DE3702039A1 - Novel amine derivatives, processes for their preparation, and their use - Google Patents

Abstract

The invention relates to novel amine and ether derivatives, in particular compounds of the formula <IMAGE> processes for their preparation, and their use as antimycotics and agricultural fungicides.

Description

The invention relates to the use of amine derivatives as antifungals and agrofungicides.

In particular, the invention relates to the use of compounds of the formula wherein

• a) R _{1 is} a group of the formulas and R _{2 is} hydrogen or a lower alkyl group or R ₁ and R ₂ together are a group of the formula mean, in the formulas IIa to IIg R ₇ and R ₈ independently representing hydrogen, halogen, trifluoromethyl, lower alkyl or lower alkoxy and R _{9 representing} hydrogen, halogen, lower alkyl or lower alkoxy, R ₁₀ and R ₁₁ independently represent hydrogen, mean lower alkyl, halogen, trifluomethyl, lower alkoxy or lower alkylthio, where if R ₁₀ or R _{11 is} hydrogen, halogen or a lower alkoxy group, the other substituent is not hydrogen, X is oxygen, sulfur, imino, lower alkylimino or a radical of the formula - (CH ₂ ) - or - (O · CH ₂ ) -, p for 1, 2 or 3, s for 3, 4 or 5 and v for 3, 4, 5 or 6 and in the group of formula IId one or two CH ₂ groups can be replaced by oxygen or sulfur, R ₄ and R _{5 are the} same or different and each represents hydrogen or a lower alkyl group, R _{3 represents} hydrogen, a cycloalkyl, a haloalkyl or is an alkyl group and R _{6 is} a group d he formulas means, where R ₇ and R _{8 have the} above meaning, w for an integer from 2 to 6, Z for oxygen, sulfur or an NR ₃ group, in which R _{3 has the} above meaning, and R ₁₂ for an alkyl, a Alkenyl, an alkynyl, a cycloalkyl, a cycloalkylalkyl, a lower alkoxy, a lower alkoxycarbonyl, a lower alkylthio, the phenyl, a phenylalkyl, a trialkylsilyl, a dialkylphenylsilyl group or for halogen, where the alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, phenyl and phenylalkyl groups can be substituted by phenyl, lower alkoxy, lower alkylthio, phenylalkoxy, lower alkoxyphenyl, lower alkylphenyl, halogenophenyl, halogen or an optionally substituted heterocycle and a carbonyl group may contain or
• b) R _{1 is} a group of the formulas IIa to IIf, as defined under a), R ₂ and R ₃ together form a - (CH ₂ ) _u group, where u is an integer from 1 to 8, and R ₄ , R ₅ and R _{6 have the} above meaning as antifungals and agrofungicides.

Each lower alkyl or lower alkoxy radical has 1 to 4 carbon atoms, especially 2 or 1 carbon atom. Alkyl units have 1 to 12 carbon atoms, especially 2 to 8 carbon atoms, in particular 2 to 6 carbon atoms and preferably 2 to 4 carbon atoms. Everyone Alkenyl or alkynyl has 3 to 6 carbon atoms, especially 3 or 4 carbon atoms, for example allyl, propenyl or propynyl. These alkyl, alkoxy, alkenyl and alkynyl groups can be straight chain or be branched. A preferred cycloalkylidene radical is cyclohexylidene. The term cycloalkyl must be understood to mean polycyclo groups includes, such as bornyl or adamantyl, but is preferably Cyclohexyl, cyclopentyl or cyclopropyl.

Conveniently, R ₇ , R ₈ and R _{9 are} hydrogen or halogen. X is conveniently sulfur, imino or lower alkylimino. R ₁ is preferably a radical of the formulas IIc or IId, or in particular IIa and IIb. R ₂ is preferably hydrogen and R _{3 is} expediently lower alkyl.

The values for p, s, u, v and w are expediently chosen so that a seven-, preferably a five- or six-membered ring is formed. Halogen stands for fluorine, chlorine or bromine.

The present invention also includes methods of making Compounds of formula I, characterized in that

• a) a compound of the formula wherein R ₁ to R _{3 have the} above meaning, with a compound of the formula wherein A is a removable group and R ₄ to R _{6 have the} above meaning, or a compound of the formula wherein R ₁ , R ₂ and A are as defined above, with a compound of the formula wherein R ₃ to R _{6 have the} above meaning, or
• b) for the preparation of compounds of the formula wherein R ₁ , R ₂ , R ₄ , R ₅ and R _{6 have the} above meaning and R ' _{3 represents} a cycloalkyl, haloalkyl or lower alkyl group, in a compound of the formula wherein R ₁ , R ₂ , R ₄ , R ₅ and R _{6 have the} above meaning, the group R ' ₃ introduces or
• c) for the preparation of compounds of the formula wherein R ₁ , R ₂ , R ₃ and R _{6 have the} above meaning, a compound of the formula wherein R ₁ to R _{3 have the} above meaning and R represents a lower alkyl group, with a compound of the formula R ₆ -Me, 6 (VII) wherein R _{6 has the} above meaning and Me stands for a metal equivalent, or for the preparation of compounds of formula wherein R ₁ , R ₃ , R ₄ , R ₅ and R _{6 have the} above meaning, a compound of the formula wherein R and R ₃ to R ₆ have the above significance, with a compound of formula _R1-Me, 6 (VIIa) wherein R ₁ and Me have the above meanings, or
• d) for the preparation of compounds of the formula wherein R ₁ to R _{3 have the} above meaning and R ' ₆ for a group of the formula stands, wherein R ₁₃ , R ₁₄ and R _{15 are the} same or different and each represents hydrogen, a lower alkyl, lower alkoxy, phenyl, phenylalkoxy, lower alkoxyphenyl, lower alkylphenyl, halophenyl group, halogen or an optionally substituted Heterocycle stand, a compound of the formula wherein R ₁ to R ₅ and R _{13 have the} above meaning, with a Wittig reagent of the formula wherein R ₁₄ and R _{15 have the} above meaning, implemented in a manner known per se, or
• e) for the preparation of compounds of the formula wherein R ₁ , R ₂ , R ₄ , R ₅ and R _{6 have the} above meaning, a Schiff base of the formula wherein R ₁ , R ₂ , R ₄ , R ₅ and R _{6 have the} above meaning, reduced.

Process a) can be conventional in the manufacture of tertiary amines Way carried out by condensation of analog starting materials will. The process can be carried out in an inert solvent such as a lower alkanol, for example ethanol, optionally in a mixture with Water, an aromatic hydrocarbon such as benzene or toluene,  a cyclic ether such as dioxane, or a carboxylic acid dialkylamide such as dimethylformamide. The reaction temperature expediently lies between room temperature and boiling temperature of the reaction mixture, preferably at room temperature. The procedure is conveniently in the presence of an acid binder, for example Alkali metal carbonate such as sodium carbonate. The Leaving group A is expediently iodine or preferably bromine or Chlorine or an organic sulfonyloxy radical having 1 to 10 carbon atoms, for example alkylsulfonyloxy, preferably having 1 to 4 carbon atoms such as mesyloxy, or alkylphenylsulfonyloxy, preferably with 7 to 10 Carbon atoms such as tosyloxy.

Process b) can be carried out in a conventional manner for alkylation of secondary amines, e.g. B. by direct alkylation with an alkylating agent, e.g. B. with a halide or sulfate, or by reductive alkylation, in particular by reaction with a suitable aldehyde and subsequent or simultaneous reduction. Reductive alkylation can conveniently be carried out by reacting a compound of formula Ib in an inert solvent, e.g. B. in a lower alkanol such as methanol with the corresponding aldehyde. The reduction can be carried out, for example, using a complex metal hydride as reducing agent, such as NaBH ₄ or NaCNBH ₃ . The reduction can also be carried out, for example, by aqueous NaH ₂ PO ₃ solution (H. Loibner et al., Tetrahedron Letters 1984/2535) or by using formic acid, which can simultaneously serve as a reducing agent and reaction medium.

Process c) can be carried out in a conventional manner for organometallic reactions be performed. The reaction is preferably carried out in an inert Solvents, e.g. B. in an ether, between -20 ° C and + 50 ° C. carried out.  

Process d) can be carried out in a conventional manner for Wittig reactions, preferably in an aprotic solvent such as a cyclic ether, e.g. B. Tetrahydrofuran or an aromatic hydrocarbon, e.g. B. toluene carried out between 20 ° C and the boiling point of the reaction mixture will.

The reduction according to process e) can be carried out, for example, with a complex hydride such as NaBH ₄ . Is preferably in an inert under the reaction conditions, for. B. reacted in a lower alcohol such as methanol and at room temperature.

The end compounds can be prepared from the reaction mixture in a manner known per se Way isolated and cleaned if necessary.

Free base forms of the compounds of formula I can be in salt forms be transferred and vice versa. Suitable acid addition salts are e.g. B. Hydrochloride, hydrogen fumarate or naphthalene 1,5-disulfonate.

The starting compounds of the formulas VI and VIa can be reacted the corresponding amines of the formula IV or Va with formaldehyde and a lower alcohol of the formula ROH can be obtained.

The compounds of the formula Ih can be obtained by reacting a compound of the formula wherein R ₁ and R _{2 have the} above meaning, with a compound of the formula wherein R ₄ and R _{6 have the} above meaning, the starting compounds of the formula Ii by reacting a compound of the formula wherein R ₄ to R _{6 have the} above meaning, with a compound of the formula wherein R ₁ and R _{2 have the} above meaning, are obtained.

The other starting compounds are known or can be analogous to known methods or, analogously as described in the examples, getting produced.

The invention also relates to compounds of the formula wherein

• a) R is a group of the formulas and R is hydrogen or a lower alkyl group or R and R together are a group of the formula mean, in the formulas IIa to IIg R ₇ and R ₈ independently representing hydrogen, halogen, trifluoromethyl, lower alkyl or lower alkoxy and R _{9 representing} hydrogen, halogen, lower alkyl or lower alkoxy, R ₁₀ and R ₁₁ independently represent hydrogen, mean lower alkyl, halogen, trifluomethyl, lower alkoxy or lower alkylthio, where if R ₁₀ or R _{11 is} hydrogen, halogen or a lower alkoxy group, the other substituent is not hydrogen, X is oxygen, sulfur, imino, lower alkylimino or a radical of the formula - (CH ₂ ) - or - (O · CH ₂ ) -, p for 1, 2 or 3, s for 3, 4 or 5 and v for 3, 4, 5 or 6 and in the group of formula IId one or two CH ₂ groups can be replaced by oxygen or sulfur, R ₄ and R _{5 are the} same or different and each represent hydrogen or a lower alkyl group, R represents hydrogen, a cycloalkyl, a haloalkyl or one Alkyl group and R is a group of Formulas means, where R ₇ and R _{8 have the} above meaning, w for an integer from 2 to 6, Z for oxygen, sulfur or an NR group, in which R _{3 has the} above meaning, and R ₁₂ for an alkyl, an alkenyl -, an alkynyl, a cycloalkyl, a cycloalkylalkyl, a lower alkoxy, a lower alkoxycarbonyl, a lower alkylthio, the phenyl, a phenylalklyl, a trialkylsilyl, a dialkylphenylsilyl group or halogen, where the Alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, phenyl or phenylalkoxy, lower alkoxyphenyl, lower alkylphenyl, halophenyl or an optionally substituted heterocycle may be substituted and may contain a carbonyl group, or
• b) R is a group of the formulas IIa to IIf, as defined under a), R and R together form a - (CH ₂ ) _u group, where u is an integer from 1 to 8, and R ₄ , R ₅ and R have the above meaning,
  with the proviso that
  • a) when R is the naphthyl radical, R, R ₄ and R _{5 are} hydrogen, R is hydrogen and R is a group of the formula IIIa in which R _{8 is} hydrogen, R ₁₂ and R _{7 are} not simultaneously halogen and R ₁₂ is not halogen or methyl when R _{7 is} hydrogen, and
  • b) if R for a group of the formulas wherein R and R are hydrogen, a lower alkyl, a lower alkoxy group or halogen and s has the above meaning, R is hydrogen or a lower alkyl group, X is oxygen, sulfur or nitrogen, R ₄ and R _{5 are} hydrogen, R is not for a group of formulas wherein Z ^{I is} oxygen or sulfur, R is hydrogen, R is hydrogen, halogen or a lower alkyl group and R is hydrogen, an alkyl, a cycloalkyl, a haloalkyl group or halogen.

A preferred group of compounds for use as antifungals and agrofungicides are the compounds of formula Ij.

Another preferred group of compounds of the formula I are those wherein

• a) R _{1 is} a group of the formulas IIa to IIf and R _{2 is} hydrogen or a lower alkyl group or R ₁ and R ₂ together are a group of the formula IIg, where in the formulas IIa to IIg R ₇ and R _{8 are} independently Are hydrogen, halogen, trifluoromethyl, lower alkyl or lower alkoxy and R _{9 is} hydrogen, halogen, lower alkyl or lower alkoxy, R ₁₀ and R _{11 are} independently hydrogen, lower alkyl, halogen, trifluomethyl, lower alkoxy or lower alkylthio, where, when R ₁₀ or R _{11 is} hydrogen, halogen or a lower alkoxy group, the other substituent is not hydrogen, X is oxygen, sulfur, imino, lower alkylimino or a radical of the formula - (CH ₂ ) -, p is 1, 2 or 3, s is 3, 4 or 5 and v is 3, 4, 5 or 6 and one or two CH ₂ groups in the group of the formula IId can be replaced by oxygen or sulfur, R ₄ and R _{5 are the} same or are different and each for hydrogen or are a lower alkyl group, R _{3 is} hydrogen, a cycloalkyl, a haloalkyl or an alkyl group and R _{6 is} a group of the formulas IIIa, IIIb, IIIc, IIId or IIIe, where R ₇ and R _{8 are as defined} above, w for an integer from 2 to 6, Z for oxygen, sulfur or an NR ₃ group, in which R _{3 has the} above meaning, and R ₁₂ for an alkyl, an alkenyl, an alkynyl, a cycloalkylalkyl or a lower alkoxy -, a lower alkylthio which is phenyl, a phenylalkyl, a trialkylsilyl, a dialkylphenylsilyl group or represents halogen, the alkyl, alkenyl, alkynyl, cycloalkylalkyl, phenyl and phenylalkyl groups being substituted by lower alkoxy and one May contain carbonyl group, or
• b) R _{1 is} a group of the formulas IIa to IIf, as defined under a), R ₂ and R ₃ together form a - (CH ₂ ) _u group, where u is an integer from 1 to 8, and R ₄ , R ₅ and R _{6 have the} above meaning.

Another preferred group of compounds of the formula I are those wherein

• a) R ₁ for a group of the formulas IIa or IIb
  b) R ₂ for hydrogen or lower alkyl, especially for hydrogen
  c) R ₃ for hydrogen or alkyl, especially for lower alkyl and
  d) R _{6 represents} a group of the formula IIIa,

where R ₇ and R ₈ for hydrogen, halogen or alkoxy, in particular for hydrogen, X for oxygen or sulfur, in particular for sulfur, R ₄ and R ₅ for hydrogen or lower alkyl, in particular for hydrogen, and R ₁₂ for an alkyl, an alkenyl, an alkynyl, a cycloalkylalkyl, a lower alkoxy, a lower alkoxycarbonyl, a lower alkylthio, the phenyl, a phenylalkyl, a trialkylsilyl, a dialkylphenylsilyl group or for halogen, where the alkyl, Alkenyl, alkynyl, cycloalkylalkyl, phenyl and phenylalkyl groups can be substituted by phenyl, lower alkoxy, lower alkylthio, phenylalkoxy, lower alkoxyphenyl, lower alkylphenyl, halophenyl, halogen or an optionally substituted heterocycle and can contain a carbonyl group.

Another preferred group of compounds of the formula I are those in which R _{1 is} a group of the formulas IIa, IIb, IIc, IId or IIe and R _{2 is} hydrogen or a lower alkyl group or R ₁ and R ₂ together are a group of the formula IIg, where R ₇ and R ₈ independently represent hydrogen, halogen, trifluoromethyl, lower alkyl or lower alkoxy and R _{9 represent} hydrogen, halogen, lower alkyl or lower alkoxy, R ₁₀ and R ₁₁ independently represent hydrogen, lower alkyl, halogen, Trifluoromethyl, lower alkoxy or lower alkylthio, where if R ₁₀ or R _{11 is} hydrogen, halogen or a lower alkoxy group, the other substituent is not hydrogen, X is oxygen, sulfur, imino, lower alkylimino or a radical of the formula - (CH ₂ ) - or - (O · CH ₃ ) -, p stands for 1, 2 or 3, s stands for 3, 4 or 5 and v stands for 3, 4, 5 or 6 and one or in the group of formula IId two CH ₂ groups replaced by oxygen or sulfur may be, R ₄ and R _{5 are the} same or different and each represents hydrogen or a lower alkyl group, R _{3 represents} hydrogen, a cycloalkyl, a haloalkyl or an alkyl group and R _{6 is} a group of the formulas IIIa, IIIb, IIIc , IIId or IIIe, where R ₇ and R _{8 have the} above meaning, w for an integer from 2 to 6, Z for oxygen, sulfur or an NR ₃ group, in which R _{3 has the} above meaning, and R ₁₂ for one Alkyl, an alkenyl, an alkynyl, a cycloalkyl, a cycloalkylalkyl, a lower alkoxy, a lower alkoxycarbonyl, a lower alkylthio, the phenyl, a phenylalkyl, a trialkylsilyl, a dialkylphenylsilyl group or for Halogen is, the alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, phenyl and phenylalkyl groups being substituted by phenyl, lower alkoxy, lower alkylthio, phenylalkoxy, lower alkoxyphenyl, lower alkylphenyl, halophenyl, halogen or an optionally substituted one n heterocycle may be substituted and may contain a carbonyl group, or R ₁ denotes a group of the formulas IIa to IIe, R ₂ and R ₃ together form an a (CH ₂ ) _u group, u being an integer from 1 to 8, and R ₄ , R ₅ and R _{6 have the} above meaning.

The compounds of formula I have advantageous chemotherapeutic Properties, in particular they show when used locally or orally an antifungal effect. This effect could be verified using different genera and species of mycetes, e.g. B. from Trichophyton spp, Aspergillus spp, Microsporum spp, Sporothrix scheckii and Candida spp, both in vitro in the tube dilution test  Concentrations from 0.003 to 50 µg / ml as well as in vivo in the experimental Skin mycosis model on guinea pigs and by intravaginal intrauterine or disseminated infection can be detected. At the Skin mycosis model, the substance is taken up in polyethylene glycol and once a day on the infected skin surface for 7 days rubbed. The antifungal effect could be achieved from a concentration of 0.1 to 2% can be determined. The oral effectiveness was in vivo on Guinea pig trichophytic model in a dose range from approx. 2 to 70 mg / kg body weight detected.

For the application, the dose to be administered depends on the one used Connection and the mode of administration and the type of treatment. Man obtains satisfactory administration results in larger mammals a daily dose of approximately 70 to 2000 mg. This amount can if necessary in correspondingly small doses two to four times a day or given in extended release. The compounds of formula I can in a similar way to the preparations known for this purpose, e.g. B. Griseofulvin can be applied. The appropriate daily dose for a particular connection will depend on several factors, e.g. B. of their relative effectiveness. For example, it was found that the preferred compound of this invention, the N-methyl-N- (1-naphthylmethyl) - 4- (2-phenyl-2-propyl) benzylamine a curative dose (i.e. the dose, where all infected with Trichophyton mentagrophytes Δ 158 Guinea pigs are cured mycologically) of about 9 × 6 mg / kg in Miglyol in Comparison to the curative dose of about 9 × 60 mg / kg for griseofulvin in owns this test. It is therefore appropriate that these compounds in Dosage similar or lower than that normally used for griseofulvin used.

The compounds of formula I can be in the form of the free bases or in Form of pharmaceutically acceptable acid addition salts can be used, the salts being of the same order of magnitude the same effectiveness possess like the corresponding free bases. Suitable acid addition salts are z. B. the hydrochloride, hydrogen fumarate and naphthalene-1,5-disulfonate.  

The compounds of formula I can be oral, topical, intravenous or administered parenterally. When making appropriate Administration forms can the compounds of formula I with corresponding Carriers and auxiliaries such as lactose, corn starch, talc, magnesium stearate etc. are mixed. The compounds of formula I can also in Form of ointments or tinctures can be administered.

The compounds of the invention in free form or in one for the Agriculture suitable salt form or in the form of metal complexes are suitable as fungicides for combating phytopathogenic fungi. The good fungicidal activity goes u. a. from in vivo tests against Uromyces Appendiculatus (bean grate) on runner beans as well as against others Rust mushrooms (Hemileia, Puccinia) on coffee, wheat, flax, pelargonium and snapdragon and against Erysiphe cichoracearum on the cucumber and against other powdery mildew fungi (E. graminis f. sp. tritici, E. gram. f. sp. hordei, Podosphaera leucotricha, Uncinula necator) on wheat, barley, apples and Vine at test concentrations from 0.0008 to 0.05%. Further interesting effects are u. a. in vitro against Ustilago maydis with Concentrations from 0.8 to 200 ppm, in vivo against Rhizoctonia solani with Concentrations from 10 to 160 ppm, calculated on the volume of the Substrate. Because in the tests also good plant tolerance and good systemic behavior is found, they are suitable Accordingly, compounds according to the invention for the treatment of above-ground Parts of plants, of planting and seeds, and of the soil Combating phytopathogenic fungi, for example to combat Basidiomycetes, Ascomycetes, Oomycetes, Deuteromycetes, in particular of Basidiomycetes of the order Uredinales (rust fungi) such as Puccinia spp, Hemileia spp, Uromyces spp, from Ascomycetes of the order Erysiphales (powdery mildew) such as Erysiphe spp, Podosphaera spp and Uncinula spp, such as also from Phoma, Rhizoctonia, Helminthosporium.

The amount of the compound according to the invention used is from  various factors, such as the type the compound according to the invention, the subject of the treatment (plant, Soil, seeds), the type of treatment (watering, spraying, spraying, dusting, Spreading, dry pickling, wet pickling, wet pickling, slurry pickling, incrustation), the purpose of treatment (prophylactic or therapeutic) that Type of fungi to be treated and the time of use.

In general, satisfactory results are obtained when the Compound according to the invention in the case of a plant or soil treatment in an amount from about 0.005 to 2, advantageously from about 0.01 to 1 kg / hectare is used. Treatment can if desired be repeated, e.g. B. in an 8 to 30 day interval. Will the Compound used in a seed treatment is obtained in general satisfactory results when the compound is in an amount of about 0.05 to 0.5, advantageously from about 0.1 to 0.3 g / kg of seeds is used.

The term "soil" includes any wax medium, i. H. Soil type, be it natural or artificial.

The compounds of the invention can be used in a wide range of Cultivated plants are used, for example in soya, coffee, Ornamental plants (including geranium, rose), vegetables (including pea, cucumber, celery, Tomato and bean plant), sugar beet, sugar cane, cotton, flax, Corn, grapevine, pome and stiff fruits (apples, pears, plums), and are particularly suitable for use in cereals (e.g. wheat, oats, Barley), especially in wheat.

The invention further comprises fungicidal compositions, containing as a fungicide a compound of the invention in free form or in an agricultural salt form and an inert fungicidal carrier or a solvent. In general the compositions advantageously contain about 0.0005 to 90 about 0.1 to 60 percent by weight of active substance.  

The compositions can be in a concentrated form, which one before diluted in application, or in diluted form that is used directly can be. Examples of preferred forms are wettable Powders, emulsion concentrates, dust forms, spray forms, granules and Forms in which the usual carriers and / or thinners and / or others Tools are installed, which are common in agriculture or are suitable. Application forms of such compositions generally contain between 0.0005 and 10 percent by weight of one Compound according to the invention as an active substance. Typical spray suspensions can, for example, 0.0005 to 0.05, advantageously 0.001 to 0.02 Percentages by weight of active ingredient. Concentrated forms of compositions for fungicidal use generally contain about 2 to 90, advantageously about 5 to 70 percent by weight a compound of the invention as an active ingredient.

Forms of emulsion concentrates contain about 10 to 70, advantageously about 20 to 60 percent by weight of active ingredient. Are preferred solid compositions.

The compositions, which are especially prepared for sprays, advantageously contain a surface-active auxiliary, such as one liquid polyglycol ether, a fatty alkyl sulfate or a lignin sulfonate. In addition to the usual carriers and surfactants the formulations according to the invention can further additional Contain aids with special properties for special purposes, e.g. B. stabilizers, deactivators (for solid formulations on carriers bound with a surface-active compound), active ingredients or auxiliaries contain with special properties for special purposes, e.g. B. Stabilizers, deactivators, (for solid formulations on carriers with bound to a surface-active compound), active substances or auxiliaries, to improve adherence to plants, corrosion inhibitors, Anti-foaming agents and dyes. In addition, other fungicides, Bactericides or other active substances that promote the effect, e.g. B.  Insecticides to which formulations are added.

Examples of fungicidal formulations are described below:

• a) Wettable powder formulation
  50 parts of a compound of formula I are ground with 2 parts of lauryl sulfate, 3 parts of sodium lignin sulfonate and 45 parts of finely divided kaolinite until the average particle size is below 5 microns. The spray liquid obtained can be used as a spray for the foliage as well as for soaking the roots or as a root spray.
• b) Granule formulation
  0.5 part by weight of a binder (a nonionic surfactant) is sprayed onto 94.5 parts by weight of quartz sand in a drum mixer and the whole is mixed vigorously. 5 parts by weight of a compound of the formula I are then added and mixed vigorously to obtain a granule formulation with a particle range of 0.3 to 0.7 mm. The granulate can be added to the soil in which the plants are to be treated or raised.
• c) emulsion concentration
  25 parts by weight of a compound of formula I are mixed with 30 parts by weight of iso-octylphenyl octaglycol ether and 45 parts by weight of a petroleum fraction with a boiling point range of 210-280 ° C (D ₂₀ : 0.92). This concentrate can be diluted with water to the desired concentration.
• d) seed coating or seed treatment
  45 parts of a compound of formula I are mixed with 1.5 parts of an ethylene oxide adduct of diamylphenol decaglycol ether, 2 parts of spindle oil, 51 parts of finely ground talc and 0.5 part of rhodamine B. The mixture is milled in a Contraplex mill at 10,000 rpm until the average particle size is less than 20 microns. The dry powder thus obtained has good adhesiveness and can be added to the seed or the seed, e.g. B. by mixing for 2 to 5 minutes in a slowly rotating kettle.

In the following examples, which explain the invention in more detail, but are not intended to restrict its scope in any way, all the temperatures are in degrees Celsius.

Example 1: N- (5,7-difluoro-1-naphthylmethyl) -N-methyl-4-tert-butylbenzylamine (Method a)

To a mixture of 0.3 g of N-methyl-4-tert-butylbenzylamine, 0.25 g Potassium carbonate and 5 ml of absolute dimethylformamide are 0.4 g of 5.7- Difluoro-1-bromomethylnaphthalene was added dropwise and the mixture was stirred overnight. The Solvent is removed in vacuo and the residue between ether and distributed water. The organic phase is dried and evaporated. The pure product is after chromatography on silica gel (Eluent: hexane / ethyl acetate = 95/5) obtained as an oil.

Example 2: N- (4-tert-butyl-1-cyclohexenylmethyl) -1-naphthylmethylamine (Method e)

2 g of 4-tert-butyl-1-cyclohexenecarbaldehyde, 1.9 g of 1-naphthylmethylamine and 15 ml of toluene are heated to 70 ° with a 4 Å molecular sieve for four hours. The mixture is filtered, washed with ether and the filtrate evaporated. The residue is dissolved in 30 ml of absolute methanol and 2 portions of 0.5 g of sodium borohydride are added within half an hour. The mixture is stirred at room temperature for two hours, evaporated and the residue is partitioned between water and dichloromethane. The organic phase is dried and evaporated. The residue is dissolved in a little methanol, an excess of methanolic hydrochloric acid solution is added and the mixture is evaporated to dryness. The residue is recrystallized from isopropanol / ether. The title compound is obtained as a pure base as an oil by treatment with 1 N sodium hydroxide solution and extraction with ether.
Mp (hydrochloride): 153-155 °.

Example 3: N- (4-tert-butyl-1-cyclohexenylmethyl) -N- (1-naphthylmethyl) - methylamine (method b)

0.8 g of N- (4-tert-butyl-1-cyclohexenylmethyl) -1-naphthylmethylamine are mixed with 13 ml of 1 N NaH ₂ PO ₃ solution and brought into solution by adding 15 ml of dioxane. After adding 1.1 ml of 37% formalin solution, the mixture is heated to 60 ° for half an hour, made alkaline with sodium hydroxide solution and etherified. After drying and evaporating the organic phase, the pure product is obtained as an oil.

Example 4: N-methyl-N- (1-naphthylmethyl) -4- (2-phenyl-2-propyl) benzylamine (Method c)

3 g of 2- (4-bromophenyl) -2-phenylpropane and 265 mg of magnesium are converted into 25 ml ether made the Grignard compound. With vigorous stirring 2.5 g of N-ethoxymethyl-N-methyl-1-naphthylmethylamine at room temperature added dropwise in 5 ml ether and the mixture then 4 Heated to reflux for hours. After the addition of saturated ammonium chloride solution is stirred for 1/2 hour and the aqueous phase with ether extracted. The combined organic phases are dried and that Distilled off solvent. By column chromatography on silica gel (Eluent: toluene / ethyl acetate = 95/5) becomes the pure product as an oil receive.

Example 5: N-methyl-N- (1-naphthylmethyl) -4- [1- (4-methoxyphenyl) - ethyl] benzylamine (method d):

1.37 g of methyltriphenylphosphonium bromide / sodium amide in 5 ml Toluene stirred at room temperature for 15 minutes. 1 g of N-methyl-N- (1- naphthylmethyl) -4- (4-methoxybenzoyl) benzylamine and heated 1.5 hours to reflux. After concentration, the residue is in ether recorded, the precipitate filtered off and the filtrate after concentration chromatographed on silica gel using toluene. The title compound is called an oil receive.

Analogously to that described in Examples 1 to 5, the following compounds of the formula Ik can also be obtained:

The required starting products can be as follows, for example will be obtained:

• A) 4- (3,3-Dimethyl-1-butyl) benzyl bromide (for example 6):
  a3.35 g of 4- (3,3-dimethyl-1-butynyl) toluene, 3.47 g of N-bromosuccinimide and 100 mg of dibenzoyl peroxide in 50 ml of carbon tetrachloride are heated to reflux for 8 hours. The mixture is filtered and the solvent is removed in vacuo. Chromatographic purification on silica gel with hexane as eluent gives the pure product as an oil.

Analogous to that described under A), the following compounds can also will be obtained:

• B) 4-Bromomethyl-4'-methylbenzophenone (for Example 29): oil
  C) 2- (4-Bromomethylphenyl) -2- (4-toluene) propane (for Example 35): oil
  D) 3-tert-butylbenzyl bromide (for Examples 17 and 52): oil
  E) 2- (3,3-Dimethyl-1-butynyl) benzyl bromide (for Example 23): oil
  F) 4- (2-methoxy-2-propyl) benzyl bromide (for Example 25): oil
  G) 3-bromomethyl-6-tert.butylpyridine (for example 72): oil
  H) N-methyl-4-phenylbenzylamine (for example 7):
  10 g of 4-biphenylcarbaldehyde and 40 ml of 33% methylamine solution in ethanol are stirred with 4A molecular sieve overnight at room temperature. The mixture is filtered and concentrated in vacuo. The residue in 60 ml of ethanol is mixed with 2 g of sodium borohydride and stirred for 3 hours. The solvent is removed in vacuo, the residue is partitioned between ether and water and the organic phase is dried and evaporated. The pure base is obtained by silica gel chromatography with dichloromethane / ethanol (9/1) as an oil.
  The following compounds can also be obtained analogously as described under H):
  I) N- (2,3-methylenedioxybenzyl) methylamine (for example 10): oil
  J) N- (1-Naphthylmethyl) cyclopropylamine (for Example 18): oil
  K) N-methyl-2,3-dimethylbenzylamine (for Examples 60 and 61): oil
  L) N-ethoxymethyl-N-methyl-1-naphthylmethylamine (for Examples 4, 37, 50 and 71):
  21 g of N-methyl-1-naphthylmethylamine and 9 g of abs. 3.6 g of paraformaldehyde are added in portions to ethanol while cooling with ice. The mixture is stirred at room temperature for 1 hour. The reaction mixture is mixed with dichloromethane, filtered and evaporated. The pure product is obtained after a vacuum distillation (1.3 mbar / 135-138 °) as a light yellow oil.
  M) N- (5,7-difluoro-1-naphthylmethyl) methylamine (for Examples 1 and 59):
  • a) 4- (2,4-difluorophenyl) -4-one-butyric acid:
    11.4 g of 1,3-difluorobenzene and 28 g of aluminum chloride are placed in 75 ml of dichloromethane, and 10 g of succinic anhydride are added in small portions at 38 °. After the addition, the mixture is refluxed for 6 hours. The mixture is poured onto ice / hydrochloric acid, dichloromethane is added and the mixture is stirred for 1/2 hour. The phases are separated, the aqueous is extracted with dichloromethane and the combined organic phases are shaken out with dilute sodium hydroxide solution. The aqueous alkaline solution is washed with ether and acidified with hydrochloric acid. The precipitate is filtered off, washed with water and dried.
    Mp: 113-115 °.
    b) 4- (2,4-difluorophenyl) butyric acid:
    50 g zinc, 5 g mercury (II) chloride, 2.5 ml conc. Hydrochloric acid and 75 ml of water are stirred well for 10 minutes. The liquid is decanted off and the amalgamated zinc with 30 ml water, 75 ml conc. Hydrochloric acid, 3 ml of acetic acid and 16 g of 4- (2,4-difluorophenyl) -4-one-butyric acid in 40 ml of toluene. The mixture is heated to reflux for 8 hours, 10 ml of conc. Hydrochloric acid are given. The organic phase is separated off, the solution decanted from zinc is extracted with toluene and the combined organic phases are washed with water, dried and evaporated. The residue is dissolved in excess 1N sodium hydroxide solution, 200 mg of palladium on activated carbon are added and the mixture is hydrogenated for 36 hours at room temperature and normal pressure. The mixture is filtered, acidified and extracted with ether. The crystalline crude product can be purified by bulb tube distillation at 0.13 mbar / 120 °.
    Mp: 45-47 °
    c) 5,7-difluoro-1-tetralone:
    120 g of polyphosphoric acid and 12 g of phosphorus pentoxide are stirred at 60 ° until the mixture is homogeneous. 4.3 g of 4- (2,4-difluorophenyl) butyric acid are introduced and the mixture is stirred at 80 ° for 1.5 hours. For working up, it is poured onto ice water and extracted with ether. The combined organic phases are washed with sodium carbonate solution and sodium chloride solution, dried, stirred with a little activated carbon and evaporated. The crude product can be purified by silica gel chromatography (eluent: hexane / ethyl acetate = 4/1) or by vacuum sublimation at 0.65 mbar / 100 °.
    Mp: 89-91 °.
    d) 5,7-difluoro-1-methyl-1-tetralol:
    2 g of 5,7-difluoro-1-tetralone are dissolved in 20 ml of ether and added dropwise to the Grignard compound prepared from 0.34 g of magnesium and 2 g of methyl iodide in ether. After refluxing for 2.5 hours, the mixture is poured onto ice saturated ammonium chloride solution and stirred for 1/2 hour. The aqueous phase is extracted with ether and pure product as a colorless oil is obtained by column chromatography on silica gel (mobile solvent: toluene / ethyl acetate = 9/1).
    e) 5,7-difluoro-1-methylnaphthalene:
    2.5 g of 5,7-difluoro-1-methyl-1-tetralol, 3.6 g of triphenylmethanol and 2.6 g of trifluoroacetic anhydride are refluxed in 16 ml of trifluoroacetic acid for 5 hours. The mixture is poured onto ice water and extracted with dichloromethane. The organic phase is washed neutral with sodium bicarbonate solution, dried and evaporated. The oily crude product can be purified by chromatography on silica gel (eluent: hexane).
    f) 5,7-difluoro-1-bromomethylnaphthalene:
    1.35 g of 5,7-difluoro-1-methylnaphthalene are refluxed in 10 ml of carbon tetrachloride for 4.5 hours with 1.4 g of N-bromosuccinimide and 50 mg of dibenzoyl peroxide. The cooled mixture is filtered and the solvent removed in vacuo. The purity of the crystalline raw product is sufficient for further processing.
    Mp: 74-76.5 °.
    g) N- (5,7-difluoro-1-naphthylmethyl) methylamine:
    2.3 g of 5,7-difluoro-1-bromomethylnaphthalene are dissolved in 10 ml of ethanol and slowly added dropwise with cooling to 15 ml of a 33% methylamine solution in ethanol. After 1 hour the cooling is removed and the mixture is stirred at room temperature overnight. The solvent is removed in vacuo, the residue is taken up in 2N hydrochloric acid, the aqueous phase is washed with ether and made alkaline with solid potassium carbonate. Extraction with ether gives the title compound as a colorless oil.
    Mp (HCl): 224-228 °.
• N) 5,8-difluoro-1-bromomethylnaphthalene (for example 19):
  • a) 5,8-difluoro-4-methyl-1-tetralol:
    5 g of 5,8-difluoro-4-methyl-1-tetralone are dissolved in 75 ml of methanol and 1 g of sodium borohydride is added in small portions. After 2 hours at room temperature, the mixture is concentrated and the residue is partitioned between water and ether. The aqueous phase is extracted with ether and the combined organic phases are dried and evaporated. The pure product is obtained as colorless crystals by recrystallization from n-hexane.
    Mp: 73-75 °.
    b) 5,8-difluoro-1-methylnaphthalene:
    3 g of 5,8-difluoro-4-methyl-1-tetralol are refluxed with 1 g of sulfur for 5 hours. The cold mixture is diluted with ether, filtered and the solvent removed at 0 °. The product is purified by column chromatography on silica gel (mobile phase: hexane).
    c) 5,8-difluoro-1-bromomethylnaphthalene:
    The procedure is analogous to that described under If) and the pure compound is obtained after chromatography on silica gel (mobile phase: hexane / ethyl acetate = 98/2).
• O) (5-fluoro-1-naphthylmethyl) methylamine (for Examples 53 and 65):
  • a) 5-fluoro-1-naphthaldehyde:
    1.95 g of 5-fluoro-1-naphthonitrile in 40 ml abs. Toluene dissolved and cooled to -30 °. At this temperature, 11 ml of diisobutylaluminum hydride (20% in toluene) are added dropwise and then stirring is continued for 2 hours without cooling. The mixture is poured onto 75 ml of ice-cooled 3N hydrochloric acid and stirred vigorously for 4 hours. The phases are separated, the aqueous is extracted with toluene and the combined organic phases are dried and evaporated. The pure product is obtained as colorless crystals after recrystallization from ether / petroleum ether.
    Mp: 93 °.
    b) (5-fluoro-1-naphthylmethyl) methylamine:
    The compound is obtained from 5-fluoro-1-naphthaldehyde and methylamine analogously to that described in Example 2 as a colorless oil.
• P) 4- (dimethylphenylsilyl) benzyl bromide (for example 24):
  • a) 4- (dimethylphenylsilyl) toluene:
    5 g of bromotoluene are dissolved in 30 ml of tetrahydrofuran and the equimolar amount of butyllithium solution in hexane is slowly added at -65 °. After 30 minutes at -65 °, 5 g of dimethylphenylchlorosilane are added dropwise and the cooling is then removed. After 2 hours at room temperature, the mixture is poured onto ice water, extracted with dichloromethane and then distilled in a bulb tube (0.13 mbar / 95 °).
    b) 4- (dimethylphenylsilyl) benzyl bromide:
    The procedure is analogous to that described under A) and a crude product is obtained which is suitable for further reaction without further purification.
• Q) 1-Phenyl-1- (4-bromomethylphenyl) ethylene (for Example 31):
  • a) 1-methoxy-1-phenyl-1-tolylethane:
    2 g of 1-phenyl-1-tolylethanol are stirred overnight with 0.56 g of 80% NaH in 50 ml of tetrahydrofuran, 3.7 g of methyl iodide are added and the mixture is stirred for 6 hours. The mixture is worked up with aqueous HCl, extracted with dichloromethane and the oily product is purified on silica gel using cyclohexane as the eluent.
    b) 1-phenyl-1- (4-bromomethylphenyl) ethylene:
    The procedure is as described under A) and, starting from 1-methoxy-1-phenyl-1-tolylethane, the title compound is obtained as an oil.
• R) 5-chloro-2- (4-bromomethylbenzoyl) thiophene (for example 32):
  • a) 5-chloro-2- (4-methylbenzoyl) thiophene:
    5.17 g of AlCl ₃ are suspended in 1.2 dichloroethane. With cooling, 3.84 g of 2-chlorothiophene and 5 g of p-toluyl chloride are added dropwise, the mixture is stirred for 1.5 hours at room temperature, worked up with aqueous HCl, extracted with dichloromethane and the oily product is purified on silica gel using toluene as the eluent.
    b) 5-chloro-2- (4-bromomethylbenzoyl) thiophene:
    The procedure is analogous to that described under A) and, starting from 5-chloro-2- (4-methylbenzoyl) thiophene, the title compound is obtained as an oil.
• S) 1- (4-chlorophenyl) -1- (4-aminomethylphenyl) cyclopropane (for example 34):
  • a) 1- (4-chlorophenyl) -1- (4-cyanophenyl) ethylene:
    The procedure is analogous to that described in Example 5 and, starting from 4-chloro-4'-cyanobenzophenone, an oily product can be reacted directly.
    b) 1- (4-chlorophenyl) -1- (4-cyanophenyl) cyclopropane:
    600 mg copper powder are etched with 10 mg J ₂ in 10 ml toluene. 1.2 g of Dÿodmethan and 500 mg of 1- (4-cyanophenyl) -1- (4-chlorophenyl) ethylene are added and the mixture is boiled under reflux for 140 hours. The mixture is filtered, the filtrate is concentrated and the oily residue is chromatographed on silica gel using toluene as the eluent.
    c) 1- (4-chlorophenyl) -1- (4-aminomethylphenyl) cyclopropane:
    230 g of lithium aluminum hydride are suspended in 10 ml of tetrahydrofuran. 234 mg of 1- (4-chlorophenyl) -1- (4-cyanophenyl) cyclopropane in 5 ml of tetrahydrofuran are added dropwise and the mixture is heated under reflux for 18 hours. It is hydrolyzed with 1N HCl and extracted with dichloromethane. The oily title compound is reacted further without purification.
• T) N-methyl-3-tert-butyl-2-methoxybenzylamine (for Examples 62 and 63):
  • a) 3-tert-butyl-2-methoxybenzyl bromide:
    The procedure is analogous to that described under A) and, starting from (2-tert-butyl-6-methylphenyl) methyl ether, a crude product is obtained which is suitable for further processing.
    b) N-methyl-3-tert-butyl-2-methoxybenzylamine:
    The procedure is analogous to that described under M / g) and the compound is obtained as a colorless oil.
• U) 1-phenyl- [1- (4-aminomethyl) phenyl] cyclopropane (for example 12):
  The procedure is analogous to that described under S) and, starting from 1-phenyl-1- (4-cyanophenyl) ethylene, the title compound is obtained as an oil.

NMR spectra

Ex .: spectrum

17.9-8.1 (m, 1H); 7.6-7.8 (m, 1H); 7.2-7.6 (m, 6H); 6.98 (ddd, J = 10.5 + 8.5 + 2.5 Hz, 1H); 3.83 (s, 2H); 3.57 (s, 2H); 2.19 (s, 3H); 1.31 (s, 9H). 28.0-8.25 (m, 1H); 7.65-8.0 (m. 2H); 7.30-7.65 (m, 4H); 5.55-5.80 (m, 1H); 4.18 (s, 2H); 3.26 (s, 2H); 1.55-2.30 (m, 5H); 1.50 (s, 1H); 1.0-1.4 (m, 2H); 0.87 (s, 9H). 38.2-8.45 (m, 1H); 7.65-7.95 (m, 2H); 7.30-7.65 (m, 4H); 5.55-5.75 (m, 1H); 3.85 (s, 2H); 2.94 (s, 2H); 2.12 (s, 3H); 1.65-2.2 (m, 5H); 1.05-1.50 (m, 2H); 0.86 (s, 9H). 48.10-8.34 (m, 1H); 7.64-7.95 (m. 2H); 7.03-7.58 (m, 13H); 3.92 (s, 2H); 3.55 (s, 2H); 2.19 (s, 3H); 1.65 (s, 6H). 58.20-8.44 (m, 1H); 7.75-7.85 (m, 2H); 7.37-7.58 (m, 4H); 7.23-7.36 (m, 6H); 6.82-6.87 (m, 2H); 5.34-5.38 (m, 2H); 3.95 (s, 2H); 3.81 (s, 3H); 3.60 (s, 2H); 2.21 (s, 3H). 68.18-8.36 (m, 1H); 7.65-7.95 (m, 2H); 7.18-7.60 (m, 8H); 3.90 (s, 2H); 3.55 (s, 2H); 2.15 (s, 3H); 1.30 (s, 9H). 78.26-8.33 (m, 1H); 7.75-7.88 (m, 2H); 7.28-7.62 (m, 13H); 3.96 (s, 2H); 3.63 (s, 2H); 2.23 (s, 3H). 87.64-8.05 (m, 3H); 7.27-7.53 (m, 4H); 6.86 (s, 2H); 3.85 (s, 2H); 3.58 (s, 2H); 2.33 (s, 6H); 2.25 (s, 3H); 2.13 (s, 3H). 98.20-9.00 (br, 1H); 7.10-7.95 (m, 10H); 3.75-3.95 (m, 1H); 3.77 (d, 1H, J = 13.5 Hz); 3.00-3.25 (m, 1H); 2.80 (d, 1H, J = 13.5 Hz); 1.45-2.10 (m, 7H); 1.27 (s, 9H). 107.32 (s, 4H); 6.70-6.95 (m, 3H); 5.95 (s, 2H); 3.54 (s, 2H); 3.52 (s, 2H); 2.20 (s, 3H); 1.30 (s, 9H). 118.15-8.40 (m, 1H); 7.68-7.95 (m, 2H); 7.25-7.65 (m, 8H); 3.94 (s, 2H); 3.60 (s, 2H); 2.20 (s, 3H); 0.24 (s, 9H). 128.16-8.27 (m, 1H); 7.70-7.88 (m, 2H); 6.84-7.52 (m, 13H); 3.88 (s, 2H); 3.50 (s, 2H); 2.25 (s, 3H); 1.22-1.28 (m, 4H). 137.2-7.85 (m, 10H); 4.9 (dd, J = 7.5 + 4 Hz, 1H); 3.95 (s, 2H); 3.74 (dd, J = 18 + 7.5 Hz, 1H); 3.25 (dd, J = 18 + 4 Hz, 1H); 1.7 (s, 1H); 1.30 (s, 9H). 147.2-7.8 (m, 10H); 5.0 (dd, J = 7.5 + 4 Hz, 1H); 3.25-3.6 (m, 4H); 2.19 (s, 3H); 1.30 (s, 9H). 158.0-8.25 (m, 1H); 7.7-8.0 (m, 2H); 7.2-7.65 (m, 8H); 3.96 (s, 2H); 3.84 (qua, J = 6.5 Hz, 1H); 2.15 (s, 3H); 1.54 (d, J = 6.5 Hz, 3H); 1.33 (s, 9H). 168.15-8.45 (m, 1H); 7.65-8.0 (m. 2H); 7.15-7.65 (m, 13H); 7.1 (s, 2H); 3.95 (s, 2H); 3.6 (s, 2H); 2.2 (s, 3H). 177.15-7.5 (m, 8H); 3.54 (s, 2H); 3.49 (s, 2H); 2.21 (s, 3H); 1.34 (s, 9H); 1.32 (s, 9H). 187.95-8.2 (m, 1H); 7.6-7.95 (m. 2H); 7.1-7.6 (m, 8H); 4.1 (s, 2H); 3.73 (s, 2H); 1.7-2.05 (m, 1H); 1.32 (s, 9H); 0.1-0.4 (m, 4H). 198.0 (d, J = 8 Hz, 1H); 7.76 (d, J = 7 Hz, 1H); 7.52 (dd, J = 8 + 7 Hz, 1H); 7.25-7.35 (AA′BB′-system, 4 H); 7.0-7.13 (m, 2H); 4.11 (d, J = 3 Hz, 2H); 3.64 (s, 2H); 2.21 (s, 3H); 1.3 (s, 9H). 208.05-8.27 (m, 1H); 6.75-7.90 (m, 10H); 3.90 (s, 2H); 3.53 (s, 2H); 2.18 (s, 3H); 1.30 (s, 9H). 218.15-8.40 (m, 1H); 7.65-7.95 (m, 2H); 7.15-7.65 (m, 8H); 4.50 (dt, J = 48 + 5.5 Hz, 2H); 4.12 (s, 2H); 3.70 (s, 2H); 2.84 (dt, J = 26 + 5.5 Hz, 2H); 1.29 (s, 9H). 228.14-8.42 (m, 4H); 7.03 (s, 1H); 3.48 (s, 2H); 3.45 (s, 2H); 2.75-3.05 (m, 8H); 2.08 (s, 3H); 1.85-2.20 (m, 4H); 1.30 (s, 9H). 238.16-8.40 (m, 1H); 7.68-7.95 (m, 2H); 7.04-7.64 (m, 7H); 3.99 (s, 2H); 3.81 (s, 2H); 2.22 (s, 3H); 1.36 (s, 9H). 248.20-8.42 (m, 1H); 7.70-8.00 (m, 2H); 7.24-7.68 (m, 13H); 4.00 (s, 2H); 3.66 (s, 2H); 2.27 (s, 3H); 0.59 (s, 6H). 258.12-8.40 (m, 1H); 7.66-7.95 (m, 2H); 7.20-7.62 (m, 8H); 3.95 (s, 2H); 3.60 (s, 2H); 3.07 (s, 3H); 2.22 (s, 3H); 1.53 (s, 6H). 268.20-8.42 (m, 1H); 7.72-8.12 (m, 4H); 7.30-7.68 (m, 6H); 3.95 (s, 2H); 3.90 (s, 3H); 3.62 (s, 2H); 2.20 (s, 3H). 278.20-8.42 (m, 1H); 7.26-7.98 (m, 10H); 3.97 (s, 2H); 3.61 (s, 2H); 2.21 (s, 3H); 1.34 (s, 9H). 288.20-8.38 (m, 1H); 7.36-7.84 (m, 12H); 6.86-6.98 (m, 2H); 3.98 (s, 2H); 3.86 (s, 3H); 3.64 (s, 2H); 2.21 (s, 3H). 298.27-8.39 (m, 1H); 7.24-7.94 (m, 14H); 4.00 (s, 2H); 3.66 (s, 2H); 2.44 (s, 3H); 2.24 (s, 3H). 308.24-8.34 (m, 1H); 7.74-7.92 (m, 2H); 7.08-7.60 (m, 12H); 5.40 (s, 2H); 3.95 (s, 2H); 3.60 (s, 2H); 2.34 (s, 3H); 2.20 (s, 3H). 318.24-8.35 (m, 1H); 7.74-7.92 (m, 2H); 7.12-7.60 (m, 13H); 5.42-5.47 (m, 2H); 3.95 (s, 2H); 3.60 (s, 2H); 2.20 (s, 3H). 328.30-8.41 (m, 1H); 7.74-7.96 (m, 4H); 7.36-7.64 (m, 7H); 6.98-7.03 (d, J = 4 Hz, 1H); 4.02 (s, 2H); 3.68 (s, 2H); 2.26 (s, 3H). 338.24-8.28 (m, 1H); 7.72-7.85 (m, 3H); 7.34-7.52 (m, 7H); 6.74 (d, J = 4 Hz, 1H); 6.64 (d, J = 4 Hz, 1H); 5.44 (s, 1H); 5.18 (s, 1H); 3.95 (s, 2H); 3.60 (s, 2H); 2.24 (s, 3H). 348.18-8.24 (m, 1H); 7.76-7.84 (m, 2H); 7.08-7.48 (m, 12H); 3.92 (s, 2H); 3.54 (s, 2H); 2.17 (s, 3H); 1.20-1.29 (m, 4H). 358.16-8.28 (m, 1H); 7.74-7.90 (m, 2H); 7.10-7.57 (m, 12H); 3.96 (s, 2H); 3.60 (s, 2H); 2.25 (s, 3H); 2.21 (s, 3H); 1.64 (s, 6H). 368.13-8.35 (m, 1H); 7.64-7.92 (m, 2H); 7.24-7.60 (m, 8H); 3.92 (s, 2H); 3.57 (s, 2H); 2.20 (s, 3H); 1.30 (s, 9H). 378.05-8.4 (m, 1H); 7.6-8.0 (m, 2H); 7.1-7.6 (m, 8H); 3.92 (s, 2H); 3.58 (s, 2H); 2.2 (s, 3H); 1.66 (qua, J = 7 Hz, 6H); 0.64 (t, J = 7 Hz, 9H); 388.20-8.35 (m, 1H); 7.70-7.92 (m, 2H); 7.36-7.60 (m, 4H); 7.05-7.35 (m, 4H); 3.90 (s, 2H); 3.56 (s, 2H); 2.32 (s, 3H); 2.18 (s, 3H). 398.20-8.36 (m, 1H); 7.70-7.95 (m, 2H); 7.15-7.62 (m, 8H); 3.93 (s, 2H); 3.52 (s, 2H); 2.18 (s, 3H). 408.18-8.36 (m, 1H); 7.30-7.96 (m, 8H); 7.00-7.18 (m, 2H); 3.92 (s, 2H); 3.50 (s, 2H); 2.17 (s, 3H). 417.70-7.90 (m, 1H); 7.20-7.55 (m, 7H); 3.82 (s, 2H); 3.59 (s, 2H); 2.16 (s, 3H); 1.32 (s, 9H). 428.18-8.40 (m, 1H)); 7.16-7.90 (m, 10H); 3.99 (s, 2H); 3.58 (s, 2H); 2.56 (qua, 2H, J = 6.75 Hz); 1.28 (s, 9H); 1.10 (t, 3H, J = 6.75 Hz). 438.20-8.42 (m, 1H); 7.30-8.00 (m, 10H); 3.97 (s, 2H); 3.61 (s, 2H); 2.20 (s, 3H). 448.10-8.40 (m, 2H); 7.15-7.65 (m, 7H); 6.75 (d, J = 8 Hz, 1H); 3.99 (s, 3H); 3.84 (s, 2H); 3.55 (s, 2H); 2.08 (s, 3H); 1.30 (s, 9H). 457.75-8.05 (m, 2H); 7.20-7.55 (m, 7H); 3.76 (s, 2H); 3.56 (s, 2H); 2.12 (s, 3H); 1.31 (s, 9H). 467.65-7.90 (m, 1H); 7.20-7.55 (m, 8H); 3.82 (s, 2H); 3.60 (s, 2H); 2.18 (s, 3H); 1.31 (s, 9H). 477.76 (dd, J = 7 + 3 Hz, 1H); 7.2-7.55 (m, 7H); 3.81 (s, 2H); 3.58 (s, 2H); 2.15 (s, 3H); 1.3 (s, 9H). 487.95-8.2 (m, 1H); 7.65-7.95 (m, 2H); 7.10-7.6 (m, 8H); 4.23 (s, 2H); 3.88 (s, 2H); 2.9 (sept, J = 7 Hz, 1H); 1.73 (s, 1H); 1.23 (d, J = 7 Hz, 6H). 498.1-8.4 (m, 1H); 7.65-8.0 (m. 2H); 7.10-7.6 (m, 8H); 3.92 (s, 2H); 3.58 (s, 2H); 2.90 (sept, J = 7 Hz, 1H); 2.2 (s, 3H); 1.24 (d, J = 7 Hz, 6H). 508.1-8.35 (m, 1H); 7.7-7.95 (m, 2H); 7.25-7.65 (m, 8H); 3.95 (s, 2H); 3.6 (s, 2H); 2.2 (s, 3H); 1.64 (qua, J = 7.5 Hz, 2H); 1.26 (s, 6H); 0.66 (t, J = 7.5 Hz, 3H). 517.63-7.7 (m, 1H); 7.15-7.45 (m, 7H); 3.59 (s, 2H); 3.55 (s, 2H); 2.22 (s, 3H); 1.32 (s, 9H). 528.2-8.45 (m, 1H); 7.65-8.0 (m. 2H); 7.10-7.6 (m, 8H); 3.92 (s, 2H); 3.61 (s, 2H); 2.22 (s, 3H); 1.33 (s, 9H). 537.9-8.15 (m, 2H); 7.0-7.6 (m, 8H); 3.9 (s, 2H); 3.56 (s, 2H); 2.19 (s, 3H); 1.3 (s, 9H). 546.73-7.48 (m, 8H); 5.75-5.85 (m, 1H); 4.70-4.85 (m, 2H); 3.52 (s, 2H); 3.28 (d, J = 1.5 Hz, 2H); 2.20 (s, 3H); 1.31 (s, 9H). 557.96-8.18 (m, 1H); 7.62-7.94 (m. 2H); 7.05-7.62 (m, 8H); 4.23 (s, 2H); 3.87 (s, 2H); 2.60 (tr, J = 7.5 Hz, 2H); 2.00 (s, 1H); 1.10-1.80 (m, 4H); 0.91 (tr, J = 7 Hz, 3H). 568.15-8.36 (m, 1H); 7.65-7.95 (m, 2H); 7.04-7.62 (m, 8H); 3.92 (s, 2H); 3.58 (s, 2H); 2.60 (tr, J = 7.5 Hz, 2H); 2.20 (s, 3H); 1.10-1.80 (m, 4H); 0.91 (tr, J = 7 Hz, 3H). 578.02-8.24 (m, 1H); 7.66-8.0 (m, 2H); 7.22-7.64 (m, 8H); 4.26 (s. 2H); 3.90 (s, 2H); 1.69 (s, 1H); 1.33 (s, 9H). 588.16-8.40 (m, 1H); 7.60-7.82 (m, 1H); 7.12-7.58 (m, 8H); 3.90 (s, 2H); 3.56 (s, 2H); 2.20 (s, 3H); 1.32 (s, 9H). 597.96-8.03 (m, 1H); 7.62-7.70 (m, 1H); 7.48-7.55 (m, 1H); 7.36-7.45 (m, 1H); 7.12-7.32 (m, 9H); 6.97 (ddd, J = 10.5, 8.5 and 2.5 Hz, 1H); 3.82 (s, 2H); 3.54 (s, 2H); 2.19 (s, 3H); 1.67 (s, 6H). 607.00-7.45 (m, 7H); 3.52 (s, 2H); 3.50 (s, 2H); 2.27 (s, 6H); 2.13 (s, 3H); 1.31 (s, 9H). 617.00-7.45 (m, 12H); 3.52 (s, 2H); 3.50 (s, 2H); 2.30 (s, 3H); 2.27 (s, 3H); 2.15 (s, 3H); 1.70 (s, 6H). 626.92-7.60 (m, 7H); 3.78 (s, 3H); 3.61 (s, 2H); 3.52 (s, 2H); 2.19 (s, 3H); 1.40 (s, 9H); 1.31 (s, 9H). 636.90-7.60 (m, 12H); 3.78 (s, 3H); 3.61 (s, 2H); 3.51 (s, 2H); 2.19 (s, 3H); 1.68 (s, 6H); 1.40 (s, 9H). 647.74-8.02 (m, 1H); 7.12-7.45 (m, 12H); 3.79 (s, 2H); 3.56 (s, 2H); 2.15 (s, 3H); 1.66 (s, 6H). 657.90-8.15 (m, 2H); 7.02-7.60 (m, 13H); 3.90 (s, 2H); 3.55 (s, 2H); 2.19 (s, 3H); 1.66 (s, 6H). 667.65-7.86 (m, 1H); 7.15-7.55 (m, 13H); 3.82 (s, 2H); 3.59 (s, 2H); 2.18 (s, 3H); 1.68 (s, 6H). 677.10-7.60 (m, 12H); 3.67 (s, 2H); 3.58 (s, 2H); 2.22 (s, 3H); 1.68 (s, 6H). 687.46-7.56 (m, 1H); 7.25-7.40 (m, 5H); 7.14-7.24 (m, 1H); 3.66 (s, 2H); 3.58 (s, 2H); 2.22 (s, 3H); 1.31 (s, 9H). 698.86 (d, J = 5 Hz, 1H); 6.08-6.20 (m, 2H); 7.65-7.73 (m, 1H); 7.46-7.56 (m, 2H); 7.25-7.40 (m, 4H); 3.93 (s, 2H); 3.62 (s, 2H); 2.25 (s, 3H); 1.32 (s, 9H). 708.25 (br s, 1H); 7.70-7.77 (m, 1H); 7.05-7.40 (m, 8H); 3.73 (s, 2H); 3.53 (s, 2H); 2.22 (s, 3H); 1.32 (s, 9H). 718.20-8.25 (m, 1H); 7.74-7.84 (m, 2H); 7.07-7.47 (m, 12H); 3.93 (s, 2H); 3.92 (s, 2H); 3.55 (s, 2H); 2.29 (s, 3H); 2.18 (s, 3H). 728.44-8.60 (m, 1H); 8.16-8.42 (m, 1H); 7.70-7.96 (m, 2H); 7.20-7.68 (m, 6H); 3.98 (s, 2H); 3.56 (s, 2H); 2.22 (s, 3H); 1.35 (s, 9H). A7.22-7.48 (m, 4H); 4.46 (s, 2H); 1.30 (s, 9H). B7.10-7.80 (m, 8H); 4.48 (s, 2H); 2.26 (s, 3H). C7.20 (s, 4H); 7.10 (s, 4H); 4.45 (s. 2H); 2.27 (s, 3H); 1.62 (s, 6H). D7.1-7.5 (m, 4H); 4.48 (s, 2H); 1.34 (s, 9H). E7.15-7.50 (m, 4H); 4.67 (s, 2H); 1.37 (s, 9H). F7.40 (s, 4H); 4.52 (s, 2H); 3.09 (s, 3H); 1.63 (s, 6H). G8.50-8.66 (m, 1H); 7.20-7.80 (m, 2H); 4.50 (s, 2H); 1.35 (s, 9H). H7.20-7.70 (m, 9H); 3.75 (s, 2H); 2.42 (s, 3H); 1.80 (s, 1H). I6.68 (s, 3H); 5.93 (s, 2H); 3.73 (s, 2H); 2.43 (s, 3H); 1.36 (s, 1H). J7.85-8.25 (m, 1H); 7.2-7.8 (m, 6H); 4.2 (s, 2H); 2.1 (qui, J = 5 Hz, 1H); 1.7 (s, 1H); 0.35 (d, J = 5 Hz, 4H). K6.95-7.25 (m, 3H); 3.70 (s, 2H); 2.50 (s, 3H); 2.28 (s, 3H); 2.25 (s, 3H); 1.10 (s, 1H). L8.05-8.35 (m, 1H); 7.15-8.0 (m, 6H); 4.15 (s, 4H); 3.48 (qua, J = 7 Hz, 2H); 2.45 (s, 3H); 1.2 (t, J = 7 Hz, 3H). Ma) 7.98 (dt, J = 9 + 6.5 Hz, 1H); 6.8-7.1 (m, 2H); 5.8-6.8 (br, 1H); 3.2-3.4 (m, 2H); 2.8 (t, J = 6.5 Hz, 2H).
b) 7.15 (dt, J = 8 + 7 Hz, 1H); 6.7-6.9 (m, 2H); 2.68 (t, J = 7 Hz, 2H); 2.38 (t, J = 7 Hz, 2H); 1.75-2.1 (m, 2H).
c) 7.57 (ddd, J = 9, 2.5 + 1.5 Hz, 1H); 7.02 (ddd, J = 9.8 + 2.5 Hz, 1H); 2.93 (t, J = 6.5 Hz, 2H); 2.7 (t, J = 6.5 Hz, 2H); 2.0-2.3 (m, 2H).
d) 7.12 (dd, J = 9 + 2.5 Hz, 1H); 6.86 (ddd, J = 9.8 + 2.5 Hz, 1H); 2.63-2.71 (m, 2H); 1.96 (s, 1H); 1.7-2.0 (m, 4H); 1.51 (s, 3H).
e) 7.8-8.0 (m, 1H); 7.3-7.5 (m, 3H); 6.98 (ddd, J = 10.5, 9 + 2.5 Hz, 1H); 2.6 (s, 3H).
f) 7.85-8.15 (m, 1H); 7.30-7.65 (m, 3H); 6.98 (ddd, J = 10.5, 9 + 2.5 Hz, 1H); 4.80 (s, 2H).
g) 7.80-8.15 (m, 1H); 7.15-7.65 (m, 3H); 6.90 (ddd, J = 10.5, 9 + 2.5 Hz, 1H); 4.02 (s, 2H); 2.48 (s, 3H); 1.38 (s, 1H). Na) 6.8-6.95 (m, 2H); 5.03-5.1 (m, 1H); 3.09 (sext, J = 7 Hz, 1H); 2.57 (dd, J = 7 + 3 Hz, 1H); 1.7-2.02 (m, 4H); 1.34 (dd, J = 7 + 1.5 Hz, 3H).
b) 7.8-8.1 (m, 1H); 6.8-7.6 (m, 4H); 2.8 (d, J = 7.5 Hz, 3H).
c) 7.8-8.2 (m, 1H); 6.85-7.6 (m, 4H); 5.05 (d, J = 2.5 Hz, 2H). Oa) 10.4 (d, J = 1 Hz, 1H); 9.03 (dt, J = 8.8 + 0.7 Hz, 1H); 8.41 (dqui, J = 7.5 + 0.7 Hz, 1H); 8.05 (dd, J = 7 + 1.3 Hz, 1H); 7.71 (dd, J = 7.5 + 7 Hz, 1H); 7.63 (ddd, J = 8.8, 7.8 + 5.9 Hz, 1H); 7.27 (ddd, J = 10.4, 7.8 + 1.0 Hz, 1H).
b) 8.0-8.16 (m, 1H); 7.85-8.0 (m, 1H); 7.35-7.6 (m, 3H); 7.17 (ddd, J = 10.5, 8 + 1 Hz, 1H); 4.20 (s, 2H); 2.56 (s, 3H); 1.5 (s, 1H). Pa) 7.05-7.60 (m, 9H); 2.35 (s, 3H); 0.52 (s, 6H).
b) 7.10-7.60 (m, 9H); 4.38 (s, 2H); 0.52 (s, 6H). Qa) 7.10-7.40 (m, 9H); 3.10 (s, 3H); 2.28 (s, 3H); 1.82 (s, 3H).
b) 7.23 (s, 9H); 5.43 (s, 2H); 4.5 (s, 2H). Ra) 7.71 (d, J = 9 Hz, 2H); 7.39 (d, J = 4 Hz, 1H); 7.25 (d, J = 9 Hz, 2H); 6.95 (d, J = 4 Hz, 1H); 2.40 (s, 3H).
b) 7.30-7.90 (m, 5H); 6.97 (d, J = 4 Hz, 1H); 4.50 (s, 2H). Sa) 7.10-7.80 (m, 8H); 5.55 (s, 2H).
b) 7.15-7.70 (m, 8H); 1.30 (s, 4H).
c) 7.15-7.30 (m, 8H); 3.80 (s. 2H); 1.80 (br s, 2H); 1.25 (s, 4H). Ta) 6.90-7.50 (m, 3H); 4.60 (s, 2H); 3.93 (s, 3H); 1.40 (s, 9H).
b) 6.85-7.40 (m, 3H); 3.80 (s, 5H); 2.46 (s, 3H); 1.50 (br s, 1H); 1.39 (s, 9H). Ub) 7.00-7.50 (m, 9H); 1.32 (s, 4H).
c) 7.15-7.25 (m, 9H); 3.80 (s. 2H); 1.60 (br s, 2H); 1.25 (s, 4H).

Claims (3)

1. Use of compounds of the formula wherein

• a) R _{1 is} a group of the formulas and R _{2 is} hydrogen or a lower alkyl group or R ₁ and R ₂ together are a group of the formula mean, wherein in the formulas IIa to IIg R ₇ and R ₈ independently represent hydrogen, halogen trifluoromethyl, lower alkyl or lower alkoxy and R _{9 represent} hydrogen, halogen, lower alkyl or lower alkoxy, R ₁₀ and R ₁₁ independently represent hydrogen, lower Alkyl, halogen, trifluoromethyl mean lower alkoxy or lower alkylthio, where if R ₁₀ or R _{11 is} hydrogen, halogen or a lower alkoxy group, the other substituent is not hydrogen, X is oxygen, sulfur, imino, lower alkylimino or a radical of the formula - (CH ₂ ) - or - (O · CH ₂ ) -, p for 1, 2 or 3, s for 3, 4 or 5 and v for 3, 4, 5 or 6 and in the group of the formula IIb one or two CH ₂ groups can be replaced by oxygen or sulfur, R ₄ and R _{5 are the} same or different and each represents hydrogen or a lower alkyl group, R _{3 represents} hydrogen, a cycloalkyl, a haloalkyl or an alkyl group and R _{6 is} a group of Formulas means, where R ₇ and R _{8 have the} above meaning, w for an integer from 2 to 6, Z for oxygen, sulfur or an NR ₃ group, in which R _{3 has the} above meaning, and R ₁₂ for an alkyl, a Alkenyl, an alkynyl, a cycloalkyl, a cycloalkylalkyl, a lower alkoxy, a lower alkoxycarbonyl, a lower alkylthio, the phenyl, a phenylalkyl, a trialkylsilyl, a dialkylphenylsilyl group or for halogen, where the alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, phenyl and phenylalkyl groups can be substituted by phenyl, lower alkoxy, lower alkylthio, phenylalkoxy, lower alkoxyphenyl, lower alkylphenyl, halogenophenyl, halogen or an optionally substituted heterocycle and a carbonyl group may contain or
• b) R _{1 is} a group of the formulas IIa to IIf, as defined under a), R ₂ and R ₃ together form a - (CH ₂ ) _u group, where u is an integer from 1 to 8, and R ₄ , R ₅ and R _{6 have the} above meaning as antifungals and agrofungicides.

2. Process for the preparation of compounds of the formula wherein

• a) R _{1 is} a group of the formulas and R _{2 is} hydrogen or a lower alkyl group or R ₁ and R ₂ together are a group of the formula mean, in the formulas IIa to IIg R ₇ and R ₈ independently representing hydrogen, halogen, trifluoromethyl, lower alkyl or lower alkoxy and R _{9 representing} hydrogen, halogen, lower alkyl or lower alkoxy, R ₁₀ and R ₁₁ independently represent hydrogen, mean lower alkyl, halogen, trifluoromethyl, lower alkoxy or lower alkylthio, where if R ₁₀ or R _{11 is} hydrogen, halogen or a lower alkoxy group, the other substituent is not hydrogen, X is oxygen, sulfur, imino, lower alkylimino or a radical of the formula - (CH ₂ ) - or - (O · CH ₂ ) -, p for 1, 2 or 3, s for 3, 4 or 5 and v for 3, 4, 5 or 6 and in the group of formula IId one or two CH ₂ groups can be replaced by oxygen or sulfur, R ₄ and R _{5 are the} same or different and each represents hydrogen or a lower alkyl group, R _{3 represents} hydrogen, a cycloalkyl, a haloalkyl or is an alkyl group and R _{6 is} a group of the formulas means, where R ₇ and R _{8 have the} above meaning, w for an integer from 2 to 6, Z for oxygen, sulfur or an NR ₃ group, in which R _{3 has the} above meaning, and R ₁₂ for an alkyl, a Alkenyl, an alkynyl, a cycloalkyl, a cycloalkylalkyl, a lower alkoxy, a lower alkoxycarbonyl, a lower alkylthio, the phenyl, a phenylalkyl, a trialkylsilyl, a dialkylphenylsilyl group or for halogen, where the alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, phenyl or phenylalkyl groups can be substituted by phenyl, lower alkoxy, lower alkylthio, phenylalkoxy, lower alkoxyphenyl, lower alkylphenyl, halogenophenyl, halogen or an optionally substituted heterocycle and a carbonyl group may contain or
• b) R _{1 is} a group of the formulas IIa to IIf, as defined under a), R ₂ and R ₃ together form a - (CH ₂ ) _u group, where u is an integer from 1 to 8, and R ₄ , R ₅ and R _{6 have the} above meaning, characterized in that
  • a) a compound of the formula wherein R ₁ to R _{3 have the} above meaning, with a compound of the formula wherein A is a removable group and R ₄ to R _{6 have the} above meaning, or a compound of the formula wherein R ₁ , R ₂ and A are as defined above, with a compound of the formula wherein R ₃ to R _{6 have the} above meaning, or
  • b) for the preparation of compounds of the formula wherein R ₁ , R ₂ , R ₄ , R ₅ and R _{6 have the} above meaning and R ' _{3 represents} a cycloalkyl, haloalkyl or lower alkyl group, in a compound of the formula wherein R ₁ , R ₂ , R ₄ , R ₅ and R _{6 have the} above meaning, the group R ' ₃ introduces or
  • c) for the preparation of compounds of the formula wherein R ₁ , R ₂ , R ₃ and R _{6 have the} above meaning, a compound of the formula wherein R ₁ to R _{3 have the} above meaning and R represents a lower alkyl group, with a compound of the formula R ₆ -Me, 6 (VII) wherein R _{6 has the} above meaning and Me stands for a metal equivalent, or for the preparation of compounds of formula wherein R ₁ , R ₃ , R ₄ , R ₅ and R _{6 have the} above meaning, a compound of the formula wherein R and R ₃ to R ₆ have the above significance, with a compound of formula _R1-Me, 6 (VIIa) wherein R ₁ and Me have the above meanings, or
  • d) for the preparation of compounds of the formula wherein R ₁ to R _{3 have the} above meaning and R ' ₆ for a group of the formula stands, wherein R ₁₃ , R ₁₄ and R _{15 are the} same or different and each represents hydrogen, a lower alkyl, lower alkoxy, phenyl, phenylalkoxy, lower alkoxyphenyl, lower alkylphenyl, halophenyl group, halogen or an optionally substituted Heterocycle stand, a compound of the formula wherein R ₁ to R ₅ and R _{13 have the} above meaning, with a Wittig reagent of the formula wherein R ₁₄ and R _{15 have the} above meaning, implemented in a manner known per se, or
  • e) for the preparation of compounds of the formula wherein R ₁ , R ₂ , R ₄ , R ₅ and R _{6 have the} above meaning, a Schiff base of the formula respectively. wherein R ₁ , R ₂ , R ₄ , R ₅ and R _{6 have the} above meaning, reduced.

3. Compounds of the formula wherein

• a) R is a group of the formulas and R is hydrogen or a lower alkyl group or R and R together are a group of the formula mean, in the formulas IIa to IIg R ₇ and R ₈ independently representing hydrogen, halogen, trifluoromethyl, lower alkyl or lower alkoxy and R _{9 representing} hydrogen, halogen, lower alkyl or lower alkoxy, R ₁₀ and R ₁₁ independently represent hydrogen, mean lower alkyl, halogen, trifluoromethyl, lower alkoxy or lower alkylthio, where if R ₁₀ or R _{11 is} hydrogen, halogen or a lower alkoxy group, the other substituent is not hydrogen, X is oxygen, sulfur, imino, lower alkylimino or a radical of the formula - (CH ₂ ) - or - (O · CH ₂ ) -, p for 1, 2 or 3, s for 3, 4 or 5 and v for 3, 4, 5 or 6 and in the group of formula IId one or two CH ₂ groups can be replaced by oxygen or sulfur, R ₄ and R _{5 are the} same or different and each represent hydrogen or a lower alkyl group, R represents hydrogen, a cycloalkyl, a haloalkyl or one Alkyl group and R is a group of Formulas means, where R ₇ and R _{8 have the} above meaning, w for an integer from 2 to 6, Z for oxygen, sulfur or an NR group, in which R _{3 has the} above meaning, and R ₁₂ for an alkyl, an alkenyl -, an alkynyl, a cycloalkyl, a cycloalkylalkyl, a lower alkoxy, a lower alkoxycarbonyl, a lower alkylthio, the phenyl, a phenylalkyl, a trialkylsilyl, a dialkylphenylsilyl group or for halogen, where the Alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, phenyl and phenylalkyl groups can be substituted by phenyl, lower alkoxy, lower alkylthio, phenylalkoxy, lower alkoxyphenyl, lower alkyl phenyl, halophenyl or an optionally substituted heterocycle and can contain a carbonyl group , or
• b) R is a group of the formulas IIa to IIf, as defined under a), R and R together form a - (CH ₂ ) _u group, where u is an integer from 1 to 8, and R ₄ , R ₅ and R have the above meaning,
• with the proviso that
  • a) when R is the naphthyl radical, R, R ₄ and R _{5 are} hydrogen, R is hydrogen and R is a group of the formula IIIa in which R _{8 is} hydrogen, R ₁₂ and R _{7 are} not simultaneously halogen and R ₁₂ is not halogen or methyl when R _{7 is} hydrogen, and
  • b) if R for a group of the formulas wherein R and R are hydrogen, a lower alkyl, a lower alkoxy group or halogen and s has the above meaning, R is hydrogen or a lower alkyl group, X is oxygen, sulfur or nitrogen, R ₄ and R _{5 are} hydrogen, R is not for a group of formulas wherein Z ^{I is} oxygen or sulfur, R is hydrogen, R is hydrogen, halogen or a lower alkyl group and R is hydrogen, an alkyl, a cycloalkyl, a haloalkyl group or halogen.