WO1996021354A1 - Composes pesticides - Google Patents

Composes pesticides Download PDF

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Publication number
WO1996021354A1
WO1996021354A1 PCT/GB1996/000041 GB9600041W WO9621354A1 WO 1996021354 A1 WO1996021354 A1 WO 1996021354A1 GB 9600041 W GB9600041 W GB 9600041W WO 9621354 A1 WO9621354 A1 WO 9621354A1
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WIPO (PCT)
Prior art keywords
group
compound
alkyl
formula
optionally substituted
Prior art date
Application number
PCT/GB1996/000041
Other languages
English (en)
Inventor
Bhupinder Pall Singh Khambay
Duncan Batty
Original Assignee
British Technology Group Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from GBGB9500389.3A external-priority patent/GB9500389D0/en
Priority claimed from GBGB9500394.3A external-priority patent/GB9500394D0/en
Priority claimed from GBGB9523165.0A external-priority patent/GB9523165D0/en
Priority to BR9606742A priority Critical patent/BR9606742A/pt
Priority to CZ972141A priority patent/CZ214197A3/cs
Priority to JP8521515A priority patent/JPH10511976A/ja
Application filed by British Technology Group Limited filed Critical British Technology Group Limited
Priority to SK905-97A priority patent/SK90597A3/sk
Priority to MX9705211A priority patent/MX9705211A/es
Priority to NZ298116A priority patent/NZ298116A/xx
Priority to AU43524/96A priority patent/AU699685C/en
Priority to PL96321274A priority patent/PL185703B1/pl
Priority to EP96900136A priority patent/EP0802729A1/fr
Publication of WO1996021354A1 publication Critical patent/WO1996021354A1/fr
Priority to US08/891,079 priority patent/US6043286A/en

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Classifications

    • 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
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical containing keto or thioketo groups as part of a ring, e.g. cyclohexanone, quinone; Derivatives thereof, e.g. ketals
    • 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
    • A01N35/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical
    • A01N35/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen
    • A01N35/10—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having two bonds to hetero atoms with at the most one bond to halogen, e.g. aldehyde radical at least one of the bonds to hetero atoms is to nitrogen containing a carbon-to-nitrogen double bond
    • 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
    • A01N37/02—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
    • A01N37/10—Aromatic or araliphatic carboxylic acids, or thio analogues thereof; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
    • C07C251/32—Oximes
    • C07C251/34—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals
    • C07C251/44—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups being part of a ring other than a six-membered aromatic ring
    • C07C251/46—Quinone oximes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C46/00—Preparation of quinones
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C50/00—Quinones
    • C07C50/26—Quinones containing groups having oxygen atoms singly bound to carbon atoms
    • C07C50/32—Quinones containing groups having oxygen atoms singly bound to carbon atoms the quinoid structure being part of a condensed ring system having two rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/013—Esters of alcohols having the esterified hydroxy group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/18—Systems containing only non-condensed rings with a ring being at least seven-membered

Definitions

  • the present invention relates to the use of certain 1,2,3,4-substituted naphthalene compounds as pesticides active, inter alia, against whitefly and certain fungi; to methods for preparation of these compounds; to compositions containing them and to use of the compounds and compositions for the control of whitefly, Lepidoptera and fungal pests.
  • R is a radical, containing from 6 to 15 carbon atoms, selected from alkyl. cyclohexyl and cvclohexylalkvl groups; n-alkyl, iso-alkyl, alkvlcycloalkvl and aralkyl groups being exemplified. No specific miticidal or aphicidal data is given for these compounds and thus no indication is given as to which of the many compounds is best or. indeed, whether these are useful for control of pests other than mites and aphids.
  • R j is a straight, branched or cyclic Cg. ] 4 alkyl group
  • R2 is a straight or branched C 7 alkyl.
  • alkenyl, C 3 . 6 cycloalkyl, C j _ 4 alkoxy, -CH 2 OCH , -CH 2 OCH 2 CH, or -CH CH-COOH group
  • X and Y represent a hydrogen, fluorine, chlorine or bromine atom or a methyl or methoxy group.
  • Y is hydrogen, fluorine, chlorine or bromine
  • R* is branched, cyclic or straight chain Cg. j 4 alkyl
  • R 2 is branched or straight chain C ⁇ _ ⁇ saturated alkyl or C3.22 unsaturated alkyl optionally substituted by one or two chlorine, bromine, methoxy or ethoxy substituents, or C3.6 cycloalkyl.
  • GB 1553424 discloses compound of general formula (P3) wherein R ⁇ is H and R* is optionally substituted cyclohexyl, for use as an active agent for treatment of infection of cattle with theilerosis, while EP 0123238 and EP 0123230 relate to similar such compounds for use as anti-protozoan and anti-coccodiosis agents.
  • R 1 represents hydrogen or an optionally substituted alkyl.
  • R ⁇ is a hydrogen atom and R* ⁇ is a 4-(t-butyl)cyclohexyl, 4-(trimethylsilyl)cyclohexyl, 4-(cyclohexyl)-cyclohexyl, 2-trifluoromethylcyclohexyl or 3,5-di(trifluoromethyl)- cyclohexyl group or n is 0,
  • R* is an ethanoyl group and R* ⁇ is a 4-(t-butyl)cyclohexyl,
  • EP 0077550 discloses compounds of general formula (P5)
  • R is an alkyl group of from 1 to 10 carbon atoms and describes their use in veterinary formulations, particularly for prophylaxis against protozoan infection.
  • R represents a hydrogen atom or a hydroxyl or an ethanoyloxy group
  • R relates to their use as pesticides, especially fungicides, insecticides and/or acaricides.
  • the present inventors have determined that many of the prior art naphthoquinones do not have high activity against whitefly, and particularly that most of the aphicidal and acaricidal compounds specifically disclosed in the prior art have disappointing efficacy when tested against whitefly of resistant and susceptible types.
  • -_>- and related 1 ,4 derivatized compounds have advantageous pesticidal properties over those disclosed for such use in the prior art, particularly as applied to treatment of whitefly.
  • Preferred synthetic compounds for the use of the invention have excellent pesticidal activity against, inter alia, whitefly and/or fungi, with most preferred compounds also showing good activity against mites and/or aphids.
  • the compounds identified by the present inventors have particular use against strains of whitefly and fungi that have become resistant to one or more of the currently commercially available pesticides.
  • 3-position is from 4 to 8. more preferably from 5 to 7. Where the number of carbon atoms is restricted to 1 or 2 whitefly activity is lost but antifungal activity remains high. Where -CHR R5 f orm a carbocyclic ring this is preferably directly attached to the naphthalene 3- position as increasing numbers of carbon atoms between the naphthalene ring and the naphthalene ring result in decreased whitefly activity.
  • the present use particularly provides compounds for use against whitefly, particularly of species of Bemisia. and/or fungi, particularly of species of Rhizoctonia. Aspergillus and Pyricularia eg. R. solani, P. oryzae and A. niger, that have developed resistance to one or more commercially available non-naphthoquinone based pesticides, and most preferably for use against whitefly of species Bemisia tabaci such as Ned 1/2, Ned 7, and Pak types; these having been determined by the present inventors to be particularly susceptible to the pesticidal actions of the presently identified compounds as compared to those of. for example, those compounds specifically tested in US 2572946, US 4110473 and DE 2641343.
  • DE 3801743 lists some of the presently used compounds per se and describes them as useful against many different species of insect and fungi, no indication is given as to the significantly advantageous application of such compounds to combatting whitefly.
  • the compounds of formula I contain a group defined as an alkyl, alkenyl or alkynyl substituent group otherwise undefined, this may be linear or branched and may contain up to 12, preferably up to 6 and especially up to 4. carbon atoms.
  • a cycloalkyl or cycloalkenyl group may contain from 3 to 10, but most preferably contains 5 to 8 carbon atoms.
  • An aryl group may be any aromatic hydrocarbon group, especially a phenyl or naphthyl group.
  • An aralkyl group may be any alkyl group as defined above which is substituted by an aryl group as defined above, especially a benzyl group, or may be an aryl group substituted by an alkyl group.
  • substituent groups which are optionally present may be any one or more of those customarily employed in the development of pesticidal compounds and/or the modification of such compounds to influence their activity, persistence, penetration or other property.
  • substituents include, for example, halogen atoms, nitro, cvano, hydroxyl, alkyl, alkenyl, haloalkyl, haloalkenyl, alkoxy, haloalkoxv, amino. alkylamino, dialkvlamino, alkoxycarbonyl, carboxyl, alkanoyl, alkylthio, alkylsulphinyl.
  • alkylsulphonyl carbamoyl, alkylamido. cycloalkyl, phenyl and benzyl groups.
  • 0-3 substituents may be present.
  • alkyl substituent group this may be linear or branched and may contain up to 12, preferably up to 6. and most preferably up to 4, carbon atoms.
  • substituents represents or contains an aryl or cycloalkyl moiety, the aryl or cycloalkyl moiety may itself be substituted by one or more halogen atoms, nitro. cyano. alkyl, alkenyl.
  • haloalkyl haloalkenyl, alkoxy or haloalkoxy groups.
  • the aryl moiety is a phenyl moiety and the cycloalkyl moiety contains from 3 to 8, preferably 4 to 7. carbon atoms.
  • R represents a halogen atom or a nitro. cyano, hydroxyl, C j _4 alkyl, C j _4 haloalkyl, C _4 alkenyl, C 2 _4 haloalkenyl, C j .4 alkoxy, C ] _4 haloalkoxy, C ⁇ _4 alkylamino, di-C*,_4 alkylamino, C j _4 alkoxycarbonyl, C j _4 alkylthio, C j . alkylsulphinyl or Cj_4 alkylsulphonyl group. More preferably, R, if present, represents a halogen atom or a C j _4 alkyl,
  • C ⁇ _4 haloalkyl C 2 _4 alkenyl, C 2 _4 haloalkenyl, C ⁇ _4 alkoxy or C* _4 haloalkoxy group.
  • n is 0, 1 or 2 and it is especially preferred that n is 0.
  • R J is a group -OL where L is a leaving group, or a group which in vivo is transformed into a group -OL ⁇ where L ⁇ is a leaving group
  • the leaving group may be any group customarily employed as a leaving group. It is preferred that the leaving group is such that the pK a value of the acid LOH or L 1 OH in water is from 1 to 7, more preferably from 1 to 6 and especially from 1 to 5.
  • R- 7 represents a group which in vivo is transformed into a group -OL* where L is a leaving group, it is preferred that the transformation is carried out in a plant to be protected or a pest to be combated, preferably by action of enzymes within the plant or pest.
  • R 3 represents a ⁇ -acid group, such as -O-CH 2 CH CO-OH where -CH 2 CH 2 CO-OH is not a leaving group
  • R 3 may be subjected to enzymatic oxidation in vivo to form a group -O-CO-CH 2 -CO-OH, e.g. by a ⁇ -oxidase.
  • -CO-CH -CO-OH is a leaving group.
  • R J represents a group -OR*" where R*0 represents a hydrogen atom, an optionally substituted alkyl, alkenyl, aryl or aralkyl group or a group -CO-R ⁇ * , -CO-O- R 1 -SOR 1 K -SO ⁇ -R 1 * .
  • R' * represents a hydrogen atom, an optionally substituted alkyl, alkenyl.
  • aryl or aralkyl group or a group -NR- ⁇ R* 3 independently representing a hydrogen atom or an optionally substituted alkyl group and X represents an oxygen or sulphur atom.
  • K ⁇ or R ⁇ * represents an optionally substituted aryl or aralkyl group
  • the aryl group or moiety is a phenyl group or moiety and that the optional substituents are selected from halogen atoms, nitro and C j ⁇ alkyl groups. Substitution at the 4-position of the phenyl ring is particularly preferred.
  • the term optionally substituted includes, e.g.. substitution with silicon containing groups, e.g..
  • R 3 represents a hydroxyl group or a group -0-C0-R11 or -O-CO-OR* * where R* l represents a hydrogen atom or a C j _ ⁇ alkyl, C j_i2 haloalkyl. C ⁇ _i2 hydroxyalkyl, C J. J 2 carboxylalkyl, phenyl or benzyl group.
  • R 3 represents a group -OH or -O-CO-R* * , where R! 1 represents a hydrogen atom or a C ] .g alkyl, C j .g haloalkyl, phenyl or benzyl group. Most preferred for R* * is a methyl, ethyl, propyl or butyl group.
  • _4 alkyl group, but it is especially preferred that R 7 and R° are both methoxy or together represent a group O.
  • R ⁇ and R each independently represent hydrogen, or a C j .7 alkyl, C j . 7 haloalkyl, C 2 _7 alkenyl or C 2 _7 haloalkenyl group or, together with the interjacent carbon atom, represent a C4_ cycloalkyl or cycloalkenyl ring which is optionally substituted with substitutents selected from halogen and methyl, ethyl, ethenyl, halomethyl, haloethyl and haloethenyl groups. More preferably R + and R are independently selected from C ⁇ _4 alkyl. C j _4 haloalkyl, C 2 _4 alkenyl and C .4 haloalkenyl groups or form a ring.
  • the compounds of formula I may form salts, e.g. when R 3 represents a hydroxyl group.
  • Suitable bases for forming such salts include inorganic bases, such as sodium hydroxide, potassium hydroxide or sodium carbonate, and organic bases, for example tertiary amines such as triethylamine and cyclic amines such as pyrrolidine.
  • R. R 1 . R 2 , R 3 , R 7 and R 8 and n are as defined for formula I and R 4 and R 5 independently represent a hydrogen or halogen or an alkyl or alkenyl group that is optionally halo-substituted while remaining within the limits for carbon chain length set out for formula I.
  • R 3 is preferably -OH, -O-CO-R 1 1 or -O-CO-O-R 1 ] where R 1 * is C1.3 alkyl; and most preferably -OH. Most preferably -CHR 4 R ⁇ contains from 2 to 5 carbons.
  • compounds of this first preferred group generally have good activity against whitefly and, when the longest 3 position chain is 7 carbons or less, fungi, eg. R. solani, P. oryzae and A. niger, while retaining activity against mites.
  • n, A. R, R 1 , R 2 , R 3 , R 7 and R 8 are as defined for general formula (I); m represents an integer 0 to 1 ; and R 4 and R together with the interjacent carbon atom represent an optionally substituted
  • R 4 and R J together with the interjacent carbon atom represent a C5.7 saturated cycloalkyl ring substituted with halogen, most preferably chlorine or fluorine, or with C j _4 alkyl or haloalkyl or C _4 alkenyl or haloalkenyl group R ⁇ .
  • R 4 and R? together with the interjacent carbon atom represent a cyclopentyl or cyclohexyl ring substituted in one or more of the 2. 3 or 4 positions with a group R ⁇ .
  • the moiety -CHR 4 R 5 does not represent a cycloalkyl or cycloalkenyl ring and is provided spaced by i between 1 and 6 carbon atoms length away from the naphthalene ring, and most preferably between 2 and 4 carbon atoms length away from the naphthalene ring.
  • R, R 1 , R 2 , R 3 , R 7 and R 8 are as defined for general formula (I);
  • R 4 and R ⁇ each independently represent a halogen or optionally substituted alkyl or alkenyl group.
  • 5 More preferred compounds of this group are of formula (IV) wherein n is 0, R! with
  • A is a C j .g alkyl, C ⁇ . haloalkyl, C 2 _6 alkenyl or C 2 .g haloalkenyl chain, which may be substituted by a halogen or a branch chain which may be halogenated.
  • R 4 and R$ are C 2 .g alkyl or haloalkyl or C _6 alkenyl or haloalkenyl.
  • R 3 is preferably -OH, -O-CO-R 1 1 or -O-CO-O-R 1 ! where R 1 1 is C ⁇ alkyl. Q and most preferably OH.
  • Particularly effective compounds of formula (III) for the use of the invention are those wherein one or more of A, R 4 and R$ includes a haloalkyl or haloalkenyl group, particularly a trifluoromethyl group.
  • Preferred compounds include those where -A-CHR 4 R 5 is an isofluoroalkyl group, eg. such as 2-trifluoromethylpropyl or 2,2-di- trifluoromethylethyl. Both unsubstituted and halogenated compounds have good activity against the aforesaid fungi when the longest chain at the 3 position is up to 7 carbons.
  • a second aspect of the present invention provides novel compounds of formula (I), wherein -CHR 4 R ⁇ forms a 2-substituted cycloalkyl ring, preferably 2-substituted by C j . alkyl or C j _4 haloalkyl; or -(A) m -CHR 4 R* is an isohaloalkyl group.
  • Preferred 2-substituted cycloalkyl compounds such as 2-hydroxy-3-(2-methyl- cyclohexyl)-naphthalene-l,4-dione, are not only novel, but have surprisingly high activity against whitefly as compared to the 3- and 4- substituted cycloalkyl compounds.
  • this aspect of the invention particularly provides a compound of formula (VI)
  • n, m, A, R, R*, R 2 . R 3 , R 7 and R 8 are as defined for general formula (I) and R " is selected from C j _4 alkyl, C j _4 haloalkyl, C 2 _4 alkyl and C _4 haloalkyl.
  • This aspect of the invention further particularly provides a compound of formula (VII)
  • n, m, A, R, R*, R 2 , R 3 , R 7 and R 8 are as defined for general formula (I) and one or more of A, R 4 and R ⁇ is or includes a haloalkyl group.
  • Preferred such compounds have A as a C j _4 alkylene group and one or both of R 4 and R-> is trifluoromethyl.
  • Preferred isohaloalkyl compounds of formula (VI), such as 2-hydroxy-3-(2- trifluoromethylpropyl)-naphthalene-l,4-dione, are not only novel, but have high activity against mites as well as whitefly.
  • a third aspect of the present invention provides a method of combatting whitefly
  • Lepidoptera and/or fungal pests at a locus which comprises treating the locus with a compound of the general formula (I), preferably of general formula (II), (HI) or (IV).
  • the locus comprises the pests, i.e. whitefly, Lepidoptera and/or fungi, per se or environments subject to or subjected to attack by pests. More preferably, the locus comprises the pests per se, stored food material, plants or animals subject to or subjected to attack by pests, seeds of such plants or the medium in which such plants are growing or are to be grown.
  • compounds of formula I may be used in a domestic environment for spraying rooms to combat infestation by houseflies or other insects, acarids or fungi, in a horticultural or agricultural environment for treatment of stored crops, especially cereals, or to spray growing crops such as cotton or rice to combat infestation by pests, particularly whitefly and related species, and in a medical or veterinary environment, for instance, as a cattle spray to prevent or treat infestation the pests.
  • the present invention also provides processes for the preparation of compounds of formula (I) and particularly of formula (II), (III) and (IV) as defined above.
  • n, R and R J are as defined above, is reacted with a carboxylic acid CHR 4 R 5 -(A) m -COOH where R 4 and R 5 are as defined above, in the presence of a free radical initiator, such as ammonium peroxysulphate and silver nitrate in a suitable solvent. such as aqueous acetonitrile, to form a compound of the general formula (I), (II), (III) or (IV).
  • a free radical initiator such as ammonium peroxysulphate and silver nitrate
  • a suitable solvent such as aqueous acetonitrile
  • Compounds of formula (V) are commercially available but in any case may be prepared from corresponding available benzoquinones and substituted alkenes using eg. Diels Alder conditions.
  • the compound of formula (V) is reacted with a compound of formula X-(A) m -CHR 4 R ⁇ wherein R 4 , R- ⁇ A and m are as defined for formula I and X is a leaving group that will leave the compound to give a charged radical + (A) m -CHR R- ⁇ ; eg. X may be a halogen atom or tosyl group.
  • This reaction is carried out in the presence of an acid, eg. a Lewis acid such as aluminium chloride, using conditions broadly as described by Fieser and Gates (J. Am. Chem. Soc. (1941) 63, 2943-2953.
  • the corresponding monobromo-substituted cycloalkyl or cycloalkenyl compounds may be converted to the carboxylates by formation of the Grignard compound using magnesium and then treating this with CO 2 , e.g.. in the form of dry ice.
  • the carboxylic acid so formed may be converted to the alkyl carboxylate by alkylation using, e.g. a compound R"-I, e.g. methyl iodide, in the presence of butyl-lithium, where R ⁇ is a group as defined above that is stable under these conditions.
  • Substitutions, e.g. alkylation, of the cycloalkyl/cycloalkylene ring at positions other than the 1 -position to the carboxylate may be accomplished by methods known to those skilled in the art. Starting from the ring mono-unsaturated cycloalkylene carboxylic alkyl esters, alkylation may be directed at the desired position as previously described and then, using light as initiator, reaction with e.g. CF3X allows introduction of CF3- groups with reduction using palladium carbon catalysis conditions allowing saturation of the unsaturated bond. Many other manipulations will occur to those skilled in the art for the purposes of accessing other compounds of the general formula (I).
  • R J represents a leaving group as defined above
  • R J represents a leaving group as defined above
  • a compound of formula (I) in which R J represents a hydroxyl group with a compound X-L, where X represents a halogen atom, in the presence of an organic base, preferably a tertiary amine such as triethylamine, or an inorganic base such as sodium carbonate.
  • an organic base preferably a tertiary amine such as triethylamine, or an inorganic base such as sodium carbonate.
  • compounds of formula I in which R J represents a group -O-CO-R , where R* * is as defined above may be prepared by acylation of the hydroxy group in a suitable compound of formula I, for instance, by using an acyl chloride R' 1-CO- Cl in a suitable solvent, such as dichloromethane, in the presence of a base, such as triethylamine.
  • a suitable solvent such as dichloromethane
  • a base such as triethylamine
  • a further route to such compounds is provided by reacting a metal salt of a compound of formula (I) in which R 3 represents a hydroxyl group, that is, R 3 represents a group -OM where M is a metal ion, with a compound X-L as defined above.
  • Compounds of formula (I) in which R ⁇ with R 2 and or R 7 with R 8 each independently represent an optionally substituted alkoxy group may be prepared by ketalisation of one or both carbonyl groups in a suitable compound of formula (I) or( V), for instance, by using a suitable alcohol in basic or acidic conditions, such as by use of a solution of potassium hydroxide in methanol.
  • a thiating agent such as Lawesson's Reagent (2,4-bis(4-methoxyphenyl)-l,3-dithia-2,4- diphosphetane-2,4-disulphide
  • an insecticidal and/or fungicidal composition which comprises a compound of formula (I) and preferably of formula (II), (III) or (IV), as defined above, in association with at least one carrier.
  • a composition may contain a single compound or a mixture of several compounds of the present invention. It is also envisaged that different isomers or mixtures of isomers may have different levels or spectra of activity and thus compositions may comprise individual isomers or mixture of isomers.
  • compositions of the invention typically contain from 0.001 to 95% by weight of the active ingredient of formula I.
  • the compositions Preferably contain from 0.001 to 25% by weight of the active ingredient when they are in ready-to-use form.
  • higher concentrations, for instance, up to 95% may be present in compositions to be sold as concentrates for dilution before use.
  • compositions of the invention may be mixed with a variety of appropriate inert carriers such as solvents, diluents and/or surface-active agents to form dusts, granular solids, wettable powders, mosquito coils or other solid preparations or emulsions, emulsifiable concentrates, sprays, aerosols or other liquid preparations.
  • suitable solvents and diluents include water, aliphatic and aromatic hydrocarbons such as xylene or other petroleum fractions and alcohols such as ethanol.
  • Surface-active agents may be of an anionic, cationic or non-ionic type. Anti-oxidants or other stabilisers may also be included as well as perfumes and colourings.
  • inert carriers may be of the type and in proportions such as are conventionally used in pesticidal compositions.
  • These inert carriers may be of the type and in proportions such as are conventionally used in pesticidal compositions and thus are conveniently inert with respect to the physiology of a plant to be treated.
  • Examples of carriers known to be suitable for use in compositions incorporating naphthalene- 1 ,4-diones for pesticidal use include those described in the specifications, and more specifically the Examples, of US 2572946, US 4110473, US 4970328 and JP 90/152943 (the latter to Agro-Kanesho KK).
  • compositions of the invention may also contain one or more further active ingredients.
  • These further active ingredients may be other compounds which exhibit pesticidal activity and these other compounds may exhibit a synergistic effect with the compounds of the present invention.
  • Example 1 The method of Example 1 was followed using lawsone, ie. (2-hydroxynaphthalene- 1,4-dione (1.00 g), and 4-methylcyclohexanecarboxylic acid (1.23 g), and yielded the title compound (100 mg, m.p. 101 °C).
  • lawsone ie. (2-hydroxynaphthalene- 1,4-dione (1.00 g)
  • 4-methylcyclohexanecarboxylic acid (1.23 g
  • Example 2 The method of Example 1 was followed using 2-acetyloxynaphthalene-1.4-dione (1.24 g, 5.74 mmol) and 2-methylpentanoic acid (1.00 g) yielded the title compound (608 mg) after hydrolysis in. 30 ml THF using potassium hydroxide (5 x exess) in water (8ml) (mp 82-83°C). This compound is listed as compound 3 in the Tables below.
  • NB n D signifies refractive index for the sodium D lines; ' - ' indicates absence of a group A
  • Pesticidal activity was assessed against houseflies. mustard beetles, mites and whitefly using the following methods.
  • Houseflies MD1 (Musca domestica) Female flies were treated on the thorax with a one microlitre drop of test compound dissolved in acetone. Two replicates of 15 flies were used at each dose rate and 6 dose rates were used per compound under test. After treatment, the flies were maintained at a temperature of 20° ⁇ 1 °C and kill was assessed 24 and 48 hours after treatment.
  • LD50 values were calculated in micrograms of test compound per fly (see Sawicki et al.. Bulletin of the World Health Organisation. 35. 893 (1966) and Sawicki et al.. Entomologia and Exp. Appli 10, 253, (1967). Mustard beetles (PC. (Phaedon cochleariae Fab)
  • BT Whitefly
  • Acetone solutions (0.100 ml) of the test compounds were placed in 10 ml glass vials and evaporated with rotation to deposit a film of the compound. Thirty adult whiteflies were placed inside the vial, then after 60 minutes, the treated insects were transferred onto untreated cotton leaf discs which were kept moist on a bed of agar gel. The temperature was maintained at 25 °C and mortality assessed after 48 hours. Three replicates were used at each of 5 to 7 dose levels per compound. LC50 values were calculated by using a computer software package ("Polo-PC available from LeOra Software. Berkeley, California). (See M.R. Cahill and B. hackett in Proceedings Brighton Crop Protection Conference, 1992). The test was carried out using a susceptible strain of whitefly (SUD-S) which was collected in Sudan in 1978 from cotton. The results of these tests are set out in Tables 3 and 4 below. The values given are
  • BT. Activity against resistant whitefly
  • the whitefly test on (BT (SUD-S) was repeated using a resistant strain of whitefly (Ned 1/2).
  • the Ned 1/2 strain is a composite collection which was collected in the Netherlands in 1992 from Gerbera and Bouvardia by ICI Netherlands and exhibits high resistance to pyrethroid insecticides, such as cypermethrin, organophosphate and carbamate insecticides and the insect growth regulator buprofezin.
  • Table 5 The result of this test is set out in Table 5 below. The value given ise LC50 (ppm solution of test compound).
  • the presently investigated compounds were also found to have activity against Diabrotica (Western Corn Root worm), and Lepidoptera. eg. Spodoptera eg. S. littoralis and S. frugiperda.
  • Diabrotica Western Corn Root worm
  • Lepidoptera eg. Spodoptera
  • S. littoralis eg. S. littoralis
  • S. frugiperda e.g. S. littoralis and S. frugiperda.
  • Compound 4 has LC50 ppm topical of the order of 5, 10 and 20 for these three species, while Compound 13 has LC50 values of approximately 20, 12 and 20 respectively; Diabrotica. S. littoralis and S. frugiperda.
  • Antifeedant activity is also evident in the species specified.
  • Each compound was incorporated into potato dextrose agar in solvent (50/50 ethanol/acetone) at 0.5 ml solvent per 250 ml agar while the autoclaved agar was still molten and cooled to 50°C. Each compound was tested at a single concentration (100 rag l' 1 ).
  • Each test usually of two compounds, included three control treatments: a standard fungicide (carbendazim at 1 or 5 mg l *1 or prochloraz at 1 mg l '1 ); ethanol/acetone only; no additions.
  • a standard fungicide carbendazim at 1 or 5 mg l *1 or prochloraz at 1 mg l '1
  • ethanol/acetone only no additions.
  • the fungicides used as standards may be considered as representative of active commercially available compounds.
  • Each fungus was tested on agar in four Petri dishes per treatment, with three replicate fungal colonies per plate (one colony for R. solani). A. niger and R. solani were incubated for 4 days at 20-25°C , and P. oryzae for 7 days. Increase in colony diameter was then measured and used to determine activity: The results of these tests are set out in Table 6 below. The values given are % inhibition of growth in colony diameter in agar plates at a given concentration of agent.

Abstract

La présente invention concerne un composé pesticide, ou un de ses sels, utilisé pour lutter contre la mouche blanche, les lépidoptères et certains champignons et représenté par la formule générale (I). Dans cette formule, n représente un entier de 0 à 4; m représente un entier qui est 0 ou 1; chaque R représente indépendamment un atome d'halogène ou un groupe nitro, cyano, hydroxyle, alkyle, alkényle, haloalkyle, haloalkényle, alkoxy, haloalkoxy, haloalkénoxy, amino, alkylamino, dialkylamino, alkoxycarbonyle, carboxyle, alkanoyle, alkhylthio, alkylsulphinyle, alkylsulphonyle, carbamoyle, alkylamido, cycloalkyle, aryle ou aralkyle; R1 et R2 représente chacun, pris indépendamment, un groupe alkoxy éventuellement substitué ou, pris conjointement, un groupe =O, =S, ou =N-OR?9, où R9¿ représente un atome d'hydrogène ou un groupe alkyle éventuellement substitué; R3 représente un groupe hydroxyle, ou un groupe -OL où L est un nucléofuge, ou un groupe qui est transformé in vivo en un groupe -OL1 où L1 est un nucléofuge; R7 et R8 représentent, pris indépendamment, un groupe alkoxy éventuellement substitué ou, pris conjointement, un groupe =O, =S, ou =N-OR?9, où R9¿ est tel que précédemment défini; R4 et R5 représentent, pris indépendamment, un atome halogène ou un groupe alkyle ou alkényle éventuellement substitué, ou, pris conjointement avec l'atome de carbone intermédiaire, représentent un cycle cycloalkyle ou cycloalkényle éventuellement substitué; et A représente un groupe alkyle ou alkényle à chaîne droite ou ramifiée, qui peut être éventuellement substitué, dont une chaîne de carbones acyclique est liée à la position 3 du cycle naphtalène indiqué et à la fraction -CHR4R5 et A ne comporte pas d'atome de carbone quaternaire dans cette chaîne; et le nombre total d'atomes de carbone dans la chaîne de carbones la plus longue démarrant à la position 3 du cycle naphtalène indiqué ne dépasse pas 8.
PCT/GB1996/000041 1995-01-10 1996-01-10 Composes pesticides WO1996021354A1 (fr)

Priority Applications (10)

Application Number Priority Date Filing Date Title
EP96900136A EP0802729A1 (fr) 1995-01-10 1996-01-10 Composes pesticides
PL96321274A PL185703B1 (pl) 1995-01-10 1996-01-10 Nowy związek naftalenowy, sposób jego wytwarzaniai kompozycja grzybobójcza zawierająca ten związek
AU43524/96A AU699685C (en) 1995-01-10 1996-01-10 Pesticidal compounds
CZ972141A CZ214197A3 (en) 1995-01-10 1996-01-10 1,2,3,4-substituted naphthalenes, process of their preparation and their use
JP8521515A JPH10511976A (ja) 1995-01-10 1996-01-10 病害虫防除化合物
BR9606742A BR9606742A (pt) 1995-01-10 1996-01-10 Compostos pesticidas
SK905-97A SK90597A3 (en) 1995-01-10 1996-01-10 Pesticidal compounds
MX9705211A MX9705211A (es) 1995-01-10 1996-01-10 Compuestos pesticidas.
NZ298116A NZ298116A (en) 1995-01-10 1996-01-10 1,2,3,4-substituted naphthalene pesticidal compositions
US08/891,079 US6043286A (en) 1995-01-10 1997-07-10 Pesticidal compounds

Applications Claiming Priority (12)

Application Number Priority Date Filing Date Title
GBGB9500389.3A GB9500389D0 (en) 1995-01-10 1995-01-10 Pesticidal compounds
GBGB9500394.3A GB9500394D0 (en) 1995-01-10 1995-01-10 Pesticidal compounds
GBGB9513594.3A GB9513594D0 (en) 1995-01-10 1995-07-04 Pesticidal compounds
GBGB9513584.4A GB9513584D0 (en) 1995-01-10 1995-07-04 Pesticidal compounds
US109995P 1995-07-13 1995-07-13
US60/001,099 1995-07-13
GB9513584.4 1995-11-13
GB9500394.3 1995-11-13
GBGB9523165.0A GB9523165D0 (en) 1995-11-13 1995-11-13 Pesticidal compounds
GB9500389.3 1995-11-13
GB9513594.3 1995-11-13
GB9523165.0 1995-11-13

Related Child Applications (1)

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JP (1) JPH10511976A (fr)
CA (1) CA2209998A1 (fr)
CZ (1) CZ214297A3 (fr)
HU (1) HUP9702397A3 (fr)
MX (1) MX9705211A (fr)
NZ (1) NZ298116A (fr)
PL (1) PL185703B1 (fr)
SK (1) SK90597A3 (fr)
TR (1) TR199700609T2 (fr)
WO (1) WO1996021354A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1051909A1 (fr) * 1999-05-11 2000-11-15 Sorex Limited Traitement d'animaux nuisibles au moyen de naphtoquinones substituées
WO2008018645A1 (fr) * 2006-08-10 2008-02-14 Korea Research Institute Of Bioscience And Biotechnology Pesticides
WO2009122432A3 (fr) * 2008-03-07 2010-08-26 Alkem Laboratories Ltd. Préparation de composés naphtoquinone en utilisant de la 2,3-dihalonaphtoquinone

Citations (6)

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Publication number Priority date Publication date Assignee Title
US2398418A (en) * 1943-08-27 1946-04-16 Louis F Fieser Introduction of organic radicals into quinones
US2572946A (en) * 1949-11-19 1951-10-30 Du Pont Composition comprising 2-aliphatic-3-hydroxy-1, 4 napthoquinone and method for controlling mites and aphids
DE2520739A1 (de) * 1974-05-10 1975-11-20 Du Pont Pestizid
DE2641343A1 (de) * 1975-09-15 1977-04-07 Du Pont Akarizid und aphizid wirksame 2- hoeheralkyl-3-hydroxy-1,4-naphthochinon- carbonsaeureester
EP0002228A2 (fr) * 1977-11-22 1979-06-13 The Wellcome Foundation Limited Dérivés d'hydroxynaphtochinones, leurs préparations utilisées dans le traitement et la prévention de la theilériose chez le bétail et les moutons; leurs procédés de préparation; dérivés de naphtoquinones
DE3801743A1 (de) * 1987-07-03 1989-01-19 Bayer Ag Schaedlingsbekaempfungsmittel auf basis von substituierten 1,4-naphthochinonen und neue substituierte 1,4-naphthochinone

Patent Citations (8)

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Publication number Priority date Publication date Assignee Title
US2398418A (en) * 1943-08-27 1946-04-16 Louis F Fieser Introduction of organic radicals into quinones
US2572946A (en) * 1949-11-19 1951-10-30 Du Pont Composition comprising 2-aliphatic-3-hydroxy-1, 4 napthoquinone and method for controlling mites and aphids
DE2520739A1 (de) * 1974-05-10 1975-11-20 Du Pont Pestizid
DE2641343A1 (de) * 1975-09-15 1977-04-07 Du Pont Akarizid und aphizid wirksame 2- hoeheralkyl-3-hydroxy-1,4-naphthochinon- carbonsaeureester
FR2323676A1 (fr) * 1975-09-15 1977-04-08 Du Pont Esters d'acides 2-alcoyl superieur-3-hydroxy-1,4 naphthoquinone carboxyliques a proprietes acaricides et aphicides
EP0002228A2 (fr) * 1977-11-22 1979-06-13 The Wellcome Foundation Limited Dérivés d'hydroxynaphtochinones, leurs préparations utilisées dans le traitement et la prévention de la theilériose chez le bétail et les moutons; leurs procédés de préparation; dérivés de naphtoquinones
DE3801743A1 (de) * 1987-07-03 1989-01-19 Bayer Ag Schaedlingsbekaempfungsmittel auf basis von substituierten 1,4-naphthochinonen und neue substituierte 1,4-naphthochinone
EP0300218A1 (fr) * 1987-07-03 1989-01-25 Bayer Ag Utilization de 1,4-naphthochinones substituées comme acaricide et fongicide

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L.F. FIESER ET AL.: "Naphtoquinone antimalarials. II. Correlation of structure and activity against P. lophurae in ducks.", JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, vol. 70, no. 10, 2 November 1948 (1948-11-02), WASHINGTON DC US, pages 3156 - 3165, XP002002276 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1051909A1 (fr) * 1999-05-11 2000-11-15 Sorex Limited Traitement d'animaux nuisibles au moyen de naphtoquinones substituées
WO2008018645A1 (fr) * 2006-08-10 2008-02-14 Korea Research Institute Of Bioscience And Biotechnology Pesticides
WO2009122432A3 (fr) * 2008-03-07 2010-08-26 Alkem Laboratories Ltd. Préparation de composés naphtoquinone en utilisant de la 2,3-dihalonaphtoquinone

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TR199700609T2 (xx) 1999-05-21
AU699685B2 (en) 1998-12-10
HUP9702397A3 (en) 1999-01-28
NZ298116A (en) 1999-11-29
AU4352496A (en) 1996-07-31
PL321274A1 (en) 1997-11-24
EP0802729A1 (fr) 1997-10-29
CA2209998A1 (fr) 1996-07-18
JPH10511976A (ja) 1998-11-17
MX9705211A (es) 1997-10-31
CZ214297A3 (en) 1997-12-17
SK90597A3 (en) 1997-12-10
HUP9702397A2 (hu) 1998-03-30
PL185703B1 (pl) 2003-07-31

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