Synthesis and Reactions of 2,2-[60]Fullerenoalkanoyl Chlorides

Tada, Tomoyuki; Ishida, Yasuhiro; Saigo, Kazuhiko

doi:10.1021/jo052399l

Cited by 24 publications

(20 citation statements)

References 35 publications

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“…In a reaction of isopropyl diazoacetate with the fullerene C 60 (molar ratio 5 : 1) in the presence of 20 mol.% of three component catalyst Pd(acac) 2 -PPh 3 -Et 3 Al (1 : 2 : 4) in 1,2 dichlorobenzene at 80 °C, in 1 h a mixture of [6,6] closed (1) and two stereoisomeric [5,6] open (2, 3) adducts of C 60 with a total yield* ~70% is formed (Scheme 1). An increasing of the reaction duration to 2 h does not result in a noticeable increasing of the total yield (~76%) of the target cycloadducts.…”

Section: Resultsmentioning

confidence: 99%

“…One ( 1 H and 13 C) and two dimensional (COSY, HSQC, HMBC) NMR experiments showed that the mixture of * Hereafter the yields are based on the starting fullerene C 60 . [6,6] closed (1) and stereoisomeric [5,6] open (2, 3) monoadducts of the fullerene was formed.…”

Section: Resultsmentioning

confidence: 99%

“…During the cycloaddition using the components molar ra tio of this catalytic system equal to 1 : 4 : 4, only the meth anofullerenes were formed regardless of the substituent structure in the diazo compound. Therefore, all the fol lowing experiments were carried out using the catalytic system Pd(acac) 2 -PPh 3 -Et 3 Al (1 : 2 : 4) with a purpose of more detailed study of the influence of the structure of initial diazoacetates on the composition of the cyclo adducts formed.In a reaction of isopropyl diazoacetate with the fullerene C 60 (molar ratio 5 : 1) in the presence of 20 mol.% of three component catalyst Pd(acac) 2 -PPh 3 -Et 3 Al (1 : 2 : 4) in 1,2 dichlorobenzene at 80 °C, in 1 h a mixture of [6,6] closed (1) and two stereoisomeric [5,6] open (2, 3) adducts of C 60 with a total yield* ~70% is formed (Scheme 1). An increasing of the reaction duration to 2 h does not result in a noticeable increasing of the total yield (~76%) of the target cycloadducts.…”

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Cycloaddition of diazoacetates to C60 fullerene catalysed by Pd complexes

et al. 2010

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An efficient catalytic method of the cycloaddition to C 60 fullerene of the diazoacetates, containing substituents of diverse structures in ester groups, in the presence of a Pd based three component catalyst was developed. An influence of nature and the structure of substi tuent in the ester group on the activity of diazoacetates in the reaction with C 60 was studied. Yields of respective cycloadducts were determined.An interest in carboxy derivatives of methanofullerenes is caused by a possibility of obtaining of promising prepa rations for medicine and agriculture on their base. 1-5 However, a synthesis of these C 60 derivatives containing substituents in the ester group consists in multi stage con version of carboxymethanofullerene which results in low yields of the target products. 1,3,6-9Recently, an efficient catalytic method of cycloaddi tion of diazoacetic ester and α substituted ethyl diazoace tates to the C 60 fullerene using the three component cata lyst Pd(acac) 2 -PPh 3 -Et 3 Al (20 mol.%) was suggest ed. 10,11 As it is noted, by a ratio of the starting components of catalytic system and the nature of the substituent in α position to the diazo group of the initial diazoacetate, it is possible to definitely regulate a direction of the cycload dition and to selectively obtain both methanofullerenes and homofullerenes.In order to develop our earlier elaborated 10,11 method of the catalytic cycloaddition of the diazoacetates to the C 60 fullerene under the action of catalysts on a basis of low valent Pd complexes, as well as to investigate the in fluence of the structure of substituent in the ester group of diazoacetate on the direction and the structural selectivity of the reaction of the latters with the fullerene C 60 , we studied the cycloaddition of diazoacetates with alkyl, cycloalkyl, allyl, and steroid substituents to the fullerene C 60 catalysed by Pd(acac) 2 -PPh 3 -Et 3 Al (1 : 2 : 4) Results and DiscussionIt was earlier shown, 11 that the influence of nature and substituent structure in the α substituted ethyl diazoace tates on the selectivity of formation of homo and methano fullerenes in the reaction with C 60 is most evident when the three component catalyst Pd(acac) 2 -PPh 3 -Et 3 Al (components molar ratio is 1 : 2 : 4, respectively) is used. During the cycloaddition using the components molar ra tio of this catalytic system equal to 1 : 4 : 4, only the meth anofullerenes were formed regardless of the substituent structure in the diazo compound. Therefore, all the fol lowing experiments were carried out using the catalytic system Pd(acac) 2 -PPh 3 -Et 3 Al (1 : 2 : 4) with a purpose of more detailed study of the influence of the structure of initial diazoacetates on the composition of the cyclo adducts formed.In a reaction of isopropyl diazoacetate with the fullerene C 60 (molar ratio 5 : 1) in the presence of 20 mol.% of three component catalyst Pd(acac) 2 -PPh 3 -Et 3 Al (1 : 2 : 4) in 1,2 dichlorobenzene at 80 °C, in 1 h a mixture of [6,6] closed (1) and two stereoisomeric [5,6] open...

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

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Cycloaddition of diazoacetates to C60 fullerene catalysed by Pd complexes

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“…был полу-чен из компании НеоТекПродакт (Санкт-Петербург). Соединения II-VII были синтезированы по извест-ным методикам [11][12][13][14][15]. Эфиры III-VII были очищены методом колоночной хроматографии на силикагеле (поры 6 нм, зернение 57-250 мкм (60-250 меш), фирма Acros Organics), элюент -толуол-гексан (объемное соотношение 1 : 1).…”

Section: экспериментальная частьunclassified

Characterization of fullerene derivatives by maldi fragment mass spectra

Milman¹,

Piotrovsky²,

Nikolaev³

et al. 2013

АиК

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1ФГБУ «Научно-исследовательский институт экспериментальной медицины» СЗО РАМН (ИЭМ) Россия, 197376, Санкт-Петербург, ул. акад. Павлова, д. 12 bmilman@mail.rcom.ru; bormilman@yandex.ru 2 ФГБУН «Институт токсикологии» ФМБА России Россия, 192019, Санкт-Петербург, ул. Бехтерева, д. 1 Поступила в редакцию 9 апреля 2013 г., В статье обсуждаются масс-спектры фуллерена C 60 и его шести производных, а именно метано[60]фуллеренкарбоновой кислоты, ее этилового эфира, диэтилового эфира метано [60] фуллерендикарбоновой кислоты и трех изомерных тетраэтиловых эфиров бис-метано [60] фуллерентетракарбоновой кислоты (соединения I-VII соответственно), полученные методом МАЛДИ и МАЛДИ-ЛИФТ (MALDI LIFT-TOF/TOF). Второй из методов впервые использован в масс-спектрометрии фуллеренов. Рассмотрены его перспективы в отношении характери-зации и установления структуры этих соединений Ключевые слова: масс-спектрометрия, МАЛДИ, МАЛДИ-ЛИФТ, производные фулле-рена, справочные масс-спектры.Мильман Борис Львович -доктор химических наук, заведующий лабораторией биомедицинской и фармацевтической масс-спектрометрии ИЭМ.Область научных интересов: масс-спектрометрия, теория и принципы химиче-ской идентификации, анализ проб неизвестного состава, биохимический анализ.Автор более 90 публикаций.Пиотровский Левон Борисович -доктор биологических наук, заведующий лабо-раторией синтеза и нанотехнологий лекарственных веществ ИЭМ.Область научных интересов: синтез лекарственных веществ, связь химическая структура -биологическая активность, биологические свойства наноструктур углерода.Автор более 210 публикаций.Николаев Дмитрий Николаевич -научный сотрудник лаборатории синтеза и на-нотехнологий лекарственных веществ ИЭМ.Область научных интересов: синтез лекарственных веществ, связь химическая структура -биологическая активность, биологические свойства наноструктур углерода.Автор 12 публикаций.Думпис Марина Анатольевна -кандидат химимических наук, ведущий научный сотрудник лаборатории синтеза и нанотехнологий лекарственных веществ ИЭМ.Область научных интересов: синтез биологически активных веществ, биологи-ческие свойства наноструктур углерода.Автор более 140 публикаций.Литасова Елена Викторовна -кандидат биологических наук, старший научный сотрудник лаборатории синтеза и нанотехнологий лекарственных веществ ИЭМ.Область научных интересов: синтез биологически активных веществ, биологи-ческие свойства наноструктур углерода.Автор 33 публикаций.Луговкина Наталья Владимировна -научный сотрудник лаборатории токсиколо-гической химии органических соединений Института токсикологии.Область научных интересов: подготовка проб для хроматографического и масс-спектрометрического анализа.Автор 11 публикаций.

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“…Ciclopropanação descrita por Bingel (1993) substratos contendo metileno ativo (ao invés de a-haloésteres), [22][23][24] iodo molecular (ou CBr 4 ) 25 e o uso de outras bases como DBU, 26 LDA, 27 NEt 3 e piridina, 28 além de Na 2 CO 3 . 29 A Tabela 2 apresenta alguns exemplos de reação usando esta metodologia.…”

Section: Esquema 3 Ciclopropanação Do C 60unclassified

Fulereno[C60]: química e aplicações

Santos¹,

Rocha²,

Alves³

et al. 2010

Quím. Nova

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Recebido em 7/5/09; aceito em 22/9/09; publicado na web em 25/2/10 FULLERENE C 60 : CHEMISTRY AND APPLICATIONS. Fullerene chemistry has become a very active research field in the two last decades, largely because of the exceptional properties of the C 60 molecule and the variety of fullerene derivatives that appear to be possible. In this review, a general analysis of fullerene C 60 reactivity is performed. The principal methods for the covalent modification of this fascinating carbon cage are presented. The prospects of using fullerene derivatives as medicinal drugs and photoactive materials in light converting devices are demonstrated.Keywords: fullerene C 60 ; nanomaterials; carbon allotropes. Este artigo de revisão teve o objetivo de sistematizar as principais informações relacionadas à reatividade singular desta forma de carbono e aos principais métodos até então desenvolvidos para a funcionalização química do fulereno [C 60 ] bem como exemplificar a grande e versátil gama de aplicações encontradas até hoje para esta nanomolécula e seus derivados quimicamente modificados. INTRODUÇÃO HISTÓRICO, MÉTODOS DE OBTENÇÃO E PURIFICAÇÃOEmbora desde 1966 cálculos teóricos demonstrassem a possibilidade da existência de "gaiolas" estáveis formadas exclusivamente por átomos de carbono, 2 somente em 1985 um experimento realizado por Kroto et al. comprovou experimentalmente a existência de tais compostos. 3 Nesse experimento, uma placa de grafite foi submetida a um laser pulsado de alta frequência e os agregados gerados no plasma foram analisados por espectrometria de massas. O experimento mostrou a formação de moléculas grandes constituídas exclusivamente por átomos de carbono, com fórmula C n onde n= 30-190, sendo C 60 e C 70 os mais abundantes. Sob condições específicas para a formação destes agregados, o espectro de massas apresentou o pico do C 60 como principal. Esta molécula, excepcionalmente estável e simétrica, foi chamada pelos pesquisadores de fullerene em homenagem ao arquiteto americano B. Fuller, responsável pela invenção dos domos geodési-cos, forma arquitetônica que segue o mesmo princípio de simetria e estabilidade. Sir H. W. Kroto, R. F. Curl e R. E. Smalley procuravam, neste experimento, mimetizar condições interestelares para comprovar a existência de grandes e excepcionais cadeias de carbono no espaço e não suspeitavam que, graças a sua descoberta, seriam agraciados com o Nobel de Química alguns anos mais tarde, em 1996.A descoberta destas espécies moleculares de carbono excitou profundamente a comunidade científica. Entretanto, somente em 1990, R. Taylor, um especialista em cromatografia, foi capaz de obter pela primeira vez 4 amostras puras de C 60 e C 70 em quantidades mínimas, mas suficiente para começar a exploração de suas propriedades químicas e espectroscópicas. No mesmo ano, o desenvolvimento por Krätschmer et al. 5 de um método para a síntese de C 60 em quantidades "macroscópicas" representou uma etapa decisiva para a área que se tornou, nos últimos 20 anos, um tema maior da química contempo...

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Synthesis and Reactions of 2,2-[60]Fullerenoalkanoyl Chlorides

Cited by 24 publications

References 35 publications

Cycloaddition of diazoacetates to C60 fullerene catalysed by Pd complexes

Cycloaddition of diazoacetates to C60 fullerene catalysed by Pd complexes

Characterization of fullerene derivatives by maldi fragment mass spectra

Fulereno[C60]: química e aplicações

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