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WO2003076409A1 - Derivatives of 1-phenyl-3-phenylpyrazole as herbicides - Google Patents

Derivatives of 1-phenyl-3-phenylpyrazole as herbicides Download PDF

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Publication number
WO2003076409A1
WO2003076409A1 PCT/EP2003/002646 EP0302646W WO03076409A1 WO 2003076409 A1 WO2003076409 A1 WO 2003076409A1 EP 0302646 W EP0302646 W EP 0302646W WO 03076409 A1 WO03076409 A1 WO 03076409A1
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Prior art keywords
halogen
ocf3
independently
alkyl
compound
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French (fr)
Inventor
Michel Muehlebach
Roman Fisera
Milan Karvas
Hermann Rempfler
Hans-Georg Brunner
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Syngenta Participations AG
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Syngenta Participations AG
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Priority to AU2003218758A priority Critical patent/AU2003218758A1/en
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/16—Halogen atoms or nitro radicals

Definitions

  • the present invention relates to novel herbicidally active 1 ,3-diphenylpyrazoles, to processes for their preparation, to compositions comprising those compounds, and to their use in controlling weeds, especially in crops of useful plants, or in inhibiting plant growth.
  • Substituted 1 ,5-diphenylpyrazoles are described, for example, in EP-A-268 554.
  • Substituted 1 ,3-diphenylpyrazoles are also known from Tetrahedron Lett. 2000, 41 , 4713-16. No reference is made to those compounds having biological activity, however.
  • the present invention accordingly relates to compounds of formula I
  • Ri and R 2 are each independently of the other C h alky!, C-*. 6 haloalkyl, C-*- 6 alkoxy, d- ⁇ halo- alkoxy, C-*- 6 alkylthio, d-ehaloalkylthio, C ⁇ .
  • R 9 , R 10 , Rn and R 12 are each independently of the others hydrogen, C ⁇ - 4 alkyl, C ⁇ . 4 - haloalkyl, C 3 . 6 cycloalkyl, C 2 . alkenyl, C 2 . 4 haloalkenyl, C 2 . 3 alkynyl, benzyl or phenyl, and R-* 0 may additionally be an alkali metal or alkaline earth metal, ammonium, a quaternary ammonium base or an amine, or
  • R ⁇ and R 12 together are C 2 . 5 alkylene, p is 0 or 1 ,
  • R 4 and R 6 are each independently of the other hydrogen, C ⁇ alkyl, d shaloalkyl or halogen, or
  • R 4 and R 6 together form a chemical bond
  • R 4 and R 6 together form a radical -CH 2 - or -CH 2 CH 2 -, which may be substituted by d ⁇ alkyl, d- 3 haloalkyl or by halogen, and
  • R 5 , R 7 and R 8 are each independently of the others hydrogen, d- 4 alkyl, d- 3 haloalkyl or halogen, and to enantiomers, and also to configurationally pure E or Z compounds as well as to
  • the alkyl groups appearing in the substituent definitions may be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert- butyl.
  • the alkenyl radicals may be mono- or poly-unsaturated. Halogen is preferably fluorine, bromine or especially chlorine.
  • the radicals R 4 and R 6 may together form a chemical bond, so that a double bond is formed between the carbon atoms to which those radicals are bonded.
  • the present invention then includes both the configurationally pure E or Z compounds and E/Z mixtures.
  • radicals R 4 and R 6 together form a -CH 2 - or -CH 2 CH 2 - group, then together with the carbon atoms to which those radicals are bonded there is formed a three- or four-membered carbocyclic ring in the side chain which may be further substituted by C h alky!, d- 3 haloalkyl or by halogen.
  • Two adjacent R* ⁇ radicals or two adjacent R 2 radicals may together form a d- 3 alkylene chain and thus, together with the carbon atoms to which they are bonded, form a three- to five-membered carbocyclic ring.
  • Such rings may additionally contain one or two oxygen atoms, but two oxygen atoms cannot be adjacent to one another.
  • the resulting heterocyclic rings and also the said carbocyclic rings can be further substituted by halogen.
  • Benzyl and phenyl radicals may be in substituted form.
  • suitable substituents are halogen, d- alkyl, C ⁇ - 4 haloalkyl, d. alkoxy, C ⁇ alkyl- sulfonyl, -CN and -NO 2 .
  • Preferred alkali metal and alkaline earth metal atoms are sodium, potassium, calcium and magnesium.
  • Suitable quaternary ammonium bases are mono-, di-, tri- or tetra-alkylammonium and also corresponding hydroxyalkylammonium compounds, the alkyl radicals preferably containing from 1 to 6 carbon atoms. Accordingly, preferred amines have such alkyl and/or hydroxyalkyl substituents.
  • Enantiomers of the compounds of formula I can be formed by virtue of asymmetric centres which may be present in the molecule.
  • Preferred compounds of formula I are those wherein at least one of the substituents R , R 5) R 6 , R 7 and R 8 is halogen.
  • a further group of preferred compounds of formula I comprises those wherein R 4 and R 6 together form a chemical bond, special importance being attached to those compounds wherein R 8 is halogen, and especially to those wherein R 7 and R 8 are halogen.
  • R 4 and R 6 together form a chemical bond
  • m is 1
  • R occupies the meta-position of the phenyl ring
  • R 5 , R 7 and R 8 are as defined above.
  • R 4 and R 6 together form a chemical bond
  • m 2
  • the two R-* substituents occupy the meta- and ortho-positions or the meta- and para-positions of the phenyl ring
  • R 5 , R 7 and R 8 are each independently of the others hydrogen or halogen
  • p is 1 and R 3 is d- alkyl > C 2 -3alkynyl, halogen or -CN.
  • R and R 6 together form a chemical bond
  • n is 1
  • R 2 occupies the meta-position of the phenyl ring
  • R 5 , R 7 and R 8 are as defined above.
  • R 4 and R 6 together form a chemical bond
  • n is 2
  • the two R 2 substituents occupy the meta- and ortho-positions or the meta- and para-positions of the phenyl ring
  • R 5 , R 7 and R 8 are as defined above.
  • R 4 and R 6 together form a chemical bond
  • n is 1
  • R 2 occupies the meta- position of the phenyl ring
  • R 5 is each independently of the others hydrogen or halogen
  • p is 0.
  • R 4 and R 6 together form a chemical bond
  • n is 2
  • the two R 2 substituents occupy the meta- and ortho-positions or the meta- and para-positions of the phenyl ring
  • R 5 , R 7 and R 8 are each independently of the others hydrogen or halogen
  • p is O.
  • the sum of m + n is greater than or equal to 1.
  • the compounds of formula I can be prepared by means of processes known perse, for example those described in the following Schemes 1 to 4, for example by aiming to synthes- ise the 4- or 5-formylpyrazole intermediate, which can then be further modified en route to the end product (see Schemes 1 , 3 and 4), or instead taking the route by way of the appropriately substituted arylpentadienone intermediate (see Scheme 2).
  • Substituents R-* to R 12 in the Schemes are as defined above.
  • Compounds 6 are suitable as starting compounds for the synthesis of the compounds of formula I.
  • Compounds of formula I wherein the group (R 8 R 7 R 6 )C(R 5 R 4 )C- is to occupy the 5-position of the pyrazole ring are obtained by metallation of compounds 6 wherein Y is H or halogen using a customary metallating reagent, such as n-, sec- or tert- butyllithium or i-PrMgCI or (i-Pr) 2 Mg, optional transmetallation with a reagent such as e.g.
  • the metallated compounds 6 are reacted with, for example, B(OR') 3 , CISnR' 3 or CISiR' 3 and the new products 6_wherein Y is B(OR') 2 , SnR' 3 or SiR' 3 , R' being lower alkyl, are first isolated, optionally subjected to modification (for example hydrolysis of the boric acid ester to form the organoboric acid), and then, optionally in the presence of a Pd or Ni catalyst, reacted with a compound of the formula (R 8 R 7 R 6 )C(R 5 R )C-Q wherein Q is a halogen atom or a radical of the formula -0-SO 2 CF 3 .
  • the radical (R 8 R 7 R 6 )C(R 5 R 4 )C- may already be present in the compound (R 8 R 7 R 6 )C(R 5 R 4 )C-Q, or the substituents R 8 , R 7 , R 6 , R 5 or R 4 are introduced at a later stage by methods known perse.
  • compounds of formula I in which the group (R 8 R 7 R 6 )C(R 5 R 4 )C- is to occupy the 5-position of the pyrazole ring can also be obtained by reaction of compounds 6 wherein Y is halogen or a radical of the formula -O-SO 2 CF 3 (-OTf) (Heck reaction) or wherein Y is -N 2 + (Matsuda reaction), optionally in the presence of a Pd or Ni catalyst, with an olefin to form the compounds 7.
  • the compounds 6 wherein Y is H or halogen are converted by direct metallation or by means of a halogen-metal exchange, with, for example, n-butyl- lithium, into the corresponding organometal compounds, followed by quenching either with a CHO-donor, such as DMF, 1 -formylpiperidine, methyl formate or ethyl formate, or with a compound of the formula R 5 CO-L wherein L is a leaving group, such as halogen, -OMe or -OEt (Step 5).
  • a CHO-donor such as DMF, 1 -formylpiperidine, methyl formate or ethyl formate
  • L is a leaving group, such as halogen, -OMe or -OEt
  • the compounds 9 are obtained from 8 under conditions other than Wittig conditions by carrying out a reaction with (b) a compound of formula R 7 R 8 CXH wherein X is halogen in the presence of a base, for example KOH or DBU (1 ,8-diazabicyclo[5.4.0]undec-7-ene) (see V.K. Aggarwal et al., J. Org. Chem.
  • the intermediate carbinols of formula 6 wherein Y is (R 7 R 8 CX)-(R 5 )C(OH)- which are initially formed in this variant (b) are acylated in a one-pot process with the addition of, for example, acetic anhydride, and the acylated intermediate carbinols of formula 6 wherein Y is (R 7 R 8 CX)-(R 5 )C(OCOCH 3 )- are finally reduced to form the compounds 9, with dilution with e.g. acetic acid and addition of zinc, magnesium or sodium.
  • Dihalovinyl compounds 9 can accordingly be obtained, for example, by Pd- or Ni-catalysed reaction of trichloroethylene with a metallated form of the compounds 6, as described, for example, by G.
  • Compounds 6 wherein Y is trifluoromethanesulfon- ate (triflate) can also be obtained from compounds 3 (J. Fluorine Chem. 02, 135, 2000).
  • the compounds 3 are obtainable by customary condensation of the keto esters 1 with the arylhydrazines 2 (Step 1 a) in solvents such as acetic acid, methanol, ethanol or toluene, optionally in the presence of catalytic amounts of acid, e.g. HCI, H 2 SO , p-TsOH.
  • the compounds 6 can also be obtained by Sandmeyer reaction of the aminopyrazoles 5 (Step 3) either under the customary aqueous conditions (e.g. NaNO 2 , HCI, CuCI or NaNO 2 , AcOH/H 2 SO 4 , Cu 2 0, EtOH for reductive deamination) or under anhydrous conditions such as t-BuONO, Cul, CH 2 I -
  • Compounds 5 are obtained by condensation of cyanoketones 4 with arylhydrazines 2 (Step 1 b) in various solvents such as acetic acid, methanol, ethanol or toluene, optionally in the presence of catalytic amounts of acid, e.g. HCI, H 2 SO 4 , p-TsOH.
  • the starting compounds 1, 2 and 4 are either known or can be prepared by known methods.
  • Compounds of formula I can also be prepared from the starting compounds 4 (Scheme 2).
  • the aryldihalopentadienones 4 are condensed with appropriately substituted hydrazines 5 (Step 3) to form substituted ⁇ 2 -pyrazolines 6 (A.A. Dudinov et al., Chem. Heterocycl. Cmpd. (Engl. Transl.) 31, 1311 , 1995).
  • That reaction can be carried out in various solvents such as acetic acid, methanol, ethanol or toluene, optionally in the presence of catalytic amounts of acid, e.g.
  • the oxidation to form the corresponding dihalovinylpyrazoles 7 can be carried out under various conditions, e.g. by the use of air, DDQ (J.A. Katzenellenbogen et al., Org. Letters 2, 2833, 2000), chloranil, MnO 2 , KMnO 4 or Phl(OAc) 2 in various solvents such as DMSO, benzene, toluene, xylene, water, acetone or methylene chloride.
  • DDQ J.A. Katzenellenbogen et al., Org. Letters 2, 2833, 2000
  • chloranil MnO 2 , KMnO 4 or Phl(OAc) 2
  • solvents such as DMSO, benzene, toluene, xylene, water, acetone or methylene chloride.
  • the starting compounds 4 are obtainable by aldol condensation of compounds 2 with various aryl alkyl ketones 3 (Step 2) (YN. Maeskii et al., Chem. Heterocycl. Cmpd (Engl. Transl.) 6, 1081 , 1970).
  • Compounds 2 can be obtained by free radical R 8 R 7 CX 2 -addition to vinyl ethers, (Step 1). They are described e.g. in Houben-Weyl, Vol. V/3, p. 973, 1962. It is possible to use free radical starters, for example dibenzoyl peroxide, AIB ⁇ , sodium dithionite (W.-Y. Huang et al., J. Fluorine Chem.
  • the compounds of formula I can also be prepared from compounds 4 (Scheme 3).
  • the compounds 4 are converted into the compounds 5 (Step 3) under conditions as described in Step 6 of Scheme 1.
  • the compounds of formula I can also be prepared from the pyrazolones 6.
  • the preparation of those compounds is illustrated in Scheme 1.
  • the compounds 6 are formylated (Step 5, see DE 2438779) and the aldehyde compounds 7 so obtained are converted into the products 8 under the conditions described for Step 6 in Scheme 1.
  • the compounds of formula I can also be prepared from the compounds 10.
  • the compounds 10 are converted into the compounds 4 (Step 8) under conditions as described in Step 5 of Scheme 1.
  • the compounds 10 are converted into the compounds 5 (Step 9) under conditions as described in Step 7 of Scheme 1.
  • compounds of formula I having a radical (R 8 R 7 R 6 )C(R 5 R )C- in the 4- postion of the pyrazole ring compounds H are obtained from 10 (Step 10) under conditions as described in Step 4 of Scheme 1.
  • the radical (R 8 R 7 R 6 )C(R 5 R 4 )C- may already be present in the starting compound 10, or the substituents R 8 , R 7 , R 6l R5 or R are introduced at a later stage by methods known per se.
  • the compounds 10 can be obtained from the 1 ,3-diphenylpyrazoles 9 by halogenation of the 4-pyrazole position (Step 7) under conditions as described, for example, in Can. J. Chem. 1986, 64, 2211-19.
  • the starting compounds 9 are either known or can be prepared by known methods.
  • the compounds of formula I can also be prepared from compounds 4 by 1 ,3-dipolar cyclo- addition of diphenylnitrile imine, prepared in situ, to alkenes and alkynes to form 1 ,3-di- phenyl- ⁇ 2 -pyrazolines and 1 ,3-diphenylpyrazoles (R. Huisgen et al., Chem. Ber. 776, 3438, 1983; ibid., Tetrahedron 77, 3, 1962) (Scheme 4).
  • the preferred compounds of formula I having a dihalovinyl substituent in the 5-position of the pyrazole ring can be obtained by reaction of the compounds 4 with a base, preferably triethylamine, in the presence of either an alkyne, e.g. propargylaldehyde acetal, or an alkene, e.g. acrolein or acrolein acetal (Step 3).
  • the compounds 5 are then obtainable by hydrolysis or oxidation (under the conditions described in Step 4 of Scheme 2).
  • the compounds 5 can be converted (Step 4) into the products 6 under the conditions described in Step 6 of Scheme 1.
  • the compounds 4 are obtainable by known methods from the hydrazides 3 (Step 2). Those compounds are known per se or can be prepared by customary methods.
  • R-i and R 2 are each independently of the other d. 6 alkyl, d-ehaloalkyl, d- 6 alkoxy, d-ehalo- alkoxy, d- 6 alkylthio, d- 6 haloalkylthio, d- 6 alkylsulfinyl, C ⁇ . 6 haloalkylsulfinyl, d- 6 alkylsulfonyl, d-ehaloalkylsulfonyl, C ⁇ - 8 alkylcarbonyl, d.
  • haloalkylcarbonyl, halogen, -CN, -NO 2 or -SF 5 , or two adjacent R-* substituents or two adjacent R 2 substituents are, independently of one another, d- 3 alkylene, d- 3 alkylene containing 1 or 2 oxygen atoms, there being no oxygen- oxygen bond, C ⁇ - 3 haloalkylene or d.
  • 3 haloalkylene containing 1 or 2 oxygen atoms, there being no oxygen-oxygen bond, m and n are each independently of the other 0, 1 , 2 or 3,
  • R 3 is d- 4 alkyl, C ⁇ . 4 haloalkyl, C ⁇ - 4 alkoxy, C*
  • R 9 , R 10 , R- 11 and R 12 are each independently of the others hydrogen, d- 4 alkyl, d. - haloalkyl, C 3 - 6 cycloalkyl, C 2 - 4 alkenyl, C 2 .
  • R 10 may additionally be an alkali metal or alkaline earth metal, a quaternary ammonium base or an amine, or R- 11 and R- 12 together are C 2 - 5 alkylene, p is 0, 1 , 2 or 3, preferably 0 or 1 ,
  • R 4 and R 6 are each independently of the other hydrogen, d- 4 alkyl, d- 3 haloalkyl or halogen, or
  • R 4 and R 6 together form a chemical bond
  • R 4 and R 6 together form a radical -CH 2 - or -CH 2 CH 2 -, which may be substituted by d- alkyl,
  • R 5 , R 7 and R 8 are each independently of the others hydrogen, C ⁇ - 4 alkyl, C ⁇ . 3 haloalkyl or halogen, at least one of those substituents being other than hydrogen, the compounds of formulae
  • the reactions to form compounds of formula I are advantageously performed in aprotic, inert organic solvents.
  • solvents are hydrocarbons, such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons, such as dichloromethane, trichloromethane, tetra- chloromethane and chlorobenzene, ethers, such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and dioxane, nitriles, such as aceto- nitrile and propionitrile, amides, such as N,N-dimethylformamide, diethylformamide and N- methylpyrrolidinone.
  • the reaction temperatures are preferably from -78°C to +120°C.
  • the reactions generally proceed slightly exothermically and can generally be carried out at room temperature.
  • the reaction mixture may, if appropriate, be heated for a short time to a temperature up to its boiling point.
  • the reaction times may likewise be shortened by the addition of a few drops of base as reaction catalyst.
  • Suitable bases are especially tertiary amines, such as trimethyl- amine, triethylamine, quinuclidine, 1 ,4-diazabicyclo[2.2.2]octane, 1 ,5-diazabicyclo[4.3.0]non- 5-ene and 1 ,5-diazabicyclo[5.4.0]undec-7-ene, but it is also possible to use inorganic bases, such as hydrides, e.g. sodium or calcium hydride, hydroxides, such as sodium or potassium hydroxide, carbonates, such as sodium or potassium carbonate, or hydrogen carbonates, such as potassium or sodium hydrogen carbonate.
  • hydrides e.g. sodium or calcium hydride
  • hydroxides such as sodium or potassium hydroxide
  • carbonates such as sodium or potassium carbonate
  • hydrogen carbonates such as potassium or sodium hydrogen carbonate.
  • the compounds of formula I can be isolated in customary manner by concentration and/or evaporation of the solvent and can be purified by recrystallisation or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons.
  • the compounds of formula I may be used as herbicides in their unmodified form, that is to say as obtained in the synthesis, but they are preferably formulated in customary manner together with the adjuvants conventionally employed in formulation technology, for example into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules.
  • Such formulations are described, for example, on pages 9 to 13 of WO 97/34485.
  • the methods of application such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
  • compositions, preparations or mixtures comprising the compound (active ingredient) of formula I or at least one compound of formula I and, usually, one or more solid or liquid formulation adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with the formulation adjuvants, for example solvents or solid carriers.
  • formulation adjuvants for example solvents or solid carriers.
  • Surface-active compounds surfactants
  • solvents and solid carriers are given, for example, on page 6 of WO 97/34485.
  • suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties.
  • suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of WO97/34485.
  • surfactants conventionally employed in formulation technology which are described, inter alia, in "McCutcheon's Detergents and Emulsifiers Annual” MC Publishing Corp., Ridgewood New Jersey, 1981 , Stache, H., “Tensid-Taschenbuch", Carl Hanser Verlag, Kunststoff/Vienna 1981 , and M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-81 , are also suitable for the preparation of the herbicidal compositions according to the invention.
  • the herbicidal formulations generally contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of herbicide, from 1 to 99.9 % by weight, especially from 5 to 99.8 % by weight, of a solid or liquid formulation adjuvant, and from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant.
  • a surfactant especially from 0.1 to 25 % by weight
  • compositions may also comprise further ingredients, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), anti-foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
  • stabilisers for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), anti-foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
  • the compounds of formula I are generally applied to plants or the locus thereof at rates of application of from 0.001 to 4 kg/ha, especially from 0.005 to 2 kg/ha.
  • concentration required to achieve the desired effect can be determined by experiment. It is dependent on the nature of the action, the stage of development of the cultivated plant and of the weed and on the application (place, time, method) and may vary within wide limits as a function of those parameters.
  • the compounds of formula I are distinguished by herbicidal and growth-inhibiting properties, allowing them to be used in crops of useful plants, especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and also for non-selective weed control.
  • crops of useful plants especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and also for non-selective weed control.
  • crops is to be understood as including also crops that have been made tolerant to herbicides or classes of herbicides as a result of conventional methods of breeding or genetic techniques.
  • the weeds to be controlled may be either monocotyledonous or dicotyledonous weeds, such as, for example, Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
  • Stellaria Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon,
  • Example P1 Preparation of 4-(2,2-dichlorovinyl)-1 -(2,4-difluorophenyl)-3-(3-trifluoro- methylphenyl)-1 H-pyrazole (3)
  • Step 1 Preparation of ⁇ /-(2,4-dif luorophenyl)- ⁇ / '-[1 -(3-trifluoromethylphenyl)-ethylidene]- hydrazine (1 )
  • Step 2 Preparation of 1 -(2,4-dif luorophenyl)-3-(3-trif luoromethylphenyl)-1 H-pyrazole-4- carbaldehyde (2)
  • reaction mixture is discharged into ice/water and adjusted to a pH value of 7 with concentrated NaOH; the resulting suspension is briefly cooled, then filtered and washed with water. The precipitate is dried. 11.3 g (95% of theory) of the aldehyde (2) are obtained in the form of a solid having a melting point of 55-57°C.
  • Step 3 Preparation of 4-(2,2-dichlorovinyl)-1-(2,4-difluorophenyl)-3-(3-trifluoromethyl- phenyl)-1 H-pyrazole (3)
  • Step 1 Preparation of 3-(4-chlorophenyl)-1 -(3-trif luoromethylphenyl)-1 H-pyrazole-4- carbaldehyde (4)
  • Step 2 Preparation of 3-(4-chlorophenyl)-4-(2,2-dichlorovinyl)-1-(3-trifluoromethylphenyl)- 1 H-pyrazole (5)
  • the cooled reaction mixture is clarified by filtration and the filtrate is concentrated by evaporation.
  • the residue is purified by means of preparative HPLC on silica gel (gradient ethyl acetate/hexane from 9% to 100%) and the product is crystallised from hexane with the addition of a small amount of ethyl acetate. 780 mg (16% of theory) of the dichlorovinyl- pyrazole (5) are obtained in the form of a solid having a melting point of 94-96°C.
  • Example P3 Preparation of 1 -(3-chlorophenyl)-5-(2,2-dichlorovinyl)-3-(4-trifluoromethyl- phenyl)-1 H-pyrazole (8)
  • Step 1 Preparation of ethyl-(1 ,3,3,3-tetrachloropropyl) ether (6)
  • Step 2 Preparation of 5,5-dichloro-1 -(4-trif luoromethylphenyl)-penta-2,4-dien-1 -one (7)
  • Step 3 Preparation of 1 -(3-chlorophenyl)-5-(2,2-dichlorovinyl)-3-(4-trifluoromethyl- phenyl)-1 H-pyrazole (8)
  • Example P4 Preparation of 3-(4-chlorophenyl)-5-(2,2-dichlorovinyl)-1 -(3-trifluoromethyl- phenyl)-4.5-dihydro-1 H-pyrazole (10) and 3-(4-chlorophenyl)-5-(2,2-dichlorovinyl)-1-(3- trifluoromethylphenyl)-1 H-pyrazole (11)
  • Step 1 Preparation of 5,5-dichloro-1 -(4-chlorophenyl)-penta-2,4-dien-1 -one (9)
  • Step 2 Preparation of 3-(4-chlorophenyl)-5-(2,2-dichlorovinyl)-1 -(3-trif luoromethylphenyl)- 4,5-dihydro-1 H-pyrazole (10) and 3-(4-chlorophenyl)-5-(2,2-dichlorovinyl)-1-(3-tri- fluoromethylphenyl)-1 H-pyrazole (11 )
  • Example P6 Preparation of 3-(4-chlorophenyl)-5-(2.2-dibromovinyl)-1 -(3-trif luoromethyl- phenvD-1 H-pyrazole (16) and 5-(2,2-difluorovinyl)-3-(4-fluorophenyl)-1-(3-trifluoromethyl- phenyl)-1 H-pyrazole (17)
  • Step 1 Preparation of 5-(4-chlorophenyl)-2-(3-trifluoromethylphenyl)-2,4-dihydro-pyrazol- 3-one (13)
  • the reaction mixture is completely concentrated, the residue is taken up in saturated Na 2 CO 3 solution and the aqueous phase is extracted with ethyl acetate. The organic phase is dried over sodium sulfate, filtered and concentrated by evaporation.
  • the product is partially crystallised from ethyl acetate/hexane 1 :1 (5.7 g).
  • the mother liquor is purified by column chromatography on silica gel using hexane/ethyl acetate 4:1 (2.45 g). In total, 8.15 g (45% of theory) of the pyrazolone (13) are obtained in the form of a solid having a melting point of 173-174°C.
  • Step 2 Preparation of 5-bromo-3-(4-chlorophenyl)-1 -(3-trif luoromethylphenyl)-1 H-pyrazole (14)
  • the reaction mixture is slowly discharged into ice/water, the organic phase is separated off and the aqueous phase is extracted with ethyl acetate; the combined organic phases are washed with water, then dried over sodium sulfate, filtered and concentrated by evaporation.
  • the residue is purified by means of preparative HPLC on silica gel (gradient ethyl acetate/hexane from 9% to 100%). 1.09 g (54% of theory) of the bromo-pyrazole (14) are obtained in the form of a viscous oil.
  • Step 4 Preparation of 3-(4-chlorophenyl)-5-(2,2-dibromovinyl)-1 -(3-trif luoromethylphenyl)- 1 H-pyrazole (16)
  • triphenylphosphine 950 mg are added in portions to a solution, cooled to -20°C, of 210 mg of aldehyde (15) (Example P6, Step 3) and 600 mg of carbon tetrabromide in 10 ml of methylene chloride.
  • the reaction mixture is stirred at from -20°C to -30°C for one hour.
  • Saturated sodium chloride solution is added to the reaction mixture; the organic phase is separated off and the aqueous phase is extracted with methylene chloride.
  • the combined organic phases are dried over sodium sulfate, filtered and concentrated by evaporation.
  • Step 5 Preparation of 5-(2,2-difluorovinyl)-3-(4-fluorophenyl)-1 -(3-trifluoromethylphenyl)- 1 H-pyrazole (17)
  • Step 1 Preparation of 5-(4-chlorophenyl)-2-(3-trifluoromethylphenyl)-2H-pyrazol-3-yl- amine (18)
  • reaction mixture is completely concentrated and the residue is caused to crystallise by azeotropic treatment with toluene (4x 20 ml) and diethyl ether (3x 20ml).
  • 14.0 g (97% of theory) of the aminopyrazole (18) are obtained in the form of a solid having a melting point of 128-130°C, which is used in the next reaction without further purification.
  • Step 3 Preparation of 3-(4-chlorophenyl)-1 -(3-trif luoromethylphenyl)-5-vinyl-1 H-pyrazole (20)
  • reaction mixture is completely concentrated and the residue is purified by column chromatography on silica gel using hexane/ethyl acetate 9:1. 110 mg (78% of theory) of the vinyl-pyrazole (20) are obtained in the form of a solid having a melting point of 97-99°C.

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Abstract

Compounds of formula I: (Formula I); wherein the substituents are as defined in claim 1, are suitable for use as herbicides.

Description

DERIVATIVES OF l-PHENYL-3-PHENYLPYRAZOLE AS HERBICIDES
The present invention relates to novel herbicidally active 1 ,3-diphenylpyrazoles, to processes for their preparation, to compositions comprising those compounds, and to their use in controlling weeds, especially in crops of useful plants, or in inhibiting plant growth.
Substituted 1 ,5-diphenylpyrazoles are described, for example, in EP-A-268 554. Substituted 1 ,3-diphenylpyrazoles are also known from Tetrahedron Lett. 2000, 41 , 4713-16. No reference is made to those compounds having biological activity, however.
Novel substituted 1 ,3-diphenylpyrazoles having herbicidal and growth-inhibiting properties have now been found.
The present invention accordingly relates to compounds of formula I
Figure imgf000002_0001
wherein
Ri and R2 are each independently of the other Chalky!, C-*.6haloalkyl, C-*-6alkoxy, d-βhalo- alkoxy, C-*-6alkylthio, d-ehaloalkylthio, Cι.6alkylsulfinyl, Cι-6haloalkylsulfinyl, Ct-ealkylsu'fonyl, Ci-ehaloalkylsulfonyl, Cι-6alkylcarbonyl, C^haloalkylcarbonyl, halogen, -CN, -NO2 or -SF5, or two adjacent Rn substituents or two adjacent R2 substituents are, independently of one another, C*ι-3alkylene, Cι-3alkylene containing 1 or 2 oxygen atoms, there being no oxygen- oxygen bond, C|-3haloalkylene or C^haloalkylene containing 1 or 2 oxygen atoms, there being no oxygen-oxygen bond, m and n are each independently of the other 0, 1 , 2 or 3, R3 is C-i-4alkyl, d-4haloalkyl,
Figure imgf000003_0001
d- - alkylsulfinyl, d-4alkylsulfonyl, C2. alkenyl, C2.4haloalkenyl, C2-3alkynyl, halogen, -CN, -NO2,
-CHO, -COR9, -COOR10 or -CONRnR^, wherein R9, R10, Rn and R12 are each independently of the others hydrogen, Cι-4alkyl, Cι.4- haloalkyl, C3.6cycloalkyl, C2. alkenyl, C2.4haloalkenyl, C2.3alkynyl, benzyl or phenyl, and R-*0 may additionally be an alkali metal or alkaline earth metal, ammonium, a quaternary ammonium base or an amine, or
Rιι and R12 together are C2.5alkylene, p is 0 or 1 ,
R4 and R6 are each independently of the other hydrogen, C^alkyl, d shaloalkyl or halogen, or
R4 and R6 together form a chemical bond, or
R4 and R6 together form a radical -CH2- or -CH2CH2-, which may be substituted by d^alkyl, d-3haloalkyl or by halogen, and
R5, R7 and R8 are each independently of the others hydrogen, d-4alkyl, d-3haloalkyl or halogen, and to enantiomers, and also to configurationally pure E or Z compounds as well as to
E/Z mixtures of such compounds.
The alkyl groups appearing in the substituent definitions may be straight-chain or branched and are, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl and tert- butyl. The alkenyl radicals may be mono- or poly-unsaturated. Halogen is preferably fluorine, bromine or especially chlorine. The radicals R4 and R6 may together form a chemical bond, so that a double bond is formed between the carbon atoms to which those radicals are bonded. The present invention then includes both the configurationally pure E or Z compounds and E/Z mixtures. When the radicals R4 and R6 together form a -CH2- or -CH2CH2- group, then together with the carbon atoms to which those radicals are bonded there is formed a three- or four-membered carbocyclic ring in the side chain which may be further substituted by Chalky!, d-3haloalkyl or by halogen. Two adjacent R*ι radicals or two adjacent R2 radicals may together form a d-3alkylene chain and thus, together with the carbon atoms to which they are bonded, form a three- to five-membered carbocyclic ring. Such rings may additionally contain one or two oxygen atoms, but two oxygen atoms cannot be adjacent to one another. The resulting heterocyclic rings and also the said carbocyclic rings can be further substituted by halogen. Benzyl and phenyl radicals may be in substituted form. Examples of suitable substituents are halogen, d- alkyl, Cι-4haloalkyl, d. alkoxy, C^alkyl- sulfonyl, -CN and -NO2. Preferred alkali metal and alkaline earth metal atoms are sodium, potassium, calcium and magnesium. Suitable quaternary ammonium bases are mono-, di-, tri- or tetra-alkylammonium and also corresponding hydroxyalkylammonium compounds, the alkyl radicals preferably containing from 1 to 6 carbon atoms. Accordingly, preferred amines have such alkyl and/or hydroxyalkyl substituents. Enantiomers of the compounds of formula I can be formed by virtue of asymmetric centres which may be present in the molecule.
Preferred compounds of formula I are those wherein at least one of the substituents R , R5) R6, R7 and R8 is halogen.
A further group of preferred compounds of formula I comprises those wherein R4 and R6 together form a chemical bond, special importance being attached to those compounds wherein R8 is halogen, and especially to those wherein R7 and R8 are halogen.
Also preferred are compounds wherein R4 and R6 together form a chemical bond, the radical -CR5=CR7R8 thus formed occupies the 5-position, m is 1 , and R occupies the meta-position of the phenyl ring, and R5, R7 and R8 are as defined above.
Preference is also given to those compounds wherein R and R6 together form a chemical bond, the radical -CR5=CR7R8 thus formed occupies the 5-position, m is 2, and the two R-* substituents occupy the meta- and ortho-positions or the meta- and para-positions of the phenyl ring, and R5l R7 and R8 are as defined above.
Special importance is attached to compounds of formula I wherein R4 and R6 together form a chemical bond, the radical -CR5=CR7R8 thus formed occupies the 5-position, m is 1 , and R-* occupies the meta-position of the phenyl ring, and R5, R7 and R8 are each independently of the others hydrogen or halogen, and p is 0.
Preferred compounds of formula I are also those wherein R4 and R6 together form a chemical bond, the radical -CR5=CR7R8 occupies the 5-position, m is 1 , and R-* occupies the meta- position of the phenyl ring, and R5, R7 and R8 are each independently of the others hydrogen or halogen, and p is 1 and R3 is C1- alkyl, C2.3alkynyl, halogen or -CN. Special importance is also attached to the compounds of formula I wherein R4 and R6 together form a chemical bond, the radical -CR5=CR7R8 thus formed occupies the 5-position, m is 2, and the two R-i substituents occupy the meta- and ortho-positions or the meta- and para-positions of the phenyl ring, and R5, R7 and R8 are each independently of the others hydrogen or halogen, and p is 0.
Also preferred are compounds of formula I wherein R4 and R6 together form a chemical bond, the radical -CR5=CR7R8 occupies the 5-position, m is 2, the two R-* substituents occupy the meta- and ortho-positions or the meta- and para-positions of the phenyl ring, R5, R7and R8 are each independently of the others hydrogen or halogen, and p is 1 and R3 is d- alkyl> C2-3alkynyl, halogen or -CN.
In a further group of preferred compounds of formula I, R and R6 together form a chemical bond, the radical -CR5=CR7R8 thus formed occupies the 4-position, n is 1 , and R2 occupies the meta-position of the phenyl ring, and R5, R7 and R8 are as defined above.
Further preferred compounds of formula I are those wherein R4 and R6 together form a chemical bond, the radical -CR5=CR7R8 occupies the 4-position, n is 2, and the two R2 substituents occupy the meta- and ortho-positions or the meta- and para-positions of the phenyl ring, and R5, R7 and R8 are as defined above.
In an especially suitable group of compounds of formula I, R4 and R6 together form a chemical bond, the radical -CR5=CR7R8 occupies the 4-position, n is 1 , and R2 occupies the meta- position of the phenyl ring, and R5) R7 and R8 are each independently of the others hydrogen or halogen, and p is 0.
Preferred compounds of formula I are also those wherein R4 and R6 together form a chemical bond, the radical -CR5=CR7R8 occupies the 4-position, n is 1 , R2 occupies the meta- position of the phenyl ring, and R5, R7 and R8are each independently of the others hydrogen or halogen, and p is 1 and R3 is d^alkyl, C2-3alkynyl, halogen or -CN.
In a further especially suitable group of compounds of formula I, R4 and R6 together form a chemical bond, the radical -CR5=CR7R8 occupies the 4-position, n is 2, and the two R2 substituents occupy the meta- and ortho-positions or the meta- and para-positions of the phenyl ring, and R5, R7 and R8 are each independently of the others hydrogen or halogen, and p is O.
Preference is also given to those compounds of formula I wherein R4 and R6 together form a chemical bond, the radical -CR5=CR7R8 occupies the 4-position, n is 2, and the two R2 substituents occupy the meta- and ortho-positions or the meta- and para-positions of the phenyl ring, R5, R7 and R8 are each independently of the others hydrogen or halogen, and p is 1 and R3 is C1- alkyl, C2.3alkynyl, halogen or -CN.
In another group of suitable compounds, the sum of m + n is greater than or equal to 1.
The compounds of formula I can be prepared by means of processes known perse, for example those described in the following Schemes 1 to 4, for example by aiming to synthes- ise the 4- or 5-formylpyrazole intermediate, which can then be further modified en route to the end product (see Schemes 1 , 3 and 4), or instead taking the route by way of the appropriately substituted arylpentadienone intermediate (see Scheme 2). Substituents R-* to R12 in the Schemes are as defined above.
Scheme 1
Figure imgf000007_0001
Compounds 6 (Scheme 1 ) are suitable as starting compounds for the synthesis of the compounds of formula I. Compounds of formula I wherein the group (R8R7R6)C(R5R4)C- is to occupy the 5-position of the pyrazole ring are obtained by metallation of compounds 6 wherein Y is H or halogen using a customary metallating reagent, such as n-, sec- or tert- butyllithium or i-PrMgCI or (i-Pr)2Mg, optional transmetallation with a reagent such as e.g. ZnCI2, and subsequent reaction of the organometallic compound, optionally in the presence of a Pd or Ni catalyst, with a compound of the formula (R8R7R6)C(R5R4)C-Q wherein Q is a halogen atom or a radical of the formula -O-SO2CF3. As an alternative to the preparation of compounds of formula I having a radical (R8R7R6)C(R5R4)C- in the 5-position of the pyrazole ring, the metallated compounds 6 are reacted with, for example, B(OR')3, CISnR'3 or CISiR'3 and the new products 6_wherein Y is B(OR')2, SnR'3 or SiR'3, R' being lower alkyl, are first isolated, optionally subjected to modification (for example hydrolysis of the boric acid ester to form the organoboric acid), and then, optionally in the presence of a Pd or Ni catalyst, reacted with a compound of the formula (R8R7R6)C(R5R )C-Q wherein Q is a halogen atom or a radical of the formula -0-SO2CF3. Using the above-described reactions for the formation of a C-C bond there are obtained compounds 7 (Step 4) under conditions such as are typically known from the Negishi coupling (organozinc compounds, especially organozinc halides), the Suzuki coupling (organoboron compounds, especially organoboric acids), the Stille coupling (organotin compounds, especially organotrialkyltin), the Kumada coupling (Grignard reagent, especially organomagnesium halides) and the Hiyama coupling (organosilicon compound, especially organotrialkylsilicon). The radical (R8R7R6)C(R5R4)C- may already be present in the compound (R8R7R6)C(R5R4)C-Q, or the substituents R8, R7, R6, R5 or R4 are introduced at a later stage by methods known perse.
The polarity of the reactants in Step 4 can also be reversed. Such a reversal of polarity is suitable when secondary reactions occur or when the reagents are more readily obtainable. Compounds of formula I in which the group (R8R7R6)C(R5R4)C- is to occupy the 5-position of the pyrazole ring are accordingly obtained by reaction of a compound 6 wherein Y is halogen, a radical of formula -O-SO2CF3 (-OTf) or -N2 +, optionally in the presence of a Pd or Ni catalyst, with a compound of the formula (R8R7R6)C(R5R4)C-M wherein M is a mono- to tetra-valent metal atom, for example lithium, sodium, potassium, magnesium halide, zinc halide, boric acid or boric acid ester, trialkyltin or trialkylsilicon, under the above-described conditions of the methods of forming a C-C bond by cross-coupling. For an illustration of such a process, reference is made to the reaction of a substrate of type 6. wherein Y is bromine, with tributylvinylstannane (Stille coupling) (X. Wang et al., Tetrahedron Lett. 41, 4713, 2000). Furthermore, compounds of formula I in which the group (R8R7R6)C(R5R4)C- is to occupy the 5-position of the pyrazole ring can also be obtained by reaction of compounds 6 wherein Y is halogen or a radical of the formula -O-SO2CF3 (-OTf) (Heck reaction) or wherein Y is -N2 + (Matsuda reaction), optionally in the presence of a Pd or Ni catalyst, with an olefin to form the compounds 7.
For the preparation of the compounds of formula I having a dihalovinyl substituent in the 5- position of the pyrazole ring, the compounds 6 wherein Y is H or halogen are converted by direct metallation or by means of a halogen-metal exchange, with, for example, n-butyl- lithium, into the corresponding organometal compounds, followed by quenching either with a CHO-donor, such as DMF, 1 -formylpiperidine, methyl formate or ethyl formate, or with a compound of the formula R5CO-L wherein L is a leaving group, such as halogen, -OMe or -OEt (Step 5). The formylated or acylated compounds 8 thus obtained are converted into the key vinyl compounds 9 by reaction (Step 6) either (Wittig conditions) with (a) a compound of the formula R7R8C=P(C6H5)3, which may possibly be generated in situ, which can be prepared, for example, from CHCI3 and a base such as t-BuOK in the presence of P(C6H5)3 (A.J. Speziale et al., Org. Synth. V, 361 , 1973), or from CCI or CBr4 in the presence of P(C6H5)3 (S.A. Giacobbe et al., Synth. Commun. 29, 3125, 1999; R. Appel et al., Angew. Chem. Int. Ed. Engl. 14, 801 , 1975), or from, for example, CIF2CCOONa in the presence of P(C6H5)3 (R.M. Silverstein et al., Org. Synth. 47, 49, 1967). Alternatively, the compounds 9 are obtained from 8 under conditions other than Wittig conditions by carrying out a reaction with (b) a compound of formula R7R8CXH wherein X is halogen in the presence of a base, for example KOH or DBU (1 ,8-diazabicyclo[5.4.0]undec-7-ene) (see V.K. Aggarwal et al., J. Org. Chem. 65, 7211 , 2000), or with a compound of formula R7R8CXCOOH / R7R8CXCOONa wherein X is halogen (Z. Wang et al., Tetrahedron Lett. 41, 4007, 2000). The intermediate carbinols of formula 6 wherein Y is (R7R8CX)-(R5)C(OH)- which are initially formed in this variant (b) are acylated in a one-pot process with the addition of, for example, acetic anhydride, and the acylated intermediate carbinols of formula 6 wherein Y is (R7R8CX)-(R5)C(OCOCH3)- are finally reduced to form the compounds 9, with dilution with e.g. acetic acid and addition of zinc, magnesium or sodium.
Furthermore, compounds of formula I having a dihalovinyl substituent in the 5-position of the pyrazole ring can be obtained by reacting the compounds 6 with a compound of the formula (R8R7)C=CR5-Q or (R8R7)C=CR5— , optionally in the presence of a Pd or Ni catalyst (Step 7), wherein Y, Q and M are as defined in Step 4 and the variants and conditions of the C-C linkage mentioned therein apply. Dihalovinyl compounds 9 can accordingly be obtained, for example, by Pd- or Ni-catalysed reaction of trichloroethylene with a metallated form of the compounds 6, as described, for example, by G. Linstrumelle et al., Tetrahedron Lett. 26, 2575, 1985. The polarity of the reactants occurring in that Step 7 can be reversed in accordance with D.J. Burton et al., J. Org. Chem. 63, 1714, 1998 and J. Org. Chem. 62, 7758, 1997, for example by reaction of an organometallic compound of the F2C=CHZnCI type with a compound 6 wherein Y is halogen or a radical of the formula -O-SO2CF3(-OTf), it likewise being possible for Pd or Ni catalysts to be present.
Compounds 10 having a halogen substituent in the 4-position are obtained, for example, by treatment of compounds 9 with N-halosuccinimide NR3S (R3 = CI, Br, I), (Step 8) in an inert solvent, preferably methylene chloride, DMF or acetonitrile. The compounds 6 are obtainable by reaction of pyrazolones 3 with POZ3 or PZ3 (Z = CI, Br, I), (Step 2), preferably in solvents such as benzene, toluene, xylene or acetonitrile (X. Wang et al., Tetrahedron Lett. 41, 4713, 2000). Compounds 6 wherein Y is trifluoromethanesulfon- ate (triflate) can also be obtained from compounds 3 (J. Fluorine Chem. 02, 135, 2000). The compounds 3 are obtainable by customary condensation of the keto esters 1 with the arylhydrazines 2 (Step 1 a) in solvents such as acetic acid, methanol, ethanol or toluene, optionally in the presence of catalytic amounts of acid, e.g. HCI, H2SO , p-TsOH.
The compounds 6 can also be obtained by Sandmeyer reaction of the aminopyrazoles 5 (Step 3) either under the customary aqueous conditions (e.g. NaNO2, HCI, CuCI or NaNO2, AcOH/H2SO4, Cu20, EtOH for reductive deamination) or under anhydrous conditions such as t-BuONO, Cul, CH2I - Compounds 5 are obtained by condensation of cyanoketones 4 with arylhydrazines 2 (Step 1 b) in various solvents such as acetic acid, methanol, ethanol or toluene, optionally in the presence of catalytic amounts of acid, e.g. HCI, H2SO4, p-TsOH.
The starting compounds 1, 2 and 4 are either known or can be prepared by known methods.
Scheme 2
r F, CI,
Figure imgf000011_0002
Compounds of formula I can also be prepared from the starting compounds 4 (Scheme 2). For the preparation of the preferred compounds of formula I having a dihalovinyl group in the 5-position of the pyrazole ring, the aryldihalopentadienones 4 are condensed with appropriately substituted hydrazines 5 (Step 3) to form substituted Δ2-pyrazolines 6 (A.A. Dudinov et al., Chem. Heterocycl. Cmpd. (Engl. Transl.) 31, 1311 , 1995). That reaction can be carried out in various solvents such as acetic acid, methanol, ethanol or toluene, optionally in the presence of catalytic amounts of acid, e.g. HCI, H2SO4, p-TsOH. The oxidation to form the corresponding dihalovinylpyrazoles 7 (Step 4) can be carried out under various conditions, e.g. by the use of air, DDQ (J.A. Katzenellenbogen et al., Org. Letters 2, 2833, 2000), chloranil, MnO2, KMnO4 or Phl(OAc)2in various solvents such as DMSO, benzene, toluene, xylene, water, acetone or methylene chloride.
The starting compounds 4 are obtainable by aldol condensation of compounds 2 with various aryl alkyl ketones 3 (Step 2) (YN. Maeskii et al., Chem. Heterocycl. Cmpd (Engl. Transl.) 6, 1081 , 1970). Compounds 2 can be obtained by free radical R8R7CX2-addition to vinyl ethers, (Step 1). They are described e.g. in Houben-Weyl, Vol. V/3, p. 973, 1962. It is possible to use free radical starters, for example dibenzoyl peroxide, AIBΝ, sodium dithionite (W.-Y. Huang et al., J. Fluorine Chem. 80, 91 , 1996), or transition metal amine complexes. The reaction can also be initiated with UV light (E.G. Stump et al., J. Org. Chem. 29, 1198, 1964). For the synthesis of the preferred choro-substituted compounds 4 (R8,R7=CI), 3,3-dichloro- acrolein 8 (Houben-Weyl, Vol. VII/1 , p. 119, 1954) is suitable as an alternative to the tetra- chloroether 2 (X,R8,R7=CI). Other synthetic equivalents to the compounds 2 (X,R8,R7= CI) and 8 are the known compounds 9, 10 and V2 (for the preparation of a Br/F analogue of 12 see F.-L. Qing et al., J. Fluorine Chem. 703, 135, 2000), and also 13 and the methylene- iminium salts J . (W. Schroth et al., Synthesis, 573, 1997). Those compounds and their synthetic equivalents can also be used for the synthesis of those compounds 4 wherein R8 and R are other than chlorine. Steps 3 and 4 can also be carried out in a one-pot process, which simplifies and speeds up the synthesis of compounds 7 (Step 5).
Scheme 3
Figure imgf000013_0001
The compounds of formula I can also be prepared from compounds 4 (Scheme 3). For the preparation of the preferred compounds of formula I having a dihalovinyl substituent in the 4- position of the pyrazole ring, the compounds 4 are converted into the compounds 5 (Step 3) under conditions as described in Step 6 of Scheme 1. Compounds 8 having a halogen substituent in the 5-position are obtained by treatment of compounds 5 with N-halosuccinimide NR3S (R3 = CI, Br, I), (Step 4), under conditions as described in Step 8 of Scheme 1. The compounds 4 (R5=H) can be obtained by Vilsmeier formylation from the hydrazones 3 (Step 2, see DE 2 141 125), which are known compounds that can be prepared by customary methods.
The compounds of formula I can also be prepared from the pyrazolones 6. The preparation of those compounds is illustrated in Scheme 1. For the preparation of the preferred compounds of formula I having a dihalovinyl substituent in the 4-position of the pyrazole ring and a halogen substituent R3, the compounds 6 are formylated (Step 5, see DE 2438779) and the aldehyde compounds 7 so obtained are converted into the products 8 under the conditions described for Step 6 in Scheme 1.
The compounds of formula I can also be prepared from the compounds 10. For the preparation of the preferred compounds of formula I having a dihalovinyl substituent in the 4-position of the pyrazole ring, the compounds 10 are converted into the compounds 4 (Step 8) under conditions as described in Step 5 of Scheme 1. Alternatively, the compounds 10 are converted into the compounds 5 (Step 9) under conditions as described in Step 7 of Scheme 1. For the preparation of compounds of formula I having a radical (R8R7R6)C(R5R )C- in the 4- postion of the pyrazole ring, compounds H are obtained from 10 (Step 10) under conditions as described in Step 4 of Scheme 1. The radical (R8R7R6)C(R5R4)C- may already be present in the starting compound 10, or the substituents R8, R7, R6l R5 or R are introduced at a later stage by methods known per se.
The compounds 10 can be obtained from the 1 ,3-diphenylpyrazoles 9 by halogenation of the 4-pyrazole position (Step 7) under conditions as described, for example, in Can. J. Chem. 1986, 64, 2211-19. The starting compounds 9 are either known or can be prepared by known methods.
Scheme 4
Figure imgf000015_0001
The compounds of formula I can also be prepared from compounds 4 by 1 ,3-dipolar cyclo- addition of diphenylnitrile imine, prepared in situ, to alkenes and alkynes to form 1 ,3-di- phenyl-Δ2-pyrazolines and 1 ,3-diphenylpyrazoles (R. Huisgen et al., Chem. Ber. 776, 3438, 1983; ibid., Tetrahedron 77, 3, 1962) (Scheme 4). The preferred compounds of formula I having a dihalovinyl substituent in the 5-position of the pyrazole ring can be obtained by reaction of the compounds 4 with a base, preferably triethylamine, in the presence of either an alkyne, e.g. propargylaldehyde acetal, or an alkene, e.g. acrolein or acrolein acetal (Step 3). The compounds 5 are then obtainable by hydrolysis or oxidation (under the conditions described in Step 4 of Scheme 2). The compounds 5 can be converted (Step 4) into the products 6 under the conditions described in Step 6 of Scheme 1. Another variant for the preparation of compounds of formula I is based on the reaction of compounds 4 with an excess of base, preferably triethylamine, in the presence of, for example, 1 ,1-dichloro- ethylene (Step 5), which results in the chloropyrazoles 7 (Y=CI), which can then be convert- ed (Step 6) into the compounds 6 in accordance with the conditions described in connection with Scheme 1 , Steps 5, 6 and 7.
The compounds 4 are obtainable by known methods from the hydrazides 3 (Step 2). Those compounds are known per se or can be prepared by customary methods.
The compounds of formula la
Figure imgf000016_0001
wherein
R-i and R2 are each independently of the other d.6alkyl, d-ehaloalkyl, d-6alkoxy, d-ehalo- alkoxy, d-6alkylthio, d-6haloalkylthio, d-6alkylsulfinyl, Cι.6haloalkylsulfinyl, d-6alkylsulfonyl, d-ehaloalkylsulfonyl, Cι-8alkylcarbonyl, d.6haloalkylcarbonyl, halogen, -CN, -NO2 or -SF5, or two adjacent R-* substituents or two adjacent R2 substituents are, independently of one another, d-3alkylene, d-3alkylene containing 1 or 2 oxygen atoms, there being no oxygen- oxygen bond, Cι-3haloalkylene or d.3haloalkylene containing 1 or 2 oxygen atoms, there being no oxygen-oxygen bond, m and n are each independently of the other 0, 1 , 2 or 3,
R3 is d-4alkyl, Cι.4haloalkyl, Cι-4alkoxy, C*|.4haloalkoxy, d. alkylthio, Cι-4haloalkylthio, d-4- alkylsulfinyl, d.4alkylsulfonyl, C2-4alkenyl, C2-4haloalkenyl, C2.3alkynyl, halogen, -CN, -NO2) -CHO, -COR9, -COOR10 or -CONRnR12, wherein R9, R10, R-11 and R12 are each independently of the others hydrogen, d-4alkyl, d. - haloalkyl, C3-6cycloalkyl, C2-4alkenyl, C2.4haloalkenyl, C2-3alkynyl, benzyl or phenyl, and R10 may additionally be an alkali metal or alkaline earth metal, a quaternary ammonium base or an amine, or R-11 and R-12 together are C2-5alkylene, p is 0, 1 , 2 or 3, preferably 0 or 1 ,
R4 and R6 are each independently of the other hydrogen, d-4alkyl, d-3haloalkyl or halogen, or
R4 and R6 together form a chemical bond, or
R4 and R6 together form a radical -CH2- or -CH2CH2-, which may be substituted by d- alkyl,
C*|.3haloalkyl or by halogen, and
R5, R7 and R8 are each independently of the others hydrogen, Cι-4alkyl, Cι.3haloalkyl or halogen, at least one of those substituents being other than hydrogen, the compounds of formulae
Figure imgf000017_0001
Figure imgf000018_0001
Figure imgf000018_0002
being excluded, which compounds of formula la may occur as intermediates in the synthesis of the compounds of formula I or can be used specifically as intermediates for the synthesis of the compounds of formula I, are novel and likewise form part of the subject matter of the present invention. Those compounds also exhibit herbicidal action. The compounds of formulae la-i to la are described in A.A. Dudinov et al., Chem. Heterocycl. Cmpd. (Engl. Transl.) 31, 1311 , 1995).
The reactions to form compounds of formula I are advantageously performed in aprotic, inert organic solvents. Such solvents are hydrocarbons, such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons, such as dichloromethane, trichloromethane, tetra- chloromethane and chlorobenzene, ethers, such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran and dioxane, nitriles, such as aceto- nitrile and propionitrile, amides, such as N,N-dimethylformamide, diethylformamide and N- methylpyrrolidinone. The reaction temperatures are preferably from -78°C to +120°C. The reactions generally proceed slightly exothermically and can generally be carried out at room temperature. In order to shorten the reaction time or alternatively to initiate the reaction, the reaction mixture may, if appropriate, be heated for a short time to a temperature up to its boiling point. The reaction times may likewise be shortened by the addition of a few drops of base as reaction catalyst. Suitable bases are especially tertiary amines, such as trimethyl- amine, triethylamine, quinuclidine, 1 ,4-diazabicyclo[2.2.2]octane, 1 ,5-diazabicyclo[4.3.0]non- 5-ene and 1 ,5-diazabicyclo[5.4.0]undec-7-ene, but it is also possible to use inorganic bases, such as hydrides, e.g. sodium or calcium hydride, hydroxides, such as sodium or potassium hydroxide, carbonates, such as sodium or potassium carbonate, or hydrogen carbonates, such as potassium or sodium hydrogen carbonate.
The compounds of formula I can be isolated in customary manner by concentration and/or evaporation of the solvent and can be purified by recrystallisation or trituration of the solid residue in solvents in which they are not readily soluble, such as ethers, aromatic hydrocarbons or chlorinated hydrocarbons.
For the use according to the invention of the compounds of formula I, or of compositions comprising them, there come into consideration all methods of application customary in agriculture, for example pre-emergence application, post-emergence application and seed dressing, and also various methods and techniques such as, for example, the controlled release of active ingredient. For that purpose a solution of the active ingredient is applied to mineral granule carriers or polymerised granules (urea/formaldehyde) and dried. If required, it is additionally possible to apply a coating (coated granules), which allows the active ingredient to be released in metered amounts over a specific period of time.
The compounds of formula I may be used as herbicides in their unmodified form, that is to say as obtained in the synthesis, but they are preferably formulated in customary manner together with the adjuvants conventionally employed in formulation technology, for example into emulsifiable concentrates, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granules or microcapsules. Such formulations are described, for example, on pages 9 to 13 of WO 97/34485. As with the nature of the compositions, the methods of application, such as spraying, atomising, dusting, wetting, scattering or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances. The formulations, that is to say the compositions, preparations or mixtures comprising the compound (active ingredient) of formula I or at least one compound of formula I and, usually, one or more solid or liquid formulation adjuvants, are prepared in known manner, e.g. by homogeneously mixing and/or grinding the active ingredients with the formulation adjuvants, for example solvents or solid carriers. Surface-active compounds (surfactants) may also be used in addition in the preparation of the formulations. Examples of solvents and solid carriers are given, for example, on page 6 of WO 97/34485.
Depending upon the nature of the compound of formula I to be formulated, suitable surface- active compounds are non-ionic, cationic and/or anionic surfactants and surfactant mixtures having good emulsifying, dispersing and wetting properties. Examples of suitable anionic, non-ionic and cationic surfactants are listed, for example, on pages 7 and 8 of WO97/34485. In addition, the surfactants conventionally employed in formulation technology, which are described, inter alia, in "McCutcheon's Detergents and Emulsifiers Annual" MC Publishing Corp., Ridgewood New Jersey, 1981 , Stache, H., "Tensid-Taschenbuch", Carl Hanser Verlag, Munich/Vienna 1981 , and M. and J. Ash, "Encyclopedia of Surfactants", Vol. I-III, Chemical Publishing Co., New York, 1980-81 , are also suitable for the preparation of the herbicidal compositions according to the invention.
The herbicidal formulations generally contain from 0.1 to 99 % by weight, especially from 0.1 to 95 % by weight, of herbicide, from 1 to 99.9 % by weight, especially from 5 to 99.8 % by weight, of a solid or liquid formulation adjuvant, and from 0 to 25 % by weight, especially from 0.1 to 25 % by weight, of a surfactant. Whereas commercial products will preferably be formulated as concentrates, the end user will normally employ dilute formulations. The compositions may also comprise further ingredients, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (epoxidised coconut oil, rapeseed oil or soybean oil), anti-foams, for example silicone oil, preservatives, viscosity regulators, binders, tackifiers, and also fertilisers or other active ingredients.
The compounds of formula I are generally applied to plants or the locus thereof at rates of application of from 0.001 to 4 kg/ha, especially from 0.005 to 2 kg/ha. The concentration required to achieve the desired effect can be determined by experiment. It is dependent on the nature of the action, the stage of development of the cultivated plant and of the weed and on the application (place, time, method) and may vary within wide limits as a function of those parameters.
The compounds of formula I are distinguished by herbicidal and growth-inhibiting properties, allowing them to be used in crops of useful plants, especially cereals, cotton, soybeans, sugar beet, sugar cane, plantation crops, rape, maize and rice, and also for non-selective weed control. The term "crops" is to be understood as including also crops that have been made tolerant to herbicides or classes of herbicides as a result of conventional methods of breeding or genetic techniques. The weeds to be controlled may be either monocotyledonous or dicotyledonous weeds, such as, for example, Stellaria, Nasturtium, Agrostis, Digitaria, Avena, Setaria, Sinapis, Lolium, Solanum, Echinochloa, Scirpus, Monochoria, Sagittaria, Bromus, Alopecurus, Sorghum halepense, Rottboellia, Cyperus, Abutilon, Sida, Xanthium, Amaranthus, Chenopodium, Ipomoea, Chrysanthemum, Galium, Viola and Veronica.
The following Examples further illustrate, but do not limit, the invention.
Preparation Examples:
Example P1 : Preparation of 4-(2,2-dichlorovinyl)-1 -(2,4-difluorophenyl)-3-(3-trifluoro- methylphenyl)-1 H-pyrazole (3)
Figure imgf000021_0001
Step 1 : Preparation of Λ/-(2,4-dif luorophenyl)-Λ/ '-[1 -(3-trifluoromethylphenyl)-ethylidene]- hydrazine (1 )
A few drops of glacial acetic acid and 9.47 g of 3-trifluoromethylacetophenone are added dropwise to a solution of 10 g of 2,4-dif luorophenylhydrazine hydrochloride in 50 ml of ethanol. The reaction mixture is heated to reflux and, with the addition of small portions of hydrazine, stirred until the reaction is complete (TLC monitoring). The reaction mixture is concentrated by evaporation, discharged into 2N NaOH and the aqueous phase is extracted with ethyl acetate. The organic phase is washed with water and saturated sodium chloride solution, dried over sodium sulfate, filtered and concentrated by evaporation. The residue is filtered over silica gel with ethyl acetate/hexane 5:95 and the product is crystallised from hexane. 10.64 g (67% of theory) of the hydrazone (1) are obtained in the form of a solid having a melting point of 77-79°C.
Step 2: Preparation of 1 -(2,4-dif luorophenyl)-3-(3-trif luoromethylphenyl)-1 H-pyrazole-4- carbaldehyde (2)
At 5-10°C, 11.41 g of phosphorus oxychloride are added dropwise to 21.73 g of dimethyl- formamide and, after removal of the cooling, the mixture is stirred for a further one hour. Then, at 20°C, 10.64 g of hydrazone (1) (Example P1 , Step 1), dissolved in a small amount of dimethylformamide, are added dropwise and the reaction mixture is heated at 70°C overnight.
The reaction mixture is discharged into ice/water and adjusted to a pH value of 7 with concentrated NaOH; the resulting suspension is briefly cooled, then filtered and washed with water. The precipitate is dried. 11.3 g (95% of theory) of the aldehyde (2) are obtained in the form of a solid having a melting point of 55-57°C.
Step 3: Preparation of 4-(2,2-dichlorovinyl)-1-(2,4-difluorophenyl)-3-(3-trifluoromethyl- phenyl)-1 H-pyrazole (3)
0.74 ml of DBU (1 ,8-diazabicyclo[5.4.0]undec-7-ene) are added dropwise under argon to a solution of 1.7 g of aldehyde (2) (Example P1 , Step 2) in 0.79 ml of chloroform. The reaction mixture is stirred at 25°C for three hours, then cooled to 0°C. 0.49 ml of acetic anhydride is added and the mixture is stirred for a further two hours and diluted with 1.0 ml of glacial acetic acid. With ice-cooling, 340 mg of zinc powder are added and the reaction mixture is stirred at 60°C for one hour.
Water and ethyl acetate are added to the cooled reaction mixture, the organic phase is separated off, washed with water and saturated sodium chloride solution, dried over sodium sulfate, filtered and concentrated by evaporation. The residue is purified by preparative HPLC on silica gel (gradient ethyl acetate/hexane from 9% to 100%). 1.05 g (51% of theory) of the dichlorovinyl-pyrazole (3) are obtained in the form of a solid having a melting point of 103-104°C.
Example P2: Preparation of 3-(4-chlorophenvD-4-(2,2-dichlorovinyl)-1 -(3-trifluoromethyl- phenvD-1 H-pyrazole (5)
Figure imgf000023_0001
Step 1 : Preparation of 3-(4-chlorophenyl)-1 -(3-trif luoromethylphenyl)-1 H-pyrazole-4- carbaldehyde (4)
Analogously to Preparation Example P1 / Step 2, starting from 3.99 g of the corresponding hydrazone, 4.3 g of phosphorus oxychloride and 8.2 g of dimethylformamide, there are obtained 4.2 g (94% of theory) of the aldehyde (4) in the form of a solid having a melting point of 123-125°C.
Step 2: Preparation of 3-(4-chlorophenyl)-4-(2,2-dichlorovinyl)-1-(3-trifluoromethylphenyl)- 1 H-pyrazole (5)
3.2 g of triphenylphosphine are added all at once to a cooled suspension of 1.35 g of potassium te/t-butanolate in 20 ml of heptane; then in the course of one hour under argon a solution of 0.98 ml of chloroform in 12 ml of heptane is added dropwise in such a manner that the temperature does not exceed 5°C. The reaction mixture is stirred for one hour before 4.2 g of aldehyde (4) (Example P2, Step 1 ) are added in portions in the course of 0.5 hour at a temperature of less than 10°C. The mixture is left overnight at room temperature to complete the reaction.
The cooled reaction mixture is clarified by filtration and the filtrate is concentrated by evaporation. The residue is purified by means of preparative HPLC on silica gel (gradient ethyl acetate/hexane from 9% to 100%) and the product is crystallised from hexane with the addition of a small amount of ethyl acetate. 780 mg (16% of theory) of the dichlorovinyl- pyrazole (5) are obtained in the form of a solid having a melting point of 94-96°C.
Example P3: Preparation of 1 -(3-chlorophenyl)-5-(2,2-dichlorovinyl)-3-(4-trifluoromethyl- phenyl)-1 H-pyrazole (8)
Figure imgf000024_0001
Step 1 : Preparation of ethyl-(1 ,3,3,3-tetrachloropropyl) ether (6)
From tetrachloromethane, ethyl vinyl ether and dibenzoyl peroxide in accordance with a procedure of W. Schroth et al., Z. Chem. 29, 419-420, 1989. The crude fluid, obtained in approximately quantitative yield, is used in the next reaction without further purification.
Step 2: Preparation of 5,5-dichloro-1 -(4-trif luoromethylphenyl)-penta-2,4-dien-1 -one (7)
A solution of 7.63 g of ethyl-(1 ,3,3,3-tetrachloropropyl) ether (6) (Example P3, Step 1) and
5.3 g of 4-trifluoromethylacetophenone in 40 ml of glacial acetic acid is stirred at 25°C for four days until the reaction is complete (TLC monitoring).
The reaction mixture is completely concentrated and the residue is purified by column chromatography on silica gel by means of hexane/ethyl acetate 9:1. 8.1 g (97% of theory) of the aryldichloropentadienone (7) are obtained in the form of a solid having a melting point of
80-82°C.
Step 3: Preparation of 1 -(3-chlorophenyl)-5-(2,2-dichlorovinyl)-3-(4-trifluoromethyl- phenyl)-1 H-pyrazole (8)
A solution of 287 mg of 3-chlorophenylhydrazine hydrochloride and 443 mg of aryldichloropentadienone (7) (Example P3, Step 2) in 8 ml of glacial acetic acid is heated at 105°C for 1.5 hours. After brief cooling, 363 mg of DDQ (2,3-dichloro-5,6-dicyano-1 ,4-benzoquinone) are added and the reaction mixture is heated further at 85-105°C until the reaction is complete (TLC monitoring).
After cooling, the solid is filtered off and the filtrate is concentrated. The residue is taken up in methylene chloride; 5.0 g of silica gel are added and the mixture is again concentrated by evaporation. The adsorbed crude mixture is purified by column chromatography on silica gel using hexane/ethyl acetate 40:1. 280 mg (45% of theory) of the dichlorovinyl-pyrazole (8) are obtained in the form of a solid having a melting point of 100-102°C.
Example P4: Preparation of 3-(4-chlorophenyl)-5-(2,2-dichlorovinyl)-1 -(3-trifluoromethyl- phenyl)-4.5-dihydro-1 H-pyrazole (10) and 3-(4-chlorophenyl)-5-(2,2-dichlorovinyl)-1-(3- trifluoromethylphenyl)-1 H-pyrazole (11)
Figure imgf000025_0001
Step 1 : Preparation of 5,5-dichloro-1 -(4-chlorophenyl)-penta-2,4-dien-1 -one (9)
Analogously to Preparation Example P3 / Step 2, starting from 500 mmol of ethyl-(1 ,3,3,3- tetrachloropropyl) ether (6) and 74.6 g of 4-chloroacetophenone, there are obtained 67.58 g (54% of theory) of the aryldichloropentadienone (9) in the form of a solid having a melting point of 119-121 °C.
Step 2: Preparation of 3-(4-chlorophenyl)-5-(2,2-dichlorovinyl)-1 -(3-trif luoromethylphenyl)- 4,5-dihydro-1 H-pyrazole (10) and 3-(4-chlorophenyl)-5-(2,2-dichlorovinyl)-1-(3-tri- fluoromethylphenyl)-1 H-pyrazole (11 )
A solution of 571 mg of aryldichloropentadienone (9) (Example P4, Step 1 ) and 404 mg of 3- trifluoromethylphenylhydrazine in 9 ml of glacial acetic acid is heated at 80°C for three hours until the reaction is complete (TLC monitoring). The reaction mixture is completely concentrated, the residue is purified by column chromatography on silica gel using hexane/ethyl acetate 9:1 and the products are crystallised from hexane. First 9 mg (1 % of theory) of the dichlorovinyl-Δ2-pyrazoline (10) are obtained in the form of a solid having a melting point of 110-112°. Then 180 mg (20% of theory) of the dichlorovinyl-pyrazole (11 ) are isolated in the form of a solid having a melting point of 116- 117°C.
Example P5 Preparation of 4-bromo-3-(4-chlorophenyl)-5-(2,2-dichlorovinyl)-1 -(3-tri- fluoromethylphenyl)-1 H-pyrazole (12)
Figure imgf000026_0001
214 mg of Λ/-bromosuccinimide are added to a solution of 417 mg of dichlorovinyl-pyrazole (1 1) (Example P4, Step 2) in 3 ml of acetonitrile. The reaction mixture is stirred overnight at 25°C. After complete concentration, the product is crystallised from hexane. 250 mg (50% of theory) of the brominated dichlorovinyl-pyrazole (12) are obtained in the form of a solid having a melting point of 68-69°C.
Example P6: Preparation of 3-(4-chlorophenyl)-5-(2.2-dibromovinyl)-1 -(3-trif luoromethyl- phenvD-1 H-pyrazole (16) and 5-(2,2-difluorovinyl)-3-(4-fluorophenyl)-1-(3-trifluoromethyl- phenyl)-1 H-pyrazole (17)
Figure imgf000026_0002
Step 1 : Preparation of 5-(4-chlorophenyl)-2-(3-trifluoromethylphenyl)-2,4-dihydro-pyrazol- 3-one (13)
A solution of 10.45 g of 3-trif luoromethylphenylhydrazine and 12.2 g of 4-chlorobenzoylacetic acid ethyl ester in 210 ml of glacial acetic acid is heated at 100°C until the reaction is complete (TLC monitoring; about 3 hours).
The reaction mixture is completely concentrated, the residue is taken up in saturated Na2CO3 solution and the aqueous phase is extracted with ethyl acetate. The organic phase is dried over sodium sulfate, filtered and concentrated by evaporation. The product is partially crystallised from ethyl acetate/hexane 1 :1 (5.7 g). The mother liquor is purified by column chromatography on silica gel using hexane/ethyl acetate 4:1 (2.45 g). In total, 8.15 g (45% of theory) of the pyrazolone (13) are obtained in the form of a solid having a melting point of 173-174°C.
Step 2: Preparation of 5-bromo-3-(4-chlorophenyl)-1 -(3-trif luoromethylphenyl)-1 H-pyrazole (14)
1.43 g of phosphorus oxybromide are added in portions at 25°C to a suspension of 1.69 g of pyrazolone (13) (Example P6, Step 1) in 20 ml of toluene and the reaction mixture is heated at reflux overnight.
The reaction mixture is slowly discharged into ice/water, the organic phase is separated off and the aqueous phase is extracted with ethyl acetate; the combined organic phases are washed with water, then dried over sodium sulfate, filtered and concentrated by evaporation. The residue is purified by means of preparative HPLC on silica gel (gradient ethyl acetate/hexane from 9% to 100%). 1.09 g (54% of theory) of the bromo-pyrazole (14) are obtained in the form of a viscous oil. NMR (CDCI3): 7.92 (s,1 H), 7.83 (d,1 H), 7.73 (d,J=7.9Hz, 2H), 7.72-7.57 (m,2H), 7.38 (d,J=7.9Hz, 2H), 6.78 (s,1 H).
Step 3: Preparation of 5-(4-chlorophenyl)-2-(3-trifluoromethylphenyl)-2H-pyrazole-3- carbaldehyde (15)
1.7 ml of an approximately 1.6M BuLi solution in hexane are added dropwise under argon to a solution, cooled to -78°C, of 1.0 g of bromo-pyrazole (14) (Example P6, Step 2) in 6 ml of tetrahydrofuran. The reaction mixture is stirred at -78°C for 0.5 hour, and then a solution of 0.23 ml of dimethylformamide in a small amount of tetrahydrofuran is added dropwise. After stirring at -78°C for a further 0.5 hour, the cooling bath is removed and the mixture is allowed to warm up to room temperature.
Saturated NH CI solution is added to the reaction mixture and the aqueous phase is extracted with ethyl acetate. The combined organic phases are washed with water and saturated sodium chloride solution, dried over sodium sulfate, filtered and concentrated by evaporation. The residue is purified by means of preparative HPLC on silica gel (gradient ethyl acetate/hexane from 9% to 100%). 470 mg (54% of theory) of the aldehyde (15) are obtained in the form of a solid having a melting point of 73-75°C.
Step 4: Preparation of 3-(4-chlorophenyl)-5-(2,2-dibromovinyl)-1 -(3-trif luoromethylphenyl)- 1 H-pyrazole (16)
950 mg of triphenylphosphine are added in portions to a solution, cooled to -20°C, of 210 mg of aldehyde (15) (Example P6, Step 3) and 600 mg of carbon tetrabromide in 10 ml of methylene chloride. The reaction mixture is stirred at from -20°C to -30°C for one hour. Saturated sodium chloride solution is added to the reaction mixture; the organic phase is separated off and the aqueous phase is extracted with methylene chloride. The combined organic phases are dried over sodium sulfate, filtered and concentrated by evaporation. The residue is purified by means of preparative HPLC on silica gel (gradient ethyl acetate/hexane from 9% to 100%). 230 mg (76% of theory) of the dibromovinyl-pyrazole (16) are obtained in the form of a solid having a melting point of 110-112°C.
Step 5: Preparation of 5-(2,2-difluorovinyl)-3-(4-fluorophenyl)-1 -(3-trifluoromethylphenyl)- 1 H-pyrazole (17)
A solution of 334 mg of 5-(4-fluorophenyl)-2-(3-trifluoromethylphenyl)-2H-pyrazole-3-carb- aldehyde (obtained analogously to aldehyde (15), Preparation Example P6 / Steps 1 ,2,3), 244 mg of sodium chlorodifluoroacetate and 266 mg of triphenylphosphine in 7 ml of diethylene glycol dimethyl ether (Diglyme) is degassed and then slowly heated to 170°C under argon. After 3 hours, small portions of sodium chlorodifluoroacetate and triphenylphosphine are again added, and the mixture is left at 170°C to complete the reaction for a further one hour. After cooling, the reaction mixture is concentrated completely under reduced pressure. The residue is taken up in ethyl acetate; 5.0 g of silica gel are added and the mixture is again concentrated by evaporation. The adsorbed crude mixture is purified by column chromatography using hexane/ethyl acetate 95:5 on silica gel. 200 mg (54% of theory) of the difluoro- vinyl-pyrazole (17) are obtained in the form of a solid having a melting point of 102-103°C.
Example P7 Preparation of 3-(4-chlorophenyl)-1 -(3-trifluoromethylphenyl)-5-vinyl-1 H- pyrazole (20)
Figure imgf000029_0001
Step 1 : Preparation of 5-(4-chlorophenyl)-2-(3-trifluoromethylphenyl)-2H-pyrazol-3-yl- amine (18)
A solution of 7.93 g of 3-trifluoromethylphenylhydrazine and 7.69 g of 4-chlorobenzoyl- acetonitrile in 40 ml of glacial acetic acid and 40 ml of ethanol is heated at 120°C for two hours until the reaction is complete (TLC monitoring).
The reaction mixture is completely concentrated and the residue is caused to crystallise by azeotropic treatment with toluene (4x 20 ml) and diethyl ether (3x 20ml). 14.0 g (97% of theory) of the aminopyrazole (18) are obtained in the form of a solid having a melting point of 128-130°C, which is used in the next reaction without further purification.
Step 2 Preparation of 3-(4-chlorophenyl)-5-iodo-1 -(3-trif luoromethylphenyl)-1 H-pyrazole (19)
A suspension of 446 mg of aminopyrazole (18) (Example P7, Step 1), 302 mg of tert-butyl nitrite and 503 mg of copper(l) iodide in 15 ml of acetonitrile is stirred at 25°C for one hour, then for three hours at 70°C. The reaction mixture is diluted with ethyl acetate, washed with 10% Na2S2O3 solution and the organic phase is separated off. The aqueous phase is extracted with ethyl acetate, the combined organic phases are washed with saturated sodium chloride solution, dried over sodium sulfate, filtered and concentrated by evaporation. The residue is purified by column chromatography on silica gel using hexane/ethyl acetate 9:1. 314 mg (53% of theory) of the iodo- pyrazole (19) are obtained in the form of an oil.
Step 3: Preparation of 3-(4-chlorophenyl)-1 -(3-trif luoromethylphenyl)-5-vinyl-1 H-pyrazole (20)
A solution of 183 mg of iodopyrazole (19) (Example P7, Step 2), 155 mg of vinyl-tributyl- stannane and 24 mg of tetrakis(triphenylphosphine)palladium in 10 ml of toluene is stirred at 25°C for one hour, then for eight hours at 100°C.
The reaction mixture is completely concentrated and the residue is purified by column chromatography on silica gel using hexane/ethyl acetate 9:1. 110 mg (78% of theory) of the vinyl-pyrazole (20) are obtained in the form of a solid having a melting point of 97-99°C.
Example P8: Preparation of 5-(2,2-dichlorovinyl)-3-(4-fluorophenyl)-1 -(3-trif luoromethyl- phenyl)-4,5-dihvdro-1 H-pyrazole (21 )
Figure imgf000030_0001
A degassed solution of 335 mg of 5,5-dichloro-1-(4-fluorophenyl)-penta-2,4-dien-1 -one (obtained analogously to the aryldichloropentadienone (9), Preparation Example P4 / Step 1), 241 mg of 3-trifluoromethylphenylhydrazine and 20 mg of p-toluenesulfonic acid monohydrate in 15 ml of toluene is heated at reflux overnight under argon until the reaction is complete (TLC monitoring).
The reaction mixture is completely concentrated and the residue is purified by column chromatography on silica gel using hexane/ethyl acetate 9:1. 383 mg (70% of theory) of the dichlorovinyl-Δ2-pyrazoline (21) are obtained in the form of a solid having a melting point of 119-120°C.
The compounds of formula I listed in the following Tables are prepared analogously, the following explanations applying to the physical data:
HPLC/MS: "M=383, t=4.07" is the retention time t (in min) of the positively charged molecule ion M (in Daltons) when the compound of formula I is analysed with coupled HPLC (High Performance Liquid Chromatography) and MS (Mass Spectrometry) apparatus. HPLC/MS conditions: column: YMC-ODSAQ, 4.6 x 50 mm, 5 μm; pump/UV detector: Waters 2790, 996 PDA; gradient: 20-100% water/acetonitrile in 4.5 min, flow = 1.5 ml/min; MS: Micromass ZMD-2000, ES+.
Table 1 : Compounds of formula lι
Figure imgf000031_0001
Comp.
Ri R2 R3 R4 Re R5 R7 R8 Phys. data No.
1.001 3-F H H H F H F F
1.002 3-F H H F H F H H
1.003 3-F H H - CH2 - H CI CI
1.004 3-F H H - CF2CF2 - H H H
1.005 3-F 4-CI H H H H H H
1.006 3-F 4-CI H H F H F F
1.007 3-F 4-F H H H H H H
1.008 3-F 4-F H H F H F F
1.009 3-F 4-F H F H F H H
1.010 3-F 4-F H H CI H CI CI Comp.
Ri R2 R3 R4 Re R5 R7 R8 Phys. data No.
1.011 3-F 4-F H CI H CI H H
1.012 3-F 4-F H - CH2 - H CI CI
1.013 3-F 4-F H - CF2CF2 - H H H
1.014 3-F 2-F, 4-F H H H H H H
1.015 3-F 2-F, 4-F H H F H F F
1.016 3-F 2-F, 4-F H F F F F F
1.017 3-F 2-F, 4-F H F H F H H
1.018 3-F 2-F, 4-F H H CI H CI CI
1.019 3-F 2-F, 4-F H CI CI CI CI CI
1.020 3-F 2-F, 4-F H CI H CI H H
1.021 3-F 2-F, 4-F H CF3 F H F F
1.022 3-F 2-F, 4-F H CH3 F CH3 F F
1.023 3-F 2-F, 4-F H - CH2 - H CI CI
1.024 3-F 2-F, 4-F H - CF2CF2 - H H H
1.025 3-CF3 H H H F H F F
1.026 3-CF3 H H F H F H H
1.027 3-CF3 H H H CI H CI CI
1.028 3-CF3 H H CI H CI H H
1.029 3-CF3 H H - CH2 - H CI CI
1.030 3-CF3 H H - CF2CF2 - H H H
1.031 3-CF3 4-CI H H H H H H M.p. 100-102°C
1.032 3-CF3 4-CI H H F H F F
1.033 3-CF3 4-F H H H H H H
1.034 3-CF3 4-F H H F H F F M.p. 100-102°C
1.035 3-CF3 4-F H F H F H H M.p. 99-101 °C
1.036 3-CF3 4-F H H CI H CI CI
1.037 3-CF3 4-F H CI H CI H H
1.038 3-CF3 4-F H - CH2 - H CI CI oil
1.039 3-CF3 4-F H - CF2CF2 - H H H
1.040 3-CF3 2-F, 4-F H H H H H H
1.041 3-CF3 2-F, 4-F H H F H F H
1.042 3-CF3 2-F, 4-F H H F H F F
1.043 3-CF3 2-F, 4-F H F F F F F
1.044 3-CF3 2-F, 4-F H F H H H H Comp.
Ri R2 R3 R4 e R5 R7 R8 Phys. data No.
1.045 3-CF3 2-F, 4-F H F H F H H
1.046 3-CF3 2-F, 4-F H H CI H CI H
1.047 3-CF3 2-F, 4-F' H H CI H CI CI
1.048 3-CF3 2-F, 4-F H CI CI CI CI CI
1.049 3-CF3 2-F, 4-F H CI H H H H
1.050 3-CF3 2-F, 4-F H CI H CI H H
1.051 3-CF3 2-F, 4-F H CF3 F H F F
1.052 3-CF3 2-F, 4-F H F CH3 F CH3 CH3
1.053 3-CF3 2-F, 4-F H CH3 F CH3 F F
1.054 3-CF3 2-F, 4-F Br H F H F F
1.055 3-CF3 2-F, 4-F C≡CH H F H F F
1.056 3-CF3 2-F, 4-F COCH3 H F H F F
1.057 3-CF3 2-F, 4-F H - CH2 - H H H
1.058 3-CF3 2-F, 4-F H - CH2 - CI H H
1.059 3-CF3 2-F, 4-F H - CH2 - H CI CI
1.060 3-CF3 2-F, 4-F H - CH2 - H Br Br
1.061 3-CF3 2-F, 4-F H - CH2 - CH3 CI CI
1.062 3-CF3 2-F, 4-F H - CH2 - CI CI CI
1.063 3-CF3 ' 2-F, 4-F H - C(CI)2 - H CI CI
1.064 3-CF3 2-F, 4-F H - C(CI)2 - CH3 CI CI
1.065 3-CF3 2-F, 4-F H - C(CI)2 - CF3 CI CI
1.066 3-CF3 2-F, 4-F H - CH2CH2 - H H H
1.067 3-CF3 2-F, 4-F H - CH2CH2 - H CI CI
1.068 3-CF3 2-F, 4-F H - CF2CF2 - H H H
1.069 3-CF3 2-F, 4-F H - CF2CF2 - H CI CI
1.070 3-OCF3 H H H F H F F
1.071 3-OCF3 H H F H F H H
1.072 3-OCF3 H H H CI H CI CI
1.073 3-OCF3 H H CI H CI H H
1.074 3-OCF3 H H - CH2 - H CI CI
1.075 3-OCF3 H H - CF2CF2 - H H H
1.076 3-OCF3 4-CI H H H H H H
1.077 3-OCF3 4-CI H H F H F F
1.078 3-OCF3 4-F H H H H H H Comp.
Ri R2 R3 R4 Re R5 R7 R8 Phys. data No.
1.079 3-OCF3 4-F H H F H F F
1.080 3-OCF3 4-F H F H F H H
1.081 3-OCF3 4-F H H CI H CI CI
1.082 3-OCF3 4-F H CI H CI H H
1.083 3-OCF3 4-F H - CH2 - H CI CI
1.084 3-OCF3 4-F H - CF2CF2 - H H H
1.085 3-OCF3 2-F, 4-F H H H H H H
1.086 3-OCF3 2-F, 4-F H H F H F H
1.087 3-OCF3 2-F, 4-F H H F H F F
1.088 3-OCF3 2-F, 4-F H F F F F F
1.089 3-OCF3 2-F, 4-F H F H H H H
1.090 3-OCF3 2-F, 4-F H F H F H H
1.091 3-OCF3 2-F, 4-F H H CI H CI H
1.092 3-OCF3 2-F, 4-F H H CI H CI CI
1.093 3-OCF3 2-F, 4-F H CI CI CI CI C)
1.094 3-OCF3 2-F, 4-F H CI H H H H
1.095 3-OCF3 2-F, 4-F H CI H CI H H
1.096 3-OCF3 2-F, 4-F H CFC 1 F H F F
1.097 3-OCF3 2-F, 4-F H F CH3 F CH3 CH3
1.098 3-OCF3 2-F, 4-F H CH3 F CH3 F F
1.099 3-OCF3 2-F, 4-F Br H F H F F
1.100 3-OCF3 2-F, 4-F C≡CH H F H F F
1.101 3-OCF3 2-F, 4-F COCH3 H F H F F
1.102 3-OCF3 2-F, 4-F H - CH2 - H H H
1.103 3-OCF3 2-F, 4-F H - CH2 - CI H H
1.104 3-OCF3 2-F, 4-F H - CH2 - H CI CI
1.105 3-OCF3 2-F, 4-F H - CH2 - H Br Br
1.106 3-OCF3 2-F, 4-F H - CH2 - CH3 CI CI
1.107 3-OCF3 2-F, 4-F H - CH2 - CI CI CI
1.108 3-OCF3 2-F, 4-F H - C(CI)2 - H CI CI
1.109 3-OCF3 2-F, 4-F H - C(CI)2 - CH3 CI CI
1.110 3-OCF3 2-F, 4-F H - C(CI)2 - CF3 CI CI
1.111 3-OCF3 2-F, 4-F H - CH2CH2 - H H H
1.112 3-OCF3 2-F, 4-F H - CH2CH2 - H CI CI Comp.
Ri R2 R3 R Re R5 R7 R8 Phys. data No.
1.113 3-OCF3 2-F, 4-F H - CF2CF2 - H H H
1.114 3-OCF3 2-F, 4-F H - CF2CF2 - H CI CI
1.115 3-SF3 H H H F H F F
1.116 3-SF3 H H F H F H H
1.117 3-SF3 H H - CH2 - H CI CI
1.118 3-SF3 H H - CF2CF2 - H H H
1.119 3-SF3 4-CI H H H H H H
1.120 3-SF3 4-CI H H F H F F
1.121 3-SF3 4-F H H H H H H
1.122 3-SF3 4-F H H F H F F
1.123 3-SF3 4-F H F H F H H
1.124 3-SF3 4-F H H CI H CI CI
1.125 3-SF3 4-F H CI H CI H H
1.126 3-SF3 4-F H - CH2 - H CI CI
1.127 3-SF3 4-F H - CF2CF2 - H H H
1.128 3-SF3 2-F, 4-F H H H H H H
1.129 3-SF3 2-F, 4-F H H F H F F
1.130 3-SF3 2-F, 4-F H F F F F F
1.131 3-SF3 2-F, 4-F H F H F H H
1.132 3-SF3 2-F, 4-F H H CI H CI CI
1.133 3-SF3 2-F, 4-F H CI CI CI CI CI
1.134 3-SF3 2-F, 4-F H CI H CI H H
1.135 3-SF3 2-F, 4-F H CF3 F H F F
1.136 3-SF3 2-F, 4-F H CH3 F CH3 F F
1.137 3-SF3 2-F, 4-F H - CH2 - H CI CI
1.138 3-SF3 2-F, 4-F H - CF2CF2 - H H H
1.139 2,3-(-OCF20-) H H H F H F F
1.140 2,3-(-OCF20-) H H F H F H H
1.141 2,3-(-OCF20-) 4-CI H H H H H H
1.142 2,3-(-OCF20-) 4-CI H H F H F F
1.143 2,3-(-OCF20-) 4-F H H H H H H
1.144 2,3-(-OCF20-) 4-F H H F H F F
1.145 2,3-(-OCF20-) 4-F H F H F H H
1.146 2,3-(-OCF20-) 4-F H H CI H CI CI Comp.
Ri R2 R3 R4 Re R5 R7 R8 Phys. data No.
1.147 2,3-(-OCF2O- 4-F H CI H CI H H
1.148 2,3-(-OCF2O- 2-F, 4-F H H H H H H
1.149 2,3-(-OCF2O- ) 2-F, 4-F H H F H F F
1.150 2,3-(-OCF2O- | 2-F, 4-F H F F F F F
1.151 2,3-(-OCF2O- | 2-F, 4-F H F H F H H
1.152 2,3-(-OCF2O- | 2-F, 4-F H H CI H CI CI
1.153 2,3-(-OCF2O- 2-F, 4-F H CI CI CI CI CI
1.154 2,3-(-OCF2O- | 2-F, 4-F H CI H CI H H
1.155 2,3-(-OCF2O- | 2-F, 4-F H CF3 F H F F
1.156 2,3-(-OCF2O- I 2-F, 4-F H CH3 F CH3 F F
Table 2: Compounds of formula l2
Figure imgf000037_0001
Comp.
Ri R R3 R5 R7 R8 Phys. data No.
2.001 H H H H CI CI M.p. 107-108°C
2.002 H 2-F H H CI CI
2.003 H 2-CH3 H H CI CI
2.004 H 4-F H H CI CI M.p. 118-120°C
2.005 H 3-CI H H CI CI M=348, t=4.00
2.006 H 3-CI H H CF3 CI M=382, t=3.90
2.007 H 4-CI H H CI CI M.p. 109-110°C
2.008 H 4-OCH3 H H CI CI M.p. 113-115°C
2.009 H 3-CF3 H H CI CI M=382, t=3.90
2.010 H 3-CF3 H H CF3 CI M=416, t=3.91
2.011 H 4-CF3 H H CI CI M.p. 111 -113°C
2.012 H 2-F, 4-F H H CI CI M.p. 114-116°C
2.013 H 2-CI, 5-CI H H CI CI M=382, t=4.20
2.014 3-F H H H CI CI
2.015 3-F H H H Br Br
2.016 3-F 2-F H H CI CI M.p. 99-101°C
2.017 3-F 2-CH3 H H CI CI
2.018 3-F 4-F H H F F
2.019 3-F 4-F H H CI CI M.p. 144-146°C
2.020 3-F 4-F H H Br Br
2.021 3-F 4-CI H H CI CI
2.022 3-F 4-CF3 H H CI CI Comp.
Ri R2 R3 R5 R7 R8 Phys. data No.
2.023 3-F 2-F, 4-F H H F F
2.024 3-F 2-F, 4-F H H CI CI M.p. 116-117°C
2.025 3-F 2-F, 4-F H H Br Br
2.026 3-F H H CI CI CI
2.027 3-F 4-F H F CI CI
2.028 3-F 2-F, 4-F H F CI CI
2.029 3-F 2-F, 4-F H CI CI CI
2.030 3-F 2-F, 4-F H CH3 CI CI
2.031 3-F 4-F Br H CI CI
2.032 3-F 2-F, 4-F C≡CH H CI CI
2.033 3-F 2-F, 4-F Br H CI CI
2.034 3-F 2-F, 4-F COCH3 H CI CI
2.035 3-F 2-F, 4-F Br F CI CI
2.036 2-CI 4-CI H H CI CI M=382, t=3.88
2.037 2-CI 3-CF3 H H CI CI M=416, t=3.90
2.038 2-CI 4-CF3 H H CI CI M=416, t=3.89
2.039 3-CI H H H CI CI M.p. 113-115°C
2.040 3-CI 2-F H H CI CI
2.041 3-CI 2-CH3 H H CI CI
2.042 3-CI 4-F H H F F
2.043 3-CI 4-F H H CI CI M.p. 126-128°C
2.044 3-CI 4-F H H Br Br
2.045 3-CI 3-CI H H CI CI M=382, t=4.00
2.046 3-CI 4-CI H H CI CI M.p. 120-122°C
2.047 3-CI 4-CI H H CF3 CI M=416, t=4.10
2.048 3-CI 3-CF3 H H CI CI M=416, t=4.08
2.049 3-CI 4-CF3 H H CI CI M.p. 100-102°C
2.050 3-CI 2-F, 4-F H H F F
2.051 3-CI 2-F, 4-F H H CI CI M.p. 124-126°C
2.052 3-CI 2-F, 4-F H H Br Br
2.053 4-CI H H H CI CI M=348, t=3.87
2.054 4-CI 3-CI H H CI CI M=382, t=4.15
2.055 4-CI 4-CI H H CI CI M=382, t=4.14
2.056 4-CI 3-CF3 H H CI CI M.p. 118-120°C Comp.
Ri R2 R3 R5 R7 R8 Phys. data No.
2.057 4-CI 4-CF3 H H CI CI M=416, t=4.10
2.058 3-Br H H H CI CI
2.059 3-Br 2-F H H CI CI
2.060 3-Br 2-CH3 H H CI CI
2.061 3-Br 4-F H H CI CI
2.062 3-Br 4-CI H H CI CI
2.063 3-Br 4-CF3 H H CI CI
2.064 3-Br 2-F, 4-F H H CI CI
2.065 3-CF3 H H H H H
2.066 3-CF3 H H H F F
2.067 3-CF3 H H H CI CI M.p. 109-111 °C
2.068 3-CF3 H H H Br Br
2.069 3-CF3 2-F H H F F
2.070 3-CF3 2-F H H CI CI M.p. 114-116°C
2.071 3-CF3 2-F H H Br Br
2.072 3-CF3 2-CI H H CI CI M.p. 89-90°C
2.073 3-CF3 2-CH3 H H F F
2.074 3-CF3 2-CH3 H H CI CI M.p. 71-73°C
2.075 3-CF3 2-CH3 H H Br Br
2.076 3-CF3 2-OCH3 H H CI CI M.p. 60-61 °C
2.077 3-CF3 3-F H H CI CI M.p. 96-98°C
2.078 3-CF3 3-CI H H CI CI M.p. 94-95°C
2.079 3-CF3 3-Br H H CI CI M.p. 96-98°C
2.080 3-CF3 3-OCF3 H H CI CI M.p. 76-78°C
2.081 3-CF3 4-F H H H H M.p. 49-50°C
2.082 3-CF3 4-F H H CI H
2.083 3-CF3 4-F H H H CI
2.084 3-CF3 4-F H H Br H solid
2.085 3-CF3 4-F H H H Br solid
2.086 3-CF3 4-F H H F F M.p. 102-103°C
2.087 3-CF3 4-F H H CI F
2.088 3-CF3 4-F H H F CI
2.089 3-CF3 4-F H H CI CI M.p. 134-136°C
2.090 3-CF3 4-F H H Br CI Comp.
Ri R2 R3 Rs R7 Ra Phys. data No.
2.091 3-CF3 4-F H H CI Br
2.092 3-CF3 4-F H H CH3 CI
2.093 3-CF3 4-F H H CI CH3
2.094 3-CF3 4-F H H CF3 CI
2.095 3-CF3 4-F H H CI CF3
2.096 3-CF3 4-F H H Br Br M.p. 136-138°C
2.097 3-CF3 4-F H H CF3 CF3
2.098 3-CF3 4-CI H H H H M.p. 97-99°C
2.099 3-CF3 4-CI H H F F
2.100 3-CF3 4-CI H H CI CI M.p. 117°C
2.101 3-CF3 4-CI H H CF3 CI M=450, t=4.04
2.102 3-CF3 4-CI H H Br Br M.p. 110-112°C
2.103 3-CF3 4-Br H H CI CI
2.104 3-CF3 3-CF3 H H CI CI M=450, t=4.10
2.105 3-CF3 3-CF3 H H CF3 CI M=484, t=4.01
2.106 3-CF3 4-CF3 H H F F
2.107 3-CF3 4-CF3 H H CI CI M.p. 94°C
2.108 3-CF3 4-CF3 H H Br Br
2.109 3-CF3 4-OCF3 H H CI CI
2.110 3-CF3 4-SCF3 H H CI CI M.p. 114-116°C
2.111 3-CF3 4-S02CF3 H H F F
2.112 3-CF3 4-S02CF3 H H CI CI
2.113 3-CF3 4-S02CF3 H H Br Br
2.114 3-CF3 4-S02CH3 H H CI CI M.p. 144-146°C
2.115 3-CF3 4-CN H H CI CI solid
2.116 3-CF3 4-N02 H H CI CI M.p. 137-139°C
2.117 3-CF3 4-SF5 H H CI CI
2.118 3-CF3 4-F, 3-F H H F F
2.119 3-CF3 4-F, 3-F H H CI CI M.p. 125-127°C
2.120 3-CF3 4-F, 3-F H H Br Br
2.121 3-CF3 4-F, 3-CI H H CI CI
2.122 3-CF3 4-F, 3-CN H H CI CI
2.123 3-CF3 4-F, 3-CF3 H H CI CI
2.124 3-CF3 2-F, 4-CF3 H H CI CI Comp.
Ri R2 R3 R5 R7 R8 Phys. data No.
2.125 3-CF3 2-CF3, 4-CF3 H H CI CI
2.126 3-CF3 3-F, 5-F H H CI CI
2.127 3-CF3 3-CF3, 5-CF3 H H CI CI
2.128 3-CF3 2-F, 4-F H H H H
2.129 3-CF3 2-F, 4-F H H CI H M.p. 128-129°C
2.130 3-CF3 2-F, 4-F H H H CI M.p. 98-101 °C
2.131 3-CF3 2-F, 4-F H H Br H
2.132 3-CF3 2-F, 4-F H H H Br
2.133 3-CF3 2-F, 4-F H H F F
2.134 3-CF3 2-F, 4-F H H CI F M.p. 30-32°C
2.135 3-CF3 2-F, 4-F H H F CI M.p. 30-32°C
2.136 3-CF3 2-F, 4-F H H CI CI M.p.124-126°C
2.137 3-CF3 2-F, 4-F H H Br CI
2.138 3-CF3 2-F, 4-F H H CI Br
2.139 3-CF3 2-F, 4-F H H CH3 CI
2.140 3-CF3 2-F, 4-F H H CI CH3
2.141 3-CF3 2-F, 4-F H H CF3 CI
2.142 3-CF3 2-F, 4-F H H CI CF3
2.143 3-CF3 2-F, 4-F H H Br Br
2.144 3-CF3 2-F, 4-F H H CF3 CF3
2.145 3-CF3 2-F, 6-F H H F F
2.146 3-CF3 2-F, 6-F H H CI CI
2.147 3-CF3 2-F, 6-F H H Br Br
2.148 3-CF3 2-CI, 4-F H H CI CI M.p. 94-96°C
2.149 3-CF3 2-CI, 4-CI H H CI CI M.p. 85-88°C
2.150 3-CF3 2-CI, 5-CI H H CI CI M=450, t=4.20
2.151 3-CF3 2-F, 4-F, 6-F H H CI CI
2.152 3-CF3 H H CI CI CI
2.153 3-CF3 2-F H CI CI CI
2.154 3-CF3 4-F H F CI CI
2.155 3-CF3 4-F H CI CI CI
2.156 3-CF3 2-F, 4-F H F CI CI
2.157 3-CF3 2-F, 4-F H F CI H
2.158 3-CF3 2-F, 4-F H F H CI Comp.
Ri R2 R3 R5 R7 R8 Phys. data No.
2.159 3-CF3 2-F, 4-F H CI CI CI oil
2.160 3-CF3 2-F, 4-F H CI CI H
2.161 3-CF3 2-F, 4-F H CI H CI
2.162 3-CF3 2-F, 4-F H CH3 CI CI oil
2.163 3-CF3 H CI H CI CI
2.164 3-CF3 H Br H CI CI
2.165 3-CF3 4-F CI H CI CI M.p. 75-77°C
2.166 3-CF3 4-F Br H CI CI oil
2.167 3-CF3 4-F CN H CI CI
2.168 3-CF3 4-CI Br H CI CI M.p. 68-69°C
2.169 3-CF3 2-F, 4-F CH3 H CI CI
2.170 3-CF3 2-F, 4-F CH=CH2 H CI CI
2.171 3-CF3 2-F, 4-F C≡CH H CI CI
2.172 3-CF3 2-F, 4-F CI H CI CI oil
2.173 3-CF3 2-F, 4-F Br H CI CI
2.174 3-CF3 2-F, 4-F I H CI CI oil
2.175 3-CF3 2-F, 4-F CN H CI CI M.p. 82-84°C
2.176 3-CF3 2-F, 4-F N02 H CI CI oil
2.177 3-CF3 2-F, 4-F COCH3 H CI CI
2.178 3-CF3 2-F, 4-F COOCH3 H CI CI
2.179 3-CF3 2-F, 4-F Br F CI CI
2.180 3-CF3 2-F, 4-F CN F CI CI
2.181 3-CF3 2-F, 4-F C≡CH F CI CI
2.182 4-CF3 H H H CI CI M=382, t=3.90
2.183 4-CF3 3-CI H H CI CI =416, t=4.07
2.184 4-CF3 4-CI H H CI CI M=416, t=4.10
2.185 4-CF3 3-CF3 H H CI CI M=450, t=4.10
2.186 4-CF3 4-CF3 H H CI CI M=450, t=4.00
2.187 3-CF2CF3 H H H CI CI M.p. 65-67°C
2.188 3-CF2CF3 2-F H H CI CI
2.189 3-CF2CF3 2-CH3 H H CI CI
2.190 3-CF2CF3 3-F H H CI CI
2.191 3-CF2CF3 3-CF3 H H CI CI
2.192 3-CF2CF3 4-F H H CI H Comp.
Ri R2 R3 Rs R7 R8 Phys. data No.
2.193 3-CF2CF3 4-F H H H CI
2.194 3-CF2CF3 4-F H H F F
2.195 3-CF2CF3 4-F H H CI CI
2.196 3-CF2CF3 4-F H H Br Br
2.197 3-CF2CF3 4-CI H H CI CI
2.198 3-CF2CF3 4-CF3 H H CI CI
2.199 3-CF2CF3 4-OCF3 H H CI CI
2.200 3-CF2CF3 4-SCF3 H H CI CI
2.201 3-CF2CF3 4-SO2CF3 H H CI CI
2.202 3-CF2CF3 4-CN H H CI CI
2.203 3-CF2CF3 4-SF5 H H CI CI
2.204 3-CF2CF3 4-F, 3-F H H CI CI
2.205 3-CF2CF3 4-F, 3-F H H Br Br
2.206 3-CF2CF3 4-F, 3-CF3 H H CI CI
2.207 3-CF2CF3 2-F, 4-CF3 H H CI CI
2.208 3-CF2CF3 3-F, 5-F H H CI CI
2.209 3-CF2CF3 3-CF3, 5-CF3 H H CI CI
2.210 3-CF2CF3 2-F, 4-F H H CI H
2.211 3-CF2CF3 2-F, 4-F H H H CI
2.212 3-CF2CF3 2-F, 4-F H H F F
2.213 3-CF2CF3 2-F, 4-F H H CI CI
2.214 3-CF2CF3 2-F, 4-F H H Br Br
2.215 3-CF2CF3 2-F, 6-F H H CI CI
2.216 3-CF2CF3 2-F, 4-F, 6-F H H CI CI
2.217 3-CHF2 H H H CI CI
2.218 3-CHF2 2-F H H CI CI
2.219 3-CHF2 2-CH3 H H CI CI
2.220 3-CHF2 3-F H H CI CI
2.221 3-CHF2 3-CF3 H H CI CI
2.222 3-CHF2 4-F H H F F
2.223 3-CHF2 4-F H H CI CI
2.224 3-CHF2 4-F H H Br Br
2.225 3-CHF2 4-CI H H CI CI
2.226 3-CHF2 4-CF3 H H CI CI Comp.
Ri R2 R3 R5 R7 R8 Phys. data No.
2.227 3-CHF2 4-OCF3 H H CI CI
2.228 3-CHF2 4-SCF3 H H CI CI
2.229 3-CHF2 4-SO2CF3 H H CI CI
2.230 3-CHF2 4-CN H H CI CI
2.231 3-CHF2 4-SF5 H H CI CI
2.232 3-CHF2 4-F, 3-F H H CI CI
2.233 3-CHF2 4-F, 3-CF3 H H CI CI
2.234 3-CHF2 2-F, 4-CF3 H H CI CI
2.235 3-CHF2 3-F, 5-F H H CI CI
2.236 3-CHF2 3-CF3, 5-CF3 H H CI CI
2.237 3-CHF2 2-F, 4-F H H CI H
2.238 3-CHF2 2-F, 4-F H H H CI
2.239 3-CHF2 2-F, 4-F H H F F
2.240 3-CHF2 2-F, 4-F H H CI CI
2.241 3-CHF2 2-F, 4-F H H Br CI
2.242 3-CHF2 2-F, 4-F H H CI Br
2.243 3-CHF2 2-F, 4-F H H Br Br
2.244 3-CHF2 2-F, 6-F H H CI CI
2.245 3-CHF2 2-F, 4-F, 6-F H H CI CI
2.246 3-OCF3 H H H H H
2.247 3-OCF3 H H H F F
2.248 3-OCF3 H H H CI CI M.p. 55-57°C
2.249 3-OCF3 H H H Br Br
2.250 3-OCF3 2-F H H F F
2.251 3-OCF3 2-F H H CI CI oil
2.252 3-OCF3 2-F H H Br Br
2.253 3-OCF3 2-CH3 H H F F
2.254 3-OCF3 2-CH3 H H CI CI oil
2.255 3-OCF3 2-CH3 H H Br Br
2.256 3-OCF3 3-F H H CI CI M.p. 35-38°C
2.257 3-OCF3 3-CF3 H H CI CI
2.258 3-OCF3 3-OCF3 H H CI CI M.p. 40-42°C
2.259 3-OCF3 4-F H H H H
2.260 3-OCF3 4-F H H CI H Comp.
Ri R2 -R3 R5 R7 Rs Phys. data No.
2.261 3-OCF3 4-F H H H CI
2.262 3-OCF3 4-F H H Br H
2.263 3-OCF3 4-F H H H Br
2.264 3-OCF3 4-F H H F F
2.265 3-OCF3 4-F H H CI F
2.266 3-OCF3 4-F H H F CI
2.267 3-OCF3 4-F H H CI CI M.p. 59-61 °C
2.268 3-OCF3 4-F H H Br CI
2.269 3-OCF3 4-F H H CI Br
2.270 3-OCF3 4-F H H CH3 CI
2.271 3-OCF3 4-F H H CI C 3
2.272 3-OCF3 4-F H H CF3 CI
2.273 3-OCF3 4-F H H CI CF3
2.274 3-OCF3 4-F H H Br Br
2.275 3-OCF3 4-F H H CF3 CF3
2.276 3-OCF3 4-CI H H F F
2.277 3-OCF3 4-CI H H CI CI solid
2.278 3-OCF3 4-CI H H Br Br
2.279 3-OCF3 4-Br H H CI CI
2.280 3-OCF3 4-CF3 H H F F
2.281 3-OCF3 4-CF3 H H CI CI
2.282 3-OCF3 4-CF3 H H Br Br
2.283 3-OCF3 4-OCF3 H H ci CI
2.284 3-OCF3 4-SCF3 H H CI CI M.p. 68-73°C
2.285 3-OCF3 4-SO2CF3 H H F F
2.286 3-OCF3 4-SO2CF3 H H CI a solid
2.287 3-OCF3 4-SO2CF3 H H Br Br
2.288 3-OCF3 4-SO2CH3 H H CI CI M.p. 136-138°C
2.289 3-OCF3 4-CN H H CI CI solid
2.290 3-OCF3 4-NO2 H H CI CI M.p. 92-95°C
2.291 3-OCF3 4-SF5 H H CI CI
2.292 3-OCF3 4-F, 3-F H H F F
2.293 3-OCF3 4-F, 3-F H H CI CI M.p. 77-81 °C
2.294 3-OCF3 4-F, 3-F H H Br Br Comp.
Ri R2 R3 R5 R7 R8 Phys. data No.
2.295 3-OCF3 4-F, 3-CI H H CI CI
2.296 3-OCF3 4-F, 3-CN H H CI CI
2.297 3-OCF3 4-F, 3-CF3 H H CI CI
2.298 3-OCF3 2-F, 4-CF3 H H CI CI
2.299 3-OCF3 2-CF3, 4-CF3 H H CI CI
2.300 3-OCF3 3-F, 5-F H H CI CI
2.301 3-OCF3 3-CF3, 5-CF3 H H F F
2.302 3-OCF3 3-CF3, 5-CF3 H H CI CI
2.303 3-OCF3 2-F, 4-F H H H H
2.304 3-OCF3 2-F, 4-F H H CI H
2.305 3-OCF3 2-F, 4-F H H H CI
2.306 3-OCF3 2-F, 4-F H H Br H
2.307 3-OCF3 2-F, 4-F H H H Br
2.308 3-OCF3 2-F, 4-F H H F F
2.309 3-OCF3 2-F, 4-F H H CI F
2.310 3-OCF3 2-F, 4-F H H F CI
2.311 3-OCF3 2-F, 4-F H H CI CI M.p. 30-32°C
2.312 3-OCF3 2-F, 4-F H H Br CI
2.313 3-OCF3 2-F, 4-F H H CI Br
2.314 3-OCF3 2-F, 4-F H H CH3 CI
2.315 3-OCF3 2-F, 4-F H H CI CH3
2.316 3-OCF3 2-F, 4-F H H CF3 CI
2.317 3-OCF3 2-F, 4-F H H CI CF3
2.318 3-OCF3 2-F, 4-F H H Br Br
2.319 3-OCF3 2-F, 4-F H H CF3 CF3
2.320 3-OCF3 2-F, 6-F H H F F
2.321 3-OCF3 2-F, 6-F H H CI CI
2.322 3-OCF3 2-F, 6-F H H Br Br
2.323 3-OCF3 2-F, 4-F, 6-F H H CI CI
2.324 3-OCF3 H H CI CI CI
2.325 3-OCF3 2-F H CI CI CI
2.326 3-OCF3 4-F H F CI CI
2.327 3-OCF3 4-F H CI CI CI
2.328 3-OCF3 2-F, 4-F H F CI CI Comp.
Ri R2 R3 R5 R R8 Phys. data No.
2.329 3-OCF3 2-F, 4-F H F CI H
2.330 3-OCF3 2-F, 4-F H F H CI
2.331 3-OCF3 2-F, 4-F H CI CI CI
2.332 3-OCF3 2-F, 4-F H CI CI H
2.333 3-OCF3 2-F, 4-F H CI H CI
2.334 3-OCF3 2-F, 4-F H CH3 CI CI
2.335 3-OCF3 H CI H CI CI
2.336 3-OCF3 H Br H CI CI
2.337 3-OCF3 4-F Br H CI CI
2.338 3-OCF3 4-F CN H CI CI
2.339 3-OCF3 2-F, 4-F CH3 H CI CI
2.340 3-OCF3 2-F, 4-F CH=CH2 H CI CI
2.341 3-OCF3 2-F, 4-F C≡CH H CI CI
2.342 3-OCF3 2-F, 4-F CI H CI CI
2.343 3-OCF3 2-F, 4-F Br H CI CI
2.344 3-OCF3 2-F, 4-F CN H CI CI
2.345 3-OCF3 2-F, 4-F NO2 H CI CI
2.346 3-OCF3 2-F, 4-F COCH3 H CI CI
2.347 3-OCF3 2-F, 4-F COOCH3 H CI CI
2.348 3-OCF3 2-F, 4-F Br F CI CI
2.349 3-OCF3 2-F, 4-F CN F CI CI
2.350 3-OCF3 2-F, 4-F C≡CH F CI CI
2.351 3-OCHF2 H H H F F
2.352 3-OCHF2 H H H CI CI M.p. 55-57°C
2.353 3-OCHF2 H H H Br Br
2.354 3-OCHF2 2-F H H CI CI
2.355 3-OCHF2 2-CH3 H H CI CI
2.356 3-OCHF2 3-F H H CI CI
2.357 3-OCHF2 3-CF3 H H CI CI
2.358 3-OCHF2 4-F H H F F
2.359 3-OCHF2 4-F H H CI CI
2.360 3-OCHF2 4-F H H Br Br
2.361 3-OCHF2 4-CI H H CI CI
2.362 3-OCHF2 4-CF3 H H CI CI Comp.
Ri R2 R3 R5 R7 Rs Phys. data No.
2.363 3-OCHF2 4-OCF3 H H CI CI
2.364 3-OCHF2 4-SCF3 H H CI CI
2.365 3-OCHF2 4-SO2CF3 H H CI CI
2.366 3-OCHF2 4-CN H H CI CI
2.367 3-OCHF2 4-SF5 H H CI CI
2.368 3-OCHF2 4-F, 3-F H H CI CI
2.369 3-OCHF2 4-F, 3-CF3 H H CI CI
2.370 3-OCHF2 2-F, 4-CF3 H H CI CI
2.371 3-OCHF2 3-F, 5-F H H CI CI •
2.372 3-OCHF2 3-CF3, 5-CF3 H H CI CI
2.373 3-OCHF2 2-F, 4-F H H CI H
2.374 3-OCHF2 2-F, 4-F H H H CI
2.375 3-OCHF2 2-F, 4-F H H F F
2.376 3-OCHF2 2-F, 4-F H H CI CI M.p. 70-72°C
2.377 3-OCHF2 2-F, 4-F H H Br CI
2.378 3-OCHF2 2-F, 4-F H H CI Br
2.379 3-OCHF2 2-F, 4-F H H Br Br
2.380 3-OCHF2 2-F, 6-F H H CI CI
2.381 3-OCHF2 2-F, 4-F, 6-F H H CI CI
2.382 3-OCF2CF3 H H H F F
2.383 3-OCF2CF3 H H H CI CI M.p. 66-67°C
2.384 3-OCF2CF3 H H H Br Br
2.385 3-OCF2CF3 2-F H H CI CI
2.386 3-OCF2CF3 2-CH3 H H CI CI
2.387 3-OCF2CF3 3-F H H CI CI
2.388 3-OCF2CF3 3-CF3 H H CI CI
2.389 3-OCF2CF3 4-F H H F F
2.390 3-OCF2CF3 4-F H H CI CI
2.391 3-OCF2CF3 4-F H H Br Br
2.392 3-OCF2CF3 4-CI H H CI CI
2.393 3-OCF2CF3 4-CF3 H H CI CI
2.394 3-OCF2CF3 4-OCF3 H H CI CI
2.395 3-OCF2CF3 4-SCF3 H H CI CI
2.396 3-OCF2CF3 4-SO2CF3 H H CI CI Comp.
Ri R2 R3 R5 R7 R8 Phys. data No.
2.397 3-OCF2CF3 4-CN H H CI CI
2.398 3-OCF2CF3 4-SF5 H H CI CI
2.399 3-OCF2CF3 4-F, 3-F H H CI CI
2.400 3-OCF2CF3 4-F, 3-CF3 H H CI CI
2.401 3-OCF2CF3 2-F, 4-CF3 H H CI CI
2.402 3-OCF2CF3 3-F, 5-F H H CI CI
2.403 3-OCF2CF3 3-CF3, 5-CF3 H H CI CI
2.404 3-OCF2CF3 2-F, 4-F H H CI H
2.405 3-OCF2CF3 2-F, 4-F H H H CI
2.406 3-OCF2CF3 2-F, 4-F H H F F
2.407 3-OCF2CF3 2-F, 4-F H H CI CI oil
2.408 3-OCF2CF3 2-F, 4-F H H Br CI
2.409 3-OCF2CF3 2-F, 4-F H H CI Br
2.410 3-OCF2CF3 2-F, 4-F H H Br Br
2.411 3-OCF2CF3 2-F, 6-F H H CI CI
2.412 3-OCF2CF3 2-F, 4-F, 6-F H H CI CI
2.413 3-OCF2CHF2 H H H F F
2.414 3-OCF2CHF2 H H H CI CI M.p. 57-58°C
2.415 3-OCF2CHF2 . H H H Br Br
2.416 3-OCF2CHF2 2-F H H CI CI oil
2.417 3-OCF2CHF2 2-CH3 H H CI CI oil
2.418 3-OCF2CHF2 3-F H H CI CI
2.419 3-OCF2CHF2 3-CF3 H H CI CI
2.420 3-OCF2CHF2 4-F H H F F
2.421 3-OCF2CHF2 4-F H H CI CI M.p. 70-72°C
2.422 3-OCF2CHF2 4-F H H Br Br
2.423 3-OCF2CHF2 4-CI H H CI CI
2.424 3-OCF2CHF2 4-CF3 H H CI CI
2.425 3-OCF2CHF2 4-OCF3 H H CI CI
2.426 3-OCF2CHF2 4-SCF3 H H CI CI
2.427 3-OCF2CHF2 4-SO2CF3 H H CI CI
2.428 3-OCF2CHF2 4-CN H H CI CI
2.429 3-OCF2CHF2 4-SF5 H H CI CI
2.430 3-OCF2CHF2 4-F, 3-F H H CI CI Comp.
Ri R2 Rs Rs R7 Rs Phys. data No.
2.431 3-OCF2CHF2 4-F, 3-CF3 H H CI CI
2.432 3-OCF2CHF2 2-F, 4-CF3 H H CI CI
2.433 3-OCF2CHF2 3-F, 5-F H H CI CI
2.434 3-OCF2CHF2 3-CF3, 5-CF3 H H CI CI
2.435 3-OCF2CHF2 2-F, 4-F H H CI H
2.436 3-OCF2CHF2 2-F, 4-F H H H CI
2.437 3-OCF2CHF2 2-F, 4-F H H F F
2.438 3-OCF2CHF2 2-F, 4-F H H CI CI resin
2.439 3-OCF2CHF2 2-F, 4-F H H Br CI
2.440 3-OCF2CHF2 2-F, 4-F H H CI Br
2.441 3-OCF2CHF2 2-F, 4-F H H Br Br
2.442 3-OCF2CHF2 2-F, 6-F H H CI CI
2.443 3-OCF2CHF2 2-F, 4-F, 6-F H H CI CI
2.444 3-OCH2CF3 H H H CI CI
2.445 3-OCH2CF3 2-F H H CI CI
2.446 3-OCH2CF3 2-CH3 H H CI CI
2.447 3-OCH2CF3 4-F H H F F
2.448 3-OCH2CF3 4-F H H CI CI
2.449 3-OCH2CF3 4-F H H Br Br
2.450 3-OCH2CF3 4-CI H H CI CI
2.451 3-OCH2CF3 4-CF3 H H CI CI
2.452 3-OCH2CF3 2-F, 4-F H H F F
2.453 3-OCH2CF3 2-F, 4-F H H CI CI
2.454 3-OCH2CF3 2-F, 4-F H H Br Br
2.455 3-SCF3 H H H F F
2.456 3-SCF3 H H H CI CI oil
2.457 3-SCF3 H H H Br Br
2.458 3-SCF3 2-F H H CI CI
2.459 3-SCF3 2-CH3 H H CI CI
2.460 3-SCF3 3-F H H CI CI
2.461 3-SCF3 3-CF3 H H CI CI
2.462 3-SCF3 4-F H H CI H
2.463 3-SCF3 4-F H H H CI
2.464 3-SCF3 4-F H H F F Comp. i R2 R3 R5 R7 R8 Phys. data No.
2.465 3-SCF3 4-F H H CI CI
2.466 3-SCF3 4-F H H Br Br
2.467 3-SCF3 4-CI H H CI CI
2.468 3-SCF3 4-Br H H CI CI
2.469 3-SCF3 4-CF3 H H CI CI
2.470 3-SCF3 4-OCF3 H H CI CI
2.471 3-SCF3 4-SCF3 H H CI CI
2.472 3-SCF3 4-SO2CF3 H H CI CI
2.473 3-SCF3 4-SO2CH3 H H CI CI
2.474 3-SCF3 4-CN H H CI CI
2.475 3-SCF3 4-N02 H H CI CI
2.476 3-SCF3 4-SF5 H H CI CI
2.477 3-SCF3 4-F, 3-F H H CI CI
2.478 3-SCF3 4-F, 3-CI H H CI CI
2.479 3-SCF3 4-F, 3-CN H H CI CI
2.480 3-SCF3 4-F, 3-CF3 H H CI CI
2.481 3-SCF3 2-F, 4-CF3 H H CI CI
2.482 3-SCF3 2-CF3, 4-CF3 H H CI CI
2.483 3-SCF3 3-F, 5-F H H CI CI
2.484 3-SCF3 3-CF3, 5-CF3 H H CI CI
2.485 3-SCF3 2-F, 4-F H H CI H
2.486 3-SCF3 2-F, 4-F H H H CI
2.487 3-SCF3 2-F, 4-F H H F F
2.488 3-SCF3 2-F, 4-F H H CI CI oil
2.489 3-SCF3 2-F, 4-F H H Br Br
2.490 3-SCF3 2-F, 6-F H H CI CI
2.491 3-SCF3 2-F, 4-F, 6-F H H CI CI
2.492 3-SCF3 H H CI CI CI
2.493 3-SCF3 4-F H F CI CI
2.494 3-SCF3 2-F, 4-F H F CI CI
2.495 3-SCF3 2-F, 4-F H CI CI CI
2.496 3-SCF3 2-F, 4-F H CH3 CI CI
2.497 3-SCF3 4-F Br H CI CI
2.498 3-SCF3 2-F, 4-F C≡CH H CI CI Comp.
Ri R2 R3 Rs R7 Rs Phys. data No.
2.499 3-SCF3 2-F, 4-F Br H CI CI
2.500 3-SCF3 2-F, 4-F COCH3 H CI CI
2.501 3-SCF3 2-F, 4-F Br F CI CI
2.502 3-SCHF2 H H H CI CI
2.503 3-SCHF2 2-F H H CI CI
2.504 3-SCHF2 2-CH3 H H CI CI
2.505 3-SCHF2 3-F H H CI CI
2.506 3-SCHF2 3-CF3 H H CI CI
2.507 3-SCHF2 4-F H H F F
2.508 3-SCHF2 4-F H H CI CI
2.509 3-SCHF2 4-F H H Br Br
2.510 3-SCHF2 4-CI H H CI CI
2.511 3-SCHF2 4-CF3 H H CI CI
2.512 3-SCHF2 4-OCF3 H H CI CI
2.513 3-SCHF2 4-SCF3 H H CI CI
2.514 3-SCHF2 4-S02CF3 H H CI CI
2.515 3-SCHF2 4-CN H H CI CI
2.516 3-SCHF2 4-SF5 H H CI CI
2.517 3-SCHF2 4-F, 3-F H H CI CI
2.518 3-SCHF2 4-F, 3-CF3 H H CI CI
2.519 3-SCHF2 2-F, 4-CF3 H H CI CI
2.520 3-SCHF2 3-F, 5-F H H CI CI
2.521 3-SCHF2 3-CF3, 5-CF3 H H CI CI
2.522 3-SCHF2 2-F, 4-F H H F F
2.523 3-SCHF2 2-F, 4-F H H CI CI
2.524 3-SCHF2 2-F, 4-F H H Br Br
2.525 3-SCHF2 2-F, 6-F H H CI CI
2.526 3-SCHF2 2-F, 4-F, 6-F H H CI CI
2.527 3-SOCF3 H H H CI CI oil
2.528 3-SOCF3 2-F H H CI CI
2.529 3-SOCF3 2-CH3 H H CI CI
2.530 3-SOCF3 3-F H H CI CI
2.531 3-SOCF3 3-CF3 H H CI CI
2.532 3-SOCF3 4-F H H F F Comp.
Ri Ra R3 R5 R7 Rs Phys. data No.
2.533 3-SOCF3 4-F H H CI CI
2.534 3-SOCF3 4-F H H Br Br
2.535 3-SOCF3 4-CI H H CI CI
2.536 3-SOCF3 4-CF3 H H CI CI
2.537 3-SOCF3 4-OCF3 H H CI CI
2.538 3-SOCF3 4-SCF3 H H CI CI
2.539 3-SOCF3 4-S02CF3 H H CI CI
2.540 3-SOCF3 4-CN H H CI CI
2.541 3-SOCF3 4-SF5 H H CI CI
2.542 3-SOCF3 4-F, 3-F H H CI CI
2.543 3-SOCF3 4-F, 3-CF3 H H CI CI
2.544 3-SOCF3 2-F, 4-CF3 H H CI CI
2.545 3-SOCF3 3-F, 5-F H H CI CI
2.546 3-SOCF3 3-CF3, 5-CF3 H H CI CI
2.547 3-SOCF3 2-F, 4-F H H CI H
2.548 3-SOCF3 2-F, 4-F H H H CI
2.549 3-SOCF3 2-F, 4-F H H F F
2.550 3-SOCF3 2-F, 4-F H H CI CI
2.551 3-SOCF3 2-F, 4-F H H Br CI
2.552 3-SOCF3 2-F, 4-F H H CI Br
2.553 3-SOCF3 2-F, 4-F H H Br Br
2.554 3-SOCF3 2-F, 6-F H H CI CI
2.555 3-SOCF3 2-F, 4-F, 6-F H H CI CI
2.556 3-S02CF3 H H H CI CI M.p. 87-88°C
2.557 3-S02CF3 2-F H H CI CI
2.558 3-S02CF3 2-CH3 H H CI CI
2.559 3-S02CF3 3-F H H CI CI
2.560 3-S02CF3 3-CF3 H H CI CI
2.561 3-S02CF3 4-F H H F F
2.562 3-S02CF3 4-F H H CI CI
2.563 3-S02CF3 4-F H H Br Br
2.564 3-S02CF3 4-CI H H CI CI
2.565 3-S02CF3 4-Br H H CI CI
2.566 3-S02CF3 4-CF3 H H CI CI Comp.
Ri R2 R3 Rs R7 Rs Phys. data No.
2.567 3-SO2CF3 4-OCF3 H H CI CI
2.568 3-SO2CF3 4-SCF3 H H CI CI
2.569 3-SO2CF3 4-SO2CF3 H H CI CI
2.570 3-SO2CF3 4-SO2CH3 H H CI CI
2.571 3-SO2CF3 4-CN H H CI CI
2.572 3-SO2CF3 4-NO2 H H CI CI
2.573 3-SO2CF3 4-SF5 H H CI CI
2.574 3-SO2CF3 4-F, 3-F H H CI CI
2.575 3-SO2CF3 4-F, 3-CI H H CI CI
2.576 3-SO2CF3 4-F, 3-CN H H CI CI
2.577 3-SO2CF3 4-F, 3-CF3 H H CI CI
2.578 3-SO2CF3 2-F, 4-CF3 H H CI CI
2.579 3-SO2CF3 2-CF3, 4-CF3 H H CI CI
2.580 3-SO2CF3 3-F, 5-F H H CI CI
2.581 3-SO2CF3 3-CF3, 5-CF3 H H CI CI
2.582 3-SO2CF3 2-F, 4-F H H CI H
2.583 3-SO2CF3 2-F, 4-F H H H CI
2.584 3-SO2CF3 2-F, 4-F H H F F
2.585 3-SO2CF3 2-F, 4-F H H CI CI
2.586 3-SO2CF3 2-F, 4-F H H Br CI
2.587 3-SO2CF3 2-F, 4-F H H CI Br
2.588 3-SO2CF3 2-F, 4-F H H Br Br
2.589 3-SO2CF3 2-F, 6-F H H CI CI
2.590 3-SO2CF3 2-F, 4-F, 6-F H H CI CI
2.591 3-SO2CH3 H H H CI CI
2.592 3-SO2CH3 2-F H H CI CI
2.593 3-SO2CH3 2-CH3 H H CI CI
2.594 3-SO2CH3 4-F H H CI CI
2.595 3-SO2CH3 4-CI H H CI CI
2.596 3-SO2CH3 4-CF3 H H CI CI
2.597 3-SO2CH3 2-F, 4-F H H F F
2.598 3-SO2CH3 2-F, 4-F H H CI CI
2.599 3-SO2CH3 2-F, 4-F H H Br Br
2.600 3-SF5 H H H CI CI M.p. 92-94°C Comp.
Ri R2 R3 R5 R7 Rs Phys. data No.
2.601 3-SF5 2-F H H CI CI
2.602 3-SF5 2-CH3 H H CI CI
2.603 3-SF5 3-F H H CI CI
2.604 3-SF5 4-F H H CI CI M.p. 125-128°C
2.605 3-SF5 4-CI H H CI CI
2.606 3-SF5 4-CF3 H H CI CI
2.607 3-SF5 4-OCF3 H H CI CI
2.608 3-SF5 4-SCF3 H H CI CI
2.609 3-SF5 4-SO2CF3 H H CI CI
2.610 3-SF5 4-CN H H CI CI
2.611 3-SF5 4-SF5 H H CI CI
2.612 3-SF5 4-F, 3-F H H CI CI
2.613 3-SF5 4-F, 3-CF3 H H CI CI
2.614 3-SF5 2-F, 4-CF3 H H CI CI
2.615 3-SF5 3-F, 5-F H H CI CI
2.616 3-SF5 2-F, 4-F H H F F
2.617 3-SF5 2-F, 4-F H H CI CI M.p. 118-120°C
2.618 3-SF5 2-F, 4-F H H Br Br
2.619 3-SF5 2-F, 6-F H H CI CI
2.620 3-SF5 2-F, 4-F, 6-F H H CI CI
2.621 3-OCF2CHFCF3 H H H CI CI oil
2.622 3-OCF2CHFCF3 2-F H H CI CI
2.623 3-OCF2CHFCF3 2-F H H Br Br
2.624 3-OCF2CHFCF3 2-CH3 H H CI CI
2.625 3-OCF2CHFCF3 4-F H H F F
2.626 3-OCF2CHFCF3 4-F H H CI CI
2.627 3-OCF2CHFCF3 4-F H H Br Br
2.628 3-OCF2CHFCF3 4-CI H H CI CI
2.629 3-OCF2CHFCF3 4-CF3 H H CI CI
2.630 3-OCF2CHFCF3 2-F, 4-F H H F F
2.631 3-OCF2CHFCF3 2-F, 4-F H H CI F
2.632 3-OCF2CHFCF3 2-F, 4-F H H F CI
2.633 3-OCF2CHFCF3 2-F, 4-F H H CI CI oil
2.634 3-OCF2CHFCF3 2-F, 4-F H H Br Br Comp.
Ri R2 R3 R5 R Rs Phys. data No.
2.635 3-CH2CH3 H H H CI CI
2.636 3-CH2CH3 2-F H H CI CI
2.637 3-CH2CH3 2-CH3 H H CI CI
2.638 3-CH2CH3 4-F H H CI CI
2.639 3-CH2CH3 4-CI H H CI CI
2.640 3-CH2CH3 4-CF3 H H CI CI
2.641 3-CH2CH3 2-F, 4-F H H F F
2.642 3-CH2CH3 2-F, 4-F H H CI CI
2.643 3-CH2CH3 2-F, 4-F H H Br Br
2.644 3-CH(CH3)2 H H H CI CI oil
2.645 3-CH(CH3)2 2-F H H CI CI
2.646 3-CH(CH3)2 2-CH3 H H CI CI
2.647 3-CH(CH3)2 4-F H H CI CI
2.648 3-CH(CH3)2 4-CI H H CI CI
2.649 3-CH(CH3)2 4-CF3 H H CI CI
2.650 3-CH(CH3)2 2-F, 4-F H H F F
2.651 3-CH(CH3)2 2-F, 4-F H H CI CI
2.652 3-CH(CH3)2 2-F, 4-F H H Br Br
2.653 3-C(CH3)3 H H H CI CI oil
2.654 3-C(CH3)3 2-F H H CI CI
2.655 3-C(CH3)3 2-CH3 H H CI CI
2.656 3-C(CH3)3 4-F H H CI CI
2.657 3-C(CH3)3 4-CI H H CI CI
2.658 3-C(CH3)3 4-CF3 H H CI CI
2.659 3-C(CH3)3 2-F, 4-F H H F F
2.660 3-C(CH3)3 2-F, 4-F H H CI CI
2.661 3-C(CH3)3 2-F, 4-F H H Br Br
2.662 3-NO2 H H H CI CI M=359, t=3.55
2.663 3-NO2 2-F H H CI CI
2.664 3-NO2 2-CH3 H H CI CI
2.665 3-NO2 4-F H H CI CI
2.666 3-NO2 4-CI H H CI CI M=393, t=3.80
2.667 3-NO2 4-CF3 H H CI CI M=427, t=3.70
2.668 3-NO2 2-F, 4-F H H F F Comp.
Ri R2 Rs R5 R7 Rs Phys. data No.
2.669 3-N02 2-F, 4-F H H CI CI
2.670 3-N02 2-F, 4-F H H Br Br
2.671 3-CN H H H CI CI M.p. 155-157°C
2.672 3-CN 2-F H H CI CI
2.673 3-CN 2-CH3 H H CI CI
2.674 3-CN 3-F H H CI CI
2.675 3-CN 4-F H H CI CI
2.676 3-CN 4-CI H H CI CI
2.677 3-CN 4-CF3 H H CI CI
2.678 3-CN 4-OCF3 H H CI CI
2.679 3-CN 4-SCF3 H H CI CI
2.680 3-CN 4-SO2CF3 H H CI CI
2.681 3-CN 4-CN H H CI CI
2.682 3-CN 4-SF5 H H CI CI
2.683 3-CN 4-F, 3-F H H CI CI
2.684 3-CN 4-F, 3-CF3 H H CI CI
2.685 3-CN 2-F, 4-CF3 H H CI CI
2.686 3-CN 3-F, 5-F H H CI CI
2.687 3-CN 2-F, 4-F H H F F
2.688 3-CN 2-F, 4-F H H CI CI
2.689 3-CN 2-F, 4-F H H Br Br
2.690 3-CN 2-F, 6-F H H CI CI
2.691 3-CN 2-F, 4-F, 6-F H H CI CI
2.692 3-CF3, 2-F H H H CI CI M.p. 132-134°C
2.693 3-CF3, 2-F 2-F H H CI CI
2.694 3-CF3, 2-F 2-CH3 H H CI CI
2.695 3-CF3, 2-F 4-F H H CI CI
2.696 3-CF3, 2-F 4-CI H H CI CI
2.697 3-CF3, 2-F 4-CF3 H H CI CI
2.698 3-CF3, 2-F 2-F, 4-F H H F F
2.699 3-CF3, 2-F 2-F, 4-F H H CI CI M.p. 137-139°C
2.700 3-CF3, 2-F 2-F, 4-F H H Br Br
2.701 3-CF3, 4-F H H H CI CI M.p. 128-130°C
2.702 3-CF3, 4-F 2-F H H CI CI solid Comp.
Ri R2 R3 R5 R7 R8 Phys. data No.
2.703 3-CF3, 4-F 2-CH3 H H CI CI solid
2.704 3-CF3 4-F 3-F H H CI CI
2.705 3-CF3, 4-F 3-CF3 H H CI CI
2.706 3-CF3 4-F 4-F H H CI CI M.p. 156-157°C
2.707 3-CF3, 4-F 4-F H H Br Br
2.708 3-CF3 4-F 4-CI H H CI CI M.p. 126-128°C
2.709 3-CF3 4-F 4-CF3 H H CI CI
2.710 3-CF3 4-F 4-OCF3 H H CI CI
2.711 3-CF3 4-F 4-SCF3 H H CI CI
2.712 3-CF3 4-F 4-S02CF3 H H CI CI
2.713 3-CF3 4-F 4-CN H H CI CI
2.714 3-CF3 4-F 4-SF5 H H CI CI
2.715 3-CF3 4-F 4-F, 3-F H H CI CI
2.716 3-CF3 4-F 4-F, 3-CF3 H H CI CI
2.717 3-CF3 4-F 2-F, 4-CF3 H H CI CI
2.718 3-CF3 4-F 3-F, 5-F H H CI CI
2.719 3-CF3 4-F 3-CF3, 5-CF3 H H CI CI
2.720 3-CF3 4-F 2-F, 4-F H H CI CI M.p. 142-143°C
2.721 3-CF3 4-F 2-F, 4-F H H Br CI
2.722 3-CF3 4-F 2-F, 4-F H H CI Br
2.723 3-CF3 4-F 2-F, 4-F H H Br Br
2.724 3-CF3 4-F 2-F, 6-F H H CI CI
2.725 3-CF3 4-F 2-F, 4-F, 6-F H H CI CI
2.726 3-CF3 4-F H H CI CI CI
2.727 3-CF3 4-F 4-F H F CI CI
2.728 3-CF3 4-F 2-F, 4-F H F CI CI
2.729 3-CF3 4-F 2-F, 4-F H CI CI CI
2.730 3-CF3 4-F 2-F, 4-F H CH3 CI CI
2.731 3-CF3 4-F 4-F Br H CI CI
2.732 3-CF3 4-F 2-F, 4-F C≡CH H CI CI
2.733 3-CF3 4-F 2-F, 4-F Br H CI CI
2.734 3-CF3 4-F 2-F, 4-F COCH3 H CI CI
2.735 3-CF3 4-F 2-F, 4-F Br F CI CI
2.736 3-CF3, 6-CI H H H CI CI M=416, t=3.79 Comp.
Ri R2 R3 R5 R7 Rs Phys. data No.
2.737 3-CF3, 6-CI 3-CI H H CI CI M=450, t=4.05
2.738 3-CF3, 6-CI 4-CI H H CI CI M=450, t=4.03
2.739 3-CF3, 6-CI 4-CI H H CF3 CI M=484, t=4.07
2.740 3-CF3, 6-CI 3-CF3 H H CI CI M=484, t=4.03
2.741 3-CF3, 6-CI 4-CF3 H H CI CI M=484, t=4.00
2.742 3-OCF3, 4-F H H H CI CI
2.743 3-OCF3, 4-F 2-F H H CI CI
2.744 3-OCF3, 4-F 2-CH3 H H CI CI
2.745 3-OCF3, 4-F 3-F H H CI CI
2.746 3-OCF3, 4-F 3-CF3 H H CI CI
2.747 3-OCF3, 4-F 4-F H H CI CI
2.748 3-OCF3, 4-F 4-F H H Br Br
2.749 3-OCF3, 4-F 4-CI H H CI CI
2.750 3-OCF3, 4-F 4-CF3 H H CI CI
2.751 3-OCF3, 4-F 4-OCF3 H H CI CI
2.752 3-OCF3, 4-F 4-SCF3 H H CI CI
2.753 3-OCF3, 4-F 4-SO2CF3 H H CI CI
2.754 3-OCF3, 4-F 4-CN H H CI CI
2.755 3-OCF3, 4-F 4-SF5 H H CI CI
2.756 3-OCF3, 4-F 4-F, 3-F H H CI CI
2.757 3-OCF3, 4-F 4-F, 3-CF3 H H CI CI
2.758 3-OCF3, 4-F 2-F, 4-CF3 H H CI CI
2.759 3-OCF3, 4-F 3-F, 5-F H H CI CI
2.760 3-OCF3, 4-F 3-CF3, 5-CF3 H H CI CI
2.761 3-OCF3, 4-F 2-F, 4-F H H CI CI
2.762 3-OCF3, 4-F 2-F, 4-F H H Br CI
2.763 3-OCF3, 4-F 2-F, 4-F H H CI Br
2.764 3-OCF3, 4-F 2-F, 4-F H H Br Br
2.765 3-OCF3, 4-F 2-F, 6-F H H CI CI
2.766 3-OCF3, 4-F 2-F, 4-F, 6-F H H CI CI
2.767 3-CI, 4-F H H H CI CI M.p. 130-132°C
2.768 3-CI, 4-F 2-F H H CI CI
2.769 3-CI, 4-F 2-CH3 H H CI CI
2.770 3-CI, 4-F 3-F H H CI CI Comp.
Ri R2 R3 R5 R7 Rs Phys. data No.
2.771 3-CI, 4-F 3-CF3 H H CI CI
2.772 3-CI, 4-F 4-F H H CI CI
2.773 3-CI, 4-F 4-F H H Br Br
2.774 3-CI, 4-F 4-CI H H CI CI
2.775 3-CI, 4-F 4-CF3 H H CI CI
2.776 3-CI, 4-F 4-OCF3 H H CI CI
2.111 3-CI, 4-F 4-SCF3 H H CI CI
2.778 3-CI, 4-F 4-SO2CF3 H H CI CI
2.779 3-CI, 4-F 4-CN H H CI CI
2.780 3-CI, 4-F 4-SF5 H H CI CI
2.781 3-CI, 4-F 4-F, 3-F H H CI CI
2.782 3-CI, 4-F 4-F, 3-CF3 H H CI CI
2.783 3-CI, 4-F 2-F, 4-CF3 H H CI CI
2.784 3-CI, 4-F 3-F, 5-F H H CI CI
2.785 3-CI, 4-F 3-CF3, 5-CF3 H H CI CI
2.786 3-CI, 4-F 2-F, 4-F H H CI CI M.p. 144-146°C
2.787 3-CI, 4-F 2-F, 4-F H H Br CI
2.788 3-CI, 4-F 2-F, 4-F H H CI Br
2.789 3-CI, 4-F 2-F, 4-F H H Br Br
2.790 3-CI, 4-F 2-F, 6-F H H CI CI
2.791 3-CI, 4-F 2-F, 4-F, 6-F H H CI CI
2.792 2-F, 4-F 3-CF3 H H CI CI M.p. 120-121 °C
2.793 2-CI, 4-CI H H H CI CI M=382, t=3.82
2.794 2-CI, 4-CI 4-CI H H CI CI M=416, t=4.11
2.795 2-CI, 4-CI 3-CF3 H H CI CI M=450, t=4.06
2.796 2-CI, 4-CI 4-CF3 H H CI CI M=450, t=4.07
2.797 2-CI, 6-CI H H H CI CI M=382, t=3.71
2.798 2-CI, 6-CI 4-CI H H CI CI M=416, t=3.95
2.799 2-CI, 6-CI 3-CF3 H H CI CI M=450, t=3.94
2.800 2-CI, 6-CI 4-CF3 H H CI CI M=450, t=3.90
2,801 3-F, 4-F H H H CI CI
2.802 3-F, 4-F 2-F H H CI CI
2.803 3-F, 4-F 2-CH3 H H CI CI
2.804 3-F, 4-F 3-F H H CI CI Comp.
Ri R2 Rs Rs R7 R8 Phys. data No.
2.805 3-F, 4-F 3-CF3 H H CI CI
2.806 3-F, 4-F 4-F H H CI CI
2.807 3-F, 4-F 4-F H H Br Br
2.808 3-F, 4-F 4-CI H H CI CI
2.809 3-F, 4-F 4-CF3 H H CI CI
2.810 3-F, 4-F 4-OCF3 H H CI CI
2.811 3-F, 4-F 4-SCF3 H H CI CI
2.812 3-F, 4-F 4-S02CF3 H H CI CI
2.813 3-F, 4-F 4-CN H H CI CI
2.814 3-F, 4-F 4-SF5 H H CI CI
2.815 3-F, 4-F 4-F, 3-F H H CI CI
2.816 3-F, 4-F 4-F, 3-CF3 H H CI CI
2.817 3-F, 4-F 2-F, 4-CF3 H H CI CI
2.818 3-F, 4-F 3-F, 5-F H H CI CI
2.819 3-F, 4-F 3-CF3, 5-CF3 H H CI CI
2.820 3-F, 4-F 2-F, 4-F H H CI CI
2.821 3-F, 4-F 2-F, 4-F H H Br CI
2.822 3-F, 4-F 2-F, 4-F H H CI Br
2.823 3-F, 4-F 2-F, 4-F H H Br Br
2.824 3-F, 4-F 2-F, 6-F H H CI CI
2.825 3-F, 4-F 2-F, 4-F, 6-F H H CI CI
2.826 2,3-(-OCF2O-) H H H CI CI M.p. 116-117°C
2.827 2,3-(-OCF2O-) 2-F H H CI H
2.828 2,3-(-OCF2O-) 2-F H H H CI
2.829 2,3-(-OCF2O-) 2-F H H CI CI M.p. 112-114°C
2.830 2,3-(-OCF20-) 2-CH3 H H CI CI
2.831 2,3-(-OCF20-) 3-F H H CI CI
2.832 2,3-(-OCF2O-) 3-CF3 H H CI CI
2.833 2,3-(-OCF2O-) 4-F H H CI H
2.834 2,3-(-OCF2O-) 4-F H H H CI
2.835 2,3-(-OCF20-) 4-F H H CI CI M.p. 154-156°C
2.836 2,3-(-OCF2O-) 4-F H H Br Br
2.837 2,3-(-OCF2O-) 4-CI H H CI CI
2.838 2,3-(-OCF2O-) 4-CF3 H H CI CI Comp.
Ri R2 R3 R5 R7 R8 Phys. data No.
2.839 2,3-(-OCF2O- 4-OCF3 H H CI CI
2.840 2,3-(-OCF2O-; ) 4-SCF3 H H CI CI
2.841 2,3-(-OCF2O-J 4-SO2CF3 H H CI CI
2.842 2,3-(-OCF2O- 4-CN H H CI CI
2.843 2,3-(-OCF2O- 4-SF5 H H CI CI
2.844 2,3-(-OCF2O-) 4-F, 3-F H H CI CI
2.845 2,3-(-OCF2O-1 4-F, 3-CF3 H H CI CI
2.846 2,3-(-OCF2O-; 2-F, 4-CF3 H H CI CI
2.847 2,3-(-OCF2O-j 3-F, 5-F H H CI CI
2.848 2,3-(-OCF2O-1 3-CF3, 5-CF3 H H CI CI
2.849 2,3-(-OCF2O-1 2-F, 4-F H H CI H
2.850 2,3-(-OCF2O- 2-F, 4-F H H H CI
2.851 2,3-(-OCF2O- 2-F, 4-F H H CI CI M.p. 118-120°C
2.852 2,3-(-OCF2O-1 2-F, 4-F H H Br CI
2.853 2,3-(-OCF2O- 2-F, 4-F H H CI Br
2.854 2,3-(-OCF2O- 2-F, 4-F H H Br Br
2.855 2,3-(-OCF2O-1 2-F, 6-F H H CI CI
2.856 2,3-(-OCF2O- 2-F, 4-F, 6-F H H CI CI
2.857 2,3-(-OCF2O-; H H CI CI CI
2.858 2,3-(-OCF2O- 4-F H F CI CI
2.859 2,3-(-OCF2O- I 2-F, 4-F H F CI CI
2.860 2,3-(-OCF2O-, ) 2-F, 4-F H CI CI CI
2.861 2,3-(-OCF2O- 2-F, 4-F H CH3 CI CI
2.862 2,3-(-OCF2O- 4-F Br H CI CI
2.863 2,3-(-OCF2O-/ 2-F, 4-F C≡CH H CI CI
2.864 2,3-(-OCF2O- 2-F, 4-F Br H CI CI
2.865 2,3-(-OCF20- 2-F, 4-F COCH3 H CI CI
2.866 2,3-(-OCF2O-] 2-F, 4-F Br F CI CI
2.867 3,4-(-OCF2O- H H H CI CI M.p. 114-116°C
2.868 3,4-(-OCF2O-1 2-F H H CI CI
2.869 3,4-(-OCF2O- 2-CH3 H H CI CI
2.870 3,4-(-OCF2O- > 4-F H H CI CI M.p. 131-133°C
2.871 3)4-(-OCF2O-1 4-CI H H CI CI
2.872 3,4-(-OCF2O- 4-CF3 H H CI CI Comp.
Ri R2 R3 R5 R7 R8 Phys. data No.
2.873 3,4-(-OCF20-) 2-F, 4-F H H F F
2.874 3,4-(-OCF20-) 2-F, 4-F H ' H CI CI M.p. 128-130°C
2.875 3,4-(-OCF2O-) 2-F, 4-F H H Br Br
2.876 2,3-(-OCF2CF2O- ) H H H CI CI M.p. 80-83°C
2.877 2,3-(-OCF2CF2O-, > 2-F H H CI CI
2.878 2,3-(-OCF2CF2O- 2-CH3 H H CI CI
2.879 2,3-(-OCF2CF2O- I 3-F H H CI CI
2.880 2,3-(-OCF2CF2O-< 1 3-CF3 H H CI CI
2.881 2,3-(-OCF2CF2O- 4-F H H CI CI M.p. 95-98°C
2.882 2,3-(-OCF2CF2O- I 4-F H H Br Br
2.883 2,3-(-OCF2CF2O- 1 4-CI H H CI CI
2.884 2,3-(-OCF2CF2O- 4-CF3 H H CI CI
2.885 2,3-(-OCF2CF2O- I 4-OCF3 H H CI CI
2.886 2,3-(-OCF2CF2O- I 4-SCF3 H H CI CI
2.887 2,3-(-OCF2CF2O- ) 4-SO2CF3 H H CI CI
2.888 2,3-(-OCF2CF2O- I 4-CN H H CI CI
2.889 2,3-(-OCF2CF2O- I 4-SF5 H H CI CI
2.890 2,3-(-OCF2CF2O- ) 4-F, 3-F H H CI CI
2.891 2,3-(-OCF2CF2O- I 4-F, 3-CF3 H H CI CI
2.892 2,3-(-OCF2CF2O- 2-F, 4-CF3 H H CI CI
2.893 2,3-(-OCF2CF2O- 3-F, 5-F H H CI CI
2.894 2,3-(-OCF2CF2O- > 3-CF3, 5-CF3 H H CI CI
2.895 2,3-(-OCF2CF2O- 2-F, 4-F H H CI CI solid
2.896 2,3-(-OCF2CF2O- 2-F, 4-F H H Br CI
2.897 2,3-(-OCF2CF2O- 1 2-F, 4-F H H CI Br
2.898 2,3-(-OCF2CF2O- 2-F, 4-F H H Br Br
2.899 2,3-(-OCF2CF2O- 2-F, 6-F H H CI CI
2.900 2,3-(-OCF2CF2O- 1 2-F, 4-F, 6-F H H CI CI
2.901 3,4-(-OCF2CF2O- H H H CI CI
2.902 3,4-(-OCF2CF2O- 2-F H H CI CI
2.903 3,4-(-OCF2CF2O-, 1 2-CH3 H H CI CI
2.904 3,4-(-OCF2CF2O- 4-F H H CI CI
2.905 3,4-(-OCF2CF2O-1 4-CI H H CI CI
2.906 3,4-(-OCF2CF2O- 4-CF3 H H CI CI Comp.
Ri R2 R3 R5 R7 Rs Phys. data No.
2.907 3,4-(-OCF2CF20-) 2-F, 4-F H H F F
2.908 3,4-(-OCF2CF2O-) 2-F, 4-F H H CI CI
2.909 3,4-(-OCF2CF20-) 2-F, 4-F H H Br Br
2.910 2,3-(-OCF2CF2O-), 4-F H H H CI CI
2.911 2,3-(-OCF2CF2O-), 4-F 2-F H H CI CI
2.912 2,3-(-OCF2CF2O-), 4-F 2-CH3 H H CI CI
2.913 2,3-(-OCF2CF2O-), 4-F 4-F H H CI CI
2.914 2,3-(-OCF2CF2O-), 4-F 4-CI H H CI CI
2.915 2,3-(-OCF2CF2O-), 4-F 4-CF3 H H CI CI
2.916 2,3-(-OCF2CF2O-), 4-F 2-F, 4-F H H F F
2.917 2,3-(-OCF2CF2O-), 4-F 2-F, 4-F H H CI CI
2.918 2,3-(-OCF2CF2O-), 4-F 2-F, 4-F H H Br Br
Table 3: Compounds of formula l3
Figure imgf000064_0001
Comp.
Ri R2 R3 R4 Re R5 R7 Rs Phys. data No.
3.001 H 3-F H H F H F F
3.002 H 3-F H F H F H H
3.003 H 3-F H - CH2 - H CI CI
3.004 H 3-F H - CF2CF2 - H H H
3.005 4-CI 3-F H H H H H H
3.006 4-CI 3-F H H F H F F
3.007 4-F 3-F H H H H H H Comp.
Ri R2 R3 R4 Re R5 R7 Rs Phys. data No.
3.008 4-F 3-F H H F H F F
3.009 4-F 3-F H F H F H H
3.010 4-F 3-F H H CI H CI CI
3.011 4-F 3-F H CI H CI H H
3.012 4-F 3-F H - CH2 - H CI CI
3.013 4-F 3-F H - CF2CF2 - H H H
3.014 2-F, 4-F 3-F H H H H H H
3.015 2-F, 4-F 3-F H H F H F F
3.016 2-F, 4-F 3-F H F F F F F
3.017 2-F, 4-F 3-F H F H F H H
3.018 2-F, 4-F 3-F H H CI H CI CI
3.019 2-F, 4-F 3-F H CI CI CI CI CI
3.020 2-F, 4-F 3-F H CI H CI H H
3.021 2-F, 4-F 3-F H CF3 F H F F
3.022 2-F, 4-F 3-F H CH3 F CH3 F F
3.023 2-F, 4-F 3-F H - CH2 - H CI CI
3.024 2-F, 4-F 3-F H - CF2CF2 - H H H
3.025 H 3-CF3 H H F H F F
3.026 H 3-CF3 H F H F H H
3.027 H 3-CF3 H H CI H CI CI
3.028 H 3-CF3 H CI H CI H H
3.029 H 3-CF3 H - CH2 - H CI CI
3.030 H 3-CF3 H - CF2CF2 - H H H
3.031 4-CI 3-CF3 H H H H H H
3.032 4-CI 3-CF3 H H F H F F
3.033 4-F 3-CF3 H H H H H H
3.034 4-F 3-CF3 H H F H F F
3.035 4-F 3-CF3 H F H F H H
3.036 4-F 3-CF3 H H CI H CI CI
3.037 4-F 3-CF3 H CI H CI H H
3.038 4-F 3-CF3 H - CH2 - H CI CI
3.039 4-F 3-CF3 H - CF2CF2 - H H H
3.040 2-F, 4-F 3-CF3 H H H H H H
3.041 2-F, 4-F 3-CF3 H H F H F H Comp.
F lι R2 R3 R Rε R5 R7 Rs Phys. data No.
3.042 2-F, 4-F 3-CF3 H H F H F F
3.043 2-F, 4-F 3-CF3 H F F F F F
3.044 2-F, 4-F 3-CF3 H F H H H H
3.045 2-F, 4-F 3-CF3 H F H F H H
3.046 2-F, 4-F 3-CF3 H H CI H CI H
3.047 2-F, 4-F 3-CF3 H H CI H CI CI
3.048 2-F, 4-F 3-CF3 H CI CI CI CI Cl
3.049 2-F, 4-F 3-CF3 H CI H H H H
3.050 2-F, 4-F 3-CF3 H CI H CI H H
3.051 2-F, 4-F 3-CF3 H CF3 F H F F
3.052 2-F, 4-F 3-CF3 H F CH3 F CH3 CH3
3.053 2-F, 4-F 3-CF3 H CH3 F CH3 F F
3.054 2-F, 4-F 3-CF3 Br H F H F F
3.055 2-F, 4-F 3-CF3 C≡CH H F H F F
3.056 2-F, 4-F 3-CF3 COCH3 H F H F F
3.057 2-F, 4-F 3-CF3 H - CH2 - H H H
3.058 2-F, 4-F 3-CF3 H - CH2 - CI H H
3.059 2-F, 4-F 3-CF3 H - CH2 - H CI Cl
3.060 2-F, 4-F 3-CF3 H - CH2 - H Br Br
3.061 2-F, 4-F 3-CF3 H - CH2 - CH3 CI Cl
3.062 2-F, 4-F 3-CF3 H - CH2 - CI CI Cl
3.063 2-F, 4-F 3-CF3 H - C(CI)2 - H CI Cl
3.064 2-F, 4-F 3-CF3 H - C(CI)2 - CH3 CI Cl
3.065 2-F, 4-F 3-CF3 H - C(CI)2 - CF3 CI Cl
3.066 2-F, 4-F 3-CF3 H - CH2CH2 - H H H
3.067 2-F, 4-F 3-CF3 H - CH2CH2 - H CI Cl
3.068 2-F, 4-F 3-CF3 H - CF2CF2 - H H H
3.069 2-F, 4-F 3-CF3 H - CF2CF2 - H CI Cl
3.070 H 3-OCF3 H H F H F F
3.071 H 3-OCF3 H F H F H H
3.072 H 3-OCF3 H H CI H CI Cl
3.073 H 3-OCF3 H CI H CI H H
3.074 H 3-OCF3 H - CH2 - H CI Cl
3.075 H 3-OCF3 H - CF2CF2 - H H H Comp.
Ri R2 R3 R4 Re R5 R7 Rs Phys. data No.
3.076 4-CI 3-OCF3 H H H H H H
3.077 4-CI 3-OCF3 H H F H F F
3.078 4-F 3-OCF3 H H H H H H
3.079 4-F 3-OCF3 H H F H F F
3.080 4-F 3-OCF3 H F H F H H
3.081 4-F 3-OCF3 H H Cl H Cl Cl
3.082 4-F 3-OCF3 H Cl H Cl H H
3.083 4-F 3-OCF3 H - CH2 - H Cl Cl
3.084 4-F 3-OCF3 H - CF2CF2 - H H H
3.085 2-F, 4-F 3-OCF3 H H H H H H
3.086 2-F, 4-F 3-OCF3 H H F H F H
3.087 2-F, 4-F 3-OCF3 H H F H F F
3.088 2-F, 4-F 3-OCF3 H F F F F F
3.089 2-F, 4-F 3-OCF3 H F H H H H
3.090 2-F, 4-F 3-OCF3 H F H F H H
3.091 2-F, 4-F 3-OCF3 H H Cl H Cl H
3.092 2-F, 4-F 3-OCF3 H H Cl H Cl Cl
3.093 2-F, 4-F 3-OCF3 H Cl Cl Cl Cl Cl
3.094 2-F, 4-F 3-OCF3 H Cl H H H H
3.095 2-F, 4-F 3-OCF3 H Cl H Cl H H
3.096 2-F, 4-F 3-OCF3 H CF3 F H F F
3.097 2-F, 4-F 3-OCF3 H F ( H3 F CH3 CH3
3.098 2-F, 4-F 3-OCF3 H CH3 F CH3 F F
3.099 2-F, 4-F 3-OCF3 Br H F H F F
3.100 2-F, 4-F 3-OCF3 C≡CH H F H F F
3.101 2-F, 4-F 3-OCF3 COCH3 H F H F F
3.102 2-F, 4-F 3-OCF3 H - CH2 - H H H
3.103 2-F, 4-F 3-OCF3 H - CH2 - Cl H H
3.104 2-F, 4-F 3-OCF3 H - CH2 - H Cl Cl
3.105 2-F, 4-F 3-OCF3 H - CH2 - H Br Br
3.106 2-F, 4-F 3-OCF3 H - CH2 - CH3 Cl Cl
3.107 2-F, 4-F 3-OCF3 H - CH2 - Cl Cl Cl
3.108 2-F, 4-F 3-OCF3 H - C(CI)2 - H Cl Cl
3.109 2-F, 4-F 3-OCF3 H - C(CI)2 - CH3 Cl Cl Comp.
Ri R2 R3 R4 Re R5 R7 Rs Phys. data No.
3.110 2-F, 4-F 3-OCF3 H - C(CI)2 - CF3 Cl Cl
3.111 2-F, 4-F 3-OCF3 H - CH2CH2 - H H H
3.112 2-F, 4-F 3-OCF3 H - CH2CH2 - H Cl Cl
3.113 2-F, 4-F 3-OCF3 H - CF2CF2 - H H H
3.114 2-F, 4-F 3-OCF3 H - CF2CF2 - H Cl Cl
3.115 H 3-SF3 H H F H F F
3.116 H 3-SF3 H F H F H H
3.117 H 3-SF3 H - CH2 - H Cl Cl
3.118 H 3-SF3 H - CF2CF2 - H H H
3.119 4-CI 3-SF3 H H H H H H
3.120 4-CI 3-SF3 H H F H F F
3.121 4-F 3-SF3 H H H H H H
3.122 4-F 3-SF3 H H F H F F
3.123 4-F 3-SF3 H F H F H H
3.124 4-F 3-SF3 H H Cl H Cl Cl
3.125 4-F 3-SF3 H Cl H Cl H H
3.126 4-F 3-SF3 H - CH2 - H Cl Cl
3.127 4-F 3-SF3 H - CF2CF2 - H H H
3.128 2-F, 4-F 3-SF3 H H H H H H
3.129 2-F, 4-F 3-SF3 H H F H F F
3.130 2-F, 4-F 3-SF3 H F F F F F
3.131 2-F, 4-F 3-SF3 H F H F H H
3.132 2-F, 4-F 3-SF3 H H Cl H Cl Cl
3.133 2-F, 4-F 3-SF3 H Cl Cl Cl Cl Cl
3.134 2-F, 4-F 3-SF3 H Cl H Cl H H
3.135 2-F, 4-F 3-SF3 H CF3 F H F F
3.136 2-F, 4-F 3-SF3 H CH3 F CH3 F F
3.137 2-F, 4-F 3-SF3 H - CH2 - H Cl Cl
3.138 2-F, 4-F 3-SF3 H - CF2CF2 - H H H
3.139 H 2,3-(-OCF20-) H H F H F F
3.140 H 2,3-(-OCF20-) H F H F H H
3.141 4-CI 2,3-(-OCF2O-) H H H H H H
3.142 4-CI 2,3-(-OCF2O-) H H F H F F
3.143 4-F 2,3-(-OCF20-) H H H H H H Comp.
Ri R2 R3 R4 Re Rs R7 R8 Phys. data No.
3.144 4-F 2,3-(-OCF20-) H H F H F F
3.145 4-F 2,3-(-0CF2O) H F H F H H
3.146 4-F 2,3-(-0CF2O) H H Cl H Cl Cl
3.147 4-F 2,3-(-OCF2O-) H Cl H Cl H H
3.148 2-F, 4-F 2,3-(-OCF2O-) H H H H H H
3.149 2-F, 4-F 2,3-(-OCF20-) H H F H F F
3.150 2-F, 4-F 2,3-(-OCF2O-) H F F F F F
3.151 2-F, 4-F 2,3-(-OCF2O-) H F H F H H
3.152 2-F, 4-F 2,3-(-OCF20-) H H Cl H Cl Cl
3.153 2-F, 4-F 2,3-(-OCF2O-) H Cl Cl Cl Cl Cl
3.154 2-F, 4-F 2,3-(-OCF20-) H Cl H Cl H H
3.155 2-F, 4-F 2,3-(-OCF2O-) H CF3 F H F F
3.156 2-F, 4-F 2,3-(-OCF2O-) H CH3 F CH3 F F
Table 4: Compounds of formula l
Figure imgf000069_0001
Comp.
Ri R2 R3 Rs R7 Rs Phys. data No.
4.001 H H H H Cl Cl
4.002 2-F H H H Cl Cl
4.003 2-CH3 H H H Cl Cl
4.004 4-F H H H Cl Cl
4.005 3-CI H H H Cl Cl
4.006 3-CI H H H CF3 Cl Comp.
Ri ■ *2 R3 Rs R7 Rs Phys. data No.
4.007 4-CI H H H Cl Cl
4.008 4-OCH3 H H H Cl Cl
4.009 3-CF3 H H H Cl Cl
4.010 3-CF3 H H H CF3 Cl
4.011 4-CF3 H H H Cl Cl
4.012 2-F, 4-F H H H Cl Cl
4.013 2-CI, 5-CI H H H Cl Cl
4.014 H 3-F H H Cl Cl M.p. 114-115°C
4.015 H 3-F H H Br Br
4.016 2-F 3-F H H Cl Cl
4.017 2-CH3 3-F H H Cl Cl
4.018 4-F 3-F H H F F
4.019 4-F 3-F H H Cl Cl
4.020 4-F 3-F H H Br Br
4.021 4-CI 3-F H H Cl Cl
4.022 4-CF3 3-F H H Cl Cl
4.023 2-F, 4-F 3-F H H F F
4.024 2-F, 4-F 3-F H H Cl Cl M.p. 136-137°C
4.025 2-F, 4-F 3-F H H Br Br
4.026 H 3-F H Cl Cl Cl
4.027 4-F 3-F H F Cl Cl
4.028 2-F, 4-F 3-F H F Cl Cl
4.029 2-F, 4-F 3-F H Cl Cl Cl
4.030 2-F, 4-F 3-F H CH3 Cl Cl
4.031 4-F 3-F Br H Cl Cl
4.032 2-F, 4-F 3-F C≡CH H Cl Cl
4.033 2-F, 4-F 3-F Br H Cl Cl
4.034 2-F, 4-F 3-F COCH3 H Cl Cl
4.035 2-F, 4-F 3-F Br F Cl Cl
4.036 4-CI 2-CI H H Cl Cl
4.037 3-CF3 2-CI H H Cl Cl
4.038 4-CF3 2-CI H H Cl Cl
4.039 H 3-CI H H Cl Cl
4.040 2-F 3-CI H H Cl Cl Comp.
Ri R2 R3 Rs R7 Rs Phys. data No.
4.041 2-CH3 3-CI H H Cl Cl
4.042 4-F 3-CI H H F F
4.043 4-F 3-CI H H Cl Cl
4.044 4-F 3-CI H H Br Br
4.045 3-CI 3-CI H H Cl Cl
4.046 4-CI 3-CI H H Cl Cl
4.047 4-CI 3-CI H H CF3 Cl
4.048 3-CF3 3-CI H H Cl Cl
4.049 4-CF3 3-CI H H Cl Cl
4.050 2-F, 4-F 3-CI H H F F
4.051 2-F, 4-F 3-CI H H Cl Cl
4.052 2-F, 4-F 3-CI H H Br Br
4.053 H 4-CI H H Cl Cl
4.054 3-CI 4-CI H H Cl Cl
4.055 4-CI 4-CI H H Cl Cl
4.056 3-CF3 4-CI H H Cl Cl M.p. 94-96°C
4.057 4-CF3 4-CI H H Cl Cl
4.058 H 3-Br H H Cl Cl
4.059 2-F 3-Br H H Cl Cl
4.060 2-CH3 3-Br H H Cl Cl
4.061 4-F 3-Br H H Cl Cl
4.062 4-CI 3-Br H H Cl Cl
4.063 4-CF3 3-Br H H Cl Cl
4.064 2-F, 4-F 3-Br H H Cl Cl
4.065 H 3-CF3 H H H H
4.066 H 3-CF3 H H F F
4.067 H 3-CF3 H H Cl Cl M.p. 120-121 °C
4.068 H 3-CF3 H H Br Br
4.069 2-F 3-CF3 H H F F
4.070 2-F 3-CF3 H H Cl Cl oil
4.071 2-F 3-CF3 H H Br Br
4.072 2-CI 3-CF3 H H Cl Cl
4.073 2-CH3 3-CF3 H H F F
4.074 2-CH3 3-CF3 H H Cl Cl oil Comp.
Ri R2 R3 Rs R7 Rs Phys. data No.
4.075 2-CH3 3-CF3 H H Br Br
4.076 2-OCH3 3-CF3 H H Cl Cl
4.077 3-F 3-CF3 H H Cl Cl
4.078 3-CI 3-CF3 H H Cl Cl
4.079 3-Br 3-CF3 H H Cl Cl
4.080 3-OCF3 3-CF3 H H Cl Cl
4.081 4-F 3-CF3 H H H H
4.082 4-F 3-CF3 H H Cl H
4.083 4-F 3-CF3 H H H Cl
4.084 4-F 3-CF3 H H Br H
4.085 4-F 3-CF3 H H H Br
4.086 4-F 3-CF3 H H F F
4.087 4-F 3-CF3 H H Cl F
4.088 4-F 3-CF3 H H F Cl
4.089 4-F 3-CF3 H . H Cl Cl
4.090 4-F 3-CF3 H H Br Cl
4.091 4-F 3-CF3 H H Cl Br
4.092 4-F 3-CF3 H H CH3 Cl
4.093 4-F 3-CF3 H H Cl CH3
4.094 4-F 3-CF3 H H CF3 Cl
4.095 4-F 3-CF3 H H Cl CF3
4.096 4-F 3-CF3 H H Br Br
4.097 4-F 3-CF3 H H CF3 CF3
4.098 4-CI 3-CF3 H H H H
4.099 4-CI 3-CF3 H H F F
4.100 4-CI 3-CF3 H H Cl Cl
4.101 4-CI 3-CF3 H H CF3 Cl
4.102 4-CI 3-CF3 H H Br Br
4.103 4-Br 3-CF3 H H Cl Cl
4.104 3-CF3 3-CF3 H H Cl Cl
4.105 3-CF3 3-CF3 H H CF3 Cl
4.106 4-CF3 3-CF3 H H F F
4.107 4-CF3 3-CF3 H H Cl Cl
4.108 4-CF3 3-CF3 H H Br Br Comp.
Ri R2 R3 Rs R7 Rs Phys. data No.
4.109 4-OCF3 3-CF3 H H Cl Cl
4.110 4-SCF3 3-CF3 H H Cl Cl
4.111 4-S02CF3 3-CF3 H H F F
4.112 4-S02CF3 3-CF3 H H Cl Cl
4.113 4-S02CF3 3-CF3 H H Br Br
4.114 4-S02CH3 3-CF3 H H Cl Cl
4.115 4-CN 3-CF3 H H Cl Cl
4.116 4-NO2 3-CF3 H H Cl Cl
4.117 4-SF5 3-CF3 H H Cl Cl
4.118 4-F, 3-F 3-CF3 H H F F
4.119 4-F, 3-F 3-CF3 H H Cl Cl
4.120 4-F, 3-F 3-CF3 H H Br Br
4.121 4-F, 3-CI 3-CF3 H H Cl Cl
4.122 4-F, 3-CN 3-CF3 H H Cl Cl
4.123 4-F, 3-CF3 3-CF3 H H Cl Cl
4.124 2-F, 4-CF3 3-CF3 H H Cl Cl
4.125 2-CF3, 4-CF3 3-CF3 H H Cl Cl
4.126 3-F, 5-F 3-CF3 H H Cl Cl
4.127 3-CF3, 5-CF3 3-CF3 H H Cl Cl
4.128 2-F, 4-F 3-CF3 H H H H
4.129 2-F, 4-F 3-CF3 H H Cl H
4.130 2-F, 4-F 3-CF3 H H H Cl
4.131 2-F, 4-F 3-CF3 H H Br H
4.132 2-F, 4-F 3-CF3 H H H Br
4.133 2-F, 4-F 3-CF3 H H F F
4.134 2-F, 4-F 3-CF3 H H Cl F
4.135 2-F, 4-F 3-CF3 H H F Cl
4.136 2-F, 4-F 3-CF3 H H Cl Cl M.p. 103-104°C
4.137 2-F, 4-F 3-CF3 H H Br Cl
4.138 2-F, 4-F 3-CF3 H H Cl Br
4.139 2-F, 4-F 3-CF3 H H CH3 Cl
4.140 2-F, 4-F 3-CF3 H H Cl CH3
4.141 2-F, 4-F 3-CF3 H H CF3 Cl
4.142 2-F, 4-F 3-CF3 H H Cl CF3 Comp.
Ri R2 R3 Rs R7 Rs Phys. data No.
4.143 2-F, 4-F 3-CF3 H H Br Br M.p. 68-78°C
4.144 2-F, 4-F 3-CF3 H H CF3 CF3
4.145 2-F, 6-F 3-CF3 H H F F
4.146 2-F, 6-F 3-CF3 H H Cl Cl
4.147 2-F, 6-F 3-CF3 H H Br Br
4.148 2-CI, 4-F 3-CF3 H H Cl Cl
4.149 2-CI, 4-CI 3-CF3 H H Cl Cl
4.150 2-CI, 5-CI 3-CF3 H H Cl Cl
4.151 2-F, 4-F, 6-F 3-CF3 H H Cl Cl
4.152 H 3-CF3 H Cl Cl Cl
4.153 2-F 3-CF3 H Cl Cl Cl
4.154 4-F 3-CF3 H F Cl Cl
4.155 4-F 3-CF3 H Cl Cl Cl
4.156 2-F, 4-F 3-CF3 H F Cl Cl
4.157 2-F, 4-F 3-CF3 H F Cl H
4.158 2-F, 4-F 3-CF3 H F H Cl
4.159 2-F, 4-F 3-CF3 H Cl Cl Cl
4.160 2-F, 4-F 3-CF3 H Cl Cl H
4.161 2-F, 4-F 3-CF3 H Cl H Cl
4.162 2-F, 4-F 3-CF3 H CH3 Cl Cl
4.163 H 3-CF3 Cl H Cl Cl
4.164 H 3-CF3 Br H Cl Cl
4.165 4-F 3-CF3 Cl H Cl Cl
4.166 4-F 3-CF3 Br H Cl Cl
4.167 4-F 3-CF3 CN H Cl Cl
4.168 4-CI 3-CF3 Br H Cl Cl
4.169 2-F, 4-F 3-CF3 CH3 H Cl Cl
4.170 2-F, 4-F 3-CF3 CH=CH2 H Cl Cl
4.171 2-F, 4-F 3-CF3 C≡CH H Cl Cl
4.172 2-F, 4-F 3-CF3 Cl H Cl Cl
4.173 2-F, 4-F 3-CF3 Br H Cl Cl
4.174 2-F, 4-F 3-CF3 I H Cl Cl
4.175 2-F, 4-F 3-CF3 CN H Cl Cl
4.176 2-F, 4-F 3-CF3 NO2 H Cl Cl Comp.
Ri R2 Rs Rs R7 R8 Phys. data No.
4.177 2-F, 4-F 3-CF3 COCH3 H Cl Cl
4.178 2-F, 4-F 3-CF3 COOCH3 H Cl Cl
4.179 2-F, 4-F 3-CF3 Br F Cl Cl
4.180 2-F, 4-F 3-CF3 CN F Cl Cl
4.181 2-F, 4-F 3-CF3 C≡CH F Cl Cl
4.182 H 4-CF3 H H Cl Cl
4.183 3-CI 4-CF3 H H Cl Cl
4.184 4-CI 4-CF3 H H Cl Cl
4.185 3-CF3 4-CF3 H H Cl Cl
4.186 4-CF3 4-CF3 H H Cl Cl
4.187 H 3-CF2CF3 H H Cl Cl
4.188 2-F 3-CF2CF3 H H Cl Cl
4.189 2-CH3 3-CF2CF3 H H Cl Cl
4.190 3-F 3-CF2CF3 H H Cl Cl
4.191 3-CF3 3-CF2CF3 H H Cl Cl
4.192 4-F 3-CF2CF3 H H Cl H
4.193 4-F 3-CF2CF3 H H H Cl
4.194 4-F 3-CF2CF3 H H F F
4.195 4-F 3-CF2CF3 H H Cl Cl
4.196 4-F 3-CF2CF3 H H Br Br
4.197 4-CI 3-CF2CF3 H H Cl Cl
4.198 4-CF3 3-CF2CF3 H H Cl Cl
4.199 4-OCF3 3-CF2CF3 H H Cl Cl
4.200 4-SCF3 3-CF2CF3 H H Cl Cl
4.201 4-S02CF3 3-CF2CF3 H H Cl Cl
4.202 4-CN 3-CF2CF3 H H Cl Cl
4.203 4-SF5 3-CF2CF3 H H Cl Cl
4.204 4-F, 3-F 3-CF2CF3 H H Cl Cl
4.205 4-F, 3-F 3-CF2CF3 H H Br Br
4.206 4-F, 3-CF3 3-CF2CF3 H H Cl Cl
4.207 2-F, 4-CF3 3-CF2CF3 H H Cl Cl
4.208 3-F, 5-F 3-CF2CF3 H H Cl Cl
4.209 3-CF3, 5-CF3 3-CF2CF3 H H Cl Cl
4.210 2-F, 4-F 3-CF2CF3 H H Cl H Comp. i R2 R3 Rs R7 R8 Phys. data No.
4.211 2-F, 4-F 3-CF2CF3 H H H Cl
4.212 2-F, 4-F 3-CF2CF3 H H F F
4.213 2-F, 4-F 3-CF2CF3 H H Cl Cl
4.214 2-F, 4-F 3-CF2CF3 H H Br Br
4.215 2-F, 6-F 3-CF2CF3 H H Cl Cl
4.216 2-F, 4-F, 6-F 3-CF2CF3 H H Cl Cl
4.217 H 3-CHF2 H H Cl Cl
4.218 2-F 3-CHF2 H H Cl Cl
4.219 2-CH3 3-CHF2 H H Cl Cl
4.220 3-F 3-CHF2 H H Cl Cl
4.221 3-CF3 3-CHF2 H H Cl Cl
4.222 4-F 3-CHF2 H H F F
4.223 4-F 3-CHF2 H H Cl Cl
4.224 4-F 3-CHF2 H H Br Br
4.225 4-CI 3-CHF2 H H Cl Cl
4.226 4-CF3 3-CHF2 H H Cl Cl
4.227 4-OCF3 3-CHF2 H H Cl Cl
4.228 4-SCF3 3-CHF2 H H Cl Cl
4.229 4-S02CF3 3-CHF2 H H Cl Cl
4.230 4-CN 3-CHF2 H H Cl Cl
4.231 4-SF5 3-CHF2 H H Cl Cl
4.232 4-F, 3-F 3-CHF2 H H Cl Cl
4.233 4-F, 3-CF3 3-CHF2 H H Cl Cl
4.234 2-F, 4-CF3 3-CHF2 H H Cl Cl
4.235 3-F, 5-F 3-CHF2 H H Cl Cl
4.236 3-CF3, 5-CF3 3-CHF2 H H Cl Cl
4.237 2-F, 4-F 3-CHF2 H H Cl H
4.238 2-F, 4-F 3-CHF2 H H H Cl
4.239 2-F, 4-F 3-CHF2 H H F F
4.240 2-F, 4-F 3-CHF2 H H Cl Cl
4.241 2-F, 4-F 3-CHF2 H H Br Cl
4.242 2-F, 4-F 3-CHF2 H H Cl Br
4.243 2-F, 4-F 3-CHF2 H H Br Br
4.244 2-F, 6-F 3-CHF2 H H Cl Cl Comp.
Ri R2 R3 Rs R7 R8 Phys. data No.
4.245 2-F, 4-F, 6-F 3-CHF2 H H Cl Cl
4.246 H 3-OCF3 H H H H
4.247 H 3-OCF3 H H F F
4.248 H 3-OCF3 H H Cl Cl M.p. 81-82°C
4.249 H 3-OCF3 H H Br Br
4.250 2-F 3-OCF3 H H F F
4.251 2-F 3-OCF3 H H Cl Cl oil
4.252 2-F 3-OCF3 H H Br Br
4.253 2-CH3 3-OCF3 H H F F
4.254 2-CH3 3-OCF3 H H Cl Cl oil
4.255 2-CH3 3-OCF3 H H Br Br
4.256 3-F 3-OCF3 H H Cl Cl
4.257 3-CF3 3-OCF3 H H Cl Cl
4.258 3-OCF3 3-OCF3 H H Cl Cl
4.259 4-F 3-OCF3 H H H H
4.260 4-F 3-OCF3 H H Cl H
4.261 4-F 3-OCF3 H H H Cl
4.262 4-F 3-OCF3 H H Br H
4.263 4-F 3-OCF3 H H H Br
4.264 4-F 3-OCF3 H H F F
4.265 4-F 3-OCF3 H H Cl F
4.266 4-F 3-OCF3 H H F Cl
4.267 4-F 3-OCF3 H H Cl Cl
4.268 4-F 3-OCF3 H H Br Cl
4.269 4-F 3-OCF3 H H Cl Br
4.270 4-F 3-OCF3 H H CH3 Cl
4.271 4-F 3-OCF3 H H Cl CH3
4.272 4-F 3-OCF3 H H CF3 Cl
4.273 4-F 3-OCF3 H H Cl CF3
4.274 4-F 3-OCF3 H H Br Br
4.275 4-F 3-OCF3 H H CF3 CF3
4.276 4-CI 3-OCF3 H H F F
4.277 4-CI 3-OCF3 H H Cl Cl
4.278 4-CI 3-OCF3 H H Br Br Comp.
Ri R2 R3 R5 Rr Rs Phys. data No.
4.279 4-Br 3-OCF3 H H Cl Cl
4.280 4-CF3 3-OCF3 H H F F
4.281 4-CF3 3-OCF3 H H Cl Cl
4.282 4-CF3 3-OCF3 H H Br Br
4.283 4-OCF3 3-OCF3 H H Cl Cl
4.284 4-SCF3 3-OCF3 H H Cl Cl
4.285 4-S02CF3 3-OCF3 H H F F
4.286 4-S02CF3 3-OCF3 H H Cl Cl
4.287 4-S02CF3 3-OCF3 H H Br Br
4.288 4-S02CH3 3-OCF3 H H Cl Cl
4.289 4-CN 3-OCF3 H H Cl Cl
4.290 4-NO2 3-OCF3 H H Cl Cl
4.291 4-SF5 3-OCF3 H H Cl Cl
4.292 4-F, 3-F 3-OCF3 H H F F
4.293 4-F, 3-F 3-OCF3 H H Cl Cl
4.294 4-F, 3-F 3-OCF3 H H Br Br
4.295 4-F, 3-CI 3-OCF3 H H Cl Cl
4.296 4-F, 3-CN 3-OCF3 H H Cl Cl
4.297 4-F, 3-CF3 3-OCF3 H H Cl Cl
4.298 2-F, 4-CF3 3-OCF3 H H Cl Cl
4.299 2-CF3, 4-CF3 3-OCF3 H H Cl Cl
4.300 3-F, 5-F 3-OCF3 H H Cl Cl
4.301 3-CF3, 5-CF3 3-OCF3 H H F F
4.302 3-CF3, 5-CF3 3-OCF3 H H Cl Cl
4.303 2-F, 4-F 3-OCF3 H H H H
4.304 2-F, 4-F 3-OCF3 H H Cl H
4.305 2-F, 4-F 3-OCF3 H H H Cl
4.306 2-F, 4-F 3-OCF3 H H Br H
4.307 2-F, 4-F 3-OCF3 H H H Br
4.308 2-F, 4-F 3-OCF3 H H F F
4.309 2-F, 4-F 3-OCF3 H H Cl F
4.310 2-F, 4-F 3-OCF3 H H F Cl
4.311 2-F, 4-F 3-OCF3 H H Cl Cl oil
4.312 2-F, 4-F 3-OCF3 H H Br Cl Comp.
Ri R2 R3 Rs R7 R8 Phys. data No.
4.313 2-F, 4-F 3-OCF3 H H Cl Br
4.314 2-F, 4-F 3-OCF3 H H CH3 Cl
4.315 2-F, 4-F 3-OCF3 H H Cl CH3
4.316 2-F, 4-F 3-OCF3 H H CF3 Cl
4.317 2-F, 4-F 3-OCF3 H H Cl CF3
4.318 2-F, 4-F 3-OCF3 H H Br Br
4.319 2-F, 4-F 3-OCF3 H H CF3 CF3
4.320 2-F, 6-F 3-OCF3 H H F F
4.321 2-F, 6-F 3-OCF3 H H Cl Cl
4.322 2-F, 6-F 3-OCF3 H H Br Br
4.323 2-F, 4-F, 6-F 3-OCF3 H H Cl Cl
4.324 H 3-OCF3 H Cl Cl Cl
4.325 2-F 3-OCF3 H Cl Cl Cl
4.326 4-F 3-OCF3 H F Cl Cl
4.327 4-F 3-OCF3 H Cl Cl Cl
4.328 2-F, 4-F 3-OCF3 H F Cl Cl
4.329 2-F, 4-F 3-OCF3 H F Cl H
4.330 2-F, 4-F 3-OCF3 H F H Cl
4.331 2-F, 4-F 3-OCF3 H Cl Cl Cl
4.332 2-F, 4-F 3-OCF3 H Cl Cl H
4.333 2-F, 4-F 3-OCF3 H Cl H Cl
4.334 2-F, 4-F 3-OCF3 H CH3 Cl Cl
4.335 H 3-OCF3 Cl H Cl Cl
4.336 H 3-OCF3 Br H Cl Cl
4.337 4-F 3-OCF3 Br H Cl Cl
4.338 4-F 3-OCF3 CN H Cl Cl
4.339 2-F, 4-F 3-OCF3 CH3 H Cl Cl
4.340 2-F, 4-F 3-OCF3 CH=CH2 H Cl Cl
4.341 2-F, 4-F 3-OCF3 C≡CH H Cl Cl
4.342 2-F, 4-F 3-OCF3 Cl H Cl Cl
4.343 2-F, 4-F 3-OCF3 Br H Cl Cl
4.344 2-F, 4-F 3-OCF3 CN H Cl Cl
4.345 2-F, 4-F 3-OCF3 NO2 H Cl Cl
4.346 2-F, 4-F 3-OCF3 COCH3 H Cl Cl Comp.
Ri R2 R3 Rs R7 R8 Phys. data No.
4.347 2-F, 4-F 3-OCF3 COOCH3 H Cl Cl
4.348 2-F, 4-F 3-OCF3 Br F Cl Cl
4.349 2-F, 4-F 3-OCF3 CN F Cl Cl
4.350 2-F, 4-F 3-OCF3 C≡CH F Cl Cl
4.351 H 3-OCHF2 H H F F
4.352 H 3-OCHF2 H H Cl Cl
4.353 H 3-OCHF2 H H Br Br
4.354 2-F 3-OCHF2 H H Cl Cl
4.355 2-CH3 3-OCHF2 H H Cl Cl
4.356 3-F 3-OCHF2 H H Cl Cl
4.357 3-CF3 3-OCHF2 H H Cl Cl
4.358 4-F 3-OCHF2 H H F F
4.359 4-F 3-OCHF2 H H Cl Cl
4.360 4-F 3-OCHF2 H H Br Br
4.361 4-CI 3-OCHF2 H H Cl Cl
4.362 4-CF3 3-OCHF2 H H Cl Cl
4.363 4-OCF3 3-OCHF2 H H Cl Cl
4.364 4-SCF3 3-OCHF2 H H Cl Cl
4.365 4-S02CF3 3-OCHF2 H H Cl Cl
4.366 4-CN 3-OCHF2 H H Cl Cl
4.367 4-SF5 3-OCHF2 H H Cl Cl
4.368 4-F, 3-F 3-OCHF2 H H Cl Cl
4.369 4-F, 3-CF3 3-OCHF2 H H Cl Cl
4.370 2-F, 4-CF3 3-OCHF2 H H Cl Cl
4.371 3-F, 5-F 3-OCHF2 H H Cl Cl
4.372 3-CF3, 5-CF3 3-OCHF2 H H Cl Cl
4.373 2-F, 4-F 3-OCHF2 H H Cl H
4.374 2-F, 4-F 3-OCHF2 H H H Cl
4.375 2-F, 4-F 3-OCHF2 H H F F
4.376 2-F, 4-F 3-OCHF2 H H Cl Cl
4.377 2-F, 4-F 3-OCHF2 H H Br Cl
4.378 2-F, 4-F 3-OCHF2 H H Cl Br
4.379 2-F, 4-F 3-OCHF2 H H Br Br
4.380 2-F, 6-F 3-OCHF2 H H Cl Cl Comp. i R2 R3 Rs R7 Rs Phys. data No.
4.381 2-F, 4-F, 6-F 3-OCHF2 H H Cl Cl
4.382 H 3-OCF2CF3 H H F F
4.383 H 3-OCF2CF3 H H Cl Cl
4.384 H 3-OCF2CF3 H H Br Br
4.385 2-F 3-OCF2CF3 H H Cl Cl
4.386 2-CH3 3-OCF2CF3 H H Cl Cl
4.387 3-F 3-OCF2CF3 H H Cl Cl
4.388 3-CF3 3-OCF2CF3 H H Cl Cl
4.389 4-F 3-OCF2CF3 H H F F
4.390 4-F 3-OCF2CF3 H H Cl Cl
4.391 4-F 3-OCF2CF3 H H Br Br
4.392 4-CI 3-OCF2CF3 H H Cl Cl
4.393 4-CF3 3-OCF2CF3 H H Cl Cl
4.394 4-OCF3 3-OCF2CF3 H H Cl Cl
4.395 4-SCF3 3-OCF2CF3 H H Cl Cl
4.396 4-S02CF3 3-OCF2CF3 H H Cl Cl
4.397 4-CN 3-OCF2CF3 H H Cl Cl
4.398 4-SF5 3-OCF2CF3 H H Cl Cl
4.399 4-F, 3-F 3-OCF2CF3 H H Cl Cl
4.400 4-F, 3-CF3 3-OCF2CF3 H H Cl Cl
4.401 2-F, 4-CF3 3-OCF2CF3 H H Cl Cl
4.402 3-F, 5-F 3-OCF2CF3 H H Cl Cl
4.403 3-CF3, 5-CF3 3-OCF2CF3 H H Cl Cl
4.404 2-F, 4-F 3-OCF2CF3 H H Cl H
4.405 2-F, 4-F 3-OCF2CF3 H H H Cl
4.406 2-F, 4-F 3-OCF2CF3 H H F F
4.407 2-F, 4-F 3-OCF2CF3 H H Cl Cl
4.408 2-F, 4-F 3-OCF2CF3 H H Br Cl
4.409 2-F, 4-F 3-OCF2CF3 H H Cl Br
4.410 2-F, 4-F 3-OCF2CF3 H H Br Br
4.411 2-F, 6-F 3-OCF2CF3 H H Cl Cl
4.412 2-F, 4-F, 6-F 3-OCF2CF3 H H Cl Cl
4.413 H 3-OCF2CHF2 H H F F
4.414 H 3-OCF2CHF2 H H Cl Cl Comp.
Ri R2 R3 Rs R Rs Phys. data No.
4.415 H 3-OCF2CHF2 H H Br Br
4.416 2-F 3-OCF2CHF2 H H Cl Cl
4.417 2-CH3 3-OCF2CHF2 H H Cl Cl
4.418 3-F 3-OCF2CHF2 H H Cl Cl
4.419 3-CF3 3-OCF2CHF2 H H Cl Cl
4.420 4-F 3-OCF2CHF2 H H F F
4.421 4-F 3-OCF2CHF2 H H Cl Cl
4.422 4-F 3-OCF2CHF2 H H Br Br
4.423 4-CI 3-OCF2CHF2 H H Cl Cl
4.424 4-CF3 3-OCF2CHF2 H H Cl Cl
4.425 4-OCF3 3-OCF2CHF2 H H Cl Cl
4.426 4-SCF3 3-OCF2CHF2 H H Cl Cl
4.427 4-SO2CF3 3-OCF2CHF2 H H Cl Cl
4.428 4-CN 3-OCF2CHF2 H H Cl Cl
4.429 4-SF5 3-OCF2CHF2 H H Cl Cl
4.430 4-F, 3-F 3-OCF2CHF2 H H Cl Cl
4.431 4-F, 3-CF3 3-OCF2CHF2 H H Cl Cl
4.432 2-F, 4-CF3 3-OCF2CHF2 H H Cl Cl
4.433 3-F, 5-F 3-OCF2CHF2 H H Cl Cl
4.434 3-CF3, 5-CF3 3-OCF2CHF2 H H Cl Cl
4.435 2-F, 4-F 3-OCF2CHF2 H H Cl H
4.436 2-F, 4-F 3-OCF2CHF2 H H H Cl
4.437 2-F, 4-F 3-OCF2CHF2 H H F F
4.438 2-F, 4-F 3-OCF2CHF2 H H Cl Cl
4.439 2-F, 4-F 3-OCF2CHF2 H H Br Cl
4.440 2-F, 4-F 3-OCF2CHF2 H H Cl Br
4.441 2-F, 4-F 3-OCF2CHF2 H H Br Br
4.442 2-F, 6-F 3-OCF2CHF2 H H Cl Cl
4.443 2-F, 4-F, 6-F 3-OCF2CHF2 H H Cl Cl
4.444 H 3-OCH2CF3 H H Cl Cl
4.445 2-F 3-OCH2CF3 H H Cl Cl
4.446 2-CH3 3-OCH2CF3 H H Cl Cl
4.447 4-F 3-OCH2CF3 H H F F
4.448 4-F 3-OCH2CF3 H H Cl Cl Comp.
Ri R2 R3 Rs R7 Rs Phys. data No.
4.449 4-F 3-OCH2CF3 H H Br Br
4.450 4-CI 3-OCH2CF3 H H Cl Cl
4.451 4-CF3 3-OCH2CF3 H H Cl Cl
4.452 2-F, 4-F 3-OCH2CF3 H H F F
4.453 2-F, 4-F 3-OCH2CF3 H H Cl Cl
4.454 2-F, 4-F 3-OCH2CF3 H H Br Br
4.455 H 3-SCF3 H H F F
4.456 H 3-SCF3 H H Cl Cl
4.457 H 3-SCF3 H H Br Br
4.458 2-F 3-SCF3 H H Cl Cl
4.459 2-CH3 3-SCF3 H H Cl Cl
4.460 3-F 3-SCF3 H H Cl Cl
4.461 3-CF3 3-SCF3 H H Cl Cl
4.462 4-F 3-SCF3 H H Cl H
4.463 4-F 3-SCF3 H H H Cl
4.464 4-F 3-SCF3 H H F F
4.465 4-F 3-SCF3 H H Cl Cl
4.466 4-F 3-SCF3 H H Br Br
4.467 4-CI 3-SCF3 H H Cl Cl
4.468 4-Br 3-SCF3 H H Cl Cl
4.469 4-CF3 3-SCF3 H H Cl Cl
4.470 4-OCF3 3-SCF3 H H Cl Cl
4.471 4-SCF3 3-SCF3 H H Cl Cl
4.472 4-S02CF3 3-SCF3 H H Cl Cl
4.473 4-SO2CH3 3-SCF3 H H Cl Cl
4.474 4-CN 3-SCF3 H H Cl Cl
4.475 4-N02 3-SCF3 H H Cl Cl
4.476 4-SF5 3-SCF3 H H Cl Cl
4.477 4-F, 3-F 3-SCF3 H H Cl Cl
4.478 4-F, 3-CI 3-SCF3 H H Cl Cl
4.479 4-F, 3-CN 3-SCF3 H H Cl Cl
4.480 4-F, 3-CF3 3-SCF3 H H Cl Cl
4.481 2-F, 4-CF3 3-SCF3 H H Cl Cl
4.482 2-CF3, 4-CF3 3-SCF3 H H Cl Cl Comp.
Ri R2 Ra Rs R7 Rs Phys. data No.
4.483 3-F, 5-F 3-SCF3 H H Cl Cl
4.484 3-CF3, 5-CF3 3-SCF3 H H Cl Cl
4.485 2-F, 4-F 3-SCF3 H H Cl H
4.486 2-F, 4-F 3-SCF3 H H H Cl
4.487 2-F, 4-F 3-SCF3 H H F F
4.488 2-F, 4-F 3-SCF3 H H Cl Cl
4.489 2-F, 4-F 3-SCF3 H H Br Br
4.490 2-F, 6-F 3-SCF3 H H Cl Cl
4.491 2-F, 4-F, 6-F 3-SCF3 H H Cl Cl
4.492 H 3-SCF3 H Cl Cl Cl
4.493 4-F 3-SCF3 H F Cl Cl
4.494 2-F, 4-F 3-SCF3 H F Cl Cl
4.495 2-F, 4-F 3-SCF3 H Cl Cl Cl
4.496 2-F, 4-F 3-SCF3 H CH3 Cl Cl
4.497 4-F 3-SCF3 Br H Cl Cl
4.498 2-F, 4-F 3-SCF3 C≡CH H Cl Cl
4.499 2-F, 4-F 3-SCF3 Br H Cl Cl
4.500 2-F, 4-F 3-SCF3 COCH3 H Cl Cl
4.501 2-F, 4-F 3-SCF3 Br F Cl Cl
4.502 H 3-SCHF2 H H Cl Cl
4.503 2-F 3-SCHF2 H H Cl Cl
4.504 2-CH3 3-SCHF2 H H Cl Cl
4.505 3-F 3-SCHF2 H H Cl Cl
4.506 3-CF3 3-SCHF2 H H Cl Cl
4.507 4-F 3-SCHF2 H H F F
4.508 4-F 3-SCHF2 H H Cl Cl
4.509 4-F 3-SCHF2 H H Br Br
4.510 4-CI 3-SCHF2 H H Cl Cl
4.511 4-CF3 3-SCHF2 H H Cl Cl
4.512 4-OCF3 3-SCHF2 H H Cl Cl
4.513 4-SCF3 3-SCHF2 H H Cl Cl
4.514 4-SO2CF3 3-SCHF2 H H Cl Cl
4.515 4-CN 3-SCHF2 H H Cl Cl
4.516 4-SF5 3-SCHF2 H H Cl Cl Comp.
Ri R2 R3 Rs R7 Rs Phys. data No.
4.517 4-F, 3-F 3-SCHF2 H H Cl Cl
4.518 4-F, 3-CF3 3-SCHF2 H H Cl Cl
4.519 2-F, 4-CF3 3-SCHF2 H H Cl Cl
4.520 3-F, 5-F 3-SCHF2 H H Cl Cl
4.521 3-CF3, 5-CF3 3-SCHF2 H H Cl Cl
4.522 2-F, 4-F 3-SCHF2 H H F F
4.523 2-F, 4-F 3-SCHF2 H H Cl Cl
4.524 2-F, 4-F 3-SCHF2 H H Br Br
4.525 2-F, 6-F 3-SCHF2 H H Cl Cl
4.526 2-F, 4-F, 6-F 3-SCHF2 H H Cl Cl
4.527 H 3-SOCF3 H H Cl Cl
4.528 2-F 3-SOCF3 H H Cl Cl
4.529 2-CH3 3-SOCF3 H H Cl Cl
4.530 3-F 3-SOCF3 H H Cl Cl
4.531 3-CF3 3-SOCF3 H H Cl Cl
4.532 4-F 3-SOCF3 H H F F
4.533 4-F 3-SOCF3 H H Cl Cl
4.534 4-F 3-SOCF3 H H Br Br
4.535 4-CI 3-SOCF3 H H Cl Cl
4.536 4-CF3 3-SOCF3 H H Cl Cl
4.537 4-OCF3 3-SOCF3 H H Cl Cl
4.538 4-SCF3 3-SOCF3 H H Cl Cl
4.539 4-S02CF3 3-SOCF3 H H Cl Cl
4.540 4-CN 3-SOCF3 H H Cl Cl
4.541 4-SF5 3-SOCF3 H H Cl Cl
4.542 4-F, 3-F 3-SOCF3 H H Cl Cl
4.543 4-F, 3-CF3 3-SOCF3 H H Cl Cl
4.544 2-F, 4-CF3 3-SOCF3 H H Cl Cl
4.545 3-F, 5-F 3-SOCF3 H H Cl Cl
4.546 3-CF3, 5-CF3 3-SOCF3 H H Cl Cl
4.547 2-F, 4-F 3-SOCF3 H H Cl H
4.548 2-F, 4-F 3-SOCF3 H H H Cl
4.549 2-F, 4-F 3-SOCF3 H H F F
4.550 2-F, 4-F 3-SOCF3 H H Cl Cl Comp.
Ri R2 R3 Rs R R8 Phys. data No.
4.551 2-F, 4-F 3-SOCF3 H H Br Cl
4.552 2-F, 4-F 3-SOCF3 H H Cl Br
4.553 2-F, 4-F 3-SOCF3 H H Br Br
4.554 2-F, 6-F 3-SOCF3 H H Cl Cl
4.555 2-F, 4-F, 6-F 3-SOCF3 H H Cl Cl
4.556 H 3-S02CF3 H H Cl Cl
4.557 2-F 3-S02CF3 H H Cl Cl
4.558 2-CH3 3-S02CF3 H H Cl Cl
4.559 3-F 3-S02CF3 H H Cl Cl
4.560 3-CF3 3-S02CF3 H H Cl Cl
4.561 4-F 3-S02CF3 H H F F
4.562 4-F 3-S02CF3 H H Cl Cl
4.563 4-F 3-S02CF3 H H Br Br
4.564 4-CI 3-S02CF3 H H Cl Cl
4.565 4-Br 3-S02CF3 H H Cl Cl
4.566 4-CF3 3-S02CF3 H H Cl Cl
4.567 4-OCF3 3-S02CF3 H H Cl Cl
4.568 4-SCF3 3-S02CF3 H H Cl Cl
4.569 4-S02CF3 3-S02CF3 H H Cl Cl
4.570 4-SO2CH3 3-S02CF3 H H Cl Cl
4.571 4-CN 3-S02CF3 H H Cl Cl
4.572 4-N02 3-S02CF3 H H Cl Cl
4.573 4-SF5 3-S02CF3 H H Cl Cl
4.574 4-F, 3-F 3-S02CF3 H H Cl Cl
4.575 4-F, 3-CI 3-S02CF3 H H Cl Cl
4.576 4-F, 3-CN 3-S02CF3 H H Cl Cl
4.577 4-F, 3-CF3 3-S02CF3 H H Cl Cl
4.578 2-F, 4-CF3 3-S02CF3 H H Cl Cl
4.579 2-CF3, 4-CF3 3-S02CF3 H H Cl Cl
4.580 3-F, 5-F 3-S02CF3 H H Cl Cl
4.581 3-CF3, 5-CF3 3-S02CF3 H H Cl Cl
4.582 2-F, 4-F 3-S02CF3 H H Cl H
4.583 2-F, 4-F 3-S02CF3 H H H Cl
4.584 2-F, 4-F 3-S02CF3 H H F F Comp.
Ri R2 R3 Rs R7 Rs Phys. data No.
4.585 2-F, 4-F 3-SO2CF3 H H Cl Cl
4.586 2-F, 4-F 3-SO2CF3 H H Br Cl
4.587 2-F, 4-F 3-S02CF3 H H Cl Br
4.588 2-F, 4-F 3-SO2CF3 H H Br Br
4.589 2-F, 6-F 3-S02CF3 H H Cl Cl
4.590 2-F, 4-F, 6-F 3-SO2CF3 H H Cl Cl
4.591 H 3-SO2CH3 H H Cl Cl
4.592 2-F 3-SO2CH3 H H Cl Cl
4.593 2-CH3 3-SO2CH3 H H Cl Cl
4.594 4-F 3-SO2CH3 H H Cl Cl
4.595 4-CI 3-SO2CH3 H H Cl Cl
4.596 4-CF3 3-SO2CH3 H H Cl Cl
4.597 2-F, 4-F 3-SO2CH3 H H F F
4.598 2-F, 4-F 3-SO2CH3 H H Cl Cl
4.599 2-F, 4-F 3-S02CH3 H H Br Br
4.600 H 3-SF5 H H Cl Cl
4.601 2-F 3-SF5 H H Cl Cl
4.602 2-CH3 3-SF5 H H Cl Cl
4.603 3-F 3-SF5 H H Cl Cl
4.604 4-F 3-SF5 H H Cl Cl
4.605 4-CI 3-SF5 H H Cl Cl
4.606 4-CF3 3-SF5 H H Cl Cl
4.607 4-OCF3 3-SF5 H H Cl Cl
4.608 4-SCF3 3-SF5 H H Cl Cl
4.609 4-S02CF3 3-SF5 H . H Cl Cl
4.610 4-CN 3-SF5 H H Cl Cl
4.611 4-SF5 3-SF5 H H Cl Cl
4.612 4-F, 3-F 3-SF5 H H Cl Cl
4.613 4-F, 3-CF3 3-SF5 H H Cl Cl
4.614 2-F, 4-CF3 3-SF5 H H Cl Cl
4.615 3-F, 5-F 3-SF5 H H Cl Cl
4.616 2-F, 4-F 3-SF5 H H F F
4.617 2-F, 4-F 3-SF5 H H Cl Cl
4.618 2-F, 4-F 3-SF5 H H Br Br Comp.
Ri R2 R3 Rs R7 Rs Phys. data No.
4.619 2-F, 6-F 3-SF5 H H Cl Cl
4.620 2-F, 4-F, 6-F 3-SF5 H H Cl Cl
4.621 H 3-OCF2CHFCF3 H H Cl Cl
4.622 2-F 3-OCF2CHFCF3 H H Cl Cl
4.623 2-F 3-OCF2CHFCF3 H H Br Br
4.624 2-CH3 3-OCF2CHFCF3 H H Cl Cl
4.625 4-F 3-OCF2CHFCF3 H H F F
4.626 4-F 3-OCF2CHFCF3 H H Cl Cl
4.627 4-F 3-OCF2CHFCF3 H H Br Br
4.628 4-CI 3-OCF2CHFCF3 H H Cl Cl
4.629 4-CF3 3-OCF2CHFCF3 H H Cl Cl
4.630 2-F, 4-F 3-OCF2CHFCF3 H H F F
4.631 2-F, 4-F 3-OCF2CHFCF3 H H Cl F
4.632 2-F, 4-F 3-OCF2CHFCF3 H H F Cl
4.633 2-F, 4-F 3-OCF2CHFCF3 H H Cl Cl
4.634 2-F, 4-F 3-OCF2CHFCF3 H H Br Br
4.635 H 3-CH2CH3 H H Cl Cl
4.636 2-F 3-CH2CH3 H H Cl Cl
4.637 2-CH3 3-CH2CH3 H H Cl Cl
4.638 4-F 3-CH2CH3 H H Cl Cl
4.639 4-CI 3-CH2CH3 H H Cl Cl
4.640 4-CF3 3-CH2CH3 H H Cl Cl
4.641 2-F, 4-F 3-CH2CH3 H H F F
4.642 2-F, 4-F 3-CH2CH3 H H Cl Cl
4.643 2-F, 4-F 3-CH2CH3 H H Br Br
4.644 H 3-CH(CH3)2 H H Cl Cl
4.645 2-F 3-CH(CH3)2 H H Cl Cl
4.646 2-CH3 3-CH(CH3)2 H H Cl Cl
4.647 4-F 3-CH(CH3)2 H H Cl Cl
4.648 4-CI 3-CH(CH3)2 H H Cl Cl
4.649 4-CF3 3-CH(CH3)2 H H Cl Cl
4.650 2-F, 4-F 3-CH(CH3)2 H H F F
4.651 2-F, 4-F 3-CH(CH3)2 H H Cl Cl
4.652 2-F, 4-F 3-CH(CH3)2 H H Br Br Comp.
Ri R2 R3 Rs R7 Rs Phys. data No.
4.653 H 3-C(CH3)3 H H Cl Cl
4.654 2-F 3-C(CH3)3 H H Cl Cl
4.655 2-CH3 3-C(CH3)3 H H Cl Cl
4.656 4-F 3-C(CH3)3 H H Cl Cl
4.657 4-CI 3-C(CH3)3 H H Cl Cl
4.658 4-CF3 3-C(CH3)3 H H Cl Cl
4.659 2-F, 4-F 3-C(CH3)3 H H F F
4.660 2-F, 4-F 3-C(CH3)3 H H Cl Cl
4.661 2-F, 4-F 3-C(CH3)3 H H Br Br
4.662 H 3-NO2 H H Cl Cl
4.663 2-F 3-N02 H H Cl Cl
4.664 2-CH3 3-NO2 H H Cl Cl
4.665 4-F 3-N02 H H Cl Cl
4.666 4-CI 3-NO2 H H Cl Cl
4.667 4-CF3 3-N02 H H Cl Cl
4.668 2-F, 4-F 3-NO2 H H F F
4.669 2-F, 4-F 3-N02 H H Cl Cl
4.670 2-F, 4-F 3-N02 H H Br Br
4.671 H 3-CN H H Cl Cl
4.672 2-F 3-CN H H Cl Cl
4.673 2-CH3 3-CN H H Cl Cl
4.674 3-F 3-CN H H Cl Cl
4.675 4-F 3-CN H H Cl Cl
4.676 4-CI 3-CN H H Cl Cl
4.677 4-CF3 3-CN H H Cl Cl
4.678 4-OCF3 3-CN H H Cl Cl
4.679 4-SCF3 3-CN H H Cl Cl
4.680 4-S02CF3 3-CN H H Cl Cl
4.681 4-CN 3-CN H H Cl Cl
4.682 4-SF5 3-CN H H Cl Cl
4.683 4-F, 3-F 3-CN H H Cl Cl
4.684 4-F, 3-CF3 3-CN H H Cl Cl
4.685 2-F, 4-CF3 3-CN H H Cl Cl
4.686 3-F, 5-F 3-CN H H Cl Cl Comp.
Ri R2 R3 Rs R7 R8 Phys. data No.
4.687 2-F, 4-F 3-CN H H F F
4.688 2-F, 4-F 3-CN H H Cl Cl
4.689 2-F, 4-F 3-CN H H Br Br
4.690 2-F, 6-F 3-CN H H Cl Cl
4.691 2-F, 4-F, 6-F 3-CN H H Cl Cl
4.692 H 3-CF3, 2-F H H Cl Cl
4.693 2-F 3-CF3, 2-F H H Cl Cl
4.694 2-CH3 3-CF3, 2-F H H Cl Cl
4.695 4-F 3-CF3, 2-F H H Cl Cl
4.696 4-CI 3-CF3, 2-F H H Cl Cl
4.697 4-CF3 3-CF3, 2-F H H Cl Cl
4.698 2-F, 4-F 3-CF3, 2-F H H F F
4.699 2-F, 4-F 3-CF3, 2-F H H Cl Cl
4.700 2-F, 4-F 3-CF3, 2-F H H Br Br
4.701 H 3-CF3, 4-F H H Cl Cl M.p. 82-83°C
4.702 2-F 3-CF3, 4-F H H Cl Cl
4.703 2-CH3 3-CF3, 4-F H H Cl Cl
4.704 3-F 3-CF3, 4-F H H Cl Cl
4.705 3-CF3 3-CF3, 4-F H H Cl Cl
4.706 4-F 3-CF3, 4-F H H Cl Cl
4.707 4-F 3-CF3, 4-F H H Br Br
4.708 4-CI 3-CF3, 4-F H H Cl Cl
4.709 4-CF3 3-CF3, 4-F H H Cl Cl
4.710 4-OCF3 3-CF3, 4-F H H Cl Cl
4.711 4-SCF3 3-CF3, 4-F H H Cl Cl
4.712 4-S02CF3 3-CF3, 4-F H H Cl Cl
4.713 4-CN 3-CF3, 4-F H H Cl Cl
4.714 4-SF5 3-CF3, 4-F H H Cl Cl
4.715 4-F, 3-F 3-CF3, 4-F H H Cl Cl
4.716 4-F, 3-CF3 3-CF3, 4-F H H Cl Cl
4.717 2-F, 4-CF3 3-CF3, 4-F H H Cl Cl
4.718 3-F, 5-F 3-CF3, 4-F H H Cl Cl
4.719 3-CF3, 5-CF3 3-CF3, 4-F H H Cl Cl
4.720 2-F, 4-F 3-CF3, 4-F H H Cl Cl M.p. 91-92°C Comp.
Ri R2 R3 Rs R7 Rs Phys. data No.
4.721 2-F, 4-F 3-CF3, 4-F H H Br Cl
4.722 2-F, 4-F 3-CF3, 4-F H H Cl Br
4.723 2-F, 4-F 3-CF3, 4-F H H Br Br
4.724 2-F, 6-F 3-CF3, 4-F H H Cl Cl
4.725 2-F, 4-F, 6-F 3-CF3, 4-F H H Cl Cl
4.726 H 3-CF3, 4-F H Cl Cl Cl
4.727 4-F 3-CF3, 4-F H F Cl Cl
4.728 2-F, 4-F 3-CF3, 4-F H F Cl Cl
4.729 2-F, 4-F 3-CF3, 4-F H Cl Cl Cl
4.730 2-F, 4-F 3-CF3, 4-F H CH3 Cl Cl
4.731 4-F 3-CF3, 4-F Br H Cl Cl
4.732 2-F, 4-F 3-CF3, 4-F C≡CH H Cl Cl
4.733 2-F, 4-F 3-CF3, 4-F Br H Cl Cl
4.734 2-F, 4-F 3-CF3, 4-F COCH3 H Cl Cl
4.735 2-F, 4-F 3-CF3, 4-F Br F Cl Cl
4.736 H 3-CF3, 6-CI H H Cl Cl
4.737 3-CI 3-CF3, 6-CI H H Cl Cl
4.738 4-CI 3-CF3, 6-CI H H Cl Cl
4.739 4-CI 3-CF3, 6-CI H H CF3 Cl
4.740 3-CF3 3-CF3, 6-CI H H Cl Cl
4.741 4-CF3 3-CF3, 6-CI H H Cl Cl
4.742 H 3-OCF3, 4-F H H Cl Cl
4.743 2-F 3-OCF3, 4-F H H Cl Cl
4.744 2-CH3 3-OCF3, 4-F H H Cl Cl
4.745 3-F 3-OCF3, 4-F H H Cl Cl
4.746 3-CF3 3-OCF3, 4-F H H Cl Cl
4.747 4-F 3-OCF3, 4-F H H Cl Cl
4.748 4-F 3-OCF3, 4-F H H Br Br
4.749 4-CI 3-OCF3, 4-F H H Cl Cl
4.750 4-CF3 3-OCF3, 4-F H H Cl Cl
4.751 4-OCF3 3-OCF3, 4-F H H Cl Cl
4.752 4-SCF3 3-OCF3, 4-F H H Cl Cl
4.753 4-S02CF3 3-OCF3, 4-F H H Cl Cl
4.754 4-CN 3-OCF3, 4-F H H Cl Cl Comp. i R2 R3 Rs R7 Rs Phys. data No.
4.755 4-SF5 3-OCF3, 4-F H H Cl Cl
4.756 4-F, 3-F 3-OCF3, 4-F H H Cl Cl
4.757 4-F, 3-CF3 3-OCF3, 4-F H H Cl Cl
4.758 2-F, 4-CF3 3-OCF3, 4-F H H Cl Cl
4.759 3-F, 5-F 3-OCF3, 4-F H H Cl Cl
4.760 3-CF3, 5-CF3 3-OCF3, 4-F H H Cl Cl
4.761 2-F, 4-F 3-OCF3, 4-F H H Cl Cl
4.762 2-F, 4-F 3-OCF3, 4-F H H Br Cl
4.763 2-F, 4-F 3-OCF3, 4-F H H Cl Br
4.764 2-F, 4-F 3-OCF3, 4-F H H Br Br
4.765 2-F, 6-F 3-OCF3, 4-F H H Cl Cl
4.766 2-F, 4-F, 6-F 3-OCF3, 4-F H H Cl Cl
4.767 H 3-CI, 4-F H H Cl Cl
4.768 2-F 3-CI, 4-F H H Cl Cl
4.769 2-CH3 3-CI, 4-F H H Cl Cl
4.770 3-F 3-CI, 4-F H H Cl Cl
4.771 3-CF3 3-CI, 4-F H H Cl Cl
4.772 4-F 3-CI, 4-F H H Cl Cl
4.773 4-F 3-CI, 4-F H H Br Br
4.774 4-CI 3-CI, 4-F H H Cl Cl
4.775 4-CF3 3-CI, 4-F H H Cl Cl
4.776 4-OCF3 3-CI, 4-F H H Cl Cl
4.111 4-SCF3 3-CI, 4-F H H Cl Cl
4.718 4-S02CF3 3-CI, 4-F H H Cl Cl
4.119 4-CN 3-CI, 4-F H H Cl Cl
4.780 4-SF5 3-CI, 4-F H H Cl Cl
4.781 4-F, 3-F 3-CI, 4-F H H Cl Cl
4.782 4-F, 3-CF3 3-CI, 4-F H H Cl Cl
4.783 2-F, 4-CF3 3-CI, 4-F H H Cl Cl
4.784 3-F, 5-F 3-CI, 4-F H H Cl Cl
4.785 3-CF3, 5-CF3 3-CI, 4-F H H Cl Cl
4.786 2-F, 4-F 3-CI, 4-F H H Cl Cl
4.787 2-F, 4-F 3-CI, 4-F H H Br Cl
4.788 2-F, 4-F 3-CI, 4-F H H Cl Br Comp.
Ri R2 R3 Rs R7 Rs Phys. data No.
4.789 2-F, 4-F 3-CI, 4-F H H Br Br
4.790 2-F, 6-F 3-CI, 4-F H H Cl Cl
4.791 2-F, 4-F, 6-F 3-CI, 4-F H H Cl Cl
4.792 3-CF3 2-F, 4-F H H Cl Cl
4.793 H 2-CI, 4-CI H H Cl Cl
4.794 4-CI 2-CI, 4-CI H H Cl Cl
4.795 3-CF3 2-CI, 4-CI H H Cl Cl
4.796 4-CF3 2-CI, 4-CI H H Cl Cl
4.797 H 2-CI, 6-CI H H Cl Cl
4.798 4-CI 2-CI, 6-CI H H Cl Cl
4.799 3-CF3 2-CI, 6-CI H H Cl Cl
4.800 4-CF3 . 2-CI, 6-CI H H Cl Cl
4.801 H 3-F, 4-F H H Cl Cl
4.802 2-F 3-F, 4-F H H Cl Cl
4.803 2-CH3 3-F, 4-F H H Cl Cl
4.804 3-F 3-F, 4-F H H Cl Cl
4.805 3-CF3 3-F, 4-F H H Cl Cl
4.806 4-F 3-F, 4-F H H CI Cl
4.807 4-F 3-F, 4-F H H Br Br
4.808 4-CI 3-F, 4-F H H Cl Cl
4.809 4-CF3 3-F, 4-F H H Cl Cl
4.810 4-OCF3 3-F, 4-F H H Cl Cl
4.811 4-SCF3 3-F, 4-F H H Cl Cl
4.812 4-S02CF3 3-F, 4-F H H Cl Cl
4.813 4-CN 3-F, 4-F H H Cl Cl
4.814 4-SF5 3-F, 4-F H H Cl Cl
4.815 4-F, 3-F 3-F, 4-F H H Cl Cl
4.816 4-F, 3-CF3 3-F, 4-F H H Cl Cl
4.817 2-F, 4-CF3 3-F, 4-F H H Cl Cl
4.818 3-F, 5-F 3-F, 4-F H H Cl Cl
4.819 3-CF3, 5-CF3 3-F, 4-F H H Cl Cl
4.820 2-F, 4-F 3-F, 4-F H H Cl Cl
4.821 2-F, 4-F 3-F, 4-F H H Br Cl
4.822 2-F, 4-F 3-F, 4-F H H Cl Br Comp.
Ri R2 R3 Rs R7 Rs Phys. data No.
4.823 2-F, 4-F 3-F, 4-F H H Br Br
4.824 2-F, 6-F 3-F, 4-F H H Cl Cl
4.825 2-F, 4-F, 6-F 3-F, 4-F H H Cl Cl
4.826 H 2,3-(-OCF2O- ) H H Cl Cl M.p. 121-122°C
4.827 2-F 2,3-(-OCF2O- > H H Cl H oil
4.828 2-F 2,3-(-OCF20- H H H Cl oil
4.829 2-F 2,3-(-OCF2O- 1 H H Cl Cl M.p. 102-103°C
4.830 2-CH3 2,3-(-OCF2O- ) H H Cl Cl M.p. 83-84°C
4.831 3-F 2,3-(-OCF2O- ) H H Cl Cl
4.832 3-CF3 2,3-(-OCF2O- ) H H Cl Cl
4.833 4-F 2,3-(-OCF2O- ) H H Cl H
4.834 4-F 2,3-(-OCF2O- 1 H H H Cl
4.835 4-F 2,3-(-OCF2O- ) H H Cl Cl
4.836 4-F 2,3-(-OCF2O- ) H H Br Br
4.837 4-CI 2,3-(-OCF2O- ) H H Cl Cl
4.838 4-CF3 2,3-(-OCF20- ) H H Cl Cl
4.839 4-OCF3 2,3-(-OCF2O- I H H Cl Cl
4.840 4-SCF3 2,3-(-OCF20- ) H H Cl Cl
4.841 4-SO2CF3 2,3-(-OCF2O- ) H H Cl Cl
4.842 4-CN 2,3-(-OCF2O- ) H H Cl Cl
4.843 4-SF5 2,3-(-OCF2O- ) H H Cl Cl
4.844 4-F, 3-F 2,3-(-OCF2O- H H Cl Cl
4.845 4-F, 3-CF3 2,3-(-OCF2O- I H H Cl Cl
4.846 2-F, 4-CF3 2,3-(-OCF2O- 1 H H Cl Cl
4.847 3-F, 5-F 2,3-(-OCF2O- H H Cl Cl
4.848 3-CF3, 5-CF3 2,3-(-OCF20- 1 H H Cl Cl
4.849 2-F, 4-F 2,3-(-OCF20- H H Cl H
4.850 2-F, 4-F 2,3-(-OCF20- 1 H H H Cl oil
4.851 2-F, 4-F 2,3-(-OCF20- H H Cl Cl M.p. 86-87°C
4.852 2-F, 4-F 2,3-(-OCF20- H H Br Cl
4.853 2-F, 4-F 2,3-(-OCF2O- H H Cl Br
4.854 2-F, 4-F 2,3-(-OCF2O- H H Br Br
4.855 2-F, 6-F 2,3-(-OCF2O-1 H H Cl Cl
4.856 2-F, 4-F, 6-F 2,3-(-OCF20- H H Cl Cl Comp.
Ri R2 R3 Rs R7 Rs Phys. data No.
4.857 H 2,3-(-OCF2O-) H Cl Cl Cl
4.858 4-F 2,3-(-OCF2O-) H F Cl Cl
4.859 2-F, 4-F 2,3-(-OCF20-) H F Cl Cl
4.860 2-F, 4-F 2,3-(-OCF2O-) H Cl Cl Cl
4.861 2-F, 4-F 2,3-(-OCF2O-) H CH3 Cl Cl
4.862 4-F 2,3-(-OCF2O-) Br H Cl Cl
4.863 2-F, 4-F 2,3-(-OCF2O-) C≡CH H Cl Cl
4.864 2-F, 4-F 2,3-(-OCF2O-) Br H Cl Cl
4.865 2-F, 4-F 2,3-(-OCF2O-) COCH3 H Cl Cl-
4.866 2-F, 4-F 2,3-(-OCF2O-) Br F Cl Cl
4.867 H 3,4-(-OCF2O-) H H Cl Cl
4.868 2-F 3,4-(-OCF2O-) H H Cl Cl
4.869 2-CH3 3,4-(-OCF2O-) H H Cl Cl
4.870 4-F 3,4-(-OCF2O-) H H Cl Cl
4.871 4-CI 3,4-(-OCF2O-) H H Cl Cl
4.872 4-CF3 3,4-(-OCF20-) H H Cl Cl
4.873 2-F, 4-F 3,4-(-OCF20-) H H F F
4.874 2-F, 4-F 3,4-(-OCF2O-) H H Cl Cl
4.875 2-F, 4-F 3,4-(-OCF20-) H H Br Br
4.876 H 2,3-(-OCF2CF2O-) H H Cl Cl
4.877 2-F 2,3-(-OCF2CF2O-) H H Cl Cl
4.878 2-CH3 2,3-(-OCF2CF2O-) H H Cl Cl
4.879 3-F 2,3-(-OCF2CF2O-) H H Cl Cl
4.880 3-CF3 2,3-(-OCF2CF2O-) H H Cl Cl
4.881 4-F 2,3-(-OCF2CF2O-) H H Cl Cl
4.882 4-F 2,3-(-OCF2CF2O-) H H Br Br
4.883 4-CI 2,3-(-OCF2CF2O-) H H Cl Cl
4.884 4-CF3 2,3-(-OCF2CF2O-) H H Cl Cl
4.885 4-OCF3 2,3-(-OCF2CF2O-) H H Cl Cl
4.886 4-SCF3 2,3-(-OCF2CF2O-) H H Cl Cl
4.887 4-SO2CF3 2,3-(-OCF2CF2O-) H H Cl Cl
4.888 4-CN 2,3-(-OCF2CF2O-) H H Cl Cl
4.889 4-SF5 2,3-(-OCF2CF2O-) H H Cl Cl
4.890 4-F, 3-F 2,3-(-OCF2CF2O-) H H Cl Cl Comp.
Ri R2 R3 Rs R7 R8 Phys. data No.
4.891 4-F, 3-CF3 2,3-(-OCF2CF20-) H H Cl Cl
4.892 2-F, 4-CF3 2,3-(-OCF2CF2O-) H H Cl Cl
4.893 3-F, 5-F 2,3-(-OCF2CF20-) H H Cl Cl
4.894 3-CF3, 5-CF3 2,3-(-OCF2CF2O-) H H Cl Cl
4.895 2-F, 4-F 2,3-(-OCF2CF20-) H H Cl Cl
4.896 2-F, 4-F 2,3-(-OCF2CF2O-) H H Br Cl
4.897 2-F, 4-F 2,3-(-OCF2CF20-) H H Cl Br
4.898 2-F, 4-F 2,3-(-OCF2CF2O-) H H Br Br
4.899 2-F, 6-F 2,3-(-OCF2CF20-) H H Cl Cl
4.900 2-F, 4-F, 6-F 2,3-(-OCF2CF20-) H H Cl Cl
4.901 H 3,4-(-OCF2CF2O-) H H Cl Cl
4.902 2-F 3,4-(-OCF2CF20-) H H Cl Cl
4.903 2-CH3 3,4-(-OCF2CF20-) H H Cl Cl
4.904 4-F 3,4-(-OCF2CF20-) H H Cl Cl
4.905 4-CI 3,4-(-OCF2CF2O-) H H Cl Cl
4.906 4-CF3 3,4-(-OCF2CF20-) H H Cl Cl
4.907 2-F, 4-F 3,4-(-OCF2CF2O-) H H F F
4.908 2-F, 4-F 3,4-(-OCF2CF20-) H H Cl Cl
4.909 2-F, 4-F 3,4-(-OCF2CF20-) H H Br Br
4.910 H 2,3-(-OCF2CF2O-), 4-F H H Cl Cl
4.911 2-F 2,3-(-OCF2CF2O-), 4-F H H Cl Cl
4.912 2-CH3 2,3-(-OCF2CF2O-), 4-F H H Cl Cl
4.913 4-F 2,3-(-OCF2CF2O-), 4-F H H Cl Cl
4.914 4-CI 2,3-(-OCF2CF2O-), 4-F H H Cl Cl
4.915 4-CF3 2,3-(-OCF2CF2O-), 4-F H H Cl Cl
4.916 2-F, 4-F 2,3-(-OCF2CF2O-), 4-F H H F F
4.917 2-F, 4-F 2,3-(-OCF2CF2O-), 4-F H H Cl Cl
4.918 2-F, 4-F 2,3-(-OCF2CF20-), 4-F H H Br Br
Biological Examples
Example B1 : Herbicidal action prior to emergence of the plants (pre-emerqence action) Monocotyledonous and dicotyledonous test plants are sown in standard soil in pots. Immediately after sowing, the test compounds, in the form of an aqueous suspension (prepared from a wettable powder (Example F3, b) according to WO 97/34485) or in the form of an emulsion (prepared from an emulsifiable concentrate (Example F1 , c) according to
WO 97/34485), are applied by spraying in an optimum concentration (500 litres water/ha).
The test plants are then grown in a greenhouse under optimum conditions.
After a test duration of 4 weeks, the test is evaluated in accordance with a scale of nine ratings (1 = total damage, 9 = no action). Ratings of from 1 to 4 (especially from 1 to 3) indicate good to very good herbicidal action.
Table B1 :
Pre-emergence action at 1000 g ai/ha
Figure imgf000097_0001
The same results are obtained when the compounds of formula I are formulated in accordance with the other Examples according to WO 97/34485.
Example B2: Post-emergence herbicidal action
Monocotyledonous and dicotyledonous test plants are sown in standard soil in pots. When the test plants are at the 2- to 3-leaf stage, the test compounds, in the form of an aqueous suspension (prepared from a wettable powder (Example F3, b) according to WO 97/34485) or in the form of an emulsion (prepared from an emulsifiable concentrate (Example F1 , c) according to WO 97/34485), are applied by spraying in an optimum concentration (500 litres water/ha). The test plants are then grown on in a greenhouse under optimum conditions.
After a test duration of 2 to 3 weeks, the test is evaluated in accordance with a scale of nine ratings (1 = total damage, 9 = no action). Ratings of from 1 to 4 (especially from 1 to 3) indicate good to very good herbicidal action.
Table B2:
Post-emergence herbicidal action at 1000 g ai/ha
Figure imgf000098_0001
The same results are obtained when the compounds of formula I are formulated in accordance with the other Examples according to WO 97/34485.

Claims

What is claimed is:
1. A compound of formula
Figure imgf000099_0001
wherein
Ri and R2 are each independently of the other C^alkyl, C*ι-6haloalkyl, d-6alkoxy, C^halo- alkoxy, C-*.6alkylthio, C^ehaloalkylthio, Cι.6alkylsulfinyl, Cι-6haloalkylsulfinyl, Cι.6alkylsulfonyl, Ci-6haloalkylsulfonyl, C^ealkylcarbonyl, Cι-6haloalkylcarbonyl, halogen, -CN, -NO2 or -SF5, or two adjacent Rn substituents or two adjacent R2 substituents are, independently of one another, Cι.3alkylene, Cι.3alkylene containing 1 or 2 oxygen atoms, there being no oxygen- oxygen bond, C^haloalkylene or Cι-3haloalkylene containing 1 or 2 oxygen atoms, there being no oxygen-oxygen bond, m and n are each independently of the other 0, 1 , 2 or 3,
R3 is Cι.4alkyl, Cι- haloalkyl, C**- alkoxy, Cι-4haloalkoxy, Cι. alkylthio, Cι. haloalkylthio, C^- alkylsulfinyl, C^alkylsulfonyl, C2.4alkenyl, C2-4haloalkenyl, C2.3alkynyl, halogen, -CN, -NO2, -CHO, -CORg, -COOR10 or -CONRnR12, wherein R9, Rι0, Rn and R 2 are each independently of the others hydrogen, Chalky!, C14- haloalkyl, C3.6cycloalkyl, C2. alkenyl, C2.4haloalkenyl, C2-3alkynyl, benzyl or phenyl, and R10 may additionally be an alkali metal or alkaline earth metal, ammonium, a quaternary ammonium base or an amine, or R11 and R12 together are C2.5alkylene, p is 0 or 1 ,
R and R6 are each independently of the other hydrogen, Cι.4alkyl, Cι- haloalkyl or halogen, or R and R6 together form a chemical bond, or R4 and R6 together form a radical -CH2- or -CH2CH2-, which may be substituted by C^alkyl,
C-*-3haloalkyl or by halogen, and
R5, R7 and R8 are each independently of the others hydrogen, Cι-4alkyl, Cι-3haloalkyl or halogen, or an enantiomer, a configurationally pure E or Z compound or an E/Z mixture of such compounds.
2. A compound according to claim 1 , wherein at least one of the substituents R4, R5, R6, R and R8 is halogen.
3. A compound according to claim 1 , wherein R4 and R6 together form a chemical bond.
4. A compound according to claim 1 , wherein R and R6 together form a chemical bond and R8 is halogen.
5. A compound according to claim 1 , wherein R4 and R6 together form a chemical bond and R7 and R8 are halogen.
6. A compound according to claim 1 , wherein R4 and R6 together form a chemical bond, the radical -CR5=CR7R8 occupies the 5-position, m is 1 , R occupies the meta-position of the phenyl ring, and R5, R7 and R8 are as defined in claim 1.
7. A compound according to claim 1 , wherein R4 and R6 together form a chemical bond, the radical -CR5=CR7R8 occupies the 5-position, m is 2, the two R^ substituents occupy the meta- and ortho-positions or the meta- and para-positions of the phenyl ring, and R5, R7 and R8 are as defined in claim 1.
8. A compound according to claim 1 , wherein R4 and R6 together form a chemical bond, the radical -CR5=CR R8 occupies the 5-position, m is 1 , and Ri occupies the meta-position of the phenyl ring, and R5, R7 and R8 are each independently of the others hydrogen or halogen, and p is 0.
9. A compound according to claim 1 , wherein R4 and R6 together form a chemical bond, the radical -CR5=CR7R8 occupies the 5-position, m is 1 , and Ri occupies the meta-position of the phenyl ring, and R5, R and R8 are each independently of the others hydrogen or halogen, and p is 1 and R3 is Cι- alkyl, C2-3alkynyl, halogen or -CN.
10. A compound according to claim 1 , wherein R4 and R6 together form a chemical bond, the radical -CR5=CR7R8 occupies the 5-position, m is 2, the two Ri substituents occupy the meta- and ortho-positions or the meta- and para-positions of the phenyl ring, R5, R7 and R8 are each independently of the others hydrogen or halogen, and p is 0.
11. A compound according to claim 1 , wherein R4 and R6 together form a chemical bond, the radical -CR5=CR7R8 occupies the 5-position, m is 2, the two Ri substituents occupy the meta- and ortho-positions or the meta- and para-positions of the phenyl ring, R5, R7 and R8 are each independently of the others hydrogen or halogen, and p is 1 and R3 is C^alkyl, C2-3alkynyl, halogen or -CN.
12. A compound according to claim 1 , wherein R4 and R6 together form a chemical bond, the radical -CR5=CR7R8 occupies the 4-position, n is 1 , R2 occupies the meta-position of the phenyl ring, and R5, R7 and R8 are as defined in claim 1.
13. A compound according to claim 1 , wherein R and R6 together form a chemical bond, the radical -CR5=CR7R8 occupies the 4-position, n is 2, the two R substituents occupy the meta- and ortho-positions or the meta- and para-positions of the phenyl ring, and R5, R7 and R8 are as defined in claim 1.
14. A compound according to claim 1 , wherein R4 and R6 together form a chemical bond, the radical -CRs=CR7R8 occupies the 4-position, n is 1 , R2 occupies the meta-position of the phenyl ring, and R5, R7 and R8 are each independently of the others hydrogen or halogen, and p is 0.
15. A compound according to claim 1 , wherein R4 and R6 together form a chemical bond, the radical -CR5=CR7R8 occupies the 4-position, n is 1 , R2 occupies the meta-position of the phenyl ring, and R5, R7 and R8 are each independently of the others hydrogen or halogen, and p is 1 and R3 is Cι-4alkyl, C2-3alkynyl, halogen or -CN.
16. A compound according to claim 1 , wherein R and R6 together form a chemical bond, the radical -CR5=CR7R8 occupies the 4-position, n is 2, and the two R2 substituents occupy the meta- and ortho-positions or the meta- and para-positions of the phenyl ring, R5, R7 and R8 are each independently of the others hydrogen or halogen, and p is 0.
17. A compound according to claim 1 , wherein R4 and R6 together form a chemical bond, the radical -CR5=CR7R8 occupies the 4-position, n is 2, and the two R2 substituents occupy the meta- and ortho-positions or the meta- and para-positions of the phenyl ring, R5, R7 and R8 are each independently of the others hydrogen or halogen and p is 1 and R3 is Cι-4alkyl, C2.3alkynyl, halogen or -CN.
18. A compound according to claim 1 , wherein m + n is greater than or equal to 1.
19. A process for the preparation of a compound of formula I according to claim 1 , wherein a compound of formula II
Figure imgf000102_0001
wherein
Ri and R2 are each independently of the other Cι-6alkyl, C -6haloalkyl, Cι-6alkoxy, Cι.6halo- alkoxy, Cι.6alkylthio, Cι-6haloalkylthio, Cι-6alkylsulfinyl, Cι_6haloalkylsulfinyl, Cι-6alkylsulfonyl, Cι.6haloalkylsulfonyl, Cι-6alkyIcarbonyl, Cι-6haloalkylcarbonyl, halogen, -CN, -NO2 or -SF5, or two adjacent R substituents or two adjacent R2 substituents are, independently of one another, Cι.3alkylene, Cι-3alkylene containing 1 or 2 oxygen atoms, there being no oxygen- oxygen bond, Cι-3haloalkylene or Cι-3haloalkylene containing 1 or 2 oxygen atoms, there being no oxygen-oxygen bond, m and n are each independently of the other 0, 1 , 2 or 3, _ _ _
- 102 -
R3 is Cι-4haloalkyl, Cι-4alkoxy, Cι. haloalkoxy,
Figure imgf000103_0001
Cι.4haloalkyIthio, Cι- - alkylsulfinyl, Cι-4alkylsulfonyl, C2.4alkenyl, C2-4haloalkenyl, C2-3alkynyl, halogen, -CN, -NO2,
-CHO, -CORg, -COOR10 or -CONRnR12, wherein R9, Rι0, Rn and R12 are each independently of the others hydrogen, Cι-4alkyl, C^- haloalkyl, C3.6cycloalkyl, C2.4alkenyl, C2.4haloalkenyl, C2-3alkynyl, benzyl or phenyl, and Rι0 may additionally be an alkali metal or alkaline earth metal, a quaternary ammonium base or an amine, or
R11 and Ri 2 together are C2.5alkylene, p is 0 or 1 , and wherein
(a) Y is hydrogen or halogen, is metallated with a metallating reagent, optionally transmetallated with a second metallating reagent, then reacted with a compound of formula III Q-CR R5-CR6R R8 wherein Q is a halogen atom or a radical of the formula -O-SO2CF3, and R4 and R6 are each independently of the other hydrogen, C1- alkyl) Cι-3haloalkyI or halogen, or R4 and R6 together form a chemical bond, or R4 and R6 together form a radical -CH2- or -CH2CH2-, which may be substituted by Cι-4alkyl, Cι-3haloalkyl or by halogen, and
R5, R7 and R8 are each independently of the others hydrogen, Chalky!, Cι-3haloalkyl or halogen, optionally in the presence of a Pd or Ni catalyst, and the compound of formula I is isolated, or wherein
(b) Y is a mono-, di-, tri- or tetra-valent metal atom, is reacted with a compound of formula III Q-R4R5-CR6R R8 wherein Q is a halogen atom or a radical of the formula -O-S02CF3, and R4 and R6 are each independently of the other hydrogen, C -4alkyl, Cι-3haloalkyl or halogen, or R4 and R6 together form a chemical bond, or R4 and R6 together form a radical -CH2- or -CH2CH2-, which may be substituted by Cι. alkyl, Cι-3haloalkyl or by halogen, and
R5, R7 and R8 are each independently of the others hydrogen, Cι.4alkyl, Cι-3haloalkyI or halogen, optionally in the presence of a Pd or Ni catalyst, and the compound of formula I is isolated.
20. A process for the preparation of a compound of formula I according to claim 1 , wherein a compound of formula II
Figure imgf000104_0001
wherein
R-i and R2 are each independently of the other Cι-6alkyl, Cι.6haIoalkyl, C -6alkoxy, Cι-6halo- alkoxy, C-ι-6alkylthio, Cι.6haloalkylthio, Cι.6alkylsulfinyl, Cι-6haloalkylsulfinyl, Cι-6alkylsulfonyl, C1.6haloalkylsulfonyl, Cι-6alkylcarbonyl, Cι-6haloalkylcarbonyl, halogen, -CN, -NO2 or -SF5, or two adjacent Ri substituents or two adjacent R2 substituents are, independently of one another, Cι-3alkylene, Cι.3alkylene containing 1 or 2 oxygen atoms, there being no oxygen- oxygen bond, Cι-3haloalkylene or Cι-3haloalkylene containing 1 or 2 oxygen atoms, there being no oxygen-oxygen bond, m and n are each independently of the other -0, 1 , 2 or 3,
R3 is Cι-4alkyl, Cι.4haloalkyl, Cι-4alkoxy, Cι- haloalkoxy, C1-4alky!thio, Cι-4haloalkylthio, Cι--r alkylsulfinyl, Cι-4alkylsulfonyl, C2. alkenyl, C2-4haloaIkenyl, C2-3alkynyl, halogen, -CN, -NO , -CHO, -COR9, -COOR10 or -CONRnRι2, wherein R9, Rι0, Rn and Rι2 are each independently of the others hydrogen,
Figure imgf000104_0002
haloalkyl, C3-6cycloalkyl, C2- alkenyl, C2.4haloalkenyl, C2.3alkynyl, benzyl or phenyl, and R10 may additionally be an alkali metal, an alkaline earth metal, a quaternary ammonium base or an amine, or
R11 and R12 together are C2-5alkylene, p is 0 or 1 , and
Y is halogen or a radical of the formula -O-SO2CF3 or -N2 +, is reacted with a compound of formula IV M-CR4R5-CR6R7R8 wherein M is a mono-, di-, tri- or tetra-valent metal atom, and R4 and R6 are each independently of the other hydrogen, Cι-4alkyl, Cι-3haloalkyl or halogen, or R4 and R6 together form a chemical bond, or R4 and R6 together form a radical -CH2- or -CH2CH2-, which may be substituted by C^alkyl, Ci-shaloalkyl or by halogen, and R5, R7 and R8 are each independently of the others hydrogen, Cι.4alkyl, Cι-3haloalkyl or halogen, optionally in the presence of a Pd or Ni catalyst, and the compound of formula I is isolated.
21. A process for the preparation of a compound of formula I according to claim 1 , wherein R4 and R6 together form a chemical bond, R5 is hydrogen, C1- alkyl or Cι-3haloalkyl, and R7 and R8 are each independently of the other hydrogen, Cι.4alkyl, Cι-3haloalkyl or halogen, wherein a compound of formula II
Figure imgf000105_0001
wherein
Ri and R2 are each independently of the other Cι-6alkyl, d-6haloalkyl, Cι-6alkoxy, d.6halo- alkoxy, Cι.6alkylthio, Cι.6haloalkylthio, Cι-6alkylsulfinyl, Cι.6haloalkylsulfinyl, Cι-6alkylsulfonyl, d-ehaloalkylsulfonyl, d.6alkylcarbonyl, Cι.6haloalkylcarbonyl, halogen, -CN, -NO2 or -SF5, or two adjacent Ri substituents or two adjacent R2 substituents are, independently of one another, d.3alkylene, Cι-3alkylene containing 1 or 2 oxygen atoms, there being no oxygen- oxygen bond, Cι.3haloalkylene or Cι-3haloalkylene containing 1 or 2 oxygen atoms, there being no oxygen-oxygen bond, m and n are each independently of the other 0, 1 , 2 or 3, R3 is Cι-4alkyl, Cι-4haloalkyl,
Figure imgf000106_0001
C -4haloalkoxy, Cι-4alkylthio, Cι-4haloalkylthio, Cι-4- alkylsulfinyl, Cι-4alkylsulfonyl, C2- alkenyl, C2. haloalkenyI, C2-3alkynyl, halogen, -CN, -N02,
-CHO, -CORg, -COOR10 or -CONR11R12, wherein R9, R10, Rn and R 2 are each independently of the others hydrogen, Cι- alkyl, Cι^- haloalkyl, C3-6cycloalkyl, C2-4alkenyl, C -4haloalkenyl, C2-3alkynyl, benzyl or phenyl, and R10 may additionally be an alkali metal or alkaline earth metal, a quaternary ammonium base or an amine, or
Rn and R12 together are C2-5alkylene, p is 0 or 1 , and
Y is a radical of formula -C(O)R5,
(a) is reacted with a compound of formula Va R7R8C=P(C6H5)3 wherein R7 and R8 are each independently of the other hydrogen, Cι. alkyl, d.3haloalkyl or halogen, and the compound of formula I is isolated, or
(b) is reacted with a compound of formula Vb R7R8CXH wherein X is halogen and R7 and R8 are each independently of the other hydrogen, Cι-4alkyl, Cι-3haloalkyl or halogen, in the presence of a base, optionally acylated and then reduced, and the compound of formula I is isolated, or
(c) is reacted with a compound of formula Vc R7R8CXCOOH / R7R8CXCOONa wherein X is halogen and R7 and R8 are each independently of the other hydrogen, Cι-4alkyl, d-3haloalkyl or halogen, optionally acylated and then reduced, and the compound of formula I is isolated.
22. A process for the preparation of a compound of formula I according to claim 21 , wherein the reaction of a compound of formula II according to variant (b) or (c) is carried out as a one-pot reaction.
23. A process for the preparation of a compound of formula I according to claim 1 , wherein a compound of formula VI
Figure imgf000107_0001
wherein
R2 is Cι-6alkyl, d-6haloalkyl, d-6alkoxy, Cι-6haloalkoxy, Cι-6alkylthio, Cι-6haloalkylthio,
Cι.6alkylsulfinyl, Ci-ehaloalkylsulfinyl, Cι.6alkylsulfonyl, Cι-6haloalkylsulfonyl, Cι.6alkylcarbonyl,
Ci-ehaloalkylcarbonyl, halogen, -CN, -NO2 or -SF5, or two adjacent R2 substituents are Cι-3alkylene, Cι-3alkylene containing 1 or 2 oxygen atoms, there being no oxygen-oxygen bond, d.3haloalkyIene or d-3haloalkylene containing 1 or 2 oxygen atoms, there being no oxygen-oxygen bond, n is 0, 1 , 2 or 3,
R3 is Cι.4haloalkyl, Cι.4alkoxy, Cι-4haloalkoxy, Cι-4alkylthio, Cι- haloalkylthio, Cι-4- alkylsulfinyl, Cι-4aIkylsulfonyl, C2.4alkenyl, C2-4haloalkenyl, C2.3alkynyl, halogen, -CN, -NO2,
-CHO, -COR9, -COOR10 or -CONR11R12, wherein R9, R10, Rn and R12 are each independently of the others hydrogen, d^alkyl, Cι-4- haloalkyl, C3.6cycloalkyl, C2- alkenyl, C2-4haloalkenyl, C2.3alkynyl, benzyl or phenyl, and Rι0 may additionally be an alkali metal or alkaline earth metal, a quaternary ammonium base or an amine, or
R11 and Ri2 together are C2-5alkylene, p is 0 or 1 , and
R4 and R6 are each independently of the other hydrogen, C -4 alkyl, d-3haloalkyl or halogen, or
R and R6 together form a chemical bond, or
R4 and R6 together form a radical -CH2- or -CH2CH2-, which may be substituted by Cι.4alkyl,
C1.3haloalkyl or by halogen, and
R5, R7 and R8 are each independently of the others hydrogen, Cι-4alkyl, d-3haloalkyl or halogen, is reacted with a compound of formula VII
Figure imgf000108_0001
wherein Ri is as defined for R2, and m is as defined for n, the pyrazoline compound of formula la so obtained
Figure imgf000108_0002
wherein the substituents R-*, R2, R3, R4, R5, Re, R7 and R8 and also m and n and p are as defined, is oxidised to form the corresponding pyrazole compound and the latter is isolated.
24. A process for the preparation of a compound of formula I according to claim 23, wherein the formation of the pyrazoline ring and the oxidation thereof to form the corresponding pyrazole ring is carried out as a one-pot reaction.
25. A compound of formula la
Figure imgf000109_0001
wherein
Ri and R2 are each independently of the other d.6alkyl, d.6haloalkyl, Cι-6alkoxy, Cι-6halo- alkoxy, d-6alkylthio, Ci-ehaloalkylthio, d-6alkylsulfinyl, d-6haloalkylsulfinyl, d-6alkylsulfonyl, Ci-ehaloalkylsulfonyl, C -6alkylcarbonyl, Cι-6haloalkylcarbonyl, halogen, -CN, -NO2 or -SF5, or two adjacent Ri substituents or two adjacent R2 substituents are, independently of one another, d-3alkylene, d-3alkylene containing 1 or 2 oxygen atoms, there being no oxygen- oxygen bond, Cι-3haloalkylene or d-3haloalkylene containing 1 or 2 oxygen atoms, there being no oxygen-oxygen bond, m and n are each independently of the other 0, 1 , 2 or 3,
R3 is Cι- alkyl, C -4haloalkyl, Cι-4alkoxy, d-4haloalkoxy, d^alkylthio, Cι-4haloalkylthio, Cι-4- alkylsulfinyl, Cι-4alkylsulfonyl, C2-4alkenyl, C2.4haloalkenyl, C2-3alkynyl, halogen, -CN, -NO2, -CHO, -CORg, -COOR10 or -CONRnRι2, wherein R9, R 0, Rn and R12 are each independently of the others hydrogen, C^alkyl, Cι^- haloalkyl, C3.6cycloalkyl, C2.4alkenyl, C2.4haloalkenyl, C2-3alkynyl, benzyl or phenyl, and R10 may additionally be an alkali metal or alkaline earth metal, a quaternary ammonium base or an amine, or
Rn and R12 together are C2.5alkylene, p is 0, 1 , 2 or 3,
R4 and R6 are each independently of the other hydrogen, Cι.4alkyl, Cι-3haloalkyl or halogen, or R4 and R6 together form a chemical bond, or R4 and R6 together form a radical -CH2- or -CH2CH2-, which may be substituted by Cι-4alkyl,
Cι-3haloalkyI or by halogen, and
R5, R7 and R8 are each independently of the others hydrogen, C1-4alkyl, d-3haloalkyl or halogen, at least one of those substituents being other than hydrogen, the compounds of formulae
Figure imgf000110_0001
Figure imgf000110_0002
Figure imgf000111_0001
being excluded.
26. A herbicidal and plant-growth-inhibiting composition, comprising a herbicidally effective amount of a compound of formula I on an inert carrier.
27. A method of controlling undesired plant growth, which method comprises applying a compound of formula I, or a composition comprising such a compound, in a herbicidally effective amount to the plants or to the locus thereof.
28. A method of inhibiting plant growth, which method comprises applying a compound of formula I, or a composition comprising such a compound, in a herbicidally effective amount to the plants or to the locus thereof.
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