- Reactivity of several deactivated 3-aminobenzo[b]thiophenes in the Buchwald-Hartwig C-N coupling. Scope and limitations
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Di(hetero)arylamines were prepared in moderate to high yields by Buchwald-Hartwig C-N coupling of bromobenzenes bearing electron-withdrawing groups and of a bromobiphenyl with several methyl 3-aminobenzo[b]thiophene-2-carboxylates, using the coupling cond
- Queiroz, Maria-Jo?o R.P.,Calhelha, Ricardo C.,Kirsch, Gilbert
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Read Online
- 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 0077-0079
(2020/08/22)
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- 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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- 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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- A preparation method for 4-methoxy-2-nitrobenzoic acid
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An industrial preparation method for 4-methoxy-2-nitrobenzoic acid is disclosed. In the method, p-difluorobenzene is adopted as an initial raw material and subjected to nitration, ammonolysis, diazotization bromination, cyaniding, methoxylation and hydrolysis which are six steps to synthesize the 4-methoxy-2-nitrobenzoic acid. The 4-methoxy-2-nitrobenzoic acid obtained by the method is white powdered solid with purity being 98.5%, the raw material conversion ratio in each step is 100%, and the total yield of the whole process is 35.8%.
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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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- SUBSTITUTED 2- AMIDOQUINAZOL-4-ONES AS MATRIX METALLOPROTEINASE-13 INHIBITORS
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The present invention provides a novel amide derivative having a matrix metalloproteinase inhibitory activity, and useful as a pharmaceutical agent, which is a compound represented by the formula (I) wherein ring A is an optionally substituted, nitrogen containing heterocycle, ring B is an optionally substituted monocyclic homocycle or an optionally substituted monocyclic heterocycle, Z is N or NR1 (R1 is a hydrogen atom or an optionally substituted hydrocarbon group), is a single bond or a double bond, R2 is a hydrogen atom or an optionally substituted hydrocarbon group, X is an optionally substituted spacer having 1 to 6 atoms, ring C is (1) an optionally substituted homocycle or (2) an optionally substituted heterocycle other than a ring represented by (II) (X′ is S, O, SO, or CH2), and at least one of ring B and ring C has substituent(s), provided that N-{(1S,2R)-1-(3,5-difluorobenzyl)-3-[(3-ethylbenzyl)amino]2 hydroxypropyl}5,6 dimethyl 4 oxo 1,4 dihydrothieno[2,3-d]pyrimidine-2-carboxamide is excluded, or a salt thereof.
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Paragraph 1554
(2015/12/23)
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- Synthesis and biological evaluation of N-aryl-7-methoxybenzo[b]furo[3,2-d] pyrimidin-4-amines and their N-arylbenzo[b]thieno[3,2-d]pyrimidin-4-amine analogues as dual inhibitors of CLK1 and DYRK1A kinases
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Novel N-aryl-7-methoxybenzo[b]furo[3,2-d]pyrimidin-4-amines (1) and their N-arylbenzo[b]thieno[3,2-d]pyrimidin-4-amine analogues (2) were designed and prepared for the first time via microwave-accelerated multi-step synthesis. Various anilines were conden
- Loidreau, Yvonnick,Marchand, Pascal,Dubouilh-Benard, Carole,Nourrisson, Marie-Renee,Duflos, Muriel,Loaec, Nadege,Meijer, Laurent,Besson, Thierry
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p. 283 - 295
(2013/03/14)
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- Carbopalladation of nitriles: Synthesis of 2,3-diarylindenones and polycyclic aromatic ketones by the Pd-catalyzed annulation of alkynes and bicyclic alkenes by 2-iodoarenenitriles
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2-Iodobenzonitrile, its derivatives, and various heterocyclic analogues undergo palladium(O)-catalyzed annulation onto diarylacetylenes or bicyclic alkenes to afford 2,3-diarylindenones and polycyclic aromatic ketones in very good to excellent yields. This reaction represents one of the first examples of the addition of an organopalladium moiety to the carbon-nitrogen triple bond of a nitrile. The reaction is compatible with a number of functional groups. A reaction mechanism, as well as a model accounting for the electronic effects of substituents on the aromatic ring of the nitrile, is proposed.
- Pletnev, Alexandre A.,Tian, Qingping,Larock, Richard C.
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p. 9276 - 9287
(2007/10/03)
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- Asymmetric Synthesis of Functionalized 1,2,3,4-Tetrahydroquinolines
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Highly enantioselective rhodium-catalyzed asymmetric hydrogenation (>98% ee) and Sharpless epoxidation (>90% ee) of o-nitrocinnamyl substrates lead to intermediates that can be transformed into tetrahydroquinoline derivatives. Starting materials are produced in high-yielding Heck reactions of an o-nitroaryl iodide and α-acetamidoacrylate or methyl acrylate.
- Gallou-Dagommer, Isabelle,Gastaud, Philippe,RajanBabu
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p. 2053 - 2056
(2007/10/03)
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- 2- OR 3-(SUBSTITUTEDAMINOALKOXYPHENYL)QUINAZOLIN-4-ONES
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This invention relates to 2-or 3-(substituted aminoalkoxyphenyl) quinazolin-4-ones which are partial estrogen agonists and are useful in treating osteoporosis, prostatic hypertrophy, breast cancer and endometrial cancer.
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- The Reactions of 2,4-Dinitro- and 2,6-Dinitro-benzonitriles with Methoxide Ions
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The reactions of 1-cyano-2,4-dinitrobenzene (1) and 1-cyano-2,6-dinitrobenzene (2) with methoxide ions in methanol or in 98/2 (v/v) DMSO/methanol have been examined by uv/visible and 1H n.m.r. spectroscopies.In methanol reaction occurs in two stages.In the first there is competitive attack by methoxide at the cyano-group, leading to the solvate, and at ring-carbon atoms leading to substitution products.In the second stage the solvate is converted to substitution products via the parent.Rate coefficients are reported for methoxide attack and equilibrium constants for solvate formation have been calculated.The initial reversible reactions in DMSO give ?-adducts by methoxide attack at unsubstituted ring-positions and these are followed by irreversible substitution of nitro-groups.
- Crampton, Michael R.,Elsegood, Simon E.,Atherton, John H.
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p. 1371 - 1382
(2007/10/02)
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- Nucleophilic photosubstitutions of o-methoxynitrobenzenes
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We report a new synthesis of 3-nitroveratrole, based on the directed lithiation of veratrole, and photochemical substitutions of both 3-nitroveratrole and o-nitroanisole with several nucleophiles.Both aromatic substrates undergo photocyanation meta to the nitro group.With hydroxide ion, 3-nitroveratrole reacts meta to the nitro group, but 2-nitroanisole undergoes replacement of either substituent, the proportion of reaction at each site depending upon the OH(-) concentration. 3-Nitroveratrole undergoes an inefficient reaction with butylamine at each methoxy group; this reaction is apparently second order in amine.The reaction between o-nitroanisole and diethylamine results only in photohydrolysis.Keywords: photosubstitution, nucleophilic, 3-nitroveratrole, o-nitroanisole
- Bunce, Nigel J.,Stephenson, Karen Labonte
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p. 220 - 226
(2007/10/02)
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