WO2003079788A2 - Benzamides and compositions benzamides for use as fungizide - Google Patents

Benzamides and compositions benzamides for use as fungizide Download PDF

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Publication number
WO2003079788A2
WO2003079788A2 PCT/US2003/008205 US0308205W WO03079788A2 WO 2003079788 A2 WO2003079788 A2 WO 2003079788A2 US 0308205 W US0308205 W US 0308205W WO 03079788 A2 WO03079788 A2 WO 03079788A2
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component
compound
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socf
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WO2003079788A3 (en
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Stephen Ray Foor
Michael Paul Walker
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to IL16289503A priority Critical patent/IL162895A0/en
Priority to SI200332299T priority patent/SI1484970T1/en
Priority to MXPA04009001A priority patent/MXPA04009001A/en
Priority to BRPI0308457-4A priority patent/BR0308457B1/en
Priority to DK03716661.8T priority patent/DK1484970T3/en
Priority to ES03716661T priority patent/ES2425941T3/en
Priority to US10/501,126 priority patent/US20050164999A1/en
Priority to AU2003220361A priority patent/AU2003220361A1/en
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to EP03716661.8A priority patent/EP1484970B1/en
Priority to JP2003577631A priority patent/JP2005520839A/en
Publication of WO2003079788A2 publication Critical patent/WO2003079788A2/en
Publication of WO2003079788A3 publication Critical patent/WO2003079788A3/en
Priority to ZA2004/05644A priority patent/ZA200405644B/en
Anticipated expiration legal-status Critical
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    • 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
    • A01N47/02—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 no bond to a nitrogen atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings

Definitions

  • This invention relates to certain benzamides, their N-oxides, agriculturally suitable salts, certain advantageous compositions containing a mixture of benzamides and other fungicides and methods of their use as fungicides.
  • WO 99/42447 discloses certain benzamides of formula i as fungicides
  • R 1 is H, alkyl or acyl
  • R 2 is H or alkyl
  • WO 02/16322 discloses a novel process for preparing certain benzamides of formula ii that are useful as fungicides
  • n X is halogen
  • Y is halogen, haloalk l, alkoxycarbonyl or al ylsulfonyl; each R 1 and R 2 is idependently halogen; mis 0,1 or 2; and nis 0 to 3.
  • Fungicides that effectively control plant fungi are in constant demand by growers.
  • Combinations of fungicides are often used to facilitate disease control and to retard resistance development. It is desirable to enhance the activity spectrum and the efficacy of disease control by using mixtures of active ingredients that provide a combination of curative, systemic andpreventative control of plant pathogens. Also desirable are combinations that provide greater residual control to allow for extended spray intervals. It is also very desirable to combine fungicidal agents that inhibit different biochemical pathways in the fungal pathogens to retard development of resistance to any one particular plant disease control agent.
  • This invention provides a composition for controlling plant diseases caused by fungal plant pathogens comprising (a) at least one compound of Formula I (including all geometric and stereoisomers), N-oxides and agriculturally suitable salts thereof:
  • A is a substituted pyridinyl ring
  • B is a substituted phenyl ring
  • L is O or S
  • R 1 and R 2 are each independently H; or C r C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl or
  • C3-C6 cycloalkyl each optionally substituted; 3 is H; or C r C 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 3 -C 6 cycloalkyl, C 2 -C 10 alkoxyalkyl, C -Cg alkylcarbonyl, C 2 -Cg alkoxycarbonyl, C 2 -Cg alkylaminocarbonyl or C 3 -Cg dialkylaminocarbonyl; and n is 1 or 2; and (b) at least one compound selected from the group consisting of (bl) alkylenebis(dithiocarbamate) fungicides;
  • This invention also relates to a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed or seedling, a f ngicidally effective amount of a composition of the invention.
  • This invention also provides a compound of Formula la (including all geometric and stereoisomers), N-oxides and agriculturally suitable salts thereof:
  • R 4 is halogen
  • R 5 is Ci-Cg alkyl, halogen, ⁇ O 2 , -C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C 4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulf ⁇ nyl or C1-C 4 haloalkylsulfonyl; each R 6 is independently C j -Cg alkyl, Ci-Cg haloalkyl, halogen, NO , C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C 4 haloalkylthio, C1-C4 haloalkyl
  • This invention also provides a compound of Formula lb (including all geometric and stereoisomers), N-oxides and agriculturally suitable salts thereof: lb
  • R 4 is halogen
  • R 5 is C1-C4 haloalkoxy, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl or C -C4 haloalkylsulfonyl; eachR 6 is independently Cj-C6 alkyl, Ci-Cg haloalkyl, halogen, NO 2 , C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C 1 -C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl or C1-C4 haloalkylsulfonyl; or two R attached to contiguous carbon atoms are taken together with said carbon atoms to form a fused 5- or 6-membered nonaromatic heterocyclic ring
  • This invention also provides a compound of Formula Ic (including all geometric and stereoisomers), N-oxides and agriculturally suitable salts thereof:
  • R 4 is Cl orBr
  • R 5 is Br orI; each R 6 is independently Cj-Cg alkyl, C j -C ⁇ haloalkyl, halogen, ⁇ O 2 , C1-C4 alkoxy, C r C4 haloalkoxy, alkylsulfonyl, C 1 -C4 haloalkylthio, -C 4 haloalkylsulfinyl or C1-C4 haloalkylsulfonyl; or two R 6 attached to contiguous carbon atoms are taken together with said carbon atoms to form a fused 5- or 6-membered nonaromatic heterocyclic ring containing one or two oxygen atoms and optionally substituted with from one to four substituents independently selected from F or methyl; and p is 1, 2, 3 or 4.
  • A is a substituted pyridinyl ring and B is a substituted phenyl ring.
  • substituted in connection with these A or B groups refers to groups that have at least one non-hydrogen substituent that does not extinguish the fungicidal activity.
  • R 5 , B is substituted with 1 to 4 R 6 include the rings illustrated in Exhibit 1 wherein m and p are independently integers from 1 to 4. Note that the attachment point between (R 5 ) m and
  • a and (R 6 ) p and B is illustrated as floating, and (R 5 ) m and (R 6 ) p can be attached to any available carbon atom of the A and B rings respectively.
  • R 5 when attached to A and R 6 when attached to B include: each R 5 and R 6 is independently Ci -Cg alkyl, C -Cg alkenyl, C -C6 alkynyl, C 3 -CQ cycloalkyl, C ⁇ -Cg haloalkyl, C -Cg haloalkenyl, C -C6 haloalkynyl, C3-C6 halocycloalkyl, halogen, CN, CO 2 H, CONH , NO , hydroxy, C1-C4 alkoxy, C1-C 4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C 4 alkylsulfonyl, C ⁇ C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C 4 haloalkylsulfonyl, Cj
  • R 1 and R 2 are each independently H; or C ⁇ -Cg alkyl, C 2 -Cg alkenyl, C 2 -C ⁇ alkynyl or C3-C6 cycloalkyl, each optionally substituted.
  • the term "optionally substituted" in connection with these R 1 and R 2 groups refers to groups that are unsubstituted or have at least one non-hydrogen substituent that does not extinguish the fungicidal activity possessed by the unsubstituted analog.
  • R 1 and R 2 groups are those that are optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO 2 , hydroxy, C 1 -C4 alkoxy, -C4 alkylthio, C 1 -C4 alkylsulfinyl, C 1 -C4 alkylsulfonyl, C 2 -C4 alkoxycarbonyl, Ci -C 4 alkylamino, C 2 -Cg dialkylamino and C3-C6 cycloalkylamino.
  • substituents are listed in the examples above, it is noted that they do not need to be present since they are optional substituents.
  • R 1 and R 2 groups that are optionally substituted with one to four substituents selected from the group above.
  • N-oxides of Formula I are illustrated as 1-4 through 1-6 in Exhibit 2, wherein R 1 , R 2 , R 3 , R 5 , R 6 , W, m and p are as defined above.
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, z-propyl, or the different butyl, pentyl or hexyl isomers.
  • 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, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
  • Alkoxyalkyl denotes alkoxy substitution on alkyl.
  • alkoxyalkyl examples include CH3OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • Alkoxyalkoxy denotes alkoxy substitution on alkoxy.
  • alkenyloxy includes straight chain or branched alkenyloxy moieties.
  • alkynyloxy includes straight chain or branched alkynyloxy moieties. Examples of “alkynyloxy” include HC ⁇ CCH 2 O, CH 3 C ⁇ CCH 2 O and CH3C ⁇ CCH 2 CH 2 O.
  • Alkylthio includes branched or straight chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio andhexylthio isomers.
  • Alkylsulfinyl includes both enantiomers of an alkylsulfinyl group. Examples of “alkylsulfinyl” include CH 3 S(O), CH 3 CH 2 S(O), CH 3 CH 2 CH 2 S(O), (CH 3 ) 2 CHS(O) and the different butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers.
  • alkylsulfonyl examples include CH 3 S(O) 2 , CH 3 CH 2 S(O) 2 , CH 3 CH 2 CH 2 S(O) 2 , (CH 3 ) 2 CHS(O) 2 and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers.
  • alkylamino "dialkylamino”, “alkenylthio”, “alkenylsulfinyl”, “alkenylsulfonyl”, “alkynylthio”, “alkynylsulfinyl”, “alkynylsulfonyl”, and the like, are defined analogously to the above examples.
  • Cycloalkyl includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • cycloalkoxy includes the same groups linked through an oxygen atom such as cyclopentyloxy and cyclohexyloxy.
  • halogen either alone or in compound words such as “haloalkyl” includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl”, said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of “haloalkyl” include F3C, C1CH 2 , CF 3 CH 2 and CF 3 CC1 2 .
  • haloalkenyl “haloalkynyl”, “haloalkoxy”, “haloalkylthio”, and the like, are defined analogously to the term “haloalkyl”.
  • haloalkynyl examples include HC ⁇ CCHCl, CF 3 C---C, CCI3G- and FCH 2 C ⁇ CCH 2 .
  • haloalkoxy examples include CF 3 O, CCl 3 CH 2 O, HCF 2 CH 2 CH 2 O and CF 3 CH 2 O.
  • haloalkylthio examples include CCI3S, CF 3 S, CC1 3 CH 2 S and C1CH 2 CH 2 CH 2 S.
  • haloalkylsulfinyl examples include CF 3 S(O), CCl 3 S(O), CF 3 CH 2 S(O) and CF 3 CF 2 S(O).
  • haloalkylsulfonyl examples include CF 3 S(O) 2 , CCl 3 S(O) 2 , CF 3 CH 2 S(O) 2 and CF 3 CF 2 S(O) 2 .
  • alkylcarbonyl include C(O)CH 3 , C(O)CH 2 CH 2 CH 3 and C(O)CH(CH 3 ) 2 .
  • Aromaatic indicates that each of the ring atoms is essentially in the same plane and has a ⁇ -orbital pe ⁇ endicular to the ring plane, and in which (4n + 2) ⁇ electrons, when n is 0 or a positive integer, are associated with the ring to comply with H ⁇ ckel's rule.
  • aromatic carbocyclic ring includes fully aromatic carbocycles (e.g. phenyl).
  • nonaromatic carbocyclic ring denotes fully saturated carbocycles as well as partially or fully unsaturated carbocycles where the H ⁇ ckel rule is not satisfied.
  • hetero in connection with rings refers to a ring in which at least one ring atom is not carbon and which can contain 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, provided that each ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs.
  • heteroring includes fully aromatic heterocycles.
  • nonaromatic heterocyclic ring denotes fully saturated heterocycles as well as partially or fully unsaturated heterocycles where the H ⁇ ckel rule is not satisfied.
  • the heterocyclic ring can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
  • nitrogen containing heterocycles can form N-oxides since the nitrogen requires an available lone pair for oxidation to the oxide; one skilled in the art will recognize those nitrogen containing heterocycles which can form N-oxides.
  • nitrogen containing heterocycles which can form N-oxides.
  • tertiary amines can form N-oxides.
  • C ] -C 3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl
  • C 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
  • C4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH 3 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • substituents When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents. Further, when the subscript indicates a range, e.g. (R)i_ j , then the number of substituents may be selected from the integers between i and j inclusive.
  • Compounds of Formula I can exist as one or more stereoisomers.
  • the various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers.
  • one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s).
  • the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers.
  • the present invention comprises compounds selected from Formula I, N-oxides and agriculturally suitable salts thereof.
  • the compounds of Formula I may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form. In particular, when R 1 and R 2 of Formula I are different, then said Formula possesses a chiral center at the carbon to which R 1 and R 2 are commonly bonded.
  • This invention includes racemic mixtures of equal parts of Formula I' and Formula I".
  • compositions that are emiched compared to the racemic mixture in an enantiomer of the Formula I' or Formula I This invention also includes compositions wherein component (a) is emiched in a component (a) enantiomer of Formula I' compared to the racemic mixture of component (a). Included are compositions comprising the essentially pure enantiomers of Formula F. This invention also includes compositions wherein component (a) is enriched in a component (a) enantiomer of Formula I" compared to the racemic mixture of component (a). Included are compositions comprising the essentially pure enantiomers of Formula I".
  • enantiomer excess("ee") 100(2x-l) where x is the mole fraction of the dominant enantiomer in the enantiomer mixture (e.g., an ee of 20% corresponds to a 60:40 ratio of enantiomers).
  • the more active enantiomer with respect to the relative positions of R 1 , R 2 , A and the rest of the molecule bonded through nitrogen corresponds to the configuration of the enantiomer of Formula I that, when in a solution of CDCI 3 , rotates plane polarized light in the (+) or dextro direction.
  • enantiomerically pure embodiments of the more active isomer of Formula I are enantiomerically pure embodiments of the more active isomer of Formula I.
  • the salts of the compounds of Formula I 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 Formula I 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
  • Formula I for reasons of better activity and/or ease of synthesis are: Preferred 1.
  • Preferred are compositions wherein in Formula I A is a pyridinyl ring substituted with from 1 to 4 R 5 ; B is a phenyl ring substituted with from 1 to 4 R 6 ; W is C O;
  • R 1 and R 2 are each independently H; or Ci-Cg alkyl, C 2 -C 6 alkenyl, C 2 -C6 alkynyl or C 3 -C6 cycloalkyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO 2 , hydroxy, C r C 4 alkoxy, -C4 alkylthio, C r C 4 alkylsulfinyl, CX-C4 alkylsulfonyl, C 2 -C 4 alkoxycarbonyl, alkylamino, C 2 -C 8 dialkylamino and C 3 -C6 cycloalkylamino;
  • R 3 is H; and each R 5 and R 6 is independently Ci -Cg alkyl, C 2 -Cg alkenyl, C 2 -Cg alkynyl, C3-C6 cycloalkyl, Cj-Cg haloalkyl
  • A is a 2-pyridinyl ring substituted with from 1 to 4 R 5 ;
  • B is substituted with from 1 to 4 R 6 , with at least one R 6 located in a position ortho to the link with W.
  • eachR 6 is independently F, CI, Br, I, CH 3 , OCH 3 , OCF3, OCHF 2 , CF 3 or NO 2 .
  • at least one R 6 is iodo.
  • each R 6 is either halogen or methyl.
  • Preferred 5 Compositions of Preferred 4 wherein A is 3-chloro-5-CF 3 -2-pyridinyl.
  • Preferred compositions of this invention include those of Preferred 1 through Preferred 5 wherein R 1 is H and R 2 is H or CH 3 . More preferred are compositions of Preferred 1 through Preferred 5 wherein R 1 is H and R 2 is CH .
  • compositions comprising a compound selected from the group consisting of
  • compositions comprising a compound selected from the group consisting of
  • This invention also relates to a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed or seedling, a fungicidally effective amount of the composition of the invention (i.e., as a composition described herein).
  • a fungicidally effective amount of the composition of the invention i.e., as a composition described herein.
  • the preferred methods of use are those involving the above- preferred compositions.
  • This invention also provides a compound of Formula la as described above.
  • Preferred compounds of Formula la are:
  • R 5 is CI, Br, I, CH3, OCF3, OCHF 2 , OCH 2 CF 3 , OCF 2 CF 3 , OCF 2 CF 2 H, OCHFCF3, SCF 3 , SCHF 2 , SCH 2 CF 3 , SCF 2 CF 3 , SCF 2 CF 2 H, SCHFCF3, SOCF3, SOCHF 2 , SOCH 2 CF 3 , SOCF 2 CF 3 , SOCF 2 CF 2 H, SOCHFCF3, SO 2 CF 3 , SO 2 CHF 2 , SO 2 CH 2 CF 3 , SO 2 CF 2 CF 3 , SO 2 CF 2 CF 2 H or SO 2 CHFCF 3 .
  • This invention also provides a compound of Formula lb as described above.
  • Preferred compounds of Formula lb are:
  • R 5 is, OCF 3 , OCHF 2 , OCH 2 CF 3 , OCF 2 CF 3 , OCF 2 CF 2 H, OCHFCF3, SCF 3 , SCHF 2 , SCH 2 CF 3 , SCF 2 CF 3 , SCF 2 CF 2 H, SCHFCF3, SOCF3, SOCHF 2 , SOCH 2 CF 3 , SOCF 2 CF 3 , SOCF 2 CF 2 H, SOCHFCF3, SO 2 CF 3 , SO 2 CHF 2 , SO 2 CH 2 CF 3 , SO 2 CF 2 CF 3 , SO 2 CF 2 CF 2 H or SO 2 CHFCF 3 .
  • This invention also provides a compound of Formula Ic as described above.
  • Preferred compounds of Formula Ic are:
  • Compounds of Formula I can be prepared by one or more of the methods and variations described in WO99/42447 (See e.g., Example 4). Some compounds of Formula I can also be prepared by methods described in WO02/16322.
  • Examples of compounds of Formula I suitable for use in component (a) of the compositions of this invention include the following compounds of Tables 1-7.
  • the following abbreviations are used in the Tables which follow: Me is methyl, Et is ethyl, Ph is phenyl, OMe is methoxy, OEt is ethoxy, CN is cyano, NO 2 is nitro.
  • the substituents Q and R are equivalent to independent R 5 substituents that have been located in the positions indicated.
  • the substituents T, U and V are equivalent to independent R 6 substituents that have been located in the positions indicated.
  • T and V are both Cl andUis H
  • T and V are both Cl and U is CH 3
  • T Cl and V andU arebofliMe
  • T is Cl
  • V is I
  • U H
  • T Cl, Vis I andUi- Me
  • T F
  • Vis I andU Me
  • T and V are both Cl andU is CH 3
  • T Cl and V and U are both Me
  • T F. Vis I andU is Me
  • the fungicides of component (b) of the compositions of the invention are selected from the group consisting of
  • the weight ratios of component (b) to component (a) typically is from 100:1 to 1:100, preferably is from 30:1 to 1 :30, and more preferably is from 10:1 to 1:10. Of note are compositions wherein the weight ratio of component (b) to component (a) is from 10: 1 to 1:1. Included are compositions wherein the weight ratio of component (b) to component (a) is from 9:1 to 4.5:1.
  • Strobilurin fungicides such as azoxystrobin, kresoxim-methyl, metominostrobin/fenominostrobin (SSF-126), picoxystrobin, pyraclostrobin and trifloxystrobin are known to have a fungicidal mode of action which inhibits the bc complex in the mitochondrial respiration chain (Angew. Chem. Int. Ed., 1999, 38, 1328- 1349).
  • Methyl (E)-2-[[6-(2-cyanophenoxy)-4-pyrimidinyl]oxy]- ⁇ - (memoxyimino)benzeneacetate (also known as azoxystrobin) is described as a bc ⁇ complex inhibitor in Biochemical Society Transactions 1993, 22, 68S.
  • Methyl (E)- ⁇ - (memoxyimino)-2-[(2-methylphenoxy)methyl]benzeneacetate also known as kresoxim- methyl
  • a bc ⁇ complex inhibitor is described as a bc ⁇ complex inhibitor in Biochemical Society Transactions 1993, 22, 64S.
  • the bc ⁇ complex is sometimes referred to by other names in the biochemical literature, including complex III of the electron transfer chain, and ubihydroquinonexytochrome c oxidoreductase. It is uniquely identified by the Enzyme Commission number EC1.10.2.2.
  • the bc ⁇ complex is described in, for example, J. Biol. Chem. 1989, 264, 14543-38; Methods Enzymol. 1986, 126, 253-71; and references cited therein.
  • the Sterol Biosynthesis Inhibitor Fungicides component (b4 or (b5)
  • the class of sterol biosynthesis inhibitors includes DMI andnon-DMI compounds, that control fungi by inhibiting enzymes in the sterol biosynthesis pathway.
  • DMI fungicides have a common site of action within the fungal sterol biosynthesis pathway; that is, an inhibition of demethylation at position 14 of lanosterol or 24-methylene dihydrolanosterol, which are precursors to sterols in fungi.
  • Compounds acting at this site are often referred to as demethylase inhibitors, DMI fungicides, or DMIs.
  • the demethylase enzyme is sometimes referred to by other names in the biochemical literature, including cytochrome P-450 (14DM). The demethylase enzyme is described in, for example, J.
  • DMI fungicides fall into several classes: azoles (including triazoles and imidazoles), pvrimidines, piperazines and pyridines.
  • the triazoles includes bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, ipconazole, metconazole, penconazole, propiconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole anduniconazole.
  • the imidazoles include clotrimazole, econazole, imazalil, isoconazole, miconazole and prochloraz.
  • the pyrimidines include fenarimol, nuarimol and triarimol.
  • the piperazines include triforine.
  • the pyridines include buthiobate and pyrifenox. Biochemical investigations have shown that all of the above mentioned fungicides are DMI fungicides as described by K. H. Kuck, et al. in Modern Selective Fungicides - Properties, Applications and Mechanisms of Action, Lyr, H., Ed.; Gustav Fischer Verlag: New York, 1995, 205-258.
  • the DMI fungicides have been grouped together to distinguish them from other sterol biosynthesis inhibitors, such as, the mo ⁇ holine and piperidine fungicides.
  • the mo ⁇ holines and piperidines are also sterol biosynthesis inhibitors but have been shown to inhibit later steps in the sterol biosynthesis pathway.
  • the mo ⁇ holines include aldimo ⁇ h, dode o ⁇ h, fenpropimo ⁇ h, tridemo ⁇ h and trimo ⁇ hamide.
  • the piperidines include fenpropidin.
  • Biochemical investigations have shown that all of the above mentioned mo ⁇ holine and piperidine fungicides are sterol biosynthesis inhibitor fungicides as described by K. H. Kuck, et al. in Modern Selective Fungicides - Properties, Applications and Mechanisms of Action, Lyr, H., Ed.; Gustav Fischer Verlag: New York, 1995, 185-204. Pyrimidinone Fungicides (component (bl))
  • Pyrimidinone fungicides include compounds of Formula II
  • G is a fused phenyl, thiophene or pyridine ring
  • R 1 is C r C 6 alkyl
  • R 2 is CyC alkyl or C ⁇ -C ⁇ alkoxy
  • R 3 is halogen
  • R 4 is hydrogen or halogen.
  • pyrimidinone fungicides selected from the group: 6-bromo-3-propyl-2-propyloxy-4(3H)-quinazolinone,
  • Phenylamides such as metalaxyl, benalaxyl and oxadixyl
  • fungicides which can be included in combination with a Formula I compound or as an additional component in combination with component (a) and component (b) are acibenzolar, benalaxyl, benomyl, blasticidin-S, Bordeaux mixture (tribasic copper sulfate), ca ⁇ ropamid, captafol, captan, carbendazim, chloroneb, chlorothalonil, copper oxychloride, copper salts such as copper sulfate and copper hydroxide, cyazofamid, cymoxanil, cyprodinil, (S)-3,5-dic oro-N-(3-cMoro-l-e1hyl-l-methyl- 2-oxopropyl)-4-methylbenzamide (R ⁇ 7281), diclocymet (S-2900), diclomezine, dicloran, dimethomo ⁇ h, diniconazole-M, dodem
  • Compound 1 with strobilurins such as azoxystrobin, kresoxim-methyl, pyraclosfrobin and trifloxystrobin; carbendazim, mitochondrial respiration inhibitors such as famoxadone and fenamidone; benomyl, cymoxanil; dimethomo ⁇ h; folpet; fosetyl-aluminum; metalaxyl; mancozeb and maneb.
  • strobilurins such as azoxystrobin, kresoxim-methyl, pyraclosfrobin and trifloxystrobin
  • carbendazim mitochondrial respiration inhibitors such as famoxadone and fenamidone
  • benomyl cymoxanil
  • dimethomo ⁇ h folpet
  • fosetyl-aluminum metalaxyl
  • metalaxyl mancozeb and maneb.
  • fungicides for controlling grape diseases including alkylenebis(dithiocarbamate)s such as mancozeb, maneb, propineb and zineb, phthalimids such as folpet, copper salts such as copper sulfate and copper hydroxide, strobilurins such as azoxystrobin, pyraclostrobin and trifloxystrobin, mitochondrial respiration inhibitors such as famoxadone and fenamidone, phenylamides such as metalaxyl, phosphonates such as fosetyl-Al, dimethomo ⁇ h, pyrimidinone fungicides such as 6-iodo-3-propyl-2-propyloxy-4(3H)-quinazolinone and 6-chloro-2-propoxy-3- propyltMeno[
  • alkylenebis(dithiocarbamate)s such as mancozeb, maneb, propineb and zineb
  • fungicides for controlling potato diseases including alkylenebis(dithiocarbamate)s such as mancozeb, maneb, propineb and zineb; copper salts such as copper sulfate and copper hydroxide; strobilurins such as pyraclostrobin and trifloxystrobin; mitochondrial respiration inhibitors such as famoxadone and fenamidone; phenylamides such as metalaxyl; carbamates such as propamocarb; phenylpyridylamines such as fluazinam and other fungicides such as chlorothalonil, cyazofamid, cymoxanil, dimethomo ⁇ h, zoxamid and iprovalicarb.
  • alkylenebis(dithiocarbamate)s such as mancozeb, maneb, propineb and zineb
  • copper salts such as copper sulfate and copper hydroxide
  • component (b) comprises at least one compound from each of two different groups selected from (bl), (b2), (b3), (b4), (b5), (b6), (bl), (b8) and (b9).
  • the weight ratio of the compound(s) of the first of these two component (b) groups to the compound(s) of the second of these component (b) groups typically is from 100:1 to 1:100, more typically from 30:1 to 1:30 and most typically from 10:1 to 1:10.
  • compositions wherein component (b) comprises at least one compound selected from (bl), for example mancozeb, and at least one compound selected from a second component (b) group, for example, from (b2), (b3), (b6), (b7), (b8) or (b9).
  • component (b) comprises at least one compound selected from (bl), for example mancozeb, and at least one compound selected from a second component (b) group, for example, from (b2), (b3), (b6), (b7), (b8) or (b9).
  • the overall weight ratio of component (b) to component (a) is from 30:1 to 1:30 and the weight ratio of component (bl) to component (a) is from 10: 1 to 1:1.
  • the weight ratio of component (bl) to component (a) is from 9:1 to 4.5:1.
  • compositions comprising mixtures of component (a) (preferably a compound from Index Table A) with mancozeb and a compound selected from the group consisting of famoxadone, fenamidone, azoxystrobin, kresoxim-methyl, pyraclostrobin, trifloxystrobin, cymoxanil, metalaxyl, benalaxyl, oxadixyl, 6-iodo-3-propyl-2-propyloxy-4(3H)-quinazolinone, 6-chloro-2- propoxy-3-propylthieno[2,3-rf]pyrimidin-4(3H)-one, folpet, captan and fosetyl-aluminum.
  • component (a) preferably a compound from Index Table A
  • compositions wherein component (b) comprises at least one compound selected from (b2), for example famoxadone, and at least one compound selected from a second component (b) group, for example, from (bl), (b3), (b6), (b7), (b8) or (b9).
  • component (b) comprises at least one compound selected from (b2), for example famoxadone, and at least one compound selected from a second component (b) group, for example, from (bl), (b3), (b6), (b7), (b8) or (b9).
  • the overall weight ratio of component (b) to component (a) is from 30:1 to 1:30 and the weight ratio of component (b2) to component (a) is from 10:1 to 1:1.
  • the weight ratio of component (b2) to component (a) is from 9:1 to 4.5:1.
  • compositions comprising mixtures of component (a) (preferably a compound from Index Table A) with famoxadone and a compound selected from the group consisting of mancozeb, maneb, propineb, zineb, cymoxanil, metalaxyl, benalaxyl, oxadixyl, 6-iodo-3 -propy 1-2-propyloxy- 4(3H)-quinazolinone, 6-cMoro-2-propoxy-3-propylt eno[2,3- ⁇ pyrimidin-4(3H)-one, folpet, captan and fosetyl-aluminum.
  • component (a) preferably a compound from Index Table A
  • famoxadone a compound selected from the group consisting of mancozeb, maneb, propineb, zineb, cymoxanil, metalaxyl, benalaxyl, oxa
  • compositions wherein component (b) comprises the compound of (b3), in other words cymoxanil, and at least one compound selected from a second component (b) group, for example, from (bl), (b2), (b6), (b7), (b8) or (b9).
  • component (b) comprises the compound of (b3), in other words cymoxanil, and at least one compound selected from a second component (b) group, for example, from (bl), (b2), (b6), (b7), (b8) or (b9).
  • the overall weight ratio of component (b) to component (a) is from 30:1 to 1:30 and the weight ratio of component (b3) to component (a) is from 10 : 1 to 1:1.
  • the weight ratio of component (b3) to component (a) is from 9:1 to 4.5:1.
  • compositions comprising mixtures of component (a) (preferably a compound from Index Table A) with cymoxanil and a compound selected from the group consisting of famoxadone, fenamidone, azoxystrobin, kresoxim-methyl, pyraclostrobin, trifloxystrobin, mancozeb, maneb, propineb, zineb, metalaxyl, benalaxyl, oxadixyl, 6-iodo-3-propyl-2-propyloxy-4(3H)-quinazolinone, 6- chloro-2-propoxy-3-propylthieno[2,3- ⁇ pyrimidin-4(3H)-one, folpet, captan and fosetyl- aluminum.
  • component (a) preferably a compound from Index Table A
  • compositions wherein component (b) comprises at least one compound selected from (b6), for example metalaxyl, and at least one compound selected from a second component (b) group, for example, from (bl), (b2), (b3), (bl), (b8) or (b9).
  • component (b) comprises at least one compound selected from (b6), for example metalaxyl, and at least one compound selected from a second component (b) group, for example, from (bl), (b2), (b3), (bl), (b8) or (b9).
  • the overall weight ratio of component (b) to component (a) is from 30: 1 to 1 :30 and the weight ratio of component (b6) to component (a) is from 10:1 to 1:3.
  • the weight ratio of component (b6) to component (a) is from 9:1 to 4.5:1.
  • compositions comprising mixtures of component (a) (preferably a compound from Index Table A) with metalaxyl or oxadixyl and a compound selected from the group consisting of famoxadone, fenamidone, azoxystrobin, kresoxim-methyl, pyraclostrobin, trifloxystrobin, cymoxanil, mancozeb, maneb, propineb, zineb, 6-iodo-3-propyl- 2-propyloxy-4(3H)-quinazolinone, 6-chloro-2-propoxy-3-propylt eno[2,3-- ⁇ pyrimidin- 4(3H)-one, folpet, captan and fosetyl-aluminum.
  • component (a) preferably a compound from Index Table A
  • the overall weight ratio of component (b) to component (a) is from 30: 1 to 1 :30 and the weight ratio of component (b7) to component (a) is from 1:1 to 1 :20.
  • compositions wherein the weight ratio of component (b6) to component (a) is from 1:4.5 to 1 :9.
  • these compositions include compositions comprising mixtures of component (a) (preferably a compound from Index Table A) with 6-iodo-3-propyl-2-propyloxy-4(3H)-quinazolinone or 6-chloro-2-propoxy-3-propylthieno[2,3- ⁇
  • compositions wherein component (b) comprises the compound of (b9), in other words fosetyl-aluminum, and at least one compound selected from a second component (b) group, for example, from (bl), (b2), (b3), (b6) or (bl).
  • component (b) comprises the compound of (b9), in other words fosetyl-aluminum, and at least one compound selected from a second component (b) group, for example, from (bl), (b2), (b3), (b6) or (bl).
  • the overall weight ratio of component (b) to component (a) is from 30: 1 to 1 :30 and the weight ratio of component (b9) to component (a) is from 10: 1 to 1:1.
  • the weight ratio of component (b9) to component (a) is from 9:1 to 4.5:1.
  • compositions comprising mixtures of component (a) (preferably a compound from Index Table A) with fosetyl- aluminum and a compound selected from the group consisting of famoxadone, fenamidone, azoxystrobin, kresoxim-methyl, pyraclostrobin, trifloxystrobin, mancozeb, maneb, propineb, zineb, metalaxyl, benalaxyl, oxadixyl, 6-iodo-3-propyl-2-propyloxy-4(3H)-quinazolinone, 6- cMoro-2-propoxy-3-propylthieno[2,3-rf]pyrimidin-4(3H)-one, folpet, captan and cymoxanil.
  • component (a) preferably a compound from Index Table A
  • strobilurins such as azoxystrobin, kresoxim-methyl, pyraclostrobin and trifloxystrobin
  • mo ⁇ holines such as fenpropidine and fenpropimo ⁇ h
  • triazoles such as bromuconazole, cyproconazole, difenoconazole, epoxyconazole, flusilazole, ipconazole, metconazole, propiconazole, tebuconazole and triticonazole
  • pyrimidinone fungicides benomyl; carbendazim; chlorothalonil; dimethomo ⁇ h; folpet; mancozeb; maneb; quinoxyfen; validamycin and vinclozolin.
  • Preferred compositions comprise a compound of component (a) mixed with cymoxanil.
  • Preferred compositions comprise a compound of component (a) mixed with a compound selected from (bl). More preferred is a composition wherein the compound of (bl) is mancozeb.
  • Preferred compositions comprise a compound of component (a) mixed with a compound selected from (b2). More preferred is a composition wherein the compound of (b2) is famoxadone.
  • compositions of this invention will generally be used as a formulation or composition comprising at least one carrier selected from agriculturally suitable liquid diluents, solid diluents and surfactants.
  • 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 (e.g. from 0.01-99.99 weight percent) of active ingredients together with diluent and/or surfactant within the following approximate ranges which add up to 100 percent by weight.
  • Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon 's Detergents and Emulsifiers Annual, Allured Publ. Co ⁇ ., 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, N,N-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 tefrahydroi-urfuryl alcohol.
  • Solutions can be prepared by simply mixing the ingredients. Dusts and powders can be prepared by blending and, usually, grinding as in a hammer mill or fluid-energy mill. Suspensions are usually prepared by wet-milling; see, for example, U.S. 3,060,084.
  • Preferred suspension concentrates include those containing, in addition to the active ingredient, from 5 to 20% nonionic surfactant (for example, polyethoxylated fatty alcohols) optionally combined with 50-65% liquid diluents and up to 5% anionic surfactants.
  • Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques.
  • 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.
  • Active ingredients 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium hgninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.
  • Active ingredients 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.
  • Active ingredients 20 0% polyethoxylated fatty alcohol nonionic surfactant 15.0% ester derivative of montan wax 3.0% calcium lignosulfonate anionic surfactant 2.0% polyethoxylated/polypropoxylated polyglycol block copolymer surfactant 1.0% propylene glycol diluent 6.4% poly(dimethylsiloxane) antifoam agent 0.6% antimicrobial agent 0.1% water diluent 51.9% The formulation ingredients are mixed together as a syrup, the active ingredients are added and the mixture is homogenized in a blender. The resulting slurry is then wet-milled to form a suspension concentrate.
  • compositions of this invention can also be mixed with one or more insecticides, nematocides, bactericides, acaricides, growth regulators, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection.
  • compositions of this invention can be formulated are: insecticides such as abamectin, acephate, azinphos-methyl, bifenthrin, buprofezin, carbofuran, chlorfenapyr, chlo ⁇ yrifos, chlo ⁇ yrifos-methyl, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, deltamethrin, diafenthiuron, diazinon, diflubenzuron, dimethoate, esfenvalerate, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flucythrinate, tau-fluvalinate, fonophos, imidacloprid, isofenphos, malathion, metaldehyde, methamidophos, methidathi
  • compositions of this invention are useful as plant disease control agents.
  • the present invention therefore further comprises a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof to be protected, or to the plant seed or seedling to be protected, an effective amount of a compound of the invention or a fungicidal composition containing said compound.
  • the compounds and compositions of this invention provide control of diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete, Ascomycete, Oomycete and Deuteromycete classes. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, vegetable, field, cereal, and fruit crops.
  • pathogens include Plasmopara viticola, Phytophthora infestans, Peronospora tabacina, Pseudoperonospora cubensis, Pythium aphanidermatum, Alternaria brassicae, Septoria nodorum, Septoria tritici, Cercosporidiumpersonatum, Cercospora arachidicola, Pseudocercosporella herpotrichoides, Cercospora beticola, Botrytis cinerea, Monilinia fructicola, Pyricularia oryzae, Podosphaera leucotricha, Venturia inaequ ⁇ lis, Erysiphe graminis, Uncinula necatur, Puccinia recondita, Puccinia graminis, Hemileia vastatrix, Puccinia striiformis, Puccinia arachidis, Rhizoctonia solani, Sphaerothecaful
  • Plant disease control is ordinarily accomplished by applying an effective amount of a compound of this invention either pre- or post-infection, to the portion of the plant to be protected such as the roots, stems, foliage, fruit, seeds, tubers or bulbs, or to the media (soil or sand) in which the plants to be protected are growing.
  • the compounds can also be apphed to the seed to protect the seed and seedling.
  • Rates of application for these compounds can be influenced by many factors of the environment and should be determined under actual use conditions. Foliage can normally be protected when treated at a rate of from less than 1 g/ha to 5,000 g/ha of active ingredient. Seed and seedlings can normally be protected when seed is treated at a rate of from 0.1 to 10 g per kilogram of seed.
  • Synergism has been described as "the cooperative action of two components of a mixture, such that the total effect is greater or more prolonged than the sum of the effects of the two (or more) taken independently" (see Tames, P. M. L., Neth. J. Plant Pathology, 1964, 70, 73-80). It is found that compositions containing the compound of Formula I and fungicides with a different mode of action exhibit synergistic effects.

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Abstract

Compositions for controlling plant diseases caused by fungal plant pathogens are described, comprising: (a) a fungicidally effective amount of a compound of Formula (I) (including all geometric and stereoisomers, N-oxides, and agriculturally suitable salts thereof) wherein A, B, W, R1, R2, and R3 are as defined in the disclosure; and (b) at least one compound selected from the group consisting of (b1) alkylenebis(dithiocarbamate) fungicides; (b2) compounds acting at the bc1complex of the fungal mitochondrial respiratory electron transfer site; (b3) cymoxanil; (b4) compounds acting at the demethylase enzyme of the sterol biosynthesis pathway; (b5) morpholine and piperidine compounds that act on the sterol biosynthesis pathway; (b6) phenylamide fungicides; (b7) pyrimidinone fungicides; (b8) phthalimides; and (b9) fosetyl-aluminum.Also disclosed are methods for controlling plant diseases caused by fungal plant pathogens that involves applying an effective amount of the combinations described. Also disclosed are certain compounds of Formula (I).

Description

TITLE
BENZ AMIDES AND ADVANTAGEOUS COMPOSITIONS THEREOF FOR USE AS
FUNGICIDES
BACKGROUND OF THE INVENTION
This invention relates to certain benzamides, their N-oxides, agriculturally suitable salts, certain advantageous compositions containing a mixture of benzamides and other fungicides and methods of their use as fungicides.
The control of plant diseases caused by fungal plant pathogens is extremely important in achieving high crop efficiency. Plant disease damage to ornamental, vegetable, field, cereal, and fruit crops can cause significant reduction in productivity and thereby result in increased costs to the consumer. Many products are commercially available for these purposes, but the need continues for new products that are more effective, less costly, less toxic, or environmentally safer.
WO 99/42447 discloses certain benzamides of formula i as fungicides
wherein, among others,
R1 is H, alkyl or acyl;
R2 is H or alkyl; and
L is -(CO)-, -S02- or -(C=S)-
Figure imgf000002_0001
WO 02/16322 discloses a novel process for preparing certain benzamides of formula ii that are useful as fungicides
Figure imgf000002_0002
O wherein, among others, n X is halogen;
Y is halogen, haloalk l, alkoxycarbonyl or al ylsulfonyl; each R1 and R2 is idependently halogen; mis 0,1 or 2; and nis 0 to 3.
Fungicides that effectively control plant fungi, particularly of the class Oomycetes, such as Phytophthora spp. and Plasmopara spp., are in constant demand by growers. Combinations of fungicides are often used to facilitate disease control and to retard resistance development. It is desirable to enhance the activity spectrum and the efficacy of disease control by using mixtures of active ingredients that provide a combination of curative, systemic andpreventative control of plant pathogens. Also desirable are combinations that provide greater residual control to allow for extended spray intervals. It is also very desirable to combine fungicidal agents that inhibit different biochemical pathways in the fungal pathogens to retard development of resistance to any one particular plant disease control agent.
It is in all cases particularly advantageous to be able to decrease the quantity of chemical agents released in the environment while ensuring effective protection of crops from diseases caused by plant pathogens. Mixtures of fungicides may provide significantly better disease control than could be predicted based on the activity of the individual components. This synergism has been described as "the cooperative action of two components of a mixture, such that the total effect is greater or more prolonged than the sum of the effects of the two (or more) taken independently" (see Tames, P. M. L., Neth. J. Plant Pathology, (1964), 70, 73-80).
There is a desire to find fungicidal agents that are particularly advantageous in achieving one or more of the preceding objectives.
SUMMARY OF THE INVENTION
This invention provides a composition for controlling plant diseases caused by fungal plant pathogens comprising (a) at least one compound of Formula I (including all geometric and stereoisomers), N-oxides and agriculturally suitable salts thereof:
Figure imgf000003_0001
wherein
A is a substituted pyridinyl ring;
B is a substituted phenyl ring;
W is C=L or SOn;
L is O or S;
R1 and R2 are each independently H; or CrC6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl or
C3-C6 cycloalkyl, each optionally substituted; 3 is H; or CrC6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C2-C10 alkoxyalkyl, C -Cg alkylcarbonyl, C2-Cg alkoxycarbonyl, C2-Cg alkylaminocarbonyl or C3-Cg dialkylaminocarbonyl; and n is 1 or 2; and (b) at least one compound selected from the group consisting of (bl) alkylenebis(dithiocarbamate) fungicides;
(b2) compounds acting at the bcγ complex of the fungal mitochondrial respiratory- electron transfer site;
(b3) cymoxanil;
(b4) compounds acting at the demethylase enzyme of the sterol biosynthesis pathway;
(b5) morpholine and piperidine compounds that act on the sterol biosynthesis pathway;
(b6) phenylamide fungicides;
(b7) pyrimidinone fungicides;
(b8) phthalimides; and
(b9) fosetyl-aluminum.
This invention also relates to a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed or seedling, a f ngicidally effective amount of a composition of the invention.
This invention also provides a compound of Formula la (including all geometric and stereoisomers), N-oxides and agriculturally suitable salts thereof:
Figure imgf000004_0001
la
wherein
R4 is halogen; ,
R5 is Ci-Cg alkyl, halogen, ΝO2, -C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfϊnyl or C1-C4 haloalkylsulfonyl; each R6 is independently Cj-Cg alkyl, Ci-Cg haloalkyl, halogen, NO , C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl or C1-C4 haloalkylsulfonyl; or two R6 attached to contiguous carbon atoms are taken together with said carbon atoms to form a fused 5- or 6-membered nonaromatic heterocyclic ring containing one or two oxygen atoms and optionally substituted with from one to four substituents independently selected from F or methyl; and p is 1, 2, 3 or 4.
This invention also provides a compound of Formula lb (including all geometric and stereoisomers), N-oxides and agriculturally suitable salts thereof:
Figure imgf000005_0001
lb
wherein
R4 is halogen;
R5 is C1-C4 haloalkoxy, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl or C -C4 haloalkylsulfonyl; eachR6 is independently Cj-C6 alkyl, Ci-Cg haloalkyl, halogen, NO2, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl or C1-C4 haloalkylsulfonyl; or two R attached to contiguous carbon atoms are taken together with said carbon atoms to form a fused 5- or 6-membered nonaromatic heterocyclic ring containing one or two oxygen atoms and optionally substituted with from one to four substituents independently selected from F or methyl; and p is 1, 2, 3 or 4.
This invention also provides a compound of Formula Ic (including all geometric and stereoisomers), N-oxides and agriculturally suitable salts thereof:
Figure imgf000005_0002
wherein
R4 is Cl orBr;
R5 is Br orI; each R6 is independently Cj-Cg alkyl, Cj-C^ haloalkyl, halogen, ΝO2, C1-C4 alkoxy, CrC4 haloalkoxy,
Figure imgf000005_0003
alkylsulfonyl, C1-C4 haloalkylthio, -C4 haloalkylsulfinyl or C1-C4 haloalkylsulfonyl; or two R6 attached to contiguous carbon atoms are taken together with said carbon atoms to form a fused 5- or 6-membered nonaromatic heterocyclic ring containing one or two oxygen atoms and optionally substituted with from one to four substituents independently selected from F or methyl; and p is 1, 2, 3 or 4. DETAILS OF THE INVENTION
As noted above, A is a substituted pyridinyl ring and B is a substituted phenyl ring.
The term "substituted" in connection with these A or B groups refers to groups that have at least one non-hydrogen substituent that does not extinguish the fungicidal activity.
Examples of Formula I incorporating said pyridinyl rings in which A is substituted with 1 to
4 R5, B is substituted with 1 to 4 R6 include the rings illustrated in Exhibit 1 wherein m and p are independently integers from 1 to 4. Note that the attachment point between (R5)m and
A and (R6)p and B is illustrated as floating, and (R5)m and (R6)p can be attached to any available carbon atom of the A and B rings respectively.
Exhibit 1
Figure imgf000006_0001
1-1 1-2
Figure imgf000006_0002
1-3
Examples of R5 when attached to A and R6 when attached to B include: each R5 and R6 is independently Ci -Cg alkyl, C -Cg alkenyl, C -C6 alkynyl, C3-CQ cycloalkyl, C^-Cg haloalkyl, C -Cg haloalkenyl, C -C6 haloalkynyl, C3-C6 halocycloalkyl, halogen, CN, CO2H, CONH , NO , hydroxy, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, Cι~C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, Cj-C4 alkylamino, C2-Cg dialkylamino, C3-C6 cycloalkylamino, C2-Cg alkylcarbonyl, C2-Cg alkoxycarbonyl, C2-Cg alkylaminocarbonyl, C3-C dialkylaminocarbonyl or C3-C6 trialkylsilyl; or each R5 and 6 is independently a phenyl, a benzyl, a phenoxy, a 5- or 6-membered heteroaromatic ring or a 5- or 6-membered nonaromatic heterocyclic ring, each ring optionally substituted with from one to three substituents independently selected from R7; or two R6 attached to contiguous carbon atoms are taken together with said carbon atoms to form a fused phenyl ring, a fused 5- or 6-membered nonaromatic carbocyclic ring, a fused 5- or 6-membered heteroaromatic ring or a fused 5- or 6-membered nonaromatic heterocyclic ring, each fused ring optionally substituted with from one to four substituents independently selected from R7; each R7 is independently C1-C4 alkyl, C2-C4 alkenyl, C -C4 alkynyl, C -Cg cycloalkyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-C6 halocyclo alkyl, halogen, CN, NO2, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, Cj-Qψ alkylamino, C -Cg dialkylamino, C3-C6 cycloalkylamino, C3-C6 (alkyl)cycloalkylamino, C2-C4 alkylcarbonyl, C -Cg alkoxycarbonyl, C2-Cg alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl or C3-C6 trialkylsilyl. As noted above, R1 and R2 are each independently H; or C^-Cg alkyl, C2-Cg alkenyl, C2-Cβ alkynyl or C3-C6 cycloalkyl, each optionally substituted. The term "optionally substituted" in connection with these R1 and R2 groups refers to groups that are unsubstituted or have at least one non-hydrogen substituent that does not extinguish the fungicidal activity possessed by the unsubstituted analog. Examples of optionally substituted R1 and R2 groups are those that are optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO2, hydroxy, C1-C4 alkoxy, -C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C2-C4 alkoxycarbonyl, Ci -C4 alkylamino, C2-Cg dialkylamino and C3-C6 cycloalkylamino. Although these substituents are listed in the examples above, it is noted that they do not need to be present since they are optional substituents. Of note are R1 and R2 groups that are optionally substituted with one to four substituents selected from the group above.
Examples of N-oxides of Formula I are illustrated as 1-4 through 1-6 in Exhibit 2, wherein R1, R2, R3, R5, R6, W, m and p are as defined above.
Exhibit 2
Figure imgf000007_0001
1-4
Figure imgf000007_0002
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, n-propyl, z-propyl, or the different butyl, pentyl or hexyl isomers. "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, n-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. "Alkoxyalkoxy" denotes alkoxy substitution on alkoxy. The term "Alkenyloxy" includes straight chain or branched alkenyloxy moieties. Examples of "alkenyloxy" include H2C=CHCH2O, (CH3)2C=CHCH2O, (CH3)CH=CHCH2O, (CH3)CH=C(CH3)CH2O and CH =CHCH2CH2O. "Alkynyloxy" includes straight chain or branched alkynyloxy moieties. Examples of "alkynyloxy" include HC≡CCH2O, CH3C≡CCH2O and CH3C≡CCH2CH2O. "Alkylthio" includes branched or straight chain alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio andhexylthio isomers. "Alkylsulfinyl" includes both enantiomers of an alkylsulfinyl group. Examples of "alkylsulfinyl" include CH3S(O), CH3CH2S(O), CH3CH2CH2S(O), (CH3)2CHS(O) and the different butylsulfinyl, pentylsulfinyl and hexylsulfinyl isomers. Examples of "alkylsulfonyl" include CH3S(O)2, CH3CH2S(O)2, CH3CH2CH2S(O)2, (CH3)2CHS(O)2 and the different butylsulfonyl, pentylsulfonyl and hexylsulfonyl isomers. "Alkylamino", "dialkylamino", "alkenylthio", "alkenylsulfinyl", "alkenylsulfonyl", "alkynylthio", "alkynylsulfinyl", "alkynylsulfonyl", and the like, are defined analogously to the above examples. "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.
The term "halogen", either alone or in compound words such as "haloalkyl", includes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as "haloalkyl", said alkyl may be partially or fully substituted with halogen atoms which may be the same or different. Examples of "haloalkyl" include 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, CCI3G- and FCH2C≡CCH2. Examples of "haloalkoxy" include CF3O, CCl3CH2O, HCF2CH2CH2O and CF3CH2O. Examples of "haloalkylthio" include CCI3S, CF3S, CC13CH2S and C1CH2CH2CH2S. Examples of "haloalkylsulfinyl" include CF3S(O), CCl3S(O), CF3CH2S(O) and CF3CF2S(O). Examples of "haloalkylsulfonyl" include CF3S(O)2, CCl3S(O)2, CF3CH2S(O)2 and CF3CF2S(O)2. 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.
"Aromatic" indicates that each of the ring atoms is essentially in the same plane and has a^-orbital peφendicular to the ring plane, and in which (4n + 2) π electrons, when n is 0 or a positive integer, are associated with the ring to comply with Hύckel's rule. The term "aromatic carbocyclic ring" includes fully aromatic carbocycles (e.g. phenyl). The term "nonaromatic carbocyclic ring" denotes fully saturated carbocycles as well as partially or fully unsaturated carbocycles where the Hϋckel rule is not satisfied. The term "hetero" in connection with rings refers to a ring in which at least one ring atom is not carbon and which can contain 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur, provided that each ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs. The terms "heteroaromatic ring includes fully aromatic heterocycles. The term "nonaromatic heterocyclic ring" denotes fully saturated heterocycles as well as partially or fully unsaturated heterocycles where the Hϋckel rule is not satisfied. The heterocyclic ring 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 m-chloroperbenzoic acid (MCPB A), hydrogen peroxide, alkyl hydroperoxides such as t-butyl hydroperoxide, sodium perborate, and dioxiranes such as dimethydioxirane. 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. V. 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 andB. 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 m. Advances in Heterocyclic Chemistry, vol. 22, pp 390-392, A. R. Katritzky and A. J. Boulton, Eds., Academic Press. The total number of carbon atoms in a substituent group is indicated by the "Ci-Cj" prefix where i and j are numbers from 1 to 8. For example, C]-C3 alkylsulfonyl designates methylsulfonyl through propylsulfonyl; C alkoxyalkyl designates CH3OCH2; C3 alkoxyalkyl designates, for example, CH3CH(OCH3), CH3OCH2CH2 or CH3CH2OCH2; and C4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH3CH2CH2OCH2 and CH3CH2OCH2CH2.
When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents. Further, when the subscript indicates a range, e.g. (R)i_j, then the number of substituents may be selected from the integers between i and j inclusive.
When a group contains a substituent which can be hydrogen, for example R1 or R2 then, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted.
Compounds of Formula I 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. Accordingly, the present invention comprises compounds selected from Formula I, N-oxides and agriculturally suitable salts thereof. The compounds of Formula I may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form. In particular, when R1 and R2 of Formula I are different, then said Formula possesses a chiral center at the carbon to which R1 and R2 are commonly bonded.
This invention includes racemic mixtures of equal parts of Formula I' and Formula I".
Figure imgf000010_0001
r I"
wherein A, B W, R1, R2 and R3 are as defined above. In addition, this invention includes compositions that are emiched compared to the racemic mixture in an enantiomer of the Formula I' or Formula I". This invention also includes compositions wherein component (a) is emiched in a component (a) enantiomer of Formula I' compared to the racemic mixture of component (a). Included are compositions comprising the essentially pure enantiomers of Formula F. This invention also includes compositions wherein component (a) is enriched in a component (a) enantiomer of Formula I" compared to the racemic mixture of component (a). Included are compositions comprising the essentially pure enantiomers of Formula I".
When enantiomerically enriched, one enantiomer is present in greater amounts that the other and the extent of enrichment can be defined by an expression of enantiomer excess("ee"), which is defined as 100(2x-l) where x is the mole fraction of the dominant enantiomer in the enantiomer mixture (e.g., an ee of 20% corresponds to a 60:40 ratio of enantiomers).
The more active enantiomer with respect to the relative positions of R1, R2, A and the rest of the molecule bonded through nitrogen corresponds to the configuration of the enantiomer of Formula I that, when in a solution of CDCI3, rotates plane polarized light in the (+) or dextro direction.
Preferably there is at least a 50% enantiomeric excess; more preferably at least a 75 % enantiomeric excess; still more preferably at least a 90% enantiomeric excess; and the most preferably at least a 94% enantiomeric excess of the more active isomer of Formula I. Of particular note are enantiomerically pure embodiments of the more active isomer of Formula I.
The salts of the compounds of Formula I 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 Formula I 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. Preferred compositions of the invention, wherein (a) comprises compounds of
Formula I, for reasons of better activity and/or ease of synthesis are: Preferred 1. Preferred are compositions wherein in Formula I A is a pyridinyl ring substituted with from 1 to 4 R5; B is a phenyl ring substituted with from 1 to 4 R6; W is C=O;
R1 and R2 are each independently H; or Ci-Cg alkyl, C2-C6 alkenyl, C2-C6 alkynyl or C3-C6 cycloalkyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO2, hydroxy, CrC4 alkoxy, -C4 alkylthio, CrC4 alkylsulfinyl, CX-C4 alkylsulfonyl, C2-C4 alkoxycarbonyl,
Figure imgf000011_0001
alkylamino, C2-C8 dialkylamino and C3-C6 cycloalkylamino; R3 is H; and each R5 and R6 is independently Ci -Cg alkyl, C2-Cg alkenyl, C2-Cg alkynyl, C3-C6 cycloalkyl, Cj-Cg haloalkyl, C2-Cg haloalkenyl, C2-C6 haloalkynyl, C3-C6 halocycloalkyl, halogen, CN, CO2H, CONH2, NO2, hydroxy, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, Cj-Qφ haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, C1-C4 alkylamino, C2-Cg dialkylamino, C3-Cg cycloalkylamino, C2-C6 alkylcarbonyl, C2-Cg alkoxycarbonyl, C -Cg alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl or C3-Cg trialkylsilyl; or each R5 and R6 is independently a phenyl, a benzyl, a phenoxy, a 5- or 6-membered heteroaromatic ring or a 5- or 6-membered nonaromatic heterocyclic ring, each ring optionally substituted with one to three substituents independently selected from R7; or two R6 attached to contiguous carbon atoms are taken together with said carbon atoms to form a fused phenyl ring, a fused 5- or 6-membered nonaromatic carbocyclic ring, a fused 5- or 6-membered heteroaromatic ring or a fused 5- or 6-membered nonaromatic heterocyclic ring, each fused ring optionally substituted with one to four substituents independently selected from R7; and each R7is independently C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-Cg cycloalkyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-Cg halocycloalkyl, halogen, CN, NO , Cj-C4 alkoxy, C1-C4 haloalkoxy, -C4 alkylthio, C1-C4 alkylsulfinyl, -C4 alkylsulfonyl, C1-C4 alkylamino, C2-Cg dialkylamino, C -C6 cycloalkylamino, C3-Cg (alkyl)cycloalkylamino, C2-C4 alkylcarbonyl, C2-Cg alkoxycarbonyl, C2-Cg alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl or C3-C6 trialkylsilyl. Of note are compositions of Preferred 1 wherein A is a substituted 3-pyridinyl ring. Preferred 2. Compositions of Preferred 1 wherein
A is a 2-pyridinyl ring substituted with from 1 to 4 R5; and
B is substituted with from 1 to 4 R6, with at least one R6 located in a position ortho to the link with W. Of note are compositions wherein eachR6 is independently F, CI, Br, I, CH3, OCH3, OCF3, OCHF2, CF3 or NO2. Also of note are compositions wherein at least one R6 is iodo. Preferred 3. Compositions of Preferred 2 wherein B is substituted with an R6 at each position ortho to the link with W, and optionally one additional R6, and each R6 is independently F, CI, Br, I, CH3, OCH3 or CF3. Of note are compositions wherein each R6 is either halogen or methyl. Preferred 4. Compositions of Preferred 3 wherein B is substituted with one R6 as a CI located at the 2-position ortho to the link with W, another R6 is selected from CI or methyl and is located at the 6-position ortho to the link with W and a third optional R6 is methyl at the 4-position. Preferred 5. Compositions of Preferred 4 wherein A is 3-chloro-5-CF3-2-pyridinyl. Preferred compositions of this invention include those of Preferred 1 through Preferred 5 wherein R1 is H and R2 is H or CH3. More preferred are compositions of Preferred 1 through Preferred 5 wherein R1 is H and R2 is CH .
Specifically preferred are compositions comprising a compound selected from the group consisting of
2,6-ώcMoro-N-[[3-chloro-5-(1rifluoromemyl)-2-pyridinyl]memyl]benzamide, 2,6-dicMoro-N-[l-[3-chloro-5-(trifluoromemyl)-2-pyridinyl]ethyl]benzamide, 2,6-dic oro-N-[[3-chloro-5-(trifluoromethyl)-2-pyridinyl]methyl]-4- methylbenzamide,
2,6-cUcMoro-N-[l-[3-chloro-5-(trifluoromethyl)-2-pyridinyl]ethyl]-4- methylbenzamide,
2,6-dichloro-N-[(3,5-dichloro-2-pyridinyl)methyl]benzamide, 2,6-dichloro-N-[l-(3,5-dichloro-2-pyridinyl)ethyl]benzamide, 2,6-dichloro-N-[(3,5-dichloro-2-pyridinyl)methyl]-4-methylbenzamide, and 2,6-dicUoro-N-[l-(3,5-dicMoro-2-pyridinyl)ethyl]-4-methylbenzamide. Of note are compositions comprising a compound selected from the group consisting of
2,6-dic oro-N-[[3-chloro-5-(1nfluoromethyl)-2-pyridinyl]methyl]berιzamide (also known as N-[(3-chloro-5-trifluoromethyl-2-pyridyl)methyl]-2,6- dichlorobenzamide),
N-[[(3-chloro-5-(trifluoromemyl)-2-pyridinyl]memyl]-2,6-dfluorobenzamide (also known as N-[(3-chloro-5-trifluoromethyl-2-pyridyl)methyl]-2,6- difluorobenzamide),
2-cMoro-N-[[3-chloro-5-(Mfluorome yl)-2-pyridinyl]methyl]-6-fluorobenzamide
(also known as N-[(3-chloro-5-trifl.uoromethyl-2-pyridyl)methyl]-2-chloro-6- fluorobenzamide),
N-[[(3-chloro-5-(lrifluoromethyl)-2-pyridinyl]methyl]-2,3-difluorobenzamide (also known as N-[(3-chloro-5-trifluoromethyl-2-pyridyl)methyl]- 2,3- difluorobenzamide),
N-[[(3-cWoro-5-(trifluoromemyl)-2-pyridinyl]methyl]-2,4,6-trifluorobenzamide
(also known as N-[(3-chloro-5-trifluoromethyl-2-pyridyl)methyl]-2,4,6- trifluorobenzamide), and 2-bromo-6-chloro-N-[[3-cMoro-5-(trifluorome yl)-2-pyridinyl]memyl]benzamide (also known as N-[(3-chloro-5-trifluoromethyl-2-pyridyl)methyl]-2-bromo-6- chlor obenzamide) . This invention also relates to a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed or seedling, a fungicidally effective amount of the composition of the invention (i.e., as a composition described herein). The preferred methods of use are those involving the above- preferred compositions.
This invention also provides a compound of Formula la as described above. Preferred compounds of Formula la are:
Preferred A. Compounds of Formula la wherein R5 is CI, Br, I, CH3, OCF3, OCHF2, OCH2CF3, OCF2CF3, OCF2CF2H, OCHFCF3, SCF3, SCHF2, SCH2CF3, SCF2CF3, SCF2CF2H, SCHFCF3, SOCF3, SOCHF2, SOCH2CF3, SOCF2CF3, SOCF2CF2H, SOCHFCF3, SO2CF3, SO2CHF2, SO2CH2CF3, SO2CF2CF3, SO2CF2CF2H or SO2CHFCF3.
Preferred B. Compounds of Preferred A wherein at least one R6 is located in a position ortho to the link with the C=O moiety and each R6 is independently F, CI, Br, I, CH3, OCH3, OCF3, OCHF2, CF3 or ΝO2. Preferred C. Compounds of Preferred B wherein there is an R6 at each position ortho to the link with the 0=0 moiety, and optionally one additional R6, and each R6 is independently F, CI, Br, I, CH3, OCH3 or CF3. This invention also provides a compound of Formula lb as described above. Preferred compounds of Formula lb are:
Preferred D. Compounds of Formula lb wherein R5 is, OCF3, OCHF2, OCH2CF3, OCF2CF3, OCF2CF2H, OCHFCF3, SCF3, SCHF2, SCH2CF3, SCF2CF3, SCF2CF2H, SCHFCF3, SOCF3, SOCHF2, SOCH2CF3, SOCF2CF3, SOCF2CF2H, SOCHFCF3, SO2CF3, SO2CHF2, SO2CH2CF3, SO2CF2CF3, SO2CF2CF2H or SO2CHFCF3.
Preferred E. Compounds of Preferred D wherein at least one R6 is located in a position ortho to the link with the C=O moiety and each R6 is independently F, CI, Br, I, CH3, OCH3, OCF3, OCHF2, CF3 orNO2. Preferred F. Compounds of Preferred E wherein there is an R^ at each position ortho to the link with the C=O moiety, and optionally one additional R6, and each R6 is independently F, CI, Br, I, CH3, OCH3 or CF3. This invention also provides a compound of Formula Ic as described above. Preferred compounds of Formula Ic are:
Preferred G. Compounds of Formula Ic wherein at least one R6 is located in a position ortho to the link with the C=O moiety and each R6 is independently F, CI, Br, I, CH3, OCH3, OCF3, OCHF2, CF3 or NO2. Preferred H. Compounds of Preferred G wherein there is an R^ at each position ortho to the link with the C=O moiety, and optionally one additional R6, and each R6 is independently F, CI, Br, I, CH3, OCH3 or CF3. Compounds of Formula I can be prepared by one or more of the methods and variations described in WO99/42447 (See e.g., Example 4). Some compounds of Formula I can also be prepared by methods described in WO02/16322.
Examples of compounds of Formula I suitable for use in component (a) of the compositions of this invention include the following compounds of Tables 1-7. The following abbreviations are used in the Tables which follow: Me is methyl, Et is ethyl, Ph is phenyl, OMe is methoxy, OEt is ethoxy, CN is cyano, NO2 is nitro. The substituents Q and R are equivalent to independent R5 substituents that have been located in the positions indicated. The substituents T, U and V are equivalent to independent R6 substituents that have been located in the positions indicated.
Table 1
Figure imgf000015_0001
T U V T U V T U V T U V
Me Me Me OMe Me Me CI N02 Me Br Me Me
Me Me F OMe Me F CI N02 F Br Me F
Me Me CI OMe Me CI CI N02 CI Br Me CI
Me Me Br OMe Me Br CI N02 Br Br Me Br
Me Me CF3 OMe Me CF3 CI N02 CF3 Br Me CF3
Me Me N02 OMe Me N02 CI N02 N02 Br Me N02
Me Me OMe OMe Me OMe CI N02 OMe Br Me OMe
F Me Me OMe F Me CF3 OMe Me CF3 Me Me
F Me F OMe F F CF3 OMe F CF3 Me F
F Me CI OMe F CI CF3 OMe CI CF3 Me CI
F Me Br OMe F Br CF3 OMe Br CF3 Me Br
F Me CF3 OMe F CF3 CF3 OMe CF3 CF3 Me CF3
F Me N02 OMe F N02 F OMe Me CF3 Me N02
F Me OMe OMe F OMe F OMe F CF3 Me OMe
CI Me Me OMe CI Me F OMe CI N02 Me Me
CI Me F OMe CI F F OMe Br N02 Me F
CI Me CI OMe CI CI F OMe CF3 N02 Me CI T U V T U V T U V T U V
CI Me Br OMe CI Br F OMe N02 N02 Me Br
CI Me CF3 OMe CI CF3 F OMe OMe N02 Me CF3
CI Me N02 OMe CI N02 CF3 OMe N02 N02 Me N02
CI Me OMe OMe CI OMe CF3 OMe OMe N02 Me OMe
Me F Me OMe H Me Br OMe N02 Br F Me
Me F F OMe H F Br OMe OMe Br F F
Me F CI OMe H CI N02 N02 Me Br F CI
Me F Br OMe H OMe N02 N02 F Br F Br
Me F CF3 OMe OMe CF3 N02 N02 CI Br F CF3
Me F N02 OMe OMe N02 N02 N02 Br Br F N02
Me F OMe OMe OMe OMe N02 N02 CF3 Br F OMe
F F Me OMe Br Me N02 N02 N02 CF3 F Me
F F F OMe Br F N02 N02 OMe CF3 F F
F F CI OMe Br CI Br OMe Me CF3 F CI
F F Br OMe Br Br Br OMe F CF3 F Br
F F CF3 OMe Br CF3 Br OMe CI CF3 F CF3
F F N02 OMe Br N02 Br OMe Br CF3 F N02
F F OMe OMe Br OMe Br OMe CF3 CF3 F OMe
CI F Me OMe CF3 Me Me N02 Me N02 F Me
CI F F OMe CF3 F Me N02 F N02 F F
CI F CI OMe CF3 CI Me N02 CI N02 F CI
CI F Br OMe CF3 Br Me N02 Br N02 F Br
CI F CF3 OMe CF3 CF3 Me N02 CF3 N02 F CF3
CI F N02 OMe CF3 N02 Me N02 N02 N02 F N02
CI F OMe OMe CF3 OMe Me N02 OMe N02 F OMe
Me CI Me OMe N02 Me F N02 Me Br CI Me
Me CI F OMe N02 F F N02 F Br CI F
Me CI CI OMe N02 CI F N02 CI Br CI CI
Me CI Br OMe N02 Br F N02 Br Br CI Br
Me CI CF3 OMe N02 CF3 F N02 CF3 Br CI CF3
Me CI N02 OMe N02 N02 F N02 N02 Br CI N02
Me CI OMe OMe N02 OMe F N02 OMe Br CI OMe
F CI Me OMe H Br Br H Me CF3 CI Me
F CI F OMe H CF3 Br H F CF3 CI F
F CI CI OMe H N02 Br H CI CF3 CI CI
F CI Br OMe OMe Me Br H Br CF3 CI Br
F CI CF3 OMe OMe F Br H CF3 CF3 CI CF3 T U V T u V T U V T U V
F CI N02 OMe OMe CI Br H N02 CF3 CI N02
F CI OMe OMe OMe Br Br H OMe CF3 CI OMe
CI CI Me F H Me Me OMe Me N02 CI Me
CI CI F F H F Me OMe F N02 CI F
CI CI CI F H CI Me OMe CI N02 CI CI
CI CI Br F H Br Me OMe Br N02 CI Br
CI CI CF3 F H CF3 Me OMe CF3 N02 CI CF3
CI CI N02 F H N02 Me OMe N02 N02 CI N02
CI CI OMe F H OMe Me OMe OMe N02 CI OMe
Me Br Me CI H Me Br N02 Me Br Br Me
Me Br F CI H F Br N02 F Br Br F
Me Br CI CI H CI Br N02 CI Br Br CI
Me Br Br CI H Br Br N02 Br Br Br Br
Me Br CF3 CI H CF3 Br N02 CF3 Br Br CF3
Me Br N02 CI H N02 Br N02 N02 Br Br N02
Me Br OMe CI H OMe Br N02 OMe Br Br OMe
F Br Me CF3 H Me CF3 N02 Me CF3 Br Me
F Br F CF3 H F CF3 N02 F CF3 Br F
F Br CI CF3 H CI CF3 N02 CI CF3 Br CI
F Br Br CF3 H Br CF3 N02 Br CF3 Br Br
F Br CF3 CF3 H CF3 CF3 N02 CF3 CF3 Br CF3
F Br N02 CF3 H N02 CF3 N02 N02 CF3 Br N02
F Br OMe CF3 H OMe CF3 N02 OMe CF3 Br OMe
CI Br Me N02 H Me CI CF3 Me N02 Br Me
CI Br F N02 H F CI CF3 F N02 Br F
CI Br CI N02 H CI CI CF3 CI N02 Br CI
CI Br Br N02 H Br CI CF3 Br N02 Br Br
CI Br CF3 N02 H CF3 CI CF3 CF3 N02 Br CF3
CI Br N02 N02 H N02 CI CF3 N02 N02 Br N02
CI Br OMe N02 H OMe CI CF3 OMe N02 Br OMe
Me CF3 Me CI OMe Me N02 OMe Me Br CF3 Me
Me CF3 F CI OMe F N02 OMe F Br CF3 F
Me CF3 CI CI OMe CI N02 OMe CI Br CF3 CI
Me CF3 Br CI OMe Br N02 OMe Br Br CF3 Br
Me CF3 CF3 CI OMe CF3 N02 OMe CF3 Br CF3 CF3
Me CF3 N02 CI OMe N02 N02 OMe N02 Br CF3 N02
Me CF3 OMe CI OMe OMe N02 OMe OMe Br CF3 OMe T U V T U V T U V T U V
F CF3 Me Me H Me N02 CF3 Me CF3 CF3 Me
F CF3 F Me H F N02 CF3 F CF3 CF3 F
F CF3 CI Me H CI N02 CF3 CI CF3 CF3 CI
F CF3 Br Me H Br N02 CF3 Br CF3 CF3 Br
F CF3 CF3 Me H CF3 N02 CF3 CF3 CF3 CF3 CF3
F CF3 N02 Me H N02 N02 CF3 N02 CF3 CF3 N02
F CF OMe Me H OMe N02 CF3 OMe CF3 CF3 OMe
Table 2
Figure imgf000018_0001
T u V T U V T U V T U V
Me Me Me OMe Me Me CI N02 Me Br Me Me
Me Me F OMe Me F CI N02 F Br Me F
Me Me CI OMe Me CI CI N02 CI Br Me CI
Me Me Br OMe Me Br CI N02 Br Br Me Br
Me Me CF3 OMe Me CF3 CI N02 CF3 Br Me CF3
Me Me N02 OMe Me N02 CI N02 N02 Br Me N02
Me Me OMe OMe Me OMe CI N02 OMe Br Me OMe
F Me Me OMe F Me CF3 OMe Me CF3 Me Me
F Me F OMe F F CF3 OMe F CF3 Me F
F Me CI OMe F CI CF3 OMe CI CF3 Me CI
F Me Br OMe F Br CF3 OMe Br CF3 Me Br
F Me CF OMe F CF3 CF3 OMe CF3 CF3 Me CF3
F Me N02 OMe F N02 F OMe Me CF3 Me N02
F Me OMe OMe F OMe F OMe F CF3 Me OMe
CI Me Me OMe CI Me F OMe CI N02 Me Me
CI Me F OMe CI F F OMe Br N02 Me F
CI Me CI OMe CI CI F OMe CF3 N02 Me CI
CI Me Br OMe CI Br F OMe N02 N02 Me Br
CI Me CF3 OMe CI CF3 F OMe OMe N02 Me CF3
CI Me N02 OMe CI N02 CF3 OMe N02 N02 Me N02
CI Me OMe OMe CI OMe CF3 OMe OMe N02 Me OMe T U V T U V T U V T U V
Me F Me OMe H Me Br OMe N02 Br F Me
Me F F OMe H F Br OMe OMe Br F F
Me F CI OMe H CI N02 N02 Me Br F CI
Me F Br OMe H OMe N02 N02 F Br F Br
Me F CF3 OMe OMe CF3 N02 N02 CI Br F CF3
Me F N02 OMe OMe N02 N02 N02 Br Br F N02
Me F OMe OMe OMe OMe N02 N02 CF3 Br F OMe
F F Me OMe Br Me N02 N02 N02 CF3 F Me
F F F OMe Br F N02 N02 OMe CF3 F F
F F CI OMe Br CI Br OMe Me CF3 F CI
F F Br OMe Br Br Br OMe F CF3 F Br
F F CF3 OMe Br CF3 Br OMe CI CF3 F CF3
F F N02 OMe Br N02 Br OMe Br CF3 F N02
F F OMe OMe Br OMe Br OMe CF3 CF3 F OMe
CI F Me OMe CF3 Me Me N02 Me N02 F Me
CI F F OMe CF3 F Me N02 F N02 F F
CI F CI OMe CF3 CI Me N02 CI N02 F CI
CI F Br OMe CF3 Br Me N02 Br N02 F Br
CI F CF OMe CF3 CF3 Me N02 CF3 N02 F CF3
CI F N02 OMe CF3 N02 Me N02 N02 N02 F N02
CI F OMe OMe CF3 OMe Me N02 OMe N02 F OMe
Me CI Me OMe N02 Me F N02 Me Br CI Me
Me CI F OMe N02 F F N02 F Br CI F
Me CI CI OMe N02 CI F N02 CI Br CI CI
Me CI Br OMe N02 Br F N02 Br Br CI Br
Me CI CF3 OMe N02 CF3 F N02 CF3 Br CI CF3
Me CI N02 OMe N02 N02 F N02 N02 Br CI N02
Me CI OMe OMe N02 OMe F N02 OMe Br CI OMe
F CI Me OMe H Br Br H Me CF3 CI Me
F CI F OMe H CF3 Br H F CF3 CI F
F CI CI OMe H N02 Br H CI CF3 CI CI
F CI Br OMe OMe Me Br H Br CF3 CI Br
F CI CF3 OMe OMe F Br H CF3 CF3 CI CF3
F CI N02 OMe OMe CI Br H N02 CF3 CI N02
F CI OMe OMe OMe Br Br H OMe CF3 CI OMe
CI CI Me F H Me Me OMe Me N02 CI Me
CI CI F F H F Me OMe F N02 CI F T U V T U V T U V T U V
CI CI CI F H CI Me OMe CI N02 CI CI
CI CI Br F H Br Me OMe Br N02 CI Br
CI CI CF3 F H CF3 Me OMe CF3 N02 CI CF3
CI CI N02 F H N02 Me OMe N02 N02 CI N02
CI CI OMe F H OMe Me OMe OMe N02 CI OMe
Me Br Me CI H Me Br N02 Me Br Br Me
Me Br F CI H F Br N02 F Br Br F
Me Br CI CI H CI Br N02 CI Br Br CI
Me Br Br CI H Br Br N02 Br Br Br Br
Me Br CF3 CI H CF3 Br N02 CF3 Br Br CF3
Me Br N02 CI H N02 Br N02 N02 Br Br N02
Me Br OMe CI H OMe Br N02 OMe Br Br OMe
F Br Me CF3 H Me CF3 N02 Me CF3 Br Me
F Br F CF3 H F CF3 N02 F CF3 Br F
F Br CI CF3 H CI CF3 N02 CI CF3 Br CI
F Br Br CF3 H Br CF3 N02 Br CF3 Br Br
F Br CF3 CF3 H CF3 CF3 N02 CF3 CF3 Br CF3
F Br N02 CF3 H N02 CF3 N02 N02 CF3 Br N02
F Br OMe CF3 H OMe CF3 N02 OMe CF3 Br OMe
CI Br Me N02 H Me CI CF3 Me N02 Br Me
CI Br F N02 H F CI CF3 F N02 Br F
CI Br CI N02 H CI CI CF3 CI N02 Br CI
CI Br Br N02 H Br CI CF3 Br N02 Br Br
CI Br CF3 N02 H CF3 CI CF3 CF3 N02 Br CF3
CI Br N02 N02 H N02 CI CF3 N02 N02 Br N02
CI Br OMe N02 H OMe CI CF3 OMe N02 Br OMe
Me CF3 Me CI OMe Me N02 OMe Me Br CF3 Me
Me CF3 F CI OMe F N02 OMe F Br CF3 F
Me CF3 CI CI OMe CI N02 OMe CI Br CF3 CI
Me CF3 Br CI OMe Br N02 OMe Br Br CF3 Br
Me CF3 CF3 CI OMe CF3 N02 OMe CF3 Br CF3 CF3
Me CF3 N02 CI OMe N02 N02 OMe N02 Br CF3 N02
Me CF3 OMe CI OMe OMe N02 OMe OMe Br CF3 OMe
F CF3 Me Me H Me N02 CF3 Me CF3 CF3 Me
F CF3 F Me H F N02 CF3 F CF3 CF3 F
F CF3 CI Me H CI N02 CF3 CI CF3 CF3 CI
F CF3 Br Me H Br N02 CF3 Br CF3 CF3 Br T U V T U V T U V T U V
F CF3 CF3 Me H CF3 N02 CF3 CF3 CF3 CF3 CF3
F CF3 N02 Me H N02 N02 CF3 N02 CF3 CF3 N02
F CF3 OMe Me H OMe N02 CF3 OMe CF3 CF3 OMe
Table 3
Figure imgf000021_0001
T and V are both Cl andUis H
Q R Q R Q R Q R
Cl Cl Cl OCH2CF3 Br Cl Br OCH2CF3
CI Br Cl OCF2CF2H Br Br Br OCF2CF2H
Cl OCF3 Cl OCHFCF3 Br OCF3 Br OCHFCF3
Cl OCHF2 Cl SCH2CF3 Br OCHF2 Br SCH2CF3
Cl SCF3 Cl SCF2CF3 Br SCF3 Br SCF2CF3
Cl SCHF2 Cl SCF2CF2H Br SCHF2 Br SCF2CF2H
Cl SOCF3 Cl SOCH2CF3 Br SOCF3 Br SOCH2CF3
Cl SOCHF2 Cl SOCF2CF3 Br SOCHF2 Br SOCF2CF3
Cl S02CF3 Cl SOCF2CF2H Br S02CF3 Br SOCF2CF2H
Cl S02CHF2 Cl SOCHFCF3 Br S02CHF2 Br SOCHFCF3
Cl CN Cl S02CH2CF3 Br CN Br S02CH2CF3
Cl I Cl S02CF2CF3 Br I Br S02CF2CF3
Cl OCH2F Cl S02CF2CF2H Br OCH2F Br S02CF2CF2H
Cl SCH2F Cl S02CHFCF3 Br SCH2F Br S02CHFCF3
Cl Et Cl 0CF2CF3 Br Et Br OCF2CF3
Cl OCF2Cl Cl SCHFCF3 Br 0CF2C1 Br SCHFCF3
T and V are both Cl and U is CH3
Q R Q R Q R Q R
Cl Cl Cl OCH2CF3 Br Cl Br OCH2CF3
Cl Br Cl OCF2CF2H Br Br Br OCF2CF2H
Cl OCF3 Cl OCHFCF3 Br OCF3 Br OCHFCF3
Cl OCHF2 Cl SCH2CF3 Br OCHF2 Br SCH2CF3
Cl SCF3 Cl SCF2CF3 Br SCF3 Br SCF2CF3 T and V are both Cl and U is CH3
Q R Q R Q R Q R
Cl SCHF2 Cl SCF2CF2H Br SCHF2 Br SCF2CF2H
Cl SOCF3 Cl S0CH2CF3 Br SOCF3 Br SOCH2CF3
Cl SOCHF2 Cl SOCF2CF Br SOCHF2 Br SOCF2CF3
Cl S02CF Cl SOCF2CF2H Br S02CF3 Br SOCF2CF2H
Cl S02CHF2 Cl SOCHFCF3 Br S02CHF2 Br SOCHFCF3
Cl CN Cl S02CH2CF3 Br CN Br S02CH2CF3
Cl I Cl S02CF2CF3 Br I Br S02CF2CF3
Cl OCH2F Cl S02CF2CF2H Br OCH2F Br S02CF2CF2H
Cl SCH2F Cl S02CHFCF3 Br SCH2F Br S02CHFCF3
Cl Et Cl 0CF2CF3 Br Et Br OCF2CF3
Cl 0CF2C1 Cl SCHFCF3 Br OCF2Cl Br SCHFCF3
T is Cl and V andU arebofliMe
Q R Q R Q R Q R
Cl Cl Cl OCH2CF3 Br Cl Br OCH2CF3
Cl Br Cl OCF2CF2H Br Br Br OCF2CF2H
Cl OCF3 Cl OCHFCF3 Br OCF3 Br OCHFCF3
Cl OCHF2 Cl SCH2CF3 Br OCHF2 Br SCH2CF3
Cl SCF3 Cl SCF2CF3 Br SCF3 Br SCF2CF3
Cl SCHF2 Cl SCF2CF2H Br SCHF2 Br SCF2CF2H
Cl SOCF3 Cl SOCH2CF3 Br SOCF3 Br SOCH2CF3
Cl SOCHF2 Cl SOCF2CF3 Br SOCHF2 Br SOCF2CF3
Cl S02CF3 Cl SOCF2CF2H Br S02CF3 Br SOCF2CF2H
Cl S02CHF2 Cl SOCHFCF3 Br S02CHF2 Br SOCHFCF3
Cl CN Cl S02CH2CF3 Br CN Br S02CH2CF
Cl I Cl S02CF2CF3 Br I Br S02CF2CF3
Cl OCH2F Cl S02CF2CF2H Br OCH2F Br S02CF2CF2H
Cl SCH2F Cl S02CHFCF Br SCH2F Br S02CHFCF3
Cl Et Cl 0CF2CF3 Br Et Br 0CF2CF3
Cl 0CF2C1 Cl SCHFCF3 Br 0CF2C1 Br SCHFCF3
T is Cl, V is I andU is H
Q R Q R Q R Q R
Cl Cl Cl 0CH2CF3 Br Cl Br 0CH2CF3
Cl Br Cl 0CF2CF2H Br Br Br 0CF2CF2H
Cl OCF3 Cl OCHFCF3 Br OCF3 Br OCHFCF3 Tis Cl, Vis I andUi sH
Q R Q R Q R Q R
Cl OCHF2 Cl SCH2CF3 Br OCHF2 Br SCH2CF3
Cl SCF3 Cl SCF2CF3 Br SCF3 Br SCF2CF3
Cl SCHF2 Cl SCF2CF2H Br SCHF2 Br SCF2CF2H
Cl SOCF3 Cl S0CH2CF3 Br SOCF3 Br S0CH2CF3
Cl SOCHF2 Cl S0CF2CF3 Br SOCHF2 Br S0CF2CF3
Cl S02CF3 Cl SOCF2CF2H Br S02CF3 Br SOCF2CF2H
Cl S02CHF2 Cl SOCHFCF3 Br S02CHF2 Br SOCHFCF3
Cl CN Cl S02CH2CF Br CN Br S02CH2CF3
Cl I Cl S02CF2CF3 Br I Br S02CF2CF3
Cl 0CH2F Cl S02CF2CF2H Br OCH2F Br S02CF2CF2H
Cl SCH2F Cl S02CHFCF3 Br SCH2F Br S02CHFCF3
Cl Et Cl OCF2CF3 Br Et Br 0CF2CF3
Cl 0CF2C1 Cl SCHFCF3 Br 0CF2C1 Br SCHFCF3
T is Cl, Vis I andUi- Me
Q R Q R Q R Q R
Cl Cl Cl 0CH2CF3 Br Cl Br 0CH2CF3
Cl Br Cl OCF2CF2H Br Br Br 0CF2CF2H
Cl OCF3 Cl OCHFCF3 Br OCF3 Br OCHFCF3
Cl OCHF2 Cl SCH2CF3 Br OCHF2 Br SCH2CF3
Cl SCF3 Cl SCF2CF3 Br SCF3 Br SCF2CF3
Cl SCHF2 Cl SCF2CF2H Br SCHF2 Br SCF2CF2H
Cl SOCF3 Cl SOCH2CF3 Br SOCF3 Br SOCH2CF3
Cl SOCHF2 Cl SOCF2CF3 Br SOCHF2 Br SOCF2CF3
Cl S02CF3 Cl SOCF2CF2H Br S02CF3 Br SOCF2CF2H
Cl S02CHF2 Cl SOCHFCF3 Br S02CHF2 Br SOCHFCF3
Cl CN Cl S02CH2CF3 Br CN Br S02CH2CF3
Cl I Cl S02CF2CF3 Br I Br S02CF2CF3
Cl 0CH2F Cl S02CF2CF2H Br 0CH2F Br S02CF2CF2H
Cl SCH2F Cl S02CHFCF3 Br SCH2F Br S02CHFCF3
Cl Et Cl 0CF2CF3 Br Et Br 0CF2CF3
Cl 0CF2C1 Cl SCHFCF3 Br 0CF2C1 Br SCHFCF3 T is F. Vis I andU isH
Q R Q R Q R Q R
Cl Cl Cl 0CH2CF3 Br Cl Br 0CH2CF3
Cl Br Cl OCF2CF2H Br Br Br OCF2CF2H
Cl OCF3 Cl OCHFCF3 Br OCF3 Br 0CHFCF3
Cl OCHF2 Cl SCH2CF3 Br OCHF2 Br SCH2CF3
Cl SCF3 Cl SCF2CF3 Br SCF3 Br SCF2CF3
Cl SCHF2 Cl SCF2CF2H Br SCHF2 Br SCF2CF2H
Cl SOCF3 Cl SOCH2CF3 Br SOCF3 Br S0CH2CF3
Cl SOCHF2 Cl SOCF2CF3 Br SOCHF2 Br S0CF2CF3
Cl S02CF3 Cl SOCF2CF2H Br S02CF3 Br S0CF2CF2H
Cl S02CHF2 Cl SOCHFCF3 Br S02CHF2 Br S0CHFCF3
Cl CN Cl S02CH2CF Br CN Br S02CH2CF3
Cl I Cl S02CF2CF3 Br I Br S02CF2CF3
Cl OCH2F Cl S02CF2CF2H Br 0CH2F Br S02CF2CF2H
Cl SCH2F Cl S02CHFCF3 Br SCH2F Br S02CHFCF3
Cl Et Cl OCF2CF3 Br Et Br 0CF2CF3
Cl 0CF2C1 Cl SCHFCF3 Br OCF2Cl Br SCHFCF3
T is F, Vis I andU is Me
Q R Q R Q R Q R
Cl Cl Cl OCH2CF3 Br Cl Br OCH2CF3
Cl Br Cl OCF2CF2H Br Br Br OCF2CF2H
Cl OCF3 Cl OCHFCF3 Br OCF3 Br OCHFCF3
Cl OCHF2 Cl SCH2CF3 Br OCHF2 Br SCH2CF3
Cl SCF3 Cl SCF2CF3 Br SCF3 Br SCF2CF3
Cl SCHF2 Cl SCF2CF2H Br SCHF2 Br SCF2CF2H
Cl SOCF3 Cl SOCH2CF3 Br SOCF3 Br SOCH2CF
Cl SOCHF2 Cl SOCF2CF3 Br SOCHF2 Br SOCF2CF3
Cl S02CF3 Cl SOCF2CF2H Br S02CF3 Br SOCF2CF2H
Cl S02CHF2 Cl SOCHFCF3 Br S02CHF2 Br SOCHFCF3
Cl CN Cl S02CH2CF3 Br CN Br S02CH2CF3
Cl I Cl S02CF2CF Br I Br S02CF2CF3
Cl 0CH2F Cl S02CF2CF2H Br OCH2F Br S02CF2CF2H
Cl SCH2F Cl S02CHFCF3 Br SCH2F Br S02CHFCF3
Cl Et Cl OCF2CF3 Br Et Br OCF2CF3
Cl 0CF2C1 Cl SCF£FCF3 Br 0CF2C1 Br SCHFCF3 Table 4
Figure imgf000025_0001
T and V are both Cl and U is H
Q R Q R Q R Q R
Cl Cl Cl OCH2CF3 Br Cl Br 0CH2CF3
Cl Br Cl OCF2CF2H Br Br Br 0CF2CF2H
Cl OCF3 Cl OCHFCF3 Br OCF3 Br OCHFCF3
Cl OCHF2 Cl SCH2CF3 Br OCHF2 Br SCH2CF3
Cl SCF3 Cl SCF2CF3 Br SCF3 Br SCF2CF3
Cl SCHF2 Cl SCF2CF2H Br SCHF2 Br SCF2CF2H
Cl SOCF3 Cl SOCH2CF3 Br SOCF3 Br S0CH CF3
Cl SOCHF2 Cl SOCF2CF3 Br SOCHF2 Br SOCF2CF3
Cl S02CF3 Cl SOCF2CF2H Br S02CF3 Br SOCF2CF2H
Cl S02CHF2 Cl SOCHFCF3 Br S02CHF2 Br SOCHFCF3
Cl CN Cl S02CH2CF3 Br CN Br S02CH2CF3
Cl I Cl S02CF2CF3 Br I Br S02CF2CF3
Cl OCH2F Cl S02CF2CF2H Br 0CH2F Br S02CF2CF2H
Cl SCH2F Cl S02CHFCF3 Br SCH2F Br S02CHFCF3
Cl Et Cl 0CF2CF3 Br Et Br OCF2CF3
Cl 0CF2C1 Cl SCHFCF3 Br 0CF2C1 Br SCHFCF3
T and V are both Cl andU is CH3
Q R Q R Q R Q R
Cl Cl Cl 0CH2CF3 Br Cl Br OCH2CF3
Cl Br Cl OCF2CF2H Br Br Br OCF2CF2H
Cl OCF3 Cl OCHFCF3 Br OCF3 Br OCHFCF3
Cl OCHF2 Cl SCH2CF3 Br OCHF2 Br SCH2CF3
Cl SCF3 Cl SCF2CF3 Br SCF3 Br SCF2CF3
Cl SCHF2 Cl SCF2CF2H Br SCHF2 Br SCF2CF2H
Cl SOCF3 Cl SOCH2CF3 Br SOCF3 Br SOCH2CF3
Cl SOCHF2 Cl SOCF2CF3 Br SOCHF2 Br SOCF2CF3
Cl S02CF3 Cl SOCF2CF2H Br S02CF3 Br SOCF2CF2H
Cl S02CHF2 Cl SOCHFCF3 Br S02CHF2 Br SOCHFCF3 T and N are both Cl and U is CH3
Q R Q R Q R Q R
Cl CΝ Cl S02CH2CF3 Br CΝ Br S02CH2CF3
Cl I Cl S0 CF2CF3 Br I Br S02CF2CF3
Cl OCH2F Cl S02CF2CF2H Br OCH2F Br S02CF2CF2H
Cl SCH2F Cl S02CHFCF3 Br SCH2F Br S02CHFCF3
Cl Et Cl 0CF2CF3 Br Et Br OCF2CF3
Cl OCF2Cl Cl SCHFCF3 Br 0CF2C1 Br SCHFCF3
T is Cl and V and U are both Me
Q R Q R Q R Q R
Cl Cl Cl 0CH2CF3 Br Cl Br OCH2CF3
Cl Br Cl OCF2CF2H Br Br Br OCF2CF2H
Cl OCF3 Cl OCHFCF3 Br OCF3 Br OCHFCF3
Cl OCHF2 Cl SCH2CF3 Br OCHF2 Br SCH2CF3
Cl SCF3 Cl SCF2CF3 Br SCF3 Br SCF2CF3
Cl SCHF2 Cl SCF2CF2H Br SCHF2 Br SCF2CF2H
Cl SOCF3 Cl SOCH2CF3 Br SOCF3 Br SOCH2CF3
Cl SOCHF2 Cl SOCF2CF3 Br SOCHF2 Br SOCF2CF3
Cl S02CF3 Cl SOCF2CF2H Br S02CF3 Br SOCF2CF2H
Cl S02CHF2 Cl SOCHFCF3 Br S02CHF2 Br SOCHFCF3
Cl CΝ Cl S02CH2CF3 Br CΝ Br S02CH2CF3
Cl I Cl S02CF2CF3 Br I Br S02CF2CF3
Cl OCH2F Cl S02CF2CF2H Br OCH2F Br S02CF2CF2H
Cl SCH2F Cl S02CHFCF3 Br SCH2F Br S02CHFCF3
Cl Et Cl OCF2CF3 Br Et Br OCF2CF3
Cl 0CF2C1 Cl SCHFCF3 Br OCF2Cl Br SCHFCF3
T is CL Vis I andUis H
Q R Q R Q R Q R
Cl Cl Cl OCH2CF3 Br Cl Br OCH2CF3
Cl Br Cl OCF2CF2H Br Br Br OCF2CF2H
Cl OCF3 Cl OCHFCF3 Br OCF3 Br OCHFCF3
Cl OCHF2 Cl SCH2CF3 Br OCHF2 Br SCH2CF3
Cl SCF3 Cl SCF2CF3 Br SCF3 Br SCF2CF3
Cl SCHF2 Cl SCF2CF2H Br SCHF2 Br SCF2CF2H
Cl SOCF3 Cl SOCH2CF3 Br SOCF3 Br SOCH2CF3
Cl SOCHF2 Cl SOCF2CF3 Br SOCHF2 Br SOCF2CF3 T is Cl, Vis I andUi s H
Q R Q R Q R Q R
Cl S02CF3 Cl SOCF2CF2H Br S02CF3 Br S0CF2CF2H
Cl S02CHF2 Cl SOCHFCF3 Br S02CHF2 Br SOCHFCF3
Cl CN Cl S02CH2CF3 Br CN Br S02CH2CF3
Cl I Cl S02CF2CF3 Br I Br S02CF2CF3
Cl OCH2F Cl S02CF2CF2H Br 0CH2F Br S02CF2CF2H
Cl SCH2F Cl S02CHFCF3 Br SCH2F Br S02CHFCF3
Cl Et Cl 0CF2CF3 Br Et Br 0CF2CF3
Cl 0CF2C1 Cl SCHFCF3 Br 0CF2C1 Br SCHFCF3
Tis Cl. V is I andU is Me
Q R Q R Q R Q R
Cl Cl Cl OCH2CF3 Br Cl Br OCH2CF3
Cl Br Cl OCF2CF2H Br Br Br 0CF2CF2H
Cl OCF3 Cl OCHFCF3 Br OCF3 Br OCHFCF3
Cl OCHF2 Cl SCH2CF3 Br OCHF2 Br SCH2CF3
Cl SCF3 Cl SCF2CF3 Br SCF3 Br SCF2CF3
Cl SCHF2 Cl SCF2CF2H Br SCHF2 Br SCF2CF2H
Cl SOCF3 Cl SOCH2CF3 Br SOCF3 Br SOCH2CF3
Cl SOCHF2 Cl SOCF2CF3 Br SOCHF2 Br SOCF2CF3
Cl S02CF3 Cl SOCF2CF2H Br S02CF3 Br SOCF2CF2H
Cl S02CHF2 Cl SOCHFCF3 Br S02CHF2 Br SOCHFCF3
Cl CN Cl S02CH2CF3 Br CN Br S02CH2CF3
Cl I Cl S02CF2CF3 Br I Br S02CF2CF3
Cl OCH2F Cl S02CF2CF2H Br OCH2F Br S02CF2CF2H
Cl SCH2F Cl S02CHFCF3 Br SCH2F Br S02CHFCF3
Cl Et Cl 0CF2CF3 Br Et Br OCF2CF3
Cl 0CF2C1 Cl SCHFCF3 Br 0CF2C1 Br SCHFCF3
Tis F. Vis I andUisH
Q R Q R Q R Q R
Cl Cl Cl 0CH2CF3 Br Cl Br 0CH2CF3
Cl Br Cl 0CF2CF2H Br Br Br 0CF2CF2H
Cl OCF3 Cl OCHFCF3 Br OCF3 Br 0CHFCF3
Cl 0CHF2 Cl SCH2CF3 Br 0CHF2 Br SCH2CF3
Cl SCF3 Cl SCF2CF3 Br SCF3 Br SCF2CF3
Cl SCHF2 Cl SCF2CF2H Br SCHF2 Br SCF2CF2H T is F. Vis I andU isH
Q R Q R Q R Q R
Cl SOCF3 Cl SOCH2CF3 Br SOCF3 Br SOCH7CF3
Cl SOCHF2 Cl SOCF2CF3 Br SOCHF2 Br S0CF2CF3
Cl S02CF3 Cl SOCF2CF2H Br S02CF Br S0CF2CF2H
Cl S02CHF2 Cl SOCHFCF3 Br S02CHF2 Br SOCHFCF3
Cl CN Cl S02CH2CF3 Br CN Br S02CH2CF3
Cl I Cl S02CF2CF3 Br I Br S02CF2CF3
Cl OCH2F Cl S02CF2CF2H Br 0CH2F Br S02CF2CF2H
Cl SCH2F Cl S02CHFCF3 Br SCH2F Br S02CHFCF3
Cl Et Cl 0CF2CF3 Br Et Br 0CF2CF3
Cl 0CF2C1 Cl SCHFCF3 Br 0CF2C1 Br SCHFCF3
T is F. Vis I andU is Me
Q R Q R Q R Q R
Cl Cl Cl OCH2CF3 Br Cl Br 0CH2CF3
Cl Br Cl OCF CF2H Br Br Br OCF2CF2H
Cl OCF3 Cl OCHFCF3 Br OCF3 Br OCHFCF3
Cl OCHF2 Cl SCH2CF3 Br OCHF2 Br SCH2CF3
Cl SCF3 Cl SCF CF3 Br SCF3 Br SCF2CF3
Cl SCHF2 Cl SCF2CF2H Br SCHF2 Br SCF2CF2H
Cl SOCF3 Cl SOCH2CF3 Br SOCF3 Br SOCH2CF3
Cl SOCHF2 Cl SOCF2CF3 Br SOCHF2 Br SOCF2CF3
Cl S02CF Cl SOCF2CF2H Br S02CF3 Br SOCF2CF2H
Cl S02CHF2 Cl SOCHFCF3 Br S02CHF2 Br SOCHFCF3
Cl CN Cl S02CH2CF3 Br CN Br S02CH2CF3
Cl I Cl S02CF2CF3 Br I Br S02CF2CF3
Cl OCH2F Ci S02CF2CF2H Br OCH2F Br S02CF2CF2H
Cl SCH2F Cl S02CHFCF3 Br SCH2F Br S02CHFCF3
Cl Et Cl OCF2CF3 Br Et Br 0CF2CF3
Cl 0CF2C1 Cl SCHFCF3 Br 0CF2C1 Br SCHFCF3 Table 5
Figure imgf000029_0001
Q R2 U R R2 U R R2 U
I H H I Me H I Me Me
OCHF2 H H OCHF2 Me H OCHF2 Me Me
OCH2F H H OCH2F Me H OCH2F Me Me
OCF Cl H H OCF2Cl Me H OCF2Cl Me Me
OCH2CF3 H H OCH2CF3 Me H OCH2CF3 Me Me
Et H H Et Me H Et Me Me
CN H H CN Me H CN Me Me
NH2 H H NH2 Me H NH2 Me Me
NHCOMe H H NHCOMe Me H NHCOMe Me Me
NHCOCF3 H H NHCOCF3 Me H NHCOCF Me Me
SCF3 H H SCF3 Me H SCF3 Me Me
SCHF2 H H SCHF2 Me H SCHF2 Me Me
SCH2F H H SCH2F Me H SCH2F Me Me
Ph H H Ph Me H Ph Me Me
Me3Si H H Me3Si Me H Me3Si Me Me
I H Me Et H Me SCF3 H Me
OCHF2 H Me CN H Me SCHF2 H Me
OCH2F H Me NH2 H Me SCH2F H Me
0CF2C1 H Me NHCOMe H Me Ph H Me
OCH2CF3 H Me NHCOCF3 H Me Me3Si H Me
Table 6
Figure imgf000029_0002
Q R2 U R R2 U R R2 U
I H H I Me H I Me Me Q R2 U R R2 U R R2 U
OCHF2 H H OCHF2 Me H OCHF2 Me Me
OCH2F H H OCH2F Me H OCH2F Me Me
OCF2Cl H H OCF2Cl Me H OCF2Cl Me Me
OCH2CF3 H H OCH2CF3 Me H OCH CF3 Me Me
Et H H Et Me H Et Me Me
CN H H CN Me H CN Me Me
NH2 H H NH2 Me H NH2 Me Me
NHCOMe H H NHCOMe Me H NHCOMe Me Me
NHCOCF3 H H NHCOCF3 Me H NHCOCF3 Me Me
SCF3 H H SCF3 Me H SCF3 Me Me
SCHF2 H H SCHF2 Me H SCHF2 Me Me
SCH2F H H SCH2F Me H SCH2F Me Me
Ph H H Ph Me H Ph Me Me
Me3Si H H Me3Si Me H Me3Si Me Me
I H Me Et H Me SCF3 H Me
OCHF2 H Me CN H Me SCHF2 H Me
OCH2F H Me NH2 H Me SCH2F H Me
0CF2C1 H Me NHCOMe H Me Ph H Me
OCH2CF3 H Me NHCOCF3 H Me Me3Si H Me
Table 7
Figure imgf000030_0001
R Q R2 T W V U R Q R2 T W V U
Cl Cl H Cl H H H Br Cl H Cl H H H
Cl Cl H N02 H H H Br Cl H N02 H H H
Cl Cl H F H H H Br Cl H F H H H
Cl Cl H F F F H Br Cl H F F F H
Cl Cl H F H F H Br Cl H F H F H
Cl Cl H F H Cl H Br Cl H F H Cl H
Cl Cl H F H Br H Br Cl H F H Br H
Cl Cl H F H OMe H Br Cl H F H OMe H
Cl Cl H F H CF3 H Br Cl H F H CF3 H R Q R2 T W V U R Q R2 T W V U
Cl Cl H Cl H F H Br Cl H Cl H F H
Cl Cl H Cl H Br H Br Cl H Cl H Br H
Cl Cl H Cl H OMe H Br Cl H Cl H OMe H
Cl Cl H Cl H CF3 H Br Cl H Cl H CF3 H
Cl Cl H Br H F H Br Cl H Br H F H
Cl Cl H Br H Cl H Br Cl H Br H Cl H
Cl Cl H Br H Br H Br Cl H Br H Br H
Cl Cl H Br H I H Br Cl H Br H I H
Cl Cl H Br H OMe H Br Cl H Br H OMe H
Cl Cl H Br H CF3 H Br Cl H Br H CF3 H
Cl Cl H H F H Br Cl H H F H
Cl Cl H H Cl H Br Cl H H Cl H
Cl Cl H H Br H Br Cl H H Br H
Cl Cl H H I H Br Cl H H I H
Cl Cl H H OMe H Br Cl H H OMe H
Cl Cl H H CF3 H Br Cl H H CF3 H
Cl Cl H OMe H F H Br Cl H OMe H F H
Cl Cl H OMe H Cl H Br Cl H OMe H Cl H
Cl Cl H OMe H Br H Br Cl H OMe H Br H
Cl Cl H OMe H I H Br Cl H OMe H I H
Cl Cl H OMe H OMe H Br Cl H OMe H OMe H
Cl Cl H OMe H CF3 H Br Cl H OMe H CF3 H
Cl Cl H CF3 H F H Br Cl H CF3 H F H
Cl Cl H CF3 H Cl H Br Cl H CF3 H Cl H
Cl Cl H CF3 H Br H Br Cl H CF3 H Br H
Cl Cl H CF3 H I H Br Cl H CF3 H I H
Cl Cl H CF3 H OMe H Br Cl H CF3 H OMe H
Cl Cl H CF3 H CF3 H Br Cl H CF3 H CF3 H
Cl Cl H Cl H H Me Br Cl H Cl H H Me
Cl Cl H N02 H H Me Br Cl H N02 H H Me
Cl Cl H F H H Me Br Cl H F H H Me
Cl Cl H F F F Me Br Cl H F F F Me
Cl Cl H F H F Me Br Cl H F H F Me
Cl Cl H F H Cl Me Br Cl H F H Cl Me
Cl Cl H F H Br Me Br Cl H F H Br Me
Cl Cl H F H OMe Me Br Cl H F H OMe Me
Cl Cl H F H CF3 Me Br Cl H F H CF3 Me R Q R2 T W V U R Q R2 T W V U
Cl Cl H Cl H F Me Br Cl H Cl H F Me
Cl Cl H Cl H Br Me Br Cl H Cl H Br Me
Cl Cl H Cl H OMe Me Br Cl H Cl H OMe Me
Cl Cl H Cl H CF3 Me Br Cl H Cl H CF3 Me
Cl Cl H Br H F Me Br Cl H Br H F Me
Cl Cl H Br H Cl Me Br Cl H Br H Cl Me
Cl Cl H Br H Br Me Br Cl H Br H Br Me
Cl Cl H Br H I Me Br Cl H Br H I Me
Cl Cl H Br H OMe Me Br Cl H Br H OMe Me
Cl Cl H Br H CF3 Me Br Cl H Br H CF3 Me
Cl Cl H I H F Me Br Cl H H F Me
Cl Cl H I H Cl Me Br Cl H H Cl Me
Cl Cl H I H Br Me Br Cl H H Br Me
Cl Cl H I H I Me Br Cl H H I Me
Cl Cl H I H OMe Me Br Cl H H OMe Me
Cl Cl H I H CF3 Me Br Cl H H CF3 Me
Cl Cl H OMe H F Me Br Cl H OMe H F Me
Cl Cl H OMe H Cl Me Br Cl H OMe H Cl Me
Cl Cl H OMe H Br Me Br Cl H OMe H Br Me
Cl Cl H OMe H I Me Br Cl H OMe H I Me
Cl Cl H OMe H OMe Me Br Cl H OMe H OMe Me
Cl Cl H OMe H CF3 Me Br Cl H OMe H CF3 Me
Cl Cl H CF3 H F Me Br Cl H CF3 H F Me
Cl Cl H CF3 H Cl Me Br Cl H CF3 H Cl Me
Cl Cl H CF3 H Br Me Br Cl H CF3 H Br Me
Cl Cl H CF3 H I Me Br Cl H CF3 H I Me
Cl Cl H CF3 H OMe Me Br Cl H CF3 H OMe Me
Cl Cl H CF3 H CF3 Me Br Cl H CF3 H CF3 Me
Cl Cl Me Cl H H H Br Cl Me Cl H H H
Cl Cl Me N02 H H H Br Cl Me N02 H H H
Cl Cl Me F H H H Br Cl Me F H H H
Cl Cl Me F F F H Br Cl Me F F F H
Cl Cl Me F H F H Br Cl Me F H F H
Cl Cl Me F H Cl H Br Cl Me F H Cl H
Cl Cl Me F H Br H Br Cl Me F H Br H
Cl Cl Me F H OMe H Br Cl Me F H OMe H
Cl Cl Me F H CF3 H Br Cl Me F H CF3 H R Q R2 T W V U R Q R2 T V U
Cl Cl Me Cl H F H Br Cl Me Cl H F H
Cl Cl Me Cl H Br H Br Cl Me Cl H Br H
Cl Cl Me Cl H OMe H Br Cl Me Cl H OMe H
Cl Cl Me Cl H CF3 H Br Cl Me Cl H CF3 H
Cl Cl Me Br H F H Br Cl Me Br H F H
Cl Cl Me Br H Cl H Br Cl Me Br H Cl H
Cl Cl Me Br H Br H Br Cl Me Br H Br H
Cl Cl Me Br H I H Br Cl Me Br H I H
Cl Cl Me Br H OMe H Br Cl Me Br H OMe H
Cl Cl Me Br H CF3 H Br Cl Me Br H CF3 H
Cl Cl Me I H F H Br Cl Me H F H
Cl Cl Me I H Cl H Br Cl Me H Cl H
Cl Cl Me I H Br H Br Cl Me H Br H
Cl Cl Me I H I H Br Cl Me H I H
Cl Cl Me I H OMe H Br Cl Me H OMe H
Cl Cl Me I H CF3 H Br Cl Me H CF3 H
Cl Cl Me OMe H F H Br Cl Me OMe H F H
Cl Cl Me OMe H Cl H Br Cl Me OMe H Cl H
Cl Cl Me OMe H Br H Br Cl Me OMe H Br H
Cl Cl Me OMe H I H Br Cl Me OMe H I H
Cl Cl Me OMe H OMe H Br Cl Me OMe H OMe H
Cl Cl Me OMe H CF3 H Br Cl Me OMe H CF3 H
Cl Cl Me CF3 H F H Br Cl Me CF3 H F H
Cl Cl Me CF3 H Cl H Br Cl Me CF3 H Cl H
Cl Cl Me CF3 H Br H Br Cl Me CF3 H Br H
Cl Cl Me CF3 H I H Br Cl Me CF3 H I H
Cl Cl Me CF3 H OMe H Br Cl Me CF3 H OMe H
Cl Cl Me CF3 H CF3 H Br Cl Me CF3 H CF3 H
Cl Cl Me Cl H H Me Br Cl Me Cl H H Me
Cl Cl Me N02 H H Me Br Cl Me N02 H H Me
Cl Cl Me F H H Me Br Cl Me F H H Me
Cl Cl Me F F F Me Br Cl Me F F F Me
Cl Cl Me F H F Me Br Cl Me F H F Me
Cl Cl Me F H Cl Me Br Cl Me F H Cl Me
Cl Cl Me F H Br Me Br Cl Me F H Br Me
Cl Cl Me F H OMe Me Br Cl Me F H OMe Me
Cl Cl Me F H CF3 Me Br Cl Me F H CF3 Me R Q R2 T W V U R Q R2 T W V U
Cl Cl Me Cl H F Me Br Cl Me Cl H F Me
Cl Cl Me Cl H Br Me Br Cl Me Cl H Br Me
Cl Cl Me Cl H OMe Me Br Cl Me Cl H OMe Me
Cl Cl Me Cl H CF3 Me Br Cl Me Cl H CF3 Me
Cl Cl Me Br H F Me Br Cl Me Br H F Me
Cl Cl Me Br H Cl Me Br Cl Me Br H Cl Me
Cl Cl Me Br H Br Me Br Cl Me Br H Br Me
Cl Cl Me Br H I Me Br Cl Me Br H I Me
Cl Cl Me Br H OMe Me Br Cl Me Br H OMe Me
Cl Cl Me Br H CF3 Me Br Cl Me Br H CF3 Me
Cl Cl Me H F Me Br Cl Me H F Me
Cl Cl Me H Cl Me Br Cl Me H Cl Me
Cl Cl Me H Br Me Br Cl Me H Br Me
Cl Cl Me H I Me Br Cl Me H I Me
Cl Cl Me H OMe Me Br Cl Me H OMe Me
Cl Cl Me H CF3 Me Br Cl Me H CF3 Me
Cl Cl Me OMe H F Me Br Cl Me OMe H F Me
Cl Cl Me OMe H Cl Me Br Cl Me OMe H Cl Me
Cl Cl Me OMe H Br Me Br Cl Me OMe H Br Me
Cl Cl Me OMe H I Me Br Cl Me OMe H I Me
Cl Cl Me OMe H OMe Me Br Cl Me OMe H OMe Me
Cl Cl Me OMe H CF3 Me Br Cl Me OMe H CF3 Me
Cl Cl Me CF3 H F Me Br Cl Me CF3 H F Me
Cl Cl Me CF3 H Cl Me Br Cl Me CF3 H Cl Me
Cl Cl Me CF3 H Br Me Br Cl Me CF3 H Br Me
Cl Cl Me CF3 H I Me Br Cl Me CF3 H I Me
Cl Cl Me CF3 H OMe Me Br Cl Me CF3 H OMe Me
Cl Cl Me CF3 H CF3 Me Br Cl Me CF3 H CF3 Me
Cl Br H Cl H H H Br Br H Cl H H H
Cl Br H N02 H H H Br Br H N02 H H H
Cl Br H F H H H Br Br H F H H H
Cl Br H F F F H Br Br H F F F H
Cl Br H F H F H Br Br H F H F H
Cl Br H F H Cl H Br Br H F H Cl H
Cl Br H F H Br H Br Br H F H Br H
Cl Br H F H OMe H Br Br H F H OMe H
Cl Br H F H CF3 H Br Br H F H CF3 H R Q R2 T W V U R Q R2 T W V U
Cl Br H Cl H F H Br Br H Cl H F H
Cl Br H Cl H Br H Br Br H Cl H Br H
Cl Br H Cl H OMe H Br Br H Cl H OMe H
Cl Br H Cl H CF3 H Br Br H Cl H CF3 H
Cl Br H Br H F H Br Br H Br H F H
Cl Br H Br H Cl H Br Br H Br H Cl H
Cl Br H Br H Br H Br Br H Br H Br H
Cl Br H Br H I H Br Br H Br H I H
Cl Br H Br H OMe H Br Br H Br H OMe H
Cl Br H Br H CF3 H Br Br H Br H CF3 H
Cl Br H H F H Br Br H H F H
Cl Br H H Cl H Br Br H H Cl H
Cl Br H H Br H Br Br H H Br H
Cl Br H H I H Br Br H H I H
Cl Br H H OMe H Br Br H H OMe H
Cl Br H H CF3 H Br Br H H CF3 H
Cl Br H OMe H F H Br Br H OMe H F H
Cl Br H OMe H Cl H Br Br H OMe H Cl H
Cl Br H OMe H Br H Br Br H OMe H Br H
Cl Br H OMe H I H Br Br H OMe H I H
Cl Br H OMe H OMe H Br Br H OMe H OMe H
Cl Br H OMe H CF3 H Br Br H OMe H CF3 H
Cl Br H CF3 H F H Br Br H CF3 H F H
Cl Br H CF3 H Cl H Br Br H CF3 H Cl H
Cl Br H CF3 H Br H Br Br H CF3 H Br H
Cl Br H CF3 H I H Br Br H CF3 H I H
Cl Br H CF3 H OMe H Br Br H CF3 H OMe H
Cl Br H CF3 H CF3 H Br Br H CF3 H CF3 H
Cl Br H Cl H H Me Br Br H Cl H H Me
Cl Br H N02 H H Me Br Br H N02 H H Me
Cl Br H F H H Me Br Br H F H H Me
Cl Br H F F F Me Br Br H F F F Me
Cl Br H F H F Me Br Br H F H F Me
Cl Br H F H Cl Me Br Br H F H Cl Me
Cl Br H F H Br Me Br Br H F H Br Me
Cl Br H F H OMe Me Br Br H F H OMe Me
Cl Br H F H CF3 Me Br Br H F H CF3 Me R Q R2 T W V U R Q R2 T W V U
Cl Br H Cl H F Me Br Br H Cl H F Me
Cl Br H Cl H Br Me Br Br H Cl H Br Me
Cl Br H Cl H OMe Me Br Br H Cl H OMe Me
Cl Br H Cl H CF3 Me Br Br H Cl H CF3 Me
Cl Br H Br H F Me Br Br H Br H F Me
Cl Br H Br H Cl Me Br Br H Br H Cl Me
Cl Br H Br H Br Me Br Br H Br H Br Me
Cl Br H Br H I Me Br Br H Br H I Me
Cl Br H Br H OMe Me Br Br H Br H OMe Me
Cl Br H Br H CF3 Me Br Br H Br H CF3 Me
Cl Br H H F Me Br Br H H F Me
Cl Br H H Cl Me Br Br H H Cl Me
Cl Br H H Br Me Br Br H H Br Me
Cl Br H H I Me Br Br H H I Me
Cl Br H H OMe Me Br Br H H OMe Me
Cl Br H H CF3 Me Br Br H H CF3 Me
Cl Br H OMe H F Me Br Br H OMe H F Me
Cl Br H OMe H Cl Me Br Br H OMe H Cl Me
Cl Br H OMe H Br Me Br Br H OMe H Br Me
Cl Br H OMe H I Me Br Br H OMe H I Me
Cl Br H OMe H OMe Me Br Br H OMe H OMe Me
Cl Br H OMe H CF3 Me Br Br H OMe H CF3 Me
Cl Br H CF3 H F Me Br Br H CF3 H F Me
Cl Br H CF3 H Cl Me Br Br H CF3 H Cl Me
Cl Br H CF3 H Br Me Br Br H CF3 H Br Me
Cl Br H CF3 H I Me Br Br H CF3 H I Me
Cl Br H CF3 H OMe Me Br Br H CF3 H OMe Me
Cl Br H CF3 H CF3 Me Br Br H CF3 H CF3 Me
Cl Br Me C 1l H H H Br Br Me Cl H H H
Cl Br Me N02 H H H Br Br Me N02 H H H
Cl Br Me F H H H Br Br Me F H H H
Cl Br Me F F F H Br Br Me F F F H
Cl Br Me F H F H Br Br Me F H F H
Cl Br Me F H Cl H Br Br Me F H Cl H
Cl Br Me F H Br H Br Br Me F H Br H
Cl Br Me F H OMe H Br Br Me F H OMe H
Cl Br Me F H CF3 H Br Br Me F H CF3 H R Q R2 T W V U R Q R2 T W V U
Cl Br Me Cl H F H Br Br Me Cl H F H
Cl Br Me Cl H Br H Br Br Me Cl H Br H
Cl Br Me Cl H OMe H Br Br Me Cl H OMe H
Cl Br Me Cl H CF3 H Br Br Me Cl H CF3 H
Cl Br Me Br H F H Br Br Me Br H F H
Cl Br Me Br H Cl H Br Br Me Br H Cl H
Cl Br Me Br H Br H Br Br Me Br H Br H
Cl Br Me Br H I H Br Br Me Br H I H
Cl Br Me Br H OMe H Br Br Me Br H OMe H
Cl Br Me Br H CF3 H Br Br Me Br H CF3 H
Cl Br Me H F H Br Br Me H F H
Cl Br Me H Cl H Br Br Me H Cl H
Cl Br Me H Br H Br Br Me H Br H
Cl Br Me H I H Br Br Me H .1 H
Cl Br Me H OMe H Br Br Me H OMe H
Cl Br Me H CF3 H Br Br Me H CF3 H
Cl Br Me OMe H F H Br Br Me OMe H F H
Cl Br Me OMe H Cl H Br Br Me OMe H Cl H
Cl Br Me OMe H Br H Br Br Me OMe H Br H
Cl Br Me OMe H I H Br Br Me OMe H I H
Cl Br Me OMe H OMe H Br Br Me OMe H OMe H
Cl Br Me OMe H CF3 H Br Br Me OMe H CF3 H
Cl Br Me CF3 H F H Br Br Me CF3 H F H
Cl Br Me CF3 H Cl H Br Br Me CF3 H Cl H
Cl Br Me CF3 H Br H Br Br Me CF3 H Br H
Cl Br Me CF3 H I H Br Br Me CF3 H I H
Cl Br Me CF3 H OMe H Br Br Me CF3 H OMe H
Cl Br Me CF3 H CF3 H Br Br Me CF3 H CF3 H
Cl Br Me Cl H H Me Br Br Me Cl H H Me
Cl Br Me N02 H H Me Br Br Me N02 H H Me
Cl Br Me F H H Me Br Br Me F H H Me
Cl Br Me F F F Me Br Br Me F F F Me
Cl Br Me F H F Me Br Br Me F H F Me
Cl Br Me F H Cl Me Br Br Me F H Cl Me
Cl Br Me F H Br Me Br Br Me F H Br Me
Cl Br Me F H OMe Me Br Br Me F H OMe Me
Cl Br Me F H CF3 Me Br Br Me F H CF3 Me R Q R2 T W V U R Q R2 T W V U
Cl Br Me Cl H F Me Br Br Me Cl H F Me
Cl Br Me Cl H Br Me Br Br Me Cl H Br Me
Cl Br Me Cl H OMe Me Br Br Me Cl H OMe Me
Cl Br Me Cl H CF3 Me Br Br Me Cl H CF3 Me
Cl Br Me Br H F Me Br Br Me Br H F Me
Cl Br Me Br H Cl Me Br Br Me Br H Cl Me
Cl Br Me Br H Br Me Br Br Me Br H Br Me
Cl Br Me Br H I Me Br Br Me Br H I Me
Cl Br Me Br H OMe Me Br Br Me Br H OMe Me
Cl Br Me Br H CF3 Me Br Br Me Br H CF3 Me
Cl Br Me H F Me Br Br Me H F Me
Cl Br Me H Cl Me Br Br Me H Cl Me
Cl Br Me H Br Me Br Br Me H Br Me
Cl Br Me H I Me Br Br Me H I Me
Cl Br Me H OMe Me Br Br Me H OMe Me
Cl Br Me H CF3 Me Br Br Me H CF3 Me
Cl Br Me OMe H - F Me Br Br Me OMe H F Me
Cl Br Me OMe H Cl Me Br Br Me OMe H Cl Me
Cl Br Me OMe H Br Me Br Br Me OMe H Br Me
Cl Br Me OMe H I Me Br Br Me OMe H I Me
Cl Br Me OMe H OMe Me Br Br Me OMe H OMe Me
Cl Br Me OMe H CF3 Me Br Br Me OMe H CF3 Me
Cl Br Me CF3 H F Me Br Br Me CF3 H F Me
Cl Br Me CF3 H Cl Me Br Br Me CF3 H Cl Me
Cl Br Me CF3 H Br Me Br Br Me CF3 H Br Me
Cl Br Me CF3 H I Me Br Br Me CF3 H I Me
Cl Br Me CF3 H OMe Me Br Br Me CF3 H OMe Me
Cl Br Me CF3 H CF3 Me Br Br Me CF3 H CF3 Me
The fungicides of component (b) of the compositions of the invention are selected from the group consisting of
(bl) alkylenebis(dithiocarbamate) fungicides;
(b2) compounds acting at the bc complex of the fungal mitochondrial respiratory electron transfer site;
(b3) cymoxanil;
(b4) compounds acting at the demethylase enzyme of the sterol biosynthesis pathway;
(b5) moφholine and piperidine compounds that act on the sterol biosynthesis pathway; (b6) phenylamide fungicides;
(b7) pyrimidinone fungicides;
(b8) phthalimides; and
(b9) fosetyl-aluminum.
The weight ratios of component (b) to component (a) typically is from 100:1 to 1:100, preferably is from 30:1 to 1 :30, and more preferably is from 10:1 to 1:10. Of note are compositions wherein the weight ratio of component (b) to component (a) is from 10: 1 to 1:1. Included are compositions wherein the weight ratio of component (b) to component (a) is from 9:1 to 4.5:1. The bcγ Complex Fungicides (component (b2))
Strobilurin fungicides such as azoxystrobin, kresoxim-methyl, metominostrobin/fenominostrobin (SSF-126), picoxystrobin, pyraclostrobin and trifloxystrobin are known to have a fungicidal mode of action which inhibits the bc complex in the mitochondrial respiration chain (Angew. Chem. Int. Ed., 1999, 38, 1328- 1349). Methyl (E)-2-[[6-(2-cyanophenoxy)-4-pyrimidinyl]oxy]-α- (memoxyimino)benzeneacetate (also known as azoxystrobin) is described as a bc\ complex inhibitor in Biochemical Society Transactions 1993, 22, 68S. Methyl (E)-α- (memoxyimino)-2-[(2-methylphenoxy)methyl]benzeneacetate (also known as kresoxim- methyl) is described as a bc\ complex inhibitor in Biochemical Society Transactions 1993, 22, 64S. (E)-2-[(2,5--αme lphenoxy)memyl]- -(memoxyimino)-N- methylbenzeneacetamide is described as a be γ complex inhibitor in Biochemistry and Cell Biology 1995, 55(3), 306-311. Other compounds that inhibit the bc\ complex in the mitochondrial respiration chain include famoxadone and fenamidone.
The bcγ complex is sometimes referred to by other names in the biochemical literature, including complex III of the electron transfer chain, and ubihydroquinonexytochrome c oxidoreductase. It is uniquely identified by the Enzyme Commission number EC1.10.2.2. The bcγ complex is described in, for example, J. Biol. Chem. 1989, 264, 14543-38; Methods Enzymol. 1986, 126, 253-71; and references cited therein. The Sterol Biosynthesis Inhibitor Fungicides (component (b4 or (b5))
The class of sterol biosynthesis inhibitors includes DMI andnon-DMI compounds, that control fungi by inhibiting enzymes in the sterol biosynthesis pathway. DMI fungicides have a common site of action within the fungal sterol biosynthesis pathway; that is, an inhibition of demethylation at position 14 of lanosterol or 24-methylene dihydrolanosterol, which are precursors to sterols in fungi. Compounds acting at this site are often referred to as demethylase inhibitors, DMI fungicides, or DMIs. The demethylase enzyme is sometimes referred to by other names in the biochemical literature, including cytochrome P-450 (14DM). The demethylase enzyme is described in, for example, J. Biol. Chem. 1992, 267, 13175-79 and references cited therein. DMI fungicides fall into several classes: azoles (including triazoles and imidazoles), pvrimidines, piperazines and pyridines. The triazoles includes bromuconazole, cyproconazole, difenoconazole, diniconazole, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, ipconazole, metconazole, penconazole, propiconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole anduniconazole. The imidazoles include clotrimazole, econazole, imazalil, isoconazole, miconazole and prochloraz. The pyrimidines include fenarimol, nuarimol and triarimol. The piperazines include triforine. The pyridines include buthiobate and pyrifenox. Biochemical investigations have shown that all of the above mentioned fungicides are DMI fungicides as described by K. H. Kuck, et al. in Modern Selective Fungicides - Properties, Applications and Mechanisms of Action, Lyr, H., Ed.; Gustav Fischer Verlag: New York, 1995, 205-258.
The DMI fungicides have been grouped together to distinguish them from other sterol biosynthesis inhibitors, such as, the moφholine and piperidine fungicides. The moφholines and piperidines are also sterol biosynthesis inhibitors but have been shown to inhibit later steps in the sterol biosynthesis pathway. The moφholines include aldimoφh, dode oφh, fenpropimoφh, tridemoφh and trimoφhamide. The piperidines include fenpropidin. Biochemical investigations have shown that all of the above mentioned moφholine and piperidine fungicides are sterol biosynthesis inhibitor fungicides as described by K. H. Kuck, et al. in Modern Selective Fungicides - Properties, Applications and Mechanisms of Action, Lyr, H., Ed.; Gustav Fischer Verlag: New York, 1995, 185-204. Pyrimidinone Fungicides (component (bl))
Pyrimidinone fungicides include compounds of Formula II
Figure imgf000040_0001
II wherein
G is a fused phenyl, thiophene or pyridine ring;
R1 is CrC6 alkyl;
R2 is CyC alkyl or C\-C^ alkoxy;
R3 is halogen; and
R4 is hydrogen or halogen.
Pyrimidinone fungicides are described in International Patent Application WO94/26722, U.S. Patent No. 6,066,638, U.S. Patent No. 6,245,770, U.S. Patent No. 6,262,058 and U.S. Patent No. 6,277,858.
Of note are pyrimidinone fungicides selected from the group: 6-bromo-3-propyl-2-propyloxy-4(3H)-quinazolinone,
6 , 8 -diiodo-3 -propyl-2-propyloxy-4(3H)-quinazolinone,
6-iodo-3-propyl-2-propyloxy-4(3H)-quinazolinone,
6-chloro-2-propoxy-3-propylthieno[2,3-Λf]pyrimidin-4(3H)-one,
6-bromo-2-propoxy-3 -propy lthieno [2,3 -c pyrimidin-4(3H)-one,
7-bromo-2-propoxy-3-propylthieno[3,2-c/]pyrimidin-4(3H)-one,
6-bromo-2-propoxy-3-propylpyrido[2,3-c ]pyrimidin-4(3H)-one,
6 , 7-dibromo-2-propoxy-3 -propy lthieno [3 ,2-^pyrimidin-4(3H)-one, and
3-(cyclopropylmemyl)-6-iodo-2-(propyltMo)pyrido[2,3-^pyrimidin-4(3H)-one.
Table 8 Examples of component (b)
(bl) Alkylenebis(dithiocarbamate)s such as mancozeb, maneb, propineb and zineb
(b3) Cymoxanil
(b6) Phenylamides such as metalaxyl, benalaxyl and oxadixyl
(b8) Phthalimids such as folpet or captan
(b9) Fosetyl-aluminum Other fungicides which can be included in combination with a Formula I compound or as an additional component in combination with component (a) and component (b) are acibenzolar, benalaxyl, benomyl, blasticidin-S, Bordeaux mixture (tribasic copper sulfate), caφropamid, captafol, captan, carbendazim, chloroneb, chlorothalonil, copper oxychloride, copper salts such as copper sulfate and copper hydroxide, cyazofamid, cymoxanil, cyprodinil, (S)-3,5-dic oro-N-(3-cMoro-l-e1hyl-l-methyl- 2-oxopropyl)-4-methylbenzamide (RΗ 7281), diclocymet (S-2900), diclomezine, dicloran, dimethomoφh, diniconazole-M, dodemoφh, dodine, edifenphos, fencaramid (SZX0722), fenpiclonil, fentin acetate, fentin hydroxide, fluazinam, fludioxonil, flumetover (RPA 403397), flutolanil, folpet, fosetyl- aluminum, furalaxyl, furametapyr (S-82658), iprobenfos, iprodione, isoprothiolane, iprovalicarb, kasugamycin, mancozeb, maneb, mefenoxam, epronil, metalaxyl, metiram- zinc, myclobutanil, neo-asozin (ferric methanearsonate), oxadixyl, pencycuron, prochloraz, procymidone, propamocarb, propineb, pyrifenox, pyrimethanil, pyroquilon, quinoxyfen, spiroxamine, sulfur, thifluzamide, thiophanate-methyl, thiram, triadimefon, tricyclazole, validamycin, vinclozolin, zineb and zoxamid.
Descriptions of the commercially available compounds listed above may be found in The Pesticide Manual, Twelfth Edition, C.D.S. Tomlin, ed., British Crop Protection Council, 2000.
Of note are combinations of Formula I with fungicides of a different biochemical mode of action (e.g. mitochondrial respiration inhibition, inhibition of protein synthesis by interference of the synthesis of ribosomal RΝA or inhibition of beta-tubulin synthesis) that can be particularly advantageous for resistance management. Examples include combinations of compounds of Formula I (e.g. Compound 1) with strobilurins such as azoxystrobin, kresoxim-methyl, pyraclosfrobin and trifloxystrobin; carbendazim, mitochondrial respiration inhibitors such as famoxadone and fenamidone; benomyl, cymoxanil; dimethomoφh; folpet; fosetyl-aluminum; metalaxyl; mancozeb and maneb. These combinations can be particularly advantageous for resistance management, especially where the fungicides of the combination control the same or similar diseases.
Of note are combinations of Formula I with fungicides for controlling grape diseases (e.g. Plasmopara viticola, Botrytis cinerea and Uncinula necatur) including alkylenebis(dithiocarbamate)s such as mancozeb, maneb, propineb and zineb, phthalimids such as folpet, copper salts such as copper sulfate and copper hydroxide, strobilurins such as azoxystrobin, pyraclostrobin and trifloxystrobin, mitochondrial respiration inhibitors such as famoxadone and fenamidone, phenylamides such as metalaxyl, phosphonates such as fosetyl-Al, dimethomoφh, pyrimidinone fungicides such as 6-iodo-3-propyl-2-propyloxy-4(3H)-quinazolinone and 6-chloro-2-propoxy-3- propyltMeno[2,3-<-fJpyrimidin-4(3H)-one, and other fungicides such as cymoxanil.
Of note are combinations of Formula I with fungicides for controlling potato diseases (e.g. Phytophthora infestans, Alternaria solani mdRhizoctonia solani) including alkylenebis(dithiocarbamate)s such as mancozeb, maneb, propineb and zineb; copper salts such as copper sulfate and copper hydroxide; strobilurins such as pyraclostrobin and trifloxystrobin; mitochondrial respiration inhibitors such as famoxadone and fenamidone; phenylamides such as metalaxyl; carbamates such as propamocarb; phenylpyridylamines such as fluazinam and other fungicides such as chlorothalonil, cyazofamid, cymoxanil, dimethomoφh, zoxamid and iprovalicarb.
Of note are compositions wherein component (b) comprises at least one compound from each of two different groups selected from (bl), (b2), (b3), (b4), (b5), (b6), (bl), (b8) and (b9). The weight ratio of the compound(s) of the first of these two component (b) groups to the compound(s) of the second of these component (b) groups typically is from 100:1 to 1:100, more typically from 30:1 to 1:30 and most typically from 10:1 to 1:10.
Of note are compositions wherein component (b) comprises at least one compound selected from (bl), for example mancozeb, and at least one compound selected from a second component (b) group, for example, from (b2), (b3), (b6), (b7), (b8) or (b9). Of particular note are such compositions wherein the overall weight ratio of component (b) to component (a) is from 30:1 to 1:30 and the weight ratio of component (bl) to component (a) is from 10: 1 to 1:1. Included are compositions wherein the weight ratio of component (bl) to component (a) is from 9:1 to 4.5:1. Examples of these compositions include compositions comprising mixtures of component (a) (preferably a compound from Index Table A) with mancozeb and a compound selected from the group consisting of famoxadone, fenamidone, azoxystrobin, kresoxim-methyl, pyraclostrobin, trifloxystrobin, cymoxanil, metalaxyl, benalaxyl, oxadixyl, 6-iodo-3-propyl-2-propyloxy-4(3H)-quinazolinone, 6-chloro-2- propoxy-3-propylthieno[2,3-rf]pyrimidin-4(3H)-one, folpet, captan and fosetyl-aluminum.
Also of note are compositions wherein component (b) comprises at least one compound selected from (b2), for example famoxadone, and at least one compound selected from a second component (b) group, for example, from (bl), (b3), (b6), (b7), (b8) or (b9). Of particular note are such compositions wherein the overall weight ratio of component (b) to component (a) is from 30:1 to 1:30 and the weight ratio of component (b2) to component (a) is from 10:1 to 1:1. Included are compositions wherein the weight ratio of component (b2) to component (a) is from 9:1 to 4.5:1. Examples of these compositions include compositions comprising mixtures of component (a) (preferably a compound from Index Table A) with famoxadone and a compound selected from the group consisting of mancozeb, maneb, propineb, zineb, cymoxanil, metalaxyl, benalaxyl, oxadixyl, 6-iodo-3 -propy 1-2-propyloxy- 4(3H)-quinazolinone, 6-cMoro-2-propoxy-3-propylt eno[2,3-^pyrimidin-4(3H)-one, folpet, captan and fosetyl-aluminum.
Also of note are compositions wherein component (b) comprises the compound of (b3), in other words cymoxanil, and at least one compound selected from a second component (b) group, for example, from (bl), (b2), (b6), (b7), (b8) or (b9). Of particular note are such compositions wherein the overall weight ratio of component (b) to component (a) is from 30:1 to 1:30 and the weight ratio of component (b3) to component (a) is from 10 : 1 to 1:1. Included are compositions wherein the weight ratio of component (b3) to component (a) is from 9:1 to 4.5:1. Examples of these compositions include compositions comprising mixtures of component (a) (preferably a compound from Index Table A) with cymoxanil and a compound selected from the group consisting of famoxadone, fenamidone, azoxystrobin, kresoxim-methyl, pyraclostrobin, trifloxystrobin, mancozeb, maneb, propineb, zineb, metalaxyl, benalaxyl, oxadixyl, 6-iodo-3-propyl-2-propyloxy-4(3H)-quinazolinone, 6- chloro-2-propoxy-3-propylthieno[2,3-^pyrimidin-4(3H)-one, folpet, captan and fosetyl- aluminum.
Also of note are compositions wherein component (b) comprises at least one compound selected from (b6), for example metalaxyl, and at least one compound selected from a second component (b) group, for example, from (bl), (b2), (b3), (bl), (b8) or (b9). Of particular note are such compositions wherein the overall weight ratio of component (b) to component (a) is from 30: 1 to 1 :30 and the weight ratio of component (b6) to component (a) is from 10:1 to 1:3. Included are compositions wherein the weight ratio of component (b6) to component (a) is from 9:1 to 4.5:1. Examples of these compositions include compositions comprising mixtures of component (a) (preferably a compound from Index Table A) with metalaxyl or oxadixyl and a compound selected from the group consisting of famoxadone, fenamidone, azoxystrobin, kresoxim-methyl, pyraclostrobin, trifloxystrobin, cymoxanil, mancozeb, maneb, propineb, zineb, 6-iodo-3-propyl- 2-propyloxy-4(3H)-quinazolinone, 6-chloro-2-propoxy-3-propylt eno[2,3--^pyrimidin- 4(3H)-one, folpet, captan and fosetyl-aluminum.
Also of note are compositions wherein component (b) comprises at least one compound selected from (b7), for example 6-iodo-3-propyl-2-propyloxy-4(3H)- quinazolinone or 6-cUoro-2-propoxy-3-propyltMeno[2,3-^pyrimidin-4(3H)-one, and at least one compound selected from a second component (b) group, for example, from (bl), (b2), (b3), (b6), (b8) or (b9). Of particular note are such compositions wherein the overall weight ratio of component (b) to component (a) is from 30: 1 to 1 :30 and the weight ratio of component (b7) to component (a) is from 1:1 to 1 :20. Included are compositions wherein the weight ratio of component (b6) to component (a) is from 1:4.5 to 1 :9. Examples of these compositions include compositions comprising mixtures of component (a) (preferably a compound from Index Table A) with 6-iodo-3-propyl-2-propyloxy-4(3H)-quinazolinone or 6-chloro-2-propoxy-3-propylthieno[2,3-ώ |pyrimidin-4(3H)-one and a compound selected from the group consisting of famoxadone, fenamidone, azoxystrobin, kresoxim-methyl, pyraclostrobin, trifloxystrobin, cymoxanil, mancozeb, maneb, propineb, zineb, metalaxyl, benalaxyl, oxadixyl, folpet, captan and fosetyl-aluminum.
Also of note are compositions wherein component (b) comprises the compound of (b9), in other words fosetyl-aluminum, and at least one compound selected from a second component (b) group, for example, from (bl), (b2), (b3), (b6) or (bl). Of particular note are such compositions wherein the overall weight ratio of component (b) to component (a) is from 30: 1 to 1 :30 and the weight ratio of component (b9) to component (a) is from 10: 1 to 1:1. Included are compositions wherein the weight ratio of component (b9) to component (a) is from 9:1 to 4.5:1. Examples of these compositions include compositions comprising mixtures of component (a) (preferably a compound from Index Table A) with fosetyl- aluminum and a compound selected from the group consisting of famoxadone, fenamidone, azoxystrobin, kresoxim-methyl, pyraclostrobin, trifloxystrobin, mancozeb, maneb, propineb, zineb, metalaxyl, benalaxyl, oxadixyl, 6-iodo-3-propyl-2-propyloxy-4(3H)-quinazolinone, 6- cMoro-2-propoxy-3-propylthieno[2,3-rf]pyrimidin-4(3H)-one, folpet, captan and cymoxanil.
Of note are combinations of compounds of Formula I with fungicides giving an even broader spectrum of agricultural protection including strobilurins such as azoxystrobin, kresoxim-methyl, pyraclostrobin and trifloxystrobin; moφholines such as fenpropidine and fenpropimoφh; triazoles such as bromuconazole, cyproconazole, difenoconazole, epoxyconazole, flusilazole, ipconazole, metconazole, propiconazole, tebuconazole and triticonazole; pyrimidinone fungicides, benomyl; carbendazim; chlorothalonil; dimethomoφh; folpet; mancozeb; maneb; quinoxyfen; validamycin and vinclozolin.
Preferred 6. Preferred compositions comprise a compound of component (a) mixed with cymoxanil. Preferred 7. Preferred compositions comprise a compound of component (a) mixed with a compound selected from (bl). More preferred is a composition wherein the compound of (bl) is mancozeb.
Preferred 8. Preferred compositions comprise a compound of component (a) mixed with a compound selected from (b2). More preferred is a composition wherein the compound of (b2) is famoxadone.
Of particular note are combinations of Compound 1 or 5 with azoxystrobin, combinations of Compound 1 or 5 with kresoxim-methyl, combinations of Compound 1 or 5 with pyrclostrobin, combinations of Compound 1 or 5 with trifloxystrobin, combinations of Compound 1 or 5 with carbendazim, combinations of Compound 1 or 5 with chlorothalonil, combinations of Compound 1 or 5 with dimethomoφh, combinations of Compound 1 or 5 with folpet, combinations of Compound 1 or 5 with mancozeb, combinations of Compound 1 or 5 with maneb, combinations of Compound 1 or 5 with quinoxyfen, combinations of Compound 1 or 5 with validamycin, combinations of Compound 1 or 5 with vinclozolin, Compound 1 or 5 with fenpropidine, combinations of Compound 1 or 5 with fenpropimoφh, combinations of Compound 1 or 5 with bromuconazole, combinations of Compound 1 or 5 with cyproconazole, combinations of Compound 1 or 5 with difenoconazole, combinations of Compound 1 or 5 with epoxyconazole, combinations of Compound 1 or 5 with flusilazole, combinations of Compound 1 or 5 with ipconazole, combinations of Compound 1 or 5 with metconazole, combinations of Compound 1 or 5 with propiconazole, combinations of Compound 1 or 5 with tebuconazole, combinations of Compound 1 or 5 with triticonazole, combinations of Compound 1 or 5 with famoxadone, combinations of Compound 1 or 5 with fenamidone, combinations of Compound 1 or 5 with benomyl, combinations of Compound 1 or 5 with cymoxanil, combinations of Compound 1 or 5 with fosetyl-aluminum, combinations of Compound 1 or 5 with metalaxyl, combinations of Compound 1 or 5 with propineb, combinations of Compound 1 or 5 with zineb, combinations of Compound 1 or 5 with copper sulfate, combinations of Compound 1 or 5 with copper hydroxide, combinations of Compound 1 or 5 with propamocarb, combinations of Compound 1 or 5 with cyazofamid, combinations of Compound 1 or 5 with zoxamid, combinations of Compound 1 or 5 with fluazinam and combinations of Compound 1 or 5 with iprovalicarb. Compound numbers refer to compounds in Index Table A.
Formulation/Utility
Compositions of this invention will generally be used as a formulation or composition comprising at least one carrier selected from agriculturally suitable liquid diluents, solid diluents and surfactants. 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 (e.g. from 0.01-99.99 weight percent) of active ingredients together with diluent and/or surfactant within the following approximate ranges which add up to 100 percent by weight.
Weight Percent
Active Ingredients Diluent Surfactant
Water-Dispersible and Water-soluble 5-90 0-94 1-15 Granules, Tablets and Powders.
Suspensions, Emulsions, Solutions 5-50 40-95 0-25 (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. Coφ., 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, N,N-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 tefrahydroi-urfuryl 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. Preferred suspension concentrates include those containing, in addition to the active ingredient, from 5 to 20% nonionic surfactant (for example, polyethoxylated fatty alcohols) optionally combined with 50-65% liquid diluents and up to 5% anionic surfactants. 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; andHance 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. 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 where otherwise indicated. Example A Wettable Powder
Active ingredients 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium hgninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.
Example B Granule
Active ingredients 10.0% attapulgite granules (low volatile matter,
0.71/0.30 mm; U.S.S. No.25-50 sieves) 90.0%.
Example C Extruded Pellet
Active ingredients 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.
Example D Emulsifiable Concentrate
Active ingredients 20.0% blend of oil soluble sulfonates and polyoxyethylene ethers 10.0% isophorone 70.0%.
Example E Suspension Concentrate
Active ingredients 20.0% polyethoxylated fatty alcohol nonionic surfactant 15.0% ester derivative of montan wax 3.0% calcium lignosulfonate anionic surfactant 2.0% polyethoxylated/polypropoxylated polyglycol block copolymer surfactant 1.0% propylene glycol diluent 6.4% poly(dimethylsiloxane) antifoam agent 0.6% antimicrobial agent 0.1% water diluent 51.9% The formulation ingredients are mixed together as a syrup, the active ingredients are added and the mixture is homogenized in a blender. The resulting slurry is then wet-milled to form a suspension concentrate.
Compositions of this invention can also be mixed with one or more insecticides, nematocides, bactericides, acaricides, growth regulators, chemosterilants, semiochemicals, repellents, attractants, pheromones, feeding stimulants or other biologically active compounds to form a multi-component pesticide giving an even broader spectrum of agricultural protection. Examples of such agricultural protectants with which compositions of this invention can be formulated are: insecticides such as abamectin, acephate, azinphos-methyl, bifenthrin, buprofezin, carbofuran, chlorfenapyr, chloφyrifos, chloφyrifos-methyl, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, deltamethrin, diafenthiuron, diazinon, diflubenzuron, dimethoate, esfenvalerate, fenoxycarb, fenpropathrin, fenvalerate, fipronil, flucythrinate, tau-fluvalinate, fonophos, imidacloprid, isofenphos, malathion, metaldehyde, methamidophos, methidathion, methomyl, methoprene, methoxychlor, methyl 7-chloro-2,5-dihydro-2-[[N-(methoxycarbonyl)-N-[4- (trifluoromethoxy)phenyl] amino] carbonyl]indeno [ 1 ,2-e] [1,3 ,4]oxadiazine-4a(3H)- carboxylate (indoxacarb), monocrotophos, oxamyl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, rotenone, sulprofos, tebufenozide, tefluthrin, terbufos, tetrachlorvinphos, thiodicarb, tralomethrin, trichlorfon and triflumuron; bactericides such as streptomycin; acaricides such as amitraz, chinomethionat, chlorobenzilate, cyhexatin, dicofol, dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad; nematocides such as aldoxycarb and fenamiphos; and biological agents such as Bacillus thuringiensis, Bacillus thuringiensis delta endotoxin, baculovirus, and entomopathogenic bacteria, virus and fungi. The weight ratios of these various mixing partners to compounds of Formula I of this invention typically are between 100:1 and 1:100, preferably between 30:1 and 1:30, more preferably between 10:1 and 1:10 and most preferably between 4:1 and 1:4.
The compositions of this invention are useful as plant disease control agents. The present invention therefore further comprises a method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof to be protected, or to the plant seed or seedling to be protected, an effective amount of a compound of the invention or a fungicidal composition containing said compound. The compounds and compositions of this invention provide control of diseases caused by a broad spectrum of fungal plant pathogens in the Basidiomycete, Ascomycete, Oomycete and Deuteromycete classes. They are effective in controlling a broad spectrum of plant diseases, particularly foliar pathogens of ornamental, vegetable, field, cereal, and fruit crops. These pathogens include Plasmopara viticola, Phytophthora infestans, Peronospora tabacina, Pseudoperonospora cubensis, Pythium aphanidermatum, Alternaria brassicae, Septoria nodorum, Septoria tritici, Cercosporidiumpersonatum, Cercospora arachidicola, Pseudocercosporella herpotrichoides, Cercospora beticola, Botrytis cinerea, Monilinia fructicola, Pyricularia oryzae, Podosphaera leucotricha, Venturia inaequάlis, Erysiphe graminis, Uncinula necatur, Puccinia recondita, Puccinia graminis, Hemileia vastatrix, Puccinia striiformis, Puccinia arachidis, Rhizoctonia solani, Sphaerothecafuliginea, Fusarium oxysporum, Verticillium dahliae, Pythium aphanidermatum, Phytophthora megasperma, Sclerotinia sclerotiorum, Sclerotium rolfsii, Erysiphe olygoni, Pyrenqphora teres, Gaeumannomyces graminis, Rynchosporium secaiis, Fusarium roseum, Bremia lactucae and other generea and species closely related to these pathogens. The compositions of the invention are especially effective in controlling Plasmopara viticola on grapes and Phytophthora infestans on potatoes and tomatoes.
Plant disease control is ordinarily accomplished by applying an effective amount of a compound of this invention either pre- or post-infection, to the portion of the plant to be protected such as the roots, stems, foliage, fruit, seeds, tubers or bulbs, or to the media (soil or sand) in which the plants to be protected are growing. The compounds can also be apphed to the seed to protect the seed and seedling.
Rates of application for these compounds can be influenced by many factors of the environment and should be determined under actual use conditions. Foliage can normally be protected when treated at a rate of from less than 1 g/ha to 5,000 g/ha of active ingredient. Seed and seedlings can normally be protected when seed is treated at a rate of from 0.1 to 10 g per kilogram of seed.
Synergism has been described as "the cooperative action of two components of a mixture, such that the total effect is greater or more prolonged than the sum of the effects of the two (or more) taken independently" (see Tames, P. M. L., Neth. J. Plant Pathology, 1964, 70, 73-80). It is found that compositions containing the compound of Formula I and fungicides with a different mode of action exhibit synergistic effects.
The presence of a synergistic effect between two active ingredients (e.g. componet (a) and component (b)) is established with the aid of the Colby equation (see Colby, S. R. In Calculating Synergistic and Antagonistic Responses of Herbicide Combinations, Weeds, 1967, 15, 20-22): p =A+B- A x B
100
Using the methods of Colby, the presence of a synergistic interaction between two active ingredients is established by first calculating the predicted activity, p, of the mixture based on activities of the two components apphed alone. If p is lower than the experimentally established effect, synergism has occurred. In the equation above, A is the fungicidal activity in percentage control of one component apphed alone at rate x. The B term is the fungicidal activity in percentage control of the second component applied at rate y. The equation estimates p, the fungicidal activity of the mixture of A at rate x with B at rate y if their effects are strictly additive and no interaction has occurred.
The following TESTS can be used to demonstrate the control efficacy of compositions of this invention on specific pathogens. The pathogen control protection afforded by the compositions is not limited, however, to these species. See Index Tables A for compound designations for component (a) compounds used in the TESTS.
Index Table A
Figure imgf000051_0001
CmpdNo. (R5)m Rl R2 (R m. p. (° C)
1 3-Cl-5-CF3 H H 2,6-di-Cl 164-168
2 3-CI-5-CF3 H CH3 2,6-di-Cl
3 3-CI-5-CF3 H H 2,6-di-Cl-4-CH3
4 3-CI-5-CF3 H CH3 2,6-di-Cl-4-CH3
5 3,5-di-Cl H H 2,6-di-Cl
6 3,5-di-Cl H CH3 2,6-di-Cl
7 3,5-di-Cl H H 2,6-di-Cl-4-CH3
8 3,5-di-Cl H CH3 2,6-di-Cl-4-CH3
BIOLOGICAL EXAMPLES OF THE INVENTION
The following TESTS demonstrate the control efficacy of compositions of this invention on specific pathogens. The pathogen control protection afforded by the compounds is not limited, however, to these species.
Test suspensions comprising a single active ingredient are sprayed to demonstrate the control efficacy of the active ingredient individually. To demonstrate the control efficacy of a combination, (a) the active ingredients can be combined in the appropriate amounts in a single test suspension, (b) stock solutions of individual active ingredients can be prepared and then combined in the appropriate ratio, and diluted to the final desired concentration to form a test suspension or (c) test suspensions comprising single active ingredients can be sprayed sequentially in the desired ratio. Composition 1
Ingredients Wt.%
Compound 1 Technical Material 20
Polyethoxylated stearyl alcohol 15
Montan wax ester 3
Desugared calcium lignosulfate 2
Polyoxypropylene-polyoxyethylene block copolymer 1
Propylene Glycol 6.4
Polyorganosiloxanes + emulsifying agent 0.6
19% (l,2-benzisothiazolin-3-one) in aqueous dipropylene glycol 0.1
Water 51.9
Composition 2
Ingredients Wt. %
Famoxadone Technical Material 51.7
Sodium lignosulfate 36.0 Sodium alkylnaphthalene sulfonate 2.0
Polyvinyl pyrrolidone 4.0
Polyoxypropylene-polyoxyethylene block copolymer 3.0 Sodium dodecylbenzene sulfonate 3.0
Fluoroalkyl acid mixture 0.3
Composition 3
Ingredients Wt. %
Cymoxanil Technical Material 61.9
Sodium alkylnaphthalene sulfonate formaldehyde condensate 5.0 Sodium alkylnaphthalene sulfonate 1.0
Polyvinyl pyrrolidone 4.0
Monosodium phosphate 4.0
Fumaric acid 1.0
Fumed silica 1.0
Sodium 0.2
Sugar 14.0
Sodium lignosulfate 7.9
Test compositions were first mixed with purified water containing 250 ppm of the surfactant Trem® 014 (polyhydric alcohol esters). The resulting test suspensions were then used in the following tests. Test suspensions were sprayed to the point of run-off on the test plants at the equivalent rates of 5, 10, 20, 25, 50 or 100 g/ha of active ingredient. Spraying a 40 ppm test suspension to the point of run-off on the test plants is the equivalent of a rate of 100 g/ha. The tests were replicated three times and the results reported as the average of the three replicates.
TEST A (Preventive Control) The test suspensions were sprayed to the point of run-off on Potato seedlings. The following day the seedlings were inoculated with a spore suspension of Phytophthora infestans (the causal agent of tomato and potato late blight) and incubated in a saturated atmosphere at 20 °C for 24 hours, and then moved to a growth chamber at 20 °C for 5 days, after which disease ratings were made.
TEST B (Curative ControD Potato seedlings were inoculated with a spore suspension of Phytophthora infestans (the causal agent of tomato and potato late blight) 24 hours prior to application and incubated in a saturated atmosphere at 20 °C for 24 hours. The test suspensions were then sprayed to the point of run-off on the potato seedlings. The following day the seedlings were moved to a growth chamber at 20 °C for 5 days, after which disease ratings were made.
TEST C (Extended Preventive Control)
The test suspensions was sprayed to the point of run-off on potato seedlings. Six days later, the seedlings were inoculated with a spore suspension of Phytophthora infestans (the causal agent of tomato and potato late blight) and incubated in a saturated atmosphere at 20 °C for 24 h, and then moved to a growth chamber at 20 °C for 5 days, after which disease ratings were made.
Results for Tests A-C are given in Table A. In the table, a rating of 100 indicates 100% disease control and a rating of 0 indicates no disease control (relative to the controls). Columns labeled Avg indicates the average of three replications. Columns labeled Exp indicate the expected value for each treatment mixture using the Colby equation. Tests demonstrating control greater than expected are indicated with *.
Table A
Composition Test A Test B Test C
Number Rate Avg Exp Avg Exp Avg Exp
1 5 0 XX 0 XX 0 XX
1 10 32 XX 0 XX 37 XX
1 20 100 XX 0 XX 98 XX
2 25 100 XX 0 XX 0 XX
2 50 100 XX 0 XX 0 XX
2 100 100 XX 0 XX 0 XX
3 25 0 XX 0 XX 0 XX
3 50 0 XX 0 XX 0 XX
3 100 32 XX 0 XX 0 XX Composition Test A TestB Test C
Number Rate Avg Exp Avg Exp Avg Exp
1 +2 5 + 25 100 100 0 0 0 0
1 + 2 10 + 50 100 100 0 0 75* 37
1 + 2 20 + 100 100 100 0 0 99 98
1 + 3 5 + 25 0 0 0 0 37* 0
1 + 3 10 + 50 100* 32 0 0 88* 37
1 + 3 20 + 100 100 100 9 0 76 98
Based on the description of synergism developed by Colby, compositions of the present invention are illustrated to be synergistically useful. Moreover, compositions comprising components (a) and (b) alone can be conveniently mixed with an optional diluent prior to applying to the crop to be protected. Accordingly, this invention provides an improved method of combating fungi, particularly fungi of the class Oomycetes such as Phytophthora spp. mάPlasmopara spp., in crops, especially potatoes, grapes and tomatoes.

Claims

CLAIMSWhat is claimed is:
1. A composition for controlling plant diseases caused by fungal plant pathogens comprising:
(a) at least one compound of Formula I, N-oxides and agriculturally suitable salts thereof
Figure imgf000055_0001
wherein
A is a substituted pyridinyl ring;
B is a substituted phenyl ring;
W is C=L or SOn;
L is O or S;
Rl and R2 are each independently H; or Cι-C6 alkyl, C2-Cg alkenyl, C2-C6 alkynyl or C3-C6 cycloalkyl, each optionally substituted;
R is H; or CrC6 alkyl, C2-C6 alkenyl, C2-C6 alkynyl, C3-C6 cycloalkyl, C2-C10 alkoxyalkyl, C2-C6 alkylcarbonyl, C2-Cg alkoxycarbonyl, C2-C6 alkylaminocarbonyl or C3-Cg dialkylaminocarbonyl; and n is 1 or 2; and
(b) at least one compound selected from the group consisting of
(bl) alkylenebis(dithiocarbamate) fungicides;
(b2) compounds acting at the bc\ complex of the fungal mitochondrial respiratory electron transfer site;
(b3) cymoxanil;
(b4) compounds acting at the demethylase enzyme of the sterol biosynthesis pathway;
(b5) moφholine and piperidine compounds that act on the sterol biosynthesis pathway;
(b6) phenylamide fungicides;
(b7) pyrimidinone fungicides;
(b8) phthalimides; and
(b9) fosetyl-aluminum.
2. A composition of Claim 1 in which component (a) is a compound of Formula I wherein
A is a pyridinyl ring substituted with from 1 to 4 R5; B is a phenyl ring substituted with from 1 to 4 R6;
W is C=O;
Rl and R2 are each independently H; or Ci -Cg alkyl, C -Cg alkenyl, C2-Cg alkynyl or C3-C6 cycloalkyl, each optionally substituted with one or more substituents selected from the group consisting of halogen, CN, NO2, hydroxy, C1-C4 alkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C2-C4 alkoxycarbonyl, C1-C4 alkylamino, C2-Cg dialkylamino and C3-C6 cycloalkylamino;
R3 is H; and each R5 and R6 is independently C1-C6 alkyl, C2-Cg alkenyl, C2-Cg alkynyl, C -Cg cycloalkyl, C^-Cg haloalkyl, C2-C6 haloalkenyl, C2-Cg haloalkynyl, C3-Cg halocycloalkyl, halogen, CN, CO2H, CONH2, NO2, hydroxy, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl, C1-C4 haloalkylsulfonyl, -C4 alkylamino, C2-Cg dialkylamino, C3-C6 cycloalkylamino, C2-Cg alkylcarbonyl, C2-Cg alkoxycarbonyl, C -Cg alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl or C3-C6 trialkylsilyl; or each R5 and R6 is independently a phenyl, a benzyl, a phenoxy, a 5- or 6-membered heteroaromatic ring or a 5- or 6-membered nonaromatic heterocyclic ring, each ring optionally substituted with from one to three substituents independently selected from R7; or two R6 attached to contiguous carbon atoms are taken together with said carbon atoms to form a fused phenyl ring, a fused 5- or 6-membered nonaromatic carbocyclic ring, a fused 5- or 6-membered heteroaromatic ring or a fused 5- or 6-membered nonaromatic heterocyclic ring, each fused ring optionally substituted with from one to three substituents independently selected from R7; each R7is independently C1-C4 alkyl, C -Qφ alkenyl, C2-C4 alkynyl, C3-C6 cycloalkyl, -C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, C3-Cg halocycloalkyl, halogen, CN, NO2, C1-C4 alkoxy, -C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 alkylamino, C2-Cg dialkylamino, C3-Cg cycloalkylamino, C3-Cg (alkyl)cycloalkylamino, C -Q alkylcarbonyl, C2-Cg alkoxycarbonyl, C2-C6 alkylaminocarbonyl, C3-Cg dialkylaminocarbonyl or C3-C6 trialkylsilyl.
3. A composition of Claim 2 wherein component (b) is cymoxanil.
4. A composition of Claim 2 wherein component (b) is a compound selected from
(b2).
A composition of Claim 4 wherein component (b) is famoxadone.
6. The composition of Claim 1 wherein component (b) comprises at least one compound from each of two different groups selected from (bl), (b2), (b3), (b4), (b5), (b6), (bl), (b8) and (b9).
7. The composition of Claim 6 wherein component (b) comprises at least one compound selected from (b2) and at least one compound selected from (bl), (b3), (b6), (b7), (b8) or (b9); wherein the overall weight ratio of component (b) to component (a) is from 30:1 to 1:30; and wherein the weight ratio of component (b2) to component (a) is from 10:1 to 1:1.
8. The composition of Claim 6 wherein component (b) comprises cymoxanil and at least one compound selected from (bl), (b2), (b6), (b7), (b8) or (b9); wherein the overall weight ratio of component (b) to component (a) is from 30: 1 to 1 :30; and wherein the weight ratio of cymoxanil to component (a) is from 10:1 to 1:1.
9. A method for controlling plant diseases caused by fungal plant pathogens comprising applying to the plant or portion thereof, or to the plant seed or seedling, a fungicidally effective amount of a composition of Claim 1.
10. The method of Claim 9 wherein the disease to be controlled is caused by the fungal pathogen Phytophthora infestans.
11. The method of Claim 9 wherein the disease to be controlled is caused by the fungal pathogen Plasmopara viticola.
12. A compound of Formula la and N-oxides and agriculturally suitable s alts thereof
Figure imgf000057_0001
wherein
R4 is halogen;
R5 is Ci-C6 alkyl, halogen, ΝO2, C1-C4 alkoxy, C1-C4 haloalkoxy,
Figure imgf000057_0002
alkylthio,
C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl or -C4 haloalkylsulfonyl; each R6 is independently Cj-Cg alkyl, C^-Cg haloalkyl, halogen, NO2, -C4 alkoxy,
C!-C4 haloalkoxy, Cj-C4 alkylthio, C1-C alkylsulfinyl, C1-C4 alkylsulfonyl,
C1-C4 haloalkylthio, -C4 haloalkylsulfinyl or C1-C4 haloalkylsulfonyl; or two R6 attached to contiguous carbon atoms are taken together with said carbon atoms to form a fused 5- or 6-membered nonaromatic heterocyclic ring containing one or two oxygen atoms and optionally substituted with from one to four substituents independently selected from F or methyl; and p is 1, 2, 3 or 4.
13. The compound of Claim 12 wherein R5 is Cl, Br, I, CH3, OCF3, OCHF2, OCH2CF3, OCF2CF3, OCF2CF2H, OCHFCF3, SCF3, SCHF2, SCH2CF3, SCF2CF3, SCF2CF2H, SCHFCF3, SOCF3, SOCHF2, SOCH2CF3, SOCF2CF3, SOCF2CF2H, SOCHFCF3, SO2CF3, SO2CHF2, SO2CH2CF3, SO2CF2CF3, SO2CF2CF2H or SO2CHFCF3.
14. A compound of Formula lb and N-oxides and agriculturally suitable salts thereof
Figure imgf000058_0001
lb
wherein
R4 is halogen;
R5 is C1-C4 haloalkoxy, C1-C4 haloalkylthio, -C4 haloalkylsulfinyl or C1-C4 haloalkylsulfonyl; each R6 is independently C^-Cs alkyl, C^-Cg haloalkyl, halogen, ΝO2, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl or C1-C4 haloalkylsulfonyl; or two R6 attached to contiguous carbon atoms are taken together with said carbon atoms to form a fused 5- or 6-membered nonaromatic heterocyclic ring containing one or two oxygen atoms and optionally substituted with from one to four substituents independently selected from F or methyl; and p is 1, 2, 3 or 4.
15. The compound of Claim 14 wherein R5 is OCF3, OCHF2, OCH2CF3, OCF2CF3, OCF2CF2H, OCHFCF3, SCF3, SCHF2, SCH2CF3, SCF2CF3, SCF2CF2H, SCHFCF3, SOCF3, SOCHF2, SOCH2CF3, SOCF2CF3, SOCF2CF2H, SOCHFCF3, SO2CF3, SO2CHF2, SO2CH2CF3, SO2CF2CF3, SO2CF2CF2H or SO2CHFCF3.
16. A compound of Formula Ic and N-oxides and agriculturally suitable salts thereof
Figure imgf000059_0001
Ic
wherein
R4 is Cl or Br;
R5 is Br or I; each R6 is independently C^-Cg alkyl, C^-Cg haloalkyl, halogen, NO2, C1-C4 alkoxy, C1-C4 haloalkoxy, C1-C4 alkylthio, C1-C4 alkylsulfinyl, C1-C4 alkylsulfonyl, C1-C4 haloalkylthio, C1-C4 haloalkylsulfinyl or C1-C4 haloalkylsulfonyl; or two R6 attached to contiguous carbon atoms are taken together with said carbon atoms to form a fused 5- or 6-membered nonaromatic heterocyclic ring containing one or two oxygen atoms and optionally substituted with from one to four substituents independently selected from F or methyl; and p is 1, 2, 3 or 4.
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