RU2313521C1 - Method for preparing 1-(4-quinolinamino)-1,2-dihydro[60]fullerene - Google Patents

Abstract

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of functionally substituted fullerenes. Invention describes a method for synthesis of 1-(4-quinolinamino)-1,2-dihydro[60]fullerene of the general formula (1):

. Method involves interaction of C₆₀-fullerene with 4-quinolinamine in the mole ratio C₆₀-fullerene : 4-quinolinamine = 0.01:(0.01-0.011) in the presence of titanocene dichloride (Cp₂TiCl₂) taken in the amount 15-25 mole% with respect to C₆₀-fullerene in toluene medium as a solvent, at temperature 140-160⁰C for 6-10 h. Synthesized substituted fullerenes can be used as chelating agents, sorbents, biologically active compounds and in development 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- (4-quinolinamino) -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.

The known method ([1], M.F. Goldschleger, A.S. Lobach, A.S. Astakhov, M.G. Kaplunov, A.V. Kulikov, A.P. Moravsky, O.S. Roshchupkina, Yu M.Shulga, Izv. AN Ser.chem., 1994, 1143) for the preparation of 1 - ([1- (hydroxyethyl) ethyl] amino) -1,2-dihydro [60] fullerene of the formula (2) by a C ₆₀ s reaction 3-amino-1-butanol, where it is a medium, at room temperature.

The known method does not allow to obtain 1 - (4-quinolinamino) -1,2-dihydro [60] fullerene (1).

The known method ([2], L. L. Gumanov, G. A. Volkov, A. Shastin, B. L. Korsunsky. Izv. AN Ser.chem., 1996, 4, 814) for the preparation of 1-silica gel -1,2-dihydro [60] fullerene of formula (3) by the addition of an amine-containing silica gel to C ₆₀ in xylene at a boiling point of the solvent for 36 hours according to the scheme

The known method does not allow to obtain 1- (4-quinolinamino) -1,2-dihydro [60] fullerene (1).

Thus, in the literature there is no information on the selective synthesis of 1- (4-quinolinamino) -1,2-dihydro [60] fullerene (1).

A new method is proposed for producing 1- (4-quinolinamino) -1,2 dihydro [60] fullerene (1).

The essence of the method consists in the interaction of fullerene C ₆₀ with 4-quinolinamine, taken in a molar ratio of 0.01: (0.01-0.011), preferably 0.01: 0.0105, in the presence of a titanocene dichloride catalyst (Cp ₂ TiCl ₂ ), taken in an amount of 15-25 mol.% in relation to fullerene C ₆₀ at a temperature of 140-160 ° C for 6-10 hours in a toluene solution. The yield of 1- (4-quinolinamino) -1,2-dihydro [60] fullerene (1) is (according to HPLC) 42-70%. The reaction proceeds according to the scheme.

4-Quinolinamine is taken in excess with respect to fullerene C ₆₀ in order to increase the yield of the target product (1). The decrease in the amount of 4-quinolinamine with respect to C _{60 is} impractical, since it leads to a decrease in the yield of the target product.

1- (4-Quinolinamino) -1,2-dihydro [60] fullerene (1) is formed only with the participation of fullerene [60] and 4-quinolinamine.

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 catalyst Ср 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 towards a significant increase in the content of 4-quinolinamine with respect to fullerene [60] leads to the addition of additional molecules of the starting secondary amine to the C ₆₀ molecule.

Significant differences of the proposed method:

1. The proposed method is based on the use of 4-quinolinamine and a catalyst Cr ₂ TiCl ₂ as a starting reagent. In the known method, silica gelamine is used. The proposed method, unlike the known one, allows one to selectively introduce into the fullerene molecule one fragment of the starting 4-quinolinamine with the production of 1- (4-quinolinamino) -1,2-dihydro [60] fullerene (1), the synthesis of 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 C ₆₀ , 10 ml of “dry” toluene, 0.0105 mmol of 4-quinolinamine and 0.002 mmol of catalyst Cp ₂ TiCl ₂ are placed, stirred for 8 hours at a temperature of 150 ° C, get 1- (4-quinolinamino) -1,2-dihydro [60] fullerene of the general formula (1) with a yield of 60% (according to HPLC).

¹³ C NMR spectrum of 1- (4-quinolinamino) -1,2-dihydro [60] fullerene (1) (δ, ppm):

56.42 (C ² ), 74.56 (C ¹ ), 95.20 (C ⁵ ), 121.83 (C ¹¹ ), 123.17 (C ¹⁰ ), 126.85 (C ¹² ), 128.70 (C ^8.9 ), 148.05 (C ¹³ ), 150.67 (C ⁶ ), 155.39 (C ⁴ ). The signals of the carbon atoms of the fullerene fragment are located in the region 130-161.

Other examples confirming the method are given in the table.

Table №№

:Cp₂TiCl₂, ммольMolar ratio
C ₆₀ :

: Cp ₂ TiCl ₂ , mmol The reaction temperature, ° C Reaction time, hour Yield (1),% one 2 3 four 5 one. 0.01: 0.0105: 0.002 150 8 60 2. 0.01: 0.011: 0.002 150 8 64 3. 0.01: 0.01: 0.002 150 8 56 four. 0.01: 0.0105: 0.0025 150 8 70 5. 0.01: 0.0105: 0.0015 150 8 53 6. 0.01: 0.0105: 0.002 160 8 67 7. 0.01: 0.0105: 0.002 140 8 42 8. 0.01: 0.0105: 0.002 150 10 63 9. 0.01: 0.0105: 0.002 150 6 49

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

Claims (1)

The method of obtaining 1- (4-quinolinamino) -1,2-dihydro [60] fullerene of the General formula (1)

characterized in that the fullerene C ₆₀ is reacted with 4-quinolinamine in a molar ratio of C ₆₀ : 4-quinolinamine equal to 0.01: (0.01-0.011) in the presence of a titanocene dichloride catalyst (Cp ₂ TiCl ₂ ), taken in an amount 15-25 mol.% In relation to fullerene C ₆₀ in toluene as a solvent at a temperature of 140-160 ° C for 6-10 hours