WO1996007633A1 - Phenylessigsäurealkylester - Google Patents

Phenylessigsäurealkylester Download PDF

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Publication number
WO1996007633A1
WO1996007633A1 PCT/EP1995/003405 EP9503405W WO9607633A1 WO 1996007633 A1 WO1996007633 A1 WO 1996007633A1 EP 9503405 W EP9503405 W EP 9503405W WO 9607633 A1 WO9607633 A1 WO 9607633A1
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iii
compounds
methoxy
radical
bond
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PCT/EP1995/003405
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German (de)
English (en)
French (fr)
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Klaus Oberdorf
Hubert Sauter
Hartmann König
Albrecht Harreus
Bernd Müller
Reinhard Kirstgen
Wassilios Grammenos
Herbert Bayer
Franz Röhl
Gisela Lorenz
Eberhard Ammermann
Volker Harries
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Basf Aktiengesellschaft
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Priority to JP8509172A priority Critical patent/JPH10505596A/ja
Priority to BR9509004A priority patent/BR9509004A/pt
Priority to AU33878/95A priority patent/AU3387895A/en
Priority to EP95930531A priority patent/EP0781266A1/de
Publication of WO1996007633A1 publication Critical patent/WO1996007633A1/de

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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
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    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/32—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • C07C235/34—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton containing six-membered aromatic rings having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
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    • C07C239/08—Hydroxylamino compounds or their ethers or esters
    • C07C239/20—Hydroxylamino compounds or their ethers or esters having oxygen atoms of hydroxylamino groups etherified
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    • C07C251/48—Oximes with oxygen atoms of oxyimino groups bound to hydrogen atoms or to carbon atoms of unsubstituted hydrocarbon radicals with the carbon atom of at least one of the oxyimino groups bound to a carbon atom of a six-membered aromatic ring
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    • C07C251/50—Oximes having oxygen atoms of oxyimino groups bound to carbon atoms of substituted hydrocarbon radicals
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/56—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton containing six-membered aromatic rings
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    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/734—Ethers
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    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/734—Ethers
    • C07C69/736—Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring
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    • 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
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms
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    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
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    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more 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, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/52—Two oxygen atoms
    • C—CHEMISTRY; METALLURGY
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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
    • C07D249/12—Oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D277/34—Oxygen atoms
    • C—CHEMISTRY; METALLURGY
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
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    • C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
    • C07F9/02—Phosphorus compounds
    • C07F9/28—Phosphorus compounds with one or more P—C bonds
    • C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
    • C07F9/40—Esters thereof
    • C07F9/4003—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
    • C07F9/4056—Esters of arylalkanephosphonic acids

Definitions

  • the present invention relates to alkyl phenylacetate of the formula I.
  • Amino oxi (-NHO-); V oxygen (-O-), sulfur (-S-) or amino (-NH-);
  • R halogen, hydroxy, mercapto, amino, carboxyl, carbonylamino or an organic radical which is bonded directly or via an oxy, mercapto, amino, carboxyl or carbonylamino group, or together with a group X and the phenyl ring to which they are bonded, an optionally subst.
  • Bicyclic, partially or completely unsaturated system which, in addition to carbon ring members, can contain heteroatoms from the group consisting of oxygen, sulfur and nitrogen.
  • Alkyl phenylacetates are known from the literature as pharmaceuticals or intermediates for their preparation [EP-A 486 011, EP-A 462 531, JP-A 03 / 284.665, FR-A 2 572 076, EP-A 166 650, JP-A 59 / 164,766, JP-A 56 / 005,439, DE-A 29 31 735, DE-A 24 49 990, JP-A 49 / 108,039, US-A 3,607,941, GB-A 1 230 347, DE-A 12 77 127, EP -A 065 874, NL-A 75 / 13,439, NL-A 73 / 09,425, BE-A 77 / 06,316, FR-A 2 054 532, EP-A 565 965, WO-A 91 / 17,987 and US-A 4,752,616 ] known.
  • EP-A 206 772 such compounds with herbicidal properties
  • the present invention was based on new compounds with fungicidal properties as an object.
  • the compounds I are prepared analogously to various methods known per se from the literature. During production, it is irrelevant whether the grouping R or the grouping -CH (UR ') -COVR "is built up first.
  • the compounds I in which U and V are oxygen are obtained, for example, by converting a benzaldehyde of the formula II in a manner known per se with a cyanide into the corresponding cyanohydrin of the formula III, III in the presence saponified an acid with an alcohol of the formula IV to give the corresponding ⁇ -hydroxyphenylacetic acid alkyl ester of the formula V and etherified V to I with a derivative of the formula Via.
  • L 1 in the formula Via stands for a nucleophilically exchangeable leaving group such as halogen (for example chlorine, bromine or iodine) or alkyl or aryl sulfonate (for example methyl sulfonate, trifluoromethyl sulfonate, phenyl sulfonate or methylphenyl sulfonate).
  • halogen for example chlorine, bromine or iodine
  • alkyl or aryl sulfonate for example methyl sulfonate, trifluoromethyl sulfonate, phenyl sulfonate or methylphenyl sulfonate.
  • the cyanohydrin III is prepared in a manner known per se [cf. Organikum, 15th edition (1977) page 557f; Houben Weyl Vol. VIII, 274f (1952)] usually at temperatures from 0 ° C. to 40 ° C., preferably 0 ° C. to 20 ° C. without solvent, in water or in an inert solvent, if appropriate with phase transfer catalysis. Hydrogen cyanide itself and cyanides, from which HCN is formed by adding a mineral acid, are suitable as the HCN source.
  • Alkali metal cyanides e.g. potassium cyanide or sodium cyanide
  • Alkali metal cyanides are particularly suitable as cyanides.
  • Suitable solvents are water, aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol, particularly preferably water and / or alcohols. Mixtures of the solvents
  • the reaction is usually carried out by gradually adding equimolar amounts of a mineral acid (e.g. hydrohalic acids such as hydrochloric acid and hydrobromic acid or sulfuric acid or phosphoric acid).
  • a mineral acid e.g. hydrohalic acids such as hydrochloric acid and hydrobromic acid or sulfuric acid or phosphoric acid.
  • acid salts e.g. ammonium chloride or ammonium sulfate
  • the acids or acid salts are generally used in equimolar amounts based on the cyanide.
  • Alkali metal cyanides, alkali metal carbonates, ammonia or organic bases such as alkylamines and alcoholates are used as basic catalysts.
  • benzaldehyde II required for the preparation of the compounds I are known in the literature (EP-A 400 417) or can be prepared in accordance with the literature cited.
  • ⁇ -Hydroxyphenylacetic acid alkyl esters of the formula V are carried out in a manner known per se [Org. Synth. Col. Vol. I (1941) 336;
  • Suitable inert solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, as well as dimethyl sulfoxide and dimethylformamide.
  • aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether
  • aromatic hydrocarbons such as toluene, o-, m- and
  • Inorganic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, sulfuric acid and perchloric acid, in particular hydrochloric acid and sulfuric acid, are used as acids and acidic catalysts.
  • the acids are generally in
  • This reaction usually takes place at temperatures from 0 ° C. to 80 ° C., preferably 0 ° C. to 30 ° C., in an inert solvent.
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene,
  • Ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, and also dimethyl sulfoxide and dimethylformamide, particularly preferably tetrahydrofuran. Mixtures of the solvents mentioned can also be used
  • inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide are used as bases,
  • alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and magnesium oxide
  • alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and
  • alkali metal amides such as lithium amide, sodium amide and potassium amide
  • alkali metal and alkaline earth metal carbonates such as
  • Lithium carbonate and calcium carbonate and alkali metal bicarbonates such as sodium bicarbonate, organometallic
  • alkali metal alkyls such as methyl lithium, butyllithium and phenyllithium
  • alkyl magnesium halides such as methyl magnesium chloride as well as alkali metal and alkaline earth metal alcoholates such as sodium methoxide, sodium ethanolate, potassium ethanolate, potassium tert-butanolate and dimethoxy-magnesium triethyl triethylamine, such as tert-methylamine, tertiary amine, for example, tertiary butylamine, also tertiary triethylamine, such as tertiary butylamine, such as tertiary amine, such as tertiary amine, such as tertiary amine, such as tertiary amine, such as tertiary amine, for example, Isopropylethylamine and N-methylpiperidine, pyridine, substituted pyridines such as collidine, lutidine and 4-di
  • ⁇ -Hydroxyphenylacetic acid alkyl esters of the formula V also by first converting the compounds V in a manner known per se using a halogenating agent into the corresponding ⁇ -halophenylacetic acid alkyl esters of the formula VII and VII subsequently to I in the presence of a base with an alcohol of the formula VIb etherified.
  • Hal in formula VII means a halogen atom, especially chlorine, bromine or iodine.
  • the halogenation of the compounds V takes place in a manner known per se [cf. Chem. Ber. 120, 1825 (1987)] usually at temperatures from 0 ° C to 60 ° C, preferably 10 ° C to 30 ° C.
  • Suitable halogenating agents are phosphorus tribromide, phosphorus trichloride, thionyl chloride, tetrabromomethane / triphenylphosphine, boron tribromide and hydrogen bromide.
  • the halogenating agents are generally used in excess.
  • the reaction is generally carried out in an inert solvent.
  • Suitable inert solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as Methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol as well as dimethyl sulfoxide and
  • haloform for example chloroform or bromoform
  • R'OH an alcohol of the formula R'OH in the corresponding ⁇ -alkoxyphenylacetic acids
  • the compounds I are obtained starting from ⁇ -ketophenylacetic acid alkyl esters of the formula VIII by reduction to the corresponding ⁇ -hydroxyphenylacetic acid alkyl esters of the formula V and then converting V to I in accordance with the processes described above.
  • the reduction of the ⁇ -ketophenylacetic acid alkyl ester VIII is carried out in a manner known per se [J. Chem. Soc. 520 (1954); Chem. Ber. 76, 308 (1943); Chem. Ber. 120, 1825 (1987)] usually at temperatures from -100 ° C to 100 ° C, preferably 0 ° C to 30 ° C in an inert solvent.
  • suitable reducing agents are hydrides (for example sodium borohydride) or hydrogen.
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane , Anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, organic acids such as acetic acid, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol as well as dimethyl sulfoxide and dimethylformamide, particularly preferably methanol and tetrahydrofuran. Mixtures of the solvents mentioned can also be
  • the reduction with hydrogen is usually carried out in the presence of a catalyst such as nickel, Raney nickel, palladium or palladium on a support such as coal.
  • a catalyst such as nickel, Raney nickel, palladium or palladium on a support such as coal.
  • the ⁇ -ketocarboxylic acid real alkyl esters of the formula VII required for this production process are known in the literature
  • the compounds of the formula I in which U is amino and V is oxygen are prepared, for example, by reacting a compound of the formula VII in a manner known per se (US Pat. No. 4,723,031) with a primary amine or a corresponding ammonium salt of the formula VIc implements.
  • L in the formula VIIa means, for example, halogen (in particular chlorine, bromine and iodine), 1-imidazolyl, hydroxy and
  • the synthesis of the compounds I can also be carried out in such a way that the group -CH (UR ') COVR "is first synthesized and then the group R is built up.
  • group -CH (UR ') COVR "is first synthesized and then the group R is built up.
  • R represents alkyl
  • This halogenation is usually carried out at temperatures from 0 ° C to 100 ° C, preferably 20 ° C to 80 ° C in an inert solvent either in the presence of a radical initiator (e.g. Dibenzoyl peroxide or azobisisobutyronitrile or under UV radiation, for example with a mercury vapor lamp.
  • a radical initiator e.g. Dibenzoyl peroxide or azobisisobutyronitrile
  • UV radiation for example with a mercury vapor lamp.
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, and ethers such as diethyl ether, diisopropyl ether, tert-butylmethyl ether, dioxane, anisole and tetrahydrofuran, particularly preferably cyclohexane, methylene chloride and carbon tetrachloride. Mixtures of the solvents mentioned can also be used.
  • halogenating agents for example Cl 2 , Br 2 , I 2 ), N-bromosuccinimide, N-chlorosuccinimide or dibromodimethylhydrantoin are used as halogenating agents.
  • the halogenating agents are generally used in equimolar amounts, in excess or, if appropriate, as a solvent.
  • the compounds I.2, in which shark stands for iodine, can also be known [J. Chem. Soc. PTI, 416 (1976)] from the chlorides or bromides by reaction with iodides (e.g.
  • the benzyl halide I.2 is obtained by cleaving an appropriate ether 1.3 with a halogenating agent [Hai].
  • This ether cleavage usually takes place at temperatures from -30 ° C. to 50 ° C. in an inert solvent.
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane , Anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol and tert-butanol as well as dimethyl sulfoxide and Dimethylformamide, particularly
  • Lewis acids such as aluminum trichloride, boron trichloride and boron tribromide or hydrogen halides such as hydrogen chloride or hydrogen bromide serve as halogenating agents.
  • Halogenating agents are generally used in equimolar amounts or in excess.
  • nucleophiles preferably N, O or S nucleophiles, e.g. With alcohols, carboxylic acids, thiols or amines, the corresponding ethers, esters, thioethers or amines 1.4 are obtained.
  • Y * stands for oxygen, sulfur, amino or alkylamino;
  • a 1 may mean subst. Alkyl, acyl or an optionally
  • subst. saturated or partially unsaturated cyclic radical which in addition to carbon atoms as ring members can contain heteroatoms from the group consisting of oxygen, sulfur and nitrogen, or an optionally subst. aromatic ring system, which besides
  • Carbon ring members can contain heteroatoms from the group consisting of oxygen, sulfur and nitrogen.
  • This reaction usually takes place at temperatures from 0 ° C. to 80 ° C., preferably 20 ° C. to 60 ° C., in an inert solvent in the presence of a base by standard processes [cf. Organikum, 17th ed. P. 172 f (1988)].
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether , Dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, as well as dimethyl sulfoxide and dimethyl formamide, particularly preferably methylene chloride, toluene, acetone, acetonitrile and dimethyl formamide. Mixtures of the solvents mentioned
  • inorganic bases such as alkali metal and alkaline earth metal hydroxides (e.g. lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide), alkali metal and alkaline earth metal oxides (e.g. lithium oxide, sodium oxide, calcium oxide and magnesium oxide), silver oxide, alkali metal and alkaline earth metal hydride, e.g. hydride
  • alkali metal and alkaline earth metal hydroxides e.g. lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide
  • alkali metal and alkaline earth metal oxides e.g. lithium oxide, sodium oxide, calcium oxide and magnesium oxide
  • silver oxide alkali metal and alkaline earth metal hydride, e.g. hydride
  • alkali metal amides e.g. lithium amide, sodium amide and potassium amide
  • alkali metal and alkaline earth metal carbonates e.g. lithium carbonate and calcium carbonate
  • alkali metal bicarbonates e.g. sodium bicarbonate
  • organometallic compounds especially alkali metal alkyls (e.g. such as methyl lithium and phenyl halide, magnesium halide, magnesium halide, (e.g. methyl magnesium chloride) and alkali metal and alkaline earth metal alcoholates (e.g.
  • tertiary amines such as trimethylamine, triethylamine, tri-isopropylethylamine and N-methylpiperidine
  • pyridine substituted pyridines such as collidine, lutidine and 4-dimethylaminopyridine and bicyclic amines.
  • Sodium hydroxide, potassium carbonate and potassium tert-butoxide are particularly preferred.
  • the bases are generally used in equimolar amounts, in excess or, if appropriate, as a solvent.
  • reaction may be advantageous for the reaction to add a catalytic amount of a crown ether (e.g. 18-crown-6 or 15-crown-5) or 0.01 to 10% by weight of potassium iodide as a catalyst.
  • a catalytic amount of a crown ether e.g. 18-crown-6 or 15-crown-5
  • 0.01 to 10% by weight of potassium iodide as a catalyst.
  • the corresponding ethenylene derivatives 1.6 are obtained by phosphorylation of the benzyl halides I.2 and subsequent Wittig or Wittig-Horner reaction of the phosphorus compounds 1.5 with aldehydes.
  • ⁇ in formula IXa represents aryl, especially phenyl
  • R x in formula IXb represents alkyl or aryl, in particular C 1 -C 4 alkyl or phenyl.
  • a 1 stands for subst. Alkyl, alkenyl or alkynyl, or an optionally subst. saturated or partially unsaturated cyclic radical, which in addition to carbon atoms as ring members can contain heteroatoms from the group consisting of oxygen, sulfur and nitrogen, or an optionally subst. aromatic ring system which, in addition to carbon ring members, can contain heteroatoms from the group consisting of oxygen, sulfur and nitrogen.
  • the starting materials I.2 and IXa or IXb are generally in
  • the phosphorus derivatives 1.5 obtained in this way are then subjected to a Wittig or Wittig-Horner reaction at temperatures from -30 ° C. to 60 ° C., preferably 0 ° C. to 40 ° C., in an inert solvent in the presence of a base with an aldehyde of the formula X implemented.
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene,
  • Ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, alcohols such as methanol, ethanol, n-propanol, isopropanol, n- Butanol and tert-butanol as well
  • inorganic compounds e.g., inorganic compounds, e.g., inorganic compounds, e.g., inorganic compounds, e.g., inorganic compounds, e.g., inorganic compounds, e.g., inorganic compounds, e.g., inorganic compounds, e.g., inorganic compounds, e.g., inorganic compounds, e.g., inorganic compounds, e.g.
  • Alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, alkali metal and alkaline earth metal oxides such as lithium oxide, sodium oxide, calcium oxide and sodium hydride, potassium hydride and calcium hydride, alkali metal amide such as lithium amide, sodium amide and potassium and carbonate such as alkali metal carbonate and alkali metal carbonate and alkali metal carbonate and alkali metal alkali metal carbonate and alkali metal carbonate as well as alkali metal carbonate and alkali metal carbonate , organometallic compounds, in particular alkali metal alkyls such as methyl lithium, butyllithium and phenyllithium, alkyl magnesium halides such as methyl magnesium chloride as well as alkali metal and alkaline earth metal alcoholates such as sodium methoxide, sodium ethanolate, potassium ethanolate, potassium tert-butoxide and, for example, dimethoxymagnesium,
  • Sodium methoxide, potassium t-butoxide, sodium hydride, potassium carbonate and n-butyllithium are particularly preferred.
  • the bases are generally used in equimolar amounts, but they can also be used in excess or, if appropriate, as a solvent.
  • the starting materials 1.5 and X are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use X in an excess based on 1.5.
  • the compounds 1.6 are also obtained by first oxidizing the benzyl halide I.2 to the corresponding benzaldehyde I.7 and then reacting I.7 with a phosphorus compound Xa or Xb in the sense of a Wittig or Wittig-Homer reaction .
  • methylmorpholine-N-oxide monohydrate cf. EP-A 393 4278
  • dimethyl sulfoxide cf. J. Chem. Soc. 1964, p. 520; J. Org. Chem. 24, 1792 (1959)].
  • B.3 R organic radical bonded via oxy, mercapto or amino
  • Leaving group such as halogen (e.g. chlorine, bromine and iodine) or alkyl or aryl sulfonate (e.g. methyl sulfonate, trifluoromethyl sulfonate, phenyl sulfonate and 4-methylphenyl sulfonate).
  • halogen e.g. chlorine, bromine and iodine
  • alkyl or aryl sulfonate e.g. methyl sulfonate, trifluoromethyl sulfonate, phenyl sulfonate and 4-methylphenyl sulfonate.
  • This reaction is usually carried out in an inert solvent in the presence of a base, if appropriate in the presence of a transition metal catalyst in the sense of a Ullmann reaction [cf. Soot. Chem. Rev. 43, 679 (1974); J. Org. Chem. 29, 911 (1964)] or in the sense of a nucleophilic substitution reaction [cf. J.
  • Suitable solvents are aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, chloroform and chlorobenzene, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether , Dioxane, anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone, as well as dimethyl sulfoxide and dimethyl formamide, particularly preferably acetone and dimethyl formamide. Mixtures of the solvents mentioned can also be used. The starting materials are generally reacted with one another in e
  • R a is hydrogen, alkyl, haloalkyl or optionally subst.
  • Z a oxygen, amino or alkylamino
  • Carbon ring members can contain heteroatoms from the group consisting of oxygen, sulfur and nitrogen.
  • reaction conditions correspond in general and in particular to the conditions described in the literature mentioned.
  • ketones 1.10 (R a ⁇ H) are obtained from the aldehydes I.7 by oxidation to the carboxylic acids [cf. Organikum, 15th edition, 447 (1977)], conversion of the carboxylic acids to the corresponding carboxylic acid halides [cf. Organikum, 15th edition, 526 (1977)] and subsequent reaction with zinc-organic compounds [cf. Org. React. (8), 28 (1954)].
  • EP-A 472 300 EP-A 585 751, WO-A 90 / 07,493, WO-A 92 / 13,830, WO-A 92 / 18,487, WO-A 92 / 18,494, WO-A 93 / 16,986 and
  • JP-A 05 / 201,946 described methods according to the following reaction scheme.
  • R b is hydrogen, cyano, nitro, halogen, alkyl, haloalkyl,
  • R c is hydrogen, alkyl or cycloalkyl
  • Alkyl alkenyl or alkynyl, or
  • Carbon ring members can contain heteroatoms from the group consisting of oxygen, sulfur and nitrogen.
  • reaction conditions correspond in general and in particular to the conditions described in the literature mentioned.
  • R f , R e , R d and A 4 in the formulas I.2, XIV and I.13 have the following meaning: R d , R e hydrogen, cyano, nitro, halogen, alkyl, haloalkyl, cycloalkyl, alkoxy, haloalkoxy or optionally subst.
  • Aryl
  • R f is hydrogen, alkyl or cycloalkyl
  • Alkyl alkenyl or alkynyl, or
  • the reaction is carried out in a manner known per se in an inert organic solvent in the presence of a base (e.g. sodium hydride, sodium hydroxide, potassium carbonate and triethylamine) according to the methods described in Houben-Weyl, vol. E14b, p. 370f. and Houben-Weyl, Vol. 10/1, pp. 1189f. described methods.
  • a base e.g. sodium hydride, sodium hydroxide, potassium carbonate and triethylamine
  • L 2 in the formula XVI stands for a nucleophilically exchangeable leaving group, for example halogen or sulfonate groups, preferably chlorine, bromine, iodine, methyl sulfonate, trifluoromethyl sulfonate, phenyl sulfonate or 4-methylphenyl sulfonate.
  • halogen or sulfonate groups preferably chlorine, bromine, iodine, methyl sulfonate, trifluoromethyl sulfonate, phenyl sulfonate or 4-methylphenyl sulfonate.
  • the reaction is carried out in a manner known per se in an inert organic solvent in the presence of a base (e.g. potassium carbonate, potassium hydroxide, sodium hydride, pyridine and triethylamine) according to the methods described in Houben-Weyl Vol. El4b, p. 307f., P. 370f. and pp. 385f., Houben-Weyl Vol. 10/4, pp. 55f., pp. 180f. and p. 217f. and Houben-Weyl, Vol. E5, pp. 780f. described methods.
  • a base e.g. potassium carbonate, potassium hydroxide, sodium hydride, pyridine and triethylamine
  • the dioxime XIV is obtained by reacting the corresponding ketoxime XVII with an O-substituted hydroxylamine or its salt (XVIII) according to the following reaction scheme.
  • Q ⁇ in formula XVIII stands for the anion of an acid, in particular an inorganic acid (for example halide such as
  • reaction is carried out in a manner known per se in an inert organic solvent in accordance with the methods described in EP-A 513 580, HoubenWeyl Vol. 10/4, p. 73f. or Houben-Weyl Vol. E14b, page 369f. and p. 385f. described methods.
  • the compounds 1.13 are also obtained by first treating the benzyl halide I.2 with the dioxin. XV is converted to the corresponding benzyloxime I.14 and I.14 is then converted to I.13 with a compound XVI.
  • the reaction is carried out in a manner known per se in an inert organic solvent in the presence of a base (e.g. potassium carbonate, potassium hydroxide, sodium hydride, pyridine and triethylamine according to the methods described in Houben-Weyl Vol. 10/1, p. 1189f., Houben-Weyl
  • a base e.g. potassium carbonate, potassium hydroxide, sodium hydride, pyridine and triethylamine according to the methods described in Houben-Weyl Vol. 10/1, p. 1189f., Houben-Weyl
  • a further possibility for the preparation of the compounds I.13 consists in first reacting the benzyl halide of the formula I.2 with N-hydroxyphthalimide, converting the product obtained by hydrazinolysis into the corresponding benzylhydroxylamine (I.15) and then I.15 with a ketoxime of the formula XVIIa to implement I.13.
  • R t here means hydrogen, possibly subst. Alkyl, a possibly subst. saturated or partially unsaturated cyclic radical, which in addition to carbon atoms as ring members can contain heteroatoms from the group consisting of oxygen, sulfur and nitrogen, or one. if necessary subst. aromatic ring which, in addition to carbon ring members, can contain heteroatoms from the group consisting of oxygen, sulfur and nitrogen.
  • Alkyl phenylacetates of the formula I in which R represents a group A 1 -Y 1 - are particularly preferred, where A 1 and Y 1 have the following meanings: Y 1 is a direct bond, oxygen, sulfur, amino or
  • Alkyl alkenyl or alkynyl, or
  • alkyl phenylacetates of the formula I are preferred in which R represents CH 2 OA 1 , where A 1 is in particular a optionally subst. saturated or partially unsaturated cyclic radical which, in addition to carbon atoms as ring members, contains heteroatoms from the group consisting of oxygen, sulfur and nitrogen ten can, or wherein A 1 in particular for a possibly subst. aromatic ring which, in addition to carbon ring members, can contain heteroatoms from the group consisting of oxygen, sulfur and nitrogen.
  • Z a oxygen, amino or alkylamino
  • R c is hydrogen, alkyl or cycloalkyl; A 3 if necessary subst. Alkyl, alkenyl or alkynyl, or
  • R f is hydrogen, alkyl or cycloalkyl; A 4 if necessary subst. Alkyl, alkenyl or alkynyl, or
  • a possibly subst. saturated or partially unsaturated cyclic radical which in addition to carbon atoms as ring members can contain heteroatoms from the group consisting of oxygen, sulfur and nitrogen, or an optionally subst. aromatic ring system which, in addition to carbon ring members, can contain heteroatoms from the group consisting of oxygen, sulfur and nitrogen.
  • Phenyl ring To which they are bound, a possibly subst. Form bicycles from the following group: benzofuran, benzothiophene, indole, isoindole or naphthalene.
  • Alkyl saturated, straight-chain or branched hydrocarbon radicals with 1 to 10 carbon atoms, for example C 1 -C 6 -alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1 -Dimethylethyl, pentyl, 1-methylbutyl,
  • Haloalkyl straight-chain or branched alkyl groups with 1 to 10 carbon atoms (as mentioned above), in which case the hydrogen atoms in these groups can be partially or completely replaced by halogen atoms as mentioned above, for example C 1 -C 2 -haloalkyl such as chloromethyl, bromomethyl, dichloromethyl, Trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl,
  • Alkoxy straight-chain or branched alkyl groups with 1 to
  • Haloalkoxy straight-chain or branched haloalkyl groups with 1 to 10 carbon atoms (as mentioned above) which are bonded to the skeleton via an oxygen atom (-O-);
  • Alkylthio straight-chain or branched alkyl groups with 1 to 10 or 1 to 4 carbon atoms (as mentioned above) which are bonded to the skeleton via a sulfur atom (-S-);
  • Alkylamino a straight-chain or branched alkyl group with 1 to 10 carbon atoms (as mentioned above) which is bonded to the skeleton via an amino group (-NH-) or which is bonded to the skeleton via a group -NY 1 - or -NZ a is;
  • Alkenyl unsaturated, straight-chain or branched hydrocarbon radicals with 2 to 10 carbon atoms and a double bond in any position, for example C 2 -C 6 alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl,
  • 2-tetrahydrothienyl 3-tetrahydropyridazinyl, 4-tetrahydropyridazinyl, 2-tetrahydropyrimidinyl, 4-tetrahydropyrimidinyl, 5-tetrahydropyrimidinyl, 2-tetrahydropyrazinyl, 1,3,5-tetrahydro-triazin-2-triazine-2-triazine-2-triazine-2-triazine-2-triazine-2-triazine-2-triazine-2-triazine-2-triazine-2-triazine-2-triazine-2-triazine-2-triazine-2-triazine-2-tetrahydropyrazidyl Tetrahydrotriazin-3-yl;
  • Aryl a one to three core aromatic ring system containing 6 to 14 carbon ring members, e.g. Phenyl, naphthyl and anthracenyl; aromatic ring system which, in addition to carbon ring members, can contain heteroatoms from the group consisting of oxygen, sulfur and nitrogen: aryl as mentioned above or mono- or dinuclear heteroaryl, e.g.
  • 5-membered heteroaryl containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom
  • 5-ring heteroaryl groups which, in addition to carbon atoms, contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members can, for example 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl , 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2 , 4-oxadiazol-3-yl, 1,2,4-ox
  • 6-membered heteroaryl containing one to three or one to four nitrogen atoms 6-ring heteroaryl groups which, in addition to carbon atoms, can contain one to three or one to four nitrogen atoms as ring members, e.g. 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl,
  • Alkylene divalent unbranched chains from 3 to 5 CH 2 groups, e.g. -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH 2 CH 2 CH 2 CH 2 - and - CH 2 CH 2 CH 2 CH 2 -;
  • Oxyalkylene divalent unbranched chains of 2 to 4 CH 2 groups, one valence being attached to the skeleton via an oxygen atom, for example -OCH 2 CH 2 -, -OCH 2 CH 2 CH 2 - and -OCH 2 CH 2 CH 2 CH 2 -;
  • Oxyalkyleneoxy divalent unbranched chains from 1 to 3
  • CH 2 groups both valences being bonded to the skeleton via an oxygen atom, for example -OCH 2 O-, -OCH 2 CH 2 O- and -OCH 2 CH 2 CH 2 O-;
  • Oxyalkenyleneoxy divalent unbranched chains from 0 to 2
  • -OCH CHCH 2 CH 2 O-.
  • Alkynyl groups are intended to express that these groups can be partially or completely halogenated (ie the hydrogen atoms of these groups can be partially or completely replaced by the same or different halogen atoms as mentioned above (preferably fluorine, chlorine or bromine) and / or one, to can carry three (preferably one) of the following radicals: cyano, nitro, hydroxy, amino, formyl, carboxyl, aminocarbonyl, alkoxy, haloalkoxy, alkylthio, haloalkylthio, alkylamino, dialkylamino, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, alkylaminocarbonyl, dialkylaminocarbonyl, alkylcarbonylamino, alkoxycarbonylamino , Alkylcarbonyl-N-alkylamino and alkylcarbonyl-N-alkylamino, where the alkyl groups in these radicals preferably contain 1 to 6 carbon
  • Contain 10 ring members in particular 6 ring members (phenyl), the hetaryl residues in particular contain 5 or 6 ring members and the alkyl groups in these residues preferably contain 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms.
  • cyclic (saturated, unsaturated or aromatic) groups can be partially or completely halogenated (ie the hydrogen atoms of these groups can be partially or completely replaced by the same or different halogen atoms as mentioned above (preferably fluorine, chlorine or bromine, in particular fluorine or chlorine) can be replaced and / or one to four (in particular one to three) of the following radicals
  • Cyano nitro, hydroxy, amino, carboxyl, aminocarbonyl, alkyl, haloalkyl, alkenyl, haloalkenyl, alkenyloxy, haloalkenyloxy, alkynyl, haloalkynyl, alkynyloxy, haloalkynyloxy, alkoxy,
  • alkyl groups in these radicals preferably contain 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms and the alkenyl or alkynyl groups mentioned in these radicals contain 2 to 8, preferably 2 to 6, in particular 2 to 4 carbon atoms; and / or one to three (in particular one) of the following radicals, unsubstituted or substituted by customary groups, cycloalkyl, cycloalkoxy, cycloalkylthio, cycloalkylamino, cycloal
  • Contain 8 ring members, in particular 3 to 6 ring members and the alkyl groups in these radicals preferably contain 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms; aryl, aryloxy, arylthio, arylamino, aryl-N-alkylamino, arylalkoxy, arylalkylthio, arylalkylamino, arylalkyl-N-alkylamino, hetaryl, hetaryloxy, hetarylthio, hetarylamino, hetaryloxyarylaryl, arylthioaryl, arylthio, arylthio, arylthio Hetarylalkylamino and hetarylalkyl-N-alkylamino, the aryl radicals preferably 6 to
  • Contain 10 ring members in particular 6 ring members (phenyl), the hetaryl residues in particular contain 5 or 6 ring members and the alkyl groups in these radicals preferably contain 1 to 6 carbon atoms, in particular 1 to 4 carbon atoms and or one or two (in particular one) of the following radicals
  • aryl means in particular phenyl, which is unsubstituted or can be substituted by customary groups, or in which two adjacent C atoms of the cyclic systems are a C 3 -C 5 alkylene,
  • Oxy-C 2 -C 4 -alkenylene, oxy-C 2 -C4-alkenyleneoxy or butadienediyl group can carry, these bridges in turn can be partially or completely halogenated and / or one to three, in particular one or two of the following Residues can carry: C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 1 -C 4 haloalkoxy and C 1 -C 4 alkylthio.
  • R i CHO, CH (OH) CN, CH (OH) CO 2 R ", CH (Hal) CO 2 R” and CH (Hal) -CO- Hal, R "C 1 -C 4 alkyl,
  • Bicyclic, partially or completely unsaturated system which, in addition to carbon ring members, can contain heteroatoms from the group consisting of oxygen, sulfur and nitrogen.
  • n 0, 1, 2 or 3, where the radicals X can be different if n is>1;
  • R a hydrogen, alkyl, haloalkyl or optionally subst.
  • R c , R f are hydrogen, alkyl or cycloalkyl
  • R ⁇ is hydrogen, alkyl, alkylcarbonyl or, if appropriate. subst. Aryl,
  • n 0, 1, 2 or 3, where the radicals X can be different if n is>1;
  • Y a oxymethylene, methyleneoxy, ethylene or ethenylene
  • a a aryl or heteroaryl which can be substituted by conventional groups and / or can carry one or two (in particular one) of the following radicals: formyl or CR iii -zNOR iv .
  • compounds IA are particularly preferred in which Y a is oximethylene.
  • compounds IA in which Y a is ethenylene.
  • compounds IA are particularly preferred in which Y a is ethylene.
  • compounds IA are preferred in which A a for optionally subst.
  • Aryl stands.
  • compounds IA are particularly preferred in which A a for an optionally subst. 6-membered heteroaryl ring.
  • compounds IA are particularly preferred in which A a for optionally subst.
  • compounds IA are particularly preferred in which A a for optionally subst.
  • compounds IA are particularly preferred in which A a for optionally subst.
  • Butadienediyl group these chains in turn being able to carry one to three of the following radicals: halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy,
  • compounds IB are particularly preferred in which Y b represents sulfur.
  • compounds IB are preferred, in which A b for optionally subst. Aryl stands.
  • compounds IB are particularly preferred in which A b represents a subst. 6-membered heteroaryl ring.
  • a b represents a subst. Aryl or hetaryl ring from the group phenyl, pyridyl, pyrimidyl, pyrazinyl and 1,3,5-triazinyl.
  • compounds IB are particularly preferred in which A b for optionally subst. 4-pyridinyl is, which in the 6-position a possibly subst. Phenoxy residue carries.
  • compounds IB are particularly preferred in which A b for optionally subst.
  • Pyrimidyl stands, which is a subst. Pyridinyloxy residue carries.
  • compounds IB are particularly preferred in which A b for optionally subst. 1,3,5-triazinyl is, which in the 4-position a possibly subst. Phenoxy residue carries.
  • R ' R "C 1 -C 4 alkyl
  • R ⁇ is hydrogen, cyano, nitro, halogen or alkyl
  • W is oxygen, sulfur, amino or alkylamino, c 0 or 1
  • n 0, 1, 2 or 3, where the radicals X are different
  • a d cycloalkyl which can carry one to four of the following substituents: cyano, halogen, alkyl, haloalkyl, alkoxycarbonyl, or unsubstituted or substituted by usual groups aryl, arylalkyl or arylalkenyl.
  • compounds ID are preferred in which A d for optionally subst. Cyclopropyl stands.
  • R ' R "C 1 -C 4 alkyl
  • R a is hydrogen, alkyl, haloalkyl or unsubstituted or substituted by customary aryl,
  • Cycloalkyl heterocyclyl, aryl, arylalkyl, aryloxyalkyl, arylalkenyl, aryloxyalkenyl, arylcarbonyl, aryloxycarbonyl, hetaryl, hetarylalkyl, hetaryloxyalkyl, hetarylalkenyl, hetaryloxyalkenyl, hetarylcarbonyl and hetaryloxycarbonyl.
  • compounds IE are particularly preferred in which A e for optionally subst. Arylalkyl.
  • R ' R "C 1 -C 4 alkyl
  • R g hydrogen, halogen, cyano, nitro, optionally subst.
  • compounds IF are particularly preferred in which R g is haloalkyl. Furthermore, compounds IF in which R g is cyano are particularly preferred.
  • compounds IF are particularly preferred in which R g represents alkylthio.
  • compounds IF are particularly preferred in which R g represents methyl, ethyl, n-propyl, cyclopropyl, trifluoromethyl, cyano or methylthio.
  • compounds IF are preferred, in which R h for optionally subst. Aryl stands.
  • compounds IF are particularly preferred in which R h for optionally subst. Phenyl or pyridyl.
  • compounds of the formula IG are preferred
  • R ' R "C 1 -C 4 alkyl
  • a g hydrogen optionally subst.
  • compounds I. G preferred, in which A g for optionally subst. Aryl stands.
  • compounds IG are particularly preferred in which A g for optionally subst. Phenyl stands.
  • compounds IG are particularly preferred in which A g for subst. Alkyl, alkenyl or alkynyl.
  • compounds IG are particularly preferred in which A g for optionally subst. Triazolyl stands.
  • Butadienediyl group these chains in turn being able to carry one to three of the following radicals: halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy,
  • Compounds IH in which X h is hydrogen are particularly preferred.
  • compounds IH are particularly preferred in which A h for subst. Alkenyl stands. Furthermore, compounds IH are particularly preferred in which A h for subst. Alkynyl.
  • compounds IH are particularly preferred in which A h is phenyl substituted by customary groups.
  • Butadienediyl group these chains in turn being able to carry one to three of the following radicals: halogen, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy,
  • R d , R e hydrogen, cyano, nitro, halogen, alkyl, haloalkyl,
  • R f is hydrogen, alkyl or cycloalkyl
  • Z represents oxygen, sulfur or nitrogen and the nitrogen carries hydrogen or C 1 -C 6 alkyl; o 0 or 1;
  • R 1 is hydrogen or C 1 -C 6 alkyl
  • R 2 is hydrogen or C 1 -C 6 alkyl.
  • compounds IK are particularly preferred in which A k for optionally subst.
  • compounds IK are particularly preferred in which A k for optionally subst.
  • Aryl or heteroaryl are particularly preferred.
  • compounds IK are particularly preferred in which A k is methyl or ethyl.
  • compounds I are particularly preferred in which U denotes aminooxi and V denotes oxygen.
  • the compounds I can in relation to the grouping
  • racemates or, if the radical R can take on different spatial shapes, are generally used in the preparation,
  • both the racemates or isomer mixtures and the pure isomers can be used, the pure isomers being able to develop a better action than the racemates or isomer mixtures.
  • Binding to A a is and A a corresponds to one of the groups listed in Table A.

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PCT/EP1995/003405 1994-09-10 1995-08-30 Phenylessigsäurealkylester WO1996007633A1 (de)

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EP0754672A1 (en) * 1994-04-06 1997-01-22 Shionogi & Co., Ltd. Gamma-substituted phenylacetic acid derivative, process for producing the same, and agricultural bactericide containing the same
WO1997009302A1 (en) * 1995-09-08 1997-03-13 Shionogi & Co., Ltd. α-ALKOXYPHENYLACETIC ACID DERIVATIVES, INTERMEDIATE FOR PRODUCING THE SAME, AND PESTICIDE CONTAINING THE SAME
WO1997043248A1 (en) * 1996-05-13 1997-11-20 Shionogi & Co., Ltd. α-SUBSTITUTED BENZYL ETHER DERIVATIVES AND PESTICIDES COMPRISING THE SAME AS ACTIVE INGREDIENTS
US5849758A (en) * 1995-05-30 1998-12-15 American Cyanamid Company Herbicidal 2, 6-disubstituted pyridines and 2, 4-disubstituted pyrimidines
US5929279A (en) * 1995-04-08 1999-07-27 Basf Aktiengesellschaft Preparation of Bisoximes
WO2008072784A1 (en) * 2006-12-14 2008-06-19 Astellas Pharma Inc. Polycyclic acid compounds useful as crth2 antagonists and antiallergic agents
WO2010032873A1 (en) 2008-09-19 2010-03-25 Sumitomo Chemical Company, Limited Seed treatment agent and method for protecting plant
US8592438B2 (en) 2008-03-21 2013-11-26 Sumitomo Chemical Intellectual Property Service, Ltd Plant disease control composition
EP2690954A1 (en) * 2011-03-30 2014-02-05 Sumitomo Chemical Company Limited Method for promoting plant growth
US8871762B2 (en) 2010-03-03 2014-10-28 Sumitomo Chemical Company, Limited Plant disease controlling composition and method for controlling plant disease
US8916595B2 (en) 2010-03-03 2014-12-23 Sumitomo Chemical Company, Limited Plant disease controlling composition and method for controlling plant disease
US8940795B2 (en) 2010-03-03 2015-01-27 Sumitomo Chemical Company, Limited Plant disease controlling composition and method for controlling plant disease
US8940717B2 (en) 2010-03-03 2015-01-27 Sumitomo Chemical Company, Limited Plant disease controlling composition and method for controlling plant disease
US8946298B2 (en) 2010-03-03 2015-02-03 Sumitomo Chemical Company, Limited Plant disease controlling composition and method for controlling plant disease
US9107408B2 (en) 2010-03-03 2015-08-18 Sumitomo Chemical Company, Limited Plant disease controlling composition and method for controlling plant disease
US10051860B2 (en) 2010-03-03 2018-08-21 Sumitomo Chemical Company, Limited Plant disease controlling composition and method for controlling plant disease

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CO5050364A1 (es) * 1997-05-28 2001-06-27 Basf Ag Metodo para controlar hongos nocivos
EP2397459B1 (en) * 2009-02-16 2015-12-16 Sumitomo Chemical Company, Limited Method for producing phenylacetamide compound
JP5326891B2 (ja) * 2009-07-14 2013-10-30 住友化学株式会社 シバ病害の防除方法
JP2011201857A (ja) * 2010-03-03 2011-10-13 Sumitomo Chemical Co Ltd 植物病害防除組成物及び植物病害防除方法
JP2011201852A (ja) * 2010-03-03 2011-10-13 Sumitomo Chemical Co Ltd 植物病害防除組成物及び植物病害防除方法
JP5793896B2 (ja) * 2010-10-07 2015-10-14 住友化学株式会社 植物病害防除組成物及び植物病害防除方法
JP2012097063A (ja) * 2010-10-07 2012-05-24 Sumitomo Chemical Co Ltd 植物病害防除組成物及び植物病害防除方法
JP2012102076A (ja) * 2010-10-14 2012-05-31 Sumitomo Chemical Co Ltd 有害生物防除用組成物及び有害生物防除方法
JP2012102075A (ja) * 2010-10-14 2012-05-31 Sumitomo Chemical Co Ltd 有害生物防除用組成物及び有害生物防除方法
JP2012136503A (ja) * 2010-10-14 2012-07-19 Sumitomo Chemical Co Ltd 有害生物防除用組成物及び有害生物防除方法
JP2012102074A (ja) * 2010-10-14 2012-05-31 Sumitomo Chemical Co Ltd 有害生物防除用組成物及び有害生物防除方法
JP2012106984A (ja) * 2010-10-28 2012-06-07 Sumitomo Chemical Co Ltd 有害生物防除用組成物及び有害生物防除方法

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Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0754672A4 (en) * 1994-04-06 1998-07-08 Shionogi & Co GAMMA-SUBSTITUTED PHENYLACETIC ACID DERIVATIVE, PROCESS FOR OBTAINING SAME, AND AGRICULTURAL BACTERICIDE CONTAINING THE SAME
EP0754672A1 (en) * 1994-04-06 1997-01-22 Shionogi & Co., Ltd. Gamma-substituted phenylacetic acid derivative, process for producing the same, and agricultural bactericide containing the same
US5929279A (en) * 1995-04-08 1999-07-27 Basf Aktiengesellschaft Preparation of Bisoximes
US5849758A (en) * 1995-05-30 1998-12-15 American Cyanamid Company Herbicidal 2, 6-disubstituted pyridines and 2, 4-disubstituted pyrimidines
WO1997009302A1 (en) * 1995-09-08 1997-03-13 Shionogi & Co., Ltd. α-ALKOXYPHENYLACETIC ACID DERIVATIVES, INTERMEDIATE FOR PRODUCING THE SAME, AND PESTICIDE CONTAINING THE SAME
WO1997043248A1 (en) * 1996-05-13 1997-11-20 Shionogi & Co., Ltd. α-SUBSTITUTED BENZYL ETHER DERIVATIVES AND PESTICIDES COMPRISING THE SAME AS ACTIVE INGREDIENTS
US8273745B2 (en) 2006-12-14 2012-09-25 Astellas Pharma Inc Polycyclic acid compounds useful as CRTH2 antagonists and antiallergic agents
WO2008072784A1 (en) * 2006-12-14 2008-06-19 Astellas Pharma Inc. Polycyclic acid compounds useful as crth2 antagonists and antiallergic agents
US8592438B2 (en) 2008-03-21 2013-11-26 Sumitomo Chemical Intellectual Property Service, Ltd Plant disease control composition
US8293681B2 (en) 2008-09-19 2012-10-23 Sumitomo Chemical Company, Ltd. Seed treatment agent and method for protecting plant
WO2010032873A1 (en) 2008-09-19 2010-03-25 Sumitomo Chemical Company, Limited Seed treatment agent and method for protecting plant
US8871762B2 (en) 2010-03-03 2014-10-28 Sumitomo Chemical Company, Limited Plant disease controlling composition and method for controlling plant disease
US8916595B2 (en) 2010-03-03 2014-12-23 Sumitomo Chemical Company, Limited Plant disease controlling composition and method for controlling plant disease
US8940795B2 (en) 2010-03-03 2015-01-27 Sumitomo Chemical Company, Limited Plant disease controlling composition and method for controlling plant disease
US8940717B2 (en) 2010-03-03 2015-01-27 Sumitomo Chemical Company, Limited Plant disease controlling composition and method for controlling plant disease
US8946298B2 (en) 2010-03-03 2015-02-03 Sumitomo Chemical Company, Limited Plant disease controlling composition and method for controlling plant disease
US9107408B2 (en) 2010-03-03 2015-08-18 Sumitomo Chemical Company, Limited Plant disease controlling composition and method for controlling plant disease
US10051860B2 (en) 2010-03-03 2018-08-21 Sumitomo Chemical Company, Limited Plant disease controlling composition and method for controlling plant disease
EP2690954A1 (en) * 2011-03-30 2014-02-05 Sumitomo Chemical Company Limited Method for promoting plant growth
EP2690954A4 (en) * 2011-03-30 2014-09-24 Sumitomo Chemical Co PROCESS FOR PROMOTING PLANT GROWTH

Also Published As

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JPH10505596A (ja) 1998-06-02
AU3387895A (en) 1996-03-27
BR9509004A (pt) 1998-06-02
ZA957545B (en) 1997-03-10
EP0781266A1 (de) 1997-07-02
CA2199422A1 (en) 1996-03-14
IL115158A0 (en) 1995-12-31

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