96396-91-7

Upstream product

• 124-38-9 carbon dioxide 
• 536-74-3 phenylacetylene 
• 67-64-1 acetone 
• 1966-65-0 3-methyl-1-phenyl-1-pentyn-3-ol 
• 1719-19-3 2-Methyl-4-phenyl-3-butyn-2-ol 

Downstream Products

• 22609-91-2 δ,δ-dimethyl-α-phenyltetronic acid 
• 121409-72-1 3,3-Dimethyl-1-phenylhex-5-en-2-one 

Relevant academic research and scientific papers

AgX@carbon (X = Br and I) as robust and efficient catalysts for the reaction of propargylic alcohols and CO2 to carbonates under ambient conditions

Development of new efficient catalytic systems for chemical transformation of CO2 is a very attractive topic in green chemistry. In this work, we studied the synthesis of α-alkylidene cyclic carbonates through the coupling reaction between propargylic alcohols and CO2 with new silver catalysts. It was found that activated carbon supported AgX (X = Br and I) was a simple and efficient catalyst for the carboxylative cyclization of propargyl alcohols with CO2 at atmospheric pressure and room temperature. Nearly 99% yield of the desired product was obtained, and the product could be simply separated through solvent extraction. Moreover, the catalyst could be easily recovered and reused at least ten times without a decrease in the catalytic activity and selectivity. These findings are useful for the development of an environmentally friendly chemical process for the production of α-alkylidene cyclic carbonates.

A CO2-induced ROCO2Na/ROCO2H buffer solution promoted the carboxylative cyclization of propargyl alcohol to synthesize cyclic carbonates

A CO2-induced ROCO2Na/ROCO2H buffer solution is developed and employed in the carboxylative cyclization of propargyl alcohol to generate α-alkylene cyclic carbonates. The introduction of CO2 into the propargyl a

Synthesis Cu(I)–CN-based MOF with in-situ generated cyanogroup by cleavage of acetonitrile: Highly efficient for catalytic cyclization of propargylic alcohols with CO2

Developing a highly effective process for synthesis a cyano-bridged compound to avoid toxic organic or inorganic cyanides is very significant method for alleviating cyanides pollution. Here, a CN-based MOF catalyst (Cu(I)–CN–BPY) was synthesized by using copper ions coupled with Na4W10O32 in CH3CN under solvothermal conditions. The cyano-groups are generated in situ from the cleavage of C(sp3)–C(sp) in CH3CN. Because Cu(I) sites have ability to activate π-activate internal alkynes of carbon–carbon triple bonds for carboxylic cyclization reactions, which was applied in the cyclization of propargylic alcohols with CO2 and exhibited high efficiency with >95 % yields. For seeking out the active sites of MOF structure in carboxylic cyclization, we also synthesized two MOFs of Cu(I)–Cl–BPY and Cu(I)–I–BPY, and investigated for this reaction.

Ag Nanoparticles Supported on a Resorcinol-Phenylenediamine-Based Covalent Organic Framework for Chemical Fixation of CO2

Covalent organic frameworks are a new class of crystalline organic polymers possessing a high surface area and ordered pores. Judicious selection of building blocks leads to strategic heteroatom inclusion into the COF structure. Owing to their high surface area, exceptional stability and molecular tunability, COFs are adopted for various potential applications. The heteroatoms lining in the pores of COF favor synergistic host–guest interaction to enhance a targeted property. In this report, we have synthesized a resorcinol-phenylenediamine-based COF which selectively adsorbs CO2 into its micropores (12 ?). The heat of adsorption value (32 kJ mol?1) obtained from the virial model at zero-loading of CO2 indicates its favorable interaction with the framework. Furthermore, we have anchored small-sized Ag nanoparticles (≈4–5 nm) on the COF and used the composite for chemical fixation of CO2 to alkylidene cyclic carbonates by reacting with propargyl alcohols under ambient conditions. Ag@COF catalyzes the reaction selectively with an excellent yield of 90 %. Recyclability of the catalyst has been demonstrated up to five consecutive cycles. The post-catalysis characterizations reveal the integrity of the catalyst even after five reaction cycles. This study emphasizes the ability of COF for simultaneous adsorption and chemical fixation of CO2 into corresponding cyclic carbonates.

A rose bengal-functionalized porous organic polymer for carboxylative cyclization of propargyl alcohols with CO2

A Rose bengal-functionalized porous organic polymer (RB-POP) was prepared with a specific surface area of up to 562 m2 g-1. In the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene, RB-POP supported Ag(0) nanoparticles exhibited excellent performance for catalyzing cyclization of propargyl alcohols with CO2 at 30 °C, achieving a TOF of 5000 h-1, the highest value among the reported ones.

Unusual Missing Linkers in an Organosulfonate-Based Primitive-Cubic (pcu)-Type Metal-Organic Framework for CO2 Capture and Conversion under Ambient Conditions

A noninterpenetrated organosulfonate-based metal-organic framework (MOF) with a defective primitive-cubic (pcu) topology was successfully synthesized. The unusual missing linkers, along with the highest permanent porosity (～43%) in sulfonate-MOFs, offer a versatile platform for the incorporation of alkynophilic Ag(I) sites. The cyclic carboxylation of alkyne molecules (e.g., propargyl alcohol and propargyl amine) into α-alkylidene cyclic carbonates and oxazolidinones were successfully catalyzed by the use of Ag(I)-embedded sulfonate-MOF under atmospheric pressure of CO2. In all the three catalytic reactions using CO2 as a C1 feedstock, the highly robust sulfonate-based MOF catalyst exhibit at least three-cycle reusability.

CO2 transformation under mild conditions using tripolyphosphate-grafted KCC-1-NH2

Fibrous nanosilica (KCC-1) as a catalyst support was investigated in terms of stability, recycling, and reusability. For the first time, CO2 transformation was performed via the synthesis and application of KCC-1 together with sodium tripolyphosphate (STPP) and 3-aminopropyltriethoxysilane (APTES) as its functionalized derivative. To this goal, KCC-1/STPP NPs were applied to act as a nanocatalyst with excellent catalytic activities under green reaction conditions.

Alkyne Activation by a Porous Silver Coordination Polymer for Heterogeneous Catalysis of Carbon Dioxide Cycloaddition

The widely studied porous coordination polymers, possessing large pores to adsorb waste carbon dioxide gas and further transform it into valuable chemical products, have been attracting research interest, both industrially and academically. The active silver(I) ions endow the specific alkynophilicity to activate C≡C bonds of alkyne-containing molecules via π activation. Incorporating catalytic Ag metal sites into the porous frameworks represents a promising approach to construct heterogeneous catalysts that cyclize propargylic alcohols with CO2, which is highly desirable for the environmentally benign conversion of carbon dioxide to fine chemicals. We report the preparation of porous coordination polymers (PCPs) with active silver sites and efficient silver-silver bond formation by carefully modifying the coordination geometries of the silver sites. The decentralized silver(I) chains in the porous frameworks enable the efficient conversion of CO2 and derivatives of acetylene to α-alkylidene cyclic carbonates in a heterogeneous manner. X-ray structure analysis reveals two kinds of substrate molecules positioned within the pores of the framework, which correspond to trapping and activated modes through the multiple interactions with the functional Ag chains. The example of tandem conversion of simple alkynes and carbon dioxide to α-alkylidene cyclic carbonates is also presented. The well-positioned catalytic silver(I) sites and the crystalline properties of the frameworks facilitated the structural analyses of the intermediates of each catalytic step, providing knowledge of the synergistic nature of the σ and π activation of C≡C bonds. The successful catalysis of azide-alkyne cycloaddition and synthesis of propargylic alcohols via terminal alkynes could also give another indicator for the activation properties of Ag sites.

A simple and robust AgI/KOAc catalytic system for the carboxylative assembly of propargyl alcohols and carbon dioxide at atmospheric pressure

A simple and robust AgI/KOAc system was developed for the cyclization of propargyl alcohols and carbon dioxide under mild conditions, and was identified to have excellent activities for numerous substrates, especially sterically hindered terminal alkynes and internal alkynes. Notably, the Ag loading involved was an unprecedentedly low level of 0.05 mol%.

One-pot carboxylative cyclization of propargylic alcohols and CO2 catalysed by N-heterocyclic carbene/Ag systems

A series of N-heterocyclic carbene (NHC)/Ag systems were developed for the carboxylative assembly of propargylic alcohols and carbon dioxide (CO2). With the catalysis of these catalytic systems, a variety of target α-alkylidene cyclic carbonates could be obtained smoothly under atmospheric CO2 pressure in straightforward one-pot processes. Particularly, these reactions could be performed without any stoichiometric addition of bases or additives. Further mechanistic investigation reveals that the excellent activities are attributed to the effective activations of CO2 accomplished by the NHCs via the formation of the NHC-CO2 adducts.