Oxidation of Alkanes and Olefins with Hydrogen Peroxide in Acetonitrile Solution Catalyzed by a Mesoporous Titanium-Silicate Ti-MMM-2 | Sciact - CRIS-система Института катализа

Oxidation of Alkanes and Olefins with Hydrogen Peroxide in Acetonitrile Solution Catalyzed by a Mesoporous Titanium-Silicate Ti-MMM-2 Научная публикация

Конференция

14th International Congress on Catalysis
13-18 июл. 2008 , Seoul

Журнал

Applied Catalysis A: General
ISSN: 0926-860X , E-ISSN: 1873-3875

Вых. Данные

Год: 2009, Том: 365, Номер: 1, Страницы: 96-104 Страниц : 8 DOI: 10.1016/j.apcata.2009.05.060

Ключевые слова

Alkanes, Alkyl hydroperoxides, Epoxidation, Heterogeneous catalysis, Limonene, Mesoporous materials, Terpenes, Titanium-silicates

Авторы

Bonon Anderson J. ¹ , Mandelli Dalmo ¹ , Kholdeeva Oxana A. ² , Barmatova Marina V. ² , Kozlov Yuriy N. ³ , Shulʹpin Georgiy B. ³

Организации

1	Pontifı´cia Universidade Cato´lica de Campinas, Faculdade de Quı´mica, Campinas, SP, 13086-900, Brazil
2	Boreskov Institute of Catalysis, Russian Academy of Sciences, Prospekt Akad. Lavrentieva, dom 5, Novosibirsk 630090, Russia
3	Semenov Institute of Chemical Physics, Russian Academy of Sciences, Ulitsa Kosygina, dom 4, Moscow 119991, Russia

Информация о финансировании (8)

1	Российский фонд фундаментальных исследований	06-03-32344
2	National Council for Scientific and Technological Development	300601/01-8
3	National Council for Scientific and Technological Development	300984/2004-9
4	National Council for Scientific and Technological Development	305014/2007-2
5	National Council for Scientific and Technological Development	478165/2006-4
6	São Paulo Research Foundation	2005/51579-2
7	São Paulo Research Foundation	2006/03984-8
8	São Paulo Research Foundation	2006/03996-6

Mesoporous titanium-silicate Ti-MMM-2 catalyzes oxidation of alkanes (cyclooctane, n-heptane, n-octane, isooctane, methylcyclohexane, cis- and trans-1,2-dimethylcyclohexane) and olefins (cyclooctene, 1-decene, (S)-limonene) by H2O2 in acetonitrile solution at 60 °C. The catalytic reaction is truly heterogeneous in nature. The oxidation occurs via the formation of a ‘Ti–OOH’ species on the catalyst surface which either epoxidizes a nucleophilic double bond or generates, after O–O bond splitting, hydroxyl radical. The HOradical dot radical attacks an alkane or olefin C–H bond producing alkyl radical. The reaction Rradical dot + O2 → ROOradical dot leads to the formation of alkyl hydroperoxide as the main product of the alkane oxidation. In the case of alkenes this reaction leads to allylic oxidation products. The composition of products of the olefin oxygenation (the epoxide/alkyl hydroperoxide or epoxide/diol ratios, etc.) strongly depends on the nature of the substrate. In the oxidation of (S)-limonene, isomeric diepoxides are formed along with monoepoxides even at the early stage of the reaction and (SRR)-diepoxide predominates among other products. This can be rationalized by suggesting the epoxidation of the two double bonds to occur simultaneously on two adjacent ‘Ti–O–OH’ centers on the catalyst surface.

Bonon A.J. , Mandelli D. , Kholdeeva O.A. , Barmatova M.V. , Kozlov Y.N. , Shulʹpin G.B.
Oxidation of Alkanes and Olefins with Hydrogen Peroxide in Acetonitrile Solution Catalyzed by a Mesoporous Titanium-Silicate Ti-MMM-2
Applied Catalysis A: General. 2009. V.365. N1. P.96-104. DOI: 10.1016/j.apcata.2009.05.060 WOS Scopus РИНЦ CAPlusCA OpenAlex

Поступила в редакцию:	19 апр. 2009 г.
Принята к публикации:	29 мая 2009 г.
Опубликована online:	8 июн. 2009 г.
Опубликована в печати:	15 авг. 2009 г.

Web of science:	WOS:000268981300012
Scopus:	2-s2.0-67650459576
РИНЦ:	13604829
Chemical Abstracts:	2009:869959
Chemical Abstracts (print):	151:336623
OpenAlex:	W2037555252

БД	Цитирований
Web of science	44
Scopus	45
РИНЦ	44
OpenAlex	42