RU2605453C2 - METHOD OF PRODUCING FULLERENE OXIMES: BIS-ADDUCTS OF 1-[HYDROXO]-9-[1'-HYDROXYIMINO-2'-OXO-2'-ALKYL-ETHYL]-1,9-DIHYDRO-[C60-Ih][5,6]FULLERENES - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to organic chemistry, particularly to a method of producing bis-adducts of 1-[hydroxo]-9-[1'-hydroxyimino-2'-oxo-2'-alkyl-ethyl]-1,9-dihydro-[C₆₀-I_h][5,6]fullerene, which can be used as complexing agents, biologically active compounds, as well as synthons for synthesis of novel compounds of fullerene C₆₀ with given properties. Method involves reaction of fullerene C₆₀ with ketones ((Me)₂CO, or (Me)(Ph)CO, or (Et)(Me)CO, or (i-Pr)(Me)CO) in presence of sodium nitrite and hydrochloric acid, taken in molar ratio 0.01:(0.01-100):(0.01-25):(0.01-50) in medium of CCl₄ as a solvent at ~20 °C for 30 minutes.

EFFECT: method for selective production of finished products.

R=Me, Et, i-Pr, Ph

1 cl, 1 tbl

Description

The invention relates to organic chemistry, specifically to a method for producing bis adducts of 1- [hydroxy] -9- [1'-hydroxyimino-2'-oxo-2'-alkyl-ethyl] -1,9-dihydro [C ₆₀ - I _h ] [5,6] fullerenes of the general formula (1).

C ₆₀ fullerene compounds containing an oxime group can be used as complexing agents, biologically active compounds, and also as synthons for the synthesis of new C ₆₀ fullerene compounds with desired properties (Troshin P.A., Troshina O.A., Lyubovskaya R .N., Razumov VF Functional derivatives of fullerenes: synthesis methods and prospects for use in organic electronics and biomedicine. Ivanovo: Ivan. State university, 2008, 139 pp .; Sidorov L.N., Yurovskaya N.A. ., Borschevsky A.Ya., Trushkov IV, Ioffe I.N. Fullerenes. M: Examination, 2005, 39 7 pp .; Piotrovsky LB, Kiselev O.I. Fullerenes in Biology.St. Petersburg: Rostock, 2006, 110 pp.).

In the literature there is a very limited number of works devoted to the production of fullerene C ₆₀ oximes. In the reaction of nitroalkanes with fullerene C ₆₀ [A. Yashiro, Y. Nishida, K. Kobayashi, M. Ohno β-Hydroxy Nitrile and β-Hydroxy Oxime Derivatives of [60] Fullerene by nucleophilic Ring Cleavage of Fulleroisoxazoline and - Isoxazolidine in the Presence of Methanol] in the presence of triethylamine Et ₃ N and trimethylsilyl chloride Me ₃ SiCl (-20 ° С, argon, 30 min) an intermediate cycloduct of C ₆₀ fullerene - isooxosolidine fullerene was obtained, during which treatment tetraethylammonium fluoride (-20 ° С, argon, 1 hour) and β-hydroxy oxime was synthesized by neutralization with hydrochloric acid fullerene C ₆₀ (yield 34-65%).

The disadvantages of this method include the multi-stage process for producing this fullerene oxime, including the formation of intermediate products.

The one-reactor synthesis of β-hydroxy oximes of fullerene C ₆₀ with a yield of 34-46% was carried out using an excess of nitroalkane (RCH ₂ NO ₂ ) with respect to fullerene C ₆₀ at room temperature for 2 hours [M. Ohno, A. Yashiro, Y. Tsunenishi, S. Eguchi Unusual redox-type addition of nitroalkanes on the C ₆₀ surface // Chem. Commun., 1999, 827-828].

As a result of chemical modification of the compound of fullerene C ₆₀ containing an oxylamine group, the authors of [S. Abe, H. Moriyama, K. Niikura, F. Feng, K. Monde, S. - I. Nishimura. Versatile synthesis of oligosaccharide-containing fullerenes // Tetrahedron: Asymmetry 16 (2005) 15-19] succeeded in attaching oligosaccharides of various structures to the fullerene framework through stable oxime bonding (yields of target products are not indicated).

Thus, in the literature there is no information on the selective synthesis of 1- [hydroxy] -9- [1'-hydroxyimino-2'-oxo-2'-alkyl-ethyl] -1,9-dihydro [C ₆₀ - I _h ] [5,6] fullerenes of the formula (1).

A new method is proposed for the selective production of bis adducts of 1- [hydroxy] -9- [1'-hydroxyimino-2'-oxo-2'-alkyl-ethyl] -1,9-dihydro [C ₆₀ -I _h ] [5 , 6] fullerenes of the general formula (1).

The essence of the method consists in the interaction of fullerene C ₆₀ with ketones ((Me) ₂ CO, or (Me) (Ph) CO, or (Et) (Me) CO, or (i-Pr) (Me) CO) in the presence of sodium nitrite and hydrochloric acid, taken in a molar ratio of 0.01: (0.01-100) :( 0.01-25) :( 0.01-50) in CCl ₄ medium as a solvent at ~ 20 ° C for 30 minutes. The yield of reaction products is 24-100% (according to HPLC). The reaction proceeds according to the scheme:

Ketones are taken in excess with respect to fullerene C ₆₀ in order to increase the yield of the target product (1).

Significant differences of the proposed method:

The proposed method is characterized by the possibility of one-reactor production of bis adducts of 1- [hydroxy] -9- [1'-hydroxyimino-2'-oxo-2'-alkyl-ethyl] -1,9-dihydro [C ₆₀ -I _h ] [ 5,6] fullerenes and high yields of the target product. In contrast to the known methods, the proposed method allows to selectively obtain bis adducts of 1- [hydroxo] -9- [1'-hydroxyimino-2'-oxo-2'-alkyl-ethyl] -1,9-dihydro [C ₆₀ - I _h ] [5,6] fullerenes of the general formula (1), which are not described in the literature.

The method is illustrated by the following examples:

Example.

In a 100 ml glass flask mounted on a magnetic stirrer, 0.04 mmol C ₆₀ and 40 ml CCl _{4 are} placed. After the fullerene is completely dissolved at room temperature, 0.4 mol (29 ml) of acetone, 0.1 mol of sodium nitrite and 0.2 mol (6 ml) of hydrochloric acid are added. The solution immediately turns dark brown. The mixture is stirred for 30 minutes. Next, the reaction mass is neutralized with CaCO ₃ and the reaction products are isolated by semi-preparative HPLC. Additional purification is carried out by refining with water (3 × 50 ml). The solution is then dried over anhydrous MgSO ₄ . The solvent was distilled off and the solid residue was dried in vacuo. The yield of 1- [hydroxy] -9- [1'-hydroxyimino-2'-oxo-2'-methyl-ethyl] -1,9-dihydro [C ₆₀ -I _h ] [5,6] fullerene 95% ( 35 mg). The obtained fullerene oxime has the following physicochemical characteristics.

The powder is dark brown. ¹³ C (1) NMR spectrum (CDCl ₃ , δ, ppm): 103 56 (C ¹ ), 85. 67 (C ² ), 162.39-175.16 (C ³ ), 185.57-195.07 (C ⁴ ), 18.96-20.54 (C ⁵ ). The signals of the carbon atoms of the fullerene fragment are located in the range 138.6–158.28 ppm.

NMR spectrum ¹ H (1) (CDCl ₃ , δ, ppm): 2.64 (s, 3H); 6.50 (s, 1H).

Mass spectrum Maldi TOF / TOF (m / z) 907.0685.

IR spectrum (ν, cm ^-1 ): 3402 (O-H), 1803 (C = O), 1709 (C = N), 1605, 1366, 1159, 946 (NO), 617.

Other examples confirming the method are given in table. one.

Claims (1)

The method of producing bis adducts of 1- [hydroxy] -9- [1′-hydroxyimino-2′-oxo-2′-alkyl-ethyl] -1,9-dihydro [C ₆₀ -I _h ] [5,6] fullerenes of the general formula (1)

characterized in that C ₆₀ fullerene interacts with ((Me) ₂ CO, or (Me) (Ph) CO, or (Et) (Me) CO, or (i-Pr) (Me) CO) ketones in the presence of sodium nitrite and hydrochloric acid, taken in a molar ratio of 0.01: (0.01-100) :( 0.01-25) :( 0.01-50) in CCl ₄ medium as a solvent at ~ 20 ° C for 30 min