- Synthesis of 4-phenylethynylphthalic anhydride, a useful end-capping agent for polyimides
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Hydrolysis and bromination of phthalic anhydride in water gave a mixture of the monosodium salt of 4-bromophthalic acid. These were reacted with phenylacetylene under Sonogashira coupling reaction conditions in an aqueous medium. Acidification afforded 4-phenylethynylphthalic acid and then dehydration of this gave 4-phenylethynylphthalic anhydride in 76% overall yield. Compared with traditional synthetic methods, this method has the advantage of low cost, convenient manipulation and is environmentally friendly.
- Yang, Mei-Jia,Shao, Tao,Men, Jian,Gao, Guo-Wei,Chen, Hua
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Read Online
- CYCLIC PEPTIDE ANALOGS OF MELANOCORTIN AND AMANITIN AND METHODS OF MAKING SUCH
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The invention described herein is based in part on the discovery of a protein/peptide crosslink, which introduces fluorescent properties, and which has been applied to synthesize analogues of melanocortin and amanitin as choice peptides to be explored in the context of isoindole peptides. Without limitation, it is expected that those trained in the art of peptide synthesis and stapling would appreciate the consequences of this invention such that other peptides of varied length can be similarly constrained by isoindole staples as featured herein.
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Paragraph 0114-0115; 0122
(2021/01/29)
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- Fluorescent Isoindole Crosslink (FlICk) Chemistry: A Rapid, User-friendly Stapling Reaction
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The stabilization of peptide secondary structure via stapling is a ubiquitous goal for creating new probes, imaging agents, and drugs. Inspired by indole-derived crosslinks found in natural peptide toxins, we employed ortho-phthalaldehydes to create isoindole staples, thus transforming inactive linear and monocyclic precursors into bioactive monocyclic and bicyclic products. Mild, metal-free conditions give an array of macrocyclic α-melanocyte-stimulating hormone (α-MSH) derivatives, of which several isoindole-stapled α-MSH analogues (Ki≈1 nm) are found to be as potent as α-MSH. Analogously, late-stage intra-annular isoindole stapling furnished a bicyclic peptide mimic of α-amanitin that is cytotoxic to CHO cells (IC50=70 μm). Given its user-friendliness, we have termed this approach FlICk (fluorescent isoindole crosslink) chemistry.
- Todorovic, Mihajlo,Schwab, Katerina D.,Zeisler, Jutta,Zhang, Chengcheng,Bénard, Francois,Perrin, David M.
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supporting information
p. 14120 - 14124
(2019/07/31)
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- Synthesis and biological evaluation of chemokine receptor ligands with 2-benzazepine scaffold
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Targeting CCR2 and CCR5 receptors is considered as promising concept for the development of novel antiinflammatory drugs. Herein, we present the development of the first probe-dependent positive allosteric modulator (PAM) of CCR5 receptors with a 2-benzazepine scaffold. Compound 14 (2-isobutyl-N-({[N-methyl-N-(tetrahydro-2H-pyran-4-yl)amino]methyl}phenyl)-1-oxo-2,3-dihydro-1H-2-benzazepine-4-carboxamide) activates the CCR5 receptor in a CCL4-dependent manner, but does not compete with [3H]TAK-779 binding at the CCR5. Furthermore, introduction of a p-tolyl moiety at 7-position of the 2-benzazepine scaffold turns the CCR5 PAM 14 into the selective CCR2 receptor antagonist 26b. The structure affinity and activity relationships presented here offer new insights into ligand recognition by CCR2 and CCR5 receptors.
- Thum, Simone,Kokornaczyk, Artur K.,Seki, Tomoaki,De Maria, Monica,Ortiz Zacarias, Natalia V.,de Vries, Henk,Weiss, Christina,Koch, Michael,Schepmann, Dirk,Kitamura, Masato,Tschammer, Nuska,Heitman, Laura H.,Junker, Anna,Wünsch, Bernhard
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supporting information
p. 401 - 413
(2017/05/04)
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- Industrial preparation method of 5-bromophthalide
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The invention relates to a preparation method of 5-bromophthalide and mainly solves such production technical problems of an existing preparation method as expensive raw material, dangerous and complex operation, relatively low yield, high quantity of generated three wastes and etc. The technical scheme of the invention is as follows: an industrial preparation method of 5-bromophthalide is characterized in that 5-bromophthalide is obtained through three step reactions of bromination, ammoniation and reduction by taking a conventional and easily available ammoniation as a raw material. The chemical reaction formula is as shown in the description. The method provided by the invention is mainly used for industrial preparation of 5-bromophthalide.
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Paragraph 0012; 0013; 0014; 0015; 0016
(2017/09/01)
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- Naphthalenes Oxidation by Aqueous Sodium Hypochlorite Catalyzed by Ruthenium Salts under Phase-Transfer Catalytic Conditions
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Highly effective and fast oxidation of naphthalene(s) to phthalic acid(s) under biphasic conditions using nominal catalyst loading (0.5 mol%) of ruthenium chloride, 2.5 mol% tetrabutyl ammonium bromide as phase transfer catalyst and inexpensive aqueous sodium hypochlorite (NaOCl) as reagent has developed. Recovery, regeneration and reuse of the catalytic system add its merit to green chemistry.
- Patil, Rajendra D.,Sasson, Yoel
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p. 991 - 997
(2016/04/20)
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- Design, synthesis and structure-activity relationship studies of morpholino-1H-phenalene derivatives that antagonize Mcl-1/Bcl-2
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We report herein characteristic studies of Mcl-1 and Bcl-2 dual inhibitors. It was found that a protruding carbonyl group forming hydrogen bond with R263 plays a predominant role compared with the hydrophobic group that occupies the p2 pocket. A series of dual inhibitors representing different parts of the morpholino-1H-phenalene were designed, synthesized and evaluated.
- Li, Xiangqian,Liang, Xiaomeng,Song, Ting,Su, Pengchen,Zhang, Zhichao
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p. 5738 - 5746
(2015/02/02)
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- Polymeric phthalates: Potential nonmigratory macromolecular plasticizers
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The synthesis of 4-vinyl-1,2-phthalate esters via Suzuki coupling is described, followed by nitroxide-mediated polymerization to prepare short homopolymers (degree of polymerization [DP] = 10-40, polydispersity index [PDI] = 1.1-1.3). Random copolymers with n-butyl acrylate (NBA) were prepared. Copolymers rich in phthalate ester residues of medium lengths (DP = 16-48, PDI = 1.2-1.8) and of shorter lengths (DP = 8-17, PDI = 1.2-1.3) were prepared. Copolymers rich in NBA residues were also prepared (DP = 13-19, PDI = 1.2-1.3). All polymers were oily liquids, with glass transitions temperatures undetected between 75 and -40 °C, indicating these polymeric phthalates hold promise as potential nonmigratory phthalate plasticizers. 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013. Copyright
- Braslau, Rebecca,Schaeffner, Friederike,Earla, Aruna
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p. 1175 - 1184
(2013/03/29)
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- An anthraquinone scaffold for putative, two-face bim BH3 α-helix mimic
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Bim BH3 peptide features an α-helix with hotspot residues on multiple faces. Compound 5 (6-bromo-2,3-dihydroxyanthracene-9,10-dione), which adopts a rigid-plan amphipathic conformation, was designed and evaluated as a scaffold to mimic two faces of Bim α-helix. It reproduced the functionalities of both D67 and I65 on two opposing helical sides. Moreover, it maintained the two-faced binding mode during further evolution. A putative BH3 α-helix mimic and nanomolar Bcl-2/Mcl-1 dual inhibitor, 6, was obtained based on the structure of 5.
- Zhang, Zhichao,Li, Xiangqian,Song, Ting,Zhao, Yan,Feng, Yingang
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p. 10735 - 10741
(2013/02/23)
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- Metallo-β-lactamase inhibitory activity of phthalic acid derivatives
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4-Butyl-3-methylphthalic acid was recognized as a metallo-β-lactamase inhibitor. The structure-activity relationship study of substituted phthalic acids afforded 3-phenylphthalic acid derivatives as potent IMP-1 inhibitors. On the other hand, 3-substituted with 4-hydroxyphenyl phthalic acid derivative displayed a potent combination effect with biapenem (BIPM) against Pseudomonas aeruginosa that produce IMP-1.
- Hiraiwa, Yukiko,Morinaka, Akihiro,Fukushima, Takayoshi,Kudo, Toshiaki
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scheme or table
p. 5162 - 5165
(2010/03/24)
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- Tetrakis(diethyl phosphonate), Tetrakis(ethyl phenylphosphinate)-, and Tetrakis(diphenylphosphine oxide)-Substituted Phthalocyanines
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The title compounds 7,9, and 11 are obtained by tetramerization of diethyl (3,4-dicyanophenyl)phosphonate (5), ethyl (3,4-dicyanophenyl)phenylphosphinate (8), and 4-(diphenylphosphinyl)benzene-1,2-dicarbonitrile (10). The 31P-NMR spectra of the phthalocyanines 7,9, and 11 and of their metal complexes present five to eight signals confirming the formation of four constitutional isomers with the expected C4h, D2h, C 2v, and Cs symmetry. In the FAB-MS of the Zn, Cu, and Ni complexes of 7 and 9, the peaks of dimeric phthalocyanines are observed. By gel-permeation chromatography, the monomeric complex [Ni(7)] and a dimer [Ni(7)]2 can be separated. These dimers differ from the known phthalocyanine dimers, i.e., possibly the P(O)(OEt)2 and P(O)(Ph)(OEt) substituents in 7 and 9 are involved in complexation. The free phosphonic acid complex [Zn(12)] and [Cu(12)] are H2O-soluble. In the FAB-MS of [Zn(12)], only the peaks of the dimer are present; the ESI-MS confirms the existence of the dimer and the metal-free dimer. In the UV/VIS spectrum of [Zn(12)], the hypsochromic shift characteristic for the known type of dimers from 660-700 nm to 620-640 nm is observed. As in the FAB-MS of [Zn(12)], the free phosphinic acid complex [Zn(13)] shows only the monomer, an ESI-MS cannot be obtained for solubility problems. The UV/VIS spectrum of [Zn(13)] demonstrates the existence of the monomer as well as of the dimer.
- Maerkl, Gottfried,Gschwendner, Karl,Roetzer, Ingrid,Kreitmeier, Peter
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p. 825 - 844
(2007/10/03)
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- Asymmetric dihydroxylations using immobilized alkaloids with an anthraquinone core
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In osmium-catalyzed dihydroxylations use of polymer-supported alkaloids with an anthraquinone core allows to obtain optically active diols with high enantioselectivities. Soluble as well as insoluble polymers have been tested for immobilization.
- Bolm,Maischak
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- Benzocyclobutenes. Part 4. Synthesis of Benzocyclobutene-1,2-diones by Pyrolytic Methods
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Oxidation of the cyclic hydrazides prepared from phthalic anhydrides in the presence of anthracene gives the corresponding Diels-Alder adducts which, on flash vacuum pyrolysis, give benzocyclobutene-1,2-dione (BBD) and its 4-chloro, 3,6- and 4,5-dichloro, 4,5-dibromo, and 4,5-dimethyl derivatives in 75-98percent yield.Cyclobuta- and cyclobuta-naphthalene-1,2-dione as well as cyclobuta- and cyclobuta-pyridine-1,2-dione have been prepared similarly; the last three of these diones are very unstable.Cyclobutanaphthalene-1,2-dione has also been made by pyrolysis of benzindene-1,2,3-trione.Attempts to make thiophen and furan analogues of BBD from appropriate anthracene adducts failed as did attempts to make tetrachloro- and tetrabromo-derivatives of BBD by the pyrolysis of tetrahalogenophthalimidosulphoximides.
- Gould, Ken J.,Hacker, Nigel P.,McOmie, John F. W.,Perry, David H.
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p. 1834 - 1840
(2007/10/02)
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