Nhng hiu bit v Alcaloid c cu trc steroid

I.Khi qut v Alcaloid:

1.nh ngha: - Alcaloid l nhng hp cht hu c cha nit, cacbon, hyro, oxy v thnh thong cha lu hunh c trong thc vt, a s c nhn d vng, c tnh cht baz, c phn ng kim, cho cc mui vi cc axit v cc mui ny d kt tinh, c hot tnh sinh hc v c mt s phn ng chung l to ta. 2.Alcaloid trong thc vt: Alcaloid c nhiu trong cy c hai l mm c bit l h : A phin, c ph, m tin, c, trc oAlcaloid khng ph bin nm, a y, cc cy mt l mm. Alcaloid tn ti trong thc vt dng mui vi cc axit hu c nh axit malic, axit xitric, axit oxalic v cc axit c hiu cho tng loi alcaloit. Alcaloid khng c trng cho mt h thc vt no v ngi ta thy mt alcaloid c th c trong nhiu cy thuc nhiu h khc nhau. Mt cy cng khng c trng cho mt alcaloid no.Chng hn: cy ba gc c ti 40 alcaloid khc nhau, hay cy da cn c 72 alcaloid. Alcaloid khng tp trung trong tng b phn ca cy m nhiu b phn khc nhau nh hoa, qu, l, v v phn b khng u nhau.Chng hn: quinin c nhiu trong v cy canhkina, cocain c nhiu trong l coca Thnh phn v s lng ca alcaloid thay i theo thi gian trong nm, theo cc giai on pht trin ca thc vt, v theo iu kin t ai, cch trng trtc bit nhng cy c hm lng alcaloid cao thng gp vng nhit i. 3.Phn loi alcaloid: - Trc y ngi ta chia alcaloid thnh 2 loi: + Loi 1: Alcaloid khng c oxi + Loi 2: Alcaloid c oxi - Ngy nay, theo cu trc ca nhn m ngi ta phn loi cc alcaloid: a. Alcaloid khng c nhn d vng
OH NH
HO H3C N CH3

CH3

H3C

Hordenin C10H15NO (c trong mch nha)

Ephedrin C10H15NO (c trong ma hong)

b. Alcaloid l dn xut ca nhn pyrol

H N

O N CH3 CH3

Pyrolidin C4H9N (c trong c rt )

Hygrin C8H15NO (c trong l coca)

c.Alcaloid l dn xut ca nhn pyridin

O O N CH3 CH3

N H3C
Nicotin C10H14N2 (c trong thuc l)

Arecolin C8H13NO2 (c trong ht cau)

d.Alcaloid l dn xut ca nhn indol

N

Strychnin C21H22N2O2 (c trong m tin)

N O H

e. Alcaloid l dn xut ca nhn tropan

H N

OH

O O

Atropin C17H23NO3 ( c trong Atropan beladoza)

f.Alcaloid l dn xut ca nhn imidazol

g.Alcaloid l dn xut ca nhn purin

H3C N N H3C O N N CH3 O

O H3C N O N CH3

H N N

Cafein C5H2(CH3)2N4O2 (c trong ch, c ph) h.Alcaloid l dn xut ca nhn quinolin

Theophyllin C5H2(CH3)2N4O2 (c trong ch)

OH HC OH3C N HN HN CH N CH2

Quinin C20H24N2O2 ( c trong v canhkina)

i.Alcaloid l dn xut ca nhn isoquinolin

O O

CH3O OH3C

Berberin C20H19NO5 (c trong hong lin gai)

N CH3

j.Alcaloid l dn xut ca nhn phenanthren

CH3O

OH 3C

Thebain C19H19NO3 (c trong thuc phin)

k. Alcaloid c nhn sterol l. Alcaloid c cu trc tecpen

II. Alcaloid c cu trc steroit:

1.Cu trc Steroid: Cc alcaloid c cu trc steroid c nhiu trong nhin nhin nh sterol, acid mt, glycosid tr tim, nha c ca con cc, v cc sapogenin Cc alcaloid ny cha h vng cyclopentanoperhydrophenanthren hoc trong trng hp rt him dng bin i ca h vng . Cc alcaloid c cu trc steroit th t do hoc th ho hp nh ester hoc glycosid. Chng thng dng phc hp, cc thnh phn trong rt kh phn tch. Cc alcaloid c cu trc steroid khi un nng vi selen 360oC to ra hp cht 1,2xyclopentenophentren Chnh v vy , khung c bn ca steroid l xyclopentanophenantren bao gm vng xyclohecxan A, B, C v vng xyclopentan D. 3 3' 2 4 2' 5 1 6 S e 1' Steroid 3 6 0 7 C 10 8 9

S
Steroid

e 2 0 C

+
H3C 3 4 5 2

2.Phn loi : - Bao gm cc loi chnh sau: Sterol - Sterol c trong ng vt c xng sng, ng vt khng xng sng v cy. - Qu trnh kh cc sterol bng cch un nng vi selen 360oC u to ra hyrocacbon C18H16(rn, nng chy 126-127oC) v mt s sn phm khc. C th l :

3'

2' 1'

S
Sterol

e 7

6 7 C 8

1 Picen(sn phm ph) 10 Chrisen 9

2- 1 6 2

3'- metyl-1,2 xyclopentanophenatren

H3C

a.Sterol ca ng vt bin khng xng sng : - Trong sterol ca ng vt khng xng sng, chui bn 8 carbon ca cholesterol c thay bng mt n v c 9 carbon vi nhnh methyl hoc bng mt n v 10 carbon vi nhm ethyl. Nhng sterol ca ng vt bin in hnh : spongesterol, clionasterol, 24 methylencholesterol, fucosterol. Clionasterol

CH3 CH3 CH3

C24

H H H HO H H

b. Sterol thc vt: - Sterol thc vt cng c chui bn, C9 hoc C10. Cc steroid thc vt c trong tt c cc b phn ca cy nhng nhiu nht cc ht c du di dng th do hoc eter. in hnh l sitosterol, stigmasterol,
H

CH3 CH3 H CH3 H H H

H H

Beta- Sitosterol
HO

c.Sterol nm men: - in hnh ca dng ny l :ergosterol, zymosterol Ergossterol

H3C CH3

CH3 H3C CH3 CH3

HO

H3C CH H3C CH3

CH2

CH2

CH3 CH3

Acid mt - Acid mt c phn tch t mt ng vt bc cao, chng dng mui natri ca cc kt hp peptidic vi taurin v glycin. - Acid mt c 2 lp chnh : Acid C 27-28 v acid Cholesterol C24
HO

CH2 HC

- Acid mt c to nn trong gan t cholesterol Glycosid tr tim - C hai loi l cardenolid v bufadienolid +Cardenolid l steroid C23 c chui bn l mt vng , lacton 5 cnh, khng no v 1 nhm C14 hydroxyl .in hnh l strophanthidin, oleandrigenin, sarmentogenin Strophanthidin
O

O O

H H

OH

HO
O OH O

+Bufadienolid l sterolid C24 c mt chui bn l vng lacton 6 cnh, hai dy ni khng no v mt nhm hydroxyl 14 hoc l nhm tng t c thay i mt t. in hnh l bufalin, marinobufagin Bufalin
HO

HO H3C H H H CH3

Sapogenin - Sapogenin l nhng glycosid ca cy, chng c tnh cht to bt x phng vi nc . in hnh l digitonin
HO H3C H HO

H3C H3C H H OH H

CH3

O H

CH3

3.Tnh cht vt l : Cc alcaloid c cu trc steroid thng th rn v kt tinh Cc baz ca chng t tan trong nc nhng tan trong dung mi hu c nh benzen, eter, cn, chlorofoc.Ngc li cc mui ca chng t tan trong dung mi hu c li tan nhiu trong nc. Mi alcaloid u c im nng chy v nhit si khc nhau Ngi ta dng quang ph t ngoi v hng ngoi xc nh cu trc ca chng. V phn ln chng c nng sut quay cc, l hng s quan trng kim tra tinh khit. Dng L c tc dng v mt sinh l r rt so vi dng D. 4.Tnh cht ho hc:

 Phn ng vi H2, to: mi trng trung tnh (etanol) Phn ng vi CrO3 : +Oxy ho nhm OH th C3 thnh = O, mi trng trung tnh (aceton) +Oxyl ho to ceton v t dy ankyl nhnh ra khi nhn, mi trng acid acetid, to +Oxyl ho v t mch C=C to acid, ceton, mi trng acid, t Phn ng ozon phn : gim cp to sn phm cacbonyl do t ni i C=C Phn ng gim cp C so vi acid gc(acid allocholanic, acid cholanic l sn phm ca s oxy ho cholesterol, coprosterol) gi l phn ng Barbier Wieland. 5.Phng php xc nh : - Yu cu: Xc nh khung cacbon. Cc nhm ho chc c trong alcaloid. c trng ca nhm amin c trng ca nhm cha oxi - Nghin cu yu cu gm cc bc Bc1: Thng dng phng php oxi ho phn ly tng phn phn t alcaloid Bc 2: Nghin cu cc sn phm ng v. Bc 3: Ri trn cc s liu m d nh cu trc phn t ca cc alcaloid Bc 4: Tng hp li alcaloid l cu trc ho hc ng n ca n. - p dng yu cu v cc bc nghin cu xc nh cc alcaloid bng cch chit xut: Chit xut cc alcaloid dng baz: o Dc liu tn nh cho tc dng vi kim yu nh NH4OH hay NaHCO3( nu s dng kim mnh c th mt s alcaloid c cu to este s b phn hu ) o Chit bng dung mi huu c v hn hp alcaloid di dng baz v cc tp cht s tan trong dung mi hu c. o Tinh ch cc alcaloid y bng cch chuyn cc alcaloid baz thnh mui. Tch mui khi dung mi hu c, lc cc tp cht s li trong dung mi hu c. o Sau chuyn cc dng mui thnh dng baz, ri li chit cc baz bng dung mi hu c. o C tip tc nh vy nhiu ln cho n khi thu c baz tng i tinh khit. Chit xut cc alcaloid di dng mui: o Dc liu tn nh cho tc dng vi acid v c hay hu c o Chit bng nc hay cn, lc ny cc alcaloid di dng mui v cc tp cht (nha, protit, cht ng) s ho tan trong dch chit o tinh ch cc alcaloid th trc tin chuyn chng thnh dng baz bng cch cho dch chit acid tc dng vi kim.Ri dng cc dung mi hu c thch hp chit ring cc alcaloid baz. o Tip tc loi hp cht bng cch lc cc dung mi hu c vi dung dch acid.Lc ny cc alcaloid baz li bin thnh mui v cc mui ny li tan trong dung dch nc acid, cn cc tp cht li trong dung mi hu c. o Tch ring dung dch nc acid c cha cc mui alcaloid v lm kim ho, ri li chit cc alcaloid baz bng dung mi hu c. o Cui cng cho bc hi dung mi h c ta thu c cc alcaloid. - Ngoi ra xc nh cc alcaloid ngi ta dng phn ng gy ta v phn ng mu c hiu: Phn ng gy ta l cc phn ng to hp cht khng tan trong nc khi cho tc dng vi cc thuc th nh mui kim loi nng, cc phc ioua, cc phc acid

Dung dch tanin : Trong mi trng trung tnh v acid cho kt ta hi vng v dung dch cc mui alcaloid . Dung dch iot trong kali ioua Loi ny gm cc thuc th Busacda, Vacgne, Lugol, chng khc nhau v nng ca iot v kali ioua. Thuc ny cho ta xm nu vi cc dung dch mui alcaloid acid ho. I2KI KI3 Dung dch thu ngn ioua trong kaliioua Thuc th Maye.Thuc th ny cho ta trng hay hi vng vi cc alcaloid trong dung dch acid hay trung tnh.Tr cafein v colchicin khng cho phn ng: HgI2.2KI K2HgI4 Dung dch acid picric1% trong nc Thuc ny cho kt ta mu vng di dng picrat vi tt c cc alcaloid tr cafein, colchicin, morphin, nicotin, v theobromin. Phn ng mu : L nhng phn ng dc hiu xc nh tng loi alcaloid, thng dng dng cc loi acid sau: Thuc th Frt (Frode): ch yu l cha acid sufuric c Thuc th Ecman(Erdman): hn hp acid sunfuric v acid nitric c. Thuc th Macki:gm acid sunfuric c v formol Thuc th acid sufurric c Thuc th nitric c. 6. Phng php sn xut: a. Phng php cn : - Dch chit vo bnh d cn sn, cho bc hi dung mi. - Sy cn cho n trng lng khng i. - Lm lnh ri cn. - tnh trng lng ca mui da vo trng lng ca alcaloid baz. b. Phng php th tch: - Chun cc alcaloid baz th tin hnh nh sau: Sau khi cho bc hi dung mi th cho qu tha dung dch acid chun vo, ri nh lng acid th bng dung dch kim vi phenol phtalien. - Chun cc mui alcaloiid c th bng kim vi phenol phtalein. Mu s xut hin khi tt c cc baz c y khi mui kt hp vi kim chun cho thm. c. Phng php ho l: - Phng php ho l nh phng php o quang lng cc alcaloid. 7. Cng dng ca cc ancaloit c cu trc steroit: a. Tc dng trn h thn kinh trung ng: - C cc cht gy trm ut nh morphin, codein, scopolanin, reserpin. - C cc cht lm kch thch nh strychnin, cafein, lobelin. b. Tc dng trn h thn kinh t ch: - C cht kch thch giao cm ephedrin, hordein. - C cht gy lit giao cm: ergotanin, yohimbin.

- C cht kch thch ph giao cm: pilocpin, eserin. - C cht lm lit ph giao cm: eyxoiamin, tropin. - C cht phong b hch giao cm: nicotin, spartein, xicutin. c. Thuc gy t, tr co git: - Gy t ti ch: cocain. - Gin c: d-tubecurarin. - Tr co git: papaverin. d. Thuc tc dng trn tim: - C anpha fagarin, ajmalin v quinidin l thuc chng rung tim. - Quinin, emetin c tc dng gy trm ut. e. Thuc huyt p: - Gy tng huyt p c ephedrin, hydrastin. - Gy h huyt p c alcaloid ca cy ba gc. f. Tc dng trn vi khun, k sing trng. - Nhiu alcaloid ch c tc dng dit vi khun liu cao. - Tr k sinh trng st rt c quinin. - Tr l amip c emetin, conexin. - Tr giun sn c: phelentierin, arecolin