80445-36-9Relevant articles and documents
A milk lactone perfume continuous compound into method (by machine translation)
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Paragraph 0045; 0053; 0054; 0068; 0069, (2019/05/08)
The invention belongs to the technical field of synthetic perfume, and in particular relates to a milk lactone perfume continuous compound into a method, including the role of the alkali under the condition of the aldol reaction, then by hydrogenation reaction, Baeyer - Villiger oxidation, acid continuous hydrolysis, dehydrating and gets milk lactone perfume; the aldol condensation reactions include: part of the as a footing of a cyclohexanone with a alkali mixing, heating processing, the rest [...] butyraldehyde mixture of cyclohexanone with, side drop edge added stirring, and after dropping to continue stirring, thermal insulation reaction-butyraldehyde content to 1% following the end of the reaction; static divider separating the oil, collected and recycled water; collecting oil layer after washing the processing and then transferred to the distillating still distillation recovery excessive cyclohexanone mechanically, the collection of the condensation product of the pan bottom; the invention by adding cyclohexanone in a different way, improving the yield of the aldol condensation reaction; and, of the present invention under the conditions of reaction temperature, can step from an aldol condensation product. (by machine translation)
A ε - decalactone with synthetic perfume production method (by machine translation)
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Paragraph 0073; 0084; 0085; 0086; 0087; 0089; 0100-0103, (2019/05/28)
The invention belongs to the technical field of spice production, and in particular relates to relates to a ε - decalactone with synthetic perfume production method, including: (1) preparing an aqueous alkali; (2) the preparation of cyclohexanone and butyraldehyde mixture A; (3) the alkali is added to the reactor, the footing cyclohexanone is added to the mix in the reactor; (4) is added to the mixture in the reactor A drop, side drop edge added stirring, after dropping to continue stirring, thermal insulation to react to the detected in-butyraldehyde content of 1% until the following; (5) the step (4) and the product and sequentially through the hydrogenation, separation and purification, oxidation, obtained after the separation and purification of the ε - decalactone synthetic perfume; the invention to butyraldehyde and cyclohexanone as the starting material to aldol condensation reaction, and then after hydrogenation of peracetic acid oxidation ring enlargement reaction synthesis ε - decalactone perfume, to excessive cyclohexanone as the reaction solvent, recovery after mechanically, reduce the reaction solvent separation and purification, and raw materials are easy, the reaction yield is high. (by machine translation)
Synthetic method of epsilon-decalactone perfume
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Paragraph 0062; 0069-0073; 0074; 0082-0086, (2019/05/15)
The invention belongs to the technical field of perfume synthesis, and particularly relates to a synthetic method of epsilon-decalactone perfume. The synthetic method comprises the following steps: (1) mixing an alkaline solution with a part of cyclohexanone, then dropwise adding a mixture of n-butyraldehyde and the rest of cyclohexanone into the mixture, carrying out stirring, and carrying out heat preservation for a reaction; (2) standing the reactants in the step (1), collecting a water layer, collecting an oil layer, and washing the oil layer with water to obtain a condensed product 2-butenyl cyclohexanone crude product; (3) carrying out distilling to recover cyclohexanone to obtain 2-butenyl cyclohexanone; (4) carrying out a hydrogenation reaction; (5) collecting a liquid-phase intermediate product 2-butyl cyclohexanone crude product, and carrying out distilling to obtain 2-butyl cyclohexanone; (6) carrying out an oxidation reaction; and (7) carrying out distilling purification toobtain the epsilon-decalactone perfume product. According to the invention, the cyclohexanone is added into the reaction system in different ways, the excess cyclohexanone is used as a reaction solvent through a stirring dripping technology, and the cyclohexanone is reused after being recycled, so that separation and purification processes of the reaction solvent are reduced, and a high reactionyield is ensured.
Direct room-temperature lactonisation of alcohols and ethers onto amides: An "amide strategy" for synthesis
Valerio, Viviana,Petkova, Desislava,Madelaine, Claire,Maulide, Nuno
supporting information, p. 2606 - 2610 (2013/03/14)
Last-minute deal: A direct lactonisation of ethers and alcohols onto amides that proceeds at room temperature under mild conditions is reported (see scheme). This allows the effective saving of up to two unproductive, sequential deprotection operations in synthetic sequences. Mechanistic studies are described, and a new "amide strategy" that exploits the dual robustness/late-stage selective activation properties of this functional group is outlined. Copyright
Enantioselective synthesis of ε-lactones by lipase-catalyzed resolution
Shimotori, Yasutaka,Aoyama, Masakazu,Tsukasa, Hidetaka,Miyakoshi, Tetsuo
, p. 1061 - 1075 (2012/07/28)
Synthesis of optically active ε-dodecalactone (1) by lipase-catalyzed enantioselective acylation with racemic N-alkyl-6-hydroxydodecanamide (rac-2) as a substrate was attempted. Lipase PS-catalyzed acetylation using rac-2 progressed efficiently, and both
Induced allostery in the directed evolution of an enantioselective Baeyer-Villiger monooxygenase
Wu, Sheng,Acevedo, Juan Pablo,Reetz, Manfred T.
experimental part, p. 2775 - 2780 (2010/10/03)
The molecular basis of allosteric effects, known to be caused by an effector docking to an enzyme at a site distal from the binding pocket, has been studied recently by applying directed evolution. Here, we utilize laboratory evolution in a different way, namely to induce allostery by introducing appropriate distal mutations that cause domain movements with concomitant reshaping of the binding pocket in the absence of an effector. To test this concept, the thermostable Baeyer-Villiger monooxygenase, phenylacetone monooxygenase (PAMO), was chosen as the enzyme to be employed in asymmetric Baeyer-Villiger reactions of substrates that are not accepted by the wild type. By using the known X-ray structure of PAMO, a decision was made regarding an appropriate site at which saturation mutagenesis is most likely to generate mutants capable of inducing allostery without any effector compound being present. After screening only 400 transformants, a double mutant was discovered that catalyzes the asymmetric oxidative kinetic resolution of a set of structurally different 2-substituted cyclohexanone derivatives as well as the desymmetrization of three different 4-substituted cyclohexanones, all with high enantioselectivity. Molecular dynamics (MD) simulations and covariance maps unveiled the origin of increased substrate scope as being due to allostery. Large domain movements occur that expose and reshape the binding pocket. This type of focused library production, aimed at inducing significant allosteric effects, is a viable alternative to traditional approaches to designed directed evolution that address the binding site directly.
Laboratory evolution of robust and enantioselective Baeyer-Villiger monooxygenases for asymmetric catalysis
Reetz, Manfred T.,Wu, Sheng
experimental part, p. 15424 - 15432 (2010/02/16)
The Baeyer-Villiger Monooxygenase, Phenylacetone Monooxygenase (PAMO), recently discovered by Fraaije, Janssen, and co-workers, is unusually thermostable, which makes it a promising candidate for catalyzing enantioselective Baeyer-Villiger reactions in organic chemistry. Unfortunately, however, its substrate scope is very limited, reasonable reaction rates being observed essentially only with phenylacetone and similar linear phenyl-substituted analogs. Previous protein engineering attempts to broaden the range of substrate acceptance and to control enantioselectivity have been met with limited success, including rational design and directed evolution based on saturation mutagenesis with formation of focused mutant libraries, which may have to do with complex domain movements. In the present study, a new approach to laboratory evolution is described which has led to mutants showing unusually high activity and enantioselectivity in the oxidative kinetic resolution of a variety of 2-aryl and 2-alkylcyclohexanones which are not accepted by the wild-type (WT) PAMO and of a structurally very different bicyclic ketone. The new strategy exploits bioinformatics data derived from sequence alignment of eight different Baeyer-Villiger Monooxygenases, which in conjunction with the known X-ray structure of PAMO and induced fit docking suggests potential randomization sites, different from all previous approaches to focused library generation. Sites harboring highly conserved proline in a loop of the WT are targeted. The most active and enantioselective mutants retain the high thermostability of the parent WT PAMO. The success of the "proline" hypothesis in the present system calls for further testing in future laboratory evolution studies.
Assessing the Substrate Selectivities and Enantioselectivities of Eight Novel Baeyer-Villiger Monooxygenases toward Alkyl-Substituted Cyclohexanones
Kyte, Brian G.,Rouviere, Pierre,Cheng, Qiong,Stewart, Jon D.
, p. 12 - 17 (2007/10/03)
Genes encoding eight Baeyer-Villiger monooxygenases have recently been cloned from bacteria inhabiting a wastewater treatment plant. We have carried out a systematic investigation in which each newly cloned enzyme, as well as the cyclohexanone monooxygenase from Acinetobacter sp. NCIB 9871, was used to oxidize 15 different alkyl-substituted cyclohexanones. The panel of substrates included equal numbers of 2-, 3-, and 4-alkyl-substituted compounds to probe each enzyme's stereoselectivity toward a homologous series of synthetically important compounds. For all 4-alkyl-substituted cyclohexanones tested, enzymes were discovered that afforded each of the corresponding (S)-lactones in ≥98% ee. This was also true for the 2-alkyl-substituted cyclohexanones examined. The situation was more complex for 3-akyl-substituted cyclohexanones. In a few cases, single Baeyer-Villiger monooxygenases possessed both high regio- and enantioselectivities toward these compounds. More commonly, however, they showed only one type of selectivity. Nonetheless, enzymes with such properties might be useful as parts of a two-step bioprocess where an initial kinetic resolution is followed by a regioselective oxidation on the isolated, optically pure ketone.
Recombinant baker's yeast as a whole-cell catalyst for asymmetric Baeyer - Villiger oxidations
Stewart, Jon D.,Reed, Kieth W.,Martinez, Carlos A.,Zhu, Jun,Chen, Gang,Kayser, Margaret M.
, p. 3541 - 3548 (2007/10/03)
Cyclohexanone monooxygenase (E.C. 1.14.13.22) from Acinetobacter sp. NCIB 9871 has been expressed in baker's yeast (Saccharomyces cerevisiae) to create a general reagent for asymmetric Baeyer - Villiger oxidations. This 'designer yeast' approach combines
Chemoenzymatic autocatalytic Baeyer-Villiger oxidation
Pchelka, Beata K.,Gelo-Pujic, Mirjana,Guibe-Jampel, Eryka
, p. 2625 - 2627 (2007/10/03)
Autocatalytic Baeyer-Villiger oxidation of cyclic ketones to lactones mediated by lipases has been achieved under extremely mild conditions in dry media using urea-hydrogen peroxide as the primary oxidant. Lipase catalysed perhydrolysis is enantiospecific and gives 6-substituted caprolactones or the corresponding hydroxy acids in enantiomerically enriched form.
