RU2342380C2 - Method of obtaining 2,5-diphenyl-3,4-fullero[60]tetrahydrothiophen-1-on - Google Patents

Abstract

FIELD: chemistry.

SUBSTANCE: claimed invention relates to field of organic chemistry, namely to method of obtaining 2,5-diphenyl-3,4-fullero[60]tetrahydrothiophen-1-on of general formula (I)

. Essence of method lies in interaction of fullerene C₆₀ with dibenzylsulfoxide in presence of catalyst Cp₂HfCl₂ in toluol medium at temperature 140-160°C during 5-7 hours. Target product output is 43-68%.

EFFECT: obtaining compounds, which can be used as complex-forming agents, sorbents, biologically active compounds, as well as in creation of novel materials with set electronic, magnetic and optical properties.

1 tbl, 9 ex

Description

The present invention relates to organic chemistry, specifically to a method for producing 2,5-diphenyl-3,4-fullero [60] tetrahydrothiophen-1-one (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 (J. Llacay, J. Veciana, J. Vidal-Gancedo, JL Bourdelande, R. Gonzalez-Noreno, C. Rovira. J. Org. Chem., 1998, 63, 5201-5210) to obtain sulfur-containing fullerene derivatives of the general formula (2) by the reaction of addition of the sulfylene derivative of tetrathiafulvalene to C ₆₀ in toluene at a temperature of 110 ° C according to the scheme:

The known method does not allow to obtain 2,5-diphenyl-3,4-fullero [60] tetrahydrothiophen-1-one (1).

A known method (H. Ishida, K. Itoh, M.Ohno. Tetrahrdron, 2001, 57, 1737-1747) for preparing fullerotetrahydrothiophen-1-one of formula (3) by the reaction of addition of bis (trimethylsilylmethyl) sulfoxide to C ₆₀ in o-dichlorobenzene at a temperature of 110 ° C followed by oxidation of the product of accession according to the scheme:

The known method does not allow to obtain 2,5-diphenyl-3,4-fullero [60] tetrahydrothiophen-1-one (1).

Thus, in the literature there is no information on the selective synthesis of 2,5-diphenyl-3,4-fullero [60] tetrahydrothiophen-1-one (1).

A new method is proposed for producing 2,5-diphenyl-3,4-fullero [60] tetrahydrothiophen-1-one (1).

The essence of the method consists in the interaction of fullerene C ₆₀ with dibenzyl sulfoxide (PhCH ₂ ) ₂ S = O ₂ S in the presence of a hafnacenedichloride catalyst (Cp ₂ HfCl ₂ ), taken in a molar ratio, respectively, of 0.01: (0.045-0.055) :( 0.0015-0.0025 ), preferably 0.01: 0.05: 0.0020, at a temperature of 140-160 ° C for 5-7 hours in a toluene solution. The yield of 2,5-diphenyl-3,4-fullero [60] tetrahydrothiophen-1-one (1) is 43-68% (according to HPLC). The reaction proceeds according to the scheme:

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

2,5-Diphenyl-3,4-fullero [60] tetrahydrothiophen-1-one (1) is formed only with the participation of fullerene [60] and dibenzyl sulfoxide.

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 the specified reaction in the presence of a catalyst of hafnacenedichloride Ср ₂ HfCl ₃ 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 a catalyst of the hafnacenedichloride Cp ₂ HfCl ₂ catalyst with 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 sites in the reaction mass.

A change in the ratio of the starting reagents to a significant increase in the content of dibenzyl sulfoxide with respect to fullerene [60] leads to the addition of additional molecules of the starting sulfoxide to the C ₆₀ molecule.

Significant differences of the proposed method.

The proposed method is based on the use of dibenzyl sulfoxide and a catalyst of hafnacenedichloride Cp ₂ HfCl ₂ as a starting reagent, the reaction proceeds in toluene. In the known method, bis (trimethylsilylmethyl) sulfoxide and m-chloroperbenzoic acid are used as starting reagents, the reaction proceeds in o-dichlorobenzene. The proposed method, unlike the known one, allows one to selectively obtain 2,5-diphenyl-3,4-fullero [60] tetrahydrothiophen-1-one (1) in a single step, the synthesis of which is not described in the literature.

The method is illustrated by the following examples.

Example 1. In a metal autoclave with a volume of 17 ml in an argon atmosphere is placed 0.01 mmol of fullerene C ₆₀ , 10 ml of “dry” toluene, 0.05 mmol of dibenzyl sulfoxide and 0.002 mmol of catalyst Cp ₂ HfCl ₂ , stirred for 6 hours at a temperature of 150 ° C, get 2, 5-diphenyl-3,4-fullero [60] tetrahydrothiophen-1-one (1) with a yield of 53% (according to HPLC).

¹³ C NMR spectrum of 2,5-diphenyl-3,4-fullero [60] tetrahydrothiophen-1-one (1) (δ, ppm):

51.07 (C ^2.5 ), 74.65 (C ^3.4 ), 146.41 (C ^6.12 ), 126.19 (C ^7.17 ), 128.67 (C ^8.10.14.14 ), 127.36 (C ^9.15 ), 127.53 (C ^11.13 ). The signals of the carbon atoms of the fullerene fragment are located in the region of 137-158 ppm.

Other examples confirming the method are given in the table.

Table №№ Molar ratio, C ₆₀ : (PhCH ₂ ) ₂ S = O: Cp ₂ TiCl ₂ , mmol The reaction temperature, ° C Reaction time, h Yield (1),% one 2 3 four 5 one. 0.01: 0.05: 0.002 150 6 53 2. 0.01: 0.055: 0.002 150 6 62 3. 0.01: 0.45: 0.002 150 6 51 four. 0.01: 0.05: 0.0025 150 6 68 5. 0.01: 0.05: 0.0015 150 6 49 6. 0.01: 0.05: 0.002 160 6 58 7. 0.01: 0.05: 0.002 140 6 43 8. 0.01: 0.05: 0.002 150 7 57 9. 0.01: 0.05: 0.002 150 5 46

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

Claims (1)

The method of obtaining 2,5-diphenyl-3,4-fullero [60] tetrahydrothiophen-1-one of the General formula (1)

by the interaction of fullerene C ₆₀ with dibenzyl sulfoxide (PhCH ₂ ) ₂ S = O in the presence of a hafnacene dichloride catalyst Cp ₂ HfCl ₂ taken in a molar ratio of C ₆₀ : dibenzyl sulfoxide: Cp ₂ HfCl ₂ = 0.01: (0.045-0.055) :( 0 , 0015-0.0025), in toluene, at a temperature of 140-160 ° C for 5-7 hours.