The way to obtain 1-(n-butyl)-2-mg(n-butyl)[60]fullerenes

 

(57) Abstract:

The invention relates to organic chemistry, and in particular to methods of obtaining new magyarkanizsa compounds. The method consists in the interaction of toluene solution of fullerene (C60with excess ethereal solution of di(n-butyl)magnesium (H-Bu2Mg) in the presence of a catalyst of zirconatetitanate (Cp2Zr Cl2) in an amount of 1 to 3 mol.% in relation to n-Bu2Mg. The reaction is carried out in an argon atmosphere under normal conditions for 8 to 12 h, when the molar ratio C60:: (n-Bu2Mg) = 1 : (35 - 90). The obtained magnesium-containing fullerenes can find application in thin organic and ORGANOMETALLIC synthesis. table 1.

The invention relates to methods for new magnesium-organic compounds, specifically, to a method for producing 1-(n-butyl)-2-mg(n-butyl) [60] fullerenes General formula (I):

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where n = 1-6,

C60- new allotropic modification of carbon;

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, extractants, sorbents, the sultans. News of art of the USSR. The series of chem., 1983, page 218) 1,2-carbamazipine-olefins using diethylamine (Et2Mg) in the presence of catalytic amounts Cp2ZrCl2at room temperature in air, leading to 1-ethyl-2-magnesium-containing alkaram scheme:

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By a known method cannot be obtained 1-(n-butyl)-2-mg(n-butyl) [60] fullerenes (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) 1,2-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. The reaction 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 obtain 1-(n-butyl)-2-mg(n-butyl) [60]fullerenes (1).

Thus, to date, the literature contains no information on the synthesis of 1-(n-butyl)-2-magnesium [60] fullerenes (1).

We propose a new method for the synthesis of 1-(n-butyl)-2-mg-(n-butyl) [60] fullerenes.

The essence of IPN(n-butyl)magnesium (n-Bu2Mg), taken in a molar ratio of C60:(n-Bu2Mg)=1:(35 - 90), preferably 1: 60, in the presence of zirconatetitanate (Cp2ZrCl2) in an amount of 1 to 3 mol.% in relation to n-Bu2Mg, preferably 2 mol.%, in an argon atmosphere at room temperature (22-23oC) and normal pressure for 8 to 12 hours, preferably 10 hours. Output 1-(n-butyl)-2-mg(n-butyl)-[60]fullerene (1) 70-94%. Output alkyl Mg-containing fullerenes (1) was determined by the products of hydrolysis. The reaction proceeds according to the scheme:

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Dibutylamine (n-Bu2Mg) taken in excess with respect to the original fullerene C60with the purpose of introducing into the molecule of fullerene as much as possible the number of h-Budilnik groups. The reduction in the number of n-Bu2Mg relative to C60leads to some reduction of the yield of the target products, as well as lower input to the fullerene molecule n-Budilnik and n-butylmagnesium groups. Changing the ratio of initial reagents in the direction of increasing the content of n-Bu2Mg relative to C60does not lead to a significant increase in the yield of target products (1).

The conduct of a specified reaction in the presence of a catalyst Cp2ZrCl2more than 3 mol.% does not lead to significant Overlaminating fullerenes (1), due, perhaps, with a reduction of catalytically active sites in the reaction mass. Experiments were performed at room temperature. At higher temperatures, for example, 60oC there is no significant increase in the yield of the target products, at a lower temperature, for example, 0oC decreases the reaction rate. The reaction was carried out in toluene solution, because it is the best solvent for fullerene. The original n-Bu2Mg synthesized in the ether, because it is one of the best solvents for Mg-organic reagents.

Significant differences of the proposed method:

The proposed method is based on using as initial reagents di(n-butyl)magnesium (n-Bu2Mg) 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 1-(n-butyl)-2-mg-(n-butyl) [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 and in which-Bu2Mg (0.8 M ether solution) in 20 ml of ether and the catalyst Cp2ZrCl2in the amount of 0.06 mmol (2 mol% relative to n-Bu2Mg), stirred for 10 hours at room temperature. Get 1-(n-butyl)-2-mg(n-butyl)[60]fullerenes (1) with a total yield of 82%. Exit (1) was determined by the products of hydrolysis (2)

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The spectral characteristics of 1-(n-butyl)-2-hydro[C60]-fullerenes (2):

Range of the MRP , M. D.): 0,89 - 1,26 M. D. (CH3, leaf n-butylene), 1,32-1.89 m (CH2n-butylene), 4,32-5,20 m (CH, fullerene). The mass spectrum of negative ions n-butylacetamide fullerenes (2) consists of the following mass lines: 778 (n-Bu1C60H1), 836 (n-Bu2C60H2), 894 (n-Bu3C60H3), 952 (n-Bu4C60H4), 1010 (n-Bu5C60H5), 1068 (n-Bu6C60H6).

Other examples of the method are given in table. 1

The reaction was carried out at room temperature (22-23oC). The temperature rise is not advisable, since there is no significant increase in the yield of the target products. At a lower temperature decreases the reaction rate. As a solvent, it is advisable to use toluene and ether, because they are the highest solubility ACC is Ulanov. Izvestiya an SSSR. The series of chem., 1983, page 218.

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.

The way to obtain 1-(n-butyl)-2-mg-(n-butyl)[60]fullerenes, wherein the toluene solution of fullerene C60interacts with excess ethereal solution of di(n-butyl) magnesium (n-Bu2Mg) in a molar ratio WITH60: (n-Bu2Mg)=1:(35-90) in the presence of a catalyst of zirconatetitanate (Cp2ZrCl2) in an amount of 1 to 3 mol.% in relation to n-Bu2Mg, in argon atmosphere, under normal conditions within 8 - 12 hours.

 

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where n = 1 to 4;

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< / BR>
where n = 1-6, C60- new allotropic modification of carbon;

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< / BR>
where n = 1 to 4;

C60- new allotropic modification of carbon;

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Hal = Br, Cl

The invention relates to organic chemistry, and in particular to methods of obtaining new compounds magyarkanizsa

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< / BR>
where n = 1-6, C60- new allotropic modification of carbon;

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1 tbl, 10 ex

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1 tbl, 5 ex

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2 tbl

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