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    6 views7 pages

    $ exHNMR

    Uploaded by

    Novida Rizani

    Copyright:

    Attribution Non-Commercial (BY-NC)
    Download as PDF, TXT or read online from Scribd
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    Rue dteey Dr, Taston Erna MS ae “20 SEP 1998 » NIP. 5 190 781344 ee Colouring Matters of the Wood of Arcocarpus heterophyllus: tN | Pat VI"—Cycloheterophyllin, a Flavone Linked to Bet la Three Isoprenoid Groupst¢ ny + A.V. RAMA RAO, Glia MALA VARADAN & K. VENKATARAMAN National Chemical Laboratery. Yoone 8 From the bark of A. hecerophyllus Lark. (wo new a Mennscript received 30 July 1970 shave been Isolated, The structure of the relatively major pigment, cyciohe whan been deduced as (1), batéd on UV, IR, NAR and mace spectral dace, ln is the frse avons having three Isopreasld groupe attached te the chromont ie aspects of ‘Morus and Artocarpus flaveaoids are dlecusted. 'N recent years we have reported" the isolation I of a new flavanone and seven new flavones from : the heartwood of A. heterophvilus Lamk. (A. | acelin Seater ste ai A flavonoids, including morin ‘and eyanomaclutin Teolated earlier be Perkin: ie the ry ‘ylic orientation of hydroxy] groups in the tT) ing. The A-ring, as in numerous flavonoids, is derived from. phloroglucinol. Six of the new flayones earry one or two isoprenoid units attached to the chromone nucleus. Examination of the trunk bark has now revealed ile presence of at least two flavonoids present in very minute quantities, which were different from the compounds isolated from the heartwood. The relatively major pigment, for which the trivial name cycleheterophvllin is Proposed, is assigned the structure I on the basix of spectral cvidence. aD Hexane and benzene extracts of the trunk bark, 2a removal of solvent and shaking with cold methta- Rol, gave = colourless crystalline compound, m.p. Sigs Wdentied as petulindg acid’ Frome te acne: pol-oluble portion two flavonoid pigments were Bolated in yields of Jess than 0-01 and 0001% Fisrectively by an elaborate procedure described fn the experimental part. Pat Ve Tadinn J-Chome 7 94, 101 TREE Communion Na” fe ; : sepaistel Cot Tin athe on the een of hi voin Tay cee Cycloheternphyilin erystallizes from methanol yellow needles, im.y. 205-65. It giver 3. wine-red colour in the Shinoda test and i green colour with alcoholic ferric chloride. The ‘elements! analy and molecular weight (il* 502) are in agreement with the molecular formula CyuHaOy. It forms 1 dimethyl ether (M* 530) with ethereal diazomethane: a green cokiuration with alcoholic ferric elke indicates the presence af a banded hiydeuxy' On prolonged treatment witht excess sulphate and potassium earbonate in builing acetone, 2 trimethy) ether (BI* 544) was obtained Hydro genation of the trimethyl ether in aeetic 3 I lyst yielded ative (4° 550), showing il nic bonds. Tnits UV spectrum Dette", mg (log e), 264 (4-326), 297 (4°57), 402 (4-342): eyeloheterophiyllin closely fesembies evcloattacarpin (II), rather than am carpin (ly Rare 2] We two major flave Fier elated from ic heartwood? The long wavelength absorption in_artocarpin and cyclo: artocarpin is at 324 and 370 ma tespectively. and the large bathochromic shift in the latter was ex- plained? by the caplanarity of rings B, C and D, Fesulting in maximum conjugation betwee chromone and pens} rings. In artocarpin ,Y-dimethylally] substituent forces the. 2-;henyl group out-of-plane with the chromene ring. The Presence of a free 4'-Wvdroxyl group as in all the other Artocarpus pigments was established by the shift of the 402 mp band to 440 mg with 2 marked increase in intensity on adding sodium ethoxide to the ethanolic solu ‘The TR spectrum (nujol) of cycloheterophy i showed characteristic features for the 22-dimethy chromene system? with bands at 1378 and 1360 cm attributable £0 the gew-dimethyl groups and a —C=C— band at 1630 em. addition, hands were abserved at 3460 (ishenolic OH) and 1645 cm" (CoO in a S-hydroxyfavene). The NMR spectra of cyeloheter derivatives data, ‘The NM spectrum of eyeloheter Fig. allyl Protons and the c) indicates the absence (solvents DMSO and pytidin : tkoxyi jand the presence of three dimethyl- on pa. Two vioyl doublet v4 (chemical shifts on the + scale) & six-proton singlet at 8:53 f ts at 342 and 4.27 ) in conjunction with correspond to the olefinic ‘groups in a chromene tem. Two vinylic methyis at 8-03 and 8.37, to, gether with dooblets +58, suggest that the 2-hydroxy! o =95 at 393 and ak the Being ts 3 favort has oxidatively cycled with the dosbiy lic methylexic of a ‘chain in the 3-position isla cpeneoneel Mpube both tes eae asin . are split by the vinylic a broad doublet at 458, interaction of the proton suppressed. "Confirmation n ring system that the hydrogen of D appear as which while the homoallylic ‘af cing D is sercally of the presence of the is provided by the face the trimethyl ether (solvent CDCL, see By appears as a doublet at 3-68 and shifts to 4-42 as ponding hexahydro derivat ison an asymmetric carbon and t And 5°60, not disappearing in the ve, bec nated quartet in the comres- rause this hydrogen the adjacent methy- Product forms an ‘unit is in the form hed to an aromatic Is at 8-12 and 8-37 U = 7 cps) at 6-52 let signals at 2-83 1¢ hexahydro deri- with two aromatic hydro terophy'llin, all the flavones wood of A. terophytieg fave the unique feature of having the Bove oes Genated at the 2’ and 4 posit only, and ti Sromatic hy of the Bering showed the et istic ABC pattem of the B-resoreylic acid {pe. En all these compounds fae eos Wwone nucleus is cycloheterophyllin proved beyond doubt that exctization of the Samet group 38 in Teotrtecaniin 1s igen Place, the appearance of te 6-Droton at 285 ana gic (ge? prance upfield i thet Sapo eee ‘ached to the 3-position of the hydroxy! in roblers is to deci the 3. or 6- or 3-position. Th in the region of an aromatic proton tetaec two Satbon atoms carrying ontgensubetiuentr seen? repeat 8H oF 3H, butt can be assigeed cae latter for two Teasons: (a) in cycloartocarpin and Gegbig BH appeared ata Slightly higher and (38), and (b) no coupling Y= 0607

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