RU2447062C2 - METHOD FOR SELECTIVE SYNTHESIS OF 1'-[2-METHYLSULPHANYL)-ETHYL]-1'-ETHYLFORMYLCYCLOPROPA [2'3':1,9] (C60-Ih) [5,6] FULLERENE - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: invention relates to organic chemistry. The method involves reaction of C₆₀-fullerene with 1-[2-(methylsulphanyl)ethyl]diazoacetic ether in o-dichlorobenzene (o-DCB) in the presence of a three-component catalyst {Pd(acac)₂:4PPh₃:4Et₃Al} at temperature 80°C for 0.2-1.0 hours. 1'-[2-(methylsulphanyl)-ethyl]-1'-ethylformylcyclopropa[2',3':1,9](C₆₀-I_h)[5,6]fullerene (1) is obtained with output 31-55%.

EFFECT: obtaining functionally substituted fullerenes, which can be used as effective nanocomponent additives to industrial oil, as well as novel optoelectronic materials.

1 cl, 1 tbl, 1 ex

Description

The present invention relates to the field of organic synthesis, and in particular to a method for the selective preparation of 1 '- [2- (methylsulfanyl) ethyl] -1'-ethyl formylcycloprop [2', 3 ': 1.9] (C ₆₀ -I _h ) [ 5,6] fullerene of the general formula (1):

Sulfur derivatives of fullerenes can be used as effective nanocomponent additives for industrial oils, as well as new materials for optoelectronics (U.M.Dzhemilev, G.N. Kirichenko, V.I. Glazunova, A.G. Ibrahimov, A.R. Tuktarov, M. Pudas, A. A. Desyatkin, N. R. Popodko, V. V. Korolev, RF Patent No. 2382816 dated 02.27.10, Bull. No. 6 [1], A. Cravino, NSSariciftci. J. Mater. Chem., 2002, 12, 1931 [2]).

The known method (C. Bingel. Chem. Ber., 1993, 126, 1957 [3]) for producing (1,1-diethoxycarbonylmethane) fullerene 4 with a total yield of 45% by reaction of C ₆₀ -fullerene (2) with diethyl bromomalonate 3 in the presence of hydride sodium for 7 hours

In a known manner, 1 '- [2- (methylsulfanyl) ethyl] -1'-ethylformylcyclopropa [2', 3 ': 1.9] (C ₆₀ -I _h ) [5,6] fullerene of the general formula ( one).

A known method (R. Pellicciari, D. Annibali, G. Costantino, M. Marinozzi, B. Natalini. Synlett. 1997, 1196 [4]) to obtain 1'-ethyl formyl- (C ₆₀ -I _h ) [5,6] fullero [2 ', 3': 1.9] cyclopropane (5) in 42% yield of C _60- fullerene (2) with diazoacetate in 1-methylnaphthalene at room temperature for 8 hours in the presence of stoichiometric amounts of the Rh ₂ complex ( OAc) ₄ .

The disadvantage of this method is the use of Rh-complex in stoichiometric quantities and expensive 1-methylnaphthalene as a solvent, which leads to high economic costs.

A new method is proposed for the preparation of 1 '- [2- (methylsulfanyl) ethyl] -1'-ethyl formylcycloprop [2', 3 ': 1.9] (C ₆₀ -I _h ) [5,6] fullerene (1).

The essence of the method consists in the interaction of fullerene (C ₆₀ ) with 1- [2- (methylsulfanyl) ethyl] diazoacetic ester in o-dichlorobenzene (o-DCB) in the presence of a three-component catalyst {Pd (acac) ₂ : 4PPh ₃ : 4Et ₃ Al} taken in a molar ratio of C ₆₀ : diazo compound: Pd (acac) ₂ : PPh ₃ : Et ₃ Al = 0.01: (0.03-0.07) :( 0.0015-0.0025) :( 0.006-0.01) :( 0.006-0.01), preferably 0.01: 0.05: 0.002: 0.008: 0.008, at a temperature of 80 ° C for 0.2-1.0 hours. Receive 1 '- [2- (methylsulfanyl) ethyl] -1'-ethylformylcycloprop [2', 3 ': 1.9 ] (C ₆₀ -I _h ) [5,6] fullerene (1) with a yield of 31-55%. The reaction proceeds according to the scheme:

Carrying out the specified reaction in the presence of a palladium catalyst [Pd] more than 20 mol. % with respect to fullerene C ₆₀ does not lead to a significant increase in the yield of the target product (1). The use of palladium catalyst [Pd] in an amount of less than 20 mol. % with respect to fullerene C ₆₀ reduces the yield of the target product, which is possibly associated with a decrease in reaction centers. The reaction should be carried out at a temperature of 80 ° C. Carrying out the reaction at a higher temperature (for example, 110 ° C) is associated with an increase in energy consumption; at a lower temperature (for example, 40 ° C), the reaction rate decreases.

Significant differences of the proposed method

The proposed method is based on the use of a palladium complex in catalytic amounts, the reaction proceeds in available o-dichlorobenzene. In the known method, the Rh complex is used in stoichiometric amounts, the reaction proceeds in less accessible 1-methylnaphthalene.

The proposed method, unlike the known ones, allows one to selectively obtain 1 '- [2- (methylsulfanyl) ethyl] -1'-ethyl formylcycloprop [2', 3 ': 1.9] (C ₆₀ -I _h ) [5,6 ] fullerene (1), the synthesis of which is not described in the literature.

The method is illustrated by examples.

To a solution of 0.002 mmol Pd (acac) ₂ in 0.1 ml of o-DCB in a stream of dry argon at a temperature of -5 ° C and stirring, add 0.008 mmol of PPh ₃ , 0.008 mmol of Et ₃ Al and 0.01 mmol of C ₆₀ -fullerene in 1 ml of o- DHB. The reaction mixture is heated to 80 ° C and 0.05 mmol of 1- [2- (methylsulfanyl) ethyl] diazoacetate in 0.5 ml of o-DCB is added dropwise. After 0.5 h, the reaction mass is cooled and passed through a column with a small layer of silica gel. Obtain 1 '- [2- (methylsulfanyl) ethyl] -1'-ethylformylcyclopropa [2', 3 ': 1.9] (C ₆₀ -I _h ) [5,6] fullerene (1) with a yield of 45% ( according to HPLC).

Spectral characteristics (1):

¹ H NMR spectrum: 1.53 (t, 3H, CH ₃ , J = 7 Hz), 2.30 (s, 3H, CH ₃ ), 3.11 (t, 2H, CH ₂ J = 8 Hz), 3.20 (t, 2H, CH ₂ J = 8 Hz), 4.54 (q, 2H, CH ₂ J = 7 Hz).
¹³ C NMR spectrum: 14.75, 16.48, 29.60, 32.16, 48.84, 62.73, 75.64, 166.70. The signals of the carbon atoms of the fullerene fragment are located in the region of 130-150 ppm.

Other examples confirming the method are given in table 1.

Table 1 No. p / p The molar ratio of C ₆₀ : 1- [2- (methylsulfanyl) ethyl] diazoacetic ester: Pd (acac) ₂ : PPh ₃ : Et ₃ Al, mmol Reaction time, hour The total yield of target products (1) and (2),% one 0.01: 0.05: 0.002: 0.008: 0.008 0.5 45 2 0.01: 0.07: 0.002: 0.008: 0.008 0.5 48 3 0.01: 0.03: 0.002: 0.008: 0.008 0.5 40 four 0.01: 0.05: 0.0025: 0.01: 0.01 0.5 55 5 0.01: 0.05: 0.0015: 0.006: 0.006 0.5 31 6 0.01: 0.05: 0.002: 0.008: 0.008 1.0 49 7 0.01: 0.05: 0.002: 0.008: 0.008 0.2 34

Reactions were carried out at a temperature of 80 ° C in o-dichlorobenzene.

Claims (1)

Method for the selective preparation of 1 '- [2- (methylsulfanyl) ethyl] -1'-ethylformylcycloprop [2', 3 ': 1.9] (C ₆₀ -I _h ) [5,6] fullerene (1)

characterized in that the C ₆₀ fullerene interacts with 1- [2- (methylsulfanyl) ethyl] diazoacetic ester in o-dichlorobenzene (o-DCB) in the presence of a three-component catalyst {Pd (acac) ₂ : 4PPh ₃ : 4Et ₃ Al}, taken in a molar ratio of C ₆₀ : diazo compound: Pd (acac) ₂ : PPh ₃ : Et ₃ Al = 0.01: (0.03-0.07) :( 0.0015-0.0025) :( 0.006-0 , 01) :( 0.006-0.01), preferably 0.01: 0.05: 0.002: 0.008: 0.008, at a temperature of 80 ° C for 0.2-1.0 hours