EP1187818A1 - Pesticidally active tetrazine derivatives - Google Patents

Pesticidally active tetrazine derivatives

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Publication number
EP1187818A1
EP1187818A1 EP00938800A EP00938800A EP1187818A1 EP 1187818 A1 EP1187818 A1 EP 1187818A1 EP 00938800 A EP00938800 A EP 00938800A EP 00938800 A EP00938800 A EP 00938800A EP 1187818 A1 EP1187818 A1 EP 1187818A1
Authority
EP
European Patent Office
Prior art keywords
och
alkyl
formula
och3
cycloalkyl
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP00938800A
Other languages
German (de)
French (fr)
Inventor
Werner Zambach
Rudolf Naef
Stephan Trah
André Jeanguenat
Martin Eberle
Arthur Steiger
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Syngenta Participations AG
Original Assignee
Syngenta Participations AG
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Filing date
Publication date
Application filed by Syngenta Participations AG filed Critical Syngenta Participations AG
Publication of EP1187818A1 publication Critical patent/EP1187818A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member 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
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/713—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with four or more nitrogen atoms as the only ring hetero atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
    • C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D257/08—Six-membered rings

Definitions

  • Pesticidally active tetrazine derivatives are:
  • the present invention relates to compounds of formula
  • X 2 and X 3 are each independently of the other H or F ⁇ ,
  • Ri is halogen, CN, NO 2 , d-C 6 alkyl, C 3 -C 8 cycloalkyl, d-dhaloalkyl, C 3 -C 8 halocycloalkyl d-C 6 alkoxy, C 3 -C 8 cycloalkoxy, d-C 6 haloalkoxy, C 3 -C 8 halocycloalkoxy, d-C 6 alkylth ⁇ o,
  • An is unsubstituted or mono- to tetra-substituted aryl or heteroaryl, the substituents being selected from the group consisting of OH, halogen, CN, NO 2 , C C 6 alkyl, C 3 -C 8 cycloalkyl, d-Cealkyl-d-C ⁇ cycloalkyl, C 3 -C 8 cycloalkyl-d-C 6 alkyl, CrC 6 haloalkyl, C 3 -C 8 halocycloalkyl,
  • Ar 2 is unsubstituted or mono- to penta-substituted aryl or heteroaryl, the substituents being selected from the group consisting of OH, halogen, CN, NO 2 , d-C 6 alkyl, C 3 -C 8 cycloalkyl, d-C 6 alkyl-C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl-d-C 6 alkyl, Ci-Cehaloalkyl, C 3 -C 8 halocycloalkyl,
  • A is a single bond, d-d_.alky.ene, O, O(C C 12 alkylene), S(O) n ,
  • Z is O, NR 4 , NNR 4 R 5 or NOR 4 ;
  • R 2 is H, C ⁇ -C 6 alkyl or C 3 -C 8 cycloalkyl
  • R 9 ⁇ - (CH 2 )m R 3 is Q ⁇ Q ;
  • R 4 and R 5 are each independently of the other H, d-C 6 alkyl or d-C 6 haloalkyl;
  • R 6 is H, d-C 6 alkyl, C 3 -C 8 cycloalkyl, CrC 6 haloalkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, aryl- d-C 6 alkyl, (CH 2 ) p C(O)R 7 or d-C 6 alkoxy-C 2 -C 6 alkyl;
  • R 7 is H, C ⁇ -C 6 alkyl, C 3 -C 8 cycloalkyl, C C 6 haloalkyl, d-C 6 alkoxy, N(R 8 ) 2 or d-C 6 alkoxy-C 2 -C 6 alkyl;
  • R 8 is H, d-C 6 alkyl, C 3 -C 8 cycloalkyl, C C 6 haloalkyl or aryl-C C 6 alkyl;
  • R 9 and R 10 are each independently of the other H or d-C 6 alkyl; m is 1 , 2, 3 or 4; n is O, 1 or 2; p is 0, 1 , 2, 3, 4, 5 or 6; and
  • Q is O or S; with the proviso, that when T-V is -NH-NH-, Xi is halogen, X 2 and X 3 are both hydrogen, Ari and Ar 2 are both phenyl which may be unsubstituted or substituted, A is not a single bond; or, where applicable, a possible E/Z isomer, mixture of E/Z isomers and/or tautomer thereof, in each case in free form or in salt form, to a process for the preparation of those compounds and to the use thereof, to pesticidal compositions in which the active ingredient is selected from those compounds, in each case in free form or in agrochemically acceptable salt form, and to a process for the manufacture of those compositions and to their use.
  • 1,2,4,5-triazine derivatives are proposed in the literature as active ingredients in compositions for controlling pests on domestic animals and productive livestock and in crops of useful plants.
  • the biological properties of those known compounds are not entirely satisfactory in the field of pest control, however, for which reason there is a need to provide further compounds having pesticidal properties, that problem being solved according to the invention by the provision of the present compounds of formula (I).
  • the compounds of formula (I) may be in the form of salts or may form e.g. acid addition salts.
  • the latter are formed, for example, with strong inorganic acids, such as mineral acids, e.g. sulfuric acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxyiic acids, such as unsubstituted or substituted, e.g. halo-substituted, C 1 -C alkanecarboxylic acids, for example acetic acid, saturated or unsaturated dicarboxylic acids, e.g. oxalic, malonic, maleic, fumaric or phthalic acid, hydroxycarboxylic acids, e.g.
  • compounds of formula (I) having at least one acid group may form salts with bases.
  • Suitable salts with bases are, for example, metal salts, such as alkali metal or alkaline earth metal salts, e.g.
  • sodium, potassium or magnesium salts or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, e.g. ethyl-, diethyl-, triethyl- or dimethyl-propyl-amine, or a mono-, di- or tri-hydroxy-lower alkylamine, e.g. mono-, di- or tri-ethanolamine. It may also be possible for corresponding internal salts to be formed. Within the scope of the invention preference is given to agrochemically advantageous salts; also included, however, are other salts, which can be used, for example, for the isolation or purification of free compounds of formula (I) or the agrochemically acceptable salts thereof.
  • any reference to the free compounds of formula (I) or to their salts is to be understood as including also the corresponding salts or the free compounds of formula (I), respectively, as appropriate and expedient.
  • the free form is preferred.
  • carbon-containing groups and compounds each contain from 1 up to and including 6, preferably from 1 up to and including 4, especially 1 or 2, carbon atoms.
  • Aryl is phenyl or naphthyl, preferably phenyl.
  • Heteroaryl is pyridyl, pyrimidyl, s-triazinyl, 1,2,4-triazinyl, thienyl, furanyl, pyrryl, pyrazolyl, imidazolyl, thiazolyl, triazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, benzothienyl, benzofuranyl, benzothiazolyl, indolyl or indazolyl, preferably pyridyl, pyrimidyl, s-triazinyl or 1,2,4-triazinyl, especially pyridyl.
  • Halogen - as a group perse and as a structural element of other groups and compounds, such as haloalkyl, haloalkoxy and haloalkylthio - is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine, more especially fluorine or chlorine.
  • Alkyl - as a group per se and as a structural element of other groups and compounds, such as haloalkyl, alkoxy and alkylthio - is, in each case giving due consideration to the number of carbon atoms contained in the group or compound in question, either straight-chained, i.e. methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, or branched, for example isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.
  • Cycloalkyl - as a group per se and as a structural element of other groups and compounds, such as halocycloalkyl, cycloalkoxy and cycloalkylthio - is, in each case giving due consideration to the number of carbon atoms contained in the group or compound in question, cyclo- propyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
  • Alkenyl - as a group perse and as a structural element of other groups and compounds - is, in each case giving due consideration to the number of carbon atoms and conjugated or isolated double bonds contained in the group or compound in question, either straight- chained, e.g. allyl, 2-butenyl, 3-pentenyl, 1-hexenyl, 1-heptenyl, 1 ,3-hexadienyl or 1 ,3- octadienyl, or branched, e.g. isopropenyl, isobutenyl, isoprenyl, tert-pentenyl, isohexenyl, isoheptenyl or isooctenyl.
  • straight- chained e.g. allyl, 2-butenyl, 3-pentenyl, 1-hexenyl, 1-heptenyl, 1 ,3-hexadienyl or 1 ,3- o
  • Alkynyl - as a group perse and as a structural element of other groups and compounds - is, in each case giving due consideration to the number of carbon atoms and conjugated or isolated double bonds contained in the group or compound in question, either straight- chained, e.g. propargyl, 2-butynyl, 3-pentynyl, 1-hexynyl, 1-heptynyl, 3-hexen-1-ynyl or 1 ,5- heptadien-3-ynyl, or branched, e.g. 3-methylbut-1-ynyl, 4-ethylpent-1-ynyl, 4-methylhex-2- ynyl or 2-methylhept-3-ynyl.
  • straight- chained e.g. propargyl, 2-butynyl, 3-pentynyl, 1-hexynyl, 1-heptynyl, 3-hexen-1-ynyl or 1
  • Halo-substituted carbon-containing groups and compounds such as haloalkyl, haloalkoxy and haloalkylthio, may be partially halogenated or perhalogenated, the halogen substituents in the case of polyhalogenation being the same or different.
  • haloalkyl - as a group per se and as a structural element of other groups and compounds, such as haloalkoxy and haloalkylthio - are methyl substituted from one to three times by fluorine, chlorine and/or bromine, such as CHF 2 or CF 3 ; ethyl substituted from one to five times by fluorine, chlorine and/or bromine, such as CH 2 CF 3 , CF 2 CF 3 , CF 2 CCI 3 , CF 2 CHCI 2 , CF 2 CHF 2 , CF 2 CFCI 2 , CF 2 CHBr 2 , CF 2 CHCIF, CF 2 CHBrF or CCIFCHCIF; propyl or isopropyl substituted from one to seven times by fluorine, chlorine and/or bromine, such as CH 2 CHBrCH 2 Br, CF 2 CHFCF 3 , CH 2 CF 2 CF 3 or CH(CF 3 ) 2 ; butyl or an
  • X 1 is Rf
  • X 2 and X 3 are each independently of the other H or R,;
  • Ri is halogen, CN, NO 2 , C ⁇ -C 6 alkyl, C 3 -C 8 cycloalkyl, d-C 6 haloalkyl, C 3 -C 8 halocycloalkyl,
  • Ar ! is unsubstituted or mono- to tetra-substituted aryl or heteroaryl, the substituents being selected from the group consisting of OH, halogen, CN, NO 2 , d-C 6 alkyl, C 3 -C 8 cycloalkyl, d-C 6 alkyl-C 3 -C 8 cycloalkyl, C 3 -C 8 cycloalkyl-d-C 6 alkyl, d-C 6 haloalkyl, C 3 -C 8 halocycloalkyl, d-C 6 alkoxy, C 3 -C 8 cycloalkoxy, d-C 6 haloalkoxy, C 3 -C 8 halocycloalkoxy, d-C 6 alkylthio,
  • Ar 2 is unsubstituted or mono- to penta-substituted aryl or heteroaryl, the substituents being selected from the group consisting of OH, halogen, CN, NO 2 , d-C 6 alkyl, C 3 -C 8 cycloalkyl, d-Cealkyl-d-C ⁇ cycloalkyl, C 3 -C 8 cycloalkyl-C ⁇ -C 6 alkyI, CrCehaloalkyl, C 3 -C 8 halocycloalkyl,
  • Z is O, NR 4 , NNR 4 R 5 or NOR.,
  • R 2 is H, C ⁇ -C 6 alkyl or C 3 -C 8 cycloalkyl;
  • R 3 is Q Q ;
  • R 4 and R 5 are each independently of the other H, d-C 6 alkyl or C C 6 haloalkyl;
  • R 6 is H, d-C 6 alkyl, C 3 -C 8 cycloalkyl, d-C 6 haloalkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, aryl- d-C ⁇ alkyl, (CH 2 ) p C(O)R 7 or d-C 6 alkoxy-C 2 -C 6 alkyl;
  • R 7 is H, d-C ⁇ alkyl, C 3 -C 8 cycloalkyl, C ⁇ -C 6 haloalkyl, d-C 6 alkoxy, N(R 8 ) 2 or C C 6 alkoxy-
  • R 8 is H, d-C 6 alkyl. C 3 -C 8 cycloalkyl, d-dhaloalkyl or aryl-d-C 6 alkyl;
  • R 9 and R 10 are each independently of the other H or d-C 6 alkyl; m is 1 , 2, 3 or 4; n is 0, 1 or 2; p is 0, 1 , 2, 3, 4, 5 or 6; and Q is O or S.
  • R is halogen, d-C alkyl, C 3 -C 6 cycloalkyl, d-C 4 haloalkyl, d-C 4 alkoxy, C -C 4 haloalkoxy, d-C 4 alkylthio or d-C haloalkylthio; especially halogen, d-C 2 alkyl, d-C 2 haloalkyl, d-C 2 - alkoxy or C C 2 haloalkoxy; more especially fluorine, chlorine, methyl, trifluoromethyl or methoxy;
  • the invention relates also to a process for the preparation of compounds of formula (I), in each case in free form or in salt form, which process comprises, for example, a) reacting a compound of formula
  • the reactants can be reacted with one another as such, that is to say without the addition of a solvent or diluent, for example in the molten state. Generally, however, it is advantageous to add an inert solvent or diluent or a mixture thereof.
  • solvents and diluents include: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, Tetralin, chlorobenzene, dichlorobenzene, bromo- benzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetra- chloromethane, dichloroethane, trichloroethene and tetrachloroethene; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran and di
  • Preferred leaving groups are halogens, tosylates, mesylates and triflates, especially halogens, more especially chlorine and bromine.
  • Suitable basic catalysts are tertiary amines and aza-aromatic compounds, preferably trialkylamines and substituted pyridines, especially triethylamine and 4-dimethylamino- pyridine.
  • Suitable chlorinating agents are (COCI) 2 , SOCI 2 , SO 2 CI 2 , PCI 3 , POCI 3 and PCI 5 , preferably PCI 5 .
  • Suitable oxidising agents are halogens, O 2 and nitrite salts, preferably sodium nitrite.
  • the reactions are advantageously effected in a temperature range of from about 0°C to about +120°C, preferably from about 0°C to about +80°C.
  • a compound of formula (Ila) is reacted with a compound of formula (III) at from about 0° to about 30°, preferably about 10°, in a halogenated hydrocarbon, preferably methylene chloride, in the presence of a basic catalyst mixture, preferably a mixture of triethylamine and 4-dimethylaminopyridine; the resulting product is isolated, reacted with a chlorinating agent, preferably PCI 5 , at from about 80° to about 120°, preferably about 110°, in a halogenated hydrocarbon, preferably chlorobenzene, and the resulting chlorination product is then isolated again and reacted with hydrazine at about from 0° to 40°, preferably 20°, in an ether, preferably tetrahydrofuran; the resulting dihydro- tetrazine derivative is isolated and reacted with an oxidising agent, preferably sodium nitrite, at from about 0° to about
  • an oxidising agent preferably
  • the reactants can be reacted with one another as such, that is to say without the addition of a solvent or diluent, for example in the molten state. Generally, however, it is advantageous to add an inert solvent or diluent or a mixture thereof. Examples of solvents and diluents are given in variant a).
  • Suitable leaving groups, basic catalysts, chlorinating agents and oxidising agents are those mentioned in variant a).
  • Suitable catalysts for the reaction with a compound of formula (V) are palladium complexes, e.g. tetrakis(triphenylphosphine)palladium.
  • a tetrazine derivative is first prepared in accordance with variant a) and is then reacted with a compound of formula (V) at about from 0° to 80°, preferably 50°, in an ether, preferably dimethoxyethane, in the presence of a catalyst, preferably tetrakis(triphenylphosphine)palladium.
  • Salts of compounds of formula (I) can be prepared in a manner known per se. For example, acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchange reagent and salts with bases are obtained by treatment with a suitable base or a suitable ion exchange reagent.
  • Salts of compounds of formula (I) can be converted into the free compounds of formula (I) in customary manner: acid addition salts, for example, by treatment with a suitable basic agent or a suitable ion exchange reagent and salts with bases, for example, by treatment with a suitable acid or a suitable ion exchange reagent.
  • Salts of compounds of formula (I) can be converted in a manner known per se into other salts of compounds of formula (I); for example, acid addition salts can be converted into other acid addition salts, for example by treatment of a salt of an inorganic acid, such as a hydrochloride, with a suitable metal salt, such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt that forms, for example silver chloride, is insoluble and thus precipitates out from the reaction mixture.
  • a salt of an inorganic acid such as a hydrochloride
  • a suitable metal salt such as a sodium, barium or silver salt
  • the compounds of formula (I) that have salt-forming properties may be obtained in free form or in the form of salts.
  • the compounds of formula (I) may also be obtained in the form of their hydrates and/or may include other solvents, for example solvents used for the crystallisation of compounds in solid form.
  • the invention relates to all those forms of the process in which a compound obtainable as starting compound or intermediate at any stage of the process is used as starting material and all or some of the remaining steps are carried out or a starting material is used in the form of a derivative or salt or, especially, is formed under the reaction conditions.
  • the invention relates especially to the processes described in the Preparation Examples.
  • the invention relates also to novel starting materials and intermediates, in each case in free form or in salt form, used according to the invention for the preparation of the compounds of formula (I) and their salts, to the use of those novel starting materials and intermediates and to processes for their preparation.
  • the invention relates especially also to compounds of formula
  • the compounds of formula (I) according to the invention are active ingredients exhibiting valuable preventive and/or curative activity with a very advantageous biocidal spectrum, even at low rates of concentration, while being well tolerated by warmblooded animals, fish and plants.
  • the active ingredients according to the invention are effective against all or individual development stages of normally sensitive animal pests, but also of resistant animal pests, such as insects and representatives of the order Acarina.
  • the insecticidal, ovicidal and/or acaricidal activity of the active ingredients according to the invention may manifest itself directly, i.e. in the mortality of the pests, which occurs immediately or only after some time, for example during moulting, or of their eggs, or indirectly, for example in reduced oviposition and/or hatching rate, good activity corresponding to a mortality of at least 50 to 60 %.
  • the said animal pests include, for example, those mentioned in European Patent Application EP-A-736 252, page 5, line 55, to page 6, line 55.
  • the pests listed therein are therefore included by reference in the subject matter of the present invention.
  • the compounds according to the invention can be used to control, i.e. to inhibit or destroy, pests of the mentioned type occurring especially on plants, more especially on useful plants and ornamentals in agriculture, in horticulture and in forestry, or on parts of such plants, such as the fruits, blossoms, leaves, stems, tubers or roots, while in some cases parts of plants that grow later are still protected against those pests.
  • Target crops include both natural crops and crops that have been modified by breeding or genetic methods, especially cereals, such as wheat, barley, rye, oats, rice, maize and sorghum; beet, such as sugar beet and fodder beet; fruit, e.g. pomes, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries and berries, e.g.
  • strawberries, raspberries and blackberries leguminous plants, such as beans, lentils, peas and soybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil, cocoa and groundnuts; cucurbitaceae, such as marrows, cucumbers and melons; fibre plants, such as cotton, flax, hemp and jute; citrus fruits, such as oranges, lemons, grapefruit and mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes and paprika; lauraceae, such as avocado, cinnamon and camphor; and tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, bananas, natural rubber plants and ornamentals.
  • the compounds according to the invention are especially suitable for controlling insects and representatives of the order Acarina, especially plant-destructive feeding insects, such as Anthonomus grandis, Diabrotica balteata, Heliothis virescens larvae, Plutella xylostella and Spodoptera littoralis larvae, and spider mites, such as Tetranychus spp., in cotton, fruit, citrus, maize, soybean, rape and vegetable crops.
  • plant-destructive feeding insects such as Anthonomus grandis, Diabrotica balteata, Heliothis virescens larvae, Plutella xylostella and Spodoptera littoralis larvae
  • spider mites such as Tetranychus spp., in cotton, fruit, citrus, maize, soybean, rape and vegetable crops.
  • compositions according to the invention are also suitable for protecting plant propagation material, e.g. seed, such as fruits, tubers or grains, or plant cuttings, against fungal infections and animal pests.
  • the propagation material can be treated with the composition before planting: seed, for example, can be dressed before being sown.
  • the active ingredients according to the invention can also be applied to grains (coating), either by impregnating the seeds in a liquid formulation or by coating them with a solid formulation.
  • the composition can also be applied to the planting site when the propagation material is being planted, for example to the seed furrow during sowing.
  • the invention relates also to such methods of treating plant propagation material and to the plant propagation material so treated.
  • Further areas of use of the compounds according to the invention are the protection of stored goods and storerooms and the protection of raw materials, and also in the hygiene sector, especially in the protection of warm-blooded animals, including farm animals, such as cows, pigs, sheep and goats, poultry, such as hens, turkeys and geese, animals bred for their fur, such as mink, foxes, chinchillas, rabbits and the like, and also domestic animals and pets, such as cats and dogs, and even human beings, against pests of the mentioned type.
  • farm animals such as cows, pigs, sheep and goats
  • poultry such as hens, turkeys and geese
  • animals bred for their fur such as mink, foxes, chinchillas, rabbits and the like
  • domestic animals and pets such as cats and dogs, and even human beings, against pests of the mentioned type.
  • flea infestation in domestic animals and pets is a problem for the animal owner for which there is still no adequate solution.
  • none of the known methods of controlling fleas is totally satisfactory, especially since most of the known methods are aimed principally at controlling the fully grown fleas in the coat and take no account at all of the various juvenile stages of the fleas, which live not only in the animal's coat, but also on the floor, on carpets, on the animal's sleeping place, on chairs, in the garden and in all the other places with which the infested animal comes into contact.
  • Flea treatment is generally expensive and must be continued for prolonged periods, success generally being achieved only when the treatment is applied not only to the affected animal, e.g. the dog or cat, but also simultaneously to all the places frequented by the affected animal.
  • the compounds of formula (I) according to the invention can be used alone or in combination with other biocides.
  • biocides for example, in order to enhance the effect they can be combined with pesticides having the same direction of action or in order to broaden the spectrum of activity they can be combined with substances having a different direction of action.
  • the compounds of formula (I) are advantageously combined with substances having endoparasiticidal properties. They can, of course, also be used in combination with anti-bacterial agents.
  • Especially suitable mixing partners are, for example: azamethiphos; chlorfenvinphos; cypermethrin, cypermethrin high-cis; cyromazine; diafenthiuron; diazinon; dichlorvos; dicrotophos; dicyclanil; fenoxycarb; fluazuron; furathiocarb; isazofos; iodofenphos; kinoprene; lufenuron; methacriphos; methidathion; monocrotophos; phosphamidon; profenofos; diofenolan; a substance obtainable from the Bacillus thuringiensis strain GC91 or from NCTC11821; pymetrozine; bromopropylate; methoprene; disulfoton; quinalphos; tau- fluvalinate; thiocyclam; thiometon; aldicarb; azinphos-methyl;
  • the good pesticidal activity of the compounds of formula (I) according to the invention corresponds to a mortality of at least 50-60 % of the mentioned pests.
  • the methods of applying the crop protection agents i.e. the methods for controlling pests of said type, such as spraying, atomizing, dusting, coating, dressing, scattering or pouring (chosen in accordance with the intended objectives and prevailing circumstances), and the use of the compositions for controlling pests of said type are further objects of the invention.
  • Typical concentrations of active ingredient are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm.
  • the compounds of formula (I) are used in unmodified form or, preferably, together with the adjuvants conventionally employed in formulation technology and can therefore be formulated in known manner e.g. into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and also encapsulations in polymer substances.
  • the methods of application such as spraying, atomising, dusting, scattering or pouring, are selected in accordance with the intended objectives and the prevailing circumstances and the invention relates also thereto.
  • compositions, preparations or mixtures comprising the compound (active ingredient) of formula (I), or a combination of that active ingredient with other agrochemical active ingredients and, as appropriate, a solid or liquid adjuvant are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, for example with solvents, solid carriers, and optionally surface-active compounds (surfactants) and the invention relates also thereto.
  • auxiliaries there are used, for example, solid carriers, solvents, stabilisers, "slow release” auxiliaries, dyes and optionally surface-active substances (surfactants).
  • Suitable carriers and auxiliaries include all those substances customarily used in crop protection products.
  • Suitable auxiliaries such as solvents, solid carriers, surface-active compounds, non-ionic surfactants, cationic surfactants, anionic surfactants and other auxiliaries in the compositions used according to the invention, include e.g. those described in EP-A-736 252, page 7, line 51 to page 8, line 39; they are included by reference in the subject matter of the present invention.
  • Suitable anionic surfactants include both so-called water-soluble soaps and water-soluble synthetic surface-active compounds.
  • Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C 10 -C 22 ), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tall oil. Mention may also be made of fatty acid methyltaurine salts as surfactants.
  • the compounds of formula (I) are distinguished inter alia also by excellent activity against fleas, not only adult fleas being rapidly killed but also, by a circuitous route, the juvenile stages of the fleas. Flea larvae hatching out from the flea eggs feed substantially on the excreta of the adult fleas. Since the compounds of formula (I) according to the invention kill the adult fleas very rapidly, the necessary excreta are absent and the juvenile stages are deprived of nutrient medium, so that they perish before reaching the adult stage.
  • the present invention therefore relates preferably to a method of controlling parasites on human beings, domestic animals, productive livestock and pets, wherein an effective amount of a composition comprising at least one compound of formula (I), or a physiologically tolerable salt thereof, is administered systemically or, preferably, topically to the warmblooded animal.
  • the long-term action is achieved by the compounds of formula (I) according to the invention with various forms of administration, for example by administering the active ingredient in a formulated form externally or internally to the animal to be treated.
  • "Formulated" in this case means, for example, in the form of a powder, a tablet or granules, in liposomes or a capsule, in the form of an emulsion, a foam or a spray, in microencapsulated form or in pour-on or spot-on form.
  • all orally administrable compositions comprise, in addition to customary formulation substances, further additives that encourage the host animal to take the composition orally voluntarily, e.g. suitable odorants and flavourings.
  • Percutaneous administration e.g. by subcutaneous or intramuscular injection or as a depot preparation in the form of an implant, and topical application, for example in pour-on or spot- on form, represent preferred subjects of this invention on account of their being easy to carry out.
  • a further mode of administration is oral administration, e.g. in the form of a tablet.
  • Percutaneous and topical forms of administration are of particular interest and give excellent results.
  • Percutaneous forms of administration include, for example, subcutaneous, intramuscular and even intravenous administration of injectable forms.
  • customary syringes with needles it is also possible to use needle-less high-pressure syringe devices.
  • pour-on and spot-on formulations are especially preferred forms of topical administration, but administration in the form of sprays, ointments, solutions or powders may also be expedient.
  • a suitable formulation it is possible to enhance the ability of the active ingredients to penetrate the living tissue of the host animal and/or to maintain their availability. That is important when, for example, more sparingly soluble active ingredients are used, the low solubility of which requires means for enhancing solubility, since in such cases the animal's body fluid is capable of dissolving only small amounts of active ingredients at a time.
  • a compound of formula (I) according to the invention may also be present in a matrix formulation which physically prevents the active ingredient from being released and excreted prematurely and maintains the bioavailability of the active ingredient.
  • a matrix formulation is injected into the body, e.g. intramuscularly or subcutaneously, and remains there as a form of depot from which the active ingredient is released continuously.
  • matrix formulations are known to the person skilled in the art. They are generally wax-like, semi-solid substances, for example vegetable waxes and polyethylene glycols having a high molecular weight, or solid polymer formulations, for example so-called microspheres.
  • the rate of release of the active ingredient from the implant and thus the period of time over which the implant exhibits an action is generally determined by the accuracy with which the implant has been calibrated (amount of active ingredient in the implant), the environment around the implant and the polymer formulation from which the implant has been made.
  • premix in which the active ingredient is dispersed in a liquid or is in finely divided form in solid carriers.
  • That premix can normally comprise about 1 to 800 mg of compound per kg of premix, depending on the desired final concentration in the feed.
  • the compounds of formula (I) according to the invention may be hydrolysed by the constituents of the feed, they should be formulated in a protective matrix, for example in gelatin, before being added to the premix.
  • the present invention accordingly relates also to the aspect of controlling parasites by administering to the host animal with its food a compound of formula (I) that has been protected against hydrolysis.
  • a compound of formula (I) according to the invention is advantageously administered in a dose of from 0.01 to 800 mg/kg, preferably from 0.1 to 200 mg/kg, especially from 0.5 to 30 mg/kg, body weight, based on the host animal.
  • a good dose that can be routinely administered to the host animal is from 0.5 to 100 mg/kg, especially from 0.1 to 40 mg/kg, body weight.
  • the administration is effected at suitable intervals in dependence upon the mode of administration and body weight.
  • the total dose may vary from one species of animal to another and also within a species of animal for the same active ingredient, since it depends inter alia on the weight, age and constitution of the host animal.
  • the compound of formula (I) according to the invention will normally be administered not in pure form but, preferably, in the form of a composition that comprises, in addition to the active ingredient, constituents that assist administration, suitable constituents being those which are tolerated by the host animal. It is of course possible, in addition to controlling the adult parasites in accordance with the invention, also to use conventional methods to control the juvenile stages of the fleas, although the latter is not absolutely essential.
  • compositions to be administered in accordance with the invention generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of a compound of formula (I) according to the invention and from 99.9 to 1 % by weight, especially from 99.9 to 5 % by weight, of a solid or liquid, physiologically tolerable carrier, including from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a non-toxic dispersant.
  • Such formulations may also comprise further auxiliaries, such as stabilisers, antifoams, viscosity regulators, binders and tackifiers as well as other active ingredients for obtaining special effects.
  • auxiliaries such as stabilisers, antifoams, viscosity regulators, binders and tackifiers as well as other active ingredients for obtaining special effects.
  • physiologically tolerable carriers known from veterinary medicinal practice for oral, percutaneous and topical administration can be used as formulation auxiliaries. Some examples are given below.
  • Suitable carriers are especially fillers, such as sugars, e.g. lactose, saccharose, mannitol or sorbitol, cellulose preparations and/or calcium phosphates, for example tricalcium phosphate or calcium hydrogen phosphate, and binders, such as starch pastes using, for example, maize, wheat, rice or potato starch, gelatin, tragacanth, methylcellulose and/or, if desired, disintegrators, such as the above-mentioned starches, also carboxymethyl starch, cross- linked polyvinylpyrrolidone, agar, alginic acid or a salt thereof, such as sodium alginate.
  • fillers such as sugars, e.g. lactose, saccharose, mannitol or sorbitol, cellulose preparations and/or calcium phosphates, for example tricalcium phosphate or calcium hydrogen phosphate
  • binders such as starch pastes using, for example, maize, wheat
  • Adjuvants are especially flow conditioners and lubricants, for example silicic acid, talc, stearic acid or salts thereof, such as magnesium or calcium stearate, and/or polyethylene glycol.
  • Dragee cores can be provided with suitable, optionally enteric, coatings, there being used inter alia concentrated sugar solutions which may comprise gum arabic, talc, polyvinylpyrrolidone, polyethylene glycol and/or titanium dioxide, or coating solutions in suitable organic solvents or solvent mixtures, or, for the preparation of enteric coatings, solutions of suitable cellulose preparations, such as acetylcellulose phthalate or hydroxypropylmethyl- cellulose phthalate. Dyes, flavourings or pigments may be added to the tablets or dragee coatings, for example for identification purposes or to indicate different doses of active ingredient.
  • hard gelatin capsules and also soft sealed capsules made of gelatin and a plasticiser, such as glycerol or sorbitol.
  • the hard gelatin capsules may comprise the active ingredient in the form of granules, for example in admixture with fillers, such as lactose, binders, such as starches, and/or glidants, such as talc or magnesium stearate, and, if desired, stabilisers.
  • the active ingredient is preferably dissolved or suspended in suitable liquids, such as fatty oils, paraffin oil or liquid polyethylene glycols, to which stabilisers may likewise have been added. Preference is given inter alia to capsules that may either easily be bitten through or swallowed without being chewed.
  • the pour-on or spot-on method comprises applying the compound of formula (I) to a locally defined area of the skin or coat, advantageously on the back of the neck or the backbone of the animal. This is carried out, for example, by applying a swab or spray of the pour-on or spot-on formulation to a relatively small area of the coat from where the active ingredient becomes distributed over a wide area of the coat almost automatically as a result of the spreading constituents of the formulation assisted by the movements of the animal.
  • Pour-on and spot-on formulations advantageously comprise carriers that promote rapid distribution over the surface of the skin or in the coat of the host animal and are generally termed spreading oils.
  • suitable oils for example, oily solutions; alcoholic and iso- propanolic solutions, e.g.
  • solutions of 2-octyl dodecanol or oleyl alcohol solutions in esters of monocarboxylic acids, such as isopropyl myristate, isopropyl palmitate, lauric acid oxalic ester, oleic acid oleyl ester, oleic acid decyl ester, hexyl laurate, oleyl oleate, decyl oleate, capric acid esters of saturated fatty alcohols of chain length C 12 -C ⁇ 8 ; solutions of esters of dicarboxylic acids, such as dibutyl phthalate, diisopropyl isophthalate, adipic acid diisopropyl ester, di-n-butyl adipate or solutions of esters of aliphatic acids, e.g.
  • glycols It may be advantageous for a dispersant known from the pharmaceutical or cosmetic industry also to be present.
  • a dispersant known from the pharmaceutical or cosmetic industry also to be present. Examples are pyrrolidin-2-one, N-alkylpyrrolidin-2-one, acetone, polyethylene glycol and its ethers and esters, propylene glycol or synthetic triglycerides.
  • the oily solutions include e.g. vegetable oils, such as olive oil, groundnut oil, sesame oil, pine oil, linseed oil and castor oil.
  • vegetable oils may also be in epoxidised form. It is also possible to use paraffins and silicone oils.
  • a pour-on or spot-on formulation will contain from 1 to 20 % by weight of a compound of formula (I), from 0.1 to 50 % by weight dispersant and from 45 to 98.9 % by weight solvent.
  • the pour-on or spot-on method can be used especially advantageously for herd animals, such as cattle, horses, sheep and pigs, where it is difficult or time-consuming to treat all the animals orally or via injection.
  • this method can of course also be used for all other animals, including individual domestic animals and pets, and is very popular with the keepers of the animals because it can often be carried out without the expert assistance of a veterinary surgeon.
  • Suitable for parenteral and percutaneous administration are oily injection solutions or suspensions, there being used suitable lipophilic solvents or vehicles, such as fatty oils, for example sesame oil, or synthetic fatty acid esters, for example ethyl oleate, or triglycerides, or aqueous injection solutions or suspensions that comprise viscosity-increasing substances, for example sodium carboxymethylcellulose, sorbitol and/or dextran, and, optionally, stabilisers.
  • suitable lipophilic solvents or vehicles such as fatty oils, for example sesame oil, or synthetic fatty acid esters, for example ethyl oleate, or triglycerides
  • aqueous injection solutions or suspensions that comprise viscosity-increasing substances, for example sodium carboxymethylcellulose, sorbitol and/or dextran, and, optionally, stabilisers.
  • preparations of the present invention can be prepared in a manner known perse, for example by means of conventional mixing, granulating, confectioning, dissolving or lyophi- lising processes.
  • pharmaceutical preparations for oral administration can be obtained by combining the active ingredient with solid carriers, optionally granulating the resulting mixture, and processing the mixture or granules, if desired or necessary after the addition of suitable excipients, to form tablets or dragee cores.
  • Preferred formulations have especially the following composition (throughout, percentages are by weight):
  • Emulsifiable concentrates active ingredient: 1 to 90 %, preferably 5 to 20 % surface-active agent: 1 to 30 %, preferably 10 to 20 % liquid carrier: 5 to 94 %, preferably 70 to 85 %
  • Dusts active ingredient: 0.1 to 10 %, preferably 0.1 to 1 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
  • Suspension concentrates active ingredient: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surface-active agent: 1 to 40 %, preferably 2 to 30 %
  • Wettable powders active ingredient: 0.5 to 90 %, preferably 1 to 80 % surface-active agent: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 %
  • Granules active ingredient: 0.5 to 30 %, preferably 3 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
  • Injection solution active ingredient: 0.1 to 10 %, preferably 0.5 to 5 % non-ionic surfactant: 0.1 to 30 %, preferably 0.5 to 10 % mixture of ethanol and propylene glycol: 60 to 99 %, preferably 85 to 90 %
  • Injection suspension aqueous or oily: active ingredient: 0.1 to 20 %, preferably 1 to 10 % non-ionic surfactant: 0.1 to 20 %, preferably 1 to 10 % water or vegetable oil: 60 to 99 %, preferably 85 to 95 %
  • compositions may also comprise further ingredients, such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), anti- foams, e.g. silicone oil, preservatives, viscosity regulators, binders and tackifiers as well as fertilisers or other active ingredients for obtaining special effects.
  • stabilisers e.g. vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil)
  • anti- foams e.g. silicone oil, preservatives, viscosity regulators, binders and tackifiers as well as fertilisers or other active ingredients for obtaining special effects.
  • Example 1 3-(4'-Chlorobiphenyl-4-yl)-6-(2,6-difluorophenyl)-1 ,2-dihvdro ⁇ ,2,4.51tetrazine a) 6.1 g of 4-bromobenzoic acid ethyl ester and 1.84 g of tetrakis(triphenylphosphine)- palladium are stirred in 140 ml of dimethoxyethane at room temperature for 1 h. 140 ml of 2M sodium carbonate solution and 5.0 g of 4-chlorophenylboronic acid are then added.

Abstract

The invention relates to compounds of general formula (I), wherein T-V is -N=N- or -NH-NH-; X1 is R1; X2 and X3 are each independently of the other H or R1; R1 is for instance halogen, CN, NO2, C1-C6alkyl, C3-C8cycloalkyl, C1-C6haloalkyl, C3-C8halocycloalkyl, C1-C6alkoxy, C3-C8cycloalkoxy or C1-C6haloalkoxy; Ar1 is unsubstituted or mono- to tetra-substituted aryl or heteroaryl; Ar2 is unsubstituted or mono- to penta-substituted aryl or heteroaryl; A is a single bond, C1-C12alkylene, O, O(C1-C12alkylene), S(O)n, S(O)n(C1-C12alkylene), C2-C8alkenylene, C2-C8alkynylene; NR6, NR6(C1-C12alkylene) or C(=Z); Z is O, NR4, NNR4R5 or NOR4; R2 is H, C1-C6alkyl or C3-C8cycloalkyl; R4 and R5 are each independently of the other H, C1-C6alkyl or C1-C6haloalkyl; R6 is H, C1-C6alkyl, C3-C8cycloalkyl, C1-C6haloalkyl, C2-C8alkenyl, C2-C8alkynyl, aryl-C1-C6alkyl, (CH2)pC(O)R7 or C1-C6alkoxy-C2-C6alkyl; R7 is H, C1-C6alkyl, C3-C8cycloalkyl, C1-C6haloalkyl, C1-C6alkoxy, N(R8)2 or C1-C6alkoxy-C2-C6alkyl; R8 is H, C1-C6alkyl, C3-C8cycloalkyl, C1-C6haloalkyl or aryl-C1-C6alkyl; n is 0, 1 or 2; p is 0, 1, 2, 3, 4, 5, or 6; and Q is O or S; a process for the preparation of those compounds and their use; pesticides, the active ingredient of which is selected from those compounds; and a method of preparing those compositions and their use; intermediates in the preparation of those compounds; and a process for the preparation of those intermediates and their use.

Description

Pesticidally active tetrazine derivatives
The present invention relates to compounds of formula
wherein
T-V ιs -N=N- or -NH-NH-,
X2 and X3 are each independently of the other H or F^ ,
Ri is halogen, CN, NO2, d-C6alkyl, C3-C8cycloalkyl, d-dhaloalkyl, C3-C8halocycloalkyl d-C6alkoxy, C3-C8cycloalkoxy, d-C6haloalkoxy, C3-C8halocycloalkoxy, d-C6alkylthιo,
C3-C8cycloalkylthιo, d-C6haloalkylthιo or C3-C8halocycloalkylthιo,
An is unsubstituted or mono- to tetra-substituted aryl or heteroaryl, the substituents being selected from the group consisting of OH, halogen, CN, NO2, C C6alkyl, C3-C8cycloalkyl, d-Cealkyl-d-Cβcycloalkyl, C3-C8cycloalkyl-d-C6alkyl, CrC6haloalkyl, C3-C8halocycloalkyl,
C C6alkoxy, C3-C8cycloalkoxy, d-C6haloalkoxy, C3-C8halocycloalkoxy, d-dalkylthio,
C3-C8cycloalkylthιo, d-C6 aloalkylthιo, C3-C8halocycloalkylthιo, d-Cealkylsulfinyl, C3-C8- cycloalkylsulfinyl, d-C6haloalkyisulfιnyl, C3-C8halocycloalkylsulfιnyl, d-C6alkylsulfonyl,
C3-C8cycloalkylsulfonyl, d-d-haloalkylsulfonyl, C3-C8halocycloalkylsuifonyl, C2-C8alkenyl,
C2-C8alkynyl, d-C6alkylcarbonyl, d-C6alkyl-C(=NOR2) and R3,
Ar2 is unsubstituted or mono- to penta-substituted aryl or heteroaryl, the substituents being selected from the group consisting of OH, halogen, CN, NO2, d-C6alkyl, C3-C8cycloalkyl, d-C6alkyl-C3-C8cycloalkyl, C3-C8cycloalkyl-d-C6alkyl, Ci-Cehaloalkyl, C3-C8halocycloalkyl,
Cι-C6alkoxy, C3-C8cycloalkoxy, d-C6haloalkoxy, C3-C8halocycloalkoxy, d-C6alkylthιo,
C3-C8cycloalkylthιo, d-C6haloalkylthιo, C3-C8halocycloalkylthιo, d-C6alkylsulfιnyl, C3-C8cyc- loalkylsulfinyl, d-dshaloalkylsulfinyl, C3-C8halocycloalkylsulfιnyl, d-C6alkylsulfonyl,
C3-C8cycloalkylsulfonyl, d-d-haloalkylsulfonyl, C3-C8halocycloalkylsulfonyl, C2-C8alkenyl,
C2-C8alkynyl, d-C6alkylcarbonyl, d-C6alkyl-C(=NOR2) and R3,
A is a single bond, d-d_.alky.ene, O, O(C C12alkylene), S(O)n,
S(O)n(d-C12alkylene), C2-C8alkenylene, C2-C8alkynylene, NR6, NR6(d-C12alkylene) or
C(=Z), Z is O, NR4, NNR4R5 or NOR4;
R2 is H, Cι-C6alkyl or C3-C8cycloalkyl;
R9^- (CH2)m R3 is Q^Q ;
Rιo
R4 and R5 are each independently of the other H, d-C6alkyl or d-C6haloalkyl;
R6 is H, d-C6alkyl, C3-C8cycloalkyl, CrC6haloalkyl, C2-C8alkenyl, C2-C8alkynyl, aryl- d-C6alkyl, (CH2)pC(O)R7 or d-C6alkoxy-C2-C6alkyl;
R7 is H, Cι-C6alkyl, C3-C8cycloalkyl, C C6haloalkyl, d-C6alkoxy, N(R8)2 or d-C6alkoxy-C2-C6alkyl;
R8 is H, d-C6alkyl, C3-C8cycloalkyl, C C6haloalkyl or aryl-C C6alkyl;
R9 and R10 are each independently of the other H or d-C6alkyl; m is 1 , 2, 3 or 4; n is O, 1 or 2; p is 0, 1 , 2, 3, 4, 5 or 6; and
Q is O or S; with the proviso, that when T-V is -NH-NH-, Xi is halogen, X2 and X3 are both hydrogen, Ari and Ar2 are both phenyl which may be unsubstituted or substituted, A is not a single bond; or, where applicable, a possible E/Z isomer, mixture of E/Z isomers and/or tautomer thereof, in each case in free form or in salt form, to a process for the preparation of those compounds and to the use thereof, to pesticidal compositions in which the active ingredient is selected from those compounds, in each case in free form or in agrochemically acceptable salt form, and to a process for the manufacture of those compositions and to their use.
Certain 1,2,4,5-triazine derivatives are proposed in the literature as active ingredients in compositions for controlling pests on domestic animals and productive livestock and in crops of useful plants. The biological properties of those known compounds are not entirely satisfactory in the field of pest control, however, for which reason there is a need to provide further compounds having pesticidal properties, that problem being solved according to the invention by the provision of the present compounds of formula (I).
The compounds of formula (I) may be in the form of salts or may form e.g. acid addition salts. The latter are formed, for example, with strong inorganic acids, such as mineral acids, e.g. sulfuric acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxyiic acids, such as unsubstituted or substituted, e.g. halo-substituted, C1-C alkanecarboxylic acids, for example acetic acid, saturated or unsaturated dicarboxylic acids, e.g. oxalic, malonic, maleic, fumaric or phthalic acid, hydroxycarboxylic acids, e.g. ascorbic, lactic, malic, tartaric or citric acid, or benzoic acid, or with organic sulfonic acids, such as unsubstituted or substituted, e.g. halo-substituted, d-C4alkane- or aryl-sulfonic acids, e.g. methane- or p- toluene-sulfonic acid. Furthermore, compounds of formula (I) having at least one acid group may form salts with bases. Suitable salts with bases are, for example, metal salts, such as alkali metal or alkaline earth metal salts, e.g. sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, e.g. ethyl-, diethyl-, triethyl- or dimethyl-propyl-amine, or a mono-, di- or tri-hydroxy-lower alkylamine, e.g. mono-, di- or tri-ethanolamine. It may also be possible for corresponding internal salts to be formed. Within the scope of the invention preference is given to agrochemically advantageous salts; also included, however, are other salts, which can be used, for example, for the isolation or purification of free compounds of formula (I) or the agrochemically acceptable salts thereof.
Hereinabove and hereinbelow any reference to the free compounds of formula (I) or to their salts is to be understood as including also the corresponding salts or the free compounds of formula (I), respectively, as appropriate and expedient. The free form is preferred.
The general terms used hereinabove and hereinbelow have the meanings given below, unless defined otherwise.
Unless defined otherwise, carbon-containing groups and compounds each contain from 1 up to and including 6, preferably from 1 up to and including 4, especially 1 or 2, carbon atoms.
Aryl is phenyl or naphthyl, preferably phenyl.
Heteroaryl is pyridyl, pyrimidyl, s-triazinyl, 1,2,4-triazinyl, thienyl, furanyl, pyrryl, pyrazolyl, imidazolyl, thiazolyl, triazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, benzothienyl, benzofuranyl, benzothiazolyl, indolyl or indazolyl, preferably pyridyl, pyrimidyl, s-triazinyl or 1,2,4-triazinyl, especially pyridyl.
Halogen - as a group perse and as a structural element of other groups and compounds, such as haloalkyl, haloalkoxy and haloalkylthio - is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine, more especially fluorine or chlorine.
Alkyl - as a group per se and as a structural element of other groups and compounds, such as haloalkyl, alkoxy and alkylthio - is, in each case giving due consideration to the number of carbon atoms contained in the group or compound in question, either straight-chained, i.e. methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, or branched, for example isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl.
Cycloalkyl - as a group per se and as a structural element of other groups and compounds, such as halocycloalkyl, cycloalkoxy and cycloalkylthio - is, in each case giving due consideration to the number of carbon atoms contained in the group or compound in question, cyclo- propyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
Alkenyl - as a group perse and as a structural element of other groups and compounds - is, in each case giving due consideration to the number of carbon atoms and conjugated or isolated double bonds contained in the group or compound in question, either straight- chained, e.g. allyl, 2-butenyl, 3-pentenyl, 1-hexenyl, 1-heptenyl, 1 ,3-hexadienyl or 1 ,3- octadienyl, or branched, e.g. isopropenyl, isobutenyl, isoprenyl, tert-pentenyl, isohexenyl, isoheptenyl or isooctenyl.
Alkynyl - as a group perse and as a structural element of other groups and compounds - is, in each case giving due consideration to the number of carbon atoms and conjugated or isolated double bonds contained in the group or compound in question, either straight- chained, e.g. propargyl, 2-butynyl, 3-pentynyl, 1-hexynyl, 1-heptynyl, 3-hexen-1-ynyl or 1 ,5- heptadien-3-ynyl, or branched, e.g. 3-methylbut-1-ynyl, 4-ethylpent-1-ynyl, 4-methylhex-2- ynyl or 2-methylhept-3-ynyl.
Alkylene, alkenylene and alkynylene are straight-chained or branched hydrocarbon bridges, especially -CH2-, -CH2-CH2-, -CH(CH3)-, -CH(CH3)CH2-, -CH(CH3)CH2-CH2-, -CH2C(CH3)2-CH2-, -CH=CH-, -CH2-CH=CH-, -CH2-CH=CH-CH2-; -C≡C- and -CH2C-=C-; more especially -CH2-.
Halo-substituted carbon-containing groups and compounds, such as haloalkyl, haloalkoxy and haloalkylthio, may be partially halogenated or perhalogenated, the halogen substituents in the case of polyhalogenation being the same or different. Examples of haloalkyl - as a group per se and as a structural element of other groups and compounds, such as haloalkoxy and haloalkylthio - are methyl substituted from one to three times by fluorine, chlorine and/or bromine, such as CHF2 or CF3; ethyl substituted from one to five times by fluorine, chlorine and/or bromine, such as CH2CF3, CF2CF3, CF2CCI3, CF2CHCI2, CF2CHF2, CF2CFCI2, CF2CHBr2, CF2CHCIF, CF2CHBrF or CCIFCHCIF; propyl or isopropyl substituted from one to seven times by fluorine, chlorine and/or bromine, such as CH2CHBrCH2Br, CF2CHFCF3, CH2CF2CF3 or CH(CF3)2; butyl or an isomer thereof substituted from one to nine times by fluorine, chorine and/or bromine, such as CF(CF3)CHFCF3 or CH2(CF2) 2CF3; pentyl or an isomer thereof substituted from one to eleven times by fluorine, chlorine and/or bromine, such as CF(CF3)(CHF)2CF3 or CH2(CF2)3CF3; and hexyl or an isomer thereof substituted from one to thirteen times by fluorine, chlorine and/or bromine, such as (CH2)4CHBrCH2Br, CF2(CHF)4CF3, CH2(CF2)4CF3 or C(CF3)2(CHF)2CF3.
Preference is given to compounds of formula (I) wherein
X1 is Rf,
X2 and X3 are each independently of the other H or R,;
Ri is halogen, CN, NO2, Cι-C6alkyl, C3-C8cycloalkyl, d-C6haloalkyl, C3-C8halocycloalkyl,
C C6alkoxy, C3-C8cycloalkoxy, d-C6haloalkoxy, C3-C8halocycloalkoxy, d-Cealkylthio,
C3-C8cycloalkylthio, d-C6haloalkylthio or C3-C8halocycloalkylthio;
Ar! is unsubstituted or mono- to tetra-substituted aryl or heteroaryl, the substituents being selected from the group consisting of OH, halogen, CN, NO2, d-C6alkyl, C3-C8cycloalkyl, d-C6alkyl-C3-C8cycloalkyl, C3-C8cycloalkyl-d-C6alkyl, d-C6haloalkyl, C3-C8halocycloalkyl, d-C6alkoxy, C3-C8cycloalkoxy, d-C6haloalkoxy, C3-C8halocycloalkoxy, d-C6alkylthio,
C3-C8cycloalkylthio, d-C6haloalkylthio, C3-C8halocycloalkylthio, d-C6alkylsulfinyl,
C3-C8cycloalkylsulfinyl, d-C6haloalkylsulfιnyl, C3-C8halocycloalkylsulfinyl, d-C6alkylsulfonyl,
C3-C8cycloalkylsulfonyl, d-C6haloalkylsulfonyl, C3-C8halocycloalkylsulfonyl, C2-C8alkenyl,
C2-C8alkynyl, d-C6alkylcarbonyl, d-C6alkyl-C(=NOR2) and R3;
Ar2 is unsubstituted or mono- to penta-substituted aryl or heteroaryl, the substituents being selected from the group consisting of OH, halogen, CN, NO2, d-C6alkyl, C3-C8cycloalkyl, d-Cealkyl-d-Cβcycloalkyl, C3-C8cycloalkyl-Cι-C6alkyI, CrCehaloalkyl, C3-C8halocycloalkyl,
C C6alkoxy, C3-C8cycloalkoxy, d-C6haloalkoxy, C3-C8halocycloalkoxy, d-C6alkylthio,
C3-C8cycloalkylthio, d-Cehaloalkylthio, C3-C8halocycloalkylthio, C C6alkylsulfinyl,
C3-C8cycloalkylsulfinyI, d-C6haloalkylsulfinyl, C3-C8halocycloalkylsulfinyl, d-C6alkylsulfonyl,
C3-C8cycloalkylsulfonyl, d-C6haloalkylsulfonyl, C3-C8halocycloalkylsulfonyl, C2-C8alkenyl,
C2-C8alkynyl, Cι-C6alkylcarbonyl, d-C6alkyl-C(=NOR2) and R3;
A is (CR4R5)P, O(CR R5)p, S(O)n(CR4R5)p, unsubstituted or substituted C2-C8alkenylene, unsubstituted or substituted C2-C8alkynylene, the substituents in each case being selected from the group consisting of R4 and R5l or NR6(CH2)P or C(=Z);
Z is O, NR4, NNR4R5 or NOR.,;
R2 is H, Cι-C6alkyl or C3-C8cycloalkyl; R3 is Q Q ;
R10
R4 and R5 are each independently of the other H, d-C6alkyl or C C6haloalkyl;
R6 is H, d-C6alkyl, C3-C8cycloalkyl, d-C6haloalkyl, C2-C8alkenyl, C2-C8alkynyl, aryl- d-Cβalkyl, (CH2)pC(O)R7 or d-C6alkoxy-C2-C6alkyl;
R7 is H, d-Cβalkyl, C3-C8cycloalkyl, Cι-C6haloalkyl, d-C6alkoxy, N(R8)2 or C C6alkoxy-
C2-C6alkyl;
R8 is H, d-C6alkyl. C3-C8cycloalkyl, d-dhaloalkyl or aryl-d-C6alkyl;
R9 and R10 are each independently of the other H or d-C6alkyl; m is 1 , 2, 3 or 4; n is 0, 1 or 2; p is 0, 1 , 2, 3, 4, 5 or 6; and Q is O or S.
Especially preferred embodiments within the scope of the invention are
(1) a compound of formula (I), wherein X2 is R,;
(2) a compound according to group (1) above of formula (I), wherein X3 is H;
(3) a compound according to anyone of the groups (1) or (2) above of formula (I), wherein R is halogen, d-C alkyl, C3-C6cycloalkyl, d-C4haloalkyl, d-C4alkoxy, C -C4haloalkoxy, d-C4alkylthio or d-C haloalkylthio; especially halogen, d-C2alkyl, d-C2haloalkyl, d-C2- alkoxy or C C2haloalkoxy; more especially fluorine, chlorine, methyl, trifluoromethyl or methoxy;
(4) a compound according to anyone of the groups (1) to (3) above of formula (I), wherein An is unsubstituted or mono- or di-substituted aryl or heteroaryl, the substituents being selected from the group consisting of OH, halogen, CN, NO2, Cι-C4alkyl, C3-C6cycloalkyl, d-dalkyl-d-dcycloalkyl, C3-C6cycloalkyl-d-C alkyl, d-C haloalkyl, C3-C6halocycloalkyl, d-dalkoxy, C3-C6cycloalkoxy, d-dhaloalkoxy, C3-C6halocycloalkoxy, Cι-C alkylthio, C3-C6cycloalkylthio, d-C haloalkylthio, C3-C6halocycloalkylthio, C C4alkylsulfinyl, C3-C5- cycloalkylsulfinyl, d-C4haloalkylsulfinyl, C3-C6halocycloalkylsulfιnyl, d-C alkylsulfonyl, C3-C6cycloalkylsulfonyl, Cι-C haloalkylsulfonyl, C3-C6halocycloalkylsulfonyl, C2-C6alkenyl, C2-C6alkynyl, d-C4alkylcarbonyl, C1-C4alkyl-C(=NOR2) and R3; especially unsubstituted or mono- or di-substituted aryl or heteroaryl, the substituents being selected from the group consisting of OH, halogen, CN, NO2) d-C4alkyl, C3-C6cycloalkyl, CrC4haloalkyl, d-dalkoxy, d-C4haloalkoxy, d-dalkylthio, C C4haloalkylthio, C2-C6alkenyl, C2-C6alkynyl and d-dalkylcarbonyl; more especially unsubstituted or mono-substituted pyridyl or phenyl, the substituents being selected from the group consisting of halogen, d-C4alkyl, d-C4haloalkyl, d-dalkoxy, d-C haloalkoxy, d-C4alkylthio and d-C4haloalkylthio; preferably unsubstituted or mono-substituted phenyl, the substituents being selected from the group consisting of methyl, trifluoromethyl, methoxy, trifluoromethoxy and chlorine; most preferably unsubstituted phenyl;
(5) a compound according to anyone of the groups (1) to (4) above of formula (I), wherein Ar2 is unsubstituted or mono- to tri-substituted aryl or heteroaryl, the substituents being selected from the group consisting of OH, halogen, CN, NO2, Cι-C alkyl, C3-C6cycloalkyl, d-C4alkyl-C3-C4cycloalkyl, C3-C6cycloalkyl-d-C4alkyl, d-C4haloalkyl, C3-C6halocycloalkyl, d-C4alkoxy, C3-C6cycloalkoxy, C C4haloalkoxy, C3-C6halocycloalkoxy, d-dalkylthio, C3-C6cycioalkylthio, C C4haloalkylthio, C3-C6halocycloalkylthio, d-dalkylsulfinyl, C3-C6- cycloalkylsulfinyl, d-C4haloalkylsulfinyl, C3-C6halocycloalkylsulfinyl, d-C4alkylsulfonyl, C3-C6cycloalkylsulfonyl, d-C4haloalkylsulfonyl, C3-C6halocycloalkylsulfonyl, C2-C6alkenyl, C2-C6alkynyl, Cι-C4alkylcarbonyl, C C4alkyl-C(=NOR2) and R3; especially unsubstituted or mono- or di-substituted aryl or heteroaryl, the substituents being selected from the group consisting of OH, halogen, CN, NO2, d-dalkyl, C3-C6cycloalkyl, C C4haloalkyl, d-dalkoxy, d-C haloalkoxy, Cι-C4alkylthio, d-C4haloalkylthio, C2-C6alkenyl, C2-C6alkynyl and d-C alkylcarbonyl; more especially unsubstituted or mono-substituted phenyl, the substituents being selected from the group consisting of halogen, Cι-C alkyl, d-C haloalkyl, d-dalkoxy, d-C4haloalkoxy, d-C alkylthio and d-dhaloalkylthio; most preferably substituted phenyl, the substituents being selected from the group consisting of fluorine, chlorine, d-C4alkyl, trifluoromethyl, methoxy, trifluoromethoxy and methylthio;
(6) a compound according to anyone of the groups (1) to (5) above of formula (I), wherein A is -CH2-, -O-CH2-, C2-C4alkenylene, C2-C4alkynylene or NR3; especially a single bond, -CH2-, O, CH=CH, C≡C or NH; more especially -CH2- or a single bond; very preferably a single bond;
(7) a compound according to anyone of the groups (1) to (6) above of formula (I), wherein Z is O;
(8) a compound according to anyone of the groups (1) to (7) above of formula (I), wherein R2 is H or d-C2alkyl, especially H or methyl;
(9) a compound according to anyone of the groups (1) to (8) above of formula (I), wherein R., and R5 are each independently of the other H or Cι-C2alkyl, especially H or methyl; (10) a compound according to anyone of the groups (1) to (9) above of formula (I), wherein R6 is H, d-dalkyl, C3-C6cycloalkyl or Cι-C4haloalkyi, especially H or d-C2alkyl;
(11) a compound according to anyone of the groups (1) to (10) above of formula (I), wherein n is 0 or 1 ;
(12) a compound according to anyone of the groups (1) to (11) above of formula (I), wherein p is 0, 1 , 2, 3 or 4, especially 0, 1 or 2, more especially 0;
(13) a compound according to anyone of the groups (1) to (12) above of formula (I), wherein X2 is Rύ X3 is H; Ri is halogen, d-C alkyl, C3-C6cycloalkyl, d-C haloalkyl, d-C4alkoxy, d-C4haloalkoxy, d-C alkylthio or d-dhaloalkylthio; Aη is unsubstituted or mono- or di- substituted aryl or heteroaryl, the substituents being selected from the group consisting of OH, halogen, CN, NO2, d-C4alkyl, C3-C6cycloalkyl, d-C4alkyl-C3-C4cycloalkyl, C3-C6- cycloalkyl-d-C4alkyl, Cι-C4haloalkyl, C3-C6halocycloalkyl, d-C4alkoxy, C3-C6cycloalkoxy, d-C haloalkoxy, C3-C6halocycloalkoxy, C1-C4alkylthio, C3-C6cycloalkylthio, C1-C4halo- alkylthio, C3-C6halocycloalkylthio, d-dalkylsulfinyl, C3-C6cycloalkylsulfinyl, d-dhaloalkyl- sulfinyl, C3-C6halocycloalkylsulfinyl, d-dalkylsulfonyl, C3-C6cycloalkylsulfonyl, C -C4halo- alkylsulfonyl, C3-C6halocycloalkylsulfonyl, C2-C6alkenyl, C2-C6alkynyl, d-C alkylcarbonyl, Cι-C4alkyl-C(=NOR2) and R3; Ar2 is unsubstituted or mono- to tri-substituted aryl or heteroaryl, the substituents being selected from the group consisting of OH, halogen, CN, NO2, d-dalkyl, C3-C6cycloalkyl, C C4alkyl-C3-C4cycloalkyl, d-dcycloalkyl-d-dalkyl, d-C4haloalkyl, C3-C6halocycloalkyl, CrC4alkoxy, C3-C6cycloalkoxy, d-C4haloalkoxy, C3-C6halocycloalkoxy, d-dalkylthio, C3-C6cycloalkylthio, d-C4haloalkylthio, C3-C6halo- cycloalkylthio, d-C4alkylsulfinyl, C3-C6cycloalkylsulfinyl, C C4haloalkylsulfinyl, C3-C6halo- cycloalkylsulfinyl, d-dalkylsulfonyl, C3-C6cycloalkylsulfonyl, C C haloalkylsulfonyl, C3-C6halocycloalkylsulfonyl, C2-C6alkenyl, C2-C6alkynyl, d-C alkylcarbonyl, d-dalkyl- C(=NOR2) and R3; and A is a single bond, (CH2), O(CH2), C2-C alkenylene, C2-C4alkynylene or NR3;
(14) a compound according to anyone of the groups (1) to (13) above of formula (I), wherein X2 is R,; X3 is H; R is halogen, d-C2alkyl, C C2haloalkyl, d-C2alkoxy or C C2haloalkoxy; Ar, is unsubstituted or mono- or di-substituted aryl or heteroaryl, the substituents being selected from the group consisting of OH, halogen, CN, NO2, d-dalkyl, C3-C6cycloalkyl, d-dhaloalkyl, d-dalkoxy, d-C4haloalkoxy, d-C4alkylthio, d-dhaloalkylthio, C2-C6alkenyl, C2-C6alkynyl and C C alkylcarbonyl; Ar2 is unsubstituted or mono- or di- substituted aryl or heteroaryl, the substituents being selected from the group consisting of OH, halogen, CN, NO2, d-C4alkyl, C3-C6cycloalkyl, d-C4haloalkyl, d-dalkoxy, d-C4halo- alkoxy, d-C4alkylthio, d-dhaloalkylthio, C2-C6alkenyl, C2-C6alkynyl and Cι-C alkylcarbonyl; and A is a single bond, CH2, O, C≡C, CH=CH or NH;
(15) a compound according to anyone of the groups (1) to (14) above of formula (I), wherein X2 is Rf, X3 is H; R-. is fluorine, chlorine, methyl, trifluoromethyl or methoxy; A is an unsubstituted or mono-substituted pyridyl or phenyl ring, the substituents being selected from the group consisting of halogen, d-C4alkyl, d-C4haloalkyl, C C4alkoxy, d-C4halo- alkoxy, Cι-C4alkylthio and Cι-C4haloalkylthio; Ar2 is unsubstituted or mono-substituted phenyl, the substituents being selected from the group consisting of halogen, d-C4alkyl, d-dhaloalkyl, d-C4alkoxy, C C4haloalkoxy, d-dalkylthio and C C haloalkylthio; and A is a single bond;
(16) a compound according to anyone of the groups (1) to (15) above of formula (I), wherein the group T-V is -N=N-;
(17) a compound according to anyone of the groups (1) to (15) above of formula (I), wherein the group T-V is -NH-NH-;
(18) a compound according to anyone of the groups (1) to (17) above of formula (I), wherein X^ and X2 are halogen and X3 is H; especially X, and X2 are flurorine or chlorine; especially Xi is fluorine and X2 is fluorine or chlorine; particularly X, and X2 are fluorine;
(19) a compound according to anyone of the groups (3) to (17) above of formula (I), wherein XT and X3 are halogen and X2 is H; especially X and X3 are flurorine or chlorine; especially Xi is chlorine and X3 is fluorine or chlorine; particularly X1 is chlorine and X3 is fluorine;
(20) a compound according to anyone of the groups (3) to (17) above of formula (I), wherein Xi is fluorine, X2 is H and X3 is chlorine; in each case including the physiologically tolerable addition compounds.
Within the scope of the invention preference is given especially to the compounds of formula (I) listed in Tables 1 to 5 and more especially to the compounds of formula (I) mentioned in the Synthesis Examples.
The invention relates also to a process for the preparation of compounds of formula (I), in each case in free form or in salt form, which process comprises, for example, a) reacting a compound of formula
which compounds are known or can be prepared analogously to corresponding known compounds and in which X1 ( X2 and X3 are as defined for formula (I) and Q-. is a leaving group, optionally in the presence of a catalyst, with a compound of formula
Q, H2N-HN
^-Ar, — A — Ar2 (Ilia) or V~Arι — A — Ar2 (1Mb), respectively,
O O which compounds are known or can be prepared analogously to corresponding known compounds and in which An, A and Ar2 are as defined for formula (I) and Q-. is a leaving group, reacting the resulting product, optionally after isolation thereof, with a chlorinating agent, reacting the resulting chlorination product, optionally after isolation thereof again, with hydrazine, and reacting the resulting dihydrotetrazine derivative, optionally after isolation thereof again, with an oxidising agent, or b) for the preparation of a compound of formula (I) wherein A is a single bond, reacting in accordance with process a) a compound of formula (II) with a compound of formula
Q, H2N-HN
^Ar— Q2 (Iva) or ^-Arι - Q2 (iVb),
O O which compounds are known or can be prepared analogously to corresponding known compounds and in which An is as defined for formula (I) and d and Q2 are leaving groups, and reacting the resulting product with a compound of formula
OH
Ar2 B (V),
OH which compound is known or can be prepared analogously to corresponding known compounds and in which Ar2 is as defined for formula (I), and in each case, if desired, converting a compound of formula (I), in each case in free form or in salt form, obtainable in accordance with the process or by another method into a different compound of formula (I), separating a mixture of isomers obtainable in accordance with the process and isolating the desired isomer and/or converting a free compound of formula (I) obtainable in accordance with the process into a salt or converting a salt of a compound of formula (I) obtainable in accordance with the process into the free compound of formula (I) or into a different salt.
Variant a):
The reactants can be reacted with one another as such, that is to say without the addition of a solvent or diluent, for example in the molten state. Generally, however, it is advantageous to add an inert solvent or diluent or a mixture thereof. Examples of solvents and diluents include: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, Tetralin, chlorobenzene, dichlorobenzene, bromo- benzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetra- chloromethane, dichloroethane, trichloroethene and tetrachloroethene; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, tetrahydrofuran and dioxane; ketones, such as acetone, methyl ethyl ketone and methyl isobutyl ketone; amides, such as N,N-dimethylformamide, N,N-diethyl- formamide, N,N-dimethylacetamide, N-methylpyrrolidone and hexamethylphosphoric acid triamide; nitriles, such as acetonitrile and propionitrile; and sulfoxides, such as dimethyl sulfoxide.
Preferred leaving groups are halogens, tosylates, mesylates and triflates, especially halogens, more especially chlorine and bromine.
Suitable basic catalysts are tertiary amines and aza-aromatic compounds, preferably trialkylamines and substituted pyridines, especially triethylamine and 4-dimethylamino- pyridine.
Suitable chlorinating agents are (COCI)2, SOCI2, SO2CI2, PCI3, POCI3 and PCI5, preferably PCI5.
Suitable oxidising agents are halogens, O2 and nitrite salts, preferably sodium nitrite.
The reactions are advantageously effected in a temperature range of from about 0°C to about +120°C, preferably from about 0°C to about +80°C.
In a preferred embodiment of variant a), a compound of formula (Ila) is reacted with a compound of formula (III) at from about 0° to about 30°, preferably about 10°, in a halogenated hydrocarbon, preferably methylene chloride, in the presence of a basic catalyst mixture, preferably a mixture of triethylamine and 4-dimethylaminopyridine; the resulting product is isolated, reacted with a chlorinating agent, preferably PCI5, at from about 80° to about 120°, preferably about 110°, in a halogenated hydrocarbon, preferably chlorobenzene, and the resulting chlorination product is then isolated again and reacted with hydrazine at about from 0° to 40°, preferably 20°, in an ether, preferably tetrahydrofuran; the resulting dihydro- tetrazine derivative is isolated and reacted with an oxidising agent, preferably sodium nitrite, at from about 0° to about 80°, preferably about 40°, in a water/acid mixture, preferably water/acetic acid, to form the tetrazine derivative.
Variant b):
The reactants can be reacted with one another as such, that is to say without the addition of a solvent or diluent, for example in the molten state. Generally, however, it is advantageous to add an inert solvent or diluent or a mixture thereof. Examples of solvents and diluents are given in variant a).
Suitable leaving groups, basic catalysts, chlorinating agents and oxidising agents are those mentioned in variant a).
Suitable catalysts for the reaction with a compound of formula (V) are palladium complexes, e.g. tetrakis(triphenylphosphine)palladium.
In a preferred embodiment of variant b), a tetrazine derivative is first prepared in accordance with variant a) and is then reacted with a compound of formula (V) at about from 0° to 80°, preferably 50°, in an ether, preferably dimethoxyethane, in the presence of a catalyst, preferably tetrakis(triphenylphosphine)palladium.
Salts of compounds of formula (I) can be prepared in a manner known per se. For example, acid addition salts of compounds of formula (I) are obtained by treatment with a suitable acid or a suitable ion exchange reagent and salts with bases are obtained by treatment with a suitable base or a suitable ion exchange reagent.
Salts of compounds of formula (I) can be converted into the free compounds of formula (I) in customary manner: acid addition salts, for example, by treatment with a suitable basic agent or a suitable ion exchange reagent and salts with bases, for example, by treatment with a suitable acid or a suitable ion exchange reagent.
Salts of compounds of formula (I) can be converted in a manner known per se into other salts of compounds of formula (I); for example, acid addition salts can be converted into other acid addition salts, for example by treatment of a salt of an inorganic acid, such as a hydrochloride, with a suitable metal salt, such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt that forms, for example silver chloride, is insoluble and thus precipitates out from the reaction mixture.
Depending upon the procedure and reaction conditions, the compounds of formula (I) that have salt-forming properties may be obtained in free form or in the form of salts.
The compounds of formula (I) may also be obtained in the form of their hydrates and/or may include other solvents, for example solvents used for the crystallisation of compounds in solid form.
The invention relates to all those forms of the process in which a compound obtainable as starting compound or intermediate at any stage of the process is used as starting material and all or some of the remaining steps are carried out or a starting material is used in the form of a derivative or salt or, especially, is formed under the reaction conditions.
In the process of the present invention it is preferable to use those starting materials and intermediates which result in the compounds of formula (I) described at the beginning as being especially valuable.
The invention relates especially to the processes described in the Preparation Examples.
The invention relates also to novel starting materials and intermediates, in each case in free form or in salt form, used according to the invention for the preparation of the compounds of formula (I) and their salts, to the use of those novel starting materials and intermediates and to processes for their preparation.
The invention relates especially also to compounds of formula
wherein Xi, X2, X3, Q1 t An, A and Ar2 are as defined above, to the use thereof and to processes for their preparation. Furthermore, the compounds of formula (la) exhibit a spectrum of activity similar to that of compounds of formula (I) and can be used in the same manner. The present invention relates also to the compounds of formula (la) as active ingredients and in respect of their use in agrochemical compositions.
In the area of pest control, the compounds of formula (I) according to the invention are active ingredients exhibiting valuable preventive and/or curative activity with a very advantageous biocidal spectrum, even at low rates of concentration, while being well tolerated by warmblooded animals, fish and plants. The active ingredients according to the invention are effective against all or individual development stages of normally sensitive animal pests, but also of resistant animal pests, such as insects and representatives of the order Acarina. The insecticidal, ovicidal and/or acaricidal activity of the active ingredients according to the invention may manifest itself directly, i.e. in the mortality of the pests, which occurs immediately or only after some time, for example during moulting, or of their eggs, or indirectly, for example in reduced oviposition and/or hatching rate, good activity corresponding to a mortality of at least 50 to 60 %.
The said animal pests include, for example, those mentioned in European Patent Application EP-A-736 252, page 5, line 55, to page 6, line 55. The pests listed therein are therefore included by reference in the subject matter of the present invention.
The compounds according to the invention can be used to control, i.e. to inhibit or destroy, pests of the mentioned type occurring especially on plants, more especially on useful plants and ornamentals in agriculture, in horticulture and in forestry, or on parts of such plants, such as the fruits, blossoms, leaves, stems, tubers or roots, while in some cases parts of plants that grow later are still protected against those pests.
Target crops include both natural crops and crops that have been modified by breeding or genetic methods, especially cereals, such as wheat, barley, rye, oats, rice, maize and sorghum; beet, such as sugar beet and fodder beet; fruit, e.g. pomes, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries and berries, e.g. strawberries, raspberries and blackberries; leguminous plants, such as beans, lentils, peas and soybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil, cocoa and groundnuts; cucurbitaceae, such as marrows, cucumbers and melons; fibre plants, such as cotton, flax, hemp and jute; citrus fruits, such as oranges, lemons, grapefruit and mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes and paprika; lauraceae, such as avocado, cinnamon and camphor; and tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, bananas, natural rubber plants and ornamentals.
The compounds according to the invention are especially suitable for controlling insects and representatives of the order Acarina, especially plant-destructive feeding insects, such as Anthonomus grandis, Diabrotica balteata, Heliothis virescens larvae, Plutella xylostella and Spodoptera littoralis larvae, and spider mites, such as Tetranychus spp., in cotton, fruit, citrus, maize, soybean, rape and vegetable crops.
The compositions according to the invention are also suitable for protecting plant propagation material, e.g. seed, such as fruits, tubers or grains, or plant cuttings, against fungal infections and animal pests. The propagation material can be treated with the composition before planting: seed, for example, can be dressed before being sown. The active ingredients according to the invention can also be applied to grains (coating), either by impregnating the seeds in a liquid formulation or by coating them with a solid formulation. The composition can also be applied to the planting site when the propagation material is being planted, for example to the seed furrow during sowing. The invention relates also to such methods of treating plant propagation material and to the plant propagation material so treated.
Further areas of use of the compounds according to the invention are the protection of stored goods and storerooms and the protection of raw materials, and also in the hygiene sector, especially in the protection of warm-blooded animals, including farm animals, such as cows, pigs, sheep and goats, poultry, such as hens, turkeys and geese, animals bred for their fur, such as mink, foxes, chinchillas, rabbits and the like, and also domestic animals and pets, such as cats and dogs, and even human beings, against pests of the mentioned type.
For example, flea infestation in domestic animals and pets is a problem for the animal owner for which there is still no adequate solution. Owing to the complicated life cycle of the flea, none of the known methods of controlling fleas is totally satisfactory, especially since most of the known methods are aimed principally at controlling the fully grown fleas in the coat and take no account at all of the various juvenile stages of the fleas, which live not only in the animal's coat, but also on the floor, on carpets, on the animal's sleeping place, on chairs, in the garden and in all the other places with which the infested animal comes into contact. Flea treatment is generally expensive and must be continued for prolonged periods, success generally being achieved only when the treatment is applied not only to the affected animal, e.g. the dog or cat, but also simultaneously to all the places frequented by the affected animal.
The compounds of formula (I) according to the invention can be used alone or in combination with other biocides. For example, in order to enhance the effect they can be combined with pesticides having the same direction of action or in order to broaden the spectrum of activity they can be combined with substances having a different direction of action. Where it is desired to extend the spectrum of activity to endoparasites, e.g. worms, the compounds of formula (I) are advantageously combined with substances having endoparasiticidal properties. They can, of course, also be used in combination with anti-bacterial agents.
Especially suitable mixing partners are, for example: azamethiphos; chlorfenvinphos; cypermethrin, cypermethrin high-cis; cyromazine; diafenthiuron; diazinon; dichlorvos; dicrotophos; dicyclanil; fenoxycarb; fluazuron; furathiocarb; isazofos; iodofenphos; kinoprene; lufenuron; methacriphos; methidathion; monocrotophos; phosphamidon; profenofos; diofenolan; a substance obtainable from the Bacillus thuringiensis strain GC91 or from NCTC11821; pymetrozine; bromopropylate; methoprene; disulfoton; quinalphos; tau- fluvalinate; thiocyclam; thiometon; aldicarb; azinphos-methyl; benfuracarb; bifenthrin; buprofezin; carbofuran; dibutylaminothio; cartap; chlorfluazuron; chlorpyrifos; cyfluthrin; lambda-cyhalothrin; alpha-cypermethrin; zeta-cypermethrin; deltamethrin; diflubenzuron; endosulfan; ethiofencarb; fenitrothion; fenobucarb; fenvalerate; formothion; methiocarb; heptenophos; imidacloprid; isoprocarb; methamidophos; methomyl; mevinphos; parathion; parathion-methyl; phosalone; pirimicarb; propoxur; teflubenzuron; terbufos; triazamate; abamectin; fenobucarb; tebufenozide; fipronil; beta-cyfluthrin; silafluofen; fenpyroximate; pyridaben; fenazaquin; pyriproxyfen; pyrimidifen; nitenpyram; NI-25, acetamiprid; avermectin ι (abamectin); an insect-active extract from a plant; a preparation containing insect-active nematodes; a preparation obtainable from Bacillus subtilis; a preparation containing insect- active fungi; a preparation containing insect-active viruses; AC 303 630; acephate; acrinathrin; alanycarb; alphamethrin; amitraz; AZ 60541 ; azinphos A; azinphos M; azo- cyclotin; bendiocarb; bensultap; beta-cyfluthrin; BPMC; brofenprox; bromophos A; bufen- carbe; butocarboxim; butylpyridaben; cadusafos; carbaryl; carbophenothion; chloethocarb; chlorethoxyfos; chlormephos; cis-res-methrin; clocythrin; clofentezine; cyanophos; cyclo- prothrin; cyhexatin; demeton-M; demeton-S; demeton-S-methyl; dichlofenthion; dicliphos; diethion; dimethoate; dimethylvinphos; dioxathion; edifenphos; emamectin; esfenvalerate; ethion; ethofenprox; ethoprophos; etrimphos; fenamiphos; fenbutatin oxide; fenothiocarb; fenpropathrin; fenpyrad; fenthion; fluazinam; flucycloxuron; flucythrinate; flufenoxuron; flufenprox; fonophos; fosthiazate; fubfenprox; HCH; hexaflumuron; hexythiazox; iprobenfos; isofenphos; isoxathion; ivermectin; lambda-cyhalothrin; malathion; mecarbam; mesulfen- phos; metaldehyde; metolcarb; milbemectin; moxidectin; naled; NC 184; omethoate; oxamyl; oxydemethon M; oxydeprofos; permethrin; phenthoate; phorate; phosmet; phoxim; pirimiphos M; pirimiphos A; promecarb; propaphos; prothiofos; prothoate; pyraclophos; pyrida-phenthion; pyresmethrin; pyrethrum; RH 5992; salithion; sebufos; sulfotep; sulprofos; tebufenpyrad; tebupirimphos; tefluthrin; temephos; terbam; tetrachlorvinphos; thiacloprid; thiamethoxam; thiafenox; thiodicarb; thiofanox; thionazin; thuringiensin; tralomethrin; triarathen; triazophos; triazuron; trichlorfon; triflumuron; trimethacarb; vamidothion; xylylcarb; Yl 5301/5302; zetamethrin; DPX-MP062; RH-2485; D 2341 or XMC (3,5-xylyl methyl- carbamate).
The good pesticidal activity of the compounds of formula (I) according to the invention corresponds to a mortality of at least 50-60 % of the mentioned pests.
The methods of applying the crop protection agents, i.e. the methods for controlling pests of said type, such as spraying, atomizing, dusting, coating, dressing, scattering or pouring (chosen in accordance with the intended objectives and prevailing circumstances), and the use of the compositions for controlling pests of said type are further objects of the invention. Typical concentrations of active ingredient are between 0.1 and 1000 ppm, preferably between 0.1 and 500 ppm. The rates of application are generally 1 to 2000 g of active ingredient (a.i.) per hectare (ha = approximately 2.471 acres), especially 10 to 1000 g a.i./ha, and preferably 20 to 600 g a.i./ha.
The compounds of formula (I) are used in unmodified form or, preferably, together with the adjuvants conventionally employed in formulation technology and can therefore be formulated in known manner e.g. into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules, and also encapsulations in polymer substances. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, scattering or pouring, are selected in accordance with the intended objectives and the prevailing circumstances and the invention relates also thereto.
The formulations, that is to say the compositions, preparations or mixtures comprising the compound (active ingredient) of formula (I), or a combination of that active ingredient with other agrochemical active ingredients and, as appropriate, a solid or liquid adjuvant, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with extenders, for example with solvents, solid carriers, and optionally surface-active compounds (surfactants) and the invention relates also thereto.
As formulation auxiliaries there are used, for example, solid carriers, solvents, stabilisers, "slow release" auxiliaries, dyes and optionally surface-active substances (surfactants). Suitable carriers and auxiliaries include all those substances customarily used in crop protection products. Suitable auxiliaries, such as solvents, solid carriers, surface-active compounds, non-ionic surfactants, cationic surfactants, anionic surfactants and other auxiliaries in the compositions used according to the invention, include e.g. those described in EP-A-736 252, page 7, line 51 to page 8, line 39; they are included by reference in the subject matter of the present invention.
Suitable anionic surfactants include both so-called water-soluble soaps and water-soluble synthetic surface-active compounds.
Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C10-C22), e.g. the sodium or potassium salts of oleic or stearic acid, or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tall oil. Mention may also be made of fatty acid methyltaurine salts as surfactants.
More frequently, however, so-called synthetic surfactants are used, as mentioned in EP-A-736 252, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives and alkylarylsulfonates.
The compounds of formula (I) are distinguished inter alia also by excellent activity against fleas, not only adult fleas being rapidly killed but also, by a circuitous route, the juvenile stages of the fleas. Flea larvae hatching out from the flea eggs feed substantially on the excreta of the adult fleas. Since the compounds of formula (I) according to the invention kill the adult fleas very rapidly, the necessary excreta are absent and the juvenile stages are deprived of nutrient medium, so that they perish before reaching the adult stage.
The present invention therefore relates preferably to a method of controlling parasites on human beings, domestic animals, productive livestock and pets, wherein an effective amount of a composition comprising at least one compound of formula (I), or a physiologically tolerable salt thereof, is administered systemically or, preferably, topically to the warmblooded animal.
The long-term action is achieved by the compounds of formula (I) according to the invention with various forms of administration, for example by administering the active ingredient in a formulated form externally or internally to the animal to be treated. "Formulated" in this case means, for example, in the form of a powder, a tablet or granules, in liposomes or a capsule, in the form of an emulsion, a foam or a spray, in microencapsulated form or in pour-on or spot-on form. It will be understood that all orally administrable compositions comprise, in addition to customary formulation substances, further additives that encourage the host animal to take the composition orally voluntarily, e.g. suitable odorants and flavourings.
Percutaneous administration, e.g. by subcutaneous or intramuscular injection or as a depot preparation in the form of an implant, and topical application, for example in pour-on or spot- on form, represent preferred subjects of this invention on account of their being easy to carry out. A further mode of administration is oral administration, e.g. in the form of a tablet. Percutaneous and topical forms of administration are of particular interest and give excellent results.
Percutaneous forms of administration include, for example, subcutaneous, intramuscular and even intravenous administration of injectable forms. In addition to the customary syringes with needles, it is also possible to use needle-less high-pressure syringe devices.
Pour-on and spot-on formulations are especially preferred forms of topical administration, but administration in the form of sprays, ointments, solutions or powders may also be expedient.
By selection of a suitable formulation, it is possible to enhance the ability of the active ingredients to penetrate the living tissue of the host animal and/or to maintain their availability. That is important when, for example, more sparingly soluble active ingredients are used, the low solubility of which requires means for enhancing solubility, since in such cases the animal's body fluid is capable of dissolving only small amounts of active ingredients at a time.
Furthermore, in order to obtain a strongly delayed release of active ingredient, a compound of formula (I) according to the invention may also be present in a matrix formulation which physically prevents the active ingredient from being released and excreted prematurely and maintains the bioavailability of the active ingredient. Such a matrix formulation is injected into the body, e.g. intramuscularly or subcutaneously, and remains there as a form of depot from which the active ingredient is released continuously. Such matrix formulations are known to the person skilled in the art. They are generally wax-like, semi-solid substances, for example vegetable waxes and polyethylene glycols having a high molecular weight, or solid polymer formulations, for example so-called microspheres.
The rate of release of the active ingredient from the implant and thus the period of time over which the implant exhibits an action is generally determined by the accuracy with which the implant has been calibrated (amount of active ingredient in the implant), the environment around the implant and the polymer formulation from which the implant has been made.
The administration of veterinary medicinal additives to animal feed is well known in the field of animal health. It is usual first to prepare a so-called premix in which the active ingredient is dispersed in a liquid or is in finely divided form in solid carriers. That premix can normally comprise about 1 to 800 mg of compound per kg of premix, depending on the desired final concentration in the feed.
Since the compounds of formula (I) according to the invention may be hydrolysed by the constituents of the feed, they should be formulated in a protective matrix, for example in gelatin, before being added to the premix.
The present invention accordingly relates also to the aspect of controlling parasites by administering to the host animal with its food a compound of formula (I) that has been protected against hydrolysis.
A compound of formula (I) according to the invention is advantageously administered in a dose of from 0.01 to 800 mg/kg, preferably from 0.1 to 200 mg/kg, especially from 0.5 to 30 mg/kg, body weight, based on the host animal.
A good dose that can be routinely administered to the host animal is from 0.5 to 100 mg/kg, especially from 0.1 to 40 mg/kg, body weight. The administration is effected at suitable intervals in dependence upon the mode of administration and body weight.
The total dose may vary from one species of animal to another and also within a species of animal for the same active ingredient, since it depends inter alia on the weight, age and constitution of the host animal.
When used according to the invention, the compound of formula (I) according to the invention will normally be administered not in pure form but, preferably, in the form of a composition that comprises, in addition to the active ingredient, constituents that assist administration, suitable constituents being those which are tolerated by the host animal. It is of course possible, in addition to controlling the adult parasites in accordance with the invention, also to use conventional methods to control the juvenile stages of the fleas, although the latter is not absolutely essential.
Such compositions to be administered in accordance with the invention generally comprise from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of a compound of formula (I) according to the invention and from 99.9 to 1 % by weight, especially from 99.9 to 5 % by weight, of a solid or liquid, physiologically tolerable carrier, including from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a non-toxic dispersant.
Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations.
Such formulations may also comprise further auxiliaries, such as stabilisers, antifoams, viscosity regulators, binders and tackifiers as well as other active ingredients for obtaining special effects.
The physiologically tolerable carriers known from veterinary medicinal practice for oral, percutaneous and topical administration can be used as formulation auxiliaries. Some examples are given below.
Suitable carriers are especially fillers, such as sugars, e.g. lactose, saccharose, mannitol or sorbitol, cellulose preparations and/or calcium phosphates, for example tricalcium phosphate or calcium hydrogen phosphate, and binders, such as starch pastes using, for example, maize, wheat, rice or potato starch, gelatin, tragacanth, methylcellulose and/or, if desired, disintegrators, such as the above-mentioned starches, also carboxymethyl starch, cross- linked polyvinylpyrrolidone, agar, alginic acid or a salt thereof, such as sodium alginate. Adjuvants are especially flow conditioners and lubricants, for example silicic acid, talc, stearic acid or salts thereof, such as magnesium or calcium stearate, and/or polyethylene glycol. Dragee cores can be provided with suitable, optionally enteric, coatings, there being used inter alia concentrated sugar solutions which may comprise gum arabic, talc, polyvinylpyrrolidone, polyethylene glycol and/or titanium dioxide, or coating solutions in suitable organic solvents or solvent mixtures, or, for the preparation of enteric coatings, solutions of suitable cellulose preparations, such as acetylcellulose phthalate or hydroxypropylmethyl- cellulose phthalate. Dyes, flavourings or pigments may be added to the tablets or dragee coatings, for example for identification purposes or to indicate different doses of active ingredient.
Other orally administrable preparations are hard gelatin capsules, and also soft sealed capsules made of gelatin and a plasticiser, such as glycerol or sorbitol. The hard gelatin capsules may comprise the active ingredient in the form of granules, for example in admixture with fillers, such as lactose, binders, such as starches, and/or glidants, such as talc or magnesium stearate, and, if desired, stabilisers. In soft capsules, the active ingredient is preferably dissolved or suspended in suitable liquids, such as fatty oils, paraffin oil or liquid polyethylene glycols, to which stabilisers may likewise have been added. Preference is given inter alia to capsules that may either easily be bitten through or swallowed without being chewed.
The pour-on or spot-on method comprises applying the compound of formula (I) to a locally defined area of the skin or coat, advantageously on the back of the neck or the backbone of the animal. This is carried out, for example, by applying a swab or spray of the pour-on or spot-on formulation to a relatively small area of the coat from where the active ingredient becomes distributed over a wide area of the coat almost automatically as a result of the spreading constituents of the formulation assisted by the movements of the animal.
Pour-on and spot-on formulations advantageously comprise carriers that promote rapid distribution over the surface of the skin or in the coat of the host animal and are generally termed spreading oils. There are suitable, for example, oily solutions; alcoholic and iso- propanolic solutions, e.g. solutions of 2-octyl dodecanol or oleyl alcohol; solutions in esters of monocarboxylic acids, such as isopropyl myristate, isopropyl palmitate, lauric acid oxalic ester, oleic acid oleyl ester, oleic acid decyl ester, hexyl laurate, oleyl oleate, decyl oleate, capric acid esters of saturated fatty alcohols of chain length C12-Cι8; solutions of esters of dicarboxylic acids, such as dibutyl phthalate, diisopropyl isophthalate, adipic acid diisopropyl ester, di-n-butyl adipate or solutions of esters of aliphatic acids, e.g. glycols. It may be advantageous for a dispersant known from the pharmaceutical or cosmetic industry also to be present. Examples are pyrrolidin-2-one, N-alkylpyrrolidin-2-one, acetone, polyethylene glycol and its ethers and esters, propylene glycol or synthetic triglycerides.
The oily solutions include e.g. vegetable oils, such as olive oil, groundnut oil, sesame oil, pine oil, linseed oil and castor oil. The vegetable oils may also be in epoxidised form. It is also possible to use paraffins and silicone oils.
Generally a pour-on or spot-on formulation will contain from 1 to 20 % by weight of a compound of formula (I), from 0.1 to 50 % by weight dispersant and from 45 to 98.9 % by weight solvent.
The pour-on or spot-on method can be used especially advantageously for herd animals, such as cattle, horses, sheep and pigs, where it is difficult or time-consuming to treat all the animals orally or via injection. By virtue of its simplicity, this method can of course also be used for all other animals, including individual domestic animals and pets, and is very popular with the keepers of the animals because it can often be carried out without the expert assistance of a veterinary surgeon. Suitable for parenteral and percutaneous administration are oily injection solutions or suspensions, there being used suitable lipophilic solvents or vehicles, such as fatty oils, for example sesame oil, or synthetic fatty acid esters, for example ethyl oleate, or triglycerides, or aqueous injection solutions or suspensions that comprise viscosity-increasing substances, for example sodium carboxymethylcellulose, sorbitol and/or dextran, and, optionally, stabilisers.
The preparations of the present invention can be prepared in a manner known perse, for example by means of conventional mixing, granulating, confectioning, dissolving or lyophi- lising processes. For example, pharmaceutical preparations for oral administration can be obtained by combining the active ingredient with solid carriers, optionally granulating the resulting mixture, and processing the mixture or granules, if desired or necessary after the addition of suitable excipients, to form tablets or dragee cores.
The following Examples serve merely to illustrate the invention and do not limit the invention.
Preferred formulations have especially the following composition (throughout, percentages are by weight):
Emulsifiable concentrates: active ingredient: 1 to 90 %, preferably 5 to 20 % surface-active agent: 1 to 30 %, preferably 10 to 20 % liquid carrier: 5 to 94 %, preferably 70 to 85 %
Dusts: active ingredient: 0.1 to 10 %, preferably 0.1 to 1 % solid carrier: 99.9 to 90 %, preferably 99.9 to 99 %
Suspension concentrates: active ingredient: 5 to 75 %, preferably 10 to 50 % water: 94 to 24 %, preferably 88 to 30 % surface-active agent: 1 to 40 %, preferably 2 to 30 %
Wettable powders: active ingredient: 0.5 to 90 %, preferably 1 to 80 % surface-active agent: 0.5 to 20 %, preferably 1 to 15 % solid carrier: 5 to 95 %, preferably 15 to 90 % Granules: active ingredient: 0.5 to 30 %, preferably 3 to 15 % solid carrier: 99.5 to 70 %, preferably 97 to 85 %
Injection solution: active ingredient: 0.1 to 10 %, preferably 0.5 to 5 % non-ionic surfactant: 0.1 to 30 %, preferably 0.5 to 10 % mixture of ethanol and propylene glycol: 60 to 99 %, preferably 85 to 90 %
Injection suspension (aqueous or oily): active ingredient: 0.1 to 20 %, preferably 1 to 10 % non-ionic surfactant: 0.1 to 20 %, preferably 1 to 10 % water or vegetable oil: 60 to 99 %, preferably 85 to 95 %
The compositions may also comprise further ingredients, such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), anti- foams, e.g. silicone oil, preservatives, viscosity regulators, binders and tackifiers as well as fertilisers or other active ingredients for obtaining special effects.
The following Examples illustrate the invention described above but do not limit the scope thereof in any way. Temperatures are given in degrees Celsius. The symbol 'h' stands for ■hour'.
1. Synthesis Examples
Example 1 : 3-(4'-Chlorobiphenyl-4-yl)-6-(2,6-difluorophenyl)-1 ,2-dihvdroπ ,2,4.51tetrazine a) 6.1 g of 4-bromobenzoic acid ethyl ester and 1.84 g of tetrakis(triphenylphosphine)- palladium are stirred in 140 ml of dimethoxyethane at room temperature for 1 h. 140 ml of 2M sodium carbonate solution and 5.0 g of 4-chlorophenylboronic acid are then added. After being stirred at room temperature for 17 h, the reaction mixture is poured into water and extracted with ethyl acetate; the organic phase is dried with sodium sulfate and concentrated and the crude product is purified by means of flash chromatography. In this way 4'-chlorobiphenyl-4-carboxylic acid ethyl ester is obtained. b) 3.04 g of 2,6-difluorobenzoic acid hydrazide, 2.7 g of triethylamine and 0.11 g of 4-di- methylaminopyridine are introduced into 20 ml of methylene chloride at 5°C and, in the course of 20 min. at 5-10°C, 3.91 g of 4-(4'-chlorophenyl)-benzoyl chloride dissolved in 20 ml of methylene chloride are added dropwise thereto. After being stirred at room temperature for 24 h, the reaction mixture is diluted with methylene chloride and washed with water; the organic phase is dried and concentrated and the residue is recrystallised from ethanol. In this way 4'-chlorobiphenyl-4-carboxylic acid N'-(2,6-difluorobenzoyl)-hydrazide having a melting point of 261-265°C is obtained. c) At 110°C, 6.97 g of phosphorus pentachloride are introduced into 30 ml of dichloro- benzene and, in the course of 15 min., 2.88 g of 4'-chlorobiphenyl-4-carboxylic acid N'-(2,6- difluorobenzoyl)-hydrazide are added in portions thereto. After then being stirred for 2.5 h, the reaction mixture is concentrated and the residue is suspended in methanol and filtered. In this way N-[chloro-(4'-chlorobiphenyl-4-yl)-methylidene]-N'-[chloro-(2,6-difluorophenyl)- methylidenej-hydrazine having a melting point of 149-161 °C is obtained in the form of an E/Z mixture. d) 2.2 g of N-[chloro-(4'-chlorobiphenyl-4-yl)-methylidene]-N'-[chloro-(2,6-difluorophenyl)- methylidenej-hydrazine are added, in portions, at 15-20°C to 22 ml of hydrazine (0.5 molar) in THF and stirring is carried out at room temperature for 45 h. The reaction mixture is then poured into water and the precipitated crystals are filtered and washed with water. Recrystal- lisation from ethyl acetate yields the title compound having a melting point of 242-248°C.
Example 2: 3-(4'-Chlorobiphenyl-4-yl)-6-(2,6-difluorophenyl)-π .2.4.51tetrazine
At 40°C, 500 mg of 3-(4'-chlorobiphenyl-4-yl)-6-(2,6-difluorophenyl)-1,2-dihydro[1, 2,4,5]- tetrazine are introduced into 12 ml of acetic acid and 0.25 ml of water; 90 mg of sodium nitrite are added and stirring is carried out at room temperature for 5 h. After filtration, the crude product is suspended first in diethyl ether and then in ethyl acetate. In this way, the title compound having a melting point of 230-232°C is obtained.
Example 3: 3-(4'-Trifluoromethylbiphenyl-4-yl)-6-(2,6-difluorophenyl)-f 1 ,2,4,51tetrazine
At room temperature, 0.5 g of 3-(4-bromophenyl)-6-(2,6-difluorophenyl)-[1,2,4,5]tetrazine, 0.3 g of 4-trifluoromethylphenylboronic acid and 0.44 g of caesium fluoride are placed in 11 ml of dimethoxyethane and 11 ml of methanol. After the addition of 19.3 mg of palladium acetate and 54.1 mg of tri-o-tolylphosphine, the reaction mixture is stirred at 50°C for 3 h and is then poured into water and extracted with ethyl acetate; the organic phase is dried and concentrated. The residue is stirred with 20 ml of diethyl ether and filtered off. In this way, the title compound having a melting point of 251-252°C is obtained.
Analogously to the procedures described above it is also possible to prepare the substances listed in the following Tables 1 to 4. The melting point values are given in °C.
Table 1 : Compounds of the formula
No. Xi χ2 Ri R2 Phys. data
1.1 F F H 4-(4-F-Ph)
1.2 F F H 4-(2-CI-Ph)
1.3 F F H 4-(4-CI-Ph) 242-248°
1.4 F F H 4-(3-CF3-Ph)
1.5 F F H 4-(4-CF3-Ph)
1.6 F F H 4-(2-CH3-Ph)
1.7 F F H 4-(3-CH3-Ph)
1.8 F F H 4-(4-CH3-Ph)
1.9 F F H 4-(3-OCF3-Ph)
1.10 F F H 4-(4-OCF3-Ph)
1.11 F F H 4-(4-t-butyl-Ph)
1.12 F F H 4-(2,4-CI2-Ph)
1.13 F F H 4-(3,5-CI2-Ph)
1.14 F F H 4-(2,4-F2-Ph)
1.15 F F H 4-(3,5-F2-Ph)
1.16 F F H 4-(2-CF3-Ph)
1.17 F F H 4-(4-OCH3-Ph)
1.18 F F H 4-(4-SCH3-Ph)
1.19 F F H 4-(3-OCH3-Ph)
1.20 F F H 4-(3-CI-Ph)
1.21 F F H 4-(3,4-CI2-Ph)
1.22 F F H 4-(3-CI-4-F-Ph)
1.23 F Cl H 4-(4-F-Ph) No. Xi X2 R, R2 Phys. data
1.24 F Cl H 4-(2-CI-Ph)
1.25 F Cl H 4-(4-CI-Ph)
1.26 F Cl H 4-(3-CF3-Ph)
1.27 F Cl H 4-(4-CF3-Ph)
1.28 F Cl H 4-(2-CH3-Ph)
1.29 F Cl H 4-(3-CH3-Ph)
1.30 F Cl H 4-(4-CH3-Ph)
1.31 F Cl H 4-(3-OCF3-Ph)
1.32 F Cl H 4-(4-OCF3-Ph)
1.33 F Cl H 4-(4-t-butyl-Ph)
1.34 F Cl H 4-(2,4-CI2-Ph)
1.35 F Cl H 4-(3,5-CI2-Ph)
1.36 F Cl H 4-(2,4-F2-Ph)
1.37 F Cl H 4-(3,5-F2-Ph)
1.38 F Cl H 4-(2-CF3-Ph)
1.39 F Cl H 4-(4-OCH3-Ph)
1.40 F Cl H 4-(4-SCH3-Ph)
1.41 F Cl H 4-(3-OCH3-Ph)
1.42 F Cl H 4-(3-CI-Ph)
1.43 F Cl H 4-(3,4-CI2-Ph)
1.44 F Cl H 4-(3-CI-4-F-Ph)
1.45 Cl Cl H 4-(4-F-Ph)
1.46 Cl Cl H 4-(2-CI-Ph)
1.47 Cl Cl H 4-(4-CI-Ph)
1.48 Cl Cl H 4-(3-CF3-Ph)
1.49 Cl Cl H 4_(4-CF3-Ph)
1.50 Cl Cl H 4-(2-CH3-Ph)
1.51 Cl Cl H 4-(3-CH3-Ph)
1.52 Cl Cl H 4-(4-CH3-Ph)
1.53 Cl Cl H 4-(3-OCF3-Ph)
1.54 Cl Cl H 4-(4-OCF3-Ph)
1.55 Cl Cl H 4-(4-t-butyl-Ph)
1.56 Cl Cl H 4-(2,4-CI2-Ph) No. Xi X2 Ri R2 Phys. data
1.57 Cl Cl H 4-(3,5-CI2-Ph)
1.58 Cl Cl H 4-(2,4-F2-Ph)
1.59 Cl Cl H 4-(3,5-F2-Ph)
1.60 Cl Cl H 4-(2-CF3-Ph)
1.61 Cl Cl H 4-(4-OCH3-Ph)
1.62 Cl Cl H 4-(4-SCH3-Ph)
1.63 Cl Cl H 4-(3-OCH3-Ph)
1.64 Cl Cl H 4-(3-CI-Ph)
1.65 Cl Cl H 4-(3,4-CI2-Ph)
1.66 Cl Cl H 4-(3-CI-4-F-Ph)
1.67 F F H 3-(4-F-Ph)
1.68 F F H 3-(2-CI-Ph)
1.69 F F H 3-(4-CI-Ph)
1.70 F F H 3-(3-CF3-Ph)
1.71 F F H 3-(4-CF3-Ph)
1.72 F F H 3-(2-CH3-Ph)
1.73 F F H 3-(3-CH3-Ph)
1.74 F F H 3-(4-CH3-Ph)
1.75 F F H 3-(3-OCF3-Ph)
1.76 F F H 3-(4-OCF3-Ph)
1.77 F F H 3-(4-t-butyl-Ph)
1.78 F F H 3-(2,4-CI2-Ph)
1.79 F F H 3-(3,5-CI2-Ph)
1.80 F F H 3-(2,4-F2-Ph)
1.81 F F H 3-(3,5-F2-Ph)
1.82 F F H 3-(2-CF3-Ph)
1.83 F F H 3-(4-OCH3-Ph)
1.84 F F H 3-(4-SCH3-Ph)
1.85 F F H 3-(3-OCH3-Ph)
1.86 F F H 3-(3-CI-Ph)
1.87 F F H 3-(3,4-CI2-Ph)
1.88 F F H 3-(3-CI-4-F-Ph)
1.89 F Cl H 3-(4-F-Ph) No. Xi x2 i R2 Phys. data
1.90 F Cl H 3-(2-CI-Ph)
1.91 F Cl H 3-(4-CI-Ph)
1.92 F Cl H 3-(3-CF3-Ph)
1.93 F Cl H 3-(4-CF3-Ph)
1.94 F Cl H 3-(2-CH3-Ph)
1.95 F Cl H 3-(3-CH3-Ph)
1.96 F Cl H 3-(4-CH3-Ph)
1.97 F Cl H 3-(3-OCF3-Ph)
1.98 F Cl H 3-(4-OCF3-Ph)
1.99 F Cl H 3-(4-t-butyl-Ph)
1.100 F Cl H 3-(2,4-CI2-Ph)
1.101 F Cl H 3-(3,5-CI2-Ph)
1.102 F Cl H 3-(2,4-F2-Ph)
1.103 F Cl H 3-(3,5-F2-Ph)
1.104 F Cl H 3-(2-CF3-Ph)
1.105 F Cl H 3-(4-OCH3-Ph)
1.106 F Cl H 3-(4-SCH3-Ph)
1.107 F Cl H 3-(3-OCH3-Ph)
1.108 F Cl H 3-(3-CI-Ph)
1.109 F Cl H 3-(3,4-CI2-Ph)
1.110 F Cl H 3-(3-CI-4-F-Ph)
1.111 Cl Cl H 3-(4-F-Ph)
1.112 Cl Cl H 3-(2-CI-Ph)
1.113 Cl Cl H 3-(4-CI-Ph)
1.114 Cl Cl H 3-(3-CF3-Ph)
1.115 Cl Cl H 3-(4-CF3-Ph)
1.116 Cl Cl H 3-(2-CH3-Ph)
1.117 Cl Cl H 3-(3-CH3-Ph)
1.118 Cl Cl H 3-(4-CH3-Ph)
1.119 Cl Cl H 3-(3-OCF3-Ph)
1.120 Cl Cl H 3-(4-OCF3-Ph)
1.121 Cl Cl H 3-(4-t-butyl-Ph)
1.122 Cl Cl H 3-(2,4-CI2-Ph) No. Xi χ2 Ri R2 Phys. data
1.123 Cl Cl H 3-(3,5-CI2-Ph)
1.124 Cl Cl H 3-(2,4-F2-Ph)
1.125 Cl Cl H 3-(3,5-F2-Ph)
1.126 Cl Cl H 3-(2-CF3-Ph)
1.127 Cl Cl H 3-(4-OCH3-Ph)
1.128 Cl Cl H 3-(4-SCH3-Ph)
1.129 Cl Cl H 3-(3-OCH3-Ph)
1.130 Cl Cl H 3-(3-CI-Ph)
1.131 Cl Cl H 3-(3,4-CI2-Ph)
1.132 Cl Cl H 3-(3-CI-4-F-Ph)
1.133 F F 2-CH3 4-(4-F-Ph)
1.134 F F 2-CH3 4-(2-CI-Ph)
1.135 F F 2-CH3 4-(4-CI-Ph)
1.136 F F 2-CH3 4-(3-CF3-Ph)
1.137 F F 2-CH3 4-(4-CF3-Ph)
1.138 F F 2-CH3 4-(2-CH3-Ph)
1.139 F F 2-CH3 4-(3-CH3-Ph)
1.140 F F 2-CH3 4-(4-CH3-Ph)
1.141 F F 2-CH3 4-(3-OCF3-Ph)
1.142 F F 2-CH3 4-(4-OCF3-Ph)
1.143 F F 2-CH3 4-(4-t-butyl-Ph)
1.144 F F 2-CH3 4-(2,4-CI2-Ph)
1.145 F F 2-CH3 4-(3,5-CI2-Ph)
1.146 F F 2-CH3 4-(2,4-F2-Ph)
1.147 F F 2-CH3 4-(3,5-F2-Ph)
1.148 F F 2-CH3 4-(2-CF3-Ph)
1.149 F F 2-CH3 4-(4-OCH3-Ph)
1.150 F F 2-CH3 4-(4-SCH3-Ph)
1.151 F F 2-CH3 4-(3-OCH3-Ph)
1.152 F F 2-CH3 4-(3-CI-Ph)
1.153 F F 2-CH3 4-(3,4-CI2-Ph)
1.154 F F 2-CH3 4-(3-CI-4-F-Ph)
1.155 F Cl 2-CH3 4-(4-F-Ph) No. Xi Ri R2 Phys. data
1.156 F Cl 2-CH3 4-(2-CI-Ph)
1.157 F Cl 2-CH3 4-(4-CI-Ph)
1.158 F Cl 2-CH3 4-(3-CF3-Ph)
1.159 F Cl 2-CH3 4-(4-CF3-Ph)
1.160 F Cl 2-CH3 4-(2-CH3-Ph)
1.161 F Cl 2-CH3 4-(3-CH3-Ph)
1.162 F Cl 2-CH3 4-(4-CH3-Ph)
1.163 F Cl 2-CH3 4-(3-OCF3-Ph)
1.164 F Cl 2-CH3 4-(4-OCF3-Ph)
1.165 F Cl 2-CH3 4-(4-t-butyl-Ph)
1.166 F Cl 2-CH3 4-(2,4-CI2-Ph)
1.167 F Cl 2-CH3 4-(3,5-CI2-Ph)
1.168 F Cl 2-CH3 4-(2,4-F2-Ph)
1.169 F Cl 2-CH3 4-(3,5-F2-Ph)
1.170 F Cl 2-CH3 4-(2-CF3-Ph)
1.171 F Cl 2-CH3 4-(4-OCH3-Ph)
1.172 F Cl 2-CH3 4-(4-SCH3-Ph)
1.173 F Cl 2-CH3 4-(3-OCH3-Ph)
1.174 F Cl 2-CH3 4-(3-CI-Ph)
1.175 F Cl 2-CH3 4-(3,4-CI2-Ph)
1.176 F Cl 2-CH3 4-(3-CI-4-F-Ph)
1.177 Cl Cl 2-CH3 4-(4-F-Ph)
1.178 Cl Cl 2-CH3 4-(2-CI-Ph)
1.179 Cl Cl 2-CH3 4-(4-CI-Ph)
1.180 Cl Cl 2-CH3 4-(3-CF3-Ph)
1.181 Cl Cl 2-CH3 4-(4-CF3-Ph)
1.182 Cl Cl 2-CH3 4-(2-CH3-Ph)
1.183 Cl Cl 2-CH3 4-(3-CH3-Ph)
1.184 Cl Cl 2-CH3 4-(4-CH3-Ph)
1.185 Cl Cl 2-CH3 4-(3-OCF3-Ph)
1.186 Cl Cl 2-CH3 4-(4-OCF3-Ph)
1.187 Cl Cl 2-CH3 4-(4-t-butyl-Ph)
1.188 Cl Cl 2-CH3 4-(2,4-CI2-Ph) No. X, X2 R, R2 Phys. data
1.189 Cl Cl 2-CH3 4-(3,5-CI2-Ph)
1.190 Cl Cl 2-CH3 4-(2,4-F2-Ph)
1.191 Cl Cl 2-CH3 4-(3,5-F2-Ph)
1.192 Cl Cl 2-CH3 4-(2-CF3-Ph)
1.193 Cl Cl 2-CH3 4-(4-OCH3-Ph)
1.194 Cl Cl 2-CH3 4-(4-SCH3-Ph)
1.195 Cl Cl 2-CH3 4-(3-OCH3-Ph)
1.196 Cl Cl 2-CH3 4-(3-CI-Ph)
1.197 Cl Cl 2-CH3 4-(3,4-CI2-Ph)
1.198 Cl Cl 2-CH3 4-(3-CI-4-F-Ph)
1.199 F F 2-CH3 3-(4-F-Ph)
1.200 F F 2-CH3 3-(2-CI-Ph)
1.201 F F 2-CH3 3-(4-CI-Ph)
1.202 F F 2-CH3 3-(3-CF3-Ph)
1.203 F F 2-CH3 3-(4-CF3-Ph)
1.204 F F 2-CH3 3-(2-CH3-Ph)
1.205 F F 2-CH3 3-(3-CH3-Ph)
1.206 F F 2-CH3 3-(4-CH3-Ph)
1.207 F F 2-CH3 3-(3-OCF3-Ph)
1.208 F F 2-CH3 3-(4-OCF3-Ph)
1.209 F F 2-CH3 3-(4-t-butyl-Ph)
1.210 F F 2-CH3 3-(2,4-CI2-Ph)
1.211 F F 2-CH3 3-(3,5-CI2-Ph)
1.212 F F 2-CH3 3-(2,4-F2-Ph)
1.213 F F 2-CH3 3-(3,5-F2-Ph)
1.214 F F 2-CH3 3-(2-CF3-Ph)
1.215 F F 2-CH3 3-(4-OCH3-Ph)
1.216 F F 2-CH3 3-(4-SCH3-Ph)
1.217 F F 2-CH3 3-(3-OCH3-Ph)
1.218 F F 2-CH3 3-(3-CI-Ph)
1.219 F F 2-CH3 3-(3,4-CI2-Ph)
1.220 F F 2-CH3 3-(3-CI-4-F-Ph)
1.221 F Cl 2-CH3 3-(4-F-Ph) No. X! χ2 Ri R2 Phys. data
1.222 F Cl 2-CH3 3-(2-CI-Ph)
1.223 F Cl 2-CH3 3-(4-CI-Ph)
1.224 F Cl 2-CH3 3-(3-CF3-Ph)
1.225 F Cl 2-CH3 3-(4-CF3-Ph)
1.226 F Cl 2-CH3 3-(2-CH3-Ph)
1.227 F Cl 2-CH3 3-(3-CH3-Ph)
1.228 F Cl 2-CH3 3-(4-CH3-Ph)
1.229 F Cl 2-CH3 3-(3-OCF3-Ph)
1.230 F Cl 2-CH3 3-(4-OCF3-Ph)
1.231 F Cl 2-CH3 3-(4-t-butyl-Ph)
1.232 F Cl 2-CH3 3-(2,4-CI2-Ph)
1.233 F Cl 2-CH3 3-(3,5-CI2-Ph)
1.234 F Cl 2-CH3 3-(2,4-F2-Ph)
1.235 F Cl 2-CH3 3-(3,5-F2-Ph)
1.236 F Cl 2-CH3 3-(2-CF3-Ph)
1.237 F Cl 2-CH3 3-(4-OCH3-Ph)
1.238 F Cl 2-CH3 3-(4-SCH3-Ph)
1.239 F Cl 2-CH3 3-(3-OCH3-Ph)
1.240 F Cl 2-CH3 3-(3-CI-Ph)
1.241 F Cl 2-CH3 3-(3,4-CI2-Ph)
1.242 F Cl 2-CH3 3-(3-CI-4-F-Ph)
1.243 Cl Cl 2-CH3 3-(4-F-Ph)
1.244 Cl Cl 2-CH3 3-(2-CI-Ph)
1.245 Cl Cl 2-CH3 3-(4-CI-Ph)
1.246 Cl Cl 2-CH3 3-(3-CF3-Ph)
1.247 Cl Cl 2-CH3 3-(4-CF3-Ph)
1.248 Cl Cl 2-CH3 3-(2-CH3-Ph)
1.249 Cl Cl 2-CH3 3-(3-CH3-Ph)
1.250 Cl Cl 2-CH3 3-(4-CH3-Ph)
1.251 Cl Cl 2-CH3 3-(3-OCF3-Ph)
1.252 Cl Cl 2-CH3 3-(4-OCF3-Ph)
1.253 Cl Cl 2-CH3 3-(4-t-butyl-Ph)
1.254 Cl Cl 2-CH3 3-(2,4-CI2-Ph) No. X2 Ri R7 Phys. data
1.255 Cl Cl 2-CH3 3-(3,5-CI2-Ph)
1.256 Cl Cl 2-CH3 3-(2,4-F2-Ph)
1.257 Cl Cl 2-CH3 3-(3,5-F2-Ph)
1.258 Cl Cl 2-CH3 3-(2-CF3-Ph)
1.259 Cl Cl 2-CH3 3-(4-OCH3-Ph)
1.260 Cl Cl 2-CH3 3-(4-SCH3-Ph)
1.261 Cl Cl 2-CH3 3-(3-OCH3-Ph)
1.262 Cl Cl 2-CH3 3-(3-CI-Ph)
1.263 Cl Cl 2-CH3 3-(3,4-CI2-Ph)
1.264 Cl Cl 2-CH3 3-(3-CI-4-F-Ph)
1.265 F F 2-CI 4-(4-F-Ph)
1.266 F F 2-CI 4-(2-CI-Ph)
1.267 F F 2-CI 4-(4-CI-Ph)
1.268 F F 2-CI 4-(3-CF3-Ph)
1.269 F F 2-CI 4-(4-CF3-Ph)
1.270 F F 2-CI 4-(2-CH3-Ph)
1.271 F F 2-CI 4-(3-CH3-Ph)
1.272 F F 2-CI 4-(4-CH3-Ph)
1.273 F F 2-CI 4-(3-OCF3-Ph)
1.274 F F 2-CI 4-(4-OCF3-Ph)
1.275 F F 2-CI 4-(4-t-butyl-Ph)
1.276 F F 2-CI 4-(2,4-CI2-Ph)
1.277 F F 2-CI 4-(3,5-CI2-Ph)
1.278 F F 2-CI 4-(2,4-F2-Ph)
1.279 F F 2-CI 4-(3,5-F2-Ph)
1.280 F F 2-CI 4-(2-CF3-Ph)
1.281 F F 2-CI 4-(4-OCH3-Ph)
1.282 F F 2-CI 4-(4-SCH3-Ph)
1.283 F F 2-CI 4-(3-OCH3-Ph)
1.284 F F 2-CI 4-(3-CI-Ph)
1.285 F F 2-CI 4-(3,4-CI2-Ph)
1.286 F F 2-CI 4-(3-CI-4-F-Ph)
1.287 F Cl 2-CI 4-(4-F-Ph) No. Xi X2 Ri R2 Phys. data
1.288 F Cl 2-CI 4-(2-CI-Ph)
1.289 F Cl 2-CI 4-(4-CI-Ph)
1.290 F Cl 2-CI 4-(3-CF3-Ph)
1.291 F Cl 2-CI 4-(4-CF3-Ph)
1.292 F Cl 2-CI 4-(2-CH3-Ph)
1.293 F Cl 2-CI 4-(3-CH3-Ph)
1.294 F Cl 2-CI 4-(4-CH3-Ph)
1.295 F Cl 2-CI 4-(3-OCF3-Ph)
1.296 F Cl 2-CI 4-(4-OCF3-Ph)
1.297 F Cl 2-CI 4-(4-t-butyl-Ph)
1.298 F Cl 2-CI 4-(2,4-CI2-Ph)
1.299 F Cl 2-CI 4-(3,5-CI2-Ph)
1.300 F Cl 2-CI 4-(2,4-F2-Ph)
1.301 F Cl 2-CI 4-(3,5-F2-Ph)
1.302 F Cl 2-CI 4-(2-CF3-Ph)
1.303 F Cl 2-CI 4-(4-OCH3-Ph)
1.304 F Cl 2-CI 4-(4-SCH3-Ph)
1.305 F Cl 2-CI 4-(3-OCH3-Ph)
1.306 F Cl 2-CI 4-(3-CI-Ph)
1.307 F Cl 2-CI 4-(3,4-CI2-Ph)
1.308 F Cl 2-CI 4-(3-CI-4-F-Ph)
1.309 Cl Cl 2-CI 4-(4-F-Ph)
1.310 Cl Cl 2-CI 4-(2-CI-Ph)
1.311 Cl Cl 2-CI 4-(4-CI-Ph)
1.312 Cl Cl 2-CI 4-(3-CF3-Ph)
1.313 Cl Cl 2-CI 4-(4-CF3-Ph)
1.314 Cl Cl 2-CI 4-(2-CH3-Ph)
1.315 Cl Cl 2-CI 4-(3-CH3-Ph)
1.316 Cl Cl 2-CI 4-(4-CH3-Ph)
1.317 Cl Cl 2-CI 4-(3-OCF3-Ph)
1.318 Cl Cl 2-CI 4-(4-OCF3-Ph)
1.319 Cl Cl 2-CI 4-(4-t-butyl-Ph)
1.320 Cl Cl 2-CI 4-(2,4-CI2-Ph) No. Xi χ2 Ri R2 Phys. data
1.321 Cl Cl 2-CI 4-(3,5-CI2-Ph)
1.322 Cl Cl 2-CI 4-(2,4-F2-Ph)
1.323 Cl Cl 2-CI 4-(3,5-F2-Ph)
1.324 Cl Cl 2-CI 4-(2-CF3-Ph)
1.325 Cl Cl 2-CI 4-(4-OCH3-Ph)
1.326 Cl Cl 2-CI 4-(4-SCH3-Ph)
1.327 Cl Cl 2-CI 4-(3-OCH3-Ph)
1.328 Cl Cl 2-CI 4-(3-CI-Ph)
1.329 Cl Cl 2-CI 4-(3,4-CI2-Ph)
1.330 Cl Cl 2-CI 4-(3-CI-4-F-Ph)
1.331 F F 2-CI 3-(4-F-Ph)
1.332 F F 2-CI 3-(2-CI-Ph)
1.333 F F 2-CI 3-(4-CI-Ph)
1.334 F F 2-CI 3-(3-CF3-Ph)
1.335 F F 2-CI 3-(4-CF3-Ph)
1.336 F F 2-CI 3-(2-CH3-Ph)
1.337 F F 2-CI 3-(3-CH3-Ph)
1.338 F F 2-CI 3-(4-CH3-Ph)
1.339 F F 2-CI 3-(3-OCF3-Ph)
1.340 F F 2-CI 3-(4-OCF3-Ph)
1.341 F F 2-CI 3-(4-t-butyl-Ph)
1.342 F F 2-CI 3-(2,4-CI2-Ph)
1.343 F F 2-CI 3-(3,5-CI2-Ph)
1.344 F F 2-CI 3-(2,4-F2-Ph)
1.345 F F 2-CI 3-(3,5-F2-Ph)
1.346 F F 2-CI 3-(2-CF3-Ph)
1.347 F F 2-CI 3-(4-OCH3-Ph)
1.348 F F 2-CI 3-(4-SCH3-Ph)
1.349 F F 2-CI 3-(3-OCH3-Ph)
1.350 F F 2-CI 3-(3-CI-Ph)
1.351 F F 2-CI 3-(3,4-CI2-Ph)
1.352 F F 2-CI 3-(3-CI-4-F-Ph)
1.353 F Cl 2-CI 3-(4-F-Ph) No. Xi Ri Phys. data
1.354 F Cl 2-CI 3-(2-CI-Ph)
1.355 F Cl 2-CI 3-(4-CI-Ph)
1.356 F Cl 2-CI 3-(3-CF3-Ph)
1.357 F Cl 2-CI 3-(4-CF3-Ph)
1.358 F Cl 2-CI 3-(2-CH3-Ph)
1.359 F Cl 2-CI 3-(3-CH3-Ph)
1.360 F Cl 2-CI 3-(4-CH3-Ph)
1.361 F Cl 2-CI 3-(3-OCF3-Ph)
1.362 F Cl 2-CI 3-(4-OCF3-Ph)
1.363 F Cl 2-CI 3-(4-t-butyl-Ph)
1.364 F Cl 2-CI 3-(2,4-CI2-Ph)
1.365 F Cl 2-CI 3-(3,5-CI2-Ph)
1.366 F Cl 2-CI 3-(2,4-F2-Ph)
1.367 F Cl 2-CI 3-(3,5-F2-Ph)
1.368 F Cl 2-CI 3-(2-CF3-Ph)
1.369 F Cl 2-CI 3-(4-OCH3-Ph)
1.370 F Cl 2-CI 3-(4-SCH3-Ph)
1.371 F Cl 2-CI 3-(3-OCH3-Ph)
1.372 F Cl 2-CI 3-(3-CI-Ph)
1.373 F Cl 2-CI 3-(3,4-CI2-Ph)
1.374 F Cl 2-CI 3-(3-CI-4-F-Ph)
1.375 Cl Cl 2-CI 3-(4-F-Ph)
1.376 Cl Cl 2-CI 3-(2-CI-Ph)
1.377 Cl Cl 2-CI 3-(4-CI-Ph)
1.378 Cl Cl 2-CI 3-(3-CF3-Ph)
1.379 Cl Cl 2-CI 3-(4-CF3-Ph)
1.380 Cl Cl 2-CI 3-(2-CH3-Ph)
1.381 Cl Cl 2-CI 3-(3-CH3-Ph)
1.382 Cl Cl 2-CI 3-(4-CH3-Ph)
1.383 Cl Cl 2-CI 3-(3-OCF3-Ph)
1.384 Cl Cl 2-CI 3-(4-OCF3-Ph)
1.385 Cl Cl 2-CI 3-(4-t-butyl-Ph)
1.386 Cl Cl 2-CI 3-(2,4-CI2-Ph) No. Xi χ2 Ri R2 Phys. data
1.387 Cl Cl 2-CI 3-(3,5-CI2-Ph)
1.388 Cl Cl 2-CI 3-(2,4-F2-Ph)
1.389 Cl Cl 2-CI 3-(3,5-F2-Ph)
1.390 Cl Cl 2-CI 3-(2-CF3-Ph)
1.391 Cl Cl 2-CI 3-(4-OCH3-Ph)
1.392 Cl Cl 2-CI 3-(4-SCH3-Ph)
1.393 Cl Cl 2-CI 3-(3-OCH3-Ph)
1.394 Cl Cl 2-CI 3-(3-CI-Ph)
1.395 Cl Cl 2-CI 3-(3,4-CI2-Ph)
1.396 Cl Cl 2-CI 3-(3-CI-4-F-Ph)
1.397 F F 2-OCH3 4-(4-F-Ph)
1.398 F F 2-OCH3 4-(2-CI-Ph)
1.399 F F 2-OCH3 4-(4-CI-Ph)
1.400 F F 2-OCH3 4-(3-CF3-Ph)
1.401 F F 2-OCH3 4-(4-CF3-Ph)
1.402 F F 2-OCH3 4-(2-CH3-Ph)
1.403 F F 2-OCH3 4-(3-CH3-Ph)
1.404 F F 2-OCH3 4-(4-CH3-Ph)
1.405 F F 2-OCH3 4-(3-OCF3-Ph)
1.406 F F 2-OCH3 4-(4-OCF3-Ph)
1.407 F F 2-OCH3 4-(4-t-butyl-Ph)
1.408 F F 2-OCH3 4-(2,4-CI2-Ph)
1.409 F F 2-OCH3 4-(3,5-CI2-Ph)
1.410 F F 2-OCH3 4-(2,4-F2-Ph)
1.411 F F 2-OCH3 4-(3,5-F2-Ph)
1.412 F F 2-OCH3 4-(2-CF3-Ph)
1.413 F F 2-OCH3 4-(4-OCH3-Ph)
1.414 F F 2-OCH3 4-(4-SCH3-Ph)
1.415 F F 2-OCH3 4-(3-OCH3-Ph)
1.416 F F 2-OCH3 4-(3-CI-Ph)
1.417 F F 2-OCH3 4-(3,4-CI2-Ph)
1.418 F F 2-OCH3 4-(3-CI-4-F-Ph)
1.419 F Cl 2-OCH3 4-(4-F-Ph) No. Xi χ Ri R2 Phys. data
1.420 F Cl 2-OCH3 4-(2-CI-Ph)
1.421 F Cl 2-OCH3 4-(4-CI-Ph)
1.422 F Cl 2-OCH3 4-(3-CF3-Ph)
1.423 F Cl 2-OCH3 4-(4-CF3-Ph)
1.424 F Cl 2-OCH3 4-(2-CH3-Ph)
1.425 F Cl 2-OCH3 4-(3-CH3-Ph)
1.426 F Cl 2-OCH3 4-(4-CH3-Ph)
1.427 F Cl 2-OCH3 4-(3-OCF3-Ph)
1.428 F Cl 2-OCH3 4-(4-OCF3-Ph)
1.429 F Cl 2-OCH3 4-(4-t-butyl-Ph)
1.430 F Cl 2-OCH3 4-(2,4-CI2-Ph)
1.431 F Cl 2-OCH3 4-(3,5-CI2-Ph)
1.432 F Cl 2-OCH3 4-(2,4-F2-Ph)
1.433 F Cl 2-OCH3 4-(3,5-F2-Ph)
1.434 F Cl 2-OCH3 4-(2-CF3-Ph)
1.435 F Cl 2-OCH3 4-(4-OCH3-Ph)
1.436 F Cl 2-OCH3 4-(4-SCH3-Ph)
1.437 F Cl 2-OCH3 4-(3-OCH3-Ph)
1.438 F Cl 2-OCH3 4-(3-CI-Ph)
1.439 F Cl 2-OCH3 4-(3,4-CI2-Ph)
1.440 F Cl 2-OCH3 4-(3-CI-4-F-Ph)
1.441 Cl Cl 2-OCH3 4_(4-F-Ph)
1.442 Cl Cl 2-OCH3 4-(2-CI-Ph)
1.443 Cl Cl 2-OCH3 4-(4-CI-Ph)
1.444 Cl Cl 2-OCH3 4-(3-CF3-Ph)
1.445 Cl Cl 2-OCH3 4-(4-CF3-Ph)
1.446 Cl Cl 2-OCH3 4-(2-CH3-Ph)
1.447 Cl Cl 2-OCH3 4-(3-CH3-Ph)
1.448 Cl Cl 2-OCH3 4-(4-CH3-Ph)
1.449 Cl Cl 2-OCH3 4-(3-OCF3-Ph)
1.450 Cl Cl 2-OCH3 4-(4-OCF3-Ph)
1.451 Cl Cl 2-OCH3 4-(4-t-butyl-Ph)
1.452 Cl Cl 2-OCH3 4-(2,4-CI2-Ph) No. Xi Ri Phys. data
1.453 Cl Cl 2-OCH3 4-(3,5-CI2-Ph)
1.454 Cl Cl 2-OCH3 4-(2,4-F2-Ph)
1.455 Cl Cl 2-OCH3 4-(3,5-F2-Ph)
1.456 Cl Cl 2-OCH3 4-(2-CF3-Ph)
1.457 Cl Cl 2-OCH3 4-(4-OCH3-Ph)
1.458 Cl Cl 2-OCH3 4-(4-SCH3-Ph)
1.459 Cl Cl 2-OCH3 4-(3-OCH3-Ph)
1.460 Cl Cl 2-OCH3 4-(3-CI-Ph)
1.461 Cl Cl 2-OCH3 4-(3,4-CI2-Ph)
1.462 Cl Cl 2-OCH3 4-(3-CI-4-F-Ph)
1.463 F F 2-OCH3 3-(4-F-Ph)
1.464 F F 2-OCH3 3-(2-CI-Ph)
1.465 F F 2-OCH3 3-(4-CI-Ph)
1.466 F F 2-OCH3 3-(3-CF3-Ph)
1.467 F F 2-OCH3 3-(4-CF3-Ph)
1.468 F F 2-OCH3 3-(2-CH3-Ph)
1.469 F F 2-OCH3 3-(3-CH3-Ph)
1.470 F F 2-OCH3 3-(4-CH3-Ph)
1.471 F F 2-OCH3 3-(3-OCF3-Ph)
1.472 F F 2-OCH3 3-(4-OCF3-Ph)
1.473 F F 2-OCH3 3-(4-t-butyl-Ph)
1.474 F F 2-OCH3 3-(2,4-CI2-Ph)
1.475 F F 2-OCH3 3-(3,5-CI2-Ph)
1.476 F F 2-OCH3 3-(2,4-F2-Ph)
1.477 F F 2-OCH3 3-(3,5-F2-Ph)
1.478 F F 2-OCH3 3-(2-CF3-Ph)
1.479 F F 2-OCH3 3-(4-OCH3-Ph)
1.480 F F 2-OCH3 3-(4-SCH3-Ph)
1.481 F F 2-OCH3 3-(3-OCH3-Ph)
1.482 F F 2-OCH3 3-(3-CI-Ph)
1.483 F F 2-OCH3 3-(3,4-CI2-Ph)
1.484 F F 2-OCH3 3-(3-CI-4-F-Ph)
1.485 F Cl 2-OCH3 3-(4-F-Ph) No. Xi X2 RT R2 Phys. data
1.486 F Cl 2-OCH3 3-(2-CI-Ph)
1.487 F Cl 2-OCH3 3-(4-CI-Ph)
1.488 F Cl 2-OCH3 3-(3-CF3-Ph)
1.489 F Cl 2-OCH3 3-(4-CF3-Ph)
1.490 F Cl 2-OCH3 3-(2-CH3-Ph)
1.491 F Cl 2-OCH3 3-(3-CH3-Ph)
1.492 F Cl 2-OCH3 3-(4-CH3-Ph)
1.493 F Cl 2-OCH3 3-(3-OCF3-Ph)
1.494 F Cl 2-OCH3 3-(4-OCF3-Ph)
1.495 F Cl 2-OCH3 3-(4-t-butyl-Ph)
1.496 F Cl 2-OCH3 3-(2,4-CI2-Ph)
1.497 F Cl 2-OCH3 3-(3,5-CI2-Ph)
1.498 F Cl 2-OCH3 3-(2,4-F2-Ph)
1.499 F Cl 2-OCH3 3-(3,5-F2-Ph)
1.500 F Cl 2-OCH3 3-(2-CF3-Ph)
1.501 F Cl 2-OCH3 3-(4-OCH3-Ph)
1.502 F Cl 2-OCH3 3-(4-SCH3-Ph)
1.503 F Cl 2-OCH3 3-(3-OCH3-Ph)
1.504 F Cl 2-OCH3 3-(3-CI-Ph)
1.505 F Cl 2-OCH3 3-(3,4-CI2-Ph)
1.506 F Cl 2-OCH3 3-(3-CI-4-F-Ph)
1.507 Cl Cl 2-OCH3 3-(4-F-Ph)
1.508 Cl Cl 2-OCH3 3-(2-CI-Ph)
1.509 Cl Cl 2-OCH3 3-(4-CI-Ph)
1.510 Cl Cl 2-OCH3 3-(3-CF3-Ph)
1.511 Cl Cl 2-OCH3 3-(4-CF3-Ph)
1.512 Cl Cl 2-OCH3 3-(2-CH3-Ph)
1.513 Cl Cl 2-OCH3 3-(3-CH3-Ph)
1.514 Cl Cl 2-OCH3 3-(4-CH3-Ph)
1.515 Cl Cl 2-OCH3 3-(3-OCF3-Ph)
1.516 Cl Cl 2-OCH3 3-(4-OCF3-Ph)
1.517 Cl Cl 2-OCH3 3-(4-t-butyl-Ph)
1.518 Cl Cl 2-OCH3 3-(2,4-CI2-Ph) No. Xi χ2 Ri R2 Phys. data
1.519 Cl Cl 2-OCH3 3-(3,5-CI2-Ph)
1.520 Cl Cl 2-OCH3 3-(2,4-F2-Ph)
1.521 Cl Cl 2-OCH3 3-(3,5-F2-Ph)
1.522 Cl Cl 2-OCH3 3-(2-CF3-Ph)
1.523 Cl Cl 2-OCH3 3-(4-OCH3-Ph)
1.524 Cl Cl 2-OCH3 3-(4-SCH3-Ph)
1.525 Cl Cl 2-OCH3 3-(3-OCH3-Ph)
1.526 Cl Cl 2-OCH3 3-(3-CI-Ph)
1.527 Cl Cl 2-OCH3 3-(3,4-CI2-Ph)
1.528 Cl Cl 2-OCH3 3-(3-CI-4-F-Ph)
1.529 F F 2-CF3 4-(4-F-Ph)
1.530 F F 2-CF3 4-(2-CI-Ph)
1.531 F F 2-CF3 4-(4-CI-Ph)
1.532 F F 2-CF3 4-(3-CF3-Ph)
1.533 F F 2-CF3 4-(4-CF3-Ph)
1.534 F F 2-CF3 4-(2-CH3-Ph)
1.535 F F 2-CF3 4-(3-CH3-Ph)
1.536 F F 2-CF3 4-(4-CH3-Ph)
1.537 F F 2-CF3 4-(3-OCF3-Ph)
1.538 F F 2-CF3 4-(4-OCF3-Ph)
1.539 F F 2-CF3 4-(4-t-butyl-Ph)
1.540 F F 2-CF3 4-(2,4-CI2-Ph)
1.541 F F 2-CF3 4-(3,5-CI2-Ph)
1.542 F F 2-CF3 4-(2,4-F2-Ph)
1.543 F F 2-CF3 4-(3,5-F2-Ph)
1.544 F F 2-CF3 4-(2-CF3-Ph)
1.545 F F 2-CF3 4-(4-OCH3-Ph)
1.546 F F 2-CF3 4-(4-SCH3-Ph)
1.547 F F 2-CF3 4-(3-OCH3-Ph)
1.548 F F 2-CF3 4-(3-CI-Ph)
1.549 F F 2-CF3 4-(3,4-CI2-Ph)
1.550 F F 2-CF3 4-(3-CI-4-F-Ph)
1.551 F Cl 2-CF3 4-(4-F-Ph) No. Xi X2 Ri R2 Phys. data
1.552 F Cl 2-CF3 4-(2-CI-Ph)
1.553 F Cl 2-CF3 4-(4-CI-Ph)
1.554 F Cl 2-CF3 4-(3-CF3-Ph)
1.555 F Cl 2-CF3 4-(4-CF3-Ph)
1.556 F Cl 2-CF3 4-(2-CH3-Ph)
1.557 F Cl 2-CF3 4-(3-CH3-Ph)
1.558 F Cl 2-CF3 4-(4-CH3-Ph)
1.559 F Cl 2-CF3 4-(3-OCF3-Ph)
1.560 F Cl 2-CF3 4-(4-OCF3-Ph)
1.561 F Cl 2-CF3 4-(4-t-butyl-Ph)
1.562 F Cl 2-CF3 4-(2,4-CI2-Ph)
1.563 F Cl 2-CF3 4-(3,5-CI2-Ph)
1.564 F Cl 2-CF3 4-(2,4-F2-Ph)
1.565 F Cl 2-CF3 4-(3,5-F2-Ph)
1.566 F Cl 2-CF3 4-(2-CF3-Ph)
1.567 F Cl 2-CF3 4-(4-OCH3-Ph)
1.568 F Cl 2-CF3 4-(4-SCH3-Ph)
1.569 F Cl 2-CF3 4-(3-OCH3-Ph)
1.570 F Cl 2-CF3 4-(3-CI-Ph)
1.571 F Cl 2-CF3 4-(3,4-CI2-Ph)
1.572 F Cl 2-CF3 4-(3-CI-4-F-Ph)
1.573 Cl Cl 2-CF3 4-(4-F-Ph)
1.574 Cl Cl 2-CF3 4-(2-CI-Ph)
1.575 Cl Cl 2-CF3 4-(4-CI-Ph)
1.576 Cl Cl 2-CF3 4-(3-CF3-Ph)
1.577 Cl Cl 2-CF3 4_(4-CF3-Ph)
1.578 Cl Cl 2-CF3 4-(2-CH3-Ph)
1.579 Cl Cl 2-CF3 4-(3-CH3-Ph)
1.580 Cl Cl 2-CF3 4-(4-CH3-Ph)
1.581 Cl Cl 2-CF3 4-(3-OCF3-Ph)
1.582 Cl Cl 2-CF3 4-(4-OCF3-Ph)
1.583 Cl Cl 2-CF3 4-(4-t-butyl-Ph)
1.584 Cl Cl 2-CF3 4-(2,4-CI2-Ph) No. Xi Ri Phys. data
1.585 Cl Cl 2-CF3 4-(3,5-CI2-Ph)
1.586 Cl Cl 2-CF3 4-(2,4-F2-Ph)
1.587 Cl Cl 2-CF3 4-(3,5-F2-Ph)
1.588 Cl Cl 2-CF3 4-(2-CF3-Ph)
1.589 Cl Cl 2-CF3 4-(4-OCH3-Ph)
1.590 Cl Cl 2-CF3 4-(4-SCH3-Ph)
1.591 Cl Cl 2-CF3 4-(3-OCH3-Ph)
1.592 Cl Cl 2-CF3 4-(3-CI-Ph)
1.593 Cl Cl 2-CF3 4-(3,4-CI2-Ph)
1.594 Cl Cl 2-CF3 4-(3-CI-4-F-Ph)
1.595 F F 2-CF3 3-(4-F-Ph)
1.596 F F 2-CF3 3-(2-CI-Ph)
1.597 F F 2-CF3 3-(4-CI-Ph)
1.598 F F 2-CF3 3-(3-CF3-Ph)
1.599 F F 2-CF3 3-(4-CF3-Ph)
1.600 F F 2-CF3 3-(2-CH3-Ph)
1.601 F F 2-CF3 3-(3-CH3-Ph)
1.602 F F 2-CF3 3-(4-CH3-Ph)
1.603 F F 2-CF3 3-(3-OCF3-Ph)
1.604 F F 2-CF3 3-(4-OCF3-Ph)
1.605 F F 2-CF3 3-(4-t-butyl-Ph)
1.606 F F 2-CF3 3-(2,4-CI2-Ph)
1.607 F F 2-CF3 3-(3,5-CI2-Ph)
1.608 F F 2-CF3 3-(2,4-F2-Ph)
1.609 F F 2-CF3 3-(3,5-F2-Ph)
1.610 F F 2-CF3 3-(2-CF3-Ph)
1.611 F F 2-CF3 3-(4-OCH3-Ph)
1.612 F F 2-CF3 3-(4-SCH3-Ph)
1.613 F F 2-CF3 3-(3-OCH3-Ph)
1.614 F F 2-CF3 3-(3-CI-Ph)
1.615 F F 2-CF3 3-(3,4-CI2-Ph)
1.616 F F 2-CF3 3-(3-CI-4-F-Ph)
1.617 F Cl 2-CF3 3-(4-F-Ph) No. Xi X2 Ri R2 Phys. data
1.618 F Cl 2-CF3 3-(2-CI-Ph)
1.619 F Cl 2-CF3 3-(4-CI-Ph)
1.620 F Cl 2-CF3 3-(3-CF3-Ph)
1.621 F Cl 2-CF3 3-(4-CF3-Ph)
1.622 F Cl 2-CF3 3-(2-CH3-Ph)
1.623 F Cl 2-CF3 3-(3-CH3-Ph)
1.624 F Cl 2-CF3 3-(4-CH3-Ph)
1.625 F Cl 2-CF3 3-(3-OCF3-Ph)
1.626 F Cl 2-CF3 3-(4-OCF3-Ph)
1.627 F Cl 2-CF3 3-(4-t-butyl-Ph)
1.628 F Cl 2-CF3 3-(2,4-CI2-Ph)
1.629 F Cl 2-CF3 3-(3,5-CI2-Ph)
1.630 F Cl 2-CF3 3-(2,4-F2-Ph)
1.631 F Cl 2-CF3 3-(3,5-F2-Ph)
1.632 F Cl 2-CF3 3-(2-CF3-Ph)
1.633 F Cl 2-CF3 3-(4-OCH3-Ph)
1.634 F Cl 2-CF3 3-(4-SCH3-Ph)
1.635 F Cl 2-CF3 3-(3-OCH3-Ph)
1.636 F Cl 2-CF3 3-(3-CI-Ph)
1.637 F Cl 2-CF3 3-(3,4-CI2-Ph)
1.638 F Cl 2-CF3 3-(3-CI-4-F-Ph)
1.639 Cl Cl 2-CF3 3-(4-F-Ph)
1.640 Cl Cl 2-CF3 3-(2-CI-Ph)
1.641 Cl Cl 2-CF3 3-(4-CI-Ph)
1.642 Cl Cl 2-CF3 3-(3-CF3-Ph)
1.643 Cl Cl 2-CF3 3-(4-CF3-Ph)
1.644 Cl Cl 2-CF3 3-(2-CH3-Ph)
1.645 Cl Cl 2-CF3 3-(3-CH3-Ph)
1.646 Cl Cl 2-CF3 3-(4-CH3-Ph)
1.647 Cl Cl 2-CF3 3-(3-OCF3-Ph)
1.648 Cl Cl 2-CF3 3-(4-OCF3-Ph)
1.649 Cl Cl 2-CF3 3-(4-t-butyl-Ph)
1.650 Cl Cl 2-CF3 3-(2,4-CI2-Ph) No. Xi Ri R2 Phys. data
1.651 Cl Cl 2-CF3 3-(3,5-CI2-Ph)
1.652 Cl Cl 2-CF3 3-(2,4-F2-Ph)
1.653 Cl Cl 2-CF3 3-(3,5-F2-Ph)
1.654 Cl Cl 2-CF3 3-(2-CF3-Ph)
1.655 Cl Cl 2-CF3 3-(4-OCH3-Ph)
1.656 Cl Cl 2-CF3 3-(4-SCH3-Ph)
1.657 Cl Cl 2-CF3 3-(3-OCH3-Ph)
1.658 Cl Cl 2-CF3 3-(3-CI-Ph)
1.659 Cl Cl 2-CF3 3-(3,4-CI2-Ph)
1.660 Cl Cl 2-CF3 3-(3-CI-4-F-Ph)
Table 2: Compounds ; of the formula
No. Xi χ2 Ri R2 Phys. data
2.1 F F H 4-(4-F-Ph) 213-215°
2.2 F F H 4-(2-CI-Ph)
2.3 F F H 4-(4-CI-Ph) 230-232°
2.4 F F H 4-(3-CF3-Ph) 215-216°
2.5 F F H 4-(4-CF3-Ph) 251-252°
2.6 F F H 4-(2-CH3-Ph)
2.7 F F H 4-(3-CH3-Ph)
2.8 F F H 4-(4-CH3-Ph) 205-207°
2.9 F F H 4-(3-OCF3-Ph)
2.10 F F H 4-(4-OCF3-Ph) 232-234°
2.11 F F H 4-(4-t-butyl-Ph)
2.12 F F H 4-(2,4-CI2-Ph)
2.13 F F H 4-(3,5-CI2-Ph) 242-243°
2.14 F F H 4-(2,4-F2-Ph)
2.15 F F H 4-(3,5-F2-Ph)
2.16 F F H 4-(2-CF3-Ph) No. Xi χ2 Ri R2 Phys. data
2.17 F F H 4-(4-OCH3-Ph) 237-238°
2.18 F F H 4-(4-SCH3-Ph)
2.19 F F H 4-(3-OCH3-Ph) 204-205°
2.20 F F H 4-(3-CI-Ph) 209-210°
2.21 F F H 4-(3,4-CI2-Ph)
2.22 F F H 4-(3-CI-4-F-Ph) 239-242°
2.23 F Cl H 4-(4-F-Ph)
2.24 F Cl H 4-(2-CI-Ph)
2.25 F Cl H 4-(4-CI-Ph)
2.26 F Cl H 4-(3-CF3-Ph)
2.27 F Cl H 4-(4-CF3-Ph) 227-230
2.28 F Cl H 4-(2-CH3-Ph)
2.29 F Cl H 4-(3-CH3-Ph)
2.30 F Cl H 4-(4-CH3-Ph)
2.31 F Cl H 4-(3-OCF3-Ph)
2.32 F Cl H 4-(4-OCF3-Ph) 198-200
2.33 F Cl H 4-(4-t-butyl-Ph)
2.34 F Cl H 4-(2,4-CI2-Ph)
2.35 F Cl H 4-(3,5-CI2-Ph)
2.36 F Cl H 4-(2,4-F2-Ph)
2.37 F Cl H 4-(3,5-F2-Ph)
2.38 F Cl H 4-(2-CF3-Ph)
2.39 F Cl H 4-(4-OCH3-Ph)
2.40 F Cl H 4-(4-SCH3-Ph)
2.41 F Cl H 4-(3-OCH3-Ph)
2.42 F Cl H 4-(3-CI-Ph)
2.43 F Cl H 4-(3,4-CI2-Ph)
2.44 F Cl H 4-(3-CI-4-F-Ph)
2.45 Cl Cl H 4-(4-F-Ph)
2.46 Cl Cl H 4-(2-CI-Ph)
2.47 Cl Cl H 4-(4-CI-Ph) 192-195°
2.48 Cl Cl H 4-(3-CF3-Ph)
2.49 Cl Cl H 4-(4-CF3-Ph) 214-215° No. Xi X2 R, R2 Phys. data
2.50 Cl Cl H 4-(2-CH3-Ph)
2.51 Cl Cl H 4-(3-CH3-Ph)
2.52 Cl Cl H 4-(4-CH3-Ph)
2.53 Cl Cl H 4-(3-OCF3-Ph)
2.54 Cl Cl H 4-(4-OCF3-Ph) 155-159°
2.55 Cl Cl H 4-(4-t-butyl-Ph)
2.56 Cl Cl H 4-(2,4-CI2-Ph)
2.57 Cl Cl H 4-(3,5-CI2-Ph)
2.58 Cl Cl H 4-(2,4-F2-Ph)
2.59 Cl Cl H 4-(3,5-F2-Ph)
2.60 Cl Cl H 4-(2-CF3-Ph)
2.61 Cl Cl H 4-(4-OCH3-Ph)
2.62 Cl Cl H 4-(4-SCH3-Ph)
2.63 Cl Cl H 4-(3-OCH3-Ph)
2.64 Cl Cl H 4-(3-CI-Ph)
2.65 Cl Cl H 4-(3,4-CI2-Ph)
2.66 Cl Cl H 4-(3-CI-4-F-Ph)
2.67 F F H 3-(4-F-Ph) 155-157°
2.68 F F H 3-(2-CI-Ph)
2.69 F F H 3-(4-CI-Ph) 140-141 °
2.70 F F H 3-(3-CF3-Ph) 165-167°
2.71 F F H 3-(4-CF3-Ph) 162-168°
2.72 F F H 3-(2-CH3-Ph)
2.73 F F H 3-(3-CH3-Ph)
2.74 F F H 3-(4-CH3-Ph) 178-179°
2.75 F F H 3-(3-OCF3-Ph)
2.76 F F H 3-(4-OCF3-Ph) 149-150°
2.77 F F H 3-(4-t-butyl-Ph)
2.78 F F H 3-(2,4-CI2-Ph)
2.79 F F H 3-(3,5-CI2-Ph) 187-189°
2.80 F F H 3-(2,4-F2-Ph)
2.81 F F H 3-(3,5-F2-Ph)
2.82 F F H 3-(2-CF3-Ph) No. Xi X2 Ri R2 Phys. data
2.83 F F H 3 (4-OCH3-Ph) 208-210°
2.84 F F H 3- (4-SCH3-Ph)
2.85 F F H 3 (3-OCH3-Ph) 165-166°
2.86 F F H 3- (3-CI-Ph) 162-163°
2.87 F F H 3 (3,4-CI2-Ph)
2.88 F F H 3- (3-CI-4-F-Ph)
2.89 F Cl H 3 (4-F-Ph)
2.90 F Cl H 3- (2-CI-Ph)
2.91 F Cl H 3 (4-CI-Ph)
2.92 F Cl H 3- (3-CF3-Ph)
2.93 F Cl H 3- (4-CF3-Ph)
2.94 F Cl H 3 (2-CH3-Ph)
2.95 F Cl H 3- (3-CH3-Ph)
2.96 F Cl H 3 (4-CH3-Ph)
2.97 F Cl H 3 (3-OCF3-Ph)
2.98 F Cl H 3 (4-OCF3-Ph)
2.99 F Cl H 3 (4-t-butyl-Ph)
2.100 F Cl H 3- (2,4-CI2-Ph)
2.101 F Cl H 3- (3,5-CI2-Ph)
2.102 F Cl H 3- (2,4-F2-Ph)
2.103 F Cl H 3- (3,5-F2-Ph)
2.104 F Cl H 3- (2-CF3-Ph)
2.105 F Cl H 3- (4-OCH3-Ph)
2.106 F Cl H 3- (4-SCH3-Ph)
2.107 F Cl H 3- (3-OCH3-Ph)
2.108 F Cl H 3- (3-CI-Ph)
2.109 F Cl H 3- (3,4-CI2-Ph)
2.110 F Cl H 3- (3-CI-4-F-Ph)
2.111 Cl Cl H 3- (4-F-Ph)
2.112 Cl Cl H 3 (2-CI-Ph)
2.113 Cl Cl H (4-CI-Ph)
2.114 Cl Cl H 3 (3-CF3-Ph)
2.115 Cl Cl H 3 (4-CF3-Ph) No. Ri R2 Phys. data
2.116 Cl Cl H 3-(2-CH3-Ph)
2.117 Cl Cl H 3-(3-CH3-Ph)
2.118 Cl Cl H 3-(4-CH3-Ph)
2.119 Cl Cl H 3-(3-OCF3-Ph)
2.120 Cl Cl H 3-(4-OCF3-Ph)
2.121 Cl Cl H 3-(4-t-butyl-Ph)
2.122 Cl Cl H 3-(2,4-CI2-Ph)
2.123 Cl Cl H 3-(3,5-CI2-Ph)
2.124 Cl Cl H 3-(2,4-F2-Ph)
2.125 Cl Cl H 3-(3,5-F2-Ph)
2.126 Cl Cl H 3-(2-CF3-Ph)
2.127 Cl Cl H 3-(4-OCH3-Ph)
2.128 Cl Cl H 3-(4-SCH3-Ph)
2.129 Cl Cl H 3-(3-OCH3-Ph)
2.130 Cl Cl H 3-(3-CI-Ph)
2.131 Cl Cl H 3-(3,4-CI2-Ph)
2.132 Cl Cl H 3-(3-CI-4-F-Ph)
2.133 F F 2-CH3 4-(4-F-Ph)
2.134 F F 2-CH3 4-(2-CI-Ph)
2.135 F F 2-CH3 4-(4-CI-Ph)
2.136 F F 2-CH3 4-(3-CF3-Ph)
2.137 F F 2-CH3 4-(4-CF3-Ph)
2.138 F F 2-CH3 4-(2-CH3-Ph)
2.139 F F 2-CH3 4-(3-CH3-Ph)
2.140 F F 2-CH3 4-(4-CH3-Ph)
2.141 F F 2-CH3 4-(3-OCF3-Ph)
2.142 F F 2-CH3 4-(4-OCF3-Ph)
2.143 F F 2-CH3 4-(4-t-butyl-Ph)
2.144 F F 2-CH3 4-(2,4-CI2-Ph)
2.145 F F 2-CH3 4-(3,5-CI2-Ph)
2.146 F F 2-CH3 4-(2,4-F2-Ph)
2.147 F F 2-CH3 4-(3,5-F2-Ph)
2.148 F F 2-CH3 4-(2-CF3-Ph) No. Xi Ri R2 Phys. data
2.149 F F 2-CH3 4-(4-OCH3-Ph)
2.150 F F 2-CH3 4-(4-SCH3-Ph)
2.151 F F 2-CH3 4-(3-OCH3-Ph)
2.152 F F 2-CH3 4-(3-CI-Ph)
2.153 F F 2-CH3 4-(3,4-CI2-Ph)
2.154 F F 2-CH3 4-(3-CI-4-F-Ph)
2.155 F Cl 2-CH3 4-(4-F-Ph)
2.156 F Cl 2-CH3 4-(2-CI-Ph)
2.157 F Cl 2-CH3 4-(4-CI-Ph)
2.158 F Cl 2-CH3 4-(3-CF3-Ph)
2.159 F Cl 2-CH3 4-(4-CF3-Ph)
2.160 F Cl 2-CH3 4-(2-CH3-Ph)
2.161 F Cl 2-CH3 4-(3-CH3-Ph)
2.162 F Cl 2-CH3 4-(4-CH3-Ph)
2.163 F Cl 2-CH3 4-(3-OCF3-Ph)
2.164 F Cl 2-CH3 4-(4-OCF3-Ph)
2.165 F Cl 2-CH3 4-(4-t-butyl-Ph)
2.166 F Cl 2-CH3 4-(2,4-CI2-Ph)
2.167 F Cl 2-CH3 4-(3,5-CI2-Ph)
2.168 F Cl 2-CH3 4-(2,4-F2-Ph)
2.169 F Cl 2-CH3 4-(3,5-F2-Ph)
2.170 F Cl 2-CH3 4-(2-CF3-Ph)
2.171 F Cl 2-CH3 4-(4-OCH3-Ph)
2.172 F Cl 2-CH3 4-(4-SCH3-Ph)
2.173 F Cl 2-CH3 4-(3-OCH3-Ph)
2.174 F Cl 2-CH3 4-(3-CI-Ph)
2.175 F Cl 2-CH3 4-(3,4-CI2-Ph)
2.176 F Cl 2-CH3 4-(3-CI-4-F-Ph)
2.177 Cl Cl 2-CH3 4-(4-F-Ph)
2.178 Cl Cl 2-CH3 4-(2-CI-Ph)
2.179 Cl Cl 2-CH3 4-(4-CI-Ph)
2.180 Cl Cl 2-CH3 4-(3-CF3-Ph)
2.181 Cl Cl 2-CH3 4-(4-CF3-Ph) No. Ri R2 Phys. data
2.182 Cl Cl 2-CH3 4-(2-CH3-Ph)
2.183 Cl Cl 2-CH3 4-(3-CH3-Ph)
2.184 Cl Cl 2-CH3 4-(4-CH3-Ph)
2.185 Cl Cl 2-CH3 4-(3-OCF3-Ph)
2.186 Cl Cl 2-CH3 4-(4-OCF3-Ph)
2.187 Cl Cl 2-CH3 4-(4-t-butyl-Ph)
2.188 Cl Cl 2-CH3 4-(2,4-CI2-Ph)
2.189 Cl Cl 2-CH3 4-(3,5-CI2-Ph)
2.190 Cl Cl 2-CH3 4-(2,4-F2-Ph)
2.191 Cl Cl 2-CH3 4-(3,5-F2-Ph)
2.192 Cl Cl 2-CH3 4-(2-CF3-Ph)
2.193 Cl Cl 2-CH3 4-(4-OCH3-Ph)
2.194 Cl Cl 2-CH3 4-(4-SCH3-Ph)
2.195 Cl Cl 2-CH3 4-(3-OCH3-Ph)
2.196 Cl Cl 2-CH3 4-(3-CI-Ph)
2.197 Cl Cl 2-CH3 4-(3,4-CI2-Ph)
2.198 Cl Cl 2-CH3 4-(3-CI-4-F-Ph)
2.199 F F 2-CH3 3-(4-F-Ph)
2.200 F F 2-CH3 3-(2-CI-Ph)
2.201 F F 2-CH3 3-(4-CI-Ph)
2.202 F F 2-CH3 3-(3-CF3-Ph)
2.203 F F 2-CH3 3-(4-CF3-Ph)
2.204 F F 2-CH3 3-(2-CH3-Ph)
2.205 F F 2-CH3 3-(3-CH3-Ph)
2.206 F F 2-CH3 3-(4-CH3-Ph)
2.207 F F 2-CH3 3-(3-OCF3-Ph)
2.208 F F 2-CH3 3-(4-OCF3-Ph)
2.209 F F 2-CH3 3-(4-t-butyl-Ph)
2.210 F F 2-CH3 3-(2,4-CI2-Ph)
2.211 F F 2-CH3 3-(3,5-CI2-Ph)
2.212 F F 2-CH3 3-(2,4-F2-Ph)
2.213 F F 2-CH3 3-(3,5-F2-Ph)
2.214 F F 2-CH3 3-(2-CF3-Ph) No. Xi χ2 Ri R2 Phys. data
2.215 F F 2-CH3 3-(4-OCH3-Ph)
2.216 F F 2-CH3 3-(4-SCH3-Ph)
2.217 F F 2-CH3 3-(3-OCH3-Ph)
2.218 F F 2-CH3 3-(3-CI-Ph)
2.219 F F 2-CH3 3-(3,4-CI2-Ph)
2.220 F F 2-CH3 3-(3-CI-4-F-Ph)
2.221 F Cl 2-CH3 3-(4-F-Ph)
2.222 F Cl 2-CH3 3-(2-CI-Ph)
2.223 F Cl 2-CH3 3-(4-CI-Ph)
2.224 F Cl 2-CH3 3-(3-CF3-Ph)
2.225 F Cl 2-CH3 3-(4-CF3-Ph)
2.226 F Cl 2-CH3 3-(2-CH3-Ph)
2.227 F Cl 2-CH3 3-(3-CH3-Ph)
2.228 F Cl 2-CH3 3-(4-CH3-Ph)
2.229 F Cl 2-CH3 3-(3-OCF3-Ph)
2.230 F Cl 2-CH3 3-(4-OCF3-Ph)
2.231 F Cl 2-CH3 3-(4-t-butyl-Ph)
2.232 F Cl 2-CH3 3-(2,4-CI2-Ph)
2.233 F Cl 2-CH3 3-(3,5-CI2-Ph)
2.234 F Cl 2-CH3 3-(2,4-F2-Ph)
2.235 F Cl 2-CH3 3-(3,5-F2-Ph)
2.236 F Cl 2-CH3 3-(2-CF3-Ph)
2.237 F Cl 2-CH3 3-(4-OCH3-Ph)
2.238 F Cl 2-CH3 3-(4-SCH3-Ph)
2.239 F Cl 2-CH3 3-(3-OCH3-Ph)
2.240 F Cl 2-CH3 3-(3-CI-Ph)
2.241 F Cl 2-CH3 3-(3,4-CI2-Ph)
2.242 F Cl 2-CH3 3-(3-CI-4-F-Ph)
2.243 Cl Cl 2-CH3 3-(4-F-Ph)
2.244 Cl Cl 2-CH3 3-(2-CI-Ph)
2.245 Cl Cl 2-CH3 3-(4-CI-Ph)
2.246 Cl Cl 2-CH3 3-(3-CF3-Ph)
2.247 Cl Cl 2-CH3 3-(4-CF3-Ph) No. Xi χ2 Ri R2 Phys. data
2.248 Cl Cl 2-CH3 3-(2-CH3-Ph)
2.249 Cl Cl 2-CH3 3-(3-CH3-Ph)
2.250 Cl Cl 2-CH3 3-(4-CH3-Ph)
2.251 Cl Cl 2-CH3 3-(3-OCF3-Ph)
2.252 Cl Cl 2-CH3 3-(4-OCF3-Ph)
2.253 Cl Cl 2-CH3 3-(4-t-butyl-Ph)
2.254 Cl Cl 2-CH3 3-(2,4-CI2-Ph)
2.255 Cl Cl 2-CH3 3-(3,5-CI2-Ph)
2.256 Cl Cl 2-CH3 3-(2,4-F2-Ph)
2.257 Cl Cl 2-CH3 3-(3,5-F2-Ph)
2.258 Cl Cl 2-CH3 3-(2-CF3-Ph)
2.259 Cl Cl 2-CH3 3-(4-OCH3-Ph)
2.260 Cl Cl 2-CH3 3-(4-SCH3-Ph)
2.261 Cl Cl 2-CH3 3-(3-OCH3-Ph)
2.262 Cl Cl 2-CH3 3-(3-CI-Ph)
2.263 Cl Cl 2-CH3 3-(3,4-CI2-Ph)
2.264 Cl Cl 2-CH3 3-(3-CI-4-F-Ph)
2.265 F F 2-CI 4-(4-F-Ph)
2.266 F F 2-CI 4-(2-CI-Ph)
2.267 F F 2-CI 4-(4-CI-Ph)
2.268 F F 2-CI 4-(3-CF3-Ph)
2.269 F F 2-CI 4-(4-CF3-Ph)
2.270 F F 2-CI 4-(2-CH3-Ph)
2.271 F F 2-CI 4-(3-CH3-Ph)
2.272 F F 2-CI 4-(4-CH3-Ph)
2.273 F F 2-CI 4-(3-OCF3-Ph)
2.274 F F 2-CI 4-(4-OCF3-Ph)
2.275 F F 2-CI 4-(4-t-butyl-Ph)
2.276 F F 2-CI 4-(2,4-CI2-Ph)
2.277 F F 2-CI 4-(3,5-CI2-Ph)
2.278 F F 2-CI 4-(2,4-F2-Ph)
2.279 F F 2-CI 4-(3,5-F2-Ph)
2.280 F F 2-CI 4-(2-CF3-Ph) No. Ri R2 Phys. data
2.281 F F 2-CI 4-(4-OCH3-Ph)
2.282 F F 2-CI 4-(4-SCH3-Ph)
2.283 F F 2-CI 4-(3-OCH3-Ph)
2.284 F F 2-CI 4-(3-CI-Ph)
2.285 F F 2-CI 4-(3,4-CI2-Ph)
2.286 F F 2-CI 4-(3-CI-4-F-Ph)
2.287 F Cl 2-CI 4-(4-F-Ph)
2.288 F Cl 2-CI 4-(2-CI-Ph)
2.289 F Cl 2-CI 4-(4-CI-Ph)
2.290 F Cl 2-CI 4-(3-CF3-Ph)
2.291 F Cl 2-CI 4-(4-CF3-Ph)
2.292 F Cl 2-CI 4-(2-CH3-Ph)
2.293 F Cl 2-CI 4-(3-CH3-Ph)
2.294 F Cl 2-CI 4-(4-CH3-Ph)
2.295 F Cl 2-CI 4-(3-OCF3-Ph)
2.296 F Cl 2-CI 4-(4-OCF3-Ph)
2.297 F Cl 2-CI 4-(4-t-butyl-Ph)
2.298 F Cl 2-CI 4-(2,4-CI2-Ph)
2.299 F Cl 2-CI 4-(3,5-CI2-Ph)
2.300 F Cl 2-CI 4-(2,4-F2-Ph)
2.301 F Cl 2-CI 4-(3,5-F2-Ph)
2.302 F Cl 2-CI 4-(2-CF3-Ph)
2.303 F Cl 2-CI 4-(4-OCH3-Ph)
2.304 F Cl 2-CI 4-(4-SCH3-Ph)
2.305 F Cl 2-CI 4-(3-OCH3-Ph)
2.306 F Cl 2-CI 4-(3-CI-Ph)
2.307 F Cl 2-CI 4-(3,4-CI2-Ph)
2.308 F Cl 2-CI 4-(3-CI-4-F-Ph)
2.309 Cl Cl 2-CI 4-(4-F-Ph)
2.310 Cl Cl 2-CI 4-(2-CI-Ph)
2.311 Cl Cl 2-CI 4-(4-CI-Ph)
2.312 Cl Cl 2-CI 4-(3-CF3-Ph)
2.313 Cl Cl 2-CI 4-(4-CF3-Ph) No. Xi Ri Phys. data
2.314 Cl Cl 2-CI 4-(2-CH3-Ph)
2.315 Cl Cl 2-CI 4-(3-CH3-Ph)
2.316 Cl Cl 2-CI 4-(4-CH3-Ph)
2.317 Cl Cl 2-CI 4-(3-OCF3-Ph)
2.318 Cl Cl 2-CI 4-(4-OCF3-Ph)
2.319 Cl Cl 2-CI 4-(4-t-butyl-Ph)
2.320 Cl Cl 2-CI 4-(2,4-CI2-Ph)
2.321 Cl Cl 2-CI 4-(3,5-CI2-Ph)
2.322 Cl Cl 2-CI 4-(2,4-F2-Ph)
2.323 Cl Cl 2-CI 4-(3,5-F2-Ph)
2.324 Cl Cl 2-CI 4-(2-CF3-Ph)
2.325 Cl Cl 2-CI 4-(4-OCH3-Ph)
2.326 Cl Cl 2-CI 4-(4-SCH3-Ph)
2.327 Cl Cl 2-CI 4-(3-OCH3-Ph)
2.328 Cl Cl 2-CI 4-(3-CI-Ph)
2.329 Cl Cl 2-CI 4-(3,4-CI2-Ph)
2.330 Cl Cl 2-CI 4-(3-CI-4-F-Ph)
2.331 F F 2-CI 3-(4-F-Ph)
2.332 F F 2-CI 3-(2-CI-Ph)
2.333 F F 2-CI 3-(4-CI-Ph)
2.334 F F 2-CI 3-(3-CF3-Ph)
2.335 F F 2-CI 3-(4-CF3-Ph)
2.336 F F 2-CI 3-(2-CH3-Ph)
2.337 F F 2-CI 3-(3-CH3-Ph)
2.338 F F 2-CI 3-(4-CH3-Ph)
2.339 F F 2-CI 3-(3-OCF3-Ph)
2.340 F F 2-CI 3-(4-OCF3-Ph)
2.341 F F 2-CI 3-(4-t-butyl-Ph)
2.342 F F 2-CI 3-(2,4-CI2-Ph)
2.343 F F 2-CI 3-(3,5-CI2-Ph)
2.344 F F 2-CI 3-(2,4-F2-Ph)
2.345 F F 2-CI 3-(3,5-F2-Ph)
2.346 F F 2-CI 3-(2-CF3-Ph) No. Xi Ri Phys. data
2.347 F F 2-CI 3-(4-OCH3-Ph)
2.348 F F 2-CI 3-(4-SCH3-Ph)
2.349 F F 2-CI 3-(3-OCH3-Ph)
2.350 F F 2-CI 3-(3-CI-Ph)
2.351 F F 2-CI 3-(3,4-CI2-Ph)
2.352 F F 2-CI 3-(3-CI-4-F-Ph)
2.353 F Cl 2-CI 3-(4-F-Ph)
2.354 F Cl 2-CI 3-(2-CI-Ph)
2.355 F Cl 2-CI 3-(4-CI-Ph)
2.356 F Cl 2-CI 3-(3-CF3-Ph)
2.357 F Cl 2-CI 3-(4-CF3-Ph)
2.358 F Cl 2-CI 3-(2-CH3-Ph)
2.359 F Cl 2-CI 3-(3-CH3-Ph)
2.360 F Cl 2-CI 3-(4-CH3-Ph)
2.361 F Cl 2-CI 3-(3-OCF3-Ph)
2.362 F Cl 2-CI 3-(4-OCF3-Ph)
2.363 F Cl 2-CI 3-(4-t-butyl-Ph)
2.364 F Cl 2-CI 3-(2,4-CI2-Ph)
2.365 F Cl 2-CI 3-(3,5-CI2-Ph)
2.366 F Cl 2-CI 3-(2,4-F2-Ph)
2.367 F Cl 2-CI 3-(3,5-F2-Ph)
2.368 F Cl 2-CI 3-(2-CF3-Ph)
2.369 F Cl 2-CI 3-(4-OCH3-Ph)
2.370 F Cl 2-CI 3-(4-SCH3-Ph)
2.371 F Cl 2-CI 3-(3-OCH3-Ph)
2.372 F Cl 2-CI 3-(3-CI-Ph)
2.373 F Cl 2-CI 3-(3,4-CI2-Ph)
2.374 F Cl 2-CI 3-(3-CI-4-F-Ph)
2.375 Cl Cl 2-CI 3-(4-F-Ph)
2.376 Cl Cl 2-CI 3-(2-CI-Ph)
2.377 Cl Cl 2-CI 3-(4-CI-Ph)
2.378 Cl Cl 2-CI 3-(3-CF3-Ph)
2.379 Cl Cl 2-CI 3-(4-CF3-Ph) No. Xi Ri R2 Phys. data
2.380 Cl Cl 2-CI 3-(2-CH3-Ph)
2.381 Cl Cl 2-CI 3-(3-CH3-Ph)
2.382 Cl Cl 2-CI 3-(4-CH3-Ph)
2.383 Cl Cl 2-CI 3-(3-OCF3-Ph)
2.384 Cl Cl 2-CI 3-(4-OCF3-Ph)
2.385 Cl Cl 2-CI 3-(4-t-butyl-Ph)
2.386 Cl Cl 2-CI 3-(2,4-CI2-Ph)
2.387 Cl Cl 2-CI 3-(3,5-CI2-Ph)
2.388 Cl Cl 2-CI 3-(2,4-F2-Ph)
2.389 Cl Cl 2-CI 3-(3,5-F2-Ph)
2.390 Cl Cl 2-CI 3-(2-CF3-Ph)
2.391 Cl Cl 2-CI 3-(4-OCH3-Ph)
2.392 Cl Cl 2-CI 3-(4-SCH3-Ph)
2.393 Cl Cl 2-CI 3-(3-OCH3-Ph)
2.394 Cl Cl 2-CI 3-(3-CI-Ph)
2.395 Cl Cl 2-CI 3-(3,4-CI2-Ph)
2.396 Cl Cl 2-CI 3-(3-CI-4-F-Ph)
2.397 F F 2-OCH3 4-(4-F-Ph)
2.398 F F 2-OCH3 4-(2-CI-Ph)
2.399 F F 2-OCH3 4-(4-CI-Ph)
2.400 F F 2-OCH3 4-(3-CF3-Ph)
2.401 F F 2-OCH3 4-(4-CF3-Ph)
2.402 F F 2-OCH3 4-(2-CH3-Ph)
2.403 F F 2-OCH3 4-(3-CH3-Ph)
2.404 F F 2-OCH3 4-(4-CH3-Ph)
2.405 F F 2-OCH3 4-(3-OCF3-Ph)
2.406 F F 2-OCH3 4-(4-OCF3-Ph)
2.407 F F 2-OCH3 4-(4-t-butyl-Ph)
2.408 F F 2-OCH3 4-(2,4-CI2-Ph)
2.409 F F 2-OCH3 4-(3,5-CI2-Ph)
2.410 F F 2-OCH3 4-(2,4-F2-Ph)
2.411 F F 2-OCH3 4-(3,5-F2-Ph)
2.412 F F 2-OCH3 4-(2-CF3-Ph) No. Xi X2 Ri R2 Phys. data
2.413 F F 2-OCH3 4-(4-OCH3-Ph)
2.414 F F 2-OCH3 4-(4-SCH3-Ph)
2.415 F F 2-OCH3 4-(3-OCH3-Ph)
2.416 F F 2-OCH3 4-(3-CI-Ph)
2.417 F F 2-OCH3 4-(3,4-CI2-Ph)
2.418 F F 2-OCH3 4-(3-CI-4-F-Ph)
2.419 F Cl 2-OCH3 4-(4-F-Ph)
2.420 F Cl 2-OCH3 4-(2-CI-Ph)
2.421 F Cl 2-OCH3 4-(4-CI-Ph)
2.422 F Cl 2-OCH3 4-(3-CF3-Ph)
2.423 F Cl 2-OCH3 4-(4-CF3-Ph)
2.424 F Cl 2-OCH3 4-(2-CH3-Ph)
2.425 F Cl 2-OCH3 4-(3-CH3-Ph)
2.426 F Cl 2-OCH3 4-(4-CH3-Ph)
2.427 F Cl 2-OCH3 4-(3-OCF3-Ph)
2.428 F Cl 2-OCH3 4-(4-OCF3-Ph)
2.429 F Cl 2-OCH3 4-(4-t-butyl-Ph)
2.430 F Cl 2-OCH3 4-(2,4-CI2-Ph)
2.431 F Cl 2-OCH3 4-(3,5-CI2-Ph)
2.432 F Cl 2-OCH3 4-(2,4-F2-Ph)
2.433 F Cl 2-OCH3 4-(3,5-F2-Ph)
2.434 F Cl 2-OCH3 4-(2-CF3-Ph)
2.435 F Cl 2-OCH3 4-(4-OCH3-Ph)
2.436 F Cl 2-OCH3 4-(4-SCH3-Ph)
2.437 F Cl 2-OCH3 4-(3-OCH3-Ph)
2.438 F Cl 2-OCH3 4-(3-CI-Ph)
2.439 F Cl 2-OCH3 4-(3,4-CI2-Ph)
2.440 F Cl 2-OCH3 4-(3-CI-4-F-Ph)
2.441 Cl Cl 2-OCH3 4-(4-F-Ph)
2.442 Cl Cl 2-OCH3 4-(2-CI-Ph)
2.443 Cl Cl 2-OCH3 4-(4-CI-Ph)
2.444 Cl Cl 2-OCH3 4-(3-CF3-Ph)
2.445 Cl Cl 2-OCH3 4-(4-CF3-Ph) No. Xi Ri R2 Phys. data
2.446 Cl Cl 2-OCH3 4-(2-CH3-Ph)
2.447 Cl Cl 2-OCH3 4-(3-CH3-Ph)
2.448 Cl Cl 2-OCH3 4-(4-CH3-Ph)
2.449 Cl Cl 2-OCH3 4-(3-OCF3-Ph)
2.450 Cl Cl 2-OCH3 4-(4-OCF3-Ph)
2.451 Cl Cl 2-OCH3 4-(4-t-butyl-Ph)
2.452 Cl Cl 2-OCH3 4-(2,4-CI2-Ph)
2.453 Cl Cl 2-OCH3 4-(3,5-CI2-Ph)
2.454 Cl Cl 2-OCH3 4-(2,4-F2-Ph)
2.455 Cl Cl 2-OCH3 4-(3,5-F2-Ph)
2.456 Cl Cl 2-OCH3 4-(2-CF3-Ph)
2.457 Cl Cl 2-OCH3 4-(4-OCH3-Ph)
2.458 Cl Cl 2-OCH3 4-(4-SCH3-Ph)
2.459 Cl Cl 2-OCH3 4-(3-OCH3-Ph)
2.460 Cl Cl 2-OCH3 4-(3-CI-Ph)
2.461 Cl Cl 2-OCH3 4-(3,4-CI2-Ph)
2.462 Cl Cl 2-OCH3 4-(3-CI-4-F-Ph)
2.463 F F 2-OCH3 3-(4-F-Ph)
2.464 F F 2-OCH3 3-(2-CI-Ph)
2.465 F F 2-OCH3 3-(4-CI-Ph)
2.466 F F 2-OCH3 3-(3-CF3-Ph)
2.467 F F 2-OCH3 3-(4-CF3-Ph)
2.468 F F 2-OCH3 3-(2-CH3-Ph)
2.469 F F 2-OCH3 3-(3-CH3-Ph)
2.470 F F 2-OCH3 3-(4-CH3-Ph)
2.471 F F 2-OCH3 3-(3-OCF3-Ph)
2.472 F F 2-OCH3 3-(4-OCF3-Ph)
2.473 F F 2-OCH3 3-(4-t-butyl-Ph)
2.474 F F 2-OCH3 3-(2,4-CI2-Ph)
2.475 F F 2-OCH3 3-(3,5-CI2-Ph)
2.476 F F 2-OCH3 3-(2,4-F2-Ph)
2.477 F F 2-OCH3 3-(3,5-F2-Ph)
2.478 F F 2-OCH3 3-(2-CF3-Ph) No. Xi X2 Ri R2 Phys. data
2.479 F F 2-OCH3 3-(4-OCH3-Ph)
2.480 F F 2-OCH3 3-(4-SCH3-Ph)
2.481 F F 2-OCH3 3-(3-OCH3-Ph)
2.482 F F 2-OCH3 3-(3-CI-Ph)
2.483 F F 2-OCH3 3-(3,4-CI2-Ph)
2.484 F F 2-OCH3 3-(3-CI-4-F-Ph)
2.485 F Cl 2-OCH3 3-(4-F-Ph)
2.486 F Cl 2-OCH3 3-(2-CI-Ph)
2.487 F Cl 2-OCH3 3-(4-CI-Ph)
2.488 F Cl 2-OCH3 3-(3-CF3-Ph)
2.489 F Cl 2-OCH3 3-(4-CF3-Ph)
2.490 F Cl 2-OCH3 3-(2-CH3-Ph)
2.491 F Cl 2-OCH3 3-(3-CH3-Ph)
2.492 F Cl 2-OCH3 3-(4-CH3-Ph)
2.493 F Cl 2-OCH3 3-(3-OCF3-Ph)
2.494 F Cl 2-OCH3 3-(4-OCF3-Ph)
2.495 F Cl 2-OCH3 3-(4-t-butyl-Ph)
2.496 F Cl 2-OCH3 3-(2,4-CI2-Ph)
2.497 F Cl 2-OCH3 3-(3,5-CI2-Ph)
2.498 F Cl 2-OCH3 3-(2,4-F2-Ph)
2.499 F Cl 2-OCH3 3-(3,5-F2-Ph)
2.500 F Cl 2-OCH3 3-(2-CF3-Ph)
2.501 F Cl 2-OCH3 3-(4-OCH3-Ph)
2.502 F Cl 2-OCH3 3-(4-SCH3-Ph)
2.503 F Cl 2-OCH3 3-(3-OCH3-Ph)
2.504 F Cl 2-OCH3 3-(3-CI-Ph)
2.505 F Cl 2-OCH3 3-(3,4-CI2-Ph)
2.506 F Cl 2-OCH3 3-(3-CI-4-F-Ph)
2.507 Cl Cl 2-OCH3 3-(4-F-Ph)
2.508 Cl Cl 2-OCH3 3-(2-CI-Ph)
2.509 Cl Cl 2-OCH3 3-(4-CI-Ph)
2.510 Cl Cl 2-OCH3 3-(3-CF3-Ph)
2.511 Cl Cl 2-OCH3 3-(4-CF3-Ph) No. Ri Phys. data
2.512 Cl Cl 2-OCH3 3-(2-CH3-Ph)
2.513 Cl Cl 2-OCH3 3-(3-CH3-Ph)
2.514 Cl Cl 2-OCH3 3-(4-CH3-Ph)
2.515 Cl Cl 2-OCH3 3-(3-OCF3-Ph)
2.516 Cl Cl 2-OCH3 3-(4-OCF3-Ph)
2.517 Cl Cl 2-OCH3 3-(4-t-butyl-Ph)
2.518 Cl Cl 2-OCH3 3-(2,4-CI2-Ph)
2.519 Cl Cl 2-OCH3 3-(3,5-CI2-Ph)
2.520 Cl Cl 2-OCH3 3-(2,4-F2-Ph)
2.521 Cl Cl 2-OCH3 3-(3,5-F2-Ph)
2.522 Cl Cl 2-OCH3 3-(2-CF3-Ph)
2.523 Cl Cl 2-OCH3 3-(4-OCH3-Ph)
2.524 Cl Cl 2-OCH3 3-(4-SCH3-Ph)
2.525 Cl Cl 2-OCH3 3-(3-OCH3-Ph)
2.526 Cl Cl 2-OCH3 3-(3-CI-Ph)
2.527 Cl Cl 2-OCH3 3-(3,4-CI2-Ph)
2.528 Cl Cl 2-OCH3 3-(3-CI-4-F-Ph)
2.529 F F 2-CF3 4-(4-F-Ph)
2.530 F F 2-CF3 4-(2-CI-Ph)
2.531 F F 2-CF3 4-(4-CI-Ph)
2.532 F F 2-CF3 4-(3-CF3-Ph)
2.533 F F 2-CF3 4-(4-CF3-Ph)
2.534 F F 2-CF3 4-(2-CH3-Ph)
2.535 F F 2-CF3 4-(3-CH3-Ph)
2.536 F F 2-CF3 4-(4-CH3-Ph)
2.537 F F 2-CF3 4-(3-OCF3-Ph)
2.538 F F 2-CF3 4-(4-OCF3-Ph)
2.539 F F 2-CF3 4-(4-t-butyl-Ph)
2.540 F F 2-CF3 4-(2,4-CI2-Ph)
2.541 F F 2-CF3 4-(3,5-CI2-Ph)
2.542 F F 2-CF3 4-(2,4-F2-Ph)
2.543 F F 2-CF3 4-(3,5-F2-Ph)
2.544 F F 2-CF3 4-(2-CF3-Ph) No. Xi X2 Ri R2 Phys. data
2.545 F F 2-CF3 4-(4-OCH3-Ph)
2.546 F F 2-CF3 4-(4-SCH3-Ph)
2.547 F F 2-CF3 4-(3-OCH3-Ph)
2.548 F F 2-CF3 4-(3-CI-Ph)
2.549 F F 2-CF3 4-(3,4-CI2-Ph)
2.550 F F 2-CF3 4-(3-CI-4-F-Ph)
2.551 F Cl 2-CF3 4-(4-F-Ph)
2.552 F Cl 2-CF3 4-(2-CI-Ph)
2.553 F Cl 2-CF3 4-(4-CI-Ph)
2.554 F Cl 2-CF3 4-(3-CF3-Ph)
2.555 F Cl 2-CF3 4-(4-CF3-Ph)
2.556 F Cl 2-CF3 4-(2-CH3-Ph)
2.557 F Cl 2-CF3 4-(3-CH3-Ph)
2.558 F Cl 2-CF3 4-(4-CH3-Ph)
2.559 F Cl 2-CF3 4-(3-OCF3-Ph)
2.560 F Cl 2-CF3 4-(4-OCF3-Ph)
2.561 F Cl 2-CF3 4-(4-t-butyl-Ph)
2.562 F Cl 2-CF3 4-(2,4-CI2-Ph)
2.563 F Cl 2-CF3 4-(3,5-CI2-Ph)
2.564 F Cl 2-CF3 4-(2,4-F2-Ph)
2.565 F Cl 2-CF3 4-(3,5-F2-Ph)
2.566 F Cl 2-CF3 4-(2-CF3-Ph)
2.567 F Cl 2-CF3 4-(4-OCH3-Ph)
2.568 F Cl 2-CF3 4-(4-SCH3-Ph)
2.569 F Cl 2-CF3 4-(3-OCH3-Ph)
2.570 F Cl 2-CF3 4-(3-CI-Ph)
2.571 F Cl 2-CF3 4-(3,4-CI2-Ph)
2.572 F Cl 2-CF3 4-(3-CI-4-F-Ph)
2.573 Cl Cl 2-CF3 4-(4-F-Ph)
2.574 Cl Cl 2-CF3 4-(2-CI-Ph)
2.575 Cl Cl 2-CF3 4-(4-CI-Ph)
2.576 Cl Cl 2-CF3 4-(3-CF3-Ph)
2.577 Cl Cl 2-CF3 4-(4-CF3-Ph) No. Xi Ri R2 Phys. data
2.578 Cl Cl 2-CF3 4-(2-CH3-Ph)
2.579 Cl Cl 2-CF3 4-(3-CH3-Ph)
2.580 Cl Cl 2-CF3 4-(4-CH3-Ph)
2.581 Cl Cl 2-CF3 4-(3-OCF3-Ph)
2.582 Cl Cl 2-CF3 4-(4-OCF3-Ph)
2.583 Cl Cl 2-CF3 4-(4-t-butyl-Ph)
2.584 Cl Cl 2-CF3 4-(2,4-CI2-Ph)
2.585 Cl Cl 2-CF3 4-(3,5-CI2-Ph)
2.586 Cl Cl 2-CF3 4-(2,4-F2-Ph)
2.587 Cl Cl 2-CF3 4-(3,5-F2-Ph)
2.588 Cl Cl 2-CF3 4-(2-CF3-Ph)
2.589 Cl Cl 2-CF3 4-(4-OCH3-Ph)
2.590 Cl Cl 2-CF3 4-(4-SCH3-Ph)
2.591 Cl Cl 2-CF3 4-(3-OCH3-Ph)
2.592 Cl Cl 2-CF3 4-(3-CI-Ph)
2.593 Cl Cl 2-CF3 4-(3,4-CI2-Ph)
2.594 Cl Cl 2-CF3 4-(3-CI-4-F-Ph)
2.595 F F 2-CF3 3-(4-F-Ph)
2.596 F F 2-CF3 3-(2-CI-Ph)
2.597 F F 2-CF3 3-(4-CI-Ph)
2.598 F F 2-CF3 3-(3-CF3-Ph)
2.599 F F 2-CF3 3-(4-CF3-Ph)
2.600 F F 2-CF3 3-(2-CH3-Ph)
2.601 F F 2-CF3 3-(3-CH3-Ph)
2.602 F F 2-CF3 3-(4-CH3-Ph)
2.603 F F 2-CF3 3-(3-OCF3-Ph)
2.604 F F 2-CF3 3-(4-OCF3-Ph)
2.605 F F 2-CF3 3-(4-t-butyl-Ph)
2.606 F F 2-CF3 3-(2,4-CI2-Ph)
2.607 F F 2-CF3 3-(3,5-CI2-Ph)
2.608 F F 2-CF3 3-(2,4-F2-Ph)
2.609 F F 2-CF3 3-(3,5-F2-Ph)
2.610 F F 2-CF3 3-(2-CF3-Ph) No. Xi Ri R2 Phys. data
2.611 F F 2-CF3 3-(4-OCH3-Ph)
2.612 F F 2-CF3 3-(4-SCH3-Ph)
2.613 F F 2-CF3 3-(3-OCH3-Ph)
2.614 F F 2-CF3 3-(3-CI-Ph)
2.615 F F 2-CF3 3-(3,4-CI2-Ph)
2.616 F F 2-CF3 3-(3-CI-4-F-Ph)
2.617 F Cl 2-CF3 3-(4-F-Ph)
2.618 F Cl 2-CF3 3-(2-CI-Ph)
2.619 F Cl 2-CF3 3-(4-CI-Ph)
2.620 F Cl 2-CF3 3-(3-CF3-Ph)
2.621 F Cl 2-CF3 3-(4-CF3-Ph)
2.622 F Cl 2-CF3 3-(2-CH3-Ph)
2.623 F Cl 2-CF3 3-(3-CH3-Ph)
2.624 F Cl 2-CF3 3-(4-CH3-Ph)
2.625 F Cl 2-CF3 3-(3-OCF3-Ph)
2.626 F Cl 2-CF3 3-(4-OCF3-Ph)
2.627 F Cl 2-CF3 3-(4-t-butyl-Ph)
2.628 F Cl 2-CF3 3-(2,4-CI2-Ph)
2.629 F Cl 2-CF3 3-(3,5-CI2-Ph)
2.630 F Cl 2-CF3 3-(2,4-F2-Ph)
2.631 F Cl 2-CF3 3-(3,5-F2-Ph)
2.632 F Cl 2-CF3 3-(2-CF3-Ph)
2.633 F Cl 2-CF3 3-(4-OCH3-Ph)
2.634 F Cl 2-CF3 3-(4-SCH3-Ph)
2.635 F Cl 2-CF3 3-(3-OCH3-Ph)
2.636 F Cl 2-CF3 3-(3-CI-Ph)
2.637 F Cl 2-CF3 3-(3,4-CI2-Ph)
2.638 F Cl 2-CF3 3-(3-CI-4-F-Ph)
2.639 Cl Cl 2-CF3 3-(4-F-Ph)
2.640 Cl Cl 2-CF3 3-(2-CI-Ph)
2.641 Cl Cl 2-CF3 3-(4-CI-Ph)
2.642 Cl Cl 2-CF3 3-(3-CF3-Ph)
2.643 Cl Cl 2-CF3 3-(4-CF3-Ph) No. Xi χ2 Ri R2 Phys. data
2.644 Cl Cl 2-CF3 3-(2-CH3-Ph)
2.645 Cl Cl 2-CF3 3-(3-CH3-Ph)
2.646 Cl Cl 2-CF3 3-(4-CH3-Ph)
2.647 Cl Cl 2-CF3 3-(3-OCF3-Ph)
2.648 Cl Cl 2-CF3 3-(4-OCF3-Ph)
2.649 Cl Cl 2-CF3 3-(4-t-butyl-Ph)
2.650 Cl Cl 2-CF3 3-(2,4-CI2-Ph)
2.651 Cl Cl 2-CF3 3-(3,5-CI2-Ph)
2.652 Cl Cl 2-CF3 3-(2,4-F2-Ph)
2.653 Cl Cl 2-CF3 3-(3,5-F2-Ph)
2.654 Cl Cl 2-CF3 3-(2-CF3-Ph)
2.655 Cl Cl 2-CF3 3-(4-OCH3-Ph)
2.656 Cl Cl 2-CF3 3-(4-SCH3-Ph)
2.657 Cl Cl 2-CF3 3-(3-OCH3-Ph)
2.658 Cl Cl 2-CF3 3-(3-CI-Ph)
2.659 Cl Cl 2-CF3 3-(3,4-CI2-Ph)
2.660 Cl Cl 2-CF3 3-(3-CI-4-F-Ph)
Table 3: Compounds of the formula
No. Xi R* Rv Phys. data
3.1 F F H 4-F
3.2 F F H 2-CI
3.3 F F H 4-CI
3.7 F F H 3-CH3
3.8 F F H 4-CH3 No. Xi X2 Rw Rv Phys. data
3.9 F F H 3-OCF3
3.10 F F H 4-OCF3
3.11 F F H 4-t-butyl
3.12 F F H 2,4-CI2
3.13 F F H 3,5-CI2
3.14 F F H 2,4-F2-Ph
3.15 F F H 3,5-F2
3.20 F F H 3-CI
3.21 F F H 3,4-CI2
3.22 F F H 3-CI-4-F
3.23 F F H 2-F
3.24 Cl Cl H 4-F
3.25 Cl Cl H 2-CI
3.26 Cl Cl H 4-CI
3.34 Cl Cl H 4-t-butyl
3.35 Cl Cl H 2,4-CI2
3.36 Cl Cl H 3,5-CI2
3.37 Cl Cl H 2,4-F2-Ph
3.38 Cl Cl H 3,5-F2
3.40 Cl Cl H 4-OCH3
3.41 Cl Cl H 4-SCH3 No. Xi X2 Rw Rv Phys. data
3.42 Cl Cl H 3-OCH3
3.43 Cl Cl H 3-CI
3.44 Cl Cl H 3,4-CI2
3.45 Cl Cl H 3-CI-4-F
3.46 Cl Cl H 2-F
3.47 F Cl H 4-F
3.48 F Cl H 2-CI
3.49 F Cl H 4-CI
3.50 F Cl H 3-CF3
3.51 F Cl H 4-CF3
3.52 F Cl H 2-CH3
3.53 F Cl H 3-CH3
3.54 F Cl H 4-CH3
3.55 F Cl H 3-OCF3
3.56 F Cl H 4-OCF3
3.57 F Cl H 4-t-butyl
3.58 F Cl H 2,4-CI2
3.59 F Cl H 3,5-CI2
3.60 F Cl H 2,4-F2-Ph
3.61 F Cl H 3,5-F2
3.62 F Cl H 2-CF3
3.63 F Cl H 4-OCH3
3.64 F Cl H 4-SCH3
3.65 F Cl H 3-OCH3
3.66 F Cl H 3-CI
3.67 F Cl H 3,4-CI2
3.68 F Cl H 3-CI-4-F
3.69 F Cl H 2-F Table 4: Compounds of the formula
x.
No. Xi χ2 Ri R2 Phys. data
4.1 F F H 4-F
4.2 F F H 2-CI
4.3 F F H 4-CI
4.4 F F H 3-CF3
4.5 F F H 4-CF3
4.6 F F H 2-CH3
4.7 F F H 3-CH3
4.8 F F H 4-CH3
4.9 F F H 3-OCF3
4.10 F F H 4-OCF3
4.11 F F H 4-t-butyl
4.12 F F H 2.4-CI2
4.14 F F H 2,4-F2-Ph
4.15 F F H 3,5-F2
4.16 F F H 2-CF3
4.17 F F H 4-OCH3
4.18 F F H 4-SCH3
4.19 F F H 3-OCH3
4.20 F F H 3-CI
4.21 F F H 3,4-CI2
4.22 F F H 3-CI-4-F
4.23 F F H 2-F
4.24 Cl Cl H 4-F
4.25 Cl Cl H 2-CI No. Xi χ2 Ri R2 Phys. data
4.26 Cl Cl H 4-CI
4.27 Cl Cl H 3-CF3
4.28 Cl Cl H 4-CF3
4.29 Cl Cl H 2-CH3
4.34 Cl Cl H 4-t-butyl
4.35 Cl Cl H 2,4-CI2
4.36 Cl Cl H 3,5-CI2
4.37 Cl Cl H 2,4-F2-Ph
4.38 Cl Cl H 3,5-F2
4.39 Cl Cl H 2-CF3
4.43 Cl Cl H 3-CI
4.44 Cl Cl H 3,4-CI2
4.45 Cl Cl H 3-CI-4-F
4.46 Cl Cl H 2-F
4.47 F Cl H 4-F
4.48 F Cl H 2-CI
4.49 F Cl H 4-CI
4.51 F Cl H 4-CF3
4.57 F Cl H 4-t-butyl
4.58 F Cl H 2.4-CI2 No. Xi χ2 Ri R2 Phys. data
4.59 F Cl H 3,5-CI2
4.60 F Cl H 2,4-F2-Ph
4.61 F Cl H 3,5-F2
4.62 F Cl H 2-CF3
4.65 F Cl H 3-OCH3
4.66 F Cl H 3-CI
4.67 F Cl H 3,4-CI2
4.68 F Cl H 3-CI-4-F
4.69 F Cl H 2-F
Table 5: Compounds of the formula
No. Xi Ro Phys. data
5.1 F F H -C(=O)C6H4-4-CH3 Smpt.: 196-197°C
5.2 F F H -C(=NOCH3)C6H4-3-CH3 Smpt.: 133-136°C
5.3 CH3 H H -C6H4-4-CF3 Smpt.: 224-227°C
5.4 CH3 H H -C6H4-4-OCF3
5.5 CH3 H H -C6H43-3,4-CI2
5.6 CH3 H H -C6H4-3-CI
5.7 CH3 H H -C6H3-3-CI, 4-F
5.8 CH3 H H -C6H4-4-SCH3
5.9 CH3 H H -C6H4-4-CI
5.10 CH3 H H -C6H4-4-F
5.11 CH3 H H -C6H4-4-SCF3
5.12 Cl H F -C6H4-4-CF3
5.13 Cl H F -C6H4-4-OCF3
5.14 Cl H F -C6H43-3,4-CI2
5.15 Cl H F -C6H4-3-CI No. Xi χ2 χ3 Rq Phys. data
5.16 Cl H F -C6H3-3-CI, 4-F
5.17 Cl H F -C6H4-4-SCH3
5.18 Cl H F -C6H4-4-CI
5.19 Cl H F -C6H4-4-F
5.20 Cl H F -C6H4-4-SCF3
5.21 F CH3 H -C6H4-4-CF3
5.22 F CH3 H -C6H4-4-OCF3
5.23 F CH3 H -C6H43-3,4-CI2
5.24 F CH3 H -C6H4-3-CI
5.25 F CH3 H -C6H3-3-CI, 4-F
5.26 F CH3 H -C6H4-4-SCH3
5.27 F CH3 H -C6H4-4-CI
5.28 F CH3 H -C6H4-4-F
5.29 F CH3 H -C6H4-4-SCF3
5.30 F H Cl -C6H4-4-CF3
5.31 F H Cl -C6H4-4-OCF3
5.32 F H Cl -C6H43-3,4-CI2
5.33 F H Cl -C6H4-3-CI
5.34 F H Cl -C6H3-3-CI, 4-F
5.35 F H Cl -C6H4-4-SCH3
5.36 F H Cl -C6H4-4-CI
5.37 F H Cl -C6H4-4-F
5.38 F H Cl -C6H4-4-SCF3
5.39 CH3 H F -C6H4-4-CF3
5.40 CH3 H F -C6H4-4-OCF3
5.41 CH3 H F -C6H43-3,4-CI2
5.42 CH3 H F -C6H4-3-CI
5.43 CH3 H F -C6H3-3-CI, 4-F
5.44 CH3 H F -C6H4-4-SCH3
5.45 CH3 H F -C6H4-4-CI
5.46 CH3 H F -C6H4-4-F
5.47 CH3 H F -C6H4-4-SCF3
5.48 OCH3 OCH3 H -C6H4-4-CF3 No. Xi χ2 X3 Rq Phys. data
5.49 OCH3 OCH3 H -C6H4-4-OCF3
5.50 OCH3 OCH3 H -C6H43-3,4-CI2
5.51 OCH3 OCH3 H -C6H4-3-CI
5.52 OCH3 OCH3 H -C6H3-3-CI, 4-F
5.53 OCH3 OCH3 H -C6H4-4-SCH3
5.54 OCH3 OCH3 H -C6H4-4-CI
5.55 OCH3 OCH3 H -C6H4-4-F
5.56 OCH3 OCH3 H -C6H4-4-SCF3
2. Formulation Examples
2.1. Emulsifiable concentrates a) b) c) a compound of Tables 2 to 4 25% 40% 50% calcium dodecylbenzenesulfonate 5% 8% 6% castor oil polyethylene glycol ether (36 mol of ethylene oxide) 5 % tributylphenol polyethylene glycol ether (30 mol of ethylene oxide) 12% 4% cyclohexanone 15% 20% xylene mixture 65 % 25% 20%
Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.
2.2. Emulsifiable concentrates a) b) c) a compound of Tables 2 to 4 10% 8% 60% octylphenol polyethylene glycol ether (4-5 mol of ethylene oxide) 3% 3% 2% calcium dodecylbenzenesulfonate 3% 4% 4% castor oil polyethylene glycol ether (35 mol of ethylene oxide) 4% 5% 4% cyclohexanone 30% 40% 15% xylene mixture 50% 40% 15%
Emulsions of any desired concentration can be prepared from such concentrates by dilution with water. 2.3. Suspension concentrate a compound of Tables 2 to 4 40 % ethylene glycol 10 % nonylphenol polyethylene glycol ether
(15 mol of ethylene oxide) 6 % sodium lignosulfonate 10 % carboxymethylcellulose 1 %
37 % aqueous formaldehyde solution 0.2 % silicone oil in the form of a 75 % aqueous emulsion 0.8 % water 32 %
The finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.
2.4. Powder mixtures dispersible in water a) b) c) a compound of Tables 2 to 4 25 % 50 % 75 % sodium lignosulfonate 5 % 5 % - oleic acid 3 % - 5 % sodium diisobutylnaphthalenesulfonate - 6 % 10 % octylphenol polyethylene glycol ether
(7-8 mol of ethylene oxide) - 2 % - highly dispersed silicic acid 5 % 10 % 10 % kaolin 62 % 27 % -
The active ingredient is thoroughly mixed with the adjuvants and the mixture is thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of any desired concentration.
2.5. Dusts a) b) a compound of Tables 2 to 4 2 % 5 % highly dispersed silicic acid 1 % 5 % talcum 97 % - kaolin - 90 °
Ready-for-use dusts are obtained by intimately mixing the carriers with the active ingredient and grinding the mixture. 2.6. Granules a) b) a compound of Tables 2 to 4 5 % 10 % kaolin 94 % - highly dispersed silicic acid 1 % - attapulgite - 90 %
The active ingredient is dissolved in methylene chloride and the solution is sprayed onto the carrier, and the solvent is subsequently evaporated in vacuo. Such granules can be mixed with animal feed.
2.7. Granules a compound of Tables 2 to 4 10 % sodium lignosulfonate 2 % carboxymethylcellulose 1 % kaolin 87 %
The active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water. The mixture is extruded and then dried in a stream of air.
2.8. Granules a compound of Tables 2 to 4 3 % polyethylene glycol (MW 200) 3 % kaolin 94 %
(MW = molecular weight)
The finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
2.9. Tablets
Constituents (for 1000 tablets): a compound of Tables 2 to 4 25.0 g lactose 100.7 g wheat starch 7.5 g polyethylene glycol 6000 5.0 g talcum 5.0 g magnesium stearate 1 8 g demineralised water q.s.
All the solid ingredients are first forced through a sieve of 0.6 mm mesh size. Then the active ingredient, the lactose, the talcum and half the starch are mixed together. The other half of the starch is suspended in 40 ml of water and the suspension is added to a boiling solution of the polyethylene glycol in 100 ml of water. The resulting starch paste is added to the main batch and the mixture is granulated, if necessary with the addition of water. The granules are dried overnight at 35°, forced through a sieve of 1.2 mm mesh size, mixed with the magnesium stearate and compressed to form tablets which have a mesh size of about 6 mm and which are concave on both sides.
2.10. Injectable formulations
A. Oily vehicle (slow release) a compound of Tables 2 to 4 0.1-1.0 g groundnut oil ad 100 ml a compound of Tables 2 to 4 0.1-1.0 g sesame oil ad 100 ml
The active ingredient is dissolved in a portion of the oil with stirring and optionally with gentle heating, and after cooling the solution is made up to the desired volume and sterile-filtered through a suitable 0.22 mm membrane filter.
B. Water-miscible solvent (medium rate of release) a compound of Tables 2 to 4 0.1-1.0 g 4-hydroxymethyl-1 ,3-dioxolane (glycerol formal) 40 g 1 ,2-propanediol ad 100 ml a compound of Tables 2 to 4 0.1-1.0 g glycerol dimethyl ketal 40 g 1 ,2-propanediol ad 100 ml
The active ingredient is dissolved in a portion of the solvent with stirring, and the solution is made up to the desired volume and sterile-filtered through a suitable 0.22 mm membrane filter.
C. Aqueous solubilisate (rapid release) a compound of Tables 2 to 4 0.1-1.0 g polyethoxylated castor oil (40 ethylene oxide units) 10 g
1 ,2-propanediol 20 g benzyl alcohol 1 g aqua ad inject. ad 100 ml a compound of Tables 2 to 4 0.1-1.0 g polyethoxylated sorbitan monooleate (20 ethylene oxide units) 8 g
4-hydroxymethyl-1 ,3-dioxolane (glycerol formal) 20 g benzyl alcohol 1 g aqua ad inject. ad 100 ml
Preparation: The active ingredient is dissolved in the solvents and the surfactant, and the solution is made up to the desired volume with water. Sterile-filtration is then carried out through a suitable membrane filter of 0.22 mm pore diameter.
The aqueous systems can be used in a preferred manner also for oral and/or intraruminal administration.
2.11. Pour on A. a compound of Tables 2 to 4 10% epoxidised soybean oil 5% oleyl alcohol 85%
B. a compound of Tables 2 to 4 20% pyrrolidin-2-one 15% isopropyl myristate 65%
It is also possible to add to the described compositions further biologically active substances or additives that have neutral behaviour towards the compounds of formula (I) and have no adverse effect on the host animal to be treated, and also mineral salts or vitamins.
3. Biological Examples
A. Insecticidal action
3.1. Action against Aphis craccivora
Pea seedlings are infested with Aphis craccivora, subsequently sprayed with a spray mixture comprising 100 ppm of active ingredient and then incubated at 20°C. 3 and 6 days later the percentage reduction in population (% activity) is determined by comparing the number of dead aphids on the treated plants with that on untreated plants.
Compounds of formula (I) exhibit good activity in this test. 3.2. Action against Diabrotica balteata
Maize seedlings are sprayed with an aqueous emulsion spray mixture comprising 100 ppm of active ingredient and, after the spray-coating has dried, are populated with 10 Diabrotica balteata larvae in the second stage and then placed in a plastics container. 6 days later, the percentage reduction in population (% activity) is determined by comparing the number of dead larvae on the treated plants with that on untreated plants.
Compounds of formula (I) exhibit good activity in this test. For example, especially compounds 2.13 and 2.17 bring about a more than 80% reduction in the pest population.
3.3. Action against Heliothis virescens
Young soybean plants are sprayed with an aqueous emulsion spray mixture comprising 100 ppm of active ingredient and, after the spray-coating has dried, are populated with 10 caterpillars of Heliothis virescens in the first stage and then placed in a plastics container. 6 days later, the percentage reduction in population and in feeding damage (% activity) are determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on untreated plants.
Compounds of formula (I) exhibit good activity in this test. For example, especially compounds 2.13, 2.17 ad 2.27 bring about a more than 80% reduction in the pest population.
3.4. Action against Spodoptera littoralis
Young soybean plants are sprayed with an aqueous emulsion spray mixture comprising 100 ppm of active ingredient and, after the spray-coating has dried, are populated with 10 caterpillars of Spodoptera littoralis in the third stage and then placed in a plastics container. 3 days later, the percentage reduction in population and the percentage reduction in feeding damage (% activity) are determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on untreated plants.
Compounds of formula (I) and (VII) exhibit good activity in this test. For example, especially compounds 1.3, 2.1 , 2.3, 2.4, 2.5, 2.8, 2.10, 2.13, 2.17, 2.20, 2.22, 2.27, 2.32, 2.47, 2.49 and 2.54 bring about a more than 80% reduction in the pest population.
3.5. Action against Nilaparvata luqens
Rice plants are treated with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient. After the spray-coating has dried, the rice plants are populated with cicada larvae in the 2nd and 3rd stages. The evaluation is carried out 21 days later. The percentage reduction in population (% activity) is determined by comparing the number of surviving cicadas on the treated plants with that on untreated plants.
Compounds of formula (I) exhibit good activity in this test.
3.6. Action against Crocidolomia binotalis
Young cabbage plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient. After the spray-coating has dried, the cabbage plants are populated with 10 Crocidolomia binotalis caterpillars in the third stage and placed in a plastics container. The evaluation is carried out 3 days later. The percentage reduction in population and the percentage reduction in feeding damage (% activity) are determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on untreated plants.
Compounds of formula (I) exhibit good activity in this test.
3.7. Action against Anthonomus grandis
Young cotton plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient. After the spray-coating has dried, the cotton plants are populated with 10 Anthonomus grandis adults and placed in a plastics container. The evaluation is carried out 3 days later. The percentage reduction in population and the percentage reduction in feeding damage (% activity) are determined by comparing the number of dead weevils and the feeding damage on the treated plants with that on untreated plants.
Compounds of formula (I) exhibit good activity in this test.
3.8. Action against Aonidiella aurantii
Potato tubers are populated with crawlers of Aonidiella aurantii. After about 2 weeks the potatoes are immersed in an aqueous emulsion or suspension spray mixture comprising 400 ppm of active ingredient. When the tubers have dried they are incubated in a plastics container. For evaluation, 10 to 12 weeks later the survival rate of the crawlers of the first subsequent generation of the treated population is compared with that of untreated controls.
Compounds of formula (I) exhibit good activity in this test.
3.9. Action against Bemisia tabaci
Dwarf bean plants are placed in gauze cages and populated with adults of Bemisia tabaci. After oviposition has taken place, all adults are removed. 10 days later the plants and the nymphs located thereon are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of active ingredient. After a further 14 days, the percentage of eggs that have hatched is evaluated in comparison with untreated controls.
Compounds of formula (I) exhibit good activity in this test.
B. Acaricidal action
3.10. Action against Tetranvchus urticae
Young bean plants are populated with a mixed population of Tetranychus urticae and sprayed 1 day later with an aqueous emulsion spray mixture comprising 100 ppm of active ingredient, incubated for 6 days at 25°C and then evaluated. The percentage reduction in population (% activity) is determined by comparing the number of dead eggs, larvae and adults on the treated plants with that on untreated plants.
Compounds of formula (I) exhibit good activity in this test. For example, especially compounds 2.4, 2.20, 2.22, 2.27, 2.47, 2.49 and 2.54 bring about a more than 80% reduction in the pest population.
3.11. Action against Panonvchus ulmi (OP and carb. resistant)
Apple seedlings are populated with adult females of Panonychus ulmi. After seven days the infested plants are sprayed to drip point with an aqueous emulsion spray mixture comprising 400 ppm of the test compound and are cultivated in a greenhouse. The evaluation is carried out after 14 days. The percentage reduction in population (% activity) is determined by comparing the number of dead spider mites on the treated plants with that on untreated plants.
Compounds of formula (I) exhibit good activity in this test.
C. Ectoparasiticidal action
3.12. Control of adult fleas in cats by means of pour-on application
In order to determine the effectiveness of the test compounds against fully grown fleas, four groups each of two cats are used. Each cat is infested with 100 cat fleas [Ctenocephalides felis (Bouche)] and treated with 20 mg of active ingredient per kg body weight. The treatment is effected by applying the formulation to a locally defined area on the back of the cat's neck. One group is infested with fleas but is treated only with a placebo, that is to say a formulation without active ingredient, and serves as control. Another group is treated with nitenpyram as comparison substance; the two remaining groups are treated with the test compounds. Evaluation is carried out in each case by combing surviving fleas out of the animal's coat, counting them and comparing the number counted with the number of fleas in the control group and in the group treated with nitenpyram. The procedure in detail is as follows: each cat is infested with 100 fleas immediately after treatment on day 0. On day +1 , each animal is combed and the number of surviving fleas is determined; the surviving fleas are then replaced on the same cat and after 24 hours the combing and evaluation are repeated. The fleas still surviving after those 24 hours are not returned to the cat. The described procedure is then repeated on days +3, +7, +9, +14, +21 , +28, +35, +42 and +49 and in this way the effectiveness and duration of action are determined. On every day on which surviving fleas are combed out, a blood sample of about 2.7 ml is taken from each cat - with the exception of the control group - and the content of active ingredient is measured. The effectiveness is determined in accordance with the following formula:
number of living fleas minus number of living fleas per control animal per test animal
% effectiveness = * 100 number of living fleas per control animal
It is shown that the compounds of formula (I) according to the invention achieve excellent long-term action in comparison with nitenpyram.
In dogs the test proceeds in an entirely analogous manner. Similar effects are also observed when the substances are administered not in the form of a pour-on but in the form of an injection solution.
3.13. Control of adult fleas in cats by means of subcutaneous injection In order to determine the effectiveness of the test compounds against fully grown fleas, four groups each of two cats aged from 1.5 to 4 years are used. Each cat is infested with 100 cat fleas [Ctenocephalides felis (Bouche)] and treated with 20 mg of active ingredient per kg body weight. The treatment is effected by subcutaneous injection of a solution of the active ingredient behind the left shoulder blade. One group is infested with fleas but is treated only with a placebo, that is to say a formulation without active ingredient, and serves as control. Another group is treated with nitenpyram as comparison substance; the two remaining groups are treated with the test compounds. The evaluation is in each case carried out analogously to the preceding Example.
It is shown that after subcutaneous injection the compounds of formula (I) according to the invention achieve excellent long-term action in comparison with nitenpyram.
The analogous test with dogs gives comparable results.

Claims

What is claimed is:
1. A compound of formula
wherein
TN is -Ν=Ν- or -NH-NH-;
X2 and X3 are each independently of the other H or Ri;
Ri is halogen, CN, NO2, d-C6alkyl, C3-C8cycloalkyl, d-C6haloalkyl, C3-C8halocycloalkyl,
Cι-C6alkoxy, C3-C8cycloalkoxy, Cι-C6haloalkoxy, C3-C8halocycloalkoxy, Cι-C6alkylthio,
C3-C8cycloalkylthio, Cι-C6haloalkylthio or C3-C8halocycloalkylthio;
Ari is unsubstituted or mono- to tetra-substituted aryl or heteroaryl, the substituents being selected from the group consisting of OH, halogen, CN, NO2, d-C6alkyl, C3-C8cycloalkyl,
Cι-C6alkyl-C3-C8cycloalkyl, C3-C8cycloalkyl-C C6alkyl, Cι-C6haloalkyl, C3-C8halocycloalkyl,
Cι-C6alkoxy, C3-C8cycloalkoxy, Cι-C6haloalkoxy, C3-C8halocycloalkoxy, d-C6alkylthio,
C3-C8cycloalkylthio, Cι-C6haloalkylthio, C3-C8halocycloalkylthio, Cι-C6alkylsulfinyl, C3-C8- cycloalkylsulfinyl, Cι-C6haloalkylsulfinyl, C3-C8halocycloalkylsulfιnyl, Cι-C6alkylsulfonyl,
C3-C8cycloalkylsulfonyl, Cι-C6haloalkylsulfonyl, C3-C8halocycloalkylsulfonyl, C2-C8alkenyl,
C2-C8alkynyl, Cι-C6alkylcarbonyl, Cι-C6alkyl-C(=NOR2) and R3;
Ar2 is unsubstituted or mono- to penta-substituted aryl or heteroaryl, the substituents being selected from the group consisting of OH, halogen, CN, NO2, Cι-C6alkyl, C3-C8cycloalkyl,
Cι-C6alkyl-C3-C8cycloalkyl, C3-C8cycloalkyl-d-C6alkyl, d-C6haloalkyl, C3-C8halocycloalkyl,
Cι-C6alkoxy, C3-C8cycloalkoxy, Cι-C6haloalkoxy, C3-C8halocycloalkoxy, Cι-C6alkylthio,
C3-C8cycloalkylthio, Cι-C6haloalkylthio, C3-C8halocycloalkylthio, d-C6alkylsulfinyl, C3-C8cyc- loalkylsulfinyl, Cι-C6haloalkylsulfιnyl, C3-C8halocycloalkylsulfιnyl, d-dalkylsulfonyl,
C3-C8cycloalkylsulfonyl, Cι-C6haloalkylsulfonyl, C3-C8halocycloalkylsulfonyl, C2-C8alkenyl,
C2-C8alkynyl, C C6alkylcarbonyl, Cι-C6alkyl-C(=NOR2) and R3;
A is a single bond, d-Cι2alkylene, O, O(d-C12alkylene), S(O)n,
S(O)n(Cι-Cι2alkylene), C2-C8alkenylene, C2-C8alkynylene; NR6, NR6(Cι-C12alkylene) or
C(=Z);
Z is O, NR4, NNR4R5 or NOFt,; R2 is H, Cι-C6alkyl or C3-C8cycloalkyl;
R4 and R5 are each independently of the other H, Cι-C6alkyl or Cι-C6haloalkyl;
R6 is H, Cι-C6alkyl, C3-C8cycloalkyl, Cι-C6haloalkyl, C2-C8alkenyl, C2-C8alkynyl, aryl- d-C6alkyl, (CH2)pC(O)R7 or Cι-C6alkoxy-C2-C6alkyl;
R7 is H, Cι-C6alkyl, C3-C8cycloalkyl, d-C6haloalkyl, Cι-C6alkoxy, N(R8)2 or
Cι-C6alkoxy-C2-C6alkyl;
R8 is H, Cι-C6alkyl, C3-C8cycloalkyl, d-C6haloalkyl or aryl-C C6alkyl;
R9 and Rio are each independently of the other H or d-C6alkyl; m is 1 , 2, 3 or 4; n is O, 1 or 2; p is O, 1 , 2, 3, 4, 5 or 6; and
Q is O or S; with the proviso, that when T-V is -NH-NH-, Xi is halogen, X2 and X3 are both hydrogen, An and Ar2 are both phenyl which may be unsubstituted or substituted, A is not a single bond; or, where applicable, a possible E/Z isomer, mixture of E/Z isomers and/or tautomer thereof, in each case in free form or in salt form.
2. A compound according to claim 1 of formula (I) in free form.
3. A compound according to either claim 1 or claim 2 of formula (I) wherein X3 is H.
4. A compound according to anyone of claims 1 to 3 of formula (I) wherein Ar2 is unsubstituted or mono- to tri-substituted aryl or heteroaryl, the substituents being selected from the group consisting of OH, halogen, CN, NO2, Cι-C alkyl, C3-C6cycloalkyl, C C4alkyl- C3-C4cycloalkyl, C3-C6cycloalkyl-Cι-C4alkyl, d-C4haloalkyl, C3-C6halocycloalkyl, d-dalkoxy, C3-C6cycloalkoxy, d-C4haloalkoxy, C3-C6halocycloalkoxy, d-dalkylthio, C3-C6cycloalkylthio, d-C4haloalkylthio, C3-C6halocycloalkylthio, d-dalkylsulfinyl, C3-C6cycloalkylsulfιnyl, Cι-C4haloalkylsulfιnyl, C3-C6halocycloalkylsulfιnyl, d-dalkylsulfonyl, C3-C6cycloalkylsulfonyl, d-dhaloalkylsulfonyl, C3-C6halocycloalkylsulfonyl, C2-C6alkenyl, C2-C6alkynyl, d-dalkylcarbonyl, d-C4alkyl-C(=NOR2) and R3.
5. A compound according to anyone of claims 1 to 4 of formula (I) wherein wherein A is -CH2-, -O-CH2-, C2-C4alkenylene, C2-C4alkynylene or NR3.
6. A compound according to anyone of claims 1 to 5 of formula (I) wherein T-V is -N=N-.
7. A compound according to anyone of claims 1 to 6 of formula (I) wherein Xi and X2 are halogen and X3 is H.
8. A composition for the control of pests, which comprises as active ingredient a compound of formula (I) as described in claim 1 and at least one adjuvant.
9. A method of controlling pests, which comprises using a pesticidally effective amount of at least one compound of formula (I) as described in claim 1 against the pests or at the locus thereof.
10. The use of a compound of formula (I) as described in claim 1 in the control of pests.
EP00938800A 1999-06-21 2000-06-19 Pesticidally active tetrazine derivatives Withdrawn EP1187818A1 (en)

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CN105104407B (en) * 2012-03-10 2017-06-16 陕西韦尔奇作物保护有限公司 A kind of Efficient insecticidal composition
CN102702122B (en) * 2012-05-16 2014-05-14 南通大学 Method for preparing tetrazine by oxidizing dihydro tetrazine
CN105130962B (en) * 2015-09-06 2017-09-26 浙江博仕达作物科技有限公司 A kind of tetrazine pyrazoles acaricide
CN105037329B (en) * 2015-09-06 2017-03-22 青岛科技大学 Fluorine-containing tetrazine pyrazol acaricide
CN105061399B (en) * 2015-09-06 2017-03-22 青岛科技大学 Fluorine-containing tetrazine pyridine compounds and application thereof
CN107573332B (en) * 2016-07-05 2022-04-19 广州再极医药科技有限公司 Aromatic acetylene or aromatic vinyl compound, intermediate thereof, preparation method, pharmaceutical composition and application
SG11202005962YA (en) 2017-12-29 2020-07-29 Guangzhou Maxinovel Pharmaceuticals Co Ltd Aromatic vinyl or aromatic ethyl derivative, preparation method therefor, intermediate, pharmaceutical composition, and application

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DE2963331D1 (en) * 1978-05-25 1982-09-02 Fbc Ltd Acaricidal, larvicidal and ovicidal tetrazine derivatives and compositions, processes for their preparation and methods of using them
EP0029657A3 (en) * 1979-11-16 1981-08-26 Fbc Limited Pesticidal tetrazines, their use and compositions, processes for their preparation and preparation intermediates
EP0036711B1 (en) * 1980-03-22 1985-12-04 Fbc Limited Pesticidal heterocyclic compounds, processes for preparing them, compositions containing them, and their use
HU212613B (en) * 1993-07-21 1996-09-30 Chinoin Gyogyszer Es Vegyeszet Tetrazine-derivatives, process for production of the compounds, acaricidal,larvicidal and ovicidal compositions containing the compounds as active ingredient and process for their production and their use

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EG22089A (en) 2002-07-31

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