Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D335/00—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom
  • C07D335/04—Heterocyclic compounds containing six-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
  • C07D335/06—Benzothiopyrans; Hydrogenated benzothiopyrans
• • 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
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
  • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
  • A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
  • A01N43/18—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings with sulfur as the ring hetero atom
• • 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
  • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
  • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
  • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
  • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
  • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
  • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
  • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
  • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
  • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
  • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D337/00—Heterocyclic compounds containing rings of more than six members having one sulfur atom as the only ring hetero atom
  • C07D337/02—Seven-membered rings
  • C07D337/06—Seven-membered rings condensed with carbocyclic rings or ring systems
  • C07D337/08—Seven-membered rings condensed with carbocyclic rings or ring systems condensed with one six-membered ring
• • 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
  • C07D409/06—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 carbon chain containing only aliphatic carbon atoms
• • 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
  • C07D413/06—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 linked by a carbon chain containing only aliphatic carbon atoms

Definitions

• This invention relates to certain bicyclic hydrazones, 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 pu ⁇ oses, but the need continues for new compounds which are more effective, less costly, less toxic, environmentally safer or have different modes of action.
• WO 94/08988 discloses oxime derivatives of Formula i as herbicides:
• R is lower alkyl
• R ! -R 6 are H or lower alkyl
• X 1 is lower alkyl; and X 2 is H or lower alkyl.
• the hydrazone compounds of the present invention are not disclosed in this publication. SUMMARY OF THE INVENTION
• 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:
• X is O, S(O) n , N(C r C 2 alkyl) or CH 2 optionally substituted with 1-2 C r C 2 alkyl; each R 1 is independently C ⁇ -C 6 alkyl, Cj-C 6 haloalkyl, C ] -C 6 alkoxy, C ⁇ -C 6 haloalkoxy, S(O) n R 17 , SO 2 N(R 13 ) 2 , halogen, cyano or nitro;
• R 2 is NR 18 R 19 ; or R 2 is a five-membered heterocyclic aromatic ring, or a five- or six- membered heterocyclic ring which may be partially or fully saturated, each ring containing 1 to 4 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, and containing at least one nitrogen and no more than one oxygen and no more than 2 sulfurs, and the ring is optionally substituted with one to three groups independently selected from the group C j -C 3 alkyl, halogen, cyano, and nitro, provided that (a) said heterocyclic ring is bonded to the parent bicyclic structure through a ring nitrogen and (b) that when a nitrogen atom of the heterocyclic ring is substituted, then the nitrogen substituent is other than halogen; each R 3 is independently C ⁇ -C 2 alkyl;
• R 4 is OR 14 , SH, S(O) n R 17 , halogen or NR 15 R 16 ; or R 4 is phenylthio or phenylsulfonyl, each optionally substituted with C1-C3 alkyl, halogen, cyano or nitro; each R 5 is independently C1-C3 alkyl, C 3 -Cg alkenyl, C3- alkynyl, C1-C3 alkoxy, formyl, C 2 -C 6 alkoxycarbonyl, -CH (C r C 3 alkoxy), -CH(C 1 -C 3 alkoxy) 2 , C1-C3 alkylthio, cyano or halogen; or when two R 5 are attached to the same carbon atom, then they can be taken together to form -OCH 2 CH 2 O-, -OCH 2 CH 2 CH 2 O-, -SCH 2 CH 2 S- or -SCH 2 CH 2 CH 2 S-, each group optional
• R 6 is H, C r C 6 alkyl, C r C 6 haloalkyl, C 2 -C 6 alkoxyalkyl, formyl, C 2 -C 6 alkylcarbonyl, C 2 -Cg alkoxycarbonyl, C 2 -Cg alkylaminocarbonyl, C3-C 7 dialkylaminocarbonyl or SO 2 R 17 ; or R 6 is phenyl, benzyl, benzoyl, -CH 2 C(O)phenyl or phenylsulfonyl, each optionally substituted on the phenyl ring with 1 to 3 groups selected from the group C1-C3 alkyl, halogen, cyano, and nitro;
• R 7 is H, C r C 6 alkyl, C r C 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl or
• R 7 is phenyl or benzyl, each optionally substituted on the phenyl ring with C1-C3 alkyl, halogen, cyano or nitro;
• R 8 is H, Ci-Cg alkyl, C Cg haloalkyl, Cj-Cg alkoxy, C Cg haloalkoxy, halogen, cyano or nitro;
• R 9 is H, C ⁇ -C 6 alkyl, C r C 6 haloalkyl, C3-C6 cycloalkyl or C3-C6 halocycloalkyl;
• R 10 is H, C 2 -Cg alkoxycarbonyl, C 2 -Cg haloalkoxy carbonyl, CO H or cyano;
• R 1 1 is C r C 6 alkyl, C r C 6 haloalkyl, C 3 -C 6 halocycloalkyl or C 3 -C 6 cycloalkyl optionally substituted with 1-4 C1-C3 alkyl;
• R 12 is cyano, C 2 -C 6 alkoxycarbonyl, C 2 -C 6 alkylcarbonyl, S(O) n R 16 or C(O)NR 15 R 16 ; each R 13 is independently H or Ci-Cg alkyl;
• R 14 is H, C r C 6 alkyl, C r C 6 haloalkyl, C 2 -C 6 alkoxyalkyl, formyl, C 2 -C 6 alkylcarbonyl, C 2 -C 6 alkoxycarbonyl, C(O)NR 15 R 16 or SO 2 R 17 ; or R 14 is phenyl, benzyl, benzoyl, -CH 2 C(O)phenyl or phenylsulfonyl, each optionally substituted on the phenyl ring with 1 to 3 groups selected from group C1-C 3 alkyl, halogen, cyano and nitro; R 15 is H or C r C 6 alkyl; R 16 is C r C 6 alkyl or C r C 6 alkoxy; or
• R 15 and R 16 can be taken together as -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 - , -CH 2 CH 2 CH 2 CH 2 - or -CH 2 CH 2 OCH 2 CH 2 -;
• R 17 is C r C 6 alkyl or C r C 6 haloalkyl;
• R 18 is H or C r C 6 alkyl
• R 20 is phenyl or a five- or six-membered aromatic heterocyclic ring, containing 1 to 4 heteroatoms independently selected from the group nitrogen, oxygen, and sulfur, provided that the heterocyclic ring contains no more than one oxygen and no more than one sulfur, and the phenyl and heterocyclic ring are each optionally substituted with one to three groups independently selected from the group
• 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 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.
• Alkoxyalkyl denotes alkoxy substitution on alkyl. Examples of “alkoxyalkyl” include CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 CH 2 OCH 2 and
• Alkoxyalkoxy denotes alkoxy substitution on alkoxy.
• Alkylamino dialkylamino
• alkenylthio alkenylsulfinyl
• alkenylsulfonyl alkynylthio
• alkynylsulfinyl alkynylsulfonyl
• Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
• cycloalkoxy includes the same groups linked through an oxygen atom such as cyclopentyloxy and cyclohexyloxy.
• aromatic ring system denotes fully unsaturated carbocycles and heterocycles in which the polycyclic ring system is aromatic (where aromatic indicates that the H ⁇ ckel rule is satisfied for the ring system).
• aromatic heterocyclic ring system includes fully aromatic heterocycles and heterocycles in which at least one ring of a polycyclic ring system is aromatic (where aromatic indicates that the H ⁇ ckel rule is satisfied).
• nonaromatic heterocyclic ring system denotes fully saturated heterocycles as well as partially or fully unsaturated heterocycles where the H ⁇ ckel 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.
• 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 n-chloroperbenzoic acid (MCPB A), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane.
• peroxy acids such as peracetic and n-chloroperbenzoic acid (MCPB A)
• hydrogen peroxide 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 .
• 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 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 CH 3 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
• alkylcarbonyl include
• 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.
• Some compounds of this invention can exist as one or more tautomers.
• compounds of Formula la (Formula I where Q is Q-l, R 4 is OR 14 , and R 14 is H) can also exist as the tautomers of Formulae lb and Ic as shown below.
• said tautomers often exist in equilibrium with each other. As these tautomers interconvert under environmental and physiological conditions, they provide the same useful biological effects.
• the present invention includes mixtures of such tautomers as well as the individual tautomers of compounds of Formula I.
• 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 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 Q-l. Preferred 2. Compounds of Preferred 1 wherein: X is SO 2 . Preferred 3. Compounds of Preferred 1 wherein:
• R 2 is ⁇ R 18 R!9.
• Preferred 4 Compounds of Formula I above, and N-oxides and agriculturally suitable salts thereof, wherein: Q is Q-2; Preferred 5. Compounds of Preferred 4 wherein:
• X is SO 2 .
• Preferred 6 Compounds of Preferred 5 wherein: R 2 is NR1SR1 . Most preferred is the compound of Preferred 3 selected from the group:
• 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 1-14.
• the definitions of Q, R ⁇ -R 20 , Z, X, m, n, p, and r in the compounds of Formulae 1-17 below are as defined above in the Summary of the Invention.
• Compounds of Formulae Ia-Ig are subsets of the compounds of Formula I, and all substituents for Formulae Ia-Ig are as defined above for Formula I.
• compounds of Formula Id below are compounds of Formula I wherein Q is Q-l.
• Id Scheme 1 illustrates the preparation of compounds of Formula Id whereby an enol ester of Formula 1 is reacted with a base such as triethylamine in the presence of a catalytic amount of a cyanide source (e.g., acetone cyanohydrin or potassium cyanide).
• a cyanide source e.g., acetone cyanohydrin or potassium cyanide.
• Enol esters of Formula 1 can be prepared by reacting the acid of Formula 2 with N- methyl-2-chloropyridinium iodide, followed by treatment of the formed intermediate with the dione of Formula 3 in the presence of a base such as triethylamine (Scheme 2). This coupling is carried out by methods known in the art (or by slight modification of these methods): for example, see E. Haslam Tetrahedron (1980), 36, 2409-2433.
• Enol esters of Formula 1 can also be prepared by reacting a dione of Formula 3 with an acid chloride of Formula 17 in the presence of a slight excess of a base such as triethylamine in an inert organic solvent such as acetonitrile, dichloromethane or toluene at temperatures between 0 °C and 110 °C (Scheme 3a).
• a base such as triethylamine
• an inert organic solvent such as acetonitrile, dichloromethane or toluene
• the acid chlorides of Formula 17 can be prepared by one skilled in the art by reacting an acid of Formula 2 with chlorinating agents such as oxalyl chloride or thionyl chloride and a catalytic amount of dimethylformamide (Scheme 3b). This chlorination is well known in the art: for example, see W. J. Michaely, EP 369,803. Scheme 3 b
• Scheme 4 illustrates the preparation of compounds of Formula 4 whereby a compound of Formula 5 is stirred in a hydrochloric acid aqueous solution (O.lNto 12N) at temperatures between 0 °C and 100 °C for a period of time ranging from 30 minutes to 3 days.
• This conversion is carried out by methods known in the art (or by slight modification of these methods): for example; see P. A. Grieco, et al., J. Am. Chem. Soc. (1977), 99, p 5773; P. A. Grieco, et al., J. Org. Chem. (1978), 43, p 4178.
• Scheme 5 illustrates the preparation of acids of Formula 5 (X is S(O) n and n is 1 or 2) whereby an acid of Formula 5 (X is S(O) n and n is 0) is reacted with a oxidizing reagent such as peroxyacetic acid, -chloroperoxybenzoic acid, potassium peroxymonosulfate or hydrogen peroxide.
• a oxidizing reagent such as peroxyacetic acid, -chloroperoxybenzoic acid, potassium peroxymonosulfate or hydrogen peroxide.
• the reaction may be buffered with a base such as sodium acetate or sodium carbonate.
• the oxidation is carried out by general methods known in the art (see for example, B. M. Trost, et al., J. Org. Chem. (1988), 53, 532; B. M. Trost, et al., Tetrahedron Lett. (1981), 21, 1287; S. Patai, e
• Scheme 7 illustrates the preparation of phenyl bromides of Formula 6 (n is 0 when X is S(O) n ) whereby a ketone of Formula 7 (n is 0 when X is S(O) n ) is reacted with HO(CH 2 ) 2 OH in the presence of a protic acid catalyst such as/?-toluenesulfonic acid (or a Lewis acid such as BF3) in an inert organic solvent such as toluene.
• a protic acid catalyst such as/?-toluenesulfonic acid (or a Lewis acid such as BF3)
• a Lewis acid such as BF3
• ketones of Formula 7 can also be prepared by general methods known in the art (or by slight modification of these methods); see, for example, W. Flemming, et al., Chem. Ber. (1925), 58, 1612; I. W. J. Still, et al., Can. J. Chem. (1976), 54, 453-470; V. J. Traynelis, et al, J. Org. Chem. (1961), 26, 2728; I. Nasuno, et al., WO 94/08988; F. Camps, et al., J. Heterocycl. Chem. (1985), 22(5), p. 1421 ; T. S. Rao, et al, Indian J. Chem.
• the dicarbonyl compounds of Formula 3 are either commercially available or can be prepared by general methods known in the art (or by slight modification of these methods): for example, see D. Cartwright, et al., EP 0283261-B1; J. Dangelo, et al., Tet. Lett. (1991), 32(26), p. 3063; T. Okado, et al., J. Org. Chem. (1977), 42, p. 1163; B. E. Maryanoff, et al., J. Am. Chem Soc. (1975), 97, p. 2718; E. Er, et al., Helv. Chim. Ada. (1992), 75(7), p.
• cyanide source e.g., acetone cyanohydrin or potassium cyanide.
• Compounds of Formula 8 or 8a can be prepared by reacting the acid of Formula 2 with N-methyl-2-chloropyridinium iodide, followed by treatment of the formed intermediate with the hydroxypyrazole of Formula 9 in the presence of a base such as triethylamine (Scheme 8a).
• a base such as triethylamine
• Esters of Formula 8 or amides of Formula 8a can also be prepared by reacting a hydroxypyrazole of Formula 9 with an acid chloride of Formula 17 in the presence of a slight mole excess of a base such as triethylamine in an inert organic solvent such as acetonitrile, methylene chloride or toluene at temperatures between 0 °C and 110 °C (Scheme 9).
• a base such as triethylamine
• an inert organic solvent such as acetonitrile, methylene chloride or toluene
• Scheme 10 illustrates the preparation of compounds of Formula If whereby a compound of Formula 10 is reacted with a salt of hydroxylamine such as hydroxylamine hydrochloride in the presence of a base or acid acceptor such as triethylamine or sodium acetate.
• a base or acid acceptor such as triethylamine or sodium acetate.
• the substituents of the immediate products may be further modified if appropriate. This cyclization is carried out by methods known in the art (or by slight modification of these methods): for example, see P. A. Cain, et al., EP 560,483; C. J. Pearson, et al., EP 636,622.
• L is a leaving group such as C j -C jalkoxy (e.g., OC 2 H5) or NN-dialkylamino (e.g., dimethyl amino)
• Scheme 11 illustrates the preparation of compounds of Formula 10 whereby a compound of Formula 11 is reacted with a reagent of Formula 12 or Formula 13. This conversion is carried out by methods known in the art (or by slight modification of these methods): for example, see P. A. Cain, et al., EP 560,483; C. J. Pearson, et al., EP 636,622.
• Scheme 12 illustrates the preparation of compounds of Formula 11 whereby an ester of Formula 14 is decarboxylated in the presence of a catalyst, such as j-toluenesulfonic acid, in an inert solvent such as toluene.
• a catalyst such as j-toluenesulfonic acid
• an inert solvent such as toluene.
• Esters of Formula 14 can be prepared by reacting the metal salt of a compound of Formula 1 with an acid chloride of Formula 17 (Scheme 13). This type of coupling is known in the art: for example see P. A. Cain, et al., EP 560,483; C. J. Pearson, et al., EP 636,622.
• Scheme 14 illustrates the preparation of compounds of Formula Ig whereby a compound of Formula 17 is reacted with a compound of Formula 16 in the presence of a base such as triethylamine, potassium carbonate, sodium hydride or Mg(OEt) 2 in an inert organic solvent such as diethyl ether, tetrahydrofuran, NN-dimethylformamide, dichloromethane or acetonitrile.
• a base such as triethylamine, potassium carbonate, sodium hydride or Mg(OEt) 2
• an inert organic solvent such as diethyl ether, tetrahydrofuran, NN-dimethylformamide, dichloromethane or acetonitrile.
• Step B Preparation of 2,3-dihvdro-5,8-dimethyl-4_ 1 /- 1 -benzopyran-4-one
• Step E Preparation of 2,3-dihydro-5, 8-dimethylspiror4H-l-be ⁇ _zothiopyran-4,2'-
• Step F Preparation of 2,3-dihydro-5.8-dimethylspiror4 _ " - 1 -benzothiopyran-4,2'- ⁇ ,31dioxolanel-6-carboxylic acid 1,1 -dioxide 4.73 g (0.017 mol) of the title compound of Step E and 2.08 g (0.025 mol) of sodium acetate were added to 85 mL of methanol. The solution was cooled to about 0 °C, and a solution of 17.66 g (0.029 mol) of OXONE® (purchased from Aldrich Chemical Company) in 85 mL of water was added dropwise while keeping the temperature below 6 °C.
• OXONE® purchased from Aldrich Chemical Company
• Step H Preparation of 4-(dimethylhydrazono)-3,4-dihydro-5,8-dimethyl-27 -l- benzothiopyran-6-carboxylic acid 1,1 -dioxide
• Step I Preparation of 3-oxo- 1 -cyclohexen- 1 -yl 4-(dimethylhydrazono)-3 ,4-dihydro-
• Step J Preparation of 2-rr4-(dimethylhydrazono)-3,4-dihvdro-5,8-dimethyl-2 - " -l- benzothiopyran-6-yllcarbonyll- 1 ,3-cvclohexanedione 5,S-dioxide
• acetone cyanohydrin purchased from Aldrich Chemical Company
• potassium cyanide purchased from Janssen
• 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.
• 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, 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.
• 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 2 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.
• Example C Granule Compound 3 10.0% attapulgite granules (low volatile matter
• Example D Extruded Pellet Compound 10 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.
• Test results indicate that the compounds of the present invention are highly active preemergent and postemergent herbicides or plant growth regulants. Many of them have utility for broad-spectrum pre- and/or postemergence weed control in areas where complete control of all vegetation is desired such as around fuel storage tanks, industrial storage areas, parking lots, drive-in theaters, air fields, river banks, irrigation and other waterways, around billboards and highway and railroad structures.
• 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).
• 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,
• 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, bifenox, bispyribac and its sodium salt, bromacil, bromoxynil, bromoxynil octanoate, butachlor, butralin, butroxydim (ICIA0500), butylate, caloxydim (BAS 620H), carfentrazone-ethyl,
• a lH NMR data are in ppm downfield from tetramethylsilane. Couplings are designated by (s)-singlet, (m)-multiplet, (br m)-broad multiplet.
• Plants ranged in height from 2 to 18 cm (1- to 4-leaf stage) for postemergence treatments. 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.
• Sorghum 10 Sorghum 1 Sorghum 9
• Seeds of broadleaf signalgrass (Brachiaria decumbens), bedstraw (Galium aparine), blackgrass (Alopecurus myosuroides), cocklebur (Xanthium strumarium), com (Zea mays), crabgrass (Digitaria sanguinalis), giant foxtail (Setariafaberii), momingglory (Ipomoea hederacea), rape (Brassica napus), redroot pigweed (Amaranthus retrofiexus), soybean (Glycine max), sugar beet (Beta vulgaris), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum), wild oat (Avenafatua) and purple nutsedge (Cyperus rotundus) tubers were planted and treated preemergence with test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant.
• Plants ranged in height from 2 to 18 cm (1- to 4-leaf stage) for postemergence treatments.
• Plant species in the flood test consisted of rice (Oryza sativa), smallflower flatsedge (Cyperus difformis), duck salad (Heteranthera limosa) and bamyardgrass (Echinochloa crus-galli) 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 B 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.
• Rate 500 g/ha 5 6 Rate 500 g/ha 5 6 Rate 250 g/ha 5 6
• Soybean 10 Wild oats 1 1 Soybean 10 10
• Soybean 1 0 0 0 0 0 0 0 0 0 0 0 0 0
• Rate 4 g/ha 2 10 Rate 4 : g/ha 2 10 Rate 4 g/ha 2 10
• bamyardgrass Echinochloa crus-galli
• bindweed Concolculus arvensis
• black nightshade Solanum ptycanthum duna ⁇
• cassia Cassia obtusifolia
• cocklebur Xanthium strumarium
• common ragweed Ambrosia artemisiifolia
• com Zea mays designated 'Co 2', 'Com 4' and 'Com 5'
• cotton Gossypium hirsutam
• crabgrass Digitaria spp.
• fall panicum Panicum dichotomiflorum
• giant foxtail Setariafaberii
• green foxtail Setaria viridis
• jimsonweed Datura stramoni um
• johnsongrass Sorghum halepense
• lambsquarter Chenopodium album
• momingglory Ipomoea spp.
• pigweed Amaranthus retroflex
• Bamyardgrass 85 Bamyardgrass 20 Bamyardgrass 85
• Cocklebur 85 Cocklebur 0 Cocklebur 85
• Jimsonweed 100 Green foxtail 30 Jimsonweed 100
• Shattercane 85 Signalgrass 20 Shattercane 80
• Soybean 1 100 Sunflower 30 Soybean 1 100
• Soybean 2 100 Velvetleaf 100 Soybean 2 100
• Soybean 1 15 Signalgrass 100 Soybean 1 15
• Soybean 2 30 Smartweed 100 Soybean 2 25
• Bindweed 45 Bindweed 10 Bindweed 40
• Jimsonweed 100 Green foxtail 0 Jimsonweed 100
• Shattercane 75 Signalgrass 0 Shattercane 75
• Soybean 2 85 Velvetleaf 20 Soybean 2 85
• the compounds evaluated in this test were formulated in a non-phytotoxic solvent mixture which included a surfactant and applied to the soil surface before plant seedlings emerged (preemergence application), to water that covered the soil surface (flood application), and to plants that were in the one- to four-leaf stage (postemergence application).
• preemergence application to water that covered the soil surface
• postemergence application to plants that were in the one- to four-leaf stage
• a sandy loam soil was used for the preemergence and postemergence tests, while a silt loam soil was used in the flood application. Water depth was approximately 2.5 cm for the flood application and was maintained at this level for the duration of the test.
• Plant species in the preemergence and postemergence tests consisted of bamyardgrass
• Plant species in the flood test consisted of rice (Oryza sativa), umbrella sedge (Cyperus difformis), duck salad (Heteranthera limosa) and bamyardgrass 1 (Echinochloa crus-galli). All plant species were grown using normal greenhouse practices. Visual evaluations of injury expressed on treated plants, when compared to untreated controls, were recorded approximately fourteen to twenty one days after application of the test compound. Plant response to the test compound is summarized in Table D, recorded on a 0 to 100 scale where 0 is no effect and 100 is complete control. A dash (-) response means no test result.
• Bamyardgrass 90 Bamyardgrass 30 Bamyardgras s 90
• Rape 80 Sugar beet 90 Rape 60
• Redroot pigweed 90 Velvetleaf 100 Redroot pigweed 90
• Umbrella sedge 80 Umbrel la sedge 60
• Barley (winter) 0 Barley (winter) 20 Barley (winter) 0
• Bamyardgrass 0 Bamyardgrass 90 Bamyardgrass 0
• Bedstraw 50 Bamyardgrass 1 0 Bedstraw 50
• Rate 8 g/ha 1 Rate 8 g/ha 1
• Crop and weed species include arrowleaf sida (Sida rhombifolia), bamyardgrass (Echinochloa crus-galli), cocklebur (Xanthium strumarium), common ragweed (Ambrosia elatior), com 1 (Zea mays), cotton (Gossypium hirsutum), eastern black nightshade (Solanum ptycanthum), fall panicum (Panicum dichotomiflorum), field bindweed (Convolvulus arvensis), giant foxtail (Setariafaberii), hairy beggarticks (Bidens pilosa), ivyleaf momingglory (Ipomoea hederacea), johnsongrass (Sorghum halepense), ladysthumb smartweed (Polygonum per
• 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 E, 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.
• Field bindweed 85 Field bindweed 95 Field bindweed 95 Giant foxtai l 100 Giant foxtai l 95 Giant foxtai l 90 H . beggarticks 85 H . beggarticks 80 H . beggarticks 70 I . momingglory 100 I . momingglory 100 I . momingglory 100 Johnsongrass 90 Johnsongrass 75 Johnsongrass 50
• bamyardgrass Echinochloa crus-galli
• crabgrass Digitaria spp.
• momingglory Ipomoea spp.
• velvetleaf Abutilon theophrasti
• Plants ranged in height from two to eighteen cm and were in the one- to two-leaf stage for the postemergence treatment. Treated plants and untreated controls were maintained in a greenhouse for approximately eleven days, after which all treated plants were compared to untreated controls and visually evaluated for injury. Plant response ratings, summarized in Table F, are based on a 0 to 10 scale where 0 is no effect and 10 is complete control. A dash (-) response means no test results.
• Rate 2000 g/ha 3 7 8 9 Rate 1000 g/ha 3 7 8 9

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