- Synthesis and investigation of sulfonated poly(: P -phenylene)-based ionomers with precisely controlled ion exchange capacity for use as polymer electrolyte membranes
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To achieve precise control of sulfonated polymer structures, a series of poly(p-phenylene)-based ionomers with well-controlled ion exchange capacities (IECs) were synthesised via a three-step technique: (1) preceding sulfonation of the monomer with a protecting group, (2) nickel(0) catalysed coupling polymerisation, and (3) cleavage of the protecting group of the polymers. 2,2-Dimethylpropyl-4-[4-(2,5-dichlorobenzoyl)phenoxy]benzenesulfonate (NS-DPBP) was synthesised as the preceding sulfonated monomer by treatment with chlorosulfuric acid and neopentyl alcohol. NS-DPBP was readily soluble in various organic solvents and stable during the nickel(0) catalysed coupling reaction. Sulfonated poly(4-phenoxybenzoyl-1,4-phenylene) (S-PPBP) homopolymer and seven types of random copolymers (S-PPBP-co-PPBP) with different IECs were obtained by varying the stoichiometry of NS-DPBP. The IECs and weight average molecular weights (Mws) of ionomers were in the range of 0.41-2.84 meq. g-1 and 143 000-465 000 g mol-1, respectively. The water uptake, proton conductivities, and water diffusion properties of ionomers exhibited a strong IEC dependence. Upon increasing the IEC of S-PPBP-co-PPBPs from 0.86 to 2.40 meq. g-1, the conductivities increased from 6.9 × 10-6 S cm-1 to 1.8 × 10-1 S cm-1 at 90% RH. S-PPBP and S-PPBP-co-PPBP (4 : 1) with IEC values >2.40 meq. g-1 exhibited fast water diffusion (1.6 × 10-11 to 8.0 × 10-10 m2 s-1), and were comparable to commercial perfluorosulfuric acid polymers. When fully hydrated, the maximum power density and the limiting current density of membrane electrode assemblies (MEAs) prepared with S-PPBP-co-PPBP (4 : 1) were 712 mW cm-2 and 1840 mA cm-2, respectively.
- Rikukawa, Masahiro,Takahashi, Satoshi,Takeoka, Yuko,Yoshida-Hirahara, Miru,Yoshizawa-Fujita, Masahiro
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p. 12810 - 12822
(2020/04/22)
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- A substituted boric acid ester compound preparation method and its crystalline form (by machine translation)
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The invention of the formula (A) compound and its crystalline form, its preparation method, the invention also discloses the formula (A) compound of the pharmaceutical composition, and the use of said compounds for treating with a proteasome related diseases. (by machine translation)
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Paragraph 0190; 0192; 0193; 0194; 0195
(2019/02/04)
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- Conformations, equilibrium thermodynamics and rotational barriers of secondary thiobenzanilides
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The article deals with conformational behaviour of 2-methoxy-2′-hydroxythiobenzanilides. The CS-NH group of these compounds preferentially adopts the Z-conformation. Entropy favours the Z-conformer over the E-conformer, whereas enthalpy slightly favours the E-conformer over the Z-conformer. The rotational barrier about the CS-NH bond was determined to be (81.5±0.4) kJ/mol. No significant rotational barrier was found on the Ar-CS and Ar-NH bonds. All experimental outcomes are compared with the results of quantum-chemical calculations.
- Kozic, Ján,Novák, Zdeněk,?ímal, Václav,Profant, Václav,Kune?, Ji?í,Vin?ová, Jarmila
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p. 2072 - 2083
(2016/04/09)
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- Design, synthesis and fungicidal activity of N-substituted benzoyl-1,2,3,4-tetrahydroquinolyl-1-carboxamide
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To find a new lead compound with high biological activity, a series of N-substituted benzoyl-1,2,3,4-tetrahydroquinolyl-1-carboxamide were designed using linking active substructures method. The target compounds were synthesized from substituted benzoic acid by four steps and their structures were confirmed by 1H NMR, IR spectrum and elemental analysis. The in vitro bioassay results indicated that some target compounds exhibited excellent fungicidal activities, and the position of the substituents played an important role in fungicidal activities. Especially, compound 5n, exhibited better fungicidal activities than the commercial fungicide flutolanil against two tested fungi Valsa Mali and Sclerotinia sclerotiorum, with EC50 values of 3.44 and 2.63 mg/L, respectively. And it also displayed good in vivo fungicidal activity against S. sclerotiorum with the EC50 value of 29.52 mg/L.
- Lei, Peng,Xu, Yan,Du, Juan,Yang, Xin-Ling,Yuan, Hui-Zhu,Xu, Gao-Fei,Ling, Yun
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supporting information
p. 2544 - 2546
(2016/07/07)
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- Anion conductive aromatic copolymers from dimethylaminomethylated monomers: Synthesis, properties, and applications in alkaline fuel cells
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A novel series of anion conductive aromatic copolymers were synthesized from preaminated monomers (2,5-, 3,5-, or 2,4-dichloro-N,N-dimethylbenzylamine), and their properties were investigated for alkaline fuel cell applications. The targeted copolymers (QPE-bl-11a, -11b, and -11c) were synthesized via nickel-mediated Ullmann coupling polymerization, followed by quaternization and ion exchange reactions. Unlike the conventional method involving chloromethylation or bromination, this method provided copolymers with well-defined chemical structure. The hydrophilic components of the copolymers were composed of chemically stable phenylene main chain modified with high-density ammonium groups. Oligo(arylene ether sulfone ketone)s were employed as a hydrophobic block. QPE-bl-11a gave tough and bendable membranes by solution casting. The obtained membrane with the highest ion exchange capacity value (IEC = 2.47 mequiv g-1) showed high hydroxide ion conductivity (130 mS cm-1) in water at 80 °C. The QPE-bl-11a membrane showed reasonable alkaline stability in 1 M KOH aqueous solution for 1000 h at 60 °C. A platinum-free fuel cell was successfully operated with hydrazine as a fuel, the QPE-bl-11a as a membrane, and an electrode binder. The maximum power density of 380 mW cm-2 was achieved at a current density of 1020 mA cm-2 with O2.
- Akiyama, Ryo,Yokota, Naoki,Nishino, Eriko,Asazawa, Koichiro,Miyatake, Kenji
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p. 4480 - 4489
(2016/07/07)
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- Regioselective synthesis of 1-substituted indazole-3-carboxylic acids
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In this article, we study the synthesis of 1-substituted indazole-3-carboxylic acids from 2-halobenzoic acids.
- Veerareddy, Arava,Gogireddy, Surendrareddy,Dubey
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p. 1311 - 1321
(2015/04/27)
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- Polymerization of novel methacrylated anthraquinone dyes
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A new series of polymerizable methacrylated anthraquinone dyes has been synthesized by nucleophilic aromatic substitution reactions and subsequent methacrylation. Thereby, green 5,8-bis(4-(2-methacryloxyethyl)phenylamino)-1,4- dihydroxyanthraquinone (2), blue 1,4-bis(4-((2-methacryloxyethyl)oxy) phenylamino)anthraquinone (6) and red 1-((2-methacryloxy-1,1- dimethylethyl)amino)anthraquinone (12), as well as 1-((1,3-dimethacryloxy-2- methylpropan-2-yl)amino)anthraquinone (15) were obtained. By mixing of these brilliant dyes in different ratios and concentrations, a broad color spectrum can be generated. After methacrylation, the monomeric dyes can be covalently emplaced into several copolymers. Due to two polymerizable functionalities, they can act as cross-linking agents. Thus, diffusion out of the polymer can be avoided, which increases the physiological compatibility and makes the dyes promising compounds for medical applications, such as iris implants.
- Dollendorf, Christian,Kreth, Susanne Katharina,Choi, Soo Whan,Ritter, Helmut
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supporting information
p. 453 - 459
(2013/04/23)
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- One-pot preparation of 2,5-dichloro-4'-phenyloxybenzophenone
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Friedel-Crafts-type acylation of phenyl ether with 2,5-dichlorobenzoic acid could be accomplished in a single step using trifluoroacetic anhydride and phosphoric acid. The method gave a greater yield (78%) than the conventional two-step process (71%) of acid chloride generation followed by aluminum trichloride-mediated acylation. Copyright Taylor & Francis Group, LLC.
- Davis, Matthew C.,Groshens, Thomas J.
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experimental part
p. 255 - 261
(2011/03/20)
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- Synthesis and gas permeability of ester substituted poly(p-phenylene)s
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Polymerizations of various ester substituted 2,5-dichlorobenzoates [substituent: linear alkyl groups (1a-f), branched alkyl groups (1g-l), cyclohexyl groups (1m-o), phenyl groups (1p-r), and oxyethylene units (1s-v)] were investigated with Ni-catalyzed/Zn-mediated system in 1-methyl-2-pyrrolidone (NMP) at 80 °C. Most of monomers bearing linear and branched alkyl groups successfully polymerized to give relatively high-molecular-weight polymers (Mn = 10,000-20,800). However, the molecular weight of the polymer having eicocyl groups was low because of steric hindrance of long alkyl chain. The polymerizations of cyclohexyl 2,5-dichlorobenzoate and phenyl 2,5-dichlorobenzoate produced low-molecular-weight polymers, while the polymerizations of monomers with alkyl cyclohexyl and alkyl phenyl groups proceeded to afford polymers with relatively high-molecular-weights. The polymers possessing oxyethylene units were obtained, but the molecular weights were low when the oxyethylene chains were long. The gas permeability of membranes of poly(p-phenylene)s with alkyl chains increased as increasing the length of alkyl chain. The membranes of poly(p-phenylene)s with phenyl groups and oxyethylene units exhibited high densities and relatively low gas permeability. However, the CO2/N2 separation factor of membrane of poly(p-phenylene) having oxyethylene units was as large as 73.6.
- Sakaguchi, Toshikazu,Tominaga, Shinichi,Hashimoto, Tamotsu
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experimental part
p. 2163 - 2169
(2012/05/05)
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- Synthesis of (2-chlorophenyl)(phenyl)methanones and 2-(2-chlorophenyl)-1- phenylethanones by Friedel-Crafts acylation of 2-chlorobenzoic acids and 2-(2-chlorophenyl)acetic acids using microwave heating
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Several 2-(2-chlorophenyl)-1-phenylethanones and (2-chlorophenyl)(phenyl) methanones were prepared by the Friedel-Crafts acylation reaction of 2-(2-chlorophenyl) acetic acids and 2-chlorocarboxylic acids, respectively, in the presence of cyanuric chloride, pyridine, and AlCl3 or FeCl 3 using microwave heating. The yields of the ketones were significantly higher than those obtained using conventional heating. In addition, similar reactions carried out with the less inexpensive and less toxic FeCl3 gave titled ketones in comparable yields. Interestingly, the FeCl3 catalyzed reactions gave pure ketones (no chromatographic purification required), whereas the AlCl3 catalyzed reaction gave impure product that required chromatographic purification.
- Mahdi, Jasia,Ankati, Haribabu,Gregory, Jill,Tenner, Brian,Biehl, Edward R.
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experimental part
p. 2594 - 2596
(2011/06/21)
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- Considerations of polymerization method and molecular weight for proton-conducting poly(p-phenylene) derivatives
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Ni(0)-catalyzed coupling polymerization of 2,5-dichloro-4′- phenoxybenzophenone was investigated by varying the ligand and coligand, temperature, reaction time, and solvent. The weight-average molecular weight (Mw) of poly(4-phenoxybenzoyl-1,4-phenylene)s (PPBPs) could be controlled by the polymerization conditions and reached a maximum of 4.4 × 105 g mol-1. Sulfonated PPBPs (S-PPBPs) with various Mws were prepared with sulfuric acid to study the effect of molecular weight on the chemical and electrical properties of PPBP-based electrolytes. The strong molecular interactions in S-PPBP provided an ion exchange capacity of 2.9 meq g-1 without loss of high mechanical properties. High molecular weight S-PPBPs had more desirable properties for fuel cell applications. While the swelling ratios and hydration numbers of S-PPBPs decreased with increasing molecular weight, the mechanical strength, proton conductivity, and fuel cell performance increased. S-PPBP also showed anisotropic behavior in the swelling and proton conductivity; such behavior is caused by the rigid-rod nature and the liquid-crystal structure.
- Tonozuka, Isao,Yoshida, Miru,Kaneko, Keiichi,Takeoka, Yuko,Rikukawa, Masahiro
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experimental part
p. 6020 - 6028
(2012/04/10)
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- Synthesis and properties of sulfonated copoly(p-phenylene)s containing aliphatic alkyl pendant for fuel cell applications
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A series of novel copoly(p-phenylene)s (PPs) containing an alkyl pendant were successfully synthesized via Ni(0)-catalyzed coupling polymerization. Sulfonated copolymers (SPPs) were achieved by postsulfonation from concentrated H2SO4. SPPs showed good solubility in polar aprotic solvents and gave flexible, tough, and transparent free-standing films by solvent casting. The ion exchange capacities (IECs) of the membranes ranged from 2.50 to 2.65?meq/g. All SPP membranes displayed proton conductivity similar to or higher than that of Nafion, especially at high relative humidity (>70% RH) (SPP-1: 0.271 Scm-1, SPP-2: 0.284 Scm-1, SPP-3: 0.212?S?cm-1, Nafion: 0.127 Scm-1; at 80?°C and 95% RH). They also exhibited acceptable water uptake in the range of 52-56?vol% at 80?°C with little dimensional change. The gas permeability of the SPP membranes was much lower than that of Nafion 112. Therefore, these materials are promising for fuel cell application.
- Seesukphronrarak, Surasak,Ohira, Kayo,Kidena, Koh,Takimoto, Naohiko,Kuroda, Carlos Seiti,Ohira, Akihiro
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experimental part
p. 623 - 631
(2011/02/16)
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- NOVEL COMPOUNDS AS CANNABINOID RECEPTOR LIGANDS AND USES THEREOF
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The present invention relates to compounds of formula (I), or pharmaceutical salts, prodrugs, salts of prodrugs, or combinations thereof, wherein R1, R2, R3, and L1 are defined in the specfication, compositions comprising such compounds, and methods of treating conditions and disorders using such compounds and compositions. The present invention also relates to compounds of formula (II), or pharmaceutical salts, prodrugs, salts of prodrugs, or combinations thereof, wherein R1a, R2a and (Rx)n are as defined in the specification, compositions comprising such compounds, and methods of treating conditions and disorders using such compounds and compositions.
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Page/Page column 38
(2008/06/13)
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- Accelerating effect of meta substituents in the ester-mediated nucleophilic aromatic substitution reaction
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The ester-mediated nucleophilic aromatic substitution (SNAr) reaction of 2-methoxybenzoic ester 1 with Grignard reagents 11 is greatly accelerated by introduction of a methoxy or halo substituent at the 3-position of the benzoate ring (7-10). The substituent effects of these groups at the 3-position are compared with those at the 5-position to suggest that the activation mechanism of the methoxy substituent is different from that of the halo substituent; the ligating ability of the 3-methoxy group plays a crucial role in enhancing the reactivity of the 2-methoxy moiety, while the electron-withdrawing ability is more important in the case of the halo groups. It has also been found that introduction of an additional methoxy substituent at the meta-position (33, 34) enables the SNAr methoxy-displacement reaction even at the para-position to the ester activator. The accelerating effect of the 3-bromo substituent is advantageously utilized for regioselective allylation of 3-bromo-2,6-dimethoxybenzoic ester 55 at the 2-position to provide an easy access to a multisubstituted naphthol 59, which is a key compound for the syntheses of michellamines A-C and the related naphthylisoquinoline alkaloids.
- Hattori, Tetsutaro,Takeda, Ayanobu,Suzuki, Kenji,Koike, Nobuyuki,Koshiishi, Eiji,Miyano, Sotaro
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p. 3661 - 3671
(2007/10/03)
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