WO2000051992A1 - Fused bicyclic oxazinone and thiazinone fungicides - Google Patents

Fused bicyclic oxazinone and thiazinone fungicides Download PDF

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WO2000051992A1
WO2000051992A1 PCT/US2000/004578 US0004578W WO0051992A1 WO 2000051992 A1 WO2000051992 A1 WO 2000051992A1 US 0004578 W US0004578 W US 0004578W WO 0051992 A1 WO0051992 A1 WO 0051992A1
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och
sch
fused
formula
optionally substituted
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PCT/US2000/004578
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French (fr)
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James Francis Bereznak
Eric Allen Marshall
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E.I. Du Pont De Nemours And Company
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Priority to AU37044/00A priority Critical patent/AU3704400A/en
Publication of WO2000051992A1 publication Critical patent/WO2000051992A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/04—1,3-Oxazines; Hydrogenated 1,3-oxazines
    • C07D265/12—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems
    • C07D265/14—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring
    • C07D265/20—1,3-Oxazines; Hydrogenated 1,3-oxazines condensed with carbocyclic rings or ring systems condensed with one six-membered ring with hetero atoms directly attached in position 4
    • C07D265/22—Oxygen atoms
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/86—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/70—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings condensed with carbocyclic rings or ring systems
    • C07D239/72—Quinazolines; Hydrogenated quinazolines
    • C07D239/95—Quinazolines; Hydrogenated quinazolines with hetero atoms directly attached in positions 2 and 4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
    • C07D279/04—1,3-Thiazines; Hydrogenated 1,3-thiazines
    • C07D279/08—1,3-Thiazines; Hydrogenated 1,3-thiazines condensed with carbocyclic rings or ring systems

Definitions

  • 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.
  • Me means methyl.
  • Alkenyl includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.
  • Examples of substituted fused phenyl rings (G-22) and substituted fused aromatic heterocychc rings (G- 1 to G-21 ) wherein said rings are substituted with R 3 and optionally substituted with R 4 include the ring systems illustrated in Exhibit 1. As with the carbon atoms in the ring, the nitrogen atoms that require substitution to fill their valence are substituted with hydrogen or with R 3 or R 4 . Although the R 3 and R 4 groups are shown in the structures G-l to G-22, it is noted that R 4 does not need to be present since it is an optional substituent. In the exemplified G groups, the upper right bond is attached to the available carbon adjacent to carbon 4 of Formula I and/or Formula II and the lower right bond is attached to the available carbon adjacent to the Z group of Formula I and/or Formula II.
  • Cj-C j The total number of carbon atoms in a substituent group is indicated by the "Cj-C j " prefix where i and j are numbers from 1 to 10.
  • C j -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
  • C 4 alkoxyalkyl designates the various isomers of an alkyl group substituted with an alkoxy group containing a total of four carbon atoms, examples including CH 3 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 .
  • all substituents are attached to these rings through any available carbon or nitrogen by replacement of a hydrogen on said carbon
  • substituents When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents. Further, when the subscript indicates a range, e.g. (R)i_ j , then the number of substituents may be selected from the integers between i and j inclusive.
  • Stereoisomers of this invention can exist as one or more stereoisomers.
  • the various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers.
  • one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s).
  • the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers.
  • the present invention comprises compounds selected from Formula I, N-oxides and agriculturally suitable salts thereof.
  • the compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.
  • the salts of the compounds of the invention include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
  • inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids.
  • the salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine, ammonia, or triethylamine) or inorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic group such as a carboxylic acid or phenol.
  • organic bases e.g., pyridine, ammonia, or triethylamine
  • inorganic bases e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium
  • Preferred compounds for reasons of better activity and/or ease of synthesis are: Preferred 1. Compounds of Formula I and II above, N-oxides and agriculturally suitable salts thereof, wherein each fused phenyl and fused heterocychc ring of G is substituted with R 3 and is optionally substituted with R 4 ; and each phenyl, fused carbobicychc ring system, fused heterobicyclic fused ring system, and heteromonocyclic ring of R l is optionally substituted with R 8 , optionally substituted with R 9 and optionally substituted with R 10 ; wherein
  • R 3 is halogen; C 2 -C 8 alkyl or C 2 -C 8 alkenyl, each optionally substituted with hydroxy, cyano or CO 2 R 6 ; CH 2 OH; CH 2 C ⁇ ; CH 2 CO 2 R 6 ; C 3 -C 8 cycloalkyl; C 2 -C 8 alkynyl; C r C 8 haloalkyl; C 3 -C 8 haloalkenyl; C 3 -C 8 haloalkynyl; C Cg alkoxy; Cj-C 8 haloalkoxy; C 3 -C 8 alkenyloxy; C 3 -C alkynyloxy; C j -Cs alkylthio;
  • R 4 is hydrogen, halogen, C1-C4 alkyl, 0 ⁇ 4 haloalkyl, C1-C4 alkoxy or 1-C4 haloalkoxy; each R 8 is independently Cj-C 6 alkyl; C j -Cg alkoxy; C C6 haloalkyl; halogen; C 2 -C 8 alkynyl; Cj-C 6 alkylthio; phenyl or phenoxy each optionally substituted with at least one R 12 ; cyano; nitro; C ⁇ -Cg haloalkoxy;
  • each Rl and R 2 is independently C r C 5 alkyl; C 3 -C 6 cycloalkyl; C 3 -C 5 alkenyl; C 3 -C 5 alkynyl; C r C 5 haloalkyl; C 3 -C 5 haloalkenyl; C 3 -C 5 haloalkynyl; C 2 -C 5 alkoxyalkyl; C 2 -C 5 alkylthioalkyl; C4-C7 cycloalkylalkyl, phenyl or thienyl, each optionally substituted with R 8 ,
  • R 9 and RlO; and Z is O.
  • Preferred 3 Compounds of Preferred 1 above, N-oxides and agriculturally suitable salts thereof, wherein G is, together with the two linking carbons, a fused thienyl or fused pyridinyl, each optionally substituted with R 3 and optionally substituted with R 4 ; each Rl and R 2 is independently C j -C5 alkyl; C 3 -C 6 cycloalkyl; C 3 -C 5 alkenyl; C 3 -C 5 alkynyl; C!-C 5 haloalkyl; C 3 -C 5 haloalkenyl; C 3 -C5 haloalkynyl; C 2 -C 5 alkoxyalkyl; C 2 -C 5 alkylthioalkyl; C4-C7 cycloalkylalkyl, phenyl or thienyl, each optionally substituted with R 8 ,
  • R 9 and R i0 ; and Z is O or S.
  • Preferred 4 Compounds of Prefe ⁇ ed 1 above, N-oxides and agriculturally suitable salts thereof, wherein R 3 is halogen, C 2 -C 8 alkynyl or C j -C 8 haloalkyl; and
  • R 4 is halogen, C 2 -C 8 alkynyl or C j -Cs haloalkyl.
  • Prefe ⁇ ed 5 Compounds of Prefe ⁇ ed 2 above, N-oxides and agriculturally suitable salts thereof, wherein R 3 is 6-halogen and R 4 is 8-halogen.
  • This invention also relates to fungicidal compositions comprising fungicidally effective amounts of the compounds of the invention and at least one of a surfactant, a solid diluent or a liquid diluent.
  • fungicidal compositions comprising fungicidally effective amounts of the compounds of the invention and at least one of a surfactant, a solid diluent or a liquid diluent.
  • the preferred compositions of the present invention are those which comprise the above preferred compounds.
  • This invention also relates to a method for controlling 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 compounds of the invention (e.g., as a composition described herein).
  • a fungicidally effective amount of the compounds of the invention e.g., as a composition described herein.
  • the prefe ⁇ ed methods of use are those involving the preferred compounds describe above.
  • Z is O, S(O) n or ⁇ R 5 ; n is 0, 1, or 2;
  • Q is O or S; G is, together with the two linking carbons, a substituted fused phenyl or a substituted fused 5- or 6-membered aromatic heterocychc ring; each Rl and R 2 is independently C r C 10 alkyl optionally substituted with NR 6 R 7 , nitro, cyano, CO 2 R 6 , one or more hydroxy, or Rl l; C 3 -C 6 cycloalkyl; C 3 -C ⁇ ) alkenyl; C -C ⁇ o alkynyl; C ⁇ C ⁇ haloalkyl; C 3 -C 10 haloalkenyl; C 3 -CJO haloalkynyl; C 2 -C 10 alkoxyalkyl; C 2 -C 10 alkylthioalkyl; C 2 -CJO alkylsulfonylalkyl; C -C 10 cycloalkylalkyl; C -C 10 alkenyloxyalkyl;
  • R 5 is hydrogen or C1-C4 alkyl; each R 6 and R 7 is independently hydrogen; C1-C4 alkyl optionally substituted with
  • each pair of R 6 and R 7 when attached to the same nitrogen atom, can be taken together as -CH 2 CH 2 CH 2 CH 2 -, -CH 2 (CH 2 ) 3 CH 2 -, -CH 2 CH 2 OCH 2 CH 2 -, -CH 2 CH(Me)CH 2 CH(Me)CH 2 - or -CH 2 CH(Me)OCH(Me)CH 2 -; and each Rl is independently optionally substituted phenyl; an optionally substituted 8-, 9- or 10-membered fused carbobicychc or fused heterobicyclic ring system; or an optionally substituted 3-, 4-, 5- or 6-membered heteromonocyclic ring; wherein said heterobicyclic ring systems and heteromonocyclic rings contain 1 to 4 heteroatoms independently selected from the group nitrogen, oxygen and sulfur, provided that each heterobicyclic ring system or heteromonocyclic ring contains no more than 4 nitrogens, no more than 2
  • the compounds of Formula I can be prepared by one or more of the following methods and variations as described in Schemes 1-23.
  • the definitions of G, Q, R 1 , R 2 , R 5 and Z in the compounds of Formulae 1-24 below are as defined above in the Summary of the Invention.
  • Compounds of Formulae la-Id are various subsets of the compounds of Formula I and all substituents for Formulae la-Id are as defined above for Formula I.
  • the reaction may be conducted in a fashion analogous to that described in Pharmazie, 1969, 24, 100.
  • the transformation can be accomplished in a variety of solvents such as DMF, dieththyl ether, THF, dioxane, etc., at temperatures ranging from ambient to reflux for 2 to 48 hours. Workup and purification can be achieved via concentration to dryness and subsequent silica gel chromatography of the resulting residue to deliver la.
  • the acids of Formula 4 are first converted to the co ⁇ esponding acid chlorides using thionyl chloride or phosphorous pentachloride in accordance with similar methods described in J. Amer. Chem. Soc. , 1906, 28, 111 , and J. Med. Chem. , 1983, 26, 765.
  • the reaction is usually conducted in an inert halocarbon or hydrocarbon solvent (i.e., benzene, chlorobenzene or CH 2 C1 ) at temperatures ranging from ambient to reflux for 0.25 to 2 hours.
  • an appropriate solvent i.e., dioxane or DMF
  • reaction mixture is then poured into a water-immiscible solvent and extracted with dilute aqueous HC1. Separation of the organic phase and concentrated in vacuo delivers the crude product of Formula 3 which may further purified via recrystallization or trituration using appropriate solvents.
  • Hydroxy acids of Formula 4 are either commercially available or accessible using methods cited in the literature (J. Org. Chem., 1954, 19, 1633; Monatsh. Chem., 1950, 81, 83; J. Heterocycl. Chem., 1986, 23, 1465; Hoppe-Seyler's Z. Physiol. Chem., 1957, 306, 49). Amines of Formula 5 are commercially available.
  • Amines of Formula 6 are either commercially available, or prepared using known means.
  • Compounds of Formula 7 are readily prepared from the esters of Formula 8 as depicted in Scheme 5 and described inJ. Heterocycl. Chem., 1991, 28, 133.
  • Alk is Methyl or Ethyl
  • the reaction is conducted by stirring a mixture of a compound of Formula 8, cyanogen bromide, and a suitable base (i.e. Et 3 N, DBU or Na 2 CO 3 ) in a suitable solvent at temperatures ranging from 0 °C to reflux for 1 to 48 hours.
  • suitable solvents for this reaction include acetone, benzene, toluene or dioxane.
  • the desired product may be isolated from the reaction mixture by addition of IN HCl and filtration.
  • the Compound of Formula 7 so obtained may be additionally purified via trituration or recrystallization using appropriate solvents.
  • Alk is Methyl or Ethyl
  • Compounds of Formulae la and Ila can alternatively be produced via reaction of compounds of Formula 9 with electrophiles of Formula 10 (Scheme 7). Similar approaches are known in the art (J. Heterocycl. Chem., 1991, 28, 131).
  • the reaction can be run in solvents such as DMF, THF, dioxane, or chloroform with bases such as triethylamine, DBU, sodium hydride, potassium carbonate, or sodium carbonate at temperatures ranging from 0 °C to reflux.
  • bases such as triethylamine, DBU, sodium hydride, potassium carbonate, or sodium carbonate at temperatures ranging from 0 °C to reflux.
  • the reaction mixture is poured into water and extracted with a water-immiscible solvent.
  • the organic phase is then separated, dried (anhydrous Na 2 SO 4 ), and concentrated in vacuo.
  • the crude isomers of Formulae la and Ila so obtained can be separated by column chromatography to afford the pure, desired compounds.
  • Electrophiles of Formula 10 are either commercially available or can be readily prepared by one skilled in the art.
  • Alk is Methyl or Ethyl
  • Precursors of Formula 11 can be assembled from amides of Formula 12 via base- promoted cychzation with carbon disulfide (Scheme 10).
  • X is halogen
  • the reaction is performed in dioxane, DMF or THF in the presence of 1-3 equivalents of a suitable base and 1-2 equivalents of carbon disulfide.
  • Suitable bases for this transformation include sodium hydride, triethylamine, or 1,8-diazabicyclo 5.4.0]undec-7ene (DBU).
  • a mixture of a compound of Formula 12 and CS 2 in a small amount of suitable solvent is added to a mixture of suitable base in the same solvent. The addition is conducted so as to maintain a reaction temperature below 45 °C.
  • the resulting melange is stirred at ambient temperatures for 12 to 48 hours, at which time the reaction is quenched with saturated ammonium chloride (aqueous).
  • the precipitated product is filtered, dried and may be utilized without further purification. However, additional purification can be achieved through trituration or recrystallization using an appropriate solvent.
  • Amides of Formula 12 are readily prepared from acid chlorides of Formula 13 by treatment with amines of Formula 5 as depicted in Scheme 11.
  • Acyl chlorides of Formula 13 are either commercially available, or can be prepared as cited in the literature (see J. Prakt. Chem., 1937, 148, 13; Nippon Kagaku Zasshi, 1958, 79, 1366; J. LiebigsAnn. Chem., 1936, 17, 27; J. Med. Chem., 1983, 26, 765; J. Org. Chem., 1995, 60, 2292; J. Chem. Res. Miniprint, 1984, 12, 3485).
  • the syntheses of compounds of Formula lb are advantageously achieved through cychzation of compounds of Formula 14 as shown in Scheme 12.
  • the cychzation may be run either neat or in solvents such as DMF, toluene, dioxane or acetonitrile at temperatures ranging from ambient to reflux for 2 hours to 1 week.
  • base is optional; suitable bases for this transformation include triethylamine, sodium carbonate, DBU or sodium hydride.
  • the base when utilized, is present in 1-5 equivalents.
  • saturated aqueous ammonium chloride is added until a precipitate forms.
  • the solid so precipitated is filtered, washed with water and dried.
  • Subjection of this material to silica gel chromatography delivers pure lb. In those instances when the cychzation is conducted neat, silica gel chromatography is performed directly on the reaction residue to obtain pure lb.
  • the reaction is performed using equimolar amounts of an acid chloride of Formula 13 and a thiourea of Formula 15 in solvents such as THF, DMF, dioxane, toluene or acetonitrile at temperatures ranging from 0 °C to reflux for 1 to 48 hours.
  • solvents such as THF, DMF, dioxane, toluene or acetonitrile
  • base is optional; however, when present, 1-5 equivalents of base may be employed.
  • the reaction mixture is poured into methanol water and extracted with a water-immiscible solvent.
  • the organic phase is separated, dried over anhydrous a 2 SO 4 , and concentrated to a crude residue.
  • Silica gel chromatography of this residue affords a pure compound of Formula 14. Workup may also be achieved via filtration of the reaction mixture through a silica gel plug to deliver the crude compound of Formula 14 which may be utilized without further purification.
  • I 3 X is halogen Transformations such as this have precedence in the art and can be conducted in accordance with the specifications cited therein (J. Org. Chem., 1994, 59, 7688).
  • Thioureas of Formula 15 are either commercially available, or may readily prepared as described in J. Amer. Chem. Soc., 1997, 119, 4882 and Synth. Commun., 1997, 27, 3565.
  • Precursors of Formula 17 are preparable through reaction of amino acids of Formula 18 with isothiocyanates of Formula 19 as prescribed in J. Prakt. Chem., 1897, 55, 133 and Khim. Geterosikl. Soedin., 1986, 22, 1236.
  • the reaction is conducted in glacial acetic acid at temperatures ranging from 50-200 °C for 1 to 48 hours using 1-5 molar equivalents of an isothiocyanate of Formula 19. Workup can be accomplished by pouring the reaction mixture into water followed by filtration of the crude precipitate. Recrystallization of the precipitate from an appropriate solvent delivers the precursor of Formula 17.
  • Isothiocyanates of Formula 19 are either commercially available or preparable from -imines of Formula 5 using well-established methods (see, for example, J. Heterocycl. Chem., 1990, 27, 407).
  • Compounds of Formula 18 can be prepared from amino acids of Formula 20 and alkyl halides or sulfonates using procedures outlined in Chem. Ber., 1906, 39, 3237 orJ. Amer, Chem. Soc, 1946, 68, 1810.
  • Amino acids of Formula 20 are available commercially, or readily synthesized by known means (see J. Heterocycl. Chem., 1966, 3, 252; J. Org. Chem., 1952, 17, 547; J. Org. Chem., 1949, 14, 97; Synth. Commun., 1979, 9, 731).
  • the alkyl halides R 5 -X and sulfonates R 5 O-SO 2 -OR 5 are commercially available.
  • compounds of Formula Ic are advantageously prepared from anhydrides of Formula 21 and isothioureas of Formula 22 as cited in J. Heterocycl. Chem., 1985, 22, 193 (Scheme 19).
  • the anhydride precursors of Formula 21 are prepared from compounds of Formula 23 in Scheme 20 using methods outlined inJ. Med. Chem., 1981, 24, 735; J. Heterocycl. Chem., 1979, 16, 661 and 829, or Chem. Ber., 1995, 128, 627.
  • Compounds of Formula 23 are either available commercially or prepared from the amino acids 20 using established methods (see Synthesis, 1980, 505).
  • Isothioureas of Formula 22 are well known in the art and can easily be prepared by the skilled practitioner from the previously described ureas of Formula 15 using procedures cited inJ. Amer. Chem. Soc, 1951, 73, 602; Collect. Czech. Chem. Commun., 1975, 40, 3904; J. Amer. Chem., Soc, 1933, 55, 4986 orJ. Med. Chem., 1992, 35, 3942.
  • CH 2 CH 2 OCH 2 CH CH 2 CH 2 CH 2 SCH 2 CsCH CH 2 OCF 3 CH 2 0CH 2 CH 2 C1
  • CH 2 CH 2 OCH 2 CH CH 2 CH 2 CH 2 SCH 2 C ⁇ CH CH 2 OCF 3 CH 2 0CH 2 CH 2 C1
  • CH 2 CH CHCH 2 SCH 3 2-furanyl CH 2 CH 2 Si(CH 3 ) 3 CH 2 CH 2 C0 2 CH 3
  • CH 2 CH CHCH 2 SCH 3 2-fi ⁇ ranyl CH 2 CH 2 Si(CH 3 ) 3 CH 2 CH 2 C0 2 CH 3
  • CH 2 CH 2 OCH 2 CH CH 2 CH 2 CH 2 SCH 2 C--CH CH 2 OCF 3 CH 2 0CH 2 CH 2 C1
  • CH 2 CH CHCH 2 SCH 3 2-furanyl CH 2 CH 2 Si(CH 3 ) 3 CH 2 CH 2 C0 2 CH 3
  • CH 2 CH 2 OCH 2 CH CH 2 CH 2 CH 2 SCH 2 C ⁇ CH CH 2 OCF 3 CH 2 0CH 2 CH 2 C1
  • CH 2 CH CHCH 2 SCH 3 2-furanyl CH 2 CH 2 Si(CH 3 ) 3 CH 2 CH 2 C0 2 CH 3 CH 2 CH 2 CH 2 NHCH 3 3-benzo[b]thienyl CH 2 CH 2 CH 2 CN Ph
  • CH 2 CH 2 OCH 2 CH CH 2 CH 2 CH 2 SCH 2 C--CH CH 2 OCF 3 CH 2 0CH 2 CH 2 C1
  • CH 2 CH CHCH 2 SCH 3 2-furanyl CH 2 CH 2 Si(CH 3 ) 3 CH 2 CH 2 C0 2 CH 3
  • CH 2 CH CHCH 2 SCH 3 2-furanyl CH 2 CH 2 Si(CH 3 ) 3 CH 2 CH 2 C0 2 CH 3
  • CH 2 CH 2 OCH 2 CH CH 2 CH 2 CH 2 SCH 2 CsCH CH 2 OCF 3 CH 2 OCH 2 CH 2 Cl
  • CH 2 CH CHCH 2 SCH 3 2-furanyl CH 2 CH 2 Si(CH 3 ) 3 CH 2 CH 2 C0 2 CH 3
  • CH 2 CH 2 OCH 2 CH CH 2 CH 2 CH 2 SCH 2 CsCH CH 2 OCF 3 CH 2 0CH 2 CH 2 C1
  • CH 2 CH CHCH 2 SCH 3 2-furanyl CH 2 CH 2 Si(CH 3 ) 3 CH 2 CH 2 C0 2 CH 3
  • CH 2 CH 2 OCH 2 CH CH 2 CH 2 CH 2 SCH 2 OCH CH OCF 3 CH 2 0CH 2 CH 2 C1
  • CH 2 CH CHCH 2 SCH 3 2-furanyl CH 2 CH 2 Si(CH 3 ) 3 CH 2 CH 2 C0 2 CH 3
  • CH 2 CH 2 OCH 2 CH CH 2 CH CH 2 SCH 2 C ⁇ CH CH 2 OCF 3 CH 2 0CH 2 CH 2 C1
  • CH 2 CH CHCH 2 SCH 3 2-furanyl CH 2 CH 2 Si(CH 3 ) 3 CH 2 CH 2 C0 2 CH 3
  • CH 2 CH CHCH 2 SCH 3 2-furanyl CH 2 CH 2 Si(CH 3 ) 3 CH 2 CH 2 C0 2 CH 3
  • CH 2 CH 2 OCH 2 CH CH 2 CH 2 CH 2 SCH 2 CsCH CH 2 OCF 3 CH 2 0CH 2 CH 2 C1
  • CH 2 CH CHCH 2 SCH 3 2-furanyl CH 2 CH 2 Si(CH 3 ) 3 CH 2 CH 2 C0 2 CH 3
  • CH 2 CH 2 OCH 2 CH CH 2 CH 2 CH 2 SCH 2 C ⁇ CH CH 2 OCF 3 CH 2 0CH 2 CH 2 C1
  • CH 2 CH CHCH 2 SCH 3 2-furanyl CH 2 CH 2 Si(CH 3 ) 3 CH 2 CH 2 C0 2 CH 3
  • CH 2 CH 2 OCH 2 CH CH CH 2 CH 2 SCH 2 C ⁇ CH CH 2 OCF 3 CH 2 0CH 2 CH 2 C1
  • CH 2 CH CHCH 2 SCH 3 2-furanyl CH 2 CH 2 Si(CH 3 ) 3 CH 2 CH 2 C0 2 CH 3
  • CH 2 CH 2 OCH 2 CH CH 2 CH 2 CH 2 SCH 2 C ⁇ CH CH 2 OCF 3 CH 2 0CH 2 CH 2 C1
  • CH 2 CH CHCH 2 SCH 3 2-fi ⁇ ranyl CH 2 CH 2 Si(CH 3 ) 3 CH 2 CH 2 C0 2 CH 3
  • CH 2 C ⁇ CBr CH 2 CH 2 OCH 2 C CH CH 2 OCH 2 CH 3 CH 2 CH 2 OCH 3

Abstract

Compounds of Formulae (I) and (II), and their N-oxides and agriculturally suitable salts, are disclosed which are useful as fungicides wherein Z is O, S(O)n or NR5; n is 0, 1, or 2; Q is O or S; G is, together with the two linking carbons, a substituted fused phenyl or a substituted fused 5- or 6-membered aromatic heterocyclic ring; and R?1, R2 and R5¿ are as defined in the disclosure. Also disclosed are compositions containing the compounds of Formulae (I) and (II) and a method for controlling plant diseases caused by fungal plant pathogens which involves applying an effective amount of a compound of Formulae (I) or (II).

Description

TITLE
FUSED BICYCLIC OXAZINONE AND THIAZINONE FUNGICIDES
BACKGROUND OF THE INVENTION This invention relates to certain oxazinones and thiazinones, their N-oxides, agriculturally suitable salts and compositions, 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 compounds that are more effective, less costly, less toxic, environmentally safer or have different modes of action.
Certain 2-(trifluoromethyl)imino benzoxazinones, benzothiazinones, and quinazolinones have previously been cited as fungicides (DE 2218301).
Additional benzoxazinones, benzothiazinones and quinazolinones are reported in the literature (Tetrahedron, 1967, 23 (11), 4449). Additional fused phenyl, fused pyridizine or fused imidazole compounds have been reported (WO91/19707; WO90/06921; Arch. Pharm.
(Weinheim), 1988, 321, 527; Tetrahedron Lett, 1984, 3837; Chem. Ber., 1980, 113, 2818;
JP54020504; Chem. Pap, 1992, 46(6), 405; US 3470168; DE 1807165 and JP47017781).
Additional fused imidazole or fused thiophene compounds have been reported (Bull. Chem. Soc. Fr., 1974, 9-10(Pt. 2), 2161; Khim.-Farm. Zh. 1972, 6(7), 13; Khim.-Farm. Zh. 19769,
3(7), 4; Khim.-Farm. Zh. 1969, 3(8), 21 and Khim.-Farm. Zh. 1968, 2(2), 18. Additional fused pyridine or fused pyrimidine compounds have been reported (Arch. Immunol. Ther.
Exp., 1989, 37(3-4), 487; Farmaco. Ed. Sci., 1986, 41, 899 and 964; Farmaco. Ed. Sci.,
1982, 37(4), 247 and 266; Pol. J. Chem., 1980, 54(10), 1875; Acta Pol. Pharm., 1981, 38(2), 145; PL122833; WO97/17970 and Collect. Czech. Chem. Commun., 1983, 48(12), 3426).
Additional fused phenyl compounds have been reported (Chem. Ber., 1964, 97, 3036).
Additional compounds are reported in the literature (Heterocycles, 1984, 709; Khim.
Geterosikl. Soedin., 1984, 20(3), 407; Arch. Pharm. (Weinheim), 1982, 315, 324; J.
Heterocycl. Chem., 1991, 28, 133; J. Org. Chem., 1994, 59, 7688; Chem. Letters, 1990, 2205; Chem., Ber., 1971, 104, 3757; Pharmazie, 1969, 24, 100; J. Org. Chem., 1971, 36,
157; J. Heterocycl. Chem., 1985, 22, 193; Chem. Ber., 1982, 115, 1662; andJ. Chem. Soc,
1957, 2159).
SUMMARY OF THE INVENTION This invention is directed to compounds of Formula I and Formula II, including all geometric and stereoisomers, N-oxides, and agriculturally suitable salts thereof, agricultural compositions containing them and their use as fungicides:
Figure imgf000004_0001
π
wherein
Z is O, S(O)n orNR5; n is O, l, or 2; Q is O or S;
G is, together with the two linking carbons, a substituted fused phenyl or a substituted fused 5- or 6-membered aromatic heterocychc ring; each R1 and R2 is independently Ci -Ci o alkyl optionally substituted with NR6R7, nitro, cyano, CO R6, one or more hydroxy, or R11; C3-C10 alkenyl; C3-C10 alkynyl; Cι-C10 haloalkyl; C3-C10 haloalkenyl; C3-C10 haloalkynyl;
C2-C10 alkoxyalkyl; C2-C10 alkylthioalkyl; C2-C10 alkylsulfonylalkyl; C4-C10 alkenyloxyalkyl; C4-C10 alkynyloxyalkyl; C4-C10 alkenylthioalkyl; C4-CK) alkynylthioalkyl; C -C10 haloalkoxyalkyl; C4-C10 alkoxyalkenyl; C4-C10 alkylthioalkenyl; C4-C10 trialkylsilylalkyl; C4-C10 alkoxy; COR6; CO2R6; or RH; or
R1 and R2 in Formula II can be taken together as -CH2CH CH2CH2-,
-CH2(CH2)3CH2-, -CH2CH2OCH2CH2-, -CH2CH(Me)CH2CH(Me)CH2- or -CH2CH(Me)OCH(Me)CH2-; R5 is CrC4 alkyl; each R6 and R7 is independently hydrogen; Ci -C4 alkyl optionally substituted with
R^ or RUj or each pair of R6 and R7, when attached to the same nitrogen atom, can be taken together as -CH2CH2CH2CH2-, -CH2(CH2)3CH2-, -CH2CH2OCH2CH2-, -CH2CH(Me)CH2CH(Me)CH2- or -CH2CH(Me)OCH(Me)CH2-; and each R1 * is independently an optionally substituted phenyl; an optionally substituted
3-, 4-, 5- or 6-membered non-aromatic carbocyclic ring, an optionally substituted 8-, 9- or 10-membered fused carbobicyclic or fused heterobicyclic ring system; or an optionally substituted 3-, 4-, 5- or 6-membered heteromonocyclic ring; wherein said heterobicyclic ring systems and heteromonocyclic rings may be aromatic or nonaromatic and contain 1 to 4 heteroatoms independently selected from the group nitrogen, oxygen and sulfur, provided that each heterobicyclic ring system and heteromonocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs, and wherein each heterobicyclic ring system and heteromonocyclic ring is bonded through a ring carbon atom; provided that i) when G is a fused phenyl ring, then R2 is other than trifluoromethyl or cyclohexyl; ii) when G in Formula II is, together with the two linking carbons, a fused phenyl or a fused pyridizine and R1 and R2 are taken together as -CH2CH2CH2CH2-, -CH2(CH2)3CH2-, -CH2CH2OCH2CH2-, -CH2CH(Me)CH2CH(Me)CH2- or -CH2CH(Me)OCH(Me)CH2-, then G must be substituted with at least two groups, one of which must be other than /-propyl, methoxy or NO2; iii) when G in Formula II is, together with the two linking carbons, a fused phenyl, fused pyridizine or fused imidazole and R1 is allyl, Ci to C4 alkyl or unsubstituted phenyl, then G must be substituted with at least two groups, one of which must be other than methyl or methoxy; iv) when G in Formula II is, together with the two linking carbon atoms, a fused imidazole or fused thiophene and R1 is methyl, ethyl or allyl, then G cannot be substituted with methyl or CO2CH3; v) when G is , together with the two linking carbons, a fused pyridine or pyrimidine and Z is oxygen or sulfur, then G cannot be substituted with methyl, unsubstituted phenyl or morpholino; and vi) when G in Formula II is, together with the two linking carbon atoms, a fused phenyl ring and R1 and R2 are either both methyl or taken together to form -CH2CH2OCH2CH2-, then G cannot be substituted with methyl, CH3CO2- or unsubstituted phenyl.
DETAILS OF THE INVENTION In the above recitations, the term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl" includes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, z'-propyl, or the different butyl, pentyl or hexyl isomers. The term "Me" means methyl. "Alkenyl" includes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers. "Alkenyl" also includes polyenes such as 1 ,2-propadienyl and 2,4-hexadienyl. "Alkynyl" includes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers. "Alkynyl" can also include moieties comprised of multiple triple bonds such as 2,5-hexadiynyl. "Alkoxy" includes, for example, methoxy, ethoxy, «-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers. "Alkoxyalkyl" denotes alkoxy substitution on alkyl. Examples of "alkoxyalkyl" include CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2CH2OCH2 and CH3CH OCH2CH2. "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 CH2=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 and hexylthio isomers. "Alkylthioalkyl" denotes alkylthio substitution on alkyl. Examples of "alkylthioalkyl" include CH3SCH2, CH3SCH2CH2, CH3CH2SCH2, CH3CH2CH2CH2SCH2 and CH3CH2SCH2CH2. 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. "Alkenylthioalkyl", "alkylthioalkenyl" and the like, are defined analogously to the above examples.
"Cycloalkyl" includes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclopentylethyl, and other cycloalkyl moieties bonded to straight-chain or branched alkyl groups. The term "aromatic ring system" denotes fully unsaturated carbocycles and heterocycles in which the polycyclic ring system is aromatic (where aromatic indicates that the Hύckel rule is satisfied for the ring system). The term "aromatic carbocyclic ring system" includes fully aromatic carbocycles and carbocycles in which at least one ring of a polycyclic ring system is aromatic (where aromatic indicates that the Hύckel rule is satisfied). The term "nonaromatic carbocyclic ring system" denotes fully saturated carbocycles as well as partially or fully unsaturated carbocycles where the Hύckel rule is not satisfied by any of the rings in the ring system. The term "fused carbobicyclic ring system" includes a ring system comprised of two fused rings in which all ring atoms are carbon and can be aromatic or non aromatic, as defined above. The term "aromatic heterocychc ring system" includes fully aromatic heterocycles and heterocycles in which at least one ring of a polycyclic ring system is aromatic (where aromatic indicates that the Hύckel rule is satisfied). The term "nonaromatic heterocychc ring system" denotes fully saturated heterocycles as well as partially or fully unsaturated heterocycles where the Hύckel rule is not satisfied by any of the rings in the ring system. The heterocychc ring systems can be attached through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen. The term "heteromonocyclic ring" includes ring systems comprised of a single ring in which one ring atom is not carbon and can be aromatic or nonaromatic, as defined above. The term "fused heterobicyclic ring system" includes a ring system comprised of two fused rings in which at least one ring atom is not carbon and can be aromatic or non aromatic, as defined above.
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, CC13C≡C and FCH2C≡CCH2. Examples of "haloalkoxy" include CF3O, CCl3CH2O, HCF2CH2CH2O and CF3CH2O. Examples of "haloalkylthio" include CC13S, CF3S, CC13CH2S and C1CH2CH2CH2S. Examples of "haloalkoxyalkyl" include CF3OCH2, ClCH2CH2OCH2CH2, Cl3CCH2OCH2 as well as branched alkyl derivatives.
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 well known by one skilled in the art. These methods include 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 Heterocychc 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 Heterocychc Chemistry, vol. 43, pp 149-161, A. R. Katritzky, Ed., Academic Press; M. Tisler and B. Stanovnik in Advances in Heterocychc Chemistry, vol. 9, pp 285-291, A. R. Katritzky and A. J. Boulton, Eds., Academic Press; and G. W. H. Cheeseman and E. S. G. Werstiuk in Advances in Heterocychc Chemistry, vol. 22, pp 390-392, A. R. Katritzky and A. J. Boulton, Eds., Academic Press. A fused phenyl group that has an iodine attached to the sequence of four carbon atoms in the phenyl ring that are not common to the other ring respectively shown in Formula I and Formula II, and a fused 5- or 6-membered aromatic heterocychc ring that has an iodine attached to the sequence of atoms in the aromatic heterocychc ring that are not common to the other ring respectively shown in Formula I and Formula II are examples of G rings that provide Formula I and Formula II compounds with fungicidal activity. The term "substituted fused phenyl" (see G) refers to a fused phenyl that has at least one non-hydrogen group attached to the sequence of four carbon atoms in the phenyl ring that are not common to the other ring respectively shown in Formula I and Formula II, and that does not extinguish the fungicidal activity possessed by the iodo-substituted compounds. Similarly, the term "substituted fused aromatic heterocychc ring" (see G) refers to a fused aromatic heterocychc ring that has at least one non-hydrogen group attached to the sequence of atoms in the aromatic heterocychc ring that are not common to the other ring respectively shown in Formula I and Formula II, and that does not extinguish the fungicidal activity possessed by the iodo-substituted compounds. Examples of substituted fused phenyl rings and substituted fused aromatic heterocychc rings are those wherein said rings are substituted with R3 and optionally substituted with R4, wherein
R3 is halogen; C2-C8 alkyl or C2-C8 alkenyl, each optionally substituted with hydroxy, cyano or CO2R6; CH2OH; CH2CN; CH2CO2R6; C3-C8 cycloalkyl; C2-C8 alkynyl; Cι-C8 haloalkyl; C3-C8 haloalkenyl; C3-Cg haloalkynyl; Cι-C alkoxy; Ci-Cg haloalkoxy; C3-Cg alkenyloxy; C3-Cg alkynyloxy; Cι-C8 alkylthio; CrC8 alkylsulfonyl; C2-C8 alkoxyalkyl; C3-C8 trialkylsilyl; NR6R7; C5-C8 trialkylsilylalkynyl; or phenyl optionally substituted with at least one R12; SF5; CrC8 haloalkylthio; or SCN;
R4 is halogen; C1-C4 alkyl, C1-C4 haloalkyl; C1-C4 alkoxy or C1-C4 haloalkoxy; and Rl2 (see R3) js halogen, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, nitro or cyano. Of note are compounds of Formula I, N-oxides and agriculturally suitable salts thereof, wherein G is, together with the two linking carbons, a fused phenyl, substituted with R3 and optionally substituted with R4. Also of note are compounds of Formula II, N-oxides and agriculturally suitable salts thereof wherein G is, together with the two linking carbons, a fused phenyl, substituted with R3 and optionally substituted with R4. Also of note are compounds of Formula I, N-oxides and agriculturally suitable salts thereof, wherein G is, together with the two linking carbons, a fused 5- or 6-membered heteroaromatic ring, substituted with R3 and optionally substituted with R4. Also of note are compounds of
Formula II, N-oxides and agriculturally suitable salts thereof, wherein G is, together with the two linking carbons, a fused 5- or 6-membered heteroaromatic ring, substituted with R3 and optionally substituted with R4.
Examples of substituted fused phenyl rings (G-22) and substituted fused aromatic heterocychc rings (G- 1 to G-21 ) wherein said rings are substituted with R3 and optionally substituted with R4 include the ring systems illustrated in Exhibit 1. As with the carbon atoms in the ring, the nitrogen atoms that require substitution to fill their valence are substituted with hydrogen or with R3 or R4. Although the R3 and R4 groups are shown in the structures G-l to G-22, it is noted that R4 does not need to be present since it is an optional substituent. In the exemplified G groups, the upper right bond is attached to the available carbon adjacent to carbon 4 of Formula I and/or Formula II and the lower right bond is attached to the available carbon adjacent to the Z group of Formula I and/or Formula II.
The wavy line indicates that the G ring is fused to the heterocychc ring as illustrated below.
Figure imgf000009_0001
II
Exhibit 1
Figure imgf000009_0002
G-ll G-12
Figure imgf000009_0003
As noted above, each R11 is independently an optionally substituted phenyl ring, one of certain optionally substituted 3-, 4-, 5- or 6-membered carbomonocyclic rings, one of certain optionally substituted 8-, 9- or 10-membered fused carbobicychc or fused heterobicyclic ring systems, or one of certain optionally substituted 3-, 4-, 5- or 6-membered heteromonocyclic rings. The term "optionally substituted" in connection with these R11 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 R11 groups are those that are optionally substituted with R8, R9 and/or R10, wherein R8 is C i -C6 alkyl; C { -C6 alkoxy; C j -C6 haloalkyl; halogen; C2-C8 alkynyl;
C^Cg alkylthio; phenyl or phenoxy each optionally substituted with at least one R12; cyano; nitro; C^Cg haloalkoxy; Cχ-C-6 haloalkylthio; C2-C6 alkenyl; C2-C6 haloalkenyl; acetyl; CO2Me; or N(CrC2 alkyl)2; R9 is methyl; ethyl; methoxy; methylthio; halogen; CO2(CrC3 alkyl); C(O)NR6R7 or trifluoromethyl; and
R10 is halogen.
Examples of optionally substituted phenyl (Y-102), optionally substituted 3-, 4-, 5- or 6-membered non-aromatic carbocyclic rings (Y-103 through Y-109), optionally substituted 8-, 9- or 10-membered fused carbobicychc or fused heterobicyclic ring systems (Y-66 through Y-90 and Y-101) and optionally substituted 3-, 4-, 5- or 6-membered heteromonocyclic ring (Y-l through Y-65 and Y-91 through Y-100), wherein said rings are optionally substituted with R8, R9 and/or R10 include the ring systems illustrated in Exhibit 2. As with the carbon atoms in the ring, the nitrogen atoms that require substitution to fill their valence are substituted with hydrogen or with R8, R9 or R10. Although the R8, R9 and/or R10 groups are shown in the structures Y-l to Y-109, it is noted that they do not need to be present since they are optional substituents.
Exhibit 2
Figure imgf000010_0001
Figure imgf000011_0001
Y-6 Y-7 Y-8 Y-9 Y-10
Figure imgf000011_0002
Y-ll Y-l 2 Y-13 Y-14 Y-15
Figure imgf000011_0003
Y-21 Y-22 Y-23 Y-24 Y-25
Figure imgf000011_0004
Y-26 Y-27 Y-28 Y-29 Y-30
Figure imgf000011_0005
Y-31 Y-32 Y-33 Y-34 Y-35
Figure imgf000012_0001
Figure imgf000012_0002
Y46 Y-47 Y-48 Y-49 Y-50
Figure imgf000012_0003
Figure imgf000012_0004
Y-56 Y-57 Y-58 Y-59 Y-60
Figure imgf000013_0001
Y-61 Y-62 Y-63 Y-64 Y-65
Figure imgf000013_0002
Y-67 Y-68 Y-69
Figure imgf000013_0003
Y- 70 Y-71 Y-72 Y-73
Figure imgf000013_0004
Y-74 Y-75 Y-76 Y-77
Figure imgf000013_0005
Y-78 Y-79 Y-80 Y-81
Figure imgf000014_0001
Y-82 Y-83 Y-84 Y-85
Figure imgf000014_0002
Y-86 Y-87
Figure imgf000014_0003
Figure imgf000014_0004
Figure imgf000014_0005
Y-96 Y-97 Y-98 Y-99 Y-100
Figure imgf000015_0001
Y-101 Y-l 02
Figure imgf000015_0002
The total number of carbon atoms in a substituent group is indicated by the "Cj-Cj" prefix where i and j are numbers from 1 to 10. For example, Cj-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. In the above recitations, when a compound of Formula I or II is comprised of one or more heterocychc rings, all substituents are attached to these rings through any available carbon or nitrogen by replacement of a hydrogen on said carbon or nitrogen.
When a compound is substituted with a substituent bearing a subscript that indicates the number of said substituents can exceed 1, said substituents (when they exceed 1) are independently selected from the group of defined substituents. Further, when the subscript indicates a range, e.g. (R)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 R5 or R6, then, when this substituent is taken as hydrogen, it is recognized that this is equivalent to said group being unsubstituted.
Compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers, atropisomers and geometric isomers. One skilled in the art will appreciate that one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate, enrich, and/or to selectively prepare said stereoisomers. Accordingly, the present invention comprises compounds selected from Formula I, N-oxides and agriculturally suitable salts thereof. The compounds of the invention may be present as a mixture of stereoisomers, individual stereoisomers, or as an optically active form.
The salts of the compounds of the invention include acid-addition salts with inorganic or organic acids such as hydrobromic, hydrochloric, nitric, phosphoric, sulfuric, acetic, butyric, fumaric, lactic, maleic, malonic, oxalic, propionic, salicylic, tartaric, 4-toluenesulfonic or valeric acids. The salts of the compounds of the invention also include those formed with organic bases (e.g., pyridine, ammonia, or triethylamine) or inorganic bases (e.g., hydrides, hydroxides, or carbonates of sodium, potassium, lithium, calcium, magnesium or barium) when the compound contains an acidic group such as a carboxylic acid or phenol.
Preferred compounds for reasons of better activity and/or ease of synthesis are: Preferred 1. Compounds of Formula I and II above, N-oxides and agriculturally suitable salts thereof, wherein each fused phenyl and fused heterocychc ring of G is substituted with R3 and is optionally substituted with R4; and each phenyl, fused carbobicychc ring system, fused heterobicyclic fused ring system, and heteromonocyclic ring of R l is optionally substituted with R8, optionally substituted with R9 and optionally substituted with R10; wherein
R3 is halogen; C2-C8 alkyl or C2-C8 alkenyl, each optionally substituted with hydroxy, cyano or CO2R6; CH2OH; CH2CΝ; CH2CO2R6; C3-C8 cycloalkyl; C2-C8 alkynyl; CrC8 haloalkyl; C3-C8 haloalkenyl; C3-C8 haloalkynyl; C Cg alkoxy; Cj-C8 haloalkoxy; C3-C8 alkenyloxy; C3-C alkynyloxy; Cj-Cs alkylthio;
CrC8 alkylsulfonyl; C2-C8 alkoxyalkyl; C3-C8 trialkylsilyl; NR6R7; C5-C8 trialkylsilylalkynyl; or phenyl optionally substituted with at least one R12; SF5; CrC8 haloalkylthio; or SCN; R4 is hydrogen, halogen, C1-C4 alkyl, 0^4 haloalkyl, C1-C4 alkoxy or 1-C4 haloalkoxy; each R8 is independently Cj-C6 alkyl; Cj-Cg alkoxy; C C6 haloalkyl; halogen; C2-C8 alkynyl; Cj-C6 alkylthio; phenyl or phenoxy each optionally substituted with at least one R12; cyano; nitro; C^-Cg haloalkoxy; C Cg haloalkylthio; C2-C6 alkenyl; Gj-Cg haloalkenyl; acetyl; CO2Me; or N(C C2 alkyl)2; each R9 is independently methyl, ethyl, methoxy, methylthio, halogen,
CO2(CrC3 alkyl), C(O)NR6R7 or trifluoromethyl; each RlO is independently halogen; and each Rl2 is independently halogen, Cj^ alkyl, C1-C4 alkoxy, C1-C4 haloalkyl, nitro or cyano. Preferred 2. Compounds of Preferred 1 above, N-oxides and agriculturally suitable salts thereof, wherein G is, together with the two linking carbons, a fused phenyl, substituted with
R3 and optionally substituted with R4; each Rl and R2 is independently CrC5 alkyl; C3-C6 cycloalkyl; C3-C5 alkenyl; C3-C5 alkynyl; CrC5 haloalkyl; C3-C5 haloalkenyl; C3-C5 haloalkynyl; C2-C5 alkoxyalkyl; C2-C5 alkylthioalkyl; C4-C7 cycloalkylalkyl, phenyl or thienyl, each optionally substituted with R8,
R9 and RlO; and Z is O. Preferred 3. Compounds of Preferred 1 above, N-oxides and agriculturally suitable salts thereof, wherein G is, together with the two linking carbons, a fused thienyl or fused pyridinyl, each optionally substituted with R3 and optionally substituted with R4; each Rl and R2 is independently Cj-C5 alkyl; C3-C6 cycloalkyl; C3-C5 alkenyl; C3-C5 alkynyl; C!-C5 haloalkyl; C3-C5 haloalkenyl; C3-C5 haloalkynyl; C2-C5 alkoxyalkyl; C2-C5 alkylthioalkyl; C4-C7 cycloalkylalkyl, phenyl or thienyl, each optionally substituted with R8,
R9 and Ri0; and Z is O or S. Preferred 4. Compounds of Prefeπed 1 above, N-oxides and agriculturally suitable salts thereof, wherein R3 is halogen, C2-C8 alkynyl or Cj-C8 haloalkyl; and
R4 is halogen, C2-C8 alkynyl or Cj-Cs haloalkyl. Prefeπed 5. Compounds of Prefeπed 2 above, N-oxides and agriculturally suitable salts thereof, wherein R3 is 6-halogen and R4 is 8-halogen.
Specifically preferred for fungicidal activity and/or ease of synthesis is:
2,3-dihydro-6-iodo-3-propyl-2-(propylimino)-4H- 1 ,3-benzoxazin-4-one. This invention also relates to fungicidal compositions comprising fungicidally effective amounts of the compounds of the invention and at least one of a surfactant, a solid diluent or a liquid diluent. The preferred compositions of the present invention are those which comprise the above preferred compounds.
This invention also relates to a method for controlling 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 compounds of the invention (e.g., as a composition described herein). The prefeπed methods of use are those involving the preferred compounds describe above.
Of note are compounds of Formula I and Formula II, including all geometric and stereoisomers, N-oxides, and agriculturally suitable salts thereof, agricultural compositions containing them and their use as fungicides:
Figure imgf000018_0001
i π
wherein
Z is O, S(O)n orΝR5; n is 0, 1, or 2;
Q is O or S; G is, together with the two linking carbons, a substituted fused phenyl or a substituted fused 5- or 6-membered aromatic heterocychc ring; each Rl and R2 is independently CrC10 alkyl optionally substituted with NR6R7, nitro, cyano, CO2R6, one or more hydroxy, or Rl l; C3-C6 cycloalkyl; C3-Cκ) alkenyl; C -Cιo alkynyl; C^C^ haloalkyl; C3-C10 haloalkenyl; C3-CJO haloalkynyl; C2-C10 alkoxyalkyl; C2-C10 alkylthioalkyl; C2-CJO alkylsulfonylalkyl; C -C10 cycloalkylalkyl; C -C10 alkenyloxyalkyl; C4-C10 alkynyloxyalkyl; C -C10 alkenylthioalkyl; C4-CK) alkynylthioalkyl; C2-C 10 haloalkoxyalkyl; C4-C γ 0 alkoxyalkenyl; C4-C j 0 alkylthioalkenyl;
C4-C10 trialkylsilylalkyl; C4-C10 alkoxy; COR6; CO2R6; or RU; or the pair of R1 and R2 in Formula II can be taken together as -CH2CH2CH2CH -, -CH2(CH2)3CH2-, -CH2CH2OCH2CH2-, -CH2CH(Me)CH2CH(Me)CH2- or -CH2CH(Me)OCH(Me)CH2-; R5 is hydrogen or C1-C4 alkyl; each R6 and R7 is independently hydrogen; C1-C4 alkyl optionally substituted with
RU; or RH; or each pair of R6 and R7, when attached to the same nitrogen atom, can be taken together as -CH2CH2CH2CH2-, -CH2(CH2)3CH2-, -CH2CH2OCH2CH2-, -CH2CH(Me)CH2CH(Me)CH2- or -CH2CH(Me)OCH(Me)CH2-; and each Rl is independently optionally substituted phenyl; an optionally substituted 8-, 9- or 10-membered fused carbobicychc or fused heterobicyclic ring system; or an optionally substituted 3-, 4-, 5- or 6-membered heteromonocyclic ring; wherein said heterobicyclic ring systems and heteromonocyclic rings contain 1 to 4 heteroatoms independently selected from the group nitrogen, oxygen and sulfur, provided that each heterobicyclic ring system or heteromonocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs, and wherein said heterobicyclic ring system or heteromonocyclic ring is bonded through a ring carbon atom; provided that the requirements of provisos i) through vi) are met. Of particular note are these compounds of note wherein the fused G rings are substituted with R3 as defined above or NO2, and are optionally substituted with R4 as defined above.
The compounds of Formula I can be prepared by one or more of the following methods and variations as described in Schemes 1-23. The definitions of G, Q, R1, R2, R5 and Z in the compounds of Formulae 1-24 below are as defined above in the Summary of the Invention. Compounds of Formulae la-Id are various subsets of the compounds of Formula I and all substituents for Formulae la-Id are as defined above for Formula I.
Figure imgf000019_0001
i π
Compounds of Formula la, a subset of compounds of Formula 1 wherein Z is O and Q is O, can be prepared from precursors of Formula 1 as illustrated in Scheme 1 below.
Scheme 1
Figure imgf000019_0002
2 la
The reaction may be conducted in a fashion analogous to that described in Pharmazie, 1969, 24, 100. The transformation can be accomplished in a variety of solvents such as DMF, dieththyl ether, THF, dioxane, etc., at temperatures ranging from ambient to reflux for 2 to 48 hours. Workup and purification can be achieved via concentration to dryness and subsequent silica gel chromatography of the resulting residue to deliver la.
Amines of Formula 2 are commercially available, whereas compounds for Formula 1 are accessible as shown in Scheme 2.
Scheme 2
Figure imgf000020_0001
Such cyclizations have been cited in the art (J. Heterocychc Chem., 1994, 31, 1589; J. Med. Chem., 1978, 21, 1178; Pharmazie, 1974, 29, 681). The reaction is usually conducted in ethereal solvents such as diethyl ether, THF, dioxane, or glyme for 2-48 hours at temperatures ranging from ambient to 150 °C. Bases such as sodium hydride, sodium methoxide, or triethylamine may be added to facilitate the cychzation. Workup is achieved by concentrating the reaction to dryness in vacuo, followed by partitioning between dilute aqueous acid and a water-immiscible solvent. Separation of the organic phase, following by drying (Na2SO4, anhydrous) and concentration in vacuo delivers the crude product 1 which may be further purified via recrystallization or trituration using appropriate solvents. Intermediate materials of Formula 3 are obtained from the hydroxyacids of Formula 4 and amines of Formula 5 as shown in Scheme 3 below.
Scheme 3
Figure imgf000020_0002
4
The acids of Formula 4 are first converted to the coπesponding acid chlorides using thionyl chloride or phosphorous pentachloride in accordance with similar methods described in J. Amer. Chem. Soc. , 1906, 28, 111 , and J. Med. Chem. , 1983, 26, 765. The reaction is usually conducted in an inert halocarbon or hydrocarbon solvent (i.e., benzene, chlorobenzene or CH2C1 ) at temperatures ranging from ambient to reflux for 0.25 to 2 hours. After concentration in vacuo, the crude residue may then be treated with the desired amines of Formula 5 for 1-48 hours in an appropriate solvent (THF, dioxane or DMF) at temperatures ranging from ambient to reflux. The reaction mixture is then poured into a water-immiscible solvent and extracted with dilute aqueous HC1. Separation of the organic phase and concentrated in vacuo delivers the crude product of Formula 3 which may further purified via recrystallization or trituration using appropriate solvents.
Hydroxy acids of Formula 4 are either commercially available or accessible using methods cited in the literature (J. Org. Chem., 1954, 19, 1633; Monatsh. Chem., 1950, 81, 83; J. Heterocycl. Chem., 1986, 23, 1465; Hoppe-Seyler's Z. Physiol. Chem., 1957, 306, 49). Amines of Formula 5 are commercially available.
Compounds of Formula Ila, a subset of compounds of Formula II wherein Z is O and Q is O, are assembled from precursors of Formula 7 as shown in Scheme 4.
Scheme 4
Figure imgf000021_0001
Such transformations are known in the art (J. Heterocycl. Chem., 1991, 28, 133). The reaction can be carried out in a variety of solvents such as THF, diethyl ether, benzene, toluene or acetone at temperatures ranging from ambient to reflux for 1 to 48 hours. The crude, desired product Ila is obtained following concentrated in vacuo of the reaction mixture. Purification may be achieved through trituration or silica gel chromatography using appropriate solvents.
Amines of Formula 6 are either commercially available, or prepared using known means. Compounds of Formula 7 are readily prepared from the esters of Formula 8 as depicted in Scheme 5 and described inJ. Heterocycl. Chem., 1991, 28, 133.
Scheme 5
Figure imgf000021_0002
Alk is Methyl or Ethyl
The reaction is conducted by stirring a mixture of a compound of Formula 8, cyanogen bromide, and a suitable base (i.e. Et3N, DBU or Na2CO3) in a suitable solvent at temperatures ranging from 0 °C to reflux for 1 to 48 hours. Suitable solvents for this reaction include acetone, benzene, toluene or dioxane. The desired product may be isolated from the reaction mixture by addition of IN HCl and filtration. The Compound of Formula 7 so obtained may be additionally purified via trituration or recrystallization using appropriate solvents.
Compounds of Formula 8 can be assembled from compounds of Formula 4 using the procedure outlined in Scheme 3 above, with the exception that methanol or ethanol are utilized in place of the amines Formula 5.
Scheme 6
Figure imgf000022_0001
Alk is Methyl or Ethyl
Compounds of Formulae la and Ila can alternatively be produced via reaction of compounds of Formula 9 with electrophiles of Formula 10 (Scheme 7). Similar approaches are known in the art (J. Heterocycl. Chem., 1991, 28, 131).
Scheme 7
Figure imgf000022_0002
la
Figure imgf000022_0003
Ha
The reaction can be run in solvents such as DMF, THF, dioxane, or chloroform with bases such as triethylamine, DBU, sodium hydride, potassium carbonate, or sodium carbonate at temperatures ranging from 0 °C to reflux. Upon completion, the reaction mixture is poured into water and extracted with a water-immiscible solvent. The organic phase is then separated, dried (anhydrous Na2SO4), and concentrated in vacuo. The crude isomers of Formulae la and Ila so obtained can be separated by column chromatography to afford the pure, desired compounds.
Electrophiles of Formula 10 are either commercially available or can be readily prepared by one skilled in the art.
Compounds of Formula 9 are readily prepared from compounds of Formula 7 using the method outlined in Scheme 4 above, with the exception that amines of Formula 2 are utilized in place of amines of Formula 6 (Scheme 8).
Scheme 8
Figure imgf000023_0001
7 9
Alk is Methyl or Ethyl
Compounds of Formula lb, a subset of compounds of Formula I wherein Z is S and Q is O, are prepared by reacting precursors of Formula 11 with amines of Formula 2 (Scheme 9).
Scheme 9
Figure imgf000023_0002
11 lb
This transformation can be conducted according to the protocol outlined in Scheme 1 above for the analogous conversion of compounds of Formula 1 to compounds of Formula la and cited in Pharmazie, 1967, 22, 611 and Pharmazie, 1969, 24, 100.
Precursors of Formula 11 can be assembled from amides of Formula 12 via base- promoted cychzation with carbon disulfide (Scheme 10).
Scheme 10
Figure imgf000023_0003
X is halogen The reaction is performed in dioxane, DMF or THF in the presence of 1-3 equivalents of a suitable base and 1-2 equivalents of carbon disulfide. Suitable bases for this transformation include sodium hydride, triethylamine, or 1,8-diazabicyclo 5.4.0]undec-7ene (DBU). A mixture of a compound of Formula 12 and CS2 in a small amount of suitable solvent is added to a mixture of suitable base in the same solvent. The addition is conducted so as to maintain a reaction temperature below 45 °C. The resulting melange is stirred at ambient temperatures for 12 to 48 hours, at which time the reaction is quenched with saturated ammonium chloride (aqueous). The precipitated product is filtered, dried and may be utilized without further purification. However, additional purification can be achieved through trituration or recrystallization using an appropriate solvent.
Amides of Formula 12 are readily prepared from acid chlorides of Formula 13 by treatment with amines of Formula 5 as depicted in Scheme 11.
Scheme 11
Figure imgf000024_0001
Such transformations are well known in the art and may be accomplished by several methods (Indian J. Chem. Sect B., 1990, 29, 111; Arch, Pharm. , 1956, 289, 651 ; Reel. Trav. Chem. Pays-Bas, 1900, 19, 56; J. Org. Chem., 1958, 23, 1403; J. Med. Chem., 1997, 40, 2674; Synthesis, 1997, 4, 431; Chem. Pharm. Bull, 1995, 43, 693).
Acyl chlorides of Formula 13 are either commercially available, or can be prepared as cited in the literature (see J. Prakt. Chem., 1937, 148, 13; Nippon Kagaku Zasshi, 1958, 79, 1366; J. LiebigsAnn. Chem., 1936, 17, 27; J. Med. Chem., 1983, 26, 765; J. Org. Chem., 1995, 60, 2292; J. Chem. Res. Miniprint, 1984, 12, 3485).
In certain instances, the syntheses of compounds of Formula lb are advantageously achieved through cychzation of compounds of Formula 14 as shown in Scheme 12.
Scheme 12
Figure imgf000024_0002
14 X is Halogen The cychzation may be run either neat or in solvents such as DMF, toluene, dioxane or acetonitrile at temperatures ranging from ambient to reflux for 2 hours to 1 week. The presence of base is optional; suitable bases for this transformation include triethylamine, sodium carbonate, DBU or sodium hydride. The base, when utilized, is present in 1-5 equivalents. Upon completion of the reaction, saturated aqueous ammonium chloride is added until a precipitate forms. The solid so precipitated is filtered, washed with water and dried. Subjection of this material to silica gel chromatography delivers pure lb. In those instances when the cychzation is conducted neat, silica gel chromatography is performed directly on the reaction residue to obtain pure lb.
Intermediates of Formula 14 may be prepared from thioureas of Formula 15 and acid chlorides of Formula 13 as shown in Scheme 13.
Scheme 13
Figure imgf000025_0001
The reaction is performed using equimolar amounts of an acid chloride of Formula 13 and a thiourea of Formula 15 in solvents such as THF, DMF, dioxane, toluene or acetonitrile at temperatures ranging from 0 °C to reflux for 1 to 48 hours. The presence of base is optional; however, when present, 1-5 equivalents of base may be employed. Upon completion of the reaction, the reaction mixture is poured into methanol water and extracted with a water-immiscible solvent. The organic phase is separated, dried over anhydrous a2SO4, and concentrated to a crude residue. Silica gel chromatography of this residue affords a pure compound of Formula 14. Workup may also be achieved via filtration of the reaction mixture through a silica gel plug to deliver the crude compound of Formula 14 which may be utilized without further purification.
In certain instances, the reaction of thioureas of Formula 15 with acid chlorides of Formula 13 directly produces compounds of Formula lb as depicted in Scheme 14.
Scheme 14
Figure imgf000025_0002
I3 X is halogen Transformations such as this have precedence in the art and can be conducted in accordance with the specifications cited therein (J. Org. Chem., 1994, 59, 7688). Thioureas of Formula 15 are either commercially available, or may readily prepared as described in J. Amer. Chem. Soc., 1997, 119, 4882 and Synth. Commun., 1997, 27, 3565.
Compounds of Formula lib, a subset of I wherein Z is S and Q is O, may be synthesized from acid chlorides of Formula 13 via intermediary of acyl isothiocyanates of Formula 16 as in Scheme 15.
Scheme 15
Figure imgf000026_0001
lib
Such transformations are cited in Collect. Czech. Chem. Commun., 1983, 48, 3315 and 3426, which the skilled practitioner may consult for the preparation of compounds of Formula lib via acyl isothiocyanates of Formula 16.
Compounds of Formula Ic, a subset of compounds of Formula I wherein Z is NR5 and Q is O, may be prepared from precursors of Formula 17 and amines of Formula 2 as illustrated in Scheme 16.
Figure imgf000026_0002
Similar transformations are outlined in J. Chem. Soc, 1957, 2159. The protocol for preparing compounds of Formula Ic from precursors of Formula 17 is analogous to those outlined in Schemes 1 and 9 for the preparation of Compounds of Formulae la and lb from the respective thione precursors of Formulae 1 and 11. The skilled practitioner may consult the above sources for protocol regarding the analogous synthesis of compounds of Formula Ic from compounds of Formula 17.
Precursors of Formula 17 are preparable through reaction of amino acids of Formula 18 with isothiocyanates of Formula 19 as prescribed in J. Prakt. Chem., 1897, 55, 133 and Khim. Geterosikl. Soedin., 1986, 22, 1236.
Figure imgf000027_0001
18 17
The reaction is conducted in glacial acetic acid at temperatures ranging from 50-200 °C for 1 to 48 hours using 1-5 molar equivalents of an isothiocyanate of Formula 19. Workup can be accomplished by pouring the reaction mixture into water followed by filtration of the crude precipitate. Recrystallization of the precipitate from an appropriate solvent delivers the precursor of Formula 17.
Isothiocyanates of Formula 19 are either commercially available or preparable from -imines of Formula 5 using well-established methods (see, for example, J. Heterocycl. Chem., 1990, 27, 407). Compounds of Formula 18 can be prepared from amino acids of Formula 20 and alkyl halides or sulfonates using procedures outlined in Chem. Ber., 1906, 39, 3237 orJ. Amer, Chem. Soc, 1946, 68, 1810.
Scheme 18
Figure imgf000027_0002
Amino acids of Formula 20 are available commercially, or readily synthesized by known means (see J. Heterocycl. Chem., 1966, 3, 252; J. Org. Chem., 1952, 17, 547; J. Org. Chem., 1949, 14, 97; Synth. Commun., 1979, 9, 731). The alkyl halides R5-X and sulfonates R5O-SO2-OR5 are commercially available.
In certain instances, compounds of Formula Ic are advantageously prepared from anhydrides of Formula 21 and isothioureas of Formula 22 as cited in J. Heterocycl. Chem., 1985, 22, 193 (Scheme 19).
Figure imgf000028_0001
The anhydride precursors of Formula 21 are prepared from compounds of Formula 23 in Scheme 20 using methods outlined inJ. Med. Chem., 1981, 24, 735; J. Heterocycl. Chem., 1979, 16, 661 and 829, or Chem. Ber., 1995, 128, 627.
Figure imgf000028_0002
Compounds of Formula 23 are either available commercially or prepared from the amino acids 20 using established methods (see Synthesis, 1980, 505).
Isothioureas of Formula 22 are well known in the art and can easily be prepared by the skilled practitioner from the previously described ureas of Formula 15 using procedures cited inJ. Amer. Chem. Soc, 1951, 73, 602; Collect. Czech. Chem. Commun., 1975, 40, 3904; J. Amer. Chem., Soc, 1933, 55, 4986 orJ. Med. Chem., 1992, 35, 3942.
Compounds of Formula lie, a subset of compounds of Formula II wherein Z is NR5 and Q is O, are accessible by reaction of compounds of Formula 24 with amines of Formula 6 as illustrated in Scheme 21.
Figure imgf000028_0003
The transformation can be accomplished according to the previously described protocol for assembling the analogous compounds of Formula Ic from precursors of Formula 17 and amines of Formula 2 (see Scheme 16). Precursors of Formula 24 are obtained from amino acids of Formula 18 according to the method described in Pharmazie, 1984, 39, 868 and depicted in Scheme 22.
Figure imgf000029_0001
Compounds of Formula Id, a subset of compounds of Formula Id wherein Q is S and Z is O, can be prepared from compounds of Formula la as shown in Scheme 23.
Figure imgf000029_0002
Reagent
Ia Id
Treatment of compounds of Formula Ia with phosphorous pentasulfide or Lawesson's reagent [2,4-bis(4-methoxyphenyl)-l,3-dithia-2,4-diphosphetane-2,4-disulfide] in an inert solvent such as dioxane at temperatures ranging from 0 °C to reflux for 0.1-72 hours affords compounds of Formula Id. This procedure is described in US 3,755,582 and incorporated herein by reference. The skilled chemist recognizes that the previously cited materials of Formula Ib-c and Ila-c can also be individually subjected to the reaction conditions alluded to in Scheme 23 for preparation of the coπesponding products wherein Q is S.
It is recognized that some reagents and reaction conditions described above for preparing compounds of Formula I may not be compatible with certain functionalities present in the intermediates. In these instances, the incorporation of protection/deprotection sequences or functional group interconversions into the synthesis will aid in obtaining the desired products. The use and choice of the protecting groups will be apparent to one skilled in chemical synthesis (see, for example, Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic Synthesis, 2nd ed.; Wiley: New York, 1991). One skilled in the art will recognize that, in some cases, after the introduction of a given reagent as it is depicted in any individual scheme, it may be necessary to perform additional routine synthetic steps not described in detail to complete the synthesis of compounds of Formula I. One skilled in the art will also recognize that it may be necessary to perform a combination of the steps illustrated in the above schemes in an order other than that implied by the particular sequence presented to prepare the compounds of Formula I.
One skilled in the art will also recognize that compounds of Formula I and the intermediates described herein can be subjected to various electrophilic, nucleophilic, radical, organometallic, oxidation, and reduction reactions to add substituents or modify existing substituents.
Without further elaboration, it is believed that one skilled in the art using the preceding description can utilize the present invention to its fullest extent. The following Examples are, therefore, to be construed as merely illustrative, and not limiting of the disclosure in any way whatsoever. Percentages are by weight except for chromatographic solvent mixtures or where otherwise indicated. Parts and percentages for chromatographic solvent mixtures are by volume unless otherwise indicated. lH NMR spectra are reported in ppm downfield from tetramethylsilane; s is singlet, d is doublet, t is triplet, q is quartet, m is multiplet, dd is doublet of doublets, dt is doublet of triplets, br s is broad singlet. EXAMPLE 1
Step A: Preparation of Methyl 2-(cvanato)-5-iodobenzoate
To a solution of 5.0 g (19.0 mmol) of methyl-5-iodosalicylate and 2.4 g (20.9 mmol) of cyanogen bromide in 85 mL of acetone was added 2.6 mL (19.0 mmol) of triethylamine at 0 °C. The reaction was allowed to warm to room temperature and stirred for overnight. The reaction mixture was filtered through a sintered glass funnel and the filtrate was treated with 10 mL of IN hydrochloric acid. Water was added to the filtrate until a solid precipitated. The solid was collected by filtration, washed with water, and air dried to provide 4.87 g of methyl 2-(cyanato)-5-iodobenzoate, m.ρ.66-8 °C; lH ΝMR (300 MHz, CDC13): δ 3.96 (s,3H); 7.33 (d,lH); 7.95 (dd,lH); 8.31 (d,lH); IR (polyethylene card) 2245 cm"l. Step B : Preparation of 6-Iodo-2-(propylamino)-4H- 1.3-benzoxazin-4-one
To 1.0 g (3.3 mmol) of methyl 2-(cyanato)-5-iodobenzoate in 15 mL of acetone was added 0.19 g (3.3 mmol) of propylamine. The reaction mixture was stirred for 2 hours at room temperature. The ensuing precipitate was filtered, washed with diethyl ether, and air dried to obtain 0.35 g of 6-iodo-2-(propylamino)-4H-l,3-benzoxazin-4-one, m.p. 240-2 °C; *Η ΝMR (300 MHz, Me2SO-d6): δ 0.90 (t,3H); 1.58 (m,2H); 3.25 (m,2H); 7.14 (d,lH); 7.98 (dd,lH); 8.10 (d,lH); 8.75 (t,lH); m/e 331, protonated parent molecular ion (m/e) measured by mass spectrometry using atmospheric pressure chemical ionization in the positive ion mode (APCI+). Step C: Preparation of 2.3-Dihvdro-6-iodo-3-propyl-2-(propylimino)-4H-l,3- benzoxazin-4-one
To a solution of 0.6 g (1.83 mmol) of 6-iodo-2-(proρylamino)-4H-l,3-benzoxazin-4- one in 10 mL of dimethylformamide at 0 °C was added 0.08 g of 60% sodium hydride dispersed in mineral oil (delivers 2.0 mmol of sodium hydride). The reaction mixture was stirred at 0 °C for 5 min, then 0.46 g (2.7 mmol) of 1-iodopropane was added and the resulting mixture was allowed to warm to room temperature. After stirring for 3 hours, the reaction was quenched with 5 mL of IN hydrochloric acid and partitioned between water and dichloromethane. The phases were separated and the aqueous phase was extracted with additional dichloromethane. The organic layers were combined, washed with water, and dried over sodium sulfate. Concentration at reduced pressure afforded the crude product, which was purified by flash chromatography on silica (70:30 hexanes:ethyl acetate) to give 0.21 g of 2,3-dmydro-6-iodo-3-propyl-2-(propylimino)-4H-l,3-benzoxazin-4-one, m.p. 44-8 °C; lΗ ΝMR (300 MHz, CDC13): δ 0.96 (m,6H); 1.65 (m,4H); 3.39 (t,2H); 3.98 (t,2H); 6.88 (d,lH); 7.83 (dd,lH); 8.31 (d,lH); m/e 373, protonated parent molecular ion (m/e) measured by mass spectrometry using atmospheric pressure chemical ionization in the positive ion mode (APCI+). Also isolated was 0.22 g of 2-(dipropylamino)-6-iodo-4H-l,3- benzoxazin-4-one, m.p.120-2 °C; lΗ ΝMR (300 MHz, CDC13): δ 0.97 (m,6H); 1.71 (m,4H); 3.48 (t,2H); 3.58 (t,2H); 6.96 (d,lH); 7.83 (dd,lH); 8.44 (d,lH); m e 373, protonated parent molecular ion (m/e) measured by mass spectrometry using atmospheric pressure chemical ionization in the positive ion mode (APCI+). Step D: Preparation of 2-(Dipropylamino)-6-iodo-4H-1.3-benzoxazin-4-one
To 0.5 g (1.65 mmol) of methyl 2-(cyanato)-5-iodobenzoate in 7.5 mL of acetone was added 0.17 g (1.65 mmol) of dipropylamine. The reaction mixture was stirred at room temperature overnight, concentrated in vacuo, and triturated with hexanes to provide a solid. The solid was filtered and air dried to obtain 0.178 g of 2-(dipropylamino)-6-iodo-4H-l,3- benzoxazin-4-one, m.p. 120-2 °C; lΗ ΝMR (300 MHz, CDC13): δ 0.97 (m,6H); 1.71 (m,4H); 3.48 (t,2H); 3.58 (t,2H); 6.96 (d,lH); 7.83 (dd,lH); 8.44 (d,lH); m/e 373, protonated parent molecular ion (m/e) measured by mass spectrometry using atmospheric pressure chemical ionization in the positive ion mode (APCI+).
Example 2 Step A: Preparation of 2.3.5-Triiodo-N-propylbenzenecarboxamide
To 5.0 g (10.0 mmol) of 2,3,5 triiodobenzoic acid was added 25 mL of thionyl chloride. The reaction mixture was refluxed overnight, concentrated in vαcuo, treated with toluene and concentrated in vαcuo again. The residue was dissolved in 20 mL of tetrahydrofuran and treated dropwise with a solution of 2.46 mL (30.0 mmol) of propylamine in 30 mL of tetrahydrofuran. The resulting mixture was stiπed for 30 minutes, poured into 100 mL of IN hydrochloric acid, and extracted with diethyl ether. The organic phase was separate and hexanes were added to precipitate a solid. The solid was collected by filtration and air dried to give 5.25 g of crude 2,3,5-triiodo-N-propylbenzenecarboxamide, m.p.192-5 °C; H ΝMR (300 MHz, CDC13): δ 1.01 (t,3H); 1.65 (m,2H); 3.39 (m,2H); 5.75 (bs,lH); 7.52 (d,lH); 8.21 (d,lH); m/e 542, protonated parent molecular ion (m/e) measured by mass spectrometry using atmospheric pressure chemical ionization in the positive ion mode (APCI+).
Step B: Preparation of 2 -Dihvdro-6,8-diiodo-3-propyl-2-thioxo-4H-l,3-benzothiazin-4- one To a mixture of 0.14 g of 60% sodium hydride dispersed in mineral oil (delivers
3.7 mmol of sodium hydride) in 7mL of dimethylformamide was added a solution of 1.0 g (1.85 mmol) of 2,3,5-triiodo-N-propylbenzenecarboxamide, 0.12 mL (1.94 mmol) of carbon disulfide and 3 mL of dimethylformamide keeping the temperature <45 °C. The resulting mixture was stirred at room temperature overnight and poured into 100 mL of saturated ammonium chloride. The ensuing precipitate was filtered and washed with hexanes to provide 0.28 g of crude 2,3-dihydro-6,8-diiodo-3-propyl-2-thioxo-4H-l,3-benzothiazin-4- one, lΗ ΝMR (300 MHz, CDC13): δ 0.98 (t,3H); 1.76 (m,2H); 4.59 (t,2H); 8.31 (d,lH); 8.63 (d,lH). This material was used without further purification in Step C. Step C: Preparation of 2.3-Dihvdro-6.8-diiodo-3-propyl-2-(propylimino -4H-l,3- benzothiazin-4-one
A mixture 0.28 g of the product from Step B above, 0.05 mL (0.62 mmol) of propylamine, and 0.13 g (0.57 mmol) of yellow mercury(II) oxide in 3 mL of dioxane was stirred at room temperature overnight. The reaction mixture was concentrated under a stream of nitrogen and purified by flash chromatography on silica (90: 10 hexanes:ethyl acetate) to deliver 0.069 g of 2,3-dmydro-6,8-diiodo-3-propyl-2-(propylimino)-4H-l,3- benzothiazin-4-one, m.p.120-5 °C; JΗ ΝMR (300 MHz, CDC13): δ 0.94 (t,3H); 1.02 (t,3H); 1.70 (m,4H); 3.38 (t,2H); 4.18 (t,2H); 8.23 (dd,lH); 8.65 (dd,lH); m/e 515, protonated parent molecular ion (m/e) measured by mass spectrometry using atmospheric pressure chemical ionization in the positive ion mode (APCI+). Example 3
Step A: Preparation of 2.5-DicMoro-N-propyl-N-[(propylamino thioxomethyll-3- thiophenecarboxamide To a mixture of 1.39 g (8.71 mmol) of NN'-di-H-propylthiourea and 6.0 mL (43.5 mmol) of triethylamine in 20 mL of acetonitrile was added 1.86 g (8.68 mmol) of 2,5-dichlorothiophene-3-carbonyl chloride over 1 minute with slight exotherm. The reaction mixture was stirred for 10 minutes and refluxed for 30 minutes. This reaction mixture was then allowed to cool to room temperature, poured into 25 mL of methanol, diluted with water, and extracted multiple times with hexanes. The organic phases were combined, dried over sodium sulfate, and concentrated at reduced pressure to deliver 1.25 g of crude product. The crude material was purified by flash chromatography on silica (90: 10 hexanes:ethyl acetate) to give 0.4 g of product, which was further purified by trituration with petroleum ether, to yield 0.325 g of 2,5-dicMoro-N-propyl-N-[(propylamino)thioxomethyl]-3-thiophenecarboxamide, m.p. 69-71 °C; lH NMR (300 MHz, CDC13): δ 0.81 (t,3H); 1.0 (t,3H); 1.68 (m,4H); 3.62 (m,2H); 4.18 (t,2H); 6.84 (s,lH); 10.70 (bs,lH); m/e 339/341/343 (di-chlorine pattern), protonated parent molecular ions (m/e) measured by mass spectrometry using atmospheric pressure chemical ionization in the positive ion mode (APCI+). Step B: Preparation of 6-Chloro-2.3-dihvdro-3-propyl-2-(propylimino -4H-thienor3.2-g1- 1.3-thiazin-4-one To a solution of 0.3 g (0.89 mmol) of 2,5-dichloro- N-propyl-N-[(propylamino)tWoxomemyl]-3-thiophenecarboxamide in 8 mL of dimethylformamide was added 0.36 g of 60% sodium hydride dispersed in mineral oil (delivers 0.89 mmol of sodium hydride). The reaction mixture was stirred at room temperature overnight and poured into dilute aqueous ammonium chloride. The ensuing solid precipitate was filtered, washed with water, and dried to give 0.24 g of crude product. The crude material was purified by flash chromatography on silica (98:2 hexanes:ethyl acetate) to provide 0.050 g 6-cMoro-2,3-dmy( o-3-propyl-2-(propylimino)-4H-thieno[3,2-e]- l,3-thiazin-4-one, m.p.78-9 °C; *Η ΝMR (300 MHz, CDC13): δ 0.95 (t,3H); 0.99 (t,3H); 1.69 (m,4H); 3.22 (t,2H); 4.18 (t,2H); 7.35 (s,lH); m/e 303/305 (mono-chlorine pattern), protonated parent molecular ions (m/e) measured by mass spectrometry using atmospheric pressure chemical ionization in the positive ion mode (APCI+). Also isolated 0.050 g of 6- cWoro-2,3-dihydro-l,3-dipropyl-2-t oxotWeno[2,3--i]pyrirm^m-4(lH)-one m.p.90-2 °C; *Η ΝMR (300 MHz, CDC13): δ 0.98 (t,3H); 1.04 (t,3H); 1.78 (m,2H); 1.90 (m,2H); 4.34 (t,2H); 4.47 (t,2H); 7.22 (s,lH); m/e 303/305 (mono-chlorine pattern), protonated parent molecular ions (m/e) measured by mass spectrometry using atmospheric pressure chemical ionization in the positive ion mode (APCI+).
By the procedures described herein together with methods known in the art, the following compounds of Tables 1 to 33 can be prepared. The following abbreviations are used in the Tables which follow: t is tertiary, s is secondary, n is normal, i is iso, c is cyclo, Me is methyl, Et is ethyl, Pr is propyl, z'-Pr is isopropyl, Bu is butyl, Ph is phenyl, OMe is methoxy, OEt is ethoxy, SMe is methylthio, SEt is ethylthio, CΝ is cyano, ΝO2 is nitro, TMS is trimethylsilyl, THF is tetrahydrofuran, S(O)Me is methylsulfinyl, and S(O)2Me is methylsulfonyl.
Figure imgf000033_0001
π Table 1 Compounds of Formula I wherein Q is O; R2 is n-Pr; G is
Figure imgf000034_0001
Z is O
Figure imgf000034_0002
Me w-Bu n-pentyl n-hexyl
Et t-Pr t-Bu s-Bu c-propyl c-butyl c-pentyl 2-propenyl
3-butenyl 2-ρropynyl 3-butynyl CF3
2-Cl-Et 3-Br-w-Pr CH2CH=CHC1 CH2C≡CC1
CH2OCH3 CH2OCH2CH3 CH2SCH3 CH2SCH2CH3
CH2CH2SCH3 CH2CH2OCH2C≡CH CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
CH2CH2OCH2CH=CH2 CH2CH2SCH2C≡CH CH2OCF3 CH20CH2CH2C1
CH2CH2SCH2CH=CH2 CH2CH2N02 CH2CH=CHCH2OCH3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 2-furanyl CH2CH2Si(CH3)3 CH2CH2C02CH3
CH2CH2CH2NHCH3 3-benzo[b]thienyl CH2CH2CH2CN Ph
OCH2CH2CH3 3-MeO-Ph 2-thienyl (2-THF)CH2
2-pyridinyl 4-PhO-Ph 3-quinolinyl 4-F-Ph
5-benzofuranyl c-hexyl 2-F-4-Cl-Ph 3-CF30-Ph
2-F-4-Me-Ph (c-propyl)CH2 4-Ph-Ph 4-Cl-Ph
4-MeS-Ph CH2C02Me C02CH2CH2CH3 3-N02-Ph
CH2CH(CH)CH2OH C02Me
Z is S
Figure imgf000034_0003
Me n-Bu n-pentyl n-hexyl
Et t-Pr t-Bu 5-Bu c-propyl c-butyl c-pentyl 2-propenyl
3-butenyl 2-propynyl 3-butynyl CF3
2-Cl-Et 3-Br-n-Pr CH2CH=CHC1 CH2C≡CC1
CH2OCH3 CH2OCH2CH3 CH2SCH3 CH2SCH2CH3
CH2CH2SCH3 CH2CH2OCH2C≡CH CH2CH2CH2S(0)2CH3 (c-ρentyl)CH
CH2CH2OCH2CH=CH2 CH2CH2SCH2C≡CH CH2OCF3 CH20CH2CH2C1
CH2CH2SCH CH=CH2 CH2CH2N02 CH2CH=CHCH2OCH3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 2-furanyl CH2CH2Si(CH3)3 CH2CH2C02CH3 CH2CH2CH2NHCH3 3-benzo[b]thienyl CH2CH2CH2CN Ph
OCH CH2CH3 3-MeO-Ph 2-thienyl (2-THF)CH2
2-pyridinyl 4-PhO-Ph 3-quinolinyl 4-F-Ph
5-benzofuranyl c-hexyl 2-F-4-Cl-Ph 3-CF30-Ph
2-F-4-Me-Ph (c-propyl)CH2 4-Ph-Ph 4-Cl-Ph
4-MeS-Ph CH2C02Me C02CH2CH2CH3 3-N02-Ph
CH2CH(CH)CH2OH C02Me
Z is NMe
Figure imgf000035_0001
Me n-Bu n-pentyl n-hexyl
Figure imgf000035_0002
c-propyl c-butyl c-pentyl 2-ρropenyl
3-butenyl 2-propynyl 3-butynyl CF3
2-Cl-Et 3-Br-n-Pr CH2CH=CHC1 CH2C≡CC1
CH2OCH3 CH2OCH2CH3 CH2SCH3 CH2SCH2CH3
CH2CH2SCH3 CH2CH2OCH2C≡CH CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
CH2CH2OCH2CH=CH2 CH2CH2SCH2CsCH CH2OCF3 CH20CH2CH2C1
CH2CH2SCH2CH=CH2 CH2CH2N02 CH2CH=CHCH2OCH3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 2-furanyl CH2CH2Si(CH3)3 CH2CH2C02CH3
CH CH2CH2NHCH3 3-benzo[b]thienyl CH2CH2CH2CN Ph
OCH2CH2CH3 3-MeO-Ph 2-thienyl (2-THF)CH2
2-pyridinyl 4-PhO-Ph 3-quinolinyl 4-F-Ph
5-benzofuranyl c-hexyl 2_F-4-Cl-Ph 3-CF30-Ph
2-F-4-Me-Ph (c-propyl)CH2 4-Ph-Ph 4-Cl-Ph
4-MeS-Ph CH2C02Me C02CH2CH2CH3 3-N02-Ph
CH2CH(CH)CH2OH C02Me
Table 2
Compounds of Formula I wherein Q is O; R2 is «-Pr; G is
Figure imgf000035_0003
Zis O
Figure imgf000035_0004
Me n-Bu n-pentyl n-hexyl
Et t-Pr z'-Bu s-Bu c-propyl c-butyl c-pentyl 2-propenyl
3-butenyl 2-propynyl 3-butynyl CF3
2-Cl-Et 3-Br-n-Pr CH CH=CHC1 CH2C≡CC1
CH2OCH3 CH2OCH2CH3 CH2SCH3 CH2SCH2CH3
CH2CH2SCH3 CH2CH2OCH C≡CH CH2CH2CH2S(0)2CH3 (c-ρentyl)CH2
CH2CH2OCH2CH=CH2 CH2CH2SCH2C≡CH CH2OCF3 CH20CH2CH2C1
CH CH2SCH2CH=CH2 CH2CH2N02 CH2CH=CHCH2OCH3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 2-furanyl CH2CH2Si(CH3)3 CH2CH2C02CH3
CH2CH2CH2NHCH3 3-benzo[b]thienyl CH2CH2CH2CN Ph
OCH2CH2CH3 3-MeO-Ph 2-thienyl; (2-THF)CH2
2-pyridinyl 4-PhO-Ph 3-quinolinyl 4-F-Ph
5-benzofuranyl c-hexyl 2-F-4-Cl-Ph 3-CF30-Ph
2-F-4-Me-Ph (c-propyl)CH2 4-Ph-Ph 4-Cl-Ph
4-MeS-Ph CH2C02Me C02CH2CH2CH3 3-N02-Ph
CH2CH(CH)CH2OH C02Me
Z is S
Figure imgf000036_0001
Me n-Bu n-pentyl n-hexyl
Et i-Pτ z'-Bu s-Bu c-propyl c-butyl c-pentyl 2-propenyl
3-butenyl 2-propynyl 3-butynyl CF3
2-Cl-Et 3-Br-n-Pr CH2CH=CHC1 CH2C≡CC1
CH2OCH3 CH2OCH2CH3 CH2SCH3 CH2SCH2CH3
CH2CH2SCH3 CH2CH2OCH2C≡CH CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
CH2CH2OCH2CH=CH2 CH2CH2SCH2CsCH CH2OCF3 CH20CH2CH2C1
CH2CH2SCH2CH=CH2 CH2CH2N02 CH2CH=CHCH2OCH3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 2-fiιranyl CH2CH2Si(CH3)3 CH2CH2C02CH3
CH2CH2CH2NHCH3 3-benzo[b]thienyl CH2CH2CH2CN Ph
OCH2CH2CH3 3-MeO-Ph 2-thienyl (2-THF)CH2
2-pyridinyl 4-PhO-Ph 3-quinolinyl 4-F-Ph
5-benzofuranyl c-hexyl 2-F-4-Cl-Ph 3-CF30-Ph
2-F-4-Me-Ph (c-propyl)CH2 4-Ph-Ph 4-Cl-Ph
4-MeS-Ph CH C02Me C02CH2CH2CH3 3-N02-Ph
CH2CH(CH)CH2OH C02Me Z is NMe
Figure imgf000037_0001
Me n-Bu n-pentyl n-hexyl
Et *'-Pr t-Bu s-Bu c-propyl c-butyl c-pentyl 2-propenyl
3-butenyl 2-proρynyl 3-butynyl CF3
2-Cl-Et 3-Br-n-Pr CH2CH=CHC1 CH2C≡CC1
CH2OCH3 CH2OCH2CH3 CH2SCH3 CH2SCH2CH3
CH2CH2SCH3 CH2CH2OCH2C≡CH CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
CH2CH2OCH2CH=CH2 CH2CH2SCH2C--CH CH2OCF3 CH20CH2CH2C1
CH2CH2SCH2CH=CH2 CH CH N02 CH2CH=CHCH2OCH3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 2-furanyl CH2CH2Si(CH3)3 CH2CH2C02CH3
CH2CH2CH2NHCH3 3-benzo[b]thienyl CH2CH2CH2CN Ph
OCH2CH2CH3 3-MeO-Ph 2-thienyl (2-THF)CH2
2-pyridinyl 4-PhO-Ph 3-quinolinyl 4-F-Ph
5-benzofuranyl c-hexyl 2-F-4-Cl-Ph 3-CF30-Ph
2-F-4-Me-Ph (c-propyl)CH2 4-Ph-Ph 4-Cl-Ph
4-MeS-Ph CH C02Me C02CH2CH2CH3 3-N02-Ph
CH2CH(CH)CH2OH C02Me
Table 3 Compounds of Formula I wherein Q is O; R2 is «-Pr; G is
Figure imgf000037_0002
Zis O
Figure imgf000037_0003
Me n-Bu n-pentyl n-hexyl
Et i-?τ /-Bu s-Bu c-propyl c-butyl c-pentyl 2-propenyl
3-butenyl 2-propynyl 3-butynyl CF3
2-Cl-Et 3-Br-n-Pr CH2CH=CHC1 CH2C≡CC1
CH2OCH3 CH2OCH CH3 CH2SCH3 CH2SCH2CH3
CH2CH2SCH3 CH2CH2OCH2C≡CH CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
CH2CH2OCH2CH=CH2 CH2CH2SCH2C≡CH CH2OCF3 CH20CH2CH2C1
CH2CH2SCH2CH=CH2 CH2CH2N02 CH2CH=CHCH2OCH3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 2-furanyl CH2CH2Si(CH3)3 CH2CH2C02CH3 CH2CH2CH2NHCH3 3-benzo[b]thienyl CH2CH2CH2CN Ph
OCH2CH2CH3 3-MeO-Ph 2-thienyl (2-THF)CH2
2-pyridinyl 4-PhO-Ph 3-quinolinyl 4-F-Ph
5-benzofuranyl c-hexyl 2-F-4-Cl-Ph 3-CF30-Ph
2-F-4-Me-Ph (c-proρyl)CH2 4-Ph-Ph 4-Cl-Ph
4-MeS-Ph CH2C02Me C02CH2CH2CH3 3-N02-Ph
CH CH(CH)CH2OH C02Me
Z is S
Figure imgf000038_0001
Me n-Bu n-pentyl n-hexyl
Et i-Pτ /-Bu s-Bu c-propyl c-butyl c-pentyl 2-propenyl
3-butenyl 2-propynyl 3-butynyl CF3
2-Cl-Et 3-Br-n-Pr CH2CH=CHC1 CH2C≡CC1
CH2OCH3 CH2OCH2CH3 CH2SCH3 CH2SCH2CH3
CH2CH2SCH3 CH2CH2OCH2C≡CH CH2CH2CH2S(0)2CH3 (c-ρentyl)CH2
CH2CH2OCH2CH=CH2 CH2CH2SCH2C--CH CH2OCF3 CH20CH2CH2C1
CH2CH2SCH2CH=CH2 CH2CH2N02 CH2CH=CHCH2OCH3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 2-furanyl CH2CH2Si(CH3)3 CH2CH2C02CH3
CH2CH2CH2NHCH3 3-benzo[b]thienyl CH2CH2CH2CN Ph
OCH2CH2CH3 3-MeO-Ph 2-thienyl (2-THF)CH2
2-pyridinyl 4-PhO-Ph 3-quinolinyl 4-F-Ph
5-benzofuranyl c-hexyl 2-F-4-Cl-Ph 3-CF30-Ph
2-F-4-Me-Ph (c-propyl)CH2 4-Ph-Ph 4-Cl-Ph
4-MeS-Ph CH2C02Me C02CH2CH2CH3 3-N02-Ph
CH2CH(CH)CH2OH C02Me
Z is NMe
Figure imgf000038_0002
Me n-Bu n-pentyl n-hexyl
Et .-Pr f-Bu s-Bu c-propyl c-butyl c-pentyl 2-propenyl
3-butenyl 2-propynyl 3-butynyl CF3
2-Cl-Et 3-Br-n-Pr CH2CH=CHC1 CH2C≡CC1
CH2OCH3 CH2OCH2CH3 CH2SCH3 CH2SCH2CH3
CH2CH2SCH3 CH CH2OCH2C≡CH CH2CH2CH2S(0)2CH3 (c-ρentyl)CH2
CH2CH2OCH2CH=CH2 CH2CH2SCH2C≡CH CH2OCF3 CH2OCH2CH2Cl CH2CH2SCH2CH=CH2 CH2CH2N02 CH2CH=CHCH2OCH3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 2-furanyl CH2CH2Si(CH3)3 CH2CH2C02CH3
CH2CH2CH2NHCH3 3-benzo[b]thienyl CH2CH2CH2CN Ph
OCH2CH2CH3 3-MeO-Ph 2-thienyl (2-THF)CH2
2-pyridinyl 4-PhO-Ph 3-quinolinyl 4-F-Ph
5-benzofiιranyl c-hexyl 2-F-4-Cl-Ph 3-CF30-Ph
2-F-4-Me-Ph (c-proρyl)CH2 4-Ph-Ph 4-Cl-Ph
4-MeS-Ph CH2C02Me C02CH2CH2CH3 3-N02-Ph
CH2CH(CH)CH2OH C02Me
Table 4
Compounds of Formula I wherein Q is O; R2 is n-Pr; G is
Figure imgf000039_0001
Z is O
Figure imgf000039_0002
Me n-Bu n-pentyl n-hexyl
Et .-Pr /-Bu s-Bu c-propyl c-butyl c-pentyl 2-propenyl
3-butenyl 2-propynyl 3-butynyl CF3
2-Cl-Et 3-Br-n-Pr CH2CH=CHC1 CH2C≡CC1
CH2OCH3 CH2OCH2CH3 CH2SCH3 CH2SCH2CH3
CH2CH2SCH3 CH2CH2OCH2C≡CH CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
CH2CH2OCH2CH=CH2 CH2CH2SCH2CsCH CH2OCF3 CH2OCH2CH2Cl
CH2CH2SCH2CH=CH2 CH2CH2N02 CH2CH=CHCH2OCH3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 2-furanyl CH2CH2Si(CH3)3 CH2CH2C02CH3
CH2CH2CH2NHCH3 3-benzo[b]thienyl CH2CH2CH2CN Ph
OCH2CH2CH3 3-MeO-Ph 2-thienyl (2-THF)CH2
2-pyridinyl 4-PhO-Ph 3-quinolinyl 4-F-Ph
5-benzofuranyl c-hexyl 2-F-4-Cl-Ph 3-CF30-Ph
2-F-4-Me-Ph (c-propyl)CH2 4-Ph-Ph 4-Cl-Ph
4-MeS-Ph CH2C02Me C02CH2CH2CH3 3-N02-Ph
CH2CH(CH)CH2OH C02Me Z is S
Figure imgf000040_0001
Me n-Bu n-pentyl n-hexyl
Figure imgf000040_0002
c-propyl c-butyl c-pentyl 2-propenyl
3-butenyl 2-propynyl 3-butynyl CF3
2-Cl-Et 3-Br-n-Pr CH2CH=CHC1 CH2C≡CC1
CH2OCH3 CH2OCH2CH3 CH2SCH3 CH2SCH2CH3
CH2CH2SCH3 CH2CH2OCH C≡CH CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
CH2CH2OCH2CH=CH2 CH2CH2SCH2CsCH CH2OCF3 CH20CH2CH2C1
CH2CH2SCH2CH=CH2 CH CH2N02 CH2CH=CHCH2OCH3 CH CH2N(CH3)2
CH2CH=CHCH2SCH3 2-furanyl CH2CH2Si(CH3)3 CH2CH2C02CH3
CH2CH2CH2NHCH3 3-benzo[b]thienyl CH2CH2CH2CN Ph
OCH2CH2CH3 3-MeO-Ph 2-thienyl (2-THF)CH2
2-pyridinyl 4-PhO-Ph 3-quinolinyl 4-F-Ph
5-benzofuranyl c-hexyl 2-F-4-Cl-Ph 3-CF30-Ph
2-F-4-Me-Ph (c-propyl)CH 4-Ph-Ph 4-Cl-Ph
4-MeS-Ph CH2C02Me C02CH2CH2CH3 3-N02-Ph
CH2CH(CH)CH2OH C02Me
Z is NMe
Figure imgf000040_0003
Me n-Bu n-pentyl n-hexyl
Figure imgf000040_0004
c-propyl c-butyl c-pentyl 2-proρenyl
3-butenyl 2-propynyl 3-butynyl CF3
2-Cl-Et 3-Br-n-Pr CH2CH=CHC1 CH2C≡CC1
CH2OCH3 CH2OCH2CH3 CH2SCH3 CH SCH2CH3
CH2CH2SCH3 CH2CH2OCH2C≡CH CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
CH2CH2OCH2CH=CH2 CH2CH2SCH2OCH CH OCF3 CH20CH2CH2C1
CH2CH2SCH2CH=CH2 CH2CH2N02 CH2CH=CHCH2OCH3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 2-furanyl CH2CH2Si(CH3)3 CH2CH2C02CH3
CH2CH CH2NHCH3 3-benzo[b]thienyl CH2CH2CH2CN Ph
OCH2CH2CH3 3-MeO-Ph 2-thienyl (2-THF)CH2
2-pyridinyl 4-PhO-Ph 3-quinolinyl 4-F-Ph
5-benzofuranyl c-hexyl 2.F-4-Cl-Ph 3-CF30-Ph
2-F-4-Me-Ph (c-propyl)CH2 4-Ph-Ph 4-Cl-Ph 4-MeS-Ph CH2C02Me C02CH2CH2CH3 3-N02-Ph CH2CH(CH)CH2OH C02Me
Table 5 Compounds of Formula I wherein Q is O; R2 is w-Pr; G is
Figure imgf000041_0001
Z is O
Figure imgf000041_0002
Me n-Bu n-pentyl n-hexyl
Figure imgf000041_0003
c-propyl c-butyl c-pent l 2-propenyl
3-butenyl 2-propynyl 3-butynyl CF3
2-Cl-Et 3-Br-n-Pr CH2CH=CHC1 CH2C≡CC1
CH2OCH3 CH2OCH2CH3 CH2SCH3 CH2SCH2CH3
CH2CH2SCH3 CH2CH2OCH2C≡CH CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
CH2CH2OCH2CH=CH2 CH CH2SCH2C≡CH CH2OCF3 CH20CH2CH2C1
CH2CH2SCH2CH=CH2 CH2CH N02 CH2CH=CHCH2OCH3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 2-furanyl CH2CH2Si(CH3)3 CH2CH2C02CH3
CH2CH2CH2NHCH3 3-benzo[b]thienyl CH2CH2CH2CN Ph
OCH2CH2CH3 3-MeO-Ph 2-thienyl (2-THF)CH2
2-pyridinyl 4-PhO-Ph 3-quinolinyl 4-F-Ph
5-benzofuranyl c-hexyl 2-F-4-Cl-Ph 3-CF30-Ph
2-F-4-Me-Ph (c-ρropyl)CH2 4-Ph-Ph 4-Cl-Ph
4-MeS-Ph CH2C02Me C02CH2CH2CH3 3-N02-Ph
CH2CH(CH)CH2OH C02Me
Z is S
Figure imgf000041_0004
Me n-Bu n-pentyl n-hexyl
Et /-Pr /-Bu s-Bu c-propyl c-butyl c-pentyl 2-propenyl
3-butenyl 2-propynyl 3-butynyl CF3
2-Cl-Et 3-Br-n-Pr CH2CH=CHC1 CH2C≡CC1
CH2OCH3 CH2OCH2CH3 CH2SCH3 CH2SCH2CH3
CH2CH2SCH3 CH2CH2OCH2G≡CH CH2CH2CH2S(0)2CH3 (c-pentyl)CH2 CH2CH2OCH2CH=CH2 CH2CH2SCH2C≡CH CH2OCF3 CH20CH2CH2C1
CH2CH2SCH2CH=CH2 CH2CH2N02 CH2CH=CHCH2OCH3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 2-furanyl CH2CH2Si(CH3)3 CH2CH2C02CH3
CH2CH2CH NHCH3 3-benzo[b]thienyl CH2CH2CH2CN Ph
OCH2CH2CH3 3-MeO-Ph 2-thienyl (2-THF)CH2
2-pyridinyl 4-PhO-Ph 3-quinolinyl 4-F-Ph
5-benzofuranyl c-hexyl 2-F-4-Cl-Ph 3-CF30-Ph
2-F-4-Me-Ph (c-propyl)CH2 4-Ph-Ph 4-Cl-Ph
4-MeS-Ph CH2C02Me C02CH2CH2CH3 3-N0 -Ph
CH2CH(CH)CH2OH C02Me
Z is NMe
Figure imgf000042_0001
Me n-Bu n-pentyl n-hexyl
Et t-Pr r'-Bu s-Bu c-propyl c-butyl c-penty 2-proρenyl;
3-butenyl 2-propynyl 3-butynyl CF3
2-Cl-Et 3-Br-n-Pr CH2CH=CHC1 CH2C≡CC1
CH2OCH3 CH2OCH2CH3 CH2SCH3 CH2SCH2CH3
CH2CH2SCH3 CH2CH2OCH2C≡CH CH2CH2CH2S(0)2CH3 (c-ρentyl)CH2
CH2CH2OCH2CH=CH2 CH2CH2SCH2CsCH CH2OCF3 CH20CH2CH2C1
CH2CH2SCH2CH=CH2 CH2CH2N02 CH2CH=CHCH2OCH3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 2-furanyl CH2CH2Si(CH3)3 CH2CH2C02CH3
CH2CH2CH2NHCH3 3-benzo[b]thienyl CH2CH2CH2CN Ph
OCH2CH2CH3 3-MeO-Ph 2-thienyl; (2-THF)CH2
2-pyridinyl 4-PhO-Ph 3-quinolinyl 4-F-Ph
5-benzofuranyl c-hexyl 2-F-4-Cl-Ph 3-CF30-Ph
2-F-4-Me-Ph (c-propyl)CH2 4-Ph-Ph 4-Cl-Ph
4-MeS-Ph CH2C02Me C02CH2CH2CH3 3-N02-Ph
CH2CH(CH)CH2OH C02Me
Table 6
Compounds of Formula I wherein Q is O; R2 is n-Pr; G is
Figure imgf000042_0002
Z is O
Figure imgf000043_0001
Me n-Bu n-pentyl n-hexyl
Et /-Pr /-Bu s-Bu c-propyl c-butyl c-pentyl 2-propenyl
3-butenyl 2-propynyl 3-butynyl CF3
2-Cl-Et 3-Br-n-Pr CH2CH=CHC1 CH C≡CC1
CH2OCH3 CH2OCH CH3 CH2SCH3 CH2SCH2CH3
CH2CH2SCH3 CH2CH OCH2C≡CH CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
CH2CH2OCH2CH=CH2 CH2CH2SCH2C≡CH CH2OCF3 CH20CH2CH2C1
CH2CH2SCH2CH=CH2 CH2CH2N02 CH2CH=CHCH2OCH3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 2-furanyl CH2CH2Si(CH3)3 CH2CH2C02CH3
CH2CH2CH2NHCH3 3-benzo[b]thienyl CH2CH2CH2CN Ph
OCH2CH2CH3 3-MeO-Ph 2-thienyl (2-THF)CH2
2-pyridinyl 4-PhO-Ph 3-quinolinyl 4-F-Ph
5-benzofiαranyl c-hexyl 2-F-4-Cl-Ph 3-CF30-Ph
2-F-4-Me-Ph (c-propyl)CH2 4-Ph-Ph 4-Cl-Ph
4-MeS-Ph CH2C0 Me C02CH2CH2CH3 3-N02-Ph
CH2CH(CH)CH2OH C02Me
Z is S
Figure imgf000043_0002
Me n-Bu n-pentyl n-hexyl
Et /-Pr /-Bu s-Bu c-propyl c-butyl c-pentyl 2-propenyl
3-butenyl 2-propynyl 3-butynyl CF3
2-Cl-Et 3-Br-n-Pr CH2CH=CHC1 CH2OCCl
CH2OCH3 CH2OCH2CH3 CH2SCH3 CH2SCH2CH3
CH2CH2SCH3 CH2CH2OCH2C≡CH CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
CH2CH2OCH2CH=CH CH2CH2SCH2C≡CH CH2OCF3 CH20CH2CH2C1
CH2CH2SCH2CH=CH2 CH2CH2N02 CH2CH=CHCH2OCH3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 2-furanyl CH2CH2Si(CH3)3 CH2CH2C02CH3
CH2CH2CH2NHCH3 3-benzo[b]thienyl CH2CH2CH2CN Ph
OCH2CH2CH3 3-MeO-Ph 2-thienyl (2-THF)CH2
2-pyridinyl 4-PhO-Ph 3-quinolinyl 4-F-Ph
5-benzofuranyl c-hexyl 2-F-4-Cl-Ph 3-CF30-Ph
2-F-4-Me-Ph (c-propyl)CH2 4-Ph-Ph 4-Cl-Ph 4-MeS-Ph CH2C02Me C02CH2CH2CH3 3-N02-Ph
CH2CH(CH)CH2OH C02Me
Z is Me
Figure imgf000044_0001
Me n-Bu n-pentyl n-hexyl
Et -Pr /-Bu s-Bu c-propyl c-butyl c-pentyl 2-propenyl
3-butenyl 2-propynyl 3-butynyl CF3
2-Cl-Et 3-Br-n-Pr CH2CH=CHC1 CH2C≡CC1
CH2OCH3 CH2OCH2CH3 CH2SCH3 CH2SCH2CH3
CH2CH2SCH3 CH2CH2OCH2C≡CH CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
CH2CH2OCH2CH=CH2 CH2CH2SCH2C≡CH CH2OCF3 CH20CH2CH2C1
CH2CH2SCH2CH=CH2 CH2CH2N02 CH2CH=CHCH2OCH3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 2-fiιranyl CH2CH2Si(CH3)3 CH2CH2C02CH3
CH2CH2CH2NHCH3 3-benzo[b]thienyl CH2CH2CH2CN Ph
OCH2CH2CH3 3-MeO-Ph 2-thienyl (2-THF)CH2
2-pyridinyl 4-PhO-Ph 3-quinolinyl 4-F-Ph
5-benzofuranyl c-hexyl 2-F-4-Cl-Ph 3-CF30-Ph
2-F-4-Me-Ph (c-propyl)CH2 4-Ph-Ph 4-Cl-Ph
4-MeS-Ph CH2C02Me C02CH2CH2CH3 3-N02-Ph
CH2CH(CH)CH2OH C02Me
Table 7
Compounds of Formula I wherein Q is O; Rl is n-Propyl; G is
Figure imgf000044_0002
Zis O
R2. R2. l E
Et n-Pr /-Pr n-Bu z-Bu s-Bu n-pentyl n-hexyl n-decyl 5-decenyl 2-ρroρenyl 2-butenyl
3-butenyl CH2OCH3 2-ρropynyl 2-butynyl
3-butynyl CH2CH2SCH3 CH2CF3 CH2CH=CHC1
CH2C≡CBr CH2CH2OCH2C≡CH CH2OCH2CH3 CH2CH2OCH3
CH2SCH3 CH2CH OCF3 CH2CH2CH2S(Q)2CH3 (c-pentyl)CH2 43
2-Cl-Et CH2CH2C02Et CH2CH2SCH2CH=CH2 CH2CH2CH2CN
CH2CH2Si(CH3)3 CH2Ph CH2CH2SCH2OCH CH2OCH2CH2Cl
Ph CH2CH2N02 CH2CH2CH2N(CH3)2 CH2CH2(4-F-Ph)
4-MeO-Ph 2,4,6-triF-Ph CH2CH2OCH2CH=CH2 2-CN-Ph
CH2CH2CH2NHCH3 (c-propyl)CH2 4-CF3-Ph CH2CH2CH2Ph
2,4-diCl-Ph c-propyl CH2CN 4-Cl-Ph
(2-THF)CH2 CH2CH2CH2OH CH2CH(OH)CH2OH
Z is S
R2 El R2. R2.
Et n-Pr /-Pr n-Bu
/-Bu s-Bu n-pentyl n-hexyl n-decyl 5-decenyl 2-proρenyl 2-butenyl
3-butenyl CH2OCH3 2-propynyl 2-butynyl
3-butynyl CH2CH2SCH3 CH2CF3 CH2CH=CHC1
CH2C≡CBr CH2CH2OCH2C--CH CH2OCH2CH3 CH2CH2OCH3
CH2SCH3 CH2CH2OCF3 CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
2-Cl-Et CH2CH2C02Et CH2CH2SCH2CH=CH2 CH2CH2CH2CN
CH2CH2Si(CH3)3 CH2Ph CH2CH2SCH2C≡CH CH20CH2CH2C1
Ph CH2CH2N02 CH2CH2CH2N(CH3)2 CH2CH2(4-F-Ph)
4-MeO-Ph 2,4,6-triF-Ph CH2CH2OCH2CH=CH2 2-CN-Ph
CH2CH2CH2NHCH3 (c-propyl)CH2 4-CF3-Ph CH2CH2CH2Ph
2,4-diCl-Ph c-propyl CH2CN 4-Cl-Ph
(2-THF)CH2 CH2CH2CH2OH CH2CH(OH)CH2OH
Z is Me
R2. E2. R2. R2
Et n-Pr /-Pr n-Bu
/-Bu s-Bu n-pentyl n-hexyl n-decyl 5-decenyl 2-propenyl 2-butenyl
3-butenyl CH2OCH3 2-ρropynl 2-butynyl
3-butynyl CH2CH2SCH3 CH2CF3 CH2CH=CHC1
CH2C≡CBr CH2CH2OCH2CsCH CH2OCH2CH3 CH2CH2OCH3
CH2SCH3 CH2CH2OCF3 CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
2-Cl-Et CH2CH2C02Et CH2CH2SCH2CH=CH2 CH2CH2CH2CN
CH2CH2Si(CH3)3 CH2Ph CH2CH2SCH2C≡CH CH20CH2CH2C1
Ph CH2CH2N02 CH2CH2CH2N(CH3)2 CH2CH2(4-F-Ph)
4-MeO-Ph 2,4,6-triF-Ph CH2CH2OCH2CH=CH2 2-CN-Ph CH CH2CH2NHCH3 (c-propyl)CH2 4-CF3-Ph CH2CH2CH2Ph
2,4-diCl-Ph c-propyl CH2CN 4-Cl-Ph
(2-THF)CH2 CH2CH2CH2OH CH2CH(OH)CH2OH
Table 8
Compounds of Formula I wherein Q is O; R1 is n-Propyl; G is
Figure imgf000046_0001
Z is O
E2. El S R2
Et n-Pr /-Pr n-Bu
/-Bu s-Bu n-pentyl n-hexyl n-decyl 5-decenyl 2-propenyl 2-butenyl
3-butenyl CH2OCH3 2-propynyl 2-butynyl
3-butynyl CH2CH2SCH3 CH2CF3 CH2CH=CHC1
CH2C≡CBr CH CH2OCH2C≡CH CH2OCH2CH3 CH2CH2OCH3
CH2SCH3 CH2CH2OCF3 CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
2-Cl-Et CH2CH2C02Et CH2CH2SCH2CH=CH2 CH2CH2CH2CN
CH2CH2Si(CH3)3 CH2Ph CH2CH2SCH2OCH CH2OCH2CH2Cl
Ph CH2CH2N02 CH CH2CH2N(CH3)2 CH2CH2(4-F-Ph)
4-MeO-Ph 2,4,6-triF-Ph CH2CH2OCH2CH=CH2 2-CN-Ph
CH2CH2CH2NHCH3 (c-propyl)CH2 4-CF3-Ph CH2CH2CH2Ph
2,4-diCl-Ph c-propyl CH2CN 4-Cl-Ph
(2-THF)CH2 CH2CH2CH2OH CH2CH(OH)CH2OH
Z is S
R2 B2 Bl R2
Et n-Pr /-Pr n-Bu
/-Bu s-Bu n-pentyl n-hexyl n-decyl 5-decenyl 2-proρenyl 2-butenyl
3-butenyl CH2OCH3 2-propynyl 2-butynyl
3-butynyl CH2CH2SCH3 CH2CF3 CH2CH=CHC1
CH2C≡CBr CH2CH2OCH2C=CH CH2OCH2CH3 CH2CH2OCH3
CH2SCH3 CH2CH2OCF3 CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
2-Cl-Et CH2CH2C02Et CH2CH2SCH2CH=CH2 CH2CH2CH2CN
CH2CH2Si(CH3)3 CH2Ph CH2CH2SCH2OCH CH2OCH2CH2Cl Ph CH2CH2N02 CH2CH2CH2N(CH3)2 CH2CH2(4-F-Ph)
4-MeO-Ph 2,4,6-triF-Ph CH2CH2OCH2CH=CH2 2-CN-Ph
CH2CH2CH2NHCH3 (c-propyl)CH2 4-CF3-Ph CH2CH2CH2Ph
2,4-diCl-Ph c-propyl CH2CN 4-Cl-Ph
(2-THF)CH2 CH2CH2CH2OH CH2CH(OH)CH2OH
Z is NMe
E2. B2 R2 El
Et n-Pr /-Pr n-Bu
/-Bu s-Bu n-pentyl n-hexyl n-decyl 5-decenyl 2-ρropenyl 2-butenyl
3-butenyl CH2OCH3 2-propynyl 2-butynyl
3-butynyl CH2CH2SCH3 CH2CF3 CH2CH=CHC1
CH2C≡CBr CH2CH2OCH2C≡CH CH2OCH2CH3 CH2CH2OCH3
CH2SCH3 CH2CH2OCF3 CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
2-Cl-Et CH2CH2C02Et CH2CH2SCH2CH=CH2 CH2CH2CH2CN
CH2CH2Si(CH3)3 CH2Ph CH2CH2SCH2C≡CH CH20CH2CH2C1
Ph CH2CH2N02 CH2CH2CH2N(CH3)2 CH2CH2(4-F-Ph)
4-MeO-Ph 2,4,6-triF-Ph CH2CH2OCH2CH=CH2 2-CN-Ph
CH CH2CH2NHCH3 (c-propyl)CH2 4-CF3-Ph CH2CH2CH2Ph
2,4-diCl-Ph c-propyl CH2CN 4-Cl-Ph
(2-THF)CH2 CH2CH2CH2OH CH2CH(OH)CH2OH
Table 9
Compounds of Formula I wherein Q is O; R1 is n-Propyl; G is
Figure imgf000047_0001
Z is O
R2. R2 E2. R2.
Et n-Pr /-Pr n-Bu i-Bu s-Bu n-pentyl n-hexyl n-decyl 5-decenyl 2-propenyl 2-butenyl
3-butenyl CH2OCH3 2-propynyl 2-butynyl
3-butynyl CH2CH2SCH3 CH2CF3 CH2CH=CHC1
CH2CsCBr CH2CH2OCH2C--CH CH2OCH2CH3 CH2CH2OCH3 CH2SCH3 CH2CH2OCF3 CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
2-Cl-Et CH2CH2C02Et CH2CH2SCH2CH=CH2 CH2CH2CH2CN
CH2CH2Si(CH3)3 CH2Ph CH2CH2SCH2C≡CH CH2OCH2CH2Cl
Ph CH2CH2N02 CH2CH2CH2N(CH3)2 CH2CH2(4-F-Ph)
4-MeO-Ph 2,4,6-triF-Ph CH2CH2OCH2CH=CH2 2-CN-Ph
CH2CH2CH2NHCH3 (c-proρyl)CH2 4-CF3-Ph CH2CH2CH2Ph
2,4-diCl-Ph c-propyl CH2CN 4-Cl-Ph
(2-THF)CH2 CH2CH2CH2OH CH2CH(OH)CH2OH
Z is S
E2. R2. R2 S2
Et n-Pr /-Pr n-Bu
/-Bu s-Bu n-pentyl n-hexyl n-decyl 5-decenyl 2-propenyl 2-butenyl
3-butenyl CH2OCH3 2-propynyl 2-butynyl
3-butynyl CH2CH2SCH3 CH2CF3 CH CH=CHC1
CH2C≡CBr CH2CH2OCH2C≡CH CH2OCH2CH3 CH2CH2OCH3
CH2SCH3 CH2CH2OCF3 CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
2-Cl-Et CH2CH2C02Et CH2CH2SCH2CH=CH2 CH2CH2CH2CN
CH2CH2Si(CH3)3 CH2Ph CH2CH2SCH2C≡CH CH2OCH2CH2Cl
Ph CH2CH2N02 CH2CH2CH2N(CH3)2 CH2CH2(4-F-Ph)
4-MeO-Ph 2,4,6-triF-Ph CH2CH2OCH2CH=CH2 2-CN-Ph
CH2CH CH2NHCH3 (c-propyl)CH2 4-CF3-Ph CH2CH2CH2Ph
2,4-diCl-Ph c-propyl CH2CN 4-Cl-Ph
(2-THF)CH2 CH2CH2CH2OH CH2CH(OH)CH2OH
Z is NMe
B2 R2. R2. R2
Et n-Pr /-Pr n-Bu
/-Bu s-Bu n-pentyl n-hexyl n-decyl 5-decenyl 2-proρenyl 2-butenyl
3-butenyl CH2OCH3 2-propynyl 2-butynyl
3-butynyl CH2CH2SCH3 CH2CF3 CH2CH=€HC1
CH2C≡CBr CH2CH2OCH2C≡CH CH OCH2CH3 CH2CH2OCH3
CH2SCH3 CH2CH2OCF3 CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
2-Cl-Et CH2CH2C02Et CH2CH2SCH2CH=CH2 CH2CH2CH CN
CH2CH2Si(CH3)3 CH2Ph CH2CH2SCH2C≡CH CH2OCH2CH2Cl
Ph CH2CH2N02 CH2CH2CH2N(CH3)2 CH2CH2(4-F-Ph) 4-MeO-Ph 2,4,6-triF-Ph CH2CH2OCH2CH=CH2 2-CN-Ph
CH2CH2CH2NHCH3 (c-ρropyl)CH2 4-CF3-Ph CH2CH2CH2Ph 2,4-diCl-Ph c-propyl CH2CN 4-Cl-Ph (2-THF)CH2 CH2CH2CH2OH CH2CH(OH)CH2OH
Table 10 Compounds of Formula I wherein Q is O; R1 is n-Propyl; G is
Figure imgf000049_0001
Z is O
Figure imgf000049_0002
Et n-Pr /-Pr n-Bu
/-Bu s-Bu n-pentyl n-hexyl n-decyl 5-decenyl 2-propenyl 2-butenyl
3-butenyl CH2OCH3 2-propynyl 2-butynyl
3-butynyl CH2CH2SCH3 CH2CF3 CH2CH=CHC1
CH2C≡CBr CH2CH2OCH2C≡CH CH2OCH2CH3 CH2CH2OCH3
CH2SCH3 CH2CH2OCF3 CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
2-Cl-Et CH2CH2C02Et CH2CH2SCH2CH=CH2 CH2CH2CH2CN
CH2CH2Si(CH3)3 CH2Ph CH2CH2SCH2C≡CH CH2OCH2CH Cl
Ph CH2CH2N02 CH2CH2CH2N(CH3)2 CH2CH2(4-F-Ph)
4-MeO-Ph 2,4,6-triF-Ph CH2CH2OCH2CH=CH2 2-CN-Ph
CH2CH2CH2NHCH3 (c-propyl)CH2 4-CF3-Ph CH2CH2CH2Ph
2,4-diCl-Ph c-propyl CH2CN 4-Cl-Ph
(2-THF)CH2 CH2CH2CH2OH CH2CH(OH)CH2OH
Z is S
R2 R2. R2 2
Et n-Pr /-Pr n-Bu i-Bu s-Bu n-pentyl n-hexyl n-decyl 5-decenyl 2-propenyl 2-butenyl
3-butenyl CH2OCH3 2-propynyl 2-butynyl
3-butynyl CH2CH2SCH3 CH2CF3 CH2CH=CHC1
CH2C≡CBr CH2CH2OCH2C--CH CH2OCH CH3 CH2CH2OCH3
CH2SCH3 CH2CH2OCF3 CH2CH2CH2S(0) CH3 (c-pentyl)CH2 2-Cl-Et CH2CH2C02Et CH2CH2SCH2CH=CH2 CH2CH2CH2CN
CH2CH2Si(CH3)3 CH2Ph CH2CH2SCH2C≡CH CH20CH2CH2C1
Ph CH2CH2N02 CH2CH2CH2N(CH3)2 CH2CH2(4-F-Ph)
4-MeO-Ph 2,4,6-triF-Ph CH2CH2OCH2CH=CH2 2-CN-Ph
CH2CH2CH2NHCH3 (c-propyl)CH2 4-CF3-Ph CH2CH2CH2Ph
2,4-diCl-Ph c-propyl CH2CN 4-Cl-Ph
(2-THF)CH CH2CH2CH2OH CH2CH(OH)CH2OH
Z is NMe
R2 2 E El
Et n-Pr /-Pr n-Bu
/-Bu s-Bu n-pentyl n-hexyl n-decyl 5-decenyl 2-propenyl 2-butenyl
3-butenyl CH2OCH3 2-propynyl 2-butynyl
3-butynyl CH2CH2SCH3 CH2CF3 CH2CH=CHC1
CH2OCBr CH2CH2OCH2OCH CH2OCH2CH3 CH2CH2OCH3
CH2SCH3 CH2CH2OCF3 CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
2-Cl-Et CH2CH2C02Et CH2CH2SCH2CH=CH2 CH2CH CH2CN
CH2CH2Si(CH3)3 CH2Ph CH2CH2SCH2C≡CH CH2OCH2CH2Cl
Ph CH2CH2N02 CH2CH2CH2N(CH3)2 CH2CH2(4-F-Ph)
4-MeO-Ph 2,4,6-triF-Ph CH2CH2OCH2CH=CH2 2-CN-Ph
CH2CH2CH2NHCH3 (c-ρropyl)CH2 4-CF3-Ph CH2CH2CH2Ph
2,4-diCl-Ph c-propyl CH2CN 4-Cl-Ph
(2-THF)CH2 CH2CH2CH2OH CH2CH(OH)CH2OH
Table 11
Compounds of Formula I wherein Q is O; R1 is n-Propyl; G is
Figure imgf000050_0001
Z is O
Figure imgf000050_0002
Et n-Pr /-Pr n-Bu -Bu s-Bu n-pentyl n-hexyl n-decyl 5-decenyl 2-propenyl 2-butenyl
3-butenyl CH2OCH3 2-propynyl 2-butynyl
3-butynyl CH2CH2SCH3 CH2CF3 CH2CH=CHC1 CH2C≡CBr CH2CH2OCH2C--CH CH2OCH2CH3 CH2CH2OCH3
CH2SCH3 CH2CH2OCF3 CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
2-Cl-Et CH2CH2C02Et CH2CH2SCH2CH=CH2 CH2CH2CH2CN
CH2CH2Si(CH3)3 CH2Ph CH2CH2SCH2C≡CH CH2OCH2CH2Cl
Ph CH2CH2N02 CH2CH2CH2N(CH3)2 CH2CH2(4-F-Ph)
4-MeO-Ph 2,4,6-triF-Ph CH2CH OCH2CH=CH2 2-CN-Ph
CH2CH2CH2NHCH3 (c-propyl)CH2 4-CF3-Ph CH2CH2CH2Ph
2,4-diCl-Ph c-propyl CH2CN 4-Cl-Ph
(2-THF)CH2 CH2CH2CH2OH CH2CH(OH)CH2OH
Z is S
S2. E R2 E
Et n-Pr /-Pr n-Bu i-Bu s-Bu n-pentyl n-hexyl n-decyl 5-decenyl 2-propenyl 2-butenyl
3-butenyl CH OCH3 2-propynyl 2-butynyl
3-butynyl CH2CH2SCH3 CH2CF3 CH2CH=CHC1
CH2C≡CBr CH2CH2OCH2C≡CH CH2OCH2CH3 CH2CH2OCH3
CH2SCH3 CH2CH2OCF3 CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
2-Cl-Et CH2CH2C02Et CH2CH2SCH2CH=CH2 CH2CH2CH2CN
CH2CH2Si(CH3)3 CH2Ph CH2CH2SCH2C≡CH CH2OCH2CH2Cl
Ph CH2CH2N02 CH2CH2CH2N(CH3)2 CH2CH2(4-F-Ph)
4-MeO-Ph 2,4,6-triF-Ph CH2CH2OCH2CH=CH2 2-CN-Ph
CH2CH2CH2NHCH3 (c-propyl)CH2 4-CF3-Ph CH2CH2CH2Ph
2,4-diCl-Ph c-propyl CH2CN 4-Cl-Ph
(2-THF)CH2 CH2CH2CH2OH CH2CH(OH)CH2OH
Z is NMe
El E E R2.
Et n-Pr /-Pr n-Bu
/-Bu s-Bu n-pentyl n-hexyl n-decyl 5-decenyl 2-propenyl 2-butenyl
3-butenyl CH2OCH3 2-propynyl 2-butynyl
3-butynyl CH2CH2SCH3 CH2CF3 CH2CH=CHC1
CH2OCBr CH2CH2OCH2OCH CH2OCH2CH3 CH2CH2OCH3
CH2SCH3 CH2CH2OCF3 CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
2-Cl-Et CH2CH2C02Et CH2CH2SCH2CH=CH2 CH2CH2CH2CN
CH2CH2Si(CH3)3 CH2Ph CH2CH2SCH2OCH CH2OCH2CH2Cl Ph CH2CH2N02 CH2CH2CH2N(CH3)2 CH2CH2(4-F-Ph)
4-MeO-Ph 2,4,6-triF-Ph CH2CH2OCH2CH=CH2 2-CN-Ph
CH2CH2CH2NHCH3 (c-proρyl)CH2 4-CF3-Ph CH2CH2CH2Ph
2,4-diCl-Ph c-propyl CH2CN 4-Cl-Ph
(2-THF)CH2 CH2CH2CH2OH CH2CH(OH)CH2OH
Table 12 Compounds of Formula I wherein Q is O; R1 is n-Propyl; G is
Figure imgf000052_0001
Z is O
Figure imgf000052_0002
Et n-Pr /-Pr n-Bu
/-Bu s-Bu n-pentyl n-hexyl n-decyl 5-decenyl 2-propenyl 2-butenyl
3-butenyl CH OCH3 2-propynyl 2-butynyl
3-butynyl CH2CH2SCH3 CH2CF3 CH2CH=CHC1
CH C≡CBr CH2CH2OCH2C≡CH CH2OCH2CH3 CH2CH2OCH3
CH2SCH3 CH2CH2OCF3 CH2CH2CH2S(0)2CH3 (c-ρentyl)CH2
2-Cl-Et CH2CH2C02Et CH2CH2SCH2CH=CH2 CH2CH2CH2CN
CH2CH2Si(CH3)3 CH2Ph CH2CH2SCH2CsCH CH20CH2CH2C1
Ph CH2CH2N02 CH2CH2CH2N(CH3)2 CH2CH2(4-F-Ph)
4-MeO-Ph 2,4,6-triF-Ph CH2CH2OCH2CH=CH2 2-CN-Ph
CH2CH2CH2NHCH3 (c-propyl)CH2 4-CF3-Ph CH2CH2CH2Ph
2,4-diCl-Ph c-propyl CH2CN 4-Cl-Ph
(2-THF)CH2 CH2CH2CH2OH CH2CH(OH)CH2OH
Z is S
R2 l El R2.
Et n-Pr /-Pr n-Bu
/-Bu s-Bu n-pentyl n-hexyl n-decyl 5-decenyl 2-propenyl 2-butenyl
3-butenyl CH2OCH3 2-propynyl 2-butynyl
3-butynyl CH2CH2SCH3 CH2CF3 CH2CH=CHC1
CH2OCBr CH2CH2OCH2C≡CH CH2OCH2CH3 CH2CH2OCH3 CH2SCH3 CH2CH2OCF3 CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
2-Cl-Et CH2CH2C02Et CH2CH2SCH2CH=CH2 CH2CH2CH2CN
CH2CH2Si(CH3)3 CH2Ph CH2CH2SCH2C≡CH CH20CH2CH2C1
Ph CH2CH2N02 CH2CH2CH2N(CH3)2 CH2CH2(4-F-Ph)
4-MeO-Ph 2,4,6-triF-Ph CH2CH2OCH2CH=CH2 2-CN-Ph
CH2CH2CH2NHCH3 (c-propyl)CH2 4-CF3-Ph CH2CH2CH2Ph
2,4-diCl-Ph c-propyl CH2CN 4-Cl-Ph
(2-THF)CH2 CH2CH2CH2OH CH2CH(OH)CH2OH
Z is Me
R2 l2 S2 S2
Et n-Pr /-Pr n-Bu -Bu s-Bu n-pentyl n-hexyl n-decyl 5-decenyl 2-propenyl 2-butenyl
3-butenyl CH2OCH3 2-ρropynl 2-butynyl
3-butynyl CH2CH2SCH3 CH2CF3 CH2CH=CHC1
CH2C≡CBr CH2CH2OCH2C≡CH CH2OCH2CH3 CH2CH2OCH3
CH2SCH3 CH2CH2OCF3 CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
2-Cl-Et CH2CH2C02Et CH2CH2SCH2CH=CH2 CH2CH2CH2CN
CH2CH2Si(CH3)3 CH2Ph CH2CH2SCH2C≡CH CH20CH2CH2C1
Ph CH2CH2N02 CH2CH2CH2N(CH3)2 CH2CH2(4-F-Ph)
4-MeO-Ph 2,4,6-triF-Ph CH2CH2OCH2CH=CH2 2-CN-Ph
CH2CH2CH2NHCH3 (c-propyl)CH2 4-CF3-Ph CH2CH2CH2Ph
2,4-diCl-Ph c-propyl CH2CN 4-Cl-Ph
(2-THF)CH2 CH2CH2CH2OH CH2CH(OH)CH2OH
Table 13
Compounds of Formula I wherein Z is Q is O; R2 is n-Pr, G is
Figure imgf000053_0001
l R I R10
CH2(Y-96) - -
(CH2)2CH(CH3)(CH2)2(Y-96) 2-CH3 3-CH3
(CH2)10(Y-96) 3-(CH2)5CH3 3-CH3
CH20T-97) 1-C6F5 3-CH2CH3
CH2(Y-98) - - CH2(Y-99) 3-(4-Me-Ph) 2-OCH3 -
CH2(Y-100) 2-OCH3 - -
CH2(Y-52) - - -
(CH2)5(Y-52) 3-0(CH2)5CH3 - -
(CH2)2CH(CH3)(CH2)2(Y-52) 4-CN - -
(CH2)10(Y-93) 3-CF3 - -
CH2(Y-52) 4-(CF2)5CF3 5-F 5-F
CH20"-52) 3-C1 4-CF3 -
CH2(Y-93) 2-C≡CH 4-SCH3 -
CH2(Y-3) - - -
CH2(Y-3) 4-C≡C(CH2)5CH3 5-1 -
(CH2)10(Y-4) 4-SCH3 5-C1 -
CH2(Y-2) - - -
CH2(Y-2) 3-OCF3 - -
CH2(Y-2) 3-0(CF2)5CF3 4-CH3 -
CH2(Y-1) - - -
CH2(Y-1) - - 5-C1
(CH2)5(Y-5) 2-Br 4-Br 5-Br
CH2(Y-16) 2-CH3 3-CH2CH3 -
CH2(Y-15) 3-Br - -
CH2(Y-15) - 3-C02CH2CH3 -
CH2 M5) - 3-C(0)N(CH3)2 -
CH2(Y-15) - 3-C(0)N(CH2CH3)2 -
CH2(Y-15) 3-SCH2CH2CH3 - -
(CH2)10 -15) 3-N(CH3)2 - -
(CH2)5(Y-17) 3-N(CH2CH3)2 5-CH3 -
CH2(Y-14) 3-Br - -
CH20T-14) - 3-C02CH2CH3 -
CH2(Y-14) - 3-C(0)N(CH3)2 -
CH2(Y-14) - 3-C(0)N(CH2CH3)2 -
CH2(Y-13) 3-OCH2CH2CH3 5-CH2CH3 -
CH2(Y-14) 3-OCH2CH2CH3 4-CH2CH3 -
CH2(Y-60) 2-(4-Cl-Ph) 5-C02CH3 -
CH2(Y-60) 2-(2,4-diBr-Ph) 5-C02CH3 -
(CH2)8(Y-21) 2-(3-N02-Ph) 5-C02CH3 -
CH2(Y-11) 3-(2-CN-PhO) - -
CH2(Y-91) l-(4-CF3-Ph) - -
(CH2)4(Y-27) 3-CF2CF2CF3 - - CH2(Y-37) - -
CH20f-38) - -
(CH2)7(Y-38) 6-SCCl3 5-C1 2-C1
CH2(Y-39) 2-S(CF2)5CF3 6-CF3
CH20T-44) - -
(CH2)9(Y-45) 2-F 5-F 6-F
CH2(Y-46) 4-(C(0)CH3) 6-1
CH2 -51) 3-C(CH3)3 -
CH2(Y-51) 3-Ph -
CH2(Y-51) 3-[4-CF3(CF2)3-Ph] -
CH2(Y-92) 5-CF3 6-CF3
CH(CH3)CH2(Y-66) 4-CH=CH2 3-OCH3
CH2(Y-71) 1-1 3-Br 4-C1
CH2(Y-75) - -
CH20r-75) 7-[4-CH30-Ph] -
(CH2)2(Y-75) 4-(CH2)4CH=CH2 2-SCH3
CH2C---85) 6-(CH2)CH=CH(CF3) 2-1 4-1
CH2(Y-85) - -
CH20:-85) 6-[4-CH3(CH2)30-Ph] -
CH2(Y-78) 5-CCl=CCl2 -
CH2(Y-78) 6-CF=CF(CF2)3CH3 -
CH2(Y-79) 2-CF2CF=CFCF3 -
Figure imgf000055_0001
CH2(Y-87) 7-C1 5-C1 3-C1
CH2(Y-89) 4-[4-(CH3)3C-Ph] 2-CH3
CH2(Y-54) 2-CH3 2-CH3
CH2(Y-54) 2-Ph -
CH20 -95) - -
CH2(Y-94)
Table 14
Compounds of Formula I wherein Z is S, Q is O; R2 is n-Pr, G is
Figure imgf000055_0002
CH2(Y-96) (CH2)2CH(CH3)(CH2)2(Y-96) 2-CH3 3-CH3
(CH2)10(Y-96) 3-(CH2)5CH3 3-CH3
CH2 -97) -C6F5 3-CH2CH3
CH2(Y-98)
CH2(Y-99) 3-(4-Me-Ph) 2-OCH3
CH2 M00) 2-OCH3
CH2CT-52)
(CH2)5(Y-52) 3-0(CH2)5CH3
(CH2)2CH(CH3)(CH2)2C^-52) 4-CN
(CH2)10(Y-93) 3-CF3
CH2(Y-52) 4-(CF2)5CF3 5-F 5-F
CH2CT-52) 3-C1 4-CF3
CH2(Y-93) 2-C≡CH 4-SCH3
CH2(Y-3)
CH2(Y-3) 4-C≡C(CH2)5CH3 5-1
(CH2)10(Y-4) 4-SCH3 5-C1
CH2(Y-2)
CH2(Y-2) 3-OCF3
CH2C---2) 3-0(CF2)5CF3 4-CH3
CH2(Y-1)
CH2(Y-1) 5-C1
(CH2)5(Y-5) 2-Br 4-Br 5-Br
CH2 -16) 2-CH3 3-CH2CH3
CH2(Y-15) 3-Br
CH2(Y-15) 3-C02CH2CH3
CH2o-i5) 3-C(0)N(CH3)2
CH2(Y-15) 3-C(0)N(CH2CH3)2
CH2 M5) 3-SCH2CH2CH3 (CH2)10(Y-15) 3-N(CH3)2 (CH2)5(Y-17) 3-N(CH2CH3)2 5-CH3
CH2OM4) 3-Br
CH2(Y-14) 3-C02CH2CH3
CH2(Y-14) 3-C(0)N(CH3)2
CH2(Y-14) 3-C(0)N(CH2CH3)2
CH2(Y-13) 3-OCH2CH2CH3 5-CH2CH3
CH2(Y-14) 3-OCH2CH2CH3 4-CH2CH3
CH2(Y-60) 2-(4-Cl-Ph) 5-C02CH3
CH2O -60) 2-(2,4-diBr-Ph) 5-C02CH3 (CH2)8(Y-21) 2-(3-N02-Ph) 5-C02CH
CH2O l) 3-(2-CN-PhO) -
CH2(Y-91) l-(4-CF3-Ph) -
(CH2)4(Y-27) 3-CF2CF2CF3 -
CH2(Y-37) - -
CH2CT-38) - -
(CH2)7(Y-38) 6-SCCl3 5-C1 2-C1
CH2(Y-39) 2-S(CF2)5CF3 6-CF3
CH2(Y-44) - -
(CH2)9 r-45) 2-F 5-F 6-F
CH^^ό) 4-(C(0)CH3) 6-1
CH2(Y-51) 3-C(CH3)3 -
CH20^-51) 3-Ph -
CH2OT-51) 3-[4-CF3(CF2)3-Ph] -
CH2(Y-92) 5-CF3 6-CF3
(CH2)CH(CH3)CH2(Y-66) 4-CH=CH2 3-OCH3
CH2CT-71) 1-1 3-Br 4-C1
CH2(Y-75) - -
CH2(Y-75) 7-[4-CH30-Ph] -
(CH2)2(Y-75) 4-(CH2)4CH=CH2 2-SCH3
CH2O -85) 6-(CH2)CH=CH(CF3) 2-1 4-1
CH2CT-85) - -
CH2CT-85) 6-[4-CH3(CH2)30-Ph] -
Figure imgf000057_0001
CH2(Y-78) 6-CF=CF(CF2)3CH3 -
CH2(Y-79) 2-CF2CF=CFCF3 -
CH2(Y-87) - -
CH2Or-87) 7-C1 5-C1 3-C1
CH2C^-89) 4-[4-(CH3)3C-Ph] 2-CH3
CH2(Y-54) 2-CH3 2-CH3
CH2(Y-54) 2-Ph -
CH2(Y-95) - -
CH20f-94) - - Table 15 Compounds of Formula I wherein Q is O; Z is NMe, R2 is n-Pr, G is
Figure imgf000058_0001
CH2(Y-96)
(CH2)2CH(CH3)(CH2)2(Y-96) 2-CH3 3-CH3
(CH2)10(Y-96) 3-(CH2)5CH3 3-CH3
CH2(Y-97) 1-C6F5 3-CH2CH3
CH2CY-98)
CH2(Y-99) 3-(4-Me-Ph) 2-OCH3
CH2(Y-100) 2-OCH3
CH2(Y-52)
(CH2)5(Y-52) 3-0(CH2)5CH3
(CH2)2CH(CH3)(CH2)2O -52) 4-CN
Figure imgf000058_0002
CH2(Y-52) 4-(CF2)5CF3 5-F 5-F
CH2(Y-52) 3-C1 4-CF3
CH2(Y-93) 2-CsCH 4-SCH3
CH2(Y-3)
CH2(Y-3) 4-C≡C(CH2)5CH3 5-1
(CH2)10(Y- ) 4-SCH3 5-C1
CH2(Y-2)
CH2(Y-2) 3-OCF3
CH2(Y-2) 3-0(CF2)5CF3 4-CH3
CH2(Y-1)
CH2(Y-1) 5-C1 (CH2)5(Y-5) 2-Br 4-Br 5-Br
CH2(Y-16) 2-CH3 3-CH2CH3
CH2(Y-15) 3-Br
CH2(Y-15) 3-C02CH2CH3
CH2(Y-15) 3-C(0)N(CH3)2
CH2(Y-15) 3-C(0)N(CH2CH3)2
CH2(Y-15) 3-SCH2CH2CH3 (CH2)10(Y-15) 3-N(CH3)2 (CH2)5(Y-17) 3-N(CH2CH3)2 5-CH3
Figure imgf000059_0001
CH2(γ-14) - 3-C02CH2CH3
CH2(Y-14) - 3-C(0)N(CH3)2
CH2(Y-14) - 3-C(0)N(CH2CH3)2
CH2(Y-13) 3-OCH2CH2CH3 5-CH2CH3
CH2 -14) 3-OCH2CH2CH3 4-CH2CH3
CH2CT-60) 2-(4-Cl-Ph) 5-C02CH3
CH2(Y-60) 2-(2,4-diBr-Ph) 5-C02CH3
(CH2)8(Y-21) 2-(3-N02-Ph) 5-C02CH3
CH2(Y-11) 3-(2-CN-PhO) -
CH2(Y-91) l-(4-CF3-Ph) -
(CH2)4(Y-27) 3-CF2CF2CF3 -
CH2OT-37) - -
CH2 f-38) - -
(CH2)7(Y-38) 6-SCCl3 5-C1 2-C1
CH2 T-39) 2-S(CF2)5CF3 6-CF3
CH2(Y-44) - -
(CH2)9(Y-45) 2-F 5-F 6-F
CH2(Y-46) 4-(C(0)CH3) 6-1
CH2C^-51) 3-C(CH3)3 -
CH2(Y-51) 3-Ph -
CH2(Y-51) 3-[4-CF3(CF2)3-Ph] -
CH2(Y-92) 5-CF3 6-CF3
(CH2)CH(CH3)CH2(Y-66) 4-CH=CH2 3-OCH3
CH2(Y-71) 1-1 3-Br 4-C1
CH2(Y-75) - -
CH2CT-75) 7-[4-CH30-Ph] -
(CH2)2(Y-75) 4-(CH2)4CH=CH2 2-SCH3
CH2(Y-85) 6-(CH2)CH=CH(CF3) 2-1 4-1
CH2CT-85) - -
CH2(Y-85) 6-[4-CH3(CH )30-Ph] -
CH2(Y-78) 5-CCl=CCl2 -
CH2(Y-78) 6-CF=CF(CF2)3CH3 -
Figure imgf000059_0002
CH2(Y-87) - -
CH2(Y-87) 7-C1 5-C1 3-C1
CH2(Y-89) 4-[4-(CH3)3C-Ph] 2-CH3
CH2(Y-54) 2-CH3 2-CH3 CH2CT-54) 2-Ph CH2CT-95) CH2 r-94)
Table 16 Compounds of Formula I wherein Q is O, R1 and R2 are both n-propyl, G is
Figure imgf000060_0001
Z is O
R4 E R4
6-F H 6-SF5 H
6-F 8-F 6-CH=CHC02Me H
6-C≡CSiMe3 H 6-CH=CHCN H
6-C≡CH H 6-C≡CH 8-Br
6-N02 H 6-OCH3 7-OCH3
6-OCF3 H 6-OCF2H H
6-CF3 H 6-SCF2H H
6-SCF3 H 6-C=CH 8-C≡CH
6-SCN H 6-CH=CH2 5-C1
Z is S
Bl Bl Bl R4 6-F H 6-SF5 H 6-F 8-F 6-CH=CHC02Me H
6-C≡CSiMe3 H 6-CH=CHCN H 6-C=CH H 6-C≡CH 8-Br 6-N02 H 6-OCH3 7-OCH3 6-OCF3 H 6-OCF2H H 6-CF3 H 6-SCF2H H 6-SCF3 H 6-C≡CH 8-C≡CH 6-SCN H 6-CH=CH2 5-C1
Z is NMe
R3 R4 RJ R4
6-F H 6-SF5 H 6-F 8-F 6-CH=CHC02Me H
6-C≡CSiMe3 H 6-CH=CHCN H
6-C=CH H 6-C≡€H 8-Br
6-N02 H 6-OCH3 7-OCH3
6-OCF3 H 6-OCF2H H
6-CF3 H 6-SCF2H H
6-SCF3 H 6-C≡CH 8-C≡CH
6-SCN H 6-CH=CH2 5-C1
Table 17
Compounds of Formula I wherein Q is O; R2 is n-Pr; G is
Figure imgf000061_0001
Z is O
Bl Bl Bl Bl
Me n-Bu n-pentyl n-hexyl
Et /-Pr /-Bu s-Bu c-propyl c-butyl c-pentyl 2-propenyl
3-butenyl 2-propynyl 3-butynyl CF3
2-Cl-Et 3-Br-n-Pr CH2CH=CHC1 CH2C≡CC1
CH2OCH3 CH2OCH2CH3 CH2SCH3 CH2SCH2CH3
CH2CH2SCH3 CH2CH2OCH2C≡CH CH2CH2CH2S(0)2CH3 (c-ρentyl)CH2
CH2CH2OCH2CH=CH2 CH2CH2SCH2C≡CH CH2OCF3 CH 0CH2CH2C1
CH2CH2SCH2CH=CH2 CH2CH2N02 CH2CH=CHCH2OCH3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 CH2CH2Si(CH3)3 CH2CH2C02CH3
CH2CH2CH2NHCH3 2-furanyl CH2CH2CH2CN Ph
OCH2CH2CH3 3-benzo[b]thienyl (2-THF)CH2
2-pyridinyl 3-MeO-Ph 2-thienyl 4-F-Ph
5-benzofuranyl 4-PhO-Ph 3-quinolinyl 3-CF30-Ph
2-F-4-Me-Ph c-hexyl 2-F-4-Cl-Ph 4-Cl-Ph
4-MeS-Ph (c-propyl)CH2 4-Ph-Ph 3-N02-Ph
CH2CH(CH)CH2OH CH2C02Me C02CH2CH2CH3 C02Me Z is S
Bl Bl Bl Bl
Me n-Bu n-pentyl n-hexyl
Et /-Pr /-Bu s-Bu c-propyl c-butyl c-pentyl 2-propenyl
3-butenyl 2-propynyl 3-butynyl CF3
2-Cl-Et 3-Br-n-Pr CH2CH=CHC1 CH2C≡CC1
CH2OCH3 CH2OCH2CH3 CH2SCH3 CH2SCH2CH3
CH2CH2SCH3 CH2CH2OCH2C≡CH CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
CH2CH2OCH2CH=CH2 CH2CH2SCH2C≡CH CH2OCF3 CH20CH2CH2C1
CH2CH2SCH2CH=CH2 CH2CH2N02 CH2CH=CHCH2OCH3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 CH2CH2Si(CH3)3 CH2CH2C02CH3
CH2CH2CH2NHCH3 2-furanyl CH2CH2CH2CN Ph
OCH2CH2CH3 3-benzo[b]thienyl (2-THF)CH2
2-pyridinyl 3-MeO-Ph 2-thienyl 4-F-Ph
5-benzofuranyl 4-PhO-Ph 3-quinolinyl 3-CF30-Ph
2-F-4-Me-Ph c-hexyl 2-F-4-Cl-Ph 4-Cl-Ph
4-MeS-Ph (c-propyl)CH2 4-Ph-Ph 3-N02-Ph
CH2CH(CH)CH2OH CH2C02Me C02CH2CH2CH3 C02Me
Z is NMe
Bl Bl Bl Bl
Me n-Bu n-pentyl n-hexyl
Et /-Pr /-Bu s-Bu c-propyl c-butyl c-pentyl 2-propenyl
3-butenyl 2-propynyl 3-butynyl CF3
2-Cl-Et 3-Br-n-Pr CH2CHisCHCl CH2C≡CC1
CH2OCH3 CH2OCH2CH3 CH2SCH3 CH2SCH2CH3
CH2CH2SCH3 CH2CH2OCH2CsCH CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
CH2CH2OCH2CH=CH2 CH2CH2SCH2C≡CH CH2OCF3 CH20CH2CH2C1
CH2CH SCH CH=CH2 CH2CH2N02 CH2CH=CHCH2OCH3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 CH2CH2Si(CH3)3 CH2CH2C02CH3
CH2CH2CH2NHCH3 2-furanyl CH2CH2CH2CN Ph
OCH2CH2CH3 3-benzo[b]thienyl (2-THF)CH2
2-pyridinyl 3-MeO-Ph 2-thienyl 4-F-Ph
5-benzofuranyl 4-PhO-Ph 3-quinolinyl 3-CF30-Ph
2-F-4-Me-Ph c-hexyl 2-F-4-Cl-Ph 4-Cl-Ph 4-MeS-Ph (c-propyl)CH2 4-Ph-Ph 3-N02-Ph
CH2CH(CH)CH2OH CH2C02Me C02CH2CH2CH3 C02Me
Table 18
Compounds of Formula I wherein Q is O; R2 is n-Pr; G is
Figure imgf000063_0001
Z is O
Bl Bl Bl Bl
Me n-Bu n-pentyl n-hexyl
Et -Pr /-Bu s-Bu c-propyl c-butyl c-pentyl 2-propenyl
3-butenyl 2-propynyl 3-butynyl CF3
2-Cl-Et 3-Br-n-Pr CH2CH=CHC1 CH2C≡€C1
CH2OCH3 CH2OCH2CH3 CH2SCH3 CH2SCH2CH3
CH2CH2SCH3 CH2CH2OCH2C≡CH CH2CH2CH2S(0)2CH3 (c-ρentyl)CH2
CH CH2OCH2CH=CH2 CH2CH2SCH2C≡CH CH2OCF3 CH20CH2CH2C1
CH2CH SCH2CH=CH2 CH2CH2N0 CH2CH=CHCH2OCH3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 2-furanyl CH2CH2Si(CH3)3 CH2CH2C02CH3
CH2CH2CH2NHCH3 3-benzo[b]thienyl CH2CH2CH2CN Ph
OCH2CH2CH3 3-MeO-Ph 2-thienyl (2-THF)CH2
2-pyridinyl 4-PhO-Ph 3-quinolinyl 4-F-Ph
5-benzofuranyl c-hexyl 2-F-4-Cl-Ph 3-CF30-Ph
2-F-4-Me-Ph (c-propyl)CH2 4-Ph-Ph 4-Cl-Ph
4-MeS-Ph CH2C02Me C02CH2CH2CH3 3-N02-Ph
CH2CH(CH)CH2OH C0 Me
Z is S
Bl Bl Bl Bl
Me n-Bu n-pentyl n-hexyl
Et /-Pr /-Bu s-Bu c-propyl c-butyl c-pentyl 2-propenyl
3-butenyl 2-propynyl 3-butynyl CF3
2-Cl-Et 3-Br-n-Pr CH2CH=CHC1 CH2G≡CC1
CH2OCH3 CH2OCH2CH3 CH2SCH3 CH2SCH2CH3 CH2CH2SCH3 CH2CH OCH2C≡CH CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
CH2CH2OCH CH=CH2 CH2CH2SCH2C≡CH CH2OCF3 CH20CH2CH2C1
CH2CH2SCH2CH=CH2 CH2CH2N02 CH2CH=CHCH2OCH3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 2-fiιranyl CH2CH2Si(CH3)3 CH2CH2C02CH3
CH2CH2CH2NHCH3 3-benzo[b]thienyl CH2CH2CH2CN Ph
OCH2CH2CH3 3-MeO-Ph 2-thienyl (2-THF)CH2
2-pyridinyl 4-PhO-Ph 3-quinolinyl 4-F-Ph
5-benzofuranyl c-hexyl 2-F-4-Cl-Ph 3-CF30-Ph
2-F-4-Me-Ph (c-propyl)CH2 4-Ph-Ph 4-Cl-Ph
4-MeS-Ph CH2C02Me C02CH2CH2CH3 3-N02-Ph
CH2CH(CH)CH2OH C02Me
Z is NMe
Bl Bl Bl Bl
Me n-Bu n-pentyl n-hexyl
Et /-Pr /-Bu s-Bu c-propyl c-butyl c-pentyl 2-propenyl
3-butenyl 2-propynyl 3-butynyl CF3
2-Cl-Et 3-Br-n-Pr CH2CH=CHC1 CH2G≡CC1
CH2OCH3 CH2OCH2CH3 CH2SCH3 CH2SCH2CH3
CH2CH2SCH3 CH2CH2OCH2C≡CH CH2CH2CH2S(0)2CH3 (c-ρentyl)CH2
CH2CH2OCH2CH=CH2 CH2CH2SCH2C-≡CH CH2OCF3 CH20CH2CH2C1
CH2CH2SCH2CH=CH2 CH2CH2N02 CH2CH=CHCH2OCH3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 2-furanyl CH2CH2Si(CH3)3 CH2CH2C02CH3
CH2CH2CH2NHCH3 3-benzo[b]thienyl CH2CH2CH2CN Ph
OCH2CH2CH3 3-MeO-Ph 2-thienyl (2-THF)CH2
2-pyridinyl 4-PhO-Ph 3-quinolinyl 4-F-Ph
5-benzofaranyl c-hexyl 2-F-4-Cl-Ph 3-CF30-Ph
2-F-4-Me-Ph (c-propyl)CH2 4-Ph-Ph 4-Cl-Ph
4-MeS-Ph CH2C02Me C0 CH2CH2CH3 3-N02-Ph
CH2CH(CH)CH2OH C02Me Table 19
Compounds of Formula I wherein Q is O; R2 is n-Pr; G is
Figure imgf000065_0001
Z is O
Bl Bl Bl Bl
Me n-Bu n-pentyl n-hexyl
Et /-Pr /-Bu s-Bu c-propyl c-butyl c-pentyl 2-propenyl
3-butenyl 2-propynyl 3-butynyl CF3
2-Cl-Et 3-Br-n-Pr CH2CH=CHC1 CH2C≡CC1
CH2OCH3 CH2OCH2CH3 CH2SCH3 CH2SCH2CH3
CH2CH2SCH3 CH2CH2OCH2C- CH CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
CH2CH2OCH2CH=CH2 CH2CH2SCH2C≡ CH CH2OCF3 CH20CH2CH2C1
CH2CH2SCH2CH=CH2 CH2CH2N02 CH2CH=CHCH2OCH3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 2-fiιranyl CH2CH2Si(CH3)3 CH2CH2C02CH3
CH2CH2CH2NHCH3 3-benzo[b]thienyl CH2CH2CH2CN Ph
OCH2CH2CH3 3-MeO-Ph 2-thienyl (2-THF)CH2
2-pyridinyl 4-PhO-Ph 3-quinolinyl 4-F-Ph
5-benzofuranyl c-hexyl 2-F-4-Cl-Ph 3-CF30-Ph
2-F-4-Me-Ph (c-propyl)CH 4-Ph-Ph 4-Cl-Ph
4-MeS-Ph CH2C02Me C02CH2CH2CH3 3-N02-Ph
CH2CH(CH)CH2OH C02Me
Z is S
Bl Bl Bl Bl
Me n-Bu n-pentyl n-hexyl
Et /-Pr /-Bu s-Bu c-propyl c-butyl c-pentyl 2-proρenyl
3-butenyl 2-proρynyl 3-butynyl CF3
2-Cl-Et 3-Br-n-Pr CH CH=CHC1 CH2C≡CC1
CH2OCH3 CH2OCH2CH3 CH2SCH3 CH2SCH2CH3
CH2CH2SCH3 CH2CH2OCH2C≡CH CH2CH2CH2S(0)2CH3 (c-pentyl)CH
CH2CH2OCH2CH=CH2 CH2CH2SCH2C≡ sCH CH2OCF3 CH2OCH2CH2Cl
CH2CH2SCH2CH=CH2 CH2CH2N02 CH2CH=CHCH2OCH3 CH2CH2N(CH3)2 CH2CH=CHCH2SCH3 2-furanyl CH2CH2Si(CH3)3 CH2CH2C02CH3
CH2CH CH2NHCH3 3-benzo[b]thienyl CH2CH2CH2CN Ph
OCH2CH2CH3 3-MeO-Ph 2-thienyl (2-THF)CH2
2-pyridinyl 4-PhO-Ph 3-quinolinyl 4-F-Ph
5-benzofuranyl c-hexyl 2-F-4-Cl-Ph 3-CF30-Ph
2-F-4-Me-Ph (c-propyl)CH2 4-Ph-Ph 4-Cl-Ph
4-MeS-Ph CH2C02Me C02CH2CH2CH3 3-N02-Ph
CH2CH(CH)CH2OH C02Me
Z is NMe
Bl Bl Bl Bl
Me n-Bu n-pentyl n-hexyl
Et /-Pr /-Bu s-Bu c-propyl c-butyl c-pentyl 2-ρropenyl
3-butenyl 2-propynyl 3-butynyl CF3
2-Cl-Et 3-Br-n-Pr CH2CH=CHC1 CH2C≡CC1
CH2OCH3 CH2OCH2CH3 CH2SCH3 CH2SCH2CH3
CH2CH2SCH3 CH2CH2OCH2CsCH CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
CH2CH2OCH2CH=CH2 CH2CH2SCH2C≡CH CH2OCF3 CH2OCH2CH2Cl
CH2CH2SCH2CH=CH2 CH2CH2N02 CH2CH=CHCH2OCH3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 2-furanyl CH2CH2Si(CH3)3 CH2CH2C0 CH3
CH2CH2CH2NHCH3 3-benzo[b]thienyl CH2CH2CH2CN Ph
OCH2CH2CH3 3-MeO-Ph 2-thienyl (2-THF)CH2
2-pyridinyl 4-PhO-Ph 3-quinolinyl 4-F-Ph
5-benzofuranyl c-hexyl 2-F-4-Cl-Ph 3-CF30-Ph
2-F-4-Me-Ph (c-propyl)CH2 4-Ph-Ph 4-Cl-Ph
4-MeS-Ph CH2C02Me C02CH2CH2CH3 3-N02-Ph
CH2CH(CH)CH2OH C0 Me Table 20 Compounds of Formula I wherein Q is O; R1 is n-Propyl; G is
Figure imgf000067_0001
Z is O
Figure imgf000067_0002
Et n-Pr /-Pr n-Bu
/-Bu s-Bu n-pentyl n-hexyl n-decyl 5-decenyl 2-propenyl 2-butenyl
3-butenyl CH2OCH3 2-propynyl 2-butynyl
3-butynyl CH2CH2SCH3 CH2CF3 CH2CH=CHC1
CH2C≡CBr CH2CH2OCH2C≡CH CH2OCH2CH3 CH2CH2OCH3
CH2SCH3 CH2CH2OCF3 CH2CH2CH2S(0)2CH3 (c-ρentyl)CH2
2-Cl-Et CH2CH2C02Et CH2CH2SCH2CH=CH2 CH CH2CH2CN
CH2CH2Si(CH3)3 CH2Ph CH2CH2SCH2C≡CH CH20CH2CH2C1
Ph CH2CH2N02 CH2CH2CH2N(CH3)2 CH2CH (4-F-Ph)
4-MeO-Ph 2,4,6-triF-Ph CH2CH2OCH2CH=CH2 2-CN-Ph
CH2CH2CH2NHCH3 (c-propyl)CH2 4-CF3-Ph CH2CH2CH2Ph
2,4-diCl-Ph c-propyl CH2CN 4-Cl-Ph
(2-THF)CH2 CH2CH2CH2OH CH2CH(OH)CH2(
Z is S
El El Bl El
Et n-Pr /-Pr n-Bu
/-Bu s-Bu n-pentyl n-hexyl n-decyl c-hexyl 2-propenyl 2-butenyl
3-butenyl 5-decenyl 2-propynyl 2-butynyl
3-butynyl CH2OCH3 CH2CF3 CH2CH=CHC1
CH2OCBr CH2CH2SCH3 CH2OCH2CH3 CH2CH2OCH3
CH2SCH3 CH2CH2OCH2C≡CH CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
2-Cl-Et CH2CH2OCF3 CH2CH2SCH2CH=CH2 CH2CH2CH2CN
CH2CH2Si(CH3)3 CH2CH2C02Et CH2CH2SCH C≡CH CH20CH2CH2C1
Ph CH2Ph CH2CH2CH2N(CH3)2 CH2CH2(4-F-Ph)
4-MeO-Ph CH2CH2N02 CH2CH2OCH2CH=CH2 2-CN-Ph
CH2CH2CH2NHCH3 2,4,6-triF-Ph 4-CF3-Ph CH2CH2CH2Ph 2,4-diCl-Ph (c-propyl)CH2 CH2CN 4-Cl-Ph
(2-THF)CH2 c-propyl CH2CH2CH2OH CH2CH(OH)CH2OH
Z is NMe
Bl E2. El El
Et n-Pr /-Pr n-Bu
/-Bu s-Bu n-pentyl n-hexyl n-decyl 5-decenyl 2-propenyl 2-butenyl
3-butenyl CH2OCH3 2-propynyl 2-butynyl
3-butynyl CH2CH2SCH3 CH2CF3 CH2CH=CHC1
CH2C≡CBr CH2CH2OCH2CsCH CH2OCH2CH3 CH2CH2OCH3
CH2SCH3 CH2CH2OCF3 CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
2-Cl-Et CH2CH2C02Et CH2CH2SCH2CH=CH2 CH2CH2CH2CN
CH2CH2Si(CH3)3 CH2Ph CH2CH2SCH2C≡CH CH20CH2CH2C1
Ph CH2CH2N02 CH2CH2CH2N(CH3)2 CH2CH2(4-F-Ph)
4-MeO-Ph 2,4,6-triF-Ph CH2CH2OCH2CH=CH2 2-CN-Ph
CH2CH2CH2NHCH3 (c-propyl)CH 4-CF3-Ph CH2CH2CH2Ph
2,4-diCl-Ph c-propyl CH2CN 4-Cl-Ph
(2-THF)CH2 CH2CH2CH2OH CH2CH(OH)CH2OH
Table 21
Compounds of Formula I wherein Q is O; Rl is n-Propyl; G is
Figure imgf000068_0001
Z is O
El El Bl El
Et n-Pr /-Pr n-Bu
/-Bu s-Bu n-pentyl n-hexyl n-decyl 5-decenyl 2-ρropenyl 2-butenyl
3-butenyl CH2OCH3 2-propynyl 2-butynyl
3-butynyl CH2CH2SCH3 CH CF3 CH2CH=CHC1
CH2C≡CBr CH2CH2OCH2C≡CH CH2OCH2CH3 CH2CH2OCH3
CH2SCH3 CH2CH2OCF3 CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
2-Cl-Et CH2CH2C02Et CH2CH2SCH2CH=CH2 CH2CH2CH2CN
CH2CH2Si(CH3)3 CH2Ph CH2CH2SCH2C≡CH CH20CH2CH2C1 Ph CH2CH2N02 CH2CH2CH2N(CH3)2 CH2CH2(4-F-Ph)
4-MeO-Ph 2,4,6-triF-Ph CH2CH2OCH2CH=CH2 2-CN-Ph
CH CH2CH2NHCH3 (c-propyl)CH2 4-CF3-Ph CH2CH2CH2Ph
2,4-diCl-Ph c-propyl CH2CN 4-Cl-Ph
(2-THF)CH2 CH2CH2CH2OH CH2CH(OH)CH2OH
Z is S
Bl El El El
Et n-Pr /-Pr n-Bu
/-Bu s-Bu n-pentyl n-hexyl n-decyl 5-decenyl 2-propenyl 2-butenyl
3-butenyl CH2OCH3 2-propynyl 2-butynyl
3-butynyl CH2CH2SCH3 CH2CF3 CH2CH=CHC1
CH2C≡CBr CH2CH2OCH2C≡CH CH2OCH CH3 CH2CH2OCH3
CH2SCH3 CH2CH2OCF3 CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
2-Cl-Et CH2CH2C02Et CH2CH2SCH2CH=CH2 CH2CH2CH2CN
CH2CH2Si(CH3)3 CH2Ph CH2CH2SCH2C≡CH CH20CH2CH2C1
Ph CH2CH2N02 CH2CH2CH2N(CH3)2 CH2CH2(4-F-Ph)
4-MeO-Ph 2,4,6-triF-Ph CH2CH2OCH2CH=CH2 2-CN-Ph
CH2CH2CH2NHCH3 (c-propyl)CH2 4-CF3-Ph CH2CH2CH2Ph
2,4-diCl-Ph c-propyl CH2CN 4-Cl-Ph
(2-THF)CH2 CH2CH2CH2OH CH2CH(OH)CH2OH
Z is NMe
El El El El
Et n-Pr /-Pr n-Bu
/-Bu s-Bu n-pentyl n-hexyl n-decyl 5-decenyl 2-propenyl 2-butenyl
3-butenyl CH2OCH3 2-propynyl 2-butynyl
3-butynyl CH2CH2SCH3 CH2CF3 CH2CH=CHC1
CH2OCBr CH2CH2OCH2C≡CH CH2OCH2CH3 CH2CH2OCH3
CH2SCH3 CH2CH2OCF3 CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
2-Cl-Et CH2CH2C02Et CH2CH2SCH2CH=CH2 CH2CH2CH2CN
CH2CH2Si(CH3)3 CH2Ph CH2CH2SCH2C≡CH CH20CH2CH2C1
Ph CH2CH2N02 CH2CH2CH2N(CH3)2 CH2CH2(4-F-Ph)
4-MeO-Ph 2,4,6-triF-Ph CH2CH2OCH2CH=CH2 2-CN-Ph
CH2CH2CH2NHCH3 (c-propyl)CH2 4-CF3-Ph CH2CH2CH2Ph 2,4-diCl-Ph c-propyl CH2CN 4-Cl-Ph (2-THF)CH2 CH2CH2CH2OH CH2CH(OH)CH2OH
Table 22 Compounds of Formula I wherein Q is O; Rl is n-Propyl; G is
Figure imgf000070_0001
Z is O
El Bl El El
Et n-Pr /-Pr n-Bu
/-Bu s-Bu n-pentyl n-hexyl n-decyl c-hexyl 2-propenyl 2-butenyl
3-butenyl 5-decenyl 2-propynyl 2-butynyl
3-butynyl CH2OCH3 CH2CF3 CH2CH=CHC1
CH2C≡CBr CH CH2SCH3 CH2OCH2CH3 CH2CH2OCH3
CH2SCH3 CH2CH2OCH2C≡CH CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
2-Cl-Et CH CH2OCF3 CH2CH2SCH2CH=CH2 CH2CH2CH2CN
CH2CH2Si(CH3)3 CH2CH2C02Et CH2CH2SCH2C≡CH CH20CH2CH2C1
Ph CH2Ph CH2CH2CH2N(CH3)2 CH2CH2(4-F-Ph)
4-MeO-Ph CH2CH2N02 CH2CH2OCH2CH=CH2 2-CN-Ph
CH2CH2CH2NHCH3 2,4,6-triF-Ph 4-CF3-Ph CH2CH2CH2Ph
2,4-diCl-Ph (c-propyl)CH2 CH2CN 4-Cl-Ph
(2-THF)CH2 c-propyl CH2CH2CH2OH CH2CH(OH)CH2OH
Z is S
Bl El El El
Et n-Pr /-Pr n-Bu
/-Bu s-Bu n-pentyl n-hexyl n-decyl c-hexyl 2-propenyl 2-butenyl
3-butenyl 5-decenyl 2-propynyl 2-butynyl
3-butynyl CH2OCH3 CH2CF3 CH2CH=CHC1
CH2C≡CBr CH2CH2SCH3 CH2OCH2CH3 CH2CH2OCH3
CH2SCH3 CH2CH2OCH2CsCH CH2CH2CH2S(0)2CH3 (c-pentyl)CH2
2-Cl-Et CH2CH2OCF3 CH2CH2SCH2CH=CH2 CH2CH2CH2CN
CH2CH2Si(CH3)3 CH2CH2C02Et CH2CH2SCH2CsCH CH2OCH2CH2Cl Ph CH2Ph CH2CH2CH2N(CH3)2 CH2CH2(4-F-Ph)
4-MeO-Ph CH2CH2N02 CH2CH2OCH2CH=CH2 2-CN-Ph
CH2CH2CH2NHCH3 2,4,6-triF-Ph 4-CF3-Ph CH2CH2CH2Ph
2,4-diCl-Ph (c-ρropyl)CH2 CH2CN 4-Cl-Ph
(2-THF)CH2 c-propyl CH2CH2CH2OH CH2CH(OH)CH2OH
Z is NMe
Bl El El El
Et n-Pr /-Pr n-Bu
/-Bu s-Bu n-pentyl n-hexyl n-decyl c-hexyl 2-propenyl 2-butenyl
3-butenyl 5-decenyl 2-propynyl 2-butynyl
3-butynyl CH2OCH3 CH2CF3 CH2CH=CHC1
CH2C≡CBr CH2CH2SCH3 CH2OCH2CH3 CH2CH2OCH3
CH2SCH3 CH2CH2OCH2C≡CH CH2CH2CH2S(0)2CH3 (c-pentyl)CH
2-Cl-Et CH2CH2OCF3 CH2CH2SCH2CH=CH2 CH2CH CH2CN
CH2CH2Si(CH3)3 CH2CH2C02Et CH2CH2SCH2G≡CH CH20CH2CH C1
Ph CH2Ph CH2CH2CH2N(CH3)2 CH CH2(4-F-Ph)
4-MeO-Ph CH2CH2N02 CH2CH2OCH2CH=CH2 2-CN-Ph
CH2CH2CH2NHCH3 2,4,6-triF-Ph 4-CF3-Ph CH2CH2CH2Ph
2,4-diCl-Ph (c-propyl)CH2 CH2CN 4-Cl-Ph
(2-THF)CH2 c-propyl CH2CH2CH2OH CH2CH(OH)CH2OH
Table 23
Compoimds of Formula I wherein Z is Q is O; R2 is n-Pr, G is
Figure imgf000071_0001
El Bl El R 10
CH2(Y-96) - -
(CH2)2CH(CH3)(CH2)2(Y-96) 2-CH3 3-CH3
(CH2)10 -96) 3-(CH2)5CH3 3-CH3
CH2(Y-97) 1-C6F5 3-CH2CH3
CH2(Y-98) - -
CH2(Y-99) 3.(4_Me-Ph) 2-OCH3
CH2(Y-100) 2-OCH3 -
CH2C -52) - - (CH2)5(Y-52) 3-0(CH2)5CH3
(CH2)2CH(CH3)(CH2)2(Y-52) 4-CN
(CH2)10(Y-93) 3-CF3
CU2(Y-52) 4-(CF2)5CF3 5-F 5-F
CH2(Y-52) 3-C1 4-CF3
CH2(Y-93) 2-C≡CH 4-SCH3
CH2(Y-3)
CH2(Y-3) 4-CsC(CH2)5CH3 5-1 (CH2)10(Y-4) 4-SCH3 5-C1
CH2(Y-2)
CH2(Y-2) 3-OCF3
CH2(Y-2) 3-0(CF2)5CF3 4-CH3
CH2(Y-1)
CH2(Y-1) 5-C1 (CH2)5(Y-5) 2-Br 4-Br 5-Br
CH2(Y-16) 2-CH3 3-CH2CH3
CH2(Y-15) 3-Br
CH2(Y-15) 3-C02CH2CH3
CH2(Y-15) 3-C(0)N(CH3)2
CH2(Y-15) 3-C(0)N(CH2CH3)2
CH2(Y-15) 3-SCH2CH2CH3 (CH2)10(Y-15) 3-N(CH3)2 (CU2)5(Y-ll) 3-N(CH2CH3)2 5-CH3
CH2(Y-14) 3-Br
CH2(Y-14) 3-C02CH2CH3
CH2(Y-14) 3-C(0)N(CH3)2
CH2(Y-14) 3-C(0)N(CH2CH3)2
CH2(Y-13) 3-OCH2CH2CH3 5-CH2CH3
CH2(Y-14) 3-OCH2CH2CH3 4-CH2CH3
CH2(Y-60) 2-(4-Cl-Ph) 5-C02CH3
CH2(Y-60) 2-(2,4-diBr-Ph) 5-C02CH3 (CH2)80r-21) 2-(3-N02-Ph) 5-C02CH3
CH2(Y-11) 3-(2-CN-PhO)
CH2(Y-91) l-(4-CF3-Ph) (CH2)4(Y-27) 3-CF2CF2CF3
CH2(Y-37)
CH2(Y-38) (CH2)7(Y-38) 6-SCCl3 5-C1 2-C1 CH2OT-39) 2-S(CF2)5CF3 6-CF3 CH2(Y-44) (CH2)9(Y-45) 2-F 5-F 6-F CH2(Y-46) 4-(C(0)CH3) 6-1 CH20"-51) 3-C(CH3)3 CH2 -51) 3-Ph CH2(Y-51) 3-[4-CF3(CF2)3-Ph] CH2(Y-92) 5-CF3 6-CF3 (CH2)CH(CH3)CH2(Y-66) 4-CH=CH2 3-OCH3 CH2(Y-71) 1-1 3-Br 4-C1 CH2(Y-75) CH2(Y-75) 7-[4-CH30-Ph] (CH2)2(Y-75) 4-(CH2)4CH=CH2 2-SCH3 CH2(Y-85) 6-(CH2)CH=CH(CF3) 2-1 4-1 CH2 -85) CH2O -85) 6-[4-CH3(CH2)30-Ph] CH2(Y-78) 5-CCl=CCl2 CH2(Y-78) 6-CF=CF(CF2)3CH3 CH2(Y-79) 2-CF2CF=CFCF3 CH2(Y-87) CH2Q 87) 7-C1 5-C1 3-C1 CH2CY-89) 4-[4-(CH3)3C-Ph] 2-CH3 CH2(Y-54) 2-CH3 2-CH3 CH2(Y-54) 2-Ph CH2(Y-95) CH2(Y-94)
Table 24 Compounds of Formula I wherein Q is O; Z is S, R2 is n-Pr, G is
Figure imgf000073_0001
Bl Bl Bl R 10
CH2(Y-96) - -
(CH2)2CH(CH3)(CH2)20'-96) 2-CH3 3-CH3
(CH2)10(Y-96) 3-(CH2)5CH3 3-CH3
CH2(Y-97) 1-C6F5 3-CH CH3 CH2(Y-98)
CH2(Y-99) 3-(4-Me-Ph) 2-OCH3
CH2(Y-100) 2-OCH3
CH2(Y-52)
(CH2)5(Y-52) 3-0(CH2)5CH3
(CH2)2CH(CH3)(CH2)2(Y-52) 4-CN
(CH2)10(Y-93) 3-CF3
CH2(Y-52) 4-(CF2)5CF3 5-F 5-F
CH2(Y-52) 3-C1 4-CF3
CH2(Y-93) 2-C≡CH 4-SCH3
CH2(Y-3)
CH2(Y-3) 4-C≡C(CH2)5CH3 5-1
(CH2)10(Y-4) 4-SCH3 5-C1
CH2(Y-2)
CH2(Y-2) 3-OCF3
CH2(Y-2) 3-0(CF2)5CF3 4-CH3
CH2(Y-1)
CH2(Y-1) 5-C1
(CH2)5OT-5) 2-Br 4-Br 5-Br
CH2(Y-16) 2-CH3 3-CH2CH3
CH2(Y-15) 3-Br
CH2(Y-15) 3-C02CH2CH3
CH2(Y-15) 3-C(0)N(CH3)2
CH2(Y-15) 3-C(0)N(CH2CH3)2
CH2(Y-15) 3-SCH2CH2CH3
(CH2)10(Y-15) 3-N(CH3)2
(CH2)5OM7) 3-N(CH2CH3)2 5-CH3
CH2Q 4) 3-Br
CH2(Y-14) 3-C02CH2CH3
CH2(Y-14) 3-C(0)N(CH3)2
CH2(Y-14) 3-C(0)N(CH2CH3)2
CH2(Y-13) 3-OCH2CH2CH3 5-CH2CH3
CH2(Y-14) 3-OCH2CH2CH3 4-CH2CH3
CH2(Y-60) 2-(4-Cl-Ph) 5-C02CH3
CH2(Y-60) 2-(2,4-diBr-Ph) 5-C02CH3
(CH2)8(Y-21) 2-(3-N02-Ph) 5-C02CH3
CH2(Y-11) 3-(2-CN-PhO)
CH2(Y-91) l-(4-CF3-Ph) (CH2)4(Y-27) 3-CF2CF2CF3
CH2(Y-37)
(CH2)7(Y-38) 6-SCCl3 5-C1 2-C1
CH2(Y-39) 2-S(CF2)5CF3 6-CF3
CH20f-44) (CH2)9(Y-45) 2-F 5-F 6-F
CH2(Y-46) 4-(C(0)CH3) 6-1
CH2(Y-51) 3-C(CH3)3
CH2(Y-51) 3-Ph
CH2(Y-51) 3-[4-CF3(CF2)3-Ph]
CH2(Y-92) 5-CF3 6-CF3 (CH2)CH(CH3)CH2(Y-66) 4-CH=CH2 3-OCH3
CH2(Y-71) 1-1 3-Br 4-C1
CH2(Y-75)
CH2(Y-75) 7-[4-CH30-Ph] (CH2)2(Y-75) 4-(CH2)4CH=CH2 2-SCH3
CH2(Y-85) 6-(CH2)CH=CH(CF3) 2-1 4-1
CH2(Y-85)
CH2(Y-85) 6-[4-CH3(CH2)30-Ph]
CH2(Y-78) 5-CCl=CCl2
CH2(Y-78) 6-CF=CF(CF2)3CH3
CH2(Y-79) 2-CF2CF=CFCF3
CH2(Y-87)
CH2(Y-87) 7-C1 5-C1 3-C1
CH2(Y-89) 4-[4-(CH3)3C-Ph] 2-CH3
CH2(Y-54) 2-CH3 2-CH3
CH2(Y-54) 2-Ph
CH2(Y-95)
CH2(Y-94)
Table 25 Compounds of Formula I wherein Z is Q is O, R2 is n-Pr, G is
Figure imgf000075_0001
El Bl Bl R 10
CH2(Y-96)
(CH2)2CH(CH3)(CH2)2(Y-96) 2-CH3 3-CH3
(CH2)10(Y-96) 3-(CH2)5CH3 3-CH3
CH2(Y-97) 1-C6F5 3-CH2CH3
CH2(Y-98)
CH2(Y-99) 3-(4-Me-Ph) 2-OCH3
CH2(Y-100) 2-OCH3
CH2(Y-52)
(CH2)5(Y-52) 3-0(CH2)5CH3
(CH2)2CH(CH3)(CH2)2(Y-52) 4-CN
(CH2)10(Y-93) 3-CF3
CH2(Y-52) 4-(CF2)5CF3 5-F 5-F
CH2(Y-52) 3-C1 4-CF3
CH2(Y-93) 2-C≡CH 4-SCH3
CH2(Y-3)
CH2(Y-3) 4-C≡C(CH2)5CH3 5-1
(CH2)10(Y-4) 4-SCH3 5-C1
CH2(Y-2)
CH2OT-2) 3-OCF3
CH2(Y-2) 3-0(CF2)5CF3 4-CH3
CH2rγ-l)
CH2(Y-1) 5-C1 (CH2)5(Y-5) 2-Br 4-Br 5-Br
CH2Cy-16) 2-CH3 3-CH2CH3
CH2(Y-15) 3-Br
CH2(Y-15) 3-C02CH2CH3
CH2Q 5) 3-C(0)N(CH3)2
CH2(Y-15) 3-C(0)N(CH2CH3)2
CH2(Y-15) 3-SCH2CH2CH3 (CH2)10(Y-15) 3-N(CH3)2 (CH2)5(Y-17) 3-N(CH2CH3)2 5-CH3
Figure imgf000076_0001
CH2(Y-14) 3-C02CH2CH3
CH2C^-14) 3-C(0)N(CH3)2
CH2QM4) 3-C(0)N(CH2CH3)2
CH2(Y-13) 3-OCH2CH2CH3 5-CH2CH3
CH2O 4) 3-OCH2CH2CH3 4-CH2CH3 CH2(Y-60) 2.(4.C1-Ph) 5-C02CH3
CH2(Y-60) 2-(2,4-diBr-Ph) 5-C02CH3 (CH2)8(Y-21) 2-(3-N02-Ph) 5-C02CH3
CH2(Y-11) 3-(2-CN-PhO)
CH2(Y-91) l-(4-CF3-Ph) (CH2)4(Y-27) 3-CF2CF2CF3
CH2(Y-37)
CH2(Y-38) (CH2)7 -38) 6-SCCl3 5-C1 2-C1
CH2(Y-39) 2-S(CF2)5CF3 6-CF3
CH2(Y-44) (CH2)9(Y-45) 2-F 5-F 6-F
CH2(Y-46) 4-(C(0)CH3) 6-1
CH2(Y-51) 3-C(CH3)3
CH2(Y-51) 3-Ph
CH2(Y-51) 3-[4-CF3(CF2)3-Ph]
CH2(Y-92) 5-CF3 6-CF3 (CH )CH(CH3)CH2(Y-66) 4-CH=CH2 3-OCH3
CH2(Y-71) 1-1 3-Br 4-C1
CH2(Y-75)
CH2(Y-75) 7-[4-CH30-Ph] (CH2)2(Y-75) 4-(CH2)4CH=CH2 2-SCH3
CH2(Y-85) 6-(CH2)CH=CH(CF3) 2-1 4-1
CH2(Y-85)
CH2(Y-85) 6-[4-CH3(CH2)30-Ph]
CH2(Y-78) 5-CCl=CCl2
CH2(Y-78) 6-CF=CF(CF2)3CH3
CH2(Y-79) 2-CF2CF=CFCF3
CH2(Y-87)
CH2(Y-87) 7-C1 5-C1 3-C1
CH2(Y-89) 4-[4-(CH3)3C-Ph] 2-CH3
CH2(Y-54) 2-CH3 2-CH3
CH2(Y-54) 2-Ph
CH2(Y-95)
CH2(Y-94) Table 26 Compounds of Formula I wherein Z is S, Q is O; R2 is n-Pr, G is
Figure imgf000078_0001
El Bl R9 R 10 CH2(Y-96)
(CH2)2CH(CH3)(CH2)2(Y-96) 2-CH3 3-CH3 (CH2)10 -96) 3-(CH2)5CH3 3-CH3 CH2(Y-97) 1-C6F5 3-CH2CH3 CH2 -98) CH2CT-99) 3-(4-Me-Ph) 2-OCH3 CH2(Y-100) 2-OCH3 CH2(Y-52) (CH2)5(Y-52) 3-0(CH2)5CH3
(CH2)2CH(CH3)(CH2)2(Y-52) 4-CN (CH2)10(Y-93) 3-CF3 CH2CT-52) 4-(CF2)5CF3 5-F 5-F CH2(Y-52) 3-C1 4-CF3 CH2(Y-93) 2-C=CH 4-SCH3 CH2(Y-3) CH2(Y-3) 4-CsC(CH2)5CH3 5-1 (CH2)10(Y-4) 4-SCH3 5-C1 CH2(Y-2) CH2C^-2) 3-OCF3 CH20^-2) 3-0(CF2)5CF3 4-CH3 CH2(Y-1) CH2(Y-1) 5-C1 (CH2)5(Y-5) 2-Br 4-Br 5-Br CH2O 6) 2-CH3 3-CH2CH3 CH2 -15) 3-Br CH2(Y-15) 3-C02CH2CH3 CH2(Y-15) 3-C(0)N(CH3)2 CH2 T-15) 3-C(0)N(CH2CH3)2 CH2O:-15) 3-SCH2CH2CH3 (CH2)10(Y-15) 3-N(CH3)2 (CH2)5 7) 3-N(CH2CH3)2 5-CH3 CH2(Y-14) 3-Br
CH2(Y-14) 3-C02CH2CH3
CH2(Y-14) 3-C(0)N(CH3)2
CH2(Y-14) 3-C(0)N(CH2CH3)2
CH2C^-13) 3-OCH2CH2CH3 5-CH2CH3
CH2(Y-14) 3-OCH2CH2CH3 4-CH2CH3
CH2(Y-60) 2-(4-Cl-Ph) 5-C02CH3
CH2(Y-60) 2-(2,4-diBr-Ph) 5-C02CH3
(CH2)8(Y-21) 2-(3-N02-Ph) 5-C02CH3
CH2(Y-11) 3-(2-CN-PhO)
CH2(Y-91) l-(4-CF3-Ph)
(CH2)4(Y-27) 3-CF2CF2CF3
CH2(Y-37)
CH2(Y-38)
(CH2)7(Y-38) 6-SCCl3 5-C1 2-C1
CH2(Y-39) 2-S(CF2)5CF3 6-CF3
CH2(Y-44)
(CH2)9(Y-45) 2-F 5-F 6-F
CH20T-46) 4-(C(0)CH3) 6-1
CH2C^-51) 3-C(CH3)3
CH2(Y-51) 3-Ph
CH2(Y-51) 3-[4-CF3(CF2)3-Ph]
CH2(Y-92) 5-CF3 6-CF3
(CH2)CH(CH3)CH2(Y-66) 4-CH=CH2 3-OCH3
CH2(Y-71) 1-1 3-Br 4-C1
CH2 f-75)
CH2(Y-75) 7-[4-CH30-Ph]
(CH2)2(Y-75) 4-(CH2)4CH=CH2 2-SCH3
CH2(Y-85) 6-(CH2)CH=CH(CF3) 2-1 4-1
CH2 T-85)
CH2(Y-85) 6-[4-CH3(CH2)30-Ph]
CH2(Y-78) 5-CCl=CCl2
CH2(Y-78) 6-CF=CF(CF2)3CH3
CH2(Y-79) 2-CF2CF=CFCF3
CH2(Y-87)
CH2(Y-87) 7-C1 5-C1 3-C1
CH2(Y-89) 4-[4-(CH3)3C-Ph] 2-CH3
CH2(Y-54) 2-CH3 2-CH3 CH2(Y-54) 2-Ph CH2(Y-95) CH2(Y-94)
Table 27 Compounds of Formula I wherein Q is O, Rl and R2 are both n-propyl, Z is O, G is
Figure imgf000080_0001
Bl Bl El El El El
4-Br H 5-C≡CSiMe3 H 5-C≡CH H
4-C1 H 4-C≡CH H 4-CH=CH2 H
4-1 H 5-1 H 5-CH=CH2 H
4-1 5-1 5-C≡CH 4-Br
4-Br 5-Br 4-CF3 H 5-Br 4-Me
5-Br H 4-1 5-Et
Figure imgf000080_0002
R3 R4 R3 R4 R R4
4-Br H 5-1 H 4-CH2Br H -C1 H 4-C≡CH H 4-CH=CH2 H -1 H 5-C=CiSiMe3 H 5-CH=CH2 H -1 5-1 4-c-propyl H 5-C≡CH 4-Br -Br 5-Br 4-CF3 H 5-Br 4-Me -Br H 5-C=CH H 5-1 4-Et
Figure imgf000081_0001
El El El R4 Bl El -Br H 5-C≡CSiMe3 H 5-C≡CH H -C1 H 4-C≡CH H 4-CH=CH2 H -1 H 5-1 H 5-CH=CH2 H -1 5-1 4-CF3 H 5-C≡CH 4-Br -Br 5-Br 4-c-propyl H 5-Br 4-Me -Br H 5-C1 H 4-1 5-Et
Figure imgf000081_0002
Figure imgf000082_0001
R3 El El El El El
6-Br H 6-Br 5-Br 6-CH2F H
6-C1 H 6-CsCH H 6-CH=CH2 H
6-1 H 6-C≡CiSiMe3 H 6-Br 4-Me
6-C1 4-C1 6-c-propyl H 4-Br H
6-Br 4-Br 6-CF3 H 4-1 H
6-1 4-1 6-1 4-Me
Figure imgf000082_0002
Figure imgf000082_0003
Figure imgf000083_0001
Figure imgf000083_0002
Table 28 Compounds of Formula I wherein Q is O, Rl and R2 are both n-propyl, Z is S
Figure imgf000083_0003
R3 R4 El R« El R4
4-Br H 5-1 H 4-CH2Br H 4-C1 H 4-CsCH H 4-CH=CH2 H 4-1 H 5-C≡CSiMe3 H 5-CH=CH2 H
4-1 5-1 4-c-propyl H 5-C≡CH 4-Br -Br 5-Br 4-CF3 H 5-Br 4-Me -Br H 5-C≡€H H 5-1 4-Et
Figure imgf000084_0001
El El El El El El -Br H 5-CsCSiMe3 H 5-Ca≡CH H -C1 H 4-C≡CH H 4-CH=CH2 H -1 H 5-1 H 5-CH=CH2 H -1 5-1 H H 5-C≡CH 4-Br -Br 5-Br 4-CF3 H 5-Br 4-Me -Br H 4-1 5-Et
Figure imgf000084_0002
El El Bl J R4 El El -Br H 5-1 H 4-CH2Br H -C1 H 4-C≡CH H 4-CH=CH2 H -1 H 5-C≡CiSiMe3 H 5-CH=CH2 H -1 5-1 4-c-propyl H 5-CsCH 4-Br -Br 5-Br 4-CF3 H 5-Br 4-Me -Br H 5-C≡€H H 5-1 4-Et
Figure imgf000084_0003
Bl El El El El I R4 -Br H 5-C≡CSiMe3 H 5-C≡CH H -C1 H 4-G≡CH H 4-CH=CH2 H -1 H 5-1 H 5-CH=CH2 H -1 5-1 4-CF3 H 5-C≡CH 4-Br -Br 5-Br 4-c-propyl H 5-Br 4-Me -Br H 5-C1 H 4-1 5-Et
Figure imgf000085_0001
R3 Bl El R4 El El -Br H 6-Br 5-Br 6-CH2F H -C1 H 6=C≡CH H 6-CH=CH2 H -1 H 6-CsCiSiMe3 H 6-Br 4-Me -C1 4-C1 6-c-propyl H 4-Br H
6-Br 4-Br 6-CF3 H 4-1 H
6-1 4-1 6-1 4-Me
Figure imgf000085_0002
Bl Bl El R4 R El
Br H Br H Br H
CI CF3 CI CF3 CI CF3
I CH2Br I CH2Br I CH2Br
Me CH=CH2 Me CH=CH2 Me CH=CH2
Et F Et F Et F
OCH MeO C≡CH MeO C≡CH MeO
Figure imgf000086_0001
El El El R4 El R4 Br CF3 6-Br H 6-Br H CI CH2Br 6-C=CH H 6-G≡CH H I CH=CH2 6-1 H 6-1 H C≡CH F 6-Br 5-Br 6-1 5-1 MeO 6-1 5-1 6-1 5-Me H H H H
Figure imgf000086_0002
Bl El El R El R4
6-Br H 2-Br H 4-Br H
6-C≡CH H 2-C≡CH H 6-C≡CH H
6-1 H 2-1 H 4-1 H
6-Br 2-Br 2-Br 6-Br 4-Br 6-Br
6-1 2-1 2-1 6-1 4-1 6-1
6-CH=CH2 H 2-CH=CH2 H
Figure imgf000086_0003
6-CH=CH H
Table 29
Compounds of Formula I wherein Q is O, Rl and R2 are both n-propyl, Z is NMe, G is
Figure imgf000087_0001
El El El El El El
4-Br H 5-C≡CSiMe3 H 5-C=CH H
4-C1 H 4-C≡CH H 4-CH=CH2 H
4-1 H 5-1 H 5-CH=CH2 H
4-1 5-1 5-CsCH 4-Br
4-Br 5-Br 4-CF3 H 5-Br 4-Me
5-Br H 4-1 5-Et
Figure imgf000087_0002
El El El El Bl ϊ R4
4-Br H 5-1 H 4-CH2Br H
4-C1 H 4-C≡CH H 4-CH=CH2 H
4-1 H 5-C≡CiSiMe3 H 5-CH=CH2 H
4-1 5-1 4-c-propyl H 5-C=CH 4-Br -Br 5-Br 4-CF3 H 5-Br 4-Me -Br H 5-C≡CH H 5-1 4-Et
Figure imgf000088_0001
El El El El El El -Br H 5-C≡CSiMe3 H 5-C≡CH H -C1 H 4-C≡CH H 4-CH=CH2 H -1 H 5-1 H 5-CH=CH2 H -1 5-1 4-CF3 H 5-C≡CH 4-Br -Br 5-Br 4-c-propyl H 5-Br 4-Me -Br H 5-C1 H 4-1 5-Et
Figure imgf000088_0002
El Bl El El El Bl -Br H 4-Br 5-Br 5-CH2F H -C1 H 5-C≡CH H 5-CH=CH2 H -1 H 5-C≡CiSiMe3 H 5-Br 6-Me -1 4-1 5-c-propyl H 4-Br H -Br 6-Br 5-CF3 H 4-Br 6-Br -1 6-1 5-1 6-Me
-Br -C1 -1 -C1
Figure imgf000088_0003
6-Br 4-Br 6-CF3 H 4-1 H 6-1 4-1 6-1 4-Me
Figure imgf000089_0001
El R R R3 R E Br Br Br
CI CF3 CI CF3 CI CF3 I CH2Br I CH2Br I CH2Br
CH=CH2 CH=CH2 CH=CH2
Et F Et F Et F OCH MeO C≡CH MeO C≡CH MeO
Figure imgf000089_0002
El El El R4 El El Br CF3 6-Br H 6-Br H CI CH2Br 6-C≡CH H 6-C≡CH H I CH=CH2 6-1 H 6-1 H C≡CH F 6-Br 5-Br 6-1 5-1
MeO 6-1 5-1 6-1 5-Me
Figure imgf000089_0003
El Bl Bl El El F R4 6-Br H 2-Br H 4-Br H 6-C≡CH H 2-C≡CH H 6-C≡CH H 6-1 H 2-1 H 4-1 H 6-Br 2-Br 2-Br 6-Br 4-Br 6-Br 6-1 2-1 2-1 6-1 4-1 6-1
Figure imgf000090_0001
Figure imgf000090_0002
El R4
6-Br H
6-C≡CH H
6-1 H
6-Br 2-Br
6-1 2-1
6-CH=CH2 H
Table 30 Compounds of Formula I wherein Q is O, Rl is n-propyl, R2 is n-propyl, Z is N-propyl, G is
Figure imgf000090_0003
El El El R4
6-C1 H 6-C=C-SiMe3 H
6-C1 8-C1 6-C≡C-CH H
6-Br H 6-OCF2H H
6-Br 8-Br 6-CF3 H
6-1 H 6-CH=CHC02Me H
6-1 8-1 6-CH=CHCN H
Figure imgf000090_0004
B3 E4 E3 E4 B3 R4
4-Br H 5-C≡CSiMe3 H 5-C≡CH H
4-C1 H 4-C≡CH H 4-CH=CH2 H
4-1 H 5-1 H 5-CH=CH2 H 4-1 5-1 4-CF3 H 5-CsCH 4-Br
4-Br 5-Br 4-c-propyl H 5-Br 4-Me
5-Br H 5-C1 H 4-1 5-Et
Figure imgf000091_0001
E3 E4 E3 E4 B3 R
5-Br H 4-Br 5-Br 5-CH2F H
5-C1 H 5-C≡CH H 5-CH=CH2 H
5-1 H 5-C≡CSiMe3 H 5-Br 6-Me
5-1 4-1 5 -c-propyl H 4-Br H
5-Br 6-Br 5-CF3 H 4-Br 6-Br
5-1 6-1 5-1 6-Me
Figure imgf000091_0002
R R4 E3 R4 E3 E4
6-Br H 6-Br 5-Br 6-CH2F H
6-C1 H 6-C≡CH H 6-CH=CH2 H
6-1 H 6-C≡CSiMe3 H 6-Br 4-Me
6-C1 4-C1 6-c-propyl H 4-Br H
6-Br 4-Br 6-CF3 H 4-1 H
6-1 4-1 6-1 4-Me
Figure imgf000091_0003
R3 R R E3
Br H
CI CF3
I CH2Br
Et CH=CH2
Et
Figure imgf000091_0004
Figure imgf000091_0005
F C≡CH MeO C≡CH MeO C≡CH MeO
Figure imgf000092_0001
E3 B3 B3 E4 E3 E4 Br CF3 6-Br H 6-Br H
CI CH2Br 6-C≡CH H 6-C≡CH H
I CH=CH2 6-1 H 6-1 H
C≡CH F 6-Br 5-Br 6-1 5-1 MeO 6-1 5-1 6-1 5-Me
Figure imgf000092_0002
B3 E4
6-Br H
6-C≡CH H
6-1 H
6-Br 2-Br
6-1 2-1
6-CH=CH2 H Table 31 Compounds of Formula II wherein Q is O, R2 is n-propyl, G is
Figure imgf000093_0001
Z is O.
E1 E1 E1 E1 c-propyl c-butyl n-pentyl n-hexyl
3-butenyl 2-propynyl c-pentyl CF3
2-Cl-Et 3-Br-n-Pr 3-butynyl CH2C≡CC1
CH2OCH3 CH2OCH2CH3 CH2CH=CHC1 CH2SCH2CH3
CH2CH2SCH3 CH2CH2OCH2C≡CH CH2SCH3 (c-pentyl)CH2
CH2CH2OCH2CH=CH2 CH2CH2SCH2C≡CH CH2CH2CH2S(0)2CH3 CH20CH2CH2C1
CH2CH2SCH2CH=CH2 CH2CH2N02 CH2OCF3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 2-furanyl CH2CH=CHCH2OCH3 CH CH2C02CH3
CH2CH2CH2NHCH3 3-benzo[b]thienyl CH2CH2Si(CH3)3 (2-THF)CH2
OCH2CH2CH3 3-MeO-Ph CH2CH2CH2CN 4-F-Ph
2-pyridinyl 4-PhO-Ph 2-thienyl 3-CF30-Ph
5-benzofuranyl c-hexyl 3-quinolinyl 4-Cl-Ph
2-F-4-Me-Ph (c-propyl)CH2 2-F-4-Cl-Ph 3-N02-Ph
4-MeS-Ph CH2C02Me 4-Ph-Ph C0 Me
CH2CH(OH)CH2OH (c-ρropyl)CH C0 CH2CH2CH3
Z is S.
B1 E1 B1 E1 c-propyl c-butyl n-pentyl n-hexyl
3-butenyl 2-ρroρynyl c-pentyl CF3
2-Cl-Et 3-Br-n-Pr 3-butynyl CH2C≡CC1
CH2OCH3 CH2OCH2CH3 CH2CH=CHC1 CH2SCH2CH3
CH2CH2SCH3 CH2CH2OCH2C≡CH CH2SCH3 (c-pentyl)CH2
CH2CH2OCH2CH=CH2 CH2CH2SCH2C≡CH CH2CH2CH2S(0)2CH3 CH2OCH2CH2Cl
CH2CH SCH2CH=CH2 CH2CH2N02 CH2OCF3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 2-furanyl CH2CH=CHCH2OCH3 CH2CH2C02CH3
CH2CH2CH2NHCH3 3-benzo[b]thienyl CH2CH2Si(CH3)3 (2-THF)CH2
OCH2CH2CH3 3-MeO-Ph CH2CH2CH2CN 4-F-Ph
2-pyridinyl 4-PhO-Ph 3-quinolinyl 3-CF30-Ph 5-benzofuranyl c-hexyl 2-F-4-Cl-Ph 4-Cl-Ph
2-F-4-Me-Ph (c-propyl)CH2 4-Ph-Ph 3-N02-Ph
4-MeS-Ph CH2C02Me C02CH2CH2CH3 C02Me
CH2CH(OH)CH2OH (c-propyl)CH2 C02CH2CH2CH3 3-N0 -Ph
Z is NMe.
B1 B1 E1 E1 c-propyl c-butyl n-pentyl n-hexyl
3-butenyl 2-propynyl c-pentyl CF3
2-Cl-Et 3-Br-n-Pr 3-butynyl CH2C≡CC1
CH2OCH3 CH2OCH2CH3 CH2CH=CHC1 CH2SCH2CH3
CH2CH2SCH3 CH2CH2OCH2C≡CH CH2SCH3 (c-ρentyl)CH2
CH CH2OCH2CH=CH2 CH2CH2SCH2C≡CH CH2CH2CH2S(0)2CH3 CH20CH2CH2C1
CH2CH2SCH2CH=CH2 CH2CH2N02 CH2OCF3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 2-furanyl CH2CH=CHCH2OCH3 CH2CH2C02CH3
CH2CH2CH2NHCH3 3-benzo[b]thienyl CH2CH2Si(CH3)3 (2-THF)CH2
OCH2CH2CH3 3-MeO-Ph CH2CH2CH2CN 4-F-Ph
2-pyridinyl 4-PhO-Ph 2-thienyl 3-CF30-Ph
5-benzofuranyl c-hexyl 3-quinolinyl 4-Cl-Ph
2-F-4-Me-Ph (c-propyl)CH 2-F-4-Cl-Ph 3-N02-Ph
4-MeS-Ph CH2C02Me 4-Ph-Ph C02Me
CH2CH(OH)CH2OH C02CH2CH2CH3
Table 32
Compounds of Formula II wherein Q is O, R^ is n-propyl, G is
Figure imgf000094_0001
Z is O.
B1 E1 E1 B1 c-propyl c-butyl n-pentyl n-hexyl
3-butenyl 2-propynyl c-pentyl CF3
2-Cl-Et 3-Br-n-Pr 3-butynyl CH2C≡CC1
CH2OCH3 CH2OCH2CH3 CH2CH=CHC1 CH2SCH2CH3
CH2CH2SCH3 CH2CH2OCH2C≡CH CH2SCH3 (c-pentyl)CH2 CH2CH2OCH2CH=CH2 CH2CH2SCH2C≡CH CH2CH2CH2S(0)2CH3 CH2OCH2CH2Cl
CH2CH2SCH2CH=CH2 CH2CH2N02 CH2OCF3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 2-fiιranyl CH2CH=CHCH2OCH3 CH2CH2C02CH3
CH2CH2CH2NHCH3 3-benzo[b]thienyl CH2CH2Si(CH3)3 (2-THF)CH2
OCH2CH2CH3 3-MeO-Ph CH2CH2CH2CN 4-F-Ph
2-pyridinyl 4-PhO-Ph 2-thienyl 3-CF30-Ph
5-benzofuranyl c-hexyl 3-quinolinyl 4-Cl-Ph
2-F-4-Me-Ph (c-propyl)CH2 2-F-4-Cl-Ph 3-N02-Ph
4-MeS-Ph CH2C02Me 4-Ph-Ph C02Me
CH2CH(OH)CH2OH C02CH2CH CH3
Z is S,
E1 B1 E1 E1 c-propyl c-butyl n-pentyl n-hexyl
3-butenyl 2-propynyl c-pentyl CF3
2-Cl-Et 3-Br-n-Pr 3-butynyl CH2C≡CC1
CH2OCH3 CH2OCH2CH3 CH2CH=CHC1 CH2SCH2CH3
CH2CH2SCH3 CH2CH2OCH2C≡CH CH2SCH3 (c-ρentyl)CH2
CH2CH2OCH2CH=CH2 CH2CH2SCH2C≡CH CH2CH2CH2S(0)2CH3 CH2OCH2CH2Cl
CH2CH2SCH2CH=CH2 CH2CH2N02 CH2OCF3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 2-furanyl CH2CH=CHCH2OCH3 CH2CH2C02CH3
CH2CH2CH2NHCH3 3-benzo[b]thienyl CH2CH2Si(CH3)3 (2-THF)CH2
OCH2CH2CH3 3-MeO-Ph CH2CH2CH2CN 4-F-Ph
2-pyridinyl 4-PhO-Ph 2-thienyl 3-CF30-Ph
5-benzofuranyl c-hexyl 3-quinolinyl 4-Cl-Ph
2-F-4-Me-Ph (c-propyl)CH2 2-F-4-Cl-Ph 3-N02-Ph
4-MeS-Ph CH2C02Me 4-Ph-Ph C02Me
Z is NMe.
E1 B1 E1 B1 c-propyl c-butyl n-pentyl n-hexyl
3-butenyl 2-propynyl c-pentyl CF3
2-Cl-Et 3-Br-n-Pr 3-butynyl CH2C≡CC1
CH2OCH3 CH2OCH2CH3 CH2CH=CHC1 CH2SCH2CH3
CH2CH2SCH3 CH2CH2OCH C≡CH CH2SCH3 (c-ρentyl)CH2
CH2CH2OCH CH=CH2 CH2CH2SCH2C≡CH CH2CH2CH2S(0)2CH3 CH2OCH2CH2Cl CH2CH2SCH2CH=CH2 CH2CH2N02 CH2OCF3 CH2CH2N(CH3)2
CH2CH=CHCH2SCH3 2-furanyl CH2CH=CHCH2OCH3 CH2CH2C02CH3
CH2CH2CH2NHCH3 3-benzo[b]thienyl CH2CH2Si(CH3)3 (2-THF)CH2
OCH2CH2CH3 3-MeO-Ph CH2CH2CH2CN 4-F-Ph
2-pyridinyl 4-PhO-Ph 2-thienyl 3-CF30-Ph
5-benzofuranyl c-hexyl 3-quinolinyl 4-Cl-Ph
2-F-4-Me-Ph (c-propyl)CH2 2-F-4-Cl-Ph 3-N02-Ph
4-MeS-Ph CH2C02Me 4-Ph-Ph C02Me
CH2CH(OH)CH2OH C02CH2CH2CH3
Table 33
Compounds of Formula II wherein Q is O, Z is O, R is n-propyl, Rl is n-butyl, G is
Figure imgf000096_0001
Z is O.
E3 E4 E3 R4
6-C1 H 6-C≡CSiMe3 H
6-C1 8-C1 6-C≡CH H
6-Br H 6-OCF2H H
6-Br 8-Br 6-CF3 H
6-1 H 6-CH=CHC02Me H
6-1 8-1 6-CH=CHCN H
Formulation/Utilitv
Compounds of this invention will generally be used as a formulation or composition with an agriculturally suitable carrier comprising at least one of a liquid diluent, a solid diluent or a surfactant. The formulation or composition ingredients are selected to be consistent with the physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. Useful formulations include liquids such as solutions (including emulsifiable concentrates), suspensions, emulsions (including microemulsions and/or suspoemulsions) and the like which optionally can be thickened into gels. Useful formulations further include solids such as dusts, powders, granules, pellets, tablets, films, and the like which can be water-dispersible ("wettable") or water-soluble. Active ingredient can be (micro)encapsulated and further formed into a suspension or solid formulation; alternatively the entire formulation of active ingredient can be encapsulated (or "overcoated"). Encapsulation can control or delay release of the active ingredient. Sprayable formulations can be extended in suitable media and used at spray volumes from about one to several hundred liters per hectare. High-strength compositions are primarily used as intermediates for further formulation.
The formulations will typically contain effective amounts of active ingredient, diluent and surfactant within the following approximate ranges which add up to 100 percent by weight.
Weight Percent
Active Ingredient Diluent Surfactant
Water-Dispersible and Water-soluble 5-90 0-94 1-15 Granules, Tablets and Powders.
Suspensions, Emulsions, Solutions 5-50 40-95 0-15 (including Emulsifiable Concentrates)
Dusts 1-25 70-99 0-5
Granules and Pellets 0.01-99 5-99.99 0-15
High Strength Compositions 90-99 0-10 0-2
Typical solid diluents are described in Watkins, et al., Handbook of Insecticide Dust Diluents and Carriers, 2nd Ed., Dorland Books, Caldwell, New Jersey. Typical liquid diluents are described in Marsden, Solvents Guide, 2nd Ed., Interscience, New York, 1950. McCutcheon 's Detergents and Emulsifiers Annual, Allured Publ. Corp., Ridgewood, New Jersey, as well as Sisely and Wood, Encyclopedia of Surface Active Agents, Chemical Publ. Co., Inc., New York, 1964, list surfactants and recommended uses. All formulations can contain minor amounts of additives to reduce foam, caking, corrosion, microbiological growth and the like, or thickeners to increase viscosity. Surfactants include, for example, polyethoxylated alcohols, polyethoxylated alkylphenols, polyethoxylated sorbitan fatty acid esters, dialkyl sulfosuccinates, alkyl sulfates, alkylbenzene sulfonates, organosilicones, NN-dialkyltaurates, lignin sulfonates, naphthalene sulfonate formaldehyde condensates, polycarboxylates, and polyoxyethylene/polyoxypropylene block copolymers. Solid diluents include, for example, clays such as bentonite, montmorillonite, attapulgite and kaolin, starch, sugar, silica, talc, diatomaceous earth, urea, calcium carbonate, sodium carbonate and bicarbonate, and sodium sulfate. Liquid diluents include, for example, water, NN-dimethylformamide, dimethyl sulfoxide, N-alkylpyrrolidone, ethylene glycol, polypropylene glycol, paraffins, alkylbenzenes, alkylnaphthalenes, oils of olive, castor, linseed, tung, sesame, corn, peanut, cotton-seed, soybean, rape-seed and coconut, fatty acid esters, ketones such as cyclohexanone, 2-heptanone, isophorone and 4-hydroxy-4-methyl-2-pentanone, and alcohols such as methanol, cyclohexanol, decanol and tetrahydrofurfuryl alcohol. Solutions, including emulsifiable concentrates, can be prepared by simply mixing the ingredients. Dusts and powders can be prepared by blending and, usually, grinding as in a hammer mill or fluid-energy mill. Suspensions are usually prepared by wet-milling; see, for example, U.S. 3,060,084. Granules and pellets can be prepared by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning, "Agglomeration", Chemical Engineering, December 4, 1967, pp 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546. Pellets can be prepared as described in U.S. 4,172,714. Water-dispersible and water-soluble granules can be prepared as taught in U.S. 4,144,050, U.S. 3,920,442 and DE 3,246,493. Tablets can be prepared as taught in U.S. 5,180,587, U.S. 5,232,701 and U.S. 5,208,030. Films can be prepared as taught in GB 2,095,558 and U.S. 3,299,566.
For further information regarding the art of formulation, see U.S. 3,235,361, Col. 6, line 16 through Col. 7, line 19 and Examples 10-41; U.S. 3,309,192, Col. 5, line 43 through Col. 7, line 62 and Examples 8, 12, 15, 39, 41, 52, 53, 58, 132, 138-140, 162-164, 166, 167 and 169-182; U.S. 2,891,855, Col. 3, line 66 through Col. 5, line 17 and Examples 1-4; Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961, pp 81-96; and Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989. In the following Examples, all percentages are by weight and all formulations are prepared in conventional ways. Compound numbers refer to compounds in Index Table A.
Example A Wettable Powder
Compound 1 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.
Example B Granule
Compound 1 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
Compound 1 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 Compound 1 20.0% blend of oil soluble sulfonates and polyoxyethylene ethers 10.0% isophorone 70.0%.
The compounds 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, Cercosporidium personatum, Cercospora arachidicola, Pseudocercosporella herpotrichoides, Cercospora beticola, Botrytis cinerea, Monilinia fructicola, Pyricularia oryzae, Podosphaera leucotricha, Venturia inaequalis, Erysiphe graminis, Uncinula necatur, Puccinia recondita, Puccinia graminis, Hemileia vastatrix, Puccinia striiformis, Puccinia arachidis, Rhizoctonia solani, Sphaerotheca fuliginea, Fusarium oxysporum, Verticillium dahliae, Pythium aphanidermatum, Phytophthora megasperma, Sclerotinia sclerotiorum, Sclerotium rolfsii, Erysiphe polygoni, Pyrenophora teres, Gaeumannomyces graminis, Rynchosporium secalis, Fusarium roseum, Bremia lactucae and other generea and species closely related to these pathogens.
Compounds of this invention can also be mixed with one or more other insecticides, fungicides, 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 compounds of this invention can be formulated are: insecticides such as abamectin, acephate, azinphos-methyl, bifenthrin, buprofezin, carbofuran, chlorfenapyr, chlorpyrifos, chlorpyrifos-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- (trifluoromemoxy)phenyl]amino]carbonyl]indeno[l,2-β][l,3,4]oxadiazine-4a(3H)- carboxylate (DPX-JW062), monocrotophos, oxa yl, parathion, parathion-methyl, permethrin, phorate, phosalone, phosmet, phosphamidon, pirimicarb, profenofos, rotenone, sulprofos, tebufenozide, tefluthrin, terbufos, tetrachlorvinphos, thiodicarb, tralomethrin, trichlorfon and triflumuron; fungicides such as acibenzolar, azoxystrobin, binomial, blasticidin-S, Bordeaux mixture (Triassic copper sulfate), bromuconazole, capropamid (KTU 3616), captafol, captan, carbendazim, chloroneb, chlorothalonil, copper oxychloride, copper salts, cymoxanil, cyproconazole, cyprodinil (CGA 219417),(S)-3,5-dichloro-N-(3-chloro-l- ethyl- 1 -methyl-2-oxopropyl)-4-methylbenzamide (RΗ 7281 ), diclocymet (S-2900), diclomezine, dicloran, difenoconazole,(S)-3,5-dihydro-5-methyl-2-(methylthio)-5-phenyl- 3- φhenylamino)-4H-imidazol-4-one (RP 407213), dimethomorph, diniconazole, diniconazole-M, dodine, edifenphos, epoxiconazole (BAS 480F), famoxadone, fenarimol, fenbuconazole, fencaramid (SZX0722), fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, fluazinam, fludioxonil, flumetover (RPA 403397), fluquinconazole, flusilazole, flutolanil, flutriafol, folpet, fosetyl-aluminum, furalaxyl, furametapyr (S-82658), hexaconazole, ipconazole, iprobenfos, iprodione, isoprothiolane, kasugamycin, kresoxim-methyl, mancozeb, maneb, mefenoxam, mepronil, metalaxyl, metconazole, metominostrobin/fenominostrobin (SSF-126), myclobutanil, neo-asozin (ferric methanearsonate), oxadixyl, penconazole, pencycuron, probenazole, prochloraz, propamocarb, propiconazole, pyrifenox, pyrimethanil, pyroquilon, quinoxyfen, spiroxamine, sulfur, tebuconazole, tetraconazole, thiabendazole, thifluzamide, thiophanate-methyl, thiram, triadimefon, triadimenol, tricyclazole, triticonazole, validamycin and vinclozolin; nematocides such as aldoxycarb and fenamiphos; bactericides such as streptomycin; acaricides such as amitraz, chinomethionat, chlorobenzilate, cyhexatin, dicofol, dienochlor, etoxazole, fenazaquin, fenbutatin oxide, fenpropathrin, fenpyroximate, hexythiazox, propargite, pyridaben and tebufenpyrad; and biological agents such as Bacillus thuringiensis, Bacillus thuringiensis delta endotoxin, baculovirus, and entomopathogenic bacteria, virus and fungi. In certain instances, combinations with other fungicides having a similar spectrum of control but a different mode of action will be particularly advantageous for resistance management. Plant disease control is ordinarily accomplished by applying an effective amount of a compound of this invention, either pre- or post-infection, to the portions of the plant to be protected such as the roots, stems, foliage, fruit, seeds, tubers or bulbs, or to the medium (soil or sand) in which the plant to be protected is growing. The compounds can also be applied 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.
The following TESTS demonstrate the control efficacy of compounds of this invention on specific pathogens. The pathogen control protection afforded by the compounds is not limited, however, to these species. See Index Tables A-B for compound descriptions. The following abbreviations are used in the Index Tables which follow: t is tertiary, s is secondary, n is normal, i is iso, c is cyclo, Me is methyl, Et is ethyl, Pr is propyl, /-Pr is isopropyl, Bu is butyl, Ph is phenyl, OMe is methoxy, OEt is ethoxy, SMe is methylthio, SEt is ethylthio, CN is cyano, NO2 is nitro, TMS is trimethylsilyl, S(O)Me is methylsulfinyl, and S(O)2Me is mefhylsulfonyl. The abbreviation "dec" indicates that the compound appeared to decompose on melting. The abbreviation "Ex." stands for "Example" and is followed by a number indicating in which example the compound is prepared.
INDEX TABLE A
Figure imgf000101_0001
Compound Number
Figure imgf000101_0002
CH CH2CH3 CH2CH2CH3 O 44-8 °C
Figure imgf000101_0003
CH CH2CH3 CH2CH2CH3 S 120-5 °C
CH2(c-propyl) CH2CH2CH3 O oil*
CH2CH3 CH2CH2CH2CH3 O 44-5 °C
CH2CH2CH3 CH2CH2CH2CH3 O oil*
Figure imgf000102_0002
CH2CH2CH3 CH2CH2CH3 S 78-9 °C
CH2CH2CH3 CH2CH2CH3 O 98-9 °C
Figure imgf000102_0001
INDEX TABLE B
Figure imgf000102_0003
II
Compound Number
Figure imgf000102_0004
CH2CH2CH3 CH2CH2CH3 O 120-2 °C
CH2(c-propyl) CH2CH2CH3 O 95-100 °C
CH2CH3 CH2CH2CH2CH3 O 70-6 °C
Figure imgf000103_0001
O oil*
O 110-4 °C
O oil*
Figure imgf000103_0002
Figure imgf000103_0003
*See Index Table C for IH NMR data
INDEX TABLE C
Cmpd No. IH NMR Data (CDC13 solution unless indicated otherwise)a H NMR (300 MHz, CDC13 δ 0.44 (m,4H); 0.97 (m,3H); 1.38 (m,lH); 1.66 (m,2H); 3.39 (t,2H); 3.96 (t,2H); 6.88 (d,lH); 7.82 (dd,lH); 8.31 (d,lH) lH NMR (300 MHz, CDC13 δ 0.96 (m,6H); 1.40 (m,2H); 1.57 (m,2H); 1.69 (m,2H); 3.48 (t,2H); 3.99 (t,2H); 6.88 (d,lH); 7.82 (dd,lH); 8.31 ( ,lH) lH NMR (300 MHz, CDC13 δ 1.02 (m,9H); 1.44 (m,9H); 1.76 (m,2H); 2.24 (m,lH); 4 10 (m,3H); 6.83 (d,lH); 7.83 (dd,lH); 8.32 (d,lH)
11 lH NMR (300 MHz, CDC13 δ 0.99 (m,6H); 1.40 (m,2H); 1.68 (m,4H); 3.48 (m,2H); 3.58 (m,2H); 6.96 (d,lH); 7.85 (dd,lH); 8.46 (d,lH) 14 iH NMR (330 MHz, CDC13 δ 0.90(m, 6H); 1.31(m, 12H); 1.65(m, 4H); 3.47(t, 2H); 3.60(t, 2H); 6.95(dd,lH); 7.84(dd,lH); 8.45( d,lH) 15 !H NMR (330 MHz, CDC13 δ 1.75(s, 6H); 4.03(s, 2H); 4.27(s, 2H);
4.83(s, 2H); 4.96(s, 2H); 6.97(dd, IH); 7.86(dd, IH); 8.46(d, IH) a lH NMR data are in ppm downfield from tetramethylsilane. Couplings are designated by (s)-singlet,
(d)-doublet, (t)-triplet, (q)-quartet, (m)-multiplet, (dd)-doublet of doublets, (dt)-doublet of triplets,
0?r s)-broad singlet.
BIOLOGICAL EXAMPLES OF THE INVENTION Test compounds were first dissolved in acetone in an amount equal to 3% of the final volume and then suspended at a concentration of 200 ppm in purified water containing 250 ppm of the surfactant Trem® 014 (polyhydric alcohol esters). The resulting test suspensions were then used in the following tests. Spraying these 200 ppm test suspensions to the point of run-off on the test plants is the equivalent of a rate of 500 g/ha. TEST A
The test suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore dust of Erysiphe graminis f sp. tritici, (the causal agent of wheat powdery mildew) and incubated in a growth chamber at 20°C for 7 days, after which disease ratings were made. TEST B
The test suspension was sprayed to the point of run-off on wheat seedlings. The following day the seedlings were inoculated with a spore suspension of Puccinia recondita (the causal agent of wheat leaf rust) and incubated in a saturated atmosphere at 20°C for 24 h, and then moved to a growth chamber at 20°C for 6 days, after which disease ratings were made.
TEST C The test suspension was sprayed to the point of run-off on rice seedlings. The following day the seedlings were inoculated with a spore suspension of Pyricularia oryzae (the causal agent of rice blast) and incubated in a saturated atmosphere at 27°C for 24 h, and then moved to a growth chamber at 30°C for 5 days, after which disease ratings were made.
TEST D The test suspension was sprayed to the point of run-off on tomato seedlings. The following day the seedlings were inoculated with a spore suspension of Phytophthora infestans (the causal agent of potato and tomato 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. TEST E The test suspension was sprayed to the point of run-off on grape seedlings. The following day the seedlings were inoculated with a spore suspension of Plasmopara viticola (the causal agent of grape downy mildew) and incubated in a saturated atmosphere at 20°C for 24 h, moved to a growth chamber at 20°C for 6 days, and then incubated in a saturated atmosphere at 20°C for 24 h, after which disease ratings were made.
TEST F
The test suspension was sprayed to the point of run-off on cucumber seedlings. The following day the seedlings were inoculated with a spore suspension of Botrytis cinerea (the causal agent of gray mold on many crops) and incubated in a saturated atmosphere at 20°C for 48 h, and moved to a growth chamber at 20°C for 5 days, after which disease ratings were made.
Results for Tests A-F 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). A dash (-) indicates no test results. ND indicates disease control not determined due to phytotoxicity. # indicates significant activity.
Table A
Cmpd No. Test A Test B Test C Test D Test E Test F
1 100**# 88# 0 76 - 0
2 76*# 0 0 0 - 0
3 100*# 0 0 63 - 54
4 100*# 0 0 46 - 85
5 100*# 0 0 63 - 0
6 98**# 0 0 0 - 21
7 98*# 0 0 47 - 0
8 97# 31*** 37 0 - 0
9 98*# 28 0 93# - 21
10 95*# 68# 0 86# - 54
11 99*# 68 0 93 - 91
12 91* 28 0 76# - 0
13 57* 0 0 26 - 0
14 0* 0 0 40 - 35
15 0* 22 0 92# - 0
16 0* 0 0 59 - 0
Test was run at 10 ppm.
**Test was run at 2 ppm.
***Test was run at 40 ppm.

Claims

CLAIMS What is claimed is:
1. A compound selected from Formulae I and II, N-oxides and agriculturally suitable salts thereof,
Figure imgf000106_0001
I II
wherein
Z is O, S(O)n or ΝR5; n is O, l, or 2; Q is O or S; G is, together with the two linking carbons, a substituted fused phenyl or a substituted fused 5- or 6-membered aromatic heterocychc ring system; each Rl and R2 is independently C C^ alkyl optionally substituted with NR6R7, nitro, cyano, CO2R6, one or more hydroxy, or Rl 1; C3-CIQ alkenyl; C3-CIQ alkynyl; Cj-Cio haloalkyl; C3-CIQ haloalkenyl; C3-CJO haloalkynyl; C -C10 alkoxyalkyl; C2-Cιo alkylthioalkyl; C2-C1Q alkylsulfonylalkyl; C4-C10 alkenyloxyalkyl; C4-C10 alkynyloxyalkyl; C4-C10 alkenylthioalkyl; C4-C10 alkynylthioalkyl; C2-Cιo haloalkoxyalkyl; C4-CK) alkoxyalkenyl; C4-C10 alkylthioalkenyl; C4-C10 trialkylsilylalkyl; C4-C10 alkoxy; COR6; CO2R6; or RU; or Rl and R2 in Formula II can be taken together as -CH2CH2CH2CH2-,
-CH2(CH2)3CH2-, -CH2CH2OCH2CH2-, -CH2CH(Me)CH2CH(Me)CH2- or -CH2CH(Me)OCH(Me)CH2-; R5 is C1-C4 alkyl; each R6 and R7 is independently hydrogen; C1-C4 alkyl optionally substituted with RU; or Rll; or each pair of R6 and R7, when attached to the same nitrogen atom, can be taken together as -CH2CH2CH2CH2-, -CH2(CH2)3CH2-, -CH2CH2OCH2CH2-, -CH2CH(Me)CH2CH(Me)CH2- or -CH2CH(Me)OCH(Me)CH2-; and each Rl 1 is independently an optionally substituted phenyl; an optionally substituted 3-, 4-, 5- or 6-membered non-aromatic carbocyclic ring, an optionally substituted
8-, 9- or 10-membered fused carbobicychc or fused heterobicyclic ring system; or an optionally substituted 3-, 4-, 5- or 6-membered heteromonocyclic ring; wherein said heterobicyclic ring systems and heteromonocyclic rings may be aromatic or nonaromatic and contain 1 to 4 heteroatoms independently selected from the group nitrogen, oxygen and sulfur, provided that each heterobicyclic ring system and heteromonocyclic ring contains no more than 4 nitrogens, no more than 2 oxygens and no more than 2 sulfurs, and wherein each heterobicyclic ring system and heteromonocyclic ring is bonded through a ring carbon atom; provided that i) when G is a fused phenyl ring, then R2 is other than trifluoromethyl or cyclohexyl; ii) when G in Formula II is, together with the two linking carbons, a fused phenyl or a fused pyridizine and Rl and R2 are taken together as -CH2CH2CH2CH2-, -CH2(CH2)3CH2-, -CH2CH2OCH2CH2-, -CH2CH(Me)CH2CH(Me)CH2- or -CH2CH(Me)OCH(Me)CH2-, then G must be substituted with at least two groups, one of which must be other than z'-propyl, methoxy or NO2; iii) when G in Formula II is, together with the two linking carbons, a fused phenyl, fused pyridizine or fused imidazole and R1 is allyl, C^ to C4 alkyl or unsubstituted phenyl, then G must be substituted with at least two groups, one of which must be other than methyl or methoxy; iv) when G in Formula II is, together with the two linking carbon atoms, a fused imidazole or fused thiophene and Rl is methyl, ethyl or allyl, then G cannot be substituted with methyl or CO2CH3; v) when G is , together with the two linking carbons, a fused pyridine or pyrimidine and Z is oxygen or sulfur, then G cannot be substituted with methyl, unsubstituted phenyl or morpholino; and vi) when G in Formula II is, together with the two linking carbon atoms, a fused phenyl ring and R and R2 are either both methyl or taken together to form -CH2CH2OCH2CH2-, then G cannot be substituted with methyl, CH3CO2- or unsubstituted phenyl.
2. A compound of Claim 1 , wherein each fused phenyl and fused heterocychc ring of G is substituted with R3 and is optionally substituted with R ; and each phenyl, carbocyclic ring, fused carbobicychc ring system, fused heterobicyclic fused ring system, and heteromonocyclic ring of Rl l is optionally substituted with R8, optionally substituted with R9 and optionally substituted with Rl°; wherein R3 is halogen; C2-C8 alkyl or C -C8 alkenyl, each optionally substituted with hydroxy, cyano or CO2R6; CH2OH; CH2CN; CH2CO2R6; C3-C8 cycloalkyl; C2-C8 alkynyl; C Cs haloalkyl; C3-C8 haloalkenyl; C3-C8 haloalkynyl; C Cs alkoxy; CrC8 haloalkoxy; C3-C8 alkenyloxy; C3-C8 alkynyloxy; CrC8 alkylthio; CrC8 alkylsulfonyl; C2-C8 alkoxyalkyl; C3-C8 trialkylsilyl; NR6R7; C5-C8 trialkylsilylalkynyl; or phenyl optionally substituted with at least one R12; SF5; CrC8 haloalkylthio; or SCN; R4 is hydrogen; halogen; C1-C4 alkyl; C^C haloalkyl; C1-C4 alkoxy; or C1-C4 haloalkoxy; each R8 is independently CrC6 alkyl; Cι-C6 alkoxy; Cι-C6 haloalkyl; halogen;
C2-C8 alkynyl; C Cg alkylthio; phenyl or phenoxy each optionally substituted with at least one R12; cyano; nitro; Cj-Cg haloalkoxy; Cj-Cg haloalkylthio; C2-C6 alkenyl; C2-C6 haloalkenyl; acetyl; CO2Me; or N(C C2 alkyl) ; each R9 is independently methyl; ethyl; methoxy; methylthio; halogen;
CO2(CrC3 alkyl); C(O)NR6R7; or trifluoromethyl; each Rl° is independently halogen; and each Rl2 is independently halogen; C1-C4 alkyl; C1-C4 alkoxy; C!-C haloalkyl; nitro; or cyano.
3. A compound of Claim 2, N-oxides and agriculturally suitable salts thereof wherein
G is, together with the two linking carbons, a fused phenyl, substituted with R3 and optionally substituted with R ; each Rl and R2 is independently Cj-Cs alkyl; C3-C6 cycloalkyl; C3-C5 alkenyl; C3-C5 alkynyl; CrC5 haloalkyl; C3-C5 haloalkenyl; C3-C5 haloalkynyl;
C -C5 alkoxyalkyl; C2-C5 alkylthioalkyl; C4-C7 cycloalkylalkyl, phenyl or thienyl, each optionally substituted with R8, R9 and Rl°; and Z is O.
4. A compound of Claim 3, N-oxides and agriculturally suitable salts thereof wherein
R3 is 6-halogen and R4 is 8-halogen.
5. The compound of Claim 4 which is 2,3-dihydro-6-iodo-3-propyl-2- (propylimino)-4H- 1 ,3 -benzoxazin-4-one.
6. A compound of Claim 2, N-oxides and agriculturally suitable salts thereof wherein
G is, together with the two linking carbons, a fused thienyl or fused pyridinyl, each optionally substituted with R3 and optionally substituted with R ; each Rl and R2 is independently C Cs alkyl; C3-C6 cycloalkyl; C3-C5 alkenyl; C3-C5 alkynyl; C C5 haloalkyl; C3-C5 haloalkenyl; C3-C5 haloalkynyl;
C2-C5 alkoxyalkyl; C2-C5 alkylthioalkyl; C4-C7 cycloalkylalkyl, phenyl or thienyl, each optionally substituted with R8, R9 and Rl°; and Z is O or S.
7. A compound of Claim 2, N-oxides and agriculturally suitable salts thereof wherein
R3 is halogen, C2-C alkynyl or Cj-C haloalkyl; and
R4 is halogen, C2-C8 alkynyl or Cι-C haloalkyl.
8. A fungicidal composition comprising a fungicidally effective amount of a compound of Claim 1 and at least one other component selected from the group consisting of surfactants, solid diluents and liquid diluents.
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 compound of Claim 1.
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