© Qi-l ae ; Cu trite va twong téc Y i 12 Tong Cau l: Thang diém | 8 8 16 20% Diém chim 1. Cho eée chit sau: At Az 8 hon, mdi chat déu ¢6 hai cdu dang va chi e6 mét cdu dang cing, bidentate ligand) tao phire véi kim loai (0 A2, tir do biéu didn sy ta0 phite ci ching v6i chuyén dong vai phdi tir lrdmg nha (phd te ha iu dang ctia moi chat AT 4 A wie TAH8 gu b, Chit B 6 khit ning tan trong nbidu logi dung moi tir khong phin eye dén phin cue nb hi ning thay d6i clu dang oda nd, Vo edu dong bén nhit eda B trong CCl va HO, - Liew ¥; bidu didn oie ydu t6 ben hoa quan trong. Ther, dy Cty 4 ‘Tromg hay oid 40 ; te Lo, a 2 ,tlep chit chia ving thom ludn hign how nhidu tinh chit vat ly dae bigt thudng it duge nhic din trong seh vo. Cing Kho sit hal chit Ing: hexafluorobenzene (1) vai mesitylene (2) dé tim 18 vin d8 nay, @ F F Mo’ ‘Mo rie 2 ‘a, So sinh nhigt d@ ndng chily. su va 2? re thich ngiin gon. Balm: NGGLAD nt aly Add . PF Oar Ge “Ault shin tte 9 Leim cho : cd Ait phain cue 2S HEE —? bi tal Yan do walls ae oul. — airy oh alt. gistor cat phiin th bai Ron =) ab “rout 4 Bin Aen .Qi-: b, Tat se ofl ch 2 aon #6 Kb ang pn ch tf ha 37 ——————— =) cc. Khi trn 1 va 2 voi nhau ti 25°C theo ti 1g mol 1:1, ngudi ta thiy hdn hyp. hia rin mie bd Khong c6 phan img hoa hge nio xdy ra, Hay gidi thich hign tugng trén. Bg a abt BE : yd, andioin —F Falk chin tur Quien cg. 2.4%6n wong - = a Oe alg Sie Guat bodag)—> Pa ting ll Ln Lhoat+ +8T GOA Oop 286 atu Vr ‘ethane, HBdi na | oe6 Q2-1 Higu tong dign tie rét quan trong ¥ 20 22 23 Ton Cau: | Frang ae 3 a 3 = an 7 20% eee Digm chim’ 1. Hyp chit dj vong hign dign rit nhidu trong cac chit ty nhién, duge phim va ché phim cong nghé hign dai. Nghién ciru vé céw tric va tinh chét cia ching rat quan trong trong vige ing ‘dung thy tién. Bén durdi bidu dién din xudt cia m6t sé cic hgp chit dj ving phd bién. Os. O. ge ‘a, Khoanh tron nguyén tr hydrogen c6 tinh acid nhat trong mdi chat tir AI dén Ad. Khéng cin ii thich. ‘Bai lam: Cc ° oer SO ° Oy ’b. Cae gid tr pK, trong DMSO cia cde chat tir AT dén Ad durge cho (khong theo thir t#) nhwr ‘sau: 28,2; 25,2; 30,1; 26,7. Sip xép cac gia tr pX. di cho vao bang sau. Khdng cin giai thich. Chit Al Ad Ad AZ DA Veit LSIQ pk,(DMSO) O89.8 Q2-2 2.Chat C1 la hgp chit ng thom ngumg ty chita hai nhom OMe, nhung chi mét trong hai nnhém nay phan img véi LiCl. Tinh chon toe vi tri cia phan img logi nhém methyl bén didi due gidi thich boi tinh chit diie bigt cdia mgt trong cdc déng phan hé bién cita C1. Licl, DMF 80°C, 12h ‘a Vé hai déng phin hd bién bén nit c6 thé cé ctia C1. Bai lim: 1b, Vé elu (go dong phan hd bign thye 1 cia C1 va gid thich tinh chon Igc vj tri cia phan tmg? = Cho bide: Bay 1d phan ting thé dan gin: ArOMe + CI > ArO + MeCl, sau dé anion ArO ‘doe trung hia boi acid dé tao thinh sin Bai Kim: AP era. lara,’ LB ade a! | Dany Ae OH Rere” | Bic a ea_A* , . P Re OB Bian a chtanh | _ UE chi cold "uated “2! ant e davdigy than 6 dtr Ba az, Lay Hav eb ay Bal, A en60o, “fon [dtd . ae LGR cubs Q srg -foln 6 AiDn-te Bhp ou. wang halt Lame ees 6¢. Ve dong phan ho bién ben nhat ciia C2.© Q2-4 3, Nhigt hydrogen héa née | va nde 2 ciia butael3-diene Lin lugt li 26,1 va -29,9 keal/mol. a, Néu it nhit m6t ly do ngin gon dé gidi thich sy chénh Iéch ve nhigt hydrogen hoa (= 3,8 kcal/mol) cua hai lién két doi C=C trong buta-1,3-diene nD Boo mt 148i wo coin HE > us hy Pee Sea Pa nae Ae Gel hudo 20 girls ter ge | oe L Lv | Gm cho thay nhigt hydrogen hda chuyén i but 4 kealimol, d uit nha mot ly ——___| b. Nghich ly buta-1.3-diyne: thye ng diyne thanh but-I-yne va tir but-I-yne thinh butane lin tugt la: ~70,6 v6 ding’ nha thay-Khdng 66 sy chénh Igch nio ding ké vé nhigt hydrogen hos, do ngin gon dé giai thich hign wong ni. wale CAVE C3 Cor How > cot, omlortel onbotal 2p tw NCW g Sony ong Bn dune . | 2 bn Labay Lar khong as | > NAB & hydragenDoa’ ear anlee enbhou yeltey 2© ¥ nghia nhiing chiée ving ba canh Cau 3: 1. Din chit cia cyclopropane cé kha nang cho ahiéu phan img mé ving thi vj do su ling Ko cia cic lién két oc-c trong cau tric. Phan img ejng vong [3+2] bén dudi minh hoa cho mit trong cdc tinh chét thi vj cia nhom hgp chit nay. + 9 Deukifnphanop 7-9 ‘Thue té, chi c6 mét s6 cyclopropane c6 cau tric phi hgp msi co kha nang cho phin img nay Bang bén dudi minh mét hoa edu tric cis mét din xudt cyclopropane phi hop dé thyc hita phan img trén (D1) va théng sé vé d6 dai ca cdc lién két occ cn thiéu. DAC), Lién két C-C @) (b) tc) Prva) cone, Ba aT) 130 a. Cho chu vi cia ving ba trong D1 1a 4.55 A va gid tri tuyét ddi vé chénh léch 46 dai eva lign két (a) va (©) 14 0.03 A. Tinh 45 dai liga két (a) va (6). Gidi thich, =; ay co Aw ung -T > én Rca) sth =) 2a) tcc) =0.03% © -{a) Ot boo SHS Tathay : 04 ar thom ot Adu ting -T, +e Bt mbbom —CoOMe of mabe iy diay ~T mre VAy Cad At Li keorv® —coOMe mbit" fle eS Laz 003% oF igi tS? — Sat ec= SOF | R= At fo f bar ASHE© Q3-2 \b. Thye nghigin cho théy lita kit C-C ob mic $9 phin ogo mumb abit st 2 chum phie ing obit. Trong ba bén kés wen (a - ¢), de két mao 06 enix 6 pin ope muck abit? Ve cis ic bag tising mink ipa. BE boo (B)oo D (Boe ale abet OMe py Me, oe eo Xohe | | | l ce Hy v@ clu go cus sin phim chink Go Gch KN cho DI Se Gang wa Pike (pF-CHCHO). [Baim | a | PK by it Shp aa ee 10© Q3-4 2. Dé nghi co ché cho phan img sau: oN BusSnl —_—- N Dar AIBN, Cote. a N. NtaD Be SER te, Kore, ie wien XP- ee© Q3-3 d. Khong cin giai thich, sip xép téc d6 phan img cia ba cu chit sau vin p-fluorobenzaldebyde ‘theo chiéu ting dan. CO;Me Me ‘COnMe ‘COMe ‘comme come ot Met 2 FC os ‘Bailam: 02> 503© ™ Q41 Ung dung héa hoc dai cwong vio tim hiéu phan teng Y 41 42 43 44 Tong Thang diém 6 Ss 5 6 22 1 Diém chim Cau 4: 20% 1, Khai nigm tro chuyén phin (ddng phan can quay, atropisomer) cing ngay duge cha ¥ nhiéu trong nghién ctu Héa Duge. Tro chuyén phin la cic héa ching bat 46i ximg dugc hinh thinh do sy can quay xung quanh lién két C-C, tinh chat nay thuémg duge goi la thi tinh (theo) tryc. Nam 2020, mot tie gid ngudi Vigt da céng bb mot phin ting ghép d6i C-C thong qua sir hoat héa lign két C-H dé 120 thanh mét hgp chat tri-aryl cé tinh chat vita néu, Phan img duge biéu dign nhu sau: Xiie tée ghép 461 t mec. bat a6i _ bit ah xtg tomy Pho, am ‘OMe 2 equiv fon Et Ez Hay vé edu tric cde déng phin lip thé ciia £3, cho biét déng khong quang hoat. Khéng clin gidi thich hay dgc céu hinh tuyét ai.© Q42 2. Phin ting hydrogen bia ob xis the mang habe ng Gyn ong la tie he ox. Tien, ga Keng, ky cba dupe ding dé xic dink 66 béw cba che abi 651 CHC. Tity vio v4 6 olin Hib ide 2 anh sy bydeogen ‘ia 06 thd cho tink chon Ie héa boc, choe Soe vf wh wi cam foe tp tt cw, Qui st a ydcoyen it FI vii cic ndi 46% Guage Cink du (a—c). oly fo 1 ees 4 Hat ea) en PrP npO FA one 2. So sinh & bén cua cic nii G6 tis 2 - ¢. Khing che gti dicts. meMTW >Cc) > Co) 1B. VE cies rhc pp thd cae F2 BEF chs ta dy | Ses ai am: Ra ¢ Ma 4& Q4-3 x ‘Toe GS phan ung hydrogen hda Kang chi ti 8 vei di) bn ca tlm phan dng, Mand edn phy thuge ‘do mp: dG electron cada chdag. Trong phist img hydrogen hoa ~ bilo v9 nh oxime bén dud, két quad phan img hydrogen hide od sut khae bit hing ké khi di chd vj tri nhdm oxime trén wong pyrrole. A 1) Boo, 0, ih (vatm) oA coo SEs a 5) coo RH eacet feng coy ah da, Ae 2 bude) Bor, 1) Boc,0, Hz (1atm) EROAS, PIC Bod Th ti \ —— 7 "COOMe H 2) Boc,0, DMAP Be MeCN, 2h a » 4b, 55% (2 buoc) higu suit cao hon va thdi gitin phiin img ngin hon ding ké so du kiga. Dua vio higu img dign tir cia 3a va 3b. gia thich sir shan img va d6 bén ca sin phim, a, Pay endl oxtne_cuse prolw Lut Be bt «ber erlsoren “two Ne Parrveng ugha 2 oSolaily bé a gh "EY aye y cghe 4s Luv aay + cul, dig > qduchion? a HL a, Hoss© Q4-4 1, Phdi tir S-diketiminate (hay odn ggi ld NacNac) hign tai duge sir dyng khé rong rai trong héa hoc vo sey cita nguyen t nhom chink nh dae tinh bén hoa ede hgp chide kim logi c6 86 oxid héa bat thuong. Ar An co O N, N: AQ (tat ar (MgNacNac), ~ Phite chat cita kim logi Mg(!) voi NacNae ¢6 kha niing khir héa cyclooctatetracne thu duge anion Y* chi chita C va Hy ngoai ra nd edn cd thé tham gia vio phin tng trimer-khir héa khi CO dé thu duge anion 2" ‘BaLlam: loWw 6 ce ng hoc Enzyme Qo: a x ane SA 32 33 Tong a Thang diém 8 4 4 16 Diém cham. zyme cé hoat tinh xic tac rit cao nhung thurimg bj tre ché boi mot sd chit, cdc chit nay duge ki higu vung 1a I. Gid thiét co ché cita mot phin img xiic te enzyme khi c6 mit chit tee ché thujn nghich anh tranh I nhur sau: EI aK, = ex dy vik) = oe ey Dya vio co ché da cho véi gia thiét bude tao thinh P la bude quyét dinh téc d6 phan img, ngudi ta [8 dang chimg minh biéu thie tinh téc d6 phan img xc téc enzyme trén khi oO mat I la: ke X [Elo IS] _ Vmax * (5) tye (14 2) +00 Ku + (3) voi Ky Sts nas = Ka X (Elo: Ky = Ky x (14H) ~ Dé xitedinh gid tri Ki cho phan ing trén khi [1] = 1,0 pM, ngui ta da thye hign mot log thi nghigm do lung van t6c dau cba phan img voi gradient néng 46 co chat § va thu vé duge bing két qua sau: Slam) 10 2.0 30 10,0 ‘vo(uM/phat) 0,99 178 3,60 5.61 1, Dua vao bang s6 ligu trén, hay xc dinh gid tr] Ky khi c6 mat chit tre ehé 1 BALL: a= = Te posing ‘wal gp Dye 28 = 10 4. pk uy 0092 aoa V Vinaya te max Ri quuy weedy sal ) FOOL we Wrmox= OC @ EM[ Vox = 29a dt 0,4942, Khi nghién ciru mot chat ire ché canh tranh I? khic, ngurdi ta Kip Iai ede thi n duge céc gid tr] Ky 6 cdc nong 9 chat ire ché khic nhau. Hy sit dung bang si toan hing 6K; cia I’ ght twong ty va t lig bén durai dé tt oT! 2) = ke 462 quy pall 0 ue 6)4s4 ul =) 462 0.999 5, 4SY — ABA @ wy = kyr et @) {PF} (uM) 0.0 “Wo 30 so Ku (HM) 62 Th 20,5 | 29,47 ‘Bai Jam: 7 Tea: Mae oy ‘ers \€ 53 ‘Cae phuong phap trén cho thay ring, dé tinh chinh xc mt gid tr] K, cba mét chit de ché, clin phai tién hanh vd s6 thi nyhi¢m dng hge, rit kh khdn trong ing dung sing lge nhanh chit te ché. Dé gidi quyét van dé nay, Cheng vi Prusoff di 48 xuit phurong phip wae tinh gin diing K, cua mot ché thong qua gia tr} ICwo cua nd. Cy thé, [Cs clia mét chat de ché Li ndng d6 cia no lam cho vin te xe tac enzyme gidm di 50%. 3. Ding phuong phdp todn hoc, ‘chimg minh phyong trinh Cheng-Prusoff trinh bay trén. Bailam: ; Dede = Vovox U8). d. = Vmax) __ az Fyrtsy 2 KOE) +09 © (qyt28I) a= key (1 ase) 2 see ey - a ©) =e. ky = SrCa_ Qc SS Ay tS) kM \ Thi sinh kluing diave sie ang. 1 igus Gicion thy Kling gia thick i them