RU2283844C1 - Method for production of 1-ethenyl-1-methyl-1-sila-2,3-[60]fullerocyclopentane - Google Patents

Abstract

FIELD: organic chemistry.

SUBSTANCE: Claimed method includes reaction of fullerene[60] (C60) with triethylaluminum (AlEt₃) in C60:AlEt₃ molar ratio of 1:(25-35) in presence of Cp₂ZrCl₂ as catalyst in amount of 15-25 mol.% based on C60 in argon atmosphere, in toluene medium under atmospheric pressure and at room temperature for 8 hours followed by addition to reaction mass at -15°C copper chloride (CuCl) catalyst in amount of 15-20 mol % based on C60 and methylvinyldichlorosilane in equimolar amount in relation to AlEt₃. Further reaction mass is agitated at room temperature for 6-10 hours followed by hydrolysis of reaction mass.

EFFECT: method of increased yield.

1 tbl, 7 ex

Description

The present invention relates to the field of organic chemistry, specifically to a method for producing 1-ethenyl-1-methyl-1-force-2,3- [60] fullerocyclopentane of the general formula (1):

1-Ethenyl-1-methyl-1-force-2,3- [60] fullerocyclopentane of the formula (1) can be used in fine organic synthesis, in the production of physiologically active substances and drugs.

The known method ([1], Nagao Yukinori, Takahashi Masahiro, Ave Yoshimoto, Misono Takahisa, Jung Michael E. Synthesis of 1,1-dialkoxy derivatives of 2,5-diphenylsilacyclopent-3-ene and 2,5-diphenylsilacyclopentane. Bull. Chem. Soc. Jap. 1993, 66 (8), 2294-2297) for preparing substituted silacyclopentanes (2) by reacting styrene with ethoxydichlorosilane in the presence of lithium metal with stirring in THF for 26 hours according to the scheme:

In a known manner, 1-ethenyl-1-methyl-1-force-2,3- [60] fullerocyclopentane of the formula (1) cannot be obtained.

A known method ([2], UMDzhemilev, AGIbragimov, LOKhafizova, and RRGilyazev. Zirconium catalysis in a synthesis of cyclopentanols and five-membered heterocyclic compounds. Tetrahedron, 2004, 60, 1281-1286) for the preparation of substituted silacyclopentanes (3) by the interaction of α-olef with ethyl aluminum dichloride in the presence of Cp ₂ ZrCl ₂ followed by the addition of methyl vinyl dichlorosilane and a Cu-containing catalyst to the reaction mass according to the scheme:

In a known manner, 1-ethenyl-1-methyl-1-force-2,3- [60] fullerocyclopentane (1) cannot be obtained.

A new method is proposed for producing 1-ethenyl-1-methyl-1-force-2,3- [60] fullerocyclopentane (1).

The essence of the method consists in the interaction of fullerene C ₆₀ with triethylaluminium (AlEt ₃ ), taken in a molar ratio of C ₆₀ : AlEt ₃ = 1: (25-35), preferably 1:30, in the presence of a catalyst of zirconacene dichloride (Cp ₂ ZrCl ₂ ) in an amount 15-25 mol.% With respect to C ₆₀ , preferably 20 mol.%, In an argon atmosphere at room temperature (20-21 ° C) and atmospheric pressure in a toluene solution for 8 hours, followed by addition to the reaction mass at a temperature of - 15 ° C of a catalyst for copper chloride (CuCl) in an amount of 15-25 mol.% In relation to the initial fullerene [60], p . edpochtitelno 20 mol%, and metilvinildihlorsilana in equimolar relative to the amount of AlEt _3, followed by stirring the reaction mixture at room temperature (20-21 ° C) for 6-10 hours; preferably 8 hours. The total yield of 1-ethenyl-1-methyl-1-force-2,3- [60] fullerocyclopentane of formula (1) after hydrolysis of the reaction mass is 52-76%.

The reaction proceeds according to the scheme:

1-Ethenyl-1-methyl-1-force-2,3- [60] fullerocyclopentane of the formula (1) is formed only with the participation of AlEt ₃ , C ₆₀ and the zirconium catalyst Cp ₂ ZrCl ₂ . In the presence of other aluminum compounds (e.g. Bu ⁱ ₂ AlCl, Bu ⁱ ₃ Al, Bu ⁱ ₂ AlH, EtAlCl ₂ , Et ₂ AlCl) or other catalysts (e.g. Zr (acac) ₄ , ZrCl ₄ , Cp ₂ TiCl ₂ , Pd (acac) ₂ , Ni (acac) ₂ , NiCl ₂ , Fe (acac) ₂ ) the target product (1) is not formed.

Carrying out this reaction in the presence of a catalyst Cp ₂ ZrCl ₂ or CuCl more than 25 mol.% In relation to fullerene [60] does not lead to a significant increase in the yield of the target product (1). The use of the catalyst Cp ₂ ZrCl ₂ or CuCl less than 15 mol.% Reduces the yield of the target product (1), which is probably associated with a decrease in catalytically active centers in the reaction mass. The reactions were carried out at room temperature (20-21 ° C). At a higher temperature (for example, 40 ° C), there is no significant increase in the yield of the target product (1), and at a lower temperature (for example, 0 ° C), the reaction rate decreases. A change in the ratio of the starting reagents in the direction of increasing their content with respect to the starting fullerene [60] does not lead to a significant increase in the yield of the target product (1).

The reactions were carried out in toluene solution. In other solvents (e.g., ether), the reaction does not proceed.

Significant differences of the proposed method:

In the proposed method, fullerene [60] and an organoaluminum reagent AlEt ₃ are used as starting compounds, and in the known method, α-olefins and an organoaluminum reagent EtAlCl ₂ are used as starting compounds.

The proposed method, in contrast to the known method, allows to obtain 1-ethenyl-1-methyl-1-force-2,3- [60] fullerocyclopentane of the formula (1).

The method is illustrated by the following examples.

EXAMPLE 1. 140 ml of dried toluene 0.14 mmol C ₆₀ , 0.028 mmol of catalyst Cp ₂ ZrCl ₂ , 4.2 mmol of AlEt ₃ are placed in a 250 ml glass reactor mounted on a magnetic stirrer in an argon atmosphere, stirred for 8 hours at a temperature of 20-21 ° C, then at a temperature of -15 ° C, 0.028 mmol of CuCl catalyst and 4.2 mmol of methyl vinyl dichlorosilane are added, stirred for 8 hours at a temperature of 20-21 ° C and hydrolyzed with an ethereal HCl solution. 2,3- [60] fulleromethylvinylsilacyclopentane is isolated from the organic layer in 65% yield.

Spectral characteristics of 1-ethenyl-1-methyl-1-force-2,3- [60] fullerocylopentane (1)

IR spectrum (ν, cm ^-1 ): 2910, 2850, 1520, 1430, 1370, 1250, 1180, 1080, 740, 600-500.

¹³ C NMR spectrum (δ, ppm, CDCl ₃ ): - 1.17, 11.55, 43.15, 132.74, 136.16. The signals of sp-2 carbon atoms of the fullerene sphere are in the region of 121.44-150.46.

Other examples confirming the method are shown in table 1.

Table 1 №№

Total reaction time, hour Yield of 1-ethenyl-1methyl-1-force-2,3- [60] fullerocyclopentane (1),% one. 0.14: 4.2: 0.028: 4.2: 0.028 16 65 2. 0.14: 4.9: 0.028: 4.9: 0.028 16 69 3. 0.14: 3.5: 0.028: 3.5: 0.028 16 58 four. 0.14: 4.2: 0.035: 4.2: 0.035 16 76 5. 0.14: 4.2: 0.021: 4.2: 0.021 16 52 6. 0.14: 4.2: 0.028: 4.2: 0.028 eighteen 68 7. 0.14: 4.2: 0.028: 4.2: 0.028 fourteen 60

The reactions were carried out at room temperature (20-21 ° C) in a solution of toluene in an argon atmosphere without access of light. In all experiments, the number of substituents in the fullerene molecule [60] varies from 1 to 2.

Claims (1)

The method of obtaining 1-ethenyl-1-methyl-1-force-2,3- [60] fullerocyclopentane of the formula (1)

characterized in that the fullerene C ₆₀ is reacted with triethylaluminium (AlEl ₃ ) in a molar ratio of C ₆₀ : AlEl ₃ = 1: (25-35) in the presence of a catalyst of zirconacenedichloride (Cp ₂ ZrCl ₂ ), taken in an amount of 15-25 mol. % with respect to C ₆₀ , in an argon atmosphere at room temperature (20-21 ° C) and atmospheric pressure in toluene for 8 hours, followed by the addition of a copper chloride catalyst (CuCl) to the reaction mass at a temperature of -15 ° C in an amount 15-25 mol.% with respect to C ₆₀ and metilvinildihlorsilana in equimolar relative to the amount AlEl _3, n follows the reaction was stirred at room temperature for 6-10 hours followed by hydrolysis of the reaction mass.