TRNG THPT CHUYN THNG LONG LP 12 HA

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K THI HC SINH GII QUC GIA LP 12 THPT NM HC 2008 2009

MN THI: HA HC HA HC HU C Thi gian lm bi: 180 pht (Khng k thi gian pht ) H v tn th sinh:........................................................................................................ S bo danh:................................................................................................................. ( thi gm c 2 trang) Cu 1: (3.0 im) Di y l chui chuyn ha c lin quan n mt s cht hu c Sn,HCl HCl A B C
KMnO 4 NaOH,H2 O D E F NaNO 2 ,HCl NaOH,t G H I Cc cht A, E v I l nhng ng phn, cng nh B v C. Cc cht C, F v G l nhng mui. Cht F cha 15,85% Natri theo khi lng. C th to c cht E bng cch oxi ha mt s ankaloid t nhin 1. Vit tn v cng thc cu to ca cc cht A, B, C, D, E, F, G, H ,I 2. Cht E c to ra t ankaloid no 3. Nhng phn ng chuyn ha no c xc tc bi cc dn xut ca E. Gii thch ngn gn 4. Vit cng thc cu to ca cc cht thu c khi B tc dng ln lt vi axit HNO2 v vi cht H Cu 2: (2.0 im) Mt axit cacboxylic A c cng thc nguyn l C5H8O2. Hp cht ny tn ti 2 dng ng phn lp th l A1 v A2. gii thch cu trc ca hai ng phn trn, ngi ta x l A vi ozon. Sau phn ng thu c axetanehit v axit 2-oxipropanoic. Khi hiro ha A1 v A2 bng hiro (trn thanh tip xc Platin) s sinh ra hn hp raxemic ca axit cacboxylic B. 1. Vit CTCT cc ng phn hnh hc ca A1 v A2, gi tn 2. Vit cng thc chiu Fischer cc ng phn ca B v gi tn theo danh php Cahn-Jugold-Prelog v cho bit hng quay (+ hoc ) ca cc ng phn 3. Vit phng trnh phn ng ca A1 v A2 vi Brom (dng cng thc hnh chiu Sge-bock). M t c ch ca phn ng v cho bit trong cc sn phm , sn phm no c ng phn lp th i quang Cu 3: (1.5 im) 1. Hy ch ra c ch phn ng v sn phm cui ca phn ng cng Brom (1 : 1) vi nhng cht sau: a. Axit maleic (1) b. Axit fumaric (2) c. But-2-in (3)
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H 3C C C CH3 (1) (2) (3) 2. Hy gi tn sn phm cui ca 3 phn ng trn theo danh php IUPAC, R/S, E/Z Cu 4: (1.5 im) Qu trnh tng hp aminoaxit nh sau: NH3 H 2O H2O / H + H2 O / H + CN / H + CH 3CHO A [B] C D E ( aminoaxit) 1. Vit cng thc cu to ca cc sn phm t A E 2. Vit cng thc chiu Fischer v gi tn aminoaxit E Cu 5: (2.0 im) Mt dn xut ca cc azoankan c dng lm cht khi mo cho phn ng trng hp v chng l ngun cung cp cc gc t do. 1,1-ixiano-1,1-imetylazometan (X) c tng hp nh sau: N 2 H4 Cl2 +H 2 O Y axeton A B X . Bit cht A c mt nhm OH, cht B khng cha oxi 1. Nu r vai tr ca Cl2 + H2O 2. Vit cng thc cu to ca Y v gi tn. Xc nh CTCT ca A v B 3. Vit phng trnh phn ng phn hy (dng CTCT) ca X nu to ra 2 gc t do v cho thot ra kh X (bit X c t khi hi vi oxi l 0,875). Cu 6: (1.0 im)
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Xc nh cc cht A, B, C, D trong 2 s sau v vit cng thc cu to ca chng 1.C2 H5ONa NaOH / H 2O, HCl, (a) C 2 H5 OCO CH2 COOC2 H5 A(C7 H10 O4 ) B C(C4 H6 O2 ) 2.Epoxit
3 2 2 2 2 2 4 (b) Anilin A B C D 2.H3PO2 1. Trong s (a), cho bit A c my ng phn 2. Trong s (b), gi tn C, D theo danh php IUPAC Cu 7: (2.5 im) Xiprofloxaxin (G) l mt thuc khng khun mi c ph rng. Tin trnh tng hp n l:

(CH CO) O

Cl

NaOH,H O

1.HNO /H SO

AlCl3 (C2 H5 O)3 CH NaH C8 H5Cl2 FO( A) C11 H9 Cl2 FO3 (B) (C) CH 3COCl (C2 H5 )2 CO3 C2 H5 ONa

xiclopropyla min (C) ( D)C15 H14 Cl2 FNO3 (E)C15 H13 ClFNO3

(E) (F )C13 H9 ClFNO3 (G ) 1. Xc nh CTCT cc cht A, B, D, E, F 2. Ti sao phi dng NaH bin i A thnh B nhng li dng C2H5ONa chuyn B thnh C 3. Qu trnh bin i C thnh D l mt giai on hay hai giai on. Gii thch ngn gn Cu 8: (1.5 im) Qun ty c th l (i) rt tt k c khi b ma v khng li vt st l nh kh nng bo v ca hp cht hu c X. Ngi ta c th tng hp X theo s sau: mui Na ca este malonic Cl2 / P C2 H 5OH / H + Br2 / CCl4 CH3COOH A B C(C11 H18 O6 ) D
Na / C 2 H 5OH C E ; E + D F (C22 H34 O12 ) 1. Xc nh cc cht t A F 2. Ti sao X li gi c np l (i) trn qun Cu 9: (2.0 im) 1. Somatostatin l tetraecapeptit. Trt t cc aminoaxit c xc nh bi s kt hp gia thoi bin Edman v thc nghim thy phn enzim. Da trn cc d kin sau y hy a ra cu trc bc I ca Somatostatin: - Thoi bin Edman cho PTH-Ala - Thy phn chn lc c cc peptit sau: Phe-Trp, Thr-Ser-Cys, Lys-Thr-Phe, Thr-Phe-Thr-Ser-Cys, Asn-Phe-Phe-Trp-Lys, Ala-Gly-Cys-Lys-Asn-Phe - Somotostatin c cu ni isunfua 2. Tng hp Prolin t axit aipic Cu 10: (3.0 im) 1. Arabinopyranoz (D-anopentoz c cu hnh 2S, 3R, 4R) c chuyn ha nh sau:

Ara (C5H10O5)

CH3OH/H

HIO4

1. LiAlH4 2. H2O Br2/H2O

D E

H2O/H H2O/H

HOCH2-CHO + HOCH2-CH2OH CHO-COOH + HOCH2-COOH

V cu trc ca B, C, D v E 2. Thy phn isaccarit c tnh kh turanoz ngi ta thu c D-glucoz v D-fructoz vi s mol bng nhau v bng s mol turanoz dng. Metyl ha turanoz vi metyl iodua c mt bc oxit ri thy phn k tip to thnh 2,3,4,6-tetra-O-metyl-D-fructoz. xut cu to c th c ca turanoz m khng cn xc nh ha hc lp th ti cc v tr anome 3. T pentoz hy vit s chuyn ha thnh axit aipic (qua giai on to thnh fufural) - - - - - - - - - - - - - Ht - - - - - - - - - - - - -

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