Cau 1. D-Galactoz la ong phan epime cua D-Glucoz cacbon so 4. a.

. Viet cong thc Haworth va cau dang cua D-Galactoz piranoz. b. Viet cac phng trnh phan ng cua -D-Galactoz vi CH3OH (HCl khan), nc brom va phenyl hidrazin. Cau 2 D-Idoz co cau hnh oi nhau cua D-Glucoz C2, C3, C4. a. Hay viet ca hai cau dang cua 2 ong phan dang vong a va b cua Didozpiranoz. ong phan dang vong nao ben hn. V sao? b. Khi un nong D-Idoz b mat nc thuan nghch va ton tai chu yeu la 1,6anhidro-D-idozpiranoz. Hay cho biet phan ng nay thch hp vi dang ong phan nao? Viet cong thc cau tao cua hp chat nay. Vi D-Glucoz co phan ng tren khong? V sao? Cau 3. Mot disacarit A khong co tnh kh. Khi thuy phan trong moi trng axit A cho san pham duy nhat la pentoz B. Cung co the thuy phan A nh enzim gicoziaza song khong dung c -glicoza. T B co the tao ra D-glucoz bang cach cho tac dung vi HCN roi thuy phan (xuc tac axit) va kh. a. Viet cong thc Fis va goi ten B theo danh phap he thong. b. Viet s o phan ng chuyen hoa B thanh D-glucoz. c. Viet cong thc cau truc cua A dang vong 6 canh phang. d. e jkhang nh cau truc vong 6 canh cua A, ngi ta cho A tac dung vi CH3Br trong moi trng baz roi thuy phan (xuc tac axit). Dung cong thc cau truc, viet s o cac phan ng. Cau 4. Chat A la hp chat hu c co mot lien ket O- -glicozit gia 1 disacarit G va mot -aminoaxit F a hidroxyl hoa. A b thuy phan bang enzim amino peptidaza thu c D glucoz va chat B. B b thuy phan bang dung dch HCl cho D-Galactoz va mot hidroxi amino axit F. F la -amino axit khong phan nhanh co mot nhom OH nguyen t C5 va mot nhom NH2 au mach cacbon. Phan tch nh lng chat B thay co 44,44%C, 7,46% H va 8,64%N theo khoi lng vi MB < 400. a. Xac nh cong thc cau truc cua disaccarit G. b. Xac nh cong thc cau truc cua F va A. Biet cac monosacarit co cau truc hnh 6 canh phang va lienm ket vi nhau bang lien ket -1,2-glicozit va D-galactoz co cau hnh oi nhau vi D-gluco v tr C4. 2. Mannoz (monosaccarit) HOCH2-(CHOH)4-CH=O l ng phn ca glucoz. dng vng 6 cnh mannoz ch khc glucoz ch nhm OH nguyn t C2 nm cng pha vi OH nguyn t C3. Oxi ho mannoz bng dd HNO3 100oC thu c sn phm Y cha 41,38%C; 3,45%H v 55,17%O. Y b thu phn c trong mi trng axit cng nh baz to ra axit polihiroxiicacboxylic hoc mui tng ng. Xc nh cng thc cu to ca Y, bit MY = 174 vC. Bi V: 1*) A l mt isaccarit kh c AgNO3 trong dd NH3,CHO ng phn c kh nng lm quay mt gm hai CHO phng nh H phn cc trong nhng iu kin thng nht biu th bng []25D l +92,6o v +34o. Dung dch sng H OH OH ca miHO phn ny t bin i v []25D cho ti khi cng t gi tr n nh l + 52o. ng HO H H Thu phn A (nh cht xc tc axit) sinh ra B v C: HO H H OH H OH H OH
CH2OH (B) CH2OH (C)

Cho A tc dng vi mt lng d CH3I trong mi trng baz thu c sn phm D khng c tnh kh. un nng D vi dd 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) ca B, C, A, D; bit rng trong phn t A c lin kt 1,4 - glicozit. Gii thch v vit cc phng trnh phn ng. b) V sao dd mi ng phn ca A t bin i v []25D v cui cng u t gi tr 52o? Tnh thnh phn phn trm cc cht trong dd gi tr []25D = 525 v vit cng thc cu trc ca cc cht thnh phn . 2. Metyl ho hon ton cc nhm OH ca 3,24 gam amilopectin bng cch cho tc dng vi CH3I trong mi trng baz, ri em thu 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 - i - O - metylglucoz; 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 phn trm cc gc glucoz nhng ch c nhnh ca phn t amilopectin. c) Tnh s mol 2,3,6 - tri - O - metylglucoz sinh ra trong phng th nghim trn. Cu III: T mt loi thc vt ngi ta CH=O tch c hp cht (A) c cng H OH thc phn t C18H32O16. Thu HO H phn hon ton (A) thu c HO H glucoz (B), fructoz (C) v H OH glucoz (D): CH2OH (D) 1. Vit cng thc cu trc dng vng phng 5 cnh v 6 cnh ca galactoz. 2. Hiro ho glucoz, fructoz v galactoz thu c cc poliancol (ru a chc). Vit cng thc cu trc ca cc poliancol tng ng vi (B), (C) v (D). 3. Thu phn khng hon ton (A) nh enzim -galactozidaza (enzim xc tc cho phn ng thu phn cc galactozit) thu c galactoz v saccaroz. Metyl ho hon ton (A) nh hn hp CH3I v Ag2O, sau thu phn sn phm metyl ho thu c 2,3,4,6-tetra-O-metyl galactoz (E) v 2,3,4-tri-O-metyl glucoz (G) v 1,3,4,6-tetra-O-metyl fructoz (H). Vit cng thc cu trc ca (E), (G), (H) v (A). Cu IV: 1) X l mt isaccarit khng kh c AgNO3 trong dd amoniac. Khi thu 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. H 2O CH3OH CH3I M N Q dn xut 2,3,4-tri-O-metyl ca M HCl xt baz xt xt H + a. Xc nh cng thc ca M, N, Q v X (dng vng phng). b. Hy vit s cc phn ng xy ra. Cu IV (4,5 im): Melexitoz (C18H32O16) l ng khng kh, c trong mt ong. Khi thu phn hon ton 1 mol melexitoz bng axit s nhn c 2 mol D-glucoz v 1 mol D- fructoz. Khi thu phn khng hon ton s nhn c D-glucoz v isaccarit turanoz. Khi thu phn nh enzim mantaza s to thnh D-glucoz v Dfructoz, cn khi thu phn nh enzim khc s nhn c saccaroz. Metyl ho 1 mol melexitoz ri thu 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 fomanehit trong sn phm oxi ho bng HIO 4 chng t c cu trc furanoz hoc piranoz i vi mt xch fructoz v piranoz hoc heptanoz (vng 7 cnh) i vi mt xch glucoz. 3. Cn bao nhiu mol HIO4 phn hu hai mt xch glucoz c cu trc heptanoz v s nhn c bao nhiu mol axit fomic?

Cu IV (4,5 im): 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-CO-CH3 ). 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). Cu V: (2,5 im) Oxi ho 150 mg amiloz bi NaIO4 thu c 0,0045 mmol axit fomic. (a) Tnh s lng trung bnh cc gc glucoz trong phn t amiloz; bit rng khi oxi CHO H OH ho 1 mol amiloz bng NaIO4, s gc glucoz u mch to ra 1 mol axit HO H fomic, s gc glucoz cui mch to ra 2 mol axit fomic. H OH (b) Vit s cc phng trnh phn ng xy ra. HO H Vit s cc phng trnh phn ng chuyn D-glucoz thnh L-guloz c cng thc CH2OH bn. Cu V: L-galuz isaccarit X (C12H22O11) khng tham gia phn ng trng bc, khng b thy phn bi enzim mantaza nhng b thy phn bi enzim emulsin. Cho X phn ng vi CH3I ri thy phn th ch c 2,3,4,6-tetra-O-metyl-D-guloz. Bit rng: D-guloz l ng phn cu hnh C3 v C4 ca D-glucoz; mantaza xc tc cho s thy phn ch lin kt -glicozit, cn emulsin xc tc cho s thy phn ch lin kt -glicozit. 1. Vit cng thc lp th ca X. 2. Deoxi- D-guloz A (C6H12O5) c chuyn ha theo 2 hng sau:
HIO4 CH3OH, H
+

1) LiAlH 4 2) H O 2

H3O+

Glixerin, 3-hidroxipropanal

B
HBr

C6H11BrO (E) 4

KOH

C6H10 4 (F) H2O/ DCl hn hp O G

a) Xc nh cng thc cu to ca A. b) Vit cng thc cu to ca B, C, D, E, F. c) Xc nh cng thc cu to cc cht c trong hn hp G, bit phn t khi ca chng u ln hn 160 v nh hn 170 vC. Cu III 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

a) Vit cng thc Fis ca A v B. b) A tn ti 4 dng gh (D-glicopiranoz). Vit cng thc ca cc dng v cho bit dng no bn hn c? c) 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? d) Vit cng thc cu trc ca E v G. Hy cho bit chng c tnh quang hot hay khng? Cu 4 (4 im): 1. D-Galactoz l ng phn cu hnh v tr s 4 ca D-glucoz. Trong dung dch nc D-galactoz tn ti 5 dng cu trc khc nhau trong mt h cn bng. Hy dng cng thc cu hnh biu din h cn bng v cho bit dng no chim t l cao nht.

2. D-Galactoz l sn phm duy nht sinh ra khi thu phn hp cht A (C12H22O11). thc hin phn ng ny ch c th dng cht xc tc l axit hoc enzim -galactoziaza. A khng kh c dung dch Fehling, song tc dng c vi CH3I trong mi trng baz cho sn phm ri em thu phn th ch thu c sinh ra mt hn hp sn 3. un nng D-galactoz ti 165oC2,3,4,6-tetra-O-metyl-D-galactoz. Hy tm cu trc ca A, hp cht B. Cho B tc phm, trong c mt lng nh vit cng thc vng phng v cng thc cu dng ca n.

dng vi CH3I (c baz xc tc) ri thu phn sn phm sinh ra th thu c hp cht C l mt dn xut tri-O-metyl ca D-galactoz. Hy gii thch qu trnh hnh thnh B v vit cng thc Fis ca C.

HO
Cu 5 (3,75 im): 1. Vit cng thc chiu Fis ca dng mch h cc cht sau:
OH HOCH2 CH2 OH OH OH H2C OH OH H3C OH OH OH HO OH OH

O
HO OH HO OH

CH2OH

OH

(A)

(B)

(C)

(D)

2. Trong cc cht (A), (B), (C), (D) trn, cht no: a) thuc dy L? b) l ng eoxi? c) l ng c mch nhnh? d) thuc loi xetoz? e) c dng furanoz? g) c cu hnh nhm anomeric?