Use of Dimethyldioxirane in the Epoxidation of the Main Constituents of the Essential Oils Obtained from Tagetes Lucida,Cymbopogon Citratus,Lippia Alba and Eucalyptus citriodora
Free accessResearch articleFirst published online July, 2011
Use of Dimethyldioxirane in the Epoxidation of the Main Constituents of the Essential Oils Obtained from Tagetes Lucida,Cymbopogon Citratus,Lippia Alba and Eucalyptus citriodora
Dimethyldioxirane (DMDO), a widely used oxidant in organic synthesis is considered an environmentally friendly oxygen transfer reagent because acetone is the only byproduct formed in its oxidation reactions. This work describes the isolation of the main constituents (terpenes) in the essential oils obtained from Tagetes lucida, Cymbopogon citratus, Lippia alba and Eucalyptus citriodora, their epoxidation with DMDO in acetone solution and the characterization of the resulting epoxides by GC-MS (EI) and NMR. This is one of the first reports involving the application of dioxirane chemistry to essential oils in order to generate modified compounds with potential uses in several areas of medicine and industry.
EdwardsJ.O., PaterR.H., CurciR., DiFuriaF. (1979) On the formation and reactivity of dioxirane intermediates in the reaction of peroxoanions with organic substrates. Photochemistry and Photobiology, 30, 63–70.
2.
MurrayR.W., JeyaramanR., MohanL. (1986) Chemistry of dioxiranes. 4. Oxygen atom insertion into carbon-hydrogen bonds by dimethyldioxirane. Journal of the American Chemical Society, 108, 2470–2472.
3.
AsensioG., MelloR., González-NúñezM.E. (1996) Evidence for the involvement of a sulfurane intermediate in the oxidation of simple sulfides by methyl(trifluoromethyl)dioxirane. Tetrahedron Letters, 37, 2299–2302.
4.
MurrayR.W., SinghM., RathN. (1996) Stereochemistry in the oxidation of primary amines to nitro compounds by dimethyldioxirane. Tetrahedron: Asymmetry, 7, 1611–1619.
5.
Fernandez-EscobarI., GilbertM., MesseguerA., BayonaJ.M. (1998) Complete elimination of interferences in the organotin determination by oxidation with dimethyldioxirane combined with alumina cleanup. Analytical Chemistry, 70, 3703–3707.
SharplessK.B., MichaelsonR.C. (1973) High stereo- and regioselectivities in the transition metal catalyzed epoxidations of olefinic alcohols by tert-butyl hydroperoxide. Journal of the American Chemical Society, 95, 6136–6137.
8.
MatthewsG.J., HassnerA. (1972) Synthesis of oxiranes. In Organic Reactions in Steroids Chemistry. Vol. II, FriedJ., EdwardsJ.A. (Eds.). Van Nostrand Reinhold, New York. 1–52.
9.
KatsukiT., SharplessK.B. (1980) The first practical method for asymmetric epoxidation. Journal of the American Chemical Society, 102, 5974–5976.
10.
SrinivasanK., MichaudP., KochiJ.K. (1986) Epoxidation of olefins with cationic (salen)manganese(III) complexes. The modulation of catalytic activity by substituents. Journal of the American Chemical Society, 108, 2309–2320.
11.
WengertM., SanseverinoA.M., MattosM.C.S. (2002) Trichloroisocyanuric acid: an alternate green route for the transformation of alkenes into epoxides. Journal of the Brazilian Chemical Society, 13, 700–703.
12.
WoitiskiC.B., KozlovY.N., MandelliD., NizovaG.V., SchuchardtU., Shul'pinG.B. (2004) Oxidations by the system “hydrogen peroxide-dinuclear manganese(IV) complex-carboxylic acid”: Part 5. Epoxidation of olefins including natural terpenes. Journal of Molecular Catalysis A: Chemical, 222, 103–119.
13.
SakaguchiS., NishiyamaY., IshiiY. (1996) Selective oxidation of monoterpenes with hydrogen peroxide catalyzed by peroxotungstophosphate (PCWP). The Journal of Organic Chemistry, 61, 5307–5311.
14.
MuñozA., BottiaE.J., CardenasC.Y., PatiñoJ.G., DíazO.L., MartínezJ.R. (2007) Estudio comparativo sobre la capacidad de atrapamiento del catión radical ABTS+. por los aceites esenciales de especies aromáticas con alto contenido de trans-anetol y estragol. Scientia et Technica, 33, 117–120.
15.
VillarR., CallejaJ.M., MoralesC., CaceresA. (1997) Screening of 17 guatemalan medicinal plants for platelet antiaggregant activity. Phytotherapy Research, 11, 441–445.
16.
CéspedesC.L., AvilaJ.G., MartínezA., SerratoB., Calderón-MugicaJ.C., Salgado-GarcigliaR. (2006) Antifungal and antibacterial activities of mexican Tarragon (Tagetes lucida). Journal of Agricultural and Food Chemistry, 54, 3521–3527.
17.
AquinoR., CáceresA., MorelliS., RastrelliL. (2002) An extract of Tagetes lucida and its phenolic constituents as antioxidants. Journal of Natural Products, 65, 1773–1776.
18.
SianoF., GhizzoniC., GionfriddoF., ColomboE., ServilloL., CastaldoD. (2003) Determination of estragole, safrole and eugenol methyl ether in food products. Food Chemistry, 81, 469–475.
19.
SyedM., QamarS., RiazM., ChaudharyF.M. (1995) Essential oils of the family Gramineae with antibacterial activity. Part 2. The antibacterial activity of a local variety of Cymbopogon citratus oil and its dependence on the duration of storage. Pakistan Journal of Scientific and Industrial Research, 38, 146–148.
20.
CarliniE.A., ContarJ.D.P., Silva-FilhoA.R., Silveira-FilhoN.G., FrochtengartenM.L., BuenoO.F.A. (1986) Pharmacology of lemongrass (Cymbopogon citratus Stapf). I. Effects of teas prepared from the leaves on laboratory animals. Journal of Ethnopharmacology, 17, 37–64.
21.
MishraA.K., DubeyN.K. (1994) Evaluation of some essential oils for their toxicity against fungi causing deterioration of stored food commodities. Applied and Environmental Microbiology, 60, 1101–1105.
22.
LenardãoE.J., TrechaD.O., FerreiraP.C., JacobR.G., PerinG. (2009) Green Michael addition of thiols to electron deficient alkenes using KF/alumina and recyclable solvent or solvent-free conditions. Journal of the Brazilian Chemical Society, 20, 93–99.
23.
MonsalveL.A. (2007) Comparación de la composición química de los aceites esenciales de las plantas de Lippia alba (Mill) N. E. Brown, provenientes de diferentes regiones de Colombia.Escuela de Química-Universidad Industrial de Santander, Bucaramanga-Colombia, 1–141.
24.
VianaG.S.B., do ValeT.G., RaoV.S.N., MatosF.J.A. (1998) Analgesic and anti-inflammatory effects of two chemotypes of Lippia alba: a comparative study. Pharmaceutical Biology (Formerly International Journal of Pharmacognosy), 36, 347–351.
25.
MontielJ., MesaA.C., DuránC., BuenoJ.G., BetancurL., StashenkoE.E. (2007) Evaluación de la actividad anti-candida y anti-aspergillus de aceites esenciales de Lippia alba (Miller) N.E. Brown quimiotipo carvona-limoneno y su asociación con sus componentes mayoritarios. Scientia et Technica, 33, 243–246.
26.
NogueiraM.A., DiazG., SakumoL., TagamiP.M. (2007) Antibacterial activity of Lippia alba (Lemon Herb). Latin American Journal of Pharmacy, 26, 404–406.
27.
StashenkoE.E., JaramilloB.E., MartínezJ.R. (2004) Comparison of different extraction methods for the analysis of volatile secondary metabolites of Lippia alba (Mill.) N.E. Brown, grown in Colombia, and evaluation of its in vitro antioxidant activity. Journal of Chromatography A, 1025, 93–103.
28.
SilvaJ., AbebeW., SousaS.M., DuarteV.G., MachadoM.I.L., MatosF.J.A. (2003) Analgesic and anti-inflammatory effects of essential oils of Eucalyptus. Journal of Ethnopharmacology, 89, 277–283.
29.
Nhu-TrangT.T., CasabiancaH., Grenier-LoustalotM.F. (2006) Authenticity control of essential oils containing citronellal and citral by chiral and stable-isotope gas-chromatographic analysis. Analytical and Bioanalytical Chemistry, 386, 2141–2152.
30.
PattnaikS., SubramanyamV., KoleC. (1996) Antibacterial and antifungal activity of ten essential oils in vitro. Microbios, 86, 237–246.
31.
LenardãoE.J., BotteselleG.V., de AzambujaF., PerinG., JacobR.G. (2007) Citronellal as key compound in organic synthesis. Tetrahedron, 63, 6671–6712.
32.
Song HeH., ZhangC., Ka-Wo NgC., ToyP.H. (2005) Polystyrene-supported triphenylarsines: useful ligands in palladium-catalyzed aryl halide homocoupling reactions and a catalyst for alkene epoxidation using hydrogen peroxide. Tetrahedron, 61, 12053–12057.
33.
KimS.G., LiemA., StewartB.C., MillerJ.A. (1999) New studies on trans-anethole oxide and trans-asarone oxide. Carcinogenesis, 20, 1303–1307.
34.
MohanR.S., WhalenD.L. (1993) Acid-catalyzed hydrolysis of cis- and trans-anethole oxides: discrete carbocation intermediates and syn/anti hydration ratios. The Journal of Organic Chemistry, 58, 2663–2669.
35.
GrecaM.D., MonacoP., PreviteraL., AliottaG., PintoG., PollioA. (1989) Allelochemical activity of phenylpropanes from Acorus gramineus. Phytochemistry, 28, 2319–2321.
36.
AdamW., ParedesR., SmerzA.K., VelozaL.A. (1998) Regio-, diastereo-, and chemoselectivities in the dioxirane oxidation of acyclic and cyclic allylic alcohols by methyl(trifluoromethyl)dioxirane (TFD): A comparison with dimethyldioxirane. European Journal of Organic Chemistry, 349–354.
37.
GlushkoL.P., SamsonovaV.N., MalinovskiiM.S., YanovskayaL.A. (1980) Citral oxide and some of its reactions. Russian Chemical Bulletin, 29, 754–757.
38.
PolovinkaM.P., PorublevaL.V., KorchaginaD.V., BarkhashV.A. (1992) Transformations of citral during the successive action of peracetic and fluorosulfonic acids. Zhurnal Organicheskoi Khimii, 28, 432–434.
39.
FdilN., RomaneA., AllaoudS., KarimA., CastanetY., MortreuxA. (1996) Terpenic olefin epoxidation using metals acetylacetonates as catalysts. Journal of Molecular Catalysis A: Chemical, 108, 15–21.
40.
UguinaM.A., DelgadoJ.A., RodríguezA., CarreteroJ., Gómez-DíazD. (2006) Alumina as heterogeneous catalyst for the regioselective epoxidation of terpenic diolefins with hydrogen peroxide. Journal of Molecular Catalysis A: Chemical, 256, 208–215.
41.
ThielW.R., AngstlM., HansenN. (1995) Metal catalyzed oxidations. Part 2. Molybdenum catalyzed olefin epoxidation in nonpolar solvents. Journal of Molecular Catalysis A: Chemical, 103, 5–10.
42.
AdamW., BialasJ., HadjiarapoglouL. (1991) A convenient preparation of acetone solutions of dimethyldioxirane. Chemische Berichte, 124, 2377.
43.
LajisN.H., M.Y.H., ToiaR.F. (1985) Extraction and identification of the main compound present in Elaeis Guineensis flower volatiles. Pertanika, 8, 105–108.
44.
YarovayaO.I., SalomatinaO.V., KorchaginaD.V., PolovinkaM.P., BarkhashV.A. (2002) Transformations of 6,7-epoxy derivatives of citral and citronellal in various acidic media. Russian Journal of Organic Chemistry, 38, 1594–1605.
45.
ArnoneA., DesMarteauD.D., NovoB., PetrovV.A., PregnolatoM., ResnatiG. (1996) Selective epoxidation of olefins by perfluoro-cis-2,3-dialkyloxaziridines. The Journal of Organic Chemistry, 61, 8805–8810.
