BI KIM TRA CUI CNG (FINAL TEST-1) Bi 1.

phn ln cc phn t, cc vng su cnh kt dnh trans vi nhau thng bn hn kt dnh cis. Khi x l vi kim, s kt dnh cis gia hai vng D/E trong hp cht metyl 11-oxooleanolat (A) b thay i t cis thnh trans. Tuy nhin, khi x l kim tng t vi metyl 11-oxoursolat (B) th s kt dnh cis gia D/E khng b thay i, tc l cis bn hn. Hy gii thch.

O D

E COOMe HO (A)

O D

E COOMe

HO

(B)

Bi 2. Cht Aine A is mt hexahydronaphtalenedione. H 4 H 4 3 Trong phn t bn phi (Aine A) nhm xeton th hai c th 3 [H] nm mt trong cc v tr t 1 n 4. Kh ha nhm C=O 2 2 O HO 1 1 thnh nhm hydroxyl, COH v lin kt i thnh lin kt H Aine A n nhn c ng phn lp th khc nhau, trong c 4 meso (khng quang hot). a) Xc nh v tr ca nhm xeton th hai trong cht A. b) V cc cu trc (lp th) sn phm kh ha ca A. Nu cu trc no l meso hoc cp i quang. Bi 3. 1) Cng thc ca axit quinic (A) c dn ra bn. A c bao nhiu ng phn lp th. Ghi cu hnh R- hoc S- (theo h CIP) cc tm bt i ca A.

2) Vitamin C (axit ascorbic) c cng thc sau:

a) Ghi cu hnh R/S vo cc tm bt i ca vitamin C. b) Cng thc ny c th cho bit vitamin C xut pht t ng dy D hay L khng? V cng thc ny di dng hnh chiu Fis lm sng t kin trn.

Bi 4. 1) Cho s sau:
HOBr B2H6 H2/Pd

A C E

H2/Pd H2O OH CH2N2 a.s

-

B D F
m vng Pd

to

Vit cng thc cu to ca cc cht A, B, C, D, E, F, G, H. 2) T xiclopentan, 4-clobutanal v cc cht cn thit, hy tng hp cht M: O OCH3 M Cho bit M c bao nhiu ng phn lp th? Vit cng thc ca mt trong s ng phn km theo k hiu cu hnh (R/S). Bi 5. Sulcatol (X, C8H16O), l mt phermon quang hot. Cho Sulcatol phn ng vi ozon, tip theo x l sn phm vi H2O2/HO- thu c mt hn hp gm propanon v mt hp cht vng A. Kh ha A thnh B (C5H10O2). 1) xc nh cng thc ca Sukcatol v gi tn theo IUPAC 2) V cu trc ca 2 ng phn ca B (nu r cu hnh R/S tm bt i). Bi 6. 1) Bradikinin l mt nonapeptit, khi thy phn cho Pro-Pro-Gly; Ser-Pro-Phe; Gly-Phe-Ser; Pro-Phe-Arg; Arg-Pro-Pro; Pro-Gly-Phe; Phe-Ser-Pro. (a) Vit th t lin kt ca cc aminoaxit trong phn t bradikinin. (b) Cho bit bradikinin c gi tr pHI trong khong no ? ( 6; <6; > 6). 2) miu t tnh cht axit-baz ca amino axit, glycine ( dng H3N+CH2COOH) ngi ta s dng mt ng cong chun ca glycine vi dung dch NaOH. Nhm amino khng phn li l RNH3+, cn nhm phn li l RNH2. C hai nhm u c tnh cht ca dung dch m khong pH nht nh nn c th p dng phng trnh Henderson-Hasselbach tnh pH. a) Vit phng trnh ion ca glycine vi NaOH theo 2 bc. b) Glycine c mt dng no: i) phn u ca ca ng cong chun (pH < pKa), ii) phn cui ca ng cong chun (pH > pKb)?
12 10 8

pH

6 4 2 0 0 2 4 6 8

V(NaOH) / cm

10

12

c) Tnh % glycine H3N+CH2COO-, khi i) pH = pI, ii) pH = 2.817 (pKa = 2.34), iii) pH = 10.057 (pKb = 9.58). Bi 7. Disaccarit A khi thy phn vi -galactosidaza cho hn hp D-galactoza v mt andohexoz B ch khc vi D-galactoz cu hnh C4. X l A ln lt, u tin vi nc brm, sau metyl ha cho hp cht A1. Thy phn A1 thu c dn xut tetra-O-metyl ca D-galactoza v axit tetra-O-metyl D-andonic (C). Cht C cho oxi ha vi axit nitric th thu c axit tetra-O-metylglutaric. Hy vit cc phn ng chng minh cu trc ca A.

HNG DN GII Bi 1. vng E, cht A, 2 nhm metyl nm v tr e v a nn khi D/E cis b chuyn thnh D/E trans th v tr ca 2 nhm ny khng thay i. Cn vng E, cht B, 2 nhm metyl nm v tr e,e, nn nu D/E cis b chuyn thnh D/E trans th v tr ca 2 nhm ny s l a,a khng thun li. Bi 2. a) v tr 2 (x = 2): A 1,3,4,4a,5,6-hexahydronaphthalene-2,7-dion b) V tr 3, x = 2
H H H H 1 HO 3 H H 2 HO 4 OH HO OH HO H H 6 OH HO 5 OH HO 7 OH HO OH

H H

H H

8 H OH HO H OH

1, 2, 7, 8 are meso-forms. 3 and 5, 4 and 6 are enantiomers. Bi 3. 1)

C th ghi cu hnh-R cho 2 tm bt i. hai tm cn li khng th do c hai nhm tng ng nhau. Nh vy, axit quinic l phn t quang hot nhng khng th phn bit c cc i quang hay p dia nu dng h CIP. 2)

Bi 4. 1) Sn phm t s :

Br BH2 A B raxemic C D

OH

2) * T xiclopentan iu ch andehit trung gian,thc hin cc bc sau: 1- Br2/as; 2- Mg/ete; 3- i) CO2, ii) H3O+; 4- Br2/P ; 5- loi HBr (NaOH/ru) 6- SOCl2; 7- LiAlH4.
CHO

* Tin hnh phn ng: 1- kha nhm CHO (bng HOCH2CH2OH)/H+; 4- ng vng (bn axetal) 5- CH3OH/H+. Bi 5.
OH

2- Mg/ete

3- vi andehit iu ch trn

O O A

Bi 6. 1) (a) Bradikinin : Arg-Pro-Pro-Gly-Phe-Ser-Pro-Phe-Arg. (b) pHI >> 6 v phn t cha 2 nhm guanidino, ngoi ra cn c 3 vng piroliddin. 2) a) H3N+CH2COOH + OH- = H3N+CH2COO- + H2O H3N+CH2COO- + OH- = H2NCH2COO- + H2O b) i) H3N+CH2COOH ii) H2NCH2COOc) H3N+CH2COOd) i) %(H3N+CH2COO-) = 100 [H3 N + CH 2 COO ] [H3 N + CH 2 COO ] ii) 2.817 = 2.34 + log =3 [H3 N + CH 2 COOH ] [H3 N + CH 2 COOH ] [H3N+CH2COO-] = 3[H3N+CH2COOH] c(glycine) = [H3N+CH2COOH] + [H3N+CH2COO-] = 4[H3N+CH2COO-] [H3N +CH 2 COO ] 100 = %(H3N+CH2COO-) = c(glycine)

3[H3N + CH2 COO ] 3 = 100 = 100 = 75% + 4 4[H3N CH2 COO ]

iii)

[H2NCH 2 COO ] [H2NCH 2 COO ] 10.057 = 9.58 + log =3 [H3N + CH 2 COO ] [H3N + CH 2 COO ] [H2NCH2COO-] = 3[H3N+CH2COO-] c(glycine) = [H2NCH2COO-] + [H3N+CH2COO-] = 4[H3N+CH2COO-]
%(H3N+CH2COO-) =
[H3N + CH 2 COO ] 1 100 = 100 = 25% c(glycine) 4

Bi 8. Melibioz = 6-O-(-D-galactopyranosyl)-D-glucopyranoz.