Method for preparing 1,7,8,9-tetraalkyl-10-ethyl-4-oxo-10-aluminatricyclo[5,2,1,02,6]-dec-8-ene-3,5-diones

FIELD: chemistry of metalloorganic compounds, chemical technology.

SUBSTANCE: invention relates to a method for preparing aluminum-organic compounds of the general formula (I) wherein R means ethyl (Et), n-propyl (n-Pr), n-butyl (n-Bu). Method involves interaction of di-substituted acetylenes with ethylaluminum dichloride (EtAlCl2) in the presence of metallic Mg and a catalyst in argon atmosphere under atmosphere pressure and room temperature for 8 h followed by addition of maleic anhydride at temperature -5°C and stirring the reaction mass at room temperature for 8 h. The yield of the end product is 56-78%. Proposed compounds can be used in fine organic and metalloorganic synthesis and as co-catalysts in processes of oligo- and polymerization of olefins and coupled dienes.

EFFECT: improved preparing method.

2 cl, 1 tbl, 1 ex

 

The present invention relates to methods for new alyuminiiorganicheskikh compounds (AOC), specifically, to a method for 1,7,8,9-tetraalkyl-10-ethyl-4-oxa-10-aluminasilica[5.2.1.0.2,6]Dec-8-ene-3,5-diones of General formula (1):

The proposed compounds may find application in thin and ORGANOMETALLIC synthesis, as well as socialization in the processes of oligo - and polymerization of olefins and conjugated dienes.

The known method [1. Usmjerili, Agibalov, Apolamare, RAO, Gaellic. Synthesis and transformations of metallocycles. Message 5. Regioselective synthesis of β-substituted almacenamento cyclomethicone α-olefins with Et3Al in the presence of Cp2ZrCl2// Izvestiya an SSSR. Ser. chem. 1990. S-2841] obtain unsaturated cyclic oxygen-containing alyuminiiorganicheskikh compounds (2) the interaction of 2,7-octadien-1-ol with triethylaluminium (AlEt3in the presence of catalyst zirconatetitanate (Cp2ZrCl2) according to the scheme:

The known method does not allow to get 1,7,8,9-tetraalkyl-10-ethyl-4-oxa-10-aluminasilica[5.2.1.02,6]Dec-8-ene-3,5-dione (1).

The known method [2. RF patent №2220972. BI No. 26 (20.09.2003)] obtain unsaturated cyclic oxygen-containing of aluminiowa the practical connections (3) the interaction of terminal allenes with triethylaluminium (AlEt 3in the presence of catalyst zirconatetitanate (Cp2ZrCl2with the subsequent addition of the catalyst odnoklasniki copper (CuCl) and aldehyde (RCHO) at room temperature according to the scheme:

The known method cannot be obtained 1,7,8,9-tetraalkyl-10-ethyl-4-oxa-10-aluminasilica[5.2.1.02,6]Dec-8-ene-3,5-dione (1).

Thus, the literature contains no information on the selective receiving 1,7,8,9-tetraalkyl-10-ethyl-4-oxa-10-aluminasilica[5.2.1.02,6]Dec-8-ene-3,5-diones (1).

We propose a new method of obtaining 1,7,8,9-tetraalkyl-10-ethyl-4-oxa-10-aluminasilica[5.2.1.02,6]Dec-8-ene-3,5-diones (1).

The essence of the method lies in the interaction dialkylamides acetylenes of General formulawhere R=Et, n-Pr, n-Bu, ethylaminoethanol (EtAlCl2in the presence of Mg metal (powder) and catalyst zirconatetitanate (Cp2ZrCl2), taken in a molar ratioEtAlCl2:Mg:Cp2ZrCl2equal to 20:12:12:0.5, in an argon atmosphere at room temperature (˜20°C) and atmospheric pressure in tetrahydrofuran (THF) as a solvent for 8 hours followed by the addition at a temperature of -5°With maleic anhydride in equimolar towards EtAlCl2number paramasivan the m reaction mass 6-8 hours, preferably 7 hours, at room temperature (˜20°). The reaction proceeds with the formation of 1,7,8,9-tetraalkyl-10-ethyl-4-oxa-10-aluminasilica[5.2.1.02,6]Dec-8-ene-3,5-diones (1) with output 56-78% scheme:

1,7,8,9-Tetraalkyl-10-ethyl-4-oxa-10-aluminasilica [5.2.1.02,6]Dec-8-ene-3,5-dione (1) are formed only with the participation of EtAlCl2, disubstituted acetylenes, Mg metal, zirconium catalyst Cp2ZrCl2and maleic anhydride. In the presence of other aluminum compounds (e.g., AlEt3Bui3Al, Bui2AlH), other acetylenes (e.g., terminal), other metals as acceptor halide ions (e.g., Zn, Fe, Al), other catalysts (e.g., Zr(acac)4, Cf2TiCl2Pd(acac)2, Ni(acac)2, NiCl2, Fe(acac)2other anhydrides of carboxylic acids (e.g. acetic acid or phthalic anhydrides) target products (1) are not formed.

The reaction was carried out at room temperature (˜20°). At a higher temperature (for example, 40° (C) has not been a significant increase in the yield of the target products (1), and at a lower temperature (e.g., 0° (C) decreases the reaction rate.

Changing the ratio of initial reagents (EtAlCl2, Mg, maleic anhydride) and catalyst (Cp2ZrCl2 ) increase in relation to the original the disubstituted acetylenedoes not lead to a significant increase in the yield of target products (1). Changing the ratio of initial reagents and catalyst towards their reduction in relation to the original the disubstituted acetylene reduces the yield of the target products (1).

The reaction was performed using THF as solvent. In other solvents (for example, aliphatic or aromatic) reaction is not moving.

Significant differences of the proposed method

In the proposed method for obtaining unsaturated cyclic oxygen-containing oxidants are used as starting compounds disubstituted acetylenemaleic anhydride, ethylaminoethanol (EtAlCl2) and magnesium metal (Mg). In the known method as initial reagents used terminal allene (R-=•=), triethylaluminium (Et3Al) and aldehydes (RCHO).

The proposed method has the following advantages

The method allows to obtain high selectivity 1,7,8,9-tetraalkyl-10-ethyl-4-oxa-10-aluminasilica [5.2.1.02,6]Dec-8-ene-3,5-dione (1), the synthesis of which are not described in literature.

The method is illustrated by the following examples

EXAMPLE 1. In a glass reactor with a volume of 50 ml, mounted on the magnet m is salke, in an argon atmosphere was placed 10 ml of THF, 20 mmol Gex-1-in, 12 mmol Mg (powder). The mixture is cooled to 0°add 0.5 mmol of catalyst Cp2ZrCl2and 12 mmol EtAlCl2and stirred for 8 hours at a temperature of ˜20°C. and Then at a temperature of -5°added 12 mmol of maleic anhydride, after which the reaction mass is stirred for 7 hours at room temperature. Get 1,7,8,9-tetraethyl-10-ethyl-4-oxa-10-aluminate-cyclo[5.2.1.02,6]Dec-8-ene (1) with the release of 64%. The yield of the target product identified by the product of hydrolysis (4).

The spectral characteristics of 4,5,6,7-tetraethyl-3A,4,7,7a-tetrahydro-1,3-isobenzofuran-2,9-dione (4): an NMR Spectrum13With CDCl3that δ, ppm: 172.44 (2With9), At 42.68 (1With8), 41.68 (4With7), 138.42 (5With6), 20.70 (10With16), 12.53 (C11With17), 20.01 (12With14), 14.90 (13With15).

Spectral characteristics 1,7,8,9-tetraethyl-10-ethyl-4-oxa-10-aromatizable[5.2.1.02,6]-Dec-8-ene (1). An NMR spectrum13With, (C6D6), δ, ppm: 7.15 (Al-CH2-CH3), 9.60 (Al-CH2-CH3), 12.50, 14.13, 20.18, 25.70,40.86, 42.79, 135.91, 172.77.

Other examples of the method are given in table 1.

The method of obtaining 1,7,8,9-tetraalkyl-10-ethyl-4-oxa-10-aluminasilica[5.21.0 2,6]Dec-8-ene-3,5-diones (1) the General formula:

namely, that the disubstituted acetylene General formula R-≡-R, where R=Et, n-Pr, n-Bu, interact with ethylaminoethanol EtAlCl2in the presence of Mg metal (powder) and catalyst zirconatetitanate (Cp2ZrCl2) in a molar ratio of R-≡-R:EtAlCl2:Mg:Cp2ZrCl2equal to 20:12:12:0,5, in an argon atmosphere at atmospheric pressure and room temperature in tetrahydrofuran as solvent for 8 h followed by the addition at a temperature of -5°With maleic anhydride, taken in equimolar towards EtAlCl2quantity, with stirring the reaction mass for 6-8 h at room temperature ˜20°C.



 

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