- Additive, electrolyte for rechargeable lithium battery, and rechargeable lithium battery
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An additive, an electrolyte for a rechargeable lithium battery, and a rechargeable lithium battery, the additive being represented by Chemical Formula 1.
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Paragraph 0131-0135
(2021/01/29)
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- Proteasome inhibition by new dual warhead containing peptido vinyl sulfonyl fluorides
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The success of inhibition of the proteasome by formation of covalent bonds is a major victory over the long held-view that this would lead to binding the wrong targets and undoubtedly lead to toxicity. Great challenges are now found in uncovering ensembles of new moieties capable of forming long lasting ties. We have introduced peptido sulfonyl fluorides for this purpose. Tuning the reactivity of this electrophilic trap may be crucial for modulating the biological action. Here we describe incorporation of a vinyl moiety into a peptido sulfonyl fluoride backbone, which should lead to a combined attack of the proteasome active site threonine on the double bond and the sulfonyl fluoride. Although this led to strong proteasome inhibitors, in vitro studies did not unambiguously demonstrate the formation of the proposed seven-membered ring structure. Possibly, formation of a seven-membered covalent adduct with the proteosomal active site threonine can only be achieved within the context of the enzyme. Nevertheless, this dual warhead concept may provide exclusive possibilities for duration and selectivity of proteasome inhibition.
- Brouwer, Arwin J.,Herrero álvarez, Natalia,Ciaffoni, Adriano,van de Langemheen, Helmus,Liskamp, Rob M.J.
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p. 3429 - 3435
(2016/07/21)
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- Exploiting 1,2,3-Triazolium Ionic Liquids for Synthesis of Tryptanthrin and Chemoselective Extraction of Copper(II) Ions and Histidine-Containing Peptides
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Based on a common structural core of 4,5,6,7-Tetrahydro[1,2,3]triazolo[1,5-A]pyridine, a number of bicyclic triazolium ionic liquids 1-3 were designed and successfully prepared. In our hands, this optimized synthesis of ionic liquids 1 and 2 requires no chromatographic separation. Also in this work, ionic liquids 1, 2 were shown to be efficient ionic solvents for fast synthesis of tryptanthrin natural product. Furthermore, a new affinity ionic liquid 3 was tailor-synthesized and displayed its effectiveness in chemoselective extraction of both Cu(II) ions and, for the first time, histidine-containing peptides.
- Li, Hsin-Yi,Chen, Chien-Yuan,Cheng, Hui-Ting,Chu, Yen-Ho
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- SNAAP sulfonimidate alkylating agent for acids, alcohols, and phenols 1
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Stable, crystalline ethyl N-tert-butyl-4-nitrobenzenesulfonimidate has been prepared in high yield by direct O-ethylation of N-tert-butyl-4- nitrobenzenesulfonamide with iodoethane and silver(I) oxide in dichloromethane. This sulfonimidate directly ethylates various acids to esters; the stronger the acid, the faster it alkylates and in higher yield. It readily ethylates alcohols and phenols to ethers at room temperature in the presence of tetrafluoroboric acid catalyst without molecular rearrangements or racemization. We have defined these reactions as SNAAP alkylations: [substitution, nucleophilic of acids, alcohols and phenols]. The hard sulfonimidate alkylating agent is chemoselective, preferring oxygen > nitrogen > sulfur. The sulfonamide byproduct of alkylation is readily recycled to the sulfonimidate. Georg Thieme Verlag Stuttgart . New York.
- Maricich, Tom J.,Allan, Matthew J.,Kislin, Brett S.,Chen, Andrea I-T.,Meng, Fan-Chun,Bradford, Christine,Kuan, Nai-Chia,Wood, Jeremy,Aisagbonhi, Omonigho,Poste, Alethea,Wride, Dustin,Kim, Sylvia,Santos, Therese,Fimbres, Michael,Choi, Dianne,Elia, Haydi,Kaladjian, Joseph,Abou-Zahr, Ali,Mejia, Arturo
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p. 3361 - 3368
(2014/01/06)
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- Physicochemical characterization of new sulfonate and sulfate ammonium ionic liquids
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In this work we describe the synthesis and thermal properties of nine new salts derived from ammonium that incorporate alkanesulfonate and alkanesulfate anions. Their structures were confirmed by 1H and 13C NMR and HRMS-ESI. Their thermal properties were determined by differential scanning calorimetry (DSC). Three of the synthesized salts have been shown to be room temperature ionic liquids: N-ethyl-N-(2-hydroxyethyl)-N,N-dimethylammonium butanesulfonate, N-ethyl-N,N-dimethylbutylammonium ethylsulfate, and N-ethyl-N-(2-hydroxyethyl)-N,N-dimethylammonium ethylsulfate. Experimental densities, speeds of sound, dynamic viscosities, and refractive indices of these three ionic liquids were measured at T = 298.15 K.
- Mahrova, Maria,Vilas, Miguel,Dominguez, Angeles,Gomez, Elena,Calvar, Noelia,Tojo, Emilia
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scheme or table
p. 241 - 248
(2012/05/20)
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- HETEROCYCLIC NON-PEPTIDE GNRH ANTAGONISTS
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A compound of formula (I): wherein either B is absent and A and Z are the same or different and are each hydrogen, halogen, alkyl, hydroxy, alkoxy,-CN,-C(Rc)2OH,-N(Rd)C(=X)Rc,-C(=X)N(Rc)(Rd),-S(O)m-Rc,-N(Rc)(Rd)S(O)2,-S(O)2N(R c)(Rd),-N(Re)2, aryl optionally substituted with Ra or-O-aryl optionally substituted with Ra; or B is present and is-(CH2)n-,-C(Rb)2-or-O-, or B taken together with A or Z can be-C=C(Rb)-,-C(Rb)=C-,-CH2-CH(R b)-or-CH(Rb)-CH2-; D is-O-or-S(O) m,-; E is a bond or is-(CH2)n-,-N(R d)-,-(CH2)nN(Rd)-or-N(R d)(CH2)n-; F is-C(=X)-; G is-(CH2 )n-,-N(Rd)-,-(CH2)nN(R d)-or-N(Rd)(CH2)n; J is a bond,-O-,-N(RC)C(=X)-,-C(=X)N(Rc)-,-S(O)m,-,-N(Rc)S(O)m-,-S(O)nN(Rc)-,-N(Re)-or-N(Rg)(Rh); K is a bond, alkylene, cycloalkylene, cycloalkenylene, arylene, heterocycloalkylene, heterocycloalkylene or heteroarylene; and L is hydrogen or a terminal group; has therapeutic utility.
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Page/Page column 72
(2008/06/13)
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- PROCESS FOR PRODUCING 3-AMINO-2-HYDROXYPROPIONIC ACID DERIVATIVES
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The present invention provides a process for preparing 3-amino-2-hydroxypropionic acid derivatives (1) which does not use dangerous reagents, is economically advantageous, and is suitable for an industrial production, which process comprises:treating N-protected-3-amino-2-hydroxypropionic acid derivatives (2) having a steric configuration at 2-position carbon reverse to that of derivatives (1) with a leaving group-introducing agent to convert into N-protected-3-aminopropionic acid derivatives (3),then treating the derivatives with a basic substance to convert into substituted-3-amino-2-hydroxypropionic acid derivatives (4) having an inverted steric configuration at 2-position carbon,and then converting the derivatives into 3-amino-2-hydroxypropionic acid derivatives (1).
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- Process for preparation of oxyglutaric acid ester derivatives
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A process for preparing an oxyglutaric acid ester derivative of the formula: STR1 in which each of R1 and R2 is C1-5 alkoxy, C1-7 aralkyloxy, C7-9 halogenated aralkyloxy or phenyl, R4 is a hydroxyl-protecting group, and R5 is C1-10 alkyl which may have a substituent, comprises the steps of reacting a methyl phosphonate derivative or methyl phosphine oxide derivative with an oxyglutaric acid mono-ester to give a reaction product which comprises an oxyglutaric acid derivative having a phosphorus-containing group and a pentenedioic acid mono-ester (by-product), removing the pendenedioic acid mono-ester from the reaction product to isolate the oxyglutaric acid derivative, and converting the isolated oxyglutaric acid derivative into the oxyglutaric acid ester derivative. A process for obtaining an optically active oxyglutaric acid ester derivative is also disclosed.
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- Scavenger assisted combinatorial process for preparing libraries of tertiary amine compounds
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This invention relates to a novel solution phase process for the preparation of tertiary amine combinatorial libraries. These libraries have utility for drug discovery and are used to form wellplate components of novel assay kits.
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- Facile esterification of sulfonic acids and carboxylic acids with triethylorthoacetate
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Triethylorthoacetate was found to be surprisingly more effective than triethylorthoformate in the esterification of sulfonic acids and carboxylic acids. Using this reagent, esters of sulfonic and carboxylic acids are prepared in high yields.
- Trujillo, John I.,Gopalan, Aravamudan S.
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p. 7355 - 7358
(2007/10/02)
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- Potassium Cryptate Catalysis in the Elimination Reaction of a Sulfonate Ester
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In the reaction of p-nitrophenyl methanesulfonate (1) with alkali-metal ethoxides, it is found that potassium ethoxide in the presence of excess 2.2.2 cryptand is more reactive than potassium ethoxide alone or in the presence of excess 18-crown-6.An upward curvature in the plot of kobs vs o in the presence of 2.2.2 cryptand is interpreted as arising from parallel reactions of free ethoxide ion and the ion pair of ethoxide ion with cryptated potassium ion ( 2.2.2>+EtO-), the latter being more reactive than the former.It is shown that the ester reacts predominantly by an E1cb-type elimination mechanism, and the potassium cryptate appears to stabilize the transition state for leaving-group departure by electrostatic interactions through an 18-membered ring "window" in the cryptand.
- Pregel, Marko J.,Buncel, Erwin
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- Fragmentation-Rearrangement of 2-Acyloxyalkylphosphonates - a Novel Route to Alkyl Metaphosphate Extrusion
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Thermolysis of dialkyl 2-acyloxyalkylphosphonates, resulting in the fragmentation to an alkene, ester and alkyl metaphosphate, represents the first example of a reaction in which alkyl group migration has to occur before the metaphosphate species can be extruded from the system.
- Jongh, Connie P. de,Modro, Tomasz A.
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p. 1003 - 1004
(2007/10/02)
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- Metal-Ion Catalysis in Nucleophilic Displacement Reactions at Carbon, Phosphorus, and Sulfur Centers. 5. Alkali-Metal Ion Catalysis and Inhibition in the Reaction of p-(Trifluoromethyl)phenyl Methanesulfonate with Ethoxide Ion
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The reactions of alkali-metal ethoxides with p-(trifluoromethyl)phenyl methanesulfonate (1) in anhydrous ethanol at 25 deg C, yielding p-(trifluoromethyl)phenolate ion and ethyl methanesulfonate, have been investigated in order to reveal the effects of alkali-metal ions on reaction rates.Kinetic spectrophotometric studies of the nucleophilic displacement reaction of 1 with alkali-metal ethoxides in the absence and presence of complexing agents showed that the observed rate constants increase in the order LiOEt - + inhibits the reaction of ethoxide ion, while the other alkali-metal ions all act as catalysts.The kinetic data are analyzed in terms of parallel reactions of free ethoxide ion and alkali-metal ethoxide ion pairs, and rate constants for the reactions of these species are calculated.Association constants governing the interaction of the various metal ions with the transition state for the reaction of ethoxide ion with 1 are derived from the kinetic data and compared to association constants for interaction of metal ions with ethoxide ion in the ground state.The trend in the sizes of the association constants for the methanesulfonate transition state, Li+ + + +, is believed to arise from ion pairing of the transition state with solvated metal ions.A similar ordering is observed for the transition state in the reaction of p-nitrophenyl benzenesulfonate (2) with alkali metal ethoxides, while an inverted ordering is seen for the transition state for the reaction of ethoxides with p-nitrophenyl diphenylphosphinate (3).These results are interpreted in terms of the extent of charge delocalization in the transition states and its effect on interactions with bare or solvated metal ions.
- Pregel, Marko J.,Buncel, Erwin
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p. 5583 - 5588
(2007/10/02)
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- Nucleophilic Displacement Reactions at Carbon, Phosphorus and Sulphur Centres: Reaction of Aryl Methanesulphonates with Ethoxide; Change in Mechanism with Change in Leaving Group
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The reactions of ethoxide ion with aryl methanesulphonate esters (1a-c) in anhydrous ethanol at 25 deg C have been investigated in order to determine the effect of leaving group nucleofugality on the balance between substitution and elimination pathways.The reactions of p-nitrophenyl-(1a), m-nitrophenyl-(1b) and p-trifluoromethylphenyl-(1c) methanesulphonates have been examined by means of kinetic studies, sulphene trapping experiments, and deuterium exchange experiments.It is concluded that the para-nitro-substituted ester reacts predominantly by an E1cb-type elimination mechanism via a sulphene intermediate, with nucleophilic substitution as a minor concurrent pathway.Conversely, the meta-nitro-substituted ester reacts predominantly by substitution, with elimination as a minor concurrent pathway.The evidence available indicates that the para-trifluoromethyl-substituted ester reacts solely by substitution.Thus, the mechanism of reaction changes from nucleophilic substitution to elimination-addition as leaving group nucleofugality increases.
- Pregel, Marko J.,Buncel, Erwin
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p. 307 - 311
(2007/10/02)
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- Benzophenone Dicarboxylic Acid Antagonists of Leukotriene B4. 2. Structure-Activity Relationships of the Lipophilic Side Chain
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A series of lipophilic benzophenone dicarboxylic acid derivatives were found to inhibit the binding of the potent chemotoxin leukotriene B4 (LTB4) to its receptor on intact human neutrophils.Activity at the LTB4 receptor was determined by using a 3H>LTB4-binding assay.The structure-activity relationship for the lipophilic side chain was systematically investigated.Compounds with n-alkyl side chains of varying lengths were prepared and tested.Best inhibition of 3H>LTB4 binding was observed with the n-decyl derivative.Analogues with alkyl chains terminated with an aromatic ring showed improved activity.The 6-phenylhexyl side chain was optimal.Substitution on the terminal aromatic ring was also evaluated.Methoxyl, methylsulfinyl, and methyl substituents greatly enhanced the activity of the compound.For a given substituent, the para isomer had the best activity.Thus the nature of the lipophilic side chain can greatly influence the ability of the compounds to inhibit the binding of LTB4 to its receptor on intact human neutrophils.The most active compound from this series, 84 (LY223982), bound to the LTB4 receptor with the affinity approaching that of the agonist.
- Gapinski, D. Mark,Mallett, Barbara E.,Froelich, Larry L.,Jackson, William T.
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p. 2807 - 2813
(2007/10/02)
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- Reaction of Carboxylic Acid Esters with p-Toluenesulfonic Acid
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The reaction of carboxylic acid esters with an excess of p-toluenesulfonic acid gave the corresponding p-toluenesulfonates.The mechanism of the transesterification is discussed.
- Nitta, Yoshihiro,Arakawa, Yasushi
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p. 1380 - 1386
(2007/10/02)
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- A NEW METHOD FOR THE ESTERIFICATION OF SULPHONIC ACIDS
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Sulphonic acids can be smoothly converted to their methyl and ethyl esters by reaction with trimethyl and triethyl orthoformate, respectively
- Padmapriya, A. A.,Just, G.,Lewis, N. G.
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p. 1057 - 1062
(2007/10/02)
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