- Palladium(II) phthalocyanines efficiently promote phosphine-free Sonogashira cross-coupling reaction at room temperature
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Herein we report that exceptionally simple and inexpensive Pd(II) complexes of phthalocyanines efficiently catalyze direct formation of diphenylacetylenes at ambient conditions with low loading of catalyst (0.5 mol%). Results of this study demonstrate that terminal alkynes reacted mildly with p-substituted aryl bromides at room temperature under Pd and Cu-cocatalysis to give the corresponding phenylacetylenes in yields up to 98%. Also we have examined this catalyst in Sonogashira cross-coupling with aryl chlorides and it was very effective and this reaction at room temperature that there is no examples in recent articles. This protocol represents the first use of palladium phthalocyanine as homogeneous catalyst in the Pd/Cu-promoted Sonogashira reaction. The palladium(II) phthalocyanine complex is significantly more active in Sonogashira cross-coupling between aryl halides and terminal alkynes as compared with traditional catalysts because of absence of palladium black formation through agglomeration of metal particles and deactivation of catalyst.
- Platonova, Yana B.,Tomilova, Larisa G.,Volov, Alexander N.
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- Novel Silylation of Aromatic Nitriles via Photo-induced Electron Transfer
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Photo-induced electron transfer reactions of hexamethyldisilane and aromatic nitriles have been examined; hexamethyldisilane acts as an effective ?-donor, and undergoes novel photochemical silylation of aromatic nitriles.
- Kyushin, Soichiro,Ehara, Yasushi,Nakadaira, Yasuhiro,Ohashi, Mamoru
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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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- Preparation method of aromatic nitrile compound or heteroaromatic nitrile compound
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The invention discloses a preparation method of an aromatic nitrile compound or a heteroaromatic nitrile compound. The preparation method comprises: under the protection of an inert gas, in a solvent,under the actions of a nickel catalyst, a ligand, metal zinc and an additive, carrying out a reaction on a cyanation reagent and halogenated aromatic hydrocarbon or halogenated heteroaromatic hydrocarbon. According to the present invention, by using the inexpensive and easily-available nickel catalyst and the ligand, the halogenated aromatic hydrocarbon or halogenated heteroaromatic hydrocarbon,especially the chlorinated aromatic hydrocarbon or chlorinated heteroaromatic hydrocarbon with characteristics of low price, easy obtaining and low reaction activity can mildly and efficiently react with the cyanation reagent with low toxicity to prepare the aromatic nitrile compound or heteroaromatic nitrile compound; and the preparation method has advantages of simple operation, mildness, high efficiency and the like, and further has characteristics of good functional group compatibility, good universality of substrate and the like.
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Paragraph 0148-0150
(2018/11/03)
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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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- General and Mild Nickel-Catalyzed Cyanation of Aryl/Heteroaryl Chlorides with Zn(CN)2: Key Roles of DMAP
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A new and general nickel-catalyzed cyanation of hetero(aryl) chlorides using less toxic Zn(CN)2 as the cyanide source has been developed. The reaction relies on the use of inexpensive NiCl2·6H2O/dppf/Zn as the catalytic system and DMAP as the additive, allowing the cyanation to occur under mild reaction conditions (50-80 °C) with wide functional group tolerance. DMAP was found to be crucial for successful transformation, and the reaction likely proceeds via a Ni(0)/Ni(II) catalysis based on mechanistic studies. The method was also successfully extended to aryl bromides and aryl iodides.
- Zhang, Xingjie,Xia, Aiyou,Chen, Haoyi,Liu, Yuanhong
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supporting information
p. 2118 - 2121
(2017/04/27)
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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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- Colored Dye for color filter and Preparation method thereof
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The present invention relates to a coloring dye for color filters and a photosensitive resin composition including the same. More specifically, provided are a coloring dye for color filters, which exhibits excellent heat resistance, light resistance, chemical resistance, and high brightness. To this end, a certain ionic substituent capable of increasing solubility such as cyanoacetic acid is added into phthalocyanine, and a strong electron withdrawing group capable of increasing solubility in solvents is substituted. In addition, a light-absorption region is shifted to a blue region. Also, provided is a photosensitive resin composition including the same.
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Paragraph 0116-0120
(2017/02/02)
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- On the trimerization of cyanoacetylene: Mechanism of formation of tricyanobenzene isomers and laboratory detection of their radio spectra
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In support of a deeper understanding of the chemistry of cyanoacetylene-a known constituent of planetary atmospheres and interstellar space-theoretical and experimental studies address the chemical mechanism of dimerization and trimerization, and provide high-resolution rotational spectra of two of the trimeric products, 1,2,3- and 1,2,4-tricyanobenzene. Analysis of the rotational spectra is particularly challenging because of quadrupolar coupling from three 14N nuclei. The laboratory rotational spectra provide the basis for future searches for these polar aromatic compounds in interstellar space by radio astronomy.
- Hopf, Henning,Mlynek, Cornelia,McMahon, Robert J.,Menke, Jessica L.,Lesarri, Alberto,Rosemeyer, Michael,Grabow, Jens-Uwe
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scheme or table
p. 14115 - 14123
(2011/02/22)
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- ESR-investigations on the dynamic solvent effects of degenerate electron exchange reactions. Part I: Cyanobenzenes
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The rates of degenerate electron exchange (electron self-exchange) of various cyanobenzenes have been measured by EPR line broadening technique in nine different solvents at room temperature. The molecules studied comprise besides benzene-1,2-dicarbonitrile, benzene-1,4-dicarbonitrile and benzene-1,2,4,5-tetracarbonitrile, the two isomeric tricyanobenzenes, benzene-1,2,3- tricarbonitrile and benzene-1,2,4-tricarbonitrile, the anion radicals of which have not been characterized before. The experimentally observed rates vary from 4.5 × 108 to 44.0 × 10 8 M-1 s-1 and show the pronounced dependence on the longitudinal relaxation times, τL, of the solvents. The solvent dynamical effect so manifested is confirmed with remarkable clarity using solvents spanning a wide range of τL-values, which comprise acetonitrile (0.2 ps) and o-dichlorobenzene (6.0 ps) at its extremes. The rate constants are compared with Marcus theory using the continuum model (CM) and the mean spherical approximation (MSA) for the outer sphere reorganization energies and Nelson's method for the inner sphere reorganization energies. Furthermore, an estimation of the resonance splitting energies, VRP, is given based on the experimental rates. by Oldenbourg Wissenschaftsverlag.
- Mladenova, Boryana,Kattnig, Daniel R.,Grampp, Guenter
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p. 543 - 563
(2008/02/08)
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- Vapor-phase oxidation and oxidative ammonolysis of some methyl derivatives of biphenyl
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Main pathways arc established of catalytic oxidative transformations of 3,4-di- and 3,3',4,4'-tetramethylbiphenyls in vapor phase. The possibility is analyzed of obtaining the corresponding anhydrides, imides, and nitriles of biphenylcarboxylic acids in yields of up to 59-69%.
- Shapovalov,Koshel',Sembaev,Postnova,Koshel'
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p. 1386 - 1390
(2007/10/03)
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- Synthesis and Properties of Tetra-4-cyano-substituted Metal Phthalocyanines
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Tetra-4-cyanophthalocyanine and its complexes with metals of different valence are prepared, and their optical properties are studied. The IR spectra of the compounds contain an absorption band at 2232 cm-1 due to vibrations of peripheral cyano groups. In the electronic absorption spectra, the bands of the new complexes are located between the corresponding bands of unsubstituted metal phthalocyanines and metal octa-4,5-cyanophthalocyanines. The resistance of the cobalt complex to thermooxidative degradation in air is studied.
- Gavrilin,Shishkina,Shaposhnikov,Maizlish,Kulinich,Smirnov
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p. 1687 - 1690
(2007/10/03)
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- The Effect of Pressure on the Trimerization and Diels-Alder Reaction of Cyanoacetylene. Synthesis and Reactivity of 2,3,5-Tricyanobicyclohexa-2,5-diene ("Tricyano Dewar Benzene")
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The trimerization of cyanoacetylene (1a) and the Diels-Alder reaction of 1a with 1,3-cyclohexadiene (2) show a powerful pressure-induced acceleration which allows the reaction temperature to be reduced from 160 deg C at 1 bar to 40 deg C at 12 kbar or from 100 deg C at 1 bar to room temperature at 7 kbar.At high pressure thermally unstable intermediates like the tricyano Dewar benzene 12 generated in the trimerization of 1a or the primary adduct 3a formed in the Diels-Alder reaction of 1a with 2 were isolated. - Key Words: Diels-Alder reactions / 1,2-Dicyano-1,3-cyclobutadiene / Dewar benzenes / High-pressure reactions
- Breitkopf, Volker,Hopf, Henning,Klaerner, Frank-Gerrit,Witulski, Bernhard,Zimny, Bernd
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p. 613 - 618
(2007/10/02)
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- New Dienophiles and Dienes, III. On the Addition of Cyanoacetylene to Paracyclophane
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Heating a benzene solution of paracyclophane (2) in the presence of excess cyanoacetylene (1b) at 160 deg C in a sealed ampoule provides the novel 2:1-addition product 10, as well as the previously obtained cycloadducts 7-9.It is suggested that these Nenitzescu hydrocarbon systems are formed via the cyclobutadiene intermediates 17 and 18.This hypothesis is supported by the isolation of the side-products 1,2,4- and 1,2,3-tricyanobenzene (11 and 12).When a mixture of 7 and 8 is pyrolyzed at 220 deg C the novel dihydronaphthalene 24 is formed; the mechanism of this isomerization is discussed.The structures of 10 and 24 were confirmed by X-ray structure determination.
- Witulski, Bernhard,Ernst, Ludger,Hopf, Henning,Jones, Peter G.
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p. 2015 - 2022
(2007/10/02)
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- Tetracyanophthalocyaninatoiron(II) with Isocyanides as Axial Ligands
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Tetracyanatophthalocyaninatoiron(II) (CN)4PcFe (2) is obtained by treating 1,2,4-tricyanobenzene (1) with pentacarbonyliron.Aliphatic and aromatic isocyanides RNC (R = tBu, cHx, differently substituted Ph) react with 2 to form the corresponding bisaxially substituted tetracyanophthalocyaninatoiron(II) compounds (CN)4PcFe(CNR)2 (3a-8a).Reaction of 2 with 1,4-diisocyanobenzene (dib), a bidentate bridging ligand, yields the bridged complex n (9a).The spectroscopic and thermal properties of the complexes are described and compared with the analogous compounds PcFe(CNR)2 (3b-8b), TPyPFe(CNR)2 (3c to 8c), and with n (9b). - Key Words: Phthalocyaninatoiron(II) complexes
- Hanack, Michael,Grosshans, Ronald
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p. 1665 - 1672
(2007/10/02)
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- Photoinduced Electron Transfer by Charge-transfer and Singlet-sensitized Activation. Facile Retro-pinakol via Fragmentation of Cation Radicals
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Direct comparison of the efficiency of photoinduced electron transfer by charge-transfer activation of electron donor-acceptor (EDA) complexes and diffusional quenching of excited singlet acceptors is allowed by a series of silylated pinakols derived from the p-methoxytoluene donor.
- Sankararaman, S.,Kochi, J. K.
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p. 1800 - 1802
(2007/10/02)
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- PHOTOCHEMICAL AMINATION OF TETRACYANOBENZENE WITH ACETONITRILE IN THE PRESENCE OF ALIPHATIC AMINE
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Irradiation of dicyanoxylenes and dicyanodurene in acetonitrile in the presence of triethylamine gave mainly substitution and reduction products respectively, whereas a photochemical reaction of 1,2,4,5-tetracyanobenzene in the presence of N-methylpyrrolidine or nicotine gave tricyanoaniline, an amination product, as well as substitution products.
- Yamada, Shuzo,Nakagawa, Yoshiki,Watabiki, Oserojoin,Suzuki, Shin-ichi,Ohashi, Mamoru
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p. 361 - 364
(2007/10/02)
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