WO1995016676A1 - Arthropodicidal pentafluorothio substituted anilides - Google Patents

Arthropodicidal pentafluorothio substituted anilides Download PDF

Info

Publication number
WO1995016676A1
WO1995016676A1 PCT/US1994/013917 US9413917W WO9516676A1 WO 1995016676 A1 WO1995016676 A1 WO 1995016676A1 US 9413917 W US9413917 W US 9413917W WO 9516676 A1 WO9516676 A1 WO 9516676A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
alkyl
ocf
optionally substituted
independently selected
Prior art date
Application number
PCT/US1994/013917
Other languages
French (fr)
Inventor
Michael Henry Howard, Jr.
Thomas Martin Stevenson
Original Assignee
E.I. Du Pont De Nemours And Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by E.I. Du Pont De Nemours And Company filed Critical E.I. Du Pont De Nemours And Company
Priority to AU14309/95A priority Critical patent/AU1430995A/en
Publication of WO1995016676A1 publication Critical patent/WO1995016676A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/06—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C381/00—Compounds containing carbon and sulfur and having functional groups not covered by groups C07C301/00 - C07C337/00
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D273/00—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00
    • C07D273/02—Heterocyclic compounds containing rings having nitrogen and oxygen atoms as the only ring hetero atoms, not provided for by groups C07D261/00 - C07D271/00 having two nitrogen atoms and only one oxygen atom
    • C07D273/04—Six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems

Definitions

  • TITLE ARTHROPODICIDAL PENTAFLUOROTHIO SUBSTITUTED ANILIDES U.S. 4,863,947 and GB 2,276,382 pertain to SF 5 -substituted anilides which are not disclosed in the instant invention.
  • This invention pertains to compounds of Formula I, including all geometric and stereoisomers, agriculturally suitable salts thereof, agricultural compositions containing them and their use to control arthropods in both agronomic and nonagronomic environments.
  • the compounds are:
  • A is H
  • a 1 is selected from the group CH 2 , CH 2 CH 2 , O, S(O) q , NR 7 , OCH 2 , S(O) q CH 2 , N(R 7 )CH 2 , substituted CH 2 , and substituted CH 2 CH 2 , the substituents independently selected from 1-2 halogen and 1-2 methyl;
  • E is selected from the group H and C 1 -C3 alkyl
  • a and E are taken together to form CH 2 , CH 2 CH 2 , O, S(O) q , NR 7 , OCH 2 , S(O) q CH 2 , N(R 7 )CH 2 , substituted CH2, and substituted CH 2 CH 2 , the substituents independently selected from 1-2 halogen and 1-2 methyl;
  • M is selected from the group H and C1-C3 alkyl
  • E and M are taken together as CH 2 CH 2 , CH 2 CH 2 CH 2 or CH2CH2CH2CH2, each group optionally substituted with one or more members independently selected from the group halogen, NO2, CN, C1-C3 alkyl, C1-C3 haloalkyl, OR 8 , C(O)R 16 and C(O)OR 16 ;
  • X is selected from the group O and S;
  • Y is selected from the group H, C j -Cg alkyl, C j -C6 haloalkyl, C2-C6 alkenyl, C 2 -Cg haloalkenyl, C2-Cg alkynyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C 3 -C 6 halocycloalkyl, C 4 -C 7 cycloalkylalkyl, CHO, C(O)R 16 , C(O)OR 16 , C(S)R 16 , C(S)SR 16 , C(O)C(O)OR 16 , C(O)CH 2 C(O)OR 16 , SH, S(O) r R 16 , S(O) 2 CH 2 C(O)OR 16 , P(X 1 )(OR 18 ) 2 , S(O) r N(R 12 )C(O)OR 11 , S(O) r NR 13
  • R 4 , R 5 and R 6 are independently selected from the group H, C r C 4 alkyl, C(O)R 16 and C(O)OR 16 ;
  • R 7 is selected from the group H, C1-C4 alkyl, C 1 -C 4 haloalkyl, C2-C4 alkenyl,
  • R 8 is selected from the group H, C r C 4 alkyl, C C 4 haloalkyl, C 2 -C 4 alkenyl, C 2 -C 4 haloalkenyl, C 2 -C 4 alkynyl, C 2 -C 4 haloalkynyl, C(O)R 16 , C(O)OR 16 , C(O)NR 16 R 17 , S(O) 2 NRl 6 Rl 7 , S(O) 2 R 16 , optionally substituted phenyl, and optionally substituted benzyl wherein the optional phenyl and benzyl substituents are 1-2 substituents independently selected from the W; R9 is selected from the group H, C r C 4 alkyl, C(O)R 16 and C(O)OR 16 ; R 10 is selected from the group H, C r C 4 alkyl, C r C 4 haloalkyl and phenyl optionally substituted with 1-2 substituents independently selected
  • R 11 is C r C 18 alkyl
  • R 12 is C r C 4 alkyl
  • R 13 and R 14 are independently C1-C4 alkyl
  • R 13 and R 14 are taken together as or CH2CH2OCH2CH2;
  • R 15 is selected from the group J and phenyl optionally substituted with (R 2 ) p ;
  • R 16 is selected from the group C r C 6 alkyl, C r C 6 haloalkyl, C -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, C 2 -C 6 alkoxyalkyl, C2-C 6 alkylthioalkyl, 0 ⁇ 5 nitroalkyl, C2-C 6 cyanoalkyl, C 3 -C 8 alkoxycarbonylalkyl, C3-C6 cycloalkyl, C 3 -Cg halocycloalkyl, optionally substituted phenyl and optionally substituted benzyl wherein the optional phenyl and benzyl substituents are
  • R 17 is selected from the group H and C1-C4 alkyl
  • R 16 and R 17 when attached to the same atom, are taken together as (CH2)4,
  • R 18 is selected from the group C1-C3 alkyl and phenyl optionally substituted with at least one member independently selected from W;
  • R 19 is selected from the group H, C2-C 6 alkyl, C j -Cg haloalkyl, C 2 -C 6 alkenyl, C2-C 6 haloalkenyl, C2-C 6 alkynyl, C 2 -C 6 haloalkynyl, C3-C6 cycloalkyl, C 3 -C 6 halocycloalkyl, CHO, C(O)R 16 , C(O)OR 16 , C(S)R 16 , C(S) 2 R 16 , C(O)C(O)OR 16 , C(O)CH 2 C(O)OR 16 , S(O) r R 16 , S(O) 2 CH 2 C(O)OR 16 , P(X)(OR 18 ) 2 , C(O)NR 16 R 17 , S(O) r NR 16 R 17 , S(O) r N(R 12 )C(O)OR 11 ,
  • R 19 is C j -C4 alkyl substituted with 1-2 substituents independently selected from the group C1-C2 alkoxy, C r C 2 haloalkoxy, CN, NO 2 , C(O)R 16 , C(O)OR 16 and NR 8 R 9 ;
  • R 20 and R 21 are independently C r C 4 alkyl
  • R 22 is selected from the group C1-C4 alkyl and phenyl optionally substituted with W;
  • R 23 is selected from the group C r C 6 alkyl, C r C 6 haloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, C 2 -C 6 haloalkynyl, OR 8 , C 2 -C 6 alkoxyalkyl, C 2 -C 6 alkylthioalkyl, C ⁇ -C 6 nitroalkyl, C 2 -C 6 cyanoalkyl, C 3 -C 8 alkoxycarbonylalkyl, C3-C6 cycloalkyl, C 3 -Cg halocycloalkyl, halogen, CN, N 3 , SCN, NO 2 , CHO, C(O)R 16 , C(O)OR 16 , C(O)NR 16 R 17
  • W is selected from the group halogen, CN, NO 2 , C ⁇ -C 2 alkyl, C ⁇ -C 2 haloalkyl, Cj-C 2 alkoxy, C ⁇ -C 2 haloalkoxy, C 1 -C2 alkylthio, C r C 2 haloalkylthio, C ⁇ -C 2 alkylsulfonyl, and C ⁇ -C haloalkylsulfonyl;
  • X 1 is selected from the group O or S;
  • Z 1 and Z 2 are independently selected from the group CH or N;
  • m is 1 to 3;
  • n is 1 to 3;
  • p is 0 to 3;
  • q is 0 to 3; and r is 0, 1 or 2.
  • Exemplary values of J include:
  • Preferred Compounds A are compounds of Formula I wherein
  • Y is selected from the group H, C r C 6 alkyl, C(O)Rl 6 and C(O)ORl 6 .
  • Preferred Compounds B are compounds of Preferred A wherein
  • Q is Q-1;
  • Al is selected from the group CH 2 , CH 2 CH 2 , OCH 2 , S(O) q CH 2 and
  • Preferred Compounds C are compounds of Preferred B wherein
  • Preferred Compounds D are compounds of Preferred A wherein Q is Q-2; Rl is H; and SF 5 is in the 4-position.
  • Preferred Compounds E are compounds of Preferred A wherein
  • a and E are taken together to form CH 2 , CH 2 CH 2 , OCH 2 , S(O) q CH 2 and N(R 7 )CH 2 ; and X is O.
  • Preferred Compounds F are compounds of Preferred E wherein Q is Q-3.
  • Preferred Compounds G are compounds of Preferred F wherein
  • Rl is H
  • Z is selected from the group O, S(O) q and NRl9; and SF 5 is in the 4-position.
  • Preferred Compounds H are compounds of Preferred A wherein
  • R 1 is H
  • SF 5 is in the 4-position.
  • Compound I of Preferred C which is:
  • Stereoisomers of this invention can exist as one or more stereoisomers.
  • the various stereoisomers include enantiomers, diastereomers and geometric isomers.
  • one stereoisomer may be more active and/or may exhibit beneficial effects when enriched relative to the other stereoisomer(s) or when separated from the other stereoisomer(s). Additionally, the skilled artisan knows how to separate said stereoisomers. Accordingly, the present invention comprises racemic mixtures, individual stereoisomers, and optically active mixtures of compounds of Formula I as well as agriculturally suitable salts thereof.
  • alkyl used either alone or in compound words such as “alkylthio” or “haloalkyl” denotes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, i-propyl, or the different isomers through octadecyl.
  • alkenyl denotes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers.
  • Alkenyl also denotes polyenes such as 1,3-hexadiene.
  • Alkynyl denotes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 3-propynyl and the different butynyl, pentynyl and hexynyl isomers.
  • Alkoxy denotes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers.
  • Alkoxyalkyl denotes alkoxy substitution on alkyl.
  • alkoxyalkyl examples include CH 3 OCH 2 , CH 3 OCH 2 CH 2 , CH 3 CH 2 OCH 2 , CH 3 CH 2 CH 2 OCH 2 and CH 3 CH 2 OCH 2 CH 2 and the different pentyl and hexyl isomers.
  • Alkylthioalkyl denotes alkylthio appended to straight or branched-chain alkyl groups.
  • Alkylthio denotes straight-chain or branched alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers.
  • Alkylsulfonyl denotes straight-chain or branched moieties such as CH3S(O)2 and CH 3 CH 2 S(O)2.
  • Cycloalkylene denotes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • Examples of “cycloalkylalkyl” include cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl and the different Cg and C 7 isomers bonded to straight-chain or branched alkyl groups.
  • Alkoxycarbonylalkyl denotes straight-chain or branched esters substituted on straight-chain or branched alkyl groups.
  • alkoxycarbonylalkyl examples include CH2C(O)OCH3, CH 2 C(O)OCH 2 CH 3 , CH 2 CH 2 C(O)OCH 3 and the different C 4 , C 5 , C 6 , C 7 and C 8 isomers.
  • halogen either alone or in compound words such as “haloalkyl”, denotes fluorine, chlorine, bromine or iodine. Further, when used in compound words such as “haloalkyl", said alkyl may be partially or fully substituted with halogen atoms which may be the same or different.
  • haloalkyl examples include F3C, CICH2, CF 3 CH 2 and CF 3 CC1 2 .
  • haloalkynyl examples include HOCCHC1, CF3G--C, CC1 3 C ⁇ C and FCH 2 C ⁇ CCH 2 .
  • haloalkoxy examples include CF 3 O, CCl 3 CH 2 O, CF2 H H 2 CH2O and CF 3 CH 2 O.
  • haloalkylthio examples include CC1 3 S, CF 3 S, and CC1 3 CH 2 S.
  • haloalkylsulfonyl examples include CF 3 SO 2 , CCl 3 SO 2 , CF 3 CH 2 SO 2 and CF 3 CF 2 SO 2 .
  • 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 18.
  • C j -Cg alkyl designates methyl, ethyl, and propyl through hexyl isomers
  • C 2 alkoxy designates CH 3 CH 2 O-
  • C 3 alkoxy designates CH 3 CH 2 CH 2 O- or (CH 3 ) 2 CHO-.
  • Formula HI compounds may be prepared by reaction of Formula IV anilines with a suitable carbonylating reagent such as phosgene, bis(trichloromethyl) carbonate (triphosgene) or l.T-carbonyldiimidazole in the presence of an acid scavenger such as a trialkylamine in an inert polar or nonpolar aprotic solvent as shown in Scheme 2.
  • a suitable carbonylating reagent such as phosgene, bis(trichloromethyl) carbonate (triphosgene) or l.T-carbonyldiimidazole
  • an acid scavenger such as a trialkylamine in an inert polar or nonpolar aprotic solvent as shown in Scheme 2.
  • Formula IV anilines may in turn be prepared by ring substitution reactions of Formula V anihnes using methods known to one skilled in the art (Norman and Taylor, Electrophilic Substitution in Benzenoid Compounds, American Elsevier, New York, (1965); Miller, Aromatic Nucleophilic Substitution, American Elsevier, New York, (1968)) as shown in Scheme 3.
  • anilines of Formula V can be prepared by the well-known treatment of their corresponding acid addition salts of Formula VI (wherein W 1 is equal to Cl, Br, HSO4 or other suitable counterion) with an organic or inorganic base as shown in Scheme 4.
  • Formula VI salts may be prepared by catalytic reduction of nitrobenzene derivatives of Formula VH over a suitable catalyst such as platinum oxide in an alcohol solvent in the presence of a mineral acid and under 103.5 kPa to 517.5 kPa of hydrogen as shown in Scheme 5. This reaction is usually conducted at a range of 10° to 80°C and is typically complete in 8 h.
  • a suitable catalyst such as platinum oxide in an alcohol solvent in the presence of a mineral acid and under 103.5 kPa to 517.5 kPa of hydrogen as shown in Scheme 5. This reaction is usually conducted at a range of 10° to 80°C and is typically complete in 8 h.
  • Formula VII compounds may be prepared by treatment of the corresponding disulfides of Formula VHI with silver difluoride according to methods known in the literature (7. Am. Chem. Soc. (1962), 84, 3064) as shown in Scheme 6.
  • Formula I (Q-l) compounds may be prepared by reaction of Formula DC carbamoyl chlorides with Formula VI salts in the presence of a suitable base such as a trialkylamine or substituted pyridine as shown in Scheme 7.
  • a suitable base such as a trialkylamine or substituted pyridine as shown in Scheme 7.
  • Typical solvents include polar and nonpolar aprotic solvents. The reaction is usually conducted at 0°C to the reflux temperature of the particular solvent used and is typically complete in 24 h.
  • IX Formula IX compounds can be prepared by reaction of Formula II dihydropyrazoles, or their acid addition salts, with phosgene or a phosgene equivalent in an inert solvent and in the presence of base as shown in Scheme 8.
  • Typical solvents include polar and nonpolar aprotic solvents. The reaction is usually conducted at 0°C to the reflux temperature of the particular solvent used and is typically complete in 24 h.
  • Formula I (Q-4) compounds may be prepared by reaction of Formula XIH hydrazones with an equimolar amount of Formula HI aryl isocyanate as shown in Scheme 12.
  • the Formula XIH hydrazones may in turn be prepared by condensation of hydrazine with ketones of Formula XIV as shown in Scheme 13. Examples of both of these procedures and preparation of Formulae XIH and XIV compounds are described in WO 92/06076.
  • Compounds of Formula I (Q-5) may be prepared by reaction of an acid of Formula XV with thionyl chloride or another chlorinating agent followed by treatment with a Formula IV aniline in the presence of an amine base, such as triethylamine, as shown in Scheme 14. Examples of this procedure and preparation of Formula XV compounds are described in WO 88/05046.
  • Compounds of Formula I (Q-7) can be prepared in a three-step process whereby Formula XVHI esters are saponified, converted to the acid chloride and reacted with Formula IV anilines in an inert solvent and in the presence of an acid scavenger as shown in Scheme 17. Examples of this procedure and preparation of Formula XVHI compounds are described in WO 92/06076.
  • Step B Methyl 2-fchlorocarbonylV2.3-dihvdro-7-(trifluoromethvnrn- benzopyranor4.3-c1pyrazole-3a(4H)-carboxylate
  • a suspension of methyl 2,3-dihydro-7-(trifluoromethyl)[l]benzopyrano[4,3-c]- pyrazole-3a-carboxylate hydrochloride (1.5 g, 0.0045 mol), prepared as described previously (WO 90/10623), in saturated aqueous sodium hydrogen carbonate (25 mL), was extracted with chloroform (60 mL total).
  • Step C r4-rrr3a.4-Dihvdro-3a-(methoxycarbonylV7-(trifluoromethyl n- benzopyranor4.3-c]pyrazol-2f3H)-yl1carbonvflamino1phenyl1- pentafluorosulfide
  • the compound diisopropylethylamine (0.59 g, ' 0.0046 mol) was added to a solution of the compound from Step B, methyl 2-(chlorocarbonyl)-2,3-dihydro-7- (trifluoromethyl)[l]benzopyrano-[4,3-c]pyrazole-3a(4H)-carboxylate, (0.86 g, 0.0024 mol) in dichloromethane (47 mL).
  • the compound from Step A The compound from Step A,
  • Step B r4-r(Clilorocajbonyl)(methoxycarbonyl ' )amino1phenyllpentafluorosulfur
  • An oil dispersion of 60 % sodium hydride (0.1 g, 0.0025 mol) was added to a solution of the product of Step A, [4-t(methoxycarbonyl)amino]phenyl]pentafluo ⁇ o- sulfur, (0.6 g, 0.0022 mol) in benzene (5 mL). After 15 min ethylene glycol dimethyl ether (0.4 mL) was added and the mixture was heated to 60°C for 2 h.
  • Step C After cooling to room temperature the resulting off-white suspension was transferred via syringe into a solution of 1.93M phosgene in toluene (5.6 mL, 0.0108 mol) at 5°C. After stirring at 5 °C for 30 min the reaction mixture was concentrated to dryness and then redissolved in ethyl acetate (5 mL) for use directly in the next step (Step C).
  • Step C (+/-)-r4-rrr7-Chloro-4a.5-dihydro-4a-(methoxycarbonyl)indeno- ⁇ .2-el- ⁇ .3.41oxadiazin-2(3H ' )-yllcarbonyll(methoxycarbonyl ' )aminolphenyll- pentafluorosulfur
  • Step A 1 -(4-Chlorophenyl)-2-methylene- 1 -pentanone
  • Step A l-(4-chlorophenyl)-l-pent-2-ene (31.04 g, 0.1487 mol) was added dropwise to warm (60°C) sulfuric acid such that T; ⁇ 75°C. After the addition was complete, the mixture was heated at 65°C for 4 h, cooled to room temperature, and poured in a well-stirred mixture of ice (500 g), water (300 g), dichloromethane (250 mL). The organic layer was separated and saved, and the aqueous layer was extracted with ethyl acetate (2 X 150 mL).
  • Step C r4-rrrf5-Chloro-2.3-dihvdro-2-propyl-lH-inden-l-ylideneVhydrazo1- carbonvn-aminolphenyllpentafluorosulfur Hydrazine hydrate (0.23 g, 0.0046 mol) was added to a suspension of the product of Step B, 5-chloro-2,3-dihydro-2-propyl-lH-inden-l-one (0.75 g, 0.0036 mol) in ethanol (10 mL) and the mixture was heated under reflux for 21 h, cooled to room temperature, concentrated, redissolved in ethyl acetate, washed successively with water, saturated aqueous sodium hydrogen carbonate and brine, dried over sodium sulfate, filtered and concentrated.
  • R 2 H 3-C1 3-CF3 3-OCF3 3-OCF 2 H
  • Compounds of this invention will generally be used in formulation with an agriculturally suitable carrier comprising a liquid or solid diluent.
  • Useful formulations include dusts, granules, baits, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the like, consistent with the . physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature.
  • 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 weight percent. Weight Percent
  • 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 and solvents 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.
  • Fine solid compositions are made by blending and, usually, grinding as in a hammer mill or fluid energy mill.
  • Water-dispersible granules can be produced by agglomerating a fine powder composition; see for example, Cross et al., Pesticide Formulations, Washington, D.C., 1988, pp 251-259.
  • Suspensions are prepared by wet-milling; see, for example, U.S. 3,060,084.
  • Granules and pellets can be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning,
  • Compound 1 65.0% dodecylphenol polyethylene glycol ether 2.0% sodium ligninsulfonate 4.0% sodium silicoaluminate 6.0% montmorillonite (calcined) 23.0%.
  • Compound 1 10.0% attapulgite granules (low volatile matter, 0.71/0.30 mm; U.S. S. No.
  • Compound 1 25.0% anhydrous sodium sulfate 10.0% crude calcium ligninsulfonate 5.0% sodium alkylnaphthalenesulfonate 1.0% calcium/magnesium bentonite 59.0%.
  • Compound 1 20.0% blend of oil soluble sulfonates and polyoxyethylene ethers 10.0% isophorone 70.0%.
  • the compounds of this invention exhibit activity against a wide spectrum of foliar-feeding, fruit-feeding, stem or root feeding, seed-feeding, aquatic and soil-inhabiting arthropods (term “arthropods” includes insects, mites and nematodes) which are pests of growing and stored agronomic crops, forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health. Those skilled in the art will appreciate that not all compounds are equally effective against all growth stages of all pests.
  • all of the compounds of this invention display activity against pests that include: eggs, larvae and adults of the Order Lepidoptera; eggs, foliar-feeding, fruit-feeding, root-feeding, seed-feeding larvae and adults of the Order Coleoptera; eggs, immatures and adults of the Orders Hemiptera and Homoptera; eggs, larvae, nymphs and adults of the Order Acari; eggs, immatures and adults of the Orders Thysanoptera, Orthoptera and Dermaptera; eggs, immatures and adults of the Order Diptera; and eggs, juveniles and adults of the Phylum Nematoda.
  • the compounds of this invention are also active against pests of the Orders Hymenoptera, Isoptera, Siphonaptera, Blattaria, Thysanura and Psocoptera; pests belonging to the Class Arachnida and Phylum Platyhelminthes.
  • the compounds are active against southern corn rootworm (Diabrotica undecimpunctata howardi), aster leafhopper (Mascrosteles fascifrons), boll weevil (Anthonomus grandis), two-spotted spider mite ⁇ Tetranychus urticae), fall army worm (Spodopterafrugiperda), black bean aphid (Aphis fabae), green peach aphid (Myzus persica), cotton aphid (Aphis gossypii), Russian wheat aphid (Diuraphis noxia), English grain aphid (Sitobion avenae), tobacco budworm (Heliothis virescens), rice water weevil (Lissorhoptrus oryzophilus), rice leaf beetle (Oulema oryzae), whitebacked planthopper (Sogatellafurcifera), green leafhopper (Nephotettix cincticeps), brown
  • Tetranychidae including Tetranychus urticae, Tetranychus cinnabarinus, Tetranychus mcdanieli, Tetranychus pacificus, Tetranychus turkestani, Byrobia rubrioculus, Panonychus ulmi, Panonychus citri, Eotetranychus carpini borealis, Eotetranychus, hicoriae, Eotetranychus sexmaculatus, Eotetranychus yumensis, Eotetranychus banksi and Oligonychus pratensis;
  • Tenuipalpidae including Brevipalpus lewisi, Brevipalpus phoenicis, Brevipalpus calif ornicus and Brevipalpus obovatus; Eriophyidae including Phyllocoptruta oleivora, Eriophyes sheldoni, Aculus cornutus, Epitrimerus pyri and Eriophyes mangiferae. See WO 90/10623 and WO 92/00673 for more detailed pest descriptions.
  • 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.
  • insecticides such as avermectin B, monocrotophos, carbofuran, tetrachlorvinphos, malathion, parathion-methyl, methomyl, chlordimeform, diazinon, deltamethrin, oxamyl, fenvalerate, esfenvalerate, permethrin, profenofos, sulprofos, triflumuron, diflubenzuron, methoprene, buprofezin, thiodicarb, acephate, azinphosmethyl, chlo yrifos, dimethoate, fipronil, flufenprox, fonophos, isofenphos, methidathion, metha-midophos, phosmet, phosphamidon, phosalone, pirimicarb, phorate, terbuf
  • Arthropod pests are controlled and protection of agronomic, horticultural and specialty crops, animal and human health is achieved by applying one or more of the compounds of this invention, in an effective amount, to the environment of the pests including the agronomic and or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled.
  • the present invention further comprises a method for the control of foliar and soil inhabiting arthropods and nematode pests and protection of agronomic and/or nonagronomic crops, comprising applying one or more of the compounds of Formula I, or compositions containing at least one such compound, in an effective amount, to the environment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled.
  • a preferred method of application is by spraying.
  • granular formulations of these compounds can be applied to the plant foliage or the soil.
  • Other methods of application include direct and residual sprays, aerial sprays, seed coats, microencapsulations, systemic uptake, baits, eartags, boluses, foggers, fumigants, aerosols, dusts and many others.
  • the compounds can be incorporated into baits that are consumed by the arthropods or in devices such as traps and the like.
  • the compounds of this invention can be applied in their pure state, but most often application will be of a formulation comprising one or more compounds with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use.
  • a preferred method of application involves spraying a water dispersion or refined oil solution of the compounds. Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, and synergists and other solvents such as piperonyl butoxide often enhance compound efficacy.
  • the rate of application required for effective control will depend on such factors as the species of arthropod to be controlled, the pest's life cycle, life stage, its size, location, time of year, host crop or animal, feeding behavior, mating behavior, ambient moisture, temperature, and the like. Under normal circumstances, application rates of about 0.01 to 2 kg of active ingredient per hectare are sufficient to control pests in agronomic ecosystems, but as little as 0.001 kg/hectare may be sufficient or as much as 8 kg hectare may be required. For nonagronomic applications, effective use rates will range from about 1.0 to 50 mg/square meter but as little as 0.1 mg/square meter may be sufficient or as much as 150 mg/square meter may be required.
  • Control efficacy represents inhibition of arthropod development (including mortality) that causes significantly reduced feeding.
  • the pest control protection afforded by the compounds is not limited, however, to these species. See Index Tables A-D for the compound descriptions.
  • Fall Armyworm Test units each consisting of a H.I.S. (high impact styrene) tray with 16 cells were prepared. Wet filter paper and approximately 8 cm 2 of lima bean leaf was placed into twelve of the cells. A 0.5 cm layer of wheat germ diet was placed into the four remaining cells. Fifteen to twenty third-instar larvae of fall armyworm (Spodoptera frugiperdd) were placed into a 230 mL (8 ounce) plastic cup. Solutions of each of the test compounds in 75/25 acetone/distilled water solvent were sprayed into the tray and cup.
  • H.I.S. high impact styrene
  • Spraying was accomplished by passing the tray and cup on a conveyer belt directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 0.55 kg of active ingredient per hectare (about 0.5 pounds per acre) at 207 kPa (30 p.s.i.).
  • the insects were transferred from the 230 mL cup to the H.I.S. tray (one insect per cell).
  • the trays were covered and held at 27°C and 50% relative humidity for 48 h, after which time readings were taken on the twelve cells with lima bean leaves. The 4 four remaining cells were read at 6-8 days for delayed toxicity.
  • the following gave control efficacy levels of 80% or greater: 1, 2, 3, 4, 5 * , 6 * and 10 * . * - tested at 0.14 kg/ha.
  • TEST A The test procedure of TEST A was repeated to determine efficacy against third-instar larvae of the tobacco budworm (Heliothis virescens) except that three 230 mL (8 ounce) plastic cups with wheat germ diet were used in place of the H.I.S. tray, with each cup pre-infested with 5 third-instar larvae. Of the compounds tested, the following gave mortality levels of 80% or higher: 1, 3, 4, 5 * and 10*. * - tested at 0.14 kg/ha. TEST C Southern Corn Rootworm
  • Test units each consisting of a 230 mL (8 ounce) plastic cup containing a 2.54 cm 2 plug (1 square inch) of a wheatgerm diet, were prepared. The test units were sprayed as described in TEST A with individual solutions of the test compounds. After the spray on the cups had dried, five second-instar larvae of the southern corn rootworm (Diabrotica undecimpunctata howard ⁇ ) were placed into each cup. The cups were held at 27°C and 50% relative humidity for 48 h, after which time mortality readings were taken. The same units were read again at 6-8 days for delayed toxicity. Of the compounds tested, the following gave control efficacy levels of 80% or greater: 1 and 4.
  • Test units were prepared from a series of 350 mL (12 ounce) cups, each containing oat (Avena sativa) seedlings in a 2.54 cm (1 inch) layer of sterilized soil.
  • the test units were sprayed as described in TEST A with individual solutions of the test compounds. After the oats had dried from the spraying, 10 to 15 adult aster leafhoppers (Mascrosteles fascifrons) were aspirated into each of the cups.
  • the cups were covered with vented lids and held at 27°C and 50% relative humidity for 48 h, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher: 1 and 2.
  • Test units consisting of 260 mL (9 ounce) cups containing five adult boll weevils (Anthonomus grandis grandis) were prepared. The test units were sprayed as described in TEST A with individual solutions of the test compounds. Each cup was covered with a vented lid and held at 27°C and 50% relative humidity for 48 h, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher: 1 and 3.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

Abstract

Arthropodicidal compounds, compositions and use of compounds having formula (I), wherein Q, X, Y, R1 and m are as defined in the text.

Description

TITLE ARTHROPODICIDAL PENTAFLUOROTHIO SUBSTITUTED ANILIDES U.S. 4,863,947 and GB 2,276,382 pertain to SF5-substituted anilides which are not disclosed in the instant invention.
SUMMARY OF THE INVENTION This invention pertains to compounds of Formula I, including all geometric and stereoisomers, agriculturally suitable salts thereof, agricultural compositions containing them and their use to control arthropods in both agronomic and nonagronomic environments. The compounds are:
Figure imgf000003_0001
wherein
Q is selected from the group
Figure imgf000003_0002
0-3
Figure imgf000004_0001
A is H;
A1 is selected from the group CH2, CH2CH2, O, S(O)q, NR7, OCH2, S(O)qCH2, N(R7)CH2, substituted CH2, and substituted CH2CH2, the substituents independently selected from 1-2 halogen and 1-2 methyl;
E is selected from the group H and C1-C3 alkyl; or
A and E are taken together to form CH2, CH2CH2, O, S(O)q, NR7, OCH2, S(O)qCH2, N(R7)CH2, substituted CH2, and substituted CH2CH2, the substituents independently selected from 1-2 halogen and 1-2 methyl;
M is selected from the group H and C1-C3 alkyl; or
E and M are taken together as CH2CH2, CH2CH2CH2 or CH2CH2CH2CH2, each group optionally substituted with one or more members independently selected from the group halogen, NO2, CN, C1-C3 alkyl, C1-C3 haloalkyl, OR8, C(O)R16 and C(O)OR16;
X is selected from the group O and S;
Y is selected from the group H, Cj-Cg alkyl, Cj-C6 haloalkyl, C2-C6 alkenyl, C2-Cg haloalkenyl, C2-Cg alkynyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C7 cycloalkylalkyl, CHO, C(O)R16, C(O)OR16, C(S)R16, C(S)SR16, C(O)C(O)OR16, C(O)CH2C(O)OR16, SH, S(O)rR16, S(O)2CH2C(O)OR16, P(X1)(OR18)2, S(O)rN(R12)C(O)OR11, S(O)rNR13R14, N=CR9RlO, OR8, NR8R9; benzyl optionally substituted with 1-3 groups independently selected from the group W; and C1-C6 alkyl substituted with halogen, C1-C3 alkoxy, C1-C3 haloalkoxy, CN, NO2, S(O)rR16, P(X1)(OR18)2, C(O)R16, C(O)OR16 and phenyl optionally substituted with halogen, CN, C1-C2 haloalkyl and C1-C2 haloalkoxy; Z is selected from the group CH2, O, S(O)q and NR19; R1 and R2 are independently selected from the group H, Cj-Cg alkyl, Ci-Cg haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C -C6 haloalkynyl, OR8, C2-C6 alkoxyalkyl, C2-C6 al ylthioalkyl, CrC6 nitroalkyl, C2-Cg cyanoalkyl, C3~C alkoxycarbonylalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, halogen, CN, N3, SCN, NO2, SH, S(O)rR16, OCHO, CHO, C(O)R16, C(O)OR16, C(O)NR16R17, S(O)2NR16R17, NR16R17, NR17C(O)R16, OC(O)NHR16, NR17C(O)NHR16, NR17S(O)2R16, phenyl optionally substituted with 1-3 substituents independently selected from W, and benzyl optionally substituted with 1-3 substituents independently selected from W; or when m or n is 2 and the two R1 groups or the two R2 groups are adjacent, (R1) are optionally taken together as, or (R2)2 are optionally taken together as, -OCH2O-, -OCF2O-, -OCH2CH2O-, -CH2C(CH3)2O-, -CF2CF2O- or -OCF2CF2O- to form a cyclic bridge; R3 is selected from the group J, H, halogen, Cj-Cg alkyl, Cj-Cg haloalkyl, C2-C6 alkenyl, C2-Cg haloalkenyl, C2-Cg alkynyl, C2-C6 haloalkynyl, C4-C7 cycloalkylalkyl, OR8, C3-C8 alkoxycarbonylalkyl, CHO, C(O)R16, C(O)OR^, C(O)NR16R17, C(S)NR16R17, C(S)R16, C(S)SR16, CN, Si(R20)(R21)(R22), SH, S(O)rR16, P(X1)(OR18)2, N3, NO2, NR8R9, phenyl optionally substituted with (R23)p, and benzyl optionally substituted with 1-3 substituents independently selected from W; or R3 is C2-Cg epoxyalkyl optionally substituted with 1-2 substituents independently selected from the group CrC3 alkyl, CN, C(O)R16, C(O)OR16 and phenyl optionally substituted with W; or R3 is Cj-C6 alkyl substituted with one or more members independently selected from the group OR8, C(O)NRI6R17,
C(O)R16, C(O)OR16, SH, S(O)rR16, SCN, CN, Si(R20)(R21)(R22) and NR8R9; R4, R5 and R6 are independently selected from the group H, CrC4 alkyl, C(O)R16 and C(O)OR16; R7 is selected from the group H, C1-C4 alkyl, C1-C4 haloalkyl, C2-C4 alkenyl,
C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, CHO, C(O)R16, C(O)OR16, C(O)NRl6Rl7, C(S)NR16R17, C(S)R , C(S)SRl6, SCO^R^, P(X1)(OR18)2, optionally substituted phenyl, and optionally substituted benzyl wherein the optional phenyl and benzyl substituents are 1-2 substituents independently selected from W;
R8 is selected from the group H, CrC4 alkyl, C C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, C(O)R16, C(O)OR16, C(O)NR16R17, S(O)2NRl6Rl7, S(O)2R16, optionally substituted phenyl, and optionally substituted benzyl wherein the optional phenyl and benzyl substituents are 1-2 substituents independently selected from the W; R9 is selected from the group H, CrC4 alkyl, C(O)R16 and C(O)OR16; R10 is selected from the group H, CrC4 alkyl, CrC4 haloalkyl and phenyl optionally substituted with 1-2 substituents independently selected from W; or R9 and R10 are taken together as CH2CH2CH2, CH2CH2CH2CH2 or
CH2CH2CH2CH2CH2; R11 is CrC18 alkyl; R12 is CrC4 alkyl;
R13 and R14 are independently C1-C4 alkyl; or
R13 and R14 are taken together as
Figure imgf000006_0001
or CH2CH2OCH2CH2; R15 is selected from the group J and phenyl optionally substituted with (R2 )p; R16 is selected from the group CrC6 alkyl, CrC6 haloalkyl, C -C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, 0^5 nitroalkyl, C2-C6 cyanoalkyl, C3-C8 alkoxycarbonylalkyl, C3-C6 cycloalkyl, C3-Cg halocycloalkyl, optionally substituted phenyl and optionally substituted benzyl wherein the optional phenyl and benzyl substituents are 1-3 substituents independently selected from W;
R17 is selected from the group H and C1-C4 alkyl; or
R16 and R17, when attached to the same atom, are taken together as (CH2)4,
(CH2)5, or CH2CH2OCH2CH2; R18 is selected from the group C1-C3 alkyl and phenyl optionally substituted with at least one member independently selected from W;
R19 is selected from the group H, C2-C6 alkyl, Cj-Cg haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, CHO, C(O)R16, C(O)OR16, C(S)R16, C(S)2R16, C(O)C(O)OR16, C(O)CH2C(O)OR16, S(O)rR16, S(O)2CH2C(O)OR16, P(X)(OR18)2, C(O)NR16R17, S(O)rNR16R17, S(O)rN(R12)C(O)OR11,
S(O)rN(RI2)CHO, C(O)Ph where the phenyl group is optionally substituted by a group independently selected from W; and benzyl optionally substituted by a group independently selected from W; or R19 is Cj-C4 alkyl substituted with 1-2 substituents independently selected from the group C1-C2 alkoxy, CrC2 haloalkoxy, CN, NO2, C(O)R16, C(O)OR16 and NR8R9;
R20 and R21 are independently CrC4 alkyl;
R22 is selected from the group C1-C4 alkyl and phenyl optionally substituted with W; R23 is selected from the group CrC6 alkyl, CrC6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, OR8, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, Cι-C6 nitroalkyl, C2-C6 cyanoalkyl, C3-C8 alkoxycarbonylalkyl, C3-C6 cycloalkyl, C3-Cg halocycloalkyl, halogen, CN, N3, SCN, NO2, CHO, C(O)R16, C(O)OR16, C(O)NR16R17, SH, S(O)rR16,
S(O)2NR16R17, NR16R17, NR17C(O)R16, OC(O)NHR16, NR17C(O)NHR16, NR17S(O)2R16, phenyl optionally substituted with 1-3 substituents independently selected from W, and benzyl optionally substituted with 1-3 substituents independently selected from W; or when p is 2 and the two R23 groups are adjacent, (R23)2 are optionally taken together as -OCH2O-, -OCF2O-, -OCH2CH2O-, -CH2C(CH3)2O-, -CF2CF2O- or -OCF2CF2O- to form a cyclic bridge;
J is selected from the group
Figure imgf000007_0001
J-l J-2
Figure imgf000007_0002
J-3 J-4
W is selected from the group halogen, CN, NO2, Cι-C2 alkyl, C\-C2 haloalkyl, Cj-C2 alkoxy, Cι-C2 haloalkoxy, C1-C2 alkylthio, CrC2 haloalkylthio, Cι-C2 alkylsulfonyl, and Cι-C haloalkylsulfonyl; X1 is selected from the group O or S; Z1 and Z2 are independently selected from the group CH or N; m is 1 to 3; n is 1 to 3; p is 0 to 3; q is 0 to 3; and r is 0, 1 or 2.
Exemplary values of J include:
Figure imgf000008_0001
J-l J-2(l) J-2(2)
Figure imgf000008_0002
J-3(l) 1-3(2) J-3(3)
Figure imgf000008_0003
J-3(4) J-4(l) J-4(2)
Figure imgf000008_0004
J-4(3) J-4(4) J-4(5)
Preferred Compounds A are compounds of Formula I wherein
Y is selected from the group H, CrC6 alkyl, C(O)Rl6 and C(O)ORl6. Preferred Compounds B are compounds of Preferred A wherein
Q is Q-1; Al is selected from the group CH2, CH2CH2, OCH2, S(O)qCH2 and
N(R7)CH2; and X is O. Preferred Compounds C are compounds of Preferred B wherein
R1 is H; and SF5 is in the 4-position. Preferred Compounds D are compounds of Preferred A wherein Q is Q-2; Rl is H; and SF5 is in the 4-position.
Preferred Compounds E are compounds of Preferred A wherein
A and E are taken together to form CH2, CH2CH2, OCH2, S(O)qCH2 and N(R7)CH2; and X is O.
Preferred Compounds F are compounds of Preferred E wherein Q is Q-3.
Preferred Compounds G are compounds of Preferred F wherein
Rl is H;
Z is selected from the group O, S(O)q and NRl9; and SF5 is in the 4-position.
Preferred Compounds H are compounds of Preferred A wherein
Q is Q-4
R1 is H; and
SF5 is in the 4-position.
Specifically preferred for biological activity is Compound I of Preferred C which is:
[4-[[[3a,4-dihydro-3a-(methoxycarbonyl)-7-(trifluoromethyl)[l]benzopyrano-
[4,3-c]pyrazol-2(3H)-yl]carbonyl]amino]phenyl]penta_luorosulfide.
Compounds of this invention can exist as one or more stereoisomers. The various stereoisomers include enantiomers, diastereomers 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 said stereoisomers. Accordingly, the present invention comprises racemic mixtures, individual stereoisomers, and optically active mixtures of compounds of Formula I as well as agriculturally suitable salts thereof.
In the above recitations, the term "alkyl", used either alone or in compound words such as "alkylthio" or "haloalkyl" denotes straight-chain or branched alkyl, such as, methyl, ethyl, n-propyl, i-propyl, or the different isomers through octadecyl. "Alkenyl" denotes straight-chain or branched alkenes such as ethenyl, 1-propenyl, 2-propenyl, and the different butenyl, pentenyl and hexenyl isomers. "Alkenyl" also denotes polyenes such as 1,3-hexadiene. "Alkynyl" denotes straight-chain or branched alkynes such as ethynyl, 1-propynyl, 3-propynyl and the different butynyl, pentynyl and hexynyl isomers. "Alkoxy" denotes, for example, methoxy, ethoxy, n-propyloxy, isopropyloxy and the different butoxy, pentoxy and hexyloxy isomers. "Alkoxyalkyl" denotes alkoxy substitution on alkyl. Examples of "alkoxyalkyl" include CH3OCH2, CH3OCH2CH2, CH3CH2OCH2, CH3CH2CH2CH2OCH2 and CH3CH2OCH2CH2 and the different pentyl and hexyl isomers. "Alkylthioalkyl" denotes alkylthio appended to straight or branched-chain alkyl groups. "Alkylthio" denotes straight-chain or branched alkylthio moieties such as methylthio, ethylthio, and the different propylthio, butylthio, pentylthio and hexylthio isomers. "Alkylsulfonyl" denotes straight-chain or branched moieties such as CH3S(O)2 and CH3CH2S(O)2. "Cycloalkylene" denotes, for example, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. Examples of "cycloalkylalkyl" include cyclopropylmethyl, cyclopropylethyl, cyclobutylmethyl and the different Cg and C7 isomers bonded to straight-chain or branched alkyl groups. "Alkoxycarbonylalkyl" denotes straight-chain or branched esters substituted on straight-chain or branched alkyl groups. Examples of "alkoxycarbonylalkyl" include CH2C(O)OCH3, CH2C(O)OCH2CH3, CH2CH2C(O)OCH3 and the different C4, C5, C6, C7 and C8 isomers. The term "halogen", either alone or in compound words such as "haloalkyl", denotes 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, CICH2, CF3CH2 and CF3CC12. Examples of "haloalkenyl" include (C1)2C=CHCH2 and CF3CH2CH=CHCH2. Examples of "haloalkynyl" include HOCCHC1, CF3G--C, CC13C≡C and FCH2C≡CCH2. Examples of "haloalkoxy" include CF3O, CCl3CH2O, CF2H H2CH2O and CF3CH2O. Examples of "haloalkylthio" include CC13S, CF3S, and CC13CH2S. Examples of "haloalkylsulfonyl" include CF3SO2, CCl3SO2, CF3CH2SO2 and CF3CF2SO2. 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 18. For example, Cj-Cg alkyl designates methyl, ethyl, and propyl through hexyl isomers; C2 alkoxy designates CH3CH2O-; and C3 alkoxy designates CH3CH2CH2O- or (CH3)2CHO-.
DETAILS OF THE INVENTION Compounds of Formula I (Q-l) can be prepared by reaction of a Formula II dihydropyrazole with a Formula HI aryl isocyanate as shown in Scheme 1. Details of this reaction and the preparation of Formula IH compounds are presented in EP-A-286,346.
Scheme 1
Figure imgf000010_0001
Formula HI compounds may be prepared by reaction of Formula IV anilines with a suitable carbonylating reagent such as phosgene, bis(trichloromethyl) carbonate (triphosgene) or l.T-carbonyldiimidazole in the presence of an acid scavenger such as a trialkylamine in an inert polar or nonpolar aprotic solvent as shown in Scheme 2. This reaction, usually conducted at 0°C to the reflux temperature of the particular solvent used, is typically complete in 24 h.
Scheme 2
Figure imgf000011_0001
IV
The Formula IV anilines may in turn be prepared by ring substitution reactions of Formula V anihnes using methods known to one skilled in the art (Norman and Taylor, Electrophilic Substitution in Benzenoid Compounds, American Elsevier, New York, (1965); Miller, Aromatic Nucleophilic Substitution, American Elsevier, New York, (1968)) as shown in Scheme 3.
Scheme 3
Figure imgf000011_0002
IV
The anilines of Formula V can be prepared by the well-known treatment of their corresponding acid addition salts of Formula VI (wherein W1 is equal to Cl, Br, HSO4 or other suitable counterion) with an organic or inorganic base as shown in Scheme 4.
Scheme 4
Base
Figure imgf000011_0003
Formula VI salts may be prepared by catalytic reduction of nitrobenzene derivatives of Formula VH over a suitable catalyst such as platinum oxide in an alcohol solvent in the presence of a mineral acid and under 103.5 kPa to 517.5 kPa of hydrogen as shown in Scheme 5. This reaction is usually conducted at a range of 10° to 80°C and is typically complete in 8 h.
Scheme 5
Figure imgf000012_0001
vπ
Formula VII compounds may be prepared by treatment of the corresponding disulfides of Formula VHI with silver difluoride according to methods known in the literature (7. Am. Chem. Soc. (1962), 84, 3064) as shown in Scheme 6.
Scheme 6
Figure imgf000012_0002
vm
Alternatively, Formula I (Q-l) compounds may be prepared by reaction of Formula DC carbamoyl chlorides with Formula VI salts in the presence of a suitable base such as a trialkylamine or substituted pyridine as shown in Scheme 7. Typical solvents include polar and nonpolar aprotic solvents. The reaction is usually conducted at 0°C to the reflux temperature of the particular solvent used and is typically complete in 24 h.
Figure imgf000012_0003
IX Formula IX compounds can be prepared by reaction of Formula II dihydropyrazoles, or their acid addition salts, with phosgene or a phosgene equivalent in an inert solvent and in the presence of base as shown in Scheme 8. Typical solvents include polar and nonpolar aprotic solvents. The reaction is usually conducted at 0°C to the reflux temperature of the particular solvent used and is typically complete in 24 h.
Scheme 8
Figure imgf000013_0001
π Compounds of Formula I (Q-2) can be prepared from Formula X ketones by reaction first with hydrazine and then with an aryl isocyanate of Formula m as shown in Scheme 9. Examples of this procedure and preparation of Formula X compounds are described in EP-A-300,692.
Scheme 9
Figure imgf000013_0002
Compounds of Formula I (Q-3), wherein Z = CH2, may be prepared from
Formula XI tetrahydropyridazines by reaction with triphosgene and Formula IV anilines in the presence of a base such as pyridine as shown in Scheme 10. Examples of this procedure and preparation of Formula XI compounds are described in WO 91/17983. Scheme 10
Figure imgf000014_0001
XI
Compounds of Formula I (Q-3), wherein Z = O, S(O)q or NR19, may be prepared by reaction of Formula XH compounds with Formula HI aryl isocyanates as shown in Scheme 11. Examples of this procedure and preparation of Formula XH are described in PCT publication WO 92/11249.
I(Q-3) (Z = 0, S(0)α, NRl9)
Figure imgf000014_0002
xπ Formula I (Q-4) compounds may be prepared by reaction of Formula XIH hydrazones with an equimolar amount of Formula HI aryl isocyanate as shown in Scheme 12. The Formula XIH hydrazones may in turn be prepared by condensation of hydrazine with ketones of Formula XIV as shown in Scheme 13. Examples of both of these procedures and preparation of Formulae XIH and XIV compounds are described in WO 92/06076.
Scheme 12
KQ )
Figure imgf000014_0003
Scheme 13
Figure imgf000015_0001
Compounds of Formula I (Q-5) may be prepared by reaction of an acid of Formula XV with thionyl chloride or another chlorinating agent followed by treatment with a Formula IV aniline in the presence of an amine base, such as triethylamine, as shown in Scheme 14. Examples of this procedure and preparation of Formula XV compounds are described in WO 88/05046.
Scheme 14
Figure imgf000015_0002
X
Compounds of Formula I (Q-6) wherein Z = CH2 can be prepared by reaction of Formula XVI acid chlorides with Formula IV anilines in an inert solvent and in the presence of an acid scavenger such as triethylamine as shown in Scheme 15. Examples of this procedure and preparation of Formula XVI compounds are described in WO 91/17983.
(Z = CH2)
Figure imgf000015_0003
Compounds of Formula I (Q-6), wherein Z = O, S(O)q, or NR19, may be prepared by reaction of Formula XVH acid chlorides with Formula IV anilines in an inert solvent and in the presence of an acid scavenger, such as triethylamine, as shown in Scheme 16. Examples of this procedure and preparation of Formula XVH compounds are described in WO 92/11249.
Scheme 16
Figure imgf000016_0001
xvπ
Compounds of Formula I (Q-7) can be prepared in a three-step process whereby Formula XVHI esters are saponified, converted to the acid chloride and reacted with Formula IV anilines in an inert solvent and in the presence of an acid scavenger as shown in Scheme 17. Examples of this procedure and preparation of Formula XVHI compounds are described in WO 92/06076.
Scheme 17
Figure imgf000016_0002
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 into the synthesis will aid in obtaining the desired products. The use and choice of the protecting group will be apparent to one skilled in chemical synthesis.
EXAMPLE 1 Preparation of r4-rrr3a.4-dihydro-3a-(methoxycarbonyl')-7-('trifluoromethyl)m- ber-Zopyrajior4.3-clpyrazol-2(3H)-yl1carbonyl1aminolphenyl1pentafluorosulfide
Step A: 4-(Aminophenyl)pentafluorosulfurhydrochloride
The compound 4-(nitrophenyl)pentafluorosulfur (0.60 g, 0.0025 mol), prepared according to the literature procedure (Sheppard, W.A. J. Am. Chem. Soc. (1962), 84, 3064), in absolute ethanol (7.5 mL) and aqueous 5.5 N hydrochloric acid (0.4 mL, 0.0025 mol), was treated with platinum oxide (catalyst, 0.02 g) and hydrogen at 276 kPa pressure with shaking. After 30 min the catalyst was removed by vacuum filtration of the reaction mixture and the filtrate was concentrated to dryness. The solid residue was triturated with diethyl ether to give 0.57 g (93%) of the title compound as a Ught yellow solid. IH NMR (DMSO-d6) δ 7.43 (d,2H, J = 8.7 Hz), 6.55 (d,2H, J = 8.7 Hz), 5.94 (brs, 2H); MS: m/e 219.
Step B: Methyl 2-fchlorocarbonylV2.3-dihvdro-7-(trifluoromethvnrn- benzopyranor4.3-c1pyrazole-3a(4H)-carboxylate A suspension of methyl 2,3-dihydro-7-(trifluoromethyl)[l]benzopyrano[4,3-c]- pyrazole-3a-carboxylate hydrochloride (1.5 g, 0.0045 mol), prepared as described previously (WO 90/10623), in saturated aqueous sodium hydrogen carbonate (25 mL), was extracted with chloroform (60 mL total). The combined chloroform extracts were dried over anhydrous potassium carbonate, filtered and then concentrated to a total volume of 30 mL by rotary evaporation. The resulting solution was cooled to 10°C and a 1.93M solution of phosgene in toluene (4.6 mL, 0.0089 mol) was added slowly. After 1 h, the reaction mixture was concentrated to dryness to give 1.6 g (quantitative) of the title compound as a yellow solid. Step C: r4-rrr3a.4-Dihvdro-3a-(methoxycarbonylV7-(trifluoromethyl n- benzopyranor4.3-c]pyrazol-2f3H)-yl1carbonvflamino1phenyl1- pentafluorosulfide The compound diisopropylethylamine (0.59 g,' 0.0046 mol) was added to a solution of the compound from Step B, methyl 2-(chlorocarbonyl)-2,3-dihydro-7- (trifluoromethyl)[l]benzopyrano-[4,3-c]pyrazole-3a(4H)-carboxylate, (0.86 g, 0.0024 mol) in dichloromethane (47 mL). The compound from Step A,
4-(aminophenyl)pentafluorosulfur hydrochloride, (0.47 g, 0.0018 mol) was added and the resulting solution was stirred at room temperature. After 62 h, the resulting crude suspension was dissolved in ethyl acetate (20 mL) and preadsorbed onto silica gel (3 g) and then purified by flash column chromatography (1-20% ethyl acetate in hexanes as eluent) to give 0.65 g (65%) of the title compound as an off-white solid, m.p. 236-238°C. iH NMR (CDC13) δ 8.15 (s,lH), 7.98 (d,lH, J = 8.3 Hz), 7.72 (d,2H, J = 9 Hz), 7.62 (d,2H, J = 9 Hz), 7.31-7.34 (m,lH), 5.08 (d,lH, J = 10.9 Hz), 4.53 (d,lH, J = 12.1 Hz), 4.24 (d,lH, 10.9 Hz), 3.86 (d,lH, J = 12.1 Hz), 3.78 (s,3H); MS: m/e 545. EXAMPLE 2 Preparation of (+/-)-r4-rrr7-chloro-4a.5-dihvdro-4a-(methoxycarbonyl)indeno-r 1.2-el- ri.3.41oxadiazin-2(3HVyllcarbonyl1(methoxycarbonyl ajτιinolphenyll-pentafluorosulfur Step A: r4-r(MethoxycajbonvDa-r no1phenyllpentafluorosulfur
The product from Example 1, Step A, 4-(aminophenyl)pentafluorosulfur hydrochloride, (2.3 g, 0.0091 mol) was suspended in IN aqueous NaOH (34 mL) and extracted with dichloromethane (3 X 35 mL). The combined organic layers were washed with brine (50 mL), dried over sodium sulfate, filtered and concentrated. The resulting residue (1.86 g) was dissolved in dichloromethane (42.5 mL) and cooled to 0°C. To this stirring solution was added N,N-diethylaniUne (1.89 g, 0.0127 mol) and methyl chloroformate (1.44 g, 0.0152 mol). The mixture was allowed to warm to room temperature and was stirred for 22.5 h. The crude reaction mixture was preadsorbed onto silica gel (13 g) and then purified by flash column chromatography (5-50% ethyl acetate in hexanes as eluent) to give 2.33 g (93%) of the title compound as a white solid, m.p. 130-132°C. JH NMR (CDC13) δ 7.69 (d,2H, J = 8.8 Hz), 7.50 (d,2H, J = 8.8 Hz), 6.91 (br s.lH), 3.81 (s,3H).
Step B: r4-r(Clilorocajbonyl)(methoxycarbonyl')amino1phenyllpentafluorosulfur An oil dispersion of 60 % sodium hydride (0.1 g, 0.0025 mol) was added to a solution of the product of Step A, [4-t(methoxycarbonyl)amino]phenyl]pentafluoιo- sulfur, (0.6 g, 0.0022 mol) in benzene (5 mL). After 15 min ethylene glycol dimethyl ether (0.4 mL) was added and the mixture was heated to 60°C for 2 h. After cooling to room temperature the resulting off-white suspension was transferred via syringe into a solution of 1.93M phosgene in toluene (5.6 mL, 0.0108 mol) at 5°C. After stirring at 5 °C for 30 min the reaction mixture was concentrated to dryness and then redissolved in ethyl acetate (5 mL) for use directly in the next step (Step C). Step C: (+/-)-r4-rrr7-Chloro-4a.5-dihydro-4a-(methoxycarbonyl)indeno-π.2-el- π.3.41oxadiazin-2(3H')-yllcarbonyll(methoxycarbonyl')aminolphenyll- pentafluorosulfur A 100-mL three-neck flask equipped with overhead stirrer, rubber septum and gas inlet valve with a three-way stopcock was flushed with nitrogen and charged with monobasic sodium phosphate (0.242 g, 0.0020 mol), water (1 mL), 5% palladium-on- carbon (0.040 g) and 4a-methyl 2-(phenylmethyl) 7-chloroindeno[l,2-e] [1,3,4]- oxadiazine-2,4a(3H,5H)-dicarboxylate (0.809 g, 0.0020 mol), prepared by procedures analogous to those disclosed in WO92/11249. Ethyl acetate (8 mL) was added, and the system was purged with nitrogen, evacuated, and replaced by hydrogen. A hydrogen balloon was attached and the mixture was stirred vigorously for 80 min at ambient temperature. The flask was evacuated and refilled with nitrogen, and the catalyst was filtered onto a pad of Celite and rinsed with ethyl ether (10 mL) and water (6 mL). The filtrate was separated, and the organic layer was charged to a 100-mL three-neck flask and cooled to 5 - 10°C. Aqueous saturated sodium hydrogen carbonate (1.3 mL) was added, followed by the ethyl acetate solution of the compound from Step B, [4- [(chlorocarbonyl)-(methoxycarbonyl)amino]phenyl]pentafluorosulfur, (0.0022 mol, crude), and the mixture was allowed to stir at 10°C for 5.5 h and then at room temperature overnight. The organic phase was separated, dried over magnesium sulfate, and concentrated to a foam (0.95 g) that was purified by flash column chromatography over silica gel (0-30% ethyl acetate in hexanes as eluent) to give 0.30 g (29%) of the title compound as a light yellow oil that solidified on standing, m.p. 59-60°C. JH NMR (CDC13) δ 7.72-7.83 (m, 2H), 7.40-7.52 (m, 3H), 7.30-7.38 (m, 2H), 5.73 (d, IH, J = 9.9 Hz), 5.24 (d, IH, J = 9.9 Hz), 3.76 (s, 3H), 3.72 (s, 3H), 3.51 (d, IH, J = 16.5 Hz), 3.27 (d, IH, J = 16.3 Hz); MS: m/e 569.
EXAMPLE 3 Preparation of r4-rrfr5-fluoro-2-(4-fluorophenyl)-2.3-dihydro-lH-inden-l- yUdenelhydrazolcarbonyllaminolphenyllpentafluorosulfur
Step A: (4-Isocyanatophenyl'>pentafluorosulfur
The product from Example 1, Step A, 4-(aminophenyl)pentafluorosulfur hydrochloride, (2.04 g, 0.0080 mol) was suspended in IN aqueous NaOH (30 mL) and extracted with dichloromethane (3 X 20 mL)". The combined organic layers were washed with brine (30 mL), dried over sodium sulfate, filtered and concentrated. The resulting residue (1.72 g) was dissolved in />-dioxane (40 mL), and trichloromethyl chloroformate (1.89 g, 0.0096 mol) and triethylamine (0.97 g, 0.0096 mol) were added, in order. The mixture was heated under reflux for 11 h, cooled to room temperature and filtered. The filtrate was concentrated to dryness to afford 2.16 g (110%, crude) of the title compound as a light brown oil. _R (p-dioxane solution): 2265 can"1; !H NMR (CDCI3) δ 7.73 (d, 2H, J = 9.0 Hz), 7.17 (d, 2H, J = 9.0 Hz). Step B: r4-rrrr5-Fluoro-2-f4-fluorophenvn-2.3-dihvdro-lH-inden-l-ylidene1- hvdrazolcarbonynaminolphenyllpentafluorosulfur
Hydrazine hydrate (0.21 g, 0.0041 mol) was added to a suspension of 5-fluoro-2- (4-fluorophenyl)-2,3,-dihydro-lH-inden-l-one (0.50 g, 0.0021 mol), prepared by procedures analogous to those disclosed in United States Patent No. 5,182,303, in ethanol (6 mL) and the mixture was heated under reflux for 16 h, cooled to room temperature, concentrated, redissolved in ethyl acetate (25 mL), washed successively with water, saturated aqueous sodium hydrogen carbonate and brine (20 mL each), dried over sodium sulfate, filtered and concentrated. The resulting residue (0.55 g) was dissolved in dichloromethane (6 mL) and a solution of the product of Step A, (4- isocyanatophenyl)pentafluorosulfur (0.50 g, 0.0021 mol) in dichloromethane (1 mL) was added. After 1 h the reaction mixture was concentrated to an orange foam (1.05 g) that was purified by flash chromatography over silica gel (10-20% ethyl acetate in hexanes as eluent) to give 0.34 g (33%) of the title compound as an off-white solid, m.p. 216-217°C. !H NMR (CDC13) δ 8.37 (s,lH), 7.82 (dd,lH, J = 5.3, 8.5 Hz), 7.69 (d,2H, 9.3 Hz), 7.60 (d,2H, 9.3 Hz), 6.99-7.22 (m,6H), 4.31 (dd.lH, J = 3.0, 7.0 Hz), 3.74 (dd,lH, J = 3.0, 7.25 Hz), 2.97 (d,lH, J = 20 Hz).
EXAMPLE 4 Preparation of r4-rrr(5-chloro-2.3-dihydro-2-propyl-lH-inden-l-ylidene)- hydra--olc-jbonyl1-arninolphenyllpentafluorosulfur
Step A: 1 -(4-Chlorophenyl)-2-methylene- 1 -pentanone
A mixture of l-(4-chlorophenyl)-l -pentanone (38.5 g, 0.196 mol), paraformaldehyde (26.45 g, 0.8818 mol), dimethylamine hydrochloride (71.9 g, 0.8818 mol) and glacial acetic acid (5.8 g, 0.0980 mol) in N,N-dimethylformamide (200 mL) was heated at 100°C for 24 h, cooled to room temperature, poured over ice water (500 mL) and extracted with ethyl ether (2 X 150 mL). The combined organic layers were dried over magnesium sulphate, filtered and concentrated to afford 31.04 g (76%) of the title compound as a light yellow oil. !H NMR (CDCI3) δ 7.71 (d, 2H, J = 8.1 Hz), 7.41 (d, 2H, J = 8.1 Hz), 5.83 (s, IH), 5.56 (s, IH), 2.44 (t, 2H, J = 7.5 Hz), 1.52 - (apparent sextet, 2H, J = 7.5 Hz), 0.097 (t, 3H, J = 7.5 Hz). Step B: 5-Chloro-2.3-dihydro-2-propyl-lH-inden-l-one
The product of Step A, l-(4-chlorophenyl)-l-pent-2-ene (31.04 g, 0.1487 mol) was added dropwise to warm (60°C) sulfuric acid such that T; < 75°C. After the addition was complete, the mixture was heated at 65°C for 4 h, cooled to room temperature, and poured in a well-stirred mixture of ice (500 g), water (300 g), dichloromethane (250 mL). The organic layer was separated and saved, and the aqueous layer was extracted with ethyl acetate (2 X 150 mL). The organic layer was combined with the ethyl acetate layers and washed with water (150 mL) and brine (150 mL), dried over magnesium sulfate, filtered and concentrated to afford 33.18 g (108%, crude) of the title compound as a light brown oil. !H NMR (CDCI3) δ 7.66 (d.lH, J = 8.1 Hz), 7.44 (s,lH), 7.33 (d,lH, J = 8.3 Hz), 3.30 (dd,lH, J = 7.9, 17.9 Hz), 2.79 (dd,lH, J = 3.9, 17.5 Hz), 2.63-2.73 (m,lH), 1.81-2.00 (m,lH), 1.36-1.53 (m,3H), 0.96 (t,3H, J = 7.3 Hz). Step C: r4-rrrf5-Chloro-2.3-dihvdro-2-propyl-lH-inden-l-ylideneVhydrazo1- carbonvn-aminolphenyllpentafluorosulfur Hydrazine hydrate (0.23 g, 0.0046 mol) was added to a suspension of the product of Step B, 5-chloro-2,3-dihydro-2-propyl-lH-inden-l-one (0.75 g, 0.0036 mol) in ethanol (10 mL) and the mixture was heated under reflux for 21 h, cooled to room temperature, concentrated, redissolved in ethyl acetate, washed successively with water, saturated aqueous sodium hydrogen carbonate and brine, dried over sodium sulfate, filtered and concentrated. The resulting residue (1.45 g) was dissolved in dichloromethane (10 mL) and a solution of the product of Example 3, Step A, (4- isocyanatophenyl)pentafluoro-sulfur (0.89 g, 0.0036 mol) in dichloromethane (1 mL) was added. After 23 h the reaction mixture was concentrated to an orange foam (1.74 g) that was purified by flash chromatography over silica gel (10-20% ethyl acetate in hexanes as eluent) to give 0.80 g (50%) of the title compound as an off-white solid, m.p. 177-179°C. !H NMR (CDC13) δ 8.46 (s, IH), 7.97 (s, IH), 7.61-7.77 (m, 7H), 7.31 (d, 2H, J = 8.3 Hz), 3.16-3.33 (m, 2H), 2.83 (d, IH, J = 16.1 Hz), 1.64-1.81 (m, IH), 1.32- 1.48 (m, 3H), 0.94 (t, 3H, J = 6.9 Hz).
EXAMPLE 5 Preparation of (+/- -f4-rrr3-(4-chlorophenyl)-4.5-dihydro-4-phenyl- 1 H-pyrazol- 1 -yllcarbonyllaminolphenyllpentafluorosulfur
A solution of the product of Example 3, Step A, (4-isocyanatophenyl)penta- fiuorosulfur (1.04 g, 0.0042 mol) in diethyl ether (2 mL) was added dropwise to a suspension of (+/-)-3-(4-chlorophenyl)-4,5-dihydro-4-phenyl-lH-pyrazole (0.99 g, 0.0039 mol-), prepared according to the methods described previously (US 4,070,365), in ethyl ether (4 mL) at reflux. The mixture became a thick beige slurry that was heated under reflux for 2.5 h, cooled to room temperature and filtered. The precipitate was rinsed with diethyl ether and hexanes to give 1.10 g (57%) of the title compound as a pale yellow solid, m.p. 205-207°C. iH NMR (CDCI3) δ 8.29 (s,lH), 7.71 (d,2H, J = 2.0 Hz), 7.60 (d,2H, J = 2.0 Hz), 7.58 (d,2H, J = 2.0 Hz), 7.30-7.38 (m,5H), 7.20 (d,2H, J = 2.0 Hz), 4.75 (dd,lH, J = 5.0, 11.5 Hz), 4.45 (t,lH, 11.5 Hz), 4.08 (dd,lH, J = 5.5, 11.5 Hz).
EXAMPLE 6 Preparation of (+/-)-r4-rrr3.4-bis(4-fluorophenyD-4.5-dihydro- 1 H-pyrazol- 1 -yllcarbonyll -uiiinolphenyllpentafluorosulfur Substituting (+/-)-3,4-bis(4-fluorophenyl)-4,5-dihydro-lH-pyrazole (1.0 g, 0.0039 mol), prepared according to the methods described previously (US 4,070,365), for (+/-)- 3-(4-chlorophenyl)-4,5-dihydro-4-phenyl-lH-pyrazole, and proceeding according to the method described in Example 5, above, 0.84 g (43%) of the title compound was obtained as an off-white solid, m.p. 212-213°C. H NMR (CDCI3) δ 8.28 (s,lH), 7.72 (d,2H, J = 9.3 Hz), 7.61-7.68 (m,4H), 7.17 (distorted t,2H), 7.02 (t,4H, J = 8.5 Hz),
4.75 (dd,lH, J = 5.3, 11.5 Hz), 4.43 (t,lH, J = 11.5 Hz), 4.05 (dd,lH, J = 5.3, 11.5 Hz). By the procedures described herein the following compounds of Tables 1 to 7 can be prepared. The compounds in Table 1, line 1 can be referred to as 1-1, 1-2, 1-3, 1-4,
1-5, 1-6 and 1-7 (as designated by Une and column). All the other specific compounds covered in these Tables can be designated in an analogous fashion. The following abbreviations have been used in Tables 1-7: Me - methyl, Et = ethyl, i-Pr = isopropyl and Ph = phenyl.
Table 1
Figure imgf000022_0001
COLUMN
1 2 3 4 5 6
Al= -OCH2; R3=C02Me; Y=H; R2= H Cl F CF3 OCF3 OCF2H
Al= -OCH2; R3=C02Et; Y=H; R2= H. Cl F CF3 OCF3 OCF2H
A = -OCH2; R3=4-F-Ph; Y=H; R2= H Cl F CF3 OCF3 OCF2H
Al= -OCH2; R3=4-Cl-Ph; Y=H; R2= H Cl F CF3 OCF3 OCF2H
A = -OCH2; R3=iPr; Y=H; R2= H Cl F CF3 OCF3 OCF2H
Al= -OCH2; R3=C02Me; Y=Me; R2= H Cl F CF3 OCF3 OCF2H
A = -OCH2; R3=C02Et; Y=Me; R2= H Cl F CF3 OCF3 OCF2H
Al= -OCH2; R3=4-F-Ph; Y=Me; R2= H Cl F CF3 OCF3 OCF2H
Al= -OCH2; R3=4-Cl-Ph; Y=Me; R2= H Cl F CF3 OCF3 OCF2H
Al= -OCH2; R3=iPr; Y=Me; R2= H Cl F CF3 OCF3 OCF2H
Al= -OCH2; R3=C02Me; Y=C02Me; R2= H Cl F CF3 OCF3 OCF2H
A -OCH2; R3=C02Et; Y=C02Me; R2= H Cl F CF3 OCF3 OCF2H
A ■OCH2; R3=4-F-Ph;Y=C02Me; R2= H Cl F CF3 OCF3 OCF2H
A -OCH2; R3=4-Cl-Ph;Y=C02Me; R2= H Cl F CF3 OCF3 OCF2H
Al=- -OCH2; R3=iPr; Y=C02Me; R2= H Cl F CF3 OCF3 OCF2H
A!=. -OCH2; R3=C02Me; Y=C02Et; R2= H Cl F CF3 OCF3 OCF2H
A -OCH2; R3=C02Et; Y=C02Et; R2= H Cl F CF3 OCF3 OCF2H
A -OCH2; R3=4-F-Ph; Y=C02Et; R2= H Cl F CF3 OCF3 OCF2H
A1=- ■OCH2; R3=4-Cl-Ph; Y=C02Et; R2= H Cl F CF3 OCF3 OCF2H
A1= =--OCH2; R3=iPr; Y=C02Et; R2= H Cl F CF3 OCF3 OCF2H
Figure imgf000023_0001
56 A1=-NHCH2; R3=C02Me; Y=C02Et; R2= H Cl F CF3 OCF3 OCF2H
57 A!=-NHCH2; R3=C02Et; Y=C02Et; R2= H Cl F CF3 OCF3 OCF2H
58 A!=-NHCH2; R3=4-F-Ph; Y=C02Et; R2= H Cl F CF3 OCF3 OCF2H
59 A!=-NHCH2; R3=4-Cl-Ph; Y=C02Et; R2= H Cl " F CF3 OCF3 OCF2H
60 A1=-NHCH2; R3=iPr; Y=C02Et; R2= H H F CF3 OCF3 OCF2H
Table 2
Figure imgf000024_0001
COLUIVD M
1 2 3 4 5 6
61 Rl5=4-Cl-Ph; Ϋ=H; R2= H Cl F CF3 OCF3 OCF2H
62 R15=4-F-Ph; Y=H; R2= H Cl F CF3 OCF3 OCF2H
63 Rl5=4-Cl-Ph; Y=CH3; R2= H Cl "F CF3 OCF3 OCF2H
64 Rl5=4-F-Ph; Y=CH3; R2= H Cl F CF3 OCF3 OCF2H
65 R15=4-Cl-Ph; Y=C02CH3; R2= H Cl F CF3 OCF3 OCF2H
66 Rl5=4-F-Ph; Y=C02CH3; R2= H Cl F CF3 OCF3 OCF2H
67 Rl5=4-Cl-Ph; Y=C(0)CH3; R2= H Cl F CF3 OCF3 OCF2H
68 R15=4-F-Ph; Y=C(0)CH3; R2= H Cl F CF3 OCF3 OCF2H
Figure imgf000024_0002
Figure imgf000025_0001
Figure imgf000025_0002
Figure imgf000026_0001
Figure imgf000026_0002
Figure imgf000027_0001
Figure imgf000028_0001
Tabls 3
Figure imgf000028_0002
COLUIV EN
1 2 3 4 5 6
69 R3=C02Me; Z=CH2; Y=H; R2= H Cl F CF3 OCF3 OCF2H
70 R3=C02Et; Z= CH2; Y=H; R2= H Cl F CF3 OCF3 OCF2H
71 R3=4-F-Ph; Z=CH2; Y=H; R2= H Cl F CF3 OCF3 OCF2H
72 R3=4-Cl-Ph; Z=CH2; Y=H; R2= H Cl F CF3 OCF3 OCF2H
73 R3=iPr; Z=CH2; Y=H; R2= H Cl F CF3 OCF3 OCF2H
74 R3=C02Me;Z=CH2;Y=Me; R2= H Cl F CF3 OCF3 OCF2H
75 R3=C02Et; Z=CH2; Y=Me; R2= H Cl F CF3 OCF3 OCF2H
76 R3=4-F-Ph; Z=CH2; Y=Me; R2= H Cl F CF3 OCF3 OCF2H
77 R3=4-Cl-Ph; Z=CH2; Y=Me; R2= H Cl F CF3 OCF3 OCF2H
78 R3=iPr; Z=CH2; Y=Me; R2= H Cl F CF3 OCF3 OCF2H
79 R3=C02Me;Z=CH2;Y=C02Me; R2= H Cl F CF3 OCF3 OCF2H
80 R3=C02Et; Z=CH2; Y=C02Me; R2= H Cl F CF3 OCF3 OCF2H
81 R3= -F-Ph; Z=CH2; Y=C02Me; R2= H Cl F CF3 OCF3 OCF2H 82 R3=4-Cl-Ph;Z=CH2;Y=C02Me; R2= H Cl F CF3 OCF3 OCF2H
83 R3=iPr;Z=CH2;Y=C02Me; R2= H Cl F CF3 OCF3 OCF2H
84 R3=C02Me;Z=CH2; Y=C02Et; R2= H Cl F CF3 OCF3 OCF2H
85 R3=C02Et;Z=CH2;Y=C02Et; R2= H Cl F CF3 OCF3 OCF2H
86 R3=4-F-Ph;Z=CH2;Y=C02Et; R = H Cl F CF3 OCF3 OCF2H
87 R3=4-Cl-Ph;Z=CH2;Y=C0 Et; R2= H Cl F CF3 OCF3 OCF2H
88 R3=i-Pr;Z=CH2;Y=C02Et; R2= H Cl F CF3 OCF3 OCF2H
89 R3=C02Me;Z=0;Y=H; R2= H Cl F CF3 OCF3 OCF2H
90 R3=C02Et;Z=0;Y=H; R = H Cl F CF3 OCF3 OCF2H
91 R3=4-F-Ph;Z=0;Y=H; R2= H Cl F CF3 OCF3 OCF2H
92 R3=4-Cl-Ph;Z=0;Y=H; R2= H Cl F CF3 OCF3 OCF2H
93 R3=iPr;Z=0;Y=H; R = H Cl F CF3 OCF3 OCF2H
94 R3=C02Me;Z=0;Y=Me; R2= H Cl F CF3 OCF3 OCF2H
95 R3=C02Et;Z=0;Y=Me R2= H Cl F CF3 OCF3 OCF2H
96 R3=4-F-Ph;Z=0;Y=Me; R = H Cl F CF3 OCF3 OCF2H
97 R3=Cl-Ph;Z=0;Y=Me; R2= H Cl F CF3 OCF3 OCF2H
98 R3=iPr;2=0;Y=Me; R2= H Cl F CF3 OCF3 OCF2H
99 R3=C02Me;Z=0;Y=C02Me; R2= H Cl F CF3 OCF3 OCF2H
100 R3=C02Et;Z=0;Y=C02 e; R2= H Cl F CF3 OCF3 OCF2H
101 R3=4-F-Ph;Z=0;Y=C02Me; R2= H Cl F CF3 OCF3 OCF2H
102 R3=4-Cl-Ph;Z=0;Y=C02Me; R = H Cl F CF3 OCF3 OCF2H
103 R3=iPr;Z=0;Y=C02Me; R2= H Cl F CF3 OCF3 OCF2H
104 R3=C02Me;Z=0;Y=C02Et; R2= H Cl F CF3 OCF3 OCF2H
105 R3=C02Et;Z=0;Y=C02Et; R2= H Cl F CF3 OCF3 OCF2H
106 R3=4-F-Ph;Z=0; Y=C02Et; R2= H Cl F CF3 OCF3 OCF2H
107 R3=4-Cl-Ph;Z=0;Y=C02=Et; R = H Cl F CF3 OCF3 OCF2H
108 R3=iPr;Z=0; Y=C02Et; R2= H Cl F CF3 OCF3 OCF2H
109 R3=C02Me;Z=NH;Y=H; R2= H Cl F CF3 OCF3 OCF2H
110 R3=C02Et;Z=NH;Y=H; R2 H Cl F CF3 OCF3 OCF2H
111 R3=4-F-Ph;Z=NH;Y=H; R2= H Cl F CF3 OCF3 OCF2H
112 R3=4-Cl-Ph;Z=NH;Y=H; R2= H Cl F CF3 OCF3 OCF2H
113 R3=i-Pr;Z=NH;Y=H; R2= H Cl F CF3 OCF3 OCF2H
114 R3=C02Me;Z=NMe;Y=H; R2= H Cl F CF3 OCF3 OCF2H
115 R3=C02Et;Z=NMe;Y=H; R2= H Cl F CF3 OCF3 OCF2H
116 R3=4-F-Ph;Z=NMe;Y=H; R2= H Cl F CF3 OCF3 OCF2H 117 R3=4-Cl-Ph; Z=NMe; Y=H; R2= H Cl F CF3 OCF3 OCF2H
118 R3=i-Pr; Z=NMe; Y=H; R2= H Cl F CF3 OCF3 OCF2H
119 R3=C02Me; Z=NC(0)Me; Y=H; R2= H Cl F CF3 OCF3 OCF2H
120 R3=C02Et; Z=NC(0)Me; Y=H; R2= H Cl F CF3 OCF3 OCF2H
121 R3=4-F-Ph; Z=NC(0)Me; Y=H; R2= H Cl F CF3 OCF3 OCF2H
122 R3=4-Cl-Ph; Z=NC(0)Me; Y=H; R2= H Cl F CF3 OCF3 OCF2H
123 R3=i-Pr; Z=NC(0)Me; Y=H; R^ H Cl F CF3 OCF3 OCF2H
124 R3=C02Me; Z=NC(0)OMe; Y=H; R2= H Cl F CF3 OCF3 OCF2H
125 R3=C02Et; Z=NC(0)OMe; Y=H; R2= H Cl F CF3 OCF3 OCF2H
126 R3=4-F-Ph; Z=NC(0)OMe; Y=H; R2= H Cl F CF3 OCF3 OCF2H
127 R3=4-Cl-Ph; Z=NC(0)OMe; Y=H; R2= H Cl F CF3 OCF3 OCF2H
128 R3=i-Pr; Z=NC(0)OMe; Y=H; R2= H Cl F CF3 OCF3 OCF2H
129 R3=C02Me; Z=NC(0)CF3; γ=H; R^ H Cl F CF3 OCF3 OCF2H
130 R3=C02Et; Z=NC(0)CF3; Y=H; R^ H Cl F CF3 OCF3 OCF2H
131 R3=4-F-Ph; Z=NC(0)CF3; Y=H; R2= H Cl F CF3 OCF3 OCF2H
132 R3=4-Cl-Ph; Z=NC(0)CF3; Y=H; R^ H Cl F CF3 OCF3 OCF2H
133 R3=i-Pr; Z=NC(0)CF3; Y=H; Ε = H Cl F CF3 OCF3 OCF2H
Table 4
Figure imgf000030_0001
COLUMN
1 2 3 4 5 4 R3=Ph; Y=H; R2= H Cl F CF3 OCF3 OCF2H R3=4-F-Ph; Y=H; R2= H Cl F CF3 OCF3 OCF2H R3--4-Cl-Ph; Y=H; R2= H Cl F CF3 OCF3 OCF2H R3=Me; Y=H; R2= H Cl F CF3 OCF3 OCF2H R3=4-iPr; Y=H; R2= H Cl F CF3 OCF3 OCF2H R3=Ph; Y= e; R2= H Cl F CF3 OCF3 OCF2H R3=4-F-Ph; Y=Me; R2= H Cl F CF3 OCF3 OCF2H 141 R3=4-Cl-Ph; Y=Me; R2= H Cl F CF3 OCF3 OCF2H
142 R3=Me; Y=Me; R2= H Cl F CF3 OCF3 OCF2H
143 R3=4-iPr; Y=Me; R2= H Cl F CF3 OCF3 OCF2H
144 R3=4-F-Ph; Y=Me; R2= H Cl F CF3 OCF3 OCF2H
145 R3=4-Cl-Ph; Y=Me; R2= H Cl F CF3 OCF3 OCF2H
146 R3=Me; Y=Me; R2= H Cl F CF3 OCF3 OCF2H
147 R3=iPr; Y=Me; R2= H Cl F CF3 OCF3 OCF2H
Table 5
Figure imgf000031_0001
COLUMN
148 R3=4-F-Ph; E=H; Y=H; R2= H Cl F CF3 OCF3 OCF2H
149 R3=4-Cl-Ph; E=H; Y=H; R2= H Cl F CF3 OCF3 OCF2H
150 R3=C02Me; E=Me; Y=H; R2= H Cl F CF3 OCF3 OCF2H
151 R3=4-F-Ph; E=H; Y=Me; R2= H Cl F CF3 OCF3 OCF2H
152 R3=4-Cl-Ph; E=H; Y=Me; R2= H Cl F CF3 OCF3 OCF2H
153 R3=C02Me; E=Me; Y=Me; R2= H Cl F CF3 OCF3 OCF2H
154 R3=4-F-Ph; E=H; Y=C(0)Me; R2= H Cl F CF3 OCF3 OCF2H
155 R3=4-Cl-Ph; E=H; Y=C(0)Me; R2= H Cl F CF3 OCF3 OCF2H
156 R3=C02Me; E=Me; Y=C(0)Me; R2= H Cl F CF3 OCF3 OCF2H
157 R3=4-F-Ph; E=H; Y=C02Me; R = H Cl F CF3 OCF3 OCF2H
158 R3=4-CI-Ph; E=H; Y=C02Me; R2= H Cl F CF3 OCF3 OCF2H
159 R3=C02Me; E=Me; Y=C02Me; R2= H Cl F CF3 OCF3 OCF2H Table 6
COLUMN
160 R3=C02Me; A=H; E=H; Y=H; Z=CH2; R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
161 R3=4-F-Ph; A=H; E=H; Y=H; Z=CH2; R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
162 R3=4-Cl-Ph; A=H; E=H; Y=H; Z=CH2; R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
163 R3=C02Me; A+E=OCH2; Y=H;Z=CH2; R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
164 R3=4-F-Ph; A+E=OCH2; Y=H; Z=CH2; R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
165 R3=4-Cl-Ph; A+E=OCH2; Y=H; Z=CH2; R2= H 3-C1 3-CF 3-OCF3 3-OCF2H
166 R3=C02Me; A+E=CH2;Y=H; Z=CH2; R2= H 4-C1 4-F 4-CF3 4-OCF3
167 R3=4-F-Ph; A+E=CH2; Y=H; Z=CH2; R2= H 4-C1 4-F 4-CF3 4-OCF3
168 R3=4-Cl-Ph; A+E=CH2; Y=H; Z=CH2; R = H 4-C1 4-F 4-CF3 4-OCF3
169 R3=C02Me; A=H; E=H; Y=H; Z=0; R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
170 R3=4-F-Ph; A=H; E=H; Y=H; Z=0; R2= H 3-C1 ■ 3-CF 3-OCF3 3-OCF2H
171 R3=4-Cl-Ph; A=H; E=H; Y=H; Z=0; R2= H 3-C1 3-CF 3-OCF3 3-OCF2H
172 R3=C02Me; A+E=OCH2; Y=H; Z=0; R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
173 R3=4-F-Ph; A+E=OCH2; Y=H; Z=0; R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
174 R3=4-Cl-Ph; A+E=OCH2; Y=H; Z=0; R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
175 R3=C02Me; A+E=CH2;Y=H; Z=0; R2= H 4-C1 4-F 4-CF3 4-OCF3
176 R3= -F-Ph; A+E=CH2; Y=H; Z=0; R2= H 4-C1 4-F 4-CF3 4-OCF3
177 R3=4-Cl-Ph; A+E=CH2; Y=H; Z=0; R2= H 4-C1 4-F 4-CF3 4-OCF3
178 R3=C02Me; A=H; E=H; Y=H; Z=NH; R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
179 R3=4-F-Ph; A=H; E=H; Y=H; Z=NH; R = H 3-C1 3-CF3 3-OCF3 3-OCF2H
180 R3=4-Cl-Ph; A=H; E=H; Y=H; Z=NH; R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
181 R3=C02Me; A+E=OCH2; Y=H; Z=NH; R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
182 R3=4-F-Ph; A+E=OCH2; Y=H; Z=NH; R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
183 R3=4-Cl-Ph; A+E=OCH2; Y=H; Z=NH; R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
184 R3=C02Me; A+E=CH2; Y=H; Z=NH; R2= H 4-C1 4-F 4-CF3 4-OCF3 185 R3=4-F-Ph; A+E=CH2; Y=H; Z=NH; R2= H 4-C1 4-F 4-CF3 4-OCF3
186 R3=4-Cl-Ph; A+E=CH2; Y=H; Z=NH; R2= H 4-C1 4-F 4-CF3 4-OCF3
187 R3=C02Me; A=H; E=H; Y=H; Z=NMe; R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
188 R3=4-F-Ph; A=H; E=H; Y=H; Z=NMe; R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
189 R3=4-Cl-Ph; A=H; E=H; Y=H; Z=NMe; R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
190 R3=C02Me; A+E=OCH2; Y=H; Z=NMe; R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
191 R3=4-F-Ph; A+E=OCH2; Y=H; Z=NMe; R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
192 R3=4-Cl-Ph; A+E=OCH2; Y=H; Z=NMe; R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
193 R3=C02Me; A+E=CH2; Y=H; Z=NMe; R2= H 4-C1 4-F 4-CF3 4-OCF3
194 R3=4-F-Ph; A+E=CH2; Y=H; Z=NMe; R2= H 4-C1 4-F 4-CF3 4-OCF3
195 R3=4-Cl-Ph; A+E=CH2; Y=H; Z=NMe; R2= H 4-C1 4-F 4-CF3 4-OCF3
196 R3=C02Me; A=H; E=H; Y=H; Z=NC(0)Me; R = H 3-C1 3-CF3 3-OCF3 3-OCF2H
197 R3=4-F-Ph; A=H; E=H; Y=H; Z=NC(0)Me; R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
198 R3=4-Cl-Ph; A=H; E=H; Y=H; Z=NC(0)Me; R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
199 R3=C02Me; A+E=OCH2; Y=H; Z=NC(0)Me; R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
200 R3=4-F-Ph; A+E=OCH2; Y=H; Z=NC(0)Me; . R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
201 R3=4-Cl-Ph; A+E=OCH2; Y=H; Z=NC(0)Me; R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
202 R3=C02Me; A+E=CH2; Y=H; Z=NC(0)Me; R2= H 4-C1 4-F 4-CF3 4-OCF3
203 R3=4-F-Ph; A+E=CH2; Y=H; Z=NC(0)Me; R2= H 4-C1 4-F 4-CF3 4-OCF3
204 R3=4-Cl-Ph; A+E=CH2; Y=H; Z=NC(0)Me; R2= H 4-C1 4-F 4-CF3 4-OCF3
205 R3=C02Me; A=H; E=H; Y=H; Z=NC(0)Me; R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
206 R3=4-F-Ph; A=H; E=H; Y=H; Z=NC02Me; R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
207 R3=4-Cl-Ph; A=H; E=H; Y=H; Z=NC02Me; R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
208 R3=C02Me; A+E=OCH2; Y=H; Z=NC02Me; R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
209 R3=4-F-Ph; A+E=OCH2; Y=H; Z=NC02Me; R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
210 R3=4-Cl-Ph; A+E=OCH2; Y=H; Z=NC02Me; R2= H 3-C1 3-CF3 3-OCF3 3-OCF2H
211 R3=C02Me; A+E=CH2; Y=H; Z=NC02Me; R2= H 4-C1 4-F 4-CF3 4-OCF3
212 R3=4-F-Ph; A+E=CH2; Y=H; Z=NC02Me; R2= H 4-C1 4-F 4-CF3 4-OCF3
213 R3=4-Cl-Ph; A+E=CH2; Y=H; Z=NC02Me; R2= H 4-C1 4-F 4-CF3 4-OCF3
Figure imgf000034_0001
COLUM DN
1 2 3 4 5 6
214 R3=4-F-Ph; R6=H; E=H; Y=H; R2= H Cl F CF3 OCF3 OCF2H
215 R3= -Cl-Ph; R6=H; E=H; Y=H; R2= H Cl F CF3 OCF3 OCF2H
216 R3=4-F-Ph; R6=Me; E=H; Y=H; R2= H Cl F CF3 OCF3 OCF2H
217 R3=4-Cl-Ph; R6=Me; E=H; Y=H; R2= H Cl F CF3 OCF3 OCF2H
218 R3=4-F-Ph; R6=H; E=Me; Y=H; R2= H Cl F CF3 OCF3 OCF2H
219 R3=4-Cl-Ph; R6=H; E=Me; Y=H; R2= H Cl F CF3 OCF3 OCF2H
220 R3=4-F-Ph; R6=Me; E=Me; Y=H; R2= H Cl F CF3 OCF3 OCF2H
221 R3=4-Cl-Ph; R6=Me; E=Me; Y=H; R2= H Cl F CF3 OCF3 OCF2H
Formulation/Utility
Compounds of this invention will generally be used in formulation with an agriculturally suitable carrier comprising a liquid or solid diluent. Useful formulations include dusts, granules, baits, pellets, solutions, suspensions, emulsions, wettable powders, emulsifiable concentrates, dry flowables and the like, consistent with the . physical properties of the active ingredient, mode of application and environmental factors such as soil type, moisture and temperature. 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 weight percent. Weight Percent
Active Ingredient Diluent Surfactant
Wettable Powders 5-90 0-74 1-10
Oil Suspensions, Emulsions, 5-50 40-95 0-15 Solutions, (including Emulsifiable Concentrates)
Dusts 1-25 70-99 0-5
Granules, Baits 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 and solvents 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.
Solutions are prepared by simply mixing the ingredients. Fine solid compositions are made by blending and, usually, grinding as in a hammer mill or fluid energy mill. Water-dispersible granules can be produced by agglomerating a fine powder composition; see for example, Cross et al., Pesticide Formulations, Washington, D.C., 1988, pp 251-259. Suspensions are prepared by wet-milling; see, for example, U.S. 3,060,084. Granules and pellets can be made by spraying the active material upon preformed granular carriers or by agglomeration techniques. See Browning,
"Agglomeration", Chemical Engineering, December 4, 1967, pp 147-148, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and following, and WO 91/13546.
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 exhibit activity against a wide spectrum of foliar-feeding, fruit-feeding, stem or root feeding, seed-feeding, aquatic and soil-inhabiting arthropods (term "arthropods" includes insects, mites and nematodes) which are pests of growing and stored agronomic crops, forestry, greenhouse crops, ornamentals, nursery crops, stored food and fiber products, livestock, household, and public and animal health. Those skilled in the art will appreciate that not all compounds are equally effective against all growth stages of all pests. Nevertheless, all of the compounds of this invention display activity against pests that include: eggs, larvae and adults of the Order Lepidoptera; eggs, foliar-feeding, fruit-feeding, root-feeding, seed-feeding larvae and adults of the Order Coleoptera; eggs, immatures and adults of the Orders Hemiptera and Homoptera; eggs, larvae, nymphs and adults of the Order Acari; eggs, immatures and adults of the Orders Thysanoptera, Orthoptera and Dermaptera; eggs, immatures and adults of the Order Diptera; and eggs, juveniles and adults of the Phylum Nematoda. The compounds of this invention are also active against pests of the Orders Hymenoptera, Isoptera, Siphonaptera, Blattaria, Thysanura and Psocoptera; pests belonging to the Class Arachnida and Phylum Platyhelminthes. Specifically, the compounds are active against southern corn rootworm (Diabrotica undecimpunctata howardi), aster leafhopper (Mascrosteles fascifrons), boll weevil (Anthonomus grandis), two-spotted spider mite {Tetranychus urticae), fall army worm (Spodopterafrugiperda), black bean aphid (Aphis fabae), green peach aphid (Myzus persica), cotton aphid (Aphis gossypii), Russian wheat aphid (Diuraphis noxia), English grain aphid (Sitobion avenae), tobacco budworm (Heliothis virescens), rice water weevil (Lissorhoptrus oryzophilus), rice leaf beetle (Oulema oryzae), whitebacked planthopper (Sogatellafurcifera), green leafhopper (Nephotettix cincticeps), brown planthopper
(Nilaparvata lugens), small brown planthopper (Laodelphax striatellus), rice stem borer (Chilo suppressalis), rice leafroller (Cnaphalocrocis medinalis), black rice stink bug (Scotinophara luridά), rice stink bug (Oebalus pugnax), rice bug Leptocorisa chinensis), slender rice bug (Cletus puntiger), and southern green stink bug (Nezara viridula). The compounds are active on mites, demonstrating ovicidal, larvicidal and chemosterilant activity against such families as Tetranychidae including Tetranychus urticae, Tetranychus cinnabarinus, Tetranychus mcdanieli, Tetranychus pacificus, Tetranychus turkestani, Byrobia rubrioculus, Panonychus ulmi, Panonychus citri, Eotetranychus carpini borealis, Eotetranychus, hicoriae, Eotetranychus sexmaculatus, Eotetranychus yumensis, Eotetranychus banksi and Oligonychus pratensis;
Tenuipalpidae including Brevipalpus lewisi, Brevipalpus phoenicis, Brevipalpus calif ornicus and Brevipalpus obovatus; Eriophyidae including Phyllocoptruta oleivora, Eriophyes sheldoni, Aculus cornutus, Epitrimerus pyri and Eriophyes mangiferae. See WO 90/10623 and WO 92/00673 for more detailed pest descriptions. 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 other agricultural protectants with which compounds of this invention can be formulated are: insecticides such as avermectin B, monocrotophos, carbofuran, tetrachlorvinphos, malathion, parathion-methyl, methomyl, chlordimeform, diazinon, deltamethrin, oxamyl, fenvalerate, esfenvalerate, permethrin, profenofos, sulprofos, triflumuron, diflubenzuron, methoprene, buprofezin, thiodicarb, acephate, azinphosmethyl, chlo yrifos, dimethoate, fipronil, flufenprox, fonophos, isofenphos, methidathion, metha-midophos, phosmet, phosphamidon, phosalone, pirimicarb, phorate, terbufos, trichlorfon, methoxychlor, bifenthrin, biphenate, cyfluthrin, tefluthrin, fenpropathrin, fluvalinate, flucythrinate, tralomethrin, imidacloprid, metaldehyde and rotenone; fungicides such as carbendazim, thiuram, dodine, maneb, chloroneb, benomyl, cymoxanil, fenpropidine, fenpropimoiph, triadimefon, captan, thiophanate-methyl, thiabendazole, phosethyl-Al, chlorothalonil, dichloran, metalaxyl, captafol, iprodione, oxadixyl, vinclozolin, kasugamycin, myclobutanil, tebuconazole, difenoconazole, diniconazole, fluquinconazole, ipconazole, metconazole, penconazole, propiconazole, uniconzole, flutriafol, prochloraz, pyrifenox, fenarimol, triadimenol, diclobutrazol, copper oxychloride, furalaxyl, folpet, flusilazol, blasticidin S, diclomezine, edifenphos, isoprothiolane, iprobenfos, mepronil, neo-asozin, pencycuron, probenazole, pyroquilon, tricyclazole, validamycin, and flutolanil; nematocides such as aldoxycarb, fenamiphos and fosthietan; bactericides such as oxytetracyline, streptomycin and tribasic copper sulfate; acaricides such as binapacryl, oxythioquinox, chlorobenzilate, dicofol, dienochlor, cyhexatin, hexythiazox, a itraz, propargite, tebufenpyrad and fenbutatin oxide; and biological agents such as entomopathogenic bacteria, virus and fiingi.
In certain instances, combinations with other arthropodicides having a similar spectrum of control but a different mode of action will be particularly advantageous for resistance management.
Arthropod pests are controlled and protection of agronomic, horticultural and specialty crops, animal and human health is achieved by applying one or more of the compounds of this invention, in an effective amount, to the environment of the pests including the agronomic and or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled. Thus, the present invention further comprises a method for the control of foliar and soil inhabiting arthropods and nematode pests and protection of agronomic and/or nonagronomic crops, comprising applying one or more of the compounds of Formula I, or compositions containing at least one such compound, in an effective amount, to the environment of the pests including the agronomic and/or nonagronomic locus of infestation, to the area to be protected, or directly on the pests to be controlled. A preferred method of application is by spraying. Alternatively, granular formulations of these compounds can be applied to the plant foliage or the soil. Other methods of application include direct and residual sprays, aerial sprays, seed coats, microencapsulations, systemic uptake, baits, eartags, boluses, foggers, fumigants, aerosols, dusts and many others. The compounds can be incorporated into baits that are consumed by the arthropods or in devices such as traps and the like. The compounds of this invention can be applied in their pure state, but most often application will be of a formulation comprising one or more compounds with suitable carriers, diluents, and surfactants and possibly in combination with a food depending on the contemplated end use. A preferred method of application involves spraying a water dispersion or refined oil solution of the compounds. Combinations with spray oils, spray oil concentrations, spreader stickers, adjuvants, and synergists and other solvents such as piperonyl butoxide often enhance compound efficacy.
The rate of application required for effective control will depend on such factors as the species of arthropod to be controlled, the pest's life cycle, life stage, its size, location, time of year, host crop or animal, feeding behavior, mating behavior, ambient moisture, temperature, and the like. Under normal circumstances, application rates of about 0.01 to 2 kg of active ingredient per hectare are sufficient to control pests in agronomic ecosystems, but as little as 0.001 kg/hectare may be sufficient or as much as 8 kg hectare may be required. For nonagronomic applications, effective use rates will range from about 1.0 to 50 mg/square meter but as little as 0.1 mg/square meter may be sufficient or as much as 150 mg/square meter may be required.
The following TESTS demonstrate the control efficacy of compounds of this invention on specific pests. "Control efficacy" represents inhibition of arthropod development (including mortality) that causes significantly reduced feeding. The pest control protection afforded by the compounds is not limited, however, to these species. See Index Tables A-D for the compound descriptions.
Index Table A
Figure imgf000039_0001
Compound l2 ^ Jl3 ^ X m. p. °C
1 CF3 CCOO2CCHH3„ HH 236-238 Index Table B
Figure imgf000040_0001
Compound -R__ _Rl Y m. p. °C
2 Cl CO2CH3 CO2CH3 59-60
Index Tabfe C
Figure imgf000040_0002
Compound ^ R15 Y m. p. °C
3 σ Ph H 205-207
4 F Ph H 195-196
5 F 4-OMe-Ph H 159-160
6 F 4-CH3-Ph H 159-160
7 F 4-F-Ph H 212-213
8 F 4-Cl-Ph H 205-207
9 Cl 4-Cl-Ph H 209-210 Index Table D
Figure imgf000041_0001
Compound _R_. Rl X m. p. °C 10 F 4-F-Ph H 216-217 11 Cl iPr H 177-179
TEST A
Fall Armyworm Test units, each consisting of a H.I.S. (high impact styrene) tray with 16 cells were prepared. Wet filter paper and approximately 8 cm2 of lima bean leaf was placed into twelve of the cells. A 0.5 cm layer of wheat germ diet was placed into the four remaining cells. Fifteen to twenty third-instar larvae of fall armyworm (Spodoptera frugiperdd) were placed into a 230 mL (8 ounce) plastic cup. Solutions of each of the test compounds in 75/25 acetone/distilled water solvent were sprayed into the tray and cup. Spraying was accomplished by passing the tray and cup on a conveyer belt directly beneath a flat fan hydraulic nozzle which discharged the spray at a rate of 0.55 kg of active ingredient per hectare (about 0.5 pounds per acre) at 207 kPa (30 p.s.i.). The insects were transferred from the 230 mL cup to the H.I.S. tray (one insect per cell). The trays were covered and held at 27°C and 50% relative humidity for 48 h, after which time readings were taken on the twelve cells with lima bean leaves. The 4 four remaining cells were read at 6-8 days for delayed toxicity. Of the compounds tested, the following gave control efficacy levels of 80% or greater: 1, 2, 3, 4, 5*, 6* and 10*. * - tested at 0.14 kg/ha. TEST B
Tobacco Budworm
The test procedure of TEST A was repeated to determine efficacy against third-instar larvae of the tobacco budworm (Heliothis virescens) except that three 230 mL (8 ounce) plastic cups with wheat germ diet were used in place of the H.I.S. tray, with each cup pre-infested with 5 third-instar larvae. Of the compounds tested, the following gave mortality levels of 80% or higher: 1, 3, 4, 5* and 10*. * - tested at 0.14 kg/ha. TEST C Southern Corn Rootworm
Test units, each consisting of a 230 mL (8 ounce) plastic cup containing a 2.54 cm2 plug (1 square inch) of a wheatgerm diet, were prepared. The test units were sprayed as described in TEST A with individual solutions of the test compounds. After the spray on the cups had dried, five second-instar larvae of the southern corn rootworm (Diabrotica undecimpunctata howardϊ) were placed into each cup. The cups were held at 27°C and 50% relative humidity for 48 h, after which time mortality readings were taken. The same units were read again at 6-8 days for delayed toxicity. Of the compounds tested, the following gave control efficacy levels of 80% or greater: 1 and 4.
TEST D Aster Leafhopper
Test units were prepared from a series of 350 mL (12 ounce) cups, each containing oat (Avena sativa) seedlings in a 2.54 cm (1 inch) layer of sterilized soil. The test units were sprayed as described in TEST A with individual solutions of the test compounds. After the oats had dried from the spraying, 10 to 15 adult aster leafhoppers (Mascrosteles fascifrons) were aspirated into each of the cups. The cups were covered with vented lids and held at 27°C and 50% relative humidity for 48 h, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher: 1 and 2.
TEST E Boll Weevil
Test units consisting of 260 mL (9 ounce) cups containing five adult boll weevils (Anthonomus grandis grandis) were prepared. The test units were sprayed as described in TEST A with individual solutions of the test compounds. Each cup was covered with a vented lid and held at 27°C and 50% relative humidity for 48 h, after which time mortality readings were taken. Of the compounds tested, the following gave mortality levels of 80% or higher: 1 and 3.

Claims

1. A compound of the formula
Figure imgf000043_0001
wherein
Q is selected from the group
Figure imgf000043_0002
Figure imgf000043_0003
Figure imgf000044_0001
A is H;
A1 is selected from the group CH2, CH2CH2, O, S(O)q, NR7, OCH2, S(O)qCH2, N(R7)CH2, substituted CH2, and substituted CH2CH2, the substituents independently selected from 1-2 halogen and 1-2 methyl;
E is selected from the group H and C1-C3 alkyl; or
A and E are taken together to form CH2, CH2CH2, O, S(O)q, NR7, OCH2, S(O)qCH2, N(R7)CH2, substituted CH2, and substituted CH2CH2, the substituents independently selected from 1-2 halogen and 1-2 methyl;
M is selected from the group H and C1-C3 alkyl; or
E and M are taken together as CH2CH2, CH2CH2CH2 or CH2CH2CH2CH2, each group optionally substituted with one or more members independently selected from the group halogen, NO2, CN, C1-C3 alkyl, C1-C3 haloalkyl, OR8, C(O)Rl6 and C(O)OR16;
X is selected from the group O and S;
Y is selected from the group H, C C^ alkyl, Cj-Cg haloalkyl, C2-Cg alkenyl, C2-Cg haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, C4-C7 cycloalkylalkyl, CHO, C(O)R16, C(O)OR16, C(S)R16, C(S)SR16, C(O)C(O)OR16, C(O)CH2C(O)OR16, SH, S(O)rR16,
S(O)2CH2C(O)OR16, P(X)(OR18)2, S(O)rN(R12)C(O)ORn, S(O)rNR13R14, N=CR9R10, OR8, NR8R9; benzyl optionally substituted with 1-3 groups independently selected from the group W; and Cj-Cg alkyl substituted with halogen, C1-C3 alkoxy, C1-C3 haloalkoxy, CN, NO2, S(O)rR16, P(X)(OR18)2, C(O)R16, C(O)OR16 and phenyl optionally substituted with halogen, CN, Cι-C2 haloalkyl and Cι-C2 haloalkoxy;
Z is selected from the group CH2, O, S(O)r and NR19;
R1 and R2 are independently selected from the group H, Cj^ alkyl, Cj-Cg haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-Cg alkynyl, C2-Cg haloalkynyl, OR8, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, CrC6 nitroalkyl,
C2-C6 cyanoalkyl, C3-Cg alkoxycarbonylalkyl, C3-C6 cycloalkyl, C3-Cg halocycloalkyl, halogen, CN, N3, SCN, NO2, SH, S(O)rR16, OCHO, CHO, C(O)R16, C(O)OR16, C(O)NR16R17, S(O)2NR16R17, NR16R17, NR17C(O)R16, OC(O)NHR16, NR17C(O)NHR16, NR17S(O)2R16, phenyl optionally substituted with 1-3 substituents independently selected from W, and benzyl optionally substituted with 1-3 substituents independently selected from W; or when m or n is 2 and the two R1 groups or the two R2 groups are adjacent, (R-)2 are optionally taken together as, or (R2)2 are optionally taken together as, -OCH2O-, -OCF2O-, -OCH2CH2O-, -CH2C(CH3)2O-, -CF2CF2O- or -OCF2CF2O- to form a cyclic bridge; R3 is selected from the group J, H, halogen, Cj-Cg alkyl, Cj-C6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C4-C7 cycloalkylalkyl, OR8, C3-C8 alkoxycarbonylalkyl, CHO, C(O)R16, C(O)OR16, C(O)NR16R17, C(S)NR16R17, C(S)R16, C(S)SR16, CN, Si(R20)(R21)(R22), SH, S(O)rR16, P(X)(ORl8)2, N3, NO2, NR8R9, phenyl optionally substituted with (R23)p, and benzyl optionally substituted with 1-3 substituents independently selected from W; or R3 is C2-C6 epoxyalkyl optionally substituted with 1-2 substituents independently selected from the group CrC3 alkyl, CN, C(O)R16, C(O)OR16 and phenyl optionally substituted with W; or R3 is C2-C6 alkyl substituted with one or more members independently selected from the group OR8, C(O)NR16R17, C(O)R16, C(O)OR"\ SH, S(O)rR16, SCN, CN, Si(R20)(R21)(R22) and
NR8R9; R4, R5 and R6 are independently selected from the group H, CrC4 alkyl, C(O)R16 and C(O)OR16; R7 is selected from the group H, Cj-C alkyl, C1-C4 haloalkyl, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, CHO, C(O)R16,
C(O)OR16, C(O)NR16R17, C(S)NRl6Rl7, C(S)R16, C(S)2R16, S(O)rR16, P(X)(OR18)2, optionally substituted phenyl, and optionally substituted benzyl wherein the optional phenyl and benzyl substituents are 1-2 substituents independently selected from W; R8 is selected from the group H, CrC4 alkyl, CrC4 haloalkyl, C2-C4 alkenyl,
C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, C(O)R16, C(O)OR16, C(O)NR16R17, S(O)2NR16R17, S(O)2R16, optionally substituted phenyl, and optionally substituted benzyl wherein the optional phenyl and benzyl substituents are 1-2 substituents independently selected from W; R9 is selected from the group H, CrC4 alkyl, C(O)R16 and C(O)OR16;
R10 is selected from the group H, C1-C4 alkyl, C1-C4 haloalkyl and phenyl optionally substituted with 1-2 substituents independently selected from W; or R9 and R10 are taken together as CH2CH2CH2, CH2CH2CH2CH2 or CH2CH2CH2CH2CH2;
R11 is CrC18 alkyl;
R12 is CrC4 alkyl; R13 and R14 are independently C1-C4 alkyl; or
R13 and R14 are taken together as CH2CH2CH2CH2CH2 or CH2CH2OCH2CH2;
R15 is selected from the group J and phenyl optionally substituted with (R23)p;
R16 is selected from the group CrC6 alkyl, Cj-Cg haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C2-C6 alkynyl, C2-C6 haloalkynyl, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, CrC6 nitroalkyl, C2-C6 cyanoalkyl, C3-C8 alkoxycarbonylalkyl, C3-Cg cycloalkyl, C3-C6 halocycloalkyl, optionally substituted phenyl and optionally substituted benzyl wherein the optional phenyl and benzyl substituents are 1-3 substituents independently selected fromW; R17 is selected from the group H and C1-C4 alkyl; or
R16 and R17, when attached to the same atom, are taken together as (CH2)4, (CH2)5, or CH2CH2OCH2CH2;
R18 is selected from the group C1-C3 alkyl and phenyl optionally substituted with at least one member independently selected from W; R19 is selected from the group H, CrC6 alkyl, CrC6 haloalkyl, C2-C6 alkenyl,
C2-C6 haloalkenyl, C2-Cg alkynyl, C2-C6 haloalkynyl, C3~C6 cycloalkyl, C3-C6 halocycloalkyl, CHO, C(O)R16, C(O)OR16, C(S)R16, C(S)2R16, C(O)C(O)OR16, C(O)CH2C(O)OR16, S(O)rR16, S(O)2CH2C(O)OR16, P(X)(OR18)2, C(O)NR!6R17, S(O)rNR16R17, S(O)rN(R12)C(O)ORπ, S(O)rN(R12)CHO, C(O)Ph where the phenyl group is optionally substituted by a group independently selected from W; and benzyl optionally substituted by a group independently selected from W; or R19 is C1-C4 alkyl substituted with 1-2 substituents independently selected from the group Cι-C2 alkoxy, CrC2 haloalkoxy, CN, NO2, C(O)R16, C(O)OR16 and NR8R9; R20 and R21 are independently CrC4 alkyl;
R22 is selected from the group C1-C4 alkyl and phenyl optionally substituted with W;
R23 is selected from the group CrC6 alkyl, CrC6 haloalkyl, C2-C6 alkenyl, C2-C6 haloalkenyl, C -C6 alkynyl, C2-C6 haloalkynyl, OR8, C2-C6 alkoxyalkyl, C2-C6 alkylthioalkyl, C C6 nitroalkyl, C2-C6 cyanoalkyl, C3-C8 alkoxycarbonylalkyl, C3-C6 cycloalkyl, C3-C6 halocycloalkyl, halogen, CN, N3, SCN, NO2, CHO,
Figure imgf000046_0001
SH, S(O)rRl6, S(O)2NR16R17, NR16Rl7, NR17C(O)R16, OC(O)NHRl6, NR17C(O)NHR16, NR17S(O)2R16, phenyl optionally substituted with 1-3 substituents independently selected from W, and benzyl optionally substituted with 1-3 substituents independently selected from W; or when p is 2 and the two R23 groups are adjacent, (R 3)2 are optionally taken together as -OCH2O-, -OCF2O-, -OCH2CH2O-, -CH2C(CH3)2O-,
-CF2CF2O- or -OCF2CF2O- to form a cyclic bridge; J is selected from the group
Figure imgf000047_0001
J-l J-2
Figure imgf000047_0002
J-3 J-4
W is selected from the group halogen, GN, NO2, Cι-C2 alkyl, Cj-C2 haloalkyl, Cι-C2 alkoxy, Cj-Gj haloalkoxy, C1-C2 alkylthio, Cι~C haloalkylthio, Cι-C2 alkylsulfonyl, and Cι-C2 haloalkylsulfonyl;
X1 is selected from the group O or S; Z- and Z2 are independently selected from the group CH or N; m is 1 to 3; n is 1 to 3; p is 0 to 3; q is 0 to 3; and r is 0, 1 or 2.
2. A compound according to Claim 1 wherein
Y is selected from the group H, CrC6 alkyl, C(O)R16 and C(O)OR16.
3. A compound according to Claim 2 wherein Q is Q-l;
A1 is selected from the group CH2, CH2CH2, OCH2, S(O)qCH2 and
N(R7)CH2; and X is O.
4. A compound according to Claim 3 wherein R1 is H; and
SF5 is in the 4-position.
5. A compound according to Claim 2 wherein
Q is Q-2; R1 is H; and
SF5 is in the 4-position.
6. A compound according to Claim 2 wherein
A and E are taken together to form CH2, CH2CH2, OCH2, S(O)qCH2 and N(R7)CH2; and X is O.
7. A compound according to Claim 6 wherein Q is Q-3.
8. A compound according to Claim 7 wherein
R1 is H;
Z is selected from the group O, S(O)q and NR19; and SF5 is in the 4-position.
9. A compound according to Claim 2 wherein
Q is Q-4 R1 is H; and SF5 is in the 4-position.
10. A compound according to Claim 4 which is:
[4-[[t3a,4-dihydro-3a-(methoxycarbonyl)-7-(trifluoromethyl)[l]benzopyranb- [4,3-c]pyrazol-2(3H)-yl]carbonyl]amino]phenyl]pentafluorosulfide.
11. An arthropodicidal composition comprising an arthropodicidally effective amount of a compound according to Claim 1 and a carrier therefor.
12. A method for controlling arthropods comprising contacting the arthropods or their environment with an arthropodicidally effective amount of a compound according to Claim 1.
PCT/US1994/013917 1993-12-17 1994-12-14 Arthropodicidal pentafluorothio substituted anilides WO1995016676A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU14309/95A AU1430995A (en) 1993-12-17 1994-12-14 Arthropodicidal pentafluorothio substituted anilides

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US16946293A 1993-12-17 1993-12-17
US08/169,462 1993-12-17

Publications (1)

Publication Number Publication Date
WO1995016676A1 true WO1995016676A1 (en) 1995-06-22

Family

ID=22615804

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1994/013917 WO1995016676A1 (en) 1993-12-17 1994-12-14 Arthropodicidal pentafluorothio substituted anilides

Country Status (2)

Country Link
AU (1) AU1430995A (en)
WO (1) WO1995016676A1 (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10353205A1 (en) * 2003-11-13 2005-06-16 Aventis Pharma Deutschland Gmbh Ortho-substituted pentafluorosulfurane-benzenes, processes for their preparation and their use as valuable synthesis intermediates
US7317124B2 (en) 2003-11-13 2008-01-08 Sanofi-Aventis Deutschland Gmbh Ortho-substituted pentafluorosulfanylbenzenes, process for their preparation and their use as valuable synthetic intermediates
WO2010144434A1 (en) * 2009-06-09 2010-12-16 The United States Of America, As Represented By The Secretary Of The Army, On Behalf Of U.S. Derivatives of mefloquine and associated methods for making and using

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4156007A (en) * 1974-07-12 1979-05-22 U.S. Philips Corporation Pyrazoline compounds
EP0153127A2 (en) * 1984-02-16 1985-08-28 Rohm And Haas Company N-aryl-3-aryl-4,5-dihydro-1H-pyrazole-1-carboxamides, processes for their production, insecticidal compositions containing them and methods for combatting insects
WO1992020682A1 (en) * 1991-05-24 1992-11-26 E.I. Du Pont De Nemours And Company Arthropodicidal anilides

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4156007A (en) * 1974-07-12 1979-05-22 U.S. Philips Corporation Pyrazoline compounds
EP0153127A2 (en) * 1984-02-16 1985-08-28 Rohm And Haas Company N-aryl-3-aryl-4,5-dihydro-1H-pyrazole-1-carboxamides, processes for their production, insecticidal compositions containing them and methods for combatting insects
WO1992020682A1 (en) * 1991-05-24 1992-11-26 E.I. Du Pont De Nemours And Company Arthropodicidal anilides

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10353205A1 (en) * 2003-11-13 2005-06-16 Aventis Pharma Deutschland Gmbh Ortho-substituted pentafluorosulfurane-benzenes, processes for their preparation and their use as valuable synthesis intermediates
US7317124B2 (en) 2003-11-13 2008-01-08 Sanofi-Aventis Deutschland Gmbh Ortho-substituted pentafluorosulfanylbenzenes, process for their preparation and their use as valuable synthetic intermediates
US7932416B2 (en) 2003-11-13 2011-04-26 Sanofi-Aventis Deutschland Gmbh Ortho-substituted pentafluorosulfanylbenzenes, process for their preparation and their use as valuable synthetic intermediates
WO2010144434A1 (en) * 2009-06-09 2010-12-16 The United States Of America, As Represented By The Secretary Of The Army, On Behalf Of U.S. Derivatives of mefloquine and associated methods for making and using

Also Published As

Publication number Publication date
AU1430995A (en) 1995-07-03

Similar Documents

Publication Publication Date Title
WO1995003306A1 (en) Arthropodicidal azacyclic heterocycles
EP0712394B1 (en) Arthropodicidal oxazolines and thiazolines
US5728693A (en) Arthropodicidal oxadiazine-thiadiazine-or triazine-carboxanilides
WO1995007278A1 (en) Fungicidal, miticidal and arthropodicidal aminopyrimidines
WO1993022291A1 (en) Arthropodicidal and fungicidal aminopyrimidines
US5328915A (en) Arthropodicidal amidrazone ureas
EP0632803B1 (en) Arthropodicidal amides
EP0646111B1 (en) Arthropodicidal oxazolines and thiazolines
WO1997011057A1 (en) Arthropodicidal 1,4-dihydropyridines and 1,4-dihydropyrimidines
WO1995016676A1 (en) Arthropodicidal pentafluorothio substituted anilides
WO1995019972A1 (en) Arthropodicidal 2-oxa and thia-zolines
US5444079A (en) Arthropodicidal oxazolines
US5538967A (en) Arthropodicidal oxazines and thiazines
WO1993021160A1 (en) Arthropodicidal pyrazole sulfonates
WO1995000491A1 (en) Arthropodicidal sulfonates
US5767281A (en) Arthropodicidal oxazolines and thiazolines
WO1994008954A1 (en) Arthropodicidal semicarbazones
WO1993010096A1 (en) Arthropodicidal and nematicidal sulfonates
WO1993022289A1 (en) Arthropodicidal imidazolidines
US5514678A (en) Arthropodicidal 1,2,4-triazinyl amides
WO1993021150A2 (en) Arthropodicidal aryl sulfonates
EP0629201A1 (en) Arthropodicidal amides
WO1995006631A1 (en) Polycyclic arthropodicides
HUT76814A (en) Arthropodicidal tetrahydropyrimidines, compositions containing these compounds as active ingredients and use thereof
WO1994012491A1 (en) Arthropodicidal nitroethylene diamines

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AM AU BB BG BR BY CA CN CZ EE FI GE HU JP KG KP KR KZ LK LR LT LV MD MG MN NO NZ PL RO RU SI SK TJ TT UA US UZ VN

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): KE MW SD SZ AT BE CH DE DK ES FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
122 Ep: pct application non-entry in european phase
NENP Non-entry into the national phase

Ref country code: CA