Method of obtaining polyhydro[60]fullerenes

FIELD: chemistry.

SUBSTANCE: invention concerns method of obtaining polyhydro[60]fullerenes of formula (1): , involving fullerene C60 interaction with ethylaluminium dichloride (EtAlCl2) in the presence of magnesium powder and titanocene dichloride catalyst (Cp2TiCl2) at molar ratio of C60:EtAlCl2:Mg:Cp2TiCl2=1:(55-65):(55-65):(0.15-0.25), preferably 1:60:60:0.20, in argon atmosphere in the absence of light at room temperature of (20-21°C) and atmospheric pressure in toluene and tetrahydrofuran medium for 1-3 hours, with further hydrolysis of reaction mass. The method allows obtaining 72-86% output of polyhydro[60]fullerene after reaction mass hydrolysis.

EFFECT: improved method.

1 tbl, 7 ex

 

The present invention relates to the field of organic chemistry, specifically to a method for polyhedra[60]fullerenes General formula (1):

Polyhedra[60]fullerenes of the formula (1) can be applied in thin organic synthesis, production of high-energy fuel, hydrogen batteries.

The known method ([1], A.G.Avent, A.D.Darwish, D.K.Heimbach, H.W.Kroto, M.F.Meidine, J.P.Parsons, C.Remars, R.Roers, O.Ohashi, R.Taylor, D.R.M.Walton. J. Chem. Soc. Perkin Trans.2, 1994, 15) receiving dihydro[60]fullerene (2) interaction of the benzene solution of [60]fullerene with an excess of hydrazine hydrate is added (˜1:1000) in the presence of glacial acetic acid, and copper sulfate periodate sodium under vigorous stirring ˜20 hours in an argon atmosphere.

The known method cannot be obtained polyhedra[60]fullerenes of the formula (1).

The known method ([2], S.Ballenweg, R.Gleiter, W.Kratschmer. J. Chem. Soc., Chem. Commun., 1994, 2269) receipt of polyhedra[60]fullerenes (4) hydrozirconation60using zirconolite (Schwartz reagent) at a temperature of 20-22°in toluene solution for 24 hours followed by hydrolysis of the formed in situ Zirconia-fullerene complexes (3) according to the scheme:

In a known manner can be obtained polyhedra[60]fullerenes of the formula (1) with the number of hydrogen atoms from 6 to a fullerene sphere.

We propose a new method of obtaining polyhedra[60]fullerenes of the formula (1).

The method consists in the interaction of fullerene With60with ethylaminoethanol (EtAlCl2in the presence of Mg powder and catalytic amounts Cp2TiCl2taken in a molar ratio With60:EtAlCl2:Mg:Cp2TiCl2=1:(55-65):(55-65):(0.15-0.25), preferably 1:60:60:0.20, in an argon atmosphere at room temperature (20-21°C) and atmospheric pressure in the environment toluene-THF (˜10:1, by volume) for 1-3 hours, followed by hydrolysis of the reaction mass. The total output polyhedra[60]fullerenes of the formula (1) is 72-86%.

The reaction proceeds according to the scheme:

The conduct of a specified reaction in the presence of a catalyst Cp2TiCl2greater than 0.25 mol does not lead to a significant increase in the yield of the target product (1). The use of the catalyst Cp2TiCl2less than 0.15 mol reduces the yield of the target product (1), which is probably associated with the reduction of the catalytically active sites in the reaction mass. The reaction was carried out at room temperature (20-21°). At a higher temperature (for example, 40° (C) has not been a significant increase in the yield of the target product (1), and at a lower temperature (e.g., 0° (C) decreases the reaction rate. The change in the ratio of the source is of agentov increase of their content in relation to the original fullerene[60] does not lead to a significant increase in the yield of the target product (1).

Reactions were performed in the environment toluene-THF, due to the high solubility of fullerene[60] in toluene and formed under the reaction conditions MgCl2in THF.

Significant differences of the proposed method.

In the known method is used as the starting compound inaccessible Schwartz reagent (Cp2ZrClH), and the proposed method as the original connection is produced on an industrial scale EtAlCl2.

The proposed method, in contrast to the known, allows you to get polyhedra[60]fullerenes of the formula (1).

The method is illustrated by the following examples.

EXAMPLE 1. In a glass reactor, mounted on a magnetic stirrer, an argon atmosphere was placed 30 ml of dried toluene and 3 ml of THF, 0.05 mmol C603 mg-at. Mg (powder), 0.01 mmol catalyst Cp2TiCl2and 3 mmol EtAlCl2stir in the absence of light for 2 hours at a temperature of 20-21°C. Separating the unreacted Mg, THF evaporated without heating in vacuum. The reaction mixture was treated in an argon atmosphere in the absence of light ethereal HCl solution is passed through Al2About3the solvent is evaporated in vacuum. Get polyhedra[60]fullerenes (1) yield 78%.

Spectral characteristics of polyhedra-[60]fullerene (1): IR-range (νcm-1): 2925, 2855.

Range of I Is R 1N (δ, ppm, CDCl3): 3.57, 4.90, 5.75, 5.84, 6.26, 6.43, 6.65, 7.06 ppm

M+: 726[C60H6], 732[C60H12].

Other examples of the method shown in the table.

№№ p/pThe ratio of C60:EtAlCl2:Mg:Cp2TiCl2mmolReaction time, hoursThe output polyhedra[60]fullerenes (1), %
11:60:60:0.2278
21:65:65:0.2281
31:55:55:0.2274
41:60:60:0.25286
51:60:60:0.15272
61:60:60:0.2384
71:60:60:0.2173

The reaction was carried out at room temperature (20-21° (C) in a solvent mixture of toluene-THF in an argon atmosphere without access of light.

The method of obtaining polyhedra[60]fullerenes of the formula (1)

characterized in that the fullerene C60subjected to interaction with ethylaminoethanol (EtAlCl2in the presence of Mg powder and catalyst titanocene orida (Cf 2TiCl2), taken in a molar ratio of C60:EtAlCl2:Mg:Cp2TiCl2=1:(55-65):(55-65):(0,15-0,25), preferably 1:60:60:0,20, in argon atmosphere in the absence of light at room temperature (20-21°C) and atmospheric pressure in the environment toluene-THF within 1-3 h followed by hydrolysis of the reaction mixture.



 

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SUBSTANCE: invention concerns method of obtaining polyhydro[60]fullerenes of formula (1): , involving fullerene C60 interaction with diisobutylaluminum hydride (i-Bu2AlH) in the presence of zirconium tetrachloride catalyst (ZrCl4) at molar ratio of C60:i-Bu2AlH:ZrCl4=1:(55-65):(0.15-0.25), preferably 1:60:0.20, in argon atmosphere in the absence of light at room temperature of (20-21°C) and atmospheric pressure in toluene medium for 1-5 hours, with further hydrolysis of reaction mass. The method allows obtaining 73-87% of polyhydro[60]fullerene output after reaction mass hydrolysis.

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FIELD: chemistry.

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9 ex, 1 tbl

FIELD: chemistry.

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9 ex, 1 tbl

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21 cl, 7 tbl, 15 ex, 40 dwg

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7 ex, 1 tbl

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9 ex, 1 tbl

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1 tbl, 7 ex

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8 cl, 1 tbl, 21 ex

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71 cl, 99 ex, 13 tbl

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