WO1995010188A2 - Herbicidal aza bisphosphonic acid compositions - Google Patents

Herbicidal aza bisphosphonic acid compositions Download PDF

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Publication number
WO1995010188A2
WO1995010188A2 PCT/GB1994/002183 GB9402183W WO9510188A2 WO 1995010188 A2 WO1995010188 A2 WO 1995010188A2 GB 9402183 W GB9402183 W GB 9402183W WO 9510188 A2 WO9510188 A2 WO 9510188A2
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Prior art keywords
alkyl
substituted
halo
alkoxy
hydrocarbyl
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PCT/GB1994/002183
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English (en)
French (fr)
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WO1995010188A3 (en
Inventor
Karl Joseph Fisher
Frank Xavier Woolard
John Montgomery Gerdes
Original Assignee
Zeneca Limited
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Publication date
Application filed by Zeneca Limited filed Critical Zeneca Limited
Priority to AU77901/94A priority Critical patent/AU690581B2/en
Priority to NZ274000A priority patent/NZ274000A/en
Priority to SK452-96A priority patent/SK45296A3/sk
Priority to JP7511442A priority patent/JPH09506075A/ja
Priority to BR9407762A priority patent/BR9407762A/pt
Priority to EP94928482A priority patent/EP0722268A1/en
Priority to PL94313820A priority patent/PL313820A1/xx
Publication of WO1995010188A2 publication Critical patent/WO1995010188A2/en
Publication of WO1995010188A3 publication Critical patent/WO1995010188A3/en
Priority to NO961389A priority patent/NO961389L/no
Priority to FI961520A priority patent/FI961520A/fi

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    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4025—Esters of poly(thio)phosphonic acids
    • C07F9/405—Esters of poly(thio)phosphonic acids containing nitrogen substituent, e.g. N.....H or N-hydrocarbon group which can be substituted by halogen or nitro(so), N.....O, N.....S, N.....C(=X)- (X =O, S), N.....N, N...C(=X)...N (X =O, S)
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-carbon bonds
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
    • C07F9/3839—Polyphosphonic acids
    • C07F9/3873—Polyphosphonic acids containing nitrogen substituent, e.g. N.....H or N-hydrocarbon group which can be substituted by halogen or nitro(so), N.....O, N.....S, N.....C(=X)- (X =O, S), N.....N, N...C(=X)...N (X =O, S)
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/5532—Seven-(or more) membered rings
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/568—Four-membered rings
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/572—Five-membered rings
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576—Six-membered rings
    • C07F9/58—Pyridine rings
    • C—CHEMISTRY; METALLURGY
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    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576—Six-membered rings
    • C07F9/59—Hydrogenated pyridine rings
    • C—CHEMISTRY; METALLURGY
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    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
    • C07F9/576—Six-membered rings
    • C07F9/60—Quinoline or hydrogenated quinoline ring systems
    • C—CHEMISTRY; METALLURGY
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    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6503—Five-membered rings
    • C07F9/65031—Five-membered rings having the nitrogen atoms in the positions 1 and 2
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6503—Five-membered rings
    • C07F9/6506—Five-membered rings having the nitrogen atoms in positions 1 and 3
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/645—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having two nitrogen atoms as the only ring hetero atoms
    • C07F9/6509—Six-membered rings
    • C07F9/6512—Six-membered rings having the nitrogen atoms in positions 1 and 3
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6515—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having three nitrogen atoms as the only ring hetero atoms
    • C07F9/6518—Five-membered rings
    • 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
    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
    • C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07F9/6533—Six-membered rings

Definitions

  • this invention relates to herbicidal aza-bisphosphonic acid compositions comprising (A) an azabisphosphonic acid wherein the nitrogen atom and the carbon atom to which the two phosphonic acid groups are bound are linked with a single carbon atom and (B) a suitable carrier therefor.
  • this invention is directed to a method of controlling the growth of plants comprising applying to the area where control is desired an herbicidally effective amount of such an aza-bisphosphonic acid compound.
  • this invention is directed to certain novel aza-bisphosphonic acid compounds.
  • herbicides which exhibit desirable efficacy against plants when applied postemergently, but which further exhibit little significant activity when applied preemergently. Such herbicides will, for example, permit the control of weeds already present in a field but will not harm crops which have not yet emerged. Accordingly, it is an object of this invention to provide effective novel herbicidal compositions and a novel method of controlling weeds, as well as certain novel herbicidal compounds. It is a further object of this invention to provide novel compositions, methods and herbicidal compounds which exhibit admirable postemergent control coupled with no significant preemergent control.
  • Japanese Patent Publication 54-147925 discloses herbicidal bisphosphonic acid compounds wherein the phosphonic acid groups are bound to a single carbon atom. Such compounds are of the Formula:
  • X and Y are each hydrogen, halogen, alkyl or cycloalkyl; or salts thereof.
  • R is H, lower alkyl or halogen
  • X is -CH 2 -, S or O
  • Y is H, lower alkyl or halogen; and alkali salts thereof.
  • German Patent DE 2754821 discloses compounds useful as
  • this invention is directed to a herbicidal composition
  • a herbicidal composition comprising:
  • R 1 is hydrogen, hydroxy, C 1 -C 4 alkoxy, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, hydroxy-C 1 -C 4 -alkyl, hydroxy ⁇
  • R 6 and R 7 are each independently hydrogen or C 1 -C 3 alkyl
  • R 2 and R 3 are each independently hydrogen; hydrocarbyl; substituted hydrocarbyl; hydrocarbyloxy; substituted hydrocarbyloxy; hydrocarbyl-S(O) m -; or substituted hydrocarbyl-S(O) m -; or
  • R 2 and R 3 together form a 3-6 membered carbocyclic ring, optionally substituted with halogen, hydroxy, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio or N(R 8 )(R 9 ) wherein R8 and R 9 are each independently hydrogen or C 1 -C 12 alkyl; and
  • R 4 and R 5 are each independently hydrogen; hydrocarbyl; substituted hydrocarbyl; hydrocarbyloxy; substituted hydrocarbyloxy; hydrocarbylthio; substituted hydrocarbylthio; pyridyl; substituted pyridyl; or are of the formula
  • R 10 and R 11 are independently hydrogen, hydrocarbyl or substituted hydrocarbyl; or
  • R 4 and R 5 together with the nitrogen to which they are bound form an aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethyleneimine, piperidine, tetrahydropyridine, pyrazole, imidazole, pyrrole, triazole, tetrahydropyrimidine, dihydroimidazole, pyrroline, azetidine, perhydroindole, perhydroquinoline, perhydroisoquinoline or pyrrolidine ring, any of which may be optionally substituted with C 1 -C 12 alkyl, halo,
  • R 2 and R 4 together with the nitrogen and carbon atoms to which they are bound form an aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethyleneimine, piperidine, tetrahydropyridine, pyrazole, imidazole, pyrrole, triazole, tetrahydropyrimidine, dihydroimidazole, pyrroline, azetidine, perhydroindole, perhydroquinoline, perhydroisoquinoline or pyrrolidine ring, any of which may be optionally substituted with C 1 -C 12 alkyl, halo, C 6 -C 10 aryl, C 6 -C 10 aryl substituted with halo or C 1 -C 6 alkyl, C 7 -C 16 aralkyl, C 7 -C 16 aralkyl substituted with
  • n 0, 1 or 2;
  • this invention is directed to a method of controlling the growth of plants comprising applying to the area where control is desired an herbicidally effective amount of a compound of Formula (I) above.
  • this invention is directed to certain novel compounds having a structure within the scope of Formula (I) above.
  • compositions of this invention comprise a bisphosphonic acid compound of the Formula (I):
  • R 1 is hydrogen, hydroxy, C 1 -C 4 alkoxy, halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, hydroxy-C 1 -C 4 -alkyl, hydroxy ⁇
  • R 6 and R 7 are each independently hydrogen or C 1 -C 3 alkyl
  • R 2 and R 3 are each independently hydrogen; hydrocarbyl; substituted hydrocarbyl; hydrocarbyloxy; substituted hydrocarbyloxy; hydrocarbyl-S(O) m -; substituted hydrocarbyl-S(O) m ; or
  • R 2 and R 3 together form a 3-6 membered carbocyclic ring, optionally substituted with halogen, hydroxy, C 1 -C 6 alkyl, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio or N(R 6 ) (R 7 ) wherein R and R are each independently hydrogen or C 1 -C 4 alkyl; and
  • R 4 and R 5 are each independently hydrogen; hydrocarbyl; substituted hydrocarbyl; hydrocarbyloxy; substituted hydrocarbyloxy; hydrocarbylthio; substituted hydrocarbylthio; pyridyl; substituted pyridyl; or are of the formula
  • R 10 and R 11 are independently hydrogen, hydrocarbyl or substituted hydrocarbyl; or
  • R 4 and R 5 together with the nitrogen to which they are bound form an aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethyleneimine, piperidine, tetrahydropyridine, pyrazole, imidazole, pyrrole, triazole, tetrahydropyrimidine, dihydroimidazole, pyrroline, azetidine, perhydroindole, perhydroquinoline, perhydroisoquinoline or pyrrolidine ring, any of which may be optionally substituted with C 1 -C 12 alkyl, halo, C 6 -C 10 aryl, C 6 -C 10 aryl substituted with halo or C 1 -C 6 alkyl, C 7 -C 16 aralkyl, C 7 -C 16 aralkyl substituted with halo or C 1
  • R 2 and R 4 together with the nitrogen and carbon atoms to which they are bound form an aziridine, piperazine, morpholine, thiomorpholine, thiomorpholine sulfinyl, thiomorpholine sulfonyl, hexamethyleneimine, piperidine, tetrahydropyridine, pyrazole, imidazole, pyrrole, triazole, tetrahydropyrimidine, dihydroimidazole, pyrroline, azetidine, perhydroindole, perhydroquinoline, perhydroisoquinoline or pyrrolidine ring, any of which may be optionally substituted with C 1 -C 12 alkyl, halo, C 6 -C 10 aryl, C 6 -C 10 aryl substituted with halo or C 1 -C 6 alkyl, C 7 -C 16 aralkyl, C 7 -C 16 aralkyl substituted with
  • M is 0, 1 or 2;
  • R 1 is hydrogen, hydroxy, halogen or C 1 -C 4 alkyl
  • R 2 and R 3 are independently hydrogen; C 1 -C 12 alkyl
  • R and R 5 are independently C 1 -C 6 alkyl; C 2 -C 6 alkenyl; C 2 -C 6 alkynyl; halo-C 1 -C 6 alkyl; halo-C 2 -C 6 alkenyl; halo-C 1 -C 6 -alkynyl; pyridyl; substituted pyridyl; phenyl;
  • R 4 and R 5 together with the nitrogen to which they are bound form a tetrahydropyrimidine, tetrahydropyridine, imidazole ring or a -(CH 2 ) n -N- ring wherein n is 2-6, optionally substituted with halogen, hydroxy, C 1 -C 6 alkoxy, nitro,C 1 -C 6 alkyl, C 7 -C 16 aralkyl or C 1 -C 6 alkylthio groups. More preferably,
  • R 1 is hydrogen or hydroxy
  • R 2 and R 3 are each independently hydrogen or C 1 -C 6 alkyl
  • R 4 and R 5 are each independently hydrogen, C 1 -C 6 alkyl, C 1 -C 6 alkenyl, benzyl, benzyl substituted with C 1 -C 6 alkyl or halo or
  • R 4 and R 5 together with the nitrogen to which they are bound form a pyrrolidine or piperidine ring, either of which may be optionally substituted with fluorine, hydroxy, C 1 -C 6 alkoxy or C 1 -C 6 alkyl.
  • Particularly preferred compounds for use in the herbicidal compositions and method of this invention include:
  • this invention is directed to certain classes of novel aza-bisphosphonic acid compounds.
  • R 12 and R 13 are each independently hydrogen, C 1 -C 6 straight chain or branched alkyl, hydroxy, C 2 -C 6 alkenyl, C 1 -C 6 alkoxy or C 1 -C 6 alkoxy-C 1 -C 6 alkyl; and agriculturally acceptable salts thereof.
  • Specific compounds within the scope of this genus include:
  • Novel aza-bisphosphonic acids within the scope of this invention also include those of Formula III:
  • R 14 and R 15 are each independently hydrogen or C 1 -C 6 alkyl
  • Ar is benzene, pyridine, pyrimidine, pyridazine, naphthalene, pyrazole, imidazole, triazole, thiazole, furan, thiophene, pyrrole, oxazole or thiadiazole
  • R 16 is halo, C 1 -C 10 alkyl, aryl, substituted aryl, benzyl, substituted benzyl, nitro, halo-C 1 -C 10 -alkyl, C 1 -C 10 alkoxy, C 1 -C 10 alkylthio, C 1 -C 10 alkylsulfenyl,
  • R 17 , R 18 and R 19 are each independently hydrogen, C 1 -C 10 alkyl, C 1 -C 10 substituted alkyl, C 1 -C 10 aralkyl or C 1 -C 10 alkenyl;
  • each R 14 and R 15 may themselves independently be hydrogen or C 1 -C 3 alkyl.
  • each R 16 may be the same or different.
  • A is an alkylenidene radical of 3-6 carbon atoms optionally substituted with C 1 -C 6 alkyl, and agriculturally acceptable salts thereof.
  • Specific compounds within the scope of this genus include:
  • R 20 is hydrogen or hydroxyl; and B is a C 2 -C 4
  • alkylidene linking group optionally substituted with C 1 -C 6 alkyl; and agriculturally acceptable salts thereof.
  • R 21 and R 22 are each independently C 1 -C 6 alkyl or together constitute a C 3 -C 5 alkylidene group optionally substituted with C 1 -C 6 alkyl; and agrochemically acceptable salts thereof.
  • Illustrative compounds within the scope of this invention include:
  • R 23 and R 24 are each independently hydrogen, C 1 -C 10 alkyl, halo, nitro, C 1 -C 9 alkoxy, C 1 -C 10 aralkyl, cyano, trifluoromethyl or represent a unit of unsaturation; and R 25 is hydrogen, C 1 -C 6 alkyl, C 7 -C 10 aralkyl, halo, nitro, trifluoromethyl or cyano.
  • R 23 and R 24 may themselves be different members of the group listed above.
  • Illustrative compounds within the scope of this invention include:
  • the compounds of such formulae can exist in enantiomeric forms.
  • the invention includes both individual enantiomers and mixtures of the two in all proportions.
  • hydrocarbyl whether representing a subsrituent on its own or whether it is part of the definition of a larger group (e.g., as in hydrocarbyloxy, hydrocarbyl-S(O) m -, etc.) is intended to include hydrocarbyl groups having from 1 to 16 carbon atoms.
  • hydrocarbyl therefore includes, for example, C 1 to C 16 alkyl including both straight and branched chain isomers (e.g., methyl, ethyl, propyl, isopropyl, sec-hexyl and hexyl); cycloaikyl of 3 to 16 carbon atoms (e.g., cyclopropyl, cyclobutyl and cyclohexyl); C 2 to C 16 alkenyl including for example allyl and crotyl; C 2 to C 16 alkynyl (e.g., propynyl); phenyl;
  • phenylalkyl alkylphenyl, alkenylphenyl, alkynylphenyl, alkylbenzyl, alkenylbenzyl, alkynyl benzyl, naphthyl and the like.
  • hydrocarbyl when applied to the term "hydrocarbyl” (or to a similar term unless specifically defined otherwise) is intended to include hydrocarbyl groups, as defined above, having one or more substituents selected from the group consisting of halogen (i.e., fluorine, chlorine, bromine, and iodine); C 1-10 alkoxy; C 1-10 alkyl-S(O) m -; cyano; nitro; carboxy, and salts, amides and esters thereof; alkanoyl of 2 to 10 carbon atoms; and phenyl optionally substituted by one or more C 1-10 alkyl, C 1-10 alkoxy, C 1-10 alkyl-S(O) m -, nitro, fluorine, chlorine, bromine, cyano, or CF 3 groups.
  • halogen i.e., fluorine, chlorine, bromine, and iodine
  • C 1-10 alkoxy i.e., fluorine, chlorine, bromine
  • the hydrocarbyl radical is a substituted aryl radical (e.g., phenyl, benzyl or naphthyl)
  • the substituents may include one or more of the substituents listed in the last foregoing paragraph, and may also include nitro.
  • substituted pyridyl is intended to include those substituents detailed above for substituted aryl
  • alkyl is intended to include straight chain, branched and cycloalkyl compounds.
  • halogen includes fluoro, chloro, bromo and iodo groups. In polyhalogenated groups the halogens may be the same or
  • the compounds of the present invention have been found to be active herbicides, possessing utility as post-emergence herbicides and useful against a wide range of plant species including broadleaf and grassy species.
  • This invention therefore also relates to a method for controlling undesirable vegetation comprising applying to a locus where control of such vegetation is desired subsequent to the emergence of such vegetation a herbicidally effective amount of a compound as described herein, together with an inert diluent or carrier suitable for use with herbicides.
  • herbicide and “herbicidal” are used herein to denote the inhibitive control or modification of undesired plant growth. Inhibitive control and modification include all deviations from natural development such as, for example, total killing, growth retardation, defoliation, desiccation, regulation, stunting, tillering, stimulation, leaf burn and dwarfing.
  • herbicidally effective amount is used to denote any amount which achieves such control or modification when applied to the undesired plants themselves or to the area in which these plants are growing.
  • plants is intended to include germinated seeds, emerging seedlings and established vegetation, including both roots and above-ground portions.
  • agriculturally acceptable salt is easily determined by one of ordinary skill in the art and includes alkali metal, ammonium, phosphonium, sulfonium salts, organic derivatives thereof, and the like.
  • the compounds of this invention wherein R is hydrogen may generally be prepared by reacting tetraethyl vinylidene bis(phosphonate) with an appropriate amine. Such reaction is typically carried out at between about 0° and about 100°C in the presence of a suitable nonreactive solvent, such as acetonitrile, diethyl ether, tolene, tetrahydrofuran, and the like. The ester groups may then be removed using bromotrimethylsilane or aqueous hydrochloric acid.
  • a suitable nonreactive solvent such as acetonitrile, diethyl ether, tolene, tetrahydrofuran, and the like.
  • the ester groups may then be removed using bromotrimethylsilane or aqueous hydrochloric acid.
  • Tetraethyl vinylidene bis(phosphonate) may be prepared in accordance with the method disclosed by C.
  • ester groups may first be transesterified by the use of a compound such as bromotrimethylsilane. Such groups can be subsequently unblocked by hydrolysis with water.
  • the appropriate carboxylic acid, amide or nitrile can be converted employing PCI., and phosphorous acid or P 2 O 3 utilizing means well known to those of skill in the art.
  • compositions of this invention comprise a compound of Formula (I) above and a suitable carrier, which carriers are well known to one of ordinary skill in the art.
  • the compounds of the present invention are useful as herbicides and can be applied in a variety of ways known to those skilled in the art, at various concentrations.
  • the compounds are useful in controlling the growth of undesirable vegetation by post-emergent application to the locus where control is desired.
  • the compounds are applied as formulations containing the various adjuvants and carriers known to or used in the industry for facilitating dispersion.
  • the choice of formulation and mode of application for any given compound may affect its activity, and selection will be made accordingly.
  • the compounds of the invention may thus be formulated as wettable powders, as emulsifiable concentrates, as powders or dusts, as flowables, as solutions, suspensions or emulsions, or in controlled-release forms such as microcapsules.
  • Wettable powders are in the form of finely divided particles which disperse readily in water or other liquid carriers. The particles contain the active ingredient retained in a solid matrix. Typical solid matrices include fuller's earth, kaolin clays, silicas and other readily wet organic or inorganic solids. Wettable powders normally contain about 5% to about 95% of the active ingredient plus a small amount of wetting, dispersing, or emulsifying agent.
  • Emulsifiable concentrates are homogeneous liquid compositions dispersible in water or other liquid, and may consist entirely of the active compound with a liquid or solid emulsifying agent, or may also contain a liquid carrier, such as xylene, heavy aromatic naphthas, isophorone and other non-volatile organic solvents. In use, these concentrates are dispersed in water or other liquid and normally applied as a spray to the area to be treated. The amount of active ingredient may range from about 0.5% to about 95% of the concentrate.
  • Dusts are free-flowing admixtures of the active ingredient with finely divided solids such as talc, clays, flours and other organic and inorganic solids which act as dispersants and carriers.
  • Microcapsules are typically droplets or solutions of the active material enclosed in an inert porous shell which allows escape of the enclosed material to the surroundings at controlled rates.
  • Encapsulated droplet are typically about 1 to 50 microns in diameter.
  • the enclosed material typically constitutes about 50 to 95% of the weight of the capsule, and may include solvent in addition to the active compound.
  • Shell or membrane materials include natural and synthetic rubbers, cellulosic materials, styrene-butadiene copolymers, polyacrylonitriles, polyacrylates, polyesters, polyamides, polyureas, polyurethanes and starch xanthates.
  • compositions for herbicidal applications include simple solutions of the active ingredient in a solvent in which it is completely soluble at the desired concentration, such as water acetone, alkylated naphthalenes, xylene and other organic solvents.
  • Pressurized sprayers wherein the active ingredient is dispersed in finely-divided form as a result of vaporization of a low boiling dispersant solvent carrier, such as the Freons, may also be used.
  • formulations include wetting, dispersing or emulsifying agents.
  • examples are alkyl and alkylaryl sulfonates and sulfates and their salts; polyhydric alcohols; polyethoxylated alcohols; esters and fatty amines. These agents when used normally comprise from 0.1% to 15% by weight of the formulation.
  • Each of the above formulations can be prepared as a package containing the herbicide together with other ingredients of the formulation (diluents, emulsifiers, surfactants etc.).
  • the formulations can also be prepared by a tank mix method, in which the ingredients are obtained separately and combined at the grower site.
  • the compounds of the present invention are also useful when combined with other herbicides and/or defoliants, desiccants, growth inhibitors, and the like. These other materials can comprise from about 5% to about 95% of the active ingredients in the formulations. These combinations frequently provide a higher level of effectiveness in controlling weeds and often provide results unattainable with separate formulations of the individual herbicides.
  • acetates such as DNOC, dinoterb, dinoseb and its ester, dinoseb acetate;
  • dinitroaniline herbicides such as dinitramine, trifluralin, ethalfluralin, pendimethalin; and oryzalin;
  • arylurea herbicides such as diuron, flumeturon, metoxuron, neburon, isoproturon, chlorotoluron, chloroxuron, linuron, monolinuron, chlorobromuron, daimuron, and methabenzthiazuron;
  • phenylcarbamoyloxyphenylcarbamates such as phenmedipham and desmedipham;
  • uracil herbicides such as lenacil, bromacil and terbacil;
  • J. triazine herbicides such as atrazine, simazine, aziprotryne, cyanazine, prometryn, dimethametryn, simetryne, and terbutryn;
  • K. phosphorothioate herbicides such as piperophos, bensulide, and butamifos;
  • L. thiolcarbamate herbicides such as cycloate, vernolate, molinate, thiobencarb, butylate*, EPTC*, triallate, diallate, ethyl esprocarb, tiocarbazil, pyridate, and dimepiperate;
  • N. benzoic acid herbicides such as 2,3,6-TBA, dicamba and chloramben;
  • O. anilide herbicides such as pretilachlor
  • haloalkanoic herbicides such as dalapon, TCA and salts thereof;
  • diphenylether herbicides such as lactofen, fluroglycofen or salts or esters thereof, nitrofen, bifenox, acifluorfen and salts and esters thereof, oxyfluorfen and fomesafen; chlornitrofen and chlomethoxyfen;
  • phenoxyphenoxypropionate herbicides such as diclofop and esters thereof such as the methyl ester, fluazifop and esters thereof, haloxyfop and esters thereof,
  • T. cyclohexanedione herbicides such as alloxydim and salts thereof, sethoxydim, cycloxydim, sulcotrione, tralkoxydim, and clethodim;
  • U. sulfonyl urea herbicides such as chlorosulfuron, sulfometuron, metsulfuron and esters thereof; benzsulfuron and esters thereof such as the ester thereof methyl, DPX-M6313, chlorimuron and esters such as the ethyl ester thereof, pirimisulfuron and esters such as the methyl ester thereof, DPX-LS300 and pyrazosulfuron;
  • V. imidazolidinone herbicides such as imazaquin, imazamethabenz, imazapyr and isopropylammonium salts thereof, imazethapyr;
  • arylanilide herbicides such as flamprop and esters thereof, benzoylprop-ethyl, diflufenican;
  • X. amino acid herbicides such as glyphosate and gluyfosinate and their salts and esters, sulphosate, and bilanafos;
  • Y. organoarsenical herbicides such as MSMA
  • herbicidal amide derivative such as napropamide, propyzamide, carbetamide, tebutam, bromobutide, isoxaben, naproanilide, diphenamid, and naptalam;
  • miscellaneous herbicides including ethofumesate, cinmethylin, difenzoquat and salts thereof such as the methyl sulfate salt, clomazone, oxadiazon, bromofenoxim, barban, tridiphane, (in the ratio 3:1) flurochloridone, quinchlorac and mefanacet;
  • useful contact herbicides include bipyridylium herbicides such as those in which the active entity is paraquat and those in which the active entity is diquat.
  • Dust and liquid compositions can be applied by the use of power-dusters, boom and hand sprayers and spray dusters.
  • the formulations can also be applied from airplanes as a dust or a spray or by rope wick applications.
  • These dusts are formed by mixing the components then grinding the mixture to the desired particle size.
  • Emulsifiable concentrate is prepared by intimately mixing the active compounds with the additives in suitable mixers, and grinding the resulting mixture in mills or rollers.
  • Emulsifiable concentrate is prepared by intimately mixing the active compounds with the additives in suitable mixers, and grinding the resulting mixture in mills or rollers.
  • compositions which constitute a herbicidally effective amount depends upon the nature of the seeds or plants to be controlled.
  • the rate of application of active ingredients varies from about 0.01 to about 25 pounds per acre, preferably about 0.10 to about 10 pounds per acre with the actual amount depending on the overall costs and the desired results. It will be readily apparent to one skilled in the art that compositions exhibiting lower herbicidal activity will require a higher dosage than more active compounds for the same degree of control.
  • screening are affected by a number of factors including: the amount of sunlight, soil type, soil pH, temperature, humidity, depth of planting, plant growth stage, application rate as well as many other factors. All testing procedures are administered with the least amount of variability possible. State of the art equipment and techniques are employed to enable the screening process to remain consistent and reliable.
  • AVEFA African fatua
  • EHCG barnyardgrass(Echinochloa crusgalli )
  • Broadleaf weeds utilized were wild mustard(Brassica kaber) also known as (Sinapis arvensis) (“SINAR”), velvetleaf(Abutilon theophrasti ) (“ABUTH”) and morningglory (Ipomoea spp . ) (“IPOSS”). Additionally, yellow nutsedge
  • CYPES Cerus esculentus
  • Solutions of the test compounds were prepared by weighing out 18.8 and 74.7 mg for 1 and 4 kg/ha applications respectively, of the test compound into a 60 ml wide-mouth bottle, then dissolving the compound in 14.0 ml of deionized water containing 0.5% v/v Tween 20 ® (polyoxyethylene sorbitan monolaurate emulsifier) as a surfactant. Additional solvents, not exceeding 2 ml (15% of spray volume), were used if needed to dissolve the compound.
  • Tween 20 ® polyoxyethylene sorbitan monolaurate emulsifier
  • the soil surface was sprayed inside an enclosed linear spray table with the nozzle set at 30.5 cm (12 inches) above the soil line.
  • the spray table was calibrated to deliver 748 L/ha (80 gal/A) with the application rate being 4.0 kg/ha or 1.0 kg/ha (as indicated in Table II below).
  • the greenhouse environmental systems provided the plants with natural and artificial (via metal halide lamps) lighting to attain 14 hours of light per day. Day and night temperatures were maintained at 29° and 21°C respectively.
  • the degree of weed control was evaluated and
  • Percent control is the total injury to the plants due to all factors including:
  • control ratings range from 0 to 100 percent, where 0% represents no effect with growth equal to the untreated control and where 100% represents complete kill. A dash indicates that no test was performed at that level of application.
  • the soil was prepared and seeded with the same species and methodology described for the pre-emergence test.
  • Post-emergence flats were placed in the greenhouse under the same environmental conditions as described for the pre-emergence flats and watered overhead by sprinkling. Plants were grown for 10 to 12 days (or to the appropriate growth stage) prior to compound application. Grasses were sprayed at a 3 to 4 leaf stage and broadleaves at a 1 to 2 leaf stage. Yellow nutsedge was 5 to 7 cm tall at application. Plants were sprayed 30.5 cm (12 inches) above the foliage with the same spray solution as prepared for the pre-emergence test. The application rate was 4.0 kg/ha or 1.0 kg/ha (as indicated in Table III below).
  • Treated plants were then returned to a greenhouse and watered daily without wetting the foliage.
  • the degree of weed control was evaluated 17-21 days after application and recorded as percentage of control as compared to the growth of the same species in an untreated control flat of the same age.
  • the percent control scale (0-100%) used to evaluate the pre-emergence treatment was also applied to the post-emergence treatment.

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PCT/GB1994/002183 1993-10-07 1994-10-07 Herbicidal aza bisphosphonic acid compositions WO1995010188A2 (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
AU77901/94A AU690581B2 (en) 1993-10-07 1994-10-07 Herbicidal aza bisphosphonic acid compositions
NZ274000A NZ274000A (en) 1993-10-07 1994-10-07 Use of azabisphosphonic acid derivatives as herbicides, azabisphosphonic derivatives
SK452-96A SK45296A3 (en) 1993-10-07 1994-10-07 Herbicidal composition on aza bisphosphonic acid base
JP7511442A JPH09506075A (ja) 1993-10-07 1994-10-07 除草性アザビスホスホン酸組成物
BR9407762A BR9407762A (pt) 1993-10-07 1994-10-07 Composiçao herbicida processo para controlar o crescimento de plantas e compostos
EP94928482A EP0722268A1 (en) 1993-10-07 1994-10-07 Herbicidal aza bisphosphonic acid compositions
PL94313820A PL313820A1 (en) 1993-10-07 1994-10-07 Herbicidal compositions of aza-biphosphonic acid
NO961389A NO961389L (no) 1993-10-07 1996-04-03 Herbicide aza-bisfosfonsyreblandinger
FI961520A FI961520A (fi) 1993-10-07 1996-04-04 Heribisidiset atsabisfosfonihappoyhdisteet

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Cited By (6)

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Publication number Priority date Publication date Assignee Title
WO1995034207A1 (en) * 1994-06-13 1995-12-21 Zeneca Limited Method of controlling plants by inhibition of farnesyl pyrophosphate synthase
WO1996031124A1 (en) * 1995-04-07 1996-10-10 Zeneca Limited Herbicidal aza bisphosphonic acids and compositions containing the same
WO1997008178A1 (en) * 1995-08-23 1997-03-06 Yissum Research Development Company Of The Hebrew University Of Jerusalem Novel bisphosphonates, process for their preparation and pharmaceutical compositions containing them
WO2007039635A2 (en) * 2005-10-06 2007-04-12 Innate Pharma Phosphoantigen salts of organic bases and methods for their crystallization
WO2008056129A1 (en) * 2006-11-06 2008-05-15 Hovione Inter Limited Process for the preparation of biphosphonic acids and salts thereof
EP2001486A2 (en) * 2006-03-17 2008-12-17 The Board Of Trustees Of The University Of Illinois Bisphosphonate compounds and methods

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EP0252504A1 (de) * 1986-07-11 1988-01-13 Roche Diagnostics GmbH Neue Diphosphonsäurederivate, Verfahren zu deren Herstellung und diese Verbindungen enthaltende Arzneimittel
EP0274158A1 (en) * 1986-12-19 1988-07-13 Norwich Eaton Pharmaceuticals, Inc. Novel heterocycle-substituted diphosphonate compounds, pharmaceutical compositions, and methods of treating abnormal calcium and phosphate matabolism
WO1993024496A1 (en) * 1992-05-29 1993-12-09 Procter & Gamble Pharmaceuticals, Inc. Sulfur-containing phosponate compounds for treating abnormal calcium and phosphate metabolism

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SU739076A1 (ru) * 1976-05-19 1980-06-05 Институт Химической Кинетики И Горения Со Ан Ссср Способ получени -аминоэтилидендифосфоновых кислот
EP0252504A1 (de) * 1986-07-11 1988-01-13 Roche Diagnostics GmbH Neue Diphosphonsäurederivate, Verfahren zu deren Herstellung und diese Verbindungen enthaltende Arzneimittel
EP0274158A1 (en) * 1986-12-19 1988-07-13 Norwich Eaton Pharmaceuticals, Inc. Novel heterocycle-substituted diphosphonate compounds, pharmaceutical compositions, and methods of treating abnormal calcium and phosphate matabolism
WO1993024496A1 (en) * 1992-05-29 1993-12-09 Procter & Gamble Pharmaceuticals, Inc. Sulfur-containing phosponate compounds for treating abnormal calcium and phosphate metabolism

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CHEMICAL ABSTRACTS, vol. 101, no. 19, 1984, Columbus, Ohio, US; abstract no. 171346, I. S. ALFEREV ET AL 'Addition of nucleophilic agents to vinylidenediphosphonic acid.' & IZV. AKAD. NAUK SSSR, SER. KHIM., no.5, 1984 pages 1122 - 1126 *
JOURNAL OF ENVIRONMENTAL SCIENCE AND HEALTH, PART B, vol.B18, no.4&5, 1983 pages 485 - 496 E. BAKUNIAK ET AL. 'Further studies on biological activity of aminophosphonates structurally related to n-(phosphonomethyl)glycine.' *
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5728650A (en) * 1993-10-07 1998-03-17 Zeneca Limited Herbicidal aza bisphosphonic acids and compositions containing the same
WO1995034207A1 (en) * 1994-06-13 1995-12-21 Zeneca Limited Method of controlling plants by inhibition of farnesyl pyrophosphate synthase
WO1996031124A1 (en) * 1995-04-07 1996-10-10 Zeneca Limited Herbicidal aza bisphosphonic acids and compositions containing the same
WO1997008178A1 (en) * 1995-08-23 1997-03-06 Yissum Research Development Company Of The Hebrew University Of Jerusalem Novel bisphosphonates, process for their preparation and pharmaceutical compositions containing them
WO2007039635A2 (en) * 2005-10-06 2007-04-12 Innate Pharma Phosphoantigen salts of organic bases and methods for their crystallization
WO2007039635A3 (en) * 2005-10-06 2007-06-21 Innate Pharma Sa Phosphoantigen salts of organic bases and methods for their crystallization
EP2001486A2 (en) * 2006-03-17 2008-12-17 The Board Of Trustees Of The University Of Illinois Bisphosphonate compounds and methods
EP2001486A4 (en) * 2006-03-17 2010-12-29 Univ Illinois BIPHOSPHONATE COMPOUNDS AND CORRESPONDING METHODS
WO2008056129A1 (en) * 2006-11-06 2008-05-15 Hovione Inter Limited Process for the preparation of biphosphonic acids and salts thereof

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IL111180A (en) 1999-09-22
CN1134657A (zh) 1996-10-30
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IL114381A0 (en) 1995-10-31
IL111180A0 (en) 1994-12-29
ZA947814B (en) 1995-08-14
AU7790194A (en) 1995-05-04
FI961520A (fi) 1996-05-27
CZ101596A3 (en) 1996-07-17
WO1995010188A3 (en) 1995-05-04
AU690581B2 (en) 1998-04-30
NO961389D0 (no) 1996-04-03
NO961389L (no) 1996-06-03
FI961520A0 (fi) 1996-04-04
CA2173607A1 (en) 1995-04-20
BR9407762A (pt) 1997-03-04
TW401276B (en) 2000-08-11
PL313820A1 (en) 1996-07-22
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SK45296A3 (en) 1996-09-04
JPH09506075A (ja) 1997-06-17

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