Method of 2,3-fullero[60]-7-phenyl-7-phosphabicyclo[2,2,1]heptane production

FIELD: chemistry.

SUBSTANCE: invention refers to organic chemistry, namely, to method of production of functionally substituted fullerenes to be applied as complexing agents, sorbents, biologically active compounds, as well as for production of new materials with specified electronic, magnetic and optical properties. Substance of the method consists in production of 2,3-fullero[60]-7-phenyl-7-phosphabicycklo[2.2.1]heptanes of formula (I) as resulted from reaction of fullerene C60 and phenylphospholane with catalyst Cp2TiCl2 added in toluol medium at temperature 140-160°C within 4-8 hours.

EFFECT: new method of selective production of functionally substituted fullerenes with end product yield 46-68%.

9 ex, 1 tbl

 

The present invention relates to organic chemistry, specifically to a method for producing 2,3-fullero[60]-7-phenyl-7-phosphabicyclo[2.2.1]heptane General formula (I)

Functionally substituted fullerenes can be used as complexing agents, sorbents, biologically active compounds, as well as the creation of new materials with tailored electronic, magnetic and optical properties.

The known method ([1], Yourenew, Vppsa, Nigericin, HEMPATHANE, Lsherry, Ipersev, Fgetline, Ore. WPI. An. Ser. chem., 2002, No. 2, 317-320) obtain phosphorylated methanofullerenes formula (2) by reaction With60with bis(dialkoxybenzene)bromoethanol in a solution of toluene

The known method does not allow to obtain 2,3-fullero[60]-7-phenyl-7-phosphabicyclo[2.2.1]heptane (1).

The known method ([2], S.-H.Wu, W.-Q.Sun, D.-W.Zhang, L.-H.Shu, H.-M.Wu, J.-F.Xu, X.-F.Lao. Tetrahedron Lett., 1998, 39, 9233-9236) obtain the compounds of formula (3) reaction of joining oxide trialkylphosphine to C60in boiling toluene to yield 48% scheme

The known method does not allow to obtain 2,3-fullero[60]-7-phenyl-7-phosphabicyclo[2.2.1]heptane (1).

Thus, the literature contains no information on the selective synthesis of 2,3-fullero[60]-7-phenyl-7-postaviti the lo[2.2.1]heptane (1).

We propose a new way to obtain 2,3-fullero[60]-7-phenyl-7-phosphabicyclo[2.2.1]heptane (1).

The method consists in the interaction of fullerene With60with phenylphosphino General formulataken in a molar ratio of 0.01:(0.01-0.011), preferably 0.01:0.0105, in the presence of a catalyst of titaniumdioxide (Cp2TiCl2), taken in an amount of 15 to 25 mol.% in relation to the fullerene C60at a temperature of 140-160°C for 4-8 h in a solution of toluene. The yield of 2,3-fullero[60]-7-phenyl-7-phosphabicyclo[2.2.1]heptane (1) is (according to HPLC) 46-68%. The reaction proceeds according to the scheme

Phenylphosphorus take with excess relative to the fullerene C60to improve the yield of the target product (1). Reducing the number phenylphosphine against With60impractical as it may lead to a decrease in the yield of the target product.

2,3-Fullero[60]-7-phenyl-7-phosphabicyclo[2.2.1]heptane (1) is formed only with the participation of fullerene[60] and phenylphosphine.

Carrying out the reaction at a higher temperature, for example, 200°leads to the formation of seal products. At a lower temperature, for example, 100°decreases the reaction rate.

The conduct of a specified reaction in the presence of a catalyst Cp2TiCl2more than 25 mol.% in relation to60not p is igodit to a significant increase in the yield of the target product (1). The use of the catalyst Cp2TiCl2less than 15 mol. % compared to60reduces the yield of the product (1), which is connected, possibly, with a reduction of catalytically active sites in the reaction mass.

Changing the ratio of initial reagents in a significant increase of the content of phenylphosphine towards fullerene[60] lead to the attachment of additional molecules of the original cyclic phosphine to the molecule With60.

Significant differences of the proposed method

The proposed method is based on using as starting reagent phenylphosphine and catalyst Cp2TiCl2. In the known method is used, the oxide trialkylphosphine. The proposed method, in contrast to the known, allows you to selectively obtain 2,3-fullero[60]-7-phenyl-7-phosphabicyclo[2.2.1]heptane (1), the synthesis of which is not described in literature.

The method is illustrated by the following examples:

EXAMPLE 1. In the metal "finger" autoclave with a volume of 17 ml) in an argon atmosphere put 0.01 mmole of fullerene C6010 ml of dry toluene, 0.0105 mmole phenylphosphine and 0.002 mmol of catalyst Cp2TiCl2, stirred for 6 hours at a temperature of 150°receive 2,3-fullero[60]-7-phenyl-7-phosphabicyclo[2.2.1]heptane General formula (1) with a yield of 59% (according to HPLC).

An NMR spectrum13With 2,3-fullero[60]-7-phenyl-7-phosphabicyclo the[2.2.1]heptane (1) (δ , ppm):

29.85 (5,6), 74.93 (2,3), 44.84 (1,4),
144.72 (8), 136.66 (9,13), 127.71
(With10,12), 125.68 (C11). Signals
carbon atoms of fullerene
fragment located in the field
137-156.

Other examples of the method shown in the table

№№ p/pThe molar ratio, With60::Cp2TiCl2mmolThe reaction temperature, °Reaction time, hoursOutput (1), %
12345
1.0.01:0.0105:0.002150659
2.0.01:0.011:0.002150662
3.0.01:0.010:0.002150655
4.0.01:0.0105:0.0025150668
5.0.01:0.0105:0.0015150653
6. 0.01:0.0105:0.002160661
7.0.01:0.0105:0.002140646
8.0.01:0.0105:0.002150863
9.0.01:0.0105:0.002150451

As a solvent used toluene, since it has the highest solubility of the fullerene C60.

The way to obtain 2,3-fullero[60]-7-phenyl-7-phosphabicyclo [2.2.1] heptane General formula (1)

characterized in that the fullerene C60interacts with phenylphosphino General formulawhen the molar ratio60:phenylphosphorus 0,01:(from 0.01 to 0.011), in the presence of a catalyst of titaniumdioxide Cp2TiCl2taken in the amount of 15-25 mol.% in relation to the fullerene C60in the medium of toluene as solvent, at a temperature of 140-160°C for 4-8 hours



 

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< / BR>
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FIELD: chemistry.

SUBSTANCE: invention refers to organic chemistry, namely, to method of production of functionally substituted fullerenes to be applied as complexing agents, sorbents, biologically active compounds, as well as for production of new materials with specified electronic, magnetic and optical properties. Substance of the method consists in production of 2,3-fullero[60]-7-phenyl-7-phosphabicycklo[2.2.1]heptanes of formula (I) as resulted from reaction of fullerene C60 and phenylphospholane with catalyst Cp2TiCl2 added in toluol medium at temperature 140-160°C within 4-8 hours.

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