Dai Cuong Anthranoid

8/10/2019 Dai Cuong Anthranoid

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B MN DC LIUI HC Y DC TP. H CH MINH

DC LiU CHA ANTHRANOID

1


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MC TIU HC TP

1. c im cu trc ca 3 nhm anthranoid(nhm phm nhum, nhun ty v dimer).

TRNH BY C

2. Cc tnh cht cn bn ca anthranoid

3. Nguyn tc chit xut anthranoid t dc liu

4. Cc phng php nh tnh, nh lnganthranoid trong dc liu.

5. Tc dng sinh hc Cng dng ca anthranoid

6. 06 dc liu cha anthranoid chnh(Cassia, i hong, L hi )


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Ni dung

1- nh ngha2- v tr phn loi3- Phn nhm anthanoid (3 nhm)4- cc loi glycosid5- Tnh cht ca anthranoid v cc pp nh tnh6- Chit xut7-Phn lp

8-nh lng9-Tc dng sinh hc

3


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1. NH NGHA

Anthranoid l nhng glycosid c

phn aglycon l ca 9,10 diceton-anthracen.

(= anthracenoid)

O

O1

2

3

45

6

7

8

9

10


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Trong cau truc co 2 nhom chc ceton(thng la para).Cac nhom chc ceton nay co the dang oxy hoahay

dang kh

O

O

O

OH OH

OH

dang oxy hoa dang kh


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THUT NG

nhm 1,8 di-OH AQ : C3, C6 thngc nhm th

CH3, CH3O, CH2OH, CHO, COOH, OH

gichung l Oxy Methyl Anthraquinon (OMA)

anthraquinon

anthron, anthranol

dihydroanthranol

AQ oxy ha

AQ khdngaglycon

anthraglycosid (AG)

anthraquinon (AQ)

dng O-/C-glycosid

dng aglyconANTHRANOID


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anthraquinon anthron anthranol dihydroanthranol

AQ

1 dngoxy-ha 3 dngkh

anthraquinon anthron anthranol dihydroanthranolglycosid glycosid glycosid glycosid

AG

+ oseANTHRANOID


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2. V TR PHN LOI

C6 Benzoquinon

C6C1 Phenolic acid

(C6C1)2 Anthraquinon, Stilben

C6C1C6 XanthonC6C2 Phenyl acetic acid, acetophenol

C6C4 Naphthoquinon

O

O

Anthraquinon Stilben

O

O

Xanthon


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O

O

1

2

3

45

6

7

8

9

10

O

O

OHOH

8 1 1

2

O

O

OH

OH

nhm phm nhumnhm nhun ty

3. PHN LOI ANTHRAQUINON


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3. PHN LOI ANTHRAQUINON

3.1. nhm phmnhum 3.2. nhm nhun ty

sinh tng hp :

con ng acid shikimic

sinh tng hp :

con ng polyacetat

O

O OR

OR1

28

O

O OROR1

2

8

O

O

OH

OH

alizarin istizin

O OHOH

O


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3.1. NHM PHM NHUM

2 nhmOH (hoc OR) k cn (C1v C2)

nhm 1,2 dihydroxy anthraquinon (nhm 1,2)

mu vng ti, vng cam, cam n ta.

thng gp / h Rubiaceae; trong cn trng.

O

O OR

OR1 28


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acid ruberythric

O

OOH

OH

OH O

OOH

OH

O

OO

OHglc xyl

O

O

OH

OH

OHOH

HOOC

O

O

OH

MeOH

HO

OH COOH

glucose

boletol

purpurin* alizarin*

acid carminic

3.1. NHM PHM NHUM


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O

OOH

OH

O

O

S PhNH R

NH R

SPh

NHM NHUM MU TNG HP

green dyes yellow dyes

(R = C2H4OH)


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2 nhmOH (hoc OR) C1v C8()

nhm 1,8 dihydroxy anthraquinon (nhm 1,8)

mu vng nht vng cam, cam.

gp / h Fabaceae, Polygonaceae, Asphodelaceae

C3,C6: R = CH3,OCH3, CH2OH, CHO, COOH (OMA)

1

3

8

O

O OROR

R

3.2. NHM NHUN TY


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Istizin H

Chrysophanol CH3

Aloe emodin CH2OH

Rhein COOH

O

O OHOH

R3

O

O OHOH

MeRO

H Chrysophanol

HO EmodinMeO Physcion

3.2. NHM NHUN TY


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3.3. NHM DIMER

O OHOH

OHMe

Me OH

OOH OH

O OHO

COOH

COOH

OO OHGlc

Glc O OHOH

MeHO

COOH

OOH OH

sennosid A v B

hypericin

- thng : 2 ph.t anthron dianthron,

hay dehydro-dianthron

- vi trng hp l dianthraquinon.

dngkhca(emodin + rhein)

diemodin anthron rheidin A

O

O

OHOH

OH

OH

OHOH

Me

Me


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4. CC LOI GLYCOSID

O-glycosid

O OHOH

CH2OH3

glucose

O OHOH

CH2O3

Glc Rha

O OHOH

MeO

O

3

Rha

O

O OH

O Glc Xyl

glycosid hn tp

C-glycosid

O-glycosid


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NG (OSES)

Phn ose trong AG th n gin.

- Loi ose hay gp : Glc, Rha, Xyl

- t khi gp 2 mch ng (gn vo 2 ni)

- t khi gp 1 mch c 3 ng (gn vo 1 ni)

- Thng : 1 mch (gm 1 hoc 2 ng)

AQglcglc.

AQglcxyl.


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TNH CHT V CC PHNG PHP NH TNH

5.1. L tnh chung5.2. Tnh acid5.3. Phn ng Borntreger

5.4. vi thng hoa5.5. Phn ng vi Mg acetat / MeOH,5.6. Phn ng vi Pyridin / MeOH (1 : 1)

5.7. SKLM (bn silica gel)5.8. Quang ph IR5.9. Ph UV ca anthraquinon

19


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5. TNH CHT NH TNH (OMA)

glycosid : - kh tan / dmhc km phn cc.

- khng thng hoa c.

aglycon : - d tan/ dung mi hu c km phn cc

- kh tan / acid.

- thng hoa c

c 2 dng : - d tan trong dd. kim, ROH

- tan c / nc nng, bn nhit

- km tan / dd. NaHSO3(naphthoquinon)

5.1. L tnh chung (ch yu ca cc OMA)


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ch c OH : ch tan / kim mnh

cOH : tan c / kim yu

cCOOH : tan c / kim rt yu

(bi)carbonat, ammoniac (Long)

5.2. Tnh acid

-OH (tnh acidmnh hn)

-OH (tnh acid yu hn)

O

OOH

HO

OH

HO

OH



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Dng kim khcnhau phn lp

cc cht

AG ton phn

dch thy phn/dmhu c

i hong

tp phn cc

Rhein

Emodin

chrysophanol

NaHCO35%

Na2CO35%

NaOH 5%

H2SO425%,

tnh acid

(+++)

(++)

(+)


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XC NH ACID CHRYSOPHANIC

dch AQ / benzen

dch benzen (vng)

lp kim : mu

NH4OH( L) x n ln b dch NH4OH (AQ acid mnh)

lc vi NaOH 5%

S b KL: c acid chrysophanic(tnh acid yu, khng tan / NH4OH)

18

O

OOH OH

Me3

(AQ acid yu)


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5.3. Phn ng Borntreger ***

NaOH hay KOH

longmu th

mu (1,8 di-OH)

xanh tm (1,2 di-OH)

(naphthoquinon cng cho mu )

- trong ng nghim, bnh lng

- trn bn mng, lame

- trn m thc vt. . .

Thc hin



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Bt DL + acid + thy phn

ngui, lc vi benzen

lp benzen

lc vi kim long

lp kim lp benzen

lp kim , lp benzen mt mu AQ

lp kim vng, hunh quang lc+H2O2

mu

dn cht kh

Trongng

nghim


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THC HiN PHN NG BORNTRAGER

trn lam knh (sau khi vi thng hoa)

bng kim

AQ AQ

bng kim chuyn sang mu :1,8 di-OH AQ


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5.5. Phn ng vi Mg acetat / EtOH, MeOH

O

R O O

O R

Mg

Mg

1

2

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8

- c ch : to chelat- ng dng : nh lng / UV-vis


AQ (c OH)Mg acetat

cam (1,6 v 1,8 di-OH)

tm (1,2 di-OH)

ta (1,4 di-OH)

(u bathochromic !)

ROH


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5.6. Phn ng vi Pyridin / MeOH (1 : 1)

oxy ha vng cam

kh tm violet

phn bit dng oxy ha // dng kh.

(lm thuc th hin mu / SKLM).


orange


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5.7. SKLM (bn silica gel)

kho st ton b cc anthranoid trong dc liu:

- chit bng MeOH, EtOH (hay ROH + H2O)

- ly dch chit ROH chm ln bn mng

kho st cc aglycon mi sinh + c sn:- chit(+ th.phn + oxy ha) vi H2SO425% + H2O2

- lc vi CHCl3, ly dch CHCl3chm ln bn mng

kho st cc aglycon t do (c sn):

- chitbng MeOH, EtOH (hay ROH + H2O), c

- lc vi CHCl3, ly dch CHCl3chm ln bn mng


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DUNG MI SKLM ANTHRANOID

i vi anthraglycosid :

EtOAcMeOHH2O

EtOAcPrOHH2OCHCl3MeOH

i vi anthraquinon :

BzCHCl3(1:1)

BzEtOAcBzEtOAcAcOH

BzEtOAcHCOOH

BzEtOHAcOH


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HIN MU VT TRN SKLM

a. di nh sng thngb. di UV 254 / 365 nm

c. sau khi x l vi thuc th

- hi ammoniac

- KOH / ROH

- Pyridin / MeOH

- Mg acetat / ROH


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SC K ANTHRANOID T CASSIA TORA


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V tr tng i ca cc OMA trn bn Si-gel

ChrysophanolPhyscion

Emodin

Aloe emodinRhein

Acid emodic

1,8 di-OH, 3-Me1,8 di-OH, 3-Me, 6-OMe

1,8,6 tri-OH, 3-Me

1,8 di-OH, 3-CH2OH1,8 di-OH, 3-COOH

1,8,6 tri-OH, 3-COOH

Rf cao

Rf thp

COOH > CH2OH > CH3

tri-OH > di-OHtnh phn cc :


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bng ny mnh, kh c trng

nhiu trng hp : to doublet.

1630 cm1 (chelat)

1670 cm1 (t do)

Do 2 nhm carbonyl

5.8.Quang ph IR

Do cc nhm -OH

- OH 3400 cm1 (thng yu)

- OH thng rt yu, kh thy

- CO (carbinol) cho bng r rt vng 1100 cm1

O

O

OH

OH

HO....

OH

....

.... ....HO

Do vng thm :cho bng kh r vng 3000, 1570 cm1


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anthraquinonO

O

16703400


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Istizin

O OHOH

O

16303400


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alizarin

O

O OH

OH

3400


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Purpurin

O

O OH

OH

OH

3400


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Aloin

O OHOH

CH2OH

glucose

3400


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5.9. Ph UV ca anthraquinon

200 300 400 500 600 nm

220 - 260

270 - 290

430 - 440


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hRf Hp cht cc cc i hp thu (EtOH, nm)

76 Chrysophanol 225 258 279 288 432

75 Physcion 226 255 267 288 440

52 Emodin 223 254 267 290 440

36 Aloe emodin 225 258 279 287 430

24 Rhein 230 260 432

18 acid emodic 227 252 274 290 444

PHUV-Vis CAOMA

hRf trong h BzEAAcOH (75 : 24 : 01)


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6. CHIT XUT ANTHRANOID

6.1. Csl lun

6.2. Chitcc dngkh

6.3. ChitdngOxy-ha

6.4. Chitglycosid (AG)

6.5. Chitaglycon (AQ)

- AQ c sntrong dcliu

- AQ misinh tglycosid


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6.1. C S L LUN

glycosid : - kh tan / dmhc km phn cc.

- khng thng hoa c.

aglycon : - d tan/ dung mi hu c km phn cc

- kh tan / acid.

- thng hoa c

c 2 dng : - d tan trong dd. kim, ROH

- tan c / nc nng, bn nhit

- km tan / dd. NaHSO3(naphthoquinon)

6.1.1- NHC LI TNH CHT (L tnh chung)


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i tng ch yu

Dc liu mi thu

hi

cha nhiu dng kh

kch ngtiu ha

Dcliuxl(Thu hi , boqun)

chanhiudngoxy ha

glycosid aglycon

xung rut gi

AQ

xut hintc dng

b rut non

hp thu

khng cntc dng

6.1.2 C S L LUN - ng dng thc tin


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6.2. CHIT XUT DNG KH

Mang nghakhoa hc(sinh nguyn, sinh )

t mang tnh ngdngthct

Kthut: kh (v snphmkm bn)

C thchitxut,theo iukin:

- trnh nh sng (nng!)

- thchintrong kh quynN2, CO2lng

- trnh dng dung mi nhitcao

- trnh mutipxc lu visilica gel


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6.3. CHIT XUT DNG OXY HA

C nghathcthnDngOxy ha dchithndngkh.

DngAQ dchithndngAG.

nhngtc dngnhuntycaAQ


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6.4. CHIT XUT GLYCOSID

- Chit bng 1 dung mi phn cc (ROH + H2O)

- Loi cc tp cht lin quan (c bit l Tannin)

- C thu hi dung mi

- Thu c AG th ton phn + t tp

AG tinh khit

SKC


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6.4. CHIT XUT GLYCOSID

etherpetrol

benzen

methanol

dch EP

dch Bz

dch MeOH

Dl c cha sc t+cht bo

b dc liu

Cc sct, chtbo +AQ km ph.cc

cc AG phn cc


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6.5. CHIT XUT AGLYCON

a. Dng aglycon c sn / dc liu

-chit anthranoid vi cn,(hoc dung mi km phn cc)

- c thu hi cn.

- thm nc, ta AQ th

- lng, lc, thu ta AQ th

(Nu dng dm km phn cc th c n cn- Tinh ch qua ct)

- tinh ch (SKC silica gel) loi tp phn cc

hn hp cc AQ kh sch

SKC

cc AQ pure.


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b. Dng AQ mi sinh t AG

- Chit AG bng 1 dung mi phn cc

- Loi cc tp lin quan (c bit l tannin)

- Thy phn bng acid (sulfuric 20%, acetic) nng

- Tch ring phn AQ bng dm hc km phn cc

- Tip tc tinh ch (acid base; ct silica gel )

- C dung mi, thu sn phm (AQ ton phn).

- SKC cc AQ tinh khit

6.5. CHIT XUT AGLYCON


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7. PHN LP OMA

Dng aglycon : km phn cc hn dng glycosid.

d phn lp hn dng glycosid

Dng monomer : d phn lp hn dng dimer

7.1. Phng php sc k ctCt hp ph (Silica gel, Nhm oxyt)

Dung mi khai trin :

- dng AQ : dng h dung mi km phn cc

- dng AG : dng h dung mi phn cc hn


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7.2. Thay i pHAG ton phn

dch thy phn

i hong

tp phn cc

Rhein

Emodin

chrysophanol

NaHCO35%

Na2CO35%

NaOH 5%

H2SO425%,

tnh acid

(+++)

(++)

(+)


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8. NH LNG OMA

8.1. Phng php cn (Deals Kroeber)

8.2. Phng php so mu (Auterhoff)

8.3. Phng php th tch (Tschirch - Schmitz)

8.4. Phng php to phc mu, o quang

8.5. Phng php SKLM

8.6. Phng php HPLC

8.7. Phng php sinh vt

8 NH LNG OMA


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8.1. Phng php cn (Deals Kroeber)

- Thy phn AG bng H2SO425% nng

- Tch ring AQ (c sn + mi sinh) bng CHCl3- Loi tp (naphthoquinon . . .) vi NaHSO3tha

- Loi NaHSO3tha bng HCl long

- Bc hi dung mi CHCl3n cn, sy 60OC 80OC

- Cn, tnh hm lng %

Nguyn tc

8. NH LNG OMA

8 NH LNG OMA


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8.2. Phng php so mu (Auterhoff)

Nguyn tc- Va thy phn (vi AcOH bng)

va chit AQ (vi Et2O) trc tip t bt dc liu

- Dch Et2O c lc vi kim (NaOH + NH4OH)- Lp kim () cha AQ c o Abs (= 540 nm)

- So snh vi ng cong chun :

* istizin hay chrysophanol / (NaOH + NH4OH)* CoCl2. 6H2O / H2O

- Suy ra hm lng AQ / mu

8. NH LNG OMA

8 NH LNG OMA


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Ch trong phng php so mu (Auterhoff)

Cc dn cht kh vng / mi trng kim

(cn tr s o mu) cn Oxy ha (BM 20),

ngui ri mi o quang.

Hiu kt qu trc v sau khi BM [dn cht kh ].

mun xc nh hm lng aglycon c sn / dc liu

chit ngay bng dung mi hu c km phn cc

(khng cn thy phn bng AcOH bng)

8. NH LNG OMA

8 NH LNG OMA


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8.3. Phng php th tch (Tschirch - Schmitz)

AQ

KOH 0,1 N tha

HCl 0,1 N

- bn thn AQ l ch th mu ( / kim; vng / acid)

- sai s tha do polyphenol (ch yu do Flavonoid)

Ch

8. NH LNG OMA

8 NH LNG OMA


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8.4. Phng php to phc mu viMg acetat 0,5% /MeOH, o quang

- chit AG bng nc nng + NaHCO3.

- oxy ha + thy phn (= FeCl3+ HCl) nng AQ

- chit AQ t do bng Et2O.

- cn Et2O + Mg acetat 0,5% / MeOH mu

- o quang 515 nm (mu trng = MeOH)

- [anthranoid] / mu

(thng p dng / i hong, kt qu quy v Rhein)

8. NH LNG OMA

8 NH LNG OMA


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8.5. Phng php SKLM

S T

Nguyn tc :

trn cng 1 bn mng,

chm ng th tch chun (S) // th (T)

So snh (S) v (T) v

- din tch vt,- cng mu (c / khng th th)

Suy ra [C] c trong mu th.

Mc ch : Bn nh lng // chun

8. NH LNG OMA

8 NH LNG OMA


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8.6. Phng php HPLC

Tin cy, thng dng.

Nguyn tc : Trong cng 1 iu kin,

chun (X) v (X/mu) peak c cng thi gian lu.

[X] s t l thun vi S (din tch peak).

bit nng chun, t S o c (X) v (X/mu)

[X]% trong M

8. NH LNG OMA

8 NH LNG OMA


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Phng php HPLC

mu th M (cha X)

chun X

XT

XC

ST

SC

tRXTX

C

ST=

SCpht

8. NH LNG OMA


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9 TC DNG SINH HC CA OMA


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9. TC DNG SINH HC CA OMA

9.1. Ca nhm 1,2 di-OH AQ

Ch yu : cht nhum mu. Cc cht thng dng :

alizarin *, purpurin *,

acid carminic, carminacid kermesic, acid laccaic A, B, C, D.

acid ruberythric

mt s : Khng khi u (antitumor)

Damnacanthal, nor-damnacanthal trong Morinda.

9 TC DNG SINH HC CA OMA


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dng AG (ch yu l cc -glucosid)

- khng b chuyn ha ti rut non.

- ti rut gi : b thy phn AQ (dng oxy-ha)

- tip tc b kh anthron, anthranol (c hot tnh)

- lm tng nhu ng c trn nhun ty

dng AQ : b hp thu rut non khng nhun ty.

9.2. ca nhm 1,8 di-OH AQ

9. TC DNG SINH HC CA OMA

TC DNG DC LC CA OMA


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AQ bhp thu !

NHUNTY

AQ gykch ng!

AG AQ

dng kh

mt tnhnhun ty

9 TC DNG CA OMA


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9. TC DNG CA OMA

Tngnhu ng rut v co bp c trn ( bng quang, tcung . . .)

tc dng chm (ung : sau 610 h) : nhun x ty

ph tr iu tr si thn (liu trung bnh !)

bi tit qua phn, nc tiu, sa, m hi (nhum mu)

trnh dng lu di (l thuc thuc, gim Kali-huyt)

khng dng cho ph n c thai, cho con b . . .

khng dng liu cao i vi ngi c si (gan mt, niu)thn trng : ngi gi, tr nh, bnh tr

mt s c tc dng khng nm da (hc lo), thng mt

mt s c tc dng iu ha / kch thch min dch (aK)

PHN B TRONG T NHIN


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PHN B TRONG T NHIN

a. Trong cn trng, thc vt bc thp : t

b. Trong thc vt bc cao : chim i a s

b1. Lp 1 l mm : Asphodelaceae (chi Aloe)

b2. Lp 2 l mm : kh hp, ch yu :

- Rubiaceae (chi Rubia, Morinda)

- Fabaceae (chi Cassia)

- Polygonaceae (chi Rheum, Rumex)

- Rhamnaceae (chi Rhamnus) . . .


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Dai Cuong Anthranoid