136-60-7Relevant articles and documents
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Alper,H.,Edward,J.T.
, p. 1623 - 1624 (1970)
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Alcoholysis of benzotrichloride studied by liquid beam - Multiphoton ionization technique
Horimoto, Noriko,Mafune, Fumitaka,Kondow, Tamotsu
, p. 159 - 160 (1997)
Chemical reactions of benzotrichloride in an alcohol solution initiated by multiphoton ionization were observed by irradiation of a tightly focused laser beam at wavelength of 274 nm. The product ions ejected from the liquid surface were analyzed by a time-of-flight mass spectrometer. The mass spectra of the ions indicate that alcoholysis occurs between PhCCl+2 produced by multiphoton ionization and alcohol molecules, ROH, giving PhCCl(OR)+ and PhC(OR)+2.
Mechanism of Amine-Catalyzed Ester Formation from an Acid Chloride and Alcohol
Hubbard, Patricia,Brittain, William J.
, p. 677 - 683 (1998)
Stopped-flow FT-IR spectroscopy has been used to study the amine-catalyzed reactions of benzoyl chloride with either butanol or phenol in dichloromethane at 0 °C. There is a paucity of detailed rate information available in the literature for this process. Our goal was to determine whether amine catalysis operated by a nucleophilic-, specific-base-, or general-base-catalyzed mechanism. A large isotope effect was observed for butanol versus butanol-O-d which is consistent with a general- base-catalyzed mechanism. Some anomalous rate dependencies on reactant concentration and the relative rate of benzoyl chloride loss versus butyl benzoate formation were observed. The analogous reaction of phenol was studied in more detailed. An overall reaction order of three, and a negligible isotope effect for phenol versus phenol-d6 are consistent with either a base- or nucleophilic-catalyzed mechanism. The most interesting result with phenol was a large sensitivity of the rate of phenyl benzoate formation on small structural changes in the amine (e.g., diethylmethylamine versus triethylamine). We observed the key intermediate (acylammonium salt) in the nucleophilic process via NMR for solutions of benzoyl chloride and amine in the absence of alcohol; however, we did not observe this intermediate in the IR during ester formation [with the exception of 4-(dimethylamino)- pyridine]. While we can rule out specific-base catalysis (no evidence for phenoxide intermediates), it is difficult to completely eliminate nucleophilic catalysis.
Application of a new interface for rapid optimisation of bio-catalysed processes: Proteolytic digestion and an enzyme-catalysed transesterification as examples
Stencel, Lauren M.,Leadbeater, Nicholas E.
, p. 242 - 247 (2014)
The results of an evaluation of the iChemExplorer for the study of bio-catalysed processes are reported. The iChemExplorer comprises of a specially-designed sample tray and a control unit, the former of which replaces a traditional tray in an HPLC autosampler assembly. It can be heated and reaction mixtures can be agitated. The system has been used to study the trypsin digestion of insulin chain B, cytochrome c and bovine serum albumin as well as the lipase-catalysed transesterification reaction between ethyl benzoate and 1-butanol. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2014.
Aromatic Acylation of Hydroxy Groups via the Rare SN1 Reaction Pathway
Bayliss, Mark A.,Homer, Roger B.,Shepherd, Martin J.
, p. 305 - 306 (1990)
The unusual reactivity of anthracene-9-carbonyl chloride indicates its acylation of low concentrations of hydroxy groups in aprotic organic solvents to proceed via an SN1 type mechanism.
MWCNTs/SnZrMoP nano-composite as Ba (II)-selective electrode and heterogeneous catalyst for esterification of primary alcohols
Kaur, Rupinder,Kaushal, Sandeep,Singh, Prit Pal
, p. 2379 - 2393 (2021)
The present investigation covers the synthesis, characterization and applications of a novel nano-composite of multiwalled carbon nanotubes–tin zirconium molybdophosphate (MWCNTs–SnZrMoP) ion exchanger. The synthesized material was characterized by various instrumental techniques viz. Fourier transform infrared spectroscopy (FT-IR), field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), and thermogravimetric/ differential thermal analysis (TGA/DTA). The nano-composite exhibited an ion exchange capacity of 2.56?meq?g?1, which is higher than its inorganic counterpart SnZrMoP (1.95?meq?g?1). The distribution studies confirmed that the as-synthesized nano-composite was selective for barium ions. The nano-composite was employed to fabricate an ion-selective electrode which showed a sub-Nernstian response for barium ions in the concentration range 1 × 10?7?M—1 × 10?1?M, with a response time of 11?s. The average slope of the calibration curve was observed to be 23.3?mV/decade with 1.78 × 10?8?M as limit of detection (LOD). The synthesized material was also used as a heterogeneous catalyst in esterification reactions of some primary alcohols due to its high mechanical, thermal and chemical stability. The esters produced were characterized by nuclear magnetic resonance (1H-NMR) and FT-IR techniques.
Highly Efficient Carbon Monoxide Capture by Carbanion-Functionalized Ionic Liquids through C-Site Interactions
Tao, Duan-Jian,Chen, Feng-Feng,Tian, Zi-Qi,Huang, Kuan,Mahurin, Shannon M.,Jiang, De-En,Dai, Sheng
, p. 6843 - 6847 (2017)
A novel method for the highly efficient and reversible capture of CO in carbanion-functionalized ionic liquids (ILs) by a C-site interaction is reported. Because of its supernucleophilicity, the carbanion in ILs could absorb CO efficiently. As a result, a relatively high absorption capacity for CO (up to 0.046 mol mol?1) was achieved under ambient conditions, compared with CO solubility in a commonly used IL [Bmim][Tf2N] (2×10?3 mol mol?1). The results of quantum mechanical calculations and spectroscopic investigation confirmed that the chemical interaction between the C-site in the carbanion and CO resulted in the superior CO absorption capacities. Furthermore, the subsequent conversion of captured CO into valuable chemicals with good reactivity was also realized through the alkoxycarbonylation reaction under mild conditions. Highly efficient CO absorption by carbanion-functionalized ILs provides a new way of separating and converting CO.
Mechanistic insight into the synergistic Cu/Pd-catalyzed carbonylation of aryl iodides using alcohols and dioxygen as the carbonyl source
Li, Junxuan,Zhou, Jinlei,Wang, Yumei,Yu, Yue,Liu, Qiang,Yang, Tilong,Chen, Huoji,Cao, Hua
, p. 68 - 74 (2021/11/16)
Pd-catalyzed carbonylation, as an efficient synthetic approach to the installation of carbonyl groups in organic compounds, has been one of the most important research fields in the past decade. Although elegant reactions that allow highly selective carbonylations have been developed, straightforward routes with improved reaction activity and broader substrate scope remain long-term challenges for new practical applications. Here, we show a new type of synergistic Cu/Pd-catalyzed carbonylation reaction using alcohols and dioxgen as the carbonyl sources. A broad range of aryl iodides and alcohols are compatible with this protocol. The reaction is concise and practical due to the ready availability of the starting materials and the scalability of the reaction. In addition, the reaction affords lactones and lactams in an intermolecular fashion. Moreover, DFT calculations have been performed to study the detailed mechanisms. [Figure not available: see fulltext.]
LiHMDS: Facile, highly efficient and metal-free transesterification under solvent-free condition
Gore, Kiran R.,Mittapelli, Lavanya L.
, (2020/10/27)
Transesterification is one of the important organic reactions employed in numerous industrial as well as laboratory applications for the synthesis of various esters. Herein, we report a rapid, highly efficient, and transition metal-free transesterification reaction in the presence of LiHMDS under solvent-free conditions. The transesterification reaction was carried out with three different benzoate esters and a wide range of primary and secondary alcohols (from C3-C18) in good to excellent yields (45 examples). By considering the commercial role of esters, this method will be promising for the facile synthesis of esters in industry-relevant applications.
