DE3740127A1 - Perhydrobenzofurylmethylamines - Google Patents

Abstract

Perhydrobenzofurylmethylamines of the general formula (I) <IMAGE> in which R<1> to R<6> have the meanings given in the description, their acid addition salts, their isomers and isomer mixtures, and their use for controlling pests, in particular fungi. The novel perhydrobenzofurylmethylamines of the formula (I) can be prepared, for example, from suitable perhydrobenzofuranes and suitable amines or from suitable perhydrobenzofurylmethylamines with the aid of suitable alkylating agents.

Description

The invention relates to new perhydrobenzofurylmethylamines, several processes for their manufacture and their Use as a pesticide.

It is already known that certain tetrahydrofuranylmethylamines, such as the 2- [1- (4-chlorine phenoxy) -2-methylprop-2-yl] -5- (3,5-dimethylpiperidin-1 yl-methyl) tetrahydrofuran or the 2- [1- (4-chlorine phenoxy) -2-methylprop-2-yl] -5- (2,6-dimethylmorpholin-4 yl-methyl) tetrahydrofuran possess fungicidal properties (see DE-OS 34 13 996).

The effectiveness of these previously known compounds is however, especially at low application rates and Concentrations not in all areas of application completely satisfactory.

There were new Perhydrobenzofurylmethylamine the general Formula (I),

in which
R¹ and R² independently of one another each represent hydrogen, alkyl, alkenyl, alkynyl, alkoxyalkyl, dialkoxyalkyl, hydroxyalkyl, hydroxyalkoxyalkyl, dioxolanylalkyl, oxolanylalkyl, dioxanylalkyl or each optionally substituted cycloalkylalkyl, cycloalkyl, aralkyl, aralkenyl or aryl or
R¹ and R² together with the nitrogen atom to which they are attached represent an optionally substituted saturated heterocycle which may optionally contain further heteroatoms,
R³ represents hydrogen or alkyl and
R⁴, R⁵ and R⁶ each independently represent hydrogen, alkyl, alkoxy, haloalkyl, haloalkoxy, cycloalkylalkyl, cycloalkyl or optionally substituted aralkyl or aryl,
and their plant-compatible acid addition salts, found.

The compounds of formula (I) can optionally as geometric and / or optical isomers or isomer mixtures different composition. Both the pure isomers and the isomer mixtures are claimed according to the invention.

It was also found that the new perhydrobenzofurylmethylamines of the general formula (I),

in which
R¹ and R² independently of one another each represent hydrogen, alkyl, alkenyl, alkynyl, alkoxyalkyl, dialkoxyalkyl, hydroxyalkyl, hydroxyalkoxyalkyl, dioxolanylalkyl, oxolanylalkyl, dioxanylalkyl or each optionally substituted cycloalkylalkyl, cycloalkyl, aralkyl, aralkenyl or aryl or
R¹ and R² together with the nitrogen atom to which they are attached represent an optionally substituted saturated heterocycle which may optionally contain further heteroatoms,
R³ represents hydrogen or alkyl and
R⁴, R⁵ and R⁶ each independently represent hydrogen, alkyl, alkoxy, haloalkyl, haloalkoxy, cycloalkylalkyl, cycloalkyl or optionally substituted aralkyl or aryl,
as well as their plant-compatible acid addition salts are obtained if one

• (a) substituted perhydrobenzofurans of the formula (II), in which
  R³, R⁴, R⁵ and R⁶ have the meaning given above and
  X¹ represents an electron-withdrawing leaving group,
  with amines of the formula (III), in which
  R¹ and R² have the meaning given above,
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder, or if
• (b) the perhydrobenzofurylmethylamines of the formula (Ia) obtainable by process (a), in which
  R¹, R³, R⁴, R⁵ and R⁶ have the meaning given above,
  with alkylating agents of the formula (V), R ^2-1 -X² (V) in which
  R ^{2-1 represents} alkyl, alkenyl, alkynyl, alkoxyalkyl, dialkoxyalkyl, hydroxyalkyl, hydroxyalkoxyalkyl, dioxolanylalkyl, oxolanylalkyl, dioxanylalkyl or for optionally substituted cycloalkylalkyl, cycloalkyl, aralkyl or aralkenyl and
  X² represents an electron-withdrawing leaving group,
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder and if appropriate subsequently adding an acid.

Finally, it was found that the new perhydrobenzofurylmethylamines the general formula (I) an effect against pests, especially against fungal ones Own pests.

The perhydrobenzofurylmethylamines according to the invention surprisingly show of the general formula (I) better fungicidal activity than that from the prior art known tetrahydrofuranylmethylamines, such as for example the 2- (4-chlorophenyl) -5- (3,5-dimethylpiperidin-1-yl-methyl) tetrahydrofuran or the 2- (4-chlorophenyl) -5- (2,6-dimethylmorpholin-4-yl-methyl) tetrahydrofuran, which is chemical and effective are obvious connections.  

The perhydrobenzofurylmethylamines according to the invention are generally defined by the formula (I). Compounds of the formula (I) in which
R¹ and R² are each independently hydrogen; for each straight-chain or branched alkyl having 1 to 12 carbon atoms, alkenyl having 3 to 8 carbon atoms, alkynyl having 3 to 8 carbon atoms, alkoxyalkyl or dialkoxyalkyl each having 1 to 6 carbon atoms, hydroxyalkyl having 2 to 6 carbon atoms or hydroxyalkoxyalkyl having 2 to 6 carbon atoms in the individual alkyl parts, each for straight-chain or branched dioxolanylalkyl, oxolanylalkyl or dioxanylalkyl, each having 1 to 4 carbon atoms in the alkyl part or for each, optionally in the cycloalkyl part, mono- to polysubstituted, alike or differently, cycloalkyl or cycloalkylalkyl, each having 3 to 7 carbon atoms in the cycloalkyl part and optionally 1 there are up to 4 carbon atoms in the alkyl part, the substituents in each case being: halogen, in each case straight-chain or branched alkyl, alkoxy, haloalkyl or haloalkoxy each having 1 to 4 carbon atoms and optionally 1 to 9 identical or different n halogen atoms; also for arylalkyl, arylalkenyl or aryl, each of which is optionally mono- to polysubstituted, identical or different, in the aryl part, each having 6 to 10 carbon atoms in the aryl part and optionally up to 6 carbon atoms in the straight-chain or branched alkyl or alkenyl part, the aryl substituents in each case being in question come: halogen, cyano, nitro, each straight-chain or branched alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, haloalkylthio, alkoxycarbonyl or alkoximinoalkyl, each having 1 to 4 carbon atoms in the individual alkyl parts and optionally 1 to 9 identical or different halogen atoms or
R¹ and R² together with the nitrogen atom to which they are attached represent an optionally mono- to polysubstituted, identically or differently substituted, saturated 5- to 7-membered heterocycle which may optionally contain a further heteroatom, in particular nitrogen, oxygen or sulfur, where Possible substituents: straight-chain or branched alkyl or hydroxyalkyl, each with 1 to 4 carbon atoms,
R³ represents hydrogen or straight-chain or branched alkyl having 1 to 4 carbon atoms and
R⁴, R⁵ and R⁶ independently of one another each represent hydrogen, each straight-chain or branched alkyl having 1 to 8 carbon atoms, alkoxy having 1 to 4 carbon atoms, haloalkyl or haloalkoxy each having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, in particular fluorine , Chlorine or bromine, for cycloalkylalkyl with 3 to 7 carbon atoms in the cycloalkyl part and 1 to 4 carbon atoms in the straight-chain or branched alkyl part, for cycloalkyl with 3 to 7 carbon atoms or for each optionally in the aryl part mono- or polysubstituted, identically or differently substituted, aralkyl with 1 to There are 4 carbon atoms in the straight-chain or branched alkyl part and 6 to 10 carbon atoms in the aryl part or aryl with 6 to 10 carbon atoms, the aryl substituents in each case being: halogen, cyano, nitro, in each case straight-chain or branched alkyl, alkoxy or alkylthio each with 1 to 4 carbon atoms, each straight-chain or branched haloalkyl, haloalkoxy or haloalkylthio, each with 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, each straight-chain or branched alkoxycarbonyl or alkoximinoalkyl, each with 1 to 4 carbon atoms in the individual alkyl parts or optionally singly or multiply, identically or differently by Halogen and / or straight-chain or branched alkyl having 1 to 4 carbon atoms substituted phenyl.

Compounds of the formula (I) in which
R¹ and R² are each independently hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n- or i-pentyl, n- or i-hexyl, n- or i-heptyl, n- or i-octyl, allyl, n- or i-butenyl, n- or i-pentenyl, propargyl, n- or i-butinyl, hydroxyethyl, hydroxypropyl, methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, methoxypropyl, Ethoxypropyl, propoxypropyl, butoxypropyl, hydroxyethoxyethyl, dimethoxyethyl, dimethoxypropyl, diethoxyethyl, dioxolanylmethyl, dioxolanylethyl, oxolanylmethyl, oxolanylethyl, dioxanylmethyl, dioxanylethyl, each optionally one to five times, the same or different, by fluorine, chlorine, bromine, methyl, or i-propyl, n-, i-, s- and / or t-butyl substituted cyclopropyl, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopentyl, cyclopentylmethyl, cyclohexyl or cyclohexylmethyl or for phenyl which is monosubstituted to trisubstituted identically or differently in each case, Benzyl or phenylethyl stand en, the substituents in each case being: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio, Trifluoromethyl, trifluoromethoxy, trifluoromethylthio, methoxycarbonyl, ethoxycarbonyl or methoximinomethyl or
R¹ and R² together with the nitrogen to which they are attached, for an optionally mono- to trisubstituted, identically or differently substituted heterocycle of the formula

are available, the following being suitable as substituents: methyl, ethyl or hydroxymethyl,
R³ represents hydrogen, methyl or ethyl and
R⁴, R⁵ and R⁶ independently of one another each represent hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, straight-chain or branched pentyl, straight-chain or branched hexyl, for methoxy, ethoxy, Trifluoromethyl, trifluoromethoxy, for cyclohexylmethyl, for each straight-chain or branched cyclohexylethyl, cyclohexylpropyl or cyclohexylbutyl, for cyclopropyl, cyclopentyl or cyclohexyl or for each optionally in the phenyl part mono- to trisubstituted, identically or differently substituted, benzyl, phenyl or phenylpropose, wherein as phenylprop Phenyl substituents in each case come into question: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy , Methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl, ethoximinoethyl or optionally one to three times, the same or different, by fluo r, chlorine, bromine, methyl and / or ethyl substituted phenyl.

Compounds of the formula (I) in which
R¹ and R² are each independently hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n- or i-pentyl, n- or i-hexyl, allyl, n - or i-butenyl, n- or i-pentenyl, propargyl, n- or i-butynyl, hydroxyethyl, hydroxypropyl, methoxyethyl, methoxypropyl, ethoxyethyl, ethoxypropyl, hyroxyethoxyethyl, dimethoxyethyl, diethoxyethyl, dioxolanylmethyl, dioxolanylethyl, oxolanylmethyl, dioxolanylmethyl, dioxolanylmethyl, dioxolanylmethyl, dioxolanylmethyl, dioxolanylmethyl, oxolanylmethyl, dioxolanyl Cyclopropylmethyl, dichlorocyclopropylmethyl, dimethylcyclopropylmethyl, dichlorodimethylcyclopropylmethyl, cyclopentyl, cyclohexyl or cyclohexylmethyl or
R¹ and R² together with the nitrogen atom to which they are attached, for an optionally mono- to trisubstituted, identically or differently substituted heterocycle of the formula

are available, the following being suitable as substituents: methyl, ethyl, hydroxymethyl,
R³ represents hydrogen or methyl and
R⁴, R⁵ and R⁶ each independently represent hydrogen, methyl, ethyl, i-propyl, i-butyl, t-butyl or i-amyl.

Alkyl alone, in compositions such as e.g. B. alkoxyalkyl, or as a substituent of other radicals always be branched and unbranched, even if it is not is expressly said.

Preferred compounds according to the invention are also Addition products from acids and those perhydrobenzofurylmethylamines of formula (I) in which the Substituents R¹, R², R³, R⁴, R⁵ and R⁶ have the meanings have already mentioned for these substituents were.

The acids that can be added preferably include Hydrohalic acids, such as. B. hydrochloric acid and hydrobromic acid, in particular hydrochloric acid, also phosphoric acid, Nitric acid, sulfuric acid, mono-, bi- and trifunctional Carboxylic acids and hydroxycarboxylic acids, such as. B. Acetic acid, maleic acid, succinic acid, fumaric acid, Tartaric acid, citric acid, salicylic acid, sorbic acid and  Lactic acid, and sulfonic acid, such as p-toluenesulfonic acid and 1,5-naphthalenedisulfonic acid and saccharin or Thiosaccharin.

In particular, except for the manufacturing examples mentioned compounds the following perhydrobenzofurylmethylamines of the general formula (I) called:

For example, 2-bromomethyl-5-t-butyl-perhydrobenzofuran is used and piperidine as starting materials, see above can the course of the reaction of the invention Method (a) by the following formula scheme represent:

For example, 2- (N-cyclohexylamino is used methyl) -3-methyl-isopropylperhydrobenzofuran and Allyl bromide as starting materials, so the Reaction sequence of the process (b) according to the invention represented by the following formula:

To carry out the method according to the invention (a) Substituted perhydrobenzofurans required as starting materials are general by the formula (II) Are defined. In this formula (II) are R³, R⁴, R⁵ and R⁶ preferably for those residues that are already in Connection with the description of the invention Substances of formula (I) as preferred for these substituents were called.

X¹ is preferably halogen, especially for Chlorine, bromine or iodine.

The substituted perhydrobenzofurans of the formula (II) are partially known (see e.g. Heterocycles 23, 2035-2039 [1985]; Khim. Heterotics Soedin. 1985, 170-172 or CA 103: 6168c; J. org. Chem. 48, 1557-1559 [1983]).

Substituted tetrahydrofurans are not yet known of the formula (IIa),

in which
R³, R⁴, R⁵ and R⁶ have the meaning given above and
Hal stands for halogen,
however, at least one of R³, R⁴, R⁵ and R⁶ is different from hydrogen.

The so far unknown substituted ones are obtained Perhydrobenzofurans of the formula (IIa) in analogy to known methods (cf. e.g. DE-OS 34 13 996 or Khim. Heterotics Soedin. 1985, 170-172 and CA 103: 6168c), for example, by using the generally known Cyclohexanones of the formula (VI),

in which
R⁴, R⁵ and R⁶ have the meaning given above,
first in a 1st stage with allyl bromides of the formula (VII),

in which
R³ has the meaning given above,
optionally in the presence of a diluent, such as, for example, diethyl ether, and in the presence of a base, such as, for example, sodium amide, at temperatures between 20 ° C. and 80 ° C., then the allylcyclohexanones of the formula (VIII) obtainable in this way,

in which
R³, R⁴, R⁵ and R⁶ have the meaning given above,
in a second stage in a generally customary manner using a reducing agent, such as sodium borohydride, in the presence of a diluent, such as methanol, at temperatures between 0 ° C. and 80 ° C., then the allylcyclohexanols of the formula (IX) thus obtainable ,

in which
R³, R⁴, R⁵ and R⁶ have the meanings given above,
in a third stage with a halogenating agent, such as elemental bromine, in the presence of quinoline or N-bromosuccinimide, optionally in the presence of a diluent, such as chloroform, at temperatures between -20 ° C and + 80 ° C.

Cyclohexanones of the formula (VI) and allyl bromides Formula (VII) are generally known compounds of organic chemistry or available in analogy to general known processes (cf. e.g. Organic Syntheses Coll. Vol. III, p. 44)

To carry out the method according to the invention (a) are still amines required as starting materials generally defined by formula (III). In this Formula (III) preferably represents R1 and R2 Leftovers already related to the Description of the substances of the formula (I) according to the invention were mentioned as preferred for these substituents.

The amines of the formula (III) are generally known compounds of organic chemistry.

To carry out the method according to the invention (b) Perhydrobenzofurylmethylamines required as starting materials are generally defined by the formula (Ia).  In this formula (Ia) are R¹, R³, R⁴, R⁵ and R⁶ preferably for those residues that are already in Connection with the description of the invention Substances of formula (I) as preferred for these substituents were called.

The perhydrobenzofurylmethylamines of the formula (Ia) are Compounds according to the invention and obtainable with the help of the method (a) according to the invention.

Formula (V) provides a general definition of the alkylating agents which are furthermore required as starting materials for carrying out process (b) according to the invention. In this formula (V), R ^2-1 preferably represents in each case straight-chain or branched alkyl having 1 to 12 carbon atoms, alkenyl having 3 to 8 carbon atoms, alkynyl having 3 to 8 carbon atoms, alkoxyalkyl or dialkoxyalkyl having 1 to 6 carbon atoms, hydroxyalkyl having 2 up to 6 carbon atoms or hydroxyalkoxyalkyl with 2 to 6 carbon atoms in the individual alkyl parts; for each straight-chain or branched dioxolanylalkyl, oxolanylalkyl or dioxanylalkyl, each having 1 to 4 carbon atoms in the alkyl part; for cycloalkyl or cycloalkyl, each of which is monosubstituted or polysubstituted in the cycloalkyl moiety, in each case with 3 to 7 carbon atoms in the cycloalkyl moiety and optionally 1 to 4 carbon atoms in the straight-chain or branched alkyl moiety, in each case in the cycloalkyl part, the substituents in each case being: halogen, in each case straight-chain or branched Alkyl, alkoxy, haloalkyl or haloalkoxy each having 1 to 4 carbon atoms and optionally 1 to 9 identical or different halogen atoms; in addition for arylalkyl or arylalkenyl which are each mono- or polysubstituted in the aryl part and have 6 to 10 carbon atoms in the aryl part and up to 6 carbon atoms in the straight-chain or branched alkyl or alkenyl part, which are optionally mono- or polysubstituted in the aryl part, the following being suitable in each case: Cyano, nitro, each straight-chain or branched alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, haloalkylthio, alkoxycarbonyl or alkoximinoalkyl, each having 1 to 4 carbon atoms in the individual alkyl parts and optionally 1 to 9 identical or different halogen atoms.

R ^2-1 particularly preferably represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n- or i-pentyl, n- or i-hexyl, n- or i -Heptyl, n- or i-octyl, allyl, n- or i-butenyl, n- or i-pentenyl, propargyl, n- or i-butinyl, hydroxyethyl, hydroxypropyl, methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, methoxypropyl, ethoxypropyl , Propoxypropyl, butoxypropyl, hydroxyethoxyethyl, dimethoxyethyl, dimethoxypropyl, diethoxyethyl, dioxolanylmethyl, dioxolanylethyl, oxolanylmethyl, oxolanylethyl, dioxanylmethyl, dioxanylmethyl, each optionally one to five times, the same or different by fluorine, chlorine, n-bromine or methyl, ethyl i-propyl, n-, i-, s- and / or t-butyl, substituted cyclopropyl, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopentyl, cyclopentylmethyl, cyclohexyl or cyclohexylmethyl or for benzyl or monosubstituted to trisubstituted, identically or differently in each case or Phenylethyl, being as substituents in each case are possible: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, Methoxycarbonyl, ethoxycarbonyl or methoximinomethyl.

R ^2-1 very particularly preferably represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n- or i-pentyl, n- or i-hexyl, allyl, n - or i-butenyl, n- or i-pentenyl, propargyl, n- or i-butinyl, hydroxyethyl, hydroxypropyl, methoxyethyl, methoxypropyl, ethoxyethyl, ethoxypropyl, hydroxyethoxyethyl, dimethoxyethyl, diethoxyethyl, dioxolanylmethyl, dioxolanylethyl, oxolanylmethyl, dioxolanylmethyl, dioxolanylmethyl, dioxolanylmethyl Cyclopropylmethyl, dichlorocyclopropylmethyl, dimethylcyclopropylmethyl, dichlorodimethylcyclopropylmethyl, cyclopentyl, cyclohexyl or cyclohexylmethyl.

X² preferably represents halogen, in particular Chlorine, bromine or iodine or for each optionally halogen substituted alkylsulfonyloxy or alkoxysulfonyloxy having 1 to 4 carbon atoms  and optionally 1 to 9 halogen atoms or for optionally by alkyl with 1 up to 4 carbon atoms substituted arylsulfonyloxy, such as methanesulfonyloxy, Methoxysulfonyloxy or p-toluenesulfonyloxy.

The alkylating agents of formula (V) are also generally known compounds of organic chemistry or available in analogy to generally known ones Method.

As a diluent for carrying out the inventive Processes (a) and (b) are inert organic Solvents or aqueous systems in question. These include in particular aliphatic or aromatic, optionally halogenated hydrocarbons, such as gasoline, benzene, toluene, xylene, chlorobenzene, Petroleum ether, hexane, cyclohexane, dichloromethane, Chloroform, carbon tetrachloride; Ethers, such as diethyl ether, Dioxane, tetrahydrofuran or ethylene glycol dimethyl or diethyl ether; Ketones such as acetone or Butanone; Nitriles such as acetonitrile or propionitrile; Amides, such as dimethylformamide, dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Esters, such as ethyl acetate or Sulfoxides such as dimethyl sulfoxide.

Processes (a) and (b) according to the invention can, if appropriate also in a two-phase system, such as Water / toluene or water / dichloromethane,  optionally in the presence of a phase transfer catalyst, be performed. As examples of such Catalysts may be mentioned: tetrabutylammonium iodide, Tetrabutylammonium bromide, tributyl methylphosphonium bromide, Trimethyl-C₁₃ / C₁₅-alkylammonium chloride, dibenzyldimethylammonium methyl sulfate, Dimethyl-C₁₂ / C₁₄-alkyl-benzylammonium chloride, Tetrabutylammonium hydroxide, 15-crown-5, 18-crown-6, triethylbenzylammonium chloride, Trimethylbenzylammonium chloride. It is also possible that Processes (a) and (b) according to the invention without addition a solvent.

As an acid binder for carrying out the inventive Methods (a) and (b) all come normally usable inorganic and organic bases in Question. Alkali metal hydroxides are preferably used, carbonates or bicarbonates, such as Sodium hydroxides, sodium carbonate or sodium hydrogen carbonate or also tertiary amines, such as Triethylamine, N, N-dimethylaniline, pyridine, 4- (N, N-dimethylamino) pyridine, Diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).

It is also possible to use the reactants Amines of the formulas (III) and (Ia) in a corresponding manner Surplus at the same time as an acid binder to use.

The reaction temperatures can be carried out of processes (a) and (b) in one  larger range can be varied. Generally works one at temperatures between -20 ° C and + 180 ° C, preferably at temperatures between 20 ° C and + 150 ° C.

To carry out process (a) according to the invention is used per mole of substituted perhydrobenzofuran of formula (II) generally 1.0 to 3.0 moles, preferably 1.0 to 1.5 mol of amine of the formula (III) and, if appropriate 1.0 to 3.0 moles, preferably 1.0 to 1.5 moles of acid binders, and optionally 0.1 to 1.0 Mole of phase transfer catalyst.

To carry out process (b) according to the invention is used per mole of perhydrobenzofurylmethylamine Formula (Ia) generally 1.0 to 5.0 moles, preferably 1.0 to 2.0 mol of alkylating agent of the formula (V) and 1.0 to 5.0 moles, preferably 1.0 to 2.0 moles Acid binder, and optionally 0.1 to 1.0 mol on phase transfer catalyst.

The implementation of the reaction, workup and isolation the reaction products of formula (I) take place in both Cases according to usual methods.

The acid addition salts of the compounds of formula (I) can be made in a simple manner using conventional salt formation methods, such as B. by loosening a connection Formula (I) in a suitable inert solvent and  Adding an acid such as B. hydrochloric acid, be obtained and in a known manner, e.g. B. by filtering, isolated and optionally by washing cleaned with an inert organic solvent will.

Alternatively to the preparation of the perhydrobenzofurylmethylamines according to the invention of formula (I) using the Processes (a) and (b) according to the invention are also possible compounds of the formula (I) according to the invention to get if you know the known dihydro-benzofurans Formula (X) (see e.g. DE-OS 36 20 354),

in which
R¹, R², R⁴, R⁵ and R⁶ have the meaning given above,
hydrogenated in a generally customary manner in the presence of hydrogen and in the presence of a customary hydrogenation catalyst and optionally in the presence of a diluent.

The active ingredients according to the invention have a strong Action against pests and can be used to control  practically used by unwanted harmful organisms will. The active ingredients are for use as pesticides particularly suitable as fungicides.

Fungicides in crop protection are used for Control of Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes, Deuteromycetes.

Some pathogens are exemplary but not limiting of fungal diseases listed below Generic terms fall, called:

Pythium species, such as, for example, Pythium ultimum;
Phytophthora species, such as, for example, Phytophthora infestans;
Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or Pseudoperonospora cubensis;
Plasmopara species, such as, for example, Plasmopara viticola;
Peronospora species, such as, for example, Peronospora pisi or P. brassicae;
Erysiphe species, such as, for example, Erysiphe graminis;
Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;
Podosphaera species, such as, for example, Podosphaera leucotricha;
Venturia species, such as, for example, Venturia inaequalis;
Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea
(Conidial form: Drechslera, Syn: Helminthosporium); Cochliobolus species, such as, for example, Cochliobolus sativus
(Conidial form: Drechslera, Syn: Helminthosporium); Uromyces species, such as, for example, Uromyces appendiculatus;
Puccinia species, such as, for example, Puccinia recondita;
Tilletia species, such as, for example, Tilletia caries;
Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;
Pellicularia species, such as, for example, Pellicularia sasakii;
Pyricularia species, such as, for example, Pyricularia oryzae;
Fusarium species, such as, for example, Fusarium culmorum;
Botrytis species, such as, for example, Botrytis cinerea;
Septoria species, such as, for example, Septoria nodorum;
Leptosphaeria species, such as, for example, Leptosphaeria nodorum;
Cercospora species, such as, for example, Cercospora canescens;
Alternaria species, such as, for example, Alternaria brassicae;
Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides.

The good plant tolerance of the active ingredients in the concentrations necessary to combat plant diseases allows treatment from above ground Parts of plants, of seedlings, and des Floor.  

The active compounds according to the invention can also be used particularly good success in combating cereal diseases, such as against the pathogen of the real one Powdery mildew (Erysiphe graminis) or against the pathogen the brown rust of wheat (Puccinia recondita), to combat rice diseases, such as against the pathogen of leaf blotch on rice (Pyricularia oryzae) or for fighting diseases in fruit and vegetable growing, such as against the Apple scab (Venturia inaequalis) or against Oomycetes. In addition, show the invention Active substances have a good in vitro effectiveness.

The active ingredients can depend on their respective physical and / or chemical properties in usual formulations are transferred, such as solutions, Emulsions, suspensions, powders, foams, pastes, granules, Aerosols, active ingredient-impregnated natural and synthetic Substances, very fine encapsulations in polymers Substances and in coating compositions for seeds, as well as ULV cold and warm fog formulations.

These formulations are prepared in a known manner e.g. B. by mixing the active ingredients with extenders, i.e. liquid solvents, under pressure liquefied gases and / or solid carriers, optionally using surfactants Agents, ie emulsifiers and / or dispersants  and / or foam-generating agents. In case of Use of water as an extender can e.g. Belly organic solvents used as auxiliary solvents will. Essentially come as liquid solvents in question: aromatics, such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic Hydrocarbons such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. B. petroleum fractions, Alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, Methyl isobutyl ketone or cyclohexanone, strongly polar Solvents such as dimethylformamide and dimethyl sulfoxide, as well as water; with liquefied gaseous Extenders or carriers are such liquids meant, which at normal temperature and below Normal pressure are gaseous, e.g. B. aerosol propellants, such as Halogenated hydrocarbons as well as butane, propane, nitrogen and carbon dioxide; come as solid carriers in question: e.g. B. natural stone powder, such as kaolins, Clay, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic rock powder, such as finely divided silica, aluminum oxide and silicates; come in as solid carriers for granules Question: e.g. B. broken and fractionated natural rocks such as calcite, marble, pumice, sepiolite, dolomite as well synthetic granules from inorganic and organic Flours and granules made from organic material such as sawdust, coconut shells, corn cobs and tobacco stalks; as an emulsifier and / or foam-generating agent  come into question: z. B. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkylaryl polyglycol ether, Alkyl sulfonates, alkyl sulfates, aryl sulfonates and Protein hydrolyzates; as dispersants are: e.g. B. lignin sulfite and methyl cellulose.

In the formulations, adhesives such as carboxymethyl cellulose, natural and synthetic powdery, granular or latex-shaped polymers can be used, such as Gum arabic, polyvinyl alcohol, polyvinyl acetate, as well natural phospholipids, such as cephalins and lecithins, and synthetic phospholipids. Other additives can mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. Iron oxide, titanium oxide, ferrocyan blue and organic dyes, such as alizarin, azo and metal phthalocyanine dyes and trace nutrients such as salts of iron, manganese, Boron, copper, cobalt, molybdenum and zinc can be used.

The formulations generally contain between 0.1 and 95 percent by weight of active ingredient, preferably between 0.5 and 90%.

The active compounds according to the invention can be used in the formulations in a mixture with other known active ingredients are present such as fungicides, insecticides, acaricides and herbicides as well as in mixtures with fertilizers and growth regulators.  

The active ingredients as such, in the form of their formulations or the application forms prepared from it such as ready-to-use solutions, suspensions, wettable powders, Pastes, soluble powders, dusts and granules be applied. The application is done in the usual way Way, e.g. B by pouring, spraying, spraying, scattering, Dusting, foaming, brushing, etc. It it is also possible to use the active ingredients according to the ultra-low-volume method apply or the drug preparation or inject the active ingredient into the soil yourself. It can also treat the seeds of the plants will.

When treating parts of plants, the drug concentrations can in the application forms in one larger range can be varied. They generally lie between 1 and 0.0001% by weight, preferably between 0.5 and 0.001%.

When treating seeds, amounts of active ingredient are generally used from 0.001 to 50 g per kilogram of seed, preferably 0.01 to 10 g is required.

When treating the soil are active ingredient concentrations from 0.00001 to 0.1% by weight, preferably from 0.0001 to 0.02% required at the site of action.

Manufacturing examples example 1 (Method a)

20 g (0.07 mol) of 2-bromomethyl-5-t-butylperhydrobenzofuran and 18 g (0.15 mol) of 2,6-dimethylmorpholine are heated to 140 ° C. for 16 hours, cooled, taken up in dichloromethane, washed with water, dried over sodium sulfate and concentrated. Kugelrohr distillation of the residue (190 ° C, 0.13 mbar) gives 10.3 g (46% of theory) of 5-t-butyl-2- (2,6-dimethylmorpholin-4-yl-methyl) -perhydrobenzofuran from the refractive index n 1.4812.

Preparation of the starting compound Example II-1

To 51 g (0.26 mol) of 2-allyl-4-t-butylcyclohexanol in 250 ml Chloroform is added with stirring at room temperature portions of 46.3 g (0.26 mol) of N-bromosuccinimide and after the addition has ended, stir for a further 16 hours at room temperature. To work up, wash twice with 100 ml of water each, dries over sodium sulfate and constricts in a vacuum.

46 g (64.5% of theory) of 2-bromomethyl-5-t-butyl-perhydrobenzofuran are obtained as oil, which without additional Cleaning is implemented further.  

Example IX-1

To 54 g (0.28 mol) of 2-allyl-4-t-butylcyclohexanone (cf. e.g. B. J. org. Chem. 47, 5372-80, [1982] in 250 ml Methanol is added in portions to 10.5 g (0.28 mol) Sodium borohydride and the mixture is left for 12 hours Stand at room temperature. Neutralized for processing one with dilute hydrochloric acid and concentrated in vacuo.

51 g (93.4% of theory) of 2-allyl-4-t-butylcyclohexanol are obtained as an oil (IR: γ = 2870 cm ^-1 ).

In a corresponding manner and in accordance with the general information the following perhydrobenzofurylmethylamines are obtained for the preparation of the general formula (I):

Examples of use

In the following application example, the following were Compounds listed as reference substances used:

2- [1- (4-chlorophenoxy) -2-methylprop-2-yl] -5- (3,5-dimethylpiperidin-1-ylmethyl) tetrahydrofuran
(known from DE-OS 34 13 996)

2- [1- (4-chlorophenoxy) -2-methylprop-2-yl] -5- (2,6-dimethyl-morpholin-4-yl-methyl) tetrahydrofuran
(known from DE-OS 34 13 996).

Example A Puccinia test (wheat) / protective

Solvent: 100 parts by weight of dimethylformamide
Emulsifier: 0.025 part by weight of alkylaryl polyglycol ether

For the preparation of a suitable active ingredient preparation is mixed 1 part by weight of active ingredient with the specified Amounts of solvent and emulsifier and dilute that Concentrate with water to the desired concentration.

To test for protective effectiveness, young Plants with a spore suspension of Puccinia recondita inoculated with a 0.1% aqueous agar solution. After drying, the plants are sprayed with the Active ingredient preparation dewy. The plants remain 24 hours at 20 ° C and 100% rel. Humidity in an incubation cabin.

The plants are grown in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of about 80% set up to develop Favor rust pustules.

Evaluation is carried out 10 days after the inoculation.

A clear superiority in effectiveness over the prior art show in this test z. B. the compounds according to the preparation examples: 1, 3 and 4.

Claims (11)

1. perhydrobenzofurylmethylamines of the general formula (I), in which
R¹ and R² independently of one another each represent hydrogen, alkyl, alkenyl, alkynyl, alkoxyalkyl, dialkoxyalkyl, hydroxyalkyl, hydroxyalkoxyalkyl, dioxolanylalkyl, oxolanylalkyl, dioxanylalkyl or each optionally substituted cycloalkylalkyl, cycloalkyl, aralkyl, aralkenyl or aryl or
R¹ and R² together with the nitrogen atom to which they are attached represent an optionally substituted saturated heterocycle which may optionally contain further heteroatoms,
R³ represents hydrogen or alkyl and
R⁴, R⁵ and R⁶ each independently represent hydrogen, alkyl, alkoxy, haloalkyl, haloalkoxy, cycloalkylalkyl, cycloalkyl or optionally substituted aralkyl or aryl,
and their plant-compatible acid addition salts, their isomers and isomer mixtures. 2. Pherhydrobenzofurylmethylamine according to claim 1, where in the formula (I)
R¹ and R² are each independently hydrogen; for each straight-chain or branched alkyl having 1 to 12 carbon atoms, alkenyl having 3 to 8 carbon atoms, alkynyl having 3 to 8 carbon atoms, alkoxyalkyl or dialkoxyalkyl each having 1 to 6 carbon atoms, hydroxyalkyl having 2 to 6 carbon atoms or hydroxyalkoxyalkyl having 2 to 6 carbon atoms in the individual alkyl parts, for dioxolanylalkyl, oxolanylalkyl or dioxanylalkyl, each having 1 to 4 carbon atoms in each straight-chain or branched alkyl part, or for each, optionally in the cycloalkyl part, single to multiple, identically or differently substituted cycloalkyl or cycloalkylalkyl each having 3 to 7 carbon atoms in the cycloalkyl part and optionally 1 there are up to 4 carbon atoms in the alkyl part, the substituents in each case being: halogen, in each case straight-chain or branched alkyl, alkoxy, haloalkyl or haloalkoxy each having 1 to 4 carbon atoms and optionally 1 to 9 identical or different n halogen atoms; also for arylalkyl, arylalkenyl or aryl, each of which is optionally mono- to polysubstituted, identical or different, in the aryl part, each having 6 to 10 carbon atoms in the aryl part and optionally up to 6 carbon atoms in the straight-chain or branched alkyl or alkenyl part, the aryl substituents in each case being in question come: halogen, cyano, nitro, each straight-chain or branched alkyl, alkoxy, alkylthio, haloalkyl, haloalkoxy, haloalkylthio, alkoxycarbonyl or alkoximinoalkyl, each having 1 to 4 carbon atoms in the individual alkyl parts and optionally 1 to 9 identical or different halogen atoms or
R¹ and R² together with the nitrogen atom to which they are attached represent an optionally mono- to polysubstituted, identically or differently substituted, saturated 5- to 7-membered heterocycle which may optionally contain a further heteroatom, the following being suitable as substituents: each straight-chain or branched alkyl or hydroxyalkyl each having 1 to 4 carbon atoms,
R³ represents hydrogen or straight-chain or branched alkyl having 1 to 4 carbon atoms and
R⁴, R⁵ and R⁶ independently of one another each represent hydrogen, each straight-chain or branched alkyl having 1 to 8 carbon atoms, alkoxy having 1 to 4 carbon atoms, haloalkyl or haloalkoxy each having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, for cycloalkylalkyl with 3 to 7 carbon atoms in the cycloalkyl part and 1 to 4 carbon atoms in the straight-chain or branched alkyl part, for cycloalkyl with 3 to 7 carbon atoms or for each optionally in the aryl part mono- or polysubstituted, identically or differently substituted aralkyl with 1 to 4 carbon atoms in the straight-chain or branched alkyl part and 6 to 10 carbon atoms in the aryl part or aryl having 6 to 10 carbon atoms, the aryl substituents in each case being suitable: halogen, cyano, nitro, each straight-chain or branched alkyl, alkoxy or alkylthio each having 1 to 4 carbon atoms, each straight-chain or branched Halog enalkyl, haloalkoxy or haloalkylthio, each having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms, each straight-chain or branched alkoxycarbonyl or alkoximinoalkyl, each having 1 to 4 carbon atoms in the individual alkyl parts or optionally singly or multiply, identically or differently by halogen, straight-chain or branched alkyl with 1 to 4 carbon atoms substituted phenyl. 3. Perhydrobenzofurylmethylamine according to claim 1, where in the formula (I),
R¹ and R² are each independently hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n- or i-pentyl, n- or i-hexyl, n- or i-heptyl, n- or i-octyl, allyl, n- or i-butenyl, n- or i-pentenyl, propargyl, n- or i-butinyl, hydroxyethyl, hydroxypropyl, methoxyethyl, ethoxyethyl, propoxyethyl, butoxyethyl, methoxypropyl, Ethoxypropyl, propoxypropyl, butoxypropyl, hydroxyethoxyethyl, dimethoxyethyl, dimethoxypropyl, diethoxyethyl, dioxolanylmethyl, dioxolanylethyl, oxolanylmethyl, oxolanylethyl, dioxanylmethyl, dioxanylethyl, each optionally one to five times, the same or different, by fluorine, chlorine, bromine, methyl, or i-propyl, n-, i-, s- or t-butyl substituted cyclopropyl, cyclopropylmethyl, cyclopropylethyl, cyclopropylpropyl, cyclopentyl, cyclopentylmethyl, cyclohexyl or cyclohexylmethyl or for each phenyl, benzyl or, optionally mono- to trisubstituted, identically or differently Phenylethyl, where the following are suitable as substituents: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, methylthio, trifluoromethyl, Trifluoromethoxy, trifluoromethylthio, methoxycarbonyl, ethoxycarbonyl or methoximinomethyl or
R¹ and R² together with the nitrogen to which they are attached, for an optionally mono- to trisubstituted, identically or differently substituted heterocycle of the formula are available, the following being suitable as substituents: methyl, ethyl or hydroxymethyl,
R³ represents hydrogen, methyl or ethyl and
R⁴, R⁵ and R⁶ independently of one another each represent hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, straight-chain or branched pentyl, straight-chain or branched hexyl, for methoxy, ethoxy, Trifluoromethyl, trifluoromethoxy, for cyclohexylmethyl, for each straight-chain or branched cyclohexylethyl, cyclohexylpropyl or cyclohexylbutyl, for cyclopropyl, cyclopentyl or cyclohexyl or for each optionally in the phenyl part mono- to trisubstituted, identically or differently substituted, benzyl, phenyl or phenylpropose, wherein as phenylprop Phenyl substituents in each case come into question: fluorine, chlorine, bromine, cyano, nitro, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy , Methylthio, trifluoromethyl, trifluoromethoxy, trifluoromethylthio, methoxycarbonyl, ethoxycarbonyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl, ethoximinoethyl or optionally one to three times, the same or different, by fluo r, chlorine, bromine, methyl or ethyl substituted phenyl. 4. Perhydrobenzofurylmethylamine according to claim 1, where in the formula (I)
R¹ and R² are each independently hydrogen, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, n- or i-pentyl, n- or i-hexyl, allyl, n - or i-butenyl, n- or i-pentenyl, propargyl, n- or i-butynyl, hydroxyethyl, hydroxypropyl, methoxyethyl, methoxypropyl, ethoxyethyl, ethoxypropyl, hyroxyethoxyethyl, dimethoxyethyl, diethoxyethyl, dioxolanylmethyl, dioxolanylethyl, oxolanylmethyl, dioxolanylmethyl, dioxolanylmethyl, dioxolanylmethyl, dioxolanylmethyl, dioxolanylmethyl, oxolanylmethyl, dioxolanyl Cyclopropylmethyl, dichlorocyclopropylmethyl, dimethylcyclopropylmethyl, dichlorodimethylcyclopropylmethyl, cyclopentyl, cyclohexyl or cyclohexylmethyl or
R¹ and R² together with the nitrogen atom to which they are attached, for an optionally mono- to trisubstituted, identically or differently substituted heterocycle of the formula are available, the following being suitable as substituents: methyl, ethyl, hydroxymethyl,
R³ represents hydrogen or methyl and
R⁴, R⁵ and R⁶ each independently represent hydrogen, methyl, ethyl, i-propyl, i-butyl, t-butyl or i-amyl. 5. Process for the preparation of pherhydrobenzofurylmethylamines of the general formula (I), in which
R¹ and R² independently of one another each represent hydrogen, alkyl, alkenyl, alkynyl, alkoxyalkyl, dialkoxyalkyl, hydroxyalkyl, hydroxyalkoxyalkyl, dioxolanylalkyl, oxolanylalkyl, dioxanylalkyl or each optionally substituted cycloalkylalkyl, cycloalkyl, aralkyl, aralkenyl or aryl or
R¹ and R² together with the nitrogen atom to which they are attached represent an optionally substituted, saturated heterocycle which may optionally contain further heteroatoms,
R³ represents hydrogen or alkyl and
R⁴, R⁵ and R⁶ each independently represent hydrogen, alkyl, alkoxy, haloalkyl, haloalkoxy, cycloalkylalkyl, cycloalkyl or optionally substituted aralkyl or aryl,
whose plant-compatible acid addition salts, their isomers and isomer mixtures, characterized in that

• (a) substituted perhydrobenzofurans of the formula (II), in which
  R³, R⁴, R⁵ and R⁶ have the meaning given above and
  X¹ represents an electron-withdrawing leaving group,
  with amines of the formula (III), in which
  R¹ and R² have the meaning given above,
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder, or
• (b) the perhydrobenzofurylmethylamines of the formula (Ia) obtainable by process (a), in which
  R¹, R³, R⁴, R⁵ and R⁶ have the meaning given above,
  with alkylating agents of the formula (V), R ^2-1 -X² (V) in which
  R ^{2-1 represents} alkyl, alkenyl, alkynyl, alkoxyalkyl, dialkoxyalkyl, hydroxyalkyl, hydroxyalkoxyalkyl, dioxolanylalkyl, oxolanylalkyl, dioxanylalkyl or for optionally substituted cycloalkylalkyl, cycloalkyl, aralkyl or aralkenyl and
  X² represents an electron-withdrawing leaving group,
  if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder and if appropriate subsequently adding an acid.

6. Pesticides, characterized by contains at least one perhydrobenzofurylmethylamine of formula (I) according to claims 1 and 5. 7. Use of perhydrobenzofurylmethylamine Formula (I) according to claims 1 and 5 for combating of pests. 8. Pest control method, thereby characterized in that perhydrobenzofurylmethylamine of formula (I) according to claims 1 and 5 affect pests and / or their habitat leaves.   9. Process for the preparation of pesticides, characterized in that one Perhydrobenzofurylmethylamine of formula (I) after claims 1 and 5 with extenders and / or surface active agents mixed. 10. Substituted tetrahydrofurans of the formula (IIa), in which
R³ represents hydrogen or alkyl and
R⁴, R⁵ and R⁶ each independently represent hydrogen, alkyl, alkoxy, haloalkyl, haloalkoxy, cycloalkylalkyl, cycloalkyl or optionally substituted aralkyl or aryl,
Hal stands for halogen,
however, at least one of R³, R⁴, R⁵ and R⁶ is different from hydrogen. 11. Process for the preparation of substituted tetrahydrofurans of the formula (IIa) in which
R³ represents hydrogen or alkyl and
R⁴, R⁵ and R⁶ each independently represent hydrogen, alkyl, alkoxy, haloalkyl, haloalkoxy, cycloalkylalkyl, cycloalkyl or optionally substituted aralkyl or aryl,
Hal stands for halogen,
however, at least one of the radicals R³, R⁴, R⁵ and R⁶ is different from hydrogen, characterized in that cyclohexanones of the formula (VI) in which
R⁴, R⁵ and R⁶ have the meaning given above,
first in a 1st stage with allyl bromides of the formula (VII), in which
R³ has the meaning given above,
if appropriate in the presence of a diluent and in the presence of a base at temperatures between 20 ° C. and 80 ° C., then the allylcyclohexanones of the formula (VIII) obtainable in this way, in which
R³, R⁴, R⁵ and R⁶ have the meaning given above,
in a second stage in a generally customary manner using a reducing agent, in the presence of a diluent, at temperatures between 0 ° C. and 80 ° C., then the allylcyclohexanols of the formula (IX) which are obtainable in this way, in which
R³, R⁴, R⁵ and R⁶ have the meaning given above,
in a third stage with a halogenating agent in the presence of quinoline or N-bromosuccinimide, optionally in the presence of a diluent at temperatures between -20 ° C and + 80 ° C.