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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]
(1)BO GIAO DVC vA DAo T~o DE THI CHiNH TmJC ' B~N ? "1 , 1L _ KY TID CHQN HQC SINH GIOI GIA THPT Mon:HOAHQC Thoi gian: 180 phut tkhong !d thai gian giao oJ) Ngay thi tlnr hai: 12/01/2013 (DJ thi 03 trang, g6m 06 diu) f ouoc NAM2013 CTrr',JTY ~'-'; ~ ! AI,I: tl \ ~ co i) ~'~ !:, , _·II-, _ "us,::- :.t:;. Cau (2,5 oiim) Cho day hop ch~t sau: Q-PH o Q o ABC D E Q-ro G OH 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~t vi tri phan irng uu tien A Giai thich b) So sanh (co giai thich) momen hrong eire cua A, B va C v~ dQ 160 e) So sanh (co giai thieh) nhiet dQ nong chay, nhiet dQ soi cua day hop eh~t tren, So sanh (co giai thich) tinh b~O' ella hai hop ch~t X va Y durn day: a NH2 X: H N-Q Y: 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 Cau (3,5 diim) , Hop ch~t X tao boi ba nguyen t5 hoa hoc va co kh6i lUQ11gmol bang 282 gam, 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 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 nh~t co kh6i hrong mol bang 314 gam Khir Z bang NaBH4, sau cho san pham tao tac dung voi NaI04 tao mQt h6n hop g6m o-C6H4(CHO)2 va OHC-(CH2)S-CH(OH)(CH2)rCHO Mat khac, xu ly bfing NaNH2IDMF (N,N-dimetylfomamit, (CH3)2NCHO) thi thu duoc hop ch~t X, (CJ8H1803) Cho Xl tac dung voi H2/Pd, sau dun nong san pham tao voi H2S04 (dl;ic) tao 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) Them tu ill dung dich A (metyl t-butyl xeton) vao isobutyl magie bromua Phan irng kern thee sir thoat B, bi~t rang ozon phan B thi thu duoc axeton va mQt khac Sau 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 cac ch~t B, C, D va E x Trang 1/3 (2) Cau (6,5 ili€m) Hoan thrum cac sa db phan (rug duoi day: a) OHC\_/CHO + CH3NH2 + HOOC ~ D 1) CH31 du 1) CH31 du 2) A920, H20, to 2) A920, H20, to , S1,l' e)lo eOOH E1 1) CH31 du 2) A920, H20, to D2 Hay giai thich <;? E2 1) 03 A ('C H NO) 13· -' Zn(Hg) HCI(d) - B - axit glutarie + axit oxalic 2) H202 1) 03 2) HzOz axit malonic +aXit sucxinic " hinh thrum hop chAt A sa db tren bang co ~h~'phfm (mg dd HCI b) CH3COOH B (C11H1~er202) A (C13H1406) COOCH3 1) KOH, H20 2) HCI Gia thiet co du cac hoa chAt va di8u kien phan irng cfu1thiet, hay tang hop: a) Hop chst X tu dietyl malonat b) Hop chAtY ill furan X: ~ ' , Y: ~ Bkg coochS phan irng, giai thich S\I hinh san pham cac sa db chuy~n hoa sau: a ° ) 1)Q,H® 6~ 2)~ H 9r{0 o ® 1) CH31 H 2)'r\iaOH 3)H® Cau (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 Dglyxeric (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 dung dich axit clohidric, thu diroc metyl (S)-2-metoxi-3-oxopropanoat va metyl (R)-2-hidroxi-3metoxipropanoat Hay xac dinh cAu true cua A, B va C, biSt r~g phan ill A m9t mra s6 nguyen til cacbon bAtd6i co cau hinh R Cau (1,5 iliim) Tu dietyl malonat va cac hoa chAt cfu1thi~t khac, hay trlnh bay m9t phirong phap thich hop diSu ch~ methionin (CH3SCH2CH2CH(NH2)COOH) ' 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 as Trang 2/3 (3) til MQt tetradecapeptit A di~u khi~n hoat dQng cua tuyen yen diroc tach vo nao Khi xac dinh trinh tv cua A bfutg phuong phap Edman, nguoi ta thu duoc hQ'PchAt duoi day: s 0-9: o Khi thuy phan chon IQc A tao cac dean mach peptit sau: Phe- Trp; Thr-Ser-Cys; Lys- ThrPhe; Thr-Phe- Thr-Ser-Cys; Asn-Phe.:Phe- Trp-Lys; Ala-Gly-Cys-Lys-Asn-Phe Hay xac dinh eftu true b~c I cua A, bi~t A co mQt c:1udisunfua (-S-S-) Cau (4,0 iJi&m) Khao sat bkg thuc nghiem a 2SoC 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 21 75 119 00 20,64 23,44 25,36 37,76 a) Vi~t phuong trinh hoa hoc cua cac phan irng xay b) Chimg minh phan irng thuy phan metyl axetat la phan irng b~e Tinh hang s6 t6e de) va thoi gian mra phan irng, a) Cac chftt AgCI va Cr(OH)3 khong tan nuoc, nhung mrcc amoniac lai tao nhtrng hop chftt tan D\Ia van thuyet lien k~t hoa tri (thuyet VB), hay giai thich S\I tao lien k~t giua ion Ag", Cr3+ va cac phan nr amoniac cac hop ehftt tan b) Hay thi~t l~p so d6 pin d~ pin lam vi~e thi xay phan trng: Zn2+ + 4NH3 -+ [Zn(NH3)4f+ Vi~t phirong trinh hoa hoc cua ban phan (rug xay tren m6i di~n eire Tinh E~in Bi~t: E~n2+/Zn = -O,76V; hkg a 25°C: s6 ben cua ion phirc [Zn(NH3)4f+: 13= 108,89; 2,303.RT =0,0592 F -H~T * Thl sinh khong duoc Stt dung tai li?u; * Giam thi khong giai thfch gi them Trang 3/3 (4)