N.10.5) i2072 (U) (N.10.5) i375 (W) (N.11.1) i941 (Y) (N.11.1) i1507 (Z) (N.11.1) Ϊ2073 (U) (N.11.1)
Ϊ376 (W) (N.12.1) Ϊ942 (Y) (N.12.1) Ϊ1508 (Z) (N.12.1) i2074 (U) (N.12.1)
Ϊ377 (W) (N.12.2) Ϊ943 (Y) (N.12.2) Ϊ1509 (Z) (N.12.2) i2075 (U) (N.12.2)
Ϊ378 (W) (N.12.3) Ϊ944 (Y) (N.12.3) Ϊ1510 (Z) (N.12.3) Ϊ2076 (U) (N.12.3)
Ϊ379 (W) (N.12.4) Ϊ945 (Y) (N.12.4) Ϊ1511 (Z) (N.12.4) i2077 (U) (N.12.4)
Ϊ380 (W) (N.13.1) Ϊ946 (Y) (N.13.1) Ϊ1512 (Z) (N.13.1) Ϊ2078 (U) (N.13.1) i381 (W) (N.13.2) Ϊ947 (Y) (N.13.2) Ϊ1513 (Z) (N.13.2) Ϊ2079 (U) (N.13.2)
Ϊ382 (W) (N.13.3) Ϊ948 (Y) (N.13.3) Ϊ1514 (Z) (N.13.3) i2080 (U) (N.13.3)
Ϊ383 (W) (N.13.4) Ϊ949 (Y) (N.13.4) Ϊ1515 (Z) (N.13.4) i2081 (U) (N.13.4)
Ϊ384 (W) (N.13.5) i950 (Y) (N.13.5) Ϊ1516 (Z) (N.13.5) i2082 (U) (N.13.5) i385 (W) (N.13.6) i951 (Y) (N.13.6) Ϊ1517 (Z) (N.13.6) Ϊ2083 (U) (N.13.6)
Ϊ386 (W) (N.13.7) i952 (Y) (N.13.7) Ϊ1518 (Z) (N.13.7) Ϊ2084 (U) (N.13.7)
Ϊ387 (W) (N.13.8) Ϊ953 (Y) (N.13.8) Ϊ1519 (Z) (N.13.8) Ϊ2085 (U) (N.13.8)
Ϊ388 (W) (N.13.9) Ϊ954 (Y) (N.13.9) Ϊ1520 (Z) (N.13.9) Ϊ2086 (U) (N.13.9)
Ϊ389 (W) (N.14.1) Ϊ955 (Y) (N.14.1) Ϊ1521 (Z) (N.14.1) Ϊ2087 (U) (N.14.1)
Ϊ390 (W) (N.14.2) Ϊ956 (Y) (N.14.2) Ϊ1522 (Z) (N.14.2) Ϊ2088 (U) (N.14.2) i391 (W) (N.15.1) Ϊ957 (Y) (N.15.1) Ϊ1523 (Z) (N.15.1) Ϊ2089 (U) (N.15.1)
Ϊ392 (W) (N.16.1) Ϊ958 (Y) (N.16.1) Ϊ1524 (Z) (N.16.1) i2090 (U) (N.16.1)
Ϊ393 (W) (N.16.2) Ϊ959 (Y) (N.16.2) Ϊ1525 (Z) (N.16.2) i2091 (U) (N.16.2)
Ϊ394 (W) (N.17.1) i960 (Y) (N.17.1) Ϊ1526 (Z) (N.17.1) i2092 (U) (N.17.1) i395 (W) (N.17.2) i961 (Y) (N.17.2) i1527 (Z) (N.17.2) Ϊ2093 (U) (N.17.2)
Ϊ396 (W) (N.17.3) Ϊ962 (Y) (N.17.3) Ϊ1528 (Z) (N.17.3) Ϊ2094 (U) (N.17.3)
Ϊ397 (W) (N.17.4) Ϊ963 (Y) (N.17.4) Ϊ1529 (Z) (N.17.4) Ϊ2095 (U) (N.17.4)
Ϊ398 (W) (N.17.5) Ϊ964 (Y) (N.17.5) Ϊ1530 (Z) (N.17.5) Ϊ2096 (U) (N.17.5)
Ϊ399 (W) (N.17.6) Ϊ965 (Y) (N.17.6) Ϊ1531 (Z) (N.17.6) Ϊ2097 (U) (N.17.6)
Ϊ400 (W) (N.17.7) Ϊ966 (Y) (N.17.7) Ϊ1532 (Z) (N.17.7) Ϊ2098 (U) (N.17.7)
Ϊ401 (W) (N.17.8) Ϊ967 (Y) (N.17.8) Ϊ1533 (Z) (N.17.8) Ϊ2099 (U) (N.17.8)
Ϊ402 (W) (N.17.9) Ϊ968 (Y) (N.17.9) Ϊ1534 (Z) (N.17.9) i2100 (U) (N.17.9)
Ϊ403 (W) (N.17.10) Ϊ969 (Y) (N.17.10) Ϊ1535 (Z) (N.17.10) Ϊ2101 (U) (N.17.10)
Ϊ404 (W) (N.17.11) Ϊ970 (Y) (N.17.11) Ϊ1536 (Z) (N.17.11) i2102 (U) (N.17.11)
Ϊ405 (W) (N.17.12) i971 (Y) (N.17.12) i1537 (Z) (N.17.12) i2103 (U) (N.17.12)
Ϊ406 (W) (0.1.1) Ϊ972 (Y) (0.1.1) Ϊ1538 (Z) (0.1.1) Ϊ2104 (U) (0.1.1) Ϊ407 (W) (0.1.2) Ϊ973 (Y) (0.1.2) Ϊ1539 (Z) (0.1.2) Ϊ2105 (U) (0.1.2)
Ϊ408 (W) (0.1.3) Ϊ974 (Y) (0.1.3) Ϊ1540 (Z) (0.1.3) i2106 (U) (0.1.3)
Ϊ409 (W) (0.1.4) Ϊ975 (Y) (0.1.4) Ϊ1541 (Z) (0.1.4) Ϊ2107 (U) (0.1.4)
Ϊ410 (W) (0.1.5) Ϊ976 (Y) (0.1.5) Ϊ1542 (Z) (0.1.5) i2108 (U) (0.1.5)
Ϊ411 (W) (0.1.6) Ϊ977 (Y) (0.1.6) Ϊ1543 (Z) (0.1.6) i2109 (U) (0.1.6)
Ϊ412 (W) (0.1.7) Ϊ978 (Y) (0.1.7) Ϊ1544 (Z) (0.1.7) i2110 (U) (0.1.7)
Ϊ413 (W) (0.1.8) Ϊ979 (Y) (0.1.8) Ϊ1545 (Z) (0.1.8) Ϊ2111 (U) (0.1.8)
Ϊ414 (W) (0.1.9) Ϊ980 (Y) (0.1.9) Ϊ1546 (Z) (0.1.9) Ϊ2112 (U) (0.1.9)
Ϊ415 (W) (0.1.10) i981 (Y) (0.1.10) i1547 (Z) (0.1.10) Ϊ2113 (U) (0.1.10)
Ϊ416 (W) (0.1.11) Ϊ982 (Y) (0.1.11) Ϊ1548 (Z) (0.1.11) Ϊ2114 (U) (0.1.11)
Ϊ417 (W) (0.1.12) Ϊ983 (Y) (0.1.12) Ϊ1549 (Z) (0.1.12) Ϊ2115 (U) (0.1.12)
Ϊ418 (W) (0.1.13) Ϊ984 (Y) (0.1.13) Ϊ1550 (Z) (0.1.13) Ϊ2116 (U) (0.1.13)
Ϊ419 (W) (0.1.14) Ϊ985 (Y) (0.1.14) Ϊ1551 (Z) (0.1.14) Ϊ2117 (U) (0.1.14)
Ϊ420 (W) (0.1.15) Ϊ986 (Y) (0.1.15) Ϊ1552 (Z) (0.1.15) Ϊ2118 (U) (0.1.15)
Ϊ421 (W) (0.1.16) Ϊ987 (Y) (0.1.16) Ϊ1553 (Z) (0.1.16) Ϊ2119 (U) (0.1.16)
Ϊ422 (W) (0.1.17) Ϊ988 (Y) (0.1.17) Ϊ1554 (Z) (0.1.17) i2120 (U) (0.1.17)
Ϊ423 (W) (0.1.18) Ϊ989 (Y) (0.1.18) Ϊ1555 (Z) (0.1.18) Ϊ2121 (U) (0.1.18)
Ϊ424 (W) (0.1.19) Ϊ990 (Y) (0.1.19) Ϊ1556 (Z) (0.1.19) i2122 (U) (0.1.19)
Ϊ425 (W) (0.1.20) i991 (Y) (0.1.20) i1557 (Z) (0.1.20) i2123 (U) (0.1.20)
Ϊ426 (W) (0.1.21) Ϊ992 (Y) (0.1.21) Ϊ1558 (Z) (0.1.21) Ϊ2124 (U) (0.1.21)
Ϊ427 (W) (0.1.22) Ϊ993 (Y) (0.1.22) Ϊ1559 (Z) (0.1.22) Ϊ2125 (U) (0.1.22)
Ϊ428 (W) (0.1.23) Ϊ994 (Y) (0.1.23) Ϊ1560 (Z) (0.1.23) i2126 (U) (0.1.23)
Ϊ429 (W) (0.1.24) Ϊ995 (Y) (0.1.24) Ϊ1561 (Z) (0.1.24) Ϊ2127 (U) (0.1.24)
Ϊ430 (W) (0.1.25) Ϊ996 (Y) (0.1.25) Ϊ1562 (Z) (0.1.25) i2128 (U) (0.1.25)
Ϊ431 (W) (0.1.26) Ϊ997 (Y) (0.1.26) Ϊ1563 (Z) (0.1.26) i2129 (U) (0.1.26)
Ϊ432 (W) (0.1.27) Ϊ998 (Y) (0.1.27) Ϊ1564 (Z) (0.1.27) i2130 (U) (0.1.27)
Ϊ433 (W) (0.1.28) Ϊ999 (Y) (0.1.28) Ϊ1565 (Z) (0.1.28) Ϊ2131 (U) (0.1.28)
Ϊ434 (W) (0.1.29) Ϊ1000 (Y) (0.1.29) Ϊ1566 (Z) (0.1.29) i2132 (U) (0.1.29) i435 (W) (0.1.30) Ϊ1001 (Y) (0.1.30) i1567 (Z) (0.1.30) i2133 (U) (0.1.30)
Ϊ436 (W) (0.1.31) Ϊ1002 (Y) (0.1.31) Ϊ1568 (Z) (0.1.31) Ϊ2134 (U) (0.1.31)
Ϊ437 (W) (0.1.32) Ϊ1003 (Y) (0.1.32) Ϊ1569 (Z) (0.1.32) Ϊ2135 (U) (0.1.32)
Ϊ438 (W) (0.1.33) Ϊ1004 (Y) (0.1.33) Ϊ1570 (Z) (0.1.33) i2136 (U) (0.1.33)
Ϊ439 (W) (0.1.34) i1005 (Y) (0.1.34) Ϊ1571 (Z) (0.1.34) Ϊ2137 (U) (0.1.34)
Ϊ440 (W) (0.1.35) Ϊ1006 (Y) (0.1.35) Ϊ1572 (Z) (0.1.35) i2138 (U) (0.1.35) Ϊ441 (W) (0.1.36) Ϊ1007 (Y) (0.1.36) Ϊ1573 (Z) (0.1 .36) i2139 (U) (0.1 .36)
Ϊ442 (W) (0.1.37) Ϊ1008 (Y) (0.1.37) Ϊ1574 (Z) (0.1 .37) Ϊ2140 (U) (0.1 .37)
Ϊ443 (W) (0.1.38) Ϊ1009 (Y) (0.1.38) Ϊ1575 (Z) (0.1 .38) Ϊ2141 (U) (0.1 .38)
Ϊ444 (W) (0.2.1 ) Ϊ1010 (Y) (0.2.1 ) Ϊ1576 (Z) (0.2.1 ) Ϊ2142 (U) (0.2.1 )
Ϊ445 (W) (0.2.2) Ϊ101 1 (Y) (0.2.2) i1577 (Z) (0.2.2) Ϊ2143 (U) (0.2.2)
Ϊ446 (W) (0.2.3) Ϊ1012 (Y) (0.2.3) Ϊ1578 (Z) (0.2.3) Ϊ2144 (U) (0.2.3)
Ϊ447 (W) (0.2.4) Ϊ1013 (Y) (0.2.4) Ϊ1579 (Z) (0.2.4) Ϊ2145 (U) (0.2.4)
Ϊ448 (W) (0.2.5) Ϊ1014 (Y) (0.2.5) Ϊ1580 (Z) (0.2.5) Ϊ2146 (U) (0.2.5)
Ϊ449 (W) (0.2.6) Ϊ1015 (Y) (0.2.6) Ϊ1581 (Z) (0.2.6) Ϊ2147 (U) (0.2.6)
Ϊ450 (W) (0.2.7) Ϊ1016 (Y) (0.2.7) Ϊ1582 (Z) (0.2.7) Ϊ2148 (U) (0.2.7)
Ϊ451 (W) (0.2.8) Ϊ1017 (Y) (0.2.8) Ϊ1583 (Z) (0.2.8) Ϊ2149 (U) (0.2.8)
Ϊ452 (W) (0.2.9) Ϊ1018 (Y) (0.2.9) Ϊ1584 (Z) (0.2.9) Ϊ2150 (U) (0.2.9)
Ϊ453 (W) (0.2.10) Ϊ1019 (Y) (0.2.10) Ϊ1585 (Z) (0.2.10) Ϊ2151 (U) (O.2.10)
Ϊ454 (W) (0.2.1 1 ) Ϊ1020 (Y) (0.2.1 1 ) Ϊ1586 (Z) (0.2.1 1 ) Ϊ2152 (U) (0.2.1 1 )
Ϊ455 (W) (0.2.12) Ϊ1021 (Y) (0.2.12) i1587 (Z) (0.2.12) Ϊ2153 (U) (0.2.12)
Ϊ456 (W) (0.2.13) Ϊ1022 (Y) (0.2.13) Ϊ1588 (Z) (0.2.13) Ϊ2154 (U) (0.2.13)
Ϊ457 (W) (0.2.14) Ϊ1023 (Y) (0.2.14) Ϊ1589 (Z) (0.2.14) Ϊ2155 (U) (0.2.14)
Ϊ458 (W) (0.2.15) Ϊ1024 (Y) (0.2.15) Ϊ1590 (Z) (0.2.15) Ϊ2156 (U) (0.2.15)
Ϊ459 (W) (0.2.16) i1025 (Y) (0.2.16) Ϊ1591 (Z) (0.2.16) Ϊ2157 (U) (0.2.16)
Ϊ460 (W) (0.3.1 ) Ϊ1026 (Y) (0.3.1 ) Ϊ1592 (Z) (0.3.1 ) Ϊ2158 (U) (0.3.1 )
Ϊ461 (W) (0.3.2) Ϊ1027 (Y) (0.3.2) Ϊ1593 (Z) (0.3.2) Ϊ2159 (U) (0.3.2)
Ϊ462 (W) (0.3.3) Ϊ1028 (Y) (0.3.3) Ϊ1594 (Z) (0.3.3) i2160 (U) (0.3.3)
Ϊ463 (W) (0.3.4) Ϊ1029 (Y) (0.3.4) Ϊ1595 (Z) (0.3.4) Ϊ2161 (U) (0.3.4)
Ϊ464 (W) (0.3.5) Ϊ1030 (Y) (0.3.5) Ϊ1596 (Z) (0.3.5) i2162 (U) (0.3.5) i465 (W) (0.3.6) Ϊ1031 (Y) (0.3.6) i1597 (Z) (0.3.6) i2163 (U) (0.3.6)
Ϊ466 (W) (0.3.7) i1032 (Y) (0.3.7) Ϊ1598 (Z) (0.3.7) Ϊ2164 (U) (0.3.7)
Ϊ467 (W) (0.3.8) Ϊ1033 (Y) (0.3.8) Ϊ1599 (Z) (0.3.8) Ϊ2165 (U) (0.3.8)
Ϊ468 (W) (0.3.9) Ϊ1034 (Y) (0.3.9) Ϊ1600 (Z) (0.3.9) i2166 (U) (0.3.9)
Ϊ469 (W) (O.3.10) i1035 (Y) (0.3.10) Ϊ1601 (Z) (O.3.10) Ϊ2167 (U) (O.3.10)
Ϊ470 (W) (0.3.1 1 ) Ϊ1036 (Y) (0.3.1 1 ) Ϊ1602 (Z) (0.3.1 1 ) i2168 (U) (0.3.1 1 )
Ϊ471 (W) (0.3.12) Ϊ1037 (Y) (0.3.12) Ϊ1603 (Z) (0.3.12) i2169 (U) (0.3.12)
Ϊ472 (W) (0.3.13) Ϊ1038 (Y) (0.3.13) Ϊ1604 (Z) (0.3.13) Ϊ2170 (U) (0.3.13)
Ϊ473 (W) (0.3.14) Ϊ1039 (Y) (0.3.14) Ϊ1605 (Z) (0.3.14) Ϊ2171 (U) (0.3.14)
Ϊ474 (W) (0.3.15) Ϊ1040 (Y) (0.3.15) Ϊ1606 (Z) (0.3.15) Ϊ2172 (U) (0.3.15) Ϊ475 (W) (0.3.16) Ϊ1041 (Y) (0.3.16) i1607 (Z) (0.3.16) Ϊ2173 (U) (0.3.16)
Ϊ476 (W) (0.3.17) i1042 (Y) (0.3.17) Ϊ1608 (Z) (0.3.17) Ϊ2174 (U) (0.3.17)
Ϊ477 (W) (0.3.18) Ϊ1043 (Y) (0.3.18) Ϊ1609 (Z) (0.3.18) Ϊ2175 (U) (0.3.18)
Ϊ478 (W) (0.3.19) Ϊ1044 (Y) (0.3.19) Ϊ1610 (Z) (0.3.19) Ϊ2176 (U) (0.3.19)
Ϊ479 (W) (O.3.20) i1045 (Y) (O.3.20) Ϊ1611 (Z) (O.3.20) Ϊ2177 (U) (O.3.20)
Ϊ480 (W) (0.3.21) Ϊ1046 (Y) (0.3.21) Ϊ1612 (Z) (0.3.21) Ϊ2178 (U) (0.3.21)
Ϊ481 (W) (0.3.22) Ϊ1047 (Y) (0.3.22) Ϊ1613 (Z) (0.3.22) Ϊ2179 (U) (0.3.22)
Ϊ482 (W) (0.3.23) Ϊ1048 (Y) (0.3.23) Ϊ1614 (Z) (0.3.23) i2180 (U) (0.3.23)
Ϊ483 (W) (0.3.24) Ϊ1049 (Y) (0.3.24) Ϊ1615 (Z) (0.3.24) Ϊ2181 (U) (0.3.24)
Ϊ484 (W) (0.3.25) i1050 (Y) (0.3.25) Ϊ1616 (Z) (0.3.25) i2182 (U) (0.3.25) i485 (W) (0.3.26) Ϊ1051 (Y) (0.3.26) Ϊ1617 (Z) (0.3.26) i2183 (U) (0.3.26) i486 (W) (0.3.27) i1052 (Y) (0.3.27) Ϊ1618 (Z) (0.3.27) Ϊ2184 (U) (0.3.27)
Ϊ487 (W) (0.4.1) i1053 (Y) (0.4.1) Ϊ1619 (Z) (0.4.1) Ϊ2185 (U) (0.4.1)
Ϊ488 (W) (0.4.2) i1054 (Y) (0.4.2) Ϊ1620 (Z) (0.4.2) i2186 (U) (0.4.2)
Ϊ489 (W) (0.4.3) i1055 (Y) (0.4.3) Ϊ1621 (Z) (0.4.3) Ϊ2187 (U) (0.4.3)
Ϊ490 (W) (0.4.4) i1056 (Y) (0.4.4) Ϊ1622 (Z) (0.4.4) i2188 (U) (0.4.4)
Ϊ491 (W) (0.4.5) i1057 (Y) (0.4.5) Ϊ1623 (Z) (0.4.5) i2189 (U) (0.4.5)
Ϊ492 (W) (0.4.6) i1058 (Y) (0.4.6) Ϊ1624 (Z) (0.4.6) i2190 (U) (0.4.6)
Ϊ493 (W) (0.4.7) i1059 (Y) (0.4.7) Ϊ1625 (Z) (0.4.7) Ϊ2191 (U) (0.4.7)
Ϊ494 (W) (0.4.8) Ϊ1060 (Y) (0.4.8) Ϊ1626 (Z) (0.4.8) i2192 (U) (0.4.8) i495 (W) (0.4.9) Ϊ1061 (Y) (0.4.9) i1627 (Z) (0.4.9) i2193 (U) (0.4.9)
Ϊ496 (W) (O.4.10) i1062 (Y) (0.4.10) Ϊ1628 (Z) (0.4.10) Ϊ2194 (U) (0.4.10)
Ϊ497 (W) (0.4.11) Ϊ1063 (Y) (0.4.11) Ϊ1629 (Z) (0.4.11) Ϊ2195 (U) (0.4.11)
Ϊ498 (W) (0.4.12) Ϊ1064 (Y) (0.4.12) Ϊ1630 (Z) (0.4.12) i2196 (U) (0.4.12)
Ϊ499 (W) (0.4.13) i1065 (Y) (0.4.13) Ϊ1631 (Z) (0.4.13) Ϊ2197 (U) (0.4.13)
Ϊ500 (W) (0.4.14) Ϊ1066 (Y) (0.4.14) Ϊ1632 (Z) (0.4.14) i2198 (U) (0.4.14)
Ϊ501 (W) (0.4.15) Ϊ1067 (Y) (0.4.15) Ϊ1633 (Z) (0.4.15) i2199 (U) (0.4.15)
Ϊ502 (W) (0.4.16) Ϊ1068 (Y) (0.4.16) Ϊ1634 (Z) (0.4.16) i2200 (U) (0.4.16)
Ϊ503 (W) (0.4.17) Ϊ1069 (Y) (0.4.17) Ϊ1635 (Z) (0.4.17) i2201 (U) (0.4.17)
Ϊ504 (W) (0.4.18) Ϊ1070 (Y) (0.4.18) Ϊ1636 (Z) (0.4.18) i2202 (U) (0.4.18) i505 (W) (0.4.19) Ϊ1071 (Y) (0.4.19) i1637 (Z) (0.4.19) i2203 (U) (0.4.19)
Ϊ506 (W) (O.4.20) i1072 (Y) (O.4.20) Ϊ1638 (Z) (O.4.20) i2204 (U) (O.4.20)
Ϊ507 (W) (0.4.21) Ϊ1073 (Y) (0.4.21) Ϊ1639 (Z) (0.4.21) i2205 (U) (0.4.21)
Ϊ508 (W) (0.4.22) Ϊ1074 (Y) (0.4.22) Ϊ1640 (Z) (0.4.22) i2206 (U) (0.4.22) Ϊ509 (W) (0.4.23) i1075 (Y) (0.4.23) Ϊ1641 (Z) (0.4.23) i2207 (U) (0.4.23)
Ϊ510 (W) (0.4.24) Ϊ1076 (Y) (0.4.24) Ϊ1642 (Z) (0.4.24) i2208 (U) (0.4.24)
Ϊ51 1 (W) (0.5.1 ) Ϊ1077 (Y) (0.5.1 ) Ϊ1643 (Z) (0.5.1 ) i2209 (U) (0.5.1 )
Ϊ512 (W) (0.5.2) Ϊ1078 (Y) (0.5.2) Ϊ1644 (Z) (0.5.2) i2210 (U) (0.5.2)
Ϊ513 (W) (0.5.3) Ϊ1079 (Y) (0.5.3) Ϊ1645 (Z) (0.5.3) Ϊ221 1 (U) (0.5.3)
Ϊ514 (W) (0.5.4) Ϊ1080 (Y) (0.5.4) Ϊ1646 (Z) (0.5.4) i2212 (U) (0.5.4)
Ϊ515 (W) (0.5.5) Ϊ1081 (Y) (0.5.5) i1647 (Z) (0.5.5) i2213 (U) (0.5.5)
Ϊ516 (W) (0.5.6) i1082 (Y) (0.5.6) Ϊ1648 (Z) (0.5.6) Ϊ2214 (U) (0.5.6)
Ϊ517 (W) (0.5.7) Ϊ1083 (Y) (0.5.7) Ϊ1649 (Z) (0.5.7) Ϊ2215 (U) (0.5.7)
Ϊ518 (W) (0.5.8) Ϊ1084 (Y) (0.5.8) Ϊ1650 (Z) (0.5.8) i2216 (U) (0.5.8)
Ϊ519 (W) (0.5.9) i1085 (Y) (0.5.9) Ϊ1651 (Z) (0.5.9) Ϊ2217 (U) (0.5.9)
Ϊ520 (W) (0.6.1 ) Ϊ1086 (Y) (0.6.1 ) Ϊ1652 (Z) (0.6.1 ) i2218 (U) (0.6.1 )
Ϊ521 (W) (0.6.2) Ϊ1087 (Y) (0.6.2) Ϊ1653 (Z) (0.6.2) i2219 (U) (0.6.2)
Ϊ522 (W) (0.6.3) Ϊ1088 (Y) (0.6.3) Ϊ1654 (Z) (0.6.3) i2220 (U) (0.6.3)
Ϊ523 (W) (0.6.4) Ϊ1089 (Y) (0.6.4) Ϊ1655 (Z) (0.6.4) i2221 (U) (0.6.4)
Ϊ524 (W) (0.6.5) Ϊ1090 (Y) (0.6.5) Ϊ1656 (Z) (0.6.5) i2222 (U) (0.6.5)
Ϊ525 (W) (0.6.6) Ϊ1091 (Y) (0.6.6) i1657 (Z) (0.6.6) i2223 (U) (0.6.6)
Ϊ526 (W) (0.6.7) i1092 (Y) (0.6.7) Ϊ1658 (Z) (0.6.7) i2224 (U) (0.6.7)
Ϊ527 (W) (0.7.1 ) Ϊ1093 (Y) (0.7.1 ) Ϊ1659 (Z) (0.7.1 ) i2225 (U) (0.7.1 )
Ϊ528 (W) (0.7.2) Ϊ1094 (Y) (0.7.2) Ϊ1660 (Z) (0.7.2) i2226 (U) (0.7.2)
Ϊ529 (W) (0.7.3) i1095 (Y) (0.7.3) Ϊ1661 (Z) (0.7.3) i2227 (U) (0.7.3)
Ϊ530 (W) (0.7.4) Ϊ1096 (Y) (0.7.4) Ϊ1662 (Z) (0.7.4) i2228 (U) (0.7.4)
Ϊ531 (W) (0.7.5) Ϊ1097 (Y) (0.7.5) Ϊ1663 (Z) (0.7.5) i2229 (U) (0.7.5)
Ϊ532 (W) (0.7.6) Ϊ1098 (Y) (0.7.6) Ϊ1664 (Z) (0.7.6) i2230 (U) (0.7.6)
Ϊ533 (W) (0.8.1 ) Ϊ1099 (Y) (0.8.1 ) Ϊ1665 (Z) (0.8.1 ) i2231 (U) (0.8.1 )
Ϊ534 (W) (0.8.2) i1 100 (Y) (0.8.2) Ϊ1666 (Z) (0.8.2) i2232 (U) (0.8.2) i535 (W) (0.8.3) Ϊ1 101 (Y) (0.8.3) i1667 (Z) (0.8.3) Ϊ2233 (U) (0.8.3)
Ϊ536 (W) (0.8.4) Ϊ1 102 (Y) (0.8.4) Ϊ1668 (Z) (0.8.4) Ϊ2234 (U) (0.8.4)
Ϊ537 (W) (0.8.5) Ϊ1 103 (Y) (0.8.5) Ϊ1669 (Z) (0.8.5) Ϊ2235 (U) (0.8.5)
Ϊ538 (W) (0.9.1 ) Ϊ1 104 (Y) (0.9.1 ) Ϊ1670 (Z) (0.9.1 ) Ϊ2236 (U) (0.9.1 )
Ϊ539 (W) (0.9.2) Ϊ1 105 (Y) (0.9.2) Ϊ1671 (Z) (0.9.2) Ϊ2237 (U) (0.9.2)
Ϊ540 (W) (0.9.3) Ϊ1 106 (Y) (0.9.3) Ϊ1672 (Z) (0.9.3) Ϊ2238 (U) (0.9.3)
Ϊ541 (W) (O.10.1 ) Ϊ1 107 (Y) (O.10.1 ) Ϊ1673 (Z) (O.10.1 ) Ϊ2239 (U) (O.10.1 )
Ϊ542 (W) (0.1 1 .1 ) i1 108 (Y) (0.1 1 .1 ) Ϊ1674 (Z) (0.1 1 .1 ) i2240 (U) (0.1 1.1 ) Ϊ543 (W) (0.11.2) Ϊ1109 (Y) (0.11.2) Ϊ1675 (Z) (0.11.2) Ϊ2241 (U) (0.11.2)
Ϊ544 (W) (0.11.3) Ϊ1110 (Y) (0.11.3) Ϊ1676 (Z) (0.11.3) i2242 (U) (0.11.3) i545 (W) (0.11.4) Ϊ1111 (Y) (0.11.4) i1677 (Z) (0.11.4) Ϊ2243 (U) (0.11.4)
Ϊ546 (W) (0.12.1) Ϊ1112 (Y) (0.12.1) Ϊ1678 (Z) (0.12.1) i2244 (U) (0.12.1)
Ϊ547 (W) (0.13.1) Ϊ1113 (Y) (0.13.1) Ϊ1679 (Z) (0.13.1) i2245 (U) (0.13.1)
Ϊ548 (W) (0.14.1) Ϊ1114 (Y) (0.14.1) Ϊ1680 (Z) (0.14.1) Ϊ2246 (U) (0.14.1)
Ϊ549 (W) (0.14.2) Ϊ1115 (Y) (0.14.2) Ϊ1681 (Z) (0.14.2) i2247 (U) (0.14.2)
Ϊ550 (W) (0.15.1) Ϊ1116 (Y) (0.15.1) Ϊ1682 (Z) (0.15.1) Ϊ2248 (U) (0.15.1)
Ϊ551 (W) (0.15.2) Ϊ1117 (Y) (0.15.2) Ϊ1683 (Z) (0.15.2) Ϊ2249 (U) (0.15.2)
Ϊ552 (W) (0.15.3) Ϊ1118 (Y) (0.15.3) Ϊ1684 (Z) (0.15.3) i2250 (U) (0.15.3)
Ϊ553 (W) (0.15.4) Ϊ1119 (Y) (0.15.4) Ϊ1685 (Z) (0.15.4) Ϊ2251 (U) (0.15.4)
Ϊ554 (W) (0.15.5) Ϊ1120 (Y) (0.15.5) Ϊ1686 (Z) (0.15.5) i2252 (U) (0.15.5) i555 (W) (0.15.6) Ϊ1121 (Y) (0.15.6) i1687 (Z) (0.15.6) Ϊ2253 (U) (0.15.6)
Ϊ556 (W) (0.15.7) Ϊ1122 (Y) (0.15.7) Ϊ1688 (Z) (0.15.7) i2254 (U) (0.15.7)
Ϊ557 (W) (0.15.8) Ϊ1123 (Y) (0.15.8) Ϊ1689 (Z) (0.15.8) i2255 (U) (0.15.8)
Ϊ558 (W) (0.15.9) Ϊ1124 (Y) (0.15.9) Ϊ1690 (Z) (0.15.9) Ϊ2256 (U) (0.15.9)
Ϊ559 (W) (0.15.10) Ϊ1125 (Y) (0.15.10) Ϊ1691 (Z) (0.15.10) i2257 (U) (0.15.10)
Ϊ560 (W) (0.15.11) Ϊ1126 (Y) (0.15.11) Ϊ1692 (Z) (0.15.11) Ϊ2258 (U) (0.15.11)
Ϊ561 (W) (0.16.1) Ϊ1127 (Y) (0.16.1) Ϊ1693 (Z) (0.16.1) Ϊ2259 (U) (0.16.1)
Ϊ562 (W) (0.16.2) Ϊ1128 (Y) (0.16.2) Ϊ1694 (Z) (0.16.2) i2260 (U) (0.16.2)
Ϊ563 (W) (0.16.3) Ϊ1129 (Y) (0.16.3) Ϊ1695 (Z) (0.16.3) i2261 (U) (0.16.3)
Ϊ564 (W) (0.16.4) Ϊ1130 (Y) (0.16.4) Ϊ1696 (Z) (0.16.4) i2262 (U) (0.16.4) i565 (W) (0.16.5) Ϊ1131 (Y) (0.16.5) i1697 (Z) (0.16.5) Ϊ2263 (U) (0.16.5)
Ϊ566 (W) (0.16.6) Ϊ1132 (Y) (0.16.6) Ϊ1698 (Z) (0.16.6) Ϊ2264 (U) (0.16.6)
In further specific embodiments, the present invention envisages compositions comprising as compound I (component A) at least one nitrification inhibitor as defined in Table 1 , i.e. at least one of compound A #1 to #215 and as compound II (component B) at least one fungicide selected from azoxystrobin, picoxystrobin, pyraclostrobin, trifloxystrobin cyazofamid boscalid, fluopyram, fluxapyroxad, penflufen, penthiopyrad, sedaxane fluazinam cyproconazole, difeno- conazole, flutriafol, ipconazole, prothioconazole, tebuconazole, triticonazole, prochloraz, fenpropimorph metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl 5-fluoro-2-(4- fluorophenylmethoxy)pyrimidin-4-amine,benzimidazoles, thiophanates, carbendazim, thiabendazole, diethofencarb, ethaboxam, fluopicolide, zoxamide, metrafenone, fludioxonil quinoxyfen dimethomorph, mandipropamid, oxathiapiprolin, mancozeb, maneb, metam, me- tiram, thiram, ziram anilazine, chlorothalonil cyflufenamid, and dazomet.
In further specific embodiments, the present invention envisages the use of compositions for increasing the health of a plant, which comprise the combination of a fungicide and (T) or a nitrification inhibitor as defined herein and additionally a fertilizer. Such compositions may be used and provided as agricultural mixtures.
The use of a combination as defined herein above, in particular of a combination of (T) or a nitri- fication inhibitor as defined herein above and a fungicide as defined herein above, or of a composition as defined herein for increasing the health of a plant may be a single use, or it may be a repeated use. As single use, the combination or corresponding compositions may be provided to their target sites, e.g. soil or loci, or objects, e.g. plants, only once in a physiologically relevant time interval, e.g. once a year, or once every 2 to 5 years, or once during the lifetime of a plant.
In other embodiments, the use may be repeated at least once per time period, e.g. the combination as defined herein above, or a composition as defined herein may be used for increasing the health of a plant two times within a time interval of days, weeks or months. The term "at least once" as used in the context of a use of the combination means that the combination may be used two times, or several times, i.e. that a repetition or multiple repetitions of an application or treatment with the combinationmay be envisaged. Such a repetition may a 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times or more frequent repetition of the use. The combination according to the present invention or its components may be used in any suitable form. For example, it may be used as coated or uncoated granule, in liquid or semi-liquid form, as sprayable entity, or in irrigation approaches etc. In further embodiments, the components may be used in different forms. In specific embodiments, the components may be applied or used as such, i.e.without formulations, fertilizer, additional water, coatings, or any further in- gredient.
The term "irrigation" as used herein refers to the watering of plants or loci or soils or soil substit- uents where a plant grows or is intended to grow, wherein said watering includes the provision of the combination or a corresponding composition according to the present invention together with water.
In a further aspect the invention relates to a composition for increasing the health of a plant comprising at least one nitrification inhibitor wherein said nitrification inhibitor is a compound of formula I or a derivative as defined herein above; and at least one fungicide as defined herein above. In a preferred embodiment, the composition comprises the combination of nitrification inhibitor and fungicide as defined in Table 2, supra. In a further aspect the invention relates to a composition comprising (T) and at least one fungicide as defined herein above, preferably relates to a composition for increasing the health of a plant comprising (T) and at least one fungicide as defined herein above. In a preferred embodiment, the composition comprises the combination of (T) and fungicide as defined in Table 3, supra. In another preferred embodiment, the use of the compositions comprising (T) and fungicide as defined in Table 3 for improving plant health, and/or for increasing yield of the plant, and/or for enhancing the urease inhibiting effect of the (thio)phosphoric acid triamide(s), and/or for enhancing the fungicidal effect of the fungicide was found. In further specific embodiments, the agricultural compositon further comprises a carrier.
The term "composition for increasing the health of a plant" as used herein refers to a composition which is suitable, e.g. comprises effective concentrations and amounts of ingredients such as (T) or nitrification inhibitors, in particular compounds of formula I or derivatives as defined herein, and fungicides for increasing the health of a plant. This includes the reduction of nitrification in any context or environment in which nitrification may occur and the reduction of biotic stress factors due to a fungicidal effect to fungi such as phytophathogenic fungi. In one embodiment, the nitrification and biotic stress may be reduced in or on or at the locus of a plant. Typically, the nitrification may be reduced in the root zone of a plant. In specific embodiments, the composition may be an agricultural composition, i.e. a composition adapated to the use in the agricultural field. "Effective amounts" or "effective concentrations" of (T) or nitrification inhibitors and fungicides as defined herein may be determined according to suitable in vitro and in vivo testings known to the skilled person. These amounts and concentrations may be adjusted to the locus, plant, soil, climate conditions or any other suitable parameter which may have an influ- ence on nitrification processes, and/or on competitive plant growth.
An "carrier" as used herein is a substance or composition which facilitates the delivery and/or release of the ingredients to the place or lcous of destination. The term includes, for instance, agrochemical carriers which facilitate the delivery and/or release of agrochemicals in their field of use, in particular on or into plants.
Examples of suitable carriers include solid carriers such as phytogels, or hydrogels, or mineral earths e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, bole, loess, clays, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e.g., urea, urea based NPK, UAN , ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers. Further suitable examples of carriers include fumed silica or precipitated silica, which may, for instance, be used in solid formulations as flow aid, anti-caking aid, milling aid and as carrier for liquid active ingredients. Additional examples of suitable carriers are microparticles, for instance microparticles which stick to plant leaves and release their content over a certain period of time. In specific embodiments, agrochemical carriers such as composite gel microparticles that can be used to deliver plant-protection active principles, e.g. as described in US 6,180,141 ; or com- positions comprising at least one phytoactive compound and an encapsulating adjuvant, wherein the adjuvant comprises a fungal cell or a fragment thereof, e.g. as described in WO
2005/102045; or carrier granules, coated with a lipophilic tackifier on the surface, wherein the carrier granule adheres to the surface of plants, grasses and weeds, e.g. as disclosed in US 2007/0280981 may be used. In further specific embodiments, such carriers may include specific, strongly binding molecule which assure that the carrier sticks to the plant till its content is completely delivered. For instance, the carrier may be or comprise cellulose binding domains (CBDs) have been described as useful agents for attachment of molecular species to cellulose (see US 6,124,1 17); or direct fusions between a CBD and an enzyme; or a multifunctional fu- sion protein which may be used for delivery of encapsulated agents, wherein the multifunctional fusion proteins may consist of a first binding domain which is a carbohydrate binding domain and a second binding domain, wherein either the first binding domain or the second binding domain can bind to a microparticle (see also WO 03/031477). Further suitable examples of carriers include bifunctional fusion proteins consisting of a CBD and an anti-RR6 antibody fragment binding to a microparticle, which complex may be deposited onto treads or cut grass (see also WO 03/031477). In another specific embodiment the carrier may be active ingredient carrier granules that adhere to the surface of plants, grasses and weeds etc. using a moisture-active coating, for instance including gum arabic, guar gum, gum karaya, gum tragacanth and locust bean gum. Upon application of the inventive granule onto a plant surface, water from precipita- tion, irrigation, dew, co-application with the granules from special application equipment, or gut- tation water from the plant itself may provide sufficient moisture for adherence of the granule to the plant surface (see also US 2007/0280981 ).
In another specific embodiment the carrier, e.g. an agrochemical carrier may be or comprise polyaminoacids. Polyaminoacids may be obtained according to any suitable process, e.g. by polymerization of single or multiple amino acids such as glycine, alanine, valine, leucine, isoleu- cine, phenylalanine, proline, tryptophan, serine, tyrosine, cysteine, methionine, asparagine, glu- tamine, threonine, aspartic acid, glutamic acid, lysine, arginine, histidine and/or ornithine. Polyaminoacids may be combined with a combination of a nitrification inhibitor or (T) and a fungicide according to the present invention and, in certain embodiments, also with further carriers as mentioned herein above, or other nitrification inhibitors as mentioned herein in any suitable ratio. For example, polyaminoacids may be combined with a nitrification inhibitor according to the present invention in a ratio of 1 to 10 (polyaminoacids) vs. 0.5 to 2 (combination according to the present invention, or nitrification inhibitor according to the present invention).
For compositions (including kits-of parts) according to the invention comprising nitrification inhibitor as defined herein above and a fungicide, the weight ratio of the nitrification inhibitor as defined herein above and the fungicide generally depends from the properties of the active substances used, usually it is in the range of from 1 :1000 to 1000:1 , regularly in the range of from 1 :500 to 500:1 , preferably in the range of from 1 :250 to 250:1 , more preferably in the range of from 1 :100 to 100:1 , most preferably in the range of from 1 :70 to 70:1 , particularly preferably in the range of from 1 :50 to 50:1 , particularly more preferably in the range of from 1 :30 to 30:1 , particularly most preferably in the range from 1 :20 to 20:1 , particularly in the range of from 1 :15 to 15:1 , especially preferably in the range of from 1 :10 to 10:1 , especially more preferably in the range of from 1 :8 to 8:1 , especially most preferably in the range of from 1 :6.5 to 6.5:1 , especially in the range of from 1 :5 to 5:1 , in particular preferably in the range of 1 :4 to 4:1 , in particular more preferably in the range of from 1 :3 to 3:1 , in particular most preferably in the range of from 2.5:1 to 1 :2.5, in particular in the range of from 1 :2 to 2:1 , for example in the range of from 1 :1 .5 to 1.5:1 . For compositions (including kits-of parts) according to the invention, the weight ratio of the nitrification inhibitor as defined herein above and the fungicide generally depends from the properties of the active substances used, usually it is not more than 1000:1 , regularly not more than 250:1 , preferably not more than 100:1 , more preferably not more than 50:1 , most prefera- bly not more than 30:1 , particularly preferably not more than 15:1 , particularly more preferably not more than 8:1 , particularly most preferably not more than 4:1 , particularly not more than 2:1 , especially preferably not more than 1 :1 , especially more preferably not more than 1 :2, especially most preferably not more than 1 :4, especially not more than 1 :8, in particular preferably not more than 1 :15, in particular more preferably not more than 1 :30, in particular most preferably not more than 1 :50, in particular not more than 1 : 100, for example preferably not more than
1 :250, for example not more than 1 : 1000. For compositions (including kits-of parts) according to the invention, the weight ratio of the nitrification inhibitor as defined herein above and the fungicide generally depends from the properties of the active substances used, usually it is at least 1000: 1 , regularly at least 250: 1 , preferably at least 100: 1 , more preferably at least 50: 1 , most preferably at least 30: 1 , particularly preferably at least 15:1 , particularly more preferably at least 8:1 , particularly most preferably at least 4:1 , particularly at least 2:1 , especially preferably at least 1 :1 , especially more preferably at least 1 :2, especially most preferably at least 1 :4, especially at least 1 :8, in particular preferably at least 1 :15, in particular more preferably at least 1 :30, in particular most preferably at least 1 :50, in particular at least 1 :100, for example prefera- bly at least 1 :250, for example at least 1 :1000.
For compositions (including kits-of parts) according to the invention comprising (T) and a fungicide, the weight ratio of (T) and the fungicide generally depends from the properties of the active substances used, usually it is in the range of from 1 :1000 to 1000:1 , regularly in the range of from 1 :500 to 500:1 , preferably in the range of from 1 :250 to 250:1 , more preferably in the range of from 1 :100 to 100:1 , most preferably in the range of from 1 :70 to 70:1 , particularly preferably in the range of from 1 :50 to 50:1 , particularly more preferably in the range of from 1 :30 to 30:1 , particularly most preferably in the range from 1 :20 to 20:1 , particularly in the range of from 1 :15 to 15:1 , especially preferably in the range of from 1 :10 to 10:1 , especially more preferably in the range of from 1 :8 to 8:1 , especially most preferably in the range of from 1 :6.5 to 6.5:1 , especially in the range of from 1 :5 to 5:1 , in particular preferably in the range of 1 :4 to 4:1 , in particular more preferably in the range of from 1 :3 to 3:1 , in particular most preferably in the range of from 2.5: 1 to 1 :2.5, in particular in the range of from 1 :2 to 2: 1 , for example in the range of from 1 : 1.5 to 1 .5:1. For compositions (including kits-of parts) according to the inven- tion, the weight ratio of (T) and the fungicide generally depends from the properties of the active substances used, usually it is not more than 1000:1 , regularly not more than 250:1 , preferably not more than 100:1 , more preferably not more than 50:1 , most preferably not more than 30:1 , particularly preferably not more than 15:1 , particularly more preferably not more than 8:1 , par- ticularly most preferably not more than 4:1 , particularly not more than 2:1 , especially preferably not more than 1 :1 , especially more preferably not more than 1 :2, especially most preferably not more than 1 :4, especially not more than 1 :8, in particular preferably not more than 1 :15, in particular more preferably not more than 1 :30, in particular most preferably not more than 1 :50, in particular not more than 1 : 100, for example preferably not more than 1 :250, for example not more than 1 :1000. For compositions (including kits-of parts) according to the invention, the weight ratio of (T) and the fungicide generally depends from the properties of the active substances used, usually it is at least 1000: 1 , regularly at least 250: 1 , preferably at least 100: 1 , more preferably at least 50:1 , most preferably at least 30:1 , particularly preferably at least 15:1 , particularly more preferably at least 8:1 , particularly most preferably at least 4:1 , particularly at least 2:1 , especially preferably at least 1 :1 , especially more preferably at least 1 :2, especially most preferably at least 1 :4, especially at least 1 :8, in particular preferably at least 1 :15, in particular more preferably at least 1 :30, in particular most preferably at least 1 :50, in particular at least 1 :100, for example preferably at least 1 :250, for example at least 1 :1000.
The composition for increasing the health of a plant comprising at least one nitrification inhibitor as defined herein or (T) may further comprise additional ingredients, for example at least one pesticidal compound. For example, the composition may additionally comprise at least one her- bicidal compound and/or at least one insecticidal compound and/or at least one nematicide and/or at least one biopesticide.
In further embodiments, the composition may, in addition to the above indicated ingredients, in particular in addition to (T) or the nitrification inhibitor of the compound of formula I, further comprise one or more alternative or additional nitrification inhibitors. Examples of envisaged alternative or additional nitrification inhibitors are linoleic acid, alpha-linolenic acid, methyl p- coumarate, methyl ferulate, methyl 3-(4-hydroxyphenyl) propionate (MHPP), Karanjin, brachi- alacton, p-benzoquinone sorgoleone, 2-chloro-6-(trichloromethyl)-pyridine (nitrapyrin or N- serve), dicyandiamide (DCD, DIDIN), 3,4-dimethyl pyrazole phosphate (DMPP, ENTEC), 4- amino-1 ,2,4-triazole hydrochloride (ATC), 1 -amido-2-thiourea (ASU), 2-amino-4-chloro-6- methylpyrimidine (AM), 2-mercapto-benzothiazole (MBT), 5-ethoxy-3-trichloromethyl-1 ,2,4- thiodiazole (terrazole, etridiazole), 2-sulfanilamidothiazole (ST), ammoniumthiosulfate (ATU), 3- methylpyrazol (3-MP), 3,5-dimethylpyrazole (DMP), 1 ,2,4-triazole, thiourea (TU), N-(1 H- pyrazolyl-methyl)acetamides such as N-((3(5)-methyl-1 H-pyrazole-1 -yl)methyl)acetamide, and N-(1 H-pyrazolyl-methyl)formamides such as N-((3(5)-methyl-1 H-pyrazole-1 -yl)methyl forma- mide, N-(4-chloro-3(5)-methyl-pyrazole-1 -ylmethyl)-formamide, N-(3(5),4-dimethyl-pyrazole-1 - ylmethyl)-formamide, mixtures of 3,4-dimethylpyrazole phospate succinic acid and 4,5- dimethylpyrazole phosphate succinic acid, neem, products based on ingredients of neem, cyan amide, melamine, zeolite powder, catechol, benzoquinone, sodium tetra borate, and zinc sulfate.. In a preferred embodiment, the composition according to the present invention may comprise a combination of a fungicide as defined herein above, of (T) or the nitrification inhibitor of the compound of formula I and 2-chloro-6-(trichloromethyl)-pyridine (nitrapyrin or N-serve). In a further preferred embodiment, the composition according to the present invention may comprise a combination of a fungicide as defined herein above, of (T) or the nitrification inhibitor of the compound of formula I and 5-ethoxy-3-trichloromethyl-1 ,2,4-thiodiazole (terrazole, etridi- azole).
In a further preferred embodiment, the composition according to the present invention may comprise a combination of a fungicide as defined herein above, of (T) or the nitrification inhibitor of the compound of formula I and dicyandiamide (DCD, DIDIN). In a further preferred embodiment, the composition according to the present invention may comprise a combination of a fungicide as defined herein above, of (T) or the nitrification inhibitor of the compound of formula I and 3,4-dimethyl pyrazole phosphate (DMPP, ENTEC).
In a further preferred embodiment, the composition according to the present invention may comprise a combination of a fungicide as defined herein above, of (T) or the nitrification inhibitor of the compound of formula I and 2-amino-4-chloro-6-methylpyrimidine (AM).
In a further preferred embodiment, the composition according to the present invention may comprise a combination of a fungicide as defined herein above, of (T) or the nitrification inhibitor of the compound of formula I and 2-mercapto-benzothiazole (MBT).
In a further preferred embodiment, the composition according to the present invention may comprise a combination of a fungicide as defined herein above, of (T) or the nitrification inhibitor of the compound of formula I and 2-sulfanilamidothiazole (ST).
In a further preferred embodiment, the composition according to the present invention may comprise a combination of a fungicide as defined herein above, of (T) or the nitrification inhibitor of the compound of formula I and 3-methylpyrazol (3-M P). In a further preferred embodiment, the composition according to the present invention may comprise a combination of a fungicide as defined herein above, of (T) or the nitrification inhibitor of the compound of formula I and 3,5-dimethylpyrazole (DMP).
In a further preferred embodiment, the composition according to the present invention may comprise a combination of a fungicide as defined herein above, of (T) or the nitrification inhibitor of the compound of formula I and 1 ,2,4-triazol.
In a further preferred embodiment, the composition according to the present invention may comprise a combination of a fungicide as defined herein above, of (T) or the nitrification inhibitor of the compound of formula I and thiourea (TU).
In yet another preferred embodiment, the composition according to the present invention may comprise a combination of a fungicide as defined herein above, of (T) or the nitrification inhibitor of the compound of formula I and linoleic acid. In yet another preferred embodiment, the composition according to the present invention may comprise a combination of a fungicide as defined herein above, of (T) or the nitrification inhibitor of the compound of formula I and alpha-linolenic acid.
In yet another preferred embodiment, the composition according to the present invention may comprise a combination of a fungicide as defined herein above, of (T) or the nitrification inhibitor of the compound of formula I and methyl p-coumarate. In yet another preferred embodiment, the composition according to the present invention may comprise a combination of a fungicide as defined herein above, of (T) or the nitrification inhibitor of the compound of formula I and methyl 3-(4-hydroxyphenyl) propionate (MHPP).
In yet another preferred embodiment, the composition according to the present invention may comprise a combination of a fungicide as defined herein above, of (T) or the nitrification inhibitor of the compound of formula I and methyl ferulate.
In yet another preferred embodiment, the composition according to the present invention may comprise a combination of a fungicide as defined herein above, of (T) or the nitrification inhibitor of the compound of formula I and Karanjin.
In yet another preferred embodiment, the composition according to the present invention may comprise a combination of a fungicide as defined herein above, of (T) or the nitrification inhibitor of the compound of formula I and brachialacton.
In yet another preferred embodiment, the composition according to the present invention may comprise a combination of a fungicide as defined herein above, of (T) or the nitrification inhibitor of the compound of formula I and p-benzoquinone sorgoleone. In yet another preferred embodiment, the composition according to the present invention may comprise a combination of a fungicide as defined herein above, of (T) or the nitrification inhibitor of the compound of formula I and 4-amino-1 ,2,4-triazole hydrochloride (ATC).
In yet another preferred embodiment, the composition according to the present invention may comprise a combination of a fungicide as defined herein above, of (T) or the nitrification inhibitor of the compound of formula I and 1 -amido-2-thiourea (ASU).
In further embodiments, the composition according to the present invention may comprise a combination of a fungicide as defined herein above, of (T) or the nitrification inhibitor of the compound of formula I and two entities selected from the group comprising: linoleic acid, alpha- linolenic acid, methyl p-coumarate, methyl ferulate, methyl 3-(4-hydroxyphenyl) propionate (MHPP), Karanjin, brachialacton, p-benzoquinone sorgoleone, 2-chloro-6-(trichloromethyl)- pyridine (nitrapyrin or N-serve), dicyandiamide (DCD, DIDIN), 3,4-dimethyl pyrazole phosphate (DM PP, ENTEC), 4-amino-1 ,2,4-triazole hydrochloride (ATC), 1 -amido-2-thiourea (ASU), 2- amino-4-chloro-6-methylpyrimidine (AM), 2-mercapto-benzothiazole (MBT), 5-ethoxy-3- trichloromethyl-1 ,2,4-thiodiazole (terrazole, etridiazole), 2-sulfanilamidothiazole (ST), ammoni- umthiosulfate (ATU), 3-methylpyrazol (3-M P), 3,5-dimethylpyrazole (DM P), 1 ,2,4-triazol and thiourea (TU).
In yet another group of embodiments, the composition according to the present invention may comprise a combination of a fungicide as defined herein above, of (T) or the nitrification inhibitor of the compound of formula I and three, four or more entities selected from the group comprising: linoleic acid, alpha-linolenic acid, methyl p-coumarate, methyl ferulate, methyl 3-(4- hydroxyphenyl) propionate (MHPP), Karanjin, brachialacton, p-benzoquinone sorgoleone, 2- chloro-6-(trichloromethyl)-pyridine (nitrapyrin or N-serve), dicyandiamide (DCD, DIDIN), 3,4- dimethyl pyrazole phosphate (DM PP, ENTEC), 4-amino-1 ,2,4-triazole hydrochloride (ATC), 1 - amido-2-thiourea (ASU), 2-amino-4-chloro-6-methylpyrimidine (AM), 2-mercapto-benzothiazole (MBT), 5-ethoxy-3-trichloromethyl-1 ,2,4-thiodiazole (terrazole, etridiazole), 2- sulfanilamidothiazole (ST), ammoniumthiosulfate (ATU), 3-methylpyrazol (3-MP), 3,5- dimethylpyrazole (DMP), 1 ,2,4-triazol and thiourea (TU).
In further specific embodiments, the composition may comprise the combination of (T) or nitrification inhibitor and fungicide as defined in Table 2 or Table 3 and at least one element selected from the group comprising: linoleic acid, alpha-linolenic acid, methyl p-coumarate, methyl ferulate, methyl 3-(4-hydroxyphenyl) propionate (M HPP), Karanjin, brachialacton, p-benzoquinone sorgoleone, 2-chloro-6-(trichloromethyl)-pyridine (nitrapyrin or N-serve), dicyandiamide (DCD, DIDIN), 3,4-dimethyl pyrazole phosphate (DMPP, ENTEC), 4-amino-1 ,2,4-triazole hydrochloride (ATC), 1 -amido-2-thiourea (ASU), 2-amino-4-chloro-6-methylpyrimidine (AM), 2-mercapto- benzothiazole (MBT), 5-ethoxy-3-trichloromethyl-1 ,2,4-thiodiazole (terrazole, etridiazole), 2- sulfanilamidothiazole (ST), ammoniumthiosulfate (ATU), 3-methylpyrazol (3-MP), 3,5- dimethylpyrazole (DMP), 1 ,2,4-triazole, thiourea (TU), N-(1 H-pyrazolyl-methyl)acetamides such as N-((3(5)-methyl-1 H-pyrazole-1 -yl)methyl)acetamide, and N-(1 H-pyrazolyl-methyl)formamides such as N-((3(5)-methyl-1 H-pyrazole-1 -yl)methyl formamide, N-(4-chloro-3(5)-methyl-pyrazole- 1 -ylmethyl)-formamide, N-(3(5),4-dimethyl-pyrazole-1 -ylmethyl)-formamide, mixtures of 3,4- dimethylpyrazole phospate succinic acid and 4,5-dimethylpyrazole phosphate succinic acid, neem, products based on ingredients of neem, cyan amide, melamine, zeolite powder, catechol, benzoquinone, sodium tetra borate, and zinc sulfate. In further embodiments, the composition may, in addition to the above indicated ingredients, in particular in addition to a fungicide as defined herein above, and to the nitrification inhibitor of the compound of formula I, further comprise one or more urease inhibitors. Examples of envisaged urease inhibitors include N-(n-butyl) thiophosphoric acid triamide (NBPT, Agrotain), N-(n- propyl) thiophosphoric acid triamide (NPPT), 2-nitrophenyl phosphoric triamide (2-NPT), further NXPTs known to the skilled person, phenylphosphorodiamidate (PPD/PPDA), hydroquinone, ammonium thiosulfate, and LIMUS, i.e. a mixture of NBPT and NPPT with about NBPT at 63% and NPPT at 22%, secondary compounds at 10%, further secondary compounds such as amines below 4% and dimerease derivatives below 1 %. In a preferred embodiment, the composition according to the present invention may comprise a fungicide as defined herein above and a combination of the nitrification inhibitor of the compound of formula I and N-(n-butyl) thiophosphoric acid triamide (NBPT, Agrotain).
In a further preferred embodiment, the composition according to the present invention may comprise a fungicide as defined herein above and a combination of (T) or the nitrification inhibitor of the compound of formula I and phenylphosphorodiamidate (PPD/PPDA). In a further preferred embodiment, the composition according to the present invention may comprise a fungicide as defined herein above and a combination of the nitrification inhibitor of the compound of formula I and N-(n-propyl) thiophosphoric acid triamide (N PPT).
In a further preferred embodiment, the composition according to the present invention may comprise a fungicide as defined herein above and a combination of the nitrification inhibitor of the compound of formula I and 2-nitrophenyl phosphoric triamide (2-NPT).
In a further preferred embodiment, the composition according to the present invention may comprise a fungicide as defined herein above and a combination of (T) or the nitrification inhibi- tor of the compound of formula I and hydroquinone.
In a further preferred embodiment, the composition according to the present invention may comprise a fungicide as defined herein above and a combination of (T) or the nitrification inhibitor of the compound of formula I and ammonium thiosulfate.
In a further preferred embodiment, the composition according to the present invention may comprise a fungicide as defined herein above and a combination of the nitrification inhibitor of the compound of formula I and LIMUS. In further embodiments, the composition according to the present invention may comprise a fungicide as defined herein above and a combination of the nitrification inhibitor of the compound of formula I and two or more entities selected from the group comprising: N-(n-butyl) thiophosphoric acid triamide (NBPT, Agrotain), N-(n-propyl) thiophosphoric acid triamide (NPPT), 2-nitrophenyl phosphoric triamide (2-NPT), further NXPTs known to the skilled person, phe- nylphosphorodiamidate (PPD/PPDA), hydroquinone, ammonium thiosulfate, and LIMUS.
In further embodiments, the composition may, in addition to one, more or all of the above indicated ingredients, in particular in addition to (T) or the nitrification inhibitor of the compound of formula I and a fungicide, further comprise one or more plant growth regulators. Examples of envisaged plant growth regulators are antiauxins, auxins, cytokinins, defoliants, ethylene modulators, ethylene releasers, gibberellins, growth inhibitors, morphactins, growth retardants, growth stimulators, and further unclassified plant growth regulators. In a preferred embodiment, the composition according to the present invention may comprise a combination of the nitrification inhibitor of the compound of formula I and a fungicide and at least one compound selected from the group comprising: abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine (= N-6 benzyladenine), brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, diflufenzopyr, dikegulac, dimethipin, 2,6- dimethylpyridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid, maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), 1 - methylcyclopropene (1 -MCP), naphthaleneacetic acid, N-6 benzyladenine, paclobutrazol, pro- hexadione (prohexadione calcium), prohydrojasmon, thidiazuron, triapenthenol, tributyl phos- phorotrithioate, 2,3,5-tri-iodobenzoic acid, trinexapac-ethyl, and uniconazole.
In a preferred embodiment, the composition according to the present invention may comprise a combination of (T) and a fungicide as defined herein above and at least one compound selected from the group comprising: abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine (= N-6 benzyladenine), brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, diflufenzopyr, dikegulac, dimethipin, 2,6-dimethylpyridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid, maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), 1 -methylcyclopropene (1 - MCP), naphthaleneacetic acid, N-6 benzyladenine, paclobutrazol, prohexadione (prohexadione calcium), prohydrojasmon, thidiazuron, triapenthenol, tributyl phosphorotrithioate, 2,3,5-tri- iodobenzoic acid, trinexapac-ethyl, and uniconazole.
In further specific embodiments, the agricultural compositon as defined herein above may additionally comprises an fertilizer. In case the combination of fungicides and (T) or nitrification in- hibitors is used together with a fertilizer, or when a composition is provided in combination with a fertilizer, such mixtures may be provided or used as agrochemical mixtures.
In the terms of the present invention "agrochemical mixture" means a combination of at three or more compounds. The term is, however, not restricted to a physical mixture comprising three or more compounds, but refers to any preparation form of said compounds, the use of which many be time- and/or locus-related.
The agrochemical mixtures may, for example, be formulated separately but applied in a temporal relationship, i.e. simultaneously or subsequently, the subsequent application having a time interval which allows a combined action of the compounds.
Furthermore, the individual compounds of the agrochemical mixtures according to the invention such as parts of a kit or parts of the mixture may be mixed by the user himself in a suitable mixing device. In specific embodiments further auxiliaries may be added, if appropriate.
The term "fertilizers" is to be understood as chemical compounds applied to promote plant and fruit growth. Fertilizers are typically applied either through the soil (for uptake by plant roots), through soil substituents (also for uptake by plant roots), or by foliar feeding (for uptake through leaves). The term also includes mixtures of one or more different types of fertilizers as mentioned below.
The term "fertilizers" can be subdivided into several categories including: a) organic fertilizers (composed of decayed plant/animal matter), b) inorganic fertilizers (composed of chemicals and minerals) and c) urea-containing fertilizers.
Organic fertilizers include manure, e.g. liquid manure, semi-liquid manure, biogas manure, stable manure or straw manure, slurry, liquid dungwater, sewage sludge, worm castings, peat, seaweed, compost, sewage, and guano. Green manure crops are also regularly grown to add nutrients (especially nitrogen) to the soil. Manufactured organic fertilizers include compost, blood meal, bone meal and seaweed extracts. Further examples are enzyme digested proteins, fish meal, and feather meal. The decomposing crop residue from prior years is another source of fertility.
Inorganic fertilizers are usually manufactured through chemical processes (such as the Haber- Bosch process), also using naturally occurring deposits, while chemically altering them (e.g. concentrated triple superphosphate). Naturally occurring inorganic fertilizers include Chilean sodium nitrate, mine rock phosphate, limestone, sulfate of potash, muriate of potash, and raw potash fertilizers.
Typical solid fertilizers are in a crystalline, prilled or granulated form. Typical nitrogen containing inorganic fertilizers are ammonium nitrate, calcium ammonium nitrate, ammonium sulfate, ammonium sulfate nitrate, calcium nitrate, diammonium phosphate, monoammonium phosphate, ammonium thio sulfate and calcium cyanamide.
The inorganic fertilizer may be an NPK fertilizer. "NPK fertilizers" are inorganic
fertilizers formulated in appropriate concentrations and combinations comprising the
three main nutrients nitrogen (N), phosphorus (P) and potassium (K) as well as
typically S, Mg, Ca, and trace elements. "NK fertilizers" comprise the two main
nutrients nitrogen (N) and potassium (K) as well as typically S, Mg, Ca, and trace
elements. "NP fertilizers" comprise the two main nutrients nitrogen (N) and phosphorus (P) as well as typically S, Mg, Ca, and trace elements.
Urea-containing fertilizer may, in specific embodiments, be formaldehyde urea, UAN, urea sulfur, stabilized urea, urea based NPK-fertilizers, or urea ammonium sulfate. Also envisaged is the use of urea as fertilizer. In case urea-containing fertilizers or urea are used or provided, it is particularly preferred that urease inhibitors as defined herein above may be added or additional- ly be present, or be used at the same time or in connection with the urea-containing fertilizers.
Fertilizers may be provided in any suitable form, e.g. as coated or uncoated granules, in liquid or semi-liquid form, as sprayable fertilizer, or via fertigation etc. Coated fertilizers may be provided with a wide range of materials. Coatings may, for example, be applied to granular or prilled nitrogen (N) fertilizer or to multi-nutrient fertilizers. Typically, urea is used as base material for most coated fertilizers. The present invention, however, also envisages the use of other base materials for coated fertilizers, any one of the fertilizer materials defined herein. In certain embodiments, elemental sulfur may be used as fertilizer coating. The coating may be performed by spraying molten S over urea granules, followed by an application of sealant wax to close fissures in the coating. In a further embodiment, the S layer may be covered with a layer of organic polymers, preferably a thin layer of organic polymers. In an- other embodiment, the coated fertilizers are preferably physical mixtures of coated and non- coated fertilizers.
Further envisaged coated fertilizers may be provided by reacting resin-based polymers on the surface of the fertilizer granule. A further example of providing coated fertilizers includes the use of low permeability polyethylene polymers in combination with high permeability coatings.
In specific embodiments the composition and/or thickness of the fertilizer coating may be adjusted to control, for example, the nutrient release rate for specific applications. The duration of nutrient release from specific fertilizers may vary, e.g. from several weeks to many months. The presence of (T) or nitrification inhibitors and fungicides in a mixture with coated fertilizers may accordingly be adapted. It is, in particular, envisaged that the nutrient release involves or is accompanied by the release of an nitrification inhibitor or (T) and fungicide according to the present invention. Coated fertilizers may be provided as controlled release fertilizers (CRFs). In specific embodiments these controlled release fertilizers are fully coated N-P-K fertilizers, which are homogeneous and which typically show a pre-defined longevity of release. In further embodiments, the CRFs may be provided as blended controlled release fertilizer products which may contain coated, uncoated and/or slow release components. In certain embodiments, these coated ferti- lizers may additionally comprise micronutrients. In specific embodiments these fertilizers may show a pre-defined longevity, e.g. in case of N-P-K fertilizers.
Additionally envisaged examples of CRFs include patterned release fertilizers. These fertilizers typically show a pre-defined release patterns (e.g. hi/standard/lo) and a pre-defined longevity. In exemplary embodiments fully coated N-P-K, Mg and micronutrients may be delivered in a patterned release manner.
Also envisaged are double coating approaches or coated fertilizers based on a programmed release.
In further embodiments the fertilizer mixture may be provided as, or may comprise or contain a slow release fertilizer. The fertilizer may, for example, be released over any suitable period of time, e.g. over a period of 1 to 5 months, preferably up to 3 months. Typical examples of ingre- clients of slow release fertilizers are IBDU (isobutylidenediurea), e.g. containing about 31 -32 % nitrogen, of which 90% is water insoluble; or UF, i.e. an urea-formaldehyde product which contains about 38 % nitrogen of which about 70 % may be provided as water insoluble nitrogen; or CDU (crotonylidene diurea) containing about 32 % nitrogen; or MU (methylene urea) containing about 38 to 40% nitrogen, of which 25-60 % is typically cold water insoluble nitrogen; or M DU (methylene diurea) containing about 40% nitrogen, of which less than 25 % is cold water insoluble nitrogen; or MO (methylol urea) containing about 30% nitrogen, which may typically be used in solutions; or DMTU (diimethylene triurea) containing about 40% nitrogen, of which less than 25% is cold water insoluble nitrogen; or TMTU (tri methylene tetraurea), which may be provided as component of UF products; or TM PU (tri methylene pentaurea), which may also be provided as component of U F products; or UT (urea triazone solution) which typically contains about 28 % nitrogen. The fertilizer mixture may also be long-term nitrogen-bearing fertiliser containing a mixture of acetylene diurea and at least one other organic nitrogen-bearing fertiliser selected from methylene urea, isobutylidene diurea, crotonylidene diurea, substituted triazones, triuret or mixtures thereof.
Any of the above mentioned fertilizers or fertilizer forms may suitably be combined. For instance, slow release fertilizers may be provided as coated fertilizers. They may also be combined with other fertilizers or fertilizer types. The same applies to the presence of (T) or a nitrifi- cation inhibitor or fungicide according to the present invention, which may be adapted to the form and chemical nature of the fertilizer and accordingly be provided such that its release accompanies the release of the fertilizer, e.g. is released at the same time or with the same frequency. The present invention further envisages fertilizer or fertilizer forms as defined herein above in combination with nitrification inhibitors as defined herein above and fungicides and further in combination with urease inhibitors as defined herein above. Such combinations may be provided as coated or uncaoted forms and/or as slow or fast release forms. Preferred are combinations with slow release fertilizers including a coating. In further embodiments, also different release schemes are envisaged, e.g. a slower or a faster release. The term "fertigation" as used herein refers to the application of fertilizers, optionally soil amendments, and optionally other water-soluble products together with water through an irrigation system to a plant or to the locus where a plant is growing or is intended to grow, or to a soil substituent as defined herein below. For example, liquid fertilizers or dissolved fertilizers may be provided via fertigation directly to a plant or a locus where a plant is growing or is intended to grow. Likewise, nitrification inhibitors according to the present invention, or in combination with additional nitrification inhibitors, may be provided via fertigation to plants or to a locus where a plant is growing or is intended to grow. Fertilizers and nitrification inhibitors according to the present invention, or in combination with additional nitrification inhibitors, may be provided together, e.g. dissolved in the same charge or load of material (typically water) to be irrigated. In further embodiments, fertilizers and nitrification inhibitors may be provided at different points in time. For example, the fertilizer may be fertigated first, followed by (T) or the nitrification inhibitor, or preferably, (T) or the nitrification inhibitor may be fertigated first, followed by the fertilizer. The time intervals for these activities follow the herein above outlined time intervals for the ap- plication of fertilizers and nitrification inhibitors. Also envisaged is a repeated fertigation of fertilizers and nitrification inhibitors according to the present invention, either together or intermittently, e.g. every 2 hours, 6 hours, 12 hours, 24 hours, 2 days, 3 days, 4 days, 5 days, 6 days or more.
In particularly preferred embodiments, the fertilizer is an ammonium-containing fertilizer.
The agrochemical mixture according to the present invention may comprise one fertilizer as defined herein above and (T) or one nitrification inhibitor of formula I as defined herein above and one fungicide as defined herein above. In further embodiments, the agrochemical mixture according to the present invention may comprise at least one or more than one fertilizer as defined herein above, e.g. 2, 3, 4, 5, 6, 6, 7, 8, 9, 10 or more different fertilizers (including inorganic, organic and urea-containing fertilizers) and at least one (T) or nitrification inhibitor of formula I and at least one fungicide as defined herein above, preferably a combination as defined in Table 2 or Table 3.
In another group of embodiments the agrochemical mixture according to the present invention may comprise at least one or more than one (T) or nitrification inhibitor of formula I as defined herein above, preferably more than one nitrification inhibitor of formula I selected from Table 1 , e.g. 2, 3, 4, 5, 6, 6, 7, 8, 9, 10 or more different nitrification inhibitors as defined herein above or as provided in Table 1 and at least one fertilizer as defined herein above and at least one fungicide as defined herein above.
The term "at least one" is to be understood as 1 , 2, 3 or more of the respective compound se- lected from the group consisting of fertilizers as defined herein above (also designated as compound C), and (T) or nitrification inhibitors of formula I as defined herein above (also designated as compound A), and fungicides (also designated as compound B).
In addition to at least one fertilizer and at least one nitrification inhibitor as defined herein above or (T) and at least one fungicide, an agrochemical mixture may comprise further ingredients, compounds, active compounds or compositions or the like. For example, the agrochemical mixture may additionally comprise or composed with or on the basis of a carrier, e.g. an agrochemical carrier, preferably as defined herein. In further embodiments, the agrochemical mixture may further comprise at least one additional pesticidal compound. For example, the agrochemical mixture may additionally comprise at least one fungicidal compound and/or at least one insecti- cidal compound.
In further embodiments, the agrochemical mixture may, in addition to the above indicated ingre- dientsfurther comprise alternative or additional nitrification inhibitors such as linoleic acid, alpha- linolenic acid, methyl p-coumarate, methyl ferulate, MHPP, Karanjin, brachialacton, p- benzoquinone sorgoleone, nitrapyrin, dicyandiamide (DCD), 3,4-dimethyl pyrazole phosphate (DM PP), 4-amino-1 ,2,4-triazole hydrochloride (ATC), 1 -amido-2-thiourea (ASU), 2-amino-4- chloro-6-methylpyrimidine (AM), 5-ethoxy-3-trichloromethyl-1 ,2,4-thiodiazole (terrazole), ammo- niumthiosulfate (ATU), 3-methylpyrazol (3-MP), 3,5-dimethylpyrazole (DM P), 1 ,2,4-triazol, thiourea (TU) and/or sulfathiazole (ST).
Furthermore, the invention relates to a method for increasing the health of a plant, comprising treating a plant growing on soil and/or the locus where the plant is growing or is intended to grow with a combination of at least one nitrification inhibitor or (T) and at least one fungicide as defined herein above, preferabyl with a combination as defined in Table 2 or Table 3, or a composition comprising said combination. The term "plant" is to be understood as a plant of economic importance and/or men-grown plant. In certain embodiments, the term may also be understood as plants which have no or no significant economic importance. The plant is preferably selected from agricultural, silvicultural and horticultural (including ornamental) plants. The term also relates to genetically modified plants.
The term "plant" as used herein further includes all parts of a plant such as germinating seeds, emerging seedlings, plant propagules, herbaceous vegetation as well as established woody plants including all belowground portions (such as the roots) and aboveground portions. Within the context of the method for increasing the health of plant it is assumed that the plant is growing on soil. In specific embodiments, the plant may also grow differently, e.g. in synthetic laboratory environments or on soil substituents, or be supplemented with nutrients, water etc. by artificial or technical means. In such scenarios, the invention envisages a treatment of the zone or area where the nutrients, water etc. are provided to the plant. Also envisaged is that the plant grows in green houses or similar indoor facilities.
The term "locus" is to be understood as any type of environment, soil, soil substituents, area or material where the plant is growing or intended to grow. Preferably, the term relates to soil or soil substituent on which a plant is growing.
In one embodiment, the plant to be treated according to the method of the invention is an agricultural plant. "Agricultural plants" are plants of which a part (e.g. seeds) or all is harvested or cultivated on a commercial scale or which serve as an important source of feed, food, fibres (e.g. cotton, linen), combustibles (e.g. wood, bioethanol, biodiesel, biomass) or other chemical compounds. Preferred agricultural plants are for example cereals, e.g. wheat, rye, barley, tritica- le, oats, sorghum or rice, beet, e.g. sugar beet or fodder beet; fruits, such as pomes, stone fruits or soft fruits, e.g. apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries, blackberries or gooseberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, oil-seed rape, canola, linseed, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palms, ground nuts or soybeans; cucurbits, such as squashes, cucumber or melons; fiber plants, such as cotton, flax, hemp or jute; citrus fruit, such as oranges, lemons, grapefruits or mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or paprika; lauraceous plants, such as avocados, cinnamon or camphor; energy and raw material plants, such as corn, soybean, rape, canola, sugar cane or oil palm; tobacco; nuts; coffee; tea; bananas; vines (table grapes and grape juice grape vines); hop; turf; natural rubber plants. In a further embodiment, the plant to be treated according to the method of the invention is a horticultural plant. The term "horticultural plants" are to be understood as plants which are commonly used in horticulture, e.g. the cultivation of ornamentals, vegetables and/or fruits. Examples for ornamentals are turf, geranium, pelargonia, petunia, begonia and fuchsia. Examples for vegetables are potatoes, tomatoes, peppers, cucurbits, cucumbers, melons, watermelons, garlic, onions, carrots, cabbage, beans, peas and lettuce and more preferably from tomatoes, onions, peas and lettuce. Examples for fruits are apples, pears, cherries, strawberry, citrus, peaches, apricots and blueberries.
In a further embodiment, the plant to be treated according to the method of the invention is an ornamental plants. "Ornamental plants" are plants which are commonly used in gardening, e.g. in parks, gardens and on balconies. Examples are turf, geranium, pelargonia, petunia, begonia and fuchsia.
In another embodiment of the present invention, the plant to be treated according to the method of the invention is a silvicultural plants. The term "silvicultural plant" is to be understood as trees, more specifically trees used in reforestation or industrial plantations. Industrial plantations generally serve for the commercial production of forest products, such as wood, pulp, paper, rubber tree, Christmas trees, or young trees for gardening purposes. Examples for silvicultural plants are conifers, like pines, in particular Pinus spec, fir and spruce, eucalyptus, tropical trees like teak, rubber tree, oil palm, willow (Salix), in particular Salix spec, poplar (cottonwood), in particular Populus spec, beech, in particular Fagus spec, birch, oil palm, and oak.
The term "plant propagation material" is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e.g. pota- toes), which can be used for the multiplication of the plant. This includes seeds, grains, roots, fruits, tubers, bulbs, rhizomes, cuttings, spores, offshoots, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil, meristem tissues, single and multiple plant cells and any other plant tissue from which a complete plant can be obtained.
The term "genetically modified plants" is to be understood as plants, which genetic material has been modified by the use of recombinant DNA techniques in a way that under natural circumstances it cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant. Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), oligo- or polypeptides e. g. by glycosylation or polymer additions such as prenylated, acetylated or farne- sylated moieties or PEG moieties. Plants that have been modified by breeding, mutagenesis or genetic engineering, e. g. have been rendered tolerant to applications of specific classes of herbicides, such as auxin herbicides such as dicamba or 2,4-D; bleacher herbicides such as hydroxylphenylpyruvate dioxy- genase (H PPD) inhibitors or phytoene desaturase (PDS) inhibitors; acetolactate synthase (ALS) inhibitors such as sulfonyl ureas or imidazolinones; enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such as glyphosate; glutamine synthetase (GS) inhibitors such as glufosinate; protoporphyrinogen-IX oxidase inhibitors; lipid biosynthesis inhibitors such as acetyl CoA carboxylase (ACCase) inhibitors; or oxynil (i. e. bromoxynil or ioxynil) herbicides as a result of conventional methods of breeding or genetic engineering. Furthermore, plants have been made resistant to multiple classes of herbicides through multiple genetic modifications, such as resistance to both glyphosate and glufosinate or to both glyphosate and a herbicide from another class such as ALS inhibitors, HPPD inhibitors, auxin herbicides, or ACCase inhibitors. These herbicide resistance technologies are e. g. described in Pest Managem. Sci. 61 , 2005, 246; 61 , 2005, 258; 61 , 2005, 277; 61 , 2005, 269; 61 , 2005, 286; 64, 2008, 326; 64, 2008, 332; Weed Sci. 57, 2009, 108; Austral. J. Agricult. Res. 58, 2007, 708; Science 316, 2007, 1 185; and references quoted therein. Several cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), e. g. Clearfield® summer rape (Canola, BASF SE, Germany) being tolerant to imidazolinones, e. g. imazamox, or ExpressSun® sunflowers (DuPont, USA) being tolerant to sulfonyl ureas, e. g. tribenuron. Genetic engineering methods have been used to render cultivated plants such as soybean, cotton, corn, beets and rape, tolerant to herbicides such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate-tolerant, Monsanto, U.S.A.), Cul- tivance® (imidazolinone tolerant, BASF SE, Germany) and LibertyLink® (glufosinate-tolerant, Bayer CropScience, Germany).
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as δ-endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ) or Cry9c; vegetative insecticidal pro- teins (VIP), e. g. VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, e. g. Photorhabdus spp. or Xenorhabdus s pp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; toxins produced by fungi, such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors; ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin, luffin, saporin or bryodin; steroid metabolism enzymes, such as 3-hydroxysteroid oxidase, ecdyster- oid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ion channel blockers, such as blockers of sodium or calcium channels; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilbene synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins. Hybrid proteins are characterized by a new combination of protein domains, (see, e. g. WO 02/015701 ). Further examples of such toxins or genetically modified plants ca- pable of synthesizing such toxins are disclosed, e. g., in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/18810 und WO 03/52073.
The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above. These insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins tolerance to harmful pests from all taxonomic groups of arthropods, especially to beetles (Coeloptera), two-winged insects (Diptera), and moths (Lepidoptera) and to nematodes (Nema- toda). Genetically modified plants capable to synthesize one or more insecticidal proteins are, e. g., described in the publications mentioned above, and some of which are commercially available such as YieldGard® (corn cultivars producing the Cry1 Ab toxin), YieldGard® Plus (corn culti- vars producing Cry1 Ab and Cry3Bb1 toxins), Starlink® (corn cultivars producing the Cry9c toxin), Herculex® RW (corn cultivars producing Cry34Ab1 , Cry35Ab1 and the enzyme phosphino- thricin-N-acetyltransferase [PAT]); NuCOTN® 33B (cotton cultivars producing the Cry1 Ac toxin), Bollgard® I (cotton cultivars producing the Cryl Ac toxin), Bollgard® II (cotton cultivars producing Cry1 Ac and Cry2Ab2 toxins); VIPCOT® (cotton cultivars producing a VIP-toxin); NewLeaf® (potato cultivars producing the Cry3A toxin); Bt-Xtra®, NatureGard®, KnockOut®, BiteGard®, Pro- tecta®, Bt1 1 (e. g. Agrisure® CB) and Bt176 from Syngenta Seeds SAS, France, (corn cultivars producing the Cry1 Ab toxin and PAT enyzme), M IR604 from Syngenta Seeds SAS, France (corn cultivars producing a modified version of the Cry3A toxin, c.f. WO 03/018810), MO N 863 from Monsanto Europe S.A., Belgium (corn cultivars producing the Cry3Bb1 toxin), IPC 531 from Monsanto Europe S.A., Belgium (cotton cultivars producing a modified version of the Cryl Ac toxin) and 1507 from Pioneer Overseas Corporation, Belgium (corn cultivars producing the Cryl F toxin and PAT enzyme).
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens. Examples of such proteins are the so-called "pathogenesis- related proteins" (PR proteins, see, e. g. EP-A 392 225), plant disease resistance genes (e. g. potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the Mexican wild potato Solanum bulbocastanum) or T4-lysozym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Er- winia amylvora). The methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications mentioned above.
Furthermore, plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. bio mass production, grain yield, starch content, oil content or protein content), tolerance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, e. g. oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera® rape, DOW Agro Sciences, Canada).
Furthermore, plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Amflora® potato, BASF SE, Germany).
The term "soil substituent" as used herein refers to a substrate which is able to allow the growth of a plant and does not comprise usual soil ingredients. This substrate is typically an anorganic substrate which may have the function of an inert medium. It may, in certain embodiments, also comprise organic elements or portions. Soil substituents may, for example, be used in hydrocul- ture or hydroponic approaches, i.e. wherein plants are grown in soilless medium and/or aquatic based environments. Examples of suitable soil substituents, which may be used in the context of the present invention, are perlite, gravel, biochar, mineral wool, coconut husk, phyllosilicates, i.e. sheet silicate minerals, typically formed by parallel sheets of silicate tetrahedra with S12O5 or a 2:5 ratio, or clay aggregates, in particular expanded clay aggregates with a diameter of about 10 to 40 mm. Particularly preferred is the employment of vermiculite, i.e. a phyllosilicate with 2 tetrahedral sheets for every one octahedral sheet present.
The use of soil substituents may, in specific embodiments, be combined with fertigation or irrigation as defined herein.
In specific embodiments, the treatment may be carried out during all suitable growth stages of a plant as defined herein. For example, the treatment may be carried out during the BBCH principle growth stages.
The term "BBCH principal growth stage" refers to the extended BBCH-scale which is a system for a uniform coding of phenologically similar growth stages of all mono- and dicotyledonous plant species in which the entire developmental cycle of the plants is subdivided into clearly recognizable and distinguishable longer-lasting developmental phases. The BBCH-scale uses a decimal code system, which is divided into principal and secondary growth stages. The abbreviation BBCH derives from the Federal Biological Research Centre for Agriculture and Forestry (Germany), the Bundessortenamt (Germany) and the chemical industry.
In one embodiment the invention relates to a method for increasing the health of a plant comprising treating a plant growing on soil or soil substituents and/or the locus where the plant is growing with a combination as defined herein above, or a corresponding composition or agricul- tural composition as defined herein above at a growth stage (GS) between GS 00 and GS 65 BBCH of the plant. In one embodiment the invention relates to a method for increasing the health of a plant comprising treating a plant growing on soil or soil substituents and/or the locus where the plant is growing with a combination as defined herein above, or a corresponding composition or agricultural composition as defined herein above at a growth stage (GS) between GS 00 to GS 33 BBCH of the plant.
In a preferred embodiment the invention relates to a method for increasing the health of a plant comprising treating a plant growing on soil or soil substituents and/or the locus where the plant is growing with a combination as defined herein above, or a corresponding composition or agri- cultural composition as defined herein aboveat an early growth stage (GS), in particular a GS 00 to GS 05, or GS 00 to GS 10, or GS 00 to GS 15, or GS 00 to GS 20, or GS 00 to GS 25 or GS 00 to GS 33 BBCH of the plant. In particularly preferred embodiments, the method comprises treating a plant growing on soil or soil substituents and/or the locus where the plant is growing with a combination as defined herein above, or a corresponding composition or agricultural composition as defined herein above during growth stages including GS 00.
In a further, specific embodiment of the invention a combination as defined herein above, or a corresponding composition or agricultural composition as defined herein above is applied to a plant growing on soil or soil substituents and/or the locus where the plant is growing or is in- tended to grow at a growth stage between GS 00 and GS 55 BBCH, or of the plant.
In a further embodiment of the invention a combination as defined herein above, or a corresponding composition or agricultural composition as defined herein above is applied to a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow at the growth stage between GS 00 and GS 47 BBCH of the plant.
In one embodiment of the invention a combination as defined herein above, or a corresponding composition or agricultural composition as defined herein above is applied to a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow before and at sowing, before emergence, and until harvest (GS 00 to GS 89 BBCH), or at a growth stage (GS) between GS 00 and GS 65 BBCH of the plant.
In a preferred embodiment the invention relates to a method increasing the health of a plant comprising treating a plant growing on soil or soil substituents and/or the locus where the plant is growing with a combination as defined herein above, or a corresponding composition or agricultural composition as defined herein above wherein the plant and/or the locus where plant is growing or is intended to grow is additionally provided with at least one fertilizer. The fertilizer may be any suitable fertilizer, preferably a fertilizer as defined herein above. Also envisaged is the application of more than one fertilizer, e.g. 2, 3, 4, 5, 6, 7, 8, 9, 10 fertilizers, or of different fertilizer classes or categories.
In specific embodiments of the invention, a combination as defined herein above, or a corresponding composition or agricultural composition as defined herein above and at least one ferti- lizer is applied to a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow at a growth stage between GS OOand GS 33 BBCH of the plant.
In specific embodiments of the invention a combination as defined herein above, or a corre- sponding composition or agricultural composition as defined herein above r is applied to a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow at a growth stage between GS 00 and GS 55 BBCH of the plant.
In further specific embodiments of the invention a combination as defined herein above, or a corresponding composition or agricultural composition as defined herein aboveand at least one fertilizer is applied to a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow at sowing, before emergence, or at a growth stage (GS) between GS 00 and GS 65 BBCH of the plant.
According to a preferred embodiment of the present invention the application of said nitrification inhibitor as defined herein or (T) (component A) and of said fungicide (component B) is carried out simultaneously or with a time lag. The term "time lag" as used herein means that either (T) or the nitrification inhibitor is applied before the fungicide to the plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow; or the fungicide is applied before (T) or the nitrification inhibitor to the plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow. Such time lag may be any suitable period of time which still allows to provide a nitrification inhibiting effect in the context of fungicide usage, or which provides for a reduction in growth of phytophathogenic fungi in the context of the usage of (T) or a nitrification inhibitor. For example, the time lag may be a time period of 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 1 1 days, 12 days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks , 9 weeks, 10 weeks, 1 1 weeks, 12 weeks, 4 months, 5 months, 6 months, 7 months, 8 months, 9 months, 10 months or more or any time period in between the mentioned time periods. Preferably, the time lag is an interval of 1 day, 2 days, 3 days, 1 week, 2 weeks or 3 weeks. The time lag preferably refers to situations in which the nitrification inhibitor as defined above or (T) is provided 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 1 1 days, 12 days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks , 9 weeks, 10 weeks, 1 1 weeks, 12 weeks, 4 months, 5 months, 6 months, 7 months, 8 months, 9 months, 10 months or more or any time period in between the mentioned time periods before the application of a fungicide as defined herein above.
According to a preferred embodiment of the present invention the application of said combination of a nitrification inhibitor or (T) and a fungicide as defined herein above, or a corresponding composition or agricultural composition as defined herein above and of said fertilizer (compo- nent C) as defined herein above is carried out simultaneously or with a time lag. The term "time lag" as used herein means that either (T) or the nitrification inhibitor and/or fungicide is applied before the fertilizer to the plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow; or the fertilizer is applied before (T) or the nitrification inhibitor and/or fungicide to the plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow. Such time lag may be any suitable period of time which still allows to provide a nitrification inhibiting effect in the context of fertilizer usage, or which provides for a reduction in growth of or elimination of phytopathogenic fungi in the context of the usage of (T) or nitrification inhibitor. For example, the time lag may be a time period of 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 1 1 days, 12 days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks , 9 weeks, 10 weeks,
1 1 weeks, 12 weeks, 4 months, 5 months, 6 months, 7 months, 8 months, 9 months, 10 months or more or any time period in between the mentioned time periods. Preferably, the time lag is an interval of 1 day, 2 days, 3 days, 1 week, 2 weeks or 3 weeks. The time lag preferably refers to situations in which the nitrification inhibitor as defined above or (T) is provided 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 1 1 days, 12 days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks , 9 weeks, 10 weeks, 1 1 weeks,
12 weeks, 4 months, 5 months, 6 months, 7 months, 8 months, 9 months, 10 months or more or any time period in between the mentioned time periods before the application of a fertilizer as defined herein above.
In another specific embodiment of the invention one component of a combination as defined herein above, or of a corresponding composition or agricultural composition as defined herein above is applied between GS 00 to GS 33 BBCH of the plant, or between GS 00 and GS 65 BBCH of the plant, provided that the application of the other component of said combination as defined herein above, or a of corresponding composition or agricultural composition as defined herein above is carried out with a time lag of at least 1 day, e.g. a time lag of 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 1 1 days, 12 days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks , 9 weeks, 10 weeks, or more or any time period in between the mentioned time periods. It is preferred that one component of thecombination as defined herein above, or of a corresponding composition or agricultural composition as defined herein above, which is applied between GS 00 to GS 33 BBCH of the plant, is provided 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 1 1 days, 12 days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks , 9 weeks, 10 weeks, 1 1 weeks, or 12 weeks before the application of the other component.
In another specific embodiment of the invention, at least one fertilizer as defined herein above is applied between GS 00 to GS 33 BBCH of the plant or between GS 00 and GS 65 BBCH of the plant, provided that the application of a combination as defined herein above, or of at least one component of said combination, or a corresponding composition or agricultural composition as defined herein above, is carried out with a time lag of at least 1 day, e.g. a time lag of 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 1 1 days, 12 days, 13 days, 14 days, 3 weeks 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks , 9 weeks, 10 weeks or more or any time period in between the mentioned time periods.
According to a specific embodiment of the present invention a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow is treated at least once with at least one component of a combination as defined herein above or of a corresponding composition or agricultural composition as defined herein above, or with said combination. In a further specific embodiment of the present invention a plant growing on soil or soil substitu- ents and/or the locus where the plant is growing or is intended to grow is treated at least once with a combination as defined herein above, or one of its components, or a corresponding composition or agricultural composition as defined herein above, and at least once with a fertilizer as defined herein above.
The term "at least once" means that the application may be performed one time, or several times, i.e. that a repetition of the treatment with (T) or a nitrification inhibitor and/or a fertilizer may be envisaged. Such a repetition may a 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times or more frequent repetition of the treatment with a combination as defined herein above, or one of its components, or a corresponding composition or agricultural composition as defined herein above and/or a fertilizer. The repetition of treatment with a com- bination as defined herein above, or one of its components, or a corresponding composition or agricultural composition as defined herein above and a fertilizer may further be different. For example, while the fertilizer may be applied only once, the a combination as defined herein above, or one of its components, or a corresponding composition or agricultural composition as defined herein above may be applied 2 times, 3 times, 4 times etc. Alternatively, while (T) or the nitrification inhibitor may be applied only once, the fertilizer may be applied 2 times, 3 times, 4 times etc. Further envisaged are all combinations of numerical different numbers of repetitions for the application of a combination as defined herein above, or one of its components, or a corresponding composition or agricultural composition as defined herein above and opitonally a fertilizer as defined herein above.
Such a repeated treatment may further be combined with a time lag between the treatment of the combination as defined herein above, or one of its components, or a corresponding composition or agricultural composition as defined herein above and optionally a fertilizer as described above. The time interval between a first application and second or subsequent application of a combination as defined herein above, or one of its components or a corresponding composition or agricultural composition as defined herein above and/or a fertilizer may be any suitable interval. This interval may range from a few seconds up to 3 months, e.g. from a few seconds up to 1 month, or from a few seconds up to 2 weeks. In further embodiments, the time interval may range from a few seconds up to 3 days or from 1 second up to 24 hours.
In further specific embodiments, a method for increasing the health of a plant as described above is carried out by treating a plant growing on soil or soil substituents and/or the locus where the plant is growing or is intended to grow with at least one agricultural mixture as de- fined herein above.
In another embodiment of the invention, an agrochemical mixture comprising an ammonium or urea-containing fertilizer and (T) or at least one nitrification inhibitor as defined herein above is applied before and at sowing, before emergence, and until shooting/shoot development (GS 00 to GS 33 BBCH) of the plant. In case the agricultural mixture is provided as kit of parts or as non-physical mixture, it may be applied with a time lag between the application of the nitrification inhibitor or (T) and the fertilizer or between the application of (T) or the nitrification inhibitor a secondary or further ingredient, e.g. a pesticidal compound as mentioned herein above.
In a further embodiment plant propagules are preferably treated simultaneously (together or separately) or subsequently. The term "propagules" or "plant propagules" is to be understood to denote any structure with the capacity to give rise to a new plant, e.g. a seed, a spore, or a part of the vegetative body capable of independent growth if detached from the parent. In a preferred embodiment, the term "propagules" or "plant propagules" denotes for seed. For a method as described above, or for a use according to the invention, the application rates of (T) or of nitrification inhibitors, i.e. of the compound of formula I are between 0,01 g and 5 kg of active ingredient per hectare, preferably between 1 g and 1 kg of active ingredient per hectare, especially preferred between 50 g and 300 g of active ingredient per hectare depending on different parameters such as the specific active ingredient applied and the plant species treated. In the treatment of seed, amounts of from 0.001 g to 20 g per kg of seed, preferably from 0.01 g to 10 g per kg of seed, more preferably from 0.05 to 2 g per kg of seed of (T) or nitrification inhibitors may be generally required.
As a matter of course, if (T) or nitrification inhibitors and fertilizers (or other ingredients), or if mixtures thereof are employed, the compounds may be used in an effective and non-phytotoxic amount. This means that they are used in a quantity which allows to obtain the desired effect but which does not give rise to any phytotoxic symptoms on the treated plant or on the plant raised from the treated propagule or treated soil. For the use according to the invention, the application rates of fertilizers may be between 10 kg and 300 kg per hectare, preferably be- tween 50 kg and 250 kg per hectare.
The nitrification inhibitor compounds according to the invention, e.g. compound I as defined herein above, or derivative thereof as defined herein above can be present in different structural or chemical modifications whose biological activity may differ. They are likewise subject matter of the present invention.
(T) or the nitrification inhibitor compounds according to the invention, their N-oxides and/or salts etc. may be converted into customary types of compositions, e.g. agrochemical or agricultural compositons such as solutions, emulsions, suspensions, dusts, powders, pastes and granules.
The composition type depends on the particular intended purpose; in each case, it should ensure a fine and uniform distribution of the compound according to the invention. Examples for composition types are suspensions (SC, 00, FS), emulsifiable concentrates (EC), emulsions (EW, EO, ES), microemulsions (ME), pastes, pastilles, wettable powders or dusts (WP, SP, SS, WS, OP, OS) or granules (GR, FG, GG, MG), which can be watersoluble or wettable, as well as gel formulations for the treatment of plant propagation materials such as seeds (GF). Usually the composition types (e.g. SC, 00, FS, EC, WG, SG, WP, SP, SS, WS, GF) are employed di- luted. Composition types such as OP, OS, GR, FG, GG and MG are usually used undiluted.
The compositions are prepared in a known manner (see, for example, US 3,060,084, EP 707 445 (for liquid concentrates), Browning: "Agglomeration", Chemical Engineering, Dec. 4, 1967, 147- 48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hili, New York, 1963, S. 8-57 und ff. WO 91/13546, US 4,172,714, US 4,144,050, US 3,920,442, US 5,180,587, US
5,232,701 , US 5,208,030, GB 2,095,558, US 3,299,566, Klingman: Weed Control as a Science (J. Wiley & Sons, New York, 1961 ), Hance et al.: Weed Control Handbook (8th Ed., Blackwell Scientific, Oxford, 1989) and Mollet, H. and Grubemann, A.: Formulation technology (Wiley VCH Verlag, Weinheim, 2001 ). Agrochemical compositions or mixtgures may also comprise auxiliaries which are customary in agrochemical compositions. The auxiliaries used depend on the particular application form and active substance, respectively.
Examples for suitable auxiliaries are solvents, solid carriers, dispersants or emulsifiers (such as further solubilizers, protective colloids, surfactants and adhesion agents), organic and anorganic thickeners, bactericides, anti-freezing agents, anti-foaming agents, if appropriate colorants and tackifiers or binders (e.g. for seed treatment formulations). Suitable solvents are water, organic solvents such as mineral oil fractions of medium to high boiling point, such as kerosene or die- sel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphtha- lenes or their derivatives, alcohols such as methanol, ethanol, propanol, butanol and cyclohex- anol, glycols, ketones such as cyclohexanone and gamma-butyrolactone, fatty acid dimethyla- mides, fatty acids and fatty acid esters and strongly polar solvents, e.g. amines such as N- methylpyrrolidone. Suitable surfactants (adjuvants, wetters, tackifiers, dispersants or emulsifiers) are alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, such as ligninsoulfonic acid (Borresperse® types, Borregard, Norway) phenolsulfonic acid, naphthalenesulfonic acid (Mor- wet® types, Akzo Nobel, U.S.A.), dibutylnaphthalene-sulfonic acid (Nekal® types, BASF, Ger- manY), and fatty acids, alkylsulfonates, alkylarylsulfonates, alkyl sulfates, laurylether sulfates, fatty alcohol sulfates, and sulfated hexa-, hepta- and octadecanolates, sulfated fatty alcohol glycol ethers, furthermore condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, polyoxy-ethylene octylphenyl ether, ethoxylated isooctylphenol, oc- tylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenyl polyglycol ether, tri- stearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol/ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxy- propylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and proteins, denatured proteins, polysaccharides (e. g. methylcellulose), hydrophobically modified starches, polyvinyl alcohols (Mowiol® types, Clariant, Switzerland), polycarboxylates (Sokolan® types, BASF, Germany), polyalkoxylates, polyvinylamines (Lupasol® types, BASF, Germany), polyvinylpyrrolidone and the copolymers thereof. Examples of suitable thickeners (i.e. compounds that impart a modified flowability to compositions, i.e. high viscosity under static conditions and low viscosity during agitation) are polysaccharides and organic and anorganic clays such as Xanthan gum (Kelzan®, CP Kelco, U .S.A.), Rhodopol® 23 (Rhodia, France), Veegum® (R.T. Vanderbilt, U.S.A.) or Attaclay® (Engelhard Corp., NJ, USA).
In specific embodiments, bactericides may be added for preservation and stabilization of the composition. Examples for suitable bactericides are those based on dichlorophene and benzyl alcohol hemi formal (Proxe D from ICI or Acticide® RS from Thor Chemie and Kathon® MK from Rohm & Haas) and isothiazolinone derivatives such as alkylisothiazolinones and benziso- thiazolinones (Acticide® MBS from Thor Chemie).
Examples for suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glyc- erin. Examples for anti-foaming agents are silicone emulsions (such as e.g. Silikon® SRE,
Wacker, Germany or Rhodorsil®, Rhodia, France), long chain alcohols, fatty acids, salts of fatty acids, fluoroorganic compounds and mixtures thereof.
Suitable colorants are pigments of low water solubility and water-soluble dyes, e.g. rhodamin B, C. I. pigment red 1 12, C. I. solvent red 1 , pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15: 1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 1 12, pigment red 48:2, pigment red 48:1 , pigment red 57:1 , pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
Examples for tackifiers or binders are polyvinylpyrrolidons, polyvinylacetates, polyvinyl alcohols and cellulose ethers (Tylose®, Shin-Etsu, Japan). Powders, materials for spreading and dusts can be prepared by mixing or concomitantly grinding compound of formula I and, if appropriate, further active substances, with at least one solid carrier. Granules, e.g. coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active substances to solid carriers. Examples of such suitable solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers. Examples for composition types are: i) Water-soluble concentrates (SL, LS) 10 parts by weight of (T) or a nitrification inhibitor such as a compound of formula I according to the invention are dissolved in 90 parts by weight of water or in a water-soluble solvent. As an alternative, wetting agents or other auxiliaries are added. The active substance dissolves upon dilution with water. In this way, a composition having a content of 10% by weight of active substance is obtained. ii) Dispersible concentrates (DC) 20 parts by weight of (T) or a nitrification inhibitor such as a compound of formula I according to the invention are dissolved in 70 parts by weight of cyclo- hexanone with addition of 10 parts by weight of a dispersant, e.g. polyvinylpyrrolidone. Dilution with water gives a dispersion. The active substance content is 20% by weight. iii) Emulsifiable concentrates (EC) 15 parts by weight of (T) or a nitrification inhibitor such as a compound of formula I according to the invention are dissolved in 75 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion. The composition has an active substance content of 15% by weight. iv) Emulsions (EW, EO, ES) 25 parts by weight of (T) or a nitrification inhibitor such as a compound of formula I according to the invention are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is introduced into 30 parts by weight of water by means of an emulsifying machine (Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion. The composition has an active substance content of 25% by weight. v) Suspensions (SC, 00, FS) In an agitated ball mill, 20 parts by weight of (T) or a nitrification inhibitor such as a compound of formula I according to the invention are comminuted with addi- tion of 10 parts by weight of dispersants and wetting agents and 70 parts by weight of water or an organic solvent to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. The active substance content in the composition is 20% by weight. vi) Water-dispersible granules and water-soluble granules (WG, SG) 50 parts by weight of (T) or a nitrification inhibitor such as a compound of formula I according to the invention are ground finely with addition of 50 parts by weight of dispersants and wetting agents and prepared as water-dispersible or water-soluble granules by means of technical appliances (e.g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance. The composition has an active substance content of 50% by weight. vii) Water-dispersible powders and water-soluble powders (WP, SP, SS, WS) 75 parts by weight of (T) or a nitrification inhibitor such as a compound of formula I according to the invention are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants, wetting agents and silica gel. Dilution with water gives a stable dispersion or solution of the active substance. The active substance content of the composition is 75% by weight. viii) Gel (GF) In an agitated ball mill, 20 parts by weight of (T) or a nitrification inhibitor such as a compound of formula I according to the invention are comminuted with addition of 10 parts by weight of dispersants, 1 part by weight of a gelling agent wetters and 70 parts by weight of water or of an organic solvent to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance, whereby a composition with 20% (w/w) of active substance is obtained.
2. Composition types to be applied undiluted: ix) Oustable powders (OP, OS) 5 parts by weight of (T) or a nitrification inhibitor such as a compound of formula I according to the invention are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dustable composition having an active substance content of 5% by weight. x) Granules (GR, FG, GG, MG) 0.5 parts by weight of (T) or a nitrification inhibitor such as a compound of formula I according to the invention is ground finely and associated with 99.5 parts by weight of carriers. Current methods are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted having an active substance content of 0.5% by weight. xi) ULV solutions (UL) 10 parts by weight of (T) or a nitrification inhibitor such as a compound of formula I according to the invention are dissolved in 90 parts by weight of an organic solvent, e.g. xylene. This gives a composition to be applied undiluted having an active substance content of 10% by weight. The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, most preferably between 0.5 and 90%, by weight of active substance. The active substances are employed in a purity offrom 90% to 100%, preferably from 95% to 100% (according to NMR spectrum). Water-soluble concentrates (LS), flowable concentrates (FS), powders for dry treatment (OS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES) emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds. These compositions can be applied to plant propagation materials, particularly seeds, diluted or undiluted.
The compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Application can be carried out before or during sowing.
Methods for applying or treating agrochemical or agricultural compounds or mixtures, or compositions as defined herein, respectively, on to plant propagation material, especially seeds, are known in the art, and include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material. In a preferred embodiment, the compounds or the compositions thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e.g. by seed dressing, pelleting, coating and dusting.
In a preferred embodiment, a suspension-type (FS) composition may be used. Typically, a FS composition may comprise 1 -800 g/l of active substance, 1 200 g/l surfactant, o to 200 g/l anti- freezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
The active substances can be used as such or in the form of their compositions, e.g. in the form of directly sprayable solutions, powders, suspensions, dispersions, emulsions, oil dispersions, pastes, dustable products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading, brushing, immersing or pouring.
The application forms depend entirely on the intended purposes; it is intended to ensure in each case the finest possible distribution of the active substances according to the invention. Aqueous application forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water.
To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifi- er. Alternatively, it is possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.
The active substance concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.001 to 1 % by weight of active substance. The active substances may also be used successfully in the ultra- low-volume process (ULV), it being possible to apply compositions comprising over 95% by weight of active substance, or even to apply the active substance without additives.
Various types of oils, wetters, adjuvants, herbicides, bactericides, and/or pesticides may be added to the active substances or the compositions comprising them, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions ac- cording to the invention in a weight ratio of 1 : 100 to 100 : 1 , preferably 1 : 10 to 10 : 1 .
Adjuvants which can be used are in particular organic modified polysiloxanes such as Break Thru S 240®; alcohol alkoxylates such as Atplus 245®, Atplus MBA 1303®, Plurafac LF 300® and Lutensol ON 30®; EO/PO block polymers, e.g. Pluronic RPE 2035® and Genapol B®; al- cohol ethoxylates such as Lutensol XP 80®; and dioctyl sulfosuccinate sodium such as Leo- phen RA®. In a further specific embodiment, the present invention relates to a method for treating seed or plant propagation material. The term "seed treatment" as used herein refers to or involves steps towards the control of biotic or abiotic stresses on or in seed and the improvement of shooting and development of plants from seeds. For seed treatment it is evident that a plant suffering from biotic stresses such as fungal attack or which has difficulties obtaining sufficient suitable nitrogen-sources shows reduced germination and emergence leading to poorer plant or crop establishment and vigor, and consequently, to a reduced yield as compared to a plant propagation material which has been subjected to curative or preventive treatment against the relevant pest and which can grow without the damage caused by the biotic stress factor. Abiotic stress includes drought, cold, increased UV, increased heat, or other changes in the environment of the plant, that leads to sub-optimal growth conditions. Methods for treating seed or plant proga- tion material according to the invention thus lead, among other advantages, to an enhanced plant health, a better protection against biotic stresses and an increased plant yield. Seed treatment methods for applying or treating inventive mixtures and compositions thereof, e.g. compositons or agrochemical composisitions as defined herein above, and in particular combinations of nitirificaiton inhibitors as defined herein above and fungicides to plant propagation material, especially seeds, are known in the art, and include dressing, coating, filmcoating, pelleting and soaking application methods of the propagation material. Such methods are also applicable to the combinations or compositions according to the invention.
In preferred embodiments, the seed treatment may be performed with combinations of (T) or nitrification inhibitors and fungicides as defined herein above, or with composition comprising said combinations, e.g. the combinations mentioned in Table 2 or Table 3. In specific embodi- ments these compositions as mentioned in Table 2 or Table 3 may additionally comprise further pesticides, e.g. insecticides and/or nematicides and/or biopesticides.
In a preferred embodiment, the agricultural compositon or combination comprising (T) or a nitrification inhibitor according to the present invention and a fungicide, e.g. as defined herein above, is applied or treated on to the plant propagation material by a method such that the germination is not negatively impacted. Accordingly, examples of suitable methods for applying (or treating) a plant propagation material, such as a seed, is seed dressing, seed coating or seed pelleting and alike. It is preferred that the plant propagation material is a seed, seed piece (i.e. stalk) or seed bulb.
Although it is believed that the present method can be applied to a seed in any physiological state, it is preferred that the seed be in a sufficiently durable state that it incurs no damage during the treatment process. Typically, the seed would be a seed that had been harvested from the field; removed from the plant; and separated from any cob, stalk, outer husk, and surround- ing pulp or other non-seed plant material. The seed would preferably also be biologically stable to the extent that the treatment would cause no biological damage to the seed. It is believed that the treatment can be applied to the seed at any time between harvest of the seed and sowing of the seed or during the sowing process (seed directed applications). The seed may also be primed either before or after the treatment.
Even distribution of the ingredients in compositions or mixtures as defined herein and adher- ence thereof to the seeds is desired during propagation material treatment. Treatment could vary from a thin film (dressing) of the formulation containing the combination, for example, a mixture of active ingredient(s), on a plant propagation material, such as a seed, where the original size and/or shape are recognizable to an intermediary state (such as a coating) and then to a thicker film (such as pelleting with many layers of different materials (such as carriers, for ex- ample, clays; different formulations, such as of other active ingredients; polymers; and colourants) where the original shape and/or size of the seed is no longer recognizable.
An aspect of the present invention includes application of the composition, e.g. agricultural composition or combination comprising (T) or a nitrification inhibitor according to the present invention and a fungicide, e.g. as defined herein above, onto the plant propagation material in a targeted fashion, including positioning the ingredients in the combination onto the entire plant propagation material or on only parts thereof, including on only a single side or a portion of a single side. One of ordinary skill in the art would understand these application methods from the description provided in EP954213B1 and WO06/1 12700.
The compostion, e.g. agricultural composition or combination comprising (T) or a nitrification inhibitor according to the present invention and a fungicide, e.g. as defined herein above, can also be used in form of a "pill" or "pellet" or a suitable substrate and placing, or sowing, the treated pill, or substrate, next to a plant propagation material. Such techniques are known in the art, particularly in EP1 124414, WO07/67042, and WO07/67044. Application of the composition, e.g. agricultural composition or combination comprising (T) or a nitrification inhibitor according to the present invention and a fungicide, e.g. as defined herein above, onto plant propagation material also includes protecting the plant propagation material treated with the combination of the present invention by placing one or more fungicide- and (T)- or nitrification inhibitor (Nl)- containing particles next to a fungicide- and Nl-treated seed, wherein the amount of fungicide is such that the pesticide-treated seed and the pesticide- containing particles together contain an Effective Dose of the fungicide and the fungicide dose contained in the fungicide-treated seed is less than or equal to the Maximal Non-Phytotoxic Dose of the pesticide. Such techniques are known in the art, particularly in WO2005/120226.
Application of the combinations onto the seed also includes controlled release coatings on the seeds, wherein the ingredients of the combinations are incorporated into materials that release the ingredients over time. Examples of controlled release seed treatment technologies are generally known in the art and include polymer films, waxes, or other seed coatings, wherein the ingredients may be incorporated into the controlled release material or applied between layers of materials, or both.
Seed can be treated by applying thereto the compound s present in the inventive mixtures in any desired sequence or simultaneously. The seed treatment occurs to an unsown seed, and the term "unsown seed" is meant to include seed at any period between the harvest of the seed and the sowing of the seed in the ground for the purpose of germination and growth of the plant.
Treatment to an unsown seed is not meant to include those practices in which the active ingredient is applied to the soil or soil substituents but would include any application practice that would target the seed during the planting process. Preferably, the treatment occurs before sowing of the seed so that the sown seed has been pre- treated with the combination. In particular, seed coating or seed pelleting are preferred in the treatment of the combinations according to the invention. As a result of the treatment, the ingredients in each combination are adhered on to the seed and therefore available for pest control. The treated seeds can be stored, handled, sowed and tilled in the same manner as any other active ingredient treated seed.
Solutions for seed treatment (LS), suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds. Preferred examples of seed treatment formulation types or soil application for pre-mix compositions are of WS, LS, ES, FS, WG or CS-type.
The compositions in question give, after two-to-tenfold dilution, active components concentra- tions of from 0.01 to 60% by weight, preferably from 0.1 to 40%, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying or treating compositions or combinations comprising (T) or a nitrification inhibitor according to the present invention, e.g. as defined herein above on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material. Preferably, compositions or combinations comprising (T) or a nitrification inhibitor according to the present invention, e.g. as defined herein above are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting. Typically, a pre-mix formulation for seed treatment application comprises 0.5 to 99.9 percent, especially 1 to 95 percent, of the desired ingredients, and 99.5 to 0.1 percent, especially 99 to 5 percent, of a solid or liquid adjuvant (including, for example, a solvent such as water), where the auxiliaries can be a surfactant in an amount of 0 to 50 percent, especially 0.5 to 40 percent, based on the pre-mix formulation. Whereas commercial products will preferably be formulated as concentrates (e.g., pre- mix composition (formulation)), the end user will normally employ dilute formulations (e.g., tank mix composition).
When employed in plant protection, the total amounts of active components applied are, de- pending on the kind of effect desired, from 0.001 to 10 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, in particular from 0.1 to 0.75 kg per ha. The application rates may range from about 1 x 106 to 5 x 1015 (or more) CFU/ha. Preferably, the spore concentration is about 1 x 107 to about 1 x 1011 CFU/ha. In the case of (entomopathogen- ic) nematodes as microbial pesticides (e.g. Steinernema feltiae), the application rates preferably range inform about 1 x 105 to 1 x 1012 (or more), more preferably from 1 x 108 to 1 x 1011, even more preferably from 5 x 108 to 1 x 1010 individuals (e.g. in the form of eggs, juvenile or any other live stages, preferably in an infetive juvenile stage) per ha. When employed in plant protection by seed treatment, the amount of compositions or combinations comprising (T) or a nitrification inhibitor according to the present invention and a fungicide, e.g. as defined herein above (based on total weight of active components) is in the range from 0.01 -10 kg, preferably from 0.1 -1000 g, more preferably from 1 -100 g per 100 kilogram of plant propagation material (preferably seeds). The application rates with respect to plant propagation material preferably may range from about 1 x 106 to 1 x 1012 (or more) CFU/seed. Preferably, the concentration is about 1 x 106 to about 1 x 1011 CFU/seed. Alternatively, the application rates with respect to plant propagation material may range from about 1 x 107 to 1 x 1014 (or more) CFU per 100 kg of seed, preferably from 1 x 109 to about 1 x 1011 CFU per 100 kg of seed.
The following example is provided for illustrative purposes. It is thus understood that the example is not to be construed as limiting. The skilled person in the art will clearly be able to envisage further modifications of the principles laid out herein.
Example 1
Soil was sampled fresh from a field (e.g. Limburgerhof), dried and sieved through a 500μιτι sieve. Approximately 200 mg of soil were placed into each well of a 48 well plate. Compounds, or DMSO alone, were added at a concentration of 10ppm, dissolved in 1 % DMSO. 6 μιτιοΙ ammonium sulfate was added per well as well as 4.8 mg NaCIC .
Subsequently, the samples were incubated at room temperature for up to 72 hrs. After the incubation period 64mg KCI were added and mixed. 25 μΙ of the supernatant were placed into a fresh plate and 260μΙ of a color reaction solution (from Merck Nr 1.1 1799.0100) were added.
Measurements were taken with a Tecan plate Reader at 540nm wavelength.
The results of the measurements (with a dose of 10 ppm ) were that all compounds #1 to #215 as shown in Table 1 , supra demonstrated an inhibition of > 10% compared to a control (DMSO only).
Example 2 The experimental setup below is particularly appropriate for determining the synergistic action of (T) and a fungicide having fungicidal activity which is enhanced in the composition comprising (T) and a fungicide. Microtest
The active compounds were formulated separately as a stock solution having a concentration of for example 10000 ppm in dimethyl sulfoxide.
1. Activity against the late blight pathogen Phytophthora infestans in the microtiter test (Phytin)
The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Phytophtora infestans containing a pea juice-based aqueous nutrient medium or DDC medium was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.
2. Activity against leaf blotch on wheat caused by Septoria tritici (Septtr) The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Septoria tritici in an aqueous biomalt or yeast-bactopeptone-glycerine solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an absorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation. 3. Activity against wheat leaf spots caused by Leptosphaeria nodorum (Leptno)
The stock solutions were mixed according to the ratio, pipetted onto a micro titer plate (MTP) and diluted with water to the stated concentrations. A spore suspension of Leptosphaeria nodorum in an aqueous biomalt or yeast-bactopeptone-glycerine solution was then added. The plates were placed in a water vapor-saturated chamber at a temperature of 18°C. Using an ab- sorption photometer, the MTPs were measured at 405 nm 7 days after the inoculation.
The measured parameters were compared to the growth of the active compound-free control variant (100%) and the fungus-free and active compound-free blank value to determine the relative growth in % of the pathogens in the respective active compounds.
These percentages were converted into efficacies. The expected efficacies of active compound mixtures were determined using Colby's formula [R.S. Colby, "Calculating synergistic and antagonistic responses of herbicide combinations", Weeds 15, 20-22 (1967)] and compared with the observed efficacies.

Claims

Claims:
1 . A composition comprising a) at least one (thio)phosphoric acid triamide (T) according to the general formula (la)
Ra1Ra2N-P(X)(NH2)2 (la)
wherein
X is oxygen or sulfur;
Ra1 is a Ci to C20 alkyl, C3 to C20 cycloalkyl, C& to C20 aryl, or dialkyla- minocarbonyl group;
Ra2 is H , or
Ra1 and Ra2 together with the nitrogen atom linking them define a 5- or 6-membered saturated or unsaturated heterocyclic radical, which optionally comprises 1 or 2 further heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur, and b) at least one fungicide selected from the group of fungicides comprising: i Respiration inhibitors such as:
Inhibitors of complex III at Q0 site selected from strobilurines, azoxystrobin (A.1 .1 ), coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxy- strobin/flufenoxystrobin, fluoxastrobin, kresoxim-m ethyl, mandestrobine, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin (A.1 .14), pyrametostrobin, pyraoxystrobin, tri- floxystrobin (A.1 .17) and 2-(2-(3-(2,6-dichlorophenyl)-1 -methyl-allylideneaminooxymethyl)- phenyl)-2-methoxyimino-N-methyl-acetamide, pyribencarb, triclopyricarb/chlorodincarb, famoxadone, fenamidone;
inhibitors of complex III at Q, site selected from cyazofamid, amisulbrom,
[(3S,6S,7R,8R)-8-benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl- 4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acet- oxymethoxy)-4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl]
2- methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxy-pyri- dine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate,
[(3S,6S,7R,8R)-8-benzyl-3-[[3-(1 ,3-benzodioxol-5-ylmethoxy)-4-methoxy-pyridine-2-car- bonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate; (3S,6S,7R,8R)-
3- [[(3-hydroxy-4-methoxy-2-pyridinyl)carbonyl]amino]-6-methyl-4,9-dioxo-8- (phenylmethyl)-l ,5-dioxonan-7-yl 2-methylpropanoate
inhibitors of complex II selected from benodanil, benzovindiflupyr, bixafen, boscalid (A.3.4), carboxin, fenfuram, fluopyram (A.3.7), flutolanil, fluxapyroxad (A.3.9), furametpyr, isofetamid, isopyrazam, mepronil, oxycarboxin, penflufen (A.3.14), penthiopyrad (A.3.15), sedaxane (A.3.16), tecloftalam, thifluzamide, N-(4'-trifluoromethylthiobiphenyl-2-yl)- 3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(2-(1 ,3,3-trimethyl-butyl)- phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxamide, 3-(difluoromethyl)-1 -methyl-Nil ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(trifluoromethyl)-1 -methyl-N-(1 ,1 ,3- trimethylindan-4-yl)pyrazole-4-carboxamide, 1 ,3-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyr- azole-4-carboxamide, 3-(trifluoromethyl)-1 ,5-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)- pyrazole-4-carboxamide, 1 ,3,5-trimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-car- boxamide, N-(7-fluoro-1 ,1 ,3-trimethyl-indan-4-yl)-1 ,3-dimethyl-pyrazole-4-carboxamide, N- [2-(2,4-dichlorophenyl)-2-methoxy-1 -methyl-ethyl]-3-(difluoromethyl)-1 -methyl-pyrazole-4- carboxamide;
(iv) other respiration inhibitors or complex I uncouplers selected from diflumetorim,
(5,8-difluoroquinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl}- amine; nitrophenyl derivates: binapacryl, dinobuton, dinocap, fluazinam; ferimzone; or- ganometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide; ametoctradin, silthiofam;
B) Sterol biosynthesis inhibitors (SBI fungicides) such as:
(v) C14 demethylase inhibitors (DM I fungicides) selected from triazoles, azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole (B.1 .5), diniconazole, dinicon- azole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexacona- zole, imibenconazole, ipconazole (B.1.15), metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole (B.1 .23), simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole (B.1.29), uniconazole,
(vi) 1 -[re/-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thio- cyanato-1 H-[1 ,2,4]triazole, 2-[re/-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)- oxiranylmethyl]-2H-[1 ,2,4]triazole-3-thiol, 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1 -(1 ,2,4- triazol-1 -yl)pentan-2-ol, 1 -[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -cyclopropyl-2-
(1 ,2,4-triazol-1 -yl)ethanol, 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4- triazol-1 -yl)butan-2-ol, 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1 -(1 ,2,4-triazol-1 -yl)butan- 2-ol, 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-3-methyl-1 -(1 ,2,4-triazol-1 -yl)butan- 2-ol, 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)propan-2-ol, 2- [2-chloro-4-(4-chlorophenoxy)phenyl]-3-methyl-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol, 2-[4-(4- chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)pentan-2-ol, 2-[4-(4- fluorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)propan-2-ol, 2-[2-chloro-4- (4-chlorophenoxy)phenyl]-1 -(1 ,2,4-triazol-1 -yl)pent-3-yn-2-ol; imidazoles: imazalil, pefura- zoate, prochloraz, triflumizol; pyrimidines, pyridines and piperazines: fenarimol, nuarimol, pyrifenox, triforine, [3-(4-chloro-2-fluoro-phenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]-(3- pyridyl)methanol;
(vii) Delta14-reductase inhibitors selected from aldimorph, dodemorph, dodemorph- acetate, fenpropimorph, tridemorph, fenpropidin, piperalin, spiroxamine;
(viii) Inhibitors of 3-keto reductase selected from fenhexamid;
C) Nucleic acid synthesis inhibitors such as:
(ix) phenylamides or acyl amino acid fungicides selected from benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl (C.1 .4), metalaxyl-M (mefenoxam) (C.1.5), ofurace, oxadixyl; (x) hymexazole, octhilinone, oxolinic acid, bupirimate, 5-fluorocytosine, 5-fluoro-2-(p- tolylmethoxy)pyrimidin-4-amine, or 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4-amine;
D) Inhibitors of cell division and cytoskeleton such as:
(xi) tubulin inhibitors selected from benzimidazoles, thiophanates: benomyl, car- bendazim, fuberidazole, thiabendazole (D.1.4), thiophanate-methyl; or triazolopyrimidines selected from 5-chloro-7-(4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]tri- azolo[1 ,5-a]pyrimidine
(xii) other cell division inhibitors selected from diethofencarb, ethaboxam (D.2.2), pen- cycuron, fluopicolide, zoxamide, metrafenone, pyriofenone;
E) Inhibitors of amino acid and protein synthesis such as:
(xiii) methionine synthesis inhibitors (anilino-pyrimidines) selected from cyprodinil, mep- anipyrim, pyrimethanil;
(xiv) protein synthesis inhibitors selected from blasticidin-S, kasugamycin, kasugamycin hydrochloride-hydrate, mildiomycin, streptomycin, oxytetracyclin, polyoxine, validamycin A;
F) Signal transduction inhibitors such as:
(i) MAP / histidine kinase inhibitors selected from fluoroimid, iprodione, procymidone, vinclozolin, fenpiclonil, fludioxonil;
(xv) G protein inhibitors selected from quinoxyfen;
G) Lipid and membrane synthesis inhibitors such as:
(xvi) Phospholipid biosynthesis inhibitors selected from edifenphos, iprobenfos, pyrazo- phos, isoprothiolane;
(xvii) lipid peroxidation inhibitors selected from dicloran, quintozene, tecnazene, tolclo- fos-methyl, biphenyl, chloroneb, etridiazole;
(xviii) phospholipid biosynthesis and cell wall deposition inhibitors selected from dime- thomorph, flumorph, mandipropamid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate (G.3.7) and N-(1 -(1 -(4-cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4- fluorophenyl) ester;
(xix) compounds affecting cell membrane permeability and fatty acides selected from propamocarb, propamocarb-hydrochlorid
(xx) fatty acid amide hydrolase inhibitors selected from oxathiapiprolin (G.5.1 ), 2-{3-[2- (1 -{[3,5-bis(difluoromethyl-1 H-pyrazol-1 -yl]acetyl}piperidin-4-yl)-1 ,3-thiazol-4-yl]-4,5- dihydro-1 ,2-oxazol-5-yl}phenyl methanesulfonate, 2-{3-[2-(1 -{[3,5-bis(difluoromethyl)-1 H- pyrazol-1 -yl]acetyl}piperidin-4-yl) 1 ,3-thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol-5-yl}-3- chlorophenyl methanesulfonate;
H) Inhibitors with Multi Site Action such as:
(xxi) inorganic active substances selected from Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;
(xxii) thio- and dithiocarbamates selected from ferbam, mancozeb (H.2.2), maneb, metam, metiram, propineb, thiram, zineb, ziram;
(xxiii) organochlorine compounds selected from phthalimides, sulfamides, chloronitriles, anilazine, chlorothalonil (H.3.2), captafol, captan, folpet, dichlofluanid, dichlorophen, hex- achlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid, N-(4-chloro-2- nitro-phenyl)-N-ethyl-4-methyl-benzenesulfonamide;
(xxiv) guanidines and others selected from guanidine, dodine, dodine free base, guaza- tine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate), dithianon, 2,6-dimethyM H,5H-[1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone;
I) Cell wall synthesis inhibitors such as:
(xxv) inhibitors of glucan synthesis selected from validamycin, polyoxin B; melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamid, dicyclomet, fenoxanil;
J) Plant defence inducers selected from:
(xxvi) acibenzolar-S-methyl, probenazole, isotianil, tiadinil, prohexadione-calcium; phospho- nates: fosetyl, fosetyl-aluminum, phosphorous acid and its salts;
K) Compounds with unknown mode of action selected from:
bronopol, chinomethionat, cyflufenamid, cymoxanil, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat-methylsulfate, diphenylamin, fenpyrazamine, flumetover, flusul- famide, flutianil, methasulfocarb nitrothal-isopropyl, picarbutrazox, tolprocarb, 2-[3,5- bis(difluoromethyl)-1 H-pyrazol-1-yl]-1 -[4-(4-{5-[2-(prop-2-yn-1 -yloxy)phenyl]-4,5-dihydro- 1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 -yl]ethanone, 2-[3,5-bis(difluoromethyl)-1 H- pyrazol-1 -yl]-1 -[4-(4-{5-[2-fluoro-6-(prop-2-yn-1 -yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3- yl}-1 ,3-thiazol-2-yl)piperidin-1 -yl]ethanone, 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 - [4-(4-{5-[2-chloro-6-(prop-2-yn-1-yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-
2-yl)piperidin-1 -yl]ethanone, oxin-copper, proquinazid, tebufloquin, tecloftalam, triazox- ide, 2-butoxy-6-iodo-3-propylchromen-4-one, N-(cyclopropylmethoxyimino-(6-difluoro- methoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide, N'-(4-(4-chloro-3- trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(4-(4- fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine,
N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine, N'-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N- ethyl-N-methyl formamidine, methoxy-acetic acid 6-tert-butyl-8-fluoro-2,3-dimethyl- quinolin-4-yl ester, 3-[5-(4-methylphenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine, 3-[5-(4- chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine (pyrisoxazole),
N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide, 5-chloro-1 -(4,6-di- methoxy-pyrimidin-2-yl)-2-methyl-1 H-benzoimidazole, 2-(4-chloro-phenyl)- N-[4-(3,4- dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide, ethyl (Z)-3-amino-2- cyano-3-phenyl-prop-2-enoate, pentyl N-[6-[[(Z)-[(1 -methyltetrazol-5-yl)-phenyl- methylene]amino]oxymethyl]-2-pyridyl]carbamate, 2-[2-[(7,8-difluoro-2-methyl-3- quinolyl)oxy]-6-fluoro-phenyl]propan-2-ol, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3- quinolyl)oxy]phenyl]propan-2-ol, 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1 - yl)quinoline, 3-(4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1 -yl)quinoline, 3-(4,4,5- trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1 -yl)quinolone, 9-fluoro-2,2-dimethyl-5-(3- quinolyl)-3H-1 ,4-benzoxazepine.
2. The composition according to claim 1 , wherein in the general formula (la) of (T) X is sulfur.
3. The composition according to claim 1 or 2, wherein in the general formula (la) of (T) Ra1 is C1-C20 alkyl and Ra2 is H .
4. The composition according to anyone of the claims 1 to 3, wherein the (thio)phosphoric acid triamide (T) is N-n-butylthiophosphoric acid triamide (NBPT) and/or N-n- propylthiophosphoric acid triamide (NPPT).
5. The composition according to anyone of the claims 1 to 4, wherein the fungicide is azoxystrobin (A.1 .1 ), pyraclostrobin (A.1 .14), trifloxystrobin (A.1.17), boscalid (A.3.4), fluopyram (A.3.7), fluxapyroxad (A.3.9), penflufen (A.3.14), penthiopyrad (A.3.15), sedaxane (A.3.16), difenoconazole (B.1.5), ipconazole (B.1.15), prothioconazole (B.1 .23), triticonazole (B.1.29), metalaxyl (C.1 .4), metalaxyl-M (mefenoxam) (C.1 .5), thiabendazole (D.1 .4), ethaboxam (D.2.2), valifenalate (G.3.7), oxathiapiprolin (G.5.1 ), mancozeb (H.2.2), or chlorothalonil (H.3.2).
6. A method for increasing the health of a plant and/or for increasing the fungicidal activity of a fungicide, comprising treating a plant growing on soil or soil substituents and/or the locus or soil or soil substituents where the plant is growing or is intended to grow with a) at least one (thio)phosphoric acid triamide (T) according to the general formula (la)
Ra1Ra2N-P(X)(NH2)2 (la) wherein X is oxygen or sulfur;
Ra1 is a Ci to C20 alkyl, C3 to C20 cycloalkyl, CQ to C20 aryl, or dialkyla- minocarbonyl group;
Ra2 is H , or Ra1 and Ra2 together with the nitrogen atom linking them define a 5- or 6-membered saturated or unsaturated heterocyclic radical, which optionally comprises 1 or 2 further heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur, and b) at least one fungicide selected from the group of fungicides comprising: A) Respiration inhibitors such as:
(xxvii) Inhibitors of complex III at Q0 site selected from strobilurines, azoxystrobin (A.1.1 ), coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxy- strobin/flufenoxystrobin, fluoxastrobin, kresoxim-m ethyl, mandestrobine, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin (A.1 .14), pyrametostrobin, pyraoxystrobin, tri- floxystrobin (A.1 .17) and 2-(2-(3-(2,6-dichlorophenyl)-1 -methyl-allylideneaminooxymethyl)- phenyl)-2-methoxyimino-N-methyl-acetamide, pyribencarb, triclopyricarb/chlorodincarb, famoxadone, fenamidone;
(xxviii) inhibitors of complex III at Q, site selected from cyazofamid, amisulbrom,
[(3S,6S,7R,8R)-8-benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl- 4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acet- oxymethoxy)-4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl]
2- methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxy-pyri- dine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate,
[(3S,6S,7R,8R)-8-benzyl-3-[[3-(1 ,3-benzodioxol-5-ylmethoxy)-4-methoxy-pyridine-2-car- bonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate; (3S,6S,7R,8R)-
3- [[(3-hydroxy-4-methoxy-2-pyridinyl)carbonyl]amino]-6-methyl-4,9-dioxo-8- (phenylmethyl)-l ,5-dioxonan-7-yl 2-methylpropanoate
(xxix) inhibitors of complex II selected from benodanil, benzovindiflupyr, bixafen, boscalid (A.3.4), carboxin, fenfuram, fluopyram (A.3.7), flutolanil, fluxapyroxad (A.3.9), furametpyr, isofetamid, isopyrazam, mepronil, oxycarboxin, penflufen (A.3.14), penthiopyrad (A.3.15), sedaxane (A.3.16), tecloftalam, thifluzamide, N-(4'-trifluoromethylthiobiphenyl-2-yl)- 3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(2-(1 ,3,3-trimethyl-butyl)- phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxamide, 3-(difluoromethyl)-1 -methyl-N- (1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(trifluoromethyl)-1 -methyl-N-(1 ,1 ,3- trimethylindan-4-yl)pyrazole-4-carboxamide, 1 ,3-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyr- azole-4-carboxamide, 3-(trifluoromethyl)-1 ,5-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)- pyrazole-4-carboxamide, 1 ,3,5-trimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-car- boxamide, N-(7-fluoro-1 ,1 ,3-trimethyl-indan-4-yl)-1 ,3-dimethyl-pyrazole-4-carboxamide, N- [2-(2,4-dichlorophenyl)-2-methoxy-1 -methyl-ethyl]-3-(difluoromethyl)-1 -methyl-pyrazole-4- carboxamide;
(xxx) other respiration inhibitors or complex I uncouplers selected from diflumetorim, (5,8-difluoroquinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl}- amine; nitrophenyl derivates: binapacryl, dinobuton, dinocap, fluazinam; ferimzone; or- ganometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide; ametoctradin, silthiofam;
B) Sterol biosynthesis inhibitors (SBI fungicides) such as:
(xxxi) C14 demethylase inhibitors (DM I fungicides) selected from triazoles, azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole (B.1 .5), diniconazole, dinicon- azole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexacona- zole, imibenconazole, ipconazole (B.1.15), metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole (B.1 .23), simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole (B.1 .29), uniconazole, (xxxii) 1 -[re/-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluoropheny^
cyanato-1 H-[1 ,2,4]triazole, 2-[re/-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)- oxiranylmethyl]-2H-[1 ,2,4]triazole-3-thiol, 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1 -(1 ,2,4- triazol-1 -yl)pentan-2-ol, 1 -[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -cyclopropyl-2- (1 ,2,4-triazol-1 -yl)ethanol, 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4- triazol-1 -yl)butan-2-ol, 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1 -(1 ,2,4-triazol-1 -yl)butan- 2-ol, 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-3-methyl-1 -(1 ,2,4-triazol-1 -yl)butan- 2-ol, 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)propan-2-ol, 2- [2-chloro-4-(4-chlorophenoxy)phenyl]-3-methyl-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol, 2-[4-(4- chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)pentan-2-ol, 2-[4-(4- fluorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)propan-2-ol, 2-[2-chloro-4- (4-chlorophenoxy)phenyl]-1 -(1 ,2,4-triazol-1 -yl)pent-3-yn-2-ol; imidazoles: imazalil, pefura- zoate, prochloraz, triflumizol; pyrimidines, pyridines and piperazines: fenarimol, nuarimol, pyrifenox, triforine, [3-(4-chloro-2-fluoro-phenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]-(3- pyridyl)methanol;
(xxxiii) Delta14-reductase inhibitors selected from aldimorph, dodemorph, dodemorph- acetate, fenpropimorph, tridemorph, fenpropidin, piperalin, spiroxamine;
(xxxiv) Inhibitors of 3-keto reductase selected from fenhexamid;
C) Nucleic acid synthesis inhibitors such as:
(xxxv) phenylamides or acyl amino acid fungicides selected from benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl (C.1 .4), metalaxyl-M (mefenoxam) (C.1.5), ofurace, oxadixyl;
(xxxvi) hymexazole, octhilinone, oxolinic acid, bupirimate, 5-fluorocytosine, 5-fluoro-2-(p- tolylmethoxy)pyrimidin-4-amine, or 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4-amine;
D) Inhibitors of cell division and cytoskeleton such as:
(xxxvii) tubulin inhibitors selected from benzimidazoles, thiophanates: benomyl, car- bendazim, fuberidazole, thiabendazole (D.1.4), thiophanate-methyl; or triazolopyrimidines selected from 5-chloro-7-(4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]tri- azolo[1 ,5-a]pyrimidine
(xxxviii) other cell division inhibitors selected from diethofencarb, ethaboxam (D.2.2), pen- cycuron, fluopicolide, zoxamide, metrafenone, pyriofenone;
E) Inhibitors of amino acid and protein synthesis such as:
(xxxix) methionine synthesis inhibitors (anilino-pyrimidines) selected from cyprodinil, mep- anipyrim, pyrimethanil;
(xl) protein synthesis inhibitors selected from blasticidin-S, kasugamycin, kasugamycin hydrochloride-hydrate, mildiomycin, streptomycin, oxytetracyclin, polyoxine, validamycin
A;
F) Signal transduction inhibitors such as:
(ii) MAP / histidine kinase inhibitors selected from fluoroimid, iprodione, procymidone, vinclozolin, fenpiclonil, fludioxonil;
(xli) G protein inhibitors selected from quinoxyfen;
G) Lipid and membrane synthesis inhibitors such as:
(xlii) Phospholipid biosynthesis inhibitors selected from edifenphos, iprobenfos, pyrazo- phos, isoprothiolane; (xliii) lipid peroxidation inhibitors selected from dicloran, quintozene, tecnazene, tolclo- fos-methyl, biphenyl, chloroneb, etridiazole;
(xliv) phospholipid biosynthesis and cell wall deposition inhibitors selected from dime- thomorph, flumorph, mandipropamid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate (G.3.7) and N-(1 -(1 -(4-cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4- fluorophenyl) ester;
(xlv) compounds affecting cell membrane permeability and fatty acides selected from propamocarb, propamocarb-hydrochlorid
(xlvi) fatty acid amide hydrolase inhibitors selected from oxathiapiprolin (G.5.1 ), 2-{3-[2- (1 -{[3,5-bis(difluoromethyl-1 H-pyrazol-1 -yl]acetyl}piperidin-4-yl)-1 ,3-thiazol-4-yl]-4,5- dihydro-1 ,2-oxazol-5-yl}phenyl methanesulfonate, 2-{3-[2-(1 -{[3,5-bis(difluoromethyl)-1 H- pyrazol-1 -yl]acetyl}piperidin-4-yl) 1 ,3-thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol-5-yl}-3- chlorophenyl methanesulfonate;
H) Inhibitors with Multi Site Action such as:
(xlvii) inorganic active substances selected from Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur;
(xlviii) thio- and dithiocarbamates selected from ferbam, mancozeb (H.2.2), maneb,
metam, metiram, propineb, thiram, zineb, ziram;
(xlix) organochlorine compounds selected from phthalimides, sulfamides, chloronitriles, anilazine, chlorothalonil (H.3.2), captafol, captan, folpet, dichlofluanid, dichlorophen, hex- achlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid, N-(4-chloro-2- nitro-phenyl)-N-ethyl-4-methyl-benzenesulfonamide;
(I) guanidines and others selected from guanidine, dodine, dodine free base, guaza- tine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate), dithianon, 2,6-dimethyM H,5H-[1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone;
I) Cell wall synthesis inhibitors such as:
(li) inhibitors of glucan synthesis selected from validamycin, polyoxin B; melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamid, dicyclomet, fenoxanil;
J) Plant defence inducers selected from:
(lii) acibenzolar-S-methyl, probenazole, isotianil, tiadinil, prohexadione-calcium; phospho- nates: fosetyl, fosetyl-aluminum, phosphorous acid and its salts;
K) Compounds with unknown mode of action selected from:
bronopol, chinomethionat, cyflufenamid, cymoxanil, dazomet, debacarb, diclo- mezine, difenzoquat, difenzoquat-methylsulfate, diphenylamin, fenpyrazamine, flumetover, flusulfamide, flutianil, methasulfocarb nitrothal-isopropyl, picarbutra- zox, tolprocarb, 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4-{5-[2-(prop-2-yn- 1 -yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 - yl]ethanone, 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4-{5-[2-fluoro-6-(prop- 2-yn-1 -yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 - yl]ethanone, 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4-{5-[2-chloro-6-
(prop-2-yn-1 -yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 - yl]ethanone, oxin-copper, proquinazid, tebufloquin, tecloftalam, triazoxide, 2-butoxy-6-iodo-3-propylchromen-4-one, N-(cyclopropylmethoxyimino-(6-difluoro- methoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide, N'-(4-(4-chloro-3- trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-meth formamidine, N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)- N-ethyl-N-methyl formamidine, N'-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl- propoxy)-phenyl)-N-ethyl-N-methyl formamidine, methoxy-acetic acid 6-tert-butyl- 8-fluoro-2,3-dimethyl-quinolin-4-yl ester, 3-[5-(4-methylphenyl)-2,3-dimethyl- isoxazolidin-3-yl]-pyridine, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]- pyridine (pyrisoxazole), N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide, 5-chloro-1-(4,6-di- methoxy-pyrimidin-2-yl)-2-methyl-1 H-benzoimidazole, 2-(4-chloro-phenyl)- N-[4- (3,4-dimethoxy-phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide, ethyl (Z)-3-amino-2-cyano-3-phenyl-prop-2-enoate, pentyl N-[6-[[(Z)-[(1 -methyltetrazol- 5-yl)-phenyl-methylene]amino]oxymethyl]-2-pyridyl]carbamate, 2-[2-[(7,8-difluoro- 2-methyl-3-quinolyl)oxy]-6-fluoro-phenyl]propan-2-ol, 2-[2-fluoro-6-[(8-fluoro-2- methyl-3-quinolyl)oxy]phenyl]propan-2-ol, 3-(5-fluoro-3,3,4,4-tetramethyl-3,4- dihydroisoquinolin-1-yl)quinoline, 3-(4,4-difluoro-3,3-dimethyl-3,4- dihydroisoquinolin-1-yl)quinoline, 3-(4,4,5-trifluoro-3,3-dimethyl-3,4- dihydroisoquinolin-1-yl)quinolone, 9-fluoro-2,2-dimethyl-5-(3-quinolyl)-3H-1 ,4- benzoxazepine.
7. The method according to claim 6, wherein the plant is additionally provided with a urea-containing fertilizer.
8. The method according to claim 6 or 7, wherein the fungicide is azoxystrobin (A.1 .1 ), pyraclostrobin (A.1.14), trifloxystrobin (A.1.17), boscalid (A.3.4), fluopyram (A.3.7), fluxap- yroxad (A.3.9), penflufen (A.3.14), penthiopyrad (A.3.15), sedaxane (A.3.16), difenocona- zole (B.1 .5), ipconazole (B.1.15), prothioconazole (B.1.23), triticonazole (B.1 .29), met- alaxyl (C.1.4), metalaxyl-M (mefenoxam) (C.1.5), thiabendazole (D.1 .4), ethaboxam (D.2.2), valifenalate (G.3.7), oxathiapiprolin (G.5.1 ), mancozeb (H.2.2), or chlorothalonil (H.3.2).
9. The method according to anyone of the claims 6 to 8, wherein the application of the (thio)phosphoric acid triamide (T), of the fungicide, and optionally of the urea-containing fertilizer is carried out simultaneously or with a time lag, preferably an interval of 1 day, 2 days, 3 days, 1 week, 2 weeks or 3 weeks.
10. Use of the compositions as defined in claims 1 to 5 for increasing the health of a plant or for increasing the fungicidal activity of the fungicide.
1 1 . Use of a nitrification inhibitor
wherein said nitrification inhibitor is a compound of formula I
Figure imgf000152_0001
or a stereoisomer, salt, tautomer or N-oxide thereof, wherein
A is aryl or hetaryl, wherein the aromatic ring may in each case be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other select- ed from RA;
R1 and R2 are independently of each other selected from H and Ci-C2-alkyl; and
R3 is H, Ci-C4-haloalkyl, Ci-C4-hydroxyalkyl, ethynylhydroxym ethyl, phenylhydroxymethyl, or aryl, wherein the aromatic ring may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from RB; and wherein RA is
(i) halogen, CN, NRaRb, ORc, SRC, C(=Y1)RC, C(=Y1)ORc, C(=Y1)SRC, C(=Y1)NRaRb, Y2C(=Y1)RC, Y2C(=Y1)ORc, Y2C(=Y1)SRC, Y2C(=Y1)NRaRb, Y3Y2C(=Y1)RC, NRaN=C(Rd)(Re),
Figure imgf000152_0002
S(=0)2Y2C(=Y1)Rc, S(=0)2Y2C(=Y1)ORc, S(=0)2Y2C(=Y1)SRc, S(=0)2Y2C(=Y1)NRaR , N02, NON-CN, d-Ce-alkyl, C2-C6-alkenyl, C2-C6-alkynyl, Ci-C4-haloalkyl, C1-C4- cyanoalkyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, C2-C4-alkynyl-Ci-C2-hydroxyalkyl, C2-C4- alkynyloxy;
Figure imgf000152_0003
C2-C4-alkenylene-C(=Y1)ORc,
Figure imgf000152_0004
C2-C4-alkenylene-C(=Y1)SRc,
Figure imgf000152_0005
Ci-C4-alkylene-Y2-
C(=Y1)RC, C2-C4-alkenylene-Y2-C(=Y1)Rc, Ci-C4-alkylene-NRaRb, C2-C4-alkenylene-NRaRb, Ci-C4-alkylene-ORc, C2-C4-alkenylene-ORc, Ci-C4-alkylene-SRc, C2-C4-alkenylene-SRc, wherein the Ci-C4-alkylene or C2-C4-alkenylene chain may in each case be unsubstituted or may be partially or fully substituted by ORa, CN, halogen or phenyl; (iii) aryl, aryl-Ci-C2-alkyl, hetaryl or hetaryl-Ci-C2-alkyl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from Rh;
(iv) a 3- to 14-membered saturated or unsaturated carbocycle or heterocycle, which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from
NR1b, O, and S, wherein S may be oxidized and/or wherein the carbocycle or heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R1b is H, Ci-C4-alkyl, C2-C4- alkenyl, C3-C6-cycloalkyl, C3-C6-cycloalkylmethyl, or OR9; or
(v) L-B, wherein
Lis -CH2-, -CH=CH-, -C≡C-, -C(=0)- or -CH=, and
B is aryl or hetaryl, wherein the aromatic ring of the ary or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from Rh;
or
a 3- to 14-membered saturated or unsaturated carbocycle or heterocycle, which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from NR1b, O, and S, wherein S may be oxidized and/or wherein the carbocycle or heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, inde- pendently of each other, are selected from R; and wherein R1b is H, Ci-C4-alkyl, C2-C4- alkenyl, C3-C6-cycloalkyl, C3-C6-cycloalkylmethyl, or OR9; or
(vi) two substituents RA together represent a carbocyclic or heterocyclic ring, which is fused to A and may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from N R1c, O, and S, wherein S may be oxidized and/or wherein the carbocycle or het- erocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R1c is H, C1-C4- alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6-cycloalkylmethyl, C3-C6-heterocyclyl, C3-C6- heterocyclylmethyl or OR9; and wherein
RB is NH-C(=0)-(Ci-C4-alkyl), NH-C(=0)-(C2-C4-alkenyl),
Figure imgf000153_0001
alkyl), NH-C(=0)-(C3-C6-cycloalkyl), NH-S(=0)2-(Ci-C4-alkyl), or N02; and wherein
Y1, Y2 and Y3 are independently of each other selected from O, S and NR1a, wherein R1a is in each case independently H, Ci-C4-alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6- cycloalkylmethyl, ORa, SRa or NRmRn;
Ra and Rb are independently of each other selected from
(i) H, NRRk, OR, SR, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, C(=Y1)R, C(=Y1)OR, C(=Y1)SR, C(=Y1)NRRk, C(=Y1)C(=Y2)R, S(=0)2Rf; (ii) aryl or hetaryl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from Rh; or
Ra and Rb together with the nitrogen atom to which they are bound form
(iii) a hetaryl group which may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from Rh; or
(iv) a 3- to 10-membered, saturated or unsaturated heterocycle, which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from NR1b, O, and S, wherein S may be oxidized and/or wherein the heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R1b is H, Ci-C4-alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6- cycloalkylmethyl, or OR9;
Rc is
(i) H, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C(=0)OR, C(=0)SR, C(=0)NRRk;
(ii) Ci-C4-alkylene-C(=0)R, Ci-C4-alkylene-C(=0)OR, wherein the Ci-C4-alkylene chain may in each case be unsubstituted or may be partially or fully substituted by ORa, CN , halogen, or phenyl;
(iii) aryl, aryl-Ci-C2-alkyl, hetaryl, or hetaryl-Ci-C2-alkyl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from Rh; or
(iv) a 3- to 10-membered saturated or unsaturated carbocycle or heterocycle, which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from NR1b, O, and S, wherein S may be oxidized and/or wherein the carbocycle or heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R1b is H, Ci-C4-alkyl, C2-C4- alkenyl, C3-C6-cycloalkyl, C3-C6-cycloalkylmethyl, or OR9;
Rd and Re are independently selected from Ci-C4-alkyl, Ci-C4-haloalkyl, NRRk, OR, SR, CN, C(=Y1)R, C(=Y1)OR, C(=Y1)SR, or C(=Y1)NRRk;
Rf is Ci-C4-alkyl, Ci-C4-haloalkyl, NRRk, OR, SR, aryl or hetaryl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from Rh;
Ra is H or Ci-C4-alkyl;
Rh is halogen, CN, N02, NRRk, OR, SR, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, C1-C4- haloalkyl, Ci-C4-alkoxy, C2-C4-alkynyloxy, C(=Y1)R, C(=Y1)OR, C(=Y1)SR, C(=Y1)NRRk, aryl, aryloxy, hetaryl and hetaryloxy;
R is (i) halogen, CN, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-haloalkyl, C2-C4- haloalkenyl;
(ii) =NR1d, wherein R1d is H, Ci-C4-alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6- cycloalkylmethyl, or OR9;
(iii) =0, =S, NRRk, OR, SR, C(=Y1)R, C(=Y1)OR, C(=Y1)SR, C(=Y1)NRRk;
(iv) aryl, aryl-Ci-C2-alkyl, hetaryl, or hetaryl-Ci-C2-alkyl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from halogen, CN, Ci-C4- alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, C2-C4-alkynyloxy, ORa, and SRa; or
(v) C3-C6-cycloalkyl, or 3- to 6-membered heterocyclyl, wherein the cycloalkyl ring or the heterocyclyl ring may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from halogen, CN, Ci-C4-alkyl,
Figure imgf000155_0001
R and Rk are independently selected from H, ORa, SRa, C(=Y1)Ra, C(=Y1)ORa, C(=Y1)SRa, C(=Y1)NRmRn, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-haloalkyl, aryl or hetaryl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently selected from halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, C2-C4-alkynyloxy, ORa, and SRa;
R is H, Ci-C4-alkyl, C2-C4-alkenyl, C2-C4-alkynyl, Ci-C4-haloalkyl, C(=Y1)Ra, C(=Y1)ORa,
C(=Y1)NRmRn, aryl or hetaryl, wherein the aromatic ring of the aryl or hetaryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently selected from halogen, CN, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy, C2-C4-alkynyloxy, ORa, and SRa; and
Rm and Rn are independently selected from H and Ci-C4-alkyl;
and a fungicide for increasing the health of a plant.
12. The use of claim 1 1 , wherein in said compound of formula I , A is phenyl or a 5- or 6-membered hetaryl, wherein the aromatic ring may in each case be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from RA.
13. The use of claim 1 1 or 12, wherein in said compound of formula I, R1 and R2 both represent hydrogen.
14. The use of any one of claims 11 to 13, wherein in said compound of formula I, R3 is hydrogen, Ci-C4-haloalkyl or ethinylhydroxymethyl, and preferably R3 is hydrogen.
15. The use of any one of claims 1 1 to 13, wherein in said compound of formula I, RA, if present, is (i) halogen, CN, NRaRb, ORc, C(=Y1)RC, C(=Y1)ORc, C(=Y1)SRC, C(=Y1)NRaRb, Y2C(=Y1)RC, Y2C(=Y1)NRaRb, NRaN=C(Rd)(Re), S(=0)2Rf, N02, Ci-Ce-alkyl, C2-C6- C1-C4- haloalkyl, Ci-C4-alkoxy, C2-C4-alkynyl-Ci-C2-hydroxyalkyl, C2-C4-alkynyloxy;
(ii) C2-C4-alkenylene-C(=Y1)Rc, C2-C4-alkenylene-Y2-C(=Y1)Rc, wherein the C1-C4- alkylene or C2-C4-alkenylene chain may in each case be unsubstituted or may be partially or fully substituted by CN or halogen;
(iii) aryl, wherein the aromatic ring of the aryl group may be unsubstituted or may be partially or fully substituted by substituents, which are independently of each other selected from Rh; or
(iv) a 3- to 14-membered saturated or unsaturated heterocycle, which may contain 1 , 2, or 3 heteroatoms which, independently of each other, are selected from NR1b, O, and S, wherein S may be oxidized and/or wherein the heterocycle may be unsubstituted or may be partially or fully substituted by substituents which, independently of each other, are selected from R; and wherein R1b is H , Ci-C4-alkyl, C2-C4-alkenyl, C3-C6-cycloalkyl, C3-C6- cycloalkylmethyl, or ORa.
16. The use of any one of claims 1 1 to 15, wherein said fungicide is at least one fungicide selected from the group of fungicides comprising:
Respiration inhibitors such as:
Inhibitors of complex III at Q0 site selected from strobilurines, azoxystrobin (A.1 .1 ), coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxy- strobin/flufenoxystrobin, fluoxastrobin, kresoxim-m ethyl, mandestrobine, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin (A.1 .14), pyrametostrobin, pyraoxystrobin, tri- floxystrobin (A.1 .17) and 2-(2-(3-(2,6-dichlorophenyl)-1 -methyl-allylideneaminooxymethyl)- phenyl)-2-methoxyimino-N-methyl-acetamide, pyribencarb, triclopyricarb/chlorodincarb, famoxadone, fenamidone;
inhibitors of complex III at Q, site selected from cyazofamid, amisulbrom,
[(3S,6S,7R,8R)-8-benzyl-3-[(3-acetoxy-4-methoxy-pyridine-2-carbonyl)amino]-6-methyl- 4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(acet- oxymethoxy)-4-methoxy-pyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl]
2- methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxy-pyri- dine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate,
[(3S,6S,7R,8R)-8-benzyl-3-[[3-(1 ,3-benzodioxol-5-ylmethoxy)-4-methoxy-pyridine-2-car- bonyl]amino]-6-methyl-4,9-dioxo-1 ,5-dioxonan-7-yl] 2-methylpropanoate; (3S,6S,7R,8R)-
3- [[(3-hydroxy-4-methoxy-2-pyridinyl)carbonyl]amino]-6-methyl-4,9-dioxo-8- (phenylmethyl)-l ,5-dioxonan-7-yl 2-methylpropanoate
inhibitors of complex II selected from benodanil, benzovindiflupyr, bixafen, boscalid (A.3.4), carboxin, fenfuram, fluopyram (A.3.7), flutolanil, fluxapyroxad (A.3.9), furametpyr, isofetamid, isopyrazam, mepronil, oxycarboxin, penflufen (A.3.14), penthiopyrad (A.3.15), sedaxane (A.3.16), tecloftalam, thifluzamide, N-(4'-trifluoromethylthiobiphenyl-2-yl)- 3-difluoromethyl-1 -methyl-1 H-pyrazole-4-carboxamide, N-(2-(1 ,3,3-trimethyl-butyl)- phenyl)-1 ,3-dimethyl-5-fluoro-1 H-pyrazole-4-carboxamide, 3-(difluoromethyl)-1 -methyl-N- (1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(trifluoromethyl)-1 -methyl-N-(1 ,1 ,3- trimethylindan-4-yl)pyrazole-4-carboxamide, 1 ,3-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyr- azole-4-carboxamide, 3-(trifluoromethyl)-1 ,5-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)- pyrazole-4-carboxamide, 1 ,3,5-trimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-car- boxamide, N-(7-fluoro-1 ,1 ,3-trimethyl-indan-4-yl)-1 ,3-dimethyl-pyrazole-4-carboxamide, N- [2-(2,4-dichlorophenyl)-2-methoxy-1 -methyl-ethyl]-3-(difluoromethyl)-1 -methyl-pyrazole-4- carboxamide;
other respiration inhibitors or complex I uncouplers selected from diflumetorim, (5,8-difluoroquinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)-phenyl]-ethyl}- amine; nitrophenyl derivates: binapacryl, dinobuton, dinocap, fluazinam; ferimzone; or- ganometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide; ametoctradin, silthiofam;
Sterol biosynthesis inhibitors (SBI fungicides) such as:
C14 demethylase inhibitors (DM I fungicides) selected from triazoles, azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole (B.1 .5), diniconazole, dinicon- azole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexacona- zole, imibenconazole, ipconazole (B.1.15), metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole (B.1 .23), simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole (B.1.29), uniconazole,
1 -[re/-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thio- cyanato-1 H-[1 ,2,4]triazole, 2-[re/-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)- oxiranylmethyl]-2H-[1 ,2,4]triazole-3-thiol, 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1 -(1 ,2,4- triazol-1 -yl)pentan-2-ol, 1 -[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -cyclopropyl-2- (1 ,2,4-triazol-1 -yl)ethanol, 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4- triazol-1 -yl)butan-2-ol, 2-[2-chloro-4-(4-chlorophenoxy)phenyl]-1 -(1 ,2,4-triazol-1 -yl)butan- 2-ol, 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-3-methyl-1 -(1 ,2,4-triazol-1 -yl)butan- 2-ol, 2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)propan-2-ol, 2- [2-chloro-4-(4-chlorophenoxy)phenyl]-3-methyl-1 -(1 ,2,4-triazol-1 -yl)butan-2-ol, 2-[4-(4- chlorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)pentan-2-ol, 2-[4-(4- fluorophenoxy)-2-(trifluoromethyl)phenyl]-1 -(1 ,2,4-triazol-1 -yl)propan-2-ol, 2-[2-chloro-4- (4-chlorophenoxy)phenyl]-1 -(1 ,2,4-triazol-1 -yl)pent-3-yn-2-ol; imidazoles: imazalil, pefura- zoate, prochloraz, triflumizol; pyrimidines, pyridines and piperazines: fenarimol, nuarimol, pyrifenox, triforine, [3-(4-chloro-2-fluoro-phenyl)-5-(2,4-difluorophenyl)isoxazol-4-yl]-(3- pyridyl)methanol;
Delta14-reductase inhibitors selected from aldimorph, dodemorph, dodemorph- acetate, fenpropimorph, tridemorph, fenpropidin, piperalin, spiroxamine;
Inhibitors of 3-keto reductase selected from fenhexamid;
Nucleic acid synthesis inhibitors such as:
phenylamides or acyl amino acid fungicides selected from benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl (C.1 .4), metalaxyl-M (mefenoxam) (C.1.5), ofurace, oxadixyl;
hymexazole, octhilinone, oxolinic acid, bupirimate, 5-fluorocytosine, 5-fluoro-2-(p- tolylmethoxy)pyrimidin-4-amine, or 5-fluoro-2-(4-fluorophenylmethoxy)pyrimidin-4-amine; Inhibitors of cell division and cytoskeleton such as: (Ixiii) tubulin inhibitors selected from benzimidazoles, thiophanates: benomyl, car- bendazim, fuberidazole, thiabendazole (D.1.4), thiophanate-methyl; or triazolopyrimidines selected from 5-chloro-7-(4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]tri- azolo[1 ,5-a]pyrimidine
(Ixiv) other cell division inhibitors selected from diethofencarb, ethaboxam (D.2.2), pen- cycuron, fluopicolide, zoxamide, metrafenone, pyriofenone;
E) Inhibitors of amino acid and protein synthesis such as:
(Ixv) methionine synthesis inhibitors (anilino-pyrimidines) selected from cyprodinil, mep- anipyrim, pyrimethanil;
(Ixvi) protein synthesis inhibitors selected from blasticidin-S, kasugamycin, kasugamycin hydrochloride-hydrate, mildiomycin, streptomycin, oxytetracyclin, polyoxine, validamycin A;
F) Signal transduction inhibitors such as:
(iii) MAP / histidine kinase inhibitors selected from fluoroimid, iprodione, procymidone, vinclozolin, fenpiclonil, fludioxonil;
(Ixvii) G protein inhibitors selected from quinoxyfen;
G) Lipid and membrane synthesis inhibitors such as:
(Ixviii) Phospholipid biosynthesis inhibitors selected from edifenphos, iprobenfos, pyrazo- phos, isoprothiolane;
(Ixix) lipid peroxidation inhibitors selected from dicloran, quintozene, tecnazene, tolclo- fos-methyl, biphenyl, chloroneb, etridiazole;
(Ixx) phospholipid biosynthesis and cell wall deposition inhibitors selected from dime- thomorph, flumorph, mandipropamid, pyhmorph, benthiavalicarb, iprovalicarb, valifenalate (G.3.7) and N-(1 -(1 -(4-cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4- fluorophenyl) ester;
(Ixxi) compounds affecting cell membrane permeability and fatty acides selected from propamocarb, propamocarb-hydrochlorid
(Ixxii) fatty acid amide hydrolase inhibitors selected from oxathiapiprolin (G.5.1 ), 2-{3-[2-
(1 -{[3,5-bis(difluoromethyl-1 H-pyrazol-1 -yl]acetyl}piperidin-4-yl)-1 ,3-thiazol-4-yl]-4,5- dihydro-1 ,2-oxazol-5-yl}phenyl methanesulfonate, 2-{3-[2-(1 -{[3,5-bis(difluoromethyl)-1 H- pyrazol-1 -yl]acetyl}piperidin-4-yl) 1 ,3-thiazol-4-yl]-4,5-dihydro-1 ,2-oxazol-5-yl}-3- chlorophenyl methanesulfonate;
H) Inhibitors with Multi Site Action such as:
(Ixxiii) inorganic active substances selected from Bordeaux mixture, copper acetate, cop- per hydroxide, copper oxychloride, basic copper sulfate, sulfur;
(Ixxiv) thio- and dithiocarbamates selected from ferbam, mancozeb (H.2.2), maneb, metam, metiram, propineb, thiram, zineb, ziram;
(Ixxv) organochlorine compounds selected from phthalimides, sulfamides, chloronitriles, anilazine, chlorothalonil (H.3.2), captafol, captan, folpet, dichlofluanid, dichlorophen, hex- achlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid, N-(4-chloro-2- nitro-phenyl)-N-ethyl-4-methyl-benzenesulfonamide; (Ixxvi) guanidines and others selected from guanidine, dodine, dodine free base, guaza- tine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate), dithianon, 2,6-dimethyM H,5H-[1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)-tetraone; I) Cell wall synthesis inhibitors such as:
(Ixxvii) inhibitors of glucan synthesis selected from validamycin, polyoxin B; melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamid, dicyclomet, fenoxanil;
J) Plant defence inducers selected from:
(Ixxviii) acibenzolar-S-methyl, probenazole, isotianil, tiadinil, prohexadione-calcium; phos- phonates: fosetyl, fosetyl-aluminum, phosphorous acid and its salts;
K) Compounds with unknown mode of action selected from:
(Ixxix) bronopol, chinomethionat, cyflufenamid, cymoxanil, dazomet, debacarb, diclo- mezine, difenzoquat, difenzoquat-methylsulfate, diphenylamin, fenpyrazamine,
flumetover, flusulfamide, flutianil, methasulfocarb nitrothal-isopropyl, picarbutrazox, tolpro- carb, 2-[3,5-bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4-{5-[2-(prop-2-yn-1 -yloxy)phenyl]- 4,5-dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 -yl]ethanone, 2-[3,5- bis(difluoromethyl)-1 H-pyrazol-1 -yl]-1 -[4-(4-{5-[2-fluoro-6-(prop-2-yn-1 -yloxy)phenyl]-4,5- dihydro-1 ,2-oxazol-3-yl}-1 ,3-thiazol-2-yl)piperidin-1 -yl]ethanone, 2-[3,5-bis(difluoromethyl)- 1 H-pyrazol-1 -yl]-1 -[4-(4-{5-[2-chloro-6-(prop-2-yn-1 -yloxy)phenyl]-4,5-dihydro-1 ,2-oxazol- 3-yl}-1 ,3-thiazol-2-yl)piperidin-1 -yl]ethanone, oxin-copper, proquinazid, tebufloquin, te- cloftalam, triazoxide, 2-butoxy-6-iodo-3-propylchromen-4-one, N-(cyclo- propylmethoxyimino-(6-difluoro-methoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide, N'-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(4-(4-fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N- methyl formamidine, N'-(2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)- N-ethyl-N-methyl formamidine, N'-(5-difluoromethyl-2-methyl-4-(3-trimethylsilanyl- propoxy)-phenyl)-N-ethyl-N-methyl formamidine, methoxy-acetic acid 6-tert-butyl-8-fluoro- 2,3-dimethyl-quinolin-4-yl ester, 3-[5-(4-methylphenyl)-2,3-dimethyl-isoxazolidin-3-yl]- pyridine, 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3-yl]-pyridine (pyrisoxazole), N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide, 5-chloro-1 -(4,6-dimethoxy- pyrimidin-2-yl)-2-methyl-1 H-benzoimidazole, 2-(4-chloro-phenyl)- N-[4-(3,4-dimethoxy- phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide, ethyl (Z)-3-amino-2-cyano-3-phenyl- prop-2-enoate, pentyl N-[6-[[(Z)-[(1-methyltetrazol-5-yl)-phenyl- methylene]amino]oxymethyl]-2-pyridyl]carbamate, 2-[2-[(7,8-difluoro-2-methyl-3- quinolyl)oxy]-6-fluoro-phenyl]propan-2-ol, 2-[2-fluoro-6-[(8-fluoro-2-methyl-3- quinolyl)oxy]phenyl]propan-2-ol, 3-(5-fluoro-3,3,4,4-tetramethyl-3,4-dihydroisoquinolin-1 - yl)quinoline, 3-(4,4-difluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1 -yl)quinoline, 3-(4,4,5- trifluoro-3,3-dimethyl-3,4-dihydroisoquinolin-1 -yl)quinolone, 9-fluoro-2,2-dimethyl-5-(3- quinolyl)-3H-1 ,4-benzoxazepine.
17. The use of claim 16, wherein said fungicide is azoxystrobin (A.1.1 ), pyra- clostrobin (A.1 .14), trifloxystrobin (A.1 .17), boscalid (A.3.4), fluopyram (A.3.7), fluxapyrox- ad (A.3.9), penflufen (A.3.14), penthiopyrad (A.3.15), sedaxane (A.3.16), difenoconazole (B.1.5), ipconazole (B.1.15), prothioconazole (B.1 .23), triticonazole (B.1 .29), metalaxyl (C.1 .4), metalaxyl-M (mefenoxam) (C.1.5), thiabendazole (D.1 .4), ethaboxam (D.2.2), valifenalate (G.3.7), oxathiapiprolin (G.5.1 ), mancozeb (H.2.2), or chlorothalonil (H.3.2).
18. The use of any one of claims 1 1 to 17, wherein said combination of a nitrification inhibitor and a fungicide further comprises a fertilizer.
19. A composition for increasing the health of a plant comprising at least one nitrification inhibitor as defined in any one of claims 1 1 to 15 and at least one fungicide as defined in claim 16 or 17.
20. The composition of claim 19, which additionally comprises at least one carrier.
21 . A method for increasing the health of a plant, comprising treating a plant growing on soil or soil substituents and/or the locus or soil or soil substituents where the plant is growing or is intended to grow with a combination of at least one nitrification inhibitor and at least one fungicide as defined in any one of claims 1 1 to 17, or a composition as defined in claim 9 or 10.
22. The method of claim 21 , wherein the plant and/or the locus or soil or soil substituents where the plant is growing or is intended to grow is additionally provided with a fertilizer.
23. The method of claim 21 or 22, wherein the application of said nitrification inhibitor (A) and of said fungicide (B), and optionally of said fertilizer (C) is carried out simultaneously or with a time lag, preferably an interval of 1 day, 2 days, 3 days, 1 week, 2 weeks or 3 weeks.
24. The use of any one claims 1 1 to 18, the composition of claim 19 or 20, or the method of any one claims 21 to 23, wherein said increase of the health of a plant is re- fleeted by an increase in growth of root and shoot, an overall increase in productivity and/or a faster and more efficient development of the plant.
25. The use of any one claims 1 1 to 18 or 24, the composition of claim 19, 20 or 24, or the method of any one claims 21 to 24, wherein said plant is an agricultural plant such as wheat, barley, oat, rye, soybean, corn, oilseed rape, canola, sunflower, cotton, sugar cane, sugar beet, rice, or a vegetable such as spinach, lettuce, asparagus, or cabbages; or sorghum; a silvicultural plant; an ornamental plant; or a horticultural plant, each in its natural or in a genetically modified form.
PCT/IB2015/052773 2014-04-17 2015-04-16 Combination of novel nitrification inhibitors and fungicides as well as combination of (thio)phosphoric acid triamides and fungicides WO2015104699A2 (en)

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