100-51-6Relevant articles and documents
Intracrystalline reactivity of layered double hydroxides: Carboxylate alkylations in dry media
Garcia-Ponce, Angel Luis,Prevot, Vanessa,Casal, Blanca,Ruiz-Hitzky, Eduardo
, p. 119 - 121 (2000)
This work concerns the reactivity in dry media conditions, i.e. without solvents, of layered double hydroxide (LDH) solids, containing carboxylate ions in their structure, towards alkyl and benzyl halides. Reaction occurs giving the corresponding esters, with excellent yield and selectivity, and preserving the lamellar arrangement of the pristine solids. The reactions were activated by conventional thermal treatment (100 °C) or by microwave (MW) irradiation.
Nitrous Oxide as a Nucleophile in the Formation of a New Reactive Intermediate from Benzyl Cations in the Solvolysis of Benzyl Azoxytosylate
Maskill, H.,Jencks, William P.
, p. 944 - 946 (1984)
Rate and product analytical results of solvolysis of benzyl azoxytosylate in 1:1 (v/v) trifluoroethanol : water require two product-forming routes: one involves a long-lived intermediate (formed from benzyl cations and nitrous oxide) which is trappable by
Reactivity of silole within a core-modified porphyrin environment: Synthesis of 21-silaphlorin and its conversion to carbacorrole
Skonieczny, Janusz,Latos-Grazynski, Lechoslaw,Szterenberg, Ludmila
, p. 4861 - 4874 (2008)
Condensation of 1,1-dimethyl-3,4-diphenyl-2,5-bis(p-tolylhydroxymethyl) silole with pyrrole and p-tolylaldehyde did not form the expected 21,21-dimethyl-2,3-diphenyl-5,10,15,20-tetra(p-tolyl)-21 -silaporphy rin, but rather its reduced derivative, 21-silap
REDUCTIVE COUPLING OF AROMATIC ALDEHYDES BY OCTACARBONYL DIFERRATE
Ito, Keiji,Nakanishi, Saburo,Otsuji, Yoshio
, p. 1141 - 1144 (1980)
The reaction of aromatic aldehydes with Fe(CO)5 or Fe3(CO)12 in pyridine gives the corresponding 1,2-diaryl-1,2-ethanediols as major products in good yields.A reactive species of this reaction is octacarbonyl diferrate (2-).
Novel preparation of 2,1-benzothiazine derivatives from sulfonamides with [hydroxy(tosyloxy)iodo]arenes
Misu, Yuhta,Togo, Hideo
, p. 1342 - 1346 (2003)
Cyclization of sulfonamides bearing an aromatic ring at the β-position with various organohypervalent iodine compounds was carried out to form the corresponding 2,1-benzothiazine derivatives. Among them, the cyclization effectively proceeded with [hydroxy
Manganese Catalyzed Hydrogenation of Organic Carbonates to Methanol and Alcohols
Kumar, Amit,Janes, Trevor,Espinosa-Jalapa, Noel Angel,Milstein, David
, p. 12076 - 12080 (2018)
The first example of a homogeneous catalyst based on an earth-abundant metal for the hydrogenation of organic carbonates to methanol and alcohols is reported. Based on the mechanistic investigation, which indicates metal-ligand cooperation between the manganese center and the N?H group of the pincer ligand, we propose that the hydrogenation of organic carbonates to methanol occurs via formate and aldehyde intermediates. The reaction offers an indirect route for the conversion of CO2 to methanol, which coupled with the use of an earth abundant catalyst, makes the overall process environmentally benign and sustainable.
Oxidation of toluene in NOx free air: product distribution and mechanism
Seuwen, P.,Warneck, P.
, p. 315 - 332 (1996)
Product distributuion resulting from the oxidation in air initiated by chlorine atoms, by toluene photolysis, and by hydroxyl radicals were studied at atmospheric pressure in the absence of nitrogen oxides.In the first case only benzaldehyde and benzylalcohol with a ratio of 7.8 +/- 1.7 were observed, from wich a branching ratio α = 0.76 +/- 0.05 was derived for the radical propagating pathway of the self-reaction of benzylperoxy radicals.In the second and third case the apparent branching ratio decreased to α = 0.56 +/- 0.07 and 0.37 +/- 0.08, respectively, indicating the occurence of additional reactions between benzylperoxy and other peroxy radicals.The major ring retaining products resulting from the reaction of OH with toluene were o-cresol, p-cresol, and methyl-p-benzo-quinone (57.9 +/- 12.5percent reacted carbon, corrected for secondary losses), in addition to 7.7 +/- 1.6percent benzaldehyde and benzylalcohol arising from methyl hydrogen abstraction.Formaldehyde, acetaldehyde, glyoxal, methylglyoxal, carbon monoxide, and carbon dioxide were observed as ring cleavage products (25.0 +/- 7.2percent).Except for CO2, which appears to be an important ring cleavage product only under NOx-free conditions, the distribution of ring cleavage products was similar to that found by Gery et al. (1985) in the presence of NOx.Comparison of experimental data and results from computer simulations show that self-reactions of the hydroxy-methyl-cyclo-hexadienylperoxy radicals are negligible compared to internal rearrangement reactions leading to ring stabilization or ring cleavage.The mechanisms of CO2 production appears to require the formation of a Criegee intermediate.
Iron-catalyzed hydrosilylation of esters
Bezier, David,Venkanna, Gopaladasu T.,Castro, Luis C. Misal,Zheng, Jianxia,Roisnel, Thierry,Sortais, Jean-Baptiste,Darcel, Christophe
, p. 1879 - 1884 (2012)
The first hydrosilylation of esters catalyzed by a well defined iron complex has been developed. Esters are converted to the corresponding alcohols at 100 °C, under solvent-free conditions and visible light activation. Copyright
Solvent-free reduction of carboxylic acids to alcohols with NaBH4 promoted by 2,4,6-trichloro-1,3,5-triazine and PPh3 in the presence of K2CO3
Jaita, Subin,Kaewkum, Pantitra,Duangkamol, Chuthamat,Phakhodee, Wong,Pattarawarapan, Mookda
, p. 46947 - 46950 (2014)
A simple, rapid, and eco-friendly method for NaBH4 reduction of carboxylic acids to alcohols under solvent-free conditions was developed using a combination of 2,4,6-trichloro-1,3,5-triazine (TCT) with a catalytic amount of triphenylphosphine as an acid activator. With the 1 : 0.2 : 1.5 : 2 mole ratio of TCT : PPh3 : K2CO3 : NaBH4, carboxylic acids including aromatic acids, aliphatic acids, and N-protected α-amino acids (Fmoc, Z) could readily undergo reduction to give the corresponding alcohols in good to excellent yields within 10 min.
A Pd@Zeolite Catalyst for Nitroarene Hydrogenation with High Product Selectivity by Sterically Controlled Adsorption in the Zeolite Micropores
Zhang, Jian,Wang, Liang,Shao, Yi,Wang, Yanqin,Gates, Bruce C.,Xiao, Feng-Shou
, p. 9747 - 9751 (2017)
The adsorption of molecules on metal nanoparticles can be sterically controlled through the use of zeolite crystals, which enhances the product selectivity in hydrogenations of reactants with more than one reducible group. Key to this success was the fixation of Pd nanoparticles inside Beta zeolite crystals to form a defined structure (Pd@Beta). In the hydrogenation of substituted nitroarenes with multiple reducible groups as a model reaction, the Pd@Beta catalyst exhibited superior selectivity for hydrogenation of the nitro group, outperforming both conventional Pd nanoparticles supported on zeolite crystals and a commercial Pd/C catalyst. The extraordinary selectivity of Pd@Beta was attributed to the sterically selective adsorption of the nitroarenes on the Pd nanoparticles controlled by the zeolite micropores, as elucidated by competitive adsorption and adsorbate displacement tests. Importantly, this strategy is general and was extended to the synthesis of selective Pt and Ru catalysts by fixation inside Beta and mordenite zeolites.
