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BI GING

HA HC CC HP CHT THIN NHIN


i tng: CN Ha hc
GVGD: ThS. Phm Th Chnh
B mn Ha hu c Khoa Ha hc H Khoa hc
H Thi Nguyn
NI DUNG
Chng 1: Phng php nghin cu
Chng 2: Cacbohidrat
Chng 3: Tecpenoit
Chng 4: Steorit
Chng 5: Flavonoit Chng 5: Flavonoit
Chng 6: Ancaloit
CHNG 1
PHNG PHP NGHIN CU
1.1 Lch s v i tng nghin cu
1.2 Phn loi cc hp cht thin nhin 1.2 Phn loi cc hp cht thin nhin
1.3 Sinh tng hp cc hp cht thin nhin
1.4 Qui trnh nghin cu cc hp cht thin nhin
1.1 Lch s v i tng nghin cu
- Ha hc cc hp cht thin nhin hnh thnh t cui th k XIX
- i tng nghin cu cc lp cht ha hc ca sinh vt
Phn lp, nhn dng, nh c im
-Nhim v
Xc nh cu trc
Tng hp cc hp cht phn t nh
Nghin cu hot tnh sinh hc
Nghin cu chuyn su
Xut pht
-Nhim v
Phn lp, nhn dng, nh c im
Xc nh cu trc
Tng hp cc hp cht phn t nh
Nghin cu hot tnh sinh hc
1.2 Phn loi cc hp cht thin nhin
Phn loi
Hp cht s cp
Phn loi
Hp cht th cp
Hp cht s cp
Protein
Cacbohidrat
Protein
Lipit
Axit Nucleic
Lipit
Axit Nucleic
Lipit
Axit Nucleic
Hp cht th cp
Protein
Tecpenoit
Steorit
Lipit
Axit Nucleic
Lipit
Axit Nucleic
Ankaloit
Flavonoit
1.3 Sinh tng hp cc hp cht thin nhin
CO
2
+ H
2
O
quang hop
Cacbohidrat
COOH
OH
OH
HO
shikimic
OH
COOH
O
CH
2
COOH
chorismic
Tanin
amino
axit thom
axit
nucleic
PO
4
3-
phenylpropan
CH
3
COCOOH
axit pyrovic
shikimic
chorismic
CH
3
COOH
axetic
axit bo
polyketides
CH
3
C
OH
CH
2
COOH
CH
2
CH
2
OH
axit Mevalonic
tecpen
steroit
protien
polipeptit
ancanoit
Purines
amino
axit
N
2
chu trnh axit citric
axit thom
1.4 Qui trnh nghin cu cc hp cht thin nhin
CHNG 2
CACBOHIDRAT
2.1 i cng v cacbohidrat
2.2 Monosaccarit 2.2 Monosaccarit
2.3 Oligosaccarit
2.4 Polysaccarit
2.1 i cng v cacbohidrat
Khi nim: Cacbohidrat hay cn gi l saccarit,
gluxit, l cc hp cht hu c khng mu, t nhiu
c v ngt, d tan trong nc, d kt tinh, c tm
thy trong thc vt, ng vt, a s c cng thc
chung C
n
(H
2
O)
m
. chung C
n
(H
2
O)
m
.
Ngoi ra theo ngha rng cacbohidrat c c N,
S v khng phi u c v ngt.
Tn gi cc !ng ring bit kt thc b"ng
ui oz (ose)
Phn loi: da theo thnh ph#n v tnh cht ca
cacbohidrat
Cacbohidrat
Cacbohidrat n gin hay
monoscarit (khng th thy
phn c).
VD: glucoz, riboz, fructoz...
Cacbohidrat phc
tp khi thy phn
hon ton cho cc
monosaccarit.
Oligosaccarit to nn t 2 -10
phn t monosaccarit.
VD: Saccaroz, lactoz.
Polysaccarit (glycan) to nn
t ln hn 10 n hng vn
monosacarit: tinh bt,
xenluloz, glycogen
-Chc nng:
+ Lm nhin liu cung
cp ti 60% n$ng lng cho c
th sng.
+ Lm khung cu trc v
v bo v, th!ng c mt % cc
vch t bo vi khu&n v thc vt vch t bo vi khu&n v thc vt
c'ng nh % m ni v v bo v
ng vt.
+ Lin kt vi protein v
lipit mng, ng vai tr lm
phng tin vn chuyn tn hiu
gia cc t bo.
2.2 Monosaccarit
2.2.1 Phn loi
-nh ngha: Monosaccarit l hp cht polyhidroxicacbonyl,
phn t c nhiu nhm OH % cc nguyn t cacbon k nhau.
VD: glucoz, fructoz, riboz
CH
2
OH
CH
OH
CH
OH
CH
OH
CH
OH
CHO CH
2
OH
CH
OH
CH
OH
CH
OH
C CH
2
OH
O
CH
2
OH
CH
OH
CH
OH
CH
OH
CHO
CH
2
OH
CH
OH
CH
OH
CH
OH
CH
OH
CHO CH
2
OH
CH
OH
CH
OH
CH
OH
C CH
2
OH
O
-Phn loi
Monosaccarit
-Da theo nhm C=O:
+ C=O l andehit: andoz
+ C=O l xeton: Xetoz
- Da theo s nguyn t C:
+ 2C (bioz), 3C (trioz),
4C (tetroz) 5C (pentoz), + C=O l xeton: Xetoz 4C (tetroz) 5C (pentoz),
6C (hexoz), 7C (heptoz)
- Andoz
- Xetoz
CH
2
OH
CH
OH
CH
OH
CH
OH
CH
OH
CHO
CH
2
OH
CH
OH
CH
OH
CH
OH
C CH
2
OH
O
2.2.2 Cu hnh ca monosaccarit
a, Cng thc Fisher
Qui nh cch vit cng thc hnh chiu fisher ca cc
monosaccarit:
- Nhm c nguyn t cacbon s oxi ha cao n"m trn
(nh ca trc th)ng ng (b*c-nam) (v tr s 1).
- Nguyn t cacbon bt i (C
*
) khng vit ra m
chnh l giao im ca cc trc th)ng ng v n"m ngang.
- Cc nguyn t H v nhm OH n"m % cc trc ngang
(trc ng-ty) (nguyn t H c th khng vit ra).
VD: Biu din phn t glucoz b"ng cng thc chiu
Fisher
Nhm nguyn t
cacbon c s oxi
ha cao
Nguyn t
cacbon bt
i C
*
b, Cu hnh tng i D,L
- xc nh cu hnh tng i D,L ca cc monosaccarit
ng!i ta xt cu hnh ca nguyn t cacbon chiral (C
*
) n"m
xa nhm cacbonyl nht (C4 % pentoz, C5 % hexoz). Sau
so snh vi cu hnh ca C
*
trong phn t glyxerandehit.
+ C cu hnh D khi OH n"m % bn phi ca cng
thc chiu Fisher. thc chiu Fisher.
+ C cu hnh L khi OH n"m % bn tri ca cng thc
chiu Fisher.
- +ng phn D v L l mt cp i quang, nn +ng phn D
l nh ca +ng phn L qua gng v ngc li.
- +ng phn epimer l cc monosaccarit ch( khc nhau v cu
hnh ca nguyn t cacbon s 2 (C2)
V d v cu hnh
tng i D,L ca
monosaccarit
Nguyn t
C
*
xa nhm
CHO nht
D, L- nh vt qua gng
-OH bn phi
-OH bn tri
V d v cc cp ng phn epimer ca cc pentoz
Cu hnh ca C2 khc nhau
Cp ng phn epimer
Cc cp epimer ca hexoz
Cp ng phn epimer
- Cu hnh tuyt i R,S ca monosaccarit c xc
nh theo h thng danh php ca Can, Ingol v Preloc,
ngha l phn cp ca cc nhm th.
CHO
HO H
HO H
CH
2
OH
HO H
H OH
H OH
(2S, 3S, 4R, 5R)- Mannose
2.2.3 Cu trc vng ca monosaccarit
- Monosaccarit khng tham gia c ht cc phn ng c
trng cho nhm cacbonyl. iu ny c Tollens gii
thch da trn phn ng ca nhm cacbonyl vi nhm
hidroxy trong mi tr!ng axit to ra hemiaxetal (I) v
axetal (II).
R'OH (H
+
)
H
+
H
- Khi to vng, nguyn t C % nhm cacbonyl tr% thnh
nguyn t cacbon bt i C
*
, n c gi l nguyn t C
anome.
RCHO
R'OH (H
+
)
R C
H
OH
OR'
(I)
R'OH (H
+
)
R C
H
OR'
OR'
(II)
a, Cng thc Tollens
- Cng thc Tollens biu din cc phn t monosaccarit di
dng hnh ch nht:
+ Mt cnh chiu di l cng thc Fisher ca
monosaccarit.
+ Cnh chiu di cn li c trung im l nguyn t
oxi tham gia lin kt hemiaxetan. oxi tham gia lin kt hemiaxetan.
+ Hai cnh chiu rng l cch biu din lin kt bnh
th!ng.
- Trong tr!ng hp andohexoz, s kt hp ca OH % C5 to
ra vng 6 cnh c tn l pyranoz, OH % C4 cho vng 5 cnh
gi l furanoz.
- C1 (andoz), C2 (xetoz) gi l C-anome nn HO-C1
(C2) gi l OH-anome.
- Vi dy +ng phn D:
+ OH-anome n"m bn phi ca cng thc gi l
+ng phn ,
+ OH-anome n"m bn tri ca cng thc gi l
+ng phn -
1
H OH
H OH
O
CH
2
OH
HO H
H OH
1
2
3
4
5
6
,-D-glucopyranoz
HO H
H OH
O
CH
2
OH
HO H
H OH
1
2
3
4
5
6
--D-glucopyranoz
HO H
H OH
CH
2
OH
O
HO H
1
2
3
4
5
6
H OH
--D-glucofuranoz
HOCH
2
OH
H OH
HO H
1
2
3
4
5
6
HOCH
2
H
O
HOCH
2
HO
H HO
OH H
1
2
3
4
5
6
HOCH
2
H
O
,-D-fructofuranoz
,-L-fructofuranoz
- Vi dy +ng phn L: l nh qua gng ca dy D.
HO CH
2
OH
H OH
HO H
1
2
3
4
5
6
HOCH
2
H
O
O
HOCH
2
H
6
5
4
3
2
1
OH H
H HO
OH CH
2
OH
,-L-fructofuranoz
--D-fructofuranoz
--L-fructofuranoz
D, L- nh vt qua gng
b, Cng thc Haworth
- Cng thc Haworth biu din cu hnh ca monosaccarit r
rng hn, c biu th b"ng mt hnh 6 (pyranoz) cnh
hoc 5 (furanoz) cnh, n"m trn mt mt ph)ng vung gc
vi mt ph)ng giy vi 1 nguyn t oxi n"m % pha sau.
O
O
O
O
Furan Pyran
- Dy ng phn D: nhm CH
2
OH n"m % pha trn mt
ph)ng vng:
+ +ng phn , khi OH-anome n"m % pha di mt
ph)ng vng (-CH
2
OH v OH-anome ngc chiu nhau).
+ +ng phn - khi OH-anome n"m % pha trn mt
ph)ng vng (-CH
2
OH v OH-anome cng chiu).
- Dy ng phn L: l hnh nh qua gng ca dy D. - Dy ng phn L: l hnh nh qua gng ca dy D.
O
OH
H
OH
H OH
H
H
OH
H
CH
2
OH
O
H
OH
H
OH H
OH
OH
H
CH
2
OH
H
--D-glucopyranoz --L-glucopyranoz
,-D-xilofuranoz
--D-xilofuranoz
D-Xiloz
Qu trnh hnh thnh vng ca !ng 5
D-glucoz
--D-glucopyranoz
,-D-glucopyranoz
Qu trnh hnh thnh vng ca !ng 5
O
OH
H
OH
H OH
H
H
OH
H
CH
2
OH
O
OH
H
H
OH OH
H
H
OH
H
CH
2
OH
--D-glucopyranoz --D-mannopyranoz
- c +ng phn L ta chiu D qua gng, n gin nht l
chiu theo phng ca trc z
z
O
H
OH
H
OH H
OH
OH
H
CH
2
OH
H
O
H
OH
OH
H H
OH
OH
H
CH
2
OH
H
--D-glucopyranoz
--L-glucopyranoz
--D-mannopyranoz
--L-mannopyranoz
Gng
x
y
3
2
1
O
HOCH
2
H
6
5
4
3
2
1
HO H
H OH
HO CH
2
OH
O
CH
2
OH
HOCH
2
OH
H OH
HO H
1
2
3
4
5 6
HOCH
2
H
O
,-D-fructofuranoz
--D-fructofuranoz
Cng thc Tollens
* Mi quan h gia cc cng thc biu din monosaccarit
6
5
4
3
O
CH
2
OH
OH
OH
H OH
H
H
CH
2
OH
O
OH
CH
2
OH
OH
H OH
H
H
CH
2
OH
1
2
3
4
5
6
1
2
3
4
5
6
HO H
H OH
H OH
CH
2
OH
,-D-fructofuranoz
--D-fructofuranoz
D-fructoz
Cng thc Haworth
Cng thc Fisher
c, Cng thc Reeves
- Cng thc Reeves m t trng thi thc ca phn t, cc
pyranoz c biu din % dng gh bn.
--D-galactopyranoz
Haworth Reeves
- Thc t a ph#n cc monosaccarit t+n ti trong thc t %
dng cng thc Reeves, k c cc !ng 5C.
--D-ribopyranoz (56%)
--D-ribopyranoz (18%)
,-D-ribopyranoz (20%) ,-D-ribopyranoz (6%)
D-riboz
<1%
2.2.4 Tnh cht ha hc ca monosaccarit
a, Phn ng ca nhmcacbonyl
- Trong dung dch kim cc xetoz d dng chuyn ha
thnh andoz, nn c andoz v xetoz u c phn ng
vi thuc th Fellinh v Tollens
1
CH
2
OH CHOH
CHO
CHO
6
5
4
3
2
HO H
H OH
H OH
CH
2
OH
O
CH
2
OH
HO H
H OH
H OH
C
CH
2
OH
CHOH
OH
OH
-
OH
-
HO H
H OH
H OH
CH
2
OH
CHO
HO H
H OH
CH
2
OH
CHO
H OH
H OH
HO H
+
D-Fructozo
Dang endiol
D-Mannozo D-Glucozo
-Phn ng oxi ha:
+ Cc andoz c phn ng vi Br
2
/H
2
O, y l phn
ng dng phn bit andoz v xetoz.
+ Cc monoz khi b oxi ha b%i HIO
4
to ra sn
ph&m l cc andehit v axit cacboxylic tng ng khi c*t
lin kt 1,2-diol
HOCH
2
[CHOH]
4
CHO
Br
2
, H
2
O
HOCH
2
[CHOH]
4
COOH
lin kt 1,2-diol
R CH
OH
CH
OH
R'
HIO
4
RCHO
+
R'CHO
HOCH
2
CH
OH
CH
OH
CH
OH
CH
OH
CHO
+ 5HIO
4
5HCOOH
+ HCHO
-Phn ng kh
H OH
CH
2
OH
CHO
H OH
H OH
HO H
D-Glucozo
HO H
H OH
H OH
CH
2
OH
CHO
HO H
D-Mannozo
H OH
CH
2
OH
CH
2
OH
H OH
H OH
HO H
D-Sobitol
HO H
CH
2
OH
CH
2
OH
H OH
H OH
HO H
D-Mannitol
Na-Hg
H
+
NaBH
4
H
+
HO H
H OH
H OH
CH
2
OH
O
CH
2
OH
H
2
Ni
H
2
Ni
D-Fructozo
-Phn ng osazon
HO H
H OH
H OH
CH
2
OH
CHO
HO H
D-Mannozo
H OH
CH
2
OH
CHO
H OH
H OH
HO H
D-Glucozo
+

3
C
6
H
5
N
H
N
H
2
C
H
3
C
O
O
H
+
3

C
6
H
5
N
H
N
H
2
C
O
O
H
D-Mannozo
D-Glucozo
HO H
H OH
H OH
CH
2
OH
O
CH
2
OH
HO H
H OH
H OH
H
2
O
O
H
+
C
H
3
C
O
CH
3
COOH
+3 C
6
H
5
NHNH
2
(Osazon)
C
CH
2
OH
NNHC
6
H
5
CH=NNHC
6
H
5
b, Phn ng ca nhmhydroxyl
- Phn ng vi Cu(OH)
2
O
HOCH
2
H
H
HO
HO
H
H
OH
OH
H
H OH
O
HOCH
2
H
H
O
O
H
H
OH
OH
H
H
O
CH
2
OH
H
H
O
O
H
H
HO
OH
H
H
Cu
Cu(OH)
2
1
2
3
4
5
6
1
2
3
4
5
6
- Phn ng to ete
O
OH
H
H OH
H
OH
H
CH
2
OH
C
H
3
O
H
H
C
l

(
k
h
a
n
)
O
OCH
3
H
OH
H OH
H
H
OH
H
CH
2
OH
H
OH
H OH
H
OH
(
C
H
3
O
)
S
O
2
,

N
a
O
H
C
H
3
I
,

N
a
O
H
CH
3
O
O
OCH
3
H
OCH
3
H OCH
3
H
H
H
CH
2
OCH
3
- Phn ng to este
(CH
3
CO)
2
O
CH
3
COO
O
OCOCH
3
H
OCOCH
3
H OCOCH
3
H
H
H
CH
2
OCOCH
3
O
OH
H
OH
H OH
H
H
OH
H
CH
2
OH
O
CH
2
OH
OH
OH
H OH
H
H
CH
2
OH
(CH
3
CO)
2
O
O
CH
2
OCOCH
3
OCOCH
3
H OCOCH
3
H
H
CH
2
CH
3
COO
CH
3
COO
- Phn ng to axetal v xetal vng
O
H
OH
OH
H OH
H
H
OH
H
CH
2
OH
CH
3
C CH
3
O
HCl (khan)
O
H
O
O
H OH
H
H
OH
H
CH
2
OH
C
CH
3
O
OH
H
OH
H OH
H
H
CHOH
CH
2
OH
CH
3
CH
3
O
H
H
OH
H
H
CH
CH
2
O
O
C
CH
3
CH
3
O
O
C
CH
3
CH
3
HCl (khan)
CH
3
C CH
3
O
2.3 Oligosaccarit
- Oligosaccarit l nhng cacbohydrat m khi thy phn hon
ton cho t 2 n 10 monosaccarit.
- Oligosaccarit hay gp nht l cc disaccarit v trisaccarit.
2.3.1 Disaccarit
- Disaccarit l cacbohidrat c to ra t 2 monosaccarit - Disaccarit l cacbohidrat c to ra t 2 monosaccarit
ngha l khi thy phn hon ton 1 phn t disaccarit s. thu
c 2 phn t monosaccarit.
- Cc disaccarit thi nhin quan trng l: saccaroz, mantoz,
lactoz v xenlobiz
- Hai phn t monosaccarit c lin kt vi nhau theo hai
cch:
+ Nhm OH hemiaxetal ca m/i monosaccarit lin kt
vi nhau to ra disaccarit khng kh.
+ Nhm OH hemiaxetal ca monosaccarit ny kt hp
vi 1 nhm OH khc ca monosaccarit cn li to ra vi 1 nhm OH khc ca monosaccarit cn li to ra
disaccarit kh.
a, Saccaroz
- L thnh ph#n chnh ca cy ma (14-26%), tht nt, c ci
!ng (16-20%) Cn c gi vi nhng tn khc: !ng
ma, !ng knh, !ng phn, !ng c ci
- C cng thc phn t: C
12
H
22
O
11
, tn ha hc l: 2-O-,-D-
glucopyranozyl---D-fructofuranozit hay ,-D-glucopyranozyl-
(102)---D-fructofuranozit.
6
5
6
5
4
3
2
1
2
1
O
H
CH
2
OH
OH H
CH
2
OH
O
H
H OH
H
OH
H
CH
2
OH
O
- Khi thy phn saccaroz trong dung dch axit long hoc
enzim thu c mt lng b"ng nhau D-(+)-glucoz v
D-(-)-fructoz. S thy phn ny gy ra s i du quay cc
t (+) sang (-), v vy qu trnh ny cn gi l qu trnh
nghch o !ng, h/n hp trn c gi l !ng nghch
o.
4
3
3
2
CH
2
OH
H OH
OH H
b, Lactoz
- Lactoz hay cn gi l !ng sa c v ngt km hn
saccaroz, c vai tr quan trng trong dinh d1ng ca tr2 em.
Trong sa ng!i c t 6-7% lactoz, sa b ch( c 4-5%
lactoz.
- C CTPT: C
12
H
22
O
11
, tn ha hc: 4-O---D-
galactopyranozyl-,-D-glucopyranoz hay --D- galactopyranozyl-,-D-glucopyranoz hay --D-
galactopyranozyl-(104)-,-D-glucopyranoz
O
H
OH
H OH
H
H
H
CH
2
OH
OH
O
OH
H OH
H
OH
H
H
CH
2
OH
H
O
1
2
3
4
5
6
4
5
6
3
2
1
2.3.2 Trisaccarit
- Trisaccarit l olisaccarit c cha 3 gc monosaccarit.
Trisaccarit ph bin nht v bit r hn c l rafinoz, c tn
ha hc: ,-D-galactopyranozyl-(106)-,-D-glucopyranozyl-
(102)---D-fructopyranozit
5
6
O
H OH
H
CH
2
OH
2
3
4
5
6
1
2
3
4
4
5
6
3
2
1
O
H
OH
H OH
H
H
OH
H
CH
2
H
OH
H OH
H
OH
H
H
O
O
H
CH
2
OH
OH
H OH
H
CH
2
OH
O
1
2.4 Polysaccarit
- Polysaccarit l nhng polyme thin nhin, c cu to t
hng tr$m, hng nghn m*t xch l cc monosaccarit, lin kt
cht ch. vi nhau qua lin kt glucozit.
- Polysaccarit c to thnh t mt loi monosaccarit
c gi l homopolysaccarit, i din cho nhm ny l: tinh
bt, glycogen, xenluloz. bt, glycogen, xenluloz.
- Polysaccarit c to thnh t hai loi monosaccarit
tr% ln c gi l heteropolysaccarit, hay gp nht trong
thin nhin l: pectin, aga, hemixenluloz
2.4.1 Tinh bt
- Tinh bt l mt loi polysaccarit rt ph bin trong thin
nhin. L thc $n quan trng ca c ng!i v ng vt.
- Tinh bt c d tr trong cc m thc vt di dng cc
loi ht, c qu (go, m3, ng, khoai , s*n, chui, ng), tp
chung ch yu trong cc loi ng' cc, go cha 78-80% tinh
bt, khoai ty c khong 16-19% tinh bt, m3 khong 65- bt, khoai ty c khong 16-19% tinh bt, m3 khong 65-
70%...
- Hm lng tinh bt ph thuc loi, ging, th!i v, a l v
th nhng khc nhau.
- V mt ha hc tinh bt l polyme sinh hc c to thnh
t cc monome l ,-D-glycopyranoz lin kt vi nhau qua
lin kt 1,4 v 1,6-glucozit. c chia lm 2 loi:
+ Amyloz c to thnh t cc monome l ,-D-
glycopyranoz lin kt vi nhau qua lin kt 1,4 glucozit.
O
CH
2
OH
O
CH
2
OH
L thnh ph#n chnh ca go t2 v cc ging ngu cc c ti
xp cao ( b% ln).
O
H
OH
H OH
H
H
H
O
H
OH
H OH
H
H
H
O
O
O
4
1
4
1
n
+ Amylopectin c to thnh t cc monome l ,-D-
glycopyranoz lin kt vi nhau qua lin kt 1,4 v 1,6
glucozit.
O
O
H
OH
H OH
H
H
H
CH
2
OH
O
1
L thnh ph#n chnh ca go np v cc ging ng' cc c
d2o ln
O
H
OH
H OH
H
H
H
CH
2
O
H
OH
H OH
H
H
H
CH
2
OH
O
O
O
4
1 4
1
n
6
2.4.2 Glycogen
- Glycogen l polysaccarit d tr ca c th ng vt, th!ng
tp trung trong gan (khong 20%) v trong c b*p (khong
4%), cn c gi l tinh bt ng vt.
- L cht r*n dng bt, mu tr*ng v nh hnh, d tan trong
nc, phn t khi khng 1 tru vC, c cu trc tng t
amylopectin nhng mc phn nhnh cao hn.
CH
2
OH
O
H
OH
H OH
H
H
H
CH
2
O
H
OH
H OH
H
H
H
CH
2
OH
O
O
O
O
O
H
OH
H OH
H
H
H
CH
2
OH
O
4
1 4
1
n
1
6
2.4.3 Xenluloz
- Xenluloz l mt polysaccarit cao phn t, khng c tnh
!ng, l thnh ph#n chnh ca mng t bo thc vt, l c s%
xy dng cu trc g/ ca thc vt. Xenluloz c nhiu trong
tt c cc loi g/ (40-60%), trong bng ln ti 98%.
- Xenluloz c to thnh t cc monome l --D-
glycopyranoz lin kt vi nhau qua lin kt 1,4 glucozit. glycopyranoz lin kt vi nhau qua lin kt 1,4 glucozit.
n
1
4 1
4
O
OH
H OH
H
H
H
CH
2
OH
H
O
OH
H OH
H
H
H
CH
2
OH
H
O
O
O
2.4.4 Aga
- Aga l mt polygalactopyranzit, c trong mt s loi rong t
bin v mt s c th vi sinh vt. Aga cn gi l thch tr*ng,
c dng nhiu trong cng nghip thc ph&m.
- Khi thy phn aga ng!i ta nhn c D-galactoz, L-
galactoz v axit sunfuric theo t l 9:1:1.
- Cc m*t xch ca aga l D-galactoz c g*n vi nhau qua
C1 v C3. n m*t xch th 10 li c L-galactoz, % v tr s
1 v 4 ca L-galactoz th to thnh mch, cn % v tr s 6
ca n b este b%i axit sunfuric; mch c ko di lin tc nh
vy. (cng thc l bi tp sinh vin t v.).
CHNG 3
TECPENOIT
3.1 Khi nim
3.2 Monotecpenoit
3.3 Secquitecpenoit
3.4 Ditecpenoit 3.4 Ditecpenoit
3.5 Tritecpenoit
3.6 Tetratecpenoit
3.7 Polytecpenoit
3.1 Khi nim
- Tecpen hay cn gi l tecpenoit l nhng hp cht hu
c cha C, H v O tn ti trong thin nhin m c b
khung cacbon gm nhiu mt xch ging vi khung
cacbon ca isopren, tc l c th biu din bi cng
thc (iso-C
5
)
n
vi (n2).
O
khong theo qui tac dau noi vi duoi
Squalen
Zerumbon
1
2
3
4
5
6
7
8
9
10
11
Oximen
isopren
dau
duoi
Loi tepen Khung cacbon S lng C
Monotecpen (iso-C
5
)
2
10
Secquitecpen (iso-C
5
)
3
15
- phn loi tecpen ng!i ta c$n c vo s
lng n v isopren hp thnh phn bit:
Secquitecpen (iso-C
5
)
3
15
itecpen (iso-C
5
)
4
20
Tritecpen (iso-C
5
)
6
30
Tetratecpen (iso-C
5
)
8
40
3.2 Monotecpenoit
3.2.1 Axiclic monotecpen
- Cc monotecpen khng vng l d4n xut ca 2,6-
imetyloctan, % h#u ht cc monotecpen ny u cha
nhm isopropyliden (a) (+ng phn -) v mt s t cha
nhm isopropenyl (b), (+ng phn ,). nhm isopropenyl (b), (+ng phn ,).
2
6
(b)
(a)
2,6-dimetyloctan
a, Hidrocabon tecpen
- i vi hirocacbon tecpen loi ny, ch( c hai
hirocacbon ng c cp n l Oximen v Mirxen,
m/i cht u c 3 lin kt C=C. Chng xut hin trong tinh
d#u basil (Ocimum basilicum), v tinh d#u cy nguyt qu
(laurel oil). C hai u c cha ni i lin hp, chng ch(
phn bit c vi nhau b%i v tr ca cc ni i. phn bit c vi nhau b%i v tr ca cc ni i.
Mirxen
Oximen
b, Dn xut ancol tecpen
-5ng vi 2 khung hirocacbon tecpen c nhng ancol tecpen
cha mt hoc 2 lin kt i, u l nhng cht c mi thm c
trng, nhng n hng qu tch c t tinh d#u hoa h+ng, tinh
d#u s
OH
CH
2
OH
CH OH
Linalool l mt ancol bc 3 quang ht, l thnh ph#n ca nhiu
loi tinh d#u, nh tinh d#u cy oi hng v trong tinh d#u ht
mi n xut hin vi hm lng kh cao.
Linalool
CH
2
OH
Nerol
Geraniol
Xitronellol
CH
2
OH
c, Dn xut cacbonyl tecpen
Citronellal
CHO
Geranial (Citral a)
CHO
Neral (Citral b)
CHO
H
H
+
*
C
CH
H
C
O
CH
3
H
C
CH
H
C
O
CH
3
C
CH
H
C
O
CH
3
OH
-
, H
2
O
(CH
3
)
2
CO
citral
C
O
H
3.2.2 Monoxiclic monotecpen
- Cc monoxiclic monotecpen deu l dan xuat cua p-
menthan. p-menthan xuat hien dui hai dang khong
quang hoat, cc dong phan cis v trans.
H
H
1
7
7
7
H
H
H
p-menthan
cis-p-menthan trans-p-menthan
1
2
3
4
5
6
8
9
10
1
2
3
4
5
6
8
9
10
1 2
3
4
5
6
8
9
10
a, Hidrocacbon tecpen
- Trong so 14 dong phan cua menthandien c the ton tai, chi c 6 dong phan
dui day duoc tm thay trong tinh dau thuc vat:
*
*
*
-terpinen -terpinen terpinolen -phellandrene -phellandren limonen
(R)-(+)- v (S)-(+)- Limonen, C
10
H
16
deu xuat hien trong cc tinh dau l
thong, mot so loi citrus (cam, chanh, b%i).
b, Ancol tecpen
-Menthanol hoac menthan-3-ol, C
10u
H
20
O, l ancol no c ba trung tam
chiral trong phan tu, v ket qua c tm dong phan lap the. Cau hnh
tuong doi gia nhm hidroxi v nhm isopropyl d duoc xc dinh: o
neo-menthol v neo-isomenthol 2 nhm ny dinh hung cis vi nhau,
cn o mentol v isomenthol chng l trans cua nhau.
H H
H
H
(+)-menthol (+)-Isomenthol (+)-Neomenthol (+)-Neoisomenthol
H
OH
H
H
H
OH
H
H
H
OH
H
H
H
OH
H
H
--Terpineol, C
10
H
16
O, mot trong so cc ancol khong no xuat hien
trong tinh dau bach dau khau. Khi lac -Terpineol vi dung dich axit
sunfuric long c the thu duoc hidrat cua 1,8-tecpin, C
10
H
20
O
2
.
O
(H
2
O)
(H*)
*
OH
H
3
C OH
(H
+
) H
2
O
H
2
O
OH
-Terpineol 1,8-tecpin 1,8- Cineol
- Carvomenthol, C
10
H
20
O c cong thc nhu sau
OH
c, Cacbonyl tecpen
-Carvon, p-methan-6,8(9)-dien-2-on, dang (S)-(+)- cua n duoc tm
thay trong tinh dau cay Caraum v tinh dau tha l, v c mi carum.
IsoPiperitenon
O
Piperitenon
O
Carvon
O
thay trong tinh dau cay Caraum v tinh dau tha l, v c mi carum.
Carvon c the dieu che di t limonen.
NOH
KOH
Cl
NOH
NOCl
O
- Ba xeton mot lan khong no (C
10
H
16
O) duoc nghien cu ki l
pulegon, isopulegon v piperiton, tat ca chng deu c nhm xeto o
vi tr C
3
.
isopulengon
H
O
H
Pulegon
O
Piperiton
O
- Menthon, p-menthan-3-on, C
10
H
18
O, cha 2 nguyen tu cacbon bat
doi xng, v ton tai o 4 dong phan quang hoat.
D,L-isomenthon
D,L-menthon
O
O
- Cc xeton no vi nhm chc oxo tren C2 nhu o Carvomethon
Isocarvomenthol
OH
O
OH
O
Isocarvomenthon
Neoisocarvomenthol
Isocarvomenthol
OH
Neocarvomenthol
Carvomenthon
Carvomenthol
OH
3.2.3 Bixiclo monotecpen
- Cc monotecpen hai vng duoc phan loai theo 7 nhm
vng no nhu: thujan, caran, pinan, boran, isocamphan,
fenchan, v isobornilan.
fenchan
Isobornilan Isocamphan
Thujan
Bornan (Camphan)
Pinan
Caran
a, Nhm pinan
- Hidrocabon khong no quan trong v - pinen l cc thnh
phan chu yeu (80-90%) cua tinh dau thong.
-Pinen (156
0
C) -Pinen (164
0
C) -Pinen (156 C) -Pinen (164 C)
- Khi bi hidrat ha trong moi trung axit vo co long ca v -
pinen deu mo vng 4 canh, cho -terpineol hoac 1,8-terpin hoac
hidrat cua n.
OH
OH
H
2
O
OH
H
2
O(H
2
SO
4
)
b, Nhm camphan
- Cc hidrocacbon goc cua nhm ny l camphan v isocamphan.
Ton tai tat ca 6 olephin l camphen, bornylen, isotricyclen, exo-
isocaphen, v endo-isocamphen.
Camphan exo-Isocamphan endo-Isocamphan Camphen
- Trong tat ca cc olephin ni tren, camphen l chat quan trong
nhat. T camphen ngui ta dieu che ra campho (C
10
H
16
O, mot
xeton 2 vng c trong cay long no).
Camphan exo-Isocamphan endo-Isocamphan Camphen
O
CH
3
H
3
C
CH
3
H
3
C
CH
3
CH
3
O
Campho L-campho D-campho
CH
3
CH
3
CH
3
O
3.3 Secquitecpen
3.3.1 Axiclic secquitecpen
Secquitecpen ancol farnesol v nerolidol, C
15
H
16
O, chng deu
c 3 noi doi C=C. Nerolidol phan biet vi farnesol o vi tr noi doi
C=C v nhm OH. Cc ancol ny quan he vi nhau theo cng
cch nhu gia geraniol v linalool.
Farnesol Nerolidol
CH
2
CH
3
CH
3
CH
3
OH
CH
3
CH
3
CH
3
CH
3
CH
2
OH
CH
3
3.3.2 Xiclic secquitecpen
- Hidrocacbon bisabolen duoc tm thay trong tinh dau vo
chanh v tinh dau l thong, cadinen (t tinh dau cua cc loi
bc x v tuyet tng) v -selinen (cay can tay).
O
H
OH
CH
3
H
2
O
H
+
HOCH
2
Farnesol Bisabolen Hernandulcin
Cadinen beta-selinen
- Cc azulen duoc phan lap t cc tinh dau, v du vetivasulen (tinh
dau huong lau) v guaiazulen (tinh dau phong l), -Santalen,
C
15
H
24
, t tinh dau go dn huong trang, v modhephen, C
15
H
24
,
mot dan xuat cua [3.3.3]propellan duoc phan lap t vi khuan que
c mu vng (Isocome wrightii)
HOCH
Farnesol Guaiazulen (xanh)
CH
2
OH
Farnesol Vetivazulen (tm)
HOCH
2
anfa-Santanlen
Modhephen
3.4 Ditecpen
3.4.1 Axiclic ditecpen
Phytol, C
20
H
40
O, cha mot noi doi C=C v hai trung tam bat doi
xng. Cau hnh tuyet doi cua phytol, [(2E)-(7R,11R)-3,7,11,15-
tetrametylhexandec-2-enol] duoc xc dinh mot tong hop dac th lap
the.
3.4.2 Xiclic ditecpen
Phytol
* *
(R)
(R)
OH
- Vitamin A, cn goi l vitamin A1 hoac INN: retinol, C
20
H
30
O l mot
ditecpen ancol bac 1 khong no. N duoc tm thay truc het trong tinh
dau gan c, ng do trng g v sa.
X=COOH Vitamin A, axit
X=CH
2
OH Vitamin A
vng--ionon 11-cis-Retinal
11
CHO
X
- Axit abietic, C
20
H
30
O
2
, l chat ditecpen 3 vng quan
trong nhat. N l thnh phan chnh cua colophan, nhua
thong. N chiu su dehidro ha v decacboxyl ha de tao
thnh reten khi bi dun nng vi luu huynh.
CH(CH
3
)
2
CH
3
CH
axit abietic Reten
CH
3
CH(CH
3
)
2
S
CH
3
H
CH
3
HOOC
- Phorbol, C
20
H
28
O
6
, duoc tm thay dui dang mot 12, 13-
dicacboxylat este o trong dau ba dau t hat cay Croton
tiglum L., Euphorbiaceace: n l chat dong gay ung thu.
HO
OH
OH
Phorbol
O
OH
H
HO
H
H
CH
2
OH
3.5 Tritecpen
Tat ca cc tritecpen mot vng den nam vng v cc hop chat
khc bat nguon t squanlen, C
30
H
50
. Do vay cc tritecpen cn
goi l cc squalenoit
HO
H
H
H
H
H
Lanosterol
HO
H
HO
H
Squalen
HO
H
H
H
R
HO
H
H
H
Hopan
anfa-amyrin
R=CH
3
(beta-amyrin)
R=COOH (axit oleanolic)
3.6 Tetratecpen
Tetratecpen hay cn gi l carotenoit l cc chat mau thuc pham, hay
cn goi l cc sac to polyen. Caroten l hon hop cua 3 dong phan, ,
v - caroten, Lycopen gay ra mau do tham cua c chua v nhieu
loai qua khc.
*
anfa-caroten
beta-caroten
gama-caroten
Lycopen
3.7 Polytecpen
- Polytecpen hay cn gi l polypren, trong cao su thin nhin l
mt sn ph&m quan trng (chuoi ca (Z)-1,4-prolyisopren cua
polyme all-cis).
- Cc polyprenol c cong thc chung:
n/4
H CH
2
OH
n
CHNG 4
STEROIT
4.1 i cng
4.2 Cc sterol
4.3 Cc axit mt
4.4 Cc steroit vitamin 4.4 Cc steroit vitamin
4.5 Cc steroit hocmon
4.1 i cng
- Bo khung cua cc steroit cau tao boi bon vng cacbon dnh ket vi
nhau de tao thnh penhidro xiclopenta [a] phenanthren, C
17
H
28
, hay
cn goi l gonan hoac steran.
27
26
25
24
23
22
21
20
19
18
A
B
C
D
1
2
8
9
10
11
12
13
14
15
16
17
17
16
15
14
13
12
11
10
9
8
7 3
2
1
D
C
B
A
- c im d!nh "#t $%ng. Cc vng A v B c the dnh ket vi nhau
hoac theo cis hoac theo trans, vng B v C luon trans, vng C v D
thung trans, tuy nhien cng thung gap su dnh ket cis, th du nhu
cc cacdenolit v cc bufadienoit.
Cholestan
Gonan
A
B
3
4
5
6
7
7
6
5
4
3
B
A
- Nhm metyl o nguyen tu cacbon so 10 duoc dng lm diem chuan.
Cc nhm the v cc nguyen tu hidro duoc dinh vi o cng pha trong
phan tu nhu nhm ny duoc chi dinh l cc nguyen tu : cc nhm
the hoac nguyen tu hidro o pha nguoc lai cua vng l cc nhm .
Hai dong phan lap the l 5--cholestan v 5--cholestan, cc vng
B/C v C/D duoc dnh ket trans.
17
13
17
5--Cholestan 5--Cholestan
(A-B: trans) (A-B: cis)
H
H
H
H
H
10
5
17
13
14
14
13
5
10
H
H
H
H
H
4.2 Cc sterol
Cholesterol, C
27
H
45
OH, l thnh phan chnh cua soi mat,
thnh phan chnh cua cc te bo, cholesterol xuat hien dui dang tu
do hoac dui dang este trong tat ca cc te bo dong vat v dich co the.
Ergosterol, (22E)-(24R)-24-metycholesta-5,7,22-trien-3-ol,
C
28
H
43
OH, duoc tm thay trong men bia, l chat quang hoat. Khi bi
roi sng, ergosterol chuyen sang vitamin D2.
tigmasterol, (22E)-(24S)-24-etycholesta-5,22-dien-3-ol,
C
29
H
47
OH, xuat hien trong dau nnh v chi phan biet vi cholesterol C
29
H
47
OH, xuat hien trong dau nnh v chi phan biet vi cholesterol
bang mach nhnh.
Ergosterol Stigmasterol
24
10
5
17
13
14
3
H
H H
HO
H
H
22
7 7
22
H
H H
HO
3
14
13
17
5
10
4.3 Cc axit mt
Ve mat ha lap the cc axit mat l cc dan xuat cua 5--
Cholestan. Chat ny c vng A v B dnh ket cis duoc coi l hop chat
goc cua cc axit mat.
Cc th du quan trong nhat l cc axit cholic (axit 3, 7,
12-trihidroxi-5-cholan-24-cacboxilic), axit deoxycholic (axit 3,
7,-dihidroxi-5-cholan-24-cacboxilic) v axit lithocholic (axit 3-
hidroxi-5-cholan-24-cacboxilic). Tat ca cc axit ny deu quang
hoat. hoat.
Axit cholanic Axit cholic
12
7
3
COOH
H
H
H
HO
H
OH
OH
24
24
COOH
H
H
H
HO
H
4.4 Cc steroit vitamin
!itamin "#, (Calciferol, ergocalciferol, vigantol),
C
28
H
43
OH. Cau trc cua vitamin D2 d duoc xc dinh l
(5Z,7E,22E)-(3S)-9,10-secocholesta-5,7,10 (19), 22-tetraen-3-
ol. Vitamin D2 l chat quang hoat.
23
17
22
Ergosterol Vitamin D2
Ergosta-5,7,22-trien-3-ol
5
6
7
23
9
10
19
H
H
HO
hv
10
5
17
13
14
3
H
H H
HO
7
!itamin "3 (Cholecalciferol, (5Z,7E)-(3S)-9,10-
secocholesta-5,7,10(19)-trien-3-ol) xuat hien cng vi
vitamin A trong dau gan c ng Califoni, c bon halibut v
c moruy. Calcitol duoc tao ra o trong than t vitamin D3.
24
23
17
22
7-ehirocholesterol Vitamin D3
H
H
HO
H
H H
HO
5
6
7
23
9
10
19
hv 10
5
13
14
3
7
4.5 Cc steroit hocmon
Gom 2 nhm hocmon quan trong l cc hocmon gii tnh v hocmon
tuyen thuong than. Nhm sau duoc goi l cc coticoit.
4.$.1 %ocmon gi!i tnh nam (androgen)
Cc hocmon dau tien loai ny l androsteron, C
19
H
30
O
2
v 5-
dehydroandrosteron, C
19
H
28
O
2
. Hidrocacbon goc cua ca hai androgen
ny l androstan (10,13-dimetlgenan), C
19
H
32
. Ca hai hop chat deu c
mot nhm xeto o nguyen tu cacbon 13.
Testosteron, C
19
H
29
O
2
, duoc phan lap t tinh hon b duc Testosteron, C
19
H
29
O
2
, duoc phan lap t tinh hon b duc
(Laco, 1935), l mot androgen hoat dong.
Androsteron Testosteron 16-Androsten-3-on
3--hidroxi-5-androstan-17-on 17--hidroxiandrostan-4-en-3-on
CH
3
CH
3
O
CH
3
H
H
H
CH
3
O
OH
17
O
CH
3
H
H
H
CH
3
H
HO
4.$.# %ocmon gi!i tnh n"
-Phan biet hocmon nang trng (follicular hormones) v cc
hocmon thai nghn (Pregnancy hormones).
a, %ocmon nang trng (cc estrogen)
- Hocmon nang trng duoc ket tinh t nuc tieu phu n c
thai goi l esteron, C
18
H
22
O
2
: 17-estradiol, C
18
H
26
O
2
: v
estriol, C
18
H
24
O
3
.
CH
3
OH CH
3
OH
H
O
CH
3
Estron 17--Estradiol Estriol
- Hocmon hoat dong nhat l 17--estradiol (estra-1,3,5(10)-
trien-3,17-diol)
17
18
17
CH
3
H
H H
HO
OH
OH
CH
3
H
H H
HO
H
17
3
CH
3
H
H H
HO
b, Cc hocmon th# vng (gestagen)
- Hocmon n gii dac trung t the vng hay hocmon thai
nghn l progesteron (poluton), C
21
H
30
O
2.
CH
3
H
CH
3
H CH
3
O
CH
3
H
CH
3
H
H
H
CH
3
O
CH
3
H
CH
3
H
H
H
CH
3
5-Pregnan Progesterol Pregnenolon
(d.n.c. 84
0
C [357K]) (d.n.c. 121
0
C [394K]) (d.n.c. 190
0
C [463K])
(Pregna-4-en-3,20-dion) (3-Hidroxipregna-5-en-20-on)
H H
HO
H H
O
H H
H
c, Cc steroit trnh thai
- Cc gestagen bi thay doi, th du nhu 19-norethisternoxetat,
khi phoi hop vi cc estrogen c the ngan nga su thu thai.
N
CH
3
CH
3
H
CH
3
OH
C
C CH
3
OH
C
CH
O COCH
3
C
H H
CH
19-Norethisteronaxetat 17-Ethynylosestradiol RU 486 (Mifepriston)
O
H
H
HO
H H
O
CHNG 5
FLAVONOIT
5.1 Phenolic thin nhin
5.2 Hp cht flavonoit
5.3 Sinh tng hp flavonoit
5.4 Hot tnh sinh hc ca flavonoit 5.4 Hot tnh sinh hc ca flavonoit
5.1 Phenolic thin nhin
- Yeu to dac trung cho phenolic l c mat t nhat mot nhan benzen
lien ket vi t nhat mot nhm OH o dang tu do hoac lien ket trong
mot nhm chc khc: este, ete... Chat don gian nhat ca phenolic
l phenol. Cc flavonoit l 1 nhm ca lp cht phenolic.
5.2 Hp cht flavonoit
$.#.1 &h'ng c s$ ca flavonoit
- Cc flavonoit cn duoc goi l dan xuat cua 2-phenyl chroman
(flavan). l cc hop chat c cau tao khung cacbon C
6
-C
3
-C
6
,
gom hai vng benzen A, B v mot di vng C.
- Vng A v vng C ket hop tao khung chromon. Neu vng B dnh
vi di vng C o vi tr C3 th ta c cc iso flavonoit.
- Di vng C c the l: - Di vng C c the l:
- Hai flavonoit c the ngung tu vi nhau de tao ra biflavonoit.
Ngy nay nhieu flavonoit tu nhien d duoc biet v nghien cu
$.#.# ( ph)n lo*i c+c nhm ,lavonoit
- Co so cua su phan loai cc nhm flavonoit tuy theo mc do oxi ho
vng pyran l su c mat hay khong c noi doi gia C2 v C3 v nhm
cacbonyl o C4.
a, Nhm flavon v flavonol
Ngy nay ngui ta d biet khoang 90 hop chat cua nhm
flavon v flavonol. Chng c cong thc cau tao chung nhu sau:
Su da dang cua nhm chat ny l do so luong v vi tr nhm
hidroxy lien ket vi cc nguyen tu cacbon cua khung. Cc nhm
hidroxy ny c the bi ankyl ha tao ra cc dan xuat khc nhau.
b, Nhm flavanon
Cc flavanon thung xuat hien vi nhieu nhm hidroxy
hoac metoxy v duoc phan lap t cc hoa mu trang. Chng c
mot trung tam khong trng vat anh (nguyen tu cacbon bat doi
xng C2) nen c tnh quang hoat, v lun c mt cn b"ng h/
bin.
c, Nhm flavanonol
lavanonol-3 hay cn goi l flavanon-3-ol hoac
dihidroflavonol. lavanonol gan giong nhu flavanon nhung chi khc
l c nhm hidroxy o vi tr C3. lavanonol c hai nguyen tu cacbon
bat doi xng o C2 v C3 nen chng c tnh quang hoat. lavanonol d
bi oxi ha de cho flavonol tuong ng, v ngui ta biet den khoang 30
hop chat thuoc nhm ny, phan ln o dang aglycon, chi c vi chat o
dang glycozit.
d, Nhm chalcon
Chalcon khc vi cc loai flavonoit khc l phan tu bao
gom hai vng benzen A v B noi vi nhau boi mot mach ho gom
ba cacbon.
Chalcon thung c mu t vng sam, do da cam den do
ta. oi vi phan ng mu xianidin, chalcon thung cho mu r
ret.
e, Nhm auron
Khc vi cc flavonoit khc, auron c vng C l mot di
vng nam canh. Auron c mu vng dam v khong tao phan ng
xianidin.
Trong tu nhien, cc chalcon-glycozit d bi oxi ha thnh
auron-glycozit nen hai nhm chat ny ton tai canh nhau. Cc
auron-glycozit hay xuat hien trong cc cay ho Cc (Asteaceae).
,, Nhm anthoxianin
Anthoxianin thung gap trong tu nhien o dang glycozit d
tan trong nuc. Khi dun anthoxianin trong moi trung axit (HCl
20%) th phan dung gan vo bi cat ra v cho ta phan aglycon l
anthoxianidin.
Anthoxianidin c cau trc 2-phenylbenzopyrilium hay cn
goi l cation flavylium.
Mu sac cua anthoxianin thay doi theo pH. Trong dung
dich axit vo co, anthoxianin cho muoi oxoni c mu t nhieu do,
cn trong moi trung kiem, chng tao thnh cc anhidrobazo vi
mot nhm quinoit cho mu xanh.
Tuy nhien, su xuat hien mu khc nhau cua cng mot
anthoxianin o trong cc cay khc nhau lai do su tao thnh cc
chelat kim loai khc nhau. V du, xianidin clorua tao thnh mu
do cua hoa hong, tri lai mot phc xianidino nhom sat (III) cho
mu xanh cua hoa mua.
g, Nhm le'coanthoxianin
Leucoanthoxianin cn duoc goi l flavan-3,4-diol.
Khi dun soi vi nuc hoac etanol c mat axit HCl,
leucoanthoxianin s chuyen ha thnh anthoxianin.
Cc chat thuoc nhm ny mi chi tm thay dui dang
aglycon, chua tm thay o dang glycozit.
h, Nhm catechin
Catechin l cc dan xuat flavan-3-ol. Do c hai trung tam
khong trng vat anh, chng ton tai dui dang hai cap diastereome,
v du cc cap catechin v epicatechin.
Trong so bon dong phan quang hoc ny cua catechin th
chi c (+)-catechin v (-)-epicatechin xuat hien trong thien nhien.
Catechin c nhieu trong cc qua v l ch, l hop chat
flavonoit pho bien trong thien nhien.
i, Nhm iso ,lavonoit
Iso flavonoit bao gom cc dan xuat cua 3-phenylchroman.
Ve mat cau trc, iso flavanon khc iso flavon o cho
khong c lien ket doi gia C2 v C3, loai hop chat ny cng
khong cho phan ng mu xianidin.
5.3 inh t-ng h.p c+c h.p ch/t ,lavonoit
- 6 cc flavonoit mot don vi C
15
co so bao gi cng c mat
nhu duoc the hien o cau trc sau:
- Bang cc th nghiem dnh dau bang dong vi phng xa ngui
ta d xc dinh duoc rang tieu don vi ArC
3
c nguon goc t
shikimat v kieu don vi kia (nhan thom A) c nguon goc t
polyketit.
- Kieu ket hop oxi cua vng A duoc chi ra o hnh tren v vng
B c kieu the 4-hidroxy, 3,4-dihidroxy hoac 3,4,5-trihidroxy.
5.4 %o*t t0nh sinh h1c c2a c+c ,lavonoit
- Cc flavonoitc tc dung chong oxi ha (antio&idant). ay l mot
trong nhng co so sinh ha quan trong nhat de flavonoit the hien
duoc hoat tnh sinh hoc cua chng. lavonoit c kha nang km hm
cc qu trnh oxy ha day chuyen sinh ra boi cc goc tu do hoat
dong.
- Tuy nhien, hoat tnh ny the hien manh hay yeu phu thuoc vo dac
diem cau tao ha hoc cua tng chat flavonoit cu the.
CHNG 6
ANCALOIT
6.1 Khi nim v vai tr sinh hc
6.2 Phn lp ancaloit
6.3 Phn loi v danh php
6.4 Mt s ancaloit tiu bi#u 6.4 Mt s ancaloit tiu bi#u
6.1 Khi nim v vai tr sinh hc
a, &h+i ni3m
'ncaloit l( m)t nh*m h+p ch,t thi-n nhi-n m( h.u h#t
l( c/c d0 $%ng ch1a nit2, c* t!nh 3a42, c* trong m)t s5 sinh
$6t nh,t 0nh.
13
3
1
2
O
O
N 13
12 11
10
9
8
7
6
5
4
3
OCH
3
CH
3
O
N
+
O
OH
Beberin
4
a'
Nicotin
N
N
CH
3
N
N
O
CH
3
O
CH
3
N
N
CH
3
Cofein
b, !ai tr sinh hc
- Ancaloit hnh thnh de bao ve cay, v cc ancaloit
ni chung deu rat doc vi dong vat.
- Ancaloit c vai tr gay pht duc cho cay.
- Ancaloit l chat du tr dinh dung nuoi mam cay
cho the he sau.
- Ancaloit l chat trung gian hay chat thai trong qu - Ancaloit l chat trung gian hay chat thai trong qu
trnh trao doi chat.
C the ancaloit c ca bon chc nang tren.
6.2 Phn lp ancaloit
a, Nghien nho nguyen lieu (l, than, r) thnh bot roi
ngam vi dung dich axit HCl (hoac ngam truc tiep bang dung
dich Na
2
CO
3
) de chuyen ho hon ton ancaloit thnh muoi
clohidrat d tan.
b, Loc lay dung dich muoi (bo b de d xu l giai doan
sau), kiem ho de day ancaloit hon ton ra khoi muoi.
c, Cat cuon hoi nuc (vi ancaloit d bay hoi cng c, Cat cuon hoi nuc (vi ancaloit d bay hoi cng
nuc) hoac chiet bang dung moi hu co nhu clorofom,
benzen
d, Chay cot sac k hoac sac k ban mong dieu che
phan lap rieng tng ancaloit.
c, c dinh cau trc cc ancaloit, thu hoat tnh sinh
hoc, dem san pham thu nghiem, ng dung.
6.3 Phn loi v danh php
6.3.1 Phn loi
- C/ch 78 Da theo thnh ph#n nguyn t ha hc, c th chia
ancaloit thnh 4 nhm cht nh sau:
+ Nhm 1 c cc nguyen to C, H, N.
+ Nhm 2 c cc nguyen to C, H, N, O.
+ Nhm 3 c cc nguyen to C, H, N, S.
+ Nhm 4 c cc nguyen to C, H, N, O, S. + Nhm 4 c cc nguyen to C, H, N, O, S.
Cc ancaloit nhm 3 c do doc cao nhat, thung c trong nam
doc.
- C/ch 98 Theo cau tao vng co so c cha di to N, phan
ra thnh cc loai pirole, imidazole, piridin, quinolin,
isoquinolin, tropan, indole
8
7
6
5
4
3
2
1
6
5
4
3
2
1
5
4
3
2
1
5
4 3
2
1
N
N
N
N
H
N
H
8
7
6
5
4
3
2
1
8
7
6
5
4
3
2
1
8
1
1
7
6
5
4
3
2
1
Indole
N
H
Tropan
N CH
3
Isoquinolin
N
Quinolin
N
Piridin Imidazole
H
Pirole
H
6.3.2 Danh php
- Viec dnh so trong vng ancaloit don gian tuan theo
viec dnh so trong cc di vng d biet. Th du, cc
ancaloit loai tropen dnh so theo kieu vng bixiclo:
7
6
8
5
4
3
2 1
N CH
3
Atropin
Tropan
9
'
8
'
7
'
6
'
5
'
4
'
3
'
2
'
1
'
3
N CH
3
H
O C
O
CH
CH
2
OH
1 2
4
5
8
6
7
6
5
4
- Vi cc vng phc tap hon th cch dnh so hop l l theo
cch dnh so cua cc di vng, vng thom, vng no d biet.
Th du: dnh so trong phan tu beberin theo kieu dnh so trong
phan tu pentaphen:
1
2
3
1
2
O
4
5
6
7
8
13
14 13
12
11
10
9
8
7
6
5
4
3
OCH
3
CH
3
O
N
+
O
OH
Pentaphen
Beberin
4
a'
-Vi cc vng phc tap hon th phai chon vng co so gan giong vi
vng d biet roi dnh so vng co so theo kieu dnh so vng d biet,
tiep den cc vng khc sao cho c trat tu het vng ny den vng
khc.
-Th du: nh so trong phan tu mophin, mot ancaloit loai
isoquinolin, neu dnh so vng t isoquinolin th rat phc tap, nen
Robinson d bieu din v dnh so theo kieu vng phenantren:
HO
1
2
1
2
3
4
5
6
7
8
9
10
11
12
13
14
Phenantren
Mophin kieu phenantren
O
HO
HO
N CH
3
1
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
Pilocacpin
CH
3
CH
2
O
CH
2
N
N
CH
3
Coniin
N
H
CH
2
CH
2
CH
3
N
CH
N
O
CH
3
N CH
3
6.4 Mt s ancaloit tiu bi#u
Nicotin
N
CH
3
Quinin
N
CH
3
O
CHOH
N
CH CH
2
13
12
11
10
9
8
7
6
5
4
3
2
1
N
O
O
CH
3
O
OCH
3
OH
Cofein
N O
CH
3
N
Beberin
Ti liu tham kho Ti liu tham kho
Carey F.A. Carey F.A. Organic chemistry Organic chemistry (5ed., MGH, (5ed., MGH, 2004 2004)(T)(C)(1335s). )(T)(C)(1335s).
M. C. Steven, J. M. Russell, M. C. Steven, J. M. Russell, Bioactive Natural Products, detection, Isolation and Structural Bioactive Natural Products, detection, Isolation and Structural
Determination Determination. CRC Press, . CRC Press, 1993 1993
. J. A. March , M. B. Smith"Advanced Organic Chemistry. Reactions, Mechanisms and . J. A. March , M. B. Smith"Advanced Organic Chemistry. Reactions, Mechanisms and
Structure (Fifth Edition), J. Wiley & Sons, Structure (Fifth Edition), J. Wiley & Sons, 2001 2001..
J. Clayden, N. Greeves, S. Warren and P. Wothers, J. Clayden, N. Greeves, S. Warren and P. Wothers, Organic Chemistry Organic Chemistry, Oxford University , Oxford University
Press, Oxford, Press, Oxford, 2000 2000 Press, Oxford, Press, Oxford, 2000 2000
Ng Th Thun, ng Nh Ti, Ha hu c tp 2, NXB GD Ng Th Thun, ng Nh Ti, Ha hu c tp 2, NXB GD 2012 2012..
Phm Th Chnh, Phm Th Chnh, Bi ging Ho hc cc hp cht Thin nhin, ti liu ni b, HKH, H Bi ging Ho hc cc hp cht Thin nhin, ti liu ni b, HKH, HTN TN
Phan Tng Sn, Phan Tng Sn, Bi ging Ho hc cc hp cht Thin nhin, ti liu ni b, HKHTN, Bi ging Ho hc cc hp cht Thin nhin, ti liu ni b, HKHTN,
HQGHN. HQGHN.
Nguyn V$n u, Nguyn V$n u, Bi ging Ho hc cc hp cht Thin nhin, ti liu ni b, HKHTN, Bi ging Ho hc cc hp cht Thin nhin, ti liu ni b, HKHTN,
HQGHN HQGHN..
Phm V$n Th(nh, Phm V$n Th(nh, Bi ging Ho hc cc hp cht Thin nhin v hot tnh sinh l ca chng, Bi ging Ho hc cc hp cht Thin nhin v hot tnh sinh l ca chng,
ti liu ni b, HSP, HTN. ti liu ni b, HSP, HTN.
L Huyn Trm, L Huyn Trm, Thc hnh Ho hc cc hp cht Thin nhin, ti liu ni b, Phng TN Thc hnh Ho hc cc hp cht Thin nhin, ti liu ni b, Phng TN
HCTN, HKHTN, HQGHN, 2006. HCTN, HKHTN, HQGHN, 2006.

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