1. Khi nim chung v anthranoid 2. Cu trc ho hc, phn loi 3. Tnh cht, nh tnh, nh lng 4. Chit xut 5.

Tc dng, cng dng 6. Ti liu tham kho

Dc liu cha anthranoid thuc chi cassia. Phan t dip, Tho quyt minh, Ct kh mung, Mung tru... Dc liu cha anthraglycosid thuc h rau rm: Ct kh c, i hong, H th , Dc liu cha anthranoid khc: Ba kch, L hi, Dm dng hoc,

KHI NIM CHUNG V ANTHRANOID

Nhng hp cht anthranoid nm trong nhm ln hydroxyquinon. Nhng hp cht quinon c tm thy ch yu trong ngnh nm, a y, thc vt bc cao v c trong ng vt. Cn c vo s vng thm nh thm vo nhn quinon m ngi ta sp xp thnh benzoquinon, naphthoquinon, anthraquinon v naphthacenequinon hay cn gi l anthracyclinon (4 vng). Anthranoid hay anthraquinon khi tn ti di dng glycosid th c gi l anthraglycosid hay anthracenosid. Cng nh cc loi glycosid khc Anthraglycosid l nhng glycosid khi b thu phn s cho phn ng v phn aglycon (genin) l dn cht 9,10 anthraquinon*, (9,10-anthracendion*) (9,10 dixeton ca anthraxen). a s cc anthraglycosid l cc polyoxy anthraquinon. Gn vo nhn thng c cc nhm chc -OH, -OCH3, -CH3, -COOH... Tu theo v tr cc nhm chc nh vo nhn m c cc dn cht khc nhau: V trong t nhin hu nh cha gp cc dn cht 1,2 hoc 1,4anthracendion nn khi ni n cc dn cht anthraquinon trong t nhin th ngi ta hiu rng l nhng dn cht 9,10anthracendion. S to thnh cc dn cht anthraquinon xut pht t

2 con ng: 1. i vi nhng dn cht 1,8-dihydroxyanthraquinon hay gp trong cc h thc vt Polygonaceae, Caesalpiniaceae, Rhamnaceae cng nh trong mt s nm v a y, con ng sinh nguyn xut pht t cc n v acetat. Ngi ta a acetat c nh du bng ng v phng x vo mi trng nui cy nm Penicillium islandicum l nm to ra dn cht anthranoid th thy cc n v acetat c ngng t ni vi nhau theo u ui. Cht poly-b-cetomethylen acid c to thnh u tin ri tip theo cc dn cht anthranoid. (S1) 2. Con ng th hai to thnh cc dn cht anthraquinon trong mt s h thc vt khc ch yu l h Rubiaceae th cht tin sinh l acid shikimic. Sau khi acid ny ngng t vi mt acid acetoglutaric th to thnh mt dn cht naphtalen ri cht ny li gn thm mt gc isoprenyl ri ng vng to ra cc dn cht anthraquinon. (S2) Anthraquinon n gin nht khng c nhm th th khng c trong t nhin nhng c c bng cch oxy ho anthracen hoc bng tng hp t anhydrid phtalic:(S3)
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Cu trc ho hc, phn loi

Dn cht Antraquinon c th chia thnh ba nhm. (Nhm phm nhum, Nhm nhun ty, Nhm dimer)

Nhm phm nhum (Cc dn cht 1,2 dihydroxy anthraquinon)

Nhng dn cht thuc nhm ny c mu t cam n ta. trong cu trc c 2 nhm OH k cn v tr a v b v hay gp trong mt s chi thuc h C ph - Rubiaceae (chi Rubia, Coprosma...) i din nhm ny c: alizarin (1,2 dihydroxy anthraquinon); acid ruberythric (=2-primeverosid ca alizarin), purpurin (= 1,2,4trihydroxyanthraquinon). Boletol l cht c mu sng c trong mt s loi nm thuc chi

Boletus. Acid carminic (7- C- glucopyranosyl - 3,5,6,8-tetrahydroxy1-methylanthraquinon-2-carboxylic acid) dng mui nhm c gi l carmin c mu l thuc nhum dng lm t dc mu trong bo ch, thc phm, m phm, nhum vi phu thc vt. Acid carminic c chit t loi su Dactylopius coccus Costa (Coccus cacti L.). Loi su ny sng trn nhiu loi xng rng thuc chi Opuntia h Xng rng - Cactaceae Trung M, ch yu Mexico. Ngi ta ly trng ca nhng con su ci trc khi trng cha pht trin hon ton, em sy kh- nguyn liu cha 10% cht mu. Acid carminic l mt C-glycosid.(CT) Acid kermesic l cht mu ly t loi su Kermococcus ilicus (CT). nc ta c cnh kin l sn phm do loi su Laccifer lacca Kerr to ra trn cnh mt s cy ch nh cy u chiu Cajanus indicus, cy (Ficus religiosa L.)...thnh phn chnh ca cnh kin l nha dng ch shellac dng nh bng vecni g, my tre; sn phm ph l cht mu sm gi l acid laccaic . y l mt hn hp nhiu cht, trong Acid laccaic A,B,C c mu . Acid laccaic D v khng c 2 nhm OH nn c mu vng.(CT) Nhm ny cn gp trong mt s chi thuc h: Rubiaceae (Rubia tinctoria)....

Nhm nhun ty (cc dn cht 1,8 dihydroxy anthraquinon).

Dn cht 1,8 dihydroxy anthraquinon (oxymethylanthraquinon) thng c nhm CH3, CH2OH, CHO hoc COOH v tr 3. Dn cht 1,8 dihydroxyantraquinon c th dng t do hoc kt hp vi phn ng dng glycosid. Mt s cht thng gp thuc nhm ny: Cryzophanol (Acid Cryzophanic), Aloe emodin, Rein, Reum emodin (Emodin), (Phyxion) Tu thuc mc oxyho ca cc dn cht anthraxen ngi ta chia thnh: anthraquinon (dng oxy ho), anthron v anthranol (dng kh). Nu kh mt trong hai nhm chc ceton ca anthraquinon s cho dn cht anthron hoc ng phn h bin ca cht ny l anthranol (dng enol). Nu kh tip th dn n dn cht

dihydroanthranol. Dng kh c tc dng x mnh nhng hay gy au bng v vy mt s dc liu cha anthranoid phi 1 nm sau khi thu hi mi dng dng kh chuyn thnh dng oxyho. Phn ng trong antraglycosid thng v tr 1,6,8 c khi v tr 3.

Nhm dimer
Mt s dn cht anthranoid dimer do 2 phn t dng anthron b oxy ho ri trng hp vi nhau to thnh dianthron hoc tip n cc dn cht dehydrodianthron v d s to thnh hypericin l cht c trong cy Hypericum perforatum, c tc dng khng khun dng cha vim d dy, rut, rng, ming. Mt s v d khc l cc cht: ararobinol (c trong ct kh mung v trong cc loi Rumex spp.), sennosid A,B,C (c trong Phan t dip) hoc rheidin A,B,C (c trong i hong). Khi to thnh dimer nu 2 na phn t ging nhau th gi l homodianthron v d ararobinol, sennosid A,B; nu 2 na phn t khng ging nhau th gi l heterodianthron v d sennosid C, rheidin A.(CT) Trong chi Cassia ngi ta cn gp mt s dimer dng dianthraquinon nh cassianin, cassiamin. Loi dianthraquinon cn gp trong mt s loi nm Penicillium. Trong thc vt ngoi nhng dn cht anthranoid xp vo 3 nhm trn cn c nhng dn cht khc c mt s nhm th c bit, v d cht fragilin c trong a y Sphaerophorus globosus hoc nalgiolaxin c trong nm Penicillium c gc Cl. Cc dn cht anthranoid c phn b trong khong 30 h thc vt khc nhau, ch yu l nhng cy 2 l mm. Cc h hay gp: Caesalpiniaceae, Rhamnaceae, Rubiaceae, Polygonaceae. Trong cy mt l mm rt him. Cho n nay c 2 cy c bit: L hi - Aloe spp. v Hemerocallis aurantiaca. Trong nm, a y cng c. Trong ng vt th gp trong cc loi su nh Coccus cacti, Kermococcus ilicus, Lacifer lacca. Di y l bng ghi mt s dn

cht anthranoid cng vi ngun thc vt:

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Tnh cht, nh tnh, nh lng

Tnh cht, nh tnh: (Ch yu nhm nhun ty). - Nhng dn cht anthraquinon u c mu t vng, vng cam n . - D thng hoa nn c th li dng tnh cht ny nh tnh bng cch lm vi thng hoa anthraquinon trn lam knh ri soi tinh th qua knh hin vi, s thy hnh kim mu vng. - th glycosid d tan trong nc, cn th t do (aglycon) th tan trong ether, chloroform v mt s dung mi hu c khc. - OH v tr th c tinh acid yu hn v tr do to dy ni hydro vi nhm carbonyl nn cc dn cht ch c OH a th ch tan c trong dung dch NaOH. Cc dn cht c OH nhng khng c nhm COOH trong phn t th tan c trong dung dch NaOH v carbonat. Cc dn cht c nhm COOH th tan trong dung dch NaOH, carbonat, v c hydrocarbonat. - Dn cht oxyanthraquinon m c t nht mt nhm OH th cho mu vi Mg acetat trong cn, ngoi ra mu m nht cn ph thuc vo cc nhm OH khc, nu l dn cht 1,2-dihydroxy th cho mu tm, 1,4-dihydroxy th cho mu ta, cn 1,6 v 1,8 mu cam. - Dn cht c 1,4-dihydroxy s c hunh quang trong dung dch acid acetic. Ngoi ra cc dn cht ny cn cho mu xanh dng r vi H2SO4. - Cc dn cht thuc nhm nhun ty khi trong dung dch kim to phenolat c mu v di nh sng U.V (365 nm) cho hunh quang tm hoc nu. Da vo tnh cht ny nh tnh (phn ng Bortrager): ly mt t bt dc liu cho vo ng nghim, thm dung dch H2SO4 25%, un nh thy phn glycosid (nu c) ra dng aglycon. i vi mt s dn cht anthranol v d barbaloin th phi cho thm mt t dung dch H2O2 hoc FeCl3 chuyn sang dng oxy ho. ngui, lc vi mt dung mi hu c v d ether,

gn lp ether ra mt ng nghim khc ri thm mt t dung dch NaOH 10%. Lp kim s c mu . - Mun pht hin s c mt ca acid chrysophanic trong hn hp oxymethylanthraquinon c th tin hnh nh sau: sau khi thy phn, hn hp oxymethylanthraquinon c chit bng benzen, tch lp benzen ra ng nghim, thm dung dch ammoniac v lc u, nu lp benzen cn mu vng th tch lp benzen ra ri cho tc dng vi dung dch NaOH, lp NaOH c mu hng cn lp benzen mt mu th s b kt lun trong hn hp c mt acid chrysophanic. - Cc dn cht anthranol c phn ng vi p-nitroso dimethylanilin to thnh azomethin c mu. Trong trng hp cc C-glycosid anthron th c th pht hin bng s xut hin hunh quang khi c mt natri borat (phn ng Schouteten). SC K sc k pht hin ton b cc dn cht dng t do v dng glycosid ngi ta un bt dc liu vi MeOH, ngui, lc. Chm dch lc trn bn sc k. tch cc glycosid, dng silicagel G vi cc h dung mi sau: Ethylacetat - methanol - nc (100:17:13). Ethylacetat - n-propanol - nc (4:4:3). Chloroform - methanol (4:1).

Nu ch mun pht hin cc aglycon dng oxy ho, th chit nh sau: 0,2g bt dc liu cho vo ng nghim, cho thm 5 ml H2SO4 25% v 1 ml dung dch H2O2. un si trong vi pht, ngui, lc vi 4 ml chloroform, chm dch chloroform ln bn sc k trng bng siilicagel vi NaOH 0,01 N, bn dy 0,25 mm, thc hin trn 3 h dung mi tng dn lng acid nh sau: (I) benzen - EtOH - AcOH (75:24:1); (II) h dung mi nh trn (75:20:5); (III) h dung mi nh trn (7:2:1). Di y l Rf x 100 ca mt s dn cht anthraquinon (theo J.W.Fairbairn): Thuc th pht hiin: a) dung dch KOH trong cn, quan st nh sng thng v nh sng U.V. bc sng di. b) dung dch Mg

acetat trong cn. c) Pyridin - methanol (1:1), thuc th ny dng phn bit cc dn cht anthraquinon vi cc dn cht anthron, dianthron. Trn sc cc dn cht anthraquinon cho mu vng cn cc dn cht anthron v dianthron cho mu tm. QUANG PH: Ph t ngoi ca cc dn cht oxymethylanthraquinon thng c nhiu nh: 4 nh trong vng 200-300 nm v mt nh vng kh kin trong khong 430-440 nm. Sau y l ph U.V. ca mt s cht: Emodin (4,36) Chrysophanol (4,07) 432 (4,08). Physcion 226 nm (4,45) 440 (4,02). Aloe emodin (4,03) 430 (4,03). Rhein 230 nm ( 4,57) 260 (4,34) 432 (4,07). 225 nm (4,59) 258 ( 4,36) 279 (4,03) 287 255 (4,22) 267 (4,25) 288 (4,22) 223 nm (log e 4,56) 254 (4,25) 267 (4,24) 290 440 (4,09). 225 nm (4,57) 258 (4,33) 279 (4,01) 288

Ph IR c nhng pic: 1630 cm-1 (C=O c dy ni hydro vi -OH), 1670 (C=O t do), 1570 (C=C thm), 2890 (-CH=), 3400 (OH) nh lng ( nhm nhun ty) 1 - Phng php cn: phng php ca Daels v Kroeber. Nguyn tc ca phng php ny nh sau: Dc liu c un vi acid sulfuric 25% thy phn cc glycosid, cc aglycon c chit ra bng chloroform. Dung dch chloroform em ra vi dung dch natri bisulfit ri tip theo vi dung dch HCl long. Sau bc hi dung mi, cn c em sy v cn. Dc in Lin X IX ng dng phng php ny nh lng cc oxymethylanthraquinon trong v cy Rhamnus frangula L. v trong i hong.

Cch tin hnh: cn chnh xc 2 g bt dc liu, un cch thy trong bnh c ng sinh hn hi lu trong 2 gi ri vi 200 ml CHCl3 v 50 ml H2SO4 25%. Sau lc cc dch chit CHCl3 vi 50 ml dung dch natri bisulfit 10% trong 5 pht. Sau khi yn tch lp CHCl3, lc v lc vi dung dch acid hydrochloric 1% trong 5 pht. Sau khi 2 lp phn cch r rng, ngi ta tch lp di, lc v bc hi CHCl3, sy, lc u 600 ri sau 800C n khi khi lng khng i. 2- Phng php so mu: Phng php ny da trn phn ng mu Brntraeger. Tschirch l ngi u tin a ra phng php nh lng anthranoid trong i hong. Theo tc gi, bt i hong c un si vi dung dch H2SO4 long, sau chit bng ether. T dch ether li chit bng kim ri o mu. Nhiu tc gi khc c thay i mt s iu kin v dung mi hu c, acid, thi gian thy phn, loi dung dch kim lm phn ng mu. Sau y ch trnh by phng php ca Auterhoff l phng php c nhiu ngi chp nhn. Nguyn tc ca phng php l un dc liu vi acid acetic thy phn cc glycosid, sau thm ether chit aglycon. T dch acid acetic ether (ch acid acetic ho tan trong ether) cc aglycon c lc nhanh vi dung dch xt cng vi ammoniac. Dung dch kim c mu , c em o mt quang. ng cong chun c xy dng vi cht mu istizin (= 1,8-dihydroxyanthraquinon) hoc acid chrysophanic c pha cng trong dung dch xt + ammoniac hoc da vo dung dch cobalt chlorid; dung dch ny c mu hng nh mu ca phn ng. Mt quang ca 0,36mg istizin trong 100ml dung dch xt + ammoniac (5g NaOH trong 50ml nc thm 2ml ammoniac m c v thm 100ml vi nc ct) bng mt quang ca dung dch cobalt chlorid 1%. Phng php ny hn ch ti mc thp nht s oxy ho cc cht dng kh anthron. Cc cht ny c mu vng trong mi trng kim nn khng cn tr s nh lng. Nu mun nh lng anthranoid ton phn cn oxy ho cc dn cht anthron bng cch t cc

dung dch phn ng vi kim ln ni cch thy trong 20 pht. mi trng kim cng vi nhit v khng kh, cc dn cht anthron s b oxyho thnh anthraquinon. Hiu gia 2 ln o trc v sau khi oxy ho cho php ta tnh c hm lng ca cc dn cht anthron. Nu mun nh lng cc aglycon dng t do trong dc liu th khng qua giai on thy phn m ch cn chit cc aglycon t do bng ether ri thm dung dch kim lm phn ng mu. Phng php Auterhoff c a vo Dc in Vit Nam nh lng nhng dn cht anthranoid trong dc liu. 3 - Phng php th tch ca Tschirch v Schmitz: Nguyn tc ca phng php l dng dung dch KOH 0,1 N tc dng ln cc dn cht anthraquinon ri chun kim tha bng HCl 0,1 N; s chuyn mu t sang vng ca phn ng thay cho ch th mu. Phng php ny t c dng v thiu chnh xc. Ngoi cc phng php trn, c th kt hp sc k vi o quang nh lng tng thnh phn ring. Ngoi ra c th nh gi bng phng php sinh vt trn chut th nghim. i vi L hi khng dng phng php ny v chut km nhy cm, liu x ca sennosid l 1 mg/kg th trng chut cn barbaloin l 300 mg/kg.
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Chit xut
Mun chit xut glycosid, dng cn ethylic hoc cn methylic hoc hn hp cn - nc. Mun chit phn aglycon, thy phn bng acid sau chit bng ether hoc chloroform. tch cc dn cht anthraquinon c th s dng ho tan khc nhau trong mi trng kim khc nhau nh ni phn trn nhng s phn chia khng c tch bch m thng cn ln cht ny vi mt t cht khc. Trong nghin cu ngi ta hay dng sc k ct vi silicagel, kieselghur, bt cellulose. C th dng calcicarbonat, Mg carbonat, dicalci phosphat, calcisulfat, Mg oxyt, calci oxyd. trin khai, nu tch cc glycosid th dng ethanol

hoc methanol vi cc cn khc nhau, cn tch aglycon, dng cc dung mi hu c theo phn cc tng dn v d CHCl3, tng dn lng cn t (1-5%), theo di cc phn on bng n t ngoi.
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Tc dng sinh l v cng dng

Cc dn cht anthraglycosid, ch yu l cc -glucosid d ho tan trong nc, khng b hp thu cng nh b thy phn rut non. Khi n rut gi, di tc dng ca -glucosidase ca h vi khun rut th cc glycosid b thy phn v cc dn cht anthraquinon b kh to thnh dng anthron v anthranol l dng c tc dng ty x, do c th gii thch l do tc dng n chm sau khi ung thuc. Dng genin th b hp thu rut non nn khng c tc dng. Do tc dng lm tng nhu ng rut nn vi liu nh cc dn cht 1,8-dihydroxyanthraquinon di dng heterosid gip cho s tiu ho c d dng, liu va nhun, liu cao x. Thuc tc dng chm, 10 gi sau khi ung mi c hiu lc. V cn c tc dng ln c nhn ca bng quang v t cung nn dng phi thn trng i vi ngi c thai, vim bng quang v t cung. Bi tit qua sa nn cn ch i vi cc b m c con b, bi tit qua nc tiu nn nc tiu c th c mu hng. Cc dn cht anthraglycosid cn c tc dng thng mt. Hn hp cc dn cht anthraquinon c trong r cy Rubra tinctoria L. c tc dng thng tiu v c kh nng tng si thn. Sapa, Ngha L, vng Lai Chu c cy Thin tho Rubia cordifolia cng c nhng dn cht anthraquinon tng t nh cy trn. Chrysophanol c tc dng khng nm dng tr nm, hc lo, lang ben. Mt s nghin cu cho thy cc dn cht quinon c bit l cc dn cht anthraquinon c tc dng kch thch min dch chng ung th. Xut pht t acid chrysophanic v cc dn cht anthraquinon khc, ngi ta bn tng hp mt s dn cht c N-, S- v gc halogen c hot tnh chng ung th.

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15. nh ngha, cu trc ho hc ca anthranoid 16. Cc phng php nh tnh, nh lng anthranoid trong dc liu. 17. Nguyn tc chit xut anthranoid t dc liu. 18. Tc dng sinh hc v cng dng ca anthranoid 19. anthranoid: Phan t dip; Tho quyt minh; Mung tru; i hong, Ct kh c, H th ; Ba kch, L hi.

Ti liu tham kho

- Bi ging dc liu tp I Tr. 215-230