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.
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
O

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-MetAsp-Arg, Tyr-Ala-Gly-Cys. Nu dng xc tc chymotrypsin th thu c: Ala-Gly-Cys, Met-Gly-Lys-Ala-IlePro-Met-Asp-Arg-Tyr, Val-Trp.
Hy xc nh trnh t cc amino axit trong A.
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%

[OCH2CH 2]6 (A)

(1)

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

TsOCH2CH2OCH2CH2OCH2CH2OTs + HOCH2CH2OCH2CH2OCH2CH2OH

(CH3)3COK
hs 99%

A (2)

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.
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.
O
Vit cng thc cu trc ca 3 sn phm ph l ng phn ca A.
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.

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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.
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 cn bng
[UN]nc
(mol/L) ca UN trong pha hu c v pha nc.
--------------------------HT-----------------------

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