EP1181264A1

EP1181264A1 - Method for producing 2,2,4,4-tetra-substituted 1,3,5-cyclohexanetriones

Info

Publication number: EP1181264A1
Application number: EP00936762A
Authority: EP
Inventors: Roland Götz; Norbert Götz; Matthias Witschel; Michael Rack
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 1999-06-02
Filing date: 2000-05-19
Publication date: 2002-02-27
Also published as: HUP0201400A2; CN1353685A; KR20020006051A; IL146573A0; JP2003501408A; HUP0201400A3; BR0011111A; WO2000075095A1; MXPA01012344A; AU5214300A; US6559343B1; CA2375651A1

Abstract

The invention relates to a method for producing 2,2,4,4 tetra-substituted 1,3,5 - cyclohexanetriones of formula (I), by reacting a cyclobutane-1,3-diones of formula (II) with an O or N nucleophile and a silylation reagent and then subsequently by acetylisation and cyclisation.

Description

Process for the preparation of 2, 2, 4, 4-tetrasubstituted 1,3, 5-cyclohexanetrions

description

The present invention relates to a process for the preparation of 2, 2, 4, 4-tetrasubstituted 1, 3, 5-cyclohexanetrions of the formula I.

2, 2, 4, 4 -tetrasubstituted 1, 3, 5-cyclohexanetriones of the formula I are used as intermediates for the preparation of herbicidally active compounds, as described, for example, in EP-B 283 152.

Processes for their production are therefore of particular interest.

So far, the following syntheses are known as processes for the preparation of 2, 2, 4, 4-tetrasubstituted 1, 3, 5-cyclohexanetrions:

1. The reaction of 2, 4, 6-trihydroxyacetophenone with an excess of methyl iodide and sodium methoxide and subsequent deacetylation using hydrochloric acid. The overall yield of 2, 2, 4, 4-tetramethyl-1, 3, 5-cyclohexanetrione (based on

2,4,6-trihydroxyacetophenone) is 37%. (EP-B 283 152)

65% 57%

2. Starting from dimethyl acetone dicarboxylate, methyl tetra-C-methylacetone dicarboxylate was obtained, converted into the methyl dicarboxylic acid chloride and then methylated with dimethyl cadmium. The 2, 2, 4, 4-tetramethyl-3, 5-dioxo-hexancarboxylic acid methyl ester obtained in this way could be cyclized in the presence of sodium methoxide. The overall yield (based on dimethyl acetone dicarboxylate) is 0.01% (Chem. Ber. 92, 2033 (1959)).

62, 5

, 3 56.5 51.8

2, 4, 4-trimethyl-3-oxopentanecarboxylic acid ethyl ester was converted into the silylenol ether at -78 ° C., acetylated in the presence of ZnCl and then cyclized in the presence of lithium diisopropylamide. The overall yield (based on 2,4,4-trimethyl-3-oxopentanecarboxylic acid ethyl ester) is 50% (M. Benbakkar et al., Synth. Commun. 19 (18) 3241).

82% 62% It is also known that

4. Rearrange silyl ketene acetals under thermal stress to silylenol ether. If the silyl ketene acetal of methyl isobutyrate is thermolysed at 200 ° C. in bulk, 2, 4, 4 -trimethyl-3 - (trimethylsilyloxy) -pent-2-ene-carboxylic acid methyl ester is obtained in 75% yield. As a by-product, i.a. 2, 2, 4, 4 -tetramethyl-1,3-cyclobutadiene (C. Ainsworth et al., J. Orgmetal. Chem. 46 (1972) 59).

75%

Both the first and the second synthetic route mentioned above provide 2, 2, 4, 4-tetramethyl-1, 3, 5-cyclohexanetrione in unsatisfactory yields. In addition, the toxic dirnethyl cadmium is used in the multi-stage 2nd reaction sequence.

The third synthesis variant requires two equivalents of base to prepare the silyl ether. Furthermore, work must be carried out at low temperatures (-78 ° C.), so that this process is also problematic from a technical point of view.

The preparation of 2, 4, 4-trimethyl -3 - (trimethylsilyloxy) -pent-2-ene-carboxylic acid methyl ester according to sequence 4 requires working in a bomb tube - this is complex, complicated and expensive. In addition, the required silyl ketene acetals are difficult to manufacture.

As a result, these synthetic routes are unsatisfactory as economical and efficient processes for the preparation of 2, 2, 4, 4 - tetrasubstituted 1, 3, 5-cyclohexanetrions.

It is therefore an object of the present invention to find an alternative synthesis process for the preparation of 2, 2, 4, 4-tetrasubstituted 1, 3, 5-cyclohexanetrions which does not have the disadvantages mentioned above of the previously known preparation methods.

This object is achieved by the process according to the invention for the preparation of 2, 2, 4, 4 -tetrasubstituted 1, 3, 5-cyclohexanetrions of the formula I.

in the

R ^ R ² -C ₆ alkyl or C ₃ -C ₆ cycloalkyl, where these two radicals can be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: -C ₄ alkoxy, -C ₄ -Alkylthio or Di- (-C-C ₄ alkyl) amino; -CC ₆ alkoxy, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl; Aryl, aryloxy or heterocyclyl, which has up to three hetero atoms from the group 0, S and N, the aryl, aryloxy and heterocyclyl radicals being unsubstituted or partially or completely halogenated and / or substituted by the following radicals can: Cι-C -alkyl, C ₄ haloalkyl, Cι-C ₄ alkoxy, C ₁ -C ₄ halo-alkoxy or Cι-C alkoxycarbonyl;

or two radicals R ¹ and R ² which are bonded to the same carbon together form a - (CH ₂ ) ₂ . ₆ chain, which can be substituted by the following radicals:

Halogen, Cι-C ₄ -alkyl, C ₄ haloalkyl, C ₁ -C ₄ -alkoxy, C ₄ -haloalkoxy or Cχ-C ₄ alkoxycarbonyl; mean;

characterized in that one

a) a cyclobutane 1,3-dione of the formula II

where R ¹ and R ^{2 have} the meaning given above, with a 0- or N-nucleophile, optionally in the presence of a base, and a silylating reagent to give the silylenol ether of the formula III, in which

R ³ Ci-Cg alkoxy, amino, Cχ-C ₆ alkylamino or di- (Ci-Cβ-alkyl) amino;

R ⁴ -C ₆ alkyl or phenyl;

R ¹ and R ^{2 have} the meaning given above;

implements;

b) the compound III by acetylation, optionally in the presence of a Lewis acid, into the tricarbonyl compound of the formula IV,

wherein R ¹ to R ^{3 have} the meaning given above;

transferred;

c) the compound IV in the presence of a base to the

2, 2, 4, 4- tetrasubstituted cyclohexanetrione of formula I cyclized.

The reaction sequence for the preparation of the 2, 2, 4, 4 -tetrasubstituted 1, 3, 5-cyclohexanetriones of the formula I is summarized in the following scheme:

Scheme 1:

II stage a) III

ng e]

The individual reaction stages and preferred embodiments are explained in more detail below. The preferred embodiments of the individual reaction stages apply not only on their own but also in combination with the other process stages:

Stage a):

II III

In this reaction, Ci-Cβ alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-propan-1-ol, 2-methyl-propane are used as O-nucleophiles -2-ol, 1-pentanol,

2-pentanol, 3-pentanol, 2-methyl-butan-1-ol, 3-methyl-butan-1-ol, 1, 1-dimethylpropan-1-ol, 1, 2-dimethylpropan-1-ol, 2, 2-dimethyl-propan-1-ol, 1-hexanol, 2-hexanol, 3-hexanol or 2-ethylhexanol into consideration.

Suitable N-nucleophiles are ammonia, C 1 -C 6 -alkylamines, such as methylamine, ethylamino, 1-propylamine, 2-propylamine, 1-butylamine, 2-butylamine, 2-methylprop-1-ylamine, 2-methylprop-2-ylamine , 1-pentylamine, 2-pentylamine, 3 -pentylamine, 2-methyl-but-1-ylamine, 3-methylbut-1-ylamine, 1, 1-dimethylprop-1-ylamine, 1, 2-dimethylprop-1 -ylamine, 2,2-dimethylprop-1-ylamine, 1-hexylamine, 2-hexylamine or 3-hexylamine or di (Ci-Cβ-alkyl) amines such as dimethylamine, Diethylamine, di- (1-propyl) amine, di- (2-propyl) amine, di (l-butyl) amine, di- (2-butylamine), di- (2-methylprop-1-yl) amine, di - (2-methylprop-2-yl) amine, di- (1-pentylamine), di- (2-pentyl) amine, di- (3-pentylamine), di (2-methylbut-1-yl) amine, di - (3-methyl-but-l-yl) amine, di- (1, 1-dimethylprop-l-yl) amine, di- (1, 2-dimethylprop-1-yl) amine, di- (2 , 2-dimethylprop-l -yl) amine, di- (1-hexyl) amine, di- (2-hexyl) amine, di- (3-hexyl) amine, N-methyl-N-ethylamine, N-Me- ethyl-N-1-propylamine, N-methyl-N-2-propylamine, N-methyl-N-1-butylamine, N-methyl-N-2-butylamine, N-methyl-N-2-methyl-prop- 1-ylamine, N-methyl-N-2-methylprop- 2 -ylamine, N-methyl-N-pentylamine, N-methyl-N-2 -pentylamine, N-methyl-N-3 -pentylamine, N-Me- ethyl-N-2-methylbut-l-ylamine, N-methyl-N-3-methylbut-1-ylamine, N-methyl-N-1, 1-dimethylprop-l-ylamine, N-methyl-N-1, 2-dimethyl-prop-1-ylamine, N-methyl-N-2, 2-dimethylprop-1-ylamine, N-methyl-N-1-hexylamine, N-methyl-N-2-hexylamine, N- Methyl-N-3-hexyl-amine, N-ethyl-N-1- propylamine, N-ethyl-N-2-propylamine, N-ethyl-N-1-butylamine, N-ethyl-N-2-butylamine, N-ethyl-N-2-methylprop-1-ylamine, N-ethyl- N-2-methylprop- 2 -ylamine, N-ethyl-N-pentylamine, N-ethyl-N-2-pentylamine, N-ethyl-N-3 -pentylamine, N-ethyl-N-2-methylbut- 1 -ylamine, N-ethyl-N-3-methylbut-1-ylamine, N-ethyl-N-1, 1-dimethylprop-l -ylamine, N-ethyl-N-1, 2-dimethylprop-1 - ylamine, N-ethyl-N-2, 2-dimethylprop-1-ylamine, N-ethyl-N-1-hexylamine, N-ethyl-N-2-hexylamine or N-ethyl-N-3-hexylamine.

Also suitable are the alkali metal or alkaline earth metal salts of Ci-Cs alcohols, Ci-C _ö alkylamines or di- (Ci-C _ß- alkyl) amines and ammonia, for example the lithium, sodium, potassium, Magnesium or calcium salts.

If Ci- Ca alcohols, ammonia, Cχ-C ₆ -alkylamine or di (Ci-Cβ-alkyl) amine are used as O- or N-nucleophiles, it may be advantageous to use a base. For this purpose, hydrides such as sodium hydride or potassium hydride, carbonates such as sodium carbonate, potassium carbonate, hydrogen carbonates such as sodium hydrogen carbonate or potassium hydrogen carbonate or amine bases such as triethylamine, pyridine, etc. come into consideration.

Preferred 0- and N-nucleophilic alkali alcoholates, such as sodium methoxide, sodium ethanolate, sodium 1-propanolate,

Sodium 2-propanolate, sodium 1-butoxide, sodium 2-butoxide, sodium 2-methyl-propane-1-olate, sodium 2-methyl-propane-2-olate, sodium 2-ethyl-hexane l-olate, potassium methoxide, potassium ethanolate, potassium 1-propanolate, potassium 2-propanolate, potassium 1-butoxide, potassium 2-butoxide, potassium 2-methyl propane-1-olate, potassium 2-me- thyl-propane-2 -olate or potassium-2-ethyl-hexane-1 -olate or alkaline-earth alcoholates such as calcium methylate, calcium ethanolate, Calcium 1-propanolate, calcium 1-butanolate, magnesium methylate, magnesium ethanolate, magnesium 1-propanolate or magnesium 1-butoxide are used.

In particular, alkali alcoholates as listed above are suitable. Sodium methoxide or sodium ethanolate, in particular sodium methoxide, is particularly preferably used.

Suitable silylating reagents are alkyl- and / or phenyl-substituted silyl halides, in particular trialkylsilyl halides such as trimethylsilyl chloride, triethylsilyl chloride, trimethylsilyl bromide, trimethylsilyl iodide, tert. -Butyl-dimethylsilyl chloride, isopropyl-dimethylsilyl dichloride, tri-isopropylsilyl chloride, tri- n-propylsilyl chloride, tri-n-butylsilyl chloride, alkyl-phenylsilyl halides such as methyl-diphenylsilyl chloride, tert. -Butyl-diphenylsilyl chloride or dimethyl-phenylsilyl chloride, or triphenylsilyl halides such as triphenylsilyl chloride.

Trialkylsilyl halides as indicated above are preferably used. Trimethylsilyl chloride is particularly suitable.

Cyclobutane-1,3-diones of the formula II are preferred, wherein

R ¹ -C ₆ alkyl or C ₃ -C ₆ cycloalkyl, where these two radicals can be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: C ₁ -C ₄ alkoxy, C ₁ -C ₄ Alkylthio or di (C ₁ -C ₄ alkyl) amino; C -C ₆ alkenyl or C ₂ -C ₆ alkynyl;

Aryl or heterocyclyl, which has up to three heteroatoms from the group 0, S and N, where the aryl and heterocyclyl radicals may be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: -C-C ₄ -alkyl, C ₄ haloalkyl, Cι-C ₄ -alkoxy, C ₄ -haloalkoxy or Cι-C ₄ alkoxycarbonyl;

R ^{2 is} a radical mentioned under R ¹ , and also Ci-C _ß -alkoxy or aryloxy, which may be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: C ₁ -C ₄ -alkyl, -C-C -haloalkyl, C ₁ -C ₄ alkoxy, Ci -C haloalkoxy or Ci -C ₄ alkoxycarbonyl;

or two radicals R ¹ and R ² , which are bonded to the same carbon, together form a - (CH) _2-6 chain, which can be substituted by the following radicals:

Halogen, C ₁ -C ₄ -alkyl, C ₄ haloalkyl, C ₁ -C ₄ -alkoxy, C ₄ -haloalkoxy or Cχ-C ₄ alkoxycarbonyl; mean used. Cyclobutane-1,3-diones of the formula II are particularly preferred where:

R 1, R ² -C ₆ -alkyl which may be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: -C ₄ -C alkoxy, -C -C alkylthio or di - (Ci -C - alkyl) mino;

or two radicals R ¹ and R ² , which are bonded to the same carbon, together form a - (CH) _-6 chain, which can be substituted by the following radicals:

Halogen, Cι-C -alkyl, C ₄ haloalkyl, C ₁ -C ₄ -alkoxy, C ₄ -haloalkoxy or Cι-C ₄ alkoxycarbonyl; mean used.

The reaction is usually carried out in a solvent or diluent. Alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol or 2-butanol, ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, anisole or tetrahydrofuran, aromatic hydrocarbons such as toluene or xylene or are particularly suitable for this Dipolar aprotic solvents such as dimethylformamide or diethylformamide. However, mixtures of these can also be considered.

Is preferably carried out in alcohols such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol or 2-butanol or ethers such as diethyl ether, diisopropyl ether, tert. -Butyl methyl ether, dioxane, anisole or tetrahydrofuran. However, mixtures of these can also be considered.

The reaction is preferably carried out in an ether as indicated above or if an alcoholate is used as the O-nucleophile in the corresponding alcohol. In particular come ethers such as diethyl ether, methyl tert. -butyl ether or tetrahydrofuran.

As a rule, the 2, 2, 4, 4-tetrasubstituted cyclobutane-1, 3-dione, the 0- or N-nucleophile and the silylation reagent are approximately like the stoichiometric ratio (0.8: 1 - 1 , 2: 1) used.

In the event that a base is added, this is also used in an approximately stoichiometric ratio (0.8: 1 - 1.2: 1) with respect to the compound of the formula II. It can be advantageous to work in the absence of water.

The reaction is generally carried out in a temperature range from 0 to 120 ° C., in particular from 0 to 60 ° C.

Furthermore, this reaction is carried out at a pressure of 1 to 50 bar, preferably at 1 to 10 bar.

Usually, the cyclobutane-1,3-dione of the formula II and the O / N nucleophile are placed in a solvent / diluent and the silylation reagent is added in the desired temperature range, preferably at room temperature while ensuring the mixing. The latter can be carried out in bulk or in a solvent / diluent. The processing takes place in analogy to known processing methods.

III IV

In this reaction, acetyl halides such as acetyl chloride or acetyl bromide, acetyl cyanide, mixed anhydrides of acetic acid with inorganic acids, such as methylsulfonic acid or trifluoromethylsulfonic acid, acetylimidazolide or acetic anhydride, are used as acetylation reagents, for example. Acetyl halides, in particular acetyl chloride, are preferred.

The acetylation takes place in the presence of a Lewis acid. In particular, zinc, aluminum, antimony, titanium, tin, boron, iron, nickel and cobalt halides are used, preferably the corresponding chlorides or bromides. ZnCl ₂ , SbCl ₃ SbCl ₅ , TiCl ₄ , SnCl ₄ , BC1 ₃ , FeCl ₃ , A1C1 ₃ , AlBr ₃ etc., or mixtures thereof, are particularly suitable. In particular, ZnCl, A1C1 ₃ or SbCl ₃ are used, particularly preferably ZnCl.

The reaction is usually carried out in a solvent or diluent. Halogenated hydrocarbons, such as methylene chloride, chloroform, 1, 2-dichloroethane or chlorobenzene, or ethers such as diethyl ether, diisopropyl ether, methyl tert. -butyl ether, dioxane, tetrahydrofuran or anisole or mixtures thereof. Aliphatic, halogenated hydrocarbons, such as methylene chloride, chloroform or 1,2-dichloroethane or aliphatic / cycloaliphatic ethers such as diethyl ether, diisopropyl ether, methyl tert. -butyl ether, dioxane or tetrahydrofuran used. In particular, methylene chloride or diethyl ether or mixtures thereof can be considered.

The silylenol ether of the formula III and the acetylating reagent are usually used in a stoichiometric ratio. However, it can also be advantageous to use an excess of acetylene reagent. It is preferable to work approximately in a stoichiometric ratio. The acetylation reagent and the Lewis acid are generally used in a ratio of 1: 0.1 to 1: 2 (mol ratio), preferably a ratio of 1: 0.5 to 1: 1.5, in particular approximately a ratio of 1: 1.

Silylenol ethers of the formula III are preferably used, where R ^{3 is} Ci-Cβ-alkoxy, in particular methoxy.

Silylenol ethers of the formula III are particularly preferably used, where

R ⁱ Cχ-C ₆ alkyl or C ₃ -C ₆ cycloalkyl, where these two radicals may be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: -C -alkoxy, C ₁ -C ₄ -alkylthio or di (C ₁ -C ₄ alkyl) amino; C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl;

Aryl or heterocyclyl, which has up to three heteroatoms from the groups 0, S and N, where the aryl and heterocyclyl radicals can be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: -C ₄ -Alkyl, -CC ₄ -haloalkyl, -C-C ₄ -alkoxy, -C-C ₄ -haloalkoxy or -C-C ₄ -alkoxycarbonyl;

R ^{2 is} a radical mentioned under R ¹ , and also Ci-Cg -alkoxy or aryloxy, which may be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: -CC ₄ -alkyl, -C-C ₄ -haloalkyl, -C. -C ₄ alkoxy, Ci -C -haloalkoxy or -C-C ₄ alkoxycarbonyl;

or two radicals ⁱ and R ² , which are bonded to the same carbon, together form a - (CH ₂ ) _2-6 chain, which can be substituted by the following radicals:

Halogen, Cι-C ₄ -alkyl, C haloalkyl, C ₁ -C ₄ -alkoxy, C ₄ -haloalkoxy or C ₁ -C ₄ alkoxycarbonyl; mean. Silylenol ethers of the formula III are particularly preferably used, where:

R 1, R ² C ₁ -C 6 -alkyl, which may be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: C ₁ -C ₄ -alkoxy, Cχ-C ₄ -alkylthio or di- (C ₁ -C _4- alkyl) amino;

Halogen, C ₁ -C ₄ -alkyl, C ₄ haloalkyl, C ₁ -C ₄ alkoxy, _{Cχ-C4-haloalkoxy} or Cι-C ₄ alkoxycarbonyl; mean.

The reaction is generally carried out in a temperature range from -30 ° C. to the boiling point of the solvent / solvent mixture. Usually one works in a range of -15 to 40 ° C, preferably under ice cooling.

Furthermore, this reaction is carried out at a pressure of 1 to 50 bar, preferably at normal pressure.

The acetylating reagent and the Lewis acid are usually initially introduced into the solvent / diluent or a corresponding mixture and the silyl enol ether of the formula III in bulk or in a solvent / diluent or a corresponding mixture is added dropwise, the reaction temperature being kept in the desired range by cooling, if appropriate.

It can be advantageous to work in the absence of water.

The processing is carried out in analogy to known processing methods.

Stage c):

IV Inorganic and organic bases as well as metal hydride and organometallic bases come into consideration as bases.

In this reaction, inorganic bases such as alkali metal hydroxides, e.g. Sodium hydroxide or potassium hydroxide, alkaline earth metal hydroxides, e.g. Calcium hydroxide or magnesium hydroxide, alkali alcoholates, such as sodium methoxide, sodium ethanolate, sodium 1-propanolate, sodium 2-propanolate, sodium 1-butanolate, sodium 2-butoxide, sodium 2-methyl propane-1 -olate, sodium 2 -methyl-propane-2-olate, sodium 2-ethyl-hexan-1-olate, potassium methoxide, potassium ethanolate, potassium 1-propanolate, potassium 2-propanolate, potassium 1-butoxide, potassium 2-butoxide, potassium -2-methyl-propane-1 -olate, potassium-2-methyl-propane-2 -olate or potassium-2-ethyl-hexane-1 -olate or alkaline earth metal alcoholates such as calcium methylate, calcium ethanolate, calcium 1-propanolate,

Calcium 1-butanolate, magnesium methylate, magnesium ethanolate, magnesium 1-propanolate or magnesium 1-butanolate, alkali oxides, e.g. Sodium oxide or potassium oxide, alkaline earth oxides, e.g. Calcium oxide or magnesium oxide, alkali hydrogen carbonates such as sodium hydrogen carbonate or potassium hydrogen carbonate, earth alkali hydrogen carbonates such as magnesium hydrogen carbonate or calcium hydrogen carbonate, alkali carbonates such as sodium carbonate or potassium carbonate or alkaline earth carbonates such as calcium carbonate or magnesium carbonate.

Organic bases, for example amine bases such as trialkylamines, e.g. Triethylamine, or aromatic nitrogen bases such as pyridine.

It is also possible to use hydrides such as sodium hydride, potassium hydride or lithium aluminum hydride or organometallic bases such as butyllithium, lithium diisopropylamide etc.

In particular, inorganic bases as listed above, in particular alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal oxides, alkaline earth metal oxides, alkali metal hydrogen carbonates, alkaline earth metal hydrogen carbonates, alkali metal carbonates or alkaline earth metal carbonates, as described above, preferably alkali metal or alkaline earth metal hydroxides, are used.

Amine bases as listed above, preferably trialkylamines, are likewise used in particular.

Sodium hydroxide is particularly preferably used. Tricarbonyl compounds of the formula IV are preferably used, where R ^{3 is} Ci-Cs-alkoxy, in particular methoxy.

Tricarbonyl compounds of the formula IV are particularly preferably used, where

R ⁱ Ci-Cβ-alkyl or C ₃ -C ₆ cycloalkyl, where these two radicals can be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: -C-C ₄ alkoxy, C ₁ -C ₄ alkylthio or di- (-C ₄ alkyl) amino; C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl;

Aryl or heterocyclyl, which has up to three heteroatoms from the groups 0, S and N, where the aryl and heterocyclyl radicals can be unsubstituted or partially or fully halogenated and / or substituted by the following radicals: C ₁ -C ₄ -alkyl, C ₄ haloalkyl, C ₁ -C ₄ -alkoxy, C ₄ -haloalkoxy or C ₁ -C ₄ alkoxycarbonyl;

R ² is a said under R ^1, and _Cι-C6 alkoxy or aryloxy which is unsubstituted or may be partially or fully halogenated and / or substituted by the following radicals: C ₄ -alkyl, C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ haloalkoxy or Cχ-C ₄ alkoxycarbonyl;

or two radicals R ¹ and R ² , which are bonded to the same carbon, together form a - (CH ₂ ) _2-6 chain, which can be substituted by the following radicals:

Halogen, Cι-C ₄ -alkyl, C haloalkyl, Cι-C ₄ -alkoxy, C ₄ -haloalkoxy or Cχ-C alkoxycarbonyl; mean.

Tricarbonyl compounds of the formula IV are particularly preferably used, where

R, R ² Ci-Cβ-alkyl, which may be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: -CC ₄ -alkoxy, -C-C ₄ -alkylthio or di- (C ₁ -C ₄ - alkyl) amino;

or two radicals ⁱ and R ² , which are bonded to the same carbon, together form a - (CH) _-6 chain, which can be substituted by the following radicals:

Halogen, Cι-C ₄ -alkyl, C ₄ haloalkyl, Cχ-C ₄ -alkoxy, C ₄ haloalkoxy or _Ci-C4 alkoxycarbonyl; mean. The reaction is usually carried out in an inert solvent or diluent. For example, ethers such as diethyl ether, diisopropyl ether, methyl tert are suitable for this. -butyl ether, dioxane, tetrahydrofuran or anisole, aromatic hydrocarbons such as benzene or toluene, or aprotic, dipolar solvents such as dimethylformamide or dimethyl sulfoxide or mixtures thereof. Aliphatic / cycloaliphatic ethers such as diethyl ether, diisopropyl ether and methyl tert are preferred. - Butyl ether, dioxane or tetrahydrofuran, or aprotic, dipolar solvents as mentioned above, used.

Diethyl ether, tetrahydrofuran, dimethylformamide and dimethyl sulfoxide are particularly suitable.

The tricarbonyl compound of the formula IV and the base are usually used in a ratio of 1: 1 to 1: 4 (molar ratio), preferably in a ratio of 1: 1 to 1: 2.5.

In the case of the use of inorganic bases, as stated above, it can be advantageous to work approximately in the stoichiometric ratio.

The reaction is generally carried out in a temperature range from -75 ° C. to the boiling point of the solvent / solvent mixture. Is preferably carried out in a temperature range from -30 ° C to the boiling point of the solvent / solvent mixture. When using inorganic bases or amine bases, the procedure is preferably in a range from 0 to 120 ° C., preferably in a range from 20-100 ° C.

Furthermore, this reaction is carried out at a pressure of 1 to 100 bar, preferably at a pressure of 1 to 20 bar, in particular at normal pressure.

As a rule, the base is placed in the solvent / diluent and the tricarbonyl compound of the formula IV, if appropriate in a solvent / diluent, is added in the desired temperature range while ensuring thorough mixing. The processing takes place in analogy to known processing methods.

It is also possible to obtain the cyclobutane-1,3-dione of the formula II by reacting an acid halide of the formula V, where shark for halide and R and R ^{2 have} the meaning given for the compound I with a base.

Level al)

II

In this reaction, amine bases such as trialkylamines, e.g. Triethylamine or aromatic nitrogen base, e.g. Pyridine. Trialkylamines, in particular triethylamine, are preferably used.

Usually the chloride or bromide, especially the acid chloride, is used as the acid halide.

Acid halides of the formula V are particularly preferably used, where:

R ⁱ Ci-Cβ-alkyl or C ₃ -C ₆ cycloalkyl, where these two radicals can be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: C ₁ -C ₄ alkoxy, C ₁ -C ₄ - Alkylthio or di (C ₁ -C ₄ alkyl) amino; C ₂ -C ₆ alkenyl or C -C ₆ alkynyl; Aryl or heterocyclyl, which has up to three heteroatoms from the group 0, S and N, where the aryl and heterocyclyl radicals may be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: -C ₄ -alkyl , -C-C ₄ -haloalkyl, -C-C ₄ -alkoxy, Cι-C ₄ -haloalkoxy or Ci -C ₄ -alkoxycarbonyl;

R ^{2 is} a radical mentioned under R ¹ , and C ₁ -C ₆ -alkoxy or aryloxy, which may be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: -C ₄ -alkyl, C ₁ -C -haloalkyl, C ₁ -C ₄ alkoxy, Ci-C ₄ haloalkoxy or C ₁ -C ₄ alkoxycarbonyl;

or two radicals R ¹ and R ² , which are bonded to the same carbon, together form a - (CH ₂ ) ₂ - ₆ * chain, which can be substituted by the following radicals: halogen, C ₁ -C ₄ alkyl, Cι -C ₄ haloalkyl, Cι-C ₄ -alkoxy, C ₄ -haloalkoxy or C ₁ -C ₄ alkoxycarbonyl; mean.

Acid halides of the formula V are particularly preferably used, where: Ri, R ² Ci-Cβ-alkyl, which can be unsubstituted or partially or fully halogenated and / or substituted by the following radicals: Cχ-C ₄ alkoxy, C ₁ -C ₄ alkylthio or di - (Ci -C ₄ - alkyl) amino;

Halogen, Cι-C ₄ -alkyl, C haloalkyl, Cχ-C ₄ -alkoxy, C ₄ -haloalkoxy or C ₁ -C ₄ alkoxycarbonyl; mean.

The reaction is usually carried out in an inert solvent or diluent. For example, ethers such as diethyl ether, diisopropyl ether and methyl tert are suitable for this. butyl ether, dioxane, tetrahydrofuran or anisole, glycols such as diethylene glycol dimethyl ether, aromatic hydrocarbons such as benzene, toluene or xylene or halogenated hydrocarbons such as methylene chloride, chloroform, 1, 2-dichloroethane or chlorobenzene, or mixtures thereof. Aliphatic ethers such as diethyl ether, diisopropyl ether or methyl tert are preferred. -butyl ether, glycols, such as diethylene glycol dimethyl ether or aromatic hydrocarbons, such as benzene, toluene or xylene, in particular methyl tert. -butyl ether, diethylene glycol dimethyl ether or toluene.

As a rule, the acid halide of the formula V and the base are used in a ratio of 1: 1 to 1: 3, preferably in the range from 1: 1.5 to 1: 2.5.

In general, the reaction is carried out at elevated temperature, in particular in the range of the boiling point of the solvent / diluent.

Furthermore, the reaction is carried out at a pressure of 1 to 100 bar.

The acid chloride is usually initially introduced into the solvent / diluent and the base, if appropriate dissolved in a solvent / diluent, is added. The mixture is then heated to the reflux temperature of the solvent / diluent.

The processing takes place in analogy to known processing methods. It is also possible to use the compounds II, III or IV in the next step without purification.

It is also possible to carry out stages a) and b) or b) and c) or al) and a) or a), b) and c) or al, a) and b) or al), a), b) and c) to be designed as a "one-pot process".

Here come as solvents in particular ethers such as diethyl ether, methyl tert. butyl ether, tetrahydrofuran or dioxane or dipolar solvents such as dimethyl sulfoxide or mixtures thereof.

Stage a) of the process according to the invention is a new and advantageous process for the preparation of silylenol ethers of the formula III. The present invention therefore also relates to the process described in step a). The preferred embodiments described there apply accordingly.

Furthermore, stage c) of the process according to the invention, if an oxide, hydroxide, hydrogen carbonate or carbonate of an alkali or alkaline earth metal is used as the base, is a new and advantageous process for preparing 2, 2, 4, 4-tetrasubstituted cyclohexane -1, 3, 5- trions of formula I. This is also the subject of the present invention.

The bases include alkali metal hydroxides, such as sodium hydroxide or potassium hydroxide, alkaline earth metal hydroxides, such as calcium hydroxide or magnesium hydroxide, alkali metal oxides such as sodium oxide or potassium oxide, alkaline earth metal oxides, such as calcium oxide or magnesium oxide, alkali metal hydrogen carbonates, such as sodium hydrogen carbonate or potassium hydrogen carbonate, alkaline earth metal hydrogen carbonate or sodium carbonate, such as magnesium bicarbonate or sodium carbonate, such as magnesium bicarbonate, such as magnesium bicarbonate, Potassium carbonate or alkaline earth carbonates such as calcium carbonate or magnesium carbonate.

Alkali or alkaline earth metal hydroxides, such as sodium, potassium, calcium or magnesium hydroxide, are preferably used.

Sodium hydroxide is particularly preferably used.

The reaction is usually carried out in an inert solvent or diluent. For example, ethers such as diethyl ether, diisopropyl ether and methyl tert are suitable for this. -butyl ether, dioxane, tetrahydrofuran or anisole or aprotic solvents solvents such as dimethylformamide or dimethyl sulfoxide, or mixtures thereof.

Aliphatic / cycloaliphatic ethers such as diethyl ether, diisopropyl ether, methyl tert-tert-ether, dioxane or tetrahydrofuran, or aprotic, dipolar solvents as mentioned above are preferably used.

Diethyl ether, tetrahydrofuran and dirnethyl sulfoxide are particularly suitable.

The tricarbonyl compounds of the formula IV and the base are usually used in a ratio of 1: 1 to 1: 4 (molar ratio), preferably in a ratio of 1: 1 to 1: 2.5. It can be advantageous to work in a stoichiometric ratio.

The reaction is generally carried out in a temperature range from -75 ° C. to the boiling point of the solvent / solvent mixture. The process is preferably carried out in a range from -30 ° C. to the boiling point of the solvent / solvent mixture, particularly in the range from 0 to 120 ° C., in particular 20-100 ° C. Otherwise, the embodiments listed under stage c) apply.

Furthermore, stage c) of the process according to the invention, when an alkali or alkaline earth alcoholate in a ratio of 1: 1 to 1: 3 (compound IV: base; mol ratio) is used as the base, is a new and advantageous process for the preparation of 2, 2, 4, 4-tetrasubstituted cyclohexane-1, 3, 5-trions of the formula I.

As alkali or alkaline earth alcoholates come alkali alcoholates such as sodium methoxide, sodium ethanolate, sodium 1-propanolate, sodium 2-propanolate, sodium 2-butoxide, sodium 2-methyl-propane-1-olate, sodium 2-methyl - propane-2-olate, sodium 2-ethyl-hexane-1-olate, potassium methoxide, potassium ethanolate, potassium 1-propanolate, potassium 2-propanolate, potassium 1-butoxide, potassium 2-butoxide, potassium 2-methyl propane-1-olate, potassium 2-methyl propane-2-olate or potassium 2-ethyl-hexane-1-olate or alkaline earth alcoholates such as calcium methanolate, calcium ethanolate, calcium 1-propanolate, calcium 1-but- tanolate, magnesium methylate, magnesium methoxide, magnesium 1-propanolate or magnesium 1-butoxide.

In particular, alkali alcoholates as listed above are used. Sodium methoxide, sodium ethoxide or potassium 2-methylpropan-2-olate are particularly used. The reaction is usually carried out in an inert solvent or diluent. For example, ethers such as diethyl ether, diisopropyl ether, methyl tert are suitable for this. -butyl ether, dioxane, tetrahydrofuran or anisole or aprotic solvents such as dimethyl sulfoxide or mixtures thereof.

Aliphatic or cycloaliphatic ethers such as diethyl ether, diisopropyl ether, methyl tert are preferred. -butyl ether, dioxane or tetrahydrofuran used. Diethyl ether and tetrahydrofuran are particularly suitable.

The tricarbonyl compound of the formula IV and the alkali metal or alkaline earth metal alcoholate are usually used in a ratio of 1: 1 to 1: 3 (molar ratio), preferably in a ratio of 1: 1 to 1: 2.5.

The reaction is generally carried out in a temperature range from -75 ° C. to the boiling point of the solvent / solvent mixture. Is preferably carried out in a range from -30 ° C to boiling temperature, in particular at 20-100 ° C.

Otherwise, the statements listed under stage c) apply.

The present invention further provides the new 2, 2, 4, 4-tetrasubstituted 1, 3, 5-cyclohexanetriones of the formula I ',

wherein R ⁱ and R ² , which are bonded to the same carbon, a

- (CH ₂ ) _-6 "chain, which can be substituted by the following radicals:

Halogen, Cι-C ₄ -alkyl, C ₄ haloalkyl, Cι-C ₄ -alkoxy, C ₄ genalkoxy -Halo- or C ₁ -C ₄ -alkoxycarbonyl.

The compounds of the formula I are particularly preferred, where R 1 and R ² which are bonded to the same carbon are one

- Form (CH) -6 chain.

Likewise, the new silylenol ethers of the formula III ' where the variables have the following meaning:

R ⁱ , R ² -C ₆ alkyl or C ₃ -C ₆ cycloalkyl, where these two radicals can be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: C ₁ -C ₄ alkoxy, Cχ-C ₄ alkylthio or di - (Ci-C ₄ alkyl) amino;

-C-C ₆ alkoxy, C -C ₆ alkenyl or C ₂ -C ₆ alkynyl; Aryl, aryloxy or heterocyclyl, which has up to three hetero atoms from the groups 0, S and N, where the aryl, aryloxy and heterocyclyl radicals can be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: Cι-C ₄ -alkyl, C ₄ haloalkyl, Cι-C ₄ -alkoxy, C ₄ -haloalkoxy or C ₁ -C ₄ alkoxycarbonyl;

or two radicals R ⁱ and R ² , which are bonded to the same carbon, together form a - (CH) _-6 chain, which can be substituted by the following radicals:

Halogen, Cι-C ₄ -alkyl, C ₄ haloalkyl, Cι-C -alkoxy, C ₄ -haloalkoxy or Ci-C ₄ alkoxycarbonyl;

R ³ amino, Cχ-C ₆ alkylamino or di- (-CC ₆ alkyl) amino;

R ⁴ -C ₆ alkyl or phenyl;

Subject of the present invention.

Particularly preferred are the compounds of formula III 'wherein R ³ represents di- (C _I -C _east alkyl) amino.

The present invention furthermore relates to the new tricarbonyl compounds of the formula IV,

where the variables have the following meaning: R !, R ² Ci-Cβ alkyl or C ₃ -C ₆ cycloalkyl, these two

Residues unsubstituted or partially or completely halogenated and / or can be substituted by the following radicals: C ₁ -C ₄ alkoxy, Cχ-C alkylthio or di- (Ci-C -alkyl) amino;

Ci-Cβ-alkoxy, C ₂ -C ₆ alkenyl or C ₂ -C ₆ alkynyl; Aryl, aryloxy or heterocyclyl, which has up to three hetero atoms from the groups 0, S and N, the aryl, aryloxy and heterocyclyl radicals being unsubstituted or partially or completely halogenated and / or substituted by the following radicals can be: -C ₄ -alkyl, -C-C ₄ -haloalkyl, -C-C -alkoxy, -C-C ₄ -haloalkoxy or C ₁ -C ₄ -alkoxycarbonyl;

Halogen, C ₁ -C ₄ -alkyl, C ₄ haloalkyl, Cι-C alkoxy, ^C ι ~ C ₄ haloalkoxy or C1-C4 alkoxycarbonyl;

R ³ amino, Ci-C _δ alkylamino or di- (-CC ₆ alkyl) amino.

The compounds of the formula IV are particularly preferred, where R ^{3 is} di- (Ci-Cβ-alkyl) amino.

The present invention also relates to the new tricarbonyl compounds of the formula IV ',

where R 1 and R ² , which are bonded to the same carbon, form a - (CH) _-6 "chain which can be substituted by the following radicals:

Halogen, C ₃ -C ₄ -alkyl, C ₄ haloalkyl, Cι-C ₄ -alkoxy, C ₄ -Halo- genalkoxy or _Ci-C4 alkoxycarbonyl;

R ³ Ci-C ₈ alkoxy;

mean.

The compounds of the formula IV 'are particularly preferred, where R ⁱ and R ² , which are bonded to the same carbon, form a - (CH ₂ ) _2-6 chain. The organic molecule parts mentioned for the substituents R ⁱ to R ⁴ or as radicals on phenyl or heterocyclyl radicals represent collective terms of individual lists of the individual group members. All hydrocarbon chains, ie all alkyl, haloalkyl, alkoxy, haloalkoxy, alkylthio -, Alkylamino, dialkylamino or alkoxycarbonyl parts can be straight-chain or branched. Unless stated otherwise, halogenated substituents preferably carry one to five identical or different halogen atoms. Halogen is fluorine, chlorine, bromine or iodine.

Furthermore, for example:

-C -C alkyl: e.g. Methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl or 1, 1-dimethylethyl;

C ₁ -C ₆ alkyl, C ₁ -C ₄ alkyl, as mentioned above, and for example

Pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl,

2, 2-dimethylpropyl, 1-ethylpropyl, hexyl, 1, 1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1, 1-dimethylbutyl, 1, 2-dimethylbutyl, 1,3-dimethylbutyl, 2, 2-dimethylbutyl, 2, 3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1-ethyl- l-methylpropyl or l-ethyl-3-methylpropyl;

C ₁ -C ₄ -haloalkyl: a Cι-C ₄ -alkyl radical as mentioned above which, chlorine, bromine / iodine or partially or completely substituted by fluorine and is substituted, eg chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl,

Trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorofluoromethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2-iodoethyl, 2, 2-difluoroethyl, 2, 2, 2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2- Chloro-2, 2-difluoroethyl, 2, 2-dichloro-2-fluoroethyl, 2, 2, 2-trichloroethyl, pentafluoroethyl, 2-fluoropropyl, 3-fluoropropyl, 2, 2-difluoropropyl, 2, 3-difluoropropyl, 2-chloropropyl, 3-chloropropyl, 2,3-dichloropropyl, 2-bromopropyl, 3-bromopropyl, 3,3, 3-trifluoropropyl, 3, 3, 3-trichloropropyl, 2, 2, 3, 3, 3- Pentafluoropropyl, heptafluoropropyl, 1- (fluoromethyl) -2-fluoroethyl, 1- (chloromethyl) -2-chloroethyl, 1- (bromomethyl) -2-bromomethyl, 4-fluorobutyl, 4-chlorobutyl, 4-bromobutyl or nonafluorobutyl;

C ₁ -C ₄ alkoxy: for example methoxy, Ξthoxy, propoxy, 1-methylethoxy, butoxy, 1-methylpropoxy, 2-methylpropoxy or 1, 1-dimethylethoxy; Ci-Cβ-alkoxy: -C-C ₄ alkoxy, as mentioned above, and for example pentoxy, 1-methylbutoxy, 2-methylbutoxy, 3-methylbutoxy,

1, 1-dimethylpropoxy, 1, 2-dimethylpropoxy, 2, 2-dimethylpropoxy, 1-ethylpropoxy, hexoxy, 1-methylpentoxy, 2-methylpentoxy, 3-methylpentoxy, 4-methylpentoxy, 1, 1-dimethyl butoxy, 1, 2-dimethylbutoxy, 1, 3-dimethylbutoxy, 2, 2-dimethylbutoxy, 2, 3-dimethylbutoxy, 3, 3-dimethylbutoxy, 1-ethylbutoxy, 2-ethylbutoxy, 1, 1, 2- Trimethylpropoxy, 1,2,2-trimethylpropoxy, 1-ethyl-1-methylpropoxy or 1-ethyl-2-methylpropoxy;

Ci-Cβ-alkoxy: Cχ-C ₆ -alkoxy, as mentioned above and 1-heptoxy, 1-octoxy or 2-ethylhexoxy;

- Cι-C ₄ -haloalkoxy: a _{Cι-C4-alkoxy} as mentioned above which is partially or completely, chlorine, bromine substituted by fluorine and / or iodine, ie for example fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, Bromdi - fluoromethoxy , 2-fluoroethoxy, 2-chloroethoxy, 2-bromomethoxy, 2-iodoethoxy, 2, 2-difluoroethoxy, 2, 2, 2-trifluoroethoxy,

2-chloro-2-fluoroethoxy, 2-chloro-2, 2-difluoroethoxy, 2,2-di-chloro-2-fluoroethoxy, 2, 2, 2-trichloroethoxy, pentafluoroethoxy, 2-fluoropropoxy, 3-fluoropropoxy, 2- Chloropropoxy, 3-chloropropoxy, 2-bromopropoxy, 3-bromopropoxy, 2, 2-difluoropropoxy, 2, 3-difluoropropoxy, 2, 3-dichloropropoxy, 3, 3, 3-trifluoropropoxy, 3,3,3-trichloropropoxy, 2, 2, 3, 3, 3-pentafluoropropoxy, heptafluoropropoxy, 1- (fluoromethyl) -2-fluoroethoxy, 1- (chloromethyl) -2-chloroethoxy, 1- (bromomethyl) -2-bromoethoxy, 4-fluorobutoxy, 4-chlorobutoxy, 4-bromobutoxy or nonafluorobutoxy;

C ₁ -C ₄ alkylthio: for example methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio or 1, 1-dimethylethylthio;

Ci-Cg-alkylamino: e.g. methylamino, ethylamino, propylamino, 1-methylethylamino, butylamino, 1-methylpropylamino, 2-methylpropylamino, 1, 1-dimethylethylamino, pentylamino, 1-methylbutylamino, 2-methylbutylamino, 3-methylbutylamino 2-Dirnethylpropylamino, 1-Ethylpropylamino, Hexylamino, 1, 1-Dirnethylpropylamino, 1, 2-Dirnethylpropylamino, 1-Methyl-pentylamino, 2-Methylpentylamino, 3-Methylpentylamino, 4-Methylpentylamino, 1, 1-Dimethylbutylamino Dimethylbutylamino, 1, 3-dimethylbutylamino, 2, 2-dimethylbutylamino, 2, 3-dimethylbutylamino, 3, 3-dimethylbutylamino, 1-ethylbutylamino, 2-ethylbutylamino, 1, 1, 2-trimethylpropylamino, 1, 2, 2-trimethylpropylamino, 1-ethyl-l-methylpropylamino or

1-Ethy1-2-methylpropylamino;

Di- (-C-alkyl) amino: e.g. N, N-dimethylamino, N, N-diethylamino, N, N-dipropylamino, N, N-di- (1-methylethyl) amino, N, N-dibutylamino, N, N-di- (1-methylpropyl ) amino, N, N-di- (2-methylpropyl) amino, N, N-di- (1, 1-dimethylethyl) - amino, N-ethyl-N-methylamino, N-methyl-N-propylamino, N- Methyl-N- (1-methylethyl) amino, N-butyl-N-methylamino, N-methyl-N- (1-methylpropyl) amino, N-methyl-N- (2-methylpropyl) amino, N- ( 1, 1-dimethylethyl) -N-methylamino, N-ethyl-N-propylamino, N-ethyl-N- (1-methylethyl) amino, N-butyl-N-ethyl-amino, N-ethyl-N- (1 -methylpropyl) amino, N-ethyl-N- (2-methyl-propyl) amino, N-ethyl-N- (1, 1-dimethylethyl) mino, N- (1-methylethyl) -N-propylamino, N -Butyl-N-propylamino, N- (1-methylpropyl) -N-propylamino, N- (2-methylpropyl) -N-propylamino, N- (1, 1-dimethylethyl) -N-propylamino, N-butyl -N- (1-methylethyl) amino, N- (1-methylethyl) -N- (1-methylpropyl) amino, N- (l-methylethyl) -N- (2-methylpropyl) amino, N- (1 -Dimethyl-ethyl) -N- (1-methylethyl) amino, N-butyl-N- (1-methylpro pyl) - amino, N-butyl-N- (2-methylpropyl) amino, N-butyl-N- (1, 1-dimethylethyl) amino, N- (1-methylpropyl) -N- (2-methylpropyl) amino , N- (1, 1-dimethylethyl) -N- (1-methylpropyl) amino or N- (1, 1-dimethylethyl) -N- (2-methylpropyl) amino;

Di- (-C ₆ -alkyl) amino: di- (Cχ-C ₄ -alkyl) amino as mentioned above, and N, N-dipentylamino, N, N-dihexylamino, N-methyl-N-pentylamino, N- Ethyl-N-pentylamino, N-methyl-N-hexylamino or N-ethyl -N-hexylamino;

C ₂ -C ₆ ~ alkenyl: for example ethenyl, prop-2-en-1-yl, but-1-en-4-yl, 1-methyl-prop-2-en-1-yl, 2-methyl-prop -2-en-l-yl, 2-butene-l-yl, l-penten-3-yl, l-penten-4-yl, 2-penten-4-yl, 1-methyl-but -2-en-l-yl, 2-methyl-but-2-en-l-yl, 3-methyl-but-2-en-l-yl, l-methyl-but-3-en-l-yl , 2-methyl-but-3-en-1-yl, 3-methyl-but-3-en-1-yl, 1, 1-dimethyl-prop-2-en-1-yl, 1, 2-dimethyl -prop-2-en-l-yl, 1-ethyl-prop-2-en-l-yl, hex-3-en-l-yl, hex-4-en-l-yl, hex-5-ene -l-yl, l-methyl-pent-3-en-l-yl, 2-methyl-pent-3-en-l-yl, 3-methyl-pent-3-en-l-yl, 4-methyl -pent-3-en-l-yl, 1-methyl-pent-4-en-l-yl, 2-methyl-pent-4-en-l-yl, 3-methyl-pent-4-en-l -yl, 4-methyl-pent-4-en-1-yl, 1, 1-dimethyl-but-2-en-1-yl, 1, 1-dimethyl-but-3-en-1-yl, 1 , 2-Dimethyl-but-2-en-l-yl, 1, 2-dimethyl-but-3-en-l-yl, 1, 3-dimethyl-but-2-en-l-yl, 1, 3 -Dimethyl-but-3-en-1-yl, 2, 2-dimethyl-but-3-en-1-yl, 2, 3-dimethyl-but-2-en-1-yl, 2, 3-dimethyl - but-3-en-l-yl, 3,3-dimethyl-but-2-en-l-yl, l-ethyl-but-2- en-l-yl, l-ethyl-but-3-en-l-yl, 2-ethyl-but-2-en-l-yl,

2-ethyl-3-en-1-yl, 1, 1, 2-trimethyl-prop-2-en-1-yl, 1-ethyl-1-methyl-prop-2-en-1-yl or 1-ethyl-2-methyl-prop-2-en-1-yl;

C ₂ -C ₆ alkynyl: for example ethynyl, propargyl, but-1-yn-3-yl,

But-l-in-4-yl, but-2-in-l-yl, pent-l-in-3-yl, pent-l-in-4-yl,

Pent-1-in-5-yl, Pent-2-in-1-yl, Pent-2-in-4-yl, Pent-2-in-5-yl, 3-methyl-but-1-yl 3-yl, 3-methyl-but-l-in-4-yl, hex-l-in-3-yl, hex-l-in-4-yl, hex-l-in-5-yl, hex l-in-6-yl,

Hex-2-in-1-yl, hex-2-in-4-yl, hex-2-in-5-yl, hex-2-in-6-yl,

Hex-3-in-l-yl, hex-3-in-2-yl, 3-methyl-pent-l-in-3-yl, 3-methyl-pent-l-in-4-yl, 3-methyl-pent-1-yl-5-yl, 4-methyl-pent-2-yn-4-yl or 4-methyl-pent-2-yn-5-yl;

C ₃ -C ₆ cycloalkyl: for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl;

Aryl: e.g. Phenyl or naphthy1;

Heterocyclyl: a saturated, partially saturated or unsaturated 5- or 6-membered, C-bonded, heterocyclic ring which contains one to four identical or different heteroatoms selected from the following group: oxygen, sulfur or nitrogen, i.e. e.g. 5-section

Rings with e.g. one heteroatom, with two heteroatoms, with three heteroatoms or with four heteroatoms or e.g. 6-membered rings with, for example, one heteroatom, with two heteroatoms, with three heteroatoms or with four heteroatoms, i.e. 5-membered rings with one heteroatom such as:

Tetrahydrofuran-2-yl, tetrahydrofuran-3-yl, tetrahydrothien-2-yl, tetrahydrothien-3-yl, tetrahydropyrrol-2-yl, tetrahydropyrrol-3-yl, 2, 3-dihydrofuran-2-yl, 2, 3-dihydrofuran-3-yl, 2,5-dihydrofuran-2-yl, 2,5-dihydrofuran-3-yl, 4,5-dihydrofuran-2-yl, 4,5-dihydrofuran-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,5-dihydrothien-2-yl, 2,5-dihydrothien-3-yl, 4,5-dihydrothien-2- yl, 4,5-dihydrothien-3-yl, 2,3-dihydro-lH-pyrrol-2-yl, 2,3-dihydro-lH-pyrrol-3-yl, 2,5-dihydro-lH-pyrrole 2-yl, 2,5-dihydro-lH-pyrrol-3-yl, 4,5-dihydro-lH-pyrrol-2-yl, 4,5-dihydro-lH-pyrrol-3-yl, 3,4- Dihydro-2H-pyrrol-2-yl, 3,4-dihydro-2H-pyrrol-3-yl, 3,4-dihydro-5H-pyrrol-2-yl, 3,4-dihydro-5H-pyrrol-3- yl, 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, pyrrol-2-yl or pyrrol-3-yl; 5-membered rings with two heteroatoms such as:

Tetrahydropyrazol-3-yl, tetrahydropyrazol-4-yl, tetrahydroisoxazol-3-yl, tetrahydroisoxazol-4-yl, tetrahydroisoxazol-5-yl, 1, 2-oxathiolan-3-yl, 1, 2-oxathiolane 4-yl, 1,2-oxathiolan-5-yl, tetrahydroisothiazol-3-yl, tetrahydroisothiazol-4-yl, tetrahydroisothiazol-5-yl, 1,2-dithiolan-3-yl, 1,2- Dithiolan-4-yl, tetrahydroimidazol-2-yl, tetrahydroimidazol-4-yl, tetrahydrooxazol-2-yl, tetrahydrooxazol-4-yl, tetrahydrooxazol-5-yl, tetrahydrothiazol-2-yl, tetrahydrothiazol-2-yl yl, tetrahydrothiazol-5-yl, 1, 3-dioxolan-2-yl, 1, 3-dioxolan-4-yl, 1, 3-oxathiolan-2-yl, 1, 3-oxathiolan-4-yl, l, 3-oxathiolan-5-yl, 1,3-dithiolan-2-yl, 1,3-dithiolan-4-yl, 4,5-dihydro-lH-pyrazol-3-yl, 4,5-dihydro-lH- pyrazol-4-yl, 4,5-dihydro-lH-pyrazol-5-yl, 2,5-dihydro-lH-pyrazol-3-yl, 2,5-dihydro-lH-pyrazol-4-yl, 2,2 5-dihydro-1H-pyrazol-5-yl, 4,5-dihydroisoxazol-3-yl, 4,5-dihydroisoxazol-4-yl, 4,5-dihydroisoxazol-5-yl, 2,5-dihydroisoxazole 3-yl, 2,5-dihydroisoxazol-4-yl, 2,5-dihydroisoxazole -5-yl, 2,3-dihydroisoxazol-3-yl, 2,3-dihydroisoxazol-4-yl, 2,3-dihydroisoxazol-5-yl, 4,5-dihydroisothiazol-3-yl, 4,5 -Dihydroisothiazol-4-yl, 4,5-dihydro-isothiazol-5-yl, 2,5-dihydroisothiazol-3-yl, 2,5-dihydroisothiazol-4-yl, 2,5-dihydroisothiazol-5-yl , 2, 3-dihydroisothiazol-3-yl, 2,3-dihydroisothiazol-4-yl, 2,3-dihydroisothiazol-5-yl, Δ ³ -l, 2-dithiol-3-yl, Δ ³ -l , 2-dithiol-4-yl, Δ ³ -1,2-di-thiol-5-yl, 4, 5-dihydro-lH-imidazol-2-yl, 4, 5-dihydro-lH-imi- dazol- 4-yl, 4,5-dihydro-lH-imidazol-5-yl, 2,5-dihydro-lH-imidazol-2-yl, 2,5-dihydro-lH-imidazol-4-yl, 2, 5-dihydro-lH-imidazol-5-yl, 2,3-dihydro-lH-imidazol-2-yl, 2,3-dihydro-lH-imidazol-4-yl, 4,5-dihydrooxazole 2-yl, 4,5-dihydrooxazol-4-yl, 4,5-dihydrooxazol-5-yl, 2,5-dihydrooxazol-2-yl, 2,5-dihydrooxazol-4-yl, 2,5- Dihydrooxazol-5-yl, 2, 3-dihydrooxazol-2-yl, 2, 3-dihydrooxazol-4-yl, 2, 3-dihydrooxazol-5-yl, 4,5-dihydrothiazol-2-yl, 4, 5-dihydrothiazol-4-yl, 4,5-dihydrothiazol-5-yl, 2nd , 5-dihydrothiazol-2-yl, 2,5-dihydrothiazol-4-yl, 2,5-dihydrothiazol-5-yl, 2,3-dihydrothiazol-2-yl, 2,3-dihydrothiazol-4-yl , 2,3-dihydrothiazol-5-yl, 1,3-dioxol-2-yl, 1,3-dioxol-4-yl, 1,3-dithiol-2-yl, 1,3-dithiol-4-yl , 1,3-oxathiol-2-yl, 1,3-oxathiol-4-yl, 1,3-oxathiol-5-yl, pyrazol-3-yl, pyrazol-4-yl, isoxazol-3-yl , Isoxazol-4-yl, isoxazol-5-yl, isothiazol-3-yl, isothiazol-4-yl, isothiazol-5-yl, imidazol-2-yl, imidazol-4-yl, oxazol-2-yl, oxazole -4-yl, oxazol-5-yl, thiazol-2-yl, thiazol-4-yl or thiazol-5-yl;

5-membered rings with three heteroatoms such as: 1, 2, 3-Δ ² -oxadiazolin-4-yl, 1, 2, 3-Δ ² -oxadiazolin-5-yl,

1,2, 4-Δ ⁴ -Oxadiazolin-3-yl, 1,2, 4-Δ-oxadiazoline-5-yl,

1,2, 4-Δ ² -Oxadiazolin-3-yl, 1,2, 4-Δ ² -Oxadiazolin-yl-5,

1,2, 4-Δ ³ -Oxadiazolin-3-yl, 1,2, 4-Δ ³ -Oxadiazolin-yl-5, 1, 3, 4-Δ ² -Oxadiazolin-yl-2, 1, 3, 4 -Δ ² -oxadiazolin-5-yl,

1,3, 4-Δ ³ -oxadiazolin-2-yl, 1,3, 4-oxadiazolin-2-yl, l, 2,3-Δ-thiadiazolin-4-yl, 1, 2, 3-Δ ² - Thiadiazolin-5 -yl,

1,2, 4-Δ ⁴ -Thiadiazolin-3-yl, 1,2, 4-Δ-thiadiazoline-5-yl,

1,2, 4-Δ ³ -Thiadiazolin-3-yl, 1, 2, 4-Δ ³ -Thiadiazolin-yl-5, l, 2,4-Δ ² -Thiadiazolin-yl-3, 1, 2, 4 -Δ ² -Thiadiazolin-5-yl, 1, 3, 4-Δ ² -Thiadiazolin-2-yl, 1, 3, 4-Δ ² -Thiadiazolin-5-yl, l, 3,4-Δ ³ -Thiadiazolin -2-yl, 1, 3, 4-thiadiazolin-2-yl, 1,3, 2-dioxathiolan-4-yl, 1,2, 3-Δ ² -triazolin-4-yl, 1,2, 3- Δ ² -Triazolin-5-yl, 1,2, 4-Δ ² -Triazolin-3-yl, l, 2,4-Δ ² -Triazolin-5-yl, 1, 2, 4-Δ ³ -Triazolin- 3-yl, l, 2,4-Δ ³ -triazolin-5-yl, 1, 2, 4-Δ ^! -Triazolin-2-yl, 1,2,4-tri-azolin-3-yl, 3H-1, 2, 4-dithiazol-5-yl, 2H-1, 3, 4-dithiazol-5-yl, 2H -1, 3,4-oxathiazol-5-yl, 1,2,3-oxadiazol-4-yl, l, 2,3-oxadiazol-5-yl, 1,2,4-oxadiazol-3-yl, l , 2,4, -oxadiazol-5-yl, 1, 3, 4-oxadiazol-2-yl, 1, 2, 3-thiadiazol-4-yl, 1, 2, 3-thiadiazol-5-yl, l, 2,4-thiadiazol-3-yl, 1, 2, 4-thiadiazol-5-yl, 1,3,4-thiadiazolyl-2-yl, 1, 2, 3-triazol-4-yl or 1, 2, 4-triazol-3-yl;

5-membered rings with four heteroatoms such as:

Tetrazol-5-yl;

6-membered rings with a heteroatom such as:

Tetrahydropyran-2-yl, tetrahydropyran-3-yl, tetrahydropyran-4-yl, piperidin-2-yl, piperidin-3-yl, piperidin-4-yl, tetrahydrothiopyran-2-yl, tetrahydrothiopyran-3-yl, Tetra-hydrothiopyran-4-yl, 2H-3, 4-dihydropyran-6-yl, 2H-3,4-dihydropyran-5-yl, 2H-3, 4-dihydropyran-4-yl, 2H-3, 4- Dihydropyran-3-yl, 2H-3, 4-dihydropyran-2-yl, 2H-3, 4-dihydropyran-6-yl, 2H-3, 4-dihydrothiopyran-5-yl, 2H-3, 4-dihydrothiopyran 4-yl, 2H-3, 4-dihydropyran-3-yl, 2H-3, 4-dihydropyran-2-yl, 1,2,3, 4-tetrahydropyridin-6-yl, 1,2, 3, 4- Tetrahydropyridin-5-yl, 1, 2, 3, -tetrahydropyridin-4-yl, l, 2,3,4-tetrahydropyridin-3-yl, 1, 2, 3, 4-tetrahydropyridin-2-yl, 2H -5, 6-dihydropyran-2-yl, 2H-5, 6-dihydropyran-3-yl, 2H-5, 6-dihydropyran-4-yl, 2H-5, 6-dihydropyran-5-yl, 2H-5 , 6-dihydropyran-6-yl, 2H-5, 6-dihydrothiopyran-2-yl, 2H-5, 6-dihydrothiopyran-3-yl, 2H-5, 6-dihydrothiopyran-4-yl, 2H-5, 6 -Dihydrothiopyran-5-yl, 2H-5, 6-dihydrothiopyran-6-yl, 1,2,5, 6-tetrahydropyridin-2-yl, 1,2, 5, 6-tetrahydropyr idin-3- yl, 1,2, 5, 6-tetrahydropyridin-4-yl, 1, 2, 5, 6-tetrahydropyridin-5-yl, 1, 2, 5, 6-tetrahydropyridin-6-yl, 2, 3, 4, 5-tetrahydropyridin-2-yl, 2, 3, 4, 5-tetrahydropyridin-3-yl, 2, 3, 4, 5-tetrahydropyridin-4-yl, 2,3,4, 5- Tetrahydropyridin-5-yl, 2, 3, 4, 5-tetrahydropyridin-6-yl, 4H-pyran-2-yl, 4H-pyran-3-yl, 4H-pyran-4-yl, 4H-thiopyran-2- yl, 4H-thiopyran-3-yl,

4H-thiopyran-4-yl, 1,4-dihydropyridin-2-yl, 1,4-dihydropyridin-3-yl, 1,4-dihydropyridin-4-yl, 2H-pyran-2-yl, 2H- Pyran

3-yl, 2H-pyran-4-yl, 2H-pyran-5-yl, 2H-pyran-6-yl, 2H-thiopyran-2-yl, 2H-thiopyran-3-yl, 2H-thiopyran 4-yl, 2H-thiopyran

5-yl, 2H-thiopyran-6-yl, 1, 2-dihydropyridin-2-yl,

1, 2-dihydropyridin-3-yl, 1, 2-dihydropyridin-4-yl, 1, 2-dihydropyridin-5-yl, 1, 2-dihydropyridin-6-yl, 3, 4-dihydropyridin-2-yl, 3, 4-dihydropyridin-3-yl, 3, 4-dihydropyridin-4-yl, 3, 4-dihydropyridin-5-yl,

3, 4-dihydropyridin-6-yl, 2, 5-dihydropyridin-2-yl,

2, 5-dihydropyridin-3-yl, 2, 5-dihydropyridin-4-yl,

2, 5-dihydropyridin-5-yl, 2, 5-dihydropyridin-6-yl, 2, 3-dihydropyridin-2-yl, 2, 3-dihydropyridin-3-yl, 2, 3-dihydropyridin-4-yl, 2, 3-dihydropyridin-5-yl,

2, 3-dihydropyridin-6-yl, pyridin-2-yl, pyridin-3-yl or pyridin-4-yl;

6-membered rings with two heteroatoms such as:

1,3-dioxan-2-yl, 1,3-dioxan-4-yl, 1,3-dioxan-5-yl, 1,4-dioxan-2-yl, 1,3-dithian-2-yl, 1, 3-dithian-4-yl, 1, 3-dithian-5-yl, 1, 4-dithian-2-yl, 1, 3-oxathian-2-yl, 1, 3-oxathian-4-yl, 1,3-oxathian-5-yl, 1,3-oxathian-6-yl, 1,4-oxathian-2-yl, 1,4-oxathian-3-yl, 1,2-dithian-3-yl,

1, 2-dithian-4-yl, hexahydropyrimidin-2-yl, hexahydropyrimi-din-4-yl, hexahydropyrimidin-5-yl, hexahydropyrazin-2-yl, hexahydropyridazin-3-yl, hexahydropyridazin-4-yl, tetra- hydro-1, 3-oxazin-2-yl, tetrahydro-1, 3-oxazin-4-yl, tetrahydro-1, 3-oxazin-5-yl, tetrahydro-1, 3-oxazin-6-yl, Tetrahydro-1,3-thiazin-2-yl, tetrahydro-1,3-thiazin-4-yl, tetrahydro-1,3-thiazin-5-yl, tetrahydro-1,3-thiazin-6- yl, tetrahydro-1,4-thiazin-2-yl, tetrahydro-1,4-thiazin-3-yl, tetrahydro-1,4-oxazin-2-yl, tetrahydro-1,4-oxazin- 3-yl, tetrahydro-1, 2-oxazin-3-yl, tetrahydro-1, 2-oxazin-4-yl, tetrahydro-1, 2-oxazin-5-yl, tetrahydro-1, 2- oxazin-6-yl, 2H-5,6-dihydro-1, 2-oxazin-3-yl, 2H-5, 6-dihydro-l, 2-oxazin-4-yl, 2H-5, 6- Dihydro-l, 2-oxazin-5-yl, 2H-5, 6-dihydro-l, 2-oxa-zin-6-yl, 2H-5, 6-dihydro-l, 2-thiazin-3-yl, 2H-5,6-dihydro-1,2-thiazin-4-yl, 2H-5,6-dihydro-1,2-thiazin-5-yl, 2H-5,6-dihydro-1,2 thiazin-6-yl, 4H-5,6-dihydro-1,2-oxazin-3-yl, 4H-5,6-dihydro-1,2-oxa zin-4-yl, 4H-5, 6-dihydro 1, 2-oxazin-5-yl, 4H-5, 6-dihydro-l, 2-oxazin-6-yl, 4H-5,6-dihydro-1, 2-thiazin-3-yl, 4H- 5, 6-dihydro-l, 2-thiazin-4-yl,

4H-5,6-dihydro-l, 2-thiazin-5-yl, 4H-5, 6-dihydro-l, 2-thiazin-6-yl, 2H-3, 6-dihydro-l, 2- oxazin-3-yl, 2H-3, 6-dihydro-1, 2-oxazin-4-yl, 2H-3, 6-dihydro-l, 2-oxazin-5-yl, 2H-3,6-di- hydro-1, 2-oxazin-6-yl, 2H-3, 6-dihydro-l, 2-thiazin-3-yl,

2H-3,6-dihydro-l, 2-thiazin-4-yl, 2H-3, 6-dihydro-l, 2-thiazin-5-yl, 2H-3, 6-dihydro-l, 2- thiazin-6-yl, 2H-3, 4-dihydro-l, 2-oxazin-3-yl, 2H-3, 4-dihydro-l, 2-oxazin-4-yl, 2H-3,4-di- hydro-1, 2-oxazin-5-yl, 2H-3, 4-dihydro-l, 2-oxazin-6-yl,

2H-3,4-dihydro-1,2-thiazin-3-yl, 2H-3,4,4-dihydro-1,2-thiazin-4-yl, 2H-3,4-dihydro-1,2 thiazin-5-yl, 2H-3,4,4-dihydro-1,2-thiazin-6-yl, 2,3,4,5-tetrahydropyridazin-3-yl, 2,3,4,5-tetrahydropyridazin-4- yl, 2,3,4,5-tetrahydropyridazin-5-yl, 2, 3, 4, 5-tetrahydropyridazin-6-yl, 3, 4, 5, 6-tetrahydropyridazin-3-yl, 3, 4,5, 6-tetrahydropyridazin-4-yl, 1,2,5, 6-tetrahydropyridazin-3-yl, 1,2, 5, 6-tetrahydropyridazin-4-yl, 1, 2, 5, 6- Tetrahydropyridazin-5-yl, 1, 2, 5, 6-tetrahydropyridazin-6-yl, 1,2,3, 6-tetrahydropyridazin-3-yl, l, 2,3,6-tetrahydropyridazin-4-yl, 4H-5, 6-dihydro-l, 3-oxazin-2-yl, 4H-5, 6-dihydro-l, 3-oxazin-4-yl, 4H-5,6-dihydro-1, 3-oxazin-5-yl, 4H-5, 6-dihydro-l, 3-oxazin-6-yl, 4H-5, 6-dihydro-l, 3-thiazin-2-yl, 4H-5, 6- Dihydro-l, 3-thiazin-4-yl, 4H-5, 6-dihydro-l, 3-thiazin-5-yl, 4H-5, 6-dihydro-1,3-thiazin-6-yl, 3, 4, 5, 6-tetrahydropyrimidin-2-yl,

3,4,5, 6-tetrahydropyrimidin-4-yl, 3,4,5, 6-tetrahydropyrimidin-5-yl, 3, 4, 5, 6-tetrahydropyrimidin-6-yl, 1,2,3, 4-tetrahydropyrazin-2-yl, 1,2,3, 4-tetrahydropyrazin-5-yl, 1,2,3, 4-tetrahydropyrimidin-2-yl, 1,2,3,4-tetrahydropyrimi-din- 4-yl, 1, 2, 3, 4-tetrahydropyrimidin-5-yl, 1, 2, 3, 4-tetrahydropyrimidin-6-yl, 2, 3-dihydro-l, 4-thiazin-2-yl, 2,3-di-hydro-1, 4-thiazin-3-yl, 2,3-dihydro-l, 4-thiazin-5-yl, 2,3-di-hydro-l, 4-thiazin-6- yl, 2H-1, 2-oxazin-3-yl, 2H-1, 2-oxazin-4- yl, 2H-l, 2-oxazin-5-yl, 2H-1, 2-oxazin-6-yl, 2H-1, 2-thiazin-3-yl, 2H-1, 2-thiazin-4-yl, 2H-1, 2-thiazin-5-yl, 2H-1, 2-thiazine-6-yl, 4H- l, 2-oxazin-3-yl, 4H-1, 2-oxazin-4-yl, 4H-1, 2-oxazin-5-yl, 4H-l, 2-oxazin-6-yl, 4H-1, 2-thiazin-3-yl, 4H-1,2-thiazin-4-yl, 4H-1, 2-thiazin-5-yl, 4H-1, 2-thiazin-6-yl, 6H-1, 2-oxazin-3-yl, 6H-1, 2-oxazin-4-yl, 6H-1, 2-oxazin-5-yl, 6H-l, 2-oxazin-6-yl, 6H-1, 2- Thiazin-3-yl, 6H-1, 2-thiazin-4-yl, 6H-l, 2-thiazin-5-yl, 6H-1, 2-thiazin-6-yl, 2H-1, 3-oxazin- 2-yl, 2H-l, 3-ox azin-4-yl, 2H-1, 3-oxazin-5-yl, 2H-1, 3-oxazin-6-yl, 2H-l, 3-thiazin-2-yl, 2H-1, 3-thiazine 4-yl, 2H-1, 3-thiazin-5- yl, 2H-l, 3-thiazin-6-yl, 4H-1, 3-oxazin-2-yl, 4H-1, 3-oxazin-4- yl, 4H-l, 3-oxazin-5-yl, 4H-1, 3-oxazin-6-yl, 4H-1, 3-thiazine-2-yl, 4H-l, 3-thiazin-4-yl, 4H-1, 3-thiazin-5-yl, 4H-1,3-thiazin-6-yl, 6H-1, 3-oxazin-2-yl, 6H-1, 3-oxazin-4-yl, 6H-l, 3-oxa- zin-5-yl, 6H-1, 3-oxazin-6-yl, 6H-1, 3-thiazin-2-yl, 6H-l, 3-oxazin-4-yl, 6H-1, 3-oxazin- 5-yl, 6H-1, 3-thiazin-6-yl, 2H-l, 4-oxazin-2-yl, 2H-1, 4-oxazin-3-yl, 2H-1, 4-oxazin-5- yl, 2H-l, 4-oxazin-6-yl, 2H-1, 4-thiazin-2-yl, 2H-1, 4-thiazin-3-yl, 2H-l, 4-thiazin-5-yl, 2H-1, 4-thiazin-6-yl, 4H-1, 4-oxazin-2-yl, 4H-1, 4-oxazin-3-yl, 4H-1, 4-thiazin-2-yl, 4H- 1,4-thiazin-3-yl, 1,4-dihydropyridazin-3-yl, 1,4-dihydropyridazin-4-yl, 1,4-dihydropyridazin-5-yl, 1,4-dihydropyridazin-6- yl, 1,4-dihydropyrazine-2-yl, 1,2-dihydropyrazine-2-yl, 1,2-dihydropyrazine-3-yl, 1,2-dihydropyrazine-5-yl, 1,2-dihydropyrazine 6-yl,

1,4-dihydropyrimidin-2-yl, 1,4-dihydropyrimidin-4-yl, 1,4-dihydropyrimidin-5-yl, 1,4-dihydropyrimidin-6-yl, 3,4-dihydropyrimidin- 2-yl, 3,4-dihydropyrimidin-4-yl, 3,4-dihydropyrimidin-5-yl or 3,4-dihydropyrimidin-6-yl, pyridazin-3-yl, pyridazin-4-yl, pyrimidin- 2-yl, pyrimidin-4-yl, pyrimidin-5-yl or pyrazin-2-yl;

6-membered rings with three heteroatoms such as:

1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl, 1,2,4-triazin-5-yl, 1,2,4-triazin-6-yl;

6-membered rings with four heteroatoms such as:

1,2,5,5-tetrazin-3-yl;

where necessary. the sulfur of the heterocycles mentioned can be oxidized to S = 0 or S (= 0).

Manufacturing examples

1. 2,2,4,4-tetramethyl -1,3-cyclobutanedione

To a solution of 106 g (1 mol) of isobutyric acid chloride in 800 ml tert. Butyl methyl ether was added dropwise, 172 g (1.7 mol)

Triethylamine and then heated under reflux for 15 h. It was washed with dil. Hydrochloric acid, the phases were separated and the org. Solvent. Yield: 55 g (78%). iH-NMR (CDC1 ₃ ): δ = 1.3 (s, 12 H).

2,2,4-rimethyl-3-silyloxy-pen - 3-en-carboxylic acid methyl ester

84 g (0.6 mol) of 2, 2, 4, 4-tetramethyl-cyclobutane-1, 3-dione and 32.4 g (0.6 mol) of sodium methylate were combined in 320 ml of tetrahydrofuran. 65.1 g (0.6 mol) of trimethylsilyl chloride were added dropwise and the mixture was stirred. The reaction mixture was then concentrated and the residue was treated with diethyl ether added. The solid was suction filtered and the mother liquor was concentrated. Yield: 135 g (89%).

^! H-NMR (CDC1 ₃ ): δ = 0.3 (s, 9 H), 1.3 (s, 6 H), 1.5 (s, 3 H), 1.7 (s, 3H), 3 , 6 (s, 3H).

2,2,4,4-tetramethyl-3,5-dioxo-hexanoic acid methyl ester

20 g (82 mmol) of 2,2,4-trimethyl-3-silyloxy were added dropwise to a mixture of 11.2 g (82 mmol) of zinc chloride, 6.45 g (82 mmol) of acetyl chloride in dichloromethane and diethyl ether while cooling with ice -pent-3-en-carboxylic acid methyl ester. The mixture was then allowed to warm to room temperature, ice water was added dropwise and the phases were separated. This gave 13.6 g (78%) of 2,2,4,4-tetramethyl-3,5-dioxo-hexanoic acid methyl ester. H-NMR (CDC1 ₃ ): δ = 1.3 (s, 6 H), 1.4 (s, 6 H), 2.1 (s, 3 H), 4.6 (s, 3 H).

2,2,4,4-etramethyl-1,3,5-cyclohexanetrione

106 g (495 mmol) of 2,2,4,4-tetramethyl -3,5-dioxo-hexanoic acid methyl ester were added dropwise to a suspension of 19.8 g (495 mmol) of sodium hydroxide in 500 ml of dimethyl sulfoxide. The mixture was stirred at room temperature, treated with 500 ml of water and adjusted to pH 1 with hydrochloric acid, and then the precipitate which had separated out was filtered off with suction. After drying, 70 g (95%) of 2,2,4,4-tetramethyl-1,3,5-cyclohexanetrione was obtained. ⁱ H-NMR (CDC1 ₃ ): δ = 1.3 (s, 12 H), 5.4 (s, 1 H), 12 (br., OH).

Bis-cyclohexane-1-spiro-2 ', 4' -cyclobutane-1, 3-dione

A solution of 100 g (0.68 mol) of cyclohexane carboxylic acid chloride and 117 g (1.156 mol) of triethylamine in 800 ml of toluene was heated under reflux for 21 hours. The precipitated solid was then suctioned off; this was then washed with water. After drying, 77 g of bis-cyclohexane-1-spiro-2 ', 4' -cyclobutane-1, 3-dione were obtained. ⁱ H-NMR (CDC1 ₃ ): δ = 1.4 (m, 4 H), 1.6 (m, 8 H), 1.8 (m, 8 H).

Silylation of bis-cyclohexane-1-spiro-2 ', 4' -cyclobutane-1,3-dione

To a suspension of 41.7 g (189 mmol) bis-cyclohexane-1-spiro-2 ', 4' -cyclobutan-1, 3-dione and 10.3 g (189 mmol) sodium methylate in 100 ml tetrahydrofuran 20.6 g (189 mmol) of chlorotrimethylsilane. The mixture was left to stir at room temperature for 18 hours and filtered off over silica gel. The mother liquor was concentrated and 32 g (51%) of the Si lylation product. ⁱ H-NMR (CDCI ₃ ): δ = 0 (s, 9 H), 0, 9 - 1, 9 (m, 20 H),

3, 4 (s, 3H).

Bis-cyclohexane-1-spiro-2 ', 4' - (3, 5 -dioxo-hexanoic acid methyl ester)

10.4 g was added dropwise to the suspension of 6.3 g (46 mmol) of zinc chloride and 3.61 g (46 mmol) of acetyl chloride in 46 ml of dichloromethane and 12 ml of diethyl ether

(46 mmol) of the silyl compound described above, then the mixture was stirred for 2 hours at room temperature. Water was added and the phases were separated. The organic phase gave 13.2 g of bis-cyclohexane-l-spiro-2 ', 4' - (3, 5-dio-xo-hexanoic acid methyl ester), which was directly reacted further.

Bis-cyclohexane-1-spiro-2 ', 4' -cyclohexane-1, 3, 5-trione

To a solution of 2.5 g (22 mmol) potassium tert. -butylate in 25 ml of tetrahydrofuran, a solution of 2.86 g of bis-cyclohexane-1-spiro-2 ', 4' - (3, 5-dioxo-hexanoic acid methyl ester) was added dropwise

Tetrahydrofuran and read for 4 hours at room temperature.

It was adjusted to pH 1 with hydrochloric acid and extracted with

Dichloromethane. The combined organic phases were dried and the solvent was removed, giving 2.5 g

(95%) bis-cyclohexane-1-spiro-2 ', 4' -cyclohexane-1, 3, 5-trione. ⁱ H-NMR (CDCI ₃ ): δ = 1.1-1.9 (m, 20 H), 3.4 (s, 2 H).

Claims

claims

1. Process for the preparation of 2, 2, 4, 4-tetrasubstituted 1, 3, 5-cyclohexanetrions of the formula I.

in the

Ri, R ² -C ₆ alkyl or C -C ₆ cycloalkyl, where these two radicals can be unsubstituted or partially or completely halogenated and / or substituted by the following radicals: -C ₄ alkoxy, C ₁ -C ₄ Alkylthio or di (C ₁ -C ₄ alkyl) amino;

Ci-C _ß alkoxy, C ₂ -C ₆ alkenyl or C -C ₆ alkynyl; Aryl, aryloxy, or heterocyclyl, up to three

Has heteroatoms from the group 0, S and N, where the aryl, aryloxy and heterocyclyl radicals can be unsubstituted or partially or completely halogenated and / or substituted by the following radicals:

C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₃ -C ₄ alkoxy, Cχ-C ₄ haloalkoxy or C ₁ -C ₄ alkoxycarbonyl;

or two radicals R ¹ and R ² , which are bonded to the same carbon, together form a - (CH ₂ ) _-6 chain, which can be substituted by the following radicals: halogen, -CC ₄ -alkyl, C ₁ -C ₄ haloalkyl, Cι-C ₄ -alkoxy, C ₄ -haloalkoxy or Ci-C ₄ alkoxycarbonyl; mean;

characterized in that one

a) a cyclobutane-1,3-dione of the formula II

wherein R ¹ and R ^{2 have} the meaning given above, with an O- or N-nucleophile, optionally in the presence of a base, and a silylating reagent to the

Silylenol ethers of the formula III,

in which

R ³ Ci-Cβ-alkoxy, amino, -C-C ₆ alkylamino or di - (Ci - C_ -alkyl) amino;

R ⁴ -C ₆ alkyl or phenyl;

R and R ^{2 have} the meaning given above;

implements;

wherein R ⁱ to R ^{3 have} the meaning given above;

transferred;

c) the compound IV is cyclized in the presence of a base to give the 2, 2, 4, 4-tetrasubstituted cyclohexanetrione of the formula I.

2. Process for the preparation of 2, 2, 4, 4 tetrasubstituted

1, 3, 5 -cyclohexantrions of formula I according to claim 1, wherein the cyclobutane-1, 3-dione of formula II is obtained by

al) implementation of an acid halide of the formula VR ⁱ

> _r ^ _r V

Shark wherein shark is halogen and R ¹ and R ^{2 have} the meaning given in claim 1, with a base.

3. The method according to claims 1 or 2, characterized in that in step a) the cyclobutane-1, 3-dione of the formula

II with an alkali or alkaline earth metal salt of a C ₆ -C ₆ alcohol, C ₁ -C ₆ alkylamine, di (C ₆ -C ₆ alkyl) amine or ammonia.

4. Process according to claims 1 to 3, characterized in that in step a) the cyclobutane-1, 3 -dione of the formula

II with an alkali or alkaline earth alcoholate.

5. Process according to claims 1 to 4, characterized in that in step a) the cyclobutane-1, 3-dione of the formula II is reacted with sodium methoxide.

6. Process according to claims 1 to 5, characterized in that ethers or alcohols are used as solvent in stage a).

7. The method according to claims 1 to 6, characterized in that the reaction described in step a) is carried out in a temperature range from 0 to 120 ° C.

8. Process according to claims 1 to 7, characterized in that an inorganic or organic base is used in step c).

9. Process according to claims 1 to 8, characterized in that an oxide, hydroxide, as base in step c),

Alcoholate, bicarbonate or carbonate of an alkali or alkaline earth metal is used.

10. The method according to claims 1 to 9, characterized in that an oxide, hydroxide, as base in step c),

Bicarbonate or carbonate of an alkali or alkaline earth metal used.

11. The method according to claims 1 to 8, characterized in that an amine base is used as base in step c).

12. The method according to claims 1 to 11, characterized in that ether, alcohols or aprotic dipolar solvents are used as solvent in step c).

13. The method according to claims 1 to 12, characterized in that the reaction described in step c) is carried out in a temperature range from 0 to 120 ° C.

14. Process for the preparation of silylenol ether of the formula III, where the radicals R ¹ to R ^{4 have} the meaning given in claim 1, according to step a) as in claims 1 or 3 to 7 or according to steps al) and a ) as described in claims 2 to 7. 10

15. A process for the preparation of 2, 2, 4, 4 tetrasubstituted

1, 3, 5 -cyclohexantrions of the formula I, where the radicals R ¹ and R ^{2 have} the meaning given in claim 1, according to step c) as indicated in claims 10 to 13. 15

16. Process for the preparation of 2, 2, 4, 4 -tetrasubstituted

1, 3, 5 -cyclohexantrions of formula I, wherein R ¹ and R ^{2 have} the meaning given in claim 1, according to step c) as indicated in claim 1, wherein as base an alkali or earth 20 alkali alcoholate in the ratio 1: 1 to 1: 3 is used.

17. The method according to claim 16, wherein an ether is used as solvent.

25 18. The method according to claims 16 or 17, wherein the reaction from -75 ° C to the boiling point of the solvent / solvent mixture is carried out.

19. 2, 2, 4, 4-tetrasubstituted 1, 3, 5 -cyclohexanetrione of the formula 30 mel I '

in which R ¹ and R ² , which are bonded to the same carbon, form a - (CH) _-6 chain, which can be substituted by the following radicals:

Halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ -alkoxy, C ₄ -Halogenalkσxy or Ci -C ₄ alkoxycarbonyl.

5

20th Silylenol ether of the formula III '

wherein the variables R ¹ , R ² and R ^{4 have} the meaning given in claim 1 and 10

R ³ amino, CI-C _Ö "alkylamino or di- (-C-C ₆ alkyl) amino;

means.

15 21. Tricarbonyl compounds of the formula IV

wherein the variables R ¹ to R ^{3 have} the meaning given in claim 20.

22. Tricarbonyl compounds of the formula IV '

30 where R ¹ and R ² , which are bonded to the same carbon, form a - (CH) _2-6 chain which can be substituted by the following radicals:

Halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, Cι-35 C ₄ -haloalkoxy or C ₁ -C ₄ alkoxycarbonyl;

R ³ C -C ₈ alkoxy;

mean.

40

23. Use of cyclobutane-1,3-dions of the formula II, as in

Described claim 1, for the synthesis of 2, 2,, 4-tetrasubstituted 1,3, 5-cyclohexanetrions of the formula I, as described in claim 1. 5