2171-74-6Relevant articles and documents
Aqueous microwave-assisted synthesis of non-interpenetrated metal-organic framework for room temperature cycloaddition of CO2 and epoxides
Babu, Robin,Kim, Seol-Hee,Kathalikkattil, Amal Cherian,Kuruppathparambil, Roshith Roshan,Kim, Dong Woo,Cho, Sung June,Park, Dae-Won
, p. 126 - 136 (2017)
A multilinker non-interpenetrated metal-organic framework, UMCM-15, was synthesized by using microwave power as an alternative energy-efficient tool for the first time. The synergistic catalytic activity, when combined with a co-catalyst containing a strongly nucleophilic anion, was studied in the solventless room temperature cycloaddition between epoxides and CO2. Unlike previous reports on UMCM-15 synthesized in the high-boiling solvent dimethylformamide, low boiling water/ethanol mixture was used as the solvent herein. This approach holds potential as a sustainable green methodology. Crystal formation during the microwave-assisted (MW) synthesis was monitored at certain time intervals. The favorable role of non-interpenetrated pillared structures in promoting room temperature CO2-epoxide cycloaddition reactions was explained by comparing the catalytic efficiency of the three-linker extended pillar-layered non-interpenetrated UMCM-15 with its analogous pillared structures built from two- and three-fold interpenetrated ([Zn2(BDC)2(4,4′-bipy)] and [Zn2(NDC)2(4,4′-bipy)]) catalytic systems with a single dicarboxylate linker. The efficacy of the microwave-assisted UMCM-15(M) catalyst in cycloaddition reactions was proved by comparing the catalytic activity of UMCM-15(M) with that of the congener made by solvothermal synthesis, UMCM-15(S). In addition, a plausible mechanism for the synergistic operation of the Lewis acid sites and nucleophiles was suggested.
Two Cu(II)-organic frameworks: Effective CO2 fixation and protective activity on the motor function after stroke by increasing neural stem cells differentiation
Ye, Qing,Zhang, Li,Shao, Zhou-Li,Zhang, Wei,Li, Chao,Ye, Xiang-Ming
, (2020)
In the present research, two novel metal–organic frameworks (MOFs) containing Cu(II) ions as nodes {[Cu(L)]·2DMF·2H2O}n (1) and {[(CH3)2NH2][Cu2(L)(H2O)PO4]·2DMF}
Photo-on-Demand Base-Catalyzed Phosgenation Reactions with Chloroform: Synthesis of Arylcarbonate and Halocarbonate Esters
Dai, Namin,Eda, Kazuo,Harada, Hidefumi,Hashimoto, Yuka,Hosokawa, Sasuga,Kakiuchi, Toshifumi,Liang, Fengying,Okazoe, Takashi,Suzuki, Yuto,Tana, Gegen,Tsuda, Akihiko
, p. 9811 - 9819 (2021/07/20)
Carbonate esters are utilized as solvents and reagents for C1 building blocks in organic synthesis. This study reports a novel photo-on-demand in situ synthesis of carbonate esters with CHCl3 solutions containing a mixture of an aromatic or haloalkyl alcohol having relatively high acidity, and an organic base. We found that the acid-base interaction of the alcohol and base in the CHCl3 solution plays a key role in enabling the photochemical reaction. This reaction allows practical syntheses of diphenyl carbonate derivatives, haloalkyl carbonates, and polycarbonates, which are important chemicals and materials in industry.
Method for simultaneously preparing 2-ethoxyphenol and 1,3-benzodioxolane-2-one
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Paragraph 0024-0027, (2020/06/09)
The invention belongs to the field of organic synthesis, and provides a method for simultaneously preparing 2-ethoxyphenol and 1,3-benzodioxolane-2-one. According to the preparation method, catechol and diethyl carbonate are subjected to transesterification under the action of a catalyst, so that the 2-ethoxyphenol and the 1,3-benzodioxolane-2-one can be obtained. The combined selectivity of the 2-ethoxyphenol and the 1,3-benzodioxolane-2-one can reach 97%, and the method has the advantages of high conversion rate, high selectivity, high economic benefit, environmental friendliness and the like.
CARBONATE DERIVATIVE PRODUCTION METHOD
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Paragraph 0114-0115, (2020/04/09)
The objective of the present invention is to provide a method for producing a carbonate derivative in a safe and efficient manner. The method for producing a carbonate derivative according to the present invention is characterized in comprising irradiating light on a composition containing a C1-4 halogenated hydrocarbon having one or more kinds of halogen atoms selected from the group consisting of a chlorine atom, a bromine atom and an iodine atom, a nucleophilic functional group-containing compound and the specific base in the presence of oxygen.
Fluorodesulfurization of Thionobenzodioxoles with Silver(I) Fluoride
Newton, Josiah J.,Brooke, Alan J.,Duhamel, Bastian,Pulfer, Jason M.,Britton, Robert,Friesen, Chadron M.
, p. 13298 - 13305 (2020/11/26)
Difluorobenzodioxole is an important functional group found in both pharmaceuticals and agrochemicals. The late-stage introduction of this functional group is challenged by typical fluorination conditions of HF and strong oxidants. Here, we demonstrate that a range of difluorobenzodioxoles can be prepared from catechols in two steps through conversion into thionobenzodioxoles, followed by desulfurative fluorination with silver(I) fluoride. These mild reaction conditions are compatible with a variety of functional groups and enable access to a range of functionalized difluorobenzodioxoles.
Diphenyl Carbonate: A Highly Reactive and Green Carbonyl Source for the Synthesis of Cyclic Carbonates
Baral, Ek Raj,Lee, Jun Hee,Kim, Jeung Gon
, p. 11768 - 11776 (2018/09/27)
A practical, safe, and highly efficient carbonylation system involving a diphenyl carbonate, an organocatalyst, and various diols is presented herein and produces highly valuable cyclic carbonates. In reactions with a wide range of diols, diphenyl carbonate was activated by bicyclic guanidine 1,5,7-triazabicyclo[4.4.0]dec-5-ene (TBD) as a catalyst, which successfully replaced highly toxic and unstable phosgene or its derivatives while maintaining the desired high reactivity. Moreover, this new system can be used to synthesize sterically demanding cyclic carbonates such as tetrasubstituted pinacol carbonates, which are not accessible via other conventional methods.
The design of efficient carbonate interchange reactions with catechol carbonate
Tabanelli,Monti,Cavani,Selva
supporting information, p. 1519 - 1528 (2017/05/01)
Catechol carbonate (CC) has been investigated as an innovative and highly active reactant for carbonate interchange reactions (CIRs). Under mild conditions (atmospheric pressure, and 60-80°C), the selective synthesis of symmetric aliphatic carbonates (ROCO2R) has been achieved by the reaction of a slight excess of both primary and secondary alcohols with CC in the presence of NaOMe or MgO as a catalyst. Quantitative conversions have been reached in only 1 hour and products have been isolated in yields of up to 58% for dibutylcarbonate. Of note is that the reaction of glycerol with CC also proceeded under similar conditions (40-60°C, 1 atm) to afford glycerol carbonate (96-98%). The comparison of the reactivity of CC with that of conventional dialkyl carbonates, including dimethyl carbonate (DMC) and ethylene carbonate (EC), proved the superior performance of CC in all the investigated CIR processes. Accordingly, a mechanism has been formulated based on the leaving group ability of a catecholate anion originating from CC.
Continuous Flow Synthesis of Carbonylated Heterocycles via Pd-Catalyzed Oxidative Carbonylation Using CO and O2 at Elevated Temperatures and Pressures
Chen, Yuesu,Hone, Christopher A.,Gutmann, Bernhard,Kappe, C. Oliver
, p. 1080 - 1087 (2017/07/26)
A continuous-flow Pd-catalyzed oxidative carbonylation protocol utilizing CO and O2 gas for the synthesis of carbonylated heterocycles is described. The optimization of temperature, pressure, CO/O2 ratio, catalyst loading, and reaction time resulted in process intensified conditions for this transformation. The optimized continuous flow conditions (120 °C, 20 bar pressure, 24 min residence time) were used to prepare a number of benzoxazolone, 2-benzoxazolidinone, and other biologically and synthetically important five- and six-membered carbonylated heterocycles in good overall yield and purity (14 examples). The continuous-flow process enables the safe and scalable oxidative carbonylation using CO/O2 under elevated pressures and temperatures.
Lanthanide-catalyzed cyclocarbonylation and cyclothiocarbonylation: A facile synthesis of benzannulated 1,3-diheteroatom five- and six-membered heterocycles
Jing, Yufeng,Liu, Ruiting,Lin, Yanghui,Zhou, Xigeng
, p. 1117 - 1125 (2014/08/18)
La[N(SiMe3)2]3 proves to be an efficient catalyst system for the cyclocarbonylation of 1,2-disubstituted benzenes with isocyanates. In this approach, aryl/alkyl isocyanates react with o-phenylenediamine, o-aminophenol, o-aminothiophenol, catechols and anilines ortho-substituted by CH2NH2 and CONH2 to form, respectively, the corresponding benzimidazolones, benzoxazolones, benzothiazolones, benzodioxolones, 3,4-dihydroquinazolin-2(1H)-one, and quinazolinediones. These results represent the first example of lanthanide-catalyzed carbonylation. This methodology is also applicable for the preparation of various benzannulated 1,3-diheteroatom cyclic thioketones starting from aryl/alkyl isothiocyanates or CS2 in good to excellent yields. Based on the results of experiments performed using an o-aminobenzamido dianion lanthanide complex, a general mechanism, involving the tandem reaction of two lanthanide-ligand bonds with one heterocumulene molecule, is proposed as well.
