RU2136688C1 - Method for joint preparation of mono(cycloalkyl)dimagnesiumbromidefullerenes(60) and bis(cycloalkyl)tetramagnesiumbromid- efullerenes(60) - Google Patents

Abstract

FIELD: organic synthesis. SUBSTANCE: toluene solution of fullerene(60) interacts with excess of ether solution of α,ω- dimagnesium bromide in presence of zirconacene dichloride as catalyst for 10-20 hr under argon atmosphere and normal conditions to give products with yields 62-88%. EFFECT: extended synthetic possibilities. 1 tbl, 8 ex

Description

The invention relates to methods for producing new organomagnesium compounds, in particular, to a method for the joint production of mono [cycloalkyl] dimagnesium bromide [60] fullerenes and bis [cycloalkyl] tetramagnesium bromide [60] fullerenes of the general formula (1)
[(CH ₂ ) _m ] _n C ₆₀ (MgBr) _2n , (1)
where C ₆₀ is a new allotropic modification of carbon;
m = 4.6; n = 1,2
The obtained magnesium-containing fullerenes can be used in fine organic and organometallic synthesis, and functionalization products (1) are of interest as physiologically active substances, extractants, sorbents, additives, and photosensitive materials.

По известному способу не могут быть получены моно[циклоалкил]димагнийбромид[60] фуллерены и бис[циклоалкил] тетрамагнийбромид[60] фуллерены формулы (1).A known method ([1], U. M. Dzhemilev, O.S. Vostrikova, PM Sultanov. Izvestiya AN SSSR. Chem. Series. Chem., 1983, p. 218) carbomagnetize α-olefins using diethyl magnesium (Et ₂ Mg) in the presence of catalytic amounts of Cp ₂ ZrCl ₂ at room temperature in ether, resulting in 2-ethyl-1-magnesium-containing alkanes according to the scheme;

By a known method, mono [cycloalkyl] dimagnesium bromide [60] fullerenes and bis [cycloalkyl] tetramagnesium bromide [60] fullerenes of the formula (1) cannot be obtained.

The known method ([2], U. M. Dzhemilev, O.S. Vostrikova, R. M. Sultanov, A. G. Kukovinets, L. M. Khalilov. News of the USSR Academy of Sciences. Series of chem., 1984, No. 9 p. 2053) carbomagnetization of polyene hydrocarbons, in particular 1,4E, 9-decatriene with diethyl magnesium (Et ₂ Mg) in the presence of catalytic amounts of Cp ₂ ZrCl ₂ under mild conditions in ether solvents. Carbomagnetization proceeds exclusively along terminal double bonds, while the internal disubstituted double bond is not involved in the reaction.

Известный способ не позволяет получать моно[циклоалкил] димагнийбромид[60]фуллерены и бис[циклоалкил]тетрамагнийбромид[60]фуллерены (1).

The known method does not allow to obtain mono [cycloalkyl] dimagnesium bromide [60] fullerenes and bis [cycloalkyl] tetramagnesium bromide [60] fullerenes (1).

 A new method is proposed for the joint production of mono [cycloalkyl] dimagnesium bromide [60] fullerenes and bis [cycloalkyl] tetramagnesium bromide [60] fullerenes of the general formula (1).

The essence of the method consists in the interaction of a toluene solution of fullerene C ₆₀ with an excess of ethereal solution of α, ω-dimagnesium bromide of the general formula BrMg (CH ₂ ) _m MgBr, where m = 4.6; taken in a molar ratio of C ₆₀ : BrMg (CH ₂ ) _m MgBr = 1: (50: 150), preferably 1: 100, in the presence of a catalyst of zirconacene dichloride (Cp ₂ ZrCl ₂ ) in an amount of 0.2-2 mol% with respect to BrMg (CH ₂ ) _m MgBr, preferably 1 mol%, in an argon atmosphere at room temperature (22-23 ^° C) and normal pressure for 10-20 hours, preferably 15 hours. The total yield of mono [cycloalkyl] dimagnesium bromide [60] fullerenes (1) is 62-88% (yield (1) was determined by hydrolysis products).

α,ω- димагниевые соединения берут в избытке по отношению к фуллерену с целью повышения выхода целевых продуктов. Снижение количества α,ω- димагниевых соединений приводит к уменьшению выхода целевых продуктов.The reaction proceeds according to the scheme:

α, ω - dimagnesium compounds are taken in excess with respect to fullerene in order to increase the yield of target products. A decrease in the amount of α, ω-dimagnesium compounds leads to a decrease in the yield of the target products.

Carrying out this reaction in the presence of a catalyst Cp ₂ ZrCl ₂ more than 2 mol.% Does not lead to a significant increase in the yield of target products. The use of the catalyst Cp ₂ ZrCl ₂ less than 0.2 mol.% Reduces the yield (1), which is possibly associated with a decrease in catalytically active centers in the reaction mass. The experiments were carried out at room temperature. The reaction at a higher temperature, for example 60 ^o C, is not advisable, because however, there is no significant increase in the yield of target products. At lower temperatures, for example, 0 ^° C., the reaction rate decreases. The reactions were carried out in a solution of toluene, because it is the best solvent for fullerene. The initial α, ω-dimagnesium compounds were synthesized in ether, since it is the best solvent for Grignard reagents.

 Significant differences of the proposed method.

The proposed method is based on the use of α, ω-magnesium compounds and fullerene C ₆₀ as starting reagents, the reaction proceeds in a mixture of an aromatic (toluene) and ether solvent. In the known method, diethyl magnesium (MgEt ₂ ) and an acyclic triene (1,4E, 9-decatriene) are used.

 The proposed method, unlike the known ones, allows one to obtain mono [cycloalkyl] dimagnesium bromide [60] fullerenes and bis [cycloalkyl] tetramagnesium bromide [60] fullerenes (1), the synthesis of which is not described in the literature.

 The method is illustrated by the following examples.

Спектральные характеристики смеси моно[циклооктил]дигидро [60]фуллеренов и бис[циклооктил]тетрагидро[60]фуллеренов (2):
Спектр ЯМР ¹H (δ, м.д.): 1.31-1.86 м (CH₂, 7.01-7.47 м (C₆₀, -H);
Масс-спектр (m/z ±): 806 (H₂C₆₀(CH₂)₆); 892 ([(CH₂)₆]₂)C₆₀H₄).Example 1. In a 100 ml glass reactor mounted on a magnetic stirrer, 0.05 mmol of fullerene C ₆₀ , 40 ml of dry toluene, 5 mmol of BrMg (CH ₂ ) ₆ MgBr (0.85 M ether solution) in 20 ml of sulfuric ether and the catalyst Cp ₂ ZrCl ₂ in an amount of 0.05 mmol (1 mol% with respect to BrMg (CH ₂ ) ₆ MgBr), stirred for 15 hours at room temperature (22-23 ^o C). A mixture of mono [cyclooctyl] dimagnesium bromide [60] fullerenes and bis [cyclooctyl] tetramagnesium bromide [60] fullerenes (1) is obtained with a total yield of 77%. The yield (1) was determined by the hydrolysis products (2):

Spectral characteristics of a mixture of mono [cyclooctyl] dihydro [60] fullerenes and bis [cyclooctyl] tetrahydro [60] fullerenes (2):
¹ H NMR spectrum (δ, ppm): 1.31-1.86 m (CH ₂ , 7.01-7.47 m (C ₆₀ , -H);
Mass spectrum (m / z ±): 806 (H ₂ C ₆₀ (CH ₂ ) ₆ ); 892 ([(CH ₂ ) ₆ ] ₂ ) C ₆₀ H ₄ ).

 Other examples confirming the method are given in the table.

The reaction was carried out at room temperature (22 - 23 ^o C). A mixture of toluene and ether was used as a solvent, since the highest solubilities in them are, respectively, C ₆₀ and BrMg (CH ₂ ) _m MgBr.

Claims (1)

The method of co-production of mono [cycloalkyl] dimagnesium bromide [60] fullerenes and bis [cycloalkyl] tetramagnesium bromide [60] fullerenes of the general formula [(CH ₂ ) _m ] _n C ₆₀ (MgBr) _2n , where C _{60 is a} new allotropic carbon modification m = 4 , 6; n = 1.2, characterized in that the toluene solution of fullerene C ₆₀ interacts with an excess of ethereal solution of α, ω-dimagnesium bromide of the general formula BrMg (CH ₂ ) _m MgBr, where m = 4.6, in a molar ratio of C ₆₀ : BrMg ( CH ₂ ) _m MgBr = 1: (50: 150) in the presence of a catalyst of zirconacene dichloride (Cp _p ZrCl ₂ ), taken in an amount of 0.2-2 mol% with respect to the solution of α, ω-dimagnesium bromide, the reaction is carried out in argon atmosphere under normal conditions for 10-20 hours.

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