515-00-4Relevant academic research and scientific papers
Selective Catalytic Isomerization of β-Pinene Oxide to Perillyl Alcohol Enhanced by Protic Tetraimidazolium Nitrate
Li, Hui,Liu, Jian,Zhao, Juan,He, Huiting,Jiang, Dabo,Kirk, Steven Robert,Xu, Qiong,Liu, Xianxiang,Yin, Dulin
, p. 477 - 485 (2021)
A series of tetraimidazolium salts with different anions was prepared and applied in the isomerization of β-pinene oxide. After examining the activity of different catalysts, a remarkable enhancement of the selectivity of perillyl alcohol (47 %) was obtained over [PEimi][HNO3]4 under mild reaction conditions and using DMSO as the solvent. Furthermore, noncovalent interactions between solvent molecules and the catalyst were found by FT-IR spectroscopy and confirmed by computational chemistry. The homogeneous catalyst showed excellent stability and was reused up to six times without significant loss.
New sustainable synthetic routes to cyclic oxyterpenes using the ecocatalyst toolbox
Bihanic, Camille,Grison, Claude,Lasbleiz, Arthur,Le Blainvaux, Pierre,Petit, Eddy,Regnier, Morgan
, (2021/12/09)
Cyclic oxyterpenes are natural products that are mostly used as fragrances, flavours and drugs by the cosmetic, food and pharmaceutical industries. However, only a few cyclic oxyterpenes are accessible via chemical syntheses, which are far from being ecofriendly. We report here the synthesis of six cyclic oxyterpenes derived from ?-pinene while respecting the principles of green and sustainable chemistry. Only natural or biosourced catalysts were used in mild conditions that were optimised for each synthesis. A new generation of ecocatalysts, derived from Mn-rich water lettuce, was prepared via green processes, characterised by MP-AES, XRPD and TEM analyses, and tested in catalysis. The epoxidation of ?-pinene led to the platform molecule, ?-pinene oxide, with a good yield, illustrating the efficacy of the new generation of ecocatalysts. The opening ?-pinene oxide was investigated in green conditions and led to new and regioselective syntheses of myrtenol, 7-hydroxy-α-terpineol and perillyl alcohol. Successive oxidations of perillyl alcohol could be performed using no hazardous oxidant and were controlled using the new generation of ecocatalysts generating perillaldehyde and cuminaldehyde.
Preparation of α-terpineol and perillyl alcohol using zeolites beta
?erveny, Libor,Vysko?ilová, Eli?ka,Zítová, Kate?ina
, p. 4297 - 4310 (2021/07/26)
The preparation of α-terpineol by direct hydration of limonene catalyzed by zeolites beta was studied. The same catalyst was used to prepare perillyl alcohol by isomerization of β-pinene oxide in the presence of water. The aim was to optimize the reaction conditions to achieve high conversions of starting material and high selectivity to the desired products. In the case of limonene, it was found that the highest selectivity to α-terpineol was 88% with conversion of 36% under the conditions: 50?wt% of catalyst beta 25, 10% aqueous acetic acid (10?mL) (volume ratio limonene:H2O = 1:4.5), temperature 50?°C, after 24?h. In the case of β-pinene oxide, it was found that the highest selectivity to perillyl alcohol, which was 36% at total conversion, was obtained in the reaction under the following conditions: dimethyl?sulfoxide as solvent (volume ratio β-pinene oxide:DMSO = 1:5), catalyst beta 25 without calcination (15?wt%), demineralized water (molar ratio β-pinene oxide:H2O = 1:8), temperature 70?°C, 3?h. The present study shows that the studied reactions are suitable for the selective preparation of chosen compounds.
Design, synthesis and application of pinenyl chiral olefin and carbene ligand
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Paragraph 0045; 0050-0052, (2020/11/10)
The invention discloses design, synthesis and application of pinenyl chiral olefin and carbene ligands. According to the carbene ligand, pinene or 9-anthraceneformaldehyde is taken as a chiral source,a corresponding bromide is obtained through a two-step reaction, then benzimidazole is taken as an initial raw material, reacts with one molecule of bromide and then reacts with the other molecule ofbromide to form a salt, and corresponding pinenyl chiral olefin and carbene ligands are obtained; the carbene ligand is used as a chiral catalyst to perform asymmetric 1, 4-addition reaction, and hasfavorable selectivity.
Homogeneous Lewis and Br?nsted acids as catalysts for β-pinene oxide rearrangement to prepare myrtenol and myrtanal
Cerveny, Libor,Fidlerova, Barbora,Paterova, Iva,Vavra, Michal,Vyskocilova, Eliska
, (2020/05/19)
Myrtenol and myrtanal find their utilization as fine chemicals or intermediates for the synthesis of food additive myrtanol. β-Pinene oxide rearrangement was studied using homogeneous Lewis and Br?nsted acids as catalysts for the production of these compounds. The composition of reaction products depended on the type of active sites. Lewis active sites favoured the formation of myrtanal while in presence of Br?nsted active sites undesirable perillyl aldehyde and perillyl alcohol were formed to a high extent. Optimal reaction conditions for myrtenol and myrtanal preparation were found. With 5 mol.% of anhydrous SnCl2 as Lewis acid catalysts and 1,4-dioxane as the solvent β-pinene oxide achieved total conversion with 95% selectivity to desired products.
Selective Allylic Oxidation of Terpenic Olefins Using Co-Ag Supported on SiO2 as a Novel, Efficient, and Recyclable Catalyst
Aberkouks, Abderrazak,Mekkaoui, Ayoub Abdelkader,Ait Ali, Mustapha,El Firdoussi, Larbi,El Houssame, Soufiane
, (2020/02/15)
Co-Ag supported on the SiO2 catalyst was synthesized by the sol-gel method and characterized using XRD, FT-IR, TG-DTG, BET, CV, and SEM/EDX analysis. The catalytic performance of the resulting catalyst was examined by the oxidation of mono and sesquiterpenic olefins using hydrogen peroxide and tert-butyl peroxide as oxidant agents. Various parameters such as catalyst amount, temperature, and solvents have been studied. The Co-Ag supported on the SiO2 catalyst showed a high activity, selectivity, and recyclability for the selected oxidation reaction.
Zeolite Y encaged Ru(III) and Fe(III) complexes for oxidation of styrene, cyclohexene, limonene, and α-pinene: An eye-catching impact of H2SO4 on product selectivity
Godhani, Dinesh R.,Nakum, Haresh D.,Parmar, Digvijaysinh K.,Mehta, Jignasu P.,Desai, Nisheeth C.
, p. 223 - 237 (2016/12/09)
A novel Ru(III) and Fe(III) complexes of ligands 1 and/or 2 {where 1 = 2,2'-((1E,1'E)-((azanediylbis(ethane-2,1-diyl))bis(azanylylidene))bis(methanylylidene))diphenol and 2 = 2,2'-((1E,1'E)-((azanediylbis(ethane-2,1-diyl))bis(azanylylidene))bis(methanylylidene)) bis(4-nitrophenol)} have been synthesized as ‘neat’ and zeolite Y encapsulated complexes. These catalysts are characterized by various analytical tools such as FTIR, UV–vis, elemental analysis, ICP-AES, molar conductivity, 1H- and 13C NMR, TGA, SEM, AAS, BET, magnetic susceptibility and powder XRD to endorse the complex formation, absence of peripheral redundant ligands and complexes, conservation of zeolite Y morphology and crystallinity, and the encapsulation of complexes without devastation in the zeolite Y framework. Out of these synthesized catalysts, 5Y is found to be a potent candidate for styrene (Conv. 76.1%, TOF: 2130 h?1), cyclohexene (Conv. 84.4%, TOF: 2351 h?1), limonene (Conv. 81.6%, TOF: 2273 h?1), and α-pinene (Conv. 72.6%, TOF: 2023 h?1) oxidation with high selectivity of respective allylic products excluding the styrene oxidation, which undergoes epoxidation only. The addition of H2SO4 in an identical reaction catalyzed by 5Y not only surge the conversion up to 100% in a short time span with high TOF but also increase the selectivity of respective epoxidation products. This switchover in the selectivities could be credited to the presence of H2SO4 that facilitates the heterolytic [sbnd]O[sbnd]O[sbnd] bond cleavage of metal hydroperoxide and stimulates the epoxidation over allylic oxidation. Furthermore, the results establish that the heterogeneous systems are effortlessly recovered and reused without ample drop in the activity and selectivity.
Solvent and additive-free selective aerobic allylic hydroxylation of β-pinene catalyzed by metalloporphyrins
Xu, Shi-Chao,Zhu, Shou-Ji,Bi, Liang-Wu,Chen, Yu-Xiang,Wang, Jing,Lu, Yan-Ju,Gu, Yan,Zhao, Zhen-Dong
, p. 575 - 578 (2017/06/19)
Metallodeuteroporphyrins (MDPs) were employed as the catalysts for aerobic oxidation of β-pinene in absence of solvents and additives. Allylic hydroxylation products were found to be the main products from this protocol. The catalytic activity of MDPs with different metal nuclei and the influences of technological conditions on this reaction were investigated. This catalytic system has bright application prospect since only eco-friendly and readily available dioxygen were needed.
Beta-pinene selective hydroxylation oxidation method and product thereof
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Paragraph 0032; 033; 0334;, (2016/10/10)
The invention discloses a beta-pinene selective hydroxylation oxidation method and a product thereof. The beta-pinene selective hydroxylation oxidation method uses ordinary-pressure oxygen or oxygen-enriched air as an oxidant, uses metal porphyrin or their solid carriers as a catalyst and is performed in the absence of an additional solvent or a co-oxidation reducer, and the beta-pinene hydroxylation oxidation product is obtained by means of the method in a high-selectivity mode. Main oxidation products include pinocarveol, 2,10-epoxy pinane and myrtenol, wherein the overall selectivity of the hydroxylation oxidation products 1 and 3 is above 90%. The usage amount of the catalyst used in method is small, a reaction process is simple, the temperature is low, the initiation rate is high, the selectivity is good, homogeneous catalysis can be achieved, and heterogeneous catalysis can also be performed after immobilization.
Biologically Inspired and Magnetically Recoverable Copper Porphyrinic Catalysts: A Greener Approach for Oxidation of Hydrocarbons with Molecular Oxygen
Henriques, César A.,Fernandes, Auguste,Rossi, Liane M.,Ribeiro, M. Filipa,Calvete, Mário J. F.,Pereira, Mariette M.
, p. 3359 - 3368 (2016/06/06)
An efficient synthetic method for magnetically recoverable hybrid copper porphyrinic nanomaterials is reported. These functionalized magnetic materials prove to be efficient bioinspired oxidation catalysts of olefins and thiols, using molecular oxygen as oxidant, in total absence of reductants and solvents, with the highest TON (turnover number) yet achieved for this reaction (≈200 000). A comparative study between homogeneous and heterogeneous oxidation of cyclohexene is discussed, revealing the heterogeneous system to be the most promising concerning stability and reusability of the catalysts. The full characterization of the magnetic hybrid porphyrinic nanomaterials, by transmission electron microscopy, flame atomic absorption spectrometry, thermogravimetry, N2 sorption, and infrared spectroscopy, is also described.
