The search for innovative fragrant molecules

An overview of the recent research subjects in the perfumery field and, more precisely the synthesis of novel compounds for the hesperidic family of odorants, is presented. The new derivatives possess very different structures; nevertheless, they all share an aldehydic odor, but with diverse nuances, which make them all attractive for different purposes.     

Quantitative determination of guggulsterone in existing natural populations of Commiphora wightii (Arn.) Bhandari for identification of germplasm having higher guggulsterone content

Guggulsterone is an aromatic steroidal ketonic compound obtained from vertical rein ducts and canals of bark of Commiphora wightii (Arn.) Bhandari (Family - Burseraceae). Owing to its multifarious medicinal and therapeutic values as well as its various other significant bioactivities, guggulsterone has high demand in pharmaceutical, perfumery and incense industries. More and more pharmaceutical and perfumery industries are showing interest in guggulsterone, therefore, there is a need for its quantitative determination in existing natural populations of C. wightii. Identification of elite germplasm having higher guggulsterone content can be multiplied through conventional or biotechnological means. In the present study an effort was made to estimate two isoforms of guggulsterone i.e. E and Z guggulsterone in raw exudates of 75 accessions of C. wightii collected from three states of North-western India viz. Rajasthan (19 districts), Haryana (4 districts) and Gujarat (3 districts). Extracted steroid rich fraction from stem samples was fractionated using reverse-phase preparative High Performance Liquid Chromatography (HPLC) coupled with UV/VIS detector operating at wavelength of 250 nm. HPLC analysis of stem samples of wild as well as cultivated plants showed that the concentration of E and Z isomers as well as total guggulsterone was highest in Rajasthan, as compared to Haryana and Gujarat states. Highest concentration of E guggulsterone (487.45 μg/g) and Z guggulsterone (487.68 μg/g) was found in samples collected from Devikot (Jaisalmer) and Palana (Bikaner) respectively, the two hyper-arid regions of Rajasthan, India. Quantitative assay was presented on the basis of calibration curve obtained from a mixture of standard E and Z guggulsterones with different validatory parameters including linearity, selectivity and specificity, accuracy, auto-injector, flow-rate, recoveries, limit of detection and limit of quantification (as per norms of International conference of Hormonization). Present findings revealed the role of environmental factors on biosynthesis of guggulsterone isomers under natural conditions.     

Roses in the middle ages

Though we now tend to consider roses only as subjects for horticulture and perfumery, there were times when their significance extended far beyond that. Their religious symbolism among the Christian Europeans merits a section to itself; and the section on their practical significance in medicine occupies almost half of the present article. Yet it is not because roses were less important in perfumery and horticulture that the latter two are eclipsed in this way, but only because they were so much more important in areas where they are now forgotten.     

Forgotten Perfumery Plants – Part I: Balm of Judea

Perfumes have always been products of great importance, mainly composed of natural, valuable and vegetal raw materials. Today, some of them have completely disappeared in perfumery, even though they are part of our cultural heritage and were commonly used in the past. Balm of Judea is one of the most noble, rare and fascinating ingredient long used in perfumery and medicine, that is missing today. After years of research, we collected a resin and an essential oil (steam distillation of fresh aerial parts) from Commiphora gileadensis (L.) C.Chr . native from Saudi Arabia and cultivated in Israel. The aims of this study were to i) identify the main reasons of the loss of the balm of Judea, ii) characterize the volatile composition of the resin and the essential oil and iii) evaluate their olfactory profile and assess their biological activity. Eighty‐three compounds were identified in the resin, by a combination of GC‐MS and GC/FID techniques, using direct injection and HS‐SPME. α‐Pinene (24.0 %), sabinene (43.8 %), β‐pinene (6.3 %) and cymene (3.6 %) were the main identified compounds, giving an intense, terpenic and lemony smell to the resin. Anti‐inflammatory, wound‐healing and whitening activities were highlighted. Sabinene (22.7 %), terpinen‐4‐ol (18.7 %), α‐pinene (14.4 %) and cymene (13.6 %) were identified as the main components of the essential oil, giving a spicy, woody and lemony fragrance. Anti‐inflammatory and whitening activities were emphasized.     

Enzyme-triggered and self-cleaving fragrant alcohol precursors

The high volatility and water solubility of many natural perfumery alcohols leads to their rapid loss in fabric-care and personal-care applications. A dramatically enhanced substantivity is achieved by the use of fragrance precursors as controlled-release systems. In the first part of this article, we present multi-odorant precursors, in which the enzymatic cleavage of esters or carbonates of fragrant alcohols triggers subsequent steps leading to the release of fragrant ketones, lactones, and additional fragrant alcohols. In the second part, a study on oligocarbonates of fragrant alcohols is presented. Therein, the outstanding enzyme-independent performance of gluconolactone oligocarbonate 27 for the long-lasting release of (Z)-hex-3-en-1-ol is highlighted. We show that these polyfunctional compounds undergo complex rearrangements and intramolecular substitution reactions which lead to the observed release kinetics.     

Rosewood exploitation in the Brazilian Amazon: Options for sustainable production

The authors report on ongoing work in the Brazilian Amazon to assess the current and prospective management of rosewood (Aniba rosaeodora Ducke) populations threatened by a half-century of predatory extraction for the valuable essential oil linalool used widely in perfumery. The report synthesizes prior research on rosewood exploitation and markets and recent research to develop new essential oil products derived from rosewood leaves and stems. The study suggests alternative rosewood production systems, to guide investment in management and certification of sustainable rosewood oil supplies.     

A smelling trip into the past: the influence of synthetic materials on the history of perfumery

Contemporary perfumery has its roots in the work of the past, and many of the perfumes from this time have long since disappeared. What follows is a short account of some of the most famous perfumes from the past which have been inspired by the novel synthetic materials of the time. These important creations include, ‘Fougère Royale’ by Houbigant (1884) containing coumarin ( 1 ), ‘Jicky’ by Guerlain (1889) containing vanillin ( 2 ) and linalool ( 3 ), ‘Vera Violetta’ by Roger & Gallet (1892) containing α‐ and β‐ionone ( 4 and 5 , resp.), ‘Trèfle Incarnat’ by Piver (1898) containing isoamyl salicylate ( 6 ), ‘La Rose Jacqueminot’ of Coty (1904) containing Rhodinol ( 7 ), ‘Après l'Ondée’ by Guerlain (1906) containing para‐anisaldehyde ( 8 ), ‘Quelques Fleurs’ by Houbigant (1912) containing hydroxycitronellal ( 9 ), ‘N°5’ by Chanel (1921) containing the aldehydes C‐10 ( 10 ), C‐110 ( 11 ), and C‐12 ( 12 ), ‘Nuit De Noël’ by Caron (1922) containing 6‐isobutylquinoline ( 14 ), and ‘Femme’ by Rochas (1944) containing the so‐called ‘aldehyde C‐14’ ( 15 , γ‐undecalactone). The Osmotheque, the International Conservatory of Perfumes, was launched in 1990 and is regarded as a primary source of knowledge for the history of perfumery. Its vocation is to compile an amazing collection of 1700 perfumes (400 of them almost forgotten fragrances) – jewels of perfumery.     

Oxidative metabolism of ambrox and sclareolide by Botrytis cinerea

Ambrox (1), a perfumery diterpene, was oxidatively metabolised by a plant pathogenic fungus Botrytis cinerea in a xenobiotic fashion to afford a major product, i.e., 1beta-hydroxy-8-epiambrox (13) (60%) along with three minor metabolites 3beta-hydroxyambrox (2), sclareolide (5) and 3beta-hydroxysclareolide (7). Sclareolide (5), a cytotoxic diterpenoidal lactone was fermented with the same fungus to yield 3beta-hydroxysclareolide (7) (59%) as a major metabolite together with two minor metabolites characterised as 1-ketosclareolide (15), and 3beta,14-dihydroxysclareolide (16).     

A novel approach to prezizaane sesquiterpenes

Prezizaane sesquiterpenes are an olfactorily interesting class of tricyclic natural products, which occur in some precious perfumery raw materials. These compounds are biosynthetically derived from farnesyl pyrophosphate via cyclization, but some questions regarding the stereoselectivity of this process have not yet been answered. We discuss a novel and concise access to the tricyclic framework of these sesquiterpenes, as exemplified by the synthesis of (+/-)-5-epi-sesquithuriferone (5-epi-4).     

Vandachostylis ‘Sri-Siam’: an intergeneric hybrid with superior qualities as evidenced by its biochemical fragrance and transcriptome profiles

Journal of Plant Biochemistry and Biotechnology - Vandachostylis ‘Sri-Siam’ is a fragrant orchid, suitable as a potted plant for the floriculture and perfumery industries due to its...     

Recent developments in the chemistry of sandalwood odorants

Natural sandalwood oil, a unique and valuable ingredient in fine perfumery, has been the focus of scientific interest for many years. Due to its scarcity and its high price, the search for novel synthetic raw materials imitating the characteristic odor profile of sandalwood oil is as challenging as ever. In this context, the preparation of the novel sandalwood odorants 26, 33, and 39 will be discussed, including their sensory properties and structure-odor relationship.     

紫茎泽兰精油的香气成分及应用研究

紫茎泽兰(Eupatorium adenophorum Spreng.)为一有害杂草,本文从利用紫茎泽兰出发,对其精油进行了化学成分分析、香气质量评定及应用试验。精油经色谱-质谱分析,定性定量地鉴定了45个化合物,主要成分为对聚伞花素、乙酸龙脑酯等;紫茎泽兰精油的香气由辛甜香、凉气和药草香、花香、甜香及萜气组成,初步试用表明紫茎泽兰为一有利用前景的香原料,广泛推广使用,不仅可以产生一定的经济效益,而且对这一恶性杂草的防治也将有重要作用。     

A fruity note: crossmodal associations between odors and musical notes

Odors are notoriously difficult to describe, but they seem prone to a variety of crossmodal associations. In the present study, we generalize the previously-shown association between odors (from perfumery) and pitch (Belkin et al. 1997) to odors related to food and drink (in this case those associated with wine). We also demonstrate that, to a lesser extent (25% of the odor tested), participants preferentially match specific odors to certain types of instruments. The ratings of the odors along a number of dimensions are used in principal components analysis (PCA) to explore the psychological dimensions underlying the odor-pitch associations. The results demonstrate that both pleasantness and complexity, but not intensity, appear to play a role when choosing a pitch to match an odor. Our results suggest that these features of odor stimuli constitute psychological dimensions that can be consistently matched to auditory features.     

Chemical diversity in the essential oil of Indian valerian (Valeriana jatamansi Jones)

To explore the diversity in the essential oil yield and composition of Valeriana jatamansi Jones (syn. V. wallichii DC) growing wild in Uttarakhand (Western Himalaya), 17 populations were collected from different locations and grown under similar conditions. Comparative results showed considerable variations in the essential oil yield and composition. The essential oil yield varied from 0.21 to 0.46% in the fresh roots and rhizomes of different populations of V. jatamansi. Analysis of the essential oils by GC (RI) and GC/MS and the subsequent classification by principal component analysis (PCA) resulted in six clusters with significant variations in their terpenoid composition. Major components in the essential oils of the different populations were patchouli alcohol (1; 13.4-66.7%), α-bulnesene (3; <0.05-23.5%), α-guaiene (4; 0.2-13.3%), guaiol (5; <0.05-12.2%), seychellene (6; 0.2-9.9%) viridiflorol (<0.05-7.3%), and β-gurjunene (7; 0.0-7.1%). V. jatamansi populations with contents of 1 higher than 60% may be utilized commercially in perfumery.     

Identification of the components of the essential oil from Trollius europaeus flowers

The essential oil of Trollius europaeus flowers obtained by hydrodistillation was analyzed by gas chromatography coupled with mass spectrometry (GC–MS). The compounds giving fragrance of essential oils commonly used in perfumery 3,7-dimethyl-1,6-octadien-3-ol, nonanal, 3-methyl-2-pent-2-enyl-cyclopent-2-enone and oxacycloheptadec-8-en-2-one, rare in the Plant Kingdom, were tentatively identified. In the analyzed essential oil, the saturated fatty acids hexadecanoic acid (7.54 %), tetradecanoic acid (4.24 %), dodecanoic acid (3.10 %) and unsaturated fatty acids 9,12,15-octadecatrienoic acid (3.47 %), hydrocarbons, namely eicosane (20.03 %), hexadecane (8.63 %) and 1,2-benzenedicarboxylic acid (2.39 %), were also found.     

Carboxamides combining favorable olfactory properties with insect repellency

By a simple methodology, we have synthesized 68 carboxamides, with structural analogy to the most efficient mosquitoes repellent DEET (N,N-diethyl-m-toluamide, 9). Eight of them have very promising olfactory profiles. In addition, 34 carboxamides have been tested for their repellency properties against three breeds of cockroach; six of them are excellent in this domain. Two of these, the 2-ethyl-N-isopropyl-N-methylbutanamide and N,N-diallyl-2-ethylbutanamide combine both the positive aspects, and are thus very good candidates for use in functional perfumery, and more particularly in home-care formulations.     

Essential oil production: relationship with abundance of glandular trichomes in aerial surface of plants

The terpenoids, or isoprenoids, are a large family of natural products that are best known as constituents of the essential oils in plants. Because of their pleasant flavor and aromatic properties, essential oils have an economic importance in perfumery, cosmetic, pharmaceutical and various other industries. However, expression profiles of regulatory genes in essential oil production have not been dissected entirely, which may be an interesting topic of future research. In this report, we review recent studies on isoprenoids biosynthesis in plants. We also discuss the progress of our recent research activities on isoprenoid studies.     

Polymerase chain reaction with lesion scrapping for the diagnosis of human American tegumentary leishmaniasis

The objective of this work was to compare the polymerase chain reaction (PCR) using lesion scrapping with other conventional techniques for the diagnosis of the American tegumentary leishmaniasis (ATL). For this, patients with cutaneous lesions suspected to be ATL were studied. The DNA was amplified with the MP1L/MP3H primers. From the 156 studied patients, 79 (50.6%) presented positive parasite direct search (PD), 81 (51.9%) had positive Montenegro skin test (MST), and 90 (57.7%) presented PD and/or MST positive. The PCR was positive in all of the positive-PD patients (100% sensitivity), in 91.1% of the positive PD and/or MST patients, and in 27.3% of the patients that presented negative PD and positive MST. The PCR positivity was similar to the PD (P = 0.2482) and inferior to the MST (P = 0.0455), and to the PD/MST association (P = 0.0133). The high PCR sensitivity, and positivity in those cases where the PD was negative, highlights the importance of this technique as an auxiliary tool for the diagnosis of ATL.     

Synthesis of (R)- and (S)- muscone

(R)-(-)-Muscone (3-methylcyclopentadecanone, 1) the key perfumery component isolated from the male musk deer, Moschus moschiferus,* was synthesized from the easily available chiral building block, (R)-3-tert-butoxycarbonyl-2-methylpropanoic acid (2), by employing ring-closing olefin metathesis (RCM). Antipode (+)-1 was also synthesized in a similar manner from tert-butyl (S)-3-methoxycarbonylbutanoate (10). *(a) Walbaum, H. J. J. Prakt. Chem., 73, 488 (1906); (b) Ruzicka, L., Further considerations on the constitution of muscone. Helv. Chim. Acta, 9, 715, 1008-1017 (1926).     

New alicyclic musks: the fourth generation of musk odorants

Musk odorants are one of the most important classes of fragrances in perfumery because they impart sensuality to perfume-oil compositions. Among the three well-known classes of musks, a new and very exciting generation of musk odorants, the so-called alicyclic musks, was discovered recently, of which Helvetolide (2) and Romandolide (3) are the most popular representatives so far. To find new, structurally related alicyclic musks, we have synthesized a library of 114 unique alicyclic molecules with modified cyclohexyl moieties. The olfactory properties of all compounds were evaluated to identify the structural requirements to be met for a musk odorant.