RU2315038C1 - Method for preparing 1-(2,7-octadienyl)-2,5-dimethyl-3,4-fullero[60]pyrrolidine - Google Patents

Abstract

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of 1-(2,7-octadienyl)-2,5-dimethyl-3,4-fullero[60]pyrrolidine of the general formula (1):

. Method involves interaction of fullerene[60] with N,N-diethyl-2,7-octadiene-1-ylamine taken in the mole ratio fullerene-C₆₀ : N,N-diethyl-2,7-octadiene-1-ylamine = 0.01:(0.011-0.012) in the presence of Cp₂TiCl₂ as a catalyst taken in the amount 15-25 mole% with respect to fullerene[60], in toluene medium as a solvent, at temperature 150-170°C for 2-4 h. Method provides preparing the end substance with the yield 65-86%.

EFFECT: improved method of synthesis.

1 tbl, 1 ex

Description

The present invention relates to organic chemistry, specifically, to a method for producing 1- (2,7-octadienyl) -2,5-dimethyl-3,4-fullero [60] pyrrolidine 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.

The known method ([1], Sheng-Gao Liu, Lianhe Shu, Jose Rivera, Haiying Liu, Jean-Manuel Raimundo, Jean Roncali, Alain Gorgues, Luis Echegoyen. J. Org. Chem., 1999, 64, 4884-4886) for preparing the pyrrolidine derivative of fullerene [60] of the formula (2) by reacting C ₆₀ with HCNO and CH ₃ NHCH ₂ COOH in a toluene solution at the boiling point of the solvent (~ 110 ° C) in 40% yield.

The known method does not allow to obtain 1- (2-propenyl) -2,5-dimethyl-3,4-fullero [60] pyrrolidine (1).

A known method ([2], GELawson, A. Kitaygorodskiy, B. Ma, CE Bunker, Y.-P. Sun. J. Chem. Soc., Chem. Commun., 1995, 21, 2225-2226) to obtain a pyrrolidine derivative of fullerene [60] of formula (4) by the reaction of photocycloaddition of triethylamine (3) to C ₆₀ in toluene at 20 ° C in a nitrogen atmosphere with a yield of 32% according to the scheme.

In a known manner, 1- (2-propenyl) -2,5-dimethyl-3,4-fullero [60] pyrrolidine (1) cannot be obtained.

Thus, in the literature there is no information on the selective synthesis of 1- (2,7-octadienyl) -2,5-dimethyl-3,4-fullero [60] pyrrolidine (1).

A new method is proposed for the preparation of 1- (2,7-octadienyl) -2,5-dimethyl-3,4-fullero [60] pyrrolidine (1).

The essence of the method consists in the interaction of fullerene [60] with N, N-diethyl-2,7-octadiene-1-ylamine (5), taken in a molar ratio, respectively 0.01: (0.011-0.012), preferably 0.01: 0.0115, in the presence of titanium catalyst Cp ₂ TiCl ₂ in an amount of 15-25 mol% with respect to fullerene [60], at a temperature of 150-170 ° C for 2-4 hours in a toluene solution. The yield of 1- (2,7-octadienyl) -2,5-dimethyl-3,4-fullero [60] pyrrolidine (1) is 65-86% (according to HPLC). The reaction proceeds according to the scheme:

N, N-diethyl-2,7-octadiene-1-ylamine (5) is taken in excess with respect to fullerene [60] in order to increase the yield of the target product (1). The reduction in the amount of N, N-diethyl-2,7-octadiene-1-ylamine (5) with respect to C _{60 is} impractical, since it leads to a sharp decrease in the yield of the target product.

1- (2,7-Octadienyl) -2,5-dimethyl-3,4-fullero [60] pyrrolidine (1) is formed only with the participation of fullerene [60] and N, N-diethyl-2,7-octadiene-1 -ylamine (5).

Carrying out the reaction at a higher temperature, for example 200 ° C, leads to the formation of compaction products. At lower temperatures, for example 100 ° C, the reaction rate decreases.

Carrying out this reaction in the presence of a titanium 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 the catalytically active centers in the reaction mass.

A change in the ratio of the starting reagents to a significant increase in the content of N, N-diethyl-2,7-octadiene-1-ylamine (5) with respect to fullerene [60] leads to the addition of additional pyrrolidine fragments to the C ₆₀ molecule.

Significant differences of the proposed method:

1. The proposed method is based on the use of N, N-diethyl-2,7-octadiene-1-ylamine (5) as a starting reagent, the reaction proceeds under the influence of a Cp ₂ TiCl ₂ catalyst. In the known method, triethylamine is used, the reaction proceeds by photo-irradiation. The proposed method, unlike the known one, allows the pyrrolidine fragment with an octadienyl substituent to be introduced into the fullerene molecule with nitrogen to obtain 1- (2,7-octadienyl) -2,5-dimethyl-3,4-fullero [60] pyrrolidine (1), synthesis which is not described in the literature.

The method is illustrated by the following examples:

EXAMPLE 1. In a metal “finger” autoclave with a volume of 17 ml, 0.01 mmol of fullerene [60], 10 ml of “dry” toluene, 0.0115 mmol of N, N-diethyl-2,7-octadiene-1-ylamine (5) and 0.002 mmol are placed catalyst Cp ₂ TiCl ₂ , stirred for 3 hours at a temperature of 160 ° C, get 1- (2,7-octadienyl) -2,5-dimethyl-3,4-fullero [60] pyrrolidine of General formula (1) with a yield of 78% (according to HPLC).

¹³ C NMR spectrum of 1- (2,7-octadienyl) -2,5-dimethyl-3,4-fullero [60] pyrrolidine (1) (δ, ppm):

¹³ C NMR spectrum (δ, ppm): 15.04 (C ^6.7 ), 26.45 (C ¹² ), 31.60 (C ^11.13 ), 51.10 (C ⁸ ), 67.14 (C ^2.5 ), 75.20 (C ^3.4 ), 116.10 (C ¹⁵ ), 129.14 (C ⁹ ), 133.35 (C ¹⁰ ), 137.73 (C ¹⁴ ). The signals of the carbon atoms of the fullerene fragment are located in the region 139.20-158.57. Mass spectrum m / z (I _rel ,%): 899 [M] ⁺

Other examples confirming the method are given in table 1.

Table 1 №№

, ммольMolar ratio

mmol The reaction temperature, ° C Reaction time, hour Yield (1),% one 2 3 four 5 one. 0.01: 0.0115: 0.002 160 3 78 2. 0.01: 0.012: 0.002 160 3 81 3. 0.01: 0.011: 0.002 160 3 75 four. 0.01: 0.0115: 0.0025 160 3 86 5. 0.01: 0.0115: 0.0015 160 3 72 6. 0.01: 0.0115: 0.002 170 3 80 7. 0.01: 0.0115: 0.002 150 3 65 8. 0.01: 0.0115: 0.002 160 four 83 9. 0.01: 0.0115: 0.002 160 2 67

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

Claims (1)

The method of obtaining 1- (2,7-octadienyl) -2,5-dimethyl-3,4-fullero [60] pyrrolidine of the general formula (1)

characterized in that fullerene [60] interacts with N, N-diethyl-2,7-octadiene-1-ylamine in a molar ratio of C ₆₀ : N, N-diethyl-2,7-octadiene-1-ylamine equal to 0, 01: (0.011-0.012), in the presence of a Cp ₂ TiCl ₂ catalyst in an amount of 15-25 mol.% With respect to fullerene [60], in toluene as a solvent at a temperature of 150-170 ° C for 2-4 hours .