Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
  • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
  • C07D271/06—1,2,4-Oxadiazoles; Hydrogenated 1,2,4-oxadiazoles
  • C07D271/07—1,2,4-Oxadiazoles; Hydrogenated 1,2,4-oxadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
• • 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
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
  • C07C271/62—Compounds containing any of the groups, X being a hetero atom, Y being any atom, e.g. N-acylcarbamates
  • C07C271/66—Y being a hetero atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
  • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
  • C07D271/08—1,2,5-Oxadiazoles; Hydrogenated 1,2,5-oxadiazoles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D271/00—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms
  • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
  • C07D271/10—1,3,4-Oxadiazoles; Hydrogenated 1,3,4-oxadiazoles
• • 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
  • 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
• • 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
  • C07D413/12—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 chain containing hetero atoms as chain links
• • 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
• • 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
  • C07D417/06—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 linked by a carbon chain containing only aliphatic carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic System
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/0803—Compounds with Si-C or Si-Si linkages
  • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
  • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic System
  • C07F9/02—Phosphorus compounds
  • C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
  • C07F9/6527—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having nitrogen and oxygen atoms as the only ring hetero atoms
  • C07F9/653—Five-membered rings
  • C07F9/65306—Five-membered rings containing two nitrogen atoms
  • C07F9/65318—Five-membered rings containing two nitrogen atoms having the two nitrogen atoms in positions 1 and 3

Definitions

• This invention relates to certain oxadiazolidines, processes for their preparation, their N-oxides, agriculturally suitable salts and compositions, and methods of their use for controlling undesirable vegetation.
• This invention also relates to mixtures of herbicides that have a synergistic effect on weeds or have a safening effect on crops while retaining or increasing weed control.
• This invention is directed to compounds and processes to prepare compounds of Formula 1 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 H; or C r C 12 alkyl, C 3 -C 10 cycloalkyl, C 6 -C 14 bicycloalkyl, C 3 -C 12 alkenyl, C 3 -C 10 cycloalkenyl, C 6 -C 14 bicycloalkenyl or C 3 -C 12 alkynyl, each optionally substituted with one or more R 1 ; or Q is a 3- to 7-membered fully saturated or 5- to 7-membered partially saturated heterocyclic ring containing one or two X, provided that (a) when X is other than O or S(O) n , then only one X may be present and (b) when two X are present in the ring, they cannot be bonded directly to each other; or 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
• Y is, together with the carbons to which it is attached, a fully or partially saturated 5-,
• Y is, together with the carbons to which it is attached, a fully or partially saturated 5-, 6- or 7-membered heterocyclic ring which contains one or two X and is optionally substituted with one or more R 12 , provided that when said heterocyclic ring contains two X, then one X is other than O;
• Z is phenyl or 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 phenyl and heterocyclic ring system is optionally substituted with one or more R 16 ;
• 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 -C 6 haloalkynyl, C ⁇ -
• R 1 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 with one or more R 16 ;
• R 2 is C r C 6 alkyl, C r C 6 haloalkyl, C 3 -C 7 cycloalkyl, C r C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkynyl, C j -Cg alkoxy, C 2 -C 6 alkoxyalkyl, C 2 -C 6 haloalkoxyalkyl or NR 3 R 4 ; or
• R 1 and R 2 are 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 -,
• R 3 is C r C 6 alkyl, C r C 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C r C 6 alkynyl,
• R 3 is C 3 -C 7 cycloalkyl or C 3 -C 7 cycloalkenyl, each optionally substituted with one or more R 5 ; or R 3 is a saturated or partially saturated 5-, 6- or 7-membered heterocyclic ring containing 1 to 2 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, and each heterocyclic ring is optionally substituted with one or more R 5 ; or
• R 3 is phenyl optionally substituted with one or more R 26 groups;
• R 1 and R 3 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 the group consisting of oxygen, sulfur and nitrogen, and said heterocyclic ring is optionally substituted with one or more R 9 ; or R 2 and R 13 , together with the two atoms to which they are attached and the atom between them, form a fully saturated 5-, 6- or 7-membered carbocyclic or heterocyclic ring containing one oxygen, one sulfur or one or two nitrogen atoms, said heterocyclic ring is optionally substituted with one or more R 12 , provided that when said heterocyclic ring contains two nitrogen atoms, they are other than bonded directly to each other; R 4 is H or C C 4 alkyl; or R 3 and R 4 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 hetero
• W is, together with the carbons to which it is attached, a fully or partially saturated 5-, 6- or 7-membered heterocyclic ring containing one or two X, provided that (a) when X is other than O or S(O) n , then only one X may be present; (b) when two X are present in the ring, they cannot be bonded directly to each other; and (c) said heterocyclic ring is bonded to the group (CR ⁇ R 18 ) q through other than X;
• R 10 is H, C r C 4 alkyl, C r C 4 haloalkyl, C 3 -C 4 alkenyl, C 3 -C 4 alkynyl, C 2 -C 4 alkoxycarbonyl or C 2 -C4 alkylcarbonyl; or R 10 is phenyl optionally substituted with Cj-C 3 alkyl, halogen, cyano, nitro or C 2 -C4 alkoxycarbonyl; each R 1 1 is C r C 4 alkyl; each R 12 is independently halogen, C1-C4 alkyl, C1-C4 haloalkyl, Cj-C4 alkoxy,
• each R 13 is independently halogen, C r C 3 alkyl, C C haloalkyl, Cj-C 3 alkoxy,
• R 14 is H, C C 6 alkyl, C C 6 haloalkyl or C 2 -C 6 alkoxyalkyl; or R 14 and R 6 , together with the carbon atoms to which they are bonded, form a 5- or 6- membered saturated carbocyclic ring optionally substituted with one or more C1-C 4 alkyl groups;
• R 15 is H, C C 6 alkyl, C r C 6 haloalkyl, C 3 -C 4 alkenyl or C 3 -C 4 alkynyl; each R 16 is independently halogen, nitro, cyano, C C alkyl, -C4 haloalkyl, C 3 -C 4 alkenyl, C 3 -C 4 alkynyl, OR 22 , NR 23 R 24 or S(O) n R 1 9; each R 17 and R 18 are independently H or C1-C4 alkyl; each R 19 and R 20 are independently C r C ⁇ 2 alkyl, C 3 -C 8 cycloalkyl, C 3 -C l2 alkenyl, C 3 -Cg cycloalkenyl or C 3 -Cj 2 alkynyl, each optionally substituted with one or more R 21 ; each R l is halogen, C 4 -C 8 trialkylsilylalkyl, CN,
• each R 22 is C r C 8 alkyl, C 3 -C 8 cycloalkyl, C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C C 8 haloalkyl, C 2 -C 8 alkoxyalkyl, C -C 8 alkylthioalkyl, C 2 -C 8 alkylsulfinylalkyl, C 2 -C alkylsulfonylalkyl, Q-Cs alkoxyalkoxyalkyl, C 4 -C 8 cycloalkylalkyl,
• each R 23 is H or C r C 4 alkyl; each R 24 is C1-C4 alkyl or phenyl optionally substituted with one or more R 26 groups; R 23 and R 24 may be taken together as -(CH 2 ) 5 -, -(CH 2 ) 4 - or -CH 2 CH 2 OCH 2 CH 2 -, each ring optionally substituted with C j -C 3 alkyl, phenyl or benzyl; each R 25 is H or C r C 4 alkyl; each R 26 is C r C 3 alkyl, C C 3 haloalkyl, C r C 3 alkoxy, C C 3 haloalkoxy, C r C 3 alkylthio, Q2-C5 alky
• R 28 is H or C r C 4 alkyl; X 1 and X 2 are independently O or S; X 3 is O, S orNR 28 ; m is O, 1, 2, 3 or 4; each n is independently 0, 1 or 2; p is O or l; each q is independently 0, 1 or 2; and t is O, 1 or 2; provided that when Q is unsubstituted phenyl, X 1 , X 2 and X 3 are O, q is 0 and R 2 is methyl, then R 1 is other than methyl.
• 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, z ' -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, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
• Alkoxyalkyl denotes alkoxy substitution on alkyl.
• alkoxyalkyl examples 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 CH 3 CH 2 OCH 2 CH 2 .
• Alkylthio includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.
• Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.
• “Saturated Carbocyclic” ring denotes a ring having a backbone consisting of carbon atoms linked to one another by single bonds; unless otherwise specified, the remaining carbon valences are occupied by hydrogen atoms.
• 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.
• haloalkyl include F 3 C, C1CH 2 , CF 3 CH 2 and CF 3 CC1 2 .
• 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.
• C ⁇ -C 3 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 .
• a compound of Formula 1 contains a heterocyclic ring, all substituents are attached to this ring through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
• 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 1, 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.
• 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 /n-chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethydioxirane.
• MCPBA peroxy acids
• alkyl hydroperoxides such as t-butyl hydroperoxide
• sodium perborate sodium perborate
• dioxiranes such as dimethydioxirane
• 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.
• Preferred compounds for reasons of better activity and/or ease of synthesis are:
• C 3 -C ⁇ 2 alkynyl each optionally substituted with one or more R 21 ; or Q is a 3- to 7-membered fully saturated or 5- to 7-membered partially saturated heterocyclic ring containing one or two X, provided that (a) when X is other than
• 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 with one or more R 16 ; and when Q is a 5- or 6- membered aromatic heterocyclic ring system containing a nitrogen, then Q is bonded through any available carbon or nitrogen atom by replacement of a hydrogen on said carbon or nitrogen atom; or
• Q is phenyl optionally substituted with one or more substituents independently selected from the group consisting of R 16 , phenoxy and Z.
• Preferred 2 Compounds of Preferred 1 wherein
• Q is C
• Q is a 3- to 7-membered fully saturated or 5- to 7-membered partially saturated heterocyclic ring containing one or two X, provided that (a) when X is other than O or S(O) n , then only one X may be present and (b) when two X are present in the ring, they cannot be bonded directly to each other; or 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 with one or more
• Q is phenyl optionally substituted with one or more substituents independently selected from the group consisting of R 16 , phenoxy and Z. Preferred 5.
• Q is C Cg alkyl optionally substituted with one or more R 21 , C 5 -C 7 cycloalkyl, C 3 -C 7 alkenyl or C 3 -C 6 alkynyl.
• Q is a 5- or 6-membered aromatic heterocyclic ring system ⁇ x>ntaining 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 with one or more R 16 ; and when Q is a 5- or 6-membered aromatic heterocyclic ring system containing a nitrogen, then Q is bonded through any available carbon or nitrogen atom by replacement of a hydrogen on said carbon or nitrogen atom.
• Q is phenyl optionally substituted with one or more substituents independently selected from the group consisting of R 16 .
• Preferred 8. Compounds of Preferred 2, Preferred 3 or Preferred 4 wherein X 1 , X 2 and X 3 are O.
• Q is phenyl with substituents on the 2-, and 6- ⁇ osition independently selected from the group consisting of R 16 .
• Preferred 10 Compounds of Preferred 5 wherein q is O or l.
• R 2 is C 2 -C 6 alkyl, C 2 -C 6 haloalkyl or C 2 -C 6 alkoxyalkyl.
• Most preferred is the compound of Formula 1 which is selected from the group consisting of: (a) N-(4-fluorophenyl)-N-( 1 -methylethyl)-4-(2-methylphenyl)-3,5-dioxo-
• the oxadiazolidines of Formula 1 are useful as herbicides.
• the present invention also relates to processes for preparing an oxadiazolidine of Formula 1.
• the present processes for preparing the oxadiazolidines of Formula 1 provided herein are characterized by employing a process sequence selected from process sequences A, B, C, D or E as described below.
• R 27 is -(CR 6 R 7 ) q -Q, with a compound of Formula 4
• PROCESS SEQUENCE B A process for preparing a compound of Formula 1
• R 27 is -(CR 6 R 7 ) q -Q, with an alcohol of Formula 6
• R 27 is -(CR 6 R 7 ) q -Q, with a carbamoyl or thiocarbamoyl chloride of Formula 2
• R 27 is -(CR 6 R 7 ) q -Q, in the presence of a base.
• PROCESS SEQUENCE G A process for preparing a compound of Formula 1
• the present invention also relates to an intermediate compound of Formula 5
• R 27 is -(CR 6 R 7 ) q -Q; R 6 , R 7 , q, Q, ⁇ l and X 2 are as defined above for Formula 1; provided that when ⁇ l and X 2 are O and q is 0, then Q is other than unsubstituted benzyl.
• the present invention also relates to intermediate compounds of Formula 8 and Formula 20
• R 6 , R 7 , q, Q and X 2 are as defined above for Formula 1 ; and X J is O; provided that when X 2 is O and q is 0, then Q is other than unsubstituted benzyl.
• the oxadiazolidines of Formula 1 can be used alone or in combination with other commercial pesticides.
• the present invention also relates to certain rare combinations that surprisingly give greater-than-expected or synergistic effect, or give a less-than-additive or safening effect on crops while retaining or increasing synergistically weed control.
• the mixtures of compounds of Formula 1 and certain sulfonylureas have now been discovered to synergistically control weeds.
• This invention also relates to a herbicidal composition
• a herbicidal composition comprising a herbicidally effective amount of a compound of Formula 1 and at least one of 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 the growth of undesired vegetation comprising contacting the vegetation or its environment with a herbicidally effective amount of a compound of Formula 1.
• DETAILS OF THE INVENTION Compounds of the Formula 1 can be readily prepared by one skilled in the art by using the reactions and techniques described in Scheme 1 to Scheme 10 below. In cases where a substituent of the starting material is not compatible with the reaction conditions described for any of the reaction schemes, the substituent can be converted to a protected form prior to the described reaction scheme and then deprotected after the reaction using commonly accepted protection/deprotection techniques (see Green, T. W and Wuts, P. G., Protecting Groups in Organic Transformations, 2nd Edition, John Wiley and Sons, New York, 1991).
• compounds of Formula 1 can be obtained by the reaction of oxadiazolidines of Formula 8 with carbamyl chlorides of Formula 2.
• the preferred solvent for the carbamoylation reaction is an inert solvent such as tetrahydrofuran, toluene, benzene or dioxane.
• a tertiary amine base such as triethylamine or diisopropylethylamine is preferable.
• Use of an acylation catalyst such as 4-dimethylaminopyridine or 4-pyrrolidinopyridine in a catalytic or stoichiometric amount is preferred.
• Other bases such as alkali hydroxide, carbonates or hydrides may also be employed.
• the reaction can be carried out at temperatures between 20 to 150 °C.
• Oxadiazolidines of Formula 8 can be prepared by methods known in the literature. Zinner reported the preparation of a wide variety of oxadiazolidines. See, for example: Arch. Pharm. (1965), 298, 580-587; Arch. Pharm. (1971), 303, 139-144, German patent application, DE 2010396 (1971). As shown in Scheme 2, a hydroxyurea or hydroxythiourea of Formula 9 is reacted with an activated carbonyl or thiocarbonyl compound of Formula 10 in the presence of a base to give compounds of Formula 8.
• Suitable activated carbonyl compounds are ethyl chloroformate, phenyl chloroformate, carbonyl diimidazole, phosgene, diphosgene or triphosgene.
• suitable activated thiocarbonyl compounds are carbon disulfide, thiophosgene and thiocarbonyldiimidazole.
• Suitable bases include alkali carbonates, tertiary amines such as trie ylamine and alkali hydroxides. The reaction can be carried out in a variety of solvents including tetrahydrofuran, toluene, dichloromethane, chloroform, acetonitrile or dioxane.
• the reaction may also be carried out in two-phase mixtures of water and an organic solvent such as dichloromethane, ethyl acetate or toluene. Depending on the reactivity of the carbonyl or thiocarbonyl compound, the reaction may be carried out at temperatures from 0 to 150 °C.
• Carbamyl chlorides of Formula 2a (which are compounds of Formula 2 wherein X 3 is O) are well known in the literature and can be made by the reaction of amines of Formula 13 with phosgene or a phosgene equivalent such as di- or triphosgene as shown in Scheme 4.
• phosgene or a phosgene equivalent such as di- or triphosgene as shown in Scheme 4.
• the presence of a base is useful and the use of hindered tertiary amines such as diisopropylethyl amine is preferred.
• the reaction can be carried out in a variety of solvents such as toluene or benzene that are inert to phosgene and its equivalents.
• the reaction can be carried out at temperatures from 0 to 120 °C.
• hydroxyureas and thioureas of Formula 9 can be prepared from the reaction of hydroxylamine with isocyanates or isothiocyanates of Formula 11.
• the reaction is carried out in a two-phase reaction medium consisting of water and an organic solvent such as toluene, benzene, dichloroethane, dichloromethane, ethyl acetate or chlorobutane.
• the hydroxylamine employed can be a commercially available aqueous solution or can be prepared in situ from the reaction of an acid addition salt of hydroxylamine with an alkali hydroxide or carbonate.
• the reaction is generally carried out at temperatures between 0 and 40 °C.
• Isocyanates of Formula 11 a are commercially available or can be prepared from amines of Formula 14 as shown in Scheme 6.
• the reaction of phosgene or its equivalents (such as di- and triphosgene) with amines or amine hydrochlorides of Formula 14 gives the isocyanates of Formula 11a.
• This reaction is well known in the literature and can be carried out in a variety of solvents such as toluene, benzene, ethyl acetate or dichloroethane which are inert to phosgene.
• the reaction may be carried out at temperatures from 0 to 200 °C.
• isocyanates of Formula 11a can also be formed from activated acids of Formula 15. Acid halides, anhydrides, imidazolides and the like can be reacted with various azides to provide, after a Curtius rearrangement, the isocyanates of Formula 11 a.
• the azide used may be an alkali azide, trialkylsilyl azide or trialkylstannyl azide.
• the reaction may be carried out in solvents such as toluene, tetrahydrofuran, ethyl acetate, dioxane, benzene, or methyl tert-butyl ether.
• T is halogen, imidazole, etc.
• M is alkali metal, trialkylsilyl or trialkylstannyl
• compounds of Formula 9 can also be made by the reaction of compounds of Formula 16 with hydroxylamine.
• the reaction may be carried out in a number of different solvents including tetrahydrofuran, dioxane, acetonitrile, dimethylformamide and dimethylsulfoxide. Temperatures from 0 to 160 °C maybe employed in this transformation.
• Many compounds of Formula 16 are known, and can be made by the reaction of commercially available chloroformates and chlorothioformates with compounds of Formula 14.
• compounds of Formula 9 can also be made by the reaction of activated hydroxylamines of Formula 17 with amines of Formula 14.
• the reaction may be carried out in a number of different solvents including tetrahydrofuran, dioxane, acetonitrile, dimethylformamide and dimethylsulfoxide. In some cases lower alcohols or even mixtures of water and alcohols may also be employed. Temperatures from 0 to 160 °C maybe employed in this transformation.
• Compounds of Formula 17 are known in the literature and can be made from hydroxylamine and activated esters or thioesters (See Oesper and Broker, J. Am. Chem. Soc, 1925, 47, 2607; Defoin et. al., Helv. Chim. Acta., 1992, 75, 109-123; and Stewart and Brooks, J. Org. Chem., 1992, 57, 5020-5023).
• Compounds of Formula 2b (which are compounds of Formula 2 wherein X 3 is NR23) can b e made by the chlorination of ureas of Formula 18 as shown in Scheme 10.
• the chlorination may be carried out with a wide variety of reagents such as phosphorus oxychloride, thionyl chloride, phosphorous pentachloride, or triphenylphosphine reagents with carbon tetrachloride or chlorine.
• a variety of solvents may be used including halogenated solvents such as dichloromethane, dichloroethane, or trichloroethane.
• a preferred solvent of the transformation is dimethylformamide.
• the reaction may be carried out from 0 to 150 °C.
• isothiocyanates of Formula 1 la are commercially available.
• Amines of Formula 13 are commercially available or can be prepared by methods disclosed in the literature. See the following references and references cited therein for synthesis of these materials: Kim, World Patent Application 98/51683 (1998); Dhar, World Patent Application 98/35961 (1998); Rorer, World Patent Application 98/25912 (1998); and Morita et. al., World Patent Application WO 98/11079 (1998).
• Amines of Formula 14 are commercially available or can be synthesized by methods known in the art. See the following references and references cited therein for synthesis of these materials: Kim, World Patent Application 98/51683 (1998); Dhar, World Patent Application 98/35961(1998); Rorer, World Patent Application 98/25912 (1998), Goto et. al., European Patent Application EP 695748 (1996); Goto et. al., European Patent Application EP 771,797 (1997); and Goto et. al. US patent 5,589,439 (1996).
• Activated carboxylic acids of Formula 10 are commercially available or can be prepared by methods disclosed in the literature.
• Step 1 forms compounds of Formula 3 by contacting compounds of Formula 5 with compounds of Formula 4 in the presence of a suitable base either neat or in a suitable solvent.
• Compounds of Formula 5 may be prepared, for example, by methods described in Synthesis, 1991, 265.
• the reaction temperature is generally from -10 to 250 °C, preferably from 0 to 100 °C.
• the reaction times are generally from 0.25 to 48 h, preferably from 0.25 to 24 h.
• the pressure is in the range of 1.013 x 10 2 to 2.026 x 10 2 KPa, preferably ambient pressure.
• Suitable solvents include typical organic solvents in which the reactants can be dissolved and the process of Step 1 can proceed without interference.
• Such reactants include aromatics such as benzene, toluene, xylene, chlorobenzene and dichlorobenzene, ethers such as dioxane and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ethyl acetate, dichloromethane, dichloroethane, and polar aprotic solvents such as dimethylformamide and dimethylsulfoxide.
• aromatics such as benzene, toluene, xylene, chlorobenzene and dichlorobenzene
• ethers such as dioxane and tetrahydrofuran
• nitriles such as acetonitrile and propionitrile
• ethyl acetate dichloromethane
• dichloroethane dichloroethane
• polar aprotic solvents such as dimethylformamide and dimethylsulfoxide.
• Suitable bases include organic trialkylamines such as trimemylamine, triethylamine, diisopropylethylamine, tributylamine and the like, dimethylaniline, N,N-dimethylamino- pyridine, N-methylmorpholine, l,8-diazabicyclo[5.4.0]undec-7-ene, 1,4- diazabicyclo[2.2.2]octane and l,5-diazabicyclo[4.3.0]non-5-ene. 1,8-Diazabicyclo[5.4.0]- undec-7-ene is a particularly useful organic base for this reaction.
• organic trialkylamines such as trimemylamine, triethylamine, diisopropylethylamine, tributylamine and the like, dimethylaniline, N,N-dimethylamino- pyridine, N-methylmorpholine, l,8-diazabicyclo[5.4.0]und
• Inorganic bases include, but are not limited to, potassium carbonate, sodium carbonate, potassium hydride, sodium hydride, lithium carbonate and cesium carbonate.
• a phase transfer catalyst can accelerate the reaction in the presence of inorganic bases.
• Phase transfer catalysts include tetraalkylammonium halides, crown ethers, phosphonium salts, silicon analogs of crown ethers and acyclic analogs of crown ethers.
• Particularly useful as a base is the combination of potassium carbonate and a phase transfer catalyst.
• at least an equimolar amount of the Formula 4 compound is used in respect to the Formula 5 compound, and preferably at least a small molar excess of the Formula 4 compound is used.
• the molar ratio of the Formula 4 compound to the Formula 5 compound is usually in the range of 1.05: 1 to 10: 1. In most cases, the molar ratio of the Formula 5 compound to the Formula 4 compound is preferably in the range of 1.1 : 1 to 1.5: 1. Generally at least an equivalent of base is used in respect to the Formula 5 compound, and preferably at least a small equivalent excess of the base is used. More particularly, the ratio of the number of equivalents of base to number of moles of the Formula 5 compound is usually in the range of 1.05: 1 to 10: 1. In most cases, the ratio of the number of equivalents of base to number of moles of the Formula 5 compound is preferably in the range of 1.1 : 1 to 1.5: 1.
• the equivalent amount of base may be similar to the molar amount of the Formula 4 compound, but this is not necessary.
• the compound of Formula 4 is preferably added to the reaction mixture containing the compound of Formula 5 and a base either neat or in a solvent. The reaction temperature is maintained during and after the addition and until the reaction reaches completion.
• Step 2 forms compounds of Formula 1 from the reaction of compounds of Formula 3 with compounds of Formula 2 in the presence of a suitable base in a suitable solvent.
• Step 2 the general and preferred reaction conditions are the same as the ones described above for Step 1.
• Step 1 and 2 can be combined without isolating product of Step 1 and preferably, the reaction conditions (e.g. temperature, mole ratio, reaction time etc) are balanced to achieve a high yield of compound of Formula 1.
• the compound of Formula 1 can be isolated by standard procedures. PROCESS SEQUENCE B
• Step 1 forms the compounds of Formula 3 from the reaction of compounds of Formula 5 with compounds of Formula 6 under Mitsunobu reaction conditions involving a tertiary phosphine and an azo compound.
• a tertiary phosphine and azo compound are examples of the tertiary phosphine and azo compounds as well as solvents useful for this transformation in Synthesis, 1981, 1 and Org. Reactions, 1992, 42, 335.
• the reaction temperature is generally from about -40 to 250 °C, preferably from -20 to 80 °C.
• the reaction times are generally from about 0.20 to 24 h, preferably from 0.5 to 12 h.
• the pressure is from 1.013 x 10 2 to 5.065 xlO 2 KPa; preferably ambient pressure.
• at least an equimolar amount of the Formula 5 compound is used in respect to the Formula 6 compound, and preferably at least a small molar excess of the Formula 6 compound is used. More particularly, the molar ratio of the Formula 6 compound to the Formula 5 compound is usually in the range of 1.05: 1 to 10: 1. In most cases, the molar ratio of the Formula 6 compound to the Formula 5 compound is preferably in the range of 1.1 : 1 to 1.5:1.
• Isolation of product of Step 1 can be accomplished by standard workup procedures.
• Step la forms the compounds of Formula 1 by contacting compounds of Formula 5 with compounds of Formula 2 in the presence of a suitable base either neat or in a suitable solvent.
• Step la the general and preferred reaction conditions are the same as the ones described above for Step 1 in Process Sequence A.
• a solution of compound of Formula 2 can be added to a solution/suspension of compound of Formula 5 and a base in a solvent. Reaction temperature is maintained during and after the addition and until the reaction reaches completion. Isolation of product of Step la can be accomplished by standard workup procedures.
• Step lb forms the compounds of Formula 7 from the reaction of compounds of Formula 5 and compounds of Formula 2 in the presence of a base either neat or in a suitable solvent.
• Step lb the general and preferred reaction conditions are the same as the ones described above for Step 1 in Process Sequence A.
• Step lb The product of Step lb can be isolated by standard workup procedures.
• Step 2a forms the compounds of Formula 1 from the reaction of compounds of Formula 7 and compounds of Formula 6 under Mitsunobu reaction conditions involving a tertiary phosphine and an azo compoimd.
• a tertiary phosphine and azo compounds as well as solvents useful for this transformation in Synthesis, 1981, 1 and Org. Reactions, 1992, 42, 335.
• the reaction temperature is generally from about -40 to 250 °C, preferably from -20 to 80 °C.
• the reaction times are generally from about 0.20 to 24 h, preferably from 0.5 to 12 h.
• the pressure is from 1.013 x 10 2 to 5.065 xlO 2 KPa; preferably ambient pressure.
• the molar ratio of the Formula 6 compound to the Formula 7 compound is usually in the range of 1.05 : 1 to 10: 1. In most cases, the molar ratio of the Formula 7 compound to the Formula 6 compound is preferably in the range of 1.1 : 1 to 1.5:1.
• Isolation of product of Step 2a can be accomplished by standard workup procedures.
• Step 2b forms compounds of Formula 1 by contacting compounds of Formula 7 with compounds of Formula 4 in the presence of a suitable base either neat or in a suitable solvent.
• a suitable base either neat or in a suitable solvent.
• the general and preferred reaction conditions are similar to the ones described above for Step 1 in Process Sequence A.
• Isolation of product of Step 2b can be accomplished by standard workup procedures.
• PROCESS SEQUENCE D Compounds of the Formula 8 can be readily prepared by one skilled in the art by using the reactions and techniques described in Steps 1 and 2. In cases where a substituent of the starting material is not compatible with the reaction conditions described for any of the reaction schemes, the substituent can be converted to a protected form prior to the described reaction scheme and then deprotected after the reaction using commonly accepted protection/deprotection techniques (see Green, T. W. and Wuts, P. G., Protecting Groups in Organic Transformations, 2nd Edition, John Wiley and Sons, New York, 1991). Otherwise, alternative approaches known to one skilled in the art are available. STEP 1
• Step 1 forms compounds of Formula 20 from the reaction of compounds of Formula
• Step 2 forms compounds of Formula 8 in the form of a salt by treatment of compounds of Formula 20 with hydroxylamine and a base. The salt is then converted to compound of Formula 8 by treatment with an acid.
• the reaction is conducted in a suitable organic solvent such as, but not limited to, tetrahydrofuran, dioxane or toluene at a temperature between - 20 and 100 °C with 10-50 °C being the preferred temperature.
• Hydroxylamine may be generated from one of its salts by use of a suitable base such as, but not limited to, potassium carbonate, potassium hydroxide or sodium hydroxide. Alternatively, hydroxylamine in water may be used. Judicious use of an appropriate co-solvent such as water or a phase transfer catalyst may be effective in facilitating the reaction. Further amounts of the base (vide supra) can be added to scavenge the HCI formed in the reaction.
• an excess amount of hydroxylamine can be used to achieve the same purpose.
• the intermediate compound of Formula 21 is not usually isolated, but converted directly to compounds of Formula 8 by addition of further quantities of base. It is apparent to one skilled in the art that salts of compounds of Formula 8 generated from this reaction may be used directly in the preparation of compounds of Formula 1 as described in Scheme 1. To facilitate the transformation, it may be desirable to adjust the solvent composition by removal of co-solvents such as water prior to the reaction. Alternatively, compounds of Formula 8 may be isolated from their salts by addition of an appropriate mineral acid such as, but not limited to, HCI before being subjected to the reaction conditions as described in Scheme 1 to produce compounds of Formula 1.
• an appropriate mineral acid such as, but not limited to, HCI
• PROCESS SEQUENCE E Compounds of the Formula 7 can be readily prepared by one skilled in the art by using the reactions and techniques described in Steps 1 and 2. Since hydroxylamine is unstable upon heating, this sequence allows a safe and efficient route to the compounds of the Formula 7 under mild conditions. STEP 1
• Step 1 forms the compounds of Formula 22 by contacting a compound of Formula 2 with hydroxylamine in the presence of a suitable base in a suitable solvent.
• Hydroxylamine may be generated from one of its salts or hydroxylamine in water may be used.
• the reaction temperature is generally from -10 to 150 °C, preferably from 0 to 100 °C.
• the reaction times are generally from 0.10 to 24 h, preferably from 0.10 to 2 h.
• the pressure is in the range of 1.013 x 10 2 to 2.026 x 10 2 KPa; preferably ambient pressure.
• Suitable solvents include typical organic solvents in which the reactants can be dissolved and the process of Step 1 can proceed without interference.
• solvents examples include aromatics such as benzene, toluene, xylene, chlorobenzene and dichlorobenzene, ethers such as dioxane and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ethyl acetate, dichloromethane, dichloroethane, and polar aprotic solvents such as dimethylformamide and dimethylsulfoxide. Judicious use of an appropriate co-solvent such as water or a phase transfer catalyst may be effective in facilitating the reaction.
• aromatics such as benzene, toluene, xylene, chlorobenzene and dichlorobenzene
• ethers such as dioxane and tetrahydrofuran
• nitriles such as acetonitrile and propionitrile
• ethyl acetate dichloromethane
• dichloroethane dichloroethane
• Suitable bases include organic trialkylamines such as trimethylamine, triemylamine, diisopropylethylamine, tributylamine and the like, dimethylaniline, NN-dimethylamino- pyridine, N-methylmorpholine, l,8-diazabicyclo[5.4.0]undec-7-ene, 1,4- diazabicyclo[2.2.2]octane and l,5-diazabicyclo[4.3.0]non-5-ene.
• Trialkylamines is a particularly useful organic base for this reaction. When an excess quantity of hydroxylamine is employed, the excess hydroxylamine can also serve as a base.
• Inorganic bases include, but are not limited to, potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, lithium carbonate and cesium carbonate.
• At least an equimolar amount of the Formula 2 compound is used in respect to hydroxylamine, and preferably at least a small molar excess of hydroxylamine is used.
• the molar ratio of the Formula 2 compound to hydroxylamine is usually in the range of 1 : 1.05 to 1 : 10. In most cases, the molar ratio of the Formula 2 compound to hydroxylamine is preferably in the range of 1:1.1 to 1:1.5. Generally at least an equivalent of base is used in respect to the Formula 2 compound, and preferably at least a small equivalent excess of the base is used. More particularly, the ratio of the number of equivalents of base to number of moles of the Formula 2 compound is usually in the range of 1.05 : 1 to 10: 1. In most cases, the ratio of the number of equivalents of base to number of moles of the Formula 2 compound is preferably in the range of 1.1 : 1 to 1.5: 1. The equivalent amount of base may be similar to the molar amount of the Formula 2 compound, but this is not necessary.
• Isolation of product of Step 1 can be accomplished by standard workup procedures.
• a filtration can be employed to collect compounds of Formula 22.
• the reaction temperature is generally from -10 to 150 °C, preferably from 0 to 100 °C.
• the reaction times are generally from 0.10 to 24 h, preferably from 0.10 to 2 h.
• the pressure is in the range of 1.013 x 10 2 to 2.026 x 10 2 KPa; preferably ambient pressure.
• Suitable solvents include typical organic solvents in which the reactants can be dissolved and the process of Step 1 can proceed without interference.
• Such reactants include aromatics such as benzene, toluene, xylene, chlorobenzene and dichlorobenzene, ethers such as dioxane and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ethyl acetate, dichloromethane, dichloroethane, and polar aprotic solvents such as dimethylformamide and dimethylsulfoxide.
• Suitable bases for Step 2 are similar to the ones described above for Step 1.
• the molar ratio of the Formula 22 compound to the Formula 23 compound is usually in the range of 1 : 1.05 to 1 : 10. In most cases, the molar ratio of the Formula 22 compound to the Formula 23 compound is preferably in the range of 1 : 1.1 to 1:1.5.
• at least an equivalent of base is used in respect to the Formula 22 compound, and preferably at least a small equivalent excess of the base is used. More particularly, the ratio of the number of equivalents of base to number of moles of the Formula 22 compound is usually in the range of 1.05:1 to 10:1.
• the ratio of the number of equivalents of base to number of moles of the Formula 22 compound is preferably in the range of 1.1 : 1 to 1.5: 1.
• the equivalent amount of base may be similar to the molar amount of the Formula 22 compound, but this is not necessary. Isolation of product of Step 2 can be accomplished by standard workup procedures.
• Compounds 7 can be readily converted into alkali salts when treated with potassium carbonate or sodium carbonate in water.
• the salts may be useful in alkylation reactions.
• PROCESS SEQUENCE F Compounds of the Formula 1 can be readily prepared by one skilled in the art by using the reactions and techniques described in the scheme below.
• R 27 is - ⁇ CR ⁇ J-Q
• the compounds of Formula 1 are formed by contacting a compound of Formula 7 with an orthoformate of Formula 24 either neat or in the presence of a suitable solvent.
• the reaction temperature is generally from -10 to 150 °C, preferably from 0 to 100 °C.
• the reaction times are generally from 0.10 to 24 h, preferably from 0.10 to 2 h.
• the pressure is in the range of 1.013 x 10 2 to 2.026 x 10 2 KPa; preferably ambient pressure.
• Suitable solvents include typical organic solvents in which the reactants can be dissolved and the process can proceed without interference.
• Such reactants include aromatics such as benzene, toluene, xylene, chlorobenzene and dichlorobenzene, ethers such as dioxane and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ethyl acetate, dichloromethane, dichloroethane, and polar aprotic solvents such as dimethylformamide and dimethylsulfoxide.
• aromatics such as benzene, toluene, xylene, chlorobenzene and dichlorobenzene
• ethers such as dioxane and tetrahydrofuran
• nitriles such as acetonitrile and propionitrile
• ethyl acetate dichloromethane
• dichloroethane dichloroethane
• polar aprotic solvents such as dimethylformamide and dimethylsulfoxide.
• the molar ratio of the Formula 7 compound to the Formula 24 compound is usually in the range of 1 : 1.05 to 1 : 10. In most cases, the molar ratio of the Formula 7 compound to the Formula 24 compound is preferably in the range of 1:1.1 to 1:1.5.
• PROCESS SEQUENCE G Compounds of the Formula 1 can be readily prepared by one skilled in the art by using the reactions and techniques described in Steps 1 and 2. STEP 1
• Step 1 forms the compounds of Formula 25 by contacting a compound of Formula 8 with a compound of Formula 26 either neat or in a suitable solvent.
• the reaction temperature is generally from -10 to 150 °C, preferably from 0 to 100 °C.
• the reaction times are generally from 0.10 to 24 h, preferably from 0.10 to 2 h.
• the pressure is in the range of 1.013 x 10 2 to 2.026 x 10 2 KPa; preferably ambient pressure.
• Suitable solvents include typical organic solvents in which the reactants can be dissolved and the process of Step 1 can proceed without interference.
• reactants include aromatics such as benzene, toluene, xylene, chlorobenzene and dichlorobenzene, ethers such as dioxane and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ethyl acetate, dichloromethane and dichloroethane.
• aromatics such as benzene, toluene, xylene, chlorobenzene and dichlorobenzene
• ethers such as dioxane and tetrahydrofuran
• nitriles such as acetonitrile and propionitrile
• ethyl acetate dichloromethane and dichloroethane.
• the molar ratio of the Formula 8 compound to the Formula 26 compound is usually in the range of 1 : 1.05 to 1 : 10. In most cases, the molar ratio of the Formula 8 compound to the Formula 26 compoimd is preferably in the range of 1:1.1 to 1:1.5.
• Step 2 the general and preferred reaction conditions are the same as the ones described above for Step 1 in Process Sequence A.
• Step A Preparation of N-(2.4-dichlorophenylVN -hydroxyurea
• a solution of 14.2 g (75 mmol) of 2,4-dichlorophenylisocyanate in 50 mL of toluene was added to a mixture of 8.26 g (120 mmol) of hydroxylamine hydrochloride and 4.8 g (120 mmol) of sodium hydroxide in a two-phase solvent mixture consisting of 50 mL of water and 50 mL of toluene.
• the resulting mixture was stirred at 25 °C for 30 minutes and filtered.
• the solid thus obtained was washed with water and then dissolved in 200 mL of ethyl acetate.
• Step B Preparation of 4-(2.4-dichlorophenyl)- 1.2.4-oxadiazolidine-3.5-dione
• a IL three neck round bottom flask equipped with a nitrogen inlet, a thermometer and two addition funnels was charged with 600 mL of toluene and 36.0 g (0.22 mol) of the compound of Step C. This stirred mixture was cooled to 3 °C, and then 116 mL (0.22 mol) of a 20% solution of phosgene in toluene was added dropwise over 15 min while maintaining the temperature below 10 °C. Ten min after the addition, diisopropyl ethylamine (39 mL, 0.22 mol) was added dropwise over 15 min while maintaining the temperature below 7 °C. The reaction mixture was allowed to warm to room temperature and stirred for 14 hours.
• Step E Preparation of 4-(2.4-dichlorophenviyN-(4-fiuorophenvO-N-f 1 - methylethyl)-3.5-dioxo- 1.2.4-oxadiazolidine-2-carboxamide
• a solution of 0.6 g (2.4 mmol) of the compound of Step B in toluene (25 mL) was treated with 0.42 g (1.9 mmol) of the compound of Step D and 0.35 g (2.9 mmol) of 4- dimethylaminopyridine.
• the resulting mixture was heated at 80 °C for 1 hour, and subsequently diluted with IN hydrochloric acid (20 mL) and ethyl acetate (50 mL).
• Step A Preparation of N-f2.6-dimethylphenylVN ' -hvdroxylurea
• a 500 mL side arm flask equipped with a thermometer and an addition funnel with a nitrogen inlet was charged with 100 mL of toluene and 2.00 g (0.10 mol) of 50% hydroxylamine in water.
• Step B Preparation of 4-f2.6-dimethylphenyl)- 1.2.4-oxadiazolidine-3.5-dione
• Step A Preparation of 4-(2-propenyl)-l .2.4-oxadiazolidine-3.5-dione To a 500 mL round-bottom flask were added acetone (300 mL), allyl isocyanate
• Step B Preparation of N- ⁇ -fluorophenylVN-d -methylethylV3.5-dioxo-4-C2- propenyl)- 1.2.4-oxadiazolidine-2-carboxamide
• a dry 100 mL round-bottom flask was changed with dry tetrahydrofuran (20 mL), the compound of step A (1.0 g, 7.0 mmol), the compound of Step D in Example 1 (1.5 g, 7.0 mmol), triethylamine (1.0 g, 10.0 mmol) and 4-dimethylaminopyridine (0.2 g, 1.6 mmol) respectively at room temperature under nitrogen atmosphere with stirring.
• the reaction mixture was heated at reflux for 1.5 h during which time a white solid precipitated out.
• the reaction mixture was cooled to room temperature and diluted with 150 mL of ethyl acetate.
• Step B Preparation of N-hvdroxy-2.2-dimeth ylh vdrazinecarboxamide
• Step B The compound of Step B (4.25 g, 29 mmol) was suspended in tetrahydrofuran (25 mL) at 5 °C under nitrogen. To the mixture was added portion- wise 1,1'- carbonyldiimidazole (5.78 g, 29 mmol) while maintaining the reaction temperature under 10 °C. The reaction was partitioned between ethyl acetate (125 mL) and IN HCI (60 mL). The organic layer was separated. The aqueous layer was further extracted with ethyl acetate (2 x 100 mL). The combined organic layers were dried over MgSO- j and concentrated under reduced pressure to afford the title compound as an oil (2.9 g).
• Step A Preparation of 4-r(2-methylphenyl)methyll-3-(phenylmethoxyV 1.2.4- oxadiazol-5(4HVone
• Step B Preparation of N-i4-chlorophenylVN-( 1 -methylethylV4-[T2- methylphenyl)methyl1-3.5-dioxo- 1.2.4-oxadiazolidine-2-carboxamide
• the mixture was heated to reflux for 3 hours, then cooled to room temperature and poured into IN HCI (50 mL). The mixture was extracted with diethyl ether (3 x 25 mL). The organic layer was dried over MgS0 4 and concentrated under reduced pressure to provide a thick oil. The oil was purified by flash chromatography on silica gel using 9: 1 hexane-ethyl acetate to provide 0.22 g (28%) of the title compound as a white solid melting at 90-91 °C.
• Step A Preparation of 4-methyl-3-(phenylmethoxy)- 1.2.4-oxadiazol-5(4H)-one
• Step B Preparation of N-(4-fluorophenv ⁇ -N-d-methylethyl')-4- 2-methylpropy ⁇ -3.5- dioxo- 1.2.4-oxadiazolidine-2-carboxamide
• Step A Preparation of N-(4-fluorophenylVN- ⁇ -methyl ethylV3.5-dioxo-4-
• Step A Preparation of N-(4-fluorophenvD-N-(l -methylethylV3.5-dioxo-l .2.4- oxadiazolidine-2-carboxamide and N-(4-fluorophenylV4-rnethyl-N-(l- methyl ethyl)-3.5-dioxo- 1.2.4-oxadiazolidine-2-carboxamide
• Step B Preparation of N-C4-fluorophenyl)-N-( 1 -methylethyl)-4-(2-methylpropyl)-3.5- dioxo- 1 ,2.4-oxadiazolidine-2-carboxamide
• a 50 mL round bottom flask equipped with a thermometer, a stirrer, an addition funnel, and a nitrogen inlet was charged with N-(4-fluorophenyl)-N-(l-methylethyl)-3,5- dioxo-l,2,4-oxadiazolidine-2-carboxamide (5.5 g, 0.019 m), 2-methyl-l-propanol (3 g, 0.04 mol), triphenylphosphine (6.3 g, 0.021 mol) and tetrahydrofuran (60 mL).
• reaction solution was cooled to 15 °C and diethyl azodicarboxylate (4.2 g, 0.024 mol) in tetrahydrofuran (10 mL) was added dropwise over a period of 10 min.
• the reaction mixture was stirred at room temperature for 18 h.
• the solvent was removed under reduced pressure and the residue was flash chromatographed (silica gel, 9: 1 hexane-ethyl acetate) to provide the title compound as a white solid (5.6 g, 88%).
• the solid has a melting range of 80-81 °C, and was identical to the material prepared in Example 8, Step B.
• Step B Preparation of 4-(2.6-dimethylphenyl ' )-2-methyl-1.2.4-oxadiazolidine-3.5- dione
• a portion of the compoimd from Step A (3.72 g, 15.4 mmol) in dioxane (15 mL) was added to a mixture of aqueous hydroxylamine (2.03 g, 30.7 mmol, 50% by weight) in dioxane (15 mL).
• a solution of potassium hydroxide (2.22 g, 33.6 mmol, 85 %) in water was added dropwise to the mixture so that the temperature did not rise beyond 30 °C.
• the solvent was removed until the volume was reduced to about 5 mL.
• Step A Preparation of N-hvdroxy-N-( 1 -methylethvD-N-phenylurea
• Step B Preparation of N-(l-methylethylV3.5-dioxo-N-phenyl-1.2.4-oxadiazolidine-2- carboxamide
• a solution of chlorocarbonyl isocyanate (5.0 g, 0.047 mol) was added dropwise to a slurry of the title compound of Step A (9.2 g, 0.047 mol) and triethylamine (5.3 g, 0.052 mol) in 200 mL of THF while maintaining the reaction temperature below 30 °C using an ice bath. After 2 hours, TLC showed the presence of starting material.
• Another 0.5 g of chlorocarbonyl isocyanate was added, and the reaction mixture was stirred for another hour.
• Step B Preparation of N-( -fluorophenyl)-N.4-b/,s , (' 1 -methylethylV3.5-dioxo- 1.2.4- oxadiazolidine-2-carboxamide
• Step B Preparation of N,4-bisf 1 -methylethvD-S.S-dioxo-N-phenyl- 1.2.4- oxadiazolidine-2-carboxamide
• 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, 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 tetiahydrofurfuryl 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 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%.
• Compound 2 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.
• Compound 2 10.0% attapulgite granules (low volatile matter, 0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90.0%.
• 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). Those skilled in the art will appreciate that not all compounds are equally effective against all weeds. Alternatively, 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, bifenox, bispyribac and its sodium salt, bromacil, bromoxynil, bromoxynil octanoate, butachlor, butralin, butroxydim (ICIA0500), butylate, caloxydim (BAS 620H), carfentrazone-ethyl,
• 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.
• Certain combinations of compounds of this invention with other herbicides may provide synergistic herbicidal effects on weeds or may provide enhanced crop safety.
• Preferred for better control of undesired vegetation in com e.g., lower use rate, broader spectrum of weeds controlled, or enhanced crop safety
• Preferred for preventing the development of resistant weeds in com are mixtures of a compound of this invention with one or more of the herbicides selected from the group rimsulfuron, nicosulfuron, thifensulfuron, prosulfuron, halosulfuron, naphthalic anhydride, flurazole, dichlormid, fenchlorazole ethyl, naphthalic anhydride, MG-191 (2-dichloromethyl)-2-methyl-l,3- dioxolane), dicyclonon, benoxacor, cyometrinil, furilazole, oxabetrinil, cloquintocet mexyl, fluxofenim, fenclorim, menfenpyr diethyl, and R-29148 (3-(dichloroace
• mixtures for use in com are selected from the group consisting of: a) Compound 113 (Index Table C, mixture partner A, generally applied at a rate of 10 to 1000 g/ha, preferably applied at a rate of 50 to 500 g/ha) in combination with:
• Combination 1 is generally used in a ratio of A to B of 3:1 to 50:1, preferably 5:1 to 30:1, with B being applied at a rate of 1 to 100 g/ha, preferably 5 to 50 g/ha.
• Combination 2 is generally used in a ratio of A to B of 2:1 to 20:1, preferably 4:1 to 10:1, with B being applied at a rate of 1 to 100 g/ha, preferably 20 to 70 g/ha.
• Combination 3 is generally used in a ratio of A to B of 1 : 10 to 10:1, preferably 1 :2 to 2: 1 , with B being applied at a rate of 10 to 1000 g/ha, preferably 50 to 500 g/ha.
• Combination 4 is generally used in a ratio of A to B of 1 : 10 to 10: 1 , preferably 1 :2 to 4: 1 , with B being applied at a rate of 1 to 1000 g/ha, preferably 20 to 500 g/ha.
• Combination 5 is generally used in a ratio of A to B of 1 :500 to 50:1, preferably 1 :20 to 10:1, with B being applied at a rate of 10 to 1000 g/ha, preferably 50 to 500 g/ha.
• Combination 6 is generally used in a ratio of A to BI of 3:1 to 50:1, preferably 5:1 to 30:1, and a ratio of A to B2 of 1:10 to 10:1, preferably 1:2 to 2:1, with Bl being applied at a rate of 1 to 100 g/ha, preferably 5 to 50 g/ha, and B2 being applied at a rate of 10 to 1000 g/ha, preferably 50 to 500 g/ha.
• Combination 7 is generally used in a ratio of A to B3 of 2:1 to 20:1, preferably 4:1 to 10:1, and a ratio of A to B4 of 1:10 to 10:1, preferably 1 :2 to 2: 1 , with B3 being applied at a rate of 1 to 100 g/ha, preferably 20 to 70 g/ha, and B4 being applied at a rate of 10 to 1000 g/ha, preferably 50 to 500 g/ha.
• Combination 1 is generally used in a ratio of A to B of 3:1 to 50:1, preferably 5:1 to 30:1, with B being applied at a rate of 1 to 100 g/ha, preferably 5 to 50 g/ha.
• Combination 2 is generally used in a ratio of A to B of 2:1 to 20:1, preferably 4:1 to 10:1, with B being applied at a rate of 1 to 100 g/ha, preferably 20 to 70 g ha.
• Combination 3 is generally used in a ratio of A to B of 1:10 to 10:1, preferably 1:2 to 2:1, with B being applied at a rate of 10 to 1000 g/ha, preferably 50 to 500 g/ha.
• Combination 4 is generally used in a ratio of A to B of 1 : 10 to 10: 1 , preferably 1 :2 to 4: 1 , with B being applied at a rate of 1 to 1000 g/ha, preferably 20 to 500 g/ha.
• Combination 5 is generally used in a ratio of A to B of 1 :500 to 50:1, preferably 1 :20 to 10: 1 , with B being applied at a rate of 10 to 1000 g/ha, preferably 50 to 500 g/ha.
• Combination 6 is generally used in a ratio of A to B 1 of 3 : 1 to 50: 1 , preferably 5:1 to 30:1, and a ratio of A to B2 of 1:10 to 10:1, preferably 1:2 to 2:1, with BI being applied at a rate of 1 to 100 g/ha, preferably 5 to 50 g/ha, and B2 being applied at a rate of 10 to 1000 g/ha, preferably 50 to 500 g/ha.
• Combination 7 is generally used in a ratio of A to B3 of 2:1 to 20:1, preferably 4: 1 to 10:1, and a ratio of A to B4 of 1:10 to 10:1, preferably 1 :2 to 2: 1, with B3 being applied at a rate of 1 to 100 g/ha, preferably 20 to 70 g/ha, and B4 being applied at a rate of 10 to 1000 g/ha, preferably 50 to 500 g/ha.
• Combination 1 is generally used in a ratio of A to B of 3:1 to 50:1, preferably 5:1 to 30:1, with B being applied at a rate of 1 to 100 g/ha, preferably 5 to 50 g/ha.
• Combination 2 is generally used in a ratio of A to B of 2:1 to 20:1, preferably 4:1 to 10:1, with B being applied at a rate of 1 to 100 g/ha, preferably 20 to 70 g/ha.
• Combination 3 is generally used in a ratio of A to B of 1:10 to 10:1, preferably 1:2 to 2:1, with B being applied at a rate of 10 to 1000 g/ha, preferably 50 to 500 g/ha.
• Combination 4 is generally used in a ratio of A to B of 1:10 to 10:1, preferably 1 :2 to 4:1, with B being applied at a rate of 1 to 1000 g/ha, preferably 20 to 500 g/ha.
• Combination 5 is generally used in a ratio of A to B of 1 :500 to 50:1, preferably 1 :20 to 10: 1, with B being applied at a rate of 10 to 1000 g/ha, preferably 50 to 500 g/ha.
• Combination 6 is generally used in a ratio of A to BI of 3:1 to 50:1, preferably 5:1 to 30:1, and a ratio of A to B2 of 1:10 to 10:1, preferably 1:2 to 2:1, with BI being applied at a rate of 1 to 100 g/ha, preferably 5 to 50 g/ha, and B2 being applied at a rate of 10 to 1000 g/ha, preferably 50 to 500 g/ha.
• Combination 7 is generally used in a ratio of A to B3 of2:l to 20:1, preferably 4:1 to 10:1, and a ratio of A to B4 of l:10 to 10:1, preferably 1 :2 to 2: 1 , with B3 being applied at a rate of 1 to 100 g/ha, preferably 20 to 70 g/ha, and B4 being applied at a rate of 10 to 1000 g/ha, preferably 50 to 500 g/ha.
• Compound 146 (Index Table C, mixture partner A, generally applied at a rate of 10 to 1000 g/ha, preferably applied at a rate of 50 to 500 g/ha) in combination with:
• Combination 1 is generally used in a ratio of A to B of 3 : 1 to 50: 1 , preferably 5 : 1 to 30:1, with B being applied at a rate of 1 to 100 g/ha, preferably 5 to 50 g/ha.
• Combination 2 is generally used in a ratio ofA to B of 2:1 to 20:1, preferably 4:1 to 10:1, with B being applied at a rate of 1 to 100 g/ha, preferably 20 to 70 g/ha.
• Combination 3 is generally used in a ratio of A to B of 1 : 10 to 10:1, preferably 1 :2 to 2: 1 , with B being applied at a rate of 10 to 1000 g/ha, preferably 50 to 500 g/ha.
• Combination 4 is generally used in a ratio of A to B of 1 : 10 to 10: 1 , preferably 1 :2 to 4: 1 , with B being applied at a rate of 1 to 1000 g/ha, preferably 20 to 500 g/ha.
• Combination 5 is generally used in a ratio of A to B of 1 :500 to 50:1, preferably 1 : :20 to 10: 1 , with B being applied at a rate of 10 to 1000 g/ha, preferably 50 to 500 g/ha.
• Combination 6 is generally used in a ratio of A to BI of 3:1 to 50:1, preferably 5:1 to 30:1, and a ratio of A to B2 of 1:10 to 10:1, preferably 1:2 to 2:1, with BI being applied at a rate of 1 to 100 g/ha, preferably 5 to 50 g/ha, and B2 being applied at a rate of 10 to 1000 g/ha, preferably 50 to 500 g/ha.
• Combination 7 is generally used in a ratio of A to B3 of 2:1 to 20:1, preferably 4:1 to 10:1, and a ratio of A to B4 of 1:10 to 10:1, preferably 1 :2 to 2: 1 , with B3 being applied at a rate of 1 to 100 g/ha, preferably 20 to 70 g/ha, and B4 being applied at a rate of 10 to 1000 g/ha, preferably 50 to 500 g/ha.
• a H 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 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 A, are based on a 0 to 10 scale where 0 is no effect and 10 is complete control.
• 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 barnyardgrass (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.
• Redroot pigweed 8 0 0 7 7 0 0 0 3 0 0 0 0 0 6 6 0 6 6 5 4 0 6 4
• Soybean 1 1 1 4 5 5 2 5 0 4 0 0 2 2 2 3 5 6 4 4 7 3 3 4-
• Soybean 4 5 5 7 5 1 1 2 4 3 0 6 5 6 1 5 5 7 7 5 7 7 7 4
• Velvetleaf 4 6 0 1 0 2 1 0 5 3 2 0 0 3 2 3 0 3 0 0 0 0 0 0

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