626-44-8Relevant academic research and scientific papers
Preparation of Functionalized Diorganomagnesium Reagents in Toluene via Bromine or Iodine/Magnesium-Exchange Reactions
Desaintjean, Alexandre,Danton, Fanny,Knochel, Paul
supporting information, p. 4461 - 4476 (2021/08/13)
A wide range of polyfunctionalized di(hetero)aryl- and dialkenyl-magnesium reagents are prepared in toluene within 10 to 120 minutes between 78 C and 25 C via an I/Mg- or Br/Mg-exchange reaction using reagents of the general formula R2Mg (R = sBu, Mes). Highly sensitive functional groups, such as triazene or nitro, are tolerated in these exchange reactions, enabling the synthesis of various functionalized (hetero)arene and alkene derivatives after quenching with several electrophiles including allyl bromides, acyl chlorides, aldehydes, ketones, and aryl iodides.
Copper-Free Sonogashira Coupling for High-Surface-Area Conjugated Microporous Poly(aryleneethynylene) Networks
Trunk, Matthias,Herrmann, Anna,Bildirir, Hakan,Yassin, Ali,Schmidt, Johannes,Thomas, Arne
supporting information, p. 7179 - 7183 (2016/05/24)
A modified one-pot Sonogashira cross-coupling reaction based on a copper-free methodology has been applied for the synthesis of conjugated microporous poly(aryleneethynylene) networks (CMPs) from readily available iodoarylenes and 1,3,5-triethynylbenzene. The polymerization reactions were carried out by using equimolar amounts of halogen and terminal alkyne moieties with extremely small loadings of palladium catalyst as low as 0.65 mol %. For the first time, CMPs with rigorously controlled structures were obtained without any indications of side reactions, as proven by FTIR and solid-state NMR spectroscopy, while showing Brunauer-Emmett-Teller (BET) surface areas higher than any poly(aryleneethynylene) network reported before, reaching up to 2552 m2 g-1. A modified one-pot Sonogashira cross-coupling reaction based on a copper-free methodology has been applied for the synthesis of conjugated microporous polymers (CMPs). Not only are the resulting structures much more defined than previously published materials, but they also show far superior Brunauer-Emmett-Teller (BET) surface areas of up to 2552 m2 g-1, setting a new record for this type of materials (see scheme).
Size-controlled synthesis of conjugated polymer nanoparticles in confined nanoreactors
Deng, Sheng,Zhi, Jian,Zhang, Xianmei,Wu, Qingqing,Ding, Yun,Hu, Aiguo
supporting information, p. 14144 - 14148 (2015/02/19)
Soluble conjugated polymeric nanoparticles are synthesized by Suzuki-type polycondensation of two monomers (Ax + By, x>2, y≥2) in the channel of ordered mesoporous silica-supported carbon nano-membranes (nanoreactors). These synthesized soluble conjugated microporous polymers (SCMPs) exhibit uniform particle-size distributions and well-controlled particle sizes. The control of particle size stems from the fact that the polycondensations exclusively take place inside the mesochannels of the nano-reactors. Photo-luminescence studies show that polymeric nanoparticles with tetraphenylethene and pyrene substructures are highly fluorescent. The combination of both physical stability and process-ability offered by the soluble polymeric nanoparticles makes them particularly attractive in light emitting and other optoelectronic applications.
Polyfluorinated functionalized m-terphenyls. New substituents and ligands in organometallic synthesis
Olaru, Marian,Beckmann, Jens,Rat, Ciprian I.
, p. 3012 - 3020 (2014/07/08)
The synthesis and structural characterization of polyfluorinated arenes 2,4,6-(C6F5)3C6H2X and 2,6-(C6F5)2-4-BrC6H2X (X = NO2, Cl, Br) obtained in the Ullmann-type cross coupling reaction is reported. The nitro derivatives were reduced to the aromatic amines. The α-diimine [2,4,6-(C6F5)3C 6H2NCMe]2 and 2,4,6-(C6F 5)3C6H2I were obtained in condensation and Sandmeyer reactions, respectively, from the corresponding amine. The syntheses of 2,4,6-(C6F5)3C 6H2NHC(O)H, 2,4,6-(C6F5) 3C6H2NC, and 2,4,6-(C6F 5)3C6H2Si(X)Me2 (X = H, F, Cl) are also described.
Optically active, amphiphilic poly(meta -phenylene ethynylene)s: Synthesis, hydrogen-bonding enforced helix stability, and direct AFM observation of their helical structures
Banno, Motonori,Yamaguchi, Tomoko,Nagai, Kanji,Kaiser, Christian,Hecht, Stefan,Yashima, Eiji
supporting information; experimental part, p. 8718 - 8728 (2012/06/30)
Optically active, amphiphilic poly(meta-phenylene ethynylene)s (PPEa) bearing l- or d-alanine-derived oligo(ethylene glycol) side chains connected to the backbone via amide linkages were prepared by microwave-assisted polycondensation. PPEa's exhibited an intense Cotton effect in the π-conjugated main-chain chromophore regions in various polar and nonpolar organic solvents due to a predominantly one-handed helical conformation stabilized by an intramolecular hydrogen-bonding network between the amide groups of the pendants. The stable helical structure was retained in the bulk and led to supramolecular column formation from stacked helices in oriented polymer films as evidenced by X-ray diffraction. Atomic force microscopy was used to directly visualize the helical structures of the polymers in two-dimensional crystalline layers with molecular resolution, and, for the first time, their absolute helical senses could unambiguously be determined.
Facile aromatic finkelstein iodination (AFI) reaction in 1,3-dimethyl-2-imidazolidinone (DMI)
Yamashita, Ken-Ichi,Tsuboi, Michihiro,Asano, Motoko S.,Sugiura, Ken-Ichi
experimental part, p. 170 - 175 (2011/11/29)
In this communication, we report the superior role of 1,3-dimethyl-2- imidazolidinone (DMI) as a solvent for aromatic Finkelstein iodination (AFI), the conversion of aryl bromides to aryl iodides. DMI accelerates the reaction rate and affords product(s) that could not be prepared using previous methods. Our findings for AFI avoid the use of toxic solvents such as N,N-dimethylformamide and hexamethylphosphoramide. Taylor & Francis Group, LLC.
Synthesis of oligosilyldi- and trianions
Mechtler, Christian,Zirngast, Michaela,Gaderbauer, Walter,Wallner, Andreas,Baumgartner, Judith,Marschner, Christoph
, p. 150 - 158 (2007/10/03)
1,3- and 1,4-Bis[tris(trimethylsilyl)silylethynyl]benzenes as well as 1,3,5-tris[tris(trimethylsilyl)silylethynyl]benzene were synthesized employing Sonogashira cross-coupling conditions. All three molecules underwent facile di- or trimetalation with potassium tert-butoxide to afford the respective oligosilyldi- and trianions.
Oligofunctional amphiphiles featuring geometric core group preorganization: Synthesis and study of Langmuir and Langmuir-Blodgett films
Mueller, Petra U.,Weber, Edwin,Rheinwald, Gerd,Seichter, Wilhelm
, p. 3757 - 3766 (2007/10/03)
Based on the principle of supramolecular preorganization, a new type of oligofunctional amphiphile, of which compounds 1-4 are representative structures, has been designed and synthesized. The typical feature of their structure is a highly rigid and geometrically well-defined central unit composed of ethynylene substituted aromatic spacers with different numbers of amphiphilic segment groups (also of a rigid geometric design) attached to it. The molecules form well-defined Langmuir films when spread from a solution at the air/water interface or when a 10-4 M aqueous CaCl2 solution was used as the subphase. By analysis of the surface pressure-surface area (π-A) isotherms, information on the packing behavior and orientation of the amphiphilic molecules depending on the molecular structure could be obtained. Morphological characterization of the dynamic process of monolayer compression at the air/water interface was carried out by Brewster angle microscopy, illustrating several phase states visualized as snap shots. Thin monolayer films produced on a 10-4 M aqueous CaCl2 subphase can be transferred to a mica solid support by the Langmuir-Blodgett technique. Tapping mode atomic force microscopy reveals a surface topography of the monofilms composed of 1 and 3 that differ in roughness and also in the properties of elasticity, hardness and adhesive strength. X-Ray crystal structure analysis of three relevant intermediate compounds of the synthesis were successfully determined giving an indication of the potential structural features inherent in the new amphiphiles. The Royal Society of Chemistry 2005.
Synthesis of diiodo- and triiodoanilines by iodination of aniline with potassium dichloroiodate and preparation of 1,3,5-triiodobenzene
Vatsadze,Titanyuk,Chernikov,Zyk
, p. 471 - 473 (2007/10/03)
A new chemoselective procedure was developed for the synthesis of 2,4,6-triiodoaniline and 2,4-diiodoaniline by the reaction of aniline with potassium dichloroiodate in dilute HCl. Subsequent deamination of 2,4,6-triiodoaniline afforded 1,3,5-triiodobenzene in good yield.
Synthesis of nanostructures based on 1,4- and 1,3,5-ethynylphenyl subunits with π-extended conjugation. Carbon dendron units
Gonzalo Rodriguez,Esquivias, Jorge,Lafuente, Antonio,Diaz, Cristina
, p. 8120 - 8128 (2007/10/03)
Nanometer-sized conjugated 1,4- and 1,3,5-ethynylphenyl oligomers were synthesized starting from 3,5-di(trimethylsilylethynyl)phenylacetylene and p-[3,5-di(trimethylsilylethynyl)-1-ethynylphenyl]-phenyl acetylene by cross-coupling reaction with a convenient haloaryl derivative, catalyzed by palladium(II)/copper(I), in excellent yield. The terminal acetylenes were efficiently prepared by a specific protection-deprotection methodology. All ethynylphenyl homologues obtained show fluorescence emission, with the bathochromic shift of approximately 20 nm by each ethynylphenyl unit increasing the conjugate chain. Parallel conjugated ethynylphenyl chains were prepared through the insertion of a 1,5-naphthalene subunit, and the compounds exhibit fluorescence radiation emission.
