The way to obtain 1-(n-propyl)-2-minihaloes [60]- fullerene


(57) Abstract:

Describes a new method to produce 1-(n-propyl)-2-minihaloes([60] fullerenes, wherein the toluene solution of fullerene C60interacts with excess ethereal solution of n-propylaniline (n-PrMgBr) or n-propylaniline (n-PrMgCl), taken in a molar ratio of C60: n-PrgHal =1:(50-150), in the presence of zirconatetitanate (Cp2ZrCl2as the catalyst, taken in the amount of 1-3 mol.% in relation to n-PrMgHal, in an argon atmosphere under normal conditions within 8-12 hours New magnesium-containing fullerenes can find application in thin organic and ORGANOMETALLIC synthesis. table 1.

The invention relates to methods for new magyarkanizsa compounds, specifically, to a method for producing 1-(n - propyl)-2-minihaloes [60] fullerenes General formula (1):

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

Hal = Br, Cl.

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, shotacon 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:

< / BR>
By a known method cannot be obtained 1-(n-propyl)-2-minihaloes [60] fullerenes (1).

The known method ([2], U. M. Dzhemilev, O. S. Vostrikova, P. 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. Carbamazipine is solely on the terminal double bonds, with internal disubstituted double bond in the reaction is not involved.

< / BR>
The known method does not allow to obtain 1-(n-propyl)-2-minihaloes[60] fullerenes (1).

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

We propose a new method (synthesis of 1-(n-propyl)-2-magnesium-halogen bonds[60] fullerenes.

The method consists in the(n-PrMgBr) or n-propylaniline (n-PrMgCl), taken in a molar ratio of C60: n-PrMgHal = 1 : (50-150), preferably 1:100, in the presence of a catalyst of zirconatetitanate (Cp2ZrCl2) in an amount of 1 to 3 mol.% in relation to PrMgHal, 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-propyl)-2 - minihaloes[60]fullerenes (1) 76-92%. Output alkyl Mg-containing fullerenes (1) was determined by the products of hydrolysis. The reaction proceeds according to the scheme

< / BR>
n = 1 - 6, Hal = Br, Cl

n-Propylaniline (n-PrMgHal) take in excess relative to the fullerene C60with the purpose of introducing into the molecule of fullerene greatest number of n-sawn and holodnognutyh groups. The reduction in the number of n-PrMgHal relative to C60leads to some reduction of the yield of the target products, as well as lower input to the fullerene molecule n-sawn and minigallery groups. Changing the ratio of initial reagents in the direction of increasing the content of n-PrMgHal relative to C60does not lead to a significant increase in the yield of carmagnani fullerene molecules (1).

The conduct of a specified reaction in the presence of a catalyst Cp2ZrCl2more than 3 mol.%2 less than 1 mol.% reduces output 1-(n-propyl)-2-minihaloes[60] fullerenes, possibly associated with some decrease in the catalytically active sites in the reaction mass. Experiments were performed at room temperature. At higher temperatures, for example 60oC, no significant increase of the yield of the target products, at a lower temperature, for example 0oC, decreases the reaction rate. Carbamazipine fullerene carried out in toluene solution, as it is the best solvent for fullerene. The original n-propylaniline 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 n-propylaniline (n-PrMgBr or n-PrMgCl) and fullerene C60the reaction proceeds in a mixture of aromatic (toluene) and ether solvent. In the known method are used determine (Et2Mg) and acyclic triene (1,4 E,9-decatriene).

The proposed method, in contrast to the known, allows to obtain 1-(n-propyl)-2-minihaloes[60] -fullerene (1), the synthesis of which are not described in literature.

The way peaslake in the atmosphere of argon at room temperature was placed 0.05 mmol of fullerene C60, 40 ml dry toluene, 5 mmol n-PrMgBr (0.95 M ether solution) in 20 ml of ether and the catalyst Cp2ZrCl2in the amount of 0.1 mmol (2 mol. % relative to n-PrMgHal), stirred for 10 hours at room temperature (22-23oC). Get 1-(n-propyl)-2 - mineraloid[C60]-fullerenes General formula (1) with the number n-sawn and minigallery fragments from 1 to 6 with a total yield of 84%. Exit (1) was determined by the products of hydrolysis (2):

< / BR>
n = 1 - 6.

The spectral characteristics of 1-(n-propyl)-2-hydro[C60]- fullerenes (2): the Range of the MRP , M. D.): 0,95 t (CH3, 'J C-H = 7 Hz), 1.29 - 1.50 m (CH2, sawn), 3.70 - 4.05 m (CH, fullerene). The mass spectrum of negative ions n-propylsilane fullerenes (2) consists of the following mass lines: 764 (n-Pr1C60H1), 808 (n-Pr2C60H2), 852 (n-Pr3C60H3), 896 (n-Pr4C60H4), 940 (n-Pr5C60H5), 984 (n-Pr6C60H6).

Other examples of the method shown in the table.

The reaction was carried out at room temperature (22-23oC). The temperature rise is impractical because there is no significant increase in the yield of the target products. At lower temperatures sijaitsevalle respectively fullerene C60and PrMgHal.

The way to obtain 1-(n-propyl)-2-minihaloes[60]fullerenes, wherein the toluene solution of fullerene C60interacts with excess ethereal solution of n-propylaniline (n-PrMgBr) or n-propylaniline (n-PrMgCl), taken in a molar ratio of C60: n-PrMgHal = 1 : (50 - 150), in the presence of zirconatetitanate (Cp2ZrCl2as the catalyst, taken in an amount of 1 to 3 mol.% in relation to n-PrMgHal, in an argon atmosphere under normal conditions within 8 - 12 hours


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