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. 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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.