WO1998051683A1 - Tetrazolinones herbicides - Google Patents

Tetrazolinones herbicides Download PDF

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Publication number
WO1998051683A1
WO1998051683A1 PCT/US1998/008884 US9808884W WO9851683A1 WO 1998051683 A1 WO1998051683 A1 WO 1998051683A1 US 9808884 W US9808884 W US 9808884W WO 9851683 A1 WO9851683 A1 WO 9851683A1
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compound
och
heterocyclic ring
alkyl
optionally substituted
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PCT/US1998/008884
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English (en)
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Hyeong Baik Kim
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E.I. Du Pont De Nemours And Company
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Priority to AU73656/98A priority Critical patent/AU7365698A/en
Publication of WO1998051683A1 publication Critical patent/WO1998051683A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
    • C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D257/04—Five-membered rings
    • 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
    • C07D403/06—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 linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • This invention relates to certain tetrazolinones, their N-oxides, agriculturally suitable salts and compositions, 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.
  • U.S. 5,019,152 discloses herbicidal tetrazolinones of the formula
  • R is alkyl, alkenyl, C7-C9 aralkyl, phenyl or substituted phenyl; and R 1 and R 2 are independently C r Cg alkyl, C3-C6 alkenyl or C 5 -Cg cycloalkyl.
  • This invention is directed to compounds of Formula I including all geometric and stereoisomers, N-oxides, and agriculturally suitable salts thereof, agricultural compositions containing them and their use for controlling undesirable vegetation:
  • Q is C r Ci 2 alkyl, C 2 -Cj 3 alkoxyalkyl, C -C cycloalkyl, C 3 -Cg cycloalkenyl, C3-C J 2 alkenyl or C ⁇ -Cg alkynyl, each group optionally substituted with 1-3 substituents independently selected from C1-C4 alkyl, C1-C 4 haloalkyl or halogen; or Q is Ar-(CH2) p - optionally substituted on the methylene carbon by 1-2 C j -C 2 alkyl; or
  • Q is a 5- or 6-membered aromatic heterocyclic ring system containing 1 to 3 heteroatoms independently selected from the group 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 one or more groups selected from halogen, nitro, cyano, C 1 -C4 alkyl, C C4 haloalkyl, C3-C 4 alkenyl, C3-C4 alkynyl, -C4 alkoxy, C 1 -C4 haloalkoxy, S(O) n R 6 , and SO 2 NR 7 R 8 ; and when Q is a 5- or 6-membered aromatic heterocyclic ring system containing a nitrogen, then Q can be bonded through any available carbon or nitrogen atom to the tetrazolinone ring by replacement of a hydrogen on said carbon or nitrogen atom;
  • R 1 is H, 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, C3-C6 haloalkynyl; or R 1 is C3-C 7 cycloalkyl or C3-C 7 cycloalkenyl, each optionally substituted with 1-4 R 4 ; or R 1 is a saturated or partially saturated 5-, 6- or 7-membered heterocyclic ring containing 1 to 2 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, and each heterocyclic ring is optionally substituted with 1-4 R 4 ; or R 1 is phenyl optionally substituted on the phenyl ring with C 1 -C3 alkyl, C1-C3 haloalkyl, halogen, cyano or nitro; R 2 is C r C 6 alkyl, C r C 6 hal
  • R 2 is C 3 -C7 cycloalkyl or C3-C 7 cycloalkenyl, each optionally substituted with 1-4 R 4 ; or R 2 is a saturated or partially saturated 5-, 6- or 7-membered heterocyclic ring containing 1 to 2 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, and each heterocyclic ring is optionally substituted with 1-4
  • R 4 or R 2 is phenyl optionally substituted on the phenyl ring with Cj-C 3 alkyl, CJ-C3 haloalkyl, halogen, cyano or nitro; or R 1 and R 2 are taken together with the two nitrogen atoms to which they are attached to form a saturated or partially saturated 5-, 6- or 7-membered heterocyclic ring containing an optional third heteroatom selected from oxygen, sulfur or nitrogen, and said heterocyclic ring can be optionally substituted with 1-4 R 5 ; R 3 is H or C r C 4 alkyl; or R 2 and R 3 are taken together with the nitrogen atom to which they are attached to form a saturated or partially saturated 5-, 6- or 7-membered heterocyclic ring containing an optional second heteroatom selected from oxygen, sulfur or nitrogen, and said heterocyclic ring can be optionally substituted with 1-4 R 5 ; Ar is phenyl or pyridyl, each optionally substituted with 1 -3 substituents independently selected from
  • R 7 is H or C r C 4 alkyl
  • R 8 is H or C r C 4 alkyl
  • each n is independently 0, 1 or 2
  • p is 0 or 1 ; provided that if R 1 and R 2 are taken together to form a heterocyclic ring, then R 2 and
  • R 3 are other than taken together to form a heterocyclic ring; and provided that if R 2 and R 3 are taken together to form a heterocyclic ring, then R 1 and R 2 are other than taken together to form a heterocyclic ring.
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, H-propyl, /-propyl, or the different butyl, pentyl or hexyl isomers.
  • the term "1-2 alkyl” indicates that one or two of the available positions for that substituent may be alkyl which are independently selected.
  • Alkenyl includes straight-chain or branched alkenes such as ethenyl, 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 ethynyl, 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, «-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
  • Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • Cycloalkenyl includes groups such as cyclopentenyl and cyclohexenyl as well as groups with more than one double bond such as 1,3- and 1 ,4-cyclohexadienyl.
  • nonaromatic carbocyclic ring system denotes fully saturated carbocycles as well as partially or fully unsaturated carbocycles where the Huckel rule is not satisfied by any of the rings in the ring system.
  • nonaromatic heterocyclic ring system denotes fully saturated heterocycles as well as partially or fully unsaturated heterocycles where the Huckel rule is not satisfied by any of the rings in the ring system.
  • the heterocyclic ring systems can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
  • nitrogen containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen containing heterocycles which can form N-oxides.
  • nitrogen containing heterocycles which can form N-oxides.
  • tertiary amines can form N-oxides.
  • N-oxides of heterocycles and tertiary amines are very well known by one skilled in the art including the oxidation of heterocycles and tertiary amines with peroxy acids such as peracetic and w-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane.
  • MCPBA peroxy acids
  • alkyl hydroperoxides such as t-butyl hydroperoxide
  • sodium perborate sodium perborate
  • dioxiranes such as dimethyldioxirane
  • halogen either alone or in compound words such as “haloalkyl”, includes fluorine, chlorine, bromine or iodine.
  • 1-2 halogen indicates that one or two of the available positions for that substituent may be halogen which are independently selected. 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 .
  • haloalkenyl include F 3 C, C1CH 2 , CF 3 CH 2 and CF 3 CC1 2 .
  • haloalkynyl haloalkoxy
  • haloalkynyl include HC ⁇ CCHCl, CF 3 C ⁇ C, CC1 3 C ⁇ C and FCH 2 C ⁇ CCH 2 .
  • haloalkoxy include CF 3 O, CCl 3 CH 2 O, HCF 2 CH 2 CH 2 O and CF 3 CH 2 O.
  • Cj-C j The total number of carbon atoms in a substituent group is indicated by the "Cj-C j " prefix where i and j are numbers from 1 to 13.
  • C j -C3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl
  • C 2 alkoxyalkyl designates CH 3 OCH 2
  • C 3 alkoxyalkyl designates, for example, CH 3 CH(OCH 3 ), CH 3 OCH 2 CH 2 or CH 3 CH 2 OCH 2
  • C 4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH 3 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • alkylcarbonyl examples include C(O)CH 3 , C(O)CH 2 CH 2 CH 3 and C(O)CH(CH 3 ) 2 .
  • substituents When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1 , said substituents (when they exceed 1 ) are independently selected from the group of defined substituents. Further, when the subscript indicates a range, e.g. (R)i_ j , then the number of substituents may be selected from the integers between i and j inclusive.
  • Stereoisomers 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).
  • the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers.
  • the present invention comprises compounds selected from Formula I, N-oxides and agriculturally suitable salts thereof.
  • 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,
  • 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 phenol.
  • organic bases e.g., pyridine, ammonia, or triethylamine
  • inorganic bases e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium
  • Preferred compounds for reasons of better activity and/or ease of synthesis are: Preferred 1. Compounds of Formula I above, and N-oxides and agriculturally-suitable salts thereof, wherein
  • Q is Ar-(CH 2 ) p - optionally substituted on the methylene carbon by 1-2 C j -C 2 alkyl; or Q is a 5- or 6-membered aromatic heterocyclic ring system containing 1 to 3 heteroatoms independently selected from the group 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 one or more groups selected from halogen, nitro, cyano, C j -C 4 alkyl, Cj-C 4 haloalkyl, C3-C 4 alkenyl, C3-C4 alkynyl, C r C 4 alkoxy, C r C 4 haloalkoxy, S(O) n R 6 , and SU2 ⁇ R 7 R 8 ; and when Q is a 5- or 6-membered aromatic heterocyclic ring system containing a nitrogen, then Q can be bonded through any available carbon or nitrogen atom to
  • Ar is phenyl optionally substituted with 1 -3 substituents independently selected from halogen, cyano, nitro, Cj-C 4 alkoxy, C 1 -C 4 haloalkoxy, C r C 4 alkyl, C r C 4 haloalkyl, C 2 -C 4 alkoxycarbonyl or S(O) n R 6 ; and p is 0.
  • substituents independently selected from halogen, cyano, nitro, Cj-C 4 alkoxy, C 1 -C 4 haloalkoxy, C r C 4 alkyl, C r C 4 haloalkyl, C 2 -C 4 alkoxycarbonyl or S(O) n R 6 ; and p is 0.
  • R 1 is C3-C7 cycloalkyl or C3-C7 cycloalkenyl, each optionally substituted with 1-4 R 4 .
  • Preferred 4 Compounds of Preferred 2 wherein
  • R 2 and R 3 are taken together with the nitrogen atom to which they are attached to form a saturated or partially saturated 5-, 6- or 7-membered heterocyclic ring containing an optional second heteroatom selected from oxygen, sulfur or nitrogen, and said heterocyclic ring can be optionally substituted with 1-4 R 5 .
  • Q is thienyl optionally substituted by 1 -2 groups selected from halogen, nitro, cyano, C j -C 4 alkyl, C 1 -C 4 haloalkyl, C3-C4 alkenyl, C3-C 4 alkynyl, S(O) 2 R 6 , and SO 2 NR 7 R 8 .
  • Preferred 7 Compounds of Preferred 6 wherein
  • R 1 is C3-C7 cycloalkyl or C3-C7 cycloalkenyl, each optionally substituted with l-4 R 4 .
  • Preferred 8 Compounds of Preferred 6 wherein
  • R 2 and R 3 are taken together with the nitrogen atom to which they are attached to form a saturated or partially saturated 5-, 6- or 7-membered heterocyclic ring containing an optional second heteroatom selected from oxygen, sulfur or nitrogen, and said heterocyclic ring can be optionally substituted with 1-4 R 5 .
  • the compound of Formula I selected from the group: (a) 4-(2-chlorophenyl)-4,5-dihydro-N-( 1 -methylethyl)-5-oxo-N-( 1 -piperidinyl)- 1H- tetrazole- 1 -carboxamide;
  • 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.
  • a surfactant a solid diluent or a liquid diluent.
  • the preferred compositions of the present invention are those which comprise the above preferred compounds.
  • 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 1-15.
  • the definitions of Q, Ar, Z, R ⁇ -R 8 , n, and p in the compounds of Formulae 1-17 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 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 acetonitrile or toluene
  • 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 hydrazine of Formula 3, optionally in the presence of a suitable base such as pyridine (Scheme 2).
  • 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.
  • Scheme 2 See, for example, Covey, R. A. et al. U.S. Patent 5,019,152.
  • Hydrazines of Formula 3 can be made by the sequence of reactions shown in Scheme 3 whereby a ketone of Formula 4 is treated with an appropriate hydrazine of Formula 16 and the formed intermediate hydrazone of Formula 17 is subsequently reduced to the hydrazine of Formula 3.
  • This type of reaction can be carried out by methods known in the art (or slight modification of these methods); see, for example, Takahashi, H et al. Chem. Pharm. Bull. , (1981), 29, p 3387 and Spialter, L. et al. J. Org. Chem. (1965), 30, p 3278.
  • Hydrazines of Formula 3 can also be made starting from commercially-available amines by methods well-established in the art; for example, see Witte, J. et al. J. Org. Chem. (1972), 37, 2849. Scheme 3
  • R a and R ⁇ are independently H, alkyl or are taken together as cycloalkyl.
  • ketones of Formula 4 are commercially available or can be prepared by methods well-established in the art.
  • Carbamyl chlorides of Formula 2 can be made by treating compounds of Formula 3 or Formula 17 with either phosgene or a phosgene equivalent such as diphosgene in the presence of a suitable base such as triethylamine (Scheme 4).
  • Scheme 5 illustrates a preferred method for preparing tetrazolinones of Formula 1 whereby an isocyanate of Formula 5 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.
  • alkyl and phenyl isocyanates of Formula 5 are commercially available.
  • Other isocyanates of Formula 5 can be prepared by treatment of corresponding amines of Formula 9 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;
  • amines of Formula 6 are commercially available, including both simple and substituted alkyl, alkenyl, alkynyl, phenyl, pyridyl, and heteroaryl amines.
  • amines of Formula 6 can be prepared by reduction of the corresponding nitro compounds of Formula 7 (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- 1104.
  • Nitro compounds of Formula 7 are commercially available or can be synthesized by methods well-established in the art.
  • Nitro compounds of Formula 7a can be prepared as illustrated in Scheme 8 whereby an appropriate nitro compound of Formula 8 in an inert solvent is reacted with a nucleophilic heterocycle of Formula 9 in the presence of a suitable base.
  • Suitable bases include alkali carbonates such as potassium carbonate, potassium tert- butoxide, and sodium hydride.
  • Suitable solvents include dimethylformamide, 2-butanone, and tetrahydrofuran. The reaction is carried out at a temperature range of about 0 °C to 150 °C, preferably about 80 °C to 120 °C, with dimethylformamide as the solvent and potassium carbonate as the base.
  • the compound of Formula 6a can be purified by recrystallization or flash column chromatography on silica gel by those skilled in the art.
  • Protecting and deprotecting functional groups not compatible with reaction conditions may be necessary for compounds with such functional groups.
  • X is F, Cl, Br, CH3S0 2 0 or CF3S0 2 0 and X is ortho or para to the N0 2 group;
  • Nu is an optionally-substituted imidazole, pyrazole, triazole or tetrazole;
  • Al is an optionally-substituted 1 /-imidazole, l//-pyrazole, l//-l,2,4-triazole, 4//-l,2,4-triazole or tetrazole and Al is ortho or para to the N0 2 group; and W is CH or N.
  • Nitro compounds of Formula 7 wherein Q is Ar and Ar is phenyl or a heterocyclic ring further substituted with another phenyl or heterocyclic ring can be synthesized by known coupling methods reviewed in Kalinin, V. Synthesis (1992), pp 413-432.
  • isocyanates of Formula 5 can be also be prepared by Curtius rearrangement of appropriate acid chlorides of Formula 10 using methods generally known in the art (Scheme 9); see, for example, March, J. Advanced Organic Chemistry, 3rd edition; John Wiley & Sons, 1985; pp 984-985 and 380.
  • Acid chlorides of Formula 10 can be prepared by reacting an acid of Formula 1 1 with oxalyl chloride (or thionyl chloride) and optionally a catalytic amount of dimethylformamide (Scheme 10).
  • 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 1 1 can be prepared as illustrated in Scheme 11, whereby an ester of Formula 12 is saponified (e.g., potassium hydroxide in methanol, then acidified with an acid such as hydrochloric acid) or, alternatively, is acid hydrolyzed (e.g., 5NHC1 in acetic acid) by methods known in the art (or slight modification of these methods); see for example, Ogliaruso, M. A. et al. Synthesis of Carboxylic Acids, Esters and Their Derivatives; John Wiley & Sons, 1991 , pp 5-7.
  • Scheme 12 illustrates the preparation of many esters of Formula 12a whereby an appropriate ester of Formula 13 in an inert solvent is reacted with a nucleophilic heterocycle of Formula 14 in the presence of a suitable base. Reaction conditions are as described for Scheme 8.
  • X is F, Cl, Br, CH3SO2O or CF3SO2O and X is ortho or para to the C ⁇ 2R a group;
  • Nu is an optionally-substituted imidazole, pyrazole, triazole or tetrazole;
  • Al is an optionally-substituted 1 /-imidazole, l//-pyrazole, l//-l,2,4-triazole, 4//-l,2,4-triazole or tetrazole and A ⁇ is ortho or para to the CO2R 7 group; and W is CH or N.
  • Esters of Formula 12 wherein Q is Ar and Ar is phenyl or a heterocyclic ring further substituted with another phenyl or heterocyclic ring can be synthesized by known coupling methods reviewed in Kalinin, V. Synthesis (1 92), pp 413-432.
  • Scheme 13 illustrates an alternative preparation of many carboxylic acids of Formula 11 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 slights 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, 773; Franke, C. et al. Angew. Chem. Int. Ed. (1969), 8, 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 aromatic or 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. Heterocycl. Chem. (1969), 6, 517; Gilman, H. J. Am. Chem. Soc. (1955), 77, 6059.
  • nitro compounds of Formula 7, bromo compounds of Formula 15, and ester compounds of Formula 12 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. 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 14 illustrates another method for preparing tetrazolinones of Formula 1 whereby an isocyanate of Formula 5 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 15, whereby an appropriate acid chloride of Formula 5 is refluxed 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. J. 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 A Preparation of cvclohexanone dimethylhvdrazone
  • Step B Preparation of l-(l-cvclohexen-l-yl)-2-2-dimethylhvdrazinecarbonyl chloride
  • Step C Preparation of 4-(2-chlorophenyl)-4,5-dihvdro-5-oxo-l-(2,2-dimethyl-l-
  • reaction mixture was re fluxed for 2 h, cooled to room temperature, poured into IN aqueous HCl solution and extracted with ethyl acetate to give an oil which was purified using silica gel column chromatography (15% ethyl acetate/hexane) to give 952 mg of the title compound of Step C, a compound of this invention, as a colorless oil.
  • Step A Preparation of tetrahvdro-4H-pyran-4-one dimethylhydrazone
  • Step B Preparation of 1 -(5,6-dihydro-2H-pyran-4-yl)-2,2-dimethylhvdrazinecarbonyl chloride
  • a stirred solution of 3.1 g of the title compound of step A in 30 mL of dichloromethane at 0 °C under nitrogen was added dropwise 13.2 mL of a 3.5 M solution of phosgene in toluene.
  • the solution was stirred at room temperature for 1 h and concentrated to give 4.3 g of the title compound of Step B as an oil which was immediately used in the next step without further purification.
  • Step C Preparation of4-(2,6-dichlorophenyl)-4,5-dihydro-5-oxo-lH-tetrazole-l- carboxylic acid 1 -(5,6-dihvdro-2H-pyran-4-vD-2,2-dimethylhydrazide
  • l-(2,6-dichlorophenyl)-5(4 )-tetrazolinone prepared according to Goto, T. et al. EP 578,090 A2
  • 10 mL of anhydrous toluene followed by 0.49 g of dimethylaminopyridine and 0.89 g of the title compound of step B.
  • Step B Preparation of ethyl(l-piperidinyl)carbamic chloride
  • Step C Preparation of 4-(2-chlorophenyl)-N-ethyl-4,5-dihvdro-5-oxo-N-( 1 - piperidinyl)- IH- tetrazole- 1 -carboxamide
  • A-l is 1-cyclohexen-l-yl and A-2 is 3,6-dihydro-2H-pyran-4-yl
  • A-l is 1-cyclohexen-l-yl and A-2 is 3,6-dihydro-2H-pyran-4-yl
  • A-l -CH CHCH 2 CH 2 - Q-l ]
  • A-l -CH CHCH 2 CH 2 -
  • 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 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.
  • 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, tung, 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.
  • 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. 4,172,714.
  • 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 12 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%.
  • Compound 137 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 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, benzofenap, bifenox, bispyribac and its sodium salt, bromacil, bromobutide, bromoxynil, bromoxynil octanoate, butachlor, butralin, butroxydim (ICIA0500), butylate, cafenstrole, caloxydim (
  • combinations with other herbicides having a similar spectrum of control but a different mode of action will be particularly advantageous for preventing the development of resistant weeds.
  • Preferred for better control of undesired vegetation in rice (e.g., lower use rate, broader spectrum of weeds controlled, or enhanced crop safety) or for preventing the development of resistant weeds in rice are mixtures of a compound of this invention with a herbicide selected from the group 2,4-D, anilofos, azimsulfuron, benfuresate, bensulfuron-methyl, bensulfuron- methyl in combination with metsulfuron-methyl, benzofenap, bispyribac-sodium, bromobutide, cafenstrole, carfentrazone-ethyl, chlorimuron-ethyl, cinosulfuron, clomazone, cumyluron, cyclosulfamuron, cyhalofop-butyl, dimepiperate, di
  • Specifically preferred mixtures are selected from the group: compound 12 and azimsulfuron, compound 12 and benfuresate, compound 12 and bensulfuron-methyl, compound 12 and benzofenap, compound 12 and bispyribac-sodium, compound 12 and carfentrazone-ethyl, compound 12 and chlorimuron-ethyl, compound 12 and cinosulfuron, compound 12 and cyclosulfamuron, compound 12 and dymron, compound 12 and ethoxysulfuron, compound 12 and halosulfuron-methyl, compound 12 and imazosulfuron, compound 12 and metsulfuron- methyl, compound 12 and oxaziclomefone, compound 12 and pentoxazone, compound 12 and propanil, compound 12 and pyrazolate, compound 12 and pyrazosulfuron-ethyl, compound 12 and pyribenzoxim, compound 12 and pyriminobac-methyl

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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 des composés de formule I et leurs N-oxydes et sels appropriés à l'agriculture, qui sont utiles pour la lutte contre toute végétation parasite. Dans ladite formule, Q, R?1, R2 et R3¿ sont tels que définis dans le corps de l'invention. L'invention concerne aussi des compositions à base des composés représentés par la formule I, et un procédé pour lutter contre toute végétation parasite qui consiste à mettre une quantité efficace d'un composé représenté par ladite formule en contact avec la végétation ou son milieu ambiant.
PCT/US1998/008884 1997-05-15 1998-05-12 Tetrazolinones herbicides WO1998051683A1 (fr)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006067139A1 (fr) * 2004-12-21 2006-06-29 Janssen Pharmaceutica N.V. Derives de triazolone, tetrazolone et imidazolone utilises comme antagonistes des recepteurs alpha2c-adrenergiques
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 (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0202929A2 (fr) * 1985-05-23 1986-11-26 UNIROYAL CHEMICAL COMPANY, Inc. Tetrazolinones substitués
EP0419917A1 (fr) * 1989-09-23 1991-04-03 BASF Aktiengesellschaft Amides l'acide pyrazole-3-carboxylique
EP0695748A1 (fr) * 1994-08-05 1996-02-07 Nihon Bayer Agrochem K.K. Herbicides tétrazolinones

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0202929A2 (fr) * 1985-05-23 1986-11-26 UNIROYAL CHEMICAL COMPANY, Inc. Tetrazolinones substitués
EP0419917A1 (fr) * 1989-09-23 1991-04-03 BASF Aktiengesellschaft Amides l'acide pyrazole-3-carboxylique
EP0695748A1 (fr) * 1994-08-05 1996-02-07 Nihon Bayer Agrochem K.K. Herbicides tétrazolinones

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006067139A1 (fr) * 2004-12-21 2006-06-29 Janssen Pharmaceutica N.V. Derives de triazolone, tetrazolone et imidazolone utilises comme antagonistes des recepteurs alpha2c-adrenergiques
JP2008524312A (ja) * 2004-12-21 2008-07-10 ジヤンセン・フアーマシユーチカ・ナームローゼ・フエンノートシヤツプ アルファ−２ｃアドレノレセプターアンタゴニストとしての使用のためのトリアゾロン、テトラゾロン及びイミダゾロン誘導体
EA011514B1 (ru) * 2004-12-21 2009-04-28 Янссен Фармацевтика Н.В. Производные триазолона, тетразолона и имидазолона для применения в качестве антагонистов альфа-2с-адренорецептора
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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