RU2434843C2 - METHOD OF PRODUCING 1'a-METHYL-1'a-ETHYLFORMYL-1'a-CARBA-1'(2')a-HOMO(C60-Ih)[5,6]FULLERENE - Google Patents

METHOD OF PRODUCING 1'a-METHYL-1'a-ETHYLFORMYL-1'a-CARBA-1'(2')a-HOMO(C60-Ih)[5,6]FULLERENE Download PDF

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RU2434843C2
RU2434843C2 RU2008142156/04A RU2008142156A RU2434843C2 RU 2434843 C2 RU2434843 C2 RU 2434843C2 RU 2008142156/04 A RU2008142156/04 A RU 2008142156/04A RU 2008142156 A RU2008142156 A RU 2008142156A RU 2434843 C2 RU2434843 C2 RU 2434843C2
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fullerene
methyl
ethylformyl
carba
homo
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Усеин Меметович Джемилев (RU)
Усеин Меметович Джемилев
Айрат Рамилевич Туктаров (RU)
Айрат Рамилевич Туктаров
Арслан Рифхатович Ахметов (RU)
Арслан Рифхатович Ахметов
Асхат Габдрахманович Ибрагимов (RU)
Асхат Габдрахманович Ибрагимов
Раис Асхатович Садыков (RU)
Раис Асхатович Садыков
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Учреждение Российской Академии Наук Институт Нефтехимии И Катализа Ран
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Abstract

FIELD: chemistry.
SUBSTANCE: invention relates to organic chemistry and specifically to a method of producing functionally substituted fullerenes used as complexing agents, sorbents and biologically active compounds. The method of producing 1'a-methyl-1'a-ethylformyl-1'a-carba-1'(2')a-homo(C60-Ih)[5,6]fullerene of formula
Figure 00000008
(1) is characterised by that C60-fullerene reacts with α-methyldiazoacetic ester of formula N2C(Me)COOEt, in α-dichlorobenzene in the presence of a three-component catalyst {Pd(acac)2 : 2PPh3:4Et3Al}, taken in molar ratio C60:α-methyldiazoacetic ester :Pd(acac)2:PPh3:Et3Al = 0.01:(0.01-0.10):(0.0015-0.0025):(0.003-0.005):(0.006-0.01), preferably 0.01:0.05:0.002:0.004:0.008 at temperature 40°C for 0.25-1.0 hours.
EFFECT: desired product is obtained with 58-86% output.
1 tbl

Description

Предлагаемое изобретение относится к области органического синтеза, а именно к способу получения 1′а-метил-1′а-этилформил-1′а-карба-1′(2′)a-гомо(С60-Ih)[5,6]фуллерена формулы (1):The present invention relates to the field of organic synthesis, and in particular to a method for producing 1′a-methyl-1′a-ethylformyl-1′a-carba-1 ′ (2 ′) a-homo (C 60 -I h ) [5, 6] fullerene of the formula (1):

Figure 00000001
Figure 00000001

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.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.

Известен способ (S.R.Wilson, Y.Wu. J. Chem. Soc., Chem. Commun., 1993, 784 [1]) получения краун-эфир содержащего фуллероида (4) с выходом 42% реакцией С60-фуллерена (2) с диазокраун-эфиром (3) при температуре 5-10°С в течение 2-3 ч.A known method (SRWilson, Y.Wu. J. Chem. Soc., Chem. Commun., 1993, 784 [1]) for producing crown ether containing fulleroid (4) in 42% yield with a reaction of C 60 -fullerene (2) with diazocrown ether (3) at a temperature of 5-10 ° C for 2-3 hours

Figure 00000002
Figure 00000002

Известный способ не позволяет получить 1′а-метил-1′а-этилформил-1′а-карба-1′(2′)а-гомо(С60-Ih)[5,6]фуллерен формулы (1).The known method does not allow to obtain 1′a-methyl-1′a-ethylformyl-1′a-carba-1 ′ (2 ′) a-homo (C 60 -I h ) [5,6] fullerene of the formula (1).

Известен способ (R.Sijbesma, G.Srdanov, F.Wudl, J.A.Castoro, C.Wilkins, S.H.Friedman, D.L.DeCamp, G.L.Kenyon. J. Am. Chem. Soc. 1993, 115, 6510 [2]) получения фуллероциклопропана (6) с выходом 93% реакцией С60-фуллерена (2) с 4,4′-бис(N-ацетил-2-аминоэтил)дифенилдиазометаном (5) в сухом пиридине в присутствии янтарного ангидрида при комнатной температуре в течение 24 ч.A known method (R. Sijbesma, G. Srdanov, F.Wudl, JACastoro, C.Wilkins, SHFriedman, DLDeCamp, GLKenyon. J. Am. Chem. Soc. 1993, 115, 6510 [2]) for producing fullerocyclopropane (6) with in a 93% yield by reaction of C 60- fullerene (2) with 4,4′-bis (N-acetyl-2-aminoethyl) diphenyldiazomethane (5) in dry pyridine in the presence of succinic anhydride at room temperature for 24 hours.

Figure 00000003
Figure 00000003

Известный способ не позволяет получить 1′а-метил-1′а-этилформил-1′а-карба-1′(2′)а-гомо(С60-Ih)[5,6]фуллерен формулы (1).The known method does not allow to obtain 1′a-methyl-1′a-ethylformyl-1′a-carba-1 ′ (2 ′) a-homo (C 60 -I h ) [5,6] fullerene of the formula (1).

Предлагается новый способ получения 1′а-метил-1′а-этилформил-1′а-карба-1′(2′)а-гомо(С60-Ih)[5,6]фуллерена (1).A new method is proposed for preparing 1′a-methyl-1′a-ethylformyl-1′a-carba-1 ′ (2 ′) a-homo (C 60 -I h ) [5,6] fullerene (1).

Сущность способа заключается во взаимодействии фуллерена (С60) с α-метилдиазоуксусным эфиром формулы N2C(Me)COOEt, в присутствии трехкомпонентного катализатора {Pd(acac)2:2PPh3:4Et3Al}, взятыми в мольном соотношении С60:α-метилдиазоуксусный эфир:Pd(acac)2:PPh3:Et3Al=0.01:(0.01-0.10):(0.0015-0.0025):(0.003-0.005):(0.006-0.01), предпочтительно 0.01:0.05:0.002:0.004:0.008, в о-дихлорбензоле (о-ДХБ) в качестве растворителя при температуре 40°С в течение 0.25-1.0 ч. Получают 1′а-метил-1′а-этилформил-1′а-карба-1′(2′)а-гомо(С60-Ih)[5,6]фуллерен (1) с общим выходом 58-86%. Реакция протекает по схеме:The essence of the method consists in the interaction of fullerene (C 60 ) with an α-methyldiazoucetic ester of the formula N 2 C (Me) COOEt, in the presence of a three-component catalyst {Pd (acac) 2 : 2PPh 3 : 4Et 3 Al}, taken in a molar ratio of C 60 : α-methyl diazoacetic ester: Pd (acac) 2 : PPh 3 : Et 3 Al = 0.01: (0.01-0.10) :( 0.0015-0.0025) :( 0.003-0.005) :( 0.006-0.01), preferably 0.01: 0.05: 0.002 : 0.004: 0.008, in o-dichlorobenzene (o-DCB) as a solvent at a temperature of 40 ° C. for 0.25-1.0 hours. 1′a-methyl-1′a-ethylformyl-1′a-carba-1 ′ is obtained (2 ′) a-homo (C 60 -I h ) [5,6] fullerene (1) with a total yield of 58-86%. The reaction proceeds according to the scheme:

Figure 00000004
Figure 00000004

Проведение указанной реакции в присутствии палладиевого катализатора [Pd] больше 20 мол.% по отношению к фуллерену С60 не приводит к существенному увеличению выходов целевого продукта (1). Применение палладиевого катализатора [Pd] в количестве меньше 20 мол.% по отношению к фуллерену С60 снижает выход целевого продукта, что связано с уменьшением реакционных центров. Реакцию следует проводить при температуре 40°С. Проведение реакции при более высокой температуре (например, 80°С) связано с увеличением энергозатрат, при меньшей температуре (например, 20°С) снижается скорость реакции.Carrying out this reaction in the presence of a palladium catalyst [Pd] more than 20 mol.% In relation to fullerene C 60 does not lead to a significant increase in the yields of the target product (1). The use of a palladium catalyst [Pd] in an amount of less than 20 mol% with respect 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 40 ° C. The reaction at a higher temperature (for example, 80 ° C) is associated with an increase in energy consumption, at a lower temperature (for example, 20 ° C), the reaction rate decreases.

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

Предлагаемый способ базируется на использовании α-метилдиазоуксусного эфира и каталитических количеств комплекса палладия, реакция идет в доступном о-дихлорбензоле.The proposed method is based on the use of α-methyldiazoucetic ester and catalytic amounts of a palladium complex, the reaction proceeds in available o-dichlorobenzene.

Предлагаемый способ, в отличие от известных, позволяет получать 1′а-метил-1′а-этилформил-1′а-карба-1′(2′)а-гомо(С60-Ih)[5,6]фуллерен (1), синтез которого в литературе не описан.The proposed method, unlike the known ones, allows to obtain 1′a-methyl-1′a-ethylformyl-1′a-carba-1 ′ (2 ′) a-homo (C 60 -I h ) [5,6] fullerene (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 о-ДХБ в токе сухого аргона при температуре -5°С и перемешивании добавляют 0.004 ммолей PPh3, 0.008 ммолей Et3Al и 0.01 ммолей С60-фуллерена в 1 мл о-ДХБ. Реакционную массу нагревают до 40°С и по каплям добавляют 0.05 ммолей α-метилдиазоуксусного эфира в 0.5 мл о-ДХБ. Через 0.5 ч реакционную массу охлаждают и пропускают через колонку с небольшим слоем силикагеля. Получают 1′а-метил-1′а-этилформил-1′а-карба-1′(2′)а-гомо(С60-Ih)[5,6]фуллерен (1) с выходом 72% (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 40 ° C and 0.05 mmol of α-methyldiazouxacetate in 0.5 ml of o-DCB is added dropwise. After 0.5 h, the reaction mass is cooled and passed through a column with a small layer of silica gel. Get 1′a-methyl-1′a-ethylformyl-1′a-carba-1 ′ (2 ′) a-homo (C 60 -I h ) [5,6] fullerene (1) with a yield of 72% (by HPLC data).

Спектральные характеристики (1)Spectral characteristics (1)

Figure 00000005
Figure 00000005
Спектр ЯМР 1Н: 1.36 (т, 3Н, СН3, J=7.2 Гц), 3.22 с (3Н, СН3), 4.23 (к, 2Н, CH2, J=7.2 Гц). 1 H NMR spectrum: 1.36 (t, 3H, CH 3 , J = 7.2 Hz), 3.22 s (3H, CH 3 ), 4.23 (q, 2H, CH 2 , J = 7.2 Hz). Спектр ЯМР 13С (CDCl3: CS2=1:5 (υ/υ)), δ, м.д.: 14.08 (C6), 25.52 (C7), 53.44 (C3), 61.50 (C5), 134.06, 134.64, 135.41, 136.61 (C1,2), 137.65, 138.31, 138.67, 138.72, 139.91, 140.56, 141.41, 141.58, 141.75, 141.90, 142.21, 142.56, 142.59, 142.69, 142.88, 142.95, 143.15, 143.29, 143.48, 143.65, 143.83, 144.51, 144.73, 147.26, 168.88 (С4). 13 C NMR spectrum (CDCl 3 : CS 2 = 1: 5 (υ / υ)), δ, ppm: 14.08 (C 6 ), 25.52 (C 7 ), 53.44 (C 3 ), 61.50 (C 5 ), 134.06, 134.64, 135.41, 136.61 (C 1.2 ), 137.65, 138.31, 138.67, 138.72, 139.91, 140.56, 141.41, 141.58, 141.75, 141.90, 142.21, 142.56, 142.59, 142.69, 142.88, 142.95, 143.15, 143.29, 143.48, 143.65, 143.83, 144.51, 144.73, 147.26, 168.88 (C 4 ).

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

ТаблицаTable № п/пNo. p / p Мольное соотношение C60:N2C(Me)COOEt:Pd(acac)2:PPh3:Et3Al, ммольThe molar ratio of C 60 : N 2 C (Me) COOEt: Pd (acac) 2 : PPh 3 : Et 3 Al, mmol Время реакции, чReaction time, h Выход целевого продукта (1), %The yield of the target product (1),% 1one 0.01:0.05:0.002:0.004:0.0080.01: 0.05: 0.002: 0.004: 0.008 0.50.5 7272 22 0.01:0.10:0.002:0.004:0.0080.01: 0.10: 0.002: 0.004: 0.008 0.50.5 7979 33 0.01:0.01:0.002:0.004:0.0080.01: 0.01: 0.002: 0.004: 0.008 0.50.5 6767 4four 0.01:0.05:0.0025:0.005:0.010.01: 0.05: 0.0025: 0.005: 0.01 0.50.5 8686 55 0.01:0.05:0.0015:0.003:0.0060.01: 0.05: 0.0015: 0.003: 0.006 0.50.5 5858 66 0.01:0.05:0.002:0.004:0.0080.01: 0.05: 0.002: 0.004: 0.008 1one 8484 77 0.01:0.05:0.002:0.004:0.0080.01: 0.05: 0.002: 0.004: 0.008 0.250.25 6363

Реакцию проводили при температуре 40°С в о-дихлорбензоле в качестве растворителя.The reaction was carried out at a temperature of 40 ° C in o-dichlorobenzene as a solvent.

Claims (1)

Способ получения 1′а-метил-1′а-этилформил-1′а-карба-1′(2′)а-гомо(С60-Ih)[5,6]фуллерена формулы (1):
Figure 00000006

характеризующийся тем, что С60-фуллерен взаимодействует с α-метилдиазоуксусным эфиром формулы N2C(Me)COOEt, в о-дихлорбензоле в присутствии трехкомпонентного катализатора {Pd(acac)2 : 2PPh3 : 4Et3Al}, взятыми в мольном соотношении С60 : α-метилдиазоуксусный эфир : Pd(acac)2 : PPh3 : Et3Al = 0,01:(0,01-0,10):(0,0015-0,0025):(0,003-0,005):(0,006-0,01), предпочтительно, 0,01:0,05:0,002:0,004:0,008, при температуре 40°С в течение 0,25-1,0 ч. The method of obtaining 1′a-methyl-1′a-ethylformyl-1′a-carba-1 ′ (2 ′) a-homo (C 60 -I h ) [5,6] fullerene of the formula (1):
Figure 00000006

characterized in that the C 60 fullerene interacts with an α-methyldiazoucetic ester of the formula N 2 C (Me) COOEt, in o-dichlorobenzene in the presence of a three-component catalyst {Pd (acac) 2 : 2PPh 3 : 4Et 3 Al}, taken in a molar ratio C 60 : α-methyldiazouzoacetate: Pd (acac) 2 : PPh 3 : Et 3 Al = 0.01: (0.01-0.10) :( 0.0015-0.0025) :( 0.003-0.005) : (0.006-0.01), preferably 0.01: 0.05: 0.002: 0.004: 0.008, at a temperature of 40 ° C for 0.25-1.0 hours
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Title
DATABASE CAS on STN реферат №142:411057 Li, Yu Jin; Peng. Ru Fang; Liu You Cheng; Wang Guan Wu Solvent-free mechanochemical and liquid-phase reaction of [60]fullerene with ethyl 2-diazopropionate Chinese Chemical Letters, 15 (11), c.1265-1268, 2004. DATABASE CAS on STN реферат №135:303661 Hino Т.; Kinbara K.; Saigo K. Synthesis of methano[60]fullerene derivatives: the fluoride ion-mediated reaction of [60]fullerene with silylated nucleophiles. Tetrahedron Letters, 42 (30), c.5065-5067, 2001. R.Sijbesma, G.Srdanov, F.Wudl, J.A.Castoro, Charles Wilkins, Simon H. Friedman, Dianne L. DeCamp, George L. Kenyon Synthesis of a fullerene derivative for the inhibition of HIV enzymes J. Am. Chem. Soc, 1993, 115 (15), c.6510-6512. *

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