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  • C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
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  • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

• the present invention relates to the use of 4-aminopyrimidines of the formula I.
• R 1 is hydrogen, halogen, cyano, C 1 -C 4 -alkyl, C r C 14 haloalkyl, C 2 -C 2 -alkenyl,
• C 2 -C 2 alkynyl C 3 -C 8 cycloalkyl, C 1 -C 12 -alkoxy, C r C 12 alkoxy-C r C 12 alkyl, benzyl zyloxy--C 12 alkyl, CrCl 2 - Alkoxy-C 2 -C 12 -alkenyl or C 1 -C 12 -alkoxy-C 2 -C 12 -alkynyl;
• R 2 is hydrogen, halogen, cyano, C r Ci 2 -alkyl, C r C 12 haloalkyl, C 2 -C 12 alkenyl,
• R a, R b are independently hydrogen, -C 6 alkyl, C 2 -C 6 alkenyl, C 2 - C 6 alkynyl, C 3 -C 6 -cycloalkyl or C 4 -C 6 cycloalkenyl;
• R ⁇ is halogen, cyano, hydroxy, mercapto, C 1 -C 10 -alkyl, C r C 10 -haloalkyl, C 2 -C 10 -alkenyl, C 2 -C 10 -alkynyl and C 1 -C 6 -alkoxy .
• R 1 and R 2 may together with the carbon atoms to which they are attached form a five to seven membered ring which may contain one to three identical or different heteroatoms from the group O, N or S;
• D d-C ⁇ -alkyl C 3 -C 8 alkenyl, C 3 -C 8 alkynyl, C r C 6 haloalkyl, C 3 -C 8 - Cyclalkyl; m is O, 1 or 2;
• R z is a group R a which may be bonded directly or via a carbonyl group
• R c is one of the groups mentioned in R a , R b ;
• R d is halogen, cyano, one of the groups mentioned for R a , R b or, together with the carbon to which it is attached, may denote a carbonyl group;
• Z is oxygen or NR c ; YC (H) -R ⁇ , CR e, NN (H) -R C, or NR c; R e is halogen, cyano or one of the groups mentioned under R a , R b ;
• R 3 , R a , R b , R c , R d or R e may be partially or completely halogenated or may carry one to four groups R A :
• R A is halogen, cyano, C r C 8 alkyl, C 2 -C 10 alkenyl, C 2 -C 10 alkynyl, C 1 -C 6 -alkoxy,
• a 1 A ' A "independently of one another hydrogen, C 1 -C 6 -alkyl, C 2 -C 6 -
• the invention relates to novel 4-amniopyrimidines, processes for the preparation of these compounds and agents containing them.
• EP-A 407 899 and EP-A 12 54 903 fungicidal or microbicidal aminopyrimidines are generally proposed. Their action against phytopathogenic harmful fungi, however, is in many cases unsatisfactory. On this basis, the object of the present invention is to provide compounds with improved action and / or broadened spectrum of activity.
• the compounds of formula I have an over known fungicidal compounds increased activity against harmful fungi.
• novel compounds of the formula I can be obtained in various ways.
• the compounds of the formula I are advantageously obtained by reacting substituted ⁇ -keto esters of the formula II with thiourea of the formula III to give 2-thio-4-hydroxypyrimidine of the formula IV.
• the variables in formulas II and IV have the meanings as for formula I and the group R in formula II means C 1 -C 4 -alkyl, for practical reasons, methyl, ethyl or propyl is preferred therein.
• reaction of the substituted .beta.-keto esters of the formula II with thiourea of the formula III can be carried out in the presence or absence of solvents. It is advantageous to use those solvents to which the feed substances are largely inert and in which they are completely or partially soluble.
• the solvents used are, in particular, alcohols such as ethanol, propanols, butanols, glycols or glycol monoethers, diethylene glycols or their monoethers, aromatic hydrocarbons such as toluene, benzene or mesitylene, amides such as dimethylformamide, diethylformamide, dibutylformamide, N, N-dimethylacetamide, lower alkanoic acids such as formic acid, Acetic acid, propionic acid or bases, such as alkali metal and alkaline earth metal hydroxides, alkali metal and alkaline earth metal oxides, alkali metal and alkaline earth metal hydrides, alkali metal amides, alkali metal and alkaline earth metal carbonates and alkali metal hydrogencarbonates, organometallic compounds, in particular alkali metal alkyls, alkyl magnesium halides and alkali metal and alkaline earth metal alkoxides and dimethoxy magnesium, also organic bases, e
• Suitable catalysts are bases, as mentioned above, or acids, such as sulfonic acids or mineral acids.
• the reaction is particularly preferably ne solvent or in chlorobenzene, xylene, dimethyl sulfoxide, N-methyl-pyrrolidone performed.
• Particularly preferred bases are tertiary amines such as tri-isopropylamine, tributylamine, N-methylmorpholine or N-methylpiperidine.
• the temperatures are between 50 and 300 ° C, preferably at 50 to 18O 0 C when working in solution [see. EP-A 770 615; Adv. Het. Chem. Vol. 57, p. 81 ff. (1993)].
• the bases are generally used in catalytic amounts, but they can also be used equimolar, in excess or optionally as a solvent.
• the ⁇ -keto esters of formula II can be prepared as in Organic Synthesis Coli. Vol. 1, p. 248, or are commercially available.
• the 2-thio-4-hydroxypyrimidines of the formula IV are converted into the thioethers V by alkylating agents DX, such as alkyl halides, preferably methyl chloride or methyl bromide, or dimethyl sulfate or methanesulfonic acid methyl ester.
• alkylating agents DX such as alkyl halides, preferably methyl chloride or methyl bromide, or dimethyl sulfate or methanesulfonic acid methyl ester.
• the reaction can be carried out in water or else in a dipolar aprotic solvent, for example N, N-dimethylformamide [cf. No. 5,250,689], it is advantageously carried out in the presence of a base such as, for example, KOH, NaOH, NaHCO 3 and Na 2 CO 3 or pyridine.
• the reaction temperature is preferably 10-60 ° C.
• the compounds of the formula V are reacted with halogenating agents, in particular chlorinating or brominating agents, to give the compounds of the formula VI in which Hal is chlorine or bromine, in particular chlorine.
• halogenating agents in particular chlorinating or brominating agents
• Suitable chlorinating agents for the reaction of the hydroxy compounds V with the compounds VI are, for example, POCl 3 , PCI 3 / CI 2 or PCI 5 , or mixtures of these reagents.
• the reaction may be carried out in excess chlorinating agent (POCl 3 ) or an inert solvent such as acetonitrile, toluene, chlorobenzene or 1,2-dichloroethane.
• POCl 3 chlorinating agent
• This reaction is usually carried out between 10 and 180 0 C. From practical
• Reasons usually corresponds to the reaction temperature of the boiling point of the chlorinating agent used (POCl 3 ) or the solvent.
• the process is advantageously carried out with addition of N, N-dimethylformamide in catalytic or substoichio- metric quantities or nitrogen bases, such as N, N-dimethylaniline carried out.
• the halogenation product VI is then mittein with ammonia in inert solvents at 100 ° C to 200 0 C to the 4-aminopyrimidines I in which R 3 is a group SD (formula 1.1) is reacted.
• the reaction is preferably carried out with 1 to 10 molar excess of ammonia under pressure of 1 to 100 bar.
• Thioether 1.1 wherein R 3 is a group SD can be oxidized to the corresponding sulfides or the sulfones 1.1.
• the oxidation is carried out [cf .: B. Kor preferably from 10 to 5O 0 C in the presence of protic or aproptischer solvent. Chem. Soc., Vol. 16, pp. 489-492 (1995); Z. Chem., Vol. 17, p. 63 (1977)].
• Suitable oxidizing agents are, for example, hydrogen peroxide or 3-chloroperbenzoic acid.
• Particularly suitable oxidizing agents are hydrogen peroxide or peracids of organic carboxylic acids.
• the oxidation can also be carried out with selenium dioxide [cf .: Ref. WO 02/88127].
• the compounds of the formula I.2 are valuable intermediates for the preparation of further compounds I.
• the compounds I.2 in which D is C 1 -C 4 -alkyl, in particular methyl, are particularly preferred.
• the substituents R 1 and R 2 have the meaning as in formula I.
• the sulfones of formula 1.2 are reacted with compounds of formula VII under basic conditions.
• the alkali metal, alkaline earth metal or ammonium salt of compound VII can be used directly.
• This reaction occurs in the case of reagents with sufficient nucleophilicity under the conditions of nucleophilic substitution; usually at 0 to 200 ° C., preferably at 10 to 150 ° C., in the presence of a dipolar aprotic solvent, such as N, N-dimethylformamide, tetrahydrofuran or acetonitrile [cf. DE-A 39 01 084; Chimia, Vol. 50, pp. 525-530 (1996); Khim. Geterotsikl. Soedin, Vol. 12, pp. 1696-1697 (1998)].
• a dipolar aprotic solvent such as N, N-dimethylformamide, tetrahydrofuran or acetonitrile
• the components are used in an approximately stoichiometric ratio. However, it may be advantageous to use the nucleophile of the formula R 3 -H in excess.
• a base which can be used equimolar or in excess.
• bases are alkali metal carbonates and bicarbonates, for example, Na tert potassium 2 CO 3 and NaHCO 3, nitrogen bases such as triethylamine, tributylamine and pyridine, AlkalimetaJIalkoholate as methoxide or Natriu-. butoxide, alkali metal amides such as NaNH 2 or alkali metal hydrides, such as LiH or NaH, in question.
• Suitable solvents are halogenated hydrocarbons, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, 1,2-dimethoxyethane, dioxane, anisole and tetrahydrofuran, as well as dimethyl sulfoxide, dimethylformamide and dimethylacetamide. Particularly preferred are ethanol, dichloromethane, acetonitrile and tetrahydrofuran. It is also possible to use mixtures of the solvents mentioned.
• Suitable bases are generally inorganic compounds such as alkali metal and alkaline earth metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide and calcium hydroxide, alkali metal and alkaline earth metal hydrides such as lithium hydride, sodium hydride, potassium hydride and calcium hydride, alkali metal and alkaline earth metal carbonates such as lithium carbonate, potassium carbonate and calcium carbonate and into consideration ,
• the bases are generally used in catalytic amounts, but they can also be used in excess.
• the starting materials are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use VII in up to 10 times, in particular up to 3 times the excess, based on 1.2.
• the compounds Va are first halogenated analogously to the reaction sequence described above to give the 4-halopyrimidines VIa, which compounds VIa are reacted with ammonia under the conditions described for the compounds VI to give the corresponding compounds of the formula I.
• Hydroxypyrimidines of the formula Vb are converted with halogenating agents, in particular chlorinating or brominating agents, into halogen compounds of the formula VIb in which Hal is chlorine or bromine, in particular chlorine.
• Suitable chlorinating agents are, for example, POCl 3 , PCI 3 / CI 2 or PCI 5 , or mixtures of these reagents.
• the reaction may be carried out in excess chlorinating agent (POCl 3 ) or an inert solvent such as acetonitrile, toluene, chlorobenzene or 1,2-dichloroethane.
• POCl 3 an inert solvent
• the implementation in POCl 3 is preferred [cf. J. Chem. Soc. (1943) p. 383; Helv. Chim. Acta (1981) Vol. 64, pp. 113-152].
• This reaction is usually carried out between 10 and 180 ° C.
• the reaction temperature usually corresponds to the boiling point of the chlorinating agent (POCl 3 ) or the solvent used.
• the process is advantageously carried out with the addition of N, N-dimethylformamide in catalytic or substoichiometric amounts or nitrogen bases, such as N, N-dimethylaniline.
• VIb By reaction with ammonia, VIb gives 2,4-diaminopyrimidines of the formula I in which R 3 is NH 2 .
• This reaction is usually carried out with ammonia in inert solvents at 100 0 C to 200 0 C.
• the reaction is preferably carried out with 1 to 10 molar excess of ammonia under pressure of 1 to 100 bar.
• the 2-amino group in the formula I can be converted by well-known alkylation or acylation into other groups R 3 , which are bonded via nitrogen.
• Suitable alkylating or acylating agents are preferably the alkylating agents DX, such as dialkyl sulfate, alkyl halides, carboxylic acid chlorides, carboxylic acid anhydrides [cf. Chem. Ber. Vol. 87, p.1769 (1954)]
• the introduction of the substituent R 3 into the nitriles of the formula 1.3 takes place in the case of strong nucleophiles R 3 -H of the formula VII under the conditions of nucleophilic substitution.
• the introduction may also be transition metal catalyzed, such as. B: under the reaction conditions of Suzuki coupling done. This reaction is advantageously carried out under J. Chem. Soc. (1943) p. 388 and J. Org. Chem. (1952) Vol. 17, p. 1320.
• compounds of the formula I can be obtained by reacting substituted acyl cyanides of the formula VIII, in which R 1 and R 2 have the meanings according to formula I, with thiourea of the formula III.
• the reaction can be carried out in the presence or absence of solvents. It is advantageous to use those solvents to which the starting materials are largely inert and in which they are completely or partially soluble.
• Particularly suitable solvents are alcohols such as ethanol, propanols, butanols, glycols or glycol monoethers, diethylene glycols or their monoethers, aromatic hydrocarbons such as toluene, benzene or mesitylene, amides such as dimethylformamide, Diethylformamide, dibutylformamide, N, N-dimethylacetamide, lower alkanoic acids such as formic acid, acetic acid, propionic acid or bases, as mentioned above, and mixtures of these solvents with water in question.
• the reaction temperatures are between 50 and 300 ° C, preferably at 50 to 150 ° C, when working in solution.
• substituted alkyl cyanides of the formula VIII required for the preparation of the compounds I are known in some cases or can be prepared by known methods from alkyl cyanides and carboxylic acid esters with strong bases, e.g. Alkali hydrides, alkali metal alkoxides, alkali metal amides or metal alkyls, are prepared (see: J. Amer., Chem. Soc., Vol. 73, (1951), page 3766).
• compounds of the formula I in which R 3 is NR a CN can also be prepared from 5,6-dialkyl-7-aminotriazolopyrimidines of the formula IX which are reacted under basic conditions with alkylating agents of the formula VIIa.
• x is a nucleophilically exchangeable group, such as a halogen atom, in particular an iodine atom.
• the reaction of VIIa with IX is usually carried out at temperatures of from -78 ° C to 100 0 C, preferably 1O 0 C to 80 0 C, in an inert organic solvent in the presence of a base [cp. WO 01/96314].
• R 1 is C 1 -Cu-haloalkyl, C 1 -C 12 -haloalkoxy-C 1 --C-
• R 1 * is a halogen-free group R 1 .
• R 1 represents a halogenated group R 1 :
• the halogenation is usually carried out at temperatures of 0 ° C to 200 0 C, preferably 20 0 C to 11O 0 C, in an inert organic solvent in the presence of a radical initiator (eg dibenzoyl peroxide or azobisisobutyronitrile or under UV irradiation, eg with a Hg vapor lamp ) or an acid [cf. Synthetic Reagents, Vol. 2, pp. 1-63, Wiley, New York (1974)].
• a radical initiator eg dibenzoyl peroxide or azobisisobutyronitrile or under UV irradiation, eg with a Hg vapor lamp
• an acid cf. Synthetic Reagents, Vol. 2, pp. 1-63, Wiley, New York (1974)
• the reactants are generally reacted with one another in equimolar amounts. It may be advantageous for the yield to use the halogenating agent in an excess based on I '.
• halogenating agents are, for example, elemental halogens (eg Cl 2 , Br 2 , J 2 ), N-bromo-succinimide, N-chloro-succinimide or Dibromdimethylhydrantoin.
• the halogenating agents are generally used in equimolar amounts, in excess or, if appropriate, as solvents.
• the reaction mixtures are worked up in the usual way, e.g. by mixing with water, separation of the phases and optionally chromatographic purification of the crude products.
• the intermediate and end products are z.T. in the form of colorless or pale brownish, viscous oils, which are freed or purified under reduced pressure and at moderately elevated temperature from volatile constituents. If the intermediate and end products are obtained as solids, the purification can also be carried out by recrystallization or trituration.
• Halogen fluorine, chlorine, bromine and iodine
• Alkyl saturated, straight-chain or branched hydrocarbon radicals having from 1 to 4, 6, 8 or 10 carbon atoms, for example C r C 6 alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1, 1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, hexyl, 1, 1-dimethylpropyl, 1,2-dimethylpropyl, 1 Methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1, 3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3- Dimethylbutyl, 1-ethylbutyl, 2-ethylbut
• Haloalkyl straight-chain or branched alkyl groups having 1 to 2, 4 or 6 carbon atoms (as mentioned above), where in these groups partially or completely the hydrogen atoms may be replaced by halogen atoms as mentioned above: in particular CrC 2 -haloalkyl such as chloromethyl, bromomethyl, dichloro methyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2 Chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl
• Alkenyl unsaturated, straight-chain or branched hydrocarbon radicals having 2 to 4, 6, 8 or 10 carbon atoms and one or two double bonds 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, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2 - Butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-benzenyl, 1, 1-dimethyl-2-propenyl, 1,
• Alkynyl straight-chain or branched hydrocarbon groups having 2 to 4, 6, 8 or 10 carbon atoms and one or two triple bonds in any position, for example C 2 -C 6 alkynyl, such as ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2 Butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl 3-butynyl, 3-methyl-1-butynyl, 1, 1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl , 1-methyl-2-pentynyl
• Cycloalkyl mono- or bicyclic, saturated hydrocarbon groups having 3 to 6 or 8 carbon ring members, for example C 3 -C 8 -cycloalkyl, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl;
• 5- or 6-membered heterocyclyl containing one to three nitrogen atoms and / or one oxygen or sulfur atom or one or two oxygen and / or sulfur atoms e.g. 2-tetrahydrofuranyl, 3-tetrahydrofuranyl, 2-tetrahydrothienyl, 3-tetrahydrodienediyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 3-isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5- isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolindinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4-oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imid
• 5-membered heteroaryl containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom 5-membered heteroaryl groups, which besides carbon atoms can contain one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or oxygen atom as ring members.
• 6-membered heteroaryl containing one to three or one to four nitrogen atoms 6-membered ring heteroaryl groups, which in addition to carbon atoms may 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, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl;
• Alkylene divalent linear chains of 1 to 5 CH 2 groups, eg 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 CH 2 ;
• Oxyalkylene divalent unbranched chains of 2 to 4 CH 2 groups, wherein a valence is bonded 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 ;
• Oxyalkylenoxy divalent unbranched chains of 1 to 3 CH 2 groups, both valences being bonded to the skeleton via an oxygen atom, eg OCH 2 O, OCH 2 CH 2 O and OCH 2 CH 2 CH 2 O;
• R 1 and R 2 are independently halogen, cyano, C 1 -C 12 -alkyl, C r C 12 haloalkyl, C 2 -C 12 - alkenyl, C 2 -C 12 alkynyl, , C 3 -C 8 -cycloalkyl, C 1 -C 12 -alkoxy, C 1 -C 6 -alkoxy-C 1 -C 6 -alkyl, where the carbon chains in R 1 and / or R 2 are substituted by one to four identical or different of the following groups R a may be substituted: halogen, cyano, C 1 -C 10 -alkyl, C 1 -C 4 -haloalkyl, C 3 -C 8 -cycloalkyl, C 2 -Ci 0 -
• R 1 and R 2 are independently C 1 -C 2 -alkyl, Ci-C 12 haloalkyl, C 2 -C 2 -alkenyl, C 2 -C 12 alkynyl, C 3 -C 8 cycloalkyl, C 1 -C 2 -alkoxy, Ci-C 6 alkoxy-C 6 -alkyl, where the carbon chains in R 1 and / or R 2 may be substituted as described above.
• R 2 is dC 5 alkyl
• C 1 -C 5 are - haloalkyl
• C 2 -C 5 -alkenyl -alkyl C 2 -C 5 kinyl -alkyl
• C 3 -C 5 cycloalkyl C 1 -C 5 -alkoxy
• C 1 -C 4 -AIk- oxy-CrC 4 alkyl which groups are unsubstituted or substituted by halogen, cyano, methyl or ethyl.
• R 2 is C r C 5 alkyl, C r C 5 haloalkyl, C 2 -C 5 alkenyl, C 2 -C 5 alkynyl, C 3 -C 5 -CyCIo - alkyl, C r C 5 alkoxy, C r C 4 alkoxy-C 1 -C 4 alkyl, which groups are unsubstituted or substituted by halogen, cyano, methyl or ethyl.
• R 1 is C 1 -C 12 -AIk ⁇ , C r C 12 haloalkyl, C 2 -C 12 -alkenyl, C 3 -C 12 alkynyl, C 1 - C 6 -
• C r C 4 alkyl where the carbon chains in R 1 and / or R 2 may be partially or completely halogenated or substituted by C 2 -C 5 alkenyl or C 2 -C 5 alkynyl.
• R 2 represents C-pCs-alkyl, C r C 5 haloalkyl, C 2 -C 5 alkenyl, C 2 -C 5 alkynyl, -C 4 alkoxy-C 1 C 4 alkyl, wherein the carbon chains in R 1 and / or R 2 may be partially or completely halogenated.
• R 2 is methyl, ethyl, isopropyl, n-propyl or n-butyl, in particular methyl.
• Halogen atoms in the groups R 1 and / or R 2 are preferably on the ⁇ or on the terminal carbon atom.
• Cyano groups in R 1 and / or R 2 are preferably on the terminal carbon atom. In a further preferred embodiment of the compounds of the formula I, there is no group R b .
• R 3 represents halogen, cyano, hydroxy, mercapto, amino, C 2 -C 6 alkyl, halo-CrC 6 alkyl, C 3 -C 8 cycloalkyl, C r C 6 Alkoxy or C r C 6 alkylthio.
• R 3 is an aromatic five-membered heterocycle, which is preferably bonded via N and / or may be substituted by one or two groups R A.
• R a, R b and R c are preferably independently hydrogen, C 1 -C 6 - alkyl, C 2 -C 6 alkenyl, C 2 -C 6 -Alkiny [or C 3 -C 6 cycloalkyl.
• R z preferably represents the above preferred meanings of R a , R b and R c . Particularly preferred is the meaning -CO-R a .
• D is in particular C 1 -C 4 -alkyl, preferably methyl.
• R is GyC 4 -alkyl, in particular methyl, and R A and R A 'are in particular methyl.
• Table A corresponds, R 2 is n-propyl and R, R A and R A 'are methyl
• Table 164 Compounds of the formula 1.35 in which R 1 for each compound corresponds to one row of Table A, R 2 isopropyl and R, R A and R A 'are methyl
• R 2 denotes n-hexyl and R denotes n-propyl
• Table A corresponds to R 2 n-heptyl and R, R A and R A 'are methyl
• R 2 denotes n-octyl and R denotes iso-propyl

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