- Conversions of aryl carboxylic acids into aryl nitriles using multiple types of Cu-mediated decarboxylative cyanation under aerobic conditions
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Here, we used malononitrile or AMBN as a cyanating agent to develop efficient and practical protocols for Cu-mediated decarboxylative cyanations, under aerobic conditions, of aryl carboxylic acids bearing nitro and methoxyl substituents at the ortho position as well as of heteroaromatic carboxylic acids. These protocols involved economical methods to synthesize value-added aryl nitriles from simple and inexpensive raw materials. Further diversification of the 2-nitrobenzonitrile product was performed to highlight the practicality of the protocols. This journal is
- Cai, Hu,Cao, Xihan,Fu, Zhengjiang,Guo, Shengmei,Wang, Shuiliang
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supporting information
p. 8381 - 8385
(2020/11/05)
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- Method for synthesizing aryl cyanide by taking aryl carboxylic acid as raw material
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The invention discloses a method for synthesizing aryl cyanide by taking aryl carboxylic acid as a raw material, which is characterized in that aryl cyanide is synthesized by taking aryl carboxylic acid as a raw material, taking a combination of NH4X and N, N-dimethylformamide as a cyanide source and taking silver sulfate and copper acetate as catalysts under the action of acid and oxygen. Compared with a conventional aryl cyanide synthesis method, the method disclosed by the invention has the advantages that reaction raw materials (aryl carboxylic acid, NH4X and N, N-dimethylformamide) are cheap and easy to obtain, and the dosage of a metal catalyst is small; meanwhile, oxygen is used as an oxidizing agent, so that the method has the obvious advantages of small environmental pollution, good tolerance to various functional groups on an aromatic ring, high yield and the like; the method disclosed by the invention can be widely applied to synthesis of medicines, functional materials, natural products and other fields in the industry and academic circles.
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Paragraph 0074-0076
(2020/08/22)
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- Ag/Cu-mediated decarboxylative cyanation of aryl carboxylic acids with K4Fe(CN)6 under aerobic conditions
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A method for facile synthesis of aryl nitriles has been well established via Ag/Cu-mediated decarboxylative cyanation of benzoic acids with K4Fe(CN)6 under aerobic conditions. The approach of using readily accessible aryl carboxylic acids and green K4Fe(CN)6 as starting material provides a feasible alternative to previous cyanation protocols. Control experiments revealed the key role of Cu for the process and excluded the possibility of a radical mechanism for the transformation.
- Fu, Zhengjiang,Jiang, Ligao,Li, Zhaojie,Jiang, Yongqing,Cai, Hu
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supporting information
p. 917 - 924
(2019/03/17)
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- Decarboxylative Halogenation and Cyanation of Electron-Deficient Aryl Carboxylic Acids via Cu Mediator as Well as Electron-Rich Ones through Pd Catalyst under Aerobic Conditions
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Simple strategies for decarboxylative functionalizations of electron-deficient benzoic acids via using Cu(I) as promoter and electron-rich ones by employing Pd(II) as catalyst under aerobic conditions have been established, which lead to smooth synthesis of aryl halides (-I, Br, and Cl) through the decarboxylative functionalization of benzoic acids with readily available halogen sources CuX (X = I, Br, Cl), and easy preparation of benzonitriles from decarboxylative cyanation of aryl carboxylic acids with nontoxic and low-cost K4Fe(CN)6 under an oxygen atmosphere for the first time.
- Fu, Zhengjiang,Li, Zhaojie,Song, Yuanyuan,Yang, Ruchun,Liu, Yanzhu,Cai, Hu
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p. 2794 - 2803
(2016/04/26)
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- Noncovalent tripeptidic thrombin inhibitors incorporating amidrazone, amine and amidine functions at P1
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A series of noncovalent tripeptidic thrombin inhibitors incorporating amidrazone, amine and amidine functions at P1 was investigated. While the amidrazone and the amine series displayed limited oral absorption, the amidine series demonstrated generally good oral absorption and strong antithrombotic activity; the single-digit picomolar Ki achieved from this series is among the best yet reported. The present work highlights the benzamidine compound 11f (LB30812) that exhibits excellent overall profiles of potency, oral absorption and antithrombotic efficacy.
- Lee, Koo,Jung, Won-Hyuk,Park, Cheol Won,Park, Hee Dong,Lee, Sun Hwa,Kwon, O Hwan
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p. 1017 - 1022
(2007/10/03)
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- Sandmeyer reactions. Part 5.1 Estimation of the rates of 1,5-aryl/aryl radical translocation and cyclisation during Pschorr fluorenone synthesis with a comparative analysis of reaction energetics
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During the Pschorr cyclisation of 2-aroylphenyl radicals, a rearrangement occurs reversibly by 1,5-hydrogen transfer to give 2-benzoylaryl radicals. Rate constants of (1.2 ± 0.2) × 106 s-1 at 293 K are estimated for both the forward and back reactions in the equilibrium between 2-(4-methylbenzoyl)phenyl and 2-benzoyl-5-methylphenyl radicals. Assuming an empirical estimate of 1.6 × 10-2 dm3 mol-1 s-1 for the hypothetical rate of abstraction of hydrogen from benzene by phenyl radicals, the radical translocation is calculated to occur with a statistically corrected effective molarity of 2.2 × 108 mol dm-3. By contrast, the competing cyclisation, though occurring at a rate of (8.0 ± 0.9) × 105 s-1, exhibits an effective molarity of only 5.3 mol dm-3. The causes of these differences are analysed in terms of reaction mechanism.
- Chandler, Stephen A.
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p. 214 - 228
(2007/10/03)
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- Utilisation du cyanure de tetraethylammonium pour la preparation de complexes cyclopentadienyl fer cyclohexadienyl cyanes. Etude de leur oxydation electrochimique et chimique
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Addition of tetraethylammonium cyanide to a solution of η5-cyclopentadienyl)(η6-arene)iron (1 +), in acetonitrile can be studied by voltammetry.With electron-withdrawing groups such as nitro, keto, sulfone, azo and azoxy bonded to the arene, the reaction occurs immediately and a wave resulting form oxidation of hexadienyl species is observed in the range 0-IV vs.SCE.Preparation of various hexadienyl compounds was achieved with good yields.In order to obtain ortho-substituted benzonitriles, electrochemical and chemical oxidations of hexadienyl complexes were compared.The best results were obtained with N-bromosuccinimide (NBS) and a demetallation generally occurs.A one-pot synthesis of benzonitrile compounds can be achieved after addition of cyanide ion and then NBS to a solution of (η5-cyclopentadienyl)(η6-arene) iron (1 +) in acetonitrile. 6-C6H5N(O)=NC6H4Cn-2>>+ is directly obtained from the azoxy dicationic compound 2+.Keywords: Iron; Ferrocenes; Electrochemistry; Arene complexes; Oxidation
- Guennec, N.,Moinet, C.
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p. 171 - 184
(2007/10/03)
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- Substituted Isatoic Anhydrides: Selective Inactivators of Trypsin-like Serine Proteases
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Derivatives of isatoic anhydride were prepared and tested as inhibitors of serine proteases.A number of isatoic anhydrides with positively charged substituents irreversibly inactivated several trypsin-like enzymes and preferentially inactivated trypsin over chymotrypsin.Further selectivity was obtained by introduction of an aromatic group on the N-1 position of isatoic anhydride. 7-(Aminomethyl)-1-benzylisatoic anhydride was prepared and was a selective inactivator of thrombin; thus it is possible to prepare derivatives of isatoic anhydride that are highly enzyme selective without attaching peptide recognition structures.
- Gelb, Michael H.,Abeles, Robert H.
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p. 585 - 589
(2007/10/02)
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