Method of obtaining aryl(c60-ih)[5,6]fullerene-(9h)-yl ketones

FIELD: chemistry.

SUBSTANCE: claimed invention relates to method of obtaining aryl (C60-Ih)[5,6]fullerene-1(9H)-yl ketones of generatl formula (1): , . Functionally substituted fullerenes can be applied as complexants, sorbents, biologically active compounds, as well as in creation of novel materials with specified electronic, magnetic and optic properties. Method consists in interaction of C60-fullerene with ethers of aromatic carboxylic acids of formula ArC(O)OMe (Ar = phenyl, biphenyl, in toluene under action of catalyst Ti(OiPr)4 in presence of EtMgBr, with molar ratio C60: ether: Ti(OiPr)4: EtMgBr=1:(5-15):(5-15):(30-50), at temperature 0°C for 5-30 min.

EFFECT: invention makes it possible to obtain target products with output 44-68%.

1 tbl, 9 ex

 

The present invention relates to the field of organic synthesis, and in particular to a method for producing aryl(C60-Ih)[5,6]fullerene-1(9H)-yl ketone of General formula (1):

;;,

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. (L. N. Sidorov, M. A. Yurovsky, A. J. Borshevsky, I. C. Trushkov, I. N. Ioffe. Fullerenes: a tutorial, M.: Publishing house "Examination", 2005, 688 [1], L. B. Piotrovsky, O. I. Kiselev. Fullerenes in biology, SPb.: LLC "Publishing house "sprout", 2006, 336 p [2]).

The known method (Li, F. - B.; Liu, T. - H.; Huang, Y. - S.; Wang, G. - W. J. Org. Chem. 2009, 74, 7743-7749 [3]) obtain a mixture of products consisting of 1,2 - and 1,4-bisadduct 4 under the reaction conditions of fullerene C602 with carboxylic acids 3 in the presence of leads to compounds, which lead [Pb(SLA)4] as a catalyst.

The known method does not allow to get aryl(C60-4)[5,6]fullerene-1(9H)-yl ketones of General formula (1).

The known method (Dzhemilev, U. M.; Ibragimov, A. G.; Khafizova, L. O.; Khalilov, L. M.; Vasil ev, Yu. V.; Tomilov, Yu. V. Russ. Chem. Bull. 2001, 50, 297-299 [4]) get fullarticlenonav 6 formed by the interaction of insitu fullerenepyrazolines 5 with esters of carboxylic acids under the action of Ni-catalyst at room temperature.

The known method does not allow to get aryl(C60-Ih)[5,6]fullerene-1(9H)-yl ketones of General formula (1).

Thus, in the literature there are no data on the synthesis of aryl(C60-Ih)[5,6]fullerene-1(9H)-yl ketone (1).

We propose a new method of obtaining aryl(C60-Ih)[5,6]fullerene-1(9H)-yl ketone (1).

The method consists in the interaction of fullerene (ASD) (2) with esters arylcarboxylic acids of the formula ArC(O)OMe (Ar=phenyl, biphenyl,) in toluene under the action of the catalyst Ti(OiPr)4in the presence of EtMgBr taken in a molar ratio With60:air:Ti(OiPr)4: EtMgBr= 1:(5-15):(5-15):(30-50), preferably 1:10:10:40 at a temperature of 0°C for 5-30 minutes Get aryl(C60-Ih)[5,6]fullerene-1(9H)-yl ketones (1) with output 44-68%. The reaction proceeds according to the scheme:

;;

The conduct of a specified reaction in the presence of a titanium catalyst [Ti] more than 10-fold excess relative to the fullerene C60does not lead to a significant increase in the yield of the target product (1). The use of titanium catalyst [Ti] in the amount of less than 10-fold excess relative to the fullerene C60reduces the yield of the target product, because arr is using by-products in the form of adducts of carbamazipine. The reaction should be carried out at a temperature of 0°C. Carrying out the reaction at a higher temperature (e.g. 20°C) is impractical because it leads to the formation of side reaction products, at a lower temperature (for example, -5-(-10)°C) decreases the reaction rate.

Aryl(C60-Ih)[5,6]fullerene-1(9H)-yl ketones (1) are formed only with the participation of fullerene[60] and esters of aromatic carboxylic acids under the action of Ti-catalyst.

Significant differences of the proposed method:

The proposed method is based on the use as catalyst exclusively Ti(Oi-Pr)4. The proposed method in contrast to the known allows you to selectively receive aryl(C60-Ih)[5,6]fullerene-1(9H)-yl ketones (1), the synthesis of which are not described in literature.

The method is illustrated by examples.

To a cooled to 0°C. a solution of 20 mg (0.0278 mmol) With6on-fullerene in 20 ml dry toluene in an argon atmosphere successively added 0.03 ml (0.278 mmol) of the methyl ester of benzoic acid, 0.08 ml (0.278 mmol) of Ti-catalyst and dropwise 1.112 mmol solution of EtMgBr in diethyl ether. After 10 min the reaction mass is treated with 5% aqueous HCl solution. The organic layer is passed through a column with a small layer of silica gel. Receive phenyl(C60-Ih)[5,6]fullerene-1(9H)-yl ketone with exit 57% (according to HPLC).

Spectral characteristics (1)
Yield 57%. An NMR spectrumlH: 7.39 (s, 1H, C60-H), 7.73 (t, 2H, 2CH, J=7), 7.79 (t, 1H, CH, J=7), 8.72 (d, 2H, 2CH, J=7).
An NMR spectrum13With: 57.15, 77.35, 129.10, 129.64, 133.39, 136.00, 136.05, 136.48, 140.19, 140.76, 141.69, 141.73, 141.88, 142.21, 142.27, 142.76, 142.85, 143.16, 143.39, 144.50, 144.78, 145.51, 145.57, 145.59, 145.82, 146.33, 146.34, 146.50, 146.52, 147.03, 147.34, 147.49, 150.68, 152.06, 197.60.
Yield 45%. An NMR spectrum1N: 7.4-7.64 (m, N, SN), 7.71 (s, 1H, C60-N).
An NMR spectrum13From: 55.99, 79.36,
127.14, 128.53, 128.99, 129.45,
129.58, 129.88, 130.73, 135.33,
135.99, 138.13, 139.32, 139.56,
140.44, 140.73, 141.21, 141.49,
141.74, 142.04, 142.18, 142.54,
142.71, 143.16, 144.14, 144.71,
145.24, 145.32, 145.51, 145.78,
146.14, 146.27, 146.46, 147.05,
147.28, 147.36, 149.05, 153.39,
197.77.
Yield 53%. An NMR spectrum1N: 4.03 (s, 3H, CH3), 7.48 (s, 1H, C 60-H), 8.35 (d, 2H, 2CH, J=8), 8.63 (d, 2H, 2CH, J=8).
An NMR spectrum13From: 52.47, 57.12, 79.20,
129.21, 130.08, 135.61, 136.23,
136.40, 141.72, 142.24, 142.85,
143.16, 143.41, 144.40, 144.79,
145.49, 145.55, 145.64, 145.87,
146.49, 146.97, 147.49, 147.93,
148.25, 152.03, 165.67, 196.24.

Other examples of the method shown in the table

№ p/pArThe molar ratio of C60: air: Ti(Oi-Pr)4: EtMgBr, mmolReaction time, minThe yield of the target products, %
Ph
11:10:10:401057
21:15:10:401061
31:5:10:40 1053
41:10:15:501068
51:10:5:301044
61:10:10:403062
71:10:10:40551
81:10:10:403045
91:10:10:402053

Reactions were carried out in an inert atmosphere at a temperature of 0°C in toluene as solvent.

The method of obtaining aryl(C60-Ih)[5,6]fullerene-1(9H)-yl ketone of General formula (1):
;;
characterized by the fact that C60-full the Ren interacts with esters of aromatic carboxylic acids of the formula ArC(O)OMe (Ar=phenyl, biphenyl,) in toluene under the action of the catalyst Ti(OiPr)4in the presence of EtMgBr, when the molar ratio C60: air: Ti(OiPr)4: EtMgBr=1:(5-15):(5-15):(30-50), at 0°C for 5-30 minutes



 

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1 ex, 1 tbl

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1 ex, 1 tbl

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25 cl, 3 tbl, 12 ex

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EFFECT: improved method of synthesis.

3 ex

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