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51.
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Studies on the mechanism and intermediate products in the Friedel–Crafts reaction between oxetanols and phenols are presented. The formation of O-alkylated intermediates is identified using 1H NMR spectroscopy, in a reversible formation of the kinetic oxetane ether products. An interesting relationship between the electronic nature of the nucleophile and the degree of O-alkylation is uncovered. For phenols substituted with an electron withdrawing group such as CN, oxetane ethers are the only products isolated regardless of reaction time. Increasing the electron rich nature of the phenol leads to an increased proportion of the thermodynamic C-alkylated Friedel–Crafts products after just 1?h and as the sole product/s after extended reaction times. These studies have enabled a more complete catalytic cycle to be proposed. Using the same lithium catalyst and carefully selected reaction times, several examples of oxetane ethers are successfully isolated as novel bioisosteres for ester groups. 相似文献
53.
Robert S.L. Chapman Molly Francis Ruth Lawrence Joshua D. Tibbetts Steven D. Bull 《Tetrahedron》2018,74(44):6442-6452
Formyloxyacetoxyphenylmethane, symmetric 1,1-diacylals and mixed 1-pivaloxy-1-acyloxy-1-phenylmethanes have been used as moisture stable O-formylating and O-acylating reagents for primary and secondary alcohols, allylic alcohols and phenols under solvent/catalyst free conditions to afford their corresponding esters in good yield. 相似文献
54.
Bach J Blachère C Bull SD Davies SG Nicholson RL Price PD Sanganee HJ Smith AD 《Organic & biomolecular chemistry》2003,1(11):2001-2010
A study of the properties of N-hydrocinnamoyl- derivatives of 5,5-dimethyloxazolidin-2-one, 4,4-dimethyloxazolidin-2-one and oxazolidin-2-one upon hydride reduction with DIBAL-H demonstrates that the 5,5-dimethyl-group is essential for inhibition of endocyclic nucleophilic attack. For instance, treatment of N-hydrocinnamoyl-5,5-dimethyloxazolidin-2-one with DIBAL-H results in the selective formation of the stable N-1'-hydroxyalkyl derivative which may be regarded as a masked hydrocinnamaldehyde equivalent, as treatment under basic conditions affords the parent aldehyde in excellent yield. Treatment of N-hydrocinnamoyl-4,4-dimethyloxazolidin-2-one with DIBAL-H under identical conditions affords a complex mixture of products, including the formate ester product of endocyclic cleavage. As an alternate strategy, DIBAL-H reduction of straight chain and branched N-acyl-5,5-dimethyloxazolidin-2-one derivatives, followed by a Horner-Wadsworth-Emmons reaction affords alpha,beta-unsaturated esters in good yields. Branching alpha- to the exocyclic carbonyl in N-acyl-oxazolidinones inhibits DIBAL-H reduction, but this can be overcome by precomplexation with ZnCl2, with subsequent fragmentation generating either the corresponding aldehyde or alpha,beta-unsaturated esters. The addition of ZnCl2 has been shown to increase the diastereoselectivity observed in Wadsworth-Horner-Emmons reactions of lithiated phosphonates. 相似文献
55.
Araujo E Rodríguez-Malave AJ González AM Rojas OJ Peñaloza N Bullón J Lara MA Dmitrieva N 《Applied biochemistry and biotechnology》2002,97(2):91-103
In this work, the effect of Fento’s reagent on the degradation of residual Kraft black liquor was investigated. The effect
of Fenton’s reagent on the black liquor degradation was dependent on the concentration of H2O2. At low concentrations (5 and 15 mM) of H2O2, Fenton’s reagent caused the degradation of phenolic groups (6.8 and 44.8%, respectively), the reduction of reaction medium
pH (18.2%), and the polymerization of black liquor lignin. At a high concentration (60 mM) of H2O2, Fenton’s reagent induced an extensive degradation of lignin (95–100%) and discoloration of the black liquor. In the presence
of traces of iron, the addition of H2O2 alone induced mainly lignin fragmentation. In conclusion, Fenton’s reagent and H2O2 alone can degrade residual Kraft black liquor under acidic conditions at room temperature. 相似文献
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Ohne Zusammenfassung
Fellow of the National Research Council of the U. S. A.
Es ist uns eine angenehme Pflicht, auch an dieser Stelle Herrn Prof. Dr. H. Freundlich für seine Anteilnahme und dauernde
Hilfe bei dieser Arbeit unseren verbindlichsten Dank auszusprechen. 相似文献
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59.
Friedel-Crafts acylation of pyrroles and indoles using 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) as a nucleophilic catalyst 总被引:1,自引:0,他引:1
1,5-Diazabicyclo[4.3.0]non-5-ene (DBN) has been shown to be an effective catalyst for the regioselective Friedel-Crafts C-acylation of pyrroles and indoles in high yields. A detailed mechanistic study implies that DBN is acting as a nucleophilic organocatalyst, with the X-ray crystal structure of a key N-acyl-amidine intermediate having been determined for the first time. 相似文献
60.
Martin Gutowski Jonathan M. Bull Timothy J. Henstock Tom Hiller Paul R. White 《Applied Acoustics》2008,69(3):262-271
Chirp sub-bottom profilers are marine acoustic devices that use a known and repeatable frequency-modulated source signature to produce vertical seismic reflection cross-sections of the sub-seabed. Here a 3D Chirp system is described that operates in the frequency range of 1.5-13 kHz, to produce a three-dimensional image of the sub-seabed, with typical penetration of 10-30 m and decimetric horizontal and vertical resolution. The system design incorporates a rigid frame that contains the Chirp source array together with 60 receiver elements, with positioning provided by an integrated real-time-kinematic (RTK) global positioning system (GPS). The system can be surface towed from a small survey vessel and can be applied to targets of marine geological, engineering, archaeological and defence interest. Data acquisition and processing are described for a case study which images a buried engineering structure in the Port of Southampton. 相似文献