- ELECTRONIC STRUCTURE AND CONFORMATIONAL PROPERTIES OF THE AMIDE LINKAGE
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The photoelectron spectra of N-vinyllactams 4-6 have been obtained.Based on band shape analyses and AM1 calculations the ionization potentials are assigned to molecular orbitals.The sequence of the three highest occupied MOs was found to be: ?3 (HOMO), n0, ?2.The MOs ?3 and ?2 are essentially linear combinations of ?N and ?C=C.Some conformational properties of N-vinyllactams have been studied by AM1 calculations on N-methyl-N-vinylacetamide (1) as a model compound for torsions of the vinyl and the acetyl group.Planar forms (ap and sp) were found as stable conformers.For 3-6 AM1 calculations also revealed essen tially planar vinyllactam units, while the α-lactam derivative 2 has a pyramidal nitrogen atom.
- Woydt, M.,Rademacher, P.,Kaupp, G.,Sauerland, O.
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- SYNTHESIS OF N-VINYL COMPOUNDS BY REACTING CYLIC NH-COMPOUNDS WITH ACETYLENE IN PRESENCE OF HOMOGENOUS CATALYST
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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).
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Page/Page column 17-18; 21
(2021/06/26)
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- Phosphine-Catalyzed Vinylation at Low Acetylene Pressure
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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.
- Bienewald, Frank,Comba, Peter,Hashmi, A. Stephen K.,Menche, Maximilian,Rominger, Frank,Schafer, Ansgar,Schaub, Thomas,Sitte, Nikolai A.,Tuzina, Pavel
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p. 13041 - 13055
(2021/09/18)
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- Ruthenium-catalyzed synthesis of vinylamides at low acetylene pressure
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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.
- Semina, Elena,Tuzina, Pavel,Bienewald, Frank,Hashmi,Schaub, Thomas
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supporting information
p. 5977 - 5980
(2020/06/04)
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- N-vinyl amide and used in the production of hydroxylapatite
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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).
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Paragraph 0048
(2016/12/26)
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- PROCESS FOR ALKENYLATING CARBOXAMIDES
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The present invention relates to a process for preparing N-(1-alkenyl)carboxamides of the formula I, which comprises reacting a carboxamide of the formula II with an alkyne of the formula III in the presence of a catalyst selected from among carbonyl complexes, halides and oxides of rhenium, manganese, tungsten, molybdenum, chromium and iron.
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Page/Page column 7-8
(2009/05/28)
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- Method for producing n-alkenyl amides
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A process for preparing N-alkenyl-amides by reacting the corresponding NH-amides with acetylenes in the liquid phase in the presence of basic alkali metal compounds and of a cocatalyst comprises using as the cocatalyst compounds of the general formulae (Ia) and/or (Ib) R1O—(CH2CH2CH2CH2O)n—H??(Ia): R1O—(CH2CH2CH2CH2O)n—R2,??(Ib): where n is 1, 2 or 3 and R1 and R2 are independently C1- to C6-alkyl or C2- to C6-alkenyl, or together a butenyl unit.
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- Purification of alkenyl compounds
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A process for purifying alkenyl compounds having a divalent or trivalent heteroatom in the à-position relative to the double bond by distillation comprises carrying out at least two distillations in which the purified alkenyl compounds are obtained from the gas phase by condensation, where the time between the first distillation after the synthesis of the alkenyl compounds and at least one further distillation is at least one day and the purified alkenyl compounds have an APHA color number of 30.
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Page column 7
(2008/06/13)
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- ELECTROCHEMICAL STUDIES ON HALOAMIDES. PART VIII. ELECTROSYNTHESIS OF N-(HALO)VINYLAMIDES
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The electrochemical reduction of N-haloethylamides 1a,b-4a,b (X = OCOCH3, Cl) at a mercury pool cathode in HCON(CH3)2 (or CH3CN) - 0.1 mol dm-3 Et4NClO4 solution has been investigated. 2,2,2-trichloroethyl derivatives 1a-4a (X = OCOCH3, Cl) give rise to the corresponding N-(2,2-dichlorovinyl)amides 5a-8a in good to excellent yields, whereas in the case of N-(2,2-dichloroethyl)amides 1b-4b the course of the reduction depends on the nature of the substituent at N-Cα and/or of the amide moiety.Acetamides 1b (X = OCOCH3, Cl) yield a mixture isomeric 5b, but pyrrolidone derivatives 2b behave differently depending on X.If X = Cl the expected isomeric dehydrohalogenation products 6b are formed, whereas vinylpyrrolidone 6c, in addition to 6b, is formed from 2b, X = OCOCH3.High yields of 6c are attained by treatment of N-(2-chloroethyl)-2-pyrrolidone, 9, with the electrogenerated pyrrolidone anion.
- Casadei, Maria Antonietta,Cesa, Stefania,Moracci, Franco Micheletti,Inesi, Achille
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p. 457 - 462
(2007/10/02)
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