WO1998035961A1 - Herbicidal tetrazolinones - Google Patents

Herbicidal tetrazolinones Download PDF

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Publication number
WO1998035961A1
WO1998035961A1 PCT/US1998/002737 US9802737W WO9835961A1 WO 1998035961 A1 WO1998035961 A1 WO 1998035961A1 US 9802737 W US9802737 W US 9802737W WO 9835961 A1 WO9835961 A1 WO 9835961A1
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compound
alkyl
dihydro
haloalkyl
heterocyclic ring
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PCT/US1998/002737
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French (fr)
Inventor
T. G. Murali Dhar
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E.I. Du Pont De Nemours And Company
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Priority to JP53590798A priority Critical patent/JP2001512460A/en
Priority to AU61611/98A priority patent/AU6161198A/en
Publication of WO1998035961A1 publication Critical patent/WO1998035961A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
    • C07D307/04—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D307/10—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D307/16—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
    • C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D309/14—Nitrogen atoms not forming part of a nitro radical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/16—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D309/28—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • 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
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • 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
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings

Definitions

  • This invention relates to certain tetrazolinones, their N-oxides, agriculturally suitable salts and compositions thereof, and methods of the use of the aforesaid compositions for controlling undesirable vegetation.
  • This invention further relates to certain carbamyl chloride intermediates useful in the synthesis of said tetrazolinones.
  • the control of undesired vegetation is extremely important in achieving high crop efficiency. Achievement of selective control of the growth of weeds especially in such useful crops as rice, soybean, sugar beet, corn (maize), potato, wheat, barley, tomato and plantation crops, among others, is very desirable. Unchecked weed growth in such useful crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. The control of undesired vegetation in noncrop areas is also important. Many products are commercially available for these purposes, but the need continues for new compounds which are more effective, less costly, less toxic, environmentally safer or have different modes of action.
  • U.S. 5,019,152 discloses herbicidal tetrazolinones of the formula
  • R is alkyl, alkenyl, C7-C 9 aralkyl, phenyl or substituted phenyl;
  • R 1 and R 2 are independently C C 6 alkyl, C ⁇ -Cg alkenyl or C 5 -C6 cycloalkyl.
  • This invention is directed to compounds of Formula I including all geometric and stereoisomers, N-oxides, and agriculturally suitable salts thereof:
  • a together with the carbon to which it is attached form 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 6 R 7 ) q through other than X;
  • X is O, S(O) n , NR3 or Si(R ) 2 ;
  • each R 1 is independently C 1 -C 4 alkyl or C1-C 4 haloalkyl;
  • R 2 is C r C 6 alkyl, C r C 6 haloalkyl, C 3 -C 7 cycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkyny
  • Q is Ar-(CH 2 ) p - optionally substituted on the methylene carbon by 1-2 C ⁇ -C 2 alkyl;
  • X is O, S or NR 3 .
  • Preferred 5 Compounds of Preferred 4 wherein R 2 is C ⁇ -C 6 alkyl, C , -C 6 haloalkyl or C 3 -C 7 cycloalkyl; or R 2 is phenyl optionally substituted with C C 3 alkyl, halogen, cyano, nitro or C 2 -C 4 alkoxycarbonyl.
  • a together with the carbon to which it is attached form 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 6 R 7 ) q through other than X;
  • X is O, S(O) n , NR 3 or Si(R 4 ) 2 ; each R 1 is independently C1-C 4 alkyl or C1-C 4 haloalkyl;
  • R 2 is C r C 6 alkyl, C r C 6 haloalkyl, C 3 -C 7 cycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 haloalkenyl, C 3 -C 6 alkynyl, C Cg alkoxy, C 2 -C 6 alkoxyalkyl or C 2 -C 6 haloalkoxyalkyl;
  • R 3 is H, C1-C 4 alkyl, C r C 4 haloalkyl, C 3 -C 4 alkenyl
  • Preferred 7 Compounds of Formula 2 above, geometric and stereoisomers thereof, wherein A together with the carbon to which it is attached form a fully or partially saturated 5-, 6- or 7-membered heterocyclic ring containing one X; and q is 0.
  • Preferred 8 Compounds of Preferred 7 wherein X is O, S or NR 3 .
  • Preferred 9 Compounds of Preferred 8 wherein
  • R 2 is C r C 6 alkyl, C r C 6 haloalkyl or C 3 -C 7 cycloalkyl.
  • Preferred 10 Compounds of Preferred 9 wherein X is O. Most preferred are compounds of Preferred 10 selected from the group: (a) (3 ,6-dihydro-2H-pyran-4-yl)( 1 -methylethyl)carbamic chloride;
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, /j-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 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, rc-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
  • Alkylthio includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.
  • Alkylthioalkyl denotes alkylthio substitution on alkyl. Examples of “alkylthioalkyl” include CH 3 SCH 2 , CH 3 SCH 2 CH 2 , CH 3 CH 2 SCH 2 , CH 3 CH 2 CH 2 CH 2 SCH 2 and CH 3 CH 2 SCH 2 CH 2 .
  • Alkylthioalkoxy denotes alkylthio substitution on alkoxy.
  • Cyanoalkyl denotes an alkyl group substituted with one cyano group. Examples of “cyanoalkyl” include NCCH 2 , NCCH 2 CH 2 and CH 3 CH(CN)CH 2 .
  • Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • cycloalkoxy includes the same groups linked through an oxygen atom such as cyclopentyloxy and cyclohexyloxy.
  • Cycloalkenyl includes groups such as cyclopentenyl and cyclohexenyl as well as groups with more than one double bond such as 1,3- and 1,4-cyclohexadienyl.
  • Examples of “cycloalkylalkyl” include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to straight-chain or branched alkyl groups.
  • Examples of “cycloalkylalkoxy” include cyclopropylmethoxy, cyclopentylethoxy, and other cycloalkyl moieties bonded to straight-chain or branched alkoxy groups.
  • Alkylcycloalkyl denotes alkyl substitution on a cycloalkyl moiety. Examples include 4-methylcyclohexyl and 3-ethylcyclopentyl.
  • Cyanocycloalkyl denotes a cycloalkyl group substituted with one cyano group. Examples of “cyanocycloalkyl” include 4-cyanocyclohexyl and 3-cyanocyclopentyl.
  • aromatic ring denotes fully unsaturated carbocycles and heterocycles in which the ring is aromatic (where aromatic indicates that the H ⁇ ckel rule is satisfied for the ring).
  • aromatic heterocyclic ring includes fully aromatic heterocycles in which the ring aromatic (where aromatic indicates that the H ⁇ ckel rule is satisfied).
  • 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 -chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane.
  • MCPBA peroxy acids
  • alkyl hydroperoxides such as t-butyl hydroperoxide
  • sodium perborate sodium perborate
  • dioxiranes such as dimethyldioxirane
  • halogen either alone or in compound words such as "haloalkyl”, includes fluorine, chlorine, bromine or iodine.
  • 1-2 halogen indicates that one or two of the available positions for that substituent may be halogen which are independently selected.
  • haloalkyl 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 .
  • haloalkenyl is used in compound words such as “haloalkyl”
  • haloalkynyl “haloalkoxy”, “haloalkylthio”, and the like, are defined analogously to the term “haloalkyl”.
  • 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.
  • haloalkylthio include CC1 3 S, CF 3 S, CC1 3 CH 2 S and C1CH 2 CH 2 CH 2 S.
  • C j -Cj The total number of carbon atoms in a substituent group is indicated by the "C j -Cj" prefix where i and j are numbers from 1 to 13.
  • 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 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH 3 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • alkylcarbonyl examples include C(O)CH 3 , C(O)CH 2 CH 2 CH 3 and C(O)CH(CH 3 ) 2 .
  • substituents When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents. Further, when the subscript indicates a range, e.g. (R) j _ j , then the number of substituents may be selected from the integers between i and j inclusive.
  • the compounds of this invention thus include compounds of Formula I, geometric and stereoisomers thereof, N-oxides thereof and agriculturally suitable salts thereof.
  • the compounds of this invention further include compounds of Formula 2, as well as geometric and stereoisomers thereof.
  • the compound of the invention can exist as one or more stereoisomers.
  • the various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers.
  • one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers.
  • the compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.
  • the salts of the compounds of the invention include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
  • inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
  • the salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine, ammonia, or triethylamine) or inorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic group such as a carboxylic acid or 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
  • the compounds of Formula I and Formula 2 can be prepared by one or more of the following methods and variations as described in Schemes 1-17.
  • the definitions of A, Q, Ar, Ar 1 , X, R ⁇ -R 9 , m, n, p, and q in the compounds of Formulae 1-22 below are as defined above in the Summary of the Invention.
  • Scheme 1 illustrates the preparation of compounds of Formula I whereby a tetrazolinone of Formula 1 is reacted with a carbamyl chloride of Formula 2 in the presence of a suitable acid acceptor agent.
  • Suitable acid acceptor agents include alkali carbonates, alkali bicarbonates, alkyl tertiary amines such as triethylamine, pyridine, and, preferably, 4- dimethylaminopyridine (DMAP). Furthermore, DMAP can be used as a catalyst in the presence of another suitable acid acceptor agent in order to selectively synthesize a compound of Formula I.
  • the reaction is carried out in an inert solvent such as tetrahydrofuran, acetone, chloroform, chlorobenzene or preferably acetonitrile or toluene, and at a temperature range between 0 °C and 110 °C by methods known in the art (or slight modification of these methods); for example, see Yanagi, A. et al. EP 646,577; Goto, T. et al. EP 708,097; Covey, R. A. et al. U.S. Patent 4,618,365.
  • Carbamyl chlorides of Formula 2 can be made by treating compounds of Formula 3 with phosgene or a phosgene equivalent such as diphosgene in the presence of a suitable base such as triethylamine or diisopropylethylamine (Scheme 2).
  • Amines of Formula 3 (wherein q is 0) can be made by the sequence of reactions shown in Scheme 3 whereby a ketone of Formula 4 is treated with an appropriate amine and the formed intermediate imine is subsequently reduced to the amine.
  • This type of reaction can be carried out by methods known in the art (or slight modification of these methods); see, for example, Borch, R. Org. Synthesis, Collective Volume VI, (1988), p 499 and Bomann, M. et al. J. Org. Chem. (1995), 60, p 5995.
  • ketones of Formula 4 are either commercially available or can be prepared by methods known in the art; for example, see Soderquist, J. and Negron, A. J. Org. Chem. (1989), 54, pp 2464-2466 for the preparation of l-silacyclohexan-4-ones or Howard, E. and Lindsey, R. J. Am. Chem. Soc. (1960), 82, pp 158-164 for the preparation of 5- ⁇ w- dithianones.
  • Carbamyl chlorides of Formula 2a wherein a carbon-carbon double bond is present within the heterocyclic ring can be made as illustrated in Scheme 4.
  • a ketone of Formula 16 is reacted with an appropriate amine in the presence of a dehydrating agent and the resulting imine intermediate of Formula 18 is treated with phosgene in the presence of a base such as triethylamine to yield the carbamyl chloride of Formula 2a.
  • Carbamyl chlorides of Formula 2c (wherein q is 1 or 2) can be made as illustrated in Scheme 5a.
  • An amine of Formula 19 is reacted with an appropriate carbonyl compound in the presence of molecular sieves, followed by reduction of the imine with sodium cyanoborohydride to give the amine of Formula 22.
  • the amine is treated with phosgene in the presence of a base such as triethylamine to yield the carbamyl chloride of Formula 2c.
  • compounds of Formula I can be prepared whereby a tetrazolinone of
  • Scheme 7 illustrates a preferred method for preparing tetrazolinones of Formula 1 whereby an isocyanate of Formula 5 is reacted with refluxing trimethylsilylazide (also known as azidotrimethylsilane), followed by treatment of the product of such reaction with a protic solvent such as water or preferably with methanol.
  • a protic solvent such as water or preferably with methanol.
  • alkyl and phenyl isocyanates of Formula 5 are commercially available.
  • Other isocyanates of Formula 5 can be prepared by treatment of corresponding amines of Formula 9 with phosgene or known phosgene equivalents (e.g., diphosgene or triphosgene) by methods generally known in the art (Scheme 8); see for example, March, J. Advanced Organic Chemistry, 3rd edition; John Wiley & Sons, 1985, p 370; Chem. Rev. (1972), 72, pp 457-496; Sandier, R. S. et al. Organic Functional Group Preparations, 2nd edition; Academic Press; Vol. II, pp 152 and 260; Lehman, G. et al. Preparative Organic Chemistry; John Wiley & Sons, 1972; p 472.
  • amines of Formula 6 are commercially available, including both simple and substituted alkyl, alkenyl, alkynyl, phenyl, pyridyl, and heteroaryl amines.
  • amines of Formula 6 can be prepared by reduction of the corresponding nitro compounds of Formula 7 (Scheme 9).
  • Scheme 9 A wide variety of methods are documented in the chemical literature for carrying out such transformations; see for example, Rorer, M. P. U.S. Patent 4,511,392; Ohme, R. et al. Preparative Organic Chemistry; John Wiley & Sons, 1972; p 557; Groggins Unit Processes in Organic Chemistry; McGraw-Hill Book Co.: New York, 1947; pp 73-128; March, J. Advanced Organic Chemistry, 3rd edition; John Wiley & Sons, 1985; pp 1103- 1104.
  • Nitro compounds of Formula 7 are commercially available or can be synthesized by methods well-established in the art.
  • Nitro compounds of Formula 7a can be prepared as illustrated in Scheme 10 whereby an appropriate nitro compound of Formula 8 in an inert solvent is reacted with a nucleophilic heterocycle of Formula 9 in the presence of a suitable base.
  • Suitable bases include alkali carbonates such as potassium carbonate, potassium tert- butoxide, and sodium hydride.
  • Suitable solvents include dimethylformamide, 2-butanone, and tetrahydrofuran. The reaction is carried out at a temperature range of about 0 °C to 150 °C, preferably about 80 °C to 120 °C, with dimethylformamide as the solvent and potassium carbonate as the base.
  • the compound of Formula 6a can be purified by recrystallization or flash column chromatography on silica gel by those skilled in the art.
  • Protecting and deprotecting functional groups not compatible with reaction conditions may be necessary for compounds with such functional groups.
  • X is F, Cl, Br, CH 3 S0 0 or CF 3 S0 2 0 and X is ortho or para to the N0 2 group;
  • Nu is an optionally-substituted imidazole, pyrazole, triazole or tetrazole;
  • Al is an optionally-substituted lH-imidazole, l /-pyrazole, l//-l,2,4-triazole, 4//-l,2,4-triazole or tetrazole and A 1 is ortho o para to the N0 2 group; and W is CH or N.
  • Nitro compounds of Formula 7 wherein Q is Ar and Ar is phenyl or a heterocyclic ring further substituted with another phenyl or heterocyclic ring can be synthesized by known coupling methods reviewed in Kalinin, V. Synthesis (1992), pp 413-432.
  • isocyanates of Formula 5 can be also be prepared by Curtius rearrangement of appropriate acid chlorides of Formula 10 using methods generally known in the art (Scheme 1 1); see, for example, March, J. Advanced Organic Chemistry, 3rd edition; John Wiley & Sons, 1985; pp 984-985 and 380.
  • O Q— CC1 e.g., NaN 3 (Curtius Rearrangement)
  • Acid chlorides of Formula 10 can be prepared by reacting an acid of Formula 11 with oxalyl chloride (or thionyl chloride) and optionally a catalytic amount of dimethylformamide (Scheme 12).
  • This chlorination is well known in the art; see, for example, Michaely, W. J. EP 369,803; Goto, T. et al. EP 695,748.
  • Other methods are also well known in the art for converting carboxylic acids to acid chlorides; see, for example, Ogliaruso, M. A. et al. Synthesis of Carboxylic Acids, Esters and Their Derivatives; John Wiley & Sons, 1991, pp 172-174.
  • Carboxylic acids of Formula 11 can be prepared as illustrated in Scheme 13, whereby an ester of Formula 12 is saponified (e.g., potassium hydroxide in methanol, then acidified with an acid such as hydrochloric acid) or, alternatively, is acid hydrolyzed (e.g., 5NHC1 in acetic acid) by methods known in the art (or slight modification of these methods); see for example, Ogliaruso, M. A. et al. Synthesis of Carboxylic Acids, Esters and Their Derivatives; John Wiley & Sons, 1991, pp 5-7.
  • Scheme 14 illustrates the preparation of many esters of Formula 12a whereby an appropriate ester of Formula 13 in an inert solvent is reacted with a nucleophilic heterocycle of Formula 14 in the presence of a suitable base. Reaction conditions are as described for Scheme 10.
  • X is F, Cl, Br, CH 3 S ⁇ 2 ⁇ or CF 3 S ⁇ 2 ⁇ and X is ortho o ⁇ para to the C ⁇ 2R a group;
  • Nu is an optionally-substituted imidazole, pyrazole, triazole or tetrazole;
  • a 1 is an optionally-substituted 1/t-imidazole, l -pyrazole, l ,2,4-triazole, 4f7-l,2,4-triazole or tetrazole and A 1 is ortho or para to the C0 2 R 7 group; and W is CH orN.
  • Esters of Formula 12 wherein Q is Ar and Ar is phenyl or a heterocyclic ring further substituted with another phenyl or heterocyclic ring can be synthesized by known coupling methods reviewed in Kalinin, V. Synthesis (1992), pp 413-432.
  • Scheme 15 illustrates an alternative preparation of many carboxylic acids of Formula 11 whereby a bromide compound of Formula 15 is treated with n-butyllithium (or magnesium) and the lithium salt (or the Grignard reagent) generated in situ is then reacted with carbon dioxide followed by acidification with an acid such as hydrochloric acid.
  • This conversion is carried out by using methods known in the art (or by slights modification of these methods); see for example, Ogliaruso, M. A. et al. Synthesis of Carboxylic Acids, Esters and Their Derivatives; John Wiley & Sons; pp 27-28; Bridges, A. J. et al. J. Org. Chem. (1990), 55, 773; Franke, C. et al. Angew. Chem. Int. Ed. (1969), 8, 68. Protecting and deprotecting functional groups not compatible with the reaction conditions may be necessary for compounds with such functional groups.
  • bromo compounds of Formula 15 are commercially available, while others can be prepared by bromination of their corresponding aromatic or heteroaromatic precursors with bromine or other equivalent reagents in an inert solvent. This type of bromination is carried out by general methods known in the art; see for example, Campaigne, E. et al. J. Heterocycl. Chem. (1969), 6, 517; Gilman, H. J. Am. Chem. Soc. (1955), 77, 6059.
  • nitro compounds of Formula 7, bromo compounds of Formula 15, and ester compounds of Formula 12 can be prepared by those skilled in the art using methods known in the art (or by obvious modification of these methods); see for example, Rorer, M. P. U.S. Patent 4,511,392; Wolf, A. D. U.S. Patent 4,465,505; Sauers, R. F. U.S. Patent 4,460,401; Denes, R. WO 93/11097; Petersen, C. et al. WO 96/31517; Denes, R. WO 95/09846; Katritzky, A. R. et al. Comprehensive Heterocyclic Chemistry; Pergamon Press; Volumes 2- 6. Protecting and deprotecting functional groups not compatible with the reaction conditions may be necessary for compounds with such functional groups.
  • Scheme 16 illustrates another method for preparing tetrazolinones of Formula 1 whereby an isocyanate of Formula 5 is reacted with sodium azide and aluminum chloride in an inert solvent such as N-N-dimethylformamide (DMF) followed by addition of water and a mineral acid in excess, such as hydrochloric acid.
  • an inert solvent such as N-N-dimethylformamide (DMF)
  • DMF N-N-dimethylformamide
  • This type of reaction can be carried out by methods known in the art (or slight modification of these methods); see for example, Horwitz, J. P. et al. J. Am. Chem. Soc. (1959), 81, 3076; Yanagi, A. et al. U.S. Patent 5,530,135; Covey, R. A. et al. U.S. Patent 4,618,365.
  • Step A Preparation of (4-N-ethyl-tetrahvdro-4H-pyran) To a dry flask under a nitrogen atmosphere was added 5.3 g of ethylamine hydrochloride followed by 50 mL of anhydrous methanol. 1 g of powdered KOH was added and the reaction mixture stirred at room temperature for 15 min. 5 g of tetrahydro-4H-pyran- 4-one (commercially available from Aldrich) was added followed by the batchwise addition of 1.2 g of sodium cyanoborohydride over a 30 minute period. The reaction was stirred at room temperature for 30 minutes.
  • Step B Preparation of ethyl(tetrahvdro-2//-pyran-4-yl)carbamic chloride
  • Step C Preparation of 4-(2-chlorophenylVN-ethyl-4,5-dihvdro-5-oxo-N-ftetrahydro-
  • Step C Preparation of 1 ,4-dihvdro-4-
  • Step D Preparation of N-ethyl-4.5-dihvdro-5-oxo-N-(tetrahvdro-2H-pyran-4-yl)-4-r2- r3-(trifluoromethyl)- l/ -pyrazol- 1 -yllphenyl]- 1 H-tetrazole- 1 -carboxamide
  • To 1.43 g of the title compound of Step C was added 8 mL of anhydrous toluene, 0.59 g of dimethylaminopyridine, and 0.925 g of the title compound of Step B in Example 1 and the reaction was refluxed for 2 hours.
  • Step B Preparation of cvclopropyl(tetrahvdro-2H-pyran-4-yl)carbamic chloride To a dry flask under a nitrogen atmosphere was added 1.69 g of triphosgene followed by 15 mL of anhydrous toluene.
  • Step C Preparation of 4-(2-chlorophenyl)-N-cvclopropyl-4,5-dihvdro-5-oxo-N-
  • Step B Preparation of (3.6-dihvdro-2H- ⁇ yran-4-v ⁇ (l-methylethv ⁇ carbamic chloride
  • a dry flask under a nitrogen atmosphere was added 11.3 g of the title compound of Step A, followed by 15.3 mL of diisopropylethylamine and 45 mL of anhydrous benzene.
  • the flask was cooled to 0 °C and 44 mL of a 20% solution of phosgene in toluene was added over a period of 10 minutes. After stirring at room temperature for 90 minutes, the reaction mixture was partitioned between benzene/ethyl acetate and water.
  • Step C Preparation of 4-(2.6-dichlorophenyl)-N-(3.6-dihvdro-2H-pyran-4-yl -4.5- dihydro-N-( 1 -methylethylVS-oxo- 1 H-tetrazole- 1 -carboxamide
  • Step D Preparation of 4-f2-chlorophenyl)-N-ethyl-4,5-dihydro-5-oxo-N-r(tetrahvdro-
  • II II II. II II. II II II II. II II II. II II II II. II II II II I III II II II II II II II II II II. II II II II II II.

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Abstract

Compounds of Formula (I), and their N-oxides and agriculturally suitable salts, are disclosed which are useful for controlling undesired vegetation wherein Q, A, R?1, R2, R6, R7¿, m, and q are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formula (I) and a method for controlling undesired vegetation which involves contacting the vegetation or its environment with an effective amount of a compound of Formula (I).

Description

TITLE HERBICIDAL TETRAZOLINONES BACKGROUND OF THE INVENTION This invention relates to certain tetrazolinones, their N-oxides, agriculturally suitable salts and compositions thereof, and methods of the use of the aforesaid compositions for controlling undesirable vegetation. This invention further relates to certain carbamyl chloride intermediates useful in the synthesis of said tetrazolinones.
The control of undesired vegetation is extremely important in achieving high crop efficiency. Achievement of selective control of the growth of weeds especially in such useful crops as rice, soybean, sugar beet, corn (maize), potato, wheat, barley, tomato and plantation crops, among others, is very desirable. Unchecked weed growth in such useful crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. The control of undesired vegetation in noncrop areas is also important. Many products are commercially available for these purposes, but the need continues for new compounds which are more effective, less costly, less toxic, environmentally safer or have different modes of action.
U.S. 5,019,152 discloses herbicidal tetrazolinones of the formula
Figure imgf000003_0001
wherein, inter alia,
R is alkyl, alkenyl, C7-C9 aralkyl, phenyl or substituted phenyl; and
R1 and R2 are independently C C6 alkyl, Cβ-Cg alkenyl or C5-C6 cycloalkyl.
The tetrazolinones 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:
Figure imgf000003_0002
wherein
A together with the carbon to which it is attached form 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 (CR6R7)q through other than X; X is O, S(O)n, NR3 or Si(R )2; each R1 is independently C1-C4 alkyl or C1-C4 haloalkyl; R2 is CrC6 alkyl, CrC6 haloalkyl, C3-C7 cycloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, Ci-Cg alkoxy, C2-C6 alkoxyalkyl, C2-C6 haloalkoxyalkyl; or R2 is phenyl optionally substituted with C C3 alkyl, halogen, cyano, nitro or C2-C4 alkoxycarbonyl; R3 is H, C1-C4 alkyl, -C4 haloalkyl, C3-C4 alkenyl, C3-C4 alkynyl, C2-C4 alkoxycarbonyl or C2-C4 alkylcarbonyl; or R3 is phenyl optionally substituted on the phenyl ring with Cι-C3 alkyl, halogen, cyano, nitro or C2-C4 alkoxycarbonyl; each R4 is independently C1-C4 alkyl; Q is CrC12 alkyl, CrC6 haloalkyl, C2-C13 alkoxyalkyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, C3-Ci2 alkenyl or C3-Cg alkynyl, each group optionally substituted with C1-C4 alkyl, C C4 haloalkyl, halogen, cyano, nitro or C2-C4 alkoxycarbonyl; or
Q is Ar-(CH )p- optionally substituted on the methylene carbon by 1-2 C]-C2 alkyl; or Q is a 5- or 6-membered aromatic heterocyclic ring containing 1 to 3 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 each heterocyclic ring is optionally substituted by one or more groups selected from halogen, nitro, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 alkenyl, C3-C4 alkynyl, CrC4 alkoxy, CrC haloalkoxy, S(O)nR5, C2-C4 alkoxycarbonyl, NR<>R7, SF5, NR8C(=O)R9, NR°>SO2R5, and SO2NR6R7; and when Q is a 5-membered aromatic heterocyclic ring containing a nitrogen, then Q can be bonded through any available carbon or nitrogen atom to the tetrazolinone ring by replacement of a hydrogen on said carbon or nitrogen atom; Ar is phenyl or pyridyl, each optionally substituted with halogen, cyano, nitro, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 alkynyl, C2-C4 alkoxycarbonyl, NR^R?, NR8C(=O)R9, NR8SO2R5, SF5, S(O)nR5, C1-C4 halothioalkoxy, phenoxy or Ar1;
Ar1 is phenyl or a 5- or 6-membered aromatic heterocyclic ring containing 1 to 3 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 each phenyl and heterocyclic ring is optionally substituted by one or more groups selected from halogen, nitro, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 alkenyl, C3-C4 alkynyl, C1-C4 alkoxy, C1-C4 haloalkoxy, C2-C4 alkoxycarbonyl, NR^R7, SF5, NR8C(=O)R9, NR SO2R5,
Figure imgf000005_0001
each R5 is independently C1-C4 alkyl or C1-C4 haloalkyl; each R6 is independently H or C J-C4 alkyl; each R7 is independently H or C1-C4 alkyl; each R8 is independently H or C1-C4 alkyl; each R9 is independently C1-C4 alkyl, C1-C4 haloalkyl or C1-C4 alkoxy; m is 0, 1, 2, 3 or 4; each n is independently 0, 1 or 2; p is 0 or 1 ; and q is 0, 1 or 2. Preferred compounds of the invention for reasons of better activity and/or ease of synthesis are:
Preferred 1. Compounds of Formula I above, geometric and stereoisomers thereof, N-oxides thereof and agriculturally-suitable salts thereof, wherein
Q is Ar-(CH2)p- optionally substituted on the methylene carbon by 1-2 Cι-C2 alkyl; or
Q is a 5- or 6-membered aromatic heterocyclic ring containing 1 to 3 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 each heterocyclic ring is optionally substituted by one or more groups selected from halogen, nitro, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 alkenyl, -C4 alkynyl, CrC4 alkoxy, CrC4 haloalkoxy, S(O)nR5, C2-C4 alkoxycarbonyl, ΝR^R7, SF5, NR8C(=O)R9, NR SO2R5, and SO2NR6R7; and when Q is a 5-membered aromatic heterocyclic ring containing a nitrogen, then Q can be bonded through any available carbon or nitrogen atom to the tetrazolinone ring by replacement of a hydrogen on said carbon or nitrogen atom. Preferred 2. Compounds of Preferred 1 wherein Q is Ar-(CH2)p-; Ar is phenyl optionally substituted with halogen, cyano, nitro, C1-C4 alkoxy,
C1-C4 haloalkoxy, C1-C4 alkyl, C1-C4 haloalkyl, C -C4 alkoxycarbonyl or S(O)nR5; R5 is methyl; each R6, R7, R8, and R9 is independently H or methyl; and p is O. Preferred 3. Compounds of Preferred 2 wherein
A together with the carbon to which it is attached form a fully or partially saturated 5-, 6- or 7-membered heterocyclic ring containing one X; and q is 0. Preferred 4. Compounds of Preferred 3 wherein
X is O, S or NR3. Preferred 5. Compounds of Preferred 4 wherein R2 is C ι -C6 alkyl, C , -C6 haloalkyl or C3-C7 cycloalkyl; or R2 is phenyl optionally substituted with C C3 alkyl, halogen, cyano, nitro or C2-C4 alkoxycarbonyl. Preferred 6. Compounds of Preferred 5 wherein X is O. Most preferred are compounds of Preferred 6 selected from the group:
(a) 4-(2,6-dichloroρhenyl)-N-(3,6-dihydro-2H-pyran-4-yl)-4,5-dihydro-N-(l- methylethyl)-5-oxo- lH-tetrazole- 1 -carboxamide;
(b) 4-(2-chloro-6-fluoroρhenyl)-N-(3,6-dihydro-2H-pyran-4-yl)-4,5-dihydro-N-(l- methylethyl)-5-oxo-lH-tetrazole-l-carboxamide; (c) 4-(2,6-dichlorophenyl)-N-(3,6-dihydro-2H-pyran-4-yl)-N-ethyl-4,5-dihydro-5- oxo- lH-tetrazole- 1 -carboxamide;
(d) N-(3 ,6-dihydro-2H-pyran-4-yl)-4-(2-fluorophenyl)-4,5-dihydro-N-( 1 - methylethyl)-5-oxo-lH-tetrazole-l-carboxamide;
(e) 4-(2,6-difluorophenyl)-N-(3,6-dihydro-2H-pyran-4-yl)-4,5-dihydro-N-( 1 - methylethyl)-5-oxo-lH-tetrazole-l-carboxamide;
(f) 4-(2,6-dichlorophenyl)-N-(5,6-dihydro-2H-pyran-3-yl)-4,5-dihydro-N-(l- methylethyl)-5-oxo-lH-tetrazole-l-carboxamide; and
(g) 4-(2-chloro-4-fluorophenyl)-N-(3,6-dihydro-2H-pyran-4-yl)-4,5-dihydro-N-( 1 - methylethyl)-5-oxo- lH-tetrazole- 1 -carboxamide. This invention is further directed to compounds of Formula 2, including all geometric and stereoisomers thereof:
Figure imgf000006_0001
wherein
A together with the carbon to which it is attached form 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 (CR6R7)q through other than X; X is O, S(O)n, NR3 or Si(R4)2; each R1 is independently C1-C4 alkyl or C1-C4 haloalkyl; R2 is CrC6 alkyl, CrC6 haloalkyl, C3-C7 cycloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C Cg alkoxy, C2-C6 alkoxyalkyl or C2-C6 haloalkoxyalkyl; R3 is H, C1-C4 alkyl, CrC4 haloalkyl, C3-C4 alkenyl, C3-C4 alkynyl, C2-C4 alkoxycarbonyl or C2-C4 alkylcarbonyl; or R3 is phenyl optionally substituted on the phenyl ring with C C3 alkyl, halogen, cyano, nitro or C2-C4 alkoxycarbonyl; each R4 is independently C1-C4 alkyl; each R6 is independently H or C1-C4 alkyl; each R7 is independently H or C1-C4 alkyl; m is O, 1, 2, 3 or 4; each n is independently 0, 1 or 2; and q is 0, 1 or 2.
Further preferred compounds of Formula 2 are: Preferred 7. Compounds of Formula 2 above, geometric and stereoisomers thereof, wherein A together with the carbon to which it is attached form a fully or partially saturated 5-, 6- or 7-membered heterocyclic ring containing one X; and q is 0. Preferred 8. Compounds of Preferred 7 wherein X is O, S or NR3. Preferred 9. Compounds of Preferred 8 wherein
R2 is CrC6 alkyl, CrC6 haloalkyl or C3-C7 cycloalkyl. Preferred 10. Compounds of Preferred 9 wherein X is O. Most preferred are compounds of Preferred 10 selected from the group: (a) (3 ,6-dihydro-2H-pyran-4-yl)( 1 -methylethyl)carbamic chloride;
(b) (5,6-dihydro-2H-pyran-3-yl)(l -methylethyl)carbamic chloride;
(c) (3,6-dihydro-2H-pyran-4-yl)ethylcarbamic chloride; and
(d) [2,5-dihydro-5-(trifluoromethyl)-3-furanyl](l -methylethyl)carbamic chloride. DETAILS OF THE INVENTION In the above recitations, the term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl" includes straight-chain or branched alkyl, such as, methyl, ethyl, /j-propyl, z'-propyl, or the different butyl, pentyl or hexyl isomers. The term "1-2 alkyl" indicates that one or two of the available positions for that substituent may be alkyl which are independently selected. "Alkenyl" includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers. "Alkenyl" also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl. "Alkynyl" includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. "Alkynyl" can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl. "Alkoxy" includes, for example, methoxy, ethoxy, rc-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers. "Alkoxyalkyl" denotes alkoxy substitution on alkyl. Examples of "alkoxyalkyl" include CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2CH2OCH2 and
CH3CH2OCH2CH2. "Alkylthio" includes branched or straight-chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers. "Alkylthioalkyl" denotes alkylthio substitution on alkyl. Examples of "alkylthioalkyl" include CH3SCH2, CH3SCH2CH2, CH3CH2SCH2, CH3CH2CH2CH2SCH2 and CH3CH2SCH2CH2. "Alkylthioalkoxy" denotes alkylthio substitution on alkoxy. "Cyanoalkyl" denotes an alkyl group substituted with one cyano group. Examples of "cyanoalkyl" include NCCH2, NCCH2CH2 and CH3CH(CN)CH2. "Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. The term "cycloalkoxy" includes the same groups linked through an oxygen atom such as cyclopentyloxy and cyclohexyloxy. "Cycloalkenyl" includes groups such as cyclopentenyl and cyclohexenyl as well as groups with more than one double bond such as 1,3- and 1,4-cyclohexadienyl. Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to straight-chain or branched alkyl groups. Examples of "cycloalkylalkoxy" include cyclopropylmethoxy, cyclopentylethoxy, and other cycloalkyl moieties bonded to straight-chain or branched alkoxy groups. "Alkylcycloalkyl" denotes alkyl substitution on a cycloalkyl moiety. Examples include 4-methylcyclohexyl and 3-ethylcyclopentyl. "Cyanocycloalkyl" denotes a cycloalkyl group substituted with one cyano group. Examples of "cyanocycloalkyl" include 4-cyanocyclohexyl and 3-cyanocyclopentyl. The term "aromatic ring" denotes fully unsaturated carbocycles and heterocycles in which the ring is aromatic (where aromatic indicates that the Hϋckel rule is satisfied for the ring). The term "aromatic heterocyclic ring" includes fully aromatic heterocycles in which the ring aromatic (where aromatic indicates that the Hϋckel rule is satisfied). The heterocyclic ring systems can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen. One skilled in the art will appreciate that not all 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. One skilled in the art will also recognize that tertiary amines can form N-oxides. Synthetic methods for the preparation of 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 -chloroperbenzoic acid (MCPBA), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethyldioxirane. These methods for the preparation of N-oxides have been extensively described and reviewed in the literature, see for example: T. L. Gilchrist in Comprehensive Organic Synthesis, vol. 7, pp 748-750, S. N. Ley, Ed., Pergamon Press; M. Tisler and B. Stanovnik in Comprehensive Heterocyclic Chemistry, vol. 3, pp 18-20, A. J. Boulton and A. McKillop, Eds., Pergamon Press; M. R. Grimmett and B. R. T. Keene in Advances in Heterocyclic Chemistry, vol.43, pp 149-161, A. R. Katritzky, Ed., Academic Press; M. Tisler and
B. Stanovnik in Advances in Heterocyclic Chemistry, vol. 9, pp 285-291, A. R. Katritzky and A. J. Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G. Werstiuk in Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A. R. Katritzky and A. J. Boulton, Eds., Academic Press. The term "halogen", either alone or in compound words such as "haloalkyl", includes fluorine, chlorine, bromine or iodine. The term "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 F3C, C1CH2, CF3CH2 and CF3CC12. The terms "haloalkenyl",
"haloalkynyl", "haloalkoxy", "haloalkylthio", and the like, are defined analogously to the term "haloalkyl". Examples of "haloalkenyl" include (C1)2C=CHCH2 and CF3CH2CH=CHCH2. Examples of "haloalkynyl" include HC≡CCHCl, CF3C≡C, CC13C≡C and FCH2C≡CCH2. Examples of "haloalkoxy" include CF3O, CCl3CH2O, HCF2CH2CH2O and CF3CH2O. Examples of "haloalkylthio" include CC13S, CF3S, CC13CH2S and C1CH2CH2CH2S.
The total number of carbon atoms in a substituent group is indicated by the "Cj-Cj" prefix where i and j are numbers from 1 to 13. For example, Cι-C3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl; C2 alkoxyalkyl designates CH3OCH2; C3 alkoxyalkyl designates, for example, CH3CH(OCH3), CH3OCH2CH2 or CH3CH2OCH2; and C alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH3CH2CH2OCH2 and CH3CH2OCH2CH2. Examples of "alkylcarbonyl" include C(O)CH3, C(O)CH2CH2CH3 and C(O)CH(CH3)2. Examples of "alkoxycarbonyl" include CH3OC(=O), CH3CH2OC(=O), CH3CH2CH2OC(=O), (CH3)2CHOC(=O) and the different butoxy- or pentoxycarbonyl isomers. In the above recitations, when a compound of Formula I is comprised of one or more heterocyclic rings, all substituents are attached to these rings through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
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)j_j, then the number of substituents may be selected from the integers between i and j inclusive.
When a group contains a substituent which can be hydrogen, for example R3, then, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted. The compounds of this invention thus include compounds of Formula I, geometric and stereoisomers thereof, N-oxides thereof and agriculturally suitable salts thereof. The compounds of this invention further include compounds of Formula 2, as well as geometric and stereoisomers thereof. The compound of the invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. The compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.
The salts of the compounds of the invention include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids. 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.
The compounds of Formula I and Formula 2 can be prepared by one or more of the following methods and variations as described in Schemes 1-17. The definitions of A, Q, Ar, Ar1, X, Rϊ-R9, m, n, p, and q in the compounds of Formulae 1-22 below are as defined above in the Summary of the Invention. Scheme 1 illustrates the preparation of compounds of Formula I whereby a tetrazolinone of Formula 1 is reacted with a carbamyl chloride of Formula 2 in the presence of a suitable acid acceptor agent. Suitable acid acceptor agents include alkali carbonates, alkali bicarbonates, alkyl tertiary amines such as triethylamine, pyridine, and, preferably, 4- dimethylaminopyridine (DMAP). Furthermore, DMAP can be used as a catalyst in the presence of another suitable acid acceptor agent in order to selectively synthesize a compound of Formula I. The reaction is carried out in an inert solvent such as tetrahydrofuran, acetone, chloroform, chlorobenzene or preferably acetonitrile or toluene, and at a temperature range between 0 °C and 110 °C by methods known in the art (or slight modification of these methods); for example, see Yanagi, A. et al. EP 646,577; Goto, T. et al. EP 708,097; Covey, R. A. et al. U.S. Patent 4,618,365.
Scheme 1
Figure imgf000011_0001
Carbamyl chlorides of Formula 2 can be made by treating compounds of Formula 3 with phosgene or a phosgene equivalent such as diphosgene in the presence of a suitable base such as triethylamine or diisopropylethylamine (Scheme 2).
Scheme 2
Figure imgf000011_0002
Amines of Formula 3 (wherein q is 0) can be made by the sequence of reactions shown in Scheme 3 whereby a ketone of Formula 4 is treated with an appropriate amine and the formed intermediate imine is subsequently reduced to the amine. This type of reaction can be carried out by methods known in the art (or slight modification of these methods); see, for example, Borch, R. Org. Synthesis, Collective Volume VI, (1988), p 499 and Bomann, M. et al. J. Org. Chem. (1995), 60, p 5995. Scheme 3
Figure imgf000012_0001
Many ketones of Formula 4 are either commercially available or can be prepared by methods known in the art; for example, see Soderquist, J. and Negron, A. J. Org. Chem. (1989), 54, pp 2464-2466 for the preparation of l-silacyclohexan-4-ones or Howard, E. and Lindsey, R. J. Am. Chem. Soc. (1960), 82, pp 158-164 for the preparation of 5-τw- dithianones.
Carbamyl chlorides of Formula 2a wherein a carbon-carbon double bond is present within the heterocyclic ring can be made as illustrated in Scheme 4. A ketone of Formula 16 is reacted with an appropriate amine in the presence of a dehydrating agent and the resulting imine intermediate of Formula 18 is treated with phosgene in the presence of a base such as triethylamine to yield the carbamyl chloride of Formula 2a.
Figure imgf000012_0002
Carbamyl chlorides of Formula 2b (wherein q is 1 or 2) can be made as illustrated in
Scheme 5. An amine of Formula 19 is reacted with an appropriate acid anhydride in the presence of a base to provide the amide of Formula 20. Reduction of the amide with lithium aluminum hydride results in the amine of Formula 21 which is treated with phosgene in the presence of a base such as triethylamine to yield the carbamyl chloride of Formula 2b. Compounds of Formula 19 are either commercially available or can be prepared by methods well-established in the art. Scheme 5
lithium aluminum hydride
Figure imgf000013_0001
(Ra is alkyl)
Figure imgf000013_0002
benzene 21 2b
Carbamyl chlorides of Formula 2c (wherein q is 1 or 2) can be made as illustrated in Scheme 5a. An amine of Formula 19 is reacted with an appropriate carbonyl compound in the presence of molecular sieves, followed by reduction of the imine with sodium cyanoborohydride to give the amine of Formula 22. The amine is treated with phosgene in the presence of a base such as triethylamine to yield the carbamyl chloride of Formula 2c.
Scheme 5a
molecular sieves
Figure imgf000013_0003
NaCNBH3
19 (Ra and Rb are alkyl)
phosgene triethylamine
Figure imgf000013_0005
benzene
Figure imgf000013_0004
Alternatively, compounds of Formula I can be prepared whereby a tetrazolinone of
Formula 1 in an inert solvent such as toluene or ethyl acetate is reacted with phosgene and a suitable tertiary amine base such as triethylamine, and the product of such reaction is reacted with a secondary amine of Formula 3, optionally in the presence of a suitable base such as pyridine (Scheme 6). This type of reaction can be carried out by methods known in the art (or slight modification of these methods); see, for example, Covey, R. A. et al. U.S. Patent 5,019,152. Scheme 6
Figure imgf000014_0001
Scheme 7 illustrates a preferred method for preparing tetrazolinones of Formula 1 whereby an isocyanate of Formula 5 is reacted with refluxing trimethylsilylazide (also known as azidotrimethylsilane), followed by treatment of the product of such reaction with a protic solvent such as water or preferably with methanol. This type of reaction can be carried out by methods known in the art (or slight modification of these methods); see, for example, Tsuge, O. et al. J. Org. Chem. (1980), 45, 5130; Goto, T. et al. EP 695,748 and EP 692,482.
Scheme 7
(CH3)3 SϊN3; then e.g., CH3OH
Q— NCO
5
Many alkyl and phenyl isocyanates of Formula 5 are commercially available. Other isocyanates of Formula 5 can be prepared by treatment of corresponding amines of Formula 9 with phosgene or known phosgene equivalents (e.g., diphosgene or triphosgene) by methods generally known in the art (Scheme 8); see for example, March, J. Advanced Organic Chemistry, 3rd edition; John Wiley & Sons, 1985, p 370; Chem. Rev. (1972), 72, pp 457-496; Sandier, R. S. et al. Organic Functional Group Preparations, 2nd edition; Academic Press; Vol. II, pp 152 and 260; Lehman, G. et al. Preparative Organic Chemistry; John Wiley & Sons, 1972; p 472.
Scheme 8
phosgene Q— NH2 *► 5
6
Many amines of Formula 6 are commercially available, including both simple and substituted alkyl, alkenyl, alkynyl, phenyl, pyridyl, and heteroaryl amines. Alternatively, amines of Formula 6 can be prepared by reduction of the corresponding nitro compounds of Formula 7 (Scheme 9). A wide variety of methods are documented in the chemical literature for carrying out such transformations; see for example, Rorer, M. P. U.S. Patent 4,511,392; Ohme, R. et al. Preparative Organic Chemistry; John Wiley & Sons, 1972; p 557; Groggins Unit Processes in Organic Chemistry; McGraw-Hill Book Co.: New York, 1947; pp 73-128; March, J. Advanced Organic Chemistry, 3rd edition; John Wiley & Sons, 1985; pp 1103- 1104.
Scheme 9
Reduction
Q— -N02
7
Many nitro compounds of Formula 7 are commercially available or can be synthesized by methods well-established in the art. Nitro compounds of Formula 7a can be prepared as illustrated in Scheme 10 whereby an appropriate nitro compound of Formula 8 in an inert solvent is reacted with a nucleophilic heterocycle of Formula 9 in the presence of a suitable base. Suitable bases include alkali carbonates such as potassium carbonate, potassium tert- butoxide, and sodium hydride. Suitable solvents include dimethylformamide, 2-butanone, and tetrahydrofuran. The reaction is carried out at a temperature range of about 0 °C to 150 °C, preferably about 80 °C to 120 °C, with dimethylformamide as the solvent and potassium carbonate as the base. Following workup by generally-known methods, the compound of Formula 6a can be purified by recrystallization or flash column chromatography on silica gel by those skilled in the art. Protecting and deprotecting functional groups not compatible with reaction conditions may be necessary for compounds with such functional groups.
Scheme 10
Figure imgf000015_0001
7a wherein X is F, Cl, Br, CH3S0 0 or CF3S020 and X is ortho or para to the N02 group; Nu is an optionally-substituted imidazole, pyrazole, triazole or tetrazole; Al is an optionally-substituted lH-imidazole, l /-pyrazole, l//-l,2,4-triazole, 4//-l,2,4-triazole or tetrazole and A1 is ortho o para to the N02 group; and W is CH or N. Nitro compounds of Formula 7 wherein Q is Ar and Ar is phenyl or a heterocyclic ring further substituted with another phenyl or heterocyclic ring can be synthesized by known coupling methods reviewed in Kalinin, V. Synthesis (1992), pp 413-432.
Many isocyanates of Formula 5 can be also be prepared by Curtius rearrangement of appropriate acid chlorides of Formula 10 using methods generally known in the art (Scheme 1 1); see, for example, March, J. Advanced Organic Chemistry, 3rd edition; John Wiley & Sons, 1985; pp 984-985 and 380.
Scheme 1 1
O Q— CC1 e.g., NaN3 (Curtius Rearrangement)
Acid chlorides of Formula 10 can be prepared by reacting an acid of Formula 11 with oxalyl chloride (or thionyl chloride) and optionally a catalytic amount of dimethylformamide (Scheme 12). This chlorination is well known in the art; see, for example, Michaely, W. J. EP 369,803; Goto, T. et al. EP 695,748. Other methods are also well known in the art for converting carboxylic acids to acid chlorides; see, for example, Ogliaruso, M. A. et al. Synthesis of Carboxylic Acids, Esters and Their Derivatives; John Wiley & Sons, 1991, pp 172-174.
Scheme 12
oxalyl chloride
0— C02H • 10
(optionally a catalytic amount 11 of DMF)
Carboxylic acids of Formula 11 can be prepared as illustrated in Scheme 13, whereby an ester of Formula 12 is saponified (e.g., potassium hydroxide in methanol, then acidified with an acid such as hydrochloric acid) or, alternatively, is acid hydrolyzed (e.g., 5NHC1 in acetic acid) by methods known in the art (or slight modification of these methods); see for example, Ogliaruso, M. A. et al. Synthesis of Carboxylic Acids, Esters and Their Derivatives; John Wiley & Sons, 1991, pp 5-7. Scheme 13
Q — C02Ra ■ 11
KOH in CH3OH,
12 then H+ wherein Ra is C i -C2 alkyl
Scheme 14 illustrates the preparation of many esters of Formula 12a whereby an appropriate ester of Formula 13 in an inert solvent is reacted with a nucleophilic heterocycle of Formula 14 in the presence of a suitable base. Reaction conditions are as described for Scheme 10.
Scheme 14
Figure imgf000017_0001
13 12a wherein X is F, Cl, Br, CH3Sθ2θ or CF3Sθ2θ and X is ortho oτpara to the Cθ2Ra group; Nu is an optionally-substituted imidazole, pyrazole, triazole or tetrazole; A1 is an optionally-substituted 1/t-imidazole, l -pyrazole, l ,2,4-triazole, 4f7-l,2,4-triazole or tetrazole and A1 is ortho or para to the C02R7 group; and W is CH orN.
Esters of Formula 12 wherein Q is Ar and Ar is phenyl or a heterocyclic ring further substituted with another phenyl or heterocyclic ring can be synthesized by known coupling methods reviewed in Kalinin, V. Synthesis (1992), pp 413-432.
Scheme 15 illustrates an alternative preparation of many carboxylic acids of Formula 11 whereby a bromide compound of Formula 15 is treated with n-butyllithium (or magnesium) and the lithium salt (or the Grignard reagent) generated in situ is then reacted with carbon dioxide followed by acidification with an acid such as hydrochloric acid. This conversion is carried out by using methods known in the art (or by slights modification of these methods); see for example, Ogliaruso, M. A. et al. Synthesis of Carboxylic Acids, Esters and Their Derivatives; John Wiley & Sons; pp 27-28; Bridges, A. J. et al. J. Org. Chem. (1990), 55, 773; Franke, C. et al. Angew. Chem. Int. Ed. (1969), 8, 68. Protecting and deprotecting functional groups not compatible with the reaction conditions may be necessary for compounds with such functional groups. Scheme 15
«-BuLi (or Mg)
Q — Br 1 1
2. C02 15 3. H+
Many bromo compounds of Formula 15 are commercially available, while others can be prepared by bromination of their corresponding aromatic or heteroaromatic precursors with bromine or other equivalent reagents in an inert solvent. This type of bromination is carried out by general methods known in the art; see for example, Campaigne, E. et al. J. Heterocycl. Chem. (1969), 6, 517; Gilman, H. J. Am. Chem. Soc. (1955), 77, 6059.
In general, nitro compounds of Formula 7, bromo compounds of Formula 15, and ester compounds of Formula 12 can be prepared by those skilled in the art using methods known in the art (or by obvious modification of these methods); see for example, Rorer, M. P. U.S. Patent 4,511,392; Wolf, A. D. U.S. Patent 4,465,505; Sauers, R. F. U.S. Patent 4,460,401; Denes, R. WO 93/11097; Petersen, C. et al. WO 96/31517; Denes, R. WO 95/09846; Katritzky, A. R. et al. Comprehensive Heterocyclic Chemistry; Pergamon Press; Volumes 2- 6. Protecting and deprotecting functional groups not compatible with the reaction conditions may be necessary for compounds with such functional groups.
Scheme 16 illustrates another method for preparing tetrazolinones of Formula 1 whereby an isocyanate of Formula 5 is reacted with sodium azide and aluminum chloride in an inert solvent such as N-N-dimethylformamide (DMF) followed by addition of water and a mineral acid in excess, such as hydrochloric acid. This type of reaction can be carried out by methods known in the art (or slight modification of these methods); see for example, Horwitz, J. P. et al. J. Am. Chem. Soc. (1959), 81, 3076; Yanagi, A. et al. U.S. Patent 5,530,135; Covey, R. A. et al. U.S. Patent 4,618,365.
Scheme 16
A1C13, DMF; then
5 + ΝaΝ3 H2θ/H+
In addition, many tetrazolinones of Formula 1 can be prepared as illustrated in Scheme
17, whereby an appropriate acid chloride of Formula 5 is refluxed with excess trimethylsilylazide, and the product of such reaction is treated with a protic solvent such as water or, preferably, with methanol. This type of reaction can be carried out by methods known in the art (or by slight modification of these methods): see, for example, Toselli, M. et al. J. Chem. Soc. Perkin Trans. 1 (1992), 1101; Goto, T. et al. EP 695,748 and EP 692,482; Horwitz, J. et al. J. Am. Chem. Soc. (1959), 81, 3076.
Scheme 17
(CH3)3SiN3
5 >■ 1 then CH3OH
It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula I may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of protection/deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as it is depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula I. One skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in the above schemes in an order other than that implied by the particular sequence presented to prepare the compounds of Formula I.
One skilled in the art will also recognize that compounds of Formula I and the intermediates described herein can be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents. Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Percentages are by weight except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated. !H NMR spectra are reported in ppm downfield from tetramethylsilane; s = singlet, d = doublet, t = triplet, q = quartet, m = multiplet, dd = doublet of doublets, dt = doublet of triplets, br s = broad singlet, br m = broad multiplet.
EXAMPLE 1 Step A: Preparation of (4-N-ethyl-tetrahvdro-4H-pyran) To a dry flask under a nitrogen atmosphere was added 5.3 g of ethylamine hydrochloride followed by 50 mL of anhydrous methanol. 1 g of powdered KOH was added and the reaction mixture stirred at room temperature for 15 min. 5 g of tetrahydro-4H-pyran- 4-one (commercially available from Aldrich) was added followed by the batchwise addition of 1.2 g of sodium cyanoborohydride over a 30 minute period. The reaction was stirred at room temperature for 30 minutes. An additional 2.63 g of powdered KOH was added and the reaction was stirred for 18 hours at room temperature. Methanol was removed under reduced pressure and 10 mL brine and 100 mL of ether were added. The reaction mixture was filtered, the ether layer separated, and the aqueous phase was reextracted with 100 mL of ether. The ether layers are combined and made acidic using 6 N HCl. The aqueous phase was separated and extracted once with 50 mL of ether. The aqueous phase was cooled to 0 °C and the pH adjusted to 10 by the slow addition of KOH pellets. The cloudy solution was filtered, extracted with 200 mL of ether and concentrated under reduced pressure to yield 5.6 g of the title compound as a liquid which was used as a starting material in the next step without further purification. Step B: Preparation of ethyl(tetrahvdro-2//-pyran-4-yl)carbamic chloride
To an dry flask under a nitrogen atmosphere was added 1.85 g of triphosgene followed by 15 mL of anhydrous toluene. The flask was cooled to 0 °C and to it was added a mixture of 2 g of the title compound of Step A, 1.3 mL of triethylamine, and 10 mL of anhydrous toluene over a period of 10 min. The reaction mixture is refluxed for 9 hours, cooled to room temperature and partitioned between 1 N HCl and 125 mL of ethyl acetate. The ethyl acetate layer was washed with 40 mL of saturated aqueous sodium bicarbonate and concentrated under reduced pressure to yield the 1.9 g of the title compound of Step B as a liquid which was used as a starting material in the next step without further purification. Step C: Preparation of 4-(2-chlorophenylVN-ethyl-4,5-dihvdro-5-oxo-N-ftetrahydro-
2H-pyran-4-yl)- lH-tetrazole- 1 -carboxamide To 0.482 g of l-(2-chlorophenyl)-l,4-dihydro-5H-tetrazol-5-one (prepared according to Goto, T. et al. EP 578,090 A2) was added 8 mL of anhydrous toluene, 0.299 g of dimethylaminopyridine, and 0.470 g of the title compound of Step B and the reaction was refluxed for 2 hours. The reaction mixture was cooled to room temperature, filtered and the filter cake was washed with 50 mL of ether. The filtrate was concentrated under reduced pressure and purified using silica gel column chromatography to yield 0.667 g of the title compound of Step C, a compound of this invention, as an oil. Η ΝMR (CDC13): δ 7.55 (m, 4H), 4.3-3.9 (br m, 3H), 3.4 (br m, 4H), 1.9 (br m, 4H), 1.3 (br m, 3H).
. EXAMPLE 2 Step A: Preparation of 4-(2-bromόphenyl')-N-ethyl-4,5-dihvdro-5-oxo-N-(tetrahvdro-
2H-pyran-4-yl)- lH-tetrazole- 1 -carboxamide To 1.25 g of l-(2-bromophenyl)-l,4-dihydro-5H-tetrazol-5-one (prepared by modification of the method according to Goto, T. et al. EP 578,090 A2) was added 8 mL of anhydrous toluene, 0.636 g of dimethylaminopyridine, and 1.0 g of the title compound of Step B in Example 1 and the reaction was refluxed for 2 hours. The reaction mixture was cooled to room temperature, filtered and the filter cake was washed with 50 mL of ether. The filtrate was concentrated under reduced pressure and purified using silica gel column chromatography to yield 0.87 g of the title compound of Step A, a compound of this invention, as an oil. Η NMR (CDC13): δ 7.8 (d, 1H), 7.55 (m, 3H), 4.3-3.9 (br m, 3H), 3.4 (br m, 4H), 1.9 (br m, 4H), 1.3 (br m, 3H).
EXAMPLE 3 Step A: Preparation of l-f2-nitrophenylV3-ftrifluorometfayl)-lH-pyrazole
To 135 mL ofNN-dimethylformamide was added 20.2 g (0.149 mol) of 3- (trifluoromethyl)pyrazole (purchased from Maybridge Chemical Co.), 20.0 g (0.142 mol) of l-fluoro-2-nitrobenzene (purchased from Aldrich Chemical Co.) and 20.6 g (0.149 mol) of potassium carbonate. The suspension was stirred and heated under nitrogen for 7.5 h at 80 °C, then cooled to 25 °C and poured into excess water. The aqueous suspension was filtered, and the isolated solid was washed three times with water (70 mL), then suction dried to yield 36.6 g of the title compound of Step A as a solid melting at 52-55 °C. JH ΝMR (CDC13): δ 6.65 (d, 1H), 7.65 (m, 2H) 7.75 (m, 2H), 8.0 (d, 1H).
Step B: Preparation of 2-r3-(trifluoromethyl)-lH-pyrazol-l-yl1benzenamine
A suspension containing 31.65 g (0.123 mol) of the title compound of Step A, 274.5 mL of glacial acetic acid and 44.7 mL of water was stirred and heated to 70 °C. Iron powder (22.7 g; 0.406 mol) was then added portionwise to the suspension at such a rate as to maintain the reaction temperature between 80 °C and 90 °C. Following completion of addition, the suspension was heated at about 85 °C for about 0.5 h, then filtered while hot through a Celite® pad. After washing the pad with warm glacial acetic acid (about 40 mL at 80 °C), the filtrates were combined, poured into excess cold water and the resulting suspension was filtered. The isolated solid was washed thoroughly four times with water (40 mL), redissolved in dichloromethane and dried over magnesium sulfate, and the filtered solution evaporated to dryness under reduced pressure to yield 23.2 g of the title compound of Step B as a solid melting at 58-61 °C. lK ΝMR (CDC13): δ 4.55 (s, 2H) 6.7 (d, 1H), 6.8 (m, 2H), 7.2 (m, 2H), 7.75 (d, 1H). Step C: Preparation of 1 ,4-dihvdro-4-|"2-r3-(trifluoromethyl')- lH-pyrazol- 1 -yl henyl]- 5H-tetrazol-5-one
3.0 g (0.0132 mol) of the title compound of Step B was added portionwise to a solution under a nitrogen atmosphere containing 4.9 g (0.0264 mol) of trichloromethyl chloroformate dissolved in 50 mL of ethyl acetate, while maintaining the reaction temperature at about 5 °C with external cooling. After addition was complete, the suspension was refluxed under nitrogen for 7 h, then evaporated to dryness under reduced pressure. The residue was azeotroped with ethyl acetate (twice with about 20 mL at 70 °C) to yield 3.4 g of oil. This oil was added to 3.1 g (0.027 mol) of azidotrimethylsilane (Aldrich). The suspension was refluxed under nitrogen for 20 h, then evaporated to dryness under reduced pressure at about 90 °C to remove excess azidotrimethylsilane. After cooling the residue to 25 °C, 20 mL of methanol was added. The suspension was stirred about 0.5 h and then concentrated under reduced pressure at about 80 °C. The residue was purified by flash column chromatography on silica gel with hexane:ethyl acetate (7.5:2.5, then 6:4, then 1:1) as eluant to yield 1.46 g of the title compound of Step C as a solid melting at 152-156 °C. !H NMR ((CD3)2SO): δ 6.95 (d, 1H), 7.7-7.8 (m, 4H) 7.85 (m, 1H) 8.35 (d, 1H) 14.5 (s, 1H).
Step D: Preparation of N-ethyl-4.5-dihvdro-5-oxo-N-(tetrahvdro-2H-pyran-4-yl)-4-r2- r3-(trifluoromethyl)- l/ -pyrazol- 1 -yllphenyl]- 1 H-tetrazole- 1 -carboxamide To 1.43 g of the title compound of Step C was added 8 mL of anhydrous toluene, 0.59 g of dimethylaminopyridine, and 0.925 g of the title compound of Step B in Example 1 and the reaction was refluxed for 2 hours. The reaction mixture was cooled to room temperature, filtered and the filter cake was washed with 50 mL of ether. The filtrate was concentrated under reduced pressure and purified using silica gel column chromatography to yield 0.895 g of the title compound of Step A, a compound of this invention, as an oil. Η ΝMR (CDC13): δ 7.82 (s 1H), 7.55 (m, 4H), 6.7 (s, 1H), 4.3-3.9 (br s, 3H), 3.4 (br s, 4H), 1.9 (br s, 4H), 1.3 (br m, 3H).
EXAMPLE 4 Step A: Preparation of N-cvclopropyltetrahydro-2H-ρyran-4-amine
Prepared according to the protocol described by Bomann, M. D. et al., J. Org. Chem. (1995), 60, pp 5995-5996. To 50 mL of anhydrous methanol containing 3.5 g of powdered and activated 4 A molecular sieves was added sequentially 4 g of tetrahydro-4//-pyran-4-one (available from Aldrich), 2.76 mL of cyclopropylamine and 3.5 mL of pyridine-borane. After 18 hours at room temperature, the resulting mixture was treated with 15 mL of 6 Ν HCl and stirred at room temperature for 1 hour. The pH of the solution is then adjusted to 14 using 8 Ν ΝaOH. Three extractions were performed with 100 mL of ether and the combined organic extracts were washed with brine and concentrated under reduced pressure to give the 5.5 g of the title compound of Step A as an oil, which was used as a starting material in the next step without further purification. Step B: Preparation of cvclopropyl(tetrahvdro-2H-pyran-4-yl)carbamic chloride To a dry flask under a nitrogen atmosphere was added 1.69 g of triphosgene followed by 15 mL of anhydrous toluene. The flask was cooled to 0 °C and to it was added a mixture of 2 g of the title compound of Step A, 1.16 mL of triethylamine, and 10 mL of anhydrous toluene over a period of 10 min. The reaction mixture was refluxed for 18 hours, cooled to room temperature and partitioned between 1NHC1 and 125 mL of ethyl acetate. The ethyl acetate layer was washed with 40 mL of saturated aqueous sodium bicarbonate and concentrated under reduced pressure to yield the 1.4 g of the title compound of Step B as a liquid which was used as a starting material in the next step without further purification. Step C: Preparation of 4-(2-chlorophenyl)-N-cvclopropyl-4,5-dihvdro-5-oxo-N-
(tetrahvdro-2H-pyran-4-ylV lH-tetrazole- 1 -carboxamide To 1.35 g of l-(2-chlorophenyl)-l,4-dihydro-5H-tetrazol-5-one (prepared according to Goto, T. et al. EP 578,090 A2) was added 15 mL of anhydrous toluene, 0.837 g of dimethylaminopyridine, 1.4 g of the title compound of Step B and the reaction was refluxed for 2 hours. The reaction mixture was cooled to room temperature, filtered and the filter cake was washed with 50 mL of ether. The filtrate was concentrated under reduced pressure and purified using silica gel column chromatography to yield 1.1 g of the title compound of Step C, a compound of this invention, as a solid melting at 140-142 °C. Η ΝMR (CDC13): δ 7.5 (m, 4H), 4.2 (m, 3H), 3.5 (t, 2H), 3.0 (m, 1H), 2.2 (m, 2H), 1.95 (br d, 2H), 0.9 (m, 4H).
EXAMPLE 5 Step A: Preparation of tetrahvdro-N-( 1 -methylethyl)-4H-pyran-4-imine
To a dry flask under a nitrogen atmosphere was added 2.5 g of tetrahydro-4H-pyran-4- one followed by 4.5 mL of isopropylamine. The reaction mixture was stirred at room temperature for 10 minutes followed by the addition of 1.8 g of powdered KOH. After stirring overnight at room temperature, 20 mL of anhydrous benzene was added and the reaction mixture was filtered over a thin pad of Celite®. The Celite® pad was washed with an additional 20 mL of benzene. The filtrate was concentrated under reduced pressure to give 3.1 g of the title compound of Step A as a liquid which was used as a starting material in the next step without further purification. IR (neat): 1663 cm-1. *H ΝMR (CDC13): δ 3.86 (t, 2H), 3.7 (m, 3H), 2.47 (t, 2H), 2.41 (t, 2H), 1.1 (d, 6H).
Step B: Preparation of (3.6-dihvdro-2H-ρyran-4-vπ(l-methylethvπcarbamic chloride To a dry flask under a nitrogen atmosphere was added 11.3 g of the title compound of Step A, followed by 15.3 mL of diisopropylethylamine and 45 mL of anhydrous benzene. The flask was cooled to 0 °C and 44 mL of a 20% solution of phosgene in toluene was added over a period of 10 minutes. After stirring at room temperature for 90 minutes, the reaction mixture was partitioned between benzene/ethyl acetate and water. The benzene/ethyl acetate layer was successively washed with 15 mL of 1 Ν HCl, brine, and then dried over sodium sulfate and concentrated under reduced pressure to yield 15.5 g of the title compound of Step B as a liquid (solidified upon standing) which was used as a starting material in the next step without further purification. lE ΝMR (CDC13): δ 1.2 (d, 6H), 2.3 (br s, 2H), 3.86 (br s, 2H), 4.28 (m, 2H), 4.38 (m, 1H), 5.71 (br s, 1H). Step C: Preparation of 4-(2.6-dichlorophenyl)-N-(3.6-dihvdro-2H-pyran-4-yl -4.5- dihydro-N-( 1 -methylethylVS-oxo- 1 H-tetrazole- 1 -carboxamide
To 0.6 g of l-(2,6-dichlorophenyl)-l,4-dihydro-5 -tetrazol-5-one (prepared according to Goto, T. et al. EP 578,090 A2) was added 10 mL of toluene, 316 mg of DMAP, and 528 mg of the title compound of Step B, and the reaction was refluxed for 2 hours. The reaction mixture was cooled to room temperature, concentrated under reduced pressure and partitioned between 100 mL of methylene chloride and 20 mL of saturated aqueous ammonium chloride. The methylene chloride layer was dried over sodium sulfate, concentrated under reduced pressure and purified using silica gel column chromatography to yield 567 mg of the title compound of Step C, a compound of this invention, as a solid melting at 110-112 °C. lH NMR (CDC13): δ 7.5 (m, 3H), 5.7 (br s, 1H), 4.4 (m, 1H), 4.1 (m, 2H), 3.7 (m, 2H), 2.3 (br s, 2H), 1.4 (d, 6H).
EXAMPLE 6 Step A: Preparation of N-r(tetrahydro-2-furanvDmethyl1acetamide To a solution of 5 g of tetrahydrofurfurylamine in 7.5 mL of triethylamine was added
5.1 mL of acetic anhydride over a period of 5 min. at 0 °C. The reaction mixture was stirred overnight at room temperature, concentrated under reduced pressure, made basic (pH = 10) using IN sodium hydroxide and extracted into 100 mL of methylene chloride. The methylene chloride layer was dried over sodium sulfate and concentrated to yield 7.0 g of the title compound of Step A as a liquid which was used as a starting material in the next step without further purification. !H ΝMR, CDC13: 6.0 (br s, 1H), 3.97 - 3.78 (m, 3H), 3.6 (m, 1 H), 3.1 (m, 1H), 1.9 (s, 3H), 1.94 (m, 3H), 1.5 (m, 1H). Step B: Preparation of N-ethyltetrahvdro-2-furanmethanamine
To 3.15 g of lithium aluminum hydride in an oven dry flask was added 100 mL of anhydrous tetrahydrofiiran. The flask is cooled to 0 °C and 7.0 g of the title compound of Step A was added over a 30 minute period. The reaction mixture was refluxed for 4 hours and cooled to room temperature. The reaction mixture was quenched by the sequential and cautious addition of 3.1 mL of water, 3.1 mL of 15% ΝaOH and 9.3 mL of water. To the white heterogeneous mixture was then added 50 mL of tetrahydrofuran. The reaction mixture was refluxed for 1 hour, filtered and the filtrate evaporated under reduced pressure. To the residue that was obtained was added 100 mL of methylene chloride. The methylene chloride layer was dried over sodium sulfate and concentrated under reduced pressure to yield 6.6 g of the title compound of Step B as a liquid which was used as a starting material in the next step without further purification. *H ΝMR, CDC13: 4.0 - 3.7 (m, 3H), 2.7 (m, 4H), 1.9 (m, 3H), 1.6 (m, 1H), 1.3 (br s, 1H), 1.1 (t, 3H).
Step C: Preparation of N-ethyl-N-[(tetrahvdro-2-furanv0methyl1acetamide
To a dry flask under a nitrogen atmosphere was added 0.5 g of the title compound of Step B, followed by 0.53 mL of triethylamine and 10 mL of anhydrous benzene. The flask was cooled to 0 °C and 1.92 mL of a 20% solution of phosgene in toluene was added over a period of 3 minutes. After stirring at room temperature for 45 min, the reaction mixture was partitioned between benzene/ethyl acetate and 1 Ν hydrochloric acid. The benzene/ethyl acetate layer was washed with brine, dried over sodium sulfate and concentrated to yield 0.6 g of the title compound of Step C as a liquid which was used as a starting material in the next step without further purification.
Step D: Preparation of 4-f2-chlorophenyl)-N-ethyl-4,5-dihydro-5-oxo-N-r(tetrahvdro-
Σ-furanvPmethyl"!" lH-tetrazole- 1 -carboxamide To 0.615 g of 1 -(2-chlorophenyl)- 1 ,4-dihydro-5H-tetrazol-5-one (prepared according to
Goto, T. et al. EP 578,090 A2) was added 10 mL of toluene, 382 mg of DMAP, 0.6 g of the title compound of Step C and the reaction was refluxed for 1 hour. The reaction mixture was cooled to room temperature, concentrated under reduced pressure and partitioned between 40 mL of methylene chloride and 25 mL of saturated aqueous ammonium chloride. The methylene chloride layer was dried over sodium sulfate, concentrated under reduced pressure and purified using silica gel column chromatography to yield 640 mg of the title compound of Step D, a compound of this invention, as a oil. JΗ ΝMR, CDC13: 7.6 - 7.4 (m, 4H), 4.2 - 3.2 (m, 7H), 2.1 - 1.2 (m, 7H).
EXAMPLE 7 Step A: Preparation of 1 -f2-chloro-6-fluorophenvD-l ,4-dihydro-5H-tetrazol-5-one
To 10 g of 2-chloro-6-fluorobenzoic acid was added 35 mL of thionyl chloride while keeping the reaction temperature at 0 °C. After the addition was complete the reaction mixture was refluxed for 4 hours, cooled to room temperature, and the excess thionyl chloride was removed under reduced pressure. To the resulting crude acid chloride was added 17.2 mL of trimethylsilyl azide and the contents refluxed for 18 hours. The reaction mixture was concentrated under reduced pressure and 20 mL of methanol was added. The reaction mixture was stirred at room temperature for 30 minutes and then concentrated under reduced pressure. The residue was crystallized from hexane to yield 11.2 g of the title compound of Step A as a solid melting at 136-138 °C. Ste B: Preparation of 4-(2-chloro-6-fluorophenyl)-N-(3 ,6-dihvdro-2H-pyran-4-yl)-
4.5-dihvdro-N-(l-methylethylV5-oxo-l /-tetrazole-l-carboxamide To 8.0 g of the title compound of Step A was added 60 mL of dioxane, 4.54 g of DMAP, 7.6 g of the title compound of Step B in Example 5 and the reaction was refluxed for 6 hours. The reaction mixture was then cooled to room temperature, concentrated under reduced pressure and partitioned between 300 mL of ethyl acetate and 150 mL of saturated aqueous ammonium chloride. The ethyl acetate layer was separated, dried over sodium sulfate, concentrated under reduced pressure and purified using silica gel column chromatography to yield 9.5 g of the title compound of Step B, a compound of this invention, as a solid melting at 91-93 °C. By the procedures described herein together with methods known in the art, the following compounds of Tables 1 and 2 can be prepared. The following notations have been used in Tables 1 and 2:
Figure imgf000026_0001
Figure imgf000027_0001
Figure imgf000027_0002
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
TABLE 1
Figure imgf000030_0002
0 2 B Q. R2 B
Q-4 C H5 B-l Q-4 cyc/o-C3H5 B-l
Q-4 C H5 B-2 Q-4 cclo-C^B.^ B-2
Q-4 C H5 B-3 Q-4 cyc/o-C3H5 B-3
Figure imgf000031_0001
Figure imgf000032_0001
Figure imgf000033_0001
Figure imgf000034_0001
Figure imgf000035_0001
Figure imgf000036_0001
Figure imgf000037_0001
Figure imgf000038_0001
Q-41 C H5 B-2 Q-41 cyclo-C3Hζ B-2
Q-41 C2H5 B-3 Q-41 cyclo-C3Η.ζ B-3
Q-41 C H5 B-4 Q-41 cyclo-C3Hζ B-4
Q-41 C2H5 B-5 Q-41 cyclo-C3 ζ B-5
Q-41 C2H5 B-6 Q-41 cyclo-C3Hζ B-6
Q-41 C H5 B-7 Q-41 cyclo-C3Η.ζ B-7
Q-41 C2H5 B-8 Q-41 cyclo-C3Ηζ B-8
Q-41 C2H5 B-9 Q-41 cyclo-C3Hζ B-9
Q-41 C2H5 B-10 Q-41 cyclo-C3Hζ B-10
Q-41 C2H5 B-l l Q-41 cyclo-C3Hζ B-l l
Q-41 C2H5 B-12 Q-41 cyclo-C3Hζ B-12
Q-41 C H5 B-13 Q-41 cycIo-C Hζ B-13
Q-41 C2H5 B-14 Q-41 cyclo-C3Hζ B-14
Q-41 C2H5 B-15 Q-41 cyclo-C Hζ B-15
Q-41 C H5 B-16 Q-41 cycIo-C Hζ B-16
Q-41 C2H5 B-17 Q-41 cyclo-C Hζ B-17
Q-41 C2H5 B-18 Q-41 cyclo-C Hζ B-18
Q-41 C H5 B-19 Q-41 cyclo-C Lζ B-19
Q-41 C2H5 B-20 Q-41 cyclo-C Hζ B-20
Q-41 C2H5 B-21 Q-41 cyclo-C Hζ B-21
Q-41 C2H5 B-22 Q-41 cyclo-C3Hζ B-22
Q-41 C2H5 B-23 Q-41 cyclo-C Hζ B-23
Q-41 C2H5 B-24 Q-41 cyclo-C3Hζ B-24
Q-41 C H5 B-25 Q-41 cyclo-C3 ζ B-25
Q-41 C2H5 B-26 Q-41 cyclo-C3Hζ B-26
Q-41 C H5 B-27 Q-41 cyclo-C3Hζ B-27
Q-41 C H5 B-28 Q-41 cyc!o-C Hζ B-28
Q-41 C2H5 B-29 Q-41 cycIo-C3Hζ B-29
Q-41 C2H5 B-30 Q-41 cyclo-C3Hζ B-30
Q-41 C2H5 B-31 Q-41 cyclo-C3Hs B-31
Q-41 C2H5 B-32 Q-41 cyclo-C3Η.$ B-32
Q-41 C H5 B-33 Q-41 cyclo-C3Hζ B-33
Q-41 C2H5 B-34 Q-41 cyclo-C Hζ B-34
Q-4 CH(CH3)2 B-l Q-4 CH2CH=CH2 B-l
Q-4 CH(CH3)2 B-2 Q-4 CH2CH=CH2 B-2
Q-4 CH(CH3)2 B-3 Q-4 CH2CH=CH2 B-3
Q-4 CH(CH3)2 B-4 Q-4 CH2CH=CH2 B-4
Q-4 CH(CH3)2 B-5
Figure imgf000039_0001
Q-4 CH2CH=CH2 B-5 Q-4 CH(CH3)2 B-6 B-6
Q-4 CH(CH3)2 B-7 B-7
Q-4 CH(CH3)2 B-8 B-8
Q-4 CH(CH3)2 B-9 B-9
Q-4 CH(CH3)2 B-10 B-10
Q-4 CH(CH3)2 B-l l B-l l
Q-4 CH(CH3)2 B-12 B-12
Q-4 CH(CH3)2 B-13 B-13
Q-4 CH(CH3)2 B-14 B-14
Q-4 CH(CH3)2 B-15 B-15
Q-4 CH(CH3)2 B-16 B-16
Q-4 CH(CH3)2 B-17 B-17
Q-4 CH(CH3)2 B-18 B-18
Q-4 CH(CH3)2 B-19 B-19
Q-4 CH(CH3)2 B-20 B-20
Q-4 CH(CH3)2 B-21 B-21
Q-4 CH(CH3)2 B-22 B-22
Q-4 CH(CH3)2 B-23 B-23
Q-4 CH(CH3)2 B-24 B-24
Q-4 CH(CH3)2 B-25 B-25
Q-4 CH(CH3)2 B-26 B-26
Q-4 CH(CH3)2 B-27 B-27
Q-4 CH(CH3)2 B-28 B-28
Q-4 CH(CH3)2 B-29 B-29
Q-4 CH(CH3)2 B-30 B-30
Q-4 CH(CH3)2 B-31 B-31
Q-4 CH(CH3)2 B-32 B-32
Q-4 CH(CH3)2 B-33 B-33
Q-4 CH(CH3)2 B-34 B-34
Q-10 CH(CH3)2 B-l B-l
Q-10 CH(CH3)2 B-2 B-2
Q-10 CH(CH3)2 B-3 B-3
Q-10 CH(CH3)2 B-4 B-4
Q-10 CH(CH3)2 B-5 B-5
Q-10 CH(CH3)2 B-6 B-6
Q-10 CH(CH3)2 B-7 B-7
Q-10 CH(CH3)2 B-8 B-8
Q-10 CH(CH3)2 B-9
Figure imgf000040_0001
B-9 Q-10 CH(CH3)2 B-10 B-10
Q-10 CH(CH3)2 B-l l B-l l
Q-10 CH(CH3)2 B-12 B-12
Q-10 CH(CH3)2 B-13 B-13
Q-10 CH(CH3)2 B-14 B-14
Q-10 CH(CH3)2 B-15 B-15
Q-10 CH(CH3)2 B-16 B-16
Q-10 CH(CH3)2 B-17 B-17
Q-10 CH(CH3)2 B-18 B-18
Q-10 CH(CH3)2 B-19 B-19
Q-10 CH(CH3)2 B-20 B-20
Q-10 CH(CH3)2 B-21 B-21
Q-10 CH(CH3)2 B-22 B-22
Q-10 CH(CH3)2 B-23 B-23
Q-10 CH(CH3)2 B-24 B-24
Q-10 CH(CH3)2 B-25 B-25
Q-10 CH(CH3)2 B-26 B-26
Q-10 CH(CH3)2 B-27 B-27
Q-10 CH(CH3)2 B-28 B-28
Q-10 CH(CH3)2 B-29 B-29
Q-10 CH(CH3)2 B-30 B-30
Q-10 CH(CH3)2 B-31 B-31
Q-10 CH(CH3)2 B-32 B-32
Q-10 CH(CH3)2 B-33 B-33
Q-10 CH(CH3)2 B-34 B-34
Q-15 CH(CH3)2 B-l B-l
Q-15 CH(CH3)2 B-2 B-2
Q-15 CH(CH3)2 B-3 B-3
Q-15 CH(CH3)2 B-4 B-4
Q-15 CH(CH3)2 B-5 B-5
Q-15 CH(CH3)2 B-6 B-6
Q-15 CH(CH3)2 B-7 B-7
Q-15 CH(CH3)2 B-8 B-8
Q-15 CH(CH3)2 B-9 B-9
Q-15 CH(CH3)2 B-10 B-10
Q-15 CH(CH3)2 B-l l B-l l
Q-15 CH(CH3)2 B-12 B-12
Q-15 CH(CH3)2 B-13
Figure imgf000041_0001
B-13 Q- 15 CH(CH3)2 B-14 B- 14
Q- 15 CH(CH3)2 B-15 B- l 5
Q-15 CH(CH3)2 B-16 B- 16
Q- 15 CH(CH3)2 B- 17 B- 17
Q-15 CH(CH3)2 B-18 B- 18
Q-15 CH(CH3)2 B-19 B-19
Q-15 CH(CH3)2 B-20 B-20
Q- 15 CH(CH3)2 B-21 B-21
Q-15 CH(CH3)2 B-22 B-22
Q-15 CH(CH3)2 B-23 B-23
Q-15 CH(CH3)2 B-24 B-24
Q-15 CH(CH3)2 B-25 B-25
Q-15 CH(CH3)2 B-26 B-26
Q-15 CH(CH3)2 B-27 B-27
•Q-15 CH(CH3)2 B-28 B-28
Q-15 CH(CH3)2 B-29 B-29
Q-15 CH(CH3)2 B-30 B-30
Q-15 CH(CH3)2 B-31 B-31
Q-15 CH(CH3)2 B-32 B-32
Q-15 CH(CH3)2 B-33 B-33
Q-15 CH(CH3)2 B-34 B-34
Q-13 CH(CH3)2 B-l B-l
Q-13 CH(CH3)2 B-2 B-2
Q-13 CH(CH3)2 B-3 B-3
Q-13 CH(CH3)2 B-4 B-4
Q-13 CH(CH3)2 B-5 B-5
Q-13 CH(CH3)2 B-6 B-6
Q-13 CH(CH3)2 B-7 B-7
Q-13 CH(CH3)2 B-8 B-8
Q-13 CH(CH3)2 B-9 B-9
Q-13 CH(CH3)2 B-10 B-10
Q-13 CH(CH3)2 B-l l B-l l
Q-13 CH(CH3)2 B-12 B-12
Q-13 CH(CH3)2 B-13 B-13
Q-13 CH(CH3)2 B-14 B-14
Q- 13 CH(CH3)2 B-15 B- 15
Q-13 CH(CH3)2 B-16 B- l 6
Q-13 CH(CH3)2 B-17
Figure imgf000042_0001
B- 17 Q-13 CH(CH3)2 B-18 B-18
Q-13 CH(CH3)2 B-19 B-19
Q-13 CH(CH3)2 B-20 B-20
Q-13 CH(CH3)2 B-21 B-21
Q-13 CH(CH3)2 B-22 B-22
Q-13 CH(CH3)2 B-23 B-23
Q-13 CH(CH3)2 B-24 B-24
Q-13 CH(CH3)2 B-25 B-25
Q-13 CH(CH3)2 B-26 B-26
Q-13 CH(CH3)2 B-27 B-27
Q-13 CH(CH3)2 B-28 B-28
Q-13 CH(CH3)2 B-29 B-29
Q-13 CH(CH3)2 B-30 B-30
Q-13 CH(CH3)2 B-31 B-31
Q-13 CH(CH3)2 B-32 B-32
Q-13 CH(CH3)2 B-33 B-33
Q-13 CH(CH3)2 B-34 B-34
Q-22 CH(CH3)2 B-l B-l
Q-22 CH(CH3)2 B-2 B-2
Q-22 CH(CH3)2 B-3 B-3
Q-22 CH(CH3)2 B-4 B-4
Q-22 CH(CH3)2 B-5 B-5
Q-22 CH(CH3)2 B-6 B-6
Q-22 CH(CH3)2 B-7 B-7
Q-22 CH(CH3)2 B-8 B-8
Q-22 CH(CH3)2 B-9 B-9
Q-22 CH(CH3)2 B-10 B-10
Q-22 CH(CH3)2 B-ll B-ll
Q-22 CH(CH3)2 B-12 B-12
Q-22 CH(CH3)2 B-13 B-13
Q-22 CH(CH3)2 B-14 B-14
Q-22 CH(CH3)2 B-15 B-15
Q-22 CH(CH3)2 B-16 B-16
Q-22 CH(CH3)2 B-17 B-17
Q-22 CH(CH3)2 B-18 B-18
Q-22 CH(CH3)2 B-19 B-19
Q-22 CH(CH3)2 B-20 B-20
Q-22 CH(CH3)2 B-21
Figure imgf000043_0001
B-21 Q-22 CH(CH3)2 B-22 B-22
Q-22 CH(CH3)2 B-23 B-23
Q-22 CH(CH3)2 B-24 B-24
Q-22 CH(CH3)2 B-25 B-25
Q-22 CH(CH3)2 B-26 β-26
Q-22 CH(CH3)2 B-27 B-27
Q-22 CH(CH3)2 B-28 B-28
Q-22 CH(CH3)2 B-29 B-29
Q-22 CH(CH3)2 B-30 B-30
Q-22 CH(CH3)2 B-31 B-31
Q-22 CH(CH3)2 B-32 B-32
Q-22 CH(CH3)2 B-33 B-33
Q-22 CH(CH3)2 B-34 B-34
Q-27 CH(CH3)2 B-l B-l
Q-27 CH(CH3)2 B-2 B-2
Q-27 CH(CH3)2 B-3 B-3
Q-27 CH(CH3)2 B-4 B-4
Q-27 CH(CH3)2 B-5 B-5
Q-27 CH(CH3)2 B-6 B-6
Q-27 CH(CH3)2 B-7 B-7
Q-27 CH(CH3)2 B-8 B-8
Q-27 CH(CH3)2 B-9 B-9
Q-27 CH(CH3)2 B-10 B-10
Q-27 CH(CH3)2 B-l l B-ll
Q-27 CH(CH3)2 B-12 B-12
Q-27 CH(CH3)2 B-13 B-13
Q-27 CH(CH3)2 B-14 B-14
Q-27 CH(CH3)2 B-15 B-15
Q-27 CH(CH3)2 B-16 B-16
Q-27 CH(CH3)2 B-17 B-17
Q-27 CH(CH3)2 B-18 B-18
Q-27 CH(CH3)2 B-19 B-19
Q-27 CH(CH3)2 B-20 B-20
Q-27 CH(CH3)2 B-21 B-21
Q-27 CH(CH3)2 B-22 B-22
Q-27 CH(CH3)2 B-23 B-23
Q-27 CH(CH3)2 B-24 B-24
Q-27 CH(CH3)2 B-25
Figure imgf000044_0001
B-25 Q-27 CH(CH3)2 B-26 B-26
Q-27 CH(CH3)2 B-27 B-27
Q-27 CH(CH3)2 B-28 B-28
Q-27 CH(CH3)2 B-29 B-29
Q-27 CH(CH3)2 B-30 B-30
Q-27 CH(CH3)2 B-31 B-31
Q-27 CH(CH3)2 B-32 B-32
Q-27 CH(CH3)2 B-33 B-33
Q-27 CH(CH3)2 B-34 B-34
Q-14 CH(CH3)2 B-l B-l
Q-14 CH(CH3)2 B-2 B-2
Q-14 CH(CH3)2 B-3 B-3
Q-14 CH(CH3)2 B-4 B-4
Q-14 CH(CH3)2 B-5 B-5
Q-14 CH(CH3)2 B-6 B-6
Q-14 CH(CH3)2 B-7 B-7
Q-14 CH(CH3)2 B-8 B-8
Q-14 CH(CH3)2 B-9 B-9
Q-14 CH(CH3)2 B-10 B-10
Q-14 CH(CH3)2 B-l l B-l l
Q-14 CH(CH3)2 B-12 B-12
Q-14 CH(CH3)2 B-13 B-13
Q-14 CH(CH3)2 B-14 B-14
Q-14 CH(CH3)2 B-15 B-l 5
Q-14 CH(CH3)2 B-16 B-l 6
Q-14 CH(CH3)2 B-17 B-17
Q-14 CH(CH3)2 B-18 B-18
Q-14 CH(CH3)2 B-19 B-19
Q-14 CH(CH3)2 B-20 B-20
Q-14 CH(CH3)2 B-21 B-21
Q-14 CH(CH3)2 B-22 B-22
Q-14 CH(CH3)2 B-23 B-23
Q-14 CH(CH3)2 B-24 B-24
Q-14 CH(CH3)2 B-25 B-25
Q-14 CH(CH3)2 B-26 B-26
Q-14 CH(CH3)2 B-27 B-27
Q-14 CH(CH3)2 B-28 B-28
Q-14 CH(CH3)2 B-29
Figure imgf000045_0001
B-29 Q-14 CH(CH3)2 B-30 B-30
Q-14 CH(CH3)2 B-31 B-31
Q-14 CH(CH3)2 B-32 B-32
Q-14 CH(CH3)2 B-33 B-33
Q-14 CH(CH3)2 B-34 B-34
Q-32 CH(CH3)2 B-l B-l
Q-32 CH(CH3)2 B-2 B-2
Q-32 CH(CH3)2 B-3 B-3
Q-32 CH(CH3)2 B-4 B-4
Q-32 CH(CH3)2 B-5 B-5
Q-32 CH(CH3)2 B-6 B-6
Q-32 CH(CH3)2 B-7 B-7
Q-32 CH(CH3)2 B-8 B-8
Q-32 CH(CH3)2 B-9 B-9
Q-32 CH(CH3)2 B-10 B-10
Q-32 CH(CH3)2 B-ll B-l l
Q-32 CH(CH3)2 B-12 B-12
Q-32 CH(CH3)2 B-13 B-13
Q-32 CH(CH3)2 B-14 B-14
Q-32 CH(CH3)2 B-15 B-15
Q-32 CH(CH3)2 B-16 B-16
Q-32 CH(CH3)2 B-17 B-17
Q-32 CH(CH3)2 B-18 B-18
Q-32 CH(CH3)2 B-19 B-19
Q-32 CH(CH3)2 B-20 B-20
Q-32 CH(CH3)2 B-21 B-21
Q-32 CH(CH3)2 B-22 B-22
Q-32 CH(CH3)2 B-23 B-23
Q-32 CH(CH3)2 B-24 B-24
Q-32 CH(CH3)2 B-25 B-25
Q-32 CH(CH3)2 B-26 B-26
Q-32 CH(CH3)2 B-27 B-27
Q-32 CH(CH3)2 B-28 B-28
Q-32 CH(CH3)2 B-29 B-29
Q-32 CH(CH3)2 B-30 B-30
Q-32 CH(CH3)2 B-31 B-31
Q-32 CH(CH3)2 B-32 B-32
Q-32 CH(CH3)2 B-33
Figure imgf000046_0001
B-33 Q-32 CH(CH3)2 B-34 B-34
Q-16 CH(CH3)2 B-l B-l
Q-16 CH(CH3)2 B-2 B-2
Q-16 CH(CH3)2 B-3 B-3
Q-16 CH(CH3)2 B-4 B-4
Q-16 CH(CH3)2 B-5 B-5
Q-16 CH(CH3)2 B-6 B-6
Q-16 CH(CH3)2 B-7 B-7
Q-16 CH(CH3)2 B-8 B-8
Q-16 CH(CH3)2 B-9 B-9
Q-16 CH(CH3)2 B-10 B-10
Q-16 CH(CH3)2 B-l l B-l l
Q-16 CH(CH3)2 B-12 B-12
Q-16 CH(CH3)2 B-13 B-13
Q-16 CH(CH3)2 B-14 B-14
Q-16 CH(CH3)2 B-15 B-15
Q-16 CH(CH3)2 B-16 B-16
Q-16 CH(CH3)2 B-17 B-17
Q-16 CH(CH3)2 B-18 B-18
Q-16 CH(CH3)2 B-19 B-19
Q-16 CH(CH3)2 B-20 B-20
Q-16 CH(CH3)2 B-21 B-21
Q-16 CH(CH3)2 B-22 B-22
Q-16 CH(CH3)2 B-23 B-23
Q-16 CH(CH3)2 B-24 B-24
Q-16 CH(CH3)2 B-25 B-25
Q-16 CH(CH3)2 B-26 B-26
Q-16 CH(CH3)2 B-27 B-27
Q-16 CH(CH3)2 B-28 B-28
Q-16 CH(CH3)2 B-29 B-29
Q-16 CH(CH3)2 B-30 B-30
Q-16 CH(CH3)2 B-31 B-31
Q-16 CH(CH3)2 B-32 B-32
Q-16 CH(CH3)2 B-33 B-33
Q-16 CH(CH3)2 B-34 B-34
Q-41 CH(CH3)2 B-l B-l
Q-41 CH(CH3)2 B-2 B-2
Q-41 CH(CH3)2 B-3
Figure imgf000047_0001
B-3 Q-41 B-4
Q-41 B-5
Q-41 B-6
Q-41 B-7
Q-41 B-8
Q-41 B-9
Q-41 B-10
Q-41 B-l l
Q-41 B-12
Q-41 B-13
Q-41 B-14
Q-41 B-15
Q-41 B-16
Q-41 B-17
Q-41 B-18
Q-41 B-19
Q-41 B-20
Q-41 B-21
Q-41 B-22
Q-41 B-23
Q-41 B-24
Q-41 B-25
Q-41 B-26
Q-41 B-27
Q-41 B-28
Q-41 B-29
Q-41 B-30
Q-41 B-31
Q-41 B-32
Q-41 B-33
Q-41 B-34
Q-4 B-l
Q-4 B-2
Q-4 B-3
Q-4 B-4
Q-4 B-5
Q-4 B-6
Q-4
Figure imgf000048_0001
B-7
Figure imgf000049_0001
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Q-22 C(=CH2)CH3 B-25 B-25
Q-22 C(=CH2)CH3 B-26 B-26
Q-22 C(=CH2)CH3 B-27 B-27
Q-22 C(=CH2)CH3 B-28 B-28
Q-22 C(=CH2)CH3 B-29 B-29
Q-22 C(=CH2)CH3 B-30 B-30
Q-22 C(=CH2)CH3 B-31 B-31
Q-22 C(=CH2)CH3 B-32 B-32
Q-22 C(=CH2)CH3 B-33 B-33
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Q-5 CH5 B-24 Q-5 CH(CH3)2 B-24
Q-5 C2H5 B-26 Q-5 CH(CH3)2 B-26
Q-5 CH5 B-27 Q-5 CH(CH3)2 B-27
Q-5 CH5 B-31 Q-5 CH(CH3)2 B-31
Q-6 CH5 B-l Q-6 CH(CH3)2 B-l
Q-6 CH5 B-2 Q-6 CH(CH3)2 B-2
Q-6 CH5 B-3 Q-6 CH(CH3)2 B-3
Q-6 C2H5 B-7 Q-6 CH(CH3)2 B-7
Q-6 CH5 B-9 Q-6 CH(CH3)2 B-9
Q-6 CH5 B-12 Q-6 CH(CH3)2 B-12
Q-6 C2H5 B-16 Q-6 CH(CH3)2 B-16
Q-6 C2H5 B-18 Q-6 CH(CH3)2 B-18
Q-6 C2H5 B-20 Q-6 CH(CH3)2 B-20
Q-6 C2H5 B-22 Q-6 CH(CH3)2 B-22
Q-6 C H5 B-23 Q-6 CH(CH3)2 B-23
Q-6 C2H5 B-24 Q-6 CH(CH3)2 B-24
Q-6 C H5 B-26 Q-6 CH(CH3)2 B-26
Q-6 C H5 B-27 Q-6 CH(CH3)2 B-27
Q-6 C2H5 B-31 Q-6 CH(CH3)2 B-31
Q-7 C2H5 B-l Q-7 CH(CH3)2 B-l
Q-7 C2H5 B-2 Q-7 CH(CH3)2 B-2
Q-7 C2H5 B-3 Q-7 CH(CH3)2 B-3
Q-7 C2H5 B-7 Q-7 CH(CH3)2 B-7
Q-7 C2H5 B-9 Q-7 CH(CH3)2 B-9
Q-7 C2H5 B-12 Q-7 CH(CH3)2 B-12
Q-7 C2H5 B-16 Q-7 CH(CH3)2 B-16
Q-7 CH5 B-18 Q-7 CH(CH3)2 B-18
Q-7 C2H5 B-20 Q-7 CH(CH3)2 B-20
Q-7 C2H5 B-22 Q-7 CH(CH3)2 B-22
Q-7 C2H5 B-23 Q-7 CH(CH3)2 B-23
Q-7 C2H5 B-24 Q-7 CH(CH3)2 B-24
Q-7 C2H5 B-26 Q-7 CH(CH3)2 B-26
Q-7 CH5 B-27 Q-7 CH(CH3)2 B-27
Q-7 CH5 B-31 Q-7 CH(CH3)2 B-31
Q-8 C2H5 B-l Q-8 CH(CH3)2 B-l
Q-8 C2H5 B-2 Q-8 CH(CH3)2 B-2
Q-8 C2H5 B-3 Q-8 CH(CH3)2 B-3
Q-8 CH5 B-7
Figure imgf000055_0001
Q-8 CH(CH3)2 B-7 Q-8 C2H5 B-9 Q-8 CH(CH3)2 B-9
Q-8 CH5 B-12 Q-8 CH(CH3)2 B-12
Q-8 C2H5 B-16 Q-8 CH(CH3)2 B-16
Q-8 C2H5 B-18 Q-8 CH(CH3)2 B-18
Q-8 CH5 B-20 Q-8 CH(CH3)2 B-20
Q-8 C2H5 B-22 Q-8 CH(CH3)2 B-22
Q-8 C2H5 B-23 Q-8 CH(CH3)2 B-23
Q-8 C2H5 B-24 Q-8 CH(CH3)2 B-24
Q-8 C2H5 B-26 Q-8 CH(CH3)2 B-26
Q-8 CH5 B-27 Q-8 CH(CH3)2 B-27
Q-8 CH5 B-31 Q-8 CH(CH3)2 B-31
Q-9 C2H5 B-l Q-9 CH(CH3)2 B-l
Q-9 C2H5 B-2 Q-9 CH(CH3)2 B-2
Q-9 C2H5 B-3 Q-9 CH(CH3)2 B-3
Q-9 CH5 B-7 Q-9 CH(CH3)2 B-7
Q-9 C2H5 B-9 Q-9 CH(CH3)2 B-9
Q-9 C2H5 B-12 Q-9 CH(CH3)2 B-12
Q-9 CH5 B-16 Q-9 CH(CH3)2 B-16
Q-9 C H5 B-18 Q-9 CH(CH3)2 B-18
Q-9 C2H5 B-20 Q-9 CH(CH3)2 B-20
Q-9 CH5 B-22 Q-9 CH(CH3)2 B-22
Q-9 C2H5 B-23 Q-9 CH(CH3)2 B-23
Q-9 C2H5 B-24 Q-9 CH(CH3)2 B-24
Q-9 C2H5 B-26 Q-9 CH(CH3)2 B-26
Q-9 C2H5 B-27 Q-9 CH(CH3)2 B-27
Q-9 C2H5 B-31 Q-9 CH(CH3)2 B-31
Q-ll C2H5 B-l Q-ll CH(CH3)2 B-l
Q-ll C2H5 B-2 Q-ll CH(CH3)2 B-2
Q-ll C2H5 B-3 Q-ll CH(CH3)2 B-3
Q-ll C2H5 B-7 Q-ll CH(CH3)2 B-7
Q-ll C2H5 B-9 Q-ll CH(CH3)2 B-9
Q-ll C2H5 B-12 Q-ll CH(CH3)2 B-12
Q-ll C H5 B-16 Q-ll CH(CH3)2 B-16
Q-ll C2H5 B-18 Q-ll CH(CH3)2 B-18
Q-ll C2H5 B-20 Q-ll CH(CH3)2 B-20
Q-ll C2H5 B-22 Q-ll CH(CH3)2 B-22
Q-ll C2H5 B-23 Q-ll CH(CH3)2 B-23
Q-ll C2H5 B-24
Figure imgf000056_0001
Q-ll CH(CH3)2 B-24 Q-ll C2H5 B-26 Q-ll CH(CH3)2 B-26
Q-ll CH5 B-27 Q-ll CH(CH3)2 B-27
Q-ll C2H5 B-31 Q-ll CH(CH3)2 B-31
Q-12 C2H5 B-l Q-12 CH(CH3)2 B-l
Q-12 C2H5 B-2 Q-12 CH(CH3)2 B-2
Q-12 C2H5 B-3 Q-12 CH(CH3)2 B-3
Q-12 CH5 B-7 Q-12 CH(CH3)2 B-7
Q-12 C2H5 B-9 Q-12 CH(CH3)2 B-9
Q-12 C H5 B-12 Q-12 CH(CH3)2 B-12
Q-12 C2H5 B-16 Q-12 CH(CH3)2 B-16
Q-12 C2H5 B-18 Q-12 CH(CH3)2 B-18
Q-12 C2H5 B-20 Q-12 CH(CH3)2 B-20
Q-12 CH5 B-22 Q-12 CH(CH3)2 B-22
Q-12 C2H5 B-23 Q-12 CH(CH3)2 B-23
Q-12 C2H5 B-24 Q-12 CH(CH3)2 B-24
Q-12 C H5 B-26 Q-12 CH(CH3)2 B-26
Q-12 C2H5 B-27 Q-12 CH(CH3)2 B-27
Q-12 C2H5 B-31 Q-12 CH(CH3)2 B-31
Q-21 C2H5 B-l Q-21 CH(CH3)2 B-l
Q-21 C2H5 B-2 Q-21 CH(CH3)2 B-2
Q-21 C2H5 B-3 Q-21 CH(CH3)2 B-3
Q-21 C2H5 B-7 Q-21 CH(CH3)2 B-7
Q-21 C2H5 B-9 Q-21 CH(CH3)2 B-9
Q-21 CH5 B-12 Q-21 CH(CH3)2 B-12
Q-21 C2H5 B-16 Q-21 CH(CH3)2 B-16
Q-21 C2H5 B-18 Q-21 CH(CH3)2 B-18
Q-21 C H5 B-20 Q-21 CH(CH3)2 B-20
Q-21 C2H5 B-22 Q-21 CH(CH3)2 B-22
Q-21 C H5 B-23 Q-21 CH(CH3)2 B-23
Q-21 C2H5 B-24 Q-21 CH(CH3)2 B-24
Q-21 C2H5 B-26 Q-21 CH(CH3)2 B-26
Q-21 C2H5 B-27 Q-21 CH(CH3)2 B-27
Q-21 C2H5 B-31 Q-21 CH(CH3)2 B-31
Q-29 C H5 B-l Q-29 CH(CH3)2 B-l
Q-29 C H5 B-2 Q-29 CH(CH3)2 B-2
Q-29 C2H5 B-3 Q-29 CH(CH3)2 B-3
Q-29 C2H5 B-7 Q-29 CH(CH3)2 B-7
Q-29 C H5 B-9
Figure imgf000057_0001
Q-29 CH(CH3)2 B-9 Q-29 C2H5 B-12 Q-29 CH(CH3)2 B-12
Q-29 C2H5 B-16 Q-29 CH(CH3)2 B-16
Q-29 CH5 B-18 Q-29 CH(CH3)2 B-18
Q-29 C2H5 B-20 Q-29 CH(CH3)2 B-20
Q-29 C2H5 B-22 Q-29 CH(CH3)2 B-22
Q-29 C2H5 B-23 Q-29 CH(CH3)2 B-23
Q-29 CH5 B-24 Q-29 CH(CH3)2 B-24
Q-29 C2H5 B-26 Q-29 CH(CH3)2 B-26
Q-29 CH5 B-27 Q-29 CH(CH3)2 B-27
Q-29 CH5 B-31 Q-29 CH(CH3)2 B-31
Q-34 C2H5 B-l Q-34 CH(CH3)2 B-l
Q-34 C2H5 B-2 Q-34 CH(CH3)2 B-2
Q-34 CH5 B-3 Q-34 CH(CH3)2 B-3
Q-34 C2H5 B-7 Q-34 CH(CH3)2 B-7
Q-34 C2H5 B-9 Q-34 CH(CH3)2 B-9
Q-34 C2H5 B-12 Q-34 CH(CH3)2 B-12
Q-34 C2H5 B-16 Q-34 CH(CH3)2 B-16
Q-34 C2H5 B-18 Q-34 CH(CH3)2 B-18
Q-34 C2H5 B-20 Q-34 CH(CH3)2 B-20
Q-34 CH5 B-22 Q-34 CH(CH3)2 B-22
Q-34 CH5 B-23 Q-34 CH(CH3)2 B-23
Q-34 CH5 B-24 Q-34 CH(CH3)2 B-24
Q-34 C2H5 B-26 Q-34 CH(CH3)2 B-26
Q-34 CH5 B-27 Q-34 CH(CH3)2 B-27
Q-34 CH5 B-31 Q-34 CH(CH3)2 B-31
Q-17 C2H5 B-l Q-17 CH(CH3)2 B-l
Q-17 C2H5 B-2 Q-17 CH(CH3)2 B-2
Q-17 C2H5 B-3 Q-17 CH(CH3)2 B-3
Q-17 C2H5 B-7 Q-17 CH(CH3)2 B-7
Q-17 C2H5 B-9 Q-17 CH(CH3)2 B-9
Q-17 C2H5 B-12 Q-17 CH(CH3)2 B-12
Q-17 C H5 B-16 Q-17 CH(CH3)2 B-16
Q-17 C2H5 B-18 Q-17 CH(CH3)2 B-18
Q-17 C2H5 B-20 Q-17 CH(CH3)2 B-20
Q-17 C2H5 B-22 Q-17 CH(CH3)2 B-22
Q-17 C2H5 B-23 Q-17 CH(CH3)2 B-23
Q-17 C2H5 B-24 Q-17 CH(CH3)2 B-24
Q-17 C2H5 B-26
Figure imgf000058_0001
Q-17 CH(CH3)2 B-26 Q-17 C2H5 B-27 Q-17 CH(CH3)2 B-27
Q-17 C2H5 B-31 Q-17 CH(CH3)2 B-31
Q-18 C2H5 B-l Q-18 CH(CH3)2 B-l
Q-18 C2H5 B-2 Q-18 CH(CH3)2 B-2
Q-18 C2H5 B-3 Q-18 CH(CH3)2 B-3
Q-18 C2H5 B-7 Q-18 CH(CH3)2 B-7
Q-18 C2H5 B-9 Q-18 CH(CH3)2 B-9
Q-18 C2H5 B-12 Q-18 CH(CH3)2 B-12
Q-18 C2H5 B-16 Q-18 CH(CH3)2 B-16
Q-18 C2H5 B-18 Q-18 CH(CH3)2 B-18
Q-18 C2H5 B-20 Q-18 CH(CH3)2 B-20
Q-18 C2H5 B-22 Q-18 CH(CH3)2 B-22
Q-18 C2H5 B-23 Q-18 CH(CH3)2 B-23
Q-18 C2H5 B-24 Q-18 CH(CH3)2 B-24
Q-18 C2H5 B-26 Q-18 CH(CH3)2 B-26
Q-18 C2H5 B-27 Q-18 CH(CH3)2 B-27
Q-18 C2H5 B-31 Q-18 CH(CH3)2 B-31
Q-19 CH5 B-l Q-19 CH(CH3)2 B-l
Q-19 C2H5 B-2 Q-19 CH(CH3)2 B-2
Q-19 CH5 B-3 Q-19 CH(CH3)2 B-3
Q-19 CH5 B-7 Q-19 CH(CH3)2 B-7
Q-19 C2H5 B-9 Q-19 CH(CH3)2 B-9
Q-19 C2H5 ' B-12 Q-19 CH(CH3)2 B-12
Q-19 C2H5 B-16 Q-19 CH(CH3)2 B-16
Q-19 C2H5 B-18 Q-19 CH(CH3)2 B-18
Q-19 C2H5 B-20 Q-19 CH(CH3)2 B-20
Q-19 C2H5 B-22 Q-19 CH(CH3)2 B-22
Q-19 C2H5 B-23 Q-19 CH(CH3)2 B-23
Q-19 C2H5 B-24 Q-19 CH(CH3)2 B-24
Q-19 C2H5 B-26 Q-19 CH(CH3)2 B-26
Q-19 C2H5 B-27 Q-19 CH(CH3)2 B-27
Q-19 CH5 B-31 Q-19 CH(CH3)2 B-31
Q-20 C2H5 B-l Q-20 CH(CH3)2 B-l
Q-20 C2H5 B-2 Q-20 CH(CH3)2 B-2
Q-20 C2H5 B-3 Q-20 CH(CH3)2 B-3
Q-20 C2H5 B-7 Q-20 CH(CH3)2 B-7
Q-20 C2H5 B-9 Q-20 CH(CH3)2 B-9
Q-20 CH5 B-12
Figure imgf000059_0001
Q-20 CH(CH3)2 B-12 Q-20 C2H5 B-16 Q-20 CH(CH3)2 B-16
Q-20 C2H5 B-18 Q-20 CH(CH3)2 B-18
Q-20 C2H5 B-20 Q-20 CH(CH3)2 B-20
Q-20 C2H5 B-22 Q-20 CH(CH3)2 B-22
Q-20 C2H5 B-23 Q-20 CH(CH3)2 B-23
Q-20 C2H5 B-24 Q-20 CH(CH3)2 B-24
Q-20 C2H5 B-26 Q-20 CH(CH3)2 B-26
Q-20 C2H5 B-27 Q-20 CH(CH3)2 B-27
Q-20 C2H5 B-31 Q-20 CH(CH3)2 B-31
Q-23 C H5 B-l Q-23 CH(CH3)2 B-l
Q-23 C2H5 B-2 Q-23 CH(CH3)2 B-2
Q-23 C2H5 B-3 Q-23 CH(CH3)2 B-3
Q-23 C H5 B-7 Q-23 CH(CH3)2 B-7
Q-23 C2H5 B-9 Q-23 CH(CH3)2 B-9
Q-23 C2H5 B-12 Q-23 CH(CH3)2 B-12
Q-23 C2H5 B-16 Q-23 CH(CH3)2 B-16
Q-23 CH5 B-18 Q-23 CH(CH3)2 B-18
Q-23 CH5 B-20 Q-23 CH(CH3)2 B-20
Q-23 C2H5 B-22 Q-23 CH(CH3)2 B-22
Q-23 C2H5 B-23 Q-23 CH(CH3)2 B-23
Q-23 C2H5 B-24 Q-23 CH(CH3)2 B-24
Q-23 C2H5 B-26 Q-23 CH(CH3)2 B-26
Q-23 C2H5 B-27 Q-23 CH(CH3)2 B-27
Q-23 C2H5 B-31 Q-23 CH(CH3)2 B-31
Q-24 CH5 B-l Q-24 CH(CH3)2 B-l
Q-24 C2H5 B-2 Q-24 CH(CH3)2 B-2
Q-24 C2H5 B-3 Q-24 CH(CH3)2 B-3
Q-24 C2H5 B-7 Q-24 CH(CH3)2 B-7
Q-24 C H5 B-9 Q-24 CH(CH3)2 B-9
Q-24 C2H5 B-12 Q-24 CH(CH3)2 B-12
Q-24 C2H5 B-16 Q-24 CH(CH3)2 B-16
Q-24 C2H5 B-18 Q-24 CH(CH3)2 B-18
Q-24 C2H5 B-20 Q-24 CH(CH3)2 B-20
Q-24 C2H5 B-22 Q-24 CH(CH3)2 B-22
Q-24 CH5 B-23 Q-24 CH(CH3)2 B-23
Q-24 C2H5 B-24 Q-24 CH(CH3)2 B-24
Q-24 CH5 B-26 Q-24 CH(CH3)2 B-26
Q-24 C2H5 B-27
Figure imgf000060_0001
Q-24 CH(CH3)2 B-27 CQ CQ CQ CQ CQ CQ
Figure imgf000061_0001
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ιrι in >r] t ι 'rs ιn ι >rs tn ιn ι ι ιn iΛ i ιn ιn ι ιn ιΛ in ι 'Λ in ιn ι ι ιn tn < ι^ x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x
P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P P
VO
Figure imgf000061_0003
O O O' O' O' O O' O' O' O O' O O o
o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o J OO OO OJ oo oo oo oo oo oo oo OJ J J OJ J OJ OJ OJ OO OO OO OO OJ J t to to to to t to to
_ _ © © © © © © © © o o o © © © © oo 00 oo oo 00 00 oo oo
Figure imgf000062_0001
to o too too too too too too too too too too too too too too too too too to too too too too too o o o o o o o o o o o o o o Xn oXn oXn oXn oXn oXn oXn oXn oXn oXn oXn oXft oXn oXn oXn oXn oXn oXn oXn oXn oXn oXn oXn oXn
Figure imgf000062_0002
oXn oXn oXn oXn oXn oXn oXn oXn oXn oXn oXn oXn oXn
co co co oo oo oo co co oo co CO CO 00 φ co co oo co co oo co co oo CO CO CO 00 00 ϋo oo oo co co co co co J to t to t to to >—* »_ CO CO
Os J> OJ t © oo O to <o - . OJ to >— j to to to t to t >_.
-. σs 4- J t © oo t to to to to to >—
»—* ~4 00 σs to o - . -4 σs 4- OJ to © 00
o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o oo oo oo oo oo oo oo oo oo OJ OJ oo o OJ OJ .OJ OJ OJ OJ OJ OJ OJ OJ OJ to to to to to to to to
© © © o © © © © © © © © © © © oo oo oo oo oo oo oo oo
O O O O -! >X >>X X o o o o
OJ OJ oo oo to to to to
Figure imgf000062_0003
ω OO CO OO OO DO OO OO DO OO rø tjj tjrj βj rø OO W DO CO CO CO 00 CO ^ ^ co co co co co ζ° oo oo co co cσ oo cσ
OJ to to to to to t »_ ' J to to t t
>— J _ _ _ ι ' ι ι i J tO rO O tO tO tO —
^1 σs 4- oo to o oo σs to VO -O J to 4- oo to © oo σs to vo ^J <J K' '^ ι-- ^ι σs 4- oo to © oo
Q-33 C2H5 B-l Q-33 CH(CH3)2 B-l
Q-33 C2H5 B-2 Q-33 CH(CH3)2 B-2
Q-33 C2H5 B-3 Q-33 CH(CH3)2 B-3
Q-33 C2H5 B-7 Q-33 CH(CH3)2 B-7
Q-33 C2H5 B-9 Q-33 CH(CH3)2 B-9
Q-33 C2H5 B-12 Q-33 CH(CH3)2 B-12
Q-33 C H5 B-16 Q-33 CH(CH3)2 B-16
Q-33 C2H5 B-18 Q-33 CH(CH3)2 B-18
Q-33 C2H5 B-20 Q-33 CH(CH3)2 B-20
Q-33 C2H5 B-22 Q-33 CH(CH3)2 B-22
Q-33 C2H5 B-23 Q-33 CH(CH3)2 B-23
Q-33 C2H5 B-24 Q-33 CH(CH3)2 B-24
Q-33 C2H5 B-26 Q-33 CH(CH3)2 B-26
Q-33 C2H5 B-27 Q-33 CH(CH3)2 B-27
Q-33 C2H5 B-31 Q-33 CH(GH3)2 B-31
Q-35 CH5 B-l Q-35 CH(CH3)2 B-l
Q-35 C2H5 B-2 Q-35 CH(CH3)2 B-2
Q-35 C2H5 B-3 Q-35 CH(CH3)2 B-3
Q-35 C2H5 B-7 Q-35 CH(CH3)2 B-7
Q-35 CH5 B-9 Q-35 CH(CH3)2 B-9
Q-35 C2H5 B-12 Q-35 CH(CH3)2 B-12
Q-35 C2H5 B-16 Q-35 CH(CH3)2 B-16
Q-35 C2H5 B-18 Q-35 CH(CH3)2 B-18
Q-35 C2H5 B-20 Q-35 CH(CH3)2 B-20
Q-35 C2H5 B-22 Q-35 CH(CH3)2 B-22
Q-35 C2H5 B-23 Q-35 CH(CH3)2 B-23
Q-35 CH5 B-24 Q-35 CH(CH3)2 B-24
Q-35 C2H5 B-26 Q-35 CH(CH3)2 B-26
Q-35 C2H5 B-27 Q-35 CH(CH3)2 B-27
Q-35 C2H5 B-31 Q-35 CH(CH3)2 B-31
Q-36 C2H5 B-l Q-36 CH(CH3)2 B-l
Q-36 C2H5 B-2 Q-36 CH(CH3)2 B-2
Q-36 C2H5 B-3 Q-36 CH(CH3)2 B-3
Q-36 C2H5 B-7 Q-36 CH(CH3)2 B-7
Q-36 C2H5 B-9 Q-36 CH(CH3)2 B-9
Q-36 C2H5 B-12 Q-36 CH(CH3)2 B-12
Q-36 CH5 B-16 Q-36 CH(CH3)2 B-16
Q-36 CH5 B-18
Figure imgf000063_0001
Q-36 CH(CH3)2 B-18 O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O O
OO 00 OO OO OO oo OO OO oo OJ OJ OJ OJ OJ J OJ J OJ OO OO OO oo oo OJ oo J OO oo J oo oo oo OO oo OO oo oo oo
VO oo 00 oo oo 00 oo oo oo oo 00 00 oo oo oo oo -o ^) -4 -4 ^4 - ^J ^J ^J -4 4 ^1 -^1 ^) ^1 σs σs σs σs σs σs Os
to o too too too too too too too too too too too too too too too too too too too too too too o o o o o o o o o o o o o o o X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X X on on on on on on on on on on on on on on on on Oh On on on on on on on oi on on on on on on on on on on on on OΛ
CO w co co oo co co co co co co CO CO CO CO CO CO OO OO M M r-i M tri CO CO CO CO CO CO OO
- OJ to t to to t to -_ -_ -_ φ φ φ CO CO OO OO to to to t to o to to to to σs 4- OJ to o 00 σs to to ' to
>— -4 σs 4- OJ to © 00 σs to VO t "o^ >- ω_* to t -o. OS 4- OJ t ©
Figure imgf000064_0001
o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o o
OJ OJ OJ J OJ OJ OJ OJ J J J J OJ OJ J OJ OJ OJ OJ OJ OJ J J J J J J OJ OJ OJ OJ OJ J OJ J
VO 00 00 oo 00 00 00 oo 00 00 00 00 00 00 00 00 ^1 ^1 ~ -4 ~1 -o J OJ OJ -4 -4 -4 σs σs σs OS' σs σs σs
o o n o o o o o o o o o o p o o o o o o o o o o o o o o o o o o o O O O o
X X X X X X X X X X X 5 z X— \ z X— \ S Ε X hH X t-H S Ε S l-H I-H X X x x x x x x x x X o o o o o o o o o o o o o o O o o o o o O O O O O O o ._ o .- o O
X XJ O XO O X X O O XJ O XJ O XJ O XJ O XJ O XJ O XJ .OXJ O X o o o o o o o
OO O J XJ. OJ O XJ O .XJ .OX X J O XJ OJ O XJ O XJ OJ .OXJ .OXJ .OxJ O XJ OJ OJ OJ OJ OJ OJ OJ OJ OJ O XJ O XJ to to to to to to to to to to to to to to to to to to to to to to to to t^ to' to to' to' to' to' to' to' to'
φ φ φ φ φ φ CO CO CO CO CO CO CO t φto -φ_ φ -_ w w a a oo
Figure imgf000064_0002
I_. --j t to to
Figure imgf000064_0003
O ' OJ to ' OJ to to to to to to σs 4- J to © oo t V' σs 4- OJ to ©
Q-39 C2H5 B-2 Q-39 CH(CH3)2 B-2
Q-39 C2H5 B-3 Q-39 CH(CH3)2 B-3
Q-39 C2H5 B-7 Q-39 CH(CH3)2 B-7
Q-39 C2H5 B-9 Q-39 CH(CH3)2 B-9
Q-39 C2H5 B-12 Q-39 CH(CH3)2 B-12
Q-39 C2H5 B-16 Q-39 CH(CH3)2 B-16
Q-39 C2H5 B-18 Q-39 CH(CH3)2 B-18
Q-39 C2H5 B-20 Q-39 CH(CH3)2 B-20
Q-39 C H5 B-22 Q-39 CH(CH3)2 B-22
Q-39 C2H5 B-23 Q-39 CH(CH3)2 B-23
Q-39 CH5 B-24 Q-39 CH(CH3)2 B-24
Q-39 C2H5 B-26 Q-39 CH(CH3)2 B-26
Q-39 C2H5 B-27 Q-39 CH(CH3)2 B-27
Q-39 C2H5 B-31 Q-39 CH(CH3)2 B-31
Q-40 C2H5 B-l Q-40 CH(CH3)2 B-l
Q-40 C2H5 B-2 Q-40 CH(CH3)2 B-2
Q-40 C2H5 B-3 Q-40 CH(CH3)2 B-3
Q-40 C2H5 B-7 Q-40 CH(CH3)2 B-7
Q-40 C2H5 B-9 Q-40 CH(CH3)2 B-9
Q-40 C2H5 B-12 Q-40 CH(CH3)2 B-12
Q-40 C2H5 B-16 Q-40 CH(CH3)2 B-16
Q-40 C2H5 B-18 Q-40 CH(CH3)2 B-18
Q-40 C2H5 B-20 Q-40 CH(CH3)2 B-20
Q-40 C2H5 B-22 Q-40 CH(CH3)2 B-22
Q-40 CH5 B-23 Q-40 CH(CH3)2 B-23
Q-40 CH5 B-24 Q-40 CH(CH3)2 B-24
Q-40 C2H5 B-26 Q-40 CH(CH3)2 B-26
Q-40 C2H5 B-27 Q-40 CH(CH3)2 B-27
Q-40 C2H5 B-31 Q-40 CH(CH3)2 B-31
Q-42 C2H5 B-l Q-42 CH(CH3)2 B-l
Q-42 C2H5 B-2 Q-42 CH(CH3)2 B-2
Q-42 C2H5 B-3 Q-42 CH(CH3)2 B-3
Q-42 C2H5 B-7 Q-42 CH(CH3)2 B-7
Q-42 C2H5 B-9 Q-42 CH(CH3)2 B-9
Q-42 C2H5 B-12 Q-42 CH(CH3)2 B-12
Q-42 CH5 B-16 Q-42 CH(CH3)2 B-16
Q-42 CH5 B-18 Q-42 CH(CH3)2 B-18
Q-42 CH5 B-20
Figure imgf000065_0001
Q-42 CH(CH3)2 B-20 Q-42 C2H5 B-22 Q-42 CH(CH3)2 B-22
Q-42 C2H5 B-23 Q-42 CH(CH3)2 B-23
Q-42 C2H5 B-24 Q-42 CH(CH3)2 B-24
Q-42 C2H5 B-26 Q-42 CH(CH3)2 B-26
Q-42 C2H5 B-27 Q-42 CH(CH3)2 B-27
Q-42 C2H5 B-31 Q-42 CH(CH3)2 B-31
Q-43 C H5 B-l Q-43 CH(CH3)2 B-l
Q-43 C2H5 B-2 Q-43 CH(CH3)2 B-2
Q-43 C2H5 B-3 Q-43 CH(CH3)2 B-3
Q-43 C2H5 B-7 Q-43 CH(CH3)2 B-7
Q-43 C H5 B-9 Q-43 CH(CH3)2 B-9
Q-43 C2H5 B-12 Q-43 CH(CH3)2 B-12
Q-43 C2H5 B-16 Q-43 CH(CH3)2 B-16
Q-43 C2H5 B-18 Q-43 CH(CH3)2 B-18
Q-43 C2H5 B-20 Q-43 CH(CH3)2 B-20
Q-43 C2H5 B-22 Q-43 CH(CH3)2 B-22
Q-43 C2H5 B-23 Q-43 CH(CH3)2 B-23
Q-43 C2H5 B-24 Q-43 CH(CH3)2 B-24
Q-43 C H5 B-26 Q-43 CH(CH3)2 B-26
Q-43 C2H5 B-27 Q-43 CH(CH3)2 B-27
Q-43 C2H5 B-31 Q-43 CH(CH3)2 B-31
Q-l cyclo-C3Hζ B-l Q-23 cyclo-C3Ηζ B-l
Q-l cyclo-C3 ζ B-2 Q-23 cycio-C3H5 B-2
Q-l cyclo-C3Kζ B-3 Q-23 cyclo-C3Hζ B-3
Q-l cyc/o-C3H5 B-7 Q-23 cyclo-C Hζ B-7
Q-l cyclo-C3Hζ B-9 Q-23 cyclo-C3ϊiζ B-9
Q-l cyclo-C3H5 B-12 Q-23 cyclo-C3U5 B-12 Q-l cyclo-C Η.ζ B-16 Q-23 cyclo-C3H5 B-16
Q-l cyclo-C3Hζ B-18 Q-23 cyclo-C3Hζ B-18 Q-l cyc!o-C3Η.ζ B-20 Q-23 cyclo-C3U5 B-20
Q-l cyclo-C3H$ B-22 Q-23 cyclo-C3H5 B-22 Q-l cyclo-C Hζ B-23 Q-23 cyclo-C H§ B-23 Q-l cyclo-C3Hζ B-24 Q-23 cyclo-C3Hζ B-24 Q-l cyclo-C Η.ζ B-26 Q-23 cych-C Ηζ B-26 Q-l cyclo-C3liζ B-27 Q-23 cyclo-C3Hζ B-27 Q-l cyclo-C3Hζ B-31 Q-23 cyclo-C3H$ B-31 Q-2 cyclo-C3Uζ B-l Q-24 cycIo-C Hζ B-l Q-2 cyclo-C3H.ζ B-2
Figure imgf000066_0001
Q-24 cyclo-C3Hζ B-2 Q-2 B-3
Q-2 B-7
Q-2 B-9
Q-2 B-12
Q-2 B-16
Q-2 B-18
Q-2 B-20
Q-2 B-22
Q-2 B-23
Q-2 B-24
Q-2 B-26
Q-2 B-27
Q-2 B-31
Q-3 B-l
0-3 B-2
Q-3 B-3
Q-3 B-7
Q-3 B-9
Q-3 B-12
Q-3 B-16
Q-3 B-18
Q-3 B-20
Q-3 B-22
Q-3 B-23
Q-3 B-24
Q-3 B-26
Q-3 B-27
Q-3 B-31
Q-5 B-l
Q-5 B-2
Q-5 B-3
Q-5 B-7
Q-5 B-9
Q-5 B-12
Q-5 B-16
Q-5 B-18
Q-5 B-20
Q-5
Figure imgf000067_0001
B-22 Q-5 B-23
Q-5 B-24
Q-5 B-26
Q-5 B-27
Q-5 B-31
Q-6 B-l
Q-6 B-2
Q-6 B-3
Q-6 B-7
Q-6 B-9
Q-6 B-12
Q-6 B-16
Q-6 B-18
Q-6 B-20
Q-6 B-22
Q-6 B-23
Q-6 B-24
Q-6 B-26
Q-6 B-27
Q-6 B-31
Q-7 B-l
Q-7 B-2
Q-7 B-3
Q-7 B-7
Q-7 B-9
Q-7 B-12
Q-7 B-16
Q-7 B-18
Q-7 B-20
Q-7 B-22
Q-7 B-23
Q-7 B-24
Q-7 B-26
Q-7 B-27
Q-7 B-31
Q-8 B-l
Q-8 B-2
Q-8 B-3
Figure imgf000068_0001
Q-8 cyclo-C Hζ B-7 B-7
Q-8 cyclo-C Uζ B-9 B-9
Q-8 cyclo-C3Hζ B-12 B-12
Q-8 cyclo-C3Uζ B-16 B-16
Q-8 cyclo-C3E.ζ B-18 B-18
Q-8 cyclo-C3Hζ B-20 B-20
Q-8 cyclo-C Η.ζ B-22 B-22
Q-8 cyclo-C3Hζ B-23 B-23
Q-8 cyclo-C3Η.ζ B-24 B-24
Q-8 cyclo-C Hζ B-26 B-26
Q-8 cycIo-C3Hζ B-27 B-27
Q-8 cyclo-C3Hζ B-31 B-31
Q-9 cyc/o-C3H5 B-l B-l
Q-9 cych-C3Hζ B-2 B-2
Q-9 cyclo-C3Hζ B-3 B-3
Q-9 cyclo-C Η.ζ B-7 B-7
Q-9 cyclo-C3H§ B-9 B-9
Q-9 cyclo-C3Hζ B-12 B-12
Q-9 cyclo-C Hζ B-16 B-16
Q-9 cyclo-C Η.ζ B-18 B-18
Q-9 cyclo-C3Hζ B-20 B-20
Q-9 cyclo-C3Hζ B-22 B-22
Q-9 cyclo-C E.ζ B-23 B-23
Q-9 cyclo-C3H5 B-24 B-24
Q-9 cycIo-C3Hζ B-26 B-26
Q-9 cyclo-C3Hζ B-27 B-27
Q-9 cyclo-C3H5 B-31 B-31
Q-ll cycIo-C Hζ B-l B-l
Q-ll cycIo-C3Hζ B-2 B-2
Q-ll cycIo-C Η.ζ B-3 B-3
Q-ll cych-C3Hζ B-7 B-7
Q-ll cyclo-C3Hζ B-9 B-9
Q-ll cyclo-C Hζ B-12 B-12
Q-ll cyclo-C3H$ B-16 B-16
Q-ll cyclo-C3Jiζ B-18 B-18
Q-ll cyclo-C3Hζ B-20 B-20
Q-ll cyclo-C3H§ B-22 B-22
Q-ll cyclo-C3Hζ B-23 B-23
Figure imgf000069_0001
Q-l l B-24
Q-l l B-26
Q-l l B-27
Q-l l B-31
Q-12 B-l
Q-12 B-2
Q-12 B-3
Q-12 B-7
Q-12 B-9
Q-12 B-12
Q-12 B-16
Q-12 B-18
Q-12 B-20
Q-12 B-22
Q-12 B-23
Q-12 B-24
Q-12 B-26
Q-12 B-27
Q-12 B-31
Q-21 B-l
Q-21 B-2
Q-21 B-3
Q-21 B-7
Q-21 B-9
Q-21 B-12
Q-21 B-16
Q-21 B-18
Q-21 B-20
Q-21 B-22
Q-21 B-23
Q-21 B-24
Q-21 B-26
Q-21 B-27
Q-21 B-31
Q-29 B-l
Q-29 B-2
Q-29 B-3
Q-29
Figure imgf000070_0001
B-7 Q-29 B-9
Q-29 B-12
Q-29 B-16
Q-29 B-18
Q-29 B-20
Q-29 B-22
Q-29 B-23
Q-29 B-24
Q-29 B-26
Q-29 B-27
Q-29 B-31
Q-34 B-l
Q-34 B-2
Q-34 B-3
Q-34 B-7
Q-34 B-9
Q-34 B-12
Q-34 B-16
Q-34 B-18
Q-34 B-20
Q-34 B-22
Q-34 B-23
Q-34 B-24
Q-34 B-26
Q-34 B-27
Q-34 B-31
Q-17 B-l
Q-17 B-2
Q-17 B-3
Q-17 B-7
Q-17 B-9
Q-17 B-12
Q-17 B-16
Q-17 B-l 8
Q-17 B-20
Q-17 B-22
Q-17 B-23
Q-17
Figure imgf000071_0001
B-24 Q-40 cyclo-C3H$ B-26
Q-40 cyclo-C3H5 B-27
Q-40 cyclo-C3U5 B-31
Q-42 cyclo-C3H$ B-l
Q-42 cyclo-C3 H5 B-2
Q-42 cyclo-C3U5 B-3
Q-42 cyclo-C3H5 B-7
Q-42 cyclo-C3Hζ B-9
Q-42 cyclo-C3U5 B-12
Q-42 cyclo-C Hζ B-16
Q-42 cyclo-C3ϊlζ B-18
Q-42 cyclo-C3H5 B-20
Q-42 cyclo-C Hζ B-22
Q-42 cyclo-C Hζ B-23
Q-42 cyclo-C H$ B-24
Q-42 cych-C3Η.ζ B-26
Q-42 cyclo-C3Uζ B-27
Q-42 cyclo-C3Hζ B-31
Q-43 cyclo-C3Hζ B-l
Q-43 cyclo-C3Hζ B-2
Q-43 cyclo-C3H5 B-3
Q-43 cyclo-C3Hζ B-7
Q-43 cyc/o-C3H5 B-9
Q-43 cyclo-C3H5 B-12
Q-43 cyclo-C3Hζ B-16
Q-43 cyclo-C Η.ζ B-18
Q-43 cyclo-C3U5 B-20
Q-43 cyclo-C3H$ B-22
Q-43 cyc/o-C3H5 B-23
Q-43 cyclo-C Hζ B-24
Q-43 cyclo-C3Hζ B-26
Q-43 cyclo-C3Kζ B-27
Q-43 cyclo-C3U5 B-31
Figure imgf000072_0001
Figure imgf000073_0001
TABLE 3
Figure imgf000073_0002
Figure imgf000074_0001
Formulation/Utilitv
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.
Weight Percent
Active Ingredient Diluent Surfactant
Water-Dispersible and Water-soluble 5-90 0-94 1-15 Granules, Tablets and Powders.
Suspensions, Emulsions, Solutions 5-50 40-95 0-15 (including Emulsifiable Concentrates)
Dusts 1-25 70-99 0-5
Granules and Pellets 0.01-99 5-99.99 0-15
High Strength Compositions 90-99 0-10 0-2 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, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. Dusts and powders can be prepared by blending and, usually, grinding as in a hammer mill or fluid-energy mill. Suspensions are usually prepared by wet-milling; see, for example, U.S. 3,060,084. Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry 's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. 4,172,714.
Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566. For further information regarding the art of formulation, see U.S. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41; U.S. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; and Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989.
In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. Compound numbers refer to compounds in Index Tables A-H.' Example A
High Strength Concentrate
Compound 27 98.5% silica aerogel 0.5% synthetic amorphous fine silica 1.0%. Example B
Wettable Powder
Compound 52 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%. Example C Granule
Compound 53 10.0% attapulgite granules (low volatile matter, 0.71/0.30 mm; U.S.S. No. 25-50 sieves) 90.0%.
Example D Extruded Pellet
Compound 65 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). 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. 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, chlomethoxyfen, chloramben, chlorbromuron, chloridazon, chlorimuron-ethyl, chlornitrofen, chlorotoluron, chlorpropham, chlorsulfuron, chlorthal-dimethyl, cinmethylin, cinosulfuron, clethodim, clomazone, clopyralid, clopyralid-olamine, cyanazine, cycloate, cyclosulfamuron, 2,4-D and its butotyl, butyl, isoctyl and isopropyl esters and its dimethylammonium, diolamine and trolamine salts, daimuron, dalapon, dalapon-sodium, dazomet, 2,4-DB and its dimethylammonium, potassium and sodium salts, desmedipham, desmetryn, dicamba and its diglycolammonium, dimethylammonium, potassium and sodium salts, dichlobenil, dichlorprop, diclofop-methyl, 2-[4,5-dihydro-4-methyl-4-(l-methylethyl)-5-oxo-lH-imidazol-2-yl]-5-methyl-3- pyridinecarboxylic acid (AC 263,222), difenzoquat metilsulfate, diflufenican, dimepiperate, dimethenamid, dimethylarsinic acid and its sodium salt, dinitramine, diphenamid, diquat dibromide, dithiopyr, diuron, DNOC, endothal, EPTC, esprocarb, ethalfluralin, ethametsulfuron-methyl, ethofumesate, ethoxysulfuron, fenoxaprop-ethyl, fenoxaprop-P-ethyl, fenuron, fenuron-TCA, flamprop-methyl, flamprop-M-isopropyl, fiamprop-M-methyl, flazasulfuron, fluazifop-butyl, fluazifop-P-butyl, fluchloralin, flumetsulam, flumiclorac-pentyl, flumioxazin, fluometuron, fluoroglycofen-ethyl, flupoxam, flupyrsulfuron-methyl and its sodium salt, fluridone, flurochloridone, fluroxypyr, fluthiacet-methyl, fomesafen, fosamine-ammonium, glufosinate, glufosinate-ammonium, glyphosate, glyphosate-isopropylammonium, glyphosate-sesquisodium, glyphosate-trimesium, halosulfuron-methyl, haloxyfop-etotyl, haloxy fop-methyl, hexazinone, imazamethabenz-methyl, imazamox, imazapyr, imazaquin, imazaquin-ammonium, imazethapyr, imazethapyr-ammonium, imazosulfuron, ioxynil, ioxynil octanoate, ioxynil-sodium, isoproturon, isouron, isoxaben, isoxaflutole, lactofen, lenacil, linuron, maleic hydrazide, MCPA and its dimethylammonium, potassium and sodium salts, MCPA-isoctyl, mecoprop, mecoprop-P, mefenacet, mefluidide, metam-sodium, methabenzthiazuron, methylarsonic acid and its calcium, monoammonium, monosodium and disodium salts, methyl [[[l-[5-[2-chloro-4-(trifluoromethyl)phenoxy]-2-nitrophenyl]-2- methoxyethylidene]amino]oxy]acetate (AKH-7088), methyl 5-[[[[(4,6-dimethyl-2- pyrimidinyl)amino]carbonyl]amino]sulfonyl]- 1 -(2-pyridinyl)- lH-pyrazole-4-carboxylate (NC-330), metobenzuron, metolachlor, metosulam, metoxuron, metribuzin, metsulfuron-methyl, molinate, monolinuron, napropamide, naptalam, neburon, nicosulfuron, norflurazon, oryzalin, oxadiazon, oxasulfuron, oxyfluorfen, paraquat dichloride, pebulate, pendimethalin, pentoxazone (KPP-314), perfluidone, phenmedipham, picloram, picloram-potassium, pretilachlor, primisulfuron-methyl, prometon, prometryn, propachlor, propanil, propaquizafop, propazine, propham, propyzamide, prosulfuron, pyrazolynate, pyrazosulfuron-ethyl, pyridate, pyriminobac-methyl, pyrithiobac, pyrithiobac-sodium, quinclorac, quizalofop-ethyl, quizalofop-P-ethyl, quizalofop-P-tefuryl, rimsulfuron, sethoxydim, siduron, simazine, sulcotrione (ICIA0051), sulfentrazone, sulfometuron-methyl, TCA, TCA-sodium, tebuthiuron, terbacil, terbuthylazine, terbutryn, thenylchlor, thiafluamide (BAY 11390), thifensulfuron-methyl, thiobencarb, tralkoxydim, tri-allate, triasulfuron, triaziflam, tribenuron-methyl, triclopyr, triclopyr-butotyl, triclopyr-triethylammonium, tridiphane, trifluralin, triflusulfuron-methyl, vernolate, benzofenap, bromobutide, cafenstrole, cumyluron, cyhalofop-butyl, dymron, etobenzanid, fentrazamide, molinate, oxadiargyl, oxaziclomefone, pyribenzoxim, and pyributicarb.
In certain instances, combinations with other herbicides having a similar spectrum of control but a different mode of action will be particularly advantageous for preventing the development of resistant weeds. Preferred for better control of undesired vegetation in rice (e.g., lower use rate, broader spectrum of weeds controlled, or enhanced crop safety) or for preventing the development of resistant weeds in rice are mixtures of a compound of this invention with a herbicide selected from the group 2,4-D, anilofos, azimsulfuron, benfuresate, bensulfuron-methyl, bensulfuron- methyl in combination with metsulfuron-methyl, benzofenap, bispyribac-sodium, bromobutide, cafenstrole, carfentrazone, chlorimuron-ethyl, cinosulfuron, clomazone, cumyluron, cyclosulfamuron, cyhalofop-butyl, dimepiperate, dithiopyr, dymron, esprocarb, ethoxysulfuron, etobenzanid, fentrazamide, halosulfuron-methyl, imazosulfuron, indanofan, MCPA, mefenacet, metsulfuron-methyl, metsulfuron-methyl in combination with chlorimuron-ethyl, molinate, oxadiargyl, oxadiazon, oxaziclomefone, pentoxazone, pretilachlor, propanil, pyrazolate, pyrazosulfuron-ethyl, pyribenzoxim, pyributicarb, pyriminobac-methyl, quinchlorac, thenylchlor, and thiobencarb.
Specifically preferred mixtures (compound numbers refer to compounds in Index Tables A-H) are selected from the group: compound 27 and azimsulfuron, compound 27 and benfuresate, compound 27 and bensulfuron-methyl, compound 27 and benzofenap, compound 27 and bispyribac-sodium, compound 27 and carfentrazone, compound 27 and chlorimuron-ethyl, compound 27 and cinosulfuron, compound 27 and cyclosulfamuron, compound 27 and dymron, compound 27 and ethoxysulfuron, compound 27 and halosulfuron-methyl, compound 27 and imazosulfuron, compound 27 and metsulfuron- methyl, compound 27 and oxaziclomefone, compound 27 and pentoxazone, compound 27 and propanil, compound 27 and pyrazolate, compound 27 and pyrazosulfuron-ethyl, compound 27 and pyribenzoxim, compound 27 and pyriminobac-methyl; compound 46 and azimsulfuron, compound 46 and benfuresate, compound 46 and bensulfuron-methyl, compound 46 and benzofenap, compound 46 and bispyribac-sodium, compound 46 and carfentrazone, compound 46 and chlorimuron-ethyl, compound 46 and cinosulfuron, compound 46 and cyclosulfamuron, compound 46 and dymron, compound 46 and ethoxysulfuron, compound 46 and halosulfuron-methyl, compound 46 and imazosulfuron, compound 46 and metsulfuron-methyl, compound 46 and oxaziclomefone, compound 46 and pentoxazone, compound 46 and propanil, compound 46 and pyrazolate, compound 46 and pyrazosulfuron-ethyl, compound 46 and pyribenzoxim, compound 46 and pyriminobac- methyl; compound 50 and azimsulfuron, compound 50 and benfuresate, compound 50 and bensulfuron-methyl, compound 50 and benzofenap, compound 50 and bispyribac-sodium, compound 50 and carfentrazone, compound 50 and chlorimuron-ethyl, compound 50 and cinosulfuron, compound 50 and cyclosulfamuron, compound 50 and dymron, compound 50 and ethoxysulfuron, compound 50 and halosulfuron-methyl, compound 50 and imazosulfuron, compound 50 and metsulfuron-methyl, compound 50 and oxaziclomefone, compound 50 and pentoxazone, compound 50 and propanil, compound 50 and pyrazolate, compound 50 and pyrazosulfuron-ethyl, compound 50 and pyribenzoxim, compound 50 and pyriminobac-methyl; compound 52 and azimsulfuron, compound 52 and benfuresate, compound 52 and bensulfuron-methyl, compound 52 and benzofenap, compound 52 and bispyribac-sodium, compound 52 and carfentrazone, compound 52 and chlorimuron-ethyl, compound 52 and cinosulfuron, compound 52 and cyclosulfamuron, compound 52 and dymron, compound 52 and ethoxysulfuron, compound 52 and halosulfuron-methyl, compound 52 and imazosulfuron, compound 52 and metsulfuron-methyl, compound 52 and oxaziclomefone, compound 52 and pentoxazone, compound 52 and propanil, compound 52 and pyrazolate, compound 52 and pyrazosulfuron-ethyl, compound 52 and pyribenzoxim, compound 52 and pyriminobac-methyl; compound 53 and azimsulfuron, compound 53 and benfuresate, compound 53 and bensulfuron-methyl, compound 53 and benzofenap, compound 53 and bispyribac-sodium, compound 53 and carfentrazone, compound 53 and chlorimuron-ethyl, compound 53 and cinosulfuron, compound 53 and cyclosulfamuron, compound 53 and dymron, compound 53 and ethoxysulfuron, compound 53 and halosulfuron-methyl, compound 53 and imazosulfuron, compound 53 and metsulfuron- methyl, compound 53 and oxaziclomefone, compound 53 and pentoxazone, compound 53 and propanil, compound 53 and pyrazolate, compound 53 and pyrazosulfuron-ethyl, compound 53 and pyribenzoxim, compound 53 and pyriminobac-methyl; compound 65 and azimsulfuron, compound 65 and benfuresate, compound 65 and bensulfuron-methyl, compound 65 and benzofenap, compound 65 and bispyribac-sodium, compound 65 and carfentrazone, compound 65 and chlorimuron-ethyl, compound 65 and cinosulfuron, compound 65 and cyclosulfamuron, compound 65 and dymron, compound 65 and ethoxysulfuron, compound 65 and halosulfuron-methyl, compound 65 and imazosulfuron, compound 65 and metsulfuron-methyl, compound 65 and oxaziclomefone, compound 65 and pentoxazone, compound 65 and propanil, compound 65 and pyrazolate, compound 65 and pyrazosulfuron-ethyl, compound 65 and pyribenzoxim, compound 65 and pyriminobac- methyl; compound 111 and azimsulfuron, compound 1 11 and benfuresate, compound 111 and bensulfuron-methyl, compound 111 and benzofenap, compound 111 and bispyribac- sodium, compound 111 and carfentrazone, compound 111 and chlorimuron-ethyl, compound 111 and cinosulfuron, compound 111 and cyclosulfamuron, compound 111 and dymron, compound 111 and ethoxysulfuron, compound 111 and halosulfuron-methyl, compound 111 and imazosulfuron, compound 111 and metsulfuron-methyl, compound 111 and oxaziclomefone, compound 111 and pentoxazone, compound 111 and propanil, compound 111 and pyrazolate, compound 111 and pyrazosulfuron-ethyl, compound 111 and pyribenzoxim, compound 111 and pyriminobac-methyl.
The following Tests demonstrate the control efficacy of the compounds of this invention against specific weeds. The weed control afforded by the compounds is not limited, however, to these species. See Index Tables A-J for compound descriptions. The abbreviation "Ex." stands for "Example" and is followed by a number indicating in which example the compound is prepared.
INDEX TABLE A
Figure imgf000081_0001
Cmpd Y E_ X mp (°C)
1 (Ex. 1) Cl CH2CH3 0 oil *
2 Cl CH2CH3 NC02CH2CH3 oil *
3 Cl CH2CH3 S oil *
4 Cl CH2CH3 S02 oil *
5 Cl CH2CH3 NC02C(CH3)3 oil *
Figure imgf000081_0002
8 (Ex. 4) Cl oC3H5 0 140-142
9 Cl CHoCFi O 135-137
*See Index Table J for Η NMR data. INDEX TABLE B
Figure imgf000082_0001
Cmpd w Yi Yi Yi E2 mp r°o 10 Cl CH H H H CH(CH3)2 oil *
11 Br CH H H H CH(CH3)2 135-137 12 Cl CH H H Cl CH2CH3 112-115 13 H CC1 Cl H H CH2CH3 107-110 14 Cl N H H H CH2CH3 oil * 15 Cl CH Cl H H CH2CH3 99-101 16 Cl CC1 H H H CH2CH3 oil * 17 Cl CH H Cl H CH2CH3 170-173 18 H CC1 H Cl H CH2CH3 102-104 19 Cl CH H H CH3 CH2CH3 oil * 20 Cl CH H H Cl CH(CH3)2 138-141 21 Cl N H H H CH(CH3)2 119-122 22 Cl N /'-butyl H H CH2CH3 170-172 23 C02CH3 CH H H H CH2CH3 102-104 24 CH2C1 CH H H H CH2CH3 127-130 25 CH2SCN CH H H H CH2CH3 oil * 26 Cl CH Cl H H CH2CH3 99-101
*See Index Table J for lU NMR data. INDEX TABLE C
Figure imgf000083_0001
Cmpd Yl w γ2 Y3 γ4 R2 mp (°C) 7 (Ex. 5) Cl CH H H Cl CH(CH3)2 110-112
28 CH3 CH H H H CH(CH3)2 75-77
29 Cl CH H H H CH(CH3)2 120-122
30 Cl CH Cl H H CH(CH3)2 80-83
31 CH3 CH H H CH3 CH(CH3)2 oil *
32 CH3 CH H H Cl CH(CH3)2 oil *
33 Cl N H H H CH(CH3)2 127-129
34 CH3 CH CH3 H CH3 CH(CH3)2 100-103
35 Cl N CH3 H H CH(CH3)2 82-85
36 CH3 CH H H CH2CH3 CH(CH3)2 oil *
37 CH(CH3)2 CH H H H CH(CH3)2 65-68
38 CH3 N H H CH3 CH(CH3)2 95-97
39 Cl CH H H H CH2CH=CH2 64-65
40 H CC1 Cl H H CH(CH3)2 oil *
41 OCH3 CH H H H CH(CH3)2 oil *
42 Cl CH H H Cl CH2CH=CH2 73-76
43 CH3 N H H H CH(CH3)2 103-106
44 Cl CH Cl H H CH2CH=CH2 78-80
45 OCH2CH3 CH H H H CH(CH3)2 oil *
46 F CH H H F CH(CH3)2 98-100
47 Cl CH Cl H Cl CH2CH=CH2 83-86
48 Cl CH CH3 H CH3 CH(CH3)2 98-101
49 Cl CH H H F CH2CH=CH2 oil *
50 F CH H H H CH(CH3)2 120-122
51 CF3 CH H H H CH(CH3)2 123-125 (Ex. 7) Cl CH H H F CH(CH3)2 93-95
53 Cl CH F H H CH(CH3)2 78-81
54 Cl CH Cl H Cl CH(CH3)2 94-96 vo 00 00 00 oo 00 00 00 00 o——o 00 -J -o -o -o. -j -J -J -o -J -J σs σs σs σs σs OS OS σs Os σs Oh Oh Oh Oh Oh © VO oo σs Oh J> oo t © VO 00 -o σs Oh 4^ J to © VO oo ^1 σs Oh J t © vo OO ^J σs Oh
O
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" X CO C j o
X x x S' X Ω Ω x Ω Ω Ω x Ω ^ Ω X Ω Ω Ω X Ω o Tl ** Ω T] X -r] Ep T) O TJ
o
X
Figure imgf000084_0001
o o o o O Q o o τι o ^ X K Ω X X X X X X X ^ X ^ Ω Ω Ω
OJ O XO x x S? Q a x g X X Ω X X X X Ω
00 o
X X τι x x x x x x x x x x x x x x x x x x x x x x x x x x x x x x X g X
o o x x x x x x x x Sp x x x x x x x x Q a x X X X X X X Ω X X W K X X X X X X
o o o o o o o o o o o o o o o o
X X X o o o o o o o o O O O o o o o o
X o o o o o o o o o o o o o o o X X X X X X o o X X X o to to to to to to to X
O O O O O O O O O "o
X X X X X .X .X .X .X .X X . X X X X X to t
Q O O Q O J X .X Q 7 Q ~ O 7 Q K - I H oo o XH > o o X— i X X X X X X o oo oo oo oo oo oo X to' o xo oxo oxo oxo oxo oxo oxo oxo to' to' to' o to' t to' to to to to to to to to to
Figure imgf000084_0002
92 SCHF2 CH H H H CH(CH3)2 oil*
93 OCHF2 CH H H H CH(CH3)2 oil* *See Index Table J for JH NMR data.
INDEX TABLE D
Figure imgf000085_0001
Cmpd yi γ2 γ4 R2 mp TO
94 Cl H Cl CH2CH3 oil*
95 Cl Cl H CH2CH3 oil*
96 Cl Cl Cl CH2CH3 oil*
97 Cl H F CH2CH3 oil*
98 F Cl H CH2CH3 oil *
99 Cl F H CH2CH3 oil*
100 CH3 H CH3 CH2CH3 oil1
101 (Ex.6) Cl H H CH2CH3 oil :
*See Index Table J for JH NMR data.
INDEX TABLE E
Figure imgf000085_0002
Cmpd Yi γ2 Yi E2. mp (°C
102 Cl H H CH(CH3)2 oil*
103 Cl H Cl CH(CH3)2 oil *
104 Cl Cl H CH(CH3)2 oil*
105 Cl Cl Cl CH(CH3)2 oil*
106 Cl H Cl CH2CH3 oil* 107 CH3 H CH3 CH2CH3 oil*
108 Cl Cl Cl CH2CH3 oil*
109 Cl H F CH(CH3)2 oil*
110 Cl H F CH2CH3 oil *
*See Index Table J for JH NMR data.
INDEX TABLE F
Figure imgf000086_0001
Cmpd Yi W Yi mp (00
111 Cl CH Cl oil*
112 F CH H oil*
113 Cl CH F oil*
114 F CH F oil*
115 CH3 N CH3 oil*
116 OCF3 CH H oil*
117 F CH CH3 oil*
118 SCF3 CH H oil*
119 SCHF2 CH H oil*
120 OCHF2 CH H oil*
*See Index Table J for lH NMR data.
INDEX TABLE G
Figure imgf000086_0002
Cmpd Yi Yi Yi Yi mp TO
121 Cl H Cl H 128-130 122 Cl H F H 125-127
123 Cl F H H 95-97
124 F Cl H H 78-80
125 CH3 H CH3 H 112-115
126 Cl H Cl CH3 100-103
127 Cl H F CH3 100-103
128 F H H CH3 115-117
129 F H F CH3 106-108
INDEX TABLE H
Cmpd Structure mp (°C)
Figure imgf000087_0001
Figure imgf000087_0002
Figure imgf000088_0001
Figure imgf000089_0001
Figure imgf000089_0002
Figure imgf000090_0001
Figure imgf000090_0002
*See Index Table J for !H NMR data.
INDEX TABLE I
Cmpd Structure mp (°0
Figure imgf000090_0003
Figure imgf000091_0001
Figure imgf000091_0002
Figure imgf000091_0003
Figure imgf000092_0001
*See Index Table J for tø NMR data. ** No data available INDEX TABLE J
Cmpd No. *H NMR Data (CDC13 solution unless indicated otherwise)3
1 δ 7.55 (m, 4H), 4.3-3.9 (brm, 3H), 3.4 (brm, 4H), 1.9 (brm, 4H), 1.3 (br m, 3H).
2 δ 7.55 (m, 4H), 4.4-3.8 (br m, 5H), 3.5 (m, 2H), 2.8 (br s, 2H), 1.8 (br m, 4H), 1.3 (brm, 6H).
3 δ 7.55 (m, 4H), 3.65-4 (brm, 3H), 2.7 (brm, 4H), 1.9-2.4 (brm, 4H), 1.3 (brm,3H).
4 δ 7.55 (m, 4H), 3.9-4.3 (br s, IH), 3.5 (q, 2H), 3.2 (br s, 4H), 2.4 (br s, 4H),1.3(brs,3H).
5 δ 7.55 (m, 4H), 3.7-4.3 (br m, 3H), 3.5 (m, 2H), 2.7 (br s, 2H), 1.8 (br m, 4H), 1.5(brs,9H), 1.3(brs,3H).
6 δ 7.8 (d, IH), 7.55 (m, 3H), 4.3-3.9 (br m, 3H), 3.4 (br m, 4H), 1.9 (br m, 4H), 1.3 (brm, 3H).
7 δ 7.82 (s IH), 7.55 (m, 4H), 6.7 (s, IH), 4.3-3.9 (br s, 3H), 3.4 (br s, 4H), 1.9(brs,4H),1.3(brm,3H).
10 δ 7.5 (m, 4H), 4.0 (m, 2H), 3.8 (br s, IH), 3.6 (br s, IH), 3.4 (t, 2H), 1.8
(brs,4H), 1.4(brm,6H). 14 δ 8.6 (d, IH), 7.9 (d, IH), 7.5 (m, IH), 4.3-3.9 (br m, 3H), 3.4 (br m, 4H),
1.9(brm,4H), 1.3(brm,3H). 16 δ 7.7 (d, IH), 7.4 (m, 2H), 4.8 - 3.3 (brm, 5H), 4.1 (brm, 2H), 1.9 (brm,
4H), 1.3(brs,3H). 19 δ 7.4 l(m, 3H), 4.8 - 3.3 (brm, 5H), 4.1 (brm, 2H), 2.2 (s, 3H), 1.9 (brm,
4H), 1.3(brs,3H). 25 δ 7.6 (m, 4H), 4.4 (s, 2H), 4.1 (m, 3H), 3.5 (m, 4H), 2.0 (m, 3H), 1.3 (m,
4H).
31 δ 7.3-7.1 (m, 3H), 5.7 (br s, IH), 4.4-4.3 (m, IH), 4.15 (m, 2H), 3.78 (t, 2H), 2.38 (br s, 2H), 2.16 (s, 6H), 1.41 (d, 6H).
32 δ 7.4-7.2 (m, 3H), 5.7 (br s, IH), 4.48-4.39 (m, IH), 4.1 (m, 2H), 3.78 (br s, 2H), 2.38 (br s, 2H), 2.2 (s, 3H), 1.4 (d, 6H).
36 δ 7.4-7.2 (m, 3H), 5.7 (br s, IH), 4.4 (m, IH), 4.15 (m, 2H), 3.78 (t, 2H),
2.4 (m, 4H), 2.1 (s, 3H), 1.4 (d, 6H), 1.15 (t, 3H).
40 58.11 (s, lH),7.85(d, lH),7.59(d, lH),5.7(brs, lH),4.4(m, 1H),4.15 ( , 2H), 3.78 (t, 2H), 2.38 (br s, 2H), 1.4 (d, 6H).
41 δ 7.5 (t, IH), 7.3 (d, IH), 7.0 (t, IH), 5.7 (br s, IH), 4.4 (m, IH), 4.15 (m, 2H), 3.8 (s, 3H), 3.78 (t, 2H), 2.38 (br s, 2H), 1.4 (d, 6H). δ 7.45 (t, IH), 7.34 (d, IH), 7.0 (t, IH), 5.7 (br s, IH), 4.41 (m, IH), 4.15
(m, 4H), 3.78 (t, 2H), 2.38 (br s, 2H), 1.4 (m, 9H). δ 7.5 (m, IH), 7.42 (d, IH), 7.23 (m, IH), 5.9 (m, IH), 5.5 (br s, IH), 5.38
(m, IH), 4.24 (m, 2H), 4.15 (m, 2H), 3.8 (t, 2H), 2.38 (br s, 2H). δ 7.47 (t, IH), 7.35 (m, 2H), 5.7 (br s, IH), 4.41 (m, IH), 4.15 (m, 2H), 3.78 (t, 2H), 2.38 (br s, 2H), 1.4 (d, 6H). δ 7.8 (d, IH), 7.47 (d, IH), 5.7 (br s, IH), 4.41 (m, IH), 4.15 (m, 2H), 3.78 (t, 2H), 2.38 (br s, 2H), 1.4 (d, 6H). δ 7.34 (d, IH), 7.05 (d, IH), 5.7 (br s, IH), 4.41 (m, IH), 4.15 (m, 2H), 3.9 (s, 3H), 3.78 (t, 2H), 2.38 (br s, 2H), 1.4 (d, 6H). δ 7.5 (m, IH), 7.09 (m, 2H), 5.7 (br s, IH), 4.41 (m, IH), 4.15 (m, 2H),
3.78 (t, 2H), 2.38 (br s, 2H), 1.4 (d, 6H). δ 7.3 (m, IH), 7.0 (m, 2H), 5.7 (br s, IH), 4.41 (m, IH), 4.15 (m, 2H), 3.78
(t, 2H), 2.38 (br s, 2H), 2.26 (s, 3H), 1.4 (d, 6H). δ 8.0 (d, IH), 7.6 (m, 3H), 5.7 (br s, IH), 4.41 (m, IH), 4.15 (m, 2H), 3.78
(t, 2H), 2.38 (br s, 2H), 1.4 (d, 6H). δ 7.5 (m, IH), 7.4 (m, 2H), 5.54 (br s, IH), 4.41 (m, IH), 4.13 (m, 2H),
3.85 (t, 2H), 3.66 (q, 2H), 2.37 (br s, 2H), 1.29 (t, 3H). δ 7.34 (d, IH), 7.08 (d, IH), 6.93 (dd, IH), 5.79 (br s, IH), 4.43 (m, IH), 4.15 (m, 2H), 3.84 (s, 3H), 3.77 (t, 2H), 2.35 (d, 2H), 1.4 (d, 6H). δ 7.8 (d, 2H), 7.5 (m, 2H), 7.4 (t, IH), 5.7 (br s, IH), 4.4 (m, IH), 4.15 (m, 2H), 3.78 (t, 2H), 2.38 (br s, 2H), 1.4 (d, 6H). δ 7.9 (d, 2H), 7.4 (d, 2H), 5.7 (br s, IH), 4.4 (m, IH), 4.15 (m, 2H), 3.78
(t, 2H), 2.38 (br s, 2H), 1.4 (d, 6H). δ 7.5 (m, 3H), 5.7 (br s, IH), 4.4 (m, IH), 4.15 (m, 2H), 3.78 (t, 2H), 2.38 (br s, 2H), 1.4 (d, 6H). δ 7.6 (d, IH), 7.5 (t, IH), 7.3 (t, IH), 7.1 (d, IH), 5.7 (br s, IH), 4.4 (m, IH), 4.15 (m, 2H), 3.78 (t, 2H), 2.38 (br s, 2H), 1.4 (d, 6H), 1.3 (s, 9H). δ 7.5 (m, 2H), 7.2 (m, IH), 5.7 (br s, IH), 4.4 (m, IH), 4.15 (m, 2H), 3.78 (t, 2H), 2.38 (br s, 2H), 2.3 (s, 3H), 1.4 (d, 6H). δ 7.7 (s, IH), 7.5 (d, IH), 7.4 (d, IH), 5.7 (br s, IH), 4.4 (m, IH), 4.15 (m, 2H), 3.78 (t, 2H), 2.38 (br s, 2H), 1.4 (d, 6H). δ 8.1 (d, IH), 7.8 (m, 3H), 6.83 (t, IH), 5.74 (br s, IH), 4.5 (m, IH), 4.2 (br s, 2H), 3.8 (t, 2H), 2.4 (br s, 2H), 1.4 (d, 6H). δ 7.54 (m, 2H), 7.4 (t, 2H), 6.55 (t, IH), 5.72 (br s, IH), 4.5 (m, IH), 4.2 (br s, 2H), 3.76 (t, 2H), 2.35 (br s, 2H), 1.4 (d, 6H). δ 7.5 (m, 3H), 4.3-3.3 (m, 7H), 2.2-1.2 (m, 7H). 95 δ 7.6 (s, IH), 7.5 (m, 2H), 4.3-4.0 (m, IH), 4.0-3.3 (m, 6H), 2.2-1.2 (m, 7H).
96 δ 7.54 (s, 2H), 4.2 (m, 2H), 3.6 (brm, 4H), 3.4 (m, IH), 2.2-1.2 (m, 7H).
97 δ 7.5 (m, IH), 7.4 (d, IH), 7.2 (m, IH), 4.2 (m, 2H), 3.6 (brm, 4H), 3.4 (m, IH), 2.2-1.2 (m, 7H).
98 δ 7.5 (t, IH), 7.3 (m, 2H), 4.21 (m, 2H), 3.6 (brm, 4H), 3.4 (m, IH), 2.2-1.2 (m,7H).
99 δ 7.5 (t, IH), 7.4 (d, IH), 7.2 (m, IH), 4.21 (m, 2H), 3.6 (brm, 4H), 3.4 (m, IH), 2.2-1.2 (m, 7H).
100 δ 7.3 (m, 3H), 4.21 (m, 2H), 3.6 (brm, 4H), 3.4 (m, IH), 2.2 (s, 6H), 2.2-1.2 (m,7H).
101 δ 7.6-7.4 (m, 4H), 4.2-3.2 (m, 7H), 2.1-1.2 (m, 7H).
102 δ 7.5 (m, 4H), 4.2-3.4 (m, 7H), 2.1 (m, IH), 1.6-1.3 (m, 8H).
103 δ 7.5 (m, 3H), 4.1 (m, IH), 3.8 (m, 2H), 3.6 (br s, IH), 3.4 (m, 2H), 2.8 (br s, IH), 2.1 (m, IH), 1.8-1.2 (m, 8H).
104 δ 7.6 (s, IH), 7.5 (m, 2H), 4.1 (m, IH), 3.8 (m, 2H), 3.6 (br s, IH), 3.4 (m, 2H), 2.8 (br s, IH), 2.1 (m, IH), 1.8-2.1 (m, 8H).
105 δ 7.5 (s, 2H), 4.1 ( , IH), 3.8 (m, 3H), 3.6 (br s, IH), 3.4 (m, 2H), 2.1 (m, IH), 1.7-1.3 (m, 8H).
106 δ 7.5 (m, 3H), 4.0-3.4 (m, 7H), 2.8 ( , IH), 2.1 (m, IH), 1.8-1.2 (m, 5H).
107 δ 7.3 (m, 3H), 4.0-3.4 (m, 7H), 2.8 (m, IH), 2.2 (s, 6H), 2.1 (m, IH), 1.8-1.2 (m,5H).
108 δ 7.54 (s, 2H), 4.0-3.4 (m, 7H), 2.8 (m, IH), 2.1 (m, IH), 1.8-1.2 (m, 5H).
109 δ 7.5 (m, IH), 7.4 (d, IH), 7.2 (m, IH), 4.1 (m, IH), 3.8 (m, 2H), 3.6 (br s, IH), 3.4 (m, 2H), 2.8 (br s, IH), 2.1 (m, IH), 1.8-1.2 (m, 8H).
110 δ 7.5 (m, IH), 7.4 (d, IH), 7.2 (m, IH), 4.0-3.4 (m, 7H), 2.8 (m, IH), 2.1 (m, IH), 1.8-1.2 (m,5H).
111 δ 7.53 (m, 3H), 5.88 (br s, IH), 4.4 (m, IH), 4.18 (m, 2H), 3.7 (t, 2H), 2.2 (brs,2H), 1.4(d,6H).
112 δ 7.51 (m, 2H), 7.31 (m, 2H), 5.90 (br s, IH), 4.4 (m, IH), 4.16 (m, 2H), 3.7 (t, 2H), 2.2 (brs, 2H), 1.4 (d, 6H).
113 δ 7.51 (m, IH), 7.4 (d, IH), 7.2 (m, IH), 5.88 (br s, IH), 4.4 (m, IH), 4.16 (m, 2H), 3.7 (t, 2H), 2.2 (br s, 2H), 1.4 (d, 6H).
114 δ 7.53 (m, IH), 7.14 (t, 2H), 5.89 (br s, IH), 4.4 (m, IH), 4.16 (m, 2H), 3.7 (t, 2H), 2.2 (br s, 2H), 1.4 (d, 6H).
115 δ 8.5 (d, IH), 7.17 (d, IH), 5.9 (br s, IH), 4.4 (m, IH), 4.16 (m, 2H), 3.7 (t, 2H), 2.4 (s, 3H), 2.2 (br s, 5H), 1.4 (d, 6H). 116 δ 7.5 (m, 4H), 5.9 (br s, IH), 4.4 (m, IH), 4.16 (m, 2H), 3.7 (t, 2H), 2.2 (brs,2H), 1.4(d,6H).
117 δ 7.4 (m, IH), 7.1 (m, 2H), 5.9 (br s, IH), 4.4 (m, IH), 4.16 (m, 2H), 3.7 (t, 2H), 2.26 (s, 3H), 2.2 (br s, 2H), 1.4 (d, 6H).
118 δ 8.0 (d, IH), 7.6 (m, 3H), 5.9 (brs, IH), 4.4 (m, IH), 4.16 (m, 2H), 3.7 (t, 2H), 2.2 (br s, 2H), 1.4(d,6H).
119 δ 7.9 (d, IH), 7.6 (m, 3H), 6.83 (t, IH), 5.91 (br s, IH), 4.5 (m, IH), 4.2 (br s, 2H), 3.71 (t, 2H), 2.25 (br s, 2H), 1.4 (d, 6H).
120 δ 7.54 (m, 2H), 7.49 (t, 2H), 6.55 (t, IH), 5.9 (br s, IH), 4.4 (m, IH), 4.16 (br s, 2H), 3.7 (t, 2H), 2.24 (br s, 2H), 1.4 (d, 6H).
130 δ 8.5 (s, IH), 5.68 (br s, IH), 4.4 (m, IH), 4.16 (m, 2H), 4.0 (s, 6H), 3.77 (t, 2H), 2.33 (br s, 2H), 1.4 (d, 6H).
132 δ 5.7 (br s, IH), 4.41 (m, IH), 4,3 (t, 2H), 4.15 (m, 2H), 3.9 (t, 2H), 3.78 (t, 2H), 2.38 (br s, 2H), 1.4 (d, 6H).
133 δ 5.8 (br s, IH), 4.41 (m, IH), 4.1 (m, 3H), 3.7 (t, 2H), 2.38 (br s, 2H), 2.1-1.7 (m, 8H), 1.4 (d, 6H), 1.5-1.2 (m, 2H).
134 δ 5.8 (br s, IH), 4.41 (m, IH), 4.1 (m, 2H), 3.7 (t, 3H), 2.2-1.1 (m, 1 IH), 1.4(d,6H),0.7(d,3H).
135 δ 5.6 (br s, IH), 4.4 (m, IH), 4.1 (m, 2H), 3.7 (t, 3H), 2.38 (br s, 2H), 2.1-1.1 (m, 9H), 1.4 (d, 6H), 0.8 (d, 3H).
136 δ 5.9 (m, IH), 5.6 (br s, IH), 5.3 (m, 2H), 4.54 (m, 2H), 4.4 (m, IH), 4.1 (m, 2H), 3.7 (t, 2H), 2.38 (br s, 2H), 1.4 (d, 6H).
137 δ 6.0-5.8 (m, 2H), 5.3 (m, 2H), 4.5 (m, 2H), 4.4 (m, IH), 4.1 (m, 2H), 3.7 (t, 2H), 2.38 (br s, 2H), 1.4 (d, 6H).
143 δ 4.3 (q, 2H), 4.1 (brd, 2H), 3.8 (s, 3H), 3.5-3.3 (m, 5H), 2.2 (s, 3H), 2.18
(s, 3H), 2.1-1.8 (brm, 2H), 1.36-1.2 (m, 8H). 147 δ 7.43 (dd, IH), 7.21 (dd, IH), 7.04 (dd, IH), 5.7 (br s, IH), 4.4 (m, IH),
4.13 (d, 2H), 3.76 (t, 2H), 2.36 (br s, 2H), 1.4 (d, 6H).
149 δ 7.19 (d, IH), 6.87 (d, IH), 5.68 (br s, IH), 4.4 (m, IH), 4.13 (m, 2H), 3.76 (t, 2H), 2.35 (br s, 2H), 1.4 (d, 6H).
150 δ 5.7 (br s, IH), 4.4 (m, IH), 4.13 (m, 2H), 3.76 (t, 2H), 2.47 (s, 3H), 2.35 (br s, 2H), 2.34 (s, 3H), 1.4 (d, 6H).
151 δ 7.39-7.37 (m, 2H), 7.09-7.-01 (m, 2H), 5.58 (br s, IH), 5.05 (s, 2H), 4.37 (m, IH), 3.97 ( , 2H), 3.63 (t, 2H), 2.27 (d, 2H), 1.33 (d, 6H).
152 δ 7.6 (d, IH), 7.59-7.19 (m, 3H), 5.62 (br s, IH), 5.2 (s, 2H), 4.4 (m, IH), 4.11 (m, 2H), 3.69 (t, 2H), 2.29 (br s, 2H), 1.34 (d, 6H).
153 δ 7.43-7.25 (m, 4H), 5.61 (br s, IH), 5.21 (s, 2H), 4.38 (m, IH), 4.03 (m, 2H), 3.66 (t, 2H), 2.29 (br s, IH), 1.4 (d, 6H). 154 δ 7.36-7.29 (d, 2H), 6.88 (d, 2H), 5.55 (br s, IH), 5.01 (s, 2H), 4.37 (m, IH), 3.95 (m, 2H), 3.79 (s, 3H), 3.61 (t, 2H), 2.76 (br s, 2H), 1.33 (d, 6H).
155 δ 7.5 (m), 5.7 (s), 5.6 (s), 4.4-4.0 (m), 3.29-3.62 (m), 2.5 (m), 2.2 (m), 1.2-1.4 (m).
156 δ 1.2 (d, 6H), 2.3 (br s, 2H), 3.86 (br s, 2H), 4.28 (m, 2H), 4.38 (m, IH), 5.71 (brs, IH).
157 δ 5.89 (m, IH), 4.35 (m, IH), 4.1 (m, 2H), 3.8 (t, 2H), 2.35 (br s, 2H), 1.2 (d, 6H).
158 δ 5.6 (d, IH), 5.14 (m, IH), 4.8 (d, IH), 4.7 (m, IH), 4.5 (m, IH), 1.1 (m, 6H).
159 δ 5.69 (m, IH), 4.25 (m, 2H), 3.88 (t, 2H), 3.5 (m, 2H), 2.35 (br s, 2H), 1.23 (t, 3H).
160 δ 4.3 (m, IH), 4.1 (br d, 2H), 3.4 (m, 4H), 1.8 (m, 4H), 1.2 (m, 3H). 162 δ 4.2 (m, 5H), 3.4 (m, 2H), 2.8 (m, 2H), 1.8 (m, 4H), 1.3 (m, 6H).
164 δ 4.0 (m, 3H), 3.4 (t, 2H), 2.6 (m, IH), 2.7 (br d, 2H), 2.2 (m, 2H), 1.0 (m,
4H). 170 δ 3.9 (m, IH), 3.8 (m, IH), 3.4 (m, IH), 2.7 (m, IH), 2.6 (d, 2H), 2.3 (m,
IH), 2.0 (m, IH), 1.4 (m, 2H), 1.1 (d, 6H). 174 δ 5.9 (br s, IH), 4.3 (m, IH), 3.4 (m, IH), 3.2 (m, IH), 2.8 (br s, 2H), 2.4
(brm,2H).
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, (br d)-broad doublet, (br m)-broad multiplet.
BIOLOGICAL EXAMPLES OF THE INVENTION Test A
Seeds of barnyardgrass (Echinochloa crus-galli), crabgrass (Digitaria spp.), morningglory (Ipomoea spp.), and velvetleaf (Abutilon theophrasti) were planted into a sandy loam soil and treated preemergence by soil drench with test chemicals formulated in a non-phytotoxic solvent mixture which included a surfactant. At the same time, these crop and weed species were also treated postemergence sprayed to runoff , with test chemicals formulated in the same manner.
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. A dash (-) response means no test results.
Table A COMPOUND Table A COMPOUND Rate 1000 g/ha 80 Rate 500 g/ha 80 PRE DRENCH SPRAYED TO RUNOFF Barnyardgrass 9 Barnyardgrass 8 Crabgrass 9 Crabgrass 6 Morningglory 2 Morningglory 7 Velvetleaf 4 Velvetleaf 1
TestB
Seeds of barley (Hordeum vulgare), barnyardgrass (Echinochloa crus-gallϊ), bedstraw {Galium aparine), blackgrass (Alopecurus myosuroides), broadleaf signalgrass (Brachiaria decumbens), chickweed (Stellaria media), cocklebur (Xanthium strumarium), corn (Zea mays), cotton (Gossypium hirsutum), crabgrass (Digitaria sanguinalis), downy brome (Bromus tectorum), giant foxtail (Setariafaberii), lambsquarters Chenopodium album), morningglory (Ipomoea hederacea), rape (Brassica napus), redroot pigweed (Amaranthus retroβexus), rice (Oryza sativa), sorghum (Sorghum bicolor), soybean (Glycine max), sugar beet (Beta vulgaris), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum), wild buckwheat (Polygonum convolvulus), 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.
At the same time, these crop and weed species were also treated with postemergence applications of test chemicals formulated in the same manner. 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 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. Table B COMPOUND
Rate 1000 g/ha 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27
POSTEMERGENCE
B. signalgrass 7 0 9 0 0 5 0 9 8 9 - 0 0 0 0 6
Barley 2 0 0 0 0 0 0 0 0 0 0 - - - - - - - - - - 0 - - - - -
Barnyardgrass 9 8 3 7 0 9 0 9 0 9 9 - - - - - - - - - - 0 - - - - -
Bedstra 6 4 7 4 0 6 0 7 0 5 5 7 0 7 9 0 0 0 7 6 3 0 3 0 0 9 8
Blackgrass 8 0 0 0 0 8 0 3 0 2 0 0 0 8 0 4 7 0 6 2 8 0 0 0 0 0 3
Chick eed 7 2 6 0 0 4 0 3 0 3 3 - - - - - - - - - - 0 - - - - -
COcklebur 3 2 4 2 0 3 0 2 4 1 3 2 5 1 0 1 4 0 4 1 0 0 0 0 0 0 6
Corn 8 0 0 0 0 7 0 7 0 7 7 6 1 6 0 0 0 0 7 6 2 0 7 0 0 0 6 S -
Cotton 3 2 7 2 0 9 2 6 2 2 2 - - - - - - - - - - 0 - - - - -
Crabgrass 9 2 2 4 0 9 2 9 0 9 9 7 7 9 9 8 5 0 8 8 6 3 2 0 0 9 9
Downy brome 3 0 0 0 0 0 0 0 0 0 0 - - - - - - - - - - 0 - - - - -
Giant foxtail 9 0 2 4 0 9 0 9 0 9 9 7 0 9 8 3 4 0 6 7 4 0 5 0 0 8 9
Lambsquarters 9 4 4 3 0 5 0 7 0 0 6 - - - - - - - - - - 0 - - - - -
Morningglory 9 2 2 0 0 9 4 9 2 6 6 4 6 9 8 0 4 0 6 4 7 0 7 0 0 8 8
Nutsedge 3 0 0 0 0 6 0 0 0 0 0 2 0 8 0 0 0 0 3 0 4 0 3 0 0 0 7
Rape 4 0 6 0 0 5 1 0 0 0 0 0 0 2 0 2 0 0 5 0 0 0 0 0 0 0 2
Redroot pigweed 0 0 7 0 0 5 0 5 0 0 - 0 0 0 0 7
Rice 7 0 0 8 0 7 0 9 0 8 9 - - - - - - - - - - 0 - - - - -
Sorghum 6 0 0 0 0 7 0 4 0 8 7 - - - - - - - - - - 0 - - - - -
Soybean 7 2 2 2 2 7 2 8 2 8 8 5 0 3 7 3 6 0 7 6 3 0 8 2 2 7 3
Sugar beet 2 0 4 0 0 0 2 0 0 0 0 6 0 6 0 0 0 0 0 2 0 0 0 0 0 0 4
Figure imgf000100_0001
Velvetleaf 6 0 2 4 0 6 0 8 3 6 7 0 0 6 0 3 2 0 6 3 0 0 2 0 0 0 2
Wheat 2 0 0 0 0 5 0 0 0 0 0 0 0 4 0 0 0 0 5 3 3 0 2 0 0 0 0
Wild buckwheat 6 0 7 1 0 1 0 1 0 0 4 - - - - - - - - - - 0 - - - - -
Wild oat 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Table B COMPOUND
Rate 1000 g/ha 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27
PREEMERGENCE
B. signalgrass 10 8 10 10 10 2 4 10 9 9 - 10 0 0 10 10 00
Barley 0 0 0 0 0 2 0 0 0 2 2 - - - - - - - - - - 0 - - - - -
Barnyardgrass 10 2 9 7 0 10 0 9 0 10 10 - - - - - - - - - - 6 - - - - -
Bedstraw 3 0 2 0 0 0 0 0 0 0 0 10 2 9 1 0 0 0 8 2 4 0 5 0 0 1 9
Blackgrass 9 0 0 0 0 8 0 8 0 6 8 9 6 10 2 9 7 0 9 3 6 0 4 0 0 2 7
Chickweed 7 0 4 3 0 4 0 0 0 0 0 - - - - - - - - - - 0 - - - - -
Cocklebur 1 0 0 0 0 0 0 6 0 0 - 0 0 2 0 4 0 0 3 0 - 0 0 c 0 0 0
Corn 9 0 0 2 0 8 0 6 0 9 8 9 0 2 5 4 0 0 8 7 6 0 0 0 0 5 4
Cotton 7 0 2 0 0 6 0 5 0 0 5 - - - - - - - - - - 0 - - - - -
Crabgrass 10 4 9 7 0 9 0 9 0 10 9 9 9 10 10 9 9 0 9 9 9 0 10 0 2 10 10
Downy brome 6 0 2 0 0 4 0 0 0 7 8 - - - - - - - - - - 0 - - - - -
Giant foxtail 10 2 9 3 0 9 0 9 0 9 10 10 10 10 10 8 7 6 10 9 9 0 10 0 4 10 10
Lambsquarters 10 4 9 8 0 10 0 10 0 10 9 - - - - - - - - - - 8 - - - - -
Morningglory 8 0 0 4 0 6 0 6 0 10 10 7 0 8 2 3 0 0 6 1 7 0 0. 0 0 2 3
Nutsedge 8 0 0 0 0 0 0 0 0 0 - 0 0 6 0 0 0 0 10 0 9 0 0 0 0 0 0
Rape 7 4 0 0 0 6 0 0 0 0 5 10 5 8 5 3 7 0 7 0 2 0 0 0 0 5 7
Redroot pigweed 9 4 10 9 8 9 0 6 3 6 - 0 0 0 9 10
Rice 2 0 0 0 0 2 0 2 0 7 7 - - - - - - - - - - 0 - - - - -
Sorghum 9 0 4 0 0 9 0 8 0 9 9 - - - - - - - - - - 0 - - - - -
Soybean 8 0 0 0 0 8 0 4 0 9 9 6 0 8 6 0 0 0 8 0 9 0 2 0 2 6 0
Sugar beet 8 2 2 0 0 5 0 0 0 0 0 8 0 9 6 7 8 0 6 5 3 0 3 0 0 6 7
Velvetleaf 5 0 0 0 0 5 3 5 0 3 3 4 0 7 2 0 0 0 0 0 5 0 0 0 0 2 0
Wheat 0 0 0 0 0 6 0 3 0 7 7 5 0 6 0 0 2 0 6 0 0 0 2 0 0 0 0 i-o <-o
Wild buckwheat 5 0 0 0 0 0 0 0 0 4 0 - - - - - - - - - - 0 - - - - -
Wild oat 9 0 0 0 0 6 0 6 0 7 8 7 2 8 2 0 5 0 7 2 2 0 3 0 0 2 6
Table B COMPOUND
Rate 200 g/ha 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27
POSTEMERGENCE
B. signalgrass 0 0 0 0 0 0 0 0 0 0 - 0 0 0 0 2
Barley 2 0 0 0 0 0 0 0 0 0 0 - - - - - - - - - - 0 - - - - -
Barnyardgrass 9 0 0 0 0 9 0 9 0 9 9 - - - - - - - - - - 0 - - - - -
Bedstraw 6 0 5 0 0 4 0 2 0 2 4 2 0 3 4 0 0 0 0 2 3 0 0 0 0 4 6
Blackgrass 0 0 0 0 0 2 0 0 0 0 0 0 0 2 0 0 0 0 0 0 3 0 0 0 0 0 0
Chickweed 4 0 3 0 0 0 0 0 0 0 2 - - - - - - - - - - 0 - - - - -
Cocklebur 0 0 0 0 0 3 0 0 0 0 0 - 0 0 0 0 4 0 0 0 0 0 0 0 0 0 3
Corn 2 0 0 0 0 4 0 0 0 3 2 - 0 0 0 0 0 0 9 0 0 0 0 0 0 0 2
Cotton 2 0 2 0 0 1 0 2 0 0 0 - - - - - - - - - - 0 - - - - -
Crabgrass 5 0 0 0 0 7 0 7 0 6 9 - 2 6 3 0 0 0 7 0 0 0 0 0 0 3 6
Downy brome 0 0 0 0 0 0 0 0 0 0 0 - - - - - - - - - - 0 - - - - -
Giant foxtail 2 0 0 0 0 6 0 8 0 7 7 - 0 7 0 0 0 0 0 0 0 0 0 0 0 0 2
Lambsquarters 8 0 0 0 0 4 0 3 0 0 0 - - - - - - - - - - 0 - - - - -
Morningglory 2 0 0 0 0 2 0 7 0 0 2 - 1 3 0 0 3 0 2 1 2 0 4 0 0 0 3
Nutsedge 0 0 0 0 0 0 0 0 0 0 0 - 0 3 0 0 0 0 0 0 0 0 0 0 0 0 0
Rape 0 0 2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Redroot pigweed 0 0 0 0 0 0 0 0 0 0 - 0 0 0 0 5
Rice 5 0 0 0 0 0 0 0 0 2 2 - - - - - - - - - - 0 - - - - -
Sorghum 0 0 0 0 0 0 0 0 0 0 0 - - - - - - - - - - 0 - - - - -
Soybean 5 1 2 2 1 4 2 3 1 6 4 - 0 2 4 3 5 0 2 2 2 0 2 2 2 4 4
Sugar beet 2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Velvetleaf 2 0 2 0 0 2 0 0 0 0 0 - 0 4 0 0 0 0 0 0 0 0 0 0 0 0 0
Wheat 2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Wild buckwheat 0 0 4 0 0 0 0 0 0 0 0 - - - - - - - - - - 0 - - - - -
Wild oat 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Table B COMPOUND
Rate 200 g/ha 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27
PREEMERGENCE
B. signalgrass 10 1 10 9 10 0 0 10 7 8 - 0 0 0 9 10
Barley 0 0 0 0 0 0 0 0 0 0 0 - - - - - - - - - - 0 - - - - -
Barnyardgrass 8 0 0 0 0 8 0 4 0 8 8 - - - - - - - - - - 0 - - - - -
Bedstraw 0 0 0 0 0 0 0 0 0 0 0 8 0 4 0 0 0 0 4 0 1 0 4 0 0 0 4
Blackgrass 9 0 0 0 0 2 0 2 0 0 0 5 3 2 0 4 0 0 5 0 3 0 0 0 0 0 3
Chickweed 0 0 0 0 0 0 0 0 0 0 0 - - - - - - - - - - 0 - - - - -
Cocklebur 0 0 0 0 0 - 0 3 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Corn 7 0 0 0 0 3 0 0 0 0 0 0 0 0 2 0 0 0 0 2 2 0 0 0 0 2 2
Cotton 4 0 0 0 0 0 0 - 0 0 0 - - - - - - - - - - 0 - - - - -
Crabgrass 9 0 2 2 0 9 0 9 0 8 9 7 6 9 3 3 2 0 7 8 8 0 2 0 0 3 10
Downy brome 4 0 0 0 0 0 0 0 0 0 3 - - - - - - - - - - 0 - - - - -
Giant foxtail 0 0 0 0 0 3 0 8 0 7 9 10 7 9 9 5 0 0 7 6 7 0 9 0 0 9 9
Lambsquarters 9 0 7 0 0 8 0 8 0 0 4 - - - - - - - - - - 0 - - - - -
Morningglory 4 0' 0 0 0 2 0 3 0 0 2 0 0 2 0 0 0 0 4 0 1 0 0 • 0 0 0 0
Nutsedge 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Rape 0 0 0 0 0 0 0 0 0 0 0 7 5 2 5 0 2 0 2 0 0 0 0 0 0 5 0
Redroot pigweed 7 0 2 4 6 0 0 2 0 2 - 0 0 0 4 4
Rice 0 0 0 0 0 0 0 0 0 0 0 - - - - - - - - - - 0 - - - - -
Sorghum 0 0 0 0 0 0 0 0 0 2 0 - - - - - - - - - - 0 - - - - -
Soybean 0 0 0 0 0 0 0 0 0 0 2 0 0 3 0 0 0 0 0 0 0 0 0 0 0 0 2
Sugar beet 0 0 0 0 0 0 0 0 0 0 0 5 3 8 0 5 0 0 2 2 3 0 2 0 0 0 5
Velvetleaf 2 0 0 0 0 0 0 2 0 2 0 .0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Wheat 0 0 0 0 0 0 0 0 0 0 0 3 0 2 0 0 0 0 0 0 0 0 0 0 0 0 0
Wild buckwheat 3 0 0 0 0 0 0 0 0 0 0 - - - - - - - - - - 0 - - - - - o
Wild oat 0 0- 0 0 0 6 0 5 0 0 0 5 0 3 0 0 0 0 0 0 0 0 2 0 0 0 4
Table B COMPOUND
Rate 1000 g/ha 12 13 14 15 16 17 18 19 20 21 23 24 25 26 27
SPRAYED PADDY
Barnyardgrass 9 7 9 9 9 9 9 9 9 9 9 9 0 9 9
Ducksalad 9 5 5 8 8 9 8 9 9 8 6 6 5 8 8
Rice 8 8 8 7 7 8 8 7 8 9 7 3 2 7 8
S. flatsedge 8 8 7 8 10 9 9 9 9 8 9 7 8 8 8
Table B COMPOUND
Rate 200 g/ha 12 13 14 15 16 17 18 19 20 21 23 24 25 26 27
SPRAYED PADDY
Barnyardgrass 8 4 9 9 6 5 1 5 9 9 2 0 0 9 9
Ducksalad 8 3 2 7 5 7 3 8 4 3 0 3 0 7 8
Rice 7 1 8 3 2 5 1 2 5 8 2 0 0 3 3
S. flatsedge 8 8 7 7 9 9 8 9 8 6 8 5 5 7 8
TestC Seeds of bedstraw (Galium aparine), blackgrass (Alopecurus myosuroides), broadleaf signalgrass (Brachiaria decumbens), cocklebur (Xanthium strumarium), corn (Zea mays), crabgrass (Digitaria sanguinalis), giant foxtail (Setaria faberiϊ), morningglory (Ipomoea hederacea), rape (Brassica napus), redroot pigweed (Amaranthus retroflexus), soybean (Glycine max), sugar beet (Beta vulgaris), velvetleaf (Abutilon theophrasti), wheat (Triticum aestivum), wild oat (Avenafatud) 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.
At the same time, these crop and weed species were also treated with postemergence applications of test chemicals formulated in the same manner. 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 C, 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. Table C COMPOUND
Rate 500 g/ha 14 15 19 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51
Postemergence
Barnyardgrass 8 9 8 9 9 9 9 9 9 9 9 9 9 8 9 9 9 9 9 9 9 0 9 9 2 9 0 9 9
Blackgrass 2 4 0 4 0 9 8 6 5 0 9 7 9 0 4 9 2 0 7 0 8 0 0 5 0 0 0 7 7
B. Signalgrass 2 0 9 0 3 9 9 0 9 0 9 - - - 0 9 2 0 8 0 0 0 - -
Cocklebur 6 0 2 0 4 6 2 7 1 4 4 1 0 - 0 0 0 0 5 3 2 0 3 6 5 3 0 2 2
Corn 2 0 6 0 0 9 7 1 7 6 8 6 8 0 2 8 2 0 7 0 8 0 2 7 0 4 0 5 7
Crabgrass 8 0 9 0 7 9 9 2 9 7 9 7 9 2 - 9 9 3 9 2 9 0 9. 9 1 9 0 9 9
Ducksalad 6 9 8 9 9 9 8 8 8 9 8 9 7 5 8 9 9 8 9 9 9 9 9 9 9 9 8 9 9
Bedstraw 3 6 8 6 3 9 6 4 6 8 7 0 0 6 4 - 0 3 7 8 0 2 6 0 6 5 0 8
Giant foxtail 7 0 8 0 7 9 9 6 9 8 9 8 9 3 9 9 9 7 9 3 9 0 9 9 0 8 0 9 9
Morningglory 8 2 2 2 3 8 8 7 2 8 9 9 6 3 6 9 2 0 5 5 3 2 0 8 3 7 2 7 8
Nutsedge 0 0 0 0 0 5 .6 0 0 7 2 0 9 0 0 6 0 0 0 0 0 0 0 4 0 - 0 - 5
Rape 8 0 2 0 2 2 2 0 3 0 2 7 0 0 3 0 0 0 3 6 3 0 0 5 0 3 0 0 4
Redroot pigweed 9 4 8 4 2 8 3 0 2 0 8 0 0 3 5 4 0 0 2 7 6 0 0 2 0 6 0 6 6
Rice 8 7 6 7 6 8 8 8 7 8 7 7 8 7 7 8 8 0 8 2 6 4 8 8 7 7 2 7 6
S. Flatsedge 7 9 9 9 8 9 8 8 8 9 9 8 9 8 8 9 9 9 9 9 9 5 9 9 8 9 8 9 9
Soybean 7 5 3 5 2 7 6 7 8 8 7 7 6 3 6 6 7 3 7 3 5 1 6 7 6 2 0 6 6
Sugarbeets 9 0 0 0 5 2 0 4 3 0 6 2 0 0 2 0 0 0 3 3 2 0 0 0 0 6 0 0 1
Velvetleaf 7 1 4 1 3 4 0 1 3 3 7 0 3 0 0 8 0 0 5 4 5 0 0 3 2 0 0 5 5
Wheat 1 0 0 0 0 0 3 2 0 0 9 5 8 0 1 6 2 0 6 0 7 0 0 0 0 0 0 7 4
Wild oats 3 0 0 0 0 0 0 0 0 0 2 0 2 0 2 2 0 0 0 0 5 0 0 4 0 0 0 6 2
Table C COMPOUND
Rate 500 g/ha 52 53 54 55 56 57 59 61 79 82 83 84 85 86
Postemergence
Barnyardgrass 9 9 9 9 9 - 9 8 9 9 0 0 7 9
Blackgrass 4 8 4 7 7 6 7 7 5 9 0 0 0 7
B. signalgrass 7 8 6 7 9 0 0 0 2
Cocklebur 3 3 1 2 0 3 4 4 4 6 0 0 0 5
Corn 3 6 0 0 0 3 7 7 8 5 0 0 0 5
Crabgrass 9 8 3 8 9 8 9 9 9 9 4 2 9 9
Ducksalad 9 8 7 9 8 - 9 9 9 9 6 3 8 9
Bedstraw 7 7 1 0 0 4 6 6 0 2 2 - 8 6
Giant foxtail 9 8 0 8 9 7 9 9 9 9 2 4 3 9
Morningglory 8 8 1 1 7 2 5 7 0 2 0 4 0 8
Nutsedge 6 - 0 - 0 0 0 6 4 9 0 0 0 0
Rape 0 4 0 0 0 2 1 0 0 2 2 0 0 0
Redroot pigweed 5 5 0 0 4 3 3 3 6 7 0 0 6 3
Rice 6 6 0 6 6 - 7 7 7 7 0 0 2 6
S. Flatsedge 9 8 9 8 8 - 9 9 9 9 4 8 8 9
Soybean 7 7 3 6 1 7 7 6 2 6 2 4 1 4
Sugarbeets 0 5 0 0 2 1 2 3 3 0 0 0 0 3
Velvetleaf 5 5 0 0 0 0 0 0 0 4 0 0 0 0
Wheat 2 5 0 3 5 0 6 3 0 6 0 0 0 0
Wild oats 0 3 0 0 2 0 3 0 0 2 0 0 0 0
Table C COMPOUND
Rate 500 g/ha 14 15 19 26 27 28 29 30 31 32 33 34 35 36 37 -38 39 40 41 42 43 44 45 46 47 48 49 50 51
Preemergence
Blackgrass 7 4 5 4 0 9 9 7 2 4 9 7 8 0 0 10 3 0 8 2 10 0 10 9 0 8 4 7 7
B. signalgrass 9 8 - 8 10 - - - - 10 - - - - - - - 3 10 8 10 3 10 10 0 7 3 - -
Cocklebur 0 0 0 0 0 0 0 0 0 0 3 0 0 0 - - 0 0 0 0 - 0 0 6 0 0 0 1 0
Corn 0 0 8 0 7 9 9 8 9 8 9 8 7 7 6 9 0 0 8 0 9 0 8 9 0 0 0 7 7
Crabgrass 9 9 10 9 10 10 10 10 10 9 10 10 10 8 10 10 10 9 10 8 10 3 10 10 9 10 5 10 10
Bedstraw 8 0 8 0 3 7 8 0 0 - 8 7 10 0 0 3 - 0 9 - 10 0 7 7 0 4 4 7 0
Giant foxtail 9 9 10 9 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 10 2 10 10 10 10 8 10 10
Morningglory 2 0 0 0 0 6 5 0 0 1 8 3 4 0 0 6 0 0 5 0 7 0 0 7 0 2 0 7 8
Nutsedge 0 0 0 0 0 10 10 10 9 0 10 10 2 - 0 0 0 - 5 0 4 0 0 10 0 0 0 - -
Rape 2 0 5 0 0 9 8 0 3 7 8 2 6 0 5 7 4 0 9 0 9 0 0 7 0 4 0 9 8
Redroot pigweed 7 9 7 9 2 8 6 4 2 7 9 7 8 0 2 2 7 0 2 0 9 0 0 8 0 3 0 8 7
Soybean 0 0 8 0 0 8 8 0 8 6 9 0 5 0 0 9 0 0 9 0 8 0 2 7 0 0 0 7 1
Sugarbeets 6 4 2 4 2 8 8 3 2 7 8 6 7 0 0 0 0 0 7 0 9 0 2 7 0 7 0 8 6
Velvetleaf 2 0 0 0 0 2 3 - 4 0 - 5 6 0 5 7 0 0 4 0 8 0 0 2 0 0 0 5 5
Wheat 3 2 2 2 0 2 0 2 0 5 8 0 7 0 0 7 0 0 7 0 8 0 6 7 0 0 0 6 3
Wild oats 3 5 6 5 3 9 9 7 0 6 9 2 8 0 0 8 0 3 9 0 9 0 7 10 0 0 0 - 0
Table C COMPOUND
Rate 500 g/ha 52 53 54 55 56 57 59 61 79 82 83 84 85 86
Preemergence
Blackgrass 5 9 5 9 3 6 7 7 3 2 0 0 0 7
B. signalgrass 7 10 9 9 9 3 0 4 9
Cocklebur 0 0 0 0 2 0 7 0 0 0 0 0 - 0
Corn 5 5 0 7 3 6 9 9 8 8 0 0 0 8
Crabgrass 10 10 9 10 10 10 10 10 10 10 8 0 9 10
Bedstraw 0 7 6 2 0 2 4 0 0 6 0 0 0 3
Giant foxtail 10 10 10 10 10 10 10 10 10 10 7 0 9 10
Morningglory 6 7 2 4 3 0 6 0 2 0 0 0 0 0
Nutsedge - 7 0 0 6 0 - - 0 0 0 0 0 0
Rape 7 8 0 6 6 5 8 8 8 5 0 0 0 7
Redroot pigweed 7 7 0 7 6 0 4 3 5 7 0 0 0 9
Soybean 2 0 0 0 2 1 8 1 4 6 0 0 0 6
Sugarbeets 7 7 0 6 5 2 8 7 4 6 0 0 3 5
Velvetleaf 7 5 3 4 6 0 7 4 3 0 0 0 0 0
Wheat 0 0 0 0 0 4 9 5 0 8 0 0 0 0
Wild oats 1 4 0 5 8 5 9 7 6 8 0 0 0 5
Table C COMPOUND
Rate 250 g/ha 14 15 19 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51
Postemergence
Barnyardgrass 8 - 7 - 9 9 9 8 9 9 9 8 8 3 9 9 9 2 9 2 9 0 9 9 0 9 0 9 9
Blackgrass 1 0 0 0 0 8 8 4 0 0 8 7 9 0 0 8 0 0 3 0 5 0 0 5 0 0 0 6 4
B. signalgrass 0 0 8 0 0 9 9 0 9 0 9 - - - 0 9 0 0 8 0 0 0 - -
Cocklebur 2 0 0 0 1 3 1 1 0 3 1 0 0 0 0 0 0 - 0 3 0 0 2 6 0 2 0 2 2
Corn 0 0 0 0 0 8 2 0 7 5 7 0 6 0 0 6 0 0 7 0 7 0 0 3 0 0 0 5 5
Crabgrass 2 0 7 0 0 9 9 2 8 5 9 5 9 1 9 9 6 2 8 0 9 0 2 9 0 9 0 9 8
Ducksalad 6 4 8 4 8 9 8 7 4 9 8 8 7 - 8 9 9 7 9 7 9 9 9 9 8 9 8 9 8
Bedstraw 3 1 0 1 2 7 6 3 5 6 2 7 0 0 3 0 0 0 1 4 5 0 0 4 0 6 2 0 7
Giant foxtail 6 0 1 0 2 9 8 0 9 7 9 2 9 3 8 9 9 4 9 - 9 0 6 9 0 2 0 9 8
Morningglory 5 2 2 2 2 2 7 3 2 4 7 2 4 2 5 8 2 0 2 5 3 0 0 7 3 7 2 1 6
Nutsedge 0 0 0 0 0 2 2 0 0 0 2 0 0 0 0 4 0 0 0 0 0 0 0 4 0 - 0 7 0
Rape 7 0 0 0 0 1 0 0 2 0 0 3 0 0 2 0 0 0 0 4 0 0 0 1 0 2 0 0 3
Redroot pigweed 2 1 6 1 0 8 3 0 0 0 2 0 0 0 0 2 0 0 2 6 3 0 0 0 0 6 0 4 3
Rice 8 7 5 7 4 8 8 7 7 8 7 6 7 6 6 8 7 0 6 0 6 4 8 8 2 6 2 7 6
S. Flatsedge 7 8 9 8 8 9 8 8 8 9 9 8 8 8 8 9 9 9 9 9 9 - 9 9 8 9 8 9 8
Soybean 2 5 2 5 2 7 6 5 6 8 6 4 4 2 6 6 3 3 6 1 5 1 4 6 4 2 0 5 4
Sugarbeets 8 0 0 0 3 0 0 2 2 0 1 0 0 0 0 0 0 0 2 2 2 0 0 0 0 5 0 0 1
Velvetleaf 6 0 4 0 0 4 0 0 0 0 6 0 2 0 0 3 0 0 0 3 0 0 0 0 0 0 0 5 2
Wheat 0 0 0 0 0 0 3 0 0 0 8 3 5 0 0 5 0 0 5 0 7 0 0 0 0 0 0 5 2
Wild oats 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 0 0 0 0 1 0 0 2 0 0 0 2 0
Table C COMPOUND
Rate 250 g/na 52 53 54 55 56 57 59 61 65 66 67 68 69 70 71 72 73 77 78 79 82 83 84 85 86
Figure imgf000111_0001
Pos emergence
B Baarrnnyyaarrddggrraassss 9 9 9 9 9 9 9 9 8 8 - - 8 6 9 9 9 9 9 7 9 6 7 9 7 8 9 0 0 4 9
B Bllaacckkggrraassss 4 4 8 8 0 0 5 5 6 6 5 5 6 3 2 7 3 0 0 0 0 3 0 0 0 2 2 0 0 0 5
B B.. ssiiggnnaallggrraassss - 7 6 7 4 0 0 - - 7 6 0 0 0 1
C Coocckklleebbuurr 2 2 0 0 0 0 1 1 0 0 2 2 4 2 0 0 0 1 1 2 0 2 0 0 0 2 0 0 0 0 5
C Coorrnn 0 0 4 4 0 0 0 0 0 0 0 0 6 ■5 0 5 0 0 0 6 0 5 0 0 0 4 3 0 0 0 5
(rt c C Crraabbggrraassss 9 9 4 4 0 0 6 6 9 9 3 3 9 9 4 9 6 9 6 9 9 9 9 2 2 9 9 0 0 2 9
00 </> D Duucckkssaallaadd 8 8 8 8 4 4 8 8 7 7 - - 9 9 9 9 8 8 7 9 9 9 9 5 3 8 8 2 0 8 9
H
H Bedstraw 6 7 1 0 0 0 6 6 3 4 3 0 3 - 0 4 0 0 0 - 0 0 - 0 2
H m G Giiaanntt ffooxxttaaiill 8 77 00 88 99 66 9 9 2 8 2 9 0 9 8 9 1 7 0 9 9 0 1 0 9 n o x MMoorrnniinngggglloorryy 6 3 00 00 11 22 3 4 2 1 1 6 1 2 0 4 0 1 0 0 0 0 0 0 7 m m
H Nutsedge - 0 - 0 0 - 0 0 4 0 4 0 0 0 0 0 0 0 0 j3 RRaappee 00 00 00 00 00 11 0 0 0 1 0 0 0 2 0 0 0 0 0 0 0 0 0 0 0 m RReeddrroooott ppiiggwweeeedd 55 44 00 00 00 00 3 1 3 3 0 0 0 2 0 0 0 0 0 0 0 0 0 3 0
S> RRiiccee 66 66 00 55 66 -- 6 3 3 7 7 6 4 7 7 7 2 0 5 7 5 0 0 0 5
S. Flatsedge 8 7 9 8 8 - 9 9 8 8 8 9 8 9 9 9 9 9 3 9 9 4 7 7 9
Soybean 3 4 2 3 1 5 3 4 2 3 3 3 1 5 1 5 1 1 0 2 4 1 3 1 4
Sugarbeets 0 0 0 0 0 1 1 0 2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Velve leaf 3 4 0 0 0 0 0 0 3 0 0 3 0 0 0 0 0 0 0 0 4 0 0 0 0
Wheat 0 4 0 0 4 0 5 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 ild oats 0 2 0 0 0 0 2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Table C COMPOUND
Rate 250 g/ha 14 15 19 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51
Figure imgf000112_0001
Preemergence
Blackgrass 4 0 4 0 0 8 8 7 0 4 9 6 8 0 0 8 0 0 3 0 9 0 0 9 0 0 0 7 7
B. signalgrass 3 8 - 8 2 - - - - 10 - - - - - - - 3 10 7 10 1 9 10 0 4 3 - -
Cocklebur 0 0 0 0 0 0 0 0 0 - - 0 0 0 0 0 0 0 0 0 0 0 - 0 0 0 0 - 0
Corn 0 0 0 0 0 9 8 5 9 5 9 - 6 3 4 6 0 0 4 0 4 0 0 9 0 0 0 7 7
Crabgrass 6 9 9 9 10 10 10 9 9 9 10 10 10 4 10 10 10 5 9 6 10 0 9 10 7 8 4 10 10
Bedstraw 5 0 3 0 0 7 4 0 0 0 0 7 0 0 0 3 0 0 0 0 10 0 0 - - 0 2 7 0
Giant foxtail 7 9 9 9 6 10 10 10 10 10 9 10 10 10 10 10 10 9 10 9 10 2 10 10 0 9 6 10 10
Morningglory 1 0 0 0 0 3 5 0 0 1 8 0 4 0 0 3 0 0 3 0 5 0 0 7 0 0 0 4 6
Nutsedge 0 0 0 0 0 10 8 0 7 0 10 0 0 0 0 0 0 0 - - 3 - 0 - - - 0 5 0
Rape 1 0 2 0 0 8 2 0 2 4 6 0 4 0 0 6 0 0 4 0 4 0 0 6 0 1 0 7 7
Redroot pigweed 3 6 7 6 0 6 3 0 0 0 5 0 6 0 0 2 5 0 1 0 4 0 0 6 0 1 0 6 4
Soybean 0 0 0 0 0 8 4 0 8 2 8 0 2 0 0 6 0 0 7 0 8 0 0 0 0 0 0 4 0
Sugarbeets 2 2 0 2 0 8 6 0 0 0 7 6 6 0 0 0 0 0 2 0 7 0 0 6 0 7 0 5 3
Velvetleaf 0 0 0 0 0 2 3 0 0 0 6 3 5 0 0 5 0 0 1 0 7 0 0 2 0 0 0 1 4
Wheat 0 0 0 0 0 0 0 0 0 0 6 0 6 0 0 3 0 0 5 0 7 0 0 6 0 0 0 0 0
Wild oats 2 2 0 2 0 9 8 3 0 0 7 2 3 0 0 2 0 3 6 0 9 0 2 9 0 0 0 9 0
Table C COMPOUND
Rate 250 g/ha 52 53 54 55 56 57 59 61 65 66 67 68 69 70 71 72 73 77 78 79 82 83 84 85 86
Preemergence
Blackgrass 5 9 5 7 3 6 5 2 3 7 8 6 2 5 0 3 0 4 2 0 2 0 0 0 6
B. signalgrass 6 8 8 7 3 3 3 - - 8 9 0 0 2 9
Cocklebur 0 0 - - 0 0 - - 0 0 0 - 0 0 0 0 - 0 0 0 0 0 0 0 -
Corn 4 5 0 3 - 4 8 6 0 8 0 5 0 7 0 3 0 0 0 7 8 0 0 0 4
Crabgrass 10 10 7 9 9 9 10 10 10 9 9 9 0 10 9 8 4 8 2 10 10 6 0 9 9
Bedstraw 0 7 5 0 0 0 3 0 2 0 2 3 6 0 0 0 0 3 0 0 0 0 0 0 0
Giant foxtail 10 10 10 10 10 10 10 10 10 10 10 9 10 10 9 9 6 10 9 10 9 6 0 9 9
Morningglory 5 4 0 2 3 0 6 0 0 0 0 2 0 5 0 0 0 0 0 0 0 0 0 0 0
Nutsedge 0 0 0 0 - 0 - 0 - 0 0 0 0 0 0 - 0 0 - 0 0 0 0 0 0
Rape 4 5 0 5 3 0 5 0 0 7 0 0 0 6 8 0 0 0 0 3 2 0 0 0 1
Redroot pigweed 6 6 0 5 4 0 3 3 0 0 2 0 0 4 3 0 0 2 0 3 6 0 0 0 4
Soybean 0 0 0 0 0 0 6 0 0 0 0 0 0 5 0 0 0 0 0 0 2 0 0 0 0
Sugarbeets 0 4 0 0 3 0 8 6 0 0 2 0 0 5 4 4 0 0 0 3 0 0 0 0 2
Velvetleaf 2 0 3 1 4 0 3 4 0 3 2 2 0 0 2 0 0 2 2 0 0 0 0 0 0
Wheat 0 0 0 0 0 0 7 0 0 2 2 0 0 0 0 0 0 0 0 0 2 0 0 0 0
Wild oats 1 2 0 2 3 2 8 2 0 7 3 0 0 0 0 0 0 0 0 4 7 0 0 0 2
Figure imgf000113_0001
Table C COMPOUND
Rate 125 g/ha 14 15 19 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51
Postemergence
Barnyardgrass 7 9 0 9 9 9 8 8 9 9 9 8 8 0 9 9 9 0 3 0 - 0 9 9 0 5 0 9 9
Blackgrass 0 0 0 0 0 4 3 0 0 0 8 2 9 0 0 8 0 0 1 0 4 0 0 0 0 0 0 6 1
B. signalgrass 0 0 0 0 0 9 9 0 5 0 9 - - - 0 4 0 0 0 0 0 0 - -
Cocklebur 1 0 0 0 0 1 1 0 0 3 0 0 0 0 0 0 0 0 0 0 0 0 0 4 - 2 0 0 0
Corn 0 0 0 0 0 6 0 0 2 3 5 0 3 0 0 6 0 0 6 0 5 0 0 3 0 0 0 4 3
Crabgrass 0 0 2 0 0 9 8 0 8 2 9 0 7 1 3 9 2 2 7 0 9 0 2 8 0 3 0 8 7
Ducksalad 4 2 5 2 8 9 8 7 6 9 8 6 7 3 7 8 8 - 9 7 9 7 9 9 7 8 7 ■ 9 7
Bedstraw 1 1 0 1 0 5 0 0 2 0 2 3 0 0 0 0 0 0 0 3 0 0 0 0 0 5 0 0 7
Giant foxtail 1 0 0 0 0 8 7 0 8 1 9 0 9 - 2 9 3 - 8 0 9 - 3 9 0 1 0 9 8 r
Morningglory 1 0 0 0 0 0 2 2 0 2 7 2 0 0 5 7 1 0 1 4 2 0 0 3 2 6 0 1 4
Nutsedge 0 0 0 0 0 2 .0 0 0 0 0 0 - 0 0 3 0 0 0 0 0 0 - 0 0 0 0 6 0
Rape 3 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 2
Redroot pigweed 1 0 0 0 0 0 0 0 0 0 2 0 0 0 0 0 0 0 2 5 0 0 0 0 0 3 0 2 3
Rice 6 6 0 6 2 8 7 7 6 5 7 6 7 3 6 6 3 0 6 0 6 3 5 7 0 3 0 6 5
S. Flatsedge 6 7 9 7 8 9 8 8 8 9 8 8 - 8 8 9 9 9 9 7 9 3 8 9 8 8 8 9 7
Soybean 1 3 1 3 1 6 5 3 6 7 3 1 3 2 5 5 3 2 5 1 5 1 3 3 3 2 0 5 4
Sugarbeets 7 0 0 0 3 0 0 0 0 0 0 0 0 0 0 0 0 0 1 1 0 0 0 0 0 5 0 0 0
Velvetleaf 1 0 0 0 0 2 0 0 0 2 3 0 0 0 0 0 0 0 0 3 0 0 0 0 0 0 0 3 0
Wheat 0 0 0 0 0 0 0 0 0 0 5 2 0 0 0 2 0 0 3 0 5 0 0 0 0 0 0 3 0
Wild oats 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0
Table C COMPOUND
Rate 125 g/ha 52 53 54 55 56 57 59 61 65 66 67 68 69 70 71 72 73 77 78 79 82 83 84 85 86
Postemergence
Barnyardgrass 9 9 7 8 7 - 8 2 9 9 9 8 9 5 9 4 2 8 4 6 8 0 0 2 7
Blackgrass 4 7 0 5 3 0 6 0 0 6 3 0 0 0 0 0 0 0 0 0 2 0 0 0 0
B. signalgrass 1 1 0 0 0 0 - - 2 3 0 0 0 0
Cocklebur 2 0 0 1 0 2 0 1 0 0 0 1 0 1 0 0 0 0 0 2 0 0 0 0 3
Corn 0 0 0 0 0 0 0 4 0 4 0 0 0 1 0 0 0 0 0 0 0 0 0 0 3
Crabgrass 8 4 0 6 6 2 9 8 2 9 4 8 2 9 9 9 3 0 0 8 9 0 0 0 8
Ducksalad 8 8 2 5 6 - 8 8 8 8 7 7 3 9 9 9 8 5 0 8 8 0 0 8 8
Bedstraw 6 6 0 0 0 0 4 0 2 0 3 0 2 0 0 0 0 0 0 - 0 0 0 0 0
Giant foxtail 7 5 0 7 9 2 9 6 2 5 2 7 0 9 8 8 0 0 0 6 8 0 0 0 6 (-
Morningglory 3 3 0 0 0 2 0 0 1 1 0 2 0 2 0 2 0 1 0 0 0 0 0 0 2
Nutsedge - - 0 - 0 0 0 0 0 - 0 0 2 0 0 0 0 0 0 - 0 0 0 0
Rape 0 0 0 0 0 1 0 0 0 0 0 0 0 2 0 0 0 0 0 0 0 0 0 0 0
Redroot pigweed 4 3 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Rice 6 5 0 4 6 - 6 3 3 6 6 4 0 4 4 6 0 - 2 6 5 0 0 0 3
S. Flatsedge 8 7 4 7 8 - 9 9 8 7 7 9 8 9 9 9 9 9 0 9 9 2 7 7 9
Soybean 3 4 2 3 0 3 3 4 1 2 3 2 1 3 1 2 1 1 0 2 2 1 3 1 3
Sugarbeets 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Velvetleaf 0 0 0 0 0 0 0 0 0 0 0 2 0 0 0 0 0 0 0 0 0 0 0 0 0
Wheat 0 3 0 0 2 0 5 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Wild oats 0 2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Table C COMPOUND
Rate 125 g/ha 14 15 19 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51
Preemergence
Blackgrass 0 0 4 0 0 8 7 6 0 0 9 4 2 0 0 4 0 0 2 0 9 0 0 9 0 0 0 7 7
B. signalgrass 0 8 - 8 0 - - - - 8 - - - - - - - 0 9 3 10 0 9 10 0 2 0 - -
Cocklebur 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Corn 0 0 0 0 0 8 5 2 7 5 3 2 0 0 0 3 0 0 0 0 3 0 0 8 0 0 0 7 5
Crabgrass 6 4 7 4 2 10 10 3 8 7 9 9 9 2 9 10 10 5 9 2 9 0 9 9 0 1 0 10 9
Bedstraw 2 0 2 0 0 7 0 0 0 - 0 - 0 0 0 0 0 0 0 0 9 0 0 7 0 0 0 6 0
Giant foxtail 3 5 8 5 5 10 10 9 8 10 9 10 10 10 10 10 10 6 10 4 10 0 10 10 0 9 5 10 10
Morningglory 0 0 0 0 0 1 1 0 0 0 4 0 2 0 0 3 0 0 0 0 4 0 0 3 0 0 0 4 5
Nutsedge 0 0 0 0 0 0 0 0 - 0 10 0 0 0 0 0 0 0 - 0 2 0 - - 0 - 0 - 0
Rape 0 0 0 0 0 8 0 0 0 1 0 0 2 0 0 2 0 0 0 0 1 0 0 5 0 0 0 7 0
Redroot pigweed 0 3 0 3 0 4 .3 0 0 0 5 0 4 0 0 0 0 0 0 0 2 0 0 0 0 0 0 6 4
Soybean 0 0 0 0 0 2 0 0 0 0 8 0 0 0 0 0 0 0 0 0 3 0 0 0 0 0 0 4 0
Sugarbeets 0 2 0 2 0 6 0 0 0 0 7 6 3 0 0 0 0 0 0 0 7 0 0 0 0 6 0 3 3
Velvetleaf 0 0 0 0 0 2 - 0 0 0 3 2 0 0 0 3 0 0 0 0 7 0 0 0 0 0 0 0 3
Wheat 0 0 0 0 0 0 0 0 0 0 6 0 0 0 0 0 0 0 2 0 6 0 0 2 0 0 0 0 0
Wild oats 0 0 0 0 0 5 3 0 0 0 6 0 0 0 0 2 0 0 4 0 7 0 2 7 0 0 0 9 0
Figure imgf000116_0001
Figure imgf000116_0002
Table C COMPOUND
Rate 125 g/ha 52 53 54 55 56 57 59 61 65 66 67 68 69 70 71 72 73 77 78 79 82 83 84 85 86
Figure imgf000117_0001
Preemergence
Blackgrass 4 7 4 5 2 2 5 0 3 3 3 3 2 0 0 2 0 2 0 0 0 0 0 0 1
B. signalgrass 3 8 5 7 3 2 2 - - 4 7 0 0 0 6
Cocklebur 0 0 0 0 0 0 - 0 0 0 0 - 0 0 0 0 0 0 0 0 0 0 0 0 0
Corn 4 4 0 0 - 0 2 0 0 3 0 0 0 3 0 0 0 0 0 0 0 0 0 0 0
Crabgrass 10 9 6 9 7 9 10 10 9 5 9 9 0 9 8 8 2 6 0 10 10 3 0 0 9
Bedstraw 0 7 0 0 0 - 1 0 2 0 0 3 - 0 0 0 0 0 0 0 0 0 0 0 0
Giant foxtail 10 10 10 10 10 8 10 9 10 10 10 9 9 10 9 7 5 10 2 10 9 2 0 3 9
Morningglory 0 4 0 1 2 0 3 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Nutsedge 0 0 - - 0 - 0 0 0 0 0 - 0 0 0 0 0 0 - 0 0 0 0 0 0
Ul
Rape 0 4 0 3 0 0 5 0 0 2 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0
Redroot pigweed 5 6 0 2 2 0 3 0 0 0 0 0 0 1 0 0 0 0 0 2 3 0 0 0 1
Soybean 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Sugarbeets 0 2 0 0 0 0 7 0 0 0 0 0 0 0 3 1 0 0 0 0 0 0 0 0 0
Velvetleaf 0 0 0 0 3 0 1 0 0 0 0 0 0 0 0 0 0 0 2 0 0 0 0 0 0
Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Wild oats 1 1 0 1 3 0 1 0 0 2 0 0 0 0 0 0 0 0 0 0 6 0 0 0 1
Figure imgf000117_0002
Table C COMPOUND
Rate 62 g/ha 14 15 19 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51
Postemergence
Barnyardgrass 2 9 0 9 9 9 8 6 9 9 8 5 3 0 9 9 1 0 3 0 8 0 2 9 0 2 0 9 9
Blackgrass 0 0 0 0 0 2 0 0 0 0 4 0 8 0 0 4 0 0 0 0 0 0 0 0 0 0 0 3 0
B. signalgrass 0 0 0 0 0 3 4 0 0 0 9 - - - 0 0 0 0 0 0 0 0 - -
Cocklebur 1 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 2 0 0 0
Corn 0 0 0 0 0 3 0 0 0 0 2 0 0 0 0 2 0 0 3 0 0 0 0 0 0 0 0 2 0
Crabgrass 0 0 0 0 0 8 0 0 2 0 7 0 - 0 0 3 1 0 5 0 5 0 0 5 0 2 0 8 0
Ducksalad 0 0 0 0 6 7 7 3 4 7 7 4 2 - 4 5 5 5 8 3 8 3 4 9 2 8 5 8 0
Bedstraw 0 0 0 0 0 4 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 5 0 0 0
Giant foxtail 0 0 0 0 0 8 2 0 2 0 9 0 3 0 2 2 3 0 5 0 8 0 0 8 0 0 0 9 6
O
Morningglory 1 0 0 0 0 0 0 0 0 2 1 1 0 0 3 2 0 0 1 2 0 0 0 1 0 6 0 1 3
Nutsedge 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 4 0
Rape 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0
Redroot pigweed 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 3 0 1 0
Rice 2 1 0 1 0 7 7 5 2 4 6 4 3 0 3 6 2 0 4 0 5 2 2 5 0 2 0 4 3
S. Flatsedge 5 2 9 2 8 8 5 8 7 9 8 8 6 - 8 9 5 9 9 7 8 3 8 9 3 8 7 9 6
Soybean 1 3 1 3 1 3 5 3 3 6 1 1 2 1 5 4 1 2 1 1 4 1 3 3 0 2 0 5 4
Sugarbeets 6 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 5 0 0 0
Velvetleaf 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Wheat 0 0 0 0 0 0 0 0 0 0 2 0 0 0 0 0 0 0 0 0 4 0 0 0 0 0 0 0 0
Wild oats 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Table C COMPOUND
Rate 62 g/ha 52 53 54 55 56 57 59 61 65 66 67 68 69 70 71 72 73 77 78 79 82 83 84 85 86
Postemergence
Barnyardgrass 9 9 4 8 5 - 6 0 8 9 8 7 5 2 8 0 0 6 0 4 6 0 0 0 3
Blackgrass 0 5 0 0 0 0 1 0 0 2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
B. signalgrass 0 0 0 0 0 0 - - 0 0 0 0 0 0
Cocklebur 2 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0
Corn 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Crabgrass 0 3 0 0 2 1 9 7 0 7 0 3 0 6 9 8 0 0 0 6 2 0 0 0 7
Ducksalad 3 8 2 5 3 - 8 8 4 8 5 4 2 8 8 8 8 3 0 8 8 0 0 2 8
Bedstraw 4 5 0 0 0 0 1 0 0 0 0 0 0 - 0 0 0 0 0 0 0 0 0 0 0
Giant foxtail 0 5 0 3 8 0 8 6 0 5 0 3 0 8 3 3 0 0 0 4 7 0 0 0 0 0 5 5
Morningglory 1 3 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 1
Nutsedge 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 - 0 0 0 0
Rape 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Redroot pigweed 4 3 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Rice 0 3 0 2 5 - 2 2 2 6 5 2 0 2 4 2 0 0 0 5 2 0 0 0 0 2
S. Flatsedge 8 6 1 7 7 - 9 9 8 6 7 8 6 9 9 9 9 8 0 9 9 0 0 0 2 9
Soybean 3 3 2 2 0 3 2 1 1 2 2 2 1 2 1 2 0 0 0 1 1 0 1 1 2
Sugarbeets 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Velvetleaf 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Wheat 0 0 0 0 2. 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 Wild oats 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Table C COMPOUND
Rate 62 g/ha 14 15 19 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51
Preemergence
Blackgrass 0 0 2 0 0 5 4 3 0 0 6 3 1 0 0 2 0 0 1 0 7 0 0 0 0 0 0 6 5
B. signalgrass 0 4 - 4 0 - - - - 8 - - - - - - - 0 9 0 9 0 9 9 0 0 0 - -
Cocklebur 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Corn 0 0 0 0 0 3 3 0 0 1 3 0 0 0 0 0 0 0 0 0 0 0 0 6 0 0 0 3 3
Crabgrass 2 0 7 0 2 8 8 2 6 6 9 7 9 2 9 10 2 1 7 2 8 0 6 8 0 1 0 10 9
Bedstraw 0 0 0 0 0 0 0 0 0 0 0 4 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 3 0
Giant foxtail 0 0 7 0 2 9 9 8 7 8 8 10 10 9 10 9 9 1 10 0 9 0 9 9 0 4 0 10 10
Morningglory 0 0 0 0 0 0 0 0 0 0 3 0 0 0 0 0 0 0 0 0 2 0 0 3 0 0 0 3 1
Nutsedge 0 0 0 0 0 0 0 0 0 0 10 0 0 0 0 0 0 0 0 - 0 0 0 -
0
Rape 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 4 0
Redroot pigweed 0 2 0 2 0 3 .3 0 0 0 3 0 2 0 0 0 0 0 0 0 1 0 0 0 0 0 0 3 3
Soybean 0 0 0 0 0 0 0 0 0 0 2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Sugarbeets 0 2 0 2 0 0 0 0 0 0 5 6 2 0 0 0 0 0 0 0 4 0 0 0 0 2 0 0 0
Velvetleaf 0 0 0 0 0 0 - 0 0 0 2 2 0 0 0 2 0 0 0 0 1 0 0 0 0 0 0 0 0
Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 3 0 0 0 0 0 0 0 0
Wild oats 0 0 0 0 0 2 0 0 0 0 3 0 0 0 0 0 0 0 0 0 4 0 0 7 0 0 0 1 0
Table C COMPOUND
Rate 62 g/ha 52 53 54 55 56 57 59 61 65 66 67 68 69 70 71 72 73 77 78 79 82 83 84 85 86
Preemergence
Blackgrass 2 6 0 3 0 0 3 0 2 2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 1
B. signalgrass 0 7 2 5 3 2 0 - - 3 7 0 0 0 6
Cocklebur - 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Corn 0 0 0 0 0 0 0 0 0 0 0 0 0 2 0 0 0 0 0 0 0 0 0 0 0
Crabgrass 9 9 6 9 7 0 8 8 6 5 8 0 0 9 8 5 0 0 0 10 9 0 0 0 9
Bedstraw 0 3 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Giant foxtail 10 10 9 9 9 2 9 9 9 9 9 9 8 9 8 5 1 9 0 9 9 0 0 0 9
Morningglory 0 4 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Nutsedge 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 - 0 0 0 0 0 0
Rape 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Redroot pigweed 00 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0 0 0 0 0 2 0 0 0 0
Soybean 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Sugarbeets 0 0 0 0 0 0 6 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Velvetleaf 0 0 0 0 2 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Wheat 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
Wild oats 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 . 0
Table C COMPOUND
Rate 31 g/ha 65 66 67 68 69 70 71 72 73 77 7Ϊ
Postemergence
Barnyardgrass 1 9 5 7 3 0 3 0 0 0 0
Blackgrass 0 0 0 0 0 0 0 0 0 0 0
B. signalgrass 0 0 0 0 - -
Cocklebur 0 0 0 0 0 0 0 0 0 0 0
Corn 0 0 0 0 0 0 0 0 0 0 0
Crabgrass 0 3 0 0 0 4 4 7 0 0 0
Ducksalad 4 0 4 0 0 3 7 7 5 0 0
Bedstraw 0 0 0 0 0 0 0 0 0 0 0
Giant foxtail 0 4 0 2 0 4 0 2 0 0 0
Morningglory 0 1 0 0 0 0 0 0 0 0 0
Nutsedge 0 0 0 0 0 0 0 0 0 0 0
Rape 0 0 0 0 0 0 0 0 0 0 0
Redroot pigweed 0 0 0 0 0 0 0 0 0 0 0
Rice 0 2 3 2 0 0 2 0 0 0 0
S. Flatsedge 5 2 6 8 4 8 9 8 4 0 0
Soybean 1 1 1 1 1 2 0 0 0 0 0
Sugarbeets 0 0 0 0 0 0 0 0 0 0 0
Velvetleaf 0 0 0 0 0 0 0 0 0 0 0
Wheat 0 0 0 0 0 0 0 0 0 0 0
Wild oats 0 0 0 0 0 0 0 0 0 0 0
Table C COMPOUND
Rate 31 g/ha 65 66 67 68 69 70 71 72 73 77 78
Preemergence
Blackgrass 0 0 0 0 0 0 0 0 0 0 0
B. signalgrass 5 1 0 0 - -
Cocklebur 0 0 0 0 0 0 0 - 0 0 0
Corn 0 0 0 0 0 0 0 0 0 0 0
Crabgrass 0 4 2 0 0 6 1 4 0 0 0
Bedstraw 0 0 0 0 0 0 0 0 0 0 0
Giant foxtail 9 7 9 8 3 9 3 3 0 8 0
Morningglory 0 0 0 0 0 0 0 0 0 0 0
Nutsedge 0 0 0 0 0 0 0 0 0 0 0 Rape 0 0 0 0 0 0 0 0 0 0 0
Redroot pigweed 0 0 0 0 0 0 0 0 0 0 0
Soybean 0 0 0 0 0 0 0 0 0 0 0
Sugarbeets 0 0 0 0 0 0 0 0 0 0 0
Velvetleaf 0 0 0 0 0 0 0 0 0 0 0
Wheat 0 0 0 0 0 0 0 0 0 0 0
Wild oats 0 0 0 0 0 0 0 0 0 0 0
TestD
The compounds evaluated in this test were formulated in a non-phytotoxic solvent mixture which included a surfactant and to water that covered the soil surface (flood application), a silt loam soil was used in the flood test. Water depth was approximately 2.5 cm for the flood test and was maintained at this level for the duration of the test.
Plant species in the flood test consisted of rice (Oryza sativa), umbrella sedge (Cyperus difformis), duck salad (Heteranthera limosa), barnyardgrass (Echinochloa crus-galli, designated as 'barnyardgrass 1 ') and late watergrass (Echinochloa oryzicola) grown to the 2- leaf stage for testing.
Plantings of these species were adjusted to produce plants of appropriate size for the postemergence portion of the test. 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 ratings, summarized in Table D, were recorded on a 0 to 100 scale where 0 is no effect and 100 is complete control. A dash (-) response means no test result.
Table D COMPOUND Table D COMPOUND
Rate 4000 g/ha 5 7 9 Rate 3000 g/ha 7
FLOOD FLOOD
Barnyardgrass 1 30 20 0 Barnyardgrass 1 0
Ducksalad 15 25 10 Ducksalad 10
Rice japonica 15 0 15 Rice japonica 0
Umbrella sedge 30 85 25 Umbrella sedge 65 Table D COMPOUND
Rate 2000 g/ha 2 3 4 5 7 9
FLOOD
Barnyardgrass 1 30 65 30 20 0 0
Ducksalad 25 65 10 10 10 10
Rice japonica 25 10 20 10 0 10
Umbrella sedge 85 90 75 20 30 20
Table D COMPOUND
Rate 1000 g/ha 1 2 3 4 5 6 7 8 9 24
FLOOD
Barnyardgrass 1 80 25 30 20 20 90 0 25 0 0
Ducksalad 90 20 45 10 10 100 10 75 0 50
Rice japonica 50 15 0 15 10 80 0 35 0 0
Umbrella sedge 85 75 60 15 0 95 20 90 10 -50
Table D COMPOUND
Rate 500 g/ha 1 2 3 4 5 6 8 9 20 21 24
FLOOD
Barnyardgrass 1 80 25 25 20 20 20 15 0 85 60 0
Ducksalad 80 15 35 10 10 95 50 0 50 40 30
Rice japonica 40 10 0 10 10 20 20 0 30 30 0
Umbrella sedge 80 0 20 0 0 95 85 0 90 55 35
Table D COMPOUND
Rate 250 g/ha 1 2 3 4 6 8 20 21 24
FLOOD
Barnyardgrass 1 60 20 25 20 0 0 80 0 0
Ducksalad 80 10 25 0 45 20 25 0 0
Rice japonica 20 10 0 0 0 0 25 0 0
Umbrella sedge 75 0 0 0 90 65 85 35 25 Table D COMPOUND Table D COMPOUND
Rate 125 g/ha 1 6 8 20 21 Rate 62 g/ha 1 20 21 24
FLOOD FLOOD
Barnyardgrass 1 40 0 0 65 0 Barnyardgrass 1 15 20 0 0
Ducksalad 70 40 10 10 0 Ducksalad 25 10 0 0
Rice japonica 10 0 0 15 0 Rice japonica 10 10 0 0
Umbrella sedge 70 80 40 75 25 Umbrella sedge 75 50 20 0
TestE
Compounds evaluated in this test were formulated in a non-phytotoxic solvent mixture which included a surfactant and applied to plants that were grown for various periods of time before treatment (postemergence application). A mixture of sandy loam soil and greenhouse potting mix in a 60:40 ratio was used for the postemergence test.
Plantings of these crops and weed species were adjusted to produce plants of appropriate size for the postemergence test. All plant species were grown using normal greenhouse practices. Crop and weed species include arrowleaf sida (Sida rhombifolia), barnyardgrass (Echinochloa crus-galli), cocklebur (Xanthium strumarium), common ragweed (Ambrosia elatior), corn (Zea mays), cotton (Gossypium hirsutum), eastern black nightshade (Solanum ptycanthum), fall panicum (Panicum dichotomiflorum), field bindweed (Convolvulus arvensis), giant foxtail (Setaria faberii), hairy beggarticks (Bidens pilosa), ivyleaf morningglory (Ipomoea hederacea), johnsongrass (Sorghum halepense), ladysthumb (Polygonum persicaria), lambsquarters (Chenopodium album), large crabgrass (Digitaria sanguinalis), purple nutsedge (Cyperus rotundus), redroot pigweed (Amaranthus retroflexus), soybean (Glycine max), Surinam grass (Brachiaria decumbens), velvetleaf (Abutilon theophrasti) and wild poinsettia (Euphorbia heterophylla).
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.
Table E COMPOUND Table E COMPOUND Rate 280 g/ha 37 39 Rate 140 g/ha 52 53 PREEMERGENCE POSTEMERGENCE Arrowleaf sida 40 10 Arrowleaf sida 0 0 Barnyardgrass 80 70 Barnyardgrass 10 10 Cocklebur 0 - Cocklebur 0 0
Common ragweed - - Common ragweed 20 10
Corn 15 20 Corn 0 0
Cotton 0 5 Cotton 5 15
E. blacknightsh 100 0 E. blacknightsh 0 0
Fall panicum 85 80 Fall panicum 10 5
Field bindweed 0 0 Field bindweed 0 0
Giant foxtail 100 60 Giant foxtail 0 0
H. beggarticks 100 - H. beggarticks 5 -
I . morningglory 0 0 I . morningglory 0 0
Johnsongrass 100 60 Johnsongrass 40 0
Ladysthumb 60 0 Ladys humb 0 0
Lambsquarters - 30 Lambsquarters 0 0
Large crabgrass 100 80 Large crabgrass 5 5
Purple nutsedge 0 0 Purple nutsedge 0 -
Redroot pigweed 10 100 Redroot pigweed 0 0
Soybean 10 40 Soybean 40 20
Surinam grass 20 70 Surinam grass 0 0
Velvetleaf 0 0 Velvetleaf 0 0
Wild poinsettia 50 30 Wild poinsettia 0 0
Table E COMPOUND
Rate 140 g/ha 35 37 38 39 50 52 53 55 56
PREEMERGENCE
Arrowleaf sida 40 40 70 10 50 0 0 0
Barnyardgrass 85 70 90 40 100 70 90 70 80
Cocklebur 0 0 80 0 0 0
Common ragweed 0 50 0 0
Corn 10 10 30 5 65 50 20 40
Cotton 0 0 5 0 20 10 10 10
E. blacknightsh 85 30 80 0 0 50 50 40
Fall panicum 85 70 80 80 100 100 100 100 100
Field bindweed 0 0 0 0 0 0 0 0 0
Giant foxtail 100 70 80 40 100 60 90 100 85 H. beggarticks 30 - - - - 0 0 - 0 I. morningglory 0 0 0 0 0 30 0 0 0 Johnsongrass 50 10 70 0 100 80 100 100 85
Ladysthumb 100 - 80 0 0 100 80 80
Lambsquarters 70 - 80 10 100 40 50 60 0
Large crabgrass 80 60 90 0 100 100 100 100 85 Purple nutsedge 0 0 10 0 0 0 0 0 0
Redroot pigweed 100 10 70 70 100 80 0 80 0
Soybean 20 10 40 5 15 15 20 20 10
Surinam grass 80 20 75 5 100 70 70 30 5
Velvetleaf 0 0 0 0 40 0 40 10 0
Wild. poinsettia 60 30 80 10 50 0 30 0 0
Table E COMPOUND
Rate 70 g/ha 35 37 38 39 50 52 53 55 56
PREEMERGENCE
Arrowleaf sida 20 - 20 10 0 0 0 0 0
Barnyardgrass 75 20 80 40 90 0 30 50 5
Cocklebur 0 0 0 0 0 0 0 0 0
Common ragweed - - - - 0 0 0 0 0
Corn 10 10 10 - 40 0 10 10 0
Cotton 0 0 0 0 10 10 10 0 0
E. blacknightsh 0 0 20 0 0 50 50 0 0
Fall panicum 70 50 70 10 100 100 100 100 100
Field bindweed 0 0 0 0 0 0 0 0 0
Giant foxtail 60 0 55 0 100 20 60 0 30
H. beggarticks - 20 0 - - 0 - 0
I . morningglory 0 0 0 0 0 0 0 0 0
Johnsongrass 20 5 70 0 100 80 100 50 40
Ladysthumb 30 0 70 - 0 - 80 0 0
Lambsquarters 70 - 60 10 50 - 40 60 -
Large crabgrass 80 30 70 0 80 70 100 85 70
Purple nutsedge 0 0 0 0 0 0 0 0 0
Redroot pigweed 70 10 10 65 100 0 0 0 0
Soybean 20 10 20 5 0 0 0 5 0
Surinam grass 70 0 60 0 85 5 0 0 0
Velvetleaf 0 0 0 0 0 0 10 0 0
Wild poinsettia 50 20 40 0 0 0 20 0 0 Table E COMPOUND
Rate 35 g/ha 35 37 38 39 50 52 53 55 56
PREEMERGENCE
Arrowleaf sida 20 - 10 0 0 0 0 0 0
Barnyardgrass 60 0 70 0 70 0 0 10 0
Cocklebur 0 0 - 0 0 0 0 0 0
Common ragweed - - - - 0 0 0 0 0
Corn 0 0 5 0 5 0 0 0 0
Cotton 0 - 0 - 5 10 0 0 0
E. blacknightsh 0 0 0 0 0 0 0 0 0
Fall panicum 0 45 30 0 40 100 100 0 100
Field bindweed 0 0 0 0 0 0 0 0 0
Giant foxtail 10 0 0 0 30 0 50 0 0
H. beggarticks - - 0 - - - 0 - -
I . morningglory 0 0 0 0 0 0 0 0 0
Johnsongrass 5 0 10 0 70 50 40 0 0
Ladysthumb 0 0 0 0 0 50 - 0 0
Lambsquarters 65 - 50 0 50 - 40 0 0
Large crabgrass 20 20 10 0 - 40 50 40 0
Purple nutsedge 0 0 0 0 0 0 0 0 0
Redroot pigweed 20 10 0 20 20 0 0 0 0
Soybean 15 10 15 0 0 0 0 0 0
Surinam grass 0 0 10 0 10 0 0 0 0
Velvetleaf 0 0 0 0 0 0 0 0 0
Wild poinsettia 20 20 0 0 0 0 0 0 0
Table E COMPOUND
Rate 17 g/ha 35 38 50 52 53 55 56
PREEMERGENCE
Arrowleaf sida 10 10 0 0 0 0 0
Barnyardgrass 50 40 20 0 0 0 0
Cocklebur 0 0 0 0 0 0 0
Common ragweed - - 0 0 0 0 0
Corn 0 0 0 0 0 0 0
Cotton 0 0 0 0 0 0 0
E. blacknightsh 0 0 0 0 - 0 0 Fall panicum 0 0 0 - 0 0 0
Field bindweed 0 0 0 0 0 0 0
Giant foxtail 0 0 0 0 10 0 0
H. beggarticks - - 0 0 0 0 -
I. morningglory 0 0 0 0 0 0 0
Johnsongrass 0 5 5 10 10 0 0
Ladysthumb 0 0 0 0 - 0 -
Lambsquarters - - 0 0 - 0 0
Large crabgrass 5 5 0 0 0 0 0
Purple nutsedge 0 0 0 0 0 0 0
Redroot pigweed 0 - 0 0 0 0 0
Soybean 15 15 0 0 0 0 0
Surinam grass 0 0 0 0 0 0 0
Velvetleaf 0 0 0 0 0 0 0
Wild poinsettia 20 0 0 0 0 0 0
Test F
Plastic pots were partially filled with silt loam soil. The soil was then saturated with water. Indica Rice (Oryza sativa) seed or seedlings at the 2.0-leaf stage, seeds, tubers or plant parts selected from arrowhead (Sagittaria rigida), barnyardgrass (Echinochloa crus- galli), common water plantain (Alisma plantago-aquatica), ducksalad (Heteranthera limosa), early watergrass (Echinochloa oryzoides), gooseweed (Sphenoclea zeylanica), junglerice (Echinochloa colonum), late watergrass (Echinochloa oryzicola), onochoria (Monochoria vaginalis), river bullrush (Scirpus fluviatikis), redstem (Ammania species), rice flatsedge (Cyperus iria), smallflower flatsedge (Cyperus difformis), tighthead sprangletop (Leptochloa fasicularis) and water-clover (Marsilea quadrifolia) were planted into this soil. The various rice seed types and methods are designated as: Rice indica 1 (2 leaf direct seeded indica type rice), Rice indica 3 (2 leaf transplanted indica type rice), Rice japonica 1 (2 leaf direct seeded japonica type rice) and Rice japonica 2 (2 leaf transplanted japonica type rice). Plantings and waterings of these crops and weed species were adjusted to produce plants of appropriate size for the test. At the 2-leaf stage, water levels were raised to 3 cm above the soil surface and maintained at this level throughout the test. Chemical treatments were formulated in a non-phytotoxic solvent mixture which included a surfactant and applied directly to the paddy water by pipette, or to the plant foliage by an air pressure-assisted, calibrated belt-conveyer spray system. Treated plants and controls were maintained in a greenhouse for approximately 21 days, after which all species were compared to controls and visually evaluated. Plant response ratings, summarized in Table F, are reported on a 0 to 100 scale where 0 is no effect and 100 is complete control. A dash (-) response means no test result.
Table F COMPOUND Table F COMPOUND
Rate 1000 g/ha 20 Rate 750 g/ha 16 17 20
Paddy / silt loam Paddy / silt loam
Arrowhead Arrowhead 95
Barnyardgrass 95 Barnyardgrass 100 100 95
C. waterplantai C. waterplantai 95
Ducksalad 100 Ducksalad 100 100 100
E. watergrass 90 E. watergrass 100 100 80
Gooseweed Gooseweed 55 65 -
Junglerice Junglerice 100 100 -
L. watergrass 98 L. watergrass 100 100 85
Monochoria Monochoria 95 85 -
R. bulrush R. bulrush 90 - -
Redstem 95 Redstem 100 100 98
Rice flatsedge 100 Rice flatsedge 100 100 100
Rice indica 1 Rice indica 1 85 80 -
Rice indica 3 Rice indica 3 15 30 -
Rice japonica 1 65 Rice japonica 1 80 - 80
Rice japonica 2 45 Rice japonica 2 15 - 35
S. flatsedge 100 S. flatsedge 100 100 98
T. sprangletop 100 T. sprangletop 100 100 100
Water-clover Water clover 70
Table F COMPOUND Table F COMPOUND
Rate 500 g/ha 16 17 20 27 43 54 Rate 400 g/ha 43
Paddy / silt loam Paddy / silt loam
Arrowhead 30 Arrowhead
Barnyardgrass 100 100 98 100 100 80 Barnyardgrass 100
C. waterplantai 95 C. waterplantai
Ducksalad 100 100 100 100 100 100 Ducksalad 100 E. watergrass 100 100 85 100 100 100 E. watergrass 100 Gooseweed 45 70 Gooseweed Junglerice 100 100 - 100 100 100 Junglerice 100 L. watergrass 100 100 98 100 100 100 L. watergrass 100 Monochoria 90 80 Monochoria R. bulrush 90 R. bulrush Redstem 95 100 85 100 100 100 Redstem 100 Rice flatsedge 100 100 100 100 100 100 Rice flatsedge 100 Rice indica 1 80 85 - 85 - - Rice indica 1 Rice indica 3 20 30 - 30 - - Rice indica 3 Rice japonica 1 80 - 65 - 100 95 Rice japonica 1 90 Rice japonica 2 0 - 5 - 100 0 Rice japonica 2 100 S. flatsedge 100 100 100 100 100 100 S. flatsedge 100 T. sprangletop 100 100 100 100 100 100 T. sprangletop 100 Water -clover 80 Water-clover
Table F COMPOUND Table F COMPOUND
Rate 375 g/ha 16 17 20 27 54 Rate 300 g/ha 27 43 77
Paddy / silt loam Paddy / silt loam
Arrowhead 65 40 - - - ■ Arrowhead 60
Barnyardgrass 80 100 98 100 65 Barnyardgrass 100 100 100
C. waterplantai 90 70 - - - C. waterplantai 98
Ducksalad 85 95 98 100 100 Ducksalad - 100 100
E. watergrass 100 100 98 100 100 E. watergrass 100 100 100
Gooseweed 20 80 - - - Gooseweed 100
Junglerice 100 100 - 100 100 Junglerice 100 90
L. watergrass 100 100 98 100 100 L. watergrass 100 100 98
Monochoria 85 60 - - - Monochoria 95
R. bulrush 90 85 - - - R. bulrush 95
Redstem 90 95 75 100 98 Redstem - 95 95
Rice flatsedge 100 100 100 100 100 Rice flatsedge - 100 70
Rice indica 1 65 60 - 80 - Rice indica 1 75
Rice indica 3 10 20 - 30 - Rice indica 3 15
Rice japonica 1 75 - 65 - 80 Rice japonica 1 - 90 70
Rice japonica 2 0 - 20 - 0 Rice japonica 2 - 80 0
S. flatsedge 100 100 100 100 100 S. flatsedge - 100 100
T. sprangletop 100 100 100 100 100 T. sprangletop - 100 75
Water-clover 35 35 - - - Water -clover 75 Table F COMPOUND
Rate 250 g/ha 16 17 20 27 54 65 69 77
Paddy / silt loam
Arrowhead 35 40 - 60
Barnyardgrass 75 95 85 100 55 100 100 95
C. waterplantai 40 80 - 98
Ducksalad 65 20 20 100 80 100 98 100
E. watergrass 90 45 65 100 100 100 100 98
Gooseweed 20 70 - 100 - - -
Junglerice 98 100 - 100 100
L. watergrass 100 100 98 100 98 100 100 90
Monochoria 60 60 - 95
R. bulrush 95 90 - 90
Redstem 80 60 60 100 98 98 98 95
Rice flatsedge 95 95 100 100 100 100 100 70
Rice indica 1 20 25 - 70 - - - -
Rice indica 3 15 10 - 25 - - - -
Rice japonica 1 35 - 65 - 70 80 98 40
Rice japonica 2 0 - 0 - 0 0 0 0
S. flatsedge 100 95 98 100 100 100 100 100
T. sprangletop 100 100 100 100 100 100 100 70
Water-clover 30 20 - 85
Table F COMPOUND
Rate 200 g/ha 15 26 27 43 65 69 77
Paddy / silt loam
Arrowhead - - 35
Barnyardgrass 35 35 80 95 100 100 100
C. waterplantai - - 100 - - - -
Ducksalad 65 65 100 100 100 98 100
E. watergrass 90 90 65 100 100 100 95
Gooseweed - - 100 -
Junglerice 45 45 100 85
L. watergrass 70 70 100 100 100 100 95
Monochoria - - 95
R. bulrush - - 90 Redstem 85 85 100 95 98 98 90
Rice flatsedge 100 100 100 100 100 100 60
Rice indica 1 40 40 20
Rice indica 3 25 25 0
Rice japonica 1 - - - 80 60 95 30
Rice japonica 2 - - 45 0 0 10
S. flatsedge 100 100 100 100 100 100 100
T. sprangletop 100 100 100 100 100 100 65
Water -clover - 40
Table F COMPOUND
Rate 150 g/ha 15 26 27 31 37 39 65 69 77
Paddy / silt loam
Arrowhead - - 35 100
Barnyardgrass 15 15 50 100 90 80 98 100 95
C. waterplantai - - 100 98
Ducksalad 50 50 80 85 98 35 100 98 80
E. watergrass 40 40 55 100 95 100 98 100 95
Gooseweed - - - 100 80
Junglerice 45 45 95 100 90 70
L. watergrass 60 60 75 100 95 75 75 100 45
Monochoria - - 95 95
R. bulrush - - 90 90
Redstem 60 60 100 100 95 30 98 98 70
Rice flatsedge 100 100 100 100 100 100 100 100 40
Rice indica 1 15 15 10 85 45 65
Rice indica 3 15 15 0 10 10 0 - - -
Rice japonica 1 - - - 45 - - 50 90 35
Rice japonica 2 - - - 10 - - 0 0 0
S. flatsedge 100 100 100 100 100 85 100 100 100
T. sprangletop 65 65 100 100 100 100 100 100 55
Water -clover - - 80 75 Table F COMPOUND
Rate 125 g/ha 16 17 27 31 32 37 39 54 55 66 68
Paddy / silt loam
Arrowhead 0 40 - 100
Barnyardgrass 95 100 75 100 100 100 25 30 100 100 100
C. waterplantai 20 80 - 98
Ducksalad 0 0 95 98 80 85 0 65 100 98 100
E. watergrass 35 65 100 100 100 95 95 100 100 100 95
Gooseweed 20 70 - 70
Junglerice 95 100 100 100 100 75 70 100 100
L. watergrass 40 80 100 100 100 100 45 30 100 95 100
Monochoria 60 55 - 95
R. bulrush 75 80 - 95
Redstem . 20 0 100 100 100 90 20 95 95 95 98
Rice flatsedge 95 85 100 100 10 100 100 90 100 100 80
Rice indica 1 10 15 30 70 80 40 65
Rice indica 3 0 0 0 20 10 15 10 - - - -
Rice japonica 1 10 - - 60 - - - 50 98 75 75
Rice japonica 2 0 - - 25 - - - 0 25 25 0
S. flatsedge 95 95 100 100 100 100 85 100 100 100 100
T. sprangletop 98 100 100 100 100 100 100 100 100 100 100
Water-clover 70 0 - 80
Table F COMPOUND
Rate 100 g/ha 15 26 27 31 32 37 38 39 43 50 51 52 53 55 65 66 68 69
Paddy / silt loam
Arrowhead - - 25 60 - - - - 70
Barnyardgrass 10 10 25 90 100 98 80 100 100 100 95 100 100 100 98 100 100 100
C. waterplantai - - 95 95 - - - - - 95
Ducksalad 60 60 50 80 85 80 90 60 90 100 100 - 100 100 90 95 100 90
E. watergrass 65 65 30 100 100 100 95 85 100 100 90 100 100 100 98 98 98 90
Gooseweed - - 100 65 - - - - - 85
Junglerice 55 55 50 100 100 60 95 10 60 - 100 100 100 100
L. watergrass 35 35 65 100 100 95 80 65 100 95 90 100 100 100 60 90 95 98 <_o
LO
Monochoria - - 80 95 - - - - - 85
R. bulrush - - 90 95 - - - - - 90
Redstem 70 70 100 100 100 70 80 20 60 98 95 - 95 90 95 90 98 95
Rice flatsedge 90 90 100 100 98 98 100 100 95 100 100 100 100 100 100 100 50 100
Rice indica 1 10 10 0 60 65 30 55 35
Rice indica 3 15 15 0 0 0 10 20 0
Rice japonica 1 - - - 40 - - - - 30 90 75 99 98 95 25 60 60 85
Rice japonica 2 - - - 10 - - - - 15 0 60 0 0 0 0 10 0 0
S. flatsedge 100 .00 100 100 100 95 100 80 100 100 100 - 100 100 100 100 100 100
T. sprangletop 75 75 100 100 100 100 95 100 100 100 100 100 100 100 100 100 100 98
Water -clover - - 75 80 - - - - - 75 -
Table F COMPOUND Table F COMPOUND
Rate 80 g/ha 50 51 52 53 Rate 80 g/ha 50 51 52 53 Paddy / silt loam Paddy / silt loam Arrowhead - 60 Redstem • 98 95 98 80 Barnyardgrass 100 90 100 98 Rice flatsedge 100 100 100 98 C. waterplantai 95 Rice indica 1 . . . . Ducksalad 100 100 100 100 Rice indica 3 . . . . E. watergrass 100 100 100 100 Rice japonica 1 80 45 "80 98
Gooseweed - 75 Rice japonica 2 0 35 0 0
Junglerice - 100 100 100 S. flatsedge 100 100 100 100 L. watergrass 98 95 100 100 T. sprangletop 100 100 100 100 Monochoria - 90 Water -clover 75 R. bulrush - 90
Table F COMPOUND
Rate 75 g/ha 27 31 32 37 38 39 55 66 68 77
Paddy / silt loam
Arrowhead 65
Barnyardgrass 15 98 90 100 65 75 25 100 100 60
C. waterplantai 90
Ducksalad 35 98 80 65 75 80 98 90 100 50
E. watergrass 20 90 60 85 60 15 100 95 - 20
Gooseweed 70
Junglerice 35 100 100 45 95 20 100.
L. watergrass 20 95 100 90 80 0 100 75 98 25
Monochoria 85
R. bulrush 90
Redstem 95 98 100 55 65 30 90 80 95 60
Rice flatsedge 100 98 100 100 100 95 100 100 40 40
Rice indica 1 0 60 55 35 30 15
Rice indica 3 0 0 0 0 15 0 -
Rice japonica 1 35 - 90 55 30 15
Rice japonica 2 20 0 10 0 0
S. flatsedge 100 100 100 95 100 75 100 100 100 80
T. sprangletop 100 100 100 100 98 90 100 100 100 80
Water-clover 90 Table F COMPOUND Table F COMPOUND Rate 64 g/ha 27 54 Rate 60 g/ha 50 51 52 53 Paddy / silt loam Paddy / silt loam Arrowhead Arrowhead 50
Barnyardgrass 35 25 Barnyardgrass 100 100 90 95 C. waterplantai C. waterplantai 98 Ducksalad 90 60 Ducks'alad 100 75 100 100 E. watergrass 40 100 E. watergrass 100 100 100 100 Gooseweed Gooseweed 70
Junglerice 95 100 Junglerice 100 100 100 L. watergrass 40 25 L. watergrass 95 100 100 95 Monochoria Monochoria 90 R. bulrush R. bulrush 90
Redstem 85 80 Redstem 98 90 98 65
Rice flatsedge 100 55 Rice flatsedge 100 100 90 95
Rice indica 1 0 - Rice indica 1
Rice indica 3 0 - Rice indica 3
Rice japonica 1 - 0 Rice japonica 1 40 30 0 98
Rice japonica 2 - 0 Rice japonica 2 15 0 0 0
S. flatsedge 95 85 S. flatsedge 100 100 100 100
T. sprangletop 100 100 T. sprangletop 100 98 100 100
Water -clover - . Water -clover 60
Table F COMPOUND
Rate 50 g/ha 15 26 2 277 31 32 37 38 39 55 65 66 68 69
Paddy / silt loam
Arrowhead - - 15
Barnyardgrass 15 15 0 0 ι60 40 45 60 60 20 85 98 98 95
C. waterplantai - - 80
Ducksalad 10 10 0 0 185 75 65 20 15 95 80 70 90 75
E. watergrass 25 25 0 0 11100 60 45 45 0 100 80 90 95 20
Gooseweed - - .40
Junglerice 2 200 2200 2255 11100 100 - 25 0 100
L. watergrass 1 100 1100 1100 I60 55 45 65 45 100 25 75 30
Monochoria - - 55
R. bulrush . - <90 Redstem 0 0 45 90 95 35 10 0 85 85 65 75 85 Rice flatsedge 70 70 98 95 95 85 95 85 75 90 90 100 100 Rice indica 1 0 0 0 45 15 20 10 0 Rice indica 3 10 10 0 0 0 0 0 .0 - • - Rice japonica 1 - 15 - - - - 85 15 25 10 60 Rice japonica 2 0 - - - - 0 0 10 5 0 S. flatsedge 100 100 100 100 100 98 98 80 100 100 98 98 95 T. sprangletop 65 65 100 100 100 90 90 80 100 90 100 100 98 Water-clover - 15
Table F COMPOUND Table F COMPOUND
Rate 40 g/ha 50 51 52 53 Rate 32 g/ha 54
Paddy / silt loam Paddy / silt loam
Arrowhead 45 Arrowhead
Barnyardgrass 95 100 100 20 Barnyardgrass 20
C. waterplantai 95 C. waterplantai
Ducksalad 98 80 90 90 Ducksalad 55
E. watergrass 100 90 100 100 E. watergrass 100
Gooseweed 60 Gooseweed
Junglerice 100 100 100 Junglerice 100
L. watergrass 90 95 100 60 L. watergrass 20
Monochoria 35 Monochoria
R. bulrush 90 R. bulrush
Redstem 90 90 90 45 Redstem 70
Rice flatsedge 100 100 80 90 Rice flatsedge 40
Rice indica 1 Rice indica 1
Rice indica 3 Rice indica 3
Rice japonica 1 35 25 0 40 Rice japonica 1 0
Rice japonica 2 0 10 0 0 Rice japonica 2 0
S. flatsedge 100 100 100 100 S. flatsedge 70
T. sprangletop 100 100 90 100 T. sprangletop 65
Water-clover 85 Water-clover Table F COMPOUND Table F COMPOUND
Rate 25 g/ha 15 26 32 38 66 68 Rate 20 g/ha 50 51 52 53 55
Paddy / silt loam Paddy / silt loam
Arrowhead - - - - - - Arrowhead - 40 - - -
Barnyardgrass 0 0 40 10 65 55 Barnyardgrass 98 85 70 0 15
C. waterplantai - - - - - - C. waterplantai - 30 - - -
Ducksalad 0 0 50 20 40 55 Ducksalad 60 60 15 0 60
E. watergrass 0 0 25 0 95 70 E. watergrass 100 40 100 100 100
Gooseweed - - - - - - Gooseweed - 20 - - -
Junglerice 0 0 100 0 - - Junglerice - 100 100 100 100
L. watergrass 0 0 0 10 0 0 L. watergrass 35 90 0 95 15
Monochoria - - - - - - Monochoria - 20 - - -
R. bulrush - - - - - - R. bulrush - 85 - - -
Redstem 10 10 80 15 30 65 Redstem 30 40 80 30 80
Rice flatsedge 20 20 40 90 90 98 Rice flatsedge 50 90 70 85 60
Rice indica 1 0 0 10 0 - - Rice indica 1 - - - - -
Rice indica 3 10 10 0 0 - - Rice indica 3 - - - - -
Rice japonica 1 - - - - 0 10 Rice japonica 1 10 10 0 25 50
Rice japonica 2 - - - - 0 5 Rice japonica 2 0 0 0 0 0
S. flatsedge 10 10 100 90 95 98 S. flatsedge 100 100 98 35 100
T. sprangletop 10 10 35 75 90 40 T. sprangletop 80 95 85 100 100
Water-clover - - - - - - Water-clover - 35 - . -
Table F COMPOUND Table F COMPOUND
Rate 10 g/ha 38 Rate 10 g/ha 38
Paddy / silt loam Paddy / silt loam
Arrowhead - Redstem 0
Barnyardgrass 0 Rice flatsedge 95
C. waterplantai - Rice indica 1 10
Ducksalad 0 Rice indica 3 10
E. watergrass 10 Rice japonica 1
Gooseweed - Rice japonica 2
Junglerice 20 S. flatsedge 60
L. watergrass 0 T. sprangletop 0
Monochoria - Water-clover
R. bulrush . Test G
Compounds evaluated in this test were formulated in a non-phytotoxic solvent mixture and applied to the surface of the water which was contained in each pot. Individual containers of barnyardgrass (Echinochloa oryzicola), small flower umbrella sedge (Cyperus difformus), common falsepimpernel (Lindernia procumbens), monochoria (Monochoria vaginalis) and bulrush (Scirpus juncoides) were seeded and allowed to grow until the leaf stage of development was reached. A Sultama clay loam soil was used for this propagation. Japonica rice (Oryza sativa) was transplanted at 0 and 2 cm depth (designated Rice japonica 1 and Rice japonica 2 respectively) five days before application of the test compound to the water surface. An early and late stage of each weed species was treated, the stage of development being related to the concurrent planting of Scirpus juncoides which was then treated at the 1.5 (early (1)) and the 2.5 (late (2)) leaf stage.
Treated plants and untreated controls were maintained under greenhouse conditions for twenty to thirty days at which time treated plants were compared to untreated controls and visually evaluated. Plant response ratings, summarized in Table G, are based upon a 0 to 100 scale where 0 is no effect and 100 is complete control. A dash response (-) indicated that no test result was recorded.
Table G COMPOUND Table G COMPOUND
Rate 500 g/ha 27 54 77 Rate 500 g/ha 27 54 77 Flood Saita soil Flood Saita soil Barnyardgrass 1 100 100 100 Rice japonica 1 95 95 100 Barnyardgrass 2 100 100 100 Rice japonica 2 30 0 15 Falsepimpernell 85 90 95 S. flatsedge 1 100 100 100 Falsepimpernel2 85 85 90 S. flatsedge 2 100 100 100 Monochoria 1 100 90 100 Scirpus 1 100 100 100
Monochoria 2 95 80 95 Scirpus 2 90 95 95
Table G COMPOUND
Rate 250 g/ha 15 26 27 31 32 54 65 77
Flood Saita soil
Barnyardgrass 1 100 100 100 100 100 100 100 100
Barnyardgrass 2 100 100 100 100 100 100 100 100
Falsepimpernell 90 90 85 70 80 85 100 95
Falsepimpernel2 100 100 80 90 90 90 95 80
Monochoria 1 60 60 100 100 95 90 100 100 Monochoria 2 60 60 95 95 95 60 95 95
Rice japonica 1 95 95 95 95 95 95 100 95 Rice japonica 2 0 0 0 25 0 0 0 0
S. flatsedge 1 100 100 100 100 100 100 100 100
S. flatsedge 2 100 100 100 100 100 100 100 100
Scirpus 1 100 100 100 100 100 100 100 100
Scirpus 2 95 95 90 90 95 95 95 90
Table G COMPOUND
Rate 125 g/ha 15 26 27 31 32 50 52 53 54 65 66 77 Flood Saita soil
Barnyardgrass 1 95 95 100 100 100 100 100 100 100 100 100 95
Barnyardgrass 2 95 95 100 100 100 100 100 100 75 100 100 100
Falsepimpernell 80 80 70 90 60 95 80 95 80 90 95 70
Falsepimpernel2 90 90 85 85 90 90 85 90 85 90 85 60
Monochoria 1 70 70 100 100 100 100 100 100 90 100 100 95
Monochoria 2 50 50 95 95 95 95 95 90 70 95 95 95
Rice japonica 1 90 90 70 95 90 95 85 90 25 95 95 90 Rice japonica 2 0 0 0 0 0 50 10 0 0 0 0 0
S. flatsedge 1 100 100 100 100 100 100 100 100 100 100 100 100
S. flatsedge 2 100 100 100 100 100 100 100 100 100 100 100 100
Scirpus 1 100 100 100 100 100 100 100 100 90 100 95 95
Scirpus 2 90 90 90 90 90 90 90 95 80 95 95 85
Table G COMPOUND
Rate 64 g/ha 15 26 27 31 32 50 52 53 54 65 66 77 Flood Saita soil
Barnyardgrass 1 80 80 100 100 100 100 100 100 85 100 100 95
Barnyardgrass 2 60 60 100 100 100 100 100 100 30 90 100 85
Falsepimpernell 40 40 60 50 70 95 90 90 75 80 80 30
Falsepimpernel2 60 60 90 80 85 85 80 90 80 85 80 70
Monochoria 1 20 20 95 100 100 100 95 100 70 100 95 95
Monochoria 2 0 0 85 95 95 95 75 95 40 95 95 60
Rice japonica 1 60 60 50 85 90 95 90 80 30 85 95 75
Rice japonica 2 0 0 0 0 0 10 0 0 20 0 0 10
S. flatsedge 1 100 100 100 100 100 100 100 100 100 100 100 95 S. flatsedge 2 100 100 100 100 100 100 100 100 95 100 100 100
Scirpus 1 100 100 95 100 100 100 100 100 80 100 100 90
Scirpus 2 70 70 95 90 90 95 90 90 30 90 95 85
Table G COMPOUND
Rate 32 g/ha 15 26 31 32 50 52 53 65 66 Flood Saita soil
Barnyardgrass 1 30 30 100 100 100 100 100 100 100
Barnyardgrass 2 50 50 100 90 100 100 80 70 100
Falsepimpernell 50 50 50 60 90 90 70 70 60
Falsepimpernel2 60 60 50 70 90 85 80 70 50
Monochoria 1 0 0 95 95 95 100 95 100 95
Monochoria 2 0 0 95 80 95 95 75 80 95
Rice japonica 1 20 20 60 15 95 70 60 40 95 Rice japonica 2 0 0 0 0 0 0 0 0 0
S. flatsedge 1 100 100 100 100 100 100 100 100 100
S. flatsedge 2 100 100 95 100 100 100 100 100 100
Scirpus 1 90 90 95 100 100 95 95 95 95
Scirpus 2 80 80 90 90 90 90 90 90 90
Table G COMPOUND Table G COMPOUND
Rate 16 g/ha 50 52 53 66 Rate 16 g/ha 50 52 53 66 Flood Saita soil Flood Saita soil
Barnyardgrass 1 100 40 75 95 Rice japonica 1 75 30 40 40
Barnyardgrass 2 85 50 60 80 Rice japonica 2 0 20 0 0
Falsepimpernell 80 85 75 40 S. flatsedge 1 100 100 100 95
Falsepimpernel2 85 60 70 50 S. flatsedge 2 100 100 100 100
Monochoria 1 95 80 60 70 Scirpus 1 100 100 90 85
Monochoria 2 70 60 60 60 Scirpus 2 90 80 80 85
Test H
Compounds evaluated in this test were formulated in a non-phytotoxic solvent mixture which included a surfactant and applied to plants that were in the 1- to 4-leaf stage (postemergence application). A mixture of sandy loam soil and greenhouse potting mix in a 60:40 ratio was used for the postemergence test. Plantings of these crops and weed species were adjusted to produce plants of appropriate size for the postemergence test. All plant species were grown using normal greenhouse practices. Crop and weed species include annual bluegrass (Poa annua), blackgrass (Alopecurus myosuroides), black nightshade (Solanum nigra), chickweed (Stellaria media), common poppy (Papaver rhoeas), deadnettle (Lamium amplexicaule), downy brome (Bromus tectorum), field violet (Viola arvensis), galium (Galium aparine), green foxtail (Setaria viridis), ryegrass (Lolium multiflorum), jointed goatgrass (Aegilops cylindrica), kochia (Kochia scoparia), lambsquarters (Chenopodium album), littleseed canarygrass (Phalaris minor), rape (Brassica napus), redroot pigweed (Amaranthus retroflexus), Russian thistle (Salsola kali), scentless chamomile (Matricaria inodora), spring barley (Hordeum vulgare), sugar beet (Beta vulgaris), sunflower (Helianthus annuus), ivyleaf speedwell (Veronica hederaefolia), spring wheat (Triticum aestivum), winter wheat (Triticum aestivum), wild buckwheat (Polygonum convolvulus), wild mustard (Sinapis arvensis), wild oat (Avenafatua), windgrass (Apera spica-venti) and winter barley (Hordeum vulgare).
Treated plants and untreated controls were maintained in a greenhouse for approximately 21 to 28 days, after which all treated plants were compared to untreated controls and visually evaluated. Plant response ratings, summarized in Table H, are based upon a 0 to 100 scale where 0 is no effect and 100 is complete control. A dash response (-) means no test result.
Table H COMPOUND Table H COMPOUND
Rate 1000 g/ha 16 Rate 1000 g/ha 16
PREEMERGENCE PREEMERGENCE
Annual bluegras 100 LS canarygrass 65
Barley (winter) 30 Rape (1) 45
Blackgrass (2) 50 Redroot pigweed 50
Blk nightshade 30 Russian thistle 20
Chickweed 65 Scentless chamo
Common poppy 100 Spring Barley 30
Deadnettle 100 Sugar beet 20
Downy brome 40 Sunflower 20
Field violet 5 Ivyl speedwell 100
Galium (2) 30 Wheat (spring) 60
Green foxtail 30 Wheat (winter) 70
I . Ryegrass 100 Wild buckwheat 55
Jointed goatgra 100 Wild mustard 60 Kochia 30 Wild oat (1) 20
Lambsquarters 70 Windgrass 100
Table H i COMPOUND Table H COMPOUND
Rate 500 g/ha 28 46 Rate 250 g/ha 28 35 36 50 53
PREEMERGENCE POSTEMERGENCE
Annual bluegras 100 100 Annual bluegras 10 50 0 10 10
Barley (winter) 50 40 Barley (winter) 0 50 10 0 5
Blackgrass (2) 55 60 Blackgrass (2) 5 20 10 10 0
Blk nightshade 55 60 Blk nightshade 10 10 35 55 50
Chickweed 70 70 Chickweed 100 10 0 20 10
Common poppy 100 100 Common poppy 0 85 50 20 20
Deadnettle 100 - Deadnettle 0 10 0 20 0
Downy brome 65 30 Downy brome 30 0 0 10 0
Field violet 30 60 Field violet 10 10 0 0 10
Galium (2) 60 60 Galium (2) 0 10 10 55 20
Green foxtail 95 80 Green foxtail 70 35 10 60 10
I. Ryegrass 100 60 I . Ryegrass 20 10 10 20 10
Jointed goatgra 60 50 Jointed goatgra 20 0 5 30 10
Kochia 40 50 Kochia 20 10 0 0 10
Lambsquarters 60 100 Lambsquarters 0 0 0 0 30
LS canarygrass 65 60 LS canarygrass 0 40 10 10 0
Rape (1) 60 65 Rape (1) 30 15 30 20 30
Redroot pigweed 60 100 Redroot pigweed 10 40 0 60 0
Russian thistle 30 20 Russian thistle 5 0 20 60 30
Scentless chamo 100 70 Scentless chamo 55 10 0 60 50
Spring Barley 30 40 Spring Barley 0 10 0 0 0
Sugar beet 45 25 Sugar beet 0 55 35 10 15
Sunflower 50 60 Sunflower 20 20 10 25 10
Ivyl speedwell 100 - Ivyl speedwell 0 - - - 0
Wheat (spring) 50 60 Wheat (spring) 5 10 0 5 0
Wheat (winter) 60 60 Wheat (winter) 0 0 0 5 0
Wild buckwheat 55 60 Wild buckwheat 10 25 20 50 20
Wild mustard 65 65 Wild mustard 30 10 20 35 15
Wild oat (1) 30 0 Wild oat (1) 0 10 10 0 0
Windgrass 100 100 Windgrass 20 20 10 70 30 Table H COMPOUND Table H COMPOUND
Rate 250 g/ha 28 35 36 46 50 53 Rate 125 g/ha 28 35 36 50 53
PREEMERGENCE POSTEMERGENCE
Annual bluegras 100 70 50 100 70 70 Annual bluegras 10 0 20 10 10
Barley (winter) 20 20 0 10 0 0 Barley (winter) 0 10 10 10 0
Blackgrass (2) 50 50 0 30 40 70 Blackgrass (2) 5 10 10 5 0
Blk nightshade 40 0 20 60 60 0 Blk nightshade 10 50 20 30 0
Chickweed 70 20 30 50 0 30 Chickweed 70 0 0 0 0
Common poppy 100 100 100 100 100 100 Common poppy 5 60 30 30 10
Deadnettle 100 70 70 - 70 70 Deadnettle 0 0 0 0 0
Downy brome 60 20 20 20 20 30 Downy brome 0 0 10 0 0
Field violet 25 30 60 50 50 65 Field violet 0 40 30 0 10
Galium (2) 45 0 30 60 0 35 Galium (2) 10 50 20 50 10
Green foxtail 100 100 50 100 70 50 Green foxtail 30 25 10 45 0
I. Ryegrass 75 40 10 55 30 50 I. Ryegrass 10 10 10 10 5
Jointed goatgra 50 50 0 40 55 50 Jointed goatgra 10 0 2 10 5
Kochia 20 30 50 30 30 60 Kochia 10 50 30 25 0
Lambsquarters 60 70 0 100 70 100 Lambsquarters 0 50 10 0 0
LS canarygrass 65 10 0 50 40 70 LS canarygrass 0 10 20 5 0
Rape (1) 50 20 0 65 65 20 Rape (1) 30 40 25 10 15
Redroot pigweed 60 60 55 100 85 70 Redroot pigweed 5 60 0 0 0
Russian thistle 0 30 0 10 50 0 Russian thistle 20 30 10 30 30
Scentless chamo 100 70 75 65 100 100 Scentless chamo 60 10 0 10 65
Spring Barley 20 10 0 20 0 10 Spring Barley 10 5 0 0 0
Sugar beet 45 50 30 10 60 100 Sugar beet 0 0 0 40 20
Sunflower 30 0 0 50 35 10 Sunflower 10 10 15 10 20
Ivyl speedwell 100 100 100 - 100 100 Ivyl speedwell 0 - - - 0
Wheat (spring) 30 20 0 50 30 10 Wheat (spring) 0 20 0 0 0
Wheat (winter) 20 35 0 20 35 0 Wheat (winter) 0 0 0 0 0
Wild buckwheat 60 0 60 50 30 40 Wild buckwheat 10 20 10 20 0
Wild mustard 60 30 15 85 60 65 Wild mustard 30 10 20 15 10
Wild oat (1) 25 10 10 0 20 10 Wild oat (1) 0 10 0 0 10
Windgrass 100 100 100 100 100 100 Windgrass 10 20 10 60 30 Table H COMPOUND Table H COMPOUND
Rate 125 g/ha 28 35 36 46 50 53 Rate 62 g/ha 35 36 50 53
PREEMERGENCE POSTEMERGENCE
Annual bluegras 65 70 20 65 70 60 Annual bluegras 0 30 5 0
Barley (winter) 20 0 0 10 0 10 Barley (winter) 0 0 10 0
Blackgrass (2) 50 60 0 30 30 40 Blackgrass (2) 10 30 0 0
Blk nightshade 30 10 10 40 50 30 Blk nightshade 30 30 50 40
Chickweed 60 65 65 50 65 50 Chickweed 10 10 10 0
Common poppy 100 100 100 100 100 100 Common poppy 30 10 10 10
Deadnettle 100 70 70 - 65 65 Deadnettle 0 10 0 0
Downy brome 50 30 30 30 30 20 Downy brome 0 0 0 0
Field violet 30 65 0 60 70 0 Field violet 20 0 0 0
Galium (2) - 50 0 60 30 25 Galium (2) 50 30 40 10
Green foxtail 100 60 20 100 60 40 Green foxtail 10 0 30 20
I . Ryegrass 65 30 20 40 50 30 I. Ryegrass 0 10 0 0
Jointed goatgra 25 40 0 30 30 40 Jointed goatgra 0 0 0 0
Kochia 10 60 25 30 50 20 Kochia 0 0 10 0
Lambsquarters 65 70 - 60 65 30 Lambsquarters 0 0 0 0
LS canarygrass 30 0 0 60 20 0 LS canarygrass 0 50 0 0
Rape (1 ) 50 60 0 50 30 10 Rape (1) 10 10 10 20
Redroot pigweed 50 70 60 70 70 60 Redroot pigweed 0 0 0 0
Russian thistle 10 10 10 10 20 0 Russian thistle 50 20 50 40
Scentless chamo 85 70 70 70 100 70 Scentless chamo 0 0 20 0
Spring Barley 10 0 0 10 0 0 Spring Barley 0 0 0 0
Sugar beet 10 70 0 0 60 100 Sugar beet 45 0 10 20
Sunflower 20 30 0 20 20 0 Sunflower 5 0 10 10
Ivyl speedwell 100 100 100 - 100 100 Ivyl speedwell - - - 0
Wheat (spring) 0 10 0 30 10 0 Wheat (spring) 0 0 0 0
Wheat (winter) 10 10 0 10 10 0 Wheat (winter) 0 0 0 0
Wild buckwheat 50 60 40 60 55 50 Wild buckwheat 10 0 10 0
Wild mustard 60 40 0 65 55 30 Wild mustard 0 40 15 0
Wild oat (1) 20 30 0 10 10 0 Wild oat (1) 0 10 0 0
Windgrass 100 100 100 70 100 100 Windgrass 0 20 10 0 Table H COMPOUND Table H COMPOUND
Rate 62 g/ha 28 35 36 50 53 Rate 62 g/ha 28 35 36 50 53
PREEMERGENCE PREEMERGENCE
Annual bluegras 60 60 0 60 0 LS canarygrass 10 50 0 10 0
Barley (winter) 10 10 0 0 0 Rape (1) 30 50 0 15 10
Blackgrass (2) 0 50 0 50 0 Redroot pigweed 40 60 20 55 20
Blk nightshade 10 15 0 20 0 Russian thistle 10 30 0 20 0
Chickweed 10 50 60 70 50 Scentless chamo 70 70 70 70 20
Common poppy 100 100 70 70 100 Spring Barley 10 0 0 0 0
Deadnettle 70 70 0 70 70 Sugar beet 20 30 0 65 100
Downy brome - 0 0 20 10 Sunflower 10 15 0 20 20
Field violet 0 70 30 10 50 Ivyl speedwell 30 100 100 100 100
Galium (2) 50 10 0 20 0 Wheat (spring) 0 0 0 0 0
Green foxtail 60 50 10 50 20 Wheat (winter) 10 0 0 0 0
I. Ryegrass 55 50 0 30 25 Wild buckwheat 0 50 50 60 50
Jointed goatgra 25 0 0 20 0 Wild mustard 20 10 0 50 0
Kochia 0 60 40 30 20 Wild oat (1) 10 0 10 20 0
Lambsquarters 30 0 0 10 0 Windgrass 100 70 30 100 10
Test I
Seeds, tubers, or plant parts of alexandergrass (Brachiaria plantaginea), bermudagrass (Cynodon dactyloή), common purslane (Portulaca oleracea), common ragweed (Ambrosia elatior), common groundsel (Senecio vulgaris), dallisgrass (Paspalum dilatatum), goosegrass (Eleusine indica), guineagrass (Panicum maximum), itchgrass (Rottboellia exaltata), Johnson grass (Sorghum halepense), large crabgrass (Digitaria sanguinalis), pitted morningglory (Ipomoea lacunosa), purple nutsedge (Cyperus rotundus), sandbur (Cenchrus echinatus), sourgrass (Trichachne insularis), Spanishneedles (Bidens bipinnata), Surinam grass (Brachiaria decumbens) and tall mallow (Malva sylvestris) were planted into greenhouse pots of flats containing greenhouse planting medium. Plant species were grown grown in separate pots or individual compartments. Preemergence applications were made within one day of planting the seed or plant part. Postemergence applications were applied when the plants were in the two to four leaf stage (three to twenty cm). Test chemicals were formulated in a non-phytotoxic solvent mixture which included a surfactant and applied preemergence and postemergence to the plants. Untreated control plants and treated plants were placed in the greenhouse and visually evaluated for injury 13 to 21 days after herbicide application. Plant response ratings, summarized in Table I, are based on a 0 to 100 scale where 0 is no injury and 100 is complete control. A dash (-) response means no test result.
Table I COMPOUND Table I COMPOUND
Rate 500 g/ha 57 Rate 500 g/ha 57 POSTEMERGENCE POSTEMERGENCE
Alexandergrass 30 Johnsongrass 75
Bermudagrass 20 Large crabgrass 40
C. purslane 65 P. morninglory 80
C. ragweed 50 Purple nutsedge 0
Com. groundsel 40 Sandbur 65
Dallisgrass 90 Sourgrass 30
Goosegrass 75 Spanishneedles 50
Guineagrass 80 Surinam grass 60
Itchgrass 20 Tall Mallow 75
Table I COMPOUND Table I ( :OMPOUND Table I COMPOUND
Rate 500 g/ha 132 Rate 250 g/ha 57 132 Rate 250 g/ha 57 132 PREEMERGENCE POSTEMERGENCE PREEMERGENCE
Alexandergrass 100 Alexandergrass 10 75 Alexandergrass 100 100
Bermudagrass 100 Bermudagrass 20 40 Bermudagrass 100 100
C. purslane 0 C. purslane 40 50 C. purslane 0 0
C . ragweed 0 C. ragweed 10 20 C. ragweed 50 0
Com. groundsel 0 Com. ' groundsel 50 20 Com. groundsel 50 0
Dallisgrass 100 Dallisgrass 5 75 Dallisgrass 100 100
Goosegrass 100 Goosegrass 60 80 Goosegrass 100 100
Guineagrass 100 Guineagrass 35 50 Guineagrass 100 100
Itchgrass 90 Itchgrass 5 75 Itchgrass 30 90
Johnsongrass 100 Johnsongrass 35 20 Johnsongrass 40 100
Large crabgrass 100 Large crabgrass 20 60 Large crabgrass 100 100
P. morninglory 65 P. morninglory 75 75 P. morninglory 35 20
Purple nutsedge 85 Purple nutsedge 0 35 Purple nutsedge 0 100
Sandbur 100 Sandbur 10 40 Sandbur 50 90
Sourgrass 100 Sourgrass 10 75 Sourgrass 100 100
Spanishneedles 60 Spanishneedles 20 20 Spanishneedles 50 50
Surinam grass 100 Surinam grass 0 50 Surinam grass 85 100
Tall Mallow 100 Tall Mallow 40 75 Tall Mallow 100 90 Table I COMPOUND Table I COMPOUND Table I COMPOUND
Rate 125 g/ha 57 132 Rate 125 g/ha 57 132 Rate 64 g/ha 57 132
POSTEMERGENCE PREEMERGENCE PREEMERGENCE
Alexandergrass 5 20 Alexandergrass 95 75 Alexandergrass 35 0
Bermudagrass 20 20 Bermudagrass 100 100 Bermudagrass 100 90
C. purslane 35 55 C. purslane 0 0 C. purslane 0 0
C . ragweed 30 20 C . ragweed 0 0 C . ragweed 0 0
Com. groundsel 60 20 Com. groundsel 0 0 Com. groundsel 0 0
Dallisgrass 0 20 Dallisgrass 100 100 Dallisgrass 35 30
Goosegrass 60 65 Goosegrass 100 100 Goosegrass 90 100
Guineagrass 35 50 Guineagrass 100 100 Guineagrass 75 20
Itchgrass 5 10 Itchgrass 0 60 Itchgrass 0 60
Johnsongrass 10 20 Johnsongrass 0 95 Johnsongrass 0 0
Large crabgrass 20 40 Large crabgrass 100 100 Large crabgrass 100 100
P. morninglory 75 70 P. morninglory 0 20 P. morninglory 0 20
Purple nutsedge 0 0 Purple nutsedge 0 0 Purple nutsedge 0 0
Sandbur 10 10 Sandbur 0 75 Sandbur 0 20
Sourgrass 10 35 Sourgrass 100 100 Sourgrass 100 100
Spanishneedles 30 10 Spanishneedles 0 50 Spanishneedles - -
Surinam grass 0 5 Surinam grass 50 100 Surinam grass 0 10
Tall Mallow 20 30 Tall Mallow 5 75 Tall Mallow 5 30

Claims

CLAIMS What is claimed is:
1. A compound selected from Formula I, geometric or stereoisomers thereof, N-oxides thereof and agriculturally suitable salts thereof,
Figure imgf000150_0001
I wherein
A together with the carbon to which it is attached form 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 (CR6R7)q through other than X; X is O, S(O)n, ΝR3 or Si(R4)2; each R1 is independently C!-C alkyl or C1-C4 haloalkyl; R2 is CrC6 alkyl, CrC6 haloalkyl, C3-C7 cycloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, C Cg alkoxy, C2- alkoxyalkyl, C2-Cg haloalkoxyalkyl; or R2 is phenyl optionally substituted with C1-C3 alkyl, halogen, cyano, nitro or C2-C4 alkoxycarbonyl; R3 is H, CrC4 alkyl, CrC4 haloalkyl, C3-C4 alkenyl, C3-C4 alkynyl, C2-C4 alkoxycarbonyl or C2-C4 alkylcarbonyl; or R3 is phenyl optionally substituted on the phenyl ring with CJ-C3 alkyl, halogen, cyano, nitro or C2-C4 alkoxycarbonyl; each R4 is independently C1-C4 alkyl; Q is CrC12 alkyl, CrC6 haloalkyl, C2-C13 alkoxyalkyl, C3-C8 cycloalkyl, C3-C8 cycloalkenyl, C3-C12 alkenyl or C3-C8 alkynyl, each group optionally substituted with C1-C4 alkyl, C1-C4 haloalkyl, halogen, cyano, nitro or C2-C alkoxycarbonyl; or Q is Ar-(CH2)p- optionally substituted on the methylene carbon by 1-2 Cι-C2 alkyl; or Q is a 5- or 6-membered aromatic heterocyclic ring containing 1 to 3 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 each heterocyclic ring is optionally substituted by one or more groups selected from halogen, nitro, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 alkenyl, C3-C4 alk nyVCpC^ alkoxy, CrC4 haloalkoxy, S(O)nR5, C2-C4 alkoxycarbonyl, NR^R7, SF5, NR8C(=O)R9, NR SO2R5, and SO2NR6R7; and when Q is a 5-membered aromatic heterocyclic ring containing a nitrogen, then Q can be bonded through any available carbon or nitrogen atom to the tetrazolinone ring by replacement of a hydrogen on said carbon or nitrogen atom;
Ar is phenyl or pyridyl, each optionally substituted with halogen, cyano, nitro, C1-C4 alkoxy, C1-C4 haloalkoxy, -C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C alkynyl, C2-C4 alkoxycarbonyl, NR^R7, NR8C(=O)R9, NR8SO2R5, SF5, S(O)nR5, C C-4 halothioalkoxy, phenoxy or Ar1; Ar1 is phenyl or a 5- or 6-membered aromatic heterocyclic ring containing 1 to 3 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 each phenyl and heterocyclic ring is optionally substituted by one or more groups selected from halogen, nitro, cyano, C1-C4 alkyl, CrC4 haloalkyl, C3-C4 alkenyl, C3-C4 alkynyl, CrC4 alkoxy, CrC4 haloalkoxy, C2-C4 alkoxycarbonyl, NR6R7, SF5, NR C(=O)R9, NR8SO2R5, S(O)nR5, and SO2NR6R7; each R5 is independently C1-C4 alkyl or C1-C4 haloalkyl; each R6 is independently H or C1-C4 alkyl; each R7 is independently H or C1-C4 alkyl; each R8 is independently H or C1-C4 alkyl; each R9 is independently -C4 alkyl, C1-C4 haloalkyl or C1-C4 alkoxy; m is O, 1, 2, 3 or 4; each n is independently 0, 1 or 2; p is 0 or 1 ; and q is 0, 1 or 2.
2. A compound of Claim 1 wherein
Q is Ar-(CH )p- optionally substituted on the methylene carbon by 1-2 CrC2 alkyl; or
Q is a 5- or 6-membered aromatic heterocyclic ring containing 1 to 3 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 each heterocyclic ring is optionally substituted by one or more groups selected from halogen, nitro, cyano, C1-C4 alkyl, C1-C4 haloalkyl, C3-C4 alkenyl, C3-C4 alkynyl, CrC4 alkoxy, CrC haloalkoxy, S(O)nR5, C2-C4 alkoxycarbonyl, NR6R7, SF5, NR8C(=O)R9, NR8SO2R5, and SO2NR6R7; and when Q is a 5-membered aromatic heterocyclic ring containing a nitrogen, then Q can be bonded through any available carbon or nitrogen atom to the tetrazolinone ring by replacement of a hydrogen on said carbon or nitrogen atom.
3. A compound of Claim 2 wherein Q is Ar-(CH2)p-; Ar is phenyl optionally substituted with halogen, cyano, nitro, C1-C4 alkoxy, CJ-C4 haloalkoxy, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkoxycarbonyl or S(O)nR5; R5 is methyl; each R6, R7, R8, and R9 is independently H or methyl; and p is 0.
4. A compound of Claim 3 wherein
A together with the carbon to which it is attached form a fully or partially saturated 5-,
6- or 7-membered heterocyclic ring containing one X; and q is 0.
5. A compound of Claim 4 wherein X is O, S or NR3.
6. A compound of Claim 5 wherein
R2 is Cj-Cg alkyl, Cj-Cg haloalkyl or C3-C7 cycloalkyl; or R2 is phenyl optionally substituted with C1-C3 alkyl, halogen, cyano, nitro or C2-C4 alkoxycarbonyl.
7. A compound of Claim 6 wherein X is O.
8. A compound of Claim 7 which is selected from the group consisting of:
(a) 4-(2,6-dichlorophenyl)-N-(3 ,6-dihydro-2H-pyran-4-yl)-4,5-dihydro-N-( 1 - methylethyl)-5-oxo- lH-tetrazole- 1 -carboxamide;
(b) 4-(2-chloro-6-fluorophenyl)-N-(3 ,6-dihydro-2H-pyran-4-yl)-4,5-dihydro-N-( 1 - methylethyl)-5-oxo- lH-tetrazole- 1 -carboxamide;
(c) 4-(2,6-dichlorophenyl)-N-(3,6-dihydro-2H-ρyran-4-yl)-N-ethyl-4,5-dihydro-5- oxo- lH-tetrazole- 1 -carboxamide;
(d) N-(3,6-dihydro-2H-pyran-4-yl)-4-(2-fluorophenyl)-4,5-dihydro-N-(l- methylethyl)-5-oxo-lH-tetrazole-l-carboxamide; (e) 4-(2,6-difluorophenyl)-N-(3,6-dihydro-2H-pyran-4-yl)-4,5-dihydro-N-(l- methylethyl)-5-oxo- lH-tetrazole- 1 -carboxamide;
(f) 4-(2,6-dichlorophenyl)-N-(5,6-dihydro-2H-pyran-3-yl)-4,5-dihydro-N-( 1 - methylethyl)-5 -oxo- 1 H-tetrazole- 1 -carboxamide ; and
(g) 4-(2-chloro-4-fluorophenyl)-N-(3,6-dihydro-2H-pyran-4-yl)-4,5-dihydro-N-(l- methylethyl)-5-oxo-lH-tetrazole-l -carboxamide.
9. A compound selected from Formula 2, and geometric or stereoisomers thereof,
Figure imgf000153_0001
2 wherein A together with the carbon to which it is attached form 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 (CR6R7)q through other than X; X is O, S(O)n, NR3 or Si(R each R1 is independently C C4 alkyl or C1-C4 haloalkyl; R2 is CrC6 alkyl, CrC6 haloalkyl, C3-C7 cycloalkyl, C3-C6 alkenyl, C3-C6 haloalkenyl, C3-C6 alkynyl, Cj-Cg alkoxy, C2-C6 alkoxyalkyl or C2-Cg haloalkoxyalkyl; R3 is H, CrC4 alkyl, C^ haloalkyl, C3-C4 alkenyl, C3-C4 alkynyl, C2-C4 alkoxycarbonyl or C2-C4 alkylcarbonyl; or R3 is phenyl optionally substituted on the phenyl ring with C1-C3 alkyl, halogen, cyano, nitro or C2-C4 alkoxycarbonyl; each R4 is independently C1-C4 alkyl; each R6 is independently H or C1-C4 alkyl; each R7 is independently H or C1-C4 alkyl; m is 0, 1, 2, 3 or 4; each n is independently 0, 1 or 2; and q is 0, 1 or 2.
10. A compound of Claim 9 wherein A together with the carbon to which it is attached form a fully or partially saturated 5-,
6- or 7-membered heterocyclic ring containing one X; and q is 0.
11. A compound of Claim 10 wherein X is O, S or NR3.
12. A compound of Claim 11 wherein
R2 is CrC6 alkyl, CrC6 haloalkyl or C3-C7 cycloalkyl.
13. A compound of Claim 12 wherein X is O.
14. A compound of Claim 13 which is selected from the group consisting of: (a) (3,6-dihydro-2H-pyran-4-yl)(l-methylethyl)carbamic chloride; (b) (5,6-dihydro-2H-pyran-3-yl)(l-methylethyl)carbamic chloride;
(c) (3,6-dihydro-2H-pyran-4-yl)ethylcarbamic chloride; and
(d) [2,5-dihydro-5-(trifluoromethyl)-3-furanyl](l-methylethyl)carbamic chloride.
15. A herbicidal composition comprising a herbicidally effective amount of a compound of Claim 1 and at least one of a surfactant, a solid diluent or a liquid diluent.
16. 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 Claim 1.
PCT/US1998/002737 1997-02-18 1998-02-13 Herbicidal tetrazolinones WO1998035961A1 (en)

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WO1999048890A1 (en) * 1998-03-26 1999-09-30 E.I. Du Pont De Nemours And Company Herbicidal tetrazolinones
JP2001114769A (en) * 1999-08-10 2001-04-24 Nippon Bayer Agrochem Co Ltd Tetrazolinone derivative and herbicide
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US9346769B2 (en) 2010-05-05 2016-05-24 Infinity Pharmaceuticals, Inc. Tetrazolones as inhibitors of fatty acid synthase
EP3059233A1 (en) * 2013-10-17 2016-08-24 Sumitomo Chemical Company, Limited Tetrazolinone compound and application for same
US9822095B2 (en) 2014-03-28 2017-11-21 Sumitomo Chemical Company, Limited Tetrazolinone compound and application thereof
US9826741B2 (en) 2014-03-28 2017-11-28 Sumitomo Chemical Company, Limited Tetrazolinone compound and application thereof
US10070646B2 (en) 2014-03-28 2018-09-11 Sumitomo Chemical Company, Limited Tetrazolinone compound and application thereof
US11046658B2 (en) 2018-07-02 2021-06-29 Incyte Corporation Aminopyrazine derivatives as PI3K-γ inhibitors
CN117567446A (en) * 2023-11-28 2024-02-20 东北农业大学 Triazolinone compound containing heterocyclic structure, preparation method and application thereof
US11926616B2 (en) 2018-03-08 2024-03-12 Incyte Corporation Aminopyrazine diol compounds as PI3K-γ inhibitors

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Cited By (14)

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Publication number Priority date Publication date Assignee Title
US6277790B1 (en) 1997-08-06 2001-08-21 Basf Aktiengesellschaft Substituted herbicide tetrazolinonecarboxylic acid amides
WO1999048890A1 (en) * 1998-03-26 1999-09-30 E.I. Du Pont De Nemours And Company Herbicidal tetrazolinones
JP2001114769A (en) * 1999-08-10 2001-04-24 Nippon Bayer Agrochem Co Ltd Tetrazolinone derivative and herbicide
US9346769B2 (en) 2010-05-05 2016-05-24 Infinity Pharmaceuticals, Inc. Tetrazolones as inhibitors of fatty acid synthase
US10077254B2 (en) 2013-10-17 2018-09-18 Sumitomo Chemical Company, Limited Tetrazolinone compound and use thereof
EP3059233A4 (en) * 2013-10-17 2017-04-05 Sumitomo Chemical Company, Limited Tetrazolinone compound and application for same
EP3059233A1 (en) * 2013-10-17 2016-08-24 Sumitomo Chemical Company, Limited Tetrazolinone compound and application for same
US9822095B2 (en) 2014-03-28 2017-11-21 Sumitomo Chemical Company, Limited Tetrazolinone compound and application thereof
US9826741B2 (en) 2014-03-28 2017-11-28 Sumitomo Chemical Company, Limited Tetrazolinone compound and application thereof
US10070646B2 (en) 2014-03-28 2018-09-11 Sumitomo Chemical Company, Limited Tetrazolinone compound and application thereof
US11926616B2 (en) 2018-03-08 2024-03-12 Incyte Corporation Aminopyrazine diol compounds as PI3K-γ inhibitors
US11046658B2 (en) 2018-07-02 2021-06-29 Incyte Corporation Aminopyrazine derivatives as PI3K-γ inhibitors
CN117567446A (en) * 2023-11-28 2024-02-20 东北农业大学 Triazolinone compound containing heterocyclic structure, preparation method and application thereof
CN117567446B (en) * 2023-11-28 2024-05-10 东北农业大学 Triazolinone compound containing heterocyclic structure, preparation method and application thereof

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