627-40-7Relevant academic research and scientific papers
Raman spectroscopic study of allyl methyl ether (3-methoxy-1-propene), CH2=CHCH2OCH3, and some isotopically labelled analogues
Bowen, R. D.,Edwards, H. G. M.,Farwell, D. W.
, p. 77 - 86 (1995)
Fourier-transform Raman spectra of allyl methyl ether, CH2=CHCH2OCH3, three deuterated derivatives and one 13C derivative have been obtained.Comparison of the spectra of the deuterated and protiated compounds in conjunction with polarization data has enabled full vibrational assignments to be made for the carbon-hydrogen modes and the 13C data have identified some skeletal modes of the CO and CC bonds.As a result of the data obtained from the deuterated compounds in particular, some initial suggestions have been revised for tentative literature assignments of molecules of biological interest.In other cases, confirmation of existing assignments have been made.
Controlling the Lewis Acidity and Polymerizing Effectively Prevent Frustrated Lewis Pairs from Deactivation in the Hydrogenation of Terminal Alkynes
Geng, Jiao,Hu, Xingbang,Liu, Qiang,Wu, Youting,Yang, Liu,Yao, Chenfei
, p. 3685 - 3690 (2021/05/31)
Two strategies were reported to prevent the deactivation of Frustrated Lewis pairs (FLPs) in the hydrogenation of terminal alkynes: reducing the Lewis acidity and polymerizing the Lewis acid. A polymeric Lewis acid (P-BPh3) with high stability was designed and synthesized. Excellent conversion (up to 99%) and selectivity can be achieved in the hydrogenation of terminal alkynes catalyzed by P-BPh3. This catalytic system works quite well for different substrates. In addition, the P-BPh3 can be easily recycled.
Piperazine-promoted gold-catalyzed hydrogenation: The influence of capping ligands
Barbosa, Eduardo C. M.,Camargo, Pedro H. C.,Fiorio, Jhonatan L.,Hashmi, A. Stephen K.,Kikuchi, Danielle K.,Rossi, Liane M.,Rudolph, Matthias
, p. 1996 - 2003 (2020/04/22)
Gold nanoparticles (NPs) combined with Lewis bases, such as piperazine, were found to perform selective hydrogenation reactions via the heterolytic cleavage of H2. Since gold nanoparticles can be prepared by many different methodologies and using different capping ligands, in this study, we investigated the influence of capping ligands adsorbed on gold surfaces on the formation of the gold-ligand interface. Citrate (Citr), poly(vinyl alcohol) (PVA), polyvinylpyrrolidone (PVP), and oleylamine (Oley)-stabilized Au NPs were not activated by piperazine for the hydrogenation of alkynes, but the catalytic activity was greatly enhanced after removing the capping ligands from the gold surface by calcination at 400 °C and the subsequent adsorption of piperazine. Therefore, the capping ligand can limit the catalytic activity if not carefully removed, demonstrating the need of a cleaner surface for a ligand-metal cooperative effect in the activation of H2 for selective semihydrogenation of various alkynes under mild reaction conditions.
Deoxygenation of Epoxides with Carbon Monoxide
Maulbetsch, Theo,Jürgens, Eva,Kunz, Doris
, p. 10634 - 10640 (2020/07/30)
The use of carbon monoxide as a direct reducing agent for the deoxygenation of terminal and internal epoxides to the respective olefins is presented. This reaction is homogeneously catalyzed by a carbonyl pincer-iridium(I) complex in combination with a Lewis acid co-catalyst to achieve a pre-activation of the epoxide substrate, as well as the elimination of CO2 from a γ-2-iridabutyrolactone intermediate. Especially terminal alkyl epoxides react smoothly and without significant isomerization to the internal olefins under CO atmosphere in benzene or toluene at 80–120 °C. Detailed investigations reveal a substrate-dependent change in the mechanism for the epoxide C?O bond activation between an oxidative addition under retention of the configuration and an SN2 reaction that leads to an inversion of the configuration.
A HPPO by-product recycling synthetic 1, 3 - propanediol (by machine translation)
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Paragraph 0030-0035, (2019/07/04)
The invention belongs to the technical field of organic chemical industry, relates to a HPPO by-product recycling synthetic 1, 3 - propanediol, more specifically, relates to a propylene HPPO process with methanol the reaction product of propylene glycol monomethyl ether as the raw material, and sequentially passes through the dewatering, borohydrite oxidation, hydrolysis of the three-step reaction synthesizes the high value added 1, 3 - propylene glycol, 1, 3 - propylene glycol total yield of 80% or more, purity 99.5% or more, the invention has the simple process route, rationalization of resources use, 1, 3 - propylene glycol yield and purity and the like. (by machine translation)
Accessing Frustrated Lewis Pair Chemistry through Robust Gold@N-Doped Carbon for Selective Hydrogenation of Alkynes
Fiorio, Jhonatan Luiz,Gon?alves, Renato Vitalino,Teixeira-Neto, Erico,Ortu?o, Manuel A.,López, Núria,Rossi, Liane Marcia
, p. 3516 - 3524 (2018/04/14)
Pyrolysis of Au(OAc)3 in the presence of 1,10-phenanthroline over TiO2 furnishes a highly active and selective Au nanoparticle (NP) catalyst embedded in a nitrogen-doped carbon support, Au@N-doped carbon/TiO2 catalyst. Parameters such as pyrolysis temperature, type of support, and nitrogen ligands as well as Au/ligand molar ratios were systematically investigated. Highly selective hydrogenation of numerous structurally diverse alkynes proceeded in moderate to excellent yield under mild conditions. The high selectivity toward the industrially important alkene substrates, functional group tolerance, and the high recyclability makes the catalytic system unique. Both high activity and selectivity are correlated with a frustrated Lewis pairs interface formed by the combination of gold and nitrogen atoms of N-doped carbon that, according to density functional theory calculations, can serve as a basic site to promote the heterolytic activation of H2 under very mild conditions. This "fully heterogeneous" and recyclable gold catalyst makes the selective hydrogenation process environmentally and economically attractive.
Gold-Ligand-Catalyzed Selective Hydrogenation of Alkynes into cis-Alkenes via H2 Heterolytic Activation by Frustrated Lewis Pairs
Fiorio, Jhonatan L.,López, Núria,Rossi, Liane M.
, p. 2973 - 2980 (2017/05/31)
The selective hydrogenation of alkynes to alkenes is an important synthetic process in the chemical industry. It is commonly accomplished using palladium catalysts that contain surface modifiers, such as lead and silver. Here we report that the adsorption of nitrogen-containing bases on gold nanoparticles results in a frustrated Lewis pair interface that activates H2 heterolytically, allowing an unexpectedly high hydrogenation activity. The so-formed tight-ion pair can be selectively transferred to an alkyne, leading to a cis isomer; this behavior is controlled by electrostatic interactions. Activity correlates with H2 dissociation energy, which depends on the basicity of the ligand and its reorganization on activation of hydrogen. High surface occupation and strong Au atom-ligand interactions might affect the accessibility and stability of the active site, making the activity prediction a multiparameter function. The promotional effect found for nitrogen-containing bases with two heteroatoms was mechanistically described as a strategy to boost gold activity. (Graph Presented).
Unexpected cleavage of ether bonds of 1,3-dimethoxypropane in Grignard-Wurtz synthesis of a MgCl2-donor adduct
Nissinen, Ville,Pirinen, Sami,Pakkanen, Tuula T.
, p. 94 - 99 (2016/01/15)
Diethers are an important group of electron donors in Ziegler-Natta catalysts. A simple diether, 1,3-dimethoxypropane was studied as an electron donor in Grignard-Wurtz synthesis of a MgCl2-donor adduct. 1,3-Dimethoxypropane was unexpectedly found to undergo a cleavage reaction during the synthesis producing methoxy groups (OCH3). Each mole of 1,3-dimethoxypropane produced approximately 2 moles of methoxy groups, which are probably bound to magnesium chloride as methoxymagnesium chloride. A Grignard reagent, BuMgCl formed in the Grignard-Wurtz reaction most likely causes the cleavage of the ether bonds in 1,3-dimethoxypropane and there seem to be at least two parallel reaction paths taking place and producing at least two different by-products. The first step in the cleavage of 1,3-dimethoxypropane is a Grignard reagent (BuMgCl) induced elimination of OCH3, which gives 3-methoxy-1-propene. This intermediate product reacts further in a substitution reaction caused by the Grignard reagent producing 1-heptene as the by-product. The cleavage of the ether bond in 3-methoxy-1-propene and formation of OCH3 can also occur through another reaction path, which produces propene as the by-product.
Technological method for preparation of allyl ether compounds
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Paragraph 0056-0058, (2017/02/17)
The invention discloses a technological method for preparation of allyl ether compounds; the technological method can obtain the high-purity allyl ether compounds in low cost and high yield, has the advantages of high selectivity of the allyl ether compounds, less side reaction, easy separation and purification of the products, friendly technological process environment and the like, and is suitable for large-scale industrialized production.
Hydrogen-bond-activated palladium-catalyzed allylic alkylation via allylic alkyl ethers: Challenging leaving groups
Huo, Xiaohong,Quan, Mao,Yang, Guoqiang,Zhao, Xiaohu,Liu, Delong,Liu, Yangang,Zhang, Wanbin
supporting information, p. 1570 - 1573 (2014/04/17)
C-O bond cleavage of allylic alkyl ether was realized in a Pd-catalyzed hydrogen-bond-activated allylic alkylation using only alcohol solvents. This procedure does not require any additives and proceeds with high regioselectivity. The applicability of this transformation to a variety of functionalized allylic ether substrates was also investigated. Furthermore, this methodology can be easily extended to the asymmetric synthesis of enantiopure products (99% ee).
