WO2018156554A1 - 1-hydroxy-1,3-dihydrobenzo[c][1,2]oxaboroles et utilisation de ces derniers en tant qu'herbicides - Google Patents

1-hydroxy-1,3-dihydrobenzo[c][1,2]oxaboroles et utilisation de ces derniers en tant qu'herbicides Download PDF

Info

Publication number
WO2018156554A1
WO2018156554A1 PCT/US2018/018913 US2018018913W WO2018156554A1 WO 2018156554 A1 WO2018156554 A1 WO 2018156554A1 US 2018018913 W US2018018913 W US 2018018913W WO 2018156554 A1 WO2018156554 A1 WO 2018156554A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
alkynyl
alkenyl
alkoxy
unsubstituted
Prior art date
Application number
PCT/US2018/018913
Other languages
English (en)
Inventor
Karla BRAVO-ALTAMIRANO
Olena CASTELLO
Joseph M. Gruber
Lowell MARKLEY
Dilpreet S. RIAR
Joshua Roth
Maurice C. Yap
Original Assignee
Dow Agrosciences Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dow Agrosciences Llc filed Critical Dow Agrosciences Llc
Publication of WO2018156554A1 publication Critical patent/WO2018156554A1/fr

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • A01N55/08—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur containing boron
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds

Definitions

  • R represents H or an agriculturally acceptable salt or ester
  • Ri represents cyano; C1-C12 alkyl in which the alkyl is unsubstituted or substituted with OH, NH2, C1-C2 alkylamino, di-(Ci-C2 alkyl)amino, C1-C2 alkoxy, C1-C2 haloalkoxy, C1-C2 alkylthio or C1-C2 haloalkylthio; Ci-Cs haloalkyl; C3-C8 cycloalkyl; C2-C8 alkenyl; C2- C 8 haloalkenyl; C 2 -C 8 alkynyl; C 2 -C 8 haloalkynyl; -C(0)OR 6 ; -C(0)NR 7 R 8 ; C 8 -Ci 4 arylalkyl; C8-C14 arylalkenyl; Cs-Ci 4 arylalkynyl
  • R2, R3, R4 and R5 independently represent H; cyano; halo; nitro; N3 ⁇ 4; Ci-C 6 alkylamino; di-(Ci-C6 alkyl)amino; C1-C12 alkyl; Ci-C 8 alkoxy; Ci-C 8 haloalkyl; Ci-C 8 haloalkoxy; C3-C8 cycloalkyl; C2-C8 alkenyl; C2-C8 haloalkenyl; C2-C8 alkynyl; C2-C8 haloalkynyl; -C(0)OR6; -C(0)NR 7 Rs; aryl or aryloxy in which the aryl or aryloxy is unsubstituted or substituted with one or more R9; or where R3 and R 4 are taken together as -OCH2O-, -OCH2CH2O-, -OCH2CH2- or -OCF2O-, provided that R 2 , R 3
  • R 6 , R 7 and Rs independently represent H; C1-C12 alkyl; C3-C8 alkenyl; or C3-C8 alkynyl; in which the alkyl, alkenyl or alkynyl is unsubstituted or substituted with one or more OH, Ci-C 4 alkoxy, Ci-C 4 alkylthio, or phenyl groups, provided that R 6 , R 7 and Rs are sterically compatible; and
  • R9 represents halo, C1-C12 alkyl, Ci-Cs alkoxy, Ci-Cs haloalkyl, or Ci-Cs haloalkoxy; with the proviso that R3 is not -XYC(0)ORio, wherein
  • X represents O, NRn, S, SO, or SO2 where Rn is H, Ci-C6-alkyl, C3-C6-alkenyl, or
  • Y represents Ci-C6-alkyl, C3-C6-alkenyl, or C3-C 6 -alkynyl, in which the alkyl, alkenyl or alkynyl is unsubstituted or substituted with one or more halogen, Ci-C6-alkyl, Ci-C 6 - haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, C(0)0(Ci-C6-alkyl) or phenyl which is unsubstituted or substituted by halogen, Ci-C6-alkyl, Ci-C6-haloalkyl; and
  • Rio represents H, Ci-C6-alkyl, C3-C6-alkenyl, C3-C6- alkynyl, (Ci-C6-alkoxy)-Ci-C6- alkyl, (Ci-C6-alkoxy)-C3-C6-alkenyl, (C1-C6- alkoxy)-C3-C6-alkynyl, phenyl, phenyl-Ci-C6- alkyl, where the aliphatic and phenyl parts of the aforementioned radicals are unsubstituted, partly or completely halogenated.
  • herbicidal composition comprising a compound of Formula
  • R represents H or an agriculturally acceptable salt or ester
  • Ri represents cyano; C1-C12 alkyl in which the alkyl is unsubstituted or substituted with OH, NH2, C1-C2 alkylamino, di-(Ci-C2 alkyl)amino, C1-C2 alkoxy, C1-C2 haloalkoxy, C1-C2 alkylthio or C1-C2 haloalkylthio; Ci-Cs haloalkyl; C3-C8 cycloalkyl; C2-C8 alkenyl; C2- C 8 haloalkenyl; C 2 -C 8 alkynyl; C 2 -C 8 haloalkynyl; -C(0)OR 6 ; -C(0)NR 7 R 8 ; C 8 -Ci 4 arylalkyl; C 8 -Ci 4 arylalkenyl; C 8 -Ci 4 arylalkynyl; or aryl in which the aryl
  • R2, R3, R 4 and R5 independently represent H; cyano; halo; nitro; NH2; ⁇ -Ce alkylamino; di-(Ci-C6 alkyl)amino; C1-C12 alkyl; Ci-C 8 alkoxy; Ci-C 8 haloalkyl; Ci-C 8 haloalkoxy; C3-C 8 cycloalkyl; C2-C 8 alkenyl; C2-C 8 haloalkenyl; C2-C 8 alkynyl; C2-C 8 haloalkynyl; -C(0)OR6; -C(0)NR 7 R 8 ; aryl or aryloxy in which the aryl or aryloxy is unsubstituted or substituted with one or more R9; or where R3 and R 4 are taken together as -OCH2O-, -OCH2CH2O-, -OCH2CH2- or -OCF2O-, provided that R 2 ,
  • R 6 , R 7 and R 8 independently represent H; C1-C12 alkyl; C3-C 8 alkenyl; or C3-C 8 alkynyl; in which the alkyl, alkenyl or alkynyl is unsubstituted or substituted with one or more OH, Ci-C 4 alkoxy, Ci-C 4 alkylthio, or phenyl groups, provided that R 6 , R 7 and R 8 are sterically compatible;
  • R9 represents halo, C1-C12 alkyl, Ci-C 8 alkoxy, Ci-C 8 haloalkyl, or Ci-C 8 haloalkoxy; with the proviso that R3 is not -XYC(0)ORio, wherein
  • X represents O, NRn, S, SO, or SO2 where Rn is H, Ci-C6-alkyl, C3-C6-alkenyl, or C 3 -C6-alkynyl;
  • Y represents Ci-C6-alkyl, C3-C6-alkenyl, or C3-C 6 -alkynyl, in which the alkyl, alkenyl or alkynyl is unsubstituted or substituted with one or more halogen, Ci-C6-alkyl, Ci-C 6 - haloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, C(0)0(Ci-C6-alkyl) or phenyl which is unsubstituted or substituted by halogen, Ci-C6-alkyl, Ci-C6-haloalkyl; and Rio represents H, Ci-C6-alkyl, C3-C6-alkenyl, C3-C6- alkynyl, (Ci-C6-alkoxy)-Ci-C6- alkyl, (Ci-C6-alkoxy)-C3-C6-alkenyl, (Ci
  • Also provided are methods of controlling undesirable vegetation comprising
  • herbicide As used herein, herbicide, herbicide composition, and herbicidal active ingredient mean a compound that controls undesirable vegetation when applied in an appropriate amount.
  • control of or controlling undesirable vegetation means killing or preventing the vegetation, or causing some other adversely modifying effect to the vegetation e.g., deviations from natural growth or development, regulation, desiccation, retardation, and the like.
  • a herbicidally effective or vegetation controlling amount is an amount of herbicidal active ingredient the application of which controls the relevant undesirable vegetation.
  • applying a herbicide, herbicidal composition, or herbicidal active ingredient means delivering it directly to the targeted vegetation or to the locus thereof or to the area where control of undesired vegetation is desired.
  • Methods of application include, but are not limited to, pre-emergently contacting soil or water, or post-emergently contacting the undesirable vegetation or area adjacent to the undesirable vegetation.
  • plants and vegetation include, but are not limited to, dormant seeds, germinant seeds, emerging seedlings, plants emerging from vegetative propagules, immature vegetation, and established vegetation.
  • agriculturally acceptable salts and esters for R refer to salts and esters of compounds of Formula (I) that exhibit herbicidal activity, or that are or can be converted in plants, water, or soil to the referenced herbicide.
  • exemplary agriculturally acceptable esters are those that are or can be hydrolyzed, oxidized, metabolized, or otherwise converted, e.g., in plants, water, or soil, to the corresponding 1-hydroxy-oxaborole or boronic acid which, depending upon the pH, may be in the dissociated or undissociated form.
  • Suitable agriculturally acceptable salts include those derived from alkali or alkaline earth metals and those derived from ammonia and amines.
  • Preferred cations include sodium, potassium, magnesium, and aminium cations of the formula:
  • Salts of the compounds of Formula (I) can be prepared by treatment of compounds of Formula (I) with a metal hydroxide, such as sodium hydroxide, with an amine, such as ammonia, trimethylamine, diethanolamine, 2-methyl- thiopropylamine, bisallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine, or benzylamine, or with a tetraalkylammonium hydroxide, such as tetramethylammonium hydroxide or choline hydroxide.
  • Amine salts of compounds of Formula (I) are useful forms or derivatives of compounds of Formula (I) because they are water-soluble and lend them- selves to the preparation of desirable aqueous based herbicidal compositions.
  • Suitable agriculturally acceptable esters include straight chain or branched chain alkyl groups.
  • Typical C1-C12 alkyl groups include, but are not limited to, methyl, ethyl, propyl, 1- methylethyl, butyl, 1,1-dimethylethyl, 1-methylpropyl, pentyl, hexyl, heptyl, 1-methyl-hexyl, octyl, 2-ethylhexyl, nonyl, decyl and dodecyl. Methyl and ethyl are often preferred.
  • alkyl refers to saturated, straight-chained or branched hydrocarbon moieties. Unless otherwise specified, C1-C12 alkyl groups are intended (e.g., Ci-C 6 alkyl). Examples include, but are not limited to, methyl, ethyl, propyl, 1 -methyl-ethyl, butyl, 1- methyl-propyl, 2-methyl-propyl, 1,1 -dimethyl-ethyl, pentyl, 1 -methyl-butyl, 2-methyl-butyl, 3-methyl-butyl, 2,2-dimethyl-propyl, 1-ethyl-propyl, hexyl, 1,1-dimethyl-propyl, 1,2- dimethyl-propyl, 1-methyl-pentyl, 2-methyl-pentyl, 3-methyl-pentyl, 4-methyl-pentyl, 1,1- dimethyl-butyl, 1,2-dimethyl-butyl, 1,3-di
  • haloalkyl refers to straight-chained or branched alkyl groups, where in these groups the hydrogen atoms may partially or entirely be substituted with one or more halogen atom(s).
  • Ci-Cs groups are intended (e.g., Ci-C 6 haloalkyl). Examples include, but are not limited to, chloromethyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl,
  • chlorofluoromethyl dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1- bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2- fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl, and l,l,l-trifluoroprop-2-yl.
  • cycloalkyl refers to saturated, cyclic hydrocarbon moieties. Unless otherwise specified, C3-C8 cycloalkyl groups are intended. Examples include cyclopropyl, 2,2-dimethyl-cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • alkenyl refers to unsaturated, straight-chained, or branched hydrocarbon moieties containing one or more double bond(s). Unless otherwise specified, C2-C8 alkenyl groups are intended (e.g., C3-C6 alkenyl). Alkenyl groups may contain more than one unsaturated bond.
  • Examples include, but are not limited to, ethenyl, 1-propenyl, 2- propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1 -methyl- 1-propenyl, 2-methyl- 1-propenyl, l-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-l-butenyl, 2-methyl- 1-butenyl, 3-methyl- 1-butenyl, l-methyl-2- butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, l-methyl-3-butenyl, 2-methyl-3 -butenyl, 3- methyl-3-butenyl, l,l-dimethyl-2-propenyl, 1 ,2-dimethyl- 1-propenyl, 1 ,2-dimethyl-2- propenyl, 1 -eth
  • haloalkenyl refers to straight-chained or branched alkenyl groups, where in these groups the hydrogen atoms may partially or entirely be substituted with one or more halogen atom(s). Unless otherwise specified, C2-C8 groups are intended.
  • Examples include, but are not limited to 1-chloroethenyl, 1-chloro- 1 -propenyl, 2-chloro-l -propenyl, 1- chloro-2-propenyl, 2-chloro-2-propenyl, 1-chloro- 1-butenyl, 2-chloro-l -butenyl, 3-chloro-l- butenyl, l-chloro-2-butenyl, 2-chloro-2-butenyl, 3-chloro-2-butenyl, l-chloro-3-butenyl, 2- chloro-3-butenyl, 3-chloro-3-butenyl, 1-fluoroethenyl, 1-fluoro-l -propenyl, 2-fluoro-l- propenyl, l-fluoro-2-propenyl, 2-fluoro-2-propenyl, 1-fluoro-l-butenyl, 2-fluoro-butenyl, 3-fluor
  • alkynyl represents straight-chained or branched hydrocarbon moieties containing one or more triple bond(s). Unless otherwise specified, C2-C8 alkynyl groups are intended (e.g., C3-C6 alkynyl). Alkynyl groups may contain more than one unsaturated bond.
  • Examples include, but are not limited to, C2-Cs-alkynyl, such as ethynyl, 1-propynyl, 2-propynyl (or propargyl), 1-butynyl, 2-butynyl, 3-butynyl, l-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 3-methyl- 1-butynyl, l-methyl-2-butynyl, l-methyl-3-butynyl, 2-methyl-3-butynyl, l,l-dimethyl-2-propynyl, l-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 3-methyl- 1-pentynyl, 4-methyl-l- pentynyl,
  • haloalkynyl refers to straight-chained or branched alkynyl groups, where in these groups the hydrogen atoms may partially or entirely be substituted with one or more halogen atom(s). Unless otherwise specified, C2-C8 groups are intended.
  • Examples include, but are not limited to, l-chloro-2-butynyl, l-chloro-3-butynyl, 2-chloro-3-butynyl, l,l-dichloro-2-propynyl, l-chloro-2-propynyl, 3 -chloro- 1-pentynyl, 4-chloro- 1-pentynyl, 1- chloro-2-pentynyl, 4-chloro-2-pentynyl, l-chloro-3-pentynyl, 2-chloro-3-pentynyl, 1-chloro- 4-pentynyl, 2-chloro-4-pentynyl, 3-chloro-4-pentynyl, l,l-dichloro-2-butynyl, 1,1-dichloro- 3-butynyl, l,2-dichloro-3-butynyl, 2,2-dichloro
  • alkoxy refers to a group of the formula R-0-, where R is alkyl as defined above (e.g., Ci-C 6 alkoxy). Unless otherwise specified, alkoxy groups wherein R is a Ci-C 8 alkyl group are intended.
  • Examples include, but are not limited to, methoxy, ethoxy, propoxy, 1-methyl-ethoxy, butoxy, 1 -methyl -propoxy, 2-methyl-propoxy, 1,1-dimethyl- ethoxy, pentoxy, 1-methyl-butyloxy, 2-methyl-butoxy, 3-methyl-butoxy, 2,2-dimethyl- propoxy, 1-ethyl-propoxy, hexoxy, 1,1-dimethyl-propoxy, 1,2-dimethyl-propoxy, 1-methyl- pentoxy, 2-methyl-pentoxy, 3-methyl-pentoxy, 4-methyl-pentoxy, 1,1-dimethyl-butoxy, 1,2- dimethyl-butoxy, 1,3-dimethyl-butoxy, 2,2-dimethyl-butoxy, 2,3-dimethyl-butoxy, 3,3- dimethyl-butoxy, 1-ethyl-butoxy, 2-ethylbutoxy, 1 , 1 ,2-trimethyl-propoxy, 1,2,2-trimethyl- propoxy, 1 -ethyl
  • haloalkoxy refers to a group of the formula R-0-, where R is haloalkyl as defined above. Unless otherwise specified, haloalkoxy groups wherein R is a Ci-C 8 alkyl group are intended (e.g., Ci-C 6 haloalkoxy). Examples include, but are not limited to, chloromethoxy, bromomethoxy, dichloromethoxy, trichloromethoxy,
  • dichlorofluoromethoxy chlorodifluoromethoxy, 1-chloroethoxy, 1-bromoethoxy, 1- fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2- fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2- trichloroethoxy, pentafluoroethoxy, and l,l,l-trifluoroprop-2-oxy.
  • alkylthio refers to a group of the formula R-S- where R is alkyl as defined above. Unless otherwise specified, alkylthio groups wherein R is a Ci-C 8 alkyl group are intended. Examples include, but are not limited to, methylthio, ethyl thio, propylthio, 1- methylethylthio, butylthio, 1-methyl-propylthio, 2-methylpropylthio, 1,1-dimethylethylthio, pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 1- methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1-
  • haloalkylthio refers to an alkylthio group as defined above wherein the carbon atoms are partially or entirely substituted with one or more halogen atoms. Unless otherwise specified, haloalkylthio groups wherein R is a Ci-C 8 alkyl group are intended. Examples include, but are not limited to, chloromethylthio, bromomethylthio,
  • chlorodifluoromethylthio 1-chloroethylthio, 1-bromoethylthio, 1 -fluoroethylthio, 2- fluoroethylthio, 2,2-difluoroethylthio, 2,2,2-trifluoroethylthio, 2-chloro-2-fluoroethylthio, 2- chloro-2-difluoroethylthio, 2,2-dichloro-2-fluoroethylthio, 2,2,2-trichloroethylthio, pentafluoroethylthio, and l,l,l-trifluoroprop-2-ylthio.
  • aryl refers to a phenyl, indanyl, or naphthyl group. In some embodiments, phenyl is preferred. Unless otherwise specified, the aryl groups may be unsubstituted or substituted with one or more substituents selected from, e.g.
  • halogen hydroxy, nitro, cyano, formyl, Ci-C 6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, Ci-C 6 alkoxy, Ci-C 6 haloalkyl, Ci-C 6 haloalkoxy, Ci-C 6 acyl, Ci-C 6 alkylthio, Ci-C 6 alkylsulfinyl, Ci-C 6 alkylsulfonyl, (Ci-Ce alkoxy)carbonyl, Ci-C 6 carbamoyl, hydroxycarbonyl, (Ci-Ce alkyl)carbonyl, aminocarbonyl, (Ci-C6 alkylamino)carbonyl, (di(Ci- C 6 alkyl)amino)carbonyl, provided that the substituents are sterically compatible and the rules of chemical bonding and strain energy are satisfied.
  • preferred substituents include, for example, halogen, C1-C
  • arylalkyl refers to an alkyl, alkenyl, or alkynyl group substituted with an aryl group as defined herein.
  • alkoxycarbonyl refers to a group of the formula wherein is alkyl.
  • alkylamino refers to an amino group substituted with one or two alkyl, alkenyl, or alkynyl groups, which may be the same or different, e.g., Ci-C 6 alkyl, C3-C6 alkenyl, or C3-C6 alkynyl.
  • alkylcarbamyl refers to a carbamyl group substituted on the nitrogen with an alkyl group.
  • alkylsulfonyl refers to -SO2R, wherein R is alkyl (e.g. , C1-C10 alkyl).
  • X can for example be S, SO, or SO2.
  • carbamoyl or aminocarbonyl refers to a group of the formula
  • haloalkylamino refers to an alkylamino group wherein the alkyl carbon atoms are partially or entirely substituted with one or more halogen atoms.
  • Me refers to a methyl group
  • halogen refers to fluorine, chlorine, bromine, or iodine (or fluoride, chloride, bromide, or iodide).
  • plants and vegetation include, but are not limited to, germinant seeds, emerging seedlings, plants emerging from vegetative propagules, immature vegetation, and established vegetation.
  • R is H.
  • Ri is cyano
  • Ri is C1-C4 alkyl. In one embodiment, Ri is Me.
  • Ri is C2-C4 alkynyl. In one embodiment, Ri is ethynyl.
  • Ri is a substituted phenyl. In one embodiment, Ri is 4- chlorophenyl. In another embodiment, Ri is 2,4-dichlorophenyl.
  • R 4 is cyano. In another embodiment, R 4 is trifluoromethyl. In another embodiment, R 4 is fluoro.
  • Ri is methyl and one of R2, R3, R 4 , R5 is not hydrogen
  • a nucleophile for example a Grignard reagent, such as methylmagnesium bromide or
  • step a of Scheme 2 a 2-bromobenzaldehyde of Formula 2.0 is transformed into the 2-formylphenylboronate of Formula 2.1 , wherein Z 2 is an acyclic boronate such as
  • B(0(Ri5)) 2 and R15 Ci-C 4 alkyl, by treatment with an alkylboron reagent, such as trimethylborate or triisopropylborate, in the presence of n-butyllithium (n-BuLi), in an ethereal solvent, such as THF, at low temperature, for example -78 °C under an inert atmosphere.
  • an alkylboron reagent such as trimethylborate or triisopropylborate
  • a nucleophile for example a Grignard reagent, such as methylmagnesium bromide or ethynylmagnesium bromide, or a lithium reagent, such as methyllithium or phenyllithium, in an ethereal solvent,
  • the compounds of Formula 2.2 can be generated in a two-step, one pot process wherein the aforementioned steps (a and b) are reversed (b, then a).
  • step b of Scheme 4 the 1-hydroxy- oxaborole 4.1 is then allowed to react with a strong mineral acid, such as 6 Normal (N) hydrochloric acid (HC1), in a polar protic solvent, such as ethyl alcohol, at an elevated temperature, for example reflux under an inert atmosphere to provide the compound of
  • a strong mineral acid such as 6 Normal (N) hydrochloric acid (HC1)
  • a polar protic solvent such as ethyl alcohol
  • the geminal dibromide is hydrolyzed in the presence of silver nitrate in an aqueous alcohol, such as ethyl alcohol in water at an elevated temperature, such as reflux, to provide 4-bromo-3- formylbenzonitrile(5.2), as in step b.
  • an aqueous alcohol such as ethyl alcohol in water at an elevated temperature, such as reflux
  • the hydroxyl group is alkylated with an alkylating reagent such as methyl chloromethyl ether (MOMC1), in the presence of a base, such N,N- diisopropylethylamine (DIPEA), in a halogenated hydrocarbon solvent, such as
  • step e the substituted methoxymethoxymethyl derivative is converted to the 1 hydroxy-l,3-dihydrobenzo-[c][l,2]oxaborole-5-carbonitrile 5.5, wherein R 4 is cyano, and Ri, R2, R3, and R5 are as originally defined, by treatment with triisopropylborate and n-BuLi at low temperature in an anhydrous ether solvent, such as THF.
  • an anhydrous ether solvent such as THF.
  • a mineral acid such as concentrated HC1
  • the compounds of Formulae 1.2, 2.2, 3.2, 4.1, 4.2, 5.5, 5.6, and 5.7, wherein R, Ri, R2, R3, R4 and R5 are as originally defined, obtained by any of these processes, can be recovered by conventional means and purified by standard procedures, such as by trituration, recrystallization or chromatography.
  • the compounds of Formula (I) where R is an agriculturally acceptable salt or ester can be prepared from compounds of Formulae 1.2, 2.2, 3.2, 4.1, 4.2, 5.5, 5.6, and 5.7 using standard methods well known in the art.
  • the compounds provided herein are employed in mixtures containing a herbicidally effective amount of the compound along with at least one agriculturally acceptable adjuvant or carrier.
  • exemplary adjuvants or carriers include those that are not phytotoxic or significantly phytotoxic to valuable crops, e.g. , at the
  • compositions for selective weed control in the presence of crops can be designed for application directly to weeds or their locus or can be concentrates or formulations that are diluted with additional carriers and adjuvants before application.
  • They can be solids, such as, for example, dusts, granules, water dispersible granules, or wettable powders, or liquids, such as, for example, emulsifiable concentrates, solutions, emulsions or suspensions. They can also be provided as a pre-mix or tank-mixed.
  • Suitable agricultural adjuvants and carriers that are useful in preparing the herbicidal mixtures of the disclosure are well known to those skilled in the art.
  • Some of these adjuvants include, but are not limited to, crop oil concentrate (mineral oil (85%) + emulsifiers (15%)); nonylphenol ethoxylate; benzylcocoalkyldimethyl quaternary ammonium salt; blend of petroleum hydrocarbon, alkyl esters, organic acid, and anionic surfactant; C9-C11
  • alky lpoly glycoside phosphated alcohol ethoxylate; natural primary alcohol (C12-C16) ethoxylate; di-s ⁇ ?obutylphenol EO-PO block copolymer; polysiloxane-methyl cap;
  • Liquid carriers that can be employed include water and organic solvents.
  • the organic solvents typically used include, but are not limited to, petroleum fractions or hydrocarbons such as mineral oil, aromatic solvents, paraffinic oils, and the like; vegetable oils such as soybean oil, rapeseed oil, olive oil, castor oil, sunflower seed oil, coconut oil, corn oil, cottonseed oil, linseed oil, palm oil, peanut oil, safflower oil, sesame oil, tung oil and the like; esters of the above vegetable oils; esters of monoalcohols or dihydric, trihydric, or other lower polyalcohols (4-6 hydroxy containing), such as 2-ethylhexyl stearate, n -butyl oleate, isopropyl myristate, propylene glycol dioleate, di-octyl succinate, di-butyl adipate, di-octyl phthalate and the like; esters of mono-, di-
  • organic solvents include toluene, xylene, petroleum naphtha, crop oil, acetone, methyl ethyl ketone, cyclohexanone, trichloroethylene, perchloroethylene, ethyl acetate, amyl acetate, butyl acetate, propylene glycol monomethyl ether and diethylene glycol monomethyl ether, methyl alcohol, ethyl alcohol, isopropyl alcohol, amyl alcohol, ethylene glycol, propylene glycol, glycerine, N-methyl-2-pyrrolidinone, NN-dimethyl alkylamides, dimethyl sulfoxide, liquid fertilizers, and the like.
  • water is the carrier for the dilution of concentrates.
  • Suitable solid carriers include talc, pyrophyllite clay, silica, attapulgus clay, kaolin clay, kieselguhr, chalk, diatomaceous earth, lime, calcium carbonate, bentonite clay, Fuller's earth, cottonseed hulls, wheat flour, soybean flour, pumice, wood flour, walnut shell flour, lignin, and the like.
  • one or more surface- active agents are utilized in the compositions of the present disclosure. Such surface-active agents are, in some
  • the surface-active agents can be anionic, cationic or nonionic in character and can be employed as emulsifying agents, wetting agents, suspending agents, or for other purposes.
  • Surfactants conventionally used in the art of formulation and which may also be used in the present formulations are described, inter alia, in
  • Typical surface-active agents include salts of alkyl sulfates, such as diethanolammonium lauryl sulfate; alkylarylsulfonate salts, such as calcium
  • dodecylbenzenesulfonate alkylphenol-alkylene oxide addition products, such as
  • nonylphenol-Ci8 ethoxylate alcohol-alkylene oxide addition products, such as tridecyl alcohol-Ci6 ethoxylate
  • soaps such as sodium stearate
  • alky lnaphthalene- sulfonate salts such as sodium dibutylnaphthalenesulfonate
  • dialkyl esters of sulfosuccinate salts such as sodium di(2-ethylhexyl) sulfosuccinate
  • sorbitol esters such as sorbitol oleate
  • quaternary amines such as lauryl trimethylammonium chloride
  • polyethylene glycol esters of fatty acids such as polyethylene glycol stearate
  • salts of mono- and dialkyl phosphate esters such as soybean oil, rapeseed/canola oil, olive oil, castor oil, sunflower seed oil, coconut
  • some of these materials can be used interchangeably as an agricultural adjuvant, as a liquid carrier or as a surface active agent.
  • compositions may also contain other compatible components, for example, other herbicides, plant growth regulants, fungicides, insecticides, and the like and can be formulated with liquid fertilizers or solid, particulate fertilizer carriers such as ammonium nitrate, urea and the like.
  • concentration of the active ingredients in the herbicidal compositions of this disclosure is generally from about 0.001 to about 98 percent by weight.
  • compositions designed to be employed as concentrates the active ingredient is generally present in a concentration from about 5 to about 98 weight percent, preferably about 10 to about 90 weight percent.
  • Such compositions are typically diluted with an inert carrier, such as water, before application.
  • the diluted compositions usually applied to weeds or the locus of weeds generally contain about 0.0001 to about 1 weight percent active ingredient and preferably contain about 0.001 to about 0.05 weight percent.
  • compositions can be applied to weeds or their locus by the use of conventional ground or aerial dusters, sprayers, and granule applicators, by addition to irrigation or flood water, and by other conventional means known to those skilled in the art.
  • the compounds and compositions described herein are applied as a post-emergence application, pre-emergence application, in-water application to flooded paddy rice or water bodies (e.g. , ponds, lakes and streams), or burn-down application.
  • the compounds and compositions provided herein are utilized to control weeds in crops, including but not limited to citrus, apple, rubber, oil, palm, forestry, direct-seeded, water-seeded and transplanted rice, wheat, barley, oats, rye, sorghum, corn/maize, pastures, grasslands, rangelands, fallowland, turf, tree and vine orchards, aquatics, or row-crops, as well as non-crop settings, e.g. , industrial vegetation management (IVM) or rights-of-way.
  • the compounds and compositions are used to control woody plants, broadleaf and grass weeds, or sedges.
  • the compounds and compositions provided herein are utilized to control undesirable vegetation in rice.
  • the undesirable vegetation is Brachiaria platyphylla (Groseb.) Nash (broadleaf signalgrass, BRAPP), Digitaria sanguinalis (L.) Scop, (large crabgrass, DIGSA), Echinochloa crus-galli (L.) P. Beauv. (barnyardgrass, ECHCG), Echinochloa colonum (L.) LINK (junglerice, ECHCO),
  • Echinochloa oryzoides (Ard.) Fritsch (early watergrass, ECHOR), Echinochloa oryzicola (Vasinger) Vasinger (late watergrass, ECHPH), Ischaemum rugosum Salisb. (saramollagrass, ISCRU), Leptochloa chinensis (L.) Nees (Chinese sprangletop, LEFCH), Leptochloa fascicularis (Lam.) Gray (bearded sprangletop, LEFFA), Leptochloa panicoides (Presl.) Hitchc.
  • AMMCO Eclipta alba
  • Hassk. American false daisy, ECLAL
  • Heteranthera limosa SW.
  • Willd./Vahl ducksalad
  • Heteranthera reniformis R. & P. roundleaf mudplantain, HETRE
  • Ipomoea hederacea L.
  • Jacq. ivyleaf morningglory, IPOHE
  • Lindernia dubia (L.) Pennell (low false pimpernel, LIDDU), Monochoria korsakowii Regel & Maack (monochoria, MOOKA), Monochoria vaginalis (Burm. F.) C. Presl ex Kuhth, (monochoria, MOOVA), Murdannia nudiflora (L.) Brenan (doveweed, MUDNU),
  • Polygonum pensylvanicum L. (Pennsylvania smartweed, POLPY), Polygonum persicaria L. (ladysthumb, POLPE), Polygonum hydropiperoides Michx. (mild smartweed, POLHP), Rotala indica (Willd.) Koehne (Indian toothcup, ROTIN), Sagittaria species, (arrowhead, SAGSS), Sesbania exaltata (Raf.) Cory/Rydb. Ex Hill (hemp sesbania, SEBEX), or Sphenoclea zeylanica Gaertn. (gooseweed, SPDZE).
  • the compounds and compositions provided herein are utilized to control undesirable vegetation in cereals.
  • the undesirable vegetation is Alopecurus myosuroides Huds. (blackgrass, ALOMY), Apera spica-venti (L.) Beauv. (windgrass, APESV), Avenafatua L. (wild oat, AVEFA), Bromus tectorum L.
  • the compounds and compositions provided herein are utilized to control undesirable vegetation in range and pasture.
  • the undesirable vegetation is Ambrosia artemisiijolia L. (common ragweed, AMBEL), Cassia obtusifolia (sickle pod, CASOB), Centaurea maculosa auct. non Lam. (spotted knapweed, CENMA), Cirsium arvense (L.) Scop. (Canada thistle, CIRAR), Convolvulus arvensis L. (field bindweed, CONAR), Euphorbia esula L.
  • Wiggers (dandelion, TAROF), Trifolium repens L. (white clover, TRFRE), or Urtica dioica L. (common nettle, URTDI).
  • the compounds and compositions provided herein are utilized to control undesirable vegetation found in row crops.
  • the undesirable vegetation is Alopecurus myosuroides Huds. (blackgrass, ALOMY), Avenajatua L. (wild oat, AVEFA), Brachiaria platyphylla (Groseb.) Nash (broadleaf signalgrass, BRAPP), Digitaria sanguinalis (L.) Scop, (large crabgrass, DIGSA), Echinochloa crus-galli (L.) P. Beauv. (barnyardgrass, ECHCG), Echinochloa colonum (L.) Link (junglerice, ECHCO), Lolium multiflorum Lam.
  • application rates of about 1 to about 4,000 grams/hectare (g/ha) are employed in post-emergence operations. In some embodiments, rates of about 1 to about 4,000 g/ha are employed in pre-emergence operations.
  • the compounds, compositions, and methods provided herein are used in conjunction with one or more other herbicides to control a wider variety of undesirable vegetation
  • the presently claimed compounds can be formulated with the other herbicide or herbicides, tank-mixed with the other herbicide or herbicides or applied sequentially with the other herbicide or herbicides.
  • aminocyclopyrachlor aminopyralid, amiprofos -methyl, amitrole, ammonium sulfamate, anilofos, anisuron, asulam, atraton, atrazine, azafenidin, azimsulfuron, aziprotryne, barban, BCPC, beflubutamid, benazolin, bencarbazone, benfluralin, benfuresate, bensulfuron-methyl, bensulide, benthiocarb, bentazon-sodium, benzadox, benzfendizone, benzipram,
  • dimethachlor dimethametryn, dimethenamid, dimethenamid-P, dimexano, dimidazon, dinitramine, dinofenate, dinoprop, dinosam, dinoseb, dinoterb, diphenamid, dipropetryn, diquat, disul, dithiopyr, diuron, DMPA, DNOC, DSMA, EBEP, eglinazine, endothal, epronaz, EPTC, erbon, esprocarb, ethalfluralin, ethbenzamide, ethametsulfuron, ethidimuron, ethiolate, ethobenzamid, etobenzamid, ethofumesate, ethoxyfen, ethoxysulfuron, etinofen, etnipromid, etobenzanid, EXD, fenasulam, f
  • the compounds and compositions of the present disclosure can generally be employed in combination with known herbicide safeners, such as benoxacor, benthiocarb, brassinolide, cloquintocet (e.g. , mexyl), cyometrinil, daimuron, dichlormid, dicyclonon, dimepiperate, disulfoton, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, furilazole, harpin proteins, isoxadifen-ethyl, mefenpyr-diethyl, MG 191, MON 4660, naphthalic anhydride (NA), oxabetrinil, R29148 and N-phenylsulfonylbenzoic acid amides, to enhance their selectivity.
  • known herbicide safeners such as benoxacor, benthiocarb, brassinolide, cloquintocet (e.g. , mex
  • exemplary resistant or tolerant weeds include, but are not limited to, biotypes resistant or tolerant to ALS inhibitors, photosystem II inhibitors, ACCase inhibitors, synthetic auxins, photosystem I inhibitors, 5-enolpyruvylshikimate-3- phosphate (EPSP) synthase inhibitors, microtubule assembly inhibitors, lipid synthesis inhibitors, PPO inhibitors, carotenoid biosynthesis inhibitors, very long chain fatty acid
  • VLCFA phytoene desaturase
  • PDS phytoene desaturase
  • HPPD HPPD inhibitor
  • mitosis inhibitors cellulose biosynthesis inhibitors
  • herbicides with multiple modes-of-action such as quinclorac
  • unclassified herbicides such as arylaminopropionic acids, difenzoquat, endothall, and organoarsenicals.
  • exemplary resistant or tolerant weeds include, but are not limited to, biotypes with resistance or tolerance to multiple herbicides, multiple chemical classes, and multiple herbicide modes-of-action.
  • the aqueous solution was made acidic and extracted with EtiO. None of the desired oxaborole product was identified by gas chromatography-mass spectrometry (GC-MS) in the second EtiO wash. The title compound was present in first Et20 wash, which was concentrated.
  • GC-MS gas chromatography-mass spectrometry
  • the reaction mixture was poured into 3 ⁇ 40 (30 mL), cooled in an ice bath, made basic (pH 12) with 2 N NaOH, made acidic (pH 4) with 2 N HC1 and extracted with EtOAc (2 x 25 mL).
  • the combined organic extracts were washed with brine (30 mL), dried over MgSC , concentrated under reduced pressure, and dried in vacuo at ambient temperature for 14 h. Recrystallization from EtOAc/hexanes afforded the title compound as a white solid (17 mg, 19%).
  • the mother liquor was concentrated under reduced pressure and dried in vacuo at room temperature for 14 h to leave a waxy pink solid which contained additional less pure material (40 mg, 45%).
  • Herbicidal evaluations were made visually on a scale of 0 to 100 where 0 represents no activity and 100 represents complete plant death. The data are displayed as indicated in Table A.
  • Post- Emergent Test I Seeds of test species were obtained from commercial suppliers and planted into a 13 centimeter (cm) diameter-round pot containing soil-less media mix (Metro-Mix 360 ® , Sun Gro Horticulture). Postemergence treatments were planted 8-12 days (d) prior to application and cultured in a greenhouse equipped with supplemental light sources to provide a 16 hour (h) photoperiod at 24-29 °C. All pots were surface irrigated.
  • a weighed amount, determined by the highest rate to be tested, of each compound was dissolved in 1.3 milliliters (mL) acetone-dimethyl sulfoxide (DMSO; 97:3, volume per volume (v/v)) and diluted with 4.1 mL water-isopropanol-crop oil concentrate (78:20:2, v/v/v) containing 0.02% Triton X-155 to obtain concentrated stock solutions.
  • DMSO acetone-dimethyl sulfoxide
  • v/v volume per volume
  • Formulated compounds were applied using a DeVilbiss ® compressed air sprayer at 2-
  • pots 4 pounds per square inch (psi). Following treatment, pots were returned to the greenhouse for the duration of the experiment. All pots were subirrigated as needed to provide optimum growing conditions. All pots were fertilized one time per week by subirrigating with Peters Peat-Lite Special ® fertilizer (20-10-20).
  • Phytotoxicity ratings were obtained 10 days after postemergence applications. All evaluations were made visually on a scale of 0 to 100 where 0 represents no activity and 100 represents complete plant death, and the data are presented as indicated in Table A. Visual assessments of plant injury were made based on growth reduction, discoloration, leaf deformity and necrosis.
  • APESV windgrass ( Apera spica-venti (L.) Beauv.)
  • ECHCG bamyardgrass (Echinochloa crus-galli)
  • HELAN sunflower (Helianthus annuus)
  • PANDI fall panicum (Panicum dichotomiflorum (L.) Michx.)
  • PHAMI littleseed canarygrass (Phalaris minor Retz.)
  • SETFA giant foxtail (Setaria faberi)

Abstract

La présente invention concerne des 1-hydroxy-1,3-dihydrobenzo[c][1,2]oxaboroles et leurs dérivés, et des compositions et des procédés d'utilisation de ceux-ci en tant qu'herbicides.
PCT/US2018/018913 2017-02-21 2018-02-21 1-hydroxy-1,3-dihydrobenzo[c][1,2]oxaboroles et utilisation de ces derniers en tant qu'herbicides WO2018156554A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201762461469P 2017-02-21 2017-02-21
US62/461,469 2017-02-21

Publications (1)

Publication Number Publication Date
WO2018156554A1 true WO2018156554A1 (fr) 2018-08-30

Family

ID=63254107

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2018/018913 WO2018156554A1 (fr) 2017-02-21 2018-02-21 1-hydroxy-1,3-dihydrobenzo[c][1,2]oxaboroles et utilisation de ces derniers en tant qu'herbicides

Country Status (1)

Country Link
WO (1) WO2018156554A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10765117B2 (en) 2013-01-30 2020-09-08 Agrofresh Inc. Volatile applications against pathogens
US10966429B2 (en) 2016-03-07 2021-04-06 Agrofresh Inc. Synergistic methods of using benzoxaborole compounds and preservative gases as an antimicrobial for crops
US11039617B2 (en) 2013-01-30 2021-06-22 Agrofresh Inc. Large scale methods of uniformly coating packaging surfaces with a volatile antimicrobial to preserve food freshness
CN115010622A (zh) * 2022-06-20 2022-09-06 山东百启生物医药有限公司 一种2-溴-5-氰基苯甲醛的制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6511940B1 (en) * 1998-06-23 2003-01-28 Hoechst Schering Agrevo Gmbh Combination of herbicides and safeners
WO2013050591A2 (fr) * 2011-10-07 2013-04-11 Syngenta Participations Ag Procédé pour protéger des plantes utiles ou un matériau de propagation de plantes
US20150353581A1 (en) * 2013-03-15 2015-12-10 Eli Lilly And Company 1-hydroxy-benzooxaboroles as antiparasitic agents
US9416146B2 (en) * 2008-03-06 2016-08-16 Anacor Pharmaceuticals, Inc. Boron-containing small molecules as anti-inflammatory agents
US9440994B2 (en) * 2009-08-14 2016-09-13 Anacor Pharmaceuticals, Inc. Boron containing small molecules as antiprotozoal agents
WO2016164589A1 (fr) * 2015-04-09 2016-10-13 The Penn State Research Foundation Composition antifongicide contenant du benzoxaborole

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6511940B1 (en) * 1998-06-23 2003-01-28 Hoechst Schering Agrevo Gmbh Combination of herbicides and safeners
US9416146B2 (en) * 2008-03-06 2016-08-16 Anacor Pharmaceuticals, Inc. Boron-containing small molecules as anti-inflammatory agents
US9440994B2 (en) * 2009-08-14 2016-09-13 Anacor Pharmaceuticals, Inc. Boron containing small molecules as antiprotozoal agents
WO2013050591A2 (fr) * 2011-10-07 2013-04-11 Syngenta Participations Ag Procédé pour protéger des plantes utiles ou un matériau de propagation de plantes
US20150353581A1 (en) * 2013-03-15 2015-12-10 Eli Lilly And Company 1-hydroxy-benzooxaboroles as antiparasitic agents
WO2016164589A1 (fr) * 2015-04-09 2016-10-13 The Penn State Research Foundation Composition antifongicide contenant du benzoxaborole

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10765117B2 (en) 2013-01-30 2020-09-08 Agrofresh Inc. Volatile applications against pathogens
US11039617B2 (en) 2013-01-30 2021-06-22 Agrofresh Inc. Large scale methods of uniformly coating packaging surfaces with a volatile antimicrobial to preserve food freshness
US11202448B2 (en) 2013-01-30 2021-12-21 Agrofresh Inc. Volatile applications against pathogens
US11771089B2 (en) 2013-01-30 2023-10-03 Agrofresh Inc. Large-scale methods of uniformly coating packaging surfaces with a volatile antimicrobial to preserve food freshness
US11917997B2 (en) 2013-01-30 2024-03-05 Agrofresh Inc. Volatile applications against pathogens
US10966429B2 (en) 2016-03-07 2021-04-06 Agrofresh Inc. Synergistic methods of using benzoxaborole compounds and preservative gases as an antimicrobial for crops
CN115010622A (zh) * 2022-06-20 2022-09-06 山东百启生物医药有限公司 一种2-溴-5-氰基苯甲醛的制备方法
CN115010622B (zh) * 2022-06-20 2024-01-09 山东百启生物医药有限公司 一种2-溴-5-氰基苯甲醛的制备方法

Similar Documents

Publication Publication Date Title
AU2018264871B2 (en) 4-amino-6-(heterocyclic)picolinates and 6-amino-2-(heterocyclic)pyrimidine-4-carboxylates and their use as herbicides
EP3569600B1 (fr) 4-amino-6-(hétérocyclique)-picolinates et 6-amino-2-(hétérocyclique)-pyrimidine-4-carboxylates et leur utilisation comme herbicides
AU2014235455B2 (en) 4-amino-6-(heterocyclic)picolinates and 6-amino-2-(heterocyclic)pyrimidine-4-carboxylates and their use as herbicides
DK2967069T3 (en) 4-AMINO-6- (4-SUBSTITUTED-PHENYL) -PICOLINATES AND 6-AMINO-2- (4-SUBSTITUTED-PHENYL) -PYRIMIDIN-4-CARBOXYLATES AND THEIR USE AS HERBICIDES
US10765114B2 (en) 4-amino-6-(pyridyl and 2-substitutedphenyl)-picolinates and 6-amino-2-(pyridyl and 2-substitutedphenyl)-pyrimidine-4-carboxylates and their use as herbicides
US9006250B2 (en) 4-amino-6-(heterocyclic)picolinates and 6-amino-2-(heterocyclic)pyrimidine-4-carboxylates and their use as herbicides
WO2018156554A1 (fr) 1-hydroxy-1,3-dihydrobenzo[c][1,2]oxaboroles et utilisation de ces derniers en tant qu'herbicides
US9603364B2 (en) 4-amino-6-(halo-substituted-alkyl)-picolinates and their use as herbicides
AU2019265729B2 (en) 4-amino-6-(1,3-benzodioxole)picolinates and their use as herbicides
NZ751548B2 (en) 4-amino-6-(4-substituted-phenyl)-picolinates and 6-amino-2-(4-substituted-phenyl)-pyrimidine-4-carboxylates and their use as herbicides
OA17491A (en) 4-Amino-6-(heterocycIic) picoIinates and 6amino-2-(heterocyclic) pyrimidine-4-carboxylates and their use as herbicides.

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 18756988

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 18756988

Country of ref document: EP

Kind code of ref document: A1