TRAO I V MT VI VN TRONG THI CHN HC SINH GII QUC GIA MN HO HC LP 12 THPT NM 2010

Phm Hng Hi, Gio vin trng THPT Chuyn i hc S phm H ni

I. t vn Trong cc nm trc y thi chn hc sinh gii quc gia mn ho hc lp 12 THPT nhn chung c th coi l nhng thi hay, tng i chun xc v mt khoa hc v mt s phm, tip cn c cc vn hin i ca ho hc, c tnh thi s (nh bi v melamin, amigdalin, iu ch cc loi thuc), c kh nng phn loi hc sinh, c ni dung nng cao trn c s khung chng trnh chuyn. Tuy nhin trong thi mt vi nm gn y, phn ho hu c c mt s cu thiu chun xc, khng r rng, khng c gii hn dn ti v s li gii. Hn th phn hng dn gii (coi nh l p n) thng c nhng li gii hoc p t, hoc lm ln thiu c s l thuyt v thc t. Nhng sai st v thi v p n khng nhng gy hoang mang cho hc sinh, gy kh khn cho vic chn hc sinh gii ca k thi m cn gy tc ng tiu cc lu di cho qu trnh dy v hc. Vi mong mun rng cc thi s chun xc hn, hay hn, c tc ng tch cc cho vic hc tp v ging dy i vi hc sinh v gio vin THPT, trong bi bo ny chng ti trnh by kin ca mnh v mt vi cu trong thi chn hc sinh gii quc gia mn ho hc lp 12 THPT nm 2010. II. Ni dung Cu 7.1a: thi chn hc sinh gii quc gia mn ho hc lp 12 THPT nm 2010 c ni dung sau: Vit cng thc ca sn phm to thnh t cc phn ng sau:
O CHCl2

OH?

Mi hc sinh u hiu rng chiu hng ca mt phn ng hu c khng nhng ph thuc vo bn cht ca cc cht tham gia m cn ph thuc vo iu kin tin hnh phn ng (nhit , dung mi, nng ) [1, 4, 5, 6]. V cu ny khng cho bit OH- ly t hp cht no (KOH, NaOH, dd NH3, [Ag(NH3)2]OH.), dng no (rn hay dung dch? c hay long?), lng dng l bao nhiu (dng vi lng xc tc hay vi t l mol 1:1; 1:2; ?), dung mi cho phn ng l g (nc, ancol hay ancol-nc ?), nhit

tin hnh hnh phn ng th no? nn theo thng l ngi ta phi hiu l nhng iu kin bnh thng, tc l: dng dung dch nc ca NaOH hoc KOH, nng khng cao, nhit phng. Trn c s kin thc v phn ng ca cc cht hu c, hc sinh s tr li cu hi ny theo cc hng sau: 1. V hp cht cho thuc loi dn xut halogen c kh nng phn ng cao [5] nn d dng xy ra phn ng th ngay nhit thng vi dung dch kim long sau sn phm to ra khng bn nn b tch HCl to thnh anehit.
O CHCl2 OH-Cl(A) O CH OH Cl -HCl (B) O CHO

Hoc cng c th:

O CHCl2 OHO CH(OH)2 -H2O (A) (B) O CHO

to ra c cht B trn th phi tiu tn t nht 1 mol OH- cho 1 mol A. 2. Hp cht A l mt xeton c H linh ng nn ch cn mt lng nh OH- lm xc tc, ngay nhit phng cng gy ra phn ng kiu andol ho:
C6H5 C CHCl2 C6 H5 -H2O O OHCl O C6H5COCHCl 2 C CCl2 C6H5 C C C CHCl2 O O Cl C6H5 (C)

H2O -OHCl OH C6H5 C C C CHCl2 (D) O Cl C6H5

3. C v D u c th xy ra phn ng th ni phn t (SNi) [5] nh sau:

Cl O C6H5 C C C CHCl2 -Cl-ClO Cl C6H5

O C6H5 C C O Cl (E) C CHCl2 C6H5

Cl O CHCl C6H5 C C C O Cl C6H5 (F)

(C)

Phn ng SNi tng t nh cc phn ng to ra E v F xy ra kh d dng v c nu ra trong nhiu ti liu [2, 4, 5, 7, 8, 9, 10] v cng l d hiu i vi hc sinh. 4. Cc nguyn t clo D, E, F u d dng b thu phn ri tch HCl to ra nhiu sn phm, th d:
2

OH C6H5 C C C CHCl2 O O C6H5 (G)

O C6H5 C C C CHO O Cl C 6 H5 (H)

Cl C6H5 C C O Cl

OH C CHO C6H5 (I)

5. Hp cht D cn c th b tch nc (E1cb) tng t nh giai on tch nc phn ng ngng t croton to ra hp cht K, nu tip tc b thu phn th cho hp cht L:
Cl OH C6H5 C C C CHCl2 O Cl C6H5 (D) Cl OHC6H5 C C C CCl2 -HCl -H2O O Cl C6H5 OH(K) C6H5 C C O O (L) C CCl2 C6H5

Nm hng trn u d dng xy ra trong iu kin bnh thng v cng ph hp vi t duy logic ca hc sinh gii v ca mi ngi c kin thc v ho hu c. Vi cu hi:
O CHCl2 OH?

Hc sinh khng hiu ngi ra bt hc sinh phi phn tch c 5 hng phn ng nu trn hay ch cn nu ra mt hng l ? Hc sinh v gio vin nh phi i khi c hng dn chm thi chnh thc mn ho hc ca B V y l p n ca B:
O CHCl2 OHOH COO-

hiu c p n ny hc sinh phi c hc phn ng Cannizaro. l phn ng ca mt s anehit khng c H khi b un nng trong dung dch NaOH hoc KOH m c (nng khong 50%) [3, 4, 10, 11] th d:
2 CH2O OHt
o

HCOO- + CH3OH KOH 50% to m-BrC6H4COOH + m-BrC6H4CH2OH

2 m-BrC6H4CH=O

C ch ca phn ng ny l kh i vi nhiu hc sinh, tuy vy mt hc sinh gii khi c nhiu cng c th bit c rng phn ng Cannizaro t hai phn t anehit khng c H di tc dng ca kim c v un nng to ra mt phn t axit v mt phn t ancol tng ng. Nu u bi cho thm yu t nng v un nng, chng hn: Hy vit sn phm ca phn ng sau:
3

C6H5-CO-CH=O

NaOH ~50%

to

Th mt hc sinh gii bit v phn ng Cannizaro s c li gii hp l (tuy cha ng vi thc t) l:

2 C6H5COCHO

OH- c t
o

C6H5COCOO- + C6H5COCH2OH (M) (N)

Trong mt vi ti liu [10, 11], khi vit v phn ng Cannizaro, ngi ta cn ghi rng c th xy ra phn ng Cannizaro ni phn t nh sau:
OH- c

C6H5COCHO (B)

C6H5CH(OH)COO(S)

Nu phn ng Cannizaro l mt phn ng bt thng th phn ng Cannizaro ni phn t nh trn li l trng hp c bit ca mt phn ng bt thng. Qua phn tch nh trn chng ta thy cu 7.1a khng th coi l mt bi t c mc bnh thng.Tuy vy chng ta cng bn v cu tr li cho bi : Nu gii hn ch xt mt phn ng trn vn u tin th cu tr li ng l hp cht B hoc D. Nu mun khai thc n phn ng th hai tip theo th cu tr li ng l hp cht E, F, G, H, I, K, L. u bi khng cho iu kin un nng vi kim c nn khng th c cu tr li l M v N v cng khng th l S c v theo cc ti liu [10, 11] th S c to ra khi un nng B vi kim c ch khng phi l cho A tc dng vi OH- nh bi ra. Nh vy tht khng th hiu ni v sao tc gi li ly hp cht S lm p n chnh thc? Vy th ch ch ca tc gi ra cu 7.1a l chn c mt hc sinh thn ng hay l chn mt hc sinh c cho bit v trng hp c bit ca phn ng Canizaro mt ni no . Tm bit cu 7.1a, chng ta bn v cu 10.2 trong thi chn hc sinh gii quc gia mn ho hc lp 12 THPT nm 2010: Inulin (mt cacbohirat c trong r cy actis) khng phn ng vi thuc th Felinh; khi b thu phn c mt -glucoziaza cho 2 mol glucoz v mt polisaccarit gm cc D-fructoz kt cu theo kiu (21)-Dfructofuranoz. Phn t khi tng i ca inulin khong 5200 u. V cng thc Havooc (Haworth) ca inulin. Ta phn tch : bi (Gi thit) Inulin (mt cacbohirat c trong r cy actis) khng phn ng vi thuc th Felinh khi b thu phn c mt -glucoziaza cho Inulin c 2 mt xch -D-glucoz dng lin
4

C th suy c (Kt lun) Inulin khng c nhm OH hemiaxetal

2 mol glucoz v mt polisaccarit gm cc D- kt -glicozit, v Inulin cha mt polisaccarit fructoz kt cu theo kiu (21)-D- gm cc mt xch D-fructoz lin kt theo kiu fructofuranoz (21)-D-fructofuranozit. (Ch rng u bi cho -glucoziaza ch khng phi l glicoziaza ) Phn t khi tng i ca inulin khong 5200/162 32,0987. Vy c 32 mt xch, 5200 u trong c 2 mt xch -D-glucoz v 30 mt xch D-fructofuranoz Vi nhng d kin c trong 10.2 chng ta cha bit c nhng iu sau: a) 2 mt xch -D-glucoz (tc l 2 nhm -D-glucozyl) dng piranoz hay furanoz (tc l dng vng 5 cnh hay 6 cnh). Mc d trong hp cht thin nhin glucoz thng dng piranoz, nhng bit u li khng c nhng trng hp bt thng . b) Hai gc -D-glucozyl gn vo v tr no ca polisaccarit cho. c) 30 mt xch D-fructofuranoz to ra cc polisaccarit dng chui h hay chui vng ging nh xicloextrin. d) Cc mt xch D-fructofuranoz dng hay , v khi b thu phn c mt -glucoziaza ch bit c -Dglucoz dng lin kt -glicozit. Cn nu bi thay bng -glicoziaza th lc mi suy ra c l cc mt xch D-fructofuranoz dng , cho polisaccarit khng b thu phn. Gi s rng cc mt xch -D-glucoz dng piranoz, cc mt xch D-fructofuranoz dng tc l chui polisaccarit ca inulin gm cc mt xch D-fructoz lin kt theo kiu (21)-D-fructofuranozit th c 4 dy cu trc tho mn cc d kin ca bi nh sau:
1 2

HO

O HO

G1

HO

O HO

O G -O-G

G1 O

O HO CH2 O O HO O

G1

O HO CH2 OH

CH2 OH HO O HO CH2 OH HO O O O HO

CH2 OH O HO CH2 OH HO O HO CH2OH OH O O

HO

HO

O HO

CH2

CH2

28

28

OH HO O HO CH2 OH O

28

OH HO O HO CH2 O

28

OH 2 CH2 O G OH

(I)

(II)

(III)

(IV)

Cu trc I: gc -D-glucopiranozyl th nht (G1) lin kt vi oxi thuc C s 2 ca mt xch -D-fructoz, cn gc -D-glucopiranozyl th hai th th cho H ca bt k nhm OH no t mt xch -D-fructoz th nht n th 30. Dy ny c tt c 91 cht. Cu trc II: gc -D-glucopiranozyl th nht (G1) lin kt vi oxi thuc C s 2 ca mt xch -D-fructoz, cn gc -D-glucopiranozyl th hai (G2) th cho H mt trong 4 nhm OH ca gc -D-glucopiranozyl th nht (G1). Dy ny c 4 cht. Cu trc III: 30 mt xch -D-fructofuranoz to thnh vng, hai gc -D-glucopiranozyl (G1, G2) cng mt mt xch ca polisaccarit. Dy ny c 90 cht. Cu trc IV: 30 mt xch -D-fructofuranoz to thnh vng, hai gc -D-glucopiranozyl (G1, G2) hai mt xch khc nhau ca polisaccarit. Dy ny c 3915 cht. Nh vy c t nht 4100 cht tho mn. Nu tnh thm cc trng hp khi -D-glucoz dng furanoz cn Dfructofuranoz dng -glicozit th s cht tha mn bi s ln n hng chc vn. (Mt bi c ti hng ngn, hng vn p s c nn gi l mt thi ?) Hc sinh li mt ln na khng hiu ngi ra bt hc sinh phi lm g? Hc sinh v gio vin li nh phi i khi c Hng dn chm thi chnh thc mn ho hc ca B V y l hng dn gii ca B: Cng thc ca Inulin:

O O O CH2 O O CH2 O O CH2 OO 28 n v

(Hoc v 2 gc glucoz cng mt u). Hng dn gii trn cho thy tc gi p n p t rng D-fructofuranoz dng v -D-glucoz dng piranoz. Tc gi p n cng ch tm ra c c 2 hp cht trong 4100 hp cht ph hp vi s p t ca mnh ! cn hp cht m 2 nhm -D-glucozyl cng nh vo u di ca cu trc I m tc gi cho vo p n th thc ra li l sai v khi u trn cn nhm OH hemiaxetal. Thc t l c rt nhiu gio vin v hc sinh bc xc vi nhng bi v p n nh nu trn. Bi v chng khng phi l nhng bi nghim chnh v p n cho n ch l mt s p t khng c tnh khoa hc thm ch phn khoa

hc v bi v n nh hng khng tt n t duy khoa hc ca hc sinh, gy kh khn cho gio vin trong bi dng hc sinh gii. Trn y l i iu suy ngh ca bn thn, mc d c tham vn mt vi chuyn gia v ho hc hu c nhng c th vn cn nhiu thiu st, rt mong s trao i ca cc thy, c v cc em hc sinh v cc phn m ti ti trnh by trn. V nhn y ti mong rng chng ta hy to ra mt din n trao i v cc vn gp phi trong vic dy v hc mn ha hc THPT trn t bo ny c th giao lu hc hi nhau c nhiu hn. III. Ti liu tham kho.
1. Nguyn Hu nh, nh Rng. Ho hc hu c T1. NXB Gio Dc, nm 2003 2. nh Rng, ng nh Bch, Nguyn Th Thanh Phong. Ho hc hu c T2. NXB Gio

Dc, nm 2004.
3.

Trn Quc Sn. Ti liu gio khoa chuyn ho hc lp 11-12.T1.NXB gio dc 2008.
4. Phan Tng Sn, Trn Quc Sn, ng Nh Ti. Ho Hu c T1, T2. NXB i hc v Trung

hc chuyn nghip, nm 1979.

5. Trn Quc Sn. C s l thuyt ho hu c T2. NXB gio dc, nm 1979. 6. Janice Gorzynski Smith: Organic chemistry. Mc.Graw-Hill Higher Education. 2008 7. Paula Yurkanis Bruice: Organic chemistry. Wiley-Interscience publication. 8. John McMurry: Organic chemistry. Thomson Brooks/Cole. 2008 9. Francis A. Carey: Organic chemistry. Mc.Graw-Hill Higher Education. 2000 10. Robert Thornton Morrison, Robert Neilson Boyd. Organic chemistry. Prentice-Hall. New

Delhi. 1992
11. Andren L.Ternay J.R Contemporary: Organic Chemistry. W.B Saunder Company. London.

1980.