RU2309941C1 - Method for preparing 1-(n,n-diphenylamino)-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-diphenylamino)-1,2-dihydro[60]fullerene of the formula (I):

. Method involves interaction of fullerene-C₆₀ with diphenylamine (Ph₂NH) in the mole ratio fullerene-C₆₀ : diphenylamine = 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 as a solvent, at temperature 140-160°C for 8-10 h. The yield of the end product is 64-86%. 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-diphenylamino) -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-diphenylamino) -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 in a nitrogen atmosphere with a yield of 8.5% according to the scheme.

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

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

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

The essence of the method consists in the interaction of fullerene C ₆₀ with diphenylamine, 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. % with respect to fullerene C ₆₀ at a temperature of 140-160 ° C for 8-10 hours in a solution of toluene. The yield of 1- (N, N-diphenylamino) -1,2-dihydro [60] fullerene (1) is 64-86% (according to HPLC). The reaction proceeds according to the scheme:

Diphenylamine 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 diphenylamine with respect to C _{60 is} impractical, since it leads to a decrease in the yield of the target product.

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

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 diphenylamine 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 diphenylamine and a catalyst Cp ₂ TiCl ₂ as a starting reagent. In the known method, morpholine is used. The proposed method, unlike the known one, allows one fragment of the starting diphenylamine to be selectively introduced into the fullerene molecule to obtain 1- (N, N-diphenylamino) -1,2-dynhydro [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 diphenylamine and 0.002 mmol of Cp ₂ TiCl ₂ catalyst are placed, stirred for 9 hours at a temperature of 150 ° C, get 1- (N, N-diphenylamino) -1,2-dihydro [60] fullerene of the general formula (1) with a yield of 77% (according to HPLC).

¹³ C NMR spectrum of 1- (N, N-diphenylamino) -1,2-dihydro [60] fullerene (1) (5, ppm):

66.25 (С ¹ ), 74.10 (С ² ), 117.86 (С ^4,8,10,14 ), 121.09 (С ^6,12 ), 129.39 (С ^5,7,11,13 ), 154.20 (С ^3,9 ) The signals of the carbon atoms of the fullerene fragment are located in the region of 130.76-161.66.

Other examples confirming the method are given in table 1.

Table 1 №№ The molar ratio.
C ₆₀ : Ph ₂ NH: Cp ₂ TiCl ₂ , mmol The reaction temperature, ° C Reaction time. hour Output (1)
% one 2 3 four 5 one. 0.01: 0.0105: 0.002 150 9 77 2. 0.01: 0.011: 0.002 150 9 80 3. 0.01: 0.01: 0.002 150 9 73 four. 0.01: 0.0105: 0.0025 150 9 86 5. 0.01: 0.0105: 0.0015 150 9 71 6. 0.01: 0.0105: 0.002 160 9 79 7. 0.01: 0.0105: 0.002 140 9 64 8. 0.01: 0.0105: 0.002 150 10 81 9. 0.01: 0.0105: 0.002 150 8 69

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

Claims (1)

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

characterized in that the C ₆₀ fullerene is reacted with diphenylamine (Ph ₂ NH) in a C ₆₀ : diphenylamine molar ratio of 0.01: (0.01-0.011) in the presence of a titanocene dichloride catalyst (Cp ₂ TiCl ₂ ) taken in the amount of 15-25 mol. % with respect to fullerene C ₆₀ in toluene as a solvent at a temperature of 140-160 ° C for 8-10 hours