DE102004060248A1 - New substituted 3-amino-acrylic acid-imino ester compounds useful as ligands in metal catalysts, which are useful as catalysts in polymerization-, copolymerization- and oligomerization-reactions - Google Patents

Abstract

Substituted 3-amino-acrylic acid-imino ester compounds (A) and their tautomers are new. Substituted 3-amino-acrylic acid-imino ester compounds (A) of formulae (I-III) and their tautomers are new. R1aryl (optionally substituted), alkyl or heterocycle; R2aryl or alkyl; R3CN, CO2R6, COR6, CF3, NO2, aryl or alkyl; R4R1, alkyl-aryl or alkyl-heterocycle, bridged; R5alkyl, aryl, H or OR6; and R6 = alkyl or aryl. An independent claim is also included for a metal catalyst comprising the ligand (A). [Image].

Description

In J. Am. Chem. Soc. 68 (1946) 1246 is about a Claisen condensation of 5-chloroaniline with orthoesters and a subsequent aminolysis for illustration of carboxylic acid esters or carboxylic acid amides reported. A synthetic route for Iminoester is in this publication not specified.

In J. Org. Chem. 49 (1984) 2200, especially at page 2202, there is reported 2-amino-acrylic acid iminoester as a product of the AlCl ₃ -catalyzed dimerization of ketimines. However, this iminoester contains a methyl group as a substituent on the central, sp ² -hybridized C atom. Substituents with electron-withdrawing properties and their synthesis are not described in this publication. The alkyl-substituted imino esters are primarily in the form of 1-methoxy-1,3-bisiminopentane (tautomeric form II) and thus differ significantly from 3-amino-acrylic acid iminoesters with electron-withdrawing substituents.

3-Amino-acrylic acid-iminoesters with electron-withdrawing substituents are hereafter referred to as electron-deficient Called iminoester.

The Electron-poor imino esters have a special importance in the production of catalysts, in particular before. Metal catalysts for polymerization, Copolymerization and Oligomerisierungsreaktionen before, for them can be used as metal ligands.

task The invention is therefore to indicate iminoester, the electron-withdrawing Substituents have and thus are electron-deficient and the for the preparation of catalysts, in particular as ligands for metal catalysts own.

The The object is achieved by the chemical described in claim 1 Compound and the catalyst specified in claim 2.

• A Umsetzung 1-substituierter, primärer Essigsäureamide mit einem Oxoniumsalz zu den entsprechenden Essigsäureiminoestern und anschließende Eintopfvariante der Claisen-Kondensation mit Orthosäureestern und Aminolyse
• B Claisen-Kondensation substituierter Essigsäureester oder – amide mit Orthosäureestern und vollständige Aminolyse oder schrittweise Aminolyse führt zu den 3-Aminoacrylsäureamiden, deren Umsetzung mit Oxoniumsalzen zu den 3-Aminoacrylsäure-iminoestern.

For the synthesis of the claimed compound, there are two synthetic routes:

• A Reaction of 1-substituted, primary acetic acid amides with an oxonium salt to the corresponding Essigsäureiminoestern and subsequent one-pot variant of the Claisen condensation with ortho acid esters and aminolysis
• B Claisen condensation of substituted acetic acid esters or amides with ortho acid esters and complete aminolysis or stepwise aminolysis leads to the 3-aminoacrylic acid amides, their reaction with oxonium salts to give the 3-aminoacrylic acid imino esters.

R₁ = aryl, substituierte aryl, alkyl, heterocyclisch; R₂ = aryl, alkyl;
R₃ = CN, CO₂R₆, COR₆, CF₃, NO₂, aryl; alkyl
R₄ = alkyl, aryl, subst. aryl, aryl, heterocyclisch, alkyl-aryl, alkyl-heterocyclisch, verbrückend (alkylen, arylen, etc.)
R₅ = alkyl, aryl, H, OR₆
R₆= alkyl oder aryl Both synthetic routes are shown on the following page:

R ₁ = aryl, substituted aryl, alkyl, heterocyclic; R ₂ = aryl, alkyl;
R ₃ = CN, CO ₂ R ₆ , COR ₆ , CF ₃ , NO ₂ , aryl; alkyl
R ₄ = alkyl, aryl, subst. aryl, aryl, heterocyclic, alkyl-aryl, alkyl-heterocyclic, bridging (alkylene, arylene, etc.)
R ₅ = alkyl, aryl, H, OR ₆
R ₆ = alkyl or aryl

The Invention will be explained in more detail below with reference to experimental examples.

synthesis A

2-cyano-N- (2,6-diisopropylhenyl) -acetimidsäureethylester

A mixture of 2-cyano-N- (2,6-diisopropylphenyl) acetamide (14.70 g, 60 mmol) and a 1.0M Solution of triethyloxonium tetrafluoroborate (66 mL, 66 mmol) in dichloromethane is stirred at room temperature until a complete reaction can be seen in the thin-layer chromatogram. The solvent is then removed and the residue is washed with absolute ether. It is then covered with absolute ether (60 mL), cooled to 0 ° C and added triethylamine (9.2 mL, 66 mmol). After two hours of stirring, the ether phase is separated off and the residue is washed several times with ether. The collected ether phases are dried and the solvent removed. The crude product thus obtained is purified by vacuum distillation (103 ° C, 0.005 torr). Yield 46% (7.52 g)

2-cyano-N- (2,6-diisopropyl-phenyl) -3-ethoxyacrylimidsäureethylester

A Mixture of 2-cyano-N- (2,6-diisopropylprenyl) -acetimidic acid ethyl ester (7.3 g, 26 mmol), triethyl orthoformate (3.8g, 26mmol) and acetic anhydride (5.47g, 54mmol) as long under reflux boiled until the reaction control in thin layer chromatography a full Implementation can be seen. The solvent is stripped off under reduced pressure and the product is removed by vacuum distillation cleaned (125 ° C, 0.005 torr). Yield 64% (5.4 g, 16 mmol)

2-cyano-3- (2,6-diisopropyl-phenylamino) -N- (2,6-diisopropylphenyl) -acrylimidsäureethylester

A solution of 2-cyano-N- (2,6-diisopropylphenyl) -3-ethoxyacrylic acid ethyl ester (9.85 g, 30 mmol) and 2,6-diisopropylaniline (5.32 g, 30 mmol) in 30 mL of methanol is refluxed for 30 minutes. Of the on cooling Precipitated precipitate is filtered off and recrystallized from methanol. Yield 70% (8.8 g, 21 mmol).

synthesis B

example 1

Ethyl 3 - [(2,6-dimethylphenyl) amino] -2 - {[(2,6-dimethylphenyl) amino] carbonyl} acrylate

A Mixture of diethyl ethoxymethylenemalonate (3.0 g, 13.6 mmol) and 2,6-dimethylaniline (3.35 g, 27.4 mmol) in a molar ratio of 1: 2 is in an apartment, from the ethanol during the reaction can be distilled off, heated to 135 ° C until the calculated Amount of ethanol was distilled off. Then hexane (30 mL) is added, the mix for 1h at 0 ° C touched and finally overnight in the refrigerator stored. The resulting precipitate is filtered off and dried. Yield: 89% (4.32 g, 11.8 mmol)

Ethyl 2- {ethoxy [2,6-dimethylphenyl) imino] methyl} -3 - {(2,6-dimethylphenyl) amino] acrylate

An equimolar one Mixture of ethyl 3 - [(2,6-dimethylphenyl) amino] -2 - {[(2,6-dimethylphenyl) amino] carbonyl} acrylate (3 g, 8 mmol) and triethyloxonium tetrafluoroborate (9 mmol) in dichloromethane is at room temperature until complete reaction of the acrylate touched (Control by DC). The solvent becomes then stripped on a vacuum and the residue with absolute diethyl ether washed; after that, in abs. Diethyl ether added and on 0 ° C. cooled. An equimolar one Amount of triethylamine (1.3 g, 9 mmol) is added dropwise and at 2h Room temperature stirred. The ether phase is separated off and the residue is washed again with ether. The combined ether phases are dried over sodium sulfate and the solvent becomes deducted. Yield: about 49% (1.59 g, 4 mmol).

Example 2

Diethyl {[(4-methylphenyl) amino] methylene} malonate

equimolar Amounts of diethyl ethoxymethylenemalonate (4.06 g, 18 mmol) and para-toluidine (1.98 g, 18 mmol) are dissolved in an apparatus from while the reaction is distilled off ethanol, stirred for 5 h at 150 ° C. After that hexane is added and for 1h at 0 ° C touched. Last, the solution is overnight in the fridge stored and the resulting precipitate filtered off and dried. Yield 86% (4.34 g, 16 mmol)

Ethyl 2 - {[(2,6-dimethylphenyl) amino] carbonyl} -3 - [(4-methylphenyl) amino] acrylate

Equimolar amounts of diethyl - {[(4-methylphenyl) amino] methylene} malonate (2.0 g, 7 mmol) and 2,6-dimethylaniline (0.88 g, 7 mmol) are dissolved in an apparatus eluting during the Reaction arising Ethanol is distilled off, stirred at 150 ° C. It is heated until the expected amount of ethanol is distilled off. Then hexane (20 mL) is added, the mixture stirred for 1 h at 0 ° C and finally stored in the refrigerator overnight. The resulting precipitate is filtered off and dried. Yield: 63% (1, 6 g, 4, 5 mmol)

Ethyl 2- {ethoxy [(2,6-dimethylphenyl) imino] methyl} -3 - [(4-methylphenyl) amino] acrylate

A Mixture of ethyl 2 - {[(2,6-dimethylphenyl) amino] carbonyl} -3 - [(4-methylphenyl) amino] acrylate (1.5 g, 4 mmol) and triethyloxonium tetrafluoroborate (5 mmol) in dichloromethane is at room temperature until complete reaction of the acrylate touched (Check by DC). The solvent is then stripped off under reduced pressure and the residue is extracted with absolute diethyl ether washed; after that, in abs.

diethyl ether (50 mL) and brought to 0 ° C. cooled. An equimolar one Amount of triethylamine (0.7 mL, 5 mmol) is added dropwise and at 2h Room temperature stirred. The ether phase is separated off and the residue is washed again with ether. The combined ether phases are dried over sodium sulfate and the solvent is withdrawn. Yield: 47% (0.80 g, 2 mmol)

Example 3

Ethyl 3 - [(2,6-dimethylphenyl) amino] -3-oxopropanoate

A Mixture of diethyl malonates (28 g, 0.3 mol) and 2,6-dimethylaniline (12 g, 0.10 mol) at 150 ° C in an apparatus, during the the reaction resulting ethanol is distilled off, stirred. It will heated until the calculated amount of ethanol distilled off is. Add hexane (80 mL), add the mixture for 1 h Stirred at 0 ° C and finally overnight in the refrigerator stored. The resulting precipitate is filtered off and dried. Yield: 94% (22, 14 g, 0.104 mmol)

Ethyl 2 - {[(2,6-dimethylphenyl) amino] carbonyl} -3 - [(4-methylphenyl) amino] acrylate

A Mixture of ethyl 3 - [(2,6-dimethylphenyl) amino] -3-oxopropanoate (1.25 g, 5 mmol), p-toluidine (0.6 g, 5 mmol) and triethyl orthoformate (0.83 g, 5 mmol) is added for 4h at 150 ° C in an apparatus, during the the resulting ethanol is distilled off, then stirred Hexane (10 mL) was added, the mixture stirred for 1 h at 0 ° C and finally overnight in the refrigerator stored. The resulting precipitate is filtered off and dried. Yield 51% (0.94 g, 2.7 mmol).

The Reaction to the iminoester is carried out as described above.

Claims (2)

Substituted 3-amino-acrylic acid iminoester of the tautomeric formula

R ₁ = aryl, substituted aryl, alkyl or heterocyclic; R ₂ = aryl or alkyl; R ₃ = CN, CO ₂ R ₆ , COR ₆ , CF ₃ , NO ₂ or aryl; alkyl R ₄ = alkyl, aryl, subst. aryl, allyl, heterocyclic, alkylaryl or alkyl-heterocyclic, bridging R ₅ = alkyl or aryl, H, OR ₆ R ₆ = alkyl or aryl Metal catalyst having at least one ligand according to claim 1.