Indene Research Articles

Effects of Electron-Withdrawing and Electron-Donating Groups on Aromaticity in Cyclic Conjugated Polyenes.

Determining the aromaticity of various fluorinated benzenes is challenging as easily obtained experimental aromaticity [Δδ(Houter - Hinner)] necessitates the chemical shifts of inner and outer protons. This issue was addressed in porphyrinoids by replacing the electron-withdrawing (E.W.) groups at the meso-positions of porphyrins and allyliporphyrins. Electronic effects on aromaticity in porphyrinoids have not been thoroughly examined in the literature. In porphyrins, the effect of E.W. groups is minimal, making it difficult to establish a clear relationship between the aromaticity strength and E.W. groups. Conversely, in allyliporphyrins, stronger E.W. groups, such as indandione (IND) derivatives, significantly reduce the aromaticity of the parent structure. The IND derivatives disrupted the aromatic pathway of allyliporphyrin more effectively than those attached to porphyrins. This is attributed to the absence of β-carbons in allyliporphyrins. The effect of electron-donating (E.D.) groups on porphyrins and allyliporphyrins was further investigated. Contrary to the initial assumption that the E.D. groups might enhance aromaticity owing to their ability to increase electron density, as the strength of the E.D. groups increased, the aromaticity of the porphyrinoids decreased. Despite the modest reduction in aromaticity, any form of electron perturbation reduces aromaticity. The aromaticity of various fluorinated benzenes is expected to parallel our observations of porphyrinoids as representative aromatic polyenes.

Critical Role of Non-Halogenated Solvent Additives in Eco-Friendly and Efficient All-Polymer Solar Cells.

Organic solar cells (OSCs) demonstrating high power conversion efficiencies have been mostly fabricated using halogenated solvents, which are highly toxic and harmful to humans and the environment. Recently, non-halogenated solvents have emerged as a potential alternative. However, there has been limited success in attaining an optimal morphology when non-halogenated solvents (typically o-xylene (XY)) were used. To address this issue, we studied the dependence of the photovoltaic properties of all-polymer solar cells (APSCs) on various high-boiling-point non-halogenated additives. We synthesized PTB7-Th and PNDI2HD-T polymers that are soluble in XY and fabricated PTB7-Th:PNDI2HD-T-based APSCs using XY with five additives: 1,2,4-trimethylbenzene (TMB), indane (IN), tetralin (TN), diphenyl ether (DPE), and dibenzyl ether (DBE). The photovoltaic performance was determined in the following order: XY + IN < XY + TMB < XY + DBE ≤ XY only < XY + DPE < XY + TN. Interestingly, all APSCs processed with an XY solvent system had better photovoltaic properties than APSCs processed with chloroform solution containing 1,8-diiodooctane (CF + DIO). The key reasons for these differences were unraveled using transient photovoltage and two-dimensional grazing incidence X-ray diffraction experiments. The charge lifetimes of APSCs based on XY + TN and XY + DPE were the longest, and their long lifetime was strongly associated with the polymer blend film morphology; the polymer domain sizes were in the nanoscale range, and the blend film surfaces were smoother, as the PTB7-Th polymer domains assumed an untangled, evenly distributed, and internetworked morphology. Our results demonstrate that the use of an additive with an optimal boiling point facilitates the development of polymer blends with a favorable morphology and can contribute to the widespread use of eco-friendly APSCs.

Cytotoxicity and Oxidative Stress Effects of Indene on Coelomocytes of Earthworm (Eisenia foetida): Combined Analysis at Cellular and Molecular Levels.

Indene (IND) is a kind of important aromatic hydrocarbon that is extracted from coal tar and has important applications in industry and biology. In the process of production and utilization, it is easy to enter the soil and produce toxic effects on the soil or organisms. The earthworm is an important organism in the soil. The toxicity of indene on earthworm coelomocytes is rarely studied, and the oxidative stress effects of IND on earthworm coelomocytes remain unclear. In this study, coelomocytes from earthworms and antioxidant enzymes were selected as the research targets. In addition, IND caused oxidative stress, and its related toxic effects and mechanisms were systematically studied and evaluated at the cellular and molecular levels. The results showed that IND destroyed the redox balance in earthworm coelomocytes, and the large accumulation of reactive oxygen species (ROS) significantly inhibited the activities of the antioxidant system, including superoxide dismutase (SOD), catalase (CAT), and glutathione (GSH), and caused lipid peroxidation and membrane permeability changes, resulting in a decrease in cell viability to 74.5% of the control group. At the molecular level, IND was bound to SOD by the arene-H bond, and the binding constant was 4.95 × 103. IND changed the secondary structure of the SOD and led to a loosening of the structure of the SOD peptide chain. Meanwhile, IND caused SOD fluorescence sensitization, and molecular simulation showed that IND was mainly bound to the junction of SOD subunits. We hypothesized that the changes in SOD structure led to the increase in SOD activity. This research can provide a scientific basis for IND toxicity evaluation.

Effect of fused indanedione (IND) groups and antipodal β-substituents on electrochemical properties of unsymmetrical metalloporphyrins

The interacting effect of fused indanedione (IND) groups and antipodal Br [Formula: see text]-substituents on the electroreduction of free-base and transition metal tetraphenylporphyrins (TPPs) are elucidated through the use of cyclic voltammetry. A systematic study of the reduction potentials for mono- and di-fused derivatives of MTPP(IND)(R)2 and MTPP(IND)2(R)2 where R = Br or H and M = Cu[Formula: see text], Ni[Formula: see text], Zn[Formula: see text] or H2 is carried out in pyridine containing 0.1 M tetrabutylammonium perchlorate (TBAP) as supporting electrolyte and demonstrates how the overall electrochemical properties of these compounds can be tuned by systematic changes in the number of meso-[Formula: see text]fused IND groups on the molecule and the presence or absence of electron-withdrawing Br [Formula: see text]-substituents. Under these solution conditions, two reversible one-electron reductions are seen for H2TPP, while three reversible reductions are obtained for H2TPP(IND) or H2TPP(IND)Br2 and four for H2TPP(IND)2Br2. Multiple reductions also occur for the other investigated mono- and di-fused metalloporphyrins. Plots of measured [Formula: see text] values for the two ring-centered reductions of compounds in a given series vs. the number of fused IND groups are linear and with slopes varying in magnitude between 15 and 230 mV/IND depending upon the product of the electron transfer (anion radical or dianion), the specific central metal ion and the presence or absence of Br substituents on the pyrrole ring opposite the fused IND group(s). It is anticipated that the information from this study can be used for predicting the reduction potentials for yet to be synthesized compounds where a specific redox reactivity is desired.

Development and Investigation of an Organocatalytic Enantioselective [10 + 2] Cycloaddition

A stereoselective [10 + 2] cycloaddition for the reaction of homologated indenecarbaldehydes with α,β-unsaturated aldehydes, providing tetrahydrocyclopenta[a]indenes, has been developed and investi...

Structural, Photophysical, and Electrochemical Properties of Doubly Fused Porphyrins and Related Fused Chlorins.

The electrochemical and physicochemical properties of tetraphenylporphyrins and tetraphenylchlorins with two fused indanedione (IND) or malononitrile (MN) groups and two antipodal Br, Ph, or H β-substituents are investigated in nonaqueous media. These compounds were synthesized by oxidative fusion of free-base trans-chlorins, followed by metalation. The corresponding free-base di-fused chlorins were also isolated as intermediates and characterized for comparisons. The examined di-fused porphyrins (DFP) and di-fused chlorins (DFC) are represented as MDFP(Y)2(R)2 and H2DFC(Y)2(R)2, where M = 2H, CuII, NiII, ZnII, and CoII, Y is a fused indanedione (IND) or malononitrile group (MN), and R = H, Br, or Ph. The IND- and MN-appended compounds in both series exhibit the expected two one-electron oxidations but quite different redox behavior is observed upon reduction, where the free-base IND-appended chlorins show four reversible one-electron reductions, compared to only two for the related free-base MN-appended chlorins. Although porphyrin trianions and tetraanions have been recently described for derivatives with highly electron-withdrawing and/or π-extending substituents, this seems not to be the case for the doubly fused IND-chlorins, where the first two one-electron additions are proposed to be located at the conjugated macrocycle and the last two at the fused IND groups, each of which is reduced at a different potential, consistent with the behavior expected for two equivalent and interacting redox centers. Unlike the examined chlorins, which are all stable in their electroreduced forms, the electrogenerated anionic forms of the di-fused porphyrins are all highly reactive and characterized by cyclic voltammograms having reduction peaks not only for the synthesized compounds added to solution but also for one or more new redox active species formed at the electrode surface in homogeneous chemical reactions following electron transfer. Comparisons are made between electrochemical behavior of the structurally related porphyrins and chlorins and the sites of electron transfer assigned on the basis of known electrochemical diagnostic criteria. One of the compounds, ZnDFP(MN)2, was also structurally characterized as having a ruffled and twisted macrocyclic conformation.

QSAR and Docking Studies of Indene N-Oxide Derivatives as PPARγ Agonists

Indene N-oxide derivatives were used for docking and three dimensional quantitative structure activity relationship studies. Molecular docking and validation studies were carried out for all compounds on peroxisome proliferator activated receptor I³ active site. The reliability of the docking results was acceptable with good root mean square deviation value (ranging from 0.96 to 2A…). The three dimensional quantitative structure activity relationship studies were also carried out by advanced technique (Stepwise forward-backward variable selection method) using training set of 19 compounds and test set of 7 compounds. A statistically reliable model with good predictive power (q2 = 0.8820, Pred r2= 0.7063) was achieved. Both above approaches illustrated insights into the structure activity relationship of these compounds which may helps in the design and development of potent indene N-oxide derivatives as PPARI³ agonists.

N-Channel Organic Semiconductors Derived from Air-Stable Four-Coordinate Boron Complexes of Substituted Thienylthiazoles.

Three acceptor-π-bridge-acceptor (A-π-A) molecules derived from 2-(3-boryl-2-thienyl)thiazole have been synthesized and thoroughly characterized. Incorporation of a B-N unit into thienylthiazole and attachment of suitable acceptor moieties allowed to obtain ambient-stable A-π-A molecules with low-lying LUMO levels. Their potential for applications in organic electronics was tested in vacuum-deposited organic thin film transistors (OTFT). The OTFT device based on boryl-thienylthiazole and 1,1-dicyanomethylene-3-indanone (DCIND) acceptor moieties showed an electron mobility of ≈1.4×10-2 cm2 V-1 s-1 in air, which is the highest electron mobility reported to date for organoboron small molecules. Conversely, the device employing the malononitrile (MAL) derivative as an active layer did not show any charge transport behavior. As suggested by single crystal X-ray analysis of indandione (IND) and MAL derivatives, the enhanced mobility of IND (and DCIND) in comparison to the MAL molecule can be attributed to the effective two-dimensional π-stacking in the solid state imparted by the acceptor moieties with an extended π-surface.

ChemInform Abstract: Coupling of Titanacyclopentadienes with a Cp Ligand and Elimination of One Substituent.

AbstractTrisubstituted indenes are formed from alkynes and Cp2TiCl2 via titanacyclopentadienes in the presence of trimethylphosphine and azobenzene.

High Regio- and Stereo-selective Synthesis of Polysubstituted Alkenes and Indane Derivatives UsingN-Benzylic Sulfonamides as Alkylating Agents

在质子酸H2SO4催化下，含β氢醇与磺酰胺反应可高选择性地得到三取代烯烃和2，3-二氢茚衔生物．含β氮醇酸性条件下脱水后与磺酰胺发生偶联，可以选择性地合成热力学稳定产物Z-多取代烯烃；两者发生[3＋2]环加成反应，则可高选择性地得到2，3-二氢茚衍生物．

Asymmetric Diels-Alder Reaction of 2-Arylidene-1,3-indanediones with 2-Vinylindoles Catalyzed by a Sc(OTf)3/Bis(oxazoline) Complex：Enantioselective Synthesis of Tetrahydrocarbazole Spiro Indanedione Derivatives

报道了Sc(OTf)3/Bis(oxazoline)复合物催化的2-芳基-1,3-茚二酮与2-乙烯基吲哚的不对称Diels-Alder反应,简便、高效的构建了一系列手性四氢咔唑螺茚酮衍生物.通过考察不同的金属盐和手性配体、溶剂、温度等因素对反应的影响,获得了优良的收率(up to 92%yield)和优异的对映选择性(up to 94%ee).该反应条件温和,具有宽广的底物适用范围和较好的官能团兼容性.

ChemInform Abstract: Discovery of 2‐Aminobuta‐1,3‐enynes in Asymmetric Organocascade Catalysis: Construction of Drug‐Like Spirocyclic Cyclohexanes Having Five to Six Contiguous Stereocenters.

AbstractReaction of β‐ketoalkynes (I) and (XI) with indandione (II) and various aldehydes proceeds by a reflexive‐Michael reaction in the presence of a primary amine—benzoic acid catalyst pair to give polyfunctionalized spirocyclic compounds, e.g. (IV), (IX) or (XII), with high to excellent enantioselectivity (up to &lt;99% e.e.).

ChemInform Abstract: Synthesis of Functionalized 1H‐Indenes via Copper‐Catalyzed Arylative Cyclization of Arylalkynes with Aromatic Sulfonyl Chlorides.

AbstractIn addition to a variety of functionalized indenes (18 examples), a bis(indene) and an indacene are prepared.

ChemInform Abstract: Three‐Component Synthesis of New Unsymmetrical Oxindoles via Friedel—Crafts Type Reaction.

AbstractThree‐component reaction of indandione (II) with isatins (I) and dimethylaniline (III) is efficiently catalyzed by LiClO4 to give title oxindoles (IV) in high yields.

ChemInform Abstract: Syntheses with Nitriles. Part 88. Spiro(indole- and Spiro(indene- pyrano(2,3-c)pyrazoles) by Reaction of Cyanomethylene Derivatives with Pyrazolones.

ChemInform Abstract: Syntheses with Nitriles. Part 88. Spiro(indole- and Spiro(indene- pyrano(2,3-c)pyrazoles) by Reaction of Cyanomethylene Derivatives with Pyrazolones.

EIN ÜBERGANG AUS DEM ISOGAMEN IN DEN HETEROGAMEN ZUSTAND IN EINER SIPPE DER OENOTHERA LAMARCKIANA

HereditasVolume 1, Issue 2 p. 213-220 Open Access EIN ÜBERGANG AUS DEM ISOGAMEN IN DEN HETEROGAMEN ZUSTAND IN EINER SIPPE DER OENOTHERA LAMARCKIANA NILS HERIBERT-NILSSON, NILS HERIBERT-NILSSONSearch for more papers by this author NILS HERIBERT-NILSSON, NILS HERIBERT-NILSSONSearch for more papers by this author First published: October 1920 https://doi.org/10.1111/j.1601-5223.1920.tb02460.xCitations: 1AboutPDF ToolsExport citationAdd to favoritesTrack citation ShareShare Give accessShare full text accessShare full-text accessPlease review our Terms and Conditions of Use and check box below to share full-text version of article.I have read and accept the Wiley Online Library Terms and Conditions of UseShareable LinkUse the link below to share a full-text version of this article with your friends and colleagues. Learn more.Copy URL Share a linkShare onFacebookTwitterLinked InRedditWechat Citing Literature Volume1, Issue2October 1920Pages 213-220 ReferencesRelatedInformation

Synthesis and characterization of polyindene synthesized by cationic polymerization of indene using maghnite as catalyst

Dans le present manuscrit, on decrit la synthese du polyindene par polymerisation cationique de l'indene en utilisant la Mag-H qui est une argile de type montmorillonite qui echange avec des protons. L'indene monomere est utilise pour montrer le caractere cationique de la polymerisation. Les effets de la quantite de Mag-H, de la temperature et du temps de reaction sur la conversion de l'indene ainsi que sur les masses molaires sont etudies.

Synthesis of Substituted Indenes from 3‐Phenyl‐2‐propyn‐1‐ol Derivatives.

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

3,4-, 4,7- und 1,4,7-substituierte Indenyl-TiCl3-Komplexe: Synthese und vergleichende Diskussion der Substituenteneinflüsse / 3,4-, 4,7- and 1,4,7-Substituted Indenyl-TiCl3 Complexes: Synthesis and Comparison of Substituent Effects

Me3Si-substituted indenes of type 1-SiMe3-3,4-(CH2)3C9H5 (9), 1-SiMe3-4-R-7-R′C9H5 (11a, R = R′ = Me; 11b, R = R′ = Ph; 11c, R = Me, R′′ = Ph) and 1,1′ -(SiMe3)2-4,7-Me2C9H4 (12) were synthesised as precursors for piano-stool type halfsandwich indenyl-titanium trichloride complexes.Treatment of 9, 11, and 12 with equimolar amounts of TiCl4 gives the complexes (η5-3,4-(CH2)3C9H5)TiCl3 (13), (η5-4-R-7-R′C9H5)TiCl3 (14a, R =R′ = Me; 14b, R =R′= Ph; 14c, R = Me, R′ = Ph), and (η5-1-SiMe3-4,7-Me2C9H4)TiCl3 (15), respectively, with liberation of Me3SiCl.Detailed UV/vis spectroscopic and cyclic voltammetric studies were carried out which allow a comparison of substituent effects in 13 - 15.

Synthesis of substituted indenes from 3-phenyl-2-propyn-1-ol derivatives

Synthesis of substituted indenes from 3-phenyl-2-propyn-1-ol derivatives