Vinylic MIDA Boronates: New Building Blocks for the Synthesis of Aza‐Heterocycles

A two‐step synthesis of structurally diverse pyrrole‐containing bicyclic systems is reported. ortho‐Nitro‐haloarenes coupled with vinylic N‐methyliminodiacetic acid (MIDA) boronates generate ortho‐vinyl‐nitroarenes, which undergo a “metal‐free” nitrene insertion, resulting in a new pyrrole ring. This novel synthetic approach has a wide substrate tolerance and it is applicable in the preparation of more complex “drug‐like” molecules. Interestingly, an ortho‐nitro‐allylarene derivative furnished a cyclic β‐aminophosphonate motif.     

Mono-Aryl/Alkylthio-Substituted (Hetero)acenes of Exceptional Thermal and Photochemical Stability by the Thio-Friedel–Crafts/Bradsher Cyclization Reaction

The highly substituted mono-aryl/alkylthio-(hetero)acenes prepared in this study have been found to be thermally more stable (T_decomp.=331–354 °C) than the known di-aryl/alkylthio-substituted acenes by an average of 25 °C. They are also much more photostable at 254 and 365 nm (in both argon and air) than the parent anthracene and other reported anthracenes. The most photostable aryl/alkylthio-anthracenes at 254 nm were found to be 60–70 (in air) and 130 (in argon) times more stable in solution than the unsubstituted anthracene, and much more stable than known EDG/EWG-substituted anthracenes (EDG=electron-donating group, EWG=electron-withdrawing group) with an extended aromatic core. Furthermore, the acenes showed significantly higher photostability at 365 nm in both air and argon. The anthracenes were obtained by the novel thio-Friedel–Crafts/Bradsher cyclization reaction of hitherto unknown [o-(1,3-dithian-2-yl)aryl](aryl)methyl thioethers. The developed approach provides a general access to mono-aryl/alkylthio-substituted (hetero)acene frameworks containing at least three fused (hetero)aromatic rings. The characteristic feature of this approach, which leads to highly substituted acenes, is that the substituents, unlike in other methods, may be introduced at an early stage of the synthesis. DFT and TD-DFT calculations confirmed the stabilizing role of the aryl/alkylthio substituent in the mono-aryl/alkylthio-substituted anthracenes, which are the most stable anthracenes prepared to date. Their high photostability is mainly due to the quenching of singlet oxygen by the acene and the quenching of the acene S₁ state by molecular oxygen.     

Room-Temperature,Metal-Free,and One-Pot Preparation of 2H-Indazoles through a Mills Reaction and Cyclization Sequence

The Mills reaction and cyclization of readily available 2-aminobenzyl alcohols and nitrosobenzenes using thionyl bromide provided 2H-indazoles in up to 88 % yields. In the metal-free process, acetic acid played a crucial role for the both Mills reaction and cyclization. A brominated 2H-indazole could also be obtained through the one-pot sequence.     

Fluoroalkylation of aromatics: An intramolecular radical cyclization of 4-chloro-1,1,2,2,3,3,4,4-octafluorobutylbenzenes

In the presence of sodium dithionite and DMSO, the intramolecular radical cyclization of 4-chloro-1,1,2,2,3,3,4,4-octafluorobutylbenzenes is achieved to give the corresponding cyclic compounds in moderate to good yields.     

Photochemical attachment of polymers on planar surfaces with a covalently anchored monolayer of a novel naphthyl ketone photochemical radical generator

A monolayer of covalently anchored, novel, binaphthyl ketone is used as a surface‐confined photochemical radical generator (PRG) for anchoring a variety of polymers to silicon surfaces. The precursor PRG is synthesized by the application of a facile and novel method for the oxidation of sterically hindered benzylic hydrocarbons to carbonyl compounds. Oxidation was carried out with a stoichiometric amount of potassium peroxydisulfate, in the presence of a catalytic amount of copper sulfate in an acetonitrile/water mixture. The PRG synthesized is characterized by ¹H NMR, UV, and Fourier transform infrared (FTIR). The covalently attached monolayers are characterized by X‐ray photoelectron spectroscopy, ellipsometry, and water contact angle measurements. The method developed is applicable to the preparation of a monolayer of a variety of polymers on a wide range of substrates carrying surface hydroxyl groups. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5413–5423, 2004     

Synthesis of latonduine derivatives via intramolecular Heck reaction

The synthesis of indole ring-fused benzazepinone series as latonduine derivatives has been developed via an intramolecular Heck reaction. The scope has been enlarged not only to indole moiety but also to pyrrolo and benzo[b]thiophene nuclei. Several derivatives prepared have been evaluated in vitro for their antiproliferative activities on breast cancer cell lines. Some of them showed promising cytotoxic activities.     

4-Hydroxy-2-quinolones. 93. Synthesis and biological properties of 2-hydroxy-4-imino-1,4-dihydroquinoline-3-carboxylic acid N-R-amides

Various methods of synthesizing amides of 2-hydroxy-4-imino-1,4-dihydroquinoline-3-carboxylic acids have been studied. Results of investigations on the antitubercular and antiinflammatory activity of the obtained compounds are discussed. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 542–555, April, 2006.     

Spherical dye-doped silica particles

Organic dyes such as water soluble porphyrins were incorporated into monodispersed SiO₂ particles using the sol-gel technique (the Stober synthesis) and their monomeric and dimeric properties were investigated by aiming at the microcavity effect. Doping efficiencies of dyes into SiO₂ particles depended on dye's hydrophilic properties. The doping efficiency of a porphyrin, TTMAPP, decreased with increasing the nominal content in the starting solution and the doping content showed the maximum value of 1.6×10^–5 mol/g SiO₂. With increasing the TTMAPP content, spectra of doped particles were changed from dimeric to monomeric nature; the absorption peak due to dimers disappeared and halfwidth of absorption at Soret band decreased. This unusual change was caused by the decrease of particle sizes by dye doping. The TTMAPP-doped sample having monomeric spectrum showed the fluorescence life time of 8.5 nsec and photochemical hole burning at about 5 K.