AU601656B2 - Pesticidal polyhaloalkene derivatives - Google Patents

Pesticidal polyhaloalkene derivatives Download PDF

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AU601656B2
AU601656B2 AU61229/86A AU6122986A AU601656B2 AU 601656 B2 AU601656 B2 AU 601656B2 AU 61229/86 A AU61229/86 A AU 61229/86A AU 6122986 A AU6122986 A AU 6122986A AU 601656 B2 AU601656 B2 AU 601656B2
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trifluoro
substituted
butenylthio
butenyl
compounds
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AU61229/86A
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AU6122986A (en
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Thomas Gerard Cullen
Anthony Joseph Martinez
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FMC Corp
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FMC Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/36—Oxygen or sulfur atoms
    • C07D207/40—2,5-Pyrrolidine-diones
    • C07D207/404—2,5-Pyrrolidine-diones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. succinimide
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C33/00—Unsaturated compounds having hydroxy or O-metal groups bound to acyclic carbon atoms
    • C07C33/40—Halogenated unsaturated alcohols
    • C07C33/42—Halogenated unsaturated alcohols acyclic
    • 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
    • A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
    • A01N31/02—Acyclic compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/02—Saturated carboxylic acids or thio analogues thereof; Derivatives thereof
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/06—Unsaturated carboxylic acids or thio analogues thereof; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/10—Aromatic or araliphatic carboxylic acids, or thio analogues thereof; Derivatives thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/18—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group —CO—N<, e.g. carboxylic acid amides or imides; Thio analogues thereof
    • A01N37/32—Cyclic imides of polybasic carboxylic acids or thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/52—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being acyclic and saturated
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    • C07C33/40—Halogenated unsaturated alcohols
    • C07C33/42—Halogenated unsaturated alcohols acyclic
    • C07C33/423—Halogenated unsaturated alcohols acyclic containing only double bonds as unsaturation
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C331/00—Derivatives of thiocyanic acid or of isothiocyanic acid
    • C07C331/16—Isothiocyanates
    • C07C331/18—Isothiocyanates having isothiocyanate groups bound to acyclic carbon atoms
    • C07C331/22—Isothiocyanates having isothiocyanate groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
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    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
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    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
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    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
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    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
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    • C07D271/02—Heterocyclic compounds containing five-membered rings having two nitrogen atoms and one oxygen atom as the only ring hetero atoms not condensed with other rings
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    • C07D271/07—1,2,4-Oxadiazoles; Hydrogenated 1,2,4-oxadiazoles with oxygen, sulfur or nitrogen atoms, directly attached to ring carbon atoms, the nitrogen atoms not forming part of a nitro radical
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    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
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    • C07D277/12—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D285/01—Five-membered rings
    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
    • C07D285/08—1,2,4-Thiadiazoles; Hydrogenated 1,2,4-thiadiazoles
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    • C07D285/02—Thiadiazoles; Hydrogenated thiadiazoles
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    • C07D285/12—1,3,4-Thiadiazoles; Hydrogenated 1,3,4-thiadiazoles
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    • C07D285/04—Thiadiazoles; Hydrogenated thiadiazoles not condensed with other rings
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    • C07D307/56—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D307/70—Nitro radicals
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    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D333/52—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes
    • C07D333/54—Benzo[b]thiophenes; Hydrogenated benzo[b]thiophenes with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to carbon atoms of the hetero ring

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  • 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)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Nitrogen- Or Sulfur-Containing Heterocyclic Ring Compounds With Rings Of Six Or More Members (AREA)

Description

j' PCT WORLD NlTELLECTUAL PROPER ORA
O
INTERNATIONAL APPLICATION PU I UNERI N OPERATION TREATY (PCT) (51) International Patent Classification 4 (11) International.Publication Number: WO 86/ 07590 C07C 33/42, 69/63, 69/767 C07D 271/06, 271/10, 277/26 Al C07D 285/06, 285/12 AO1N 31/02, 37/02, 37/10 (43) International Publication Date: A01N31 December 1986 (31.12.86) A01N 43/78, 43/82 r* (21) International Application Number: PCT/US86/01284 (22) International Filing Date: 12 June 1986 (12.06.86) (31) Priority Application Numbers: 747,142 746,911 (32) Priority Dates: 20 June 1985 (20.06.85) June 1985 (20.06.85) (33) Priority Country:
US
(71) Applicant: FMC CORPORATION [US/US]; 2000 Market Street, Philadelphia, PA 19103 (US).
(72) Inventors: CULLEN, Thomas, Gerard 22 Harrison Avenue, Milltown, NJ 08850 MARTINEZ, Anthony, Joseph 20 Weyburne Road, Hamilton Square, NJ 08690 (US).
This doumrnent contains the namendinents made under Section 49 and is correct for printing.
(74) Agent: FELLOWS, Charles, FMC Corporation, 2000 Market Street, Philadelphia, PA 19103 (US).
(81) Designated States: AU, BR, CF (OAPI patent), CG (OAPI patent), CH (European patent), CM (OAPI patent), DE (European patent), DK, FR (European patent), GA (OAPI patent), GB (European patent), HU, IT (European patent), JP, KR, ML (OAPI patent), MR (OAPI patent), NL (European patent), SN (OAPI patent), TD (OAPI patent), TG (OAPI patent).
Published With international search report.
With amended claims and statement.
AUSTRALIAN
13 JAN 1 987 flArgr-.,, 9 rrC,-
I
54) Title: PESTICIDAL POLYHALOALKENE DERIVATIVES
Y
1 S4 -X
R
Y
2 (57) Abstract Polyhaloalkene compounds of formula wherein X is sulfur, oxygen, nitrogen or methylene, yl and Y2 independently are fluorine, chlorine or bromine, Z is hydrogen or the same as yl or Y2, and n is 1-4; provided that: when X is sulfur, R is thiazolyl substituted thienyl, optionally substituted thianaphthyl, optionally substituted thiazolinyl, optionally substituted thiadiazolyl, optionally substituted oxadiazolyl or 3,4,4- trifluoro-3-butenyloxycarbonyl-methyl; when X is oxygen, R is C(O)RI wherein RI is perfluoroalkyl, optionally substituted phenyl, optionally substituted thienyl, optionally substituted furanyl, optionally substituted pyrrolyl or dihydrothiazolylthiomethyl; when X is nitrogen, R taken with the nitrogen is an isothiocyanate, succinimide or saccharine group; and when X is methylene, R is hydroxy. The compounds exhibit activity against plant nematodes and helminths that are indicators of animal anthelmintic activity and therefore are useful ini agriculture and veterinary practice.
k _wN WO 86/07590 PCT/US86/01284
-I-
PESTICIDAL POLYHALOALKENE DERIVATIVES This invention relates to pesticidal polyhaloalkene derivatives and use for combatting infestations of nematodes in soil and in plant systems, particularly agricultural crops, and for combatting plantdestructive diseases caused wholly or in part by nematodes. The invention further concerns anthelmintic applications of the compounds.
U.S. Patent 3,513,172 Brokke and divisional patents thereof disclose nematicidal trifluorobutenyl derivatives of the formula F2C=CFCH2CH2-R where R is selected from various substituents including some heterocyclics such as 2-thio-4-alkylthiazolyl. These and other patents reflect ongoing efforts of industry and governmental agencies to find and commercialize chemicals for combatting nematodes and nematode-induced plant diseases, to thereby reduce the substantial economic losses resulting from nematode infestations.
A new class of polyhaloalkene derivatives has now been found having high nematicidal activity and good soil mobility. In addition, the compounds exhibit control of a variety of nematodes, and in some cases systemic activity. The compounds also are effective against helminths that are indicators of animal anthelmintic activity.
The novel nematicidal compounds of the invention are polyhaloalkene derivatives of the formula -2wherein X is sulfur, oxygen, nitrogen or methylene, Y' and y 2 independently are fluorine, chlorine or bromine, Z is hydrogen or the same asY 1 or 2, and n is 1-4, preferably 1 or 2; provided that: when X is sulfur, and R is thieriyl or substituted thienyl, thianaphthyl or substituted thianaphthyl, thiazolinyl or substituted thiazolinyl oxadiazolyl or substituted oxadiazolyl wherein the thienyl, thianaphthyl, thiazolinyl and oxadiazolyl substituents are selected from aliphatic, aromatic and heterocyclic groups, halo, nitro, cyano, alkoxy, alkylthio, haloalkyl, haloalkoxy, halo-, nitro-, cyano- or alkoxy-substituted phenyl, polyhialoalkenylthio, phenylalkylthio, phenylthioalkylthio, ,1 15 propargylthio, and cycloalkyl- methylthio; 3,4,4-trifluoro-3-butenyloxycarbonylmethyl, thiadiazolyl substituted by halogen or R2S wherein R 2 i S 3,4,4,-trifluoro-3-butenyl or R 2 is phenylmethyl or phenylthio-methyl each optionally substituted by halogen or nitro; or R is thiadiazoltyl substituted by R 3 wherein R 3 i s substituted aryl, arylalkyl, aryloxyalkyl, alkylthio, haloalkylthio, haloarylthio, cyanoalkylthio, arylalkylthio, aryloxyalkylthio, arylthioalkylthio, heterocycloalkylthio, alkeny.lthio, haloalkenylthio, halocycloalkylalkenyl thio, wherein said aryl 01' heterocyclo-substitutents of R 3 may be mono-, di-, tri-, tetra-, or pentat-substituted by q(-dy Iected from halogen, haloalkyl, alkoxy, I-Inalk-x:y, cyano, nitro and phenyl; or R 3 is an amino group mono- or di-substituted with members independently glected from alkyl, alkylcarbonyl, haloalkylcarbonyl, aryl, arylaminocarbonyl,
CO
7E -2aarylalkylcarbonyl, arylalkoxycarbonyl, and 3-(2,2-dichlorethenyl)-2,2-dimethylcyclopropanecarbonyl; when X is oxygen, and R is C(O)R' wherein R 1 is perfluoralkyl, phenyl or substituted phenyl, thienyl or substituted thienyl, furanyl or substituted furanyl, pyrollyl or substituted pyrollyl, or dihydrothiazolylthiomethyl wherein the phenyl, thienyl, furanyl, pyrollyl substituents are selected from aliphatic, aromatic and heterocyclic groups, halo, nitro, cy7no, alkoxy, alkylthio, haloal.kyl, haloalkoxy, halo-, nitro-, cyano- or alkoxy-substituted phenyl, polyhaloalkenylthio, phenylalkylthio, phenylthioalkylthio, propargylthio, and cycloalkylmethylthio; and when X is nitrogen, R taken with the nitrogen is an isothiocyanate, succinimide or saccharine group; wherein the heterocyclo substituents of and are selected from thienyl, isoxazolyl, pyridinyl, thiazolyl, thiazolinyl, benzodioxanyl, benzodioxolyl, tetrazolyl and furanyl.
when X is methylene, R is hydroxy.
Other aspects of the invention include methods of controlling .nematode populations and arresting plant and animal diseases caused by nematodes and helminths, and nematicidal and anthelmintic formulations based on the polyhaloalkene derivatives. Typical nematode species controlled in accordance with the invention are the root-knot, stunt, lesion, cyst and C. elegans nematodes.
In subclasses A and B of the compounds of formula I above, available carbon atoms of the heterocyclic rings other than thiazolyl optionally may be substituted with any group orgroups which are non-destruc- DBM:SC(2:17)(ER)
ALIL'~
r WO 86/07590 PCT/US86/01284 -3tive of the nematicidal or anthelmintic activity of the compounds. Typical substituents include aliphatic, aromatic and heterocyclic groups, halo, nitro, cyano, alkoxy, alkylthio, haloalkyl, haloalkoxy, halo-, nitro-, cyano- or alkoxy-substituted phenyl, polyhaloalkenylthio, phenylalkylthio, phenylthioalkylthio, propargylthio, cycloalkylmethylthio, and the like, further including straight and branched chain structures, and the various isomers of such substituents.
Throughout this specification the alkyl, alkenyl and alkynyl gro.ups may contain 1-11 or more carbon atoms and may be straight.chain or branched. Cycloalkyl groups may contain 3-8 or more carbon atoms.
Preferably, alkyl, alkenyl, alkynyl and alkoxy are lower alkyl, lower alkenyl, lower alkynyl or lower alkoxy, meaning that these groups contain 1-8 carbon atoms, more preferably 1-4 carbon atoms such as methyl, propenyl and methoxy. Halo or halogen means fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine. Aromatic substituents include'phenyl, naphthyl, anthracene, diphenyl, and the like.
Representative compounds of formula I are listed in Tables 1, la, lb and Ic appended.
The preferred compounds of formula I are those of subclass A wherein R is defined as follows: R is a thiadiazolyl group of the structure: RS 3 4 S 1,2,4-thiadiazol-5-yl 2 N or 1,2,4-thiadiazol-3-yl wherein R 2 is 3,4,4-trifluoro-3-butenyl, or a phenylmethyl or phenylthiomethyl group each.
:i i u WO 86/07590 PCT/US86/0 1284 -4optionally substituted with halogen or nitro.
2 The R S- group may be in the 3- or I of the 1,2,4-thiadiazole ring; R is a thiadiazolyl group as in above but 2 with iodo in place of R S, R is a thiadiazolyl group of the structure: 1,3, 3 S R1 3 wherein R is aryl, arylalkyl, aryloxyalkyl, alkylthio, haloalkylthia, cyanoalIqrlthio, arylalkylthio, aryloxyalkylthio, arylthioalkylthio, heterocycloalkyithia, alkenylthio, haloalkenylthio, halocycloalkylalkenvlthio, or an amino Iigroup mono- or disubstituted with members ifselected independently from alkyl, alkylcarbonyl, haloalkylcarbonyl, aryl, arylaminocarbonyl, arylalkylcarbonyl, arylalkoxycarbonyl and 3-(2,2-dichloroethenyl)-2, 2-dimethylcyclooropanecarbonyl; R is an oxadiazolyl group of the structure: 4 i5,2,4-oxadiazol-5-yl 0 or l,2,4-oxadiazol-3-yl 4 wherein R is aryl or arylalkyl substituted with chioro, fluoro, alkyl, haloalkyl, alkoxy, or nitro. The R4group may be in the 3- or poiion of the 1,2,4-oxadiazole ring; or R i's an oxadiazolyl group of the structure: 51 01,3, S WO 86/07590 PCT/US86/01284 5 wherein R is alkyl, haloalkyl, aryl, arylalkyl, aryloxyalkyl, arylthioalkyl, heterocycloalkyl, arylalkenyl or alkynyl (C 2 -C 1 Aryl and the heterocycles described in and above are optionally substituted with one or more groups selected independently from halogen, alkyl, haloalkyl, alkoxy, haloalkoxy, cyano, nitro and phenyl. Aryl and the heterocycles described in above are optionally substituted with one or more groups selected independently from halogen, alkyl, alkoxy, nitro, amino, hydroxy, acetyloxy and alkylaminocarbonyloxy.
R is a thiazolyl group.
Synthesis The compounds of formula I are prepared in a known manner. For example, a polyhaloalkene such as 4-bromo-l,1,2-trifluoro-l-butene is reacted with a mercaptothiazole (prepared by reaction of thiazole and elemental sulfur) or mercaptothiazoline in a reaction solvent medium containing sodium ethoxide to form the thiazolyl or thiothiazoline derivative of the polyhaloalkene. Examples 1, 2, 8-14, 16 and 17 below are representative of this and other reaction schemes for synthesis of the subclass A compounds of formula I (X sulfur). Compounds of formula I wherein X is oxygen (subclass B) may be prepared as described in Examples 3 and 4. Similarly, the subclass C (X nitrogen) and subclass D compounds (X -CH are 1 2 prepared as described in Examples 5 and 6 (subclass C) and 7 (subclass D).
Other polyhaloalkenes may be used in known ways to prepare other compounds of formula I. For example, trifluoroethylene can be chain-extended with methyl dibromide and the 1-,3-dibromo-l,l,2-trifluoropropane product then reacted with a mercaptan to form a thio WO 8607590PCT/US86/0 1284 -6intermediate. The intermediate is then dehydrohalogenated, as follows, wherein "BP" is benzoyl peroxide and "DBU" is l,8-diazabicyclo[5.4.O]undec-7-ene catalyst, as described by Tarrant and Tandon, J. Org.
Chem. 34(4), 864 (1969): 2r 2 F C CHF BrCH CHiFCF Br
BP
N
-N N C5 CF s -\CH CIFCF Br Ii Dihalopropene derivatives within the scope of formula I maybe prepared by the following general reaction, wherein Y 1and Y 2are as defined above and one of Y 1and Y 2also may be hydrogen:
Y
CH Br 2C BrCH CH C 2H~ 2C BP 2 2I S l CHCH C
M
SWO 86/07590 PCT/US86/01284 -7- Trihalopropene derivatives also may be prepared in a manner and reaction similar to the Tarrant and Tandon scheme to form other compounds of formula I, 1 2 wherein Y Y and Z are as defined in formula I: 11 y 1 Z Z Y
CH
2 Br C CH BrCHCH 2 2 2 Y Br Y S 2 Methods of preparing propenes, butenes and other alkenes having mixed halogen substituents and therefore useful in the invention for preparing compounds of formula I are described in a Ph.D. thesis of M. R.
Lillyguist, University of Florida (1955), pages 9, 39, 59 and 60. It will be apparent, therefore, that the I polyhaloalkenes and heterocyclic or other compounds used to prepare the compounds of formula I generally are known materials or can be synthesized by known procedures.
The following examples further describe methods of preparing the compounds of the invention. In the examples all parts and percentages are by weight and all temperatures are "C unless otherwise stated. The WO 86/07590 PCT/US86/01284 -8products of Examples 1-9 correspond to compounds 1-9 listed in Tables 1 and lb. Examples 10-17 identify the tabulated compounds to which they relate.
Example 1 2-(3,4,4-Trifluoro-3-butenylthio)- Sodium ethoxide was prepared by stirring 0.25 gram (0.011 mole) of sodium metal in 30 ml of absolute Sethanol. To this was added 1.2 grams (0.01 mole) of 2-mercaptothiazoline. The reaction mixture was stirred for one hour and the excess ethanol was removed under reduced pressure. The residue was dissolved in 35 ml of methyl ethyl ketone and 2.0 grams (0.01 mole) of 4-bromo-l,1,2-trifluoro-l-butene was added. The reaction mixture was stirred at ambient temperature for four hours, then concentrated under reduced pressure to a residue. The residue was dissolved in 50 ml of toluene and washed with three ml portions of water. The organic layer was dried with sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to give 1.7 grams of 2-(3,4,4-trifluoro-3-butenylthio)-4,5-dihydrothiazole as an oil. The nmr and the ir spectra were consistent with the proposed structure.
Example 2 5-Methylthio-2-(3,4,4-trifluoro- 3-butenylthio)-1,3,4-thiadiazole A solution of 2.0 grams (0.012 mole) of 2-mercapto-5-methylthio-l,3,4-thiadiazole in 25 ml of distilled acetone was added to a stirred mixture of 0.84 gram (0.006 mole) of potassium carbonate and 0.2 gram (0.001 mole) of potassium iodide in 25 ml of distilled acetone. With continued stirring 2.2 grams (0.012 mole) of 4-bromo-l,1,2-trifluoro-l-butene was added dropwise. Upon completion of addition the reaction mixture was heated under reflux for four hours.
WO 86/07590 PCT/US86/01284 9 The reaction mixture was cooled, filtered, and the filtrate concentrated under reduced pressure to a residue. The residue was dissolved in diethyl ether and washed with aqueous 5% sodium hydroxide. The organic layer was dried with magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure to give 1.3 grams of 5-methylthio-2-(3,4, 4 trifluoro-3-butenylthio)-1,3, 4 -thiadiazole as an oil.
The nmr and the ir spectra were consistent with the proposed structure.
Example 3 (3,4,4-Trifluoro-3-butenyl) heptafluorobutyrate A stirred solution of 2.6 ml (0.02 mole) of heptafluorobutyric acid in 50 ml of water was warmed to 50°C and 5.1 grams (0.022 mole) of silver oxide was added. Upon completion of addition the reaction mixture temperature was maintained at 50-60C for two hours. The reaction mixture was allowed to cool to -ambient temperature, then it was-filtered. The filtrate was concentrated under reduced pressure to give 6.4 grams of the silver salt of heptafluorobutyric acid as a solid.
To a stirred mixture of 3.2 grams (0.01 mole) of the silver salt of heptafluorobutyric acid in 40 ml of diethyl ether was added dropwise 1.9 grams (0.01 mole) of 4-bromo-l,1,2-trifluoro-l-butene in ml of diethyl ether. Upon completion of addition the reaction mixture was stirred for two hours at ambient temperature, then was heated under reflux for one hour. The ether solvent was removed by distillation and the residual oil distilled under reduced pressure to give 1.0 gram of (3,4,4-trifluoro-3-butenyl) heptafluorobutyrate; b.p. 250C/4.O mm Hg. The nmr spectrum was consistent with the proposed structure.
r L7 -I WO 86/07 5 90 PCT/US86/01284 Example 4 (3,4,4-Trifluoro-3-butenyl) 4-chlorobenzoate To a stirred solution of 1.6 grams (0.01 mole) of 4-chlorobenzoic acid in 35 ml of acetonitrile was added 1.5 ml (0.01 mole) of 1,8-diazabicyclo[5.4.0]undec-7-ene, followed by 1.9 grams (0.01 mole) of 4-bromo-l,1,2-trifluoro-l-butene. The reaction mixture was heated under reflux for four hours then allowed to cool to ambient temperature. Water, 25 ml, was added to the reaction mixture, and the reaction mixture was extracted with three 20 ml portions of diethyl ether. The combined extracts were washed in succession with one 25 ml portion of water, two 25 ml portions of aqueous 5% sodium hydroxide and, finally, one 25 ml portion of water. The organic layer was dried with sodium sulfate and filtered. The filtrate was concentrated under, reduced pressure to give 1.2 grams of (3,4,4-trifluoro-3-butenyl) 4-chlorobenzoate as an oil. The nmr and the ir spectra were consistent with the proposed structure.
Example N-(3,4,4-trifluoro-3-butenyl)succinimide This compound was prepared in a manner analogous to that of Example 1 using 1.1 grams (0.01 mole) of succinimide, 1.9 grams (0.01 mole) of 4-bromo-l,1,2trifluoro-l-butene, 0.25 gram (0.01 mole) of sodium metal, 30 ml of absolute ethanol and 20 ml of di- .7 methylformamide. The yield of N-(3,4,4-trifluoro-3butenyl)succinimide was 0.3 gram as an oil. The nmr and the ir spectra were consistent with the proposed structure.
Example 6 (3,4,4-Trifluoro-3-butenyl)isothiocyanate To a stirred solution of 10.0 grams (0.053 mole) of 4-bromo-1,1,2-trifluoro-l-butene in 50 ml of WO 86/07590 PCT/US6/01284 11 dimethylformamide was added 10.4 grams (0.056) of the commercially available potassium salt of phthalimide.
The reaction mixture was warmed to 50*C where it stirred for four hours. The reaction mixture was allowed to cool and 50 ml of chloroform was added.
The mixture was poured into 200 ml of water. The aqueous layer was separated and extracted with two ml portions of chloroform. The combined organic layers were washed with two 50 ml portions of aqueous 5% sodium hydroxide and one 50 ml portion of water.
The organic layer was dried with sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to give 4.8 grams of N-(3,4,4-trifluoro-3butenyl)phthalimide as an oil. The nmr spectrum was consistent with the proposed structure.
A stirred solution of 4.2 grams (0.016 mole) of N-(3,4,4-trifluoro-3-butenyl)phthalimide and 1.0 ml (0.032 mole) of anhydrous hydrazine in 50 ml of methanol was heated under reflux for one hour. The reaction mixture was allowed to cool and the solvent removed under reduced pressure. The residue was taken up in 25 ml of water and 30 ml of concentrated hydrochloric acid. The reaction mixture was heated under reflux for two hours and then cooled to 0°C. A solid was removed from the reaction mixture by filtration.
The filtrate was concentrated under reduced pressure to a residue. The residue was taken up in 50 ml of water and made basic with aqueous 10% sodium hydroxide. The mixture was extracted with two 25 ml portions f diethyl ether. The combined extracts were dried with sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to give 0.4 gram of 4-amino-1,1,2-trifluoro-l-butene as an oil.
The ir spectrum was consistent with the proposed structure.
WO 86/07590 PCT/US86/01284 -12- A stirred solution of 0.4 gram (0.004 mole) of 4-amino-1,1,2-trifluoro-l-butene in 25 ml of diethyl ether was saturated with gaseous hydrochloric acid. The reaction mixture was concentrated under reduced pressure to give 0,4 gram of 4-amino-l,1, 2 trifluoro-l-butene hydrochloride as a solid. The nmr spectrum was consistent with the proposed structure.
To a stirred solution of 0.4 gram (0.0027 Smole) of 4-amino-l,1,2-trifluoro-l-butene hydrochloride in 15 ml of chloroform was added 0.3 gram (0.003 mole) of thiophosgene, followed by 0.7 ml (0.009 mole) of triethylamine. Upon completion of addition the reaction mixture was stirred at ambient temperature for three hours. The reaction mixture was then washed in succession with one 25 ml portion of water, two ml portions of aqueous 5% sodium hydroxide, and, finally, one 25 ml'portion of water. The organic layer was dried with sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to give 0.3 gram of (3,4,4-trifluoro-3-butenyl) isothiocyanate as an oil. The ir spectrum was consistent with the proposed structure.
Example 7 4,5,5-Trifluoro-4-penten-l-ol To a stirred mixture of 2.4 grams (0.1 mole) of magnesium turnings in 100 ml of diethyl ether was added 18.9 grams (0.1 mole) of 4-bromo-l,1,2-trifluoro-l-butene. Upon completion of addition the reaction mixture was heated under reflux until the reaction was complete. The reaction mixture was cooled to 0OC and 9.0 grams (0.2 mole) of carbon dioxide was bubbled in slowly. Upon completion of addition the reaction mixture was stirred for one hour, then 100 ml of aqueous 20% hydrochloric acid was added to destroy the excess magnesium. The reaction WO 86/07590 PCT/US86/01284 13 mixture was extracted with three 40 ml portions of diethyl ether. The combined extracts were cooled and ml of aqueous 25% sodium hydroxide was added slowly. The organic layer was separated and extracted with one 40 ml portion of aqueous 25% sodium hydroxide. The combined base layers were cautiously acidified with aqueous 20% hydrochloric acid. The mixture was extracted with two 100 ml portions of diethyl ether. The combined extracts were dried with sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to give 6.9 grams of 4,5,5-trifluoro-4-pentenoic acid as an oil. The nmr and ir spectra were consistent with the proposed structure.
To a stirred suspension of 0.4 gram (0.01 mole) or lithium aluminum hydride in 20 ml of diethyl ether was added dropwise a solution of 1.5 grams (0.01 mole) of 4,5,5-trifluoro-4-pentenoic acid in 30 ml of diethyl ether. Upon completion of addition the reaction mixture was stirred at ambient temperature for one hour, then 20 ml of water was added carefully.
The mixture was filtered and the filtrate concentrated under reduced pressure to give 0.8 gram of 4,5,5-trifluoro-4-penten-l-ol as an oil. The nmr and the ir spectra were consistent with the proposed structure.
Example 8 3-Chloro-5-(3,4,4-trifluoro-3butenylthio)-1,2,4-thiadiazole A stirred solution of 5.0 grams (0.026 mole) of dipotassium cyanoimidodithiocarbonate [prepared by the method.of L.S. Wittenbrook et al, J. Org. Chem., 38, 3, 465 (1973)] in 19 ml of acetone and 22 ml of water was cooled to 0°C and 4.9 grams (0.026 mole) of 4-bromo-l,1,2-trifluoro-l-butene in 10 ml of acetone was added dropwise. Upon completion of addition the
I:
WO 86/07590 WO 86/07590 PCT/US86/01284 14 reaction mixture was allowed to warm to ambient temperature where it stirred for 16 hours. The reaction mixture was concentrated under reduced pressure to a residual solid. The solid was dissolved in ethyl acetate and filtered. The filtrate was concentrated under reduced pressure, and the residual solid dried in a vacuum oven. The dried solid was dissolved in hot chloroform ethyl acetate and filtered. The filtrate was concentrated under reduced pressure, and the residual solid dried in a vacuum oven to give 4.4 grams of potassium (3,4,4-trifluoro-3-butenyl) cyanoimidodithiocarbonate. The nmr spectrum was consistent with the proposed structure.
A stirred solution of 2.0 grams (0.008 mole) of potassium (3,4,4-trifluoro-3-butenyl) cyanoimidodithiocarbonate in 10 ml of chloroform was cooled to 0°C and 1.2 grams (0.009 mole) of sulfuryl chloride was added dropwise. Upon completion of addition the reaction mixture was maintained at 0°C for one hour, warmed under reflux for 4 hours, then at ambient temperature for 16 hours. Stirring was continued throughout the 21 hour period. The reaction mixture was filtered and the filtrate concentrated under reduced pressure. The concentrate was passed through silica gel using diethyl ether as an eluent. The ether eluate was filtered and the filtrate concentrated under reduced pressure to a residual oil. The oil was dried in a vacuum oven to give 0.9 gram of 3-chloro-5-(3,4,4-trifluoro-3-butenylthio)-l,2,4-thiadiazole. The nmr and the ir spectra were consistent with the proposed structure.
Example 9 3-Bromo-5-(3,4,4-trifluoro-3-butenyl thio)-1,2,4-thiadiazole A stirred solution of 3.0 grams (0.011'mole) of i WO 86/07590 86/07590 PCT/US86/01284 15 potassium (3,4,4-trifluoro-3-butenyl) cyanoimidodithiocarbonate (prepared as in Example 8, Step A) in ml of water was cooled to 0°C and 2.2 grams (0.014 mole) o mnine was added dropwise under a positive gaseous n-,tigen pressure. Upon completion of addition the reaction mixture temperature was maintained at 0°C for one hour, then was allowed to warm to ambient temperature where it stirred for 16 hours.
Sodium thiosulfate was added to the reaction mixture, which was then partitioned between chloroform and additional water. The chloroform layer was separated and dried with magnesium sulfate. The mixture was filtered and concentrated under reduced pressure to a residual oil. The oil was passed through silica gel using 4:1 hexane:diethyl ether as an eluent. The eluate was concentrated under reduced pressure to give 1.1 grams of 3-bromo-5-(3,4,4-trifluoro-3-butenylthio)-1,2,4-thiadiazole as an oil. The nmr spectrum was consistent with the proposed structure.
Example 10 (Compound 3,5-Di(3,4,4-Trifluoro-3-butenylthio)- 1,2,4-thiadiazole A stirred solution of 16.0 grams (0.08 mole) of dipotassium cyanoimidodithiocarbonate (prepared as in Example 8, Step A) and 2.6 grams (0.08 mole) of sulfur in 425 ml of methanol was heated under reflux for 15 minutes. The reaction mixture was allowed to cool then was concentrated under reduced pressure to a residual solid. The solid was dried under reduced pressure to yield 18.1 grams of the dipotassium salt of 3,5-dimercapto-l,2,4-thiadiazole.
A solution of 1.0 gram (0.004 mole) of the dipotassium salt of 3,5-dimercapto-l,2,4-thiadiazole in 35 ml of methyl ethyl ketone was stirred and 1.7 grams (0.009 mole) of 4-bromo-l,1,2-trifluoro-l-butene WO 86/07590 PCT/US86/01284 16 wa.. added. The reaction mixture was heated under reflux for two hours then allowed to cool to ambient temperature where it stirred for 18 hours. The reaction mixture was concentrated under reduced pressure to a residue. The residue was stirred in ml of water and the mixture was extracted with two ml portions of toluene. The organic layer was dried with sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to yield 1.1 grams of 3,5-di-(3,4,4-trifluoro-3-butenylthio)-l,2,4-thiadiazole as a liquid. The nmr spectrum was consistent with the proposed structure.
Example 11 (Compound 26) 3-(4-Nitrophenylmethylthio)-5-(3,4,4trifluoro-3-butenylthio)-l,2,4-thiadiazole A stirred solution of 24.7 grams (0.109 mole) of the dipotassium salt of 1,2,4-thiadiazole (prepared as in Example 10, Step A) in 200 ml of water was acidified with concentrated hydrochloric acid. The resultant solid was collected by filtration to yield 17.3 grams of wet 1,2,4-dithiazol-3-thione; m.p. 217-220*C.
A solution of 2.2 grams (0.055 mole) of sodium hydroxide in 7 ml of water and 20 ml of ethanol was stirred and 4.0 grams (0.027 mole) of 1,2,4-dithiazol-3-thione was added portionwise. After all of the 5-amino intermediate was in solution, 4.7 grams (0.027 mole) of 4-nitrophenylmethyl chloride was added dropwise. Upon completion of addition the reaction mixture was stirred at ambient temperature for 16 hours. The reaction mixture was concentrated under reduced pressure to a residue. The residue was dissolved in 20 ml of water then extracted with two 25 ml portions of diethyl ether. The aqueous layer was.
acidified with concentrated hydrochloric acid to yield L S NO 86/07590 PCT/US86/01284 17 a gummy soli.d. The solid was extracted from the aqueous layer with two 25 ml portions of ethyl acetate. The combined extracts were dried with sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to yield a gummy solid. The solid was dissolved in methylene chloride and filtered to remove a small amount of insoluble material. The filtrate was concentrated under reduced pressure to yield 2.8 grams of 3-(4-nitrophenylmethylthio)-5-mercapto-1,2,4-thiadiazole as a solid. The nmr spectrum was consistent with the proposed structure.
A solution of 0.25 gram (0.011 mole) of sodium in 35 ml of ethanol was stirred and 2.7 grams (0.0095 mole) of 3-(4-nitrophenylmethylthio)-5-mercapto-1,2,4-thiadiazole was added. Upon completion of addition the reaction mixture was stirred at ambient temperature for one hour. The ethanol solvent was removed under reduced pressure. The residue was dissolved in 35 ml of methyl ethyl ketone and 1.6 grams (0.0085 mole) of 4-bromo-l,1,2-trifluoro-l-butene was added. Upon completion of addition the reaction mixture was stirred for 16 hours, then was concentrated under reduced pressure to a residue. The residue was dissolved in 50 ml of toluene and washed with 25 ml of water, two 25 ml portions o'f aqueous sodium hydroxide solution, and 25 ml of water. The organic layer was dried with sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to yield a residual oil. The oil was dissolved in methylene chloride and passed through a column of silica gel. The eluate was concentrated under reduced pressure to yield 2.1 grams of 3-(4nitrophenylmethylthio)-5-(3,4,4-trifluoro-3-butenylthio)-1,2,4-thiadiazole. The nmr spectrum was consistent with the proposed structure.
WO 86/07590 PCT/US86/01284 18 Example 12 (Compound 2-(l-Methylethylthio)-5-(3,4,4-trifluoro-3butenylthio)-1,3,4-thiadiazol.e A solution of 22.5 grams (0.15 mole) of mercapto-l,3,4-thiadiazole in 200 ml of tetrahydrofuran was stirred and 21 ml (0:15 mole) of triethylamine was added dropwise. Upon completion of addition the reaction mixture was stirred at ambient temperature for 15 minutes, then 28.4 grams (0.15 mole) of 4-bromo-l,1,2-trifluoro-l-butene was added dropwise.
Upon completion of addition the reaction mixture was heated under reflux for two hours. The cooled reaction mixture was concentrated under reduced pressure to a residue. The residue was stirred in 250 ml of diethyl ether and extracted with two 100 ml portions of aqueous 10% potassium hydroxide. The combined extracts were acidified with aqueous 10% hydrochloric acid, then were extracted with two 100 ml portions of diethyl ether. The combined ether extracts were dried with sodium sulfate and filtered. The filtrate was concentrated under reduced pressure to yield, after drying, 35.6 grams of 2-mercapto-5-(3,4,4-trifluoro-3-butenylthio)-l,3,4-thiadiazole as a solid.
The nmr spectrum was consistent with the proposed structure.
In a manner analogous to Example 11, Step C, 1.3 grams (0.005 mole) of 2-mercapto-5-(3,4,4-trifluoro-3-butenylthio)-1,3,4-thiadiazole, 0.5 ml (0.005 mole) of 2-iodopropane, 0.15 gram (0.007 mole) of sodium were reacted in 35 ml of ethanol and 35 ml of methyl ethyl ketone by heating the mixture under reflux for five hours prior to stirring at ambient temperature for 16 hours. The yield of 2-(l-methylethylthio)-5-(3,4,4-trifluoro-3-butenylthio)-1,3,4thiadiazole was 1.3 grams as a liquid. The nmr spectrum was consistent with the proposed structure.
WO 86/07590 PCT/US86/01284 19 Example 13 (Compound 37) 2-(4-Chlorophenyl)-5-(3,4,4-trifluoro- 3-butenylthio)-1,3,4-thiadiazole A stirred solution of 8.1 grams (0.048 mole) of 4-chlorobenzoic acid hydrazide in 300 ml of triethyl orthoformate was heated under reflux for 16 hours. The excess triethyl orthoformate was removed by distillation and the residual solid was stirred with petroleum ether to yield 7.7 grams of 2-(4chlorophenyl)-1,3,4-oxadiazole; m.p. 129°C. The nmr spectrum was consistent with the proposed structure.
Under a nitrogen atmosphere, a solution of 17 grams (0.084 mole) of phosphorus pentasulfide in 100 ml of dry xylene was stirred and 7.6 grams (0.042 mole) of 2-(4-chlorophenyl)-l,3,4-oxadiazole was added. Upon completion of addition the reaction mixture was heated under reflux for 30 hours. The reaction mixture was cooled and 100 ml of water was added dropwise.. The mixture was filtered through diatomaceous earth to separate the organic and aqueous phases. The organic phase (the filtrate) was extracted with an aqueous 10% potassium hydroxide solution. The extract was acidified with an aqueous hydrochloric acid solution, and then was extracted with diethyl ether. The ether extract was concentrated under reduced pressure to yield 0.3 gram of 2-(4-chlorophenyl)-5-mercapto-1,3,4-thiadiazole; m.p.
178 0
C.
In a manner analogous to Example 2, 0.3 gram (0.0015 mole) of 2-(4-chlorophenyl)-5-mercapto-l,3,4thiadiazole, 0.4 gram (0.002 mole) of 4-bromo-l,1,2trifluoro-l-butene, 0.2 gram (0.0015 mole) of potassium carbonate, and 0.05 gram of potassium iodide were reacted in 9 ml of methyl ethyl ketone. The yield of 2-(4-chlorophenyl)-5-(3,4,4-trifluoro-3-butenylthio)i- B I^rl__ l.i ir-i.i-;i II~ ;i:ii ii:- (Ye;L~~ WO 86/07590 PCT/US86/01284 1,3,4-thiadiazole was 0.1 gram; m.p. 68-69 0 C. The nmr spectrum was consistent with the proposed structure.
Example 14 (Compound 39) 3-(4-Chlorophenyl)-5-(3,4,4-trifluoro- 3 butenylthio)-1,2,4-oxadiazole A stirred solution of 4.1 grams (0.03 mole) of 4-chlorobenzonitrile, 2.1 grams (0.03 mole) of hydroxylamine hydrochloride, and 2.1 grams (0.015 mole) of potassium carbonate in 10 ml of water and 100 ml of ethanol was heated under reflux for 16 hours.
The reaction mixture was cooled and 50 ml of water was added. The ethanol solvent was removed under reduced pressure. The concentrate was cooled in an ice bath and the resultant solid collected by filtration. The solid was dried to yield 4.4 grams of N-hydroxyimido-4-chlorobenzamide; m.p. 122-130 0
C.
A solution of 4.4 grams (0.028 mole) of N-hydroxyimido-4-chlorobenzamide in 50 ml of diethyl ether was stirred and 0.55 ml (0.007 mole) of thiophosgene was added dropwise. Upon completion of addition the reaction mixture was stirred at ambient temperature for 15 minutes then was heated under reflux for one hour. The reaction mixture was cooled and filtered to collect bis 0,0'-thiocarbonyl(4chloro-N-hydroxybenzenecarboximidamide). A 100% yield was assumed.
A solution of 10.0 grams (0.25 mole) of sodium hydroxide in 90 ml of water was stirred and 5.4 grams (0.14 mole) of bis 0,0'-thiocarbonyl(4-chloro- N-hydroxybenzenecarboximidamide) was added. Upon completion of addition the reaction mixture was heated under reflux for one hour. The reaction mixture was cooled and extracted with two 50 ml portions of diethyl ether. The aqueous layer was acidified with concentrated hydrochloric acid. The resultant preci- L77I WO 86/07590 PCT/US86/01284 21 pitate was collected by filtration, washed with water, and dried to yield 1.0 gram of 3-(4-chlorophenyl)-5mercapto-1,2,4-oxadiazole; m.p. 139-156*C, dec. The nmr spectrum was consistent with the proposed structure.
In a manner analogous to Example 2, 0.7 gram (0.003 mole) of 3-(4-chlorophenyl)-5-mercapto-l,2,4oxadiazole, 0.6 gram (0.003 mole) of 4-bromo-1,1,2trifluoro-l-butene, 0.2 gram (0.0015 mole) of potassium carbonate, and 0.1 gram of potassium iodide were reacted in 40 ml of distilled acetone. The yield of 3-(4-chlorophenyl)-5-(3,4,4-trifluoro-3-butenylthio)-1,2,4-oxadiazole was 0.3 gram; m.p. 49-52*C.
The nmr spectrum was consistent with the proposed structure.
Example 15 (Compound 43) 5-(3-4,4-Trifluoro-3-butenylthio)-1,3,4-oxadiazole A solution ot 25 grams (0.147 mole) of 4-chlorophenylacetic acid in 250 ml of acetonitrile was stirred and 15.0 grams (0.0147 mole) of bromoethane, followed by 22.0 grams (0.147 mole) of 1,8-diazabicyclo[5.4.0]undec-7-ene, were added. Upon completion of addition the reaction mixture was cooled in a water bath while being stirred for 18 hours. The reaction mixture was concentrated under reduced pressure to one-half volume and then was added to 50 ml of water. The mixture was extracted with two portions of diethyl ether. The combined extracts were dried with magnesium sulfate and filtered. The filtrate was concentrated under reduced pressure to yield 18.2 grams of ethyl (4-chlorophenyl)acetate.
A stirred solution of 18.2 grams (0.091 mole) of ethyl (4-chlorophenyl)acetate and 10 ml of hydrazine hydrate in 10 ml of ethanol was heated under reflux for one hour during which time a solid preci- -i 1
U
ii t VO 86/07 '590 PCT/US86/01284 -22ii pitated. The solid was collected by filtration to yield, when dried, 14.9 grams of 4-chlorophenylacetic acid hydrazide; m.p. 159-161°C. The nmr spectrum was consistent with the proposed structure.
A stirred solution of 7.0 grams (0.038 mole) of 4-chlorophenylacetic acid hydrazide, 3.0 grams (0.039 mole) of carbon disulfide and 2.8 grams (0.050 mole) of potassium hydroxide in 10 ml of water and 200 ml of ethanol was heated under reflux for four hours.
The ethanol was removed under reduced pressure. The concentrate was taken up in water and the mixture washed with diethyl ether. The aqueous layer was acidified with aqueous 5% hydrochloric acid and then was extracted with diethyl ether. The extract was dried with magnesium sulfate and filtered. 'The filtrate was concentrated under reduced pressure to yield 3:9 grams of 2-(4-chlorophenylmethyl)-5-mercapto-1,3,4-oxadiazole; m.p. 115 0 C. The nmr spectrum was consistent with the proposed structure.
In a manner analogous to Example 2, 2.4 grams (0.011 mole) of 2-(4-chlorophenylmethyl)- 5-mercapto-l,3,4-oxadiazole, 2.0 grams (0.011 mole) of 4-bromo-l,1,2-trifluoro-l-butene, 1.5 grams (0.011 mole) of potassium carbonate and 0.5 gram of potassium iodide were reacted in 45 ml of acetone. The yield of 2-(4-chlorophenylmethyl)-5-(3,4,4-trifluoro-3-butenylthio)-1,3,4-oxadiazole was 1.5 grams as a liquid. The nmr spectrum was consistent with the proposed structure.
Example 16 (Compound 230) Synthesis of 2-(3,4,4-trifluoro-3butenylthio)thiazole Under a nitrogen atmosphere, a stirred solution of 2.0 grams (0.024 mole) of thiazole in 30 ml of dry tetrahydrofuran is cooled to -65C and 16 ml of 1.55 1: O 86/07590 PCT/US86/01 284 -23molar n-butyllithium is added dropwise. Upon completion of addition the reaction mixture is stirred for minutes and 0.8 gram (0.024 mole) of elemental sulfur is added portionwise. The reaction mixture is stirred for an additional one hour, the temperature then being adjusted to -60°C, and 4.5 grams (0.024 mole) of 4-bromo-l,1,2-trifluoro-l-butene is added dropwise. Upon completion of addition the reaction mixture is stirred for three hours during which time it is allowed to warm to ambient temperature. The solvent is removed under reduced pressure. The residue is dissolved in diethyl ether and washed with two portions of an aqueous solution saturated with sodium chloride. The organic layer is dried with magnesium sulfate and filtered. The filtrate is concentrated under reduced pressure to a residual semi-solid. The semi-solid is subjected to column chromatography on silica gel. Elution is accomplished with 1:1'hexane:diethyl ether. The appropriate fractions are combined and concentrated under reduced pressure to give 0.4 gram of 2-(3,4,4-trifluoro-3-butenylthio) thiazole as an oil. The nmr and ir spectra are consistent with the proposed structure.
Example 17 (Compound 231) Synthesis of 2-(2,3,3-trifluoro-2propenylthio)thiazole A stainless steel autoclave is charged with grams (0.6 mole) of trifluoroethylene, 300 grams (1.7 moles) of dibromomethane, and 5 grams (0.02 mole) of benzoyl peroxide. The reaction mixture is stirred and heated at 100"C for six hours, then is cooled to The autoclave is opened and the reaction mixture fractionally distilled. The appropriate fractions are combined to give 1,3-dibromo-l,l,2-trifluoropropane.
WO 86/07590 PCT/US86/01284 -24- Under a nitrogen atmosphere a stirred solution of 20 grams (0.24 mole) of thiazole in 300 ml of dry tetrahydrofuran is cooled to -65*C and 160 ml of n-butyllithium (1.55 molar) is added dropwise. Upon completion of addition the reaction mixture is stirred for 45 minutes and 8.0 grams (0.24 mole) of elemental sulfur is added portionwise. Upon completion of addition the reaction mixture is stirred for one hour and, 1at -60'C. 61.4 grams (0.24 mole) of 1,3-dibromoi 10 1,1,2-trifluoropropane is added dropwise. Upon completion of addition the reaction mixture is allowed to warm to ambient temperature where it stirs for three hours. The reaction mixture is concentrated under reduced pressure to a residue. The residue is dissolved in diethyl ether and is washed with two portions of aqueous sodium chloride. The organic layer is dried with magnesium sulfate and filtered. The filtrate is concentrated under reduced pressure to a residue. The residue is purified by column chromatography to give 2-(3-bromo-2,3,3-trifluoropropylthio)thiazole.
A stirred solution of 2.9 grams (0.01 mole) of 2-(3-bromo-2,3,3-trifluoopropyithio)thiazole and grams (0.01 mole) of 1,8-diazabicyclo[5.4.0]undec-7-ene in 40 ml of toluene is heated under reflux for two hours. The solvent is removed by distillation and the residue is purified by column chromatography -4 to give 1.1 grams of 2-(2,3,3-trifluoro-2-propenylthio)thiazole.
The appended Tables 1, la, lb and Ic list compounds prepared as in the foregoing Examples. In Tables la and Ic the compounds are those of formula I wherein Y Y2 and Z are fluoro, based upon the use of 4-bromo-l,1,2-trifluoro-l-butene as the starting material in the synthesis.
WO 86/07590 WO 86/07590 PCT/US86/01284 Pesticidal Use The compounds of the invention can be used against a variety of pests that attack plants and animals. In agriculture, they are useful as nematicides, particularly against plant-parasitic nematodes and "free-living" nematodes, nematodes not dependent on any specific plant or other host. An example of the latter is the microbivorous nematode Caenorhabditis elegans. This nematode will feed on bacteria such as Escherichia coli and is used as a screen for both agricultural and veterinary nematicides or anthelmintics.
When used as anthelmintics, in veterinary treatments for treatment of infestations of Ascaris lumbricoides (roundworm in pigs) for example, the compounds may be administered orally, parenterally or topically either alone but more usually in a pharmaceutically acceptable carrier, to provide an appropriate dosage.
Such carriers include one or more of water, gelatine, sugars, starches, organic acids such as stearic or citric acid and salts thereof, talc, vegetable fats or oils, gums, glycols and other excipients, for administration as solids tablets or capsules) or liquids solutions, suspensions or emulsions).
The compositions may also contain preservatives, stabilizers, wetting or emulsifying agents, buffers, salts and other therapeutic agents. The compositions may be formulated by conventional methods to contain about 5 to 95% by weight of the anthelmintic compound, preferably about 25 to 75% by weight. Further guidance to anthelmintic activity, formulations and modes of treatment, utilizing the compounds of the invention, is available from publications on the subject, such as the article "Chemotherapeutics, Anthelmintic" in Kirk-Othmer, Encyclopedia of Chemical 'u I-- WO 86/07590 PCT/US86/01284 -26- Technology, Third ed., 5 451-468, and articles cited therein, and in the patent literature, such as U.S, Patent 3,576,892, col. 3, lines 29-56.
In using the compounds of the invention as agricultural nematicides, the compounds, like most agricultural chemicals, are generally not applied full strength, but are formulated with agriculturally acceptable carriers and various additives normally employed for facilitating the dispersion of active ingredients, optionally with other active ingredients, recognizing that the formulation and mode of application of a toxicant may affect the activity of the material. The present compounds may be applied, for example, as powders or liquids, the choice of application varying with the nematode species and environmental factors present at the particular locus of infestation. Thus, the compounds may be formulated as granules, dusts, wettable powders, emulsifiable concentrates, solutions, suspensions, dispersions, controlled release compositions, and the like.
A typical formulation may vary widely in concentration of the active ingredient depending on the particular agent used, additives, carriers or other active ingredients used, the nematode species to be controlled, and the desired mode of application. With due consideration to these factors, the active ingre- dient of a typical formulation may, for example, suitably be present at a concentration of from about up to about 99.5% by weight of the formulation.
Surface active agents, if employed in the formulation, may be present at various concentrations, suitably in the range of I to 30% by weight.
Dusts are admixtures of the active ingredient with finely divided solid carriers and/or diluents such as talc, natural clays, kieselguhr, pyrophyllite, WO 86/07590 PCT/US86/01284 -27chalk, diatomaceous earths, calcium phosphates, calcium and magnesium carbonates, sulfur, lime, flours, and other organic and inorganic solid carriers. These finely divided formulations generally have an average particle size of less than about microns (325 mesh, Standard U.S. Sieve Series). In most cases, the active ingredient will be present in dust formulations at a concentration in the range of I to 15%, and occasionally from 1% to about 30%, the balance of the composition typically comprising one or more agriculturally acceptable inerts as adjuvant, carrier, or diluent.
The nematicidal compounds of the invention may also be formulated as wettable powders. These formulations are in the form of finely divided particles which disperse readily in water or other liquid vehicles. The wettable powder is ultimately applied as a dry dust or a dispersion in water or other liquid.
Typical carriers for wettable powders include fuller's earth, kaolin clays, silicas, and other highly absorbent or adsorbent inorganic diluents. The concentration of active ingredient in wettable powders is dependent upon physical properties of the active ingredient and the absorbency of the carriers.
Liquids and low melting solids (mp less than 100°C) are suitably formulated in the concentration range of to 50% by weight; usually 10 to 30%; high melting i solids (mp greater than 100°C) being formulated in the range of 5 to 95% by weight, usually 50 to 85%. An agriculturally acceptable carrier or diluent, fre- quently including a small amount of a surfactant to facilitate wetting, dispersion and suspension, accounts for the balance of the formulation.
Microencapsulated or other controlled release WO 86/07590 PCT/US86/01284 -28formulations may also be used for application of compounds in accordance with this invention.
Emulsifiable concentrates (EC's) are homogeneous liquid compositions, usually containing the active ingredient dissolved in a liquid carrier. Commonly used liquid carriers include xylene, heavy aromatic naphthas, isophorone, and other nonvolatile or slightly volatile organic solvents. For application of the nematicide, these concentrates are dispersed in water, or other liquid vehicle, forming an emulsion, and are normally applied as a spray to the area to be treated. The concentration of the essential active ingredient in EC's may vary according to the manner in which the composition is to be applied, but, in general, is in the range of 0.5 to 95%, frequently to 80%, by weight of active ingredient, with the remaining 99.5% to 5% being surfactant and liquid, carrier.
Flowables are similar to EC's except that the ingredient is suspended in a liquid carrier, generally water. Flowables, like EC's, may include a small amount of a surfactant, and contain active ingredient in the range of 0.5 to 95%, frequently from 10 to by weight of the composition. For application, flowables may be.diluted in water or other liquid vehicle, and are normally applied as a spray to the area to be treated.
Typical wetting, dispersing or emulsifying agents used in these formulations include, but are not limited to, the alkyl and alkylaryl sulfonates and sulfates and their sodium or calcium salts; alkylaryl polyether alcohols; sulfated higher alcohols; polyethylene oxides; sulfonated animal and vegetable oils; sulfonated petroleum oils; fatty acid esters of polyhydric alcohols and the ethylene oxide addition WO 86/07590 PCT/US86/01284 -29products of such esters; addition products of longchain mercaptans and ethylene oxide; and addition products of alkylphenols such as nonylphenol and ethylene oxide. Many other types of useful surfaceactive agents are available in commerce. The surface-active agent, when used, normally comprises from 1 to 15% by weight of the nematicidal composition; Other useful formulations include simple solutions of the active ingredient in a relatively non-volatile solvent such as corn oil, kerosene, propylene glycol, or other organic solvents. This type of formulation is particularly useful for ultra-low volume application.
The concentration of active ingredient in use dilution is normally in the range of about 2% to about Many variations of spraying, dusting, and controlled or slow release compositions in- the art may be used by substituting or adding a compound of this invention to compositions known or apparent to the art.
The compositions may be formulated and applied with other suitable active ingredients, including other nematicides, insecticides, acaricides, fungicides, plant regulators, herbicides, fertilizers, etc.
In applying the foregoing chemicals, an effective nematode controlling amount of active ingredient must be applied, sometimes referred to herein as a "nemati- 'idal amount." While the application rate will vary widely depending on the choice of compound, the formulation and mode of application, the plant species being protected and the planting density, a suitable use rate may be in the range of 0.5 to 25 kg/hectare, preferably 1 to about 20 kg/hectare.
The compounds of this invention are usually applied by incorporating a formulation thereof into the soil in which plants or agricultural crops are or ii 1_1_ i rti~ur WO 86/07590 PCT/US86/01284 are to be planted, the locus of infestation.
This may be achieved by incorporating the compounds into the soil or by broadcasting the formulation over the planted area or the area to be planted or by limiting the application to a small area or band in the root zone where plants are or are to be planted.
It will be readily apparent where the latter method is employed that a nematicidal amount, that is, a nematicidal concentration in the soil, must be applied to the root zone. A suitable concentration for this purpose is in the range of 0.1 to about 50 parts by weight of compound of the invention per million parts of soil.
However, in a significant aspect of the invention, it has been found that certain of the polyhaloalkene derivatives of the invention have efficacy against nematodes by foliar application, the compounds are systemic nematicides. This aspect is exemplified hereinafter.
The following are specific examples of formulations which may be utilized in accordance with the present invention. In these formulations the percentages are wt/wt.
1. Typical dust formulation: Test Compound Base 96% Attaclay 2% highly purified sodium lignosulfonate (100%) 2% powdered sodium alkylnapthalene sulfonate LW WO 86/07590 PCT/US86/01284 -31- 2. Typical emulsifiable concentrates: Test Compound Emulsifier A Emulsifier B 0.4% Emulsifier C 0.8% Emulsifier D 1.3% Refined xylene solvent 88.5% Emulsifier A is the anionic calcium salt of dodecylbenzene sulfonate. Emulsifier B is a nonionic 6-molar ethylene oxide condensation product of nonylphenol. Emulsifier C is a nonionic 30-molar ethylene oxide condensation product of nonylphenol. Emulsifier D is a nonionic paste of 100% polyalkylene glycol ether.
Test compound 21.3% Emulsifier A 4.2% Emulsifier B Emulsifier C 0.9% Emulsifier D 1.4% Refined xylene solvent 71.7% Test compound Emulsifier E Emulsifier F Emulsifier G Dormant spray oil solvent (non-volatile) 85.0% Emulsifier E is an oil-soluble nonionic blend of polyoxyethylene ethers commercially available under the trademark and designation "T Mulz 808A". Emulsifier F is a formulated nonionic concentrate commercially available under the trademark and designation "FloMo 200-4". Emulsifier G is the anionic free acid of a complex organic phosphate ester commercially available under the trademark and designation "Gafac RE-410".
I a WO 86/07590 WO 86/07590 PCT/US86/01284 -32- 3. Typical granule formulations: Test compound (technical) Attapulgite carrier/diluent 95.0% The carrier/diluent is a 20/40 or 60/90 mesh hydrated aluminum magnesium silicate of low volatile matter having 2% free moisture.
Test compound (technical) Ground corn cobs, 14/40 mesh 95.0% Test compound (as emulsifiable concentrate 2(B) above) 23.5% Attapulgite carrier/diluent above] 76.5% 4. Typical solution formulation: Test compound 0.3% Acetone 55.9% Water 43.8% Biological Testing Compounds of this invention were tested as follows for nematicidal and anthelmintic activity as dust.
formulations (initial and residual activity) and as acetone/water formulations (systemic activity). The formulations are described above.
1. Initial Root-Knot Nematicidal Activity The activity against root-knot nematode (Meloidogyne incognita) was determined by incorporating the compound of the invention in nematode infested soil at rates in the range of 10 ppm to 0.078 ppm of compound. Several tomato or cucumber seedlings were planted in the nematode infested soil. Two weeks after planting the test pots were evaluated to ascertain the degree of galling (swelling) on the roots of the plants, indicating the control provided by the test chemical.
The results expressed as percent control (determined by knot index) are set forth as averages in r 1 i it i
I
WO 86/07590 PCT/US86/01284 -33- Table 2 (appended). Knot index is a numerical designation assigned at evaluation, having the following meanings: Knot Index Observations 0 No swellings complete control 1 75% less swellings than control plants 2 50% less swellings than control plants 3 25% less swellings than control plants 4 About same as control plants no control.
Percent control is related to knot index as follows: Knot Index Percent Control 0 100 1 2 3 4 0 When the Knot Index is between 0 and 1 it is further subdivided as follows to indicate w close the percent control is to 75% or 100%: Knot Index Percent Control 0.8 0.1-0.4 95-99 The results demonstrate that compounds of this invention are highly effective against root-knot nematodes at the application rates tested.
2. Residual Root-Knot Nematicidal Activity The ability of nematicidal compounds of the invention to control root-knot nematode infestations in soil over a period of time after treatment was evaluated. Dust formulations of test compound were incorporated into soil samples at test compound rates of 5 and 10 ppm. Subsequently, the treated soil L-LI-LLIL_-L-_ I__ i- ii i~ii_:r-;il.i~Ylii~MYcUC
I
WO 86/07590 PCT/US86/01284 -34samples were inoculated with nematode inoculum at weekly intervals, and Knot Index and Percent Control determined on seedlings planted in the soil samples.
Specifically, soil treated with test compound was placed in 7.6 cm diameter fiber pots and stored in a greenhouse. At'one, two and four weeks post-treatment, the appropriate number of pots was infested with root-knot nematode eggs and larvae. A cucumber or tomato seedling was planted in each pot and evaluated approximately two weeks after the soil infestation to obtain the test results reported in Tables 3 and 3a appended. The data shows that as compared with untreated, but nematode-inoculated control soil, planted with seedlings (which showed no nematode control), substantial residual activity was exhibited with most of the test compounds at the application rates tested.
3. Stunt Nematode Test The procedure was substantially the same as in the initial root-knot nematode tests described above except that rates of application of formulated compound were 2.5 and 5 ppm in soil containing a corn seedling, with subsequent inoculation of the soil with combined larvae and adult stunt nematodes. The samples were evaluated approximately four weeks after infestation. The results (Tables 4 and 4a appended) indicate good control at the test application rates as compared with untreated samples where no control was observed. "Percent control" means the difference between average population counts between untreated and treated samples, divided by average population count of untreated sample, multiplied by 100.
4. Lesion Nematode Test The procedure was substantially the same as in the stunt nematode test described above except that i WO 86/07590 PCT/US86/01284 pea seedlings were used. The results (Table appended) show good control with many of the compounds at the application rates tested as compared with untreated samples (no control). "Percent Control" is defined as follows: Topulation Count Population Count tin Check in Trtmt IWt of Roots Wt of Roots Iin Check Plant in Treated Plants 1 IX 100 Population Count in Check I Wt of Roots in Check Plant Cyst Nematode Test The procedure was substantially the same as described in the stunt nematode test except soybean seedlings were used. "Percent Control" (Table 6 appended) is as defined in the stunt nematode test results. The data indicate good control by most of the compounds at the application rates tested.
6. Soil Mobility The ability of nematicidal compounds of the invention to move through nematode-infested soil and to control the nematodes was evaluated by incorporating 5% dust formulations of test compound at 30 ppm rates into pots of root-knot nematode infested soil, and subsequently eluting the soil with 15 cm of water (equivalent to 15 cm of rainfall) into a series of two or more pots of untreated, but nematode-infested, soil. Specifically, the pots were 8 cm diameter plastic pots containing a 10 cm layer of sand over a coarse grade filter paper disc. Sufficient soil was placed over the sand to fill the pots, and a second filter paper disc was placed over the soil. Each test compound-treated pot was nested over a series of two or more pots containing untreated, but nematode- WO 86/07590 PCT/US86/01284 -36infested soil, also containing sand filter paper discs as described for the treated soil pots. Fifteen cm of water was slowly dripped into the top pots and the pots were allowed to drain for 16-18 hours to remove excess water. The top filter of each pot was then removed and the pots were planted with a cucumber or tomato seedling. The seedlings were evaluated approximately two weeks after planting to give the test results reported in Tables 7 and 7a appended.
The data indicate good soil mobility and nematicide control at the application rates tested as compared to untreated systems which showed no nematode control.
"Knot Index" and "Percent Control" are as defined in the initial root-knot nematode tests above.
8. Systemic Activity Compounds of the invention were tested for basipetal systemic activity against the root-knot nematode. In this test, tomato plants are grown in 10.2 cm diameter fiber pots containing steam-pasteurized soil mix (50% soil, 50% sand) until 4-6 true leaves appear. Three of the pots are then placed on a turntable in a spray hood and the plants sprayed with ml of water/acetone solution containing the test compound. The soil surface is covered during the spraying to prevent spraying of the soil. After treatment, the potted plants are placed in a lighted drying chamber. The plants are then grown in a growth chamber at 25 0 C for three days and inoculated with a standard nematode culture by incorporating the inoculum into the top cm of soil in the pots. The plants are returned to the growth chamber for about two weeks at which time the pots are allowed to dry until the plants begin to wilt. The rcots are shaken free of soil and the degree of galling (swelling) noted as compared to galling of untreated control i_ i liili WO 86/07590 WO 86/07590 PCT/US86/01284 -37plants. The results are expressed as Knot Index and Percent Control as defined in the initial root-knot nematode activity tests reported above in Table 2.
Table 8 appended reports the test results. The data indicate that many of the compounds exhibited good systemic nematicidal activity at the application rates tested as compared with untreated plants wherein no nematicidal activity was evident. Systemic nematicidal activity of any substantial degree is highly unusual and desirable and is not available from any commercial nematicides.
9. C. Elegans Nematode Screening Test and Evaluation This in-vitro test using the free-living nematode Caenorhabditis elegans, is a modification of the assay developed by Simpkin and Coles, J. Chem.
Tech. Tiotechnol, 31:66-69 (1981). In this test, nematicidal activity is evaluated by placing a suspension of C. elegans nematodes in a medium containing a food source coli) and a candidate nematicide at test rates of 5.0-0.156 ppm. One milliliter of a test medium consisting of 5 mg ampicillin, 10,000 units of mycostatin and 10 ml of a dense suspension of Escherichia coli per 100 ml of a buffer solution, was pipetted into each well of a 24-well microtiter plate. The candidate nematicide, suspended at the appropriate concentration in dimethylsulfoxide, was added to the wells in 2.5 1 volumes. Each rate of application was replicated two to three times. After thorough mixing of the contents of each well, 50 to 100 1 of a nematode suspension in a buffer was added so that each well received 10-15 nematodes. After the nematodes were added, the microtiter plates were incubated at 20*C for 5-6 days.
WO 86/07590 PCT/US86/01284 -38- The effect of the candidate nematicide on the survival and the reproduction of C. elegans was then evaluated by comparison of the level of population developed in the treated wells with that in untreated wells. Specific effects on population development, such as reduced egg hatch or molting disruption, were noted if they were evident. Tables 9 and 10 appended show high activity test results for many compounds of the invention at the application rates tested.
WO 86/07590 WO 8607590PCT/US86/0 1284 39 Table I
F
F
2
C=C-CH
2
CH
2
X-R
Cmpd. No.
I
x /jt 'SLCH 3
C(O)CF
2
CF
2
CF
3 4-chlorobenzoyl Empirical Formula
C
7
H
8
F
3
NS
2
C
7
H-
7
F
3 N2S3
CBH
4
F
1 0 0 2
CIIHSCIF
3 0 2
CBHBF
3 N0 2
C
5
H
4
F
3
NS
C
5
H
7
F
3 0 =c=s
OH
CH 2 cl..
N
C
6
H
4
CIF
3
N
2
S
2 1155W3Oll3Wjd-I ,t WO 86/07590 Cmpd. No.
9 PCT/US86/0 1284 40 Table 1 (Continued) x
S
S
S
-H
S
s sf Empirical Formula
C
6 H 4 BrF 3 N2 s2
CBH
7
F
3
S
2
C
13
H
11
F
3
S
2
C
1 4
H
2 lF 3
N
2
S
3 SC(CH 3 )2 CH 2 C(CH 3 )3~ s~
S
F
I CF S, S SCH CH C- 2 2 2 SSCH 2 C =-CH N -N SCH~j Cj 0 Hj 8
F
6
N
2 S3 C9H- 7
F
3
N
2
S
3
C
9
H
9
F
3
N
2
S
3 Cl 2 HqF 3
N
2 0S
C
1 2
H
8 ClF 3
N
2 0S
N-N
I 1
A
0 0 OQCl1 1155W3Oll3Wmd-2 WO 86/07590 WO 8607590PCT/US86/0 1284 41 Table 1 (Continued) Cmpd. No. X R Empirical Formula s -CH CO CH CH C~ CF 2 0 -C CE, 2 CF 3*(CH 3 CH 2 2 0
-C(O)S
NO 2 0
H
0 -C(O)CH 2S N]
N
0 0
C
1 0
H
10
F
6 0 2
S
CllH 1 4 FB0 3 CqH 6
F
3 N0 CqH 6
F
3 N0 CqH 7
F
3 N0 2
C
9 Hj 0
F
3 N0 2
S
2
C
11 HeF 3 N0 3
S
1l510O13Wmd-3
I
WO 86/07590 'NO 8607590PCT/US86/0 1284 42 Table la F F C C(CH 2) SR wherein: R 2S R is N~ Compound No.
26
-CH
2
CH
2
CF=CF
2 4-ni Lrophenylmethyl R is R 3
J
R
3 27 -SCH 2
CH
2
F
28 -SCH 2
CH
2
C=-N
29 -SC 3
H
7
-SCH(CH
3 )2 31 -SCH 2
CH=CH
2 32
-SCH
2 0 33 -SCH 2 4-bromo 1155W3Oll3Wjd-4 Empirical Formula M.P. 0
C)
Cl 0
HBF
6
N
2 S3 liquid
C
1 3
H
1 0
F
3
N
3 0 2
S
3 liquid
C
8
H
8
F
4
N
2
S
3 liquid
C
9
H
8
F
3
N
3
S
3 liquid
C
9 HllF 3
N
2 S3 liquid C9H 1 1
F
3
N
2
S
3 li qu id
C
9
H
9
F
3
N
2
S
3 liquid
C
1 3 HIjF3N 2
S
3 liquid
C
1 3
H
1 0 BrF 3
N
2
S
3 s (49-51) WO 86/07590 PCT/US86/0 1284 Table la Compound Nio.
34 36 37
-SCH
2 2-fluoro
-SCH
2 0, 4-nitro 2-thienylmethylthio -44-chloro 43 (Continued) Empirical Formula M.P. (OC) Cl 3 Hl 0
F
4
N
2
S
3 liquid C1 3 HIOF3N 3 02S 3 liquid
C
11
H
9
F
3
N
2
S
4 liquid
C
1 2
H
8 ClF 3
N
2
S
2 s (68-69) ""F7- R is -C2 4-fluoro 4-chloro -,4-nitro
C
1 3
H
10
F
4
N
2 0S .liquid
C
1 2 HBC1F 3
N
2 0S s (49-52)
C
1 2
HBF
3
N
3 0 3
S
S (61-64) R ,I0L R is 41 -C 3
H
7 42 C2 43 -CH 2 4-chloro 1155W3Oll3Wjd-5
C
9
H
1 1
F
3
N
2 0S liquid
C
1 3
H
1
F
3
N
2 0S liquid Cl 3 Hl 0 ClF 3
N
2 0S li quid 11 WO 86/07590 WO 8607590PCT/US86/01284 Table la Compound N~o.
44 46 47 48 49
-CH
2 c0, 2-fluoro -H,4-fluoro
-CH
2 2,4-difluoro
-CH
2
CH
2 0 3-chioro -ci, 4-bromo -tb, 4-fluoro 44 (Continued) Empirical Formula M.P. (OC)
C
1 3
H
10
F
4
N
2 0S liquid
C
13
H
10
F
4 N2OS liquid
C
1 3
H
9
F
5 N1 2
OS
liquid
C
1 4
HI
3
F
3
N
2 0S liquid
C
1 2
H
8 ClF 3
N
2
OS
s
C
1 2 HBBrF3N 2
OS
S (58-61)
C
1 2
H
8
F
4
N
2 0S S (56-59) 1155W30113Wjd-6 WO 86/07590 PCT/US86/01284 Table lb Cmpd. No. Name I 3,4, 4-trifluoro-3-butelylthio) dihydrothiazole 2 2-tethylthio-5-( 3, 4,4-trifluoro-3-buterlylthio)-1, 3, 4-thiadiazole 3 4, 4-trifluoro--3-butenyl) heptafluorobutyrate 4 4-trifluorc-3-butelyl) 4-chlorobenzoate 3, 4,4-trifluoro-3-butenyl)succiflimide 6 4-trifluoro-3-butenyl) isothiccyanate 7 4, 5, 5-triflur-4-pentenl-o1 8 3-chloro-5-(3, 4, 4-trifluoro-3-butenylthio)- 1, 2,4-thiadiazole 9 3-brorto-5-( 3,4, 4-trifluoro-3-butenylthio)- 1, 2,4-thiadiazole 3,4, 4-trifluoro-3-butenylthio) thiophene 11 3,4, 4-trifluoro--3-buteflylthiomethyl)thianaphthene 12 1,1,3, 3-tetz:amethylbutylthio)-5-( 3 4,4trifluoro-3-butenylthio) 3, 4-thiadiazole 13 2, 5-di( 3,4, 4-trifluoro-3-butenylthio)-1, 3,4thiadiazole 14 2-propargylthio-5-( 3,4, 4-trifluoro-3butenylthio)-1, 3, 4-thiadiazole 2-cyclopropylxnethylthio-5-( 3,4, 4-trifluoro- 3-buteriylthio) 4-thiadiazole 16 2-phenyl-5-( 3,4, 4-trifluoro-3-butenylthio) 1, 3,4-oxadiazole 17 2-(4--chlorophenyl)-5-( 3,4, 4-triflucro-3butenylthio)-1, 3, 4-oxadiazole 18 4-trifluoro-3-buteiyl) 4-trifluoro-3-butenylthio) acetate 1153W30113Wjd-1 WO 8607599PCT/US86/0 1284 Table lb (continued) Crnpd. No. Name 19 (3,4,4-trifluoro-3-butenyl) pentafluoroprcpionate, mono diethyl etherate 4-trifluoro-3-butenxyl) 2-thiophenecarboxylate 21 (3,4,4-trifluoro)-3-butenyl) 5-nitro--2furancarboxylate.
22 4-trifluoro-3-butenyl) 2-pyrrolecarboxylate 23 4-trifluoro-3-butenyl) 4 hydrothiazolyl) thio~acetate 24 3,4, 4-trifluoro--3-butenyl) saccharine 3, 5-di( 3, 4,4-trifluoro-3-butenylthio)- 1,2, 4-thiadiazole 26 3-(4-nitrop~henyLmethylthio)-5-( 3, 4,4-trifluoro- 3-butenylthio) 2, 4-thiadiazole 27 2-fluoroethylthio) 3,4, 4-trifluor--3butenylthio) 4-thiadiazole b 28 2-.(2-cyanoethylthio)-5-( 3,4, 4-trifluoro-3butenylthio) 4-thiadiazole 29 2-prcpylthio-5-( 3,4, 4-trifluoro-3-butenyl- '1 thio) 4-thiadiazole 30 2-(1-methylethylthio)-5-( 3, 4,4-trifluoro -3butenylthio) 4-thiadiazole 31 2- (2-propenylthio) 4,4-trifluoro-3butenylthio) 3, 4-thiadiazole 32 2-pbenylmethy'lthio-5-( 3,4, 4-trifluoro-3butenylthio) 4-thiadiazole 33 2-(4-bromophenylmethylthio)-5-( 3,4, 4-trifluoro-3-butenylthio) 4-thiadiazole 34 2-fluorohe-nylmethythio)-5-( 3, 4,4-trifluoro-3-butenylthio) 3, 4--thiadiazole 115 3W3 011 3Wjd-2 WO 86/07590 PCT/US86/0 1284 47 Table lb (Continued) Cmd N o. Namne 2-(4-nitrophenylmethylthio)-5-( 3,4, 4-trifluoro-3-butenylthio) 3, 4-thiadiazole 36 2-thienylmethylthia) 3,4, 4-trifluoro- 3-butenylthio) 4-thiadiazole 37 2-(4-chlorophenyl)-5-(3, 4, 4-trifluoro-3butenylthia) 3, 4-thiadiazo'1c 38 4-fluorophenylmethyl 3,4, 4-trifluoro- 3-butenylthio)-1, 2, 4-oxadiazole 39 3-(4-chlorophenyl)-5-( 3,4, 4-trifluoro-3butenylthio)-1, 2, 4-oxadiazole 3-(4-nitrophenyl)-5-(3,4,4-trifluoro-3butenylthio)-l, 2, 4-oxadiazole 41 2-propyl-5-( 3,4, 4-trifluoro-3-butenylthio)- 1, 3, 4-oxadiazole 42 2-phenrylmiethyl-5-( 3,4, 4-trifluoro--3-butenylthio)-l, 3, 4-oxadiazole 43 4-chiorophenylme thyl) 3, 4,4-trifluoro- 3-butenylthio)-l, 3, 4-oxadiazole 44 2-fluorophenylmethyl) 3,4, 4-trifluoro- 3-butenylthio) 3, 4-oxadiazole 2-(4-fluorophenylmethyl) -5-C 3,4, 4-trifluoro- 3-butenylthio) 3, 4-oxadiazole 46 2-(2,4--difluorophenylmethyl)-5-(3,4, 4-tnifluoro-3-butenylthio) 3, 4-oxadiazole 47 2-phenylethyl)-5-( 3,4, 4-trifluoro--3butenylthio) 3, 4-oxadiazole 48 3-chlorophenyl)-5-( 3,4, 4-trifluoro-3butenylthio) 3, 4-oxadiazole 49 2-(4-bromop1enyl)-5-( 3, 4,4-trifluoro-3butenylthio) 4-oxadiazole 2-(4-fluoroplienyl)-5-( 3, 4,4-trifluoro--3butenylthio) 3, 4-oxadiazole 115 f3 3011VWj d- 3 WO 86/0 Cmt 7590 PCT/US86/01284 -48 Table lb (Continued) ipd. No. Name 230 2-(3,4,4-trifluoro-3-butenylthio)thiazole 231 2-(2,3,3-trifluoro-2-.propenylthio)thiazole 232 4, 4-difluoro-3-butenylthio) thiazole 233 2-(3,3-difluoro-2-propenylthio)thiazole 234 4, 4-dichloro-3-butenylthio) thiazole 235 2-(3, 3 -dichloro-2-propenylthio)thiazole 236 4-dibromo-3-butenylthio) thiazole 237 2-(3,3-dibromo-2--propenylthio)thiazole 238 2,3, 3-trichloro-2--propenylthio) thiazole 239 2-(3,4,4-trichloro-3-butenylthio)thiazole 240 2,3, 3-tribromo-2-propenylthio) thiazole 241 2-(3,4,4-tribromo-3--butenylthio)thiazole 1153W30113Wjd-4 OWN& I I W, I i il WO 86/07590 PCT/US86/O 1284 49 Table lc subst.ituted Thiadiazolyl/Oxadiazolyl Compounds
F
F I C C(CH SR wherein:
F
R 2S R is ~N SZ Compound No.
51 52 53 M.P. C 0
C)
phenylmethyl- 4-chiorophenylme thyl- 4-chlorophenylthiomethylliquid liauid liquid 54 R is Nr liquid liquid R is N
,,S
1153W3Ol13Wjd-25 WO 86/07590 I Compound No.
56 57 58 59 K 60 16 62 [1 63 64 ~j~i 65 66 67 68 69 N 70 71 72 (1 73 74 N 75 lj~ 76 1' 77 78 79 81 PCT/US86/0 1284 50 Table lc (Continued)
N-N
4-chlorophIenylmethyl- -ScH 2 CH 3 -SC 4 H 9 -SCH 2 H(CH 3 2 -S(C a 2 )2 CClFCBrF 2 -s(CH 2 )7 CH 3 -S(C c 2 )l
M
-S(CH 2l)2 al=a 2 -Sa 2 C(C a 3 =a 2 -SCH 2
CH=CHCH
3 -S(C a 2 )3 3 al=al 2
-SCH
2 CH=C(CH 3 2 -SCH 2 C(Cl)=Cal 2 -sC 2 CCBr)=C -SH2 CHC(Br) 2 -S(C a 2 )2 2 a=CCCl)-K
-SCH
2
CN
-S(C a 2 4
C;:N
-H
2 C 1-CH 3 H 3C 1-01 2, 4-dimethylphenoxymethyl- 3-chlorophenylmethylthio- 4-chlorophenylme thyithia- M.P. OC) liquid liquid liquid liquid liquid liquid liquid liquid liquid liquid liquid liquid liquid liquid liquid liquid liquid liquid solid (550) solid (690) liquid liquid liquid liqruid liquid solid (380) 1l53W301111jd-26 WO 86/07590 PCT/US86/0 1284 51. Table lc (Continued Compound
NSO.
82 83 84 86 87 88 89 91 92 93 94 96 97 98 99 100 101 102 103 104 105 106 107 108 109 110 ill 112
R
3 3, 4-dichlorophenylmethylthio- 2, 6-dichlorophenyne thylthio- 2-bromophenylmethylthio- 3-bromophenylme thylthio- 3, 5-dibromophenyLmethylthio- 3-fluorophenylme thyithio- 4- fluorophenylmethylthio- 2, 4-difluorophenylmethylthio- 2, 5-difluorophenylmethylthio- 3, 4-difluorophenylmethylthio- 2, 6-difluorophenylxethylthio- 2, 3,4, 5, 6-pentafluorophenylmethylthio- 2-chloro-6-fluorophenyliethylthio- ;2-iodophenylme thylthio- 2-methylphenylmethylthio- 3-me thylphenfy lne thylthio- 2-trifluoromethylphenylmethylthio- 3-trif luoromethylphenylrnethylthio- 4-trifluoromethylphenylmethylthio- 3-me tboxyphenylme thylthio- 4-methoxyphenylnethylthio- 4-trifluorointhoxyphenylme thylthio- 2-cyanophenylmethylthio- 3-cyanophenylme thylthio- 4-cyanophenylmethylthio- 2-nj trohenylnethylthio- 3-ni trophenylmethylthio- 2-chioro- 4-ni trcFhenylnethylthio- 4-chloro-2-ni trophenylmethylthio- 2-f luoro-4-ni trcphenylmethylthio- 2-methyl-3-nit rophenylmethylthio- M.P. (OC) liquid liquid liquid liquid liquid liquid liquid liquid liquid liquid liquid liquid liquid liquid liquid Liquid liquid liquid liquid liouid solid (42-44*) Siou id liquid liquid solid (51-57') liquid liquid liquid liquid liquid Liquid I 153W3011 3Wjd-27 WO 86/07590 PCT/US86/0 1284 52 Table lc (Continued Compound NO. R3 113 2-nitro-5-methylpheriylmethylthio- 114 2-methoxy-5-nitrophenylmethylthio- 115 3, 5-dinitrophenylmethylthio- 116 *4-phenylphenylmethylthio- 117 2-methyl-3-phenylphenylxnethylthio- 118 anthracine-9-ylmthylthio- 119 5-chlorothien-2-ylmethylthio- 1,20 2-rn thylthiazo1-4-ylmethylthio- 121 2, 6-dichloropyridin-4-ylrnethylthio- 122 1, 3--berzodioxol-5-ylmthylthio- 123 plvanylthiornethylthio- 124 l-phenylethylthico- 125 4-riitropheriyl) ethylthio- 126 3-phenoxypropylthio- 127 -NE C(0) CF 3 1EC 2 H 5 128 -NEC(o)cH 3 ECH 3 1 129 -NCC(O)CH 3 JE4-trifluorome-thylpheny1] 130 1, 2-bis(4-chloroohenyl)urea- 131 -NEC(0)CF 3 JE4-rnethoxyphenyl] 132 4-trifluoromehylpheny.aino- 133 4-methoxyphenylainino- 134 4-chlorophenylamino- 135 -NEC(O) CH=CC1 2
IH
3 3 chloropheriyl) urea- 137 1-methyl-2-( 4-chlorophenyl) urea- M. P. 11c) liquid liquid 1. quid solid (62') sol id liquid liquid liquid liquid liquid liquid liquid liquid liquid liquid liquid solid solid solid solid solid solid liquid solid sol-id (14.L-2*) 1153W3013Jjd-28 WO 86/07590 PCT/1JS86/0 1284 53 Table Ic (Continued) Compound No. R3 138 -N[C(O)a 3 ][4-chlorophenyl] 139 -NflC(O)ai 3 ]4-fluorophenyl] 3 C3 140 -NIC(O) CM=C2 C]4-methoxxyphenyl] 141 4-nitrophenylamino- 142 1-ethyl-2- (4-cittorophenyl )urea- 143 -NC(O)CHi 3 [4-methoxypheny1] 144 1- (4-f luoroplhenyl) 4-chiorophenyl) urea 145 -NMC 2
H
5 146 4-f luorophenylamino- 147 -N[CM 3 4-dichlorophenylmethylcarbonyll 148 -NEC(o) CH=OC1 2 3EC 2 H 5 149 4-bromophenylasnino)- 150 CH=CCJ 1C4-trifluoromethyiphenyl I M. P. 0
C)
solid (84-85o) solid (96-97') liquid solid solid solid solid solid solid liquid liquid solid liquid 151 152 153 154 -NcC 2
H
5 1 [Phenylmetlcxycar1hn,,1J
-NCC(Q)CH
3
]EC
2
H
5 bromomethylthio- -NEC(O)a1 3 J4-bromophenylJ solid liquid liquid solid 1153W30113WMd-29 WO 86/07590 PCT/US86/o 1284 54 -I Table lc (Continued) Compound No. R 3 M.P. 155 CH-=CC1 2 ][4-nitrophenyl] H3 c H3 156 -NCC(0) CH=CC 2 ][4-fluorophepyl] 157 -S(CH2) 3 CH 2 c 158 -SCH 2 Cl 159 -S(CH 2 4 Cl 160 -s(cR9 2
)CH
2 C1 161 -S(CH 2 3 ci 2 Br solid liquid semi-sol id lictuid lqiuid liquid solid (67-69*) 4 R is CompoundI No.
162 163 164 165 166 M.P. OC) 4-chlorop'henylmethyl- 4-methylphenylphenylmethylpheriyl- 2-chlorophenyl'.
liquid liquid liquid liquid liauid I 153W3011 3Wjd-30 WO 86/07590 Comm PCT/US86/0 1284 55 ound 167 168 169 170 3-chlorophanyl- 3-trifluoromtthylphenyl- 4-methoxyphenylmethyl- 3-nitrolhenyl- M. P. (C) solid (48-510) solid (41-44*) liquid solid (69-7l') R is R 5-1,, Compound No. M.P. 0 c) 171 172 173' 174 175 176 177 178 179 180 181 182 183 184 185 186 187 188 189
-CH
3 -C2 HS -a (C 3 2
-CH
2
CH(CH
3 2 -C (C C 3 )3~
-(CH
2 4
CH
3 -(CH9 2 16
CH
3 -CE-C(CH 2 )4 4
CH
3 -C 2 CH(C 3 )CF 3 2-chlorophenylme thyl- 2-bromophenylmethyl- 4-brom:opherrylme~thyl- 2-methylphenylmethy- 3-te thylphenylme thyl- 2-bromo-4, 5-dimethoxyphenylmethyl- 2-ni trophenylte thyl- 4-nitrophenylmethylthien-2-ylnethyl- 1 ,4-benzodioxan-6-ylmethy1liquid liquid liquid liquid liquid liquid solid (450) liquid liquid liquid liquid solid (38-40*) liquid liquid solid (54-590) liquid liquid liquid liquid 1153W30113Wjd-31 WO 86/07590 PCT/US86/o 1284 56 Table Ic (Continued) Compound No.
190 191 192 193 194 195 196 197 198 199 200 201 202 203 204 205 206 207 208 209 210 211 212 213 214 215 216 217 1 ,3-benzodioxo1-5-ylmethy1- 7 N N -H2C-N N N 0 1-phenylethyl- 4-nitrophenyl) ethyl- 2-C 4-chlorophenyl) ethenyl- 2- (4-bromophenyl) ethenyl- 2-f luorophenyl) ethenyl- 3-phenyipropyl- 4-phenylbutyl- 4-chlorophenoxymethyl- 4-methylphenoxymethyl- 3-methyl-4-chlorophenoxymethyl- 4-ni trophenoxymethyl- 1-C 4-chiorophenoxy) ethyl- 1- (4-rnethylphIenoxy) ethyl- 2-C 4-chlorophenylthio) ethyl- 1-C 4-chiorophenoxy) propyl- 2-chiorophenyl- 2-bromophenyl- 2, 5-dichlorophenyl- 2-metboxyphenyl 3-ietboxyphenyl- 4-methoxyphenyl- 3 ,4-dimethoxyphenyl- 4-nit rophenyl- 2-aminophenyl- 4-hydroxyphenyl- M.P. 0
C)
solid (69-7lo) liquid liquid 1liqui d liquid liquid 1 icruid liquid liquid liquid liquid liquid 1 iauid liquid liquid solid (54-59') liquid liquid liquid liquid liquid liquid liquid liquid solid (510) solid (94-96*) solid (57-61*) solid (96-101') *1 1153W30113Wmd-32 WO 86/07590 PCT/US86/o 1284 57 Table lc (Continued) Compound No.- 218 219 220 221 222 223 224 225 226 227 228 229
R
5 4-acetyloxyphenyl- 4-(methylaininocarbonyloxy) phenyl- 4-phenyiphenylnaphth-2-ylnaphth-1-ylthieri-2-ylfuran-2-yl- 4-methyl-i, 2, 3-thiadiazol-5-yl- 2-C 4-chiorophenyl) ethyl- 2-chiorophenyl) ethyl- 4-fluorophenyl) ethylphenylmethyl M.P. (Oc) solid (63-66') solid (108-1110) solid (49-52*) solid (70-72') solid (680) liquid l.iquid liquid solid (43-45*) liquid liquid liquid 1153W301111jd-33 WO 86/07590 PCT/US86/o 1284 58 Table Id (Continued) Polyhaloalkeny lthio Thiazo lyl Compounds S
N
F 2 C=CF (CH 2
)S
s Compound No.
230 231 M.P. 0
C)
liquid liquid 1153W3013Wjd-36 WO 86/07590 PCT/LS86/0 1284 59 Table 2 Initial Activity Against the Root-knot Nematode Compound Nio.
Application Rate (ppm) 10.0 Percent Control 1.25 0.625 0.313 0.625 0.313 0.156 0.078 LO0.0 Vi 1.25 0.625 0.313 10.0 1.25 0.625 0.313 1.25 0.625 0.313 10.0 10.0 1153W30113Wjd-4 WO 86/07590 PCT/US86/0 1284 Table 2 (Continued) Application Compound No. Rate (ppm) 8 1.25 0.625 0.312 0.625 0.312 0.156 0.078 1.25 0.625 11 1.25 0.625 12 1.25 0.625 0.313 13 1.25 0.625 0.313 0.625 0.313 0. 156 0.078 14 1.25 0.625 0.313 1.25 0.625 0.313 Percent Control 1153W30113Wjd-5 -Em.
WO 86/07590 PCT/US86/0 1284 61 Table 2 (Continued) Application Rate (pom) Percent Control 1.25 0.625 0.313 10.0 10.0 1.25 0.625 0.313 10.0 1.25 0.625 0.313 1.25 0.625 0.313 1.25 0.625 0.313 1.0.0 10.0 1153W301.l3Wjd-6 WO 86/07590 PCT/US86/0 1284 62 Table 2 (Continued) Compound No.
26 27 28 29 31 32 Application Rate (pm) 2.5 1.25 .625 .312 2.5 1.25 .625 .312 2.5 1.25 625 .312 2.5 1.25 .625 .312 2.5 1.25 .625 .312 2.5 1.25 .625 .312 2.5 1.25 .625 .312 .625 .312 .156 .078 2.5 1.25 .625 .312 Percent Control 99 97 97 78 86 63 0 0 100 99 79 31 100 98 86 81 99 99 99 100 99 99 97 99 96 78 69 63 44 13 0 100 99 97 78 1153W301-Vid-7 WO 86/07590 PCT/US86/0 1284 63 Table 2 (Continued) Comound No..
32 cont'd Application Rate (ppm) .625 .312 .156 .078 Percent Control 1.25 .625 .312 1.25 .625 .312 .625 .312 .156 .078 1.25 .625 .312 .625 .312 .156 078 1.25 .625 .312 100 98 67 100 99 96 69 .625 .312 .156 078 .625 .312 .156 .078 1534130113Wjd-8 WO 86/07590 Compound No.
38 39 41 42 PCT/LS86/0 1284 64 Table 2 (Continued) Application Percent Rate (pM) Control 2.5 98 1.25 96 .625 76 .312 63 2.5 100 1.25 98 .625 84 .312 1.9 i00 1.25 99 .625 83 .312 19 1.25 .625 .312 1.25 .625 .312 .625 .312 .156 .078 1.25 .625 .322 .625 .312 .156 078 100 97 84 31 43 .625 99 .312 78 .156 38 .078 13 1153W30113Wjd-9 WO 86/07590 PCT/US86/0 1284 65 -1 Table 2 (Continued) Application Rate (ppm) Percent Control Cortound No.
43 cont'd 1.25 .625 1.25 625 .312 1.25 .625 .312 1.25 .625 .312 1.25 .625 .312 1.25 .625 .312 .625 .312 .156 .078 1.25 .625 .312 1.25 .625 .312 1153W13011 3Wjd-10 WO 86/07590 PCT/US86/o 1284 66 Table 2 (Continued) Compound No.
230 Application Rate (ppm) 2.5 1.25 0. 625 0.313 Percent Control 100 100 81 44 1153W30113Wjd-12 WO 86/07590 PCT/US86/0 1284 67 Table 3 Residual Activity Against t.he Root-knot Nematode Cmpd. Application No. Rate (ppm) 11~0 Inoculation, Weeks After Treatment 1.
2 4 1 2 4 1 2 4 1 2 4 1 2 4 1 2 4 1 2 4 1 2 4 1 2 4 1 2 4 1 2 4 Percent Control 98 44 0 99 42 99 63 77 56 69 96 38 98 38 42 98 99 99 98 98 0 0 0 13 8 0 1153W3013Wjd-11 7 i i I WO 86/07590 PCT/US86/01284 68 Table 3a Residual Activity Against The Root-Knot Nematode 5% Dust Application Rate: 5 ppm Compound No.
27 Inoculation Post-Treatment 1 Week 2 Weeks 4 Weeks Percent Control 100 97 98 99 97 99 Week Weeks Weeks Week Weeks Weeks Week Weeks Weeks 100 100 8 1 Week 2 Weeks 4 Weeks 1 Week 2 Weeks 4 Weeks Week Weeks Weeks 1 Week 2 Weeks 4 Weeks 1 Week 2 Weeks 4 Weeks 1 Week 2 Weeks 4 Weeks 1153W30113'jd-12 WO 86/07590 PCT/US86/01284 69 Table 3a (Continued) Compound No.
Inoculation Post-Treatment 1 Week 2 Weeks 4 Weeks Percent Control 1 Week 2 Weeks 4 Weeks I Week 2 Weeks 4 Weeks 1 Week 2 Weeks 4 Weeks i Week 2 Weeks 4 Weeks 1 Week 2 Weeks 4 Weeks Week Weeks Weeks i Week 2 Weeks 4 Weeks 1153W30113;jd-13 7 WO 86/07590 PCT/US86/0 1284 Table 4 Initial Activity Against the Stunt Nematode Rate of Appication (ppm) Compound. No.
Percent Control 61 72 51 1153W30113qjd-14 4 111
A
WO 86/07590 PCT/US86/o 1284 '71- Table 4a Initial Activity Against the Stunt Nematede Application rate: 5 ppm Commund No.
27 28 29 31 32 33 34 36 Percent Control 89 56 62 38 56 66 52 84 52 88 56 77 83 64 91 Compound No.
41 42 43 44 45 46 47 .48 49 50 Percent Control 29 76* 33 81 76 62 82 66 58 53 *Somel phytotoxicity l153V;3ll3Kjd-l5
V
WO 86/07590 PCT/US86/0 1284 72- Table Initial Activity Against the Lesion Nematod~e Compound No.
1 Rate of Application (ppm) 5 Percent Control 82 52 0 0 33 1.25 .625 115 3W30l3Kjd-16 WO 86/07590 WO 8607590PCT/CS86/0 1284 Corwmund No.
36 73 Table 5 (Continued) Rate of Application (ppm) 2.5 1.25 .625 Percent Control 59 19 2 0 71 64 73 82 93 78 88 41 77 69 78 115--30Of3Wjd-17
RL
WO 86/07590 WO 8607590PCT/LUS86/0 1284 74- Table 6 Initial Activity Against the Cyst Nemnatode Compo~und No.
I
Rate of Applcation (ppm) 5 Percent Control 94 791 92 8 33 83 57 7 16 78 0 37 0 59 86 lWhole cysts rather than homogenized cysts were used.
1153W30113iWjd-18 I7 WO 86107599) PCT/US86/O 1284 Table 7 Soil Mbility Evaluations Against the Root-knot Nematode Onpd. No.
1 Application Rate (ppm) 30 1.25 0.625 0.313 Location of Test Container
TOP
Middle Bottom 1 (Top) 2 3 4 6 (Bottom) Top Middle Bottom
TOP
Middle Bot torn Top Middle Bottom
TOP
Middle Bottom Top Middle Bottom
TOP
Middle Bottom
TOP
Middle Bottom Top Middle Bottom Top Middle Bottom Percent Control 97 100 100 100 99 97 42 100 98 99 100 100 100 100 99 96 97 98 77- 77 42 33 100 100 96 33 100 96 99 1153W30113Wjd-19 WO 86/07590 PCT/US86/o 1284 Table 7a Soil Mobility Evaluations Against The Root-Knot Nematode 5% Dust; Application Rate: 5 ppm Compound N~o.
27 28 29 31 32 34 36 38 Location of Test Container
TOP
MIDDLE
BO'CM~
TOP
MIDDLE
BcxroM
TOP
MIDDLE
BOTItM
TOP
MIDDLE
BOTTOM
TOP
MIDDLE
Bg9TCM
TOP
MIIXUE
TOP
MIDDLE
TOP
MI DDLE
TOP
MIDDLE
BOITTCM
TOP
MIDDLE
BOTTIOM
TOP
MI DDLE
BOWOM
Percent Control 100 69 8 99 100 100 68 83 68 98 81 99 100 17 98 86 98 67 8 99 0 97 17 0 0 0 0 1153W30113WJjd-20 WO 86/07590 PCT/US86/0 1284 77 Table 7a (Continued) Compound No., Location of Test Container
TOP
MIDDLE
BOTWtM Percent Control
TOP
MIDDLE
BOTTOM
TOP
MIDDLE
BOTTOM
TOP
MIDDLE
BOTTOM
TOP
MIDDLE
BOTTOM
TOP
MIDDLE
BOTTOM
TOP
MIDDLE
BOTTOM
TOP
MIDDLE
BOTTOM
TOP
MIDDLE
BOI
T
I'04
TOP
MIDDLE
BOTrOM
TOP
MIDDLE
BOTTCt4 96* 42 *Sm phytotoxicity 1153;V3Oll3Wjd-21 WO 86/07590 PCT/US86/o 1284 78 Tabl.e 8 Systemic Activity Against the Root-knot Application Test Cmpd. No.Rate (ppm) 12 2000 1000 13 2000 2000 16 2000 17 2000 31 2000 1250 32 2000 33 2500 2000 Nematodes Percent Control 73, 99 42, 79 83 67 42 71 0 17 0 97 17 17 33 2000 1250 2000 2000 2500 llS3W30lla7jd-22 ~i1 WO 86/07590 PCT7US86/0 1284 7 79- Table Evaluations Against C. Elegans Comp~ound No.
26 32 33 34 37 39 43 Rate
(PPM)
5 1.25 5 1.25 5 1.25 5 2.5 1.25 5 1.25 5 1.25 5 1.25 5 1.25 1.25 5 1.25 5 1.25 Percent Inhibition of Reproduct ion 100 58 17 100 100 100 100 42 25 100 100 100 100 100 0 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 100 42 Percent Mortality 100 0 0 100 100 100 8 0 0 100 100 100 100 100 0 100 100 100 100 100 100 100 100 100 100 67 58 100 100 100 83 67 0 V I 48 1.25 1153l301~'jd-24 4 SI WO 86/07590 PCT/US86/0 1284 Table 9 Screen Against C. Elegans -Rate: 5 ppm CompoundNo.
26 27 31 32 33 34 37 39 43 44 48 Percent Inhibition of Reproduction 100 100 38 38 100 100 100 100 100 100 100 25 25 100 Percent Mortality 100 0 0 100 100 100 100 100 0 0 88 1153W301.l3Wjd-23

Claims (14)

1. formula: Polyhaloalkene compounds characterized by the 0: 0 .0 0000 Goes j 0* 0 as S S *5@S I S. F2C=CF(CH 2 )nXR wherein X is sulfur, oxygen or nitrogen and n is 1-4; provided that: when X is sulfur, and R is thienyl or substituted thienyl, thianaphthyl or substituted thianaphthyl, thiazolinyl or substituted thiazolinyl oxadiazolyl or substituted oxadiazolyl wherein the thienyl, thianaphthyl, thiazolinyl and oxadiazolyl substituents are selected from straight chain and branched C, to C 1 1 alkyl, alkenyl and alkynyl groups, phenyl, naphthyl, diphenyl and anthracene groups which may bear alkyl substituents and heterocyclic groups, halo, nitro, cyano, alkoxy, alkylthio, haloalkyl, haloalkoxy, halo-, nitro-, cyano- or alkoxy-substituted phenyl, polyhaloalkenylthio, phenylalkylthio, phenylthioalkylthio, propargylthio, and cycloalkyl- methylthio; 3,4,4-trifluoro-3-butenyloxycarbonylmethyl, thiadiazolyl substituted by halogen or R2S, wherein R 2 is 3,4,4,-trifluoro-3-butenyl or R 2 is phenylmethyl or phenylthio-methyl each optionally substituted by halogen or nitro; or R is thiadiazolyl substituted by R 3 wherein R 3 is substituted aryl, arylalkyl, aryloxyalkyl, alkylthio, haloalkylthio, haloarylthio, cyanoalkylthio, arylalkylthio, aryloxyalkylthio, arylthioalkylthio, heterocycloalkylthio, alkenylthio, haloalkenylthio, halocycloalkylalkenylthio, wherein said aryl or heterocyclo-substitutents of R 3 may be mono-, di-, tri-, tetra-, or penta-substituted by substituents selected from halogen, haloalkyl, alkoxy, haloalkoxy, cyano, nitro and phenyl; or R 3 is an amino group mono- or di-substituted with members independently selected from alkyl, alkylcarbonyl, haloalkylcarbonyl, aryl, arylaminocarbonyl, qL' IIMi -82- arylalkylcarbonyl, arylalkoxycarbonyl, and
3-(2,2-dichlorethenyl)-2 2-dimethylcyclopropanecarbonyl; when X is oxygen, and R is C(O)R 1 wherein R 1 is perfluoralkyl, phenyl or substituted phenyl, thienyl or substituted thienyl, furanyl or substituted furanyl, pyrollyl or substituted pyrollyl, or dihydrothiazolylthiomethyl wherein the phenyl, thienyl, fuianyl, pyrollyl substituents are selected from aliphatic, aromatic and heterocyclic groups, halo, nitro, cyano, alkoxy, alkylthio, haloalkyl, haloalkoxy, halo-, nitro-, cyano- or alkoxy-substituted phenyl, polyhaloalkenylthio, phsnylalkylthio, phenylthioalkylthio, propargylthio, and cycloalkylmethylthio; and when X is nitrogen, R taken with the nitrogen is an isothiocyanate, succinimide or saccharine group; I wherein the heterocyclo substituents of and are selected from thienyl, isoxazolyl, pyridinyl, thiazolyl, ^J thiazolinyl, benzodioxanyl, benzodioxolyl, tetrazolyl and furanyl. 2. Compounds of the formula of claim 1 characterized in that X is sulfur. 3. Compounds of the formula of claim 1 characterized in that X is sulfur and R is a thiadiazolyl or an oxadiazolyl group, substituted on a nuclear carbon atom.
4. Substituted thiadiazolyl compounds of claim 3 characterized in that the substituent is R2S- wherein R 2 is 3, 4,4-trifluoro-3-butenyl, phenylmethyl optionally substituted with halogen or nitro, or phenylthiomethyl unsubstituted or substituted with halogen or nitro. Substituted thiadiazolyl compounds of claim 3 characterized in that the substituent is iodo. c I I i -;i i -82a-
6. Substituted oxadiazolyl compounds of claim 3 characterized in that the substituent is aryl, an arylalkyl group substituted with chloro, fluoro, alkyl, haloalkyl, alkoxy or nitro or the substituent is aryl substituted by halogen, haloalkyl, alkoxy, haloalkoxy, cyano, nitro or phenyl.
7. Substituted oxadiazolyl compounds of claim 3 characterized in that the substituent is alkyl, haloalkyl, aryl, aryl substituted by halogen, haloalkyl, alkoxy, haloalkoxy, cyano, nitro, or phenyl or the substituent is arylalkyl, aryloxyalkyl, arylthioalkyl, heterocycloalkyl, substituted heterocycloalkyl, arylakenyl or alkynyl. DBM:SC(2:17)(EK) a
8. Compounds of claim 2 selected from 3,4, 4-trifluoro-3-butenylthio) thiophene, thiazole, -ehlho5(,,-rfluoro-3-butenylthio)-l34hidaoe thiadiale, l 2-cyclopropylmrethyltthio-( 3,4, 4-tnfur- flo3butenylthio)- 3,4-thiadiazole, 2,-hor5(3,4,4-trifluoro-3-butenylthio)-l,2,4-- thiadiazole, 15 2-(4-chlorophenyl)-5-(3,4,4-trifluoro-3-butenyl- t' :thio)-1,3,4-oxadiazole, 3,5-di(3,4,4-trifluoro-3-butenylthio)-l,2,4- thiadiazole, 3-C 4-nitrophenylmethylthio) -5-C 3,4, 4-tri- fluoro-3-butenylthio)-1,2,4-thiadiazoie, 2-fluoroethylthio)-3-( 3,4, 4-trifluoro-3- butenylthio) 4-thiadiazole, 2-C 2-cyanoethylthio)-5-( 3, 4,4-trifluoro-3- butenylthio)-1,3,4-thiadiazole, 2-proDylthiLo-5-(3,4,4-trifluoro-3-butenylthio)- 1, 3, 4-thiadiazcle, 2-C 1-methylethylthio)-5-( 3,4, 4-trifluoro-3- butenylthio)-1,3,4-thiadiazole, see:* 2-C 2-propenylthio) 3,4, 4-trifluoro-3-butenyl- thio)-1,3,4-thiadiazole, 3,4, 4-trifluoro-3-butenyl- thio)-1,3,4.-thiadiazole, 2-C 4-bromophenylmethylthio) -5-C 3,4, 4-trifluoro-3- butenylthio)-1, 3,4-thiadiazole, 2-(2-fluorophenylmethylthio)-5-(3,4,4-trifluoro-3- butenylthio)-1,3,4-thiadiazole, 2-C 4-nitrophenylmethylthio) 3,4, 4-trifluoro-3- butenylthio)-1, 3,4-thiadiazole, 2-thienylmethylthio) -5-C 3,4, 4-trifluoro-3- butenylthio)-1, 3,4-thiadiazole, 2-(4-chlorophenyl)-5-(3,4,4-trifluoro-3butenl- thio)-1, 3,4-thiadiazole, 4-fluorophenylmethyl) 3,4, 4-trifluoro-3- bu~tenylthio) 4-oxadiazole, 4-chlorophenyl) -5-C 3,4, 4-trifluoro-3-butelyl- thio)-1,2,4-oxadiazole, 3-(4-nitrophenyl)-5-(3,4,4-trifluoro-3-butenyl- thjo)-1, 2,4-oxadiazole, 2-propyl-5-(3,4,4-trifluoro-3-butenlthio)l:J, 4 oxadiazole, ~15 2-phenylmethyl-5-C 3,4, 4-trifluoro-3-butenylthio) 1,3,4-oxadiazole, 2-C 4-chlorophenylmethyl) -5-C 3,4, 4-trifluoro-3- butenvlthio)-1,3,4-oxadiazole, see*2-C 2-fluorophenylmethyl-5-C 3,4, 4-trifluoro-3- butenylthio)-1,3,4-oxad.azole, 2-C 4-fluorophenylme-thyl) 3,4, 4-trifluoro-3- butenylthio)-1, 3,4-oxadiazole, 2-(2,4-difluorophenylmethyl)-5-C3,4,4-trifluoro- 3 butenylthio)-1,3,4-oxadiazole, 2-(2-phenylethyl)-5-(3,4,4-trifIuoro-3-butelyl- thio)-1,3,4-oxadiazole, 00*. 2-C 3-chomrophenyl) -5-C 3,4, 4-trifluoro-3-butenyl- 4-oxadiazole, 2-C 4-bromophenyl) 3,4, 4-trifluoro-3-butenyl- thio)-l,3,4-oxadiazole, 2-C3,4,4-trifluoro-3-butel 2-C 2,3, 3-trifluoro-2-buteny) thio) thiazole. 3~I 1 5
9. Compounds of the formula of claim 1 charac- A) terized in that X is oxygen. 2 Compounds of claim 9 selected from (3,4,4-trifluoro -3-butenyl) pentafluoropropionate mono diethyl etherate, (3,4,4-trifluoro-3-butenyl) heptafluorobutyrate, (3,4,4-trifluoro-3-butenyl) 4-chlorobenzoate, (3,4,4-trifluoro-3-butenyl) 2-thiophenecarboxylate, (3,4,4-trifluoro-3-butenyl) 5-nitro-2-furancar- boxylate, (3,4,4-trifluoro-3-butenyl) 2-pyrrolecarboxylate and (3,4,4-trifluoro-3-butenyl) (2-(4,5-dihydrothia- zolyl)tiioacetate.
11. Compounds of the formula of claim 1 characterized es:. in that X is nitrogen. S. 12. Compounds of claim 11 selected from (3,4,4-tri- S0 fluoro-3-butenyl) isothiocyanate, N-(3,4,4-trifluoro-3-butenyl)succinimide and ,/N-(3,4,4-trifluoro-3-butenyl saccharine.
13. A method of controlling nematodes characterized by applying to the locus where control is desired a nematicidally effective amount of a compound as claimed in any one of claims 1 to 12. S14. A method of controlling nematodes characterized by 0* applying to the locus where control is desired a nematicidally effective amount of a compound of the formula F 2 C=CF(CH 2 CH 2 OH wherein n is 1-4. 6e a 15. A method of controlling nematodes characterized by applying to the locus where control is desired a nematicidally effective amount of a compound of the formula F 2 C=CFCH 2 CH 2 C-2~q <1
16. A nematicidal composition characterized by a nematicidally effective amount of a compound as claimed in any one of claims I to 12 in an agriculturally acceptable carrier.
17. A method of controlling helminths that infect animals, characterized by administering to an animal an anthelmintic amount of a compound as claimed in any one of claims 1 to 12.
18. An anthelmintic composition characterized by an effective amount of a compound as claimed in any one of claims 1 to 12 in combination with a pharmaceutically j a tceptable carrier. 4. DATED this 16th day of November 1989 Sew'..: FMC CORPORATION a.O. WATERMARK PATENT TRADEMARK ATTORNEYS, 50 Queen Street u, MELBOURNE. VIC. 3000 AUSTRALIA DBM:LN (7.35) S. 6 (v S *Y 4 4~ A INTERNATIONAL SEARCH REPORT International Application No PCT/US86/ 01284 I, CLASSIFICATION OF SUBJECT MATTER (if several classification symbols apply, Indicate all) 3 According to International Patent Classification (IPC) or to both National Classification and IPC IPC C4) CO7C 33/42, 69/63, 69/767; C07D 271/06 271/10 277/26 285/06, 285/12 See attachment II. FIELDS SEARCHED Minimum Documentation Searched 4 Classification System Classification Symbols 260/454; 548/129, 130,132,136,142,144,182,187,210, U.S. 531,545; 549/49, 62, 79,481,484;560/11,,219227;568/84 849:514/361,363,364,369,373,423, see attachment Documentation Searched other than Minimum Documentation to the Extent that such Documents are Included In the Fields Searched a CHEMICAL ABSTRACTS 1-104 III. DOCUMENTS CONSIDERED TO BE RELEVANT e1 Category I Citation of Document, to with indication, where appropriate, of the relevant passages 17 Relevant to Claim No. Is X US, A, 3,058,990 (HARMUN) 16 October 1962 1,2,5,6,8, See entire document 11,18,19,22 23,24,27,34, 35,38-40,43, 50,51,54-56,
59-61,64-66, 69 X US, A, 3,080,405 (LARSEN 05 March 1963 1,12,13,34, See Ex. IX and column 8 line 74 44, X EP, A, 138091 (DAIKIN) 24 April 1985 1,16,17,34, See Ex. 4 48,49,60 X US, A, 3,513,172 (BROKKE) 19 May 1970 1-6,8,11,18- See entire doucment 24,34-40,43, 50-56,59-66 69 Special categories of cited documents: Is later document published after the international filing date document defining the general state of the art which is not or' piority date and not In conflict with the application but considered to be of particular relevance cited to understand the principle or theory underlying the invention earlier document but published on or after the International "X document of particular relevance; the claimed invention filig de cannot be considered novel or cannot be considered to document which may throw doubts on priority claim(s) or involve an inventive step which is cited to establish the publication date of another document of particular relevance; the claimed invention citation or other special reason (as specified) cannot be considered to involve an Inventive step when the document referring to an oral disclosure, use, exhibition or document is combined with one or more other such docu- other means ments, such combination being obvious to a person skilled document published prior to the International filing date but In the art. later than the priority date claimed document member of the same patent family IV. CERTIFICATION Date of the Actual Completion of the International Search 5 Date of Mailing of this International Search Report I September 19.86 1 SEP 1986 International Searching Authority I Signature uori Off Form PCT/ISA/210 (second sheet) (May 1986) AL4_ _I_ -^1 I International Application No. PCT/tS86/01284 III. DOCUMENTS CONSIDERED TO BE RELEVANT (CONTINUED FROM THE SECOND SHEET) Category I Citation of Document, I" with Indication, where appropriate, of the relevant passages I Relevant to Claim No Is S US, A, 3,463,856 (KADO) 26 August 1969 Chemical Abstracts, Volume 93 No. 3, issued 21 July 1980 (Columbus, Ohio) !Abstract No. 2 0 617e. Yu v. Shcheglov "Herbicide Activity of Substances containing the triallyl group 2. iTrichloroallyl esters of aliphatic carboxylic and halocarboxylic acids" Agrokhimiya 97-101 (1980) Russ. See RN 73938-53-1 K !FR, A, 1,528,170 (Agripat) 07 June 1968 See compound 2, Table III K JP, A, 49/8259 (Terakawa) 25 February 1974 See entire document ,14 ,12,34,44, i,2,4,34,35 38,60,61,65 I 1,2,5,8,34, 35,38,40,60 61,64,66 Form PCT/ISA/210 (extra sheet) (May 1986) -401 7~ International Application No CT/US 8 6/ 01 2 8 4 1 FURTHER INFORMATION CONTINUED FROM THE SECOND SHEET OBSERVATIONS WHERE CERTAIN CLAIMS WERE FOUND UNSEARCHABLE Io This international search report has not been established In respect of certain claims under Article 17(2) for the following reasons: 1.I Claim numbers because they relate to subject matter L' not required to be searched by this Authority, namely: Claim because they relate to parts of the international application that do not comply with the prescribed require- ments to such an extent that no meaningful international search can be carried out 13, specifically: VI.R OBSERVATIONS WHERE UNITY OF INVENTION IS LACKING 11 This International Searching Authority found multiple Inventions In this International application as follows: See attachment As all required additional search fees were timely paid by the applicant, this international search report covers all searchable claims of the international application. 2.F As only some of the required additional search fees were timely paid by the applicant, this international search report covers only those claims of the international application for which fees were paid, specifically claims: No required additional search fees were timely paid by the applicant. Consequently, this International search report is restricted to the invention first mentioned In the claims; It Is covered by claim numbers: 4.n As all searchable claims could be searched without effort justifying an additional fee, the International Searching Authority did not invite payment of any additional fee. Remark on Protest The additional search fees were accompanied by applicant's protest. M No protest accompanied the payment of additional search fees. Form PCT/ISA/210 (supplemental sheet (May 1986) LL.e PCT/US86/01284 Attachment to 210 Part I. IPC AOIN 31/02, 37/02, 37/10, 43/78, 43/82 US.C1. 260/454; 548/129, 130, 132, 136, 142, 144, 182, 187, 210, 531, 545 549/49, 62, 79, 481, 484 560/111, 219, 227 568/843; 849 514/361, 363, 364, 369, 373, 423, 425, 443, 445, 448, 514, 544, 549, 550, 739 Part.II. 425, 443, 445, 448, 514, 544, 549, 550, 739 Part VI. I. Compounds where X is sulfur classified in 548/129 -Claims 2-11, 19-27, 35-43, 51-59,
61-69. II. Compounds where X is Oxygen classified in 548/187 -Claims 12, 13, 28, 29, 44, III. Compounds where X is Nitrogen classified in 548/210 -Claims 14, 15, 30, 31, 46, 47. IV. Compounds where X is methylene classified in 568/843 -Claims 16, 17, 32, 33, 48, 49. Claims 1, 18, 34, 50 and 60 are generic. PCT/US86/01284 Each definition of X recites unique and distinct moieties for R which are distinct. A reference indi- cating an R moiety for group I. would not be applicable to one for group IV for example.
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EP0263066A3 (en) * 1986-09-26 1988-06-01 Ciba-Geigy Ag 2-mercapto-oxadiazole and -thiadiazole derivatives, process for their preparation and nematicides containing them
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