Essential Oils and Related Products Ernest Guenther, Gilbert Gilbertson, and Roman T. Koenig Fritzsche D o d g e & Olcott Inc., New York, N. Y. 1001 1
This fourteenth review of the analysis of essential oils and related products covers the literature from September 1970 to August 1972, inclusive. I t follows the general pattern previously established (255). Intensive investigations into the composition of essential oils and the structure of its components have continued a t an unprecedented pace. Once again it was not possible to include all papers related to the subject, though we have tried to include those dealing directly with essential oils. The new knowledge which has been acquired in respect to many of the commercially important oils, often has made it possible for the analytical chemist to be more certain of the purity and authenticity of essential oils, and, in some instances, has even enabled him to pinpoint the botanical variety or the area from which the oil was derived. Many investigations of oils of lesser commercial importance, sometimes obtained from new experimental hybrids, have been included. Some of these oils may well become articles of commerce in the future. Nearly all exploratory investigations of essential oils employed a combination of instrumental methods, most often gas chromatography with infrared, mass, nuclear magnetic resonance, or ultraviolet spectrometry, as well as chemical reactions and physical methods such as distillation and column chromatography. Because it would be too repetitious, specific mention of the methods used has often been omitted. The reader can generally surmise what methods were employed, or he may refer to the original article when necessary. Official Compendia. The second edition of the “Food Chemicals Codex” was published by the National Academy of Sciences (206). This expanded edition contains the monographs added in previous supplements to the first edition, plus 87 completely new monographs not previously published, thus bringing the total number of monographs in this edition to 639. These specifications are of particular importance to the flavor industry because it has been officially proclaimed that the Commissioner of Food and Drugs regards the applicable specifications in the current edition of “Food Chemicals Codex” as establishing food grade unless he has by Federal Register promulgation established other specifications. “Food Chemicals Codex” specifications have also been adopted, under certain conditions, by the Food and Drug Directorate of Canada (January 29, 1970) and by the Food Additives and Contaminants Committee, Ministry of Agriculture, Fisheries and Food, of Great Britain (1968). The scientific committee of the Essential Oil Association of the USA (192) established standards for six products as embodied in the following monographs: 273, citral dimethyl acetal; 286, oil thyme; 287, oil rosemary; 288, eucalyptol; 289, oil cardamom; 290, phenylpropyl aldehyde. Books and Articles. Among the books of most general interest which have been published are “Handbook of Naturally Occurring Compounds, Vol. 2: Terpenes” by Devon and Scott (162), “CRC Fenaroli’s Handbook of Flavor Ingredients” by Furia and Bellanca (228), which de-
scribes many essential oils and aromtitic synthetics in relation to their use in flavors, “ H a n d b u h der Kosmetika und Riechstoffe, Band 1: Die Kosmetischen Grundstoffe” by Janistyn (326), “Infrared Analysis of Essential Oils” by Bellanato and Hildago (71), and “Farlireaktionen in der Spektrophotometrischen Analyse Orgarkcher Verbindungen, Band 1: Organische Farbreagenzieri” by Vejdelek and Kakac (724). Two comprehensive reviews of new developments in perfumery materials including analyiical aspects were contributed by Bedoukian (68, 69). The use of oleoresins in perfumery and their advantages over essential oils, primarily due to their fixative properties, were discussed by Eiserle (189), and Gilbertson (240) described the advantages of oleoresins as flavors, whick result from their physical properties and essential oil content. General Procedures. A review of chromatographic and spectroscopic analysis of volatile subsi ances was compiled by Jennings (327). Lawrence (423) a h o discussed various techniques used in essential oil analysis. Belafi e t al. (70) employed a semimicro spinning-band column rectification technique to prepare essential oil sariples for subsequent preparative gas chromatographic separations. Issenberg and Hornstein (319) described gas chromatographic analytical procedures as well as isolation and concentration techniques. A mathematical method using rnutivariate statistics based on chromatography for the antilysis of blends of essential oils was illustrated by Elliott et al. (191). Staikov and Kalaidzhiev (663) invented a stainless steel chamber which may be connected to the entry port of a gas chromatograph. Placing dried plant material in this chamber permits the direct analysis of the cassential oil from the dried plant. The quantity of perfume oils in foaming bath oils was determined by Bruns (104). After cxtracting the oil and evaporating the solvent, he made use of a mathematical formula incorporating several correction factors. A colorimetric method was used by Grosman et al. (252) to estimate the quantity of oil directly in sweet pepper and dill. Hughes (305) designed a modified receiver for heavy essential oils, which resulted in improved oil determination accuracy. A method for absorbing essentid oils from distillation waters by passing the waters through a layer of poroplast material and then extracting the absorbed oil was described by Kozhin et al. (400). Naipawer et al. (510) designed a continuous laboratory distillation apparatus wherein volatile components from foods were absorbed and then desorbed for further identification by gas chromatography and mass spectrometrb . The processing of data from gas chromatography by computers was discussed by Schomburg et al. (623) with practical examples illustrating the demands made on a computer system in qualitative and quantitative analysis. Mazor et a1 (477) used the mathematically calculated retention index compared with the retention time a t three different temperatures of an unknown essential oil component to establish its identity. Breckler and Betts (98) employed relative retention time changes with temperature A N A L Y T I C A L C H E M I S T R Y , VOL. 45,
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for the identification of essential oil component:;. Betts (78) also demonstrated how essential oil components may be classified into five chemical groups by their relc6 t’ive retention times on columns of different polarity over a temperature range. Temperature-programmed gas chrclmatography on glass capillary columns was described by D’Aubigne et al. (153), who also illustrated the improged results possible by using mass spectrometry or chromatochemical techniques in conjunction with gas chrom&ograPhY. Ultra trace analysis, down to the range of lO-”J%, is possible by reversion gas chromatography and low temperature gas chromatography as shown by Kaiser (340). Trace analysis on capillary columns was applied b> Grob and Grob (250) to head space analysis of cognac xoma and other materials. Davis (154) suggested some simple methods to avoid loss of volatiles during head space analysis, such as losses through absorption by a rubber stopper. Kolb (386) outlined the procedure for head space analysis using a n electropneumatic sampling and S E mple injection system. Preparative gas chromatography with an efficiency of 2000-2500 theoretical plates was used by Rudenko vt al. (602) for the separation of series of structural and rkeric isomers of isoprenoid and essential oil compounds. Functional group analysis was accomplished by iIara and Ito (267) with gas chromatography of the products of pyrolysis in sulfur vapor a t 850-80°C. Walker and Wdf (754) investigated three different pyrolyzers, a capacitive boosted filament heater, a radiofrequency induction k cater using a ferromagnetic wire, and a vapor phase flowthrough tubular reactor, in an effort to find which ma,? be most suitable for interlab reproducibility of pyrolysis gas chromatographic results. Moore and Brown (492) developed gas chromatographic methods for identifying molecular fragments that result from microscale ozonolysis: of terpenes, whereas reductions in sequence with NaB114, LiAlH4, and platinum oxide were utilized by Hedin et al. (276) to effect the gas chromatographic separation of cssential oil components. The advantages of a combined gas chromatograph-msss spectropeter in the analysis of volatile mixtures was ill strated by Vallon (718), and Fedeli and Pedrinella (200) demonstrated the superior results attainable by first using a preparative gas chromatograph, followed by gas chron atography-mass spectrometry on the fractions. A new dimension in information was foreseen by Cohen and Karasek (131) with the use, in conjunction with a gas chromatograph, of the plasma chromatograph as an ion interfa-e to the mass spectrometer. Ultra-trace concentrations down to 10-12 mole fraction may be observed. Coupling of gas chromatography and infrared spectroscopy with the Extrocell system was reported by Guenthcr (256) who applied the technique to the identification of citrus oil components. Farnow (199) tested numerous et;sential oils with a combination of gas chromatography and infrared and ultraviolet spectroscopy, and Humphrey (306) combined gas chromatography with thin-layer chromatography with excellent results. Thin-layer chromatography was employed to identify numerous essential oils by Fertman and Lesnov (204), and Mancini (460) evolved comparative thin-layer chromato graphs for the essential oils in the Brazilian pharmaco. peia. Martinek (467) used a transfer technique before developing the spots with a detection reagent, and Bonzani da Silva (89) was able to identify the main components of various leaf essential oils by thin-layer chromatography of the oils obtained by extraction after brushing away the glandular hairs on the leaves. 46
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High pressure liquid chromatography has brought about revolutionary improvements in what may be accomplished with liquid chromatography, according t o Done et al. (178). Karasek (353) described a technique wherein a centrifuge provides the high pressure necessary to speed u p the chromatographic separations. The application of mass spectrometry for the determination of volatile compounds was described by McFadden and Buttery (449), and the mass spectral characteristics of such compounds found in essential oils and flavors were discussed. Kolor (388) also reviewed mass spectrometric techniques in the identification of volatile compounds. Knock et al. (382) explained the use of computer programs for the identification of compounds by matching their low resolution spectra against a library file of 8000 standard spectra. By this method, most components of a geranium oil were identified. High resolution mass spectrometry, data presentation, applications, and computer spectra interpreations were reviewed by Biemann (80). Duprey and Janes (185) described the use of a molecular separator of a modified Llewellyn design for the enrichment of the effluent from a gas chromatograph to permit improved mass spectrometric examination of natural products. Rapoport et al. (577) observed extensive H migration and double bond mobility due to electron impact, thus indicating the limitations of mass spectrometry for the detection of the position of double bonds in polyisoprenoids and other unsaturated organic compounds. Infrared emission spectra resulting from laser stimulation were cataloged by Hailey et al. (265), who correlated the spectra with the appropriate bond vibrations and indicated the wide applicability of this new technique. Low and Freeman (441) described some applications of interferometric infrared spectrometry and discussed the advantages of Fourier transform spectrometers compared with dispersion devices. The interferometric technique appeared to look promising for quality control. Atomic absorption spectroscopy was employed by Coles et al. (134) to determine copper down to 0.01 ppm. Meranger (481) used the technique to determine heavy metals in juices and beverages, and Price et al. (567) determined nickel in fatty oils with a rapid procedure, which, it was believed, could be applied to other metals. Organic compounds, which react with silver ions may be accurately determined by an indirect atomic absorption spectrometric method developed by Gupta and Boltz (260). Electron paramagnetic resonance spectroscopy was applied to the analysis of essential oil components by Revishvili (587). The spectra of excited singlet states exhibited a hyperfine structure which was typical of each component. The splitting of alkyl sidechains from monoterpenes having exocyclic C3 alkyl groups by electron pyrolysis was studied by Schildknecht and Penzien (621) as a method for structure elucidation, and useful data were obtained. Controlled thermolytic dissociation to identify functional groups a t the same time that the main structural character of the compound is identified was effected by Groenendyk et al. (251). Essential Oils-General. A general review of the analysis and production of essential oils was written by Quinet (571).
A modified oil trap permitting the determination of VOlatile oil content from plant material samples as small as 5 grams was devised by Singh et al. (640). Takaishi e t al. (688) described an improved apparatus which could measure 10-6 mole of essential oil in a sample of plant tissue of less than 1gram. The antibacterial activity of several essential oils was
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found to be of value by Jain and Kar (323), the antimicrobial efficiency of some essential oils was studied by Rao and Nigam (574), and Dayal and Purohit (156) found that a number of essential oils from India, particularly oils of Justica procumbens and Zanthoxylum alatum, had good antifungal activity. Saeki et al. (610) investigated the role of essential oil in the resistance of woods to termite attack. The physical properties and main components of many Indian essential oils were tabulated by Baslas and Baslas (52, 56). Sinha and Prakash (649) analyzed several oils from plants grown in Kumaon, including cypress and eucalyptus, Igolen (309) described the physical constants of oils from Lebanon, and Oliveros-Belardo et al. (530) ascertained the physical properties of a number of unusual essential oils from the Philippines, such as oils from sapodilla, soursop, papaya, persimmon, and guajave. Several of the oils had odors characteristic of the fresh fruits from which they were distilled. Czuba and Lehka (149) investigated the comp9sition of essential oils from plants commercially grown in Poland. Genin e t al. (235) used gas chromatography to study the composition of nine essential oils from spices, and Retamar (586) discussed the composition and properties of essential oils from Tucuman Province, Argentina. Individual Essential Oils. Oils of Abies Alba, distilled from sprigs during various seasons, were analyzed by fractionation, and thin-layer and gas chromatography by Jonczyk (330-332) who identified many of their components. Oil of Achyrocline Satureoides from the flowering tops of the plants was shown by Akisue (13) to contain cineol and caryophyllene. The oils of Acorus gramineus from plants grown in Taiwan, called Kam-seh-chang, were compared with those from plants grown in Japan. The former contained primarily methylchavicol, whereas the latter contained cisand trans-asarone. Fujita et al. (219, 221) therefore concluded that the Taiwan plant is a new variety. Oil of Agastache formosanum was shown by Fujita (218) to always contain I-isomenthone and 1-pulegone and to be distinctly different from oil of A. rugosa which contains methylchavicol. Bauer and Brasil e Silva (62) identified coumarin in oil of Ageratum conytoides. Alfalfa flower volatiles were collected by Loper and Webster (440) with a specially designed water-jacketed syringe, the content of which was then injected directly into a gas chromatograph. Steam-distilled oils from two Amomum species were investigated with gas chromatography by Lawrence (424). In the bark of Aniba hostmanniana is a n essential oil which Gottlieb and Da Rocha (247) found to contain 94.5% of 2,4,5-trimethoxyallylbenzene. Chromatographic analysis by Bonzani da Silva and Grotta (90) indicated 14 components in the essential oil of Ambrosia polystachya. Oil of Anise was investigated by Becker (64-66), who found anethole to be present in some varieties to an extent greater than 9670, and also related the formation of oil to the maturity of the plant and to other stimulating effect. Sud’eva and Senich (677) obtained an anise oil by COn extraction and compared it with the normal distilled oil. Colombo and Manitto (137) analyzed oil of star anise and recorded the mass spectrograms of estragole, cis-anethole, and trans-anethole. Anisoxide was shown to be an artifact formed by Claisen rearrangement, according to Okely and Grundon (528), and Svendsen and Karlsen (684) showed t b t cis-anethole is present in anise, star
anise, and fennel fruits, and is not an artifact formed during the distillation of the oils. Oil of Apium leptophyllum was distilled by Brasil e Silva et al. (95) and contained 32 hydrocarbons and 68 oxygenated components, the principal onc being apiole. The volatile oils from the roots, rhizomes, leaves, and flowers of various Arnica species were prepared by Willuhn (763, 764), and examined by ultraviolet spectrometry and thin-layer chromatography. Evstratova et al. (195) established the structure of arnifoline, i’solated from Arnica foliosa and A. montana, by chemical reaction methods and IR, UV, and NMR data, and Zakharov et al. (783) confirmed the structure according to its mass spectrum. Yano (775) identified the major components of oil from Artemisia feddei and established the :;tructure of a new monoterpene alcohol, “yomogi alcohol A.” The composition of oils from flowering tops and from leaves of Artemisia vestita were examined by Sinha m d Chauhan (646). They varied only slightly in percentagt: composition. Further investigation by Sinha and Baslati (645) substantiated earlier findings and also revealej the presence of cadalene. The volatile oil content of Asarum europaeum was found by Wierzchowska-Renke et al. 1‘760) to be greatest in the roots and rhizomes. Oil of Atractylodes ouata was analj’zed by column and gas chramatography and IR spectrometry by Studennikova and Khaletskii (676), who isolated 25 compounds and identified aromadendrene. The volatile aroma from balsam tolu was demonstrated by Wahlberg et al. (751) to be a complex mixture of aromatic and terpenoid compounds including benzyl ferulate or isoferulate and ferulic acid. The identification of 24 component!; in oil of sweet basil and 30 in a related variety grown in Thailand was reported by Lawrence et al. (429, 430). In another investigation, they separated 46 components by gas chromatography. Among them were 3-hexen-1-01, furfural, 3-octanone, anethole, eugenol methyl ether, methyl cinnamate, and eugenol. The composition of sweet basil oil from Jorhatn Assam was shown by Singh et al. (641) t o closely resemble the best European oils. Kapetanovic and Dugumovic (349) found that the same was true of c3weet basil oils from Herzegovina. Sweet basil oil from the Philippines contained primarily methylchavicol, according to Chantharasakul and Concha (124). The effect of fertilization and seasonal factors on the yield of oil was explored by Eksuzyan (190), and Ahmataj (3) reported on the experimental growing and distillation of Ceylon basil in Albania. The oil contained 67-73.570 eugenol. The yield and quality of bay oil distilled in Dominica was described by Ames e t al. (18). The production, uses, physical properties, and chemical composition of bergamot oil were related by La Face (415, 416). The oils resulting from an attempt to introduce bergamot into the Ivory coast and Mali were described by Huet (303, 304). The oils showed significant differences in composition from normal Italian oils, being deficient in linalool, and were also abnormal in their ultraviolet spectra, Le., C.D. value. An oil containing 55% cineol. was obtained from Blepharocalyx giganteus by Bravo and Retamar (97). Oil of Boenninghausenia albiflora was analyzed by Gupta et al. (262), who identified many major components including p-ionone. From oil of buchu, Sundt et al. (683) isolated and characterized two keto thiols which arc? also organoleptic principles in cassia, Lamparsky and Schudel (420) isolated the diastereoisosame compounds, p-menthane-8-thiol-3-one
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mers and substantiated theirestructures by IR, NMlZ, and mass spectra and chemical properties. The chief components of an oil from the flowers of Bupleurum fruticosum were identified by Peyroti and Roubaud (558). The main components of oil of Calamintha umbrosa, a type of savory, were isolated with column chromatography and identified by Gupta et al. (263). Calamus oils from several localities in Japan, examined by Fujita et al. (215), consisted' chiefly of p-asarontt and cis-methylisoeugenol. Minato et al. (486) isolated and characterized a new sesquiterpene, acoronene. Five additional sesquiterpenoids were isolated from calamus; oil, and their structures were established by Yamamura e t al. (771).
An extensive investigation of the leaf oil from Ca1,ycanthus floridus, separating 38 compounds, of which 34 were identified, was conducted by Collins and Halim ('136). Free borneol was not found. A total of 125 components were resolved from the volatiles in Capsicum frutescens by Haymon and Aurand (274).
Camphor oil occurred in greater quantity and with a higher camphor content in plants grown in full sunlight, but the per cent of safrole was higher in shaded plants, as shown in experiments by Fujita et al. (220). Hikino e l al. (296) clarified the absolute configuration of campherenone and campherenol, and Suga et al. (680) elucidated the biosynthesis of linalool in the camphor tree. A microscale essential oil determination in caraway seed was tested by Khalf-Allah et al. (374) and fount3 to be reliable. Von Schantz and Ek (737) examined cwaway oils from the flowers, fruits, leaves, stems, and roots and tabulated the results. I t was shown that carvone coes not form from limonene. Von Schantz and Huhtikangas (740) used tracer analysis to study the development of limonene and carvone in caraway seed. A volatile oil obtained from cardamon seed by COz extraction by Meerov et al. (479) proved to be of equal quidity with distilled oils. Bernhard et a1 (77) used open tubular gas chromatographic columns to analyze a coldpressed cardamon oil. Many previously reported components were confirmed and eleven compounds previou:ily not reported were identified. Isolimonene was the major terpene component of C'tzsearia sylvestris oil as proved by Brasil e Silva and Baucr (94).
Using chemical extraction, followed by gas chromatography, and identification with mass, IR, and NMR spectrometric methods, Ter Heide (700) analyzed cassia oil and identified 35 components, 23 of which had not becsn reported previously. Eleven of the newly reported components are ortho substituted benzene derivatives. Auw (32) proposed an unusual method for the rapid microdecermination of cinnamaldehyde in the oil, using the critical mixing temperature with ethylene glycol. The composition of oil of Catha edulis was elucidate1:l by Qedan (570), who employed a combination of moderii techniques. Five additional sesquiterpenes were found in both Virginia and Texas cedarwood oils by Kitchens et al. (380). Oil of Cedrus deodara obtained by extraction by Singh e t al. (642) was similar to steam distilled oil, though €1 greater yield was achieved. Pande et al. (536) discovered that the predominant isomer of atlantone in the oil is the trans form. The carbonyl compounds and esters in celery le'af and stalk oil were identified by Wilson (765). 3-Butyl phthalide and Sedanolide exhibited the characteristic odor and 48 R
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flavor of celery. Ahuja and Nigam (6, 8) reported several new components in celery oil and suggested four possible structures for a new acid having a cyclohexene nucleus. The change in yield and composition of 'oil of Chaerophyllum hirsutum was studied by thin-layer and gas chromatography by Kudrzycha-Bieloszabska and Glowniak (405, 406).
Cheng and Von Rudloff (125) analyzed the volatile oil of the leaves of Chamaecyparis nootkatensis. The terpenes and sesquiterpenes were extensively researched by Andersen and Syrdal (21, 22), who established the stereochemistry of alaskenes and acorone-related sesquiterpenes. Andersen et al. (23) also determined the absolute configuration of cis- and trans-calamene, isolated from the oil, Chamomile oils, both of the German and Roman varieties, were examined by Meisinger (480), who identified some of their important components, including bisabolol and herniarin. According to gas chromatography and thinlayer chromatography data obtained by Glad (241), the main compounds in German chamomile oil are farnesene, chamazulene, an unsaturated dicycloether, and ( - ) a bisabolol. Kiseleva et al. (377) found that the content of chamazulene varies, depending on the region where the chamomile is grown, from 0 to 14.56%, and that the flowers of plants grown in Siberia contained none. Chandra et al. (121) reported the successful growing of chamomile on saline-alkaline soil of the Indo-gangetic plains and the production of satisfactory oil from the plants. Chamazulene from German chamomile oil was characterized by mass, IR, and NMR spectrometry by Evdokimoff et al. (194), and its content in oils from various sources was determined by gas chromatography. In Roman chamomile oil, Chretien-Bessiere et al. (129) demonstrated that the main constituents are isobutyl angelaten ( -)-trans-pinocarveol, and ( -)-trans-pinocarvone. Herisset et al. (283) detected 2,3-dihydroxycinnamic acid. Kiseleva and Kibal'chich (376, 377) studied a type of chamomile growing in the Moscow region and attempted to induce the formation of chamazulene in the oil from this plant, Matricaria matricarioides, without success. Investigating the composition of thujone and camphor types of Chrysanthemum vulgare oils, Von Scha'ntz and Forsen (738) separated the oil by column chromatography, fractionated by gas chromatography, and identified the components by IR, NMR, and mass spectrometry. Ceylon cinnamon oil may be differentiated from cassia oil, according to Herisset et al. (288), by examination of their UV, IR, and Raman spectra. The former oil contains linalool and eugenol, whereas the latter contains more methyleugenol. Two new monoterpene alcohols, transand cis-yabunikkeol, were isolated from oil of Cinnamomum japonicum and characterized by Fujita et al. (222224), who also reported the major components of the oil, particulary the high content of l,g-cineole, p-cymene, and linalool. Investigating another variety, Cinnamomum nominale var linalia, they found its oil contained 86 to 92% linalool and 4.5 to 7.6% (+) trans-nerolidol. A study as to the oil content and composition of ditronella Java type as related to the seasons was made by Chandra and Singh (122, 123) in a n effort to determine the best times for harvesting. Virmani and Datta (730732) reviewed the properties of citronella Java oil, its composition, and harvesting, and gave a bibliography of past publications pertaining to the oil. Citrus oils, because of their economic importance, have again been the subject of intensive research. Where practical, such work is mentioned under the individual heading, such as lemon oil or bergamot oil. Safina (611) explained the advantages and disadvantages of expressing
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citrus oils from the whole fruit, from the peels only, or from the fruit with simultaneous pressing of the juice. Present analytical procedures for quality control were also discussed. Di Giacomo (165-169) described methods of analysis for carotenoids in citrus fruits and listed 51 such compounds which have been identified. The occurrence and identification of numerous other components and their quantitative determination in various citrus oils, primarily of Italian origin, was related with detailed compositional data. Di Giacomo and Calvarano (172) summarized the quantitative and qualitative composition of orange, grapefruit, and other citrus oils, as well as oils from citrus leaves and flowers. Balbaa e t al. (34, 35) ascertained the composition of lemon, lime, and mandarin oils, and also the flower oils from citrus sinensis, C. aurantium, C. aurantium bergama, C. reticulate, and C. aurantifolia, all of which were grown in Egypt. Karawya e t al. (355) analyzed leaf oils from bitter orange and bergamot growing in Egypt. Methyl anthranilate was present in the orange leaf oil only, and citronellol in the bergamot leaf oil only. Wolford e t al. (766) reviewed the physiocochemical properties of citrus oils from Florida, and Basker et al. (47) attempted to restrict the analytical criteria applicable to Israel orange and grapefruit oil. Standards for the detection of sophisticated adulteration were proposed. The constituents of citrus tankan oil from Taiwan were identified by Shiga (636). Kamiyama (342-344) published three papers describing detailed determinations of the components of citrus leaf oils, including 10 Japanese citrus species and 13 intergenetic hybrids. The leaf oils from the hybrids were markedly different from those of the parent plants. Oil- and water-soluble aromatics distilled from citrus fruit and processing waste were described by Veldhuis et al. (726); the products have a high flavor potential. A testing sequence using gas, column, and thin-layer chromatography, chemical tests, and IR, NMR, and mass spectrometry for the analysis of citrus oils and juices was described by Ziegler (789, 790) and the components identified were listed. Dougherty and Petrus ( I 79) proposed a colorimetric method for the quantitative determination of aldehydes in orange and grapefruit oils. Kesterson e t al. (373) showed that the spectrophotofluorometric method is superior to UV spectrometry for the differentiation of Florida, California, and Arizona grapefruit and orange oils. Luminescence investigation of citrus oils and the determination of coumarin derivatives in lemon, lime, and bergamot oil as a quality control were the subject of two papers by Madsen (452, 453). Martin (466) identified and determined coumarins in citrus flavors with liquid-liquid extraction followed by thin-layer chromatography. IR spectrometry a,nd gas chromatography were also used. The composition of' oil of Cituta virosa was established by Strzelecka and Malinowski (674), who also discussed the problems caused by oxidation products. Clove oil was examined by Deyama and Horiguchi (163), who identified the previously unreported components, benzaldehyde, benzyl alcohol, benzyl acetate, mmethoxybenzaldehyde, a-ylangene, and chavicol. Walter (755) showed that p-caryophyllene is present in clove oil and is not an artifact of distillation, as previously reported. The volatile components in coconut were identified by Lin and Wilkens (438). Aldehydes, alcohols, ketones, lactones, and dodecanoic acid were detected. Coffee aroma volatiles were reviewed by Weidemann and Mohr (757) who listed 363 known components and discussed their effect on the aroma. Buechi et al. (105) identified kahweofuran, another constituent of coffee aroma.
Eighty-one components, 24 not preiriously reported were identified in cognac oil by Schaefer and Timmer (620). Physical data relating to five oils from compositae plants were reported by Dominguez et al. (177), along with some of their terpene components The terpenes of coriander oil contsined 19 compounds, 17 of which were identified by Karken e t al. (360). The oxygenated components were analyzed and identified with the aid of a special gas chromatographic column by Karlsen and Baerheim Svendsen (359). Oil of coriander from Egypt was analyzed by Mahran et al. (454). A method for analysis consisting of purging the plant material, in this case coriander seed, with nitrogen a t devated temperature and condensing the volatiles in a ccld trap, after which the condensate is analyzed by gas chromatography, was described by Redshaw et al. (585). Lesnov and Pekhov (434) identified the m i i n component:, in oils from coriander herb and ripe seed. The volatilee obtained from coriander seed by extraction with CO:! were analyzed by Meerov and Bykova (478) and in greater detail by Bykova et al. (110) who identified many of the components. Oil of Cosmos bipinnatus from plsnts raised in Nainital, India, was examined by Baslas (54). The composition of costus root oil from Punjab was investigated by Mathur (472). Oil of cumin was analyzed by Varo (721), and Georgiev and Khadzhiiski (236) studied the decrease in oil content with extended storage of the seed, 3ut they also found that certain components increased instead of decreasing. Oil of Cupressus torulosa contained, besides hydrocarbons, a-thujone, citronellal, 1-terpir en-4-01, and verbenone, according to Sinha and Prakash (650). Ahuja and Nigam (7) determined the properties and major components of Curcuma amadtx oil. Curzerenone, a new sesquiterpenoid from oil of Curcuma zedoaria was characterized by Fukushima e t al. (227), and Hikino et al. (294, 297) established the structure and absolute configuration of curcumadiol and zederonem The composition of an oil from black currants was explored by Latrasse and Demaizieres (422) who also checked peroxide formation and stability of the oil. A number of Cymbopogon essential oils were screened by Thappa e t al. (702). Some were found to contain useful amounts of geraniol, citral, citronellal, piperitone, perillyl alcohol, or nerolidol. Cymbopogon semarensis was shown by Rovesti (601) to have a high percent -Ige of piperitone. The structure and absolute configuration of a- and protunol, sesquiterpenoids isolated fro n oil of Cyperus rotundus, were established by Hikino e t al. (290), and rotundene and rotundenol were isolated from Cyperus scariosus oil by Nerali e t al. (520). The structure of davana ether, a new constituent isolated from davana oil, was established by Thomas and Pitton (708) by means of spectral data and synthesis. Among compounds identified in deer-tongue by Appleton and Enzell (27) were 2,3-benzofuran, coumarin, and dihydrocoumarin. The properties and composition of dill oil were extensively described by Virmani and Dat ;a (729). Shah e t al. (629) analyzed two available Indian d 11 seed oils from Ane t h u m Sowa which had carvone conients of 50-6470 and dill apiole of 12-15%. Other dill seed oils from A n e t h u m graveolens contained 3 and 8.6% dill apiole and 34.5 and 14.3% carvone, as determined by Bsslas et al. (57, 58). Baslas and Baslas (48, 49), also found that Indian dill oils differed from the European oils in that they contained the undesirable dill apiole. Myint and G d e (506) prepared a terpeneless dill oil from A n e t h u m S o w a by fractionation. The dill apiole was removed and a much improved prod-
A N A L Y T I C A L CHEMISTRY, VOL. 45, NO. 5, APRIL
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uct resulted. Bykova e t al. (111) prepared an experimental dill oil obtained by first extracting the seed with CO2. The composition of the oil differed somewhat from that of a distilled oil. The volatile compounds in durian were investigated by Baldry et al. (37). Singapore durians owed their characteristic odor to a mixture of esters and thioethers, wheieas those from Kuala Lumpur contained thiols. Oil of Elsholtzia densa, analyzed by Vashist and ktal (722), contained an unidentified ester, naginata ketone, elsholtzidiol, and other more common compounds. Gas chromatography conducted by Czuba and Wozniak (151) indicated that the main components of Elsholtzia pa :rini flower oil were elsholtzia ketone and dehydroelsholtzionc?. Twenty-five compounds were separated by Crl?spo Landazabal(146) in the oil of Espeletia moritziana. A qualitative analysis of eucalyptol, limonene, and apinene in eucalyptus oil by infrared spectrophotornotry was achieved by Soares and Pereira (653). Brazilian e ticalyptus oil was shown by Yamashita (773) to contain 80.7% eucalyptol, while Eucalyptus citriodora oil contained 75.3% aldehyde. Bauer and Brasil e Silva (61) also reported findings regarding the properties and chemical composition of Brazilian E. citriodora. Briggs and Baimtley (99) identified major terpene components of E . ficifdia. Oil of E. macarthuri grown in Jammu contained principally geranyl acetate, eucalyptol, and eudesmol, as sl-own by Agarwal et at. (2). Oil of E. maculata from Angola, analyzed by Cardoso do Vale and Proenca da Cunha (117, 118) contained 56% eucalyptol, whereas oil of E. maideni contained 71%. E . microcorys oil, also from Angola, was investigated by Marques da Cunha Pinto (461), who ilientified its major components. Gas and thin-layer chrcmatography, IR, NMR, and mass spectra were utilized by Martelli et al. (465) to identify some minor compouncs in oil of E. rostrata, and oil of E . sieberiana raised in Jammu was analyzed by Arora et al. (30). Eugenia bracteata yielded 0.5% oil whose properties and composition were reported by Rao and Nigam (575), and oils obtained by steam and water distillation from E. heyneana were investigated by Garg and Nigam (230). Socolsky de Fenik and Retamar (654) found 35% verbenone, and 32.6% eucalyptol, as well as several other componcmts in oil of E. pseudomato. Thymohydroquinone dimethyl ether was the chief component found in Eupatorium triplinerue leaf oil by Garg and Nigam (231). Essential oil of feijoa fruits, distilled by Starodubtreva et al. (665), showed quantitative but not qualitative differences depending on the locality of origin. Fifteen new constituents were identified. The properties and principal components, including anethole, of a Roumanian fennel oil were establishec by Rothbaecher and Kraus (599). Indian fennel oils were examined by La1 and Sen (417), who noted that the rraximum yield of oil was obtained if distillation was conducted before the plants were fully ripe. Shah et al. (630) found that a strain grown in Ooty yielded a very high percentage of oil, which, however, contained primarily eckragole and no anethole. Oils from Ferula communis grown in Sardinia and harvested at various stages of maturity showed quantita:ive, but not qualitative, differences in composition, accor:ling to Falchi and Lai (197). Goryaev et al. (246) conductsd a detailed analysis of the oil from the roots of F. pennirzervis. Volatile components of roasted filberts were separated by Sheldon et al. (634) and analyzed by gas chromatcgraphy coupled with mass spectrometry. Thirty-eight com50 R
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pounds were identified, including aldehydes, furans, and pyrazines. Kozhin and Sulina (402) found that oil from Filipendula ulmaria contained 70% salicylaldehyde, as well as methyl salicylate, heliotropin, vanillin, phenylethyl phenylacetate, and others. In the wood oil of Fokienia hodginsii, Korthals et al. (397) detected 35 constituents, identified 24 of them, and structurally characterized 3. The existence of several thiol esters and pyrazines in galbanum oil was ascertained by gas chromatography and mass spectrometry by Burrell e t al. (107, 108). Many sulfides were identified in garlic oil by Baldrati e t al. (36), and propanal and pentanal were confirmed with thin-layer chromatography. Brodnitz et al. (102) proved the presence of diallyl thiosulfinate in garlic extract and followed its degradation to form mono-, di-, and trisulfides. Kabelik (335) tested the antimicrobial properties of garlic. The composition of Bourbon geranium oil was studied by Pesnelle et at. (548-550), who also compared it with African geranium oil. Each of the oils contained certain unique components which were not found in the other. In a similar manner, Bourbon and Marocchino geranium oils could be differentiated. Conducting a qualitative analysis of Reunion geranium oil Timmer et al. (709) identified 38 components by comparison of their retention times, mass spectra, and IR spectra with those of authentic samples. A hybrid geranium from Poland, investigated by Bankowski et al. (39), yielded an oil with a high menthol and menthone content. Oils from various hybrids grown on the Ararat plain were analyzed by Avakyan (33) and varied widely in composition, though all had a high citronellol content. Kapetanovic et al. (348) reported that oils from geraniums from Herzegovina also had high citronellol contents, 42-60%, and appeared to be of good quality. Alimov (15) tabulated the yield of oil a t various harvest times. Kotlyarova (398) also analyzed oil from geranium hybrids by gas chromatography and found wide variations, such as a variation in citronellol from 21 to 89%. Kapetanidis et al. (347) ran a microchemical determination for isomenthone by using two-dimensional thin-layer chromatography on 2,4-dinitrophenylhydrazones.Kachakhidze et al. (336, 337) were able to drastically reduce the menthone content of geranium oil. I t was postulated that the ketone is oxidized to acid. The properties of oils obtained from Geum species in Poland were given by Krupinska (404). Four major flavor-contributing compounds were statistically preselected from ginger oil before any identification work was initiated by Bednarczyk and Kramer (67). This is a practical method to restrict time-consuming identification experiments to those components which are significant to the flavor or odor. Krishnamurthy et at. (403) found that the oil from green ginger had a superior, more spicy odor than oil from dry ginger, probably due to its higher zingiberene content. Molyneux (490) described traditional and modern methods for the preparation of ginger roots and the composition of the oils obtained. Connell (139) gave the properties and composition of ginger oil and oleoresin; Connell and Jordan (140) investigated oil from Australian grown ginger, which had a high content of geranial and neral probably responsible for its distinctive citruslike aroma. Connell (138) also identified zingiberone, the major constituent, P-bisabolene, ar-curcumene, @-sequiphellandrene,and zingiberol. The analysis of grapefruit essences and oils was discussed by Coleman et al. (132). Moshonas and Shaw (499) identified 32 volatile flavor components extracted with
A N A L Y T I C A L CHEMISTRY, VOL. 45, NO. 5, A P R I L 1973
methylene chloride and ether from the aqueous essence. Twenty-three of the compounds were reported for the first time in grapefruit juice. Moshonas (495) also conducted a detailed analysis of the carbonyl and ester compounds in grapefruit oil. Using all the normal modern techniques, he identified twelve aldehydes, nine esters, and one ketone, nootkatone. Paradisiol, a new sesquiterpene alcohol was isolated, and its stereochemistry was established by Stevens et al. (667). The volatile constituents in guava were also investigated by Stevens e t al. (666), and 22 components were identified with cis-3-hexenol, hexanol and hexenal predominating. The physical and chemical properties of essential oil of Helichrysum were given by Peyron and Roubaud (557, 559, 560). The composition and properties of the oil from the Esterel, France, was compared with those of oils from many other Helichrysum species from other areas. The change in the quantity and composition of the volatile compounds in hops was recorded by Naya and Kotake (519). Laws and Elvidge (432) separated, and deduced the absolute configurations of cis- and trans-isohumulone, and the polarography of humulone was described by Schroeder (625). At least 17 volatile components of horseradish roots were isolated by Gilbert and Nursten (239), and methyl, ethyl, isopropyl, 2-butyl, allyl, 4-pentenyl, and 2-phenethyl isothiocyanates, and allyl thiocyanate were identified. Kishima et al. (378) identified several other related compounds in horseradish and in black mustard. The oil content of some Heracleum species from Azerbaidzhan and their antimicrobial activity was investigated by Aliev et al. (14). Gorvaev et al. (245) used gas chromatography and IR spectrometry to separate and identify the major components in hop oil. The physical properties of Heracleum sasnowskyi oil were reported by Sipinskaya and Rozentsveig (651) who also found that the oil contained large percentages of octyl esters, including octyl angelate. Oil of Heracleum trachyloma leaves and fruits contained, as main components in the fruit oil, hexyl butyrate, octyl acetate, octyl alcohol, anethole, and hexyl alcohol, and as main components of the leaf oil, anethole, methyl chavicol, anisaldehyde, and limonene, according to the research reported by Kozhin and Nguyen Mai Linh (401). Ninety per cent of the components of the essential oils from two varieties of jasmine flowers, Cestrum nocturnum and C. diurnum, were identified by Collins and Halim (135). trans-2-Hexenal, cis-3-hexenol and its acetate, and trans-2-hexenol were common to both oils. The essential oils of long leaved, Turkestan, and dwarf junipers were found to contain mostly monoterpene hydrocarbons, which were quantitatively determined by Teppeev et al. (697). The change in quantity of juniper oils distilled from various parts of the plants and a t various seasons was reported by Kowal and Krupinska (399). The composition of the oils remained constant. Thomas (707) isolated and characterized two new compounds from juniper oil. They had the campholenyl skeleton which is a new nonisoprenoid monoterpene system. Csedo and Racz (148) compared the oils from immature and ripe juniper berries and found, among other things, that the oil from unripe berries was dextrorotatory whereas that from ripe berries was laevorotatory. The stereochemistry of longifolenol and logifolane oxide from oil of Juniperus conferta was established by Doi et al. (176). Kerimov and Bakina (371, 372) identified the terpenes and sesquiterpenes from the oils of J. foetidissima and J. polycarpos. Sood (657) identified the components of the hydrocarbon fraction of J. macropoda oil.
The major components, among 18 sep,uated from oil of Kaempferia pandurata by Lawrence el al. (426), were camphor, camphene, cineole, and geraniol. The composition of oil of labdanum, C'istus ladaniferus, and several other species of Cistus was investigated by Patudin (541) who tried several different liquid phases in a gas chromatograph. He found Apiezon L with 10% polypropylene glycol sebacate to be most efficient. The oils from four species of Labiatae from Israel were assayed as to phenol content by Zaitschek and Levontin (782).
Peyron et al. (556) found 15% p-caryophyllene and 21.8% a-humulene among the components of Lantana camara oil from Anjouan. Bauer et al. (60) reported the physical properties and main components of an oil from L. monteuidensis. The quantity of oil from mountain laserwort growing in various locations was assayed by Stjepanovic et al. (668). Komae et al. (390, 392396) investigated the composition of many oils from the Lauraceae family. Among the oils whose components were determinc d were those from Lindera glauca, L. citriodora, L. obtusiloba, L. umbellata, L. sericea, Parabenzoin praecox, P. ti,ilobum, and Neolitsea sericea. Hayashi et al. (273) also reported the identification of important compounds ip oil of Lindera umbellata. Laurel leaves growing a t higher alti .udes had a 'greater oil content than those growing a t low altitudes, according to Putkaradze and Tavgiridze (569). Pertoldi (547) analyzed laurel leaf oils from Greek and Turkish origin and found that they did not differ significantly in composition. The major constituent was eucalyptol. Asllani (31) checked the oil content of laurel lea\,es, bark, and other plant parts. The oil from leaves and from flower; of lavender and lavandin were shown by Peyron (553, 555) to contain much the same major components, but in very different proportions. Ter Heide et al. (701) conducted investigations of the composition of lavender, lavandin, and spike lavender oils and identified many new components in lavender oil, including perillyl alcohol, perillaldehyde, and p-methylacetophenone. Mizrahi and Rojo (489) distinguished among lavender, lavandin, and spike lavender oils by differeritial infrared spectrometry. Herisset et a '. (287) achieved the same end by examination of UV, IR, and Raman spectra and with gas chromatography. The oils could be differentiated according to their eucalyptol content. A cohobated oil of Bulgarian lavender was found by Vlakhov et al. (734) to contain a high percentage 3f terpinenol-4 rather than linalyl acetate, whereas a coholiated oil examined by Karetnikova et al. (358) contained only 8.0-9.570 terpinenol-4 and 47-61% linalool, with 5-1770 linalyl acetate. The composition of oil from lavender growing wild in the hills of Siena, Italy, was ascertained by Franchi (210). Physiochemical data of essential oil of lavender from plants experimentally grown in Albania weie assembled by Gliozheni (242). Mashanova (469, 470) determined the oil content of lavender a t various seasons, and also analyzed oils originating from various areas of the Crimea, wherein she found significant differences in c a r phor content. Linalool was extracted from lavender oil by the boric acid method and was also separated by fractionation by Kapetanovic and Dugumovic (351, 352). The main components in oil of Ledum palustre were myrcene and palustrol, whereas in oils of L. groenclandicum and decumbens it was germacrone, as reported by Von Schantz and Hiltunen (739). Thirty-one volatile constituent3 of Meyer lemon oil were isolated and identified by Moshonas et al. (501). Di
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Giacomo et al. ( I 75) reported the physicochemical properties of “Femminello Commune” lemon oil. The newer methods for analyzing and studying lemon oil, including various chromatographic methods and UV and IR sDectrometric methods, were reviewed by Di Giacomti and Calvarano ( I 73, 174), who also demonstrated the de ;ection of adulterants by fluorescence spectra of Sicilian lemon oil and of its constituents separated by thin-layer chromatography. Calvarano and Calvarano (113) compared thc constituents of lemon oils obtained by cold extraction and distillation; Calvarano and Di Giacomo (114) prove1:l that certain commercial lemon oils were contaminated with bergamot oil, and Di Giacomo et al. (170) showed that dewaxing of lemon oil a t low temperatures did not gieatly change its physicochemical properties. Sato and Sudo (618) demonstrated that a mixture of a-tocopherol and citric acid is a remarkably effective antioxidant for Itbmon oil. The quality of lemongrass oil, as related to different varieties of lemongrass, growing conditions, and distillation, were discussed by Miyazaki (488), and Brasil e Silva and Bauer (96) reported about 86% citral in lemongras:; oil from Brazil. From the oil of Libanotis intermedia, Solodovnichtmko (656) isolated three bactericidal bicyclic sesquiterpenc hydrocarbons related to azulene. The properties and major components of the esseritial oils from several labiaceous plants in Egypt were aiicertained by Karawya et al. (354). The production of lilac oil based on extraction with petroleum ether was described by Fadeev and Bazhmov (196), who also identified the major volatile components of the oil, including indole. Wakayama et al. (752, 753), isolated additional constituents from lilac oil, including hexanol, czs-3-hexeno1, and lilac alcohols a, b, and d. The structure of the lilac alcohols, which are new naturally occurring odor ingredients, was established. Janistyn (2?5) investigated the composition of concrete and absolute of Bulgarian lilacs and found them to have nearly identical compositions. Chorbadzhiev and Ivanov (128) reported a quantitative analysis of concrete of lilac. The differences between Mexican lime oils obtained by distillation and centrifugation were examined by HatoGuzman and Huet (268). The main components of oil of Lippia lycioides from Brazil were identified by Bauer and Brasil e Silva (63). Some components of Litsea japonica oil were identifitLd by Komae and Hayashi (391), but 47.6% of the oil constituents remain unidentified. The essential oils from several types of liverworts weie described by Svensson and Bendz (685). Huneck and Overton (307) characterized certain new diterpenoids and other constituents of liverwort oil; Matsuo (475) estaillished the structure of a new a,@-unsaturatedsesquiterpene ketone, chiloscyphone, isolated from liverwort oil; and Matsuo e t al. (476) identified the fatty acid esters in the oil. 4-Methyl-l-phenyl-l,3-pentanedione, 2-isopropylchrorr one, as well as bullatenone were isolated from oil of Lophomyrtus bullata and identified by Briggs and White (100). The major components of mace oil were identified b.1 Forrest and Heacock (207). Komae and Hayashi (389) distilled an oil from Machilus japonica and identified many of the terpene com. pounds therein. Oils from the leaves and twigs of Magnolia salicifolic contained mainly trans-anethole and citral, as determined by Nagasawa et al. (509). Maize flower stigmas contained 0.2% of an oil consisting 52 R
partially of menthol, carvacrol, and thymol, according to Granda and G.-Serrahillos (248). Several varieties of marigolds were found by Kapelev (346) to yield essential oils with a balsamic or floweryfruity aroma eminently suitable for perfumery. Kekelidze et al. (367) analyzed the oil from one of these marigolds, Tugetes minuta, and found 50% ocimene among many other components. The differences in chemical composition between two marjoram oils from Origanum majorana and 0. uulgare were explored by Jolivet et al. (329). The composition of marjoram oil from Majorana hortensis was determined by Dayal and Purohit (155). Melissa officinalis oil from Yugoslavia was obtained in the highest yield and best quality, equal to Italian or Spanish oils, by Kapetanovic and Dugumovic (350) when the herb was gathered in September. Spectral data relating to Mentha oils of various species were shown by Ubertis et al. (715) to illustrate resinification which occurs with aging of the oils. Lassanyi (421) used a microchemical color reaction to quickly distinguish between Mentha oils of the carvone type, M . crispa, and of the menthol type, M . piperita. The yield and properties of several Mentha oils were compared by Anda and Cardenas (19) in a n effort to determine whether commercial exploitation would be profitable. Mentha aruensis, Japanese mint, contained (-)-P-caryophyllene epoxide isolated by Hashizume and Sakata (272). They (614) also isolated and identified isopentyl isovalerate and anisic acid. Baslas (51) recommended harvesting of M . aruensis plants during the flowering season and on a sunny day for high yield and menthol content. Myint et al. (507) concluded that the highest yield of oil resulted if the plants were cut a t 10 A.M.. A subspecie of M . aruensis from Austria, analyzed by Van Os and Smith (720), was entirely different in composition from the normal oil. It had 44% geraniol and no menthol. The oil from a new hybrid Japanese mint developed in Okayama contained several characteristic constituents including isopentyl isovalerate, a-bourbonone, and menthofurolactone, isolated and identified by Nakayama et a4. (512). Sacco and Nan0 (608, 609) studied the oils from a number of different species of Mentha aruensis. Two of the oils consisted principally of 3-octanol, and all the others differed from each other significantly. Fujita and Fujita (216) identified (-)-menthone, (+)-isomenthone, and (+) -pulegone as the main components of M e n tha japonica oil. A study of Philippine mint oil by Cantoria (116) revealed that the plant is a hybrid and not M . aruensis. Piperitenone was the major component of the oil. Oil of M . longifolia was analyzed and evaluated by both Sinha and Gupta (648) and Gulati and Duhan (257), and both concluded that it was similar in properties and flavor to peppermint oil, M . piperita. Oils from M . mentholifera grown in ParanB State were analyzed by Pereira de Aranjo (545). Menthol content varied between 62 and 88.5% and all constants of the oils were normal. 1,2-Epoxymenthyl acetate was identified in oil of M. rotundifolia by Hendriks (282). The physical constants and major components of oil of M . royleana were established by Grushchanskii (253). The oil from an interspecies mint hybrid, MS-183, analyzed by Nikolaev and Yakubovich (522), contains about 80% menthol; the oil from another hybrid MS-41-18-10, also proved to be a valuable source of menthol, and Yakubovich et al. (770) also identified other main components. Both hybrids inherited the chemical characteristics of the maternal plants only. Oil of Micromeria biflora was distilled by Pande and Gupta (537, 538). Its physicochemical properties and
ANALYTICAL CHEMISTRY, VOL. 45, NO. 5, APRIL ‘973
major components were given. The characteristics and chemical properties of oils from several varieties of mimosa were discussed by Fuehrer (212).
Okude and Hayashi (529) separated and identified the sesquiterpene constituents of oil of Mitsuba, Cryptotaenia japonica. A method for the identification of musk by thin-layer, gas, and paper chromatography, using muscone as the standard, was proposed by Fukuoka and Natori (226). A specially designed apparatus was employed by Vangheesdaele and Bichot (719) to study the formation of isothiocyanates in ground mustard seeds. Nakabayashi et al. (511) examined the content of isothiocyanate and oxazolidinethione in several cultivated varieties of mustard. Shankaranarayana et al. (632) proposed a n oxidimetric method for determining allyl isothiocyanate in black mustard, and a volumetric method was suggested by Chikkaputtaiah et al. (126). Myrica gale oil was investigated by Von Schantz and Kapetanidis (741), and the presence of 130 constituents was indicated. The structures of 26 hydrocarbons and 8 oxygenated compounds were established. A number of components were isolated and identified from oil of M . pensylvanica by Tattje and Bos (694). The oils from various Myrrhis odorata contained high quantities of anethole, according to investigations by Kudrzycka-Bieloszabska et al. (407, 408). Fourteen compounds, in addition to those usually reported in myrtle oil, were identified by Peyron (554) in the oil of Esterel myrtle. The essential oils and concretes from two varieties of Narcissus tazetta were studied by Shikhiev and Serkerov (637).
In the oil of Nardostachys chinensis roots, Ruecker and Kretzschmar (603) identified patchouly alcohol, ppatchoulene, and a t least 9 other compounds. Nepetalactone, along with many other components, was identified by Gupta et al. (261) in Nepeta leucophylla oil. In addition to the previously reported constituents of nutmeg oil, Sanford and Heinz (615) found a-thujene, A3carene, 1(7),2-p-menthadiene,and trans- and cis-sabinene hydrate. Some components of the flower oil of Nyctanthes arbortristis were identified by Chandra (120). An essential oil distilled from the leaves and inflorescence of Ocimum gratissimum was investigated by Sainsbury and Sofowora (612). Singh and Sharma (643) obtained 62% camphor from the oil of Ocimum kilimandscharicum, and Martelli e t al. (464) found 97% estragole in Brazilian Ocimum nudicaule oil. Yates and Wenninger (776) identified 27 sesquiterpene hydrocarbons in olibanum oil, though the identification of P-ylangene and p-cadinene was tentative. Onion oil, as well as the volatiles from fresh, boiled, and fried onions, was analyzed by Boelens et al. (84). Fortyfive constituents of the oil were listed and decomposition transformations were investigated. The compounds believed to contribute to onion flavor include propyl thiosulfonates in freshly cut onion, propyl and propenyl di- and trisulfides in boiled onion, and dimethylthiophenes in fried onion. Andrushchenko (25) reported acetaldehyde and propionaldehyde in onion oil, and Brodnitz and Pascale (101) identified thiopropanal S-oxide, a lachrymatory factor in onion. Dubois et al. (181) compared the freshly distilled oil from onions with a one-year-old distillate and found that nearly all the compounds in the freshly distilled oil had disappeared on aging and di- and trisulfides had formed.
The oil content in the peel of Vdencia oranges was shown by Hendrickson et al. (281) to increase with maturity of the fruit and to vary with the size of the fruit. Lifshitz et al. (437) found that Valencia orange oil from Florida had a higher aldehyde content than the same oil from Israel, which in turn had more than oil from California. Lund et al. (445) isolated nootkatene from Valencia orange oil. The essence and aroma oils from Valencia oranges were, shown by Coleman and Shaw (133) to be similar in composition, and 42 components were identified. The most volatile fraction of tne essence oil, which possessed most of its characteristic odor, was further investigated by Shaw and Coleman (6,33), enabling them to prepare a synthetic simulation of the fraction. Karawya et al. (356) analyzed several orange peel oils from Egyptian fruit and differentiated expressed and distilled oils by IR spectrometry. Osman et al. (533) extracted Egyptian orange peels and reported the compounds obtained. Di Giacomo et al. (171) analyzed orange oil commercially produced from oranges grown on the Rosanmo plain and identified its components. Scora et al. (627) studied the changes brought about in orange peel oil by the maturation of the fruit. Thin-layer and gas chromatography were applied by Millet et a1. (485) to differentiate between orange oils obtained by the usual expression and by direct puncture of the secretory glands. One difference was the presence of carotenoids in the expressed oil. The changes brought about in the volatile components of orange oil and juice by irradiation were studied by Braddock et al. (93). Quantitative but not qualitative changes were observed. Strocchi (673) identified, both in orange oil and essence, the terpenes, sesquiterpeni:s, alcohols, aldehydes, ketones, acids, esters, lactones, arid others. The organic components of orange juice headspace were absorbed with an organic polymeric material and analyzed by gas chromatography-mass spectrometry by Schultz et al. (626). Among 29 components identified, six were previously unreported. Moshonas and Lund (49;') described a gas chromatographic procedure for the analysis of aqueous orange essence and reported their findings. Moshonas et al. (498) further explored the differences in aromatic components in various parts of the orange and found that ethyl 3hydroxyhexanoate and valencene were only found in the juice, whereas linalool was found in the peel. Lund et al. (444) reported quantitative data in respect to 20 water soluble aromatic compounds from orange peel. Braddock and Petrus (92) identified malonddehyde in aqueous orange juice essence, and Guadagni et al. (254) observed the effect of temperature on the stability of orange aroma. The physical constants of a number of components of palmarosa oil were given by Naves '51 7). The volatile constituents of parsley leaves were analyzed by Kasting et al. (361). Forty-two compounds previously not reported were identif ed, and 1,3,8-p-menthatriene was found to be one of t h ? important contributors to parsley aroma. Pennyroyal oil from plants grcwn in Austria contained 70% piperitone but no pulegonfh, according to Zwaving and Smith (793). Fujita and Fujita (217) conducted a biochemical study of the development of oil in pennyroyal plants, introduced to Japan from France, with particular attention to the development of pulegone. The stereochemistry of components and tl- e biogenetic reactions in two pennyroyal varieties were investigated by Hefendehl (278).
Wide variations in the mono- and sesquiterpene composition of black pepper oils from different geographic sources were indicated by Nauliudiri et al. (514). Pangborn et al. (539) examined thc odor quality and other
A N A L Y T I C A L CHEMISTRY, VOL. 45, NO. 5, APRIL
1973
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characteristics of various black pepper oils as a prelimi: nary preparation for more intensive investigations. Hichard (588, 589) used a n integrator and two gas chroniatographs connected in series to identify and compare the components in oils from 17 varieties of black pepper, i n d by employing various spectral measurements, he identified, characterized, and established the structural formulas of about 50 components. Several previously unreported compounds in oil of black pepper were Characterized by Richard and Jennings (590), and artifacts due to p h o t x a talyzed rearrangements were detected. Richard et al. (591) also devised a computer program which constructed simulated chromatograms, normalized on internal slandards, to simplify comparison of the volatiles from the 17 different varieties of black pepper. The cis and trans isomers of sabinene hydrate were isolated from black pepper oil, and their spectra were obtained by Russell and Jennings (605). Statistical analysis of multivariate chromatograpliic data was applied to peppermint .oils by Hartmann and Hawkes (270). By application and extension of the method of Smith and Levi, oils from various geographic origins, as well as mixtures of any two of them, could be correci.ly identified. Virmani and Datta (728) reviewed the physi:.al and chemical properties of peppermint oils. Kustova et (11. (412, 413) set up criteria for the quality evaluation of peppermint oils based on free menthone, menthol, tertiary 311cohols, esters, and bromine number. Popov et al. (5113) determined the surface tension of different peppermint oils, and Velchev (725) measured the viscosity of peppormint oil and its fractions. The composition of Roumanim peppermint oil was determined by Rothbaecher et (21. (597). Solodovnichenko (655) reported /3-caryophyllene and guaiene in the indigo-colored residue from peppcrmint oil. Differences between Brazilian and Hungarian peppermint oils were pointed out by Zilahy Kadar arid Omboly (791): Ruminska (604) found that full sunligl~t and protection from wind resulted in a n improved cil yield. In a biogenetic study of menthone and menthol fotmation in peppermint, Yakubovich et al. (769) discovered that all theoretically possible isomers are present. Croteau and Loomis (147) explored the biosynthesis of mono- and sesquiterpenes, using tracer analysis. Baslas (50) reported the effect of various agricultural factors on the essential oil from peppermint. Herisset et al. (284, 285) showe,S that peppermint should not be harvested before flowering., and also investigated the best time of day for harvesting. They (286) also related various methods for the identification of peppermint oil components. Investigation into the composition of perilla oil by 1n:i and Ogura (312) 'and Ina and Suzuki (313) revealed il number of terpenoids, and five furyl ketone derivatives. Ito (320) classified 110 perilla oils into four chemical groups containing, respectively, perillaldehyde, furyl ke. tone derivatives, phenyl propanoids, and citral. Kawanishi and Kasai (364), however, grouped oils from 61 varieties of wild perilla into seven classes. Oil of Perovskia angustijolia, analyzed by Serkebaeva et al. (628), contained a t least 50 components of which about 36 were identified. A number of constituents of Petasites japonicus oil were shown to be present by Kurihara and Kikuchi (411). The oil from Phellodendron amurense fruit was demonstrated by Murav'eva et al. (505) to consist of 88% myrcene and four other compounds. The monoterpenes of Picea ajanensis and P. obovata were quantitatively tabulated by Vol'skii et al. (736). Myrcene, /3-phellandrene, and terpinolene were detected for the first time in the Picea genus. 54
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The constituents of pimenta berry oil were determined by Nabney and Robinson (508). The composition and antimicrobial properties of pine oils from several species were reported by Nilov et al. (523). A detailed analysis, giving physical properties of the ingredients, was performed on Polish pine oil by Strzelecka and Soroczynska (675). Juvonen (334) found 152 different compounds in pine needle oil. Pauly and Von Rudloff (544) determined the composition of Pinus contorta oil. Pinus monophylla oil was analyzed by Zavarin et al. (787). The monoterpenes of P. mugo were determined by Bambagiotti et al. (38). Bernard-Dagan et al. (75) identified phenethyl isovalerate and phenethyl 2-methylbutyrate in the oil from P. pinaster. Akimov e t al. (12) studied the oils from various parts of P. pityusa. Lawrence et al. (431) separated longifolene from oil of P.- ponderosa. Anderson et al. (24) identified the terpenes and resin acids in P. monophylla and P. quadrifolia, and Younes (780) investigated the composition of P. sylvestris leaves. The major components of Pogostemon plectrantoides oil were ascertained by Thappa et al. (703). The composition of the oils from several types of Prangos were compared by Kuznetsova et al. (414). Among other components, essential oil of Pseudocaryophyllus quili was shown by De Fenik et al. (157) to contain 50% methyleugenol, whereas P. pabstianus oil, analyzed by Campos Correa and Gottlieb (115) contained isopulegol, citronellol, and citronellal. The Bulgarian standards for rose oil were explained by Lozzi (442). Zelenetskaya and Kustova (788) used the Bromine No. together with acetylation and dehydration to estimate phenylethyl alcohol, geraniol, and citronellol in rose oil. The method of production was shown by Polyakov et al. (562) to effect changes in the composition of the rose concrete obtained, and Shlyapnikov et al. (638, 639) estimated the absolute in rose concrete by a refractometric method, and also investigated which parts of the rose contained the essential oil. Paseshnichenko et a!. (540) compared the chemical compositions of the oils from 6 varieties of perfume roses and 17 ornamental roses, and the oil content of 14 varieties of roses was tabulated by Staikov (662). The oils from roses of the Dades were found by Igolen (308, 310) to have a composition very similar to that of Turkish rose oil, but to also have a slight peppery note. The effect of meteorological factors on the quality of rose oil was studied by Savchuk e t al. (619). Petrunin and Propastin (551) observed an increase in yield with irrigation, and Mashanova (468) noted changes in rose oil composition resulting from storage of the blossoms. Kekelidze e t al. (366) found that methylene chloride was the best solvent for recovering rose oil from distillation waters. Kupenov and Georgiev (409) employed hydrolysis or enzymes to increase the yield of oil from distillation; Kupenov et al. (410) applied fermentation of exhausted rose petals with aspergillus species to obtain additional yield of oil, and Georgiev et al. (237) obtained additional oil from exhausted petals by applying acid hydrolysis or special fermentation procedures. The eleoptene from Bulgarian roses was shown by Ivanov (321, 322) to contain 50% citronellol, and stearoptene to consist of normal paraffins and smaller amounts of unsaturated hydrocarbons. Stoianova-Ivanova et al. (699-671) identified the alcohols and the free acids and ketones in rose flower and rose bud waxes. Voloshina et al. (735) observed changes in the components of rose oil resulting from the effects of various metabolites and inhibitors of the oil-forming process. The cultivation and distillation of rosemary and the properties and composition of rosemary oil were discussed by Yllera Camino (777). Maldonado and Cab0 Torres
ANALYTICAL CHEMISTRY, VOL. 45, NO. 5, APRIL 1973
(456) found quantitative but no qualitative differences
among 8 Spanish rosemary oils analyzed by thin-layer chromatography. Rasmussen et al. (579, 581, 582) determined the oil content, and the composition thereof, directly from the leaves of rosemary during their development, and the results were tabulated. The method employed permits analysis from as little as 10 mg of leaf. Granger et al. (249) found considerable variation in the optical activity of rosemary oils from different areas and noted that decanted oil had much less optical activity than the oil extracted from distillation waters. The volatile oils from the leaves and stems and roots of rue were investigated by Tattje (693). Many components, including several methyl ketones, were identified. An important component of the oil, geijerene, was characterized by Tattje and Bos (695). Corduan and Reinhard (141) found that light has a profound effect on the composition of the rue oil formed in the leaves. The composition of Ruta pinnata oil was elucidated by Estevez Reyes and Gonzales Gonzales (193, 243). An oil from Saccopetalum tomentosum contained, among other constituents, P-caryophyllene and cadinene, but no eucalyptol, see Ramaiah and Nigam (572). The volatile components of saffron were separated and identified by Zarghami (784) and Zarghami and Heinz (785, 786). The structures of several isophorone related components were substantiated by synthesis. Among 41 compounds isolated from Dalmatian sage oil by Lawrence et al. (427) were traces of cis-2-methyl-3methylenehept-5-ene, and p-dimethylstyrene. Rasmussen et al. (580) used a direct gas chromatographic analysis on leaf tissue to observe the changes in oil content and composition with the maturing of Dalmatian sage leaves. Lawrence et al. (425) identified forty terpenoids in oil of Spanish sage. The sesquiterpene hydrocarbons in Bulgarian oil of clary sage were shown by Vlakhov et al. (733) to consist of cadinene and caryophyllene, among others. Oil of Salvia leucantha was distilled by Sinha and Chauhan (647), who identified many of its major components, and Bodrug and Petov (83) compared the components of 10 types of sage growing wild in Moldavia. The qualitative compositions of sandalwood oil and also vetiver oil were given by Monir and Takacs (491). Gibson and Barneis (238) isolated exo-norbicycloekasantalal from sandalwood oil. The structure and synthesis of dihydro-psantalol, a product possessing the full woody fragrance of sandalwood oil, was described by Fanta and Erman (198), and Wolinsky et al. (767) confirmed the stereochemistry of P-santalene. The accumulation and composition of essential oils in Satureia hortensis (“summer savory”) and S. montana (“winter savory”) was investigated by Thieme and Nguyen Thi Tam (706); Many components were identified, and oil of estragon was also analyzed. The properties and composition of oil of Satureia montana was also examined by Paulet and Felisaz (542, 543), and Tavberidze et al. (696) identified 15 components in oil of S. spicigera. The yield of oil from various parts of the Seseli rhodopeum plant was ascertained by Robeva (592), and Vulev and Robeva (749) identified major components in the oil. The composition of oil from Sequoiadendron giganteum was found by Levinson et al. (435) to change considerably as the leaves matured; the concentration of allylphenyl ethers increased notably. Skimmia laureola oil from plants growing wild in the Himalayan region of India had a high linalool and linalyl acetate content, and Sarin (616) believed, it resembled fine petitgrain oil in fragrance. Fiddler et al. (205) showed that the volatile fraction of
liquid smoke, which contains the essential smoke flavor, consists primarily of phenols and carbonyl compounds. The properties and composition of Indian snakeroot oil were reported by Ahuja and Nigam (5). Two types of European spearmint oil from Mentha crisp a were investigated by Rothbaechec and Kraus (598). One type was lacking in carvone, the other had the normal flavorful characteristics. Oil of Stenoclyax michelii, a type of myrtle, was analyzed by Lalli de Viana and Retamar (429). Kemp (369) identified many vok tile components of strawberry and peach leaves. A new essential oil from the flowers of Strobilanthes auriculatus was obtained by Zutshi (792), who identified borneol and a trihydroxy sesquiterpenoid in it. Aqueous tangerine essence volatile components were separated by Moshonas and Shaw (500). They identified 34 compounds for the first time in tangerine essence. Calvarano and Calvarano (112) compared the composition of coldpressed tangerine oil with distilled oil. Many constituents of tagetes oil were identified by De Mucciarelli and Montes (159), and De Villiers et al. (161) verified cis- and trans-ocimenone as components of the oil. Isolation and analysis of essential oil from two types of “Tan-Kui” by Yang (774) showed that only one type principally contained the desirable aroma .ic constituenl. Two types of tansy oil from Poland showed considerable difference in properties and Composition, as determined by Czuba and Poradowska (150). Artemisia ketone, chrysanthenyl acetate, isopinocamphone umbellulone, and a sesquiterpene were new components identified in a tansy oil from Chrysanthemum vulgare grown in Finland by Forsen and Von Schantz (209). The composition of the essential oil in green tea and the changes occurring in it during the curing of the tea were observed by Starodubtseva and Kharebava (664). The content of undecanoic aldehyde, nerol, benzyl acetate, eugenol, and unidentified compounds increased during curing. Ota et al. (534) examined the differences in volatile components in fresh tea leaves at various seasons and locations. Only slight differences were noted in the proportions of the 27 components idevtified. A new aromatic black tea was found by Dzneladze et al. (187) to contain more methyl salicylate and less n-hexanal, n-hexanol, and cis-3-hexenal. Dzhindzholiya and Chikovani (186) isolated phenylacetaldehyde, formaldehyde, furfural, and other aldehydes from tea volatiles; 3-keto-P-ionone was identified by Ina and Eto (311). Physical data were given for an.oil from Teucrium eriocephalum by Miranda and S m e (487). Many sesquiterpenes were determined in oil from the wood of Thuja orientalis by Tomiia and Hirose (712); numerous diterpenes from oil of Thuja standishi were characterized by Kitadana (379). The components of oil of thyme were identified by Russell and Olson (606), and Schratz (2nd Hoerster (624) studied the changes in essential oil composition, with the seasons, of two varieties of thyme. Ciils from new thyme hybrids were examined over a 3-year period by Chladek and Patakova (127). Some of the new hybrids gave more oil with higher phenol content. Thv yield of oil from wild thyme in Bosnia was reported by Mihajlov and Tucakov (484). The effect of ecological influences on wild thyme oil in Italy was observed by Rovesti (630). Kaneko and Harada (345) isolated from cigar tobacco oil, a compound which had a stlong aroma. Its structure was deduced and confirmed by jynthesis as R-(+)-3-isopropyl-5-hydroxypentanoic acid la ctone.
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Many components of tomato volatiles were identified by Kazeniac and Hall (365). The essential oil of Tournefortia sibirica was shown by Abasova (1) to have an odor like saffron, and safr;mol, along with several other components, was identified i 3 the oil. Indian turpentine oil was discussed by Baslas (55,. Da Silva e Carmo (152) analyzed Portugese turpentincm oil, and Japanese turpentine oils were chromatographetl by Fujita et al. (225). Essential oils from 24 species of Umbelliferae werc examined by Williams and Harborne (761), who identified some of their major components. The composition and characteristics of oil from cultivated Japanese valerian roots were investigated and 2-isopropyl-4-methyl-anisole was demonstrated in nature for the first time by Hikino et al. (291-293, 295). They d s o identified, in the oil of wild Japanese valerian, a number of sesquiterpenoids, kongol, and 8-epikessanol. Many volatile components from Bourbon vanilla bcans were separated and identified by Bohnsack (87, 88). Potter (564) described a gas chromatographic technqiue for demonstrating that volatile flavor enhancers had t e e n added to vanilla extract. The physical properties and chemical compositior: of vetiver oil were reviewed by Garnero (232) and also by Fuehrer (211) and by Yoshikoshi (778). Manchanda et al. (459) isolated 5 alcohols from vetiver oil, 3 of which wxe. not identified. Khusitone and an aldehyde were isolated by Nanda et al. (513). Kirtany and Paknikar (375) dcmmonstrated differences in the chemical composition of North Indian vetiver oils of the Moosanagar and Bharatpur varieties. Khusimone, a new C-14 ketone was iso1a:ed and characterized by Umrani e t ai. (716); y- and d-cadinenes and khusimol were structurally elucidated by Trivedi et a!. (714); the structures of zizanene and a-amorphene were established by Klein and Schmidt (381), and certain biogenetically significant components were iso1,lted by Kaiser and Naegeli (341). Zizanene and levojuneiiol were obtained from the hydrocarbon fraction of Reunion vetiver oil by Andersen (20). An essential oil giving evidence of a t least 8 components was obtained from Wedelia paludosa by Rocha and Boiizani da Silva (593). The volatile oil obtained from witch hazel was checklzd by thin-layer chromatography in an at,tempt to identify some of its constituents by Messerschmidt (483). The physical properties and some main components of wormseed oil from India were ascertained by Gupta and Behari (259). The composition of wormwood oil was partially e1uc.idated by Baslas (53). Maksudov (455) distilled wormwood oils a t three periods of growth and gave their physicschemical properties, The oil prepared a t the blooming stage was superior. A similar study was conducted by Berezovskaya (73, 74) who also identified several main coniponents and quantiatively analyzed the major componen'a of several Siberian wormwood oils. Physicochemical properties and further data regarding the composition of these oils were published by Usynina et a1 (71 7). Akhmedov t , t al. (10, 11) established the structure of artabin, a sesquiterpenoid lactone isolated from wormwood oil. Major components of the oil from the leaves of X a n . thium strumarium were identified by Ahuja and Nigam (4). In oil of ylang ylang, Naves (515) demonstrated the presence of methyl butenols and their acetates. Dubey and Purohit (180) analyzed a n oil derived from Zanthoxylum alatum seeds, and identified its chief components. 56
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The oil of Zingiber cassumunar, a type of ginger from Thailand, was analyzed by Casey et al. (119). The main component, of many identified, was terpinen-4-01. This was also the main constituent reported by Lawrence et al. (428), who also investigated the oil. Essential oil of Ziziphora pedicellata contained high percentages of isomenthone and isopulegone, as determined by Goryaev et al. (244). Aromatic Chemicals-General. Advances in terpene chemistry, including newly obtained structural data, were reviewed by Sorm (659). Buttery et al. (109) evolved a method for estimating the volatility of organic flavor compounds in food, and thus their contribution to the aroma, either by calculation or by experimental determination of their volatility in water. Theimer et al. (704) showed that optical isomers may be differentiated by odor. Teranishi (698) noted that small changes in the chemical structure of musk, amber, and woody type odor compounds have a great effect on odor potency but not on odor quality, whereas with compounds related to nootkatone the opposite is true. Ohloff (526) found that ambergris type odor qualities result from 1,2,4-triaxial arrangement of substituents in a decalin ring system or in a molecule with an equivalent configuration. Appell (26) discussed the equivalent weights of aromatic chemicals in relation to their fragrance effect. The ignition and combustion temperatures and the concentrations in air a t which they form explosive mixtures were determined for perfume aromatics by Borovik and Zhorova (91). The biogenesis of essential oif terpenoids was reviewed by Moss (502), and Banthorpe et a!. (42, 43) discussed the biosynthesis of terpenes and employed tracer analysis to study the biosynthesis of thujane derivatives. Streibl and Herout (672) reviewed oxygenated mono-, sesqui-, and diterpenes, and Takeda (690) discussed recent discoveries and structural determinations relative to a number of sesquiterpenes having R five-membered ether ring in the molecule. The chemistry and structural determinations of diterpenoids were reviewed by Fujita (213, 214).
The mass spectra of numerous acyclic, monocyclic, and dicyclic terpenoids and sesquiterpenoids were published by Von Sydow et al. (742, 743, 745-748). Acids-General. Inglis (314) reviewed methods for the determination of acyl groups. The aliphatic acids in sapogenin were determined with gas chromatography by Hollstein et al. (302), and Harwood and Huyser (271) evolved a simplification of their previously published method for the gas chromatographic identification of volatile fatty acids in water after esterification. Acids-Individual Compounds. The structure of abscisic acid was established by Mallaby and Ryback (458), who also devised a useful color test for it. A spectrophotometric method for determining impurities in acetic acid, namely acetone, acetaldehyde, and methyl acetate, was developed by Josimovic (333). On the basis of physicochemical data and chemical reactions, Mot1 et al. (503) established the structure of cascarillic acid. The cis-trans configuration of 4-hydroxy-cis-camphoric acids were clarified by Heinanen (279). Indoleacetic acid was found in several plant tissues by Black (82). The absolute steroechemistry of analogs of optically active a-ionylideneacetic acids was determined by Oritani et al. (532). De Simone (160) deduced the stereochemistry of peruvic acid and peruvin.
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Aldehydes and Ketones-General. An improved neutral sulfite method, employing a laboratory high speed electric stirrer, was illustrated by Koke (384). Brown e t al. (103) used column chromatography to separate 2,4-dinitrophenylhydrazones, followed by further resolution with thin-layer chromatography. Martelli (463) employed thin-layer chromatography on plates impregnated with 2,4-dinitrophenylhydrazine for the detection of carbonyl compounds. Craske and Edwards (145) described a two-dimensional thin-layer chromatographic technique for the identification of monocarbony1 dinitrophenylhydrazones. Holzbecher and Bruna (302) explored the capabilities and limitations of a similar technique applied to ketones. A new sensitive and specific color test for the detection of aldehydes was discovered by Dickinson and Jacobsen (164), and Sakaguchi et al. (613) tested the relation between the structure of diketones and their reactivity in the Voges-Proskauer reaction. Bark and Bate (45) described a thermometric method for the determination of aromatic aldehydes. The stability of commonly used perfume aldehydes in contact with aerosol propellants was investigated by Aime and Peyron (9). Aldehydes a n d Ketones.-Individual Compounds. A quick determination of acetaldehyde by oximation was used by Vulterin (750), Singliar and Sestrienkova (644) used gas chromatography to determine crotonaldehyde in acetaldehyde, and Terent’ev and Fedotenkova (699) suggested a new modification of the method for determining water in acetaldehyde with Fischer reagent. The biosynthesis of (-)-camphor in various plants was studied by Banthorpe and Baxendale (40) with tracer analysis. The steric structures of caranones were indicated by Arbuzov et al. (28) to be of the hemichair form, which is the most stable. Leitereg et al. (433) showed that (+)- and (-)-cawone of high purity could easily be distinguished as caraway or spearmint flavored. A quantitative total aldehyde test on citrus essences was a useful tool for evaluation or as a blending control, according to Petrus et al. (552). Cuminal was identified by Ogan (525) in Xylopia aethiopica oil. A synthesis of davanone by Birch et al. (81) confirmed its structure and suggested its stereochemistry. The absolute configuration of delobanone and acetoxydelobanone was clarified with NMR studies by Takeda et al. (691). The natural occurrence and biological origin of ionones and related substances were discussed by Naves (516). Rautenstrauch and Ohloff (584) established the configuration of irone by correlation with camphor. The stereochemistry of isolongifolene ketone epimers was shown by Lala (418) to be different from that previously assigned. 2-Amylnonen-2-a1 was found as an impurity in jasmine aldehyde by Bogdanov (85). Its removal vastly improved the odor of the aldehyde. Many volatile carbonyl compounds in miso were separated and identified by Shibasaka and Iwabuchi (635). The relation between odor and structure in the nootkatone series was studied by Ohloff and Giersch (527). Marshall and Ruden (462) described a stereoselective total synthesis of racemic nootkatone, and Ishida et al. (315) deduced the preferred conformation of nootkatone from CD and NMR studies. The structure of petasitolone was clarified by Naya et
al. (518) by a synthesis starting with fukinone. A new furanosesquiterpene, phymaspermone, was isolated and identified by Bohlmann and Zdero (86). Suga et a1 (679) calculated the conformational energy of (+) -pulegone, and Feeley and Hargre aves (201) conducted circular dichroism studies on pulegone oxides. The structure of sabina ketone WJS confirmed by synthesis by Mori et al. (494). The stereochemistry of squamulosone, a new sesquiterpene ketone, was established by Batej, et al. (59). Additional support for the conformation of valeranone was supplied by Rao and Narasimna (576) by chemical and NMR studies. Alcohols a n d Phenols-General The separation and identification of alcohols as p-diriethylaminophenylazo benzoates by paper and thin-layer chromatography was described by Churacek et al. (130). Warevel et al. (756) described a method of analyzing duminum alcoholates. IR spectra of some unsaturated cyclic alcohols indicated to Povolyreva et al. (566) that hydrogen bonding took place between the HO group and the 6-membered ring. Baron et al. (46) were able to identify trace quantities of alcohols by gas chromatography of their trimethylsilyl derivatives. Yamasaki e t al. (772) correlated an organoleptic feeling of freshness with the stereochemical structures of terpene alcohols. Ebbighausen et al. (188) obtained the mass spectrometric fragmentation patterns of many trifluoroacetylated terpene alcohols, arid Ottnad et al. (535) determined alcohols in essential oils by NMR spectrometry of their trifluoroacetates. Bhatia et al. (79) demonstrated a general spray reagent for phenolic compounds on thin-kyer plates, and Thielemann (705) discussed methods for determining total phenol content, as well as individual phenols. Alcohols a n d Phenols-Indiviclual Compounds. Ageratriol, a new sesquiterpene alcohol, was isolated by Garanti et al. (229), who deduced itt; structure based on IR and NMR spectra. The products of oxidation of allyl alcohol and acrolein were determined with gas chromatography by Sulima I
(682).
According to chemical and 1;pectroscopic data, the structure of 6-cadinol was established by Lin et al. (439). Two epimeric sesquiterpene 10-cadinols isolated from the oils of Ocimum basilicum and pimenta by Hogg et al. (300) were characterized as to str x t u r e and stereochemistry. A gas chromatographic determination of cedrol was described by Ferguson et al. (202). A stereoselective total synthesis of the novel tricyclic sesquiterpenoids (+)-copaborneol, (+)-copacamphor, and (+)-copaisoborneol was achieved by Piers et al. (561). Kolbe-Haugwitz and Westfelt (387) established the sterochemical structure of copaborneol. m-Cresol was determined by Ono (531) by means of its urea adduct. Synthesis of cyclonerodiol by Nozoe et al. (524) confirmed its configuration. Heinanen (280) proved that epiborneol had the endo configuration and epiisoborneol the exo configuration. Tadwalkar et al. (687) described the preparation and stereochemical characterization of 1,6-epoxy-p-menthan2-01s and the corresponding ketones. Ethyl alcohol content was estimated in eau de cologne, using a microwave technique, by Janes (324). Eugenol in essential oils was estimated, using spectrophotometric measurement of a colored reaction product with the Gibbs reagent, by Kokeisu et al. (385). NMR spectrometry was applied to the configurational A N A L Y T I C A L CHEMISTRY, VOL. 45, NO. 5,
APRIL 1973
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analysis of menthol derivatives by Kat0 e t al. (362). The configurations of o-menthols were deduced, using IR, NMR, and mass spectral data, by Ferretti-Alloise ei al. (203). Stereochemical studies were performed by h g a and Watanabe (681) on 4-methyl-10-nor-8-oxomentho1:~ by circular dichroism. The conformational isomerism of nerol and geraniol was clarified by De Haan and Van de Ven (158). The configuration and stereochemistry of nopinols, isonopinols, and isonopinone were determined by N \AR spectra and conformation calculation by Baretta et al. (44). The absolute stereochemistry of occidentalol was pror'en by Amano and Heathcock ( I 7) by a synthesis. Corey et al. (143) reported a stereospecific total synthesis of a-santalol, and Poulter et al. (565) determined the absolute configuration of santolina alcohol. 'The structure of sesquichamaenol was established through a nine step synthesis by Takase et al. (689). Kaimal and Verghese (339) showed with NMR and mass spectra and chemical analysis that Wallach's syl r-eterpineol is d-m-menth-6-en-8-01. The mass spectrum of teresantalol was obtained by Von Sydow et a1 (744). The conformation of thujanols was established by Hach e t al. (264), and McDonald and Cartlidge (448) separatsd thujyl alcohols by gas chromatography. The identity of (-)-torreyo1 with 6-cadinol was demonstrated according to its stereochemistry by Westfelt (759). Esters a n d Lactones-General. The influence of ti?., stationary phase polarity on retention time of a series of homologous esters in gas chromatography was investigatcd by Allen and Haken (16). The classification, structure determination, spectr.x, and other data pertaining to natural sesquiterpene la(:tones were reviewed by Rybalko et al. (607). Matsueail (473) discussed the prediction of stereochemical relatioris of hydroxyl groups of sesquiterpene lactones from their I F1 absorption spectra, and Matsueda and Geissman (474') employed controlled catalytic hydrogenation as a methozl in establishing stereochemical relations. Herz (289) re viewed the structures and distribution of sesquiterpenoid lactones in plants of the compositae family. Geissman and Griffin (233) found that certain color reactions can be correlated with structural characteristics of sesquiterpene lactones. Hodges et al. (299) discussed characteristics of the mass spectra of some diterpene lactones. Esters a n d Lactones-Individual Compounds. Tht! structures of apachin, a new sesquiterpene lactone, and other related lactones isolated from h a am brosiaefolic' were established by Yoshioka et al. (779). The structure of arsubin was partially clarified by Tarasov e t al. (692), after isolating the sesquiterpene lactone from Artemisia sublessingiana. From other species of Artemisia, Mallabaev et al. (457) isolated and determined the structure of artemidin, and isocoumarin, and Geissmann and Lee (234) assigned structures to artemorin and dehydroartemorin. Bornyl acetate was found in oil of Abies sibirica by Lykhina e t al. (446), while oil of Pinus sibirica also contained bornyl formate. Canambrin, isolated from ragweed, was shown by Romo and Rodriguez-Hahan (594) to have the structure of a sesquiterpene dilactone of the psilostachyin series. Viart (727) developed a method based on extraction and gas chromatography for the simultaneous determination of coumarin, dihydrocoumarin, vanillin, and ethylvanillin in tobacco and its smoke, Nielsen (521) discussed the COUmarins present in umbelliferous plants. 58 R
A N A L Y T I C A L CHEMISTRY, VOL. 4 5 , NO.
By a combination of NMR, ORD, and CD measurements, Hirata e t al. (298) determined the stereochemistry of dihydro-P-campholenolactone and 1,2-campholide. A study was conducted by Liedtke and Djerassi (436) concerning the mass spectrometry of esters of the juvenile hormone class. Compounds labeled with deuterium were included in the study. The structure of laurenobiolide, from oil of laurel, was deduced by Tada and Takeda (686). Linalyl acetate was determined in lavender and sage oils produced under various conditions by Persidskaya and Tanasienko (546). The complexes formed by linalyl and nerolidyl acetates and other terpenes with disodium tetrachloropalladate were investigated by Dunne et al. (184). The structure of ligularenolide, a new sesquiterpene lactone of the eremophillane type, was ascertained by Ishizaki et al. (318). The stereochemistry of y-metasantonin was established by McMurry and Rane (451) according to NMR spectra. Methyl carbamate was isolated by Karawya et al. (357) from four Egyptian Salsola species. Srivastava et al. (660) confirmed the structure of santamarin and established its identity with balchanin. a-santonin and artemin were isolated by Arkhipova et al. (29) from Artemisia halophila. The synthesis and absolute configurations of d-and 1sirenin were reported by Rapoport and Plattner (578). A combination of techniques were employed by Mukhametzhanov et al. (504) to establish the structure of stizolin. The stereochemistry of tschimganin and tschimgin, monoterpenoid esters from Ferula tschimganica were deduced by Kadyrov and Nikonov (338). Using the double and triple irradiation technique, Romo de Vivar (596) determined the structure of zexbrevin. Ethers, Oxides, a n d Peroxides-General. The determination of ethers and epoxides was reviewed by Hall and Mair (266). Forrest e t al. (208) described a number of color reactions for detecting certain aromatic ethers found in essential oils, and Benatsky (72) detected and photometrically determined peroxo compounds in butyl alcohol. Ethers, Oxides, a n d Peroxides-Individual Compounds. Bisabolene oxide was isolated and its structure was established by Hedin e t al. (277). 10-Epiguaioxide was shown by Ishii et al. (316, 317) to be the same as bulnesoxide, and the structure of guaioxide was elucidated with the aid of microbial hydroxylation. Kat0 et al. (363) confirmed the structure of kessane according to a synthesis utilizing solvolytic rearrangement of a mesylate. Terpenes a n d Hydrocarbons-General. Terpenes and their importance in perfumery and dermatology were discussed by Vassiliev (723). Sorm (658) reviewed terpenes having ten-membered carbon rings. Romo (595) discussed recent investigations dealing with sesquiterpenes, and Banthorpe et al. (41) described the isolation and characterization of the monoterpenes from some Artemisia and Tanacetum species grown in England. Hydrogenolysis of terpenes in the gas chromatograph injection port was described by Kepner and Maarse (370). Wenninger and Yates (758) presented 24 high resolution IR spectra of naturally occurring sesquiterpenes. Luisetti and Yunes (443) utilized Kovats indexes for structural studies of mono and sesquiterpene hydrocarbons, and Dunne and McQuillin (183) studied the complexes of terpenes with transition metals, and succeeded by this means to invert cis-ocimene to trans-ocimene. The mass spectra of sesquiterpene hydrocarbons were discussed by Moshonas and Lund (496).
5, APRIL 1073
Terpenes a n d Hydrocarbons-Individual Compounds. An azulene derivative and two sesquiterpene hydrocarbons, calarene and a-gurjunene, were isolated and characterized by Sato (61 7). Synthesis of racemic a-trans and @-trans-bergamotene, leading to clarification of their identities and structures, was described by Corey et al. (142). The guaiazulenic sesquiterpenoids, a-bulnesene and bulnesol, were synthesized and their relative stereochemistry was established by Heathcock and Ratcliffe (275). A total synthesis of racemic y-2-cadinene was reported by Kelly and Eber (368), and Burk and Soffer (106) further reaffirmed its stereochemistry by a stereospecific total synthesis of (-)-y-2-cadinene. A modified iodometric method was employed by Srivastava and De (661) for the estimation of camphene. McMurry (450) reported an interconversion of copacamphene to sativene. Ramaldo and Yunes (573) studied the biogenesis of caryophyllene and humulene in clove and other essential oils. The oxidation products of cumene were determined by Wygleda and Kulicki (768) with IR and UV absorption spectrometry. The sesquiterpenes from Dipterocarpus pilosus were identified by Gupta and Dev (258). Bernardi et al. (76) isolated and characterized germacrene B, p-elemene, and other sesquiterpenes from Hedera helix leaves. Isoprene was identified in the forest atmosphere, thus proving its natural presence in plants, by Rasmussen (583), using a direct gas chromatography technique. Suga et a!. (678) synthesized a complex mixture of terpene alcohols from isoprene. Myrcene was removed from a mixture of terpenes by selective clatration by McCandless (447). Using peak heights from a fast column, the terpene composition from pine resin was rapidly analyzed by Smith and Greene (652). The NMR spectra of a-pinene type compounds were obtained and discussed by Toda and Takahashi (711). The structure of seychellene was confirmed by Schmalzl and Mirrington (622) through a total synthesis. The absolute configuration of sibirene was established with optical rotatory dispersion and circular dichroism studies by Dubovenko and Babkin (182). A synthesis of thujopsene by Mori et al. (493) helped to clarify its structure. Miscellaneous. Capsaicin in capsicum oleoresins was estimated by Mathew e t al. (471). I t was first separated on a thin-layer plate, then measured colorimetrically. Another method was used by Hartman (269) who first silanized the capsaicin and then estimated it by gas chromatography. Yum (781) assayed capsaicin by a multiple extraction and crystallization procedure. A precise method for determining dimethyl sulfide in foods was proposed by Williams et al. (762). A sensitive and specific color reaction method for detecting free indole was described by Tirimanna and Geevaratne (710). Johri (328) developed methods for separating neutral, basic, and acidic indole derivatives by thinlayer electrophoresis. Merz (482) evolved a new modified apparatus for automatically determining oxygen in organic compounds. The apparatus utilizes a vertical quartz tube for cracking and a colorimetric end-point indication. The dermination of nitrogen in foods by the Kjeldahl method using various catalysts was discussed by C6sma and Armeanu (144). A critical review of methods for determining piperine in
black pepper was given by Pruthi (5i8).Shankaranarayana et al. (631) developed a colorimetric method for determining piperine, chavicine, and piperettine in black pepper oleoresin. Other nonpungent amides interfered with the determination. Traxler (713) isolated a new pungent component of black pepper, called piperanine. Koehler et al. (383) determined tho odor threshold levels of pyrazine compounds and estimated their flavor effects in roasted foods such as peanuts and coffee. LITERATURE CITED (1) Abasova, 2. I., Aktuai. Probl. lzuch. fiflrnomaslich. Rast.' Efirn. Masei, 1970,p 131. (2) Agarwal. S. G., Flavour Ind., I , 625 (1970). (3) Ahmataj, H., Bul. Univ. Shfeteror Tirartes, Ser. Shkencat Nafyr., 24(1),21 (1970). (4) Ahuja, M. M.,Nigam, S. S., Flavour Ind. 1, 627 (1970). (5) lbid., p 721: (6) Ahuja, M. M., Nigam, S. S., Riechst., Aromen, Koerperpflegem.,
20,339 (1970). ' (7) /bid., 21,203 (1971). (8) lbid., p 281. (9) Aime, J. J., Peyron, L., f r . Ses Parfums 13,431 (1970). (10) Akhmedov, I. S.,Kasymov, S. 2.. Eiidyakin, G. P.,Khim. Prir. Soedin., 6,622 (1970). (11) ibid., p69l. (12) Akimov. Y. A,, Lishtvanova, L. N., Nilov. G. il, Rast. Resur., 6(1),99 (1972). (13) Akisue, M. K.. Rev. farm. Bioquim. Univ. Sao Paulo, 9(1), 107 (1971). (14) Aliev. N. A,, Kulieva, Kh. N., ibra!jimov, G. R., Rast. Resur., 7(1),85 (1971). (15) Alimov, F. A,. Chumakova, N. V., Maslo-Zhir. from., 37, 22 (1971). (16) Allen, I. D., Haken, J. K.. J. Chromator., 51,415 (1970). (17) Amano, Y., Heatchcock. C. H., Can. 1. Chem., 50,340 (1972). (18) Ames, G. R., Barrow, M., Borton, C ,Casey, T. E., Matthews, W. S., Nabney, J., Coward, L. D.G., TropSci., 13(1),13 (1971). (19) Anda, T. L., Cardenas, F., PoiifecnicJ, 2,385 (1970). (20) Andersen, N. H., Tetrahedron Lett., '1970,4651. (21) Andersen, N. H., Syrdal, D.'D.. Phytochemistry, 9, 1325 (1970). (22) Andersen, N. H., Syrdal, D. D., Tetrshedron Left., 1972,899. (23) Andersen, N. H.,Syrdain, D. D., Grsham, C., /bid., p 905. (24) Anderson, A. E., Riffer, R . , Wong, A.. Hoizforschung, 24, 182 (1970). (25) Andrushchenko, I. S.,Tovarovedenie, 1971 (5),12, (26) Appell. L.. Amer. Perfum. Cosmef., 85(10), 49 (1970). (27) Appleton, R. A,, Enzeil, C. R., Phyfo-hemislry, 10,447 (1971). (28) Arbuzov, E. A., Vul'fson. S. G., Vfireshchagin, A. N., Izv. Akad. Nauk SSSR, Ser. Khim. 1971,306. (29) Arkhipova. L. I., Kasymov, S. Z., Sidyakin, G. P., Khim. frir. Soedin., 6,480 (1970). (30) Arora, S.K., Agarwal, S. G., Vashist, V. N., Madan, C. L., Indian Perfum., 15(Pt. I), 16 (1971). (31) Asllani. U., Bul. Univ. Shteferor 'riranes, Ser. Shkencat Nafyr., 23(3),93 (1969). (32) Auer, W., Carinfhia I / Nafurwis,r. Beitr. Heimatk. Kaerntens, 1969,104. (33) Avakyan, T. T., Bioi. Zh. Arm., 23(13),109 (1970). (34) Ealbaa, S. I., Hifnawy, M. S., Ksrawaya, M. S . , Amer. Cosmef. Perfum, 87(5),41 (1972). (35) {bid., 86(6),53 (1971). (36) Baldrati, G.,Cagna, D., Giannonci, L.. Ind. Conserve, 45(2),125 (1970). (37) Baldry, J., Dougan, J., Howard, G , E.,Phytochemistry, 11, 2081 (1972). (38) Bambagiotli, A,, Massimo, Vinciei'i, F. F., Cosl, G., @id.,p 1455. (39) Eankowski. C., Czuba, W., Banak-Tabkowska, J.. Czas, Tech. (KrakowJ, M 1969(5),27. (40) Banthorpe, D. V., Eaxendale. D., 1. Chem. SOC.,C, 1970,2694. (41) Eanthorpe, D. V., Baxendaie, [ I . , Gatford, C., Williams, S. R., Pianfa Med.. 20,147 (1971). (42) Eanthorpe, D. V., Charlwood, El. V.. Francis, M. J. 0.. Chem. Rev., 72,115 (1972). (43) Banthorpe, D. V., Mann, J , , Tui'nbull, K. W., J. Chem. SOC., C, 1970,2689.
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(44) Baretta, A,, Jefford, C. W., Waegeil. B., Bull. SOC. Chim. F r . , 11, 3985, (1970). (45) Bark, L. S., Bate, P., Analyst (London), 96, 881 (1971). (46) Baron, C., Maume, B., Lhuguenot, J. C., Fr. Ses Parfums, 13(67), 31 (1970). (47) Basker, H. B., Lifshitz, A,, Stepak, Y . . Lebensm.-Wiss. Teciinol., 3(5).83 (1972). (48) Baslas, B. K., Baslas, R. K., lndian Perfurn., 15(Pt. 1 I , 27 (1971). (49) Baslas, 8. K.. Baslas, R. K., Riechst., Aromen, Koerperpfle(r?m., 22, 155 (1972). (50) Baslas, R. K., Flavour lnd., 1, 185 (1970). (51) lbid., p 188. (52) lbid., p 475. (53) lbid.. 2, 370 (1971). (54) Basias, R. K., lndian OilSoap J., 35, 136 (1969). (55) Baslas, R. K., lndianPerfum., 14(Pt. l ) , 67 (1970). (56) Basias, R. K., Baslas, K. K., Flavour Ind., 1, 473 (1970).
(97) Bravo, A. H., Retamar, J. A,, An. SOC. Cient. Argent., 192, 115 (1971). (98) Breckler, P. N., Betts, T. J., J. Chromatogr., 53, 387 (1970). (99) Briggs, L. H., Bartley, J. P., Aust. J. Chem., 23, 1499 (1970). (100) Briggs. L. H., White, G. W.. J. Chem. SOC.C, 1971, 3077. (101) Brodnitz, M. H., Pascale, J. V., J. Agr. Food Chem., 19, 269 (1971). (102) Brodnitz, M. H., Pascaie, J. V., Van Dersiice, L., ibid., p 273. (103) Brown, D. F., Senn, V. J., Doliear, F. G., Stanley, J. B., J. Amer. Peanut Res. Educ. Ass., 3 , 2 0 8 (1971). (104) Bruns, K., Parfuem. Kosmet., 53(4). 98 (1972). (105) Buechi, G., Degen, P., Gautschi, F., Willhaim, B., J. Org. Chem., 36, 199 (1971). (106) Burk, L. A,. Soffer, M. D., Tetrahedron Lett., 1971, 4367. (107) Burrell, J. W. K., Lucas, R. A,, Michaikiewicz, D. M., Riezebos, G., Chem. lnd. (London), 1970,1409. (108) /bid., 1971, 2837. (109) Buttery, R. G., Bomben, J. L., Guadagni, D. G.. Ling, L. C., J. Agr. FoodChem., 19,1045 (1971).
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