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.
Papers published on a yearly basis
Papers
More filters
TL;DR: In this paper, semi-empirical calculations (AMI and PM3) have been used in the framework of the Self Consistent Reaction Field (SCRF) and supermolecule models in order to analyse solvent effects on the Diels-Alder reactions of cyclopentadiene and 2-methyl-l,3-butadiene (isoprene) with acrylonitrile, acrolein, methyl vinyl ketone, and methyl acrylate.
Abstract: Semi-empirical calculations (AMI and PM3) have been used in the framework of the Self-Consistent Reaction Field (SCRF) and supermolecule models in order to analyse solvent effects on the Diels-Alder reactions of cyclopentadiene and 2-methyl-l,3-butadiene (isoprene) with acrylonitrile, acrolein, methyl vinyl ketone, and methyl acrylate. Both SCRF and supermolecule models describe correctly the effect of the solvent on endo/exo selectivities. Supermolecule calculations are suitable to explain the influence of hydrogen bonding on activation barriers, but fail to explain the effect of strong HBD solvents on para/meta regioselectivity.
24 citations
TL;DR: In this article, it was shown that a 4-CF 3 substituent on the phenyl ring at C3 of the enone strongly promotes the cyclomanganation of chalcone molecules.
24 citations
TL;DR: In this article, a series of 1-vinyl-2-pyridones using a variety of dienophilic species including dimethyl acetylenedicarboxylate, benzyne, maleic anhydride and methyl vinyl ketone has been explored in order to determine the generality of this method for generation of N -vinylisoquinuclidines.
24 citations
TL;DR: The reaction of allyltitanocenes, generated by the reductive titanation of various allylic substrates with a titanocene(II) species, with a variety of ketones produced the anti tertiary homoallylic alcohols in good diastereoselectivity, even when using sterically less congested ketones.
Abstract: A route with less congestion: A practical method for the highly diastereoselective preparation of anti tertiary homoallylic alcohols has been developed. The reaction of allyltitanocenes, generated by the reductive titanation of various allylic substrates with a titanocene(II) species, with a variety of ketones produced the anti tertiary homoallylic alcohols in good diastereoselectivity, even when using sterically less congested ketones (see scheme; Cp: cyclopentadienyl; Piv: pivaloyl).
The reaction of allyltitanocenes, generated by the reductive titanation of allylic sulfides or allylic alcohol derivatives with a titanocene(II) species, with phenyl and sterically hindered alkyl methyl ketones produced anti tertiary homoallylic alcohols with complete diastereoselectivity. Even when sterically less congested methyl ethyl ketone and methyl vinyl ketone were employed, the anti homoallylic alcohols were obtained with unprecedented high diastereoselectivity. The observed anti selectivity suggests that the reaction proceeds by the addition of primary (E)-σ-allyltitanocenes to ketones through chairlike cyclic transition states.
24 citations
TL;DR: In this article, the main reactions involved in the oxidation of propanone, butanone and pentan-3-one were elucidated by adding very small amounts of the compound individually to slowly reacting mixtures of H2 at 753 K. Although independent data are extremely limited, Arrhenius parameters were obtained by combination with the results of other workers.
Abstract: Elementary reactions involved in the oxidation of propanone,
butanone and pentan-3-one were elucidated by adding very small
amounts of the compound individually to slowly reacting mixtures of H2
+
O2 at 753 K. Kinetic studies of the relative rates of consumption
of the additive and H2 show that (21) and (22) are the key reactions
consuming the ketones. Values of k21
= 1.76 ×
109, 3.16 × 109 and 3.83 × 109
dm3 mol−1 s−1, for propanone,
butanone and pentan-3-one, respectively, are obtained, together
with k22
= 2.34 × 108, 7.2 ×
108 and 1.20 × 109 dm3 mol−1
s−1, respectively.
The values
of k21 show a 30–40% decrease by comparison
with those of the analogous rate constants obtained in this laboratory for
the structurally-related alkanes, whereas the values of k22
show a 10–15% increase. Although independent data are extremely
limited, Arrhenius parameters were obtained by combination with the results
of other workers. Arguments are presented for the occurrence of a reaction
not previously reported in the literature, namely the addition of H atoms
to propanone, which may occur prominently at relatively high temperatures.
Analytical studies of the oxidation chemistry
of the ketones at 753 K were carried out by adding individually 5 Torr of
each to a mixture containing 70, 140 and 285 Torr of O2, H2
and N2, respectively. With this approach, each oxidation occurs
under effectively the same highly controllable conditions. The mechanism for
the formation of products is discussed in the context of modern understanding
of hydrocarbon oxidation, and the use of a self-consistent set of
kinetic data gives a good prediction of the product yields in the initial
stages of reaction. The low yields of methyl vinyl ketone from butanone and
ethyl vinyl ketone from pentan-3-one were rationalised through
considerations of the thermochemistry and kinetics involved. Values of log(A/s−1) =
11.72 and E
= 136 kJ mol−1 are recommended
for the 1,5p H atom transfer reaction in CH3COCH2O2
radicals
24 citations