Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
  • C07D493/22—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains four or more hetero rings
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
  • C07H19/00—Compounds containing a hetero ring sharing one ring hetero atom with a saccharide radical; Nucleosides; Mononucleotides; Anhydro-derivatives thereof
  • C07H19/01—Compounds containing a hetero ring sharing one ring hetero atom with a saccharide radical; Nucleosides; Mononucleotides; Anhydro-derivatives thereof sharing oxygen
• • 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
  • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
• • 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
  • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
  • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
  • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
  • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
• • 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
  • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
  • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
  • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
  • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
  • A01N47/14—Di-thio analogues thereof
• • A—HUMAN NECESSITIES
  • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
  • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
  • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
  • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
  • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
• • 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
  • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
  • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
  • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
  • A01N47/30—Derivatives containing the group >N—CO—N aryl or >N—CS—N—aryl
• • 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
  • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
  • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
  • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
  • A01N47/32—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing >N—CO—N< or >N—CS—N< groups directly attached to a cycloaliphatic ring

Definitions

• the invention provides (1) a compound of the formula
• R 1 is C 1 -C 12 alkyl, C 3 -C 8 cycloalkyl or C 2 -C 12 alkenyl;
• R 2 is H, unsubstituted or mono- to pentasubstituted C 1 -C 12 alkyl or unsubstituted or mono- to pentasubstituted C 2 -C 12 alkenyl;
• R 3 is C 2 -C 12 alkyl, mono- to pentasubstituted C 1 -C 12 alkyl, unsubstituted or mono- to pentasubstituted C 3 -C 12 cycloalkyl, unsubstituted or mono- to pentasubstituted C 2 -C 12 alkenyl, unsubstituted or mono- to pentasubstituted C 2 -C 12 alkynyl; or
• R 2 and R 3 together are a three- to seven-membered alkylene or a four- to seven-membered alkenylene bridge, in which a CH 2 group may be substituted by O, S or NR 4 ;
• the substituents of the alkyl, alkenyl, alkynyl, alkylene, alkenylene and cycloalkyl radicals mentioned are selected from the group consisting of OH, halogen, halo-C 1 -C 2 alkyl, CN, NO 2 , C 2 -C 6 alkynyl, C 3 -C 8 -cycloalkyl which is unsubstituted or substituted by one to three methyl groups, norbornylenyl, C 3 -C 8 -cycloalkenyl which is unsubstituted or substituted by one to three methyl groups, C 3 -C 8 halocycloalkyl, C 1 -C 12 alkoxy, C 1 -C 6 alkoxy-C 1 -C 6 alkyl, C 3 -C 8 cycloalkoxy, C 1 -C 12 haloalkoxy, C 1 -C 12 alkylthio, C 3 -C 8
• R 4 is C 1 -C 8 alkyl, C 3 -C 8 cycloalkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, benzyl or —C( ⁇ O)—R 5 ;
• R 5 is H, OH, SH, NH 2 , NH(C 1 -C 12 alkyl), N(C 1 -C 12 alkyl) 2 , C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 1 -C 12 alkoxy, C 1 -C 12 haloalkoxy, C 1 -C 6 alkoxy-C 1 -C 6 alkoxy, C 1 -C 12 alkylthio, C 2 -C 8 alkenyloxy, C 2 -C 8 alkynyloxy; phenyl, phenoxy, benzyloxy, NH-phenyl, —N(C 1 -C 6 alkyl)-phenyl, NH—C 1 -C 6 alkyl-C( ⁇ O)—R 7 , —N(C 1 -C 6 alkyl)-C 1 -C 6 alkyl-C( ⁇ O)—R 7 ; or phenyl,
• R 6 is H, C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 2 -C 8 alkenyl, C 2 -C 8 alkynyl, phenyl, benzyl, NH 2 , NH(C 1 -C 12 alkyl), N(C 1 -C 12 alkyl) 2 , —NH-phenyl or —N(C 1 -C 12 alkyl)-phenyl; and
• R 7 is H, OH, C 1 -C 12 alkyl, C 1 -C 12 alkoxy, C 1 -C 6 alkoxy-C 1 -C 6 alkoxy, C 2 -C 8 alkenyloxy, phenyl, phenoxy, benzyloxy, NH 2 , NH(C 1 -C 12 alkyl), N(C 1 -C 12 alkyl) 2 , —NH-phenyl or —N(C 1 -C 12 alkyl)phenyl;
• R 1 is not sec-butyl or isopropyl if R 2 is H and R 3 is 2-hydroxyethyl, isopropyl, n-octyl or benzyl;
• the compounds claimed according to the invention are derivatives of avermectin.
• Avermectins are known to the person skilled in the art. They are a group of structurally closely related pesticidally active compounds which are obtained by fermenting a strain of the microorganism Streptomyces avermitilis . Derivatives of avermectins can be obtained by conventional chemical syntheses.
• the avermectins which can be obtained from Streptomyces avermitilis are referred to as A1a, A1b, A2a, A2b, B1a, B1b, B2a and B2b.
• the compounds referred to as “A” and “B” have a methoxy radical and an OH group, respectively, in the 5-position.
• the “a” series and the “b” series are compounds in which the substituent R 1 (in position 25) is a sec-butyl radical and an isopropyl radical, respectively.
• the number 1 in the name of the compounds means that atoms 22 and 23 are linked by double bonds; the number 2 means that they are linked by a single bond and that the C atom 23 carries an OH group.
• the above nomenclature is adhered to in the description of the present invention to denote the specific structure type in the not naturally occurring avermectin derivatives according to the invention which corresponds to the naturally occurring avermectin.
• What is claimed according to the invention are derivatives of compounds of the B1 series, in particular mixtures of derivatives of avermectin B1a and avermectin B1b.
• carbon-containing groups and compounds contain in each case 1 up to and including 6, preferably 1 up to and including 4, in particular 1 or 2, carbon atoms.
• Halogen as a group per se and also as a structural element of other groups and compounds, such as haloalkyl, haloalkoxy and haloalkylthio—is fluorine, chlorine, bromine or iodine, in particular fluorine, chlorine or bromine, especially fluorine or chlorine.
• Alkyl as a group per se and also as a structural element of other groups and compounds, such as haloalkyl, alkoxy and alkylthio—is, in each case taking into account the number of carbon atoms contained in each case in the group or compound in question, either straightchain, i.e. methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl, or branched, for example
• Cycloalkyl as a group per se and also as a structural element of other groups and compounds, such as, for example, of halocycloalkyl, cycloalkoxy and cycloalkylthio—is, in each case taking into account the number of carbon atoms contained in each case in the group or compound in question, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.
• Alkenyl as a group per se and also as a structural element of other groups and compounds—is, taking into account the number of carbon atoms and conjugated or isolated double bonds contained in the group, either straight-chain, for example vinyl, allyl, 2-butenyl, 3-pentenyl, 1-hexenyl, 1-heptenyl, 1,3-hexadienyl or 1,3-octadienyl, or branched, for example isopropenyl, isobutenyl, isoprenyl, tert-pentenyl, isohexenyl, isoheptenyl or isooctenyl. Preference is given to alkenyl groups having 3 to 12, in particular 3 to 6, especially 3 or 4, carbon atoms.
• Alkynyl as a group per se and also as a structural element of other groups and compounds—is, in each case taking into account the number of carbon atoms and conjugated or isolated double bonds contained in the group or compound in question, either straight-chain, for example ethynyl, propargyl, 2-butynyl, 3-pentynyl, 1-hexynyl, 1-heptynyl, 3-hexen-1-ynyl or 1,5-heptadien-3-ynyl, or branched, for example 3-methylbut-1-ynyl, 4-ethylpent-1-ynyl, 4-methylhex-2-ynyl or 2-methylhept-3-ynyl.
• Preference is given to alkynyl groups having 3 to 12, in particular 3 to 6, especially 3 or 4, carbon atoms.
• Alkylene and alkenylene are straight-chain or branched bridge members; they are in particular —CH 2 —CH 2 —CH 2 —, —CH 2 —CH 2 —CH 2 —, —CH 2 —CH 2 —CH 2 —CH 2 —, —CH 2 (CH 3 )CH 2 —CH 2 —, —CH 2 C(CH 3 ) 2 —CH 2 —, —CH 2 —CH ⁇ CH—CH 2 — or —CH 2 —CH ⁇ CH—CH 2 —CH 2 —.
• Halogen-substituted carbon-containing groups and compounds such as, for example, halogen-substituted alkyl, alkenyl, alkynyl, cycloalkyl, alkoxy or alkylthio, can be partially halogenated or perhalogenated, where in the case of polyhalogenation the halogen substituents can be identical or different.
• haloalkyl as a group per se and also as a structural element of other groups and compounds, such as haloalkoxy or haloalkylthio—are methyl which is mono- to trisubstituted by fluorine, chlorine and/or bromine, such as CHF 2 or CF 3 ; ethyl which is mono- to pentasubstituted by fluorine, chlorine and/or bromine, such as CH 2 CF 3 , CF 2 CF 3 , CF 2 CCl 3 ,CF 2 CHCl 2 , CF 2 CHF 2 , CF 2 CFCl 2 , CF 2 CHBr 2 , CF 2 CHClF, CF 2 CHBrF or CClFCHClF; propyl or isopropyl which is mono- to heptasubstituted by fluorine, chlorine and/or bromine, such as CH 2 CHBrCH 2 Br, CF 2 CHFCF 3 , CH 2
• Aryl is in particular phenyl, naphthyl, anthracenyl or perylenyl, preferably phenyl.
• Heterocyclyl is in particular pyridyl, pyrimidyl, s-triazinyl, 1,2,4-triazinyl, thienyl, furanyl, tetrahydrofuranyl, pyranyl, tetrahydropyranyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, triazolyl, oxazolyl, thiadiazolyl, oxadiazolyl, benzothienyl, quinolinyl, quinoxalinyl, benzofuranyl, benzimidazolyl, benzpyrrolyl, benzthiazolyl, indolyl, cumarinyl or indazolyl, which are preferably attached via a C atom; thienyl, thiazolyl, benzofuranyl, benzothiazolyl, furanyl, tetrahydropyranyl or indolyl is preferred
• R 3 are selected from the group consisting of halogen, C 3 -C 8 cycloalkyl, C 2 -C 8 alkynyl, —C( ⁇ O)R 5 , —NHC( ⁇ O)R 6 , —P( ⁇ O)(OC 1 -C 6 alkyl) 2 ; phenyl, naphthyl, anthracenyl, pyridyl, thiazolyl, imidazolyl, furanyl, quinolinyl, pyrazolyl, which are unsubstituted or, depending on the possibility of substitution on the ring, mono- to trisubstituted;
• R 5 is H, OH, NH 2 , NH(C 1 -C 2 alkyl), N(C 1 -C 2 alkyl) 2 , —O—C 1 -C 2 alkyl-C( ⁇ O)—R 7 , NHC,—C 2 alkyl-C( ⁇ O)—R 7 , C 1 -C 6 alkyl, C 1 -C 2 alkoxy, C 1 -C 2 alkoxy-C 1 -C 2 alkoxy, C 2 -C 4 alkenyloxy, C 2 -C 4 alkynyloxy; phenyl, phenoxy, benzyloxy, NH-phenyl, NH—C 1 -C 6 alkyl-C( ⁇ O)—R 7 ; or phenyl, phenoxy, benzyloxy, NH-phenyl which are substituted by halogen, nitro, methoxy, trifluoromethyl or trifluoromethoxy;
• R 6 is H, C 1 -C 3 alkyl, phenyl or benzyl
• R 7 is H, OH, NH 2 , NH(C 1 -C 12 alkyl), N(C 1 -C 12 alkyl) 2 , C 1 -C 12 alkyl, C 1 -C 12 alkoxy, C 1 -C 6 alkoxy-C 1 -C 6 alkoxy, C 2 -C 8 alkenyloxyl, phenyl, phenoxy, benzyloxy or NH-phenyl;
• R 5 is H, OH, NH 2 , NH(C 1 -C 2 alkyl), N(C 1 -C 2 alkyl) 2 , C 1 -C 4 alkyl, C 1 -C 12 alkoxy, C 2 -C 4 alkenyloxy, phenyl, phenoxy, benzyloxy, NH-phenyl, NH-C 1 -C 2 alkyl-C( ⁇ O)—O—C 1 -C 2 alkyl-phenyl, —P( ⁇ O)(OC 1 -C 6 alkyl) 2 ; or phenyl, phenoxy, benzyloxy or NH-phenyl which are substituted by chlorine, fluorine, methoxy, trifluoromethyl or trifluoromethoxy;
• R 5 is C 1 -C 12 alkoxy
• R 3 is C 2 -C 10 alkenyl, in particular C 2 -C 4 alkenyl, which is unsubstituted or mono- or disubstituted, in particular monosubstituted, by C 2 -C 4 alkynyl, —C( ⁇ O)—C 1 -C 4 alkoxy, —C( ⁇ O)—O—C 1 -C 4 alkylbenzoyl, phenyl or halogen; in particular those in which R 3 is —CH 2 —CH ⁇ CH 2 ;
• the invention also provides a process for preparing the compounds of the formula (I) and, if appropriate, tautomers thereof, wherein
• R 1 has the same meanings as given above under (1) for formula (I)
• R 2 is hydrogen and R 3 is a group R 31 —CH—R 32 in which R 31 is C 1 -C 6 alkyl, phenyl, heterocyclyl or unsubstituted or [sic] substituted C 1 -C 6 alkyl, phenyl or heterocyclyl and R 32 is H or unsubstituted or substituted C 1 -C 5 alkyl;
• reaction time is not critical; preference is given to a reaction time of from about 0.1 to about 24 hours, in particular from about 0.5 to about 10 hours.
• the product is isolated by customary methods, for example by filtration, crystallization, distillation or chromatography, or by any suitable combination of these methods.
• solvents or diluents which may be mentioned are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons, such as benzene, toluene, xylene, mesitylene, tetraline, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, carbon tetrachloride, dichloroethane, trichloroethene or tetrachloroethene; ethers, such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxydiethyl ether, te
• ethers particularly suitable are ethers, alcohols, water and carboxylic acids, in particular tetrahydrofuran, acetic acid or water.
• the reactions are advantageously carried out in a temperature range of from about room temperature to the boiling point of the solvent used; preference is given to carrying out the reaction at room temperature.
• the reaction is carried out at room temperature in tetrahydrofuran in the presence of acetic acid. Particularly preferred conditions for the reaction are described in Example H1.1.
• solvents or diluents which may be mentioned are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons and ethers as listed above under process variant (A); ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone; alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol or glycerol; carboxylic esters such as methyl acetate, ethyl acetate or esters of benzoic acid; amides as listed above under process variant (A); nitrites, such as acetonitrile or propionitrile; and sulfoxides, such as dimethyl sulfoxide; and also water; or mixtures of the solvents mentioned.
• ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone
• alcohols such as methanol,
• [0109] particularly [sic] suitable are water, esters of organic acids, halogenated hydrocarbons and aromatic hydrocarbons; in particular two-phase mixtures of such an organic solvent with water.
• the reactions are advantageously carried out in a temperature range of from about room temperature to the boiling point of the solvent used, preferably from room temperature to 90° C., in particular to 60° C., and in the presence of a base, preferably an inorganic base such as, for example, sodium hydroxide, potassium hydroxide, sodium carbonate or sodium bicarbonate.
• a base preferably an inorganic base such as, for example, sodium hydroxide, potassium hydroxide, sodium carbonate or sodium bicarbonate.
• solvents or diluents which may be mentioned are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons and ethers, amides and nitrites as listed above under process variant (A); and sulfoxides, such as dimethyl sulfoxide; or mixtures of the solvents mentioned; particularly suitable are ethers and hydrocarbons; [sic]
• the reactions are advantageously carried out in a temperature range of from 0° C. to the boiling point of the solvent used, preferably from 0° C. to room temperature. Particularly preferred conditions for the reaction are described, for example, in Example H2.2.
• Suitable solvents are the same as mentioned under variant (A), and additionally also ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone; and carboxylic acids such as acetic acid or formic acid; carboxylic esters such as methyl acetate, ethyl acetate or esters of benzoic acid.
• ketones such as acetone, methyl ethyl ketone or methyl isobutyl ketone
• carboxylic acids such as acetic acid or formic acid
• carboxylic esters such as methyl acetate, ethyl acetate or esters of benzoic acid.
• the reactions are advantageously carried out in a temperature range of from about room temperature to the boiling point of the solvent used, preferably in the presence of an inorganic base such as, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate or sodium bicarbonate.
• an inorganic base such as, for example, lithium hydroxide, sodium hydroxide, potassium hydroxide, sodium carbonate or sodium bicarbonate.
• a reaction variant in which a reducing agent, in particular molecular hydrogen, in particular in a mixture of tetrahydrofuran and water as solvent and in the presence of a heavy metal catalyst, in particular a Pd catalyst, is used.
• a reducing agent in particular molecular hydrogen
• a heavy metal catalyst in particular a Pd catalyst
• Suitable solvents are the same as mentioned under variant (B); particularly suitable are esters of organic acids, halogenated hydrocarbons and aromatic hydrocarbons; in particular two-phase mixtures of an ester with water.
• the reactions are advantageously carried out in a temperature range of from 0° C. to the boiling point of the solvent used, preferably from room temperature to 60° C., and in the presence of a base, preferably an inorganic base such as, for example, sodium hydroxide, potassium hydroxide, sodium carbonate or sodium bicarbonate.
• a base preferably an inorganic base such as, for example, sodium hydroxide, potassium hydroxide, sodium carbonate or sodium bicarbonate.
• Suitable for use in an alternative embodiment are the same solvents as mentioned above, preferably ethers, alcohols, water and carboxylic acids, in combination with a hydride such as a borohydride, in particular NaCNBH 3 .
• solvents or diluents which may be mentioned are: aromatic, aliphatic and alicyclic hydrocarbons and halogenated hydrocarbons; ethers, amides and nitrites, as listed above under process variant (A); ketones, such as acetone, methyl ethyl ketone or methyl isobutyl ketone; carboxylic esters such as methyl acetate, ethyl acetate or esters of benzoic acid; and sulfoxides, such as dimethyl sulfoxide; or mixtures of the solvents mentioned.
• esters of organic acids such as ethyl acetate.
• Suitable for use as dehydrating agent are the customary peptide coupling reagents, in particular carbodiimides and hydroxybenzotriazoles.
• the reactions are advantageously carried out in a temperature range of from 0° C. to the boiling point of the solvent used, preferably at room temperature.
• solvents or diluents which may be mentioned are: aromatic, aliphatic and alicyclic hydrocarbons and ethers as listed above under process variant (A); and sulfoxides, such as dimethyl sulfoxide; or mixtures of the solvents mentioned; particularly suitable are ethers, especially tetrahydrofuran.
• the reactions are advantageously carried out in a temperature range of from 0° C. to the boiling point of the solvent used, preferably from 0° C. to room temperature.
• Suitable solvents are the same as mentioned under variant (B), particularly suitable are water, esters of organic acids, halogenated hydrocarbons and aromatic hydrocarbons; in particular two-phase mixtures of such an organic solvent with water.
• the reactions are advantageously carried out in a temperature range of from 0° C. to the boiling point of the solvent used, preferably from 90° C. to the boiling point of the solvent, and in the presence of a base, preferably an inorganic base such as, for example, sodium hydroxide, potassium hydroxide, sodium carbonate or sodium bicarbonate.
• a base preferably an inorganic base such as, for example, sodium hydroxide, potassium hydroxide, sodium carbonate or sodium bicarbonate.
• Suitable solvents are the same as mentioned under variant (B), particularly suitable are water, esters of organic acids, halogenated hydrocarbons and aromatic hydrocarbons; in particular two-phase mixtures of such an organic solvent with water.
• the reactions are advantageously carried out in a temperature range of from 0° C. to the boiling point of the solvent used, preferably from 90° C. to the boiling point, and in the presence of a base, preferably an inorganic base such as, for example, sodium hydroxide, potassium hydroxide, sodium carbonate or sodium bicarbonate.
• a base preferably an inorganic base such as, for example, sodium hydroxide, potassium hydroxide, sodium carbonate or sodium bicarbonate.
• Suitable solvents are the same as mentioned under variant (B), particularly suitable are water, ethers [sic] of organic acids, alcohols and water; in particular two-phase mixtures of an ether with water.
• the reactions are advantageously carried out in a temperature range of from 0° C. to the boiling point of the solvent used, preferably at room temperature.
• the compounds of the formula (I) may be present in the form of one of the possible isomers or as a mixture thereof, as pure isomers or as isomer mixtures, i.e. as a racemic mixture; the invention relates both to the pure isomers and the racemic mixtures and should be understood accordingly in each case above and below, even if stereochemical details are not mentioned specifically in each case.
• racemates may be resolved by known methods into the enantiomers, for example by recrystallization from an optically active solvent, by chromatography on chiral adsorbents, for example high-pressure liquid chromatography (HPLC) on acetylcellulose, with the aid of suitable microorganisms, by cleavage with specific immobilized enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, where only one isomer is complexed.
• HPLC high-pressure liquid chromatography
• optically pure isomers may also be obtained in accordance with the invention by commonly known methods of enantioselective synthesis, for example by performing the process of the invention with starting materials of appropriate stereochemistry.
• the compounds of the formula (I) may also be obtained in the form of their hydrates and/or may include other solvents, examples being those used, where appropriate, for the crystallization of compounds present in solid form.
• the invention relates to all those embodiments of the process which start from a compound obtainable at any stage of the process as a starting material or intermediate and in which all or some of the absent steps are carried out or a starting material is used in the form of a derivative and/or salt and/or its racemates and/or enantiomers or in particular is formed under the reaction conditions.
• the invention relates in particular to the preparation processes described in the examples.
• the compounds of the invention of the formula (I) are preventively and/or curatively valuable active compounds having a very favourable biocidal and very broad spectrum in the field of pest control, even at low use concentrations, while being favourably tolerated by homeotherms, fish and plants.
• they are equally suitable for controlling plant pests and ecto- and endoparasites on humans and especially on useful and domestic animals and pets. They are active against all or individual development stages of normally sensitive, but also resistant, animal pests, such as insects or representatives of the order Acarina, nematodes, cestodes and trematodes, while at the same time sparing useful animals.
• the insecticidal or acaricidal action of the active compounds of the invention may be manifested directly, i.e. in the death of the pests, which occurs directly or only after a certain time, for example during ecdysis, or indirectly, for example in reduced oviposition and/or hatching rate, the good action corresponding to a kill rate (mortality) of at least 50% to 60%.
• Suitable additives are, for example, representatives of the following classes of active compounds: organic phosphorus compounds, nitrophenols and derivatives, formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons, neonicotinoids and Bacillus thuringiensis preparations.
• Particularly suitable mixing partners are, for example: azamethiphos; chlorfenvinphos, bupirimate; cypermethrin, cypermethrin high-cis; cyromazin; diafenthiuron; diazinon; dichlorvos; dicrotophos; dicyclanil; fenoxycarb; fluazuron; furathiocarb; isazofos; jodfenphos; kinoprene; lufenuron; methacriphos; methidathion; monocrotophos; phosphamidon; profenofos; diofenolan; is a substance obtainable from Bacillus thuringiensis strain GC91 or from NCTC11821; pymetrozine; bromopropylate; methoprene; disulfuton; quinalphos; taufluvalinat; thiocyclam; thiometon; aldicarb;
• Examples of the animal pests mentioned include those which are set out in the European Patent Application EP-A-736,252, page 5, line 55, to page 6, line 55. The pests mentioned therein are therefore incorporated by reference in the subject-matter of the present invention.
• the compounds according to the invention can also be used to control pests from the class Nematoda. These include, for example,
• root gall nematodes cyst-forming nematodes, stem nematodes and leaf nematodes; in particular of Heterodera spp., for example Heterodera schachtii, Heterodera avenae and Heterodera trifolii ; Globodera spp., for example Globodera rostochiensis ; Meloidogyne spp., for example Meloidogyne incoginita and Meloidogyne javanica ; Radopholus spp., for example Radopholus simiis ; Pratylenchus, for example Pratylenchus neglectans and Pratylenchus penetrans ; Tylenchulus, for example Tylenchulus semipenetrans ; Longidorus, Trichodorus, Xiphinema, Ditylenchus, Apheenchoides and Anguina; in particular Meloidogyne, for
• the active compounds according to the invention can be used to control pests of the type mentioned which occur on plants, especially on useful plants and ornamentals, in agriculture, in horticulture and in forestry, or on parts of such plants, such as fruits, flowers, foliage, stems, tubers or roots, such control meaning containment or destruction, with the protection against these pests in some cases also extending to plant parts which are formed at a later point in time.
• Particularly suitable target crops include cereals, such as wheat, barley, rye, oats, rice, maize or sorghum, beet, such as sugar beet or fodder beet; fruit, for example pome fruit, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries or berries, for example strawberries, raspberries or blackberries; pulses, such as beans, lentils, peas or soya beans; oil crops, such as oil seed rape, mustard, poppies, olives, sunflowers, coconut, castor-oil plant, cacao or peanuts; curcurbits, such as squash, cucumbers or melons; fibre crops, such as cotton, flax, hemp or jute; citrus fruits, such as oranges, lemons, grapefruit or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes or capsicum; Lauraceae, such as avocado, cinnamon or camphor; and also tobacco, nuts, coffee
• the invention therefore also relates to pesticide compositions, such as—to be chosen in accordance with the intended objectives and prevailing circumstances—emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, sprayable powders, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations of polymeric materials, which comprise—at least—one of the active compounds according to the invention.
• pesticide compositions such as—to be chosen in accordance with the intended objectives and prevailing circumstances—emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, sprayable powders, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations of polymeric materials, which comprise—at least—one of the active compounds according to the invention.
• the active compound is used in pure form, a solid active compound for example in a specific particle size or, preferably, together with—at least—one of the auxiliaries common in the art of formulation, such as extenders, for example solvents or solid carriers, or such as surface-active compounds (surfactants).
• auxiliaries common in the art of formulation, such as extenders, for example solvents or solid carriers, or such as surface-active compounds (surfactants).
• extenders for example solvents or solid carriers, or such as surface-active compounds (surfactants).
• surfactants surface-active compounds
• Suitable for use as formulation auxiliaries are, for example, solid carriers, solvents, stabilizers, slow-release auxiliaries, colorants and, where appropriate, surface-active compounds (surfactants).
• Suitable carriers and auxiliaries here include all of the substances commonly used at [lacuna].
• Suitable auxiliaries, such as solvents, solid carriers, surface-active compounds, nonionic surfactants, cationic surfactants, anionic surfactants and further auxiliaries in the compositions used in accordance with the invention are, for example, the same as those described in EP-A-736 252, page 7, line 51, to page 8, line 39.
• compositions for use in crop protection and on humans and domestic and useful animals generally comprise from 0.1 to 99%, in particular from 0.1 to 95%, of active compound and from 1 to 99.9%, in particular from 5 to 99%, of—at least—one solid or liquid auxiliary, it being possible in general for from 0 to 25%, in particular from 0.1 to 20%, of the compositions to comprise surfactants (% denotes in each case per cent by weight). While concentrated compositions tend to be the preferred commercial product, the end user generally uses dilute compositions with substantially lower concentrations of active compounds.
• compositions according to the invention may also comprise further solid or liquid auxiliaries, such as stabilizers, for example unepoxidized or epoxidized vegetable oils (e.g. epoxidized coconut oil, rape seed oil or soya bean oil), defoamers, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, and also fertilizers or other active compounds for achieving specific effects, for example acaricides, bactericides, fungicides, nematocides, molluscicides or selective herbicides.
• auxiliaries such as stabilizers, for example unepoxidized or epoxidized vegetable oils (e.g. epoxidized coconut oil, rape seed oil or soya bean oil), defoamers, for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, and also fertilizers or other active compounds for achieving specific effects, for example acaricides
• the crop protection compositions according to the invention are prepared in a known manner, in the absence of auxiliaries for example by grinding, sieving and/or compressing a solid active compound or a mixture of active compounds, for example to a particular particle size, and in the presence of at least one auxiliary for example by intimate mixing and/or grinding of the active compound or a mixture of active compounds with the auxiliary or auxiliaries.
• auxiliaries for example by grinding, sieving and/or compressing a solid active compound or a mixture of active compounds, for example to a particular particle size
• at least one auxiliary for example by intimate mixing and/or grinding of the active compound or a mixture of active compounds with the auxiliary or auxiliaries.
• the application techniques for the crop protection compositions i.e. the methods of controlling pests of the abovementioned type, such as spraying, fogging, dusting, brushing, dressing, scattering or watering, which are to be chosen in accordance with the desired objectives and prevailing circumstances, and the use of the compositions for controlling pests of the abovementioned type are also provided by the invention.
• Typical use concentrations are from 0.1 to 1000 ppm, preferably from 0.1 to 500 ppm, of active compound.
• the application rates per hectare are generally from 1 to 2000 g of active compound per hectare, in particular from 10 to 1000 g/ha, preferably from 20 to 600 g/ha.
• a preferred application technique in the field of crop protection is that of application to the foliage of the plants (foliar application), the frequency and the rate of application being guided by the intensity of infestation of the pest in question.
• the active compound may also pass into the plants through the root system (systemic action), by the locus of the plants being drenched with a liquid composition or the active compound in solid form being incorporated into the locus of the plants, for example into the soil, for example in the form of granules (soil application). In the case of paddy rice crops, such granules may be added to the flooded paddy field.
• the crop protection compositions according to the invention are also suitable for protecting plant propagation material, for example seed material, such as fruits, tubers or kernels, or plant cuttings, against animal pests.
• the propagation material may be treated with the composition prior to planting; seed, for example, may be dressed before sowing.
• the active compounds of the invention may also be applied to seed kernels (coating) by either drenching the kernels in a liquid composition or coating them with a solid composition.
• the composition may also be applied to the site of planting where the propagation material is being planted, for example to the seed furrow at the time of sowing.
• the compounds are present as mixtures of the avermectin derivatives B1a and B1b, characterization by customary physical data such as melting point or refractive index makes little sense. For this reason, the compounds are characterized by the retention times which are determined in an analysis by HPLC (high performance liquid chromatography).
• B1a refers to the main component in which R 1 is sec-butyl, with a content of usually more than 80%.
• B1b denotes the minor component in which R 1 is isopropyl.
• the compounds where two retention times are given both for the B1a and for the B1b derivative are mixtures of diastereomers which can be separated chromatographically.
• the pure B1a or B1b component can be obtained during work-up.
• the correct structures of the B1a and B1b components are assigned by mass spectrometry.
• the YMC-Pack ODS-AQ column used for the chromatography of the compounds is manufactured by YMC, Alte Raesfelderstrasse 6, 46514 Schermbeck, Germany. TABLE 1 Compounds of the formula (I) in which R 1 is sec-butyl (B1a) or isopropyl (B1b) and R 2 is hydrogen. Retention time (min) No.
• Example F1 Emulsion concentrates a) b) c) Active compound 25% 40% 50% Calcium dodecylbenzenesulphonate 5% 8% 6% Castor oil polyethylene glycol ether (36 mol of EO) 5% — — Tributylphenol polyethylene glycol ether (30 mol — 12% 4% of EO) Cyclohexanone — 15% 20% Xylene mixture 65% 25% 20%
• Example F2 Solutions a) b) c) d) Active compound 80% 10% 5% 95% Ethylene glycol monomethyl ether 20% — — Polyethylene glycol (MW 400) — 70% — N-methylpyrrolid-2-one 20% — — — — Epoxidized coconut oil — — — 1% Petroleum ether (boiling range: 160-190°) — — 94% —
• Example F3 Granules a) b) c) d) Active compound 5% 10% 8% 21% Kaolin 94% — 79% 54% Finely divided silicic acid 1% — 13% 7% Attapulgite — 90% — 18%
• Example F4 Wettable powder a) b) c) Active compound 25% 50% 75% Sodium lignosulphonate 5% 5% — Sodium lauryl sulphate 3% — 5% Sodium diisobutylnaphthalene sulphonate — 6% 10% Octylphenol polyethylene glycol ether (7-8 mol of — 2% — EO) Finely divided silicic acid 5% 10% 10% Kaolin 62% 27% —
• Example F5 Emulsion concentrate Active compound 10% Octylphenol polyethylene glycol ether (4-5 mol of EO) 3% Calcium dodecylbenzenesulphonate 3% Castor oil polyethylene glycol ether (36 mol of EO) 4% Cyclohexanone 30% Xylene mixture 50%
• Example F6 Extruder granules Active compound 10% Sodium lignosulphonate 2% Carboxymethylcellulose 1% Kaolin 87%
• Example F7 Coated granules Active compound 3% Polyethylene glycol (MW 200) 3% Kaolin 94%
• Example F8 Suspension concentrate Active compound 40% Ethylene glycol 10% Nonylphenol polyethylene glycol ether (15 mol of EO) 6% Sodium lignosulphonate 10% Carboxymethylcellulose 1% Aqueous formaldehyde solution (37%) 0.2% Aqueous silicone oil emulsion (75%) 0.8% Water 32%
• Young soya bean plants are sprayed with an aqueous emulsion spray liquor which comprises 12.5 ppm of active compound, and, after the spray coating has dried on, populated with 10 caterpillars of the first stage of Spodoptera littoralis and then introduced into a plastic container. 3 days later, the reduction in the population in per cent and the reduction in the feeding damage in per cent (% activity) are determined by comparing the number of dead caterpillars and the feeding damage between the treated and the untreated plants.
• the compounds of the tables show good activity.
• the compounds 1.001, 1.002, 1.003, 1.004, 1.005, 1.006, 1.007, 1.008, 1.009, 1.010, 1.011, 1.012, 1.013, 1.014, 1.015, 1.016, 1.017, 1.018, 1.019, 1.020, 1.021, 1.022, 1.023, 1.024, 1.025, 1.026, 1.027, 1.028, 1.029, 1.030, 1.031, 1.032, 1.033, 1.034, 1.035, 1.036, 1.037, 1.038, 1.039, 1.040, 1.041, 1.042, 1.043, 1.044, 1.045 1.046, 1.047, 1.048, 1.050, 1.051, 1.052, 1.053, 1.054, 1.055, 1.056, 1.057, 1.058, 1.059, 1.0
• the compounds of the tables show good activity.
• the compounds 1.001, 1.002, 1.003, 1.004, 1.005, 1.006, 1.007, 1.008, 1.009, 1.010, 1.012, 1.013, 1.014, 1.015, 1.016, 1.017, 1.018, 1.019, 1.020, 1.021, 1.022, 1.023, 1.024, 1.025, 1.026, 1.027, 1.028, 1.029, 1.030, 1.031, 1.032, 1.033, 1.034, 1.035, 1.036, 1.037, 1.038, 1.039, 1.040, 1.041, 1.042, 1.044, 1.045 1.046, 1.047, 1.048, 1.049, 1.050, 1.051, 1.052, 1.053, 1.054, 1.055, 1.056, 1.057, 1.058, 1.059, 1.060, 1.0
• the compounds of the tables show good activity.
• the compounds 1.001, 1.002, 1.003, 1.004, 1.005, 1.006, 1.007, 1.008, 1.009, 1.010, 1.011, 1.012, 1.013, 1.014, 1.015, 1.016, 1.017, 1.018, 1.019, 1.020, 1.021, 1.022, 1.023, 1.024, 1.025, 1.026, 1.027, 1.028, 1.029, 1.030, 1.031, 1.032, 1.033, 1.034, 1.035, 1.036, 1.037, 1.038, 1.039, 1.040, 1.041, 1.042, 1.043, 1.044, 1.045, 1.047, 1.048, 1.052, 1.053, 1.054, 1.055, 1.056, 1.057, 1.069, 1.070, 1.071, 1.072, 1.073,
• Young cabbage plants are sprayed with an aqueous emulsion spray liquor which comprises 12.5 ppm ppm [sic] of the active compound. After the spray coating has dried on, the cabbage plants are populated with 10 caterpillars of the first stage of Plutella xylostella and introduced into a plastic container. Evaluation is carried out after 3 days. The reduction in the population in per cent and the reduction in the feeding damage in per cent (% activity) are determined by comparing the number of dead caterpillars and the feeding damage on the treated and the untreated plants.
• the compounds of Table 1 [sic] show good activity against Plutella xylostella .
• the compounds 1.001, 1.002, 1.003, 1.004, 1.005, 1.006, 1.007, 1.008, 1.009, 1.010, 1.011, 1.012, 1.013, 1.014, 1.015, 1.016, 1.017, 1.018, 1.019, 1.020, 1.021, 1.022, 1.023, 1.024, 1.025, 1.026, 1.027, 1.028, 1.029, 1.030, 1.031, 1.032, 1.033, 1.034, 1.035, 1.037, 1.038, 1.039, 1.040, 1.041, 1.042, 1.043, 1.046, 1.050, 1.051, 1.052, 1.053, 1.054, 1.055, 1.056, 1.057, 1.058, 1.060, 1.061,
• Maize seedlings are sprayed with an aqueous emulsion spray liquor which comprises 12.5 ppm of active compound and, after the spray coating has dried on, populated with 10 larvae of the second stage of Diabrotica balteata and then introduced into a plastic container. After 6 days, the reduction in the population in per cent (% activity) is determined by comparing the number of dead larvae between the treated and the untreated plants.
• the compounds of the tables show good activity.
• Young bean plants are populated with a mixed population of Tetranychus urticae and, after 1 day, sprayed with an aqueous emulsion spray liquor which comprises 12.5 ppm of active compound, incubated at 25° C. for 6 days and then evaluated. The reduction in the population in per cent (% activity) is determined by comparing the number of dead eggs, larvae and adults on the treated and on the untreated plants.
• the compounds of the tables show good activity.
• the compounds 1.001, 1.002, 1.003, 1.004, 1.005, 1.006, 1.007, 1.008, 1.009, 1.010, 1.011, 1.012, 1.013, 1.014, 1.015, 1.016, 1.017, 1.018, 1.019, 1.020, 1.021, 1.022, 1.023, 1.024, 1.025, 1.026, 1.027, 1.028, 1.029, 1.030, 1.031, 1.032, 1.033, 1.034, 1.035, 1.036, 1.037, 1.038, 1.039, 1.040, 1.041, 1.042, 1.043, 1.044, 1.045 1.046, 1.047, 1.048, 1.049, 1.050, 1.051, 1.052, 1.053, 1.054, 1.055, 1.056, 1.057, 1.058, 1.0

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