(19) United States
`(12) Patent Application Publication (10) Pub. No.: US 2016/0212993 Al
`Jul. 28, 2016
`(43) Pub. Date:
`Stock et al.
`
`US 20160212993A1
`
`(54) ADJIJVANT COMPOSITIONS
`
`(71) Applicants:SYNCENTA LIMITED. Berkshire
`(GB); SYNGENTA
`PARTICIPATIONS AG. Basel (CH)
`
`(72)
`
`Inventors: David Stock, Berkshire (GB); Philip
`Taylor. Berkshire (GB); Richard Brian
`Perry. Berkshire (GB); Julia Lynn
`Ramsey. Berkshire (GB), Gordon
`.Alaslair Bell. Berkshire (GB); Emma
`Jane Ashford, Base! (CR)
`
`(73) Assignees: SYNGENTA LIMITED, Berkshire
`(GB); SYNGENTA
`PARTICIPATIONS AG, Basel (CR)
`
`(21) AppI. No.: 15/091,027
`
`(22)
`
`Filed:
`
`Apr. 5,2016
`
`(60)
`
`Provisional application No. 61/589,864. flied on Jan.
`23, 2012.
`
`Publication Classification
`
`(51)
`
`Tnt. Cl.
`AOIN3I/03
`Ao1]v43/4o
`49JV3”O8
`AOIN43i88
`A01N43/56
`AOIN4J/9O
`A01N43/54
`(52) U.S. CI.
`CPC
`
`(2006.0!)
`(2006.0!)
`(2006.01)
`(2006.01)
`(2006.01)
`(2006.01)
`(200601)
`
`AOINII/O4 (2013.01); 401N43/9O
`(2013.01);AOIN4J/40 (2013.01); A01N43/54
`(2013.01); AOIN4J/88 (2013.01): 401N43/56
`(2013.01); .401N37/08 (2013.01)
`
`Related U.S. Application Data
`(62) Division ofapplicalion No. 14/370,062, filed on Jul. 1,
`2014, filcdasapplicaiionNo. PCT/EP2013/050922on
`Jan. 18, 2013.
`
`(57)
`
`ABSTRACT
`
`Adjuvant compositions are provided which comprise at least
`one lerpenic a]koxylate and at least one agrochemical active
`ingredient.
`
`J
`
`T. Alt
`
`SYNGENTA EXHIBIT 1042
`Syngenta v. UPL, PGR2023-00017
`
`

`

`US 2016/0212993 Al
`
`Jul. 28, 2016
`
`I
`
`ADJUVANT COMPOSITIONS
`
`100011 This application is a divisional filing of U.S. appli
`cation Ser. No. 14/370,062, filed Jul. 1,2014, which is a U.S.
`371 of International Application No. PCT/EP2013/050922,
`filed Jan. 18, 2013, which claims priority benefit to U.S.
`Provisional PatentApplication No. 61/589,864, filed Jar,. 23,
`2012, the contents of all of which are incorporated herein by
`reference.
`100021 The present iovention relates generally to adjuvants
`for agrochemicals. In particular, the present invention relates
`to the use of certain terpenic alkoxylatcs as adjuvants to
`improve the performance of agrochemicals and to agro
`chemical compositions containing such adjuvants.
`(0003j The present invention provides mixtures compris
`ing certain terpenic alkoxylate adjuvants A and an agrnchcmi
`cal component B. Component B is an agrochemical active
`ingredient. Suitable agrochemical active ingredients include
`insecticides, acaricides, aematocides, molluscicides, fungi
`cides, herbicides, plant growthregulators as well as fertilizers
`and micronutrients.
`It has now been found, surprisingly, that the agro
`[0004]
`adjuvant mixture according to
`chemical active ingredient
`the invcntioncan extend the range of actionofthe agrocbemi
`cal active ingredient e.g. by achieving a synergistic effect.
`Thus, tberates of application of thecomponents are lowered
`whilst the action remains equally good. Secondly, the active
`ingrcdicnt mixture still achieves a high degree ofpcst orwccd
`control, sometimes even where the Iwo individual compo
`nents have become totally inettèctive in such a low applica
`tion rate range. This allows increased safcty in use or any
`other advantages familiar to a person skilled in the art.
`invention provides an
`(0005] Accordingly,
`the present
`adjuvant composition comprising at
`least one terpenic
`alkoxylate A and at Icast onc agrochemical active ingredient
`B. When used hcrein, the term “terpenic” in the context of the
`terpenic alknxylate component is indicative of a moiety hav
`ing terpenic origin. In a further embodiment, the adjuvant
`composition of the invention may also contain water and/or
`one or more organic diluents such alkyl alcohols and/or gly
`cols.
`(0006] The present invention also provides a method of
`using of the above described adjuvant composition to
`enhance plant growth in plant growth media by contacting the
`plants, parts of plants, seeds, their locus of growthorthe plant
`growth media with an effective amount of said adjuvant com
`position.
`In another aspect of the present invention, there is
`10007]
`provided a mcthod of cnhancing thc bio-efficacy orbio-avail
`ability of at least one agrochemical B said method comprising
`applying the agrochemical to plants, parts of plants, seeds, or
`at their locus of growth in any desired sequence, including
`simultaneously, separately, or in succession with a terpenic
`alknxylate component according to the present invention in
`an amount effective to enhance bio-efficacy or bio-availabil
`ity of said at least one agrochemical.
`In the practice of the invention, the terpenic alkoxy
`100081
`late component of the invention can be applied as a concen
`trate or by dispersing the concentrate according to the present
`invention in water for use as a dilutcd aqueous cnd-use for
`mulation.
`10009] The inventive adjuvant composition may be applied
`directly or with dilution in watcr alone or in combination with
`insecticides, acaricides,
`agrocbemieal materials such as
`
`nematocides, molluscicides, fungicides, herbicides, plant
`growth regulators as well as fertilizers and micronutrients.
`100101 The various aspects of the present invention men
`tioned above, as well as many other aspects of the invention
`are described in greater detail below.
`100111 Accordingly, in one embodiment, the at least one
`terpenic alkoxylate is selected from a compound of the for
`mulae (II):
`
`R3—o(cH(R4)cn7o)-—(cn(n.4)cIt,o),-—it5
`(tt)
`wherein R3 is a terpenic moiety selected from the group
`consisting of terpenic carbides, oxidized derivatives of ter
`penic carbides (such as hydroformylntion derivatives), ter
`penic alcohols, terpenic aldehydes and ketones, and mixtures
`thereof; R4 is selected from hydrogen and methyl (i.e., the
`{CH(R4)CH,0)_.. units of the alkylene oxide moiety of
`formula (H) are selected from ethylene oxide (HO) and pro
`pylene oxide (P0) in either a block or random configm-ation);
`R5 is selected from hydrogen and linear or branched C,-C3
`alkyl; and where n and mare each other than zero and wherein
`the sum of n and mis chosen so that there are from 2 to 10
`propylene oxide units and from 5 to 25 ethylene oxide units.
`[0012]
`In one aspect, the terpenic moiety R3 is a moiety
`derived from monoterpenes, sesquiterpenes. diterpenes, and
`hydroformylation derivatives thereof. In particular, there may
`he mentioned the terpcnes containing ten carbon atoms in
`their structure and, more specifically, acyclic, monocyclic or
`bicyclic monoterpenes. Among the suitable monoterpenes
`there are, for example, monocyclie terpenic carbides such as
`limonene, etc.; bicyclic
`dipentene, terpinolene, p-cymene,
`terpenic carbides such as a-pinene, [1-pinene or b-3-carene,
`etc.; and terpenic alcohols such as bomeol, fenchol, meotha
`nol, terpineols, geraniol, etc.; hydroformylation derivatives
`thereof; and mixtures thereof.
`In another aspect, in the terpenic alkoxylate of for
`[0013]
`mula (II) the sum of n and mis chosen so that there are from
`3 to 7 propylene oxide units and from 5 to 15 ethylene oxide
`units;morc particularly, from3 to 7 propylene oxide units and
`from 5 to 9 ethylene oxide nnits—in any case, ioeithera block
`or a random configuration.
`In one embodiment, the terpenic alkoxylate of for
`(0014]
`mula (It) is selected from a block copolymer of the formulae
`(JIa) or (JIb):
`
`RrPO,..EO,,.R,
`
`(ita)
`
`(llb)
`RrEO,PO,,R
`In another embodiment, the terpenic alkoxylate of
`[0015]
`formula (II) is a random HO/PD copnlymcr (llc):
`(tic)
`tt3-(randorn Eo/Po), ,,,-R5
`In a specific embodiment, the R3 moiety of fnnnula
`100161
`(11) is derived from the hydrofnrmulation of 3-pincne so that
`(he terpenic alkoxylate (b) is a Nopol alkoxylate of the for
`mula (lId)
`
`H3C
`
`CH3
`
`(lid)
`
`/
`
`n—(crr(R4)cH1o)n— (CH(R,)01J10)m—R,
`
`

`

`US 20 16/0212993 Al
`
`Jul. 28, 2016
`
`2
`
`wherein R4. R5, m and n are as defined above. ]n a more
`specific embodiment, the terpenic alkoxylate (b) is Nopol’
`(PO-EOj-H. where Nopol is the hydrofonnylation product
`of 3-pinene, and wherein n—5 and rn=7.
`[0017]
`Suitable terpenic alkoxylates b) for use in the adju
`vaiit composition of the present
`invention generally are
`known from the literature or may be prepared by processes
`known front the literature and are also commercially avail
`able, For example. wider the RHODOCLEAN® family of
`terpenic alkoxylates (Rhodia).
`100181 The components B are known. e.g. from “The Pes
`ticide anuat”. Fifteenth Edition. Edited by Clive Tomlin.
`British Crop Protection Council.
`j0019] The combinations according to the invention may
`also comprise more than one of the active components B. if,
`for example, a broadening of the spectnttn of pest control is
`desired. For instance, it may be advantageous in the agrictil
`tural practice to combine two or three components B with a
`terpenic alkoxylate. The mixtures of tbe invention may also
`comprise other active ingredients in addition to a terpenic
`alkoxylate and component B.
`[0020]
`Suitably, component B is
`a herbicide such as
`pinoxaden or fluazifop P butyl, or is also selected front
`I ,2,4-triazin-5-ones such as metamitron and metribuzin
`dimethylpyrazoles such as benzofenap, pyrazolynate (pyra
`zolate) and pyrazoxyfen.
`acylanilides such as propanil
`amide herbicides such as benfluamid, bromobutidc, carbeta
`wide, flufenacet, isoxaben, naproanilide, napropamide, nap
`talam, propyzamide and tebutam
`amino acids and salts and esters thereo1 such as bialaphos
`and salts and esters thereot glufnsinate salts and esters
`thereof. glyphosate and salts andesters thereof, and sulfosae.
`aryloxypropionates,
`thcluding the optically active isomers
`thereoL sucb as clodinafop-propargyl, cyhalofop-butyl.
`diclofop & esters thereof e.g. methyl ester. feitoxaprop &
`esters thereof eg ethyl ester, fluazifop-butyt, haloxfop and
`esters thereof, pmpaquizafop. quizalofop and esters thereof
`and quizalofnp-p-teftiryl
`arylanilidt such as dillufenican, flamprop. flamprop-M and
`esters thereof
`ary]ureas such as cblorbromuron, chiorotoluron. daimuron
`(dymron), dimefuron. diuron, fenuron. fluometuron, isopro
`turon. isouron, linuron, methabenzthiazuron. methyldynaron.
`metobrornumn, metoxuron. monolinuron. ncburon and
`tebuthiuron
`benzo-2. 1,3-thiadiazin-4-one-dioxides such as bentazone
`betizoic acids such as 2,3,6-trichlorobenzoic acid. chloraits
`ben and dicamba
`bipyridyliunts such as diquat and salts thereof, and paraquat
`and salts thereof.
`carbamates such as chlorprophaiti and propham. and phenyl
`carbamoyloxyphenyl carbamates such as desmedipham and
`phenmedipham
`acetamides such as acetochlor, alachlor, butachlor, dirneth
`achior, dimetbcnamid and isomers thereof, mctazachlor.
`metolachior and isomers thereof; pretilachior, propachior.
`propisochior and thenylchior.
`cyclohexanediones such as alloxydim and salts thereof.
`butroxydim, clethodim, cycloxydirn, sethoxydim, tepraloxy
`dim and tralkoxydim.
`dihalobeozonitriles such as dichiobenil
`dinitrophenols such as dinoterb and dintro ortho-crcsol
`(DNOC)
`
`diphenyl ethers such as acifittmfen a:id salts and esters
`thereof; aclonifen. bifenox, chlomethoxyfen. chioruitrofen,
`flurogiycofen or salts or ester thereof, fontesafea. lactofen
`and oxyfluorfen.
`dinitroanilines suchasdinitramine, ethaltiuralin, fiuchloralin,
`otyzalin. pendimethalin, prodiamine and trifiuralin.
`haloalkanoic herbicides such as dalapon and trichloroacetic
`acid and salts thereof.
`hydroxybetizonitrile (HBN) herbicides such as brontoxynil
`and ioxynil, and l-IBN precursors such as bromofenoxiin
`hormone herbicides such as 2,4.5-trichlorophenoxyacetic
`acid, 2,4-dichtorophenoxacetic acid, 2,4-dichlorophenoxy-
`butvrie acid,
`clopyralid. dichlorprop & dichlorprop-p,
`finroxypyr, 4-chloro-2-methoxyacctic acid (MCPA), MCPA
`thincthyl,
`4-(4-ehloro-2-methylphenoxy)butyric
`acid
`(MCPB), mecoprop & meeoprop-p, picloram, thiazopyr and
`triclopyr.
`imidazolinones such as imazapic, imazamox, iinazametha
`benz-methyl, itnazapyr & isopropylamrnoniuin salts thereof;
`imazaquin and imazetltapyr.
`methyl isothiocyanate precursors such as dazoniet.
`miscellaneous herbicides such as ammoniurn sulfamate. asu
`lam, azafen.idin, benazolin, benrobicyclon/benbiclon, cinm
`ethylin, clomazone, difenzoquat & salts thereof eg methyl
`sulphate salt, diflufenzopyr-sodium (SAN-835H), dime
`thipio, dimexyflam, diphenamid, dithiopyr, epoprodan, etho
`fttmesate, etobenzanid, fluazolate, fentrazantide, fiuearba
`zone, flumiclornc-pentyl, flumioxazin, flupoxarn, finrenol
`butyl,
`flurochloridone,
`fluthiacet-methyl,
`flurtamone,
`hexnzinone, mefenacet, oxadiazon, oxaziclomefone, pentox
`azone, pyraflufen-ethyl, pyridatol/pyridafol, pyridate, isox
`aehlortole, isoxaflutole and sodium chlorate.
`organoarsenical herbicides such as disodium methylarsonate
`tDSN{A) and monosodium methylarsotiate (MStvLAI
`organuphosphonis herbicides such as anilofos and fosantine
`soditim
`phnsphorothioates such as butamifos, bensulide and pipero
`phos
`pyridazinones snelt as chloridazon and norfiurazon
`pyndnnes such as fluridone
`pyrintidinyloxybenzoic acids and salts and esters thereof;
`such as pyrithiobac-sodium. bispyriboc-sodit;m. pyrirnino
`bac-methyl and pyribenzoxim
`quinolinecnrhnxylic acids such as quimerac and quinelorac
`herbicide antidotes such as bcnoxacor, cloquinttocet-mexyl.
`dichionnid,
`fencblorazole-ethyl,
`fencloritn,
`fluxofenim.
`furilazole. naphthalic anhydride. oxabentrinil, mefenpyr-di
`ethyl. N-(dichloroacetvl)-l-oxa-4-azaspirobicyclo-(4,5)-de-
`cane (AD-67), 3-dichloroacetyl-2,2.5-trimethyloxazolidine
`(R-291 48)
`and 2-dichloromethyl-2-nietltyl- I ,3-dioxolane
`(MG-WI).
`sulfamoylurens such as cyclosulfaniuron.
`sulfonanilides such as chioransulam-methy]. diclosulam, fib
`rasulam, flumetsulam and metosulam.
`sulfonylureas such as amidosulfuron, azimsulfuron. bensul
`fliron and esters thereof; chlorimuron & esters eg ethyl ester
`thereof, ehiorsulfliron, cinosulfuron. ethametsulfuron-me
`thyl, tlazasulfi,roa, flupyrsulfuron and salts thereof, halosul
`furon-methyl, ethoxysulfliron, imazosultiaron, iodosultiamn,
`metsulfnron and esters thereof; nicosulfuron, oxasnlfumn,
`primisulfuron & esters eg methyl ester thereof. prosulfuron,
`pyrazosulfuron-ethyl,
`sulfometuron-methyl,
`riinsulfuron,
`sulfosulfitron, thifensulfuron-methyl,
`triasulfiaron, tnbenu
`ron, tribenut-on-methyl and trifiusulfuron-methyl
`
`

`

`US 2016/0212993 Al
`
`3
`
`Jul. 28, 2016
`
`Ihiocarbamates such as butylate, cycloate, dimepiperale.
`S-ethyl diprupylthiocarbamate (EPIC), esprocarb. molinate,
`orheucarb. pebulate. prosuifccarb. thiobencarb. tiocarbazil,
`sri-al late and vemolate.
`triazine herbicides such as ametryn, airazine. cyanaziuc.
`dimethametryn. promelon. prorneiryn, propazine. simazine,
`sirneiryn. Ierbuthylaziae, terbunyn and Irietazine.
`triazole herbicides such as ainitrole.
`triazolinones such as carfentrazone-ethyl and sulfentrazone.
`triketones such as sulcotrione and mesotrione.
`uracils such as bromacil, lenacil and lerbacil.
`In one embodiment, componeol B is a flingicida]
`(0021j
`(E)-N-methyl-2-[2-(2.5-dimethylphe-
`compound such as
`noxymethyl)phenyl}-2-methoxv-iniinoacetamide
`(SSF
`4-bromo-2-cyano-N.N-dimethyl-6-trilluoromethy]-
`129),
`benzitnidazole-l-sulfouamide. a-[N-(3-chioro-2,6-xylyl)-2-
`ineihoxyacelainidol-y-butyrolactone,
`4-chloro-2-cyano-N.
`N-dill1elhyl-5-p-tolylimidazole-l -sulfonamide
`(IKP-9 16.
`3-5-dichloro-N-(3-chloro-1-ethyl-1-
`cyamidazosuifamrd),
`methyl-2-oxopropyl)-4-inethylbenzamide (RH-7281, zoxa
`mide), N-allyl-4,5,-dimethyl-2-trirnethylsilylthiophenc-3-
`N-(1-cyano-l,2-
`(M0N65500),
`carboxamide
`dimeihylpropyl)-2-(2,4-dichlorophenoxy)propionamide
`(AC382042), N-(2-methoxy-5-pyridyl)-cyclopropane ear
`boxamide, N-[(1RS,4SR)-9-(Dichloromethylidene)-1 2,34-
`teirahydro-] ,4-rnelhanonaphthalen-5-yI]-3.(difiuorom-
`acibeniolar
`ethyl)- 1-methyl-i I-l-pyrazoie-4-carboxamide,
`(CGA245704). alanycarb. aldimurph. anilazine. azacuna
`zole. azoxystrobin. benalaxyl, benomyi, hiloxazol, bixafen,
`biterlanoi. blasticidin S. boscalid. bromuconazole. bupiri
`mate, bulvlamine. caplafu]. captan. carbendaziju. carbenda
`earvone,
`carpropamid,
`aim chiorhydrate,
`carboxin,
`chlorani
`chinomethiounte,
`CGA4 1397,
`CGA4 1396,
`formethan, chlorothalonil, chiorozolinate, elozylacon, cop
`per containing compounds such as copper oxycliloride, cop
`per oxyquinolate, copper sulfate, copper lallate and Bordeaux
`mixture, cyllufenamid, cymoxanil. cyprocenazole, cyprodi.
`nil. debacarb, di-2-pyridyl disulfidc 1,1-dioxide, dichioflu
`anid, dic]ocvmet, dielornezine. diclornu, diethofencar’o,
`difenoconazole. difeozoquat. diflumetorim. (J.O-di-iso-pro
`thiophospliate. dimefluazole. dirnetcnnnzole,
`pyl-S-benzyl
`dinocap.
`dimethirimol,
`dinicunazole,
`dimetiumorph.
`diihianon, dodecyl dimeihyl ammonium chloride, dode
`morph, tiodicin. dodine. doguadine, edifenphos, epoxicona
`zole, etbamoxam, ethirimol, ethyl-(Z)-—N-benzyl-N-([me
`thyl(methyl-thioethylideneaminooxycarbonyl)amino]thin)
`fenamidone
`famoxadone,
`-alaninate.
`etridiazole,
`(RPA4072 13), fenaritnol, fenbuconazole, fenfuram, fenhexa
`mid (KBR2738), fenoxanil, fenpiclonil. fenpropidin, fen
`propimorph, fentin acetate, fentin hydroxide, ferbam, fermi
`fluoroimide,
`flumetover.
`fludioxonil.
`zone,
`fluazinam.
`flutriafoL fluxapy
`(lutolanil,
`flusilazolc,
`fluquinconazoic,
`roxad. folpet, fuberidazole, fitralax-yl. fur-ametpyr, fiarfur-al,
`guazatine, hexaconazole, hydroxyisoxazole. hymexazole,
`imazalil. imibenconazole. iminoctadine, iminoctadine triac
`iprovalicarb
`iprodione.
`ipconazule,
`iprobeufos,
`etate,
`isoprothiolane,
`isopropanyl buty] carbamale.
`(SZX0722),
`isopyrazam, isotianil, kasugamyeio, kresoxim-methyl, lepto
`mycits, LY186054, LY2I 1795, TY248908, mancozeb, mart
`dipropamid, maneb, mefenoxarn, mepanipyrim, mepronii,
`metalaxyl, metconazole, meliram, metiram-zinc, metomi
`•netsulfovax. myclobutanil. neoaso7in, nickel
`nosirobin,
`dimethyldithiocarbamaic,
`nuarimol.
`nitrothal-i sopropyl,
`OCH, ofurace, organomercury compouuds. oxadixyl, oxas
`
`ulfuron, oxolinic acid, oxpoconazole, oxycarhoxin, pefura
`zoate, penconazole. pencycuron, penthiopyrad. phenazin
`oxide, phoseivl-Al. phosphonis acids, phtha!ide. picox
`ystrobin (ZA1963j, polyoxin 1). poiyram, probenazole,
`propamocarb.
`propiconazole,
`procymidone,
`prochloraz.
`propineb, propionic acid, prothiaconazole, pyrazophos,
`pyi-ifenox, pyriniethanil, pyroquilon, pyroxyfur, pyrrolnitrin,
`quatemary ammonium compounds, quinazainid, quinome
`thionale, quinoxyfen, quintuzene, silthiofaot, sipconazole
`(F-I55), sodium pentachlorophenate, spiroxarnine, strepto
`tecnazene, tetra
`mycio, sui bar, tebuconazole, tecloflalam,
`thifluzatuid, 2-(lhiocyanotneth-
`thiahendazole,
`conazole,
`thiophanate-methyl.
`ylthio)benzothiazole,
`thiram,
`lijnibenconazo]e, tolclofos-methyl. tolylfluanid, triadimefon,
`tricvclazole.
`(ricyclic
`triazoxide.
`triazbutil,
`Iriadimenol.
`amine derivatives as disclosed in WO 07/48556, tridemorph,
`trifluusizole, triti
`tritloxystrobin (CGA279202).
`triforine,
`conazole, validamycin A, valifenaiate, vaparn. vinelozolin.
`xiwojunan, zineb and ziram.
`in another embodintent, component B is an insecti
`[0022j
`cides including:
`a) a pyrethsoid selected from the group consisting of per
`feuvalerate, esfenvalerate, delta
`cypermethrin,
`methrin,
`lambdn-cyhalothrin, gamma-cyhalo
`methrin, eyhalothrin,
`tefluthrin,
`fenpropathrin,
`cyfluthrin,
`bifenthrin,
`thrin,
`ethofenpmx, natural pyrethr-in, letramethrin, S-hioallethrin,
`fenflulhrin. prallethrin and 5-benzv]-3-furvlmethyl-(E)-(l R,
`3S)-2,2-dimethyi.3-(2-oxothiolan-3-ylidcnentethyl)cvclo-
`pro pane carboxylate;
`b) an organophosphate selected from the group consisting of
`ineihamidophos,
`profenofos,
`Iriazophos.
`acephale.
`dimethoate. chlorpyi-ifos, pirimiphos-methyl. pirimiphos
`ethyl, fenitrotlj.ion, fosthiazate;
`c) a carbatnate selected from (he group consisting of pirinii
`carb, triazamate, carbosulfan, bendiocarb, fenobucarb, pro
`puxur, methomyl and oxamyl;
`d) a heuzoyl urea selected from the group consisting of
`hexaflumuron, flufenoxuron. lufenuron and chlorfluazut-on;
`an organic tin compound selected from the group consisting
`ofcyhexatin. fenbutaun oxide and azocyclotin:
`I) a pyrazole selected from the group consisting of tebufen
`pyrad and fenpyroximate;
`g) a macrolide selected from the group consisting of abam
`ectin.emamectin(c.g. emamectinbenzoatc), ivermectin. mil
`bemycin. spinosad, azadii-nchiia and spinetoram;
`h) an organochlorine compound selected from the group con
`sisting of endosulfan (in patlicular alpha-endosulfan),
`j) a fumigant agent selected from the group consisting of
`chloropicrin, dichloropropane, methyl bromide and metam;
`k) a neonicotinoid compound selected from the group con
`sisting ofimidacloprid. Ihiacloprid, acetamiprid, nitenpyram,
`thiamethoxam, c]othianidin, nilhiazine and
`dinolefuran.
`flonicamid;
`I) a diacylhydrazine selected from the group consisting of
`tebufenozide. chromafenozide and methoxyfenozide;
`m) a diphenyl ether selected from the group consisting of
`pvriproxyfen:
`n) indoxacarb;
`o) ehlorfenapyr;
`p) pymetrozine;
`q) spirotetramat, spirodiclofen and spiromesifen;
`r) a diamide selected from the group consisting of flubendia
`mide, ehlorantraniliprole (Rynaxypyr) and cyantranilip
`role;
`
`

`

`US 2016/0212993 Al
`
`Jul. 28, 2016
`
`4
`
`s) sulfoxaflor;
`t) metaflumizone;
`u) fipronil and ethiprole;
`v) pyrifluqinazon; and
`w) buprofezin
`[0023]
`Inone embodiment of the invention component B is
`a compound selected from a neonicotinoid compound
`selected from the group consisting of imidacloprid, thiaclo
`prid, acetanjiprid, nilenpyram, dinotefuran, thiamethoxam,
`clothianidin, nithiazine and flonicamid.
`Plant growth regulators Examples of suitable plnnt
`10024]
`growth regulators that may be used as a further active ingre
`dient in the mixture of the invention may be any compound
`selected from ancymidol, ehlormequat chloride, ethephon,
`fiurprimidol,
`gibberellic
`acid,
`gibberellin
`flunietralin,
`A4/gibberellin A7. maleic hydrazide, mepiquat chloride,
`paclobutrazol, prohexadione calcium.
`thiadiazuron. trinex
`apac ethyl and uniconazole.
`[0025] The adjuvant composition of the present invention
`may further contain other inert additives such as standard
`formulation components and diluents. Such inert additives
`include flow enhancers, other wetting agents, antifoaining
`agents, biocides, drift control agents, deposition enhancers,
`adjuvants, evaporation retardants, freeze protecting agents,
`liv protecting agents, fragrances, and the like.
`[0026]
`In addition, adjuvant composition according to the
`invention maybe applied with other horticultural components
`for lawn, garden, or other vegetation treatment, including,
`further wetting agents, colorants (for aesthetic purposes or for
`application identification), perfumes, watei electrolytes, fer
`tilizer, growth hormones, minerals, spray pattern indicators
`and the like. Suitably, application to plants, parts of plants,
`seeds, or at rheir locus of growth may be made in any desired
`sequence, including simultaneously, separately, or in succes
`sion, and soil or foliar applied.
`[0027] According to the invention “useful plants” typically
`comprise thefollowing species of plants: grapevines; cereals,
`such as wheat, barley, rye or oats; beet, such as sugar beet or
`fodder beet; fruits, such as pomes, stone fruits or soft fruits,
`forexainple apples, pears, plums, peaches, almonds, cherries,
`strawberries, raspberries or blackberries; leguminous plants,
`such as beans, lentils, peas or soybeans; oil plants, such as
`rape, mustard, poppy, olives, sunflowers, coconut, castor oil
`plants, cocoa beans or groundnuts; cucumber plants, such as
`marrows, cucumbers or melons; fibre plants, such as cotton,
`flax, hemp orjute; citrus fruit, such as oranges, lemons, grape
`lettuce,
`fruit or mandarins; vegetables, such as spinach,
`asparagus, cabbages, carrots, onions,
`tomatoes, potatoes,
`cueurbits or paprika; lauraeeae, such as avocados, cinnamon
`or camphor; maize; tobacco; nuts; coffee; sugar cane; tea;
`vines; hops; durian; bananas; natural rubber plants; turf or
`omamentals, such as flowers, shrubs, broad-leaved trees or
`evergreens, for example conifers, ibis list does not represent
`any limitation and is to be understood as including also useful
`plants which have been so transformed by the use of recom
`binant DNA techniques
`In one embodiment, the adjuvant of the invention is
`[0028]
`well tolerated by all major turf species various turf grasses
`including the cool-season turt’ grasses (at seeding orto estab
`fine fescue, Kentucky bluegrass.
`lished annual ryegrass,
`perennial ryegrass, tall fescue) and warm-season turf grasses
`(centipede, hybrid bennudagrass, and St. Augustinegrass.
`There may also be mentioned common bermuda and zoysia
`grass).
`
`In general, the formulations include front 0.01 to
`[0029j
`90% by weight of active agent, from 0 to 20% agriculturally
`acceptable surfactant and 10 to 99.99% solid or liquid forinu
`lation inerts and adjuvant(s), the active agent consisting of at
`least the terpenie alkoxylate A together with a compound of
`component H. and optionally other active agents, particularly
`mierobiocides or conservatives or the like. Concentrated
`forms of compositions generally contain in between about 2
`and 80%, preferably between about 5 and 70% by weight of
`active agent. Application forms of formulation may for
`example contain from 0.01 to 2O% by weight. preferably fmm
`0.01 to 5% by weight of active agent. Whereas coimuercial
`products will preferably be formulated as concentrates, the
`end user will normally employ diluted formulations.
`In one embodiment, the adjuvant component A of
`[0030]
`the invention is applied in an effective amount which is typi
`cally at a rate of 20 1/ha in a water volume of 200-1000 lures
`per hectare using conventional spray equipment.
`
`EXAMPLES
`
`[0031] The following examples are provided for illustra
`tion piuposes and should not be considered as limiting the
`scope of the invention.
`In general, active ingredient is formulated (SC, SL)
`[0032)
`and just before spraying the formulations are mixed with
`water and ultrasonically agitated in order to achieve homo
`geneous distribution. Spray solutions are made up in water.
`Adjuvants are added as tank mix to the spray solution just
`before application. Foliar application is at 200 L/ha in an
`application device spraying with a single nozzle (type
`Lechler) 60 cm above the plants. Preventative tests are per
`formed as I or 2 day preventative applications, i.e. plants are
`treated with the compounds 1 or 2 days prior to artificial
`inoculation with fungal spores, whereas for curative tests the
`inoculation is carried out prior to application. A single evalu
`ation of disease level is made 5 to 48 days after inoculation,
`depending on the pathosystem. Disease control relative to the
`untreated check plants is then calculated. In the following
`examples, all treatments were sprayed at 2001/ha spray vol
`ume in I0% isopropanol solution to normalise foliar reten
`tion: Azoxystmbin;—Quadris 5C250, Isopyrazam;—5C250,
`Cyproconazole: —Alto SL100, Chlorothalonil; Bravo
`5C720
`
`DETAILED METHOD DESCRIPTIONS
`
`[0033] Alternaria solanilfoniato/Preventative A1ten,aria
`on Tomato)->ALTELYP/ff-pr-S:
`4-week old tomato plants cv. Roter Gnom are
`[00341
`sprayed in a spray chamber with the formulated test com
`pound diluted in water. The test plants are inoculated by
`spraying them with a spore suspension two days after appli
`cation. The inoculated test plants are incubated at 22/18° C.
`(day/night) and 95% rh in a greenhouse and the percentage
`leaf area covered by disease is assessed when an appropriate
`level of disease appears on untreated cheek plants (5-7 days
`after application).
`tritici)f
`(Septoria
`[0035j Mj’cosphoerella granuio:co!a
`Wheat/Preventative (Septoria h-itici Leaf Spot on Wheat)
`>SEI’FFRZ/ff-pr-S:
`2-week old wheatplants cv. Riband are sprayed in a
`10036]
`spray chamber with the formulated test compound diluted in
`water. The test plants are inoculated by spraying a spore
`suspension on them one day after application. After an incu
`
`

`

`US 2016/0212993 Al
`
`Jul. 28, 2016
`
`5
`
`bation period of I day at 22° C./2 1° C. (day/night) and 95%
`rh. Ihe inoculated test plants are kept at 22° C./21° C. (day!
`night) and 70% rh in a greenhouse. Percenlage leaf area
`covered by disease was assessed and efficacy was calculated
`compare to untreated controls when an appropriate level of
`disease appears on untreated check plants (16-19 days after
`application).
`Puccinia recondite f. Sp. Trilici/Wheat/Preventa
`(0037]
`live (Brown Rust onWheat)->PUCCTRZ/ff-pr-S:
`2-week otd wheat plants cv. Ama are sprayed in a
`0038]
`spray chamber with the formulated test compound dituted in
`waler. The lest plants are inoculated by spraying them with a
`spore suspension one day after application. After an incuba
`tion period of 1 day at 200 C. and 95% rh, the inoculated test
`plants are kept at 20° C/IS0 C. (day/night) and 60% rh in a
`greenhouse. The perceotage leaf area covered by disease is
`assessed when an appropriate level of disease appears on
`untreated check plants (12-14 days after application).
`
`Puccinia recondita f. Sp. Ti-ilicilWhent/Curative
`10039]
`(Brown Rust on Wheat)->PTJCCTRZ/ff-cti-S:
`2-week old wheat plants cv. Anna arc inoculated by
`(0040]
`spraying thctu with a spore suspension two days before appli
`cation. Afteran incubationperiod of 1 day at 20° C. and 95%
`fit tollowedby 1 day at 20’ C. and 60% rh in a greenhouse, the
`inoculated test plants are sprayed in a spray chamber withthe
`formulated test compound diluted in water. After additional
`incubation at 20° C./18° C. (day/night) and 60% rh in a
`greenhouse. the percentage leaf area covered by disease is
`assessed when an appropriate level of disease appears on
`untreated check plants (9-12 days after application).
`Examples 1-6
`
`Azoxystrobin
`[00411 Results for Puccinia preventative test (pr-colunm)
`and Puccinia curative test (cu-column) on wheat. Visual
`assessments of control; average of three replicates per treat
`ment. Nimbus commercial adjuvant and methyl oleate are
`standard adjuvants for comparison.
`
`TABLE 1
`
`Substance
`
`(mc. in
`ppm ai
`
`Cone. in
`g riOts
`
`Adjuv. Coac.
`In %
`
`PUCCIRY)
`if-pr
`
`PUCCTRZ/
`if-cu
`
`(1) Control
`
`Water + Isopiopanot
`Nopot-5P0-9E0
`(Rtrndoclean MSC)
`Nopot-SPO-25E0
`iRtodccean 515
`Nopzt-5PG-’O
`CRtodccean EEC1
`Methyl oteare
`Ninbus
`?.zoxystrobin
`(Quadets SC 250)
`
`.ksoxystrobLn
`(Quadria SC 250) +
`Nopol-SPO-9E0
`
`Azoxystrobin
`(Quadiis SC 250) +
`Nopot-SPO-25E0
`
`A2oxyatrobin
`(Quadde SC 250).
`Nct,c.U5?O7EO
`
`Azoxystrebin
`Quadris SC 250 *
`Methyl oleate
`
`0.20
`
`0.20
`
`0.20
`
`0.20
`0.20
`
`0.20
`0.20
`(1.20
`0.20
`0.20
`0.20
`
`0.20
`0.20
`0.20
`0.20
`0.20
`0.20
`
`0.10
`0.20
`0.20
`0.20
`0.20
`0.20
`
`0.20
`0.20
`0.20
`0.20
`
`880
`200
`50
`I 2.5
`3
`0.75
`
`800
`200
`50
`12.5
`3
`0.75
`
`800
`200
`50
`12.5
`3
`0.75
`
`800
`200
`50
`2.5
`3
`0.75
`
`800
`200
`52
`12.5
`
`:50
`40
`10
`2.5
`0.6
`0.15
`
`t60
`40
`tO
`2.5
`0.6
`0.15
`
`160
`40
`10
`2.5
`0.6
`0.t5
`
`160
`40
`20
`2.5
`0.6
`0.15
`
`160
`40
`tO
`2.5
`
`(2)
`
`(3)
`
`(4)
`
`(5)
`
`0
`0
`
`0
`
`0
`
`0
`0
`
`99
`90
`54
`0
`0
`
`98
`97
`97
`79
`42
`
`96
`96
`93
`71
`
`94
`99
`85
`85
`33
`
`98
`1 (N)
`90
`
`t3
`
`0
`96
`93
`79
`79
`54
`
`100
`tOO
`tOO
`96
`88
`
`98
`96
`98
`96
`79
`
`97
`100
`98
`96
`93
`
`tOO
`100
`99
`tOO
`
`

`

`US 2016/0212993 Al
`
`Jul. 28, 2016
`
`6
`
`TABLE 1 -continued
`
`Subatnoce
`
`Cone, in
`ppm ai
`
`Cone, in Mjuv. Cone.
`g al/ha
`In %
`
`PUCCTRZJ
`if-pr
`
`PtJCCTRZI
`if-cu
`
`.-5zoxystrobin
`(Quidris SC 250) +
`Nimbus 0.2%
`
`3
`0.75
`
`800
`200
`50
`12-5
`3
`035
`
`0.6
`0.15
`
`(6)
`
`160
`40
`10
`2.5
`0.6
`0.15
`
`0.20
`0.20
`
`0.20
`0.20
`0.20
`0.20
`0.20
`0.20
`
`bxamples 7-12
`
`100
`
`100
`100
`98
`100
`
`92
`38
`
`99
`98
`94
`87
`29
`
`Isopyrazarn
`(0042! Results for Puccipiha preventative test and Pitcriniu
`curative test on wheal. Visual assessments of control: average
`of three replicates per treatment. Nimbus commercial adju
`vantandmetliyloleaieare standardadjuvantsforcoinparison.
`
`TABLE 2
`
`Substance
`
`Cone, in
`ppm ii
`
`Cone, in Mjuv. Cone.
`p siTha
`to %
`
`PUCCTRZ/
`if-pr
`
`PUCCfRZ/
`if-cu
`
`(7) Control
`
`Water + Isopropanol
`Nopol-5IO-900
`(ceSeclean MSC)
`Nepo!-5iO-2500
`(RhMean 5251
`Ncpol-5P0-7E0
`(Rhodoclean EFC)
`Methyl cleats
`Nimbus
`tsopyrazam
`(SC 250i
`
`laopyrazam
`(SC 250) +
`NopoI-5P0-9E0
`
`Esopyrazana
`(SC)50)+
`NcpzI-5P25EO
`
`Sb’S 520 453
`SC 250
`A15300C+
`Noa!-5?O-7EO
`
`Isopyrazam
`(SC 250) +
`Methyl oleate
`
`0.20
`
`0.20
`
`0,20
`
`0.20
`0,20
`
`0.20
`0.20
`0.20
`0.20
`0.20
`0.20
`
`0.20
`0.20
`0.20
`0.20
`0.20
`0.20
`
`0,20
`0,20
`0.20
`0.20
`0.20
`0.20
`
`0,20
`0.20
`0.20
`
`25:1)
`625
`156
`39
`9.75
`2.5
`
`2500
`625
`156
`39
`9,75
`2.5
`
`2500
`623
`156
`39
`9,75
`2.5
`
`2500
`625
`156
`39
`935
`2.5
`
`251)0
`625
`156
`
`500
`125
`3
`
`7.8
`1.95
`0.5
`
`500
`125
`31
`7.8
`1,95
`0.5
`
`500
`125
`31
`7.8
`:95
`0,5
`
`500
`125
`31
`7,5
`1.95
`0.5
`
`500
`125
`31
`
`(8)
`
`(9)
`
`(10)
`
`(II)
`
`0
`0
`
`0
`
`0
`
`0
`0
`
`83
`67
`29
`4
`0
`
`93
`83
`46
`21
`0
`
`90
`88
`88
`21
`0
`
`96
`83
`54
`0
`0
`
`95
`96
`
`13
`0
`
`0
`
`0
`
`0
`0
`94
`79
`50
`42
`4
`
`97
`100
`96
`67
`21
`
`95
`98
`95
`92
`33
`
`100
`98
`98
`79
`42
`
`100
`96
`92
`
`

`

`US 2016/0212993 Al
`
`7
`
`JuL. 28, 2016
`
`TABLE 2-continued
`
`Substance
`
`Cone, in
`ppm ai
`
`Cone. in Mjuv. Cone-
`In %
`g al-ha
`
`?UCCTRZJ
`if-pr
`
`PL’CCTR.ZJ
`if-ca
`
`Teopyrazam
`(SC 250) +
`Nimbus 0.2%
`
`39
`9.75
`2.5
`
`2500
`625
`156
`39
`9.75
`2.5
`
`7.8
`1.95
`0.5
`
`(12)
`
`500
`125
`31
`YR
`l.9S
`0.5
`
`0.20
`0.20
`0.20
`
`0.20
`0.20
`0.20
`0.20
`0.20
`0.20
`
`Examples 13-18
`
`77
`46
`17
`
`98
`99
`79
`38
`21
`
`88
`46
`
`90
`97
`94
`79
`42
`
`Cyproc