hóa học các hợp chất thiên nhiên - phạm thế chính

8/10/2019 Ha Hc Cc Hp Cht Thin Nhin - Phm Th Chnh

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BI GING

HA HC CC H P CHT THIN NHINi t ng: CN Ha hc

GVGD: ThS. Phm Th Chnh

B mn Ha hu c Khoa Ha hc H Khoa hc

H Thi Nguyn


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NI DUNGCh ng 1: Ph ng php nghin c u

Ch ng 2: CacbohidratCh ng 3: TecpenoitCh ng 4: Steorit

h ng 5: Flavono tCh ng 6: Ancaloit


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CH NG 1PH NG PHP NGHIN C U

1.1 Lch s v i t ng nghin c u1.2 Phn lo i cc h cht thin nhin 1.3 Sinh tng h p cc h p cht thin nhin1.4 Qui trnh nghin c u cc h p cht thin nhin


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5/125

Nghin cu chuyn su

Xut pht

-Nhim v

Phn lp, nhn dng,nhc im

Xcnh cu trc

Tng h p cc h p cht phn t nh

Nghin cu hot tnh sinh hc


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1.2 Phn loi cch p cht thin nhin

H p cht s cp

n o

H p cht th cp


7/125

H p cht s cpProtein

Cacbohidrat

Protein

Lipit

Axit Nucleic

Lipit

Axit Nucleic

Lipit

Axit Nucleic


8/125

H p cht th cp

Protein

Tecpenoit

Steorit

Lipit

Axit Nucleic

Lipit

Axit Nucleic

Ankaloit

Flavonoit


9/125

1.3 Sinh tng h pcch p cht thin nhinCO2+ H2O

quang hp

CacbohiratCOOH

OHOH

HO

OH

COOH

O

CH2

COOH

Tanin

amino

axitnucleic

PO43-

phenylpropan

CH3COCOOHaxit pyrovic

CH3COOHaxetic

axit bopolyketides

CH3COH

CH2COOHCH2CH2OH

axit Mevalonictecpensteroit

protienpolipeptitancanoit

Purines

aminoaxit

N2

chu trnh axit citric


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1.4 Qui trnh nghin c ucch p cht thin nhin


11/125

CH NG 2

CACBOHIDRAT2.1 i c ng vcacbohidrat

2.2 Monosaccarit2.3 Oligosaccarit2.4 Polysaccarit


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2.1i c ng v cacbohidrat

Khi nim: Cacbohidrat hay cn gi l saccarit,gluxit, l cc h p cht hu c khng mu, t nhiuc v ngt, dtan trong n c, dkt tinh, c tmthy trong thc vt, ng vt, a s c cng thc

n 2 m.

Ngoi ra theo ngh a rng cacbohidrat c cN,S v khng phi u c v ngt.

Tn gi cc ! ng ring bit kt thc b"ngui oz (ose)


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Phn loi: da theo thnh ph#n v tnh cht cacacbohidrat

Cacbohidrat

Cacbohidrat n gin haymonoscarit (khng th thyphn c).VD: glucoz , riboz , fructoz ...

Cacbohidrat ph c

tp khi thy phnhon ton cho ccmonosaccarit.

Oligosaccaritto nn t 2 -10phn tmonosaccarit.VD: Saccaroz , lactoz .

Polysaccarit (glycan)to nnt l n h n 10 n hng vnmonosacarit: tinh bt,

xenluloz , glycogen


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-Ch c nng:+ Lm nhin liu cung

cp t i 60% n$ng l ng cho c thsng.

+ Lm khung cu trc vv b o v, th! ng c mt % cc

c' ng nh % m ni v vb o vng vt.

+ Lin kt v i protein vlipit mng, ng vai tr lmph ng tin vn chuyn tn hiugiacctbo.


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2.2 Monosaccarit2.2.1 Phn loi-nh ngh a: Monosaccarit l h p cht polyhidroxicacbonyl,phn tc nhiu nhm OH % cc nguyn tcacbon knhau.VD: glucoz , fructoz , riboz

CH2OH

CHOH

CHOH

CHOH

CHOH

CHO CH2OH

CHOH

CHOH

CHOH

C CH2OHO

CH2OH

CHOH

CHOH

CHOH

CHO

CH2OH

CHOH

CHOH

CHOH

CHOH

CHO CH2OH

CHOH

CHOH

CHOH

C CH2OHO


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-Phn loiMonosaccarit

-Da theo nhm C=O:

+ C=O l andehit: andoz

- Da theo s nguyn t C:

+ 2C (bioz ), 3C (trioz ),

,

6C (hexoz ), 7C (heptoz )

- Andoz

- Xetoz

CH2OH

CHOH

CHOH

CHOH

CHOH

CHO CH2OH

CHOH

CHOH

CHOH

C CH2OHO


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2.2.2 Cu hnh ca monosaccarita, Cng th c FisherQui nh cch vit cng thc hnh chiu fisher ca cc

monosaccarit:- Nhm c nguyn t cacbon soxi ha cao n"m trn

(nh ca trc th)ng ng (b*c-nam) (v tr s1).

- Nguyn t cacbon bt i (C*) khng vit ra mchnh l giao im ca cc trc th)ng ngvn"m ngang.

- Cc nguyn tH v nhm OH n"m % cc trc ngang(trc ng-ty) (nguyn tHcthkhng vit ra).


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VD: Biu din phn t glucoz b"ng cng thc chiuFisher

Nhm nguyn t cacbon c s oxiha cao

Nguyn t cacbon bti C*


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b, Cu hnh t ng i D,L- xc nh cu hnh t ng i D,L ca cc monosaccaritng! i ta xt cu hnh ca nguyn t cacbonchiral (C*) n"mxa nhm cacbonyl nht (C4 % pentoz , C5 % hexoz ). Sau so snh v i cu hnh ca C* trong phn tglyxerandehit.

+ C cu hnh D khi OH n"m % bn ph i ca cngthc chiu Fisher.

+ C cu hnh L khi OH n"m % bn tri ca cng thcchiu Fisher.

- +ng phn D v L l mt cp i quang, nn +ng phn Dl nh ca +ng phn L qua g ng v ng c li.

- +ng phnepimer l cc monosaccarit ch( khc nhau vcu

hnh ca nguyn tcacbon s2 (C2)


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V d v cu hnht ng i D,L camonosaccarit

Nguyn t C* xa nhmCHO nht D, L- nh vt qua g ng

-OH bn phi-OH bn tri


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V dvcc cp ng phn epimer ca cc pentoz

Cu hnh ca C2 khc nhau

Cp ng phnepimer


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Cc cp epimer ca hexoz

Cp ng phnepimer


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- Cu hnh tuyt i R,S ca monosaccarit c xcnh theo hthng danh php ca Can, Ingol v Preloc,ngh a l phn cp ca cc nhm th.

CHOHO H

CH2OH

H OHH OH

(2S, 3S, 4R, 5R)- Mannose


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2.2.3 Cu trc vng ca monosaccarit- Monosaccarit khng tham gia c ht cc ph n ng ctrng cho nhm cacbonyl. iu ny c Tollens giithch da trn phn ng ca nhm cacbonyl v i nhmhidroxy trong mi tr! ng axit to ra hemiaxetal (I) vaxetal (II).

- Khi to vng, nguyn t C % nhm cacbonyl tr% thnhnguyn tcacbon bt i C * , n c gi l nguyn tC anome.

RCHO R'OH (H ) R C OHOR'(I)

R'OH (H+

) R C OR'OR'(II)


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a, Cng th c Tollens- Cng thc Tollens biu din cc phn tmonosaccarit d idng hnh chnht:

+ Mt cnh chiu di l cng thc Fisher camonosaccarit.

+ Cnh chiu di cn li c trung im l nguyn t

oxi tham gia lin k t hemiaxetan.+ Hai cnh chiu rng l cch biu din lin kt bnh

th! ng.

- Trong tr! ng h p andohexoz , skt h p ca OH % C5 tora vng 6 cnh c tn l pyranoz , OH % C4 cho vng 5 cnhgi l furanoz .


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- C1 (andoz ), C2 (xetoz ) gi lC-anome nn HO-C1(C2) gi lOH-anome.- V i 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 -

H OHH OH

O

CH2OH

HO H

H OH

1

2

3

4

56

, -D-glucopyranoz

HO HH OH

O

CH2OH

HO H

H OH

1

2

3

4

56

- -D-glucopyranoz

HO HH OH

CH2OH

OHO H

1

2

3

4

56

H OH

- -D-glucofuranoz


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HOCH2 OH

H OHHO H

1 2

3

4

56HOCH2 H

O

HOCH2HO

HHO

OHH

12

3

4

5 6HOCH2H

O

, -D-fructofuranoz -L-fructofuranoz

- V i dy +ng phn L: l nh qua g ng ca dy D.

HO CH2OH

H OH

HO H

12

3

4

56HOCH2 H

O O

HOCH2H65

4

3

21

OHH

HHO

OHCH2OH

- -D-fructofuranoz --L-fructofuranoz

D, L- nh vt qua g ng


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b, Cng th c Haworth- Cng thc Haworth biu din cu hnh ca monosaccarit rrng h n, c biu th b"ng mt hnh 6 ( pyranoz ) cnhhoc 5 ( furanoz ) cnh, n"m trn mt mt ph)ng vung gcv i mt ph)ng giy v i 1 nguyn toxi n"m % pha sau.

O

Furan Pyran


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- Dy ng phn D: nhm CH2OH n"m % pha trn mt

ph)ng vng:+ +ng phn , khi OH-anome n"m % pha d i mt

ph)ng vng (-CH2OH vOH-anome ng c chiu nhau).

+ +ng phn - khi OH-anome n"m % pha trn mtph)ng vng (-CH2OH vOH-anome cng chiu).

- y ng p n : n n qua g ng c a y .

OOH

H

OH

HOH

H

H

OH

H

CH2OHO

H

OH

H

OHH

OH

OH

H

CH2OH

H

- -D-glucopyranoz --L-glucopyranoz


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, -D-xilofuranoz

- -D-xilofuranoz

D-Xiloz

Qu trnh hnh thnh vng ca ! ng 5


31/125

D-glucoz

- -D-glucopyranoz , -D-glucopyranoz

Qu trnh hnh thnh vng ca ! ng 5


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OOH

H

OH

HOH

H

H

OH

H

CH2OHO

OH

H

H

OHOH

H

H

OH

H

CH2OH

- c+ng phn L ta chiu D qua g ng, n gi n nht l

chiu theo ph ng ca trc z

z

OH

OH

H

OHH

OH

OH

H

CH2OH

HO

H

OH

OH

HH

OH

OH

H

CH2OH

H

- -

- -L-glucopyranoz

- -

- -L-mannopyranoz

G ng xy


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2

1

O

HOCH2 H6

5

4

3

21

HO H

H OH

HO CH2OH

OCH2OH

HOCH2 OH

H OH

HO H

1 2

3

4

56HOCH2 H

O

, -D-fructofuranoz --D-fructofuranoz

Cng thc Tollens

* Mi quan hgia cc cng thc biu din monosaccarit

6

5

4

3

O CH2OH

OHOH

HOH

HH

CH2OH O OH

CH2OHOH

HOH

HH

CH2OH

12

34

5

61

2

34

5

6

HO H

H OHH OH

CH2OH

, -D-fructofuranoz --D-fructofuranoz

D-fructoz

Cng thc Haworth

Cng thc Fisher


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c, Cng th c Reeves- Cng thc Reeves m t trng thi thc ca phn t, ccpyranoz c biu din % dng ghbn.

- -D-galactopyranoz

Haworth Reeves


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- Thc t a ph#n cc monosaccarit t+n ti trong thc t % dng cng thc Reeves, kc cc ! ng 5C.

- -D-ribopyranoz (56%) --D-ribopyranoz (18%)

, -D-ribopyranoz (20%) , -D-ribopyranoz (6%)D-riboz


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2.2.4 Tnh chthahc ca monosaccarita, Phn ng ca nhm cacbonyl- Trong dung dch kim cc xetoz d dng chuyn ha

thnh andoz , nn c andoz v xetoz u c ph n ngv i thuc thFellinh v Tollens1CH OH CHOH

6

5

4

32HO H

OHH OH

CH2OH

OHO H

H OHH OH

C

CH2OH

OHOH- OH- HO H

H OHH OH

CH2OH

HO H H OH

CH2OH

H OHH OH

HO H+

D-Fructoz Dng endiol D-Mannoz D-Glucoz


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-Ph n ng oxi ha:

+ Cc andoz c ph n ng v i Br2 /H2O, y l phnng dng phn bit andoz v xetoz .

+ Cc monoz khi b oxi ha b% i HIO4 to ra s nph&m l cc andehit v axit cacboxylic t ng ng khi c*t

HOCH2[CHOH]4CHOBr2, H2O HOCH2[CHOH]4COOH

n t , - o

R CHOH

CHOH

R' HIO4 RCHO + R'CHO

HOCH2 CHOH

CHOH

CHOH

CHOH

CHO + 5HIO4 5HCOOH + HCHO


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-Ph n ng kh

H OH

CH2OH

CHO

H OHOH

HO H

D-Glucoz

HO H

H OH

H OH

CH2OH

CHOHO H

D-Mannoz

H OH

CH2OH

CH2OH

H OHH OH

HO H

D-Sobitol

HO H

CH2OH

CH2OH

H OHH OH

HO H

D-Mannitol

Na-Hg

H+

NaBH4H+

HO H

H OHH OH

CH2OH

OCH2OH

H2Ni

H2Ni

D-Fructoz


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-Ph n ng osazon

HO H

H OHH OH

CH2OH

CHOHO HH OH

CH2OH

CHO

H OH

H OH

HO H

-

+ 3 C 6 H

5 N H N C H

3 C O + 3 C 6

H 5 N H N

H 2

O O H

- annoz

HO H

H OHH OH

CH2OH

OCH2OH

HO H

H OHH OH

2 H C 3

CH3COOH+3 C6H5NHNH2 (Osazon)

C

CH2OH

NNHC6H5

CH=NNHC6H5


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b, Phn ng ca nhm hydroxyl- Ph n ng v i Cu(OH)2

OHOCH2

H

H

HO

HO

H

OHH

OHOCH2

H

H

O

O

H

H

OHOH

H

HO CH2OH

H

H

O

O

H

H

HOOH

H

H

Cu

Cu(OH)2

1

2

3

45

6

12

3

45

6


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- Ph n ng to ete

OOHH H

CH2OH C H 3 O H H C l

( k h a n )

OOCH3

H

OH

HOH

H

H

OH

H

CH2OH

OHH

( C H 3 O ) S O

2 , N a O H

C H 3 I , N a O H

CH3O

OOCH3

HOCH3

HOCH3

H

H H

CH2OCH3


42/125

- Ph n ng to este

(CH3CO)2O

CH3COO

OOCOCH3

H

OCOCH3

HOCOCH3

H

H H

CH2OCOCH3O

OH

H

OH

HOH

H

H

OH

H

CH2OH

O CH2OH

OH

OH

HOH

H

H

CH2OH(CH3CO)2O

O CH2OCOCH3

OCOCH3

HOCOCH3

HH

CH2CH3COO

CH3COO


43/125

- Ph n ng to axetal v xetal vng

OH

OH

OH

HOH

H

H

OH

H

CH2OH

CH3 C CH3O

HCl (khan)

OH

O

O

HOH

H

H

OH

H

CH2OH

C

O OH

HOH

HOH

HH

CHOHCH2OH CH3

O H

H

OH

HH

CHCH2O

OC

CH3

CH3

OO C

CH3

CH3

HCl (khan)

CH3 C CH3O


44/125

2.3 Oligosaccarit- Oligosaccarit l nhng cacbohydrat m khi thy phn honton cho t2 n 10 monosaccarit.

- Oligosaccarit hay gp nht l cc disaccarit v trisaccarit.2.3.1 Disaccarit- saccar cac o ra c o ra monosaccarngh a l khi thy phn hon ton 1 phn t disaccarit s. thu c2phntmonosaccarit.

- Cc disaccarit thi nhin quan trng l: saccaroz , mantoz ,lactoz v xenlobiz


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46/125

- C cng thc phn t: C12H22O11, tn ha hc l: 2-O-, -D-

glucopyranozyl-- -D-fructofuranozit hay , -D-glucopyranozyl-(10 2)-- -D-fructofuranozit.

6

5

6

5

4

2

1 2

1

O H

CH OHOHH

CH2OHO H

HOH

H

OH

H

CH2OH

O

- Khi thy phn saccaroz trong dung dch axit long hocenzim thu c mt l ng b"ng nhau D-(+)-glucoz vD-(-)-fructoz . S thy phn ny gy ra s i du quay cct (+) sang (-), v vy qu trnh ny cn gi l qu trnhnghch o ! ng, h/ n h p trn c gi l ! ng nghch

o.

433

HOHOHH


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b, Lactoz

- Lactoz hay cn gi l ! ng sa c v ngt km h nsaccaroz , c vai tr quan trng trong dinh d1 ng ca tr2 em.Trong sa ng! i c t 6-7% lactoz , sa b ch( c 4-5%

lactoz .- C CTPT: C12H22O11, tn ha hc: 4-O-- -D-

galactopyranozyl-(10 4)-, -D-glucopyranoz

OH

OH

HOH

H

H H

CH2OH

OH

O

OH

HOH

H

OH

H

H

CH2OH

HO

1

23

4

5

6

4

5

6

3 2

1


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2.3.2 Trisaccarit- Trisaccarit l olisaccarit c cha 3 gc monosaccarit.Trisaccarit phbin nht v bit r h n c l rafinoz , c tnha hc: , -D-galactopyranozyl-(10 6)-, -D-glucopyranozyl-(10 2)-- -D-fructopyranozit

5

6

OHOH

CH2OH

2

3 4

5

6

1

23

4

4

5

6

3 2

1

OH

OH

HOH

H

H

OH

H

CH2OH

HOH

H

HO

O H

CH2OHOH

HOH

H

CH2OH

O

1


49/125

2.4 Polysaccarit- Polysaccarit l nhng polyme thin nhin, c cu to thng tr$m, hng nghn m*t xch l cc monosaccarit, lin ktcht ch. v i nhau qua lin kt glucozit.

- Polysaccarit c to thnh tmt loi monosaccarit c gi l homopolysaccarit, i din cho nhm ny l: tinh

, , .

- Polysaccarit c to thnh t hai loi monosaccarittr% ln c gi l heteropolysaccarit, hay gp nht trongthin nhin l: pectin, aga, hemixenluloz


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2.4.1 Tinh bt- Tinh bt l mt loi polysaccarit rt ph bin trong thinnhin. L thc $n quan trng ca c ng! i v ng vt.

- Tinh bt c d tr trong cc m thc vt d i dng ccloi ht, cqu (go, m3, ng, khoai , s*n, chui, ng), tpchung chyu trong cc loi ng' cc, go cha 78-80% tinh

, - , -70%...- Hm l ng tinh bt phthuc loi, ging, th! i v, a l vthnhng khc nhau.

h h h b l l h h h h


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- Vmt ha hc tinh bt l polyme sinh hc c to thnh

t cc monome l , -D-glycopyranoz lin kt v i nhau qualin kt 1,4 v 1,6-glucozit. c chia lm 2 loi:

+ Amyloz c to thnh t cc monome l , -D-

glycopyranoz lin kt v i nhau qua lin kt 1,4 glucozit.CH2OHCH2OH

L thnh ph#n chnh ca go t2 v cc ging ngu cc c t ixpcao(b% l n).

H

OH

HOH

H

H HH

OH

HOH

H

HH

O OO

4 1 4 1

n

A l i h h l D


52/125

+ Amylopectin c to thnh tcc monome l , -D-

glycopyranoz lin kt v i nhau qua lin kt 1,4 v 1,6glucozit.

O

OH

OH

HOH

H

HH

CH2OH

O1

L thnh ph#n chnh ca go np v cc ging ng' cc c d2o l n

O H

OH

HOH

H

H H

CH2

O H

OH

HOH

H

H H

CH2OH

O OO

4 1 4 1

n

6

2.4.2 Glycogen


53/125

- Glycogen l polysaccarit d trca c th ng vt, th! ngtp trung trong gan (khong 20%) v trong c b*p (kho ng4%), cn c gi l tinh bt ng vt.

- L cht r*n dng bt, mu tr*ng v nh hnh, d tan trongn c, phn t khi kh ng 1 tru vC, c cu trc t ng tamylopectin nhng mc phn nhnh cao h n.

CH2OH

OH

OH

HOH

H

H H

CH2O

H

OH

HOH

H

H H

CH2OH

O OO

O

O

H

OH

HOH

H

H H

O

4 1 4 1

n

1

6

2 4 3 X l l


54/125

2.4.3 Xenluloz - Xenluloz l mt polysaccarit cao phn t, khng c tnh! ng, l thnh ph#n chnh ca mng tbo thc vt , l c s% xy dng cu trc g/ ca thc vt. Xenluloz c nhiu trongtt c cc loi g/ (40-60%), trong bng ln t i 98%.- Xenluloz c to thnh t cc monome l --D-

, .

n

1414

O

OH

HOH

H

H H

CH2OH

H

O

OH

HOH

H

H H

CH2OH

HOO

O

2 4 4 Ag


55/125

2.4.4 Aga- Aga l mt polygalactopyranzit, c trong mt s loi rong tbin v mt sc thvi 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 l9:1:1.

- Cc m*t xch ca aga l D-galactoz c g*n v i nhau quaC1 v C3. n m*t xch th10 li c L-galactoz , % v tr s1 v 4 ca L-galactoz th to thnh mch, cn % v tr s 6ca n b este b% i axit sunfuric; mch cko di lin tc nhvy. (cng thc lb i tp sinh vin tv. ).


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CH NG 3TECPENOIT

3.1 Khi nim3.2 Monotecpenoit3.3 Secquitecpenoit

3.4 Ditecpenoit3.5 Tritecpenoit3.6 Tetratecpenoit

3.7 Polytecpenoit

3 1 Khi nim


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3.1 Khi nim- Tecpen hay cn g i l tecpenoit l nh ng h p ch t h uc ch a C, H v O t n t i trong thin nhin m c b khung cacbon g m nhi u m t xch gi ng v i khungcacbon c a isopren, t c l c th bi u di n b i cngth c (iso-C 5)n v i (n 2). O

khng theo qui t c !u n"i v#i uiSqualen

Zerumbon

1 2

34

56

78

910

11

Oximenisopren

!uui


58/125

Loi tepen Khung cacbon S l ng CMonotecpen (iso-C5)2 10-

- phn loi tecpen ng! i ta c$n c vo sl ng n v isopren h p thnh phn bit:

5 3

itecpen (iso-C5)4 20Tritecpen (iso-C5)6 30Tetratecpen (iso-C

5)8

40

3 2 Monotecpenoit


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3.2 Monotecpenoit3.2.1 Axiclic monotecpen- Cc monotecpen khng vng l d4n xut ca 2,6-

imetyloctan, % h#u ht cc monotecpen ny u chanhm isopropyliden (a) (+ng phn -) v mt s t chanhm iso ro en l b +n hn , .

2

6

(b)(a)2,6-imetyloctan

a Hidrocabon tecpen


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a, Hidrocabon tecpen- i v i hirocacbon tecpen loi ny, ch( c haihirocacbon ng c cp n l Oximen v Mirxen ,m/ i cht u c 3 lin kt C=C. Chng xut hin trong tinhd#u basil (Ocimum basilicum ), v tinh d#u cy nguyt qu(laurel oil). C hai u c cha ni i lin h p, chng ch(hn bit c v i nhau b% i v tr caccni i.

MirxeOximen

b Dn xut ancol tecpen


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b, Dn xut ancol tecpen-5 ng v i 2 khung hirocacbon tecpen c nhng ancol tecpencha mt hoc 2 lin kt i, u l nhng cht c mi th m ctrng, nhng n h ng qu tch c t tinh d#uhoah+ng, tinh

d#u s OHCH2OH

Linalool l mt ancol bc 3 quang ht, l thnh ph#n ca nhiuloi tinh d#u, nh tinh d#u cy o i h ng v trong tinh d#u htmi n xut hin v ihml ng kh cao.

Linalool

CH2OH

NerolGeraniolitronellol

2

c Dn xut cacbonyl tecpen


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c, Dn xut cacbonyl tecpen

Citronellal

CHO

Geranial (Citral a)

CHO

Neral (Citral b)

CHO

H+

*C CH

H

CO

CH3H

C CH

H

CO

CH3

C CH

H

CO

CH3

OH-, H2O

(CH3)2CO

citral

C O

3 2 2 Monoxiclic monotecpen


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3.2.2 Monoxiclic monotecpen- C$c monoxiclic monotecpen %u l& d'n xu(t c)a p*menthan+ p*menthan xu(t hi,n d-#i hai dng khngquang hot. c$c /ng ph0n cis v& trans.

HH

77

7

H H

p-menthan cis - p-menthan trans - p-menthan

2

345

6

89 10

1 2

345

6

8

910

1 2

345

6

8

910

a, Hidrocacbon tecpen


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* 1rong s" 23 /ng ph0n c)a menthanien c4 th5 t/n ti. ch6 c4 7 /ng ph0nd-#i 0y -c tm th(y trong tinh d!u th8c v9t:

***

*terpinen *terpinen terpinolen *phellandrene *phellandren limonen; R


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*Benthanol ho c menthan*D*ol. C2?- @E?F. l& ancol no c4 ba trung t0mchiral trong ph0n tG. v& kHt quI c4 t$m /ng ph0n l9p th5+ C(u hnt-ng "i giJa nh4m hiroxi v& nh4m isopropyl K -c x$c LnhM

neo*menthol v& neo*isomenthol E nh4m n&y Lnh h-#ng cis v#i nhau.cOn N mentol v& isomenthol chPng l& trans c)a nhau+

H

;Q


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trong tinh d!u bch 9u kh(u+ Thi l c*1erpineol v#i dung dLch axitsunUuric loKng c4 th5 thu -c hirat c)a 2.V*tecpin. C2?@E?F E+

O

(H2O )

(H*)

*O H

H3C O H(H+)H2O

H2OO H

*1erpineol 2.V*tecpin 2.V* Cineol

* Carvomenthol. C2?@E?F c4 cng thWc nhsau

OH

c, Cacbonyl tecpen


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*Carvon . p*methan*7.V;X


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pulegon. isopulegon v& piperiton. t(t cI chPng %u c4 nh4m xeto N vL tr_ CD+

isopulengon

H

OH

Pulegon

O

Piperiton

O

* Benthon. p*menthan*D*on. C2?@2VF. chWa E nguy]n tG cacbon b(t"i xWng. v& t/n ti N 3 /ng ph0n quang hot+

D,L-isomenthonD,L-menthon

OO


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* C$c xeton no v#i nh4m chWc oxo tr]n CE nh- N Carvomethon

OH

O

OH

O

Isocarvomenthon

Neoisocarvomenthol

Isocarvomenthol

OH

Neocarvomenthol

Carvomenthon

Carvomenthol

OH

3.2.3 Bixiclo monotecpen


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p- C$c monotecpen hai vOng -c ph0n loi theo ` nh4mvOng no nh-: thu an. caran. pinan. boran. isocamphan.Uenchan. v& isobornilan+

fenchanIsobornilanIsocamphan

hujan

Bornan (Camphan)PinanCaran

a, Nhm pinan


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* @irocabon khng no quan tr ng v& * pinen l& c$c th&nhph!n ch) yHu ;V?*X? < c)a tinh d!u thng+

* inen ;2 7?C< * inen ;273?C+. uphorbiaceaceM n4 l& ch(t /ng g0y ung th-+

OH OH

PhorbolO OH

H HH

CH2OH

3.5 Tritecpen1(t cI c$c tritecpen mAt vOng Hn n m vOng v& c$c hp ch(t


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kh$c b t ngu/n t[ squanlen. CD?@ ?+ o v9y c$c tritecpen cOng i l& c$c squalenoit

HO H

H

H

H

H

Lanosterol

HO H

Squalen

HOH

H

H

R

HOH

H

H

Hopan anfa-amyrin R=CH3 (beta-amyrin)R=COOH (axit oleanolic)

3.6 Tetratecpen1etratecpen hay cn gi l carotenoit l& c$c ch(t m!u th8c ph m. hay


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cOn g i l& c$c s c t" polyen+ Caroten l& h n hp c)a D /ng ph0n. . v& * caroten. >ycopen g0y ra m!u th'm c)a c& chua v& nhi%uloi quI kh$c+

*

anfa-caroten

beta-caroten

gama-caroten

Lycopen

3.7 Polytecpen* olytecpen hay cn gi l polypren, trong cao su thin nhin l


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mt s n ph&m quan trng (chu i ca ;w


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CH NG 4STEROIT

4.1i c ng4.2 Cc sterol4.3 Cc axit mt

4.4 Cc steroit vitamin4.5 Cc steroit hocmon

4.1 i c ng* \A khung c)a c$c steroit c(u to bNi b"n vOng cacbon d_nh kHt v#i


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nhau 5 to th&nh penhiro xiclopenta a phenanthren. C2`@EV. haycOn g i l& gonan ho c steran+

27

262524

232221

20

19

18

B

C D12 8

9

10

11

12 13

14 15

16

1717

16

1514

1312

11

10

982

1 DC

BA

- c i m d!nh "#t $%ng + C$c vOng v& \ c4 th5 d_nh kHt v#i nhauho c theo cis ho c theo trans. vOng \ v& C lun trans. vOng C v& th-fng trans. tuy nhi]n c ng th-fng g p s8 d_nh kHt cis. th_ dj nh- c$c cacdenolit v& c$c buUadienoit+

CholestanGonan

3

4

56

776

54

3

- Sh4m metyl N nguy]n tG cacbon s" 2? -c dZng l&m i5m chu n+C$c nh4m thH v& c$c nguy]n tG hidro -c Lnh vL N cZng ph_a tron


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ph0n tG nh- nh4m n&y -c ch6 Lnh l& c$c nguy]n tG M c$c nh4mthH ho c nguy]n tG hiro N ph_a ng-c li c)a vOng l& c$c nh4m +@ai /ng ph0n l9p th5 l& **cholestan v& **cholestan. c$c vOng\ C v& C -c d_nh kHt trans+

1717

**Cholestan **Cholestan; *\: trans< ; *\: ciseucoanthoxianin cOn -c g i l Ulavan*D.3*diol+


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Thi un si v#i n-#c ho c etanol c4 m t axit @Cl.leucoanthoxianin s chuy5n h4a thnh anthoxianin+C$c ch(t thuAc nh4m ny m#i ch6 tm th(y d-#i dng

aglycon. ch-a tm th(y N dng glyco it+

h, Nhm catechinCatechin l c$c d'n xu(t Ulavan*D*ol+ o c4 hai trung t0m

khng trZng v9t Inh. chPng t/n ti d-#i dng hai c p diastereome.dj $ hi i hi


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g g g g pv_ dj c$c c p catechin v epicatechin+

1rong s" b"n /ng ph0n quang h c ny c)a catechin thch6 c4 ;=


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% m t c(u trPc. iso Ulavanon kh$c iso Ulavon N ch

khng c4 li]n kHt i giJa CE v CD. loi hp ch(t ny c ngkhng cho phIn Wng mu xianidin+

5.3 inh t ng h p c+c h p ch/t lavonoit- 6 c$c Ulavonoit mAt n vL C2 c sN bao gif c ng c4 m tnh- -c th5 hi,n N c(u trPc sau:


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(

* \zng c$c th_ nghi,m $nh d(u bzng /ng vL ph4ng x ng-fita K x$c Lnh -c rzng ti5u n vL rCD c4 ngu/n g"c t[ shikimat v ki5u n vL kia ;nh0n thm < c4 ngu/n g"c t[

polyketit+* Ti5u kHt hp oxi c)a vOng -c ch6 ra N hnh tr]n v vOng\ c4 ki5u thH 3*hidroxy. D.3*dihidroxy ho c D.3. *trihidroxy+


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109/125


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5.4%o*t t0nh sinh h c c2a c+c lavonoit- C$c Ulavonoitc4 t$c djng ch"ng oxi h4a ;antio&idant


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-c hot t_nh sinh h c c)a chPng+ lavonoit c4 khI n ng km hKmc$c qu$ trnh oxy h4a d0y chuy%n sinh ra bNi c$c g"c t8 do hotAng+* 1uy nhi]n. hot t_nh ny th5 hi,n mnh hay yHu phj thuAc vo ci5m c(u to h4a h c c)a t[ng ch(t Ulavonoit cj th5+


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CH NG 6ANCALOIT


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ANCALOIT6.1 Khi nim v vai tr sinh hc6.2 Phn l p ancaloit6.3 Phn loi v danh php

6.4 Mt s ancaloit tiu bi u

6.1 Khi nim v vai tr sinh hc

a, &h+i ni m 'ncaloit l m t nh*m h+p ch t thi n nhi n m h u h#t


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l c/c d0 $%ng ch1a nit2, c* t!nh 3a42, c* trong m t s5 sinh$6t nh t 0nh.

3

12

O

O

1211

109

8 7 6

5

4

OCH 3

CH 3ON+

OH

Beberin

4 a' NicotinN

CH3

N

N

O

CH3

OCH3

N

N

CH3

Cofein

b, !ai tr sinh hc

* ncaloit hnh th&nh 5 bIo v, c0y. v c$c ancaloitn4i chung %u r(t Ac v#i Ang v9t+


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g ( g* ncaloit c4 vai trO g0y ph$t djc cho c0y+* ncaloit l& ch(t d8 trJ dinh d-ng nui m!m c0y

cho thH h, sau+* ncaloit l& ch(t trun ian ha ch(t thIi tron u$

trnh trao i ch(t+C4 th5 ancaloit c4 cI b"n chWc n ng tr]n+

6.2 Phn l p ancaloit

a. Sghi%n nh nguy]n li,u ;l$. th0n. r< th&nh bAt r/ing0m v#i dung dLch axit @Cl ;ho c ng0m tr8c tiHp bzng dung


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dLch SaECFD< 5 chuy5n ho$ ho&n to&n ancaloit th&nh mu"iclohidrat d tan+

b. > c l(y dung dLch mu"i ;b bK 5 xG l_ giai onsau


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ancaloit thnh 4 nhm cht nhsau:= Sh4m 2 c4 c$c nguy]n t" C. @. S+= Sh4m E c4 c$c nguy]n t" C. @. S. F+= Sh4m D c4 c$c nguy]n t" C. @. S. Y+= Sh4m 3 c4 c$c nguy]n t C. @. S. F. Y+

C$c ancaloit nh4m D c4 A Ac cao nh(t. th-fng c4 trong n(mAc+


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6.3.2 Danh php

* i,c $nh s" trong vOng ancaloit n giIn tu0n theovi,c $nh s" trong c$c dL vOng K biHt+ 1h_ dj. c$c


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ancaloit loi tropen $nh s" theo ki5u vOng bixiclo:

78 3

21

NCH 3

Atropin

Tropan

9 '

8 '

7 '6 ' 5 '

4 '

3 '2 '1 '

3NCH 3

H

O CO

CH

CH 2OH

1 2

45

8

6

7

5


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* #i c$c vOng phWc tp hn th phIi ch n vOng c sN g!n gi"ng v#ivOng K biHt r/i $nh s" vOng c sN theo ki5u $nh s" vOng K biHtiHp Hn c$c vOng kh$c sao cho c4 tr9t t8 hHt vOng n&y Hn vOnkh$c+


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kh$c*1h_ dj: {$nh s" trong ph0n tG mophin. mAt ancaloit loi

isoquinolin. nHu $nh s" vOng t[ isoquinolin th r(t phWc tp. n]nobinson K bi5u din v& $nh s" theo ki5u vOng phenantren:2

12

34

567

8

9

10

11

1213

14

PhenantrenMophinki5u phenantren

O

HO

N CH3

34

5

67

8

9

1011

1213 14 15

1617


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Ti liu tham khoTi liu tham khoCarey F.A.Carey F.A.Organic chemistryOrganic chemistry (5ed., MGH,(5ed., MGH,20042004)(T)(C)(1335s).)(T)(C)(1335s).


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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,19931993

. J. A. March , M. B. Smith"Advanced Organic Chemistry. Reactions, Mechanisms and. J. A. March , M. B. Smith"Advanced Organic Chemistry. Reactions, Mechanisms andStructure (Fifth Edition), J. Wiley & Sons,Structure (Fifth Edition), J. Wiley & Sons,20012001..J. Clayden, N. Greeves, S. Warren and P. Wothers,J. Clayden, N. Greeves, S. Warren and P. Wothers,Organic ChemistryOrganic Chemistry , Oxford University, Oxford University

, ,, ,Ng Th Thun, ng Nh Ti, Ha hu c tp 2, NXB GDNg Th Thun, ng Nh Ti, Ha hu c tp 2, NXB GD20122012..

Phm Th Chnh,Phm Th Chnh, Bi gi ng Ho h c cc h p ch t Thin nhin, ti li u ni b , HKH, H Bi gi ng Ho h c cc h p ch t Thin nhin, ti li u ni b , HKH, HTN TN Phan Tng S n,Phan Tng S n, Bi gi ng Ho h c cc h p ch t Thin nhin, ti li u ni b , HKHTN, Bi gi ng Ho h c cc h p ch t Thin nhin, ti li u ni b , HKHTN, HQGHN. HQGHN.Nguyn V$n u,Nguyn V$n u, Bi gi ng Ho h c cc h p ch t Thin nhin, ti li u ni b , HKHTN, Bi gi ng Ho h c cc h p ch t Thin nhin, ti li u ni b , HKHTN, HQGHN HQGHN. .

Phm V$n Th(nh,Phm V$n Th(nh, Bi gi ng Ho h c cc h p ch t Thin nhin v ho t tnh sinh l c a chng, Bi gi ng Ho h c cc h p ch t Thin nhin v ho t tnh sinh l c a chng,ti li u ni b , HSP, HTN.ti li u ni b , HSP, HTN.L Huyn Trm,L Huyn Trm,Th c hnh Ho h c cc h p ch t Thin nhin, ti li u ni b , Phng TNTh c hnh Ho h c cc h p ch t Thin nhin, ti li u ni b , Phng TN

HCTN, HKHTN, HQGHN, 2006. HCTN, HKHTN, HQGHN, 2006.


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