WO1999048890A1 - Tetrazolinones herbicides - Google Patents

Tetrazolinones herbicides Download PDF

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Publication number
WO1999048890A1
WO1999048890A1 PCT/US1999/005981 US9905981W WO9948890A1 WO 1999048890 A1 WO1999048890 A1 WO 1999048890A1 US 9905981 W US9905981 W US 9905981W WO 9948890 A1 WO9948890 A1 WO 9948890A1
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alkyl
haloalkyl
cyclohexen
optionally substituted
formula
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PCT/US1999/005981
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English (en)
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Jill Deanna Coleman
T. G. Murali Dhar
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E.I. Du Pont De Nemours And Company
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Priority to AU30110/99A priority Critical patent/AU3011099A/en
Publication of WO1999048890A1 publication Critical patent/WO1999048890A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/04—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • This invention relates to certain tetrazolinones, their N-oxides, agriculturally suitable salts, compositions thereof, and methods of their use for controlling undesirable vegetation.
  • the control of undesired vegetation is extremely important in achieving high crop efficiency. Achievement of selective control of the growth of weeds especially in such useful crops as rice, soybean, sugar beet, corn (maize), potato, wheat, barley, tomato and plantation crops, among others, is very desirable. Unchecked weed growth in such useful crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. The control of undesired vegetation in noncrop areas is also important. Many products are commercially available for these purposes, but the need continues for new compounds which are more effective, less costly, less toxic, environmentally safer or have different modes of action.
  • Patent application EP 695,748 discloses compounds of Formula i as herbicides:
  • R is an optionally substituted 5-membered heterocyclic ring
  • R 1 and R 2 are independently alkyl, haloalkyl, cycloalkyl, alkenyl, haloalkenyl, alkynyl, alkoxy or phenyl.
  • the tetrazolinones of the present invention are not disclosed in this publication.
  • This invention is directed to compounds of Formula I including all geometric and stereoisomers, N-oxides, and agriculturally suitable salts thereof, as well as agricultural compositions containing them and a method of their use for controlling undesirable vegetation: O O
  • Q is a 5- or 6-membered aromatic heterocyclic ring system containing 1 to 3 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, provided that the heterocyclic ring system contains no more than one oxygen and no more than one sulfur, and each heterocyclic ring system is optionally substituted by 1-3 groups selected from halogen, nitro, cyano, C1-C4 alkyl, C 3 -C 7 cycloalkyl, C r C 4 haloalkyl, C3-C4 alkenyl, C3-C 4 alkynyl, C r C 4 alkoxy, C r C 4 haloalkoxy, S(O) n R 4 , SO 2 NR 5 R 6 or phenyl optionally substituted with C 1 -C 4 alkyl, C3-C7 cycloalkyl, Cj-C 4 haloalkyl, halogen, cyano or nitro; and when Q is a 5- or 6-membered aromatic heterocycl
  • R 1 is C r C 6 alkyl, C r C 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -Cg haloalkynyl; or R 1 is C3-C7 cycloalkyl or C3-C7 cycloalkenyl, each optionally substituted with 1-2 R 3 ; each R 2 is independently C1-C4 alkyl or C1-C4 haloalkyl; each R 3 is independently C1-C 4 alkyl or C1-C4 alkoxy;
  • R 4 is C r C 4 alkyl or C r C 4 haloalkyl
  • R 5 is H or C r C 4 alkyl
  • R 6 is C r C 4 alkyl; each n is independently 0, 1 or 2; x is 1, 2 or 3; y is O, 1, 2, 3 or 4; and wherein the dashed lines in the 5-, 6- or 7-membered carbocyclic ring of Formula I shown below
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, ⁇ -propyl, /-propyl, or the different butyl, pentyl or hexyl isomers.
  • 1-2 alkyl indicates that one or two of the available positions for that substituent may be alkyl.
  • Alkenyl includes straight-chain or branched alkenes such as 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.
  • Alkenyl also includes polyenes such as 1 ,2-propadienyl and 2,4-hexadienyl.
  • Alkynyl includes straight-chain or branched alkynes such as 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers.
  • Alkynyl can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl.
  • Alkoxy includes, for example, methoxy, ethoxy, H-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
  • Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • Cycloalkenyl includes, for example, cyclopropenyl, cyclobutenyl, cyclopentenyl, and cyclohexenyl.
  • halogen either alone or in compound words such as “haloalkyl” includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl”, said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” include F 3 C, C1CH 2 , CF 3 CH 2 and CF 3 CC1 2 .
  • haloalkynyl examples include HC ⁇ CCHCl, CF 3 C ⁇ C, CC1 3 C ⁇ C and FCH 2 C ⁇ CCH 2 .
  • haloalkoxy examples include CF 3 O, CCl 3 CH 2 O, HCF 2 CH 2 CH 2 O and CF 3 CH 2 O.
  • C1-C3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl
  • C 2 alkoxyalkyl designates CH 3 OCH 2
  • C3 alkoxyalkyl designates, for example, CH 3 CH(OCH 3 ), CH 3 OCH 2 CH 2 or CH 3 CH 2 OCH 2
  • C4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH3CH2CH2OCH2 and CH3CH2OCH2CH2.
  • Examples of the 5-, 6- or 7-membered carbocyclic ring of Formula I include
  • the compounds of this invention thus include compounds of Formula I, geometric and stereoisomers thereof, N-oxides thereof, and agriculturally suitable salts thereof.
  • the compounds of this invention can exist as one or more stereoisomers.
  • the various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers.
  • one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers.
  • the compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.
  • the salts of the compounds of the invention include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
  • inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
  • the salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine, ammonia, or triethylamine) or inorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic group such as a carboxylic acid or enol.
  • organic bases e.g., pyridine, ammonia, or triethylamine
  • inorganic bases e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium
  • Q is selected from the group lH-pyrrolyl; furanyl; thienyl; lH-pyrazolyl; lH-imidazolyl; isoxazolyl; oxazolyl; isothiazolyl; thiazolyl; lH-lJJ-triazolyl; 2H-l,2,3-triazolyl; lH-lJ,4-triazolyl; 4H-l,2,4-triazolyl; 1,2,3-oxadiazolyl; 1,2,4-oxadiazolyl; 1,2,5-oxadiazolyl; 1,3,4-oxadiazolyl; 1,2,3-thiadiazolyl; 1,2,4-thiadiazolyl; 1,2,5-thiadiazolyl; 1,3,4-thiadiazolyl; lH-tetrazolyl;_ 2H-tetrazolyl; pyridinyl; pyridazinyl; pyrimidinyl;
  • R 1 is C Cg alkyl or C3-C7 cycloalkyl; and wherein the carbon-carbon double bond in the 5-, 6- or 7-membered carbocyclic ring is located as shown in Formula la below
  • Q is selected from the group IH-pyrrolyl; furanyl; thienyl; lH-pyrazolyl; isoxazolyl; oxazolyl; isothiazolyl; thiazolyl; pyridinyl; and pyrimidinyl; each heterocyclic group being optionally substituted by 1-3 groups selected from halogen, nitro, cyano, C1-C 4 alkyl, C3-C 7 cycloalkyl, C r C 4 haloalkyl, C3-C4 alkenyl, C 3 -C 4 alkynyl, C r C 4 alkoxy, C r C 4 haloalkoxy, S(O) n R 4 , SO 2 NR 5 R 6 or phenyl optionally substituted with C1-C4 alkyl, C3-C7 cycloalkyl, Cj-C4 haloalkyl, halogen, cyano or nitro; and when Q is
  • Q is isoxazole optionally substituted by 1-2 groups selected from halogen, nitro, cyano, C1-C4 alkyl, Cj-C 4 haloalkyl, C3-C4 alkenyl, C3-C4 alkynyl, C r C 4 alkoxy, C r C 4 haloalkoxy, S(O) n R 4 , SO 2 NR 5 R6 or phenyl optionally substituted with C1-C4 alkyl, CJ-C4 haloalkyl, halogen, cyano or nitro.
  • Most preferred is the compound of Preferred 4 which is selected from the group consisting of
  • This invention also relates to herbicidal compositions comprising herbicidally effective amounts of the compounds of the invention and at least one of a surfactant, a solid diluent or a liquid diluent.
  • This invention also relates to a method for controlling undesired vegetation comprising applying to the locus of the vegetation herbicidally effective amounts of the compounds of the invention (e.g., as a composition described herein).
  • the preferred methods of use are those involving the above preferred compounds.
  • the compounds of Formula I can be prepared by one or more of the following methods and variations as described in Schemes 1-13.
  • the definitions of Q, R ⁇ R 6 , n, x, and y in the compounds of Formulae 1-15 below are as defined above in the Summary of the Invention.
  • Scheme 1 illustrates the preparation of compounds of Formula I whereby a tetrazolinone of Formula 1 is reacted with a carbamyl chloride of Formula 2 in the presence of a suitable acid acceptor agent.
  • suitable acid acceptor agents include alkali carbonates, alkali bicarbonates, alkyl tertiary amines such as triethylamine, pyridine, and, preferably, 4- dimethylaminopyridine (DMAP).
  • DMAP can be used as a catalyst in the presence of another suitable acid acceptor agent in order to selectively synthesize a compound of Formula I.
  • the reaction is carried out in an inert solvent such as tetrahydrofuran, acetone, chloroform, chlorobenzene or preferably dioxane, acetonitrile or toluene, and at a temperature range between 0 °C and 110 °C by methods known in the art (or slight modification of these methods); for example, see Yanagi, A. et al. EP 646,577; Goto, T. et al. EP 708,097; Covey, R. A. et al. U.S. Patent 4,618,365.
  • an inert solvent such as tetrahydrofuran, acetone, chloroform, chlorobenzene or preferably dioxane, acetonitrile or toluene
  • Carbamyl chlorides of Formula 2 wherein a carbon-carbon double bond is present within the ring can be synthesized by methods known in the art (or slight modification of these methods); see, for example, Chupp, J.P. J. Het. Chem. (1971), 5, 557-563; Sakairi, N. et al. Tetrahedron Letters (1987), 28, 2871; Nogel, E. et al. Angew. Chem., I.E.E. (1979), 18, 962; Harris, H. C. J et al. Tetrahedron Letters (1995), 36, 4287; and Overman, L. Ace. Chem. Res. (1980), 73, 218-224.
  • Scheme 2 illustrates the method wherein a ketone of Formula 3 is reacted with an appropriate amine in the presence of a dehydrating agent and the resulting imine intermediate of Formula 4 is treated with phosgene in the presence of a base such as triethylamine to yield the carbamyl chloride of Formula 2a.
  • X is a leaving group such as halogen
  • compounds of Formula I can be prepared whereby a tetrazolinone of Formula 1 in an inert solvent such as toluene or ethyl acetate is reacted with phosgene and a suitable tertiary amine base such as triethylamine, and the product of such reaction is reacted with a secondary amine of Formula 8, optionally in the presence of a suitable base such as pyridine (Scheme 4).
  • This type of reaction can be carried out by methods known in the art (or slight modification of these methods); see, for example, Covey, R. A. et al. U.S. Patent 5,019,152.
  • Amines of Formula 8 wherein the endocyclic carbon-carbon double bond is adjacent to the amine substituent may exist as their imine tautomers; for example, see the compound of Formula 4. These enamine/imine tautomers are well-documented in the literature.
  • Scheme 5 illustrates a preferred method for preparing tetrazolinones of Formula 1 whereby an isocyanate of Formula 9 is reacted with refluxing trimethylsilylazide (also known as azidotrimethylsilane), followed by treatment of the product of such reaction with a protic solvent such as water or preferably with methanol.
  • This type of reaction can be carried out by methods known in the art (or slight modification of these methods); see, for example, Tsuge, O. et al. J. Org. Chem. (1980), 45, 5130; Goto, T. et al. EP 695,748 and EP 692,482.
  • isocyanates of Formula 9 are commercially available.
  • Other isocyanates of Formula 9 can be prepared by treatment of corresponding amines of Formula 10 with phosgene or known phosgene equivalents (e.g., diphosgene or triphosgene) by methods generally known in the art (Scheme 6); see for example, March, J. Advanced Organic Chemistry, 3rd edition; John Wiley & Sons, 1985, p 370; Chem. Rev. (1972), 72, pp 457-496; Sandier, R. S. et al. Organic Functional Group Preparations, 2nd edition; Academic Press; Vol. II, pp 152 and 260; Lehman, G. et al. Preparative Organic Chemistry; John Wiley & Sons, 1972; p 472.
  • amines of Formula 10 are commercially available.
  • amines of Formula 10 can be prepared by reduction of the corresponding nitro compounds of Formula 11 (Scheme 7).
  • Scheme 7 A wide variety of methods are documented in the chemical literature for carrying out such transformations; see for example, Rorer, M. P. U.S. Patent 4,511,392; Ohme, R. et al. Preparative Organic Chemistry; John Wiley & Sons, 1972; p 557; Groggins Unit Processes in Organic Chemistry; McGraw-Hill Book Co.: New York, 1947; pp 73-128; March, J. Advanced Organic Chemistry, 3rd edition; John Wiley & Sons, 1985; pp 1103- 10 Scheme 7
  • Nitro compounds of Formula 11 wherein Q is a heterocyclic ring further substituted with a phenyl ring can be synthesized by known coupling methods reviewed in Kalinin, V. Synthesis (1992), pp 413-432.
  • isocyanates of Formula 9 can be also be prepared by Curtius rearrangement of appropriate acid chlorides of Formula 12 using methods generally known in the art (Scheme 8); see, for example, March, J. Advanced Organic Chemistry, 3rd edition; John Wiley & Sons, 1985; pp 984-985 and 380.
  • Acid chlorides of Formula 12 can be prepared by reacting an acid of Formula 13 with oxalyl chloride (or thionyl chloride) and optionally a catalytic amount of dimethylformamide (Scheme 9).
  • This chlorination is well known in the art; see, for example, Michaely, W. J. EP 369,803; Goto, T. et al. EP 695,748.
  • Other methods are also well known in the art for converting carboxylic acids to acid chlorides; see, for example, Ogliaruso, M. A. et al. Synthesis of Carboxylic Acids, Esters and Their Derivatives; John Wiley & Sons, 1991, pp 172-174.
  • Carboxylic acids of Formula 13 can be prepared as illustrated in Scheme 10, whereby an ester of Formula 14 is saponified (e.g., potassium hydroxide in methanol, then acidified - with an acid such as hydrochloric acid) or, alternatively, is acid hydrolyzed (e.g., 5 N HCI in acetic acid) by methods known in the art (or slight modification of these methods); see for 11 example, Ogliaruso, M. A. et al. Synthesis of Carboxylic Acids, Esters and Their Derivatives; John Wiley & Sons, 1991, pp 5-7.
  • an ester of Formula 14 is saponified (e.g., potassium hydroxide in methanol, then acidified - with an acid such as hydrochloric acid) or, alternatively, is acid hydrolyzed (e.g., 5 N HCI in acetic acid) by methods known in the art (or slight modification of these methods); see for 11 example, Ogliaruso, M. A.
  • R b is Cj-C 2 alkyl
  • Esters of Formula 14 wherein Q is a heterocyclic ring further substituted with a phenyl ring can be synthesized by known coupling methods reviewed in Kalinin, V. Synthesis (1992), pp 413-432.
  • Scheme 11 illustrates an alternative preparation of many carboxylic acids of Formula 13 whereby a bromide compound of Formula 15 is treated with «-butyllithium (or magnesium) and the lithium salt (or the Grignard reagent) generated in situ is then reacted with carbon dioxide followed by acidification with an acid such as hydrochloric acid.
  • This conversion is carried out by using methods known in the art (or by slight modification of these methods); see for example, Ogliaruso, M. A. et al. Synthesis of Carboxylic Acids, Esters and Their Derivatives; John Wiley & Sons; pp 27-28; Bridges, A. J. et al. J. Org. Chem. (1990), 55, 113; Franke, C. et al. Angew. Chem. Int. Ed. (1969), 5, 68. Protecting and deprotecting functional groups not compatible with the reaction conditions may be necessary for compounds with such functional groups.
  • bromo compounds of Formula 15 are commercially available, while others can be prepared by bromination of their corresponding heteroaromatic precursors with bromine or other equivalent reagents in an inert solvent. This type of bromination is carried out by general methods known in the art; see for example, Campaigne, E. et al. J. Heterocyci. Chem. (1969), 6, 517; Gilman, H. J. Am. Chem. Soc. (1955), 77, 6059.
  • nitro compounds of Formula 11, bromo compounds of Formula 15, and ester compounds of Formula 14 can be prepared by those skilled in the art using methods known in the art (or by obvious modification of these methods); see for example, Rorer, M. P. U.S. 12
  • Patent 4,511,392 Wolf, A. D. U.S. Patent 4,465,505; Sauers, R. F. U.S. Patent 4,460,401; Denes, R. WO 93/11097; Petersen, C. et al. WO 96/31517; Denes, R. WO 95/09846; Katritzky, A. R. et al. Comprehensive Heterocyclic Chemistry; Pergamon Press; Volumes 2- 6.
  • Protecting and deprotecting functional groups not compatible with the reaction conditions may be necessary for compounds with such functional groups.
  • Scheme 12 illustrates another method for preparing tetrazolinones of Formula 1 whereby an isocyanate of Formula 9 is reacted with sodium azide and aluminum chloride in an inert solvent such as NN-dimethylformamide (DMF) followed by addition of water and a mineral acid in excess, such as hydrochloric acid.
  • an inert solvent such as NN-dimethylformamide (DMF)
  • NN-dimethylformamide DMF
  • This type of reaction can be carried out by methods known in the art (or slight modification of these methods); see for example, Horwitz, J. P. et al. J. Am. Chem. Soc. (1959), 81, 3076; Yanagi, A. et al. U.S. Patent 5,530,135; Covey, R. A. et al. U.S. Patent 4,618,365.
  • tetrazolinones of Formula 1 can be prepared as illustrated in Scheme 13, whereby an appropriate acid chloride of Formula 12 is refiuxed with excess trimethylsilylazide, and the product of such reaction is treated with a protic solvent such as water or, preferably, with methanol.
  • a protic solvent such as water or, preferably, with methanol.
  • This type of reaction can be carried out by methods known in the art (or by slight modification of these methods): see, for example, Toselli, M. et al. /. Chem. Soc. Perkin Trans. 1 (1992), 1101; Goto, T. et al. EP 695,748 and EP 692,482; Horwitz, J. et al. J. Am. Chem. Soc. (1959), 81, 3076.
  • Step B Preparation of 1 -cyclohexen- l-yl(l-methylethyl)carbamic chloride
  • Step B Preparation of l,4-dihydro-l-[l-phenyl-5-(trifluoromethyl)-lH-pyrazol-4-yl]-
  • Step D Preparation of N-( 1 -cyclohexen- 1 -yl)-4,5-dihydro-N-( 1 -methylethyl)-5-oxo-4-
  • Step D Preparation of N-( 1 -cyclohexen- 1 -yl)-4-(3,5-dimethyl-4-isoxazolyl)-4,5- dihydro-N-( 1 -methylethyl)- 1 H-tetrazole- 1 -carboxamide
  • Step B Preparation of 1 -cyclohexen- 1 -yl-ethylcarbamic chloride
  • Step C Preparation of N-( 1 -cyclohexen- 1 -yl)-4-(3 ,5-dimethyl-4-isoxazolyl)-4,5- dihydro-N-ethyl- lH-tetrazole- 1 -carboxamide
  • R 1 is CH 3 s Q Q 0.
  • Rl is CH ⁇ CH
  • R 1 is CH(CH Q Q Q Q 2 Q Q 19
  • Rl is cyclopropyl
  • Rl is CH 3
  • Rl is CH 7 CH 3
  • Rl is CH(CH ) 2
  • Rl is cyclopropyl 2 Q 2 2 2 2 Q 20
  • R 1 is CH3
  • Rl is CH2CH3
  • R l is CH(CH 3 ) 2
  • Rl is cyclopropyl
  • Compounds of this invention will generally be used as a formulation or composition with an agriculturally suitable carrier comprising at least one of a liquid diluent, a solid diluent or a surfactant.
  • the formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature.
  • Useful formulations include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels.
  • Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films, and the like which can be water-dispersible ("wettable") or water-soluble.
  • Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or "overcoated”). Encapsulation can control or delay release of the active ingredient.
  • Sprayable formulations can be extended in suitable media and used at spray 23 volumes from about one to several hundred liters per hectare. High-strength compositions are primarily used as intermediates for further formulation.
  • the formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.
  • Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon 's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth and the like, or thickeners to increase viscosity.
  • Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, NN-dialkyltaurates, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polycarboxylates, and polyoxyethylene/polyoxypropylene block copolymers.
  • Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate.
  • Liquid diluents include, for example, water, NN-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, rung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, and alcohols such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol. 24
  • Solutions can be prepared by simply mixing the ingredients. Dusts and powders can be prepared by blending and, usually, grinding as in a hammer mill or fluid-energy mill. Suspensions are usually prepared by wet-milling; see, for example, U.S. 3,060,084. Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S.
  • Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.
  • Compound 1 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%.
  • Compound 2 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.
  • Some of the compounds are useful for the control of selected grass and broadleaf weeds with tolerance to important agronomic crops which include but are not limited to alfalfa, barley, cotton, wheat, rape, sugar beets, corn (maize), sorghum, soybeans, rice, oats, peanuts, vegetables, tomato, potato, perennial plantation crops including coffee, cocoa, oil palm, rubber, sugarcane, citrus, grapes, fruit trees, nut trees, banana, plantain, pineapple, hops, tea and forests such as eucalyptus and conifers (e.g., loblolly pine), and turf species (e.g., Kentucky bluegrass, St. Augustine grass, Kentucky fescue and Bermuda grass).
  • the subject compounds are useful to modify plant growth.
  • a herbicidally effective amount of the compounds of this invention is determined by a number of factors. These factors include: formulation selected, method of application, amount and type of vegetation present, growing conditions, etc. In general, a herbicidally effective amount of compounds of this invention is 0.001 to 20 kg/ha with a preferred range of 0.004 to 1.0 kg/ha. One skilled in the art can easily determine the herbicidally effective amount necessary for the desired level of weed control.
  • Compounds of this invention can be used alone or in combination with other commercial herbicides, insecticides or fungicides. Compounds of this invention can also be* used in combination with commercial herbicide safeners such as benoxacor, dichlormid and furilazole to increase safety to certain crops.
  • commercial herbicide safeners such as benoxacor, dichlormid and furilazole to increase safety to certain crops.
  • a mixture of one or more of the following 26 herbicides with a compound of this invention may be particularly useful for weed control: acetochlor, acifluorfen and its sodium salt, aclonifen, acrolein (2-propenal), alachlor, ametryn, amidosulfuron, amitrole, ammonium sulfamate, anilofos, asulam, atrazine, azafenidin, azimsulfuron, benazolin, benazolin-ethyl, benfluralin, benfuresate, bensulfuron-methyl, bensulide, bentazone, bifenox, bispyribac and its sodium salt, bromacil, bromoxynil, bromoxynil octanoate, butachlor, butralin, butroxydim (ICIA0500), butylate, caloxydim (BAS 620H), carfentrazone-ethyl,
  • N N A-
  • a iH NMR data are in ppm downfield from tetramethylsilane. Couplings are designated by (s)-singlet, (d)-doublet, (t)-triplet, (q)-quartet, (m)-multiplet, (dd)-doublet of doublets, (dt)-doublet of triplets, (br s)-broad singlet.
  • Plants ranged in height from 2 to 18 cm (1- to 4-leaf stage) for postemergence treatments.
  • a flood test was also conducted with plant species consisting of rice (Oryza sativa), smallflower flatsedge (Cyperus difformis), duck salad (Heteranthera limosa) and barnyardgrass (Echinochloa crus-gall ⁇ ) grown to the 2-leaf stage for testing.
  • Treated plants and controls were maintained in a greenhouse for twelve to sixteen days, after which all species were compared to controls and visually evaluated.
  • Plant response ratings, summarized in Table A are based on a scale of 0 to 10 where 0 is no effect and 10 is complete control.
  • a dash (-) response means no test result.
  • Soybean 1 8 4 6 6 7 8 3 6 5 7 7 4 8 8 8 4 35
  • Giant foxtail 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10
  • Soybean 1 4 4 3 4 5 5 2 3 5 2 3 2 2 2 - 6 4 - 4 4 4 4 8 8 2
  • Morningglory 0 1 0 0 4 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 3
  • Crop and weed species include arrowleaf sida (Sida rhombifolia), barnyardgrass (Echinochloa crus-galli), cocklebur (Xanthium strumarium), common ragweed (Ambrosia elatior), corn (Zea mays), cotton (Gossypium hirsutum), eastern black nightshade (Solanum ptycanthum), fall panicum (Panicum dichotomi ⁇ orum), field bindweed (Convolvulus arvensis), giant foxtail (Setaria faberii), hairy beggarticks (Bidens pilosa), ivyleaf morningglory (Ipomoea hederacea), johnsongrass (Sorghum halepense), ladysthumb smartweed (Polygonum persic
  • Treated plants and untreated controls were maintained in a greenhouse for approximately 14 to 21 days, after which all treated plants were compared to untreated controls and visually evaluated. Plant response ratings, summarized in Table B, were based upon a 0 to 100 scale where 0 was no effect and 100 was complete control. A dash response (-) means no test result.
  • Johnsongrass 100 85 100 100 70 60 100
  • Surinam grass 100 85 100 100 100 50 65
  • alexandergrass Brachiaria plantaginea
  • bermudagrass Cronodon dactylo ⁇
  • common purslane Purslane
  • Portulaca oleracea common ragweed
  • Ambrosia elatior common groundsel
  • dallisgrass Paspalum dilatatum
  • goosegrass Eleusine indica
  • guineagrass Pieranicum maximum
  • itchgrass Rottboellia exaltata
  • johnsongrass Sorghum halepense
  • large crabgrass Digitaria sanguinalis
  • pitted morningglory Ipomoea lacunosa
  • purple nutsedge Ipomoea lacunosa
  • Purple nutsedge Ipomoea lacunosa
  • sandbur Crochrus echinatus
  • sourgrass Terichachne insularis
  • Spanishneedles Bodens bipinnata
  • sugarcane Saccharum officinarum
  • Plant species were grown in separate pots or individual compartments. Preemergence applications were made within one day of planting the seed or plant part. Postemergence applications were applied, to sugarcane, when the plants were in the two to four leaf stage (three to twenty cm). Test chemicals were formulated in a non-phytotoxic solvent mixture which included a surfactant and applied preemergence and postemergence to the plants. Untreated control plants and treated plants were placed in the greenhouse and visually evaluated for injury 13 to 21 days after herbicide application. Plant response ratings, summarized in Table C, are based on a 0 to 100 scale where 0 is no injury and 100 is complete control. A dash (-) response means no test result.
  • Rate 500 g/ha 5 Rate 500 g/ha 2 5
  • Dallisgrass 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100
  • Guineagrass 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100
  • Sourgrass 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100
  • Dallisgrass 100 100 100 98 98 98
  • Guineagrass 100 100 98 100 90 100
  • Sourgrass 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100
  • Surinam grass 50 100 70 80 80 75
  • Dallisgrass 100 90 85 90 80 60
  • Surinam grass 70 50 50 40 50 0 Tall Mallow 0 0 0 0 0 0 30

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Dentistry (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Agronomy & Crop Science (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

L'invention concerne les composés de la formule (I), géométriques et stéréoisomères, leur N-oxyde et leurs sels adaptés sur le plan agricole, lesquels sont utiles pour éliminer la végétation indésirable, formule dans laquelle Q, R1, R2, x et y ont la notation ci-définie. L'invention concerne également des compositions contenant les composés de la formule (I) ainsi qu'un procédé d'élimination de la végétation indésirable consistant à mettre la végétation ou son environnement en contact avec une dose efficace d'un composé de la formule (I).
PCT/US1999/005981 1998-03-26 1999-03-19 Tetrazolinones herbicides WO1999048890A1 (fr)

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US7939498P 1998-03-26 1998-03-26
US60/079,394 1998-03-26

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015056811A1 (fr) * 2013-10-17 2015-04-23 住友化学株式会社 Composé tétrazolinone et son application
US9346769B2 (en) 2010-05-05 2016-05-24 Infinity Pharmaceuticals, Inc. Tetrazolones as inhibitors of fatty acid synthase
US9822095B2 (en) 2014-03-28 2017-11-21 Sumitomo Chemical Company, Limited Tetrazolinone compound and application thereof
US9826741B2 (en) 2014-03-28 2017-11-28 Sumitomo Chemical Company, Limited Tetrazolinone compound and application thereof
US10070646B2 (en) 2014-03-28 2018-09-11 Sumitomo Chemical Company, Limited Tetrazolinone compound and application thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0692482A2 (fr) * 1994-07-12 1996-01-17 Nihon Bayer Agrochem K.K. Dérivés de 1-pyridyltétrazolinone
EP0695748A1 (fr) * 1994-08-05 1996-02-07 Nihon Bayer Agrochem K.K. Herbicides tétrazolinones
EP0708097A1 (fr) * 1994-10-18 1996-04-24 Nihon Bayer Agrochem K.K. Tétrazolinones à activité herbicide
WO1998025912A1 (fr) * 1996-12-13 1998-06-18 E.I. Du Pont De Nemours And Company Amides heterocycliques herbicides
WO1998035961A1 (fr) * 1997-02-18 1998-08-20 E.I. Du Pont De Nemours And Company Tetrazolinones herbicides
EP0902028A1 (fr) * 1997-09-11 1999-03-17 E.I. Du Pont De Nemours And Company Tétrazolines herbicides

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0692482A2 (fr) * 1994-07-12 1996-01-17 Nihon Bayer Agrochem K.K. Dérivés de 1-pyridyltétrazolinone
EP0695748A1 (fr) * 1994-08-05 1996-02-07 Nihon Bayer Agrochem K.K. Herbicides tétrazolinones
EP0708097A1 (fr) * 1994-10-18 1996-04-24 Nihon Bayer Agrochem K.K. Tétrazolinones à activité herbicide
WO1998025912A1 (fr) * 1996-12-13 1998-06-18 E.I. Du Pont De Nemours And Company Amides heterocycliques herbicides
WO1998035961A1 (fr) * 1997-02-18 1998-08-20 E.I. Du Pont De Nemours And Company Tetrazolinones herbicides
EP0902028A1 (fr) * 1997-09-11 1999-03-17 E.I. Du Pont De Nemours And Company Tétrazolines herbicides

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9346769B2 (en) 2010-05-05 2016-05-24 Infinity Pharmaceuticals, Inc. Tetrazolones as inhibitors of fatty acid synthase
WO2015056811A1 (fr) * 2013-10-17 2015-04-23 住友化学株式会社 Composé tétrazolinone et son application
JPWO2015056811A1 (ja) * 2013-10-17 2017-03-09 住友化学株式会社 テトラゾリノン化合物及びその用途
US10077254B2 (en) 2013-10-17 2018-09-18 Sumitomo Chemical Company, Limited Tetrazolinone compound and use thereof
US9822095B2 (en) 2014-03-28 2017-11-21 Sumitomo Chemical Company, Limited Tetrazolinone compound and application thereof
US9826741B2 (en) 2014-03-28 2017-11-28 Sumitomo Chemical Company, Limited Tetrazolinone compound and application thereof
US10070646B2 (en) 2014-03-28 2018-09-11 Sumitomo Chemical Company, Limited Tetrazolinone compound and application thereof

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ID23229A (id) 2000-03-30

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