PDF Vu Binh Hoang*'

chiKhoahtjc va Cong nghe 133 (2019) 079-0

Thanh phin hoa hoc cua qua xoan ta (Melia azedarach L.) & Viet Nam

Chemical Constituents from Fruit o^ Melia azedarach L. in Vietnam

Vu Thi min''^, Nguyin Ngoc Tudn^ Hoang Van Luu\ Vu Binh Hoang*'

'Trirdng Dgi hgc Vinh - 182 Le Duan - Thdnh PhS Vinh - tinh Nghe An

-Tnrdng Dgi hgc Tdi nguyen vd Moi birdng - Thdnh phd Hd Chi Mnh

^Truang Dai hpc Cong nghiep Thanh pho Hd ChiMinh

^Trudng Dgi hoc Bdch khoa Hd Noi - S6 I, Dgi Co Viet, Hai Bd Trimg, Hd Noi Den Toa sogn: 29-11-2018; chdp nhdn ddng: 20-3-2019

Tom tat

TCr dtch chiSt metanol cua xoan ta (tvlelia azedarach L) (l<Aeliaceae) bang cac phaang phap sac ki da phan lap hai flavonoid (apigenin, quercetin 3-0-[a-L-rhamnopyranosyl-(1~*6)-p- D-glucopyranoside}), mot coumarin (scopoletin), mgt phenolic (acid vanilic), mot triterpenoid (taraxerol) va hai steroid (^-sitosterol va

^•sitosterol-3-O-0-D-glucopyranoside) C^u true cac hgp chSt nay dagc xac dinh bSng cae phuang phap pho ta ngoai (UV), phd hdng ngoai (IR), pho khdi luvng (tVIS), phd cong hoang ta hat nhan ('H-, '^C-NMR, DEPT, HtfBC, HSQC va COSY) va so sanh ta li$u tham khao. Cac chSt nay lim dSu tien daac phan lap ta thanh phan qua xoan ta mgc a Viet Nam.

Jia khoa' Melia azedarach, Meliaceae, flavonoid. scopoletin, apigenm, taraxerol Abstract

Two flavonoids (apigenin and quercetin 3 - 0 -[a- L - rhamnopyranosyl - (l—'S) - {3- D-glucopyranoside]), a coumarin (scopoletin), a phenolic (vanilic acid), a triterpenoid (taraxerol) and two steroids (p-sitosterol and 13- sitosterol-3-O-0-D-glucopyranoside) were isolated from the methanolic extract of the fruits of Melia azedarach L, using silica gel column chromatography methods. The structures of these compounds were elucidated using a combination of UV, IR, ID and 2D NtViR techniques ('H-, '^C-NMR, COSY, HSQC and l-IMBC), MS analyses, and the comparison with the literature data. This is the first isolation of the compounds from fi/lelia azedarach growing in Vietnam.

Keywords: Melia azedarach, Meliaceae, flavonoid, scopoletin, apigenin. taraxerol

I. Mtfdau

Xoan ta (Melia azedarach L.) (Meliaceae) la Ioai ban dia a Viet Nam, Nhat Ban, Dai Loan, Tmng Quoc, va Dong Nam A [1-3]. Tir thai c6 dai, cac loai nay da dupe sii dung trong y hoc dan gian hoac y hpc Tmng Quoc dg digu tri benh cho con nguai. Ci Nhat Ban, vo cay va hoa qua ciia M azedarach da dupe sir dung lam thuoc digt co, benb di iing va benh da. Cac bo phan cua M azedarach thuang duac su dung cho thuoc tni sau, thuoc lgi tieu, lam se va da day nhu y hoc CO tmyen An Dp o Ayurveda [4-6], Tir cac bg phan khac nhau ciia M azedarach nhiSu thanh phan bao gom limonoid, triterpenoid va steroid da dugc phan tap [7-16], Mpt so cac hgp chat dugc phan lap tit M. azedarach cho thay kha nang gay ngan an doi v6i con tning [8, 10], va cac hoat tinh diet con triing [7], cac hoat chit khang khuk [9,13], cac boat dgng gay dge tg bao [14, 15].

'Oiachi lien he : Tel.: (+84) 914661299

Xoan ta (Melia azedarach L.) (Meliaceae) dugc tim thay a mot so vimg a Viet Nam nhu Nghe An, Thira Thien-Hug... Tir nguon nguyen lieu qua xoan tu nhien a khu bao t6n thign nhien Pu Huong - Nghe An, chiing toi tiln hanh phan lap bang cac phuang phap sac ky va xac dinh dugc cau tnic ciia bay hgp chdt bao g6m hai flavonoid (apigenin, quercetin 3 - 0 -[a - L rhamnopyranosyl - (l^'fi) P- D- glucopyranoside]), mot coumarin (scopoletin), mot phenolic (acid vanilic), mpt triterpenoid (taraxerol) va hai steroid (p-sitosterol va p-sitosterol-3-O-P'D- glucopyranoside) tir qua xoan ta. Cau tnic boa hoc ciia cac hgp chat dugc lam sang to bang sir ket hop cac phuang phap pho hong ngoai (IR), pho khoi lugng (MS), ph6 cong huang hi (NMR).

2. Thirc nghiem 2.1. Thiit bi

sac ky lop mong sir dung Ioai trang sin silica gel 6OF245 (Merck), hign hinh bang den UV va hoi iot.

Chdt hip phu silica gel 230-400mesh (Merck) dugc

Tap chi Khoa ni^c ^ may Yanaco MP-S3. Pho tii ngoai UV dugc ghi tren may Agilent UV-VIS, Pho h6ng ngoai IR dugc ghi tren may Bmker 270-30, dang vien nen KBr, Pho khoi Iugng va cham electron El-MS do tren may MS- Engine-5989-HP. Ph6 HR-ESI-MS do nen may micr OTOF-Q n 10187 (Phong Phan tich Trang tam, Tnrang Dai hpc Khoa hpc Tu nhien Tp. HCM), Pho cpng huong ni hat nhan dugc do tren may Bruker 500 MHz (Phong Phan tich ciu tnic, Vien Hoa hgc, Vien Han Iam Khoa hpc va Cong nghe Viet Nam).

2.2. Nguyen lieu

Qua xoan ta (Melia azedarach L,) con xanh dugc thu hai a khu bao ton thien nhign Pu Huong- Nghe An vao thang 2/2016. Mau dugc dinh danh bai PGS.TS. TrAn Huy Thai, Vien Sinh thai va Tai nguyen Sinh vat, Vien Han lam Khoa hpc va Cong nghe Viet Nam. Tieu ban dugc luu giii Vien Hoa, Sinh va Moi tmcmg, Tmong Dai hpc Vinh, Nghe An.

2.3. Phdn lap cdc hgp chat

Mau thuc vat thu thap va say kho a nhiet do tir 40''-50''C trong 48 gio, sau khi say kho va xay nho (5,0 kg) ngam vai MeOH, voi thai gian 8 ngay, sau do lpc va dich lpc dugc cat giam ap suat bang thiet bi quay cat chan khong thu dugc cao metanol (425 g).

Phan bo cao metanol trong nuac, sau do chiet lan lugt vcri cac dung moi etyl axetat va butanol, quay cat chan khong thu dugc 125 g cao etyl axetat va 67 g cao butanol,

Cao etyl axetat dugc pban tach tren cpt silicagel, voi be dung moi rira giai la cloroform: metanol (100:0, 40:1: 30:1; 20:i; 10:1; 4:1; 2:1) thu dugc 7 phan doan. Phan doan 1 dugc phan tach lai bang sac ky cot voi he dung moi hexan: acetone (15:1) thu dugc chat hgp chat 6 (128 mg). Phan doan 3 duac phan tach lai bang sac ky cot vai he dung moi hexan:

axeton (7:1) thudugc chat hpp chat 3 (28 mg) v a h g p chat 5 (31 mg). Phan doan 5 dugc tien hanh sac ky cpt vai silica gel voi he dung moi rira giai cloroform:

metanol (10:1) thu dugc chit 4 (5Img).

Cao butanol dugc phan tach trgn cpt silicagel, vgi he dung moi nia giai la cloroform: metanol (30:1;

20:1; 10:1:4:1; 2:1) thu dugc 5 phan doan. Pban doan 2 dugc phan tach lai bang sac ky cot voi he dung moi cloroform: metanol (15:1) tbu dugc cbat hgp chat 1 (12) mg) va phan doan 3 dugc phan tach lai bang sac ky cpt voi he dung moi cloroform: metanol (10:1) thu dugc chit hpp chat 2 (21,5 mg) Phan Phan doan 5 dugc phan tach tiep vai hg dung moi cloroform;

metano!(10:l) thu dugc chat hgp chat 7(41 mg).

Hgp chat 1; chat bot mau vang nhat, d.n.c. 115- 1 1 7 ° C : ' H R - E S I - M S m/z 467,2669 [M]^ (mong irng C2SH37O5N, tmh man m/z 467,2672); 'H-NMR (500 MHz, CDCb) (5 ppm): 12,96 (IH, 5, 5-OH), 10.83

(IH, 5, 7-OH), 10,35(IH, s, 4 ' - 0 H ) . 7,93 (IH, d, J- 8,0 Hz, H-2'), 7,93 (IH, d, J = 8,0 Hz, H-6'), 6,93 (IH, d, J= 8,0 Hz, H-3'), 6.93 (IH. d / = 8,0 Hz, H- 5'), 6,78 (IH, 5, H-3), 6,20 ( I H . dJ= 2,0 Hz, H-6), 6,49 (IH, rf, y = 2,0 Hz, H-8); "C-NMR (125 MHz, CDCb) (8 ppm); 181,7 (C-4), 164,1 (C-2), 163,7 (C- 7), 161,4 (C-5), 161,1 (C-4'), 157.3 (C-9), 128,4 (C- 6'), 128,4 (C-2'), 121,2 ( C - l ' ) , 115,9 (C-5'), 115,9 (C-3'), 103,7 (C-10), 102,8 (C-3), 98,8 (C-6), 93,9 (C-8).

Hgp chit 2: tinh thg mau vang, d.n.c. 214 - 215°C; UVA^'^'O^nm (loge): 256 (4,14), 267 (4,11), 293 (4,02), 346 (3,83); I R v ^ . ' ^ ' c m " ' : 3415 (OH), 1660 ( C = 0 ) , 1500, 1490 (C=C), 1060 (C-O), 1015;

ESI-MS (positive) m/z: 611 [M+H]"; 'H-NMR (500 MHz, DMSO^rffi) 5 (ppm): 12,59 (IH, 5, 5-OH), 7,55 (IH, rf, J - 2,5 Hz, H-2'), 7,54 (IH, dd. > 2,0, 12,5 Hz, H-6'), 6,85 (IH, rf, J = 8,8 Hz, H-5'), 6,38 (IH, rf, J = L 8 H 2 , H-8), 6 , I 9 ( 1 H , d , J - l , 8 H z , H-6), 5,34 (IH, rf, J = 7,0 Hz, glc H-1), 4,38 ( I H brs, rbam-l), 3,71-3,05 (cac proton ciia duong) va 1,00 (3H, d, J = 6,0, rham-CHs). ^C-NMR (125 MHz, DMSO-rfe) 5 (ppm): 177,5 (C-4),164,2 (C-7), 161,3 (C-5), 156,5 (C-2), 156,7 (C-9), 148,5 (C-4'), 144,8 (C-3'), 133,4 (C-3), 121,7 (C-6'), 121,3 ( C - l ' ) , 115,3 (C-2'), 116,4 (C-5'), 104,1 (C-10), 101,3 ( C - l " ) , 100,8 ( C - l ' " ) , 98,8 (C-6), 93,7 (C-8), 76,5 ( C - 3 " ) , 76,0(C-5"), 74,2 (C-2"), 71,9 ( C - 4 " ' ) , 70,7 ( C - 3 ' " ) , 70,5 ( C - 2 ' " ) , 70,1 (C-4"), 68,3 ( C - 5 ' " ) , 67.1 ( C - 6 " ) , 17,8 (C- 6 " ' )

Hgp chat 3; tinh thg mau v a n g ; d.n.c. 203- 204°C; ESI-MS m/z 193 [M+H]^(CioH804); 'H-NMR (CDCI3, 500 MHz), 5 (ppm): 7,60 (IH, rf, J^ 9,5 Hz, H-4), 6,92 (IH, s, H-5). 6.85 ( I H . 5, H-8), 6,28 (IH, rf, V - 9,5 Hz, H-3), 3,95 (3H, 5, 6-OCH3); '^C-NMR (CDCI3, 125 MHz), 5 (ppra): 161.5 (C-2), 150,3 (C- 7), 149,8 (C-9), 144,1 (C-6), 143,3 (C-A), 113,4 (C- 5), 1H,5 (C-10), 107.5 (C-3), 103.2 (C-8), 56,6 (6- OCH3).

Hgp chat 4: Tinh thg hinh k u n khong mau;

d.n.c: 210-211''C: 'H-NMR (500 MHz, CDCb) (5 ppm): 'H-NMR (500 MHz, CDCb) (5 ppm); 7,57 (IH, rfrf,/= 2,0, 6,5 Hz, H-2), 7.55 (IH, rf,rf= 2 H z . H-6), 6,99 (IH, rf, y = 8,5 Hz. H-5), 3 92 (3H / OCH3); '^C-NMR (125 MHz, CDCb) (5 ppm); 123,7 (C-l), 111,8 (C-2), 147,3 (C-3), 153,3 (C-4), 117,4 (C-5), 144,5 (C-6), 170,0 ( - 0 C 0 - ) , 56.4 (-OCHj).

Hgp chat 5: chat bpt mau tring- 'H-NMR (500 MHz, CDCb) (6 ppm): 5,53 ( I H , rfrf. J = 7 6 3 6 Hz, H-15), 3,19 ( I H , rfrf, J = 11,2 4 4 H z ' H 3) 1,09 (3H, 5, CH3), 0,98 (3H, 5. CH3),'o 91 (6H 5 2xCH3), 0,95 (3H, 5, CH3), 0,93 (3H, s. ^ 3 ) o'82 (3H, s, CH3), 0,80 (3H, 5, CH3): '^C-NMR (125MHz. CDCb) (5 0Dm):I58.1 (C-141 I I / ; Q Z^-

/

chi Khoa hoc va Cong nghe 133 (2019) 079-084 15) 79,1 (C-3), 55,6 (C-5), 49,3 (C-9), 48,8 (C-18),

41 i (C-19), 39,0 (C-8), 38,8 (C-4), 38,0 (C-13), 37,8 (C-l), 37,8 (C-16), 37,6 (C-10), 36,7 (C-7), 35,8 (C- 17), 35,2 (C-22), 33,7 (C-12), 33,4 (C-29), 33,1 (C- 21)' 29,9 (C-26), 29,9 (C-28), 28,8 (C-20), 28,0 (C- 23)' 27,2 (C-2), 25,9 (C-27), 21,3 (C-30), 18,8 (C-6), 17,5 (C-11), 15,5 (C-24), 15,4(0-25)

Hap chat 6; Tinh the hitih kim, d n . c . l 3 5 - 136'C;" El-MS mh (%)• 414 (M*, CjsHsoO, 20), 413(41), 398 (28), 397(100), 395(32), 383 (11), 361 (11), 257 (3), 255 (6,3), 151 (5,6), 139 (11); 'H-NMR (500 MHz, CDClj) 5(ppm). 5,31(1H, m, H-6), 3,51 (IH, IB, H-3), 1,01 (3H, s, I9-CH3), 0,92 (3H, d, J = 6,2 Hz, 2I-CH3), 0,84 (3H, I, J - 7,0 Hz, 29-CH3), 0,83 (3H, d,J' 6,5 Hz, H-26), 0,81 (3H, rf, J =6,5 Hz, 27-CH,), 0,68 (3H, s, 18-CH,); " C - N M R (125 MHz, CDCW 6(ppm)' 140,8 (C-5), 121,7 (C-6), 71,8 (C-3), 56,8 (C-14), 56,1 (C-17), 50,2 (C-9), 45,9 (C- 24), 42,3 (C-4), 42,3 (C-13), 39,8 (C-12), 37,3 (C-l), 36,5 (C-10), 36,2 (C- 20), 34,0 (C-22), 31,9 (C-8), 31,9 (C-7), 31,7 (C-2), 29,2 (C-25), 28,3 (C-16), 26,1 (C-23), 24,3 (C-15), 23,1 (C-28), 21,1 (C-11), 19, 8 (C-26), 19,1 (C-19), 19,4 (C-27), 18,8 (0-21), 12,0 (C-29)va 11,9 (C-18).

Hcrp chat 7: Chat bot mau trang, d.n.c. 283 - 2g5"C; El-MS m/z (%): 396 [M^-CtHiaOs] (9), 273 (2), 255 (9), 185 (5), 161(15), 145 (25), 133 (21), 105 (42), 91 (46), 81 (51), 69 (100); 'H-NMR (500 MHz, DMSO-4) 8(ppm)' 5,38 (IH, m, H-6), 5,03 (IH, rf, J

• 7,0 Hz, H - r ) , 4,05-4,60 (5H, m, H-2-- 6'), 3,99 (IH, m, H-3), 3,98 (IH, m, H-5'), 1,00 (3H, rf, J - 6,5 Hz, 2I-CH3), 0,94 (3H, s, I9-CH3), 0,90 (3H, t, J- 7,0 Hz, 29-CH3), 0,89 (3H, rf, J - 6 , 5 Hz, 26-CH3), 0,89 (3H, rf, y= 6,5 Hz, 27-CH3), 0,67 (3H, s, 18- CHi); "C-NMR (125 MHz, DMSO-rfs) 5(ppm): 140,6 (C-5), 121,3 (C-6), 100,9 ( C - l ' ) , 77,1 (C-3'), 76,8 (C- 5'), 76,8 (C-3), 73,6 (C-2'), 70,2 (C-4'), 61,2 (C-6'), 56,3 (C-14), 55,5 (C-17), 50,7 (C-9), 49,7 (C-24), 45,2 (C-13), 38,4 (C-4), 36,9 (C-12), 36,3 (C-l), 35,6 (C-10), 33,4 (C-20), 31,5 (C-22), 31,5 (C-8), 29,4 (C- 7), 27,7 (C-16) 28,8 (C-23), 27,9 (C-2), 25,5 (C-25), 24,0 (C-15), 22,7 (C-28), 21,0 (C-11), 20,7 (C- 27), 19.8 (C-19), 19,0 (C-26), 18,9 (C-21), 12,2 (C-29) va 11.9 (C-18).

3, Ket qua va thao lu3n

Tir cao metanol ciia qua xoan {Melia azedarach ' " g cac phirong phap sic ki cot silica gel, chiing toi da phan lap dugc 7 hgp chat bao g6m hat flavonoid, mgt coumann, mgt phenolic, mot terpenoid va hai steroid, cau triic ciia cac hgp chat lay dirge xac dinh bang cac phuong phap pho.

Hop chat 1 CO pho khoi luong ESI MS m/z: 269 [MH] tuong ung vol cong thuc phan tu la C15H9O5.

I , "

chat 1 la CijHioOs. Ph6 'H-NMR cua hgp chit 1 cho thay tm hieu dac hrung cua lop chit flavonoid tiiugc khuug cacbon apigenin, diSn hinh la su xudt hien ciia m6t tm higu singlet ciia proton H-3 tai 5H 6,78 (IH, s\ va hai tin hieu proton doublet H-6 va H-8 tai 6H 6,20 (IH, rf, / = 2,0 Hz), 6,49 (IH, rf, J = 2,0 Hz) diic tnmg cho cac proton vong A vii B. Ngoai ra, tin hieu dac tnmg cua vong C (vong benzyl thg tai 1,4 cua phan cSu tnic apigenin) la cac proton thom tai 5H 7,93 (2H, rf, J - 8,0 Hz, H-2' va -6') ya 6,93 (IH, rf, J - 8,0 Hz, H - 3 ' va -5'). Ph6 'H-NMR cua hgp chat 1 con cho thay tin hieu ciia 3 proton nhom hydroxy ISn lugt tai 5H 12,96 (IH, s, 5-OH), 10,83 (IH, s, 7-OH), 10,35 (IH, s, 4 ' - 0 H ) . Ph6 '^C-NMR ciia hop chSt 1 cho thay tin hieu cua 15 cacbon, cac tin hieu dac trgng la cac tui hieu ciia cacbon thom cua vong C tai 6c 121,2 ( C - r ) , 128,4 (C-2' va -6'), 115,9 (C-3' ya - 5'), 161,1 (C-4'). Ngoai ra ph6 '=C-NMR cua hgp chat 1 con xuat hien cac tin hieu dac tnmg cho vong A cila apigenin tai 6c 161,4 (C-5), 98,8 (C-6), 163.7 (C-7), 93,9 (C-8), 157,3 (C-9), 103,7 (C-10) . Hai tin hieu cacbon a ya p ciia vong B dugc xac dinh tai 5c 164,1 (C-2), 102,8 (C-3). Tit s6 liSu ph6 'H v i " C - NMR cua hgp chat 1, ket hop v6i viec so sanh vol tai heu [17] CO the ket luan hgp chat 1 la hop chat apigenm, co ten RJPAC la 5,7-dihydroxy-2-(4- hydrgxyphenyl)-4H-l-beiizopyran-4-one.

Hgp chat 2 thu dugc dugi dang bgt mau viing, d.n.c. 214 - 215°C, PhS 'H-NMR cho tm hieu singlet tai 5H 12,59 ppm cua nhom OH tai C-5 lien hgp voi nhora carbonyl Co nam tin hieu proton thgm, hai prgton ghep cap kieu ortho cua H-5' tai S,i 6,84 (IH, rf, J = 8,0 Hz) v « H-6' tai S„ 7,54 (IH, rfrf J = 8,0;

2,0 Hz), hai proton ghep cap kiSu m^ta cua H-6 tai dn 6,19 (IH, rf 2,0 Hz) yoi H-8 tai SH 6,38 (IH, d,J = 2,0 Hz), mgt tin hiSu proton thcrai singlet cua H-2' tai SH 7,53 (IH, s). Tm hiSu proton anomeric cua goc rhamnose tai SH 4,38 (IH, rf, / = 1,0 Hz), tin hieu proton anomeric cua goc glucose tai Sa 5,34 (IH, rf, J

= 7,5 Hz) Cac proton con lai nam trong yung SH 3,81 den 5H 3,32 ppm Tin hieu nhom methyl cua goc rhamuose tai & 0,99 (3H, rf, J - 6,0 Hz). Ph6 'H- NMR ciia hop chat 2 cho thdy tin hieu cua vong nhan thom thS 3 vi tri 6 7,54 (2H, m, H-2', 6'), va 6,84 (IH, rf, rf = 8,0 Hz, H-5') va 2 proton anomeric tai 5,34 (IH, rf / = 7,5 Hz, glc H-l") va 4,38 (IH, rf, J = 1,0 Hz, rham H-l"'). Tuy nhi6n, ph6 'H-NMR cua hgp chat 2 cho thdy tin hieu proton cua 2 nhom glycosit g 3,71 - 3 , 0 5 ( m , 12H) va nhom methyl ft 0,99 (3H, rf /

= 6,0, rham-CH3). Ph6 '=C-NMR va DEPT ciia hgp chdt 2 cho thdy tin hieu cila 27 cacbon, bao gom 15 cacbon cua khung flavonoid ya 12 cacbon cUa 6 tin hieu carbon thuoc g6c duong glucose, 6 tin hieu carbon thuoc g6c duong rharanose, 1 gftc ducmg cua nitin (S-O-glucose: S 101,3; 74,2; 76,5; 70,1; 76,0;

Tap chi Khe, 70,5, 17,8). Qua so heu pho cac pho thu dirge cua hgp chat nay va so sanh voi cac tai lieu da cong bo t m a c day [18] co the nhan thay sir mong dong ve cau tnic cua chat nay voi mot flavonoid co ten la quercetin 3-0-[a-L-rhamnopyranosyl-(i—>6)]-[3-D- glucopyranoside). Hgp chdt nay da dugc phan lap tir cay Rata graveolens va tim thay trong nhieu ho thuc vat, CO boat tinh chong oxy hoa va Iam ben thanh mach mau. Hgp ch§t mtin cung dugc phan lap tu Solanum tuberosum, Solanum lyratum, Solanum lycopersicum, va Ian dau tien dugc phan lap tu Solanum palinacanthum. no c6 boat tinh khang nam, chong oxi hoa.

Hgp chat 3 la tinb the mau vang co nhiet do nong chay khoang 203 - 204°C. Pho khoi Iugng ESI- MS cho pic ion gia phan tir voi gia tri m/z 193 [M-i-H]* khang dinh cong thitc phan tir cua hgp chat 3 la C10H8O4- Ph6 'H-NMR cho thay tin hieu doublets rieng biet tai S 6,28 (IH, rf, J = 9,5 Hz, H-3) va 7,60 (IH, rf, J = 9,5 Hz, H-4) mong ung vgi 2 protons vong pyrone ciia coumarin. Trong vimg trucmg thap CO tin hieu cua 2 proton thom tai 6,92 (IH, s, H-5) va 6,85 (IH, s, H-8) ppm Ngoai ra, 1 tin hieu ciia nhom methoxy xuk hien tai .5 3,95 (3H, s, 6-CH3). Pho '^C- NMR cho thay hgp chat 3 co 10 cacbon, bao gom tin hieu tai 5c 161,5 (C-2) va 150,3 (C-7) mcmg iing voi nhom carbonyl va cacbon phenolic, Nhom methoxy cung xuat hien tai dc 56,0 ppm. Dir lieu pho cung cho thay bgp chat 3 co kieu khung coumarin. Ket hpp so sanh du lieu pho ciia hgp chat 2 voi tai heu khang dinh hgp chat 3 la scopoletin [19].

Hgp chat 4 la 6 dang tinh the hinh kim, diem nong chay 210-212"C. Pho khoi lugng El-MS cua chat 4 cho pic ion phan hi m/z 168 mong ung voi cong thuc phan tir CgH804. Pho 'H-NMR cua hpp chat 4 cho thay cac tin hieu ciia cac proton thom H-2 6 SH 7,57ppm, H-5 a 5H 6,99 ppm, H-6 o 5H 7,55 ppm trong vong benzen va mpt nhom metoxy 6 5H 3,92 ppm. Qua phan tich cac du lieu ciia pho MS, 'H- NMR va '•' C-NMR so sanh voi tai lieu cho ket luan chat 4 la acid vanilic [20], Hop chat nay tim tbay rpng rai o thuc vat bac cao.

Hgp chat 5 la Tinh the hinh kim man trang, d.n.c 281-283"C. Ph6 tu ngoai (UV) ciia hpp chat 5 cho hap tbu cue dai tai 240, 258, 319, 366 nm, chiing to hgp chat 5 co vong thom. Pho khoi lugng phun mii

electron (ESI-MS) negtive [ M + H ] ' cho pic 427, positive cho pic [M-H]^ 425, hgp chat 5 co khoi lugng phan tir 426, irng voi cong thiic CjoHioO. Ph6 cpng huong tir bat nhan '^C-NMR va DEPT cho thay tin hieu 30 cacbon bao g6m: 8 cacbon methyl, 10 cacbon methylen, 5 cacbon metin va 7 cacbon bac_4.

Tir cac s6 lieu ph6 UV, MS, NMR mot va hai chieu, v a s o sanh vol tai lieu [21], hop chat 5 dugc xac dinh la taraxerol. Hgp chit nay dugc phan lap tir cay Taraxacum officinale va cung tim thay a cac loai Alnus spp., Skimmia japonica. Rhododendron spp..

Euphorbia spp. Hgp chat taraxerol co hoat tinh khang vi sinh vat, chong viem va chong khoi u.

Hpp chat 6 la tmh the hinh kim khong mau, nong chay a 135-I36''C, Ph6 El-MS cho pic ion phan tir m/z 414 [M]'^ , ung vai cong thirc C39H50O. Pho 'H-NMR cua hop chat 6 cho tbay tin bieu cua 6 nhom metyl a 3 1,01 (3H, 5, I9-CH3), 0,92 (3H, rf, J - 6,5 Hz, 2I-CH3), 0,84 (3H, t,J=l,Q Hz, 29-CH3), 0,83 (3H, d,J=6,5 Hz, H-26), 0,81 (3H, rf / = 6 , 5 Hz, 27- CH3), 0,68 (3H, s, I8-CH5). Ph6 '^C-NMR ctia hgp chat 6 CO 29 tin hieu cho thay co 29 nguyen hi cacbon bao gom 9 nhom CH, 11 nhom CH2, 6 nhom CH3 va 3 cacbon bac 4. Cac so lieu ve pho El-MS va NMR deu phii hgp vai vol [3-sitosterol [22]. Hgp chat nay ton tai pho bien trong thuc vat.

Hgp chat 7 la chat ran vo dinh hinh, khong mau, nong chay o 283- 2 8 5 ^ . Tren ph6 El-MS xuit hien pic ion phan tu m/z 396 (M-CgHisOe). Ph6 '^C-NMR cho thay co 35 tin hieu cua nguyen tii cacbon, trong do CO 7 nguyen ti> cacbon gan voi oxy (n^m trong viing 61,2 den 100,9 ppm), co 2 tin hieu 6 140,6 va 121,3 ppm thupc ve mpt lien k^t olefin. Ph6 'H-NMR cijng cho tbay proton anomeric ( H - l ' ) cua phin duong xuat hien duoi dang doublet tai 5 5,03 ppm, co J = 7,0 Hz va 6 C- r mcmg img la 100,9 ppm. S6 lieu tir cac phS El-MS, 'H- va '-'C-NMR cho thiy co th£

day la cau true ciia mot hgp chit glucosit co cong thirc CssHscOg. D6ng then su co mat ciia manh 396 m/z (M-CsHiiOe) tren ph6 El-MS ciing xac nhan mot phan tir hexoza da bi diit khoi phan Ui sitosterol glucosit. Tir nhmig s6 lieu tren cho phep xac nhan hgp chaf tren la p-sitosterol-3-O-p-D- glucopyranoside [22]. Hgp chat nay t6n tai ph6 bi6n trong thuc vat

ri.it chi Khoa hoc \k Cang nghg 133 (2019) 079-084

4. Ket luan

Nghien cihi thanh phan hoa hpc ciia xoan ta (Melia azedarach L.) thu hai 6 vuon qu6c gia Pii Huong-Nghe An, chiing toi da tien hanh phan lap va uic dinh dirpc cac hpp chat apigenin, quercetin 3 - 0 - [a-L-rhaninopyranosyI-(l—•6)-p-D-gtucopyranoside], scopoletin, acid vanilic, taraxerol va hai steroid (p- sitosterol va P-sitosteroI-3-O-p-D-glucopyranoside.

Day la cong bo dau tien ve thanh phan hoa hpe qua xoan ta. Cac b6 phan khac cila cay xoan ta dang dugc tiep tue nghien ciiu.

LM cam gn

Cac tac gia cam on A% tai Nafosted da tai trg kinh phi,

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