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KIM TRA S 1

K THI HC SINH GII QUC GIA LP 12 THPT

HNG DN CHM THI TH MN HA HC HU C

Cu 1: (3.0 im) Di y l chui chuyn ha c lin quan n mt s cht hu c A B C ; D 4 E N aNO ,H Cl 2 I
S n ,H Cl H Cl K Mn O N aOH

2 F ; G

o ,H

aOH

,t

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 BI GII: 1. Cc chui chuyn ha l: NO2 NH2 NH3Cl CH3 COOH
N N COONa N N SO3Na OH N OH O N N

2. C th to acid nicotinic (cht E) bng cch oxy ha nicotin N N 3. CH3 [O] N COOH

Cc dn xut c bit ca acid nicotinic u lm xc tc cho cc qu trnh oxi ha v kh c bit l cho vic chuyn i ion hidrua gia cc phn t 4. Cho anilin (B) tc dng ln lt vi acid nitro v phenol (H) ta c cht mu azo N N OH 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 HNG DN CHM THI TH MN HA HC 1

ch ca phn ng v cho bit trong cc sn phm , sn phm no c ng phn lp th i quang

HNG DN CHM THI TH MN HA HC

BI GII: 1. Xc nh ng phn A1, A2 CH3 C H C CH3 COOH (A1 cng nh A2) H C CH 3 C COOH CH3

Acid cis-2-metyl-but-2-enoic Acid trans-2-metyl-but-2-enoic 2. Vit cng thc chiu Fischer cc ng phn ca B. Khi hidro ha A1 v A2 th u cho acid carbocylic B nh nhau c cha mt trung tm chiral (hp cht m nh ca n qua gng phng khng trng kht c vi hnh ca n) bt i. Do chng l hn hp racemic COOH COOH CH3 H C 2H 5 Acid (S)-2-metylbuatnoic H CH3 C 2H 5 acid (R)-2-metylbutanoic

Hng ca gc quay quang hc khng th suy ra t cu hnh tuyt i 3. Phn ng cng Brom hnh thnh qua 2 trung tm chiral bt i mi. Br H3C CH3 COOH H 3C H + Br2 COOH CH3 H

Br Acid (2S,3R)-2,3-dibrommetylbutan-2-oic H 3C Br CH3 Br COOH

H Acid (2R,3S)-2,3-dibrommetylbutan-2-oic Br H3C CH3 COOH H CH 3 + Br2 H COOH CH3

Br Acid (2S,3S)-2,3-dibrommetylbutan-2-oic H 3C Br H Br COOH

CH3 Acid (2R,3R)-2,3-dibrommetylbutan-2-oic N thuc loi phn ng lp th chn lc: Cng hp trans giai on u tin to thnh mt ion brom v n tn cng vo pha sau to thnh sn phm mi.

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)

H 3C C C CH 3 (1) (2) (3) 2. Hy gi tn sn phm cui ca 3 phn ng trn theo danh php IUPAC, R/S, E/Z BI GII: 1. a. H H COOH COOH + Br Br H COOH Br H COOH a)

b) Br

To thnh mt hn hp racemic COOH a) H Br H Br H b) H Br COOH acid (2R,3R)-2,3-dibrombutandioc COOH Br COOH acid (2R,3R)-2,3-dibrombutandioc

b. Axit fumaric (2) H HOOC H

-

H COOH + Br Br HOOC H Br COOH

C 4 cch tn cng ca ion Br nh u cho chung 1 sn phm l acid (2R, 3S)- 2,3-dibrombutanoic c. Sn phm l E-2,3-dibrombut-2-en H3C C C CH3 Br C C Br H 3C Br C C CH3 Br

H3C

CH3

Br Br

Cu 4: (1.5 im) Qu trnh tng hp aminoaxit nh sau:

NH3 H2O / H H2O / H /H H2O CH 3CHO A [BCN ] 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 BI GII: OH NH3 - H2O CH3CHO H3C C NH2 [H 3C CH H CONH2 H3C C NH2 H H 2O H+ CONH2 H3C C H E l alanin NH2

NH]

CN H
+

CN H3C C H NH2

H 2O H
+

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: axeton A 2 4 B 2 2 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). BI GII: 1. Phn ng Cl2 + H2O HClO + HCl to HclO l cht oxi ha 2. Cht Y l hidro cyanur HCN CH3 CH3 H 3C C CN OH A 3. Ta c: MX = 32.0,875 = 28 g/mol nn X l N2 CH3 CH3 CH3 C N N CN C CN CH3 CH3 C NH CN B CH3 CH3 C CN + N2 NH
Y N H C l + H O

CH3 C CH3 CN

Cu 6: (1.0 im) Xc nh cc cht A, B, C, D trong 2 s sau v vit cng thc cu to ca chng (a) C H OCO CH COOC H 2 5 2 2 5 2.Epoxit (b) Anilin (CH CO ) O 3 2
C l 1.C 2 H5 ONa H 2 O,

A(C 7 H10O 4 )(C H O ) B C

aOH

NaOH /

HCl,

A 2 B

C 2 2.H 3 PO 2

,H

.HN

O 2 /H

2 4 D

SO

Cu 4: (1.5 im) 1. Trong s (a), cho bit A c my ng phn 2. Trong s (b), gi tn C, D theo danh php IUPAC

BI GII: 1. A c 2 ng phn. A, B, C l: COOCH2CH3 O COOH O O

O 2.

O NH2 Cl

C l 2,4-dicloanilin ; D l 1,3-diclobenzen NHCOCH3 NHCOCH3 Cl

Cl

Cl

Cl

Cl

Cu 7: (2.5 im) Xiprofloxaxin (G) l mt thuc khng khun mi c ph rng. Tin trnh tng hp n l:
N a H C H Cl FO()C A Cl F H O ()() 8 5 2 CH 3COCl (C2 H5 )CO 2 3 AlC l3

11

B C H

C 2H

O5 Na

5O

)C

C
3

(C)
m in

iclo

prop

yla

15

()DC H

C14l F2NO

()CE H 15Cl1F3 NO

(E) ()FC H13 C9 lFNO

() 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 BI GII: 1. Xc nh CTCT cc cht A, B, D, E, F O F Cl C CH3 Cl F Cl O C Cl O COOC2H5 NH F Cl N COOC2H5 F Cl N O C Cl COOC2H5 OC2H5 O COOH

O F Cl C Cl

HNG DN CHM THI TH MN HA HC

2.

Gii thch: - Tnh acid ca A yu hn nn phi dng NaH - Tnh acid ca B mnh hn nn c th dng EtONa

HNG DN CHM THI TH MN HA HC

3.

Qua 1 giai on to cht trung gian trc khi to D => phn ng 2 giai on O F C COOC2H5 H 2N F O C Cl Cl C 2H 5O NH COOC2H5

Cl

Cl

OC 2H5 O

C Cl

COOC2H5 NH

Cl

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: CH 3COOH 2 A 2 5 C 2 H5 OH E
N a/C C l / P C
+

OH

mui Na ca este malonic /H

B C(C H O ) 2 11 18 6

r /

CCl 4

; E + D

F (C 22 H 34O12 )

1. Xc nh cc cht t A F 2. Ti sao X li gi c np l (i) trn qun 1. Xc nh cc cht t A F BI GII:

A l acid cloacetic - E l dn xut Natri ca C B l etyl este ca acid cloacetic - F l etyl este ca acid enanhexacarbonic C l etyl este ca acid enantricarbonic - X l acid butantetracarbonic D l etyl este ca acid 2-brom-2carbocylbutandiol 2. X tham gia phn ng ngng t vi cellulose v to ra nhiu cu gia cc si vi. 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 BI GII: 1. Thoi bin Edman cho PTH-Ala => u N l Ala, khi thy phn tng phn cho hexapeptide Ala-Gly-Cys-Lys-Asn-Phe Dng cht ny lm xut pht im kho st s ni tip cc aminoacid Ala-Gly-Cys-Lys-Asn-Phe Asn-Phe-Phe-Trp-Lys Phe-Trp Lys-Thr-Phe Thr-Phe-Thr-Ser-Cys 6 HNG DN CHM THI TH MN HA HC

Thr-Ser-Cys

HNG DN CHM THI TH MN HA HC

Ngha l: Ala-Gly-Cys-Lys-Asn-Phe-Phe-Trp-Lys-Thr-Phe-Thr-Ser-Cys 1 2 3 4 5 6 7 8 9 10 11 12 13 14 Cu disulfur trong somotostatin nm gia Cys 3 v cys 14. Vy cu trc bc 1 ca somotostatin l: Lys-Asn-Phe-Phe-Trp-Lys Ala-Gly-Cys S-S-Cys-Ser-Thr-Phe-Thr 2. S tng hp CH2COOH CH 2COOH HN3 H2SO4 CH2NH2 CH2COOH
1)SOCl 2 2 )NH

P, Br2 H+

CH2NH3 CHBrCOOH

OH

NH COOH

hoc: HOOC(CH 2 )C4 OOH

3 2 H NCO(CH ) 2 4 COOH

2 A
KOH

r /

ri tip tc nh trn

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

HOCH2-CHO + HOCH2-CH2OH CH O-COOH + HOCH2-COOH

H2O/H+

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) BI GII: 1. Arabinopyranoz (D-anopentoz c cu hnh 2S, 3R, 4R) c chuyn ha nh sau:
CHO
CH3OH/H+

O OMe

HIO4

CHO CHO

OMe

CH2OH Ara
1. LiAlH4 2. H2O

B
O HOH2C OMe HO H2C O HOOC OMe HOOC
H3O+ H3O+

CH 2OH-CH 2OH + CH2 OH-CHO

Br2/H2O

CH2OH-COOH

+ CHO-COOH

2. Turanose l -D-glucopyranosyl-(13)--D-fructofuranose HNG DN CHM THI TH MN HA HC 7

3. T pentose hy vit s chuyn ha thnh axit adipic (qua giai on to thnh fufural)

HNG DN CHM THI TH MN HA HC

HO

OH CHO -2 OH2 OH HO CHO OH2 O CHO KMnO4 O COOH

OH HO

Hidro xt

HCl

Cl Cl

1. KCN 2. H3O+

CO2

COOH COOH

- - - - - - - - - - - - - Ht - - - - - - - - - - - - -

HNG DN CHM THI TH MN HA HC