56621-35-3

Upstream product

• 21634-43-5 5,5-Dimethyl-3-vinylcyclohex-2-en-1-one 
• 77822-59-4 3-(1',2'-Epoxy-2'-methyl-1'-propyl)-5,5-dimethyl-2-cyclohexen-1-on 
• 77822-66-3 5,5-Dimethyl-3-(1',2'-dihydroxy-2'-methylpropyl)-2-cyclohexen-1-on 
• 4694-17-1 5,5-dimethlycyclohex-2-en-1-one 
• 108946-84-5 3,3-dimethyl-5-(nitromethyl)cyclohexanone 
• 3212-51-9 5,5-Dimethyl-3-(2'-methyl-1'-propen-1'-yl)-2-cyclohexen-1-on 
• 78-59-1 3,5,5-Trimethylcyclohex-2-en-1-one 
• 471-01-2 3,5,5-trimethylcyclohex-3-en-1-one 
• 546-67-8 lead(IV) tetraacetate 
• 77822-60-7 5,5-Dimethyl-3-(2'-hydroxy-2'-methyl-1'-propyl)-2-cyclohexen-1-on 

Downstream Products

• 97345-36-3 (4RS)-3-(1'-hydroxy-8'-methoxy-4',8'-dimethylnonyl)-5,5-dimethylcyclohex-2-en-1-one 
• 700-13-0 Trimethylhydroquinone 

Relevant academic research and scientific papers

Selective synthesis of 4-hydroxyisophorone and 4-ketoisophorone by fungal peroxygenases

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.

Two catalytic systems of l-proline/Cu(II) catalyzed allylic oxidation of olefins with tert-butyl hydroperoxide

The nontoxic and water-soluble l-proline combined with two different forms of copper(ii): recoverable Cu-Al hydrotalcite-like compounds (Cu-Al HTLcs) and water-soluble CuCl2, as a heterogeneous catalytic system (l-proline/Cu-Al HTLcs) and two-phase catalytic system (l-proline/CuCl2) to catalyze allylic oxidation with tert-butyl hydroperoxide. The results showed that l-proline/Cu(ii) is highly active for oxidizing isophorone (IP) into ketoisophorone (KIP). Maximum catalytic effects were afforded respectively under the optimal reaction conditions, which obtained 77.9% IP conversion with 74.3% KIP selectivity catalyzed by l-proline/Cu-Al HTLcs and 73.5% conversion with 81.6% selectivity by l-proline/CuCl2. Recycling experiments of the two catalytic systems of l-proline/Cu(ii) showed they are stable and recyclable for at least six cycles with appreciable catalytic activity. And various hydrocarbons could be smoothly transformed into corresponding ketones with satisfactory conversion and selectivity by the two catalytic systems.

Novel catalytic system: N-hydroxyphthalimide/hydrotalcite-like compounds catalysing allylic carbonylation of cyclic olefins

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.

An efficient and mild oxidation of α-isophorone to ketoisophorone catalyzed by N-hydroxyphthalimide and copper chloride

N-hydroxyphthalimide (NHPI) and copper chloride (CuCl2) were first utilized for aerobic oxidation of α-isophorone (α-IP) to ketoisophorone (KIP) and the effects of co-catalysts, temperature, reaction time, solvent, amount of CuCl2 and pressure of oxygen were investigated extensively. NHPI/CuCl2 turned out to be highly efficient to this oxidation with up to 91.3% conversion and 81.0% selectivity under mild conditions. And various hydrocarbons including benzylic compounds, cycloalkene and its derivatives were also oxidized smoothly under optimized conditions. Moreover, the possible reaction mechanism was proposed and verified by FT-IR spectra.

Process and apparatus for producing ketoisophorone

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.

Enhanced catalytic activity and selectivity in oxidation of α-isophorone to ketoisophorone with phosphomolybdic acid

Aerobic allylic oxidation of α-isophorone with phosphomolybdic acid as catalyst in combination with DMSO and potassium tert-butoxide provides ketoisophorone in unprecedented high yield. This study suggests that the solvent can play a pivotal role in directing selectivity in allylic oxidations of highly substituted cyclic olefins.

Selective aerobic oxidation of isophorone catalyzed by molybdovanadophosphate supported on carbon (NPMoV/C)

Isophorone was smoothly oxidized with molecular oxygen by molybdovanadophosphate supported on the active carbon ((NPMoV/C) to give 3-formyl-5,5-dimethyl-2-cyclohexen-1-one in relatively high selectivity. The regioselectivity of the oxidation by NPMoV/C was found to be just opposite to that of the conventional oxidations, The pore size of the supports appears to be an important factor governing the regioselectivity.

The Vinylogous Tricarbonyl Chromophore. Violerythrine End Groups and Related Six-Membered Ring Compounds. Their Synthesis, Conformation, and Investigation by Photoelectron, UV, and NMR Spectroscopy and by Crystal Structure Analysis

The synthesis of five- and six-membered rings 3a, 4, 5b, 5c, and 17a, containing the structural moiety 3-pentene-1,2,5-trione, is described.The chromophoric properties of these vinylogous tricarbonyls together with related compounds are investigated.The conformation in solution, particularly the torsion angle ring/sidechain, can be derived from measurements of 3JCH coupling constants, NOE difference spectra, and force-field calculations.X-ray structure analyses of 11a, 17a, 18a, and 35 afford geometries in the solid state.Ionization energies are determined by means of photoelectron spectroscopy.The theoretical calculations and interpretation of absorption spectra and colour are carried out using the models CNDO/S-CI and HAM/3.

Zur Photospaltung konjugierter γ,δ-Epoxyenone. UV.-Bestrahlung von 3-(1',2'-Epoxy-2'-methyl-prop-1'-yl)-5,5-dimethyl-2-cyclohexen-1-on

On 1?,?*-excitation (λ=254 nm) 9 undergoes cleavage of the C(γ),C(δ)-bond yielding 17 and a, which gives 18 by photofragmentation.In presence of maleinic ester the photolysis of 9 yields 20, in the presence of methanol 21 and 22 are

Process for producing ketoisophorone

Process for producing ketoisophorone from β-isophorone by oxidation utilizing a metal salt catalyst and an organic nitrogen base.