B GIO DC V O TO

K THI CHN HC SINH VO CC I TUYN QUC GIA D THI OLYMPIC QUC T NM 2010 HNG DN CHM THI CHNH THC Mn: HO HC Ngy thi th hai: 18/04/2010

Cu 1. (4 im) 1. (0,5 im); 2. (1,5 im); 3. (2,0 im). 1. Hy vit mt cng thc cu to ca hirocacbon X (C14H26) m c hn 50 ng phn quang hc. 2. V cc cu trc ng phn c cng cng thc phn t C4H8O trong cc trng hp sau: a. L cc ng phn hnh hc. b. L cc ng phn quang hc. c. Va l ng phn hnh hc, va l ng phn quang hc. 3. T tinh du bc h ngi ta tch c (-)-menton (trans-2-isopropyl-5-metylxiclohexanon). Khi ch ha (-)-menton vi axit hoc kim, n chuyn mt phn thnh xeton ng phn (+)-isomenton. Khi ch ha (-)-menton vi anhirit axetic trong dung dch natri axetat th thu c hai ng phn A v B c cng thc phn t C12H20O2. a. V cc cu trc ng phn lp th ca (-)-menton. b. Dng cng thc cu trc, hy gii thch s to thnh (+)-isomenton, A v B t (-)-menton. Hng dn gii: 1. Nu X c n cacbon bt i th s ng phn quang hc ti a ca X l 2n . Theo bi ra ta c: 2n > 50, vy n 6. Di y l mt s cc cng thc cu to c th c ca X tha mn iu kin ca bi (du * ch cacbon bt i).
* * *

* *

* * * *

* *

* * *

* * *

** * *

(Ghi ch: hc sinh ch cn v mt trong s cc cng thc trn hoc c th v cng thc cu to c s cacbon bt i n 6, khc vi v d trn, vn cho im ti a). 2. Cc hp cht bn c cng thc phn t C4H8O tha mn cc iu kin sau: a. L ng phn hnh hc:
CH3 C H C CH2OH
H

CH3 C C

CH2OH H

CH3 C H C

H OCH3

CH3 C H C

OCH3 H

E b. L ng phn quang hc:

H CH2 CH C * CH3 OH

Z
CH3 * H O

E
O

C 2H 5 H

c. Va l ng phn hnh hc , va l ng phn quang hc:

CH3 H O H CH3 CH3 H O CH3 H

CH3 H

H OH

CH3 H

OH H

meso

Trang 1/7

3. a.

II
3

O
III
2

O
IV

b. (-)-Menton b enol ha, C2 c lai ha sp tr thnh lai ha sp , khi tr li xeton C2 c lai ha sp3 vi cu hnh S ( I) hoc R ( III):
+ + -

H (OH )

H (OH )

OH

I III I c 2 dng enol, phn ng khng thun nghch vi Ac 2O to ra 2 este ng phn A v B .

Ac2O -NaAc

NaAcO

NaAcO

Ac2O -NaAc

OAc

OAc

Cu 2. (4 im). 1. (3,0 im); 2. (1,0 im). 1. Atenolol (C14H22N2O3) c s dng iu tr mt s bnh tim mch. Atenolol c th c tng hp qua cc bc sau: tng hp p-hiroxiphenylaxetamit (A) t phenol; tng hp epiclohirin Cl (B) t propen; cho A phn ng vi B (xc tc NaOH), thu c hai sn phm chnh l D v E cng vi mt sn phm ph l G. Isopropylamin phn ng vi D, E u cho atenolol. Bit phn t khi ca D = 207, E = 243,5 v G = 358. c s dng cc ha cht cn thit. a. Vit s cc phn ng tng hp A t phenol; B t propen. Xc nh cng thc cu to ca D, E, G. b. Vit cc phn ng ca isopropylamin vi D, E to thnh atenolol, bit rng atenolol l mt ete thm. 2. Thy phn hon ton polypeptit A ngi ta thu c cc amino axit: Val Trp Met2 Gly2 Lys Ala2 Ile Pro Asp Arg Tyr Cys. Thy phn A bng xc tc trypsin th thu c cc phn on sau: Val-Trp-Met-Gly-Lys, Ala-Ile-Pro-Met-Asp-Arg, Tyr-Ala-Gly-Cys. Nu dng xc tc chymotrypsin th thu c: Ala-Gly-Cys, Met-Gly-Lys-Ala-Ile-Pro-Met-Asp-Arg-Tyr, Val-Trp. Hy xc nh trnh t cc amino axit trong A. Hng dn gii: 1. a. Tng hp A:
OH
HCHO/HCl
O

OH
NaCN/DMF

OH
1. H3O
+ o

OH

2.NH3, t

CH2Cl

CH2CN

CH2CONH2

(Ch : phn ng clometyl ha phenol cho sn phm ph l ng phn ortho-, cn tch loi) C th tng hp A theo cch khc nh sau: Trang 2/7

OH
OHC-COOH H
+

OH + HC-OH COOH Axit p-hiroximanelic

OH CH-OH COOH

Axit o-hiroximanelic

OH
[H]

OH
l. CH3OH/H+ 2.NH3(30%)

OH

HC-OH COOH

CH2-COOH

CH2CONH2 A

b. Tng hp B:
CH2=CH-CH3
Cl2, 500 C
o

CH2=CH-CH2Cl
OH

H2O2 hay RCO3H

Cl

O A+B NaOH +

O + CH2CONH2 E

Cl

O OH

CH2CONH2 D

CH2CONH2 CH2CONH2 G

c. Tng hp atenolol:
O CH2-CH CH2 O + D CH2CONH2 O CH2-CH-CH2-Cl OH + E CH2CONH2 H2N-CH-CH3 CH3 CH2CONH2 Atenolol H2N-CH-CH3 CH3 CH3 O CH2-CH-CH2-N-CH-CH3 OH H

2. Theo bi ra, ta c cc phn on sau: Val-Trp-Met-Gly-Lys Met-Gly-Lys-Ala-Ile-Pro-Met-Asp-Arg-Tyr Val-Trp Ala-Ile-Pro-Met-Asp-Arg Tyr-Ala-Gly-Cys Ala-Gly-Cys Trang 3/7

Da vo cc phn on trn, c th kt lun trnh t cc amino axit ca polypeptit A l: Val-Trp-Met-Gly-Lys-Ala-Ile-Pro-Met-Asp-Arg-Tyr-Ala-Gly-Cys Cu 3. (4 im). 1. (2,0 im); 2. (2,0 im). Ete crao v criptan l nhng hp cht vng c nhiu ng dng thc tin. 1. Ete crao c kh nng to phc chn lc vi kim loi kim. Ete [18]crao-6 (A) sinh ra trong phn ng Williamson thng thng (1) vi hiu sut (hs) rt thp:

HOCH2CH2[OCH2CH2]4OCH2CH2Cl

Wiliamson hs 2%

[OCH 2CH 2]6(A)

(CH3)3COK hs 99%

(1)
A (2)

Tri li, c th iu ch A vi hiu sut rt cao theo phn ng (2):

TsOCH2CH2OCH2CH2OCH2CH2OTs + HOCH2CH2OCH2CH2OCH2CH2OH

Gii thch s khc nhau v hiu sut ca hai phn ng. Trnh by c ch phn ng (2). 2. Criptan B c cng thc N(CH2CH2OCH2CH2OCH2CH2)3N. Dng cng thc cu trc, vit s cc phn ng tng hp B t 3,6-ioxaoctan-1,8-iamin, axit 3,6-ioxaoctanioic v cc ha cht cn thit. Hng dn gii: 1. Phn ng (1) theo c ch SN2 ni phn t, xy ra kh khn v hai trung tm phn ng rt xa nhau:
O SN2
-

O O A O

O O

Cl

-Cl-

Phn ng (2) theo c ch hai ln SN2. Ln th nht xy ra bnh thng; ln th hai rt thun li nh c s to phc vi ion K+ lm cho cc trung tm phn ng gn nhau hn:
OTs
-

O O O O O
K
+ -

O O O
-TsO
-

O O

O O OTs

K+
-

O O

K+ O

O O -K+ A

-TsO

OTs

2.
HOOC O O Cl COOH
SOCl2

Cl O O O

O NH2 Cl O O

O H 2N Cl O O
- 2HCl

O
NH O

O
HN
[H]

O
O NH

O
HN

O
NH

O
Cl HN + O Cl O O N

O O

O O O N
[H]

O O N

O N O B

O
O O O

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Cu 4. ( 4,5 im). 1. (1,0 im); 2. (1,0 im); 3. (1,5 im); 4. (1,0 im). Ancol X (C15H26O) c trong tinh du patchoulis, c th c tng hp nh sau: 1. Hp cht imetylxiclohexaien tc dng vi metyl vinyl xeton sinh ra hp cht A l sn phm chnh. Vit tn y ca imetylxiclohexaien dng v s phn ng to thnh A. Vit cng thc cu trc ca 3 sn phm ph l ng phn ca A.

2. Cho A tc dng vi hp cht c km (sinh ra t etyl bromoetanoat v km trong ete), sau thy phn sn phm trong dung dch axit long th thu c monoeste B (C16H26O3). B tc dng vi (CH3CO)2O sinh ra ieste C. Cht C b tch CH3COOH to thnh monoeste khng no lin hp D (C16H24O2). Vit cng thc cu trc ca B, C, D v cc sn phm ng phn ca D c th sinh ra cng vi D. 3. Hiro ha chn lc ni i ngoi vng ca D, thu c este E (C16H26O2). Kh E bng LiAlH4 cho ancol F. Cho F tc dng vi (C6H5)3CCl trong piriin, to thnh G (C33H38O). Hiro-bo ha G (dng B2H6 tip n H2O2/NaOH), sau oxi ha (CrO3/piriin), sinh ra xeton P. Cho P tc dng vi NaH ( sinh ra cacbanion) sau vi CH3I th c sn phm Q (C34H40O2). Vit cng thc cu trc ca E, F, G, P v Q cng vi s cc phn ng. 4. Trong mi trng axit, Q chuyn thnh R ng thi gii phng (C6H5)3COH. R tc dng vi TsCl sinh ra sn phm S. Cht S phn ng vi KI/axeton to thnh T (C15H25IO). T tham gia phn ng ng vng (nh Na/THF) cho ancol X. Dng cng thc cu trc, vit s cc phn ng v cho bit X cha bao nhiu nguyn t cacbon bt i. Hng dn gii: Ancol X (C15H26O) c trong tinh du patchoulis, c th c tng hp nh sau: 1.

O O

1,3-imetylxiclohexa-1,3-ien

Metyl vinyl xeton

Cng thc cu trc ca 3 trong s cc sn phm ph l ng phn ca A:

O
O

O
2.
BrCH2COOEt
Zn Ete

BrZnCH2COOEt
Ac2O

1. BrZnCH2COOEt 2.H3O
+

OAc OH B COOEt C COOEt

-AcOH

OEt
(E)

Cc sn phm ng phn ca D c th sinh ra cng vi D l: Trang 5/7

(Z)

O
(Z)

(E)

OEt O

OEt

O OEt

EtO

3.

H2/Pd

OEt E HO O

LiAlH4

Ph3CCl Piridin

F O
CrO3/piridin

OH

OCPh3 G

1. B2H6 2. H2O2/HO-

OCPh3 O
CH3I

OCPh3

NaH

OCPh3

OCPh3

4.
Q
H
+

TsCl

KI/axeton

Na/THF

HO

- Ph3COH OH R S OTs T
Ancol X

Ancol X cha 5 C* Cu 5. (3,5 im). 1. (1,5 im); 2. (2,0 im). 1. Urani dng lm nguyn liu cho l phn ng ht nhn. tinh ch urani, ngi ta ha tan mui uranyl nitrat UO2(NO3)2 (k hiu UN) vo trong nc, sau chit nhiu ln vi tributyl photphat (TBP) pha long trong du ha. Bit rng TBP l cht lng kh bay hi. 25 oC, TBP c khi lng ring l 972,7 kg/m3, cn du ha c khi lng ring trong khong t 780 - 810 kg/m3. V sao ngi ta phi chit UN bng TBP pha long trong du ha m khng chit bng TBP nguyn cht? 2. Hy tm s ln chit thch hp c th chit c trn 95% UN cha trong 90 ml nc, s dng 90 ml TBP. [UN]hc Cho: KD = = 6; trong KD l hng s phn b, [UN]hc v [UN]nc ln lt l nng [UN]nc cn bng (mol/L) ca UN trong pha hu c v pha nc. Hng dn gii: 1. TBP c khi lng ring 972,7 kg/m3 gn bng khi lng ring ca dung dch nc cha uranyl nitrat. Nu chit bng TBP nguyn cht, s tch pha hu c v pha nc s kh khn. S pha long pha hu c bng du ha c khi lng ring nm trong khong t 780 kg/m3 n 810kg/m3 lm cho khi lng ring ca pha hu c gim i, s phn pha trong khi chit tr nn d dng hn.

Trang 6/7

2. Gi s ngi ta tin hnh chit UN n ln bng nhng lng dung mi hu c bng nhau. Gi Vnc l th tch ca pha nc (ml). Vhc l tng th tch ca pha hu c (ml). xo l hm lng ban u ca UN trong pha nc (mmol). xi (i = 1, 2,...n) l hm lng cn li ca UN trong pha nc sau ln chit th i (mmol). Khi : th tch pha hu c s dng trong mi ln chit s l Vhc/n. ( xo x1 )n Vhc 1 Sau ln chit th nht, ta c : KD = . Rt ra: x1 = xo. V x1 1 + K D hc Vnc nVnc . 1 Theo bi ra, Vhc=Vnc (= 90 ml), v vy x1 = x0. K 1+ D n 2 n 1 1 1 Sau ln chit th 2: x2 = x1. = xo. . Tng t, sau ln chit th n: xn = xo. . K 1+ KD 1+ KD 1+ D n n n n 1 xn Vy % UN cn li trong pha nc sau ln chit th n l: .100 = .100 xo 1+ KD n chit c hn 95% UN vo pha hu c th % UN cn li trong pha nc phi nh hn 5%, ngha n 1 l: < 0,05. 1+ KD n Lp bng bin thin [1/(1+KD/n)]n theo n ( y KD = 6), ta c: n [1/(1+KD/n)]n 1 0,1428 2 0,0625 3 0,0370

T s liu bng trn, nhn thy: t sau ln chit th 3, hm lng UN cn li trong nc nh hn 5%. Kt lun: chit c trn 95% UN vo pha hu c, ngi ta c th chia 90 ml dung mi hu c thnh 3 phn bng nhau v tin hnh chit lm 3 ln .
--------------------------HT-----------------------

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