BQ GIAO DUC VA PAO TAO. KY THI CHON HOC SINH GIOL QUOC GIA THPT - a ‘i NAM 2019 Db THI CHiNH THUC Mén: HOA HOC 9 Z Thoi gian: 180 phit (kidng ké thdi gian giao dé) B A N CHINH ‘Nga thi thir hai: 14/01/2019 (Dé thi cé 04 trang, gom 06 céu) MOt s6 ki higu viét tie: Ac: acetyl; AIBN: 2,2! isisobutyronitril; Bn: benzyl; Bu: butyl; CAS: Co(NH,)((SO,) (la chat oxi héa 1 electron); DDQ: 2,3-dielo-5,6- -yanobenzoquinon (la chat oxi hoa); DMF: N,N-dimetylformamid; DMSO: dimetyisulfoxid; Et: etyl; Me: metyl; NIS: N-iodosucinimid; NMO: N-metylmorpholin (Ia cht oxi hod); PPA: acid poliphosphoric; PCC: piridinium clorocromat; PDC: piridinium dicromat; Ph: phenyl; Pr: propyl, TBS: butyldiphenylsilyl; Ts: tosyl; THF: tetrahydrofuran; xt; xii téc; xt [Pd]: xic tde phite Pd Trong cde quy trinh téng hgp hitu co, ¢6 dii cée chat vé co va digu kién can thiét. Cfiu 1 (4,0 diém) : . ‘ 1.1. Dua trén edu tric phan ti, so sinh va gidi thich 46 bén twong di gitta edu dang xen ké va ofu dang che khudit eta phan tir etan, 12, Phan ting cOng gitta CoH, v6i Bro tgo thanh ion bromonium trung gian. Gée tgo béi trye lién két cee vi huténg tuomg tée gitta 2 phan tit khodng 90°, Tuy nhién, khi tién hanh phin ting eéng CN” vio lign két C=0 ctia aceton, géc tao béi hudng tuong téc cua CN v6i truc lign ket 6c.0 Iai xAp xi 107°. ‘Trén co sé ede orbital m lién két va m* phan lign két trong phan tir etilen, aceton va ede gde tong tac duge cho du6i day, giai thich sy khée biét nay, omit: ORY M98 | oe wang te Br: ps rbital x: A oS Jéc trong tée etia Czy va Bry: J BrBr HOO Mel e a ae Ho oH Me, ; neers NO g Orbital x: ih, a8 Gbe twang tée eta aceton va CN": to, wo Me 13, Trén co sé xem xét anh hudng cla cde nhom thé hit electron dén lye acid, hay gan cfc gid tri pKy tuong ting cho céc ion tir dén 7 duéi day. Bidt ring céc gid tr} pK, (xép ngau nhién) cita chting la: 7,5; 0,95 ~0,45 7,9; 10,8; 8,3; 14,5 va lye acid cita 2 manh hon cita 3 NHCONH, nn HON HNO the ok ok Y ok ok HAN? NH, HAN? NH2 — HaN*“NH, HN? “NH, HN SNH 3 4 5 6 i 1.4, Cé thé tach hén hgp ¢6 s6 mol gan bing nhau cita lysin (H2N(CH2)4CH(NH2)COdH), acid aspatic (HO2CCH2CH(NHz)CO-H) va valin (MeyCHCH(NH)CO2H) bing cach héa tan hén hop nay trong lutgng via dit dung dich gm (dd) pH = 6,0 rdi dé vao mét c6t téch chita sin polyme dang [-CHy-CH(p-Cell,SOs1-CH,-CH(Ph)-], trong dung dich dem pH = 6,0 (nhu m6 hinh bén). Tiép dé, thém tir tir dung dich dém pH = 6,0 lén ct tich dé dung dich dém mang theo céc amino acid chay qua, dong thoi thiét lap tong tic va can bing trao déi ion véi khéi polyme. Céc tuong tac va cn bing nay Khée nhau tmg véi mdi amino acid khién ching téch din ra khdi nhau, Neudi ta huing lan uot dung dich chay ra khdi e6t téch bing cde binh khde nhau (goi IA phan oan) va lin Iugt thu duge eée amino acid e6 a6 tinh khiét nhdt dinh trong ede phn oan tuong én, A A A Cho bidt pk, ca acid acetic la 4,75; pK, cia acd p-Me-Cal1,SO3H fa -3,0; py va pg cia valin tvomg img 1a 2,32 va 9,62. Dur dosn dang tn tai va gi thich rin ty ra khdi et tic cia lysin, acid aspatic va valin, Cau Il (3,0 diém) ILI. MGi hgp chit trong s6 10 déng phan lap thé ciia miét din xudt dudmg ©6 thé duge tong hyp qua qua trinh gdm nhiéu bude, di tir glucuronolacton 8D ho§e dong phan di quang 8L cia nd, Trong qua trinh trang 1/4 + polyme Trong cd p= 60chuyén hod nay, edu hinh tia cacbon sé 4 khong thay déi, nhung céu hinh eta eacbon x6 2, 3, 5 e6 thé thay d6i tuy vao digu kign phan tng oy thé rns 620 Nee iS si el, oe oF Non HO on 80 ede sin phém ¢6 edu tric lap thé xée dinh a, Vé cu trtic clia hp chat 8L. b. Vé cf tric cia 10 sin phim e6 thé duge tng hop tiy 8D va 8L. ©. Vé li thuyét, 4 sin phim e6 thé duge tgo thinh tir ed 8D va 8L. Xée dinh (c6 gi thich) 4 sin phim nay. 11.2. Dé xuat eo ché hinh thanh sin phim cho méi qué trinh sau: Np Et 9 Cine cas BI - a 7 Sl oy 10 ae, eee -- ac c ROH 6 et, 1) NaH, wT BR. eee Nv o* ehcHen OH Wteon 0 ‘cote (CS y ange UO he ® Meo” 3) 0% CHCl, CHjC=CH, aceton va ast phan img véi nhaw trong m6i trang kiém, dung moi DMSO tao think 2 chit trang gian a va 9b c6 cing cOng thie phn i CsHyyNO. Trong du kign phn tg, hai chit 9a va 9b ty chuyén thinh hai chat o6 tinh thom 9e va 9d tuong ting e6 cling eBng thite phan tir CoHN. Cho 9e phan tmg voi MeMgCl, sau 6 thm BrCH,CO3Et vao hén hyp phan tmg thi thu drge chét hitu co 10. Cho 9d phan img voi KHCOs va BrCH,CO;Et thu duge chét hitu co 11. VE céng thie cu tao tia cdc chat 9a, 9b, Ye, 9d, 10 va 11. Cfiu II (3,0 diém) IIL1. Nhiéu hop chat thién nhién chtta nhan tropon cé hoat tinh sinh hgc phong phi, a. Tir benzen va céc chat can thiét chtia khéng qué 3 nguyén tir cacbon trong phan ti, dé xudt 0 d6 (¢6 diéu kign phan img) tong hop 4,5-benzotropon (12). OC b. Khir hod 12 bang LiAIH, r6i metyl hod sin pham tao thinh bing hg NaFI va Mel, thu duge 3 chit 13. Hgp chit 13 phin ting voi MeMgl tgo thanh hai dng phan 1S va 16 (phan tir khéi bing 156). Qué trinh chuyén héa nay di qua tién phén trung gian 14, Sau d6, 14 tiép tye phan tmg tgo thin 15 va 16. Vé cng thite edu tao eita 13, 14, 15 va 16. Giai thich sy hinh thinh 14, 1112. Eugenol la hop chat thién nhign c6 nhiéu ting dung trong yo, t6ng hop hitu eo va duge phim. aS a. Hop chit 17 1a sin phdm trung gian trong téng hop Afrilo, mot Meo” cchat tie ché enzym GSK phosphatase. Tir eugenol, hay d Eugenol dé (cé diéu kién phan ting) ting hop chat 17. i b. Cling tir eugenol, ngudi ta da ting hop duge hyp chft 21 theo so dd chuyén hod sau: 1) TBS-CI, imidazol 4) H0, H® PhNHNHg 1) BuNF Eugenol 18 PEC 19 20 S 21 2) NaOH, © ie PPA, t 2)H40% 6 ygNO ‘Ve cong thite cfu tao cia cée chit tir 18 dén 21. TIL3. Cac hgp chit dj vong tir 22 dén 24 duge didu ché theo so dd sau: NH anhydrid sucinic SOCI, ELOH K,CO3, OMF 2 23 =e 24 en, CICH,COZEt Pere CraHNeOp Bee CigHaoNzO4 trang 2/4Cho biét quy tinh diu ché chat 22 tir o-phenylendiamin va quy trinh diéu ché chat 24 tir chét 23 hur sau: - Diéu ché chét 22: Dun hdi law o-phenylendiamin, anhydrid sucinic va xylen trong 3 gid. Lam lanh, gan lay ket tia dem hda tan trong dung djch HCI 1 M6 60°C. Lm naugi va lge bo phan cin, thu léy dich loc cchita chat tan (hiru co) X. Sau dé xtr lf dich Igc nay bing NaOAc dén pH = 6 thi két tia mau tring duge tao thanh, Loc ly ket tua, Lam khé thu duoc n phim 22. - Diéu ché chdt 24: Tién hanh phan img gitia chat 23, K>COs khan va CICH:CO,Et trong dung méi DMF khan, 6 digu kign khan (sue khi No két hop véi ngan hoi am bing CaO). Khi phan tmg két thite, thu lay hop. chat 24, a, Vé cong thite edu tao cita cfc chit 22, 23 va 24, 1b, Hay gidi thich va vé cdng thirc cdu tao cda chét tan X Hay cho biét vai tro ctia KxCO, khan trong qué trinh diéu ché chat 24. Tai sao trong qua trinh nay, phai tin hanh phan img trong diéu kién khan? Caw 1V (3,0 dién) IV.1. Tir chat 25 dudi day, ngudi ta digu ché duge chat 30 theo so dé chuyén héa sau: Bn Br 09 Bn, Pcc PhsP=CHCO,'Bu Nis "BusSnHt Meo! re on POC, Pha a7 28 9 EOF nc 30 WO MeOH AIBN. He 25 MeO“ ~oMe Ve cong thite céu triie cita ede chat tir 26 dén 30. : , 1V.2, Peribysin (31) lt hop chat c6 hoat tinh sinh hc. Hp chit 31 duge tng hop theo sod sau: 9 1) 32, BF5*Et,0, < 25°C Hz, (PhgP)sRhCI Ph3PMeBr, THF ZA DO op TPR 35 - ‘Me 2) KOH 15%, MeOH benzen, -25 °C. 'BuOk, 0 °C Meteo 1) SeO2,'Bu00H 1) Ac,O, EtyN H202, NaQH, Eon HOCH yg UAHOEWN 5, 1hO,NEOH 4 38 2) NaBHy, CeCls 2) PDC, 'BuOOH MeOH, 25 °C oO OH NaBH, p-TsCl, EtN 0804, NMO 385 — + 39 40 MeOH, 25 °C. 'BUOH 38 ~ Peribysin (31) a, Cho biét 32 1a (E)-2-metylbut-2-enal, Tir cdc chét cung cap khéng qua 2 nguyén tir cacbon (ché chira nhigu hon 2 cacbon nhung chi str dung khdng qué 2 caebon vio phan img), hay d8 xudt sod t hop chat 32 (c6 diéu kign phan img) b. Vé céng thite céu tao ctia chdt 31 va cae chit tir 33 dén 40. IV.3. Chat 41 duge ting hop theo so dé sau: e 43 by 1) KOH, H20 Ag2CO,, Br, "BugSnH PINS tae gg MONO. pg MOO By "BusSOH gg e 25°C CiaHyoBr0, 2) HO AIBN CroHi2 Biét ring, chat 41 1a hop chat bao hoa (no) e6 2 mat phiing d6i ximg, chtta 4 logi hydro va chi chita cacbon bic 2 va bie 3 vai ti 1é tuong tmg 1:43 chat 43 (CoH2B1202) chi chita Cy? vacé tam déi xiing, VE cng thite cdu tao etia cde chit tir 41 dén 47, Cfiu V (3,0 diém) V.1. Hop chat Furoclausine-B (48) duge phan lap tir eée duge liga truyén thong, 6 tée dyng chtta nhigu bénh viém nhiém. Hop chat 48 duge tng hgp ton phan theo so dd sau: 1) (CF,CO),0, EtN H, er {CO3H eg Fees e ON TUT oe ta Pest tn si VRCOH A 2) 2-metyl-5-nitrophienol; xt Lindlar 140°C 2) KOH, Mé Me ‘CuCh+H,0, EtyN 4 (=o ° aaa 8 owe x IP u(OAelz, Ciotuno, * Pz TPA C2005 aNOSSi MOAC)a, trang 3/4cHO DDQ BuyNF a 55 aS og \ 73 on Furoclausine-B (48) Cz7HygNO3Si ‘N K, HO q me"? ‘Vé céng thite edu tao eiia cde chat tir 49 dén 56, V.2. Hap chit $7 (Cirt1g03) la chat tw v8 ctia mét s6 loti céy, Thay phan chat 57 véi enzym p-glycosidase thu duge chat $8 (CyHé0s) va D-glucose. Chit 58 c6 thé duge téng hyp theo so dé sau: 1) BnBr, KxCO3 1) Mg/Et,0| 1) Hp, Pale 1).CO, HCL Paic o Dea HA oD) sock, EN 3 ae ) Br, x 2) Aa Ho! NSOCRERN gg, 12) Ac,0, ACONa, ® Biét ring chét 59 (CoH,O2) c6 tinh thom, chtta 4 loai hydro trong phan tir, ¢6 phan img tgo mau die trang voi dung dich FeCls va khéng e6 phan img dc trang véi phenylhydrazin, Khi dun néng trong nude thi chat 57 bi dng phiin hod thinh chat 64. Thy phan chat 64 vi enzym feglycosidase thu duige chét 65 (CurF0)). Bun néng chat 65 trong moi trudmg acid thi thu durge chat 58. a, Vé cong thite céu tao cita cdc chat tir 58 dén 63 va céng thie edu trie cita chét 57. b, Diing céng thite edu tgo, vé so dé giai thich qua trinh chuyén tir chat 57 > 64 —> 65 > 58, V.3. Hyp chat Sinigrin (66) c6 trong ea gia vj hoge mit tat. Chit 66 & dang mudi kali, phan tit khdi nho hhon 500, chita 30,22% C, 4,06% H, 3,52% N, 36,23% ©, 16,13% S theo khOi long, con Iai la K. Thiiy phan chit 66 bing enzym f-glycosidase tach duge dudng D-aldopyranose (67) va hoat chét 68 (chita 20,42% C, 2,57% H, 5,95% N, 27,20% O theo khdi lugng, cdn Iai lA K va $). Hogt chat 68 dé dang phan hiiy theo co ché twong ty phan ting chuyén vj Beckmann tgo thinh isothiocyanat (R-NCS) 69 mach h (chita 48,45% C, 32,34% S theo KhOi rong, con Iai la H va N; ti Ié cc logi nguyén tir hydro la 2:1:2). © cu dang bén, chit 67 chita ci nhém thé déu 6 dang equatorial, a. VE cau tric ca cdc chit tir 66 dén 69. b. Dé xudt oo ché phan img tir chat 68 thanh chit 69, Biét C = 12,01; H= 1,01; N= 14,01; 0 =16,00; S = 32,06. Cau VI (4,0 diém) Vi. a, Vé cdiu trie hinh hoe ctia ede phan tir sau: BCls, PCls, NCls (biéu dién cd céc e€p electron héa tri khéng tham gia lién két ciia nguyén tit trung tam, néu c6). b, So siinh va gid thich g6e lign két CIXCI (X 1B, P, N) eta cde phan tir BCs, PC vaNCls. ¢. Giai thich tai sao trong pha khi, phan tir PBrs kém bén hon PCls. 4. Khi ngung ty hoi PCls thu durge pha rin la hgp chit ion (PCL]"[PCL. VE edu tric hink hoc cua ede ion [PCle va[PCL). V1.2. Trong co thé, hemoglobin (Hb) ¢6 vai trd vn chuyén Op tdi ede té bio. Co @ thé bj ng6 dc khi CO do sy hinh thanh phite chét HbCO, kim gim hrong Hb. Hinh bén md ta hgp phiin phic chit duge to thinh gitta CO va trung tam hoat dong chia Fe cia Hb. Khi lvgng Hb trong méu mat di khodng 25% thi sé gay nh huémg nghiém trong t6i tinh mang. Cho biét cdc efin bing ciia cdc khi O2 vay CO v6i Hb trong méu nh sa (1) Hb +0; = HbO, — K;=60 (2)Hb+CO = HbCO K>=1,5.104 a, Giai thich tai sao phite chat HbCO bén, ct ie b. Xét mot hé cén bang chi gdm hai phan img (1) va (2) etia Hb véi khéng khi bi 6 nhiém (gia thiét 06 21% Op vé thé bang trong khéng khi khi 25% Iutong Hb bi chuyén hod thanh HbCO. Bigt Zp=5, Zy= 7, Zp= 15, Ze1= 11, Zee = 26, Zar = 35; Ap sudt Khé quyén 1a 1 atm. -HET- © Thi sinh khong dage sit dng ti ligu; * Cain bG coi thi khong gid thich gi them. trang 4/4,