- The synthesis of poly-nitrile aromatic and oligopyridine ligands via palladium-catalyzed cyanation of aryl halides
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Modification of Seller's palladium-catalyzed cyanation procedure for simple aromatic halides leads to a versatile and rapid route to complex multi-nitrile aryl and oligopyridyl ligands that improves on known literature methods. By heating the reagents in the high boiling solvent mesitylene to reflux temperatures at ambient pressure, we have observed the conversion of halogenated precursors to the corresponding nitrile compounds. The resulting compounds can be precipitated from CH2Cl2 solutions of the reaction mixtures and isolated as pure compounds in moderate to high yields. The current approach offers a safer alternative to the pressure tube method, as it does not involve the use of KCN at high pressures. Georg Thieme Verlag Stuttgart.
- Veauthier, Jacqueline M.,Carlson, Christin N.,Collis, Gavin E.,Kiplinger, Jaqueline L.,John, Kevin D.
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- Instant Photochromism Caused by Radical Formation in Photocatalytic Decarboxylation of Dihydrothiazole Derivative?
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A pair of new enantiomeric compounds, (R)/(S)-1,3,5-benzene-triyl-2,2',2”-tris(4,5-dihydrothiazole-4-carboxylic acid) (H3LRRR and H3LSSS) are synthesized in one step synthetic route with high yield. Instant photochromism has been investigated to elaborate the photocatalytic decarboxylation of the dihydrothiazole derivative by electron paramagnetic resonance spectroscopy (EPR), photoluminescence (PL), FT-IR, high resolution mass spectra, X-ray photoelectron spectroscopy and UV-Vis spectroscopic techniques. The results indicate that the photochromic transformation is originated from the formation of the radical during the photocatalytic decarboxylation of the 4,5-dihydrothiazole-4-carboxylic acid units.
- Xu, Zhen,Malik, Abaid Ullah,Shu, Mouhai,Cui, Yong
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- Synthesis of poly-nitrile aromatics via palladium-catalyzed cyanation of aryl bromides with potassium hexacyanoferrate(II)
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(Chemical Equation Presented) Modification of Beller's palladium-catalyzed cyanation procedure leads to a versatile and rapid route to poly-nitrile aromatics via easily available aryl bromides that improve on known literature methods. All cyanide ions on the iron(II) center of the non-toxic cyanide source [potassium hexacyanoferrate(II)] can be transferred to the aryl halide using palladium(II) acetate and 1,1′-bis(diphenylphosphino)ferrocen (dppf). Copyright Taylor & Francis Group, LLC.
- Becker, Martin,Schulz, Axel,Voss, Karsten
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- Structural evolution of 2D microporous covalent triazine-based framework toward the study of high-performance supercapacitors
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A series of nitrogen-containing micropore-donimated materials, porous triazine-based frameworks (PTFs), are constructed through the structural evolution of a 2D microporous covalent triazine-based framework. The PTFs feature predictable and controllable nitrogen doping and pore structures, which serve as a model-like system to more deeply understand the heteroatom effect and micropore effect in ionic liquid-based supercapacitors. The experimental results reveal that the nitrogen doping can enhance the supercapacitor performance mainly through affecting the relative permittivity of the electrode materials. Although microspores' contribution is not as obvious as the doped nitrogen, the great performances of the micropore-dominated PTF suggest that micropore-dominated materials still have great potential in ionic liquid-based supercapacitors.
- Hao, Long,Ning, Jing,Luo, Bin,Wang, Bin,Zhang, Yunbo,Tang, Zhihong,Yang, Junhe,Thomas, Arne,Zhi, Linjie
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- Organic molecular material based on benzene ring unit and having long-afterglow effect and preparation method thereof
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The invention discloses an organic molecular material based on benzene ring unit and having long-afterglow effect and a preparation method thereof. The structural formula of the organic material is represented as the specification, wherein Y1 to Y4 are respectively one or two of hydrogen atom and cyano group. By introducing the cyano groups in different number to different sites as electron withdrawing groups, the material has high synthetic efficiency and small molecule. When an excitation source is turned off, the material holds durable luminescence for a couple of seconds and has high fluorescent quantum efficiency. The material has an extensive potential application value in the fields such as anti-counterfeiting, bio-imaging, optic-electronic materials and the like.
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Paragraph 0058-0062
(2020/04/17)
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- Corresponding amine nitrile and method of manufacturing thereof
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The present invention relates to a nitrile manufacturing method, which has characteristics of significantly-reduced ammonia source consumption, low environmental pressure, low energy consumption, low production cost, high nitrile purity, high nitrile yield and the like compared with the method in the prior art, wherein nitrile having a complicated structure can be obtained through the method. The present invention further relates to a method for producing a corresponding amine from the nitrile.
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Paragraph 0135; 0136; 0137; 0140; 0141
(2018/05/24)
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- Immobilization of an Aminobisphosphine–PdII Complex over Graphene Oxide: An Efficient and Reusable Catalyst for Suzuki–Miyaura, Ullmann Coupling and Cyanation Reactions
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The grafting of an aminobis(phosphine)–PdII complex (PNP–PdII) [PdCl2{(Ph2P)2N(CH2)3Si(OMe)3}] (2) on graphene oxide (GO) has been carried out by a condensation reaction between methoxysilane groups of 2 and hydroxyl groups of GO. The composite material was characterized by FTIR spectroscopy, solid-state 31P NMR spectroscopy, SEM, TEM, XPS and ICP-AES techniques. All these tools support the clean immobilization of compound 2 on GO. The composite material showed high catalytic activity in Suzuki–Miyaura, Ullmann coupling and cyanation reactions. The heterogeneity of the composite was confirmed by a hot filtration test. The immobilized PNP–PdII shows comparable activity to its homogeneous analogue 2. The recycling ability of the catalyst was examined for five consecutive runs, which showed little or no reduction in its catalytic efficiency.
- Sengupta, Debasish,Pandey, Madhusudan K.,Mondal, Dipanjan,Radhakrishna, Latchupatula,Balakrishna, Maravanji S.
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p. 3374 - 3383
(2018/05/08)
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- Corresponding amine nitrile and method of manufacturing thereof
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The invention relates to a preparation method of nitrile. Compared with the prior art, the preparation method has the characteristics of obvious reduction of the usage amount of ammonia sources, low environmental pressure, low energy consumption, low production cost, high purity and yields of nitrile products, and the like, and can be used for obtaining nitrile with a more complex structure. The invention also relates to a method for preparing corresponding amine with nitrile.
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Paragraph 0132; 0133; 0134; 0136; 0138
(2018/05/24)
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- Pd-Metalated Conjugated Nanoporous Polycarbazoles for Additive-Free Cyanation of Aryl Halides: Boosting Catalytic Efficiency through Spatial Modulation
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Transition-metal-catalyzed cyanation of aryl halides is a common route to benzonitriles, which are integral to many industrial procedures. However, traditional homogeneous catalysts for such processes are expensive and suffer poor recyclability, so a heterogeneous analogue is highly desired. A novel spatial modulation approach has been developed to fabricate a heterogeneous Pd-metalated nanoporous polymer, which catalyzes the cyanation of aryl halides without need for ligands. The catalyst displays high activity in the synthesis of benzonitriles, including high product yields, excellent stability and recycling, and broad functional-group tolerance.
- Ding, Shunmin,Tian, Chengcheng,Zhu, Xiang,Abney, Carter W.,Tian, Ziqi,Chen, Bo,Li, Meijun,Jiang, De-En,Zhang, Ning,Dai, Sheng
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p. 2348 - 2351
(2017/06/13)
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- Corresponding amine nitrile and method of manufacturing thereof (by machine translation)
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The invention relates to a method of manufacturing one kind of nitrile, compared with the prior art, has significantly reduced the amount of ammonia, the environmental pressure of the small, low energy consumption, low production cost, nitrile product purity and yield and the like, and can obtain more complex structure of the nitriles. The invention also relates to the corresponding amine by the nitrile manufacture method. (by machine translation)
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Paragraph 0134; 0138-0139
(2017/10/22)
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- Molecular Cage Impregnated Palladium Nanoparticles: Efficient, Additive-Free Heterogeneous Catalysts for Cyanation of Aryl Halides
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Two shape-persistent covalent cages (CC1r and CC2r) have been devised from triphenyl amine-based trialdehydes and cyclohexane diamine building blocks utilizing the dynamic imine chemistry followed by imine bond reduction. The cage compounds have been characterized by several spectroscopic techniques which suggest that CC1r and CC2r are [2+3] and [8+12] self-assembled architectures, respectively. These state-of-the-art molecules have a porous interior and stable aromatic backbone with multiple palladium binding sites to engineer the controlled synthesis and stabilization of ultrafine palladium nanoparticles (PdNPs). As-synthesized cage-embedded PdNPs have been characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), and powder X-ray diffraction (PXRD). Inductively coupled plasma optical emission spectrometry reveals that Pd@CC1r and Pd@CC2r have 40 and 25 wt% palladium loading, respectively. On the basis of TEM analysis, it has been estimated that as small as ~1.8 nm PdNPs could be stabilized inside the CC1r, while larger CC2r could stabilize ~3.7 nm NPs. In contrast, reduction of palladium salts in the absence of the cages form structure less agglomerates. The well-dispersed cage-embedded NPs exhibit efficient catalytic performance in the cyanation of aryl halides under heterogeneous, additive-free condition. Moreover, these materials have excellent stability and recyclability without any agglomeration of PdNPs after several cycles.
- Mondal, Bijnaneswar,Acharyya, Koushik,Howlader, Prodip,Mukherjee, Partha Sarathi
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p. 1709 - 1716
(2016/02/20)
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- Single-walled polytetrazolate metal-organic channels with high density of open nitrogen-donor sites and gas uptake
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The self-assembly between zinc dimer and 1,3,5-tris(2H-tetrazol-5-yl) benzene (H3BTT), promoted by a urea derivative, leads to a highly porous 3D framework with a large percentage (67%) of N-donor sites unused for bonding with metals. The material exhibits high gas storage capacity (ca. 1.89 wt % H2 at 77 K and 1 atm; 98 cm3/g CO2 at 273 K and 1 atm), even in the absence of open metal sites. The high percentage of open N-donor sites, coupled with the low framework density resulting from single-walled channels, is believed to contribute to the high uptake capacity.
- Lin, Qipu,Wu, Tao,Zheng, Shou-Tian,Bu, Xianhui,Feng, Pingyun
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supporting information; experimental part
p. 784 - 787
(2012/03/07)
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- Thermolysis of free-radical initiators: tert-butylazocumene and its 1,3- and 1,4-bisazo and 1,3,5-trisazo analogues
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Four tert-butylazocumenes (4-7) were prepared from the corresponding cyanobenzenes, and their nitrogen evolution kinetics and products were analyzed. In combination with TEMPO, the simplest compound, tert-butylazocumene (4), shows promise as a "one-radical" initiator of styrene polymerization. The ABNO-trapped cumyl radical 29 is a particularly stable trialkylhydroxylamine, whose thermolysis half-life is 2.1 h at 150 °C. Taking advantage of this stability, we trapped the cumyl radical centers from 7 to afford tris adduct 32a. While the behavior of the meta bisazoalkane 6 can be mostly predicted from that of 4, the para isomer 5 exhibits both unusual products and kinetics, attributed to the formation of quinodimethane 33 via azo-containing radical 34. In fact, flash vacuum pyrolysis of 5 allowed observation of the 1H and 13C NMR spectra of 33, whose persistence even at ambient temperature showed that this quinodimethane is far more stable than the parent 36. Finally, evidence is presented that 7 is an initiator of star polymerization.
- Engel,Pan,Ying,Alemany
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p. 3706 - 3715
(2007/10/03)
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- Regioselectivity of the photochemical addition of ammonia, phosphine, and silane to olefinic and acetylenic nitriles
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An investigation of the regioselectivity and mechanisms of the photochemical addition of NH3, PH3, and SiH4 to olefinic and acetylenic nitriles is described. The photolysis of NH3 in the presence of acrylonitrile led to the α-addition product 2-aminopropanenitrile (2), propanenitrile, and 2,3-dimethylbutanedinitrile (3). When NH3 was photolyzed in the presence of substituted derivatives (crotononitrile, methacrylonitrile, or 1-cyclohexenecarbonitrile), the α-addition products were still obtained. However, under similar reaction conditions, only the β-addition products, 7 and 8, were obtained from acrylonitrile and PH3, or acrylonitrile and SiH4, respectively. On the other hand, the photolysis of 2-butynenitrile and NH3 gave the β-addition products, (Z)- and (E)-3-aminocrotononitrile (10). The photolysis of these acetylenic nitriles with PH3 or SiH4 also gave the β-adducts (12) and (13). The α-addition of NH3 proceeds by the stepwise addition of H· and ·NH2, respectively, to the α,β-unsaturated nitriles. The β-addition products are formed by a radical chain mechanism initiated by photochemically generated radicals. The radical chain pathway provides an explanation for a number of previously described photochemical additions to olefins and acetylenes. Photochemical processes similar to the addition of ammonia and phosphine to unsaturated organic compounds may have played a role in the evolution of the atmosphere of the primitive Earth, and may even be currently occurring in the atmospheres of other planets.
- Guillemin, Jean-Claude,Breneman, Curt M.,Joseph, Jeffrey C.,Ferris, James P.
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p. 1074 - 1082
(2007/10/03)
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- Tris(triorganostannyltetrazoles): Synthesis and supramolecular structures
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Six trifunctional triorganotin tetrazoles, (R3SnN4CCH2CH2)3C(NO 2) and 1,3,5-(R3SnN4C)3C6H3(R = Me, Et or Bu), have been synthesised by a cycloaddition route from SnR3(N3) and either (NCCH2CH2)3C(NO2) or 1,3,5-(NC)3C6H3 as dipblarophile. The compounds have been characterised by 1H, 13C, 119Sn NMR and 119Moessbauer spectroscopies, while the crystal structures of the tributyltin examples of each series reveal they adopt layered supramolecular arrays.
- Hill, Michael,Mahon, Mary F.,Molloy, Kieran C.
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p. 1857 - 1865
(2007/10/03)
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- Kinetics and mechanism of oxidative ammonolysis of mesitylene on a vanadium-titanium oxide catalyst
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A staged scheme is proposed for the oxidative ammonolysis of mesitylene on a vanadium-titanium oxide catalyst. Numerical values of the rate constants of the stages were found on a computer on the basis of the condition of minimization of the function of deviations between experimental and calculated values of the observed rates with the aid of the conjugate gradient method.
- Vorob'yev,Suvorov
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p. 533 - 539
(2007/10/03)
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- Process for the preparation of a mixture of aminomethylenated glutaconic acid dinitriles
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Aminomethylenated glutaconic acid dinitriles of the formula STR1 in which R1 and R2 independently of one another represent hydrogen, straight-chain or branched C1 -C8 -alkyl, C3 -C8 -alkenyl, C2 -C8 -alkoxyalkyl, C4 -C8 -alkoxyalkenyl, C3 -C8 -cycloalkyl, C6 -C12 -aryl, C7 -C10 -aralkyl or a 5- to 8-membered, saturated or unsaturated heterocyclic ring containing 1 or 2 heteroatoms from the group comprising N, O and S, are obtained by reacting 3-amino-acrylonitriles of the formula STR2 in which the radicals R1 and R2 have the meaning mentioned, with one another at from 0° to 100° C. in the presence of at least 0.5 equivalents of an acidic compound.
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- Photochemical cycloaddition reactions of cyanoacetylene and dicyanoacetylene.
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Photolysis of cyanoacetylene with 185- or 206-nm light yields 1,3,5-tricyanobenzene while 254-nm radiation yields a mixture of tetracyanocyclooctatetraenes, 1,2,4- and 1,3,5-tricyanobenzene. A polymer of cyanoacetylene is the major photoproduct. 1,3,5-Tricarbomethoxybenzene was the only photoproduct identified from the irradiation of methyl propiolate at 254 nm. Mono-, di-, and tricyanobenzenes are formed by irradiation of mixtures of acetylene and cyanoacetylene at 185, 206, and 254 nm along with trace amounts of cyclooctatetraenes. No photoadducts were detected on photolysis of mixtures of cyanoacetylene and CO or HCN. The tetracyanocyclooctatetraene structures were established by UV, MS, and NMR analyses. The 1H NMR of the product mixture exhibited a singlet at delta 7.028 consistent with either 1 or 2 and two singlets at delta 6.85 and 6.91 assigned to 3. Photolysis of mixtures of dicyanoacetylene and acetylene with either 185- or 206-nm light yielded 1,2-dicyanobenzene and (E,Z)-1-buten-3-yne-1,4-dicarbonitrile. These products were also obtained using 254-nm light along with a mixture of tetracyanocyclooctatetraenes. The same three singlets were observed in this product mixture as were observed in the tetracyanocyclooctatetraenes obtained from cyanoacetylene. From this observation it was concluded that the delta 7.02 signal is due to 2 and not 1. The photolysis of cyanoacetylene and dicyanoacetylene in the presence of ethylene with 185-nm light yields 1-cyanocylobutene and 1,2-dicyanocyclobutene, respectively. 2-Cyanobutadiene and 2,3-dicyanobutadiene are the photoproducts with 254-nm light. Reaction pathways are proposed to explain these findings.
- Ferris,Guillemin
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p. 5601 - 5606
(2007/10/02)
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- Method for producing aromatic nitriles
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Aromatic nitriles can be produced in high yields by ammoxidation of an alkyl-substituted aromatic compound in the presence of a catalyst containing oxides of (1) vanadium, (2) antimony and (3) at least one of uranium and chromium, even when concentration of the starting aromatic compound in the starting gas is high or mixing ratio of ammonia to the starting aromatic compound is reduced to the neighborhood of the stoichiometric equivalent.
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