Composition of Elsholtzia polystachya leaf essential oil

Composition of Elsholtzia polystachya leaf essential oil

Phytochem~stry,Vol 27, No 4, pp 10651067, Prmted m Great Bntam COMPOSITION 1988 0 003 l-9422/88 $3 00 + 0 00 1988 Pergamon Journals Ltd OF ELSHOLT...

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Phytochem~stry,Vol 27, No 4, pp 10651067, Prmted m Great Bntam

COMPOSITION

1988 0

003 l-9422/88 $3 00 + 0 00 1988 Pergamon Journals Ltd

OF ELSHOLTZIA POLYSTACH YA LEAF ESSENTIAL ATEEQUE

OIL

AHMAD, MOHAMMAD S. SIDDIQUI and LAXMI N MISRA

Department of Phytochemlstry, Central Insutute of Medlcmal and Aromatlc Plants, Lucknow 226016, India (Rewed

receroed 15 [email protected]

1987)

Key Word Index-Elsholtzm pofystachya,Lamlaceae, monoterpenolds, column CC-MS, chemotaxonomy

sesqmterpenes, essential 011,capillary

Abstract-Fragrance components of the leaves of Elsholtzza polystachya have been investigated to afford rune monoterpene hydrocarbons, 11 oxygenated monoterpenes, 16 sesqmterpenes, two ahphatlc esters, several sesquiterpene alcohols and a phenyl propanold A chemical grouping of EIsholtzza species 1s dlscussed briefly.

INTRODUCTION

The genus Elsholtzia is an ornamental, usually aromatic herb or undershrub, distributed chiefly in Asia and a few m Africa and Europe [l] The essential 011of 13 species of Elsholtzia has been chemically investigated [2-181 EIsholtzla polystuchyu Benth syn. E frutlcosu D. Don, a pubescent shrub of 3.5 m height, grows m the Himalayas from Kashmir to Slkklm and m Khasi hills at altitudes of 400&9000 feet where it IS often used as a fuel [l]. The essential 011 of E polystuchya has been the subject of a limited earlier mvestlgatlon [18] A detailed GC-MS analysis of its essential oil 1s described in this paper. RESULTS AND

DISCUSSION

In our continued effort of searching new sources of aromatic products [19-211, we surveyed the Kumaon hills of Himalayas and collected the leaves of E. polystuchyu, which impart a strong odour reminiscent of Eucalyptus oil. After hydrodistlllatlon it afforded a yellowish 011 m 14% yield (dry basis). The oil was subjected to GC-MS analysis which showed the presence of 78 well-resolved constituents. Nine were monoterpene hydrocarbons (16.02%), 11 oxygenated monoterpenes (69.03%), 16 sesqulterpenes (6.67%), several sesquiterpene alcohols (2.16%), two aliphatic esters (0.75%), a phenyl propanoid (2.11%) and a few unidentified (see Table 1). The major constituents included 1,4-cineole (20 04%), 1,8-cmeole (26 11%), perdlaldehyde (7.24%), neryl acetate (10.12%), geranyl acetate (2 14%) and pcaryophyllene (2.56%) The GC-MS spectra indicated the presence of 16 sesqulterpene alcohols including four with [M] + at m/z 220 while the others possess an M + at m/z 222 Their total percentage has been given m Table 1 The total number of sesqulterpene hydrocarbons was 24 including eight umdentlEed (W%). ‘l-he other umdentlfied constituents (15 m number) showed [M]’ at m/z 136 and 150 amounting to ca 102% of the total 011. All constituents were identified by their R,, Kovats index and MS fragmentation [22] but the chief components, 1.e. 1,8cmeole and 1,4-cineole were further confirmed by isolation m pure form and recording their ‘H NMR spectra. The presence of five valuable oxygenated monoterpenes

in high percentage (cu 68%) makes the oil strongly odorous. The 011 also contains fi-caryophyllene and cadinenes (3 59%) The desirable sesqulterpenes along with sesquiterpene alcohols (2.16%) makes the oil long lasting and thus more attractive. The occurrence of 1,8-cmeole as the major component has earlier been reported from the esssentlal 011s of Artemwzu cma, Suluu~ trtlobu, Eucalyptus globulus, Cmnumomum camphoru and Italian laurel leaf 011 The co-

occurrence of 1,4-cmeole with 1,8-cineole has been reported m the 011of Elleturiu curdumomum, clary sage 011, hme 011and several other essential oils either m traces or m ~5% of total 011. Therefore, it 1s worth mentioning that the essential 011of Elsholtzw polystuchyu IS probably the first source m which 1,4-cmeole IS found m such a high percentage. A survey of the literature showed that the essential oil of 13 species of Elsholtzru has been chemically investigated [2-181. These studies suggested that Elsholtziu species can be divided into three groups with the following compounds as the mam constituents: (I) oxygenated monoterpenoids (E. pzlosu [6], E. blundu [8] and E. strobllzfira [9, lo]), (u) furano-monoterpenoids (E ciliutu [3,4], E. densu [S], E. crlstutu [ll], E. oldharm [12,13], E. urgyl [2], E. purtrzmi [14, 151) and (iii) phenylpropanoids (E splendens [7], E. mctsu [16], and E urgyt var. nzppomcu [17]). According to our investigation, the essential 011 of E polystuchyu IS comprised of monoterpenoids; therefore it may be included in the first category along with E. strobdferu, E. blundu and E prlosu Further work on other Elsholtzm species is desirable before chemosystematic conclusions can be drawn.

EXPERIMENTAL The

plant matenai was collected m the month of-March f9gJ from Kumaon region of Himalayas. The speemen voucher has been deposlted m the herbarium of our mstltute. Three kg of plant matenal after hydro-distillation yleidtid~42 rnI ofessentiar 011,da50 9461, nis 1 4788, LY;* -0 03”, actd value 5 43, ester value 28.54, ester value after acetylatlon 55.78. Pure 1,8-cmeole and 1,4-cmeole were obtamed after column and preparative TLC on AgNOa impregnated slllca gel, 80 MHz ‘H NMR spectra were

1065

A AHMAD ef al

1066 Table

I Constituents

___.___Peak No I

2 3 4 5 6 7 8 9 IO II 12 I3 14 I5 I6 I7 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41

of the essential 011 of E pol~,\t~ /?~a _-___.

Compound

Identified

?-Thtljene r-Pmene Cdmphene Sabmene Myrcene /I-Pmene h-3-Cdrene

a. b c

t 1 Tentative Identdicatlon t Trace (~005%) a co-InJection with duthentlc material, fragmentation, d ‘F-INMR spectrum

recorded on V-arlan FT 8tJ A instrument m CDCT, with TMS as Internal reference CC-MS data was obtamed with CC Varlan model 3700 coupled with MS-Varlan MAT model 71 I (70 eV direct Inlet) usmg 25 m Chromapack CP SII 5 capillary column programmed as mltlal temperature, 70” for 4 mm then 10”/mm to 330’ and Isothermal for 4 mm with He as carrier gas The CC work was carried out with d Perkm-Elmer 3920B CC using a Carbowax 20 m packed column, mltiaffy at 60^” for 4 mm then 4‘jmm to 180 and lsothermai for 16 mm using H, ds cdrrler gas The spectra of known compounds were compared with the hbrary estabhshed by us and with the ddta available m the

“i, or total 011 0 56 I 03 0 07 0 07

n. b, c

a, b, a. b, a, b. d, b, a. b. d. b, d. b, a, b, a, b. A, b.

1,4-Cmeole 1,X-Cmcole c rc-Oclmene y-Terpmene Terpmen-4-01 a-p-DImethyl-ytyrene Lmalyl acetdte Perlllaldehyde Myrtenol (t 1) Cltronellyl dcetate n-Terpmyl acetate Neryl Acetate Geranyl acetate Irrtdomyrmecm (t 1) 7-Methyl-3-methylene-7octen- 1-yl proplondte 3,7-Dimethyl-2,7-octadlen-I propionatc z-Longlpmene (t 1) r-Ylangene p-Elemene /I-Fdmesene cc-Gurjunene /?-Caryophyllene Germacrene-D r-Humulene Santalene (t I ) &Sehnene y-Muurolene p-Risdbolene I-Muurolene (t 1) &Cddmene Caldmenene ;I-Cadmene Sesqui, alcohols (M + 220) Sesqul alcohols (M + 222)

by

b, a, a, b, a, a, A a, b,

c b, b. L b, b, b, b, c

c c c c c L d c. d c L c c c c c c c

t 2 x7 651 20 04 26 I I IO1 1 90 I 31 7 II 0 54 7 24 OS1 0 3x 0 41 IO I7 2 I4 0 73

b, c

0 65

b, b, b. b. b. b, b. b. b. b.

0 IO 0 IO 0 IO 0 IO 0 05 0 3x 2 56 0 35 0 54 0 25 0 15 062 0 20 0 04 0 38 0 IO 065 0 21 I 95 ____

yl c c c c c c ‘ c c c

b, c b, c b. c b, b, b, b, c c

c c c c

b Kovats

hterature Table I

Index and retentlon

122, ZJJ

time, c mass

The ldentlfied

constituents

are Lsted

In

Ackno~ledllemmrc-The authors thank Dr Akhtar Husam, Director, for hi, keen interest m the work and to Prof Dr F Bohlmann, Director, Institute of Organic Chenustry. Techmcal Cimverslty ofBeriln, West Germany. rhr Lmdiy recordmg GCMS spectra of the 011 Dr N- c‘ Shah. Scclentl\t CTMAP. IS gratefully thanked for his help In plant collectjon and Identlficdtlon

Composltlon

of Elsholtzra polystachya

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