New Phenylethanoid Glycosides soti nan Cistanche Tubulosa (SCHRENK) HOOK. F. I.

HIROMI KOBAYASHI. HIROKO OGUCHI, NOBUO TAKIZAWA, TOSHIO MIYASE, AKIRA UENO, KHAN USMANGHANI, ak MANSOOR AHMAD

Laboratwa Rechèch Santral, Yomeishu Seizo co, Ltd,, 2132-37 Nakaminowa, Minowa-machi, Kamiina-zam, Nagano 399-46, Japon, Shizuoka College of Famasi, 2-2-1 Oshika, Shizuoka-shi 422, Japon ak Depatman Famasi, Fakilte Fakilte, Inivèsite nan Karachi, c Karachi-32, Pakistan

Kontak:joanna.jia@wecistanche.com

Abstrè

Kat nouvoaladi rafalèglikozi, tibèkiloz A (II), B (VII), C (VII), ak D (VIII), gen te izole deSispanntibouloz(SCHRENK) HOOK. f. (Orobanchaceae), ansanm ak kat Konnenaladi rafalèglikozi, echinacoside (I), acteoside (III), izomer acteoside (IV), ak 2'- asetylacteoside (V). Estrikti II, VII, VII, ak VIII te etabli ki baze sou pwodui chimik prèv ak done spektak. Konpoze VII ak VIII posse yon tri acetyl rhamnosyl moiety kòm sik tèminal.

Sispannaladi rafalè glikozGen anpil benefis sante

Mo kle:Sispanntibouloz;Orobanchaceae; plant parazit;aladi rafalè glikoz; tibèkiloz A; tibèkiloz B; tib c; wouble

Nan seri nou an nan envestigasyon sou konstitiyan chimik yo nan Cistanche spp. (Orobanchaceae),aladi rafalèglycosides1-3) ak iridoide4) soti nan Cistanche salsa (C. A. MEY.) G. BECK te rapòte. Papye prezan an fè fas ak fenomèn nan glikozi soti nan Cistanche tubulosa (SCHRENK) HOOK. f. ranmase nan Pakistan. Sispann Tubulosa (SCHRENK) HOOK. f.5) se yon plant parazit k ap grandi sou rasin salvadò ak Calotropis spp., ak rive lajman nan Lafrik di Nò, Arabi, Arabi, Lwès Azi nan Pakistan, ak peyi Zend. Se plant la antye itilize medsin nan Pakistan kòm yon remèd pou dyare ak mal.6)

Kounye a nou vle rapòte izolasyon kat nouvoaladi rafalèglikoziyo te rele tibulosides A (II), B (VII), C (VII), ak D (VIII), osi byen ke kat fenomèn li te ye glycosides, echinacoside (I), acteoside (III), izomerik acteoside (IV) ak 2-acetylacteoside (V). Estrikti konpoze sa yo te detèmine ki baze sou prèv chimik ak etid espektakilè.

PhenylethanoidGlycosidesNansispannkapab anti-enflamatwa

Ekstrè ekstrè nan tout plant la te sispann nan dlo. Sispansyon sa a te ekstrè ak etyl ak Lè sa a, ak n-men satire ak dlo. Fraksyon n-menan an te kwomatografi sou polyamide ak kolòn jèl silika ak sibi wo-pèfòmans likid kwomatografi (HPLC) siksè, bay uitaladi rafalèglikozi(I-VIII).

Konpoze III, III, IV, ak V yo te izole kòm poud amorphorphous, ki montre menm jan an espektakilè sa yo ki nan ekonomi,1) acteoside,1) aktyote isomer7) ak 2'-acetylacteoside,2) respektivman, epi yo te idantifye pa konparezon dirèk ak echantiyon natif natal [kouch mens kwomatografi (TLC), enfrawouj (IR), pwoton rezon nikleyè mayetik (1H-NMR), ak kabòn-13 rezònman mayetik (13C-NMR) spectra].

Tubuloside A (II) te izole kòm yon poud amorphous, [ƒ¿]D-103.7 /‹ (MeOH), C37H48O21.3/2 H2O. Spectre IR la sijere prezans nan gwoup idwoksikl (3440 cm-1), yon estè konjige (1705 cm-1), yon kosyon doub (1634 cm-1) ak bag aromat (1608, 1522 cm-1), ak iltravyolèt la (UV) spectre te montre absòpsyon maxima nan 220, 250 sh, 292 sh ak 334 nm. Spectre an 1H-NMR nan II te montre siyal nan yon gwoup methyl rhamnose [6 1.07 (3H, d, J= 6 Hz)]] yon siyal methyl nan yon gwoup acetoxyl [6 1.98 (3H, s), benzylic methylene protons [6 2.70 (2H, t, J= 7 Hz)], de pwoton glikoz-anomerik [6 4.32, 4.54 (1H chak, d, J = 8 Hz)], yon pwoton rhamnose-anomerik [6 5.11 (1H, br s), de transpò pwoton olefin [6.25, 7.64 (1H chak, d, J= 16 Hz)] ak pwoton aromat [6.5 7 .2 (6H)]. Sou aksetylasyon, II te peye anba acetate (IIa), ki te idantik ak aksesib la dodeca nan echinacoside (I). Spectre an 13C-NMR nan II te prèske idantik ak sa yo ki nan Mwen, eksepte pou siyal yo akòz glikoz la obligatwa dirèkteman nan aglycone a ak acetoxyl la gwoup [6 20.9 (CH3), 171.5 (C = 0)], sijere ke gwoup la acetoxyl tache ak glikoz moiety. Nan spectre an 13C-NMR nan II, chanjman nan acylation81 [-2.3 (C-1), -0.9 (C-2) ak-1.0 (C-3)] yo te obsève nan C-1, C-2, ak C-3 nan glikoz ench la pa detaye konparezon ak spectre an nan mwen, ki endike ke gwoup la acetoxyl lye nan C-2 a gwoup idwoksikl nan moieti a glikoz nan II. Sou methanolysis nan II ak klorid asetyl nan methanol, kafe methyl, ak 3,4-didroksyphenethy alkòl te detekte pa TLC ak HPLC. Asid idwolizasyon nan II ak 10% asid silfirik ki ofri glikoz ak rhamnose nan yon rapò 2 a 1.

Baze sou prèv ki anwo a mansyone, estrikti a nan tibulo A te detèmine pou yo dwe 2-(3,4-dihydroxy phenyl) ethyl 0-a-L-rhamnopyranosyl-(1) ̈3)-[ƒÀ-D-glucopyranosyl-(1-6)]-(4-O-caffeoy1)-2-O-acetyl-fl-D-glucopyranoside (II).

Tibuloside B (VI) te izole kòm yon poud anfòm, [a]D, 39.0 /0•‹ (MeOH), C31 H38016, ki gen 1H-NMR spectre te montre prezans nan yon gwoup acetoxyl aliphatic [6 1.98 (3H, yo]. Spectre an 13C-NMR nan VI te trè menm jan ak sa yo ki an izoside acteoside (IV) men diferan yon ti kras nan siyal yo akòz moiet la glikoz ak prezans nan acetoxyl la gwoup [6 20.9 (CH3), 171.6 (C = 0)]. Kote gwoup la acetoxyl nan moiet la glikoz nan VI te detèmine soti nan spectre 13C-NMR li yo pa konparezon detaye ak sa yo ki an IV.

Siyal yo nan C-1, C-2, ak C-3 nan modènizasyon glikoz la te montre chanjman akselere (-2.5 (C-1), -0 .6 (C-2) ak-1.4 (C-3)] tankou nan ka AI, ki endike ke gwoup la acetoxy lye nan gwoup la C-2 hydroxyl nan gwoup la glikoz nan VI. Sou aksetil, VI peye octacetate (VIa) ki te idantik ak nonasetate nan IV. Sou methanolysis nan VI ak klorid asetil nan vle di, methyl kafe, ak 3,4-didroksifin alkòl te detekte pa TLC ak HPLC. Asid idwolizasyon nan VI ak 10% silfirik asid glikoz ak Rhamnose nan yon rapò ki gen 1 a 1. Rezilta sa yo te mennen nou nan di ke estrikti a tibuloside B se 2-(3,4-4-4-4). 2-0-aksepte143-D-glucopyranoside (VI).

Engredyan aktifSispanngen yonkansè nan ovèEfè

Tibuloside C (VII) te izole kòm yon poud amorphous, [a], -104.8 /‹ (MeOH), C43H54024 H20, ki gen 1H-NMR spectre te montre prezans nan kat acetoxyl aliphatic gwoup [6 1.80, 1.92, 1.95 ak 2.08 (3H chak, yo]. "C-NMR spectre nan VII te prèske idantik ak sa yo ki an tibèkiloz A (II), ki posede yon gwoup aliphatic aliphatic nan glikoz ensije, eksepte pou siyal yo akòz moiet la Rhamnose. Anplis de sa, nan spectre an 13CNMR nan VII, chanjman acylation') yo te obsève nan siyal yo akòz C-2, C-3, ak C-4 nan moiet la Rhamnose pa konparezon detaye ak done yo pou II. Se poutèt sa, kote kat gwoup acetoxyl yo te detèmine yo dwe C-2 nan glikoz enteryè a ak C-2, C-3, C-4 nan moiet la Rhamnose nan VII. Sou aksetil, VII te peye octacetate a ki te idantik ak tibèkiloz A anba aksepta (IIa). Sou methanolysis nan VII ak acetyl klorid nan methanol, methyl kafe, ak 3,4-didroksifin alkòl te detekte pa TLC ak HPLC. Asid idwoliz nan VII ak 10% silfirik asid silfirik glikoz ak Rhamnose nan yon rapò ki gen 2 a 1.

Soti nan rezilta ki anwo yo, estrikti a nan tibuloside C te detèmine yo dwe 2-(3,4) fenomèn dizidwon)ethyl 2,3,4-Tri-O-Acetyl-a-L-thamnopyranosyl-(1- 3)-[9-D-glucopyranosyl-(1- + 6)]-(4-0-kafeoy1)-2-0-acetyl-fl-D-glucopyranoside (VII).

Tibuloside D (VIII) te izole kòm yon poud amorphorphous, [oc], -91.4° (MeOH), C43H54023. H2O, ki gen 1H-NMR spectre te montre prezans nan kat acetoxyl aliphatic gwoup [6 1.81, 1.93, 1.96, ak 2.09 (3H chak, yo]. Sou aksetil, VIII te peye heptaacetate (VIIa), ki gen 1H-NMR spectre te montre uit alifatik [6 1.87, 1.94, 1.96, 1.99, 2.10 (3H chak, yo) ak 2.02 (9H, yo] ak twa aromat [6 2.27, 2.30 ak 2.32 (3H chak, yo)] siyal acetoxyl methyl. Spectre nan 13C-NMR nan VIII te prèske idantik ak sa yo ki nan tibèkiloz C (VII), eksepte pou siyal yo akòz modèn asid la p-koumaric. Sou methanolysis nan VIII ak klori acetyl nan methanol, methyl p-komarate, ak 3,4-didroksifizyon alkòl te detekte pa TLC ak HPLC. Asid idwoliz nan VIII ak 10% asid silfirik glikoz ak rhamnose nan yon rapò 2 a 1.

Baze sou rezilta sa yo, estrikti a nan tibuloside D te detèmine yo dwe 2-(3,4- dihydroxy fenomèn) ethyl 2,3,4-tri-O-Acetyl-a-Lrhamnopyranosyl-(3,4) ethyl 2,3,4-tri-O-Acetyl-a-Lrhamnopyranosyl-(1). • ̈3)-[ƒÀ-D-glucopyranosy-](1→6)} (4-0-p-koumary1) -2-0-acetyl-fl-D-glucopyranoside (VIII).

Anpilaladi rafalèglikozitankou forsyhoside A,'°) leucosceptoside A,7 isomartynoside) ak sou sa, li te gen yon moiet rhamnose kòm sik tèminal la te rapòte. Nan ka sa yo, moieti rhamnose a pa aksepte. Tibuloside C (VII) ak D (VIII) genyen yon moiety rhamnose ak yo se premye natirèlman ki fèt konpoze ki gen yon tristès rhamnose moiety yo dwe rapòte.

Engredyan aktifSispanngenyenewopeyènEfè

Eksperimantal

Pwen fonn yo te detèmine sou yon aparèy mikwo-fonn mikwo-fonn epi yo pa kòrèk. Ptik wotasyon yo te mezire ak yon POLARIMASYON DIP-140 dijital. IR spectra te anrejistre ak Hitachi 270-30 spectrophomèteter enfrawouj ak UV spectra ak yon Hitachi 200-20 spectromètr. ' H-NMR ak "C-NR spectra yo te anrejistre ak yon machin JEOL FX-90Q (89.55 ak 22.5 MHz, respektivman). Yo bay chanjman chimik yo sou 6 la (ppm) echèl ak tetrameilsilan (TMS) kòm yon estanda entèn (s, yon sèl; d, doublet; triplet; br, laj). Gaz-likid kwomatografi (GC) te kouri sou yon Aparèy Shimadzu GC-4CM ak yon detektè flanm dife. HPLC te fèt sou yon Hitachi 655A-11 machin. Silica gel (Wako Gel C-300, Wako Pure Chimik) te itilize pou kolòn chromatografi. Kieselgel 60 F254 (Merck) yo te itilize plak pou TLC ak deteksyon te pote soti nan flite 10% H2SO4 ki te swiv pa chofaj.

Izolman

Fresh tout plant nan C. Tubulosa (22 kg), kolekte nan mwa desanm 1984, nan Karachi, Pakistan, te ekstrè ak ETOH. Ekstrè ekstrè a te sispann nan H2O, ak ekstrè ak ETOAc ak Lè sa a, ak n-BUOH satire ak H20. Ekstrè n-BUOH la (99.1 g) te absòbe sou yon Diaion HP-20 (Nippon Rensui co.) kolòn ak rès la te elimine ak Me0H apre yo te lave ak H20. Me0H la eli (15.4g) te kwomatografi sou yon polyamide C-200 (Wako pi chimik) kolòn lè l sèvi avèk H20 ak Lè sa a, Me0H. Fraksyon an te elimine ak Me0H te konsantre yo bay yon rès (fizik glikozif) (8.0 g). Apre repete kwomatografi rès la sou silica jèl ak CHC13-Me0H-H20 (70: 30: 5) ak HPLC ak yon H2O-CH3CN oswa H2O-MeOH sistèm solvay, uit Glikozi (mwen ---VIII) te izole. Mwen, 230 mg; II, 200 mg; III, 240 mg; IV, 60 mg; V, 210 mg; VI, 100 mg; VII, 60 mg; VIII, 65 mg. Kondisyon pou HPLC: kolòn, Develosil ODS-10 (20 x 250 mm); solvay, II (17% CH3CN), III, IV (20% CH3CN), V (22% CH3CN), VI (25% CH3CN), VII (53% Me0H), VIII (55% Me0H); detektè (UV), 220 nm; pousantaj koule, 6.9 ml / min.

Echinacoside (I)

Poud nòmal. IR 0,;, Eas, r, cm-1: 3400, 1690, 1625, 1600, 1518. 11-I-NMR (methanol-d4) 6: 1.09 (3H, d, J= 6 Hz, CH3 nan rhamnose), 2.79 (2H, t, J= 7 Hz, Ar-CH2-), 4.29, 4.37 (1H chak, d, J=8 Hz, H-1 nan glucose), 5.16 (1H, d, J= 1 Hz, H-1 nan rhamnose), 6.26 (1H, d, J=16 Hz, Ar-CH=CH-), 6.4-7.1 (6H, aromatic H), 7.59 (1H, d, J = 16 Hz, Ar-CH=CH-). 13C-NMR: Tab mwen.

Tibuloside A (H)

Poud amorphous, [a]3 -103.7 (c = 1.08, Me0H). Anal. Calcd for C371-14021 3/2 H20: C, 51.93; H, 6.01. Jwenn: C, 51.80; H, 5.81. IR vrtr, cm': 3440, 1732, 1705, 1634, 1608, 1522. UV An?" nm (louvri sesyon an): 220 (4.14), 250 sh (3.85), 292 sh (3.95), 334 (4.13). 1H-NMR (methanol-d4): gade tèks. 13C-NMR: Tab mwen.

Akteoy (III)

Poud nòmal. IR v cm-1: 3420, 1696, 1634, 1606, 1520. 1H-NMR (methanol-d4) 5: 1.10 (3H, d, J= 6 Hz, CH3 nan rhamnose), 2.78 (2H, t, J= 7 Hz, Ar-CH2-), 4.36 (1H, d, J= 8 Hz, H-1 nan glikoz), 5.17 (1H, d, J=1 Hz, H-1 nan rhamnose), 6.25 (1H, d, J= 16 Hz, Ar-CH =CH-), 6.4-7.1 (6H, aromatic H), 7.58 (1H, d, J=16 Hz, Ar-CH =CH-). 13C-NMR: Tab mwen.

Acteoside Isomer (IV)

Poud nòmal. IR v cm-1: 3280, 1686, 1624, 1602, 1512. 11-I-NMR (methanol-d4) 6: 1.26 (3H, d, J=6 Hz, CH3 nan rhamnose), 2.77 (2H, t, J= 7 Hz, Ar-Cl.2-I.2 4.33 (3H, d, J=8 Hz, H-1 nan glikoz), 5.18 (1H, br s, H-1 nan rhamnose), 6.28 (1H, d, 1 = 16 Hz, Ar-CH =CH-), 6.4-7.1 (6H, aromatic H), 7.54 (1H, d, J=16 Hz, Ar-CH =CH-). 13C-NMR: Tab mwen.

2'-Acetylacteoside (V)

Poud nòmal. IR vT cm-1: 3450, 1735, 1705, 1640, 1610, 1535. 1H-NMR (methanol-d4) 6: 1.07 (3H, d, 1= 6 Hz, CH3 nan rhamnose), 1.99 (3H, s, OAc), 2.69 (2H, t, J = 7 Hz, Ar-CH2-), 4.50 (1H, d, J= 8 Hz, H-1 nan glikoz), 5.16 (1H, br s, H-1 nan rhamnose), 6.25 (1H, d, J= 16 Hz, Ar-CH=CH-), 6.5-7.2 (6H, aromatic H), 7.59 (1H, d, J= 16 Hz, Ar-CH =CH-). 13C-NMR: Tab mwen.

Tibuloside B (VI)

Poud amorphous, [43 -39.0° (c = 1.05, Me0H). Anal. Calcd for Cm H38016: C, 55.85; H, 5.75. Jwenn: C, 55.91; H, 6.00. IR v:,111 cm-1: 3420, 1734, 1696, 1634, 1608, 1522. UV 4ear nm (log e): 220 (4.32), 246 sh (4.09), 292 kle (4.21), 340 (4.31). 1H-NMR (methanol-d4) 6: 1.24 (3H, d, J = 6 Hz, CH3 nan rhamnose), 1.98 (3H, s, OAc), 2.69 (2H, t, J = 7 Hz, Ar-CH2-), 4.48 (1H, d, J=8 Hz, H-1 nan glikoz), 6.32 (1H, d, J=16 Hz, Ar-CH - CH-), 6.5-7.2 (6H, aromat H), 7.61 (1H, d, J=16 Hz, Ar-CH =CH-). 13C-NMR: Tab mwen.

Tibuloside C (VII)

Poud amorphous, [a] - iO4.8© (c = 1.86, Me0H). Anal. Kalkil pou C43H54024 ' H20: C, 53.08; H, 5.80. Jwenn: C, 53.28; H, 5.68. IR v cm': 3440, 1748, 1634, 1608, 1522. UV 2 " nm (louvri sesyon an): 220 sh (4.06), 250 sh (3.7), 292 sh (3.88), 333 (4.04). 1H-NMR (methanol-d4) 6: 1.02 (3H, d, J = 6 Hz, CH3 nan rhamnose), 1.80, 1.92, 1.95, 2.08 (3H chak, s, OAc), 2.70 (2H, t, J=7 Hz, Ar-CH2-), 4.32, 4.56 (1H chak, d, J=8 Hz, H-1 nan glikoz), 5.02 (1H, br s, H-1 nan rhamnose), 6.30 (1H, d, J = 16 Hz, Ar-CH =CH-), 6.5-7.2 (6H, aromatic H), 7.66 (1H, d, J=16 Hz, Ar-CH =CH-). 13C-NMR: Tab mwen.

Tibuloside D (VIII)

Poud amorphous, [a]P5 - 91.4° (c = 1.85, Me0H). Anal. Kalkil pou C43H54023 ' H20: C, 54.00; H, 5.90. Jwenn: C, 54.10; H, 5.75. IR v:,111 cm-1: 3440, 1750, 1634, 1608, 1518. UV 2,1,2 " nm (louvri sesyon an): 228 (4.16), 292 sh (4.21), 302 sh (4.26), 318 (4.35). 11-I-NMR (methanol-d4) 6: 1.00 (3H, d, J = 6 Hz, CH3 nan rhamnose), 1.81, 1.93, 1.96, 2.09 (3H chak, s, OAc), 2.70 (2H, t, J=7 Hz, Ar-CH2-), 4.32, 4.53 (1H chak, d, J=8 Hz, H-1 nan glucose), 5.03 (1H, br s, H-1 nan rhamnose), 6.38 (1H, d, J = 16 Hz, Ar-CH =CH-), 6.52-6.75 (3H, aromatic H), 6.84 (2H, d, J= 9 Hz, H-3, H-5 nan asid p-koumaric), 7.54 (2H, d, J = 9 Hz, H-2, H-6 nan asid p-koumaric), 7.74 (1H, d, J=16 Hz, Ar-CH =CH-). 13C-NMR: Tab mwen.

Aksetil nan II ak VII

Trètman II oubyen VII (30 mg) avèk Ac20 (1 ml) ak piridin (1 ml) nan chanm tanperati a ki te swiv pa travay abityèl la peye yon akseptab crude, ki te pirifye pa kwomatografi sou jèl silica ak benzene-acetone (5: 1) bay anba acetate (IIa) (25 mg) soti nan II oswa octacetate la (22 mg) soti nan VII, kòm san koulè zegwi soti nan Me0H, mp 130-131 C. IR v cm': 1775, 1660, 1523, 1450. 1H-NMR (CDC13) 6: 1.05 (3H, d, J= 6 Hz, CH3 nan rhamnose), 1.89, 1.96, 1.97, 2.01, 2.11 (3H chak, s, OAc), 2.03 (9H, s, OAc x 3), 2.29 (3H, s, Ar-OAc), 2.31 (9H, s, Ar-OAc x 3), 2.88 (2H, t, J= 7 Hz, Ar-CH2-), 6.35 (1H, d, J= 16 Hz, Ar-CH = CH-), 7.0-7.4 (6H, aromatic H), 7.66 (1H, d, J=16 Hz, Ar-CH =CH-). Pwodwi sa yo te jwenn yo dwe idantik ak dodekastate nan echinacoside (I) pa konparezon dirèk (TLC, melanje mp, IR, ak 1H-NMR).

Aksetil nan VI

Konpoze VI (40 mg) te aksepte nan menm fason an jan sa dekri pou II ak pwodwi reyaksyon te pirifye pa kwomatografi sou jèl silica ak benzene-acetone (9: 1) bay octacetate la (VIa) (30 mg) kòm yon poud annòf. IR v cm': 1742, 1630, 1498. 1H-NMR (CDC13) 6: 1.14 (3H, d, J = 6 Hz, CH3 nan Rhamnose), 1.95, 2.03, 2.05, 2.09, 2.13 (3H chak, s, OAc), 2.27, 2.31 (6H chak, s, Ar-OAc x 2), 2.87 (2H, t, J=7 Hz, Ar-CH2-), 6.42 (1H, d, J=16 Hz, Ar-CH = CH-), 6.9-7.5 (6H, aromatic H), 7.64 (1H, d, J= 16 Hz, ArCH = CH-). VIa te jwenn yo dwe idantik ak ki pa asepte nan izomerik acteoside (IV) pa konparezon dirèk (TLC, IR, ak 11-1-NMR.

Aksetil nan VIII

Konpoze VIII (35 mg) te aksepte nan menm fason an jan sa dekri pou II bay eptaza (VIIIa) (30 mg) kòm yon poud anfòm. IR v cm': 1760, 1638, 1604, 1510. 1H-NMR (CDC13) 6: 1.03 (3H; d, J= 6 Hz, CH3 nan rhamnose), 1.87, 1.94, 1.96, 1.99, 2.10 (3H chak, s, OAc), 2.02 (9H, s, OAc x 3), 2.27, 2.30, 2.32 (3H chak, s, Ar-OAc), 2.88 (2H, t, J= 7 Hz, Ar-CH2-), 6.36 (1H, d, J=16 Hz, Ar-CH =CH-), 7.0-7.2(3H, aromatic H), 7.25 (2H, d, J=9 Hz, H-3, H-5 nan asid p-koumaric), 7.57 (2H, d, J=9 Hz, H-2, H-2, H-6 nan p-koumaric asid), 7.72 (1H, d, J = 16 Hz, Ar-CH =CH-).

Methanolysis nan II, VII, VII, ak VIII

Konpoze II, VII, VII, oswa VIII (ca. 1 mg) te reflechi ak metolik 5% CH3COCl (2 ml) pou 30 min, ak Lè sa a, reyaksyon yo te evapore koupe. Prezans nan kafe methyl ak 3,4 alkòl didwoksifi nan rès II, VII, ak VII, ak methyl p-komès ak 3,4-didroksifinethyl alkòl nan sa yo ki nan VIII, te demontre pa TLC [CHC13-MeOH (20: 1)] ak HPLC [kolòn, TSK GEL LS-410AK (4 x 300 mm); sòlda, H20-Me0H (4: 6); detektè (UV), 250 nm; pousantaj koule, 1.0 ml / min]. Methyl kafe [R•¬ 0.20, tR (min) 10.8], methyl p-koumarate [R•¬ 0.40, tR (min) 15.6], 3.4-dihydroxyphenethyl alkòl [R•¬ 0.06, tR (min) 2.8].

Asid Idwolizasyon nan II, VII, VII, ak VIII

Yon solisyon nan glikoside (ca. 2 mg) nan 10% H2SO4 (1 mililit) te chofe nan yon beny dlo bouyi pou 30 min. Solisyon an te pase nan yon kolòn Amberlite IR-45 ak eli a te konsantre bay yon rès, ki te redwi ak boyhydride odyòm (ca. 3 mg) pou 1 h. Melanj reyaksyon an te pase nan yon kolòn Amberlite IR-120 ak konsantre nan sèk. Asik boric te retire pa distilasyon ak MeOH ak rès la te asepte ak Ac2O (1 gout) ak pyridine (1 gout) nan 100 / Ž pou 1 h. Reyaktif yo yo te evapore. Glucitol ak rhamnitol ak akseptab yo te detekte nan yon rapò de 2 a 1 soti nan II, VII ak VIII, ak 1 a 1 soti nan VI pa GC. tR (min): 2.0 (rhamnitol acetate), 5.5 (glucitol akseptab). Kondisyon pou GC: kolòn, 1.5% OV-17 (3 mm x 1.5 m); kolòn temp., 180 •Ž; gaz konpayi aswè a, N2 (30 ml/ min).

Rekonesans

Nou rekonesan anvè Prof. Dr. S. I. Ali, Depatman Botanik, Inivèsite Karachi, pou idantifikasyon plant lan.

Referans ak nòt

1) H. Kobayashi, H. Karasawa, T. Miyase, ak S. Fukushima, Chem. Pharm. Bull., 32, 3009 (1984).

2) H. Kobayashi, H. Karasawa, T. Miyase, ak S. Fukushima, Chem. Pharm. Bull., 32, 3880 (1984).

3) a) H. Kobayashi, H. Karasawa, T. Miyase, ak S. Fukushima, Chem. Pharm. Bull., 33, 1452 (1985); b) H. Karasawa, H. Kobayashi, N. Takizawa, T. Miyase, ak S. Fukushima, Yakugaku Zasshi, 106, 562 (1986); c) Idem, ibid., 106, 721 (1986).

4) a) H. Kobayashi ak J. Komatsu, Yakugaku Zasshi, 103, 508 (1983); b) H. Kobayashi, H. Karasawa, T. Miyase, ak S. Fukushima, Chem. Pharm. Bull., 32, 1729 (1984); c) Lide, ibid., 33, 3645 (1985).

5) E. Nasir ak S. I. Ali, "Flora nan West Pakistan," Vol. 98, Shamin Enprime Laprès, Karachi, 1976, p. 4.

6) S. R. Baquar ak M. Tasnif, "Plant medsin nan Sid West Pakistan," Vol. 3, Konsèy Pakistan nan Syantifik ak Endistriyèl Rechèch Bulletin /Monograph, Karachi, 1967, p. 56.

7) T. Miyase, A. Koizumi, A. Ueno, T. Noro, M. Kuroyanagi, S. Fukushima, Y. Akiyama, ak T. Pranmoto, Chem. Pharm. Bull., 30, 2732 (1982).

8) K. Yoshimoto, Y. Itatani, ak Y. Tsuda, Chim. Pharm. Bull., 28, 2065 (1980).

9) Mwen. Kitagawa, H. K. Wang, M. Saito, A. Takagi, ak M. Yoshikawa, Chem. Pharm. Bull., 31, 698 (1983).

10) K. Endo, K. Takahashi, T. Abe, ak Hikino, Heterocycles, 16, 1311 (1981). 11) Mwen. Calis, M. F. Lahloub, E. Rogenmoser, ak O. Sticher, Fitochimis, 23, 2313 (1984).