RU2183634C2 - Method of synthesis of n-[(2,3-fullerene[60]-2,3-dihydro-1h-1,2,3- benzotriazole-1-yl]-n,n-dimethyl-amine - Google Patents

Abstract

FIELD: organic chemistry, chemical technology. SUBSTANCE: invention relates to a method of synthesis of functionally substituted fullerene, namely: N-[(2,3-(fullerene[60]-2,3-dihydro-1H-1,2,3-benzotriazole-1-yl]-N,N- dimethylamine of the formula (I)

Description

где n=1-3.The invention relates to organic chemistry, specifically to a method for producing N - [(2,3-fullerene [60]) - 2,3-dihydro-1H-1,2,3-benzotriazol-1-yl) methyl] -N, N dimethylamine of the general formula (1):

where n = 1-3.

 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.

Известный способ не позволяет получать N-[(2,3-фуллерен[60])-2,3-дигидро-1H-1,2,3-бензотриазол-1-ил)метил]-N,N-диметиламин (1).A known method (Zheng Dagui, Li Yuliang, Yang Jingkui, Zhu Daoben. Fullerene Sci- and Technol., 1996, V. 4, 5, 1067-1072) to obtain heterosubstituted fullerenes, namely the pyrrolidine derivative of fullerene [60] of the formula (2) by reaction With ₆₀ s (HCO) _n and DL-valine in a toluene solution at the boiling point of the solvent in a nitrogen atmosphere with a yield of 45%

The known method does not allow to obtain N - [(2,3-fullerene [60]) - 2,3-dihydro-1H-1,2,3-benzotriazol-1-yl) methyl] -N, N-dimethylamine (1) .

Известным способом не может быть получен N-[(2,3-фуллерен[60])-2,3-дигидро-1H-1,2,3-бензотриазол-1-ил)метил]-N,N-диметиламин (1).A known method (AC Tome, RF Enes, JPC Tome, J. Rocha, MGPMS Neves, JAS Cavaleiro, J. Elguero. Tetrahedron, 1998, 54, 11141-11150) for the preparation of a pyrimidine derivative of fullerene [60] of the formula (3) by reaction C ₆₀ with substituted sulfylene (4) in 1,2,4-trichlorobenzene at 214 ^o C in nitrogen atmosphere with a yield of 77%

In a known manner can not be obtained N - [(2,3-fullerene [60]) - 2,3-dihydro-1H-1,2,3-benzotriazol-1-yl) methyl] -N, N-dimethylamine (1 )

N-[(1,2,3-бензотриазол-1-ил)метил] -N, N-диметиламин (5) берут в избытке по отношению к фуллерену [60] с целью включения в молекулу фуллерена максимального количества бензотриазольных фрагментов. Снижение количества N-[(1,2,3-бензотриазол-1-ил)метил] -N, N-диметиламин (5) по отношению к С₆₀ (например, 1: 1) приводит к резкому уменьшению выхода целевых продуктов, а также к снижению вводимых в молекулу фуллерена бензотриазольных фрагментов.The essence of the method consists in the interaction of fullerene [60] with an excess of N- [1,2,3-benzotriazol-1-yl) methyl] -N, N-dimethylamine (5), taken in a molar ratio, respectively, 1: (5-15) , preferably 1:10, in an argon atmosphere at a temperature of 190-210 ^{° C.} , preferably 200 ^{° C.} , for 6-10 hours, preferably 8 hours, in a toluene solution. The yield of N - [(2,3-fullerene [60]) - 2,3-dihydro-1H-1,2,3-benzotriazol-1-yl) methyl] -N, N-dimethylamine (1) is (according to HPLC) 72-88%. The reaction proceeds according to the scheme.

N - [(1,2,3-benzotriazol-1-yl) methyl] -N, N-dimethylamine (5) is taken in excess with respect to fullerene [60] in order to include the maximum amount of benzotriazole fragments in the fullerene molecule. A decrease in the amount of N - [(1,2,3-benzotriazol-1-yl) methyl] -N, N-dimethylamine (5) with respect to C ₆₀ (for example, 1: 1) leads to a sharp decrease in the yield of the target products, and also to a decrease in the benzotriazole moieties introduced into the fullerene molecule.

 N - [(2,3-fullerene [60]) -2,3-dihydro-1H-1,2,3-benzotriazol-1-yl) methyl] -N, N-dimethylamine (1) is formed only with the participation of fullerene [60] and N - [(1,2,3-benzotriazol-1-yl) methyl] -N, N-dimethylamine (5).

The reaction at a higher temperature, for example 250 ^o With, leads to the formation of seal products. At a lower temperature, for example 150 ^o C, the reaction rate decreases.

Significant differences of the proposed method:
1. The proposed method is based on the use of substituted benzotriazole as a starting reagent (5). In the known method, substituted sulfylene (4) is used. The proposed method, unlike the known one, allows benzotriazole moieties to be introduced into the fullerene molecule to obtain N - [(2,3-fullerene [60]) -2,3-dihydro-1H-1,2,3-benzotriazol-1-yl) methyl ] -N, N - [- dimethylamine (1), the synthesis of which is not described in the literature.

The method is illustrated by the following examples:
EXAMPLE 1. 0.02 mmol of fullerene [60], 10 ml of “dry” toluene and 0.2 mmol N - [(1,2,3-benzotriazole-1-) are placed in a 17 ml metal “finger” autoclave in an argon atmosphere. il) methyl] -N, N-dimethylamine (5), stirred for 8 hours at a temperature of 200 ^o With, get N - [(2,3-fullerene [60]) - 2,3-dihydro-1H-1,2, 3-benzotriazol-1-yl) methyl] -N, N-dimethylamine (1) with the number of benzotriazole moieties from 1 to 3 and a total yield of 82% (according to HPLC).

Другие примеры, подтверждающие способ, приведены в таблице. ¹³ C NMR spectrum - [(2,3-fullerene [60]) - 2,3-dihydro-1H-1,2,3-benzotriazol-1-yl) methyl] -N, N-dimethylamine (1) (δ , ppm): 118.93; 119.19; 121.59; 124.52; 131.22; 136.16 (C ₁ -C ₆ ), 71.31 (C ⁷ ), 74.25 (C ⁸ ), 70.22 (C ⁹ ), 42.50 (C ¹⁰ , C ¹¹ ), 134.18-168.86 (fullerene)

Other examples confirming the method are given in the table.

 Toluene was used as a solvent, since it has the highest solubility of fullerene [60].

Claims (1)

The method of obtaining N - [(2,3- (fullerene [60]) -2,3-dihydro-1H-1,2,3-benzotriazol-1-yl) methyl] -N, N-dimethylamine of the general formula (1)

where n = 1-3,
characterized in that fullerene [60] interacts with an excess of N - [(1,2,3-benzotriazol-1-yl) methyl] -N, N-dimethylamine, taken in a molar ratio of 1: (5 ÷ 15), respectively, in atmosphere of argon in the presence of toluene as a solvent at 190-210 ^o C for 6-10 hours

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