Topic
Methyl vinyl ketone
About: Methyl vinyl ketone is a research topic. Over the lifetime, 1510 publications have been published within this topic receiving 26839 citations. The topic is also known as: 3-buten-2-one & gamma-oxo-alpha-butylene.
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TL;DR: In this article, a (2S,3R)-3-hydroxy-3-methylproline, a constituent of cyclodepsipeptides polyoxypeptins A and B, was efficiently synthesized by lithium chloride-induced diastereoselective tandem Michael-aldol reaction using methyl vinyl ketone and N-1-naphthylsulfonylglycine (R)-binaphTHyl ester and subsequent hydrolysis of the product in 39% overall yield and five steps.
9 citations
TL;DR: The experimental data are consistent with a kinetic model that the reaction goes through an adduct of CH3(C2H3)CIOO, similar to the cases of H/alkyl substituted Criegee intermediates, however, this vinyl adduct is less stable and decomposes to MVKO + I at a time scale of 10-3 s (faster at higher temperature), consistent with the results of quantum chemistry calculations.
Abstract: Isoprene is the most abundant alkene in the atmosphere. Ozonolysis of isoprene produces three very reactive carbonyl oxides (Criegee intermediates), including formaldehyde oxide, methyl vinyl ketone oxide (MVKO, CH3(C2H3)COO), and methacrolein oxide. The latter two Criegee intermediates are resonance-stabilized due to the vinyl group. Recently, the electronic spectrum of thermalized MVKO has been reported [Caravan, et al., Proc. Natl. Acad. Sci. U. S. A., 2020, 117, 9733]. In this work, we utilized this strong UV/visible absorption to investigate the reaction kinetics of MVKO with SO2 under a wide pressure range of 4 to 700 Torr. We followed a new method [Barber, et al., J. Am. Chem. Soc., 2018, 140, 10866], in which MVKO is produced through the reaction of a resonance-stabilized iodoalkene radical with O2. The experimental data are consistent with a kinetic model that the reaction goes through an adduct of CH3(C2H3)CIOO, similar to the cases of H/alkyl substituted Criegee intermediates. However, different from the H/alkyl adducts, which are stable over the time scales of typical kinetic experiments, this vinyl adduct CH3(C2H3)CIOO is less stable and decomposes to MVKO + I at a time scale of 10-3 s (faster at higher temperature), consistent with the results of quantum chemistry calculations and the fact that the resonance stabilization is disrupted at the adduct structure. The adduct decomposition is the major pathway that forms MVKO for pressures higher than 50 Torr. In addition, temperature dependence has been investigated for 278-319 K. The experimental activation energy of the adduct decomposition was measured to be 12.7 ± 0.3 kcal mol-1, consistent with the calculated dissociation energy of the adduct to MVKO + I (14 kcal mol-1). Furthermore, the temperature dependent rate coefficient of MVKO + SO2 reaction has been measured to be kSO2 = (4.0 ± 0.6) × 10-11 cm3 s-1 at 4-700 Torr and 298 K with a negative activation energy of -3.7 ± 0.4 kcal mol-1.
9 citations
TL;DR: The emission spectra and theoretical calculations indicate that HCN + CH2O is the only significant product channel for the C2H3 + NO reaction near room temperature, in contradiction to several reports in the literature.
Abstract: We have studied the vinyl + NO reaction using time-resolved Fourier transform emission spectroscopy, complemented by electronic structure and microcanonical RRKM rate coefficient calculations. To unambiguously determine the reaction products, three precursors are used to produce the vinyl radical by laser photolysis: vinyl bromide, methyl vinyl ketone, and vinyl iodide. The emission spectra and theoretical calculations indicate that HCN + CH2O is the only significant product channel for the C2H3 + NO reaction near room temperature, in contradiction to several reports in the literature. Although CO emission is observed when vinyl bromide is used as the precursor, it arises from the reaction of NO with photofragments other than vinyl. This conclusion is supported by the absence of CO emission when vinyl iodide or methyl vinyl ketone is used. Prompt emission from vibrationally excited NO is evidence of the competition between back dissociation and isomerization of the initially formed nitrosoethylene adduct...
9 citations
TL;DR: Amino substituted 1, 2, 3, 4, 4-tetrahydronaphthalene and 5, 6, 7, 8, TTE-6-(methylamino)-6-phenylquinoline derivatives were synthesized as discussed by the authors.
Abstract: Amino substituted 1, 2, 3, 4-tetrahydronaphthalene and 5, 6, 7, 8-tetrahydroquinoline derivatives (1, 2, 3, 4-tetrahydro-6-methoxy-N-methyl-2-phenyl-2-naphthylamine, 1, 2, 3, 4-tetrahydro-6-methoxy-N, N-dimethyl-2-phenyl-2-naphthylamine, 5, 6, 7, 8-tetrahydro-6-(methylamino)-6-phenylquinoline and 5, 6, 7, 8-tetrahydro-6-(dimethylamino)-6-phenylquinoline) were synthesized. Thus, Michael adducts of methyl vinyl ketone and acrylonitrile to methyl 5-cyano-2-oxo-5-phenylcyclohexanecarboxylate (I) were used for formation of skeleton of naphthalene and quinoline, respectively. Quinoline derivative was also obtained by condensation of cyclohexanone derivative with 3-aminoacrolein. Amino function was derived from nitrile via Hofmann reaction of amide. Furthermore, an interesting tricyclic compound, 3, 8a-ethano-3, 4, 4a, 8a, 5, 6-hexahydro-3-phenyl-2, 7 (1H, 8H)-quinolinedione, was obtained on cyclization reaction of a Michael adduct (IIa).
9 citations
TL;DR: In this paper, two regioisomeric α-naphthols obtained by aromatization of the methyl vinyl ketone adducts of an unsymmetrical isobenzofuran were differentiated from each other by the observation of significant upfield shifts of the peri proton resonances in the 1H nmr spectra of their acetates.
Abstract: Two regioisomeric α-naphthols 14 and 15 obtained by aromatization of the methyl vinyl ketone adducts of an unsymmetrical isobenzofuran 9 are differentiated from each other by the observation of significant upfield shifts of the peri proton resonances in the 1H nmr spectra of their acetates 16 and 17. Such upfield shifts of 0.3–0.6 ppm appear to be a general phenomenon and are probably due to the anisotropic effect of the acetate carbonyl group.
9 citations