91-15-6Relevant articles and documents
Polyfunctionalized Cage Compounds by Pericyclic Domino Processes of 4,5-Dicyanopyridazine with Dienes: Applications and Limits
Giomi, Donatella,Nesi, Rodolfo,Turchi, Stefania,Mura, Elena
, p. 360 - 364 (2000)
The title compound 1 was found to behave as an attractive masked bis-diene to give 4-oxatricyclo-[4.3.1.03,7]dec-8-ene, 5-aza- and 5-silatricyclo[5.3.1.03,8]undec-9-ene, tricyclo[3.2.1.02,7]oct-3-ene, and tricyclo[5.3.1.03,8]undec-9-ene derivatives through purely pericyclic, three-step homodomino processes with diverse bis-dienophiles; whereas the reaction with myrcene (21) was characterized by a complete sitoselectivity affording compound 25, treatment of 1 with (R)-(-)-β-citronellene (26a) gave a 3:1 mixture of the homochiral diastereomers 30a and 31a. Some limits of this methodology, mainly arising from competitive side reactions upon the key cyclohexa-1,3-diene intermediates, are emphasized. The structures of the new compounds were established on the basis of spectral data.
Hetero Diels-Alder reactions of 4,5-dicyanopyridazine with alkenes
Turchi, Stefania,Giomi, Donatella,Capaccioli, Caterina,Nesi, Rodolfo
, p. 11711 - 11720 (1997)
The behaviour of the title compound 1 with some linear and cyclic olefins has been investigated. Except for the reaction with diphenylcyclopropenone 22, affording 24 and 26 through cyclization processes of the primary Michael adduct 23, a remarkable reactivity as azadiene was observed. The structures of the resulting dicyanocyclohexa-1,3-dienes, aromatic phthalonitriles, and polycyclic bis-adducts were established on the basis of spectral data.
Switchable activity of a Ru catalyst bearing an annulated mesoionic carbene ligand for oxidation of primary amines
Bera, Jitendra K.,Din Reshi, Noor U,Pal, Nilay Kumar,Pal, Saikat,Pal, Sourav,Yadav, Suman
, (2022/01/31)
The catalytic activity of a Ru complex 1, bearing a fused π-conjugated imidazo[1,2–a][1,8]naphthyridine-based mesoionic carbene (MIC) ligand, is examined for the oxidation of primary amines. Complex 1 affords nitrile or imine depending on the nature of th
An overview on the progress and development on the palladium catalyzed direct cyanation
Heydari, Somayyeh,Habibi, Davood,Reza Faraji, Ali,keypour, Hassan,Mahmoudabadi, Masoumeh
, (2020/10/02)
Generation of the positive CN ion and the corresponding direct cyanation are both extremely important for cyanation of aromatic compounds. Hereby, we would like to report the simultaneous use of the new Pd nano-catalyst as well as the three types of the N-arylsulfonyl cyanamides (A, B and C) as potent reagents for the in situ generation of the positive CN ion for the direct cyanation of phenylboronic acids in acetonitrile at reflux conditions.
Pd@CeO2-catalyzed cyanation of aryl iodides with K4Fe(CN)6·3H2O under visible light irradiation
Wang, Shengyu,Wang, Jianqiang,Pan, Junyi,Liu, Cheng,Gong, Xubin,Guo, Cheng
, (2021/01/12)
Cyanation of aryl iodides is still challenging work for chemical researchers because of harsh reaction conditions and toxic cyanide sources. Herein, we have developed a new protocol based on the combination of the catalyst Pd@CeO2, nontoxic cyanide source K4[Fe (CN)6]·3H2O, and driving force visible light irradiation. The reaction is operated at relatively moderate temperature (55°C) and exhibits good catalytic efficiency of product aryl nitriles (yields of 89.4%). Moreover, the catalyst Pd@CeO2 possesses good reusability with a slight loss of photocatalytic activity after five consecutive runs. The reaction system based on the above combination shows a wide range of functional group tolerance under the same conditions. Reaction conditions such as temperature, time, the component of catalyst, and solutions are optimized by studying cyanation of 1-iodo-4-nitrobenzene as model reaction. According to these results, the possible mechanism of Pd@CeO2-catalyzed cyanation of aryl iodides under visible light irradiation is proposed based on the influence of visible light on the catalyst and reactant compounds. In all, we provided an environmental and economic method for preparation of aryl nitriles from cyanation of aryl iodides based on the goal of green chemistry for sustainable development.
Chemical Modifications Induced by Phthalic Anhydride, a Respiratory Sensitizer, in Reconstructed Human Epidermis: A Combined HRMAS NMR and LC-MS/MS Proteomic Approach
Khong, Minh-Thuong,Berl, Valérie,Kuhn, Lauriane,Hammann, Philippe,Lepoittevin, Jean-Pierre
, p. 2087 - 2099 (2021/08/30)
Chemical skin and respiratory allergies are becoming a major health problem. To date our knowledge on the process of protein haptenation is still limited and mainly derived from studies performed in solution using model nucleophiles. In order to better understand chemical interactions between chemical allergens and the skin, we have investigated the reactivity of phthalic anhydride 1 (PA), a chemical respiratory sensitizer, toward reconstructed human epidermis (RHE). This study was performed using a new approach combining HRMAS NMR to investigate the in situ chemical reactivity and LC-MS/MS to identify modified epidermal proteins. In RHE, the reaction of PA appeared to be quite fast and the major product formed was phthalic acid. Two amide type adducts on lysine residues were observed and after 8h of incubation, we also observed the formation of an imide type cyclized adducts with lysine. In parallel, RHE samples topically exposed to phthalic anhydride (13C)-1 were analyzed using the shotgun proteomics method. Thus, 948 different proteins were extracted and identified, 135 of which being modified by PA, i.e., 14.2% of the extracted proteome. A total of 211 amino acids were modified by PA and validated by fragmentation spectra. We thus identified 154 modified lysines, 22 modified histidines, 30 modified tyrosines, and 5 modified arginines. The rate of modified residues, as a proportion of the total number of modifiable nucleophilic residues in RHE, was rather low (1%). At the protein level, modified proteins were mainly type I and type II keratins and other proteins which are abundant in the epidermis such as protein S100A, Caspase 14, annexin A2, serpin B3, fatty-acid binding protein 5, histone H2, H3, H4, etc. However, the most modified protein, mainly on histidine residues, was filaggrin, a protein that is of low abundance (0.0266 mol %) and rich in histidine.
Organic molecular material based on benzene ring unit and having long-afterglow effect and preparation method thereof
-
Paragraph 0053-0057, (2020/04/17)
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.
A Versatile VMPO Catalyst Prepared In Situ for Oxidative Ammonolysis of Isomeric Picolines and Xylenes
Dutta, P.,Pathak, D. D.,Senapati, Rabinarayan
, p. 292 - 298 (2020/04/17)
Abstract: The V2O5–MoO3–P2O5 (VMPO) catalyst has been prepared in situ by thermal decomposition of vanado-molybdophosphoric acid (PMoV) on TiO2 support at 475°C. The TiO2 supported VMPO catalysts are characterized by FT–IR, XRD, BET surface area, NH3–TPD, and H2–TPR. Morphology of the catalyst has been studied by TEM. The accumulated data indicate decomposition of PMoV and presence of phosphate and pyrophosphate phases of molybdenum and vanadium after calcination. TPD and TPR studies exhibit the moderate acidity and presence of V4+ in the material, respectively. The VMPO catalyst has been used for ammoxidation of six different compounds including three isomeric picolines and three isomeric xylenes to the corresponding nitriles with the yield of 90–96%.
Organophotoredox assisted cyanation of bromoarenes: via silyl-radical-mediated bromine abstraction
Shah, Sk. Sheriff,Shee, Maniklal,Singh, N. D. Pradeep
supporting information, p. 4240 - 4243 (2020/04/22)
The insertion of a nitrile (-CN) group into arenes through the direct functionalization of the C(sp2)-Br bond is a challenging reaction. Herein, we report an organophotoredox method for the cyanation of aryl bromides using the organic photoredox catalyst 4CzIPN and tosyl cyanide (TsCN) as the nitrile source. A photogenerated silyl radical, via a single electron transfer (SET) mechanism, was employed to abstract bromine from aryl bromide to provide an aryl radical, which was concomitantly intercepted by TsCN to afford the aromatic nitrile. A range of substrates containing electron-donating and -withdrawing groups was demonstrated to undergo cyanation at room temperature in good yields.
Catalytic oxidative conversion of aldehydes into nitriles using NH3·H2O/FeCl2/NaI/Na2S2O8: A practical approach to febuxostat
Chen, Han,Sun, Sijia,Xi, Haoying,Hu, Kaifang,Zhang, Ning,Qu, Jingping,Zhou, Yuhan
supporting information, p. 1434 - 1436 (2019/05/01)
A novel approach to convert aldehydes into nitriles using NH3·H2O/FeCl2/NaI/Na2S2O8 has been developed. Both alkyl and aryl nitriles were obtained in good to excellent yields. Electron-withdrawing and electron-donating groups, such as fluoro, chloro, bromo, nitro, ester, cyano, trifluoromethyl and alkoxy were tolerated. Notably, febuxostat and its intermediate, ethyl 2-[3-cyano-4-(2-methylpropoxy)phenyl]-4-methyl-5-thiazolecarboxylate, were obtained in excellent yields.
