1071-73-4Relevant articles and documents
Solvent free permanganate oxidations
Shaabani, Ahmad,Lee, Donald G.
, p. 5833 - 5836 (2001)
The oxidations of organic compounds by permanganate under solvent free conditions have been studied. Thiols and primary aromatic amines undergo oxidative coupling reactions to give disulfides and diazenes, respectively, sulfides are oxidized to sulfones, primary and secondary alcohols are converted to aldehydes and ketones, 1,4-diols and cyclic ethers give lactones and arenes are oxidized to the corresponding α-ketones. The experimental procedure is simple and the products are easily isolated in good yields.
Regioselectivity in the Semiconductor-Mediated Photooxidation of 1,4-Pentanediol
Fox, Marye Anne,Ogawa, Haruo,Pichat, Pierre
, p. 3847 - 3852 (1989)
Optimum conditions have been established for the selective semiconductor-photocatalyzed oxidation by long-wavelength ultraviolet light of the primary alcohol functionality in 1,4-pentanediol.On platinized (2percent) TiO2 powder suspended in oxygenated aqueous (4 vol percent) acetonitrile, the initial rate ratio for oxidation of the primary/secondary alcohol site was > 7.Analysis of further oxidation products allowed for mechanistic delineation of the course of the semiconductor-mediated reaction.The selectivity is attributed to the essential role of adsorption, with the criticalphotoinduced electron transfer occurring at the surface of the irradiated particle.ZrO2 and SnO2 samples were much less active than TiO2 as photocatalysts.The effects of oxygen pressure, metal cocatalyst loading, and water content of acetonitrile are discussed.
Analytical methodology for determination of organic aerosol functional group distributions
Kalafut-Pettibone, Alicia J,McGivern, W. Sean
, p. 3553 - 3560 (2013)
Secondary organic aerosol (SOA) particles result from the condensation of oxidized volatile organic compounds (VOC) and consist of a complex mixture that is not conducive to complete compositional analysis. We present a simple methodology for determining the quantities of aldehydes and ketones, alcohols, and carboxylic acids in such samples via derivatization and high-performance liquid chromatography (HPLC) with ultraviolet-visible absorption detection and tandem mass spectrometry (MS/MS). Useful concentration ranges are presented with an examination of the specificity of these compounds in multiply substituted systems. Such data are valuable in modeling the formation of laboratory-generated aerosols and in identifying point sources of field-collected aerosol samples. Calibration curves on standard samples, MS/MS transitions, including collisionally induced dissociation (CID) products, and a quantitative examination of the specificity of the derivatization reagents toward multiple functional groups are presented for a series of aliphatic standard samples. These methods are then applied to filter extracts from SOA derived from 1-iodooctane photolysis at 254 nm to demonstrate the methodology on a complex system. Ultimately, this methodology enables the measurement of variations in the chemical nature of the oxygen within an SOA particle, providing a distribution of functional group concentrations. This article not subject to U.S. Copyright. Published 2013 by the American Chemical Society.
Fe(III)-porphyrin heterogenized on MCM-41: Matrix effects on the oxidation of 1,4-pentanediol
Molinari, Alessandra,Maldotti, Andrea,Bratovcic, Amra,Magnacca, Giuliana
, p. 64 - 69 (2011)
The metal complex iron meso-tetrakis (2,6-dichlorophenyl)porphyrin (Fe IIIP) has been covalently linked on the surface of the mesoporous material MCM-41 and of amorphous SiO2 to give the photocatalysts FeIIIP/MCM-41 and FeIIIP/SiO2 respectively. The effect of porphyrin addition on specific surface area and porosity of these materials has been evaluated by means of BET and BJH model applied to N 2 adsorption/desorption isotherms. It is seen that the MCM-41 sample presents the largest modification due to the presence of porphyrin: the pore size changes in average value and distribution, the pores formed in the presence of porphyrin being smaller and presenting a larger distribution. The photochemical characterization of FeIIIP/MCM-41 reveals that this is a robust photocatalyst able to induce the O2-assisted oxidation of 1,4-pentanediol. In particular, photoexcitation of FeIIIP/MCM-41 causes the conversion of 1,4-pentanediol to the aldehyde derivative compound with 70% regioselectivity. It is noteworthy that this product can be accumulated with no formation of further oxidized compounds. Due to its high specific surface area, which guarantees a good dispersion of the active centres, Fe IIIP/MCM-41 is about four times more efficient than Fe IIIP/SiO2. Moreover, the nature of the support controls the regioselectivity of the photocatalytic process: this is due to both uptake phenomena and steric effects, which can control the approach of the diol to the photoactive iron porphyrin.
Catalytic cascade conversion of furfural to 1,4-pentanediol in a single reactor
Liu, Fei,Liu, Qiaoyun,Xu, Jinming,Li, Lei,Cui, Yi-Tao,Lang, Rui,Li, Lin,Su, Yang,Miao, Shu,Sun, Hui,Qiao, Botao,Wang, Aiqin,Jér?me, Francois,Zhang, Tao
, p. 1770 - 1776 (2018)
The synthesis of bio-based linear diols is the subject of many research studies. However, one of the main obstacles in industrial development is the difficulty in controlling product selectivity. Here, we report the catalytic conversion of furfural to 1,4-pentanediol (PD) in the presence of Ru supported on an ordered mesoporous carbon (CMK-3) under pressure of H2 and CO2 in water. In contrast to previous catalytic pathways, this work is distinct in that it yields 1,4-PD as an exclusive product, instead of a mixture of 1,2- and 1,5-PD as usual. Under optimized conditions, 1,4-PD was obtained in 90% yield, and in a one-pot reaction, directly from furfural. We disclose that the conversion of furfural to 1,4-PD followed an unusual catalytic route. It implies a bifunctional catalytic pathway based on sequential catalytic hydrogenation reactions and an acid-catalyzed Piancatelli's rearrangement.
Tweaking the acid-sensitivity of transiently thermoresponsive Polyacrylamides with cyclic acetal repeating units
De Geest, Bruno G.,Van Herck, Simon
, (2020)
Merging the characteristics of thermoresponsive and stimuli-degradable polymers yields so-called transiently thermoresponsive polymers, which can find application for the design of injectable gels, nanoparticles, etc. within a biomedical context. Among these polymers, only a limited number is reported which shows selective degradation under mild acidic conditions. However, extension of the library of transiently thermoresponsive polymers is desired to broadening the biomaterials toolbox to suit specific needs. Three monomers were developed by modification of 2-hydroxyethylacrylamide (HEAm) via tetrahydropyranylation or -furanylation with 3,4-dihydro-2H-pyran (DHP), 2,3-dihydrofuran (DHF) or 2,3-dihydro-5-methylfuran (MeDHF). The presence of an acetal or ketal bond provided the monomers a pH-dependent hydrolysis behavior ranging from minutes to days. RAFT polymerisation allowed for the construction of homopolymers with temperature responsive behavior and pH-dependent hydrolysis which was strongly influenced by nature of the monomeric repeating units.
Catalytic production of 1,4-pentanediol from furfural in a fixed-bed system under mild conditions
Liu, Fei,Liu, Qiaoyun,Qiao, Botao,Su, Yang,Wang, Aiqin,Zhang, Leilei,Zhang, Tao
, p. 3532 - 3538 (2020)
Furfural is one of the most important biomass-derived chemicals. Its large-scale availability calls for the exploration of new transformation methods for further valorization. Here we report on the direct, one-step conversion of furfural into 1,4-pentanediols (1,4-PeDs) using a combination of Amberlyst-15 and Ru-FeOx/AC catalysts. It is interesting to find that the introduction of a suitable amount of FeOxresults in a great improvement in the dispersion of Ru and a decrease in the Lewis acidity. Both XPS and H2-TPR show that there is electron transfer from Ru to Fe, and the electronic interaction facilitates the reduction of both Ru and Fe species. When used in combination with Amberlyst-15, the Ru-6.3FeOx/AC catalyst afforded the best performance with a 1,4-PeD yield of 86%; by contrast, Ru/AC free of FeOxonly gave levulinic acid as the major product, demonstrating the key role of the acid/metal balance in the one-pot conversion of furfural to 1,4-PeD. Moreover, such a dual catalyst exhibited excellent durability within 175 h time-on-stream.
Palladium(II)-catalyzed oxidation of terminal alkenes to methyl ketones using molecular oxygen
Nishimura, Takahiro,Kakiuchi, Nobuyuki,Onoue, Tomoaki,Ohe, Kouichi,Ucmura, Sakae
, p. 1915 - 1918 (2000)
Palladium(II) acetate catalyzes the aerobic oxidation of terminal alkenes in toluene into the corresponding methyl ketones in the presence of a catalytic amount of pyridine using propan-2-ol as a reductant and molecular oxygen as an oxidant. Two catalytic cycles sharing a Pd(II)-OOH species are proposed. One is the formation of a Pd(II)-H species in the oxidation of propan-2-ol to acetone, followed by reaction with molecular oxygen to give a Pd(II)-OOH species, and the other is peroxypalladation of an alkene with the Pd(II)-OOH species produced to afford a methyl ketone in the presence of H2O2 produced by the former catalytic cycle. The Royal Society of Chemistry 2000.
Ru Nanoparticles on a Sulfonated Carbon Layer Coated SBA-15 for Catalytic Hydrogenation of Furfural into 1, 4-pentanediol
Cui, Kai,Qian, Wei,Shao, Zhengjiang,Zhao, Xiuge,Gong, Honghui,Wei, Xinjia,Wang, Jiajia,Chen, Manyu,Cao, Xiaoming,Hou, Zhenshan
, p. 2513 - 2526 (2021)
Furfural (FFR) is one of the most important biomass-derived chemicals. Its large-scale availability calls for the exploration of new transformation methods for further valorization. Herein, we demonstrate that Ru nanoparticles (Ru NPs)-supported on a sulfonated carbon layer coated SBA-15 can be employed as an efficient bi-functional catalyst for one step conversion of FFR into 1,4-pentanediol (1,4-PeDO). The optimum bi-functional catalyst can afford the full the conversion of FFR and 86% selectivity to 1,4-PeDO. The catalysts have been characterized thoroughly by using a complementary combination of powder X-ray diffraction, N2 adsorption–desorption, scanning/transmission electron microscopy, Fourier transform infrared spectroscopy, elemental analysis, and X-ray photoelectron spectroscopy. The characterization revealed that acidic groups (–SO3H) have been introduced on the surface of the carbon layer coated SBA-15 support after sulfonation with 98% H2SO4 and the surface acidity can be tuned facilely by the sulfonating time. Meantime, Ru(0) sites was highly dispersed via an impregnation and sequential reduction and directly adjacent to the surface –SO3H group. There existed an electronic interaction between Ru(0) sites and sulfonic groups, in which the electronic transfer from sulfonic sites to Ru(0) sites occurred. Br?nsted acid sites (–SO3H) have a significant influence on the FFR conversion and the selectivity to 1,4-PeDO. The ordered mesoporous structure, the appropriate density of acid sites and the electron-rich Ru(0) sites accounted for the the excellent performance of the catalyst for an efficient production of 1,4-PeDO from FFR. Graphic Abstract: [Figure not available: see fulltext.].
Supported gold nanoparticles as a reusable catalyst for synthesis of lactones from diols using molecular oxygen as an oxidant under mild conditions
Mitsudome, Takato,Noujima, Akifumi,Mizugaki, Tomoo,Jitsukawa, Koichiro,Kaneda, Kiyotomi
, p. 793 - 797 (2009)
The oxidative lactonization of various diols using molecular oxygen as a primary oxidant can be efficiently catalyzed by hydrotalcite-supported Au nanoparticles (Au/HT). For instance, lactonization of 1,4-butanediol gave γ-butyrolactone with an excellent turnover number of 1400. After lactonization, the Au/HT can be recovered by simple filtration and reused without any loss of its activity and selectivity.
