(83) Soda, AI., Hirayama, O., Yukagaku
10,24-8 (19G1). (84) Ogic. Dig. Federation SOC. Paint Technol. 32. S o . 427. Dart 2 (1960). 185’1 \ - - , Ibid.. n . ‘1517. (86) Ibid.: ‘33, KO. 434, Part 2 (1961). (87) Ohme, F.. Furbe Lack 66, 142 (1960). (88) Paint Illanuj. 31, 102, 352 (1961). (89) Ibid., 32, 222 (1962). (90) Zbid.; p. 279. (91) Palit, S. R., Chem. Eny. News 39, 40 (Aug. 7, 19611. (92) Pasciak, J., Ch,em. Anal. (Warsaw) 5, 477 (1960). (93) Ibid., 6, 411 (1961). (94) Perfetti, B., Miller, J. H., Om.Dig. Federation SOC. Paint Technol. 33, 1006 (1961). (95) Petrowitz, H. J., Pastuska, G., J. Chromatog. 7, 128 (1962). (96) Porter, R. S., Hoffman, A. S., Johnson, J. F., ANAL. CHEM. 34, 1179 (1962). (97) Ratusky, J., Bastar, L., Chem. & Ind. (London) 1962, 650. ~
(98) Rejhova, H., Clbrich, W.,Plaste Kautschuk 6, 539 (1959). (99) Ritchie, P. D., J . Oil Colour Chemists’ Assoc. 45,659 (1962). 1100) Schroder. E.. Waurick., U.., Plaste Kautschuk 7,’ 9 (1960). (101) Schulz, G., 2ellsfo.f Papier 9 , 421 (1960). (102) Shapras, P., Claver, G. C., ANAL. CHEhf. 34, 433 (1962). (103) Sodomka, J., Chem. Prunzysl 11, 333 (1961). (104) Stamulis, A., Glover, R., Am. Paint J . 45, 90 (1961). (105) Stephens, R. L., Lan-rence, R. V., ANAL.CHEY.34, 199 (1962). (106) Stetzler, R. S., Smullin, C. I?., Ibid., 34, 194 (1962). (107) Stine, I. A., Doughty, P. C., Forest Prod. J . 11, 530 (1961). (108) Studer, V. V., J . Am. Oil Chemists’ SOC.38, 423 (1961). (109) Swann, M. H., Adams, 31. L., ANAL.CHEM.34, 1319 (1962). (110) Swann, M. H., Adams, M. L., Esposito, G. G., Zbid., 33, 33R (1961). ~
(111) Sn-ann, AI. H., Esposito, G. G., Ofic. Diq. Federation SOC.Paint Technol.
33,62 (1961). (112) Turler, AI., Hogl, O., dfttt. Lebensmitt. Hyy. (Bern) 5 2 , 123 (1961). 11131 Uriu. T.. Hakamada. T.. J . Chem. ‘ SOC.Japan, ‘Ind. Chem. Sect. 62, 1421 (1959). (114) Van Rysselberge, J., Van der Stricht, hl., iVature 193, 1281 (19621. (115) T’argas, G. A., Rev Plastzcos ( M a d r z d ) 11, 409 (1960). (116) Verna, ?VI R., Mathur, S. K., Dayal P., Paint Manuf. 31, 387 (1961). (117) Vollmann, H. F., J . 021 Colour Chemzsts’ Assoc. 44, 308 (1961). (118) Vorbeck. M. I,, Mattick, L. R., Lee, F. A . Pederson, C S., ANAL. CHEhf. 33, 1512 (1961). (119) Weieel. K.. Farbe Lack 67. 494 (1961). (120) Wooldridge, W. D. S., Paint Technol. 25, 22 (1961). (121) Zielinski, W. L., Moseley, W. V., Bricker, R. C., O$lc. Dig. Federation 80c. Paint Techncl. 33, 622 (1961). I
/
I
Essential Oils and Related Products Ernesf Guenther, Kurf
Kulka, and 1. A. Rogers, Jr. N. Y.
Fritzsche Brothers, Inc., New York,
T
ninth review of analytical procedures for essential oils and related products covers the literature from September 1960 to August 1962, inclusive. During this period the number of analytical procedures of value to our industry has continued to increase. Thin-layer chromatography, one of the latest additions t o chromatographic methods, has found widespread application. Among the instrumental methods, which have come of age, nuclear magnetic resonance has to be mentioned. I n combination n-ith other established methods i t has proved to be of great assistance, particularly in structural elucidation. The following books are of interest t o our industry: HIS
“Association of Official Agricultural Chemists, Washington, D. C., “Official Methods of Analvsis of the Association of
Treibs, ed., Akademischer Verlae, - Berlin, 1960. 429 pp. K. S. Markley, “Fatty Acids. Their Chemistry, Properties, Production, and Uses.” 2nd ed.. Interscience. Sew York. 1960. J. Merory, “Flavorings. Composition, Manufacture and Use,” Reinhold, New York, 1960. 425 pp. Givaudan-Delawanna, Xew York, “Givaudan Index. Specifications of Synthetics and Isolates for Perfumery,” 1961. 431 pp. J. H. Beyon, “Mass Spectrometry and
Its Applications to Organic Chemistry,” Van Nostrand, Princeton, N. J., 1960. J . C. Martin, “NMR Spectroscopy as an Analytical Tool in Organic Chemistry,” J. Chem. Educ. 38, 286-91 (1961). F. C. Kachod and W. D. Phillips, eds., “Determination of Organic Structures by Physical Methods,” Vol. 11, Academic Press, New York, 1962. 784 pp. T. Bas$$ “Introduction h 1’Etude des Parfums, Masson et Cie., Paris, 1960. J. Pliva, M. Horak, V. Herout, and A. Sorm, “The Terpenes. Collection of Spectra and Physical Constants,’’ Part 1, “Sesquiterpenes,” Akademischer Verliag, Berlin, 1960. J. W. Parry, “Spices, Their Mor hology, Histology, and Chemistry,” 8hemical Pub. Co., Xew York, 1961. 226 pp. OFFICIAL COMPENDIA
The Scientific Committee of the Essential Oil Association of U. S. A. has published specifications for 21 additional essential oils or natural products, and 30 aromatic ahemicals, increasing the total number of specifications from 173 to 224 as of January 1963. The essential oil monographs added since the last review are:
KO. 174 175 177 178 179 180 181 182 183 194 195
Oil sandalwood. Australian Oil cascarilla Oil chamomile, English Oil clove, stem Oil costus, root Oil garlic Oil labdanum Oil mace Oil onion Castoreum Civet, natural
196 197 198 199 200 212 213 214 215 216
Oil wormseed, American Oil savory (summer variety) Oil tea tree Oil Mentha arvensis (dementholized) Oil ylang ylang Gum myrrh Balsam copaiba Balsam fir, Canada Oil bitter almond, F.F.P.A. Oil ylang ylang, complete
Specifications for the follotving aromatics were issued: NO.
176 184 185 186 187 188 189 190 191 192 193 201 202 203 204 205 206 207 205 209 210 21 1 217 218 219 220 221
Dimethyloctanol Alcohol C-12 Amyl formate Dimethyl benzyl carbinyl acetate Ethg’l formate Ethylene brassylate Hexyl cinnamic aldehyde Nerolidol Octyl formate Phenylacetaldehyde Methyl benzoate Coumarin Isoeugenol Methyl cinnamic alcohol Cinnamic aldehyde Rhodinyl acetate Citronellyl formate Methylisoeugenol Isobutyl salicylate Benzyl propionate Ethyl benzoate Anisyl acetate Anisyl alrohol Diethyl phthalate Dihydroanethole Dimethyl benzyl carbinol Guaiacwood acetate VOL. 35, NO. 5, APRIL 1963
39
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222 Methyl cinnamic aldehyde 223 p-Cresyl acetate 224 p-Cresyl methyl ether Specifications for five essential oils and t v o aromatic chemicals were rev ritten .
KO. 2 Oil bois de rose 3 Oil petitgrain Paraguay
4 Oil .pike lavender 7 Oil lemongrass 10 Oil copaiba 5 Hydroxycitronellal 8 Terpinyl acetate Specifications TTere re\ ised for one essential oil and eight aromatic chemical. under R-7 to R-10: KO.
163 9 11 17 27 42 12.5 162 169
Oil lavandin abrial Terpinyl acetate Geranyl acetate Citronellol Amyl salicylate Anisic aldehyde Citronellyl acetate Geranyl formate Benzodihydropyrone
1 nen test procedure vas added to Soteq for Specifications and Standards: 1-1D-2 Instrumental Determinations, Year-Infrared Analysis, Determination of Free Alcohols
Infrared spectra for identification purposes have been included in the monographs for 20 E O.-L aromatic chemicals. This program will continue until inqtrumental identifieation. are completed for all E.O.;i. items. ANALYTICAL PROCEDURES FROM SCIENTIFIC AND TECHNlCAL LITERATURE
Essential Oils. T ~ i h a k(478) reported a determination of the essential oil and nzulene content of Achillea rnillifoliztrn (yarrow.). Ijhargava and Haksar (34) steamdistilled seeds of ajou an (Carum copticum) 10 monthq old and obtained 2.67% of cssential oil, fresh seeds gaye a yield of 3.1%. The oil contained thvmol (42 3%) and c a n acrol (8.2%). Freed from phenols, the oil contained a-pinene (4 to 5%), p-cymene (50 to 55%), dipentene (4 to 67c\, and 7-terpinene (30 to 5%). Sharnia, Sigam, and Handa (426) u9ed column chromatography to estimate phellandrene in oil of angelica. Gottlieb and llagalhaes (154) found t h a t the IT ood of -4niba firmula yielded 1 to 3Yc of essential oil low in terpenes, but containing benzyl salicylate and benzoate. Pertsex (S33j rectified anise oil by column chromatography on silica gel. It I\ as eqtablished that the physicochemical characteristics of anise oil change according to storage conditions. 40 R
ANALYTICAL CHEMISTRY
While this latter fact is well known and applicable to essential oils in general, the observation of specific changes under various conditions is of importance to our industry. Khan and Mohiuddin (230) reported a colorimetric determination of santonin in Artem’sia. The extracted santonin, in a solution neutral to 2,4-dinitrophenol, reacts with FeCI3 to yield a color, readable nithin 3 minutes a t 500 mp, Concentration can be determined from a standard curve. Kawatani, Fujita, and Ohno (228) investigated plants in regard to seasonal variations of santonin content, and methods of harvesting. The santonin content of ilrtemisia caerulescens m s the highest (1.2%) yyhen collected on July 1st. Belova (26) examined the steanidistilled oil of Artemisia lagocephala grown in the Far East and Formosa and found I-camphor, l-borneol, terpene compounds, and sesquiterpenes yielding azulene. Ban’kovskaya and Ban’kovskiI 127) investigated constituents of Artemisia copa aria during blooming, and identified scoparon (6,7-dimethoxq~ouniarin), Petronitz, Nerdel, and Ohloff (338) subjected the volatiles of Canada balsam oil to gas chromatography, identifying a-pinene (23.5%), 0-pinene (36.4%,), CY-phellandrene (2.7%), and p-p hellandrene (37.4%). Calvarano (55) examined chromatographically 11 samples of bergamot oil and determined bergapten (0.44 to 0.75%,) and citropten (0.25 to 0.35%). Rlesnard and Bertucat (282) reported that the acetylation value of bergamot oil cannot be determined by pyridinic and phosphoric acetylations. Soucek, Herout, and Sorm (439) fractionated and chromatographed the distillation residues from bergamot oil production and obtained bisabolene, isodigeranyl, and digeranyl. Theile, Dean, and Suffis (470) used a combination of spectrophotometric and chromatographic methods for the evaluation of bergamot oil. Fluck, hlitchell, and Perry (118) studied buchu leaf oil by gas chroniatography. Limonene, menthol, diosphenol, l-pulegone, and pseudodiosphenol were found in Barosma betulina leaf oil. In leaf oil of B. crenulata, limonene, nienthone, a trace of diosphenol, and a high proportion of l-pulegone were observed. Crowley (76) reported the isolation, in 0.15% yield, of 2,3-seco-oleana-12ene-2,3,28-trioic acid from the heartwood of Bursera graveolens var. villosula. The acid is described as a unique example of 2,3-biogenetic cleavage of a triterpene. Pigulevskii and Razbegaeva (342) investigated the essential oil of seeds of Carpopodizon platycarpurn (in 1.157,
yield) ; i t contained d-limonene, d-lina1001, and a bicyclic sesquiterpene (C15H24) Infrared analysis showed the d-linalool to have the isopropylidene structure. Lin and Wang (26.5) used column chromatography in the examination of the oil of Hinoki: Chamaecin, m-isopropylphenol, and 4-isopropylguaiacol were among the identified constituents. Akaci6 and Kustrak (2) correlated constituents of the essential oil of chamomile n i t h plant part, soil type, planting conditions, and storage of herbs. Blake and O’Neill (38) described a determination of ascaridole in chenopodium oil, using hydrogen bromide in acetic acid. Tai (463) reported a determination of the constituents of American chenopodium oil. Enzell (98) found that the heartnood of Cupresses thyoides contained carvacrol methyl ether, a-cedrene, cuparene, thujopsene (aiddrene), cedrol, widdrol, cuparenic acid, hinokiic acid (widdrenic acid), and “widdringtonia acid 11”; no tropolones were observed. von Rudloff (396) using fractional distillation, gas-liquid chromatography, and crystallization, isolated from a steam-distilled oil of araucaria : guiaiol (8% yield), a-cadinol (19.5% yield), and a mixture of CY- and p-eudesmol. Johns (210) described a convenient preparative chromatographic method for the separation and identification of components of natural clove oil, a Cs-C9fraction of the crude oil, and imitation clove oil. Johns (211) furthermore differentiated betu een genuine and imitation clove oil by vapor phase chromatography using a new ionization detector in combination with infrared spectroscopy. Wagner and Vincent (486) analyzed clove oil, eugenol, and thymol by a spectrophotometric-anion exchange technique. Ehrlich, Hammarsten-Rolbert, or similar reagents w r e used to give specific colors. Chaudhury, Gautam, and Handa (621 reported the physical constants of calamus root oils gronn in Jammu and Kashmir, and identified the important constituents. Durand and Paris (92) used chromatography and electrophoresis to determine anthracene derivatives in cassia oil; 1,8- dihydroxy - 3 - carboxyanthraquinone was the most important among them. von Rudloff (395)reqolved the components of oil of eastern n hite cedar into 30 to 32 peaks, using a series of gas chromatographic columns. Gold and Wilson (145) examined the volatile compounds of celery. Gas chromatography and infrared spectra shon ed the presence of d-limonene, myrcene, isobutyric acid, valeric acid, pyruvic acid, a branched isomer of heptanoic acid, sedanoic anhydride,
guaiacol, octanjl, citral-B (neral), and heptanol. The presence of palmitic acid and a branched isomer of octanoic acid was suspected. The coritribution of these compounds to celery flavor was discussed. Teisqeire (468) fractionated French clary sage oils, chemically separated the head fraction into groups, and reported the gas-chromatographic evaluation of components. Teisseire (467) used gas-liquid partition chromatography to study fractionated French and Russian clary sage oils. I n the French oil, 30% linalool. C 9 aldehydes, hexanol, l-octen3-01, and cineole n ere detected; the terpenic fraction contains eight principal terpenes. In the Russian oil BzH, cineole, and six terpenes were found. Chikalov (64) noted t h a t the harvest of coriander seed and yield of highquality oil a e r e highest when the fruit on the central, and on the first-order umbel, a e i e of a chestnut color. Rahoka (372) noted t h a t only coriander seed stored in glass bottles showed the same oil ahsay as fresh seed. Popov (356) simplified the microanalytical technique of Grigorovich, and developed a new colorimetric quantitati) e determination of the esvntial oil in coriander seed. With a dilute IC2JIn04 solution, a color developed and was compared n i t h a color kcale. Paul, Bawdekar, Joshi, Kulkarni, Rao. Kelhar and Bhattacharyya (331) examined the essential oil of costus root. Because of its unusual thermolabile properties, this oil was extracted n ith petroleum ether at a temperature of approximately 40’ C. Some of the important constituents of this essential oil ere identified and their ph isical Ixoperties \I ere reported. Xigam and Purohit (311) steamdistilled leaves, soft stems, and flowers of Cyathocline lyrata, obtaining a n oil t h ,t contained, among other compounds, carvacrol, p-cymene, d-camphor. citral, and cythoclol, a nelv sesquiterpene alcohol. Sigani, Dhingra, and Gupta (307) elanlined the essential oil from the peel of Citrus nzacrocarpa, and described methods for idcntifying the constituents in various fractions. Sutherland, Webb, and Wells (460) examined tc o E u c a l y p t u s species not usually found in rain forests, and reported constituents of their essential oils. Rao and Sood (580) steamdistilled fresh buds of E u c a l y p t u s citriodora, yielding 0.50 to 0.857, ebsential oil; a-phtllandrene, citronellal, citral, geraniol, citronellyl acetate, and iiovalerate ere identified. Alelera and Naves ($81) isolated tis- and trans-2-(2-methylpropenyl)-4methyltetrahj dropyran from geranium oil. Studies of the stereochemistry
of these compounds based on X h I R were reported. Xaves, Lamparsky, and Ochsner (302) by distillation and chromatography identified several tetrahydropyrans in oil of geranium. Nagasawa and Koresaa-a (298) found the physicochemical properties of geranium oil gron-n in Japan different from those of Pelargonium introduced from France, Italy. and America to Japan. Naves (301) applied a combination of distillation, vapor-phase partition chromatography, and infrared for the examination of the essential oils of ginger grass (Cymbopogon m a r t i n i var. Sofia and C. densiflorus). Three isomers of perillic alcohol were identified. Schweisheimer (42.4) reviewed the composition and preparation of terpeneless oils, particularly terpeneless grapefruit oil, by Kirchner’s and Miller’s solid-liquid chromatographic methods, and the use of these products to improve perfumes. Obata and Ishikana (318) subjected a n extract of hemp leaves and tops t o paper chromatography, and determined the main constituent as eugenol, the minor component as guaiacol. D e Ropp (83) reported the chromatographic separation of the phenolic components of Cannabis sativa (hemp). The solids from a MEOH extract of the flowering tops were adsorbed on Florasil and eluted with benzene to yield a red oil. Eight phenolic components were isolated by paper chromatography. Roberts (382) investigated the oxygenated constituents of hop oil by gas chromatography, and reported the presence of 2-methylbutyl isobutyrate (12%), Me pelargonate (l%b),linalool (5%), methyl nonyl ketone and methyl caprate (2%), methyl geranate (20%), three esters (lo%), and 14 less volatile and nonsaponifiable compounds which constituted about 50% of the oxygenated fraction. Cassuto (58) subjected essential oil of hops (iilsatian) to gas chromatography. Humulene, p- or ycaryophyllene, methyl nonyl ketone, limonene, myrcene, and a-pinene were identified. Farnesene and y-pinene could not be detected. Mollan (292) reported the yields and properties of oil from the wood, leaves, and bark of the Imbuia plant. Runeberg (401) found in the heartn ood of J u n i p e r u s cedrus, thymoquinone, thujopsene, cuparene, cedrol, deltacadinol, widdrol, “TI iddringtonia acid 11,” nootkatin, p-thujaplicin, and carvacrol. Pilo and Runeberg (545)examined the heart\\-ood of J u n i p e r u s chinensis and isolated thujopsene, cuparene, cedrol, niddrol, hinokiic acid, ‘(IT iddringtonia acid 11,” carvacrol, thymohydroquinone, 3-hydroxyth~-moquinone,and 3,6dihydroxythymoquinone. The presence of nootkatin and a- and p-thujaplicin was indicated by paper chromatography;
the presence of 2-cedrene n as indicated 1 i a gas chromatography. Runeberg (402) examined the heartwood of J . phoenicea, finding thujopsene, cuparene, cedrol, widdrol, “widdringtonia acid 11,” hinokiic acid, nootkatin, p-thujaplicin, and carvacrol. Runeberg (400) investigated the heartn ood of J . thurifera and reported the presence of a-cedrene, thujopsene, two apparently new CISH24 hydrocarbons, cuparene, cedrol, a CmH1606 compound, a diol (C30HS402), carvacrol, nootkatin, p-thujapliciri, hinoliic acid, and ‘‘widdringtonia acid TI.” T n o other sesquiterpenic hydrocarbons coutaining vinylidene groups we1e present; one of these probably has a curcumene skeleton. Runeberg (398) found in the heartaood of J . utahensis, thujopsene, cuparene, a iddrol, ‘lniddringtonia diol,” carvacrol, nootkatin, hinokiic acid, a yellow compound (C20H200S), a hydroxy acid, and a carbonyl-containing compound, both probably sesquiterpenic in nature, Paper chromatography indicated the presence of p-thujaplicin; gas chromatography that of a-cedrene. Runeberg (399) identified in J . virginiana oil (commercial cedarn ood oil), cuparene, cedrol, middrol, a-cedrene, and thujopsene. The presence of a dextrorotatory curcumene (ontaining a vinylidene group n as suspected, and gas chromatography indicated several other unidentified sesquiterpenes. Bruno (59) identified by gas chromatographic analyqis and various reactions in J u n i p e r u s sabina, d-sabinene, a-pinene, sabinyl acetate, and limonene ; in T h u j a occidentalis, a- and p-3thujanone and borneol; and in R u t a graveolens, pinene, limonene, methyl heptyl ketone, and methyl nonyl ketone. Hirose, Nishimura, and Sakai (180) used vacuum fractionation, gas chromatography, liquid chromatography, and infrared spectroscopy to compare the constituents of oils of J u n i p e r u s rigida (Japanese), J . c o m m u n i s (Italian), and commercial oil of juniper berry. Goryael. and Dahalilov (149) analyzed the essential oil of leaves of J u n i p e r u s turkestanica (Turkestan juniper) by fractional distillation and chromatography on -11203. Bernhard and Scrubis (31) in\ estigated the essential oil of the epicarp of kumquat (Fortunella margarita). The ultraviolet spectrum exhibited nonr of the peaks or bands associated u i t h typical citrub oil coumarins. By gas chromatography, a-pinene, myrcene, d-limonene, n-octyl acetate, decanal, undecanal, bornyl acetate, citroneliol, geranyl propionate, and trans-carvcol nere identified. Gupta and Gupta (158)examined the petitgrain oil of Fortunella japonica and found it to contain a-pinene, citral, VOL. 35, NO. 5, APRIL 1963
41 R
bisabolene, I-linalool, terpineol, and probably a diterpene. K g a m and Purohit (513) reported the presence of dl-a-pinene (25.4%), 3-carene 18.8%), p-cymol (6.3%), humulene (38.0%), d-cadinene (10.60/,), s-guaiazulene foreruns (8.6%), and unidentified resins (2.37,) in a leaf oil of Lantana indica obtained by steam distillation in 0.07 to 0.170 yield. Nigam, Gupta, and Dhingra (309) distilled the oil from LazirzLs nobilis (laurel leaves) and reported physical properties and chemical constituents. Sokol (437) preserved flowers of lavender in a 5 to 10% aqueous CuS04 solution to ensure a high yield of oil in later extraction. Storto and D i Prima (464) studied the ratios of linalool and linalyl acetate in lavender oils by gas chromatography, and based authenticity upon this relation. Naves and Tullen (303) shon-ed by ozonolysis that the ocimene obtained from lavender oil has the b structure, not the a structure assumed from its infrared spectrum. Oil of lavender also contains camphene, benzoylborneol, and a-pinene, which were obtained by preparative chromatography. Lazur’evskii and Kal’yan (260) investigated isolates from wastes in the production of oil of lavender. A sesquiterpene (CI5HL6), a diterpene (C90H8402), a coumarin, umbelliferone, a triterpene (C30Hm02), and a crystalline substance (C26H4202)ere identified. Fenaroli (IO’?) studied by gas chromatography the various oils of lavender and lavandin produced from 1959 to 1960 in France. Constituents of these essential oils rvere separated and identified by infrared. Naves (299) investigated the essential oils of lavender and lavandin by gas chromatography. The absence of bornyl acetate from both of these oils was established. Stadler (442) identified the ketones present in the essential oil of lavandin by separation with Girard P reagent, followed by gas chromatography. Bernhard (29) applied gas-liquid chromatography For the identification of components in cold-pressed California lemon oil. Clark and Bernhard (70) tentatively identified, in the oxygenated fraction of lemon oil, 3-hexen-1-01, n-nonanal, methyl heptenone, octyl acetate, n-decanal, linalool, n-undecanal, citronellyl acetate, geranyl acetate, citral, n-octanal, cineole, linalyl acetate, linalyl propionate, decyl acetate, decanol, a-terpineol, citronellol, and d-carvone. Clark and Bernhard (69), examining the silicic acid-purified hydrocarbon fraction of lemon oil by gas chromatoggraphy, tentatively identified a-pinene, camphene, P-pinene, mgrcene, d-limonene. terpinolene, and p-cymene. 42 R *
ANALYTICAL CHEMISTRY
Stanley, Ikeda and Cook (448) developed a method of separating the terpene hydrocarbons from citrus oils for gas chromatographic investigation. Sabinene was identified in lemon oil, and a-thujene tentatively identified. Analyses of terpene hydrocarbons of 105 lemon oil samples nere reported. A direct relation betn een d-limonene concentration and optical rotation, and an inverse relation between concentration of ppinene and optical rotation, were observed. Ikeda, Stanley, S’anniw, and Rolle (197) reported that p-cymene is formed during deterioration of lemon oil from y-terpinene. Euperiments proved that citral is not the precur-or of p-cymene. y-Terpinene isolated from lcmon oil oxidized to p-c? mene n hcn e\posed to air. Slater (432) studied the h! drocarbon and oxygenated fractions of natvral and terpeneless lemon oils using gas chromatography and infrared spectrosop?. Bernhard (28) reported that among 40 liquids tested, LA4C-2-R446,L-\C-4R777, and Craig polyester adipate n-ere most efficient in the separation of lemon oil components by gas chromatographv. Stanley (447) developed a qualitative chromatostrip test for chalcones in lemon oil. Kaves (300) analyzed lemongrass oil with emphasis on the citral isomers for the production of pseudoionone, methyl pseudoinones, and nerol. Yeh (499) examined hIalabar lemongrass oil and reported several constituents, aniong them 81.4% citral. Slater (491) examined by gas chromatography the oxygenated and hydrocarbon fractions of West Indian (Dominican) hand-pressed and distilled lime oils, pointing out differences in constituents. Oxygenated compounds, terpeneq, and sesquiterpene hydrocarbons were identified. Slater (433) also compared by gas chromatography the components of West Indian and hIexican distilled lime oils. I n the Dominican oil seven additional compounds, as well as a number of compounds previously noted in the hfexican oil, were identified. Kumar and Banerjee (254)) using chemical methods, examined the oil from fresh green leaves and tnips of the lime tree (Citrus aurantijoh~and found i t to contain 20.5% terpenes, 13.2% alcohols, 36.07, aldehydes, 23.8% esters, 2.0% acids, 2.0% citropten, and 2 5% of a n unidentified fraction. Kawano and Oishi (227) established the presence of limonene and 65y0 citral in oil of Lindera cilriodora. Furst and Feustel (131) determined the carbonyl compounds in Litsea cubeba oil, using paper chromatography. Furfural, HCHO, RIeCHO, Me2C0, PrCHO, iso-BuCHO, methylheptenone,
citral, and citronellal a e r e identified as 2,4-dinitrophenylhydrazones. Pruthi, Lal, and Subrahmanyan (367) compared the ultraviolet, visible, and infrared spectra of Indian mandarin oils n-ith those of other citrus oils. Tangeritin decreased or in reased under different conditions. Betneen coldpressed and distilled mandarin oils, significant differences in ultraviolet adsorption spectra were observed. hIukherjee and Bose (296)determined the IOFSof essential oil in peel of Sikkim mandarin oranges at different stages of maturity and under various conditions of storage. h’igam and Purohit (SIZ), using column and paper chromatography, identified in essential oil of Jfurraya koenigii: pinene, sabinene, dipentene, cadinenc, a-caryophyllene, and twpineol. Bernhard (SO) analjzed oil of Citrus sinensis (orange) by gas-liquid chromatography, and reported tentative identification of 14 compounds not previously noted. Kesterson and Hendrickaon (229) recorded the physical and chemical properties of cold-pressed niurcott orange oil. I t n s established that this cil has properties similar to thobe of tangerine oil. Dallacker, Gohlke, and Lipp (80) identified safrole as a constituent of parsley seed oil. I n improved method 11as developed for determining the apiole and myricticin content of the same oil by ozonization of iaoapiole and isomyristicin. Dummond ( 9 1 ) compared the chromatograms of various patchouli oils, and reported constants for 14 oils. Kopp and Racz-Kotilla (943) discussed the growing conditions and volatile oil productions of Pelargonium mseum, and reported the properties of the oil. Jennings and Krolstad (2OS), using gas chromatography, separated oil of black pepper into 23 volatile compounds; among these nere CY- and @-pinene, d-limonene, and p-caryophyllene. a-Phellandrene was not obs e n ed. Kubrak (251) discussed the p~ocess of oil production in Mentha l o n g i f o h , noting changes in specific gravity, refractive index, and optical rotation as the plant goes from sprouting phase to full bloom. I n some cases, a maximum deviation of piperitone oxide appeared in the first stage of plant development. with a decrease of the oxide as the leaves and flowers reached full bloom. Smith and Levi (436) applied gas chromatography to oils of peppermint and Xentha artemis for the determination of their geographical origin, the evaluation of manufacturing processes, and adulteration. Ognyanov and Vlakhov (321) in-
vestigated the terpene fractions of crude Bulgarian peppermint oil, using the method of Sorm et al. From the (*)-camphene, fraction bro 63-95', (f)-a-pinene, (*)-&pinene, (-)-limonene and dipentene, b-myrcene, y-terpinene, p-cymene, o-cymene, and 1,8cineole L? ere separated and identified by gas chromatography and infrared analgsis. Jaspersen-Schib (106) employed thinlayer chromatography to identify adulterants of M e n t h a oils. Ban (16) investigated the factors influencing flavor loss duiing spray drying of peppermint oil-gum ArabicR ater emulsions. Laughlin (258) examined the physical and chemical properties of Michigan peppermint oil and found that with maturity of the plant, the optical rotation, ester content, and amount of menthol increase, n hereas the amount of menthone decreases. A good correlation b e h e e n menthol and menthone concentrations was found. Steigern ald (449) reported that pel)perniint plants from tn o areas of cultivation in Germany (1960) had 12.77, stems, yielding 1.24% oil. In Rumanian plants, this ratio n as 6.57, stems and 1.247, oil; in Hungarian plants, 4.770 stems and 1.8% oil. Rradyshev and Cherches (44) fractionally distilled oil of Picea ercelsa (Sorway spruce). The fractions mere analyzed and their composition was reported. Zanini, Dal Pozzo, and Dansi (504), using gas chromatography, found five terpenes and one ester in fractions of dwarf pine needle oil. Kagasawa (297) examined the essential oil of Radix asiaari by infrared spectroscopy. The constituents of this oil vary greatly according to the habitat of the plant. Methyleugenol, safrole, 1,8-cineole, and elemicin were among the constituents. Ferrero (108) found 1% of 3-methyl2-(3-methylbuten-2-~1) tetrahydrofuran in a fraction of Bulgarian rose oil. Gurvich and Neparidze (160) described a rapid nephelometric method for the determination of essential oils in rose and basil; results agreed well I\ ith those obtained by E t 2 0 extraction. Xigam, Kigam, and Dhingra (510) determined the stearoptene content of an Indian rose oil by a column chromatographic and gravimetric method. Sigam, Gupta, and Dhingra (308) analyzed oil of Rosa borbonica, and found 23.89% Z-citronellol, 12.78% geraniol, 16.36% phenethyl alcohol, 22.17, stearoptenes, 0.53% citral, 0.49% carvone, and 0.43% nonanal. Other minor constituents were linalool, geranvl formate, citronellyl formate, and geranyl acetate. Aka% and Srepel (5) determined the properties and condtuents of three
rue oils, including that of Ruta graveolens. For the detection of the botanical origin of the oils, color reactions were devised. Brieskorn, Leiner, and Thiele (47) isolated the bitter substance from sage leaves and reported the properties. The substance, C20H3604, was tentatively named picrosalvin. The compound does not belong to the diterpenoid group, and is not related to marrubiin. Its bitter value is 1: 14,000. Salgues (407) examined the essential oils of various species of Salvia: S. triloba, S. juriscii, S . oficinalis, S.sclarea, S.yrahami, S.lavandulaefolia, and S. carnosa. The physical properties of these oils and their ketone, ester, terpene, and sesquiterpene contents 17-ere recorded. Mollan (290) reported the physical properties of 78 samples of Ocotea pretiosa. yields of oil, and safrole contents. Mollan (291) also examined the oil from an Ocotea pretiosa variety from Brazil, and reported yields, properties, and certain constituents in different parts of the tree. Gottlieb, Fineberg, and Magalhaes (153) differentiated between certain Brazilian sassafras oils (Ocotea pretiosa) -i.e. oils containing I- and d-camphor, and those free of camphor. The latter exhibited considerable uniformity over a wide geographic and climatic area. PigulevskiY and Belova (341) obtained, from the fruit of Sium latifolium, 7,5y0of an oil consisting of d-limonene and 10% perillaldehyde. Runti and Bruni (40s) analyzed thyme oil by gas chromatography. Various phenols, alcohols, and hydrocarbons mere identified. Hodges (182) chromatographed a petroleum extract of leaves of T h u j o p s i s dolabrata (Hiba) and identified sesquiand diterpenes, ginnone, ginnol, @-sitosterol, totarol, and other compounds. Onishi (323) investigated the essential oil of yellow tobacco leaf. The oil was separated into acidic, basic, neutral, phenolic, and carbonyl fractions. The constituents of these fractions were determined by chromatographic methods. Rao and Bhave (379) analyzed the essential oil of the dried ripe fruit of Z a n t h o x y l u m rhetsa, finding y-terpinene, d-a-phellandrene, 4-carene. p-pinene. d-a-dihydrocarveol, 4-terpinenol, and dl-carvotanacetone. Fester, Retamar, and Ricciardi (Ion) examined essential oils from nine Argentine plants. Ledol from Lepechinia jloribunda was isolated and then identified by infrared spectroscopy. illvarado and Manjarrez ( 7 ) identified a number of components of Mexican essential oils by gas chromatography. Goryaev and Saldarova (151) examined the components of essential oils
of tn o n ormwood ( A r t e m i s i a ) speciesLe., terrae, and albae (a high camphorcontaining oil)-and of Cossack juniper. Podlubnaya and Babkova (34.9) discussed the application of fluorescent techniques to the analysis of many essential oils and aromatic alcohols used as flavorants. PIlisra and Krishna Rao (287) determined the essential oils in small samples of spices by hydrodistillation into acidic dichromate solution and subsequent titration of excess dichromate m ith standard thiosulfate. Gokhale (144) discussed the design of steam distillation equipment for essential oils and the efficiency of operation for different types of plant materials. Pimazzoni (345)reported that molecular distillation of essential oils gives higher yields and better quality than usual distillation. Bourbon vetiver oil 17-asused as an example. Peyron (339) described the applications of partition, ion eschange, and adsorption chromatography to the study of essential oils and perfumery chemicals. La Face (265) identified, by chromatographic and spectrophotometric methods, constituents of oils of bergamot, orange, and tangerine, mhich had not been reported previously. Shoda, Obata, and Xshida (429) described a new solid phase material uhich n a s used in the gas chromatography of essential oils such as lemon, orange, bergamot, onion, etc. Liberti and Cartoni (265) described a gas chromatographic technique for the quantitative and qualitative detection of terpenic hydrocarbons in essential oils. Quantitative data n i t h regard to the essential oils from lemon and tangerine are tabulated. von Schantz, Lopnieri, Stroemer, Salonen, and Brunni (417), using thinlayer chromatography, identified the constituents of a large number of essential oils, among them lemon, orange, bergamot, mace, marjoram, cardamom, sage, tansy, rosemary, cinnamon, cassia, clove, and anise. Landgraf (257) stated that chromatographic separation of the basic components of essential oils (specifically citrus oils) has advantages over vacuum distillation and selective solvent extraction, since there is better separation of the oxygenated fraction from the hydrocarbon fraction; moreover, possible high temperature effects are eliniinatea. Kaginaire and Guillot (495) described an iodometric determination of the peroxide number of oils of orange and lemon. I n the case of orange oil, the peroxide number is reduced up to 857, by removal of terpenes; nevertheless, further oxidation goes on in storage. I n the case of lemon oil the peroxide number rose from 10 to 1300 after 18 months. VOL 35, NO. 5, APRIL 1963
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Gattefosse ( 135), reviewing advances in the essential oil field, noted that the peroxide index is an objective measure of stability. von Schantz (416) suggested characterization of essential oils and their chief constituents by peracid values after oxidation with monoperosyphthalic acid. von Schantz (416) also discussed the methoxy number, peracid number, and acetyl number of some essential oils, and recorded the oxidation curves of anethole, anise oil, and eugenol. The acetyl number is given for rose, santal, and calamus oils. Franchi and Franchi (124) characterized essential oils by a so-called “propionyl number.” Tucakov (476) reported the pharmacological proper ties of many common and uncommon essential oils. Hills, Petley, and Roberts (179) investigated olfactory changes of irradiated essential oils. Of the oils and isolates studied, 31 showed enhancement of olfactory properties, eight showed deterioration, and eight n ere not affected. Resinous materials nere indifferent to this treatment. The order of stability of typical components of the oils n a s : aldehydes > alcohols > esters > hydrocarbons > phenols. The most outstanding effects were the enhanced flavor of peppermint oils and the preservative effect observed in oils of citrus fruits. Fazakerley, Garrett, Hills, and Roberts (103) reported the olfactory and chemical changes in essential oils subjected to gamma-irradiation. Low doses improved the olfactory properties and did not alter physical and chemical properties. Irradiation improved the characteristic note of floral oils; citrus oils showed better preservation and less resinification. Olfactory evidence indicated that the radiation resistance of oil constituents decreased thus: aldehyde, alcohol, ester, hydrocarbon, phenol. High doses of radiation destroyed camphene in Brazilian peppermint oil, producing peroxide, and ultraviolet radistion changed camphene to tricyclene. Fujita and Nagasawa (128) distinguished the crude drugs of sweet fennel, anise, and star anise by infrared spectroscopy of their essential oils. Pruthi, Parekh, Lal, and Subrahmanyan (568) analyzed (spectrophotometrically) a number of Indian citrus oils. Peroxide values and infrared mere correlated. Gjerstad (141) used ultraviolet spectrophotometry for the quantitative evaluation of oils of sweet orange, orange flower, lime bergamot, and grapefruit peel. Podlubnaya, Babkova, and Epel’man (350) studied the ultraviolet absorption spectra of lemon oil and citral, peppermint oil, and menthol in 80% alcohol. 44 R
ANALYTICAL CHEMISTRY
Zolotovich and Iskrov (507) determined the residue of the E-605 forte and parathion preparations in essential oils by saponifying their active substance and obtaining p-nitrophenol in the free state, then reducing the latter to p aminophenol, TI hich on treatment IT-ith phenol solution in KH3 medium produces a measurable blue color. The technique can be used for chlorine-e.g., DDT-by burning or mixing the oil a i t h an alcoholic alkaline base. Chlorine can be detected by both methods as AgC1. Sterrett (451) revier? ed the general nature and production of essential oils. Kulka (253) reviewed the chemistry of essential oils. K h i t e and Eiserle (692) gave a review of the history, production, marketing, and quality of essential oils, isolates, oleoresins, and certain aromatics. Bedouhian (22) in his yearly review reported recent developments in the essential oil chemistry. Acids. Janak, Dobiasoi a, and Veres (204) described a gas chromatographic separation for isomeric saturated and unsaturated C, and C6 fatty acids. Kitagawa (236)reported a paper chromatographic analysis of fatty acids which have less than 10 carbon atoms. Turgel and Kashanova (477) analyzed, by chromatography, mixtures of lower fattj. acids such as valeric, lactic, propionic, acetic, and formic. Gordillo and Montes (146) developed a semimicro chromatographic technique for determination of C1-Clo acids. Schormuller and Langner (420) identified volatile acids such as acetic, propionic, caprylic, pelargonic, valeric, isovaleric, caproic, heptanoic, and capric, by gas chromatography. Sonvolatile di- and tricarboxylic acids ~5 ere determined by ion exchange chromatography and a-keto acids as their 2,4-dinitrophenylhydrazones, by circular filterpaper chromatography. Hammarberg and Kickberg ( 167) separated C1-CI4 straight-chain fatty acids by a rapid paper chromatographic method. ChurAEek (68) reported a paper chromatographic separation and identification of C4-C14 fatty acids as 2,4-dinitrobenzyl esters. I n s d l and James (200) described a gas chromatographic method for the qualitative and quantitative analysis of C1-C20 fatty acids. Chayen and Linday (63) used ascending paper strip chromatography to separate stearic, palmitic, and myristic acids. Bhown and Gaur ( 3 6 ) , using circular paper chromatography, determined R, values for the sodium salts of acetic, propionic, butyric, caproic, caprylic, and capric acids, the respective hydroxamic acids, and lauro- and oleohydroxamic acids. A linear relation between color
intensity of the spots and amounts of hydroxamic acid derivatives was noted. Metcalfe (185) discussed the gas chromatography of unesterified fatty acids on a polyester column. Saturated and unsaturated fatty acids (C12-C2J and methyl esters were separated. Jesting and Bang (209) separat,ed Cx2-Cl8 fatty acids and their methyl esters chromatographically, using programmed temperature control. Jaky (205) discussed paper chromatographic methods for the separation and identification of C54& fatty acids, also identifying animal and plant glycerides. Fatty acids having the same E , values, called critical pairs, could be separated either a t low temperatures (-30°C.) or as their derivatives. Jones (214) studied the effect of chain length on the infrared spectra of fatt’y acids. hIangold and Kammereck (276) used thin-layer chromatography for the separation of methyl esters of fatty acids as a complementary method to gas chromatography. It was concluded that the combination of the two techniques is more accurate than the second method alone. J a r t (105) reported the infrared spectra of 43 fatty acids and fatty acid esters in CS2 solution. I n particular, trans absorption a t 962 cm.-’ was studied; extinction coefficients of the pure substances a t the trans maxima were calculated. Applewhite, Diamond, and Goldblatt (12) determined the R, values of some fatty acids and esters, using ascending chromatography in various solvent systems. Josien, Lascombe, and Vignalou (217 ) compared the infrared carbonyl bond frequencies in a series of aliphatic acids and esters, and commented on the differences when measured in the gas phase and in carbon tetrachloride solution. Schlenk and Gellerman (419) found that instantaneous esterification occurs when diazoniethane gas is introduced into a solution of the acid in Et20 containing 10% 1IeOH. I t is possible t o evaluate any side reactions of the process by paper chromatography. Slepecky and Law (434) reported that +unsaturated acids, in 80% H1S04, sholy maximum absorption a t about 250 m p ; this can be used for quantitative spectrophotomet’ricanalysis. Brouwer (51) found that separation of benzoic acid from interfering substances by chromatography makes the hlohler reaction more sensitive and specific. Stahl, Voelker, and Sullivan (446) described a determination of amino acids in vanilla extracts. The method is a compromise between the ti?-o-dimensional chromatographic method and the total color method. It provides a. means of differentiating among ex-
tracts differing in their Bourbon and/or Mexican and Tahiti bean content. Sullivan, Voelker, and Stahl (455) reported on extracts from Vanilla planifolia and Vanilla tahitensis. Determination of organic and amino acid comlrosition and fluorescence chromatograms give a clear indication regarding the authenticity of these extracts. Halniekoski (165) described a thinlayer chromatographic separation for 1)henolic carboxylic acids, such as vanillic, protocatechuic, ferulic, and isoferulic acids. Sterescu (460) determined vanillicacid by a paper chromatographic separation. Results are accurate within +2%. Fitelson (114) described a paper chromatographic analysis of the organic acids in vanilla extracts. The test is valuable in detecting foreign material o f different acid pattern. Ivanov. Panaiotov, Tchorbadjiev, and Belitcheva (2021 identified the acids occurring in rose oil by chromatographing t'he hydroxamic acid derivatives. Ting and Ileszyck (473), using a gradient elution method, isolated I-quinic acid from orange, grapefruit, tangerine, lemon, and lime fruit. Schramm (421) separated nonvolatile acids (tartaric, succinic, citric, or malic) i n plant tissues by paper chromatography. Rudol'fi, Kore. and Reingach (397) described the paper chromatography of fatty, aromatic, and fatty-aromatic acids, and a method of color development. Wagner and Isherwood (487)determined several mono- and dicarboxylic acids by extraction n.ith aqueous EtOH, purification by elution from silica gel, and titration. Hone (189) paper-chromatographed 100 organic ac,ids and arranged R,u values into two groups, depending on the number of carboxyl and other groups present. Hosoya, Tanaka, and Kagakura (188) studied ultraviolet absorption spectra of benzoic acid and met,hyl benzoate to determine the effect of dimerization on the iritramolecular charge-transfer band of 1,rnzoic acid. Gancev and Todorova (134) reacted micro amounts of cit'ric and malonic acids in solution with Xi(OH)*. The reaction products were precipitated on chromatographic paper and developed with rubeanic acid. Pohloudek-Fabini and Wollmann (3641,using ascending cylindrical paper chromatography, separated a number of organic acids of metabolic importance. Emelin and Svistunova (96) detcrmined acetic anhydride by its reaction with P h S H ? , using potentiometric titration of excess PhNH,. Aldehydes and Ketones. Levi and Laughton (262) ext'ended their barlituric acid method for determining citral, considering side reactions and
interfering substances. Their method rras applied to lemongrass oil (East Indian and West Indian), lemon, lime, orange, grapefruit, and terpeneless oils. A distilled Mexican lime oil showed furfural; geraniol and citronellal contained citral nhich increased in geraniol on storage. Yokoyama, Levi, Laughton, and Stanley (500) reported details of the mphenylenediamine method for determination of citral in citrus extracts and citrus oils, adapting absorbance readings for color measurement in genuine and artificial citrus extracts. The results mere in substantial agreement with those obtained by the barbituric acid method, but lower than those obtained by the conventional XH?OH and phenylhydrazine methods. Ail th, Stringer, Skakum, and Levi ( 1 ) collaborated on a technique for determining citral in essential oils by condensation n-ith barbituric acid and measurement of absorbance a t 336 mp. Oils of the families Gramineae, Myrtaceae, and Rutaceae were examined and good accuracy was obtained Guren (161) reported a paper chromatographic method to identify and determine citral. Calvarano (54) evaluated various determinations of citral and reported that colorimetric methods using sodium-3,5dinitrobenzoate and benzidine can be used when citral is the only carbonyl compound present. The methods using mixtures of vanillin and piperidine or barbituric acid are specific for citral evaluation. Markman and Fazylova (276) investigated the polarographic behavior of vanillin in n-ater, EtOH, and aqueous EtOH solutions. Woggon and Kohler (493) developed a chromatopraphic-oscillopolaropaper graphic method for determining vanillin and ethvlvanillin in foods. The technique i* rapid and sensitive. Woggon, Rauschler, and Kohler (494) described a quantitative paper chromatographic determination of vanillin and ethylranillin in the presence of each other. Darjdek (81)reported a polarographic method for determination of vanillin as its ouime. Figurski and hiichalska (110\, using color reactions and chromatography, found vanillin and ethvlvanillin in Platanthera bifolia. The developer was hvdrazine sulfate. Vasiliev, Sisman, and l l a n g u (479) dpscribed the determination of vanillin in HCOSMel solution with 0.1N solution of MeOXa in MeOH plus C6Hc, with thymol blue as indicator. Dhont and de Rooy (84) reported R, values for the 2,4-dinitrophenyIhydrazones of vanillin, VeratraldehT.de, ethylvanillin, salicylaldehyde, BzH, cinnamaldehyde. anisaldehyde, and CY- and p-ionone on chromatoplates using iilica gel G.
Hald (164) suggested a colorimetric method for detection of 2-alkoxyphenol impurities in vanillin and ethylvanillin. Stoll and Prat (453) by application of paper chromatography, found that the aldehydes in vanilla extracts such as vanillin, ethylvanillin, and p-hydroxybenzaldehyde are oxidized to the corresponding acids. Becher and Rudomanova (21) described a colorimetric microdetermination specific for acetaldehyde in wine and fermenting liquids. A stable color develops with the reagent p-hydroxydiphenyl; other aldehydes do not interfere. This analytical procedure might be well adapted to our industrv. hfaruta and Suzuki (278) determined small quantities of saturated and CY,@unsaturated aliphatic aldehydes hy paper chromatography and ultraviolct spectra. Using the first method, no difference was observed between the saturated and unsaturated aldehydes for Rj values of the dinitrophenylhydrazones of the same C number. With ultraviolet spectra, differences were observed, the saturated aldehyde dinitrophenylhydrazones have an absorption band a t 35'3 mp; the unsaturated at 373 nip. Gray (156) separated several longchain fatty aldehydes as their dimethyl acetals by gas chromatography on Apiezon L grease or Reoplex 400, a t 190° c. Sau-icki, Hauser, and Fox (412) employed colorimetric techniques for the determination of aliphatic aldehyde 2,4dinitrophenylhydrazones via Foimazan cation. Porsch and Farnoiv (359) reviewed the chemistry of geranial and neral, reported their presence in various essential oils, and published infrared, ultraviolet, and gas chromatographic curves of these materials. Forss, Dunstone, Hormood, and Stark (120) characterized a number of unsaturated aldehydes in microgram quantities j among these were nonanal, trans2-nonenal, trans-2-trans-4-nonadienal. The authors used various methods, and found gas chromatography on Carbowax 400 and paper chromat,ography of the 2,4-dinitrophenylhydrazonesto be the best method for distinguishing among trans-2-nonena1, trans-2-trans-6-nonadienal, and trans-2-cis-6-nonadienal. King and Vig (233) studied the nealinfrared spect,ra of a,B-saturated and unsaturated aliphatic aldehydes. Hatanaka and Ohno (169) rel'orted that, based on infrared spectroscopy and its properties, natural leaf aldehyde ( 2 hexen-1-al) has the trans structure. Rudkovskii, Gankin, and Imyariitov (392) separated aldehydes as t'heir bisulfite compounds by steam distillation. The aldehydes were fractionated and the bisulfite solution \\-as reused. Schulek and RIaros (422) proposed an iodonietric determination of formaideVOL 35, NO. 5, APRIL 1963
0
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hyde and acetaldehyde based on formation of bisulfite addition compounds, and iodometric determination of the SO, liberated by KCN. Panaiotov and Ivanov (529) applied paper partition chromatography for the detection of seven aldehydes such as acetaldehyde, valeraldehyde, and phydroxybenzaldehyde, which were previously not identified in rose oil by the classical chemical methods. Malmberg, Weinstein, Fishel, and Krause (273) described a colorimetric determination of acetaldehyde, using 2(p-phenylazophenyl) acid as reagent. Honkanen (186) developed a countercurrent technique for separating a mixture of 2,4-dinitrophenylhydrazones oi the normal C1- 9 aldehydes. Powers, Harper. and Tai ($62) determined aromatic aldehvdes such as piperonal, methoxybenzaldehydes, etc., by near-infrared spectrophotometry. These aldehydes exhibit two strong characteristic bands a t 2.21 and 2.25 microns. Kowalewski and Kowalewski ($47) investigated the nuclear magnetic resonance of benzaldehydes. The sglitting of the proton signal of the CHO in o-substituted benzaldehydes is a result of interaction with a ring proton. With increasing electronegatility of the substituents the splitting decreases. Domansk4 and Juritnkova (87) found that the formation of benzaldoxime in acid and neutral media involves a reversible reaction; the velocity of oxime formation has a distinct maximum between pH 5 and 6, due to the reaction mechanism. Rao and Rao (378) measured and interpreted the near-infrared absorption spectra of 0-, m-, and p-hydroxybenzaldehydes, employing Raman spectra. For the 0- and m- compounds, two systems of bands were observed; for the pcompound, one mas found. Albrecht, Scher, and Vogel (4) reported that hlelJH2 and o-aminobenzaldehyde react selectively with aliphatic aldehydes, forming a yellow product of the 1,2-dihydroquinazolinium type, which can be determined spectrophotometrically. Inuzuka (201) investigated the T electronic structure of cinnamaldehyde, comparing its ultraviolet absorption with model compounds. Berka, Dolezal, Janata, and Zyka (27) discussed a method for the polarometric determination of aromatic aldehydes, using 2,4-dinitrophenylhydrazine in HCI. Plessing, Concha, and Brieva (348) recommended 2-(2-hydroxy-3-nitro-5chlorobenzoyl) - 1 - isonicotinoylhydrazide and 2-hydroxy-3-nitro-5-chlorobenzoylhydrazine as reagents for the quantitative determination of aromatic aldehydes. Brooks and hlorman (50) studied the infrared spectra of a number of sub46 R
ANALYTICAL CHEMISTRY
stituted salicylaldehydes and methyl salicylate derivatives to determine chelation and bonding. Petrowitz (536) using 5% UeOH in C&., separated the following compounds by chromatography on a thin silica gel layer : p-hydroxybenzaldehyde, salicylaldehyde, anisaldehyde, syringaldehyde, protocatechol aldehyde, vanillin, o-vamllin, and veratraldehyde. Duiinskj., Tyllovit, and Gruntov&(93) estimated the cinnamaldehyde content of cinnamon bark (Cortex cinnamomi) by polarography. Linko (267) described a colorimetric determination of 2-furaldehyde, s h y droxymethyl-2-furaldehyde, cinnamaldehyde, and citral with p-aminodimethylaniline and m-phenylenediamine. Trabert (475) reported a preparative and analytical method for nitriles from aldehydes. Primarily, his method was used on sugars, but the nitrile from crotonaldehyde, as well as those from a variety of aromatic and heterocyclic aldehydes, was also prepared. La1 (256) determined the dipole moments and relaxation times of butyraldehyde, n-heptaldehyde, BzH, anisaldehyde, and cinnamaldehyde a t 40’ a t a wavelength of 3.16 cm. Relaxation time of the aldehyde increases with length of the carbon chain in the order cited. hIaros and Schulek (277) determined aldehydes in the presence of oxidizing and reducing agents by reaction with excess bisulfite, destroying the excess with iodine. The bisulfite addition compound was treated in alkaline solution with KCN or NHzOH to liberate SOz-’, which was then titrated under pentane in acid solution with iodine. Kore, Shepelenkova, and Chernova (244) used the Kirchner chromatostrip method for separating and identifying acetals and corresponding aldehydes and reported R, values for 22 compounds. Maruta and Suzuki (278) determined aldehydes by preparing their 2,4dinitrophenylhydrazones. After recrystallization from alcohol, the hydrazones were separated by reversed-phase paper chromatography. Jaunin and Godat (207) reported a new reagent for characterization of specific aldehydes: d2-1,2-dianilino-l,2diphenylethane. Only aromatic aldehydes having nitro or halo groups react with this; crotonaldehyde formed an unidentified product; chloral, MesCCHO, and citral did not react. Anger and Fischer (11) developed a micro spot test for the detection of aldehydes, using an indole reagent. Sawicki and Stanley (414) suggested a spot test for aldehydes. As little as 0.2 to 5 pg. of 70 aldehydes could be detected. Chloral and hesadecanal did not lend themselves to this test. Forrester (119) reported that because of hemiacetal formation, the carbonyl
group absorption a t about 290 m,u for aldehydes is substantially reduced when the aldehyde is in alcoholic solution. The equilibrium between the aldehyde and hemiacetal is reversibly dependent on temperature. By comparing absorbance a t two temperatures, aldehyde concentration can be estimated. Saier, Cousins, and Basila (406) introduced an improved infrared analysis of aldehydes, based on the integrated absorptivity of the aldehydic C-H stretching vibration. Saier, Cousins, and Basila (406) reported new evidence that the characteristic doublet in the 2700- to 2850-cm.-’ region for most aldehydes is a result of a Fermi resonance interaction between the aldehydic C-H bending vibrations. Belkina (23) found that aldehydes can reduce AgZO in an alkaline medium without NH3, thus without formation of an ammonia complex. The order in which reagents are added is important. Sawicki and Stanley (413) suggested a fluorometric method for detecting glyoxal, pyruvaldehyde, salicylaldehyde, and certain aromatic aldehydes. Maruta and Suzuki (279) determined small quantities of saturated and a$unsaturated aliphatic aldehydes by paper chromatography and ultraviolet spectra. Theimer, Somerville, Mitzner, and Lemberg (471) described the isolation and characterization of y-ionone and y-methylionone from commercial products. For separation, gas chromatography was used, and for identification semicarbazones and nuclear magnetic resonance spectra were analyzed. Kholkhov, Shvedov, and hletal’nikov (231) reported the use of a vacuum distillation method to separate a-ionone and other contaminants from P-ionone. hlalyusov, Umnik, and Zhavovonkov (274) separated crude mixtures of aand p-ionones by fractional distillation a t 1-mm. vacuum in a column with a rotating inner cylinder, or in a column packed with steel helixes a t 3 to 5 mm. Karyakin, Tokareva, and Skvortsova (225) reported the quantitative analyses of mixtures of a- and /3-ionone by ultraviolet absorption spectra of thin layers of substances not diluted with a solvent. Kravchina and Devyatnin (248) described methods of determining P-ionone: treatment with NH20H-HC1 and KOH and titration of excess KOH; also colorimetry, polarography, and spectrophotometry. Noguchi and Kitajima (316) suggested the determination of camphor by the oxime method; HOK”2 in excess was photometrically titrated with HCl, with bromophenol blue as indicator. From 0.1 to 0.2% of camphor in a dilute aqueous or aqueous-methanol solution may be determined with an error of less than 1%. Casanova and Corey (57) resolved
(*)-camphor by gas-liquid chromatography of the diastereo isomers formed with dl-2,3-butanediol. The diastereometric ketals formed when the camphor was refluxed with the butanediol were n ashed, dried, and distilled, then completely resolved by gas-liquid chromatography. For isolation, samples were run a t 85’ C. The ketals were hydrolyzed and the camphor was extracted. The separation was confirmed by conventional analyses, infrared spcctra, and rotation studies. Verma (481) determined carvone in Indian dill oils by ultraviolet absorption. The absorbance of dill oil or a carvonecontaining solution was compared with that of pure carvone; values obtained mere within 1% of those obtained by the H&OH HCl method. Baddeley and Brocklehurst (15) reported the reaction rates of hydroxylamine and its o-methyl derivative with carvone. Grant, Hamilton, Hanior, Hodges, RkGeachin, Raphael, Robertson, and Sim (155) proved the structure of cedrelone, using mass spectrometric determination and elemental analysis. Gofrinath, Govindachari, Parthsarathy, Viswanathan, Arigoni, and Wildmann (143) confirmed the reported structure of cedrelone by nuclear magnetic resonance and chemical analysis. Zobor, Lyalikov, and Lazur’evskiI (606) proposed a polarographic method for determination of vetivone in vetiver oil and of irone in essential oils Vrkoc, Herout, and Sorm (484) investigated the structure of acorenone, a sesquiterpenic ketone from Acorus calamus L. (sweet flag oil). Beynon, Saunders, and Williams (32) recorded the mass spectra of various cyclic ketones. It is important to note that the cis and trans isomers differ considerably. Kulka (252), after reviewing the properties and uses of diacetyl and the higher homologs of diacetyl, discussed the preparation of diketones by 11 different synthetic methods. Kimura, Kuroda, Takagi, and Kubo (238) reported the infrared spectra of diacetyl monoxime and isonitrosoacetone. ,Jungnickel (219) determined Malt01 ceriometrically in H2SO1and found it to exhibit properties of a pvrylium salt. An alternative procedure is based on the formulation of the Fe-Malt01 complex. Cullinane, Woolhouse, and Bailey’CT’ood (79) studied the infrared spectra of dilute solutions of a number of aromatic hydroxyketones, noting the effect of chelation on both the hydroxyl and carbonyl frequencies. Breuer, Leader, and Srtrel (46) separated 2,4-dinitrophenylhydrazones of alkyl-aryl, cycloalkyl-aryl, and diary1 ketones, using Whatman paper n-ith H10-dimethylformamide as stationary
phase and 20:4: 1-cyclohexane-CCLdimethylformamide as mobile phase. Rfvalues of the 2,4-dinitrophenylhydrazones of a number of ketones and aldehydes are cited. Schwartz, Parks, and Keeney (483) separated monocarbonyls into groups on a MgO-Celite column, for the purpose of classifying their 2,4-dinitrophenylhydrazone derivatives. They noted that the classes elute as follon-s: methyl ketones, saturated aldehydes, 2-enals, and 2,4-dienals. Characteristic colors are exhibited on the absorbent. Forss, Dunstone, and Stark (121) developed a separation method for 2,4-dinitrophenylhydrazones not resolved by partition chromatography, by using acid-washed AlnOswith ligroine containing increaeing amounts of Et:O. Shine (@8) reported a new technique for the preparation of 2,4-dinitrophenylhydrazones, using a diglyme solution of 2,4-dinitrophenylhyclrazine. Rosnius and De$ (389) introduced two improved techniques for the sepaof ration of 2,4-dinitrophenylhydrazones carbonyl compounds: One is based on the method of Gasparic and Vecera accelerated by centrifugal chromatography according to Pavlicek and Dcyl, and the other is the chromatoplate technique of Mottier and Potterat. Chromatogranis and R f values obtained by each method are shown. Kishi (3rd) used gas chromatography to determine carbonyl compounds by hydrolysis of their 2,4-dinitrophenylhydrazones with dicarboxvlic acids. Propion , isobutyr- and isovaleraldehydes, hIe,CO, MeCOEt, iso-PrCOWIe, and MeCOPr were detected. Goryaev, Ignatova, and Tolstikov (160) reported the ultraviolet absorption spectra of the 2,4-dinitrophenylhydrazones in heptane solution of tanacetone, thujone, pinocamphone, 2-camphor, osothujic acid, and pinonic acid. Kazarov, Kazitsyna, and Zaretskaya (304) studied the ultraviolet absorption spectra of solutions of 2,4-dinitrophenylhl-drazones of 150 carbonyl compounds of different structures and degrees of unsaturation, to identify unstable carbonyl compounds n ith conjugated double bonds. Yaroslavsky (498) examined the ultraviolet spectra of 2,4-dinitrophenylhydrazones of various aliphatic ketones and styryl ketones where the a-p-olefinic bond was conjugated to an aryl moiety. It was concluded that the derivatives of normal dienones showed a third band in the ultraviolet absorption spectrum, except those of 0-ionone, which showed many abnormal properties. Corbin, Schwartz, and Keeney (74) described two similar partition chromatographic systems, which are suitable for the separation of the 2,4-dinitrophenylhydrazones of saturated aldehydes, saturated methyl ketones, 2-
enals, and 2,4-dienals. The eluates are measured by ultraviolet absorption. Calvert and Przybylska (56)obtained x-ray powder diffraction data for 2,4dinitrophenylhydrazones of 64 aldehydes and ketones. Phillips (340) published a Colthyptype chart of the ultraviolet absorption maxima of 2,4-dinitrophenylhydrazones of 459 carbonyl compounds. Cetina and Mateos (60) measured the infrared intensities of carbonyl bands of several alicyclic and aliphatic ketones and discussed the results in terms of polar and steric effects. Slomp and a e c h t e r (435) reported a convenient determination of the oximes of @-unsaturated ketones based on NlMR resonance spectra. Wheeler, Gaind, and Rosado (490) noted that Girard T reagent reacts stoichiometrically with 4 gram atoms of iodine a t p H 7 to 8, and may be determined by addition of an excess of iodine, n i t h titration of the excess with thiosulfate. Reaction rate of cyclic ketones and substituted benzaldehydes with the reagent can be determined. Montes and Wiernik (293) applied the Girard T reagent in the separation of carbonyl components from essential oils, and of ketones from niistures n i t h aldehydes. Gaddis, Ellis, and Currie (183) found that Girard T reagent and 2,4-dinitrophenylhydrazine react n-ith the MeOH or EtOH solvent in the separation of the complex carbonyl composition from autoxidized fats. They propose BuOH as a comparatively inert solvent for use n i t h these reagents. This method is adaptable to essential oil chemistry. Franc and Celiko~ska (123) separated 28 aldehydes and 18 ketones after condensation with cyanoacetohydrazide. Relation between structure and chromatographic behavior was discussed with respect to the intermolecular H bridges. Ruch, Johnson, and Critchfield (890) reported the use of hydroxylammonium formate in the oximation analyses of aldehydes and ketones. Yakloveva, Maslennikova, and Petrov (496) studied the effects of solvents in the infrared absorption of carbonyl compounds. Lichtenstein and Reynolds (264) using spectrophotometric techniques determined small quantities of monofunctional aliphatic, alicyclic, and aromatic ketones after reduction n i t h NaBH4. Absorbances of the alcohols were determined in the ultraviolet region and the amount of ketone was calculated. Ramanathan (376) reported that the Stillman-Reed method, as well as the modified procedure advanced by Sadgopal and Zutshi, can be usefully employed for determining carbonyl values of essential oils, even when these oils contain appreciable amounts of free acids. VOL 35, NO, 5, APRIL 1963
47 R
Since vetiver oil has a high content of resinous material, special precautions must be taken in determining its carbonyl value. Kheeler, Nieto, de Storer, Antunano, and lledina (491) described the gas chromatographic determinations of some aldehydes and ketones in essential oils of citronella, lemongrass, caraway, peppermint, pennyroyal, tansy, and sage. Zaikov (605)separated lower aliphatic aldehydes and ketones as hydrazones on acetylated paper. The spots were developed, then extracted, and quantitatively determined at 480 mp. Altshuller and Cohen (6) reported the determination of higher molecular weight aliphatic aldehydes and ketones, dissolving in 2-methoxyethanol solution with p-nitrobenzenediazonium fluoborate in 2-methoxyethanol. The 380to 395- and 440- to 460-nip abaorpt'ion spectra were then measured. The method can be used to determine straight-chain 3 to 5 C aldehydes in mixtures containing HCHO, CHXHO, and MeiCO. Hamarin and Herrmann (166) developed a microtitrimetIic deterniination of unsaturated aldehydes, ketones, and other unsaturated compounds in foods. The method involves iodometric back-titration of excess Br. The authors cite results with citral, citronella, cinnamaldehyde, and furfural. h technique for separation of easily volatile aromatic materials by dist,illation and repeated titration of the distillate was described. Bartos and Burtiii (18) determined specific aldehydes and ketones colorimetrically, using oxalic acid dihydrazide in equal volume with a C u ( 0 . 1 ~ ) ~ solution as reagent. At different p H values and development times, one compound can be estimated in the presence of another. Klimova and Zabrodina (240) reported a microdetermination of the carbonyl group by oximation. Drucker and Rosen (89) detected and distinguished ketones from saturated aliphatic aldehydes by oxidation with CF3COOOH to esters or lactones. Kigam, Dhingra, and Gupta (506), observing that the usual visual standard end point methods for carbonyls in Indian vetiver oil are unsatisfactory for darker oils, suggested a potentiometric method. Alcohols, Esters, and Lactones. Obtemperanskaya, Terent'ev, and Buzlanova (319) developed a titration method for the quantitive determination of monohydric alcohols, using acrylonitrile. l h u k a m i and Kagata (288) suggested a colorimetric determination of the hydroxyl group, using the hydroxamate method. The determination is not applicable to tertiary alcohols and sublimable compounds.
48 R
ANALYTICAL CHEMISTRY
Pohloudek-Fabini and Be>-rich (351) reported a paper chromatographic analysis of K xanthates of normal alcohols, C1-C12. The xanthates are strongly absorbed a t 317 mp, and the color intensity follows the Lambert-Beer law, Pesez and Bartos (334)measured the OH group of alcohols, including polycyclic alcohols, by reaction n-ith di-8quinolinol o-vanadic acid in CHC& containing OH. An orange-red compound was formed. Beyrich and Pohloudek-Fabini (35) separated aliphatic alcohols as their phenylazobenzoic acid esters by paper chromatography followed by ultraviolet and visible spectra analysrs based on the S : S group. McGrew and Vanetten (269) described a modified Clark niicroalkosyl method for estimating small amoiints of alcohols iri aqueous starch solutions. Venkataswarlu and AIariam (480) measured the characteristics of Raman lines of methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl! isoamyl, tert-amyl, allyl, and cyclohexyl alcohols. Large variations in standard intensities of the lines are due to characteristic bonds. Porcaro and Johnston (567) used commercial alkylarylsulfonate in the gas chromatographic separation of 2-met'hy1-1-butanol and 3-met hyl- 1-butanol. This column substrate was also found useful for separating other perfume and flavor compounds. Sokolov and Kolesnikova (438) separated, by gas chromatograph>-,methyl, ethyl, isopropyl, tert-but'yl, and sec-butyl alcohols, using cetyl alcohol as stationary liquid phase. hlaruta, Suzuki, and In-aina (2S0) identified aliphatic C2-18 alcohols by reversed-phase paper chromatography, using Hg(O.ic)z addition compounds of the crotonic acid esters. Kallina and Kuff ner (222) applied gas chromatography for the separation of 15 isomeric CsHleO alcohols. Hashikuni (166) reported the changes of infrared bands of (214, '216, and CIS normal primary alcohols as varying temperatures change the physical state ol the sample. Zahn, Sharkey, and \Tender (608) converted alcohols to their trimethylsilyl derivatives, which gave characteristic mass spectra, free of interference from hydrogen ion fragnientat'ion. By this technique mass spectrometric determination of alcohols is possible nithout prior separation from other compounds. Robinson, Cundiff, and llarliunas (383) described a rapid determination of organic hydroxyl groups, using 3,5-dinitrobenzoyl chloride in pyridine. Ramanathan (376) suggested that the Ac20-pyridine technique is preferable to the acetylation method, since complete isolation of the acetylated product is
difficult. This difficulty is obviated if the oil is suspended in Eb,O and then subjected t o various washings. Katritzky, Lagowski, and Beard (226) recorded the characteristic infrared bands of alkyl groups in 104 esters of the methyl, ethyl, n- and isopropyl, and n-, iso-, and sec-butyl types, assigning most of the bands to molecular vibrational modes. Krislinan (249) assigned fundainental and combination bands and compared previous results d h his spectrograms and microphotometer records of hIeOII, EtOH, PrOH, and BuOH. Pohloudek-Fabini and Luthadt (363) determined esters of loii-er fatty acids in essential oils, using palJer chromatography based on the hydrosainic acid reaction. Hofmann and Struppe (183) s e p rated higher alcohols and paraffins by gas chromatography and proposed a simple quantitative scheme, sufficiently accurate when applied to homologous series. Tanaka (466) determined alcohols photomet'rically, using vanadium 8quinolinate. Stiller (462) developed a spectrophotometric technique for deterniining small amounts of alcohols. Micovic, Mamuzic, and hIihailovic (286) reported that S-broniosuccinimide oxidizes primary alcohols to alde hydes in the absence of solvent. I n chloroform or ethyl alcohol, the products are chiefly esters of the starting alcohol and the corresponding acid. Secondary alcohols give ketones. Critchfield and Hutchinsoii (76) developed a colorimetric method for the determination of secondary alcohols by oxidation to ketones, and reaction 15l-ith 2,4-DNPH and hIeOH to develop a color. Ginther and Finch (140) described a semimicro colorimetric determination of isopropyl alcohol, based on oxidation to acetone, color formation with salicylaldehyde, and measurement of absorbance from 470 to 530 nip MeOH, EtOH, and n-PrOH do not interfere, but isoBuOH, tert-BuOH, or h;-droxybutyric acid will give higher results. Johnson and Critchfield (213) reported a method for the colorimet1,ic determination of primary and secondary alcohols in low concentration, based on formation of a red quinoid ion from the 3,5-DKB ester of the alcohol. Prajsnar (365)identified tertiary alcohols as AT-substituted amides, using Ritter's reaction, and reported the melting points of many tertiary alcohol amide deriv, ab'ires. Emery (97) tabulated the ma-a5 spectra of the formates, acetates, propionates, butyrates, isobutyrates, and isovalerates of benzyl, phenylethyl, and cinnamyl alcohols, as well as the spectra of the methyl, ethyl, isopropyl, iso-
butyryl, and amyl esters of benzoic, cinnamic, salicyclic, and phthalic acids. Significant peaks in the ester spectra were correlated with molecular structures. Accurate analytical results for two-component ester blends were recorded. Ilosvik, Knutsen, and von Sydow (43) separated and identified alcohols in fruit flavors, as esters of p-nitrophenylazobenzenoic acid, using a combination of paper partition Chromatography, infrared analysis, and x-ray diffraction. The last tn-o methods shorr-ed marked differences among the esters of eight aliphatic alcohols studied. Kishore and La1 (236) studied the method of est,imating phenyl ethyl alcohol hy esterification with phthalic anhydride, using benzene as solvent, and suggested certain improvements. Kiseleva, Gel’perin, Bhestakova, and Zelenctskii (234) described an apparatus and a double extraction technique For the purification of phrnyl ethyl alcohol. Swift (461) proposed that the princi1)al bitter volatile constituents of orange peel and juice oils are linalool and cyterpineol. -4 gas chromatographic method for their determination was devclol)ecl. Holness (184) studied. by gas chromatography. formylation reactions of citronollol in admixture n-ith grraniol. l‘hr formylation procedure cannot be recomnicsndcd as :in accurntc analytical method. van Os and de Boer (525) discussed the formylation assay of citronellol. When formylation occurred a t elevated temI)cratiu,eq, results *cere too high. At loss than 50’ C. resultq m i c closer to the theoret-ical. v:in 0 , s anti Elenia (396) reiiorted that eit~onellolcannot bc deterniined by forniylntion in the ~)rcwnceof geraniol. I t was suggcsted that geraniol be removed a i d the citronellol determined by acrtylation in ;)yridine. van Os and Sissing (327) noted that thP int,erfrrence of citronellal in the determination of free alcohol in citronella oil can be eliminated by conducting the reaction in pyridine. Best results were achieved with an acetylation mixture of 1 1)art of 4 c 2 0 to 3 parts of pyridine. Ohloff and Klein (522) studied the absolute configuration of linalool by relation to the pinane s>‘q,.tem. Guven (162) not’ed several developments for the determination of linalool and geraniol, and their separation by 1)aperchromatography. C‘astiglioni and Pilleri (59) separated geraniol from linalool by paper chromatography. A phloroglucinol developiiig solution was used. Rogers and Toth (386) demonstrated the import’ance of gas chromatography and infrared spectrophotometry in controlling the commercial production of citronrllol from citronella oils.
Farnoiv and Porsch (101) discussed the chemistry of geraniol and nerol and their occurrence in essential oils, and reported the infrared and gas chromatographic curves of these materials. Kovikova and Dergacheva (317) determined ethyl alcohol, geraniol, citronellol, and phenethyl alcohol in absolute rose oil. Di Prima and Storto (86) employed vapor-phase chromatography to determine impurities n-hich are not detected by wet analyses, in a number of perfume constituents : I-linalool, d- and dl-lina1001, geraniol, commercial geraniol, nerol, terpineol, d- and I-borneol, linalyl acetate, geranyl acetate, and d- and 1bornyl acetate. Pohloudek-Fabini and Beyrich (352) shom-ed that a previously developed technique for determining free and esterified alcohols by conversion into azobenzene-4-carboxylic acid esters can be applied to oils of parsnip, Heracleum, peppermint, citronella, rose geranium, and lemon balm. Gurvich (169) described a microchroniatographic determination of menthol in peppermint oil. The accuracy is nithin 57,. K u and Chiang (260) discussed the determination of free menthol in Taiwan peppermint oil by a colorimetric method after chroniatographic separation. The oil contained 507, free menthol. Petron itz, Pl‘erdel, and Ohloff (337) separated menthols by pas partition chromatography. Porcaro and Johnston (358) determined the composition of a mixture of menthol isomers by the use of two types of stationary phases. Bohme, van Emster, and Warmbier (41) detected dl-isomenthol as an impurity in dl-mcnthol by the difference of solubility of the two corresponding phenylurethans in pentane. RIalla, Kigam, and Rao (2’72) observed that the liquid menthol portion of dementholized oil of Mentha arvensis contained 24.787, of I-neomenthol and 60.427, of dl-isonienthol. The isomers were isolated from the acetylated oil by column chromatography. Neudert and Huber (30.5) reported that about 0.1% of diastereoisomeric impurities can be detected in &menthol by gas chromatography. With the double freezing point method, about 1% of similar impurities can be detected. Moore and Kossoy (294), using gas chromatography, separated the stereoisomers of menthol, obtained by catalytic hydrogenation of thymol with Kion-kieselguhr catalyst. Shimizu, Ikeda, and Ueda (427) isolated (+)-neoisoisopulegone from a French Mentha rotundifolia oil, and reported the physical constants of this ketone. Catalytic reduction gave (+)neoisomenthol. Huckel, Feltkamp, and Geiger (191)
compared the isomers of 1,4-dimethyl-2cyclohesanols with those of the menthols, with particular reference to conformational relationships. Hatanaka and Ohno (170) characterized trans-3-hexen-1-01 from tea leaves as its 3,5-dinitrobenzoyl ester and by its infrared spectrum. The natural leaf alcohol was mainly the cis forni with 3 to 6% of the trans form; the latter was not an artifact. Hellyer (175) noted considerable amounts of sesquiterpene alcohols such as maaline, elemol, and globulol in some leaf oils of Australian plants. Chiurdoglu, Smolders, and Soquet (66) found cedrelanol to be identical with pilgerol and d-cadinol. Bates and Slagel (20) reported that bulnesol, a substance easily biosynthesized from farnesyl pyrophosphate, is readily convertible by carbonium-type reactions into patchouli alcohol, guaiol, and “a-guaiene.” Pines and Pillai (347) dehydrated dborneol t o 23% tricyclene and 7 7 7 , dcamphene, using a catalyst of aluminum oxide modified by ammonia. Considine (7’3) prepared mixtures consisting of various amounts of pure dbornyl acetate and pure I-bornyl acetate and established their melting points. From these data, the composition of mixtures of I- with the d- compound can be determined. Karawya and El-Deeb ($24) separated isoborneol contained in technical synthetic camphor by column chromatography. Rudenko, Kucherov, Smit, and Semeriovskii (391), using gas chromatography, studied the relation between structure and retention volume ( V R ) of more than 40 isoprenoid alcohols, their acetates, aldehydes, ketones, and methyl esters of acids. Owen (528)described an apparatus for the rapid hydrolysis of high-boiling aromatic esters. Takeda and hIinato (465) investigated the absolute configuration of methyl groups in guaiol, and concluded that these groups have d-configuration. Fraser and hIcGreer (125) reported the NhIR spectra of methyl mesaconate and methyl citroconate as AX3 systems, and of methyl cis-crotonate and methyl trans-crotonate as ABX3systems. Ichimura (194) measured fluorescence spectra of 25 different coumarins and studied the relation between the spectra and the chemical structures of these compounds. Rriggs and Colebrook (@) evaluated seven infrared absorption bands characteristic of the furano group in benzofurans and furanocoumarins. Because many of these compounds occur in nature, their finding is of importance to our industv. Polizv (555) developed a colorimetric method to determine hydroxycoumarins. VOL. 35, NO. 5, APRIL 1963
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Ichimura (196) compared the fluorescence intensity in neutral and alkaline medium of various coumarins, such as coumarin, 7-hydroxycoumarin, and 7ethoxycoumarin. The color developed in an alkaline medium varied among the coumarins. Chakraborty and Chakraborty (61) determined the ultraviolet spectra of 17 coumarins in some Indian plants. Eberhardt (94) applied paper chromatography to fluorescent coumarin derivatives and prepared p H fluorescence curves for esculetin, scopaletin, and esculin. Gruji6-VasiE (157) separated a nuniber of coumarins and furocoumarins by paper chromatography. R, values for several of these compounds, such as bergapten, esculin, etc., were recorded. Ichimura (1.95) measured the intensity of fluorescence of various furocoumarins such as angelicin, bergaptol, bergapten, auraptin, pimpinellin, and isopimpinellin. The fluorescence of these compounds was weaker than that of coumarins. Kolesnikov, Komissarenko, and Chernobai (241) reported a paper chromatographic analysis of Heracleum sibiricum. The coumarin fraction was separated and pimpinellin, isopimpinellin, bergap ten, isobergapten, and sphondin were identified. Heesterman (174) described a modified Kivoli technique for determining coumarin in plant material. Hais and Ledvinova (163) chromatographed 77 coumarins in a solvent system, using formamide as the stationary phase. The chromatographic behavior in relation to structure mas discussed. Giles and Schumacher (1%) isolated two diterpene lactones from Turkish tobacco, and identified them as a- and p-levantenolide having structures closely related to labdanoic acid. Angell, Gallagher, Ito, Smith, and Jones (10) published a study dealing with the infrared spectra of lactones. Wetherell and Hendrickson (489) found that Girard Reagent T reacted readily with chlorophyll b and its derivatives, resulting in a water-soluble compound; chlorophyll a reacted only slowly, if a t all. Phenols. Salimov, Erivanskaya, and Shuikin (408) reported the infrared spectra of ethylphenols, their ethers, and other phenol ethers such as anisole. Dumazert and Ghiglione (90) described an apparatus for vapor phase chromatography. The vapors of a volatile solvent are used as the mobile phase. Cresols, thymol, carvacrol, and eugenol were separated. Chumaevskii (67) measured the infrared spectra of o-cresol a t 756 cm.-l, m-cresol a t 778 ern.+, and p-cresol at 816 cm.-l The method is convenient for routine analyses. Feigl and Vinzenz (106) reported a
50 R
ANALYTICAL CHEMISTRY
spot test for cresol, based on coupling with diazotized p-nitroaniline, and contact with 1IgO in alkaline media to produce a blue color. The test will show 0.2 pg. of p-cresol, in the presence of oand m-cresols and phenol. Yamaguchi (496) measured the XMR spectra of p-cresol in benzene, CHC13, cC14, dioxane, acetone, and pyridine, and interpreted the results. Lindberg (266) studied the ncsr-infrared hydroxyl absorption bands of 11 o-methoxyphenols related to guaiacol and lignin, in CCl4 solution, using quartz optics. Results observed were discussed in terms of Hammett's s and r functions of chemical reactivity. Feigl and Anger (104) cited tests for distinguishing eugenol from isoeugenol in discussing the detection and differentiation of isomeric organic compounds by means of spot tests. Indo (198) reported on the ozonolysis of isoeugenol in chloroform, specifically with the peroxides formed by ozonolysis. Belova (25) described the partition chromatography and ultraviolet spectrophotometry of certain monohydric phenols, such as phenol, o-phenol, ocresol, m-cresol, and p-cresol. Sundt (459) chromatographed a number of monophenols on paper impregnated with HCOXMe2. H e found that R,, acidity (pKa), and structure relationships permit the prediction of structure from R, values. Kapur (223) cited the advantages of potentiometric titration, ion exchange resin, and paper ionophoresis methods in separating and characterizing 0-,m-, and p-diphenols. Only micro quantities of the material are required. Pridham (366) used a 0 , l M solution of razhIoO4 as a specific color reagent for the detection of o-dihydrosyphenols. The behavior of 32 phenolic compounds during electrophoresis and that of 22 phenols treated with plain and molybdate-treated papers were reported. Hidalgo and Otero (178) recorded the infrared absorption spectra of phenol, resorcinol, hydroquinone, and pyrocatechol in the range 250 t o 5000 em.-' Combining the results with Ranian data, vibrational frequencies were assigned. Herzmann and Venker (I?7) reported diphenylpicrylhydrazyl as a sensitive reagent for the detection of small amounts of phenols by paper chromatography. Pyrocatechol, hydroquinone, pyrogallol, gallic acid, and protocatechuic acid gave violet colors; m-hydroxyphenols such as resorcinol exhibited no coloration. Korshunova and Korshunova (245) developed a spot test for certain phenols using an ammoniacal tartaric acid solution of ferric chloride. Salicylic acid gives an orange color, while pyrocatechol, pyrogallol, gallic acid, and tannin show dark red. Unlike FeC13 solution, this test is not suitable for the detection of
-OH-
groups in nionohydric phenols. Klevstrand (238) separated the phenolic constituents of male fern extract by a descending chromatography of Khatman No. 1 paper. Payn (332) described a gas-liquid chroniatographic analysis useful for separating several phenols. Ingold (199) investigated the infrared frequencies intemities, and apparent half-band widths of the 0-H stretching bond of a group of 2,6-di-tert-butyl-4substituted phenols in cc14solutions, and compared these frequencies with those of the corresponding 4-substituted phenols. Colombo, Corbetta, Pirotta, and Ruffini (72) separated phenolic coinpounds by chromatography on Whatman KO. 7 paper impregnated with saturated &BO2. RI values for 34 pure phenols, and techniques for their identification, were described. Hummelstedt and Hume (192) made photometric titrations of phenols with tetra-n-butyl ammonium hydronide as titrant and 2-propanol as solvent. Drhbek (68) reported a colorimetric determination of phenols. HoEevar (181) described a chromatographic analysis of phenols by an ascending separation technique using acetylated Khatman No. 1 filter-paper strips. Jurd (220) separated phenolic compounds by chromatography on borateimpregnated paper. Feigl, Gentil, and Hagenauer-Castro (106) reported that a blue spot is produced by addition of PhOH and a small quantity of X a S 3 to a solution of N, X'diphenylbenzidine in concentrated H2S04. Thij color reaction takes place also with the phenoxy compounds and phenyl esters, which are cleaved by sulfuric acid to give phenols. Puttnam (370), by spectroscopic studies of phenols, advanced evidence that in all phenols the hydroxy group is coplanar with the aromatic ring; in osubstituted phenols the hydroxyl group exists in cis- and trans- orientations with respect to the o position. Kalinon-ska (222) estimated thymol alone and in thyme oil by coulometric bromination. The method was accurate within 0.5%. Terpenes and Hydrocarbons. Takeda, Sagai, and Ogura (464) determined camphene by titration of residual AcOH after esterification wih AcOH containing H3P04, d c 2 0 , concentrated H2S04,or 13F3as a catalyst; Lyubomilov's method \\as also tried. BF3 yielded the best result. Clunie and Robertson (7f), by using x-ray analysis, determined the structure and stereochemistry of the tricyclic sesquiterpene, isoclovene, C15H24. Hayashi and Rlizoguchi (f71) described an ultraviolet adsorption determination of 2,4(8)-p-menthadiene and
3,8(9)-p-menthadiene, d-limonene, and terpinolene. Farnon- and Porsch (102) re1 iewed the chemistry and synthcais of ocimene and its occurrence in essential oils and reported infrared, ultraviolet, and gas chromatographic curves of this and related materials. Goryaev and Tolstikov (162) stated that the infrared spectrum of the reaction of sabinene in petroleum ether with dry HC1 a t -30' to -40' C. indicates its structure to be 4-cahloro-1-menthene; thus the structure previously assumed by Senimler and Kallach (sabinene hydrochloride) is erroneous. Chiurdoglu and Descamps (65),investigating tlic strurture of sesquiterpenes, concluded that a hydronaphthalenic sesqui mpene, on dehydrogenation, yields only naphthalenic derivatives; a hydroazulenic sesquiterpene yields a misture of azulenic and naphthalenic derib ati\ es. Racz-Kotilla (371), u&g Stahl's reagent, determined the azulene content of Aclzillea ntillefolium flon-ers with a n accuracy to i5 pg. Sjkora and T'okBE (462) chromatographed a series of azulenes by an ascending technique using 10 to 25y0 aqueous HC1 on Khatman KO. 1 paper impregnated with a 10 to 30% solution of paraffin oil in petroleum ether. Hunt and Ross (193) reported on the infrared spectra of azulenes. Fundamental vibration frequencies were assigned. Potapov, Goryaev, Tolstikov, and Terent'ev (360) studied the rotational dispersion of cedrane compounds and ahowed curves for iso-octane solutions of cedrol, primary ceriranol, isocedranol, isocedranone, a-cedrene, cedrenal, 8cedrene, and isocedrenol. Cedrol and primary cedranol h a r e appreciable rotational values, especially in the ultraviolet region. Zubyk and Conrier (608) described a gas chromatographic analysis of terpene hydrocarbons and related compounds and reported the relative retention data for 44 terpene hydrocarbons. Von Rudloff (393) evaluated gaschromatographic liquid substrates as applied to terpenoid separations. Von Rudloff (394) also described the use of oleic acid esters as liquid phases in the GLC of terpenes. Stahl and Trennheuser (443) reported the retention times of a number of terpenes on a polypropylene glycolimpregnated Celite column a t 100' C. Cineole was not separated from limonene. Borneol, camphor, and a number of hydrosyphenylpropanes showed similar values on a n Apiezon-impregnated Celite column at 200'. Safrole and the eugenol group could not be adequately separated, but were distinguishable by thin-layer chromatography. Cis-trans isomers were easily separated.
Kishino (315) evaluated the mass spectrometric patterns of 350 hydrocarbons aiid oxygenated compounds, and identified their characteristic peaks. Herrick and Trowbridge (17'6) removed terpene hydrocarbons from essential oils by passing a methanol or acetone solution of the oil through a column packed with a granular nonpolar, polymeric solid such as natural rubber, neoprene, etc. Lauterbur (25s) investigated and reported the T h l R spectra of aromatic hydrocarbons such as benzene, the xylenes, biphenyl, azulene, and of phenols, anisole, and dimethoxybenzenes, d r a k i and Goto ( I S ) separated m- and p-xylenes by a vapor-phase chromatography. d column packed with 32 parts by weight of 1-naphthylamine on 100 parts of C-22 firebrick was used. Sharefkin and Shwerz (426) reported a qualitative test for olefinic bonds, based on producing the glycol monoacetate with 40y0CH3COOOH. Prey, Berger, and Berbalk (S64), in a series on paper and thin-layer chromatography of organic substances, separated C Z C ~mono-olefins ~ as Hg(0Ac)z addition compounds. RI values, spot spreading, and tailing effects were evaluated for solvent mixtures with twodimensional paper chromatography. Spengler (440)reported the separation of olefins from mixtures. The pure olefins were obtained by formation of an addition compound n i t h HgO&R (where R =Ale or Pr) in lIeOH, EtOH, or EtC02H, removal of the nonolefinic material by distillation or precipitation of Hg-olefin compound, and decomposition of the latter with HC1. Examples are ethyl cinnamate, lemon oil, and cinnamic acid. Altshuller and Cohen (5) discussed a technique for the colorimetric determination of conjugated diolefins by coupling with p-nitrobenzenediazonium fluoborate in 2-methosyethanol, in the presence of H3P04, to give products suitable for ultraviolet spectrophotometry. Among the compounds studied were isoprene, myrcene, a-phellandrene, alloocimene, and a-terpinene. KO appreciable interference occurred from paraffinic, acetylenic, simple aromatic, and most other types of olefinic hydrocarbons. Some aldehydes and ketones interfered moderately, and phenols and aromatic amines moderately t o strongly. Arbuzov, Isaeva, and Samitov (1.4) studied the nuclear magnetic resonance spectra of a number of bicyclic terpenes and their oxides, such as d-3-carene1 its oside, d-a-pinene, I-a-pinene, dl-apinene, the d-oside of a-pinene, 1-oxide of ?-pinene, p-pinene and its oside, hemicyclic carenol, and cll-trans-pinocarveol. Brieskorn and Rlahran (48) found a method of distinguishing between triterpenes and sterols by a color reaction.
Miscellaneous. Stahl, Sullivan, and Voelker (444)developed a two-dimensional paper chromatographic analysis of pule and adulterated vanilla estracts. Fluorescence chromatograms in color were studied for quality differentiation. The final conclusion was made by analysis for organic and amino acid?, vanillin, lead numbcr, and resins. Stahl, Voelker, and Sullivan (445)also reported the two-dimensional fluorescence chromatograms of a n authentic vanilla extract, and three adulterations with licorice root, cascara, and yarrolT extracts. Fitclson (112) introduced a simple, rapid paper chromatographic technique for detection of foreign plant materials in vanilla extracts. Fitelson (117') described a modification of the official dO,lC method for determining resins in vanilla extracts. Final measurements are made gravimetrically or spectrophotometrically. Fitelson (115) suggested for the Association of Official Agricultural Chemists, analytical procedure3 that confirm adoption of the previously proposed qualitative test for 1 anilla resins. Fitelson (116) detailed a two-dimensional paper chromatographic method adopted after collaborative study for detection of foreign plant material in vanilla extract. Fitelson (113) also separated by paper chromatography the resins from vanilla extracts and compared the patterns developed under long-wave ultraviolet light. This technique is useful as an additional test for the detection of adulteration in vanilla extracts. Pottier (361) detected adulteration of vanilla extracts, by paper chromatography. Changes in the official methods of the AOAC proposed a t the 75th annual meeting of the Association of Official Agricultural Chemists (1961) include a n additional qualitative test for vanilla resins, a supplemental two-dimensional paper chromatographic detection of foreign matter in vanilla extracts, and a determination of volatile oils in spices (218) * Ifratkin (488) separated flavanoids from aqueous solutions by absorption on a column of Magnesol and elution with water containing about 5% ethanol or acetone, ethyl ether, etc. Csedo, Horvath, and Nagy (77) critically evaluated the methods of determining capsaicin, and suggested adoption of the Spanyar method. Samy, Kamat, and Pandya (409) reported that the capsaicin content of four types of green peppers ranges from 7.5 t o 29.4 mg. per 100 grams of fresh material, but decreases on ripening and sun drying. Csedo, Horvath, and Nagy (7'8) described a photocolorimetric method for the determination of capsaicin. Faigle and Karrer (100) deterVOL. 35, NO. 5, APRIL 1963
* 51 R
rnin6.d the absolute configuration of natural (+)-capsanthin and natural capsorubin by oxidative degradation. Faigle and Karrer (99) also studied the constitution and configuration, and proposed stereochemical structures for capsanthin and capsorubin. Todd and Perun (474) eumined the methyl esters of the fatty acid portions of Capsicum amides, to distinguish mixtures of natural and synthetic products. S'atural spice contains a n amide other than capsaicin; C. annum contains more of this amide than C. frutescens. Zitko and Durigora (505) investigated paprika extracts by paper chromatography. Among the identified components are hydro\ycinnamic acids and four flavanoids. I n addition to capsaicin, another phenolic product with no bite was isolated. Friend and Sakayama (127) suggested a rapid chromatographic method for determining the carotenoid components of plant pigment extracts. Santa Maria and Ruix de ahsin (410) discussed the methods of analyzing Spanish red pepper. Bases for standardization and production control are pigment, iodine number. ascorbic acid, reducing sugar, and Et20indexes. ,Jorysch and llarciiq (216) determined anthranilates by chromatography and fluorescence under ultral-iolet light. The sensitivity of this procedure is reported to be equal to or better than the colorimetric method uyed in "Official 9th Methods of Llnalysis" of the alO.lC, edition. Heacock and Mahon (Ira), using ascending chromatographTT, soparated 1indole and its derivatives. Leeniann and Reller (261) reported a paper chromatographic method for the detection and determination of indole compounds. Horie (787) propoqed a colorimetric method for determining indole. Rosenthaler (388) determined nitrogen in organic compounds bv the use of a SCX test. Hozumi and Kirsten (190) described a method for the ultraniicrodetermination of nitrogen. requiring heating a t 500' and 700' C. Xukhedkar (295) studied the rotary dispersion of l-santonin in 43 solvents. The results were discussed with regard to Ingold's conception of electron displacement, r a n Sumere, Teuchy. and Parmentier (457) separated esculetin, daphnetin, and ferulic acid by paper chromatography. The spots were eluted and the yellow-brown color intensity was measured. o-Coumaric acid, umbelliferone, vanillic acid, and p-hydrosybenzoic acid gave no color. van Sumere, Parmentier, and Teuchy (458) also treated vanillic acid and phydroxybenzoic acid with 4-aminoantipyrine and K,Fe(CK)O. The absorbance maxima of the red solutions were measured.
52 R
ANALYTICAL CHEMISTRY
Rohme and van Cmster ($0) described a new method for the deCrrmination of ascaridole. Foxley (122) determined limits of detection of micro amounts for a large numbw of organic peroxides, among them cumene and p-menthane hydroperoxide., and laurovl, benzoyl, and ethyl methyl ketone peroxides. Reagents were KT, Ti.6O4j3, and 4 4'-tetramethyldiaminodii~henvlmethane Sully (456)described a determination of terminal rnouidec such as stvrene oxide bv titration n-ith HO IC Ludde (268) quggmted the measurcment of dielectric con..tants for the identification of peroxides in wsential oils. Bellamv, Connellv, Philpotts, and Williams (24) discusqed the differencein infrared snectra of open and cyclic anhydride.. and various epoxides. Komae, Sun-ada, Saito. Havashi, and Matsuura (2421 compared the infrared spectra and chemical behavior of 1.4cineole Kith 1.8-cineole. Strip chromatography and color reaction with pdimethylbenxaldehvde or vanillin gave similar rwiilts for both compounds. Tt is difficult to identify 1 ,4-cinenle contaminated with I 8-cineole hv chemical properties. Ilixtures of these compound. containing 8 to 53% of 1.4cineole can hr analyzed quantitativelr with =k2% accuracv. uqing kev irifiared handy at 1106 cm.-' for 1,4-cineole and 1079 em. -1 Tor 1 ,%-cineol.. Blake and Rahjohn (.991 determined eucalyptol inmixtureq with thymol, menthol, and camphor hy treatment n i t h an excess of HRr and In- titration after 48 hours of thP ~ Y C P ~H13r T n i t h N a 0 . k in AcOH. GenPqt, Smith, and Chavnian (138) described a qualitative teqt for the detection of safrole in foods and drugs. i color i.. produccd a t the interface of H?SO1and the qolution containin.; qafrole and gallic acid. Rud&nsk i.and Korbl (53) deqcribed an all-qlass single-joint microapparatus for alkoxy determinations. Rillitzer (37) suggested an improved Zrisel alkoxy determination, reducing the reaction time to 30 minutes and the error to 0 294. Fukuda (130) reported a qensitive detection of alkoxy groups .\ sample is reacted Jvith HI to form the alkyl iodide, which i q thermally treated to vield Iq, which is then determined using starch 4nderson and Duncan (8) used infrared spectroscopv for the quantitative determination of alkyl iodide vapors to study reaction variables in the Zeisel alkoxy determination. Rapid and accurate determinations of solids and volatile liquids were obtained. For vanillin, the standard deviation was 0.16%. Anderson and Duncan (9) applied gas-phase infrared spectroscopy for the simultaneous determination of M e 0 and Et0 groups as alkyl iodides or bromides.
K h e n the N e O : E t 0 ratio exceeds 4 : 1 the method is applicablc only to bro mides. Kliniova and Zabrodina (239) deqcribed a special apparatus for the microdetermination of methosy and ethoxy groups with accuracy better than 0.2 to 0.3%. Fukuda (129) applied a neIT combustion method for microdeterminations of methosy or ethoxy groups. Vogel and Quattrone (483) suggested a rapid gas-chromatographic method for the determination of carbon and hydrogen. Precision for carbon is one-half that obtained by the Pregl method; but for hydrogen i t is three to four times better. Gel'man and Wang (136) described a conductometric microdetermination 01 carbon and hydrogen in organic compounds. Meyer and Vettrr (285) determined carbon and hydrogen in organic compounds in seminiicro quantities by combustion in 02 a t 650' C., using Co804 as combustion catalyst. Zabrodina and Egorova (501) outlined a technique for the simultaneous determination of carbon, hydrogen, and halogen; accuracy was 50.2% for carbon and hydrogen and 1 0 . 4 % for the halogen. SpEv&k,Kratochvil, and VBEefA (441) proposed a method for nitrogen determination in organic compounds by decomposition of the organic substance nith a n alkali metal and liberation of HCN. Ogg (320) suggested an improvement on the present AOdC method for nitrogen determination. The time of digestion is reduced and the digestion conditions are made more reproducible. Gel'man, Wang, and Bryushkova (137) developed a microdetermination for oxygen in organic compounds based on the method of Korshun and Bondwevskaya. Illinko (289) studied the ter Meulen volumetric oyygen technique for organic compounds to eliminate sources of error. H e concluded that incomplete reduction of CO? and the ('fatigue phenomenon" were unrelated. Ehrenbergei , Gorbach, and hlann (96) observed that the potentiometric determination of oxygen as COZ with automatic titration is more rapid and accurate than methods used previously. Puttnam i369) pointed out the sipnificant infrared peaks of sec-butyl groups attached to an aromatic ring. The identification of these peaks is helpful in studies of intermolccular and intramolecular rearrangements in which butyl groups are involved. Gore and Gupte (147) reported a microdetermination of C-methyl groups in organic compounds. The Kuhn-Roth technique was modified by performbg the digestion in a H3P01bath at 125' to 130' C. and distilling the HOAc directly from the reaction mixtures. Gore and Gupte ( I $8) extended the modified
Kulin-Roth riiicrodeterniiiiation of C Me groups also to the determination of 0- or N-Ac groups in organic coinpounds. The reacticn requires about 30 minutes. Brandenberger, Ahas,, and Dvoretzky (45) determined C-methyl groups in alkylbenzenes by chromic acid osidation, as .lcOH, without interference from 13zOH. Tests on monoalkylbenzenes (1 to 20 carbon side chains) were in good agreement with theorctical figures. Freyniaiin, Drolaitzky, and Jacques (126) studied the nuclear magnetic resonance lines corresponding t o CH3 or C2Hs groups substituted in benzene, Tetraline, phenanthrone, and chrysene. k'amana (497) studied the internal conformation of the isopropyl group in mcntliol-like substances. Onoe (324) improved the TI-iesenbcrger determination of the acetyl group by reducing the required time. dchenk aiid Fritz (41s) reported an acid-catalyzed acetylation met,hod for the determination of phcnols, amines, arid mist,urrs. Siggia and Hanna (430) discussed the use of diffcrmtial reaction rates to analyze mistures of organic materials coiit'aining the same functional group, such as mixtures of primary and secondary alcohols and mixtures of aldehydes and ketones. Ralla (974) applied flash eschange gas chromatography t'o the steam dist'illate of peas, and idciitified various aldehydes and acids. .I misture of these compounds a t the observed conccntrations did not yii.ld :lie characteristic odor of fresh-pca distillate. Eohme and Hofmanii (42) reported a photometric determination of biphenyl aiid c-hydroxybiphenyl in the peel of citrus fruit. Thomas (472) identified by gas chromatography 1 to 10 p.p.m. of biphenyl and o-phenylphenol in the estract oi the steam distillate of concentrated orange juice. Rno and Rao (317) recorded ultraviolet absorption bands of molecules containing carbonyl groups. Dhont and de Rooy (86) studied the behavior of several 3,5-dinitrobenzoates on silica gel chromatoplates. Hexanol, phenol, thymol, 1- and 2-naphthol, 0-, m-, and p-cresol, eugenol, isoeugenol, citronellol, geraniol, maltol, benzyl alcohol, furfuryl alcohol, and terpineol were examined. Reznik and Eggttr (381) observed the reaction of basic cupric citrate complex (Benedict's reagent) with ciniiamic acid derivatives, coumarin derivatives, flavonol aglycons, flavonol glycosides, and flavones. h single O H group increases and o-dihydroxy groups decrease the ultraviolet fluorescence. Klabunovskii, Balandin, and Godunova (237) separated a mixture of menthene, menthone, and menthol on silica gel. Specially treated silica
gel permitted stereospecific separations of menthol. Saber, Rahnian, K a 4 m , and Khafagy (404, separated santonin, artemisin, and judaicin by paper chromatography using a butanol-water-acid mixture as the developer. Petranek (336) described a method for separating Clto C 4 dialkyl sulfides by gas chromatography. Retention volumes for 17 dialkyl sulfides were tabulated. Rosenthal and Oster (386) reported the ultraviolet spectra of alkyl disulfides and the relation to alkali cleavage of disulfide bonds. Furst (1.92) found that polarographic measurements on the micro l e v ~ l ,and polarographic titration on the semimicro level, are time-saving and accurate in deterniiiiing allyl thiocyanate. Distillation of the oil froin the drug is not necessary. Hediger ( 1 13) r e r i e w d qe\ era1 techniques and problems pertinent t o our industry, such as blind odor evaluation, establishment of quality samples, subjectivity of odor standards, and methods of olfactory analysis. Saunders (411) discussed the perfumer's part in determining correlations between odor and chemistry that affect the quality of pcrfume materials: among these are presence of related components, trace impurities, etc. Fiore (111) reviewed some of the factors affecting the quality of perfumery materials, and reiterated that proper chemical or analytical methods and adequate odor control techniques are necessary to maintain high standards. Rogers (584)demonstrated the instrumentation of perfume materials by gas chromatography, infrared spectrophotometry, and nuclear magnetic resonance. Theile (469) stated t h a t a combination of chemical and subjective tests achieves the best quality control of perfumery materials. Johnston (213) discussed the application of physical tests, such as color, appearance, density, arid refractive index, to perfumery materials. Holness (186) discussed the application of gas chromatography to the study of perfume raw materials and essential oil components, and identification of essential oils of similar types. Kovats (246) reported that the gas chromatographic behavior of organic compounds may be classified by a retention index based on the behavior of the normal hydrocarbons. D e Feo (82) tested 15 essential oils and 15 aromatic chemicals for compatibility mith various propellents. The results were classified according t o solubility. Rosenthaler (387) reviewed techniques for detecting organic compounds by reactions with citric, pyruvic, and
barbituric acids; color reactioiia with ninhydrin, and between quinones and I i a s S 2 0 a ; reactions with p-quinone; Ohkuina's reactioii; and a comparison of color reactions of ris- and transaconitic acid. Jones (215) published a summary chart of principal infrared group frequencies of organic compounds. Bassette and Khitnah (19) described a technique for the removal and ident'ification of organic compounds by chemical reaction in gas chromatography. Ralls (373) descrilied a fla.;h-exchange gas chromatographic method for the detection of volatiic components such as aldehydes, ketones, and acids. The method Ivill be of great value for thc determination of trace aniounts iii water. Pimazzoni (344) rcviexed the tlieoretical principles of molecular distillat,ion and its application to essential oils, as well as (346) the theoretical principles of molecular distillation and applications in the fields of fats, perfumes, cosmetics, food, pharmaceuticals, and the biological and chemical industries. Parekh, Pruthi, and La1 (330) investigated the off-flavor in a n orange drink during pasteurization and esplained it as oxidation of limonene. Gleit (142) described a n cstractor reaching rapid phasr: equilibrium by t h e use of turbulent countercurrent flow. The apparatus is useful over a wide range of organic extractions. BIeunier (284) used fluorinatcxl hydrocarbons instead of ,zlcohols to prepare essences from natural products. hlaleeny (271j developed a technique for det,ermining nonvolatile substances encapsulated by several drying methods. Nackay, Lang, and Berdick (27'0) employed gas chromatographs with ionization dctectors t'o demonstrate differences in the composition of unconcentrated vapors over unspoiled and deteriorated peppermint oil, genunine and imitation banana flavors, and coffee. T'ietti-l\Iichelina and Pilleri (482) treated benzaldehyde and benzyl alcohol by combustion a t 700" C. in a quartz tube using CuO, and measured the resulting COS and H20 by gas chromatography. Prey, Kabil, and Berbalk (365) reported preparative chromatographic microniethods for organic substances, using paper chromatography on glass fiber paper. The determinations of alkyl halides, tertiary amines, aromatic hydrocarbons, aryl halides, primary and secondary alcohols, and estrrs are described. Bidmead and Welti (36) evolved a method for stripping the flavor from a n aqueous fruit juice or extract; the technique is said t o be applicable to VOL 35, NO. 5 , APRIL 1963
53 R
any volatile or steam-volatile material. Esters provide the basic odor of strawberries, while the carbonyls and alcohols add various characteristic notes. LITERATURE CITED
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\ - - - - ,
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I
~1
Fertilizers E. D.
Schall
Department of Biochemistry, Purdue University, lafayette, Ind.
T
covers the literature reported from September 1, 1960 to September 1, 1962, and includes procedures recorded in readily available journals, in Chemical Abstracts, and in Analytical Abstracts. Some selectivity has been exercised t o include only those procedures especially pertinent to, or which, in the author’s judgment, could be adapted easily to, fertilizer analytical problems. The most recent review in the series appeared in April 1961 (65). Other reviews appearing during the biennium include the excellent and comprehensive report covering present methods for 15 fertilizer nutrients presented a t the Joint Symposium on Fertilizer Analysis organized by the Fertilizer Society and the Society for ilnalytical Chemistry (49). A review of conventional solubilization procedures as applied to fertilizer analysis also appeared (56). HIS REVIEW
OFFICIAL METHODS
The Association of Official Agricultural Chemists (AOAC) gave “official” status t o the method for the direct determination of available P2Os by the photometric niolybdovanadophosphate procedure and adopted as “first action” the direct determination of available P206by the official volumetric method. Also given first action status was the quinolinium phosphomolybdate method for total and insoluble P206.
58 R
ANALYTICAL CHEMISTRY
SAMPLING
I n a study of sampling bagged fertilizer, three sampling instruments (tubes) were compared with each other and with riffling (64). The experiment offered little evidence of systematic variations in the use of the three sampling tubes, but did show evidence that samples taken by the tubes yielded results that were different from those obtained by riffling. Factors contributing to segregation in batch-type and in continuous production of fertilizers were investigated, and the problems of sampling were discussed in relation to these variations (22). I n a related study the expected reliability of screen analyses and of average particle size of screen separates was determined ( 6 2 ) . WATER
The water content of fused ammonium nitrate-limestone and of crystalline or prilled urea was determined from the change in the dielectric constant of technical benzene containing these products (74). Results were obtained in 5 minutes and were in close agreement with those by the Karl Fischer method. The vacuum oven treatment for 2 hours at 50” under a t least 20 inches of vacuum appeared t o be a generally reliable and relatively rapid method for the determination of moisture in fertilizers and most fertilizer materials
(12). However, it was not satisfactory for fertilizer grade diammonium phosphate, 85Tc phosphoric acid, or for mononiagnesiumphosphate tetrahydrate. NITROGEN
The reduced iron method for samples containing nitrates in combination with other forms of nitrogen continued to receive attention during the biennium. I n one modification proposed, the amount of H2S04added was increased to permit continued digestion in the normal Kjeldahl manner follonTing the nitrate reduction (29). With this change the procedure was applicable to all types of fertilizers, including those with high chloride-nitrate ratios, to high organic materials, and to combinations of these. A comparative study of commercial iron powders revealed no common property, such as reduction type, mesh size, manufacturing process, was related to their efficiency in reducing nitrate (SO). Of the 36 commercial brands tested, 13 yielded complete recovery of added nitrogen. A collaborative study of the official AOAC reduced iron and the improved Kjeldahl methods with the chromous ion reduction and the modified reduced iron methods failed t o show clear-cut superiority of any of the four methods (20).
