RU2309939C1 - Method for preparing 1-(n,n-diprop-2-enylamino)-1,2-dihydro[60]fullerene - Google Patents

Abstract

FIELD: organic chemistry, chelating agents, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of 1-(N,N-diprop-2-enylamino)-1,2-dihydro[60]fullerene of the formula (1):

. Method involves interaction of fullerene-C₆₀ with N,N-diallylamine [(CH₂=CHCH₂)NH] in the mole ratio fullerene-C₆₀ : N,N-diallylamine = 0.01:(0.01-0.011) in the presence of titanocene dichloride Cp₂TiCl₂ as a catalyst taken in the amount 15-25 mol.% with respect to fullerene-C₆₀ in toluene medium, at room temperature for 18-30 h. The yield of the end product is 68-90%. Synthesized compound can be used as chelating agents, sorbents and biologically active compounds, and in creature of novel materials with desired electronic, magnetic and optical properties.

EFFECT: improved method of synthesis.

1 tbl, 1 ex

Description

The present invention relates to organic chemistry, specifically to a method for producing 1- (N, N-diprop-2-enylamino) -1,2-dihydro [60] fullerene of the general 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.

A known method ([1], M. Maggini, G. Scorrano, A. Bianco, C. Toniolo, M. Prato. Tetrahedron Lett., 1995, v. 36, No. 16, 2845-2846) to obtain 1,4-dimethyl -2,3-fullero [60] decahydroquinoxaline of formula (2) by reaction of C ₆₀ with N ¹ , N ² -dimethyl-1,2-cyclohexanediamine in a toluene solution at a boiling point of the solvent (~ 110 ° C) for a week under nitrogen atmosphere with a yield of 10%.

The known method does not allow to obtain 1- (N, N-diprop-2-enylamino) -1,2-dihydro [60] fullerene (1).

A known method ([2], G. Schick, K.-D. Kampe, A. Hirsch. J. Chem. Soc., Chem. Commun., 1995, 19, 2023-2024) for producing 1,4-dimorpholin-1 , 4-dihydro [60] fullerene of the formula (3) by the addition of morpholine to C ₆₀ in toluene at 20 ° C for a week under nitrogen atmosphere with a yield of 8.5% according to the scheme.

In a known manner, 1- (N, N-diprop-2-enylamino) -2-hydro-1,2-dihydro [60] fullerene (1) cannot be obtained.

Thus, in the literature there is no information on the selective synthesis of 1- (N, N-diprop-2-enylamino) -1,2-dihydro [60] fullerene (1).

A new method is proposed for producing 1- (N, N-diprop-2-enylamino) -1,2-dihydro [60] fullerene (1).

The essence of the method consists in the interaction of fullerene C ₆₀ with N, N-diallylamine, taken in a molar ratio, respectively 0.01: (0.01-0.011), preferably 0.01: 0.0105, in the presence of a catalyst titanocene dichloride Cp ₂ TiCl ₂ taken in an amount of 15-25 mol. % with respect to fullerene C ₆₀ at room temperature (~ 20 ° C) for 18-30 hours, preferably 24 hours, in a toluene solution. The yield of 1- (N, N-diprop-2-enylamino) -1,2-dihydro [60] fullerene (1) is (according to HPLC) 68-90%. The reaction proceeds according to the scheme:

N, N-diallylamine is taken in excess with respect to fullerene C ₆₀ in order to increase the yield of the target product (1). A decrease in the amount of N, N-diallylamine with respect to C _{60 is} impractical, since it leads to a decrease in the yield of the target product.

1- (N, N-Diprop-2-enylamino) -1,2-dihydro [60] fullerene (1) is formed only with the participation of fullerene [60] and N, N-diallylamine.

Carrying out the specified reaction in the presence of a catalyst Cp ₂ TiCl ₂ more than 25 mol. % with respect to C ₆₀ does not lead to a significant increase in the yield of the target product (1). The use of the catalyst Cp ₂ TiCl ₂ less than 15 mol.% With respect to C ₆₀ reduces the yield of the product (1), which is possibly associated with a decrease in catalytically active centers in the reaction mass.

A change in the ratio of the starting reagents towards a significant increase in the content of N, N-diallylamine with respect to fullerene C ₆₀ leads to the addition of additional molecules of the starting amine to the C ₆₀ molecule.

Significant differences of the proposed method.

The proposed method is based on the use of N, N-diallylamine and a Cp ₂ TiCl ₂ catalyst as a starting reagent. In the known method, morpholine is used. The proposed method, unlike the known one, allows one to selectively introduce into the fullerene molecule one fragment of the starting diallylamine to obtain 1- (N, N-dipron-2-enylamino) -1,2-dihydro [60] fullerene (1), the synthesis of which is not available in the literature described.

The method is illustrated by the following examples.

EXAMPLE 1. In a 50 ml glass flask, 0.01 mmol of fullerene C ₆₀ , 10 ml of “dry” toluene, 0.0105 mmol of N, N-diallylamine and 0.002 mmol of Cp ₂ TiCl ₂ catalyst are placed, stirred for 24 hours at a temperature of 20 ° C, get 1 - (N, N-diprop-2-enylamino) -1,2-dihydro [60] fullerene of the general formula (1) with a yield of 82% (according to HPLC).

¹³ C NMR spectrum of 1- (N, N-diprop-2-enylamino) -1,2-dihydro [60] fullerene (1)

(δ, ppm): 56.42 (C ^3.6 ), 61.53 (C ² ), 74.85 (C ¹ ), 116.53 (C ^5.8 ), 133.04 (C ^4.7 ). The signals of the carbon atoms of the fullerene fragment are located in the region of 131.83-160.85.

Other examples confirming the method are given in the table.

Table №№ Molar ratio, C ₆₀ : (CH ₂ = CHCH ₂ ) ₂ NH: Cp ₂ TiCl _2, mol Reaction time, h Yield (1),% one 2 3 four one 0.01: 0.0105: 0.002 24 82 2 0.01: 0.011: 0.002 24 85 3 0.01: 0.01: 0.002 24 78 four 0.01: 0.0105: 0.0025 24 90 5 0.01: 0.0105: 0.0015 24 68 6 0.01: 0.0105: 0.002 thirty 88 7 0.01: 0.0105: 0.002 eighteen 73

Toluene was used as a solvent, since it has the highest solubility of fullerene C ₆₀ ; reactions were carried out at room temperature (~ 20 ° C).

Claims (1)

The method of obtaining 1- (N, N-diprop-2-enylamino) -1,2-dihydro [60] fullerene of the general formula (1)

characterized in that the C ₆₀ fullerene is reacted with N, N-diallylamine [(CH ₂ = CHCH ₂ ) ₂ NH] in a C ₆₀ : N, N-diallylamine molar ratio of 0.01: (0.01-0.011) , in the presence of a catalyst of titanocene dichloride Cp ₂ TiCl ₂ , taken in an amount of 15-25 mol.% in relation to fullerene C ₆₀ in toluene as a solvent at room temperature (~ 20 ° C) for 18-30 hours