RU2629752C1 - Method of selective reception of isopropyline 5'-aryl-1'n-pyrrolidino[3',4':1,9](c60-ih)[5,6]fullerene-2'-carboxylates - Google Patents

Method of selective reception of isopropyline 5'-aryl-1'n-pyrrolidino[3',4':1,9](c60-ih)[5,6]fullerene-2'-carboxylates Download PDF

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RU2629752C1
RU2629752C1 RU2016116457A RU2016116457A RU2629752C1 RU 2629752 C1 RU2629752 C1 RU 2629752C1 RU 2016116457 A RU2016116457 A RU 2016116457A RU 2016116457 A RU2016116457 A RU 2016116457A RU 2629752 C1 RU2629752 C1 RU 2629752C1
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fullerene
pyrrolidino
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armgbr
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Усеин Меметович Джемилев
Айрат Рамилевич Туктаров
Зульфия Расимовна Шакирова
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Федеральное Государственное Бюджетное Учреждение Науки Институт Нефтехимии И Катализа Ран
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/04—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members
    • C07D207/10—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D207/16—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals

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Abstract

FIELD: chemistry.
SUBSTANCE: invention relates to a method for preparation of fulleropyrrolidines that can be used as complexing agents, sorbents, biologically active compounds, as well as for creation of new materials with specified electronic, magnetic, and optical properties. A method for selective preparation of isopropyl-5'-aryl-1'H-pyrrolidino[3',4':1,9](C60-Ih)[5,6]fullerene-2'-carboxylates of the general formula
Figure 00000010
is characterised by C60-fullerene reaction with ethyl isocyanoacetate of the formula EtO2CCH2N+≡C in chlorobenzene under the action of the Ti(OiPr)4 catalyst in the presence of ArMgBr (where Ar = Ph, 2-MePh), taken in the molar ratio of C60:Isocyanoacetate:Ti(OiPr)4:ArMgBr = 1:(2-6):(1-5):(6-10), at a temperature of 100°C for 5-30 minutes.
EFFECT: improved method for preparation of these compounds.
1 tbl, 1 ex

Description

Изобретение относится к области органического синтеза, а именно, к способу селективного получения изо-пропил 5'-арил-1'H-пирролидино[3', 4':1, 9] (С60-Ih) [5, 6]фуллерен-2'-карбоксилатов общей формулы 1:The invention relates to the field of organic synthesis, namely, to a method for the selective production of iso-propyl 5'-aryl-1'H-pyrrolidino [3 ', 4': 1, 9] (C 60 -I h ) [5, 6] fullerene-2'-carboxylates of the general formula 1:

Figure 00000001
Figure 00000001

Пирролидинофуллерены являются перспективными соединениями 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]).Pyrrolidino-fullerenes are promising compounds as complexing agents, sorbents, biologically active compounds, and also when creating new materials with specified electronic, magnetic and optical properties (L.N. Sidorov, M.A. Yurovskaya, A.Ya. Borschevsky, I.V. Trushkov, I. N. Ioffe. Fullerenes: Textbook, M.: Publishing House "Examination", 2005, 688 pp. [1], LB Piotrovsky, OI Kiselev. Fullerenes in Biology, St. Petersburg: LLC “Publishing house Rostock”, 2006, 336 p. [2]).

Известен способ (М. Prato, Μ. Maggini, С. Giacometti, G. Scorrano, G. Sandona, G. Farnia. Tetrahedron, 1996, 52, 5221 [3]) получения пирролидинофуллерена 5 реакцией N-метилглицина 3 и формальдегида 4 с С60-фуллереном 2 в кипящем толуоле в течение 2 ч.A known method (M. Prato, Μ. Maggini, C. Giacometti, G. Scorrano, G. Sandona, G. Farnia. Tetrahedron, 1996, 52, 5221 [3]) for the preparation of pyrrolidinofullerene 5 by reaction of N-methylglycine 3 and formaldehyde 4 s With 60- fullerene 2 in boiling toluene for 2 hours

Figure 00000002
Figure 00000002

Известный способ не позволяет получать изо-пропил 5'-арил-1'H-пирролидино [3', 4':1, 9] (С60-Ih) [5, 6]фуллерен-2'-карбоксилаты общей формулы 1.The known method does not allow to obtain isopropyl 5'-aryl-1'H-pyrrolidino [3 ', 4': 1, 9] (C 60 -I h ) [5, 6] fullerene-2'-carboxylates of the general formula 1 .

Известен способ (X. Tan, D. I. Schuster, R. Wilson. Tetrahedron Lett. 1998, 39, 4187 [4]) получения смеси стереоизомерных N-незамещенных пирролидинофуллеренов (8) с выходом 15-40% реакцией С60-фуллерена (2) с альдегидами (6) и N-незамещенными аминокислотами (7) в кипящем толуоле в течение 2 ч.A known method (X. Tan, DI Schuster, R. Wilson. Tetrahedron Lett. 1998, 39, 4187 [4]) to obtain a mixture of stereoisomeric N-unsubstituted pyrrolidinofullerenes (8) with a yield of 15-40% by reaction of C 60 -fullerene (2) with aldehydes (6) and N-unsubstituted amino acids (7) in boiling toluene for 2 hours

Figure 00000003
Figure 00000003

Известный способ не позволяет селективно получать изо-пропил 5'-арил-1'H-пирролидино [3',4':1, 9] (С60-Ih) [5, 6]фуллерен-2'-карбоксилаты общей формулы 1.The known method does not allow the selective production of iso-propyl 5'-aryl-1'H-pyrrolidino [3 ', 4': 1, 9] (C 60 -I h ) [5, 6] fullerene-2'-carboxylates of the general formula one.

Таким образом, в литературе отсутствуют сведения по селективному синтезу изо-пропил 5'-арил-1'H-пирролидино [3',4':1, 9] (С60-Ih) [5,6] фуллерен-2'-карбоксилатов 1.Thus, in the literature there is no information on the selective synthesis of iso-propyl 5'-aryl-1'H-pyrrolidino [3 ', 4': 1, 9] (C 60 -I h ) [5,6] fullerene-2 ' -carboxylates 1.

Предлагается новый способ селективного получения изо-пропил 5'-арил-1'H-пирролидино [3', 4':1, 9] (С60-Ih) [5, 6]фуллерен-2'-карбоксилатов 1.A new method is proposed for the selective preparation of iso-propyl 5'-aryl-1'H-pyrrolidino [3 ', 4': 1, 9] (C 60 -I h ) [5, 6] fullerene-2'-carboxylates 1.

Сущность способа заключается во взаимодействии фуллерена (С60) (2) с этилизоцианоацетатом формулы ЕtO2ССН2N+≡С- в хлорбензоле под действием катализатора Ti(OiPr)4 в присутствии ArMgBr (где Ar=Ph, 2-MePh), взятыми в мольном соотношении С60:изоцианоацетат:Ti(OiPr)4:ArMgBr=1:(2-6):(1-5):(6-10), предпочтительно 1:4:3:8, при температуре 100°С в течение 5-30 мин. Получают изо-пропил 5'-арил-1'H-пирролидино [3', 4':1, 9](С60-Ih) [5, 6]фуллерен-2'-карбоксилаты 1 с выходом 15-60%. Реакция протекает по схемеThe essence of the method consists in the interaction of fullerene (C 60 ) (2) with an ethyl isocyanoacetate of the formula EtO 2 CCH 2 N + ≡C - in chlorobenzene under the action of a Ti (OiPr) 4 catalyst in the presence of ArMgBr (where Ar = Ph, 2-MePh), taken in a molar ratio of C 60 : isocyanoacetate: Ti (OiPr) 4 : ArMgBr = 1: (2-6) :( 1-5) :( 6-10), preferably 1: 4: 3: 8, at a temperature of 100 ° C within 5-30 minutes Iso-propyl 5'-aryl-1'H-pyrrolidino [3 ', 4': 1, 9] (C 60 -I h ) [5, 6] fullerene-2'-carboxylates 1 was obtained in a yield of 15-60% . The reaction proceeds according to the scheme.

Figure 00000004
Figure 00000004

Проведение указанной реакции в присутствии титанового катализатора [Ti] больше 3-кратного избытка по отношению к фуллерену С60 не приводит к существенному увеличению выхода целевого продукта (1). Применение титанового катализатора [Ti] в количестве меньше 3-кратного избытка по отношению к фуллерену С60 снижает выход целевого продукта, что связано с образованием побочных продуктов в виде аддуктов карбомагнирования. Реакцию следует проводить при температуре 100°С. Проведение реакции при более высокой температуре (например, 120°С) не целесообразно, поскольку приводит к увеличению энергозатрат, при меньшей температуре (например, - 60-80°С) снижается скорость реакции.Carrying out this reaction in the presence of a titanium catalyst [Ti] more than a 3-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 3-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 100 ° C. Carrying out the reaction at a higher temperature (for example, 120 ° C) is not advisable, since it leads to an increase in energy consumption, at a lower temperature (for example, 60-80 ° C), the reaction rate decreases.

изо-Пропил 5'-арил-1'H-пирролидино [3', 4':1, 9] (С60-Ih) [5, 6]фуллерен-2'-карбоксилаты 1 образуются только с участием фуллерена [60], этил изоцианоацетата и арилмагнийорганических соединений под действием Ti-катализатора.iso-Propyl 5'-aryl-1'H-pyrrolidino [3 ', 4': 1, 9] (C 60 -I h ) [5, 6] fullerene-2'-carboxylates 1 are formed only with the participation of fullerene [60 ], ethyl isocyanoacetate and aryl organomagnesium compounds 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 получать ранее труднодоступные изо-пропил 5'-арил-1'H-пирролидино [3', 4':1, 9] (С60-Ih) [5, 6] фуллерен-2'-карбоксилаты 1, синтез которых в литературе не описан.The proposed method is based on the use as the catalyst solely Ti (Oi-Pr) 4. The proposed method, unlike the known ones, allows one to obtain previously inaccessible iso-propyl 5'-aryl-1'H-pyrrolidino [3 ', 4': 1, 9] (C 60 -I h ) [5, 6] fullerene 2'-carboxylates 1, the synthesis of which is not described in the literature.

Способ поясняется примерами.The method is illustrated by examples.

Пример 1. К охлажденному до 0°С раствору 20 мг (0.0278 ммоль) C60-фуллерена в 5 мл сухого хлорбензола в атмосфере аргона последовательно добавляют 0.03 мл (0.0834 ммоль) Ti-катализатора и по каплям 0.11 мл (0.111 ммоль) 1 Μ раствора ArMgBr в диэтиловом эфире. Через 5 мин реакционную массу нагревают до 100°С и последовательно добавляют этилизоцианоацетат 0.008 мл (0.111 ммоль), а также по каплям вторую порцию 0.11 мл (0.111 ммоль) 1 Μ раствора ArMgBr в диэтиловом эфире. Через 15 мин реакционную массу обрабатывают 5%-ным водным раствором НСl. Органический слой пропускают через колонку с небольшим слоем силикагеля. Получают изо-пропил 5'-арил-1'H-пирролидино[3', 4':1, 9](С60-Ih) [5, 6]фуллерен-2'-карбоксилаты с выходом 15-60% (по данным ВЭЖХ).Example 1. To a solution of 20 mg (0.0278 mmol) of C 60- fullerene in 5 ml of dry chlorobenzene cooled to 0 ° C in an argon atmosphere, 0.03 ml (0.0834 mmol) of Ti catalyst are successively added and 0.11 ml (0.111 mmol) 1 Μ dropwise a solution of ArMgBr in diethyl ether. After 5 min, the reaction mass is heated to 100 ° C and 0.008 ml (0.111 mmol) of ethyl isocyanoacetate is added sequentially, as well as a second drop of 0.11 ml (0.111 mmol) of a 1 Μ solution of ArMgBr in diethyl ether. After 15 minutes, the reaction mass is treated with 5% aqueous HCl. The organic layer is passed through a column with a small layer of silica gel. Iso-propyl 5'-aryl-1'H-pyrrolidino [3 ', 4 ' : 1, 9] (C 60 -I h ) [5, 6] fullerene-2'-carboxylates was obtained in a yield of 15-60% ( according to HPLC).

Figure 00000005
Figure 00000005

Figure 00000006
Figure 00000006

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

Figure 00000007
Figure 00000007

Реакции проводили в инертной атмосфере при температуре 100°С в хлорбензоле в качестве растворителя.The reactions were carried out in an inert atmosphere at a temperature of 100 ° C in chlorobenzene as a solvent.

Claims (3)

Способ селективного получения изо-пропил 5'-арил-1'H-пирролидино[3',4':1,9](С60-Ih)[5,6]фуллерен-2'-карбоксилатов общей формулы (1):A process for selectively producing iso-propyl 5'-aryl-1'H-pyrrolidino [3 ', 4': 1,9] (C 60 -I h) [5,6] fullerene-2'-carboxylates of the general formula (1) :
Figure 00000008
Figure 00000008
 характеризующийся тем, что С60-фуллерен взаимодействует с этилизоцианоацетатом формулы EtO2CCH2N+≡C- в хлорбензоле под действием катализатора Ti(OiPr)4 в присутствии ArMgBr (где Ar=Ph, 2-MePh), взятыми в мольном соотношении С60:изоцианоацетат:Ti(OiPr)4:ArMgBr = 1:(2-6):(1-5):(6-10), при температуре 100°С в течение 5-30 мин.characterized in that the C 60 fullerene interacts with an ethyl isocyanoacetate of the formula EtO 2 CCH 2 N + ≡C - in chlorobenzene under the action of a Ti (OiPr) 4 catalyst in the presence of ArMgBr (where Ar = Ph, 2-MePh) taken in the molar ratio C 60 : isocyanoacetate: Ti (OiPr) 4 : ArMgBr = 1: (2-6) :( 1-5) :( 6-10), at a temperature of 100 ° C for 5-30 minutes.
RU2016116457A 2016-04-26 2016-04-26 Method of selective reception of isopropyline 5'-aryl-1'n-pyrrolidino[3',4':1,9](c60-ih)[5,6]fullerene-2'-carboxylates RU2629752C1 (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2565782C1 (en) * 2014-05-08 2015-10-20 Федеральное государственное бюджетное учреждение науки Институт нефтехимии и катализа Российской академии наук Method of obtaining 6-alkyl(aryl)-2,3-(c60-ih)[5,6]fullero-2,3,4,5-tetrahydropyridines

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2565782C1 (en) * 2014-05-08 2015-10-20 Федеральное государственное бюджетное учреждение науки Институт нефтехимии и катализа Российской академии наук Method of obtaining 6-alkyl(aryl)-2,3-(c60-ih)[5,6]fullero-2,3,4,5-tetrahydropyridines

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Title
Airat R. Tuktarov et al, "Synthesis of [60]fulleropyrrolidine-dithienylethene conjugates and DFT calculations of their photochromic properties", Mendeleev Communications,Volume 25, Issue 6, November-December 2015, Pages 470-472. *

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