- Sulfone-Containing Methacrylate Homopolymers: Wetting and Thermal Properties
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Although the sulfonyl functional group has a large dipole moment and compounds containing them (sulfones) have correspondingly high dielectric constants, this chemical structure has been neglected for use as a functional group to render surfaces hydrophilic. We have prepared three methacrylate polymers containing side chains capped with sulfolane, methylsulfone, and ethylsulfone functionality. The sulfolane-containing polymer exhibits an unusually high glass transition temperature (Tg = 188 °C) for a methacrylate polymer and slightly different thermal degradation behavior than the other two sulfone-containing polymers, likely due to the bulky structure of the sulfolane group in the polymer side chain. At macroscopic polymer film/water interfaces, the sulfone-containing side chains exposed to the interface impart hydrophilic properties as assessed by contact angle analysis. The hydrophilicities of sulfolane and methylsulfone surfaces are similar, and greater than the ethylsulfone surface. Although the chemical compositions of the sulfolane and ethylsulfone polymers are almost identical, the five-membered ring structure of sulfolane allows the sulfonyl moiety to be exposed at the interface in a manner similar to that of the methylsulfone polymer. The sulfonyl group at the ethylsulfone polymer/water interface is slightly masked by the ethyl group. Interestingly, the sulfolane surface displays a higher affinity to methylene iodide and n-hexadecane probe fluids compared to the other sulfone surfaces, suggesting that the five-membered ring structure of the sulfolane moiety can orient in a manner that shelters the sulfonyl group at hydrophobic interfaces.
- Fujii, Shota,McCarthy, Thomas J.
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- Mechanistic analysis of an extracellular signal–Regulated kinase 2–Interacting compound that inhibits mutant BRAF-expressing melanoma cells by inducing oxidative stress
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Constitutively active extracellular signal–regulated kinase (ERK) 1/2 signaling promotes cancer cell proliferation and survival. We previously described a class of compounds containing a 1,1-dioxido-2,5-dihydrothiophen-3-yl 4-benzenesulfonate scaffold that targeted ERK2 substrate docking sites and selectively inhibited ERK1/2-dependent functions, including activator protein-1–mediated transcription and growth of cancer cells containing active ERK1/2 due to mutations in Ras G-proteins or BRAF, Proto-oncogene B-RAF (Rapidly Acclerated Fibrosarcoma) kinase. The current study identified chemical features required for biologic activity and global effects on gene and protein levels in A375 melanoma cells containing mutant BRAF (V600E). Saturation transfer difference-NMR and mass spectrometry analyses revealed interactions between a lead compound (SF-3-030) and ERK2, including the formation of a covalent adduct on cysteine 252 that is located near the docking site for ERK/FXF (DEF) motif for substrate recruitment. Cells treated with SF-3-030 showed rapid changes in immediate early gene levels, including DEF motif–containing ERK1/2 substrates in the Fos family. Analysis of transcriptome and proteome changes showed that the SF-3-030 effects overlapped with ATP-competitive or catalytic site inhibitors of MAPK/ERK Kinase 1/2 (MEK1/2) or ERK1/2. Like other ERK1/2 pathway inhibitors, SF-3-030 induced reactive oxygen species (ROS) and genes associated with oxidative stress, including nuclear factor erythroid 2–related factor 2 (NRF2). Whereas the addition of the ROS inhibitor N-acetyl cysteine reversed SF-3-030–induced ROS and inhibition of A375 cell proliferation, the addition of NRF2 inhibitors has little effect on cell proliferation. These studies provide mechanistic information on a novel chemical scaffold that selectively regulates ERK1/2-targeted transcription factors and inhibits the proliferation of A375 melanoma cells through a ROS-dependent mechanism.
- Martinez, Ramon,Huang, Weiliang,Samadani, Ramin,Mackowiak, Bryan,Centola, Garrick,Chen, Lijia,Conlon, Ivie L.,Hom, Kellie,Kane, Maureen A.,Fletcher, Steven,Shapiro, Paul
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supporting information
p. 84 - 97
(2021/01/01)
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- Erbium-Catalyzed Regioselective Isomerization-Cobalt-Catalyzed Transfer Hydrogenation Sequence for the Synthesis of Anti-Markovnikov Alcohols from Epoxides under Mild Conditions
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Herein, we report an efficient isomerization-transfer hydrogenation reaction sequence based on a cobalt pincer catalyst (1 mol %), which allows the synthesis of a series of anti-Markovnikov alcohols from terminal and internal epoxides under mild reaction conditions (≤55 °C, 8 h) at low catalyst loading. The reaction proceeds by Lewis acid (3 mol % Er(OTf)3)-catalyzed epoxide isomerization and subsequent cobalt-catalyzed transfer hydrogenation using ammonia borane as the hydrogen source. The general applicability of this methodology is highlighted by the synthesis of 43 alcohols from epoxides. A variety of terminal (23 examples) and 1,2-disubstituted internal epoxides (14 examples) bearing different functional groups are converted to the desired anti-Markovnikov alcohols in excellent selectivity and yields of up to 98%. For selected examples, it is shown that the reaction can be performed on a preparative scale up to 50 mmol. Notably, the isomerization step proceeds via the most stable carbocation. Thus, the regiochemistry is controlled by stereoelectronic effects. As a result, in some cases, rearrangement of the carbon framework is observed when tri-and tetra-substituted epoxides (6 examples) are converted. A variety of functional groups are tolerated under the reaction conditions even though aldehydes and ketones are also reduced to the respective alcohols under the reaction conditions. Mechanistic studies and control experiments were used to investigate the role of the Lewis acid in the reaction. Besides acting as the catalyst for the epoxide isomerization, the Lewis acid was found to facilitate the dehydrogenation of the hydrogen donor, which enhances the rate of the transfer hydrogenation step. These experiments additionally indicate the direct transfer of hydrogen from the amine borane in the reduction step.
- Liu, Xin,Longwitz, Lars,Spiegelberg, Brian,T?njes, Jan,Beweries, Torsten,Werner, Thomas
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p. 13659 - 13667
(2020/11/30)
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- Organic electrolytic solution and lithium battery using the same
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Provided is an organic electrolyte solution that includes a lithium salt, an organic solvent, and a sulfonate ester-based compound represented by Formula 1: [in-line-formulae]R2—O—S(═O)2—R1??[/in-line-formulae]wherein, in Formula 1, R1 may be a C1-C20 alkyl group that is unsubstituted or substituted with halogen, a C5-C20 cycloalkyl group that is unsubstituted or substituted with halogen, a C6-C40 aryl group that is unsubstituted or substituted with halogen, or a C2-C40 heteroaryl group that is unsubstituted or substituted with halogen, and R2 may be a substituted or unsubstituted cyclic sulfone group.
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Page/Page column 19
(2019/06/22)
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- The solvent for the electrolyte, and the electrolyte for the electrochemical device.
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PROBLEM TO BE SOLVED: To provide a solvent for an electrolytic solution including a sulfone compound and having a relatively low melting point, excellent thermal stability and higher decomposition voltage characteristics; a lithium primary cell, a lithium secondary cell, a lithium ion cell, a fuel cell, and a solar cell using the solvent for an electrolytic solution; and an electrolytic solution for an electrochemical device such as an electric double layer capacitor.SOLUTION: A solvent for an electrolytic solution includes a sulfone compound represented by formula (1). In the formula (1); R, Rand Rare each independently a 1-4C alkyl group, a phenyl group or an allyl group.
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Paragraph 0044
(2017/06/02)
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- Pyrano, piperidino, and thiopyrano compounds and methods of use
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The present invention provides novel compounds of formula I which may be useful in hyperpolarizing cell membranes, opening potassium channels, relaxing smooth muscle cells, and inhibiting bladder contractions.
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- Pyrano, piperidino, and thiopyrano compounds and methods of use
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The present invention provides novel compounds of formula I which may be useful in hyperpolarizing cell membranes, opening potassium channels, relaxing smooth muscle cells, and inhibiting bladder contractions.
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- Synthesis of Novel Cyclic Sulfone Dihydropyridines Facilitated by a Selective Ethyl Diazoacetate Ring Expansion
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A series of novel cyclic sulfone dihydropyridines with five to nine membered rings have been synthesized.Anomalous intermediates isolated from the Hantzch condensation were found to vary depending on the sulfone ring size and aromatic substitution.Tin tetrachloride has been shown to be a superior Lewis acid catalyst for ethyl diazoacetate ring expansion of the requisite β-keto cyclic sulfone precursors.
- Dodd, John H.,Schwender, Charles F.,Gray-Nunez, Yolanda
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p. 1453 - 1456
(2007/10/02)
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- HYDROLYSIS OF CARBAMATES AND CARBONATES OF 3-HYDROXYTHIOLANE 1,1-DIOXIDE
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Alkylcarbamates of 3-hydroxy-thiolane 1,1-dioxide are hydrolyzed in the presence of bases to give alkyl(1,1-dioxo-3-thiolanyl)amines and 2-thiolene 1,1-dioxide (I).Aryl esters undergo hydrolysis to give sulfone I and 3-hydroxythiolane 1,1-dioxide (II).The corresponding alkyl- and arylcarbonates also form sulfone I and a very small amount of hydroxy derivative II under these conditions.
- Parkhomenko, P. I.,Rybakova, M. V.,Bezmenova, T. E.,Zaika, T. D.
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p. 1122 - 1124
(2007/10/02)
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