Chemistry of Natural Compounds, Vol. 48, No. 6, January, 2013 [Russian original No. 6, November–December, 2012]

TERPENOIDS AND AROMATIC COMPOUNDS FROM ESSENTIAL OILS OF laevipes AND C. glabra

T. V. Ilina,* A. M. Kovaleva, O. V. Goryachaya, UDC 543.51:582.972.3 and B. A. Vinogradov

In continuation of the study of representatives of the family , we investigated the composition of essential oils of herb two of the genus Cruciata Mill. These were C. laevipes Opiz. (or Galium cruciata Scop.) and C. glabra (L.) Ehrend. (or Galium vernum Scop.). Previous investigations of these species detected iridoids, coumarins, flavonoids, anthraquinones, and tanning agents [1]. Raw material for the production of essential oils consisted of ground upper parts of stems with leaves and flowers collected during flowering in May-June 2011 in Ivano-Frankov Region of Ukraine (herbarium specimens No. 16/11 and No. 17/11 are preserved at the Pharmacognosy Department, NPU). Essential oil was produced by steam distillation with subsequent treatment of the distillate with high-purity pentane. This isolated essential oil contained in minor or trace amounts in the raw material [2]. The constituent composition of essential oil was determined on an Agilent Technology 6890N chromatograph with a 5973N mass-spectrometric detector. The analytical conditions were published earlier [3]. Compounds were identified by comparing their mass spectra from chromatography with those of standards and with data in the Wiley 2007 and NIST05 mass spectra libraries in combination with AMDIS and NIST programs for identification. We found that air-dried herb of C. glabra contained 0.08% essential oil in which 45 compounds were detected. Of these, 35 were identified as terpenoids (11), aromatic compounds (4), higher hydrocarbons (8), higher fatty acids and their esters (11), and fatty aldehydes (1) (Table 1).

TABLE 1. Table 1. Identified Compounds from Essential Oils of C. laevipes and C. glabra

C. glabra C. laevipes Compound RI RT, min % RT, min %

cis-3-Hexen-1-ol 904 4.15 0.1 trans-2-Hexen-1-ol 906 4.22 0.6 Hexanol 913 4.46 0.3 Benzaldehyde 977 6.57 0.3 2-Methylphenol 981 11.52 0.1 Benzyl alcohol 987 11.61 0.3 1-Octen-3-ol 992 7.09 0.5 Decane 1000 7.55 1.0 Phenylacetaldehyde 1026 12.26 0.2 8.97 2.1 trans-Linalool oxide 1075 9.86 0.3 Verbenol 1077 13.08 0.7 cis-Linalool oxide 1091 10.37 0.1 Undecane 1100 10.68 0.3 Linalool 1103 10.77 2.1 2,6-Dimethylcyclohexanol 1110 11.02 0.6 -Isophorone 1123 11.43 0.6 Borneol 1125 13.86 0.9 13.04 26.5 trans-Pinocarveol 1141 12.04 0.7 trans-Verbenol 1148 12.27 2.1 Epoxylinalool 1150 14.27 0.5

National Pharmaceutical University, Ukraine, Kharkov, Ul. Pushkinskaya, 53, fax: (8057) 714 25 40, e-mail: [email protected]. Translated from Khimiya Prirodnykh Soedinenii, No. 6, November–December, 2012, pp. 976–977. Original article submitted June 25, 2012.

1106 0009-3130/13/4806-1106 ©2013 Springer Science+Business Media New York TABLE 1. (continued)

C. glabra C. laevipes Compound RI RT, min % RT, min %

-Phenylethyl alcohol 1153 14.33 0.2 Isoborneol 1171 12.67 0.6 Terpinen-4-ol 1180 13.33 0.4 p-Cymen-8-ol 1189 13.66 0.2 -Terpineol 1194 14.76 0.7 13.80 0.2 Dodecane 1200 14.01 0.8 Decanal 1208 14.26 0.3 Verbenone 1219 14.64 7.9 Nerol 1233 15.11 0.5 Geraniol 1294 16.62 0.2 15.97 0.7 2-Methyldodecane 1264 16.13 0.6 2,9-Dimethylundecane 1271 16.36 0.4 Thymol 1309 17.64 0.2 2-Methoxy-4-vinylphenol 1317 17.90 1.1 Tetradecane 1400 20.11 1.9 Caryophyllene 1427 20.59 2.6 Capric acid 1459 19.31 0.5 Geranylacetone 1467 21.32 1.9 2,6,10-Trimethyldodecane 1475 21.46 0.5 Germacrene D 1478 21.92 2.8 -Ionone (isomer) 1482 22.02 1.0 -Farnesene 1496 22.15 0.7 Pentadecane 1500 22.22 1.7 2,4-Bis-tert-butylphenol 1536 22.58 0.4 Eugenol 1353 21.17 0.4 19.12 1.8 Hexadecane 1600 21.61 0.4 Longiborneol 1620 24.10 0.5 Tetradecanal 1628 24.23 0.9 2,6,10-Trimethylpentadecane 1657 24.76 1.1 -Ionone 1677 22.87 0.2 5,6-Epoxy-5,6-dihydro--ionone 1690 23.08 0.6 Lauric acid 1702 23.28 3.0 Heptadecane 1706 23.35 0.5 25.54 1.6 2,6,10,14-Tetramethylpentadecane 1707 25.63 1.1 Pentadecanal 1722 25.81 8.1 Hexadecanal 1734 23.79 0.4 Caryophyllene oxide 1755 24.47 2.6 Octadecane 1800 24.87 0.4 2,6,10,14-Tetramethylhexadecane 1827 27.1 0.7 Myristic acid 1915 26.28 9.9 Hexahydrofarnesylacetone 1955 26.77 1.0 27.61 0.8 Pentadecanoic acid 2020 27.56 5.0 Heneicosane 2100 30.72 0.6 Ethylpalmitate 2114 28.71 0.5 Palmitic acid 2136 28.97 37.4 Phytol 2138 30.94 2.0 Tricosane 2300 30.98 1.2 32.93 0.6 Stearic acid 2314 31.11 1.1 Ethyllinoleate 2320 31.17 0.4 28.19 1.7 Linoleic acid 2339 31.35 5.1 Ethyllinolenate 2353 31.49 1.2 28.29 6.4 Linolenic acid 2372 31.67 4.3 Tetracosane 2400 33.95 0.5 Pentacosane 2500 34.95 0.6 Hexacosane 2600 33.03 0.6 35.91 0.3 Heptacosane 2700 34.93 0.5 36.83 0.4 Nonacosane 2900 36.71 1.1 38.71 0.6 Squalene 2972 37.40 9.6 38.05 1.3 Total 91.7 97.2

1107 The dominant terpenes in essential oil of C. glabra were caryophyllene oxide (2.58%) and squalene (9.58%). Air- dried herb of C. laevipes contained 0.46% essential oil in which 61 compounds were detected. These included 25 terpenoids, 4 aromatic compounds, 20 higher hydrocarbons, 6 alcohols, 4 aldehydes, and two fatty acid esters. The dominant terpenoids in C. laevipes essential oil were borneol (26.50%) and verbenone (7.92%). The common compounds for C. glabra and C. laevipes were phenylacetaldehyde, borneol, -terpineol, geraniol, eugenol, hexahydrofarnesylacetone, squalene, ethyllinoleate, ethyllinolenate, and several saturated hydrocarbons. The compositions of these essential oils were studied for the first time.

REFERENCES

1. Plant Resources of the USSR: Flowering , Their Chemical Composition and Use; Families Caprifoliaceae-Plantaginaceae [in Russian], Nauka, Leningrad, 1990. 2. L. B. Chernogorod and B. A. Vinogradov, Rastit. Resur., 42, No. 2, 61 (2006). 3. T. V. Ilina, A. M. Kovaleva, O. V. Goryachaya, and B. A. Vinogradov, Khim. Prir. Soedin., 136 (2012).

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