1003-66-3Relevant articles and documents
Mechanistic Insight into Weak Base-Catalyzed Generation of Carbon Monoxide from Phenyl Formate and Its Application to Catalytic Carbonylation at Room Temperature without Use of External Carbon Monoxide Gas
Konishi, Hideyuki,Matsubara, Mika,Mori, Keisuke,Tokiwa, Takaki,Arulmozhiraja, Sundaram,Yamamoto, Yuta,Ishikawa, Yoshinobu,Hashimoto, Hiroshi,Shigeta, Yasuteru,Tokiwa, Hiroaki,Manabe, Kei
, p. 3592 - 3601 (2017)
The mechanisms of the weak base-catalyzed generation of carbon monoxide (CO) and phenol from phenyl formate were investigated by experimental and theoretical methods. Kinetic studies revealed a first-order reaction in both phenyl formate and the base. The reaction was found to proceed by an E2 α-elimination pathway, which involves the abstraction of the formyl proton of phenyl formate, simultaneously generating CO and phenoxide. The reaction rate was affected by the substituents on phenyl formate, the polarity of solvents, and the basicity of bases. The mechanistic insight obtained from these studies permitted the chemical control of the rate of CO generation, which was the key to the development of the external CO-free Pd-catalyzed phenoxycarbonylation of haloarenes at room temperature. Because of the mild reaction conditions and wide substrate scope, this phenoxycarbonylation constitutes a general, safe, and practical method to synthesize arenecarboxylic acid esters. (Figure presented.).
Orientational dynamics of hydrogen-bonded phenol
Rezus,Madsen,Bakker
, p. 10599 - 10604 (2004)
We use femtosecond mid-infrared pump-probe spectroscopy to study the effects of hydrogen bonding on the orientational dynamics of the OD-stretch vibration of phenol-d. We study two samples: phenol-d in chloroform and phenol-d in chloroform to which we add
Highly selective Pd@mpg-C3N4 catalyst for phenol hydrogenation in aqueous phase
Li, Yi,Xu, Xuan,Zhang, Pengfei,Gong, Yutong,Li, Haoran,Wang, Yong
, p. 10973 - 10982 (2013)
The liquid phase selective hydrogenation of phenol to cyclohexanone has been investigated over polymeric mesoporous graphitic carbon nitride (mpg-C 3N4) supported Pd catalysts (Pd@mpg-C3N 4). This Pd@mpg-C3
Photocatalytic Hydrogen-Evolution Cross-Couplings: Benzene C-H Amination and Hydroxylation
Zheng, Yi-Wen,Chen, Bin,Ye, Pan,Feng, Ke,Wang, Wenguang,Meng, Qing-Yuan,Wu, Li-Zhu,Tung, Chen-Ho
, p. 10080 - 10083 (2016)
We present a blueprint for aromatic C-H functionalization via a combination of photocatalysis and cobalt catalysis and describe the utility of this strategy for benzene amination and hydroxylation. Without any sacrificial oxidant, we could use the dual catalyst system to produce aniline directly from benzene and ammonia, and phenol from benzene and water, both with evolution of hydrogen gas under unusually mild conditions in excellent yields and selectivities.
Pair Formation of Phenol in the Vicinity of an Aqueous Solution Surface Studied by Means of Liquid Beam Multiphoton Ionization Mass Spectrometry
Mafune, Fumitaka,Hashimoto, Yuichiro,Hashimoto, Mitsuo,Kondow, Tamotsu
, p. 13814 - 13818 (1995)
An aqueous solution of phenol was introduced into vacuum as a continuous liquid flow (liquid beam) and was irradiated with a laser beam at a wavelength of 272 nm.Ions produced by multiphoton ionization in the liquid beam and ejected from it were analyzed by a time-of-flight mass spectrometer.The mass spectrum of ions ejected from the liquid beam exhibits peaks assignable to C6H5OH+(H2O)n, H3O+(H2O)n, and C6H5O+C6H5OH.The ions C6H5OH+ and H3O+ are considered to be produced in the liquid beam by multiphoton ionization of phenol and proton transfer from phenol to a water molecule, respectively; these ions are ejected into vacuum with the solvent water molecules.On the other hand, C6H5O+C6H5OH is considered to be produced mainly from a pair of phenol molecules in the vicinity of the solution surface.This ion is regarded as the precursor for formation of phenoxyphenol, C6H5OC6H4OH, which is known as a product of the ion-molecule reaction of C6H5O+ + C6H5OH in the liquid.An abrupt rise in the abundance of C6H5O+C6H5OH above 0.55 M indicates that the surface structure starts to change at this concentration to a new one where two phenol molecules are paired.
A New Method for Obtaining Isotopic Fractionation Data at Multiple Sites in Rapidly Exchanging Systems
Jarret, Ronald M.,Saunders, Martin
, p. 2648 - 2654 (1985)
A new method for rapidly and conveniently obtaining isotopic fractionation factors in dilute aqueous solutions of compounds containing rapidly exchanging OH, NH, and SH groups is described.Shifts in the positions of NMR peaks for spectroscopically observable nuclei induced by isotopic substitution are the basis of this procedure which has the unique capability of separately measuring the isotopic exchange constants simultaneously for several different groups in the same molecule.The results for a series of alcohols, amines, thiols, phenols, acids, and amides with use of 13C NMR spectroscopy are reported.Atypically low values of Kfrac are observed in several cases, indicating that there are strong internal hydrogen bonds in competition with those to water, yielding conformational information.
Room Temperature Activation of Aromatic C-H Bonds by Non-Classical Ruthenium Hydride Complexes Containing Carbene Ligands
Giunta, Daniela,H?lscher, Markus,Lehmann, Christian W.,Mynott, Richard,Wirtz, Cornelia,Leitner, Walter
, p. 1139 - 1145 (2003)
Non-classical ruthenium hydride complexes are promising lead structures for the C-H bond activation and functionalization of aromatic compounds. In the present paper, the preparation and crystallographic characterisation of the first organo-metallic complexes bearing dihydrogen ligands and N-heterocyclic carbene ligands in the same coordination sphere are described. The mixed phosphine/ carbene complex [(IMes)Ru(H)2(H2) 2(PCy3)] (IMes = 1,3-dimesityl-1,3-dihydro-2H-imidazol-2- ylidene; 3a) shows a unique reactivity pattern in the inter- and intramolecular activation of C-H bonds. In particular, complex 3a effects a rapid and remarkably selective intermolecular activation of sp2 C-H bonds in simple aromatic compounds at room temperature.
Negligible Isotopic Effect on Dissociation of Hydrogen Bonds
Ge, Chuanqi,Shen, Yuneng,Deng, Gang-Hua,Tian, Yuhuan,Yu, Dongqi,Yang, Xueming,Yuan, Kaijun,Zheng, Junrong
, p. 3187 - 3195 (2016)
Isotopic effects on the formation and dissociation kinetics of hydrogen bonds are studied in real time with ultrafast chemical exchange spectroscopy. The dissociation time of hydrogen bond between phenol-OH and p-xylene (or mesitylene) is found to be iden
Synthesis and Properties of 1-Acyl Triazenes
Landman, Iris R.,Acu?a-Bolomey, Emilio,Scopelliti, Rosario,Fadaei-Tirani, Farzaneh,Severin, Kay
supporting information, p. 6408 - 6412 (2019/09/06)
1-Acyl triazenes can be prepared by acid-catalyzed hydration, gold/iodine-catalyzed oxidation, or oxyhalogenation of 1-alkynyl triazenes. Crystallographic analyses reveal a pronounced effect of the acyl group on the electronic structure of the triazene fu
Catalytic Hydroarylation of Alkenes with Phenols using B(C6F5)3
Bentley, Jordan N.,Caputo, Christopher B.
supporting information, p. 3654 - 3658 (2018/10/20)
We demonstrate that tris(pentafluorophenyl)borane, B(C6F5)3, is shown to be an effective catalyst for the hydroarylation of olefins to yield substituted phenols. This system features fast reaction times, mild conditions, and good yields for a select scope of olefinic substrates and various phenols, resulting in C-C bond formation. Experimental data support two possible mechanisms, where the Lewis acid can activate either the olefin or the phenol as the first step in the catalytic mechanism.
