131 results on '"*TRIFLUOROMETHYL compounds"'
Search Results
2. Catalytic Asymmetric Difluoroalkylation Using In Situ Generated Difluoroenol Species as the Privileged Synthon.
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Xie, Xiongda, Dong, Shanliang, Hong, Kemiao, Huang, Jingjing, and Xu, Xinfang
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TRIFLUOROMETHYL compounds , *MANNICH reaction , *ALKYL group , *ALDOLS , *DIAZO compounds , *PHOSPHORIC acid , *ASYMMETRIC synthesis - Abstract
A robust and practical difluoroalkylation synthon, α,α‐difluoroenol species, which generated in situ from trifluoromethyl diazo compounds and water in the presence of dirhodium complex, is disclosed. As compared to the presynthesized difluoroenoxysilane and in situ formed difluoroenolate under basic conditions, this difluoroenol intermediate displayed versatile reactivity, resulting in dramatically improved enantioselectivity under mild conditions. As demonstrated in catalytic asymmetric aldol reaction and Mannich reactions with ketones or imines in the presence of chiral organocatalysts, quinine‐derived urea, and chiral phosphoric acid (CPA), respectively, this relay catalysis strategy provides an effective platform for applying asymmetric fluorination chemistry. Moreover, this method features a novel 1,2‐difunctionalization process via installation of a carbonyl motif and an alkyl group on two vicinal carbons, which is a complementary protocol to the metal carbene gem‐difunctionalization reaction. [ABSTRACT FROM AUTHOR]
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- 2024
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3. Diastereo-selective synthesis of CF3-substituted epoxide via in situ generated trifluoroethylideneiodonium ylide.
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Chenxin Ge and Chao Chen
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TRIFLUOROMETHYL compounds , *EPOXIDATION , *EPOXY compounds , *IODONIUM salts , *YLIDES , *ALDEHYDES - Abstract
The first example for the generation of 2,2,2-trifluoroethylidene ylide from corresponding iodonium salt is reported, which has been successfully applied in the epoxidation of aldehydes, achieving the corresponding trifluoromethylated epoxides in high yields and diastereo-selectivities. [ABSTRACT FROM AUTHOR]
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- 2023
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4. Novel late-stage radiosynthesis of 5-[18F]-trifluoromethyl-1,2,4-oxadiazole (TFMO) containing molecules for PET imaging.
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Turkman, Nashaat, Liu, Daxing, and Pirola, Isabella
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SMALL molecules , *TRIFLUOROMETHYL compounds , *CENTRAL nervous system , *OXADIAZOLES , *FLUORIDES - Abstract
Small molecules that contain the (TFMO) moiety were reported to specifically inhibit the class-IIa histone deacetylases (HDACs), an important target in cancer and the disorders of the central nervous system (CNS). However, radiolabeling methods to incorporate the [18F]fluoride into the TFMO moiety are lacking. Herein, we report a novel late-stage incorporation of [18F]fluoride into the TFMO moiety in a single radiochemical step. In this approach the bromodifluoromethyl-1,2,4-oxadiazole was converted into [18F]TFMO via no-carrier-added bromine-[18F]fluoride exchange in a single step, thus producing the PET tracers with acceptable radiochemical yield (3–5%), high radiochemical purity (> 98%) and moderate molar activity of 0.33–0.49 GBq/umol (8.9–13.4 mCi/umol). We validated the utility of the novel radiochemical design by the radiosynthesis of [18F]TMP195, which is a known TFMO containing potent inhibitor of class-IIa HDACs. [ABSTRACT FROM AUTHOR]
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- 2021
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5. Xanthenone-based hydrazones as potent α-glucosidase inhibitors: Synthesis, solid state self-assembly and in silico studies.
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Tariq, Qamar-un-Nisa, Malik, Sana, Khan, Ajmal, Naseer, Muhammad Moazzam, Khan, Shafi Ullah, Ashraf, Abida, Ashraf, Muhammad, Rafiq, Muhammad, Mahmood, Khalid, Tahir, Muhammad Nawaz, and Shafiq, Zahid
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HYDRAZONES , *GLUCOSIDASE inhibitors , *DIMERS , *TRIFLUOROMETHYL compounds , *MOLECULAR models - Abstract
Graphical abstract Highlights • A new series of Xanthenone based hydrazones (5a–n) was synthesized. • New hydrazones were screened for their i n vitro α -glucosidase inhibitory activity. • Structure activity relationship established. • In silico , molecular docking was carried out to study putative binding of potent hydrazones with target enzyme. • Solid state self-assembly studies to explore the role of iminoamide dimer synthon in crystal packing. Abstract Xanthenone based hydrazone derivatives (5a–n) have been synthesized as potential α-glucosidase inhibitors. All synthesized compounds (5a–n) are characterized by their FTIR, 1H NMR, 13C NMR and HRMS, and in case of 5g also by X-ray crystallographic technique. The compounds unveiled a varying degree of α-glucosidase inhibitory activity when compared with standard acarbose (IC 50 = 375.38 ± 0.12 µM). Amongst the series, compound 5l (IC 50 = 62.25 ± 0.11 µM) bearing a trifluoromethyl phenyl group is found to be the most active compound. Molecular modelling is performed to establish the binding pattern of the more active compound 5l, which revealed the significance of substitution pattern. The pharmacological properties of molecules are also calculated by MedChem Designer which determines the ADME (absorption, distribution, metabolism, excretion) properties of molecules. The solid state self-assembly of compound 5g is discussed to show the conformation and role of iminoamide moiety in the molecular packing. [ABSTRACT FROM AUTHOR]
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- 2019
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6. The common field lampricide 3-trifluoromethyl-4-nitrophenol is a potential radiosensitizer in fish cells.
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Vo, Nguyen T.K., Seymour, Colin B., and Mothersill, Carmel E.
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TRIFLUOROMETHYL compounds , *RADIATION-sensitizing agents , *INTRODUCED species , *SEA lamprey , *CHRONIC toxicity testing - Abstract
Abstract Purpose To evaluate if the common field lampricide 3-trifluoromethyl-4-nitrophenol (TFM) that is intended to eradicate the invasive species sea lampreys in the Great Lakes has the potential to sensitize radiation responses in cells from non-targeted native fish Materials and methods The TFM toxicity was assessed acutely and chronically with the clonogenic fish cell line eelB. The acute toxicity (24-h exposure) was determined by the fluorescent cell viability probe Alamar Blue. The chronic toxicity was determined either by Alamar Blue (7-d exposure) or the clonogenic survival assay (14-d exposure). Pre- and post-exposure of fish cells to environmentally relevant TFM concentrations following gamma irradiation were performed. Clonogenic survival was determined to assess the damage level of radiation-induced reproductive cell death. Results The chronic toxicity tests were more sensitive than the acute toxicity tests. The 14-d EC 50 using the clonogenic survival endpoint was 2.09 ± 0.28 μg/mL and was statistically similar to the 7-d EC 50 (1.85 ± 0.07 μg/mL) based on the Alamar Blue-based cytotoxicity endpoint. Post-exposure of cells to environmentally relevant TFM concentrations following irradiation did not have any effect as compared to the irradiation alone group. In contrast, pre-exposure of cells to TFM following irradiation had a negative additive effect when the total radiation dose was 2 Gy, but not 0.1 or 0.5 Gy. Conclusion Our results suggest that the common field lampricide TFM is a potential radiation sensitizer in cells from non-targeted native fish. This could be a health problem of concern for non-targeted native fish if a large accidental radioactive release occurs. Highlights • Effects of the lampricide TFM on the fish cells' reproductive death were studied. • Chronic TFM toxicity tests were more sensitive than acute toxicity tests. • Post-exposure of fish cells to TFM has no additive effect on the radiation responses. • Pre-exposure of fish cells to TFM sensitizes the radiation responses. [ABSTRACT FROM AUTHOR]
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- 2019
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7. 2-{[2,8-Bis(trifluoromethyl)quinolin-4-yl](hydroxy)-methyl}piperidin-1-ium trichloroacetate: crystal structure and Hirshfeld surface analysis.
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Wardell, James L., Jotani, Mukesh M., and Tiekink, Edward R. T.
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TRIFLUOROMETHYL compounds , *CRYSTAL structure , *HYDROGEN bonding - Abstract
The asymmetric unit of the centrosymmetric title salt, C17H17F6N2O+·C2Cl3O2-, comprises a single ion-pair. The hydroxy-O and ammonium-N atoms lie to the same side of the cation, a disposition maintained by a charge-assisted ammonium-N—H···O(hydroxy) hydrogen bond [the Oh—Cm—Cm–Na (h = hydroxy, m = methine, a = ammonium) torsion angle is 58.90 (19)°]. The piperidin-1-ium group is approximately perpendicular to the quinolinyl residue [Cq—Cm—Cm–Na (q = quinolinyl) is -178.90 (15)°] so that the cation, to a first approximation, has the shape of the letter L. The most prominent feature of the supramolecular association in the crystal is the formation of chains along the a-axis direction, being stabilized by charge-assisted hydrogen-bonds. Thus, ammonium-N+—H···O-(carboxylate) hydrogen bonds are formed whereby two ammonium cations bridge a pair of carboxylate-O atoms, leading to eightmembered {···O···HNH}2 synthons. The resulting four-ion aggregates are linked into the supramolecular chain via charge-assisted hydroxyl-O— H···O-(carboxylate) hydrogen bonds. The connections between the chains, leading to a three-dimensional architecture, are of the type C—X···π, for X = Cl and F. The analysis of the calculated Hirshfeld surface points to the importance of X···H contacts to the surface (X = F, 25.4% and X = Cl, 19.7%) along with a significant contribution from O···H hydrogen-bonds (10.2%). Conversely, H···H contacts, at 12.4%, make a relatively small contribution to the surface. [ABSTRACT FROM AUTHOR]
- Published
- 2018
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8. Conformational dynamics of 1-phenyl-2,2,2-trifluoroethanol by rotational spectroscopy and ab initio calculations.
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Carlson, Colton D., Seifert, Nathan A., Heger, Matthias, Xie, Fan, Thomas, Javix, and Xu, Yunjie
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TRIFLUOROMETHYL compounds , *AB initio quantum chemistry methods , *FOURIER transform spectroscopy , *CHIRPED pulse amplification - Abstract
The rotational spectrum of 1-phenyl-2,2,2-trifluoroethanol, a chiral organic alcohol, was investigated using two chirped pulse Fourier transform microwave spectrometers. The molecule is a derivate of 2,2,2-trifluoroethanol, and the phenyl substitution plays a major role in altering the conformational landscape. Three equilibrium minima were identified at the MP2 and B3LYP-D3BJ levels of theory, of which only two exist as stable conformers after applying harmonic zero-point-energy correction. Rotational spectra of the most stable conformer and its eight 13 C isotopologues were assigned and the rotational constants obtained were used to refine the ab initio structure. The second conformer was not observed experimentally, and subsequent analysis indicates that the conformational conversion barrier was too low to trap this second conformer, even in a helium jet expansion. [ABSTRACT FROM AUTHOR]
- Published
- 2018
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9. Post-exposure effects of the piscicide 3-trifluoromethyl-4-nitrophenol (TFM) on the stress response and liver metabolic capacity in rainbow trout (Oncorhynchus mykiss).
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Birceanu, Oana and Wilkie, Michael Patrick
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RAINBOW trout , *TRIFLUOROMETHYL compounds , *PHYSIOLOGICAL effects of pesticides , *NITROPHENOLS , *LIVER physiology , *PHYSIOLOGICAL stress , *PHYSIOLOGY - Abstract
The piscicide 3-trifluoromethyl-4-nitrophenol (TFM) has been used to control invasive sea lamprey (Petromyzon marinus) populations in the Great Lakes for almost 60 years. Applied to rivers and streams containing larval lampreys, TFM seldom harms non-target fishes, but the effects of sub-lethal treatments on fish physiology are not well understood. We examined the effects of 9 h exposure to TFM on the stress axis and liver metabolic capacity of rainbow trout (Oncorhynchus mykiss) using in vivo and in vitro approaches. The fish that had been acutely exposed to TFM in vivo had increased plasma cortisol levels at 12 h post-treatment, but TFM exposure did not interfere with in vitro cortisol production in head kidney preparations. Subjecting trout to an acute handling stressor 12 h post-TFM exposure resulted in a relative attenuation of the plasma cortisol and glucose response compared to pre-stress levels. We conclude that routine TFM treatments can lead to elevations of plasma cortisol following exposure, plus a relative dampening of the stress response in rainbow trout, with high cortisol levels lasting at least 12 h post-treatment. Since the ability of the fish to produce cortisol and the liver metabolic capacity were not compromised following TFM exposure, it is likely that their ability to cope with other stressors is not altered in the long-term. [ABSTRACT FROM AUTHOR]
- Published
- 2018
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10. ATPR‐induced G0/G1 phase arrest in gastric cancer cells by regulating the binding of 14‐3‐3ε and filamin A.
- Author
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Zhao, Yingli, Fang, Xing, Fang, Hui, Feng, Yubin, Chen, Feihu, and Xia, Quan
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STOMACH cancer , *CANCER cells , *FILAMINS , *TRIFLUOROMETHYL compounds , *MOLECULAR chaperones - Abstract
Abstract: 4‐amino‐2‐trifluoromethyl‐phenyl retinate (ATPR) was able to induce the G0/G1 phase arrest in gastric cancer SGC‐7901 cells by downregulating 14‐3‐3ε. However, the mechanisms underlying this effect have not been fully elucidated. Because 14‐3‐3ε functions as a molecular chaperone on cell cycle regulation, the interaction between 14‐3‐3ε and the target proteins is worth an in‐depth study. In this study, the use of targeting proteomics identified 352 14‐3‐3ε‐binding proteins in SGC‐7901 cells. Analysis of gene ontology (GO) was performed using PANTHER to annotate the biological processes, protein classes, and pathways of these proteins. In 25 cell cycle‐related proteins, filamin A was reduced following ATPR treatment, and this change was validated by immunoprecipitation. The cell cycle was arrested at the G0/G1 phase following ATPR treatment or filamin A silencing in SGC‐7901 cells. Furthermore, subcellular expression analysis showed that 14‐3‐3ε and filamin A were transferred from the cytoplasm to the nucleus after ATPR treatment. On the other hand, overexpression of 14‐3‐3ε, in SGC‐7901 cells, resulted in an increase in the total cellular level of filamin A and an increase in the subcellular localization of filamin A in the cytoplasm. ATPR treatment of the 14‐3‐3ε overexpression cells decreased the total level of filamin A and redistributed filamin A protein from the cytoplasm to the nucleus. Immunohistochemical analysis showed that the expression levels of 14‐3‐3ε and filamin A in gastric cancer tissues were significantly higher, with a predominant localization in the cytoplasm, compared to the levels in matched tissues. Taken together, our results suggest that ATPR can induce nuclear localization of filamin A by reducing the binding of 14‐3‐3ε and filamin A, which may be the mechanism of ATPR‐induced G0/G1 phase arrest. [ABSTRACT FROM AUTHOR]
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- 2018
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11. Crystal structure of 1-[3,5-bis(trifluoromethyl)-phenyl]-2-bromoethan-1-one.
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Chandrashekharappa, Sandeep, Bairagi, Keshab M., Mohan, Mahendra K., Mohanlall, Viresh, Kasumbwe, Kabange, Venugopala, Katharigatta N., and Nayak, Susanta K.
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CRYSTAL structure , *TRIFLUOROMETHYL compounds , *BROMINE compounds , *ACETOPHENONE derivatives , *WEAK interactions (Nuclear physics) - Abstract
The title compound, C10H5BrF6O, synthesized via continuous stirring of 3,5-bis(trifluoromethyl) acetophenone with bromine in an acidic medium and concentrated under reduced pressure, crystallizes with four molecules in the unit cell (Z = 4) and one formula unit in the asymmetric unit. In the crystal, molecules are linked in a head-to-tail fashion into dimers along the b-axis direction through weak C-H...Br and C-O...Csp2 interactions. C-H...O, C-F...π and F...F interactions are also observed. [ABSTRACT FROM AUTHOR]
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- 2018
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12. Vasodilator effect of 1-trifluoromethoxyphenyl-3-(1-propionylpiperidin-4-yl) urea is predominantly mediated through activation of voltage-dependent K+ channels.
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Shah, Shafiq Ali, Mehmood, Malik Hassan, Khan, Munasib, Bukhari, Ishfaq Ali, and Gilani, Anwarul Hassan
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VASODILATORS , *TRIFLUOROMETHYL compounds , *CARDIOVASCULAR diseases , *TETRAETHYLAMMONIUM , *AMMONIUM ions - Abstract
Purpose: To determine the mechanism of vasorelaxant effect of 1-trifluoromethoxyphenyl - 3 -(1- propionylpiperidin-4-yl) urea (TPPU) in cardiovascular diseases, including hypertension. Methods: Isolated rat thoracic aortic tissue preparations were mounted in an organ bath set up integrated with isometric transducer and a Power Lab assembly. TPPU (0.3 - 100 μM) was tested for vasorelaxant effect against low K+ (25 mM) and high K+ (80 mM)-induced contractions and its mechanism was determined in the presence of different antagonists (glibenclamide, 4- aminopyridine and tetraethyl ammonium). Results: In rat aortic preparations, TPPU showed a concentration-dependent (0.3 - 100 μM) and significant (p < 0.001) inhibition of low K+ induced contractions with complete inhibition obtained at 100 μM. TPPU produced significant (p < 0.05) inhibition of high K+ induced contractions with maximum relaxation of 15.36 ± 1.95 % and 15.85 ± 3.35 % at 30 and 100 μM, respectively. Glibenclamide (Gb,10 μM) pretreatment partially inhibited the vasorelaxant effect of TPPU against low K+ in a concentration range of 1 - 30 μM. 4-Aminopyridine (4-AP, 1 mM) and tetraethyl ammonium (TEA, 10 mM), markedly inhibited the vasorelexant effect of TPPU against low K+ induced contractions with maximum relaxation of 20.09 ± 2.40 and 21.67 ± 0.88 %, respectively, at 100 μM. Conclusion: TPPU possesses marked vasorelaxant properties which provides sound pharmacological evidence for its use as a potential drug candidate in the management of hypertension. [ABSTRACT FROM AUTHOR]
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- 2018
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13. Systematic comparison of force fields for molecular dynamic simulation of Au(111)/Ionic liquid interfaces.
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Wang, Runxi, Bi, Sheng, Presser, Volker, and Feng, Guang
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MOLECULAR dynamics , *MOLECULAR physics , *IONIC liquids , *TRIFLUOROMETHYL compounds , *GOLD electrodes - Abstract
Selecting the most suitable force field is a key to meaningful molecular dynamics (MD) simulation. To select the appropriate gold force field to model the Au(111)/ionic liquid interface, a systematic comparison of four different widely used force fields of gold and a typical carbon force field has been studied by MD simulations with constant potential method. We calculated the ion adsorption behavior and differential capacitance of interfaces between the gold electrode and ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([PYR][TFSI]) in comparison with the experimental results and showed the effects on the solid-liquid interfaces from the van der Waals interaction, image force effect and cumulative ions. Based on the comparison between the results of simulations and experiments, we recommend two types of force fields to properly model the Au(111)/ionic liquid interfaces. [ABSTRACT FROM AUTHOR]
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- 2018
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14. Trifluoromethyl Boron Dipyrromethene Derivatives as Potential Photosensitizers for Photodynamic Therapy.
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Liu, Jian-Yong, Zhou, Peng-Zhen, Ma, Jia-Lin, and Jia, Xiao
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BORON , *DIPYRRINS , *PHOTOSENSITIZERS , *TRIFLUOROMETHYL compounds , *ANTINEOPLASTIC agents , *PHOTODYNAMIC therapy - Abstract
In this study, two novel boron dipyrromethene-based photosensitizers (BDP3 and BDP6) substituted with three or six trifluoromethyl groups have been synthesized and characterized with various spectroscopic methods, and their photo-physical, photo-chemical, and photo-biological properties have also been explored. The two photosensitizers are highly soluble and remain nonaggregated in N,N-dimethylformamide as shown by the intense and sharp Q-band absorption. Under red light irradiation (λ = 660 nm, 1.5 J/cm2), both photosensitizers show high and comparable cytotoxicity towards HepG2 human hepatocarcinoma and HeLa human cervical carcinoma cells with IC50 values of 0.42–0.49 μM. The high photocytotoxicity of BDP3 and BDP6 can be due to their high cellular uptake and low aggregation tendency in biological media, which result in a high efficiency to generate reactive oxygen species inside the cells. Confocal laser fluorescence microscopic studies indicate that they have superior selective affinities to the mitochondria and lysosomes of HepG2 and HeLa cells. The results show that these two trifluoromethyl boron dipyrromethene derivatives are potential anticancer agents for photodynamic therapy. [ABSTRACT FROM AUTHOR]
- Published
- 2018
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15. Screening and Evaluation of Antioxidant Activities of Selected Naphthalene Compounds.
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OZEN, TEVFIK, MACIT, MUSTAFA, and TOKA, MEHMET
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OXIDANT status , *NAPHTHALENE , *TRIFLUOROMETHYL compounds , *ANILINE , *MOLYBDENUM - Abstract
The antioxidant activities of twelve naphthalene compounds containing (E)-1-((3-iodophenylimino)methyl) naphthalen-2-ol (NAPH1), (E)-1-((3-bromophenylimino) methyl) naphthalen-2-ol (NAPH2), E)-1-((4-bromo-2-(trifluoromethoxy) phenylimino) methyl) naphthalen-2-ol, (E)-1-((4-bromo-2-(trifluoromethoxy) phenylimino) methyl)naphthalen-2-ol (NAPH3), (E)-1-((2-methoxy-5-(trifluoromethyl) phenylimino) methyl) naphthalen-2-ol (NAPH4), (E)-1-((naphthalen-2-ylimino) methyl) naphthalen-2-ol (NAPH5), (E)-1-((2-bromo-3-methylphenylimino) methyl) naphthalen-2-ol (NAPH6), (E)-N-((2-ethoxynaphthalen-1-yl)methylene)-3-methylaniline (NAPH7), (E)-4-ethoxy-N-((2-ethoxynaphthalen-1-yl) methylene) aniline (NAPH8), (E)-N-((2-ethoxynaphthalen-1-yl) methylene) naphthalen-1-amine (NAPH9), (E)-1-(2,5-difluorophenyl)-N-((2-ethoxynaphthalen-1-yl) methylene) methanamine (NAPH10), (E)-N-((2-ethoxynaphthalen-1-yl) methylene)-4-fluoroaniline (NAPH11), (E)-N-((2-ethoxynaphthalen-1-yl)methylene)-2-ethylaniline (NAPH12) were investigated in vitro by antioxidant activity (phosphomolybdenum assay), reducing power, H2O2 scavenging activity, metal chelating effects and lipid peroxidation. Scavenging activities of the naphthalen compounds were tested against 1,1-diphenyl-2-picrylhydrazyl, hydroxyl and superoxide anion radicals. Most of them are potent antioxidant, radical superoxide anion scavengers and in vitro inhibition of lipid peroxidation. The compounds; NAPH5, NAPH10 and NAPH12 were found to exhibit promising antioxidant profiles at 10 and 50 mM concentrations. Among these, NAPH5 at higher concentration was the most active compound in inhibiting lipid peroxidation as shown in the homogenates of kidney, heart and spleen. The presented results validate that NAPH5, NAPH10 and NAPH12 can be possessed as a source of antioxidant potential and a rich source of synthetic antioxidant for medicinal or foods. [ABSTRACT FROM AUTHOR]
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- 2018
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16. Trifluoromethyl-Substituted Large Band-Gap Polytriphenylamines for Polymer Solar Cells with High Open-Circuit Voltages.
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Yi, Shuwang, Deng, Wanyuan, Sun, Sheng, Lan, Linfeng, He, Zhicai, Yang, Wei, and Zhang, Bin
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BAND gaps , *TRIFLUOROMETHYL compounds , *CHEMICAL structure , *FIELD-effect transistors , *SOLAR cells - Abstract
Two large band-gap polymers (PTPACF and PTPA2CF) based on polytriphenylamine derivatives with the introduction of electron-withdrawing trifluoromethyl groups were designed and prepared by Suzuki polycondensation reaction. The chemical structures, thermal, optical and electrochemical properties were characterized in detail. From the UV-visible absorption spectra, the PTPACF and PTPA2CF showed the optical band gaps of 2.01 and 2.07 eV, respectively. The cyclic voltammetry (CV) measurement displayed the deep highest occupied molecular orbital (HOMO) energy levels of -5.33 and -5.38 eV for PTPACF and PTPA2CF, respectively. The hole mobilities, determined by field-effect transistor characterization, were 2.5 × 10-3 and 1.1 × 10-3 cm2 V-1 S-1 for PTPACF and PTPA2CF, respectively. The polymer solar cells (PSCs) were tested under the conventional device structure of ITO/PEDOT:PSS/polymer:PC71BM/PFN/Al. All of the PSCs showed the high open circuit voltages (Vocs) with the values approaching 1 V. The PTPACF and PTPA2CF based PSCs gave the power conversion efficiencies (PCEs) of 3.24% and 2.40%, respectively. Hence, it is a reliable methodology to develop high-performance large band-gap polymer donors with high Vocs through the feasible side-chain modification. [ABSTRACT FROM AUTHOR]
- Published
- 2018
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17. Influence of body size, metabolic rate and life history stage on the uptake and excretion of the lampricide 3-trifluoromethyl-4-nitrophenol (TFM) by invasive sea lampreys (Petromyzon marinus).
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Tessier, Laura R., Long, Tristan A.F., and Wilkie, Michael P.
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SEA lamprey , *TRIFLUOROMETHYL compounds , *METAMORPHOSIS , *NITROPHENOLS , *BODY size - Abstract
Invasive sea lamprey ( Petromyzon marinus ) are controlled in the Great Lakes using the lampricide 3-trifluoromethyl-4-nitrophenol (TFM), which is applied to streams infested with larval lamprey. However, lamprey that survive treatments (residuals) remain a challenge because they may subsequently undergo metamorphosis into parasitic juvenile animals that migrate downstream to the Great Lakes, where they feed on important sport and commercial fishes. The goal of this study was to determine if body size and life stage could potentially influence sea lamprey tolerance to TFM by influencing patterns of TFM uptake and elimination. Because mass specific rates of oxygen consumption ( M ˙ O 2 ) are lower in larger compared to smaller lamprey, we predicted that TFM uptake would be negatively correlated to body size, suggesting that large larvae would be more tolerant to TFM exposure. Accordingly, TFM uptake and M ˙ O 2 were measured in larvae ranging in size from 0.2–4.2 g using radio-labelled TFM ( 14 C-TFM) and static respirometry. Both were inversely proportional to wet mass ( M ), and could be described usingthe allometric power relationship: Y = aM b , in which M ˙ O 2 = 1.86 M 0.53 and TFM Uptake = 7.24 M 0.34 . We also predicted that body size would extend to rates of TFM elimination, which was measured following the administration of 14 C-TFM (via intraperitoneal injection). However, there were no differences in the half-lives of elimination of TFM (T 1/2 -TFM). There were also no differences in M ˙ O 2 or TFM uptake amongst size-matched larval, metamorphosing (stages 6–7), or post-metamorphic (juvenile) sea lamprey. However, the T 1/2 -TFM was significantly lower in larval than post-metamorphic lamprey (juvenile), indicating the larval lamprey cleared TFM more efficiently than juvenile lamprey. We conclude that larger larval sea lamprey are more likely to survive TFM treatments suggesting that body size might be an important variable to consider when treating streams with TFM to control these invasive species. [ABSTRACT FROM AUTHOR]
- Published
- 2018
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18. N1-(5-Fluoro-2,4-dinitrophenyl)-N2-phenyl-4-(trifluoromethyl)benzene-1,2-diamine.
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Zissimou, Georgia A. and Koutentis, Panayiotis A.
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TRIFLUOROMETHYL compounds , *BENZENE , *DIAMINES , *DINITROBENZENES , *DIFLUOROMETHYL compounds - Abstract
Treating 1,5-difluoro-2,4-dinitrobenzene (1) with N1-phenyl-5-(trifluoromethyl)benzene-1,2-diamine (4) and N,N-diisopropylethylamine in EtOH at ca. 0 °C for 4 h affords a mixture of N1-(5-ethoxy-2,4-dinitrophenyl)-N2-phenyl-4-(trifluoromethyl)benzene-1,2-diamine (5) (38%) and N1-(5-fluoro-2,4-dinitrophenyl)-N2-phenyl-4-(trifluoromethyl)benzene-1,2-diamine (6) (51%) that can be separated by chromatography. Repeating the reaction in dichloromethane led to the sole formation of N1-(5-fluoro-2,4-dinitrophenyl)-N2-phenyl-4-(trifluoromethyl)benzene-1,2-diamine (6) in 96% yield. [ABSTRACT FROM AUTHOR]
- Published
- 2017
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19. The Unimolecular Reactions of CF3CHF2 Studied by Chemical Activation: Assignment of Rate Constants and Threshold Energies to the 1,2-H Atom Transfer, 1,1-HF and 1,2-HF Elimination Reactions, and the Dependence of Threshold Energies on the Number of F-Atom Substituents in the Fluoroethane Molecules
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Smith, Caleb A., Gillespie, Blanton R., Heard, George L., Setser, D. W., and Holmes, Bert E.
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TRIFLUOROMETHYL compounds , *UNIMOLECULAR reactions , *ACTIVATION (Chemistry) , *THRESHOLD energy , *ATOM transfer reactions , *HYDROGEN bonding - Abstract
The recombination of CF3 and CHF2 radicals in a room-temperature bath gas was used to prepare vibrationally excited CF3CHF2* molecules with 101 kcal mol-1 of vibrational energy. The subsequent 1,2-H atom transfer and 1,1-HF and 1,2-HF elimination reactions were observed as a function of bath gas pressure by following the CHF3, CF3(F)C: and C2F4 product concentrations by gas chromatography using a mass spectrometer as the detector. The singlet CF3(F)C: concentration was measured by trapping the carbene with trans-2-butene. The experimental rate constants are 3.6 × 104, 4.7 × 104, and 1.1 × 104 s-1 for the 1,2-H atom transfer and 1,1-HF and 1,2-HF elimination reactions, respectively. These experimental rate constants were matched to statistical RRKM calculated rate constants to assign threshold energies (E0) of 88 ± 2, 88 ± 2, and 87 ± 2 kcal mol-1 to the three reactions. Pentafluoroethane is the only fluoroethane that has a competitive H atom transfer decomposition reaction, and it is the only example with 1,1-HF elimination being more important than 1,2-HF elimination. The trend of increasing threshold energies for both 1,1-HF and 1,2-HF processes with the number of F atoms in the fluoroethane molecule is summarized and investigated with electronic-structure calculations. Examination of the intrinsic reaction coordinate associated with the 1,1-HF elimination reaction found an adduct between CF3(F)C: and HF in the exit channel with a dissociation energy of ~5 kcal mol-1. Hydrogen-bonded complexes between HF and the H atom migration transition state of CH3(F)C: and the F atom migration transition state of CF3(F)C: also were found by the calculations. The role that these carbene-HF complexes could play in 1,1-HF elimination reactions is discussed. [ABSTRACT FROM AUTHOR]
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- 2017
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20. d8 Nickel and palladium difluorocarbenes derived from trifluoromethyl POCOP-type pincer complexes.
- Author
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Lee, Graham M., Korobkov, Ilia, and Baker, R. Tom
- Subjects
- *
CARBENES , *TRIFLUOROMETHYL compounds , *X-ray diffraction , *PYRIDINE , *LEWIS acids - Abstract
In this study, trifluoromethyl POCOP-type pincer complexes ( iPr POCOP)Ni(CF 3 ) ( 1-CF3 ) and ( iPr POCOP)Pd(CF 3 ) ( 2-CF3 ) are prepared. These complexes undergo Lewis acid-mediated fluoride abstraction to furnish cationic d 8 difluorocarbene complexes of the type [( iPr POCOP)M(=CF 2 )] + [X] - , which are characterized in solution and for M = Ni using single-crystal X-ray diffraction analysis. The electrophilic nature of these difluorocarbene complexes is discussed, including their reactivity with pyridines. [ABSTRACT FROM AUTHOR]
- Published
- 2017
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21. Sulfonated copolyimides containing trifluoromethyl and phosphine oxide moieties: Synergistic effect towards proton exchange membrane properties.
- Author
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Mandal, Arun Kumar, Bisoi, Soumendu, Banerjee, Susanta, Komber, Hartmut, and Voit, Brigitte
- Subjects
- *
PHOSPHINE oxides , *PROTON exchange membrane fuel cells , *MOIETIES (Chemistry) , *SULFONATES , *TRIFLUOROMETHYL compounds - Abstract
This paper reports the synthesis and characterization of a series of new semi-fluorinated sulfonated copolyimides (co-SPI) using a new trifluoromethyl and phosphine oxide containing diamine monomer, namely bis[4-(4 ′ -aminophenoxy)-3-trifluoromethyl phenyl] phenylphosphine oxide (DFPPO). The copolymers were prepared by one pot polycondensation reaction of a mixture of two diamine monomers, namely 4,4 ′ -diaminostilbene-2,2 ′ -disulfonic acid (DSDSA) and DFPPO with the equimolar amount of 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA). All these copolymers were soluble in several organic solvents and size exclusion chromatography indicated the formation of high molar masses. The membranes prepared from these copolymers by solution casting route showed good mechanical properties. The polymers were characterized by FTIR and NMR spectroscopic techniques that confirmed the polymer repeat unit structures. The degree of sulfonation of the copolymers was determined from 1 H NMR signal intensities. Transmission electron microscopy (TEM) and atomic force microscopy (AFM) images of the membranes showed phase separated morphology. In general, all the copolyimides showed high proton conductivity and reasonably high oxidative and hydrolytic stability. The co-SPI membrane DFPNH-90 (90% degree of sulfonation) with IEC W = 2.86 mequiv g −1 showed proton conductivity as high as 237 mS cm −1 at 80 °C. [ABSTRACT FROM AUTHOR]
- Published
- 2017
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22. Synthesis and biological activity of a novel fungicide, pyraziflumid.
- Author
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Masatsugu ODA, Takashi FURUYA, Yukio MORISHITA, Yoshihiro MATSUZAKI, Motohiro HASEBE, and Nobutaka KUROKI
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- *
PLANT diseases , *FUNGICIDES , *CARBOXAMIDES , *PYRAZINES , *TRIFLUOROMETHYL compounds , *BASIDIOMYCETES - Abstract
Pyraziflumid was discovered as a novel SDHI fungicide chemically characterized by the 3-(trifluoromethyl)pyrazine-2-carboxamide group. This chemical series showed particularly high fungicidal activities against a broad spectrum of plant diseases in the case of N-(biphenyl-2-yl) as well as N-(1,1,3-trimethylindan-4-yl)carboxamides. Various N-(biphenyl-2-yl)pyrazine-2-carboxamides were synthesized, and their structure-activity relationships were studied. The optimization of the fungicidal performance of the series finally led to the identification of pyraziflumid, which could control a wide range of plant diseases. In this report, details of the structure-activity relationships from the lead compound to pyraziflumid are described. [ABSTRACT FROM AUTHOR]
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- 2017
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23. Forbidden Coherence Transfer of 19F Nuclei to Quantitatively Measure the Dynamics of a CF3-Containing Ligand in Receptor-Bound States.
- Author
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Yuji Tokunaga, Koh Takeuchi, and Ichio Shimada
- Subjects
- *
LIGANDS (Biochemistry) , *DRUG development , *MOIETIES (Chemistry) , *FLUORINE compounds , *TRIFLUOROMETHYL compounds - Abstract
The dynamic property of a ligand in the receptor-bound state is an important metric to characterize the interactions in the ligand-receptor interface, and the development of an experimental strategy to quantify the amplitude of motions in the bound state is of importance to introduce the dynamic aspect into structure-guided drug development (SGDD). Fluorine modifications are frequently introduced at the hit-to-lead optimization stage to enhance the binding potency and other characteristics of a ligand. However, the effects of fluorine modifications are generally difficult to predict, owing to the pleiotropic nature of the interactions. In this study, we report an NMR-based approach to experimentally evaluate the local dynamics of trifluoromethyl (CF3)-containing ligands in the receptor-bound states. For this purpose, the forbidden coherence transfer (FCT) analysis, which has been used to study the dynamics of methyl moieties in proteins, was extended to the 19F nuclei of CF3-containing ligands. By applying this CF3-FCT analysis to a model interaction system consisting of a ligand, AST-487, and a receptor, p38α, we successfully quantified the amplitude of the CF3 dynamics in the p38α-bound state. The strategy would bring the CF3-containing ligands within the scope of dynamic SGDD to improve the affinity and specificity for the drug-target receptors. [ABSTRACT FROM AUTHOR]
- Published
- 2017
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24. New poly(amide-imide)s with trifluoromethyl and chloride substituents: Synthesis, thermal, dielectric, and optical properties.
- Author
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Liu, Yu, Qian, Xinyu, Shi, Haibiao, Zhou, Weiyi, Cai, Yuting, Li, Wenze, and Yao, Hongyan
- Subjects
- *
OPTICAL properties , *TRIFLUOROMETHYL compounds , *CHEMICAL synthesis , *DIAMINES , *THERMAL stability , *ORGANIC solvents - Abstract
Two novel fluorinated diimide-diacid monomers, [2,2′-(4,4′-(4′-chloro-3′-(trifluoromethyl)biphenyl-2,5-diyl)bis(oxy)bis(3-(trifluoromethyl)-4,1-phenylene))bis(1,3-dioxoisoindoline-5-carboxylic acid)] (III) and [2,2′-(4,4′-(3′,5′-bis(trifluoromethyl)biphenyl-2,5-diyl)bis(oxy)bis(3-(trifluoromethyl)-4,1-phe-nylene))bis(1,3-dioxoisoindoline-5-carboxylic acid)] (IV), were respectively designed and synthesized viathe reactions between the diamine (I or II) and two molar equivalents of trimellitic anhydride. Based on these two diimide-diacids, two families of novel poly(amide-imide)s (PAIs) (IIIa–IIIe and IVa–IVe) bearing different trifluoromethyl groups were prepared by directly polymerizing diimide-diacids with a series of aromatic diamines (a–e). All of the PAIs exhibited high glass transition temperatures ( T g s, 236–268 °C), excellent thermal stability (only 5% weight loss at 493–542 °C under nitrogen) and good solubility in various organic solvents since the bulky pendant groups were introduced. The cast films of these PAIs (thickness = 80–90 μm) had excellent optical transparency (70–83% at 450 nm, 85–87% at 550 nm and 88–89% at 800 nm) and low dielectric constants (2.62–2.92 at 1 MHz). In addition, the spin-coated films of these PAIs presented very low birefringence values the minimum of which was 0.0073 at 650 nm. These spin-coated films also exhibited very weak absorption at the near-infrared communication wavelengths of 1310 and 1550 nm. [ABSTRACT FROM AUTHOR]
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- 2017
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25. DMT efficiently inhibits hepatic gluconeogenesis by regulating the Gaq signaling pathway.
- Author
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Ting-Ting Zhou, Fei Ma, Xiao-Fan Shi, Xin Xu, Te Du, Xiao-Dan Guo, Gai-Hong Wang, Liang Yu, Rukachaisirikul, Vatcharin, Li-Hong Hu, Jing Chen, and Xu Shen
- Subjects
- *
TYPE 2 diabetes , *DIMETHYLTRYPTAMINE , *GLUCONEOGENESIS , *GLUCOSE synthesis , *TRIFLUOROMETHYL compounds , *CYCLIC-AMP-dependent protein kinase - Abstract
Type 2 diabetes mellitus (T2DM) is a chronic metabolic disease with complicated pathogenesis and targeting gluconeogenesis inhibition is a promising strategy for antidiabetic drug discovery. G protein-coupled receptors (GPCRs) are classified as distinct families by heterotrimeric G proteins, primarily including Gas, Gai and Gaq. Gas-coupled GPCRs function potently in the regulation of hepatic gluconeogenesis by activating cyclic adenosine monophosphate (cAMP)/protein kinase A (PKA) pathway and Gaicoupled GPCRs exhibit inhibitory effect on adenylyl cyclase and reduce intracellular cAMP level. However, little is known about the regulation of Gaq-coupled GPCRs in hepatic gluconeogenesis. Here, small-molecule 2-(2,4-dimethoxy-3-methylphenyl)-7-(thiophen-2-yl)-9-(trifluoromethyl)-2,3-dihydropyrido[3',2':4,5]thieno[3,2-d]pyrimidin-4(1H)-one (DMT) was determined to suppress hepatic glucose production and reduce mRNA levels of gluconeogenic genes. Treatment of DMT in db/db mice decreased fasting blood glucose and hemoglobin A1C (HbA1c) levels, while improved glucose tolerance and pyruvate tolerance. Mechanism study demonstrated that DMT-inhibited gluconeogenesis by regulating the Gaq/phospholipase C (PLC)/inositol-1,4,5-triphosphate receptor (IP3R)-mediated calcium (Ca2+)/calmodulin (CaM)/phosphatidylinositol-4,5-bisphosphate 3-kinase (PI3K)/protein kinase B (AKT)/forkhead box protein O1 (FOXO1) signaling pathway. To our knowledge, DMT might be the first reported small molecule able to suppress hepatic gluconeogenesis by regulating Gaq signaling, and our current work has also highlighted the potential of DMT in the treatment of T2DM. [ABSTRACT FROM AUTHOR]
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- 2017
- Full Text
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26. A novel branched side-chain-type sulfonated polyimide membrane with flexible sulfoalkyl pendants and trifluoromethyl groups for vanadium redox flow batteries.
- Author
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Li, Jinchao, Liu, Suqin, He, Zhen, and Zhou, Zhi
- Subjects
- *
SULFONATES , *POLYIMIDES , *TRIFLUOROMETHYL compounds , *VANADIUM redox battery , *MELAMINE , *HYDROPHOBIC compounds - Abstract
A novel branched side-chain-type sulfonated polyimide (6F-s-bSPI) membrane with accessible branching agents of melamine, hydrophobic trifluoromethyl groups ( CF 3 ), and flexible sulfoalkyl pendants is prepared by a high-temperature polycondensation and post-sulfonation method for use in vanadium redox flow batteries (VRFBs). The chemical structure of the 6F-s-bSPI membrane is confirmed by ATR-FTIR and 1 H NMR spectra. The physico-chemical properties of the as-prepared 6F-s-bSPI membrane are systematically investigated and found to be strongly related to the specially designed structure. The 6F-s-bSPI membrane offers a reduced cost and possesses a significantly lowered vanadium ion permeability (1.18 × 10 −7 cm 2 min −1 ) compared to the linear SPI (2.25 × 10 −7 cm 2 min −1 ) and commercial Nafion 115 (1.36 × 10 −6 cm 2 min −1 ) membranes, prolonging the self-discharge duration of the VRFBs. In addition, the VRFB assembled with a 6F-s-bSPI membrane shows higher coulombic (98.3%–99.7%) and energy efficiencies (88.4%–66.12%) than that with a SPI or Nafion 115 membrane under current densities ranging from 20 to 100 mA cm −2 . Moreover, the VRFB with a 6F-s-bSPI membrane delivers a stable cycling performance over 100 cycles with no decline in coulombic and energy efficiencies. These results show that the branched side-chain-type structure is a promising design to prepare excellent proton conductive membranes. [ABSTRACT FROM AUTHOR]
- Published
- 2017
- Full Text
- View/download PDF
27. 2,4,6-Trimethyl-N-[3-(trifluoromethyl)phenyl]benzenesulfonamide increases calcium influx in lipopolisaccharide-pre-treated arteries.
- Author
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GRZEŚK, ELŻBIETA, SZADUJKIS‑SZADURSKA, KATARZYNA, BLOCH-BOGUSŁAWSKA, ELŻBIETA, WICIŃSKI, MICHAŁ, MALINOWSKI, BARTOSZ, KOŁTAN, SYLWIA, TEJZA, BARBARA, PUJANEK, MACIEJ, and GRZEŚK, GRZEGORZ
- Subjects
- *
TRIFLUOROMETHYL compounds , *BENZENESULFONAMIDES , *PHOSPHOLIPASE C , *VASCULAR smooth muscle , *POLYSACCHARIDES , *SEPTIC shock - Abstract
It has been demonstrated that 2,4,6-trimethyl-N- [3-(trifluoromethyl)phenyl]benzenesulfonamide (m-3M3FBS) activates phospholipase C (PLC) and stimulates apoptosis in smooth muscle cells, which may increase vascular reactivity. The primary aim of the present study was to evaluate the physiological effects of the direct stimulation of PLC by m-3M3FBS on vascular smooth muscle reactivity in arteries pre-treated with lipopolysaccharides (LPS) as a model of septic shock. Experiments were performed on isolated and perfused tail arteries of Wistar rats. The contraction force in the model was measured by assessing increases in perfusion pressure at a constant flow. Parameters describing the concentration-response curves (CRCs) obtained for phenylephrine and arginine-vasopressin in the presence of LPS confirmed a decrease in vessels reactivity. In comparison with the controls, m-3M3FBS treatment caused a significant increase in LPS-untreated as well as pre-treated arteries. Furthermore, in the presence of m-3M3FBS, calcium influx from intra- as well as extracellular calcium stores was significantly higher for LPS-untreated and pre-treated arteries. The results of the present study suggested that m-3M3FBS significantly increased the reactivity of vascular smooth muscle cells pre-treated with LPS by increasing the calcium influx from intra- and extracellular calcium stores. Further studies investigating this mechanism are required to evaluate whether this pathway may be a potential therapeutic strategy to treat sepsis. [ABSTRACT FROM AUTHOR]
- Published
- 2017
- Full Text
- View/download PDF
28. Antimalarial activity of novel 4-aminoquinolines active against drug resistant strains.
- Author
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Kondaparla, Srinivasarao, Katti, S.B., Soni, Awakash, Manhas, Ashan, Srivastava, Kumkum, and Puri, Sunil K.
- Subjects
- *
ANTIMALARIALS , *TRIFLUOROMETHYL compounds , *QUINOLINE , *CELL-mediated cytotoxicity , *HEME - Abstract
In the present study we have synthesized a new class of 4-aminoquinolines and evaluated against Plasmodium falciparum in vitro (3D7-sensitive strain & K1-resistant strain) and Plasmodium yoelii in vivo (N-67 strain). Among the series, eleven compounds ( 5, 6, 7, 8, 9, 11, 12, 13, 14, 15 and 21 ) showed superior antimalarial activity against K1 strain as compared to CQ. In addition, all these analogues showed 100% suppression of parasitemia on day 4 in the in vivo mouse model against N-67 strain when administered orally. Further, biophysical studies suggest that this series of compounds act on heme polymerization target. [ABSTRACT FROM AUTHOR]
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- 2017
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29. Bis(trifluoromethylsulfonyl)imide, or dicyanamide-based ionic liquids in the liquid–liquid extraction of hex-1-ene from hexane and cyclohexene from cyclohexane.
- Author
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Domańska, Urszula, Karpińska, Monika, and Wlazło, Michał
- Subjects
- *
TRIFLUOROMETHYL compounds , *HEXANE , *CYCLOHEXANE , *LIQUID-liquid extraction , *LIQUID chromatography - Abstract
In this work we studied the applicability of four imidazolium-based ionic liquids (ILs) with different allyl-, or benzyl-substituents and bis(trifluoromethylsulfonyl)imide, or dicyanamide anions in the separation of hex-1-ene/hexane and cyclohexene/cyclohexane compounds. Experimental values for liquid–liquid equilibrium (LLE) were obtained for various binary and ternary mixtures of {IL (1) + hex-1-ene (2) + hexane (3)} or {IL (1) + cyclohexene (2) + cyclohexane (3)} at T = 298.15 K and p = 0.1 MPa. The ILs studied were as follows: 1-allyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [AMIM][NTf 2 ], 1-allyl-3-methylimidazolium dicyanamide, [AMIM][DCA], 1-benzyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [BzMIM][NTf 2 ], 1-benzyl-3-methylimidazolium dicyanamide, [BzMIM][DCA]. These ILs were chosen after the analysis of the selectivities calculated from the limiting activity coefficients data. The results are useful for the design an industrial process of extraction. The dicyanamide-based ILs showed excellent results in terms of selectivity, but bis(trifluoromethylsulfonyl)imide-based ILs revealed twice better solute distribution ratio. The chromatography analysis revealed that the ILs used as an entrainers were not present in the hydrocarbon-rich layer, which is convenient for production process, because eliminates the step needed for the separation of the solvent. The [AMIM][DCA] showed suitable extractive properties to replace nowadays methods of separation for hex-1-ene/hexane and cyclohexene/cyclohexane compounds. All experimental data were correlated with the NRTL model. The experimental tie-lines were calculated in good agreement with each other. [ABSTRACT FROM AUTHOR]
- Published
- 2017
- Full Text
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30. Sulfonated poly(ether imide)s with fluorenyl and trifluoromethyl groups: Application in microbial fuel cell (MFC).
- Author
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Ganesh Kumar, Anaparthi, Bera, Debaditya, Banerjee, Susanta, Veerubhotla, Ramya, and Das, Debabrata
- Subjects
- *
POLYETHERS , *TRIFLUOROMETHYL compounds , *DIAMINES , *POLYCONDENSATION , *NAPHTHALENE , *PROTON conductivity - Abstract
A series of fluorenyl and trifluoromethyl groups containing co-poly(ether imide)s (S-co-PIs) have been prepared from a new diamine monomer; 9,9-bis(3-methoxy-4-(4-amino(3-trifluoro-methyl)biphenoxy)phenyl)-9H-fluorene (APHPF). The polymers were prepared by the polycondensation reaction of 1,4,5,8-naphthalenetetracarboxylic dianhydride (NTDA) with two different diamines; APHPF and 4,4′-diaminostilbene-2,2′-disulfonicacid (DSDSA) as a co-monomer. The monomer and polymers were well characterized by 1 H NMR and ATR-FTIR spectroscopies. The co-polymers were soluble in various organic solvents and membranes were prepared from solution cast route. The S-co-PIs showed high thermal and mechanical stability. TEM and AFM results supports the formation of phase separated morphology with well separated ionic-clusters. All these S-co-PIs displayed reasonably high proton conductivity. One of the copolymers (DAN-80; IECw ∼2.27 meq g −1 ) exhibited a proton conductivity as high as 149 mS cm −1 which was comparable to that of Nafion® 117 (165 mS cm −1 ) at 80 °C. The co-polymers maintain a good balance between water-uptake and swelling ratios and peroxide resistance. Microbial Fuel Cell (MFC) performance of the co-polymers were evaluated DAN-80 exhibited a similar performance like Nafion® 117 under similar test condition. [ABSTRACT FROM AUTHOR]
- Published
- 2016
- Full Text
- View/download PDF
31. Synthesis of starch nanoparticles in a novel microemulsion with two ILs substituting two phases.
- Author
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Ji, Guangyin, Luo, Zhigang, Xiao, Zhigang, and Peng, Xichun
- Subjects
- *
MICROEMULSIONS , *STARCH synthesis , *TRIFLUOROMETHYL compounds , *FOURIER transform infrared spectroscopy , *X-ray diffraction - Abstract
A novel ionic liquid microemulsion composed of 1-octyl-3-methylimidazolium bis ((trifluoromethyl)sulfonyl)imide ([Omim]NTf, an ionic liquid), water, surfactant 1-hexadecyl-3-methylimidazolium bromide ([Cmim]Br, an ionic liquid), and cosurfactant n-butyl alcohol was prepared in our study. Pseudo-ternary phase diagram, conductivity measurement, and dynamic light scattering (DLS) analysis identified the microregion of microemulsion and confirmed the formation of water-in-ionic liquid (W/IL) region. Starch nanoparticles were prepared in the W/IL microemulsion with epichlorohydrin as cross-linker. Fourier transform infrared spectroscopy and X-ray diffraction characterized the structure of starch nanoparticles and demonstrated that cross-linking reaction happened among starch molecules. Scanning electron microscopy intuitively revealed that starch nanoparticles were spherical granules with smooth surface and fine dispersibility. Also, starch nanoparticles with a mean diameter of 93.2 nm and relatively concentrated size distribution were confirmed by DLS. [ABSTRACT FROM AUTHOR]
- Published
- 2016
- Full Text
- View/download PDF
32. A One-Pot Tandem Strategy in Catalytic Asymmetric Vinylogous Aldol Reaction of Homoallylic Alcohols.
- Author
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Xufeng Hou, Zhenzhong Jing, Xiangbin Bai, and Zhiyong Jiang
- Subjects
- *
TRIFLUOROMETHYL compounds , *KETONES , *PHOSPHONATES , *ORGANOCATALYSIS , *ALCOHOL - Abstract
Reported is a rationally-designed one-pot sequential strategy that allows homoallylic alcohols to be employed in a catalytic, asymmetric, direct vinylogous aldol reaction with a series of activated acyclic ketones, including trifluoromethyl ketones, γ-ketoesters, and α-keto phosphonates, in high yields (up to 95%) with excellent regio- and enantio-selectivity (up to 99% ee). This modular combination, including Jones oxidation and asymmetric organocatalysis, has satisfactory compatibility and reliability even at a 20 mmol scale, albeit without intermediary purification. [ABSTRACT FROM AUTHOR]
- Published
- 2016
- Full Text
- View/download PDF
33. Photoinduced C-C Cross-Coupling of Aryl Chlorides and Inert Arenes.
- Author
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Wang, Lele, Qiu, Wenzhao, Shao, Hongge, and Yuan, Rusheng
- Subjects
- *
ARYL chlorides , *CHEMICAL bonds , *AROMATIC compounds , *ARYL radicals , *TRIFLUOROMETHYL compounds , *CHEMICAL synthesis , *NUCLEOPHILIC substitution reactions - Abstract
Here we report a facile, efficient, and catalyst-free method to realize C-C cross-coupling of aryl chlorides and inert arenes under UV light irradiation. The aryl radical upon homolytic cleavage of C-Cl bond initiated the nucleophilic substitution reaction with inert arenes to give biaryl products. This mild reaction mode can also be applied to other synthetic reactions, such as the construction of C-N bonds and trifluoromethylated compounds. [ABSTRACT FROM AUTHOR]
- Published
- 2016
- Full Text
- View/download PDF
34. Aza-Henry Reactions on C-Alkyl Substituted Aldimines.
- Author
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Pelagalli, Alessia, Pellacani, Lucio, Scandozza, Elia, and Fioravanti, Stefania
- Subjects
- *
NITROALDOL reactions , *ALDIMINES , *ETHANOL , *OXIDATION of alkanes , *TRIFLUOROMETHYL compounds - Abstract
The reactivity of C-CH3 substituted N-protected aldimines in aza-Henry addition reactions was compared with that of the analogous trifluoromethylated compounds. C-Alkyl aldimines easily reacted with nitro alkanes under solvent-free conditions and in the absence of catalyst, despite being worse electrophiles than C-CF3 aldimines, they gave the aza-Henry addition only when ZrCl4 was added. The presence of a bulky group on the imine carbon deeply influenced the reactivity. [ABSTRACT FROM AUTHOR]
- Published
- 2016
- Full Text
- View/download PDF
35. 2-Diazo-1-phenyl-2-((trifluoromethyl)sulfonyl)ethan-1-one: Another Utility for Electrophilic Trifluoromethylthiolation Reactions.
- Author
-
Huang, Zhongyan, Okuyama, Kenta, Wang, Chen, Tokunaga, Etsuko, Li, Xiaorui, and Shibata, Norio
- Subjects
- *
TRIFLUOROMETHYL compounds , *SULFONYL compounds , *ORGANOSULFUR compounds , *ETHANES , *ALKANES - Abstract
2-Diazo-1-phenyl-2-((trifluoromethyl)sulfonyl)ethan-1-one (diazo-triflone) ( 2) is not only a building block but also a reagent. In this study, diazo-triflone, which was originally used for the synthesis of β-lactam triflones as a trifluoromethanesulfonyl (SO2CF3) building block under catalyst-free thermal conditions, is redisclosed as an effective electrophilic trifluoromethylthiolation reagent under copper catalysis. A broad set of enamines, indoles, β-keto esters, pyrroles, and anilines were nicely transformed into corresponding trifluoromethylthio (SCF3) compounds in good to high yields by diazo-triflone under copper catalysis via an electrophilic-type reaction. A coupling-type trifluoromethylthiolation reaction of aryl iodides was also realized by diazo-triflone in acceptable yields. [ABSTRACT FROM AUTHOR]
- Published
- 2016
- Full Text
- View/download PDF
36. Asymmetric Formal Aza-Diels-Alder Reaction of Trifluoromethyl Hemiaminals with Enones Catalyzed by Primary Amines.
- Author
-
Sheng Zhang, Lide Cha, Lijun Li, Yanbin Hu, Yanan Li, Zhenggen Zha, and Zhiyong Wang
- Subjects
- *
DIELS-Alder reaction , *TRIFLUOROMETHYL compounds , *CARBONYL compounds , *CHIRALITY , *STEREOSELECTIVE reactions , *SUBSTITUENTS (Chemistry) - Abstract
A primary amine-catalyzed asymmetric formal aza-Diels-Alder reaction of trifluoromethyl hemiaminals with enones was developed via a chiral gem-diamine intermediate. This novel protocol allowed facile access to structurally diverse trifluoromethyl-substituted piperidine scaffolds with high stereoselectivity. The utility of this method was further demonstrated through a concise approach to biologically active 4-hydroxypiperidine. More importantly, a stepwise mechanism involving an asymmetric induction process was proposed to rationalize the positive correlation between the chirality of the gem-diamine intermediate and the formal aza-Diels-Alder product. [ABSTRACT FROM AUTHOR]
- Published
- 2016
- Full Text
- View/download PDF
37. An Energetic Guide for Estimating Trifluoromethyl Cation Donor Abilities of Electrophilic Trifluoromethylating Reagents: Computations of X-CF3 Bond Heterolytic Dissociation Enthalpies.
- Author
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Man Li, Xiao-Song Xue, Jinping Guo, Ya Wang, and Jin-Pei Cheng
- Subjects
- *
TRIFLUOROMETHYL compounds , *ELECTROPHILES , *DISSOCIATION (Chemistry) , *ENTHALPY , *CHEMICAL bonds , *SUBSTITUENTS (Chemistry) - Abstract
This work established an energetic guide for estimating the trifluoromethyl cation-donating abilities (TC+DA) of electrophilic trifluoromethylating reagents through computing X-CF3 bond (X = O, S, Se, Te, and I) heterolytic dissociation enthalpies. TC+DA values for a wide range of popular reagents were derived on the basis of density functional calculations (M06-2X). A good correspondence has been identified between the computed TC+DA values and the experimentally observed relative trifluoromethylating capabilities of the reagents. Substituent effects hold good linear free energy relationships on the TC+DAs of the most widely used reagents including Umemoto reagent, Yagupolskii-Umemoto reagent, and Togni reagents, which allow their trifluoromethylating capabilities to be rationally tuned by substituents and thus extend their synthetic utility. All the information disclosed in this work would contribute to future rational exploration of the electrophilic trifluoromethylation chemistry. [ABSTRACT FROM AUTHOR]
- Published
- 2016
- Full Text
- View/download PDF
38. Ethyl Nitroacetate in Aza-Henry Addition on Trifluoromethyl Aldimines: A Solvent-Free Procedure To Obtain Chiral Trifluoromethyl α,β-Diamino Esters.
- Author
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Parise, Luca, Pelagalli, Alessia, Pellacani, Lucio, Sciubba, Fabio, Vergari, Maria Cecilia, and Fioravanti, Stefania
- Subjects
- *
ACETATES , *TRIFLUOROMETHYL compounds , *ADDITION reactions , *ALDIMINES , *ALKYL compounds , *PALLADIUM catalysts , *NITROGEN , *NUCLEOPHILIC catalysis - Abstract
A self-catalyzed aza-Henry addition of ethyl nitroacetate on N-alkyl trifluoromethyl aldimines was reported to synthesize β-amino α-nitro trifluoromethyl esters, precursors of α,β-diamino acid derivatives. In the presence of a resident chiral center on the imine nitrogen, the use of a suitable Lewis acid leads to a good stereofacial control, always resulting from a nucleophilic unlike attack. By starting from optically pure N-protected trifluoromethyl aldimines or directly from N-α-amino ester trifluoromethyl aldimines, small ψ[CH(CF3)NH]-peptidomimetic backbones can be achieved in which a new primary amine function represents a possible center for synthetic extension. Finally, a very interesting, and never observed before, palladium-catalyzed syn β-elimination occurred, leading to the selective nitro group reduction reaction on the syn-α-amino ester functionalized aza-Henry adducts and obtaining more stable optically pure trifluoromethyl conjugated imines. [ABSTRACT FROM AUTHOR]
- Published
- 2016
- Full Text
- View/download PDF
39. Synthesis of 5,10-bis(Trifluoromethyl) Substituted β-Octamethylporphyrins and Central-Metal-Dependent Solvolysis of Their meso-Trifluoromethyl Groups.
- Author
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Masaaki Suzuki, Neya, Saburo, and Yutaka Nishigaichi
- Subjects
- *
TRIFLUOROMETHYL compounds , *SOLUTION (Chemistry) , *ALKALINE solutions , *SOLVOLYSIS , *SOLVENTS - Abstract
Abstract: 5,10-Bistrifluoromethyl substituted β-octamethylporphyrins were synthesized via a scrambling side reaction of a dipyrromethane precursor in the presence of a large excess of trifluoroacetic acid. Compared with the trans-analogs, the cis-analogs of meso-trifluoromethyl β-octaalkylporphyrin showed more red-shifted absorption bands. These meso-trifluoromethyl derivatives of β-octaalkylporphyrins underwent smooth metalation, similar to other common porphyrins, however, the corresponding zinc complexes underwent a type of solvolysis, whereby the trifluoromethyl groups were converted into methoxycarbonyl groups by the methanol used as solvent. UV-visible absorption spectra and X-ray crystal structure analyses revealed that the presence of a methoxycarbonyl substituent did not influence the deformation of the molecular framework and its absorption properties; this is because the methoxycarbonyl has a planar and perpendicular geometry, as opposed to the relatively bulky trifluoromethyl substituent. [ABSTRACT FROM AUTHOR]
- Published
- 2016
- Full Text
- View/download PDF
40. DFT Study on the Mechanism and Stereoselectivity of NHC-Catalyzed Synthesis of Substituted Trifluoromethyl Dihydropyranones with Contiguous Stereocenters.
- Author
-
Xiaoli Zhang, Mingsheng Tang, Yang Wang, Yingying Ran, Donghui Wei, Yanyan Zhu, and Wenjing Zhang
- Subjects
- *
STEREOSELECTIVE reactions , *DENSITY functional theory , *TRIFLUOROMETHYL compounds , *PYRANONES synthesis , *CATALYSIS , *SUBSTITUENTS (Chemistry) - Abstract
Recently, Smith and co-workers reported an interesting work that provides a facile approach to access substituted trifluoromethyl dihydropyranones with two contiguous stereocenters by utilizing the a,β-unsaturated trifluoromethyl ketones as a substrate for NHC-catalyzed [4 + 2] cycloadditions. The most significant point of this reaction lies in the capability of introducing substituents to the C(5) position of the dihydropyranones. In the present study, we performed detailed DFT investigations toward the catalytic mechanism of this reaction, and determined origins of the diastereo- and enatioselectivities through analyses on distortion energies of two key stationary species and on components of Gibbs free energy barriers of elementary steps in which the stereocenters are generated. The theoretically predicted configuration of the main product was well-consistent with the experimental results, and the excellent correlation between the relative free energy barriers (ΔΔG2980) with the relative enthalpy barriers (ΔΔH2980) indicates that the stereoselectivity should originate from differences of enthalpy barriers rather than distinctions of the entropy item (-TΔS2980) changes. The systematic study of the substituent effect affords conclusive evidence for the catalytic mechanism we proposed but failed to give any clue to how the various electronic properties of substituents act on the experimental yields. [ABSTRACT FROM AUTHOR]
- Published
- 2016
- Full Text
- View/download PDF
41. Binary mixtures of ([C4mim][NTf2] + molecular organic solvents): Thermophysical, acoustic and transport properties at various compositions and temperatures.
- Author
-
Malek, Naved I. and Ijardar, Sushma P.
- Subjects
- *
BINARY mixtures , *TRIFLUOROMETHYL compounds , *IMIDAZOLES , *THERMOPHYSICAL properties , *COMPLEX compounds , *ORGANIC solvents , *ISENTROPIC compression , *IONIC liquids - Abstract
In this manuscript, densities, ρ , speeds of sound, u , and viscosities, η for binary mixtures of 1-butyl-3-methylimidazoliumbis(trifluoromethylsulfonyl)imide([C 4 mim][NTf 2 ]) with molecular organic solvents (MOS) namely butyl acetate (BAC), butan-1-amine (BAM) and butanal (BAL) were measured at entire range of compositions. The measurements were collected at atmospheric pressure and temperature ranges from (298.15 to 323.15) K. The excess molar volumes, V m E , excess molar isentropic compressibilities, K S , m E , and logarithm of viscosity, ln η m were derived from measured values of densities, ρ , speeds of sound, u , and viscosity, η , respectively. The V m E , K S , m E and ln η m were correlated using Redlich–Kister polynomial equation. The non-ideal behaviour of these binary mixtures was discussed in light of temperature, nature of molecular organic solvent, structural effect and extent of molecular interactions exist in the binary mixtures. The V m E and K S , m E were negative and decrease with increasing temperature. The experimental V m E were reviewed by Prigogine–Flory–Patterson (PFP) theory. [ABSTRACT FROM AUTHOR]
- Published
- 2016
- Full Text
- View/download PDF
42. DFT Study on the Mechanism and Stereoselectivity of NHC-Catalyzed Synthesis of Substituted Trifluoromethyl Dihydropyranones with Contiguous Stereocenters.
- Author
-
Xiaoli Zhang, Mingsheng Tang, Yang Wang, Yingying Ran, Donghui Wei, Yanyan Zhu, and Wenjing Zhang
- Subjects
- *
CARBENES , *DENSITY functional theory , *REACTION mechanisms (Chemistry) , *STEREOSELECTIVE reactions , *HETEROCYCLIC compounds , *CATALYSIS synthesis , *TRIFLUOROMETHYL compounds - Abstract
Recently, Smith and co-workers reported an interesting work that provides a facile approach to access substituted trifluoromethyl dihydropyranones with two contiguous stereocenters by utilizing the α,β-unsaturated trifluoromethyl ketones as a substrate for NHC-catalyzed [4 + 2] cycloadditions. The most significant point of this reaction lies in the capability of introducing substituents to the C(5) position of the dihydropyranones. In the present study, we performed detailed DFT investigations toward the catalytic mechanism of this reaction, and determined origins of the diastereo- and enatioselectivities through analyses on distortion energies of two key stationary species and on components of Gibbs free energy barriers of elementary steps in which the stereocenters are generated. The theoretically predicted configuration of the main product was well-consistent with the experimental results, and the excellent correlation between the relative free energy barriers (ΔΔG2980) with the relative enthalpy barriers (ΔΔH2980) indicates that the stereoselectivity should originate from differences of enthalpy barriers rather than distinctions of the entropy item (-TΔS2980) changes. The systematic study of the substituent effect affords conclusive evidence for the catalytic mechanism we proposed but failed to give any clue to how the various electronic properties of substituents act on the experimental yields. [ABSTRACT FROM AUTHOR]
- Published
- 2016
- Full Text
- View/download PDF
43. Effect of 2,4,6-trimethyl-N-[3-(trifluoromethyl)phenyl]benzene-sulfonamide on calcium influx in three contraction models.
- Author
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GRZEŚK, ELŻBIETA, SZADUJKIS-SZADURSKA, KATARZYNA, WICIŃSKI, MICHAŁ, MALINOWSKI, BARTOSZ, SINJAB, THABIT A., TEJZA, BARBARA, PUJANEK, MACIEJ, JANISZEWSKA, EWA, KOPCZYŃSKA, ANNA, and GRZEŚK, GRZEGORZ
- Subjects
- *
TRIFLUOROMETHYL compounds , *CALCIUM compounds , *BENZENESULFONAMIDES , *PHOSPHOLIPASE C , *APOPTOSIS ,SULFONAMIDE drugs - Abstract
2,4,6-Trimethyl-N-[3-(trifluoromethyl)phenyl] benzenesulfonamide (m-3M3FBS) activates phospholipase C and stimulates apoptosis; however, in smooth muscle cells it may increase the perfusion pressure. The main aim of the present study was to evaluate the physiological effect of direct stimulation of phospholipase C on vascular smooth muscle reactivity using three contraction models. Experiments were performed on the isolated and perfused tail artery of Wistar rats. The contraction force in the present model was measured by an increased level of perfusion pressure with a constant flow. Concentration-response curves (CRCs) obtained for phenylephrine, arg-vasopressin, mastoparan-7 and Bay K8644 presented a sigmoidal association. In comparison to the control curves, CRCs in the presence of m-3M3FBS were significantly shifted to the left except for Bay K8644. Analyses of calcium influx suggest that in the presence of m-3M3FBS the calcium influx from intra- and extracellular calcium stores was significantly higher. The results of the present experiments suggest that m-3M3FBS significantly increases the reactivity of vascular smooth muscle stimulated with metabotropic receptors or G-protein by an increase in calcium influx from intra- and extracellular calcium stores. The current knowledge regarding the apoptotic pathway shows the significance of calcium ions involved in this process, thus, m-3M3FBS may induce apoptosis by an increase of cytoplasmic calcium concentration; however, simultaneously, the use of this mechanism in therapy must be preceded by a molecular modification that eliminates a possible vasoconstriction effect. [ABSTRACT FROM AUTHOR]
- Published
- 2016
- Full Text
- View/download PDF
44. Reactivity of triruthenium diphosphine clusters with 3,5-bis(trifluoromethyl)mercaptobenzene: Electronic and steric influence of diphosphines onto coordination modes of thiolate, capping sulfide, and phosphide groups to a Ru3 clusters.
- Author
-
Hernández-Cruz, María G., Zuno-Cruz, Francisco J., Alvarado-Rodríguez, José G., Rosales-Hoz, María J., Leyva, Marco A., Salazar, Verónica, and Sánchez-Cabrera, Gloria
- Subjects
- *
RUTHENIUM , *REACTIVITY (Chemistry) , *DIPHOSPHINE , *METAL clusters , *TRIFLUOROMETHYL compounds , *BENZENE , *PHOSPHIDES - Abstract
The bridge diphosphine triruthenium clusters [Ru 3 (μ-κ 2 P , P′ -diphosphine)(CO) 10 ] 1a–1c [diphosphine = dppe, dfppe and dppm, respectively] react with 3,5- bis (trifluoromethyl)mercaptobenzene under refluxing THF, resulting in the oxidative addition of the thiol, to give isostructural compounds [Ru 3 (μ-H)(μ-κ S -SC 6 H 3 (CF 3 ) 2 )(μ-κ 2 P , P′ -diphosphine)(CO) 8 ] [diphosphine = dppe ( 2a ); dfppe ( 2b ) and dppm ( 2c )] in moderate yields. The thermal hydrogenation reaction of clusters 2a or 2b gives the bridge diphosphine asymmetric dihydride isomeric compounds [Ru 3 (μ-H) 2 (μ 3 -S)(μ-κ 2 P 2 -diphosphine)(CO) 7 ] [diphosphine = dppe ( 3a ) and dfppe ( 3b )] that promote the formation of chelate diphosphine asymmetric dihydride isomers [Ru 3 (μ-H) 2 (μ 3 -S)(κ 2 P , P′ -diphosphine)(CO) 7 ] [diphosphine = dppe ( 4a ) and dfppe ( 4b )] respectively. Moreover, the hydrogenation reaction of 2a yielded the chelate diphosphine symmetric dihydride isomer [Ru 3 (μ-H) 2 (μ 3 -S)(κ 2 P , P′ -dppe)(CO) 7 ] ( 5a ). The hydrogenation reaction of 2b also yielded [Ru 3 (μ-H)(μ 3 -S){μ-κ 2 P , P′ -P(C 6 F 5 )CH 2 CH 2 P(C 6 F 5 ) 2 }(CO) 7 ] ( 6b ), where a C–P bond rupture promoted the formation of a phosphide group in a 50 electron unsaturated cluster. The new clusters have been characterized by spectroscopic methods, and the molecular structures of 2b , 2c , 3a, 3b , 5a , and 6b have been determined by single crystal X-ray diffraction studies. [ABSTRACT FROM AUTHOR]
- Published
- 2016
- Full Text
- View/download PDF
45. A facile trifluoromethylthiolation of 3-chloro-1H-inden-1-ones employing AgSCF3 and KI.
- Author
-
Biao Dong, Xiaofei Zhang, Ruiling Liu, and Chunhao Yang
- Subjects
- *
INDENE , *TRIFLUOROMETHYL compounds , *POTASSIUM iodide , *SILVER compounds , *NUCLEOPHILES , *ACTIVATORS (Chemistry) - Abstract
An efficient method for trifluoromethylthiolation of functionalized 3-chloro-1H-inden-1-ones was described. Within this method, AgSCF3 was employed as a nucleophilic reagent and KI was functionalized as an activator. This reaction provided the trifluoromethylthiolated indenones with excellent yields under moderate conditions. [ABSTRACT FROM AUTHOR]
- Published
- 2016
- Full Text
- View/download PDF
46. Synthesis of Phthalocyanines with a Pentafluorosulfanyl Substituent at Peripheral Positions.
- Author
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Iida, Norihito, Tanaka, Kenta, Tokunaga, Etsuko, Mori, Satoru, Saito, Norimichi, and Shibata, Norio
- Subjects
- *
PHTHALOCYANINE synthesis , *TRIFLUOROMETHYL compounds , *BENZENEDICARBONITRILE , *ULTRAVIOLET-visible spectroscopy , *FLUORESCENCE yield - Abstract
The pentafluorosulfanyl (SF5) group is more electronegative, lipophilic and sterically bulky relative to the well-explored trifluoromethyl (CF3) group. As such, the SF5 group could offer access to pharmaceuticals, agrochemicals and optoelectronic materials with novel properties. Here, the first synthesis of phthalocyanines (Pcs), a class of compounds used as dyes and with potential as photodynamic therapeutics, with a SF5 group directly attached on their peripheral positions is disclosed. The key for this work is the preparation of a series of SF5-containing phthalonitriles, which was beautifully regio-controlled by a stepwise cyanation via ortho-lithiation/iodination from commercially available pentafluorosulfanyl arenes. The macrocyclization of the SF5-containing phthalonitriles to SF5-substituted Pcs required harsh conditions with the exception of the synthesis of β-SF5-substituted Pc. The regiospecificity of the newly developed SF5-substituted Pcs observed by UV/Vis spectra and fluorescence quantum yields depend on the peripheral positon of the SF5 group. [ABSTRACT FROM AUTHOR]
- Published
- 2015
- Full Text
- View/download PDF
47. Prediction of (liquid + liquid) equilibrium for binary and ternary systems containing ionic liquids with the bis[(trifluoromethyl)sulfonyl]imide anion using the ASOG method.
- Author
-
Robles, Pedro A. and Cisternas, Luis A.
- Subjects
- *
CHEMICAL equilibrium , *IONIC liquids , *TRIFLUOROMETHYL compounds , *IMIDES , *EVAPORATION (Chemistry) - Abstract
Ionic liquids are neoteric, environmentally friendly solvents (as they do not produce emissions) composed of large organic cations and relatively small inorganic anions. They have favorable physical properties, such as negligible volatility and a wide range of liquid existence. (Liquid + liquid) equilibrium (LLE) data for systems including ionic liquids, although essential for the design, optimization and operation of separation processes, remain scarce. However, some recent studies have presented ternary LLE data involving several ionic liquids and organic compounds such as alkanes, alkenes, alkanols, ethers and aromatics, as well as water. In this work, the ASOG model for the activity coefficient is used to predict LLE data for 25 binary and 07 ternary systems at 101.3 kPa and several temperatures; all the systems are formed by ionic liquids including the bis[(trifluoromethyl)sulfonyl]imide (NTf 2 ) anion plus alkanes, alkenes, cycloalkanes, alkanols, water, thiophene and aromatics. New group interaction parameters were determined using a modified Simplex method, minimizing a composition-based objective function of experimental data obtained from the literature. The results are satisfactory, with rms deviations of approximately 3%. [ABSTRACT FROM AUTHOR]
- Published
- 2015
- Full Text
- View/download PDF
48. Stereochemical Investigation of the Products of the Photoinduced Perfluoroalkylation-Dimerization of Anthracene.
- Author
-
Emiko Nogami, Tomoko Yajima, Takashi Yamazaki, and Toshio Kubota
- Subjects
- *
ANTHRACENE , *DIASTEREOISOMERS , *X-ray crystallography , *ATROPISOMERS , *TRIFLUOROMETHYL compounds - Abstract
The photoinduced perfluoroalkylation of anthracene has been shown to provide 9,9′,10,10′-tetrahydro-10,10′-diperfluoroalkyl-9,9′-bianthracenes in over 70% yields, each perfluoroalkyl iodide producing three diastereomers. The structures of all three diastereomers (cis, cis, cis, trans, and trans, trans isomers) have been elucidated by both NMR and X-ray crystallographic analyses. Most notably, an X-ray crystallographic analysis has revealed that the trans, trans diastereomer having the two trifluoromethyl groups in 10,10′-positions adopts a 74° twisted relationship of the two dihydroanthracene rings. Furthermore, each of the two trans, trans isomers 2a,b has been shown to exist as a mixture of new types of atropisomers and the energy barrier for the interconversion of the two atropisomers has been estimated to be 12 kcal/mol by variable-temperature NMR analysis. [ABSTRACT FROM AUTHOR]
- Published
- 2015
- Full Text
- View/download PDF
49. Rh(III)-Catalyzed Trifluoromethylthiolation of Indoles via C-H Activation.
- Author
-
Qiang Wang, Fang Xie, and Xingwei Li
- Subjects
- *
TRIFLUOROMETHYL compounds , *INDOLE compounds , *CARBON-hydrogen bonds , *HETEROCYCLIC compounds , *ELECTROPHILES - Abstract
Cp*Rh(III) complexes have been applied as efficient catalysts for the C-H activation and trifluoromethylthiolation of indoles functionalized with a heterocycle. With N-trifluoromethylthiosaccharin being an electrophilic SCF3 reagent, this C-S coupling occurred selectively at the 2-position with good functional group tolerance. [ABSTRACT FROM AUTHOR]
- Published
- 2015
- Full Text
- View/download PDF
50. Stereoselective ZrCl4-Catalyzed Mannich-type Reaction of β-Keto Esters with Chiral Trifluoromethyl Aldimines.
- Author
-
Parise, Luca, Pellacani, Lucio, Sciubba, Fabio, Trulli, Laura, and Fioravanti, Stefania
- Subjects
- *
STEREOSELECTIVE reactions , *ZIRCONIUM , *MANNICH reaction , *KETONIC acids , *TRIFLUOROMETHYL compounds - Abstract
A method for the synthesis of fluorinated β'-amino β-dicarbonyl compounds using a Zr-catalyzed Mannich-type reaction has been developed, starting from N-protected trifluoromethyl aldimines and cyclic or acyclic β-keto esters bearing different ester residues. The in situ generated metallic complex reacted with optically pure trifluoromethyl aldimine derived from (R)-α-methylbenzylamine, giving a highly diastereoselective asymmetric Mannich-type addition with formation of a chiral quaternary center. The absolute configuration at the new chiral centers was assigned through two-dimensional nuclear Overhauser effect spectroscopic analysis coupled with computational studies. [ABSTRACT FROM AUTHOR]
- Published
- 2015
- Full Text
- View/download PDF
Catalog
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