Method of obtaining polyhydro[60]fullerenes

FIELD: chemistry.

SUBSTANCE: invention concerns method of obtaining polyhydro[60]fullerenes of formula (I): , involving fullerene C60 interaction with aluminium trichloride (AlCl3) in the presence of magnesium powder and zirconocene dichloride catalyst (Cp2ZrCl2) at molar ratio of C60:AlCl3:Mg:Cp2ZrCl2=1:(95-105):(95-105):(0.15-0.25), preferably 1:100:100:0.20, in argon atmosphere in the absence of light at room temperature of (20-21°C) and atmospheric pressure in toluene medium for 2-4 hours, with further hydrolysis of reaction mass. The method allows obtaining total 80-94% 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 (I):

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.) get 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.) get 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 12 who and 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 aluminum trichloride (AlCl3in the presence of Mg powder and catalytic amounts Cp2ZrCl2taken in a molar ratio With60:AlCl3:Mg:Cp2ZrCl2=1:(95-105):(95-105):(0.15-0.25), preferably 1:100:100:0.20, in argon atmosphere in the absence of light at room temperature (20-21°C) and atmospheric pressure in toluene for 2-4 hours, followed by hydrolysis of the reaction mass. The total output polyhedra[60]fullerenes of the formula (1) is 80-94%.

The reaction proceeds according to the scheme:

The conduct of a specified reaction in the presence of a catalyst Cp2ZrCl2greater than 0.25 mol does not lead to a significant increase in the yield of the target product (1). The use of the catalyst Cp2ZrCl2less 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 reagent is in the 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).

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 AlCl3.

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 40 ml of dried toluene, 0.05 mmol C60, 120 mg-at. Mg (powder), 0.01 mmole of catalyst Cu2ZrCl2and 5 mmol AlCl3mixed for 3 hours in the absence of light at a temperature of 20-21°C. Separating the unreacted Mg. The reaction mixture was treated in an argon atmosphere in the absence of light ethereal HCl solution is passed through AlCl3the solvent is evaporated in vacuum. Get polyhedra[60]fullerenes (1) with the release of 86%.

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

An NMR spectrum1N (δ, ppm, CDCl3): 3.57, 4.90, 5.75, 5.84, 6.26, 6.43, 6.65, 7.06 ppm

Other examples of the method shown in the table.

№№ p/pSoo is wearing 60: AlCl3:Mg:Cp2ZrCl2mmolReaction time, hoursThe output polyhedra[60]fullerenes (1), %
11:100:100:0.2386
21:105:105:0.2389
31:95:95:0.2382
41:100:100:0.25394
51:100:100:0.15380
61:100:100:0.2492
71:100:100:0.2291

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

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

characterized in that the fullerene C60subjected to interaction with aluminum trichloride (AlCl3in the presence of Mg powder and catalyst zirconatetitanate (Cp2ZrCl2), taken in a molar ratio of C60:AlCl3:Mg:Cp2ZrCl2=1:(95-105):(95-105):(0,15-0,25), preferably 1:100:100:0,20, in argon atmosphere in the absence of light at room temperature (20-21°C) and atmospheric pressure in the environment of toluene for 2-4 h with subsequent gidrol the zoom of the reaction mass.



 

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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

FIELD: chemistry.

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.

EFFECT: improved method.

7 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention concerns method of obtaining polyhydro[60]fullerenes of formula (1): , involving fullerene C60 interaction with diethylaluminium chloride (Et2AlCl) in the presence of magnesium powder and titanocene dichloride catalyst (Cp2TiCl2) at molar ratio of C60:Et2AlCl:Mg:Cp2TiCl2=1:(110-130):(55-65):(0.15-0.25), preferably 1:120:60:0.20, 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 total 70-88% output of polyhydro[60]fullerene after reaction mass hydrolysis.

EFFECT: improved method.

9 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention concerns method of obtaining polyhydro[60]fullerenes of formula (1): , involving fullerene C60 interaction with diisobutylaluminum chloride (i-Bu2AlCl) in the presence of zirconocene dichloride catalyst (Cp2ZrCl2) at molar ratio of C60:i-Bu2AlCl:Cp2ZrCl2=1:(55-65):(0.15-0.25), preferably 1:60:0.20, in argon atmosphere in the absence of light at room temperature of 60-100°C and atmospheric pressure in toluene medium for 1-5 hours, with further hydrolysis of reaction mass. The method allows obtaining total 77-91% output of polyhydro[60]fullerene after reaction mass hydrolysis.

EFFECT: improved method.

1 tbl, 7 ex

FIELD: CHEMISTRY.

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EFFECT: increase in catalyst activity, when catalytic process takes place under mild conditions.

2 cl, 5 tbl, 25 ex

FIELD: industrial organic synthesis.

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EFFECT: increased degree of benzene conversion.

2 ex

FIELD: petroleum processing and petrochemistry.

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EFFECT: increased activity and selectivity of catalyst with regard to formation of desired reaction products and preserved catalyst activity regarding hydrogenation of aromatics.

4 cl, 1 dwg, 14 ex

FIELD: preparation of crystal elemento-alumo-phosphates, including alumo-phosphates of zeolite-like structure.

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EFFECT: possibility of obtaining pure-phase specimens without by-phases.

39 cl, 1 dwg, 7 tbl

The invention relates to the field of chemical technology

The invention relates to the production of synthetic rubbers obtained solution polymerization, in particular to methods for hexane solvent

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

FIELD: chemistry.

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.

EFFECT: improved method.

7 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention concerns method of obtaining polyhydro[60]fullerenes of formula (1): , involving fullerene C60 interaction with diethylaluminium chloride (Et2AlCl) in the presence of magnesium powder and titanocene dichloride catalyst (Cp2TiCl2) at molar ratio of C60:Et2AlCl:Mg:Cp2TiCl2=1:(110-130):(55-65):(0.15-0.25), preferably 1:120:60:0.20, 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 total 70-88% output of polyhydro[60]fullerene after reaction mass hydrolysis.

EFFECT: improved method.

9 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention concerns method of obtaining polyhydro[60]fullerenes of formula (1): , involving fullerene C60 interaction with diisobutylaluminum chloride (i-Bu2AlCl) in the presence of zirconocene dichloride catalyst (Cp2ZrCl2) at molar ratio of C60:i-Bu2AlCl:Cp2ZrCl2=1:(55-65):(0.15-0.25), preferably 1:60:0.20, in argon atmosphere in the absence of light at room temperature of 60-100°C and atmospheric pressure in toluene medium for 1-5 hours, with further hydrolysis of reaction mass. The method allows obtaining total 77-91% output of polyhydro[60]fullerene after reaction mass hydrolysis.

EFFECT: improved method.

1 tbl, 7 ex

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21 cl, 7 tbl, 15 ex, 40 dwg

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

FIELD: chemistry.

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.

EFFECT: improved method.

7 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention concerns method of obtaining polyhydro[60]fullerenes of formula (1): , involving fullerene C60 interaction with diethylaluminium chloride (Et2AlCl) in the presence of magnesium powder and titanocene dichloride catalyst (Cp2TiCl2) at molar ratio of C60:Et2AlCl:Mg:Cp2TiCl2=1:(110-130):(55-65):(0.15-0.25), preferably 1:120:60:0.20, 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 total 70-88% output of polyhydro[60]fullerene after reaction mass hydrolysis.

EFFECT: improved method.

9 ex, 1 tbl

FIELD: chemistry.

SUBSTANCE: invention concerns method of obtaining polyhydro[60]fullerenes of formula (1): , involving fullerene C60 interaction with diisobutylaluminum chloride (i-Bu2AlCl) in the presence of zirconocene dichloride catalyst (Cp2ZrCl2) at molar ratio of C60:i-Bu2AlCl:Cp2ZrCl2=1:(55-65):(0.15-0.25), preferably 1:60:0.20, in argon atmosphere in the absence of light at room temperature of 60-100°C and atmospheric pressure in toluene medium for 1-5 hours, with further hydrolysis of reaction mass. The method allows obtaining total 77-91% output of polyhydro[60]fullerene after reaction mass hydrolysis.

EFFECT: improved method.

1 tbl, 7 ex

FIELD: chemistry.

SUBSTANCE: invention concerns method of obtaining alpha-olefins, involving reaction of ethylene during oligomerisation in the presence of catalytic system obtained by mixing in situ of: metal salt based on Fe(III); ligand of bis-iminopyridine; and (c) co-catalyst, which is a product of reaction of water with one or more organoaluminum compound where one or more organoaluminum compound is selected out of: (i) βδ-forked compounds of formula (I): Al(CH2-CR1R2-CH2-CR4R5R6)xR3yHz, where R1 is linear or forked, saturated or non-saturated C1-C20-alkyl-, C3-C20-cycloalkyl-, C6-C20-aryl- or C7-C20-alkylaryl-radical; R2 is hydrogen or linear or forked, saturated or non-saturated C1-C20-alkyl-, C6-C20-aryl-, C7-C20-alkylaryl- or -arylalkyl-radical; R3 is linear or forked, saturated or non-saturated C1-C20-alkyl-, C3-C20-cycloalkyl-, C6-C20-aryl-, C7-C20-alkylaryl- or C7-C20-arylalkyl-radical; x is integer from 1 to 3; z is 0 or 1; y is 3-x-z; R4 and R5 are the same or differ, and are linear or forked, saturated or non-saturated C1-C20-alkyl-, C3-C20-cycloalkyl-, C6-C20-aryl-, C7-C20-arylalkyl- or -alkylaryl-radicals; R1 and R4 or R4 and R5 substitutes form optionally one or two rings with 3-6 carbon atoms; R6 is hydrogen or the same as R4 and R5; (ii) (βγ-forked compounds of formula (II): Al(CH2-CR1R2-CH2-CR4R5R6)xR3yHz, where R1, R2, R3, R4, R5, R6, x, y and z are defined as for the formula (I); R4 and R5 are the same or differ, and are linear or forked, saturated or non-saturated C1-C20-alkyl-, C3-C20-cycloalkyl-, C6-C20-aryl-, C7-C20-arylalkyl- or -alkylaryl-groups; R1 andR4 or R4 and R5 form optionally one or two rings with 3-6 carbon atoms; R6 is hydrogen or the same as R4 and R5 ; and their mixes where metal salt and ligand of bis-aryliminopyridine are mixed and are soluble in aliphatic or aromatic solvent.

EFFECT: extended lifetime and enhanced catalytic activity of catalytic systems at unchanged purity and alpha-olefin output.

8 cl, 1 tbl, 21 ex

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