623-73-4Relevant articles and documents
Ethyl diazoacetate synthesis in flow
Delville, Marielle M.E.,Van Hest, Jan C. M.,Rutjes, Floris P.J.T.
, p. 1813 - 1818 (2013)
Ethyl diazoacetate is a versatile compound in organic chemistry and frequently used on lab scale. Its highly explosive nature, however, severely limits its use in industrial processes. The in-line coupling of microreactor synthesis and separation technology enables the synthesis of this compound in an inherently safe manner, thereby making it available on demand in sufficient quantities. Ethyl diazoacetate was prepared in a biphasic mixture comprising an aqueous solution of glycine ethyl ester, sodium nitrite and dichloromethane. Optimization of the reaction was focused on decreasing the residence time with the smallest amount of sodium nitrite possible. With these boundary conditions, a production yield of 20 g EDA day-1 was achieved using a microreactor with an internal volume of 100 μL. Straightforward scale-up or scale-out of microreactor technology renders this method viable for industrial application.
A pilot-scale synthesis of (1R)-trans-2-(2,3-dihydro-4-benzofuranyl) cyclopropanecarboxylic acid: A practical application of asymmetric cyclopropanation using a styrene as a limiting reagent
Simpson, James H.,Godfrey, Jollie,Fox, Rita,Kotnis, Atul,Kacsur, David,Hamm, Jason,Totelben, Michael,Rosso, Victor,Mueller, Richard,Delaney, Edward,Deshpande, Rajendra P.
, p. 3569 - 3574 (2003)
Asymmetric cyclopropanation of styrene 1 (as the limiting reagent) was demonstrated using excess ethyl diazoacetate and catalytic Ru(ip-Pybox). Selective hydrolysis of the resulting 90:10 trans:cis mixture of cyclopropane 4 generated cyclopropyl acid 2 as a 96:4 trans:cis mixture with 84% e.e. for the trans-cyclopropane. Further purification and enantiomeric enrichment was achieved by diastereoselective crystallization with (+)-dehydroabeitylamine to afford the (R,R)-isomer with ≥99.9% e.e in 60-65 M% yield starting from styrene 1.
CuSO4-catalyzed three-component reaction of α-diazo ester, water and isatin: An efficient approach to oxindole derivatives
Jing, Changcheng,Shi, Taoda,Xing, Dong,Guo, Xin,Hu, Wen-Hao
, p. 620 - 624 (2013)
A highly efficient three-component reaction of α-diazo ester, water and isatin was developed by using CuSO4 as the catalyst. In this reaction, water was used as both a reactant and the solvent. With this highly environmentally benign and economical protocol, a series of 3-hydroxyindolin-2- one derivatives were efficiently produced in good yields with moderate to high diastereoselectivities.
A Three-Component Reaction to Construct β-Aminonitroso-α-Diazocarbonyl Compounds under Metal-Free Conditions
Chen, Rongxiang,Lan, Jihong,Li, Feng,Liu, Lantao,Wang, Kai-Kai,Xu, Canran,Xue, Yinghui
supporting information, (2022/04/03)
A procedure for the transition-metal-free three-component reaction of 1,3,5-triazines, diazo compounds and tert-butyl nitrite has been described. This reaction goes through tandem nucleophilic attack to generate synthetically important β-aminonitroso-α-diazocarbonyl compounds in moderate to good yields. This protocol is distinguished by the use of readily available starting materials, wide substrate scope and operational simplicity. Notably, a N?N bond and a C?C bond were formed simultaneously. (Figure presented.).
METHOD OF PRODUCING NITRO COMPOUND
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Paragraph 0041, (2021/06/25)
PROBLEM TO BE SOLVED: To provide a production method which can efficiently provide a nitro compound in an industrial scale. SOLUTION: A method of producing a compound represented by formula (2) comprises using nitric acid to nitrate a compound represented by formula (1) in the presence of concentrated sulfuric acid that weighs 1.5-5.0 times more than the compound represented by formula (1). [In formulas (1) and (2), X1 and X2 are identical or different and represent halogen atoms, and R represents an optionally substituted 6-membered heterocyclic group.] SELECTED DRAWING: None COPYRIGHT: (C)2021,JPOandINPIT
PYRIMIDINE-BASED BICYCLES AS ANTIVIRAL AGENTS FOR THE TREATMENT AND PREVENTION OF HIV INFECTION
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Page/Page column 72; 73; 78; 79; 81-83; 85-86; 88-89; 91-94; ..., (2021/08/27)
This invention relates to pyrimidine derivatives, having HIV replication inhibiting. The present invention provides new pyrimidine compounds, designed for the treatment and prevention of HIV-mediated diseases. The invention further relates to pharmaceutical compositions and drugs contained in them. The invention also relates to the use of abovementioned compounds for the treatment and/or prevention of HIV in subjects with HIV-infection (human immunodeficiency virus) or having risk of getting HIV-infection.
B(C6F5)3-Catalyzed site-selective N1-alkylation of benzotriazoles with diazoalkanes
Guo, Jing,Mandal, Dipendu,Stephan, Douglas W.,Wu, Yile,Zhao, Yunbo
supporting information, p. 7758 - 7761 (2021/08/13)
Alkylation of benzotriazoles is synthetically challenging, often leading to mixtures of N1 and N2 alkylation. Herein, metal-free catalytic site-selective N1-alkylation of benzotriazoles with diazoalkanes is described in the presence of 10 mol% of B(C6F5)3. These reactions provide N1-alkylated benzotriazoles in good to excellent yields and this protocol is successfully adapted to gram-scale syntheses as well as a derivative with antimicrobial activity.
Catalytic Ring Expansion of Activated Heteroarenes Enabled by Regioselective Dearomatization
Kim, Jiyoung,Yoo, Eun Jeong
supporting information, p. 4256 - 4260 (2021/06/28)
Catalytic ring expansion of activated heteroarenes through 1,4-dearomative addition of diazoacetates was established for the construction of various fused azepines by an elaborate control of the reaction kinetics at each step. The use of a silver catalyst was essential to drive the overall reaction for generating the desired seven-membered azepines. Because of the excellent substrate scope and selectivity, the developed methodology presents an innovative approach for the synthesis of multifused azepines, which are biologically relevant molecules.
Tridentate Nickel(II)-Catalyzed Chemodivergent C-H Functionalization and Cyclopropanation: Regioselective and Diastereoselective Access to Substituted Aromatic Heterocycles
Nag, Ekta,Gorantla, Sai Manoj N. V. T.,Arumugam, Selvakumar,Kulkarni, Aditya,Mondal, Kartik Chandra,Roy, Sudipta
supporting information, p. 6313 - 6318 (2020/09/02)
A Schiff-base nickel(II)-phosphene-catalyzed chemodivergent C-H functionalization and cyclopropanation of aromatic heterocycles is reported in moderate to excellent yields and very good regioselectivity and diastereoselectivity. The weak, noncovalent interaction between the phosphene ligand and Ni center facilitates the ligand dissociation, generating the electronically and coordinatively unsaturated active catalyst. The proposed mechanisms for the reported reactions are in good accord with the experimental results and theoretical calculations, providing a suitable model of stereocontrol for the cyclopropanation reaction.
Catalytic C-C coupling of diazo compounds with arylboronic acids: Using surface modified sewage sludge as catalyst
Huang, Fei,Huang, He,Hughes, Timothy,Xie, Yuxing,Xu, Jun,Yu, Yang,Zhang, Zhipeng
supporting information, p. 4165 - 4173 (2020/07/14)
A green, mild and efficient synthesis of diarylmethines using sewage sludge-derived carbonaceous materials (SW) by perchloric acid catalyzed coupling reactions between diazo compounds and arylboronic acids was developed. The reaction shows a high level of functional tolerance and a broad substrate scope. Furthermore, the highly selective 1,2-alkyl shift products were furnished through the sterically demanding R4, R5 migration of diazo compounds (3-diazochromanone). The structures of 1,2-shift products have been further confirmed by single-crystal X-ray analysis. Significantly, the synthesis of the core structures of darifenacin (a clinical drug for overactive bladder syndrome, OAB) and diclofensine (a stimulant drug showing antidepressant and monoamine reuptake inhibitor activity) further demonstrated the efficacy and synthetic potential of this method. This journal is
