The way the joint production of mono[cycloalkyl] geminirose[60]fullerenes and bis[cycloalkyl] terminalbased[60]fullerenes

 

(57) Abstract:

The invention relates to the field of production of new magnesium-organic compounds, which can find application in thin organic and ORGANOMETALLIC synthesis. The method consists in the interaction of toluene solution of fullerene C60with excess ethereal solution-demineralize in the presence of a catalyst of zirconatetitanate, in argon atmosphere, under normal conditions within 10-20 h, with a yield of target products 62-88%. table 1.

The invention relates to methods for new magyarkanizsa compounds, particularly, to a method for simultaneous obtaining mono[cycloalkyl]geminirose[60]fullerenes and bis[cycloalkyl]terminalbased[60]fullerenes General formula (1)

[(CH2)m]nC60(MgBr)2n, (1)

where C60- new allotropic modification of carbon;

m = 4,6; n = 1,2

The obtained magnesium-containing fullerenes can find application in thin organic and ORGANOMETALLIC synthesis, and products functionalization of (1) are of interest as physiologically active substances, extraction agents, absorbents, additives, light-sensitive materials.

Usuwania - olefins using diethylamine (Et2Mg) in the presence of catalytic amounts Cp2ZrCl2at room temperature in air, leading to 2-ethyl-1-magnesium-containing alkaram scheme;

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By a known method cannot be obtained mono[cycloalkyl]geminirose[60] fullerenes and bis[cycloalkyl] terminalbased[60] fullerenes of the formula (1).

The known method ([2], U. M. Dzhemilev, O. S. Vostrikova, R. M. Sultanov, A., Kukovinets, L. M. Khalilov. Izvestiya an SSSR. The series of chem., 1984, No. 9, page 2053) carbamazipine polyene hydrocarbons, in particular 1,4 E,9-decatriene using diethylamine (Et2Mg) in the presence of catalytic amounts Cp2ZrCl2under mild conditions in ethereal solvents. Carbamazipine is solely on the terminal double bonds, with internal disubstituted double bond in the reaction is not involved.

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The known method does not allow to get mono[cycloalkyl] geminirose[60]fullerenes and bis[cycloalkyl]terminalbased[60]fullerenes (1).

We propose a new method for simultaneous obtaining mono[cycloalkyl]geminirose[60]fullerenes and bis[cycloalkyl]terminalbased[60]fullerenes General formula (1).

The essence is - demineralize General formula BrMg(CH2)mMgBr, where m = 4,6; taken in a molar ratio of C60: BrMg(CH2)mMgBr = 1:(50:150), preferably 1:100, in the presence of a catalyst of zirconatetitanate (Cp2ZrCl2) in an amount of 0.2-2 mol.% in relation to BrMg(CH2)mMgBr, preferably 1 mol.%, in an argon atmosphere at room temperature (22-23oC) and normal pressure for 10-20 hours, preferably 15 hours. The total yield of mono[cycloalkyl] geminirose[60]fullerenes (1) is 62-88% (output (1) was determined by the products of hydrolysis).

The reaction proceeds according to the scheme:

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,- demagnetize connection charge in excess relative to the fullerene with the aim of increasing the yield of the target products. Reduction ,- demagnify compounds leads to the decrease of the yield of the target products.

The conduct of a specified reaction in the presence of a catalyst Cp2ZrCl2more than 2 mol.% does not lead to a significant increase in the yield of the target products. The use of the catalyst Cp2ZrCl2less than 0.2 mol.% reduces output (1), which is connected, possibly, with a reduction of catalytically active sites in the reaction mass. Experiments were performed at room temperature. Conducting the reaction at higher temperatures, FL. At a lower temperature, for example 0oC, decreases the reaction rate. The reaction was performed in toluene solution, because it is the best solvent for fullerene. Source - demagnetize compounds synthesized in the ether, because it is the best solvent for Grignard reagents.

Significant differences of the proposed method.

The proposed method is based on using as initial reagents, magnesium compounds and fullerene C60the reaction proceeds in a mixture of aromatic (toluene) and ether solvent. In the known method are used determine (MgEt2and acyclic triene (1,4 E,9-decatriene).

The proposed method, in contrast to the known, allows to obtain mono[cycloalkyl] geminirose[60] fullerenes and bis[cycloalkyl]terminalbased[60]fullerenes (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 100 ml, mounted on a magnetic stirrer, an argon atmosphere at room temperature was placed 0.05 mmol of fullerene C60, 40 ml dry toluene, 5 mmol BrMg(CH2)6MgBr (0.85 M ether solution) in 20 ml of sulphuric ether and catalyst CpoC). Get a mixture of mono[cyclooctyl]geminirose[60]fullerenes and bis[cyclooctyl]terminalbased[60]fullerenes (1) with a total yield of 77%. Exit (1) was determined by the products of hydrolysis (2):

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The spectral characteristics of a mixture of mono[cyclooctyl]dihydro [60]fullerenes and bis[cyclooctyl]tetrahydro[60]fullerenes (2):

An NMR spectrum1H (, m D.): 1.31-1.86 m (CH2, 7.01-7.47 m (C60, -H);

Mass spectrum (m/z ): 806 (H2C60(CH2)6); 892 ([(CH2)6]2)C60H4).

Other examples of the method shown in the table.

The reaction was carried out at room temperature (22 - 23oC). As a solvent used a mixture of toluene and ether, because they are the highest solubility, respectively, C60and BrMg(CH2)mMgBr.

The way the joint production of mono[cycloalkyl]geminirose[60]fullerenes and bis[cycloalkyl] terminalbased[60] fullerenes General formula [(CH2)m]nC60(MgBr)2nwhere C60-new allotropic modification of carbon m = 4,6; n = 1,2, characterized in that the toluene solution of fullerene C60interacts with excess ethereal solution-demineralize General formula BrMg(CH2)concentrared (CfpZrCl2), taken in an amount of 0.2-2 mol.% with respect to solution-demineralize, the reaction is carried out in an argon atmosphere under normal conditions within 10-20 hours.

 

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< / BR>
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SUBSTANCE: plate tar cake is ground to produce fractional makeup having at least 97 mass % of <0.09 mm-fraction and at least 91 % of <0.045 mm-fraction. Grinded cake is mixed with 35-40 % of coal-tar asphalt and 0.015-1.5 mass % of organic additive at 120-130°C. As organic additive space-hindered phenols and/or phenylphosphites are used. Obtained mass is formed, cooled and crushed followed by pressing to produce semimanufactured article with density of1.01-1.06 g/cm3. Said articles are sintered at 800-1300°C and black-leaded at 3000°C. Finished black-leaded material has bulk density of 1760-1950 kg/cm3, compression strength of 90-105 MPa and blending strength of 60-75 MPa. Material of present invention is useful in production of electrodes, seal assembly and material of high purity.

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1 tbl, 10 ex

FIELD: aircraft industry, power production.

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EFFECT: decreased oxidation losses; material with increased compressive resistance and serviceability.

1 tbl, 5 ex

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2 tbl

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3 cl

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3 cl, 1 tbl, 6 ex

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