956-82-1Relevant academic research and scientific papers
METHOD FOR PRODUCING 3-METHYLCYCLOALKENONE COMPOUND
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, (2022/02/11)
The present invention relates to a method for producing a 3-methylcycloalkenone compound and a method for producing muscone. In the presence of a zirconium oxide catalyst, a diketone represented by the following general formula (1): wherein in formula (1), n represents 8, 9, 10, 11 or 12, is subjected to a vapor-phase intramolecular condensation reaction, whereby a 3-methylcycloalkenone compound can be produced with high reaction efficiency. When a 3-methylcyclopentadecenone compound produced by this method is hydrogenated in a known manner, muscone can be produced efficiently.
Preparation method of musk ketone
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Paragraph 0046; 0056-0058, (2020/12/30)
The invention relates to a preparation method of muscone, which includes the steps of: 1) adding 1,2-diol supported on polystyrene resin, 3-methyl dienone, methylbenzene and pyridinium p-toluenesulfonate, stirring and heating the materials, cooling the materials to room temperature, and filtering the materials to produce a first ketal compound; 2) adding a first solvent and a catalyst, performingheating reflux until the reaction is finished, cooling a reaction product to room temperature and filtering the reaction product to produce a second ketal compound; 3) adding a first solvent and an acid solution, stirring the mixture until the reaction is finished, cooling a reaction product to room temperature, washing the reaction product to separate a first organic layer, and performing normalpressure recovery to the solvent in the first organic layer to collect a first ketene compound; 4) adding an alcohol solution and a metal catalyst into a reaction bottle, repeatedly replacing gas in the reaction bottle with N2 and H2, and performing a reaction at normal temperature and under normal pressure, and when the reaction is finished, performing filtration and pressure reduced rectification to obtain the muscone. The preparation method is simple in technical process and low in cost, and allows industrial large-scale production.
Preparation method for L-muscone
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, (2019/05/08)
The invention provides a preparation method for L-muscone. Dehydrogenated muscone is taken as a starting material, chiral amine is taken as an inducer, homogeneous phase iridium is taken as a catalyst, hydrogen is taken as a reducing agent, and the L-muscone product is synthesized through imine synthesis, asymmetric hydrogenation and hydrolysis reaction. The homogeneous phase iridium catalyst usedin the method has low dose and low cost; the synthetic route has high total yield and few three wastes and is suitable for industrial production of L-muscone.
Transfer Hydrogenation of Alkenes Using Ethanol Catalyzed by a NCP Pincer Iridium Complex: Scope and Mechanism
Wang, Yulei,Huang, Zhidao,Leng, Xuebing,Zhu, Huping,Liu, Guixia,Huang, Zheng
supporting information, p. 4417 - 4429 (2018/04/05)
The first general catalytic approach to effecting transfer hydrogenation (TH) of unactivated alkenes using ethanol as the hydrogen source is described. A new NCP-type pincer iridium complex (BQ-NCOP)IrHCl containing a rigid benzoquinoline backbone has been developed for efficient, mild TH of unactivated C-C multiple bonds with ethanol, forming ethyl acetate as the sole byproduct. A wide variety of alkenes, including multisubstituted alkyl alkenes, aryl alkenes, and heteroatom-substituted alkenes, as well as O- or N-containing heteroarenes and internal alkynes, are suitable substrates. Importantly, the (BQ-NCOP)Ir/EtOH system exhibits high chemoselectivity for alkene hydrogenation in the presence of reactive functional groups, such as ketones and carboxylic acids. Furthermore, the reaction with C2D5OD provides a convenient route to deuterium-labeled compounds. Detailed kinetic and mechanistic studies have revealed that monosubstituted alkenes (e.g., 1-octene, styrene) and multisubstituted alkenes (e.g., cyclooctene (COE)) exhibit fundamental mechanistic difference. The OH group of ethanol displays a normal kinetic isotope effect (KIE) in the reaction of styrene, but a substantial inverse KIE in the case of COE. The catalysis of styrene or 1-octene with relatively strong binding affinity to the Ir(I) center has (BQ-NCOP)IrI(alkene) adduct as an off-cycle catalyst resting state, and the rate law shows a positive order in EtOH, inverse first-order in styrene, and first-order in the catalyst. In contrast, the catalysis of COE has an off-cycle catalyst resting state of (BQ-NCOP)IrIII(H)[O(Et)···HO(Et)···HOEt] that features a six-membered iridacycle consisting of two hydrogen-bonds between one EtO ligand and two EtOH molecules, one of which is coordinated to the Ir(III) center. The rate law shows a negative order in EtOH, zeroth-order in COE, and first-order in the catalyst. The observed inverse KIE corresponds to an inverse equilibrium isotope effect for the pre-equilibrium formation of (BQ-NCOP)IrIII(H)(OEt) from the catalyst resting state via ethanol dissociation. Regardless of the substrate, ethanol dehydrogenation is the slow segment of the catalytic cycle, while alkene hydrogenation occurs readily following the rate-determining step, that is, β-hydride elimination of (BQ-NCOP)Ir(H)(OEt) to form (BQ-NCOP)Ir(H)2 and acetaldehyde. The latter is effectively converted to innocent ethyl acetate under the catalytic conditions, thus avoiding the catalyst poisoning via iridium-mediated decarbonylation of acetaldehyde.
Continuous preparation method of DL-muscone
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Paragraph 0046; 0048; 0050; 0051; 0053; 0054; 0055; 0056, (2018/07/15)
The invention discloses a continuous preparation method of DL-muscone. The preparation method comprises the following steps: 1) dissolving 2,15-hexadecanedione diketone in an aprotic solvent, then carrying out a continuous reaction in a fixed-bed cyclization reactor for generating a 3-methylcyclopentanone analogue under the action of a cyclization catalyst; 2) carrying out desolvation on the 3-methylcyclopentanone analogue, dissolving the obtained product in a protic solvent, then carrying out a continuous reaction with hydrogen in a fixed-bed hydrogenation reactor under the action of a hydrogenation catalyst to obtain muscone; and 3) carrying out desolvation on the product obtained in the step 2), carrying out continuous chromatographic separation, and carrying out desolvation on the product liquid containing the DL-muscone to obtain the DL-muscone product. The method for preparing the DL-muscone provided by the invention has high process stability and high product yield, continuous production of the DL-muscone can be realized, the production cost is greatly reduced, and the effective capacity of a device is improved.
Method for synthesizing muscone by utilizing beta-monomethyl methylglutarate
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, (2017/12/05)
The invention discloses a method for synthesizing muscone by utilizing beta-monomethyl methylglutarate. According to the method, beta-monomethyl methylglutarate and alpha,omega-dodecanedioic acid monomethyl ester respectively prepared through a heteropoly acid catalytic transesterification method are used as raw materials, and Kolbe electrolysis, acyloin condensation and reduction reaction are performed to prepare the muscone. The method of the present invention has advantages of high raw material utilization rate, mold condition, easy control and environmental protection, and is suitable for industrial production .
Preparation method of E-2-cyclopentadecenone
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Paragraph 0005; 0039; 0040; 0041, (2017/08/31)
The invention provides a novel method for synthesizing E-2-cyclopentadecenone by utilizing 2-hydroxy-cyclopentadecanone. The 2-hydroxycyclopentadecanone, metal oxide, concentrated sulfuric acid or concentrated phosphoric acid are added into a non-polar organic solvent and are subjected to elimination reaction to obtain the E-2-cyclopentadecenone. In the reaction, a catalytic amount of the metal oxide is added so that a condition that the elimination reaction cannot be realized through the concentrated sulfuric acid before becomes possible; the raw materials in the novel method are relatively cheap; reaction conditions are moderate, the operation is simple and the production cost is reduced so that the novel method is very suitable for industrialized production.
Synthesis of Macrocyclic Ketones through Catalyst-Free Electrophilic Halogen-Mediated Semipinacol Rearrangement: Application to the Total Synthesis of (±)-Muscone
Liu, Yi,Yeung, Ying-Yeung
supporting information, p. 1422 - 1425 (2017/03/23)
A series of macrocycles were successfully prepared using electrophilic halogen-mediated semipinacol rearrangement under mild conditions. Although the expansion from small ring to medium ring is an energetically unfavorable process, the electrophilic halog
The chemistry of thiophene-based bis-(p-quinodimethanes): An approach to macrocycles
Trahanovsky, Walter S.,Klumpp, Douglas A.
supporting information, p. 2386 - 2389 (2016/05/19)
Bis-2,5-dimethylene-2,5-dihydrothiophenes have been generated in the gas-phase by flash vacuum pyrolysis (FVP) of diester precursors. These thiophene-based bis-(p-quinodimethanes) are shown to undergo reactions leading to macrocycles. The conversions are consistent with a mechanism involving cyclic diradical intermediates followed by disproportionation of the radical centers.
Efficient macrocyclization by a novel oxy-oxonia-cope reaction: Synthesis and olfactory properties of new macrocyclic musks
Zou, Yue,Mouhib, Halima,Stahl, Wolfgang,Goeke, Andreas,Wang, Quanrui,Kraft, Philip
supporting information; experimental part, p. 7010 - 7015 (2012/07/03)
Musk made to odor: A new oxy-oxonia-Cope macrocyclization to (3Z)-configured cycloalk-3-en-1-yl formates is reported, which is useful in the synthesis of unsaturated and saturated macrocyclic ketones (see scheme). The synthesized structures provide new insight into the structure-odor correlation of musks, making it likely for macrocyclic and linear alicyclic musks to address the same olfactory receptors.
