(110) Sheppard, A. J., Meeks, S. A., Elliott, L. W., J . Gas Chromatogr., 6 , 28, 34 (1968). (111) Smith, D. A., Rubber J., 150, 33, 37 (1968). (112) Smyslova, N. F., Emelin, E. B., Yamshikova, T. P., Zavod. Lab., 33, 568 (1967). (113) Spagnola, F., J . Gas Chromatogr., 6 , 609 (1968). (114) Su, H. C., Cameron, J. L., ANAL. CHEM.,39, 949 (1967). (115) Sugito, T., Ito, M., Bull. Chem. SOC. Japan, 38, 1620 (1965). (116j Sundehand, E., J . Oil Colour Chemists’ Assoc., 51, 254 (1968). (117) Suzuki, S., Japan Analyst, 15, 169R 11966). (118) Swann, M. H., J. Paint Technol., 40, 468 (1968).
(119) Swann, M. H., Adams, M. L., Esposito, G. G., ANAL. CHEM.,39, 42R (1967). (120) Swann, M. H., Lund, D. G., Esposito, G. G., J. Paint Technol., 39, 191 (1967). (121) Tan, H. L., Specialties, 3, 11 (1967). (122) Tarasov, A. I., Volodina, V. I., Spasskii, S. S.,Zh., Anal. Khim., 21, 360 (1966). (123) Tuemmler, F. D., ANAL.CHEM.,39, 157R (1967). (124) Uetsuki, M., Fujiwara, S., Japan Analyst, 15, 104R (1966). (125) Uhacz, K., Chem. Anal. (Warsaw), 12, 513 (1967). (126) Urbanski, J., Plaste Kautschuk, 15, 260 (1968). (127) Vajda, F., Acta Chim. Acad. Sci. Hung., 53, 241 (1967). (128) Vandeberg, J. T., Appl., Spectrosc., 22, 304 (1968).
(129) Wandel, M., Tengler, H., Kunststofe, 55, 655 (1965). (130) Wheals, B. B., Thomson, J., Chem. Ind. (London). 18. 753 (1967). (131) van der Wijngaard, J., Continental Paint & Resin News, 5, 2 (1967). (132) Willis, H. A., Cudby, XI. E. A., Appl. Spectrosc. Rev., 1, 237 (1968). (133)-Wise, J. K., Smith; C. D., ANAL. CHEM.,39, 1702 (1967). (134) Wolff. J. P.. Karleskind. A.. Audiau. F.;Double Liaison, No. 136,’1529 (1966): (135) Yasuda, S. K., J. Chromatogr., 27, 72 (1967). (136) ‘Zalmanski, M. A., Ind. Chim. (Paris), 55, 255 (1968). (137) Zinke1,’D. F., Lathrop, M. B., Zank, L. C., J . Gas Chromatogr., 6 , 168 (1968). (1381 Zinkel. D. F.. Zank. L. C.. ANAL. Chem., 40,’ 1145 (1968). ~
Essential Oils and Related Products Ernest Guenther, Gilberf Gilbertson, and Roman T. Koenig, Fritzsche Brothers, Inc., New York, N.Y.
T
REVIEWof theanalysis of essential oils and related products covers the literature from September 1966 t o August 1968, inclusive. It follow the general pattern previously established (204). During this period, the efforts of many outstanding chemists have continued t o increasc the already voluminous knowledge in this field. Many detailed studies of the commercially important essential oils were published; in addition, numerous investigations were concerned with oils not previously well known. Another area where advances were most noteworthy was the identification and structural elucidation of sesquiterpenoids and other higher molecular weight essential oil components. Gas chromatography was still the most frequently employed analytical technique, but other instrumental as well as chemical methods were also all effectively utilized, and the coupling of instruments was practiced more widely and with increasing expertise. An attempt has been made t o include all contributions dealing directly with the analysis of essential oils and the determination of their constituents, but in some related areas, such as the investigation of volatile flavor essences or the determination of chemical structures, the selection of papers for this review was of necessity limited t o those which appeared most directly related or more illustrative. Official Compendia. The first edition of the “Food Chemicals Codex” (412) was published. It established standards for many aromatic substances and essential oils which are employed in foods. HIS TWELFTH
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The Scientific Committee of the Essential Oil Association of the U.S.A. established standards for ten products, embodied in the following monographs: No. 269, cis-3-hexenyl acetate; 270, cis-3-hexenol; 271, oleoresin turmeric; 272, lemon oil Arizona; 273, citral dimethyl acetal; 274, linalyl isobutyrate; 275, linalyl formate; 276, iso-eugenyl acetate; 277, dimethyl phenyl ethyl carbinol; 278, cinnamic aldehyde dimethyl acetal. Revisions of previous E.O.A. specifications, including gas chromatic methods and infrared spectra, were issued for the following essential oils and aromatic chemicals: No. 3, oil petitgrain Paraguay; 66, oil tolu; 67, oil oppopanax; 68, oil olibanum; 112, oil fir needle Canadian; 114, oil wormwood; 119, oil laurel leaf; 137, oil galbanum; 141, oil myrrh; 143, oil marjoram Spanish; 5, hydroxycitronellal; 26, aldehyde C-10; 92, nonalactone; 100, hydratropic aldehyde; 123, aldehyde C-11 undecylic; 127, cedryl acetate; 134, phenyl acetaldehyde dimethyl acetal; 144, geranyl propionate; 169, benzodihydropyrone; 227, citronellal; 233, terpinyl propionate; 248, amyl caproate; 249, amyl propionate; 254, allyl cyclohexyl propionate. Some of these standards were reviewed in the Perfumery and Essential Oil Record (461), others have just been adopted by the E.O.A. as of Jan. 3, 1969. Books and Articles. Many books and articles of general interest t o the essential oil analyst have appeared. Among the most pertinent are “Die Aetherischen Oele, Band I11 d,” by Gildemeister and Hoffman (183);“Terpenoids in Plants,” edited by Pridham
(478); and a review of advances in the fields of terpene derivatives, essential oils, ionones, musks, and other perfumery compounds by Fordham (161). T h e “Internationaler RiechstoffKodex,” 1968 edition by Mueller (403), described many thousands of aromatic substances, perfume bases, and special flavors, and also gave more than 4000 pertinent references. The second edition of the well known “Perfumery and Flavoring Synthetics” by Bedoukian (39) was issued. H e (37, 38) also contributed two articles dealing with progress in perfumery materials and including analytical procedures. The correlation of objective instrumental and chemical analytical methods with the subjective evaluation of perfumery materials was discussed and illustrated by Langenau (340). A general discourse on essential oils was written by Stoll (571), and learned discussions were given on the subject of flavors and spices by Hamann and Guenther (215), and on perfumes by Shiftan (544). Quality control and analysis were discussed in all three articles. Rogers (494) related advances in the chemistry and analysis of capsicum, black pepper, and clove. A unified theory accounting for the biosynthesis of various monoterpenes in diverse plants was proposed by von Schantz (520). Labeled 14C was utilized by Loomis (365) to study the biosynthesis and metabolism of monoterpenes in peppermint and geranium, and, by a similar technique, Hefendehl (116)concluded that limonene is a precursor of the C-3 oxygenated monoterpenes in Mentha piperita.
General Procedures. A survey of current practical aspects of gas chromatography was edited by E t t r e and Zlatkis (156)) and a book dealing with the analysis of essential oils by gas chromatography was written by Masada (378). Vernin (633) reviewed recent advances in the theory and techniques of columns, detectors, supports, and qualitative and quantitative analysis as related to the investigation of essential oils. Teranishi et al. (603) summarized developments in gas chromatography techniques in conjunction with mass spectrometry and NMR for the elucidation of organic structure. Teranishi (600)further discussed these techniques, relating how the capacity of high resolution gas chromatography columns has been increased and how, combined with mass spectrometry and the utilization of submilligram sample sizes for NMR studies, gas chromatography has led to the identification of important flavor components and most of the volatile constituents of mandarin and lime oil. H e also applied gas chromatography to aroma research and related it to the odor thresholds of nine compounds (601).
Chang (93) surveyed new techniques for the isolation, gas chromatographic fractionation, and identification of volatile flavor compounds. The logarithms of the retention times of homologous series of normal alcohols and aldehydes were found by Manjarrez and Bertrand (37'0) to have a linear relationship to the chain lengths. Hawkes and Wheaton (221) described a statistical method of analysis which utilizes a large number of individually insignificant gas chromatographic differences to determine the geographic origin of complex mixtures such as peppermint oil. They felt t h a t though this is a n advance in concept over current methods, it requires further development. The concentration of volatile compounds from dilute aqueous solutions based on low temperature distillation and sublimation was described by Forss and coworkers (163). The technique is applicable to compounds t h a t would normally be lost by extraction techniques. Henke (230) discussed methods of obtaining aromatic substances from plants, emphasizing extraction with air or gas and active charcoal. Puttnam and Lee (481) described a faster method based on increased temperature and pressure for obtaining volatile products from cosmetics for gas chromatographic analysis. The application of gas chromatography to perfumery was reviewed by Peyron ( 4 6 4 , and was also discussed by Sfiras (540). He described the technique of sniffing a t the exit port, which he utilized to analyze the differences in the composition of the head space gas
as compared with the actual composition of the perfume. Stancher and Pertoldi (565) determined the impurities in 40 commercially available essential oil components and considered their use as gas chromatographic standards in the analysis of perfumes. Indian firebrick was compared with Celite as a support in GLC columns by Kulkarni et al. (336). Because the firebrick support had no catalytic effect, it was possible to analyze mixtures of labile monoterpenic alcohols without decomposition. Witte and Dissinger (662) collected gas chromatographic microfractions by adsorbing the eluate on microcrystalline organic solvent in a U-tube at liquid nitrogen or argon temperatures. Backflushing gas chromatography was a new approach t o residue analysis developed by Crossley ( 2 1 4 , and could conceivably be applied to essential oil analysis. The coupling of gas chromatography with thin layer chromatography, infrared spectrometry, radiochemical methods, and mass spectrometry was illustrated and evaluated as to limits and possibilities by Kaiser (285). Similar combinations with fast-scan mass and infrared spectrometry were discussed by van den Do01 (144, and Dijkstra (140) compared the advantages of methods of coupling a gas chromatograph to a mass spectrometer with the trapping and transfer of fractions from one instrument to the other. A gas chromatographic method using a high efficiency capillary column and a hydrogen flame ionization detector for the analysis of oxygenated aliphatic compounds, other than acids, was tested by Wang et al. (649). Shulgin (645) tabulated the relative retention times for 30 components of the volatile aromatic fractions of essential oils and described a rule for assigning unambiguously the correct structure to the olefinic side chain of an unknown component. Maekawa et al. (365) developed an equation by which retention volume may be calculated. The relation between the log of the relative retention time and the inverse absolute temperature was used by Arakelyan et al. (10) for the identification of various organic substances. Adulteration of natural products by the addition of synthetic aromatic products was detected by Bismead and Kratz ( 5 1 ) , who applied gas chromatography and infrared and mass spectrometry to the problem. Traces of volatile solvents in spice aleoresins were determined using gas Chromatographic analysis of the headspace by Labruyere and coworkers (338). -4method for the direct gas chromatography of essential oils in plant materials was employed by Baerheim Svendsen and Karlsen (21) to analyze
oils from angelica, rosemary, pine, thyme, and peppermint species. A direct vapor chromatographic determination was also employed by Lyerly (361) for the assay of menthol and other substances in cigarette smoke. Aspects of reaction gas chromatography were described by Tumlinson et al. (662), who combined i t with thin layer chromatography for the identification of carbonyl compounds in essential oils, and by Mizrahi and Nigam (392), who dehydrogenated monoterpene compounds on platinum-alumina catalyst. Pribela (477) separated volatile components of various classes by the formation of chemical derivatives which were subsequently analyzed by gas chromatography. Thin layer chromatographic methods used for identification of terpenes and similar compounds were critically examined by Petroemitz (463). Calvarano (80) reviewed the application of radial and thin layer chromatography t o the study of essential oils and their components. Various thin layer methods were used by Dyakov and Zolotovich (150) to select the best essential oilbearing plants for propagation. The quality as well as the quantity of the oils could be estimated. A simple method based on thin layer chromatography was devised by Chopra (96) for the evaluation of the purity of oils of cardamom and pepper. Liquid column chromatography was employed by Murray and Stanley (408) to separate chemical classes of volatile food flavor constituents. Salting-out chromatography resulted in the quantitive separation of 2,3butylene glycol, acetoin, and biacetyl as reported by Speckman and Collins (557). I n a review of the basic theory and practice of infrared spectrometry of essential oils, Vernin (631) tabulated characteristic absorption frequencies, discussed the influence of substituents on the vibration bands of double bonds, and presented a method for the differentiation of cis and trans bonds. Kalsi (286) also discussed the application of infrared spectra to the structural elucidation of olefinic double bonds. Ultraviolet absorption spectrometry, together with other physical characteristics, was used by Koul and Nigam (320) for structural analysis of unknown terpenes and the quantitative estimation of citral, eugenol, and anethole. Polarography mas employed by Koul and Xigam (321, 322) to study some aldehydes, ketones, and their 2,4dinitrophenylhydrazones, and the nitroso chlorides of hydrocarbons and alcohols. The half-wave potentials were determined a t different p H values and the results were interpreted. The viscosity and surface tension of terpenes and essential oils were deterVOL. 41, NO. 5, APRIL 1969
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mined by Koul and Nigam (323) and used in the quantitative analysis of known mixtures. The flashpoints of 44 essential oils and 85 synthetic aromatic substances, as well as mixtures, were recorded by Ignat’eva et al. (159). I n a study of the determination of essential oils with Brueckner-modified neoclevenger apparatus, Lossner (358) concluded that it is necessary to standardize all details of the determination to obtain consistent results. Podlubnaya et al. (473) used differences in refractive index to estimate the quantity of essential oils in aqueous alcoholic liquids. A nephelometric determination of the quantity of essential oil in small samples of coriander seed utilized by Gurvich and Neparidze (211) resulted in a high degree of accuracy. An improved apparatus for the determination of C, H , and p\T was described by Condon (98). Nitrogen was determined by Nepryakhina et al. (419), who analyzed the pyrolytic combustion mixture obtained by a modified Dumas method with gas chromatography. Unsaturation was determined, using a new, convenient, and rapid hydrogenation method, by Brown et al. (68), and Fritz and Wood (168) distinguished simple olefinic unsaturation from conjugated bonds by monitoring the absorbance at 400 mp during a rapid bromine titration. ESSENTIAL OILS
General. The chemical and physical properties of essential oils of Asiatic origin were compiled by Trabaud (616). Manjarrez and Mendoza (371) analyzed the volatile oils of Agastache Mexicana and Cunila lythrifolia and identified their major components, including furfural, undecylaldehyde, and 8-ionone. The oils from fruits of Biota orientalis and cypress were studied by Sakhatov and Belova (511), who identified many terpene and sesquiterpene compounds therein. The oils of fennel, geranium, and coriander were subjected by Paukov and coworkers (456) to capillary gas chromatography employing 30,000 t o 50,000 theoretical plates. A linear relationship between the logarithms of the retention volumes of aliphatic, monocyclic, and bicyclic hydrocarbons was observed on two different columns. Some hitherto little-known essential oils were examined by Peyron (465), using the latest analytical techniques. Properties and many components were reported for oils of lentiscus, Borneo lemon, and limonette petitgrain. The investigation of many Indian essential oils was reviewed by Baslas (30-31). The essential oils from linalool- and linayl acetate-bearing plants in India were studied by Sharma et al. (54.3, 42 R
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who identified the major components in oils of Zanthoxylum alatum, Zanthoxylum hamiltonianum, Homalomena aromatica, Michelia champaca, Skimmia laureola, Mentha citrata, lavender, and sage. Muller (406) discussed the composition of the oils of sage, laurel, and myrtle obtained from regions near Italy. The characteristics of essential oils from 15 exotic plants raised in Kumaon were determined and tabulated by Baslas and Baslas (33, 34). Kingston (307) summarized characteristics of essential oils in current production in Japan. Montes (395) continued his investigation of essential oils from plants grown in the National Park of Nahuel Huapi and reported the properties and some components of seven oils. I n further studies of the oils described in the Polish Pharmacopeia, Deryng et al. (114) analyzed fennel and anise oils by gas chromatography. Individual Essential Oils. A gas chromatographic separation of 28 terpene hydrocarbons from Abies alba was carried out by Baerheim Svendsen and Karlsen (22) at low temperatures on columns packed with 2.5% of various mobile, stationary phases. From Abies balsamea, Cerny et al. (89) isolated and determined the structure of dehydrojuvabione, a new compound with juvenile hormone activity. Higher molecular weight terpenes, including manool, were identified by Swan (582) in several Canadian Abies species, and Bardyshev and Shashkina (25) found p-phellandrene in a fraction from Abies sibirica. Two new constituents from the oil of Ageratum conyzoides were characterized by Kasturi and Manithomas (698). Quality evaluation of oil of anise based on thin layer analysis of its composition was achieved by Zacsko-Szasz and Szasz (669). Ishibashi et al. (264) identified 14 components in Chinese star anise oil and compared its composition with that of European fennel oil. A star anise oil from Illisum anisatum was found by Cook and Howard (100) to differ greatly from the commercial oil from Illisum oerum. Its major components were cineole, linalool, methyl eugenol, and others. They also identified 10 sesquiterpene hydrocarbons in the oil (101). Yamada et al. (665) isolated and determined the structure of two toxic sesquiterpenes, anisatin and neoanisatin, from the same oil. The main components of oil of Anemopsis californica were found by Acharya and Chaubal (1) to be eugenol, thymol, and piperitone. The essential oil content in the flowers of various Arnica species was determined by Guentzel et al. (106). The composition of essential oil from Artemisia species was gas chromatographically analyzed by Nigam and
Rao (431). Nano et al. (409) reported the major constituents in the oils from Artemisia pontica, A . dracunclulus, and A. spicata. Matsueda and Geissman (381, 386) isolated and established the structure of two new lactones, arglanine and douglanin, from A. douglasiana. The oil of A . annua was investigated by Goryaev et al. (191), who identified many constituents, including artemisia ketone. Spitzer and Steelink (558) isolated the sesquiterpene lactone, matricine, from A . caruthii. Essential oils from the plants of the Asarum and Asiasarum genera were investigated by Saiki et al. (509) who, with gas chromatography, identified many components. Atractylodes ovata oil was shown by Studennikova and Khaletskii (574) to contain atractylon and atractylol, two new sesquiterpenoids which were separated with vacuum fractionation and column chromatography. The oil of Baccharis dracunculifolia, a common weed growing in Brazil, contains nerolidol as a chief constituent, according to a report by Ribeiro dos Santos et al. (493). The composition of sweet basil oil from plants grown a t various temperatures was differentiated by Pogany (474). Together with Bell and Kirch, he isolated and indentified benzyl ether in the oil (475). X g a m and Rao (433) also reported a chemical investigation of the constituents of basil oil. Chorbadzhiev and coworkers (97) studied the composition of Bulgarian basil oil and found that it did not belong to the methyl cinnamate type, but is close to the American type. Bergamot oil was further investigated by Calvarano (86) who, by gas chromatographic analysis of 50 samples, identified 25 components. Farid (160) characterized a new flavone isolated from the oil. Muller (405) discussed the value of modern instruments in assuring the purity of bergamot oil, and Rudol’fi and Sharapova (504) suggested the determination of bergaptene with ultraviolet spectrometry as an indication of purity. From the alcohol portion of Biota orientalis oil Tomita et al. (613) isolated and characterized nine alcohols including two of the cedrane type, 01- and pbiotol. Oils distilled from Bothruochloa intermedia by Gulati and Gupta (809) had a n aldehydic character which would be useful in perfume formulations. The constants of the oils were given. The principal components of buchu oil, among which are menthone, isomenthone, pulegone, piperitone epoxide, and diosphenol, were identified by Klein and Rojahn (310, 311). The volatile compounds in butter oil were determined by Forss et al. (164). Though individually many of the com-
ponents were below threshold level, the total oil produced a desirable creamy flavor. I n further investigations, the same authors (165) identified many y and &lactones in butter oil. The p-asarone content of calamus oil as determined with various gas chromatographic techniques was compared by Usseglio-Tomasset (624). The sesquiterpene hydrocarbons in camphor oil were separated and identified by Hayashi et al. (222). Hikino and coworkers (248) elucidated the structure of campherenone and campherenol, two new sesquiterpenoids isolated from camphor blue oil, and Araki et al. (11) established the structure of cadina-g,11(12)-diene separated from the same oil. Caparrapi oil was investigated with a combination of modern techniques by Appel et al. ( 7 ) , who reported the identification of numerous components. Two sesquiterpene alcohols, caparrapidiol and caparrapitriol, were isolated and their structures were established by Borges del Catillo and coworkers (62). Thin layer chromatography of oil of Capsicodendron dinisii showed 12 spots according to rvlancini (368). The essential oil of Indian caraway was shown by Atal and Sood (14) to have a high carvone content, and appeared to be of excellent quality compared to oils of European origin. The chemical composition of cardamom oils from ,Mysore, Malabar, and Ceylon were determined and compared by Lewis and coworkers (348), who employed column, gas, and thin layer chromatography. I n a similar comparison of oils from various cardamom types, Wellendorf (651) concluded t h a t a high terpinyl acetate content is characteristic of better seeds. He found no a-terpineol in the oils. The results of fractionation and column chromatography of carrot seed oil conducted by Pigulevskii and Kovaleva (468, 469) demonstrated t h a t it contained a number of familiar sesquiterpenoid hydrocarbons and oxygenated compounds. The stereochemistry of carotol and daucol was established by Levisalles and Rudler (344, 345). An improved and more reliable method for the determination of volatile oil in cassia was devised by Rosebrook et al. (499), and Voelker and coworkers (644) reported a thin layer chromatographic method to differentiate among cinnamons and cassias of various geographical origins. I n a study of cassis leaves, Gospodinova and Tevekelev (197) found that 50y0 of its essential oil is water soluble and described methods of distillation to avoid the loss of this portion. Properties of the resulting oil were listed, Catnip, iyepeta cataria, from three separate locations was shown by Regnier et al. (491) to contain a much greater
quantity of nepetalactone than of epinepetalactone. However, the same authors (492) reported t h a t the reverse is true in the case of Nepeta mussini. Components of N . citriodora were also described. Regnier (490) proposed a biosynthesis for nepetalactone. From the oil of Cedrus deodara, Joseph and Dev (272) isolated a- and ,%himachalene, sesquiterpenes shown to have a new type carbon skeleton, and Bisarya and Dev (49, 50) isolated and determined the structure of himachalol and allohimachalol. Many new components of oil of Chamaecyparis taiwanensis, or hinoki oil, were quantitatively determined by Yoshida et al. (668) and Toda and coworkers (611) isolated and characterized 4, 9-dimethyl-6-isopropenyl-4-bicyclo[4.4.0]-decene from the same oil. The oil content of chamomile flowers was assayed with a modified Brueckner apparatus by Schaefer (519), who also estimated the content of azulene and some other components in the oil. An essential oil was distilled from Chrysanthemum morifolium leaves by Bahadur and Gupta (24).Its properties were reported and many of its components identified. The characteristics and the percentage content of cinnamic aldehyde and eugenol were determined by Talalaj (590) for oils from the bark and leaves of cinnamon Ceylon grown in Ghana. The properties of citronella oil from Taiwan are detailed in a field survey by Guenther (203). S a r a y a n a et al. (4f 1) studied the changes in the characteristics of citronella oil from grass dried for various periods of time. A gas chromatographic, temperatureprogrammed method for the identification of essential oils from citrus fruits !vas described by Huet (255). The method was also said to be capable of ascertaining the purity of the oils. A series of articles on the origin of citrus flavor components was written by A t t a w a y et a l . (15-17). K i t h t h e most advanced techniques, oils from leaves, petals, stamens, pistils, and peels of various citrus species were analyzed and the biological development of flavor components was studied. A programmed-temperature gas chromatographic method for the analysis of citrus flavor components in soft drinks mas developed by Kamiyama and Koguchi (288), and Rogers and Toth (495) studied the chemical changes responsible for flavor deterioration of lemon and other citrus oils in the spraydried form and in baked goods. The c i t r u s oils were described in g r e a t detail in a series of articles by Di Giacomo (130-139). Production, botany, properties, methods of analysis, and organoleptic and chemical methods of evaluation were discussed. T h e physiochemical properties of California
orange and lemon oils were compiled by Swisher (583), and Basker (29) assembled d a t a and characteristics regarding citrus oils from Israel. The terpenes from oils of tangerine and mandarin were identified by Ashoor and Bernhard ( 1 2 ) and compared with those of other citrus oils. Spectrofluorimetric characterization of mandarin, lemon, and bergamot oils was attempted by D’Amore and Corigliano (122). Leaf oils from Citrus natsudaidai, C. kokitsu, and C . limon were i n v e s t i g a t e d b y K a m i y a m a (287) who identified many components. Similarly, Kokama (313 ) identified many components, including thymol methyl ether, in the leaf oil of Citrus depressa. Three new methods were developed for functional group analysis of components of citrus juice essence by Attaway et al. (18), including tests for oxygenated terpenes, saturated aliphatic aldehydes, C Y, p-unsaturated aldehydes, and esters. An infrared spectrographic and gas chromatographic microdetermination of biphenyl in citrus peel mas described by Schunack and coworkers (528), and methods for detecting diacetyl and acetylmethylcarbinol in citrus products mere tested by Murdock (407). -1new bitter principle, ichangin, was isolated from a hybrid of Citrus ichangensis by Dreyer (145). The separation of terpenes from citrus oils was accomplished with the formation of thiourea inclusion complexes by Askitopoulos (13), and with solvent partition using dimethyl sulfoxide by Norman and Craft (436). Eighty-one volatile compounds were identified in coca by van der Wal et al. (646), who used gas chromatography. The oil of coriander was analyzed and many of its components were identified by Akimov and Voronin ( S ) , who also investigated citral obtained from the oil. Razinskaite (486) studied 11 varieties of Coriandrum sativum grown in Lithuania and reported high essential oil yields. Razinskaite and Slavenas (487, 488) determined the oil content in roots, stems, leaves, and seeds of coriander a t various stages of development and found marked differences. The oil content was increased by artificial fertilizers. Schratz and Qadry (523) used thin layer chromatography to determine the composition of coriander oils from Indian and German plants periodically during their life cycle following germination. Xotable changes were observed. Monolov and Georgiev (394) determined linalool in coriander oil by a semimicro colorimetric method. The costol fraction from costus root oil was shown to be an intimate mixture of several alcohols, including true costol, in a study by Bawdekar and coworkers
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From oil of cubeb, Ohta et al. (445) isolated and characterized two hydrocarbons having the cadinane skeleton, CY- and 8-cubebene. Ohta and Hirose ( 4 3 ) also established the structure of cubenol and epicubenol. The composition of the essential oil from 11 croton species grown in Venezuela was investigated by Bracho and Crowley (66). The physicochemical properties and major components of oil of Cyathocline lyrata were described by Devgan and Bokadia (127, 128), who also established the structure of lyratol, a terpene alcohol which, together with its acetate, comprises 70% of the oil, and the structure of which violates the isoprene rule. Components of the oil from Cyperus rotundus, or nut grass, were isolated by Hikino et a1 (237-240), who characterized the structures of a sesquiterpene oxo alcohol, cyperolone, the tricyclic sesquiterpene ketone, cyperotundone, and the keto1 sugeonol. Kapadia et al. (289) detected about 90 constituents in Indian oil of Cyperus rotundus and determined thestructure of copadiene, epoxyquaine, rotundone, and cyperolone. The oil of Cyperus scariosus was shown to contain cyperotundone by Hikino and coworkers (241), and Kerali and Chakravarti (420) characterized two new sesquiterpene alcohols isolated from the oil, cyperenol and patchoulenol. The oil of Dacrydium colensoi was shown by Corbett and Smith (102) to contain several diterpenoids, including manoyl oxide, and a new alcohol whose structure was elucidated. Corbett and Wyllie (10.4) determined the structure of rimuene, a diterpene from Dacrydium cupressinum. Many essential oil components of the fragrant Daphne odora were identified Sisido et al. (547). I n a preliminary study of davana oil, Lewis and Nambudiri (347) obtained its physical constants, I R spectra, and gas chromatographic curve. Gulati and coworkers (208) reported on the properties and quality of davana oil from a trial cultivation in LTttar Pradesh. Oil of dillseed from Indian seeds was gas chromatographed by Sethi et al. (638), who reported its quantitative composition. Singh and Gupta (546) compared the accuracy of the bisulfite, neutral sulfite, and oximation methods for the determination of ketones in dill oil. Nigam and coworkers (423)isolated carvone from dill oil, using a modified neutral sulfite method. The physicochemical properties and some components of a n elemi oil from Ghana were determined by Talalaj (587). Oil of Elsholtzia Ciliata from Japan was examined with gas chromatography by Fujita et al. (173), who identified nearly all of its components. Biogenetic views were presented which explain the variations in the composition of the 44 R
ANALYTICAL CHEMISTRY
oil from that of oils obtained from plants from other parts of the world. Such variations in composition had been noted in a n earlier investigation by Fujita and others (175). Fujita and Tanaka (172) also determined quantitatively the composition of oil of Elsholtzia nipponica, and Vashist et al. (626) gave the physicochemical properties of oil of Elsholtzia polystachya and identified a new 2-substituted furan derivative in the oil. Oils of erigeron were distilled by Lukic and coworkers (360) from fresh and dried plants. The properties of the oils were determined. The composition of the oil from the leaves of Eucalyptus aggregata was elucidated by Hellyer et al. (228), who reported a new ester, 6-phenylethyl 3,4,5-trimethoxybenzoate. Similarly, Hellyer and McKern (229) determined the main constituents of E. amplifolia and E. kitsoniana. Oil of Eucalyptus citriodora was investigated by Cristini and coworkers (112) who determined how the best yield of oil and of citronellal might be obtained; by Virmani and Datta (638) who presented physicochemical properties of oils from both Australia and India; by Talalaj (689) who determined the characteristics of a n oil from plants grown in Ghana; and by Kapur et aZ. (290) who, after a thorough chemical and instrumental study, concluded that E. citriodoragrowing in India actually exists as two different strains which yield different oils. Variations in the oil with the time of year and the age of the trees was also reported. The presence of a pinene precursor in oil of Eucalyptus globctlus was indicated by Laurent and D a Cunha ($429, and Martelli et al. (377) determined the main composition of oil of Sardinian Eucalyptus rostrata. The essential oils from fennel fruit from Germany, Poland, Hungary, and other European areas, India, China, Japan, and Argentina were differentiated by gas chromatography by Toth (614). Newly found components were reported and the oils from bitter fennel, sweet fennel, and fennel root were contrasted. The root oil contained 90% dill apiole. According to Osisiogu (460), a fennel oil fromplants grown in Nigeria contained anethole but no fenchone. Oil from Ferula jaeschkeana stems was shown by Goryaev et al. (194) to consist of a light fraction which is similar to turpentine and another fraction containing mostly sesquiterpenes such as caryophyllene and calamenene. Oils from fir needles of various species were compared by Weissmann (650). Some showed significant differences, whereas the oils from three American species were similar. Sakai et al. (510), by repetitive gas chromatography on dissimilar substrates, identified many
major and minor components in Douglas fir needle oil. The sesquiterpene alcohol, galbanol, from galbanum oil was structurally characterized by Wichtl(661). Naves (414) isolated trans-cis- and trans-trans-nundeca-l,3,5-trienes and their dimerization products from galbanum oil. The quantitative composition of Calabrian geranium oil was ascertained in detail by Calvarano (83). Corbier and Teisseire (105) isolated neoisomentho1 and copaene from a fraction of geranium oil, and Giannotti and Schwang (181) characterized two new furanoid sesquiterpenes from the ketonic fraction. Krepinsky et al. (329, 330) established the absolute configuration of the previously isolated LY- and p-bourbonenes. The oil from the flower buds of Japanese ginger was shown by Kusumot0 and coworkers (337) to contain several terpenes and havep-phellandrene as the main component. trans-Isoperillyl alcohol was isolated from gingergrass oil and characterized with I R studies by Rao et aZ. (482). The chemical changes that occur in the curing of Florida grapefruit oils were investigated by Kesterson and Hendrickson (303). Berry and coworkers (44) made a study of the flavor effect of nootkatone. Steam-distilled oil from Hammamelis virginiana leaves was analyzed by Messerschmidt (387), who identified 2-hexenal and LY- and p-ionone. Terpene alcohols were isolated from oil of Helichrysum dendroideum and characterized by Lloyd and Fales (363). Tira et al. (610) determined the structure of p-diketones newly separated from Helichrysum italicum oil. Some components of the oils of the Heracleum species were determined by Wellendorf (662). The oil of Heracleum sosnowskyi was proved to contain a high percentage of octanol by Sedzik and coworkers (535). Oils obtained from more than 25 species of the Heterotropa genus were gas chromatographed by Saiki et al. (606-508), who identified many constituents of each oil. Ho leaf oil from seedlings from the same parent plant may contain predominantly cineole, camphor, safrole, or linalool, according to Kingston (306), while the composition of oils from pIants propagated by cuttings do not vary. An oil with a spicy odor was obtained from Homalomenaaromatica by Bahadur and Gupta (23). It contained large percentages of linalool and cadinene. The vastly detailed knowledge of the chemistry of Hop oil constituents was reviewed by Stevens (669). The essential oils from different varieties of hop may be readily distinguished by their gas chromatographic patterns and by the relative percentages of certain com-
ponents, as shown by Buttery and Ling (75).Likens and Nickerson (349) demonstrated t h a t oils from specific varieties remain constant in composition in spite of environmental influences. Buttery and Lundin (77) characterized some sesquiterpene constituents. Walker ( 6 4 8 ) f o u n d o u t s t a n d i n g chemical differences in oils from New Zealand hops as compared with those from European hops. Hartley (219) isolated 2-methylbut-3-en-2-01, and van Boven and Verzele (64) characterized 4-acetyl humulinic acids X and B. Buttery and coworkers (76) identified several sesquiterpene hydrocarbons in hop oil, two of which had not previously been described. Dev et al. (126) discussed the possible conformational changes of humulene and zerumbone as indicated by nuclear magnetic resonance spectrometry. T h e m a i n acrid constituents of Japanese horseradish were shown by Kojima et al. (312) to be allyl and @phenethyl isothiocyanates. The quantitative analysis of the terpenes from Hymenoliyma trichophyllum oil was accomplished by Goryaev et al. (196). The essential oilcontent of Hypericum species from the Tara Mountains was reported by Stjepanovic et al. (570). The quantity of oil of hyssop obtained from plants growing in various regions of the U.S.S.R. was given by Kravchenko and Sviderskaya (328). Essential oils were distilled from the fragrant and nonfragrant types of ground ivy by Takemoto and coworkers (584). Many constituents, including the main monoterpenic ketone, l-pinocamphone, were identified. Many volatile components of Calabria jasmine essence were identified by Calvarano (84) after a study t o select the most appropriate conditions for gas chromatography. The essential oils from six species of North American junipers contained the same 37 constituents, though in varying quantities, according to Vasek and Scora (625). The major components of Juniperus ashei oil were identified by von Rudloff (502), mho reported isolating d-camphene hydrate for the first time from any natural source. Karryev (296) reported the yield and properties of juniper oils from a number of Central Asian species. Karlsen and Baerheim Svendsen (293), using a novel method for direct analysis from plant material, identified the terpenes in Juniperus communis. Sood (556) reported the properties of a dark green volatile oil from the heartwood of Juniperus macropoda. Teppeev and Goryaev (598) ascertained the percentage composition of Juniperus pseudo-sabina. Goryaev et al. (189) separated many constituents from the oil of Juniperus turkestanica using a combination of chemical, physi-
cal, and instrumental methods. The quantitative composition of the oil, as well as the properties of many isolates, was determined. The essential oil content of several Lagochilus species was tabulated by Ikramov and Chizh (261). The physicochemical properties and the chemical composition of essential oils from the leaves, stems, and processing wastes of laurel, Laurus nobilis, were compared by Pruidze and coworkers (480). I n a more detailed analysis, Goryaev et a1. (190) listed the quantitative composition of the high boiling fraction of laurel oil. Kekelidze (301) studied the chemical composition of laurel oil from leaves, branches, and leaf exudate. The same subject was further explored by Kekelidze et al. (309). Teisseire (593) found 25% hydrocarbons and 35% cineole in the oil. A study of the quality of oils obtained from French and Russian varieties of lavender and lavandin indicated t h a t the best lavender oils were obtained from the Russian varieties Stepnaya, Gornaya, and Record, and the French Barreme, as reported by Staikov and Chingova (563). Peyron and coworkers (467) identified and characterized by synthesis some sesquiterpene hydrocarbons in lavender and lavandin oils. Vlakhov et al. (643), starting with 140 kg of Bulgarian lavender oil, separated a residue of 7.7 kg which consisted primarily of sesquiterpene hydrocarbons, most of which were identified. Peyron and Benezet ( 4 6 6 ) demonstrated the existence of n-hexyl butyrate in lavender and lavandin oils. d-7methyl-y-vinylbutyrolactone was found in lavender oil to the extent of 0.01% by Klein and Rojahn (309). The use of double-programmed gas chromatography for the analysis of lavender oils was demonstrated by Mazor and Takacs (383). Staikov and Chingova (561) studied the changes in oil content and composition during the growth and storage of lavender. Vinot and Bouscary (637) explored the relation between the quality of lavender oils and the botanical and genetic origin of the plants. Steltenkamp and Casazza (568) isolated 48 components of lavandin oil, 22 of which had not been previously reported. They found t h a t commercial lavandin oils were often adulterated with terpenes and 3,5,5-trimethylhexanol and its acetate. Lorincz and coworkers (356) reported variations in the oils from different plants which confirmed the plant morphological differentiation. Infrared studies of lemon oil conducted by Guenther (106) clearly pinpointed the oxidation products, such as trans-carveol, carvone, and limonene epoxide, in deteriorated oils. A gas chromatographic examination of Spanish lemon oils, using a glass capillary
column, was conducted by Goretti et al. (188).The components of Italian lemon oils were tabulated by Pennisi and D i Giacomo (458). They reported finding more than 11% 7-terpinene. Platt (472) patented a fractionation process to improve the flavor of lemon oils by removing 7-terpinene and p-cymene. Ikeda et al. (261) obtained a patent for a chromatographic method of removing 7-terpinene. MacLeod and Buigues (362) distinguished lemon and lime oils from other citrus oils by a two-dimensional thin layer chromatographic technique. MacLeod and coworkers (363) also identified 40 components of lemon oil, separated with a very efficient Apiezon L open tubular column, by comparison of mass spectra and retention times with those of known compounds. Citral was determined in lemon oil by Calapaj and Sergi (78), who used a spectrophotometric method based on reaction with nicotinic acid hydrazide. The terpene hydrocarbons from the oil of Libanotis transcaucasica were identified by Borovkov and Petov (63). The chemical transformations which may occur when expressed lime oil is distilled from, or kept in contact with, lime juice were studied by Slater and Watkins (551). Talalaj (586) found t h a t the physical properties of lime oil from Ghana were similar to those reported for West Indian oils. Strickler and Kovats (579) characterized two monoterpene oxides from distilled lime oil, and Stanley and Vannier (566) isolated 10 psoralens and coumarins from expressed lime oil. Several essential oils obtained from livermosses were examined with gas and thin layer chromatography by Huneck and Klein (255). A mandarin oil of assured purity was subjected to a thorough analysis, using Apiezon L and Carbowax 20 columns, by D'Amore and Calabro (111). Many terpenes, sesquiterpenes, and oxygenated compounds were identified and quantitatively estimated. Oils of marjoram distilled from seeds, buds, flowers, or stems, as well as from plant material from six countries were found, in a n investigation by Lossner (357),to have similar qualitative chemical compositions, though the quantitative compositions varied. The chemical composition of oil of matsubusa mas explored by Morikawa et al. (398). Three kinds of Mentha oils, hi. piperita, M . pulegium, and M . crispa, were analyzed with gas chromatography and compared by Premru and Sirec (476). The oil from a hybrid of Mentha sachalinensis and M . incana was analyzed by Nikolaeva (434).It crystallized almost completely a t 19 "C and had a free alcohol content of 77.8y0. Hefendehl (223) identified 20 components in oils of Mentha aquatica and traced their VOL. 41, NO. 5, APRIL 1969
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occurrence in various parts of the plant. T h e physicochemical characteristics of oil of Mentha arvensis cultivated in the Tarai region compared favorably with those of oils from Japan, according to Dimri (141). Khrimlyan ( S O 4 found 21 chemical types of essential oils from 10 species of wild Caucasian Mentha, and speculated as to the reason for this phenomenon. Montes and Mizrahi (396) examined the oils of Menthacitrata, M . rotundifolia, and M . canadensis. Two new essential oils from winterhardy hybrids of Mentha citrata were analyzed by Todd and bZurray (612). One was lavender-like with a sage undertone, the other was a lavenderbergamot type, also reminiscent of sage. The biosynthesis of oxygenated monoterpenes in mint was studied with the aid of radioactive tracers by Hefendehl et al. (226),and Gulati (207) examined oils from Mentha sylvestris and Mentha longifolia. Essential oil from Melaleuca leucadendron grown in Ghana was investigated by Talalaj (585),and its physicochemical properties were given. Sood (555) compared the yields and the oils obtained from trees of different ages. Older trees, past 20 years of age, gave a low yield of oil. The oil of Meum athamanticum was found by Stahl and Bohrmann (559) to consist chiefly of three phthalides. The biosynthesis of essential oil componentsin Monarda punctata was studied by Scora and hlann (534). Scora (532) also steam-distilled and chromatographed the essential oils from the leaves of 20 varieties of the genus Monarda. Essential oil characteristics were proposed as a means of classification. The acidic and phenolic components of the essential oil of mulberry leaves were identified by Yamazaki (667). A significant compound in the aroma of mushroom, the volatile lenthionine, was isolated and characterized by K a d a and coworkers (645). Infrared and NMR spectra of mustard oil oxides and sulfides were utilized to elucidate their structures by Paranjpe and Gosavi (455). Rosebrook and Barney (498) proposed a method for the determination of volatile isocyanates in mustard seed, which was said to be more reliable and more rapid than either the A.O.A.C. or the A.S.T.A. method. Chatterjee and Pruthi (94) developed a simple test for the detection of taramira oil in mustard oil. Ettlinger et al. (155) described a new mustard oil, veratryl isothiocyanate, from Neliophila longifolia. The characteristics of oil of Myrrhis odorata were related by Gertig and Pic (180). The oil contained anethole but no menthol. The physicochemical properties and major components of Myristica oil from the Ilataya district of Kerala were 46 R
ANALYTICAL CHEMISTRY
ascertained by Itty and Nigam (266). Jatamansi oil from the roots of Nardostachys chinensis was investigated by Schulte and coworkers (626), who identified many components, including a new sesquiterpene ketone, nardosinone, but did not find maaliol, 8-maaliene, or jatamansic acid which had been reported by others. Sastry et al. (515) reported finding and determining the structure of three new sesquiterpenoids in oil of Nardostachys jatamansi, nardol, calarenol, and nardostachone. They subsequently further clarified the steric structures of calarenol and nardostachone (516, 517). The identification of several new sesquiterpenes from Neolitsea zeylanica and the assignment of their chemical structures was accomplished by Joshi and coworkers (276-278). The sesquiterpene hydrocarbons of opoponax oil were investigated by Nigam and Neville (429) and by Regan and Andrews (489), who identified asantalene and a-bisabolene. After a detailed analysis of the quantitative composition of bitter orange and sweet orange oils, Calvarano (81) concluded that the adulteration of the bitter oil with sweet orange oil may be suspected if certainratiosof constituents fall outside specified limits. The major components of the oils from several strains of oranges were identified by Maekawa et al. (364). Hunter and Brogden (256) isolated and identified 17 paraffins from the waxes in Valencia orange oil. Over 100 compounds were detected and many identified from the volatile essence of Valencia orange juice by Schultz et al. (527). Using a combination of modern techniques, Teranishi et al. (602) analyzed the volatiles from orange oil and established the structure of several. 310shonas (400) identified 6-methyl-5hepten-2-one a n d piperitenone by mass and infrared spectrometry. Wolford and Attaway (6%) used flame ionization and electron-capture detection systems to analyze and compare the orange flavor volatiles from oils and juices. Mannheim et al. (S7S) evaluated the orange aroma obtained from juice by a new vacuum-stripping method. Many components of the cold-pressed oil of summer orange were separated and identified by Ohta and Hirose (442). Compounds in this oil were also identified by Kadota and Nakamura (284) using thin layer chromatography, and by Okada and Takamura (446) using gas chromatography. Origanum oils from Greece, Turkey, and Spain were characterized according to variation in their chemical composition by Calzolari and coworkers (85). I n further analyses along the same lines, Pertoldi Marletta and Stancher (462) gas chromatographed oils received from rliilan firms and one from Grasse. Dif-
ferentiation of the oils was based on their percentage content of p-methylcumene, 2-methy1-5-isopropylpheno1, and 2-isopropyl-5-methylphenol. Stancher and Pertoldi Marletta (564) continued this study on nine additional originum oils, bringing the total number of components identified in these oils to 28. The yield of oilfromOriginum vulgare and Tencrium chamaedrys grown a t various altitudes in Yugoslavia was assayed by Corovic et al. (109). Brieskorn and Brunner (67) identified many components in the oil of Origanum vulgare, including six sesquiterpenes hitherto not reported in this oil, but found neither thymol nor carvacrol. They also investigated the composition of oil of 0. maru. The oil of Origanum heracleoticum was analyzed by Staicov and coworkers (561). The fragrant constituents of Ostmanthus fragrans from Japan were isolated and identified by Sisido et al. (548). The volatiles from the same botanical grown in China were found by Sisido et al. (549) to be very similar to those from the Japanese plant. The volatile oil from Ottonia vahlii was studied by Pinder and Price (470). The essential oil of paprika was subjected to thin layer chromatography by Tatar (592). p-Mentha-l13,8-triene was identified in oil of parsley leaves by Garner0 et al. (176). Hydrocarbons in patchouli oil were isolated and characterized by Tsubaki et al. (619). From the standpoint of comparative biochemistry, two pennyroyal oils from Mentha pulegonium and M . gattefossei were considered to be similar by Fujita and Fujita (170). The oil of Mentha arvensis var glabrata was found by von Rudloff and Hefendehl (503) to consist of 80 to 90% d-pulegone and smaller amounts of many other compounds. Similarly, Fujita and Fujita (169) found 71.2y0pulegone and many other components in oil of Mentha gattefossei. Schnelle and Hoerster (522) reported that the oil from Mentha repuieni also is similar t o that from pennyroyal, M . pulegium. The oil of Peperomia pellucida mas examined by Oliveros-Belardo (448) who identified a number of its components including 2,4,Mrimethoxystyrene. The major compounds in the sesquiterpene hydrocarbon fraction of oil of black pepper were identified by Muller and Jennings (404). The most reIiable method for the analysis and evaluation of peppermint oils, according to Goryaev et al. (193), was gas chromatography. Details were given of a procedure by which all components may be quantitatively assayed. Kasimovskaya et al. (297) described two essential oils obtained from two new varieties of peppermint, and studied
the relation between oil quality and treatment of the plants. The biogenesis of terpenoids in Mentha piperita was studied by Battu and Youngken (35). Vlakhov et al. ( 6 4 1 ) r e p o r t e d t h e identification of the sesquiterpene hydrocarbons from Bulgarian peppermint oil, and the structure of two which had not been reported before, d-6-cadinene and 1-e-bulgarene, were elucidated by Vlakhov and others (640). Vlakhov and Ognyanov (642) also established the structure of another new sesquiterpene with three double bonds from the same oil. Katsuhara et al. (299) isolated and determined the structure of two new cyclic diols from ,Miteham peppermint oil. Goryaev et al. (192) investigated the chemical composition of the oil from peppermint of the new variety, Prilukskii 6. Hefendehl (224) isolated peppermint oil from the external leaf glands only, and showed t h a t this oil is identical to the one obtained by steam distillation of the entire plant. Rothbaecher and coworkers (500) identified a number of components in Romanian peppermint oil. The sesquiterpenes in peppermint oil were also investigated by Katsuhara et al. (SOO), who identified many compounds including S-guaiazulene. A hybrid of Perilla nankinensis and P . frutescens gave an essential oil which Fujita and Ueda (174) analyzed and found to contain about 50% maginata ketone rather than perilla aldehyde. Reexamination of the same oil by Fujita et al. (171) resulted in more detailed knowledge of its composition. The sesquiterpene alcohols isolated from oil of Perovskia abrotanoides were identified and characterized by Serkebaeva et al. (537).They also determined in detail the quantitative composition of the oil of Perovskia scrophulariaefolia (536). The content of oil in various parts of the plant Peucedanum cervaria and from fresh and aged plant material was determined by Krupinska and TVojterska (331). Kozhin and Sorochinskaya (32.4) detected, in the oil from the fruits of Peucedanum palustre, 957, d-limonene as well as a number of other terpenes. From the essential oil of Podocarpus dacrydioides, Corbett and Smith (103) isolated and determined the structure of s e h - 11-en-4-a-o1. The sesquiterpene hydrocarbons in Bulgarian pine oil were identified by Tsankova and Ognyanov (617). The physical properties and percentage content of certain terpenes were determined for the oils from four Turkish pine species by Okay (447). Pentegova and Dubovenko (459) established the structure of d-7-murolen, a sesquiterpene hydrocarbon isolated from P i n u s sibirica. Pentegova et al. (460) also proposed a structure for sibirene, another sesquiterpene from the same oil. The
isolation, chemistry, and biosynthesis of terpenes from Pinus silvestris were discussed by Westfelt (659). H e described the identification of b-copaene and p-ylangene and the structural elucidation of a-longipinene, all isolated from Swedish sulfate turpentine and the wood of Pinus sylvestris (657, 658). From the same source, the major sesquiterpene alcohol was identified and characterized by Kolbe and Westfelt (314) as copaborneol. Juvonen (680) used correlations in seasonal variations of individual components in oil of Pinus silvestris t o suggest terpene biosynthetic pathways. Bardyshev et al. (26) distinguished two biological forms of Pinus silvestris by the composition of their turpentine oils. I n one type, the content of A-3-carene was high, 20 to 45%; in the other, no more than 3y0, The mass spectra of geraniol and other alcohols present in rose oil were obtained by Timanovich (609). Biosynthesis of terpene alcohols in isolated rose petals was demonstrated with radioactive tracers and gas chromatographic analysis by Paseshnichenko and Guseva (454). Gusevaet al. (213) also developed a photocolorimetric method for determining acyclic terpenes in aqueous distillates of rose oil. The ketones in wax from rose concretes were separated by St o y a n o v a- I v a nova and c o mo r k e r s (572). Rollet and Monghal (497') concluded, a f t e r gas chromatographic analysis of pentane extracts from distilled rose water, t h a t their composition was highly heterogenous. Subsequently, Rollet et al. (496)identified phenylethyl alcohol and citronellol among the components of rose water. Buechi et al. (7'2) confirmed the structures of rosefuran and dehydrollsholtzione by their specific syntheses. Hallaba and Raieh (214) described the photoinduced labeling of Bengal rose n-ith 1 3 1 1 . Igolen (260) related in detail many aspects of the Turkish rose oil industry, including its chemistry and analysis. A new microtechnique for direct gas chromatography of essential oils from fresh plant samples mas applied to rosemary by Karlsen and Baerheim Svendsen (294), and was used to determine changes in the terpene hydrocarbons a t three stages of development. Crabalona (111) detected 1-methyl jasmonate in the oil of Tunisian rosemary. Saleh and Mohamed (512) prepared and analyzed rosemary oils from seven plant samples grown in the United Arab Republic. The oils appeared to be of good quality. The essential oils of rue from various plant parts and a t various stages were examined by Kubeczka (332),mho identified many components quantitatively, but could find no relation between fatty acid degradation and methyl ketone synthesis. Oil from mature black seeds of rue contained mainly undecan-2-one and undecan-2-01. Kubeczka (333)
recommended a direct gas chromatographic procedure for detection of volatile and labile compounds. The procedure uses no solvent vacuum and employs an inert carrier gas, with liquid air as coolant. Detailed biogenetic studies are described. The properties of 46 fractions of sandalwood oil distilled from the wood over a 132-hr period were determined by Dwivedi et al. (149). Optical rotation varied from -14.2 t o $28.5" and other properties also showed great divergence. Lewis and coworkers (346) confirmed the structure of a-santalol by a complete synthesis. The characteristics of the oils from three Perugian salvia species were reported by Cenci and Calvarano (88), who also identified many of their components. An oil from summer savory, Satureia hortensis, was distilled by Manjanatha et al. (369). Its physicochemical properties and carvacrol content were given. An essential oil containing the aroma of sesame oil was steam-distilled by Yamanishi and coworkers (666) and the compounds responsible for the aroma, most of which were carbonyl compounds, were identified. I n the oil of Seseli indicum, Dixit et al. (142) identified seselin, 1-p-selinane, and other constituents. Many components of the oil of Severinia buxifolia were isolated and identified by Scora (533). =I volatile oil from the fruits of Siparuna nicaraguensis was analyzed by Manjarrez and hlendoza (372). Its properties and major constituents were reported. The constants of oil of Sphaeranthus indicus distilled by Nigam and Rao (432) differed somewhat from those obtained by Baslas. The quantitative composition of the oil was ascertained. The percentage content of some components, including carvone, in Indian spearmint oil was estimated chemically in two ways by La1 and La1 (339). Agreement between the two methods was good. Virmani and D a t t a (639) summarized present knowledge of the properties, composition, and production of spearmint oil. The oils from spearmint varieties grown in different parts of Europe were evaluated by Zologtovich (670). The best oils were obtained from two varieties grown in Italy and one grown in Germany. The monoterpene hydrocarbons in Norwegian spruce needle oil were determined, using a direct gas chromatographic microtechnique, by Karlsen and Baerheim Svendsen (292). Juvonen and Lako (281) reported t h a t the quantity of oil is much greater in the needles of the upper branches than it is in the lower branches of the same spruce. I n a study of oils from North American spruces, however, von Rudloff (501) VOL. 41, NO. 5, APRIL 1969
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found relatively little difference in yields and no qualitative difference in oils obtained from different parts of the same tree, or from trees of different ages. His technique made it possible to analyze the oil from one single needle. The composition of the oils from 12 species of spruce was reported by von Schantz and Juvonen (521). The purity of oil of Tagetes erecta was simply but effectively ascertained with a thin layer chromatographic technique by Fagoaga Schenkel and Canto dos Santos (158). An Indian tangerine oil was examined chemically by Chaliha et al. (91). Its properties and some of its components mere determined. I n an investigation into the sesquiterpenes found in tansy oil, Stahl and Scheu (560) revealed the presence of chamazulene and epoxydihydrocaryophyllene. They also discovered a new sesquiterpene with a lemonlike odor a t concentrations from 65 t o 71.3g”, in the essential oil of some plants of Chrysanthemum vulgare. These plants were therefore judged to constitute a separate chemical race. Czuba and coworkers (115) studied the variations in the composition of tansy oil during one year of growth. Four compounds not previously reported in the volatile oil from black tea were identified by Illueggler-Chavan et al. (402): 1-penten-3-01, trans-2-hexen1-01, a-terpineol, and pionone. Gas chromatography following preliminary preparative gas chromatography was employed. Bricout etal. (66)additionally identified trans-2-penten-1-01, l-ethyl-2formylpyrrole, 2-trans-4-cis-heptadienal, phenylacetonitrile, methyl benzoate, 2-phenylbut-2-ena1, and a complex lactone. Saijo and Kuwabara (505) observed changes in the concentration of volatile components during the fermentation of black tea. Gogiya (186) examined oils from fresh, withered, fermented, and dried Russian tea leaves by thin layer chromatography. Many terpenes and alcohols were identified. Gogiya (185) also identified many organic acids from the same oils. Kozhin et al. (325) identified 17 volatile components in the oil of Georgian tea, includingenanthaldehyde, n-amylalcohol, and a-terpineol, which had not been found before. Gas chromatographic and thin layer chromatographic analytical procedures were suggested for thyme oil by Deryng et al. (125), and standards were set to assure compliance with the quality of oil required by the Polish pharmacopeia. Kalker (647) described qualities, yields, and characteristics of various thyme oils. Damjanic and coworkers (117) compared the yield and composition of thyme oils recovered by steam distillation and adsorption on talc and silica. Granger et al. (198) found r-terpinene 48 R
ANALYTICAL CHEMISTRY
in thyme oil. The loss of essential oil and the changes in its character with drying a t various temperatures were studied by Kolodziejski and coworkers (316). A gas chromatographic determination of thymol and carvacrol in thyme oils was compared with four spectrophotometric methods by Zwaving (671). Falchi (159) obtained the physicochemical d a t a of Sardinian Thymus herba-barona oil. The compositions of the oils from 10 varieties of Thymus serpyllum were tabulated by Schratz et al. ( 5 2 4 , who also listed the substances detected in 188 samples of Thymus pulegoides and 93 samples of T. marschallianus. The headspace volatiles from tobacco were collected by a simple method developed by Swain et al. (581). I t was illustrated by typical results showing the presence of a t least 35 components in the concentrated vapors from Turkish tobacco. Ognyanov and Ivanov (441) discussed the chemistry and preparation of tobacco products for use in perfumery. Indian turpentine oil from Pinus longijolia was described by Verghese (630), and Lozzi (559) related the properties and characteristics of the various types of turpentine oil produced in the Soviet Union. Methods for the estimation and identification of turpentine in complex mixtures were given by Saxton (518). Westfelt (656), by chemical and spectral studies, elucidated the structures of two sesquiterpenes from Swedish sulfate turpentine. Numerous volatile components of Bourbon vanilla beans were identified by Bohnsack (60). The neutral fraction of Indian valerain root oil was examined by Joshi et al. (279), and many components including patchouli alcohol and niaaliol a e r e identified. The structure of valerianol, a sesquiterpene alcohol of eremophilane type from valerian oil, was established by Jommi et al. (269). Hikino et al. (242, 243, 260-262) published papers dealing, respectively, with the structures and configurations of kessanol and 8-epikessanol, kessane, fauronyl acetate and cryptofauronol, Taleranone and derivatives, and 6kessyl ketone and B-kessyl alcohol. A11 of these were isolated from valerian oil. The vetiver oil obtained by Cardoso do Vale and Proenca da Cunha (87) from Veteveria nigritana differed from the oil of V . zizalziodes be being laerorotatory, and in its chemical composition. The structures of vetiver oil components were elucidated by Jentsch and Treibs (267, 268) who clarified the tertiary vetivenols and also reported that primary alcohols could not be found in a commercial vetiver oil; Kigam et al. (430) who isolated and characterized the sesquiterpene primary alcohol, khusenol; Nigam and Komae
(426) who isolated and described two acids; and Nigam et al. (426) who clarified the structural relationships between tricyclic sesquiterpenes in the oil. I n addition to these investigations, Komae and Nigam (316) established the structures of khusenic and isokhusenic acids, Morikawa and Hirose (397) characterized khusimene, and Marshall and Andersen (575) deduced the structure of a-vetivone. These substances were isolated from vetiver oil. A Chinese wintergreen oil was reported by M u and Yang (401) to contain 94 to 98% methyl salicylate. From oil of wormwood, Huxtable and coworkers (258) isolated cl-isothujone by repeated fractionation. They also isolated E-thujone from Dalmatian sage oil. Australian wormwood oil was analyzed quantitatively by gas chromatography by Goryaev et al. (195) and the major portion of its composisition was determined. Bertelli and Crabtree (45) assigned structures to the isolated 3,6-dihydrochamazulene and 5,6-dihydrochamazulene from spectral evidence, and Geissman and Winters (179) deduced the structure of artabsin, a sesquiterpene lactone from wormwood oil. Bieloszabska and Sawicka (48) determined oil content, vitamin C, and bitters in wormwood herb. The physicochemical properties of oil of Xylopia aethiopica from Ghana were obtained by Talalaj (588). Components of oil of zedoary were intensively studied by Hikino et al. (244-246, 249) who established the structures of the sesquiterpenoid curcumol which has a vinylidene group, the diketones curidione and curdione, and the epoxy furanoid ketone zederone. The physicochemical properties and chemical composition of Bulgarian zdravets oil was discussed by Ognyanov and Ivanov (440). Components of the essential oil of Zingiber zerumbet were investigated by Damodaran and Dev (118-120) who completely analyzed the oil and determined the structure of the sesquiterpenoids, humulene epoxide-I, humulene epoxide-11, and d-humulenol-11.
ACIDS
General. Carboxylic acids were separated with a thin layer technique, which permits the use of solvent systems developed for paper chromatography, by Rasmussen (485),who also employed a new and convenient indicator system with high sensitivity. Salniinen and Koivistoinen (513) used gas chromatographic separation of the methyl esters of acids for their analysis. Methyl esters and glycerides of fatty acids were determined using thin layer chromatography by Ord and Bamford (449). n-Propyl esters were
utilized in the gas chromatographic determination of acids by Appleby and Mayne (8). D u t t a and Baruta (148) separated 01, punsaturated acids with thin layer chromatography. Cristofaro and Egli (113) adapted thin layer chromatographic methods t o the analysis of 2, 4-dinitrophenylhydrazones of ketocarboxylic acids, and Smith (526) explored their separation and identification with paper chromatography using papers loaded with silica gel. On this paper, the derivative of acetoacetic acid decomposed completely. Trop et al. (616) modified the ceric ammonium nitrate reagent of Buch et al. t o permit the differentiation of ahydroxy and a-keto acids and mercaptans. Berka and Hilgard (42) studied the effect of p H on the determination of tartaric and glycolic acids by permanganate oxidation. Individual Compounds. The structure of the sesquiterpenoid +longifolic acid mas established by hiehta and coworkers (385). ALDEHYDES A N D KETONES
General. The gas chromatographic separation of a wide range of carbonyls regenerated from their seniicarbazones was accomplished by Hunter and Walden (257). Crotonaldehyde and 2,4pentanedione were not regenerated. Nevskii et ai. (422) attempted the determination of carbonyl compounds with pyrolysis and gas chromatography. Grosch (602) identified many aldehydes by gas chromatography of the volatile neutral carbonyl components resulting from enzyme reaction on peas. The separation of the sun- and antidinitrophenylhydrazones of hydroxy methyl furfuryl alcohol was accomplished with column chromatography by Jlaroni and Ubertis (374). The olive oil system of separating 2,4-dinitrophenylhydrazones from citrus oils \vas compared with phenoxyethanol and the dimethyl formamide systems by Raymond (484,485), n ho also demonstrated three paper chromatographic techniques for d e t e r mining 2,4-di ni t r o p he nylhydrazones. Thin layer chromatographic separation and identification of aldehyde 2, 4-dinitrophenylhydrazones, using a special coating mixturc, was described by Bloem ( 5 2 ) . Ascending thin layer chromatography of similar derivatives on aluminum oxide was utilized by Kore et al. (318) t o analyze a complex mixture of perfume aldehydes. Kore and Ivanova (311) demonstrated a method for the thin layer chromatography of bisulfite derivatives of carbonyl compounds. The mass spectra of nine monoterpene aldehydes and ketones were obtained by von Buenau and coworkers ( 7 3 ) .
X-Ray powder diffraction data for semicarbazones of important perfume aldehydes and ketones were reproduced and the &spacings were tabulated by Meranger et al. (386). Specific colorimetric procedures using 3-methylbenzothiazolin-2-one hydrazone for the determination of various aldehydes were developed by Pays et al. (457). An improved technique for the potentiometric titration of hydrazones was proposed by Calderon and llilian (79). The oximation method was adapted b y Skvortsova et al. (560) t o the determination of ketones in the presence of keto aldehydes. A modification of the Strache method of determining carbonyl groups which eliminates errors in the measurement of the liberated nitrogen was described by Xowak (438). Errors in the determination of water content in carbonyl compounds with Karl Fischer solution Ivere largely eliminated by Beyer and Varga (46) by carrying out the titrations a t below -10 "C. Individual Compounds. The metabolism of acetaldehyde by plant tissue such as apples and oranges was studied by Fidler (161). The quantitative determination of benzaldehyde in flavors and cordials by ultraviolet spectrophotometry r m s described by Brunelle (70). The absolute configurations of camphor and camphor derivatives were confirmed by hlalkonen and Frostell (367). Methods for estimating carvone in dill oil were compared by Jonczyk (270). A simplified version of the hydroxylamine method using bromothymol blue was best. The nor-sesquiterpenoid chamaecynone, one of the first examples of a natural acetylenic terpene compound, was synthesized by Sozoe et ai. (439). thus confirming its structure. Polarographic titration of the oximation determination of citral in lemongrass oil reduced the error considerably compared with other titration procedures, according t o Shakunthala and Pathy (642). Sasaki (614) developed a method for separating the isomers of citral based on the difference in their reactivity to 1VaHS08 in acetic acid solution, and Joseph-Nathan and Manjarrez (275) evaluated mixtures of geranial and n e r d by nuclear magnetic resonance. Dmitrieva and coworkers (143) studied the stability of citral from coriander oil. The optical rotation of citronellal was discussed in detail by Sully and Wlliams (579). Chemical and instrumental evidence was used by Hikino et al. (247) to elucidate the structure of curcolone. Cyclocolorenone was identified in oil
of Boronia ledifolia by Hellyer and Lassak (227). Cyclohexanone a as determined by oximation in the presence of cyclohexane and cyclohexanol by Kratochvil and Bulusek (327). As much as 11% of p-cyclolavendulal, a new monoterpene aldehyde, was found in oil of Seseli indicum seed by Logani et al. (354). On the basis of infrared, ultraviolet, and nuclear magnetic resonance spectra, the structure of diosphenolene was deduced by S a v e s (415). Small amounts of formaldehyde in acetaldehyde were determined by Harrison (218) using reduction and gas chromatography. The mass spectrum of p-ionone and its fragmentation was discussed by Thomas and Villhalm (608). The estimation of impurities in commercial ionone by oximatioii before and after XaOH treatment was suggested by Sovikova et al. (437). Cathode ray polarography was utilized by Xaumann (413) to detect a,punsaturated ketones in methyl isobutyl ketone. The characteristics of novel oxyacetaldehydes and their derivatives were described by Kulka and coworkers (335). The structure of a-sinensal was proposed by Thomas (606). Spectrometric and chemical evidence enabled Anthonsen et al. (6) to give the structure of solidagenone. The sterochemistry of some cyclic ketones related to I-umbellulone was clarified by Gray and Smith (199). Vanillin gives a violet color with Millon reagent n-hich, according to studies by Seuzil et al. (421),is specific for o-methoxy phenols having a side chain in the para position with a carbonyl group on the first carbon. Vanillin and ethyl vanillin were estimated in chocolate with thin layer chromatography by 1-cnturini (628). a-Vetivone was assigned a structure differing greatly from that of p-vetivone by Endo and D e Mayo (152). Marshall and Johnson (376) arrived a t a structure for b-vetivone which again is different from the one previously acrepted. -1series of ketones related to substituted phenyl-4-hesanone were described and recommended for use in perfumes by ?\leerburg and Van Essen (384).
ALCOHOLS A N D PHENOLS
General. ai combination of several stationary phases for the more efficient gas chromatographic separation of aliphatic alcohols was described by Bober (53). Thin layer chromatography was employed by Nobuhara (435) t o analyze mixtures of saturated and unsaturated straight-chain alcohols. VOL. 41, NO. 5, APRIL 1969
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The R, values resulting from the paper chromatography of many isomeric monosubstituted phenols with different solvents were tabulated by Gumprecht and Schwartzenburg, Jr. (210). Primary and secondary aliphatic alcohols were converted to the corresponding alkyl nitrites, Lvhich were thereupon determined spectrophotometrically by Grechukhina and Nesmelov (200). Belcher et al. (41) found a spectrophotometric method based on the 3,s-dinitrobenzoates t o be best for submicrodetermination of alcohols, and a titration method t o be best for acidic hydroxyl compounds, such as phenols. A novel method for the identification of alcohols in complex mixtures was developedby LarkhanandPagington (341) based on the gas chromatography of their chloroacetates. The determination of alcoholic hydroxyl compounds by the succinic anhydride method was explored in detail by Karang and Llathur (410). and the phthalization method n-as investigated by Nigam and coworkers (424). Pyruvyl chloride 2,B-dinitrophenylhydrazones were employed for the identification and characterization of primary, secondary, and tertiary alcohols in a new method devised by Schwartz and Brewington (629). I n further explorations of this technique they described quantitative column and qualitative thin layer chromatographic procedures for separating these derivatives (531). Severin (539) produced color tests which distinguish primary, secondary, and tertiary alcohol reaction products with S-chloro, bromo, and iodosuccinimides. Individual Compounds. The structure of alcohol rl, a new sesquiterpene alcohol, was derived by Tamburrini, Jr. (591). K a t e r in butanol was estimated with dielectric constant measurements by Tsellinskaya and Ivanova (618). Levchenko et al. (343) separated the products of the butyl alcohol oxosynthesis by gas chromatography. p-bisabolol, a new sesquiterpene alcohol from cotton essential oil, was characterized by hlinyard and coworkers (389). Mass spectra and a n ion fragmentation scheme were presented for eight caranols by von Buenau et al. ( 7 4 ) . The configuration of “carquejol” and the preferred conformation of o-neoisomenthol were deduced by Thomas (607). I n a total synthesis of a-caryophyllene alcohol, Corey and Kozoe (107) confirmed its structure. The structure and absolute configuration of cedrelanol were elucidated in two papers by Smolders (553, 554). Citronellol was assayed by Adcock and Betts ( 2 ) in the presence of geraniol in oils and chemical mixtures with thin layer chromatography of the trimethyl50
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ANALYTICAL CHEMISTRY
silyl ethers of the alcohols. Secondary citronellols (elgenols) and their derivatives were discussed by Naves (416). Barton and Werstiuk (28) established the constitution and stereochemistry of culmorin. d titration with Bu4NOH of eugenol in clove oil in a pyridine solution vias compared with other methods of analysis by Covello et al. (110) and was found to be in good agreement. Karawya and K a h b a (291) developed a colorimetric method to assay eugenol in essential oils. Geraniol and citronellol ivere separated with thin layer chromatography by Kore and coworkers (319). The conformation of farnesol was confirmed with a stereospecific synthesis by Corey et al. (106). Chirality of 9-hydroxy-p-menthane compounds mas discussed by SchulteElte and Ohloff (526). Changes in linalool after irradiation n-ere studied by Sugiyama et al. (578). Menthol and triacetin were determined simultaneously by Kaburaki and coworkers (282), using gas chromatography. Tucker and Ogg (621) used gas chromatography and a colorimetric method to assay menthol in cigarette tobacco filler. When these methods were tried by 13 different labs, Tucker (620) reported good agreement. The analytical composition of natural and synthetic menthols was related to qualit y and mildness by Morishita et al. (399). Godunova et al. (184) illustrated the chromatographic analysis of mixtures of stereoisomeric menthols and menthones. Detailed evidence for the interrelation betiveen monogynol and steviol and the reverse conversion of the stachene skeleton to the kaurene skeleton was presented by Hanson (216). 1-Octen-3-01 was isolated from Psalliota campestris by Freytag and Key (167). Oplodiol, a new sesquiterpene alcohol. was separated from Oplopanazjaponicus by l l i n a t o and Ishikawa (388). and Mathur et al. (380) characterized an oxidodiol from Zanthoxylum rhetsa. A simple and rapid method for detecting small amounts of phenol in benzyl salicylate consisting of a spot test on a thin layer of silica was described by Bore and Gataud (61). Challen and Kucera (92) discussed phenolic constituents and their distribution and biosynthesis. The absolute configuration of selin11-en-4a-01. juniper camphor, and the structure of intermediol were established by Chetty et al. (95). Infrared spectra of 141 highly purified acyclic, monocyclic, and bicyclic terpene alcohols and their derivatives, mostly neiv t o the literature, were presented by Mitsner et al. (391). Infrared spectra of highly purified
terpinenols were also obtained by Mitzner and coworkers (390). Verghese (629) discussed the occurrence, properties, structure, and identification of 4-terpinenol.
ESTERS A N D LACTONES
General. Monoterpene esters were characterized m-ith the use of gas and thinlayer chromatography by Ter Heide (599) who correlated Rf values with their structures. Low molecular weight carboxylic acid esters were determined by Krasnova et al. (326) by absorption spectra in the visible region, after having been converted t o hydroxamic acids which form red colors with ferric ions. Xuclear magnetic resonance spectra \\-ere employed by Diaz et al. (129) to elucidate the structures of azulenogenic lactones. Herz and Kagan (234) used Horeau’s method of asymmetric esterification to determine the absolute configuration of hydroxylated sesquiterpene lactones. Sfiras and Demeilliers (541) found that dimethyl sulfoxide increased the rate of saponification in the more stable esters. Cedryl acetate was used as a n example. Molecular structure and odor of certain monosubstituted and disubstituted lactones and tetrahydrofurans were correlated by Dashunin et al. (123). Individual Compounds. The absolute stereochemistry of d-abscisin I1 about its center of asymmetry was deduced by Cornforth et al. (108). Acroptilin, a new sesquiterpene lactone from Acroptilon repens mas isolated and characterized by Evstratova and coworkers (157). .Ilbiocolide, a new germacranolide from Jurinea albicaulis, was described by Suchy et al. (577). Revised structures for archangelin and perezone were proposed by Thalacker (606). Four structures, two of which mere more probable, were proposed for the sesquiterpene lactone, badkhysinin, by Kir’yalov and Serkerov (308). The occurrence of sesquiterpene lactones in Compositae and their chemotaxonomy were discussed by Herout (231). The geometry of the double bonds in costunolide was investigated by Suchy et al. (575). Alicroquantities of coumarin were determined with a n impregnated paper method by Kielcsewski and Kurnatowski (305). Pate1 and Bafna (465) used column chromatography t o separate coumarins. Hata and coworkers (220) isolated neiv coumarins from Angelica anomala and A. cartilaginomarginata, and Estevez and Gonzalez Gonzalez (154) discovered new coumarins from
the Rutacae, using a new paper chromatography technique. Deacetoxymatricarin from Achillea santolina showed trans-axial conformations a t positions 5,6- and 6,7- and pseudoaxial conformation on the methyl group a t C-11, according to Linde and Ragab (350). Ethyl acetate and the impurities resulting from its synthesis were analyzed by Druskina and Shaposhnikov (147). Two sesquiterpene lactones isolated from Encelia jarinosa were assigned structures by Geissman and RIukherjee (178). Naturally occurring terpenoid furanolactones were discussed by Chakrabartty (90). Gafrinin, a sesquiterpenoid lactone from Geigeria africana, was studied by Anderson et al. ( 4 ) , who proposed a revised structure for the compound based on chemical and spectrometric evidence. The structure of heliangine, a nerv type of sesquiterpene lactone, was shon-n by Iriuchijima et al. (263). Ivalbin, a modified guaianolide from Iva dealbata, was isolated, and its structure mas established by Herz et al. (233). The structure of ivangulin was also clarified by Herz et al. (236). Methyl anthranilate and dimethyl anthranilate were assayed in natural and synthetic mixtures by Vernin and Vernin (634), who employed thin layer and gas chromatography. The constitution and absolute configuration of onopordopicrine were established by Drozdz et al. (146). Pelenolides, a ne\%-group of sesquiterpene lactone germacranolides, ivere clarified as to constitution and configuration by Suchy ct al. (576). Sieversinin, a new sesquiterpenic lactone, was isolated and characterized by Sazarenko and Leont’eva (418). Spathulin, isolated from various Gaillardia species, n as characterized by Herz et al. (235). Tubiferine wasstructurally elucidated by Bermejo et al. ( 4 3 ) . Vermeerin, a sesquiterpenoid dilactone from Geigeria africana, was isolated and its structure n-as established by Anderson et al. ( 5 ) . e/-
ETHERS, OXIDES, A N D PEROXIDES
General. The isomerization of epoxides on active alumina during chromatography was studied by h’igam and Levi (427). The main products were a,@-unsaturatedalcohols, but side reactions were observed in some cases. Individual Compounds. Barrett and Buechi ( g 7 ) clarified thestereochemistry of a-agarofuran by a total synthesis. Commercial anetholes mere examined with gas chromatography by ViettiMichelina and Pilleri (635,636).Benzyl
ether was identified as a component of the anethole fraction from pine oil. Jonczyk (271) compared methods for the determination of anethole and found the HI method for methoxy assay to be the most dependable. New poly yne epoxides were discovered by Bohlmann and Moench (55) in Centaurea deusta and their structures were established. ,Menthofuran was assayed spectrophotometrically by Tezuka and coworkers (604). Monoterpene epoxides were studied by Suzuki et al. (580), who especially elucidated the structure of (Y- and 8-3,4epoxy caranes. Traces of peroxides in ethers were spectrophotometrically determined by Griffiths (201), who utilized the absorbance of 13- after reaction with excess quarternary ammonium iodide.
TERPENES A N D HYDROCARBONS
General. The gas chromotography of sesquiterpene hydrocarbons was illustrated by Kigam and Levi (428). Wenninger et al. (656) showed t h a t the gas chromatograms of the sesquiterpene hydrocarbon portion of various oils such as patchouly, ylang ylang, and gurjon balsam oils were characteristic of the particular oil, and also reported the I R spectra for 12 sesquiterpenes. The use of combined gas chromatography and mass spectrometry in the quantitative analysis of hydrocarbon mixtures containing components such as diterpene hydrocarbons inseparable with gas chromatography alone was described by Appleton and McCormick ( 9 ) . Gas chromatography, together with ORD, I R , KMR, and mass spectrometry, was employed by Daloze (116) for the elucidation of the chemical structures of triterpenes. The separation and analysis of cis, trans-isomeric olefins on activated alumina gas chromatographic columns was demonstrated by List and coworkers (352)* Mass spectrometric studies of diterpenes, conducted by Enzell and Ryhage (153), yielded structural information from both deuterated and nondeuterated positions. Efremov (151) obtained the low voltage mass spectra of the bicyclic terpenes, pinene, carene, and camphene. Audier et al. (19) studied the effect of the aromatic nucleus on the fragmentation mass spectra of tricyclic triterpenes. Audier et al. (20) also investigated the effect of double bonds on diterpene fragmentation. High resolution infrared spectra were presented by Kenninger et al. (654) for 36 naturally occurring sesquiterpene hydrocarbons. A method to estimate the number and nature of quarternary methyls in
isoprenoids, especially sesquiterpenes, based on the Kuhn-Roth C-Me estimation, was proposed by Pansare and Dev (458). A number of specific color reactions of terpenic dienes mere described by Matawowski (379). The biological significance of terpenes in plants was explored by Goodwin (187). Specific biological effects of a number of compounds were cited as illustrations. Individual Compounds. The structure of l-aromadendrene, a tricyclic sesquiterpene, was established by Buechi and coworkers (71). The sesquiterpenes from Athrotazis selaginoides were isolated and identified by Restfelt and Kickberg (660). Azulene in the oil of Pimpinella nigrae was identified by GaFvlowska (17 7 ) . The stereochemistry of cis-p-bergamotene was confirmed through synthesis by Gibson and Erman (182). X-Ray analysis conducted by Linek et al. (351) confirmed the structure of I-e-bulgarene. -4 stereospecific total synthesis of cadinene dihydrochloride was reported by Gunay (211). Connell et al. (99) investigated the structure of d-cadinene from various sources. I t was suggested t h a t the compound from Mentha piperita should be called w-cadinene. Herout and coworkers (232) revised the suggested structure for cadinene. Stereochemistry in the carane series was discussed with respect to chemical derivatives and N M R spectra by Teisseire et al. (595). Hydroborating A3carene, Brown and Suzuki (69) proposed configuration assignments for the derivatives. The stereochemistry of the cedrane series was studied by Teisseire et al. (596). Chamigrene, a sesquiterpene hydrocarbon with a novel carbon skeleton, from Chamaecyparis taiwanensis was isolated and characterized by Ito et al. (265). The separation and identification of the sesquiterpene hydrocarbons from oil of copaiba balsam and oil of cedarwood were reported by Kenninger and comorkers (653). The absolute structures of a- and p-himachalene were determined by Joseph and Dev (273, 274) who prepared derivatives for confirmation. Pandey and Dev (451) also established the structure of ar-himachalene and himachalanes. The stereochemistry of 1-kaurene was clarified by Hanson (217 ) . The first tetracyclic sesquiterpene, longicyclene, was isolated by Kayak and Dev (417) from P i n u s longifolia. Nuclear magnetic resonance spectrometry was utilized by Noen and Makowski (393) to determine structural isomers of 2-substituted 5-norbornenes VOL. 41, NO. 5, A P R I L 1969
51 R
which had been separated by gas chromatography. Stereochemical studies in the pinane series were conducted b y Teisseire et al. (594, 597), and Stassinopoulos (567) explored the structure determination of a-pinene dimers. Tyihak andVagujfalvi (623) described a thin layer chromatographic method for the separation and identification of proazulenes. The structure of sesquicarene, isolated from theoilof Schisandra chinensis, mas determined from hydrogenation reactions and spectral data by Ohta and Hirose (444). The new sesquiterpene, sesquiguavene, isolated from the leaves of guava was partially characterized by Bhati
file, as determined by the nature and position of the functional groups, is a prime factor in odor intensity and quality. Many polyacetylene compounds were isolated from plant materials and characterized by Bohlmann and coworkers (64, 56-59). +Icolorimetric determination of volatile sulfur compounds based on reaction with .V,S-dimethyl-p-phenylenediamine was developed by Maier and Diemair (366). Prinzler et al. (479) analyzed mixtures of organic sulfur compounds with adsorption and distribution thin lager chromatography.
(29) Basker, H. B., Amer. Perjum. Cosmet., 82, (7)) 33 (1967). (30) Baslas, K. K., Perjum. Essent. Oil Rec., 58, 437 (1967). (31) Zbid., p 782. (32) Zbid., 59, 12 (1968). (33) Baslas, R. K., Baslas, K. K., ibid., n 11n +-”.
(34) Zbid., p 180. (35) Battu, R. G., Youngken, H. W.,Jr., Lloydia, 31, (l),30 (1968). (36) Bawdekar, A. S., Kelkar, G. R., Bhattacharyya, S. C., Tetrahedron, 23, 1993 (1967). (37) Bedoukian, P. Z., Amer. Perjum. Cosmet., 82, (4), 29 (1967). (38) Zbid., 83, (4), 27 (1968). (39) Bedoukian, P. Z., “Perfumery and Flavoring Synthetics,” 2nd ed., 420 pp, Elsevier, New York, N.Y., 1967. (40) Beets, M.G. J., France Parjums, 10, 113 (1967). 141) Belcher. R.. Drvhurst. G.. MacLITERATURE CITED Donald, A. hi.’ G., “Anal.’Chim. Acta, 38, 435 (1967). (1) Acharya, R. N., Chaubal, 11. G., (42) Berka, A., Hilgard, S., Mikrochim. J . Pharm. Sci., 57, 1020 (1968). Acta, 1966, p 164. (43) Bermejo Barrera, J., Breton Funes, (2) Adcock, J. W.,Betts, T. J., J . Chromatogr., 34, 411 (1968). J. L.. Faiardo. M.. Gonzales Gonzales. (3) Akimov. Yu. A.. Voronin. V. G.. Gaz. A., Anales Quim., 64, 183 (1968). Kromatoar.. Moscow. 3. 142 11965). (44) Berry, R. E., Wagner, C. J., Jr., (4) Anderson, L. A. P:, De Kock, W.T., Noshonas, 11. G., J . Food Sci., 32, 75 (1 Yel, IT., Pachler, K. G. R., Van Tonder, \ -967) ” - . ,. G., Tetrahedron, 24, 1687 (1968). (45) Bertelli, D. J., Crabtree, J. H., (5) Anderson, L. A. P., De Kock, W.T., Tetrahedron,24, 2079 (1968). Pachler, K. G. R., Van der Brink, C. PI., (46) Beyer, H., Varga, K., 2. Chem., 6, ibid., 23, 4153 (1967). 470 11966). (6) Anthonsen, T., McCabe, P. H., (47) Bhati, ‘A., Perjum. Essent. Oil Rec., McCrindle, R., MurrayL R. D. H., 58, 707 (1967). Chem. Commun., 1966, p 140. (48) Bieloszabska, F. W., Sawicka, W., (7) Appel, H. H., Brooks, C. J. W., Farm. Polska, 22, 278 (1966). Campbell, ll. hI., Perjum. Essent. Oil (49) Bisarya, S. C., Dev, S., Tetrahedron, Rec., 58, 776 (1967). 24. 3861 11968). (8) Appleby, A. J., Mayne, J. E. O., J . Gas (50) ‘Ibid., p 3869. Chromatogr., 5, 266 (1967). (51) Bismead, D. S.,Kratz, P. de C., (9) Appleton, R. A., McCormick, A., Choc. Confiserie Fr., 1967, (230), p 19. Tetrahedron,24, 633 (1967). (52) Bloem, E., J. Chromatogr., 35, 108 (10) Arakelyan, V. G., Sarycheva, L. S., (1968). Evdakov, V. P., Zh. Anal. Khim., 23, (53) Bober, H., Beckman Rep., 1965, (2), 109 (1968). p 17. (11) Araki, &I.,Ohara, T., Yamada, T., (54) Bohlmann, F., Kapteyn, H., Chem. Goto. R.. N i m o n Kaaaku Zasshi., 87., Ber., 100, 1927 (1967). 63 (19661’. (55) Bohlmann, F., Moench, H., ibid., (12) Ashoor, S. H., )I., Bernhard, R. A., p 1944. J . Agr. Food Chem., 15, 1044 (1967). (56) Bohlmann, F., Niedballa, U., ibid., (13) Askitopoulos, C., Znd. Eng. Chem., p 1936. Prod. Res. Develop., 6, 184 (1967). (57) Bohlmann., F.,, Rode, K. M.. ibid., (14) Atal. C. K.. Sood. N. hl.. Indian J . ‘ 1940. Pharm., 29, (2), 42 (1967) (58) Bohlmann, F., Rode, K. hI., Waldau, (15) Attaway, J. A., Pieringer, A. P., E., zbid., p 1915. Barabas, L. J., Phytochemistry, 5, 141 (59) Bohlmann, F., Zdero, C., ibid., (1f)fifi) \-l_-,. p 1910. (16) Zbid., p 1273. (60) Bohnsack, H., Riechst., Aromen, (17) Zbid., 6, 25 (1967). Koerperpjegem., 17, 133 (1967). (18) Attaway, J. A., Wolford, R. W., 161) Bore. P.. Gataud. P.. J . Chromatoor.. Douehertv. 11. H.. Edwards. G. J..’ 30, 261 (1967). J . A i r . Food Chem., 15, 688 (1967). (62) Borges del Catillo, J., Brooks, C. J. (19) Audier, H. E., Bory, S., Defaye, G., W., Campbell, hi. It.,Tetrahedron Lett., Fetizon, hl., Moreau, G., Bull. SOC. 1955, p 3731. Chim. Fr., 1966, p 3181. (63) Borovkov, V. A. V., Petov, G. M., (20) Audier, H. E., Bory, S., Fetizon, M., Khzm. Prir. Soedin., 3, 235 (1967). Anh, N.-T., ibid., p 4002. (64) Boven, RI. van, Verzele, M., Bull. (21) Baerheim Svendson, A., Karlsen, J., SOC.Chim. Belges, 77, 99 (1968). Planta Med., 14, 376 (1966). 165) Bracho. R.. Crowlev. K. J.. Phvtochemistry,’5, 921 (i966j.’ (22) Ibid., 15, 1 (1967). (23) Bahadur, R., Gupta, G. N., Perjum. (66) Bricout, J., Viani, R., MugglerEssent. Oil Rec., 57, 421 (1966). Chavan, F., Marion, J. P., Reymond, (24) Bahadur, R., Gupta, G. N., Riechst., D., Egli, R. H., Helv. Chim. Acta, 50, Aromen, Koerperpjlegem., 17, 60 (1967). 1517 (1967). (25) Bardyshev, I. I., Shashkina, ?VI.Ya., (67) Brieskorn, C. H., Brunner, H., Planta Dokl. Akad. Nauk Beloruss. SSR, 10, Med. Suppl., 1967, p 96. (6), 391 (1966). (68) Brown, C. A., Sethi, S. C., Brown, (26) Bardyshev, I. I., Zen’ko, R. I., H. C., ANAL.CHEM.,39, 823 (1967). Gorbacheva, I. V., Prokazin, E. P., (69) Brown, H. C., Suzuki, A., J . Amer. Chudnyi, A. V.,Kulikov, V. I., ibid., Chem. SOC.,89, 1933 (1967). 12, (3), 244 (1968). (70) Brunelle, R. L., J . Ass. Ofic. Anal. Chem., 50, 319 (1967). (27) Barrett, H. C., Buechi, G., J . Amer. Chem. SOC.,89, 5665 (1967). (71) Buechi, G., Hofheinz, W., Paukstelis, J. V., J . Amer. Chem. SOC.,88, 4113 (28) Barton, D. H. R., Werstiuk, N. H., Chem. Commun., 1967, p 30. (1966). ~
(47)‘ The structural formulas of two new sesquiterpenes from slippery elm \\-ere established by Fracheboud et al. (166). 1discussion of terpinolene, including its analysis, was prepared by Verghese (631). Seven new bicarbocyclic diterpenes were isolated from Trachylobium verrucosum by Huge1 et al. (254). They had the l-labdane skeleton. The nomenclature and structure of ylangene was clarified by Veldhuis and Hunter (627), along with those of copaene and cubebene.
MISCELLANEOUS
Certain relationships between functional groups and flavor were suggested by Kulka (334). The properties and methods of analysis of many compounds containing the allyl configuration were reviewed by Karo (295). Perfume materials related to ambergris and the effect of chemical structure on their odor was discussed by Cambie (86)’ The use of pyruvyl chloride 2,6dinitrophenylhydrazone derivatives of amines for isolation and characterization was described by Schmartz and Brewington (530). The detection and determination of biphenyl, o-hydroxybiphenyl, and diphenylamine with thin layer and gas chromatography and spectrofluorimetry was accomplished by Piorr and Toth (4711. A polarographic method for the determination of copper, lead, and zinc in aromatic essences was developed by Kaczmarek et al. (283). Studies of the far-infrared absorption spectra of compounds with a musk odor led Wright (664) to indicate that odor specificity is related to a pattern of low frequency molecular vibrations. Beets (40)studied the relation between molecular structure and the odor of musks, and suggested that the molecular pro52 R
ANALYTICAL CHEMISTRY
I
1
(72) Buechi, G., Kovats, E., Engist, P., Uhde, G., J . Org. Chem., 33,1227 (1968). (73) Buenau, G. von, Schade, G., Gollnick, K., Fresenius’ Z . Anal. Chem., 227, 173 (1967). (74) Buenau, G. von, Schade, G., Gollnick, K., ibid., p 270. (75) Buttery, R. G., Ling, L. C.. J . Agr. Food Chem., 15, 531 (1967). (76) Buttery, R. G., Lundin, R. E., Ling, L., Chem. Znd. (London), 1966, p 1225. (77) Buttery, R. G., Lundin. R. E., Ling, L., J . Agr. Food Che?., 15, 58 (1967). (78) Calapaj, R., Sergi, G., Ann. Fac. Econ. Commer., LTnzv. Studz Messina, 5 , (11, 1 (1967). (79) Calderon, J., Milian, M.>An. Real SOC.Espan. Fis. Quim., Ser. B . 62, 1185 (1966)
(8O,‘C&arano, I., Essenze Deriv. Agrumari, 35, 212 (1965). (81) Zbid.. 36, 5 (1966). (82) Calvarano, >I.>ibid., 35, 197 (1965). (83) Ibid., 36, 100 (1966). (84) Ibid., p 237. (85) Calzolari, C., Stancher, B., Pertoldi Marletta, G., Uniu. Studi Trieste, Fac. Econ. Commer., Zst. Merceol., 1966, (28), 19 PP. (86) Cambie, R. C., Chem. Znd. Xew Zealand, 3, (lo), 4 (1967). (87) Cardoso do Vale, J., Proenca da Cunha, A, Garcia Orta, 12, 673 (1964). (88) Cenci. C., Calvarano. I., Essenze Deriv. Agrumarz, 37, 141 (1967). (89) Cerny, V., Dolejs, L., Labler. L., Sorm, F., Slama, K., Collect. Czech. Chem. Commun.. 32. 3926 11967). 190) Chakrabartty, T:. J . Sci. Znd. Res., 25.I ,544 - - - f l-9-6 -, A- \
(si, Chaliha, g.’P.,
Sastry, G. P., Rao, P. R., Indian J . Chem., 5, 239 (1967). (92) Challen. S. B.. Kucera, AI.. Pharm. Weekblad, 102, 719 11967). (93) Chang, S. S., “Kirk-Othmer Encyclopedia of Chemical Technology,” Vol. 9, 2nd ed nr 336, - - - , l%6 - (94) Chatterjee, K. L., Pruthi, J. S., Indian Oil Soap J.. 33, 152 (1967). (95) Chetty, G. L., Zalkow, V.E., Zalkow, L. H., Tetrahedron Lett., 1968, p 3223. 196) Choora. 31. M..Indian Perfumer. 9. ( l ) ,3 (1965). (97) Chorbadzhiev, S., Ivanov. D., Iordanov, C., Godishnik SofLiskiya V n i v . K h i m . Fak., 59, 229 (1964-65). (98) Condon, R. D., French patent 1,489,569 (July 21. 1967). 199) Connell. D. W..Hildebrand. R. P.. Sutherland. 31. D.. Tetrahedrdn Lett., 1968, p 519. (100) Cook, K. B.. Howard, A. S., Can. J. Chem., 44, 2461 (1966). (101) Ibid., 45, 2002 (1967). (102) Corbett. R. E.. Smith, R. -4.J.. J . Chem. SOC.C.. 1967, p 300. (103) Corbett, R. E.. Smith, R. *4.J.. Tetrahedron Lett., 1967, p 1009. (104) Corbett, R. E., Wyllie, S. G., J . Chem. Soc. C.. 1966, p 1737. (105) Corbier. R., Teisseire, P , Recherches (Paris), 1966, (151, p 89. (106) Corey, E. J., Katzenellenbogen. J. A., Posner, G. H., J . Amer. Chem. SOC., 89, 4245 (1967). (107) Corey, E. J., Kozoe, S., ibid.. 87, 5733 (1965). (108) Cornforth, J. W.,Draber. W.,Milborrow, B. V., Ryback, G., Chem. Commun., 1967, p 114. (109) Corovic, AI., Stjepanovic, L., Nikolie, R., Pavlovic, S., Zivanovic, P., Arhiv. Farm., Belgrade, 15, 7 (1965). (100) Covello, W., Ciampa, G., La Rotonda, A I . I., Boll. Chim. Farm., 105, 799 (1966) (111) Crabalona, L., C. R. Acad. Sci., Paris. Ser. C., 264, 2074 (1967). (112) Cristini, B. J. C., Baruffaldi. R., Akisue, G., Rev. Fac. Farm. Biochim. >
Univ. s u o P a u b , 4, (I), 119 (1966). (113) Cristofaro, E., Egli, R. H., Chromatogr. Methods Zmmed. Separ., Proc. Meet.. Athens. 1965. (2). 95 (Pub. 1966). (114) C’rossley, J . C h e k Znd., London,
1966, p 1969. (115) Czuba, IT.>Bankowski, C., Ganszer, W., Diss. Pharm. Phurmacol., 19, (3), 281 (1967). (116) Daloze. D.. Ind. Chim. Beloe. 32. ‘ 416 11967).’ ’ (117) Darnjanic, A., Ruzic, N., Petric, T., Farm. Glasnik, 23, 553 (1967). (118) Damodaran, N. P., Dev. S., Tetrahedron, 24, 4113 (1968). (119) Ibid., p 4123. (120) Ibid., p 4133. (121) D’Amore, G., Calabro, G., Ann. Fac. Commer., Univ. Studi Messina, 4, 633 (1966). (122) D’Amore, G., Corigliano, F., ibid.! p 413. (123) Dashunin, V. ?*I., Maeva. R. V., Samotnga, G. A . , Belov, V. N.>Livshits, A. G., Kaboshina, E. S., T r . ‘C‘ses. “
I
I
Nauchn. Issled. Inst. Sintetich. Naturaln. Dushistykh. Veshchestv, 1965, ( i ) p, 77. (124) Deryng, J., Strzelecka, H., Walewska. E., Soroczynska, T., Farm. Polska,
23, 32 (1967). (125) Deryng, J., Strzelecka, H., Walewaka, E., Soroczynska, T., Malinowski, J., ibid., p 585. (126) Dev, S., Anderson, J. E., Cormier, V., Damodaran, N. P., Roberts, J. D., J . Amer. Chem. SOC.,90, 1246 (1968). (127) Devgan, 0. N., Bokadia, hl. RI., Current Sci., 36, 205 (1967). (128) Devgan, 0 . N.,Bokadia, AI. M., Bose, A. K., Tibbetts, A I . S., Trivedi, G. K., Chakravarti, K. K., Tetrahedron Lett.. 1967, p 5337. (129) Diaz, E., Joseph-Nathan, P., Romo de Vivar. A., Romo, J., Bull. Inst. Quim. V n i v . Nacl. Auton. M e r . , 17, 122 (1965). (130) Di Giacomo, A., Riechst., Aromen, Koerperpjkgem., 16, 259, (1966). (131) Ibid., p 299. (132) Ibid.. p 464. (133) Zbid., 17, 85 (1967). (134) Zbid., p 138. 1135) Zbid.. D 178. (136) Ibid.: 320. (137) Ibid., p 403. (138) Zbid., p 460. (139) Ibid., 18, 14 (1968). (140) Dijkstra, G., Mass Spectrometry, N A T O Advan. Study Inst., Glasgow
1964, p 441 (Pub. 1965). (141) Dimri, B. P., Indian Oil Soap J., 32, 177 (1966). (142) Dixit, S. 11..Rao, il. S., Paknikar, S. K., Chem. Ind., (London), 1967, p 1256. (143) Dmitrieva, L. L., Bychkova, Z. N., Deeva, I. D., Maslozhir. Prom., 33, i9), 30 (1967). (144) Dool, H. van den. France Parfums, 9, 147 (1966). (145~Dreyer, D. L., J . Org. Chem., 31, 2279 (1966). (146) Drozdz. B., Holub, AI., Samek, Z., Herout, V., Sorm, F., Collect. Czech. Chem. C o m m m . , 33, 1730 (1968). (147) Druskina, E. Z., Shaposhnikov, Yu. K., Gaz. Khromatogr., Sb., Moscow, 1965, (3), p 146. (148) Dutta, S. P , Baruta. A. K.. J . Chromatogr., 29, 263 (1967). (149) Dwivedi, U. N., Singh, K. P., Gupta, G. N., I n d i a n Perfumer, 8, (2), 91 (1964). (150) Dyakov, G., Zolotovich. G., Rastenievztdni iVauki (SofLa),4, (5), 41 (1967). (151) Efremov, Yu. Ya., Dokl. Akad. N a u k SSSR, 170, 597 (1966). (152) Endo, K., De Mavo, P., Chem. Commun., 1967, p 89. ” (153) Enzell, C. R., Ryhage, R., A r k . Kemi. 26,425 (1967).
(154) Estevez Reyes, R., Gonzales Gonzalez, A., An. Real Soc. Espan. Fis. Quim., Ser. B , 62,981 (1966). (155) Ettlinger, hi. G., Kjaer, A., Thompson, C. P., Wagnieres, AI., Acta Chem. Scand., 20, 1778 (1966). (156) Ettre, L. S., Zlatkis, A , , “The Pract,ice of Gas Chromatography,” 591 pp, Interscience, New York, N.Y., 1967. (157) Evstratova, R. I., Rybalko, K. S., Rzazade, R. Ya., K h i m . Prir. Soedin., 3, 284 (1967). (158) Fagoaga Schenkel, W.,Canto dos Santos, A.. Rev. Fac. Farm. Bioquim., Santa Maria, 9, (2), 73 (1963). (159) Falchi, L., Boll. Chim. Farm., 105, 873 (1966). (160) Farid, S.,Tetrahedron, 24, 2121 (1968). (161) Fidler, J. C., J . Erp. Bot., 19, 41 (1968). (162) Fordham, W.D.. Rep. Progr. A p p l . Chem., 50, 326 (1965). (163) Forss. D. A.. Jacobseii, T’. >I., Ramshaw, E. H., J . Agr. Food Chem.. 15, 1104 (1967). (164) Forss, D. A , , Stark. IT., Urbach, G., J . Dairy Res., 34, 131 (1967). (165) Forss, D. A,, Urbach, G.. Stark, IT., Int. Dairy Cong.. Proc. 17th. Munich.
19fifi. 3. n 211. (166) Frlc‘heboLid, M ,Rowe, J. K.>Scott, R. W., Fanega. S. AI., Buhl, A. J., Toda, J. I(.. Forest. Prod. J . , 18, 37 (1968). (167) Frevtae. JT., Sev, .(I H.. Eitr. J . Bioche;., 4’315 (1968). 1168) Fritz. .T. S.. JVood. G. E.. ASAL. CHEM.,40,-134 (1968). (169) Fujita, Y., Fujita, S., ,Vippon Kagaku Zasshi, 87, 616 (1966). (170) Ibid., 88, 767 (1967). (171) Fuiita. Y.. hlizohata, H.. Iwamura, J., ibid:, 87, 1361 (1966). Tanaka. I-.. ibid., 86, (172) Fujita, I-., 1078 (1965). (173) Fujita, Y., Tanaka, Y., Iwamura. J., ibid., 88, 763 (1967). (174) Fujita. Y., Ueda, T., ibid., 86, 1072 (1965). (175) Fujita, Y., Ceda, T.. Kzohata, H., ibid., p 1074. (176) Garnero, J., Benezet, L., Peyron, L., Chretien-Bessiere, Y., Bull. SOC.Chim. Fr., 1967, p 4679. (177) Gawlowska, XI.$Diss. Pharm. Pharmacol., 19, 181 (1967). (178) Geissman, T. A., Llukherjee. R.. J . Ora. C h m 33. 656 11968). (179)-C;ei Tetrahedron Lett., 1968, pp 3145, 3591. (180) Gertig. H., Pic, S., Poznan. Towarz. Przviaciol Aiauk. Wvdzial Lekar. Prace Komisii Farm., 1966, ( 5 ) : p 47. (181) Giannotti, C., Schwang. H., Tetrahedron, 24, 2055 (1968). (182) Gibson, T. K., Erman, IT. F., Tetrahedron Lett., 1967, p 905. (183) Gildemeister, E., Hoffman. F., “Die Aetherischen Oele,” Band I11 d , 806 pp, Akademie-T’erlag, Berlin, 1966. (184) Godunpva, L. F., Klabunovskii, E. I., Balandin. A. A., Izv. Akad. N a u k SSSR, Ser. K h i m . , 1967, p 1013. (185) Gogiya, V. T., Biokhim. Progr.
Tekhnol. Chai. Proizvod.! Akad. X a u k SSSR, Znst. Biokhim., 1966, p 50. (186) Zbid.. p 57. (187) Goodwin, T. K . , Terpenoids Plants. Proc., Aberystwyth, Engl. 1966, p 1 (Pub. 1967). (188) Goretti, G., Laencina Sanchez, J., Liberti, A,, Riv. Ztal. Essenze-Profumi, Piante Ofic., Aromi-Saponi, Cosmet.Aerosol, 49, 145 (1967). (189) Goryaev, 11. I., Ignatova, L. A., Yurina, R. A4.,Dembitskii, A. D., T r . Znst. K h i m . N a u k , Akad. N a u k K a z . SSR, 19, 103 (1967). (190) Goryaev, 11. I., Kekelidze, S . A,, VOL. 41, NO. 5, APRIL 1969
53 R
Krotova, G. I., Serkebaeva, T. E., Dembitskii, A. D., Izv. Akad. Nauk Kaz. SSR. Ser. Khim., 17, (5), 78 (1967). (191) Goryaev, M.I., Serkebaeva, T. E., Krotova, G. I., Dembitskii, A. D., Rast. Resursy, 3, (I), 63 (1967). (192) Goryaev, RI. I., Sharipova, F. S., Tikhonova, L. K., El’chibekova, L. A., Izv. Akad. Nauk Xaz. SSR, Ser. Khim., 17. 16). 73 11967). (193j Goryaev, 11. I., Sharipova, F. S., Tikhonova, L. K., El’chibekova, L. A,, Maslozhir. Prom., 33, (9),27 (1967). (194) Gorvaev, U.I., Tikhonova, L. K., Dembitskii, A. D., Lishtvanova, L. K., Izv. Akad. Nauk Kaz. SSR, Ser. Khim., 17, (3), 80 (1967). (195) Goryaev, 11. I., Tikhonova, L. K., Lishtvanova, L. K., i b i d . , ( 5 ) , p 85. (196) Goryaev, XI. I., Yurina, R. il., Ignatova, L. A , , Dembitskii, A. D., Tr. Inst. Khiwi. Nauk, Akad. Nauk Kaz. SSR, 19,99, (1967). (197) Gospodinova, V.,Tevekelev. D., Izv. Inst. Khranene, Bulg. Akad. Nauk, 5, 165 (1966). (198) Granger, R., Pawet, J., Verdier, R., Bull. Trav. SOC.Pharm. Lyon, 9, (3), 113 11965). (199) Gray,’R. T., Smith, H. E., Tetrahedron, 23, 4229 (1967). (200) Grechukhina, Z. N., Nesmelov, 5’. V., Zh. Prikl. Khim., 39,2574 (1966). 1201) Griffiths. T. R.. Colloa. Smctrosc. Int., 12th, Exeter, Engl., 1965,p226. (202) Grosch. IT., Z. Lebensm.-Unters. Forsch., 135, (2), 75 (1967). (203) Guenther, E., Amer. Perfumer Cosmet., 83, (6), 57 (1968). (204) Guenther, E . , Gilbertson, G., Koenig, R. T., ANAL. CHEM.,39, ( 5 ) , 48R 11967). 1205) H.. Biechst.. Aromen. ~- Guenther. K&rperpj?egek 18, 84 (1968). (206) Guentzel, U., Seidel, F.!Kating, H., Planta Xed., 15, 205 (196i). 1207) Gulati. B. C.. Perfum. Essent. Oil Rec.. 57. 692 11966). “ (208) Guljti, B. C.: Duhan, S. P. S., Bhattacharyya, A. IC, ibid., 58, 523 (1967). (209) Gulati, B. C., Gupta, R., Soap Perjumery Cosmetics. 40, 413 (1967). (210) Gumprecht, D. L., Schwartzenburg, F., Jr., J . Chromatogr., 23, 134 (1966). (211) Gunay, G. E., Dissertation Abstr. B, 27, 1811 (1966). (212) Gurvich, N. L., Neparidze, N. I., Dokl. Akad. Xauk Azerb. SSR. 22, (71, 54 (1966). 1213) Guseva. A. R.. Paseshnichenko. V. A , , Pchelkina, V. V., Skorobogatova, E. P., Prikl. Biokhim. Mikrobiol., 3, 105 (1967). (214) Hallaba, E., Raieh, AI., Int. J . Appl. Radiat. Isotopes, 18, 533 (1967). (215) Hamann, E. H., Guenther, E., Kirk-Othmer Encyclopedia of Chemical Technology, Vol. 9,2nd ed., p 347, 1966. (216) Hanson, J. R., Tetrahedron, 23, 793 (1967). (217) Ibid.. p 801. (218) Harrison, S., Analyst, 92,773 (1967). 1219) Hartlev. R. D.. Fawcett. C. H.. Chern. Znd: (London), 1967, p 1601. (220) Hata, K., Kozawa, hI., Ikeshiro, Y., Yakugaku Zasshi, 87, 1118 (1967). (221) Hawkes, S. J., Kheaton, AI. D., J . Food Sci., 32, 629 (1967). (222) Hayashi, S., et al., Bull. Chem. SOC. Japan, 41, 234 (1968). (223) Hefendehl, F. W.,Arch. Pharm., 300, 438 (1967). (224) Hefendehl, F. W., Naturwissenschajten, 54, (6), 142 (1967). 12253 Hefendehl. F. IT..Planta M e d . , 15, (2j, 121 (1967);. (226) Hefendehl, F. W.,Underhill, E. W., Rudloff, E. von, Phytochemistry, 6, 823 (1967). \-
~
~~
~
54 R
ANALYTICAL CHEMISTRY
(227) Hellyer, R. 0I., Lassak, E. V., Aust. J. Chem., 20,2297 (1967). (228) Hellyer, R. 0.. Lassak. E. V.. McKern, H. G., ibid., 19, 1765 (1966): (229) Hellyer, R. O., McKern, H. H. G., ihid -~ n r 1541
(230) Henke, R., Riechst., Aromen, Koerperpjegem., 17, 226 (1967). (231) Herout, V., Herba Hung., 5, (2-3), 95 11966). (232) Herout, V., Banassek, A., Romanuk, M . , Collect. Czech. Chem. Commun., 31, 3012 (1966). (233) Herz, W.,Chikamatsu, H., Viswanathan, N., Sudarsanam, V., J . Org. Chem., 32, 682 (1967). (234) Herz, R., Kagan, H. B., ibid., p 216. (235) Herz, IT., Rajappa, S., Lakshmikantham, 11.V., Raulais, D., Schmid, J. J., zbid.. p 1042. (236) Herz. W.,Sumi, Y., Sudarsanam, V.. Raulais, D., ibid., p 3658. (237) Hikino, H., Auta, K., Maebayashi, Y. Takemoto T.. Chem. Pharm. Bull. (Tokyo), 14, 1439’(1966). (238) Ibid., 15, 1349 (1967). (239) Hikino, H.. Aota, K., Takemoto, T., ibid., 14, 890 (1966). (240) Ibid., 16, 52 (1968). (241) Hikino H.. Aota. K.. Takemoto. T..
(1967). (243) Hikino, H.. Hikino, Y., Takeshita, Y., Shirata. K., Takemoto, T., ibid., p 321. (244) Hikino, H., IIeguro, K., Sakurai, Y., Takernoto, T., ibid., 14, 1241 (1966). (245) Hikino, H., Sakurai, Y., Takahashi, H., Takemoto. T., ibid., p 1310. 1246) Ibid.. 15. 1390 11967). (247j Hikino, H . . Sakurai,’Y.,Takemoto, T., ibid., p 1065. (248) Hikino, H., Suzuki, S . , Takemoto, T., Tetrahedron Lett., 1967,p 5069. (249) Hikino, H., Takahashi, H., Sakurai, Y..Takemoto. T.. Bhacca. S. S.. Chem. Pharm. Bull. (Tokyo), 14,550 (1966). (250) Hikino. H.. Takeshita, Y.>Hikino, T., Takemoto, T.. ibid., p 735. (251) Hikino, H., Takeshita, Y.,Hikino, Y., Takemoto, T., Yakugaku Zasshi. 87, 1035 (1967). 12.52) Hikino. H.. Takeshita. Y.. Hikino. Y., Takemoto, T., Ito, S., Chem. Pharm. Bull. (Tokyo), 15, 485 (1967). (253) Huet, R., Fruits (Paris). 22, (4), 177 (1967). (254) Hugel, I’,G., Oehlschlager, A. C., Ourisson. G.. Tetrahedron. S u a ~ l .8, 1966, Pt. 1, p 203. (255) Huneck. S.. Klein. E., Phytochemzstry, 6, 383 (1967). (256) Hunter, G. L. K., Brogden, IV. B., Jr., zbid., 5, 807 (1966). (257) Hunter, I. R.,Walden, M. K., J . Gas Chromatogr., 4, 246 (1966). (258) Huxtable, J. D., Johnson, J. D. A . , Saxby, 11.J., Perjum. Essent. Oil Rec., 57, 492 (1966). (259) Ignat’eva, R. I’.,Livshits, A. Ya., Pokhlebalova, L. P.. Shatskaya, N. I., Maslozhzr. Prom., 33, ( l ) ,29 (1967). (260) Igolen, G., Soap Perfumery Cosmetzcs, 39, 461 (1966). (261) Ikeda, R. ?\I.. Stanley, TV. L.. Vannier, S. H., Rolle. L. A , , U.S. patent 3,294,550(Dee. 27, 1966). (262) Ikramov, 11. I., Chizh, 11. I., Rast. Resursy, 3, 244 (1967). (263) Iriuchijima, S., Kuyama, S., Takahashi. N., Tamura, s.,Agr. Biol. Chem. (Tokyo), 30, 511 (1966). (264) Ishibashi, K., Katsuhara, J., Hashimoto. K.. Kobayashi, >I., Kogyo Kagaku Zassha, 70, 1195 (1967). (265) Ito, S., Endo, K., Yoshida, T., 1 .
Yatagai, M., Kodama, M., Chem. Commun., 1967,~ ~ 1 8 8 . (266) Itty, RI. I., higam, S. S., Riechst., Aromen, Koerperpjlegem., 16,399 (1966). (267) Jentsch, J., Treibs, W., Parfuem. Kosmetik, 49, 29 (1968). (268) Ibid., p 143. (269) Jommi, G., Krepinsky, J., Herout, V., Sorm, F., Tetrahedron Lett., 1967. p 677. (270) Jonczyk, J., Herba Pol., 11, 135 (1965). (271) Ibid., 12, 291 (1966). (272) Joseph, T. C., Dev, S., Tetrahedron, 24,3809 (1968). (273) Ibid., p 3841. (274) Ibid., p 3853. (275) Joseph-Nathan, P., Nanjarrez, A , , Rev. SOC.Qztim.Mer., 11, (4),116 (1967). (276) Joshi, B. S., Kamat, V. N., Govindachari, T. R., Tetrahedron, 23, 261 (1967). (277) Ibid., p 267. (278) Ibid., p 273. (279) Joshi, G. D., Vaidya, A. S., Kulkarni, S. N., Bhattacharyya, S. C., Perjum. Essent. Oil Rec., 59, 187 (1968). (280) Juvonen, S., Acta Bot. Fenn., 1966, (711, 92 PP. (281) Juvonen, S., Lako, H., Farm. Aikak., 76, (5-6), 126 (1967). 1282) Kaburaki. Y.. 1Iikami. Y.. Kuniyoshi, H., Nippon Senbai Kosha Chuo Kenkyiisho Kenkyu Hokoku, 1966, (108), p 179. (283) Kaczmarek, F., Rutkowska, U., Kojsa, K.. Herba Pol., 13, (1-2)> 53 (1967). (284) Kadota, R., Nakamura, T., Nippon Shokuhin Kogyo Gakkaishi, 14, ( l ) , 7 fl FIA7)
(28i)-Kaiser, R., Chimia, 21, 235 (1967). (286) Kalsi, P. S.,Perjum. Essent. Oil Rec., 58, 796 (1967). (287) Kamivama. S.. Aar. Biol. Chem. (Tokyo). 31, 1091 (1967). (288) Kamiyama, S., Koguchi, Y., Jozo Kagaku Kenkyu Hokoku, 12, ( l ) , 67 (1966). (289) Kapadia, V. H., Kaik, B. G., Kadia, 11. S..Dev. S.. Tetrahedron Lett., 1967. p 4661. (290) Kapur, K. K., Vashist, V. N., Atal, C. K., Perjum. Essent. Oil Rec., 58, 148 (1967). (291) Karawya, 11. S.. Wahba, S. K., Amer. Perfumer Cosmet., 82, (12), 55 (1967). (292) Karlsen, J., Baerheim Svendsen, A., Medd. Norsk Farm. Selskap, 28, (6), 85 (1966). (293) Ibid., 30, ( l ) ,1 (1968). (294) Karlsen, J., Baerheim Svendsen, A., Planta Med.. 16, ( l ) ,95 (1968). (295) Karo, IT., “Encycl. Ind. Chem. Anal.,” Vol. 5 , p 75, Interscience, New York, N.Y., 1967. (296) Iiarryev, 11. O., Izv. Akad. Nauk Turkm. SSR, Ser. Biol. Nauk, 1967, (I), p 40. (297) Kasimovskaya, K. N., Goryaev, 11. I., Sharipova, F. S., Tikhanova, L. K., El’chibekova, L. A,, Tr. Inst. Khim. Nauk. Akad.. Nauk Kaz. SSR. 19, 95 (1967): (298) Kasturi, T. R., Manithomas, T., Tetrahedron Lett., 1967, p 2573. (299) Katsuhara, J., Ishibashi, K., Hashimoto, K., Kobayashi, SI., Kogyo Kagaku Zasshz, 69, 1170 (1966). (300) Katsuhara, J., Yamasaki, H., Hashirnoto, K., Kobayashi, hl., ibzd., 70, 343 (1967). (301) Kekelidze, N. A,, Tr. Gruzinsk. A’auchn.-Issled. Inst. Pishch. Prom., 1967, (3), p 287. (302) Kekelidze, N. A., Goryaev, RI. I., Dembitskii, A. D., Krotova, G. I., Pruidze, V. G., Izv. Akad. Nauk Kaz. SSR, Ser. Khim., 16, (4),86 (1966).
(303) Kesterson, J. W., Hendrickson, R., Amer. Perfumer Cosmet., 82, ( l ) , 37 (1967). (304) Khrimlyan, A. I., Herba Hung., 5 , (I), 63 (1966). (305) Kielczewski, W.,Kurnatowski, R., Chem. Anal. (Warsaw), 12, 803 (1967). (306) Kingston, B. H., Perfum. Essent. Oil Rec.. 57. 356 11966). (307) Ibid., p 3j8. ‘ (308) Kir’yalov, N. P., Serkerov, S. V., Khim. Prir. Soedin., Akad. Nauk c‘z. SSR, 2,.(2), 93 (1966). (309) Klein, E., Rojahn, W.,Dragoco Rept., 14, 3 (1967). (310) Ibid., p 183. (311) Ibid., 15, 3 (1968). (312) Kojima, hl., Akahori, Y., Ichikawa, I., Mochizuki, SI.,Hakko Kogaku Zasshi, 44, 177 (1966). (313) Kokama, K.) Nippon KagakuZasshi, 87, 265 (1966). Westfelt, L., Acta Chem. (314) Kolbe, X, Scand., 21, 585 (1967). 1315) Kolodziejski. J., Dembinska, IT.) Mruk-Luczkiewicz, A., Acta Polon. Pharm., 23, 259 (1966). (316) Komae, H., Nigam, I. C., J. Org. Chem., 33, 1771 (1968). (317) Kore. S. A . , Ivanova, R. P., Tr. Vses. Nauchn.-Issletl. Inst. Sintetich. i Natural’n. Dushistykh Veshchestv, 1965, (71, P 145. (318) Kore, S. A,, Reingach, B. Ya., Shepelenkova, E. I., Chernova, E. M., Ivanova, R. P., ibid., p 141. (319) Kore, S. A , , Shepelenkova, E. I,, Chernova, E. ll.>ibid., p 149. (320) Koul, G. L., Nigam, S. S., Riechst. Aromen, Koerperpjegem., 16,159 (1966). (321) Ibid., 17, 175 (1967). (322) Ibid., p 223. (323) Ibid., p 269. 1324’1 Kozhin. S. A , . Sorochinskaya, E. I.. .968). (1965). (326) Krasnova, S. I., Man’kovs’ka, N. K., Pavlikova, E. 11..llikishina, 2. RI., Khim. Prom. Ckraini, 1966, (2), p 55. (327) Kratochvil, V., Bulusek, J., Chem. Prum., 16, 715 (1966). (328) Kravchenko, Yii. S..Sviderskaya, Z. I., Maslozhir. Prom., 32,(8), 33 (1966). (329) Krepinsky, J., Samek, Z., Sorm, F., Tetrahedron Lett., 1966, p 3209. (330) Krepinsky. J., Samek, Z., Sorm, F., Lamparsky, D., Ochsner, P., Naves, Y.R., Tetrahedron, Suppl. N o . 8, 1966, Pt. 1, p 53. (331) Krupinska, A,, Wojterska, H., Poznan. Towarz. PrzyjacioZ Nauk, Wydzial Lekar., Prace Komisji Farm., 4, 25 119661. (332) Kubeczka, K. H., Flora (Jena), Abt. A , 158, 519 (1967). 1333) Kubeczka. K. H.. Planta Med.. 14. 381 11966). (334) Kulka, K., J. Agr. Food Chem., 15, 48 (1967). (335) Kulka, K., Hansen, O., Fraucavilla, V. A.. Amer. Perfumer Cosmet., 82, (61, 29 (1967). (336) Kulkarni, Ti. K., Sankpal, T. K., Bapat, B. V., Ghatge, B. B., J . Chromatogr., 32, 648 (1968). (337) Kusumoto, S., Ohsuka, A,, Kotake, hl., Nippon Kagaku Zasshi, 87, 887 (1966). (338) Labruyere, B., Olsthoorn-de Leeuw, C., Smeenge, F., Perfum. Essent. Oil Rec., 59, 206 (1968). (339) Lal, R.,N., Lal, J. B., J . Proc. Inst. Chem. (India), 38, 127 (1966). (340) Langenau, E. E., Am. SOC.Testing Mater. Spec. Tech. Publ., 1968, (440), p 71.
(341) Larkhan, T. JV., Pagington, J. S., J . Chromatogr., 28, 422 (1967). (342) Laurent, P. A., Da Cunha, J., Omagiu Raluca Ripan., 1966,p 327. (343) Levchenko, G. T., Bogoslovskii, Yu. N., Malkova, L. G., El’manovich, V. V., Zhizhnevskaya, bl. S., Gazov. Khromatogr., 1966, (4), p 110. (344) Levisalles, J., Rudler, H., Bull. SOC. Chim. Fr., 1967, p 2059. (345) Levisalles, J., Rudler, H., Ind. Chim. Belge, 32, 424 (1967). (346) Lewis, R. G., Gustafson, D. H., Erman, W.F., Tetrahedron Lett., 1967, p 401. (347) Lewis, Y. S., Nambudiri, E. S., Perfum. Essent. Oil Rec.. 58. 613 (1967). (348)‘Lewis, Y. S., Nambddiri, E . S., Philip T., ibid., 57, 623 (1966). (349) Likens, S. T , Nickerson, G. B., J . Agr. Food Chem., 15, 525 (1967). 1350) Linde. H. H. A , . Raeab. h1. S.. Helv. Chih. Acta. 50. 1961 71967). (351) Linek, A , , Vlahtv, R., Holub, M., Herout, V., Tetrahedron Lett., 1968,p 23. (352) List, G. R.. Hoffman, R. L., Evans, C. D., Nature, 213, (5074), 380 (1967). (353) Llovd. H. A,. Fales. H. Rl.. Tetrahedron Lett., 1967, p 4891. (354) Loeani. hI. K.. Varshnev. I. P.. Pandef, R. C., Dev, S.,ibid.: ’ ~ 2 6 4 5 : (355) Loomis, W. D., Terpenoids Plants, Proc., Aberystwyth, Engl., 1966, p 59. (356) Lorincz, G.. Tvihak. E., Hethelvi. I.,Bot. Kozlem., 54; (2), 97 (1967). (357) Lossner, G., Pharmazie, 22, 324 (1967). (358) Lossner, G., Wiss. Z. Karl-Xars L’niv. Leipzig, Math. Naturw. Reihe, 14, 455 (1965). (359) Lozzi, C., Perfum. Essent. Oil Rec., 58. 705 11967). (360j Lukic, P., Savin, K., Gorunovic, hl., Arh. Farm., 15, 157 (1965). (361) Lyerly, L. A4.,Tobacco, 164, (14), 26 (1967). (362) RlacLeod, W. D., Jr., Buigues, N. AI., J. Food Sci., 31, 588 (1966). (363) RlacLeod, W. D., Jr., RlcFadden, W. H.. Buieues. N. 11..ibid.. D 491. (364) Maekawa, K., Kodama, hi., Kushi1, &I., Rlitamura, AI., Agr. Biol. Chem. (Tokyo), 31, 373 (1967). (3165) Xlaekawa, K., Kodaima, M., Kushii, M.,Mitamura, T., Yadla. N.. ‘Fukino. H.. Mem. Ehime Univ.. Sect. V I ,. 12., 13i. 131 11967). (366)’ llaier$ H. G., Diemair, W., Fresenius’ Z. Anal. Chem., 227, 187 ( 1967). (367) Rlalkonen, P. J., Frostell, R., Suomen Kemistilehti. B. 40. 14). 84 (1967). (368) llancini, B., Trib. Farm. (Brazil), 34, (3-4), 117 (1966). 1369) Iranjanatha, T. R., Rajamani, T. S., Gowda, D. R.. Ramaswamy, 11. K.> Indian Perfumer, 8 , (21, 73 (1964). (370) ManjarreL, -4.,Bertrand, C., Bol. Inst. Quem. Cniu. S a l . Aziton. Mex.., 19., 78 119k7). (371) llanjarrez. A , , llendoza, V., Perfum. Essent. Oil Rec.. 57, 561 11966). (372) llanjarrez. h.,llendoza, I-.,ibid.. 58, 23 (1967). 1373) Mannheim, H. C.. Bomben, J. L., Guadagni, D. G., lrorgan. A . I., Jr., Food Technol., 21, (3.41, l5lA (1967). (374) l I a r o n j , G.. Ubertis, 13., Riv. Ital. Essenze-Projumi, Piante O ~ C . Aromi, Saponi. Cosmet.-ilerosoZ, 48, 571 (1966). ( 3 7 5 ) llarshall, J. A , , .4ndersen, N. H., Tetrahedron Lett., 1967, p 1611. 1376) IIarshall, J. A4.,Johnson, 1.’ C., Chem. Commun., 1968, p 391. (377) llartelli. A , , Nano. G. M.,Biglino, G.. Gallino. ll.,Ann. Chim. (Rome),57, 1027 11967). (378) Masada, Y., “Analysis of Essential Oils by Gas Chromatography,” 206 pp, ~
Kirokawa Publ. Co.. Tokyo, 1968. (379) Matawowski, A . , Chern. Anal., (Warsaw), 12, 369 (1967). (380) Mathur, R. K., Ramaswamy, S. K., Rao, -4.S., Bhattacharyya, S. C., Tetrahedron, 23, 2495 (1967). (381) Matsueda, S., Geissman, T. A,, Tetrahedron Lett., 1967,p 2013. 1382) Ibid.. D 2159. (383) Mazer, L., Takacs, J., J . Chromatogr., 29, 24 (1967). (384) Meerburg, IT., Van Essen, H., German patent 1,240,609 (May 18,
_-_. 1067)
(385) iiehta, G., Nayak, U. R., Dev, S., Tetrahedron, 24, 4105 (1968). (386) Xeranger, J. C., Bartlet, J. C., Radecka, C.: Nigam. I. C., Perjum. Essent. Oil Rec.. 58, 710 (1967). 1387) Messerschmidt, I. W., Arch. Pharm., 300, 550 (1967). (388) llinato, H., Ishikawa, bl., J . Chem. Soc., C, 1967,p 423. (389) Minyard, J. P., Thompson, A. C., Hedin, P. A , J . Org. Chem., 33, 909
(1968). (390) Llitzner, B. M., Lemberg, S., hlancini, lr..Amer. Perfumer Cosmet., 81, 15), 35 (1966). 13913 Mitzner. B. 31.. IIancini. V. J.. Lemberg, S., Theimer, E. T., Appl. Spectrosc.. 22, (1). 34 (1968). (392) llizrahi, I.. Nigam, I. C., J. Chromatogr., 25, 230 (1966). 1393) Noen, R. Fr., llakowski. H. S , h ‘ A L . C H E M , 39, 1860 (1967). (394) Monolov. Ii. R.. Georeiev. E. V.. Talanta. 14. 124 11967). (396) llontes: A. ~ L . ,’An. SOC. Cient. Argent., 184, (lL2), 12 (1967). (396) Montes, A. L., Alizrahi, I., ibid., 181, (3-4),49 (1966). (397) llorikawa. K.. Hirose, Y., Kippon Kagaku, Zasshi,88, 795 (1967). (398) hlorikawa, K., Nishimura, Ii., Hirose, Y., ibid., 87, 591 (1966). (399) Morishita. I.,Takahara, H., Shinkai, T.. Shimura, IC., Kakui, S..lnumaru, H., Nippon Spnbai Kosha Chuo Kenkym h o Kenkyu Hokoku, 109, 117 (1967). 1400) Noshonas. 11. G.. J . Food Sci.. 32. 206 (1967). (401) l l u , Ch’uan-Chang, Yan, I-Ching, Yao Hsueh Hsueh Pao, 13, 451 (1966). (402) Rllieggler-Chavan, F.! Viani, R., Bricout, J., Reymoiid, D., Egli, R. H., Helv. Chim. Acta, 49, 1763 (1966). (403) llueller, 4..“Internationaler Riechstoff-Kodex,” Alfred Huettig, Verlag, Heidelberg, 1968. (404‘1 Muller. C. J., Jennings, IT. G.. J . Agr. Food Chim.,15, 762 11967). (405) Muller, Y . A . , Perfurn. Essent. Oil Rec., 58, 368 (1967). (406) Muller, P. A , , Seijen-Oele-FetteWuchse, 92, 625 (1966). (407) llurdock, D. I., Food Technol., 21, 157 1196i~). (408) JIurray. K. E., Stanley, G., J. Chromatogr.. 34, 174 (1968). (409, Sano, G. l l . , Martelli, -4., Sancin, P., Riv. Ital. Essenze-Profumi, Piante Offic.. Aromi-Saponi, Cosniet.-Aerosol, 98,409 (1966). (410) Sarang. C. K., llathur. K. I(.. Indian J. Chem.. 4, 263 (1966). ( 4 1 1 ~Narayana. 11. R., Gonda, D. R., Marijanatha, T. R., Soap Perfumery Cosmetics. 40, 336 (1967). (41‘21 National iicademy of Sciences, “Food Chemicals Codex,” 1st ed.. 1966, 846 pp. First Supplement to the “Food Chemical Codex.” effective Nov. 1. 1967, 26 pp, National Academy of Sciences-Sational Research Council, Kashinnton. D.C. 1413) Xalmann, R., Fresenius’ Z . Anal. Chem., 233, 183 (1968). (414) Saves. T.-R.. Bull. SOC.Chim. Fr.. 1967, p 3152. VOL. 41, NO. 5, APRIL 1969
55
R
(415) Naves, Y.-R., Helv. Chim. Acta, 49, 2012 (1966). (416) Naves, Y.-R., Parfums Cosmet. Savcms, 9, 314 (1966). (417) Nayak, U. R., Dev, S.,Tetrahedrm, 24, 4099 (1968). (418) Nazarenko, ?VI.V., Leont’eva, L. I., Khim. Prir. Soedin., 2, 399 (1966). (419) Nepryakhina, A. V., Chudakova, I. K., Novikova, G. A., Lukina, G. G., Zh. Anal. Khim., 22, 909 (1967). (420) Xerali, S. B., Chakravarti, K. K., Tetrahedron Lett., 1967, p 2447. (421) Neuzil, E., Josselin, J., Jensen, H., Cesaire, G. O., Ann. Pharm. Fr., 25, 215 (1967):. (422) Kevskii, V. M.,Gutsalyuk, V. G., Grabarnik, L. G., Svetov, A. Y., Izv. Akad. Nauk Kaz. SSR, Ser. Khim., 17, (2), 27 (1967). (423) Nigam, B. P., Bhatnagar, V. P., Lal, J. B., J . Proc. Inst. Chem., (India) 39, (3)) 141 (1967). (424) Nigam, B. P., Saxena, R. C., Lal, J. B., ibid., p 48. (425) Nigam, I. C., Komae, H., J . Pharm. Sci., 56, 1299 (1967). (426) Nigam, I. C., Komae, H., Neville, G. A., Radecka, C., Paknikar, S. K., Tetrahedron Lett., 1968, p 2497. (427) Nigam, I. C., Levi, L., Can. J . Chem., 46, 1944 (1968). 1428) Ninam. I. C.. Levi., L.., J . Chromatogr., 23, 217 (1966). (429) Nigam, I. C., Neville, G. A,, ibid., 34,85 (1968). (430) Nigam, I. C., Radecka, C., Komae, H., J . Pharm. Sci., 57, 1029 (1968). (431) Kigam, I. C., Rao, P. R., Parjuem. Kosmetik, 48, 64 (1967). (432) Nigam, S. S., Rao, A. K., Riechst., Aromen, Koerperpjegem., 18, 75 (1968). (433) Ibid., p 169. (434) Nikolaeva, D. A., Tr. Khim. Prir. Soedin., Kishinev. Gos. Univ., 1966, (6), P-57.
(430) Nobuhara, A., J. Chromatogr., 30, 235 (1967). (436) Norman, S., Craft, C. C., J . Food Sci., 31, 529 (1966). (437) Novikova, E. N., Korchagina, T. N., Skvortsova, A. B., Tr. Vses.Nauchn.Issled. Inst. Sintetich. i Natural’n. Dushistykh Veshchestv, 1965, (7), p 190. (438) Kowak. Z.. Chem. Anal. (Warsaw). ,, 11, 753 (1966).’ (439) Nozoe, T., Assao, T., Ando, M., Takase, K., Tetrahedron Lett., 1967, p 2821. (440) Orgnyanov, I., Ivanov, D., Recent Develop. Chem. Natur. Carbon Compounds, 2, 47 (1967). (441) Orgnyov, I., Ivanov, N., Perjum. Essent. Oil Rec., 58, 161 (1967). (442) Ohta, Y., Hirose, Y., Agr. Biol. Chem. (Tokyo), 30, 1196 (1966). (443) Ohta, Y., Hirose, Y., Tetrahedron Lett., 1967, p 2073. (444) Ibid., 1968, p 1251. (445) Ohta, Y., Sakai, T., Hirose, Y., ibid., 6365. ada, R., Nakamura, T., Nippon Shokuhin Kogyo Gakkaishi, 14 (4), 137 (1967). (447) Okay, M.,Commun. Fac. Sci. Univ. Ankara, Ser. B, 11, 1 (1963-64). (448) Oliveros-Belardo, L., Perjum. Essent. Oil Rec.. 58. 359 11967). (449) Ord, W.O., ‘Bamford, P. C., Chem. Ind. (London), 1967, p 277. (450) Osisiom. I. U. W..Planta Med. 15 ( l j , 30 (lf67). (451) Pandey, R. C., Dev, S., Tetrahedron, 24, 3829 (1968). (452) Pansare, V. S., Dev, S., ibid., p 3767. (453) Paranjpe, >I. G., Gosavi, R. K., Indian J. Chem.. 5. 125 (1967). (454) Paseshnickenko, V. A., Guseva, A. R., Biokhimiya, 32, 1020 (1967).
(4:;y6[
56 R
ANALYTICAL CHEMISTRY
(455) Patel, D. J., Bafna, S. L., Nature, 211 (5052), 963 (1966). (456) Paukov, V. N., Rudenko, B. A., Kucherov, V. F., Zzv. Akad. Nauk SSSR, Ser. Khim., 1968, p 15. (457) Pays, M., Malangeau, P., Bourdon, R., Ann. Pharm. Fr., 24, 763 (1966). (458) Pennisi, L., Di Giacomo, A., Riv. Ital. Essenze-Projumi, Piante Ofic., Aromi-Saponi, Cosmet.-Aerosol, 47, 370 (1965). (459) Pentegova, V. A,, Dubovenko, Zh. V., Khim. Prir. Soedin., Akad. Nauk U z . SSR, 2, 173 (1966). (460) Pentegova, V. A., Kashtanova, N. K., Rezvukhin, A. I., Kolipova, E. I., ibid., p 239. (461) Perfum. Essent. Oil Rec., 58, 860 (1967). (462) Pertoldi Marletta, G., Stancher, B., Univ. Studi Trieste, Fac. Ewn. Com., Ist. Merceol., 1966 (29), p 19. (463) Petroewitz, H. J. Riechst., Aromen, Koerperpjegem., 16, 345 (1966). (464) Peyron, L., France Parjums, 10,199 (1967). (465) Peyron, L., Soap, Perfumery Cosmetics, 39, 633 (1966). (466) Peyron, L., Benezet, L., France Parjums, 10, 55 (1967). (467) Peyron, L., Benezet, L., Garnero, J., Bull. SOC.Chim. France, 1967, p 3038. (468) Pigulevskii, G. V., Kovaleva, V. I., Khim. Prir. Soedin., Akad. Nauk Uz. SSR, 2, 290 (1966). (469) Pigulevskii, G. V.,Kovaleva, V. I., Rust. Resursy, 2, 527 (1966). (470) Pinder, A. R., Price, S. J., J . Chem. SOC.,C, 1967, p 2597. (471) Piorr, W., Toth, L., 2. Lebensm.Unters. Forsch., 135, 260 (1967). (472) Platt. W.C.. U.S. Patent 3.347.681 , , ‘ (oct 17, i967). (473) Podlubnaya, E. T., Babkova, A. N., Rupnevskaya, M. L., Slavutskaya, N. I., Faershtern, Ya. D., Kuznetsova, E. >I., U.S.S.R. Patent 192,491 (Feb 6, 1967). (474) Pogany, D., Dissertation Abstr. B , 28. 1871 (1967). (475j Pogany, D., Bell, C. L., Kirch, E. R., J . Pharm. Sci.,. 56, 532 (1967). (476) Premru, L., Sirec, M.,Hrana Ishrana, 8 (I), 35 (1967). (477) Pribela. A., Prumusl Potravin, 18 (ij, 51 (1967). (478) Pridham, J. B., Ed., “Terpenoids in Plants,” 257 pp, Academic Press, New York, N.Y., 1967. (479) Prinzler, H., Pape, D., Tauchmann, H., Teppke, >I., Tzscharnke, C., Ropa Uhlie, 8 (l), 13 (1966). (480) Pruidze, V. G., Tukvadze, S. G., Kekelidze, N. A., Tr. Gruz. Nauchn.Issled. Inst. Pishch. Prom., 2,352 (1966). (481) Puttnam, N. A., Lee, S.,Spenalztzes, 3 (2), 15 (1967). (482) Rao, P. R., Venkataratnam, R. V., Sidhu, G. S., Perfurn. Essent. Oil Rec., 57, 554 (1966). (483) Rasmussen. H.. J . Chromatogr., 26. 512 (1967). (484) Raymond, G. M., Parfum. Cosmet. Savons, 11, 9 (1968). (485) Ibid., p 58. (486) Razinskaite, D., Liet. T S R Mokslu Akad. Darb., Ser. C., 1966 (2), p 39. (487) Razinskaite, D., Slavenas, J., ibid., p 57. (488) Ibid.. D 71. (489) Regan; A. F., Andrews, B. R., J . Chromatogr., 31, 209 (1967). (490) Remier. F. E.. Dissertation Abstr. B. ‘ 27, 428% (1967). ’ (491) Regnier, F. E., Eisenbraun, E. J., Waller, G. R., Phytochemistry, 6, 1271 1967). (492) Regnier, F. E., Waller, G. R., Eisenbraun, E. J., ibid., p 1281. ~
~
(493) Ribeiro dos Santos, S., Mollan, T. R. RI., Pinto, A. J. D’A., Brilho, C. C., Donalisio, hi. R., Jady de Souza, C., Riu. Ital. Essenze-Projumi, Piante Ofic., Aromi-Sapmi, Cosmet.-Aerosol, 98, 428 (1966). (494) Rogers, J. A., Advan. Chem. Ser., 1966 ( 5 6 ) .D 203. (495) Rogers, J., Toth, Z., Cereal Science Today, 13, 294 (1968). (496) Rollet, RI., Cuisinaud, G., Monghal, M. A., Ann. Pharm. Fr., 25, 713 (1967). (497) Rollet, M.,Monghal, ?VI. A., ibid., ,
y
A
-
mr,
, V U .
(498) Rosebrook. D. D.. Barnev. J. E.. J.’Ass. O$lc. Anal. Chem., 51,6$3 (1968): (499) Rosebrook, D. D., Bolze, C. C., Barney, J. E., ibid., p 644. (500) Rothbaecher, H., Suteu, F., Kraus. A,. Planta Med., 15, 434 (1967). (501) Rudloff, E. von, Can. J . Botany, 45, 891 11967). (502j Ibid.,’46, 679 (1968). (503) Rudloff, E. von, Hefendehl, F. W., Can. J . Chem.. 44, 2015 (1966). (504) Rudol’fi. T. A , , Sharapova, R. I., Tr. Vses. Nauchn.-Issled. I&. Sintetich. i Naturaln. Dushistykh Veshchestv. 1965 (71. D 167. (505j’kaijo. R., Kuwabara, Y., Agr. Biol. Chem. (Tokyo), 31, 389 (1967). (506) Saiki, Y., Akahori, Y., Morinaga, K., Taira, T., Noro, T., Fukushima, S., Harada. T.. Yakuaaku Zasshi. 87. 1535 (1967). (507) Ibid., p 1539. (508) Ibid.,, p 1544. (509) Saiki, Y., Akahori, Y., Noro, T., Morinaga, K., Taira, T., Fukushima, S., Harada, T., ibid., p 1529. (510) Sakai, T., llaarse, H., Kepner. R. E., Jennings, W.G., Longhurst, W. &I., J . Agr. Food Chem., 15, 1070 (1967). (511) Sakhatov, E., Belova, X. V.,Khim. Prir. Soedin., 3, 349 (1967). (512) Saleh, 31. R. I., blohamed, Y. A., J . Pharm. Sci. U . Arab Rep.. 6.. 137 . (1965). (513) Salminen, K., Koivistoinen, P., Acta Chem. Scand.. 21. 1495 11967). (514) Sasaki, K.,Nippon Kagaku Zasshi, 87, 763 (1966). (515) Sastry, S. D., Maheswari, XI. L., Chakravarti, K. K., Bhattacharyya, S. C., Perfum. Essent. Oil Rec., 58, 154 (1967). (516) Sastry, S. D. Maheswari, M. L., Chakravarti, K. K. Bhattacharyya, S. C., Tetrahedron, 23, 1997 (1967). (517) Ibid., p 2491. (518) Saxton, W.L., J. Ass. O i c . Anal. Chem.. 49, 749 (1966). (519) Schaefer, J., Wiss. Z. Karl-MarxUniv. Leipzig, Math.-Xaturw. Reihe, 14, 435 (1965). (520) Schantz, 11.von, Farm. Aikak., 76, 265 (1967). (521) Schantz, &I. von, Juvonen, S., Planta Med.. 15. 337 11967). (522) Schnelle, F.’J., Hoerster, H., ibid., 16, 48 (1968). (523) Schratz, E., Qadry, S. 11.J. S., ibid., 14. 436 (1966). (524) Schratz, E., Schnelle, F. J., Qedan, S., Sci. Pharm., 36 ( l ) ,13 (1968). (525) Schulte, K. E., Ruecker, G.. Glauch, G., Planta Med., 15, 274 (1967). (526) Schulte-Elte, K. H., Ohloff, G., Helo. Chim. Acta, 49, 2130 (1966). (52i) Schultz, T. H.. Black, D. R., Bomben, J. L., Mon, T. R., Teranishi, R., J . Food Sci., 32, 698 (1967). (528) Schunack, W., Mutschler, E., Rochelmeyer, H., Pharm. Ztg., 112, 112 (1967). (529) Schwartz, D. P., Brewington, C. R., Microchem. J., 11, 430 (1966). (530) Ibid.,12, 192 (1967). ~
(531) Schwartz, D. P., Brewington, C. R., Shamev. J.. ibid.. D 186. (533) Scora, R. IT.: Am. J . Botany, 54, 446 (1967). Phytochemistry, 5, 823 (533) Scora, R. W., (1966). (534) Scora, R. ItT.)Mann, J. D., Lloydia, 30, 236 (1967). (535) Sedzik, D., Chabudzinski, Z., Kostecka-hIadalska, 0..Acta Polon. Pharm., 23, 149 (1966). (536) Serkevaeva, T. E., Dembitskii, A. D., Goryaev, hI. I., Tr. Inst. Khim. A-auk, Akad. N a u k Kaz. SSR., 19,. 110 (i967j. (537) Serkebaeva, T. E., Goryaev, RI. I., Dembitskii, A. D., Izv. Akad. Naztk Kaz. SSR, Ser. Khim., 18 (2), 60 (1968). (538) Sethi, S., Xigam, 31. C., Rao, P. R., Indian Perfumer: 9 ( l ) ,17 (1965). (539) Severin, V., Bull. Rech. Agron. Gembloux, 1, 289 (1966). (540) Sfiras, J., Riu. Ital. Essenze-Projumi, Piante OJic., Aronzi-Saponi, Cosmet.Aerosol, 68, 352 (1966). (541) Sfiras, J., Demeilliers, 9., Recherches, 1966 ( l 5 ) , p 83. (542) Shakunthala, A. P., Pathy, hI. S. V., J . Electround Chem., 14, 123 (1967). (543) Sharma, 11. L., Sigam, ?VI. C., Wanda, K. L., Rao, P. R.,Indian Oil Soap J . , 31, 303 (1966). (544) Shiftan. E., “Kirk-Othmer Encyclopedia of Chemical Technology,” Vol. 14, 2nd ed, p.717, 1967. (545) Shulgin, A. T., J . Chromatogr., 30, 54 (1967). (546) Singh, K. P.. Gupta, G. N., Indian Perfumer, 8 (1).25 (1964). (547) Sisido, K., Kurozumi, S., Utimoto, fi., Perfum. Essent. Oil Rec., 58, 528 (1967). (548) Sisido, K., Kurozumi, S.,Utimoto, K., Isida, T., ibid., 57, 557 (1966). (549) Sisido, K., Kurozumi, S., Utimoto, K.. Isida. T.. ibid.. 58. 212 11967). (550) Skvortsova, A: B.: Zelenetskaya, A. A., Korchagina, T. N., Petrova, L. N., Zh. Anal. Khim., 22, 1!65 (1967). (551) Slater, C. A . , Watkins, W.T., J.Sci. Food Agr., 15, 657 (1964). (552) Smith, P., J . Chromatogr., 30, 273 i1967). (553) Smolders, R. R., Can. J . Chem., 45, 889 (1967). (554) Smolders, R. R.. Zng. Chimiste, 49, 244 (1967). (555) Sood, V. K., Perfum. Essent. Oil Rec., 57, 362 (1966). (556) Zbzd., 58, 441 (1967). (557) Speckman, R. A., Collins, E. B., Anal. Biochem., 22, 154 (1968). (558) Spitzer, J. C., Steelink, C.. J . Pharm. Sci., 56, 650 (1967). (559) Stahl, E., Bohrmann, H., Naturwissenschaften, 54, 118 (1967). (560) Stahl, E., Scheu. D., Arch. Pharm., 301, 306 (1968). (561) Staicov, V., Zolotovitch, G., Kalaidjiev, V., Soap, Perfumery Cosmetics, 41, 327 11968). (562) Staikov, V. l l . , Chingova, B. G., Herba Hung.. 5 (1) 117 (1966). (563) Staikov, V., Cdingova, B., Rastenievudni Nauki (Sojia), 4 (5), 15 (1967). (564) Stancher, B., Pertoldi Marletta, G., Ann. Fac. Econ. Com. Univ. Studi Messina, 4, 663 (1966). (565) Stancher, B., Pertoldi Marletta, G., Rass. Chim., 19 (3), 99 (1967). (566) Stanley, W. L., Vannier, S. H., Phytochemistry, 6, 585 (1967). (567) Stassinopoulos. G., Dissertation Abstr. B , 27, 3049 (19673. (568) Steltenkamp, R. J., Casazza, IT. T., J . Agr. Food Chem., 15, 1063 (1967). (569) Stevens, R., Chem. Rev., 67 (11, 19 (1967). (570) Stjepanovic. L., Corovic, RI., Nikolic, R., Pavlovic, S., Zivanovic, P., Arhiv
Farm. (Belgrade), 15, 177 (1965). (571) Stoll, M., “Kirk-Othmer Enc clopedia of Chemical Technology,” Vof 14, 2nd ed, p 178, 1967. (572) Stoyanova-Ivanova, B. Khadj ieva, P., Rlladenova, K., Riv. Ital. EssenzeProfumi, Piante Ofic., Aromi-Saponi, Cosmet.-Aerosol, 49, 726 (1967). (573) Strickler, H., Kovats, E. Sz., Helv. Chim. Acta. 49. 2055 119661. (574) Studennikdva, L. D., Khaletskii, A. \I., Aptechn. Delo, 15 (5), 27 (1966). (575) Suchy, XI., Herout, V., Sorm, F., Collect. Czech. Chem. Commun., 31, 2899 (1966). (576) Suchy, M., Samek, Z., Herout, V., Bates, R. B., Snatzke, G., Sorm, F., ibid., 32, 3917 (1967). (577) Suchy, ?*I., Samek, Z., Herout, V., Sorm, F., ibid., p 3934. (578) Sugiyama, N., Oshima. >I.] Yoshioka, ?VI., Yamada, K., Nippon Kagaku Zasshi, 87, 1105 (1966). (579) Sully, B. D., Williams, P. L., Perfum. Essent. Oil Rec., 59, 365 (1968). (580) Suzuki, A., Miki, hf., Itoh, M., Tetrahedron, 23, 3621 (1967). (581) Swain, A. P., Peterson, R. F., Jr., Stedman, R. L., J . Food Agr., 17, 349 (1966). (582) Swan, E. P., Can. J . Chem., 45, 1588 11967). (583) Swisher, H. E., Perfum. Essent. Oil Rec., 57, 771 (1966). (584) Takemoto, T., Kusano, G., Hikino, H., Yakugaku Zasshi, 86, 1162 (1966). 15853 Talalai. S.. W . African Pharmacist. ~
(586) Zgid., p 46. (587) Zbid., p 48. (588) Ibid., p 72. (589) Ibid.. p 117. (590) Zbid., 9, 10 (1967). (591) Tamburrini, V., Jr., Dessertation Abstr. 26, 6996 (1966). 1592) Tatar. J.. Herba Huna.. 3.455 11964). (593) Teisseire, P., Recherchis (Paris), 1966 (151, P 85. (594) Teisseire, P., Galfre, A., Plattier, XI., Corbier, B., ibid., 1967 (16), R 59. (595) Teisseire, P., Galfre, A., Plattier, lI., Rouillier, P., Corbier, B., ibid., p 119. (596) Teisseire, P., Plattier, M Wojnarowski, W., Ourisson, G., ibid., p 89. (597) Teisseire, P., Rouillier, P., Galfre, &4.,abid., p 68. (598) Teppeev, S. B., Goryaev, &I., I. Uch. Zap. Kabardino-Balkarsk. Univ., Ser. S.-Khoz. Khim.-Biol., 1966 (29), p 371. (599) Ter Heide, R., Fresenius‘ 2. Anal. Chem., 236, 215 (1968). (600) Teranishi, R., Advan. Chem. Ser., 56, 121 (1966). (601) Teranishi, R., Perjum. Essent. Oil Rec., 58, 172 (1967). (602) Teranishi, R., Lundin, R. E., McFadden, W. H., &Ion, T. R., Schultz, T. H., Stevens, K. L., Wasserman, J., J . Agr. Food Chem., 14, 447 (1966). (603) Teranishi, R., Lundin, R.E., Scherer, J. R., Symp. Foods, 4th, Oreg. State Univ. 1966, p 161, (Pub. 1967). (604) Tezuka, S., Kamiya, K., Shimizu, S., Koryo, 1966 (81),p 17. (605) Thalacker, V. P., Dissertation Abstr. B , 28, 3660 (1968). (606) Thomas, A. F., Chem. Commun., 1967, p 947. (607) Thomas, A. F., Helv. Chim. Acta, 50, 963 (1967). (608) Thomas, A. F., Willhalm, B., Tetrahedron Lett., 1967, p 5129. (609) Timanovich, K. A., Maslob-Zhir. Prom., 34 ( l ) ,32 (1968). (610) Tira, S., Di Modica, G., Casinovi, C. G., Galeffi, C., Pela, A., Tetrahedron Lett., 1967, p 143. (611) Toda, T., Cheng, Y . S., Nozoe, T., ~
Chem. Pharm. Bull. (Tokyo), 15, 903 (1967). (612) Todd, W. A., Murray, &I.J., Perfurn. Essent. Oil Rec., 59, 97 (1968). (613) Tomita, B., Hirose, Y., Nakatsuka, T., Tetrahedron Lett., 1968, p 843. (614) Toth, L., PlantaMed., 15,157 (1967). (615) Trabaud, L., France Parfums, 9 (48), 167 (1966). (616) Trop, &I.,Sprecher, ?*I.,Pinsky, A., J. Chromatogr., 32, 426 (1968). (617) Tsankova, E.,Ognyanov, I.,Riechst., Aromen, Koerperpjegem., 18,219 (1968). (618) Tsellinskaya, T. F., Ivanova, N. I., Zavodsk. Lab., 32 830 (1966). (619) Tsubaki, N., kishimura, K., Hirose, Y., Bull. Chem. SOC.Jap., 40,597 (1967). (620) Tucker, C. L.) J . Ass. Ojic. Anal. Chem., 51, 650 (1968). (621) Tucker, C. L., Ogg, C. L., ibid., 50, 770 (1967). (622) Tumlinson, J. H., Minyard, J. P., Hedin. P. A.. Thomason. A. C.. J . Chromatogr., 29, 80 (1g67).‘ (623) Tyihak, E., Vagujfalvi, D., Planta *Wed., 15, 269 (1967). (624) Usseglio-Tomasset, L., Znd. Agr. (Florence),4 (4), 153 (1966). 1625) Vasek. F. C.. Scora. R. W.. Am. J . Botany, 54, 781 (1967). (626) Vashist, V. N.,Gandotra, C. M., Atal, C. K., Indian J. Chem., 5, 130 (1 967) \ - - - . / -
(627) Veldhuis, >I. K., Hunter, G. L. K., J . Food Sci., 32, 697 (1967). 1628) Venturini. A,. Ind. Aliment. 5 124). (629) ‘Verghese, J., Perfum. Essent. Oil Rec., 57, 694 (1966). (630) Ibzd., p 767. (631) Ibid., 58, 638 (1967). (632) Vernin, G., France Parfums, 10, 35 (1967) . (633) Ihd., p 281. (634) Vernin, G., Vernin, G., ibid., 9, 429 11966). (635) -~etti-Michelina, )I., Ann. Fac. Econ. Com., Univ. Studi Messina, 4, 733 (1966). Pilleri. R.. Atti (636) Vietti-Michelina, M., Conv. Reg. Aliment., 1st Conv. Naz. Qual., 4th, Trieste 1966, p 602 (Pub. 1966). (637) Vinot, >I., Bouscary, A,, France Parjums, 10, 279 (1967). (638) Virmani, 0. P., Datta, S. C., Perjum. Essent. Oil Rec., 58, 851 (1967). (639) Ibid., 59, 351 (1968). (640) Vlakhov, R., Holub, &I.) Herout, V., Collect. Czech. Chem. Commun., 32, 822 (1967). (641) Vlakhov, R., Holub, 1LjOgnyanov, I., Herout, V., ibid., p 808. (642) Vlakhov, R., Ognyanov, I., Riechst., Aromen, Koerperpflegem., 17,315 (1967). (643) Vlakhov, R., Ognyanov, I., Ivanov, D., Ganev, G., C. R. Acad. Bulg. Sci., 20, 1303 (1967). (644) Voelker, W. A., Skarzynski, J. pi., Stahl, R.H., J . Ass. Ojic. Anal. Chem., 50, 852b (1967). (645) Wada, S., Nakatani, H., Morita, K., J . Food Sci., 32, 559 (1967). (646) Wal, B.vander, Sipma, G., Kettenes, D. K., Semper, A. Th. J., Rec. Trav. Chim. Pays-Bas, 87, 238 (1968). (647) Walker, G. T., Seijen-Oele-FetteWachse, 93, 811 (1967). (648) Walker, J. R. L., New Zealand J . Sci., 10, 476 (1967). (649) Wang, K.-H., et al., Acta FoculioChim. Sinica, 6, 259 (1965). (650) Weissmann, G., Qualitas Plant. Mater. Vegetabiles, 14, 337 (1967). (651) Wellendorf, hf., Dansk Tidsskr. Farm., 40, 156 (1966). (652) Zbid., 42, 33 (1968). (653) Renninger, J. A., Yates, R. L., Dolinsky, hf., J . Ass. Ojic. Anal. Chem., 50, 1304 (1967). (654) Ibid., p 1313. VOL. 41, NO. 5, APRIL 1969
57 R
(655) Wenninger, J. A., Yates, R. L., Dolinsky, U.,Proc. Sci. Sect. Toilet Goods ASSOC., 1966 (46), p 44. (656) Westfelt, L., Acta Chem. Seand., 20, 2852 11966). (657) Ibid., 21, 152 (1967). (658) Ibid., p 159. (659) Westfelt, L., Svensk Kem. Tidskr., 79, 441 (1967). (660) Westfelt, L., Wickberg, B., Arkiv Kemi, 26, 545 (1967).
(661) Wichtl, M., Planta Med., 11, 53 1963). (662) (Vitte, K., Dissinger, O., Fresenius’ 2. Anal. Chem., 236, 119 (1968). (663) Wolford, R. W., Attaway, J. A., J. Agr. Food Chem., 15, 369 (1967). (664) Wright. R. H.. Perfum. Essent. Oil Rec., 58;648 (1967). ’ (665) Yamada, Iibid., 40, 456 (1966). (668) Yoshida, T., Endo, K., Ito, S., Xozoe, T.. Yakuaaku Zasshi. 87. 434 11967). (669) ZacsGo-Szasz, AI., Siasz, G., Herba Hung., 5 (2-3), 91 (1966). (6iO) Zologtovich, G., ibid., ( l ) ,p 89. (671) Zwaving, J. H., Pharm. Weekblad, 103 (11),273 (1968).
Fertilizers Charles W. Gehrke and lames P. Ussary, Department of Agricultural Chemistry, University o f Missouri, Columbia, Mo. 65201
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HIS REVIEW covers the literature reported from Jan 1, 1967, to Dec 31, 1968, and includes procedures recorded in readily available journals, in Chemical Abstracts, and in Analytical Abstracts. Some selectivity has been exercised to include only those procedures especially pertinent or those which, in the authors’ judgment, could be adapted easily to fertilizer analytical problems. Quackenbush et. a1 (60) determined the variations in results within and among 23 laboratories on the analysis of nitrogen, phosphorus, and potassium. In addition to the data on variation within and among laboratories, the observations provided information on bias, both in the analysis and in the reporting of data. Details were given of methods of analysis, including modifications of known methods, of plant nutrient solutions specifically for use in connection with hydroponic culture, and also for plant tissue tests for assessment of uptake (60). Methods include those for measuring p H (5 to 8) by using mixed indicators and for determining nitrate, ammonium, phosphate, calcium, magnesium, potassium, sulfate, iron, boron, chloride, copper, zinc, and manganese.
OFFICIAL METHODS
The Association of Official Analytical Chemists (AOAC) in 1966 gave “official” status to a n atomic absorption procedure for copper, iron, magnesium, manganese, zinc, and calcium in fertilizers. The between-laboratory precision ranged from 4 to 7y0 for copper, iron, magnesium, manganese, and zinc. The presence of phosphate interfered in the determination of calcium. Strontium and lanthanum salts or a high temperature acetylene-nitrous oxide flame eliminated the interference. A dichromate method for iron was adopted as official, A method for sampling bulk 58 R
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ANALYTICAL CHEMISTRY
fertilizers was given official status (66, 66). The Japanese National Institute of Agricultural Sciences published, in English and Japanese, a compilation of the Japanese official analytical methods for fertilizers. These methods include sampling, moisture, and 30 elemental and radical determinations (46). SAMPLING
Gehrke et al. (19) designed a study t o investigate the sampling of bulk loads of semigranular, granular, pulverized and, blended fertilizers. An accurate fertilizer sample could be secured by passing a stream sampling cup through the entire flow of material at equally timespaced intervals during the loading of a truck; this stream sample was used as the reference point. The AOAC double and single tube triers did not secure accurate samples of bulk loads. Two compartmented triers and the stream sampler were recommended as official sampling instruments. A concentric sampling pattern for taking samples was recommended. These same investigators evaluated possible mechanisms of sampler bias on dry mixed fertilizers in a n effort to develop better AOAC official sampling instruments and procedures (2). Three 1 ton lots of dry mixed fertilizer with known physical and chemical composition were prepared in the laboratory. Twelve vertical and 12 horizontal cores, arranged in a latin square sampling pattern, were secured from each lot with three triers: the AOAC double tube trier, a double tube compartmented trier, and a n experimental double halftube trier wherein the core was encompassed in place rather than being required to flow into a compartment as with conventional triers. Individual cores were analyzed physically and chemically. Only marginally significant differences were found be-
tween cores on the basis of tube opening size. The experimental double halftube trier was less selective to particle shape than either the compartmented or AOAC triers, but differences were not statistically significant. All triers produced more representative samples from vertical cores than from horizontal cores. Cores drawn at a 60” to 70’ angle from horizontal were not consistently different from vertical cores. Results of chemical analysis confirmed the sieve analysis findings quite closely. Horizontal cores secured with the experimental double half-tube trier confirmed that the bias observed in horizontal cores was due to downward drifting of small particles when the core area was disturbed by sampler insertion. Cores secured with the sample-retaining face upward contained an excess of fines, while cores secured with the sampleretaining face to the side or downward more nearly resembled vertical cores in composition. The experimental double half-tube sampler and a powered auger sampler were compared with the AOAC official compartmented probe and stream samplers on dry mixed fertilizer from three types of blending plants in six states (20). Standard deviations reflecting variability and precision of the experimental tube indicated performance comparable or superior to the official samplers in both chemical and mechanical analysis. The powered auger compared favorably to the official samplers in chemical analysis, but comparison as t o mechanical analysis could not be made because particle size reduction occurred. The official stream sampler failed to secure representative samples from baffle-type mixers when the discharge time was unusually short. Improved indices of sampling accuracy and precision were secured for all samplers used. Docherty devised a n automatic analytical system for analyzing nitrate, am-
