RU2703528C2 - Method for selective production of norbornadiene fullerene derivatives - Google Patents

Abstract

FIELD: chemistry.SUBSTANCE: present invention relates to a method of producing a norbornadiene fullerene derivative of formula 1:,which can be used as a complexing agent, a sorbent, a biologically active compound. Method consists in the fact that C-fullerene reacts with norbornadiene ether of chloroacetic acidin dry toluene in the presence of t-BuOK, taken in molar ratio C:ether:t-BuOK = 1:(1–2):(2–4), at temperature of 20 °C for 5–15 minutes.EFFECT: disclosed method enables to obtain an end product with output of 10–52 %.1 cl, 1 tbl, 7 ex

Description

The alleged invention relates to the field of organic synthesis, namely, to a method for the selective production of norbornadiene derivative fullerene C _{60 of} formula 1:

Methanofullerenes, including those containing norbornadiene addends, are promising compounds as complexing agents, sorbents, biologically active compounds, as well as in the creation of new materials with desired 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 p [1 ], LB Piotrovsky, OI Kiselev. Fullerenes in biology, St. Petersburg: Rostok Publishing House LLC, 2006, 336 p [2]).

A known method (MS Miftakhov, VV Mikheev, SA Torosyan, Yu. N. Biglova, FA Gimalova, VM Menshov, AG Mustafin. Tetrahedron. 2014, 70, 8040 [3]) for the production of norbornene-containing methanofullerene (4) with a yield of 62% C _60- fullerene (2) with compound (3) in the presence of diazobicycloundecene (DBU) in toluene at room temperature for 2 hours

The known method does not allow to obtain a norbornadiene-containing methanofullerene of the formula 1.

The known method (Khusnutdinov R.I., Gaynullin H.Kh., Muslimov Z.S., Dzhemilev U.M., Nefedov O.M., Tomilov Yu.V. Patent. 2137743.) obtaining [1 + 1] of C ₆₀ 7 and 8 fullerene adducts in the environment of chlorobenzene or 2-methylthiophene at 160-180 ° C for 5 hours by the reaction of C ₆₀ with an excess (50-200 fold) of 5 or 7-spirocyclopropannorbornadiene 6. The yield of compounds 8 and 9 amounted to 80%

The known method does not allow to obtain norbornadiene derivatives of fullerene of the formula 1.

A new method is proposed for producing norbornadiene fullerene derivatives (1).

The essence of the method consists in the interaction of fullerene (C ₆₀ ) (2) with norbornadiene ester of chloroacetic acid 9 in dry toluene in the presence of t-BuOK, taken in a molar ratio of C ₆₀ : 9: t-BuOK = 1: (1-2) :( 2-4), preferably 1: 1.5: 3, at a temperature of 20 ° C for 5-15 minutes. Get norbornadiene-containing methanofullerene (1) with a yield of 10-52%. The reaction proceeds according to the scheme:

Carrying out the specified reaction in the presence of t-BuOK more than a 3-fold excess with respect to fullerene C ₆₀ leads to the formation of an abundant precipitate, up to complete discoloration of the solution. The use of t-BuOK in an amount of less than a 3-fold excess with respect to fullerene C ₆₀ reduces the yield of the target product, and increases the reaction time. The reaction should be carried out at a temperature of 20 ° C. Carrying out the reaction at a higher temperature (for example, 110 ° C) is not advisable, since it leads to the production of [1 + 1] -ducts of fullerene C ₆₀ .

Significant differences of the proposed method:

The proposed method is based on the use of t-BuOK as a base. The proposed method, in contrast to the known ones, is more energy efficient and allows one to obtain norbornadiene-containing methanofullerene (1), the synthesis of which is not described in the literature.

The method is illustrated by examples.

Example 1. To a solution of 100 mg (0.139 mmol) of C _60- fullerene in 60 ml of dry toluene under argon atmosphere was added sequentially norbornadiene ester of chloroacetic acid (0.2085 mmol) and (0.417 mmol) t-BuOK. The reaction mass is stirred at 20 ° C. After 10 min, the reaction mass is treated with 5% aqueous HCl. The organic layer is passed through a column with a small layer of silica gel. Get norbornadiene-containing methanofullerene (1) with a yield of 49% (according to HPLC).

Spectral characteristics (1)

Yield 49%. ¹ H NMR spectrum (500 MHz, CDCl ₃ and CS ₂ = 1: 5): 2.13-2.21 (dd, 2H, CH ₂ , J = 8.32 Hz), 3.64 (m, 1H, CH), 3.67 (m, 1H , CH), 4.79 (s, 1H, CH) 5.08-5.10 (dd, 2H, CH ₂ , J = 4.8 Hz), 6.76 (d, 1H, CH, J = 4H, Hz), 6.82 (t, 1H, CH, J = 4 Hz) 6.91 (t, 1H, CH, J = 4 Hz). ¹³ C NMR (125 MHz, CDCl ₃ and CS ₂ = 1: 5): 39.36, 51.00, 52.17, 64.83, 70.71, 74.36, 136.46, 140.76, 140.77, 141.02, 141.27, 141.71, 142.09, 142.18, 142.31,

142.50, 142.53, 142.90, 143.06, 143.11, 143.18, 143.40, 143.47, 143.80, 144.05, 144.52, 144.64, 144.74, 144.81, 145.15, 145.25, 145.32, 145.58, 145.69, 145.73, 148.26, 151.68, 165.39. MALDI-TOF: found 853.027 [M] ^- , calculated 853.089 for C ₆₉ H ₁₁ N

Other examples confirming the method are given in table. one

The reactions were carried out in an inert atmosphere at a temperature of 20 ° C in dry toluene as a solvent.

Claims (3)

A method of obtaining a norbornadiene derivative of fullerene of the formula 1:

characterized in that C ₆₀ fullerene interacts with norbornadiene ester of chloroacetic acid

in dry toluene in the presence of t-BuOK, taken in a molar ratio of C ₆₀ : ether: t-BuOK = 1: (1-2) :( 2-4), at a temperature of 20 ° C for 5-15 minutes.