US 20180289005A1 ( 19) United States (12 ) Patent Application Publication ( 10) Pub . No. : US 2018 /0289005 A1 Hoffman et al. ( 43) Pub . Date : Oct. 11 , 2018

(54 ) FUNGICIDAL COMPOSITIONS Publication Classification (51 ) Int . CI. (71 ) Applicant: SYNGENTA PARTICIPATIONS AG , AOIN 43 /40 ( 2006 .01 ) Basel ( CH ) A01N 43 / 56 ( 2006 . 01) AOIN 37 /50 ( 2006 .01 ) (72 ) Inventors : Thomas James Hoffman , Stein ( CH ) ; A01N 3734 ( 2006 .01 ) Sarah Sulzer- Mosse , Stein ( CH ); Kurt AOIN 43 /44 (2006 .01 ) Nebel, Stein (CH ) ; Fredrik Emil AOIN 43 /54 ( 2006 . 01) Malcolm CEDERBAUM , Stein ( CH ) ; A01N 43 /653 (2006 . 01 ) Mathias Blum , Stein (CN ) A01N 45 /02 (2006 . 01) AOIN 47/ 14 ( 2006 .01 ) (52 ) U . S . CI. (73 ) Assignee : SYNGENTA PARTICIPATIONS AG , CPC ...... A01N 43 /40 ( 2013 .01 ); A01N 43/ 56 DarBasel ( CH ) ( 2013 .01 ) ; A01N 37 /50 ( 2013 .01 ); AOIN 37 /34 ( 2013 .01 ) ; AOIN 47 / 14 ( 2013 .01 ) ; (21 ) Appl. No. : 15 / 767, 555 A01N 43 /54 (2013 .01 ) ; A01N 437653 (2013 .01 ) ; A01N 45 /02 ( 2013 .01 ) ; AOIN (22 ) PCT Filed: Oct . 10 , 2016 43 /44 ( 2013 .01 ) ( 86 ) PCT No .: PCT/ EP2016 /074137 (57 ) ABSTRACT $ 371 ( c ) ( 1 ) , A fungicidal composition comprising a mixture of compo Apr. 11 , 2018 nents ( A ) and (B ), wherein components ( A ) and ( B ) are as ( 2 ) Date : defined in claim 1 , and use of the compositions in agriculture Foreign Application Priority Data or horticulture for controlling or preventing infestation of ( 30 ) plants by phytopathogenic microorganisms, preferably Oct. 14 , 2015 (EP ) ...... 15189809. 5 fungi. US 2018 /0289005 A1 Oct. 11 , 2018

FUNGICIDAL COMPOSITIONS [ 0006 ] wherein [0007 ] Rl represents hydrogen , chloro , bromo, cyano , [0001 ] The present invention relates to novel fungicidal C .- C2 alkyl, CO2( C , -C2 alkyl ), CO2H , CONH2, CONH compositions, to their use in agriculture or horticulture for ( C , - C4 alkyl) , CON ( C , - C4 alkyl) 2 , C , - C4 haloalkyl, or controlling diseases caused by phytopathogens, especially C -C4 haloalkoxy; phytopathogenic fungi , and to methods of controlling dis [0008 ] R2 represents Cz -Coalkyl , Cz -Coalkenyl , or Rº; eases on useful plants , especially fruits and vegetables. [0009 ] R3 and R4 independently of each other represent [ 0002 ] Certain pyridylamidines derivatives have been pro hydrogen , methyl, ethyl, isopropyl or cyclopropyl ; or posed in the literature as microbiocidal active ingredients in R3 and R4 together with the nitrogen atom to which pesticides . For example , WO 00 / 46184 and WO 03 /093224 they are attached form a 3 - , 4 - or 5 -membered saturated disclose pyridylamidines which are described to be useful as cyclic group ; fungicides. WO 2008 / 101682 and WO 2012 / 146125 also [0010 ] R represents C , -Cz alkyl , or CZ -C2 alkoxyC / -C2 disclose pyridylamidines and mixture compositions com alkyl; prising them as having biological activity against certain [0011 ] Rº represents phenyl, which can be substituted phytopathogenic fungi. However, the biological properties by chloro or CZ -fluoroalkyl ; or a salt, enantiomer , of these known compounds and their compositions are not tautomer or N -oxide thereof; entirely satisfactory for controlling or preventing infestation [0012 ] and component ( B ) is a compound selected from of plants by phytopathogenic fungi. Further, whilst many the group consisting of fungicidal compounds and compositions , belonging to vari [0013 ] (B1 ) a strobilurin fungicide selected from the ous different chemical classes, have been / are being devel group consisting of azoxystrobin , picoxystrobin , enox oped for use as fungicides in crops of useful plants , crop astrobin , pyraoxystrobin , mandestrobin , flufenox tolerance and activity against particular phytopathogenic ystrobin , coumoxystrobin , crysastrobin , dimox fungi do not always satisfy the needs of agricultural practice ystrobin , metominostrobin , fenaminostrobin , in many respects . pyrametostrobin , triclopyricarb , kresoxim -methyl , flu [0003 ] There is therefore a continuing need to find new oxastrobin , pyribencarb , pyraclostrobin and triflox compounds and new compositions having superior biologi ystrobin ; cal properties for use in controlling or preventing infestation [0014 ] (B2 ) an azole fungicide selected from the group of plants by phytopathogenic fungi; for example , com consisting of azaconazole , etaconazole , ipconazole , pounds possessing a greater biological activity , an advanta tebuconazole, bitertanol, fenbucoanzole , metconazole , geous spectrum of activity , an increased safety profile , tetraconazole , bromucoanzole , fluquinconazole , improved physico - chemical properties, increased biode myclobutanil , triadimefon , flusilazole , penconazole , gradability , or compositions possessing a broader of spec triadimenol, triticonazole, simeconazole , imibencon trum of activity , improved crop tolerance , synergistic inter azole , hexaconazole , flutriafol, diniconazole , cypro actions or potentiating properties , or compositions which conazole , difenoconazole , epoxiconazole , propicon display a more rapid onset of action or which have longer azole , prothioconazole , pyrifenox , nuarimol, fenarimol, lasting residual activity or which enable a reduction in the imizalil , triflumizole , prochloraz , pefurazoate , oxpoco number of applications and / or a reduction in the application nazole ,Mefentrifluconazole , 2 - [[ 3 - ( 2 - chlorophenyl ) - 2 rate of the compounds and compositions required for effec ( 2, 4 -difluorophenyl ) oxiran -2 -yl ] methyl ] - 4H - 1, 2 ,4 - tri tive control of a phytopathogen , thereby enabling beneficial azole - 3 - thione and 2 - [ 2 -chloro - 4 - (4 -chlorophenoxy ) resistance -management practices , reduced environmental phenyl] - 1 -( 1 ,2 , 4 -triazol - 1 - yl) propan - 2 -ol ; impact and reduced operator exposure . [ 0015 ] ( B3 ) a morpholine fungicide selected from [0004 ] The use of compositions comprising mixtures of aldimorph , dodemorph , fenpropimorph and tride different fungicidal compounds can address some of these morph ; needs ( e . g . by combining fungicides with differing spec [ 0016 ] (B4 ) a carboxamide fungicide selected from trums of activity ) . However, it is especially advantageous if , bixafen , fluopyram , fluxapyroxad , isopyrazam , sedax in such mixture compositions, one or more of the fungicidal ane, furametpyr , penflufen , penthiopyrad , benzovindi compounds themselves possess superior biological proper flupyr , thifluzamide, isofetamid , boscalid , carboxin , ties over known and closely related fungicidal compounds . oxycarboxin , fenfuram , flutolanil , pyraziflumid , pydi flumetofen , mepronil, benodanil , N - [ ( 5 - chloro - 2 - iso [0005 ] The present invention therefore provides novel propyl- phenyl ) methyl ] -N - cyclopropyl- 3 - (difluorom fungicidal compositions comprising as active ingredients a ethyl ) - 5 - fluoro - 1 -methyl - - 4 - carboxamide , mixture of component ( A ) and component ( B ) , wherein 3 - (difluoromethyl ) - N - ( 7 - fluoro - 1 , 1 , 3 - trimethyl- indan component ( A ) is a compound of formula ( I) 4 - yl ) - 1 -methyl - pyrazole - 4 - carboxamide , 3 - (difluorom ethyl) - 1- methyl - N - ( 1, 1 ,3 -trimethylindan - 4 -yl ) pyra zole - 4 -carboxamide and (R ) - 3 - ( difluoromethyl) - 1 methyl - N - ( 1 , 1 , 3 - trimethylindan - 4 -yl ) pyrazole - 4 carboxamide; [ 0017 ] (B5 ) an anilinopyrimidine fungicide selected R20 from cyprodinil , mepanipyrim and pyrimethanil ; [ 0018 ] (B6 ) an phenylpyrrole fungicide selected from fludioxonil and fenpiclonil ; [ 0019 ] (B7 ) a phenylamide fungicide selected from benalaxyl, benalaxyl- M , furalaxyl, mefenoxam (meta laxyl- M ) and metalaxyl, ofurace and oxadixyl; US 2018 /0289005 A1 Oct . 11, 2018

[ 0020 ] (B8 ) a fungicide selected from the group con ide , 2 -( difluoromethyl) - N -[ (3R )- 1, 1 -dimethyl - 3 sisting of ametoctradin , amisulbrom , anilazine , aureo propyl- indan - 4 -yl ]pyridine - 3 -carboxamide , fungin , benomyl , benthiavalicarb , benthiazole , bethox compound of the formula azin , BLAD , blasticidin - S , Bordeaux mixture , bupirimate , calcium polysulfide , captafol, captan , car baryl, carbendazim , carpropamid , chinomethionate , chitosan , chlobenthiazone , chlorfenazole , chloroneb , chlorothalonil , chlozolinate , climbazole , copper acetate , copper carbonate , copper hydroxide, copper N naphthenate , copper oleate , copper oxychloride , copper oxyquinolate , copper silicate , copper sulphate , copper tallate, cuprous oxide , cyazofamid , cyclafuramid , cyflufenamid , cymoxanil , dazomet , dichlofluanid , dichlorprop , diclocymet , diclomezine, dicloran , diethofencarb , diflumetorim , dimetachlone , dimethi [0021 ] a compound of the formula pin , dimethirimol, dimethomorph , dinocap , dinocton , dinobuton , dinopenton , dipymetitrone , ditalimfos, dithianon , dodicin , dodine , doguadine, edifenphos, etem , ethaboxam , ethirimol, ethoxyquin , etridiazole , famoxadone, fenamidone , fenarimol, fenhexamid , fenoxanil , fenpropidine , fenpyrazamine , fentin acetate , fentin hydroxide , ferbam , ferimzone, fluazinam , flu N morph , fluopicolide , fluoroimide , flusulfamide, flu tianil , folpet , fosetyl- AI, fuberidazole , gibberellic acid , guazatine, hymexazole , iminoctadine, iodocarb , iprobenfos , iprodione , iprovalicarb , isoprothiolane , kasugamycin , mancozeb , mandipropamid , maneb , metam , meptyldinocap , metiram , metrafenone , nabam , [0022 ] and a compound of the formula : oxathiapiprolin , paclobutrazol , pencycuron , phenamac ril, phosdiphen , phthalide, picarbutrazox , polyoxin D , probenazole , procymidone , prohexadione, propamo carb, propineb , proquinazid , pyrazophos, pyrifenox , pyrimorph , pyriofenone, pyroquilon , quinoxyfen , quin tozene , silthiofam , spiroxamine , streptomycin , sulphur, tebufloquin , tecloftalam , tecnazene, thiabendazole , thidiazuron , thicyofen , thiophanate -methyl , thiram , tioxymid , tolclofos -methyl , tolprocarb , tolylfluanid , tri azoxide , tribufos , tricyclazole , triforine , validamycin , N valifenalate, vapam , vinclozolin , zineb , ziram , zoxam ide , [ 2 - [ 3 - [ 2 - [ 1 - [ 2 - [ 3 , 5 - bis ( difluoromethyl) pyrazol - 1 yl] acetyl] - 4 -piperidyl ] thiazol - 4 - yl) - 4 ,5 - dihyd roisox azol- 5 -yl ] - 3 -chloro -phenyl ] methanesulfonate , but- 3 ynyl N - [ 6 - [ [ ( Z ) - [ ( 1 -methyltetrazol - 5 - yl) -phenyl [0023 ] (B9 ) a plant- bioregulator selected from the methylene ] aminojoxymethyl) - 2 -pyridyl ] , group consisting of acibenzolar- S -methyl , chlormequat N '- [4 - (4 , 5 -dichlorothiazol - 2 -yl ) oxy - 2 ,5 -dimethyl - phe chloride, ethephon , isotianil, mepiquat chloride , tiadinil nyl ]- N -ethyl - N -methyl - formamidine, 4 -( 2 -bromo - 4 and trinexapac - ethyl; fluoro - phenyl) - N - ( 2 - chloro - 6 - fluoro -phenyl ) - 2 , 5 - dim [ 0024 ] (B10 ) an selected from the group ethyl- pyrazol- 3 - amine , 2 - [ 2 - fluoro -6 - [ ( 8 - fluoro - 2 consisting of abamectin , acequinocyl, , methyl - 3 - quinolyl) oxy ]phenyl ] propan - 2 -ol , 4 ,4 , 5 , afidopyropen , alanycarb , allethrin , alpha trifluoro - 3 , 3 - dimethyl- 1 - ( 3 - quinolyl) isoquinoline , , alphamethrin , amidoflumet, 3 -chloro -6 -methyl - 5 -phenyl -4 - ( 2 , 4, 6 -trifluorophenyl ) , azocyclotin , bacillus firmus, bacillus pyridazine , 3 - chloro -4 -( 2 ,6 -difluorophenyl ) -6 -methyl thuringiensis , bensultap , benzoximate , betacyfluthrin , 5 -phenyl - pyridazine , 2 - ( difluoromethyl) -N -( 1 ,1 , 3 bifenazate , binapacryl, , bioresmethrin , trimethylindan - 4 -yl ) pyridine - 3 -carboxamide , biphenthrin , broflanilide , brofluthrinate , bromophos 2 -( difluoromethyl) - N - ( 3 - ethyl - 1 , 1 - dimethyl- indan - 4 ethyl, buprofezine , cadusafos , , , yl) pyridine - 3 - carboxamide , 2 - ( difluoromethyl) - N - ( 1 , cartap , , , chromafenoz 1 -dimethyl - 3 -propyl - indan - 4 -yl ) pyridine - 3 -carboxam ide, cloethocarb , , , cycla ide, 2 -( difluoromethyl ) - N -( 3 -isobutyl - 1, 1 -dimethyl niliprole , cycloprothrin , cycloxaprid , cyenopyrafen , indan - 4 - yl) pyridine - 3 - carboxamide, cyflumetofen , , , cypermethrin , 2 -( difluoromethyl) - N -[ ( 3R )- 1, 1, 3 - trimethylindan - 4 -yl ] , , , demeton - s pyridine- 3 - carboxamide , 2 - (difluoromethyl ) - N - [ ( 3R ) methyl, diafenthiuron , dialifos , dichloromezotiaz , 3 - ethyl- 1, 1 -dimethyl - indan -4 -yl ] pyridine - 3 - carboxam diflovidazine , , dinactin , dinocap , dinote US 2018 /0289005 A1 Oct. 11 , 2018

furan , d - , emamectin , , esfenvaler possible tautomers. The present invention includes all pos ate , , ethiprole, , etoxazole , famphur, sible tautomeric forms for a compound of formula ( I ) , and fenazaquin , fenfluthrin , , , fen also a racemic compound , i . e . a mixture of at least two propathrin , fenpyroxymate , , , flom enantiomers in a ratio of substantially 50 :50 . etoquin , flonicamid , fluacrypyrim , fluazuron , flubendi [0029 ] In each case , the compounds of formula (I ) accord amide, flucythrinate , fluensulfone , flufenerim , ing to the invention are in free form , in oxidized form as a flufenprox , flufiprole , fluhexafon , , flupyra N -oxide or in salt form , e . g . an agronomically usable salt difuron , fluvalinate , fosthiazate , gamma- cyhalothrin , form . gossyplure , guadipyr, halofenozide , halofenprox , har (0030 ) N - oxides are oxidized forms of tertiary amines or pin , hexythiazox , , imicyafos, imida oxidized forms of nitrogen containing heteroaromatic com cloprid , , , iodomethane , isoth pounds . They are described for instance in the book “ Het ioate , ivermectin , lambda - cyhalothrin , lepimectin , erocyclic N -oxides ” by A . Albini and S . Pietra , CRC Press , , , metaldehyde, , Boca Raton 1991. methoxyfenozide , , milbemectin , niclos 10031 ] Preferred groups and values for the substituents R1, amide, , , - ethyl, pasteuria R2, R3, R4 and RS in the compounds of formula (I ) are , in any nishizawae , p - cymene , , , phos combination thereof, as set out below . phocarb , piperonylbutoxide , , pirimiphos [0032 ] Preferably R is chloro , bromo, cyano , methyl or ethyl, polyhedrosis virus, , , pro C , fluoroalkyl. fenofos , propargite , propetamphos , protrifenbute , [0033 ] Preferably R² is n - propyl, iso - propyl or allyl . pyflubumide , pymetrozine, pyraclofos , pyrafluprole , [0034 ] Preferably R3 is methyl. , pyridaben , pyridalyl, pyrifluquinazon , [0035 ] Preferably R4 is ethyl or iso -propyl . pyrimidifen , pyriprole , , selamectin , sila [0036 ] Preferably R is methyl . fluofen , spinetoram , , spirodiclofen , spirome [0037 ] Preferably component ( A ) is a compound of for sifen , spirotetramat, , , tebufen mula ( l' ) which are compounds of formula (I ) wherein Rl is pyrad , , terpenoid blends , terpenoids , chloro , bromo, cyano ,methyl or C , fluoroalkyl; R² is n - pro tetradiphon , , tetranactin , tetraniliprole , pyl, iso -propyl or allyl; R * is methyl ; R * is ethyl or iso theta -cypermethrin , , , thiodi propyl; and Rºis methyl; or a salt , enantiomer, tautomer or carb , tioxazafen , tolfenpyrad , , trichlorfon , N -oxide thereof. triflumezopyrim , zeta- cypermethrin and a - terpinene ; 0038 ] Most preferably component ( A ) is a compound and selected from compound no . 67. 002 , 67 .003 , 67 .007 , [0025 ] (B11 ) glyphosate . 67. 009 , 67 .011 , 67. 013 , 67 .014 , 67 .015 and 67. 018 , as [0026 ] In general, the weight ratio of component ( A ) to defined in the Table X below : component ( B ) is from 1000 : 1 to 1 : 1000 , especially from 50 : 1 to 1 : 50 , more especially in a ratio from 40 : 1 to 1 : 40 , TABLE X even more especially in a ratio of from 20 : 1 to 1 : 20 , even Com more especially still from 10 : 1 to 1 : 10 , and very especially pound from 5 : 1 and 1 : 5 . Special preference is given to a ratio of No. Structural formula from 2 : 1 to 1 : 2 , and a ratio of from 4 : 1 to 2 : 1 is also especially preferred . Specific individual ratios that are pre 67. 002 ferred include the ratio of 1 : 1 , 5 : 1 , 5 : 2 , 5 : 3 , 5 : 4 , 4 : 1 , 4 : 2 , 4 : 3 , 3 : 1 , 3 : 2 , 2 : 1 , 1 : 5 , 2 : 5 , 3 : 5 , 4 : 5 , 1 : 4 , 2 : 4 , 3 : 4 , 1 : 3 , 2 : 3 , 1 : 2 , 1 :600 , 1 :300 , 1 : 150 , 1 : 100 , 1 : 50 , 1 : 40 , 1 : 35 , 1 : 20 , 2 : 35 , Br 4 :35 , 1: 10 1: 75 , 2 : 75 , 4 :75 , 1: 6000 , 1 :3000 , 1: 1500 , 1 :350 , 2 : 350 , 4 :350 , 1 :750 , 2 :750 , and 4 :750 . [0027 ] Compounds of formula (1 ) possess superior bio logical properties over known and closely related fungicidal compounds. Such benefits may include , inter alia , advanta N '- [ 5 - bromo - 2- methyl -6 -[ ( 1S )- 1 geous levels of biological activity for protecting plants methyl- 2 -propoxy - ethoxy ] - 3 against diseases that are caused by fungi or superior prop pyridyl ]- N - ethyl - N -methyl erties for use as agrochemical active ingredients ( for formamidine example , greater biological activity , an advantageous spec trum of activity , an increased safety profile , improved 67 .003 physico - chemical properties, or increased biodegradability ). [0028 ] The presence of one or more possible asymmetric carbon atoms in a compound of formula ( I ) means that the Br compounds may occur in optically isomeric forms, i. e . enantiomeric or diastereomeric forms. The specific substi tution pattern at the carbon atom to which R2 is attached means that the compounds of formula (I ) occur in ( at least ) two enantiomeric forms. Also atropisomers may occur as a N '- [5 -bromo - 2 -methyl - 6 - [ (1R )- 1 result of restricted rotation about a single bond . The present methyl- 2 -propoxy - ethoxy ] - 3 invention includes all those possible isomeric forms ( e . g . pyridyl ] -N - ethyl- N -methyl geometric isomers ) and mixtures thereof for a compound of formamidine formula ( I ) . Likewise , formula (I ) is intended to include all US 2018 /0289005 A1 Oct . 11, 2018

TABLE X - continued TABLE X -continued Com Com pound pound No . Structural formula No . Structural formula

67 .007 67 .014

N ' - 15 - cyano - 2 -methyl - 6 - ( 1 N - 16 - ( 2 - allyloxy- 1 -methyl - ethoxy ) - 5 methyl- 2 -propoxy - ethoxy ) - 3 chloro - 2 -methyl - 3 - pyridyl] - N - ethyl - N pyridyl] - N - ethyl- N -methyl methyl- formamidine formamidine 67 .015 NO 67 .009

N ' - [5 - chloro - 2 -methyl - 6 - ( 1 -methyl - 2 propoxy - ethoxy )- 3 -pyridyl ] - N - ethyl N -methyl - formamidine 67 . 018

Br N '- [ 5 - ( difluoromethyl) - 2 -methyl 6 -( 1- methyl - 2- propoxy -ethoxy ) N '- [ 5 -bromo - 2- methyl - 6 -( 1 -methyl - 2 3 -pyridyl ] - N - ethyl- N -methyl propoxy - ethoxy ) - 3 -pyridyl ] - N formamidine isopropyl- N -methyl - formamidine 67 .011 N . O [0039 ] Preferably component ( B ) is a compound selected from the group consisting of azoxystrobin , picoxystrobin , pyraclostrobin , and trifloxystrobin , cyproconazole , difeno conazole , epoxiconazole , metconazole , propiconazole , Mefentrifluconazole , prothioconazole , bixafen , fluopyram , fluxapyroxad , isopyrazam , sedaxane , benzovindiflupyr and pydiflumetofen , acibenzolar - S -methyl , chlorothalonil , man cozeb and dithianon . [0040 ] Most of the component ( B ) compounds are referred N ' - [ 2 , 5 - dimethyl- 6 - ( 1 -methyl - 2 to herein above by a so - called “ ISO common name” or propoxy - ethoxy ) - 3 -pyridyl ]- N another “ common name” being used in individual cases or ethyl- N -methyl - formamidine a trademark name. The component ( B ) compounds are 67 .013 known and are commercially available and / or can be pre pared using procedures known in the art and /or procedures reported in the literature . 10041 ] For example : Br [0042 ] [ 2 -[ 3 - [2 -[ 1 -[ 2 -[ 3 , 5 -bis (difluoromethyl ) pyrazol - 1 yl] acetyl ] - 4 -piperidyl ] thiazol- 4 - yl) - 4 ,5 -dihydroisoxazol - 5 yl] - 3 - chloro - phenyl] methanesulfonate can be prepared according to the the procedures described in WO 2012/ 025557. N '- [5 -bromo - 2 -methyl - 6 - ( 1 -methyl - 2 [ 0043 ] But- 3 - ynyl N - [6 - [ [ ( Z )- [ ( 1 -methyltetrazol - 5 - yl) propoxy- ethoxy )- 3 - pyridyl ]- N -ethyl phenyl- methyleneJamino ] oxymethyl] - 2 - pyridyl] carbamate N -methyl - formamidine can be prepared according to the procedures described in WO 2010 / 000841 . US 2018 /0289005 A1 Oct . 11, 2018

[ 0044 ] N - [ ( 5 - chloro - 2 - isopropyl- phenyl) methyl ] - N - cy can be prepared according to the procedures described in clopropyl- 3 - (difluoromethyl ) - 5 - fluoro - 1 -methyl - pyrazole WO 2003 /035617 . 4 - carboxamide can be prepared according to the procedures [0056 ] In a preferred embodiment composition IA com described in WO 2010 / 130767. prises as active ingredients a mixture of component ( A ) and [ 0045 ] N '- [ 4 -( 4 , 5 - dichlorothiazol- 2 - yl) oxy - 2 , 5 - dimethyl component ( B ) , wherein component ( A ) is a compound of phenyl] - N - ethyl- N -methyl - formamidine can be prepared formula (1 ) according to the procedures described in WO 2007 /031513 . [0046 ] 2 - [ [ 3 - ( 2 - chlorophenyl) - 2 - ( 2 ,4 - difluorophenyl) oxi ran -2 -yl ] methyl ] - 4H - 1 ,2 , 4 -triazole -3 - thione can be prepared according to the procedures described in WO 2010 / 146031 . [ 0047 ] 2 - [ 2 -chloro -4 -( 4 - chlorophenoxy )phenyl ] - 1 - (1 , 2 ,4 triazol- 1 - yl) propan - 2 - ol can be prepared according to the procedures described in WO 2013 /024082 . R - O [0048 ] 4 - ( 2 -bromo - 4 - fluoro - phenyl) - N - ( 2 - chloro - 6 fluoro -phenyl ) - 2, 5 - dimethyl -pyrazol - 3 -amine can be pre pared according to the procedures described in WO 2012 / RI 031061 . [0049 ] 2 - [2 - fluoro -6 -[ ( 8 - fluoro - 2 -methyl - 3 - quinolyl) oxy ] [0057 ] wherein phenyl] propan -2 - ol can be prepared according to the proce [0058 ] R represents hydrogen , chloro , bromo , cyano , dures described in WO 2011 /081174 . C , -C2 alkyl , CO2 (C2 - C2 alkyl) , CO , H , CONH2, CONH [ 0050 ) 4 , 4, 5 - trifluoro -3 ,3 -dimethyl - 1 -( 3 - quinolyl) isoqui (C1 - C4 alkyl) , CON ( C , - C4 alkyl) 2, C1- C4 haloalkyl, or noline can be prepared according to the procedures C1- C4 haloalkoxy; described in WO 2005 /070917 . [0059 ] R² represents Cz - C alkyl, Cz - Coalkenyl , or Rº; [0051 ] 3 - ( difluoromethyl) - N - ( 7 - fluoro - 1 , 1 , 3 - trimethyl- in [ 0060 ] R3 and R * independently of each other represent dan - 4 - yl) - 1 - methyl- pyrazole - 4 -carboxamide can be pre hydrogen , methyl, ethyl, isopropyl or cyclopropyl; or pared according to the procedures described in WO 2012/ R3 and R4 together with the nitrogen atom to which 084812 . they are attached form a 3 -, 4 - or 5 -membered saturated [0052 ] 3 - ( difluoromethyl) - 1 -methyl - N - ( 1 , 1 , 3 - trimethylin cyclic group ; dan -4 - yl) pyrazole -4 - carboxamide can be prepared accord ing to the procedures described in WO 2014 /013842 . [ 0061alkyl] ; R? represents C -Cz alkyl, or C -Cz alkoxyC -C2 [0053 ] 3 - chloro - 6 -methyl - 5 - phenyl- 4 - ( 2 , 4 ,6 - trifluorophe [0062 ] Rº represents phenyl, which can be substituted nyl) pyridazine can be prepared according to the procedures by chloro or C - fluoroalkyl; or a salt , enantiomer , described in WO 2005 / 121104 . tautomer or N -oxide thereof; and component ( B ) is a [ 0054 ] 3 - chloro - 4 - ( 2 , 6 - difluorophenyl ) - 6 -methyl - 5 -phe compound selected from the group consisting of azox nyl- pyridazine can be prepared according to the procedures ystrobin , picoxystrobin , pyraclostrobin , and triflox described in WO 2012 / 020774 . ystrobin , cyproconazole , difenoconazole , epoxicon [ 0055 ] 2 - ( difluoromethyl) - N - ( 1 , 1 , 3 -trimethylindan - 4 -yl ) azole , metconazole , propiconazole, pyridine - 3 - carboxamide , 2 - (difluoromethyl ) - N - ( 3 - ethyl- , Mefentrifluconazole , prothioconazole , bixafen , fluopy 1 - dimethyl- indan -4 - yl) pyridine - 3 - carboxamide , 2 - ( difluo ram , fluxapyroxad , isopyrazam , sedaxane , benzovindi romethyl) - N -( 1, 1 -dimethyl - 3 -propyl - indan -4 -yl ) pyridine -3 flupyr and pydiflumetofen , acibenzolar- S -methyl , chlo carboxamide , 2 -( difluoromethyl ) - N - ( 3 -isobutyl - , 1- dim rothalonil, mancozeb and dithianon . ethyl- indan - 4 - yl) pyridine - 3 -carboxamide , [0063 ] In composition IA it is preferred that component 2 -( difluoromethyl) -N -[ ( 3R )- 1, 1 ,3 - trimethylindan -4 -yl ] pyri ( A ) is a compound of formula ( I' ) which are compounds of dine - 3 - carboxamide, 2 - ( difluoromethyl ) - N - [ ( 3R ) - 3 - ethyl - 1 , formula (I ) wherein R ' is chloro , bromo, cyano , methyl or 1 - dimethyl- indan - 4 - yl] pyridine - 3 -carboxamide , and 2 - (dif C? fluoroalkyl; R² is n - propyl, iso -propyl or allyl; R * is luoromethyl) - N - [ ( 3R ) - 1, 1 -dimethyl - 3 -propyl - indan -4 - yl] methyl; R4 is ethyl or iso - propyl; and Ris methyl; or a salt , pyridine - 3 - carboxamide can be prepared according to the enantiomer , tautomer or N -oxide thereof. procedures described in WO 2014 /095675 and / or WO 2016 / [0064 ] In composition IA it is most preferred that com 139189 . ponent (A ) is a compound selected from N '- [ 5 -bromo - 2 methyl- 6 - [( 1S )- 1 -methyl - 2 -propoxy - ethoxy ] -3 -pyridyl ]- N ethyl- N -methyl - formamidine (compound 67 .002 ), N '- [ 5 bromo- 2 -methyl -6 - [ ( 1R ) - 1 -methyl - 2 - propoxy - ethoxy ] - 3 pyridyl] - N - ethyl - N -methyl - formamidine ( compound 67. 003 ) , N '- [5 - cyano - 2 -methyl - 6 - ( 1 -methyl - 2 - propoxy ethoxy )- 3- pyridyl] - N - ethyl- N -methyl - formamidine (com pound 67 .007 ) , N '- [ 5 - (difluoromethyl ) - 2 -methyl - 6 - ( 1 0 methyl- 2 -propoxy -ethoxy )- 3 -pyridyl ] - N - ethyl- N -methyl formamidine ( compound 67 .009 ) , N ' - [ 2 , 5 - dimethyl- 6 - ( 1 methyl- 2 - propoxy - ethoxy ) - 3 -pyridyl ]- N - ethyl - N -methyl H formamidine ( compound 67. 011 ) , N '- [5 -bromo - 2 -methyl - 6 ( 1 -methyl - 2 - propoxy - ethoxy ) - 3 -pyridyl ]- N - ethyl- N methyl- formamidine ( compound 67 .013 ), N ' -[ 6 -( 2 -allyloxy 1 -methyl - ethoxy ) - 5 - chloro - 2 -methyl - 3 -pyridyl ] - N - ethyl- N methyl- formamidine ( compound 67 .014 ), N '- [ 5 -chloro - 2 US 2018 /0289005 A1 Oct . 11, 2018 methyl- 6 - ( 1 -methyl - 2 - propoxy - ethoxy ) - 3 -pyridyl ] - N - ethyl pyrametostrobin , triclopyricarb , kresoxim -methyl , flu N -methyl - formamidine (compound 67 .015 ), and N '- [ 5 oxastrobin , pyribencarb , pyraclostrobin and triflox bromo- 2 -methyl - 6 -( 1 -methyl - 2 - propoxy - ethoxy ) - 3 ystrobin ; pyridyl] - N - isopropyl- N -methyl - formamidine ( compound [ 0076 ] (B2 ) an azole fungicide selected from the group 67 .018 ); or a salt , enantiomer , tautomer or N -oxide thereof. consisting of azaconazole , etaconazole , ipconazole , [0065 ] In a preferred composition of the embodiment of tebuconazole , bitertanol, fenbucoanzole , metconazole , composition IA component ( A ) is N ' - [ 5 - bromo - 2 -methyl - 6 tetraconazole , bromucoanzole , fluquinconazole, [ ( 1S ) - 1 -methyl - 2 - propoxy - ethoxy ] - 3 -pyridyl ] - N - ethyl- N myclobutanil, triadimefon , flusilazole , penconazole , methyl- formamidine ( compound 67 .002 ) ; or a salt , triadimenol, triticonazole , simeconazole , imibencon enantiomer , tautomer or N -oxide thereof. azole , hexaconazole , flutriafol, diniconazole , cypro 10066 ] In another preferred composition of the embodi conazole , difenoconazole , epoxiconazole , propicon ment of composition IA component (A ) is N '- [5 -bromo - 2 azole , prothioconazole , pyrifenox , nuarimol, fenarimol, methyl- 6 - [ ( 1R ) - 1 -methyl - 2 -propoxy -ethoxy ] - 3 - pyridyl] - N imizalil, triflumizole , prochloraz , pefurazoate , oxpoco ethyl- N -methyl - formamidine ( compound 67 . 003 ) ; or a salt , nazole , Mefentrifluconazole , 2 -[ [ 3 - ( 2 -chlorophenyl ) - 2 enantiomer, tautomer or N - oxide thereof . ( 2 ,4 -difluorophenyl ) oxiran -2 - yl]methyl ] - 4H - 1, 2 ,4 - tri [ 0067 ] In another preferred composition of the embodi azole - 3 -thione and 2 - [ 2 -chloro - 4 - ( 4 - chlorophenoxy ) ment of composition IA component ( A ) is N - [ 5 - cyano - 2 phenyl ] - 1 - ( 1 , 2 ,4 - triazol- 1 - yl) propan - 2 - ol; methyl- 6 - ( 1 -methyl - 2 - propoxy -ethoxy ) - 3 -pyridyl ] - N - ethyl [0077 ] (B3 ) a morpholine fungicide selected from N -methyl - formamidine ( compound 67 .007 ); or a salt , aldimorph , dodemorph , fenpropimorph and tride enantiomer, tautomer or N - oxide thereof. morph ; [0068 ] In another preferred composition of the embodi [0078 ] (B4 ) a carboxamide fungicide selected from ment of composition IA component ( A ) is N '- [5 -( difluorom bixafen , fluopyram , fluxapyroxad , isopyrazam , sedax ethyl )- 2 -methyl -6 - ( 1 -methyl - 2 -propoxy - ethoxy ) - 3 -pyridyl ] ane , furametpyr, penflufen , penthiopyrad , benzovindi N - ethyl- N -methyl - formamidine (compound 67 .009 ) ; or a flupyr, thifluzamide , isofetamid , boscalid , carboxin , salt, enantiomer, tautomer or N -oxide thereof. oxycarboxin , fenfuram , flutolanil, pyraziflumid , pydi [0069 ] In another preferred composition of the embodi flumetofen , mepronil, benodanil , N - [ ( 5 - chloro - 2 - iso ment of composition IA component ( A ) is N '- [ 2 ,5 - dimethyl propyl- phenyl ) methyl ] -N - cyclopropyl- 3 - (difluorom 6 -( 1 -methyl - 2 - propoxy - ethoxy ) - 3 - pyridyl ]- N - ethyl- N ethyl ) - 5 - fluoro - 1- methyl - pyrazole -4 -carboxamide , methyl- formamidine (compound 67. 011 ) ; or a salt , 3 - ( difluoromethyl ) - N - ( 7 - fluoro - 1 , 1 , 3 - trimethyl- indan enantiomer , tautomer or N -oxide thereof. 4 -yl ) - 1- methyl - pyrazole - 4 -carboxamide , 3 -( difluorom [0070 ] In another preferred composition of the embodi ethyl) - 1 -methyl - N - ( 1 , 1 , 3 - trimethylindan - 4 - yl) pyra ment of composition IA component ( A ) is N ' - [ 5 - bromo- 2 zole - 4 - carboxamide and ( R ) - 3 - ( difluoromethyl) - 1 methyl- 6 - ( 1 -methyl - 2 -propoxy - ethoxy ) - 3 -pyridyl ] - N - ethyl methyl - N - ( 1 , 1 , 3 - trimethylindan - 4 - yl) pyrazole - 4 N -methyl - formamidine ( compound 67 .013 ) ; or a salt , carboxamide; enantiomer, tautomer or N -oxide thereof. [ 0079 ] (B5 ) an anilinopyrimidine fungicide selected [0071 ] In another preferred composition of the embodi from cyprodinil, mepanipyrim and pyrimethanil ; ment of composition IA component ( A ) is N ' - [ 6 - (2 - allyloxy 10080 ) (B6 ) an phenylpyrrole fungicide selected from 1 - methyl- ethoxy ) - 5 - chloro - 2 -methyl - 3 - pyridyl ] - N - ethyl - N fludioxonil and fenpiclonil ; methyl- formamidine (compound 67 .014 ) ; or a salt, [0081 ] (B7 ) a phenylamide fungicide selected from enantiomer, tautomer or N - oxide thereof. benalaxyl, benalaxyl- M , furalaxyl, mefenoxam (meta [ 0072 ] In another preferred composition of the embodi laxyl- M ) and metalaxyl, ofurace and oxadixyl ; ment of composition IA component ( A ) is N '- [ 5 - chloro - 2 [ 0082 ] (B8 ) a fungicide selected from the group con methyl- 6 - ( 1 -methyl - 2 - propoxy - ethoxy ) - 3 - pyridyl ] - N - ethyl sisting of ametoctradin , amisulbrom , anilazine , aureo N -methyl - formamidine ( compound 67. 015 ) ; or a salt, fungin , benomyl , benthiavalicarb , benthiazole , bethox enantiomer, tautomer or N - oxide thereof. azin , BLAD , blasticidin -S , Bordeaux mixture, [0073 ] In another preferred composition of the embodi bupirimate , calcium polysulfide, captafol, captan , car ment of composition IA component ( A ) is N ' - [ 5 - bromo- 2 baryl , carbendazim , carpropamid , chinomethionate , methyl- 6 - ( 1 -methyl - 2 - propoxy - ethoxy ) - 3 - pyridyl] - N - iso chitosan , chlobenthiazone , chlorfenazole , chloroneb , propyl- N -methyl - formamidine ( compound 67. 018 ) ; or a chlorothalonil , chlozolinate , climbazole , copper salt , enantiomer , tautomer or N -oxide thereof. acetate , copper carbonate , copper hydroxide, copper [ 0074 ] In a further preferred embodiment composition IB naphthenate , copper oleate , copper oxychloride, copper comprises as active ingredients a mixture of component ( A ) oxyquinolate , copper silicate , copper sulphate , copper and component ( B ) , wherein component ( A ) is a compound tallate , cuprous oxide, cyazofamid , cyclafuramid , of formula ( I ') which are compounds of formula ( I) wherein cyflufenamid , cymoxanil, dazomet, dichlofluanid , Rl is chloro , bromo, cyano , methyl or C , fluoroalkyl; R2 is dichlorprop , diclocymet , diclomezine , dicloran , n - propyl, iso -propyl or allyl; R * is methyl; R4 is ethyl or diethofencarb , diflumetorim , dimetachlone , dimethi iso -propyl ; and R is methyl; or a salt , enantiomer , tautomer pin , dimethirimol, dimethomorph , dinocap , dinocton , or N -oxide thereof; and component ( B ) is a compound dinobuton , dinopenton , dipymetitrone , ditalimfos , selected from the group consisting of dithianon , dodicin , dodine , doguadine , edifenphos , [0075 ] (B1 ) a strobilurin fungicide selected from the etem , ethaboxam , ethirimol, ethoxyquin , etridiazole , group consisting of azoxystrobin , picoxystrobin , enox famoxadone , fenamidone, fenarimol, fenhexamid , astrobin , pyraoxystrobin , mandestrobin , flufenox fenoxanil , fenpropidine , fenpyrazamine , fentin acetate, ystrobin , coumoxystrobin , orysastrobin , dimox fentin hydroxide , ferbam , ferimzone , fluazinam , flu ystrobin , metominostrobin , fenaminostrobin , morph , fluopicolide, fluoroimide, flusulfamide, flu US 2018 /0289005 A1 Oct . 11, 2018

tianil , folpet , fosetyl- AI, fuberidazole , gibberellic acid , [0084 ] and a compound of the formula : guazatine, hymexazole , iminoctadine, iodocarb , iprobenfos, iprodione , iprovalicarb , isoprothiolane , kasugamycin , mancozeb , mandipropamid , maneb , metam , meptyldinocap , metiram , metrafenone , nabam , oxathiapiprolin , paclobutrazol , pencycuron , phenamac ril, phosdiphen , phthalide, picarbutrazox , polyoxin D , probenazole , procymidone , prohexadione, propamo carb , propineb , proquinazid , pyrazophos, pyrifenox , pyrimorph , pyriofenone , pyroquilon , quinoxyfen , quin tozene , silthiofam , spiroxamine , streptomycin , sulphur, tebufloquin , tecloftalam , tecnazene, thiabendazole , NIE . thidiazuron , thicyofen , thiophanate -methyl , thiram , N tioxymid , tolclofos -methyl , tolprocarb , tolylfluanid , tri azoxide, tribufos , tricyclazole , triforine, validamycin , valifenalate , vapam , vinclozolin , zineb , ziram , zoxam ide , [ 2 - 13 - [ 2 - 11 -12 -13 , 5 -bis ( difluoromethyl) pyrazol- 1 yl] acetyl] - 4 -piperidyl ] thiazol - 4 - yl) - 4 ,5 - dihyd roisox azol- 5 - yl) - 3 - chloro -phenyl ] methanesulfonate , but- 3 [ 0085 ] (B9 ) a plant- bioregulator selected from the ynyl N - [6 - [[ ( Z )- [( 1 -methyltetrazol - 5 -yl ) - phenyl group consisting of acibenzolar- S -methyl , chlormequat methylene ] aminojoxymethyl) - 2 -pyridyl ] carbamate , chloride, ethephon , isotianil ,mepiquat chloride, tiadinil N '- [ 4 - ( 4 , 5 - dichlorothiazol - 2 - yl) oxy - 2 , 5 - dimethyl- phe and trinexapac - ethyl ; nyl] - N -ethyl - N -methyl - formamidine , 4 -( 2 -bromo - 4 fluoro - phenyl) - N - ( 2 - chloro - 6 - fluoro -phenyl ) - 2 , 5 -dim [0086 ] (B10 ) an insecticide selected from the group ethyl- pyrazol - 3 -amine , 2 - [2 - fluoro - 6 -[ (8 - fluoro - 2 consisting of abamectin , acequinocyl, acetamiprid , methyl- 3 - quinolyl) oxylphenyl] propan - 2 -ol , 4 ,4 , 5 acrinathrin , afidopyropen , alanycarb , allethrin , alpha trifluoro - 3 , 3 - dimethyl - 1 - ( 3 - quinolyl) isoquinoline , cypermethrin , alphamethrin , amidoflumet , 3 -chloro -6 -methyl - 5 -phenyl - 4 - (2 , 4 ,6 - trifluorophenyl) azadirachtin , azocyclotin , bacillus firmus, bacillus pyridazine, 3 -chloro -4 -( 2 ,6 - difluorophenyl) -6 -methyl thuringiensis, bensultap , benzoximate , betacyfluthrin , 5 -phenyl -pyridazine , 2 - (difluoromethyl ) - N - ( 1 , 1 , 3 bifenazate , binapacryl, bioallethrin , bioresmethrin , trimethylindan - 4 - yl) pyridine - 3 -carboxamide , biphenthrin , broflanilide , brofluthrinate , bromophos 2 - (difluoromethyl ) - N - ( 3 - ethyl- 1 , 1 -dimethyl - indan - 4 ethyl, buprofezine , cadusafos, carbaryl, carbosulfan , yl) pyridine - 3 - carboxamide , 2 - ( difluoromethyl) - N - ( 1 , cartap , chlorantraniliprole, chlorfenapyr, chromafenoz 1 - dimethyl - 3 - propyl -indan - 4 - yl )pyridine - 3 -carboxam ide , cloethocarb , clothianidin , cyantraniliprole , cycla ide , 2 - ( difluoromethyl) - N - ( 3 - isobutyl- 1 , 1 - dimethyl niliprole , cycloprothrin , cycloxaprid , cyenopyrafen , indan - 4 -yl ) pyridine - 3 - carboxamide , cyflumetofen , cyfluthrin , cyhalothrin , cypermethrin , 2 - ( difluoromethyl) - N - [ (3R ) - 1 , 1 , 3 - trimethylindan - 4 - yl] cyphenothrin , cyromazine , deltamethrin , demeton - s pyridine- 3 - carboxamide, 2 - (difluoromethyl ) - N - [ (3R ) methyl, diafenthiuron , dialifos , dichloromezotiaz , 3 -ethyl - 1 , 1 -dimethyl - indan - 4 -yl ] pyridine - 3 - carboxam diflovidazine, diflubenzuron , dinactin , dinocap , dinote ide, 2 -( difluoromethyl ) - N -[ (3R )- 1 ,1 -dimethyl - 3 furan , d - limonene , emamectin , empenthrin , esfenvaler propyl- indan - 4 - yl] pyridine - 3 -carboxamide , ate , ethion , ethiprole , etofenprox , etoxazole , famphur , compound of the formula fenazaquin , fenfluthrin , fenobucarb , fenoxycarb , fen propathrin , fenpyroxymate , fenvalerate , fipronil, flom etoquin , flonicamid , fluacrypyrim , fluazuron , flubendi amide, flucythrinate , fluensulfone , flufenerim , flufenprox , flufiprole , fluhexafon , flumethrin , flupyra difuron , fluvalinate, fosthiazate , gamma - cyhalothrin , NH gossyplure , guadipyr, halofenozide , halofenprox , har pin , hexythiazox , hydramethylnon , imicyafos , imida cloprid , imiprothrin , indoxacarb , iodomethane , isoth ioate , ivermectin , lambda - cyhalothrin , lepimectin , lufenuron , metaflumizone , metaldehyde , methomyl, methoxyfenozide, metofluthrin , milbemectin , niclos [ 0083 ] a compound of the formula amide , nitenpyram , oxamyl, parathion - ethyl, pasteuria nishizawae , p -cymene , permethrin , phenothrin , phos phocarb , piperonylbutoxide, pirimicarb , pirimiphos ethyl, polyhedrosis virus, prallethrin , profenofos, pro F 0 fenofos , propargite , propetamphos , protrifenbute , pyflubumide , pymetrozine , pyraclofos , pyrafluprole , N pyrethrum , pyridaben , pyridalyl, pyrifluquinazon , pyrimidifen , pyriprole , pyriproxyfen , selamectin , sila fluofen , spinetoram , spinosad , spirodiclofen , spirome sifen , spirotetramat, sulfoxaflor, tebufenozide , tebufen pyrad , tefluthrin , terpenoid blends, terpenoids , tetradiphon , tetramethrin , tetranactin , tetraniliprole , theta - cypermethrin , thiacloprid , thiamethoxam , thiodi US 2018 /0289005 A1 Oct . 11, 2018

carb , tioxazafen , tolfenpyrad , transfluthrin , trichlorfon , N -methyl - formamidine (compound 67 .015 ) ; or a salt , triflumezopyrim , zeta - cypermethrin and a - terpinene ; enantiomer, tautomer or N -oxide thereof. and [0097 ] In another preferred composition of the embodi [0087 ] (B11 ) glyphosate . ment of composition IB component ( A ) is N '- [ 5 - bromo- 2 [0088 ] In composition IB it is most preferred that com methyl -6 - ( 1 -methyl - 2 - propoxy -ethoxy ) - 3 -pyridyl ] - N - iso ponent ( A ) is a compound selected from N '- [ 5 - bromo- 2 propyl- N -methyl - formamidine ( compound 67 .018 ) ; or a methyl -6 - [ ( 1S ) - 1 -methyl - 2 - propoxy - ethoxy ] - 3 -pyridyl ] - N salt, enantiomer, tautomer or N -oxide thereof. ethyl- N -methyl - formamidine (compound 67 .002 ) , N ' - [ 5 [0098 ] The term “ fungicide ” as used herein means a bromo- 2 -methyl - 6 - [ ( 1R )- 1 -methyl - 2 - propoxy - ethoxy ] - 3 compound that controls ,modifies , or prevents the growth of pyridyl] - N - ethyl - N -methyl - formamidine ( compound fungi. The term “ fungicidally effective amount" means the 67. 003 ) , N '- [5 - cyano - 2 -methyl - 6 - ( 1 -methyl - 2 - propoxy quantity of such a compound or combination of such com ethoxy ) - 3 -pyridyl ] - N - ethyl- N -methyl - formamidine ( com pounds that is capable of producing an effect on the growth pound 67 .007 ) , N - [ 5 - ( difluoromethyl) - 2 -methyl - 6 - 1 of fungi. Controlling or modifying effects include all devia methyl- 2 - propoxy - ethoxy ) - 3 - pyridyl ]- N -ethyl - N -methyl tion from natural development, such as killing, retardation formamidine ( compound 67 .009 ) , N - [ 2 , 5 - dimethyl- 6 - ( 1 and the like , and prevention includes barrier or other defen methyl - 2 - propoxy - ethoxy ) - 3 -pyridyl ] - N - ethyl- N -methyl sive formation in or on a plant to prevent fungal infection . formamidine (compound 67 .011 ) , N '- [ 5 -bromo -2 -methyl - 6 [0099 ] The term “ plants ” refers to all physical parts of a ( 1 -methyl - 2 - propoxy - ethoxy ) - 3 -pyridyl ]- N - ethyl- N plant, including seeds, seedlings, saplings , roots , tubers , methyl- formamidine ( compound 67. 013 ), N '- [6 -( 2 -allyloxy stems, stalks, foliage , and fruits . 1 -methyl - ethoxy ) - 5 - chloro - 2 -methyl - 3 -pyridyl ] - N - ethyl - N (0100 ] The term " plant propagation material” denotes all methyl- formamidine ( compound 67. 014 ), N '- [ 5 - chloro - 2 generative parts of a plant, for example seeds or vegetative methyl- 6 -( 1 -methyl - 2 -propoxy - ethoxy ) - 3 -pyridyl ] - N - ethyl parts of plants such as cuttings and tubers. It includes seeds N -methyl - formamidine ( compound 67 .015 ) , and N '- [ 5 in the strict sense, as well as roots , fruits , tubers , bulbs, bromo -2 -methyl - 6 - (1 -methyl - 2 -propoxy - ethoxy )- 3 rhizomes , and parts of plants . pyridyl] - N - isopropyl- N -methyl - formamidine (compound [0101 ] The term “ locus ” as used herein means fields in or 67 .018 ) ; or a salt , enantiomer, tautomer or N -oxide thereof. on which plants are growing , or where seeds of cultivated [0089 ] In a preferred composition of the embodiment of plants are sown , or where seed will be placed into the soil . composition IB component ( A ) is N '- [ 5 -bromo - 2- methyl - 6 It includes soil, seeds, and seedlings , as well as established [ ( 1S ) - 1 -methyl - 2 -propoxy - ethoxy ] - 3 -pyridyl ] - N - ethyl- N vegetation . methyl- formamidine (compound 67 .002 ) ; or a salt , 10102 ]. Throughout this document the expression “ compo enantiomer, tautomer or N - oxide thereof. sition ” stands for the various mixtures or combinations of [0090 ] In another preferred composition of the embodi components ( A ) and ( B ) ( including the above -defined ment of composition IB component ( A ) is N '- [ 5 -bromo - 2 embodiments ), for example in a single “ ready -mix ” form , in methyl- 6 - [ ( 1R ) - 1 -methyl - 2 - propoxy - ethoxyl- 3 -pyridyl ] - N a combined spray mixture composed from separate formu ethyl- N -methyl - formamidine (compound 67 .003 ); or a salt, lations of the single active ingredient components , such as a enantiomer , tautomer or N -oxide thereof. " tank -mix ” , and in a combined use of the single active [ 0091 ] In another preferred composition of the embodi ingredients when applied in a sequential manner, i . e . one ment of composition IB component ( A ) is N ' - [ 5 - cyano - 2 after the other with a reasonably short period , such as a few methyl- 6 - ( 1 -methyl - 2 -propoxy - ethoxy ) - 3 -pyridyl ] - N - ethyl hours or days . The order of applying the components ( A ) and N -methyl - formamidine (compound 67 .007 ) ; or a salt , ( B ) is not essential for working the present invention . enantiomer, tautomer or N -oxide thereof. [0103 ] The composition according to the invention is [0092 ] In another preferred composition of the embodi effective against harmful microorganisms, such as microor ment of composition IB component ( A ) is N ' - [ 5 - ( difluorom ganisms, that cause phytopathogenic diseases , in particular ethyl) - 2 -methyl - 6 - ( 1 -methyl - 2 - propoxy - ethoxy ) - 3 - pyridyl] against phytopathogenic fungi and bacteria . N -ethyl - N -methyl - formamidine ( compound 67. 009 ); or a 0104 ] The composition of the invention may be used to salt, enantiomer, tautomer or N - oxide thereof. control plant diseases caused by a broad spectrum of fungal [0093 ] In another preferred composition of the embodi plant pathogens in the Basidiomycete , Ascomycete , Oomy ment of composition IB component ( A ) is N ' - [ 2 , 5 - dimethyl cete and / or Deuteromycete , Blasocladiomycete , Chrytidio 6 -( 1 -methyl - 2 - propoxy - ethoxy ) - 3 - pyridyl ] - N - ethyl- N mycete , Glomeromycete and / or Mucoromycete classes. methyl- formamidine ( compound 67 .011 ) ; or a salt, [0105 ] The composition is effective in controlling a broad enantiomer, tautomer or N -oxide thereof. spectrum of plant diseases , such as foliar pathogens of [0094 ] In another preferred composition of the embodi ornamental, turf , vegetable, field , cereal, and fruit crops . ment of composition IB component ( A ) is N - [ 5 -bromo - 2 [0106 ] These pathogens may include : methyl- 6 - ( 1 -methyl - 2 - propoxy - ethoxy ) - 3 - pyridyl] - N - ethyl [0107 ] Oomycetes , including Phytophthora diseases N -methyl - formamidine (compound 67 .013 ); or a salt, such as those caused by Phytophthora capsici, Phy enantiomer, tautomer or N - oxide thereof. tophthora infestans, Phytophthora sojae , Phytophthora [0095 ] In another preferred composition of the embodi fragariae, Phytophthora nicotianae , Phytophthora cin mentof composition IB component ( A ) is N '- [ 6 -( 2 -allyloxy namomi, Phytophthora citricola , Phytophthora citrop 1 - methyl- ethoxy ) - 5 - chloro - 2 -methyl - 3 - pyridyl ] - N - ethyl - N hthora and Phytophthora erythroseptica ; Pythium dis methyl- formamidine ( compound 67 .014 ) ; or a salt , eases such as those caused by Pythium enantiomer, tautomer or N -oxide thereof. aphanidermatum , Pythium arrhenomanes , Pythium [0096 ] In another preferred composition of the embodi graminicola , Pythium irregulare and Pythium ultimum ; ment of composition IB component ( A ) is N '- [ 5 - chloro - 2 diseases caused by Peronosporales such as Perono methyl- 6 - ( 1 -methyl - 2 - propoxy - ethoxy ) - 3 - pyridyl] - N - ethyl spora destructor, Peronospora parasitica , Plasmopara US 2018 /0289005 A1 Oct. 11 , 2018

viticola , Plasmopara halstedii , Pseudoperonospora cline pseudotsugae , Rhynchosporium secalis , Sacro cubensis, Albugo candida, Sclerophthora macrospora cladium oryzae , Scedosporium spp ., Schizothyrium and Bremia lactucae ; and others such as Aphanomyces pomi, Sclerotinia sclerotiorum , Sclerotinia minor ; Scle cochlioides, Labyrinthula zosterae , Peronosclerospora rotium spp. , Typhula ishikariensis, Seimatosporium sorghi and Sclerospora graminicola ; mariae, Lepteutypa cupressi, Septocyta ruborum , [0108 ] Ascomycetes, including blotch , spot, blast or Sphaceloma perseae, Sporonema phacidioides , Stig blight diseases and /or rots for example those caused by mina palmivora , Tapesia yallundae, Taphrina bullata , Pleosporales such as Stemphylium solani, Stagono Thielviopsis basicola , Trichoseptoria fructigena, Zygo spora tainanensis , Spilocaea oleaginea, Setosphaeria phiala jamaicensis ; powdery mildew diseases for turcica, Pyrenochaeta lycoperisici , Pleospora herba example those caused by Erysiphales such as Blumeria rum , Phoma destructiva , Phaeosphaeria her graminis , Erysiphe polygoni, Uncinula necator, Spha potrichoides, Phaeocryptocus gaeumannii, Ophiospha erotheca fuligena , Podosphaera leucotricha , Podos erella graminicola , Ophiobolus graminis , paera macularis Golovinomyces cichoracearum , Lev Leptosphaeria maculans, Hendersonia creberrima , eillula taurica , Microsphaera diffusa , Oidiopsis Helminthosporium triticirepentis , Setosphaeria tur gossypii , Phyllactinia guttata and Oidium arachidis ; cica , Drechslera glycines, Didymella bryoniae, Cyclo molds for example those caused by Botryosphaeriales conium oleagineum , Corynespora cassiicola , Coch such as Dothiorella aromatica , Diplodia seriata , Guig liobolus sativus , Bipolaris cactivora , Venturia nardia bidwellii, Botrytis cinerea , Botryotinia allii , inaequalis , Pyrenophora teres , Pyrenophora tritici Botryotinia fabae , Fusicoccum amygdali , Lasiodiplo repentis , Alternaria alternata , Alternaria brassicicola , dia theobromae, Macrophoma theicola , Macro Alternaria solani and Alternaria tomatophila , Capno phomina phaseolina , Phyllosticta cucurbitacearum ; diales such as Septoria tritici , Septoria nodorum , Sep anthracnoses for example those caused by Glom toria glycines, Cercospora arachidicola , Cercospora merelales such as Colletotrichum gloeosporioides , Col sojina , Cercospora zeae -maydis , Cercosporella cap letotrichum lagenarium , Colletotrichum gossypii , sellae and Cercosporella herpotrichoides , Cladospo Glomerella cingulata , and Colletotrichum gramini rium carpophilum , Cladosporium effusum , Passalora cola ; and wilts or blights for example those caused by fulva , Cladosporium oxysporum , Dothistroma sep Hypocreales such as Acremonium strictum , Claviceps tosporum , Isariopsis clavispora , Mycosphaerella purpurea , Fusarium culmorum , Fusarium fijiensis, Mycosphaerella graminicola , Mycovellosiella graminearum , Fusarium virguliforme, Fusarium koepkeii, Phaeoisariopsis bataticola , Pseudocer oxysporum , Fusarium subglutinans , Fusarium oxyspo cospora vitis, Pseudocercosporella herpotrichoides , rum f. sp . cubense, Gerlachia nivale , Gibberella fujik Ramularia beticola , Ramularia collo -cygni , Magna uroi , Gibberella zeae, Gliocladium spp ., Myrothecium porthales such as Gaeumannomyces graminis , Magna verrucaria , Nectria ramulariae , Trichoderma viride , porthe grisea , Pyricularia oryzae , Diaporthales such as Trichothecium roseum , and Verticillium theobromae ; Anisogramma anomala , Apiognomonia errabunda , [0109 ] Basidiomycetes, including smuts for example Cytospora platani, Diaporthe phaseolorum , Discula those caused by Ustilaginales such as Ustilaginoidea destructiva , Gnomonia fructicola , Greeneria uvicola , virens, Ustilago nuda , Ustilago tritici , Ustilago zeae , Melanconium juglandinum , Phomopsis viticola , Siro rusts for example those caused by Pucciniales such as coccus clavigignenti - juglandacearum , Tubakia dryina , Cerotelium fici, Chrysomyxa arctostaphyli, Coleospo Dicarpella spp . , Valsa ceratosperma , and others such rium ipomoeae , Hemileia vastatrix, Puccinia as Actinothyrium graminis , Ascochyta pisi , Aspergillus arachidis, Puccinia cacabata , Puccinia graminis, Puc flavus, Aspergillus fumigatus , Aspergillus nidulans, cinia recondita , Puccinia sorghi, Puccinia hordei , Puc Asperisporium caricae, Blumeriella jaapii, Candida cinia striiformis f . sp . Hordei, Puccinia striiformis f . sp . spp ., Capnodium ramosum , Cephaloascus spp ., Cepha Secalis , Pucciniastrum coryli , or Uredinales such as losporium gramineum , Ceratocystis paradoxa , Chaeto Cronartium ribicola , Gymnosporangium juniperi -vig mium spp . , Hymenoscyphus pseudoalbidus, Coccid inianae , Melampsora medusae , Phakopsora pachy ioides spp. , Cylindrosporium padi, Diplocarpon malae , rhizi, Phragmidium mucronatum , Physopella ampelo Drepanopeziza campestris , Elsinoe ampelina , Epicoc sidis, Tranzschelia discolor and Uromyces viciae cum nigrum , Epidermophyton spp . , Eutypa lata , fabae ; and other rots and diseases such as those caused Geotrichum candidum , Gibellina cerealis , Gloeocer by Cryptococcus spp ., Exobasidium vexans, Maras cospora sorghi, Gloeodes pomigena , Gloeosporium miellus inoderma, Mycena spp ., Sphacelotheca reili perennans; Gloeotinia temulenta , Griphospaeria cor ana , Typhula ishikariensis , Urocystis agropyri , Iterso ticola , Kabatiella lini, Leptographium microsporum , nilia perplexans, Corticium invisum , Laetisaria Leptosphaerulinia crassiasca , Lophodermium seditio fuciformis , Waitea circinata , Rhizoctonia solani, sum , Marssonina graminicola , Microdochium nivale , Thanetephorus cucurmeris, Entyloma dahliae , Entylo Monilinia fructicola , Monographella albescens , Mono mella microspora , Neovossia moliniae and Tilletia car sporascus cannonballus , Naemacyclus spp ., Ophios ies; toma novo - ulmi, Paracoccidioides brasiliensis , Peni cillium expansum , Pestalotia rhododendri , [0110 ] Blastocladiomycetes, such as Physoderma may Petriellidium spp ., Pezicula spp . , Phialophora gregata , dis ; Phyllachora pomigena , Phymatotrichum omnivora , 10111 ] Mucoromycetes, such as Choanephora cucurbi Physalospora abdita , Plectosporium tabacinum , Poly tarum .; Mucor spp .; Rhizopus arrhizus; as well as scytalum pustulans, Pseudopeziza medicaginis, diseases caused by other species and genera closely Pyrenopeziza brassicae , Ramulispora sorghi , Rhabdo related to those listed above . US 2018 /0289005 A1 Oct . 11, 2018 10

[0112 ] In addition to their fungicidal activity , the compo [0118 ] Examples of toxins which can be expressed include sitions may also have activity against bacteria such as 6 -endotoxins , vegetative insecticidal proteins ( Vip ) , insec Erwinia amylovora , Erwinia caratovora , Xanthomonas ticidal proteins of bacteria colonising nematodes , and toxins campestris , Pseudomonas syringae, Strptomyces scabies produced by scorpions, arachnids, wasps and fungi. and other related species as well as certain protozoa . [0119 ] An example of a crop that has been modified to [0113 ] The composition according to the invention is express the Bacillus thuringiensis toxin is the Bt maize particularly effective against phytopathogenic fungi belong KnockOut® (Syngenta Seeds ) . An example of a crop com ing to the following classes: Ascomycetes ( e . g . Venturia , prising more than one gene that codes for insecticidal Podosphaera , Erysiphe , Monilinia , Mycosphaerella , Unci resistance and thus expresses more than one toxin is Vip nula ); Basidiomycetes (e . g. the genus Hemileia , Rhizocto Cot® (Syngenta Seeds) . Crops or seed material thereof can nia , Phakopsora , Puccinia , Ustilago , Tilletia ) ; Fungi imper also be resistant to multiple types of pests ( so - called stacked fecti (also known as Deuteromycetes ; e. g. Botrytis , transgenic events when created by genetic modification ) . Helminthosporium , Rhynchosporium , Fusarium , Septoria , For example, a plant can have the ability to express an Cercospora , Alternaria , Pyricularia and Pseudocer insecticidal protein while at the same time being herbicide cosporella ) ; Oomycetes ( e. g . Phytophthora , Peronospora , tolerant, for example Herculex I® (Dow AgroSciences, Pseudoperonospora , Albugo , Bremia , Pythium , Pseudoscle Pioneer Hi- Bred International) . rospora , Plasmopara ) . (0120 ] Further preferred examples of compositions [ 0114 ] Crops of useful plants in which the composition according to the invention are as follows (wherein the term according to the invention can be used include perennial and " TX1” means : " a compound selected from compound no . annual crops , such as berry plants for example blackberries, 67. 002 , 67. 003 , 67. 007 , 67. 009 , 67 .011 , 67 .013 , 67 .014 , blueberries , cranberries , raspberries and strawberries ; cere 67 .015 and 67. 018 , as defined in the Table X above” ) : als for example barley, maize ( corn ), millet , oats , rice, rye, [ 0121 ] TX1 + azoxystrobin , TX1 + picoxystrobin , TX1 + sorghum triticale and wheat ; fibre plants for example cotton , pyraclostrobin , TX1 + trifloxystrobin , TX1 + cyprocon flax , hemp, jute and sisal; field crops for example sugar and azole , TX1 + difenoconazole , TX1 + epoxiconazole , fodder beet , coffee , hops, mustard , oilseed rape (canola ), TX1+ metconazole , TX1 + propiconazole , TX1+ Mefen poppy, sugar cane, sunflower, tea and tobacco ; fruit trees for trifluconazole , TX1 + prothioconazole , TX1 + bixafen , example apple , apricot, avocado , banana , cherry , citrus, TX1+ fluopyram , TX1 + fluxapyroxad , TX1 + isopyra nectarine, peach , pear and plum ; grasses for example Ber zam , TX1 + sedaxane , TX1 + benzovindiflupyr, TX1 + py muda grass , bluegrass , bentgrass , centipede grass, fescue , diflumetofen , TX1 + acibenzolar -S -methyl , TX1 + chlo ryegrass, St. Augustine grass and Zoysia grass ; herbs such as rothalonil , TX1 + mancozeb and TX1 + dithianon . basil , borage , chives, coriander, lavender, lovage , mint, [0122 ] Compositions of this invention , including all of the oregano , parsley, rosemary , sage and thyme; legumes for above disclosed embodiments and preferred examples example beans , lentils, peas and soya beans ; nuts for thereof, can be mixed with one or more further pesticides example almond , cashew , ground nut, hazelnut, peanut, including further fungicides , , nematocides, bac pecan , pistachio and walnut; palms for example oil palm ; tericides , , growth regulators , chemosterilants , ornamentals for example flowers, shrubs and trees; other semiochemicals , repellents , attractants , pheromones , feed trees , for example cacao , coconut, olive and rubber , veg ing stimulants or other biologically active compounds to etables for example asparagus, aubergine, broccoli , cabbage , form a multi - component pesticide giving an even broader carrot, cucumber , garlic , lettuce , marrow , melon , okra , spectrum of agricultural protection . onion , pepper , potato , pumpkin , rhubarb , spinach and 101231 Examples of such agricultural protectants with tomato ; and vines for example grapes . which the composition of this invention can be formulated [0115 ] Crops are to be understood as being those which are : are naturally occurring , obtained by conventional methods [0124 ] Fungicides such as etridiazole , fluazinam , benal of breeding , or obtained by genetic engineering . They axyl, benalaxyl- M (kiralaxyl ) , furalaxyl , metalaxyl, metal include crops which contain so - called output traits ( e . g . axyl- M (mefenoxam ), dodicin , N '- ( 2 ,5 -Dimethyl -4 -phe improved storage stability , higher nutritional value and noxy -phenyl ) - N - ethyl- N -methyl - formamidine , N '- [4 - (4 , 5 improved flavour ). Dichloro - thiazol- 2 - yloxy ) - 2 , 5 - dimethyl- phenyl] - N - ethyl [0116 ] Crops are to be understood as also including those N -methyl - formamidine, N '- [ 4 - [ [ 3 - [ ( 4 - chlorophenyl ) crops which have been rendered tolerant to herbicides like methyl ) - 1 , 2 , 4 -thiadiazol - 5 - yl] oxy ] - 2 , 5 - dimethyl- phenyl ] bromoxynil or classes of herbicides such as ALS - , EPSPS -, N -ethyl - N -methyl - formamidine, ethirimol, 3' -chloro - 2 GS- , HPPD - and PPO - inhibitors . An example of a crop that methoxy - N -[ ( 3RS )- tetrahydro - 2 - oxofuran - 3 -yl ] acet - 2' , 6 ' has been rendered tolerant to imidazolinones , e .g . xylidide (clozylacon ) , cyprodinil , mepanipyrim , imazamox , by conventional methods of breeding is Clear pyrimethanil, dithianon , aureofungin , blasticidin - S , biphe field summer canola . Examples of crops that have been nyl, chloroneb , dicloran , hexachlorobenzene , quintozene , rendered tolerant to herbicides by genetic engineering meth tecnazene, ( TCNB ) , tolclofos -methyl , metrafenone, 2 , 6 - di ods include e . g . glyphosate - and glufosinate - resistant maize chloro - N - ( 4 - trifluoromethylbenzyl) - benzamide, fluopi varieties commercially available under the trade names colide ( flupicolide ) , tioxymid , flusulfamide , benomyl, car RoundupReady® , Herculex I® and LibertyLink® . bendazim , carbendazim chlorhydrate , chlorfenazole, 01171 Crops are also to be understood as being those fuberidazole , thiabendazole , thiophanate -methyl , benthia which naturally are or have been rendered resistant to valicarb , chlobenthiazone , probenazole, acibenzolar, harmful insects . This includes plants transformed by the use bethoxazin , pyriofenone ( IKF - 309 ), acibenzolar - S -methyl , of recombinant DNA techniques , for example , to be capable pyribencarb (KIF - 7767 ) , butylamine , 3 - iodo - 2 - propinyl of synthesising one or more selectively acting toxins , such n -butylcarbamate (IPBC ) , iodocarb (isopropanyl butylcar as are known , for example , from toxin - producing bacteria . bamate ), isopropanylbutylcarbamate ( iodocarb ) , picarbutra US 2018 /0289005 A1 Oct. 11 , 2018 11 zox, polycarbamate , propamocarb , tolprocarb , 3 - ( difluo dimoxystrobin , enestroburin , enoxastrobin fenamistrobin , romethyl) - N - ( 7 - fluoro - 1 , 1 , 3 , 3 -tetramethyl - indan - 4 - yl) - 1 flufenoxystrobin , fluoxastrobin , kresoxim -methyl , mande methyl -pyrazole - 4 -carboxamide diclocymet , N - [ ( 5 -chloro strobin , metaminostrobin , metominostrobin , orysastrobin , 2 - isopropyl- phenyl ) methyl ] - N -cyclopropyl - 3 -( d picoxystrobin , pyraclostrobin , pyrametostrobin , pyraox ifluoromethyl) -5 - fluoro - 1 -methyl - pyrazole -4 - carboxamide ystrobin , triclopyricarb , trifloxystrobin , amisulbrom , dichlo N -cyclopropyl - 3 - (difluoromethyl ) - 5 - fluoro -N -[ (2 - isopropy fluanid , tolylfluanid , but- 3 -ynyl N - [ 6 - [ [ ( Z ) - [ ( 1 -methyltetra lphenyl) methyl ] - 1- methyl - pyrazole - 4 -carboxamide carpro zol- 5 - yl) - phenyl- methylene ] amino ] oxymethyl ] - 2 - pyridyl] carbamate , dazomet, isotianil , tiadinil, thifluzamide , pamid , chlorothalonil, flumorph , oxine -copper , cymoxanil , benthiazole (TCMTB ) , silthiofam , zoxamide , anilazine , tri phenamacril , cyazofamid , flutianil , thicyofen , chlozolinate , cyclazole , (. + - . )- cis - 1 - ( 4 - chlorophenyl) - 2 - ( 1H - 1 , 2 , 4 - triazol iprodione , procymidone, vinclozolin , bupirimate , dinocton , 1 -yl ) - cycloheptanol (huanjunzuo ), 1 -( 5 -bromo - 2 -pyridyl ) dinopenton , dinobuton , dinocap , meptyldinocap , diphe 2 - ( 2 , 4 - difluorophenyl) - 1 , 1 - difluoro - 3 - ( 1 , 2 , 4 - triazol - 1 - yl) nylamine , phosdiphen , 2 , 6 - dimethyl - [ 1 , 4 ] dithiino 2 , 3 - c : 5 , 6 propan - 2 -ol 2 - ( 1 -tert -butyl ) - 1- ( 2 -chlorophenyl ) - 3 -( 1 ,2 , 4 c ' ] dipyrrole - 1 , 3 , 5 , 7 ( 2H ,6H ) - tetraone, azithiram , etem , fer triazol- 1 - yl) - propan - 2 - ol ( TCDP ), azaconazole , bitertanol bam , mancozeb , maneb , metam , metiram ( polyram ), (biloxazol ) , bromuconazole , climbazole, cyproconazole , metiram - zinc, nabam , propineb , thiram , vapam (metam sodium ), zineb , ziram , dithioether , isoprothiolane , etha difenoconazole , dimetconazole , diniconazole , diniconazole boxam , fosetyl, phosetyl -Al ( fosetyl- al ), methyl bromide, M , epoxiconazole , etaconazole , fenbuconazole , fluquincon methyl iodide , methyl isothiocyanate , cyclafuramid , fen azole , flusilazole , flutriafol, hexaconazole , imibenconazole , furam , validamycin , streptomycin , (2RS ) - 2 -bromo - 2 - (bro ipconazole , metconazole ,myclobutanil , penconazole , propi momethyl) glutaronitrile (bromothalonil ) , dodine, dogua conazole , prothioconazole , simeconazole , tebuconazole , tet dine , guazatine, iminoctadine, iminoctadine triacetate , 2 , 4 raconazole , triadimefon , triadimenol, triazoxide, triticon D , 2 , 4 - DB , kasugamycin , dimethirimol, fenhexamid , azole , Mefentrifluconazole , 2 - [ [ ( 1R , 5S ) - 5 - [ ( 4 - fluorophenyl ) hymexazole , hydroxyisoxazole imazalil , imazalil sulphate , methyl ] - 1 -hydroxy - 2 , 2 -dimethyl - cyclopentyl] methyl ] - 4H oxpoconazole , pefurazoate , prochloraz , triflumizole, fena 1 , 2 , 4 - triazole - 3 - thione 2 - [ [ 3 - ( 2 - chlorophenyl) - 2 - ( 2 ,4 midone , Bordeaux mixture, calcium polysulfide , copper difluorophenyl) oxiran - 2 -yl ] methyl ] - 4H -1 , 2 ,4 - triazole- 3 acetate , copper carbonate , copper hydroxide , copper naph thione, ametoctradin ( imidium ), iprovalicarb , valifenalate , thenate , copper oleate , copper oxychloride, copper oxyqui 2 -benzyl - 4 -chlorophenol (Chlorophene ), allyl alcohol, azaf nolate , copper silicate , copper sulphate , copper tallate , enidin , benzalkonium chloride, chloropicrin , cresol, cuprous oxide, sulphur , carbaryl, phthalide ( fthalide ), daracide , dichlorophen ( dichlorophene ), difenzoquat , dipy dingjunezuo ( Jun Si Qi) , oxathiapiprolin , fluoroimide, man rithione , N - ( 2 - p - chlorobenzoylethyl) - hexaminium chloride , dipropamid , KSF - 1002 , benzamorf, dimethomorph , fen NNF- 0721 , octhilinone, oxasulfuron , propamidine and pro propimorph , tridemorph , dodemorph , diethofencarb , fentin pionic acid . acetate , fentin hydroxide , carboxin , oxycarboxin , drazoxo [0125 ] Insecticides such as abamectin , , acet lon , famoxadone , m -phenylphenol , p -phenylphenol , tribro amiprid , amidoflumet ( S - 1955 ) , avermectin , azadirachtin , mophenol ( TBP ) , 2 - [ 2 - [ ( 7 , 8 - difluoro - 2 -methyl - 3 - quinolyl) azinphos- methyl , , bifenazate , , carbo oxy ] -6 - fluoro - phenyl] propan - 2 -ol 2 - [ 2 - fluoro -6 - [ ( 8 - fluoro furan , cartap , chlorantraniliprole (DPX - E2Y45 ) , chlo 2 -methyl - 3 -quinolyl ) oxy ]phenyl ] propan - 2 -ol cyflufenamid , rfenapyr, chlorfluazuron , , chlorpyrifos- methyl , ofurace, oxadixyl, flutolanil ,mepronil , isofetamid , fenpiclo chromafenozide , clothianidin , cyflumetofen , cyfluthrin , nil , fludioxonil, pencycuron , edifenphos, iprobenfos, pyra beta -cyfluthrin , cyhalothrin , lambda -cyhalothrin , cyper zophos , phosphorus acids , tecloftalam , captafol, captan , methrin , cyromazine , deltamethrin , diafenthiuron , , ditalimfos, triforine , fenpropidin , piperalin , osthol , 1 - meth , diflubenzuron , dimefluthrin , , dinote ylcyclopropene, 4 - CPA , chlormequat, clofencet, dichlo furan , diofenolan , emamectin , , , rprop , dimethipin , endothal, ethephon , flumetralin , forchlo ethiprole , fenothiocarb , fenoxycarb , , fenval rfenuron , gibberellic acid , gibberellins , hymexazol, maleic erate , fipronil , flonicamid , , flucythrinate , tau hydrazide , mepiquat, naphthalene acetamide, paclobutrazol, fluvalinate , flufenerim (UR - 50701) , , fonophos , prohexadione , prohexadione -calcium , thidiazuron , tribufos halofenozide, hexaflumuron , hydramethylnon , , ( tributyl phosphorotrithioate ) , trinexapac , uniconazole , indoxacarb , isofenphos , lufenuron , , metaflumi a -naphthalene acetic acid , polyoxin D ( polyoxrim ) , BLAD , zone , metaldehyde , , , chitosan , fenoxanil , folpet , 3 - ( difluoromethyl) - N -methoxy methomyl, , , metofluthrin , mono 1 -methyl - N -[ 1 -methyl - 2 - (2 , 4 ,6 - trichlorophenyl) ethyl] pyra crotophos, methoxyfenozide , nitenpyram , , zole - 4 - carboxamide, bixafen , fluxapyroxad , furametpyr, novaluron , noviflumuron (XDE -007 ) , oxamyl, parathion , isopyrazam , penflufen , penthiopyrad , sedaxane , fenpyra parathion -methyl , permethrin , , , , zamine , diclomezine , pyrifenox , boscalid , fluopyram , diflu , pirimicarb , profenofos, profluthrin , metorim , fenarimol, 5 - fluoro -2 - (p - tolylmethoxy )pyrimidin pymetrozine , pyrafluprole , , pyridalyl, pyrifluqui 4 -amine ferimzone, dimetachlone (dimethaclone ), nazon , pyriprole , pyriproxyfen , rotenone , , spin pyroquilon , proquinazid , ethoxyquin , quinoxyfen , 4 , 4 ,5 - tri etoram , spinosad , spirodiclofen , spiromesifen (BSN 2060 ), fluoro - 3 , 3 - dimethyl - 1 - ( 3 - quinolyl ) isoquinoline 4 , 4 - dif spirotetramat, sulprofos, tebufenozide, teflubenzuron , teflu luoro - 3, 3 -dimethyl - 1 -( 3 -quinolyl ) isoquinoline 5 - fluoro -3 , 3 , thrin , , , thiacloprid , thiame 4 , 4 - tetramethyl - 1 - ( 3 - quinolyl ) isoquinoline 9 - fluoro - 2 , 2 thoxam , thiodicarb , thiosultap - sodium , , triaza dimethyl -5 - ( 3 -quinolyl ) - 3H -1 ,4 -benzoxazepine , mate , trichlorfon and triflumuron ; tebufloquin , oxolinic acid , chinomethionate (oxythioquinox , [ 0126 ] Bactericides such as streptomycin ; quinoxymethionate ), spiroxamine , ( E ) -N -methyl - 2 -[ 2 - (2 , 5 [0127 ] Acaricides such as , chinomethionat, dimethylphenoxymethyl) phenyl] - 2 -methoxy - iminoacet chlorobenzilate , cyenopyrafen , cyhexatin , , amide , (mandestrobin ), azoxystrobin , coumoxystrobin , dienochlor, etoxazole , fenazaquin , fenbutatin oxide , US 2018 /0289005 A1 Oct . 11, 2018 12

fenpropathrin , fenpyroximate , hexythiazox , propargite , fon (1039 ) + TX , diafenthiuron (226 ) + TX , dialifos pyridaben and ; and ( 1042 ) + TX , diazinon (227 ) + TX , dichlofluanid (230 ) + [0128 ] Biological agents such as Bacillus thuringiensis , TX , (236 ) + TX , dicliphos (alternative Bacillus thuringiensis delta endotoxin , baculovirus , name) + TX , dicofol ( 242) + TX , ( 243 ) + TX , and entomopathogenic bacteria , virus and fungi. dienochlor ( 1071 ) + TX , ( 1081 ) + TX , dime [ 0129 Other examples of mixture compositions are as thoate ( 262 ) + TX , dinactin (alternative name) (653 ) + follows (wherein the term " TX ” means: " a compound TX , dinex ( 1089 ) + TX , dinex -diclexine ( 1089 ) + TX , selected from compound no . 67. 002 , 67 . 003 , 67 . 007 , dinobuton (269 ) + TX , dinocap ( 270 )+ TX , dinocap -4 67 .009 , 67 .011 , 67 .013 , 67 .014 , 67 .015 and 67 . 018 , as [ CCN ] + TX , dinocap -6 [CCN ] + TX , dinocton ( 1090 ) + defined in the Table X above” ) : TX , dinopenton (1092 ) + TX , dinosulfon ( 1097 ) + TX , [0130 ] an adjuvant selected from the group of sub dinoterbon ( 1098 ) + TX , ( 1102 ) + TX , diphe stances consisting of petroleum oils ( alternative name) nyl sulfone ( IUPAC name) ( 1103 ) + TX , disulfiram ( al (628 ) + TX , ternative name ) [ CCN ] + TX , (278 ) + TX , [0131 ] an selected from the group of sub DNOC (282 ) + TX , dofenapyn ( 1113 ) + TX , doramectin stances consisting of 1 , 1 -bis ( 4 - chloro -phenyl ) - 2 (alternative name) [CCN ]+ TX , endosulfan (294 ) + TX , ethoxyethanol ( IUPAC name) (910 ) + TX , 2 , 4 -dichloro ( 1121 ) + TX , EPN (297 ) + TX , eprinomectin phenyl benzenesulfonate (IU PAC / Chemical Abstracts (alternative name) [CCN ] + TX , ethion ( 309 ) + TX , name) ( 1059 ) + TX , 2 - fluoro - N - methyl- N - 1 - naphthy ethoate -methyl ( 1134 ) + TX , etoxazole ( 320 ) + TX , lacetamide ( IUPAC name) ( 1295 ) + TX , 4 - chlorophenyl etrimfos ( 1142 ) + TX , fenazaflor ( 1147 ) + TX , fenaza phenyl sulfone ( IUPAC name ) ( 981 )+ TX , abamectin quin ( 328 ) + TX , fenbutatin oxide (330 ) + TX , fenothio ( 1 ) + TX , acequinocyl ( 3 ) + TX , acetoprole (CCN ] + TX , carb ( 337 ) + TX , fenpropathrin (342 ) + TX , fenpyrad (al acrinathrin ( 9 ) + TX , ( 16 ) + TX , aldoxycarb ternative name ) + TX , fenpyroximate ( 345 ) + TX , fenson ( 863 ) + TX , alpha -cypermethrin (202 ) + TX , amidithion ( 1157 ) + TX , fentrifanil ( 1161) + TX , fenvalerate (349 ) + ( 870 ) + TX , amidoflumet CCN ] + TX , amidothioate TX , fipronil (354 ) + TX , fluacrypyrim (360 ) + TX , flua (872 ) + TX , amiton (875 ) + TX , amiton hydrogen oxalate zuron ( 1166 ) + TX , flubenzimine ( 1167 ) + TX , flucyclox (875 ) + TX , amitraz ( 24 ) + TX , aramite ( 881 ) + TX , arse uron ( 366 ) + TX , flucythrinate (367 ) + TX , fluenetil nous oxide (882 ) + TX , AVI 382 ( compound code ) + TX , ( 1169 ) + TX , flufenoxuron ( 370 ) + TX , flumethrin ( 372 ) + AZ 60541 ( compound code ) + TX , azinphos- ethyl (44 ) + TX , fluorbenside (1174 ) + TX , fluvalinate (1184 ) + TX , TX , azinphos -methyl (45 ) + TX , azobenzene ( IUPAC FMC 1137 (development code) ( 1185 ) + TX , formetan name) ( 888 ) + TX , azocyclotin ( 46 ) + TX , azothoate ate (405 ) + TX , hydrochloride (405 ) + TX , (889 ) + TX , benomyl (62 ) + TX , benoxafos ( alternative ( 1192 ) + TX , ( 1193 ) + TX , name) [ CCN ] + TX , benzoximate (71 ) + TX , benzyl ben gamma- HCH (430 ) + TX , glyodin ( 1205 ) + TX , halfen zoate ( IUPAC name ) [ CCN ] + TX , bifenazate (74 ) + TX , prox (424 ) + TX , heptenophos (432 ) + TX , hexadecyl bifenthrin ( 76 ) + TX , binapacryl ( 907 ) + TX , brofenval cyclopropanecarboxylate ( IUPAC /Chemical Abstracts erate ( alternative name) + TX , bromocyclen (918 ) + TX , name) ( 1216 ) + TX , hexythiazox (441 ) + TX , iodometh bromophos (920 ) + TX , bromophos - ethyl (921 ) + TX , ane ( IUPAC name) (542 ) + TX , isocarbophos (alterna bromopropylate ( 94 ) + TX , buprofezin ( 99 ) + TX , buto tive name) (473 ) + TX , isopropyl 0 - (methoxyaminoth carboxim ( 103 ) + TX , butoxycarboxim ( 104 ) + TX , iophosphoryl ) salicylate ( IUPAC name) (473 ) + TX , butylpyridaben ( alternative name ) + TX , calcium poly ivermectin ( alternative name) [ CCN ] + TX , jasmolin I sulfide ( IUPAC name) ( 111 ) + TX , camphechlor ( 941) + (696 )+ TX , jasmolin II (696 ) + TX , jodfenphos (1248 ) + TX , carbanolate ( 943) + TX , carbaryl (115 ) + TX , carbo TX , (430 ) + TX , lufenuron (490 ) + TX , mala furan ( 118 ) + TX , (947 ) + TX , CGA thion (492 ) + TX , malonoben ( 1254 ) + TX , mecarbam 50439 (development code ) (125 ) + TX , chinomethionat ( 502 ) + TX , mephosfolan ( 1261 ) + TX , mesulfen ( alter ( 126 ) + TX , chlorbenside (959 ) + TX , native name) [CCN ] + TX , methacrifos ( 1266 ) + TX , ( 964 )+ TX , chlordimeform hydrochloride ( 964 ) + TX , methamidophos (527 ) + TX , methidathion (529 ) + TX , chlorfenapyr (130 ) + TX , chlorfenethol ( 968 ) + TX , chlo (530 ) + TX , methomyl (531 ) + TX , methyl rfenson ( 970 ) + TX , chlorfensulfide (971 ) + TX , chlo bromide ( 537 ) + TX , ( 550 ) + TX , rfenvinphos (131 ) + TX , chlorobenzilate (975 ) + TX , (556 ) + TX , mexacarbate ( 1290 ) + TX , milbemectin chloromebuform ( 977 ) + TX , chloromethiuron ( 978 ) + (557 ) + TX , milbemycin oxime (alternative name) TX , chloropropylate ( 983 ) + TX , chlorpyrifos ( 145) + CCN ] + TX , ( 1293 ) + TX , TX , chlorpyrifos -methyl ( 146 ) + TX , chlorthiophos (561 ) + TX , morphothion ( 1300 ) + TX , moxidectin (alter (994 ) + TX , cinerin I (696 ) + TX , cinerin II (696 ) + TX , native name) [CCN ] + TX , ( 567) + TX , NC - 184 cinerins (696 ) + TX , clofentezine ( 158 ) + TX , closantel ( compound code ) + TX , NC - 512 ( compound code ) + TX , (alternative name ) [ CCN ]+ TX , (174 ) + TX , nifluridide ( 1309 ) + TX , nikkomycins ( alternative name ) crotamiton ( alternative name) [CCN ] + TX , crotoxyphos [CCN ] + TX , nitrilacarb ( 1313 ) + TX , nitrilacarb 1 : 1 zinc ( 1010 ) + TX , cufraneb ( 1013 ) + TX , cyanthoate ( 1020 ) + chloride complex ( 1313 ) + TX , NNI-0101 ( compound TX , cyflumetofen (CAS Reg . No .: 400882 -07 - 7 ) + TX , code ) + TX , NNI- 0250 ( compound code + TX , cyhalothrin ( 196 ) + TX , cyhexatin ( 199 ) + TX , cyper (594 ) + TX , oxamyl (602 ) + TX , oxydeprofos methrin (201 ) + TX , DCPM (1032 ) + TX , DDT (219 ) + ( 1324 ) + TX , oxydisulfoton ( 1325 ) + TX , pp ' -DDT TX , ( 1037) + TX , demephion - 0 ( 1037 ) + TX , (219 ) + TX , parathion (615 ) + TX , permethrin (626 ) + TX , demephion - S ( 1037 ) + TX , demeton ( 1038 ) + TX , deme petroleum oils ( alternative name) (628 ) + TX , phenkap ton -methyl ( 224 ) + TX , demeton - O ( 1038 ) + TX , deme ton ( 1330 ) + TX , (631 ) + TX , phorate (636 ) + ton - O -methyl (224 ) + TX , demeton - S ( 1038 ) + TX , TX , phosalone (637 ) + TX , ( 1338 ) + TX , phos demeton -S -methyl (224 ) + TX , demeton - S -methylsul met (638 ) + TX , phosphamidon (639 ) + TX , US 2018 /0289005 A1 Oct . 11, 2018

(642 ) + TX , pirimiphos -methyl (652 ) + TX , polychloro dodicin ( 1112 )+ TX , fenaminosulf ( 1144 ) + TX , formal terpenes ( traditional name) ( 1347 ) + TX , polynactins dehyde (404 ) + TX , hydrargaphen (alternative name) (alternative name) (653 ) + TX , proclonol (1350 ) + TX , [CCN ] + TX , kasugamycin (483 ) + TX , kasugamycin profenofos (662 ) + TX , promacyl (1354 ) + TX , proparg hydrochloride hydrate (483 ) + TX , nickel bis (dimethyl ite (671 ) + TX , propetamphos (673 ) + TX , dithiocarbamate ) ( IUPAC name) (1308 ) + TX , nitrapy (678 ) + TX , prothidathion ( 1360 ) + TX , rin (580 ) + TX , octhilinone (590 ) + TX , oxolinic acid ( 1362) + TX , pyrethrin 1 (696 ) + TX , pyrethrin 11 (696 ) + (606 ) + TX , oxytetracycline (611 ) + TX , potassium TX , (696 ) + TX , pyridaben (699 ) + TX , hydroxyquinoline sulfate (446 ) + TX , probenazole pyridaphenthion (701 ) + TX , pyrimidifen (706 ) + TX , (658 ) + TX , streptomycin ( 744 ) + TX , streptomycin ses pyrimitate ( 1370 ) + TX , (711 ) + TX , quintio quisulfate ( 744 ) + TX , tecloftalam ( 766 ) + TX , and thio fos ( 1381) + TX , R - 1492 (development code ) ( 1382 ) + mersal ( alternative name ) [ CCN ] + TX , TX , RA - 17 (development code ) ( 1383 ) + TX , rotenone (722 ) + TX , (1389 ) + TX , sebufos ( alternative [0136 ] a biological agent selected from the group of name) + TX , selamectin ( alternative name) [ CCN ] + TX , substances consisting of Adoxophyes orana GV ( alter SI- 0009 ( compound code ) + TX , sophamide ( 1402 ) + native name ) ( 12 ) + TX , Agrobacterium radiobacter (al TX , spirodiclofen (738 ) + TX , spiromesifen (739 ) + TX , ternative name) ( 13 ) + TX , Amblyseius spp . ( alternative name) (19 ) + TX , Anagrapha falcifera NPV ( alternative SSI - 121 ( development code ) ( 1404 ) + TX , sulfiram (al name) (28 ) + TX , Anagrus atomus ( alternative name) ternative name ) [CCN ] + TX , sulfluramid (750 ) + TX , ( 29 ) + TX , Aphelinus abdominalis ( alternative name) sulfotep (753 ) + TX , sulfur (754 ) + TX , SZI - 121 (devel ( 33 ) + TX , Aphidius colemani (alternative name ) ( 34 ) + opment code ) (757 ) + TX , tau - fluvalinate ( 398 ) + TX , TX , Aphidoletes aphidimyza ( alternative name ) ( 35 ) + tebufenpyrad ( 763) + TX , TEPP ( 1417 ) + TX , terbam ( al TX , Autographa californica NPV (alternative name ) ternative name) + TX , tetrachlorvinphos (777 ) + TX , tet ( 38 ) + TX , Bacillus firmus (alternative name ) (48 ) + TX , radifon (786 ) + TX , tetranactin ( alternative name) Bacillus sphaericus Neide ( scientific name) (49 ) + TX , (653 ) + TX , tetrasul ( 1425 ) + TX , thiafenox ( alternative Bacillus thuringiensis Berliner (scientific name) (51 )+ name) + TX , thiocarboxime ( 1431 ) + TX , TX , Bacillus thuringiensis subsp . aizawai ( scientific (800 )+ TX , thiometon (801 ) + TX , thioquinox (1436 )+ name ) (51 ) + TX , Bacillus thuringiensis subsp . israel TX , thuringiensin ( alternative name) [ CCN ] + TX , tri ensis ( scientific name) ( 51 ) + TX , Bacillus thuringiensis amiphos (1441 ) + TX , triarathene ( 1443 ) + TX , triazo subsp . japonensis ( scientific name) (51 ) + TX , Bacillus phos ( 820 ) + TX , triazuron ( alternative name ) + TX , thuringiensis subsp . kurstaki (scientific name ) (51 ) + trichlorfon (824 ) + TX , trifenofos ( 1455 ) + TX , trinactin TX , Bacillus thuringiensis subsp . tenebrionis (scien (alternative name) (653 ) + TX , vamidothion (847 ) + TX , tific name ) (51 ) + TX , Beauveria bassiana ( alternative vaniliprole [ CCN ] and Y1 -5302 ( compound code ) + TX , name) (53 ) + TX , Beauveria brongniartii (alternative [0132 ] an algicide selected from the group of substances name) ( 54 ) + TX , Chrysoperla carnea (alternative consisting of bethoxazin [CCN ] + TX , copper dioctano name ) ( 151) + TX , Cryptolaemus montrouzieri ( alterna ate ( IUPAC name) ( 170 ) + TX , copper sulfate ( 172 ) + tive name) ( 178 ) + TX , Cydia pomonella GV (alterna TX , cybutryne [CCN ] + TX , dichlone ( 1052 ) + TX , tive name ) ( 191 ) + TX , Dacnusa sibirica (alternative dichlorophen (232 ) + TX , endothal ( 295 ) + TX , fentin name) (212 ) + TX , Diglyphus isaea (alternative name) (347 ) + TX , hydrated lime [ CCN ] + TX , nabam ( 566 ) + ( 254 ) + TX , Encarsia formosa (scientific name) ( 293 ) + TX , quinoclamine (714 ) + TX , quinonamid ( 1379 ) + TX , TX , Eretmocerus eremicus (alternative name) ( 300 ) + simazine ( 730 ) + TX , triphenyltin acetate ( IUPAC TX , Helicoverpa zea NPV ( alternative name) (431 ) + name) ( 347 ) and triphenyltin hydroxide ( IUPAC name) TX , Heterorhabditis bacteriophora and H . megidis ( 347 ) + TX , ( alternative name) (433 ) + TX , Hippodamia convergens [0133 ] an anthelmintic selected from the group of sub ( alternative name) ( 442 ) + TX , Leptomastix dactylopii stances consisting of abamectin ( 1 ) + TX , crufomate ( alternative name) (488 ) + TX , Macrolophus caliginosus ( 1011) + TX , doramectin ( alternative name) [ CCN ] + TX , ( alternative name) (491 ) + TX , Mamestra brassicae emamectin ( 291 ) + TX , emamectin benzoate ( 291 ) + TX , NPV (alternative name ) (494 ) + TX , Metaphycus hel eprinomectin ( alternative name) [CCN ] + TX , ivermec volus (alternative name) (522 ) + TX , Metarhizium tin ( alternative name) [CCN ] + TX , milbemycin oxime anisopliae var. acridum (scientific name ) ( 523 ) + TX , (alternative name) [CCN ] + TX , moxidectin ( alternative Metarhizium anisopliae var. anisopliae ( scientific name) [ CCN ] + TX , piperazine [CCN ] + TX , selamectin name) ( 523 ) + TX , Neodiprion sertifer NPV and N . ( alternative name) [CCN ] + TX , spinosad ( 737 ) and lecontei NPV ( alternative name ) (575 ) + TX , Orius spp . thiophanate ( 1435 ) + TX , ( alternative name) (596 ) + TX , Paecilomyces fumosoro [0134 ] an avicide selected from the group of substances seus ( alternative name) (613 ) + TX , Phytoseiulus persi consisting of chloralose ( 127 ) + TX , ( 1122 ) + TX , milis (alternative name) (644 ) + TX , Spodoptera exigua (346 ) + TX , pyridin - 4 -amine ( IUPAC name) multicapsid nuclear polyhedrosis virus ( scientific (23 ) and strychnine ( 745 ) + TX , name) (741 ) + TX , Steinernema bibionis (alternative [0135 ] a bactericide selected from the group of sub name ) (742 ) + TX , Steinernema carpocapsae ( alterna stances consisting of 1 -hydroxy - 1H - pyridine - 2 - thione tive name ) ( 742 ) + TX , Steinernema feltiae ( alternative ( IUPAC name ) ( 1222 ) + TX , 4 - (quinoxalin - 2 -ylamino ) name ) (742 ) + TX , Steinernema glaseri ( alternative benzenesulfonamide ( IUPAC name) (748 ) + TX , 8 -hy name ) (742 ) + TX , Steinernema riobrave (alternative droxyquinoline sulfate (446 ) + TX , bronopol (97 ) + TX , name) (742 ) + TX , Steinernema riobravis ( alternative copper dioctanoate ( IUPAC name) ( 170 ) + TX , copper name ) (742 ) + TX , Steinernema scapterisci (alternative hydroxide ( IUPAC name) ( 169 ) + TX , cresol [CCN ] + name ) (742 ) + TX , Steinernema spp . ( alternative name ) TX , dichlorophen ( 232 ) + TX , dipyrithione ( 1105 ) + TX , ( 742 ) + TX , Trichogramma spp . (alternative name) US 2018 /0289005 A1 Oct . 11, 2018 14 .

(826 ) + TX , Typhlodromus occidentalis ( alternative (alternative name) [ CCN ] + TX , oryctalure ( alternative name) (844 ) and Verticillium lecanii ( alternative name) name) ( 317 ) + TX , ostramone (alternative name) (848 ) + TX , [CCN ] + TX , siglure [CCN ] + TX , sordidin (alternative [0137 ] a soil sterilant selected from the group of sub name) ( 736 ) + TX , sulcatol ( alternative name) [CCN ] + stances consisting of iodomethane ( IUPAC name) TX , tetradec - 11 -en - 1 - yl acetate ( IUPAC name) ( 785 ) + (542 ) and methyl bromide (537 ) + TX , TX , trimedlure (839 ) + TX , trimedlure A ( alternative [0138 ] a chemosterilant selected from the group of name) ( 839 ) + TX , trimedlure Bi ( alternative name) substances consisting of apholate [ CCN ] + TX , bisazir (839 ) + TX , trimedlure B2 ( alternative name) (839 ) + TX , ( alternative name ) [CCN ] + TX , busulfan (alternative trimedlure C ( alternative name) (839 ) and trunc - call name) [ CCN ] + TX , diflubenzuron ( 250 ) + TX , dimatif ( alternative name) [CCN ] + TX , ( alternative name) [CCN ] + TX , hemel [ CCN ] + TX , [ 0140 ] an insect repellent selected from the group of hempa [CCN ] + TX , metepa [CCN ] + TX , methiotepa substances consisting of 2 - ( octylthio ) - ethanol ( IUPAC [CCN ] + TX , methyl apholate [ CCN ] + TX , morzid name) (591 ) + TX , butopyronoxyl ( 933 ) + TX , butoxy [ CCN ] + TX , penfluron ( alternative name ) [CCN ] + TX , (polypropylene glycol) (936 ) + TX , dibutyl adipate (IU tepa [CCN ] + TX , thiohempa ( alternative name) PAC name) ( 1046 ) + TX , dibutyl phthalate ( 1047 ) + TX , [ CCN ] + TX , thiotepa (alternative name) [CCN ] + TX , dibutyl succinate ( IUPAC name) ( 1048 ) + TX , diethyl tretamine (alternative name) [CCN ] and uredepa (alter toluamide [ CCN ] + TX , dimethyl carbate (CCN ] + TX , native name) [CCN ] + TX , dimethyl phthalate [ CCN ] + TX , ethyl hexanediol [0139 ] an insect pheromone selected from the group of ( 1137 ) + TX , hexamide [ CCN ] + TX , methoquin -butyl substances consisting of ( E ) -dec - 5 -en - 1- yl acetate with ( 1276 ) + TX , methylneodecanamide [ CCN ] + TX , oxam ( E ) - dec - 5 - en - 1 -ol ( IUPAC name) ( 222 ) + TX , ( E ) - tri ate [CCN ] and picaridin [ CCN ] + TX , dec - 4 -en - 1 -yl acetate ( IUPAC name) (829 ) + TX , ( E ) - 6 [ 0141] an insecticide selected from the group of sub methylhept- 2 - en - 4 - ol (IUPAC name) (541 ) + TX , ( E , Z ) stances consisting of 1 -dichloro - 1 -nitroethane ( IUPACI tetradeca - 4 , 10 -dien - 1 -yl acetate (IUPAC name ) ( 779 ) + Chemical Abstracts name) ( 1058 ) + TX , 1 , 1 - dichloro - 2 , TX . ( Z ) - dodec - 7 -en - 1 - yl acetate (IUPAC name) ( 285 ) + 2 - bis ( 4 - ethylphenyl) ethane ( IUPAC name) ( 1056 ) , TX , ( Z ) -hexadec - 11 - enal ( IUPAC name) ( 436 + TX , + TX , 1 , 2 -dichloropropane (IUPAC / Chemical Abstracts ( Z ) -hexadec - 11 - en - 1 - yl acetate ( IUPAC name) (437 ) + name ) ( 1062 ) + TX , 1 , 2 -dichloropropane with 1 , 3 -di TX , ( Z ) - hexadec - 13 - en - 11- yn - 1 - yl acetate ( IUPAC chloropropene (IUPAC name) ( 1063 ) + TX , 1 -bromo - 2 name) ( 438 ) + TX , ( Z ) - icos - 13 -en - 10 -one ( IUPAC chloroethane ( IUPAC /Chemical Abstracts name ) name) (448 ) + TX , (Z ) - tetradec - 7 -en - 1 -al ( IUPAC ( 916 ) + TX , 2 , 2 , 2 - trichloro - 1 - ( 3 , 4 - dichlorophenyl) ethyl name) (782 ) + TX , ( Z ) - tetradec - 9 - en - 1 - ol ( IUPAC acetate ( IUPAC name) ( 1451 ) + TX , 2 , 2 - dichlorovinyl name) (783 ) + TX , (Z ) - tetradec - 9 - en - 1 -yl acetate (IU 2 - ethylsulfinylethyl methyl phosphate ( IUPAC name) PAC name) (784 ) + TX , (7E , 9Z ) -dodeca - 7 , 9 - dien - 1 - yl ( 1066 ) + TX , 2 - ( 1 , 3 - dithiolan - 2 - yl) phenyl dimethylcar acetate ( IUPAC name) (283 ) + TX , ( 97 , 11 E ) - tetradeca bamate ( IUPAC /Chemical Abstracts name ) ( 1109 ) + 9 ,11 -dien -1 - yl acetate ( IUPAC name) (780 ) + TX , (9Z , TX , 2 -( 2 -butoxyethoxy ) ethyl thiocyanate ( IUPACI 12E ) -tetradeca - 9 , 12 -dien - 1 - yl acetate (IUPAC name) Chemical Abstracts name) (935 ) + TX , 2 - ( 4 , 5 - dimethyl (781 ) + TX , 14 -methyloctadec - 1 -ene ( IUPAC name) 1 ,3 -dioxolan - 2 -yl ) phenyl methylcarbamate ( IUPACI ( 545 ) + TX , 4 -methylnonan - 5 - ol with 4 -methylnonan - 5 Chemical Abstracts name) ( 1084 ) + TX , 2 - ( 4 - chloro - 3 , one ( IUPAC name) (544 ) + TX , alpha -multistriatin (al 5 - xylyloxyethanol ( IUPAC name) ( 986 ) + TX , ternative name) [ CCN ] + TX , brevicomin ( alternative 2 - chlorovinyl diethyl phosphate ( IUPAC name) ( 984 )+ name ) [CCN ] + TX , codlelure (alternative name) TX , 2 - imidazolidone ( IUPAC name) ( 1225 ) + TX , 2 - is [ CCN ] + TX , codlemone (alternative name) ( 167 ) + TX , ovalerylindan - 1 , 3 -dione ( IUPAC name) (1246 ) + TX , cuelure ( alternative name) ( 179 ) + TX , disparlure ( 277 ) + 2 -methyl ( prop - 2 - ynyl ) aminophenyl methylcarbamate TX , dodec - 8 -en - 1 -yl acetate ( IUPAC name) (286 ) + TX , ( IUPAC name ) ( 1284 ) + TX , 2 - thiocyanatoethyl laurate dodec - 9 - en - 1 - yl acetate ( IUPAC name) (287 ) + TX , ( IUPAC name) (1433 )+ TX , 3 -bromo - 1 -chloroprop - 1 dodeca - 8 + TX , 10 -dien - 1 -yl acetate ( IUPAC name ) ene ( IUPAC name) (917 ) + TX , 3 -methyl - 1 - phenylpyra ( 284 ) + TX , dominicalure ( alternative name) [CCN ] + zol- 5 - yl dimethylcarbamate ( IUPAC name) ( 1283 ) + TX , ethyl 4 -methyloctanoate ( IUPAC name) (317 ) + TX , 4 -methyl ( prop - 2 - ynyl ) amino - 3 , 5 - xylyl TX , eugenol (alternative name ) [CCN ] + TX , frontalin methylcarbamate ( IUPAC name ) ( 1285 ) + TX , 5 , 5 -dim (alternative name) [CCN ] + TX , gossyplure (alternative ethyl- 3 -oxocyclohex - 1 -enyl dimethylcarbamate (IU name) (420 ) + TX , grandlure ( 421 ) + TX , grandlure I PAC name) ( 1085) + TX , abamectin ( 1 ) + TX , acephate ( alternative name) (421 ) + TX , grandlure II ( alternative ( 2 )+ TX , acetamiprid (4 ) + TX , acethion (alternative name) (421 ) + TX , grandlure III ( alternative name) name) [ CCN ] + TX , acetoprole [CCN ] + TX , acrinathrin ( 421 ) + TX , grandlure IV (alternative name) ( 421 ) + TX , ( 9 ) + TX , acrylonitrile ( IUPAC name) (861 ) + TX , alany hexalure [CCN ] + TX , ipsdienol ( alternative name) carb ( 15 ) + TX , aldicarb (16 ) + TX , aldoxycarb (863 ) + [CCN ] + TX , ipsenol ( alternative name) [ CCN ] + TX , TX , ( 864 ) + TX , allethrin ( 17 ) + TX , allosamidin japonilure (alternative name) (481 ) + TX , lineatin (alter (alternative name) [ CCN ] + TX , allyxycarb (866 ) + TX , native name) [CCN ] + TX , litlure (alternative name) alpha - cypermethrin ( 202 ) + TX , alpha- ecdysone ( alter [CCN ] + TX , looplure ( alternative name) [ CCN ] + TX , native name) [CCN ] + TX , (640 ) + medlure [CCN ] + TX , megatomoic acid ( alternative TX , amidithion (870 ) + TX , amidothioate (872 ) + TX , name) [CCN ] + TX , methyl eugenol (alternative name) (873 ) + TX , amiton (875 ) + TX , amiton (540 ) + TX , muscalure (563 ) + TX , octadeca - 2 , 13 -dien hydrogen oxalate (875 ) + TX , amitraz (24 ) + TX , ana 1 - yl acetate ( IUPAC name) ( 588) + TX , octadeca - 3 , 13 basine (877 ) + TX , athidathion (883 ) + TX , AVI 382 dien - 1 -yl acetate (IUPAC name) (589 ) + TX , orfralure (compound code )+ TX , AZ 60541 ( compound code )+ US 2018 /0289005 A1 Oct. 11 , 2018

TX , azadirachtin (alternative name) (41 ) + TX , azame (224 ) + TX , demeton -O ( 1038 )+ TX , demeton - O -methyl thiphos (42 ) + TX , azinphos - ethyl ( 44 ) + TX , azinphos (224 ) + TX , demeton -S (1038 )+ TX , demeton - S -methyl methyl (45 ) + TX , azothoate (889 ) + TX , Bacillus (224 ) + TX , demeton - S -methylsulphon ( 1039 ) + TX , thuringiensis delta endotoxins ( alternative name) (52 ) + diafenthiuron ( 226 )+ TX , dialifos (1042 )+ TX , diamida TX , barium hexafluorosilicate (alternative name) fos ( 1044 ) + TX , diazinon (227 ) + TX , dicapthon ( 1050 ) + [ CCN ] + TX , barium polysulfide ( IUPAC /Chemical TX , dichlofenthion ( 1051) + TX , dichlorvos ( 236 ) + TX , Abstracts name ) ( 892 ) + TX , barthrin [CCN ] + TX , Bayer dicliphos (alternative name) + TX , dicresyl ( alternative 22 / 190 (development code ) (893 ) + TX , Bayer 22408 name) [ CCN ] + TX , dicrotophos ( 243 ) + TX , dicyclanil ( development code ) (894 ) + TX , (58 ) + TX , ( 244 ) + TX , dieldrin ( 1070 ) + TX , diethyl 5 -methylpyra benfuracarb (60 ) + TX , bensultap ( 66 + TX , beta - cyflu zol- 3 -yl phosphate ( IUPAC name ) ( 1076 ) + TX , thrin ( 194 ) + TX , beta - cypermethrin ( 203 ) + TX , bifen diflubenzuron ( 250 ) + TX , dilor ( alternative name) thrin ( 76 ) + TX , bioallethrin ( 78 ) + TX , bioallethrin S - cy [ CCN ] + TX , dimefluthrin [ CCN ] + TX , dimefox (1081 ) + clopentenyl isomer (alternative name ) ( 79 ) + TX , TX , dimetan ( 1085 ) + TX , dimethoate ( 262) + TX , dime bioethanomethrin [CCN ] + TX , biopermethrin ( 908 ) + thrin (1083 ) + TX , dimethylvinphos (265 ) + TX , dimeti TX , bioresmethrin (80 )+ TX , bis ( 2 -chloroethyl ) ether lan ( 1086 ) + TX , dinex ( 1089 ) + TX , dinex - diclexine ( IUPAC name) ( 909 ) + TX , bistrifluron (83 ) + TX , borax ( 1089 ) + TX , dinoprop ( 1093 ) + TX , dinosam ( 1094 ) + ( 86 ) + TX , brofenvalerate (alternative name) + TX , bro TX , dinoseb ( 1095 ) + TX , (271 ) + TX , mfenvinfos (914 ) + TX , bromocyclen (918 ) + TX , diofenolan (1099 ) + TX , dioxabenzofos (1100 ) + TX , bromo -DDT (alternative name) [CCN ] + TX , bro dioxacarb ( 1101 ) + TX , dioxathion ( 1102 ) + TX , disulfo mophos ( 920 ) + TX , bromophos - ethyl ( 921) + TX , bufen ton (278 )+ TX , dithicrofos ( 1108 ) + TX , DNOC (282 ) + carb (924 ) + TX , buprofezin ( 99 ) + TX , butacarb (926 ) + TX , doramectin (alternative name ) [ CCN ] + TX , DSP TX , butathiofos ( 927 ) + TX , ( 103 ) + TX , ( 1115) + TX , ecdysterone (alternative name ) [CCN ] + butonate (932 ) + TX , butoxycarboxim ( 104 ) + TX , TX , EI 1642 (development code ) ( 1118 ) + TX , emamec butylpyridaben ( alternative name) + TX , cadusafos tin (291 ) + TX , emamectin benzoate ( 291 ) + TX , EMPC ( 109 ) + TX , (CCN ] + TX , calcium cya ( 1120 ) + TX , empenthrin ( 292 ) + TX , endosulfan (294 ) + nide (444 ) + TX , calcium polysulfide ( IUPAC name) TX , endothion (1121 ) + TX , endrin ( 1122 ) + TX , EPBP ( 111 ) + TX , camphechlor (941 ) + TX , carbanolate (943 ) + ( 1123 ) + TX , EPN (297 ) + TX , epofenonane ( 1124 ) + TX , TX , carbaryl ( 115 ) + TX , (118 ) + TX , carbon eprinomectin ( alternative name) [CCN ] + TX , esfenva disulfide ( IUPAC /Chemical Abstracts name ) (945 ) + lerate (302 ) + TX , etaphos (alternative name) [CCN ] + TX , ( IUPAC name) (946 ) + TX , TX , ethiofencarb (308 ) + TX , ethion ( 309 ) + TX , ethip carbophenothion ( 947 ) + TX , carbosulfan ( 119 ) + TX , role (310 ) + TX , ethoate -methyl ( 1134 ) + TX , cartap (123 ) + TX , cartap hydrochloride ( 123 ) + TX , (312 ) + TX , ethyl formate ( IUPAC name) cevadine (alternative name) (725 ) + TX , chlorbicyclen [ CCN ] + TX , ethyl- DDD ( alternative name) ( 1056 ) + TX , (960 ) + TX , ( 128 ) + TX , ( 963 ) + ethylene dibromide (316 ) + TX , ethylene dichloride TX , chlordimeform (964 ) + TX , chlordimeform hydro ( chemical name) (1136 ) + TX , ethylene oxide (CCN ] + chloride ( 964 ) + TX , ( 129 ) + TX , chlo TX , etofenprox ( 319) + TX , etrimfos ( 1142 ) + TX , EXD rfenapyr ( 130 ) + TX , ( 131 ) + TX , ( 1143 ) + TX , famphur ( 323 ) + TX , ( 326 ) + chlorfluazuron (132 ) + TX , chlormephos ( 136 ) + TX , TX , fenazaflor ( 1147) + TX , fenchlorphos (1148 ) + TX , chloroform (CCN ] + TX , chloropicrin ( 141 ) + TX , chlo fenethacarb ( 1149 ) + TX , fenfluthrin ( 1150 ) + TX , feni rphoxim ( 989 ) + TX , chlorprazophos (990 ) + TX , chlo trothion (335 ) + TX , fenobucarb ( 336 ) + TX , fenoxacrim rpyrifos ( 145 ) + TX , chlorpyrifos- methyl (146 ) + TX , (1153 ) + TX , fenoxycarb (340 ) + TX , fenpirithrin chlorthiophos ( 994 ) + TX , chromafenozide ( 150 ) + TX , ( 1155 ) + TX , fenpropathrin ( 342 ) + TX , fenpyrad (alter cinerin I (696 ) + TX , cinerin II (696 ) + TX , cinerins native name) + TX , fensulfothion ( 1158 ) + TX , fenthion (696 ) + TX , cis - ( alternative name) + TX , cis ( 346 ) + TX , fenthion -ethyl ( CCN ] + TX , fenvalerate methrin (80 ) + TX , clocythrin (alternative name) + TX , ( 349 ) + TX , fipronil ( 354 ) + TX , flonicamid ( 358 ) + TX , cloethocarb ( 999 ) + TX , closantel (alternative name) flubendiamide (CAS . Reg . No .: 272451 -65 - 7 ) + TX , flu [CCN + TX , clothianidin ( 165 ) + TX , copper acetoars cofuron (1168 ) + TX , flucycloxuron ( 366 ) + TX , flucyth enite (CCN ] + TX , copper arsenate (CCN ] + TX , copper rinate (367 ) + TX , fluenetil ( 1169 ) + TX , flufenerim oleate [ CCN ] + TX , coumaphos ( 174 ) + TX , coumithoate [CCN ] + TX , flufenoxuron (370 ) + TX , flufenprox ( 1006 ) + TX , crotamiton ( alternative name) [CCN ] + TX , ( 1171 ) + TX , flumethrin (372 )+ TX , fluvalinate ( 1184 ) + crotoxyphos (1010 ) + TX , crufomate ( 1011 ) + TX , cryo TX , FMC 1137 (development code ) ( 1185 ) + TX , fono lite (alternative name ) (177 ) + TX , CS 708 (develop fos ( 1191 ) + TX , formetanate ( 405 ) + TX , formetanate ment code ) ( 1012 ) + TX , cyanofenphos ( 1019 ) + TX , hydrochloride ( 405) + TX , formothion ( 1192 ) + TX , ( 184 ) + TX , cyanthoate ( 1020 ) + TX , formparanate ( 1193 ) + TX , fosmethilan ( 1194 ) + TX , fos cyclethrin [ CCN ] + TX , cycloprothrin ( 188 ) + TX , cyflu pirate ( 1195 ) + TX , fosthiazate (408 ) + TX , fosthietan thrin ( 193 ) + TX , cyhalothrin ( 196 ) + TX , cypermethrin ( 1196 + TX , furathiocarb (412 ) + TX , furethrin ( 1200 ) + ( 201 ) + TX , cyphenothrin ( 206 ) + TX , cyromazine TX , gamma- cyhalothrin ( 197 ) + TX , gamma -HCH ( 209) + TX , cythioate ( alternative name) [CCN ] + TX , (430 ) + TX , guazatine (422 ) + TX , guazatine acetates d - limonene (alternative name) [CCN ] + TX , d - tetram (422 ) + TX , GY- 81 (development code ) ( 423 ) + TX , hal ethrin (alternative name) (788 )+ TX , DAEP ( 1031) + fenprox (424 ) + TX , halofenozide (425 ) + TX , HCH TX , dazomet ( 216 ) + TX , DDT (219 ) + TX , decarbofuran (430 ) + TX , HEOD ( 1070 ) + TX , (1211 ) + TX , ( 1034 ) + TX , deltamethrin (223 ) + TX , demephion heptenophos (432 ) + TX , heterophos [CCN ] + TX , ( 1037) + TX , demephion - O ( 1037 ) + TX , demephion - S hexaflumuron (439 ) + TX , HHDN ( 864 ) + TX , hydram (1037 ) + TX , demeton ( 1038 ) + TX , demeton -methyl ethylnon (443 ) + TX , hydrogen cyanide (444 ) + TX , US 2018 /0289005 A1 Oct . 11, 2018 16

(445 ) + TX , hyquincarb (1223 ) + TX , imida TX , oxydisulfoton ( 1325 ) + TX , pp '- DDT (219 ) + TX , cloprid (458 )+ TX , imiprothrin (460 )+ TX , indoxacarb para- dichlorobenzene [CCN ] + TX , parathion (615 ) + (465 ) + TX , iodomethane ( IUPAC name) (542 ) + TX , TX , parathion - methyl (616 ) + TX , penfluron ( alternative IPSP ( 1229 ) + TX , isazofos ( 1231 ) + TX , name) [ CCN ] + TX , pentachlorophenol ( 623 ) + TX , pen ( 1232 ) + TX , isocarbophos ( alternative name) (473 ) + tachlorophenyl laurate ( IUPAC name) (623 ) + TX , per TX , isodrin ( 1235 ) + TX , isofenphos (1236 ) + TX , iso methrin (626 ) + TX , petroleum oils (alternative name) lane ( 1237 ) + TX , isoprocarb ( 472) + TX , isopropyl (628 ) + TX , PH 60 - 38 (development code ) ( 1328 ) + TX , O - methoxy - aminothiophosphoryl) salicylate ( IUPAC phenkapton ( 1330 ) + TX , phenothrin ( 630 ) + TX , name) (473 )+ TX , isoprothiolane (474 ) + TX , isothioate phenthoate (631 ) + TX , phorate (636 ) + TX , phosalone ( 1244) + TX , (480 ) + TX , ivermectin (alterna (637 ) + TX , phosfolan (1338 ) + TX , phosmet (638 ) + TX , tive name) [CCN ] + TX , jasmolin 1 (696 ) + TX , jasmolin phosnichlor ( 1339 ) + TX , phosphamidon (639 ) + TX , 11 (696 ) + TX , jodfenphos (1248 ) + TX , juvenile hor phosphine ( IUPAC name) ( 640 ) + TX , phoxim (642 ) + mone I ( alternative name) [ CCN ] + TX , juvenile hor TX , phoxim -methyl ( 1340 ) + TX , pirimetaphos ( 1344 ) + mone II (alternative name) [CCN ] + TX , juvenile hor TX , pirimicarb (651 ) + TX , pirimiphos - ethyl (1345 ) + mone III (alternative name) [CCN ] + TX , kelevan TX , pirimiphos -methyl (652 ) + TX , ( 1249 ) + TX , kinoprene (484 ) + TX , lambda - cyhalothrin polychlorodicyclopentadiene isomers ( IUPAC name ) ( 198 ) + TX , lead arsenate ( CCN ] + TX , lepimectin ( 1346 ) + TX , polychloroterpenes ( traditional name) (CCN ) + TX , (1250 ) + TX , lindane (430 ) + TX , ( 1347 ) + TX , potassium arsenite [CCN ] + TX , potassium lirimfos ( 1251) + TX , lufenuron (490 ) + TX , lythidathion thiocyanate (CCN ] + TX , prallethrin (655 ) + TX , preco (1253 ) + TX , m -cumenyl methylcarbamate ( IUPAC cene I (alternative name) [CCN ] + TX , precocene II name) ( 1014 ) + TX , magnesium phosphide ( IUPAC (alternative name) [CCN ] + TX , precocene III (alterna name) (640 ) + TX , malathion (492 )+ TX , malonoben tive name ) ICCN1 + TX , primidophos ( 1349 ) + TX , pro ( 1254 ) + TX , mazidox ( 1255 ) + TX , mecarbam (502 ) + fenofos ( 662 ) + TX , profluthrin [ CCN ] + TX , promacyl TX , mecarphon ( 1258 ) + TX , menazon ( 1260 ) + TX , ( 1354 ) + TX , promecarb ( 1355 ) + TX , propaphos mephosfolan ( 1261) + TX , mercurous chloride (513 ) + ( 1356 ) + TX , propetamphos (673 ) + TX , propoxur (678 ) + TX , mesulfenfos ( 1263 ) + TX , metaflumizone (CCN ) + TX , prothidathion ( 1360 ) + TX , prothiofos (686 ) + TX , TX , metam (519 ) + TX , metam -potassium (alternative prothoate ( 1362) + TX , protrifenbute [CCN ] + TX , name) (519 ) + TX , metam - sodium ( 519 ) + TX , methacri pymetrozine (688 ) + TX , pyraclofos (689 ) + TX , pyrazo fos ( 1266 ) + TX , methamidophos (527 ) + TX , methane phos (693 ) + TX , pyresmethrin ( 1367) + TX , pyrethrin 1 sulfonyl fluoride ( IUPAC /Chemical Abstracts name) (696 ) + TX , pyrethrin 11 (696 ) + TX , pyrethrins (696 ) + ( 1268) + TX , methidathion (529 ) + TX , methiocarb TX , pyridaben (699 ) + TX , pyridalyl (700 ) + TX , pyrida (530 ) + TX , methocrotophos (1273 ) + TX , methomyl phenthion (701 ) + TX , pyrimidifen (706 ) + TX , pyrimi (531 ) + TX , methoprene (532 ) + TX , methoquin -butyl tate ( 1370 ) + TX , pyriproxyfen (708 ) + TX , quassia ( 1276 ) + TX , methothrin ( alternative name ) (533 ) + TX , ( alternative name) [CCN ] + TX , quinalphos (711 ) + TX , methoxychlor (534 ) + TX , methoxyfenozide (535 ) + TX , quinalphos -methyl ( 1376 ) + TX , quinothion (1380 ) + methyl bromide (537 ) + TX , methyl isothiocyanate TX , quintiofos ( 1381 ) + TX , R - 1492 (development (543 ) + TX , methylchloroform ( alternative name) code ) ( 1382 ) + TX , rafoxanide ( alternative name) [CCN ] + TX , methylene chloride [ CCN ] + TX , metoflu [ CCN ] + TX , resmethrin (719 ) + TX , rotenone (722 ) + thrin ( CCN ] + TX , metolcarb ( 550 ) + TX , metoxadiazone TX , RU 15525 (development code ) (723 ) + TX , RU ( 1288 ) + TX , mevinphos (556 ) + TX , mexacarbate 25475 (development code ) ( 1386 ) + TX , ryania ( alter ( 1290 ) + TX , milbemectin (557 ) + TX , milbemycin native name) ( 1387 ) + TX , ryanodine (traditional name) oxime (alternative name) [CCN ] + TX , mipafox ( 1293 ) + ( 1387 ) + TX , sabadilla (alternative name) (725 ) + TX , TX , ( 1294 ) + TX , monocrotophos ( 561) + TX , schradan (1389 ) + TX , sebufos (alternative name ) + TX , morphothion ( 1300 ) + TX , moxidectin (alternative selamectin (alternative name ) [CCN ] + TX , SI- 0009 name) [ CCN ] + TX , naftalofos ( alternative name) ( compound code ) + TX , SI- 0205 ( compound code ) + TX , [ CCN ] + TX , naled ( 567 ) + TX , naphthalene ( IU PACI SI- 0404 (compound code ) + TX , SI -0405 ( compound Chemical Abstracts name) ( 1303 ) + TX , NC - 170 (devel code ) + TX , (728 ) + TX , SN 72129 (develop opment code ) ( 1306 ) + TX , NC - 184 ( compound code) + ment code ) ( 1397 ) + TX , sodium arsenite [CCN ] + TX , TX , nicotine (578 ) + TX , nicotine sulfate (578 ) + TX , sodium cyanide (444 ) + TX , sodium fluoride ( IUPACI nifluridide ( 1309 ) + TX , nitenpyram (579 ) + TX , nithiaz Chemical Abstracts name) (1399 )+ TX , sodium ine ( 1311) + TX , nitrilacarb (1313 ) + TX , nitrilacarb 1 : 1 hexafluorosilicate ( 1400 ) + TX , sodium pentachlorophe zinc chloride complex (1313 ) + TX , NNI- 0101 (com noxide (623 ) + TX , sodium selenate ( IUPAC name) pound code ) + TX , NN1- 0250 ( compound code ) + TX , ( 1401 ) + TX , sodium thiocyanate [ CCN ] + TX , soph nornicotine ( traditional name ) ( 1319 ) + TX , novaluron amide ( 1402 ) + TX , spinosad ( 737 ) + TX , spiromesifen (585 ) + TX , noviflumuron (586 ) + TX , O - 5 - dichloro - 4 ( 739 ) + TX , spirotetrmat (CCN ) + TX , sulcofuron (746 ) + iodophenyl O - ethyl ethylphosphonothioate (IUPAC TX , sulcofuron - sodium (746 ) + TX , sulfluramid (750 ) + name) ( 1057 ) + TX , 0 , 0 - diethyl O - 4 -methyl - 2 -oxo - 2H TX , sulfotep (753 ) + TX , sulfuryl fluoride ( 756 ) + TX , chromen - 7 -yl phosphorothioate ( IUPAC name) sulprofos ( 1408 ) + TX , tar oils ( alternative name) ( 758 ) + ( 1074 ) + TX , 0 , 0 - diethyl 0 - 6 -methyl - 2 -propylpyrimi TX , tau - fluvalinate ( 398 ) + TX , tazimcarb ( 1412 ) + TX , din -4 -yl phosphorothioate ( IUPAC name) ( 1075 ) + TX , TDE ( 1414 ) + TX , tebufenozide ( 762 ) + TX , tebufen 0 , 0 , 0 ', O ' -tetrapropyl dithiopyrophosphate ( IUPAC pyrad ( 763 ) + TX , ( 764 ) + TX , tefluben name) ( 1424 ) + TX , oleic acid ( IUPAC name) (593 ) + zuron ( 768 ) + TX , tefluthrin ( 769) + TX , temephos TX , omethoate ( 594 ) + TX , oxamyl (602 ) + TX , ( 770 ) + TX , TEPP ( 1417 ) + TX , terallethrin ( 1418 ) + TX , oxydemeton -methyl (609 ) + TX , oxydeprofos ( 1324 ) + terbam (alternative name) + TX , terbufos (773 ) + TX , tet US 2018 /0289005 A1 Oct . 11, 2018 17

rachloroethane [CCN ] + TX , tetrachlorvinphos ( 777 ) + ( 109 ) + TX , carbofuran ( 118 ) + TX , carbon disulfide TX , tetramethrin (787 ) + TX , theta -cypermethrin ( 204 )+ ( 945 ) + TX , carbosulfan ( 119) + TX , chloropicrin ( 141) + TX , thiacloprid (791 ) + TX , thiafenox (alternative TX , chlorpyrifos (145 )+ TX , cloethocarb (999 ) + TX , name) + TX , thiamethoxam ( 792) + TX , thicrofos cytokinins ( alternative name ) ( 210 ) + TX , dazomet ( 1428 ) + TX , thiocarboxime ( 1431) + TX , thiocyclam ( 216 ) + TX , DBCP ( 1045 ) + TX , DCIP (218 ) + TX , diami ( 798 ) + TX , thiocyclam hydrogen oxalate ( 798 ) + TX , dafos (1044 )+ TX , dichlofenthion ( 1051 ) + TX , dicli thiodicarb (799 ) + TX , thiofanox (800 ) + TX , thiometon phos ( alternative name) + TX , dimethoate (262 ) + TX , (801 ) + TX , thionazin ( 1434 ) + TX , thiosultap (803 ) + TX , doramectin ( alternative name ) [ CCN ] + TX , emamectin thiosultap - sodium ( 803 ) + TX , thuringiensin ( alternative ( 291 ) + TX , emamectin benzoate ( 291 ) + TX , eprinomec name) [CCN ] + TX , tolfenpyrad ( 809 ) + TX , tralomethrin tin ( alternative name) [ CCN ] + TX , ethoprophos (312 ) + (812 ) + TX , transfluthrin (813 ) + TX , transpermethrin TX , ethylene dibromide (316 ) + TX , fenamiphos ( 326 ) + ( 1440 ) + TX , triamiphos ( 1441) + TX , triazamate (818 ) + TX , fenpyrad ( alternative name) + TX , fensulfothion TX , triazophos (820 ) + TX , triazuron ( alternative ( 1158 ) + TX , fosthiazate (408 ) + TX , fosthietan ( 1196 ) + name) + TX , trichlorfon (824 ) + TX , trichlormetaphos - 3 TX , furfural ( alternative name) [ CCN ] + TX , GY- 81 (alternative name) [ CCN ] + TX , trichloronat ( 1452 ) + (development code ) (423 ) + TX , heterophos [ CCN ] + TX , trifenofos ( 1455 ) + TX , triflumuron (835 ) + TX , TX , iodomethane ( IUPAC name) (542 )+ TX , isamido trimethacarb ( 840 ) + TX , triprene (1459 ) + TX , vamido fos ( 1230 ) + TX , isazofos ( 1231 ) + TX , ivermectin ( alter thion (847 ) + TX , vaniliprole [CCN ] + TX , veratridine native name ) [CCN ] + TX , kinetin ( alternative name) (alternative name) (725 ) + TX , veratrine alternative ( 210 ) + TX , mecarphon ( 1258 ) + TX , metam (519 ) + TX , name) (725 ) + TX , XMC (853 ) + TX , xylylcarb (854 ) + metam - potassium (alternative name ) (519 ) + TX , TX , Y1- 5302 ( compound code ) + TX , zeta - cypermethrin metam -sodium (519 )+ TX , methyl bromide (537 ) + TX , (205 ) + TX , zetamethrin (alternative name) + TX , zinc methyl isothiocyanate (543 ) + TX , milbemycin oxime phosphide ( 640 ) + TX , zolaprofos ( 1469 ) and ZXI 8901 (alternative name) [ CCN ] + TX , moxidectin (alternative ( development code ) (858 ) + TX , cyantraniliprole name ) [CCN ] + TX , Myrothecium verrucaria composi [736994 -63 - 19 + TX , chlorantraniliprole [ 500008 -45 tion ( alternative name) (565 ) + TX , NC - 184 ( compound 7 ]+ TX , cyenopyrafen [560121 - 52 - 0 ] + TX , cyflu code ) + TX , Oxamyl (602 ) + TX , phorate (636 ) + TX , metofen [ 400882 - 07 - 7 ] + TX , pyrifluquinazon [337458 phosphamidon (639 ) + TX , phosphocarb [ CCN ] + TX , 27 - 2 ] + TX , spinetoram [ 187166 - 40 - 1 + 187166 - 15 - 0 ] + sebufos ( alternative name) + TX , selamectin (alternative TX , spirotetramat [ 203313 - 25 - 1 ] + TX , sulfoxaflor name) [CCN ] + TX , spinosad ( 737 ) + TX , terbam ( alter [946578 - 00 - 3 ] + TX , flufiprole [ 704886 - 18 - 0 ] + TX , native name) + TX , terbufos ( 773 ) + TX , tetrachlorothio meperfluthrin [ 915288 -13 -0 ] + TX , tetramethylfluthrin phene ( IUPAC /Chemical Abstracts name) ( 1422 ) + TX , [ 84937 - 88 - 2 ] + TX , triflumezopyrim (disclosed in WO thiafenox ( alternative name) + TX , thionazin (1434 ) + 2012 /092115 ) + TX , a molluscicide selected from the TX , triazophos (820 ) + TX , triazuron ( alternative group of substances consisting of bis ( tributyltin ) oxide name) + TX , xylenols [ CCN ] + TX , YI -5302 (compound ( IUPAC name ) ( 913) + TX , bromoacetamide [CCN ] + code ) and zeatin (alternative name) (210 ) + TX , fluen TX , calcium arsenate ( CCN ] + TX , cloethocarb ( 999 ) + sulfone [318290 - 98 - 1 ] + TX , TX , copper acetoarsenite [ CCN ] + TX , copper sulfate [0143 ] a nitrification inhibitor selected from the group ( 172 ) + TX , fentin (347 ) + TX , ferric phosphate ( IUPAC of substances consisting of potassium ethylxanthate name) ( 352 ) + TX , metaldehyde (518 ) + TX , methiocarb [CCN ] and nitrapyrin (580 ) + TX , (530 ) + TX , niclosamide (576 ) + TX , niclosamide [0144 ] a plant activator selected from the group of olamine (576 ) + TX , pentachlorophenol (623 ) + TX , substances consisting of acibenzolar (6 ) + TX , aciben sodium pentachlorophenoxide (623 )+ TX , tazimcarb zolar- S -methyl ( 6 ) + TX , probenazole (658 ) and Rey ( 1412 ) + TX , thiodicarb ( 799 ) + TX , tributyltin oxide noutria sachalinensis extract ( alternative name) (720 ) + (913 ) + TX , trifenmorph ( 1454 ) + TX , trimethacarb TX , (840 ) + TX , triphenyltin acetate ( IUPAC name ) (347 ) [0145 ] a rodenticide selected from the group of sub and triphenyltin hydroxide (IUPAC name) ( 347 ) + TX , stances consisting of 2 - isovalerylindan - 1 , 3 -dione ( IU pyriprole [ 394730 -71 - 3 ] + TX , PAC name ) ( 1246 ) + TX , 4 - quinoxalin - 2 - ylamino )ben [0142 ] a nematicide selected from the group of sub zenesulfonamide ( IUPAC name) (748 ) + TX , alpha stances consisting of AKD - 3088 ( compound code ) + chlorohydrin [CCN ] + TX , aluminium phosphide (640 ) + TX , 1, 2 -dibromo -3 - chloropropane ( IUPAC /Chemical TX , antu (880 ) + TX , arsenous oxide (882 ) + TX , barium Abstracts name) ( 1045 ) + TX , 1 ,2 -dichloropropane ( IU carbonate (891 ) + TX , bisthiosemi (912 ) + TX , brodifa PAC /Chemical Abstracts name ) ( 1062 ) + TX , 1 , 2 -di coum (89 ) + TX , bromadiolone (91 ) + TX , bromethalin chloropropane with 1 , 3 -dichloropropene ( IUPAC ( 92 ) + TX , calcium cyanide ( 444 ) + TX , chloralose name) ( 1063 ) + TX , 1 , 3 -dichloropropene ( 233 ) + TX , ( 127 ) + TX , chlorophacinone ( 140 )+ TX , cholecalciferol 3 , 4 -dichlorotetrahydrothiophene 1 , 1 -dioxide ( IUPACI (alternative name ) (850 ) + TX , coumachlor ( 1004 ) + TX , Chemical Abstracts name ) ( 1065 ) + TX , 3 - ( 4 -chlorophe coumafuryl ( 1005 ) + TX , coumatetralyl ( 175 ) + TX , nyl) - 5 -methylrhodanine ( IUPAC name ) ( 980 ) + TX , crimidine ( 1009 ) + TX , difenacoum ( 246 ) + TX , difethia 5 -methyl - 6 - thioxo - 1 , 3 , 5 - thiadiazinan - 3 - ylacetic acid lone (249 ) + TX , diphacinone ( 273 )+ TX , ergocalciferol (IUPAC name) (1286 ) + TX , 6 - isopentenylaminopurine ( 301) + TX , flocoumafen (357 ) + TX , fluoroacetamide ( alternative name) (210 ) + TX , abamectin ( 1 ) + TX , (379 ) + TX , flupropadine ( 1183) + TX , flupropadine acetoprole [ CCN ] + TX , alanycarb ( 15) + TX , aldicarb hydrochloride ( 1183 ) + TX , gamma- HCH (430 ) + TX , ( 16 ) + TX , aldoxycarb ( 863 ) + TX , AZ 60541 ( compound HCH (430 ) + TX , hydrogen cyanide ( 444 ) + TX , code ) + TX , benclothiaz [ CCN ] + TX , benomyl (62 ) + TX , iodomethane (IUPAC name) (542 ) + TX , lindane (430 )+ butylpyridaben (alternative name ) + TX , cadusafos TX , magnesium phosphide (IUPAC name) ( 640 ) + TX , US 2018 /0289005 A1 Oct . 11, 2018

methyl bromide (537 ) + TX , norbormide ( 1318 ) + TX , [74738 -17 -3 ]+ TX , fludioxonil [ 131341- 86 - 1 ]+ TX , phosacetim (1336 ) + TX , phosphine ( IUPAC name) benalaxyl [71626 - 11 - 4 ] + TX , furalaxyl [ 57646 - 30 - 7 ] + (640 ) + TX , phosphorus [ CCN ] + TX , pindone ( 1341) + TX , metalaxyl [ 57837 - 19 - 1 ] + TX , R -metalaxyl [70630 TX , potassium arsenite [CCN ] + TX , pyrinuron ( 1371 ) + 17 - 0 ] + TX , ofurace [58810 -48 - 3 ] + TX , oxadixyl TX , scilliroside ( 1390 ) + TX , sodium arsenite [CCN ] + [77732 -09 - 3 ] + TX , benomyl [ 17804 - 35 - 2 ] + TX , car TX , sodium cyanide (444 ) + TX , sodium fluoroacetate bendazim [ 10605 - 21 - 7 ] + TX , debacarb [62732 - 91 -6 ] + (735 ) + TX , strychnine (745 ) + TX , thallium sulfate TX , fuberidazole [3878 - 19 - 1 ] + TX , thiabendazole [ CCN ] + TX , warfarin ( 851 ) and zinc phosphide (640 ) + [ 148 -79 - 8 ] + TX , chlozolinate [ 84332 - 86 - 5 ] + TX , TX , dichlozoline [ 24201 - 58 - 9 ] + TX , iprodione [ 36734 - 19 [0146 ] a synergist selected from the group of substances 7 ] + TX , myclozoline [54864 -61 - 8 ] + TX , procymidone consisting of 2 - ( 2 - butoxyethoxy ) - ethyl piperonylate [ 32809 - 16 - 8 ] + TX , vinclozoline [50471 -44 - 8 ] + TX , ( IUPAC name) ( 934 ) + TX , 5 - ( 1 , 3 -benzodioxol - 5 -yl ) - 3 boscalid [ 188425 -85 -6 ] + TX , carboxin [5234 -68 - 4 ] + hexylcyclohex - 2 - enone ( IUPAC name) (903 ) + TX , TX , fenfuram [ 24691 - 80 - 3 ] + TX , flutolanil [66332 - 96 farnesol with nerolidol (alternative name) (324 ) + TX , 5 ] + TX , mepronil [55814 -41 - 0 ] + TX , oxycarboxin MB -599 (development code ) (498 ) + TX , MGK 264 [5259 - 88 - 1 ] + TX , penthiopyrad [ 183675 - 82 - 3 ] + TX , (development code) ( 296 ) + TX , piperonyl butoxide thifluzamide [ 130000 -40 - 7 ] + TX , guazatine [ 108173 (649 )+ TX , piprotal ( 1343 ) + TX , propyl isomer (1358 ) + 90 - 6 ] + TX , dodine [2439 - 10 - 3 ] [ 112 -65 - 2 ] ( free base ) + TX , S421 ( development code) (724 ) + TX , TX , iminoctadine [13516 - 27 - 3 ] + TX , azoxystrobin ( 1393 ) + TX , sesasmolin ( 1394 ) and sulfoxide ( 1406 ) + [ 131860 - 33 - 81 + TX , dimoxystrobin [ 149961- 52 - 4 ] + TX , TX , enestroburin {Proc . BCPC , Int . Congr. , Glasgow , [0147 ] an animal repellent selected from the group of 2003 , 1 , 93 } + TX , fluoxastrobin [ 361377 -29 - 9 ] + TX , substances consisting of anthraquinone ( 32 ) + TX , chlo kresoxim -methyl [ 143390 - 89 -01 + TX , metominos ralose ( 127 ) + TX , copper naphthenate [ CCN ] + TX , cop trobin [133408 - 50 - 1 ] + TX , trifloxystrobin [ 141517 -21 per oxychloride ( 171 ) + TX , diazinon ( 227 ) + TX , dicy 7 ] + TX , orysastrobin [248593 - 16 - 0 ] + TX , picoxystrobin clopentadiene ( chemical name) ( 1069 ) + TX , guazatine [ 117428 - 22 - 5 ] + TX , pyraclostrobin [ 175013 - 18 - 0 ] + (422 ) + TX , guazatine acetates (422 ) + TX , methiocarb TX , ferbam [ 14484 -64 - 1 ] + TX , mancozeb [ 8018 -01 (530 )+ TX , pyridin - 4 -amine ( IUPAC name) ( 23 ) + TX , 7 ] + TX , maneb [ 12427 - 38 - 2 ] + TX , metiram [ 9006 - 42 thiram (804 ) + TX , trimethacarb (840 ) + TX , zinc naph 2 ]+ TX , propineb [ 12071- 83 - 9 ] + TX , thiram [ 137 -26 thenate (CCN ] and ziram (856 ) + TX , 8 ] + TX , zineb [ 12122 -67 - 7 ] + TX , ziram [ 137 - 30 - 4 ] + [0148 ] a virucide selected from the group of substances TX , captafol [ 2425 -06 - 1 ] + TX , captan [ 133 - 06 - 2 ] + TX , consisting of imanin (alternative name) [CCN ] and dichlofluanid [ 1085 - 98 - 9 ] + TX , fluoroimide [41205 ribavirin ( alternative name) [CCN ] + TX , 21 - 4 ] + TX , folpet [ 133 -07 - 3 ] + TX , tolylfluanid [731 - 27 [0149 ] a wound protectant selected from the group of 1 ] + TX , bordeaux mixture [ 8011 -63 - 0 ] + TX , copperhy substances consisting of mercuric oxide (512 ) + TX , droxid [ 20427 - 59 - 2 ] + TX , copperoxychlorid [ 1332 -40 octhilinone (590 ) and thiophanate -methyl (802 ) + TX , 7 ] + TX , coppersulfat [7758 - 98 - 7 ] + TX , copperoxid [0150 ] and biologically active compounds selected [ 1317 - 39 - 1 ] + TX , mancopper [53988 - 93 - 5 ] + TX , from the group consisting of azaconazole (60207 -31 oxine - copper [ 10380 - 28 -6 ] + TX , dinocap [ 131 - 72 - 6 ] + 0 ] + TX , bitertanol [ 70585 - 36 - 3 ] + TX , bromuconazole TX , nitrothal- isopropyl [ 10552 - 74 - 6 ] + TX , edifenphos [ 116255 -48 - 2 ] + TX , cyproconazole [ 94361- 06 - 5 ] + TX , [ 17109 -49 - 8 ] + TX , iprobenphos [ 26087 -47 - 8 ] + TX , iso difenoconazole [119446 -68 -3 ] + TX , diniconazole prothiolane [ 50512 - 35 - 1 ] + TX , phosdiphen [36519 -00 183657 - 24 - 31 + TX , epoxiconazole ( 106325 -08 -01 + TX , 3 ] + TX , pyrazophos [ 13457 - 18 - 6 ] + TX , tolclofos fenbuconazole [ 114369 - 43 - 6 ] + TX , fluquinconazole methyl 557018 - 04 - 9 ] + TX , acibenzolar - S -methyl [ 136426 -54 - 5 ] + TX , flusilazole [85509 - 19 - 9 ] + TX , flu [ 135158 - 54 - 2 ] + TX , anilazine [ 101- 05 - 3 ] + TX , benthia triafol [ 76674 - 21 - 0 ] + TX , hexaconazole [79983 -71 - 4 ] + valicarb [413615 - 35 - 7 ] + TX , blasticidin - S [ 2079 - 00 TX , imazalil [35554 -44 - 0 ] + TX , imibenconazole 7 ] + TX , chinomethionat [2439 -01 - 2 ] + TX , chloroneb [ 86598 - 92 - 7 ] + TX , ipconazole [ 125225 -28 - 7 ] + TX , [ 2675 - 77 -6 ] + TX , chlorothalonil [ 1897 -45 -6 ] + TX , metconazole [ 125116 - 23 -6 ] + TX , myclobutanil cyflufenamid [ 180409 -60 - 3 ] + TX , cymoxanil [57966 [88671 -89 - 0 ] + TX , pefurazoate [ 101903 - 30 - 4 ] + TX , 95 - 7 ] + TX , dichlone [ 117 -80 - 6 ] + TX , diclocymet penconazole [66246 -88 - 6 ] + TX , prothioconazole [ 139920 -32 -41 + TX , diclomezine [62865 -36 - 5 ] + TX , [ 178928 - 70 -6 ] + TX , pyrifenox [88283 -41 - 4 ] + TX , dicloran [99 -30 - 9 ]+ TX , diethofencarb [87130 - 20 -9 ] + prochloraz [67747 -09 - 5 ] + TX , propiconazole [ 60207 TX , dimethomorph [ 110488 -70 - 5 ] + TX , SYP - L190 90 - 1 ] + TX , simeconazole [ 149508 - 90 - 7 ] + TX , tebucon (Flumorph ) [211867 - 47 - 9 ] + TX , dithianon [ 3347 -22 azole [ 107534 - 96 - 3 ] + TX , tetraconazole [ 112281 -77 6 ] + TX , ethaboxam [ 162650 -77 - 3 ] + TX , etridiazole 3 ] + TX , triadimefon [43121 -43 -3 ] + TX , triadimenol [ 2593 - 15 -9 ] + TX , famoxadone [ 131807 -57 - 3 ] + TX , [55219 -65 - 3 ] + TX , triflumizole [99387 -89 -0 ] + TX , triti fenamidone [ 161326 - 34 - 7 ] + TX , fenoxanil [ 115852 conazole [ 131983 - 72 - 7 ] + TX , ancymidol [ 12771 -68 48 - 7 ] + TX , fentin (668 - 34 - 81 + TX , ferimzone 189269 5 ] + TX , fenarimol [ 60168 - 88 - 9 ] + TX , nuarimol [63284 64 - 7 ] + TX , fluazinam [ 79622 - 59 - 6 ] + TX , fluopicolide 71 - 9 ] + TX , bupirimate [ 41483 - 43 - 6 ] + TX , dimethirimol [ 239110 - 15 - 7 ] + TX , flusulfamide [ 106917 -52 - 6 ] + TX , [5221 - 53 - 4 ] + TX , ethirimol [23947 - 60 - 6 ] + TX , dode fenhexamid [ 126833 - 17 - 8 ] + TX , fosetyl- aluminium morph [1593 - 77 - 7 ] + TX , fenpropidine [67306 - 00 - 7 ] + [39148 -24 - 8 ] + TX , hymexazol [ 10004 -44 - 1 ] + TX , TX , fenpropimorph [67564 -91 - 4 ] + TX , spiroxamine iprovalicarb [ 140923 - 17 - 7 ] + TX , IKF - 916 ( Cyazof [118134 -30 -8 ] + TX , tridemorph [81412 -43 - 3 ] + TX , amid ) [ 120116 -88 -3 ]+ TX , kasugamycin [6980 - 18 - 3 ] + cyprodinil [ 121552 -61 -2 ] + TX , mepanipyrim [ 110235 TX , methasulfocarb [66952 -49 - 6 ] + TX , metrafenone 47 - 7 ]+ TX , pyrimethanil [53112 - 28 - 0 ] + TX , fenpiclonil [ 220899 -03 -6 ]+ TX , pencycuron [66063 - 05 - 6 ] + TX , US 2018 /0289005 A1 Oct . 11, 2018 19

phthalide [ 27355 - 22 - 2 ]+ TX , polyoxins [ 11113 -80 - 7 ] + ethyl) - 2 -pyridyl ] carbamate + TX , methyl N - [ [ 5 - [ 4 - ( 2 ,4 TX , probenazole [27605 -76 - 1 ]+ TX , propamocarb dimethylphenyl) triazol- 2 -yl ] - 2 -methyl - phenyl] methyl ] [ 25606 -41 - 1 ] + TX , proquinazid [ 189278 -12 - 4 ] + TX , carbamate + TX , 3 -chloro -6 -methyl - 5 -phenyl - 4 -( 2 ,4 , 6 pyroquilon [ 57369 - 32 - 1 ] + TX , quinoxyfen [ 124495 trifluorophenyl ) pyridazine + TX , 3 - chloro - 4 -( 2 ,6 18 - 7 ] + TX , quintozene [82 -68 - 8 ] + TX , sulfur [ 7704 -34 difluorophenyl) - 6 -methyl - 5 - phenyl -pyridazine + TX , 9 ] + TX , tiadinil [ 223580 -51 - 6 ] + TX , triazoxide [72459 3 - ( difluoromethyl ) - 1 -methyl - N - [ 1 , 1 , 3 - trimethylindan 58 - 6 ] + TX , tricyclazole [41814 -78 - 2 ]+ TX , triforine 4 - yl] pyrazole - 4 -carboxamide + TX , 1- [ 2 -[ [ 1 - (4 - chloro [26644 -46 - 2 ] + TX , validamycin [ 37248 -47 - 8 ] + TX , phenyl ) pyrazol- 3 - yl] oxymethyl] - 3 -methyl - phenyl] - 4 zoxamide (RH7281 ) [ 156052 -68 - 5 ] + TX , mandiprop methyl- tetrazol - 5 -one + TX , 1 -methyl - 4 -13 -methyl - 2 amid ( 374726 -62 - 2 ] + TX , isopyrazam [881685 - 58 - 1 ] + [ [ 2 -methyl - 4 - ( 3 , 4 , 5 - trimethylpyrazol- 1 -yl ) phenoxy ] TX , sedaxane [874967 -67 - 6 ] + TX , 3 -difluoromethyl - 1 methyl] phenyl ] tetrazol- 5 -one + TX , and methyl - 1H - pyrazole - 4 - carboxylic acid ( 9 -dichloromethylene - 1, 2 ,3 , 4 -tetrahydro - 1, 4 -methano naphthalen - 5 -yl ) -amide (dislosed in WO 2007 / 048556 ) + TX , 3 - difluoromethyl- 1 -methyl - 1H -pyra zole- 4 -carboxylic acid ( 3 ,4 , 5 - trifluoro -biphenyl - 2 yl) - amide (disclosed in WO 2006 /087343 ) + TX , [( 3S , 4R ,4aR ,6S 6S, , 12R , 12aS , 12bS ) - 3 [( cyclopropylcarbonyl) oxy ) - 1, 3 , 4, 4a , 5, 6 ,6a , 12 ,12a , 12b - decahydro -6 ,12 - dihydroxy -4 ,6a , 12b - trimethyl- 11 oxo - 9 - ( 3 - pyridinyl ) - 2H , 11Hnaphtho [ 2 , 1 - b ] pyrano [ 3 ,4 e ]pyran - 4 -yl ] methyl - cyclopropanecarboxylate NH [ 915972 - 17 - 7 ] + TX and 1 , 3 , 5 -trimethyl - N - ( 2 -methyl 1 -oxopropyl ) - N - [ 3 - ( 2 -methylpropyl ) - 4 - [ 2 , 2 , 2 - trif luoro - 1 -methoxy - 1 - (trifluoromethyl )ethyl ]phenyl ) - 1H TX . pyrazole - 4 - carboxamide [ 926914 -55 - 8 ] + TX , [0151 ] or a biologically active compound selected from the group consisting of N - [ ( 5 - chloro - 2 - isopropyl- phe [0152 ] The references in brackets behind the active ingre nyl) methyl ] - N - cyclopropyl- 3 - (difluoromethyl ) - 5 dients , e . g . [3878 - 19 - 1 ] refer to the Chemical Abstracts fluoro -1 -methyl - pyrazole - 4 -carboxamide + TX , 2 ,6 -Di Registry number. The above described mixing partners are methyl- 11 , 5H - [ 1 , 4 ] dithiino [ 2 , 3 - c : 5 , 6 - c ' ] dipyrrole - 1 , 3 , known . Where the active ingredients are included in “ The 5 , 7 (2H ,6H ) - tetrone + TX , 4 - ( 2 - bromo- 4 - fluoro - phenyl) Pesticide Manual” [ The Pesticide Manual — A World Com N -( 2 - chloro - 6 - fluoro - phenyl) - 2 , 5 - dimethyl- pyrazol - 3 pendium ; Thirteenth Edition ; Editor: C . D . S . TomLin ; The amine + TX , 3 -( difluoromethyl) -N - (7 - fluoro - 1 ,1 , 3 British Crop Protection Council] , they are described therein trimethyl- indan - 4 -yl ) - 1 -methyl - pyrazole - 4 under the entry number given in round brackets hereinabove carboxamide + TX , CAS 850881 -30 - 0 + TX , 3 - (3 , 4 for the particular compound ; for example, the compound dichloro - 1 , 2 -thiazol - 5 - ylmethoxy ) - 1 , 2 -benzothiazole “ abamectin ” is described under entry number ( 1) . Where 1 , 1 -dioxide + TX , 2 - [ 2 - [ ( 2 ,5 - dimethylphenoxy )methyl ] “ [CCN ]” is added hereinabove to the particular compound , phenyl ] - 2 -methoxy - N -methyl - acetamide + TX , 3 - ( 4 , 4 the compound in question is included in the “ Compendium difluoro - 3, 4 -dihydro - 3 ,3 -dimethylisoquinolin - 1 -yl ) of Pesticide Common Names ” , which is accessible on the quinolone + TX , 2 - [ 2 - fluoro - 6 - [ ( 8 - fluoro - 2 -methyl - 3 internet [ A . Wood ; Compendium of Pesticide Common quinolyl) oxy ] phenyl] propan - 2 - ol + TX , Names , Copyright © 1995 - 2004 ]; for example, the com Oxathiapiprolin + TX , tert -butyl N -[ 6 -[ [ [( 1 -methyltetra pound “ acetoprole ” is described under the internet address zol- 5 - yl) - phenyl- methylene ] amino ]oxymethyl ) - 2 http :/ / www .alanwood .net /pesticides /acetoprole .html pyridyl] carbamate + TX , N - [ 2 - ( 3 , 4 -difluorophenyl ) phe nyl] - 3 - ( trifluoromethyl) pyrazine - 2 - carboxamide + TX , [0153 ] Most of the active ingredients described above are 3 - ( difluoromethyl) - 1 -methyl - N -[ ( 3R )- 1 , 1 , 3 -trimethyl referred to hereinabove by a so - called “ common name” , the indan - 4 - yl ] pyrazole - 4 - carboxamide + TX , 2 , 2 , 2 - trifluo relevant " ISO common name” or another " common name” roethyl N - [ 2 -methyl - 1 - [ [ ( 4 -methylbenzoyl ) amino ] being used in individual cases . If the designation is not a methyl] propyl ] carbamate + TX , (2RS )- 2 -[ 4 - ( 4 " common name” , the nature of the designation used instead chlorophenoxy )- a , a , a -trifluoro -o - tolyl ]- 1 -( 1H - 1, 2 ,4 is given in round brackets for the particular compound ; in triazol- 1 -yl ) propan - 2 -ol + TX , (2RS ) - 2 - [ 4 - ( 4 that case, the IUPAC name, the IUPAC /Chemical Abstracts chlorophenoxy ) - a , a , a - trifluoro -o - tolyl] - 3 -methyl - 1 name, a “ chemical name” , a “ traditional name" , a " com (1H - 1 , 2 , 4 - triazol- 1 - yl) butan - 2 - ol + TX , pound name” or a “ develoment code ” is used or, if neither 2 - (difluoromethyl ) - N - [ (3R ) - 3 - ethyl- 1 , 1 - dimethyl- in one of those designations nor a “ common name” is used , an dan - 4 - yl] pyridine - 3 - carboxamide + TX , N - ( 2 , 5 - dim “ alternative name” is employed . “ CAS Reg . No” means the ethyl- 4 - phenoxy -phenyl ) -N - ethyl- N -methyl - formami Chemical Abstracts Registry Number . dine + TX , N '- [ 4 - ( 4 , 5 -dichlorothiazol - 2 - yl) oxy - 2 , 5 10154 ] The active ingredient mixture of the compounds of dimethyl- phenyl ]- N -ethyl - N -methyl - formamidine + formula ( 1 ) selected from Table X (above ) with active TX , [2 - [ 3- [2 - [1 - [ 2- [3 ,5 -bis (difluoromethyl ) pyrazol - 1 ingredients described above comprises a compound selected yl] acetyl ] - 4 - piperidyl] thiazol- 4 -yl ) - 4 , 5 from Table X (above ) and an active ingredient as described dihydroisoxazol- 5 -yl ] - 3 - chloro -phenyl ] above preferably in a mixing ratio of from 100 : 1 to 1 :6000 , methanesulfonate + TX , but- 3 -ynyl N - [6 - [ [ ( Z ) - [ ( 1 especially from 50 : 1 to 1 :50 , more especially in a ratio of methyltetrazol- 5 - yl ) -phenyl - methylene ]amino ]oxym from 20 : 1 to 1 :20 , even more especially from 10 : 1 to 1 : 10 , US 2018 /0289005 A1 Oct . 11, 2018 20 very especially from 5 : 1 and 1 : 5 , special preference being f0155 ] In a preferred embodiment the compostions given to a ratio of from 2 : 1 to 1 : 2 , and a ratio of from 4 : 1 according to the invention comprise a weight ratio of to 2 : 1 being likewise preferred , above all in a ratio of 1 : 1 , or component ( A ) to component ( B ) in the range of from 30 :1 5 : 1 , or 5 : 2 , or 5 : 3 , or 5 : 4 , or 4 : 1 , or 4 : 2 , or 4 : 3 , or 3 : 1 , or 3 : 2 , to 1 : 40 . or 2 : 1 , or 1 : 5 , or 2 : 5 , or 3 : 5 , or 4 : 5 , or 1 : 4 , or 2 : 4 , or 3 : 4 , or 10156 ] Preferred field rates of mixing partner :compound 1 : 3 , or 2 : 3 , or 1 : 2 , or 1 :600 , or 1 : 300 , or 1 : 150 , or 1 : 35 , or of formula (I ) from Table X , and also the preferred ratios of 2 :35 , or 4 : 35 , or 1 :75 , or 2 : 75 , or 4 :75 , or 1 :6000 , or 1 :3000 , mixing partner :a compound of formula ( I ) from Table X , are or 1 : 1500 , or 1 : 350 , or 2 : 350 , or 4 : 350 , or 1 : 750 , or 2 : 750 , given in the Table below for certain preferred individual or 4 : 750 . Those mixing ratios are by weight . mixing partners:

Preferred field rates of Preferred ratio of Most preferred ratio of mixing partner ( B ) : mixing partner (B ) : a mixing partner ( B ) : a compound of formula compound of formula compound of formula ( I) Mixing partner (I ) from Table X (A ) (I ) from Table X (A ) from Table X ( A ) Azoxystrobin 60 g / ha : 60 g / ha 3 : 1 to 1 : 3 5 : 4 - 4 : 5 or 60 g/ ha :75 g / ha Trifloxystrobin 60 g/ ha :60 g / ha 3 : 1 to 1 : 3 5 : 4 - 4 : 5 or 60 g/ ha: 75 g/ ha Cyproconazole 60 g / ha : 60 g /ha 3 : 1 to 1 : 3 5 : 4 - 4 : 5 or 60 g/ ha :75 g / ha Difenoconazole 75 g/ ha :60 g / ha 5 : 2 to 2 : 5 5 : 4 or 75 g/ ha : 75 g / ha Prothioconazole 70 g / ha : 60 g /ha 1 : 3 to 3 : 1 7 : 5 - 5 : 7 Or 70 g/ ha: 75 g/ ha Mefentrifluconazole 100 g/ ha : 60 g/ ha 4 : 1 to 2 : 3 5 : 3 - 5 : 2 or 150 g / ha : 60 g/ ha Bixafen 60 g / ha: 60 g/ ha 1 : 3 to 3 : 1 2 : 3 to 4 : 3 or 60 g/ ha: 75 g/ ha Fluxapyroxad 60 g / ha: 60 g / ha 1 : 3 to 3 : 1 2 : 3 to 4 : 3 or 60 g / ha : 75 g / ha Isopyrazam 125 g / ha : 60 g/ ha 1 : 3 to 3 : 1 1 : 1 to 5 : 2 Sedaxane 125 g/ ha :60 g / ha 1 : 3 to 3 : 1 1 : 1 to 5 : 2 Benzovindiflupyr 45 g / ha : 60 g / ha 1 : 2 - 2 : 1 3 : 4 - 4 : 3 , or especially most 45 g /ha :45 g/ ha preferred is 3 : 4 - 1 : 1 20 g/ ha: 60 g/ ha 1 : 4 to 4 : 1 1 : 3 to 1 : 2 or 40 g/ ha : 75 g/ ha

F

F 40 g / ha: 60 g / ha 1 : 2 to 2 : 1 3 : 2 to 2 : 3 or 60 g / ha: 60 g / ha NH

Fluindapyr US 2018 /0289005 A1 Oct . 11, 2018 21

- continued Preferred field rates of Preferred ratio of Most preferred ratio of mixing partner ( B ) : mixing partner ( B ) : a mixing partner ( B ) : a compound of formula compound of formula compound of formula ( I ) Mixing partner ( I ) from Table X ( A ) ( I ) from Table X ( A ) from Table X ( A )

130 g / ha : 60 g / ha 4 : 1 to 1 : 4 3 : 1 to 1 : 1 or 130 g / ha: 75 g/ ha

UK -2A procide ( fenpicoxamid ) Chlorothalonil 1000 g/ ha : 60 g/ ha 25 : 1 to 15 : 1 16 : 1 to 23 : 1 or 1000 g / ha : 45 g / ha. Mancozeb 1500 g/ ha : 60 g/ ha 38 : 1 to 20 : 1 24 : 1 to 34 : 1 or 1500 g / ha: 45 g/ ha

[ 0157 ] The mixtures as described above can be used in a system , increased root nodulation , increased shoot growth , method for controlling pests, which comprises applying a increased tillering, stronger tillers , more productive tillers , composition comprising a mixture as described above to the increased or improved plant stand , less plant verse ( lodging) , pests or their environment , with the exception of a method an increase and /or improvement in plant height, an increase for treatment of the human or animal body by surgery or in plant weight (fresh or dry ) , bigger leaf blades , greener leaf therapy and diagnostic methods practised on the human or colour, increased pigment content, increased photosynthetic animal body. activity , earlier flowering , longer panicles , early grain matu [0158 ] The mixtures comprising a compound of formula rity , increased seed , fruit or pod size , increased pod or ear ( 1 ) selected from Table X ( above ) and one or more active number , increased seed number per pod or ear, increased ingredients as described above can be applied , for example , seed mass , enhanced seed filling , less dead basal leaves , in a single “ ready -mix ” form , in a combined spray mixture delay of senescence, improved vitality of the plant, composed from separate formulations of the single active increased levels of amino acids in storage tissues and / or less ingredient components , such as a “ tank -mix ” , and in a inputs needed ( e . g . less fertiliser, water and /or labour combined use of the single active ingredients when applied needed ) . A plantwith improved vigour may have an increase in a sequential manner, i . e . one after the other with a in any of the aforementioned traits or any combination or reasonably short period , such as a few hours or days . The two or more of the aforementioned traits. order of applying the compounds of formula ( 1 ) selected [0162 ] According to the present invention , an ‘ improve from Table X (above ) and the active ingredients as described ment in plant quality ' means that certain traits are improved above is not essential for working the present invention . qualitatively or quantitatively when compared with the same [0159 ] The compositions of the present invention may also trait in a control plant which has been grown under the same be used in crop enhancement. conditions in the absence of the method of the invention . [ 0160 ] According to the present invention , ‘ crop enhance Such traits include , but are not limited to , improved visual ment ' means an improvement in plant vigour, an improve appearance of the plant, reduced ethylene ( reduced produc ment in plant quality , improved tolerance to stress factors , tion and / or inhibition of reception ) , improved quality of and / or improved input use efficiency . harvested material, e . g . seeds , fruits , leaves, vegetables [0161 ] According to the present invention , an ‘ improve ( such improved quality may manifest as improved visual ment in plant vigour ' means that certain traits are improved appearance of the harvested material) , improved carbohy qualitatively or quantitatively when compared with the same drate content ( e . g . increased quantities of sugar and /or trait in a control plant which has been grown under the same starch , improved sugar acid ratio , reduction of reducing conditions in the absence of the method of the invention . sugars , increased rate of development of sugar ) , improved Such traits include, but are not limited to , early and /or protein content, improved oil content and composition , improved germination , improved emergence , the ability to improved nutritional value, reduction in anti- nutritional use less seeds, increased root growth , a more developed root compounds, improved organoleptic properties (e . g . US 2018 /0289005 A1 Oct. 11 , 2018 improved taste ) and /or improved consumer health benefits over the yield of the same product of the plant produced ( e . g . increased levels of vitamins and anti -oxidants ) ) , under the same conditions, but without application of the improved post -harvest characteristics ( e . g . enhanced shelf present invention . According to the present invention , it is life and /or storage stability , easier processability , easier preferred that the yield be increased by at least 0 . 5 % , more extraction of compounds ) , more homogenous crop develop preferred at least 1 % , even more preferred at least 2 % , still ment ( e . g . synchronised germination , flowering and / or fruit more preferred at least 4 % , preferably 5 % or even more. ing of plants ) , and / or improved seed quality ( e . g . for use in [0167 ] Any or all of the above crop enhancements may following seasons ) . A plant with improved quality may have also lead to an improved utilisation of land , i. e . land which an increase in any of the aforementioned traits or any was previously unavailable or sub - optimal for cultivation combination or two or more of the aforementioned traits . may become available . For example , plants which show an [0163 ] According to the present invention , an “ improved increased ability to survive in drought conditions, may be tolerance to stress factors ' means that certain traits are able to be cultivated in areas of sub -optimal rainfall, e. g . improved qualitatively or quantitatively when compared perhaps on the fringe of a desert or even the desert itself . with the same trait in a control plant which has been grown [0168 ] In one aspect of the present invention , crop under the same conditions in the absence of the method of enhancements are made in the substantial absence of pres the invention . Such traits include , but are not limited to , an sure from pests and / or diseases and /or abiotic stress. In a increased tolerance and /or resistance to abiotic stress factors further aspect of the present invention , improvements in which cause sub - optimal growing conditions such as plant vigour, stress tolerance , quality and /or yield are made drought ( e. g . any stress which leads to a lack of water in the substantial absence of pressure from pests and / or content in plants , a lack of water uptake potential or a diseases . For example pests and /or diseases may be con reduction in the water supply to plants ) , cold exposure , heat trolled by a pesticidal treatment that is applied prior to , or at exposure , osmotic stress , UV stress , flooding, increased the same time as , the method of the present invention . In a salinity ( e. g . in the soil ), increased mineral exposure , ozone still further aspect of the present invention , improvements in exposure , high light exposure and/ or limited availability of plant vigour, stress tolerance , quality and /or yield are made nutrients ( e . g . nitrogen and /or phosphorus nutrients) . A plant in the absence of pest and /or disease pressure . In a further with improved tolerance to stress factors may have an embodiment, improvements in plant vigour, quality and /or increase in any of the aforementioned traits or any combi yield are made in the absence , or substantial absence , of nation or two or more of the aforementioned traits . In the abiotic stress. case of drought and nutrient stress, such improved toler [0169 ] The compositions of the present invention may also ances may be due to , for example, more efficient uptake , use be used in the field of protecting storage goods against attack or retention of water and nutrients . of fungi. According to the present invention , the term [0164 ] According to the present invention , an “ improved " storage goods ” is understood to denote natural substances input use efficiency ' means that the plants are able to grow of vegetable and / or animal origin and their processed forms, more effectively using given levels of inputs compared to the which have been taken from the natural life cycle and for grown of control plants which are grown under the same which long - term protection is desired . Storage goods of conditions in the absence of the method of the invention . In vegetable origin , such as plants or parts thereof, for example particular , the inputs include, but are not limited to fertiliser stalks, leafs , tubers , seeds, fruits or grains , can be protected ( such as nitrogen , phosphorous, potassium , micronutrients ) , in the freshly harvested state or in processed form , such as light and water. A plant with improved input use efficiency pre -dried , moistened , comminuted , ground , pressed or may have an improved use of any of the aforementioned roasted . Also falling under the definition of storage goods is inputs or any combination of two or more of the aforemen timber , whether in the form of crude timber , such as con tioned inputs . struction timber, electricity pylons and barriers , or in the [0165 ] Other crop enhancements of the present invention form of finished articles , such as furniture or objects made include a decrease in plant height, or reduction in tillering , from wood . Storage goods of animal origin are hides , which are beneficial features in crops or conditions where it leather , furs , hairs and the like . The composition according is desirable to have less biomass and fewer tillers . the present invention can prevent disadvantageous effects [ 0166 Any or all of the above crop enhancements may such as decay , discoloration or mold . Preferably " storage lead to an improved yield by improving e .g . plant physiol goods ” is understood to denote natural substances of veg ogy, plant growth and development and /or plant architec etable origin and / or their processed forms, more preferably ture . In the context of the present invention ‘ yield ' includes , fruits and their processed forms, such as pomes , stone fruits , but is not limited to , ( i ) an increase in biomass production , soft fruits and citrus fruits and their processed forms. In grain yield , starch content, oil content and/ or protein con another preferred embodiment of the invention " storage tent, which may result from ( a ) an increase in the amount goods” is understood to denote wood . produced by the plant per se or ( b ) an improved ability to [ 0170 ] Therefore a further aspect of the present invention harvest plant matter, ( ii ) an improvement in the composition is a method of protecting storage goods, which comprises of the harvested material ( e . g . improved sugar acid ratios , applying to the storage goods a composition according to the improved oil composition , increased nutritional value , invention . reduction of anti - nutritional compounds , increased con [0171 ] The composition of the present invention may also sumer health benefits ) and /or ( iii ) an increased / facilitated be used in the field of protecting technical material against ability to harvest the crop , improved processability of the attack of fungi . According to the present invention , the term crop and / or better storage stability / shelf life . Increased yield " technical material” includes paper ; carpets ; constructions ; of an agricultural plant means that , where it is possible to cooling and heating systems; wall -boards ; ventilation and air take a quantitative measurement, the yield of a product of conditioning systems and the like ; preferably " technical the respective plant is increased by a measurable amount material” is understood to denote wall - boards . The compo US 2018 /0289005 A1 Oct . 11, 2018

sition according the present invention can prevent disadvan rolidone, ethyl acetate , 2 - ethylhexanol, ethylene carbonate , tageous effects such as decay, discoloration or mold . 1 , 1 , 1 - trichloroethane , 2 - heptanone , alpha- pinene, d - limo [0172 ] The composition according to the is generally nene , ethyl lactate , ethylene glycol, ethylene glycol butyl formulated in various ways using formulation adjuvants, ether , ethylene glycol methyl ether, gamma -butyrolactone , such as carriers, solvents and surface -active substances. The glycerol, glycerol acetate , glycerol diacetate , glycerol triac formulations can be in various physical forms, e . g . in the etate , hexadecane , hexylene glycol, isoamyl acetate , isobor form of dusting powders , gels , wettable powders , water nyl acetate , isooctane , isophorone , isopropylbenzene, iso dispersible granules , water - dispersible tablets , effervescent propyl myristate , lactic acid , laurylamine, mesityl oxide , pellets , emulsifiable concentrates , microemulsifiable con methoxypropanol, methyl isoamyl ketone , methyl isobutyl centrates, oil - in -water emulsions, oil - flowables, aqueous ketone , methyl laurate , methyl octanoate , methyl oleate, dispersions , oily dispersions, suspo - emulsions, capsule sus methylene chloride , m - xylene , n -hexane , n - octylamine , pensions, emulsifiable granules, soluble liquids, water octadecanoic acid , octylamine acetate, oleic acid , oleylam soluble concentrates ( with water or a water - miscible organic ine , o -xylene , phenol, polyethylene glycol, propionic acid , solvent as carrier ) , impregnated polymer films or in other propyl lactate , propylene carbonate , propylene glycol, pro forms known e . g . from the Manual on Development and Use pylene glycol methyl ether, p -xylene , toluene , triethyl phos of FAO and WHO Specifications for Pesticides , United phate , triethylene glycol, xylenesulfonic acid , paraffin , min Nations, First Edition , Second Revision (2010 ). Such for eral oil , trichloroethylene , perchloroethylene , ethyl acetate , mulations can either be used directly or diluted prior to use . amyl acetate , butyl acetate , propylene glycol methyl ether, The dilutions can be made , for example , with water, liquid diethylene glycol methyl ether, methanol, ethanol, isopro fertilisers , micronutrients , biological organisms, oil or sol panol, and alcohols of higher molecular weight, such as vents . amyl alcohol, tetrahydrofurfuryl alcohol, hexanol, octanol, [0173 ] The formulations can be prepared e. g. by mixing ethylene glycol, propylene glycol, glycerol, N -methyl - 2 the active ingredientwith the formulation adjuvants in order pyrrolidone and the like . to obtain compositions in the form of finely divided solids , [0176 ] Suitable solid carriers are , for example , talc , tita granules, solutions , dispersions or emulsions. The active nium dioxide , pyrophyllite clay , silica , attapulgite clay , ingredients can also be formulated with other adjuvants, kieselguhr, limestone , calcium carbonate , bentonite , calcium such as finely divided solids , mineral oils , oils of vegetable montmorillonite , cottonseed husks , wheat flour, soybean or animal origin , modified oils of vegetable or animal origin , flour, pumice , wood flour, ground walnut shells , lignin and organic solvents , water , surface - active substances or com similar substances . binations thereof. (0177 ] A large number of surface -active substances can [0174 ] The active ingredients can also be contained in advantageously be used in both solid and liquid formula very fine microcapsules. Microcapsules contain the active tions, especially in those formulations which can be diluted ingredients in a porous carrier. This enables the active with a carrier prior to use. Surface - active substances may be ingredients to be released into the environment in controlled anionic , cationic , non - ionic or polymeric and they can be amounts ( e . g . slow -release ) . Microcapsules usually have a used as emulsifiers , wetting agents or suspending agents or diameter of from 0 . 1 to 500 microns . They contain active for other purposes . Typical surface - active substances ingredients in an amount of about from 25 to 95 % by weight include , for example , salts of alkyl sulfates , such as dietha of the capsule weight. The active ingredients can be in the nolammonium lauryl sulfate ; salts of alkylarylsulfonates , form of a monolithic solid , in the form of fine particles in such as calcium dodecylbenzenesulfonate ; alkylphenol/ solid or liquid dispersion or in the form of a suitable alkylene oxide addition products , such as nonylphenol solution . The encapsulating membranes can comprise , for ethoxylate ; alcohol/ alkylene oxide addition products , such example , natural or synthetic rubbers , cellulose , styrene/ as tridecylalcohol ethoxylate ; soaps, such as sodium stear butadiene copolymers , polyacrylonitrile , polyacrylate , poly ate ; salts of alkylnaphthalenesulfonates, such as sodium esters , polyamides , polyureas , polyurethane or chemically dibutylnaphthalenesulfonate ; dialkyl esters of sulfosucci modified polymers and starch xanthates or other polymers nate salts , such as sodium di( 2 -ethylhexyl ) sulfosuccinate ; that are known to the person skilled in the art. Alternatively , sorbitol esters , such as sorbitol oleate ; quaternary amines , very fine microcapsules can be formed in which the active such as lauryltrimethylammonium chloride, polyethylene ingredient is contained in the form of finely divided particles glycol esters of fatty acids , such as polyethylene glycol in a solid matrix of base substance, but themicrocapsules are stearate; block copolymers of ethylene oxide and propylene not themselves encapsulated . oxide ; and salts of mono - and di -alkylphosphate esters ; and [0175 ] The formulation adjuvants that are suitable for the also further substances described e . g . in McCutcheon ' s preparation of the formulations according to the invention Detergents and Emulsifiers Annual, MC Publishing Corp . , are known per se . As liquid carriers there may be used : Ridgewood N . J . ( 1981 ) . water, toluene , xylene , petroleum ether, vegetable oils , [0178 ] Further adjuvants that can be used in pesticidal acetone , methyl ethyl ketone , cyclohexanone, acid anhy formulations include crystallisation inhibitors , viscosity drides , acetonitrile , acetophenone , amyl acetate , 2 - butanone , modifiers , suspending agents, dyes , anti - oxidants , foaming butylene carbonate , chlorobenzene , cyclohexane , cyclo agents , light absorbers , mixing auxiliaries , antifoams, com hexanol , alkyl esters of acetic acid , diacetone alcohol, 1 , 2 plexing agents , neutralising or pH -modifying substances and dichloropropane, diethanolamine , p - diethylbenzene , dieth buffers , corrosion inhibitors , fragrances , wetting agents , ylene glycol, diethylene glycol abietate , diethylene glycol take -up enhancers , micronutrients , plasticisers , glidants , butyl ether, diethylene glycol ethyl ether, diethylene glycol lubricants , dispersants , thickeners, antifreezes , microbi methyl ether , N ,N -dimethylformamide , dimethyl sulfoxide , cides , and liquid and solid fertilisers . 1 , 4 - dioxane , dipropylene glycol, dipropylene glycol methyl [0179 ] The formulations according to the invention can ether , dipropylene glycol dibenzoate , diproxitol, alkylpyr- include an additive comprising an oil of vegetable or animal US 2018 /0289005 A1 Oct . 11, 2018 24. origin , a mineral oil , alkyl esters of such oils or mixtures of such oils and oil derivatives. The amount of oil additive in Wettable powders a ) b) c) the formulation according to the invention is generally from active ingredients 25 % 50 % 75 % 0 .01 to 10 % , based on the mixture to be applied . For sodium lignosulfonate 5 % 5 % example , the oil additive can be added to a spray tank in the sodium lauryl sulfate 3 % 5 % desired concentration after a spray mixture has been pre sodium diisobutylnaphthalenesulfonate 6 % 10 % phenol polyethylene glycol ether - 2 % pared . Preferred oil additives comprise mineral oils or an oil ( 7 - 8 mol of ethylene oxide ) of vegetable origin , for example rapeseed oil, olive oil or highly dispersed silicic acid 5 % 10 % 10 % sunflower oil , emulsified vegetable oil , alkyl esters of oils of Kaolin 62 % 27 % vegetable origin , for example the methyl derivatives , or an oil of animal origin , such as fish oil or beef tallow . Preferred oil additives comprise alkyl esters of C8 - C22 fatty acids , The combination is thoroughly mixed with the adjuvants and especially the methyl derivatives of C12 - C18 fatty acids , for the mixture is thoroughly ground in a suitable mill, affording example the methyl esters of lauric acid , palmitic acid and wettable powders that can be diluted with water to give oleic acid (methyl laurate , methyl palmitate and methyl suspensions of the desired concentration . oleate, respectively ) . Many oil derivatives are known from the Compendium of Herbicide Adjuvants , 10th Edition , Southern Illinois University , 2010 . Powders for dry seed treatment a ) b ) c ) [0180 ] The formulations generally comprise from 0 . 1 to active ingredients 25 % 50 % 75 % 99 % by weight, especially from 0 . 1 to 95 % by weight, of light mineral oil 5 % 5 % 5 % compounds of formula (I ) and (II ) and from 1 to 99 . 9 % by highly dispersed silicic acid 5 % 5 % weight of a formulation adjuvant which preferably includes Kaolin 65 % 40 % from 0 to 25 % by weight of a surface - active substance . Talcum — 118 Whereas commercial products may preferably be formu lated as concentrates , the end user will normally employ The combination is thoroughly mixed with the adjuvants and dilute formulations . the mixture is thoroughly ground in a suitable mill, affording 10181 ] The rates of application vary within wide limits and powders that can be used directly for seed treatment . depend on the nature of the soil, the method of application , the crop plant, the pest to be controlled , the prevailing climatic conditions, and other factors governed by the Emulsifiable concentrate method of application , the time of application and the target active ingredients 10 % crop . As a general guideline compounds may be applied at octylphenol polyethylene glycol ether 3 % a rate of from 1 to 2000 1 /ha , especially from 10 to 1000 l /ha . ( 4 - 5 mol of ethylene oxide ) [0182 ] Preferred formulations can have the following calcium dodecylbenzenesulfonate 3 % castor oil polyglycol ether (35 mol of ethylene oxide ) 4 % compositions ( weight % ) : Cyclohexanone 30 % Emulsifiable Concentrates: xylene mixture 50 % [ 0183 ] active ingredient: 1 to 95 % , preferably 60 to 90 % Emulsions of any required dilution , which can be used in surface -active agent: 1 to 30 % , preferably 5 to 20 % plant protection , can be obtained from this concentrate by liquid carrier : 1 to 80 % , preferably 1 to 35 % dilution with water. Dusts: [0184 ] active ingredient: 0 . 1 to 10 % , preferably 0 . 1 to 5 % Dusts a) b) c) solid carrier : 99 . 9 to 90 % , preferably 99. 9 to 99 % active ingredients 5 % 6 % 4 % talcum 95 % 0% * Suspension Concentrates : Kaolin 94 % [0185 ] active ingredient : 5 to 75 % , preferably 10 to 50 % mineral filler 96 % water: 94 to 24 % , preferably 88 to 30 % surface - active agent: 1 to 40 % , preferably 2 to 30 % Ready - for- use dusts are obtained by mixing the combination with the carrier and grinding the mixture in a suitable mill . Wettable Powders: Such powders can also be used for dry dressings for seed . [ 0186 ] active ingredient: 0 . 5 to 90 % , preferably 1 to 80 % surface - active agent: 0 .5 to 20 % , preferably 1 to 15 % Extruder granules solid carrier : 5 to 95 % , preferably 15 to 90 % active ingredients 15 % sodium lignosulfonate 2 % Granules : carboxymethylcellulose 1 % [0187 ] active ingredient: 0 .1 to 30 % , preferably 0 . 1 to Kaolin 82 % 15 % solid carrier : 99. 5 to 70 % , preferably 97 to 85 % The combination is mixed and ground with the adjuvants , The following Examples further illustrate , but do not limit, and the mixture is moistened with water. The mixture is the invention . extruded and then dried in a stream of air . US 2018 /0289005 A1 Oct . 11, 2018 25

example for such weight ratios is compound of formula Coated granules ( I ) :component ( B ) compound 10 : 1 . The weight ratio of active ingredients 8 % component ( A ) to component (B ) is preferably from 100 : 1 polyethylene glycol (mol . wt. 200 ) 3 % to 1 : 100 ; more preferably from 20 : 1 to 1 :50 . Kaolin 89 % [0191 ] The composition comprising the compound of for mula ( I ) and the compound of formula ( I) may show a synergistic effect. This occurs whenever the action of an The finely ground combination is uniformly applied , in a active ingredient combination is greater than the sum of the mixer , to the kaolin moistened with polyethylene glycol. actions of the individual components. The action to be Non - dusty coated granules are obtained in this manner. expected E for a given active ingredient combination obeys the so - called COLBY formula and can be calculated as follows (COLBY , S . R . “ Calculating synergistic and antago Suspension concentrate nistic responses of herbicide combination ” . Weeds, Vol . 15 , active ingredients 40 % pages 20 -22 ; 1967) : propylene glycol 10 % nonylphenol polyethylene glycol ether (15 mol of ethylene oxide) 6 % ppm = milligrams of active ingredient ( = a . i. ) per liter of spray Sodium lignosulfonate 10 % mixture carboxymethylcellulose 1 % X = % action by active ingredient A ) using p ppm of active silicone oil in the form of a 75 % emulsion in water) 1 % ingredient water 32 % Y = % action by active ingredient B ) using q ppm of active ingredient. The finely ground combination is intimately mixed with the [0192 ] According to COLBY , the expected (additive ) adjuvants , giving a suspension concentrate from which action of active ingredients A ) + B ) using p + q ppm of active suspensions of any desired dilution can be obtained by ingredient is : dilution with water. Using such dilutions, living plants as well as plant propagation material can be treated and pro tected against infestation by microorganisms, by spraying , XY pouring or immersion . E = X + Y - - 100 [0193 ] If the action actually observed ( O ) is greater than Flowable concentrate for seed treatment the expected action ( E ) , then the action of the combination active ingredients 40 % is super- additive , i. e . there is a synergistic effect. In math propylene glycol 5 % ematical terms, synergism corresponds to a positive value copolymer butanol PO / EO 2 % for the difference of ( O - E ). In the case of purely comple Tristyrenephenole with 10 - 20 moles EO 2 % 1 , 2 -benzisothiazolin - 3 - one ( in the form of a 20 % solution in 0 . 5 % mentary addition of activities (expected activity ) , said dif water ) ference ( O - E ) is zero . A negative value of said difference monoazo -pigment calcium salt 5 % ( O - E ) signals a loss of activity compared to the expected Silicone oil ( in the form of a 75 % emulsion in water ) 0 . 2 % activity . water 45 . 3 % [0194 ] However , besides the actual synergistic action with respect to fungicidal activity , the composition according to The finely ground combination is intimately mixed with the the invention may also have further surprising advantageous adjuvants, giving a suspension concentrate from which properties . Examples of such advantageous properties that suspensions of any desired dilution can be obtained by may be mentioned are: more advantageous degradability ; dilution with water. Using such dilutions, living plants as improved toxicological and / or ecotoxicological behaviour ; well as plant propagation material can be treated and pro or improved characteristics of the useful plants including : tected against infestation by microorganisms, by spraying , emergence , crop yields, more developed root system , tiller pouring or immersion . ing increase , increase in plant height, bigger leaf blade , less [0188 ] Slow Release Capsule Suspension dead basal leaves , stronger tillers, greener leaf colour, less [0189 ] 28 parts of the combination are mixed with 2 parts fertilizers needed , less seeds needed ,more productive tillers , of an aromatic solvent and 7 parts of toluene diisocyanatel earlier flowering , early grain maturity , less plant verse polymethylene -polyphenylisocyanate -mixture ( 8 : 1 ) . This ( lodging ), increased shoot growth , improved plant vigor, and mixture is emulsified in a mixture of 1. 2 parts of polyvinyl early germination . alcohol, 0 .05 parts of a defoamer and 51. 6 parts of water [0195 ] The composition according to the invention can be until the desired particle size is achieved . To this emulsion applied to the phytopathogenic microorganisms, the useful a mixture of 2 .8 parts 1 ,6 - diaminohexane in 5. 3 parts of plants , the locus thereof, the propagation material thereof, water is added . The mixture is agitated until the polymer storage goods or technical materials threatened by microor ization reaction is completed . The obtained capsule suspen ganism attack . sion is stabilized by adding 0 .25 parts of a thickener and 3 [01961 . The composition according to the invention may be parts of a dispersing agent. The capsule suspension formu applied before or after infection of the useful plants , the lation contains 28 % of the active ingredients . The medium propagation material thereof, storage goods or technical capsule diameter is 8 - 15 microns. The resulting formulation materials by the microorganisms. is applied to seeds as an aqueous suspension in an apparatus f0197 ) The amount of a composition according to the suitable for that purpose . invention to be applied , will depend on various factors, such 10190 ] In general, the weight ratio of component ( A ) to as the compounds employed ; the subject of the treatment , component ( B ) is from 2000 : 1 to 1 : 1000 . A non - limiting such as , for example plants , soil or seeds; the type of US 2018 /0289005 A1 Oct . 11, 2018

treatment, such as , for example spraying , dusting or seed Preparation of N '- [5 - bromo- 2 -methyl -6 - [ ( 1S ) - 1 dressing ; the purpose of the treatment, such as, for example methyl - 2 - propoxy - ethoxy ] - 3 -pyridyl ] - N - ethyl- N prophylactic or therapeutic ; the type of fungi to be con methyl- formamidine trolled or the application time. [0198 ] When applied to the useful plants component ( A ) is [0206 ] typically applied at a rate of 5 to 2000 g a . i. /ha , particularly 10 to 1000 g a .i . / ha , e. g . 50 , 75 , 100 or 200 g a .i ./ ha , typically in association with 1 to 5000 g a . i. /ha , particularly 2 to 2000 g a . i. / ha , e . g . 100 , 250 , 500 , 800 , 1000 , 1500 g a . i . /ha of component ( B ) . OH [0199 ] In agricultural practice the application rates of the composition according to the invention depend on the type of effect desired , and typically range from 20 to 4000 g of HO total composition per hectare . [0200 ] When the composition according to the invention is used for treating seed , rates of 0 .001 to 50 g of a compound of component (A ) per kg of seed , preferably from 0 .01 to 10 g per kg of seed , and 0 . 001 to 50 g of a compound of component ( B ), per kg of seed , preferably from 0 .01 to 10 g per kg of seed , are generally sufficient . [ 0201] For the avoidance of doubt, where a literary refer ence , patent application , or patent , is cited within the text of Br this application , the entire text of said citation is herein incorporated by reference . SYNTHETIC EXAMPLES [0202 ] Using techniques described below and techniques analogous to those described in WO 12 / 146125 (pp . 370 [0207 ] To a stirring suspension of N '- ( 5 - bromo- 6 -hy 378 ) and further techniques known to the person skilled in droxy - 2 -methyl - 3 -pyridyl ) - N -ethyl - N -methyl - formamidine the art , for example as found in WO 08 / 101682 ( pp . 22 -33 ) , (0 .75 g, 2 .8 mmol ) in THF ( 15 mL ), (2R )- 1 - propoxypropan compounds of formula ( I) may be prepared . 2 - ol ( 0. 36 g, 3 mmol, 1 .1 equiv ) and triphenylphosphine ( 0 . 80 g , 3 mmol, 1 . 1 equiv ) were added at room temperature Preparation of (2R ) - 1 -propoxypropan - 2 -ol under inert atmosphere ( Ar ) . To this mixture , DIAD ( diiso propyl diazodicarboxylate ) ( 0 .60 mL , 3 mmol, 1 . 1 equiv ) [ 0203] was added dropwise over 10 minutes while keeping the temperature below 40° C . The reaction mixture was stirred for 24h at room temperature. After this time, LC -MS indi OH + cated that the starting material had been nearly consumed V OH + < i — and the reaction mixture was quenched with water (40 mL ) . The water phase was extracted with ethyl acetate ( 3x50 mL ) . The organic layer was dried over anhydrous Na , SO , and ?? filtered . The solvent was removed in vacuo to give a brown residue , which was purified by preparative reverse phase chromatography to afford the desired ( 0 . 10 g , 10 % yield ) . [ 0204 ] To an ice - bath cooled solution of THF (400 mL ) under inert atmosphere ( Ar) charged with sodium hydride [ 0208 ] " H NMR (400 MHz , CDC13 ) : d (ppm ) 7 . 45 - 7 . 30 ( 12 g , 490 mmol, 5 equiv . ) 1 -propanol (40 mL , 490 mmol, (broad s , 1H ) , 7 .24 ( s , 1H ) , 5 . 40 - 5 . 30 ( m , 1H ) , 3 . 70 - 3 .60 ( m , 5 equiv ) was added dropwise . The ice bath was removed and 1H ) , 3 . 55 - 3 . 45 ( m , 3H ) , 3 . 45 - 3 . 30 ( broad m , 2H ) , 3 .00 ( S , the reaction mixture was stirred at room temperature for 30 3H ), 2 . 35 ( s , 3H ) , 1. 65 - 1 . 50 ( m , 2H ), 1. 35 ( m , 3H ), 1 . 20 ( m , minutes then ( 2R ) - 2 -methyloxirane ( 5 . 8 g , 99 mmol) was 3H ), 0 .90 (t , 3H ) . added dropwise and the reaction was stirred for 18h under heating at 50° C . After this time , GC -MS and NMR indi Preparation of N '- [ 5 -bromo - 2 -methyl - 6 - [ ( 1R ) - 1 cated that the starting material was consumed and the methyl -2 -propoxy - ethoxy )- 3 -pyridyl ] -N - ethyl- N reaction mixture was allowed to reach room temperature methyl- formamidine before quenching with aqueous NH _ C1 solution and extract ing with dichloromethane . The organic layer was dried over anhydrous Na , SO and filtered . The solvent was removed in [0209 ] vacuo (not dropping below 200 mbar ) at 30° C . and provided the title compound (4 .4 g , 38 % yield ) as a yellow liquid . [ 0205 ] " H NMR (400 MHz, CDC13 ): 8 (ppm ) 4 .00 - 3 . 87 ( 1H , m ) 3 . 50 - 3 . 40 ( m , 3H ), 3 .30 - 3 .20 ( m , 1H ) , 2 .64 ( d , 1H ) , OH 1 .61 ( m , 2H ) , 1 . 12 ( d , 3H ) , 0 . 95 ( t, 3H ) US 2018 /0289005 A1 Oct . 11, 2018 27

- continued -continued

A

Br Br

[ 0213 ] To a stirring suspension of N '- ( 5 -bromo -6 - hy droxy -2 -methyl - 3 -pyridyl ) - N - ethyl- N -methyl - formamidine Br ( 6 . 0 g , 22 .05 mmol) in THF (30 mL ) , 1 - propoxypropan - 2 - ol ( 3 .53 mL , 26 .46 mmol, 1. 2 equiv ) and triphenylphosphine (6 . 94 g , 26 . 46 mmol, 1 . 2 equiv ) were added at room temperature under inert atmosphere ( Ar) . To this mixture , DIAD (diisopropyl diazodicarboxylate ) ( 5 .21 mL , 26 . 46 mmol, 1 . 2 equiv ) was added dropwise over 10 minutes while keeping the temperature below 40° C . The reaction mixture [0210 ] To an ice -bath cooled solution of (2R ) -1 -propoxy was stirred for 1 . 5 h at room temperature . After this time, propan - 2 - ol ( 0 .103 g , 0 .88 mmol, 1 . 2 equiv ) in DMF ( 4 mL ) LC -MS indicated that the starting material had been con under inert atmosphere ( Ar ) , potassium tertbutoxide ( 0 .25 g , sumed and the reaction mixture was concentrated in vacuo . Heptane was added to the residue and the mixture was 2 .19 mmol, 3 equiv ) and triphenylphosphine (0 .14 g , 0 .55 cooled with an ice bath to recrystallize triphenylphosphine mmol, 1 . 5 equiv ) were added . The reaction mixture was oxide . The brown residue was purified by combiflash col stirred for 20 minutes before N '- ( 5 -bromo -6 - fluoro - 2 umn chromatography (silica gel, heptanelethyl acetate , methyl- 3 - pyridyl ) - N - ethyl - N -methyl - formamidine ( 0 . 20 g , v / v = 90 / 10 to 4 / 1 ) . Fractions containing the pure compound 0 .73 mmol) was added . The reaction mixture was stirred for were collected and concentrated in vacuo to give the title 4h at room temperature and was quenched with water upon compound ( 7 . 80 g , 95 % yield ) as a light yellow oil . completion . The water phase was extracted with ethyl [0214 ] ' H NMR (400 MHz, CDC13 ): 8 (ppm ) 7 . 45 - 7 . 30 acetate ( 2x50 mL ). The organic layers were combined , (broad s , 1H ) , 7 .24 ( s , 1H ) , 5 .40 - 5 .30 ( m , 1H ) , 3 .70 - 3 .60 ( m , washed with water (3x50 mL ) , dried over anhydrous 1H ) , 3 . 55 - 3 . 45 ( m , 3H ) , 3 . 45 - 3 . 30 ( broad m , 2H ) , 3 .00 ( s , Na2SO4 , and filtered . The solventwas removed in vacuo to 3H ), 2 . 35 ( s , 3H ) , 1 .65 - 1 . 50 ( m , 2H ) , 1. 35 ( m , 3H ), 1 . 20 ( m , give a brown residue , which was purified by preparative 3H ) , 0 . 90 (t , 3H ) . reverse phase chromatography to afford the desired com pound (0 . 130 g , 13 % yield ). Preparation of N '- [ 5 -cyano - 2 -methyl - 6 -( 1 -methyl - 2 [0211 ] " H NMR (400 MHz, CDC13 ) : 8 (ppm ) 7. 45 -7 . 30 propoxy - ethoxy )- 3 -pyridyl ] - N - ethyl- N -methyl - for (broad s, 1H ), 7 .24 ( s, 1H ), 5 .40 -5 .30 (m , 1H ), 3 .70 -3 .60 (m , mamidine 1H ) , 3 .55 - 3 .45 ( m , 3H ) , 3 . 50 - 3 . 30 (broad m , 2H ) , 3 .00 ( s , [0215 ] 3H ), 2 . 35 ( s , 3H ) , 1 .65 - 1 . 50 ( m , 2H ), 1 . 35 ( m , 3H ), 1 . 20 ( m , 3H ) , 0 . 90 ( t, 3H ) . Preparation of N '- [ 5 -bromo -2 -methyl - 6 -( 1 -methyl - 2 propoxy -ethoxy ) - 3 -pyridyl ] - N - ethyl- N -methyl - for mamidine [0212 ]

OH

HO

[0216 ] To a stirred solution of N '- [5 -bromo -2 -methyl - 6 (1 -methyl - 2 -propoxy - ethoxy) -3 -pyridyl ] - N - ethyl- N US 2018 /0289005 A1 Oct . 11, 2018 20 methyl- formamidine (0 .25 g , 0 .67 mmol) in DMF ( 1 mL ) [0222 ] To a stirred solution of o - tolylmethanol ( 3 . 99 g , under inert atmosphere ( Ar ), zinc cyanide ( 0 .087 g , 0 .74 32 . 1 mmol, 1 . 2 equiv ) in THF ( 100 mL ) , 3 -chloro - 6 -methyl mmol, 1 . 1 equiv ) and tetrakis ( triphenylphosphine )palladium 5 - nitro -pyridin - 2 -ol ( 5 . 30 g , 26 . 7 mmol) and triphenylphos (0 . 23 g , 0 .20 mmol, 0 . 3 equiv ) were added and the reaction phine ( 8 .41 g , 32 . 1 mmol, 1 . 2 equiv ) were added at room mixture was stirred for 18h under heating at 120° C . After temperature under inert atmosphere ( Ar ) . To this mixture, this time, TLC and LC -MS indicated that the starting DIAD ( diisopropyl diazodicarboxylate ) (6 .58 mL , 33 . 4 material was consumed and the reaction mixture was mmol, 1 . 25 equiv ) was added dropwise over 10 minutes allowed to reach room temperature before quenching with while keeping the temperature below 40° C . The reaction water . The water phase was extracted with ethyl acetate mixture was stirred for 16 h at room temperature . At this ( 2x30 mL ) . The organic layer was washed with brine ( 3x50 time, LC -MS indicated that the starting material was con mL ) , dried over anhydrous Na2SO4 and filtered . The solvent sumed and the reaction mixture was quenched with water was removed in vacuo to give a brown residue , which was ( 20 mL ). A precipitate formed and was filtered and washed purified by combiflash column chromatography ( silica gel, with a mixture of methanol/ water ( v / v = 5 / 1 ) , suspended in heptane/ ethyl acetate, v / v = 90 / 10 to 70 /30 ) . Fractions con toluene and concentrated in vacuo to give the title compound taining the pure compound were collected and concentrated ( 5 . 28 g , 47 % yield ) as a yellow solid . in vacuo to give the title compound ( 0 . 207 g , 97 % yield ) as [0223 ] 'H NMR (400 MHz , DMSO ): 8 (ppm ) = 8 .60 ( s, a colorless oil . 1H ), 7. 45 ( d , 1H ), 7 .30 -7 .20 (m , 3H ), 5 .50 (s , 2H ), 2 .70 ( s, [0217 H NMR (400 MHz, CDC1z ) : 8 (ppm ) 7 .45 - 7 .30 3H ) , 2 .35 ( s , 3H ) . ( broad s , 1H ) , 7 . 20 ( s , 1H ) , 5 . 50 - 5 . 40 ( m , 1H ), 3 . 70 - 3 .60 ( m , 1H ) , 3 .55 - 3 . 40 ( m , 3H ) , 3 . 45 - 3 . 30 ( broad m , 2H ) , 3 .00 ( s , Preparation of 3H ), 2 . 40 ( s , 3H ) , 1. 65 - 1 . 50 ( m , 2H ), 1 . 35 ( m , 3H ), 1 . 20 ( m , 6 -benzyloxy - 5 - chloro - 2 -methyl - pyridin - 3 -amine 3H ) , 0 . 90 ( t, 3H ) . [0224 ] Preparation of 3 - chloro - 6 -methyl - 5 - nitro - pyridin - 2 -ol [ 0218 ]

HO HO NO2

NO2 NO2 0219 ] To an ice - bath cooled suspension of 6 -methyl - 5 nitro - pyridin - 2 -ol ( 0 .50 g , 3 . 24 mmol) in acetonitrile ( 5 mL ) under inert atmosphere ( Ar ) , was added N - chlorosuccinim NH2 ide (0 .43 g, 3 .24 mmol , 1 equiv ) was added portionwise . The reaction mixture was stirred for 20h under heating at 67° C . [0225 ] A solution of 2- benzyloxy - 3 -chloro -6 -methyl - 5 At this time, LC -MS indicated that the starting material was nitro -pyridine ( 250 mg, 0 . 90 mmol) , 10 % platinum on consumed and the reaction mixture was cooled to 0° C . and carbon ( 12 mg, 0 . 062 mmol) in THF ( 5 mL ) was placed the precipitate was filtered to give the title compound ( 0 . 36 under hydrogen ( 3 equiv ., 2 . 70 mmol ) pressure of 3 bar and g , 48 % yield ) as a beige -white solid . the reaction was stirred for 18 h at 37° C . After this time, TLC indicated that the starting material has been consumed . [ 0220 ] H NMR ( 400 MHz, CD , OD ): 8 (ppm ) 8 . 5 ( s, 1H ) , The reaction mixture was filtered and the residue was 2 . 7 ( s , 3H ) . washed with methanol. The organic layer was concentrated to give the title compound ( 0 .216 g , 97 % yield ) which was Preparation of 5 -chloro - 2 methyl- - 3 - nitro - 6 -( 0 -tolyl used without further purification . methoxy )pyridine [ 02261 H NMR (400 MHz, CDC12 ) : 8 (ppm ) 7 .50 - 7 . 45 [ 0221 ] ( m , 1H ) , 7 .25 - 7 .15 ( m , 3H ) , 7 . 0 ( s , 1H ) , 5 .35 ( s , 2H ) , 3 .40 - 3 . 10 (broad s, 2H ), 2 .42 (s , 3H ), 2 .30 (s , 3H ). Preparation of N '- ( 5 - chloro - 6 - hydroxy - 2 -methyl - 3 HONYHO pyridyl ) - N - ethyl- N -methyl - formamidine [0227 ] NO2

NO2 NH2 US 2018 /0289005 A1 Oct. 11 , 2018

- continued under heating at 60° C . After this time, triphenylphosphine ( 0 . 15 g , 0 . 55 mmol, 0 . 5 equiv ) and DIAD ( diisopropyl diazodicarboxylate ) ( 0 .11 mL , 0 .55 mmol, 0 . 5 equiv ) were HO V added again and the reaction mixture wasfurther stirred for H04 9 h . The reaction mixture was allowed to reach room temperature before quenching with water ( 10 mL ) and 2M NaOH aqueous solution ( 2 mL ). [0232 ] The water phase was extracted with ethyl acetate [ 0228 ] To a solution of N - ethyl- N -methyl - formamide (1x25 mL ) . The organic layers were combined , dried over ( 1 . 29 g , 14 .76 mmol, 1. 1 equiv ) in dichloromethane (70 mL ) anhydrous Na2SO4 and filtered . The solvent was removed in was added phosphorus oxychloride ( 1. 38 mL , 14 .76 mmol, vacuo to give a brown residue , which was purified by 1 . 1 equiv ) . The solution was stirred for 1 . 5 h at room combiflash column chromatography ( silica gel, heptane/ temperature and then a solution of 5 - chloro - 2 -methyl - 6 - ( 0 ethyl acetate , v / v = 9 / 1 to 1 / 1 ) . Fractions containing the pure tolylmethoxy )pyridin - 3 - amine ( 3 . 52 g , 13 . 41 mmol) in compound were collected and concentrated in vacuo to give dichloromethane ( 10 mL ) was added dropwise . After being the title compound ( 0 . 19 g , 53 % yield ) as an yellow oil. stirred for 20 h at room temperature the solid was filtered and washed with dichloromethane . The residue was purified [0233 ] ' H NMR (400 MHz, CDC13 ) : 8 (ppm ) 7 .45 - 7 . 30 by combiflash column chromatography ( silica gel, dichlo (broad s , 1H ) , 7 .05 ( s , 1H ) , 5 . 40 - 5 . 30 ( m , 1H ) , 3 .70 - 3 .60 ( m , romethane /methanol + 5 % triethylamine v / v = 10 / 0 to 9 / 1 ) . 1H ) , 3 . 55 - 3 . 40 ( m , 3H ) , 3 . 45 - 3 . 30 (broad m , 2H ) , 3 . 00 ( s , Fractions containing the compound were collected and con 3H ), 2 . 35 ( s , 3H ) , 1 .65 - 1 . 50 ( m , 2H ) , 1. 35 ( m , 3H ), 1 . 20 ( m , centrated in vacuo to give the title compound ( 2 . 52 g , 82 % 3H ), 0 . 85 ( t, 3H ) . yield ) as a yellow solid . [0229 ] ' H NMR (400 MHz, CD ,OD ): 8 (ppm ) 7 .65 - 7 .50 Preparation of 5 - bromo - 2 -methyl - 6 -( 1 -methyl - 2 ( broad s , 1H ) , 3 . 50 - 3 . 30 (broad s , 1H ) , 3 . 0 ( s , 2H ) , 2 .25 ( s , propoxy -ethoxy ) -3 - nitro -pyridine 3H ) , 1 . 35 ( m , 3H ) , 1 .25 ( m , 3H ) . [0234 ] Preparation of N '- [5 - chloro - 2 -methyl - 6 - ( 1 -methyl - 2 propoxy - ethoxy ) - 3 -pyridyl ]- N - ethyl- N -methyl - for mamidine + [0230 ] OH

+ HO OH

HO

Br

[0235 ] To a stirred suspension of 3 - bromo - 6 -methyl - 5 nitro - pyridin - 2 - ol ( 0 .23 g , 1 mmol) in THF ( 0 .08 mL ) , 1 -propoxypropan - 2 - ol ( 0 . 15 g , 1 . 2 mmol, 1 . 2 equiv ) and triphenylphosphine (0 .32 g , 1. 2 mmol, 1. 2 equiv ) were added at room temperature under inert atmosphere ( Ar) . To this mixture , DIAD ( diisopropyl diazodicarboxylate ) ( 0 . 24 mL , 1. 2 mmol, 1. 2 equiv ) was added dropwise over 10 minutes while keeping the temperature below 40° C . The [0231 ] To a stirred solution of N '- (5 -chloro -6 -hydroxy - 2 reaction mixture was stirred for 12h under heating at 65° C . methyl- 3 -pyridyl ) - N -ethyl - N -methyl - formamidine ( 0 .25 g , After this time, LC -MS still showed remaining starting 1 . 10 mmol) in THF ( 10 mL ), 1 - propoxypropan - 2 -ol ( 0 . 14 g , material but the reaction mixture was allowed to reach room 1 . 21 mmol, 1 . 1 equiv ) and triphenylphosphine ( 0 .32 g , 1 .21 temperature and the solvent was removed in vacuo to give mmol, 1 . 1 equiv ) were added at room temperature under a brown residue, which was purified by combiflash column inert atmosphere (Ar ) . To this mixture , DIAD ( diisopropyl chromatography (silica gel , heptane /triethylamine , v / v = 95 / diazodicarboxylate ) (0 .24 mL , 1. 21 mmol, 1. 1 equiv ) was 5 ) . Fractions containing the pure compound were collected added dropwise over 10 minutes while keeping the tempera and concentrated in vacuo to give the title compound ( 0 . 20 ture below 40° C . The reaction mixture was stirred for 16h 8 , 60 % yield ) as a beige oil . US 2018 /0289005 A1 Oct . 11, 2018 30

10236 ]. H NMR (400 MHz, CDC1z) : 8 (ppm ) 8 . 45 (s , 1H ), - continued 5 .50 -5 .40 ( m , 1H ), 3. 65 - 3 .60 (m , 1H ) , 3 .65 - 3. 50 (m , 1H ), 3 .50 -3 .35 (m , 2H ), 2 .70 (s , 3H ), 1 .50 (m , 2H ), 1 . 30 (m , 3H ), 0 .80 ( t , 3H ) . O . Preparation of 5 -bromo - 2 -methyl - 6 - (1 -methyl -2 propoxy - ethoxy )pyridin - 3 -amine [ 0237 ] Br

NH

[0241 ] To a solution of N -ethylformamide (0 . 070 mL , BE ANO 0 . 91 mmol, 1. 1 equiv ) in dichloromethane (6 .6 mL ) was added phosphorus oxychloride (0 .085 mL , 0 .91 mmol , 1 .1 OEZ equiv ) . The solution was stirred for 1 h at room temperature . Then a solution of 5 -bromo - 2 -methyl - 6 - ( 1 -methyl - 2 propoxy - ethoxy )pyridin - 3 -amine (0 .25 g , 0 .83 mmol) in dichloromethane ( 3 mL ) was added dropwise . The suspen sion was stirred for 2 h at room temperature then poured onto a mixture of 2N aqueous NaOH solution ( 25 mL ) and Br NH2 ice . The aqueous layer was separated , extracted with dichlo romethane ( 2x15 mL ) . The organic phase was washed with [ 0238 ] To a stirred suspension of 5 -bromo -2 -methyl - 6 -( 1 2N aqueous NaOH solution ( 25 mL ) and brine (25 mL ) , methyl- 2 - propoxy - ethoxy ) - 3 - nitro -pyridine ( 0 .47 g , 1 .41 dried over anhydrous Na2SO4 and filtered . The solvent was mmol) in ethanol ( 10 mL ) were added ammonium chloride removed in vacuo to give a dark yellow residue , which was ( 0 . 15 g , 2 . 82 mmol, 2 equiv ) , water ( 2 . 8 mL ) and then iron purified by reverse phase preparative HPLC to give the title powder ( 0 . 32 g , 5 .64 mmol, 4 equiv ) . The reaction mixture compound ( 0 .09 g , 29 % yield ) as an orange - brown oil. was stirred for 4h under heating at 85° C . As reaction [0242 ] H NMR (400 MHz, CDC1z ): 8 (ppm ) 7 .45 (s , 1H ), monitoring still showed remaining starting material, ammo 7 . 25 ( s , 1H ) , 5 . 40 - 5 . 30 ( m , 1H ) , 4 .70 - 4 . 50 (broad s , 1H ) , nium chloride ( 0 .75 g , 1 .41 mmol, 1 equiv ) and iron powder 3 . 75 - 3 . 60 ( m , 1H ) , 3 .55 - 3 . 45 ( m , 3H ) , 3 .50 - 3 . 35 ( broad m , ( 0 . 16 g , 2 . 82 mmol, 2 equiv ) were added and reaction 2H ) , 2 . 30 ( s , 3H ) , 1 .60 - 1 . 50 ( m , 2H ) , 1 . 35 ( m , 3H ) , 1 . 25 ( m , mixture was further stirred for 10 h under heating at 85° C . 3H ) , 0 . 80 ( t , 3H ) . After this time, LC -MS indicated that the starting material has been consumed and the reaction mixture was allowed to Preparation of N '- [ 5 -bromo - 2- methyl - 6 -( 1 -methyl - 2 reach room temperature before filtering it over celite . The propoxy - ethoxy )- 3 -pyridyl ] - N -methyl - formamidine solvent was removed in vacuo and the residue was redis solved with ethyl acetate ( 15 mL ) . The organic phase was [0243 ] washed with a 2N aqueous NaOH solution ( 2x25 mL ) , dried over anhydrous Na , So , and filtered . The solvent was removed in vacuo to give a brown residue, which was purified by combiflash column chromatography ( silica gel, heptane/ ethyl acetate + 10 % triethylamine , v / v = 10/ 0 to 1 / 1 ) . Fractions containing the pure compound were collected and concentrated in vacuo to give the title compound ( 0 . 27 g , 63 % yield ) as an orange -brown oil . V NH2 10239 ) ? H NMR (400 MHz, CDC1, ) : 8 (ppm ) 7 . 10 ( s , 1H ) , 5 .25 - 5 . 15 ( m , 1H ) , 3 .65 - 3 .60 ( m , 1H ) , 3 .55 - 3 .50 ( m , 3H ) , 3 .50 - 3 . 35 (broad m , 2H ) , 2 . 20 ( s , 3H ) , 1 .50 ( m , 2H ) , 1 . 25 ( m , 3H ) , 0 . 80 ( t, 3H ) . Preparation of N ' -[ 5 -bromo - 2 -methyl - 6 -( 1- methyl - 2 propoxy - ethoxy ) -3 -pyridyl ]- N - ethyl- formamidine Br [0240 ]

[0244 ] To a solution of N -methyl N - ethylformamide ( 0 . 30 g , 2 .37 mmol, 1 . 1 equiv , 80 % wt. ) in dichloromethane ( 4 . 0 mL ) was added phosphorus oxychloride (0 .20 ml , 2 .2 Br "NH2 mmol, 1 . 1 equiv ) . The solution was stirred for 1 h at room temperature . Then a solution of 5 - bromo- 2 -methyl -6 - ( 1 US 2018 /0289005 A1 Oct. 11 , 2018 31 methyl- 2 - propoxy - ethoxy) pyridin - 3 - amine ( 0 .60 g , 2 . 0 solvent was removed in vacuo to give a dark yellow residue , mmol) in dichloromethane ( 0 .5 mL ) was added dropwise . which was purified by reverse phase preparative HPLC to The suspension was stirred for 2h at room temperature , then give the title compound ( 0 .30 g , 40 % yield ) as an orange oil . poured onto a mixture of 2N aqueous NaOH solution (25 mL ) and ice . The aqueous layer was separated , extracted [0245 ] " H NMR ( 400 MHz, CDC13 ): 8 ( ppm ) 7 .47 (broad with dichloromethane (2x15 mL ) . The organic phase was s , 1H ) , 7 . 25 ( s , 1H ) , 5 . 40 - 5 . 30 ( m , 2H ) , 3 .70 - 3 .64 ( m , 3H ) , washed with 2N aqueous NaOH solution ( 25 mL ) and brine 3 .60 - 3 .40 ( m , 3H ) , 2 . 94 (broad s , 2H ) 2 .35 ( d , 3H ) , 1 .65 - 1 . ( 25 mL ) , dried over anhydrous Na2SO4 and filtered . The 50 ( m , 2H ), 1. 35 (m , 3H ) , 1 .25 ( m , 6H ), 0 . 90 (t , 3H ). TABLE 67 This table gives analytical data for compounds of formula (I ) prepared using techniques analogous to those above , as well as those described in WO 12 / 146125 ( pp. 370 -378 ) and further techniques known to the person skilled in the art, for example as found in WO 08 / 101682 (pp . 22 - 33 ).

LC -Method : R , (min ) ; Compound MS- ESI No. Structural formula ( m / z ; ( M + H ) *) ; 67. 001 Method 1 0 . 9 min .; 337

HN NN

5 - [ [ ethyl( methyl ) amino ]methyleneamino ] - 6 methyl- 2 - ( 1- methyl - 2 -propoxy ethoxy )pyridine -3 - carboxamide

67 .002 Method 1 0 .76 min . ; Iillllll 372 Br

N ' - [ 5 -bromo - 2 -methyl - 6 - [ ( 1S ) - 1 -methyl - 2 propoxy - ethoxy )- 3 -pyridyl ] -N - ethyl- N -methyl formamidine

67 . 003 Method 1 0 . 76 min . ; 372 Br

N '- [5 -bromo - 2 -methyl - 6 - [ (1R ) -1 -methyl - 2 propoxy -ethoxy ]- 3 -pyridyl ] - N - ethyl - N -methyl formamidine US 2018 /0289005 A1 Oct. 11 , 2018 32

TABLE 67 -continued This table gives analytical data for compounds of formula (I ) prepared using techniques analogous to those above, as well as those described in WO 12 / 146125 (pp . 370 -378 ) and further techniques known to the person skilled in the art, for example as found in WO 08 / 101682 (pp . 22 -33 ) .

LC -Method : R , (min ); Compound MS - ESI No . Structural formula ( m / z ; ( M + H ) * ) ;

67 .004 Method 1 0 . 8 min . ; 361

IN

5 - [[ ethyl( methyl ) amino ]methyleneamino ] N , N , 6 -trimethyl - 2 - ( 1 -methyl - 2 -propoxy ethoxy )pyridine - 3 -carboxamide

67 .005 Method 1 0 . 8 min . ; 351

N

5 - [[ ethyl (methyl ) amino ]methyleneamino ]- N ,6 dimethyl- 2 - ( 1 -methyl - 2 - propoxy ethoxy )pyridine - 3 -carboxamide

67 .006 Method 1 0 . 7 min . ; 338

?? NON

5 - [[ ethyl( methyl ) amino )methyleneamino ] - 6 methyl - 2 - ( 1- methyl - 2 -propoxy ethoxy) pyridine - 3 - carboxylic acid US 2018 /0289005 A1 Oct. 11 , 2018 33

TABLE 67 -continued This table gives analytical data for compounds of formula ( I) prepared using techniques analogous to those above, as well as those described in WO 12 /146125 (pp . 370 -378 ) and further techniques known to the person skilled in the art, for example as found in WO 08 / 101682 ( pp . 22 - 33 ) . LC -Method : R , (min ) ; Compound MS- ESI No . Structural formula ( m / z ; ( M + H ) ) ; 67. 007 NO Method 1 0 .78 min . ; 319

.

N - [ 5 - cyano - 2 -methyl - 6 - ( 1 -methyl - 2 -propoxy ethoxy ) - 3 -pyridyl ] - N - ethyl- N -methyl formamidine 67 .008 oil

DovBr N '- [ 5- bromo - 2 - methyl - 6 - (1 - methyl - 2 - propoxy ethoxy )- 3- pyridyl ] - N - isopropyl- N -methyl formamidine 67 .009 Method 2 13 .04 min . ; 342

N ' - [ 5 - ( difluoromethyl) - 2 -methyl - 6 - ( 1 -methyl - 2 propoxy - ethoxy ) - 3 - pyridyl ]- N - ethyl - N -methyl formamidine

67 .010 Method 1 Y N Methoden0 . 85 min. ; 360

F F

N '- [ 5 - (difluoromethoxy ) - 2 -methyl - 6 - ( 1 -methyl 2 -propoxy - ethoxy ) -3 -pyridyl ]- N - ethyl - N methyl- formamidine US 2018 /0289005 A1 Oct. 11 , 2018 34

TABLE 67 -continued This table gives analytical data for compounds of formula ( I) prepared using techniques analogous to those above , as well as those described in WO 12/ 146125 (pp . 370 - 378 ) and further techniques known to the person skilled in the art , for example as found in WO 08 / 101682 (pp . 22 - 33 ).

LC -Method : R , (min ) ; Compound MS - ESI No. Structural formula ( m / z ; ( M + H ) " ) ; 67. 011 Method 1 0 .79 min . ; 308

N ' - [ 2 , 5 -dimethyl - 6 - ( 1 -methyl - 2 -propoxy ethoxy ) - 3 -pyridyl ] - N -ethyl - N -methyl formamidine 67 .012 Method 1 0 .67 min. ; 294

NON

N ' - [2 -methyl -6 - ( 1- methyl - 2 -propoxy -ethoxy ) 3 -pyridyl ] - N -ethyl - N -methyl - formamidine

67 .013 N . 0 . Method 1 0 .76 min . ; ryo 372 Br

N '- [ 5 -bromo - 2 -methyl -6 - ( 1 -methyl - 2 - propoxy ethoxy )- 3 - pyridyl] - N - ethyl- N -methyl formamidine 67 .014 Method 3 1 . 08 min . ; 326

N '- [6 - ( 2 - allyloxy - 1 -methyl - ethoxy )- 5 -chloro - 2 methyl - 3 -pyridyl ] - N -ethyl - N -methyl formamidine US 2018 /0289005 A1 Oct. 11 , 2018 35

TABLE 67 -continued This table gives analytical data for compounds of formula ( I) prepared using techniques analogous to those above , as well as those described in WO 12 /146125 (pp . 370 - 378 ) and further techniques known to the person skilled in the art , for example as found in WO 08 / 101682 (pp . 22- 33 ) .

LC -Method : R , (min ); Compound MS- ESI No . Structural formula ( m /z ; (M + H ) * ) ;

67. 015 Method 1 1 . 11 min . ; 328

N '- [5 - chloro -2 - methyl - 6 - (1 - methyl - 2 - propoxy ethoxy ) - 3 -pyridyl ]- N -ethyl - N -methyl formamidine

67 .016 O . Method 3 1. 02 min .; 400

Br

N '- [6 - [ 1 - (allyloxymethyl ) - 2 -methoxy - ethoxy ]- 5 bromo - 2 -methyl - 3 -pyridyl ] - N - ethyl- N -methyl formamidine

67 .017 O Method 3 0 . 96 min . : 317

N '- [ 6 -( 2 -allyloxy -1 -methyl - ethoxy )- 5 - cyano - 2 methyl- 3 -pyridyl ] - N - ethyl- N -methyl formamidine 67 .018 beroO oil N '- [5 -bromo - 2 -methyl -6 - ( 1 -methyl - 2 - propoxy ethoxy) - 3 -pyridyl ] - N - isopropyl - N -methyl formamidine US 2018 /0289005 A1 Oct. 11 , 2018 36

TABLE 67 -continued This table gives analytical data for compounds of formula (I ) prepared using techniques analogous to those above , as well as those described in WO 12 / 146125 (pp . 370 - 378 ) and further techniques known to the person skilled in the art , for example as found in WO 08/ 101682 (pp . 22- 33 ).

LC -Method : R , (min ) ; Compound MS- ESI No . Structural formula (m /z ; (M + H )* ) ;

67. 019 Method 1 0 .80 min . ; 352

N N

Methyl 5 [ [ ethyl( methyl ) amino ]methyleneamino ] -6 methyl- 2 -( 1 -methyl - 2 -propoxy ethoxy )pyridine - 3 -carboxylate

67 .020 Method 3 1 . 33 min . ; 422

F

N ' - [ 5 - cyano - 2 -methyl - 6 - [ 1 -methyl - 2 - [ 3 ( trifluoromethyl) phenoxy ] ethoxy ]- 3 -pyridyl ]- N ethyl - N -methyl - formamidine US 2018 /0289005 A1 Oct. 11 , 2018 37

TABLE 67 -continued This table gives analytical data for compounds of formula (I ) prepared using techniques analogous to those above , as well as those described in WO 12 / 146125 (pp . 370 - 378 ) and further techniques known to the person skilled in the art , for example as found in WO 08/ 101682 (pp . 22- 33 ).

LC -Method : R , (min ) ; Compound MS- ESI No . Structural formula (m /z ; (M + H )* ) ;

67 .021 Method 3 1 .29 min . ; 387

N '- [ 6 - [2 - (4 -chlorophenoxy ) - 1 -methyl - ethoxy ] 5 - cyano - 2 -methyl - 3 -pyridyl ]- N - ethyl- N -methyl formamidine

67 .022 Method 3 1 .21 min . ; 353

ma AN

N '- [5 -cyano -2 -methyl - 6 - ( 1- methyl - 2 -phenoxy ethoxy )- 3 -pyridyl ]- N -ethyl - N -methyl formamidine US 2018 /0289005 A1 Oct. 11 , 2018 38

TABLE 67 -continued This table gives analytical data for compounds of formula (I ) prepared using techniques analogous to those above , as well as those described in WO 12 / 146125 (pp . 370 - 378 ) and further techniques known to the person skilled in the art , for example as found in WO 08/ 101682 (pp . 22- 33 ).

LC -Method : R , (min ) ; Compound MS- ESI No . Structural formula (m /z ; (M + H )* ) ;

67. 023 Method 3 1 .38 min . ; 430

N '- [ 5 - chloro - 2 -methyl - 6 - 11- methyl - 2 - [ 3 ( trifluoromethyl) phenoxyJethoxy ] - 3 - pyridyl] - N ethyl -N -methyl -formamidine

67 .024 Method 3 1 . 38 min . ; 396

N ' - [5 -chloro -6 - [ 2 - ( 4 - chlorophenoxy )- 1 -methyl ethoxy )- 2 -methyl - 3 - pyridyl] - N -ethyl - N -methyl formamidine US 2018 /0289005 A1 Oct. 11 , 2018 39

TABLE 67 -continued This table gives analytical data for compounds of formula (I ) prepared using techniques analogous to those above , as well as those described in WO 12 / 146125 (pp . 370 - 378 ) and further techniques known to the person skilled in the art , for example as found in WO 08/ 101682 (pp . 22- 33 ).

LC -Method : R , (min ) ; Compound MS- ESI No . Structural formula (m /z ; (M + H )* ) ;

67. 025 Method 3 1 . 23 min . ; 362

O

N ’ - 15 -chloro - 2 -methyl - 6 - ( 1 -methyl - 2 - phenoxy ethoxy ) - 3 -pyridyl ]- N - ethyl- N -methyl formamidine

67 .026 Method 3 1 . 37 min . ; 440

C

Br

N '- [5 -bromo - 6 - [ 2 - ( 4 - chlorophenoxy ) - 1 -methyl ethoxy )- 2 -methyl - 3 - pyridyl] - N -ethyl - N -methyl formamidine US 2018 /0289005 A1 Oct. 11 , 2018 40

TABLE 67 -continued This table gives analytical data for compounds of formula (I ) prepared using techniques analogous to those above , as well as those described in WO 12/ 146125 (pp . 370 - 378) and further techniques known to the person skilled in the art , for example as found in WO 08 /101682 (pp . 22 - 33) .

LC -Method : R , (min ); Compound MS - ESI No . Structural formula ( m / z ; ( M + H ) ') ;

67. 027 Method 3 1 . 42 min . ; 474

Br

N '- / 5- bromo - 2 -methyl - 6 -[ 1 -methyl - 2 - [3 ( trifluoromethyl) phenoxy ] ethoxy ]- 3 -pyridyl ] - N ethyl- N -methyl - formamidine

67 .028 Method 3 1 . 25 min . ; 406

N '- [ 5 -bromo - 2 -methyl - 6 - ( 1 -methyl - 2 -phenoxy ethoxy ) -3 -pyridyl ]- N - ethyl- N -methyl formamidine

67. 029 O . Method 1 0 .77 min . : 371 4W' N V Br N '- [5 - bromo- 2 -methyl - 6 - ( 1 -methyl - 2 -propoxy ethoxy )- 3 -pyridyl ] - N - cyclopropyl- N -methyl formamidine US 2018 /0289005 A1 Oct. 11 , 2018 41

TABLE 67 -continued This table gives analytical data for compounds of formula ( I) prepared using techniques analogous to those above, as well as those described in WO 12 /146125 (pp . 370 -378 ) and further techniques known to the person skilled in the art, for example as found in WO 08 / 101682 ( pp . 22 - 33 ) . LC -Method : R , (min ) ; Compound MS- ESI No . Structural formula ( m / z ; ( M + H ) ) ; 67 .030 NO_ Method 1 0 .76 min . ; 385 Br

1 - ( azetidin - 1 - yl) - N - [ 5 -bromo - 2 -methyl - 6 - ( 1 methyl- 2 -propoxy - ethoxy ) - 3 pyridyl] methanimine

[0246 ] Analytical Methods Used Temperature : 60° C . Solvent Gradient: A = water + 10 % [ 0247 ] Method 1 : MeOH + 0 . 1 % HCOOH , B = Acetonitrile + 0 . 1 % HCOOH . [0248 ] Mass spectra were recorded on a Mass Spectrom Gradient: 0 min 0 % B , 100 % A ; 2 . 5 - 2 . 8 min 100 % B ; 0 % eter from Waters (SQD or ZQ Single quadrupole mass A ; 3 . 0 min 100 % A , 0 % B : Flow (ml /min ) 0 . 85 . spectrometer ) equipped with an electrospray source ( Polar ity : positive or negative ions, Capillary : 3 .00 kV , Cone Biological Examples for Compounds of Formula (I ) range : 30 -60 V , Extractor: 2 . 00 V , Source Temperature : 150° C ., Desolvation Temperature: 350° C . , Cone Gas Flow : 0 [0253 ] Certain compositions of the invention can be dis L /Hr , Desolvation Gas Flow : 650 L /Hr , Mass range : 100 to tinguished from known compositions and compounds by 900 Da) and an Acquity UPLC from Waters : Binary pump , virtue of displaying a greater efficacy at low application heated column compartment and diode - array detector. Sol rates, which can be verified by the person skilled in the art vent degasser , binary pump, heated column compartment using the experimental procedures outlined in the Examples , and diode -array detector. Column: Waters UPLC HSS T3 , using lower application rates if necessary, for example 50 1 . 8 m , 30x2 . 1 mm , Temp: 60° C ., DAD Wavelength range ppm , 12. 5 ppm , 6 ppm , 3 ppm , 1 . 5 ppm , 0 . 8 ppm and / or 0 . 2 ( nm ): 210 to 500 , Solvent Gradient : A =water + 5 % MeOH + ppm . The use of “ concentration /dilution factors ” in biologi 0 .05 % HCOOH , B = Acetonitrile + 0 .05 % HCOOH . Gradient : cal testing to determine the intrinsic biological efficacy of O min 0 % B , 100 % A ; 1 . 2 - 1 . 5 min 100 % B : Flow (ml /min ) bioactive molecules is known in the art . 0 .85 . [0254 ] Blumeria graminis f. Sp . Tritici (Erysiphe qraminis [0249 ] Method 2 : f . Sp . Tritici ) /Wheat / Leaf Disc Preventative (Powdery Mil [0250 ] Mass spectra were recorded on a Mass Spectrom dew on Wheat ) eter from Shimadzu (SQD or ZQ Single quadrupole mass [0255 ) Wheat leaf segments cv . Kanzler were placed on spectrometer ) equipped with an electrospray source ( Polar agar in a multiwell plate ( 24 -well format) and sprayed with ity : positive or negative ions, Capillary : 1. 5 kV, Cone range : the formulated test compound or mixture composition unknown, Extractor : 5 .00 V , Source Temperature: 200° C ., diluted in water . The leaf disks were inoculated by shaking Desolvation Temperature : 250° C . , Cone Gas Flow : 90 L /Hr , powdery mildew infected plants above the test plates 1 day Desolvation Gas Flow : 90 L /Hr , Mass range : 50 to 900 Da) after application . The inoculated leaf disks were incubated at and an SPD - 20A from LC from Shimadzu : Solvent degasser, 20° C . and 60 % rh under a light regime of 24 h darkness binary pump , heated column compartment and ultraviolet followed by 12 h light/ 12 h darkness in a climate chamber detector . Column : Diamonsil C18 ( 2 ) 5u 150 * 4 .6 mm , Temp : and the activity of a compound or mixture composition was 40° C ., SPD - 20A Wavelength range ( nm ): 210 to 500 , assessed as percent disease control compared to untreated Solvent Gradient: A = water + 0 . 1 % F2CCOOH , when an appropriate level of disease damage appears on B = Acetonitrile + 0 . 1 % F CCOOH ; Gradient: 0 min 10 % B , untreated check leaf segments (6 - 8 days after application ) . 90 % A ; 15 min 100 % B ; Flow 1 .00 ( ml/min ) [0256 ] The following compounds gave at 200 ppm give at [0251 ] Method 3 : least 80 % disease control in this test when compared to [ 0252 ] Mass spectra were recorded on a ZQ2000 Mass untreated control leaf disks under the same conditions , Spectrometer from Waters (Single quadrupole mass spec which show extensive disease development : trometer ) equipped with an electrospray source (Polarity : [0257 ] 67 .002 , 67. 003, 67. 007 , 67 .008 , 67 .009 , 67 .010 , positive ions , Capillary (kV ) 3 . 5 , Cone ( V ) 60 . 00 , Extractor 67 . 011 , 67 .013 , 67 . 014 , 67 . 015 , 67 .016 , 67 . 017 , ( V ) 3 .00 , Source Temperature ( ° C . ) 150 , Desolvation Tem 67 .018 , 67. 020 , 67. 021 , 67 . 022 , 67 .023 , 67 .024 , perature ( ° C . ) 350 , Cone Gas Flow ( L /Hr ) 50 , Desolvation 67 .025 , 67. 026 , 67 .027 , 67 .028 , 67 .029 , 67 .030 . Gas Flow ( L /Hr ) 800 , Mass range : 140 to 800 Da) DAD [0258 ] Puccinia recondita f. sp . tritici/ wheat / leaf disc Wavelength range (nm ): 210 to 400 , Type of column : Waters preventative (brown rust ) Wheat leaf segments cv . Kanzler ACQUITY UPLC HSS T3 ; Column length : 30 mm ; Internal were placed on agar in multiwell plates (24 -well format ) and diameter of column: 2 . 1 mm ; Particle Size: 1 . 8 micron ; sprayed with the formulated test compound or mixture US 2018 /0289005 A1 Oct. 11 , 2018 composition diluted in water . The leaf disks were inoculated [0268 ] The following compounds gave at 200 ppm gave at with a spore suspension of the fungus 1 day after applica least 80 % disease control in this test when compared to tion . The inoculated leaf segments were incubated at 19° C . untreated control leaf disks under the same conditions, and 75 % rh under a light regime of 12 h light/ 12 h darkness which show extensive disease development: in a climate cabinet and the activity of a compound or mixture composition was assessed as percent disease control [ 0269] 67 .002 , 67 . 003 , 67 .007 , 67 .008 , 67 .009 , 67 .010 , compared to untreated when an appropriate level of disease 67 .011 , 67 .012 , 67 .013 , 67 .014 , 67. 015 , 67 .016 , damage appears in untreated check leaf segments (7 - 9 days 67 . 017 , 67 . 018 , 67 .019 67 . 020 , 67 .023 , 67 .024 , 67 . 025 , after application ). 67 .026 , 67. 027 , 67. 028 , 67 .029 , 67 .030 . [0259 ] The following compounds gave at 200 ppm gave at Further Biological Test Examples least 80 % disease control in this test when compared to untreated control leaf disks under the same conditions , Example B1 : Preventative Activity Against which show extensive disease development: Blumeria Graminis f. Sp . Tritici (Erysiphe [0260 ] 67. 002 , 67. 003 , 67 .007 , 67. 008 , 67. 009 , 67. 010 , Graminis f. Sp . Tritici) on Wheat 67 .011 , 67 .013 , 67 .014 , 67 .015 , 67 .016 , 67 .017 , 67 .018 , 67 .020 , 67. 021 , 67 .022 , 67 .023 , 67. 024 , [ 0270 ] Wheat leaf segments cv. Kanzler are placed on agar 67 .025 , 67. 026 , 67. 028 , 67 .029 , 67 .030 . in a multiwell plate ( 24 -well format ) and sprayed with the formulated test compound or mixture composition diluted in [0261 ] Puccinia recondita f. Sp . Tritici/Wheat / Leaf Disc water . The leaf disks are inoculated by shaking powdery Curative (Brown Rust ) mildew infected plants above the test plates 1 day after [ 0262] Wheat leaf segments cv. Kanzler are placed on agar application . The inoculated leaf disks are incubated at 20° C . in multiwell plates ( 24 -well format ) . The leaf segments are and 60 % rh under a light regime of 24 h darkness followed inoculated with a spore suspension of the fungus . Plates by 12 h light /12 h darkness in a climate chamber and the were stored in darkness at 19° C . and 75 % rh . The formu activity of a compound or mixture composition is assessed lated test compound or mixture composition diluted in water as percent disease control compared to untreated when an was applied 1 day after inoculation . The leaf segments were appropriate level of disease damage appears on untreated incubated at 19° C . and 75 % rh under a light regime of 12 check leaf segments (6 - 8 days after application ). h light/ 12 h darkness in a climate cabinet and the activity of a compound or mixture composition was assessed as percent disease control compared to untreated when an appropriate Example B2 : Activity Against Mycosphaerella level of disease damage appears in untreated check leaf arachidis ( Cercospora arachidicola ) segments ( 6 - 8 days after application ) . [0271 ] Conidia of the fungus from cryogenic storage are [ 0263] The following compounds gave at 200 ppm gave at directly mixed into nutrient broth (PDB potato dextrose least 80 % disease control in this test when compared to broth ) . After placing a (DMSO ) solution of test compound untreated control leaf disks under the same conditions, or mixture composition into a microtiter plate ( 96 -well which show extensive disease development: format) , the nutrient broth containing the fungal spores is [0264 ] 67 .002 , 67 . 003 , 67 .007 , 67 .008 , 67 .009 , 67 .010 , added . The test plates are incubated at 24° C . and the 67 .011 , 67 .012 , 67 .013 , 67 .014 , 67. 015 , 67 .016 , inhibition of growth is determined photometrically 4 - 5 days 67 . 017 , 67 .018 , 67 .019 , 67 . 020 , 67 .021 , 67 . 022 , after application . 67 .023 , 67 .024 , 67. 025 , 67 .026 , 67 .027 , 67. 028 , 67 . 029, 67 .030 . Example B3 : Preventative Activity Against [ 0265 ] Phakopsora pachyrhizi on Soybean , Preventive Phakopsora pachyrhizi on Soybean Treatment [0272 ] Soybean leaf disks are placed on water agar in [ 0266 ] The compound or mixture composition activity multiwell plates ( 24 - well format) and sprayed with the was tested under 1 day preventive conditions. Soybean formulated test compound or mixture composition diluted in plants with a fully enfolded first trifoliate leaf were sprayed water. One day after application leaf discs are inoculated by with a track sprayer and 50 l/ ha spray volume with the test spraying a spore suspension on the lower leaf surface . After compounds or mixture composition , either solo or in tank an incubation period in a climate cabinet of 24 - 36 hours in mix as shown in the table below . darkness at 20° C . and 75 % rh leaf disc are kept at 20° C . with 12 h light /day and 75 % rh . The activity of a compound [ 0267] 1 day after application leaf discs were cut from the or mixture composition is assessed as percent disease con first trifoliate leaf and placed in multiwell plates on water trol compared to untreated when an appropriate level of agar. 5 leaf discs per treatment where infested with spores of disease damage appears in untreated check leaf disks ( 10 - 12 a triazole tolerant soybean rust strain . The multiwell plates days after application ) . where sealed and placed in an incubator 48 h in darkness and [0273 ] The following mixture compositions ( A : B ) at the 12 h light/ dark cycle afterwards. Rust infestation on leaf reported concentration ( in ppm ) gave at least 80 % disease discs was evaluated visually 11 days after application and control in this test when compared to untreated control leaf average activity calculated in relation to disease severity on disks under the same conditions , which show extensive untreated check leaf discs . disease development: US 2018 /0289005 A1 Oct . 11, 2018 43

Conc . Ratio (ppm ) Component A Component B A : B ( A : B ) Azoxystrobin 1 : 1 66 :66

Br N ' - [ 5 -bromo - 2 -methyl - 6 - ( 1 -methyl - 2 propoxy - ethoxy ) - 3 - pyridyl] - N - ethyl- N methyl- formamidine ( Compound 67. 013 ) Compound 67 .013 Azoxystrobin 1 : 1 22 : 22 Compound 67. 013 Azoxystrobin 7 . 3 : 7 . 3 Compound 67 .013 Azoxystrobin 66 : 200 Compound 67 .013 Azoxystrobin ???? 22 : 66 Compound 67 .013 Azoxystrobin 200 :66 Compound 67. 013 Azoxystrobin 66 : 22 Compound 67 .013 Azoxystrobin 22 : 7 . 33 Compound 67 .013 Azoxystrobin 3 : 1 7 . 3 : 2 . 44 Compound 67. 013 Azoxystrobin 3: 1 2 . 44 :0 . 8 Compound 67 .013 Azoxystrobin 3 :1 0 . 8 : 0 . 27 Compound 67. 013 Trifloxystrobin 1 : 1 66 :66 Compound 67. 013 Trifloxystrobin 22 : 22 Compound 67. 013 Trifloxystrobin 66 : 200 Compound 67 .013 Trifloxystrobin ? 22 :66 Compound 67. 013 Trifloxystrobin 7 . 33 : 22 Compound 67 .013 Trifloxystrobin 200 :66 Compound 67. 013 Trifloxystrobin ??? 66 : 22 Compound 67 .013 Trifloxystrobin 22 : 7 . 33 Compound 67. 013 Trifloxystrobin 3 :1 7 . 3 : 2 . 44 Compound 67. 013 Trifloxystrobin 3: 1 2 . 44 : 0 . 8 Compound 67 .013 Cyproconazole 1 : 1 66 :66 Compound 67 .013 Cyproconazole 1: 3 66 : 200 Compound 67 .013 Cyproconazole 200 :66 Compound 67 .013 Cyproconazole ?? 66 : 22 Compound 67 .013 Cyproconazole 3 : 1 22 : 7 . 33 Compound 67 .013 Cyproconazole 7 . 3 : 2 . 44 Compound 67 .013 Cyproconazole 2 . 44 : 0 . 8 Compound 67 .013 Difenoconazole 66 : 66 Compound 67 .013 Difenoconazole ??? 22 :22 Compound 67 .013 Difenoconazole 66 :200 Compound 67 .013 Difenoconazole 22 : 66 Compound 67. 013 Difenoconazole 3 :1 200 :66 Compound 67. 013 Difenoconazole 66 : 22 Compound 67 .013 Difenoconazole 22 : 7 . 33 Compound 67. 013 Difenoconazole 7 . 3 : 2 . 44 Compound 67. 013 Prothioconazole 66 :66 Compound 67. 013 Prothioconazole 1 : 1 22 : 22 Compound 67. 013 Prothioconazole ?? 66 : 200 Compound 67 .013 Prothioconazole ?? 22 : 66 Compound 67 .013 Prothioconazole ?? 7 . 33 : 22 Compound 67 .013 Prothioconazole 200 :66 Compound 67 .013 Prothioconazole ?? 66 :22 Compound 67. 013 Prothioconazole 22 : 7 . 33 Compound 67. 013 Prothioconazole 3: 1 7 . 3 : 2 . 44 Compound 67 .013 Mefentrifluconazole 66 :66 Compound 67. 013 Mefentrifluconazole ??? 66 : 200 Compound 67 .013 Mefentrifluconazole ?? 22 :66 Compound 67. 013 Mefentrifluconazole 200 :66 Compound 67. 013 Mefentrifluconazole ? 66 : 22 Compound 67. 013 Mefentrifluconazole 22 : 7 . 33 Compound 67 .013 Mefentrifluconazole 3 : 1 7 . 3 : 2 . 44 Compound 67 .013 Bixafen 66 :66 Compound 67. 013 Bixafen ?? 22 :22 Compound 67. 013 Bixafen 66 : 200 Compound 67 .013 Bixafen ?? 22 :66 Compound 67 .013 Bixafen ? 7 . 33 : 22 Compound 67. 013 Bixafen ? 200 :66 Compound 67. 013 Bixafen 66 : 22 Compound 67 .013 Bixafen 3 : 1 22 : 7 . 33 Compound 67. 013 Bixafen 3 : 1 7 . 3 : 2 . 44 US 2018 /0289005 A1 Oct . 11, 2018 44

-continued Conc . Ratio (ppm ) Component A Component B A : B ( A : B ) Compound 67. 013 Fluxapyroxad 66 :22 Compound 67 .013 Fluxapyroxad 3 : 1 22 : 7 . 3 Compound 67. 013 Fluxapyroxad 1 : 1 66 :66 Compound 67. 013 Fluxapyroxad 1 : 1 22 : 22 Compound 67. 013 Fluxapyroxad 9: 1 200 :22 Compound 67 .013 Fluxapyroxad 9 : 1 66 : 7 . 33 Compound 67. 013 Isopyrazam 9 : 1 66 : 7 . 3 Compound 67. 013 Isopyrazam 3 : 1 66 : 22 Compound 67 .013 Isopyrazam 3 : 1 22 : 7 . 3 Compound 67. 013 Isopyrazam 55 : 2 200 : 7 . 33 Compound 67. 013 Isopyrazam 55 : 2 66 : 2 . 44 Compound 67. 013 Isopyrazam 55 :2 22 : 0 . 8 Compound 67. 013 Isopyrazam 55 : 2 7 . 3 : 0 . 27 Compound 67. 013 Sedaxane 9 : 1 66 : 7 . 3 Compound 67 .013 Sedaxane 3 : 1 66 : 22 Compound 67. 013 Sedaxane 55uüüU : 2 200 : 7 . 33 Compound 67 .013 Sedaxane 55 :! 2 66 : 2 . 44 Compound 67. 013 Sedaxane 22 : 0 . 8 Compound 67 .013 Sedaxane 7 . 3 : 0 . 27 Compound 67. 013 Benzovindifupyr 9 : 1 66 : 7 . 3 Compound 67. 013 Benzovindifupyr 22 : 2 . 44 Compound 67 .013 Benzovindifupyr 7 . 3 : 0 . 8 Compound 67. 013 Benzovindifupyr 66 :22 Compound 67. 013 Benzovindifupyr 3 : 1 22 : 7 . 3 Compound 67 .013 Benzovindifupyr 3 : 1 7 . 33 : 2 . 44 Compound 67 .013 Benzovindifupyr 3 : 1 2 . 44 : 0 . 8 Compound 67. 013 Benzovindifupyr 55 : 2 200 : 7 . 33 Compound 67 .013 Benzovindifupyr 55 : 2 66 : 2 . 44 Compound 67. 013 Benzovindifupyr 55 : 2 22 : 0 . 8 Compound 67. 013 Benzovindifupyr 55 : 2 7 . 3 : 0 . 27 Compound 67. 013 9 : 1 66 : 7 . 3

N

Compound 67. 013 9 : 1 22 : 2 . 44

? ? F NH

Compound 67 .013 3 : 1 66 : 22

FO N US 2018 /0289005 A1 Oct . 11, 2018 45

-continued Conc . Ratio (ppm ) Component A Component B A : B ( A : B )

Compound 67 .013 3 : 1 22 : 7 . 3

FO N

Compound 67. 013 3 : 1 7 . 33 : 2 .44

F IZ.

Compound 67. 013 55 : 2 200 : 7 . 33

F 0

Compound 67. 013 Sex 55 : 2 66 : 2 . 44

Compound 67 .013 55 : 2 22 :0 .8

IZ. US 2018 /0289005 A1 Oct . 11, 2018 46

-continued Conc . Ratio (ppm ) Component A Component B A : B ( A : B ) Compound 67. 013 55 : 2 7 . 3 : 0 . 27

F 0 N

Compound 67. 013 3 : 1 22 : 7 . 3

Fuindapyr Compound 67. 013 Fuindapyr 1 : 1 66 :66 Compound 67. 013 Fuindapyr 1 : 1 22 : 22 Compound 67 .013 Fuindapyr 1 : 1 7 . 3 : 7 . 3 Compound 67. 013 Fuindapyr 9 : 1 200 :22 Compound 67. 013 Fuindapyr 9 : 1 66 : 7 . 33 Compound 67. 013 Fuindapyr 22 : 2 . 44 Compound 67 .013 Fuindapyr 7 . 3 : 0 . 8 Compound 67. 013 3: 1 66 : 22

11

UK -2A procide Compound 67 .013 UK -2A procide 3 : 1 22 :7 . 3 Compound 67. 013 UK -2A procide 1 : 1 66 : 66 Compound 67. 013 UK -2A procide 1 : 1 22 : 22 Compound 67. 013 UK -2A procide 1 : 1 7 . 3 : 7 . 3 Compound 67. 013 UK -2A procide 9 : 1 200 : 22 Compound 67 .013 UK -2A procide 66 : 7 . 33 Compound 67 .013 UK -2A procide 22 : 2 . 44 Compound 67 .013 UK -2A procide 9 : 1 7 . 3 : 0 . 8 Compound 67. 013 Chlorothalonil 1 : 1 66 : 66 Compound 67 .013 Chlorothalonil 66 : 200 Compound 67. 013 Chlorothalonil 200 :66 Compound 67 .013 Chlorothalonil 66 : 22 Compound 67 .013 Chlorothalonil 22 : 7 . 33 Compound 67 .013 Chlorothalonil 7 . 3 : 2 . 44 Compound 67. 013 Chlorothalonil www 2 . 44 : 0 . 8 Compound 67 .013 Mancozeb 66 : 66 Compound 67 .013 Mancozeb 1 : 3 66 : 200 Compound 67 .013 Mancozeb 3 : 1 200 :66 US 2018 /0289005 A1 Oct . 11, 2018 47

-continued Conc . Ratio (ppm ) Component A Component B A : B ( A : B ) Compound 67. 013 Mancozeb 3 : 1 66 :22 Compound 67 .013 Mancozeb 22 : 7 . 33 Compound 67. 013 Mancozeb 7 . 3 : 2 . 44

Example B4 : Preventative Activity Against C . and the inhibition of growth is determined photometri Phakopsora pachyrhizi on Soybean cally 3 -4 days after application . [ 0274 ] 4 - week old soybean plants are sprayed in a spray 1 . A fungicidal composition comprising a mixture of chamber with the formulated test compound or mixture components ( A ) and ( B ) , wherein component ( A ) is a composition diluted in water. Leaf disks are cut from treated compound of formula (1 ) plants and placed on agar into 24 -well plates one day after application . Leaf disks are inoculated by spraying them with a spore suspension on their lower leaf surface . After an incubation period in a climate cabinet of 24 - 36 hours in darkness at 20° C . and 75 % rh , the leaf disks are then kept at 20° C . with 12 h light/ day and 75 % rh . The percentage leaf RÓ disk area covered by disease is assessed when an appropriate level of disease appears on untreated check plants ( 12 - 14 days after application ) . Example B5 : Preventative Activity Against wherein Puccinia recondita on Wheat R ! represents hydrogen , chloro , bromo, cyano , C , -C2 [ 0275 ] Wheat leaf segments cv. Kanzler are placed on agar alkyl , CO2( C2 - C2 alkyl) , CO2H , CONH2, CONH (C1 in multiwell plates (24 - well format) and sprayed with the C4 alkyl) , CON ( C ,- C4 alkyl) 2, C , -C4 haloalkyl, or formulated test compound or mixture composition diluted in CZ - C4 haloalkoxy ; water . The leaf disks are inoculated with a spore suspension R ? represents C3 -Cgalkyl , C3- Coalkenyl, or Rº; of the fungus 1 day after application . The inoculated leaf R3 and R + independently of each other represent hydro segments are incubated at 19° C . and 75 % rh under a light gen , methyl, ethyl, isopropyl or cyclopropyl; or Rº and regime of 12 h light/ 12 h darkness in a climate cabinet and R4 together with the nitrogen atom to which they are the activity of a compound or mixture composition is attached form a 3 - , 4 - or 5 -membered saturated cyclic assessed as percent disease control compared to untreated group ; when an appropriate level of disease damage appears in R $ represents C , -CZ alkyl, or C , -C2 alkoxyC ,- C2 alkyl; untreated check leaf segments ( 7 - 9 days after application ) . Rrepresents phenyl, which can be substituted by chloro or C , - fluoroalkyl; or a salt , enantiomer, tautomer or Examples B6 : Preventative Activity Against N -oxide thereof; Pyrenophora teres on Barley and component ( B ) is a compound selected from the group consisting of (B1 ) a strobilurin fungicide [ 0276 ] Barley leaf segments cv . Hasso are placed on agar selected from the group consisting of azoxystrobin , in a multiwell plate ( 24 -well format) and sprayed with the picoxystrobin , enoxastrobin , pyraoxystrobin , mande formulated test compound or mixture composition diluted in strobin , flufenoxystrobin , coumoxystrobin , orysas water. The leaf segments are inoculated with a spore sus trobin , dimoxystrobin , metominostrobin , fenaminos pension of the fungus 2 days after application . The inocu trobin , pyrametostrobin , triclopyricarb , kresoxim lated leaf segments are incubated at 20° C . and 65 % rh under methyl, fluoxastrobin , pyribencarb , pyraclostrobin and a light regime of 12 h light/ 12 h darkness in a climate cabinet trifloxystrobin ; and the activity of a compound or mixture composition is (B2 ) an azole fungicide selected from the group consist assessed as disease control compared to untreated when an ing of azaconazole , etaconazole , ipconazole , tebucon appropriate level of disease damage appears in untreated azole , bitertanol , fenbucoanzole , metconazole , tetra check leaf segments ( 5 - 7 days after application ) . conazole , bromucoanzole , fluquinconazole , myclobutanil, triadimefon , flusilazole , penconazole , Example B7 : Activity Against Thanatephorus triadimenol, triticonazole , simeconazole , imibencon azole , hexaconazole , flutriafol, diniconazole , cypro cucumeris ( Rhizoctonia solani ) conazole , difenoconazole , epoxiconazole , propicon [0277 ] Mycelia fragments of a newly grown liquid culture azole , prothioconazole , pyrifenox , nuarimol, fenarimol, of the fungus are directly mixed into nutrient broth (PDB imizalil, triflumizole , prochloraz, pefurazoate , oxpoco potato dextrose broth ) . After placing a (DMSO ) solution of nazole, Mefentrifluconazole , 2 -[ [ 3 -( 2 -chlorophenyl ) - 2 the test compound or mixture composition into a microtiter ( 2 , 4 - difluorophenyl) oxiran - 2 -yl )methyl ] - 4H - 1 , 2 , 4 - tri plate ( 96 -well format) , the nutrient broth containing the azole - 3 - thione and 2 - [ 2 - chloro - 4 - (4 - chlorophenoxy ) fungal material is added . The test plates are incubated at 24° phenyl] - 1 - ( 1 , 2 , 4 - triazol- 1 - yl) propan - 2 - ol; US 2018 /0289005 A1 Oct . 11, 2018 48

(B3 ) a morpholine fungicide selected from aldimorph , phenyl] methanesulfonate , but- 3 - ynyl N - [ 6 -[ [ ( Z ) - [ ( 1 dodemorph , fenpropimorph and tridemorph ; methyltetrazol- 5 -yl ) - phenyl- methylene ]amino ] (B4 ) a carboxamide fungicide selected from bixafen , oxymethyl ) - 2 -pyridyl ] carbamate , N '- [ 4 -( 4 ,5 fluopyram , fluxapyroxad , isopyrazam , sedaxane , dichlorothiazol- 2 -yl ) oxy - 2 ,5 -dimethyl - phenyl ]- N furametpyr, penflufen , penthiopyrad , benzovindiflupyr, ethyl- N -methyl - formamidine , 4 - ( 2 -bromo - 4 - fluoro phenyl) - N - ( 2 - chloro - 6 - fluoro -phenyl ) - 2 , 5 -dimethyl thifluzamide , isofetamid , boscalid , carboxin , oxycar pyrazol- 3 - amine, 2 -[ 2 - fluoro -6 -[ (8 - fluoro -2 -methyl - 3 boxin , fenfuram , flutolanil, pyraziflumid , pydiflu quinolyl) oxylphenyl ] propan -2 -ol , 4, 4 ,5 - trifluoro - 3 , 3 metofen , mepronil , benodanil, N - [ ( 5 - chloro - 2 -isopro dimethyl- 1 - ( 3 - quinolyl ) isoquinoline , 3 - chloro - 6 pyl- phenyl ) methyl ] - N - cyclopropyl- 3 methyl - 5 - phenyl- 4 - ( 2 , 4 , 6 - trifluorophenyl) pyridazine , (difluoromethyl ) - 5 - fluoro - 1 -methyl - pyrazole - 4 3 -chloro -4 - (2 , 6 - difluorophenyl) - 6 -methyl -5 - phenyl carboxamide , 3 - ( difluoromethyl) - N - ( 7 - fluoro - 1 , 1 , 3 pyridazine, 2 - ( difluoromethyl ) - N - ( 1 , 1 , 3 -trimethylin trimethyl- indan - 4 - yl) - 1 -methyl - pyrazole - 4 dan - 4 -yl ) pyridine - 3 - carboxamide , 2 - ( difluoromethyl) carboxamide, 3 - (difluoromethyl ) - 1 - methyl- N - ( 1 , 1 , 3 N - ( 3 - ethyl- 1 , 1 -dimethyl - indan - 4 - yl) pyridine - 3 trimethylindan - 4 - yl) pyrazole - 4 - carboxamide and ( R ) carboxamide , 2 - (difluoromethyl ) - N - ( 1 , 1 - dimethyl- 3 3 - ( difluoromethyl) - 1 -methyl - N - ( 1 , 1 , 3 - trimethylindan propyl- indan - 4 -yl ) pyridine - 3 -carboxamide , 4 - yl) pyrazole - 4 - carboxamide ; 2 - (difluoromethyl ) - N - ( 3 - isobutyl- 1 , 1 -dimethyl - indan (B5 ) an anilinopyrimidine fungicide selected from 4 -yl ) pyridine- 3 -carboxamide , 2 - ( difluoromethyl) - N cyprodinil, mepanipyrim and pyrimethanil ; [ (3R ) - 1 , 1 , 3 - trimethylindan - 4 - yl] pyridine - 3 -carboxam (B6 ) an phenylpyrrole fungicide selected from fludioxonil ide, 2 - ( difluoromethyl) - N - [ (3R ) - 3 - ethyl- 1 , 1 - dimethyl and fenpiclonil; indan - 4 -yl ] pyridine -3 -carboxamide , ( B7) a phenylamide fungicide selected from benalaxyl, 2 - (difluoromethyl ) - N -[ (3R )- 1, 1 -dimethyl - 3 -propyl - in benalaxyl- M , furalaxyl , mefenoxam (metalaxyl - M ) dan - 4 - yl] pyridine - 3 - carboxamide , a compound of the and metalaxyl, ofurace and oxadixyl; formula (B8 ) a fungicide selected from the group consisting of ametoctradin , amisulbrom , anilazine, aureofungin , benomyl, benthiavalicarb , benthiazole , bethoxazin , BLAD , blasticidin - S , Bordeaux mixture, bupirimate , calcium polysulfide, captafol, captan , carbaryl, carben dazim , carpropamid , chinomethionate , chitosan , chlobenthiazone , chlorfenazole, chloroneb , chlorotha lonil , chlozolinate , climbazole , copper acetate , copper carbonate, copper hydroxide , copper naphthenate , cop per oleate , copper oxychloride, copper oxyquinolate , copper silicate , copper sulphate, copper tallate , cuprous oxide , cyazofamid , cyclafuramid , cyflufenamid , a compound of the formula cymoxanil , dazomet , dichlofluanid , dichlorprop , diclo cymet , diclomezine , dicloran , diethofencarb , diflume torim , dimetachlone , dimethipin , dimethirimol, dime thomorph , dinocap , dinocton , dinobuton , dinopenton , dipymetitrone , ditalimfos, dithianon , dodicin , dodine , doguadine , edifenphos , etem , ethaboxam , ethirimol, ethoxyquin , etridiazole, famoxadone , fenamidone , fenarimol, fenhexamid , fenoxanil , fenpropidine , fen pyrazamine, fentin acetate , fentin hydroxide , ferbam , ferimzone, fluazinam , flumorph , fluopicolide , fluor oimide , flusulfamide , flutianil, folpet, fosetyl- Al, fuberidazole , gibberellic acid , guazatine , hymexazole , iminoctadine , iodocarb , iprobenfos, iprodione , iprov alicarb , isoprothiolane, kasugamycin , mancozeb , man and a compound of the formula : dipropamid , maneb , metam , meptyldinocap , metiram , metrafenone , nabam , oxathiapiprolin , paclobutrazol, pencycuron , phenamacril , phosdiphen , phthalide , picarbutrazox , polyoxin D , probenazole , procymidone , prohexadione , propamocarb , propineb , proquinazid , pyrazophos, pyrifenox , pyrimorph , pyriofenone , pyro o quilon , quinoxyfen , quintozene , silthiofam , spiroxam ine , streptomycin , sulphur, tebufloquin , tecloftalam , tecnazene, thiabendazole , thidiazuron , thicyofen , thio phanate- methyl , thiram , tioxymid , tolclofos- methyl , NIITIT tolprocarb , tolylfluanid , triazoxide , tribufos, tricycla N zole , triforine, validamycin , valifenalate , vapam , vin clozolin , zineb , ziram , zoxamide , [ 2 - [ 3 - [ 2 - [ 1 - [ 2 - [ 3 , 5 bis (difluoromethyl ) pyrazol - 1 -yl ] acetyl] - 4 -piperidyl ] thiazol- 4 -yl ] - 4 , 5 - dihydroisoxazol- 5 -yl ] - 3 - chloro US 2018 /0289005 A1 Oct. 11 , 2018 49

(B9 ) a plant- bioregulator selected from the group con - pydiflumetofen , acibenzolar - S -methyl , chlorothalonil, man sisting of acibenzolar- S - methyl, chlormequat chloride, cozeb , dithianon , a compound of the formula ethephon , isotianil , mepiquat chloride , tiadinil and trinexapac - ethyl; (B10 ) an insecticide selected from the group consisting of abamectin , acequinocyl, acetamiprid , acrinathrin , afi dopyropen , alanycarb , allethrin , alpha -cypermethrin , alphamethrin , amidoflumet , azadirachtin , azocyclotin , bacillus firmus , bacillus thuringiensis , bensultap , ben > zoximate , betacyfluthrin , bifenazate , binapacryl, bioal lethrin , bioresmethrin , biphenthrin , broflanilide , broflu thrinate , bromophos - ethyl, buprofezine , cadusafos, carbaryl, carbosulfan , cartap , chlorantraniliprole , chlo rfenapyr, chromafenozide , cloethocarb , clothianidin , cyantraniliprole , cyclaniliprole , cycloprothrin , cyclox a compound of the formula aprid , cyenopyrafen , cyflumetofen , cyfluthrin , cyhalo thrin , cypermethrin , cyphenothrin , cyromazine, delta methrin , demeton - s- methyl , diafenthiuron , dialifos, dichloromezotiaz , diflovidazine , diflubenzuron , dinac tin , dinocap , dinotefuran , d - limonene, emamectin , empenthrin , esfenvalerate , ethion , ethiprole , etofen prox , etoxazole , famphur, fenazaquin , fenfluthrin , fenobucarb , fenoxycarb , fenpropathrin , fenpyroxy mate , fenvalerate , fipronil, flometoquin , flonicamid , fluacrypyrim , fluazuron , flubendiamide, flucythrinate , fluensulfone , flufenerim , flufenprox , flufiprole , fluhexafon , flumethrin , flupyradifuron , fluvalinate, fos thiazate , gamma -cyhalothrin , gossyplure , guadipyr, halofenozide, halofenprox , harpin , hexythiazox , and a compound of the formula hydramethylnon , imicyafos, imidacloprid , imiprothrin , indoxacarb , iodomethane , isothioate , ivermectin , lambda - cyhalothrin , lepimectin , lufenuron , metaflumi zone , metaldehyde, methomyl, methoxyfenozide , metofluthrin , milbemectin , niclosamide , nitenpyram , oxamyl, parathion - ethyl, pasteuria nishizawae , p - cy mene, permethrin , phenothrin , phosphocarb , piperonyl butoxide , pirimicarb , pirimiphos - ethyl, polyhedrosis virus , prallethrin , profenofos, profenofos, propargite , propetamphos , protrifenbute , pyflubumide, pymetro zine , pyraclofos, pyrafluprole , pyrethrum , pyridaben , NIE pyridalyl , pyrifluquinazon , pyrimidifen , pyriprole , pyriproxyfen , selamectin , silafluofen , spinetoram , spinosad , spirodiclofen , spiromesifen , spirotetramat, sulfoxaflor, tebufenozide, tebufenpyrad , tefluthrin , ter penoid blends, terpenoids , tetradiphon , tetramethrin , 4 . A fungicidal composition according to claim 1 wherein tetranactin , tetraniliprole , theta - cypermethrin , thiaclo component ( A ) is a compound selected from N - [ 5 -bromo prid , thiamethoxam , thiodicarb , tioxazafen , tolfen 2 -methyl - 6 - [( 1S ) - 1- methyl - 2 - propoxy -ethoxy ]- 3 - pyridyl] pyrad , transfluthrin , trichlorfon , triflumezopyrim , zeta N - ethyl- N -methyl - formamidine ( compound 67. 002 ), N - [ 5 cypermethrin and a - terpinene ; and (B11 ) glyphosate , bromo- 2 -methyl - 6 - [ ( 1R ) - 1 - methyl- 2 - propoxy - ethoxy ] -3 wherein the weight ratio of component ( A ) to compo pyridyl] - N -ethyl - N -methyl - formamidine (compound nent ( B ) is from 30 : 1 to 1 :40 . 67 .003 ), N '- [ 5 -cyano -2 -methyl - 6 - ( 1 -methyl - 2 -propoxy 2 . A fungicidal composition according to claim 1 wherein ethoxy ) - 3 - pyridyl] - N - ethyl- N -methyl - formamidine ( com component ( A ) is a compound of formula ( I) wherein R is pound 67 .007 ) , N - [ 5 - (difluoromethyl ) - 2 -methyl - 6 - ( 1 chloro , bromo, cyano , methyl or C , fluoroalkyl; R2 is n - pro methyl - 2 - propoxy - ethoxy ) - 3 -pyridyl ] - N -ethyl - N -methyl pyl, iso - propyl or allyl ; R * is methyl; R4 is ethyl or iso formamidine ( compound 67 .009 ) , N ' - [ 2 , 5 -dimethyl - 6 - ( 1 propyl; andRis methyl ; or a salt , enantiomer, tautomer or methyl- 2 -propoxy - ethoxy ) - 3 -pyridyl ] - N -ethyl - N -methyl N - oxide thereof. formamidine ( compound 67 .011 ) , N -15 -bromo - 2 -methyl - 6 3 . A fungicidal composition according to either claim 1 or ( 1 -methyl - 2 - propoxy - ethoxy ) - 3 -pyridyl ] - N - ethyl- N claim 2 wherein component ( B ) is a compound selected methyl- formamidine (compound 67. 013 ), N '- [6 -( 2 -allyloxy from the group consisting of azoxystrobin , picoxystrobin , 1 -methyl - ethoxy ) -5 -chloro - 2 -methyl - 3 -pyridyl ] - N - ethyl- N pyraclostrobin , trifloxystrobin , cyproconazole , difenocon methyl- formamidine (compound 67. 014 ), N '- [5 -chloro - 2 azole , epoxiconazole , metconazole , propiconazole , prothio methyl- 6 - (1 -methyl - 2 -propoxy -ethoxy ) -3 -pyridyl ] - N - ethyl conazole ,mefentrifluconazole , bixafen , fluopyram , fluxapy - N -methyl - formamidine (compound 67 .015 ) , and N ' - [ 5 roxad, isopyrazam , sedaxane, benzovindiflupyr, bromo - 2 -methyl - 6 - ( 1 -methyl - 2 -propoxy - ethoxy ) - 3 US 2018 /0289005 A1 Oct. 11 , 2018 50

pyridyl ] - N - isopropyl- N -methyl - formamidine ( compound clozolin , bupirimate , dinocton , dinopenton , dinobuton , 67. 018 ) ; or a salt , enantiomer, tautomer or N - oxide thereof. dinocap , meptyldinocap , diphenylamine , phosdiphen , 5 . A fungicidal composition according to claim 1 wherein 2 ,6 -dimethyl - [ 1 , 4 ]dithiino [ 2 , 3 - c : 5 ,6 - c ] dipyrrole - 1 , 3 , 5 , component (A ) is N '- [ 5 -bromo - 2 -methyl - 6 - [( 1S )- 1 -methyl 7 ( 2H ,6H ) - tetraone , azithiram , etem , ferbam , manco 2 -propoxy - ethoxy ] - 3 -pyridyl ] - N -ethyl - N -methyl - formami zeb ,maneb , metam ,metiram ( polyram ), metiram - zinc , dine ( compound 67 . 002 ) ; or a salt , enantiomer, tautomer or nabam , propineb , thiram , vapam (metam sodium ), N - oxide thereof. zineb , ziram , dithioether, isoprothiolane, ethaboxam , 6 . A fungicidal composition according to claim 1 wherein fosetyl , phosetyl- Al ( fosetyl- al ) , methyl bromide , component ( A ) is N -15 -bromo - 2 -methyl -6 - [ ( 1R ) - 1 -methyl methyl iodide, methyl isothiocyanate , cyclafuramid , 2 -propoxy -ethoxy ]- 3 -pyridyl ] - N - ethyl- N -methyl - formami fenfuram , validamycin , streptomycin , (2RS ) - 2 -bromo dine ( compound 67 . 003 ) ; or a salt , enantiomer , tautomer or 2 - ( bromomethyl) glutaronitrile ( bromothalonil) , N -oxide thereof. dodine , doguadine , guazatine , iminoctadine , iminocta 7 . A fungicidal composition according to claim 1 wherein dine triacetate , 2 , 4 - D , 2 ,4 - DB , kasugamycin , dimethi component ( A ) is N '- [5 -bromo -2 -methyl -6 - ( 1- methyl - 2 rimol, fenhexamid , hymexazole, hydroxyisoxazole propoxy -ethoxy )- 3 -pyridyl ] - N -ethyl -N -methyl - formami imazalil, imazalil sulphate , oxpoconazole , pefurazoate , dine (compound 67 .013 ) ; or a salt, enantiomer, tautomer or prochloraz , triflumizole , fenamidone , Bordeaux mix N - oxide thereof. ture , calcium polysulfide, copper acetate, copper car 8 . A fungicidal composition according to claim 1 wherein bonate , copper hydroxide , copper naphthenate , copper component ( A ) is N '- [ 5 - chloro - 2 -methyl -6 - ( 1 -methyl - 2 oleate , copper oxychloride , copper oxyquinolate , cop propoxy - ethoxy ) -3 -pyridyl ]- N - ethyl- N -methyl - formami per silicate , copper sulphate , copper tallate , cuprous dine ( compound 67 .015 ) ; or a salt, enantiomer , tautomer or oxide , sulphur, carbaryl, phthalide ( fthalide ), dingjun N - oxide thereof. ezuo ( Jun Si Qi) , oxathiapiprolin , fluoroimide , mandip 9 . A fungicidal composition according to claim 1 wherein ropamid , KSF - 1002 , benzamorf, dimethomorph , fen component ( A ) is N ' - [ 5 - bromo - 2 -methyl - 6 - ( 1 -methyl - 2 propimorph , tridemorph , dodemorph , diethofencarb , propoxy - ethoxy ) - 3 -pyridyl ] - N - isopropyl- N -methyl - forma fentin acetate , fentin hydroxide , carboxin , oxycarboxin , midine ( compound 67 .018 ) ; or a salt, enantiomer, tautomer drazoxolon , famoxadone , m - phenylphenol, p - phenyl or N -oxide thereof. phenol, tribromophenol ( TBP ) , 2 - [ 2 - [ ( 7 , 8 - difluoro - 2 10 . A fungicidal composition according to claim 1 methyl - 3 - quinolyl) oxy ] -6 - fluoro - phenyl] propan - 2 - ol wherein the composition comprises one or more further 2 - R - fluoro - 6 - [ ( 8 - fluoro - 2 -methyl - 3 - quinolyl )oxy ]phe pesticides selected from the group consisting of: nyl] propan - 2 -ol cyflufenamid , ofurace , oxadixyl, flu a fungicide , selected from etridiazole , fluazinam , benal tolanil , mepronil , isofetamid , fenpiclonil, fludioxonil , axyl, benalaxyl- M (kiralaxyl ) , furalaxyl, metalaxyl, pencycuron , edifenphos , iprobenfos, pyrazophos , phos metalaxyl - M (mefenoxam ), dodicin , N ' -( 2 , 5 - Dimethyl phorus acids, tecloftalam , captafol, captan , ditalimfos , 4 - phenoxy - phenyl) - N - ethyl- N -methyl - formamidine , triforine, fenpropidin , piperalin , osthol, 1- methylcyclo N '- [ 4 - ( 4 , 5 -Dichloro - thiazol - 2 - yloxy ) - 2 , 5 -dimethyl propene , 4 -CPA , chlormequat , clofencet, dichlorprop , phenyl] - N -ethyl - N - methyl- formamidine , N - [ 4 - [ [ 3 - [ ( 4 dimethipin , endothal, ethephon , flumetralin , forchlo chlorophenyl) methyl ) - 1, 2 ,4 - thiadiazol- 5 -yl ] oxy ]- 2 ,5 rfenuron , gibberellic acid , gibberellins, hymexazol, dimethyl- phenyl] - N - ethyl- N -methyl - formamidine, maleic hydrazide , mepiquat , naphthalene acetamide , ethirimol, 3 '- chloro - 2 -methoxy - N - [ ( 3RS ) - tetrahydro paclobutrazol, prohexadione , prohexadione - calcium , 2 -oxofuran - 3 -yl ] acet -2 ', 6 ' -xylidide (clozylacon ), thidiazuron , tribufos ( tributyl phosphorotrithioate ) , cyprodinil , mepanipyrim , pyrimethanil, dithianon , trinexapac , uniconazole, a -naphthalene acetic acid , aureofungin , blasticidin -S , biphenyl , chloroneb , diclo polyoxin D (polyoxrim ), BLAD , chitosan , fenoxanil , ran , hexachlorobenzene , quintozene , tecnazene , folpet , 3 - ( difluoromethyl) - N -methoxy - 1 -methyl - N - [ 1 ( TCNB ) , tolclofos -methyl , metrafenone, 2 , 6 -dichloro methyl - 2 - ( 2 ,4 , 6 - trichlorophenyl ) ethyl] pyrazole - 4 - car N -( 4 -trifluoromethylbenzyl ) -benzamide , fluopicolide boxamide, bixafen , fluxapyroxad , furametpyr, isopyra ( flupicolide ), tioxymid , flusulfamide , benomyl, carben zam , penflufen , penthiopyrad , sedaxane , dazim , carbendazim chlorhydrate , chlorfenazole , fenpyrazamine , diclomezine, pyrifenox , boscalid , flu fuberidazole , thiabendazole , thiophanate -methyl , ben opyram , diflumetorim , fenarimol, 5 - fluoro - 2 - ( p - tolyl thiavalicarb , chlobenthiazone , probenazole , acibenzo methoxy ) pyrimidin - 4 - amine ferimzone, dimetachlone lar, bethoxazin , pyriofenone (IKF -309 ) , acibenzolar- S (dimethaclone ), pyroquilon , proquinazid , ethoxyquin , methyl, pyribencarb (KIF - 7767) , butylamine, 3 - iodo quinoxyfen , 4 ,4 , 5 - trifluoro - 3 , 3 - dimethyl- 1 - ( 3 - qui 2 - propinyl n -butylcarbamate ( IPBC ) , iodocarb nolyl) isoquinoline 4 ,4 - difluoro - 3 , 3 - dimethyl - 1 - ( 3 - qui ( isopropanyl butylcarbamate ), isopropanyl butylcar nolyl) isoquinoline 5 - fluoro - 3 , 3 , 4 , 4 - tetramethyl- 1 - ( 3 bamate ( iodocarb ), picarbutrazox , polycarbamate , pro quinolyl) isoquinoline 9 - fluoro - 2, 2 - dimethyl- 5 -( 3 pamocarb , tolprocarb , 3 - ( difluoromethyl) - N - ( 7 - fluoro quinolyl) - 3H - 1 , 4 -benzoxazepine , tebufloquin , oxolinic 1991 , 1 , 3 , 3 - tetramethyl- indan - 4 - yl) - 1 -methyl - pyrazole - 4 acid , chinomethionate (oxythioquinox , quinoxymethio carboxamide diclocymet, N - [ (5 - chloro - 2 - isopropyl nate ), spiroxamine , ( E ) - N -methyl - 2 - [ 2 - ( 2 , 5 - dimethyl phenyl) methyl ] - N - cyclopropyl- 3 - ( difluoromethyl ) - 5 phenoxymethyl) phenyl ]- 2 -methoxy -iminoacetamide , fluoro - 1 -methyl - pyrazole -4 - carboxamide (mandestrobin ) , azoxystrobin , coumoxystrobin , N -cyclopropyl - 3 - (difluoromethyl ) -5 - fluoro -N -[ (2 - iso dimoxystrobin , enestroburin , enoxastrobin fenamis propylphenyl) methyl ] - 1 -methyl - pyrazole -4 -carboxam trobin , flufenoxystrobin , fluoxastrobin , kresoxim ide carpropamid , chlorothalonil, flumorph , oxine - cop methyl, mandestrobin , metaminostrobin , metominos per, cymoxanil , phenamacril , cyazofamid , flutianil , trobin , orysastrobin , picoxystrobin , pyraclostrobin , thicyofen , chlozolinate , iprodione , procymidone , vin pyrametostrobin , pyraoxystrobin , triclopyricarb , tri US 2018 /0289005 A1 Oct. 11 , 2018 51

floxystrobin , amisulbrom , dichlofluanid , tolylfluanid , valerate , fipronil, flonicamid , flubendiamide , flucythri but- 3 -ynyl N - [ 6 - [ [ ( Z ) - [ ( 1 -methyltetrazol - 5 - yl) - phenyl nate , tau - fluvalinate , flufenerim (UR -50701 ) , flufenox methylene ]amino ]oxymethyl ) - 2 -pyridyl ] carbamate , uron , fonophos , halofenozide , hexaflumuron , dazomet , isotianil, tiadinil , thifluzamide , benthiazole hydramethylnon , imidacloprid , indoxacarb , isofen ( TCMTB ) , silthiofam , zoxamide, anilazine , tricycla phos , lufenuron , malathion , metaflumizone , metalde zole , (. + - . ) - cis - 1 - ( 4 - chlorophenyl) - 2 - ( 1H - 1 , 2 , 4 - triazol hyde , methamidophos , methidathion , methomyl, 1 - yl) -cycloheptanol (huanjunzuo ), 1 - ( 5 - bromo- 2 methoprene , methoxychlor , metofluthrin , monocroto pyridyl) - 2 - ( 2 , 4 - difluorophenyl) - 1 , 1 - difluoro - 3 - ( 1 , 2 ,4 phos , methoxyfenozide , nitenpyram , nithiazine , triazol - 1 -yl ) propan - 2 -ol 2 - ( 1- tert -butyl ) - 1 -( 2 novaluron , noviflumuron (XDE - 007 ) , oxamyl, para chlorophenyl) -3 - ( 1, 2 ,4 - triazol- 1- yl) -propan - 2 -ol thion , parathion -methyl , permethrin , phorate , phosa ( TCDP ) , azaconazole, bitertanol (biloxazol ) , bromu lone, phosmet, phosphamidon , pirimicarb , profenofos , conazole , climbazole, cyproconazole , difenoconazole , profluthrin , pymetrozine , pyrafluprole , pyrethrin , dimetconazole , diniconazole , diniconazole - M , epoxi pyridalyl, pyrifluquinazon , pyriprole , pyriproxyfen , conazole , etaconazole , fenbuconazole , fluquincon rotenone , ryanodine , spinetoram , spinosad , spirodi azole , flusilazole , flutriafol, hexaconazole , imibencon clofen , spiromesifen (BSN 2060 ) , spirotetramat, sul azole , ipconazole , metconazole , myclobutanil, profos, tebufenozide, teflubenzuron , tefluthrin , terbu penconazole , propiconazole , prothioconazole , Mefen fos, tetrachlorvinphos , thiacloprid , thiamethoxam , trifluconazole , simeconazole , tebuconazole , tetracon thiodicarb , thiosultap - sodium , tralomethrin , triazamate , azole , triadimefon , triadimenol , triazoxide , triticon trichlorfon and triflumuron ; or azole , 2 - [ [ ( 1R ,5S ) - 5 - [ ( 4 - fluorophenyl) methyl ] - 1 a bactericides selected from streptomycin ; or hydroxy - 2 , 2 -dimethyl - cyclopentyl ] methyl ] -4H - 1 , 2 ,4 an acaricide selected from amitraz , chinomethionat , chlo triazole- 3 - thione 2 - [ [ 3 - ( 2 - chlorophenyl) - 2 - ( 2 , 4 robenzilate , cyenopyrafen , cyhexatin , dicofol, dieno difluorophenyl ) oxiran - 2 - yl] methyl ] - 4H - 1 , 2 ,4 - triazole chlor, etoxazole , fenazaquin , fenbutatin oxide , fenpro 3 - thione , ametoctradin (imidium ) , iprovalicarb , pathrin , fenpyroximate , hexythiazox , propargite , valifenalate , 2 -benzyl - 4 - chlorophenol (Chlorophene ) , pyridaben and tebufenpyrad ; or allyl alcohol, azafenidin , benzalkonium chloride , chlo a biological agents selected from Bacillus thuringiensis , ropicrin , cresol, daracide , dichlorophen (dichloro Bacillus thuringiensis delta endotoxin , baculovirus , phene ), difenzoquat , dipyrithione, N - ( 2 - p - chloroben and entomopathogenic bacteria , virus and fungi. zoylethyl) -hexaminium chloride, NNF- 0721 , 11 . A fungicidal composition according to claim 1 octhilinone, oxasulfuron , propamidine and propionic wherein the composition further comprises an agriculturally acid ; or an insecticides selected from abamectin , acephate , acet acceptable carrier and , optionally, a surfactant and/ or for amiprid , amidoflumet ( S - 1955 ), avermectin , mulation adjuvants . azadirachtin , azinphos -methyl , bifenthrin , bifenazate , 12 . A method of controlling or preventing phytopatho buprofezin , carbofuran , cartap , chlorantraniliprole genic diseases , especially phytopathogenic fungi, on useful (DPX - E2Y45 ), chlorfenapyr, chlorfluazuron , chlorpy plants or on propagation material thereof, which comprises rifos, chlorpyrifos- methyl , chromafenozide, clothiani applying to the useful plants , the locus thereof or propaga din , cyflumetofen , cyfluthrin , beta - cyfluthrin , cyhalo tion material thereof a fungicidal composition as defined in thrin , lambda- cyhalothrin , cypermethrin , cyromazine, claim 1 . deltamethrin , diafenthiuron , diazinon , dieldrin , 13 . A method according to claim 12 wherein the compo diflubenzuron , dimefluthrin , dimethoate , dinotefuran , sition components ( A ) and ( B ) are applied in a sequential diofenolan , emamectin , endosulfan , esfenvalerate , manner . ethiprole , fenothiocarb , fenoxycarb , fenpropathrin , fen