88-12-0Relevant articles and documents
SYNTHESIS OF N-VINYL COMPOUNDS BY REACTING CYLIC NH-COMPOUNDS WITH ACETYLENE IN PRESENCE OF HOMOGENOUS CATALYST
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Page/Page column 17; 20, (2021/06/26)
Process to produce N-vinyl compounds by homogeneous catalysis, wherein acetylene is reacted with a cyclic compound comprising a cyclic compound having at least one nitrogen as ring member, bearing a substitutable hydrogen residue (cyclic compound C), in a liquid phase in the presence of a ruthenium complex comprising at least one phosphine as ligand (RuCat).
Phosphine-Catalyzed Vinylation at Low Acetylene Pressure
Bienewald, Frank,Comba, Peter,Hashmi, A. Stephen K.,Menche, Maximilian,Rominger, Frank,Schafer, Ansgar,Schaub, Thomas,Sitte, Nikolai A.,Tuzina, Pavel
, p. 13041 - 13055 (2021/09/18)
The vinylation of various nucleophiles with acetylene at a maximum pressure of 1.5 bar is achieved by organocatalysis with easily accessible phosphines like tri-n-butylphosphine. A detailed mechanistic investigation by quantum-chemical and experimental methods supports a nucleophilic activation of acetylene by the phosphine catalyst. At 140 °C and typically 5 mol % catalyst loading, cyclic amides, oxazolidinones, ureas, unsaturated cyclic amines, and alcohols were successfully vinylated. Furthermore, the in situ generation of a vinyl phosphonium species can also be utilized in Wittig-type functionalization of aldehydes.
Ruthenium-catalyzed synthesis of vinylamides at low acetylene pressure
Semina, Elena,Tuzina, Pavel,Bienewald, Frank,Hashmi,Schaub, Thomas
supporting information, p. 5977 - 5980 (2020/06/04)
The reaction of cyclic amides with acetylene under low pressure, using ruthenium-phosphine catalysts, afforded a broad variety ofN-vinylated amides including (azabicyclic) lactams, oxazolidinones, benzoisoxazolones, isoindolinones, quinoxalinones, oxazinanones, cyclic urea derivatives (imidazolidinones), nucleobases (thymine), amino acid anhydrides and thiazolidinone.
Efficient palladium catalysis for the upgrading of itaconic and levulinic acid to 2-pyrrolidones followed by their vinylation into value-added monomers
Haus, Moritz O.,Hofmann, Jan P.,Konrad, Marc,Louven, Yannik,Palkovits, Regina
, p. 4532 - 4540 (2020/11/02)
The production of monomers from bio-based platform chemicals shows great potential to reduce the chemical industry's demand for fossil resources. We herein present a two-step approach, which yields N-vinyl-2-pyrrolidone monomers from bio-based carboxylic acids, such as itaconic and levulinic acid. A highly active, heterogeneous palladium catalyst facilitating the reductive amidation of itaconic acid (TOF = 950 molPyr·molPd-surface-1 h-1) as well as the reductive amination of levulinic acid (TOF = 4000 molPyr·molPd-surface-1 h-1) was designed. Especially the reductive amidation of itaconic acid to 3- and 4-methyl-2-pyrrolidone was found to be structure sensitive. A clear trend between Pd particle size and catalyst activity could be shown by the synthesis of Pd/C catalysts with varying Pd particle sizes. The vinylation of the synthesized methyl-2-pyrrolidones with acetylene was tested using common industrial conditions (10-18 bar acetylene, 150 °C, KOH catalyst, no solvent). Similar to the industrial vinylation of 2-pyrrolidone, good yields of up to 80% N-vinyl-methyl-2-pyrrolidone were received. Therefore, and due to the excellent maximum yield of methyl-2-pyrrolidones in reductive amidation (95 mol%), the envisioned process can be a promising drop-in technology, directly replacing fossil resources in the production of an established monomer class. This journal is
Extending the chemical product tree: A novel value chain for the production of: N -vinyl-2-pyrrolidones from biogenic acids
Haus, Moritz Otto,Louven, Yannik,Palkovits, Regina
supporting information, p. 6268 - 6276 (2019/12/03)
The sustainable production of polymers from biogenic platform chemicals shows great promise to reduce the chemical industry's dependence on fossil resources. In this context, we propose a new two-step process leading from dicarboxylic acids, such as succinic and itaconic acid, to N-vinyl-2-pyrrolidone monomers. Firstly, the biogenic acid is reacted with ethanolamine and hydrogen using small amounts of water as solvent together with solid catalysts. For effective conversion, the optimal catalyst (carbon supported ruthenium) has to hold the ability of activating H2 as well as (imide) CO bonds. The obtained products, N-(2-hydroxyethyl)-2-pyrrolidones, are subsequently converted in a continuous gas phase dehydration over simple sodium-doped silica, with excellent selectivity of above 96 mol% and water as the sole by-product. With a final product yield of ≥72 mol% over two process steps and very little waste due to the use of heterogeneous catalysis, the proposed route appears promising-commercially as well as in terms of Green Chemistry.
A-hydroxy ethyl pyrrolidine alkone dehydration N N-vinyl pyrrolidone preparing method (by machine translation)
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Paragraph 0171; 0172; 0173; 0174, (2016/11/02)
The invention relates to a-hydroxy ethyl pyrrolidine alkone dehydration N preparation N-vinyl pyrrolidone method. The method of the invention comprises will contain an acidic component or alkaline component comprising an alkaline component of a gas or liquid and N-hydroxyethyl pyrrolidone mixed, the temperature 300-500°C, pressure 0.01-0.1 MPa with a gas-phase vhsv 10-5000h ?1 through the dehydration catalyst under the condition of a fixed bed reactor, N-vinyl pyrrolidone products obtained. The preparation method of this invention in conversion, selectivity, in service life are very clearly superior to the prior art. (by machine translation)
Palladium-Catalyzed Markovnikov-Selective Hydroselenation of N-Vinyl Lactams with Selenols Affording N,Se-Acetals
Tamai, Taichi,Yoshikawa, Megumi,Higashimae, Shinya,Nomoto, Akihiro,Ogawa, Akiya
, p. 324 - 329 (2016/01/15)
The highly regioselective hydroselenation of N-vinyl lactams has been revealed to successfully afford the corresponding N,Se-acetals as Markovnikov adducts. In the case of terminal N-vinyl lactams, Markovnikov-selective hydroselenation proceeds efficiently in the absence of any catalyst (or additive), owing to the acidity of the selenols. In contrast, the self-promoted hydroselenation is inefficient with internal N-vinyl lactams. In the presence of palladium diacetate (Pd(OAc)2), however, the desired hydroselenation of internal N-vinyl lactams proceeds efficiently to afford the corresponding N,Se-acetals.
Facile Preparation of N-Vinylisobutyramide and N-Vinyl-2-pyrrolidinone
Tu, Siyu,Zhang, Chunming
, p. 2045 - 2049 (2016/01/08)
A facile synthesis of N-vinylakylamides from commercially available N-vinylformamide and corresponding acyl chlorides was developed and exemplified by the preparation of N-vinylisobutyramide (NVIBA) and N-vinyl-2-pyrrolidinone (NVP) in high yields (80-89%). Both NVIBA and NVP are valuable monomers for water-soluble polymers with an array of applications in personal care, pharmaceutical, agricultural, and industrial products.
N-vinyl amide and used in the production of hydroxylapatite
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Paragraph 0041, (2016/12/26)
PROBLEM TO BE SOLVED: To provide a method for producing an N-vinylamide which attains extremely high conversion and selectivity in the production of an N-vinylamide by dealcoholation reaction of N-(α-alkoxyalkyl)amide, and a catalyst used in the method.SOLUTION: According to the method, an N-vinylamide is produced by subjecting N-(α-alkoxyalkyl)amide to dealcoholation reaction in the presence of a surface-modified apatite catalyst prepared by surface-modifying an apatite represented by general formula (1) with a phosphoric acid compound. (In the formula, M is at least one member selected from the group consisting of Mg, Ca, Sr, Ba, Pb, Mn and Cd; Z is at least one member selected from the group consisting of P, As and Sb; X is at least one member selected from the group consisting of OH, F, Cl, Br, I and At; and 0≤y1).
A process to produce N-ethenyl-N-alkyl-alkylamides
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Paragraph 0064; 0065; 0066, (2015/02/25)
A process to produce N-ethenyl-N-alkyl-alkylamide including the steps of reacting at least a N-monoalkyl-alkylamide with a reactant including 1,3-dioxolan-2-one in the presence of at least a catalyst to form an intermediate, and of decarboxylating said intermediate to synthesize N-ethenyl-N-alkyl-alkylamide.
