106-26-3Relevant articles and documents
Comparison of the Key Aroma Compounds in Fresh, Raw Ginger (Zingiber officinale Roscoe) from China and Roasted Ginger by Application of Aroma Extract Dilution Analysis
Schaller, Tanja,Schieberle, Peter
, p. 15292 - 15300 (2020)
By application of a comparative aroma extract dilution analysis on the volatile fractions isolated by solvent extraction and solvent-assisted flavor evaporation (SAFE) from fresh raw Chinese ginger (Zingiber officinale Roscoe) and roasted ginger, 21 or 33 odorants, respectively, with flavor dilution (FD) factors in the range of 32-4096 were identified. In raw ginger, the highest FD factors were found for (E)-isoeugenol, 1,8-cineol, vanillin, geranial, and linalool. After roasting, in particular, the FD factors of 3-(methylthio)propanal (cooked potato-like), 4-hydroxy-2,5-dimethyl-3(2H)-furanone (caramel-like), 3-hydroxy-4,5-dimethyl-2(5H)-furanone (seasoning-like), and geraniol were substantially increased. The application of static headspace/olfactometry (SHO) on ground raw ginger revealed a high FD factor for highly volatile acetaldehyde which clearly decreased after roasting. By contrast, the SHO application revealed high FD factors for malty smelling methylpropanal and 3-methylbutanal, which both were exclusively detected in roasted ginger. Thirteen odorants, namely, decanoic acid, (Z)-2-decenal, (Z)-4-decenal, (E)-4,5-epoxy-(E)-2-decenal, (E)-4,5-epoxy-(E)-2-undecenal, fenchol, (Z)-3-hexenal, 3-hydroxy-4,5-dimethyl-2(5H)-furanone, 4-hydroxy-2,5-dimethyl-3(2H)-furanone, 3-methyl-2-buten-1-thiol, 2-methylpropanal, (E)-2-nonenal, and 1-nonen-3-one, were identified in ginger for the first time. Chiral analysis showed a much higher percent by weight portion for the (R)-enantiomer in citronellal, citronellol, and linalool, which was not much changed during pan-frying.
Synthesis of (sulfonyl)methylphosphonate analogs of prenyl diphosphates
Lodewyk, Michael W.,Lui, Victor G.,Tantillo, Dean J.
, p. 170 - 173 (2010)
Syntheses of several (sulfonyl)methylphosphonate analogs of geranyl, neryl, and farnesyl diphosphates are described. Key steps include utilization of an (E)-selective Horner-Wadsworth-Emmons olefination which couples an aldehyde to the sulfone phosphonate moiety, and a selective reduction of the resulting dienyl sulfone phosphonate substrates.
Oxidations with hydrogen peroxide catalysed by the [WZnMn(II)2(ZnW9O34)2]12- polyoxometalate
Neumann,Juwiler
, p. 8781 - 8788 (1996)
Polyoxometalates can be used as catalysts for the activation of molecular oxygen and 30% aqueous hydrogen peroxide for the selective transformation of various organic substrates. In this paper results are presented for the oxidation of alkenes, dienes, alkenols, and sulfides using 30% aqueous H2O2 as oxidant and [WZnMn(II)2(ZnW9O34)2]12- as catalyst. In certain but not all cases high reactivity, chemoselectivity and stereospecificity has been observed especially in the epoxidation of alkenols with primary hydroxyl units.
Synthesis of Allyl Acetals and Their Catalytic Claisen-Cope Rearrangement
Nakabayashi, Kazuhiro,Ooho, Masato,Niino, Teppei,Kitamura, Tsugio,Yamaji, Teizo
, p. 157 - 164 (2004)
We have synthesized various types of acetals using 3-methyl-3-butenal and 2-alkenyl, furfuryl, benzyl, p-substituted benzyl, and 2-pentynyl alcohols. These acetals have given corresponding aldehydes after an acid catalytic reaction. Trifluoroacetic acid (CF3COOH) was the best catalyst. The best yield attained was 79% when 3-methyl-3-butenal di(trans-2-pentenyl) acetal was used as a substrate. We also demonstrated that this reaction proceeded via a Claisen-Cope rearrangement.
Highly efficient oxidation of alcohols and aromatic compounds catalysed by the Ru-Co-Al hydrotalcite in the presence of molecular oxygen
Matsushita, Tsuyoshi,Ebitani, Kohki,Kaneda, Kiyotomi
, p. 265 - 266 (1999)
The ruthenium hydrotalcite having cobalt cations, Ru-Co-Al-CO3 HT, is an effective heterogeneous catalyst for the oxidation of various kinds of alcohols in the presence of molecular oxygen.
Direct oxidation of benzylic and allylic silyl ethers to carbonyl compounds
Piva, Olivier,Amougay, Aicha,Pete, Jean-Pierre
, p. 3993 - 3996 (1991)
Oxidation of benzylic or allylic silyl ethers with DDQ under UV irradiation leads directly to the corresponding carbonyl compounds with moderate to good yields.
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Montavon et al.
, p. 1250,1253 (1957)
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A Convenient Method for Conversion of Allylic Chlorides to α,β-Unsaturated Aldehydes
Suzuki, Shigeaki,Onishi, Takashi,Fujita, Yoshiji,Misawa, Hiromitsu,Otera, Junzo
, p. 3287 - 3288 (1986)
Tertiary amine N-oxides were found to be effective for converting chlorides to aα,β-unsaturated aldehydes.
Total synthesis of 3,7-dimethyl-7-hydroxy-2-octen-1,6-olide and 3,7-dimethyl-2,6-octadien-1,6-olide
Dong, Hong-Bo,Yang, Ming-Yan,Jiang, Jia-Zheng,Wang, Ming-An
, p. 880 - 884 (2013)
3,7-Dimethyl-7-hydroxy-2-octen-1,6-olide (1) and 3,7-dimethyl-2,6-octadien- 1,6-olide (2), the natural bioactive compounds isolated from the fruit of Litsea cubeba and the liverwort Plagiochila rutilans, were totally synthesized using easily available cis-geraniol as raw material in short, convenient, and low-cost, five-step reactions including three steps of oxidation, cyclization, and dehydration, with an overall yield of 47.5% and 37.3%.
Selective catalytic oxidation of geraniol to citral with molecular oxygen in supercritical carbon dioxide
Dapurkar, Sudhir E.,Kawanami, Hajime,Chatterjee, Maya,Rode, Chandrasekhar V.,Yokoyama, Toshirou,Ikushima, Yutaka
, p. 209 - 214 (2011)
Selective catalytic oxidation of geraniol to citral with molecular oxygen in supercritical carbon dioxide (scCO2) has been investigated. The catalyst used was a chromium containing mesoporous molecular sieve catalyst viz. CrMCM-41. Comparison studies were performed with CoMCM-41, PtMCM-41 and PdMCM-41 catalysts. Among the various catalysts studied, CrMCM-41 showed a high conversion of geraniol and an excellent selectivity for citral. In contrast CoMCM-41, PtMCM-41 and PdMCM-41 catalysts exhibited low conversion of geraniol. However all three catalysts compared showed similar citral selectivity to CrMCM-41. The effect of CO2 pressure and reaction temperature geraniol oxidation was studied with CrMCM-41. Supercritical CO2 medium was found to enhance the conversion of geraniol and/or yield of citral. It was noticed that the catalyst can be recycled with negligible loss of conversion.
Selective Oxidation of Alcohol Function in Allylic Alcohols to α,β-Unsaturated Carbonyl Compounds Catalyzed by Zirconocene Complexes
Nakano, Tatsuya,Ishii, Yasutaka,Ogawa, Masaya
, p. 4855 - 4859 (1987)
Bis(η5-cyclopentadienyl)zirconium(IV) complexes, Cp2ZrH2 (1) and Cp2Zr(O-i-Pr)2 (4), in the presence of an appropriate hydrogen acceptor such as benzaldehyde or cyclohexanone catalyze the Oppenauer-type oxidation of allylic alcohols to α,β-unsaturated carbonyl compounds.For instance, primary allylic terpenoid alcohols, geraniol and nerol, were oxidized to α- and β-citrals, which are essential compounds in the perfumery industry, in substantial yields without any treatment.Similarly, secondary allylic alcohols such as 3-hexen-2-ol and 2-cyclohexen-1-ol were alsooxidized with ease to give 3-hexen-2-one and 2-cyclohexen-1-one in 93percent and 89percent yields, respectively.But the present OPP-type oxidation by zirconocene complexes is ineffective for propargylic alcohols.
Schwartz,Swanson
, p. 953,957 (1979)
Oxidation of terpenic alcohols with hydrogen peroxide promoted by Nb2O5 obtained by microwave-assisted hydrothermal method
Carreira Batalha, Daniel,Hadler Marins, Natália,Lenin Villarreal Carre?o, Neftalí,Marques e Silva, Ricardo,Vieira Fajardo, Humberto,da Silva, Márcio José
, (2020)
The present work describes the synthesis of niobium oxides by microwave-assisted hydrothermal method and their evaluation as a solid catalyst in oxidation reactions of terpenic alcohols with hydrogen peroxide. Effects of main parameters of synthesis were assessed and all the prepared catalysts were characterized by physical adsorption/ desorption analyses of nitrogen, infrared and Raman spectroscopies, scanning electron microscopy and powder X-rays diffraction analyses. The strength and number of acidic sites of the catalysts were determined by potentiometric titration. Morphological and structural characterization corroborate with the activity and selectivity achieved by the niobium oxides. The reusability of the catalyst was evaluated. The impacts of main reaction variables such as temperature, catalyst, and oxidant load were assessed. Niobium oxide demonstrated to be an effective catalyst, selectively converting the nerol (model molecule) to epoxide and aldehyde. Oxidation of various terpenic alcohols was investigated. Only geraniol and nerol were selectively epoxidized, suggesting a hydroxyl group assisted reaction. Although being also allylic alcohol, linalool was unreactive toward epoxidation due to the presence of a methyl group at the same carbon atom than the hydroxy group. The use of an environmentally cheap friendly oxidant (H2O2) and efficient solid catalyst (Nb2O5) are positive aspects of this process.
Iron-catalyzed aerobic oxidation of allylic alcohols: The issue of C=C bond isomerization
Liu, Jinxian,Ma, Shengming
, p. 5150 - 5153 (2013)
An aerobic oxidation of allylic alcohols using Fe(NO3) 3·9H2O/TEMPO/NaCl as catalysts under atmospheric pressure of oxygen at room temperature was developed. This eco-friendly and mild protocol provides a convenient pathway to the synthesis of stereodefined α,β-unsaturated enals or enones with the retention of the C-C double-bond configuration.
A new method for the selective oxidation of allylic and benzylic alcohols
Pearson, Anthony J.,Kwak, Yoonhyun
, p. 5417 - 5419 (2005)
A new method is described for the selective oxidation of allylic or benzylic alcohols, in the presence of saturated alcohols, using trimethylamine-N-oxide in the presence of an iron carbonyl.
Efficient and Selective Oxidation of Alcohols by Potassium Dichromate Solutions
Santaniello, Enzo,Ferraboschi, Patrizia
, p. 646 - 647 (1980)
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Highly efficient oxidation of alcohols to carbonyl compounds in the presence of molecular oxygen using a novel heterogeneous ruthenium catalyst
Ji, Hongbing,Mizugaki, Tomoo,Ebitani, Kohki,Kaneda, Kiyotomi
, p. 7179 - 7183 (2002)
A ruthenium cation combined with microcrystals of cobalt hydroxide and cerium oxide acted as a highly efficient heterogeneous catalyst for the oxidation of various types of alcohols to carbonyl compounds under atmospheric pressure of molecular oxygen at 60°C. Especially, primary aliphatic alcohols could be oxidized to afford the carboxylic acids in high yields.
Oxidizing polymers: A polymer-supported, recyclable hypervalent iodine(V) reagent for the efficient conversion of alcohols, carbonyl compounds, and unsaturated carbamates in solution
Sorg,Mengel,Jung,Rademann
, p. 4395 - 4397 (2001)
The oxidation of various alcohols and cyclization of an olefinic carbamate succeeds with the first polymer-supported iodine(v) reagent (see scheme). The novel oxidizing polymer oxidizes sensitive and complex alcohols, including protected amino alcohols, efficiency in good excellent yields. In addition, the α,β-dehydration of a ketone is demonstrated.
Efficient and Practical Catalytic Oxidation of Alcohols Using Molecular Oxygen
Markó, Istvdn E.,Gautier, Arnaud,Chellé-Regnaut, Isabelle,Giles, Paul R.,Tsukazaki, Masao,Urch, Christopher J.,Brown, Stephen M.
, p. 7576 - 7577 (1998)
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Monolacunary K8SiW11O39-Catalyzed Terpenic Alcohols Oxidation with Hydrogen Peroxide
da Silva, Márcio José,da Silva Andrade, Pedro Henrique,Ferreira, Sukarno Olavo,Vilanculo, Castelo Bandane,Oliveira, Cesar Macedo
, p. 2516 - 2527 (2018)
Abstract: Lacunar potassium undecasilicotungstate salt catalyst was highly efficient in oxidation reactions of terpenic alcohols with hydrogen peroxide. Carbonylic products were selectively obtained from alcohols such as borneol, nerol, geraniol and β-citronellol. The K8SiW11O39 catalyst was synthesized in one pot reaction starting from precursor salts (KCl, Na2WO4, and Na2SiO3). The catalyst salt was characterized by FT-IR, TG/DSC, BET, XRD analyses and potentiometric titration. The main reaction parameters were assessed. Based on experimental data, a reaction pathway was proposed. In borneol oxidation, TON of 2720 was achieved, indicating the high catalytic activity. As far we know, it is the first time where the monolacunar catalyst is used without an additional introduction of metal transition into Keggin anion. A comparison of the catalytic performance of different lacunar silicotungstic acid salts exchanged with different cations was performed. The K8SiW11O39 catalyst was used without loss activity.
ω-Hydroxy isoprenoid bisphosphonates as linkable GGDPS inhibitors
Bhuiyan, Nazmul H.,Varney, Michelle L.,Bhattacharya, Deep S.,Payne, William M.,Mohs, Aaron M.,Holstein, Sarah A.,Wiemer, David F.
, (2019)
The enzyme geranylgeranyl diphosphate synthase (GGDPS) is a potential therapeutic target for multiple myeloma. Malignant plasma cells produce and secrete large amounts of monoclonal protein, and inhibition of GGDPS results in disruption of protein geranylgeranylation which in turn impairs intracellular protein trafficking. Our previous work has demonstrated that some isoprenoid triazole bisphosphonates are potent and selective inhibitors of GGDPS. To explore the possibility of selective delivery of such compounds to plasma cells, new analogues with an ω-hydroxy group have been synthesized and examined for their enzymatic and cellular activity. These studies demonstrate that incorporation of the ω-hydroxy group minimally impairs GGDPS inhibitory activity. Furthermore conjugation of one of the novel ω-hydroxy GGDPS inhibitors to hyaluronic acid resulted in enhanced cellular activity. These results will allow future studies to focus on the in vivo biodistribution of HA-conjugated GGDPS inhibitors.
Can Br?nsted acids catalyze the epoxidation of allylic alcohols with H2O2? With a little help from the proton, the H3PMo12O40 acid did it and well
Vilanculo, Castelo Bandane,da Silva, Márcio José
, (2021/08/04)
In this work, we have explored the catalytic activity of typical Br?nsted acid in epoxidation reactions of terpene alcohols with hydrogen peroxide. Keggin heteropolyacids (HPAs) (i.e., H3PW12O40, H3PMo12O40, and H4SiW12O40) were compared to the common Br?nsted acids (i.e., sulfuric, and p-toluenesulfonic acids) in epoxidation reactions of nerol, the model molecule selected. The effects of the main reaction variable, such as temperature, time, load and sort of acid catalyst were evaluated. Among the catalysts investigated, H3PMo12O40 was the most active and selective catalyst toward epoxide nerol, the goal product. The highest conversion obtained was 99%, with a selectivity of 97% towards nerol epoxide. A discussion of the reaction mechanism was performed as the basis of experimental results and acidity properties of the catalysts. A comparison with a non-protic catalyst (i.e., Na3PMo12O40) allowed demonstrate that both Molybdenum and protons present in the H3PMo12O40 are the main active sites in this epoxidation reaction.
Method for preparing olefine aldehyde through catalytic oxidation of enol ether
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Paragraph 0082-0086; 0089, (2021/06/23)
The invention relates to the technical field of olefine aldehyde preparation, and provides a method for preparing olefine aldehyde through catalytic oxidation of enol ether. According to the invention, a palladium catalyst, a copper salt, a solvent and enol ether are mixed and subjected to a catalytic oxidation reaction to obtain olefine aldehyde. According to the method, the copper salt is used as the oxidizing agent, the mixed solvent of water and acetonitrile is used as the reaction solvent, and the volume ratio of water to acetonitrile in the mixed solvent is controlled to be (3-7): (3-7), so that the catalytic oxidation reaction can be smoothly carried out in the mixed solvent with a specific ratio, and the generation of palladium black precipitate can be avoided. The method provided by the invention has the advantages of simple steps, low reagent cost, no need of dangerous reagents, wide substrate adaptability and small catalyst dosage. Furthermore, octadecane mercaptan is added to promote the catalytic oxidation reaction, and when the dosage of the palladium catalyst is extremely low, the olefine aldehyde yield can be greatly increased by adding octadecane mercaptan.
