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   Molecules 2009 , 14, 3275-3285; doi:10.3390/molecules14093275  molecules ISSN 1420-3049  Article   Conversion of Natural Aldehydes from  Eucalyptus citriodora,   Cymbopogon citratus, and  Lippia multiflora  into Oximes: GC-MS and FT-IR Analysis †   Igor W. Ouédraogo 1 , Michael Boulvin 2 , Robert Flammang 2 , Pascal Gerbaux 2  and Yvonne L. Bonzi-Coulibaly 1, * 1 Laboratoire de Chimie Organique: Structure et Réactivité; UFR-SEA, Université de Ouagadougou, 03 BP 7021, Ouagadougou 03, Burkina Faso 2 Laboratoire de Chimie Organique, Centre de Spectrométrie de Masse, Université de Mons, Place du Parc 20, B-7000 Mons, Belgique ;   E-mail: (P.G.) † Dedicated to the memory of Prof. Guy Ourisson, Strasbourg, France (1926-2006), an inspiring mentor. * Author to whom correspondence should be addressed;   E-mail:; Tel.: +226 50 30 70 34; Fax: +226 50 30 72 42.  Received: 20 July 2009; in revised form: 11 August 2009 / Accepted: 26 August 2009 / Published: 31 August 2009 Abstract: Three carbonyl-containing extracts of essential oils from  Eucalyptus citriodora  (Myrtaceae), Cymbopogon citratus (Gramineae)   and  Lippia multiflora  (Verbenaceae) were used for the preparation of oximes. The reaction mixtures were analyzed by GC-MS and different compounds were identified on the basis of their retention times and mass spectra. We observed quantitative conversion of aldehydes to their corresponding oximes with a  purity of 95 to 99%.  E   and  Z   stereoisomers of the oximes were obtained and separated by GC-MS. During GC analysis, the high temperature in the injector was shown to cause  partial dehydratation of oximes and the resulting nitriles were readily identified. Based on FT-IR spectroscopy, that revealed the high stability and low volatility of these compounds, the so-obtained oximes could be useful for future biological studies. Keywords : essential oils; aldehydes; GC-MS; oximes; nitriles OPEN ACCESS   Molecules 2009 ,  14   3276Introduction Aldehydes are widely used compounds in perfumes and pharmaceutical preparations. The main disadvantage of these molecules is their intrinsic instability and propensity to oxidation. This inconvenience, together with their high volatility, in the case of low molecular weight molecules used in the perfumery field, for instance, makes the use of aldehydes less appealing for some applications [1,2]. In some cases, the corresponding oximes have been proven to present pleasant odour and their easy accessibility from carbonyl compounds was demonstrated. As a consequence, those compounds have been used as olfactory agents in various perfume compositions, instead of the corresponding carbonyl compounds [3,4]. Concerning pharmacology, several studies have shown that oximes present properties as antitumor [5], antimicrobial [6,7], antioxidant [8], anti-depressive [9], anticonvulsant [7], and antiviral agents [10], etc. Many oximes also were investigated in the context of heavy metal complexation [11,12] and gustative [13] properties. Consequently, finding methods dealing with oxime or oxime acetate preparations from natural molecules or starting directly from crude essential oils is of interest and indeed was already reported, albeit involving subsequent purification steps [14,15]. Recently, some of us demonstrated that natural aldehydes can be extracted in very good yields from essential oils by performing a bisulphite extraction [16]. As an alternative to the standard oximation  procedures realized on the crude essential oils [15], we propose in the present work to use the carbonyl extract (CE) rich in aldehydes obtained from essential oils by a bisulphite extraction. In this paper, we describe preparation of aldoximes from natural aldehydes from  Eucalyptus citriodora , Cymbopogon citratus , and  Lippia multiflora  essential oils in the presence of hydroxylamine hydrochloride. After chemical transformation each product was analyzed without any organic solvent extraction. GC-MS methodology was used to confirm oxime formation. FT-IR spectroscopy was used to check the stability and the volatility of crude oxime products (OP) compared with those of the initial aldehyde extracts. Results and Discussion Chemical composition of oximation products As recently reported [16], the studied essential oil aldehydic extracts are constituted by different molecules: citronellal for   Eucalyptus citriodora ; neral and geranial for Cymbopogon citratus;  and neral, geranial and perialdehyde) for  Lippia multiflora . These molecules, their expected aldoximes and the nitrile homologues observed in this study, are presented in Table 1. The oximation products (OP) of the carbonyl extracts (CE) from these three essential oils were obtained as described in the Experimental section. Such a synthetic protocol for oxime preparation is easy to use and thanks to its use of cheap starting materials, represents an economic route. The oxime  products (OP), obtained as colorless oils with a nice aromatic smell, were studied by GC-MS and FT-IR spectroscopy analysis.   Molecules 2009 ,  14   3277Table 1.  Structures of various aldehydes studied and names of oxime and nitrile homologues. Structures and names RC=OH  1a-d CHO   CHO   CHO   CHO  1a Citronellal 1b  Neral 1c Geranial 1d Perillaldehyde 2a-d (  E  ) RC=NOHH  2a (  E  ) (  E  ) Citronellal oxime 2b (  E  ) (  E  ) Neral oxime 2c (  E  ) (  E  ) Geranial oxime 2d (  E  ) (  E  ) Perillaldehyde oxime or (  E  ) Perillartine 2a-d (  Z  ) RC=NOHH  2a (  Z  ) (  Z  ) Citronellal oxime 2b (  Z  ) (  Z  ) Neral oxime 2c (  Z  ) (  Z  ) Geranial oxime --- 3a-d R C N  3a Citronellal nitrile3b  Neral nitrile 3c Geranial nitrile 3d Perillaldehyde nitrile GC-MS analysis of the OP allowed the identification and the quantification of the various components. As representative example, the chromatograms obtained from  Lippia multiflora carbonyl extract (CE) and its oximation products (OP) are shown in Figure 1. Immediately, we can establish that the chromatographic conditions are optimal since the chromatograms (Figure 1) present very good  peak separation that allows the determination of the retention times. Table 2 shows the various constituents observed in the chromatogram and identified in the three OP from the three carbonyl extracts. For each compound, retention time, mass spectra (70 eV) and % m/m are indicated. The identification of the different compounds, either in the CE and the OP, relied on the analysis of the EI mass spectra, which feature signals corresponding to the molecular ions [M  + ] and to structurally indicative fragment ions. Oximes are characterized by molecular ion peaks detected at m/z  169 for citronellal oxime radical cations (Figure 2), at m/z  167 for neral oxime (Figure 1) and for geranial oxime radical cations, and at m/z  165 for ionized perialdehyde oxime. All spectra exhibit [M-OH  ] +  peaks that are likely to correspond to nitrilium cations. The expected  E   and  Z   geometric isomers that are eluted at different retention times are treated as a sum of the two isomers in Table 2. The comparison of the CE and OP chromatograms in Figure 1 confirms the quasi quantitative conversion of aldehydes to oximes since only traces of unreacted starting carbonyl molecules (citronellal, neral, geranial and perialdehyde) are observed. Indeed, the chromatogram in Figure 1 that corresponds to the GC-MS analysis of OP from  Lippia multiflora  presents five important peaks. Four  peaks correspond to the oximes of (i) neral (molecular ion at m/z  167) (26.02 min. and 27.32 min.) and of (ii) geranial (molecular ion at m/z  167) (27.51 min. and 28.27 min.) as in the case of C. citratus . For  both oximes, the  E   and  Z   configurations are detected. Obviously, both isomers present the same mass spectra (Figure 1) and are then undistinguishable on the basis of a simple mass spectrometry analyses.   Molecules 2009 ,  14   3278Figure 1.  Comparative changes in GC chromatogram profiles of  Lippia   multiflora  a) carbonyl extract (CE), b) oximation product (OP) and mass spectra of the oximes. Spectrum A: compound 2b (Isomer I) neral oxime (I), spectrum B: compound 2b (Isomer II) neral oxime (II), spectrum C: compound 3d perialdehyde oxime. Chromatogram profiles A mass spectrum at RT 26.02 B mass spectrum at RT 27.32 C mass spectrum at RT 29.13
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