RU2517170C2 - METHOD OF PRODUCING N-ALKYL AND N-ARYLCARBOXAMIDYL-1aH,2'H-[1,2]PYRAZOLINO[3',4':1,9](C60-Ih)-[5,6]FULLERENES - Google Patents

METHOD OF PRODUCING N-ALKYL AND N-ARYLCARBOXAMIDYL-1aH,2'H-[1,2]PYRAZOLINO[3',4':1,9](C60-Ih)-[5,6]FULLERENES Download PDF

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RU2517170C2
RU2517170C2 RU2012115956/04A RU2012115956A RU2517170C2 RU 2517170 C2 RU2517170 C2 RU 2517170C2 RU 2012115956/04 A RU2012115956/04 A RU 2012115956/04A RU 2012115956 A RU2012115956 A RU 2012115956A RU 2517170 C2 RU2517170 C2 RU 2517170C2
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alkyl
fullerenes
pyrazolino
arylcarboxamidyl
acac
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Усеин Меметович Джемилев
Айрат Рамилевич Туктаров
Лилия Линатовна Хузина
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Федеральное Государственное Бюджетное Учреждение Науки Институт Нефтехимии И Катализа Ран
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Abstract

FIELD: chemistry.
SUBSTANCE: present invention relates to a method of producing functionally substituted fullerene derivatives, and specifically to a method of producing N-alkyl- and N-arylcarboxamidyl-1aH,2'H-[1,2]pyrazolino[3',4':1,9](C60-Ih)-[5,6]fullerenes of formula (1). Said compounds can be used as highly active starting substances in synthesis of new-generation medicinal preparations for treating dangerous human diseases. The method involves reacting fullerene (C60) (2) with alkyl- and aryldiazoamides of formula N2CHC(O)NR (R = cyclohexyl, phenyl, adamantyl) in o-dichlorobenzene (o-DCB) in the presence of a three-component catalyst system {Pd(acac)2 : 2PPh3 : 4Et3Al}, taken in molar ratio C60 : diazo compound : Pd(acac)2 : PPh3 : Et3Al = 1:(3-7):(0.1-0.3):(0.2-0.6):(0.4-1.2), preferably 1:5:0.2:0.4:0.8, at temperature of 80°C for 0.5-1.5 hours.
EFFECT: selective production of desired compounds with output of 44-68%
Figure 00000019
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Figure 00000020
,
Figure 00000021
,

Description

Предлагаемое изобретение относится к области органического синтеза, а именно к способу получения N-алкил- и N-арилкарбоксамидил-1aH,2'H-[1,2]пиразолино[3',4':1,9](C60-Ih)-[5,6]фуллеренов общей формулыThe present invention relates to the field of organic synthesis, and in particular to a method for producing N-alkyl- and N-arylcarboxamidyl-1aH, 2'H- [1,2] pyrazolino [3 ', 4': 1,9] (C 60 -I h ) - [5,6] fullerenes of the general formula

Figure 00000001
Figure 00000002
;
Figure 00000003
;
Figure 00000004
Figure 00000001
Figure 00000002
;
Figure 00000003
;
Figure 00000004

Карбоксипроизводные метанофуллеренов могут найти применение в качестве высокоактивных исходных веществ в синтезе лекарственных препаратов нового поколения для лечения опасных заболеваний человека (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]).Carboxy derivatives of methanofullerenes can be used as highly active starting materials in the synthesis of new generation drugs for the treatment of dangerous human diseases (L.N. Sidorov, M.A. Yurovskaya, A.Ya. Borschevsky, I.V. Trushkov, I.N. Ioffe, Fullerenes: Textbook.- M .: Examination Publishing House, 2005, 688 pp. [1], LB Piotrovsky, OI Kiselev. Fullerenes in Biology, St. Petersburg: Rostock Publishing House ”, 2006, 336 p. [2]).

Известен способ (R.Gonzalez, B.W.Knight, F.Wudl. J.Org.Chem., 1994, 59, 7949 [3]) получения продукта межмолекулярной циклизации 4 в условиях реакции фуллерена C60 2 со сложными диазоамидами 3 в присутствии тетраперфторбутирата диродия [Rh2(pfb)4] в качестве катализатора:A known method (R. Gonzalez, BWKnight, F.Wudl. J.Org.Chem., 1994, 59, 7949 [3]) to obtain the product of intermolecular cyclization 4 under the reaction of fullerene C 60 2 with complex diazoamides 3 in the presence of tetraperfluorobutyrate dirodium [ Rh 2 (pfb) 4 ] as a catalyst:

Figure 00000005
Figure 00000005

Известный способ не позволяет получать N-алкил- и N-арилкарбоксамидил-1aH,2'H-[1,2]пиразолино[3',4':1,9](C60-Ih)-[5,6]фуллерены общей формулы (1).The known method does not allow to obtain N-alkyl and N-arylcarboxamidyl-1aH, 2'H- [1,2] pyrazolino [3 ', 4': 1,9] (C 60 -I h ) - [5,6] fullerenes of the general formula (1).

Известен способ (A.Skiebe, A.Hirsch. J.Chem.Soc., Chem.Commun., 1994, 335 [4]) получения смеси метано- (5) и стереоизомерных гомофуллеренов (6, 7) с общим выходом 20-30% реакцией С60-фуллерена (2) с диазоамидами в кипящем толуоле в течение 48 ч:A known method (A. Skiebe, A. Hirsch. J. Chem. Soc., Chem. Commun., 1994, 335 [4]) for producing a mixture of methano- (5) and stereoisomeric homofullerenes (6, 7) with a total yield of 20- 30% reaction of C 60 -fullerene (2) with diazoamides in boiling toluene for 48 hours:

Figure 00000006
Figure 00000006

Figure 00000007
;
Figure 00000008
;
Figure 00000009
;
Figure 00000010
Figure 00000007
;
Figure 00000008
;
Figure 00000009
;
Figure 00000010

Известный способ не позволяет получать N-алкил- и N-арилкарбоксамидил-1aH,2'H-[1,2]пиразолино[3',4':1,9](C60-Ih)-[5,6]фуллерены общей формулы (1).The known method does not allow to obtain N-alkyl and N-arylcarboxamidyl-1aH, 2'H- [1,2] pyrazolino [3 ', 4': 1,9] (C 60 -I h ) - [5,6] fullerenes of the general formula (1).

Таким образом, в литературе отсутствуют сведения по синтезу N-алкил- и N-арилкарбоксамидил-1aH,2'H-[1,2]пиразолино[3',4':1,9](C60-Ih)-[5,6]фуллеренов (1).Thus, there is no information in the literature on the synthesis of N-alkyl- and N-arylcarboxamidyl-1aH, 2'H- [1,2] pyrazolino [3 ', 4': 1.9] (C 60 -I h ) - [ 5,6] fullerenes (1).

Предлагается новый способ получения N-алкил- и N-арилкарбоксамидил-1aH,2'H-[1,2]пиразолино[3',4':1,9](C60-Ih)-[5,6]фуллеренов (1).A new method is proposed for the preparation of N-alkyl- and N-arylcarboxamidyl-1aH, 2'H- [1,2] pyrazolino [3 ', 4': 1.9] (C 60 -I h ) - [5,6] fullerenes (one).

Сущность способа заключается во взаимодействии фуллерена (C60) (2) с алкил- или арилдиазоамидами формулы N2CHC(O)NR (R = циклогексил, фенил, адамантил) в o-дихлорбензоле (o-ДХБ) в присутствии трехкомпонентной каталитической системы {Pd(acac)2 : 2PPh3 : 4Et3Al}, взятыми в мольном соотношении C60 : диазосоединение : Pd(acac)2 : PPh3 : Et3Al = 1:(3-7):(0.1-0.3):(0.2-0.6):(0.4-1.2), предпочтительно 1:5:0.2:0.4:0.8,при температуре 80°С в течение 0.5-1.5 ч. N-алкил- и N-арилкарбоксамидил-1aH,2'H-[1,2]пиразолино[3',4':1,9](C60-Ih)-[5,6]фуллерены (1) с выходом 44-68%. Реакция протекает по схеме:The essence of the method consists in the interaction of fullerene (C 60 ) (2) with alkyl or aryl diazoamides of the formula N 2 CHC (O) NR (R = cyclohexyl, phenyl, adamantyl) in o-dichlorobenzene (o-DCB) in the presence of a three-component catalytic system { Pd (acac) 2 : 2PPh 3 : 4Et 3 Al}, taken in a molar ratio of C 60 : diazo compound: Pd (acac) 2 : PPh 3 : Et 3 Al = 1: (3-7) :( 0.1-0.3): (0.2-0.6) :( 0.4-1.2), preferably 1: 5: 0.2: 0.4: 0.8, at a temperature of 80 ° C for 0.5-1.5 hours. N-alkyl- and N-arylcarboxamidyl-1aH, 2'H- [1,2] pyrazolino [3 ', 4': 1.9] (C 60 -I h ) - [5.6] fullerenes (1) with a yield of 44-68%. The reaction proceeds according to the scheme:

Figure 00000011
Figure 00000011

Figure 00000002
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Figure 00000003
;
Figure 00000004
Figure 00000002
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Figure 00000003
;
Figure 00000004

Проведение указанной реакции в присутствии палладиевого катализатора [Pd] больше 20 мол. % по отношению к фуллерену C60 не приводит к существенному увеличению выхода целевого продукта (1). Применение палладиевого катализатора [Pd] в количестве меньше 20 мол. % по отношению к фуллерену C60 снижает выход целевого продукта, что связано с уменьшением реакционных центров. Реакцию следует проводить при температуре 80°С. Проведение реакции при более высокой температуре (например, 110°С) связано с увеличением энергозатрат, при меньшей температуре (например, 40°С) снижается скорость реакции.Carrying out the specified reaction in the presence of a palladium catalyst [Pd] more than 20 mol. % with respect to fullerene C 60 does not lead to a significant increase in the yield of the target product (1). The use of palladium catalyst [Pd] in an amount of less than 20 mol. % relative to fullerene C 60 reduces the yield of the target product, which is associated with a decrease in reaction centers. The reaction should be carried out at a temperature of 80 ° C. The reaction at a higher temperature (for example, 110 ° C) is associated with an increase in energy consumption, at a lower temperature (for example, 40 ° C), the reaction rate decreases.

N-алкил- и N-арилкарбоксамидил-1aH,2'H-[1,2]пиразолино[3',4':1,9](C60-Ih)-[5,6]фуллерены (1) образуются только с участием фуллерена [60] и диазоамидов.N-alkyl- and N-arylcarboxamidyl-1aH, 2'H- [1,2] pyrazolino [3 ', 4': 1.9] (C 60 -I h ) - [5,6] fullerenes (1) are formed only with the participation of fullerene [60] and diazoamides.

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

Предлагаемый способ базируется на использовании в качестве катализатора трехкомпонентного катализатора Pd(acac)2-PPh3-Et3Al. Предлагаемый способ в отличие от известных позволяет селективно получать N-алкил- и N-арилкарбоксамидил-1aH,2'H-[1,2]пиразолино[3',4':1,9](C60-Ih)-[5,6]фуллерены (1), синтез которых в литературе не описан.The proposed method is based on the use of a three-component catalyst Pd (acac) 2-PPh 3 -Et 3 Al as a catalyst. The proposed method, unlike the known ones, allows one to selectively obtain N-alkyl- and N-arylcarboxamidyl-1aH, 2'H- [1,2] pyrazolino [3 ', 4': 1,9] (C 60 -I h ) - [ 5,6] fullerenes (1), the synthesis of which is not described in the literature.

Способ поясняется примерами.The method is illustrated by examples.

К раствору 0.002 ммолей Pd(acac)2 в 0.5 мл o-ДХБ в токе сухого аргона при температуре -5°С и перемешивании добавляют 0.004 ммолей PPh3, 0.008 ммолей Et3Al и 0.01 ммолей C60-фуллерена в 1 мл o-ДХБ. Реакционную массу нагревают до 80°С и по каплям добавляют 0.05 ммолей циклогексил диазоамида в 0.5 мл o-ДХБ. Через 1 ч реакционную массу охлаждают и пропускают через колонку с небольшим слоем силикагеля. Получают N-циклогексилкарбоксамидил-1aH,2'H-[1,2]пиразолино[3',4':1,9](C60-Ih)-[5,6]фуллерен с выходом 57% (по данным ВЭЖХ).To a solution of 0.002 mmol Pd (acac) 2 in 0.5 ml of o-DCB in a stream of dry argon at a temperature of -5 ° C and stirring, add 0.004 mmol of PPh 3 , 0.008 mmol of Et 3 Al and 0.01 mmol of C 60 -fullerene in 1 ml of o- DHB. The reaction mass is heated to 80 ° C and 0.05 mmol of cyclohexyl diazoamide in 0.5 ml of o-DCB is added dropwise. After 1 h, the reaction mass is cooled and passed through a column with a small layer of silica gel. Receive N-cyclohexylcarboxamidyl-1aH, 2'H- [1,2] pyrazolino [3 ', 4': 1.9] (C 60 -I h ) - [5,6] fullerene with a yield of 57% (according to HPLC )

Спектральные характеристики (1):Spectral characteristics (1):

R = циклогексил

Figure 00000012
R = cyclohexyl
Figure 00000012
Выход 57%. Спектр ЯМР 1Н: 1.37 и 1.78 (оба м, 2H, CH2), 1.46 и 2.16 (оба м, 4H, 2CH2), 1.88 (м, 4Н, 2CH2), 4.01 (м, 1H, СН), 6.78 (уш.с, 1H, NH), 8.08 (уш.с, 1H, NH).Yield 57%. 1 H NMR spectrum: 1.37 and 1.78 (both m, 2H, CH 2 ), 1.46 and 2.16 (both m, 4H, 2CH 2 ), 1.88 (m, 4H, 2CH 2 ), 4.01 (m, 1H, CH), 6.78 (br s, 1H, NH); 8.08 (br s, 1H, NH). Спектр ЯМР 13С: 25.38 (2C), 26.05, 33.31 (2С), 49.08, 80.09, 136.23, 137.11, 140.28, 141.87, 141.94, 142.29, 142.41, 142.52, 142.67, 142.87, 142.93, 143.17, 144.18, 144.38, 144.67, 145.23, 145.41, 145.76, 146.02, 146.06, 146.36, 146.45, 147.17, 147.53, 147.86, 148.39, 157.61. 13 C NMR spectrum: 25.38 (2C), 26.05, 33.31 (2C), 49.08, 80.09, 136.23, 137.11, 140.28, 141.87, 141.94, 142.29, 142.41, 142.52, 142.67, 142.87, 142.93, 143.17, 144.18, 144.38, 144.67 , 145.23, 145.41, 145.76, 146.02, 146.06, 146.36, 146.45, 147.17, 147.53, 147.86, 148.39, 157.61. R = фенил
Figure 00000013
R = phenyl
Figure 00000013
 Выход 55%. Спектр ЯМР 1H 7.23 (м, 1H, СН), 7.43 (м, 2H, 2CH), 7.73 (м, 2H, 2CH), 8.81 (уш.с, 1H, NH).Yield 55%. 1 H NMR spectrum 7.23 (m, 1H, CH), 7.43 (m, 2H, 2CH), 7.73 (m, 2H, 2CH), 8.81 (br s, 1H, NH). Спектр ЯМР 13С: 62.90, 88.18, 119.92, 125.28, 127.67, 136.36, 137.06, 137.17, 140.33, 140.35, 141.93, 141.94, 142.27, 142.44, 142.56, 142.65, 142.69, 142.91, 142.96, 142.98, 143.19, 144.08, 144.20, 144.40, 144.64, 145.26, 145.29, 145.40, 145.85, 146.06, 146.61, 146.43, 146.49, 147.21, 147.57, 147.89, 148.69, 156.09. 13 C NMR spectrum: 62.90, 88.18, 119.92, 125.28, 127.67, 136.36, 137.06, 137.17, 140.33, 140.35, 141.93, 141.94, 142.27, 142.44, 142.56, 142.65, 142.69, 142.91, 142.96, 142.98, 143.19, 144.08, 144.20 , 144.40, 144.64, 145.26, 145.29, 145.40, 145.85, 146.06, 146.61, 146.43, 146.49, 147.21, 147.57, 147.89, 148.69, 156.09.

R = адамантил

Figure 00000014
R = adamantyl
Figure 00000014
Выход 44%. Спектр ЯМР 1Н: 1.76 (м, 6H, 3CH2), 2.05 (м, 6H, 3CH2), 2.21 (м, 3H, 3CH), 6.84 (с, 1H, NH), 8.08 (с, 1H, NH).Yield 44%. 1 H NMR spectrum: 1.76 (m, 6H, 3CH 2 ), 2.05 (m, 6H, 3CH 2 ), 2.21 (m, 3H, 3CH), 6.84 (s, 1H, NH), 8.08 (s, 1H, NH ) Спектр ЯМР 13С: 30.10, 36.66, 41.86, 53.16, 66.09, 80.03, 136.22, 140.27, 140.32, 141.89, 141.94, 142.25, 142.41, 142.52,42.67, 142.86, 142.93, 142.99, 144.19, 144.39, 144.48, 144.68, 145.22, 145.24, 145.42, 145.75, 146.01, 146.05, 146.36, 146.45, 147.16, 147.57, 147.84, 148.71, 157.25. 13 C NMR spectrum: 30.10, 36.66, 41.86, 53.16, 66.09, 80.03, 136.22, 140.27, 140.32, 141.89, 141.94, 142.25, 142.41, 142.52,42.67, 142.86, 142.93, 142.99, 144.19, 144.39, 144.48, 144.68, 145.22 , 145.24, 145.42, 145.75, 146.01, 146.05, 146.36, 146.45, 147.16, 147.57, 147.84, 148.71, 157.25.

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

Таблица 1Table 1 № п/пNo. p / p RR Мольное соотношение C60 : диазоамид : Pd(acac)2 : PPh3 : Et3Al, ммольThe molar ratio of C 60 : diazoamide: Pd (acac) 2 : PPh 3 : Et 3 Al, mmol Время реакции, часReaction time, hour Выход целевых продуктов, %The yield of target products,%   циклогексилcyclohexyl       1one   1:5:0.2:0.4:0.81: 5: 0.2: 0.4: 0.8 1one 5757 22   1:7:0.2:0.4:0.81: 7: 0.2: 0.4: 0.8 1one 6161 33   1:3:0.2:0.4:0.81: 3: 0.2: 0.4: 0.8 1one 5353 4four   1:5:0.3:0.6:1.21: 5: 0.3: 0.6: 1.2 1one 6868 55   1:5:0.1:0.2:0.41: 5: 0.1: 0.2: 0.4 1one 4444 66   1:5:0.2:0.4:0.81: 5: 0.2: 0.4: 0.8 1.51.5 6262 77   1:5:0.2:0.4:0.81: 5: 0.2: 0.4: 0.8 0.50.5 5151 88 фенилphenyl 1:5:0.2:0.4:0.81: 5: 0.2: 0.4: 0.8 1one 5555 99 адамантилadamantyl 1:5:0.2:0.4:0.81: 5: 0.2: 0.4: 0.8 1one 4444

Реакции проводили при температуре 80°С в o-дихлорбензоле в качестве растворителя.The reaction was carried out at a temperature of 80 ° C in o-dichlorobenzene as a solvent.

Claims (1)

Способ получения N-алкил- и N-арилкарбоксамидил-1aH,2'H-[1,2]пиразолино[3',4':1,9](C60-Ih)-[5,6]фуллеренов общей формулы (I):
Figure 00000001
Figure 00000002
;
Figure 00000003
;
Figure 00000004

характеризующийся тем, что C60-фуллерен взаимодействует с алкил- и арилдиазоамидами формулы N2CHC(O)NR в o-дихлорбензоле (o-ДХБ) в присутствии трехкомпонентной каталитической системы {Pd(acac)2 : 2PPh3 : 4Et3Al}, при мольном соотношении C60 : диазосоединение : Pd(acac)2 : PPh3 : Et3Al, равном 1:(3-7):(0.1-0.3):(0.2-0.6):(0.4-1.2), температуре 80°С в течение 0.5-1.5 ч. The method of obtaining N-alkyl- and N-arylcarboxamidyl-1aH, 2'H- [1,2] pyrazolino [3 ', 4': 1,9] (C 60 -I h ) - [5,6] fullerenes of the General formula (I):
Figure 00000001
Figure 00000002
;
Figure 00000003
;
Figure 00000004

characterized in that the C 60 fullerene interacts with alkyl and aryl diazoamides of the formula N 2 CHC (O) NR in o-dichlorobenzene (o-DCB) in the presence of a three-component catalytic system {Pd (acac) 2 : 2PPh 3 : 4Et 3 Al} , at a molar ratio of C 60 : diazo compound: Pd (acac) 2 : PPh 3 : Et 3 Al, equal to 1: (3-7) :( 0.1-0.3) :( 0.2-0.6) :( 0.4-1.2), temperature 80 ° C for 0.5-1.5 hours
RU2012115956/04A 2012-04-19 2012-04-19 METHOD OF PRODUCING N-ALKYL AND N-ARYLCARBOXAMIDYL-1aH,2'H-[1,2]PYRAZOLINO[3',4':1,9](C60-Ih)-[5,6]FULLERENES RU2517170C2 (en)

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А.Р.ТУКТАРОВ И ДР. "Ковалентное связывание фуллерена С60 с фармакозначимыми соединениями", Изв.АН, сер.хим., 2011, N4, с.648-652. A.R.TUCTAROV ET AL "Palladium-catalyzed selective cycloaddition of diazo compounds to [60]fullerene", ARKIVOC, 2011 (viii), p.54-66; . *

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