- Magnesiation of Aryl Fluorides Catalyzed by a Rhodium-Aluminum Complex
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We report the magnesiation of aryl fluorides catalyzed by an Al-Rh heterobimetallic complex. We show that the complex is highly reactive to cleave the C-F bonds across the polarized Al-Rh bond under mild conditions. The reaction allows the use of an easy-to-handle magnesium powder to generate a range of arylmagnesium reagents from aryl fluorides, which are conventionally inert to such metalation compared with other aryl halides.
- Fujii, Ikuya,Semba, Kazuhiko,Li, Qiao-Zhi,Sakaki, Shigeyoshi,Nakao, Yoshiaki
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supporting information
p. 11647 - 11652
(2020/08/06)
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- Synchronous reactor based on reaction and separation using air oxidation of substituted toluene method for producing substituted phenyl formic acid (by machine translation)
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The invention discloses a synchronous reaction and separation-based reactor utilizing air oxidizing substituted toluene method for producing substituted phenyl of formic acid, the reaction separation synchronous reactor comprises a bubbling gravity reaction tower or stirring the reaction tower and constant temperature sedimentation tower; the upper part of the gas phase area including reaction tower tower , and the reaction zone of the middle lower part of the reaction gas outlet at the top of the; reaction region of the bubbling gravity reaction tower on the tower wall is provided with a plurality of groups of alternating distribution of the gravity sedimentation plate; stirring reaction tower is provided with a stirrer within the reaction zone; the bottom of the reaction zone of the reaction tower is provided with a gas inlet and the gas distributor; the reaction tower and the constant temperature sedimentation tower through the flange connection; is arranged in the constant temperature sedimentation tower can be used for the liquid through the microporous filter plate, constant temperature sedimentation tower in a microporous filter plate is arranged at the lower part of the circulation pipeline is connected to the upper part of the reaction zone of the reaction tower; using the separated synchronization reactor device for air oxidizing substituted toluene producing substituted benzoic acid, can not only reduce the excessive reaction to the product in the reactor, to obtain the high purity product substituted benzoic acid, prevent sedimentation tower reactor is connected between the pipeline and the blockage of the circulation pipeline, but also can realize at the same time in the reaction of the substituted benzoic acid in a timely and effective separation. (by machine translation)
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Paragraph 0053; 0054
(2016/12/01)
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- METHOD OF REGIOSELECTIVE SYNTHESIS OF SUBSTITUTED BENZOATES
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A method of synthesis of para-substituted benzoate esters and acids is provided, wherein the para-substituted regioisomer is obtained substantially free of the meta-substituted impurity, the method comprising contacting a coumalate ester or acid and an un activated alkene at elevated temperature in the presence of a metal oxidation catalyst and an oxidant. The metal oxidation catalyst can be palladium, such as palladium on carbon, and the oxidant can be the oxygen gas in ambient air. The reaction can be carlied out without solvent or in high boiling hydrocarbon solvents such as mesitylene. When the un activated alkene is a monosubstituted alkene, yields of at least about 50 or 60% of para-substituted ester and acid products, respectively, are obtained, substantially free of the regioisomelic meta-substituted impurity.
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Page/Page column 11; 12; 18; 19; 20
(2013/03/26)
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- 3-Mercapto-1,2,4-triazoles and N-acylated thiosemicarbazides as metallo-β-lactamase inhibitors
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The production of β-lactamases is an effective strategy by which pathogenic bacteria can develop resistance against β-lactam antibiotics. While inhibitors of serine-β-lactamases are widely used in combination therapy with β-lactam antibiotics, there are no clinically available inhibitors of metallo-β-lactamases (MBLs), and so there is a need for the development of such inhibitors. This work describes the optimisation of a lead inhibitor previously identified by fragment screening of a compound library. We also report that thiosemicarbazide intermediates in the syntheses of these compounds are also moderately potent inhibitors of the IMP-1 MBL from Pseudomonas aeruginosa. The interactions of these inhibitors with the active site of IMP-1 were examined using in silico methods.
- Faridoon,Hussein, Waleed M.,Vella, Peter,Islam, Nazar Ul,Ollis, David L.,Schenk, Gerhard,McGeary, Ross P.
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supporting information; experimental part
p. 380 - 386
(2012/02/04)
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- Aromatics from pyrones: Para-substituted alkyl benzoates from alkenes, coumalic acid and methyl coumalate
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The Diels-Alder reaction of coumalic acid and methyl coumalate with unactivated alkenes provides only para-substituted adducts in good yield.
- Kraus, George A.,Riley, Sean,Cordes, Travis
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experimental part
p. 2734 - 2736
(2011/11/06)
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- Alpha-helical mimetics
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Benzoyl urea derivatives that are alpha helical peptides mimetics that mimic BH3-only proteins, compositions containing them, their conjugation to cell-targeting-moieties, and their use in the regulation of cell death are disclosed. The benzoyl urea derivatives are capable of binding to and neutralizing pro-survival Bcl-2 proteins. Use of benzoyl urea derivatives in the treatment and/or prophylaxis of diseases or conditions associated with deregulation of cell death are also described.
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Page/Page column 73-74
(2011/05/18)
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- Amine Compounds
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There is provided a compound exhibiting an activity of suppressing immune response with reduced adverse drug reactions, which compound is useful in the chemotherapy for preventing or treating, for example, a wide range of various autoimmune diseases including systemic erythematodes, chronic rheumatoid arthritis, Type I diabetes, inflammatory bowel disease, biliary cirrhosis, uveitis, multiple sclerosis or other disorders, or chronic inflammatory diseases, or cancers, lymphoma or leukemia, or resistance to organ or tissue transplantation or rejection against transplantation. Novel amine compounds having an S1P1/Edg1 receptor agonist effect, possible stereoisomers or racemic bodies of the compounds, or pharmacologically acceptable salts, hydrates or solvates of the compound, the stereoisomers or the racemic bodies, or prodrugs of the compounds, the stereoisomers, the racemic bodies, the salts, the hydrates or the solvates, are provided.
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Page/Page column 159
(2008/12/08)
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- Purinenucleoside derivative modified in 8-position and medical use thereof
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The present invention provides an 8-modified purinenucleoside derivative which is useful for diseases associated with an abnormality of plasma uric acid level. An 8-modified purinenucleoside derivative represented by the following formula (I), a prodrug thereof or a pharmaceutically acceptable salt thereof, or a hydrate or solvate thereof, is useful for the prevention or treatment of gout, hyperuricemia, urinary lithiasis, hyperuricemic nephropathy or the like. In the formula, n is 1 or 2; RA is a hydrogen atom or a hydroxyl group; R1 is a hydrogen atom, a hydroxyl group, a thiol group, an amino group or a chlorine atom; ring J represents an optionally substituted 2-naphthyl group, or a group represented by the following general formula (II) wherein Y represents a single bond or a connecting group; ring Z represents an optionally substituted aryl group or heteroaryl group or the like; and R2 to R4, P1 and Q represents a halogen atom, a cyano group or the like.
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Page/Page column 25
(2010/11/28)
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- Palladium-catalyzed direct arylation of aryl(azaaryl)methanes with aryl halides providing triarylmethanes
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Direct arylation of aryl(azaaryl)methanes with aryl halidas takes place at the benzylic position in the presence of a hydroxide base under palladium catalysis to yield triarylmethanes
- Niwa, Takashi,Yorimitsu, Hideki,Oshima, Koichiro
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p. 2373 - 2375
(2008/02/05)
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- ALPHA-HELICAL MIMETICS
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Benzoyl urea derivatives that are alpha helical peptide mimetics that mimic BH3-only proteins, compositions containing them, their conjugation to cell-targeting moieties, and their use in the regulation of cell death are disclosed. The benzoyl urea derivatives are capable of binding to and neutralising pro-survival Bcl-2 proteins. Use of the benzoyl urea derivatives in the treatment and/or prophylaxis of diseases or conditions associated with deregulation of cell death are also disclosed.
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Page/Page column 142
(2010/02/15)
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- 2-(substituted-phenyl)amino-imidazoline derivatives
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This invention relates to IP receptor antagonists selected from the group of compounds represented by Formula I: where:R1 is a group represented by formula (A), (B) or (C); and other substituents as defined in the specification, and their pharmaceutically acceptable salts or crystal forms thereof; and pharmaceutical compositions containing them; and methods for their use as therapeutic agents.
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- Chemistry and stereochemistry of benzyl-benzyl interactions in MH+ ions of dibenzyl esters upon chemical ionization and collision-induced dissociation conditions
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Isobutane chemical ionization mass spectra of dibenzyl esters of a wide variety of aliphatic, olefinic, alicyclic and aromatic dicarboxylic acids exhibit abundant m/z 181 C14H13+ ions, indicating a highly general rearrangement process involving the formation of a new bond between the two benzyl groups. An extensive collision-induced dissociation and deuterium labeling study suggested that these ions are an almost equimolar mixture of isomeric α-o-tolylbenzyl, α-p-tolylbenzyl and p-benzylbenzyl cation structures, and this composition is identical for all the diesters examined. This structural assignment of the C14H13 ions suggests a mechanistic pathway for their generation, based on the formation of the new bond between the benzyl methylene group of the protonated benzoxycarbonyl and the phenyl ring of the other ester moiety via π- (and/or ion-neutral) and α-complexes. Stereoisomeric diesters show an unusual steric effect: trans-isomers give rise to much more abundant C14H13+ ions than the cis counterparts. This behavior is explained by stabilized proton-bridged structures of the MH+ ions of the cis-isomers.
- Edelson-Averbukh,Mandelbaum
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p. 515 - 524
(2007/10/03)
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- Pesticidal cyclopropyl-2,4-dieneamides
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The present Application discloses pesticidally active compounds of the formula (I): or a salt thereof, wherein Q is an monocyclic aromatic ring. or fused bicyclic ring system of which at least one ring is aromatic containing 9 or 10 atoms of which one may be nitrogen and the rest carbon each optionally substituted, or Q is a dihalovinyl group or a group R6 --C C-- where R6 is C1-4 alkyl, tri C1-4 alkylsilyl, halogen or hydrogen; Q1 is a 1,2-cyclopropyl ring optionally substituted by one or more groups selected from C1-3 alkyl. halo, C1-3 haloalkyl, alkynyl, or cyano; R2,R3, R4 and R5 are the same or different with at least one being hydrogen and the others being independently selected from hydrogen, halo. C1-4 alkyl or C1-4 haloalkyl; X is oxygen or sulphur; and R1 is selected from hydrogen and C1-8 hydrocarbyl optionally substituted by dioxalanyl, halo, cyano, trifluoromethyl, trifluoromethylthio or C1-6 alkoxy. their preparation, pesticidal compositions containing them and their use against pests.
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- Evaluation of the Polar-inductive and Mesomeric Effects exerted by para-Substituted Phenyl Rings on Contiguous Functionalities
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The para C-13 shifts of the phenyl ring in PhCH2Ar (I) is used as a monitor to evaluate, in terms of the previously defined ?IB constants, the polar-inductive effect exerted by some para-substituted aryl rings.Analogously, the para C-13 shift of the phenyl ring in PhNHAr (IV) is used as a monitor to evaluate, in terms of the previously defined ?C- constants, the blended polar-inductive and mesomeric effects exerted by such para-substituted aryl rings.The same para C-13 data offer access, through a biparametric (DSP) treatment, to ?R- constants, which account for the mesomeric effects exerted by the same substituents. C-13 Shift data are also reported for the 4'-substituted sodium aryl(phenyl)amides PhN-Ar (VII) which have been prepared in Me2SO by deprotonation of PhNHAr.The ?C- values just obtained account successfully for the para C-13 shifts of the phenyl ring of (VII), for the para C-13 shifts of the phenyl ring of phenylhydrazones of para-substituted benzaldehydes, and for the acidity of aryl(phenyl)amines measured in Me2SO-H2O by Dolman and Stewart.The success of the biparametric treatment is limited by the small range of the ?IB values of the para-substituted aryl derivatives and by the scarcity of data.The ?IB set is linearly related to the set of ?I constants obtained from substituted acetic acids.Both the ?IB and the ?C- sets account successfully for the acidity of para-substituted benzoic acids in H2O, in Me2SO, and in the gas phase: a rationale is given.
- Barchiesi, Emma,Bradamante, Silvia,Pagani, Giorgio A.
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p. 1091 - 1096
(2007/10/02)
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- Liquid Crystalline Properties of Cholesteryl ω-Arylalkanoates
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The thermal properties of the homologous series of cholesteryl ω-(4-benzoylphenyl)- (I), ω-(4-benzylphenyl)- (II), ω-benzoyl- (III), and ω-phenoxyalkanoate (IV) have been investigated.For series I and II the cholesteric-isotropic (Ch-I) transition temperatures, enthalpies, and entropies show a remarkable alternation.For series III and IV, the transition temperatures, enthalpies, and entropies exhibit weak alternation and their trends are opposite to those for series I and II, and the cholesteryl ω-phenylalkanoates.The cholesteric-isotropic transition temperatures are discussed in terms of the geometrical and electrical alternations stemming from the terminal aryl groups, and also the relative importance between these two terms.
- Koden, Mitsuhiro,Miyake, Shiro,Takenaka, Shunsuke,Kusabayashi, Shigekazu
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p. 2387 - 2390
(2007/10/02)
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- Effect of Chain Length on Mesomorphism of Steroid Esters of 4-(4-Alkylphenyl-X)benzoic Acids with X = CO, O, S, and CH2
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To examine the effect of bent shapes on mesomorphic properties a homologous series of steroid esters have been prepared: H(CH2)n-4-C6H4-X-4-C6H4COOR, X = CO, O, S, CH2, R = cholesteryl, β-sitosteryl, cholestanyl, stigmasteryl, ergosteryl; n = 0-15.The chain elongation results in an increase in not only the molecular length but also the breadth due to the angular linkage, X.The steroid portions are of primary importance for the mesomorphic properties of the present series, and the thermal stability of the mesophases is strongly dependent on the mesogenic power of the aryl portions, where the effective order is CO > O > S > CH2.The transition enthalpies and entropies for the smectic A-cholesteric and cholesteric-isotropic (Ch-I) transitions are almost independent of the chain length of the alkyl group, indicating that a long alkyl chain has no role from a thermodynamical piont of view.Within the mesophases, the aryl and steroid cores are assumed to be piled up, interacting with each other, and the alkyl groups are apart from each other to avoid short-range interaction.
- Koden, Mitsuhiro,Yagyu, Tadao,Takenaka, Shunsuke,Kusabayashi, Shigekazu
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p. 4730 - 4737
(2007/10/02)
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- INFLUENCE OF THE ANGULAR LINKAGE ON THE MESOMORPHIC PROPERTIES OF CHOLESTERYL ARYLBENZOATES.
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Some cholesteryl esters of arylbenzoic acids incorporating angular linkage such as -Co-, -O-, -S-, and -CH//2-, were prepared, and the transition temperatures and heats determined. The cholesteric-isotropic transition temperatures are likely to correlate with the angular correlation parameters of these carboxylic acid moieties. The mesomorphic phenomena are discussed in terms of the molecular structure and electronic effect of these linkages.
- Koden,Takenaka,Kusabayashi
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p. 137 - 150
(2007/10/02)
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