BQ GIAO DYC VA DAO TAO KY THI CHON HOC SINH GIOI QUOC GIA TRUNG HOC PHO THONG NAM HQC 2022 - 2023 DE THI CHINH THUC Mén: HOA HOC ‘Th6i gian: 180 phiit (khong ké thai gian giao dé) Neay thi: 25/02/2023 Dé thi gdm 04 trang, 06 cau Cle cht va it hig vide tit Ac: acetyl; AIBN: azoisobutyronitrile; Bn: benzyl; n-Bu: n-butyl; DIPEA: N,N-diisopropylethylamine; DMAP: 4-dimethylaminopyridine; DMF: N,N. DMSO: di 3 Et: ethyl; Me: methyl; NBS: N-bromosuccinimide; Ph: phenyl; ‘Pr: isopropyl; TE trifluoromethanesulfonyl; THF: tetrahydrofuran; Ts: tosyl; dd: dung dich; dk: diéu Ki VSEPR: lute day gitta céc c&p electron vé héa tri. Cho: O = 16,0; F = 19,0; As = 74,9; 1= 1269; 21= 53, : Trong cc quy trinh tong hop hitu co, cé di cée chét v6 co, dung méi, xtic tée va diéu kign can thiét. Cau I (3,5 diém) 1. Cho céc chit 6 céng thite sau: Mew Me NMe, Me;N NMe2, é “oo wmarketa ‘oO ‘Oo AL AB Ad AS AG a) Vé cn bling gitta 2 déng phan cdu dang ghé, xéc dinh cdu dang bén hon va gan ki higu R, S cho timg déng, phan lap thé cia Al. Biét: tuong téc cia 2 nhém methyl in dm quyét dinh dén 46 bén cia céu dang. b) Cho gia tri pKa ciia acid lién hop voi A2 va A3 lan lugt 18 5,1 va 12,1. Gidi thich tinh base cao bat thuéng lia A3 so véi A2. ee ©) Cho gié tri pX, (img véi nhém -NH-) cia A4, AS va AG trong dung moi DMSO (xép ngdu nhién) 18 25,4; 20,7; 26,6. Gan gid tri pK, cho timg chat Ad, AS va A6. 2. Tong hop va nghién citu tinh chit dic bigt cia céc phén tir e6 site eding lon Ia théch thie va thu hit sy quan tm cia céc nha héa hoc. a) Cho so dé sau: HCI oe e ‘Biét: B2 06 céng thire phan tit CsHs va chi chita | loai hydrogen. Vé cing thie edu igo cia Bl va cdng thie edu trie eta B2. Goi ‘én B2 theo danh php TUPAC. b) Hydrocarbon [4,5]coronane B3 chia vng cé sie cng 1én durge ting hgp theo so 48 sau: seMe Ouco x 1180 t 2 SeMe Ary 804 + BA SeMe BS Bo OOD esto Mm ‘oseme AlOs ‘Ve céng thite cdu tao cila cdc chit tir B4 dén B6. Bids: BS chita mét vong 5 canh (duge tao thinh tuong tr chuyén vj pinacol), : ; ; 3. Tlludinine 6 nguén géc thién nhién va duge tong hop theo quy trinh sau day: ‘OMe acyl héa hydrocarbon thom C1 véi 3-chloropropanoyl chloride (CxHsClO) ¢6 yy oO mit AICL, thu duge C2 (CrHisCl0). Dun nong C2 c6 mit HaSOs, thu duge HCI va C3. Alkyl héa C3 voi luong dur Mel, c6 mit K2COs, sau dé khir héa Clemmensen v6i Zn vi AcOH, thu duge C4 (CrsHs). Brom héa C4 véi luong dur Bro 6 m&t AIBrs, thu due C5 (CisHieBn). Cho C5 phan img véi n-BuLi N 2H,C=CH By S-Ni _HNOs oO pe + 3Ny +HCI NEN Cy7Hp40 C7Hy40 COOH cl illudinine Trang 1/4theo ti 1@ mol 1:1, sau 46 v6i B(OH) va cudi cing véi H2Oz, thu duge C6 (CuHiyBrO). Methyl héa C6 boi Me2SOx 6 m&t K2COs, thu duge C7, Cho C7 phan tmg voi Mg trong dung méi tro, sau 46 véi CICOOMe, thu duge C8, Oxi héa C8 bling CrOs, sau dé khir héa voi NaBHs, thu duge C9 (Ci7Hz04). Dun néng C9 c6 mat H2S0s din dén téch H2O, thu duge C10. Oxi héa cit mach C10 sir dung hé téc nhén OsO4/HIO,, thu duge C11. C11 phan tng vii NHsOAc, sau 46 thy phan trong dung dich KOH, ‘Biacidhéa, thu duge iludinine. Vé cong thite cdu tao cla cdc chit tir C2 dén C11. Au II (2,5 diém) Vé co ché dé xudt cho cdc qué trinh chuyén hod sau: 1 ae Ph = COOH Ph > W aon NT I et nd fe = ° NN. yom, ‘pp == Me™ “COOH VOW ‘Pr Biét: MeCOCOOH nim cén bing voi dang enol khi tham gia phn {mg véi imine trung gian. Me BT 2 i Me H,S0¢nSOs_ 200 a xf 4 1) mBubi _ THE a De Caen (Khong yéu aT ve hi . co ché phan img v6i oxygen) Biér: giai dogn dau tién n-BuLi phan tmg voi hydrogen cia | Biét: chuyén héa c6 tao thanh trang gian cht nhém H-C=c-. nhém chife alkene va trung gian SO3H". CAu IIT (3,0 diém) 1. Quy trinh tng hgp D1 duge mé ta nhu sau: Cho D2 phin tig véi Ac2O 6 mit K2COs, thu duge D3 (CixHsNO.). Thiy phn D3 bing dung dich NaOH sau 46 acid héa, thu duge D4 (CriHinNOs). D4 tham gia phan tmg déng vong véi sy ¢6 mat cia AICIs, thu duge DS (CyiHNO,). DS phan img voi PCs, thu duge D6 (CusH>CLNOz). D6 phan tmg v6i D7 (D7 duge tong hop tir diethylamine va aziridine), thu duge D8 (C1zH22CIN;O2). D8 phan tmg voi MeOCH2CH2CH20Na, thu duge D1. eens ; Meo" N70 ome Me y DI D2 ‘Vé cong thitc cdu tao cia céc chét tir D3 dén D8. 2. a) Vé co ché dé xudt cho phan tmg cia phenol véi 2-(chloromethyl)oxirane (CsHsC1O) ¢6 mat K2COs. b) De xudt mot quy trinh téng hyp El tir 2-hydroxyphenol, Mel, 2-(chloromethylJoxirane, piperazine (CsHioNz, chia vong 6 canh va 2 nguyén tir nitrogen & vi tr 1,4), 2-chloroacetie acid va aniline, 3. Dé xudt mot con dudng tng hop E2 tir ethanol, acetic acid va benzene. Cau IV (4,0 diém) 1. Pumiliotoxine C dugc phén lép tir da cia loai &ch Dendrobates pumilio va cing duge téng hop theo so 48 sau: iS BACh Gy Edn = i G3 Mati N e ‘CHa c CisHiyNO Cy4tlgiNO, —™? CyaHlagNO2 bo oe Me © nyt. Oe os stu 6 cant : 4-NH — CigHgNj02S IB C\sHz7NO CisHaNOr ushiod AIH CwtsN02 Ha as ‘Ve céng thite cdu tao ciia cdc chit tir G1 dén G6. Biét: phan tmg khir héa GS thanh G6 xay ra theo co ché géc nr do. Trang 2/42, Alkaloid H9 la m6t hoat chit sir dung trong nghién ctu y duge. H9 duge ting hgp theo so dé sau: Mt Brno: ou oe gy HACECHMABE 4 _ Cll yy Meuitcat Me “cro bbe COOH CH yyNO2 cyto “° ¢ \ Cats thay thé nhdmm O1F fing nhém Ny, 1) 0y/Me,S. iAlHy yg NUBOH yg _DlngaHIMN arg ve Mes ay OH yg Lal i . CogHa0, Cray CypHaNO7™* Cygtig;NyO2 — CigHayNOp HO Ve céng thire cfu tao ctia cde chét tir H1 dén H8. Biér: HS chira nhém chite ketone; H8 la san phdm chuyén vi va c6 chira 2 vong 6 canh. 3. Berberine duge phan Ifp tir efy Vang ding, Hodng bé va Hoang lién. Berberine 18 thude thio duge ola Vigt Nam, duge st dung kam thude chéng tiu chay va thude nhé mit, gin day duge phat hign c6 kha nang Z ie chéng viém va bio vé than kinh, Berberine va din xuat cia né cling Meo on fe v duge téng hyp theo so dé sau: OMe | Sct Tesbeine one, 1) MeOCH,PPAyC! ? ia CBra, PPh: TC mBuli La NH, pp NBS yg SB PPhy 1g L i ‘. ~ mf 2 HCUE,O, # Cotty003 THE CgHgBr,0,°20> ® CapHigBINOs Pd(OAc), 1) Khir hoa NaBH, 1) BBrs, CHCl Duraano” berberine L7 18 CagH;Nog HOURS CapHayNOg 2™° ———CygHlgiNOg a) VE céng thite cdu tao ca cdc chat tir L1 dén L8. Biét: Pd(OAc)y/DIPEA/PPh; xtic tac cho phan img dong vvong nd phan ti ») Dé xuat so dé tng hyp L tir céc chit 2,3-dimethoxybenzoic acid va 2,2-diethoxyethan-1-amine. 4. Daldinin A téch tir nam Daldinia concentrica cé hoat tinh khéng virus HIV va géy dc té bao ung thu. Daldinin A efing dugc ting hgp theo so dé sau: DIPEA, PPh, Pea NaBH, wove tg BCOOC yyy ann yy tal KC Tce i onc—=—cH,cx,cu, ™* CisHiOs “——Cigttan7 CiotieOs oH og Me Me’ 0, or M4 _CHhONa| Mg __LIOH M6 _DCH,COCH, As CysHygO, CHOH” CyHy,0, DMSO.HO” CyyHj0, DH CHO et daldinin A ‘Vé cong thite cu tao cla cdc chét tir M1 dén M6. Biét; M1 chira vong 6 canh, phan img oxi héa M2 thanh M3 tai lién két C-H no cia nhém benzyl. Cau V (3,0 diém) : 1. Cyanoglycoside X 1a chat phong vé cia mét sé thyc vat chéng lai con tring theo co ché gidi phong HCN. Thiiy phan hodn toan X trong mdi On Vagoee gta trutmg acid, phan lap dugc carbohydrate X1 (CsHio0s) va X2 (CeH120¢). cial On Soe a) Vé céng thite chiéu Fischer (Fiso) dang mach hé ciia XI va X2. ba on om b) Dang mach hé cia X1 nim trong cn bing véi céc dang mach vong x hemiacetal furanose tuwong img. Vé cng thire Haworth (Havooc) cita cée dang mach ving furanose o6 thé e6 cia X1. ©) X1 phin img véi phenylhydrazine tao thanh phenylosazone X3. V8 cdng thie chiéu Fischer cia X3 va cho biét X3 c6 hoat déng quang hoc khong? 2, Alaloid thién nbién vindoline (CasHs4N2O¢) c6 hoat tinh chéng ung thu. Vindoline duge tng hgp theo so 4 sau: Trang 3/4Et OxpNHONH eine Ni bese} yr BChEBN, yo wooc/*-o8p y3 e fer x S53 CD CrotlaoNs0: CretlrsNsO, Cag aNsO, Meg QLD CretaNiOs 16HlygNuOx s0FlgNsOe, 8 cod be bscits YS sia Y6 eee vindoline : NaBH, Meo WL rOBn —2)Acx0 Cag HygNyO7 CasH32N207 * Cassis Y4 Me COOMe : a) Ve cong thire cdu tao ia ede chat Y1, ¥2, Y3, Y5, Y6 va vindoline, Biét: phan tmg chuyén Y1 thanh Y2 1A qué trinh déng ving 5 canh chita oxygen va nitrogen; Y6 va vindoline chtra nhém chire alcohol bac 3 bén. b) Ve co ché dé xudt cho phan img chuyén Y3 thinh Y4. Bids: phan tg di qua giai doan [4+2], sau 6 hinh thanh trung gian 1,3-ludng cue do téch loai No. 3. Mét sO tien chat thudc vugt qua cée enzyme phan hily cl thudc trong hé tiéu héa va tudn hoan dé dén té bao dich. Tai O O coon é, ching chuyén héa thanh thudc hoat d6ng. Sau khi thye 00H hign cdc chite ning, hoat chat thuéc duge chuyén héa va dio. on thai ra khdi co thé, Ny? a Z la tién chat thudc qua dudng uéng, Z bj thiy phan chon oy i OF on lgc, sau 46 dong vong tao thinh ZA (CisHi2CN2O, c6 hoat ° Zz ZA tinh an than). Z1 bj oxi héa é lién két C-H tai carbon a cia nhém carbonyl, tao thanh Z2 (CieHi2ClaNaOa, chita nhém -OH). Z4 tao lién két P-glycoside voi Z2 thanh Z3. Z3 duge dao thai qua duing bai tiét. Vé cng thire cdu tao ctia cdc chat tir Z1 dén Z3. Cf VI (4,0 diém) 1. a) Dya vao thuyét orbital phan tir: i) Viét cdu hinh electron, tinh bac lién két cia I: va ion lo* (coi gidn dé orbital phan tir cia lp va ion I2* twong ty gidn dd cia F,). So sinh d6 dai lién két I-I trong Ip va ion In". 2 if) Giai thich tai sao ion Ip" c6 thé dimer héa tgo thanh ion 14? va ion Ie? 06 2 loai d9 dai lién két [-I khée nhau. b) Cho so dd ben: 6,07, Bié: U1 dén U10 déu chia fae nguyén t6 halogen U; Ul 1a don chat 6 thé rin trong diéu kign thug va lam déi mau hd tinh 6t; Ud c6 dang hinh chit T (theo thuyét VSEPR); U7 c6 mau ving, ft tan trong nude; U9 chira 22,10% oxygen vé khéi long; U10 chi SnCl, HCH loting 15 dd Cl, v10 chita m@t cation chiém 57,33% ® M ~~) (10) vé khéi Iugng, cation nay duge tgo nén tir 4 nguyén tir halogen U. ae i) Xac dinh céng thite héa hoc ctia cdc chat tir U1 dén U10. if) Vidt che phuong trinh phn tmg tte (1) dén (10) va cho biét vai trd cia U1 trong timg phin tmg (4), (5), (6) (7), 9)» (10). 2, Dung dich Fe** dé trong khéng khi cé thé bi oxi héa thanh Fe?” bai oxygen hda tan. a) Dung dich A chita Fe** 0,010 M va H’ 0,50 M. Bang tinh ton hay dnh gid kha nang oxi héa Fe” trong dung, dich A Khi dé cn bang voi khong khi. Coi si oxi héa I’ hodn toan khi néng dé cén bing lia Fe** nhé hon 10° M. Cho: G 298 K, £Ps. 43 = 0,771 V5E6, surnyo = 229 Vs 2,303R7IF = 0,0592; Or) = Onan K =107;, 4p suat riéng phan ciia O2 trong khéng Khi 1a 0,208 atm. ap b) Dung dich A sau mét thai gian 4é trong khng khi duge ding lam thi nghiém, Syc ding khi Nz dé dudi hét hi Oo trong dung dich A. Thay ring, khi thém ti tir dén 0,50 mL dung dich chita SCN” 0,01 M vio 10,00 mL, dung dich A thi dung djch chuyén thanh mau hong cita phire FeSCN**. Tinh %Fe** trong dung dich A da bi oxi héa thanh Fe 6 thoi diém léy lim thi nghiém. Cho: [FeSCN*] > 9.10°° M thi quan sat thay mau hdng; FeSCN** cé lg = 3,03; HSCN cé pKe = 0,89. Gia thiét cc thanh phan khéc va céc qua trinh khéc la khong anh ng én © Thi sinh KHONG duege sie dung tai ligu; ‘© Gidim thi KHONG giai thich gi thém. ‘Trang 4/4