1660-04-4Relevant articles and documents
Preparation of 2-(3-hydroxy-1-adamantyl)-2-oxoacetic acid: A key intermediate for saxagliptin
Li, Jingke,Zhang, Shurong,Zhou, Hongrui,Peng, Jun,Feng, Yue,Hu, Xiangnan
, p. 347 - 350 (2012)
An optimized synthetic approach to prepare 2-(3-hydroxy-1-adamantyl)-2- oxoacetic acid has been reported in a good yield under mild experimental conditions. It was synthesized from 1-adamantanecarboxylic acid via successful reaction with thionyl chloride and sodium diethyl malonate to give dimethyl (1-adamantylcarbonyl) malonate, which was subjected to hydrolysis and decarboxylation by a mixture of acetic acid with water and sulfuric acid and then oxidation by potassium permanganate. The synthesized adamantane derivative was utilized to saxagliptin.
Synthesis of 1-acetyladamantane by reaction of 1-bromoadamantane with vinyl acetate and ethylidene diacetate catalyzed by Mn2(CO)10
Khusnutdinov,Shchadneva,Mukhametshina
, p. 820 - 822 (2010)
A procedure has been developed for the synthesis of 1-acetyladamantane in 95% yield by reaction of 1-bromoadamantane with vinyl acetate or ethylidene diacetate in the presence of manganese complexes.
The Mn(acac)3-RCN-CCl4 system as a new efficient reagent for the oxidation of secondary alcohols into ketones
Khusnutdinov,Schadneva,Baiguzina,Dzhemilev
, p. 1065 - 1067 (2002)
The Mn(acac)3-RCN-CCl4 system was found to be efficient for the oxidation of secondary alcohols into the corresponding ketones in 80-93% yields. The oxidation proceeds through the formation of alkyl hypochlorites, which are generated from CCl4 and the alcohols in the presence of the Mn(acac)3-RCN catalytic system (R = Me, Et, and Ph).
Selective Nitroxylation of Adamantane Derivatives in the System Nitric Acid–Acetic Anhydride
Ivleva, E. A.,Klimochkin, Yu. N.,Moiseev, I. K.
, p. 1532 - 1539 (2020)
Abstract: A number of new nitroxyadamantanes have been synthesized by nitroxylation of the corresponding substrates with nitric acid in acetic anhydride. High electrophilicity and reduced acidity of the system HNO3–Ac2O increases the stability of nitrates and significantly decreases the probability of formation of alcohols. In some cases, nitrolysis and oxidation of functional groups in the substrate are observed.
Nickel/Photoredox-Catalyzed Methylation of (Hetero)aryl Chlorides Using Trimethyl Orthoformate as a Methyl Radical Source
Kariofillis, Stavros K.,Shields, Benjamin J.,Tekle-Smith, Makeda A.,Zacuto, Michael J.,Doyle, Abigail G.
supporting information, p. 7683 - 7689 (2020/04/22)
Methylation of organohalides represents a valuable transformation, but typically requires harsh reaction conditions or reagents. We report a radical approach for the methylation of (hetero)aryl chlorides using nickel/photoredox catalysis wherein trimethyl orthoformate, a common laboratory solvent, serves as a methyl source. This method permits methylation of (hetero)aryl chlorides and acyl chlorides at an early and late stage with broad functional group compatibility. Mechanistic investigations indicate that trimethyl orthoformate serves as a source of methyl radical via β-scission from a tertiary radical generated upon chlorine-mediated hydrogen atom transfer.
Visible light photoredox catalyzed deprotection of 1,3-oxathiolanes
Yang, Mingyang,Xing, Zhimin,Fang, Bowen,Xie, Xingang,She, Xuegong
supporting information, p. 288 - 291 (2020/01/13)
An efficient visible light photoredox catalyzed aerobic deprotection of 1,3-oxathiolanes using organic dye Eosin Y as a photocatalyst is disclosed. The deprotection procedure features the use of a metal-free catalyst, mild conditions, a broad range of substrate scope, and good functional group tolerance. 35 examples were tested under the standard conditions and most of them afforded the deprotected products in modest to high yields.
Aminoxyl-Catalyzed Electrochemical Diazidation of Alkenes Mediated by a Metastable Charge-Transfer Complex
Siu, Juno C.,Parry, Joseph B.,Lin, Song
supporting information, p. 2825 - 2831 (2019/02/14)
We report the development of a new aminoxyl radical catalyst, CHAMPO, for the electrochemical diazidation of alkenes. Mediated by an anodically generated charge-transfer complex in the form of CHAMPO-N3, radical diazidation was achieved across a broad scope of alkenes without the need for a transition metal catalyst or a chemical oxidant. Mechanistic data support a dual catalytic role for the aminoxyl serving as both a single-electron oxidant and a radical group transfer agent.
Catalyst-Free Photodriven Reduction of α-Haloketones with Hantzsch Ester
Lu, Zheng,Yang, Yong-Qing
, p. 508 - 515 (2019/01/10)
Catalyst-free dehalogenation of α-haloketones under visible light irradiation is studied. The reactions were carried out in common organic solvent. The outcomes of dechlorination are excellent in yields up to 92%, and it is also applicable to bromides, which give even higher yields. The reaction is tolerable to a broad spectrum of substrates, especially to aromatic ketones, including various aryl and hetaryl groups. There are two examples of aliphatic ketones presented in the paper, although their reactivities are not as high as that of the aromatic ketones.
A rimantadine Schiff base synthetic method (by machine translation)
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Page/Page column 3-7, (2019/01/16)
The invention discloses a rimantadine Schiff base synthetic method, including adamantane chloride preparation, adamantane methyl preparation, 1 - adamantane methyl oxime preparation, rimantadine preparation, rimantadine Schiff base preparation, wherein the adamantane methyl preparation steps are as follows: in the flask to join the three trimethylaluminum, formic acid cerium, then dropwise adamantane formyl chloride [...], the adamantane chloride with three methyl aluminum reaction generating adamantane methyl ketone, after the reaction is completed in the reaction liquid into ice water, then filtering, drying, the resulting pale yellow precipitate adamantane methyl ketone. The beneficial effects: the reaction of this invention route changes before the adamantane methyl ketone synthesis route, the use of formic acid cerium auxiliary trimethyl aluminum reaction, mild reaction conditions, few by-products. The invention synthetic method mild condition, the process is simple and feasible, less catalyst levels, environmental protection, high product yield. (by machine translation)
Compounding agent of rimantadine hydrochloride and camphor tree essential oil and application thereof
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Page/Page column 5-9, (2019/01/24)
The invention discloses a compounding agent of rimantadine hydrochloride and camphor tree essential oil and application thereof, wherein the weight ratio of the amantadine hydrochloride to the camphortree essential oil in the compounding agent is 1: 50-50: 1, Adamantanecarbonyl chloride as a raw material, trimethylaluminum as a reagent and cerium formate as an auxiliary agent are reacted to formadamantane methyl ketone, and the rimantadine hydrochloride is prepared by oximation and platinum-carbon hydrogenation reduction of the adamantane methyl ketone; and the camphor tree essential oil isprepared by crushing camphor tree seeds, leaves, bark and the like as raw materials, using sodium glycinate and citric acid to assist breaking of cell walls and using a distillation technique; and thebeneficial effects are that: high purity and high yield of the rimantadine hydrochloride and the camphor tree essential oil. The compound composition of the rimantadine hydrochloride and the camphortree essential oil has synergistic effect, can effectively reduce the application amount of single agents, expands the sterilization spectrum, reduces the phytotoxicity, significantly improves the control effect against pathogens and viruses, alleviates the resistance problem of pathogenic bacteria, and reduces the cost of prevention.
