90-05-1Relevant articles and documents
Deposition–precipitation approach for preparing core/shell SiO2@Ni-Rh nanoparticles as an advanced catalyst for the dehydrogenation of 2-methoxycyclohexanol to guaiacol
Feng, Junbo,Jiang, Wei,Yuan, Caicai,Shi, Xiancai,Zang, Kai,Zhang, Yadong
, p. 106 - 113 (2018)
A novel core/shell nano-bimetallic catalyst SiO2@Ni-Rh was successfully prepared by deposition–precipitation method, using liquid ammonia as a precipitating agent. SEM, TEM, XRD, XPS, H2-TPR, H2-TPD and adsorption/desorption of nitrogen were employed to systematically investigate the surface morphology, size, chemical composition, reducibility, Ni dispersion and structure of the as-synthesized nanoparticles. It is found that the nickel and rhodium are uniformly dispersed on the silica surface to form core/shell SiO2@Ni-Rh nanoparticles with Ni atoms and Rh atoms as the outer shell and SiO2 as the core, which possess high dispersion of Ni on the surface and high specific surface area (234.063 m2/g) of the catalyst with the mean particle size of ca. 130 nm. The dehydrogenation of 2-methoxycyclohexanol to guaiacol was used as the model reaction for evaluating the catalytic activity of the as-synthesized core/shell various Ni and Rh-containing bimetallic nanoparticles in a tubular stainless steel reactor. SiO2@15Ni-0.4Rh nanoparticles have exhibited remarkable catalytic performance, with 98.3% conversion and 93.6% selectivity of guaiacol, due to high dispersion of metal nanoparticles and synergistic effect of bimetallic Ni-Rh over the special core/shell SiO2@Ni-Rh by the addition of rhodium. Furthermore, turn over frequency value of SiO2@15Ni-0.4Rh nanoparticles achieves 0.47 s?1, showing high catalytic efficiency. In general, the dehydrogenation of 2-methoxycyclohexanol over the core-shell-like SiO2@Ni-Rh nanoparticles in a continuous fixed-bed reactor is a more promising, high atom economy, high efficient, easy separation, environmental friendliness, green synthetic pathway of guaiacol.
Solar filters as feasible acceptors of atomic oxygen
Duran-Giner, Neus,Encinas, Susana,Miranda, Miguel A.
, p. 725 - 728 (2013)
The triazine derivative Tinosorb S has been shown to accept atomic oxygen generated by N-oxide photodeoxygenation. This is a unique example of a solar filter and mechanism-directed antioxidant. The concept has been proved by a combination of steady-state and laser-flash photolysis.
Selective dealkylations of alkyl aryl ethers in heterogeneous basic media under microwave irradiation
Oussaid, Abdelouahad,Thach, Le Ngoc,Loupy, Andre
, p. 2451 - 2454 (1997)
Ethyl isoeugenol and 2-ethoxyanisole could be selectively deethylated using potassium t-butoxide in the presence of crown ether under solvent-free conditions. By addition of ethylene glycol, selectivity was reversed to demethylation. In both cases, strong enhancements were observed under focused microwaves.
Catechol O-methylation with dimethyl carbonate over different acid-base catalysts
Luque, Rafael,Manuel Campelo, Juan,Conesa, Tomas David,Luna, Diego,Marinas, Jose Maria,Romero, Antonio Angel
, p. 1228 - 1234 (2006)
A series of meso and microporous materials, previously described and characterised, were tested in the catechol O-alkylation process using methanol (MeOH) and dimethyl carbonate (DMC) as alkylating reagents. In this regard, interesting results in terms of catalytic activity and selectivity to the desired monomethylated product (guaiacol) compared to the dimethylated one (veratrole) were found for the majority of the catalysts. Moreover, DMC is a better methylating agent than methanol with respect to the conversion ratio of catechol and guaiacol. The presence of n-type nucleophilic centres (oxygen from the OH groups) together with π-type ones (aromatic ring) in catechol led only to O-alkylated (guaiacol and veratrole), whereas no C-alkylated products were found under the reaction conditions. AlPO4 and, especially, AlPO 4-Al2O3 systems showed the best performance in this alkylation process in comparison with silicoaluminophosphates (SAPO) and some acidic commercial zeolites (H-Y, H-β and H-ZSM-5). the Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2006.
Imidazolium-urea low transition temperature mixtures for the UHP-promoted oxidation of boron compounds
Martos, Mario,Pastor, Isidro M.
, (2022/01/03)
Different carboxy-functionalized imidazolium salts have been considered as components of low transition temperature mixtures (LTTMs) in combination with urea. Among them, a novel LTTM based on 1-(methoxycarbonyl)methyl-3-methylimidazolium chloride and urea has been prepared and characterized by differential scanning calorimetry throughout its entire composition range. This LTTM has been employed for the oxidation of boron reagents using urea-hydrogen peroxide adduct (UHP) as the oxidizer, thus avoiding the use of aqueous H2O2, which is dangerous to handle. This metal-free protocol affords the corresponding alcohols in good to quantitative yields in up to 5 mmol scale without the need of further purification. The broad composition range of the LTTM allows for the reaction to be carried out up to three consecutive times with a single imidazolium salt loading offering remarkable sustainability with an E-factor of 7.9, which can be reduced to 3.2 by the threefold reuse of the system.
Semi-Batch Hydrotreatment of Lignin-Derived Phenolic Compounds over Raney-Ni with a Continuous Regeneration of the H-Donor Solvent
Kubi?ka, David,Shumeiko, Bogdan
, (2021/12/09)
Lignin can be converted into useful precursors of fuels and fine chemicals by thermochemical conversion followed by catalytic hydrogenation using metal catalysts at severe reaction conditions. Thus, mild hydrogenation would significantly improve the susta
Photophysics of Perylene Diimide Dianions and Their Application in Photoredox Catalysis
Li, Han,Wenger, Oliver S.
, (2021/12/23)
The two-electron reduced forms of perylene diimides (PDIs) are luminescent closed-shell species whose photochemical properties seem underexplored. Our proof-of-concept study demonstrates that straightforward (single) excitation of PDI dianions with green
One-Pot Transformation of Lignin and Lignin Model Compounds into Benzimidazoles
Guo, Tao,He, Jianghua,Liu, Tianwei,Zhang, Yuetao
supporting information, (2022/02/07)
It is a challenging task to simultaneously achieve selective depolymerization and valorization of lignin due to their complex structure and relatively stable bonds. We herein report an efficient depolymerization strategy that employs 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) as oxidant/catalyst to selectively convert different oxidized lignin models to a wide variety of 2-phenylbenzimidazole-based compounds in up to 94 % yields, by reacting with o-phenylenediamines with varied substituents. This method could take full advantage of both Cβ and/or Cγ atom in lignin structure to furnish the desirable products instead of forming byproducts, thus exhibiting high atom economy. Furthermore, this strategy can effectively transform both the oxidized hardwood (birch) and softwood (pine) lignin into the corresponding degradation products in up to 45 wt% and 30 wt%, respectively. Through a “one-pot” process, we have successfully realized the oxidation/depolymerization/valorization of natural birch lignin at the same time and produced the benzimidazole derivatives in up to 67 wt% total yields.
Photocatalytic synthesis of phenols mediated by visible light using KI as catalyst
Huiqin, Wei,Wu, Mei
supporting information, (2021/11/30)
A transition-metal-free hydroxylation of iodoarenes to afford substituted phenols is described. The reaction is promoted by KI under white LED light irradiation and uses atmospheric oxygen as oxidant. By the use of triethylamine as base and solvent, the corresponding phenols are obtained in moderate to good yields. Mechanistic studies suggest that KI and catalysis synergistically promote the cleavage of C-I bond to form free aryl radicals.
Thio-assisted reductive electrolytic cleavage of lignin β-O-4 models and authentic lignin
Fang, Zhen,Flynn, Michael G.,Jackson, James E.,Hegg, Eric L.
supporting information, p. 412 - 421 (2021/01/28)
Avoiding the use of expensive catalysts and harsh conditions such as elevated temperatures and high pressures is a critical goal in lignin depolymerization and valorization. In this study, we present a thio-assisted electrocatalytic reductive approach using inexpensive reticulated vitreous carbon (RVC) as the working cathode to cleave the β-O-4-type linkages in keto aryl ethers. In the presence of a pre-electrolyzed disulfide (2,2′-dithiodiethanol) and a radical inhibitor (BHT) at room temperature at a current density of 2.5 mA cm-2, cathodic reduction of nonphenolic β-O-4 dimers afforded over 90% of the corresponding monomeric C-O cleavage products in only 1.5 h. Extended to DDQ-oxidized poplar lignin, this combination of electric current and disulfide, applied over 6 h, released 36 wt% of ethyl acetate soluble fragments and 26 wt% of aqueous soluble fragments, leaving only 38 wt% of insoluble residue. These findings represent a significant improvement over the current alone values (24 wt% ethyl acetate soluble; 22 wt% aqueous soluble; 54 wt% insoluble residue) and represent an important next step in our efforts to develop a mild electrochemical method for reductive lignin deconstruction.
