RU2455273C2 - Method of producing optically active spiro-homofullerenes - Google Patents

Method of producing optically active spiro-homofullerenes Download PDF

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RU2455273C2
RU2455273C2 RU2010139062/04A RU2010139062A RU2455273C2 RU 2455273 C2 RU2455273 C2 RU 2455273C2 RU 2010139062/04 A RU2010139062/04 A RU 2010139062/04A RU 2010139062 A RU2010139062 A RU 2010139062A RU 2455273 C2 RU2455273 C2 RU 2455273C2
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optically active
homofullerenes
spiro
acac
pph
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Усеин Меметович Джемилев (RU)
Усеин Меметович Джемилев
Айрат Рамилевич Туктаров (RU)
Айрат Рамилевич Туктаров
Вячеслав Владимирович Королев (RU)
Вячеслав Владимирович Королев
Леонард Мухибович Халилов (RU)
Леонард Мухибович Халилов
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Учреждение Российской Академии Наук Институт Нефтехимии И Катализа Ран
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Abstract

FIELD: chemistry.
SUBSTANCE: invention relates to a method of producing optically active spiro-homofullerenes of formula (1) and (2):
Figure 00000001
Figure 00000013
characterised by that C60-fullerene reacts with optically active diazocompounds generated in situ via oxidation of hydrazones of (-)-menthone and D-(+)-camphor with MnO2, in o-dichlorobenzene in the presence of a three-component catalyst system Pd(acac)2-PPh3-Et3Al, taken in molar ratio C60 : optically active hydrazone : Pd(acac)2 : PPh3 : Et3Al=0.01:(0.01-0.02):(0.0015-0.0025):(0.003-0.005):(0.006-0.01), at room temperature (about 20°C) for 1-2 hours.
EFFECT: method is distinguished from existing methods by high output of end products and selectivity of the reaction, use of a palladium complex in catalytic amounts, as well as low power consumption.
1 cl, 8 ex, 1 tbl

Description

Предлагаемое изобретение относится к области органического синтеза, а именно к способу получения оптически активных спиро-гомофуллеренов формулы (1) и (2)The present invention relates to the field of organic synthesis, and in particular to a method for producing optically active spiro-homofullerenes of the formula (1) and (2)

Figure 00000001
Figure 00000002
Figure 00000001
Figure 00000002

Оптически активные производные фуллеренов могут найти применение в качестве высокоактивных исходных веществ в синтезе лекарственных препаратов нового поколения для лечения опасных заболеваний человека, а также новых перспективных материалов для оптики (S.R.Wilson, Q.Lu, J.Cao, Y.Wu, С.J.Welch, D.I.Schuster. Tetrahedron, 1996, 52, 5131 [1]).Optically active fullerene derivatives can be used as highly active starting materials in the synthesis of new generation drugs for the treatment of dangerous human diseases, as well as promising new materials for optics (SRWilson, Q. Lu, J. Cao, Y. Wu, C.J Welch, DISchuster. Tetrahedron, 1996, 52, 5131 [1]).

Известен способ (T.Ohno, N.Martin, B.Knight, F.Wudl, T.Suzuki, H.Yu. J.Org.Chem., 1996, 61, 1306 [2]) получения спиро-метанофуллеренов (3) в смеси с аддуктами полиприсоединения в условиях фотохимической или термической реакции С60-фуллерена (4) с соответствующими циклическими диазосоединениями.A known method (T.Ohno, N. Martin, B.Knight, F.Wudl, T. Suzuki, H.Yu. J.Org.Chem., 1996, 61, 1306 [2]) for producing spiro-methanofullerenes (3) mixed with polyaddition adducts under the conditions of the photochemical or thermal reaction of C 60- fullerene (4) with the corresponding cyclic diazo compounds.

Figure 00000003
Figure 00000003

Предложенным методом невозможно получить спиро-гомофуллерены, в том числе и оптически активные производные формулы (1) и (2).The proposed method cannot obtain spiro-homofullerenes, including optically active derivatives of formulas (1) and (2).

Известен способ (Z.Li, K.H.Bouhadir, P.B.Shevlin. Tetrahedron Lett., 1996, 37, 4651 [3]) получения рацемических спиро-гомофуллеренов (5) в смеси со спиро-метанофуллеренами (6) с общим выходом 10-40% реакцией С60-фуллерена (4) с рацемическими циклическими диазосоединениями, генерируемыми in situ термолизом литиевых солей соответствующих тозилгидразонов.A known method (Z. Li, KH Bouhadir, PBShevlin. Tetrahedron Lett., 1996, 37, 4651 [3]) for the preparation of racemic spiro-homofullerenes (5) in a mixture with spiro-methanofullerenes (6) with a total yield of 10-40% of reaction C 60- fullerene (4) with racemic cyclic diazocompounds generated in situ by thermolysis of lithium salts of the corresponding tosyl hydrazones.

Figure 00000004
Figure 00000004

Известным способом невозможно селективно получить спиро-гомофуллерены, в том числе и оптически активные производные формулы (1) и (2).In a known manner it is impossible to selectively obtain spiro-homofullerenes, including optically active derivatives of formulas (1) and (2).

Предлагается эффективный способ получения оптически чистых спиро-гомофуллеренов (1) и (2).An effective method is proposed for producing optically pure spiro-homofullerenes (1) and (2).

Сущность способа заключается во взаимодействии фуллерена (С60) с оптически активными циклическими диазосоединениями, генерируемыми in situ окислением гидразонов (-)-ментона и D-(+)-камфоры с помощью MnO2, в о-дихлорбензоле, в присутствии трехкомпонентной каталитической системы Pd(acac)2-PPh3-Et3Al, при мольном соотношении С60: гидразон: Pd(acac)2:PPh3:Et3Al=0.01:(0.01-0.02):(0.0015-0.0025):(0.003-0.005):(0.006-0.01), предпочтительно 0.01:0.015:0.002:0.004:0008, при комнатной температуре (~ 20°С) в течение 1-2 ч. Получают оптически активные спиро-гомофуллерены (1) и (2) с общим выходом 30-50%. Реакции протекают по схемеThe essence of the method consists in the interaction of fullerene (C 60 ) with optically active cyclic diazocompounds generated in situ by oxidation of hydrazones of (-) - menton and D - (+) - camphor with MnO 2 , in o-dichlorobenzene, in the presence of a three-component Pd catalytic system (acac) 2 -PPh 3 -Et 3 Al, with a molar ratio of C 60 : hydrazone: Pd (acac) 2 : PPh 3 : Et 3 Al = 0.01: (0.01-0.02) :( 0.0015-0.0025) :( 0.003- 0.005) :( 0.006-0.01), preferably 0.01: 0.015: 0.002: 0.004: 0008, at room temperature (~ 20 ° C) for 1-2 hours. Optically active spiro-homofullerenes (1) and (2) are obtained with total yield of 30-50%. Reactions proceed according to the scheme.

Figure 00000005
Figure 00000005

Проведение указанной реакции в присутствии палладиевого катализатора [Pd] больше 25 мол.% по отношению к фуллерену С60 не приводит к существенному увеличению выходов целевых продуктов (1) и (2). Применение палладиевого катализатора [Pd] в количестве меньше 15 мол.% по отношению к фуллерену С60 снижает выход целевых продуктов, что связано с уменьшением реакционных центров. Реакцию следует проводить при температуре 20°С. Проведение реакции при более высокой температуре (например, 40°С) приводит к увеличению энергозатрат.Carrying out this reaction in the presence of a palladium catalyst [Pd] of more than 25 mol.% With respect to fullerene C 60 does not lead to a significant increase in the yields of the target products (1) and (2). The use of a palladium catalyst [Pd] in an amount of less than 15 mol% with respect to fullerene C 60 reduces the yield of the target products, which is associated with a decrease in reaction centers. The reaction should be carried out at a temperature of 20 ° C. Carrying out the reaction at a higher temperature (for example, 40 ° C) leads to an increase in energy consumption.

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

Предлагаемый способ базируется на использовании трехкомпонентной каталитической системы (Pd(acac)2-2PPh3-4Et3Al) в каталитических количествах, реакция завершается за 1.5 ч при комнатной температуре, что позволяет селективно синтезировать оптически активные спиро-гомофуллерены. В известном способе необходимо нагревание реакционной смеси, вследствие чего образуется смесь спиро-гомо- и спиро-метанофуллеренов.The proposed method is based on the use of a three-component catalytic system (Pd (acac) 2 -2PPh 3 -4Et 3 Al) in catalytic amounts, the reaction is completed in 1.5 hours at room temperature, which makes it possible to selectively synthesize optically active spiro-homofullerenes. In the known method, it is necessary to heat the reaction mixture, as a result of which a mixture of spiro-homo-and spiro-methanofullerenes is formed.

Способ поясняется примерами. The method is illustrated by examples.

К раствору 0.001 ммолей Pd(acac)2 в 0.5 мл о-ДХБ в токе сухого аргона при температуре -5°С и перемешивании добавляют 0.002 ммолей PPh3, 0.004 ммолей Et3Al и 0.01 ммолей С60-фуллерена в 1 мл о-ДХБ. К реакционной массе при перемешивании по каплям добавляют 0.015 ммолей соответствующего оптически активного гидразона и порциями 0.07 ммоль MnO2. Через 1.5 ч реакционную массу пропускают через колонку с небольшим слоем силикагеля. Получают оптически активные спиро-гомофуллерены (1) и (2) с выходом 30-50% (по данным ВЭЖХ).To a solution of 0.001 mmol Pd (acac) 2 in 0.5 ml of o-DCB in a stream of dry argon at a temperature of -5 ° С and stirring, add 0.002 mmol of PPh 3 , 0.004 mmol of Et 3 Al and 0.01 mmol of C 60- fullerene in 1 ml of o- DHB. 0.015 mmol of the corresponding optically active hydrazone and 0.07 mmol of MnO 2 are added dropwise to the reaction mass with stirring. After 1.5 h, the reaction mass was passed through a column with a small layer of silica gel. Optically active spiro-homofullerenes (1) and (2) are obtained with a yield of 30-50% (according to HPLC).

Спектральные характеристики (1)Spectral characteristics (1)

Figure 00000006
Figure 00000006
[α]D+183±8° (c1 0.021, с2 0.024 и с3 0.028 в СНСl3). ИК спектр, см-1: 527, 723, 755, 1377, 1461. УФ спектр (СНСl3), λmax, нм: 262.07, 334.82. Спектр ЯМР 1Н, δ, м.д.: 1.08 (д, 3Н, С(10')Н3, 3J=7.2), 1.30 (д, 3Н, С(9')Н3, 3J=7.2), 1.32 (д, 3Н, С(8')Н3, 3J=7.2), 1.37-2.04 (м, 2Н, С(4')Н2), 1.46 (дд, Heq, С(6')Н2, 2J=14.8, 3J=6.4), 1.68 (дд, Нax, С(6')Н2, 2J=14.8, 3J=3.0), 2.13 (м, Н, С(5')Н), 2.16-2.40 (м, 2Н, С(3')Н2), 2.53 (м, Н, С(7')Н), 4.64 (дт, Нax С(2')Н, 2J=14.0, 3J=7.0). Спектр ЯМР 13С, δ, м.д.: 22.46, 22.67, 23.56, 24.00, 25.56, 27.83, 28.58, 29.63, 48.41, 53.38, 134.77, 135.58, 135.67, 136.44, 136.61, 137.53, 137.60, 137.81, 137.96, 139.02, 139.25, 139.78, 139.83, 140.09, 140.37, 140.42, 140.53, 140.60, 140.92, 141.13, 141.31, 141.35, 141.70, 141.77, 142.10, 142.46, 142.52, 142.55, 142.60, 142.67, 142.72, 142.88, 142.90, 143.00, 143.06, 143.08, 143.17, 143.20, 143.66, 143.69, 143.74, 143.79, 143.85, 143.99, 144.06, 144.11, 144.32, 144.48, 144.90, 145.42, 147.40, 147.49. Масс-спектр (MALDI-TOF/TOF): 858.850 [М]-.[α] D + 183 ± 8 ° (c 1 0.021, c 2 0.024 and c 3 0.028 in CHCl 3 ). IR spectrum, cm -1 : 527, 723, 755, 1377, 1461. UV spectrum (CHCl 3 ), λ max , nm: 262.07, 334.82. 1 H NMR, δ, ppm .: 1.08 (d, 3H, C (10 ') 3 H, 3 J = 7.2), 1.30 (d, 3H, C (9') 3 H, 3 J = 7.2 ), 1.32 (d, 3H, C (8 ') H 3 , 3 J = 7.2), 1.37-2.04 (m, 2H, C (4') H 2 ), 1.46 (dd, H eq , C (6 ') ) Н 2 , 2 J = 14.8, 3 J = 6.4), 1.68 (dd, Н ax , С (6 ') Н 2 , 2 J = 14.8, 3 J = 3.0), 2.13 (m, Н, С (5 ') H), 2.16-2.40 (m, 2H, C (3') H 2 ), 2.53 (m, H, C (7 ') H), 4.64 (dt, H ax C (2') H, 2 J = 14.0, 3 J = 7.0). 13 C NMR spectrum, δ, ppm: 22.46, 22.67, 23.56, 24.00, 25.56, 27.83, 28.58, 29.63, 48.41, 53.38, 134.77, 135.58, 135.67, 136.44, 136.61, 137.53, 137.60, 137.81, 137.96, 139.02, 139.25, 139.78, 139.83, 140.09, 140.37, 140.42, 140.53, 140.60, 140.92, 141.13, 141.31, 141.35, 141.70, 141.77, 142.10, 142.46, 142.52, 142.55, 142.60, 142.67, 142.72, 142.88, 142.90, 142.90, 142.90. 143.06, 143.08, 143.17, 143.20, 143.66, 143.69, 143.74, 143.79, 143.85, 143.99, 144.06, 144.11, 144.32, 144.48, 144.90, 145.42, 147.40, 147.49. Mass spectrum (MALDI-TOF / TOF): 858.850 [M] - . Спектральные характеристики (2)Spectral characteristics (2)
Figure 00000007
Figure 00000007
 [α]D+120.9±2° (c1 0.021, с2 0.024 и с3 0.028 в CHCl3). ИК спектр, см-1: 527, 755, 1189, 1389, 1463, 1514. УФ спектр (CHCl3), λmax нм: 263.94, 335.11. Спектр ЯМР 1H, δ, м.д.: 1.07 (с, 3Н, С(10')Н3), 1.13 (с, 3Н, С(9')Н3), 1.27 (м, Нax С(5')Н2), 1.32 (м, Нeq, С(3')Н2), 1.82 (м, Н, С(4')Н), 1.84 (м, Нax, С(3')Н2), 1.96 (м, Hax, С(6')Н2), 1.98 (м, Heq, С(5')Н2), 2.18 (с, 3Н, С(8')Н3), 2.44 (дд, Heq, С(6')Н2, 2J=12.0, 3J=2.4). Спектр ЯМР 13С, δ, м.д.: 20.33, 21.09, 21.32, 28.72, 34.02, 45.74, 46.43, 50.47, 56.57, 62.89, 132.99,133.97,134.29, 135.78, 137.38, 137.52, 137.78, 138.04, 138.20, 138.57, 138.77, 139.09, 140.17, 140.33, 140.38, 140.71(2С), 140.83, 141.00, 141.51, 141.57, 141.60, 141.92, 141.99, 142,11, 142.19, 142.49, 142.60, 142.63, 142.69, 142.80, 142.88, 143.16, 143.21, 143.42, 143.57, 143.77, 143.83, 143.94, 144.05, 144.36, 144.40, 144.95, 144.99, 145.30, 146.15, 147.77, 147.88. Масс-спектр (MALDI-TOF/TOF): 856.818 [М]-.[α] D + 120.9 ± 2 ° (c 1 0.021, c 2 0.024 and c 3 0.028 in CHCl 3 ). IR spectrum, cm -1 : 527, 755, 1189, 1389, 1463, 1514. UV spectrum (CHCl 3 ), λ max nm: 263.94, 335.11. 1 H NMR spectrum, δ, ppm: 1.07 (s, 3H, C (10 ') H 3 ), 1.13 (s, 3H, C (9') H 3 ), 1.27 (m, H ax C ( 5 ') H 2 ), 1.32 (m, H eq , C (3') H 2 ), 1.82 (m, H, C (4 ') H), 1.84 (m, H ax , C (3') H 2 ), 1.96 (m, H ax , C (6 ') H 2 ), 1.98 (m, H eq , C (5') H 2 ), 2.18 (s, 3H, C (8 ') H 3 ), 2.44 (dd, Heq , C (6 ') H 2 , 2 J = 12.0, 3 J = 2.4). 13 C NMR spectrum, δ, ppm: 20.33, 21.09, 21.32, 28.72, 34.02, 45.74, 46.43, 50.47, 56.57, 62.89, 132.99,133.97,134.29, 135.78, 137.38, 137.52, 137.78, 138.04, 138.20, 138.57, 138.77, 139.09, 140.17, 140.33, 140.38, 140.71 (2С), 140.83, 141.00, 141.51, 141.57, 141.60, 141.92, 141.99, 142,11, 142.19, 142.49, 142.60, 142.63, 142.69, 142.80, 142.88, 143.16 , 143.21, 143.42, 143.57, 143.77, 143.83, 143.94, 144.05, 144.36, 144.40, 144.95, 144.99, 145.30, 146.15, 147.77, 147.88. Mass spectrum (MALDI-TOF / TOF): 856.818 [M] - .

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

Таблица 1Table 1 № п/пNo. p / p RR Мольное соотношение С60:H2N-N=R:Pd(acac)2:PPh3:Et3Al, ммольThe molar ratio of C 60 : H 2 NN = R: Pd (acac) 2 : PPh 3 : Et 3 Al, mmol Время реакции, чReaction time, h Выход целевых продуктов, %The yield of target products,%  

Figure 00000008
Figure 00000008
                      1one 0.01:0.015:0.002:0.004:0.0080.01: 0.015: 0.002: 0.004: 0.008 1.51.5 4040 22 0.01:0.02:0.002:0.004:0.0080.01: 0.02: 0.002: 0.004: 0.008 1.51.5 4242 33 0.01:0.01:0.002:0.004:0.0080.01: 0.01: 0.002: 0.004: 0.008 1.51.5 3434 4four 0.01:0.015:0.0025:0.005:0.010.01: 0.015: 0.0025: 0.005: 0.01 1.51.5 50fifty 55 0.01:0.015:0.0015:0.003:0.0060.01: 0.015: 0.0015: 0.003: 0.006 1.51.5 30thirty 66 0.01:0.015:0.002:0.004:0.0080.01: 0.015: 0.002: 0.004: 0.008 22 4545 77 0.01:0.015:0.002:0.004:0.0080.01: 0.015: 0.002: 0.004: 0.008 1one 3232  
Figure 00000009
Figure 00000009
                       88 0.01:0.015:0.002:0.004:0.0080.01: 0.015: 0.002: 0.004: 0.008 1.51.5 3838 Реакции проводили при комнатной температуре (~ 20°С)The reaction was carried out at room temperature (~ 20 ° C)

Claims (1)

Способ получения оптически активных спиро-гомофуллеренов формулы (1) и (2):
Figure 00000010
Figure 00000011

характеризующийся тем, что С60-фуллерен взаимодействует с оптически активными диазосоединениями, генерируемыми in situ окислением гидразонов (-)-ментона и D-(+)-камфоры с помощью MnO3, в о-дихлорбензоле в присутствии трехкомпонентной каталитической системы Pd(асас)2-PPh3-Et3Al, взятыми в мольном соотношении С60:оптически активный гидразон: Pd(acac)2:PPh3:Et3Al=0,01:(0,01-0,02):(0,0015-0,0025):(0,003-0,005):(0,006-0,01), при комнатной температуре (~20°С) в течение 1-2 ч. The method of obtaining optically active spiro-homofullerenes of the formula (1) and (2):
Figure 00000010
Figure 00000011

characterized by the fact that C 60 fullerene interacts with optically active diazocompounds generated in situ by oxidation of hydrazones of (-) - menton and D - (+) camphor with MnO 3 in o-dichlorobenzene in the presence of a three-component Pd (acac) catalytic system 2 -PPh 3 -Et 3 Al, taken in a molar ratio of C 60 : optically active hydrazone: Pd (acac) 2 : PPh 3 : Et 3 Al = 0.01: (0.01-0.02) :( 0, 0015-0.0025) :( 0.003-0.005) :( 0.006-0.01), at room temperature (~ 20 ° C) for 1-2 hours.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006290788A (en) * 2005-04-11 2006-10-26 Matsushita Electric Ind Co Ltd Fullerene derivative, method for producing fullerene film by using the same and method for producing field-effect transistor
RU2348604C1 (en) * 2007-07-23 2009-03-10 Институт нефтехимии и катализа РАН Method of obtaining polyhydro[60]fullerenes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2006290788A (en) * 2005-04-11 2006-10-26 Matsushita Electric Ind Co Ltd Fullerene derivative, method for producing fullerene film by using the same and method for producing field-effect transistor
RU2348604C1 (en) * 2007-07-23 2009-03-10 Институт нефтехимии и катализа РАН Method of obtaining polyhydro[60]fullerenes

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Z.Li, K.H.Bouhadir, P.B.Shevlin., Convenyent Synthesys of 6,5 Open and 6,6 Closed Cycloalkylidenefullerenes, Tetrahedron Lett., 1996, 37, 4651-4654. *

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