T S CHNG- TRNG PTTH CHUYN QUNG BNH

Cacbohidrat i cng v danh php 1. Da trn cng thc chung gii thch tn gi cabohidrat.

Cng thc chung ca cabohidrat l Cn(H2O)m. Tn gi ny ch ra hai thnh phn ca cng thc l cacbon (cacbo) v nc (hidrat).

2. Cho bit hai loi nhm chc c trong cabohidrat in hnh. >C=O v -O-H. Cc cacbohidrat l cc polihydroxy andehit hoc xeton, trong nhm -OH lin kt vi cc nguyn t cacbon khng phi l cacbon ca nhm cacbonyl.

3. (a) Tn gi chung cho cc cacbohidrat l g ? (b) Tip v ng trong tn gi ca cc cacbohidrat n gin l g ? (a) ng. (b) -oz, i khi ng thuc loi xeton c c lip v ng -uloz.

4. nh ngha (a) saccarit, (b) monosaccarit, (c) disaccarit, (d) oligosaccarit v (e) polisaccarit. (a) Saccarit l tn gi khc ca cacbohidrat v l thut ng c s dng khi phn loi cc cacbohidrat. Ch saccarit xut pht t ch saccharum trong ting Latinh c ngha l ng. (b) Monosaccarit l mt ng n. (c) Disaccarit c cu thnh t hai monosaccarit. d) Oligosaccarit cu thnh t 3-10 monosaccarit. (e) Polisaccarit c cu thnh bi trn 10 monosaccarit.

5. (a) Cho bit quan h v thnh phn nguyn t gia hai monosaccarit v mt disaccarit tng ng. (b) Vit cng thc chung ca cc disaccarit. (c) Vit phng trnh thy phn trisaccarit di tc dng ca enzim (s dng ch thay cng thc). (a) S kt hp hai phn t monosaccarit hnh thnh nn mt phn t disaccarit ng thi enzim vi vic gii phng mt phn t nc. (b) Cn(H2O)n-1. (c) Trisaccarit + 2H2O 3 monosaccarit.

6. S dng tip v ng -oz trong tn gi mi monosaccarit sau : (a) HOCH2CHOHCOCH2OH, (b) HOCH2(CHOH)4CHO v (c) HOCH2(CHOH)4CH2CHO. Ngoi tip v ng trn, chng ta s dng cc tip u ng ando-, xeto- ch nhm cacbonyl tng ng v -di-, -tri-, ... ch s nguyn t cacbon trong mch, nh vy (a) xetotetroz, (b) andohexoz v (c) deoxyandopentoz (deoxy cho bit thiu mt nhm -OH trn mch). Mt cch chnh xc hn th cht ny thuc loi 2-deoxyandopentoz (thiu mt nhm -OH trn nguyn t cacbon s 2).

7. Vit cng thc phn t cho (a) mt tetroz tetrasaccarit v (b) mt polypentosit (pentosan).

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

(a) Theo lp lun ca bi tp 23.5a chng ta c 4C4(H2O)4 C16(H2O)13 + 3H2O, hay cng thc phn t ny c th vit l C16H26O13. (b) Polysaccarit c hnh thnh t n phn t monosaccarit v loi i n phn t H2O, nh vy cng thc phn t ca loi hp cht cho trn s l [C5(H2O)4]n hay (C5H8O4)n.

8. Xc nh cng thc ca glucoz t cc d kin sau : Thnh phn % cc nguyn t l C = 40,0 ; H = 6,7 ; O = 53,3. Dung dch cha 9,0g glucoz trong 100g nc ng c -0,93oC. C:H:O=
40,0 6,7 53,3 = = =1: 2 : 1 12 1 16 180 = 3, 30

cng thc nguyn (CH2O)n , M = 30n

M = 1,86. 9.1000 = 180 100.0,93

n =

Cng thc phn t ca glucoz l C6H12O6 (hexoz). Ha hc lp th 9. (a) Vit cng thc Fischer cho cc ng phn D v L ca mt ng n gin nht. (b) Vit k hiu ch chiu quay cc ca cc ng phn i quang ny. (c) Cho bit cu hnh tuyt i ca mi ng phn. (a) ng l hp cht polyhidroxy nn c ti thiu hai nhm -OH, ng n gin nht phi l mt trioz (glixerandehit) (b) Fischer p t cu hnh D cho cc ng phn enan quay phi, nh vy D l (+), L l (-). (c) D l R v L l S.
CHO H OH CH2OH HO CHO H CH2OH

D (OH bn phi)

L (OH bn tri)

10. Ch r cu hnh D/L cho cc cng thc chiu Fischer di y ca glixerandehit.

CH2OH (a) HO H CHO (b) HOH2C H OH CHO (c) H OH CHO CH2OH

Trc ht chng ta xc nh cu hnh tuyt i R/S ca chng v vi s tng ng R l D v S l R ta xc nh c cu hnh D/L. Vi trt t hn cp -OH > -CHO > -CH2OH ta c (a) R hay D, (b) R hay D, (c) S hay L. Ch rng trong cc cng thc (a) v (c) nguyn t H nm trn ng ngang.

11. (a) Vit cng thc cu to ca mt ng xetoz n gin nht. (b) Cho bit s khc nhau v cu to gia ng xetoz ny v glixerandehit (khng k n loi hp cht cacbonyl). (a) HOCH2COCH2OH. (b) ng xetoz ny khng c tm bt i.

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

12. (a) Trong andotetroz c bao nhiu tm bt i ? (b) Vit cng thc Fischer cho cc ng phn i quang ca mt andotetroz v xc nh cu hnh D/L ca chng. (a) C hai tm bt i : HOCH2-*CHOH-*CHOHCHO. (b) Theo qui c cu hnh D ca ng ng vi nhm -OH trn C* c ch s v tr cao nht pha bn phi v cu hnh L ng vi nhm -OH trn C* c ch s v tr cao nht pha bn tri :
CHO H H OH OH CH2OH D - erythro HO HO CHO H H CH2OH L - erythro HO H CHO H OH CH2OH D - Threo H HO CHO OH H CH2OH L -Threo

13. Cho bit s khc nhau gia D-erythro v D-threo khi chng b oxi ha nh nhng. Khi oxi ha nh nhng th -CH2OH v -CHO chuyn thnh nhm -COOH, to ra cc ng phn dia ca axit tactaric. Dng threo to mt ng phn i quang hot ng quang hc, trong khi dng erythro to mt ng phn mezo khng hot ng quang hc.
OH H HOH2C C C CHO H OH D - threo OH OH HOH2C C C CHO H H D - erythro [O] OH H HOOC C C COOH H OH Axit D -(-)-tactaric OH OH HOOC C C COOH H H Axit mezo-tactaric

[O]

14. Cho bit s khc nhau gia D-erythro v D-threo khi chng b kh. Nhm -CHO b kh thnh nhm -CH2OH to ra 1,2,3,4-butantetrol. Threo to c mt ng phn enan hot ng quang hc trong khi erythro to ng phn mezo khng hot ng quang hc.
OH H HOH2C C C CHO H OH D - threo OH OH HOH2C C C CHO H H D - erythro [Kh] OH H HOH2C C C CH2OH H OH D-1,2,3,4-butantetrol OH OH HOH2C C C CH2OH H H mezo-1,2,3,4-butantetrol

[Kh]

15. Ti sao cc ng phn ca axit tartric v 1,2,3,4-butantetrol hot ng quang hc c xp vo dy D ? Trong sut qu trnh oxi ha hoc kh cu hnh ca nguyn t C bt i khng thay i, do cu hnh D ban u c bo ton.

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

16. Cho bit nh ngha ca thut ng epime v dng cu hnh erythro, threo minh ha nh ngha ny . Thut ng epime c s dng ch cc ng phn dia c nhiu tm bt i, nhng ch c mt cacbon bt i c cu hnh khc nhau. D-threo v D-erythro l epime do cu hnh C2 ca chng khc nhau.

17. (a) Cc hp cht mch h sau y c bao nhiu nguyn t cacbon bt i : (i) andohexoz nh glucoz v (ii) 2-xetohexoz nh fructoz ? (b) Andohexoz c bao nhiu ng phn quang hc ? (a) (i) bn : HOCH2*CHOH*CHOH*CHOH*CHOHCHO (ii) ba : HOCH2*CHOH*CHOH*CHOHCOCH2OH

(b) Do c bn nguyn t cacbon bt i nn s c 24 = 16 ng phn quang hc. 18. Loi andohexoz mch h no c 8 ng phn quang hc ? Deoxyandohexoz c ba nguyn t cacbon bt i nn s c 23 = 8 ng phn quang hc. Phn ng 19. (a) Cho bit kh nng phn ng, hin tng v sn phm to thnh khi andohexoz v 2xetohexoz tc dng vi : (i) thuc th Tollens, (ii) thuc th Fehling, (iii) thuc th Benedict v (iv) Br2/H2O. (b) Sn phm hnh hnh t andohexoz c xp vo loi no ? (a) Cc thuc th ny u c tc dng oxi ha nhm -CHO thnh -COOH hoc mui ca n. (i) Thuc th Tollens l hp cht phc Ag(NH3)2+, c hai cht u tc dng vi thuc th ny to kt ta trng bc. S d ng xeto phn ng c l do trong mi trng kim chng chuyn ha thnh mt ng ando (xem bi 23.23). (ii) Thuc th Fehling l phc Cu2+ tartrat trong NaOH, c hai cht u tc dng vi thuc th ny lm nht mu xanh ca dung dch thuc th v hnh thnh kt ta Cu 2O mu gch. (iii) Thuc th Benedict l phc Cu2+ xitrat trong NaOH, hin tng v sn phm hnh thnh ging nh phn ng ca thuc th Fehling. (iv) Ch ng ando phn ng c lm mt mu da cam ca dung dch brom. (b) Sn phm hnh thnh t c hai loi ng trn u thuc loi axit andonic HOCH2-CHOH-CHOH-CHOH-CHOH-COOH.

20. Cho bit sn phm to thnh khi cho andotetroz tc dng vi HNO3. HNO3 oxi ha ng thi nhm -CHO v -CH2OH thnh nhm -COOH, sn phm to thnh thuc loi axit andaric HOOC-CHOH-CHOH-COOH.

21. Cho bit loi phn ng v sn phm to thnh khi cho andotetroz v xetotetroz tc dng vi H2/Ni, dung dch NaBH4 hoc Na/Hg. Cc tc tc nhn ny u ng vai tr cht kh nhm >C=O thnh nhm >CHOH, sn phm to thnh l mt anditol HOCH2-CHOH-CHOH-CH2OH. CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

22. Vit cng thc chiu Fischer ch r cc ng phn lp th hnh thnh khi kh mt Dandotetroz v mt D-xetotetroz. D-andotetroz v sn phm kh anditol u c hai nguyn t cacbon bt i (xem bi 23.14), D-xetotetroz ch c mt nguyn t cacbon bt i nhng qu trnh kh to nguyn t cacbon bt i th hai do vy sn phm kh cha hn hp hai ng phn dia anditol.
CH2OH H O OH CH2OH D - xetotetroz H H CH2OH OH OH CH2OH + CH2OH HO H H OH CH2OH D-anditol

mezo-anditol

23. Do tn ti mt cn bng gia andohexoz v 2-xetohexoz trong mi trng kim m 2xetohexoz phn ng c vi thuc th Fehling (xem bi 23.19). (a) Gii thch s tn ti ca cn bng ny. (b) Gii thch s hnh thnh hai ng phn dia andohexoz. (a) S tautome ha trong mi trng kim ca andohexoz v 2-xetohexoz to mt trng thi trung gian chung, nh m cn bng gia chng c thit lp.
H C O H C OH H C OH andoz H C OH C OH H C OH endiol
+

H CH OH H O OH

xetoz

(b) Khi hnh thnh li andoz t endiol, H c th tn cng vo C2-sp2 t hai pha khc nhau to hai ng phn epime khc nhau cu hnh ca C2.
sp3 - bt i H C OH 2 C OH H C OH endiol H C O H C OH H C O HO C H

sp2 - khng bt i

H C OH + H C OH Cc ph epime C2 ng n

24. (a) Cho bit cc sn phm to thnh khi cho HIO4 tc dng vi (i) HOCH2-CHOH-CHOHCHOH-CHOH-CHO (andoz) v (ii) HOCH2-CHOH-CHOH-CHOH-CO-CH2OH (2xetoz). (b) Da trn loi phn ng ny trnh by mt phng php n gin phn bit hai ng phn ny. (a) HIO4 ng vai tr mt tc nhn oxi ha : (i) -CHO, >CHOH chuyn thnh HCOOH v -CH2OH chuyn thnh H2C=O, vy sn phm l : 5HCOOH + H2C=O, (ii) >C=O chuyn thnh CO2, vy sn phm l : 2H2C=O + 3HCOOH + CO2. (b) Nhn bit CO2 da trn phn ng to kt ta trng CaCO3 vi dung dch Ca(OH)2 d, t nhn bit c xetoz.

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

25. (a) Cho bit cc cht trung gian v sn phm to thnh khi cho D-threo tc dng vi PhNHNH2. (b) Khi D-erythro tham gia phn ng ny th sn phm l g ? Gii thch sn phm thu c. (c) C th kt lun iu g khi tin hnh phn ng ny vi cc ng phn epime. (a) Phn ng ca D-threo :
CHO HO H H OH CH2OH D - Threo
2

+ PhNHNH2

H C NNHPh HO H H OH CH2OH

PhNHNH2 -PhNH2,-NH3

H C NNHPh C O + PhNHNH H OH CH2OH

H C NNHPh C NNHPh H OH CH2OH osazon

(b) D-erythro cng to mt osazon ging nh trn. Cu hnh C trong hp cht ng ban u khng quan trng do n b oxi ha thnh nhm >C=O to mt xeton ging nhau t c hai loi ng trn. (c) Ni chung cc ng phn epime-C2 ca ng ando to ra cng mt osazon. 26. Cho bit osazon hnh thnh t 2-xetohexoz v nh gi kh nng hnh thnh sn phm ny. Phn ng oxi ha 1o-OH d dng hn 2o-OH, nn s hnh thnh osazon din ra d dng hn.
H C NNHPh C NNHPh (H OH)3 CH2OH

27. (a) 2-xetohexoz c tng hp t osazon ca andoohexoz nh th no ? (b) Phng php ny chuyn ha glucoz thnh fructoz, vy bn c th nhn xt g v cu hnh ca cc nguyn t C3, C4, C5 ca andohexoz v ca 2-xetohexoz ? (a) Nhm phenylhidrazinyl ca osazon chuyn qua PhCHO to ra PhCH=NNHPh v mt hp cht cacbonyl gi l oson, sau nhm andehit b kh d dng (trong khi nhm xeton khng b kh) to thnh 2-xetohexoz :
H C NNHPh C NNHPh (H OH)3 CH2OH + PhCHO H C O C O (H OH)3 CH2OH oson Zn/HAc CH2 OH C O (H OH)3 CH2OH

- 2PhCH=NNHPh

(b) Cu hnh ca cc nguyn t C , C , C khng thay i trong qu trnh phn ng, do vy cc ng phi c cu hnh ging nhau cc nguyn t cacbon ny. 28. (a) Vit hai sn phm l ng phn hnh thnh trong phn ng gia D-threo v NaCN/HCN. (b) Kt qu ca phn ng ny c nh hng g n mch cacbon ? (a) Sn phm l cc ng phn xianohidrin C2-epime :

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

H C O HO H + NaCN/HCN H OH CH2OH D - Threo CN HO C H HO H H OH CH2OH + CN H C OH HO H H OH CH2OH

(b) Mch cacbon c s nguyn t cacbon tng thm mt. 29. Ti sao hai ng phn epime trong bi 23.28 li c to thnh vi hm lng khng bng nhau ? Nguyn t C2 bt i trong cc ng phn epime hnh thnh t nhm cacbonyl, qu trnh tn cng vo hai pha ca nhm ny chu nh hng khng gian lm cho tc qu trnh din ra khc nhau nn sn phm to thnh c hm lng khc nhau.

30. Cho bit s bin i cu trc ca (a) glucoz v (b) fructoz khi phn ng lin tc vi (1) NaCN/HCN, (2) H3O+, (3) HI/P. Glucoz v fructoz phn ng tng t nh nhau, bc mt l cng thm mt nhm -CN vo nhm >C=O to ra mt xianohidrin, bc hai thy phn nhm -CN thnh nhm -COOH, bc ba kh tt c cc nhm -OH thnh -H v sn phm to thnh l mt axit ankylcacboxilic. (a) Thu c axit heptanoic khng nhnh, iu ny chng t glucoz l mt andohexoz. (b) Thu c axit 2-metylhexanoic mch nhnh, iu ny chng t fructoz l mt 2-xetohexoz.

31. Cho bit cc bc chuyn ha t andopentoz thnh andohexoz theo phng php Kiliani-Fischer, bit rng bc u tin ca phng php ny l phn ng cng HCN vo nhm >C=O. Cc bc chuyn ha :
CN HC O (HC OH)2 + NaCN/HCN HC OH CH2OH D -andopentoz HC OH (HC OH)2 + H3O+ HC OH CH2OH xianohidrin COOH HC OH (HC OH)2 HC OH CH2OH axit glyconic O C HC OH (HC OH)2 O HC CH2OH -lacton HC O HC OH (HC OH)2 HC OH CH2OH D -andohexoz

+ Na/Hg - CO2

Lu rng (i) -lacton cng sinh ra ng thi vi -lacton v chng to thnh hn hp khng th tch ra khi nhau. (ii) Sn phm thu c cui cng l hn hai ng phn C2epime. 32. (a) Giai on no trong tng hp Kiliani-Fischer l tt nht tch hai ng phn dia ? (b) Hin nay ngi ta ci tin phng php Kiliani-Fischer nh th no ? (c) Andohexoz thu c thuc dy cu hnh D hay L ? (d) C th p dng phng ny tng mch cho xetoz mch thng c khng ?

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

(a) Giai on tt nht l tch cc ng phn dia ca axit glyconic, chng c tch ra di dng mui kt tinh. (b) Cc xianohidrin c kh trc tip thnh andoz bng qu trnh thy phn c xc tc thch hp. (c) Dy D, do qu trnh phn ng khng lm thay i cu hnh ca nguyn t cacbon quy nh dy D/L. (d) Khng, do s to ra axit glyconic mch nhnh.

33. (a) Cho bit cu to cc cht trong s chuyn ha di y, trong B l sn phm tch ra t cn bng thun nghch vi A : Br2 / H 2 O pyridin Na Hg H+ Andoz A B C / D (b) Cu trc mch thay i nh th no sau cc bc chuyn ha ny ? (a) A l axit andonic [xem bi 23.19(b)], B l ng phn C2-epime ca A, C l lacton, D l sn phm kh ca C v l ng phn C2-epime ca andoz ban u. (b) y l mt qu trnh epime ha.

34. (a) Cho bit cu to cc cht trong s chuyn ha di y: Br2 / H 2 O H2 Fe III Andohexoz E CaCO 3 F O 2 /() G (b) Cu trc mch thay i nh th no ? (c) Phng php ny c tn gi l g ? (d) Cho kt lun v kh nng hnh thnh ng phn epime. (a) E l axit andonic, F l mui canxi ca n [HOCH2-CHOH-CHOH-CHOH-CHOHCOO]2Ca, G l mt andopentoz HOCH2-CHOH-CHOH-CHOH-CHO. (b) Mch cacbon gim bt mt nguyn t cacbon. (c) Phng php oxi ha v decacboxilat ha ny c tn gi l thoi phn Ruff . (d) Trong qu trnh chuyn ha ch c nhm -CHOH b oxi ha thnh nhm -CH=O, cn cc nguyn t cacbon bt i khc khng tham gia nn khng c s thay i cu hnh no. Nh vy khng th c ng phn epime hnh thnh.

35. (a) Cho bit cu to cc cht trong s chuyn ha di y: NH 2 OH / Ac O NaOAc MaOMe / Andohexoz baz H 2/ J MeOH K (b) Gii thch bc cui cng. (c) Cu trc mch thay i nh th no ? (d) Phng php ny c tn gi l g ? (e) Cho kt lun v kh nng hnh thnh ng phn epime. (a) H l mt oxim HOCH2-(CHOH)4-CH=NOH, I l mt oxim b axetyl ha hon ton AcCH2-(CHOAc)4-CH=NOAc, J l sn phm ca I tch bt mt HOAc : AcCH2(CHOAc)4-C N, K l mt andopentoz HOCH2-CHOH-CHOH-CHOH-CHO. (b) Bc ny xy ra s chuyn este, axetyl trong J chuyn thnh metyl axetat v gii phng cc nhm -OH, tip sau l qu trnh tch HCN. (c) Mch cacbon gim bt mt nguyn t cacbon. (d) Thoi phn Wohl. (e) Trong qu trnh chuyn ha ch c nhm -CHOH b oxi ha thnh nhm -CH=O, cn cc nguyn t cacbon bt i khc khng tham gia nn khng c s thay i cu hnh no. Nh vy khng th c ng phn epime hnh thnh. Cu trc

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

36. Tin hnh thoi phn Ruff mt andohexoz hai ln to ra mt andotetroz, oxi ha andotetroz bng HNO3 to thnh axit meso-tartaric. Andohexoz ban u thuc dy D hay L ? Cu hnh ca cc nguyn t C4 v C5 ca andohexoz c gi nguyn trong andotetroz. V sn phm sinh ra l axit meso-tartaric nn hai nhm -OH trn cc nguyn t C ny phi cng pha. Nh vy c hai trng hp c th xy ra. Nu chng cng pha phi th andohexoz c cu hnh D, cn nu chng cng pha tri th andohexoz c cu hnh L :
H4C OH H5C OH CHO (CHOH)2 2 Ruff CHO H4C OH H5C OH CH2OH D -andotetroz + HNO3 COOH H4C OH H C OH COOH
5

+ HNO3

CHO HO4C H HO C H CH2OH L -andotetroz

5

2 Ruff

HO4C H HO5C H

CHO (CHOH)2

CH2OH D -andohexoz

CH2OH L -andohexoz

axit meso tartaric

37. D-andohexoz no khi b oxi ha bi HNO3 to ra axit meso andaric ? Axit andaric c mt phng i xng gia C3 v C4, v vy andohexoz cng phi c mt phng i xng gia C2, C3, C4 v C5. Hai kh nng c th xy ra :
CHO H C OH H3C OH H4C OH + HNO3 H5C OH CH2OH D -Alloz
2

COOH H C OH H3C OH H4C OH H5C OH COOH Axit meso allaric

2 2

COOH H C OH HO3C H HO4C H H5C OH COOH Axit meso galactaric + HNO3

CHO H C OH HO3C H HO4C H H5C OH CH2OH D -Galactoz

2

38. Tin hnh mt ln thoi phn Ruff vi D- alloz v D-galactoz sau oxi ha bng HNO3 to ra tng ng mt ng phn meso v mt ng phn hot ng quang hc ca axit pentaandaric. Kt qa ny c ph hp vi kt qu tm c bi 23.37 hay khng ? Ph hp. Khi C2 ca alloz chuyn thnh nhm -CHO do phn ng Ruff, cc nguyn t C3, C4 v C5 vn phi gi nguyn tnh i xng ca cu hnh khi oxi ha th sn phm to ra l axit meso andaric, nh vy cc nhm -OH phi cng pha v v alloz thuc dy D nn chng cng pha bn phi. Trong galactoz, tnh i xng b ph hy khi C2 chuyn thnh nhm -CHO, nh vy cc nhm -OH khng nm cng pha.

39. C cc D-andohexoz no khc to c mt (a) ng phn hot ng quang hc v (b) ng phn mezo ca axit pentaandaric khi chng chng cng tri qua cc giai on phn ng ging nh bi 23.38 ? Xem hnh 23-1

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

CHO HO C H HO C H H C OH H C OH CH2OH CHO H C OH HO C H H C OH H C OH CH2OH (a) CHO HO C H H C OH HO C H H C OH CH2OH (b) COOH H C OH H C OH HO C H H C OH CH2OH CHO HO C H HO C H HO C H H C OH CH2OH

10

Hnh 23-1
CHO HO C H H C OH H C OH H C OH CH2OH

40. Mi mt andohexoz nh D-alloz, D-glucoz v D-taloz u to c axit mesoheptandaric sau khi oxi ha mt trong hai sn phm ca phn ng tng mch Kiliani. Xc nh cu to ca andohexoz v axit meso, bit taloz l ng phn C2-epime ca galactoz. C ba axit meso-heptaandaric nh trong hnh 23-2.
CHO H C OH 1. Kiliani H C OH 2. HNO3 H C OH H C OH CH2OH D-alloz CHO HO C H HO C H HO C H H C OH CH2OH D-taloz 1. Kiliani 2. HNO3 COOH H C OH H C OH M ph t ng H C OH H C OH H C OH COOH
xng i

CHO H C OH 1. Kiliani HO C H 2. HNO3 H C OH H C OH CH2OH D-glucoz COOH H C OH HO C H M ph t ng HO C H HO C H H C OH COOH

xng i

COOH H C OH H C OH M ph t ng HO C H H C OH H C OH COOH
xng i

41. Xc nh cu to ca D-arabinoz, bit andoz ny thu c t phn ng thoi phn Ruff ca D-mannoz (mt ng phn C2-epime ca glucoz). Cu to ca D-arabinoz :

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

CHO HO C H HO C H H C OH H C OH CH2OH D-mannoz Ruff CHO HO C H H C OH H C OH CH2OH D-arabinoz

11

42. Vit cu to ca D-riboz, mt cu t ca ARN, bit rng D-riboz v D-arabinoz to osazon ging nhau. Do D-riboz v D-arabinoz to osazon ging nhau nn chng l ng phn C2-epime.
CHO H H H OH OH H C NNHPh C NNHPh H OH H C OH CH2OH osazon CHO HO H H H OH OH

OH CH2OH D - Riboz

CH2OH D - arabinoz

43. Cc andopentoz l D-xyloz v D-lyxoz to osazon ging nhau v khi b oxi ha th tng ng to mt ng phn mezo v mt ng phn hot ng quang hc ca axit andaric. Vit cng thc cu to ca chng. Chng l ng phn C2-epime. Xyloz to axit meso andaric do c i xng cu hnh C2, C3 v C4.
CHO H HO H OH H COOH H OH HNO3 HO H H OH CHO HO HO H H H COOH HO H HNO3 HO H H OH

OH CH2OH D - Xyloz

COOH Axit meso xylaric

OH CH2OH D - Lyxoz

COOH Axit D-lyxaric

44. Vit cng thc cu to cho hai vng lacton su cnh hnh thnh t axit glucaric (axit andaric ca glucoz). Cng thc :
COOH H C OH HO C H H C OH H C OH COOH Axit glucaric H+ O C H C OH HO C H H C OH H C O COOH Lacton A COOH H C O HO C H + H C OH H C OH C O Lacton B

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

12

45. Kh cc lacton trong bi 23.44 to thnh axit andonic, lacton ca axit ny c x l vi Na/Hg v CO2 to thnh andohexoz. Vit cu to ca mi andohexoz to thnh v cho bit cu hnh ca chng thuc dy D hay L. Dy chuyn ha to andohexoz ca mi lacton :
CH2OH kh H C OH HO C H H C OH H C OH COOH - H2O CH2OH H C O HO C H H C OH H C OH C O O C - H2O H C OH HO C H H C OH H C O CH2OH Na/Hg CO2 CH2OH H C OH HO C H H C OH H C OH CHO CHO HO C H HO C H H C OH HO C H CH2OH L- Guloz CHO H C OH HO C H H C OH H C OH CH2OH D-glucoz

COOH H C OH HO C H H C OH H C OH CH2OH

kh

Na/Hg CO2

46. Emil Fischer, cha ca nghnh ha hc cacbohidrat, s dng L-guloz tng hp (ng bit cu to ca n) xc nh cu to cc ng phn epime D-glucoz v D-mannoz (cu to ca cc cht ny cha thit lp c). ng suy lun iu ny nh th no ? Oxi ha L-guloz v D-glucoz to thnh cng mt axit andaric (xem cng thc trong trong bi 23.44). Fischer kt lun rng L-guloz v D-glucoz c cng cu hnh ca cacbon bt i v ch khc nhau l nhm -CHO ca L-guloz pha di, cn nhm -CHO ca D-glucoz pha trn. Do bit cu to ca L-guloz nn suy ra cu to ca D-glucoz, ng thi cu to ca D-mannoz cng c bit do D-glucoz v Dmannoz l ng phn C2-epime.

47. (a) L-andoz no c th to axit andaric ging nh D-mannoz ? (b) Axit andaric ca Dv L-mannoz quan h vi nhau nh th no ? (a) Khng. (b) Chng l cc ng phn i quang (enan), xem hnh 23-3.

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

COOH H OH H HO HO OH H

13

CHO HO H HO H H H OH

COOH HO HO HNO3 H H H H OH OH

CHO H OH H HO HO OH H

H.23-3 :
CHO H OH HO H HO OH OH

OH CH2OH D - Mannoz

COOH Axit D-andaric

H COOH Axit L-andaric

HNO3

H CH2OH L- Mannoz

H 23-4:

H CH2OH L- idoz

48. (a) Ti sao khi nghch chuyn cu hnh C5 ca D-glucoz li khng thu c L-glucoz ? (b) S nghch chuyn ny li to ra L-idoz, vit cng thc cu to ca L-idoz. (a) thu c L-glucoz (ng phn i quang ca D-glucoz) cn phi nghch chuyn cu hnh ca tt c cc nguyn t cacbon bt i trong D-glucoz. (b) Xem hnh 23-4.

49. (a) So snh v gii thch s khc nhau khi cho mt andohexoz v mt andehit tc dung vi lng d ROH trong HCl khan. (b) Cho bit tn gi chung ca sn phm sinh ra t andohexoz v tn gi ring nu andohexoz l glucoz. (a) Andehit phn ng vi 2 ng lng ROH to ra mt axetal, andohexoz ch phn ng vi 1 ng lng ROH. S d c s khc nhau ny l v andohexoz l mt semi axetal do phn ng cng khp vng ni phn t gia -OH v -CHO, nn ch cn thm mt ng lng ROH to axetal. iu ny cng chng t rng andohexoz tn ti ch yu dng vng (b) glycozit v glucozit. 50. (a) Gii thch s t hnh thnh hai ng phn dia ca glucoz trong dung dch nc. (b) Vit cu to v gi tn cc ng phn dia ny. (c) Cc ng phn dia trong trng hp ny c gi l g ?. (d) C th to bao nhiu metyl glucozit ? (a) Khi nhm -CH=O chuyn thnh semiaxtal vng th C1 ca n cng tr thnh mt tm bt i v hnh thnh nn hai ng phn, mt c nhm -OH bn phi v mt bn tri. (b) Xem hnh 23-5, -D-glucoz c C1-OH bn phi v -D-glucoz c C1-OH bn tri. (c) ng phn anome. (d) Hai. -D-glucoz to ra metyl -D-glucozit v -Dglucoz to ra metyl -D-glucozit.

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

H C OH H C O HO H C H C OH O

14

H C OH HO C H H C OH H C CH2OH

H C OH HO C H H C OH H C OH CH2OH glucozm ch h

HO C H H C OH H C CH2OH -D-glucoz

Hnh 23-5 :

-D-glucoz

51. C phi cc ng phn anome ca D-glucoz c cng gi tr gc quay cc ring nhng ngc du ? Khng, hin tng ny ch xy ra vi cc ng phn enan, ng phn anome khng phi l ng phn enan.

52. ng phn epime v anome khc nhau nh th no ? ng phn anome l ng phn C1-epime.

53. Gi tn ng phn enan ca -D-(+)-glucoz. -L-(-)-glucoz. Theo nh ngha th ng phn -enan c nhm -OH semiaxetal cng pha vi nhm -OH trn nguyn t C qui nh cu hnh D/L.

54. Ti sao cc andoz phn ng c vi dung dch Fehling v PhNHNH2 nhng li khng phn ng vi NaHSO3. Cc andoz trong t nhin tn ti cn bng gia dng , v mch h, trong ch c dng mch h l c nhm andehit nhng nng ca dng ny rt thp (khong 0,02%). Cc phn ng trn u xy ra vi nhm andehit nhng c khc bit mt cht l phn ng ca dung dch Fehling v PhNHNH2 din ra mt chiu lm chuyn di cn bng ca dng v v pha mch h, v vy phn ng c xy ra. Trong khi phn ng ca NaHSO3 l phn ng thun nghch, khi nng andehit nh th phn ng ny khng th xy ra.

55. Glycosit c phn ng vi thuc th Tollens hoc Fehling hay khng ? Khng, glycozit l mt semiaxetal bn trong mi trng kim, chng khng c nhm -CH=O nn khng kh c.

56. (a) Vit hai sn phm ca phn ng gia mt andohexoz vi lng d Ac2O/NaOAc. (b) Nhng sn phm ny c phn ng vi dung dch Fehling hoc PhNHNH2 hay khng ? Gii thch. (a) Sn phm l - v -pentaaxetat ca semiaxetal, khng c pentaaxetat ca andehit. C1-OH ca ng phn anome b axetyl ha, trong khi -OH tham gia to vng khng cn c th axetyl ha. (b) Khng, do cc pentaaxetat khng b thy phn trong mi trng kim, chng khng c nhm -CH=O t do. CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

15

57. Vit hai sn phm ca phn ng gia mt andohexoz vi lng d (MeO)2SO2 hoc MeI trong dung dch NaOH v gii thch s hnh thnh cc sn phm ny. Cc nhm -OH ca ng c tnh axit mnh hn so vi cc nhm -OH ca ru do nh hng hiu ng cm ng m gia chng. Nm nhm -OH t do s chuyn thnh cc ankoxi thng qua phn ng th SN2 vi tc nhn metyl c hot ha. Chng ta li thu c sn phm l hn hp ca - v -pentametyl glycozit.

58. Loi vng thng gp cc semiaxetan ny l g ? Gi tn mi loi. Vi mc ch to ra cc vng bn, vi tc hnh thnh nhanh th loi vng thng gp c 5 hoc 6 nguyn t, trong mt nguyn t l oxi. Cc semiaxetan vng nm cnh c gi l furanoz v cc semiaxetan vng su cnh c gi l pyranoz.

59. (a) Andoz nh nht c th hnh thnh nn semiaxetan vng l cht no ? (b) Cho bit cc nhm chc tham gia vo qu trnh to vng ny. (a) Andoz nh nht c kh nng ny l tetroz, vi bn nguyn t cacbon v mt nguyn t oxi s to c mt vng nm cnh. (b) Vng c hnh thnh bi phn ng kt hp gia nhm -CHO v nhm -OH cui mch.

60. Vit cu to v ch r hai ng phn anome ca D-threo. Cu to v ng phn anome ca D-threo :

OH C HO C H H H C OH H2C O H O C HO H C O HO C H H C OH CH2OH D-threoz HO C H H C OH H2C -D-threofuranoz

-D-threofuranoz

61. v -D-glucoz c gc quay cc ring khc nhau.Khi ho tan dng ny hoc dng kia vo nc gc quay cc ca chng u b thay i cho n mt gi tr khng i ging nhau. (a) Cho bit thut ng c s dng cho trng hp bin i ny. (b) Gii thch s bin i . (a) S chuyn i gc quay ny c gi l s nghch chuyn. (b) Dng v -Dglucoz u to c cn bng vi dng mch h cha nhm -CHO v do vy chng c th to cn bng vi nhau : -D-glucoz dng andehit -D-glucoz Khi mi anome bt u thit lp cn bng th gc quay cc ring ca chng cng bt u thay i v ch gi nguyn khi cn bng c thit lp. Cc baz nh NaOH c th lm xc tc cho qu trnh ny nhanh t n trng thi cn bng.

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

16

62. Tnh thnh phn % cc anome thu c ti cn bng hnh thnh do s nghch chuyn ca glucoz, bit gi tr gc quay cc ring ca v -D-glucoz ln lt bng +112o, +19o v gi tr gc quay cc ca hn hp ti cn bng l +52,7o. t a v b ln lt l phn mol ca v -D-glucoz, ta c : a+b=1 112a + 19b = 52,7 Gii h phng trnh ny thu c a 100% = 36,2% v b 100% = 63,8% 63. Nhng pht biu sau l ng hay sai : (a) Glucoz l andoz duy nht c kh nng nghch chuyn. (b) Xetoz cng c kh nng nghch chuyn. (c) Cc glucosit nghch chuyn c. (d) C quan h gia kh nng nghch chuyn v kh nng kh thuc th Fehling ca mt ng. (a) Sai, s nghch chuyn xy ra vi mi ng c tn ti dng semiaxetan. (b) ng, xetoz tn ti nh mt semiaxetan v cng c cc anome. (c) Sai, nhm OH ca anome tham gia qu trnh ete ha v do vy cn bng vi dng cha nhm cacbonyl t do b ph v. (d) ng, qu trnh kh thuc th Fehling v s nghch chuyn u do s c mt ca nhm cacbonyl t do.

64. T cc d kin sau cho bit D-glucoz l furanoz hay pyranoz ? Gi tn cc sn phm trung gian ca qu trnh ny : HNO 3 Me / NaOH MeOH / HCl D-glucoz A 2SO B ddHCl C axit 2,3-dimetoxisucxinic 4 + axit 2,3,4-trimetoxiglutaric. Phn ng xy ra vi cc cu to furanoz v pyranoz :
COOH H C OMe MeO C H H C OMe + CO2 COOH
HN O (a 3 )

OH

H C OMe MeO C H O H C OMe H C CH2OMe pyranoz

H C OMe MeO C H H C OMe H C OH CH2OMe d ng andehit

axit 2,3,4-trimetoxiglutaric

COOH H C OMe MeO C H + MeOCH2COOH COOH axit 2,3-dimetoxisucxinic

CHUYN GLUXIT

HN O3 ) (b

T S CHNG- TRNG PTTH CHUYN QUNG BNH

COOH H C OMe MeO C H + MeOCH2COOH COOH H
O

17

OH

O
(c ) HN
3

axit 2,3-dimetoxisucxinic

H C OMe MeO C H O H C H C OMe CH2OMe furanoz

H C OMe MeO C H H C OH H C OMe CH2OMe d ng andehit

HN O (d) 3

COOH H C OMe COOH

COOH + H C OMe CH2OMe axit metoximalonic

axit dimetoxiglyxeric

Hnh

23-6 Cc sn phm trung gian l : A = metyl D-glucosit (ete ha nhm OH-anome) B = metyl tetra-O-metyl-glucosit (ete ha 4 nhm OH khc) C = tetra-O-metyl-glucoz (OMe-anome b thy phn) Cu to cc sn phm sinh ra do s oxi ha mnh lit l : HOOCCH(OMe)CH(OMe)COOH + HOOCCH(OMe)CH(OMe)CH(OMe)COOH Cc nhm -OH trn nguyn t cacbon tham gia vo qu trnh hnh thnh vng semiaxetan th khng b metyl ha. i vi vng nm cnh furanoz th l nhm -OH C1 v C4, cn i vi vng su cnh pyranoz th l nhm -OH C1 v C5. S oxi ha mnh lit trong giai on cui cng chuyn nhm C-OH-anome thnh nhm -COOH v gy ra s ct mch lin kt bn cnh nguyn t C lin kt vi nhm -OH bc 2. Hnh 23-6 minh ha sn phm c th c sinh ra t mi loi vng, cc hng to sn phm (a) v (b) l t vng su cnh pyranoz, cn (c) v (d) l t vng nm cnh furanoz. V hng (a) v (b) to ra cc sn phm tng ng vi cc sn phm thu c t thc nghim nn glucoz phi c cu to vng pyranoz. 65. T dy chuyn ha di y, lm th no xc nh mt metyl glucosit c vng 2.dung dch O+ pyranoz hay furanoz : ng 1.HIO 4 Br2 3.H 3 u tin HIO4 gy phn ct lin kt C-C lin kt vi cc nhm -OH lin tip, sau dung dch Br2 oxi ha nhm -CHO thnh nhm -COOH, v cui cng axit c s dng thy phn cu ni axetan nh c th phn mnh hp cht ban u. Hnh 23-7 cho bit cc sn phm sinh ra t mi loi vng :

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

H C OCH3 H C OH 2HIO4 HO C H O H C OH H C CH2OH Metyl -D-glucopyranosit H C OCH3 H C OH 2HIO4 HO C H O H C H C OH CH2OH Metyl -D-glucofuranosit H C OCH3 H C O H COOH H C O H C CH2OH H C O COOH 1. dd Br2 O + + 2. H3O COOH H C OH CH2OH Axit D-glyxeric H C OCH3 H C O H C O COOH 1. dd Br2 H C O O + 2. H3O+ H C COOH H C O H C OH H2C O
+

18

- CO2

COOH H C OH H

COOH Axit hidroximalonic

Nh vy nu so snh cc sn phm thc nghim thu c vi hai hng chuyn ha trn s xc nh c loi vng. 66. (a) V cng thc Haworth cho -D-glucopyranoz. (b) Cng thc ca dng c khc im no ? Cng thc Haworth c dng vng phng t vung gc vi mt phng giy. Xoay C6 trong cng thc Fischer (A) ra phi sau mt phng giy, quay lin kt C4-C5 sao cho nhm C5-OH n gn nhm -CH=O to vng (B). Vi cch thc hin ny th nhm -CH2OH cui mch s pha trn i vi tt c cc ng-D. Trong loi vng ny nguyn t O lun xa ngi quan st v nguyn t C-anome pha bn phi, cc nhm th bn tri trong cng thc Fischer pha trn mt phng vng v nhm th bn phi s pha di. Xem hnh 23-8. (b) Trong ng phn anome dng , nhm -OH-anome pha trn.
CHO H OH HO H H OH H OH 6 CH2OH A
1

H H OH H OH OH OH CH2OH H C H H O OH

CH2OH OH H OH H B H OH H C H O OH

CH2OH O H OH H C H OH OH H

67. V cu dng gh cho -D-glucopyranoz C hai cu dng gh chuyn ha ln nhau, y chng ta chn cu dng bn hn ng vi nhm th ln nht (nhm -CH2OH) v tr bin. Xem hnh 23-9

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

Hnh 23-9 :
H OH H O HO HO H H OH OH H Ho n gin h : c n HO HO H H H OH H O OH H OH

19

68. Ti sao -D-glucopyranoz chim hm lng ln trong t nhin ? Cc nhm th trong cu dng gh u v tr bin nn cu dng ny bn. 69. V cu dng gh bn v km bn cho (a) -D-manopyranoz (xem bi 23-47) v (b) -Lglucopyranoz (a) Xem hnh 23-10(a), ng vi cu dng bn hn, nhm -CH2OH v ba nm -OH khc v tr bin. (b) Xem hnh 23-10(b).
H OH HO HO OHO H H OH OH HO H H OH OH H H OH H H H H H H OH OH OH O H OH H OH OH OH OH H

O OH H OH

(a)

(bn hn)

(km bn hn)

H H

(b)

HO H

(bn hn) Hnh 23-10

(km bn hn)

70. (a) V cu dng gh bn v km bn cho -D-idopyranoz (ng phn epime ca Dglucoz - xem bi 23.45). (b) Gii thch s la chn ca bn. (a) Xem hnh 23-11. (b) D nhm -CH2OH v tr trc, nhng li c bn nhm -OH v tr bin nn cu dng (a) bn vng hn.
OH H H OH H H H OH OH OH OHO H H OH H HO HO H

O OH H

(a)

(bn hn) bn hn) Hnh 23-11

(b)

(km

71. (a) Trong fructoz nguyn t cacbon no l C-anome ? (b) Vit cng thc chiu Fischer cho cc ng phn anome ca (i) D-fructofuranoz v (ii) D-fructopyranoz. CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

(a) C2 (b) (i) D-fructofuranoz :
1

20

CH2OH OH HO HO H H

CH2OH

CH2OH

HO H H

H OH O 6 CH2OH

H OH O 6 CH2OH

HO H H

O H OH OH 6 CH2OH

-D-fru ctofu rano z

-D-fru ctofu rano z

dng m ch h

(ii) D-fructopyranoz :
1

CH2OH OH HO HO H H

CH2OH

HO H H

H OH OH 6 CH2O

H OH OH 6 CH2O

-D-fru ctop yran oz

-D-fru ctop yrano z

72. V cng thc chiu Haworth cho cc ng phn anome ca D-fructofuranoz. Cng thc chiu Haworth cc ng phn anome ca D-fructofuranoz :
HOH 2C6 O
1

CH2OH

HOH 2C

OH

HO OH OH -D-fructofuranoz OH

HO CH OH 2

-D-fructofuranoz

Hnh 23-12

73. Tng t bi 23-66, ch ra cch hnh thnh cng thc chiu Haworth cho cc ng phn anome ca D-fructopyranoz. Nhm OH-anome quay xung di v v tr cis so vi C5-OH to to ra dng , Nhm OH-anome quay ln trn v v tr trans so vi C5-OH to to ra dng :
O HO OH -D-fructopyranoz HO
1

CH2OH HO

CH2

OH HO

CH2OH O HO OH

O HO

OH
1

OH

CH2OH

OH

-D-fructopyranoz

Hnh

23-13

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

21

74. (a) V cu dng gh bn cho a-D-fructopyranoz. (b) (b) Cng thc ca dng c khc im no ? (a) Xem hnh 23-14. (b) OH v 1CH2OH trn C2 o v tr.
H HO H H OH OH O
1

H OH

CH2OH

Hnh 23-14

Disaccarit v Polisaccarit 75. (a) Cho bit c im cu to c trng ca cc disaccarit. (b) Trong cng thc ca disaccarit trt t cc monosaccarit c quy nh nh th no ? (a) Disaccarit l mt glycosit, trong nhm OH-anome ca monosaccarit th nht to cu ni theo kiu axetan vi -OH ca monosaccarit th hai (monosaccarit th hai ny c gi l aglycon). (b) Aglycon l monosaccarit pha cui bn phi.

76. (a) Biu din cu to di dng cng thc Fischer, cng thc dng gh v (b) gi tn theo danh php IUPAC cho mantoz, mt disaccarit c aglycon l mt phn t glucoz (A), aglycon s dng C4-OH ca n lin kt vi -OH ca nt phn t glucoz th hai (B). (c) c im cu trc no ca mantoz l khng xc nh ? (a) Xem hnh 23-15. (b) 4-O-(-Dglucopyranoz)--D-glucopyranoz. (c) Cu hnh Canome ca aglycon l khng xc nh.
Axetan
H C O HO

Semiaxetan
H C H C OH O H OH HO HO O OH O HO OH O OH OH

H C OH HO C H H C OH H C CH2OH

HO C H H C O H C CH2OH

(B)

(A)

H 23-15 nh

77. Cho bit sn phm ca phn ng gia mantoz v (a) dung dch HCl, (b) enzim mantaza v (c) enzim emulsin. (a) v (b) Mantoz b thy phn to ra hai ng lng glucoz, mantaza ch xc tc cho qu trnh thy phn cu ni -glycosit. (c) Khng phn ng, emulsin ch xc tc cho qu trnh thy phn cu ni -glycosit

78. Mantoz phn ng nh th no vi (a) dung dch Fehling, (b) dung dch NaOH, (c) dung dch brom v (d) lng d PhNHNH2. V aglycon ca mantoz c nhm OH-anome t do, cc anome tn ti cn bng vi dng mch h cha nhm andehit, nn mantoz phn ng c vi tt c cc cht nu trn, lin kt glycosit khng b nh hng. (a) v (c) C1-anome ca aglycon b oxi ha thnh -COOH. (b) Xy ra s nghch chuyn. (d) Hnh thnh nn mt osazon.

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

22

79. Khi oxi ha mantoz bng dung dch brom thu c axit cacboxilic (C), axit ny phn ng vi (MeO)2SO2/NaOH to ra mt dn xut octametyl (D).Thy phn (D) trong HCl thu c 2,3,4,6-tetra-O-metyl-D-glucopyranoz (E) v axit 2,3,5,6-tetra-O-metyl-D-gluconic (F). S dng cc d liu trn v kt qu ca cc bi 23.77, 23.78 lp lun xc nh cu to mantoz v cc cht C, D, E, F. T kt qu ca cc bi 23.77 v 23.78 ta bit rng mantoz l mt -glycosit, aglycon ca n c cha OH-anome t do (lp th cha xc nh). Axit (C) hnh thnh do s oxi ha C1 ca aglycon (A) thnh nhm -COOH, kt qu l vng semiaxetan ca n b ph v. Qu trnh metyl ha trc khi thy phn thnh monosaccarit xc nh cc nhm -OH trn cc nguyn t cacbon khng tham gia vo bt kh lin kt no. Nguyn t O trn C5 ca E khng b metyl ha cho thy rng n tham gia vo s hnh thnh vng pyranoz. V tt c cc nhm -OH ca E, tr OH-anome v -OH to vng, u b metyl ha nn ta c th suy ra rng E sinh ra t B v F sinh ra t A. C 4-OH ca F khng b metyl ha cho thy rng -OH ny tham gia hnh thnh cu ni ete. Xem hnh 23-16.
H OH
2 Mantoz dd Br

H OMe O OH O HO OH OH

HO HO

Me2SO 4 NaOH
COOH OH

MeO MeO

O OMe O MeO

OMe OMe COOH OMe

H OMe

OMe O

Hnh 23-16

H3O+

MeO MeO

+
MeO OH

HO MeO

OMe MeO COOH

80. Xenlobioz, mt disaccarit thu c t xenluloz, c cu cc cu t ging nh mantoz nhng b thy phn bi enzim emulsin. Cho bit cu trc (dng gh) ca xenlobioz. Khc vi mantoz, xenlobioz l mt -glucosit. Xem hnh 23-17
OH HO HO O OH B

OH 1 HO O
4

OH O OH A

Hnh 23-17

81. (a) Lp lun xc nh cu to ca lactoz, mt disacacrit c trong sa, bit : (1) Thy phn trong emulsin to ra D-glucoz v D-galactoz, (2) l mt ng kh c kh nng nghch chuyn. (3) Khi thy phn osazon ca n thu c D-glucosazon v D-galactoz, (4) Oxi ha nh nhng, sau metyl ha ri cui cng thy phn to cc sn phm tng t nh sn phm thu c t mantoz. (b) Vit cng thc cu to osazon ca lactoz. (a) T (1) suy ra lactoz l mt -glucosit cu thnh t D-glucoz v D-galactoz. (2) cho bit lactoz c nhm OH-anome t do. (3) cho bit cu t glucoz l aglycon do n

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

23

to c osazon v galactoz l mt -galactosit. (4) cho bit c hai cu t u dng pyranoz v lin kt vi nhau qua C4-OH ca cu t glucoz. Xem hnh 23-18(a). (b) Xem hnh 23-18(b).
H OH OH O HO OH

NNHPh NNHPh

OH 1 HO O
4

OH O OH (A) D-glucoz

HO H H
4

H O OH
6

(B) D-galactoz

Hnh 23-17

CH2OH

Lactoz osazon

82. M t qu trnh ri lon tiu ha gy ra do s d ng lactoz. Lactoz khng th hp th trc tip vo mu, m cn c thy phn trc thnh cc cu t i tc dng ca men lactaza c trong rut. Lng lactoz khng b thy phn cng vi mt t lactaza s chy qua ng rut gy au bng v cc triu trng ng rut khc. S d ng lactoz thng gp nhng ngi ln tui.

83. (a) Bng cch no chng ta bit rng mantoz, xenlobioz v lactoz khng cha cu t Lmonosaccarit? (b) Cc ng L c xut hin trong t nhin hay khng ? (a) Thy phn disaccarit thnh monosaccarit sau kim tra gc quay cc ring, cc monosaccarit thu c s xy ra s nghch chuyn, nhng cc ng phn anome ca glucoz v galactoz u quay phi. y l c im ca cc ng phn quang hc khng i quang thuc dy D ca cc monosaccarit ny. (b) C nhng t. Khc vi aminoaxit trong t nhin thng thuc dy L, cc dng tn ti trong t nhin ch yu thuc dy D.

84. T cc d kin sau y hy xc nh cu trc ca saccaroz (mt loi ng n ph bin c tch t cy ma v c ci ng) : (i) n khng kh c thuc th Fehling v khng nghch chuyn. (ii) Khi thy phn bng men mantaza hoc emulsin u to sn phm l Dglucoz v D-fructoz. (iii) Metyl ha sau thy phn to ra 2,3,4,6-tetra-O-metyl-Dglucopyranoz v tetrametyl D-fructoz. (b) Phn no ca cu trc khng cha c xc nh ? (c) Gi tn saccaroz theo danh php IUPAC. (a) T (i) suy ra saccaroz khng c OH-anome t do. (ii) cho bit OH-anome ca mt cu t l (thy phn c trong mantaza) v OH-anome ca cu t kia l (thy phn c trong emulsin). (iii) cho bit cu t glucoz l mt pyranosit do C5 khng b metyl ha. Hnh 23-19 l mt v d cho cu to xc nh c. (b) Loi vng ca cu t fructoz (trong thc t n l mt furanosit) v lin kt glycosit (trong thc tes lin kt ny hnh thnh gia -glucoz v -fructoz. (c) V cha xc inh cu t ng vai tr glycon nn c th c hai trng hp sau : -D-glucopyranosyl--D-fructofuranosit hoc -D-fructofuranosyl--D-glucopyranosit.

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

OH HO HO O OH O OH HOH 2C1 O HO C6H2OH

24

Hnh 23-19

85. (a) nh ngha ng nghch chuyn. (b) Tnh gc quay cc ring ca ng nghch chuyn, bit rng D-glucoz c []D = 52,7o v D-fructoz c []D = -92,4o. (a) ng nghch chuyn l hn hp ng phn t ca D-glucoz v D-fructoz thu c do s thy phn saccaroz. (b) Gc quay cc ring bng trung bnh cng gc quay cc ca mi cu t : []D =
1 [ + 52,7 + (92,4)] = 19,9 2

86. Cho bit sn phm to thnh khi thy phn saccaroz c metyl ha hon ton. Xem hnh 23-20. (Cu hnh C-anome khng xc nh nn cc lin kt bu din c bng ng son).
OCH3 H3CO H3CO O CH3O O CH3OC1 O H3CO H3CO OCH3 O CH3OC1 H HO O H3CO C6H OCH 2 3 OCH3 2,3,4,6-tetra-O-metylD-glucopyranoz 1,3,4,6-tetra-O-metylD-glucofuranoz

H3CO C6H OCH 2 3 OCH3

H3O

CH3O OH

Hnh 23-20

87. Lp lun xc nh cu trc ca mt disaccarit (A) c cng thc phn t C10H18O9, bit rng khi oxi ha bi brom, sau metyl ha v cui cng x l vi men mantaza th thu c sn phm l 2,3,4-tri-O-metyl-D-xyloz v axit 2,3-di-O-metyl-L-arabinoic. Do thy phn c di tc dng ca mantaza nn A l mt -disacccarit. Cu t b axit ha v c t nhm -OCH3 hn l aglycon, trong trng hp ny chnh l L-arabinoz. V C5-OH ca c hai cu t u khng b metyl ha nn cc pentoz ny u l cc pyranoz. C4-OH ca L-arabinoz khng b metyl ha, iu ny cho thy n tham gia to cu ni ete vi OH--anome ca xyloz. Cu to y ca A nh trong hnh 23-21.
HO HO O OH O OH

OH

OH 4-O-( -D-xylopyranosyl)-L-arabinopyranosit

Hnh 23-21

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

25

88. Lp lun xc nh cu trc ca gentiobioz C12H22O11, bit rng gentiobioz c kh nng nghch chuyn v khi thy phn bi men emulsin to D-glucoz. Thy phn sn phm metyl ha ca gentiobioz sinh ra 2,3,4,6-tetra-O-metyl-D-glucopyranoz v 2,3,4-tri-Ometyl-D-glucopyranoz. Gentiobioz l mt -disacccarit (thy phn c bi emulsin) cu thnh t hai cu t glucoz. Glucoz-aglycon c cha nhm OH-anome t do (c kh nng nghch chuyn). C hai cu t u l pyranoz v nhm C5-OH khng b metyl ha. Nhm C6-OH ca aglycon khng b metyl ha cho bit v tr to cu ni ete. Cu to y ca gentiobioz nh trong hnh 23-22 ( y gi thit rng aglycon l -glucoz) :
OH HO HO O O OH HO HO CH2 O OH OH

6-O-( -D-glucopyranosyl)- -D-glucopyranoz

Hnh 23-22

89. Lp lun xc nh cu trc ca (a) trehaloz khng kh C12H22O11, bit khi thy phn bng mantaza thu c D-glucoz, (b) isotrehaloz c cu to tng t trehaloz, ch khc l c th thy phn bi mantaza hoc emulsin. Thy phn c hai cht ny sau khi metyl ha u to sn phm duy nht 2,3,4,6-tetra-O-metyl-D-glucopyranoz. (a) Xem hnh 23-23 (a). Trehaloz gm hai cu t D-glucoz, cc cu t ny u s dng OH--anome to lin kt. V C5-OH khng b metyl ha nn mi cu t du l mt pyranosit. (b) Xem hnh 23-23. Trong isotrehaloz, cu ni ete gia hai cu t c hnh thnh bi OH--anome ca cu t th nht vi OH--anome ca cu t th hai.
OH HO HO O OH O HO O OH -D-glucopyranosyl- -D-glucopyranosit Trehaloz(a) -D-glucopyranosyl- -D-glucopyranosit Isotrehaloz(a) HO HO OH O OH O O OH HO OH OH

OH OH

90. Cho bit tn gi hai polisacacrit c trong thc vt cu thnh t mt loi cu t duy nht l glucoz. Tinh bt v xenluloz.

91. Khi thy phn khng hon ton amyloz, mt thnh phn ca tinh bt c kh nng ha tan trong nc, to ra mantoz v D-glucoz. Metyl ha, sau thy phn hon ton th sn phm chnh l 2,3,6-tri-O-metyl-D-glucopyranoz. Cho bit cu to ca amyloz. Amyloz cha cc phn t mantoz lin kt vi nhau bng lin kt -1,4-glucosit to ra mt helix (cu to xon c).

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

26

92. Metyl ha sau thy phn amyloz thy c xut hin 2,3,4,6-tetra-O-metyl-Dglucopyranoz chim hm lng t 0,2 n 0,4%. Gii thch ngun gc pht sinh sn phm ny. Sn phm ny sinh ra t phn t glucoz cn cha C4-OH t do u mi mch polime.

93. Khi metyl ha v thy phn amylopectin, mt thnh phn ca tinh bt c kh nng ha tan trong nc, to sn phm chnh tng t amyloz. Tuy nhin cn c mt phn cc sn phm khc nh 2,3,4,6-tetra-O-metyl-D-glucopyranoz (chim hm lng khong 5%) v khong 5% 2,3-di-O-metyl-D-glucopyranoz. Lp lun xc nh cu trc ca amylopectin. Qu trnh metyl ha v thy phn to sn phm tng t nh amyloz cho thy hu ht cc lin kt trong amylopectin l tng t ging nh trong amyloz. S xut hin ca sn phm 2,3-di-O-metyl-D-glucopyranoz cho thy s khc bit u tin l trong amylopectin ngoi cc lin kt -1,4-glucosit to thnh mch chnh cn c cc lin kt 1,6-glucosit to thnh mch nhnh. Sn phm 2,3,4,6-tetra-O-metyl-D-glucopyranoz xut hin vi hm lng % ln hn cho thy rng mch polime ca amylopectin ngn hn so vi amyloz.

94. (a) Glycogen l g v glycogen khc tinh bt im no ? (b) Xenluloz l g v cu trc ca xenluloz khc g so vi tinh bt ? (a) Glycogen l mt loi polisacacrit d tr trong c th ng vt, trong khi tinh bt l mt loi polisacacrit d tr trong c th thc vt. Glycogen c cu to tng t nh amylopectin nhng s lng mch nhnh ln hn. (b) Xenluloz, loi hp cht hu c c hm lng ln nht trong t nhin, l thnh phn chnh ca g v cu to thc vt; cotton (si bng) gn nh l xenluloz nguyn cht. Ging vi tinh bt, cu t ca xenluloz cng l glucoz nhng khc vi tinh bt, lin kt trong xenluloz l -1,4glucosit, mch ca xenluloz c rt t nhnh v khi lng phn t xenluloz ln hn khi lng phn t tinh bt.

95. (a) Xc nh khi lng phn t trung bnh ca tinh bt, bit rng 25oC dung dch nc ca tinh bt c p sut thm thu = 5,0.10-3atm . (b) Vi mu th ny trung bnh c khong bao nhiu cu t glucoz trong mt phn t tinh bt. (a) T = C M RT vi CM l nng mol mol, R l hng s kh (0,082 L.atm.mol-1.K-1) v T l nhit tuyt i, ta c :
CM = M= 5,0.10 3 atm = = 2,0.10 4 mol.L1 RT (0,082 L.atm.mol 1 .K 1 ).( 298 K ) 10,0g.L1 2,0.10 4 mol.L1 = 5,0.10 4 g.mol 1

(b) Mi phn t glucoz (M = 180 g.mol-1) tham gia lin kt to thnh tinh bt u mt di mt phn t nc (M = 18 g.mol-1), nn khi lng mi cu t l M = 180-18 = 162 g.mol-1. Nh vy trong mu th ny s cu t trung bnh l 5,0.104/162 = 309 cu t.

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

27

96. (a) Cc phn t xyclodextrin l g ? (b) Trong kha cnh xc tc th xyclodextrin c g khc so vi cc ete vng ? (c) Xyclodextrin c s dng nh th no ? (a) Xyclodextrin l cc oligosaccarit (xem bi 23.4) cha t 6 n 8 n v glucopiranoz. Xyclodextrin c hnh thnh khi thy phn tng phn tinh bt. (b) Tng t nh cc ete vng, cc xyclodextrin cng c th hot ng nh cc cht mang xc tc. Tuy nhin, do cu trc bn trong ca xyclodextrin khng phn cc k dung mi, cn phn bn ngoi phn cc i dung mi, nn khc vi ete vng, xyclodextrin mang cc phn t ch khng phi l ion. (c) 97. (a) Cho bit mt phng php n gin nhn bit tinh bt. (b) Hin tng g xy ra khi tng nhit th nghim nhn bit ny ? (c) Cho bit s bin i cu trc tng ng vi cc hin tng thy c ? (d) Hin tng to ra t amyloz v amylopectin c ging nhau khng ? Gii thch.

(a) Tinh bt s c mu xanh-en thm khi thm I2 vo. (b) Mu xanh-en chuyn thnh mu nu . (c) Amyloz ca tinh bt bc cc phn t I2 trong helix, to hp cht bc c mu xanh en. Khi un nng, mt phn helix dui ra, gii phng mt lng nh I2 gy ra s bin i mu sc. Khi lm ngui, helix v hp cht bc c ti to lm cho mu sc tr li nh ban u. (d) 98. H2O1. a) Trong andotetroz c bao nhiu tm bt i? b) Vit cng thc Fischer cho cc ng phn i quang ca mt andotetroz v xc nh cu hnh D/L ca chng. Gii : a) C 2 tm bt i HO-CH2-*CHOH-*CHOH-CHO b) Theo quy c cu hnh D ca ng ng vi nhm OH trn C* no c ch s v tr cao nht pha bn phi v cu hnh l ng vi nhm OH trn C* c ch s v tr cao nht pha bn tri:
CHO H H OH OH CH2OH HO HO CHO H H CH2OH HO H CHO H OH CH2OH H HO CHO OH H CH2OH

D-erythro

L- erythro

D- Threo

L-Threo

c) Cho bit s khc nhau gia D-erythro v D-Threo khi chng b oxiho nh nhng v khi chng b kh ? Nu v d v tc nhn oxiho v tc nhn kh. Gii: - Sn phm oxiha l cc ng phn dia ca axit tactric. Dng threo to mt ng phn i quang c tnh quang hot, cn dng erythro to mt ng phn meso khng c tnh quang hot.
OHH HOH2C CHO H OH

[O]
COOH

OHH COOH H OH

OHOH CH2OH CHO H H

[O]
COOH

OHOH COOH H H

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

28

- Sn phm kh l 1,2,3,4- butantetrol. Dng threo to mt ng phn i quang c tnh quang hot, cn dng erythro to mt ng phn meso khng c tnh quang hot.
OHH HOH2C CHO H OH

[H]
CH2OH

OHH CH2OH H OH

OHOH CH2OH CHO H H

[H]
CH2OH

OHOH CH2OH H H

d) Cho bit cc cht trung gian v sn phm to thnh khi cho D-Threo tc dng vi PhNHNH2.
CHO H H OH OH CH2OH H H C=NNHPh HC=NNHPh HC=NNHPh HC=NNHPb H OH CH2OH OH OH CH2OH C=O H

+PhNHNH 2

PhNHNH2 -PhNH 2,-NH3

+PhNHNH 2
OH

CH2OH

e)Khi D-erythro tham gia phn ng ny th sn phm l g ? Gii thch sn phm thu c. Gii: D-erythro cng to mt ozazon ging nh trn . Cu hnh C2 trong ng ban u khng quan trng do n b oxiha thnh >C=O, mt xeton ging nhau t c 2 loi ng trn. f) Vit 2 sn phm l ng phn hnh thnh trong phn ng gia D-Threo v NaCN/HCN.Ti sao 2 ng phn ny c to thnh vi hm lng khng bng nhau ? 2. Cho bit cc sn phm to thnh khi cho HIO4 tc dng vi HO-CH2-(CHOH)4-CHO (A) v HO-CH2-(CHOH)3CO-C H (B). Suy ra ng dng ca phn ng ny. 99.Mt isaccarit A khng c tnh kh. Khi thu phn trong mi trng axit, A cho sn phm duy nht l pentoz B. Cng c th thu phn A nh enzim glicoziaza song khng dng c -glicoziaza. T B c th to ra D-glucoz bng cch cho tc dng vi HCN ri thu phn (xc tc axit) v kh. a) Vit cng thc Fis v gi tn B theo danh php h thng. b) Vit s cc phn ng chuyn ho B thnh D-glucoz. c) Vit cng thc cu trc ca A dng vng 6 cnh phng. d) khng nh cu trc vng 6 cnh ca A, ngi ta cho A tc dng vi CH3Br trong mi trng baz ri thu phn (xc tc H+). Dng cng thc cu trc, vit s cc phn ng. 100 .Monosaccarit A (t l glicoz A) c tn l (2S,3R , 4S , 5R)2,3,4,5,6 pentahiroxihexanal. Khi un nng ti 1000C, A b tch nc sinh ra sn phm B c tn l 1,6anhiroglicopiranoz. Dglucoz khng tham gia phn ng ny. T A c th nhn c cc sn phm E (C5H10O5) v G (C5H8O7) theo s phn ng:

Br2 H2O

CaCO3

H2O2

HNO3

1. Vit cng thc Fis ca A v B. 2. A tn ti 4 dng gh (D-glicopiranoz). Vit cng thc ca cc dng v cho bit dng no bn hn c? 3. Dng cng thc cu dng biu din phn ng chuyn ho A thnh B. V sao Dglucoz khng tham gia phn ng tch nc nh A? CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

29

4. Vit cng thc cu trc ca E v G. Hy cho bit chng c tnh quang hot hay khng? 1. T cloaxetanehit v BrMgC CMgBr vi cc cht v c cn thit tng hp c cht (A), (B) c cng thc sau. Hy vit s cc phng trnh phn ng v ghi r iu kin (nu c). CH2OH (A) H H H H OH OH OH OH CH2OH CH2OH H (B HO HO H OH H H OH CH2OH

2. Galactal (G) tc dng vi metanol nh xc tc HCl sinh ra 2 sn phm mch vng A1 v A2 c cng cng thc phn t C7H14O5. a) Hy trnh by c ch phn ng v cng thc cu trc ca A1 v A2. (G) H

OH CH2OH
H

H H

HO H

b) Cho A1 hoc A2 tc dng vi dung dch axit trong nc sinh ra mt hn hp sn phm lun lun chuyn ho ln nhau theo cn bng. Dng cng thc lp th m t cn bng . 1. Vit phng trnh phn ng iu ch D-fructoz t D-glucoz, bit rng D-glucozazon khi tc dng vi benzanehit to thnh ozon ca D-glucoz (HOCH2(CHOH)3COCHO). 2. Chitin (tch t v tm, cua...) c coi nh l dn xut ca xenluloz, trong cc nhm hiroxyl cc nguyn t C2 c thay th bng cc nhm axetylamino ( -NH-COCH3 ). a) Vit cng thc cu to mt on mch ca phn t chitin. b) Gi tn mt mt xch ca chitin. c) Vit phng trnh phn ng xy ra khi un nng chitin vi dung dch HCl c (d), un nng chitin vi dung dch NaOH c (d). 101. ( thi HSG quc gia, Vit Nam - 1998) 1. A l disaccarit kh c AgNO3 trong dung dch NH3, gm hai ng phn c kh nng lm 25 quay mt phng nh sng phn cc trong nhng iu kin thng nht biu th bng [] D l + 25 92,6o v +34o. Dung dch ca mi ng phn ny t bin i v [] D cho cho ti khi cng t gi tr n nh l + 52o. Thy phn A (nh xc tc axit) sinh ra B v C:

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

CHO H HO H H OH H OH OH CH2OH (B) H HO HO H CHO OH H H OH CH2OH (C)

30

Cho A tc dng vi lng d CH3I trong mi trng baz thu c sn phm D khng c tnh kh. un nng D vi dung dch axit long thu c dn xut 2,3,6-tri-O-metyl ca B v dn xut 2,3,4,6-tetra-O-metyl ca C . (a) Vit cng thc cu trc (dng vng 6 cnh phng) cho B, C, A, D; bit trong phn t A c lin kt -1,4-glucosit. Gii thch v vit cc phng trnh phn ng. 25 (b) V sao dung dch mi ng phn ca A t bin i v [] D v cui cng u t gi tr 25 52o ? Tnh thnh phn phn trm cc cht trong dung dch gi tr [] D = 52o v vit cng thc cu trc cc cht thnh phn . 2. Metyl ha hon ton cc nhm OH ca 3,24 gam amilopectin bng cch cho tc dng vi CH3I trong mi trng baz ri un thy phn hon ton (xc tc axit) th thu c 1,66.10-3 mol 2,3,4,6-tetra-O-metylglucoz v 1,66.10-3 mol 2,3-di-O-metylglucoz, phn cn li l 2,3,6-tri-O-metylglucoz, (a) Vit cng thc cu trc (dng vng 6 cnh phng) ca 3 sn phm trn v cho bit xut x ca chng. (b) Cho bit t l % cc gc glucoz ch c nhnh ca phn t amilopectin. (c) Tnh s mol 2,3,6-tri-O-metyl glucoz sinh ra trong th nghim trn.

1. (a) Cng thc ca B, C :

CHO H HO H H OH H OH OH CH2OH (B) CH2OCH3 O
5 6

CHO CH2OH O OH OH
2

H
1

OH H H OH CH2OH (C)

H OH

HO HO H

OH

CH2OH O OH
2

H OH

OH

OH

Dn xut 2,3,6-tri-O-metyl ca B v dn xut 2,3,4,6-tetra-O-metyl ca C c cng thc :

H OH CH3O
4

OH

OCH3
3

CH2OCH3 O 5 OCH3
3 2

H OH

OCH3

OCH3

2,3,6-tri-O-metyl ca B

dn xut 2,3,4,6-tetra-O-metyl ca C

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

31

iu ny cho thy lin kt -1,4-glucosit (theo gi thit) hnh thnh gia nhm C1-OH ca cht C vi C4-OH ca cht B v v A l disaccarit kh c AgNO3 trong dung dch NH3 nn cn nhm C1--OH-semiaxetal ca B. Cng thc ca A l :
CH2OH O OH 5
4 6

OH
3

CH2OH O
5

OH
3

H OH

OH
(A)

OH

D khng c tnh kh, nh vy OH- semiaxetal ca A cng b metyl ha. Cng thc ca D l :
CH3O
4

CH2OCH3 O 5 OCH3
3 2 1

CH2OCH3 O
5

OCH3
3

H OCH3

OCH3
(D)

OCH3

(b) Cc ng phn anome ca A c th chuyn ha ln nhau thng qua cu trc h. Do vy trong dung dch, mi ng phn ca A t bin i v hn hp cn bng ca hai ng phn 25 ng vi mt gi tr [] D duy nht bng 52o. Gi hm lng % dng th nht l x%, ta c :
x 100 x (+926). , + (+34 ). = +52 x = 30,7 100 100

Vy ng phn c kh nng lm quay mt phng nh sng phn cc trong nhng iu kin 25 thng nht biu th bng [] D l + 92,6o v +34o ln lt c gi tr bng 30,7% v 69,3%. Cng thc ca cc ng phn ny l :
CH2OH O OH 5
4 6

OH
3

CH2OH O
5

OH
3

CH2OH O OH 5
4

OH
3

OH

CH2OH O
5

OH

OH
3

OH

OH

OH

OH

2. (a) Cng thc cu trc (dng vng 6 cnh phng) :

CH2OCH3 O
5 6

CH3O

OCH3
3

H OH

CH2OH O
5

OH

OCH3
3

H OH

CH2OCH3 O
5

OH

OCH3
3

H OH

OCH3

OCH3

OCH3

2,3,4,6-tetra-O-metylglucoz(X)

2,3-di-O-metylglucoz(Y )

2,3,6-tri-O-metylglucoz(Z)

2,3,4,6-tetra-O-metylglucoz sinh ra t u mch phn t amilopectin; 2,3-di-Ometylglucoz sinh ra t ch c nhnh ca phn t amilopectin; 2,3,6-tri-O-metylglucoz sinh ra t trong mch v cui mch phn t amilopectin.

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

(b) S mol glucoz tham gia to amilopectin =
3,24 = 2010 3 . 162

32

% cc gc glucoz ch c nhnh ca phn t amilopectin =

16610 3 , . 2010 3 .

.100 = 8,3% %

(c) S mol 2,3,6-tri-O-metyl glucoz sinh ra = 20.10-3 - 2.1,66.10-3 = 16,68.10-3. 102. ( thi HSG quc gia, Vit Nam - 1999) T mt loi thc vt ngi ta tch ra c hp cht (A) c cng thc phn t C18H32O16. Thy phn hon ton (A) thu c glucoz (B), fructoz (C) v galactoz (D) : 1. Vit cng thc cu trc dng vng phng 5 v 6 cnh ca galactoz. 2. Hidro ha glucoz, fructoz v galactoz thu c cc poliancol. Vit cng thc cu trc ca cc poliancol tng ng vi (B) , (C) v (D). 3. Thy phn khng hon ton A nh enzim -galactoridaza (enzim xc tc cho phn ng thy phn cc -galactosit) thu c galactoz v saccozoz. Metyl ha hon ton (A) nh hn hp CH3I v Ag2O, sau thy phn sn phm metyl ha, thu c 2,3,4,6-tetra-Ometylgalactoz (E) v 2,3,4-tri-O-metylglucoz (G) v 1,3,4,6-tetra-O-metylfructoz (H). Vit cng thc cu trc ca (E), (G), (H) v (A). 1. Cng thc cu trc dng vng phng 5 v 6 cnh ca galactoz :
CHO H HO HO H OH H H OH CH2OH HO
1

CH2OH H O OH
3 1 2

H OH

CH2OH O OH 5
4

H OH

OH
3

OH

OH

2. Hidro ha glucoz to sn phm c s nguyn t C bt i khng i, hidro ha galactoz to ng phn meso, hidro ha fructoz to hn hp cc ng phn dia. V d :
CHO H HO H H OH H OH OH CH2OH D-glucoz H [H] HO H H CH2OH OH H OH OH CH2OH CHO H HO HO H OH H H OH H [H] HO HO H CH2OH OH H H OH CH2OH HO H H CHO O H OH OH H [H] HO H H CH2OH OH H HO HO + OH H OH CH2OH H CH2OH H H OH OH CH2OH

CH2OH D-galactoz

CH2OH D-fructoz

3. Thy phn khng hon ton A nh enzim -galactoridaza thu c galactoz v saccozoz, nh vy A c cu thnh t -galactoz, -glucoz, -fructoz, cng thc ca 2,3,4,6tetra-O-metylgalactoz (E), 2,3,4-tri-O-metylglucoz (G) v 1,3,4,6-tetra-O-metylfructoz (H) l :

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

CH2OCH3 O 5 OCH3
3 2 6

33

CH3O
4

H OH

CH2OH O 5 OCH3
3 2 1

H OH

CH3O

OCH3
(E)

OCH3
(G)

CH2OCH3 H O 2 CH3O 5 3 4 CH2OCH3 6 OCH3

(H)

Cc sn phm thy phn ny cho thy cu to ca A l :

CH2OH O OH 5
4 6

H O

OH
3

OH
4

CH2
5

O
2 1

H O

OH

OH
3

CH2OH O
3

H HO
4 6 5

OH

OH

CH2OH

103. ( thi HSG quc gia, Vit Nam - 2000) X l mt disaccarit khng kh c AgNO3 trong dung dch NH3. Khi thy phn X sinh ra sn phm duy nht l M (D-andoz, c cng thc vng dng ). M ch khc D-riboz cu hnh nguyn t C2.
3 3 2 M N Q dn xut 2,3,4- tri- O - metyl ca M

CH OH / HCl

CH I / NaOH

H O / H+

1. Xc nh cng thc ca M, N, Q v X (dng vng phng). 2. Hy vit s cc phn ng xy ra.

a. T cng thc dn xut 2,3,4-tri-O-metyl ca M suy ngc s ra cng thc ca Q, N, M t suy ra cng thc ca X :

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

CH3O H H CHO H O CH3O OCH3 CH3O OH OCH3 OCH3 CH2OH dn xut 2,3,4-tri-O-metyl ca M H2O/H+ O OH OH (N) CH3I/baz OCH3 CH3O O CH3O OCH3 (Q) O OH OH OH (X)

34

HO

OCH3

CH3OH/HCl O OH OH OH OH (M)

OH OH O O OH

H2O/xt

b. S phn ng : ... 104. ( thi HSG quc gia, Vit Nam - 2001) Melexitoz (C18H36O16) l ng khng kh, c trong mt ong. Khi thy phn hon ton 1 mol melexitoz bng axit s nhn c 2 mol D-glucoz v 1 mol D-fructoz. Khi thy phn khng hon ton s nhn c D-glucoz v disaccarit turanoz. Khi thy phn nh enzim mantaza s to thnh D-glucoz v D-fructoz, cn khi thy phn nh enzim khc s nhn c saccaroz. Metyl ha 1mol melexitoz ri thy phn s nhn c 1 mol 1,4,6-tri-O-metyl-D-fructoz v 2 mol 2,3,4,6-tetra-O-metyl-D-glucoz. 1. Hy vit cng thc cu trc ca melexitoz. Vit cng thc cu trc v gi tn h thng ca turanoz. 2. Hy ch ra rng vic khng hnh thnh fomandehit trong sn phm oxi ha bng HIO4 chng t c cu trc furanoz hoc pyranoz i vi mt xch fructoz v pyranoz hoc heptanoz (vng 7 cnh) i vi mt xch glucoz. 3. Cn bao nhiu mol HIO4 phn hy hai mt xch glucoz c cu trc heptanoz v s nhn c bao nhiu mol axit fomic ?

1. T cc d kin u bi suy ra melexitoz khng cn -OH semiaxetan, l trisaccarit c cu thnh t 2 dn v D-glucoz v 1 n v D-fructoz, trong 1 n v D-glucoz lin kt vi D-fructoz to thnh disaccarit turanoz, n v D-glucoz th hai cng lin kt vi Dfructoz to thnh disaccarit saccaroz. Thu phn 1 mol sn phm metyl ho melexitoz thu c:

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

CH2OCH3 O 2 CH3O 3 OH CH2OCH3 OH
1

35

CH3O

CH2OCH3 O 1 OCH3 2 OH OCH3

T suy ra n v D-fructoz dng furanorit, 2 n v D-glucoz u dng piranorit; 2 n v D-glucoz u to ra lin kt glicorit vi C2 v C3 ca Dfructofuranozit. Cu trc :
HO O 1 HO HO HO OH O H 1 HOH2C O 1 OH H O HO HO 2 3

H OH CH2OH HO O

1 HOH2C HO 1 OH H O 2 3

H OH CH2OH

HO HO

Melexitoz 18H36O16) (C

3-O-( -D-glucopiranozyl)-D-fructofuranoz (Turanoz)

Ho?c :
HO O 1 HO HO HO OH O 1 OH H O O 3 2 HO O CH2OH HO HOH2C 1 HO H HO HO O 1 H OH O 3 2 HO O CH2OH

HO HO

HOH2C 1 Melexitoz 18 36O16 (C H )

3-O-( -D-glucopiranozyl)-D-fructofuranoz (Turanoz)

2. Cu trc furanoz hoc piranoz i vi mt xch fructoz v piranoz hoc heptanoz (vng 7 cnh) i vi mt xch glucoz do khng c nhm 1,2-diol kiu -CHOH-CH2OH nn khng hnh thnh fomanehit trong sn phm oxi ho bng HIO4 :

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

Fructoz CH2OH HO HO H H H OH OH CH2 piranoz O HO HO H H CH2OH furanoz H OH O CH2OH HO HC H H H H OH OH OH OH CH2 heptanoz O Glucoz HO CH H H H H CH2OH piranoz OH OH OH O

36

3. Cn 6 mol HIO4 phn hu hai mt xch glucoz c cu trc heptanoz v s nhn c 4 mol axit fomic :
HO H 2 H H H H C OH OH OH OH CH2 O +6HIO4 2 CHO CH2 H HO C CHO 6HIO3 +2H2O O +4HCOOH +

105. ( thi HSG quc gia, Vit Nam - 2002) CHO Oxi ho 150 mg amiloz bi NaIO4 thu c 0,0045 mmol axit fomic. HO H (a) Tnh s lng trung bnh cc gc glucoz trong phn t amiloz; bit HO H rng khi oxi ho 1 mol amiloz bng NaIO4, s gc glucoz u mch to H OH ra 1 mol axit fomic, s gc glucoz cui mch to ra 2 mol axit fomic. HO H (b) Vit s cc phng trnh phn ng xy ra. CH2OH Vit s cc phng trnh phn ng chuyn D-glucoz thnh L-guloz c cng thc bn.

1. (a) S lng trung bnh cc gc glucoz trong phn t amiloz : (C6H10O5)n HIO4 3HCOOH
namiloz = nHCOOH =
1 3 0,0045 =0,0015 (mmol ) 3

M amiloz =

150 =100000 vC) ( 0,0015

n=

100000 617 162

(b) Phng trnh phn ng:

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

37

CH2OH O OH OH OH O

CH2OH O OH OH O n-2

CH2OH O OH OH OH

+ (n+4) HIO4 - 3 HCOOH HCHO (n+4) NaIO3

OHC

CH2OH O OHC O

CH2OH O CH HC O O O n-2

CHO CHO

2. S chuyn ha :
H HO H H CHO OH H + HNO3 OH OH CH2OH H HO H H COOH OH H OH OH COOH H HO H H CO OH O H OH COOH H + Na(Hg) HO H H CH2OH OH H OH OH COOH

- H2O

- H2O

CH2OH H OH H H OH H OH CO

+ Na(Hg)
pH = 7

H HO H H

CH2OH OH H OH OH CHO

106. ( thi HSG quc gia, Vit Nam - 1997) Mannoz (monosaccarit) HOCH2-CHOH)4-CH=O l ng phn ca glucoz. dng vng su cnh mannoz ch khc glucoz ch nhm OH nguyn t C2 nm cng pha vi OH nguyn t C3. Oxi ha mannoz bng dung dch HNO3 100oC thu c sn phm Y cha 41,38%C, 3,45%H v 55,17%O. Y b thy phn c trong mi trng axit cng nh baz to ra CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

38

axit polihidroxidicacboxilic hoc mui tng ng. Xc nh cng thc cu to ca Y, bit MY = 174vC.

t cng thc tng qut ca Y l CxHyOz

Tao c : x =
4138174 , . 3,45174 . 5517174 , . = 6, y = = 6, z = =6 12100 . 100 16100 .

Cng thc phn t ca Y l C6H6O6 Axit nitric oxi ha nhm -CH2OH v -CHO trong phn t mannoz thnh hai nhm -COOH. Nu sn phm cui l HOOC-(CHOH)4-CHO (C6H10O8) th khng ph hp vi cng thc phn t ca Y (C6H6O6). Mt khc theo gi thit Y b thy phn trong mi trng axit cng nh baz, vy Y phi l este ni phn t (lacton) hai ln este. ng vi cu trc bn (vng 5 hoc su cnh) th cu to ca Y s l :
CO HO H O H H O H OH CO CO H HO H O OH O H H CO
6 6 1 1

O hay O
6

OH C O
1

OH
2

HO O hay
4

1 3

OH
5

107. ( thi HSG quc gia, Vit Nam - 2001) 1. Vit phng trnh phn ng iu ch D-fructoz t D-glucoz, bit rng D-glucozazon khi tc dng vi benzandehit to thnh oson ca D-glucoz (HOCH2(CHOH)3COCHO). 2. Chitin (tch t v tm, cua...) c coi nh l dn xut ca xenluloz, trong cc nhm hidroxyl cc nguyn t C2 c thay th bng cc nhm axetylamino ( -NH-CO-CH3 ). c) Vit cng thc cu to mt on mch ca phn t chitin. d) Gi tn mt mt xch ca chitin. e) Vit phng trnh phn ng xy ra khi un nng chitin vi dung dch HCl c (d), un nng chitin vi dung dch NaOH c (d).

1. Phng trnh phn ng iu ch D-fructoz t D-glucoz :

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

H HO H H CHO OH H +2C6H5NHNH2 OH OH CH2OH CH N-NH-C6H5 N-NH-C6H5 HO H + 2H2O H OH H OH CH2OH

39

HO H H

HO H H

CH N-NH-C6H5 CH O N-NH-C6H5 O + H H HO H + 2C6H5CHO +2C6H5NHNH2 OH H OH OH H OH CH2OH CH2OH CH2OH CH O O O [H] HO H H H OH OH H OH OH CH2OH CH2OH

2. (a) Cng thc ca chitin

CH2OH O OH CH2OH O OH

OH O O hay HO H O NHCOCH 3 O O OH

NHCOCH 3 O

NHCOCH 3

NHCOCH 3

(b) N- axetyl-D-glucozamin (tn gi ca chitin : poly N-acetyl-D-glucosamine, -(1,4)-2-Acetamido-2-deoxy-Dglucose) (c) Sn phm phn ng khi tc dng vi dung dch HCl c (d), dung dch NaOH c (d) :
CH2OH O OH OH NH3Cl CH2OH O OH NH2 O CH2OH O OH NH2 O

OH

108. (Bi tp chun b IChO, Canada - 1997) D-andotetroz A khi phn ng vi axit nitric cho hp cht khng hot ng quang hc. Cng andotetroz ny khi phn ng vi HCN, tip theo vi dung dch nc Ba(OH)2 cho hai axit andonic epime B v C. Cc axit andonic ny nm trong cn bng vi cc -andolacton D v E tng ng ca chng. X l hn hp ny vi Na - Hg v nc pH 3-5 thu c cc cht F v G tng ng. Oxi ha F bng axit nitric thu c axit andaric khng hot ng quang hc H, trong khi thc hin phn ng ny vi E thu c axit andaric hot ng quang hc I. Cho bit cu trc cc cht t A n I

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

40

Ch D-andotetroz dng erythro mi cho sn phm khng hot ng quang hc khi b oxi ha bi axit nitric :
H H CHO OH + HNO3 OH CH2OH (A) H H COOH OH OH COOH

S l A bng HCN, tip theo vi dung dch nc Ba(OH)2 cho hai axit andonic epime B v C :
COOH COOH CHO H OH HO H H OH 1.HCN H OH H OH + H OH 2. Ba(OH)2 H OH H OH CH2OH CH2OH CH2OH (A) (B) (C) CO COOH H OH OH CH2OH (C)

Cc -lacton D v E tng ng l :
H H H COOH OH OH OH CH2OH (B) H H H OH O OH CH2OH (D) HO H H

CO HO H H H O OH CH2OH (E)

X l hn hp ny vi Na - Hg v nc pH 3-5 thu c cc cht F v G. Oxi ha bng axit nitric thu c axit andaric khng hot ng quang hc H v hot ng quang hc I :
(D) CHO OH Na(Hg) H H OH pH=3-5 H OH CH2OH (F) HNO3 H H H COOH OH OH OH COOH (H) Na(Hg) HO (E) H pH=3-5 H CHO H OH OH CH2OH (G) HNO3 COOH HO H H OH H OH COOH (I)

109. (Bi tp chun b IChO, Canada - 1997) -D-(+) mannopiranoz l epime ca -D-(+) glucopiranoz a. Hy vit cu trc dng gh bn vng nht ca n. b. Cho bit sn phm phn ng ca - D - (+) mannopiranoz vi cc cht : (a) Cu2+ + (m pH > 7) (g) 5HIO4 (b) Br2, H2O (pH = 6) (h) (CH3CO)2O d trong piridin (c) HNO3 (i) 3 mol phenylhidrazin, H+ (d) CH3OH , HCl khan (j) 1. Br2/H2O 2. Fe (III) sunfat , H2O2 (e) Sn phm (d) + (CH3)2SO4, NaOH (k) 1. HCN 2. Ba(OH)2 (f) 1. NaBH4 2.H2O 3. H3O+ 4. Na-Hg, H2O, pH=3-5

1. Cu trc dng gh bn vng nht ca -D-(+) mannopiranoz :

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

OH HO HO HO O H OH

41

2. Sn phm phn ng ca - D - (+) mannopiranoz :

(a) COO_ HO H + CuO 2 (b) COOH HO H (c) HO HO H H COOH H H OH OH COOH CH2OH H H OH OH CH2OH

(d)

OCH3

(e)

CH3O

CH3O CH3O

OCH3 O H OCH3

(f) HO HO H H

(g) H OH H H

(h) AcO AcO H H

O O 5 ng lng 1 ng lng

CHO H H OAc OAc CH2OAc CHO CHO H OH H HO H H HO H H + H OH OH H OH OH COOH COOH

(i)

NNHC6H5 NNHC6H5 HO H H OH H OH CH2OH

(j) HO H H CHO H OH OH COOH

(k) HO HO HO H H

110. (Bi tp chun b IChO, Thi Lan - 1999) 1. Dng cng thc Haworth ngh mt hay nhiu cu to vng vi ha lp th c th c cho D-tagaloz.

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

CH 2OH C O HO H HO H H OH CH 2OH

42

(D)-tagaloz 2. Hai sn phm c cng cng thc C6H10O6 thu c khi D-arabinoz tc dng vi NaCN/H+ ri thy phn trong mi trng axit. Vit cu to km theo ha lp th c th c ca hai hp cht v cho bit chng to thnh nh th no ?
CHO HO H 1. NaCN/H+ H OH 2. H3O+/ t o H OH CH2OH (D)-arabinoz

?+?

1. Cu to vng vi ha lp th c th c cho D-tagaloz :

CH2OH OH H O CH2OH (OH) HO OH (CH OH) 2 HO OH O OH (CH OH) 2 OH CH2OH (OH)

2. Phn ng ca D-arabinoz :
HO HO H H NaCN/H+

CHO HO H H OH H OH CH2OH (D)-arabinoz

CN H H OH OH CH2OH + CN OH H OH OH CH2OH

HO HO H H H3O+/ t o

COOH H H OH OH CH2OH + COOH OH H OH OH CH2OH

-H2O

CH2OH O OH OH OH

H HO H H

H HO H H

-H2O

CH2OH O OH OH OH

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

43

111. (Bi tp chun b IChO, Canada - 1997) D-idoz c cu hnh khc D-glucoz C-2, C-3 v C-4. cn bng, D-idoz gm 75% dng piranoz v 25% dng furanoz. 1. Hy vit c hai cu dng xyclohexan ca cc ng phn dng vng , ca D-idopiranoz. ng phn no bn vng nht ? V sao ? 2. Qua s ng phn ha Lobry de Bruyn Abberda van Ekenstein, D-idoz c th chuyn thnh 2-xetoz (D-socboz). Hy v dng furanoz ca D-socboz 3. Khi un nng D-idoz mt nc thun nghch v tn ti ch yu di dng 1,6-dihidro-Didopiranoz. Hy cho bit phn ng ny thch hp vi dng ng phn no ? Vit cng thc hp cht ny. Cho bit ti sao phn ng ny khng xy ra vi glucoz ?

a. Hai cu dng gh ca D-idoz l :

OH OH OH O vng HO H HO H CHO H OH H OH CH2OH OH OH HO HO OH O OH

OH

cu dng b h v nhi nhm thbin hn n n c u

OH OH OH OH O OH vng OH HO HO O OH OH

cu dng b h v nhi nhm thbin hn n n c u

b. Cu to ca D-socbofuranoz :
CHO O H HO H OH H OH CH2OH CH2OH OH H OH (CH2OH) OH O CH2OH (OH)

c. Phn ng dehidrat ha ng vng ni phn t thun li khi nhm OH trn C1 v nhm -CH2OH u v tr trc. Nh vy vi D-idoz phn ng thun li vi dng , cn glucoz khng c c phn ng ny :

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

OH O HO OH OH HO HO O O - H 2O OH

44

HO

112. (Bi tp chun b IChO, Canada - 1997) Disaccarit A b thy phn bi axit long to hn hp gm D-glucoz v D-galactoz. Hp cht A l mt ng kh v b oxi ha bi nc Br2 to axit B, axit ny c metyl ha bng (CH3)2SO4/NaOH to thnh hp cht octa-O-metyl ha. Thy phn hp cht ny thu c axit tetra-O-metylgluconic C v tetra-O-metylgalactoz D. Hp cht C b oxi ha bi axit nitric to thnh axit tetra-O-metylglucaric. Cht A b thy phn bi -galactosidaza tch t hnh nhn. Cho bit cu trc ca A, B, C, D.

OH HO

OH O H OH O HO HO (A) O H OH HO Br2

OH HO

OH O H OH O HO HO (B) OH OH COOH

H CH3O H H 1. metyl ha 2. th phn y H H3CO CH3O H

COOH OCH3 H OCH3 OCH3 CH2OH + CHO OCH3 H H OCH3 CH2OH

HNO3

H CH3O H H

(C)

COOH OCH3 H OCH3 OCH3 COOH

(D)

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

45

113. ( thi olympic quc gia ba nc min BalTic) Khi thy phn tinh bt bng axit th thng ch to thnh sn phm c v ngt (glucoz, mantoz...).Khi thy phn tinh bt trong cng nghip (30-40% huyn ph tinh bt trong dung dch HCl long, nhit 130-140oC) mt vi hp cht dng c to thnh. Ngi ta ngh rng cht ng ng X ny c to thnh do phn ng thy phn thun nghch. X c tch ra v tinh ch. xc nh cu to ca n ngi ta tin hnh cc th nghim sau : 1. Thy phn trong dung dch axit : Ch c glucoz c tch ra trong phn ng ny. 2. Th andehit : 25mg X c ha tan trong 25cm3 dung dch kalihexaxyanoferat(III) K3[Fe(CN)6] 0,01M. Sau thm 5cm3 dung dch KOH 0,1M v a hn hp ln 100oC trong khong 15 pht. Lng d K3[Fe(CN)6] c xc nh bng phng php chun iot. Thm mt lng d KI v hn hp c axit ha bng CH3COOH. 10,5cm3 Na2S2O30,01M c dng chun. 3. Metyl ha v oxi ha : X c metyl ha bng mt lng d metyliodua, c mt bc(I)oxit. Sau sn phm metyl ha c un nng vi HNO3 30%. Hai axit c tch ra t hn hp l: axit 2,3,4-trimetoxi-5-hidroxiadipic HOOC-CH(OH)[CH(CCH3)]3-COOH v axit 2,3,4,6-tetrametoxi-5-hidroxicaproic CH3OCH2-CH(OH)[CH(OCH3)]3COOH. a. Xc nh cu to ca X. b. Vit phng trnh phn ng ca cc th nghim nhn bit X. 114. ( thi olympic quc gia H Lan) D-glucoz, cht ng c nhiu trong thin nhin, l mt trong nhiu ng phn lp th ca 2,3,4,5,6-pentahidroxihexanal cng thc phn t l C6H12O6. Khi ha tan trong nc n tn ti nhiu dng vng v mt dng h. Hnh bn l hnh chiu Haworth ca mt trong nhng dng vng. Khi c mt baz, D-glucoz c th chuyn thnh nhng cht ng khc. 1. Hy cho bit hnh chiu Fisher ca hai cacbonhidrat, trong cu to m to thnh u tin trong phn ng ca dung dch D-glucoz trong nc vi baz. D-glucoz b kh bi NaBH4 thnh D-gluxitol. 2. Khi nhm c trng no trong D-glucoz b chuyn ha ? Cho D-glucoz tc dng vi peiodat d 3. Cho bit cng thc cu to ca nhng sn phm to thnh trong phn ng ny.

115. (Bi tp chun b IChO, Canada - 1997) Disaccarit A khng phn ng vi thuc th Benedict v khng nghch chuyn. A b thy phn bi -glucoridaza, khng b thy phn bi -glucosidaza. Metyl ha A, tip theo thy phn thu c 2 ng lng mol 2,3,4,6-tetra-O-metyl-D-glucoz. 1. Cho bit cu trc ca A. 2. Cho bit bao nhiu mol axit peiodic s phn ng vi A. 3. Cho bit bao nhiu mol metanal v bao nhiu mol axit metanoic c hnh thnh trong phn ng ca A vi axit peiodic. 116: Phn ng oxiha ct mch gluxit bi HIO4 c nhiu mc ch khc nhau. CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

(cc nhm-CHOH- v -CHO H-COOH ; -CH2OH H-CHO ; >C=O CO2)

46

a) D Arabinoz l ng phn cu hnh C2 ca D Riboz. xc nh cu to ca n ngi ta thc hin cc phn ng sau : O

CH 3OH HCl HIO4 1) H3O 2) Br2 / H 2O
+

HO HOOCCO HO OH

OH

DArabinoz

b) Nu phng php phn bit D glucoz vi D fructoz

Oxiha bng HIO4 :

CHO H H HO H H OH H H HO OH H OH H CH2OH OH H OH OH

+ 5 HIO4 - 5 HIO3

HCHO + 5 H-COOH

(D- Glucoz )
CH2OH O HO H H H OH OH CH2OH HO HO H H

CH2OH CH2OH

H OH OH CH2

+ 4 HIO4 O - 4 HIO3

2 HCHO + 3 H-COOH + CO2

(D-Fructoz ) Cho hi sn phm sc qua dung dch nc vi ta nhn c D Fructoz CO2 + Ca(OH)2 CaCO3 + H2O OH + HOCH2-COOH Hi D Arabinoz c cu to vng 5 cnh hay 6 cnh ? V cu to

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

Nu l vng 5 cnh th :
CHO OH H H H OH OH CH2OH OH H H CH2OH OH H OH CH3OH OH HCl H H CH2OH OCH3 H OH OCH3 HIO4 CHO CHO H CH2OH

47

COOH Br2 H2O COOH COOH CH OH

(D-Arabinoz )

CH2OH

Kt qu tri gi thit, vy D Arabinoz c cu to vng 6 cnh

CHO OH H H H OH OH CH2OH OH H H CH2 OH H OH OH CH3OH OH HCl H H CH2 OCH3 H OH OH OCH3 HIO4 CHO COOH Br2 H3O+ COOH COOH CH2 CH2OH

CHO CH2

(D-Arabinoz )

Cu to vng ca D Arabinoz l :
O OH HO OH OH

hay

117: a) X l mt isaccarit khng kh c AgNO3 trong dung dch amoniac. Khi thu phn X sinh ra sn phm duy nht l M (D-anoz , c ng thc vng dng ). M ch khc D-riboz cu hnh nguyn t C2 .
CH 3OH CH 3 I H 3O + M N Q dn xut 2,3,4-tri-O-metyl ca M HCl NaOH

Xc nh cng thc ca M , N , Q v X ( dng vng phng ) .

T cng thc dn xut 2,3,4-tri-O-metylca M suy ngc s ra cng thc ca Q , N v M , t

suy ra X. (X khng c tnh kh phn t khng c nhm OH semiaxetal )

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

CHO H H H OH OH OH CH2OH CH3O H H CHO H OCH3 OCH3 CH2OH CH3O CH3O

48

O CH3O OH

(D-Riboz )
5 O OH 2 OH CH3OH HCl HO OH O OH 1 O 1 O 2

(Dn xut 2,3,4-tri-O-metyl ca M )

OH 3 OH 5 4 OH H3O+ 5 4 HO 3 OH O OH 2 1 OH

(X) 4
HO 3

(M)

(N)
OCH3

CH3I NaOH CH3O CH3O

O CH3O OCH3

(Q)

b) A l mt isaccarit kh c AgNO3 trong dd NH3, thu phn A (nh cht xc tc axit) sinh ra D glucoz v D galactoz (ng phn cu hnh C4 ca D glucoz). Cho A tc dng vi mt lng d CH3I trong mi trng baz thu c sn phm B khng c tnh kh. un nng B vi dung dch axit long thu c dn xut 2,3,6-tri-O-metyl ca D glucoz v dn xut 2,3,4,6-tetra-O-metyl ca D galactoz. Vit cng thc cu trc (dng vng 6 cnh phng) ca B, C, A, D; bit rng trong phn t A c lin kt - 1,4 - glicozit.

Cu to vng phng ca D glucoz v D galactoz

CH2OH O OH HO OH OH OH HO OH CH2OH OH

A c tnh kh phn t c nhm OH semiaxetal

CHUYN GLUXIT

T S CHNG- TRNG PTTH CHUYN QUNG BNH

5

49

CH2OH O OH
3 2 1 O 4

CH2OH
5

CH2OCH3
1

HO
4

CH2OCH3 O O OCH3 OCH

3

O OH
3 2

OH

CH3I CH3O NaOH

O OCH3 OCH3

OH

OH

OCH3

(A)

(B)

CHUYN GLUXIT