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RU2540082C2 - Method of obtaining aryl(c60-ih)[5,6]fullerene-(9h)-yl ketones - Google Patents

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

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RU2540082C2
RU2540082C2 RU2012145640/04A RU2012145640A RU2540082C2 RU 2540082 C2 RU2540082 C2 RU 2540082C2 RU 2012145640/04 A RU2012145640/04 A RU 2012145640/04A RU 2012145640 A RU2012145640 A RU 2012145640A RU 2540082 C2 RU2540082 C2 RU 2540082C2
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fullerene
ketones
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Усеин Меметович Джемилев
Айрат Рамилевич Туктаров
Марина Альфисовна Фамутдинова
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Федеральное Государственное Бюджетное Учреждение Науки Институт Нефтехимии И Катализа Ран
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Abstract

FIELD: chemistry.
SUBSTANCE: claimed invention relates to method of obtaining aryl (C60-Ih)[5,6]fullerene-1(9H)-yl ketones of generatl formula
Figure 00000015
(1):
Figure 00000016
,
Figure 00000017
. 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,
Figure 00000017
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

Description

Предлагаемое изобретение относится к области органического синтеза, а именно к способу получения арил(С60-Ih)[5,6]фуллерен-1(9H)-ил кетонов общей формулы (1):The present invention relates to the field of organic synthesis, and in particular to a method for producing aryl (C 60 -I h ) [5,6] fullerene-1 (9H) -yl ketones of the general formula (1):

Figure 00000001
;
Figure 00000002
;
Figure 00000003
,
Figure 00000001
;
Figure 00000002
;
Figure 00000003
,

Функционально замещенные фуллерены могут найти применение в качестве комплексообразователей, сорбентов, биологически активных соединений, а также при создании новых материалов с заданными электронными, магнитными и оптическими свойствами. (Л.Н.Сидоров, М.А.Юровская, А.Я.Борщевский, И.В.Трушков, И.Н.Иоффе. Фуллерены: Учебное пособие, М.: Издательство «Экзамен», 2005, 688 с [1], Л.Б.Пиотровский, О.И.Киселев. Фуллерены в биологии, СПб.: ООО «Издательство “Росток”», 2006, 336 с [2]).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. (L.N. Sidorov, M.A. ], LB Piotrovsky, OI Kiselev. Fullerenes in biology, St. Petersburg: Rostok Publishing House LLC, 2006, 336 p [2]).

Известен способ (Li, F. - B.; Liu, Т. - Х.; Huang, Y. - S.; Wang, G. - W. J. Org. Chem. 2009, 74, 7743-7749 [3]) получения смеси продуктов, состоящей из 1,2- и 1,4-бисаддуктов 4 в условиях реакции фуллерена С60 2 с карбоновыми кислотами 3 в присутствии тетраацетата свинца [Pb(ОАс)4] в качестве катализатора.A known method (Li, F. - B .; Liu, T. - X .; Huang, Y. - S .; Wang, G. - WJ Org. Chem. 2009, 74, 7743-7749 [3]) to obtain a mixture products consisting of 1,2- and 1,4-bisadducts 4 under the reaction of fullerene C 60 2 with carboxylic acids 3 in the presence of lead tetraacetate [Pb (OAc) 4 ] as a catalyst.

Figure 00000004
Figure 00000004

Известный способ не позволяет получать арил(С60-4)[5,6]фуллерен-1(9H)-ил кетоны общей формулы (1).The known method does not allow to obtain aryl (C 60 -4) [5,6] fullerene-1 (9H) -yl ketones of the general formula (1).

Известен способ (Dzhemilev, U. М.; Ibragimov, A. G.; Khafizova, L. О.; Khalilov, L. М.; Vasil'ev, Yu. V.; Tomilov, Yu. V. Russ. Chem. Bull. 2001, 50, 297-299 [4]) получения фуллероциклопропанолов 6 взаимодействием образующихся in situ фуллереналюмациклопропанов 5 с эфирами карбоновых кислот под действием Ni-катализатора при комнатной температуре.The known method (Dzhemilev, U. M .; Ibragimov, AG; Khafizova, L. O .; Khalilov, L. M; Vasil'ev, Yu. V .; Tomilov, Yu. V. Russ. Chem. Bull. 2001 , 50, 297-299 [4]) for the preparation of fullerocyclopropanols 6 by reaction of in situ fullerenalumumacyclopropanes 5 with carboxylic acid esters under the influence of a Ni catalyst at room temperature.

Figure 00000005
Figure 00000005

Известный способ не позволяет получать арил(C60-Ih)[5,6]фуллерен-1(9H)-ил кетоны общей формулы (1).The known method does not allow to obtain aryl (C 60 -I h ) [5,6] fullerene-1 (9H) -yl ketones of the general formula (1).

Таким образом, в литературе отсутствуют сведения по синтезу арил(C60-Ih)[5,6]фуллерен-1(9H)-ил кетонов (1).Thus, in the literature there is no information on the synthesis of aryl (C 60 -I h ) [5,6] fullerene-1 (9H) -yl ketones (1).

Предлагается новый способ получения арил(C60-Ih)[5,6]фуллерен-1(9H)-ил кетонов (1).A new method is proposed for producing aryl (C 60 -I h ) [5,6] fullerene-1 (9H) -yl ketones (1).

Сущность способа заключается во взаимодействии фуллерена (Сда) (2) с эфирами арилкарбоновых кислот формулы ArC(O)OMe (Ar=фенил, бифенил,

Figure 00000003
) в толуоле под действием катализатора Ti(OiPr)4 в присутствии EtMgBr, взятыми в мольном соотношении С60:эфир:Ti(OiPr)4: EtMgBr = 1:(5-15):(5-15):(30-50), предпочтительно 1:10:10:40, при температуре 0°С в течение 5-30 мин. Получают арил(С60-Ih)[5,6]фуллерен-1(9H)-ил кетоны (1) с выходом 44-68%. Реакция протекает по схеме:The essence of the method consists in the interaction of fullerene (SDA) (2) with esters of arylcarboxylic acids of the formula ArC (O) OMe (Ar = phenyl, biphenyl,
Figure 00000003
) in toluene under the action of a Ti (OiPr) 4 catalyst in the presence of EtMgBr, taken in a molar ratio of C 60 : ether: 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 Receive aryl (C 60 -I h ) [5,6] fullerene-1 (9H) -yl ketones (1) with a yield of 44-68%. The reaction proceeds according to the scheme:

Figure 00000006
Figure 00000006

Figure 00000007
;
Figure 00000002
;
Figure 00000008
Figure 00000007
;
Figure 00000002
;
Figure 00000008

Проведение указанной реакции в присутствии титанового катализатора [Ti] больше 10-кратного избытка по отношению к фуллерену С60 не приводит к существенному увеличению выхода целевого продукта (1). Применение титанового катализатора [Ti] в количестве меньше 10-кратного избытка по отношению к фуллерену C60 снижает выход целевого продукта, что связано с образованием побочных продуктов в виде аддуктов карбомагнирования. Реакцию следует проводить при температуре 0°С. Проведение реакции при более высокой температуре (например, 20°С) нецелесообразно, поскольку приводит к образованию побочных продуктов реакции, при меньшей температуре (например, -5-(-10)°С) снижается скорость реакции.Carrying out this reaction in the presence of a titanium catalyst [Ti] more than a 10-fold excess with respect to fullerene C 60 does not lead to a significant increase in the yield of the target product (1). The use of a titanium catalyst [Ti] in an amount of less than a 10-fold excess with respect to fullerene C 60 reduces the yield of the target product, which is associated with the formation of by-products in the form of carbomagnetization adducts. The reaction should be carried out at a temperature of 0 ° C. The reaction at a higher temperature (for example, 20 ° C) is impractical because it leads to the formation of by-products of the reaction, at a lower temperature (for example, -5 - (- 10) ° C), the reaction rate decreases.

Арил(C60-Ih)[5,6]фуллерен-1(9H)-ил кетоны (1) образуются только с участием фуллерена[60] и эфиров ароматических карбоновых кислот под действием Ti-катализатора.Aryl (C 60 -I h ) [5,6] fullerene-1 (9H) -yl ketones (1) are formed only with the participation of fullerene [60] and aromatic carboxylic acid esters under the action of a Ti catalyst.

Существенные отличия предлагаемого способа:Significant differences of the proposed method:

Предлагаемый способ базируется на использовании в качестве катализатора исключительно Ti(Oi-Pr)4. Предлагаемый способ в отличие от известных позволяет селективно получать арил(C60-Ih)[5,6]фуллерен-1(9H)-ил кетоны (1), синтез которых в литературе не описан.The proposed method is based on the use of exclusively Ti (Oi-Pr) 4 as a catalyst. The proposed method, unlike the known ones, allows one to selectively obtain aryl (C 60 -I h ) [5,6] fullerene-1 (9H) -yl ketones (1), the synthesis of which is not described in the literature.

Способ поясняется примерами.The method is illustrated by examples.

К охлажденному до 0°С раствору 20 мг (0.0278 ммоль) С6о-фуллерена в 20 мл сухого толуола в атмосфере аргона последовательно добавляют 0.03 мл (0.278 ммоль) метилового эфира бензойной кислоты, 0.08 мл (0.278 ммоль) Ti-катализатора и по каплям 1.112 ммоль раствора EtMgBr в диэтиловом эфире. Через 10 мин реакционную массу обрабатывают 5%-ным водным раствором HCl. Органический слой пропускают через колонку с небольшим слоем силикагеля. Получают фенил(C60-Ih)[5,6]фуллерен-1(9H)-ил кетон с выходом 57% (по данным ВЭЖХ).To a cooled 0 ° C solution of 20 mg (0.0278 mmol) of C 6 a-fullerene in 20 ml of dry toluene under an argon atmosphere were successively added 0.03 ml (0.278 mmol) of the methyl ester of benzoic acid, 0.08 ml (0.278 mmol) Ti-catalyst and dropwise 1.112 mmol of a solution of EtMgBr in diethyl ether. After 10 min, the reaction mass is treated with 5% aqueous HCl. The organic layer is passed through a column with a small layer of silica gel. Get phenyl (C 60 -I h ) [5,6] fullerene-1 (9H) -yl ketone with a yield of 57% (according to HPLC).

Спектральные характеристики (1)Spectral characteristics (1)

Figure 00000009
Figure 00000009
Выход 57%. Спектр ЯМР lH: 7.39 (с, 1H, C60-H), 7.73 (т, 2H 2СН, J=7), 7.79 (т, 1H, СН, J=7), 8.72 (д, 2Н, 2СН, J=7).Yield 57%. Nuclear Magnetic Resonance Spectrum l H: 7.39 (s, 1H, C 60 -H), 7.73 (t, 2H 2CH, J = 7), 7.79 (t, 1H, CH, J = 7), 8.72 (d, 2H, 2CH, J = 7). Спектр ЯМР 13С: 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. 13 C NMR spectrum: 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.
Figure 00000010
Figure 00000010
 Выход 45%. Спектр ЯМР 1Н: 7.4-7.64 (м, 9Н, 9СН), 7.71 (с, 1H, С60-Н).Yield 45%. 1 H NMR spectrum: 7.4-7.64 (m, 9H, 9CH), 7.71 (s, 1H, C 60 -H). Спектр ЯМР 13С: 55.99, 79.36, 13 C NMR spectrum: 55.99, 79.36, 127.14, 128.53, 128.99, 129.45, 127.14, 128.53, 128.99, 129.45, 129.58, 129.88, 130.73, 135.33, 129.58, 129.88, 130.73, 135.33, 135.99, 138.13, 139.32, 139.56, 135.99, 138.13, 139.32, 139.56, 140.44, 140.73, 141.21, 141.49, 140.44, 140.73, 141.21, 141.49, 141.74, 142.04, 142.18, 142.54, 141.74, 142.04, 142.18, 142.54, 142.71, 143.16, 144.14, 144.71, 142.71, 143.16, 144.14, 144.71, 145.24, 145.32, 145.51, 145.78, 145.24, 145.32, 145.51, 145.78, 146.14, 146.27, 146.46, 147.05, 146.14, 146.27, 146.46, 147.05, 147.28, 147.36, 149.05, 153.39, 147.28, 147.36, 149.05, 153.39, 197.77.197.77.
Figure 00000011
Figure 00000011
 Выход 53%. Спектр ЯМР 1Н: 4.03 (с, 3Н, СН3), 7.48 (с, 1H, С60-H), 8.35 (д, 2Н, 2СН, J=8), 8.63 (д, 2Н, 2СН, J=8).Yield 53%. 1 H NMR spectrum: 4.03 (s, 3H, CH 3 ), 7.48 (s, 1H, C 60 -H), 8.35 (d, 2H, 2CH, J = 8), 8.63 (d, 2H, 2CH, J = 8). Спектр ЯМР 13С: 52.47, 57.12, 79.20, 13 C NMR spectrum: 52.47, 57.12, 79.20, 129.21, 130.08, 135.61, 136.23, 129.21, 130.08, 135.61, 136.23, 136.40, 141.72, 142.24, 142.85, 136.40, 141.72, 142.24, 142.85, 143.16, 143.41, 144.40, 144.79, 143.16, 143.41, 144.40, 144.79, 145.49, 145.55, 145.64, 145.87, 145.49, 145.55, 145.64, 145.87, 146.49, 146.97, 147.49, 147.93, 146.49, 146.97, 147.49, 147.93, 148.25, 152.03, 165.67, 196.24.148.25, 152.03, 165.67, 196.24.

Другие примеры, подтверждающие способ, приведены в таблице Other examples of the method are shown in the table.

№ п/пNo. p / p ArAr Мольное соотношение C60: эфир: Ti(Oi-Pr)4: EtMgBr, ммольThe molar ratio of C 60 : ether: Ti (Oi-Pr) 4 : EtMgBr, mmol Время реакции, минReaction time, min Выход целевых продуктов, %The yield of target products,%   PhPh       1one   1:10:10:401: 10: 10: 40 1010 5757 22   1:15:10:401: 15: 10: 40 1010 6161 33   1:5:10:401: 5: 10: 40 1010 5353 4four   1:10:15:501: 10: 15: 50 1010 6868 55   1:10:5:301: 10: 5: 30 1010 4444 66   1:10:10:401: 10: 10: 40 30thirty 6262 77   1:10:10:401: 10: 10: 40 55 5151 88

Figure 00000002
Figure 00000002
1:10:10:401: 10: 10: 40 30thirty 4545 99
Figure 00000012
Figure 00000012
 1:10:10:401: 10: 10: 40 20twenty 5353

Реакции проводили в инертной атмосфере при температуре 0°С в толуоле в качестве растворителя.The reaction was carried out in an inert atmosphere at 0 ° C in toluene as a solvent.

Claims (1)

Способ получения арил(C60-Ih)[5,6]фуллерен-1(9H)-ил кетонов общей формулы (1):
Figure 00000001
;
Figure 00000002
;
Figure 00000003

характеризующийся тем, что C60-фуллерен взаимодействует с эфирами ароматических карбоновых кислот формулы ArC(O)OMe (Ar=фенил, бифенил,
Figure 00000003
) в толуоле под действием катализатора Ti(OiPr)4 в присутствии EtMgBr, при мольном соотношении C60: эфир: Ti(OiPr)4: EtMgBr=1:(5-15):(5-15):(30-50), при температуре 0°С в течение 5-30 мин. The method of obtaining aryl (C 60 -I h ) [5,6] fullerene-1 (9H) -yl ketones of the general formula (1):
Figure 00000001
;
Figure 00000002
;
Figure 00000003

characterized in that C60-fullerene interacts with aromatic carboxylic acid esters of the formula ArC (O) OMe (Ar = phenyl, biphenyl,
Figure 00000003
) in toluene under the action of a Ti (OiPr) 4 catalyst in the presence of EtMgBr, with a molar ratio of C 60 : ether: Ti (OiPr) 4 : EtMgBr = 1: (5-15) :( 5-15) :( 30-50) at a temperature of 0 ° C for 5-30 minutes
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2610092C1 (en) * 2015-11-24 2017-02-07 Федеральное Государственное Бюджетное Учреждение Науки Институт Нефтехимии И Катализа Ран METHOD OF PRODUCING 1'-AMINO-1'-ETHYL (CYCLOALKYLIDENE) ACETYL- (C60-Ih) [5,6] FULLERO [2 ', 3': 1,9] CYCLOPROPANES
RU2714319C1 (en) * 2019-08-15 2020-02-14 Федеральное государственное бюджетное научное учреждение Уфимский федеральный исследовательский центр Российской академии наук Method for selective production of substituted 1-styryl-2-hydrofullerenes

Citations (1)

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RU2240302C1 (en) * 2003-04-14 2004-11-20 ГУ Институт нефтехимии и катализа Академии наук Республики Башкортостан и УНЦ РАН Method for preparing 1-(dialkoxymethyl)-2-hydro[60]fullerenes

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RU2240302C1 (en) * 2003-04-14 2004-11-20 ГУ Институт нефтехимии и катализа Академии наук Республики Башкортостан и УНЦ РАН Method for preparing 1-(dialkoxymethyl)-2-hydro[60]fullerenes

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Tzirakis M.D. et al, Acyl Radical Reactions in Fullerene Chemistry: Direct Acylation of [60]Fullerene through an Efficient Decatungstate-Photomediated Approach. Journal of the American Chemical Society, 2009, 131(11), 4063-4069. Fa-Bao Li et al, Synthesis of Fullerene-Fused Lactones and Fullerenyl Esters: Reaction of [60]Fullerene with Carboxylic Acids Promoted by Manganese(III) Acetate and Lead(IV) Acetate. J. Org. Chem., 2009, 74(20), 7743-7749. *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2610092C1 (en) * 2015-11-24 2017-02-07 Федеральное Государственное Бюджетное Учреждение Науки Институт Нефтехимии И Катализа Ран METHOD OF PRODUCING 1'-AMINO-1'-ETHYL (CYCLOALKYLIDENE) ACETYL- (C60-Ih) [5,6] FULLERO [2 ', 3': 1,9] CYCLOPROPANES
RU2714319C1 (en) * 2019-08-15 2020-02-14 Федеральное государственное бюджетное научное учреждение Уфимский федеральный исследовательский центр Российской академии наук Method for selective production of substituted 1-styryl-2-hydrofullerenes

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