Bhave, V G

Gangan, V D

Patil, A

Pradhan, P

Sipahimalani, A T

NOPR

Indian Journal of ChemistryVo1.36B, September 1997, pp.837 - 839N-trans-Feruloyltyramine fromTinospora cordifoliaV DGangan*a, P Pradhanb, A T Sipahimalani", V GBhave" & A PatilCaHindustan Ciba Geigy Research Centre,Chemical Development, Aarey Road,Goregaon(E), Bombay 400 063, IndiabBio-Organic Division, Bhabha Atomic Research Cen-tre, Bombay 400 085, IndiacDept. of Chemistry, Bhavan's College,Andheri(W), Bombay 400 058, IndiaReceived II February 1997; accepted 12 June 1997Nctrans-Feruloyltyramine 1 has been isolated as diacetatefrom the n-BuOH fraction of the methanolic extract of Tcordifolia stems. Its structure has been elucidated by extensive1D and 2D NMR studies.Tinospora cordifolia Miers (Menispermaceae), animportant medicinal plant cultivated thronghout In-dian subcontinent, has been used in Ayurvedic prepa-rations for treatment of various ailments':", Morerecently, Thatte and Dahanukar3 have shown that theaqueous extracts of the plant were associated withthe stimulation of phagocytic and bactericidal capac-ity of.neutrophils and macrophages. Chemical inves-tigations of the plant have indicated the presence ofseveral diterpene furan lactones", phenolic lignan',etc. Our previous studies, with the polar fraction ofthe plant, dealt with the isolation and characterisationof two phenylpropane glycosides", five norditerpenefuran glycosides'r" and two diterpene furan gly-cosides", This communication describes the isolationof N- trans-feruloyltyramine 1. It was obtained as theminor component and was characterised by highresolution ID and 2D NMR spectroscopy as well asby comparison of physical and spectral data with thatof authentic sample. Although known from Tino-spora tuberculata'", this constitutes the first reportabout its occurrence in Tinospora cordifolia. In the• 10 de to assiprevious reports ,no attempts were ma t ssignthe attachment of protons to appropriate carbons,and also some of the J3C chemical shifts assigned toferuloic acid ring were not proper. Therefore, 2DNMR techniques were applied extensively to assigno~ .. 5" ORMco~, J I 04", I N 1" J"J 06, 2 H II 2"RO 5'l;R=Hla;R=Acthe positions of all protons and carbons unequivo-cally which is depicted in Table I.Following the procedure mentioned in our earlierpublication 7, compound I was isolated as its diacetatela from the butanol extract fraction of the methanolicextract of the stem of T cordifolia.Compound la, m.p. 155°, was a colourless solidand showed bluish fluorescence under long UV afterspraying with SbCb (CHCb) and heating. The IRspectrum exhibited several strong absorptions at1700-1770 and 1190-1263 ern", indicating the pres-ence of acetoxy carbonyls and a,~unsaturated ke-tonic carbonyl. The medium intensity bands at 2936,1509-1609 and around 1653-1671 ern" were charac-teristic of aromatic ring and olefinic bond, respec-tively. The presence of > CONH group wasinferred from the presence of bands at 3384 (br),3256, 1767 (sh) and 1540 cm·l. The UV spectrumshowed bands at 276 nm (I> 3.33) and 315.8 nm (I>3.12) indicating the presence of a,~unsaturated car-bonyl system with extensive conjugation. The FABMS [Nar of compound la showed a molecular ionat 420 [M+Nar, thus indicating a molecular weightof397 [Mr. The IH NMR spectrum displayed sevenaromatic protons (OH 7.04-7.30) and a methoxylgroup (OH 3.85) substituted to one of the aromaticrings. A pair of trans- coupled doublets at OH 6.27 and7.59 with J= 16 Hz is typical of a a,p conjugatedcarbonyl system. In addition, an amide (>CONH)triplet, one methylene triplet and one methylene dou-blet of a triplet were observed. These data indicatedthe compound la to be identical with N-trans-feru-loyltyramine isolated by Fukuda et al. 10 from Tino-spora tuberculata. The unambiguous assignments. ofvarious C and H positions were achieved on the838 INDIAN J.CHEM.SEC B, SEPTEMBER 1997Table I-JD and 20 NMR data of N-trans-feruloyltyramine diacetate laDC DC DEPTRev. RepI 165.6 165.5 >C=O2 120.8 139.5 >CH-3 140.4 111.1 >CH-I' 133.7 148.8 >C<2' 111.2 121.0 >CH-3' 151.4 133.6 >C<4' 141.0 140.4 >C<5' 122.8 120.1 >CH-6' 121.8 122.8 >CH--OCH3 55.8 55.7 -CH3>NH40.6 40.7 -CH2-II 34.9 34.8 -CH2-I" 136.4 136.3 >C<2",6" 129.4 129.4 2 x > CH-3",5" 121.3 121.3 2'x> CH-4" 149.3 150.9 >C<DH' COSYFeruloyl6.27(d,16.0) H-37.59(d,16.0) H-27.08(br s) -OCH3NOESY COLOCH-6e,H-2',NHH-5"-OCH3,H-2H-5',-OCH3H-2'H-2H-2'H-2H-IIH-I,H-2",6"H-J,H-IIH-3",S"H-II,H-3",5" H-IIH-2",6"H-2",6"7.04(br s) H-6'7.12(br s) H-5'3.85(s) H-2'5.71 (t,5.8) H-ITyramine3.67(dt,5.8,7.7) H-II, > NH2.89(t, 7.7) H-I7.25( d,8.5)7.06(br s)H-3",5"H-2",6"Acetoxy2 x OCOCH3 20.6 20.521.1 21.0 2 x -CH3 2.32(br s)2 x OCOCH3 168.8 168.4169.8 169.3'Proton assignments are based on '3C_'H HECTOR and 'H COSY experiments.basis of 2D experiments involving '3C_'H COLOC,'H-'HCOSY and 'H-'HNOESYexperiments.The 'H NMR signal at bH 5.71 was assigned to> NH proton as it had no corresponding carbon inHETCOR spectrum. This proton showed COSY iIl-teraction with a methylene at bH 3.67 which in turnhad interaction with the second methylene at bH2.89.On the basis of COSY, the signals at bH 7.25 (H-2",6") and 7.06 (H-3",5") were found to constitute anA2B2 pair and therefore these protons belong to thepara-substituted aromatic ring. The rest three aro-matic protons belong to the other ring with 1, 3,4-substitution pattern. The ortho-pair appeared at bH7.04 (H-S') and 7.12 (H-6'), thus assigning the re-maining proton to H-2'(bH 7.08). The correspondingcarbons were assigned accordingly on the basis of'JCH in HETCOR (Table 1).The methoxyl resonance showed COLOC interac-tion with a carbon at bc IS1.4 and was assigned toC-3'. The former showed nOe with H-2' whereas th.•..latter carbon showed COLOC interaction with H-S',thus confirming their assignments. Similarly, peaksat bc 133.7 and 141.0 were assigned to C-l' and C-4'on account of the COLOC interactions with protonsat H-S' and H-2' respectively. In the second aromatic(tyramine) ring, the peak atbc 136.4 showed COLOCinteractions with two methylene protons at bH 3.67,2.89 as well as with H-3", S" (bH 7.06), whereas theother carbon at bc 149.3 was involved in the COLOCinteraction with H-2", 6" (bH 7.2S). This completesthe unequivocal assignments ofthe carbons.As described previously, the olefinic bond had atrans (E)-configuration on the basis of J value (J2,3=16 Hz), H-2showed nOe with H-2' and H-6' protons.This confirmed that H-2 is cis-disposed to the aro-matic ring and the aromatic ring is probably perpen-dicular to the plane passing through C-l, C-2 and C-3.Experimental SectionGeneral. As per reference No.7.Isolation N-trans-feruloyltyramine diacetate Ia.The plant materialll (5.8kg) was collected fromTrombay campus, Bhabha Atomic Research Centre,Bombay. Fresh stems were subjected to cold extrac-tion with MeOH through percolation. The non-polarcompounds were removed by extraction with petroland EtOAc. It was then extracted with n-BuOH andsubjected to column chromatography over silica gel,using increasing polarities of MeOH in CHCb. Thefractions, with similar polarities, were pooled to-gether (five fractions). The crude fractions 2 and 3were acetylated using AC20 and pyridine at roomtemperature for 48 hr. Further fractionation wasachieved by repeated radial chromatography of theacetylated crude fractions as well as by preparativeTLC. This resulted in the isolation of one morecompound, in addition to previously rer0rted cordi-folisides A, B, C7, cordifolisides D, E and palma-tosides C, F9. -It was named . asN-trans-feruloyltyramine I and was characterised asN- trans-feruloyl tyramine diacetate (La),Chromatographic systemThin layer chromatography: TLC plates were pre-pared using silica gel G (Acme, Bombay), CHCb-MeOH (99: 1) was used as the solvent system.Detection was done by spraying with 20% SbCb(CHCb) and heating (100', 10 min, bluish fluores-cence under long UV). For radial chromatography,circular glass plates (thickness lrnm) were preparedby using silica gel (PF254, E. Merck, 50 g) in colddistilled water (105 mL), and gradually increasingconcentrations of MeOt! in CHCb were employedfor elution. .NOTES 839N-trans-Feruloyltyramine diacetate (La) Colour-less solid (7 mg), Rr (TLC, 0.57, CHCI}:MeOH,99: 1); C22H23N06; m.p. 155'; IR:3384, 3256, 2936,2861, 1767, 1670, 1653, 1609, 1540, 1509,1368,1264,1190,1161, 1117cm-l, UV 276 nm (s 2177),315.8 nm (e 1344); for 'n NMR (200 MHz, CDCb)and l3C NMR (50 MHz, CDCb), see Table I; FABMS: m/z 420 [M+Nat, 398 [M+Ht, 397 [Mt, 355,251,235,219,207, 193, 181, 177, 121,77. Anal.Found C, 66.53; H, 5.83; N, 3.49 Calcd. forC22H23N06: C, 66.49, H, 5.79; N, 3.52 %.AcknowledgementWe thank Dr 0 Seligmann and Prof. Dr H Wagnerof the institute of Pharmaceutical Biology, Univer-sity of Munchen, Germany for recording theFABMS. One of the authors (V D G) thanks theDepartment of Atomic Energy for the award of asenior research fellowship.References1. Kirtikar K R & Basu B D in:Indian medicinal plants, Vol.I,edited by E Blatter, J R Cauis and K S Mhaskar (LalitMohan Basu, Allahabad, India) 1933, p.77.2. Nayampalli S, Ainapore S S & Nadkami P M, Indian JPharmacol, 14, 1982,64.3. Thatte U M & Dahanukar S A, Phyiotherapy Res, 3,1989,43.4. Bhatt R K & Sabata B K, Phytochemistry, 28,1989,2419.5. Hanuman J B, Mishra A K & Sabata B K, J Chern Soc,Perkin Trans, 1,1986,1181.6. Sipahimalani A T, Norr H & Wagner H, Planta Medica, 60,1994,596.7. Gangan V D, Pradhan P, Sipahimalani A T & Banerji A,Phytochemistry, 37,1994,781.8. Gangan V D, Pradhan P, Sipahimalani A T & Banerji A,Phytochemistry, 39, 1995, 1139.9. Gangan V D, Pradhan P, Sipahimalani A T & Banerji A,Indian J Chern, 35B, 1996,630.10. Fukuda N, Yonemitsu M & Kimura T, Chern. Pharm. Bull,31, 1983, 156 and the references cited therein.11. Identified by Dr V Abraham of Nuclear Agriculture Divi-sion, BARC, Bombay.

N-trans-Feruloyltyramine from Tinospora cordifolia

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N-trans-Feruloyltyramine from Tinospora cordifolia

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