RU2165425C1 - Method of preparing 3,4-fullrene [60]-1,2- oxythioethane-2 (2,3-dimethyl-1,4-but-2-ene)-2-oxide - Google Patents

Abstract

FIELD: organic chemistry, more particularly preparation of functionally substituted fullerenes useful as complexing agents, sorbents and biologically active compounds. SUBSTANCE: fullerene is made to react with excessive amount of 3,4-dimethyl-3-sulfolene in argon atmosphere, in toluene at temperatures from 85 to 115 C for 8-12 hours. EFFECT: new functionally substituted fullerene of formula I:

wherein C₆₀ is allotropic carbon modification, n is 1-3, and yield is 70-82%. 1 tbl

Description

где C₆₀ - аллотропная модификация углерода n = 1 - 3.The invention relates to the field of organic chemistry, specifically to a method for producing 3,4-fullerene [60] -1,2-hydroxythioethane-2 (2 ', 3'-dimethyl-1'4'-but-2'-en) -2 -oxide of the general formula (1):

where C ₆₀ is the allotropic modification of carbon n = 1 - 3.

 Functionally substituted fullerenes can be used as complexing agents, sorbents, biologically active compounds. With their help, new organic molecules can be created with predetermined electronic, magnetic and optical properties.

Известным способом не может быть получен 3,4-фуллерен[60]-1,2-окситиоэтан-2(2',3'-диметил-1'4'-бут-2'-ен)-2-оксид (1).A known method (M.Ohno, S. Kojima, S. Eguchi. J. Chem. Soc., Chea. Commun., 1995, 565-566) for the preparation of a dihydrothiopyran derivative of fullerene [60] of formula (3) by hetero-Diels-Alder reaction fullerene [60] with N-acylthioacrylamide (2) at a temperature of 65 ^o C in argon atmosphere with a yield of 43-69% according to the scheme

In a known manner, 3,4-fullerene [60] -1,2-hydroxythioethane-2 (2 ', 3'-dimethyl-1'4'-but-2'-ene) -2-oxide (1) cannot be obtained .

Известным способом не может быть получен 3,4-фуллерен[60]-1,2-окситиоэтан-2(2',3'-диметил-1'4'- бyт-2'-ен)-2-oкcид.A known method (GPMiller, MABuretea, MMBernardo, CSHsu, HL Fang. J. Chem. Soc., Chem. Commun., 1994, 1549-1550) for producing a cyclic fullerene sulfonate [60] of the formula (4) by reacting fullerene [60] with SO ₃ according to the scheme

In a known manner, 3,4-fullerene [60] -1,2-hydroxythioethane-2 (2 ', 3'-dimethyl-1'4'-but-2'-ene) -2-oxide cannot be obtained.

 Thus, in the literature there is no information on the synthesis of 3,4-fullerene [60] -1,2-hydroxythioethane-2 (2 ', 3'-dimethyl-1'4'-but-2'-ene) -2-oxide (1).

 A new method is proposed for the synthesis of 3,4-fullerene [60] -1,2-hydroxythioethane-2 (2 ', 3'-dimethyl-1'4'-but-2'-ene) -2-oxide.

3,4-диметил-3-сульфолен берут в избытке по отношению к фуллерену (C₆₀) с целью включения в молекулу C₆₀ максимального количества 3,4-диметил-3-сульфоленовых фрагментов. Снижение количества 3,4-диметил-3-сульфолена по отношению к C₆₀, например, C₆₀:3,4-диметил-3-сульфолен = 1:30, приводит к уменьшению выхода целевых продуктов (1), а также к снижению вводимых в молекулу фуллерена 3,4-диметил-3-сульфоленовых фрагментов. Изменение соотношения исходных реагентов в сторону увеличения содержания 3,4-диметил-3-сульфолена по отношению к C₆₀, например, C₆₀:3,4-диметил-3-сульфолен = 1:100, не приводит к существенному повышению выхода целевых продуктов, а также увеличению количества вводимых в молекулу фуллерена 3,4-диметил-3-сульфоленовых фрагментов.The essence of the method consists in the interaction of fullerene [60] (allotropic modification of carbon) with an excess of 3,4-dimethyl-3-sulfolene taken in a molar ratio of C ₆₀ : 3,4-dimethyl-3-sulfolene = 1: (40-80) , preferably 1:60, in an argon atmosphere at a temperature of 85-115 ^o C, preferably 100 ^o C, for 8-12 hours, preferably 10 hours, in toluene as a solvent. The yield of 3,4-fullerene [60] -1,2-hydroxythioethane-2 (2 ', 3'-dimethyl-1'4'-but-2'-ene) -2-oxide (1) is (according to HPLC ) 70-82%. The reaction proceeds according to the scheme.

3,4-dimethyl-3-sulfolene is taken in excess with respect to fullerene (C ₆₀ ) in order to include the maximum amount of 3,4-dimethyl-3-sulfolene fragments in the C ₆₀ molecule. A decrease in the amount of 3,4-dimethyl-3-sulfolene relative to C ₆₀ , for example, C ₆₀ : 3,4-dimethyl-3-sulfolene = 1:30, leads to a decrease in the yield of the target products (1), as well as to a decrease 3,4-dimethyl-3-sulfolene fragments introduced into the fullerene molecule. A change in the ratio of the starting reagents in the direction of increasing the content of 3,4-dimethyl-3-sulfolene relative to C ₆₀ , for example, C ₆₀ : 3,4-dimethyl-3-sulfolene = 1: 100, does not significantly increase the yield of the target products , as well as an increase in the number of 3,4-dimethyl-3-sulfolene fragments introduced into the fullerene molecule.

 3,4-fullerene [60] -1,2-oxythioethane-2 (2 ', 3'dimethyl-1'4'-but-2'-ene) -2-oxide (1) is formed only with the participation of fullerene [60 ] and 3,4-dimethyl-3-sulfolene.

The reaction at a higher temperature, for example, 120 ^o C does not lead to a significant increase in the target products. At a lower temperature, for example, 80 ^° C., the reaction rate decreases.

Significant differences of the proposed method: the proposed method is based on the use of 3,4-dimethyl-3-sulfolene as the starting reagent. In the known method, SO _{3 is used} . The proposed method, unlike the known one, allows 3,4-dimethyl-3-sulfolene fragments to be introduced into the fullerene molecule to obtain 3,4-fullerene [60] -1,2-oxioethane-2 (2 ', 3'-dimethyl-1'4'-but-2'-ene) -2-oxide (1), the synthesis of which is not described in the literature.

 The method is illustrated by examples.

EXAMPLE 1. In a metal “finger” autoclave with a volume of 17 ml in an argon atmosphere at room temperature, 0.02 mmol of fullerene [60], 6 ml of dry toluene and 1.2 mmol of 3,4-dimethyl-3-sulfolene are placed, stirred for 10 hours at a temperature of 190 ^o C, get 3,4-fullerene [60] -1,2-oxioethane-2 (2 ', 3'-dimethyl-1'4'-but-2'-ene) -2-oxide of the General formula (1) with the number of 3,4-dimethyl-3-sulfolene fragments from 1 to 3 (according to HPLC) with a total yield of 76%.

¹³ C NMR spectrum (δ, ppm): 14.41 (CH ₃ ), 60.45 (CS), 125.48 (C = C), 71.18, (C ₆₀ -S), 82.30 (C ₆₀ -O) 131.22-164.76 (fullerene).

 Other examples confirming the method are given in the table.

 As a solvent, it is advisable to use available toluene, because it has the highest solubility of fullerene [60].

Claims (1)

The method of obtaining 3,4-fullerene [60] -1,2-hydroxythioethane -2 (2 ', 3'-dimethyl-1', 4'-but-2'-ene) -2-oxide of the general formula

where C ₆₀ is the allotropic modification of carbon;
n = 1 - 3,
characterized in that fullerene [60] interacts with an excess of 3,4-dimethyl-3-sulfolene taken in a molar ratio of C ₆₀ : 3,4-dimethyl-3-sulfolene = 1: (40 - 80) in an argon atmosphere, in toluene medium as a solvent at 85 - 115 ^o C for 8 to 12 hours

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