Article

A Chemical Investigation of the Volatile Constituents of East Indian Sandalwood Oil (SantalumalbumL.)

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Abstract

Distillation foreruns from East Indian sandalwood oil (Santalum albumL.), representing 5–8% of the oil, have been investigated using fractional distillation, preparative column chromatography, gas liquid chromatography (GLC.), and chemical treatments. This allowed the isolation and characterization by their spectral data of 46 compounds. 32 of them were newly identified sandalwood oil constituents including 4 novel substances: santalone (2), 4-methylcyclohexa-1,3-dien-1-yl methyl ketone (4), 5,6-dimethyl-5-norbornen-exo-2-ol (7), and (E)-5-(2,3-dimethyl-3-nortricyclyl)-pent-3-en-2-one (20). The other constituents identified were 1-furfuryl-pyrrole (10) and 10 phenols accompanied by 17 terpene and sesquiterpene derivatives. Endo-2,endo-3-dimethyl-norbornan-exo-2-ol (6), an -santenol (z), precursor, was present in the last group of constituents. The compounds 2, 4, 6, 7, 20 have been synthesized as well as another novel constituent, endo-2-mythyl-3-methylidene-norbornan-exo-2-ol (5).

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... The essential oil from stem heartwood of S. album has been widely investigated [2,6,15,30,55]. Sandalwood oil is an excellent base and fixative for other highgrade perfumes and, by itself, is an excellent, mild, long-lasting and sweet perfume. ...
... Over the years, many groups isolated specialized metabolites from S. album (Fig. 2). Demole et al. [15] carried out vacuum distillation of the 1 kg of sandalwood oil at resulting in 40.3 g of a volatile fraction which was further fractionated by using Teflon spinning band distillation column, and those fractions were subjected to column chromatography to characterize the compounds . The successive treatments of 3 kg of crude sandalwood oil with inorganic bases and Girard 'P' reagent and subsequent purification led to the isolation of the compounds (42-58) [15]. ...
... Demole et al. [15] carried out vacuum distillation of the 1 kg of sandalwood oil at resulting in 40.3 g of a volatile fraction which was further fractionated by using Teflon spinning band distillation column, and those fractions were subjected to column chromatography to characterize the compounds . The successive treatments of 3 kg of crude sandalwood oil with inorganic bases and Girard 'P' reagent and subsequent purification led to the isolation of the compounds (42-58) [15]. Heartwood chips of 1.53 kg were extracted with methanol. ...
Chapter
Indian Sandalwood (Santalum album) is known for its aromatic heartwood and fragrant essential oil. For targeted tree improvement and manipulation of oil biosynthesis, biochemical pathways are to be identified. Unfortunately, due to high demand the population is dwindling and therefore there is a need to conserve and understand the biology of sandalwood using modern tools and techniques. Recently, attempts have been made to understand the Indian sandalwood genome, and large-scale transcriptome data have been generated. The basic information obtained helped us to understand the sandalwood oil biosynthesis pathway, and more information is needed for manipulating oil constituents and artificial synthesis of sesquiterpenoids. Current status of genomics, transcriptomics, proteomics and metabolomics is discussed in this chapter.
... Sandalwood oil shows a variety of biological activities, such as antiviral, anticarcinogenesis, antipyretic, antiseptic, antiscabietic, antitumor and diuretic effects (Kim et al. 2006; Misra and Dey 2013a; Bommareddy et al. 2019). Sandalwood usually yields 3-7% essential oil depending on the region and hemisphere (Demole et al. 1976). The value of a sandalwood tree depends on three important characteristics: the volume of heartwood, and the concentration and quality of its heartwood oil (Subasinghe et al. 2014). ...
... Previous studies showed that the α-santalol and β-santalol are responsible for the pleasant fragrance of sandalwood and that α-santalol is responsible for most of the essential oil's bioactivity (Burdock and Carabin 2008). However, global sandalwood resources are diminishing and are far from of being applicable for commercial-scale production due to habitat destruction, over-exploitation and complex requirements for cultivation (Demole et al. 1976; Sandeep and Manohara 2019), limitations that can to some extent be overcome through the use of biotechnology (Teixeira da Silva et al. 2016). Therefore, it is necessary to improve the production of santalol by biotechnological methods to meet rapidly increasing commercial demands. ...
... In recent years, many studies have documented the molecular regulation of sesquiterpene biosynthesis (Degenhardt et al. 2009). Santalol, a sesquiterpenoid, is the most dominant aromatic and active ingredient in sandalwood essential oil (Demole et al. 1976). ...
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Sandalwood is highly valued for its fragrant heartwood and its extracted oil. The major oil component santalols are terpenoids, which are biosynthesis through the MVA pathway. MK and PMK are the major enzymes on the MVA pathway. Little is known about the genes encoding MK and PMK in Santalum album on its expression regulation mechanism. The analysis of MK and PMK genes and their functions are important for the further study of the biosynthesis of santalol. These results will help to further study the role of MK and PMK genes in S. album santalol biosynthesis. The total RNA of sandalwood leaves was extracted, then the First-strand cDNA synthesis was obtained through the PrimeScript first-strand cDNA synthesis kit. Then sequence comparison and bioinformatics analyses of the genes homology of SaMK and SaPMK with MKs and PMKs, We also investigated subcellular localization of SaMK and SaPMK proteins. Its functional complementation of SaMK and SaPMK in yeast were also investigated. Atlast, MeJA was used to induce tissue-specific analysis and expression profiles of SaMK and SaPMK. The results showed that the full-length cDNA sequences of SaMK and SaPMK were 1409 bp and 1679 bp containing a 1381 bp open reading frame (ORF) encoding a polypeptide of 460 amino acids and a 1527 bp ORF encoding a polypeptide of 508 amino acids, respectively. Sequence comparison and bioinformatics analyses indicated that SaMK and SaPMK showed high homology with MKs and PMKs, respectively from other plant species. Further functional complementation of SaMK in an MK-deficient mutant yeast strain YMR208W and SaPMK in a PMK-deficient mutant yeast strainYMR220W confirmed that cloned SaMK and SaPMK cDNA encode a functional MK and PMK, respectively and mediated MVA biosynthesis in yeast. Tissue expression pattern analysis revealed that SaMK and SaPMK were constitutively expressed in all the tested tissues. SaMK was highly expressed in young leaves but least expressed in sapwood while SaPMK was highly expressed in roots and mature leaves, and least expressed in young leaves.
... Post-extraction, the methods for quantification and detection of sandalwood oil constituents from commercial oils [12] and heartwood samples essentially depend on gas chromatography (GC) [13] and GC-mass spectrometry (GC-MS) [14]. Furthermore, newer methods of detection have been proposed for evaluation of sandalwood oil constituents, such as Fourier transform infrared spectroscopy [15,16]. ...
... One major objective of this investigation was to develop an improved and easier method of detection for α-santalol, compared with the conventional analytical detection methods that are currently in use, i.e. GC [13] and GC-MS [12]. Moreover, an immunological tool would facilitate the development of an ELISA-based detection method that can offer a better selectivity for α-santalol in sandalwood oil and plant parts. ...
Article
Alpha-santalol is a key constituent of sandalwood essential oil and is responsible for most of its biological activities. The heartwood of a mature East Indian sandalwood tree accumulates this sesquiterpenoid-rich oil. Although gas chromatography (GC) and GC–mass spectrometry (GC–MS)-based technologies are used to detect and quantify santalols from heartwoods and the essential oil, information on the sites of deposition of these molecules remains obscure. Recently, in vitro cells of sandalwood were shown to accumulate sandalwood oil constituents. However, no reports are available on the visualization of these small molecules in planta. Immunization of rabbits with a bovine serum albumin (BSA)–α-santalol conjugate resulted in the production of anti-α-santalol polyclonal antibody in six weeks, which showed high affinity and specificity. The success and extent of cross-linking of α-santalol with BSA was further confirmed by photometric, fluorometric and chromatographic methods. These polyclonal rabbit antibodies were used to immunolocalize α-santalol in sandalwood plant materials for the first time. Results indicate the localization of α-santalol to the vascular bundles of somatic embryos and leaves, whereas distribution was evident in secondary xylem, cortical parenchyma and epidermis of the mature stem. Furthermore, the polyclonal antibody is shown to be a useful tool in detection of both free and immobilized α-santalol for screening purposes. - See more at: http://www.tandfonline.com/doi/suppl/10.1080/10412905.2014.910709#tabModule
... The hydrolyzed exhausted sandalwood powder (HESP) possesses anti-remorogenic, anti-inflammatory, anti-mitotic, antiviral, anti-cancerous, anti-hypertensive, anti-pyretic, and sedative properties (Desai et al. 1991). Recently, apoptotic (Bommareddy et al. 2012), cytotoxic (Matsuo andMimaki 2012), antiviral (Paulpandi et al. 2012), and anti-Helicobacter pylori (Takaishi et al. 2005) properties were reported for ␣-santalol [C 15 H 24 O, 220.35 Da, CAS No. 11031-45-1, FEMA No. 3006], the major constituent of sandalwood oil (Demole et al. 1976) and hence, have generated enormous interests. ...
... Sandalwood essential oil is a well known mixture of an array of sesquiterpenoid alcohols called santalols (Demole et al. 1976). Before proceeding with the in vivo biological activity screening of sandalwood oil, we obtained a GC-based profile of the commercially available essential oil used in the study. ...
Article
Sandalwood finds numerous mentions across diverse traditional medicinal systems in use worldwide. The objective of this study was to evaluate the in vivo anti-hyperglycemic and antioxidant potential of sandalwood oil and its major constituent α-santalol. The in vivo anti-hyperglycemic experiment was conducted in alloxan-induced diabetic male Swiss albino mice models. The in vivo antioxidant experiment was performed in d-galactose mediated oxidative stress induced male Swiss albino mice models. Intraperitoneal administration of α-santalol (100mg/kg BW) and sandalwood oil (1g/kg BW) for an week modulated parameters such as body weight, blood glucose, serum bilirubin, liver glycogen, and lipid peroxides contents to normoglycemic levels in the alloxan-induced diabetic mice. Similarly, intraperitoneal administration of α-santalol (100mg/kg BW) and sandalwood oil (1g/kg BW) for two weeks modulated parameters such as serum aminotransferases, alkaline phosphatase, bilirubin, superoxide dismutase, catalase, free sulfhydryl, protein carbonyl, nitric oxide, liver lipid peroxide contents, and antioxidant capacity in d-galactose mediated oxidative stress induced mice. Besides, it was observed that the beneficial effects of α-santalol were well complimented, differentially by other constituents present in sandalwood oil, thus indicating synergism in biological activity of this traditionally used bioresource.
... This compound is known to occur in the flavor of miscellaneous roasted foodstuffs, for example in coffee aroma [25]. It was also found in sandalwood oil from the stem [26]. Because of its powerful odor, it seems to play an important role in the whole fragrance of sandalwood oil [26]. ...
... It was also found in sandalwood oil from the stem [26]. Because of its powerful odor, it seems to play an important role in the whole fragrance of sandalwood oil [26]. ...
Article
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The chemical composition of volatile compounds from pericarp oils of Indian sandalwood, Santalum album L., isolated by hydrodistillation and solvent extraction, were analyzed by GC and GC-MS. The pericarps yielded 2.6 and 5.0% volatile oil by hydrodistillation and n-hexane extraction, and they were colorless and yellow in color, respectively. A total of 66 volatile components were detected. The most prominent compounds were palmitic and oleic acids, representing about 40-70% of the total oil. Many fragrant constituents and biologically active components, such as alpha- and beta-santalol, cedrol, esters, aldehydes, phytosterols, and squalene were present in the pericarp oils. This is the first report of the volatile composition of the pericarps of any Santalum species.
... The essential oil extracted from its heartwood is mainly used in the cosmetic and pharmaceutical industries due to its special aroma [7,8]. Sandalwood usually yields 3-7% essential oil depending on the region and hemisphere [9]. The value of a sandalwood tree depends on three important characteristics: the volume of heartwood and the concentration and quality of its heartwood oil [10]. ...
Article
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Plant-specific Rac/Rop small GTPases, also known as Rop, belong to the Rho subfamily. Rac proteins can be divided into two types according to their C-terminal motifs: Type I Rac proteins have a typical CaaL motif at the C-terminal, whereas type II Rac proteins lack this motif but retain a cysteine-containing element for membrane anchoring. The Rac gene family participates in diverse signal transduction events, cytoskeleton morphogenesis, reactive oxygen species (ROS) production and hormone responses in plants as molecular switches. S. album is a popular semiparasitic plant that absorbs nutrients from the host plant through the haustoria to meet its own growth and development needs. Because the whole plant has a high use value, due to the high production value of its perfume oils, it is known as the “tree of gold”. Based on the full-length transcriptome data of S. album, nine Rac gene members were named SaRac1-9, and we analyzed their physicochemical properties. Evolutionary analysis showed that SaRac1-7, AtRac1-6, AtRac9 and AtRac11 and OsRac5, OsRacB and OsRacD belong to the typical plant type I Rac/Rop protein, while SaRac8-9, AtRac7, AtRac8, AtRac10 and OsRac1-4 belong to the type II Rac/ROP protein. Tissue-specific expression analysis showed that nine genes were expressed in roots, stems, leaves and haustoria, and SaRac7/8/9 expression in stems, haustoria and roots was significantly higher than that in leaves. The expression levels of SaRac1, SaRac4 and SaRac6 in stems were very low, and the expression levels of SaRac2 and SaRac5 in roots and SaRac2/3/7 in haustoria were very high, which indicated that these genes were closely related to the formation of S. album haustoria. To further analyze the function of SaRac, nine Rac genes in sandalwood were subjected to drought stress and hormone treatments. These results establish a preliminary foundation for the regulation of growth and development in S. album by SaRac.
... After the addition of SEO (from 0.5 % to 2 %), the antioxidant capacity of the films increased significantly. Sandalwood essential oil contains a great variety of sesquiterpenoid alcohols called santalols (Demole et al., 1976). α-santalol is the main bioactive principle of the oil, therefore most of the antioxidant activities are attributed to it (Misra & Dey, 2013). ...
Article
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Chitosan with sandalwood (Santalum album) essential oil (SEO) using malic acid as solvent were evaluated as an active packaging film. It was applied as sachet to butter packaging. The effects of SEO concentration (0.5 %, 1 % and 2 % v/v) on chitosan film properties were studied by measuring the equilibrium moisture content, solubility, water vapor permeability (WVP), mechanical, optical, heat sealability, antioxidant properties, surface morphology and thermostability. SEO showed a significant effect on the film properties except for the puncture properties and the equilibrium moisture values. SEO promoted a significant decrease in tensile strength from 5.78 to 2.99 MPa, Young’s Modulus (YM) from 35.74 to 6.81 MPa, WVP from 6.70·10⁻¹¹ to 3.34·10⁻¹¹ g/m·s·Pa, and sealability from 195.20 to 107.94 N/m. The antioxidant properties of the films were improved with the presence of SEO. The addition of SEO significantly improved the UV-barrier of the films. The color and transparency of the samples showed significant variations by the addition of SEO. The active packaging film was evaluated as butter sachet. After 3 months of butter storage, a significant decrease of the thiobarbituric acid reactive substances was observed, showing a 36 % decrease in the lipid oxidation compared to unpackaged samples. The films are completely water-soluble and can be easily removed from foodstuffs after use without generating solid wastes.
... In addition to this, bergamotol and small amounts of sesquiterpene hydrocarbons such as limonene, santalene and bergamotene are also present. 3,4,5 India is amongst the top producers and exporters of natural sandalwood oil (N-SWO), contributing to meeting the demand of 80% to 90% of N-SWO in the international market. However, since 1950 the production has dropped from 4000 tons to approximately 1000 tons at the beginning of the 21st century. ...
Article
Naturally produced sandalwood oil (N-SWO) is prized for its use, both in perfumery as well as for skin benefits. However, its availability has been severely restricted in recent years due to overexploitation. The industry has responded by using biotechnology to produce santalol—the key molecule in N-SWO. Using such biotechnology-derived and natural ingredients, an oil that mimics the composition of N-SWO was created. This reconstituted oil called Sacrosantola was compared to N-SWO for its safety and skin benefits, using various in vitro models. Compared to N-SWO, Sacrosantol showed a similar safety profile, photo-protective and anti-inflammatory benefits, as well as antibacterial properties. Thus, Sacrosantol can be used as a sustainable and cost-effective alternative to natural sandalwood oil.
... Isoeugenol is a fragrant essential oil found in many different plants. It has been extracted, admixed with eugenol and other plant volatiles, from calamus, savory, basil, ylang-ylang, clove, tuberose, jonquil, nutmeg, tobacco, sandalwood, dill seed, mace, gardenia, petunia, and other flowers [4][5][6][7].Due to sweet , floral fragrance isoeugenol is incorporated into various household cleaning agents and personal hygiene products , including perfumes, cream lotions, soaps and detergents [8] .Isoeugenol finds use in food products and in medicine as an antioxidant, local antiseptic, analgesic anti-inflammatory, potential anticancer , anti-fungal etc [9][10][11][12][13][14][15][16][17].It is known to have anti-arthritic activity also [18]. Tasting like anise or licoricey isoeugenol is added to non-alcoholic drinks, baked foods, candy, and chewing gums. ...
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p>Physico-chemical properties plays an important role in determining toxicity of a material hence were calculated using acdlab/chemsketch and the data predicted is generated using ACD/Labs Percepta Platform - PhysChem Module. Gaussian 09, RevisionA.01, software package was used for the theoretical quantum chemical calculations of 2-methoxy -4-(prop-1-en-1-yl) phenol commonly called Isoeugenol. DFT/B3LYP/6-311G (d, p) basis was used to perform geometric optimization and vibrational frequency determination of the molecule. The statistical thermochemical calculations of the molecule were done at DFT/B3LYP/6-311G (d, p) basis set to calculate the standard thermodynamic functions: heat capacity (CV), entropy (S) and Enthalpy (E). DFT/B3LYP/6-311G (d, p) basis set was used to calculate the various NLO properties like dipole moment (µ), mean linear polarizability (α), anisotropic polarizability (Δα), first order hyperpolarizability (β), second order hyperpolarizability (γ) in terms of x, y, z components for Isoeugenol (2-methoxy -4-(prop-1-en-1-yl) phenol. Same basis set was used to carry out Mulliken population analysis. UV-Visible absorption spectra, ECD spectra, electronic transitions, vertical excitation energies and oscillator strengths of Isoeugenol (2-methoxy -4-(prop-1-en-1-yl) phenol) were computed by Time Dependent DFT (TD-DFT) method using the same basis set. FMO analysis, Molecular electrostatic potential study was also done using the same basis set.</p
... It is a fragrant essential oil found in many different plants. It was extracted, mixed with eugenol and other volatiles of plants, calamus, salted, basil, ylang-ylang, cloves, tuberose, jonquil, nutmeg, tobacco, sandalwood, dill seeds, mace, gardenia, petunia and other flowers [24][25][26][27]. It is commercially produced by isomerization of eugenol, which occurs in oils isolated from clove, pepper, bay leaf and cinnamon [28]. ...
Article
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Introduction: This increase in the prevalence of drug-resistant pathogens occurs at a time when the discovery and development of new antimicrobial agents occur slowly. In this context, the objective of this study was to investigate the antifungal activity of isoeugenol, a phenylpropanoid, by in vitro and in silico assays against Penicillium citrinum strains. Material and method: For in silico analysis, the software PASS online, Molinspiration and Osíris were used. For the determination of Minimum Inhibitory Concentration (MIC) and Minimal Fungicide Concentration (MFC) of isoeugenol and voriconazole were carried out using the broth microdilution technique. PASS online has shown that isoeugenol has the opportunity to present antiseptic, antifungal, antibacterial, antimycobacterial activities. Molinspiration showed that the phytoconstituent has good potential for oral bioavailability. Conclusion: In the analysis with the Osiris program, it was demonstrated that isoeugenol has low irritant and tumorigenic risk. The MIC of isoeugenol varied between 256 and 32 µg/mL, MIC50 of 64 µg/mL and MIC90 was 128 µg/mL. The MFC50, MFC90 and MFC of the isoeugenol for P. citrinum species were 64, 256 and 518 μg/mL, respectively. After analysis, it was verified that the isoeugenol have bactericidal effect against the strains of P. citrinum. After these results, it is important to discover the mechanism of action involved in the antifungal action of the compound, as well as in vitro and in vivo toxicity tests.
... It is a fragrant essential oil found in many different plants. It was extracted, mixed with eugenol and other volatiles of plants, calamus, salted, basil, ylang-ylang, cloves, tuberose, jonquil, nutmeg, tobacco, sandalwood, dill seeds, mace, gardenia, petunia and other flowers [24][25][26][27]. It is commercially produced by isomerization of eugenol, which occurs in oils isolated from clove, pepper, bay leaf and cinnamon [28]. ...
... Other hydrocarbons such as α-santalene, β-santalene, αbergamotene and epi-β-santalene are also present in the oil as well as α-curcumene, β-curcumene, γ-curcumene, β-bisabolene and α-bisabolol are also reported in heartwood [6]. New antitumor sesquiterpenoid from S. album L. also reported in methanolic extract of heartwood [7].From Indian origin heartwood of S. album, some new bisabolane and santalane type of sesquiterpenoids along with (+) α-nuciferol, (+) citronellol and geraniol were isolated [8].More oil constituents including santalone, 3-dien-1-yl methyl ketone, 4methylcyclohexa-1, (E)-5-(2, 3-dimethyl-3-nortricyclyl)-pent-3-en-2-one and 5, 6-dimethyl-5-norbornen-exo-2-olwere identified [9].Indian sandalwood oil also confirmed two new sesquiterpene aldehydes as Cyclosantalal and epicyclosantalal [10]. The heartwood oil of S. albumL. ...
Article
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Objective: Present study aimed phytochemical evaluation and antimicrobial screening of petroleum ether and ethanol extracts of Santalum album seeds.Methods: Petroleum ether and ethanol extracts were screened for presence of chemical constituents. Petroleum ether extract was investigated detail by using chromatographic and spectroscopic methods. In vitro antimicrobial activity of both extracts were investigated using disc diffusion method on two gram-positive bacteria, Bacillus subtilis, Staphylococcus aureus, gram negative Pseudomonas aeruginosa, Escherichia coli and fungus Candida albicans.Results: Santalbic acid was identified in petroleum ether extract and content determined by HPTLC was 4.7%w/w. It was seen that petroleum ether extract have MIC value for B. subtilis, P. aeruginosa, E. coli and C. albicans were 78.125 µg/ml, 19.331 µg/ml, 625 µg/ml & 39.062 µg/ml respectively while MBC was 39.062 µg/ml, 4.882 µg/ml, 312.5 µg/ml & 9.765 µg/ml, respectively. Petroleum ether extract showed MIC and MBC values for S. aureus was similar as 156.25µg/ml. So, the petroleum ether extract showed significant antimicrobial activity against both gram positive, gram negative and fungal strain.Conclusions: The results of present investigations were indicative of possible high potency of petroleum ether extract due to santalbic acid which could serve as chemotherapeutic agent.
... Unknown 1 was identified as (E)-␣-bergamotenal on the basis of the following 1 H NMR and 13 C NMR data: 1 Beyond the standard 1 H and 13 C monodimensional spectra, acquired with 16 and 4000 scans respectively, the 2Ds homonuclear NOESY COSY and TOCSY experiments, together with the heteronuclear 13 C HSQC and HMBC experiments were performed, allowing the complete and total assignment of the resonances. In fact, both ␣-santalal and (E)-␣-bergamotenal had been previously reported (but not unambiguously identified), among the volatile constituents of the East Indian sandalwood oil and the costus root oil, respectively by low-field NMR studies [17,18]. Their characterization by high field NMR and absolute identification as compounds isolated fom Cordia verbenacea essential oil is reported in this study for the first time. ...
Article
Cordia verbenacea D.C. (Boraginaceae, Varronia curassavica Jacq. synonym) is a medicinal plant, native from Brazil, especially the leaves are used in folk medicine. The aim of this study was to extend the characterization of the volatile fraction of the essential oil obtained from this plant, by using GC-FID, GC–MS, and chiral GC. Moreover, to further clarify the composition of the volatile fraction, preparative multidimensional-GC (prep-MDGC) was used to collect unknown compounds, followed by NMR characterization. Specifically, the chemical characterization, both qualitative and quantitative, of the volatile fraction of the essential oil obtained from Cordia verbenacea cultivated in the Minas Gerais area (central area of Brazil) was investigated for the first time. The principal components from a quantitative point of view were α-pinene (25.32%; 24.48 g/100 g) and α-santalene (17.90%; 17.30 g/100 g), belonging to the terpenes family. Chiral-GC data are reported for the enantiomeric distribution of 7 different components. Last, to obtain the complete characterization of the essential oil constituents, prep-MDGC analysis was used to attain the isolation of two compounds, not present in the principal MS databases, which were unambiguously identified by NMR investigation as (E)-α-santalal and (E)-α-bergamotenal, reported for the first time in Cordia verbenacea essential oil.
... Their essential oil, sandalwood oil, has been old used as a noble perfume upon producing incense sticks, deodorants, cosmetics and aromatherapy agents as well as medicines [2]. Previous phytochemical studies on sandalwood oil have revealed the occurrence of numerous phenylpropanoids [3] and sesquiterpenoids [4][5][6][7][8][9] including α-santalol [10,11] and β-santalol [10,12]. Among various biological properties reported for the oil and α-santalol are antiviral [13], anticarcinogenic [14], neuroplastic [10,15,16] and antitumor effects [17,18]. ...
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In our continuing study on a survey of biologically active natural products from heartwood ofSantalum album(Southwest Indian origin), we newly found potent fish toxic activity of ann-hexane soluble extract upon primary screening using killifish (medaka) and characterized α-santalol and β-santalol as the active components. The toxicity (median tolerance limit (TLm) after 24 h at 1.9 ppm) of α-santalol was comparable with that of a positive control, inulavosin (TLm after 24 h at 1.3 ppm). These fish toxic compounds including inulavosin were also found to show a significant antifungal effect against a dermatophytic fungus,Trichophyton rubrum. Based on a similarity of the morphological change of the immobilizedTrichophytonhyphae in scanning electron micrographs between treatments with α-santalol and griseofulvin (used as the positive control), inhibitory effect of α-santalol on mitosis (the antifungal mechanism proposed for griseofulvin) was assessed using sea urchin embryos. As a result, α-santalol was revealed to be a potent antimitotic agent induced by interference with microtubule assembly. These data suggested that α-santalol or sandalwood oil would be promising to further practically investigate as therapeutic agent for cancers as well as fungal skin infections.
... [45][46][47][48][49][50][51][52][53][54][55][56][57] Considerable work was done by Shankaranarayana and co-workers on phytochemical and other related aspects of sandalwood including separation of and -santalols by column chromatography, [58] chromatographic separation of alpha and beta santalenes, [59] simple method for extracting sandal oil in higher yield through rectification of benzene extract, [60] preparation of sodium santalbate-dimethyl sulfate inclusion complex, [61] estimation of oil in depot based sapwood of sandal, [62] possibility of developing fragrant products from less odorous sandalwood oil, [41] estimation of content and composition of oil from central and transition zones of sandal disc, [63] utilization of sandalwood extractives, [64] recovery of essential oil from hydrolyzed exhausted sandalwood powder (HESP) [65][66] and isolation of santalols from sandalwood oil. [67] Major constituents of commercially available sandalwood oil are sesquiterpene alcohols like α-and β-santalols (C 15 H 24 O), bergamotols and several of their stereoisomers, whereas minor constituents includes lanceol, nuciferol, bisabolol and the sesquiterpene hydrocarbons such as α-and β-santalenes (C 15 H 24 ), bergamotenes, α-, β-and γ-curcumenes, β-bisabolene [68][69][70][71][72] and phenylpropanoids. [73] Usually, α-santalol is more abundant than β-santalol. ...
... [45][46][47][48][49][50][51][52][53][54][55][56][57] Considerable work was done by Shankaranarayana and co-workers on phytochemical and other related aspects of sandalwood including separation of and -santalols by column chromatography, [58] chromatographic separation of alpha and beta santalenes, [59] simple method for extracting sandal oil in higher yield through rectification of benzene extract, [60] preparation of sodium santalbate-dimethyl sulfate inclusion complex, [61] estimation of oil in depot based sapwood of sandal, [62] possibility of developing fragrant products from less odorous sandalwood oil, [41] estimation of content and composition of oil from central and transition zones of sandal disc, [63] utilization of sandalwood extractives, [64] recovery of essential oil from hydrolyzed exhausted sandalwood powder (HESP) [65][66] and isolation of santalols from sandalwood oil. [67] Major constituents of commercially available sandalwood oil are sesquiterpene alcohols like α-and β-santalols (C 15 H 24 O), bergamotols and several of their stereoisomers, whereas minor constituents includes lanceol, nuciferol, bisabolol and the sesquiterpene hydrocarbons such as α-and β-santalenes (C 15 H 24 ), bergamotenes, α-, β-and γ-curcumenes, β-bisabolene [68][69][70][71][72] and phenylpropanoids. [73] Usually, α-santalol is more abundant than β-santalol. ...
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Santalum album L. (Santalaceae) commonly known as Indian Sandalwood is one of the oldest and precious sources of natural fragrance with immense medicinal and commercial significance. S. album has been grown in India for the last 25 centuries and esteemed all over the world for its sweet, long-lasting and medicinally valued fragrant oil. Sandalwood and the essential oil derived from sandal heartwood have been used in various traditional systems of medicine, like Ayurveda, Siddha and Unani medicine in the treatment and prevention of wide range of ailments. The versatile therapeutic and healthcare importance of sandawood is attributed to the rich source of phytochemicals particularly sesquiterpeness. A thorough bibliographic investigation was carried out by analyzing worldwide accepted scientific database (Pub Med, SciFinder, Scopus, ACS and Web of Science), recognized books, Indexed as well as non indexed journals. Modern pharmacological studies have demonstrated a wide range of pharmacological activities ranging from antibacterial to anti-cancer. No significant toxicity has been indicated by sandalwood oil and its individual constituents; however, further study on chemical constituents and their mechanisms in exhibiting certain biological activities are needed to understand the full phytochemical profile and the complex pharmacological effects of this plant. The increased commercial exploitation of Sandalwood and low productivity of this endangered plant has raised the concern over its conservation and productivity enhancement through modern tools and techniques. The review discusses traditional uses, ethnopharmacology, phytochemistry and biological activities of sandalwood in order to divulge its medicinal and industrial worth and gaps requiring future research.
... O. littoralis oil also contained small amounts of santene (0.3%), vitispirane (1.0%) and (9Z)tricosene (0.8%). Santene is an unsaturated terpene found in East Indian sandalwood oil (Demole et al. 1976) and black spruce needles (von Rudloff 1975). Vitispirane is a norisoprenoid found in grapes and wine (Eggers et al. 2006). ...
Article
The essential oils from the cladodes of Opuntia littoralis, Opuntia ficus-indica and Opuntia prolifera growing wild on Santa Catalina Island, California, were obtained by hydrodistillation and analysed by gas chromatography-mass spectrometry (GC-MS). Terpenoids were the dominant class of volatiles in O. littoralis, with the two main components being the furanoid forms of cis-linalool oxide (10.8%) and trans-linalool oxide (8.8%). Fatty acid-derived compounds dominated the essential oil of O. ficus-indica with linoleic acid (22.3%), palmitic acid (12.7%), lauric acid (10.5%) and myristic acid (4.2%) as major fatty acids. O. prolifera oil was composed of 46.6% alkanes and the primary hydrocarbon component was heptadecane (19.2%). Sixteen compounds were common to all the three Opuntia species.
... Traditionally, as an age-old practice the steam distillate of the heartwood is sold as marketable sandalwood essential oil. Major constituents of commercially available sandalwood oil are sesquiterpene alcohols like, α-and β-santalols, bergamotols and several of their stereoisomers, whereas minor constituents includes lanceol, nuciferol, bisabolol and the sesquiterpene hydrocarbons such as α-and β-santalenes, bergamotenes, α-, β-and γ-curcumenes and β-bisabolene (Adams et al., 1975;Christenson et al., 1981;Demole et al., 1976;Howes et al., 2004;Jones et al., 2006) and usually, α-santalol is more abundant (~46%) than β-santalol (~20%) (Anonis, 1998). ...
... The East Indian sandalwood tree, Santalum album L., is identified as one of the most important medicinal tree in the world (Fox 2000). This woody tree is a root hemiparasite tropical species belonging to the taxonomic group Santalaceae and yields precious sandalwood, which contains over 90% of santalols, a mixture of sesquiterpenoids and hence is the focus of many investigations (Demole et al. 1976). The essential oil yield from a 50-year-old matured tree ranges from 2Á5 to 6%, which is the highest among all known 20 Santalum species, depending on the age of the tree and colour of the heartwood (Shankaranarayana and Kamala 1989). ...
Article
Unlabelled: Sandalwood oil has been found in numerous therapeutic applications in traditional medicines such as Chinese traditional medicine and Ayurveda. However, there are no comparative accounts available in the literature that focused on in vitro and in vivo tree sample-derived extracts. Combined dichloromethane and methanol extracts were obtained from in vitro samples, that is, callus, somatic embryo and seedlings, and in vivo from leaves of non-oil-yielding young and oil-yielding matured trees. Phytochemical evaluation of the extracts reveals that the tree is rich in terpenoids, saponin, phenolics and tannins. The antibacterial properties of the five extracts were compared with sandalwood oil by screening against nine Gram-negative and five Gram-positive bacterial strains by disc diffusion, agar spot and TLC bioautography methods. Minimum inhibitory concentration (MIC) for sandalwood oil was determined to be in the range of 0·078-5 μg ml(-1) for most of the test micro-organisms screened. Bioautography results indicated the presence of potential antimicrobial constituents in somatic embryo extracts and sandalwood oil. Among the extracts screened, the somatic embryo extracts showed the strongest antibacterial activity comparable only with sandalwood oil and matured tree leaves' extract. The findings presented here also suggest that apart from sandalwood oil, other parts of this tree across developmental stages are also enriched with antibacterial principles. Significance and impact of study: This study constitutes the first systematic investigation on phytochemical composition and antimicrobial efficacy of sandalwood tree across in vitro and in vivo developmental stages screened against thirteen bacterial strains by four methods. Using a battery of antimicrobial assay techniques, it is possible to follow the differential bioactive metabolic richness of plant parts, to decipher, for example comparable efficacy of somatic embryo extracts and sandalwood oil.
Chapter
Indian sandalwood (Santalum album L.) is an exquisite evergreen woody tropical tree which yields one of the world’s most expensive essential oil from its matured heartwood (~US$2600 l−1). The tree accumulates sesquiterpenes, second important group of active compounds in essential oil of plants. α- and β-santalols (C15H24O) in addition to α-and β-santalenes are the major constituents. The minor constituents of essential oil includes lanceol, nuciferol, bisabolol and the sesquiterpene hydrocarbons such as, bergamotenes, α-, β- and γ-curcumenes, β-bisabolene. Oil yield vary from 3 to 4% through steam distillation (48–72 h). Sandalwood oil having incredible signature in their base and top note, Cis-α-santalol is responsible for the light woody smell, and Cis-β-santalol is more linked to the stronger woody smell with a distinctive mark which fetch high value in the perfume and fragrance industries. In addition to this, sandalwood oil is well known to aid wide range of ailments and it has long antiquity of pharmacology and aromatherapy.Keywords Santalum album Sandalwood oilSesquiterpeneα-santalenesHeartwoodSantalol
Book
This book provides a global perspective of Indian Sandalwood categorized as ‘Vulnerable’ by the International Union for Conservation of Nature. It deals with history, distribution, propagation, chemistry, utilization, improvement, trade, and conservation in the present context. This book explores ways and means for restoring its past glory by creating awareness for its conservation and sustainable utilization. The content encompasses informative tables, appropriate graphs and figures, and illustrations with photographs and line drawings. This compendium would be useful for foresters, forestry professionals, botanists, policymakers, conservationists, NGOs, and researchers in the academia and the industry sectors.
Chapter
The chemistry of Sandalwood has been studied and reported for over a century; however, the chemical understanding of Sandalwood is ever expanding with technology and applications. Major and minor constituents of the Santalum album are discussed with reference to chemical identification. Major constituents are reoccurring in S. album heartwood independent of tree variabilities. Non-reoccurring minor compounds and their possible origin can be traced back to processing and distillation practices. Biosynthesis of Sandalwood follows an enzyme-dependant pathway, leading to the synthesis of unique sandalwood molecules. Chemical analysis of sandalwood involves the extraction of the oil by and distillation, solvent extraction or by more novel methods such as solid-phase microextraction. Analysis of sandalwood essential oil components is performed by gas chromatography equipped with a mass spectrometer or flame ionization detector; gas chromatography is the most widespread industrial and trade analysis method, which is also standardized by an international standards organization. Novel analytical methods such as high-performance thin-layer chromatography and solid-phase microextraction in combination with gas chromatography have been reported in analysing Sandalwood. This chapter is a review of current knowledge on sandalwood chemistry while also exposing future development opportunities.
Chapter
Sandalwood is a valued and widely used ingredient in perfumery. It has a history of use in India that documents back to the seventh century BCE. Its use in Western perfumery is not as long, but the unique qualities of this ingredient have seen it become a key ingredient in these products. By undertaking a review of the history of perfume development, exploring how Indian sandalwood works in these compositions, the benefit that this ingredient can bring to the final product and then looking at the chemistry of the constituents of sandalwood oil will allow a better understanding on why Indian sandalwood is so valued in this purpose. A comment on the future of Indian sandalwood is offered, and while some new opportunities exist such as sustainability, origin and traceability, there are also opportunities with developing some of the well-being benefits, associated with Indian sandalwood in the East for many years, into Western perfume compositions.
Chapter
In this chapter, we focus on the current status of knowledge on the floral biology of Santalum album and the role of flower visitors in its pollination and fruit set. Flowers are bisexual, actinomorphic and epigynous, borne on axillary or terminal panicles. Based on the position of stigma, three types of flowers are observed: pin (stigma above the level of anther), thrum (stigma at a lower level) and homostylous (stigma and anther at the same level). A flower lasts for about three days, and its colour gradually changes from pale green or white to dark red with age. Though the ovary has 2‒4 embryo sacs, only one matures. From flowering to fruit maturation, it takes 80‒85 days, and the berries are eaten by birds, especially the Asian Koel, which may also be involved in the dispersion of seeds. There appear to be some contradictions concerning pollination, though many workers suggest that S. album is an obligate outcrossing species. However, the per cent fruit set under open pollination conditions appears to be very low, indicating a deficit in pollinators. Of the 46 species of flower visitors recorded, syrphids, calliphorids and honey bees have been reported as the most frequent visitors. However, there have been no studies to identify efficient pollinators, as most of the reports are subjective and are not supported by hard data. We also discuss the methods to be followed in sandalwood pollination studies.
Article
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Sandalwood ( Santalum album L.) is highly valued for its fragrant heartwood and extracted oil. Santalols, which are the main components of that oil, are terpenoids, and these are biosynthesized via the mevalonic acid (MVA) pathway. Mevalonate kinase (MK) and phosphomevalonate kinase (PMK) are key enzymes in the MVA pathway. Little is known about the genes that encode MK and PMK in S. album or the mechanism that regulates their expression. To isolate and identify the functional genes involved in santalol biosynthesis in S. album , an MK gene designated as SaMK , and a PMK gene designated as SaPMK , were cloned from S. album . The sequences of these genes were analyzed. A bioinformatics analysis was conducted to assess the homology of SaMK and SaPMK with MK and PMK genes from other plants. The subcellular localization of SaMK and SaPMK proteins was also investigated, as was the functional complementation of SaMK and SaPMK in yeast. Our results show that the full-length cDNA sequences of SaMK and SaPMK were 1409 bp and 1679 bp long, respectively. SaMK contained a 1381 bp open reading frame (ORF) encoding a polypeptide of 460 amino acids and SaPMK contained a 1527 bp ORF encoding a polypeptide of 508 amino acids. SaMK and SaPMK showed high homology with MK and PMK genes of other plant species. Functional complementation of SaMK in a MK-deficient mutant yeast strain YMR208W and SaPMK in a PMK-deficient mutant yeast strain YMR220W confirmed that cloned SaMK and SaPMK cDNA encode a functional MK and PMK, respectively, mediating MVA biosynthesis in yeast. An analysis of tissue expression patterns revealed that SaMK and SaPMK were constitutively expressed in all the tested tissues. SaMK was highly expressed in young leaves but weakly expressed in sapwood. SaPMK was highly expressed in roots and mature leaves, but weakly expressed in young leaves. Induction experiments with several elicitors showed that SaMK and SaPMK expression was upregulated by methyl jasmonate. These results will help to further study the role of MK and PMK genes during santalol biosynthesis in S. album .
Article
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Sandalwood ( Santalum album L.) is famous for its unique fragrance derived from the essential oil of heartwood, whose major components are santalols. To understand the mechanism underlying the biosynthesis of santalols, in this study, we cloned two related genes involved in the mevalonate pathway in S. album coding for acetyl-CoA C-acetyl transferase (AACT) and 3-hydroxy-3-methyglutary-CoA synthase (HMGS). These genes were characterized and functionally analyzed, and their expression profiles were also assessed. An AACT gene designated as SaAACT (GenBank accession No. MH018694) and a HMGS gene designated as SaHMGS (GenBank accession No. MH018695) were successfully cloned from S. album . The deduced SaAACT and SaHMGS proteins contain 415 and 470 amino acids, and the corresponding size of their open-reading frames is 1538 bp and 1807 bp, respectively. Phylogenetic trees showed that the SaAACT protein had the closest relationship with AACT from Hevea brasiliensis and the SaHMGS proteins had the highest homology with HMGS from Siraitia grosvenorii . Functional complementation of SaAACT and SaHMGS in a mutant yeast strain deficient in these proteins confirmed that SaAACT and SaHMGS cDNA encodes functional SaAACT and SaHMGS that mediate mevalonate biosynthesis in yeast. Tissue-specific expression analysis revealed that both genes were constitutively expressed in all examined tissues (roots, sapwood, heartwood, young leaves, mature leaves and shoots) of S. album , both genes showing highest expression in roots. After S. album seedlings were treated with 100 μM methyl jasmonate, the expression levels of SaAACT and SaHMGS genes increased, suggesting that these genes were responsive to this elicitor. These studies provide insight that would allow further analysis of the role of genes related to the sandalwood mevalonate pathway in the regulation of biosynthesis of sandalwood terpenoids and a deeper understanding of the molecular mechanism of santalol biosynthesis.
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Chemical manipulation of the cycloadduct of citraconic anhydride and cyclopentadiene enables a new synthetic route to tricyclane sesquiterpenoids. This methodology is applied to the first total synthesis of α-ekasantalic acid.
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Development of a general catalytic and highly efficient method utilizing readily available precursors for the regio- and stereoselective construction of bioactive natural-product-inspired spiro architectures remains a formidable challenge in chemical research. Transition metal-catalyzed asymmetric 1,3-dipolar cycloaddition of azomethine ylides produces numerous N-heterocycles, but reaction control with the regioselectivity opposite to the conventional fashion has rarely been demonstrated. Herein, we report a unique ligand-controlled Cu(I)-catalyzed umpolung-type 1,3-dipolar cycloaddition of azomethine ylide to realize efficient kinetic resolution of racemic alkylidene norcamphors with the concomitant construction of previously inaccessible spiro N-heterocycles with high levels of regio- and stereoselectivity. The success of this methodology relies on the strategy of kinetic resolution, and the serendipitous discovery of a unique ligand-enabled regiospecific cycloaddition, which not only provides evidence for the existence of the minor zwitterionic resonance form in metallated azomethine ylide but also diversifies the existing chemistry of azomethine ylide-involved 1,3-dipolar cycloadditions with rare polarity inversion.
Chapter
The determination of the most important olfactory contributors of a fragrant natural raw material can be an extremely long and complex task which requires the combination of very efficient analytical techniques. Indeed, the characterization of these components is often difficult since the global odor of complex mixtures is not only due to the sum of the olfactory properties of each constituent, but also involves many synergies between each odorant constituents. In addition, the main contributors are often strongly potent odorants contained only in trace amounts, and therefore, their identification requires an exhaustive analysis of the whole mixture. Finally, since the olfactory sense is characterized by strong interindividual differences, a large number of panelists must be involved in such studies in order to bring generalizable data. Consequently, there is still lack of accurate knowledge about the main odoriferous constituents for many natural raw materials, and this situation is paradoxical when it concerns materials widely used for their odorant properties in the flavor and fragrance industry. This chapter presents an overview of the published data about the main odor-active constituents of a selection of natural fragrant raw materials. It describes the chemical structures and olfactory properties of the main odorant components reported in the literature for 10 extracts and essential oils, after a brief description of the general analytical and sensorial issues concerning the determination of key odorants in a mixture.
Thesis
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Ce projet de recherche est focalisé sur le lien entre la structure des molécules odorantes et leurs interactions avec les récepteurs olfactifs exprimés dans les neurones olfactifs. Cette recherche fondamentale est d'une importance primordiale pour la construction d'un «nez virtuel », physiologiquement inspiré, qui reproduit la fonction des 400 types de récepteurs olfactifs impliqués dans la détection des odeurs. Ici, chaque récepteur olfactif est représenté par un système moléculaire qui est reproduit atome par atome dans un modèle informatique. Un protocole optimal a été conçu pour prédire les structures de ces récepteurs grâce à l’analyse bioinformatiques de leurs séquences sous contraintes de données expérimentales. Ensuite, les bases de la relation entre la séquence d’un récepteur et son mécanisme d’activation en fonction de la structure d’une molécule odorante liée à sa cavité ont été établies. Par ailleurs, l’analyse des structures de molécules d’une même famille olfactive peut conduire à l’identification des récepteurs impliqués dans leur perception. L’ensemble de ces résultats constitue les bases pour l’étude des relations structure-odeur à l’ère post-génomique.
Thesis
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This research project is focused on the link between chemical structures of odorant molecules and their interactions with odorant receptors expressed in olfactory neurons. This basic research is of primary importance for building a physiologically-inspired “computational nose” that reproduces the function of the 400 types of odorant receptors involved in the perception of smells. Here, each odorant receptor is represented as a molecular system, reproduced atom per atom in a computational model. An optimal protocol has been built to predict the structure of these receptors using bioinformatics analyses of their sequences under the constraints of experimental data. Then, the relationship between the sequence and the activation mechanism of a receptor as a function of the structure of a molecule bound to its cavity has been established. Furthermore, the structural analysis of molecules belonging to the same olfactory family was shown to lead to the prediction of some receptors involved in their perception. These results constitute a basis for structure-odor relationships studies in the postgenomic era. Ce projet de recherche est focalisé sur le lien entre la structure des molécules odorantes et leurs interactions avec les récepteurs olfactifs exprimés dans les neurones olfactifs. Cette recherche fondamentale est d'une importance primordiale pour la construction d'un «nez virtuel », physiologiquement inspiré, qui reproduit la fonction des 400 types de récepteurs olfactifs impliqués dans la détection des odeurs. Ici, chaque récepteur olfactif est représenté par un système moléculaire qui est reproduit atome par atome dans un modèle informatique. Un protocole optimal a été conçu pour prédire les structures de ces récepteurs grâce à l’analyse bioinformatiques de leurs séquences sous contraintes de données expérimentales. Ensuite, les bases de la relation entre la séquence d’un récepteur et son mécanisme d’activation en fonction de la structure d’une molécule odorante liée à sa cavité ont été établies. Par ailleurs, l’analyse des structures de molécules d’une même famille olfactive peut conduire à l’identification des récepteurs impliqués dans leur perception. L’ensemble de ces résultats constitue les bases pour l’étude des relations structure-odeur à l’ère post-génomique.
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Three qualities of Eastern Polynesian sandalwood oil were analyzed using GC and GC-MS. Sixty-six constituents were identified: 5 monoterpenes, 58 sesquiterpenes and 3 others. The main constituents of the essential oils were (Z)-α-santalol and (Z)-β-santalol. Beside chemical composition, olfactory evaluation and chiral gas chromatography of β- and epi-β-bisabolol isomers confirmed the close relationship of Eastern Polynesian to East Indian and New Caledonian sandalwood oil.
Chapter
Introduction Terpene Synthesis From Isoprene 2,6-Dimethyloctane Derivatives Tail-to-Tail Dimethyloctanes: The Marmelo Lactones Substances Related to Chrysanthemic Acid Cyclobutane Monoterpenes Cyclopentane Monoterpenes p-Menthanes o-Menthanes m-Menthanes Tri- and Tetramethylcyclohexanes Ethyldimethylcyclohexanes The Cycloheptanes Bicyclo [3.1.0] hexanes: The Thujanes Bicyclo [2.2.1] heptanes Bicyclo [3.1.1] heptanes Bicyclo [4.1.0] heptanes Furan Monoterpenoids Pyran Monoterpenoids Acknowledgments
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Four commercial qualities of Hawaiian sandalwood oil produced from wood of Santalum paniculatum originating from the island of Hawaii ("The Big Island") were analyzed using GC and GC-MS. Main constituents of the oils were (Z)-α-santalol (34.5-40.4%) and (Z)-β-santalol (11.0-16.2%). An odor evaluation of the oils was carried out against East Indian sandalwood oil. In addition, the chemical composition of Hawaiian sandalwood oil was compared with four different Santalum species originating from East India, New Caledonia, Eastern Polynesia and Australia, respectively.
Article
Essential oil from the roots of East Indian sandalwood, Santalum album L. was analyzed by GC and GC-MS. The root bark and sapwood yielded no extract. The heartwood of the plant yielded 10.3 % of oil by solvent extraction. Fifty-three compounds were detected, representing 99.9 % of the total oil. Forty-five of them were identified by close matches with standard mass spectra and those reported in the literature and by retention indices, which included 30 sesquiterpenols (78.5 %), 9 sesquiterpenes (7.8 %), 1 terpenoic acid (0.4 %), and 5 sesquiterpenoid isomers (4.4 %). The major constituents in the essential oils were α- and β-santalol, accounting for 19.6 and 16.0 %, respectively. The content of α-santalol was less than a proposed range of 41–55 %; however, β-santalol content was close to the specification of ≥ 18 %. The total content of bisabolenol A, B, C, D and their isomers was also high, 25.0 % of the oil.
Article
A series of eleven β-santalol analogs, including nine new derivatives, was prepared by semisynthesis from natural (−)-(Z)-β-santalol and studied by gas chromatography-olfactometry (GC-O) to characterize their olfactory properties and potencies. These compounds and 45 others selected in the literature were used to build three olfactophores by molecular modelling. Three models were obtained that gather structural and physicochemical constraints that will be useful for further design of new sandalwood odorants.
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Abstract 1. Isoeugenol (IEG) has been tested for toxicity and carcinogenicity due to high potential for human exposure and the structural resemblance to known carcinogenic allylbenzenes. In order to support the interpretation of toxicity and carcinogenecity study outcomes, a toxicokinetic study was performed in which both sexes of F344 rats and B6C3F1 mice were given IEG as a single intravenous (IV) or gavage administration. 2. Following IV administration, IEG was rapidly eliminated from systemic circulation in both species and sexes. Gavage administration revealed a rapid absorption of IEG with tmax values ≤20 min for both species and sexes. In rats, AUC increased in a greater than dose-proportional manner and Clapp values decreased with increasing dose in both sexes suggesting saturation of IEG metabolism. On the other hand, Clapp values in male mice increased with increasing dose suggesting induction of IEG metabolism although this was not evident in the females. 3. Absolute bioavailability was greater in female rats (19%) than male rats (10%) (p < 0.0001), but was not different between the sexes for mice (28% males; 31% females) (p = 0.2437). The collective toxicokinetic data supported that low bioavailability following administration of IEG was the result of extensive first-pass metabolism.
Article
The chem. variability particularly, the leaf-flavonoids content of Santalum insulare was studied. The leaves were collected on a single population of S. insulare var. raiateense on Moorea island in the Society Archipelago. Structures of O-glycosyl- and C-glycosylflavones extd. from the leaves were obtained using 1D and 2D NMR expts. including DEPT, gs-COSy, gs-HMQC, and gs-HMBC sequences. The 13C NMR spectra of C-glycosylflavones, vicenin-2 and lucenin-2, recorded at room temp. gave two signals that were attributed to restriction of the rotation about the C-6-C-gluc. or C-8-C-gluc. bond by steric hindrance due to the bulky ortho substituents. The following compds. were identified: chlorogenic acid, apigenin, luteolin, apigenin-7-O-neohesperidoside, luteolin-7-O-neohesperidoside, isovitexin, isoorientin, vicenin-2, and lucenin-2. [on SciFinder(R)]
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Two new minor components of East Indian sandalwood oil have been isolated by chromatography. Structure elucidation using spectroscopical methods resulted in formulae 1 and 2. The relative configurations of the epimeric sesquiterpene aldehydes 1, 2 were determined by two-dimensional NMR-analysis (HETCOR-, INADEQUATE-, and NOE-experiments) of the corresponding acids, cyclosantalic acid (3) and epicyclosantalic acid (4). The proposed structures of the aldehydes were confirmed by oxidative degradation reactions. Both aldehydes could be oxidized under normal conditions resulting in the known products acetyldihydroalbene (7) and albene (12) but also some new products such as the acids 3,4 and the formates 8,9. Trace amounts of those oxidation products could also be detected as constituents of sandalwood oil. A possible biogenetic pathway leading from p-santalane derivatives to the cyclosantalals is briefly discussed.
Article
Sandalwood (Santalum album L.) is a traditional incense, and its essential oil is used in fragrances. The hexane extract from Indian sandalwood chips had a sandalwood odour similar to sandalwood chips, but it clearly differed from that of commercial essential oil. By fractional distillation of the extract under reduced pressure, a fraction was obtained that had a sandalwood-like odour and contained several unknown formyl compounds as the main constituents. Santalyl formates were isolated as new components from this fraction by chromatography and characterized by 1H- and 13C-NMR spectroscopy. These constituents were less abundant in the commercial essential oil than in the hexane extract. Santalyl formates were synthesized from the corresponding alcohols.
Article
A comprehensive review is presented on the constituents of the heartwood from fragrant sandalwood species, including Santalum album, S. spicatum and S. austrocaledonicum, which are important raw materials in the fragrance industry, and S. insulare, a closely related species. Analytical aspects are discussed in detail, both on qualitative and quantitative standpoints, and sensory properties are also reviewed. It is shown that more than 230 constituents have been identified so far in the heartwood of these sandalwood species. These components belong to many different chemical classes and are mainly terpenoids, but some other families are also represented. Copyright © 2010 John Wiley & Sons, Ltd.
Article
Three new campherenane-type (1, 4, 7) and three new santalane-type (9, 11, 12) sesquiterpenoids, and two aromatic glycosides (21, 22) together with 12 known metabolites including α,β-santalols (14, 18), (E)-α,β-santalals (15, 19), α,β-santaldiols (16, 20), α-santalenoic acid (17), and vanillic acid 4-O-neohesperidoside were isolated from Santalum album chips of Indian origin. The structures of the new compounds, including absolute configurations, were elucidated by 1D- and 2D-NMR spectroscopic and chemical methods. The antitumor promoting activity of these isolates along with several neolignans previously isolated from the same source was evaluated for both in vitro Epstein–Barr virus early antigen (EBV-EA) activation and in vivo two-stage carcinogenesis assays. Among them, compound 1 exhibited a potent inhibitory effect on EBV-EA activation, and also strongly suppressed two-stage carcinogenesis on mouse skin.Graphical abstract
Article
2,6‐Dimethyl‐10‐( p ‐tolyl)‐2,6( E )‐undecadiene ( 1 ) is a major constituent in the essential oil of Cistus monspeliensis , an aromatic shrub common in Mediterranian countries. 1 was isolated by column chromatography, subjected to ozonolyses, and the absolute configuration was determined by enantioselective gas chromatographic correlation with the ozonolysis product of the sesquiterpene hydrocarbon ar ‐curcumene with known absolute configuration. Chirality 15:794–798, 2003. © 2003 Wiley‐Liss, Inc.
Article
A phytochemical investigation of the polar constituents in the heartwood of Indian Santalum album L. resulted in the isolation of three new neolignans (1-3) and a new aromatic ester (4), along with 14 known components. The structures of the new compounds (1-4) were established using spectroscopic methods.
Article
Six new bisabolane-type (1-3) and santalane-type (4-6) sesquiterpenoids, together with (+)-alpha-nuciferol, (+)-citronellol, and geraniol, were isolated from the heartwood of Santalum album of Indian origin. Their structures, including two bisabolol diastereomers (1, 2), were established on the basis of spectroscopic data interpretation.
Article
Based on similarities between naturally occurring (-)-(Z)-beta- or (+)-(Z)-alpha-santalol ((-)- 1 or (+)-2, resp.) and the reversed (E)-configured synthetic derivatives from campholenal (7a), a simple model A was developed. Besides reconciliation of this stereochemical aspect, this initial model also tentatively explained the enantiodiscriminations as well as the large spectra of distances separating the OH function from the lipophilic quaternary center(s) reported for different classes of substrates. Evolution, modifications, and refinement of this imperfect model allied with the research for alternative possibilities are illustrated, along with a historical guideline, in the light of olfactively challenging synthetic seco-substructures as well as literature reports. Despite evolution of the inadequate model A and a plausible interpretation of the lipophilic part, the topological positions of the OH function and its vicinal alkyl substituent could nevertheless not be fully ascertained by this approach. This apparently inconclusive empirical concept prompted us to turn our attention towards a computerized methodology, which will constitute the second and third part of this study.
Article
We have tried to elucidate the origin of phytochemical variation in trees by studying concomitantly the chemical and microsatellite variations in Santalum austrocaledonicum. Eight natural populations were sampled in the New-Caledonian archipelago, a total of 157 individuals being analyzed. The main components, as revealed by gas chromatography (GC), were α- and β-santalol (as in other sandalwood species), although the level of (Z)-lanceol was particularly high. Most of the chemical variation was observed within populations (83.7%). With microsatellites, the variation between populations was more pronounced (32% of the total variation). Although the chemical variation between populations was small, we investigated the effects of genetic drift and migration by comparing the chemical- and molecular-differentiation patterns. The poor congruence between neighbor-joining trees, confirmed by the non-significant Mantel test between the molecular and chemical distance matrices (R=0.26, P=0.12), showed that genetic drift and migration are not the main evolutionary forces acting on chemical differentiation between populations. We could not find any effect of soil and rainfall conditions neither. Although the impact of drift and migration cannot be discounted in rationalizing between-population differentiation, the low variation among populations could result from a stabilizing selection caused by the same phytopathogen charge across the natural range.
Article
The synthesis and odor properties of cyclopropano-beta-santalol, a new santalol analogue, are described. The exocyclic double bond of the original molecule, beta-santalol, is replaced by a cyclopropane ring. Despite the analogies in the binding properties between the double bond and cyclopropane this change in the bulky hydrophobic part of the molecule leads to the complete loss of the characteristic sandalwood odor: in an olfactory evaluation the (Z)-product appears spicy and sweet, the (E)-isomer woody, but neither of them exhibits the typical sandalwood character.
Article
The double bond in the furan and thiophen ring can be induced to participate in a Claisen–Cope-type rearrangement. Furans substituted in the 2-position react more readily than those substituted in the 3-position. The 2-methyl-buta-1,3-dienyl ether of 3-furylmethanol can, however, be made to rearrange thermally, and the aldehyde thereby obtained can be converted into the corresponding alcohol, and then, by a second Claisen–Cope reaction to torreyal. The related sesquiterpenes, neotorreyol and dendrolasin and the monoterpene perillene have been synthesized.
Article
Die photosensibilisierte O2-Übertragung auf (+)-α-Thujen (7) ergibt nach Reduktion der entstandenen Hydroperoxide drei bisher unbekannte Alkohole. Neben den beiden Hauptprodukten (−)-trans-4-Hydroxy-β-thujen (8) und (−)-cis-Sabinol (10) war durch Allylumlagerung aus 8 in geringer Menge das (+)-Umbellulol (9) entstanden. Der tertiäre Allylalkohol 8 gibt bei der Chromsäureoxydation in guten Ausbeuten (−)-Umbellulon (12), das als wesentlichster Inhaltsstoff des Öles von Umbellularia californica Nutt. bisher synthetisch nicht zugänglich war.
Article
The reaction of phosphonate carbanions containing electron-withdrawing groups with aldehydes or ketones in an aprotic solvent constitutes a useful olefin synthesis. These reagents were, in general, more reactive than the analogous triarylphosphoranes or "Wittig" reagents and have a number of special features which enhance their utility.
Article
The solvolysis rates of some nortricyclyl, endo- and exo-dehydranorbornyl and endo- and exo-norbornyl halides have been determined in aqueous ethanol solution. The exo-isomers solvolyze considerably more readily than the endo-isomers. The double bond in the dehydronorbornyl halides appears to contribute less "driving force" in the ionization of the C-X bonds than does the 5,6-double bond in the solvolysis of cholesteryl derivatives. Nortricyclyl bromide appears to be singularly unreactive relative to other substances containing the cyclopropylcarbinyl grouping. The cyclopropane ring in the nortricyclyl cation does not appear to contribute significantly to the stabilization of the ion. It is suggested that "steric inhibition of hyperconjugative-type resonance" may be involved.
Article
The bisdecarboxylation of meso- or d,l-1,2-diphenylsuccinic acid by lead(IV) or anodic oxidation produces trans-stilbene, a result which excludes a concerted cis elimination for this system. The intervention of a cationic intermediate is indicated as an alternative by the behavior of α,β,β-triphenyl-β-hydroxypropionic acid (I) which undergoes oxidative decarboxylation to form chiefly phenyl benzhydryl ketone (II). The reaction of lead tetraacetate with either optically active exo- or endo-norbornane-2-carboxylic acid leads to exo-norbornyl acetate as principal product with the same degree of retention of optical activity in each case. The relatively minor effect of solvent on the stereochemistry of this reaction suggests that the enantiomeric products are formed via a common intermediate, probably a classical norbornyl cation associated with the anion Pb(OAc)3- or AcO-; the norbornyl free radical is definitely excluded as a precursor of inverted (rearranged) exo-norbornyl acetate on the basis of previous studies which indicate that this intermediate rearranges only at relatively high temperatures. Other examples of oxidative decarboxylation by lead(IV) are discussed in which the products seem to be formed predominantly from cations rather than free radicals. The possible significance of this reaction in the study of electron transfer, ion-pairing phenomena or questions of carbonium ion structures is noted.
Article
Simple stereospecific syntheses of d,l-β-santalene (V) and d,l-epi-β-santalene (VIII) from norcamphor are described. The hydrocarbon VIII has been found to occur together with V in a sample of "natural β-santalene" by use of vapor phase chromatographic and nuclear magnetic resonance measurements. The stereochemistry of the major component (V) of the natural mixture corresponds to that previously assigned to β-santalene by Ourisson.
Article
L'huile essentielle de cabreuva (essence des bois de Myrocarpus frondosus et de M. fastigiatus Allem.) renferme, en faibles proportions, de l'aldéhyde tétrahydro-Δ3,-p-toluique, de la p-méthyl-acétophénone et de la 1-tétrahydro-Δ3,-p-méthyl-acétophénone. Ces deux cétones ont été identifiées en proportions trés faibles dans l'essence de bois de rose du Brésil (Aniba rosaedora var. amazonica Ducke) et se trouvent vraisemblablement dans l'essence de bois de rose de Cayenne.
Article
Eine Synthese des bisher unbekannten o-Methylen-norcamphers wird angegeben. Einige Beziehungen des kürzlich beschriebenen Dehydrosantens (2.3 -Dimethylen-norbornylans) zur Santenreihe, insbesondere seine Überführung in das Santenhydrat („β-Santenol” von Aschan) und in das α-Santenol werden verwirklicht. Die Verwendung des Dehydro-santens als Dien-Komponente bei Dien-Synthesen wird dargetan.
Article
1-Diäthylamino-butadien geht mit Acrylsäureester, Acrylnitril, Methylvinyl-keton und Acrolein Diensynthesen ein. Die Konstitution und teilweise auch die Konfiguration dieser Addukte wird bewiesen. Die thermische Abspaltung von Diäthylamin aus diesen Addukten erfolgt monomolekular und wird von Substituenten in der Reihenfolge CHO> -COCH3 > -CO2R ≫ -CN beschleunigt.
Article
Die zwei noch unbekannten diastereomeren Santenhydrate wurden aus konfigurativ gesichertem Ausgangsmaterial dargestellt, das eine durch Grignard-Reaktion aus endo-Apocamphenilon, das andere aus 2exo.3exo-Dimethyl-bicyclo-[1.2.2]-heptan-carbonsäure-(2endo) durch Azidabbau zum Amin und Umsetzung des Amins mit salpetriger Säure. Für alle vier Santenhydrate konnte eine konfigurative Zuordnung getroffen werden.
Article
Mit metallierten Mono- und Bis-phosphon- und -phosphinsäureestern sowie Phosphinoxyden werden Mono- bzw. Bis-Olefinierungen von Carbonylverbindungen durchgeführt. Phosphonsäureester mit gesättigtem Alkylrest werden durch das Metallierungsmittel gespalten und sind im Gegensatz zu den Alkylphosphinoxyden als Olefinierungsreagentien ungeeignet. Der Einfluß verschiedener Faktoren wie Metallierungsmittel, Molverhältnis, Temperatur und Lösungsmittel auf den Reaktionsverlauf wird untersucht.
Article
Die Addition substituierter Cyclopentadiene an Äthylen führt zu einer Reihe alkylsubstituierter Bicyclo-[1.2.2]-heptene, deren wichtigster Vertreter das Santen ist.
Article
Les caractères de l'extrait éthéro-pétrolique (essence concrète) de la fleur de jasmin récoltée en Italie méridionale, de la fraction de cet extrait soluble dans l'alcool (essence absolue), de l'ensemble de ses constituants volatils, sont analytiquement identiques ou analogues aux produits correspondants obtenus de la fleur de jasmin provençale. Les essences obtenues de ces deux origines renferment du benzoate de benzyle, élément non encore signalé. Ont été décélés dans l'essence italienne, en outre de constituants découverts dans l'essence provençale, de l'acide benzoïque libre, du créosol, de l'aldéhyde benzoïque, de l'-terpinéol, du nérol, et une forte proportion d'un produit ou mélange de produits répondant à la formule C18H34O. L'éther 2, 4-dinitro-phénylique du créosol, la 2,4-dinitro-phénylhydrazone de la jasmone, les allophanates de l'-terpinéol, du nérol, du géraniol, décrits ici, étaient inédits.
Article
The analysis of a coffee concentrate is described: 202 constituents have been identified, 154 of which for the first time. Some of these compounds are new chemicals; their synthesis is described. Most identifications are based upon mass spectrometry combined in many cases with IR. spectrometry and comparison with reference compounds. MS. and IR. data are given in detail. The analysis shows that a large number of minor constituents is present, many of which could not be identified.
  • Wiley
  • Horner
  • Ruzicka