1139-30-6Relevant academic research and scientific papers
A further step to sustainable palladium catalyzed oxidation: Allylic oxidation of alkenes in green solvents
dos Santos Costa, Maíra,de Camargo Faria, Amanda,Mota, Rayssa L.V.,Gusevskaya, Elena V.
, (2021/09/14)
The palladium catalyzed oxidation of alkenes with molecular oxygen is a synthetically important reaction which employs palladium catalysts in solution; therefore, a solvent plays a critical role for the process. In this study, we have tested several green solvents as a reaction medium for the allylic oxidation of a series of alkenes. Dimethylcarbonate, methyl isobutyl ketone, and propylene carbonate, solvents with impressive sustainability ranks and very scarcely exploited in palladium catalyzed oxidations, were proved to be excellent alternatives for the solvents conventionally employed in these processes, such as acetic acid. Palladium acetate alone or in the combination with p-benzoquinone efficiently operates as the catalyst for the oxidation of alkenes by dioxygen under 5–10 atm. For most substrates, the systems in green solvents showed better selectivity for allylic oxidation products as compared to pure acetic acid; moreover, the reactions in propylene carbonate solutions occurred even faster than in acetic acid.
An ultrathin amino-acid based copper(II) coordination polymer nanosheet for efficient epoxidation of β-caryophyllene
Fu, Zaihui,Huang, Hongmei,Mao, Liqiu,Mao, Wensheng,Shi, Lihan,Xiao, Yi,Yin, Dulin,Yu, Ningya,Zhang, Li,Zhao, Yaqian
, (2021/07/26)
Natural amino acids are important building blocks for the construction of intriguing coordination polymers (CPs) because of their abundance, inexpensiveness and environmental benignness. Herein, two copper(II) CPs, namely, 2D CuIle-e nanosheet (e: ethanol) and 1D CuIle-m nanoshuttle (m: methanol), were fabricated from L-isoleucine (Ile) and well characterized with single-crystal x-ray diffraction, XPS spectra, TEM and AFM, etc. More importantly, two novel and stable catalytic nanosystems, i.e. CuIle-e/acetone/TBHP (tert-butyl hydroperoxide) and CuIle-e/THF/O2/TBHP, were thus conveniently built by using ultrathin 2D CuIle-e nanosheet (~ 2.3 nm) in suitable aprotic solvents. Under mild conditions, complete conversion of β-caryophyllene and good yields (86.1% or 87.2%) for β-caryophyllene epoxide were gained via CuIle-e/acetone/TBHP or CuIle-e/THF/O2 (1 atm)/TBHP (10.0 mol%), respectively. Notably, ultrathin CuIle-e nanosheet showed fairly satisfactory stability, which may open a unique window for the facile fabrication of new amino-acid based CP nanosystems with outstanding catalytic performances in actual applications.
PROCESS FOR PREPARING CARYOPHYLLENE OXIDE
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Paragraph 0020; 0059-0061, (2021/12/29)
The present invention relates to a method for oxidizing beta-caryophyllene with oxygen, in particular atmospheric oxygen, which avoids the use of catalysts, enzymes and solvents. Furthermore, the present invention provides a mixture comprising certain caryophyllene oxides as well as their use as a flavor and/or fragrance. The present invention also relates to products and semi-finished products comprising the mixture according to the invention.
Ionic liquid-mediated catalytic oxidation of β-caryophyllene by ultrathin 2D metal-organic framework nanosheets under 1 atm O2
Li, Shiye,Shi, Lihan,Zhang, Li,Huang, Hongmei,Xiao, Yi,Mao, Liqiu,Tan, Rong,Fu, Zaihui,Yu, Ningya,Yin, Dulin
, (2020/09/16)
An ionic liquid (IL)-mediated facile method was established for the epoxidation of β-caryophyllene with molecular oxygen using ultrathin (～3?6 nm) 2D Cu-, Co- or Ce-based MOF nanosheets. Under the optimum conditions, high selectivity (92.4percent) and excellent yield (86.7percent) for β-caryophyllene epoxide were obtained over ultrathin (～5.5 nm) Cu-TCPP nanosheets (TCPP = tetrakis(4-carboxyphenyl)porphyrin) with the aid of [C12mim]Cl at 313 K and 1 atm O2. Notably, a small amount of [C12mim]Cl (1-dodecyl-3-methylimidazolium chloride, 5.0 mol percent) played pivotal roles in forming a favorable microenvironment in-situ, thus significantly improving the catalytic performances of above-mentioned Cu-TCPP nanosheets containing PVP stabilizer. Moreover, ultrathin Cu-TCPP nanosheets showed better stability during β-caryophyllene transformation in the presence of amphiphilic [C12mim]Cl, as supported by TEM and XRD analyses. Importantly, the addition of TBHP (tert-butyl hydroperoxide, 13.0 mol percent) initiator is also crucial for the aerobic oxidation of β-caryophyllene via Cu-TCPP nanosheets/[C12mim]Cl/TBHP/O2 nanosystem. Further insights into the synergistic effects and free radical mechanism were achieved by fluorescence, DRUV-Vis, UV-vis and XPS measurements.
Tailoring chemoenzymatic oxidation: Via in situ peracids
Re, Rebecca N.,Proessdorf, Johanna C.,La Clair, James J.,Subileau, Maeva,Burkart, Michael D.
supporting information, p. 9418 - 9424 (2019/11/14)
Epoxidation chemistry often suffers from the challenging handling of peracids and thus requires in situ preparation. Here, we describe a two-phase enzymatic system that allows the effective generation of peracids and directly translate their activity to the epoxidation of olefins. We demonstrate the approach by application to lipid and olefin epoxidation as well as sulfide oxidation. These methods offer useful applications to synthetic modifications and scalable green processes.
Β - caryophyllene derivative and its preparation method and application (by machine translation)
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Paragraph 0050; 0079; 0080; 0081; 0083; 0084, (2018/04/03)
The invention discloses a β - caryophyllene derivative and its preparation method and application. The present invention provides a β - caryophyllene derivatives of the general structure of formula I shown, wherein R is selected from the following an arbitrary group: hydroxy, amino, ester and amide-based. The inventor of this invention through the experimental verification: the reaction sub-have good reactivity, stability, raw materials are easy sex, at the same time has a certain reaction rate. In the corresponding protein marker and cell labeling experiment in which proves that the application of the response, a relevant biological orthogonal response development provides a new idea. (by machine translation)
Convenient synthesis of deuterium labelled sesquiterpenes
Duhamel, Nina,Martin, Damian,Larcher, Roberto,Fedrizzi, Bruno,Barker, David
supporting information, p. 4496 - 4499 (2016/09/14)
Sesquiterpenes are an important class of molecules, with roles ranging from pollination and signalling to defense mechanisms. Despite their apparent importance, the limited number of commercial standards has hindered their study and precise quantification. Herein, we report the syntheses of fourteen labelled sesquiterpenes with a high level of deuterium incorporation (>95%) for applications in MS-based studies.
Electron transfer-initiated epoxidation and isomerization chain reactions of β-caryophyllene
Steenackers, Bart,Campagnol, Nicol,Fransaer, Jan,Hermans, Ive,De Vos, Dirk
, p. 2146 - 2156 (2015/01/30)
The abundant sesquiterpene b-caryophyllene can be epoxidized by molecular oxygen in the absence of any catalyst. In polar aprotic solvents, the reaction proceeds smoothly with epoxide selectivities exceeding 70%. A mechanistic study has been performed and the possible involvement of free radical, spin inversion, and electron transfer mechanisms is evaluated using experimental and computational methods. The experimental data-including a detailed reaction product analysis, studies on reaction parameters, solvent effects, additives and an electrochemical investigation-all support that the spontaneous epoxidation of b-caryophyllene constitutes a rare case of unsensitized electron transfer from an olefin to triplet oxygen under mild conditions (80 8C, 1 bar O2). As initiation of the oxygenation reaction, the formation of a caryophyllene-derived radical cation via electron transfer is proposed. This radical cation reacts with triplet oxygen to a dioxetane via a chain mechanism with chain lengths exceeding 100 under optimized conditions. The dioxetane then acts as an in situ-formed epoxidizing agent. Under nitrogen atmosphere, the presence of a one-electron acceptor leads to the selective isomerization of b -caryophyllene to isocaryophyllene. Observations indicate that this isomerization reaction is a novel and elegant synthetic pathway to isocaryophyllene.
Chromium(III) terephthalate metal organic framework (MIL-101): Hf-free synthesis, structure, polyoxometalate composites, and catalytic properties
Bromberg, Lev,Diao, Ying,Wu, Huimeng,Speakman, Scott A.,Hatton, T. Alan
experimental part, p. 1664 - 1675 (2012/08/13)
Hybrid materials of the metal-organic framework (MOF), chromium(III) terephthalate (MIL-101), and phosphotungstic acid (PTA) were synthesized in aqueous media in the absence of hydrofluoric acid. XRD analysis of the MIL101/PTA composites indicates the presence of ordered PTA assemblies residing in both the large cages and small pores of MIL-101, which suggests the formation of previously undocumented structures. The MIL101/PTA structure enables a PTA payload 1.5-2 times higher than previously achieved. The catalytic performance of the MIL101/PTA composites was assessed in the Baeyer condensation of benzaldehyde and 2-naphthol, in the three-component condensation of benzaldehyde, 2-naphthol, and acetamide, and in the epoxidation of caryophyllene by hydrogen peroxide. The catalytic efficiency was demonstrated by the high (over 80-90%) conversion of the reactants under microwave-assisted heating. In four consecutive reaction cycles, the catalyst recovery was in excess of 75%, whereas the product yields were maintained above 92%. The simplicity of preparation, exceptional stability, and reactivity of the novel composites indicate potential in utilization of these catalytic matrices in a multitude of catalytic reactions and engineering processes.
1-HYDROXY-OCTAHYDROAZULENES AS FRAGRANCES
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Page/Page column 15-16, (2012/01/14)
(3S,5R)-3,8-dimethyl-5-(prop-1-en-2-yl)-octahydroazulen-1-ols, their use as flavour or fragrance ingredient, and a process of their production by oxidation in the presence of laccase.
