P N PHN HU C BNG A OLYMPIC HA HC CC TRNG I HC VIT NAM NM 2004 Cu I: 1) Cng thc cu to cc cht l: A: H3C

H C CH3 H C OH H C OH COOH CN H C CH3

B: H3C

H C NH2 H C N

CN O C O C CH3

C: H3C

H C CH3

D: H3C

H C CH3

2) Cng thc cu to cc sn phm: a)

Cl

3-cloxiclopenten b) CH3CH2CHBrCH=CH2 (3-brompent-1-en) + CH3CH2CH=CHCH2Br (1-brompent-2-en) c) CH2=CH-CH=CH-CHBr-CHBr: (5,6-dibromhexa-1,3-dien) CH2=CH-CHBr-CH=CH-CH2Br: (3,6-dibromhexa-1,4-dien) BrCH2-CH=CH-CH=CH-CH2Br: (1,6-dibromhexa-2,4-dien) d)
CH2OCH3

CH2 OCH3

CH3

1-(metoximetyl)-2-metylxiclopenten Cu II: 1) A phi l diamit nn c th vit nh sau:

CONH2

1-metoxi-1-metyl-2-metylenxiclopentan

CH3

C6H12N2O2

C4 H 8
CONH2

Br2; OHH2 O

NH2

C4H8
NH2

D D l diamin, deamin ha khi phn ng vi HNO2 v chuyn v ging nh pinacolin. Nh vy c th vit nh sau:

H3C

H C NH2

H C NH2

CH3

HNO2

H3C

H C OH

H C OH

CH3

H+ -H2O

CH3COCH2CH3

2,3-diaminobutan Nh vy hp cht A l diamit ca axit 2,3-dimetylsucxinic c th tn ti dng quang hot, phn ng vi axit nitr cho ra axit 2,3-dimetylsucxinic.
CH3 H H2NOC CH3 CONH2 H H HOOC CH3 CH3 COOH H CH3 O C O H3C C C H O

HNO2

toC -H2O

H3C

anhydrit-2,3-dimetyl sucxinic

2) Cng thc Fis:

CH3 H H2NOC CH3 CONH2 H H2NOC H CH3 CH3 H CONH2

Cu III: 1) a) A:

2CH 4 1500 C2 H 2 + 3H 2 HCl CH 2 = CH Cl C dpmn NaCl + H2O Cl2 + H 2 2 HCl

o o

B: CH 2 = CH 2 Cl 2 ;500 ClCH 2CH 2Cl 500 CH 2 = CH Cl C C b) Phng php B cn phi x l HCl thu Cl2 v trnh nhim. o 1 ; xt 2 HCl + O2 t Cl2 + H 2O 2 Chn phng php B v phn ng (1) ca phn ng A hiu sut thp, tiu tn nhiu nng lng v ga thnh sn phm s cao hn. c) C nguyn t C bt i:
H C C H2 CH2 CH2 Cl Cl H Cl H CH2 Cl CH2

2) Qa trnh tng hp nh sau:

CH3 O2N CH3 NO2 O2 N COOH NO2

HNO3 H2SO4

KMnO4

1)Sn + HCl 2) OH-

NO2 COOH H2N NH2 HN COOH NH

NO2 COOH O O

+H2O

NH2

NH

HO

OH

-CO2

OH

3) Qa trnh tng hp nh sau:

CH2COOH H2C H2C CH2COOH CH2NH2 CH2NH3+

H2SO4 HN3

H2C H2C C H2 COOH

H+ P, Br2

H2C H2C CH Br COOH

(A) OHNH

(B)

COOH

hoc: HOOC (CH ) COOH 2 ) NH 3 H NCO (CH ) COOH Br2 / A ri tip tc nh trn KOH 2 4 2 2 4

1) SOCl 2

4) Qa trnh tng hp nh sau:

COOH CO (CH2)2 COOH COOH CN C NH2 (CH2)2 COOH COOH COOH C -CO2 NH2 to (CH2)2 COOH COOH CHNH2 CH2 CH2 COOH

HCN NH3

H3O+

Cu IV: 1) a) CH2 = CHCH2OH + HOCl CH2Cl C*HOH CH2OH (A): hn hp raxemic. CH2 = CHCH2Cl + HOCl CH2Cl CHOH CH2Cl (B): khng quang hot b) H ca nhm OH gia linh ng hn v chu hiu ng I mnh hn. c) Do E khng hp th vng 1500 1800cm-1 chng t chng khng cha lin kt C=C v C=O suy ra chng c cu to vng. D c vn mng 3100 3400cm-1 cha nhm OH, E th khng. So snh thnh phn A vi D, B vi E thy u gim + HCl v ch ha vi NaOH to ra glixerol (qa th) nn y l iu kin cho phn ng th ch khng pho l cho phn ng tch HCl (cn iu kin phn cc v un nng). Nh vy chng c cng thc cu to: * * H2C CHCH2OH H C CHCH Cl
2 2

D d) C ch ca cc phn ng nh sau:
H2C Cl H2C Cl H C OH H C OH CH2Cl CH2OH

E
Cl H2 C H C OCl H2 C H C OCH2Cl CH2OH

OH-H2O OH
-

-Cl-

H2C O

H C

CH2OH

raxemic -Cl
-

H2C O

H C

CH2Cl

-H2O

raxemic 2) A, B, C khng lm mt mu dung dch brom khng cha lin kt bi m cha vng no. A c 4 CIII, 6 CII; B v C c 2CIII v 8CII. Cng thc cu to ca chng:

A Cng thc lp th:

B, C

B A tonc: A > B > C v tnh gn gng gim theo chiu