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61.
Studies on the Silylation Reaction of α,β-Epoxy Esters Synthesized by Darzen's Condensation Reaction
《Phosphorus, sulfur, and silicon and the related elements》2013,188(12):2545-2550
Me3SiCl/Mg in HMPA was used for silylation of α,β-epoxy esters resulting in the corresponding β-silylated esters in a one pot reaction with reasonable yields. 相似文献
62.
D. Bhaskar Reddy P. V. Ramana Reddy M. Muralidhar Reddy M. V. Ramana Reddy S. Vijayalakshmi 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):325-329
Abstract Some new 1,1,2-trisubstituted ethylenic sulfones have been prepared by the condensation of aryl- and benzylsulfonylmethylsulfonylacetic acid esters with araldehydes. 相似文献
63.
Chemoselective esterification of phenolic acids with dialkyl sulphates or alkyl halides in the presence of sodium bicarbonate in 1,3‐dialkylimidazolium ionic liquids is reported in excellent yields and less reaction time as compared to organic solvents. 相似文献
64.
Gonzalo Astray Juan F. Gálvez Juan C. Mejuto Oscar A. Moldes Iago Montoya 《Journal of computational chemistry》2013,34(5):355-359
In this article, an artificial neural network to predict the flash point of 95 esters was implemented. Four variables were used for its development. A neural network with 4‐5‐8‐5‐1 topology was encountered to gain the best agreement of the experimental results with those predicted (square correlation coefficient (R2) and root mean square error were 0.99 and 5.46 K for the training phase and 0.96 and 13.02 K for the testing set). © 2012 Wiley Periodicals, Inc. 相似文献
65.
Base free Fe(CO)5 catalyzed one-pot synthesis of E/Z alkyl 3-formyl-3-alkyl/aryl/ferrocenyl-2-propenoates (retinoid esters) was achieved by the photolysis of alcoholic solution of terminal acetylenes and carbon monoxide. 8–10 Mol% of ironpentacarbonyl was used as a catalyst for significant transformations of retinoid esters. During the photolysis, alkynes reduced by the simultaneous double functionalization esterification and formylation and resulted in regioselective E/Z isomers of alkyl 3-formyl-3-alkyl/aryl/ferrocenyl-2-propenoates. The bi-functionalization of acetylene is quite unusual and is not observed frequently. The highest yield of the retinoid esters was achieved with 3° alcohols (96%, for E and Z isomers) while the least yield was observed with 1° alcohols (25%, for E and Z isomers). All retinoid esters are regiospecific and have exceptional biological significance to serve as key structural motifs in drug and pharmaceutical applications. 相似文献
66.
AgOTf proved to be an effective catalyst for the transesterification of β‐keto esters with primary, secondary and tertiary alcohols. The products were obtained in high yield within a reasonable reaction time period. The kinetics of the transesterification reaction were also studied and the reaction was found to follow second‐order kinetics. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
67.
《Analytical letters》2012,45(14):1185-1189
Abstract A specific and non-destructive test for basic esters of benzilic and α-glycolic acids in water is described. The compounds are collected on a glass fiber filter as water insoluble complexes with sodium tetraphenylboron. The filter is dried and sprayed with a 2-diphenylacetyl-l, 3-indandione-l-imine derivative. A positive test is the visual observation of fluorescence. 相似文献
68.
Dr. Christopher R. Emerson Dr. Lev N. Zakharov Prof. Dr. Paul R. Blakemore 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(48):16342-16356
Four putative functionalized α‐chloroakyllithiums RCH2CHLiCl, where R=CHCH2 ( 18 a ), CCH ( 18 b ), CH2OBn ( 18 c ), and CH[O(CH2)2O] ( 18 d ), were generated in situ by sulfoxide–lithium exchange from α‐chlorosulfoxides, and investigated for the stereospecific reagent‐controlled homologation (StReCH) of phenethyl and 2‐chloropyrid‐5‐yl ( 17 ) pinacol boronic esters. Deuterium labeling experiments revealed that α‐chloroalkyllithiums are quenched by proton transfer from their α‐chlorosulfoxide precursors and it was established that this effect compromises the yield of StReCH reactions. Use of α‐deuterated α‐chlorosulfoxides was discovered to ameliorate the problem by retarding the rate of acid‐base chemistry between the carbenoid and its precursor. Carbenoids 18 a and 18 b showed poor StReCH efficacy, particularly the propargyl group bearing carbenoid 18 b , the instability of which was attributed to a facile 1,2‐hydride shift. By contrast, 18 d , a carbenoid that benefits from a stabilizing interaction between O and Li atoms gave good StReCH yields. Boronate 17 was chain extended by carbenoids 18 a , 18 b , and 18 d in 16, 0, and 68 % yield, respectively; α‐deuterated isotopomers D ‐ 18 a and D ‐ 18 d gave yields of 33 and 79 % for the same reaction. Double StReCH of 17 was pursued to target contiguous stereodiads appropriate for the total synthesis of (?)‐epibatidine ( 15 ). One‐pot double StReCH of boronate 17 by two exposures to (S)‐D ‐ 18 a (≤66 % ee), followed by work‐up with KOOH, gave the expected stereodiad product in 16 % yield (d.r.~67:33). The comparable reaction using two exposures to (S)‐D ‐ 18 d (≤90 % ee) delivered the expected bisacetal containing stereodiad (R,R)‐DD ‐ 48 in 40 % yield (≥98 % ee, d.r.=85:15). Double StReCH of 17 using (S)‐D ‐ 18 d (≤90 % ee) followed by (R)‐D ‐ 18 d (≤90 % ee) likewise gave (R,S)‐DD ‐ 48 in 49 % yield (≥97 % ee, d.r.=79:21). (R,S)‐DD ‐ 48 was converted to a dideuterated isotopomer of a synthetic intermediate in Corey’s synthesis of 15 . 相似文献
69.
Minami Odagi Kota Furukori Tatsuya Watanabe Prof. Dr. Kazuo Nagasawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(49):16740-16745
Highly enantioselective catalytic oxidation of 1‐tetralone‐derived β‐keto esters was achieved by using a guanidine–urea bifunctional organocatalyst in the presence of cumene hydroperoxide (CHP), a safe, commercially available oxidant. The α‐hydroxylation products were obtained in 99 % yield with up to 95 % enantiomeric excess (ee). The present oxidation was successfully applied to synthesize a key intermediate of the anti‐cancer agent daunorubicin ( 2 ). 相似文献
70.
Dr. Sheng Cao Robin Christiansen Prof. Xiaohua Peng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(27):9050-9058
A series of arylboronic esters containing different aromatic substituents and various benzylic leaving groups (Br or N+Me3Br?) have been synthesized. The substituent effects on their reactivity with H2O2 and formation of quinone methide (QM) have been investigated. NMR spectroscopy and ethyl vinyl ether (EVE) trapping experiments were used to determine the reaction mechanism and QM formation, respectively. QMs were not generated during oxidative cleavage of the boronic esters but by subsequent transformation of the phenol products under physiological conditions. The oxidative deboronation is facilitated by electron‐withdrawing substituents, such as aromatic F, NO2, or benzylic N+Me3Br?, whereas electron‐donating substituents or a better leaving group favor QM generation. Compounds containing an aromatic CH3 or OMe group, or a good leaving group (Br), efficiently generate QMs under physiological conditions. Finally, a quantitative relationship between the structure and activity has been established for the arylboronic esters by using a Hammett plot. The reactivity of the arylboronic acids/esters and the inhibition or facilitation of QM formation can now be predictably adjusted. This adjustment is important as some applications may benefit and others may be limited by QM generation. 相似文献