The way to obtain 1-ethyl-3,3-dialkyl-6,7-fullerene[60] cyclohepta-2-acs-1-alano

 

The invention relates to a method of obtaining new alyuminiiorganicheskikh derivatives of formula 1, which can be used as extractants, absorbents, additives and physiologically active substances. The method consists in the interaction of fullerene [60] with excess EtAl2in the presence of a catalyst of zirconatetitanate Cp2ZrCl2in an argon atmosphere at room temperature for 24 hours in an environment of toluene followed by the addition at a temperature of -15oWith catalyst odnoklasniki CuCl copper in the amount of 0.5-1 mol. % towards triethylaluminium and ketone of the formula RR1CO, where R=CH3, R1= C2H5; R=CH3, R1=i-C4H9; R=C2H5, R1=H-C4H9in equimolar towards triethylaluminium number, followed by stirring the reaction mixture in an argon atmosphere at room temperature for 6-10 hours Technical result - obtaining new alyuminiiorganicheskikh compounds used as sorbents, additives and extractants. table 1.

The present invention relates to methods for new alyuminiiorganicheskikh compounds, particularly to a method of obtaining 1sub>3, R'=C2H5; R=CH3, R'=i-C4H9; R=C2H5, R=n-C4H9n=1-3; With60-allotropic modification of carbon Offer fullerenelike cyclic alyuminiiorganicheskikh compounds may find application in organic and ORGANOMETALLIC synthesis, and products functionalization of (1) are of interest as extractive agents, absorbents, additives, physiologically active substances.

The known method (L. I. the Zakharkin, L. A. Savin. Synthesis of some cyclic alkylamidoamines and alkylamidoamines. WPI. An SSSR, OOHS, 1962, 5, 824-827] get 1 isobutyltrimethoxysilane (2) reaction diisobutylaluminum with diisobutylaluminium taken in a molar ratio of ~ 15: 1, at a temperature of 125-130oC for 6 hours according to scheme 1 (see end of text).

The known method does not allow to get fullerenelike cycloheptadiene (1).

The known method (EN 2160274 C1, 10.12.2000) obtain fullerensoderzhashchikh cyclic alkoxysilanes (3) the interaction of fullerene (C60with alkoxysilylated (RO-AlCl2and activated magnesium (Mg), taken in a molar ratio of 1:(50-150):(30-50), respectively, in the presence of a catalyst Cp2TiCl2PR is p> The known method does not allow to obtain 1-ethyl-3,3-dialkyl-6,7-fullerene[60]cyclohepta-2-ACS-1-Alans (1).

Thus, in the literature there are no data on the synthesis of 1-ethyl-3,3-dialkyl-6,7-fullerene[60]cyclohepta-2-ACS-1-Alans (1).

We propose a new method for the synthesis of 1-ethyl-3,3-dialkyl-6,7-fullerene[60] cyclohepta-2-ACS-1-Alans (1).

The method consists in the interaction of fullerene (C60) excess of triethylamine (AES), taken in a molar ratio With60:lEt3=1: (30-50), preferably 1:40, in the presence of a catalyst of zirconatetitanate (Cp2ZrCl2) in the amount of 0.5a 1.5 mol.% in relation to lt3preferably 1 mol. % in argon atmosphere at room temperature (21-22oC) for 24 h in toluene as solvent followed by the addition at a temperature of -15oWith catalyst odnoklasniki copper (CuCl) in the amount of 0.5a 1.5 mol.% in relation to AlEt3preferably 1 mol.%, and dialkylamino RR'CO, where R=CH3, R'=C2H5; R=CH3, R'=i-C4H9; R=C2H5, R'=n-C4H9in equimolar towards lt3the number, followed by stirring the reaction mixture for 6 to which their cycloheptadiene (1), certain products of hydrolysis by HPLC, is 59-84%. The reaction proceeds according to the scheme 3 (see end of text).

Triethylaluminium (AlEt3) and ketone (RR'CO) take in excess relative to the fullerene (C60) to include in the molecule of fullerene more cycloheptadiene fragments. Reducing the number lt3and RR'CO with respect to C60for example, With60: AlEt3:RR'CO=1:20:20 decreases the yield of the target products, and also to reduce the number of the input molecule60cycloheptadiene fragments. Changing the ratio of initial reagents in the direction of increasing the content of AlEt3and RR'CO with respect to C60for example, C60: AlEt3: RR'CO= 1:60:60, does not lead to a significant increase in the yield of target products, as well as increasing the number entered in the fullerene molecule [60J cycloheptadiene fragments.

1-Ethyl-3,3-dialkyl-6,7-fullerene[60] cyclohepta-2-ACS-1-Alans (1) are formed only with the participation of AlEt3, RR'and CO catalysts Cp2ZrCl2and Cul. In the presence of other aluminum compounds (e.g., i-AlBu3Et2AlCl, l-VI2l, i-Bu2AlCl) or other catalysts (e.g., Zr(acac)4, Py2ZrCl6, TiCl4the target issue for lighting the Sabbath. or CuCl greater than 1.5 mol.% does not lead to a significant increase in the yield of the target products. The use of the catalyst Cp2ZrCl2or CuCl less than 0.5 mol.% reduces output 1-ethyl-3,3-dialkyl-6,7-fullerene[60]cyclohepta-2-ACS-1-Alans (1), which is connected, possibly, with a reduction of catalytically active sites in the reaction mass. Experiments were performed at room temperature (21-22oC). At higher temperatures, for example, 50oWith no significant increase in the yield of the target products (1), at a lower temperature, for example, 0oWith reduced reaction rate.

Significant differences of the proposed method.

The proposed method is based on using as initial reagents AlEt3and ketones, and as catalysts Cp2ZrCl2and CuCl. In the known method are used as initial reagents alkoxysilylated (RO-AlCl2and magnesium, and as a catalyst Cp2TiCl2. In addition, if in a known way during the reaction are formed 1-alkoxy-2,3-fullerene[60] almacenadora (3), in the proposed method, form 1-ethyl-3,3-dialkyl-6,7-fullerene[60]cyclohepta-2-ACS-1-Alans (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 installed on mA the l of dry toluene, 2 mmol AlEt3and the catalyst Cf2Zrl2in the amount of 0.02 mmol (1 mol.% in relation to AlEt3), stirred for 24 h at room temperature (21-22oC) the reaction mass is then cooled to -15oTo add the catalyst CuCl in the amount of 0.02 mmol (1 mol.% in relation to AlEt3) and methyl (MeEtCO) in an amount of 2 mmol, temperature was raised to room temperature (21-22oC) and stirred for 8 hours Get 1-ethyl-3-methyl-3-ethyl-6,7-fullerene[60] cyclohepta-2-ACS-1-Alan (1) with the number cycloheptadiene fragments from 1 to 3 with a total yield of 74%. Exit (1) were determined using HPLC hydrolysis products according to scheme 4 (see end of text).

The spectral characteristics of 1-(3 methyl-3'-hydroxyphenyl)2-hydrofolate [60] (1): an NMR Spectrum1N (, M. D. CDCl3):0.89 (t, CH3), 1,20-to 1.61 (m, CH2), 2,09-of 2.28 (m, CH3), 7,07 (s, H, C60-h). An NMR spectrum13With (, M. D., CDCl3):36,72 t (1), 35,87 t (2), 73,91 d (3), 33,53 t (4), 13,50 t (5), 18,38 to (6).

Other examples of the method are given in table. 1.

The reaction was carried out at room temperature 21-22oC.

As a solvent used toluene because it is the greatest solution of the 7-fullerene[60] -cyclohepta-2-ACS-1-Alans General formula 1where R=CH3, R'=C2H5; R=CH3, R'=i-C4H9;
R=C2H5, R'=n-C4H9;
n=1-3;
With60- allotropic modification of carbon,
characterized in that the fullerene [60] interacts with an excess of triethylamine (lt3), taken in a molar ratio With60:lt3=1:(3050), in the presence of a catalyst of zirconatetitanate (Cp2ZrCl2) in an amount of 0.5 to 1.5 mol. % towards triethylaluminium in an argon atmosphere at room temperature, in the presence of toluene as solvent for 24 h followed by the addition at a temperature of -15oWith catalyst odnoklasniki copper (CuCl) in an amount of 0.5-1.5 mol.% in relation to triethylaluminium and ketone of the formula
RR'CO.,
where R is CH3, R'=C2H5; R=CH3, R'=i-C4H9; R=C2H5, R'=n-C4H9,
in equimolar towards triethylaluminium number, after which the reaction mass is stirred at room temperature in an argon atmosphere within 6-10 hours

 

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