TRNG I HC CN TH KHOA S PHM B MN HA

Gio vin hng dn:

Th.s: GVC NGUYN VN HNG.

Nhm sinh vin thc hin:

PHAN PHI HNG

HUNH VN T NGUYN MINH THNG

L TH HNG
L TH NHT HNG L NHT TRNG.

Steroid c nhiu trong thin nhin v chng to thnh mt nhm hp cht phn phi rng khp trong ng thc vt . Chng bao gm :
Cc sterol c ngun gc thc vt gi l phytosterol. I-Sterol Ngun gc ng vt gi l zoosterol. Ngi ta thy chng th t do hoc th ha hp nh ester,glycosid. Cc thnh phn chit xut t t nhin ny rt phc hp v th c II-Axit mt nhng phng php phn tch thch hp phn lp tng cht.

Cc hormon trong c th ngi ,v trong cc ng vt khc cng cthngcu .Sinh t D cng l mt hp III-V tuyn nghin thn cht steroid. Acid mt c phn tch t mt ca ng vt .Ngoi ra gn yIV-Hormon gii tnh v mt s Hydrocacbon ngi ta cn tm hiu steroid c tnh gy ung th. Cc steroid c tc ng c bit i vi c tim thng tn ti di dng glycosid trong t nhin gi l glycosid tr V-Sinh t D tim. Cc sapogenin steroid phn lp ch yu t s phn glycosid thc vt cn gi l saponin. VI-Sapogenin

Steroid l nhng hp cht thin nhin c chung c im cu to phn t c cha h vng cyclopentanoperhyrophenantren. Hoc trong trng hp rt him l dng bin i ca h vng 1- Cu trc c bn ca khung : cyclopentanoperhyrophenantren.
Trong qu trnh kh cc sterol bng cch un nng vi selen 3600C chng u to ra hydrocacbon Diels C18H16 (rn,nng chy 126-1270C) v mt s sn phm khc .V mt s phn tch v nguyn t, phn tch tiaX ,ph nghim,.. Cho cht l. 3-metyl1,2-ciclopentanophenantren. a s hp cht steroid khi un vi Selen 3600C to ra hp cht 1,2ciclopentenophenantren
4

CH3
3 2 1

3
2 1

Sterol

Se, t0

5 6 7 8 9 4 5 6 7 8 9 10 10 3 2

2 1

Steroid

Se

,t0

Mt khc Steroid

Se ,t0 4200C Chrisen

+
Picen (sn phm ph)

T nhng thc nghim trn ngi ta thy khung sn c bn ca steroid l cyclopentanoperhyrophenantren.

Sn phm a vng thm

2- Ha hc lp th v danh php ca Steroid.

Cu hnh ca steroid thng c xt theo 2 yu t : a) Cu hnh ca nhn c bn : *Cu hnh cc vng kt hp ca nhn c bn *Cu6hnh cat cacbon th tch bit v tr C13 v C17 -C nguyn cc nhm th c .a snhn(5,8,9,10,13,14) do c trong cc steroid c hydroxy ha C3, c nhm th metyl 6=64 ng phn C17 hc. th c 2 C10 ,C13 v dy quang
13 10 9 8 5

14

Xt nhn cyclopentanoperhyrophenantren. ,gi cc vng theo th t l vng cyclohexan A,B,C vng cyclopentan D. Php phn tich tia X cho thy phn t steroid di v mng,u ph hp vi R R H cu hnh vng Bv CH v tr trans vi nhau ,cn A/B,C/D c th cis hoc trans. Tt c cc steroidD bo ha tm thy trong thin nhin thuc 2 loi Cholestan v D C C Coprostan . Khung Cholestan l s kt hp A/B trans,B/C trans,C/D trans c B gi lAallo.Khung Coprostan l s kt hp A/B cis ,cc vng B khc l trans A
H R H H H R

Acid c c sau khi oxy ha hp cht c khung cholestan gy t mch nhnh ti C24 gi l acid allocholanic ( c im nhn dng nhanh l nhm metyl gc C10 v H C5 c cu hnh trans vi nhau ,do A/B trans) Cn acid tng ng vi cu hnh A/B cis tc l khung coprostan gi l acid cholanic (ch khng gi l acid coprosic). So vi 2 gc ni trn ,nu gim 1C trong dy ankyl th gi thm tip u ng nor ,gim 2C th gi thm bisnor
COOH COOH C A B D COOH COOH

Cholestan
H

Acid allocholanic(A/B cu hnh trans )

COOH

COOH

Acid cholanic (vng A v B cu hnh trans vi nhau)

H H

Acid norallocholanic.

Acid Binorallocholanic.

b) Cu hnh cc nhm th .
-Khi nhm OH ti C3 trn mt phng ca vng ,c ngha l v tr cis i vi nhm CH3 C10 cht thuc nhm .Trng hp ny thng gp trong cc sterol t nhin .
C10H19 HO

-Khi nhm OH ti C3 di mt phng ca vng , c ngha l v tr trans i vi nhm CH3 C10 cht thuc nhm hay cn gi l epi .
C10H19

HO

KL: Do steroid l mt tp hp nhiu loi nhm cht thnh vin nh th nn chng ta s ln lt phn tch v xem xt ha tnh ca tng nhm.

Sterol th rn c ngun gc ng vt hoc thc vt,cu trc 27-29 nguyn t C,nhng u c khung sn c bn l cyclopentanoperhyrophenantren. V mt nhm th ankyl mch nhnh C17..Chng c tm thy trong ng vt c xng sng,khng xng sng v sau tm thy trong thc vt. Nhm sterol ng vt (zoosterol ):Cholesterol , Cholestan-3ol,Coprostan--ol, Desosterol,Coprosterol,Cerebrosterol,Lathosterol. Nhm sterol ca ng vt bin khng xng sng: Spongesterol,Clionasterol,24-methylencholesterol,Fucosterol. Nhm sterol thc vt (phytosterol): Sistosterol (c cc ng phn ,,y) ,Stigmasterol, -Spinasterol, Brassicasterol.Cc sterol thc vt c trong tt c cc b phn ca cy nhng nhng nhiu nht cc ht c du ,di dng t do hoc eter.Mt s t dng glycosid. Nhm sterol nm men: Ergosterol,Zymosterol,Acosterol,Fecosterol (th yu )

Cu trc phn t ca cc sterol v cc dn xut .

Cc sterol u c nhm hydroxy C3,nhm th metyl C10 v C13 , v dy cacbon C17

C8H7 HO

Cholesterol
Sterol c dy ni i C=C gi l stenol

C8H7

HO
Sterol bo ha hydro gi l stanol

Cholestanol

Mt s sterol c nhm metyl C4 hoc C14 gi l metylsterol

Cng thc phn t : C27H46O . Trong phn t c 8C* . im nng chy 1490C (k thng)
L cht bo c phn t lng ln ,c c lp t phn khng b x phng ha ca cht bo du m .Cholesterol tm thy trong c th ng vt c xng sng ,c t bo no,ty sng ,thng dng t do hoc ester.
C8H17
HO Cholesterol
+ H2 Pt,t0

V mt lp th ,v tr ng/t H ca cholestanol di mt phng . P/ng c s la chn lp th ,u tin cng pha HO di nhm OH c li v mt nng lng
Oxy ha CrO3

C8H17

Cholestanol

C8H17 HO
Xu hng cng c li v mt nng lng C8H7

Cholestenol O Cholestanon C8H17

HO

Kh nhm cacbonyl,
Epi cholestanol
Sn phm cng chnh

Ergosterol

Tm thy trong men

Cng thc phn t l C28H44O : c 1 nhm OH ti C3 ; 2 ni i gia C5=C7 v C7=C8 .2 nhm CH3 ti C10 v C13 ; 1 dy hydrocacbon C9H17 ti C17 . *So vi cholesterol th hp cht ny c thm 1 nhm metyl C24 ca dy nhnh ngoi vng ,cc hp cht c cng c im cu trc vi nhnh nh vy gi l nhng hp cht loi ergosterol . To nng chy 1630C (k thng)
24

C9H17 HO

C A B

Erogosterol
L sterol thc vt ,c lp t du u nnh v nhiu loi thc vt khc .Cng thc phn t C29H48O : c mt nhm OH ti C3 ; 2 ni i gia C5=C6 v C22=C23 ,2 nhm th -CH3 ti C10 v C13 ; 1 dy hydrocacbon C10H19 ti C17 .

HO

Stigmasterol
So vi cholesterol hp cht ny c thm 1 ni i C22 v mt nhm etyl v C24 . Nhit nng chy 1700C (k thng)

C10H19
C

HO Stigmasterol

A
HO

Ha tnh c bn ca sterol

Ni chung vi khung sn c bn ging nhau, cc sterol u cho phn ng:

Vi H2 / Pt , t0 bo ha ni i trong phn t v phn ng c chn lc lp th,(cng tri pha vi nhm OH ) trong mi trng trung tnh(etanol). Din tin ngc li trong mi trng acid. Vi CrO3 : -Oxy ha nhm OH th C3 thnh =O , mi trng trung tnh(trong aceton) -Oxy ha to ceton v t dy ankyl nhnh ra khi nhn .mi trng acid acetic , t0. -Oxy ha v t mch C=C to acid , ceton . Khi mt p/ng c acid , t0

Phn ng ozon gii : gim cp to sn phm cacbonyl do t ni C=C .

Phn ng gim cp C so vi acid gc( acid allocholanic,acid cholanic l sn phm ca s oxy ha cholesterol, coprosterol) gi l p/ng Barbier Wieland.

CHIT XUT V PHN LP STEROL.

c tnh ca sterol l khng phn cc ,nn rt km tan trong nc nhng tan trong du bo v cc dung mi hu c khng phn cc nh eter, du ha,vebzen,cloroform,acetonnn dng cc cht ny chit chng.(i vi cc sterol glycosid c th chit bng etanol) Sn phm chit bng dung mi hu c thng l hn hp ca sterol v cc cht bo ,cc cht km phn cc khc trong nguyn liu nh : lipid (/v zoosterol),caroten, leucytin,(/v phytosterol). Phi thc hin phn ng x phng ha tch cc cht ny ra khi sterol,sau chit sterol bng dung mi hu c.Thc hin sc k ( ct,bn mng ,giy ..) phn lp hoc kt tinh phn on tinh ch sterol. Cc phn ng nh tnh sterol v steroid thng dng l : Phn ng lierberman Burchard : -Thuc th : 1ml Ac2O ,1ml CHCl3 lnh 00C ,thm vi git H2SO4 . -Cch th : mu th l dnh chit ha tan trong cloroform cho vo vi git thuc th pha sn nh trn ,nu xut hin mu xanh lc,hng ,cam, v mu bn l phn ng dng tnh . Phn ng Tortelli-Jaffe : Ha tan 0,5mg cht th vi 0,2ml acid acetic v 11 git Thuc th dng nhn din sterol ,d vi lng rt nh khi phn tch sc k cc cloroform ,cho vo ng nghim .Cho dc thnh ng nghim vi git dung dch Brom ha thuc th ny sau khi phun ln mu sc k ,un nh s hin mu ca vt. trong cloroform .Nu c sterol vi 1 ni i s xut hin vng mu lc gia 2 lp cht Dung dch SbCl2 10-20% trong cloroform lng.

Dung dch H2SO4 20% pha trong etanol hoc dung dch H2SO4 : H2O = 1:1

S RA I CA PROTEIN MI NH S KCH THCH CA STEROID CUNG CP VO C TH

S lk ca hocmon s n C quan cn.

T bo cht

S dc ca c quan cm nhn mng li n TT

Dch chuyn

C quan cm nhn

X gene iu tit

Sao chp S lk ca cc mng li n v tr gene t

gan

Lng trng

Ton b tch sa

Lp vn

Hy thn trng hn trong khu phn n ca mnh v c th cc bn s lm tng lng cholesterol trong c th vt qu mc cho php th s nh hng khng tt n sc khe