RU2565782C1 - Method of obtaining 6-alkyl(aryl)-2,3-(c60-ih)[5,6]fullero-2,3,4,5-tetrahydropyridines - Google Patents

Method of obtaining 6-alkyl(aryl)-2,3-(c60-ih)[5,6]fullero-2,3,4,5-tetrahydropyridines Download PDF

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RU2565782C1
RU2565782C1 RU2014118800/04A RU2014118800A RU2565782C1 RU 2565782 C1 RU2565782 C1 RU 2565782C1 RU 2014118800/04 A RU2014118800/04 A RU 2014118800/04A RU 2014118800 A RU2014118800 A RU 2014118800A RU 2565782 C1 RU2565782 C1 RU 2565782C1
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Усеин Меметович Джемилев
Айрат Рамилевич Туктаров
Артур Альбертович Хузин
Зульфия Расимовна Шакирова
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Федеральное государственное бюджетное учреждение науки Институт нефтехимии и катализа Российской академии наук
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Abstract

FIELD: chemistry.
SUBSTANCE: invention relates to field of organic synthesis, namely to method of obtaining 6-alkyl(aryl)-2,3-(C60-IH)[5,6]fullero-2,3,4,5-tetrahydropyridines of general formula
Figure 00000010
where R=C5H11, Ph, 2-Naph; characterised by the fact that C60-fullerene interacts with alkyl- or arylnitriles of formula RCN (R=C5H11, Ph, 2-Naph) in toluene under action of catalyst Ti(OiPr)4 in presence of EtMgBr,with molar ratio C60 : nitrile : Ti(OiPr)4 : EtMgBr = 1:(5-15):(5-15):(30-50), at temperature 80°C for 5-30 min.
EFFECT: method of obtaining fulleroheterocycles, which can be applied as complexants, sorbents, biologically active compounds, as well as in creation of novel materials with specified electronic, magnetic and optic properties, has been elaborated.
1 tbl

Description

Предлагаемое изобретение относится к области органического синтеза, а именно к способу получения 6-алкил(арил)-2,3-(C60-IH)[5,6]фуллеро-2,3,4,5-тетрагидропиридинов общей формулы (I):The present invention relates to the field of organic synthesis, and in particular to a method for producing 6-alkyl (aryl) -2,3- (C 60 -I H ) [5,6] fullero-2,3,4,5-tetrahydropyridines of the general formula ( I):

Figure 00000001
Figure 00000001

Фуллерогетероциклы 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]).Fulleroheterocycles can be used as complexing agents, sorbents, biologically active compounds, as well as in the creation of new materials with predetermined electronic, magnetic and optical properties. (L.N. Sidorov, M.A. Yurovskaya, A.Ya. Borschevsky, I.V. Trushkov, I.N. ], LB Piotrovsky, OI Kiselev. Fullerenes in biology, St. Petersburg: Rostok Publishing House LLC, 2006, 336 s [2]).

Известен способ (H.-T. Yang, W.-L. Ren, X.-J. Ruan, Z.-Y. Tian, X.-C. Liang, C. Han, X.-Q. Sun, C.-B. Miao. Tetrahedron Lett. 2013, 54, 1428-1431 [3]) получения фуллерооксазинов 4 реакцией фуллерена C60 2 с α-алкоксил/фенолил/ацилоксил кетоксимов 3 в присутствии карбоната натрия [Na2CO3] в качестве катализатора.The known method (H.-T. Yang, W.-L. Ren, X.-J. Ruan, Z.-Y. Tian, X.-C. Liang, C. Han, X.-Q. Sun, C .-B. Miao. Tetrahedron Lett. 2013, 54, 1428-1431 [3]) for the preparation of fulleroxazines 4 by the reaction of fullerene C 60 2 with α-alkoxyl / phenolyl / acyloxyl ketoximes 3 in the presence of sodium carbonate [Na 2 CO 3 ] as catalyst.

Figure 00000002
Figure 00000002

Известный способ не позволяет получать 6-алкил(арил)-2,3-(C60-IH)[5,6]фуллеро-2,3,4,5-тетрагидропиридины общей формулы (1).The known method does not allow to obtain 6-alkyl (aryl) -2,3- (C 60 -I H ) [5,6] fullero-2,3,4,5-tetrahydropyridines of the general formula (1).

Известен способ (G.-W. Wang, J.-X. Li. Org. Biomol. Chem., 2006, 4, 4063-4064 [4]) получения дигидропиридоизохинолиновых производных фуллерена 7 реакцией фуллерена C60 2 с изохинолином 5 и ацетилендикарбоксилатом 6 в кипящем толуоле.A known method (G.-W. Wang, J.-X. Li. Org. Biomol. Chem., 2006, 4, 4063-4064 [4]) for the preparation of dihydropyridoisoquinoline derivatives of fullerene 7 by reaction of fullerene C 60 2 with isoquinoline 5 and acetylenedicarboxylate 6 in boiling toluene.

Figure 00000003
Figure 00000003

Известный способ не позволяет получать 6-алкил(арил)-2,3-(C60-IH)[5,6]фуллеро-2,3,4,5-тетрагидропиридины общей формулы (1).The known method does not allow to obtain 6-alkyl (aryl) -2,3- (C 60 -I H ) [5,6] fullero-2,3,4,5-tetrahydropyridines of the general formula (1).

Таким образом, в литературе отсутствуют сведения по синтезу 6-алкил(арил)-2,3-(C60-IH)[5,6]фуллеро-2,3,4,5-тетрагидропиридинов (1).Thus, there is no information in the literature on the synthesis of 6-alkyl (aryl) -2,3- (C 60 -I H ) [5,6] fullero-2,3,4,5-tetrahydropyridines (1).

Предлагается новый способ получения 6-алкил(арил)-2,3-(C60-IH)[5,6]фуллеро-2,3,4,5-тетрагидропиридинов (1).A new method is proposed for producing 6-alkyl (aryl) -2,3- (C 60 -I H ) [5,6] fullero-2,3,4,5-tetrahydropyridines (1).

Сущность способа заключается во взаимодействии фуллерена (C60) (2) с алкил- и арилнитрилами формулы RCN (R=C5H11, Ph, 2-Naph) в толуоле под действием катализатора Ti(OiPr)4 в присутствии EtMgBr, взятыми в мольном соотношении C60 : нитрил : Ti(OiPr)4 : EtMgBr = 1:(5-15):(5-15):(30-50), предпочтительно 1:10:10:40, при температуре 80°C в течение 5-30 мин. Получают 6-алкил(арил)-2,3-(C60-IH)[5,6]фуллеро-2,3,4,5-тетрагидропиридины (1) с выходом 14-35%. Реакция протекает по схеме:The essence of the method consists in the interaction of fullerene (C 60 ) (2) with alkyl and aryl nitriles of the formula RCN (R = C 5 H 11 , Ph, 2-Naph) in toluene under the action of a Ti (OiPr) 4 catalyst in the presence of EtMgBr, taken molar ratio of C 60 : nitrile: Ti (OiPr) 4 : EtMgBr = 1: (5-15) :( 5-15) :( 30-50), preferably 1: 10: 10: 40, at a temperature of 80 ° C within 5-30 minutes Get 6-alkyl (aryl) -2,3- (C 60 -I H ) [5,6] fullero-2,3,4,5-tetrahydropyridines (1) with a yield of 14-35%. The reaction proceeds according to the scheme:

Figure 00000004
Figure 00000004

Проведение указанной реакции в присутствии титанового катализатора [Ti] больше 10-кратного избытка по отношению к фуллерену C60 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 80°C. Проведение реакции при более высокой температуре (например, 100°C) нецелесообразно, поскольку приводит к увеличению энергозатрат, при меньшей температуре (например, -50-60°C) 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 significantly increase 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 80 ° C. Carrying out the reaction at a higher temperature (for example, 100 ° C) is impractical because it leads to an increase in energy consumption, at a lower temperature (for example, -50-60 ° C), the reaction rate decreases.

6-Алкил(арил)-2,3-(C60-IH)[5,6]фуллеро-2,3,4,5-тетрагидропиридины (1) образуются только с участием фуллерена[60], алкил- или арилнитрилов и магнийорганических соединений под действием Ti-катализатора.6-Alkyl (aryl) -2,3- (C 60 -I H ) [5,6] fullero-2,3,4,5-tetrahydropyridines (1) are formed only with the participation of fullerene [60], alkyl or aryl nitriles and organomagnesium compounds under the action of a Ti catalyst.

Существенные отличия предлагаемого способаSignificant 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 6-алкил(арил)-2,3-(C60-IH)[5,6]фуллеро-2,3,4,5-тетрагидропиридины (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 6-alkyl (aryl) -2,3- (C 60 -I H ) [5,6] fullero-2,3,4,5-tetrahydropyridines (1), synthesis which are not described in the literature.

Способ поясняется примерами.The method is illustrated by examples.

К охлажденному до 0°C раствору 20 мг (0.0278 ммолей) C60-фуллерена в 20 мл сухого толуола в атмосфере аргона последовательно добавляют 0.08 мл (0.278 ммолей) Ti-катализатора и по каплям 0.56 ммолей раствора EtMgBr в диэтиловом эфире. Через 5 мин реакционную массу нагревают до 80°C и последовательно добавляют бензонитрила (0.278 ммолей), а также по каплям 0.56 ммолей 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 6-фенил-2,3-(C60-IH)[5,6]фуллеро-2,3,4,5-тетрагидропиридин с выходом 33% (по данным ВЭЖХ).To a solution of 20 mg (0.0278 mmol) of C 60- fullerene in 20 ml of dry toluene cooled to 0 ° C in an argon atmosphere, 0.08 ml (0.278 mmol) of Ti catalyst are successively added and 0.56 mmol of a solution of EtMgBr in diethyl ether is added dropwise. After 5 min, the reaction mass was heated to 80 ° C and benzonitrile (0.278 mmol) was successively added, as well as a 0.56 mmol solution of EtMgBr in diethyl ether dropwise. 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 6-phenyl-2,3- (C 60 -I H ) [5,6] fullero-2,3,4,5-tetrahydropyridine with a yield of 33% (according to HPLC).

Спектральные характеристики (1)Spectral characteristics (1)

Figure 00000005
Figure 00000005
Выход 20%. Спектр ЯМР 1H: 1.05 (т, 3H, CH3, J=7.5), 1.56 (м, 2H, CH2), 1.61 (м, 2H, CH2), 2.03 (м, 2H, CH2), 2.92 (т, 3H, CH3, J=7.5), 3.37 (т, 2H, CH2, J=5.6), 3.57 (т, 2H, CH2, J=5.6).Yield 20%. 1 H NMR spectrum: 1.05 (t, 3H, CH 3 , J = 7.5), 1.56 (m, 2H, CH 2 ), 1.61 (m, 2H, CH 2 ), 2.03 (m, 2H, CH 2 ), 2.92 (t, 3H, CH 3 , J = 7.5), 3.37 (t, 2H, CH 2 , J = 5.6), 3.57 (t, 2H, CH 2 , J = 5.6). Спектр ЯМР 13C: 14.54, 23.15, 26.28, 29.59, 32.23, 37.16, 42.59, 59.50, 80.89, 134.73, 135.58, 140.27, 140.37, 141.51, 141.90, 142.02, 142.19, 142.44, 142.57, 142.69, 142.75, 143.18, 144.79, 144.97, 145.29, 145.54, 145.80, 145.97, 146.39, 146.55, 146.64, 146.72, 147.96, 148.25, 155.38, 156.74, 172.76. MALDI TOF, m/z 845.107 [M]-(C68H15N). 13 C NMR spectrum: 14.54, 23.15, 26.28, 29.59, 32.23, 37.16, 42.59, 59.50, 80.89, 134.73, 135.58, 140.27, 140.37, 141.51, 141.90, 142.02, 142.19, 142.44, 142.57, 142.69, 142.75, 143.18, 144.79 , 144.97, 145.29, 145.54, 145.80, 145.97, 146.39, 146.55, 146.64, 146.72, 147.96, 148.25, 155.38, 156.74, 172.76. MALDI TOF, m / z 845.107 [M] - (C 68 H 15 N).
Figure 00000006
Figure 00000006
 Выход 33%. Спектр ЯМР 1H: 3.76 (т, 2H, CH2, J=5.6), 3.91 (т, 2H, CH2, J=5.6), 7.64 (м, 3H, 3CH), 8.34 (м, 2H, 2CH).Yield 33%. 1 H NMR spectrum: 3.76 (t, 2H, CH 2 , J = 5.6), 3.91 (t, 2H, CH 2 , J = 5.6), 7.64 (m, 3H, 3CH), 8.34 (m, 2H, 2CH) . Спектр ЯМР 13C: 26.93, 37.31, 59.51, 81.51, 127.10, 128.81, 131.10, 134.95, 135.66, 139.01, 140.30, 140.41, 141.54, 141.94, 142.04, 142.22, 142.47, 142.63, 142.72, 142.77, 143.20, 144.82, 144.98, 145.31, 145.55, 145.57, 145.60, 145.85, 145.98, 146.38, 146.40, 146.66, 146.75, 147.97, 148.29, 155.18, 156.69, 172.40. MALDI TOF, m/z 851.083 [M]- (C69H9N). 13 C NMR spectrum: 26.93, 37.31, 59.51, 81.51, 127.10, 128.81, 131.10, 134.95, 135.66, 139.01, 140.30, 140.41, 141.54, 141.94, 142.04, 142.22, 142.47, 142.63, 142.72, 142.77, 143.20, 144.82, 144.98 , 145.31, 145.55, 145.57, 145.60, 145.85, 145.98, 146.38, 146.40, 146.66, 146.75, 147.97, 148.29, 155.18, 156.69, 172.40. MALDI TOF, m / z 851.083 [M] - (C 69 H 9 N).
Figure 00000007
Figure 00000007
 Выход 25%. Спектр ЯМР 1H: 3.78 (т, 2H, CH2, J=5.6), 4.01 (т, 2H, CH2, J=5.6), 7.46 (м, H, CH), 7.63 (м, 2H, 2CH), 7.96 (с, H, CH), 8.05 (м, H, CH), 8.08 (м, H, CH), 8.60 (м, H, CH).Yield 25%. 1 H NMR Spectrum: 3.78 (t, 2H, CH 2 , J = 5.6), 4.01 (t, 2H, CH 2 , J = 5.6), 7.46 (m, H, CH), 7.63 (m, 2H, 2CH) 7.96 (s, H, CH), 8.05 (m, H, CH), 8.08 (m, H, CH), 8.60 (m, H, CH). Спектр ЯМР 13C: 26.86, 37.35, 59.59, 81.63, 126.23, 126.47, 127.98, 128.67, 129.09, 130.59, 133.14, 134.48, 134.88, 135.14, 135.00, 135.67, 136.37, 137.71, 140.27, 140.41, 141.53, 141.92, 142.03, 142.21, 142.45, 142.63, 142.73, 143.18, 144.82, 144.96, 145.31, 145.56, 145.84, 145.97, 146.37, 146.66, 148.28, 155.18, 156.72, 172.44. MALDI TOF, m/z 901.074 [M]+ (C71H11N). 13 C NMR spectrum: 26.86, 37.35, 59.59, 81.63, 126.23, 126.47, 127.98, 128.67, 129.09, 130.59, 133.14, 134.48, 134.88, 135.14, 135.00, 135.67, 136.37, 137.71, 140.27, 140.41, 141.53, 141.92, 142.03 , 142.21, 142.45, 142.63, 142.73, 143.18, 144.82, 144.96, 145.31, 145.56, 145.84, 145.97, 146.37, 146.66, 148.28, 155.18, 156.72, 172.44. MALDI TOF, m / z 901.074 [M] + (C 71 H 11 N).

Другие примеры, подтверждающие способ, приведены в табл. 1Other examples confirming the method are given in table. one

Figure 00000008
Figure 00000008

Реакции проводили в инертной атмосфере при температуре 80°C в толуоле в качестве растворителя.The reactions were carried out in an inert atmosphere at a temperature of 80 ° C in toluene as a solvent.

Claims (1)

Способ получения 6-алкил(арил)-2,3-(C60-IH)[5,6]фуллеро-2,3,4,5-тетрагидропиридинов общей формулы (1):
Figure 00000009

характеризующийся тем, что C60-фуллерен взаимодействует с алкил- или арилнитрилами формулы RCN (R=C5H11, Ph, 2-Naph) в толуоле под действием катализатора Ti(OiPr)4 в присутствии EtMgBr, при мольном соотношении C60 : нитрил : Ti(OiPr)4 : EtMgBr = 1:(5-15):(5-15):(30-50), при температуре 80°C в течение 5-30 мин. The method of obtaining 6-alkyl (aryl) -2,3- (C 60 -I H ) [5,6] fullero-2,3,4,5-tetrahydropyridines of the general formula (1):
Figure 00000009

characterized in that the C 60 fullerene interacts with alkyl or aryl nitriles of the formula RCN (R = C 5 H 11 , Ph, 2-Naph) in toluene under the influence of a Ti (OiPr) 4 catalyst in the presence of EtMgBr, in a molar ratio of C 60 : nitrile: Ti (OiPr) 4 : EtMgBr = 1: (5-15) :( 5-15) :( 30-50), at a temperature of 80 ° C for 5-30 minutes.
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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
RU2629752C1 (en) * 2016-04-26 2017-09-01 Федеральное Государственное Бюджетное Учреждение Науки Институт Нефтехимии И Катализа Ран Method of selective reception of isopropyline 5'-aryl-1'n-pyrrolidino[3',4':1,9](c60-ih)[5,6]fullerene-2'-carboxylates
RU2629754C1 (en) * 2016-05-19 2017-09-01 Федеральное Государственное Бюджетное Учреждение Науки Институт Нефтехимии И Катализа Ран Method for productio of stereoisomeric iso-propyl 5'-alkyl-1'n-pyrrolidino[3',4':1,9](c60-ih)[5,6]fullerene-2'-carboxylates mixture
RU2666726C1 (en) * 2017-07-13 2018-09-12 Федеральное государственное бюджетное научное учреждение Уфимский федеральный исследовательский центр Российской академии наук Method for selective production of 2',5'-unsubstituted 1'-benzylpyrrolidino[3',4':1,9](c60-ih)[5,6]fullerenes
CN109988113A (en) * 2019-05-14 2019-07-09 河南师范大学 A kind of synthetic method of [60] fullerene tetrahydroquinoline derivative
CN109988113B (en) * 2019-05-14 2022-04-12 河南师范大学 Synthesis method of [60] fullerene tetrahydroquinoline derivative

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