4151-97-7Relevant academic research and scientific papers
Selective synthesis of epichlorohydrin: Via liquid-phase allyl chloride epoxidation over a modified Ti-MWW zeolite in a continuous slurry bed reactor
Ding, Luoyi,Yin, Jinpeng,Tong, Wen,Peng, Rusi,Jiang, Jingang,Xu, Hao,Wu, Peng
, p. 331 - 342 (2021/01/11)
The epoxidation of allyl chloride (ALC) to epichlorohydrin (ECH) with H2O2 using a piperidine (PI)-modified Ti-MWW catalyst (Ti-MWW-PI) in a continuous slurry reactor was investigated to develop an efficient reaction system for the corresponding industrial process. The reaction parameters, including solvent, reaction temperature, t-butanol/ALC mass ratio, ALC/H2O2 molar ratio, weight hourly space velocity of H2O2, and the addition amount of ammonia, were studied in detail to pursue high H2O2 conversion and ECH selectivity. A long catalytic lifetime of 244 h was achieved at high H2O2 conversion (>97.0%) and ECH selectivity (>99.8%) under optimized reaction conditions. The crystallinity was well maintained for the deactivated Ti-MWW-PI catalyst, which was regenerated by a combination of calcination and piperidine treatment. This journal is
Cellulose sulfate: An efficient heterogeneous catalyst for the ring-opening of epoxides with alcohols and anilines
Chaudhary, Pooja,Deepa,Meena, Dhan Raj,Aalam, Mohd Jubair,Yadav, Geeta Devi,Singh, Surendra
supporting information, p. 1834 - 1846 (2021/05/10)
Cellulose sulfate was synthesized by esterification of α-cellulose with concentrated sulfuric acid at ?10°C in ethanol. Cellulose is mainly sulfated on 3-, 6- and 3, 6-positions of the cellulose. It acts as a heterogeneous catalyst for the ring-opening of epoxides with alcohols or anilines and the Friedel-Crafts reaction between N-benzylindole and crotonaldehyde at room temperature. Methanolysis of cyclic epoxides, styrene oxide, terminal aliphatic epoxides, and glycidyl ethers were carried out using the catalyst (0.4–6.8 mg/mmol of epoxide) and afforded the corresponding products in 53–97% isolated yields after 10 min–24 h. Cellulose sulfate was successfully recycled and reused up to 3 catalytic cycles for the ring-opening of styrene oxide with methanol.
Rational design 2-hydroxypropylphosphonium salts as cancer cell mitochondria-targeted vectors: Synthesis, structure, and biological properties
Amerhanova, Syumbelya K.,Dimukhametov, Mudaris N.,Gubaidullin, Aidar T.,Islamov, Daut R.,Litvinov, Igor A.,Lyubina, Anna P.,Mironov, Vladimir F.,Nemtarev, Andrey V.,Pashirova, Tatiana N.,Titov, Eugenii A.,Tsepaeva, Olga V.,Voloshina, Alexandra D.
, (2021/11/01)
It has been shown for a wide range of epoxy compounds that their interaction with triphenylphosphonium triflate occurs with a high chemoselectivity and leads to the formation of (2-hydroxypropyl)triphenylphosphonium triflates 3 substituted in the 3-position with an alkoxy, alkylcarboxyl group, or halogen, which were isolated in a high yield. Using the methodology for the disclosure of epichlorohydrin with alcohols in the presence of boron trifluoride ether-ate, followed by the substitution of iodine for chlorine and treatment with triphenylphosphine, 2-hydroxypropyltriphenylphosphonium iodides 4 were also obtained. The molecular and supramolec-ular structure of the obtained phosphonium salts was established, and their high antitumor activity was revealed in relation to duodenal adenocarcinoma. The formation of liposomal systems based on phosphonium salt 3 and L-α-phosphatidylcholine (PC) was employed for improving the bioavailabil-ity and reducing the toxicity. They were produced by the thin film rehydration method and exhibited cytotoxic properties. This rational design of phosphonium salts 3 and 4 has promising potential of new vectors for targeted delivery into mitochondria of tumor cells.
MBA-cross-linked poly(N-vinyl-2-pyrrolidone)/ferric chloride macromolecular coordination complex as a novel and recyclable Lewis acid catalyst: Synthesis, characterization, and performance toward for regioselective ring-opening alcoholysis of epoxides
Rahmatpour, Ali,Zamani, Maryam
, (2021/09/30)
A novel macromolecular-metal coordination complex, MBA-cross-linked PNVP/FeCl3 material was fabricated by immobilization of water intolerant ferric chloride onto the porous cross-linked poly(N-vinyl-2-pyrrolidone) carrier beads as a macromolecular ligand or carrier which was prepared by suspension free-radical copolymerization of N-vinyl-2-pyrrolidone (NVP) and N,N′-methylene bis-acrylamide (MBA) as a crosslinking agent in water. The obtained PNVP/FeCl3 was characterized by UV/vis and FT-IR spectroscopies, TGA, FE-SEM, EDX, and ICP techniques. This heterogenized version of ferric chloride is a convenient and safe alternative to highly water intolerant ferric chloride. The catalytic performance of (PNVP/FeCl3) as an efficient and recyclable polymeric Lewis acid catalyst was appropriately probed in the regio-and stereoselective nucleophilic ring opening of various epoxides with various alcohols in excellent yields with TOF up to 182.48 h?1 without generating any waste. The activity data indicate that this heterogeneous catalyst is very active and could be easily recovered, and reused at least six times without appreciable loss of activity indicating its stability under experimental conditions.
Readily Scalable Methodology for the Synthesis of Nonsymmetric Glyceryl Diethers by a Tandem Acid-/Base-Catalyzed Process
Leal-Duaso, Alejandro,Gracia-Barberán, Sara,Mayoral, José A.,Garciá, José I.,Pires, Elisabet
, p. 154 - 162 (2020/02/04)
A useful optimized synthetic methodology has been designed for the synthesis of nonsymmetric glyceryl diethers from epichlorohydrin. A tandem process combining a cheap, heterogeneous, and fully recoverable acid catalyst and alkaline hydroxide is used for the synthesis of a variety of glycerol-derived ethers bearing different alkyl substituents in 1 and 3 positions. Different heterogeneous acid catalysts have been tested for the reaction of epichlorohydrin with several alcohols, the best results being obtained with readily available recoverable and inexpensive montmorillonite-K10 and Nafion NR50. For the second reaction step, potassium hydroxide is used. In all the cases, good yields of the desired glyceryl diethers are obtained in smooth reaction conditions, always with total conversion of epichlorohydrin and without the need of intermediate purification. Scale-up of the tandem process has been carried out with good results.
Epoxide ring opening with alcohols using heterogeneous Lewis acid catalysts: Regioselectivity and mechanism
Deshpande, Nitish,Parulkar, Aamena,Joshi, Rutuja,Diep, Brian,Kulkarni, Ambarish,Brunelli, Nicholas A.
, p. 46 - 54 (2019/01/04)
Lewis acidic catalytic materials are investigated for the regioselective ring opening of epoxides with alcohols. For ring opening epichlorohydrin with methanol, the catalytic activity shows a strong dependence on the type of support and Lewis acidic species used. While Sn-SBA-15 is catalytically active, significantly higher catalytic activity can be achieved with hydrothermally synthesized zeolites of which Sn-Beta is 6 and 7 times more active than Zr-Beta or Hf-Beta, respectively. Sn-Beta is determined to be more active and more regioselective for epoxide ring opening of epichlorohydrin with methanol than Al-Beta. For Sn-Beta, the activation energy for the reaction between epichlorohydrin and methanol is determined to be 53 ± 7 kJ mol?1. For epichlorohydrin, the activation energy barrier and experimentally observed regioselectivity are found using DFT to be consistent with a concerted reaction mechanism involving activation of the epoxide on an alcohol adsorbed on the catalytic site and nucleophilic attack by a second alcohol. The epoxide is shown to impact the regioselectivity and the mechanism since isobutylene oxide is selectively ring opened by methanol to form the terminal alcohol. DFT calculations indicate the mechanism for isobutylene ring opening involves epoxide activation and ring opening on an alcohol adsorbed onto the catalytic site. Finally, catalyst reuse testing indicates that Sn-Beta can be used for multiple reactions with no decrease in activity and limited to no leaching of the tin site, demonstrating Sn-Beta is a promising catalytic material for epoxide ring opening reactions with alcohols.
Fiber-supported Fe(iii) complex catalyst in spinning basket reactor for cleaner ring-opening of epoxides with alcohols
Shi, Xian-Lei,Sun, Benyu,Hu, Qianqian,Chen, Yongju,Duan, Peigao
, p. 3573 - 3582 (2019/07/09)
Herein, a newly designed fiber-supported iron catalyst was successfully synthesized by rooting diamine ligands into the surface layer of commercially available polyacrylonitrile fiber and then utilizing the diamine groups to immobilize Fe(iii) ions for heterogeneous catalytic ring-opening reactions. The resulting materials were characterized and observed in detail by elemental analysis, mechanical properties, FTIR spectroscopy and morphology during both the preparation and the utilization processes. Moreover, the fiber catalyst was used in the spinning basket reactor-mediated ring-opening of various epoxides by a series of alcohols under mild reaction conditions, giving good to quantitative yields of the corresponding β-alkoxy alcohols. In addition, the fiber catalyst in the impellers of the agitation system was shown to be reusable multiple times without leaching of the Fe(iii) ions, and when stored on the shelf remained equally active for at least three months. Furthermore, the catalytic system was convenient and effective for scaling-up experiments and thereby has prospects in industrial applications.
Zirconium triflate grafted on SBA-15 as a highly efficient solid acid catalyst for ring opening of epoxides by amines and alcohols
Tayade, Kamlesh N.,Wang, Lianyue,Shang, Sensen,Dai, Wen,Mishra, Manish,Gao, Shuang
, p. 758 - 766 (2017/04/24)
Metal (Al, Ti, Zr) triflate grafted mesoporous SBA-15 (AlTf/S, TiTf/S, ZrTf/S) samples were synthesized as inexpensive solid acid materials by a simple one-pot-two-step synthesis methodology. These materials were characterized by X-ray diffraction, N2-sorption, thermogravimetric analysis, Fourier transform infrared spectroscopy (FT-IR), in-situ pyridine FT-IR spectroscopy, and elemental analysis. ZrTf/S was found to be a highly efficient and reusable solid acid catalyst for ring opening of epoxides with amines and alcohols and produced β-amino alcohols and β-alkoxy alcohols respectively under ambient reaction conditions. The ZrTf/S catalyst showed the highest activity, which was attributed to its high acidity compared with that of the Ti and Al containing samples.
Scalable and super-stable exfoliation of graphitic carbon nitride in biomass-derived γ-valerolactone: Enhanced catalytic activity for the alcoholysis and cycloaddition of epoxides with CO2
Xue, Zhimin,Liu, Feijie,Jiang, Jingyun,Wang, Jinfang,Mu, Tiancheng
, p. 5041 - 5045 (2017/11/09)
Biomass-derived γ-valerolactone (GVL) could exfoliate bulk g-C3N4 to form a super-stable dispersion of few-layer g-C3N4 nanosheets with a high concentration of up to 0.8 mg mL-1 due to the polarity and the appropriate surface energy of GVL. The exfoliation process can be easily extended to a 200 ml scale and should be extended further. The formed g-C3N4 nanosheets showed enhanced activity for the alcoholysis of epoxides and the cycloaddition of epoxides with CO2 owing to their higher specific surface areas and more exposed active centers than the bulk g-C3N4. This affords a green, facile and scalable method to form few-layer g-C3N4 nanosheets and further expand the application of g-C3N4 materials to the field of non-photocatalysis.
Enhancement of CO2 Adsorption and Catalytic Properties by Fe-Doping of [Ga2(OH)2(L)] (H4L = Biphenyl-3,3′,5,5′-tetracarboxylic Acid), MFM-300(Ga2)
Krap, Cristina P.,Newby, Ruth,Dhakshinamoorthy, Amarajothi,García, Hermenegildo,Cebula, Izabela,Easun, Timothy L.,Savage, Mathew,Eyley, Jennifer E.,Gao, Shan,Blake, Alexander J.,Lewis, William,Beton, Peter H.,Warren, Mark R.,Allan, David R.,Frogley, Mark D.,Tang, Chiu C.,Cinque, Gianfelice,Yang, Sihai,Schr?der, Martin
, p. 1076 - 1088 (2016/02/09)
Metal-organic frameworks (MOFs) are usually synthesized using a single type of metal ion, and MOFs containing mixtures of different metal ions are of great interest and represent a methodology to enhance and tune materials properties. We report the synthesis of [Ga2(OH)2(L)] (H4L = biphenyl-3,3′,5,5′-tetracarboxylic acid), designated as MFM-300(Ga2), (MFM = Manchester Framework Material replacing NOTT designation), by solvothermal reaction of Ga(NO3)3 and H4L in a mixture of DMF, THF, and water containing HCl for 3 days. MFM-300(Ga2) crystallizes in the tetragonal space group I4122, a = b = 15.0174(7) ? and c = 11.9111(11) ? and is isostructural with the Al(III) analogue MFM-300(Al2) with pores decorated with -OH groups bridging Ga(III) centers. The isostructural Fe-doped material [Ga1.87Fe0.13(OH)2(L)], MFM-300(Ga1.87Fe0.13), can be prepared under similar conditions to MFM-300(Ga2) via reaction of a homogeneous mixture of Fe(NO3)3 and Ga(NO3)3 with biphenyl-3,3′,5,5′-tetracarboxylic acid. An Fe(III)-based material [Fe3O1.5(OH)(HL)(L)0.5(H2O)3.5], MFM-310(Fe), was synthesized with Fe(NO3)3 and the same ligand via hydrothermal methods. [MFM-310(Fe)] crystallizes in the orthorhombic space group Pmn21 with a = 10.560(4) ?, b = 19.451(8) ?, and c = 11.773(5) ? and incorporates μ3-oxo-centered trinuclear iron cluster nodes connected by ligands to give a 3D nonporous framework that has a different structure to the MFM-300 series. Thus, Fe-doping can be used to monitor the effects of the heteroatom center within a parent Ga(III) framework without the requirement of synthesizing the isostructural Fe(III) analogue [Fe2(OH)2(L)], MFM-300(Fe2), which we have thus far been unable to prepare. Fe-doping of MFM-300(Ga2) affords positive effects on gas adsorption capacities, particularly for CO2 adsorption, whereby MFM-300(Ga1.87Fe0.13) shows a 49% enhancement of CO2 adsorption capacity in comparison to the homometallic parent material. We thus report herein the highest CO2 uptake (2.86 mmol g-1 at 273 K at 1 bar) for a Ga-based MOF. The single-crystal X-ray structures of MFM-300(Ga2)-solv, MFM-300(Ga2), MFM-300(Ga2)·2.35CO2, MFM-300(Ga1.87Fe0.13)-solv, MFM-300(Ga1.87Fe0.13), and MFM-300(Ga1.87Fe0.13)·2.0CO2 have been determined. Most notably, in situ single-crystal diffraction studies of gas-loaded materials have revealed that Fe-doping has a significant impact on the molecular details for CO2 binding in the pore, with the bridging M-OH hydroxyl groups being preferred binding sites for CO2 within these framework materials. In situ synchrotron IR spectroscopic measurements on CO2 binding with respect to the -OH groups in the pore are consistent with the above structural analyses. In addition, we found that, compared to MFM-300(Ga2), Fe-doped MFM-300(Ga1.87Fe0.13) shows improved catalytic properties for the ring-opening reaction of styrene oxide, but similar activity for the room-temperature acetylation of benzaldehyde by methanol. The role of Fe-doping in these systems is discussed as a mechanism for enhancing porosity and the structural integrity of the parent material.
