Achlorinatedmonoterpeneketone,acylated b-sitosterolglycosides andaflavanoneglycosidefrom Mentha longifolia (Lamiaceae) MuhammadShaiqAli a, *,MuhammadSaleem a ,WaqarAhmad a ,MasoodParvez b , RaghavYamdagni b a H.E.J. Research Institute of Chemistry, University of Karachi, Karachi-75270, Pakistan b Department of Chemistry, University of Calgary, 2500 University Drive NW, Calgary, Alberta, Canada T2N IN4 Received4June2001;receivedinrevisedform15November2001 Abstract Mentha longifolia (Lamiaceae),anaromaticherbyieldedanewhalogenatedchloro-derivativeofmenthone(longifone),twonew derivativesof b-sitosterolglycoside(longiside-Aand-B)andanewflavanone-glycoside(longitin).The b-sitosterolandflavanone glycosideswerepurifiedastheiracetatederivatives.StructuresofalltheisolatedconstituentswereelucidatedwiththeaidofHMBC techniques.However,thestructureoflongifonewasalsodeterminedthroughX-raycrystallography. # 2002ElsevierScienceLtd. Allrightsreserved. Keywords: Mentha longifolia; Lamiaceae; Halogenated-monoterpenoid; X-ray; Steroidal-glycosides; Flavanone-glycoside; Structure elucidation; Spectroscopy;2DNMR 1. Introduction The genus Mentha belongs to the family Lamiaceae (Labiatae) consisting of about 25–30 species (Ali and Nasir, 1990); most of them are found in temperate regions of Eurasia, Australia and South Africa. Although Mentha is a distinct genus of the family Lamiaceae,ithassometaxonomicdifficultiesatspecies level.Thesedifficultiesarisefromaverylonghistoryof cultivation and naturalization, vegetative plasticity and widespread.Thearomatic Mentha herbsareperennials foundindamporwetplaces.Membersofthisgenusare the most important sources of essential oil production intheworld.Ithasbeenestimatedthattheannualpro- ductionofoilsfromthreemintspecies,peppermint(M. piperita), cornmint (M. arvensis) and spearmint (M. spicata) is worth 186 million dollars (Laplinska, 1993). Somemembersofthisgenusarealsousedasherbalteas andcondimentsinbothfreshanddriedformduetotheir distinctaroma(BaserandKurkcuoglu,1999).Themost commonspeciesofthegenus Mentha foundinPakistan are: M. pulegium, M. arevensis, M. spicata, M. longifolia, M. piperita and M. royleana (AliandNasir,1990). Chemical literature surveys of the genus Mentha revealedthatmostlyithasbeenstudiedforthechemical compositionofessentialoils(Baseretal.,1997;Guido etal.,1997).Constituentsofessentialoilsandtheirgly- cosideshavebeenreportedbyseveralgroupsfromvar- ious species of this genus. They include: menthone, menthol, menthyl acetate, neo-isomenthyl acetate, 1- menthyl-b-d-glucopyranosyl (Sakata and Mitsui, 1975) and 1-menthyl-6 0 -O-acetyl-b-d-glucopyranosyl (Sakata andKoshimizu,1978).Otherthanessentialoils,various species of this genus have been afforded steroidal gly- cosides (Shimizu et al., 1990), flavone (Ahmad et al., 1886)andflavoneglycosides(Kamiyaetal.,1979). Mentha longifolia is distributed through out Eurasia andtropicalAsiabutuncommoninourregion.Several essentialoils(Ghoulamietal.,2001;Nori-Sharghetal., 2000;Abu-Al-Futuhetal.,2000),flavonesandflavone- glycosides (Ghoulami et al., 2001; Sharaf et al., 1999) have recently been obtained from this species. In the presentcommunication,wewishtoreporttheisolation and structure elucidation of four new constituents: a new chloro-derivative of menthone (longifone, 1), two 0031-9422/02/$-seefrontmatter # 2002ElsevierScienceLtd.Allrightsreserved. PII:S0031-9422(01)00490-3 Phytochemistry59(2002)889–895 www.elsevier.com/locate/phytochem * Corresponding author. Tel.: +92-21-9243232; fax: +92-21- 9243190-91. E-mail address: shaiq303@super.net.pk shaiq303@hotmail.com (M.ShaiqAli).