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111.
Aline Delamare Guillaume Naulet Brice Kauffmann Gilles Guichard Guillaume Compain 《Chemical science》2022,13(33):9507
The isobutyl side chain is a highly prevalent hydrophobic group in drugs, and it notably constitutes the side chain of leucine. Its replacement by a hexafluorinated version containing two CF3 groups may endow the target compound with new and advantageous properties, yet this modification remains overlooked due to the absence of a general and practical synthetic methodology. Herein, we report the first general method to introduce the hexafluoroisobutyl group into ketoesters, malonates, 1,3-diketones, Schiff base esters and malononitrile. We demonstrated that the reaction occurs through an elimination/allylic shift/hydrofluorination cascade process which efficiently overcomes the usual fluoride β-elimination observed with α-CF3-vinyl groups. We showed that with alkali metal bases, a pentafluorinated alkene is obtained predominantly, whereas the use of tetrabutylammonium fluoride (TBAF) allows hydrofluorination to occur. This tandem process represents a conceptually new pathway to synthesize bis-trifluoromethylated compounds. This methodology was applied to the multigram-scale synthesis of enantiopure (S)-5,5,5,5′,5′,5′-hexafluoroleucine.Hexafluoroisobutylation of ketoesters, malonates, diketones, Schiff base esters and malononitrile is reported. The reaction involves an elimination/allylic shift/hydrofluorination cascade process that efficiently overcomes the usual SN2′ mechanism. 相似文献
112.
113.
114.
Paul G. Gassman Kentaro Okuma Aline Lindbeck Richard Allen 《Tetrahedron letters》1986,27(52):6307-6310
-2,3-Epoxy-1,7,7-trimethylbicyclo[2.2.1]heptane reacted with trimethylsilyl cyanide in the presence of zinc iodide to produce a complex mixture of products. The major product,
-7-trimethylsiloxy-
-2,3,3-trimethyl-
-2-isocyanobicyclo[2.2.1]heptane was obtained in 72% yield. In addition, eight other products were identified in yields ranging from 10% to 1%. All of the products could be rationalized on the basis of initial generation of a carbocationic intermediate. 相似文献
115.
V. Rac Vesna Rakić S Gajinov Vera Dondur Aline Auroux 《Journal of Thermal Analysis and Calorimetry》2006,84(1):239-245
In this work, room temperature interaction of n-hexane with HZSM-5 (Si/Al=20) and ion-exchanged
samples containing one (CuZSM-5, FeZSM-5 and MnZSM-5) or two transition-metal
cations (Fe,CuZSM-5; Cu,MnZSM-5 and Fe,MnZSM-5) was studied by microcalorimetry
and TPD methods. Both differential heats and the amounts of n-hexane
adsorbed per one unit cell were quantitatively determined. Higher heats of
adsorption and higher amounts of adsorbed gas were found for ion-exchanged
samples than for HZSM-5. The experiments of n-hexane
adsorption on hydrated samples were also performed. The amounts of n-hexane
adsorbed on hydrated ZSM-5 were lower in comparison with dehydrated samples,
while the energies of interaction were similar. 相似文献
116.
Nierengarten JF Zhang S Gégout A Urbani M Armaroli N Marconi G Rio Y 《The Journal of organic chemistry》2005,70(19):7550-7557
[structure: see text] Branched conjugated systems with a terminal alkyne function have been prepared starting from 4-(triisopropylsilylethynyl) phenylacetylene by applying the following iterative reaction sequence: (i) metal-catalyzed cross-coupling reaction of the terminal alkyne with 3,4-dibromobenzaldehyde or 2,5- dibromobenzaldehyde; (ii) Corey-Fuchs dibromoolefination and treatment with an excess of LDA. The building blocks thus prepared have been subjected to a Pd-catalyzed cross-coupling reaction with 1,4-diiodobenzene to yield isomeric branched pi-conjugated systems containing 7 (first generation) or 15 (second generation) phenyl units connected by ethynyl spacers. The different pi-conjugation patterns in those isomeric derivatives have a dramatic effect on their electronic properties, as attested by the differences observed in their absorption and emission spectra. Finally, theoretical calculations have been performed to rationalize the optical properties of these compounds. 相似文献
117.
da Silva VM da Cunha Veloso MC de Oliveira AS Santos GV de P Pereira PA de Andrade JB 《Talanta》2005,68(2):323-328
Brominated phenols 2- and 4-bromophenol (2-BP and 4-BP); 2,4- and 2,6-dibromophenol (2,4-DBP and 2,6-DBP) and 2,4,6-tribromophenol (2,4,6-TBP) have been identified as key flavor compounds found in seafoods. Depending on their concentrations, they were responsible for marine or ocean flavor (shrimp/crab/fish/sea salt-like) or for phenolic/iodine/iodoform-like off-flavor. In this work a new analytical methodology was developed to determine, simultaneously, such bromophenols in fish meats, based on reversed-phased high-performance liquid chromatographic separation (RP-HPLC). The separation of bromophenols was made onto a Lichrospher 100 RP-18 column using water:acetonitrile gradient at a flow rate of 1.0 mL min−1, using absorbance detection at 286 nm, were the 2-BP, 4-BP, 2,4- and 2,6-DBP show significant absorbtivity values and at 297 nm for 2,4,6-TBP. They were separated in 20 min with a good chromatographic resolution (Rs) for the isomeric compounds: 2- and 4-BP, Rs = 1.23; 2,4- and 2,6-DBP, Rs = 1.63. The calibration curves were linear in the bromophenols concentration range of 200.0-1000 ng mL−1. Under optimized conditions, the detection limit of the HPLC method was 127 ng mL−1 for 2-BP; 179 ng mL−1 for 4-BP; 89.0 ng mL−1 for 2,4-DBP; 269 ng mL−1 for 2,6-DBP and 232 ng mL−1 for 2,4,6-TBP. This method has been applied in determination of bromophenols, isolated by combined steam distillation-solvent extraction with 2 mL of pentane/diethyl ether (6:4), from Brazilian fishes samples, collected on the Atlantic coast of Bahia (13°01′S and 38°31′W), Brazil. The concentration range determined were 0.20 ng g−1 (2-BP) to 299 ng g−1 (2,4,6-TBP). The method proposed here is rapid and suitable for simultaneous quantification of simple bromophenols in fish meat. As long as we know, it is the first analytical methodology, using RP-HPLC/UV, which was developed to determine simple bromophenols in fish meat. 相似文献
118.
The mathematical optimization of a continuous alcoholic fermentation process combined with a flash column under vacuum was
studied. The objective was to maximize % yield and productivity in the fermentor. The results using surface response analysis
combined with modeling and simulation were compared withy those obtained when the problem was written as a nonlinear programming
problem and was solved with a successive quadratic programming (SQP) technique. Two process models were evaluated when the
process was optimized using the SQP technique. The first one is a deterministic model, whose kinetic parameters were experimentally
determined as functions of the temperature, and the second is a statistical model obtained using the factorial design technique
combined with simulation. Although the best result was the one obtained using the rigorous model, the values for productivity
and % yield obtained using the simplified model are acceptable, and these models can be used when the development of a rigorous
model is excessively difficult, slow, or expensive. 相似文献
119.
120.
Davet Aline Carvalho Joo Luiz S. Dadalt Robson C. Vituoso Suzane Dias Josiane F.G. Miguel Marilis D. Miguel Obdlio G. 《Chromatographia》2009,69(2):245-247
This study proposes an RP 18 LC method for the analysis of some common nitrogen-containing compounds. This method has used the ionic pair concept in the mobile phase with sulfuric acid and lauril sodium sulfate in its composition. N-Methyltyramine and hordenine have been identified for the first time in this species.
相似文献