b gio dc v o to nm 2002

k thi chn i tuyn quc gia d thi olympic ho hc Quc t

thi gian giao )

Thi gian : 180 pht (khng k Ngy thi : 4 / 5 / 2002

Cu I: Axit fumaric (F), axit maleic (M) v axit squaric (S) c cng thc cu to v pKa nh sau: OH OH OH OH OH

(F) OH (M) (S) pKa: 3,0 ; 4,6 1,9 ; 6,2 1,7 ; 3,2 1. Gi tn F, M v S theo danh php h thng IUPAC. 2. Gii thch ti sao pK1 ca M nh hn pK1 ca F, cn pK2 ca M li ln hn pK2 ca F. 3. Gii thch ti sao pK1 ca S nh tng ng pK1 ca M, pK2 ca S cn nh hn nhiu so vi pK2 ca M. Cu II: un nng Dglixeranehit hoc ihiroxiaxeton (1,3ihiroxipropan2on) vi baz sinh ra hn hp cc ng phn lp th ca 1,3,4,5,6pentahiroxihexan 2on v 1,3,4,5tetrahiroxi4(hiroximetyl)pentan2on. Vit s cc phng trnh phn ng v cng thc Fis ca cc sn phm. Cu III: T pinen iu ch c tecpin v cc tecpineol theo s :
H2SO4 long, to H 3PO4 long, to

C10H18O

C10H20O2

(Pinen) (Tecpin ) (Tecpineol) Tecpin v cc tecpineol u l cc hp cht c b khung cacbon ca pmentan (1metyl4isopropylxiclohexan). 1. Vit s cc phng trnh phn ng (dng cng thc cu to). 2. Gi tn theo IUPAC v vit cu dng bn nht ca tecpin. Cu IV:
1

Erythromixin l mt loi thuc khng sinh c cng thc cu trc nh sau: CH3 OH CH 3 OH OR R: OR CH3 CH 3 (CH 3)2N OH CH3 H HO CH3 OCH 3 H3C H CH3 R: CH3 HO CH3 1. Phn t erythromixin cha bao nhiu nguyn t C ? Trong phn t c nhng nhm chc g? 2. un nng nh erythromixin vi dung dch axit long (d) phn ng xy ra hon ton. Hy vit cng thc cu to ca cc sn phm. 3. Vit cng thc vng phng v cng thc Fis ca hai trong s cc sn phm sinh ra trn. Cu V: Triglixerit X l mt cht lng quang hot. Khi ozon phn X (dng O3, Zn...) thu c mt s hp cht cacbonyl, trong ch c mt cht duy nht thuc dy ng ng ca fomanehit l nhexanal. Thu phn hon ton X ch thu c hai axit bo l axit linoleic (C17H31COOH) v axit arachionic (C19H31COOH) vi t l mol 2:1. 1. Xc nh cng thc cu trc khng gian v gi tn IUPAC ca hai axit trn, bit rng cc nhm CH=CH trong phn t ca chng u cch nhau mt nhm CH2 v u c cu hnh Z. 2. Vit cng thc cu trc khng gian ca X, gi thit rng X c cu hnh R. 3. Hiro ho hon ton X thu c triglixerit Y. Vit cng thc cu trc khng gian ca Y. So snh Y vi X v nhit nng chy v gii thch. Cu VI: Ancaloit A (C20H21NO4) c dng lm thuc gin c. Mt mol A tc dng vi mt lng d axit iothiric sinh ra 4 mol metyl ioua. Oxi ho A bng kali pemanganat thot tin sinh ra xeton B (C20H19NO5); xeton ny b oxi ho tip na cho mt hn hp sn phm, trong s c cc axit sau:
2

COOH HOOC HOOC OCH3 OCH3 (H) ( E)

N

CH3O CH 3O COOH ( F)
N

CH3O CH 3O

COOH COOH COOH ( G)

1. Hy xc nh cng thc cu to ca A v B. 2. Gi tn A, B, E, F, G, H ; bit tn ca cc d vng: Piriin: N

2 4 3 2 5 4 3 7

Isoquinolin: N
1

3. T E c th tng hp c cc dc phm P v Q theo s : P Q E M

(C6H5NO2) (C6H4ClNO) (C2H5)2NH tO NH3 SOCl2

Hy vit cng thc cu to ca M, N, P, Q v so snh nhit nng chy ca M, P, Q. ...................................................