- Effect of the Stereoselectivity of para-Menthane-3,8-diol Isomers on Repulsion toward Aedes albopictus
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Vector-borne diseases cause around 700,000 deaths every year. Insect repellents are one of the strategies to limit them. Para-menthane-3,8-diol (PMD), a natural compound, is one of the most promising alternatives to conventional synthetic repellents. This work describes a diastereodivergent method to synthesize each diastereoisomer of PMD from enantiopure citronellal and studies their repellence activity against Aedes albopictus. We found that cis-PMD is the kinetic control product of the cyclization of citronellal, while trans-PMD is the thermodynamic control product. X-ray diffraction analysis of crystals highlighted some differences in hydrogen-bond patterns between cis or trans isomers. The present paper demonstrates that (1R)-(+)-cis-PMD has the highest repellency index using a new evaluation system for 24 h. (1S)-(-)-cis-PMD has somewhat lower and (1S)-(+)-trans-PMD and (1R)-(-)-trans-PMD have a slight effect. Volunteer tests show that (1R)-(+)-cis-PMD is the most efficient. This effect could be ascribed to the interaction of PMD/insect odorant receptors and their physical properties, that is, the evaporation rate.
- Andrianjafy, Mbolatiana T.,Borrego, Lorenzo G.,Jeanneau, Erwann,Lemaire, Marc,Métay, Estelle,Ramanandraibe, Voahangy V.,Ramarosandratana, Niryhasinandrianina
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- Synthesis of: P-menthane-3,8-diol from citronellal over lignin-derived carbon acid catalysts
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p-Menthane-3,8-diol (PMD) is receiving growing attention as a natural mosquito repellent with lower toxicity compared to the widely-used N,N-diethyl m-toluamide (DEET). In this study, sustainable carbon acid catalysts derived from alkaline lignin (AL) were prepared for synthesizing PMD from a popular chemical (±)-citronellal in an environmentally friendly solvent of water. The catalytic performances of the AL-derived carbon acid catalysts prepared at different pyrolysis temperatures were better than those of other catalysts such as carbon black and H-USY. In particular, when the AL pyrolyzed at 500 °C was used as the carbon acid catalyst, the conversion of (±)-citronellal was as high as 97% with a high PMD yield of 86%, indicating that waste alkaline lignin from pulp and paper industries can be used as a source of acid catalysts. It is found that the formation of PMD is preferred over catalysts with weaker acid sites, whereas isopulegol was more easily formed over stronger acid sites. Moreover, the reaction route of the citronellal cyclization-hydration reaction was more dominant via the carbocation-hydration pathway rather than the isopulegol hydration route on the weaker carbon acid catalyst. This journal is
- Abudula, Abuliti,Chaihad, Nichaboon,Du, Xiao,Guan, Guoqing,Hao, Xiaogang,Kurnia, Irwan,Li, Shasha,Prakoso, Tirto,Yoshida, Akihiro
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p. 10441 - 10447
(2020/07/14)
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- Metal Nanoparticles Supported on Perfluorinated Superacid Polymers: A Family of Bifunctional Catalysts for the Selective, One-Pot Conversion of Vegetable Substrates in Water
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We describe the rational design of a new versatile family of bifunctional catalytic materials based on the combination of supported metal nanoparticles (Pd, Rh, Ru) and the superacid, perfluorinated Aquivion PFSA polymer. The heterogeneous catalysts were tested in the multi-step valorisation of representative plant derivatives to high-added-value chemicals. Particularly, the conversion of (+)-citronellal to (-)-menthol and levulinic acid to γ-valerolactone was achieved in one pot and in one stage in the water phase and shows full selectivity at a high conversion level under mild reaction conditions. The results are discussed in terms of the catalyst micro-structure.
- Moreno-Marrodan, Carmen,Liguori, Francesca,Barbaro, Pierluigi,Caporali, Stefano,Merlo, Luca,Oldani, Claudio
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p. 4256 - 4267
(2017/10/12)
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- Selective C-H bond hydroxylation of cyclohexanes in water by supramolecular control
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A new approach for selective hydroxylation of non-activated cyclohexanes using dioxirane generated in situ in water through supramolecular control has been developed. Using β-CD and γ-CD as the supramolecular hosts, selective hydroxylation of cyclohexane substrates, including trans/cis-1,4-, 1,3-and 1,2-dimethylcyclohexanes and trans/cis-decahydronaphthalene, was achieved in up to 54% yield in water. Furthermore, site-selective C-H bond hydroxylation of (+)-menthol was achieved by obstructing the approach of dioxirane to the C-H bond with higher steric hindrance through inclusion complexation with β-CD and γ-CD in water.
- Yang, Bin,Cui, Jian-Fang,Wong, Man Kin
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p. 30886 - 30893
(2017/07/07)
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- Solvent-free synthesis of novel para-menthane-3,8-diol ester derivatives from citronellal using a polymer-supported scandium triflate catalyst
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The use of natural resources as a chemical feedstock for the synthesis of added-value products is gaining interest; as such we report an environmentally friendly method for the synthesis of para-menthane-3,8-diol from natural citronellal oil in 96% yield, under solvent free aqueous conditions. The acylation of para-menthane-3,8-diol with various acid anhydrides over polymer-supported scandium triflate (PS-Sc(OTf)3) catalyst was subsequently developed, where both hydroxy groups of para-menthane-3,8-diol could be simultaneous acylated under mild reaction conditions to form the corresponding diesters in good yields. The advantages of this method include a simple procedure from natural resources, using solvent-free reaction conditions.
- Mafu, Lubabalo,Zeelie, Ben,Watts, Paul
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p. 2046 - 2054
(2016/10/05)
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- P-MENTHANE-3,8-DIOL ISOMER MIXTURE, COOLING SENSATION COMPOSITION COMPRISING THE SAME, AND PRODUCT COMPRISING THE COOLING SENSATION COMPOSITION
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The present invention relates to a p-menthane-3,8-diol isomer mixture 50% by mass or more of which is constituted of (1S)-isomers and a cooling sensation composition containing this mixture. The present invention also relates to a flavor and/or fragrance composition, food, beverage, cosmetic, daily use product, oral cavity composition, or pharmaceutical containing the p-menthane-3,8-diol isomer mixture in an amount of 0.0001 to 90% by mass.
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Paragraph 0076; 0077
(2014/08/19)
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- Biotransformations of terpenes by fungi from amazonian Citrus plants
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The biotransformations of (RS)-linalool (1), (S)-citronellal (2), and sabinene (3) with fungi isolated from the epicarp of fruits of Citrus genus of the Amazonian forest (i.e., C. limon, C. aurantifolia, C. aurantium, and C. paradisiaca) are reported. The
- Moreno Rueda, Maria Gabriela,Guerrini, Alessandra,Giovannini, Pier Paolo,Medici, Alessandro,Grandini, Alessandro,Sacchetti, Gianni,Pedrini, Paola
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p. 1909 - 1919
(2013/11/06)
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- Selective monoterpene-like cyclization reactions achieved by water exclusion from reactive intermediates in a supramolecular catalyst
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A polyanionic supramolecular assembly (1) is shown to catalytically cyclize the monoterpene citronellal and two homologues. In contrast to cyclization in acidic aqueous solution, the hydrophobic interior of 1 prevents the capture of reactive intermediates by water. This effect was also observed in the gold-catalyzed cycloisomerization of an enyne. Due to the steric confinement of the catalyst's interior, Prins cyclizations in 1 proceed cleanly both for substrates containing and lacking gem-dimethyl substitution. Encapsulation in 1 consequently imposes a degree of mechanistic control that, similar to enzyme catalysis, is not observed in bulk aqueous solution.
- Hart-Cooper, William M.,Clary, Kristen N.,Toste, F. Dean,Bergman, Robert G.,Raymond, Kenneth N.
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p. 17873 - 17876
(2013/01/15)
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- Hydroxylation of (+)-menthol by Macrophomina phaseolina
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Biotransformation of (+)-menthol with Macrophomina phaseolina led to hydroxylations at C-1, C-2, C-6, C-7, C-8 and C-9, with the C-8 position being preferentially oxidized. The resulting metabolites were identified as 8-hydroxymenthol (2), 6R-hydroxymenthol (3), 1R-hydroxymenthol (4), 9-hydroxymenthol (5), 2R,8-dihydroxymenthol (6), 8S,9-dihydroxymenthol (7), 6R,8-dihydroxymenthol (8), 1R,8-dihydroxymenthol (9) and 7,8-dihydroxymenthol (10). Metabolites 6-10 are described here for the first time. Their structures were characterized by spectroscopic analysis.
- Musharraf, Syed Ghulam,Ahmed, Muhammad Arif,Ali, Rahat Azher,Choudhary, Muhammad Iqbal
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experimental part
p. 77 - 82
(2012/04/11)
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- A METHOD OF PRODUCING CYCLIC DIOLS
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The invention described a method of producing a 5-alkyl-2-α-hydroxyalkyl-cyclohexanol of the formula (I), the method including the step of exposing a 6,7-unsaturated aldehyde or ketone starting material of the formula (II) in a two phase reaction system, one phase being an aqueous phase, to an acid catalyst at a temperature of above 100 degree Celcius [deg C] and 250 deg C, the amount of acid being between about 0.05 and 4.0 % (m/m) to produce the 5-alkyl-2-α-hydroxyalkyl-cyclohexanol (I).
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Page/Page column 14
(2009/12/05)
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- COMPOSITION CONTAINING P-MENTHANE-3, 8-DIOL AND ITS USE AS INSECT REPELLENT
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An economical and simple method of producing para-menthane-3,8-diol in relatively high yield is disclosed. The product is useful as a repellent against noxious insects and other arthropods.
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Page/Page column 13-14
(2009/04/25)
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- Cyclization of citronellal to p-menthane-3,8-diols in water and carbon dioxide
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A clean process has been developed for the synthesis of p-menthane-3,8-diols from cyclization of citronellal in CO2-H 2O medium without any additives. With the addition of CO2, the reaction rate could be enhanced about 6 t
- Cheng, Haiyang,Meng, Xiangchun,Liu, Ruixia,Hao, Yufen,Yu, Yanchun,Cai, Shuxia,Zhao, Fengyu
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experimental part
p. 1227 - 1231
(2010/04/29)
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- New Lewis-acidic molybdenum(II) and tungsten(II) catalysts for intramolecular carbonyl erie and prins reactions. Reversal of the stereoselectivity of cyclization of citronellal
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New Mo(II) complexes BnEt3N+[Mo(CO)4ClBr2]- (A) and Mo(CO)5(OTf)2 (B) and their W(II) congeners D and E have been developed as catalysts for the title reactions. Unlike other Lewis acids, the latter catalysts exhibit cis-stereoselectivity in the cyclization of citronellal (1 → 3 with A and 1 → 5 with B). Isotopic labeling allowed formulation of the reaction mechanism, according to which these complexes act as bulky Lewis acids, η1- coordinated to the carbonyl oxygen. The stereochemistry appears to be controlled by the protruding ligand L(p), which dictates the boatlike transition state III. The kinetically formed cis-alkenol 3 can be equilibrated by [Mo(CO)4Br2]2 (C) or ZnCl2 to its trans-epimer 2 via a retro-ene reaction.
- Kocovsky, Pavel,Ahmed, Ghafoor,Srogl, Jiri,Malkov, Andrei V.,Steele, John
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p. 2765 - 2775
(2007/10/03)
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- Method for producing para-menthane-3,8-diol
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To offer a method of producing useful para-menthane-3,8-diol having the excellent repellent action to harmful living things, including noxious insects, in high purity and high yield, simply, and economically by the use of citronellal as a raw material compound. The above-mentioned problems are resolved by the production method of this invention wherein citronellal is treated with aqueous sulfuric acid solution of 0.02 to 1.0 wt. % in concentration to produce para-menthane-3,8-diol. In case of recovering the produced para-menthane-3,8-diol, a method is preferably adopted, wherein after the reaction product is extracted with an aliphatic hydrocarbon solvent of 5 to 8 in carbon number, the extract is cooled down at temperature higher than the melting point of said aliphatic hydrocarbon solvent and of -10° C. or less to crystallize para-menthane-3,8-diol.
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- Selective oxidation of terminal isopropyl groups to tertiary alcohols by electrochemical methodology
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Selective oxidation of terminal isopropyl groups to the corresponding tertiary alcohols by an electrochemical method is described. Under the conditions using the TI(TFA)3-hematoporphyrin-O2- cathode reduction system, several substrates such as cholesterol (1) and Grundmann's alcohol (3) gave the corresponding tertiary alcohols 2 and 4, respectively, in reasonable yield.
- Maki, Shojiro,Konno, Katsuhiro,Takayama, Hiroaki
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p. 7067 - 7070
(2007/10/03)
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- Essential oil composition and allelopathic effect of the Brazilian lamiaceae Hesperozygis ringens (Benth.) epling and Hesperozygis rhododon epling
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Samples of Hesperozygis ringens (Benth.) Epling and Hesperozygis rhododon Epling essential oils were analyzed by a combination of analytical techniques: capillary gas chromatography, liquid/ solid chromatography, GC/MS coupling, and NMR spectroscopy. Twenty-four components have been identified representing altogether more than 95% of the oil content. The oil of H. ringens is constituted mainly by pulegone (79.2%) accompanied by several oxygenated derivatives (pulegone oxides, 1.2%; 8-hydroxy-p-menth-3-one, 1.3%; and 8-hydroxy-p-menth-4-en-3-one, 3.7%); that of H. rhododon contains menthone and pulegone as main compounds in almost comparable amounts (43.4% and 29.6%, respectively). Tests carried out on lettuce seeds using alcoholic extracts of the two species showed significant antigerminating properties mainly for H. ringens. The same activity was observed with its essential oil.
- Von Poser, Gilsane L.,Menut, Chantal,Toffoli, Maria E.,Verin, Pierre,Sobral, Marcos,Bessiere, Jean-Marie,Lamaty, Gerard,Henriques, Amelia T.
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p. 1829 - 1832
(2007/10/03)
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- Electroreductive Ring-Opening of α,β-Epoxy Carbonyl Compounds and Their Homologues through Recyclable Use of Diphenyl Diselenide or Diphenyl Ditelluride as a Mediator
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A novel access to β-hydroxy carbonyl compounds from the corresponding α,β-epoxy compounds has been attained through the recyclable use of diphenyl diselenide or diphenyl ditelluride as an electroreduction mediator in a MeOH-NaClO4-(Pt) system. α,β-Epoxy ketones are converted to the corresponding aldols in the presence of malonic esters.Similarly, α,β-epoxy esters and nitriles can be reduced to the corresponding β-hydroxy compounds in the presence of acetic acid.
- Inokuchi, Tsutomu,Kusumoto, Masahiko,Torii, Sigeru
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p. 1548 - 1553
(2007/10/02)
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- Heterolytic Cleavage of Homoallylic Alcohols: Part V - Stereoelectronic and Ring-Strain Factors Governing Fragmentation
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Some aspects of stereoelectronic factors governing the cleavage of hydroxycamphene derivatives with electrophiles, have been studied by the attempted fragmentation of epoxides (7, 9, 10, 12 and 14).To assess the role of ring-strain in this fragmentation, bicyclooctane derivative (28) and isopulegol (31) have been subjected to fragmentation conditions.Their failure to readily undergo fragmentation emphasises the contribution of ring-strain in providing driving force for this reaction.
- Patil, Dilip G.,Chawla, H. P. S.,Dev, Sukh
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p. 206 - 211
(2007/10/02)
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