共查询到20条相似文献,搜索用时 15 毫秒
1.
Dr. Heiko Schill Dr. Shamil Nizamov Dr. Francesca Bottanelli Dipl.‐Chem. Jakob Bierwagen Dr. Vladimir N. Belov Prof. Stefan W. Hell 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(49):16556-16565
Bright and photostable fluorescent dyes with large Stokes shifts are widely used as sensors, molecular probes, and light‐emitting markers in chemistry, life sciences, and optical microscopy. In this study, new 7‐dialkylamino‐4‐trifluoromethylcoumarins have been designed for use in bioconjugation reactions and optical microscopy. Their synthesis was based on the Stille reaction of 3‐chloro‐4‐trifluoromethylcoumarins and available (hetero)aryl‐ or (hetero)arylethenyltin derivatives. Alternatively, the acylation of 2‐trifluoroacetyl‐5‐dialkylaminophenols with available (hetero)aryl‐ or (hetero)arylethenylacetic acids followed by intramolecular condensation afforded coumarins with 3‐(hetero)aryl or 3‐[2‐(hetero)aryl]ethenyl groups. Hydrophilic properties were provided by the introduction of a sulfonic acid residue or by phosphorylation of a primary hydroxy group attached at C‐4 of the 2,2,4‐trimethyl‐1,2‐dihydroquinoline fragment fused to the coumarin fluorophore. For use in immunolabeling procedures, the dyes were decorated with an (activated) carboxy group. The positions of the absorption and emission maxima vary in the ranges 413–480 and 527–668 nm, respectively. The phosphorylated dye, 9 ,CH?CH‐2‐py,H, with the 1‐(3‐carboxypropyl)‐4‐hydroxymethyl‐2,2‐dimethyl‐1,2‐dihydroquinoline fragment fused to the coumarin fluorophore bearing the 3‐[2‐(2‐pyridyl)ethenyl] residue (absorption and emission maxima at 472 and 623 nm, respectively) was used in super‐resolution light microscopy with stimulated emission depletion and provided an optical resolution better than 70 nm with a low background signal. As a result of their large Stokes shifts, good fluorescence quantum yields, and adequate photostabilities, phosphorylated coumarins enable two‐color imaging (using several excitation sources and a single depletion laser) to be combined with subdiffractional optical resolution. 相似文献
2.
Dr. Shamil Nizamov Dr. Katrin I. Willig Dipl.‐Chem. Maksim V. Sednev Dr. Vladimir N. Belov Prof. Stefan W. Hell 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(51):16339-16348
Photostable and bright fluorescent dyes with large Stokes shifts are widely used as markers in far‐field optical microscopy, but the variety of useful dyes is limited. The present study introduces new 3‐heteroaryl coumarins decorated with a primary phosphate group (OP(O)(OH)2) attached to C‐4 in 2,2,4‐trimethyl‐1,2‐dihydroquinoline fragment fused with the coumarin fluorophore. The general synthetic route is based on the Suzuki reaction of 3‐bromocoumarines with hetarylboronic acids followed by oxidation of the methyl group at the C?C bond with SeO2 (to an aldehyde), reduction with NaBH4 (to an alcohol), and conversion into a primary phosphate. The 4 position in the coumarin system may be unsubstituted or bear a methyl group. Phosphorylated coumarins were found to have high fluorescence quantum yields in the free state and after conjugation with proteins (in aqueous buffers). In super‐resolution light microscopy with stimulated emission depletion (STED), the new coumarin dyes provide an optical resolution of 40–60 nm with a low background signal. Due to their large Stokes shifts and high photostability, phosphorylated coumarins enable to combine multilabel imaging (using one detector and several excitation sources) with diffraction unlimited optical resolution. 相似文献
3.
Antony Bulanov Igor N. Shcherbakov Leonid D. Popov E. Y. Shasheva P. A. Belikov Zoya A. Starikova 《Acta Crystallographica. Section C, Structural Chemistry》2011,67(3):o85-o88
The structures of new oxaindane spiropyrans derived from 7‐hydroxy‐3′,3′‐dimethyl‐3′H‐spiro[chromene‐2,1′‐isobenzofuran]‐8‐carbaldehyde (SP1), namely N‐benzyl‐2‐[(7‐hydroxy‐3′,3′‐dimethyl‐3′H‐spiro[chromene‐2,1′‐isobenzofuran]‐8‐yl)methylidene]hydrazinecarbothioamide, C27H25N3O3S, (I), at 120 (2) K, and N′‐[(7‐hydroxy‐3′,3′‐dimethyl‐3′H‐spiro[chromene‐2,1′‐isobenzofuran]‐8‐yl)methylidene]‐4‐methylbenzohydrazide acetone monosolvate, C27H24N2O4·C3H6O, (II), at 100 (2) K, are reported. The photochromically active Cspiro—O bond length in (I) is close to that in the parent compound (SP1), and in (II) it is shorter. In (I), centrosymmetric pairs of molecules are bound by two equivalent N—H...S hydrogen bonds, forming an eight‐membered ring with two donors and two acceptors. 相似文献
4.
Alexander J. Blake Pamela V. Mason Claire Wilson Neil R. Champness 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(6):m280-m282
The single‐crystal X‐ray structures of dimethyl 2,2′‐bipyridine‐6,6′‐dicarboxylate, C14H12N2O4, and the copper(I) coordination complex bis(dimethyl 2,2′‐bipyridine‐6,6′‐dicarboxylato‐κ2N,N′)copper(I) tetrafluoroborate, [Cu(C14H12N2O4)2]BF4, are reported. The uncoordinated ligand crystallizes across an inversion centre and adopts the anticipated anti pyridyl arrangement with coplanar pyridyl rings. In contrast, upon coordination of copper(I), the ligand adopts an arrangement of pyridyl donors facilitating chelating metal coordination and an increased inter‐pyridyl twisting within each ligand. The distortion of each ligand contrasts with comparable copper(I) complexes of unfunctionalized 2,2′‐bipyridine. 相似文献
5.
Lionel Salmon Pierre Thury Michel Ephritikhine 《Acta Crystallographica. Section C, Structural Chemistry》2003,59(6):m246-m248
The title complex, bis(acetylacetonato‐κ2O,O′)[N,N′‐bis(3‐hydroxy‐2‐oxidobenzaldimino)‐2‐methyl‐1,2‐propanediamine‐κ4N,O,O′,N′]uranium(IV) tetrahydrofuran solvate, [U(C18H18N2O4)(C5H7O2)2]·C4H8O, is a rare example of a uranium(IV) complex with a compartmental Schiff base. The U atom is located in the N2O2 inner site of the hexadentate N,N′‐bis(3‐hydroxy‐2‐oxidobenzaldimino)‐2‐methyl‐1,2‐propanediamine group and is bound also to the two O atoms of both acetylacetonate moieties, which results in a dodecahedral coordination environment. Centrosymmetric dimers are formed through intermolecular hydrogen bonds that link the terminal uncoordinated hydroxy groups to one another and to the O atoms of the acetylacetonate ligands. 相似文献
6.
Alla Zablotskaya Izolda Segal Yuris Popelis Solveiga Grinberga Irina Shestakova Vizma Nikolajeva Daina Eze 《应用有机金属化学》2013,27(2):114-124
A series of N‐methyl‐N‐(2‐triorganylsiloxyethyl)‐1,2,3,4‐tetrahydro(iso)quinolinium iodides has been synthesized via dehydrocondensation reaction of N‐(2‐hydroxyethyl)‐1,2,3,4‐tetrahydroisoquinoline, N‐(2‐hydroxyethyl)‐1,2,3,4‐tetrahydroquinoline and 4,4‐dimethyl‐N‐(2‐hydroxyethyl)‐4‐sila‐1,2,3,4‐tetrahydroisoquinoline with trialkyl(aryl)hydrosilanes and subsequent alkylation, and characterized by 1H, 13C and 29Si NMR and mass spectroscopy. The biological activity data exhibited a marked enhancement of inhibitory activity against tumour cell lines and almost all the test bacterial/fungal strains in comparison with their 2‐hydroxyethyl precursors. Cytotoxicity in the microgram range against HT‐1080 (human fibrosarcoma) and MG‐22A (mouse hepatoma) cancer cell lines was observed for most of compounds. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
7.
New 3‐(Heteroaryl)‐2‐iminocoumarin‐based Borate Complexes: Synthesis,Photophysical Properties,and Rational Functionalization for Biosensing/Biolabeling Applications 下载免费PDF全文
Benoît Roubinet Dr. Cédrik Massif Dr. Mathieu Moreau Dr. Frédéric Boschetti Dr. Gilles Ulrich Dr. Raymond Ziessel Prof. Pierre‐Yves Renard Prof. Anthony Romieu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(41):14589-14601
Members of a series of boron difluoride complexes with 3‐(heteroaryl)‐2‐iminocoumarin ligands bearing both a phenolic hydroxyl group (acting as a fluorogenic center) and an N‐aryl substituent (acting as a stabilizing moiety) have been synthesized in good yields by applying a straightforward two‐step method. These novel fluorogenic dyes belong to the family of “Boricos” (D. Frath et al., Chem. Commun. 2013 , 49, 4908–4910) and are the first examples of phenol‐based fluorophores of which the photophysical properties in the green‐yellow spectral range are dramatically improved by N,N‐chelation of a boron atom. Modulation of their fluorescence properties through reversible chemical modification of their phenol moieties has been demonstrated by the preparation of the corresponding 2,4‐dinitrophenyl (DNP) ethers, which led to a dramatic “OFF‐ON” fluorescence response upon reaction with thiols. Additionally, to expand the scope of these “7‐hydroxy‐Borico” derivatives, particularly in biolabeling, amine or carboxylic acid functionalities amenable to (bio)conjugation have been introduced within their scaffold. Their utility has been demonstrated in the preparation of fluorescent bovine serum albumin (BSA) conjugates and “Borico”‐DOTA‐like scaffolds in an effort to design novel monomolecular multimodal fluorescence‐ radioisotope imaging agents. 相似文献
8.
Sc(OTf)3‐Catalyzed Bicyclization of o‐Alkynylanilines with Aldehydes: Ring‐Fused 1,2‐Dihydroquinolines 下载免费PDF全文
Can Zhu Prof. Dr. Shengming Ma 《Angewandte Chemie (International ed. in English)》2014,53(49):13532-13535
A Sc(OTf)3‐catalyzed cascade Prins‐type cyclization reaction of o‐alkynylanilines, bearing a hydroxy or amine functionality, with aldehydes affords 1,2‐dihydroquinoline derivatives having an extra fused ring efficiently under mild reaction conditions. It is interesting to observe the reversed reactivity in the highly selective formation of 1,2‐dihydroquinoline derivatives instead of the formation of the usually favored indole derivatives. 相似文献
9.
Waseeq Ahmad Siddiqui Saeed Ahmad Muhammad Ilyas Tariq Hamid Latif Siddiqui Masood Parvez 《Acta Crystallographica. Section C, Structural Chemistry》2008,64(1):o4-o6
The structures of N‐(2‐chlorophenyl)‐4‐hydroxy‐2‐methyl‐2H‐1,2‐benzothiazine‐3‐carboxamide 1,1‐dioxide and N‐(4‐chlorophenyl)‐4‐hydroxy‐2‐methyl‐2H‐1,2‐benzothiazine‐3‐carboxamide 1,1‐dioxide, both C16H13ClN2O4S, are stabilized by extensive intramolecular hydrogen bonds. The 4‐chloro derivative forms dimeric pairs of molecules lying about inversion centres as a result of intermolecular N—H...O hydrogen bonds, forming 14‐membered rings representing an R22(14) motif; the 2‐chloro derivative is devoid of any such intermolecular hydrogen bonds. The heterocyclic thiazine rings in both structures adopt half‐chair conformations. 相似文献
10.
Isoindigo‐3,4‐Difluorothiophene Polymer Acceptors Yield “All‐Polymer” Bulk‐Heterojunction Solar Cells with over 7 % Efficiency 下载免费PDF全文
Dr. Shengjian Liu Dr. Yuliar Firdaus Dr. Simil Thomas Dr. Zhipeng Kan Federico Cruciani Dr. Sergei Lopatin Prof. Jean‐Luc Bredas Prof. Pierre M. Beaujuge 《Angewandte Chemie (International ed. in English)》2018,57(2):531-535
Poly(isoindigo‐alt‐3,4‐difluorothiophene) (PIID[2F]T) analogues used as “polymer acceptors” in bulk‐heterojunction (BHJ) solar cells achieve >7 % efficiency when used in conjunction with the polymer donor PBFTAZ (model system; copolymer of benzo[1,2‐b:4,5‐b′]dithiophene and 5,6‐difluorobenzotriazole). Considering that most efficient polymer‐acceptor alternatives to fullerenes (e.g. PC61BM or its C71 derivative) are based on perylenediimide or naphthalenediimide motifs thus far, branched alkyl‐substituted PIID[2F]T polymers are particularly promising non‐fullerene candidates for “all‐polymer” BHJ solar cells. 相似文献
11.
Anthony Linden Boyan Iliev Heinz Heimgartner 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(6):o339-o343
The title macrocycle, C26H30N2O6, (VI), was obtained by `direct amide cyclization' from the linear precursor 3‐hydroxy‐N‐[1‐methyl‐1‐(N‐methyl‐N‐phenylcarbamoyl)ethyl]‐2‐phenylpropanamide, the N‐methylanilide of rac‐2‐methyl‐2‐[(3‐hydroxy‐2‐phenylpropanoyl)amino]propanoic acid, C13H17NO4, (IV). The reaction proceeds via the intermediate rac‐2‐(2‐hydroxy‐1‐phenylethyl)‐4,4‐dimethyl‐1,3‐oxazol‐5(4H)‐one, C13H15NO3, (V), which was synthesized independently and whose structure was also established. Unlike all previously described analogues, the title macrocycle has the cis‐diphenyl configuration. The 14‐membered ring has a distorted rectangular diamond‐based [3434] configuration and intermolecular N—H⋯O hydrogen bonds link the molecules into a three‐dimensional framework. The propanoic acid precursor forms a complex series of intermolecular hydrogen bonds, each of which involves pairwise association of molecules and which together result in the formation of extended two‐dimensional sheets. The oxazole intermediate forms centrosymmetric hydrogen‐bonded dimers in the solid state. 相似文献
12.
Xuerui Wang Wenxue Zhang Hongjuan Shen Wei Zhang 《Journal of heterocyclic chemistry》2013,50(3):501-505
A one‐pot synthesis of pyrrolo[1,2‐a]quinolin‐1‐ones has been developed from the reactions of 5‐hydroxy‐1‐arylpyrrolidin‐2‐ones with 1,3‐dicarbonyl compounds under the promotion of H3PO4/P2O5 or HOAc/H2SO4. The pyrrolo[1,2‐a]quinolin‐1‐ones are formed by two‐step reactions, that is, the coupling of N‐acyliminium ion intermediates produced from 5‐hydroxy‐1‐arylpyrrolidin‐2‐ones with 1,3‐dicarbonyls and subsequent Friedel–Crafts reactions of the resulting ketone with the aryl ring. 相似文献
13.
N‐(trialkoxysilylalkyl) derivatives of 1,2,3,4‐tetrahydroquinoline, 1,2,3,4‐tetrahydroisoquinoline and 4,4‐dimethyl‐4‐sila‐1,2,3,4‐tetrahydroisoquinoline were prepared and characterized by elemental analysis, 1H, 13C and 29Si NMR spectroscopy. In vivo psychotropic properties and in vitro cytotoxic effects of 3‐[N‐(1,2,3,4‐tetrahydroisoquinolyl)]propyltriethoxysilane methiodide and 3‐[N‐(1,2,3,4‐tetrahydroisoquinolyl)]propylsilatrane are reported. Comparative study of 29Si shifts in newly synthesized compounds suggested donor–acceptor interaction between nitrogen and silicon atom, which increased electron density at Si nuclei, revealing a stronger increment of N → Si transannular bond in comparison with N → Si α‐effect. The molecular structure of 3‐[N‐(1,2,3,4‐tetrahydroisoquinolyl)]propylsilatrane features a penta‐coordinate silicon atom having CSiO3 pattern and Si…N intramolecular interaction. Copyright © 2005 John Wiley & Sons, Ltd. 相似文献
14.
Trevor R. Simmons Christopher J. Pickett Joseph A. Wright 《Acta Crystallographica. Section C, Structural Chemistry》2011,67(1):o1-o5
A new synthetic route to 2,2‐bis(sulfanylmethyl)propane‐1,3‐diol, (II), is described starting from the commercially available 2,2‐bis(hydroxymethyl)propane‐1,3‐diol. The structures of two intermediates on this route are described. 5,5‐Dimethenyl‐2,2‐dimethyl‐1,3‐dioxane bis(thiocyanate) (systematic name: {[5‐(cyanosulfanyl)‐2,2‐dimethyl‐1,3‐dioxan‐5‐yl]sulfanyl}formonitrile), C10H14N2O2S2, (X), crystallizes in the space group P21/c with no symmetry relationship between the two thiocyanate groups. There is a short intramolecular N...S contact for one thiocyanate group, while the second group is positioned such that this type of interaction is not possible. 1,3‐(Hydroxymethyl)propane‐1,3‐diyl bis(thiocyanate), C7H10N2O2S2, (XI), also features a single short N...S contact in the solid state. Hydrogen bonding between two molecules of compound (XI) results in the formation of dimers in the crystal, which are then linked together by a second hydrogen‐bond interaction between the dimers. In addition, the structures of two intermediates from an unsuccessful alternative synthesis of (II) are reported. 2,2‐Bis(chloromethyl)propane‐1,3‐diol, C5H10Cl2O2, (VI), crystallized as an inversion twin with a minor twin fraction of 0.43 (6). It forms a zigzag structure as a result of intermolecular hydrogen bonding. The structure of 9,9‐dimethyl‐2,4,8,10‐tetraoxa‐3λ4‐thiaspiro[5.5]undecan‐3‐one, C8H14O5S, (VII), shows evidence for a weak S...O contact with a distance of 3.2529 (11) Å. 相似文献
15.
John Reglinski Michelle K. Taylor Alan R. Kennedy 《Acta Crystallographica. Section C, Structural Chemistry》2004,60(3):o169-o172
We have isolated and crystallographically characterized the three homologous compounds N,N′‐bis(2‐methoxybenzylidene)ethane‐1,2‐diamine (MeSalen), C18H20N2O2, N,N′‐bis(2‐methoxybenzylidene)propane‐1,3‐diamine (MeSalpr), C19H22N2O2, and N,N′‐bis(2‐methoxybenzylidene)butane‐1,4‐diamine (MeSalbu), C20H24N2O2. In contrast with MeSalpr, the molecules of MeSalen and MeSalbu, which have an even number of methylene units, have crystallographic symmetry. Comparing these methoxy‐substituted species with their hydroxy equivalents shows that the aryl rings rotate upon removal of the O—H⋯N hydrogen bonds. The packing of MeSalen and MeSalpr is controlled by C—H⋯π interactions, whereas that of MeSalbu has only van der Waals contacts. 相似文献
16.
Tomas Rozek John H. Bowie Brian W. Skelton Allan H. White 《Acta Crystallographica. Section C, Structural Chemistry》2003,59(8):o431-o432
The Diels–Alder reaction between 5‐hydroxy‐1,4‐naphthoquinone and 5,5‐dimethyl‐3‐vinyl‐1,2‐cyclohexadienyl acetate by endo addition gives the title compound, C22H22O5, in 68% yield. This racemic diastereoisomer has the opposite regiochemistry to ochromycinone analogues produced previously and may allow access to a new type of anticancer‐active saquayamycin analogue. 相似文献
17.
Ken W. L. Yong Mary J. Garson Paul V. Bernhardt 《Acta Crystallographica. Section C, Structural Chemistry》2009,65(4):o167-o170
The absolute configurations of spongia‐13(16),14‐dien‐3‐one [systematic name: (3bR,5aR,9aR,9bR)‐3b,6,6,9a‐tetramethyl‐4,5,5a,6,8,9,9a,9b,10,11‐decahydrophenanthro[1,2‐c]furan‐7(3bH)‐one], C20H28O2, (I), epispongiadiol [systematic name: (3bR,5aR,6S,7R,9aR,9bR)‐7‐hydroxy‐6‐hydroxymethyl‐3b,6,9a‐trimethyl‐3b,5,5a,6,7,9,9a,9b,10,11‐decahydrophenanthro[1,2‐c]furan‐8(4H)‐one], C20H28O4, (II), and spongiadiol [systematic name: (3bR,5aR,6S,7S,9aR,9bR)‐7‐hydroxy‐6‐hydroxymethyl‐3b,6,9a‐trimethyl‐3b,5,5a,6,7,9,9a,9b,10,11‐decahydrophenanthro[1,2‐c]furan‐8(4H)‐one], C20H28O4, (III), were assigned by analysis of anomalous dispersion data collected at 130 K with Cu Kα radiation. Compounds (II) and (III) are epimers. The equatorial 3‐hydroxyl group on the cyclohexanone ring (A) of (II) is syn with respect to the 4‐hydroxymethyl group, leading to a chair conformation. In contrast, isomer (III), where the 3‐hydroxyl group is anti to the 4‐hydroxymethyl group, is conformationally disordered between a major chair conformer where the OH group is axial and a minor boat conformer where it is equatorial. In compound (I), a carbonyl group is present at position 3 and ring A adopts a distorted‐boat conformation. 相似文献
18.
Richard A. Bunce Takahiro Nago Nathan Sonobe 《Journal of heterocyclic chemistry》2007,44(5):1059-1064
A series of 2‐(2‐nitrobenzyl)‐substituted β‐keto ester derivatives has been subjected to reductive cyclization under catalytic hydrogenation conditions. The reactions were found to be highly dependent on the catalyst and hydrogen pressure used. Hydrogenation over 5% palladium‐on‐carbon at 4 atmospheres pressure produced complex mixtures of products that included predominantly 1,2,3,4‐tetrahydroquinoline and quinoline products; at 1 atmosphere pressure, the same reactions gave mixtures containing predominantly tetrahydroquinoline and 1,4‐dihydroquinoline derivatives. Hydrogenation using 5% platinum‐on‐carbon was much cleaner and afforded the desired cis‐ and trans‐(±)‐2‐alkyl‐1,2,3,4‐tetrahydroquinoline‐3‐carboxylic esters, with the cis product predominating by ≥ 13:1. 相似文献
19.
Chloroformylation of 5,5‐dimethyl‐1,2‐ oxathiolan‐4‐one 2,2‐dioxide 4 with Vilsmeier reagent (DMF/POCl3) led to the formation of cyclic β‐chloro‐vinylaldehyde (4‐chloro‐5,5‐dimethyl‐3‐formyl‐1,2‐oxathiolene 2,2‐dioxide 5 ). Compound 5 reacted with formamidine, o‐aminophenol, 1,2‐phenylenediamine, aminopyrazole, and aminotetrazole to give the corresponding heterocyclic compounds. © 2005 Wiley Periodicals, Inc. Heteroatom Chem 16:200–204, 2005; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20094 相似文献
20.
Nicolas Pradeille Anthony Linden Heinz Heimgartner 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(5):o249-o252
The title compounds, O‐benzyl‐N‐(benzyloxycarbonyl)threonyl‐2,N‐dimethylalaninanilide, C30H35N3O5, and methyl (4R)‐4‐benzyloxy‐N‐(benzyloxycarbonyl)valyl‐2‐(methylalanyl)prolinate, C30H39N3O7, were obtained from the `azirine coupling' of the corresponding protected amino acids with 2,2,N‐trimethyl‐2H‐azirin‐3‐amine and methyl (4R)‐4‐(benzyloxy)‐N‐(2,2‐dimethyl‐2H‐azirin‐2‐yl)prolinate, respectively. The Aib unit in each molecule has the greatest turn‐ or helix‐inducing effect on the molecular conformation. Intermolecular N—H⋯O interactions link the molecules of the tripeptide into sheets and those of the dipeptide into extended chains. 相似文献