56621-35-3Relevant articles and documents
Selective synthesis of 4-hydroxyisophorone and 4-ketoisophorone by fungal peroxygenases
Aranda, Carmen,Municoy, Martí,Guallar, Víctor,Kiebist, Jan,Scheibner, Katrin,Ullrich, René,Del Río, José C.,Hofrichter, Martin,Martínez, Angel T.,Gutiérrez, Ana
, p. 1398 - 1405 (2019/03/26)
The recently discovered unspecific peroxygenases (UPOs) from the ascomycetes Chaetomium globosum and Humicola insolens were capable of selectively hydroxylating isophorone to 4-hydroxyisophorone (4HIP) and 4-ketoisophorone (4KIP), which are substrates of interest for the pharmaceutical and flavor-and-fragrance sectors. The model UPO from the basidiomycete Agrocybe aegerita was less regioselective, forming 7-hydroxyisophorone (and 7-formylisophorone) in addition to 4HIP. However, it was the most stereoselective UPO yielding the S-enantiomer of 4HIP with 88% ee. Moreover, using H. insolens UPO full kinetic resolution of racemic HIP was obtained within only 15 min, with >75% recovery of the R-enantiomer. Surprisingly, the UPOs from two other basidiomycetes, Marasmius rotula and Coprinopsis cinerea, failed to transform isophorone. The different UPO selectivities were rationalized by computational simulations, in which isophorone and 4HIP were diffused into the enzymes using the adaptive PELE software, and the distances from heme-bound oxygen in H2O2-activated enzyme to different substrate atoms, and the corresponding binding energies were analyzed. Interestingly, for process upscaling, full conversion of 10 mM isophorone was achieved with H. insolens UPO within nine hours, with total turnover numbers up to 5500. These biocatalysts, which only require H2O2 for activation, may represent a novel, simple and environmentally-friendly route for the production of isophorone derivatives.
Novel catalytic system: N-hydroxyphthalimide/hydrotalcite-like compounds catalysing allylic carbonylation of cyclic olefins
Zhou, Yin,Tang, Rui-Ren,Song, Dan
, p. 888 - 897 (2017/02/05)
N-hydroxyphthalimide (NHPI) combined with stable and recoverable transition metal-aluminium binary hydrotalcite-like compounds (M-Al HTLcs, M = Cu, Ni, Co) as an unprecedented catalytic system was demonstrated for the allylic carbonylation, as the model reaction, of cyclic olefins with tert-butyl hydroperoxide (TBHP), using isophorone (IP) to ketoisophorone (KIP). The results showed NHPI combined with Cu-Al HTLcs to be an efficient catalytic system and the influences of various reaction conditions of the catalytic reaction were optimised. A maximum IP conversion of 68.0 % with 81.8 % selectivity to KIP was afforded under the optimal reaction conditions. Experiments of repeatability and restorability showed Cu-Al HTLcs to be stable for at least five cycles without noticeable loss of catalytic activity. Expanding substrates could also be efficiently converted to the corresponding ketones under the optimised reaction conditions with appreciable yields. A plausible catalytic reaction mechanism was proposed.
Process and apparatus for producing ketoisophorone
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, (2008/06/13)
β-isophorone is formed by isomerizing α-isophorone in the presence of an isomerizing catalyst (an aliphatic C5-20 polycarboxylic acid) in an isomerizing-reaction unit 1. The β-isophorone thus formed is oxidized with oxygen in an inert solvent in the presence of an oxidizing catalyst (a complex salt of a transition metal and an N,N'-disalicylidenediamine) in an oxidizing-reaction unit 2, thereby forming ketoisophorone. After removing a low-boiling point component, which is an impurity (non-conjugated cyclic ketone), from the reaction mixture using a distilling unit 3, a high-boiling component (oxidizing catalyst) is separated in a distilling unit 4, and then ketoisophorone is separated from the solvent in the separation unit 5. Thereafter, the solvent containing 0 to 5,000 ppm (weight basis) of the impurities and substantially free from ketoisophorone is recycled to the oxidizing reaction through a recycling line 6. According to the present invention, the combination of the isomerizing reaction and the oxidizing reaction makes it possible to produce ketoisophorone from α-isophorone while maintaining the activity of the oxydizing catalyst.
