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September 2009 Volume 5 Issue 3

NNaattuurraall PPrrAoon dIdnduuian ccJotutrnssal Trade Science Inc. Full Paper NPAIJ, 5(3), 2009 [116-119] Compositions and comparison of the leaf and stem essential oils from Nigerian Hypoestes phyllostachya ‘ ’ rosea p. Beau. [Acanthaceae]

Dorcas Olufunke Moronkola*, Odunayo Christy Atewolara- Odule, Oseyemi Omowunmi Olubomehin Department of Chemical Sciences, Olabisi Onabanjo University, P.M.B. 2002, Ago-Iwoye, Ogun-State, (NIGERIA) E-mail : [email protected] Received: 22nd May, 2009 ; Accepted: 2nd June, 2009

ABSTRACT KEYWORDS

Leaf and stem volatile oils were obtained differently from Hypoestes Hypoestes phyllostachya ‘ ’ [HR] [Acanthaceae] in 0.36% and 0.13% respectively. ‘ ’ phyllostachya Rosea Rosea ; Fourteen main volatiles were identified in the stem part which had Acanthaceae; appreciable amount of sesquiterpenes with the most abundant compounds Naphthalenones; being 3,5,6,7,8,8a-hexahydro-4,8a-dimethyl-6-(1-methylethenyl)-2(1H) Cyclohexanes; naphthalenone (38.01%), 1-ethenyl-1-methyl-2(1-methylethenyl)-4-(1- Taxonomic compounds; methylethylidene) cyclohexane (14.26%) and tetramethylcyclopropylidene Hydrodistillation. methylbenzene(7.38%). Twenty-five compounds were identified in the leaf oil of HR which also contained appreciable amount of sesquiterpenes. The most abundant compounds were 3,5,6,7,8,8a-hexahydro-4,8a-dimethyl-6- (1-methylethenyl)-2(1H)naphthalenone(23.3%), and1-ethenyl-1-methyl-2- (1-methylethenyl)-4-(1-methylethylidene) cyclohexane(20.73%), which were the same as in the stem parts. The two most abundant compounds are common to both leaf and stem essential oils. They could be taken as taxonomic compounds for identifying HR, as well as being commercial sources of the naphthalenone and cyclohexane derivatives. The oils were characterised by the presence of derivatives of azulenes and naphthalenes. The known ubiquitous monoterpenes were absent in both leaf and stem essential oils. We report the volatile composition of Hypoestes ‘Rosea’ which is scarce in literature. phyllostachya  2009 Trade Science Inc. - INDIA

INTRODUCTION to add colour in partially shaded areas. The sizes are ” to 4ft, with bushy and coloured shape. They between 8 The broad-leafed evergreen Acanthaceae are native to Madagascar, but found in most parts of ‘Rosea’ is a tropical sub Hypoestes phyllostachya the world especially West Africa, they are indigenous ‘polka dot plant’, ‘freckle shrub commonly referred to as to Nigeria. The flowers are tiny lilac in racemes[1-3]. This ’, and ‘morning glory lobelia’. It is grown as an face colourful foliage plant is ideal for desk bowls and as indoor houseplant and as accent plant in dish gardens under plant in feature beds. Naturally occurring NPAIJ, 5(3) September 2009 Dorcas Olufunke Moronkola et al. 117 Full Paper diterpenes most of which are cell-permeable, with anti- model 6890 GC-MSD system with split/splitless auto- inflammatory, antifungal and anticancer activities have mated injection interfaced to a 5973 mass selective been reported in the genus Hypoestes, they include detector operated at 70eV with a mass range of m/z hypoestoxide, fusicoserpenol, dolabeserpenic acid, 50-500. Same operations and temperature program- dihypoestoxide, roseatoxide, roseanolone and ming were used as for GC. Relative percentage amounts roseadione[4-11]. of the separated compounds were calculated from FID Acanthaceae earlier taken as a single taxon, are the chromatograms as seen in tables 1 and 2. rd third [3 ] largest tropical family of dicotyledonous plants Identification of components of about 2,500 species in 250 genera. They are mostly herbs and shrubs with general and divers, local and Identification of the essential oil components were medicinal values, ornamental and mechanical uses[12,13]. based on their retention indices (determined with a ref- Data on the chemical compositions of plants in erence to a homologous series of n-alkanes), and by Acanthaceae including their volatile constituents and the comparison of their mass spectral fragmentation pat- causative agent(s) in each plant are not adequate in terns in computer matching against in-built data and literature[14]. This study is a continuation of our research commercials such as NIST database/ Chemstation data system, Wiley GC-MS Library[15], Adams Library[16], into the chemical constituents of the poorly and rarely “Baºer Li- Mass Finder 3.1 Library[17] and in-house studied species of the Nigerian flora. ” built up by genuine brary of Essential Oil Constituents EXPERIMENTAL compounds and components of known oils.

Plant Collection and Isolation of the Volatile Oils RESULTS ‘Rosea’ Fresh shrubs of Hypoestes phyllostachya TABLE 1 : Essential Oil Composition of Leaf of Nigerian ‘ ’ were collected in January 2008, from University of Hypoestes phyllostachya rosea P ea k R T % Ibadan nursery and other parts of Ibadan, Nigeria. The C o m p oun d Ide ntified N o a (m ins) b T IC c plant was authenticated by Dr. A. A. Ayodele of the 1 10 .7 3 0 .8 0 1 -octen ol 2 25 .0 5 0 .5 3 Y lan g en e 7-m eth ylen e-2 ,4 ,4-trim eth yl-2- University Herbarium, Department of Botany and Mi- 3 25 .9 0 0 .3 8 vin ylbic yclo[4.3.0]n onan e crobiology, University of Ibadan, Nigeria where a 4 26 .8 4 1 .6 4 ca ryop h yllen e 2 ,6 -dim eth yl-6-(4 -m eth yl-3 -penten yl)- 5 27 .2 4 1 .6 4 voucher specimen was deposited. bic yclo[3 .1 .1 ]h ept-2 -en e 6 27 .9 5 3 .9 9 1 ,5,9,9-tetram eth yl-z,z ,z-1,4,7-cycloun d ecatrien e 1 -m eth yl-5 -m eth ylen e-8-(1 -m eth yeth yl)-[s-(E ,E )]- 7 28 .8 1 3 .1 7 The plant was separated into leaf and stem parts. 1 ,6 -cyclode catrien e 1 ,2,3,4,5,6,7,8-octah ydro-1,4-dim eth yl-7 -(1- 8 29 .0 5 2 .3 8 Weighed amounts of each were hydrodistilled in an all m eth yleth ylid en e),(1 S-cid )-a zulen e 1 ,2,3,4,5,6,7 ,8,8a -octah yd ro-1 ,4 -dim eth yl-7-(1 - 9 29 .5 3 2 .2 4 á ,7á ,8aâ)] glass Clevenger-type apparatus, over very little distilled m eth yleth en yl)-[1 S-(1 -az ulen e 1,2,4 a,5,6,8a -h ex ah yd ro-4 ,7 -d im eth yl-1 -(1- 10 29 .8 1 0 .9 0 hexane (0.3ml), which was removed afterwards. The m eth yleth yl)-n a phth alen e 1,2,4 a,5,8,8a -h ex ah yd ro-4 ,7 -d im eth yl-1 -(1- 11 30 .0 4 0 .7 8 á ,4aâ ,8a á )] distillation time was about 3hours in each case. m eth yleth yl),[1S -(1 -n aphth alen e 12 30 .2 7 2 .2 2 3,5 -dim eth yl-a cetate,ph en ol 1 ,2,3,4,5,6,7 ,8,8a -octah yd ro-1 ,8 a-dim eth yl-7 -(1- 13 30 .6 6 2 .0 4 á ,7 â,8a)] Gas chromatography (GC) m eth yleth en yl)-[1 R -(1 -n aph th alen e á á ,4 4-eth en yl-1 -trim eth yl-3-(1 -m eth yleth en yl)-[1 R - 14 30 .9 9 4 .5 3 á ,3á,4â ) (1 ]-cycloh exan em eth an ol The volatile oil samples were subjected to GC 1-eth en yl-1-m eth yl-2-(1 -m eth yleth en yl)-4 -(1- 15 31 .1 8 20.73 m eth yleth yliden e)-c ycloh ex an e analyses on an Agilent model 6890 gas chromatograph deca h ydro-1,1,7-trim eth yl-4-m eth ylen e- 16 31 .3 2 11.29 á,4 aâ,7á,7a â,7 bá )] [1a R (1 a -1H -cycloprop[e]a zu len e fitted with a flame ionization detector (FID) and DB-5 D eca h ydro-1,1,7-trim eth yl-4-m eth ylen e- 17 32 .6 8 2 .0 3 á,4 aá,7á,7a â,7bá )] µm film thickness). Helium was used [1a R (1 a -1 H -c yclop rop [e]az ulen e (30x0.25mm, 0.25 1a ,2,3,5,6,7,7a,7b-octah ydro-1,1,4,7-tetram eth yl- 18 34 .4 0 2 .3 9 á,7 á,7 aâ,7bá ] [1a R -(1 a -1 H -c yclop rop[e]a zu len e as carrier gas at a flow rate of 1ml/min. The GC oven 1,2,3 ,4,4a,5,6,8 a-octah ydro-4a ,8-dim eth yl-2 - 19 34 .7 2 3 .3 9  (1 -m eth yleth ylid en e)-(4a R -tran s)-na ph th alen e temperature was programmed at 60 C (held for 2mins), 3,5,6 ,7,8,8a-h exah ydro-4,8a -d im eth yl-6 -(1- 20 36 .3 2 23.30 m eth yleth en yl)-2 (1H )n aph tha len on e   á heated to 250 C at 4 C/min, with final hold time of 21 40 .6 2 1 .7 7 -fa rrn esen e (E ,E )-7,1 1,1 5-trim eth yl-3 -m eth ylen e-h exa deca - 22 42 .7 6 3 .7 8 20min. Injector and detector temperatures were fixed 1,6,1 0,1 4-tetraen e 23 43 .3 9 2 .1 2 1 -(3-m eth ylbu tyl)-2,3,6-trim eth ylb en zen e   á ,9 â at 200 C and 250 C respectively. 24 44 .7 8 1 .3 0 3 -m eth oxy-8 -estra-1,3,5 -(10)-trien -17 -on e 2 ,3,4 ,5,6,7,-h ex ah yd ro-1-(2 - 25 47 .1 1 0 .6 6 Gas chromatography-Mass spectrometry (GC-MS) h yd rox y-2 -m eth ylpropyl)-1 H -2-in den ol aAccording to the pattern of elution from the GC[Fig 1] The GC-MS analyses were performed on an Agilent bRentention time in minutes; cTotal ion concentration in %.

NaturaAln P Inrdoiand Juourcnatls 118 Compositions and comparison o.f the leaf and stem essential oils NPAIJ, 5(3) September 2009 Full Paper content of the following classes of compounds: aro- matics, hydrocarbons, azulenes, alcohols, alicyclics, sesquiterpenes, ketones and esters[table 3]. Sesquit- erpenes of appreciable amount was found in both the leaf and stem oils while the ubiquitous monoterpene was absent in both. The two most abundant compounds 3,5,6,7,8,8a-hexahydro-4,8a-dimethyl-6-(1- methylethenyl)-2(1H)naphthalenone, and 1-ethenyl-1- methyl-2-(1-methylethenyl)-4-(1-methylethylidene) cy- clohexane, are common to both leaf and stem oils.

Figure 1 : Gas chromatogram of the leaf essential oil of ‘ ’ Hypoestes phyllostachya rosea (Acanthaceae), using col-  umn fitted with DB-5 (30x0.25mm, 0.25 m film thickness).

TABLE 2 : Essential Oil Composition of Stem part of Nige- ‘ ’ rian Hypoestes phyllostachya rosea RT Peak Noa % TICc Compound Identified (mins)b 1 26.83 2.12 Caryophyllene 2,6-dimethyl-6-(4-methyl-3-pentenyl)- 2 27.26 3.25 bicyclo[3.1.1]hept-2-ene 1,5,9,9-tetramethyl-z,z,z-1,4,7- 3 27.94 3.23 cycloundecatriene 1,2,3,5,6,8a-hexahydro-4,7-dimethyl-1- 4 30.04 1.73 (1-methylethyl),(1S-cis)-naphthalene 1-ethenyl-1-methyl-2-(1-methylethenyl)-4- 5 31.14 14.26 Figure 2 : Gas chromatogram of the stem essential oil of (1-methylethylidene)-cyclohexane ‘ ’ 6-ethenyl-6-methyl-1-(1-methylethyl)-3- 6 31.29 7.26 Hypoestes phyllostachya rosea (Acanthaceae),using column (1-methylethylidene)-(S)-cyclohexene  1,2,3,4,4a,5,6,8a-octahydro-7-methyl-4-methylene-1- fitted with DB-5 (30x0.25mm, 0.25 m film thickness). 7 32.69 6.90 á,4aâ,8aá)] (1-methylethyl)-(1 -naphthalene 1a,2,3,5,6,7,7a,7b-octahydro-1,1,4,7-tetramethyl- 8 34.39 4.38 á,7á,7aâ,7bá] [1aR-(1a -1H-cycloprop[e]azulene TABLE 3 : Comparisons between the Chemical Compositions 1a,2,3,4,4a,5,6,7b-octahydro-1,1,4,7-tetramethyl- 9 34.72 4.96 á,4á,4aâ,7bá] of the Leaf and Stem Essential Oils of Hypoestes phyllostachya [1aR-(1a -1H-cycloprop[e]azulene ‘ ’ 3,5,6,7,8,8a-hexahydro-4,8a-dimethyl-6- Rosea . 10 36.31 38.01 (1-methylethenyl)-2(1H)naphthalenone Am ount in 11 43.40 2.39 2-isopropoxyphenyl,4-ethylbenzoate Class of the essential oils of [% ] 12 44.78 7.38 [(tetramethylcyclopropylidene)methyl]-benzene O rganic compound 13 47.29 2.47 Estrolactone Leaf Stem 14 47.90 1.66 Retinol Arom atics[naphthalene and a 32.53 56.41 According to the pattern of elution from the GC[Fig 2] benzene derivatives] b Rentention time in minutes; cTotal ion concentration in % Unsaturated hydrocarbons 31.67 24.75 Azulenes 20.33 9.34 DISCUSSION Alcohols 7.41 1.66 Alicyclics 1.64 3.25 Sesquiterpenes 3.94 2.12 We obtained essential oils from the stem and leaf ‘ ’ Ketones 1.30 Nil parts of Hypoestes phyllostachya Rosea in respec- Esters Nil 2.39 tively 0.36% and 0.13% yields with characteristic smells. The leaf oil is light yellow with hard woody- The two most abundant compounds 3,5,6,7,8,8a- leafy odour. Stem oil has woody slightly pungent smell. hexahydro-4,8a-dimethyl-6-(1-methylethenyl)- Twenty-five and fourteen compounds make-up the leaf 2(1H)naphthalenone, and 1-ethenyl-1-methyl-2-(1- and stem essential oils[tables 1, 2] respectively. GC methylethenyl)-4-(1-methylethylidene) cyclohexane, are analyses reveal that the oils were characterized by high common to both leaf and stem oils. They could be taken

NaturaAln PInrdioand Jouurcnatl s NPAIJ, 5(3) September 2009 Dorcas Olufunke Moronkola et al. 119 Full Paper as taxonomic compounds for identifying Hypoestes [6] E.A.Ojo-Amaize, E.J.Nchekwube, H.B.Cottam, ‘Rosea’ as well as being commercial O.A.Oyemade, A.A.Adesomoju, J.I.Okogun; phyllostachya ‘ Plasmodium berghei: Antiparasitic effects of orally sources of the naphthalenone and cyclohexane ’, Elselvier lnc. derivatives. This report is the first to provide and administered Hypoestoxide in mice compare the chemical composition of the volatile oils (2007). [7] L.Rasoamiaranjanahary, D.Guilet, A.Marston, of the leaf and stem of Hypoestes phyllostachya ‘Rosea’. F.Randimbivololona, K.Hostettmann; Antifungal isopimaranes from Hypoestes serpens Phytochemistry. 64(2), 543-548 (2003a). ACKNOWLEDGMENTS [8] L.Rasoamiaranjanahary, A.Marston, D.Guilet, K.Schenk, F.Randimbivololona, K.Hostettmann; We acknowledge the assistance of Staff of the Phytochemistry. 62(3), 333-337 (2003b). herbarium, Botany and Microbiology Department in the [9] A.A.Adesomoju, J.I.Okogun, M.P.Cava, identification and collection of the plant, and Dr Faruq P.J.Carroll; Phytochemistry. 22, 2535-2536 Usman, University of Sokoto, Nigeria where the GC, (1983a). GC-MS were done. The essential oil group (2006/2007 [10] A.A.Adesomoju, J.I.Okogun, M.P.Cava, session), Department of Chemical Sciences, OOU, P.J.Carroll; Heterocycles. 20, 2125-2128 (1983b). [11] J.I.Okogun, A.A.Adesomoju, G.A.Adesida, assisted in isolating each volatile oil. H.J.Lindner, G.Herbomelil; Z.Naturforsch. 37c, 558-561 (1982). REFERENCES [12] U.H.Botany; Flowering plant families. Acanthaceae, Wikipedia-free encyclopedia (2008). [1] Plant Finder; Hypoestes Phyllostachya Kemper – Your Path To Quality [13] Botanical dermatology database BoDD; Centre For Home Gardening Acanthaceae (2008). Gardening Home. Missouri botanical garden (2001- [14] D.O.Moronkola, I.A.Oladosu, I.A.Ogunwande; 2008). ’ guide A Chemical Compositions of Seven Essential Oil [2] Plants-in-buildings.com ambious specifiers Samples from 3 Nigerian Acanthaceae: Asystasia to Z of plants View plants (2009). gangetica(L), Brillantaisia patula T.And.var and ‘Rosea’ ISEO 2008 39 [3] L.S.Gill; Ethno-medical uses of plants in Nigeria: Hypoestes phyllostachya th Hypoestes rosea, Uniben Press Benin (1992). International Symposium on Essential Oils. Held 7th- [4] E.A.Ojo-Amaize, P.Kapahi, V.N.Kakkanaiah, 10th September, 2008 at the Congress Centre, T.Takahashi, T.Shalom-Barak, H.B.Cottam, Quedlinburg, Germany (2008). A.A.Adesomoju, E.N.Nchekwube, O.A.Oyemade, [15] Y.Massada; Analysis of Essential Oils by Gas Chro- M.Karin, J.I.Okogun; Cell.Immunol., 209, 149-157 matography and Mass Spectrometry. J. Wiley & (2001). Sons, New York, NY (1976). [5] E.A.Ojo-Amaize, E.J.Nchekwube, H.B.Cottam, [16] R.P.Adams; Allured Pub.Corp., Carol Stream, IL R.Bai, P.Verdier-Pinard, V.N.Kakkanaiah, (1995). J.A.Varner, L.Leoni, J.I.Okogun, A.A.Adesomoju, [17] D.Joulain, W.A.Koenig; The Atlas of Spectral Data O.A.Oyemade, E.Hamel; Cancer Research., 62, of Sesquiterpene Hydrocarbons. E-B Verlag, Ham- 4007-4014 (2002). burg, Germany (1998).

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