BQ GIAO DUC VADAOTAO KY THI CHON HOC SINH GIGi QU6C GiA THPT NAM 2018 HUONG DAN CHAM DE THI CHINH TRUC Mén: HOA HOC Neat thi thie hai: 12/01/2018 1 Huong dan chung 1. Can b6 chdm thi chém dung nh Huéng din chim, d4p 4n, thang diém cita BO Gido dye va Bio tao, : 2. Déi v6i cu, ¥ ma thi sinh e6 céch tra Idi khde so véi dép én nhung diing thi vn cho diém téi da cia cau, ¥ dé theo thang diém. : . 3. Cn b6 cham thi kh6ng quy tron diém thanh phan, diém timg cau, diém ciia bai thi va tng diém hai bai thi ota thi sinh, IL. Huong din cu thé ‘MOtss6 kc higu vide tit: Me: metyl; Et: ety; Ac: axetyl; PCC: print clocromat, Ph: Phenyl. ‘Trong céc quy trinh ting hgp hitu ca, cée chat v6 co va diéu kién cn thiét 06 at. Cau I (3,0 diém) 1. Cho cdc chat sau day: LoS 28 a) Gitta Al va A2, chét nao dé tham gia phan img hon véi Br, theo co ché eng electrophin (vao lign két 461 C=C)? Giai thich. b) So sinh lye axit gitta A2 va A3. Giai thich. ©) Trong sé céc chit: B1, B2 va B3, chét ndo c6 lye bazo Ién nht? Giai thich. d) DE xuat so a3 téng hop A2 ti Al. ©) Cho sod chuyén héa A2 nhu sau: ag OP dCR gp __ vornol Ci | gg HO" gg GUO.H gg PRCHO G, Moo | KOH. Castggo ot o Ve (kh6ng can giai thich) céng thtte cdu tao cia cde chét C1, C2, C3, C4, C5, C6 va C7. 2. Gian 48 nang lugng orbital (obitan) phan tir (MO) cla nhém 7 cacbonyl durge cho & hinh bén. Gia trj ning lung HOMO (orbital phan ‘tk bj chiém c6 mite nang long cao nhét) va LUMO (orbital phan tir Khéng bi chiém c6 mite ning hwong thép nhét) cla CH;CH=O, Ee [CH,CH=OHT' (khi CH;CH=O duc hogt héa bling axit), CN- va gid tr] 2+ nang Iugng ciia AO 1s cla H” duge cho trong bang sau: CHsCH=0 | [CH,CH-OH]" He HOMO (eV) [13,44 =14,04 0,00 LUMO (ev) | 9,50 TE Biét ring HOMO ouia phan tir (hoe ion) nay cé thé tuong téc véi LUMO eta phan tir (hofe ion) kia. Khodng céch ning lugng HOMO-LUMO cang gin thi tuong tée cing manh, 8) Dya vio céec dtr kign cho biét 6 trén,giaithich vi sao trong phan img cng gitta HCN va CHsCH=O thi co ché cla phan img la An (nhém CN° tn céng trade) ma khéng phai la Ag (H’ tn céng truéc), b) Dua ra minh chimg vé mat nang Iuong 4é gidi thich tai sao khi CH3CH=O duoc hoat héa bing axit thi phan img cng v6i CN- xdy ra thud Igi hom. Trang 1/103. Cho so dé chuyén héa cumen (isopropylbenzen) nhur sau: ay tHe a 2. POs CH:OMHC! — CygHpsNO Cumen OF, 1 HeSO_ pg CoH Vé (kh6ng can giai thich) céng thitc cdu tao cla céc chat D1, D2, D3 va D4. Huong din chim ee 1. a) Gita A1 va A2, chét néo d& tham gia phan img v6i Br, theo co ché cng electrophin (vao lién ket 461 C=C) hon? Gi thich, : ee ‘Theo co ché cia phan tmg cng electrophin cia Br, vao lién két doi C=C, tée nhan tén cong la Br’, néu lin két d6i gidu electron va cacbocation trung gian bén thi phan img thudn loi. A2 dé tham gia phan img cng hon A1 do hai nguyén nhén: thir nhét la nhém cacbonyl cla Al hit dign tir qua hé lién két o (higu img -1) lam cho lién két 46i C=C nghéo electron hon A2; thit hai la do cacbocation b§c ba trung gian tgo thanh tir A2 bén hon. ° 9 Br A i { et § ye pe il at b) So sénh lye axit gitta A2 va A3. Giai thich. A3 6 tinh axit cao hon A2. Khi A3 téch proton tao thanh hé c6 tinh thom. H [as ©) Trong sé cdc chét: B1, B2 va B3, chét nao c6 lye bazo Ién nhdt? Giai thich. ‘BI 6 tinh bazo cao nhat do khi bj proton héa tao thanh hé thom. awe —wy i. — mR NH Bt ' ) Be xudt so dd tng hop A2 tir Al. p o oO ° / sitet. oo Mt. CT) wee Crh moen of at ©) So dd chuyén héa A2: : Bu _Mgar MBE oH ° = ° ct os o cs cs cr 2a) : Ks iH ob thé coi AO Is la LUMO. Khodng céch nang lugng ola AO nay véi HOMO cia CHsCH-O la 13,44 eV. ~ Khodng céch nang hngng ca LUMO (CN) véi HOMO eita CHsCH=0 la 4,97 eV. ;Kooins cic ning lugng ola HOMO (CN ) vi LUMO ela CHyCH-0 la 2,96 eV. vay vé mit ning lugng, trong phan img HCN véi CHsCH=0 thi co ché ir CN" tn c6ng truéc) ma kh6ng phai la Ag (H* tén cng tnu6e, a Trang 2/10b) Tuong ty: Khodng cfich nang lugng otia HOMO (CN*) véi LUMO ella [CH,CH=OH] la 2,72 eV. Do viy khi CHCH=0 dugc hoat héa bang axit thi phan ding cGng v6i CN" xay ra thugn Ii hon do khoang cdch nang lugng HOMO-LUMO giam tir2,96 eV xuéng cin 2,72 eV. 3. Vé cng thite cu tao cita cdc cht D1, D2, D3 va D4 OH che oe om re Os OO sae o1 Cau II (3,0 diém) 1. Cho cis-2-aminoxiclohexanol phan img véi dung dich NaNO2/HCI, thu duge chét A va chét B déu 06 céng thite phan tir CeHio0. Cho trans-2-aminoxiclohexanol phan img véi dung dich NaNO,/HCI, thu duge chét A. Ca A va B déu a img v6i thudc thir 2,4-dinitrophenylhidrazin. Xéc djnh cng thite cu tao ca A va B, Dé xudt co ché giai thich sy tao thanh A va B. 2. Phan tmg da téc nhan la mt phuong phép dé ting : . 2 CUy Lime eit o7*N x eo. hgp cdc dj vong. Dj ving X duge didu ché theo phan img & hinh bén, Bé xuat co ché dé giai thich sy tao thanh X. 3. Papaverin (hinh ben) 1a hogt chét ding 48 bao ché thude chéng co thit. Dé xudt so 4 tdng hop papaverin ti 1,2-dimetoxibenzen Va jeor " cdc Wop chat hitu co chita khéng qué 2 nguyén ti cacbon. one 4. Quercetin (chét chéng oxi héa va Lim bén thinh mach méu) c6 thé duge ting PePeverin hp tir 1,2-dimetoxibenzen theo so dd sau: m0. 0H a eens aye 0 IOYKOH HH8O4 g GatiONO yy 1.140) i eos CoH, KOH CigtoaOe —CiHeaOs ——_CagHygNO 2H OH OHO — Quercetin Vé (khéng clin gidi thich) céng thite cdu tao cia céc chit E, F, G va H. ‘Hiring din chim 1. Déng phan trans-2-aminoxiclohexanol t8n tai cint yéu & cdu dang (e, e). Khi 6 nguyén tir H khéng duc uu tién téch ra. Qué trinh chuyén vj cacbocation duge wu tién. Bann BO Brie Oona a Over HO’ trans Déng phan cis-2-aminoxiclohexanol tin tai ca 2 cdu dang nén xy ra c& 2 qué trinh chuyén vj cacbocation vA téch proton. 4 4 QT~ HINO: AT oS Lamba) 1O” 2 HO! ‘N, Pa Me wi On ag? = HN # 2, 8 xudt co ché phan ting. NH\OAc ——= NHy + H+ Aco" Ry Trang 3/10o i ° 9 ° 9 ° ° BO ce cee an ae) Oe ji di ita khér 3. Da xudt so 48 tng hop papaverin tir 1,2-dimetoxibenzen va cde hgp chat hou co chita khéng qua 2 nguyén tir cacbon, | coon a CRON HO CHO NBI mee yor, “Ky Meo" er are oh pe ane MeO 3.KeN As aa 286° 1. LiAIH, Meo” monn 2.150" 4, Vé (Khong cin gidi thich) cng thite cdu tqo cia cdc chit E, F, G va H. ‘OMe ut 7 oe ome a O O oo PS so ry" 0 re J ‘N-OH ; : eae Gell 8 OMe 0 Cau DI (3,0 diém) 1. Metylarbutin (C;3H40;) duigc tim thy trong qua l, khéng phan mg v6i thuéc thir Tollens (Tolen). Khi thiy phan metylarbutin bing enzim f-glucozidaza, thu duge D-glucozo va hgp chdt thom A (CrHi02). Cho A phan img véi HI, thu duge chét B (CéHe02) khOng mau, phan tir khéng phn cue, c6 tinh axit va phan tmg duge véi nuée brom. Khi dé lau trong khong khi, chit B bj oxi héa tgo thanh sin phdm c6 mau da cam. Cho metylarbutin phan tmg véi lung du dimetyl sunfat trong moi truémg kiém, thu duge chét C. Thity phan C bing dung dich HCI lodng, thu duge 2,3,4,6-tetra-O-metylglucozo va chat A. a) Xée dinh (cé gidi thich) cOng thite cdu tao cla A, B va cu tric cila metylarbutin, b) Metylarbutin duge téng hop theo so dé sau: H OH ‘ 1Q ADO yy HBL og AS Fr —O8 Metylarbutin OH CieHlnOn— CaHBr0, ABO CysHOy, * yO + VE (khéng cn giai thich) cu tric cita cdc cht D, E va F. + BE xult co ché dé gidi thich sy hinh thanh E va F. 2. Thily phan hodn toin mét axit X (CioH va chét X: | COOEt ,COOEt a HC, Qu cg, HO Boe Hy 4 sry | ‘COE 2 Fiyra “Ycooet BOT | 3. NaBH, i ©) Céu tao cla benztropin: i Wery, Hey, | ; 1, : ou y Benzropin 2. VE clu tao cdc chat E, F, G, H, Iva K (Vitamin B6) ost on oe - a . CN ON. ON ODN. CN HN, A \ A Ho. won won AWA A [3 J E 7 & : W 7 ' Trang 6/10HO Me cot onc P ae ») Dé xudt co ché chuyén ha tir L thinh M (Phuong php Ficher cdi tin, ORO UK OL JAC CQ Op 2, —| | 133) — — NEN AS os yrs na NY NHe q Cau V (4,0 diém) 1. Hop chat thom vanillin la tidn chdt trong téng hop héa hge va sinh téng hop. ‘a) Con duémg sinh tng hop vanillin tir tyrosin theo so 48 sau: 1)E3 MeO CHO COOH pk 130°, 1 ‘HjO", £2, ON, Prior NADPH, MOVE, 7 o 2a HO wosin a HO Vantin Biét ring, pyridoxal la enzim deaminaza, NADPH ¢6 tinh khir tuong ty nh NaBH, El la enzim ‘chidrat héa, E2 la enzim hidrat héa, E3 la enzim, SAM 1a téc nhdn metyl héa tuong ty nh Mel/AgO. + Vai trd cia enzim E3 la gi? + Vé (kh6ng cdn giai thich) céng thite cfu tao ca céc chét A, B, C va. ) Vanillin chuyén héa thanh dihidroxiphenylalanin theo so 48 sau: Vanitn -MOsSOs AGO | HAPCP | 1. Brtphotpho, in © mail KOH ‘AcONa’ 2.NHy H NH \Vé (khong cdn giai thich) c6ng thite cu tao céc chét I, K, L va M. a 2. Glicozit thién nhién X chia hop phan quercetin (xem céng thie & Cau IL4). Thay phan X bing enzim a-glicozidaza, thu duge chét X1 (CéHl)20s) va chét X2. Thy phan X2 biing enzim B-glucozidaza, thu duge chat x3 (Celliz0s) va quercetin. Metyl héa hodn toan X réi thiiy phan sin phdm c6 xtc tée axit, thu duge chat X4 (CyHis0s), chat X5 (CoHis0¢) va chét X6. Oxi hda X4 bling HNOs, thu dugc chit yéu la axit QRAR)-2,3,4-trimetoxipentandioic, axit meso-2,3-dimetoxibutandioic va axit axetic. Oxi héa XS bing HINOs tao thanh axit meso-2,3,4-trimetoxipentandioic. Cho biét, X1 o6 edu hinh L, X3 c6 edu hinh D va X6 t5n tai & m6t can bing xeto - enol. Xac dinh (c6 gidi thich) cu tric cia cée chit XI, X2, X3, X4, XS va X, trong 46 cdc hop phan cacbohidrat duge biéu dién duréi dang cng thite Haworth (Havooc). 3. Peptit ty nhién ¥ 6 cu tric Pept Asn Gly. Pept 46 lau trong mi trudng kiém nhe thi cé ‘sit giai phong ‘amoniac tir dogn mach Asn-Gly. Néu 4é lau thém mét thd gian nffa trong diéu kién nay thi CON Peptit ¥ chuyén héa thinh hai peptit méi Yi va Y2 la ding phn cia nhau. Xée dinh edu i He ‘nic ella cde peptit YI va ¥2. Giai thich gué trinh chuyén héa Y thanh YI va Y2. Biét céc HN cooH oan mach 'Peptit va Peptit” khéng bj bien d6i trong digu kign trén, eek oa ‘Huong din chim 1. a) V8 cong thitc cdu tao cita cae chit A, B,C va D cook OY. Pina or Joe _ — ba Ho’ ely Tyrosin 7 ‘ HHO, Cyne eae OH Meo. cHo Fe wh ear “CY : He : Vanilin, ‘Trang 7/10b) VE cdu tgo ode chét f, K, L va M iia (me MSO, MOMS Bed Mey AHOOH HRP MO Py Venti eae OC IO Meo KOH Meo’ FEONS tec 1 K 00H 1. BrP mae in ~~ 2.NHs eo Nip xo Ne Md 5 oll : 2. Thy phan X2 bing enzyme A-glucozidaza, thu dugc chét X3 (CsH12Os) c6 cdu hinh D, do 46 X3 bén shit la -D-ghucopyranoag. XS (CsH0«) e6 ngudn géc ti X3, oxi héa bing HNOs, XS tgo thanh axit 2,3,4-trimetoxipentandioic do 46 X3, XS la: HO, 4 HO, 001 yt OMe 00H OH bao ‘OMe OMe Hy coon OMe ue xs itmeso 2,3 4-timetoxipentanioie xs X4 06 nguén géc tir X1, c6 cdu hinh L, oxi héa X4 bing HNOs, thu duge cht yéu la axit (2R,4R)-2,3,4- timetoxipentandioie (I), axit meso-2,3-dimetoxibutandioic va axit axetic nén e6 thé xéc dinh duge lip thé céc nhém OH va b9 khung cacbon, edu tric cla X1 ‘va X4 hoan toan xéc dinh: COOH COOH OMe ou CHO OMe OMe OH OMe OMe 1H Meo- CooH Ho: coor meM 0 sxit(2R,4%).234- —axitmeso ca, trimetoxipentandioic Gimetoxibutandivic x4 XI LRhamnozo fu trite cita X tir duimg L-Rhamnozo, mt dug D-glucozo va quercetin nhu sau: oH on on on HO 0. H m 1 ie OMe 9 y HO OHO Meo. i. Ho Ome 1H a v ad OH OH - aS H a OH oH (Chit y: XI thuge day L nén nhém -OH hemiaxetal c6 edu hinh a khi nim nguge chiéu véi nhém -CH). 3. Ve chu tric cia cfc peptit YI va Y2. Gia thich qué tinh chuyén ha Y thanh Y1 va Y2. HO 4 4 Hoo tpeph NP tre NP te rye ‘pape nye oF, Jo J = ~ Oo Y Og, x HOF Hy? wo 2 ¥ a 4 woe i ae we — ach ie ‘0 oo ‘0 ° Trang 8/10Cha y: Néu HS giai thich vige hinh thanh YI bing céch thily phan lién két peptit ri tao lién két méi thi kkh5ng cho diém. HS giithich vige hinh thanh ¥2 bing céch thy phan nhém amit thi van cho diém. Cau VI (4,0 diém) ; : 1, Cho céc he lrgng tir X: H, Li, B™. Ki higu ning Iugng electron cila m&i hé [& Z,[X] (don vi eV); 7 1 6 lugng tir chinh. Két hgp Ii thuyét véi thyc nghiém, ngudi ta thu duge day gid tri nng lugng cho méi hg nur sau: Ei Ey Ey Day a: BY =340,0 85,00 31,77 Day b: H =13,60 33,40 =1,51 Day ¢: Li*™ 12,4 =30,60 =13,60 8) Chi ra quy vat lién hé (dang biéu thite) gita ,[X] v6i s6 Iuong tir chinh m trong m@i day trén. Tinh E,{X] cho méi day. ) Dua vao bang trén, xéc dinh gif tr nang lugng ion héa cba mbi he. Gai thich, 2. Cho so dé chuyén héa sau: Pb NacHaic.du.t x4 COr yp ddNaOC! yg | SHISOOH. x5 4 x6 eicoomaa | f x 3. e ‘helen gis —o71eOoHgre.e yO i cH:cooH go |#NOsaezndng ~ X5 » long, tanh xe) _Peteind x7 XB +Xx3 Céc chat tir X1 dén X9 déu la hgp chit cia chi. Phan img nhigt phan X2 tién hanh trong binh kin khéng chita kh6ng khi. a) Xéc dinh c6ng thie phan ti cla céc chét tir X1 dén X9 va viét phuong trinh héa hoe cla ee phan img wxdy ra. ») Héa tan hoan toan 0,5 gam Pb:O4 (Myo, = 685 g-mol”) trong dung dich HII dic, du. Bigu chinh pH cla dung djch sau phan img vé khoang 4 + 5 rdi chudn 49 ngay dung dich thu duge bing dung dich 1Naz$:03 0,10 M thi hét Vm. Tinh V. 2 Huéng din chdm 1. a) So sénh timg cp lién nhau hay céch nhau 1 don vj cla sé lugng ti chinh n, thdy qui luat lign he gitta E,[X] v6i s6 lugng tir chinh n trong mdi day trén la: E,{X]=Constin? @, Trong 46 Const la hing sé cita m8i day a, b va c riéng ré. Ap dung quy luat 46, tinh E:[X] cho mi day trén: -Daya): BB“) =-340; [8] =-85,0. E\[B“*] = -340/1 = Const =-340/1 Vay EsB‘) = -340/4? = -21,25 (eV). ‘Trang 9/10Tuong tu, ta 06 v6i ede day b) vac). ~Dayb): — Ey[H] = -13,6 = Const = -13,6/1 vay E.{H] 13,6/4? = -0,85 (eV). Na,[Pb(OH),] + Het Pb +CHsCOOH long — PO(CH:COO), +H:t ‘Naa{Pb(OH)4] +CO, —> NaCO; + POH)! +10 (Tl sinh e6 thé viét X2 la PbCOs hode hén hop PhCOs va Pb(OH),) Pb(OH)+NaOCl_ =~ —+ PbO) +NaCl +H, Pb(OH)2 —> Pbo +H,0 6PbO. + OQ, “+ 2Pb;0, PbO, + 14HI —> 3HA{Pbl] +440 +1: (hoes) H,[PbL.] —*t Polo} +2HI 3PbOz + Pbs0, +O 2Pb3O4 + 12CHsCOOH (Aife, néng) —+ 6Pb(CHsCOO), + 6H,0 + 0) PbsOx_+ 8CH;COOH (Af, lanh) ~—> 2Pb(CHsCO0); + Pb(CHsCOO).+ 8H:0 Pb3O4_ + 4HNO; (lodng, lanh) — 2PH(NO;), + PbO» +2H;0 ») Phan tg cba Pb3O, v6i HI: PbxO; + 1ST” + 8H* —+ 3[PbLJ*+4H,0 +157 w ly +28,0;% —+3r + $02 @). $6 mol Pb3O, trong 0,5 gam la : 7.3.10 mol. Tir (1) va 2) = m(S20;7) = 1,46.10 mol => Y= 14,6 mL. He ‘Trang 10/10