RU2594562C2 - Method for producing n-arylaziridinum[2 ', 3 ': 1.9]fullerene [60] - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: present invention relates to organic chemistry, namely to a method for producing N-arylaziridinumfullerene, which can be used as complexing agents, sorbents, biologically active compounds, as well as for creating new materials with given properties. Method involves reaction of fullerene C₆₀ with arylaziridinums RN₃ (where R = Ph, 4-Cl-Ph 2-NO₂-Ph 2-MeO-Ph, Naph) in the presence of lanthanum La (OTf)₃, taken in the molar ratio C₆₀: RN₃: La (OTf)₃= 1: (0.5-2):(0.5-2), at the temperature of 80 °C, in chlorobenzene for 1-3 hours.

EFFECT: obtaining N-arylaziridinum [2′,3′: 1,9]fullerene [60] (1) with the output of 20-50 %.

1 cl, 1 tbl, 1 ex

Description

The invention relates to the field of organic synthesis, and in particular to a method for producing N-arylaziridino [2 ′, 3 ′: 1,9] fullerenes [60] of the formula (1)

Functionally substituted fullerenes can be used as complexing agents, sorbents, biologically active compounds, as well as in the creation of new materials with specified electronic, magnetic and optical properties (L.N. Sidorov, M.A. Yurovskaya, A.Ya. Borschevsky, I .V. Trushkov, I.N. Ioffe. Fullerenes: Textbook, M .: Examination Publishing House, 2005, 688 pp. [1], LB Piotrovsky, OI Kiselev. Fullerenes in Biology, St. Petersburg .: LLC “Publishing house Rostock”, 2006, 336 p. [2]).

A known method (J. Averdung, J. Mattay. Tetrahedron, 1996, 52, 5407-5420 [3]) for producing N-arylaziridinofullerenes (1) by photochemical decomposition of triazolinofullerenes C ₆₀ (2) in toluene with a wavelength of λ = 300 nm at room temperature temperature.

The disadvantage of this method is the need for preliminary synthesis of triazolinofullerenes (2), which leads to multi-stage production of the target aziridinofullerenes (1) and high energy consumption.

The known method (A. Ouchi, R. Hatsuda, BZS Awen, M. Sakuragi, R. Ogura, T. Ishii, Y. Araki, O. Ito. J. Am. Chem. Soc. 2002, 124, 13364-13365 [ 4]. A. Ouchi, BZS Awen, R. Hatsuda, R. Ogura, T. Ishii, Y. Araki, O. Ito. J. Phys. Chem. A. 2004, 108, 9584-9592 [5]) N-arylaziridinofullerenes (1) by photo rearrangement of azahomofullerenes (3) in toluene with a wavelength of λ = 600 nm at room temperature.

The disadvantage of this method is the need for preliminary synthesis of triazolinofullerenes (2) and azahomofullerenes (3), which leads to multi-stage production of the target aziridinofullerenes (1) and high energy costs.

A new method is proposed for producing N-arylaziridino [2 ′, 3 ′: 1.9] fullerenes [60] (1).

The essence of the method is the interaction of fullerene C ₆₀ (4) with aryl azides RN ₃ (where R = Ph, 4-Cl-Ph, 2-NO ₂ -Ph, 2-MeO-Ph, Naph) in the presence of La lanthanum triflate (OTf) ₃ , taken in a molar ratio of C ₆₀ : RN ₃ : La (OTf) ₃ = 1: (0.5-2) :( 0.5-2), preferably 1: 1: 1, in a solution of chlorobenzene at 80 ° C for 1 -3 hours. N-arylaziridino [2 ′, 3 ′: 1.9] fullerenes [60] (1) are obtained in a yield of 20-50%. The reaction proceeds according to the scheme:

The starting arylazide is taken in an equimolar amount with respect to fullerene C ₆₀ in order to selectively obtain the monoadduct (1) in high yield. A decrease in the amount of arylazide with respect to C _{60 is} impractical, since it leads to a decrease in yield (1). Carrying out this reaction in the presence of lanthanum triflate [La (OTf) ₃ ] more than 100 mol.% In relation to fullerene C ₆₀ does not lead to a significant increase in the yield of the target product (1). The use of a heterogeneous catalyst [La (OTf) ₃ ] in an amount of less than 100 mol% with respect to fullerene C ₆₀ reduces the yield of the target product, which is associated with a decrease in reaction centers. Conducting the reaction at higher temperature is connected with increase of energy consumption as well as increasing the number of polyaddition aryl azide to C ₆₀ products _formed.

Significant differences of the proposed method.

The proposed method is based on the use of arylazides as the starting reagent, as well as the use of stoichiometric amounts of lanthanum triflate catalyst [La (OTf) ₃ ]. The proposed method, unlike the known ones, allows one to obtain individual N-arylaziridino [2 ′, 3 ′: 1,9] fullerenes (1) with high selectivity and yields in one preparative stage.

The method is illustrated by examples.

In a two-necked glass reactor, 40 mg (0.055 mmol) of C _{60 was} dissolved in 8 ml of dry chlorobenzene, (0.055 mmol) arylazide and 20 mg of La (OTf) ₃ (0.055 mmol) were added with vigorous stirring. After the reaction mass was heated to 80 ° C and stirring was continued for another 1-3 hours. All experiments were carried out in a stream of dry argon. After time, the reaction mass was passed through a small layer of silica gel. The reaction products and fullerene C ₆₀ were separated using semi-preparative HPLC, eluent-toluene. As a result, N-arylaziridinofullerenes [60] were obtained with yields of 20–50%.

Spectral characteristics

Other examples confirming the method are given in table. one

Reactions were carried out at 80 ° C in chlorobenzene in the presence of lanthanum triflate La (OTf) ₃ .

Claims (1)

The method of obtaining N-arylaziridino [2 ′, 3 ′: 1,9] fullerenes of the General formula (1)

characterized in that the fullerene C ₆₀ interacts with aryl azides RN ₃ (where R = Ph, 4-Cl-Ph, 2-NO ₂ -Ph, 2-MeO-Ph, Naph) in the presence of lanthanum triflate La (OTf) ₃ , taken in a molar ratio of C ₆₀ : RN ₃ : La (OTf) ₃ = 1: (0.5-2) :( 0.5-2), at a temperature of 80 ° C, in chlorobenzene for 1-3 hours