RU2342381C2 - Method of obtaining 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 3,4-fullero(60)tetrahydrothiophen-1-on of formula (I)

. Essence of method lies in interaction of fullerene C₆₀ with dimethylsulfoxide in presence of catalyst Cp₂ZrCl₂ in toluol medium at temperature ~20 °C during 66-78 hours. Target product output is 56-79%.

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

1 ex, 1 tbl

Description

The present invention relates to organic chemistry, specifically to a method for producing 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 ([1], F. Effenberger, G. Grube. Synthesis, 1998, 9, 1372-1379) for the thermal production of oligothienyl fullerene of formula (2) by reaction of C ₆₀ with 2-substituted 4,6-dihydro-5H-5λ ⁶ - thieno [3,4-b] thiophene-5,5-dione in a solution of chlorobenzene or 1,2,4-trichlorobenzene according to the scheme

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

A known method ([2], H. Ishida, K. Itoh, M.Ohno. Tetrahrdron, 2001, 57, 1737-1747) for preparing fullerotetrahydrothiophen-1-one of the formula (1) 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 addition product with m-chloroperbenzoic acid according to the scheme

The disadvantage of this method is the high energy intensity of the process and the fire hazard in the first stage. At this stage, the reaction can be carried out only at elevated temperatures in boiling toluene (110 ° C). In the second stage, explosive m-chloroperbenzoic acid is used for oxidation.

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

The essence of the method consists in the interaction of fullerene C ₆₀ with dimethyl sulfoxide Me ₂ S = 0 in the presence of a catalyst of zirconacene dichloride (Cp ₂ ZrCl ₂ ), taken in a molar ratio of respectively 0.01: (0.045-0.055) :( 0.0015-0.0025), preferably 0.01: 0.05: 0.0020, at room temperature (~ 20 ° C) for 66-78 hours, preferably 72 hours, in a toluene solution. The yield of 3,4-fullero [60] tetrahydrothiophen-1-one (1) is 56-79% (according to HPLC). The reaction proceeds according to the scheme.

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

Carrying out the above reaction in the presence of a zirconium catalyst of zirconacenedichloride Cp ₂ ZrCl ₂ more than 25 mol.% With respect to C ₆₀ does not significantly increase the yield of the target product (1). The use of a catalyst of zirconacene dichloride Cp ₂ ZrCl ₂ less than 15 mol.% With respect to C ₆₀ reduces the yield of product (1), which is possibly associated with a decrease in catalytically active centers in the reaction mass.

A change in the ratio of the starting reagents towards a significant increase in the content of dimethyl 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 one-stage method is based on the use of dimethyl sulfoxide and a catalyst of zirconacenedichloride Cp ₂ ZrCl ₂ as a starting reagent. The reaction proceeds at a temperature of ~ 20 ° C in toluene. In the known two-stage method, bis (trimethylsilylmethyl) sulfoxide and m-chloroperbenzoic acid are used as starting reagents, the reaction proceeds in o-dichlorobenzene at a temperature of 110 ° C:

The proposed process, unlike the known one, is not energy consuming, fire or explosive, and allows to obtain 3,4-fullero [60] tetrahydrothiophen-1-one (1) even at room temperature.

The method is illustrated by the following examples.

EXAMPLE 1. 0.01 mmol of fullerene C ₆₀ , 10 ml of “dry” toluene, 0.05 mmol of dimethyl sulfoxide and 0.002 mmol of Cp ₂ ZrCl ₂ catalyst are placed in a 50 ml glass flask, stirred for 72 hours at a temperature of 20 ° C., 3,4-fullero is obtained [60] tetrahydrothiophen-1-one (1) in 71% yield (according to HPLC).

¹³ C NMR spectrum of 3,4-fullero [60] tetrahydrothiophen-1-one (1) (δ, ppm): 64.83 (C ^2.5 ), 74.12 (C ^3.4 ). The signals of the carbon atoms of the fullerene fragment are located in the region of 139-158 ppm.

Other examples confirming the method are given in the table.

Table 1 №№ The molar ratio, C ₆₀ : Me ₂ S = O: Cp ₂ ZrCl ₂ , mmol Reaction time, hour Yield (1),% one 2 3 four one. 0.01: 0.05: 0.002 72 71 2. 0.01: 0.055: 0.002 72 73 3. 0.01: 0.045: 0.002 72 65 four. 0.01: 0.05: 0.0025 72 79 5. 0.01: 0.05: 0.0015 72 56 6. 0.01: 0.05: 0.002 78 75 7. 0.01: 0.05: 0.002 66 63

Toluene was used as a solvent, since it has a high solubility of fullerene C ₆₀ ; reactions were carried out at room temperature (~ 20 ° C).

Claims (1)

The method of obtaining 3,4-fullero [60] tetrahydrothiophen-1-one (1)

by the interaction of fullerene C ₆₀ with dimethyl sulfoxide in the presence of a catalyst of zirconacene dichloride Cp ₂ ZrCl ₂ taken in a molar ratio of C ₆₀ : dimethyl sulfoxide: Cp ₂ ZrCl ₂ = 0.01: (0.045-0.055) :( 0.0015-0.0025), in toluene, at room temperature (~ 20 ° C) for 66-78 hours