D\Ia van thuyet lien k~t hoa tri thuyet VB, hay giai thich S\I tao thanh lien k~t giua ion Ag", Cr3+ va cac phan nr amoniac trong cac hop ehftt tan do... Vi~t phirong trinh hoa hoc cua b[r]
Trang 1BOGIAO DVC vA DAo T~o
DE THI CHiNH TmJC
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KY TID CHQN HQC SINH GIOI ouoc GIA THPT
NAM2013 Mon:HOAHQC
Thoi gian: 180 phut tkhong !dthai gian giao oJ)
Ngay thitlnr hai: 12/01/2013
(DJ thi co 03 trang, g6m 06 diu)
Cau 1 (2,5oiim)
1. Cho day hop ch~t sau:
a) Hay chi ro cac dl;icdiem du true cho th~y A la hop eh~t tham So sanh kha nang phan irng th~ electrophin ella A voi benzen va cho bi~tvitri phan irng uu tien aA Giai thich
b) So sanh (co giai thich) momen hrong eire cua A, B va C v~ dQ160.
e) So sanh (co giai thieh) nhiet dQ nong chay, nhiet dQ soi cua day hop eh~t tren,
2 So sanh (co giai thich) tinh b~O' ella hai hop ch~t X va Ydurn day:
NH2
3. Hay cho biet hop eh~t durn day co bao nhieu d6ng phan l~p the va bieu di€n c~u true khong gian cua cac d6ng phan l~p the do
o o Q
Cau 2 (3,5 diim) ,
1. Hop ch~t X tao boi ba nguyen t5 hoa hoc va co kh6i lUQ11gmol bang 282 gam, trong do oxi chiem 17,02% v~ kh5i hrong 1:)6t chay hoan toan X thu duoc s5 mol C02 g~p doi s6 mol H20 Cho X tac dung voi hrong du nhom'isopropylat trong ancol isopropylie thu duoc hop ch~t Y co kh6i luong mol bang 288 gam Ozon phan khir hoa hoac ozon phan oxi hoa X, cling thu duoc mQt hop ch~t Z duy nh~t co kh6i hrong mol bang 314 gam Khir Z bang NaBH4, sau do cho san pham
tao thanh tac dung voi NaI04 tao ra mQt h6n hop g6m o-C 6 H 4 (CHO)2 va OHC-(CH2)S-CH(OH)-(CH2)rCHO Mat khac, khi xu ly xbfing NaNH2IDMF (N,N-dimetylfomamit, (CH3)2NCHO) thi thu duoc hop ch~t X, (CJ8H1803) Cho Xl tac dung voi H2/Pd, sau do dun nong san pham tao thanh voi H2S04 (dl;ic) tao ra hop eh~t P (CJsH2oO) Hay l~p lu~ d~ xac dinh cong thirc d.u tao ella X, Y, Z, x,va P
(Cho: H= 1; C= 12; 0= 16).
2. Them tu ill dung dich A (metyl t-butyl xeton) vao isobutyl magie bromua Phan irng kern thee sir thoat khiB, bi~t rang khi ozon phan B thi thu duoc axeton va mQtkhikhac Sau khi thuy phan h6n hQ'Pphan irng, tach chi~t va chung dt phan doan thi thu diroc hai ancol C (ClOH220),D (C~J40)
va mQt xetoancol E (C12H2402)
a) Vi~t so d6 phan irng di~u eh~ A ill axeton
b) Xac dinh cong thirc du tao va giai thich flua trinh hinh thanh cac ch~t B, C, D va E.
Trang 2Cau 3 (6,5 ili€m)
1 Hoan thrum cac sa db phan (rug duoi day:
a) OHC\_/CHO + CH3NH2 + HOOC <;? eOOH e)lo A ('C H NO) Zn(Hg) - B
~ 8 13· -' HCI(d) 1) CH31 du 1) 03
D E1 axit glutarie + axit oxalic 1) CH31 du 1 2) A920, H20, to 2) H 2 02
2) A9 2 0, H 2 0, to 1) CH31 du 1) 03 axit malonic +aXit sucxinic
, D2 2) A9 2 0, H 2 0, to E2 2)HzOz "
Hay giai thich S1,l' hinh thrum hop chAt A trong sa db tren bang co ~h~'phfm (mg.
A
(C13H1406)
B (C11H1~er202) CH3COOH
COOCH3
1) KOH, H20
2 Gia thiet codu cac hoa chAtvadi8u kien phan irng cfu1thiet, hay tang hop:
b) Hop chAtY ill furan
~
3 Bkg coochS phan irng, giai thich S\Ihinh thanh san pham trong cac sadb chuy~n hoa sau:
H 1) CH31
~ 0 2)'r\iaOH
2)~ 3)H®
o
Cau 4 (2,0 iliim)
Khi cho hop chAt A (C7H1206) tac dung voi axit periodic (HI04.2H20) du, thu duoc hop chAt
B ill h6n hop san pham Thuy phan B voi xuc tac axit, thu diroc glioxal (OHC-CHO) va axit D-glyxeric (D-HOCH2CH(OH)COOH) Metyl hoa A b~g (CH3)2S04 dir, xuc tac kiem, thu diroc hop chAt C Cho C tac dung voi ozon rbi ch~ hoa san pham bang kern kim loai trong dung dich axit clohidric, thu diroc metyl (S)-2-metoxi-3-oxopropanoat va metyl (R)-2-hidroxi-3-metoxipropanoat
Hay xac dinh cAu true cua A, B va C, biSt r~g trong phan ill A m9t mra s6 nguyen til cacbon bAtd6i co cau hinh R.
Cau 5 (1,5 iliim)
1.Tu dietyl malonat va cac hoa chAt cfu1thi~t khac, hay trlnh bay m9t phirong phap thich hop as
2 Tir glyxin va alanin, hay de xu&t met So' db tang hop co dinh huong dipeptit Ala-Gly voi hieu suAt cao, gift thiet co du cac hoa chAt va dieu kien phan img cful thi~t
®
H
Trang 33 MQt tetradecapeptit A di~u khi~n hoat dQng cua tuyen yen diroc tach ratil vo nao Khi xac dinh trinh tv cua A bfutg phuong phap Edman, nguoi ta thu duoc hQ'PchAt duoi day:
s
Khi thuy phan chon IQc A tao ra cac dean mach 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
Hay xac dinh eftu true b~c IcuaA, bi~t A comQt c:1udisunfua (-S-S-)
Cau 6 (4,0 iJi&m)
1 Khao sat bkg thuc nghiem a2SoC phan irng thuy phan metyl axetat voi S\I c6 m~t cua HCI
du, n6ng dQ 0,05M Th~ tich dung dich NaOH co n3ng de)c6 dinh dung d~ trung hoa 20 ml h6n hQ'Pphan irng thea thai gian nhir sau:
t(phut)
Vdd NaOH (ml) 19,52 20,64 23,44 25,36 37,76 a) Vi~t phuong trinh hoa hoc cua cac phan irng xay ra
b) Chimg minh phan irng thuy phan metyl axetat la phan irng b~e 1 Tinh hang s6 t6e de) va thoi gian mra phan irng,
2 a) Cac chftt AgCI va Cr(OH)3 khong tan trong nuoc, nhung trong mrcc amoniac lai tao ra nhtrng hop chftt tan D\Ia van thuyet lien k~t hoa tri (thuyet VB), hay giai thich S\I tao thanh lien k~t giua ion Ag", Cr3+ va cac phan nr amoniac trong cac hop ehftt tan do.
b)Hay thi~tl~psod6 pind~ khi pinlam vi~ethixay raphan trng:
Zn2+ + 4NH3-+ [Zn(NH3)4f+
Vi~t phirong trinh hoa hoc cua ban phan (rug xay ra tren m6i di~n eire Tinh E~in
Bi~t: E~n2+/Zn =-O,76V; hkg s6 ben cua ion phirc [Zn(NH3)4f+: 13= 108,89;
a25°C: 2,303.RT =0,0592
F
-
H~T -* Thl sinh khong duoc Stt dung tai li?u;
*Giam thi khong giai thfch gi them.