- Method for synthesizing acetylenic acid by using terminal alkyne and carbon dioxide
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The invention belongs to the field of organic synthesis, and particularly relates to a method for synthesizing acetylenic acid by using terminal alkyne and carbon dioxide. The method comprises the experimental steps that alkyne, alkali and a solvent are added into a reaction tube, the alkyne serves as a raw material, the alkali and the solvent provide a strong alkaline environment, CO2 is introduced into a reaction container to form a carbon dioxide atmosphere, heating and stirring reaction are carried out, after the reaction is finished, cooling is carried out to the room temperature, extraction and liquid separation are carried out, a water layer is acidified, then separation and purification are further carried out, and the acetylenic acid compound is obtained. The method is carried out under the conditions of low temperature and normal pressure, does not need to add a metal catalyst, is single in product and convenient to separate, good in substrate applicability and safe and simple to operate, and has potential industrial application prospects and good economic benefits.
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Paragraph 0106-0114
(2021/07/24)
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- Microwave-assisted fabrication of a mixed-ligand [Cu4(μ3-OH)2]-cluster-based metal–organic framework with coordinatively unsaturated metal sites for carboxylation of terminal alkynes with carbon dioxide
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The development of efficient and stable metal–organic framework (MOF) catalysts with coordinatively unsaturated metal sites for modern organic synthesis is greatly important. Herein, a robust [Cu4(μ3-OH)2]-cluster-based MOF (Cu-MOF) with a mixed-ligand system was successfully fabricated by a microwave-assisted method under mild conditions. The as-prepared Cu-MOF catalyst possessing unsaturated Cu (II) sites exhibited excellent catalytic activity toward the direct carboxylation of 1-ethynylbenzene with CO2, and various propiolic acid derivatives were synthesized in moderate to good yields under optimized reaction conditions. Furthermore, the catalyst remained stable and could be easily recycled for five sequential runs without incredible decrease in catalytic efficiency.
- Wang, Wen-Jing,Sun, Zhong-Hua,Chen, Sheng-Chun,Qian, Jun-Feng,He, Ming-Yang,Chen, Qun
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- Silver Nanoparticles Architectured HMP as a Recyclable Catalyst for Tetramic Acid and Propiolic Acid Synthesis through CO2 Capture at Atmospheric Pressure
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The recent advancement on the tailored synthesis of hypercrosslinked microporous polymer (HMP-2) has assembled significant concentration by the virtue of its adjustable porosity, operative design and absolutely ordering structure. This perfectly structured Ag NPs supported carbocatalyst (Ag-HMP-2) has been synthesized by Friedel-Crafts alkylation between 4,4′-Bis(bromomethyl)-1,1′-biphenyl and carbazole over anhydrous iron(III)chloride catalysis followed by the appending of the silver nanoparticles (Ag NPs) onto the material. The silver nanoparticle was decorated over the HMP-2 to prepare the corresponding catalyst (Ag-HMP-2). The characterization of the newly produced material has been conducted by N2 adsorption/desorption studies, XPS, FE-SEM, transmission electron microscopy (TEM) and Powder X-ray diffraction (PXRD) methods. This microporous catalyst has spectacular activities for the production of tetramic acids from various types of propargylic amine derivatives at 60 °C under atmospheric carbon dioxide pressure. Parallel attempt on fixation of CO2 was executed over terminal alkynes to synthesize propiolic acids under 1 atm pressure. The catalyst (Ag-HMP-2) exhibited sufficient recycling ability for the generation of tetramic acids and propiolic acids up to five catalytic runs without reduction in its catalytic activity.
- Ghosh, Swarbhanu,Ghosh, Aniruddha,Riyajuddin, Sk,Sarkar, Somnath,Chowdhury, Arpita Hazra,Ghosh, Kaushik,Islam, Sk. Manirul
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p. 1055 - 1067
(2020/01/21)
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- Pd-Catalyzed decarboxylative alkynylation of alkynyl carboxylic acids with arylsulfonyl hydrazides via a desulfinative process
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In the presence of a Pd(ii)/P-ligand catalytic system, decarboxylative alkynylation of alkynyl carboxylic acids and arylsulfonyl hydrazides by desulfinative coupling could provide aryl alkynes in satisfactory yields by either judiciously selecting palladium catalysts or modulating phosphine ligands under mild conditions. The reported coupling reactions are very practical as they do not require the protection of inert gas or oxygen and are tolerant to many functional groups.
- Chang, Sheng,Liu, Ying,Yin, Shu Zhu,Dong, Lin Lin,Wang, Jian Feng
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supporting information
p. 5357 - 5362
(2019/04/04)
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- Preparation method of propiolic acid compounds
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The invention belongs to the technical fields of carbon dioxide activation and conversion and related chemistry, and discloses a preparation method of propiolic acid compounds. The preparation method comprises the following steps: (1) adding a copper catalyst, an additive, an alkali, and solid terminal alkynes into a reactor, adding an organic solvent under the protection of nitrogen gas, and filling CO2 into the reactor; or adding a copper catalyst, an additive, and an alkali into a reactor, adding an organic solvent and liquid terminal alkynes, and filling CO2 into the reactor; (2) sealing the reactor, and placing the reactor in an oil bath to carry out reactions; and (3) after reactions, opening a valve of the reactor to slowly release residual gas in the reactor, transferring the reaction liquid to a one-mouth bottle, carrying out concentration, diluting the concentrate by deionized water, adding n-hexane to carry out extraction, adding hydrochloric acid to carry out acidification, adding diethyl ether to carry out extraction, collecting the organic phase, washing the organic phase by a saturated saline solution, drying the organic phase by anhydrous sodium sulfate, filtering, and removing the solvent in vacuum to obtain the target material. The preparation method has the advantages of low reaction cost, simple experiment operation, mild reaction conditions, and easiness for industrialization.
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Paragraph 0049; 0050; 0051
(2017/12/09)
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- Cu(I)/Ag(I)-mediated decarboxylative trifluoromethylation of arylpropiolic acids with Me3SiCF3at room temperature
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A novel Cu(I)/Ag(I)-mediated decarboxylative trifluoromethylation of arylpropiolic acids with Me3SiCF3has been developed for the construction of Csp-CF3bond under mild conditions. This method proceeds smoothly at room temperature and shows a widely functional compatibility, providing a series of corresponding trifluoromethylated acetylenyl-containing aromatics in good yields.
- Yang, Lingling,Jiang, Linlin,Li, Yaming,Fu, Xinmei,Zhang, Rong,Jin, Kun,Duan, Chunying
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p. 3858 - 3862
(2016/07/06)
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- A bridged bis-amide-based rare earth amine compound and its preparation method and application
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The invention discloses bridged bisamido rare-earth amide compounds, and a preparation method and catalytic application thereof. The general formula of the rare-earth compounds is {LLn[N(SiMe3)2].THF}2, and the chemical structural formula is disclosed in the specification. In the general formula, L represents a bridged bisamido ligand, and the ligand LH2 is N,N'-(cyclohexane-1,2-diyl)bis(4-tert-butylbenzamide); and Ln is a rare-earth metal selected from lanthanum, neodymium, samarium, yttrium or ytterbium. The bridged bisamido rare-earth amide compounds have the advantages of simple synthesis process, definite structure and high yield. The invention also discloses a preparation method of the compounds and an application method of the compounds as a catalyst for catalyzing carboxylation reaction between alkynyl terminal group and carbon dioxide. The application method has the advantages of mild conditions, high activity, favorable selectivity and wide substrate application range.
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Paragraph 0119; 0120
(2017/04/21)
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- Carboxylation of terminal alkynes with CO2 catalyzed by bis(amidate) rare-earth metal amides
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Three novel bis(amidate) rare-earth metal amides {LRE[N(SiMe3)2]·THF}2 (H2L = N,N′-(cyclohexane-1,2-diyl)bis(4-tert-butylbenzamide); RE = La(1), Nd(2), Y(3)), which were prepared by the treatment of the bridged amide proligand H2L with RE[N(SiMe3)2]3 in tetrahydrofuran, have been characterized by single-crystal X-ray diffraction, elemental analyses, and NMR for complexes 1 and 3. All the complexes were found, for the first time, to be efficient catalysts for the direct carboxylation of terminal alkynes with CO2 at ambient pressure. And the Nd-based catalyst 2 showed the highest reactivity. Various propiolic acids with a good functional group tolerance were successfully synthesized in high-to-excellent yields under mild conditions. This journal is
- Cheng, Hao,Zhao, Bei,Yao, Yingming,Lu, Chengrong
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p. 1675 - 1682
(2015/03/18)
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- Copper catalysed domino decarboxylative cross coupling-cyclisation reactions: Synthesis of 2-arylindoles
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The efficient synthesis of 2-arylindoles and 6H-isoindolo[2,1-a]indol-6-one through copper catalysed domino sp-sp2 decarboxylative cross-coupling and subsequent cyclisation reactions of arylpropiolic acids with 2-iodotrifluoroacetanilide has been described. This methodology also demonstrates that indolo[1,2-c]quinazolin-6(5H)-one can be obtained with the elimination of trifluoromethyl anion.
- Ponpandian, Thanasekaran,Muthusubramanian, Shanmugam
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supporting information; experimental part
p. 4248 - 4252
(2012/08/28)
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