Kinetics of the Copolymerization of Methyl Vinyl Ketone and Acrylamide Initiated by the Adduct of Methyl Vinyl Ketone and Imidazole

N-(Butyl-3-one)imidazole acts as an initiating adduct which is formed in the anionic polymerization of methyl vinyl ketone (MVK) induced by imidazole (Im) and is directly formed from Im and the MVK monomer. The kinetics of the anionic homopolymerization of MVK and acrylamide (AAm) under argon in the presence of the adduct were investigated in tetrahydrofuran (THF). The rate of polymerization for the MVK system is expressed as R_p = k[Adduct] [MVK], where k = 3.1 × 10^?6 L/(mol·s)in THF at 30°C. The overall activation energy, E_a , was found to be 5.34 kcal/mol. The R_p for the AAm system is expressed as R_p = k[Adduct] [AAm], where k = 6.8 × 10^?6 L/(mol·s) in THF at 30°C, with E_a 7.78 kcal/mol. The mechanism of the polymerization induced by the initiator adduct is discussed on the basis of these results.     

Radical Copolymerizability of Acrylamide Derivatives with Methyl Vinyl Ketone

Radical copolymerization of methyl vinyl ketone (MVK, M₁) with acrylamide (AAm) and its derivatives, such as methacrylamide (MAAm) and N,N′ -dimethylacrylamide (DMAAm), was carried out in dioxane or ethanol using α,α - azobisisobutylonitrile as the initiator at 60°C under vacuum. The monomer reactivity ratios found in dioxane were as follows: ri = 1.06, r₂ = 6.41 for the MVK-AAm system; r₁ = 0.29, r₂ = 3.05 for the MVK-MAAm system; and r₁ = 0.95, r₂ = 0.26 for the MVK-DMAAm system. The n and r₂ values obtained in ethanol were as follows: r₁ = 0.88, r₂ = 1.18 for the MVK-AAm system; and r₁ = 0.37, r₂ = 2.04 for the MVK-MAAm system. Q₂ and e₂ values of AAm derivatives in dioxane were estimated to be 3.03 and 1.04 for MAAm and 2.15 and 1.11 for DMAAm, respectively. The Q₂ and e₂ values of MAAm in ethanol were estimated to be 2.67 and 1.21, respectively. Based on these results, the alternating copolymerizability depends on the interaction of monomer-monomer, and the strong solvent effect depends on the radical copolymerization of the AAm derivatives.     

Stereoselective Titanium Mediated Trimerisation of Methyl Vinyl Ketone: A Novel Carbocyclisation Reaction

A new “one pot” stereoselective carbocyclisation reaction involving the trimerisation of methyl vinyl ketone (MVK) in the presence of TiCl₄ is reported.     

Kinetics and Mechanism Investigation of the Reaction between Triphenylphosphine, Di-tert-butyl Acetylenedicarboxilate and OH-Acid

Kinetic studies were made for the reaction between triphenylphosphine, di‐tert‐butyl acetylenedicarboxilate in the presence of OH‐acid, such as 2‐hydroxy‐4‐methoxybenzaldehyde. To determine the kinetic parameters of the reaction, it was monitored by UV spectrophotometery. The second order fits were automatically drawn by the software associated with a Cary UV spectrophotometer model Bio‐300 at appropriate wavelength. The values of the second order rate constant (k₂) were calculated using standard equations within the program. At the temperature range studied the dependence of the second order rate constant (ln k₂) on reciprocal temperature was in a good agreement with Arrhenius equation. This provided the relevant plots to calculate the activation energy of the reaction. Furthermore useful information was obtained from studies of the effect of solvent and concentration of reactants on the rate of reaction. Proposed mechanism was confirmed according to the obtained results and steady state approximation and first step (k₂) of reaction was recognized as a rate‐determining step on the basis of experimental data. In addition, assignment of more stable isomers (Z or E) was investigated using the theoretical study.     

Anionic Copolymerizations of Acrolein with Methyl Vinyl Ketone and Acrylamide by Imidazole

The anionic copolymerizations of acrolein (AL) with methyl vinyl ketone (MVK) and acrylamide (AAm) in the presence of imidazole (Im) as an initiator have been studied in tetrahydrofuran at 0°C. The AL-MVK copolymers were found to be composed of vinyl polymer with one Im group attached and having an aldehyde and a carbonyl side chain. The monomer reactivity ratio was determined from a Fineman-Ross plot as r₁ = 2.02 and r₂ = 0.06. On the other hand, the AL-AAm copolymer were found to be composed of polymer units of 1,2 and 1,4 addition polymerization of AAm. These observations might be explained by the intermolecular hydrogen transfer mechanism of AAm. The polymerization mechanisms were discussed on the basis of these copolymerization results.     

Iffland's Reaction with Methyl Ketone Oximes of Adamantane Series

Along Iffland's reactions from 1-adamantyl methyl ketone, (1-adamantyl)acetone, 3-hydroxy-1-adamantyl methyl ketone and N-bromosuccinimide were obtained the corresponding bromonitro derivatives that on reduction with sodium borohydride afforded 1-(1-adamantyl)-1-nitroethane, 1-(1-adamantyl)-2-nitropropane, and 1-(3-hydroxy-1-adamantyl)-1-nitroethane.     

手性磷酸催化的C（3）-取代吲哚和甲基乙烯基酮不对称串联反应

3位含有季碳手性中心的吲哚啉并环化合物是一类非常重要的化合物, 广泛存在于各种天然产物和具有生物活性的分子中. 化学家们发展了多种有效的途径来合成这类化合物. 其中以方便易得的吲哚衍生物为起始原料, 利用不对称去芳构化\环化串联的方法最为简单高效, 但多数工作都是从色胺或色醇衍生物出发, 合成二氢吡咯并吲哚啉或二氢呋喃并吲哚啉化合物. 因此, 发展其他类型的吲哚衍生物的不对称去芳构化\环化反应显得非常有必要. 作者课题组发展了手性磷酸催化的吲哚衍生物与甲基乙烯基酮的不对称Michael加成\环化串联反应. 以5 mol% (R)-SPINOL为骨架的手性磷酸(R)-4c为催化剂, 以中等到良好的收率和优秀的对映选择性构建了一系列手性吲哚[2,3-b]并氢化喹啉化合物, 而且该催化体系对于克级规模反应同样能够获得很好的结果.     

Aerobic Oxidation of Methyl Vinyl Ketone in Supercritical Carbon Dioxide

Ｔｈｅａｅｒｏｂｉｃｏｘｉｄａｔｉｏｎｏｆｅｔｈｙｌｅｎｅｔｏａｃｅｔａｌｄｅｈｙｄｅａｎｄｔｅｒｍｉｎａｌｏｌｅｆｉｎｓｔｏｃｏｒｒｅｓｐｏｎｄｉｎｇａｌｋａｎ 2 ｏｎｅｓｃａｔ ａｌｙｚｅｄｂｙｐａｌｌａｄｉｕｍ(ＩＩ)ａｎｄｃｏｐｐｅｒ(ＩＩｏｒＩ)ｓａｌｔｓａｒｅｃｏｌ ｌｅｃｔｉｖｅｌｙｋｎｏｗｎａｓＷａｃｋｅｒｏｘｉｄａｔｉｏｎｓ (Ｓｃｈｅｍｅ 1) .1Ｔｈｅｙａｒｅｖｅｒｙｉｍｐｏｒｔａｎｔｉｎｂｏｔｈｓｙｎｔｈｅｔｉｃａｎｄｉｎｄｕｓｔｒｉａｌｃｈｅｍ ｉｓｔｒｙ .Ｔｒｅａｔｍｅｎｔｏｆｔ…     

Characterizations and Electric Conductivities of Phosphorous Oxychloride-Treated Polymers Containing Methyl Vinyl Ketone

Abstract

Studies have been made on the characterizations and conductivities of poly(methyl vinyl ketone) (PMVK) and its copolymer with methyl methacrylate (poly(MVK-co-MMA)) after being reacted with phosphorus oxychloride (POCl₃). The POCl₃?treated polymers containing methyl vinyl ketone (MVK) were characterized by IR and UV spectroscopies to prove the structure of conjugated double bonds. The conductivities of all the MVK-containing polymers treated with POCl₃ were very low, ca. 10^?17 S/cm, in a vacuum regardless of the treatment time. The conductivities of the polymers when doped with iodine are in the range of the order of 10^?4 to 10^?6 S/cm. It was found that the conductivity of the POCl₃?treated copolymer is slightly lower than that of PMVK.     

Modification of Vinylformamide by Michael Addition to Methyl Acrylate and Methyl Vinyl Ketone,and Copolymers Derived from the Resulting Products

Vinylformamide reacts with methyl acrylate and methyl vinyl ketone under conditions of base catalysis, following the Michael addition pattern, to give methyl 3-(vinylformylamino)propionate and previously unknown 4-(vinylformylamino)-2-butanone. Radical copolymerization of these compounds with vinylformamide and N-vinylpyrrolidone was studied.     

Polymerization of Methyl Propiolate with Palladium Chloride,Triphenylphosphine, and Palladium Chloride Triphenylphosphine Complex

Some results of the bulk polymerization of methyl propiolate in the presence of PdCl₂, triphenylphosphine, and [(C₆H₅)₃P]₂.PdCl₂ complex are presented. From the polyconjugated polymers obtained, fractions based on their solubility in various solvents were separated. Subsequently, these products were characterized by IR and ¹H NMR spectroscopies and by thermal analysis. The data obtained indicate that polymerization assisted by [(C₆H₅)₃P]₂.PCl₂ proceeds faster, giving products with a lower cyclic oligomers content. The polymers possess good thermal stability and semiconducting properties.     

Vibrational Structure of a High-Resolution UV Absorption Spectrum of Methyl Vinyl Ketone in the Gas Phase

Moscow University Chemistry Bulletin - The resolved vibrational structure of a UV absorption spectrum of the molecule in the gas phase is obtained. The (0–0) bands of the isomers are found....     

丙酮一步法合成甲基异丁基酮催化剂研究

用浸渍法制备了丙酮一步法合成甲基异丁基酮负载型催化剂，考察了载体的预处理温度、添加镧助剂对催化剂性能的影响；用BET法测定了催化剂的表面积；采用H2-O2滴定法测定Pd的分散度．结果发现，用经过1．023K焙烧过的Al2O3为载体的催化剂具有较好的催化性能，添加镧助剂后催化剂的分散度、活性有较大的提高．     

Generation of Methyl Vinyl Ketone from Oxidation of Levulinic Acid Oxidized by Cupric Oxide Complex

Methyl vinyl ketone (MVK) is a kind of high‐value chemical which has been widely used in many fields. In this paper, it is formed from oxidation of levulinic acid–a hydrolysis product of biomass. Copper oxide supported on cerium dioxide (CuO/CeO₂) and alumina (CuO/Al₂O₃) were prepared and used for the oxidation of levulinic acid (LA). The oxidants were characterized by means of X‐ray diffraction (XRD), H₂‐temperature programmed reduction (H₂‐TPR) and atomic force microscope (AFM) techniques. CuO/CeO₂ and CuO/Al₂O₃ show a different behavior with respect to pure CuO. The experiments revealed that CuO/CeO₂ and CuO/Al₂O₃ can oxidize LA and get methyl vinyl ketone [yield of 15.5% detected by head space‐gas chromatograph‐mass spectrometer (HS‐GC‐MS)] under mild reactive conditions, while pure CuO oxidizes LA to produce butanone (MEK).     

Reaction of Triphenylphosphine Oxide with Diamino Compounds

Reactions of triphenylphosphine oxide with o-phenylenediamine, urea, and thiourea were carried out for the first time to give the corresponding cyclic diiminotriphenylphosphoranes.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 2, 2005, pp. 262–263.Original Russian Text Copyright © 2005 by Bidman.     

Kinetics and Mechanism of the Kabachnic-Fields Reaction

Abstract

The Kabachnic-Fields reaction is one of the most important methods of synthesis of functionally substituted derivatives of tetracoordinated phosphorus with P-C bond. At the same time mechanism of this important and interesting reaction practically has not been investigated.     

Kinetics and Mechanism of the Pudovik Reaction

Abstract

The kinetics and the mechanism of the Pudovik reaction for the series of α, β-unsaturated carbonyl compounds have been studied. The factors which determine the addition locoselectivity and the reactivity of the hydrophosphoryl and unsaturated compounds in this process are established. The qualitative and quantitative relationships obtained allow to predict the reaction rate and its direction depending on the reagents structure and also on the nature of catalyst and solvent used.     

Reaction of Triphenylphosphine Oxide with ortho-Dihydroxyaromatic Compounds

Triphenylphosphine oxide was first reacted with 2,3-dihydroxynaphthalene, as well as with halo- and alkyl-substituted 1,2-dihydroxybenzenes to obtain the corresponding (ortho-naphthylenedioxy)- or (ortho-phenylenedioxy)triphenylphosphoranes.