- PROCESS FOR PREPARING CARYOPHYLLENE OXIDE
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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.
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Paragraph 0020; 0059-0061
(2021/12/29)
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- A further step to sustainable palladium catalyzed oxidation: Allylic oxidation of alkenes in green solvents
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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.
- dos Santos Costa, Maíra,de Camargo Faria, Amanda,Mota, Rayssa L.V.,Gusevskaya, Elena V.
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- An ultrathin amino-acid based copper(II) coordination polymer nanosheet for efficient epoxidation of β-caryophyllene
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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.
- Fu, Zaihui,Huang, Hongmei,Mao, Liqiu,Mao, Wensheng,Shi, Lihan,Xiao, Yi,Yin, Dulin,Yu, Ningya,Zhang, Li,Zhao, Yaqian
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- Ionic liquid-mediated catalytic oxidation of β-caryophyllene by ultrathin 2D metal-organic framework nanosheets under 1 atm O2
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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.
- Li, Shiye,Shi, Lihan,Zhang, Li,Huang, Hongmei,Xiao, Yi,Mao, Liqiu,Tan, Rong,Fu, Zaihui,Yu, Ningya,Yin, Dulin
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- Tailoring chemoenzymatic oxidation: Via in situ peracids
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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.
- Re, Rebecca N.,Proessdorf, Johanna C.,La Clair, James J.,Subileau, Maeva,Burkart, Michael D.
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supporting information
p. 9418 - 9424
(2019/11/14)
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- Β - caryophyllene derivative and its preparation method and application (by machine translation)
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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)
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Paragraph 0050; 0079; 0080; 0081; 0083; 0084
(2018/04/03)
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- Convenient synthesis of deuterium labelled sesquiterpenes
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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.
- Duhamel, Nina,Martin, Damian,Larcher, Roberto,Fedrizzi, Bruno,Barker, David
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supporting information
p. 4496 - 4499
(2016/09/14)
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- Electron transfer-initiated epoxidation and isomerization chain reactions of β-caryophyllene
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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.
- Steenackers, Bart,Campagnol, Nicol,Fransaer, Jan,Hermans, Ive,De Vos, Dirk
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p. 2146 - 2156
(2015/01/30)
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- Chromium(III) terephthalate metal organic framework (MIL-101): Hf-free synthesis, structure, polyoxometalate composites, and catalytic properties
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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.
- Bromberg, Lev,Diao, Ying,Wu, Huimeng,Speakman, Scott A.,Hatton, T. Alan
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experimental part
p. 1664 - 1675
(2012/08/13)
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- 1-HYDROXY-OCTAHYDROAZULENES AS FRAGRANCES
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(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.
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Page/Page column 15-16
(2012/01/14)
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- An effective synthesis of acid-sensitive epoxides via oxidation of terpenes and styrenes using hydrogen peroxide under organic solvent-free conditions
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An efficient epoxidation process for various terpenes and styrenes using a hydrogen peroxide-tungsten catalytic system with organic solvent-and halide-free conditions was developed. In the presence of the catalytic system, Na 2WO4, PhP(O)(OH)2, and [Me(n-C 8H17)3N]HSO4, and under weak acidic conditions, hydrogen peroxide successfully epoxidized -pinene to -pinene oxide in 95% selectivity at 91% conversion, while the previously published conditions utilizing NH2CH2P(O)(OH)2 as a promoter provided no epoxide. Georg Thieme Verlag Stuttgart.
- Kon, Yoshihiro,Hachiya, Houjin,Ono, Yutaka,Matsumoto, Tomohiro,Sato, Kazuhiko
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experimental part
p. 1092 - 1098
(2011/05/14)
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- An effective procedure for the synthesis of acid-sensitive epoxides: Use of 1-methylimidazole as the additive on methyltrioxorhenium-catalyzed epoxidation of alkenes with hydrogen peroxide
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An effective method for suppression of ring opening and rearrangement of acid-sensitive epoxides during methyltrioxorhenium(MTO)-catalyzed epoxidation of alkenes with H2O2 by using 1-methylimidazole as a co-additive has been found. The combined use of 3-methylpyrazole and 1-methylimidazole as the additives has been found to be an effective procedure that affords excellent yields of acid-sensitive epoxides for MTO-catalyzed epoxidation.
- Yamazaki, Shigekazu
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experimental part
p. 2377 - 2385
(2010/07/06)
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- Biomimetic syntheses of the neurotrophic natural products caryolanemagnolol and clovanemagnolol
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"Chemical Equation Presented" Separate short and modular syntheses of the isomeric natural products caryolanemagnolol and clovanemagnolol have been achieved starting from commercially available (-)-caryophyllene. The postulated biosynthetic pathways guided the syntheses of the neuroregenerative small molecules allowing their assembly In as few as two steps.
- Cheng, Xu,Harzdorf, Nicole L.,Shaw, Travis,Siegel, Dionicio
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supporting information; experimental part
p. 1304 - 1307
(2010/06/17)
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- An effective catalytic epoxidation of terpenes with hydrogen peroxide under organic solvent-free conditions
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A catalytic system that operates well for the epoxidation of α-pinene, a very challenging substrate, at near-neutral pH and ambient temperature without organic solvent was developed. With hydrogen peroxide as a terminal oxidant, combination of Na2WO4, PhP(O)(OH) 2, and [Me(n-C8H17)3N]HSO 4 successfully catalyzed the epoxidation of α-pinene to give α-pinene oxide in 95% selectivity at 91% conversion, while the previously published conditions that use NH2CH2P(O)(OH)2 as a promoter provide no epoxide. The method is also well applicable to the epoxidation of the other acidsensitive terpenes. Georg Thieme Verlag Stuttgart.
- Kon, Yoshihiro,Ono, Yutaka,Matsumoto, Tomohiro,Sato, Kazuhiko
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scheme or table
p. 1095 - 1098
(2009/09/25)
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- Transannular cyclization of epoxycaryophyllenes catalyzed by Ti III: An efficient synthesis of tricyclo[6.3.0.02,5] undecanes
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The transannular cyclization of epoxycaryophyllenes 2-7 catalyzed by TiIII has been investigated. This cyclization led to alcohols 8-15, all of them possessing a tricyclo[6.3.0.02,5]undecane skeleton. All of these compounds present pleasant aromatic properties. The cyclization takes place with high yields (> 80 %) and via the αα or ββ conformation of the intermediate radical I. Wiley-VCH Verlag GmbH & Co. KGaA, 2006.
- Barrero, Alejandro F.,Herrador, M. Mar,Quilez Del Moral, Jose F.,Arteaga, Pilar,Sanchez, Elena M.,Arteaga, Jesus F.,Piedra, Maria
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p. 3434 - 3441
(2007/10/03)
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- Synthesis of oxygenated compounds derived from caryophyllene.
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Studies of the chemical composition of clove oil indicate caryophyllene epoxide and the presence of some other oxidation derivatives.To elucidate these oxygenated compound structures, we have undertaken the synthesis of some caryophyllene oxide derivatives using 3-chloroperbenzoic acid and caryophyllene.Caryophyllene epoxide, two diepoxides, a ketoepoxide and an aldehyde were isolated.Optimization of the procedure allowed us to selectively orient the reaction towards monoepoxides (100percent), ketoepoxides (99percent) or diepoxides (84percent).The reduction of diepoxides using lithium aluminium hydride led to two cyclic ether alcohols with tetrahydrofuranic and tetrahydropyranic rings, which were obtained in high yield and good regioselectivity.The structures of these compounds have been determined from concerted application of two-dimensional NMR techniques. - Key words: oxidation; reduction; caryophyllene; epoxide; diepoxide; ether alcohol; intramolecular cyclization
- Bombarda, Isabelle,Gaydou, Emile M.,Smadja, Jacqueline,Faure, Robert
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p. 836 - 842
(2007/10/02)
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- Stereochemistry of 14-hydroxy-β-caryophyllene and related compounds
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The isomerization of β-caryophyllene (3), under treatment with SeO2, is described. Chemical correlations, between 3 and 14-hydroxy-β-caryophyllene (6) from Juniperus oxycedrus, are established. High resolution 1H NMR spectra and analysis by molecular mechanics of 3, 6 and 14-acetoxy-β-caryophyllene (7) indicate the existence of two conformational isomers, βα and ββ, in each compound. At 25°C, the βα conformer predominates in 3 and 7 but the ββ conformer predominates in 6. The higher percentage of 6ββ possibly derives from an intramolecular hydrogen bond. The treatment of 3, 6 and 7 with m-CPBA generates, in each case, two diastereomeric 4,5-epoxi-derivatives. The epoxides obtained from 6 have been isolated and analysed separately.
- Barrero,Molina,Oltra,Altarejos,Barragan,Lara,Segura
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p. 3813 - 3822
(2007/10/02)
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- Thermoconversion of caryophyllene- to farnesene-type sesquiterpenes. Short access to the enantiomers of (6RS,7RS)- and (6RS,7SR)-6,7-epoxy-6,7-dihydro-β-farnesenes
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Flash-vacuum thermolysis of the four diastereoisomeric 5,6-epoxy-5,6-dihydro-caryophyllenes 1-4 at 500-550°/0.1-0.7 Torr leads to the hitherto unreported enantiomers of (6RS,7RS)- and (6RS,7SR)-6,7-epoxy-6,7-dihydro-β-farnesenes ((±)-5 and (±)-6, resp.). In particular, (+)-5 is formed in 45% yield (ca. 90% ee) and is, thus, an attractive chiral building block for natural-product synthesis.
- Giersch,Boschung,Snowden,Schulte-Elte
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- BIOTRANSFORMATION OF CARYOPHYLLENE BY DIPLODIA GOSSYPINA
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Fermentation of caryophyllene with Diplodia gossypina affords a number of products which are all derived from the 4,5-epoxide.Twelve of these are described here for the first time.The main products are 12-hydroxy-4,5-epoxy-caryophyllene and the corresponding acid.On side reactions additional hydroxylations occured or the exo-methylene group was also epoxidized and further degraded.Two rearranged compounds were found, one resulting from an epoxide rearrangement leading to an eight-membered ring, the other one being a cyclization product possessing the rare skeleton of the punctatin antibiotics.
- Abraham, Wolf-Rainer,Ernst, Ludger,Stumpf, Burghard
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p. 115 - 120
(2007/10/02)
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- OXYMERCURATION-DEMERCURATION OF THE 4,5-EPOXIDES OF CARYOPHYLLENE AND ISOCARYOPHYLLENE
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The products from the transformations of the 4,5-epoxides of the sesquiterpene hydrocarbons caryophyllene and isocaryophyllene were studied under oxymercuration-demercuration conditions.Initially, the 4,5-epoxycaryophyllene isomers form the products from addition at the 8,13-double bond, in which intramolecular nucleophilic opening of the epoxide ring then occurs.In the case of epoxyisocaryophyllene the oxygen atom of the epoxide group takes part directly in nucleophilic attack on the intermediate mercurinium ion, formed at the 8,13-double bond.
- Tkachev, A. V.,Dubovenko, Zh. V.,Pentegova, V. A.
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p. 1593 - 1601
(2007/10/02)
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- EIGHT NEW XENIA DITERPENOIDS FROM THREE SOFT CORALS OF THE RED SEA
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Investigation of the terpenoid content of three soft corals from the Gulf of Eilat (THe Red Sea), Xenia macrospiculata, X. obscuronata and X. lilielae resulted in the isolation of 8 new diterpens.Two of the new compounds belong to the xeniolides (xenialactol-D (10a) and xeniolide-E (13)) and the other six (4,14-diepoxyxeniaphyllene (15), 4,5-epoxyxeniaphyllan-14,15-diol (17), 4,14-diepoxy-xeniaphyllenol-A (21a), xeniaphyllenol-B (23a), xeniaphyllenol-C (24a) and xeniaphyllantriol (25) are new xeniaphyllanes (prenylated caryophyllanes).The structure determination of the various compounds is based on chemical transformations as well as on the 1H and 13C NMR spectra.Several known caryophyllene derivatives have been synthesised for 13C NMR spectra and chemical comparisons.The 13C NMR has proven to be an excellent probe for structural and stereochemical determinations.
- Groweiss, Amiram,Kashman, Yoel
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p. 3385 - 3396
(2007/10/02)
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- New Sesquiterpenoids from Clary Sage Oil (Salvia sclarea L.)
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Six sesquiterpenoids, (2R,5E)-2,12-epoxycaryophyll-5-ene (1), (2R,5E)-caryophyll-5-en-12-al (2), (2S,5E)-caryophyll-5-en-12-al (3), isospathulenol (4), (1R,5R)-1,5-epoxysalvial-4(14)-ene (5), and salvial-4(14)-en-1-one (6) have been identified for the first time in clary sage oil (Salvia sclarea L.).The structures and absolute configurations of 1-6 are corroborated by partial syntheses and their organoleptic properties are discussed.The compounds 5, 6 and mintsulfide (14) possess the rare C-skeleton C, for which the semisystematic name 'salvialane' is proposed.The sesquiterpenoids 1-5 are new.
- Maurer, Bruno,Hauser, Arnold
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p. 2223 - 2235
(2007/10/02)
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