Oxidation of a wood extractive betulin to biologically active oxo-derivatives using supported gold catalysts

Ekaterina N. Kolobova, Ekaterina G. Pakrieva, Sónia A.C. Carabineiro, Nina Bogdanchikova, Andrey N. Kharlanov, Sergey O. Kazantsev, Jarl Hemming, Päivi Mäki-Arvela, Alexey N. Pestryakov, Dmitry Yu Murzin

Результат исследований: Материалы для журналаСтатья

Выдержка

Betulin (90-94%) was extracted from birch with a non-polar solvent and recrystallized from 2-propanol. Liquid-phase oxidation of betulin aimed at obtaining its biologically active oxo-derivatives (betulone, betulonic and betulinic aldehydes), exhibiting e.g. antitumor, anti-inflammatory, antiparasitic, anticancer and anti-HIV properties, was demonstrated for the first time over gold-based catalysts. Gold was deposited on pristine TiO2 and the same support modified with ceria and lanthana, followed by pretreatment with a H2 or O2 atmosphere. The catalysts were characterized by XRD, BET, ICP, TEM, XPS, DRIFT CO, TPD of NH3 and CO2 methods. The nature of the support, type of modification and the pretreatment atmosphere through the metal-support interactions significantly influenced the average particle size of gold, its distribution and the electronic state of gold, as well as the acid-base properties and, thereby, the catalytic performance (activity and selectivity) in betulin oxidation. Au/La2O3/TiO2 pretreated in H2 displayed the highest catalytic activity in betulin oxidation among the studied catalysts with selectivities to betulone, betulonic and betulinic aldehydes of 42, 32 and 27%, respectively, at 69% conversion. Side reactions resulting in oligomerization/polymerization products occurred on the catalyst surface with the participation of strong acid sites, diminishing the yield of the desired compounds. The latter was improved by adding hydrotalcite with the basic properties to the reaction mixture containing the catalyst. Kinetic modelling through numerical data fitting was performed to quantify the impact of such side reactions and determine the values of rate constants.

Язык оригиналаАнглийский
Страницы (с-по)3370-3382
Число страниц13
ЖурналGreen Chemistry
Том21
Номер выпуска12
DOI
СостояниеОпубликовано - 1 янв 2019

Отпечаток

Gold
Wood
gold
catalyst
Derivatives
oxidation
Oxidation
Catalysts
hydrotalcite
aldehyde
Aldehydes
Antiparasitic Agents
Lanthanum
Oligomerization
Acids
2-Propanol
Catalyst selectivity
atmosphere
acid
Cerium compounds

ASJC Scopus subject areas

  • Environmental Chemistry
  • Pollution

Цитировать

Kolobova, E. N., Pakrieva, E. G., Carabineiro, S. A. C., Bogdanchikova, N., Kharlanov, A. N., Kazantsev, S. O., ... Murzin, D. Y. (2019). Oxidation of a wood extractive betulin to biologically active oxo-derivatives using supported gold catalysts. Green Chemistry, 21(12), 3370-3382. https://doi.org/10.1039/c9gc00949c

Oxidation of a wood extractive betulin to biologically active oxo-derivatives using supported gold catalysts. / Kolobova, Ekaterina N.; Pakrieva, Ekaterina G.; Carabineiro, Sónia A.C.; Bogdanchikova, Nina; Kharlanov, Andrey N.; Kazantsev, Sergey O.; Hemming, Jarl; Mäki-Arvela, Päivi; Pestryakov, Alexey N.; Murzin, Dmitry Yu.

В: Green Chemistry, Том 21, № 12, 01.01.2019, стр. 3370-3382.

Результат исследований: Материалы для журналаСтатья

Kolobova, EN, Pakrieva, EG, Carabineiro, SAC, Bogdanchikova, N, Kharlanov, AN, Kazantsev, SO, Hemming, J, Mäki-Arvela, P, Pestryakov, AN & Murzin, DY 2019, 'Oxidation of a wood extractive betulin to biologically active oxo-derivatives using supported gold catalysts', Green Chemistry, том. 21, № 12, стр. 3370-3382. https://doi.org/10.1039/c9gc00949c
Kolobova, Ekaterina N. ; Pakrieva, Ekaterina G. ; Carabineiro, Sónia A.C. ; Bogdanchikova, Nina ; Kharlanov, Andrey N. ; Kazantsev, Sergey O. ; Hemming, Jarl ; Mäki-Arvela, Päivi ; Pestryakov, Alexey N. ; Murzin, Dmitry Yu. / Oxidation of a wood extractive betulin to biologically active oxo-derivatives using supported gold catalysts. В: Green Chemistry. 2019 ; Том 21, № 12. стр. 3370-3382.
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abstract = "Betulin (90-94{\%}) was extracted from birch with a non-polar solvent and recrystallized from 2-propanol. Liquid-phase oxidation of betulin aimed at obtaining its biologically active oxo-derivatives (betulone, betulonic and betulinic aldehydes), exhibiting e.g. antitumor, anti-inflammatory, antiparasitic, anticancer and anti-HIV properties, was demonstrated for the first time over gold-based catalysts. Gold was deposited on pristine TiO2 and the same support modified with ceria and lanthana, followed by pretreatment with a H2 or O2 atmosphere. The catalysts were characterized by XRD, BET, ICP, TEM, XPS, DRIFT CO, TPD of NH3 and CO2 methods. The nature of the support, type of modification and the pretreatment atmosphere through the metal-support interactions significantly influenced the average particle size of gold, its distribution and the electronic state of gold, as well as the acid-base properties and, thereby, the catalytic performance (activity and selectivity) in betulin oxidation. Au/La2O3/TiO2 pretreated in H2 displayed the highest catalytic activity in betulin oxidation among the studied catalysts with selectivities to betulone, betulonic and betulinic aldehydes of 42, 32 and 27{\%}, respectively, at 69{\%} conversion. Side reactions resulting in oligomerization/polymerization products occurred on the catalyst surface with the participation of strong acid sites, diminishing the yield of the desired compounds. The latter was improved by adding hydrotalcite with the basic properties to the reaction mixture containing the catalyst. Kinetic modelling through numerical data fitting was performed to quantify the impact of such side reactions and determine the values of rate constants.",
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T1 - Oxidation of a wood extractive betulin to biologically active oxo-derivatives using supported gold catalysts

AU - Kolobova, Ekaterina N.

AU - Pakrieva, Ekaterina G.

AU - Carabineiro, Sónia A.C.

AU - Bogdanchikova, Nina

AU - Kharlanov, Andrey N.

AU - Kazantsev, Sergey O.

AU - Hemming, Jarl

AU - Mäki-Arvela, Päivi

AU - Pestryakov, Alexey N.

AU - Murzin, Dmitry Yu

PY - 2019/1/1

Y1 - 2019/1/1

N2 - Betulin (90-94%) was extracted from birch with a non-polar solvent and recrystallized from 2-propanol. Liquid-phase oxidation of betulin aimed at obtaining its biologically active oxo-derivatives (betulone, betulonic and betulinic aldehydes), exhibiting e.g. antitumor, anti-inflammatory, antiparasitic, anticancer and anti-HIV properties, was demonstrated for the first time over gold-based catalysts. Gold was deposited on pristine TiO2 and the same support modified with ceria and lanthana, followed by pretreatment with a H2 or O2 atmosphere. The catalysts were characterized by XRD, BET, ICP, TEM, XPS, DRIFT CO, TPD of NH3 and CO2 methods. The nature of the support, type of modification and the pretreatment atmosphere through the metal-support interactions significantly influenced the average particle size of gold, its distribution and the electronic state of gold, as well as the acid-base properties and, thereby, the catalytic performance (activity and selectivity) in betulin oxidation. Au/La2O3/TiO2 pretreated in H2 displayed the highest catalytic activity in betulin oxidation among the studied catalysts with selectivities to betulone, betulonic and betulinic aldehydes of 42, 32 and 27%, respectively, at 69% conversion. Side reactions resulting in oligomerization/polymerization products occurred on the catalyst surface with the participation of strong acid sites, diminishing the yield of the desired compounds. The latter was improved by adding hydrotalcite with the basic properties to the reaction mixture containing the catalyst. Kinetic modelling through numerical data fitting was performed to quantify the impact of such side reactions and determine the values of rate constants.

AB - Betulin (90-94%) was extracted from birch with a non-polar solvent and recrystallized from 2-propanol. Liquid-phase oxidation of betulin aimed at obtaining its biologically active oxo-derivatives (betulone, betulonic and betulinic aldehydes), exhibiting e.g. antitumor, anti-inflammatory, antiparasitic, anticancer and anti-HIV properties, was demonstrated for the first time over gold-based catalysts. Gold was deposited on pristine TiO2 and the same support modified with ceria and lanthana, followed by pretreatment with a H2 or O2 atmosphere. The catalysts were characterized by XRD, BET, ICP, TEM, XPS, DRIFT CO, TPD of NH3 and CO2 methods. The nature of the support, type of modification and the pretreatment atmosphere through the metal-support interactions significantly influenced the average particle size of gold, its distribution and the electronic state of gold, as well as the acid-base properties and, thereby, the catalytic performance (activity and selectivity) in betulin oxidation. Au/La2O3/TiO2 pretreated in H2 displayed the highest catalytic activity in betulin oxidation among the studied catalysts with selectivities to betulone, betulonic and betulinic aldehydes of 42, 32 and 27%, respectively, at 69% conversion. Side reactions resulting in oligomerization/polymerization products occurred on the catalyst surface with the participation of strong acid sites, diminishing the yield of the desired compounds. The latter was improved by adding hydrotalcite with the basic properties to the reaction mixture containing the catalyst. Kinetic modelling through numerical data fitting was performed to quantify the impact of such side reactions and determine the values of rate constants.

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