- Synthesis, characterization, and some reactions of the tricarbonylchromium complexes of 1,3-indandione and ninhydrin
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The syntheses and characterization of the tricarbonylchromium complexes of 1,3-indandione and ninhydrin are described. As the direct complexation proved unsuccessful, the acetal route was tried. Although some complexes were obtained, complex deacetalization did not work in the case of ninhydrin. Finally, the oxidation of tricarbonyl(η6-1,3-indandione)chromium(0) with dimethyldioxirane gave the ninhydrin complex in 75% yield in equilibrium with the indantrione complex. The latter reacts in hetero Diels-Alder reactions with dienes with diastereoselective formation of spiro anellated pyran derivatives.
- Leinweber, Dirk,Wartchow, Rudolf,Butenschoen, Holger
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- One-step stereoselective synthesis of dialkyl 1,1-diacetyl-8a-hydroxy-8- oxo-1,2,8,8a-tetrahydrocyclopenta[a]indene-2,3-dicarboxylates from the reaction of dialkyl 2-(1-acetyl-2-oxopropyl)-3-(tributylphosphoranylidene) succinates with indene-1,2,3-trione
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Protonation of the highly reactive 1:1 intermediates produced in the reaction between tributylphosphine and dialkyl acetylenedicarboxylates by acetylacetone leads to sterically congested phosphorus ylides that undergo an intermolecular addition reaction with indene-1,2,3-trione and concomitant intramolecular Wittig reaction in CH2Cl2 at room temperature to produce dialkyl 1,1-diacetyl-8a-hydroxy-8-oxo-1,2,8,8a- tetrahydrocyclopenta[a]indene-2,3-dicarboxylates in fairly good yields. Copyright Taylor & Francis Inc.
- Ramazani, Ali,Ahmadi, Ebrahim,Noshiranzadeh, Nader
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- Total 2p? Spin Density Mapping as a Function of Hydrogen Bonding Involving an Anion Radical
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EPR spectra will utilized to generate a "map" of the 2p? spin density distribution in the indanetrione anion radical as a function of hydrogen bond formation between this anion radical and water. 17O substitution followed by computer simulation of natural abundance 13C splittings and enriched 17O splittings allowed measurements of the spin densities on each atom of the radical.The four observable 13C hyperfine splittings were found to vary upon hydrogen bond formation, and the equilibrium constant for hydrogen bonding (C9H4O3.- + HOH = C9H4O3.-...HOH) could be evaluated from the variation in these splittings.However, the 2p? spin densities on only three of the seven nonequivalent positions are perturbed.The 2p? spin densities on the two oxygen atoms are invariant even though the formation of the hydrogen bond involves the oxygen atoms.
- Reiter, Richard C.,Stevenson, Gerald R.,Wang, Zhong Yi
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- Design, synthesis, and characterization of oxadiazolopyrazine analogs with application as anticancer agents
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Here, we describe the synthesis and evaluation of a class of cell-permeable indeno-oxadiazolopyrazine analogs as the anticancer agents. A new and facile approach to the synthesis of substituted analogs of indeno-oxadiazolopyrazine is illustrated. We find that the designed indeno-oxadiazolopyrazines, 3, 4, 10, 11, 15, and 16, act as potent anticancer agents compared to camptothecin, topoisomerase I inhibitor. These observations suggest that the electron-donating group (methoxy) at the C-5, C-6, and C-8 positions or electron-withdrawing group (fluoro) at the C-6 and C-7 positions on the A ring of indeno-oxadiazolopyrazines is required for antiproliferative activities against MDA-MB-231, BT549, and MCF7 cell lines.
- Chang, Tzu-Ting,Chen, Chia-Ling,Chen, Wei-Chia,Chen, Wei-Sheng,Hsieh, Feng-Chun,Li, Wen-Shan
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- Diastereoselective synthesis of novel spiro indanone fused pyrano[3,2-: c] chromene derivatives following hetero-Diels-Alder reaction and in vitro anticancer studies
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The development of concise methods for the synthesis of small functionalised spirocyclic molecules is important in the search of new bioactive molecules. To contribute this, here we represent a diastereoselective oxa-hetero-Diels-Alder reaction for the synthesis of novel spiro indanone fused pyrano[3,2-c]chromene derivatives and studied their in vitro anticancer activities. Using previously less explored cyclic ketone i.e. indane-1,3-dione and 3-vinyl-2H-chromene derivatives, we obtained novel spiro-heterocyclic frameworks at the interphase between "drug-like" molecules and natural products. Various spiro indanone fused pyrano[3,2-c]chromene derivatives were synthesized regiospecifically bearing a quaternary stereocenter in high yields (up to 85%) with excellent diastereoselectivity in toluene using 4 ? MS as additive under reflux condition at 120 °C. In vitro cytotoxic studies of these compounds against MCF-7 (breast cancer), HCT-116 (colon cancer), H-357 (oral cancer), MD-MB-231(Breast cancer) cell lines were evaluated by MTT {3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide} assay in vitro. The screening results revealed that many of the compounds are showing moderate to high levels of anticancer activities against the tested cancer cell lines and some displayed potent inhibitory activities in comparison to the commercial anticancer drug 5-fluorouracil (5-FU). Among the series, compound 3′c showed most potent cytotoxicity (15.0-27.5 μM) in three cancer cell lines (MCF-7, HCT-116 and MD-MB-231).
- Panda, Pravati,Nayak, Sabita,Sahoo, Susanta Ku.,Mohapatra, Seetaram,Nayak, Deepika,Pradhan, Rajalaxmi,Kundu, Chanakya Nath
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p. 16802 - 16814
(2018/05/23)
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- Facile synthesis of 1,2,3-tricarbonyls from 1,3-dicarbonyls mediated by cerium(IV) ammonium nitrate
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A mild and efficient protocol for the synthesis of vicinal tricarbonyl compounds from β-dicarbonyls in a single step using cerium(IV) ammonium nitrate as a catalytic oxidant is described. Ease of execution, wide substrate scope and the suitability for the synthesis of commercially important compounds like ninhydrin, alloxan and oxoline make this reaction particularly noteworthy.
- Sivan, Akhil,Deepthi, Ani
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supporting information
p. 1890 - 1893
(2014/03/21)
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- Photolysis of indan-l,2-dione derivatives in oxygen-doped argon matrix at low temperature
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Photolysis of indan-l,2,3-trion (la), benzo[ft]furan-2,3-dione (lb), and N-methylisatin (1c) in argon matrix either with or without oxygen at 10 K was investigated by IR spectroscopy in combination with DFT calculations. The results indicate that while 1a and 1b gave the products mixture as a result of α-cleavage, followed by decarbonylation, 1c was rather photostable under similar conditions. However, when the irradiation was carried out in argon matrix doped with 20% oxygen, 1c decomposed much more efficiently than that in argon matrix and cyclic diacyl peroxide presumably formed by trapping of initial diradical originating from α-cleavage by molecular oxygen was detected. Similar irradiation of 1b also gave cyclic diacyl peroxide along with photodecarbonylation products, but irradiation of 1a in oxygen-doped matrix produced not only cyclic diacyl peroxide but also products as a result of oxidation of photodecarbonylation product. The present observation reveals that photolysis of ketones in oxygen-doped matrix at low temperature provides useful information concerning the reactivities of ketones toward α-cleavage.
- Itoh, Takayoshi,Tatsugi, Jiro,Tomioka, Hideo
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experimental part
p. 475 - 481
(2009/08/07)
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- Ozonolysis of enol ethers. Part 10. Ozonization of enol ethers from 1,2- and 1,3-dicarbonyl compounds: Direct quantitative synthesis of phthalonic acid anhydride
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The results of ozonolyses of enol ethers from 1.2- and 1.3-dicarbonyl compounds presented here strongly indicate that these reactions do not proceed via the established Criegee ozonolysis mechanism for nucleophilic C=C bonds. The quantitative one-step synthesis of phthalonic acid anhydride via ozonolysis of 2-(methoxymethyliden)-1H-inden-1.3(2H)-dione (28a) is described. Furthermore, a revision of the theory of alkene ozonolysis in the presence of tetracyanoethylene (TCNE) is proposed on the basis of a single-electron-transfer (SET) chemistry.
- Schank, Kurt,Beck, Horst,Pistorius, Susanne
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p. 2025 - 2049
(2007/10/03)
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- A convenient one-pot synthesis of Indane-1,2,3-triones by oxidation of indan-1-ones with N-bromosuccinimide-dimethyl sulfoxide reagent
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Indane 1,2,3-triones (2(a-f)) have been synthesized via brommation of indan-1-ones (1(a-f)), followed by oxidation of the resulting brominated indan-1-ones with dimethyl sulfoxide in one pot in good yields.
- Tatsugi, Jiro,Izawa, Yasuji
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p. 859 - 864
(2007/10/03)
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- Photochemical behavior of indane-1,2,3-trione in degassed alcoholic solutions: Formation of 3-substituted phthalides
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Irradiation of indane-1,2,3-trione in degassed alcoholic solutions affords 3-alkoxycarbonylphthalides as the major product together with 3-alkoxyphthalides. 3-Alkoxycarbonylphthalides may be derived from the reaction between alcohols and the spirooxiranone intermediate, generated photochemically by cleavage of the bond between two carbonyl groups of indane-1,2,3-trione via a cyclobutenone biradical derivative.
- Tatsugi, Jiro,Hara, Tomoaki,Izawa, Yasuji
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p. 177 - 178
(2007/10/03)
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- The Hydration of 1,2,3-Indanetriones and Related Triones
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A series of 5-mono- and 5,6-di-substituted 1,2,3-indanetriones, 1,2,3(2H)-phenalenetrione and 1,3-diphenyl-1,2,3-propanetrione have been shown to form 2,2-dihydroxy-1,3-dione hydrates.The rates for the uncatalysed hydrations has been measured at three temperatures and activation paramaters evaluated.The kinetic role of water and solvent isotope effects have been studied.The Hammett reaction constant, ρ, for the uncatalysed hydration of the substituted 1,2,3-indanetriones in 96.7percent (v/v) dioxane-water at 25 deg C was found to be ca. 1.05.The structure of the transition state for the hydration has been discussed and shown to involve two molecules of water, one acting as a nucleophile and the other as a general acid-base catalyst transferring protons.
- Bowden, Keith,Rumpal, Sanjay
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p. 355 - 374
(2007/10/03)
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- Copper mediated conversion of nitro compounds to aldehydes or ketones by dioxygen
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Primary and secondary nitro compounds are easily transformed to aldehydes or ketones by dioxygen catalyzed by metallic copper.
- Balogh-Hergovich, Eva,Kaizer, Jozsef,Speier, Gabor
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p. 573 - 574
(2007/10/03)
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- The Conversion of α-Bromo-β-Dicarbonyls to Vicinal Tricarbonyls Using Dimethyldioxirane and Base
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Vicinal tricarbonyls are prepared from α-bromo-β-dicarbonyl precursors by base promoted oxygen transfer from dimethyldioxirane.The α-bromo-β-dicarbonyls were prepared by the reaction of CuBr2 and benzene (Koser's reagent) with a β-dicarbonyl system.
- Coats, Steven J.,Wasserman, Harry H.
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p. 7735 - 7738
(2007/10/02)
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- Amides of 4-oxo-azetidine-2-sulfonic acids and salts thereof, processes for their preparation and their use
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The invention relates to the novel 4-oxo-azetidine-2-sulfonic acid amides and their salts of the formula I STR1 wherein the radicals have the meanings: R1 =hydrogen, halogen; R2 =hydrogen, halogen, NH2, C6 H5 CH2 CONH, C6 H5 OCH2 CONH, phthalimido, o-MeNHCOC6 H4 CONH, isoxazolylcarbonylamino; R3 =hydrogen, Me2 C=C--COOMe, H2 C=C(Me)--CH--COOMe, Me2 C=C--COOCH2 C6 H5, H2 C=C(Me)CH--COOCH2 C6 H4 NO2 -p, Me2 C=C--COOCH2 C6 H4 NO2 -p, Me2 C=C--COOCH2 C6 H4 Me-m, H2 C=C(Me)--CH--COOCH2 C6 H4 Me-m, Me2 C=C--COOH; R4 =hydrogen or sodium and R5 =hydrogen, alkyl, benzyl or heterocycle, i.e. isoxazole or pyrazole etc. The invention also relates to the procedure for the preparation thereof and the use thereof as intermediates in the synthesis of beta-lactam analogs or as active components for the preparations of the drugs for antimicrobial therapy.
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- Ene Reactions of Indane-1,2,3-trione (a Super-enophile) and Related Vicinal Tricarbonyl Systems
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Indane-1,2,3-trione 1 is conveniently prepared in quantitative yield by the azeotropic drying of ninhydrin 2 using chlorobenzene as solvent.The central C=O group of the trione is extremely electrophilic and ene addition occurs at this site with a wide range of alkenes and with terminal alkynes in aprotic solvents at moderate temperatures (70-130 deg C).The reactivity of trione 1 is somewhat attenuated by the solvent, and the ene additions are consistently faster in chloroform than in tetrahydrofuran.Stereoselectivity, when relevant, appears largely to be dictated bysteric factors.Regiochemical control can be exercised if the ene contains two reaction sites.Isoprene and 2,4-dimethylpenta-1,3-diene, however, react by Diels-Alder rather than by ene addition; the adducts are the expected regioisomers 18 and 20, respectively.Attempts to catalyse the ene reactions with Lewis acids were unsuccessful.The analogous ene reactions of 4,4,5,5-tetramethyl-cyclopentane-1,2,3-trione 44, 4,4,6,6-tetramethylcyclohexane-1,2,3-trione 45, and 2,2-dimethyl-1,3-dioxane-4,5,6-trione ('oxo-Meldrum's acid') 46 were also briefly investigated.
- Gill, G. Bryon,Idris, Muhammad S. Hj.,Kirollos, Kirollos S.
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p. 2355 - 2366
(2007/10/02)
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- Singel-Oxygen Photolysis of Dihaloketones. A Facile and Efficient Approach to Vicinal Triketones and Their Monohydrates
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The preparation of vic-triketones and/or their monohydrates by sensitized photooxidation (singlet oxygen) of gem-dihaloketones and/or vic-dihaloketones is described; some reaction mechanisms are discussed.
- Mahran, M. Refat,Abdou, Wafaa M.,Sidky, Mahmoud M.,Wamhoff, Heinrich
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p. 506 - 508
(2007/10/02)
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- Hydrated Oxocarbons,IV. Silylation of 1,1-Dihydroxy Compounds.
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The action of various silylating agents on mono- and polyvicinal 1,1-dihydroxy compounds has been investigated.Some of these reagents converted ninhydrin (2) and rhodizonic acid (17) into the corresponding geminal bis(trimethylsilyloxy) derivatives 1 and 20, respectively.Compound 1 readily fragments to form hexamethyldisiloxan and indantrione (4).The rhodizonic acid derivative 20 is, however, rather stable and even on pyrolysis at 500 deg C gives only traces of the tetraketone 21.With other silylating agents unexpected C-alkylation or C-amidation at the dihydroxy carbon is observed.Silylation of perhydroxycyclobutane and -cyclohexane leads to ring opened and contracted products.
- Yalpani, Mohamed,Wilke, Guenther
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p. 661 - 669
(2007/10/02)
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- Introduction of Oxygen Functions into the α-Position of β-Diketones, 8. Ozonolysis of Sulfonium Ylides
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(Dimethylsulfonio)diacylmethanides 1, prepared by known methods, are cleaved by equimolar amounts of ozone in aprotic medium yielding vicinal triketones 2 and DMSO.Peroxydic reaction products are not detectable.
- Schank, Kurt,Schuhknecht, Christoph
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p. 3032 - 3041
(2007/10/02)
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- INFLUENCE OF STRUCTURE OF SOME AZO COMPOUNDS ON THEIR ACID-BASE PROPERTIES AND REDUCTION
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A series of azo compounds were prepared and their acid-base equilibria in aqueous-alcoholic solutions were studied in dependence on the pH.The oxidation-reduction properties of the compounds and of their reduction products were examined polarographically and by preparative electroreduction.The effect of substituents at the azo group on the examined properties of the compounds is discussed.
- Madajova, Vlasta,Zelensky, Imrich
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p. 987 - 1001
(2007/10/02)
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- Kinetics and Thermodynamics of Ion Pair Dissociation to Yield Free Solvated Ions. Effect of Steric Hindrance
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The kinetics and thermodynamics of ion pair dissociation involving the anion radicals of ninhydrin, nitrobenzene, and trialkyl-substituted nitrobenzenes ion associated with Na+, K+, Cs+, or (Bu)4N+ in hexamethylphosphoramide (HMPA) were studied via ESR spectroscopy.The large alkyl groups on the (Bu)4N+ cation were found to sterically inhibit the close approach of the positive nitrogen to the anion radical.However, this loose ion pair dissociates less exothermically and exoenergetically than tighter ion pairs involving the other cations due to the poorer solvation of this large cation by the HMPA.The alkyl groups in the ortho positions of the nitrobenzene anion radical also prevent close approach of a solvated cation to yield intimate ion pairs.These loose ion pairs have lower free energies of activation for ion pair disociation.The observed rates and thermodynamics of ion pair dissociation and formation are explained in terms of ion solvation and steric inhibition to ion association.
- Kokosinski, Jeanette D.,Forch, Brad E.,Stevenson, Gerald R.,Echegoyen, Luis,Castillo, Carlos A.
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p. 793 - 798
(2007/10/02)
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- On Ruhemann's Purple
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The 1H nmr spectrum previously reported for Ruhemann's Purple is shown to be inconsistent with the accepted structure of this material.The discrepancy with the reported 1H nmr spectrum is shown to be due to the presence of a major impurity, identified as hydrindantin.Spectra (1H nmr, 13C nmr, ir, uv-visible) of Ruhemann's Purple , its protonated analogue DYDA, and other ninhydrin relatives are reported, and structural conclusions are based on these spectral data.
- Wigfield, Donald C.,Buchanan, Gerald W.,Croteau, Stephen M.
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p. 201 - 205
(2007/10/02)
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