Chemical composition of the leaf essential oils of Murraya koenigii (L.) Spreng and Murraya paniculata (L.) Jack
Abstract
The chemical composition of the leaf oils of Murraya koenigii (L.) Spreng and M. paniculata (L.) Jack from Bangladesh was studied by gas chromatography mass spectroscopy (GC-MS). M. koenigii oil contained 39 compounds of which the major is 3-carene (54.2%) followed by caryophyllene (9.5%). Oil of M. paniculata contained 58 compounds of which the major are caryophyllene oxide (16.6%), beta-caryophyllene (11.8%), spathulenol (10.2%), beta-elemene (8.9%), germacrene D (6.9%) and cyclooctene, 4-methylene-6-(1-propenylidene) (6.4%). The compositions of both oils varied qualitatively and quantitatively.
Introduction
A systematic study on the medicinal and aromatic plants is being carried out in Bangladesh. Among these plants one finds Murraya koenigi (L.) Spreng and M. paniculata (L.) Jack of the Rutaceae family. Murraya koenigii (L.) Spreng is a small strong smelling perennial shrub or small tree commonly found in forests as undergrowth, cultivated in India for its aromatic leaves and for ornament. Leaves are used as a condiment in the preparation of curry powder, pickle, chutney, sausages and seasonings (Anonymous, 1962; Hiremath et al., 1998). The flavor and fragrance of leaves retain even after drying (Omankutty Amma et al., 1984). Leaves relieve nausea, indigestion, vomiting; eaten as a cure for diarrhea and dysentery (Anonymous, 1962; Ghani, 2003). Essential oil composition of leaves has been studied by various workers. The major constituents responsible for the aroma and flavor have been reported as pinene, sabinene, caryophyllene, cadinol and cadinene (Anonymous, 1962; Nigam and Purohit, 1961; Prakash and Natarajan, 1974; Macleod and Pieries, 1982; Hiremath et al., 1998). Raina et al. (2002) reported four genetically divers chemotypes (1) beta-pinene (70%), beta-caryophyllene (6.5%) and beta-pinene (5.4%), (2) alpha-pinene (65.7%), beta-pinene (13.4%) and beta-phellandrene (7.4%), (3) beta-caryophyllene (53.9%), aromadendrene (10.7%) and alpha-selinene (6.3%), (4) beta-phellandrene (30.2%), beta-caryophyllene (24.2%), alpha-pinene (15%), (E)-beta-ocimene (5%) and aromadendrene (4.5%) as major constituents from various parts of India. Walde et al. (2005) reported alpha-pinene (52%) and cis-beta-ocimene (34%) as major constituents in Hyderabad plants.
M.paniculata (L) Jack. syn. Chalcas paniculata L. Chalcas exotica (L.) Millsp. is a very variable evergreen shrubby plant with small white flowers, small oblong fruits and hard wood, planted in gardens as an ornamental in many areas of the country. Leaves are stimulant and astringent and are used in the treatment of diarrhea, dysentery and diseases of teeth and gum; useful against rheumatism, coughs and hysteria (Anonymous, 1962; Chopra et al., 1956; Ghani, 2003). The essential oils showed significant anti-inflammatory and analgesic activities (Dash et al., 2004). Sawangjaroen et al. (2006) reported, it showed antiamoebic activities. The leaves and other tissues have both stimulant and astringent properties and are used to treat diarrhea, dysentery, cuts, joint pain, body aches (Parrotta, 2001), venereal disease (Kinoshita and Firman, 1996), and as an abortive (Xiao and Wang, 1991). In addition to essential oils, tissues of orange jasmine contain the indole alkaloid yuehchukene (Xiao and Wang, 1991) and at least eight highly oxygenated flavones (Kinoshita and Firman, 1996), leaves yield oil, which contains sesquiterpenes (l-cadinene), alpha-sesquiterpene alcohol and methyl anthranilate (Anonymous, 1962; Chopra et al., 1956). Nureni et al. (2004) reported, the principal constituents of the leaf oil were beta-cyclocitral (22.9%), methylsalicylate (22.4%), trans-nerolidol (11.7%), alpha-cubebene (7.9%), (-)-cubenol (6.8%), beta-cubebene (5.8%) and isogermacrene (5.7%). The most prominent compounds were beta-caryophyllene (24.1%), with lesser amounts of germacrene D (11.9%) and bicyclogermacrene (11.8%). Some reports of the chemical composition of the leaf oil of M. paniculata of Asian or Australian origin have appeared (Garg and Nigam, 1970; Qiang et al., 1988; Brophy et al., 1994). In our study the abundance of 3-carene was the highest. It has various medicinal uses (Jeong et al., 2007; Lastbom et al., 1998). On the other hand, M. paniculata contained abundance of caryophyllene oxide which has antifungal activities (Yang et al., 1999). So, the present study deals with the investigation of the chemical components in oils obtained from leaf of M. koenigii and M. paniculata grown in Bangladesh.
Materials and Methods
Plant material
Fresh leaves of M. koenigii and M. paniculata were collected from the plants grown in the campus of BCSIR Laboratory, Chittagong during June 2007. Two-voucher specimen (Y-325) was deposited in the herbarium of BCSIR Laboratory, Chittagong.
Extraction of essential oil
Leaves were harvested and air-dried for about one week. The oils were obtained by hydrodistillation for 4 hours in a Clevenger-type apparatus. The oil yields (calculated per weight of dried material) were 0.5% for M. paniculata and 1.0% for M. koenigii. The oil samples were stored at 0°C in air-tight containers after drying them over anhydrous sodium sulfate for gas chromatography mass spectroscopy (GC-MS) analyses.
GC-MS analysis
The essential oil from leaves of M. koenigii and M. paniculata were analyzed by GC-MS electron impact ionization (EI) method on GC-17A gas chromatograph (Shimadzu) coupled to a GC-MS QP 5050A mass spectrometer (Shimadzu); fused silica capillary column (30 m x 2.5 mm; 0.3 mm film thickness), coated with DB-1 (J&W); column temperature 100°C (2 min) to 250°C at the rate of 3°C/min; carrier gas, helium at constant pressure of 90Kpa. Acquisition parameters full scan; scan range 40-350 amu.
Identification of the compounds
Compound identification was done by comparing the NIST library data of the peaks with those reported in literature, mass spectra of the peaks with literature data. Percentage composition was computed from GC peak areas on BP-I column without applying correction factors.
Result and Discussion
The essential oils from the leaves of M. koenigii and M. paniculata were analyzed by GC-MS presented in Table I.
Table I: Constituents of leaf essential oil from M. koenigii and M. paniculata
| Compounds from M. koenigii | % | Compounds from M. paniculata | % | |
|---|---|---|---|---|
| 1 | alpha-Thujene | 1.5 | Sabinene | 0.1 |
| 2 | 3-Carene | 54.2 | 3-Hexen-1-ol, formate | 0.1 |
| 3 | Camphene | 0.1 | Limonene | 0.3 |
| 4 | Allyl(methoxy)dimethylsilane | 2.6 | Linalool | 0.1 |
| 5 | beta-Myrcene | 3.2 | Cyclohexene,3,4-diethenyl-3-mehyl | 0.6 |
| 6 | alpha-Phellandrene | 0.1 | Cyclohexene,5,6-diethenyl-3-methyl | 3.3 |
| 7 | alpha-Terpinene | 2.4 | Azulene | 0.1 |
| 8 | m-Cymene | 0.3 | Ocimene | 0.1 |
| 9 | Limonene | 0.8 | cis-3-Hexenyl valerate | 0.2 |
| 10 | beta-Phellandrene | 0.5 | 2-Cyceohexen-1-one, 2-methyl-5-(1-methylethenyl) | 0.1 |
| 11 | Eucalyptol | 0.1 | 1H-Imidazole -4-methanol,5-methyl | 0.1 |
| 12 | (E)-Ocimene | 0.2 | d-Elemene | 3.6 |
| 13 | g-Terpinene | 2.7 | alpha-Cubebene | 3 |
| 14 | cis-Sabinenehydrate | 1.5 | Germacrene D | 6.9 |
| 15 | Linalool | 0.2 | 3,9-Dodecadiene | 0.1 |
| 16 | 4-Terpineol | 2.8 | b-Caryophyllene | 11.8 |
| 17 | Naphthalene | 0.1 | Caryophyllene oxide | 16.6 |
| 18 | Terpinyl acetate | 0.1 | Cyclooctene, 4-methylene-6-(1-propenylidene) | 6.4 |
| 19 | cis-Piperitol | 0.1 | Retinal | 1 |
| 20 | Isobornyl acetate | 0.1 | alpha-Caryophyllene | 3.1 |
| 21 | d-Elemene | 0.04 | beta-Humulene | 0.2 |
| 22 | Neryl propionate | 0.04 | Copaene | 2.3 |
| 23 | 1-Chloroheptacosane | 0.1 | g-Elemene | 0.3 |
| 24 | beta-Elemene | 1.9 | Cubenol | 2.4 |
| 25 | Caryophyllene | 9.5 | alpha-Bulnesene | 0.1 |
| 26 | alpha-Caryophyllene | 2.8 | Calamenene | 0.3 |
| 27 | Eudesma-4(14),11-diene | 0.2 | 3-Tetradecynoic acid | 0.2 |
| 28 | g-Elemene | 2 | Lanceol, cis | 0.3 |
| 29 | d-Cadinene | 0.1 | β-Vatirenine | 0.1 |
| 30 | Nerolidyl acetate | 0.2 | β-Elemene | 8.9 |
| 31 | Caryophyllene oxide | 1 | Nerolidyl acetate | 1.2 |
| 32 | 12-Oxabicyclo[9.1.0]dodeca-3,7-diene, 1,5,5,8-tetramethyl- | 0.1 | Alloaromadendrene oxide | 0.3 |
| 33 | 1,4-Methanoazulen-9-ol, decahydro-1,5,5,8a-tetramethyl | 0.1 | Spathulenol | 10.2 |
| Compounds from M. koenigii | Compounds from M. paniculata | |||
| 34 | Cubenol | 0.1 | D-Verbenone | 0.6 |
| 35 | 2(1H)-Naphthalenone, 4a,5,6,7,8,8a-hexahydro-4a,8a-dimethyl- | 0.1 | Pyrimdine-2(1H) thione, 3,4-dihydro -6-methyl, 4-phenyl | 0.5 |
| 36 | alpha-Cadinol | 0.1 | 3-Carene | 0.9 |
| 37 | Juniper camphor | 0.5 | 12-Oxabicyclo(9,1,0) dodeca-3,7-diene,1,5,5,8 - tetramethyl | 2.1 |
| 38 | 3-Phenylbutyrophenone | 1.2 | Globulol | 0.2 |
| 39 | Phytol | 0.9 | Eremophilene | 1.5 |
| 40 | 2(1H) Naphthalenone, 4a,5,6,7,8,8a-hexahydro, 4a,8a-dimethyl | 0.3 | ||
| 41 | Tau-Muurolol | 0.9 | ||
| 42 | Ledol | 2.2 | ||
| 43 | Aromadendrene oxide | 1.5 | ||
| 44 | alpha-Calaconene | 0.3 | ||
| 45 | Longifolenealdehyde | 0.6 | ||
| 46 | 11-Hexadecyn-1-ol | 0.2 | ||
| 47 | Cycloisolongifolene, 8-hydroxyendo | 0.3 | ||
| 48 | Longipinocarveol, trans | 0.2 | ||
| 49 | Carveol | 0.1 | ||
| 50 | 1-Cyclohexene-1-ethanol, 2,6,6-trimethyl | 0.1 | ||
| 51 | 1-Methyl verbenol | 0.2 | ||
| 52 | Cyclopropane, 1-bromo-2,2,3,3-tetramethyl-1prop-1-ynyl | 0.2 | ||
| 53 | Corymbolone | 0.1 | ||
| 54 | 2(4a,8-Dimethyl-1, 3,3,4,4a,5,6,7-octahydro-naphthalene-2-yl) -prop-2-en-1-ol | 0.1 | ||
| 55 | Ledene alcohol | 0.7 | ||
| 56 | Aristolene oxide | 0.3 | ||
| 57 | 6-Isopropenyl-4,8a-dimethyl 1,2,3,5,6,7,8,8a, octahydro naphthalen-2-ol | 1 | ||
| 58 | Longifolene-[12]-epoxide | 0.1 |
M. koenigii oil contains 39 compounds of which the major is 3-carene (54.2%) followed by caryophyllene (9.5%). Other notable compounds in the M. koenigii oil are alpha-thujene (1.5%), allyl(methoxy)dimethylsilane (2.6%), beta-myrcene (3.2%), alpha-terpinene (2.4%), g-terpinene (2.7%), cis-sabinenehydrate (1.5%), 4-terpineol (2.8%), beta-elemene (1.9%), alpha-caryophyllene (2.8%), g-elemene (2.96%), caryophyllene oxide (1.02%) and 3-phenylbutyrophenone (1.15%). Oil of M. paniculata contains 58 compounds of which the major are caryophyllene oxide (16.63%), beta-caryophyllene (11.81%), spathulenol (10.21%), beta-elemene (8.94%), germacrene D (6.95%) and cyclooctene, 4-methylene-6-(1-propenylidene) (6.37%). Other major compounds in the M. paniculata oil are cyclohexene, 5,6-dietheyl-3-methyl (3.30%), d-elemene (3.57%), alpha-cubebene (2.96%), retinal (1%), alpha-caryophyllene (3.13%), copaene (2.33%), cubenol (2.36%), nerolidyl acetate (1.20%), 12-oxabicyclo(9.1.0)dodeca-3,7-diene,1,5,5,8-tetramethyl (2.1%), eremophilene (1.54%), ledol (2.2%) and aromadendrene oxide (1.5%). The presence of 3-carene as major compound in M. koenigii is not reported from elsewhere, completely differs from those reported by Raina et al. (2002) and Walde et al. (2005), where pinene, caryophyllenes and phellandrenes were the predominant compounds. This oil may be treated as a natural source of 3-carene, which may be studied for any bioactive properties for therapeutic uses. Also may serve as a useful compound of flavors and fragrances. The oil of M. paniculata also found different from the reports (Anonymous, 1962; Chopra et al., 1956). The study reveals that composition of two oils differs from the earlier reports and may, therefore be treated as different chemotypes.
Conclusion
On the basis of above fact it may be concluded that M. koenigii and M. paniculata, growing widely in Bangladesh, may be utilized as a source for the isolation of natural 3-carene and caryophyllene oxide respectively.
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