• Nghien ciJu - Ky thuat
long quan ve nhdm hop chat amid alkaloid phan lap dirffc tir chi Piper L.,
ho Ho tieu (Piperaceae)
Hoang Vidt Dung'', Do Quyen^, Nguyen Minh Chinh'
Hgc vien Qudny^ Tnrang Dgi hgc Dugc Hd Ngi E-mail- vietdungk85(^yahoo.com
Summary
Amide is a major group of phytochemical compounds observed in the genus Piper L. References available to the authors document 280 amide compounds isolated from 61 species of the genus. By their chemical structures, they are classified into 11 subgroups. Of them, 5 subgroups including 134 compounds in all are presented.
Keywords: Amide, amide alkaloid, Piper L.
Dat van de
Piper L. la chi Idn nhat trong so cac chi thudc hg Hd lieu va la mgt trong nhung chi Idn nhal cua ngdnh thge vgt hgt kin. Chi nay cd so l u g n g khoang han 1000 loai tren the gidi va 47 lodi d Viet Nam'^'^. Theo t h i n g ke, da cd khoang tren 100 lodi Piper L. d u g c nghien c u u ve thanh phan hda hgc va cac nhdm hgp chat da d u o c phan lap t u chi nay gdm cd: amid alkaloid (sau day ggi la nhdm hgp chat amid), alkanpolyenylbenzen, flavonoid, lignan, neolignan, terpen... Trong dd, amid la nhdm hgp chat chinh cd mat trong cac loai Piper L.
Qua long hgp ldi lieu, da cd ba bai bao vdi ngi dung tong quan v l nhdm hgp chat amid phan lap d u g c t d chi Piper L.. Tuy nhien, ngi dung cua hai trong ba bai bao nay chi mang tinh Net ke cac hgp chal phdn lap d u g c va ngi dung cua bdi bao cdn Igi thi phan nhdm chua that ddy du va chi tiet^''"'''''''"^, Vi vay, chung toi thuc hien ndi dung nay n h l m long hgp va cap nhat thdng tin de cd cdi nhin d l y du han ve nhdm hgp c h i t amid phan lap d u g c l u chi Piper L..
Nhom hp'p chat amid
Amid la nhu'ng hgp c h i t co chua nhdm chuc -NH-CO-. (y cdc hgp chat amid phan lap d u g c t u chi Piper L, nguyen l u nita cua nhdm chuc amid cd t h i nam d mach t h i n g hoac la dj to trong vdng 5 hogc 6 canh. T h u d n g cac amid
monomer nay cd mdt nguyen f u nito cua nhom chuc amid, chl mgt so r i t it chat cd so nguyen ti> nita nhieu hon mgt. Amid la nhom hgp ciiat chinh CO mat trong chl Piper L.. Vdi s6 lugng 280 chat phdn lap t u 61 loai thugc chi Piper l.
da d u g c bao cao, nhdm h g p chat amid khd 3a dang ve cau true vd cd f h i d u g c phan thanh 11 nhdm sau day^^"'^'*''^.
1. N h o m hg'p chat c d k h u n g cau t^o d i b e n z o q u i n o l i n
Hinh 1 : Ciu tao hda hgc cua khung dibenzo quinolin
So vdi cac nhdm con lgi, nhdm nay cd so lugng c h i t it nhdt vdi 8 hgp c h i t dugc bdo c^o.
Trong do, cdc hgp c h i t thudng cd cau tgo vd'i Rz=R3= O; R4= -H va R5=Re= -OCH3 hoac F^+Rfi=
-OCH2O-. Chi cd 2 chat cd c l u tgo vdi R2=R3= -H va 2 chat cd c l u tgo vdi R4 = -OCH3 ^^^•^^.
TAP CHI DlTgfC HQC - 09/2013 (SO 449 NAM S3)
• Nghien CLPU - Ky thuat
Bang 1 : fi^gt s6 hr^rp chat thu^c nhom dibenzo quinolin Ky ^ . ^ _^,^ Ciu trOc
hi^u °" ^ R, R2 R3 Rt Rs Rs 1 CepharadionA -CH3 =0 = 0 -H -OCH2O- 2 CepharadionB -CH3 =0 = 0 -H -OCH3 -OCH3 3 Norcepharadion B -H = 0 = 0 -H -OCH3 -OCH3
Loai P. longum L.
P. longum L.
P. longum L.
[16]
[16]
[16]
Mgc du id nhom cd so lugng chat it nhat nhung mgt so chat cua nhon lgi cd mgt trong khd nhieu lodi Piper L. khdc nhau. Dien hinh nhat la hgp chat cepharadion (1), theo thong ke, chat nay da dugc phdn ldp t o 13 lodi Piper L. khdc nhau nhu: P.
bettle L., P. longum L, P. sanctum (IVIiq.) Schlechtendal, P. argyrophylumM\c\... ''^•^^.
Z Nhdm hgp c h i t cd khung d u t ^ piperelactam Qua long hgp tdi li$u, cd 16 hgp c h i t thugc nhdm ndy phdn ldp d u g c t u mgt so lodi Piper L.
Ode d i l m chung cua cac c h i l trong nhdm t h u d n g cd c l u tgo vdi Ri=R2= -H; Ra vd R, Id - OCH3 hode -OH '^^•"'.
Hi n h 2: Cau fgo hoa hgc cua khung piperolactam
Bdng 2: M0t so hgp chat thugc nhom piperolactam
Ky hl^u 4 5 6
T6n hvp chdt Cepharanon B Piperolactam A Piperolactam B
R.
-H
• H -H
Cdu true
R I Rl
-H -OCH3 -H -OCHa
•OH -OCHs R4
•OCHs
•OH -OCH,
Loii Piper marginatum Jacq.
Piper marginatum Jacq P. longum L.
[13]
[13]
[16]
T;>P CHi DirglC HOC - 09/2013 (S6 449 NAM 53)
• Nghien CIFU - Ky thuat
Trong so cac iigp chat cua nhdm, piperdadam A (5) cd mat pho b i l n tnang nhieu loai Piper L. n h l l vdi 6 loai da dugc bao cdo gdm: P. bngum L., P.
wightii Miq., P. argyrophylum M\q., P.
boehimerifolium Wail, ex C. D C , P. aUenuatum Buch. Ham. ex IVIiq. va P. hamiltonii C. DC. '^^.
3. N h o m h g p c h a t c 6 k h u n g cau tao aryl - a l k a n p o l y e n o y l - piperidin
Hinh 3: Cau tao hoa hoc cua khung aryl - alkanpolyenoyl - piperidin
Nhdm hgp chat nay cd so l u g n g chal phdn lap d u g c l u chi Piper L. n h i l u t h u hai trong so cac nhdm hgp chat amid vdi 47 c h i t d u a c bdo oao. Trong dd, piperin (7) la amid pho b i l n nhat va da d u g c phan lgp t u 20 lodi thugc chi nay gdm cd: P. album, P. bettle L, P. longum L., P.
nigrum L., P. khasiana C. D C , P. chaba Hunt...
[4.6.14.17,19]
Dac diem chung cua nhung h g p chat thuoc nhom nay la:
- Nhdm the d nhan thom: R3 va FR4 thudng la -H hogc -CH3 hoac R3 + i ^ = -OCH2O-.
- Gdc R la goc alkanpolyenyl mach thdng trong do mach carbon c6 so carbon thay doi tir 2 ddn 13, so noi ddi thay doi t u 1 d i n 4.
Bang 3: Mot sd hgp chat thuoc nhom aryl - alkanpolyenoyl - piperidin Ky
hieu 7
8
g
Ten hop chat
Piperin 2'-methoxy-4',5'- m ethyl enedioxy-tra ns-
cinnamoylpipendin (2E,4E)-N-9-(3,4- methylenedioxophenyl-
nonadienoylpipendin R - C H , -
-C2H2-
-CiiHia- R>
-H
-OCHa
• M
Cau true Rs - H
• H
• H
Rs R4 -OCHsO-
-OCH2O-
-OCH2O- Rs
• H
-H
-H
Loai P. nigrum L, P. chaba Hunt.
P. amalago L
P. retrofractum Vahl [2], [8]
[18]
[11]
^-^^^^--^
Vdl mdt sd hgp chat, mac du d u g c xep vao nhdm nay nhung cd cau lao khac so vdi cau tgo khung tong quat cua nhdm d vj tri gdc piperidin, vi du: hgp c h i t N-(3'-methoxy-4',5'- methylenedioxy- cinnamoyi) -A^-piperidin-2-on (10) phdn lap dugc t u lodi P. aborescens Roxb. vd cd c l u lao nhu tren'^.
4. N h o m h g p c h a t co k h u n g cau tao a l k a n p o l y e n o y l p i p e r i d i n
A,
H i n h 4 : Cau tao alkanpolyenoyl pipetidin
hoa hgc cua khung
T A P CHT DlTCfC H O C - 09/21111 rSI^ ddO NAM « i
• Nghien ciru - Ky thuat
Theo k i t qud nghien c u u da cdng b l , 15 c h i t cd c l u true khung trdn da d u g c phan lap t u chi Piper L.. Hgp chat dan gian n h l l thudc nhdm ndy Id N-formyl piperidin (11) d u g c phan ldp I d lodi P. nignjm L. vdi R = -H '''^. Cac hgp c h i l cdn lgi c6 dgc diem chung Id cd goc R dgng
mgeh t h i n g , hgp c h i t cd mgeh carbon ddi n h l l Id 32 carbon v d hgp c h i t c6 il noi ddi nhat la 1 noi ddi. 3 trong so 15 amid ke tren co goc R vdi mgeh 9 carbon, t h i n g va cd nhdm ceton hoac hydroxy g i n vao'^^'^^.
Bang 4: M0t so hgp chat thugc nhom alkanpolyenoyl piperidin Ky hieu
12 13
Tin hgp chit
(2E.4E,14Z)-N-(2,4,14-octadecatrienoyl)-piperidin (±)-erythro-1-(1-oxo-4,5-dihydroxy-2E-octaenamid
R C24H43-
C9H15-
Loai P. retrofractum Vahl
P. nigrum L.
TLTK [11]
[14]
5. Nhom h g p chat co khung cau tao aryl - alkanpolyenoyl - pyrrolidin
hgp chat d u g c bao cdo phan lgp l u chi Piper L. '^••''*'^^"i. Eiac diem chung cua cdc hgp c h i t thugc nhom nay la:
- Nhdm the d goc aryl: thu'dng cd R, = R2 = Rs = -H va R3 + Fl, = -OCHzO-.
- Goc R Id goc alkanpolyenyl mgeh t h i n g trong dd mgeh carbon co so C rat khac nhau giu'a cac chat thay doi l u 2 tdi 29. So noi doi trong mach thudng Id 1, tuy nhien cung co mgt vai hgp chat co so noi ddi nhieu ban 1.
Bdng 5: M^t so hpp chSt thu0c nhom aryl - alkanpolyenoyl - pyrrolidin Hinh 5: Cdng thirc ciiu t^o cda khung aryl -
alkanpolyenoyl - pyrrolidin
Qua l i n g hgp lai li^u cho I h l y nhdm hgp c h i t ndy c6 s6 lugng amid nhieu nhat vdi 48
Ky hl$u 14 15
T&r} h9p chit - Piperamin Tnctiostachin
R -CsHa-
-C.H,
Ciu true Rf R2 Rs R4
•H -H •OCH2O-
•H -H -OCH2O- Rs -H
•H
Loai P. chaba Hunt.
P. trichostachyon C. DC [8]
[9]
o
IVIdt s6 hgp c h i t mgc dCi d u g c x i p trong nhdm ndy nhung p h i n g l c pyrrolidin d u g c Ihay bdng g l c pyrrol hode cd mgeh carbon no, v i dg:
h g p c h i t N-(3-phenylpropanoyl) pyn-ol (16) phdn
lgp d u a c l u lodi P. longum L. va co cau tgo nhu hinh vetren'^^'
(Con nO-a)
TAP CHi DUgtC Hpc - 09/2013 (S6 449 NAM 53)
Nghien ci!ru - Ky thuat
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Praveen et al (2004), "Antibactenal constituents from the berries of Piper nigrum", Phytomedicine, vol. 11, pp. 697 - 700.
16 Sanjay J. Desai, Bharathi R. Prabhu, Newand B Mulchandani (1988), "Anstolactams and 4,5 - dioxoaporphines from Piper longum", Phytochemistry.
vol. 27(5), pp. 1511-1515.
17 Virinder S. Parmar, Subhash C. Jam, Kirpal S.
Bisht et al (1996), "Phytoch^nistry of the genus Piper, Phytochemisrry, voi, 46 (4), pp, 591 - 6 7 3
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