RU2283302C1 - Method for preparing 2-(1-methyl-2-(3,4-fullero[60]-pyrrolidinyl)phenol - Google Patents

Abstract

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of 2-(1-methyl-2-(3,4-fullero[60]pyrrolidinyl)phenol of the formula (1):

Method involves interaction of fullerene[60] with 2-[(dimethylamino)methyl]phenol of the general formula: (R-CH₂-N(CH₃)₂) wherein R means

in taken in the mole ratio C60 : R-CH₂-N-(CH₃)₂ = 0.01:(0.01-0.011) in the presence of Cp₂TiCl₂ as catalyst taken in the amount 15-25 mole% relatively to fullerene[60] in argon atmosphere, in toluene medium as a solvent, at temperature 140-160°C for 2-4 h. Method provides preparing the novel compound with the yield 78-86%. Compound of the formula (1) can be used as a chelating agent, sorbent and biologically active substance.

EFFECT: improved method of synthesis.

1 tbl, 1 ex

Description

The invention relates to organic chemistry, specifically to a method for producing 2- (1-methyl-2- (3,4-fullero [60] -pyrrolidinyl) phenol 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 ([2], ACTome, RFEnes, JPCTome, J. Rocha, MGPMS Maves, JAS Cavaleiro, J. Elguero. Tetrahedron, 1998, 54, 11141-11150) for the preparation of a pyrimidine derivative of fullerene [60] of the formula (3) by reaction With ₆₀ s substituted sulfylene (2) in 1,2,4-trichlorobenzene at 214 ° C in a nitrogen atmosphere with a yield of 77% according to the scheme.

The known method does not allow to obtain 2- (1-methyl-2- (3,4-fullero [60] pyrrolidinyl) phenol (1).

A known method ([1], Zheng Dagui, Li Yuliang, Yang Jingkui, Zhu Daoben. Fulleren Sci. And Technol., 1996, v.4, No. 5, 1067-1072) to obtain a pyrrolidine derivative of fullerene [60] of the formula (4) the reaction of C ₆₀ s (HCO) _n and DL-valine in a toluene solution at the boiling point of the solvent (~ 110 ° C) in a nitrogen atmosphere with a yield of 45%.

In a known manner, 2- (1-methyl-2- (3,4-fullero [60] pyrrolidinyl) phenol (1) cannot be obtained.

Thus, in the literature there is no information on the selective synthesis of 2- (1-methyl-2- (3,4-fullero [60] pyrrolidinyl) phenol (1).

A new method is proposed for producing 2- (1-methyl-2- (3,4-fullero [60] pyrrolidinyl) phenol (1).

The essence of the method consists in the interaction of fullerene [60] with 2 - [(dimethylamino) methyl] phenol (5) in the presence of a titanium catalyst Cp ₂ TiCl ₂ , in a molar ratio, respectively 0.01: (0.01-0.011) :( 0.0015-0.0025), preferably 0.01: 0.0105: 0.002, in an argon atmosphere at a temperature of 140-160 ° C, for 2-4 hours, in a toluene solution. The yield of 2- (1-methyl-2- (3,4-fullero [60] pyrrolidinyl) phenol (1) is (according to HPLC) 62-86%. The reaction proceeds according to the scheme:

2 - [(Dimethylamino) methyl] phenol (5) is taken in excess with respect to fullerene [60] in order to increase the yield of the target product (1). A decrease in the amount of 2 - [(dimethylamino) methyl] phenol (5) with respect to C _{60 is} impractical, since it leads to a sharp decrease in the yield of the target product.

2- (1-Methyl-2- (3,4-fullero [60] pyrrolidinyl) phenol (1) is formed only with the participation of fullerene [60] and 2 - [(dimethylamino) methyl] phenol (5).

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 titanium 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 catalytically active centers in the reaction mass.

A change in the ratio of the starting reagents towards a significant increase in the content of 2 - [(dimethylamino) methyl] phenol (5) with respect to fullerene [60] leads to the addition of additional phenolpyrrolidine fragments to the C ₆₀ molecule.

Significant differences of the proposed method:

1. The proposed method is based on the use of substituted phenol (5) and Ср ₂ TiCl ₂ catalyst as a starting reagent. In the known method, formaldehyde and an amino acid (DL-valine) are used. The proposed method, unlike the known one, allows the phenolpyrrolidine fragment to be introduced into the fullerene molecule to obtain 2- (1-methyl-2- (3,4-fullero [60] pyrrolidinyl) phenol (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 in an argon atmosphere, 0.01 mmol of fullerene [60], 10 ml of “dry” toluene, 0.0105 mmol of 2 - [(dimethylamino) methyl] phenol (5) and 0.002 mmol of CP ₂ catalyst are placed TiCl ₂ , stirred for 3 hours at a temperature of 150 ° C, get 2- (1-methyl-2- (3,4-fullero [60] pyrrolidinyl) phenol of General formula (1) with a yield of 78% (according to HPLC).

¹³ C NMR spectrum of 2- (1-methyl-2- (3,4-fullero [60] pyrrolidinyl) phenol (1) (5, ppm):

¹³ C NMR spectrum (δ, ppm): 45.05 (C ¹ ), 66.19 (C ² ), 77.15 (C ³ ), 79.90 (C ⁴ ), 71.43 (C ⁵ ), 128.09 (C ⁶ ), 128.71 (C ⁷ ), 119.3 (C ⁸ ), 128.61 (C ⁹ ), 113.3 (C ¹⁰ ), 156.11 (C ¹¹ ). The signals of the carbon atoms of the fullerene fragment are located in the region 140.25-154.32.

Other examples confirming the method are given in table 1.

Table 1 №№

:Cp₂TiCl₂, ммольThe molar 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 3 78 2. 0.01: 0.01: 0.002 150 3 81 3. 0.01: 0.01: 0.002 150 3 75 four. 0.01: 0.0105: 0.0025 150 3 86 5. 0.01: 0.0105: 0.0015 150 3 72 6. 0.01: 0.0105: 0.002 160 3 80 7. 0.01: 0.0105: 0.002 140 3 62 8. 0.01: 0.0105: 0.002 150 four 83 9. 0.01: 0.0105: 0.002 150 2 65

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

Claims (1)

The method of obtaining 2- (1-methyl-2- (3,4-fullero [60] -pyrrolidinyl) phenol of the General formula (1)

characterized in that fullerene [60] interacts with 2 - [(dimethylamino) methyl] phenol of the general formula (R-CH ₂ -N - ((CH ₃ ) ₂ ) Where

, in a molar ratio of C60: R-CH ₂ -N- (CH ₃ ) ₂ equal to 0.01: (0.01-0.011), in the presence of a catalyst Cp ₂ TiCl ₂ in an amount of 15-25 mol.% in relation to fullerene [60], in an argon atmosphere in toluene as a solvent at a temperature of 140-160 ° C for 2-4 hours