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Advanced organic chemistry exams

Ti liu n thi hc sinh gii quc gia mn Ha hc (dnh cho hc sinh THPT)
HA HC HU C
BI TP XC NH CU TRC HP CHT HU C
(Ti liu n thi hc sinh gii quc gia mn Ha hc)
Bi 1
Paracetamol hay acetaminophen l mt dc cht c cng dng lm gim au v h st, c Harmon Northrop Morse tng hp nhn to ln u tin vo nm 1878 v c Bernard Brodie cng Julius Axelrod thuc s y t New York a ra ch trng s dng trong iu tr t nm 1948. Sn phm paracetamol u tin c McNeil Laboratories bn ra nm 1955 nh mt thuc gim au h st cho tr em vi tn Tylenol Children's Elixir. Sau ny, paracetamol tr thnh thuc gim au h st c s dng rng ri nht vi rt nhiu tn bit dc c lu hnh. V n c rt t tc dng ph vi liu iu tr nn c cung cp khng cn k n hu ht cc nc.
C mt chui phn ng ha hc c thc hin t cht A (cho trn) nh sau: Khi A phn ng vi O3 trong nc th cho hai hp cht B v C. C hai u phn ng vi PCl5 trong nc cho D v E tng ng. D c th phn ng vi paracetamol cho F v G. Hp cht E phn ng vi paracetamol cho H. Hi cht F cho i qua AlCl3 khan th thu c cht I. Trong s c mt ca HF + SbF5 th cht H ng phn ha thnh J v K. Khi un nng I trong axit sunfuric long th to c cht L. Trong cng iu kin th c J v K u to thnh L. Xc nh CTCT cc cht v cho bit vai tr ca HF + SbF5.
Ti liu c bin son bi cc thnh vin box Ha hc Olympiavn, yu cu khi sao lu ti liu hy gi nguyn biu tng ca din n. Nhng kin ng gp xin gi n hm th hoahoc.olympiavn@gmail.com. Xin chn thnh cm n!

Bi 2
Shikonin l hp cht c mu c tm thy r ca cy Lithospermum erythorizon mc Chu . Mt on r c s dng trong nhiu th k lm bi thuc dn gian v ngy nay c s dng lm thuc m cha cc vt bng. Shikonin c cng thc cu to nh sau:
Mt chui phn ng t shikonin tng hp nhng dn xut c hot tnh sinh hc tt hn c trnh by nh sau:
Mt dn xut c ch khc ca shikonin cng c th tng hp theo s sau:
Hy xc nh cng thc cu to ca nhng hp cht ch mi c k hiu bng cng thc phn t trong hai s phn ng trn.
Bi 3
R gng c bit nhiu v mt dc tnh v nhng tnh cht ca hng liu. Ti Ayurveda (Ni c truyn thng v thuc n ), rt nhiu n thuc c s dng gng nh l mt v thuc tr cc bnh lin quan n rut, cm lnh thng thng v mt s bnh khc. Mt vi hp cht c coi nh l nguyn nhn gy ra v cay ca gng. Rt nhiu trong s l nhng dn xut th n gin ca vng thm vi di mch c khc nhau.

Mt trong nhng dn xut quan trng nht l Zingreon c cng thc phn t l C11H14O3. Hp cht ny khng cho phn ng vi thuc t Tollens nhng c phn ng dng tnh vi FeCl3 v 2,4-initrophenylhirzin. Brom ha Zingeron bng dung dch nc brom ch thu c duy nht mt sn phm monobrom. Trong phn t Zingreon v sn phm kh ha theo Clemmensen u c lin kt hiro lin phn t (yu). a) Xc nh cng thc cu to ca Zingreon da trn nhng d kin cho. b) Zingreon c th c tng hp theo s sau:
Hy xc nh cng thc cu to ca A. c) Zingreon c th d dng chuyn ha thnh Gingerol c cng thc phn t C17H26O4, cng l mt hp cht gy ra v cay c tm thy trong cy r gng bng s sau:
Hy xc nh cng thc cu to ca B v Gingerol.
Bi 4
(-)-Atractyligenin l mt hp cht hot ng sinh hc c c lp t cy Thistle cht chc, mt loi cy c hoa c c th tm thy Scotland. Ngi Zulu dng n cha bnh nhng thng gy him ha cht ngi.
(-)-Atractyligenin

c th to mt hp cht tng ng c c tnh km hn, nay c nhiu phng php tng hp ha hc:
Xc nh cu trc ca cc hp cht B,C , D, E, G, H, I. Bit I c cha nhm cacbonyl.
Bi 5
S pht trin ca cc loi dc phm mi ph thuc ch yu vo tng hp hu c. Phng php chnh li phn t (fine-tuning) c s dng c th nhn c cc tnh cht nh mong mun. Sau y l qa trnh tng hp thuc gy m cc b proparacaine (hay cn c gi l proxymetacaine), cht ny c s dng iu tr cc bnh v mt.
(Tt c u l sn phm chnh) Hy xc nh cng thc cu to ca cc cht A, B, C, D, E trong s tng hp trn.
Bi 6
Nm Aspergillus nidulans hay cn gi l Emericella nidulans, l mt trong rt nhiu loi nm dng si ca lp nm ti. Nm Aspergillus nidulans to ra hai lacton (este vng) thm A v B (C10H10O4) mi ng phn tan trong dung dch NaOH lnh trong nc nhng khng tan trong dung dch NaHCO3 trong nc. C A v B u cho mu tm vi dung dch FeCl3 trong

nc. Phn ng ca A vi CH3I c mt K2CO3 to thnh C (C11H12O4) m ph 1H NMR ca n thy c cha ba nhm metyl khng ging nhau, mt nhm lin kt trc tip vi vng thm. S tch loi nhm metyl c chn lc ca C vi BCl3 ri x l k tip trong nc to ra D l mt ng phn mi ca A. Ph 1H NMR ca hp cht D cho thy r s hin din ca mt nhm hydroxyl c to lin kt hydro ni phn t.
Hp cht D c tng hp nh sau: Phenol E c metyl ha (MeI/K2CO3) to F(C9H12O2) sau F c kh bng liti kim loi trong amoniac lng v 2-metylpropan-2-ol cho mt dien i xng v khng lin hp G. C th chuyn dien ny thnh lin hp bng phn ng vi KNH2 trong amoniac lng ri x l k tip trong nc, qa trnh ny ch to mt sn phm H. S ozon phn H ri x l khng kh l tip to ra nhiu sn phm, trong c xetoeste I. Thc hin phn ng Diels Alder hp cht H vi dimetyl but-2-indioat J to thnh K (C15H20O6) m khi un nng s loi eten to ra mt este thm L. Thy phn L trong mi trng baz ri axit ha dung dch to thnh M(C11H12O6) m khi un nng trong chn khng to ra N (C11H10O5). Kh N bng NaBH4 trong dimetylfomamit to thnh C v mt lacton O ng phn, O cng c th thu c nh metyl ha B. Vit cng thc cu trc ca tt c cc hp cht t A n O.
Bi 7
Mt trong nhng yu cu ban u cho s pht trin cc iot pht x nh sng hu c (OLED) l s tm kim vt liu pht quang c hiu qu cao m c th l nhng phn t nh hoc nhng hp cht cao phn t. V d nh floren, mt biphenyl cu ni metylen, c hiu sut lng t hunh quang cao hn biphenyl. Nhiu dn xut floren c pht trin, chng c tim nng ng dng trong cng ngh mn hnh phng. trnh s tng tc gia cc phn t, cc nhm th ln c a vo v

tr C9 ca fluoren. Mt v d ca trng hp ny l hp cht C, mt pht minh v vt liu pht x nh sng xanh c hiu qu cao rt th v v b ch. Di y l gin tng hp cht ny.
Bi 8
Nm 1981, S. Itsuno v cc cng s ca ng l nhng ngi u tin bo co thc hin thnh cng th nghim kh xeton tng ng khng c tnh quang hot thnh ancol bc hai quang hot bng cch s dng hn hp i xng ca amino ancol v phc ca BH3 trong THF vi mt hiu sut rt cao. Vi nm sau , E.J.Corey ch ra c rng phn ng gia amino ancol v BH3 trong THF dn ti s to thnh cc oxazaborolidin. Cht ny c tc dng xc tc chn lc lp th v lm tng nhanh tc phn ng trong s c mt ca BH3 trong THF. Phn ng kh tng hp bt i chn lc xeton ny c gi l phn ng Corey - Bakishi - Shibata.
T ancol quang hot trn, ngi ta thc hin mt chui phn ng nh sau:
Bit rng A c cng thc phn t l C8H6OCl2, C c cng thc phn t l C8H9NO2 v B c cu hnh tuyt i ging A. Xc nh cng thc cu to ca A, B, C (ch ha lp th). Gii thch s hnh thnh cc sn phm B v C.

Bi 9
Nm 1966 Saturo Masamune thc hin mt chui phn ng xut pht t sn phm cng anhirit maleic vo xiclooctatetraen. Cu trc ca sn phm cui ny c xc nh chc chn nhng Masamune vn cha bit nn t tn cho n l g. Trong mt ln i ung cafe cng cc ng s, Masamune nhn thy mt gi tri cy trn bn c hnh dng rt ging vi hp cht mnh tng hp c, ng bn t tn cho n l basketen (xut pht t basket - ci gi). Hp cht m Masamune tm ra c th tng hp nh sau: t sn phm ca anhirit maleic v xiclooctatetraen, chiu x t ngoi hp cht cng trn to ra anhirit A. Thy phn anhirit A bng Na2CO3 sau trung ha bng HCl thu c mt hp cht B, trong B tn ti lin kt hiro ni phn t. Di tc dng ca ch tetraaxetat Pb(OAc)4 cht B bin i thnh mt hirocarbon vng. Qu trnh trn c th tm tt trong s sau:
O O O to O O O hv A i) Na 2CO3 ii) HCl Pb(OAc)4
a) Hiro ha hirocacbon nh xc tc Lindlar thu c mt hirocarbon mi c tn 1,1' bishomocuban. Hy v cu trc phn t ca hirocarbon mi ny . b) Xc nh cu trc ca cc cht A v B.

Bi 10
Antihistamine (khng histamin) c s dng lm gim nh hng ca cc tc ng d ng trn c th. Dc cht fexofenain (fexofenadine) c dng cha chng ht hi, nhy mi v nga mt do d ng phn hoa, m khng gy bun ng. Fexofenain c bn trn th trng nh mt loi mui hiro clorua. Cho s tng hp v cu trc km theo ca fexofenain nh sau:
O CN MeI MeONa A MeI Cl B AlCl3 Cl C NaBH4 D COOH HO NH H3C O O
RMgBr
i) RMgBr ii) HCl
HCl to
OH R
f exof enadine
Cho bit rng: Cng thc phn t ca A l C9H9N Cng thc phn t ca B l C10H11N Cng thc phn t ca C l C14H16ClNO Cng thc phn t ca D l C14H18ClNO Cng thc phn t ca E l C6H10NOR (R = gc hirocacbon) Cng thc phn t ca F l C6H11NOR2 Cng thc phn t ca G l C20H28N2O2R2
Da trn cc d kin cho, hy xc nh cng thc cu to ca cc cht t A G trong s tng hp cho.

Bi 11
Vo thng 9/2004, cng ty dc phm Sanofi-Synthelabo gii thiu mt hp cht c kh nng chng li bnh bo ph v chng nghin thuc l. Cu trc ca dc cht rimonabant ( c bn vi tn thng mi l Acomplia) c a ra sau y cng vi s tng hp ca n.
Bit rng B c cng thc phn t l C9H8ClO-Li+ Hy xc nh cng thc cu to ca cc cht A, B, C, D, E, F trong s tng hp trn.
Bi 12
Urushiol l mt nhm cc cht lng mu vng vi nhit si c 200-210oC, l hot cht chnh trong cy si c v cy sn c. Chng lm cho da ni mn v tr nn nga khi tip xc vi kh tri. S dng cc thng tin sau y xc nh cu trc ca urushiol C21H34O2, mt cht trong s h cht ny. Urushiol c metyl ha v sau ozon phn cho hai hp cht nh s di y:

CH3(CH 2) 5CHO
Urushiol
MeI NaOH
C 23 H38O 2
i) O 3, CH 2Cl2 ii) Zn, H2O
A (C 16 H24O 3)
S tng hp andehit A c tin hnh qua s sau: x l metoxybenzen bng axit sunfuric bc khi sau tin hnh nitro ha bng axit nitric c trong s c mt ca axit sunfuric c cho hp cht B (C7H7NSO6). un nng B trong dung dch axit cho hp cht C (C7H7NO3). Cho cht C phn ng vi Zn trong HCl ri sau thm vo NaNO2 trong mi trng axit sau un nng cho hp cht D (C7H8O2). Cho cht D phn ng CO2 v KHCO3 p sut cao (phn ng Kolbe) dn ti cht E (C8H8O4). Cht ny phn ng vi CH3I v NaOH cho cht F (C9H10O4). Kh cht F bng LiAlH4 v sau tip tc oxi ha bng MnO2 cho hp cht G (C9H10O3). Tin hnh phn ng Wittig ca cht G vi cht C6H5CH2O(CH2)6C-HP+(C6H5)3 cho hp cht khng no H (C23H30O3). Hiro ha cht H bng hiro vi xc tc Pd cho cht I (C16H26O3). Oxi ha cht ny bng PCC cho anehit A. Vit cng thc cu to cc cht t B n I v vit cng thc cu to ca urushiol.
Bi 13
Pseudoephedrin (thng vit tt l PSE) l mt amin c kh nng kch thch thn kinh giao cm, thng gp trong cc loi thuc chng cm thng dng, n c cng thc cu to nh sau: a) V cng thc chiu Newman v cng thc chiu Fischer ca pseudoephedrin. b) un nng pseuoephedrine vi KMnO4 trong iu kin nh nhng c methcanthinon l mt cht kch thch, c th gy nghin. Xc nh cu trc lp th ca methcanthinon.
OH KMnO4 / H + NHCH 3 to
OH
NHCH3
un nng methcanthinon vi LiAlH4 thu c cht A. Cht ny c cng thc phn t ging v c nhit si khc so vi pseudoephedrin. Hy xc nh cu trc lp th ca A v gii thch qu trnh to thnh A t methcanthinon.
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Bi 14
iclofenac l mt ha cht phi steroit rt quan trng, c tc dng chng vim v gim au. N cn c dng iu tr au bng kinh. L thnh phn chnh trong rt nhiu cc loi dc phm thng mi (V d: Voltaren). Tn gi c ngun gc t tn ha hc l axit 2-(2,6-icloanilino) phenylaxetic. Cu trc ca tc nhn hot ng ch ra rng cht ny l mt dn xut th vng thm ca axit axetic th. Qu trnh tng hp cht ny t anilin c bit nh sau:
Ta c th c bit thm mt s thng tin sau b sung cho qa trnh tng hp: B l sn phm mononitro ha Trong bc chuyn B C th hai nguyn t hydro b thay th Cht H c cng loi nhm chc vi cht A. Phn ng H I l mt qa trnh ni phn t. Phn ng E F v I sn phm cui cng c chung mt c ch
Tr li cc cu hi sau: a) Vit CTCT cc cht t A n I. b) V tr no vng benzen b th? c) A v H thuc loi hp cht no?
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Bi 15
Captodiame l mt loi thuc gim au v an thn, c to nn t mt tng hp nhiu giai on. Giai on cui ca qu trnh tng hp l s kt hp ca hai hp cht G v H di tc dng ca baz.
G + H BCaptodiame
G c tng hp t etilen oxit v imetylamin qua hai giai on:

O + HNMe 2 I C 4H 11NO SOCl2 G C 4H 10NCl
Cn vic tng hp H c xut pht t cht u l benzen thiol:

SH C 4H9Cl Na2 CO3 C 6H5COCl J C 10H 14 S AlCl3 K C 17H 18 SO NaBH 4 L C 17H 20SO
SOCl2 H 2O H C 17H 20S2 OH (-CH4 N 2O) S

-
NH 2 S
+
NH2
M C 17H 19 SCl
Da trn cc d kin cho hy xc nh cu trc cc cht t G M, tc nhn phn ng N.
Bi 16
Hp cht bixiclic C (81,82 % C; 6,06 % H) l mt hp cht trung gian trong qu trnh tng hp cc ng phn E v K. Qu trnh tng hp C nh sau:
Cl +
COOEt COOEt
EtONa EtOH
i) NaOH/H2O ii) H+, H 2 O iii) to
i) PCl3 ii) AlCl3
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tng hp hai ng phn E v K ngi ta tng hp theo cch sau:
a) Xc nh cng thc cu to ca cc cht A, B, C, D, E, F, G, H, K. b) E tham gia mt phn ng t gp hirocarbon: phn ng vi NaNH2 thu c mt mui
rn cha natri v anion L. Xc nh xem L c tnh thm hay khng?

c) T hp cht E th epoxit c hnh thnh khi cho phn ng vi MCPBA (axit m-
clopebenzoic) sau cht ny nhanh chng chuyn thnh iol N bng NaOH. Vit cc ng phn lp th c th c N v xc nh cu hnh tuyt i cc trung tm bt i. Cho bit mi quan h gia cc ng phn ny.
Bi 17
Guaiol (C15H26O) l mt ancol rn trng thi tinh th c cu trc terpen. Ancol ny c phn lp t tinh du cy g Bulnesia, mt loi cy c th tm thy khu vc bin gii Argentina - Bolivia - Paraguay. Khi ehirat ha guaiol bng lu hunh th thu c mt hirocacbon thm mu xanh da tri khng cha vng benzen X (C15H18). Khi ha tan hirocacbon thm ny vo axit sunfuric c th mu xanh bin mt. Cho nc vo dung dch ny th X c phc hi nguyn dng. Rt kh hiro ha guaiol bng hiro c xc tc. Qua mt lot cc chuyn ha di y ta nhn c mt dn xut ca naphtalen (A l sn phm duy nht ca qu trnh ozon phn).
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a) Xc nh cu trc ca guaiol v X nu bit trong phn t guaiol th nhm hiroxyl gn vi nguyn t cacbon bc ba exocyclic ca h vng. b) Gii thch mu xanh da tri ca X v nu l do n b mt mu trong dung dch axit sunfuric c. c) Xc nh CTCT A, B v gii thch s to thnh A. d) C bao nhiu mnh isopren trong cht X.
Bi 18
D l tinh du c tc dng v li ch rt ln vi sc khe con ngi nhng khng phi l tt c cc loi tinh du trn th gii u c th s dng c, c mt s loi tinh du c c tnh c th gy c t cho ngi s dng. C Thuja l loi c thuc loi tng bch c tm thy nhiu Bc M v ng (xem hnh minh ha), tinh du ca loi c ny c nhng s nghin cu v khoa hc rt phc tp, n l tc nhn gy sy thai rt mnh v cng l cht c i vi thn kinh. Carvotanaxeton trong tinh du Thuja l mt terpin c cng thc phn t C10H16O khng phn ng vi thuc th Tollens nhng lm mt mu nhanh dung dch KMnO4 (long, lnh), phn ng c vi hiroxylamin to ra sn phm kt tinh. Khi kh carvotanaxeton ngi ta thu c carvomenton (C10H18O) v carvomentol (C10H20O). Carvomenton phn ng c vi hiroxylamin nhng khng phn ng c vi dung dch KMnO4 (long, lnh) cn carvomentol th khng phn ng c vi hiroxylamin ln KMnO4 (long, lnh) nhng li tc
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dng c vi axit sunfocromic. Trong mt bi th nghim oxi ha carvotanaxeton vi hai nhm sinh vin ng thi thc hin trong cc iu kin khc nhit khc nhau th nhm th nht thu c sn phm chnh l axit 2,4-isopropylbutaioic v axit 2-oxopropanoic. Trong khi nhm th hai li thu c sn phm chnh l 3-isopropylpentanioic v axit axetic. Hy xc nh cu to ca carvotanaxeton, carvomenton v carvomentol.
Bi 19
T nha thng ngi ta tch c mt monoterpen bixiclic l xabinen (sabinene) c cng thc phn t C10H16 vi cu trc nn l h thng mt vng xiclopropanngng t vi mt vng xiclopentan. Xabinen l mt trong nhng ha cht gp phn to nn mi thm ca ht tiu en v cng l mt thnh phn chnh trong cart thuc loi du (carrot seed oil). T cht u l xabinen, ngi ta thc hin mt chui chuyn ha theo s nh sau:
Hy xc nh cng thc cu to ca cc cht t X1 X7. Cho bit phn ng oxi ha ca KMnO4 khng to ra hp phn xiclopropanon v phn t X1 c 9 nguyn t carbon.
Bi 20
Toluen (A) phn ng nitro ha vi HNO3/H2SO4 thu c hn hp cc ng phn Bx. T hn hp ny, sn phm para B c tch ring ra. Cho mt na lng cht B phn ng vi mt ng lng sunfuryl clorua cng mt lng nh azo bis-isobutylnitrin (AIBN) lm cht to gc thu c hp cht C c khi lng phn t 171,5 v.C. Cht C c chuyn ha vi triphenyl
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photphin cho mui photphonium D. K tip, cho D phn ng vi n-BuLi thu c cht ylid E. Mt na lng cht B cn li c chuyn ha vi hai ng lng sunfuryl clorua cng mt lng nh AIBN thu c hp cht F c khi lng phn t bng 206 v.C. Khi c mt axit mnh, F chuyn thnh G v gii phng kh mi hc. Cht G c th b oxi ha tip theo bng thuc th Tollens. E v G tham gia phn ng Wittig thu c H, trong cc iu kin thun li cho s to thnh ng phn dng cis. ng phn ny b chiu x bi cng mnh thc hin phn ng ng vng oxi ha cho hp cht I c cng thc thc nghim l C14H8N2O4. I b kh bng Fe trong HCl cho J. Ti 5oC, J phn ng vi NaNO2 trong dung dch axit to thnh mui iazoni. Tip theo thm CuCl vo thu c cht K. K c chuyn ha vi Mg trong ete cho L, L phn ng vi HCHO to thnh M, M phn ng vi HBr trong mi trng axit mnh l H2SO4 cho hp cht N c cng thc thc nghim l C16H12Br2. Trong mi trng baz, N phn ng vi O cho hp cht P v hai phn t HBr. Cng thc cu to ca O:
P c x l vi H2O2 d cho Q. Nhit phn Q nhit cao trong chn khng to ra hp cht X v gii phng kh SO2. X c khi lng phn t l 308 v.C v ch cha cc nguyn t cacbon v hiro. Xc nh cng thc cu to cc cht c k hiu bng cc ch ci v vit cc phng trnh phn ng xy ra.
Bi 21
Trong l cy thuc l c cc ankaloit l hot cht, trong ankaloit chnh l nicotin (khong 10 - 16% thuc l v 16% thuc lo). N trong cy thuc l di dng mui kt hp vi axit limonic. Nicotin l cht lng nh du, khng mu, si 247 C, ha nu nhanh chng trong khng kh do b oxi ha, n d bay hi gy ra mi ca thuc l, d tan trong c, dung dch c tnh baz mnh. Nicotin l mt ancaloit rt c, ch c vi mg cng gy nhc u, i ma, vi lng ln hn n km hm hot ng ca h thn kinh, lm ngng h hp, t lit hot ng
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ca tim, do khng nn ht thuc l. Mt s kt qa iu tra cho thy rng nhng ngi nghin thuc l u b nm phi, mt s ng k b ung th phi v dn n t vong. Nicotin trong thuc l c th c tng hp t s sau:
Xc nh cng thc cu to ca cc cht F, G, H, I, K, L, M, N, P v nicotin trong s trn.
Bi 22
Charles John Pedersen (1904 - 1989) l nh ha hc ngi M gc Nht, dnh c gii Nobel Ha hc cng Donald Cram vo nm 1987 cho s ng gp ca h vo ha hc siu phn t. Nm 1967, Pedersen khm ph ra cc ete vng, c bit l nhng ete vng min (crown) c kh nng to phc cht vi cc ion kim loi kim. Vi c tnh ca nhng ete ny l kh nng to lin kt vi cc kim loi kim ty thuc vo bn knh ca cc ion nn mt ng dng ca chng l c dng tch cc ion kim loi kim ra khi hn hp. Pedersen v Cram thc hin mt s tng hp i t catechol:
Hy xc nh cng thc cu to ca cc cht A, B, C, X, Y trong s tng hp trn.
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Bi 23
Anastrozole C17H19N5 c tn thng mi l Arimidex, l mt loi thuc c s dng lm t dc tr liu sau gii phu hay iu tr bnh ung th v ph n. Anastrozole c th c tng hp t 3,5-bis(brommetyl)toluen theo s nh sau:
Na + N N N KCN Br Br CH 2Cl2 MeI (d) A NaH, to B NBS (1 : 1) (PhCO) 2O 2 C D (Anastrozole)
Hy xc nh cng thc cu to ca cc cht A, B, C, D trong s chuyn ha trn. Cho bit c ch ca phn ng chuyn C thnh D.
Bi 24
Coca l mt cy nh, cao khong 2 - 4m, l mc so le, c cung ngn, c hai l km nh bin i thnh gai. Phin l nguyn, hnh bu dc; hai bn gn gia c hai ng cong li (gn gi), tng ng vi hai np gp ca l trong chi. Hoa nh, mc n hoc tp trung 3 - 4 ci thnh xim k l. Hoa lng tnh, nm l i mu xanh, trng 5 cnh mu vng nht, 10 nh, bu 3 c 3 vi ri nhau, hai ca bu lp i, th ba ng 1 - 2 non o. Hoa n r vo thng 3 v thng 4. Trong cy coca c nhiu ankaloit, ni ting nht trong l cocain vi cng thc cu to nh sau:
18

Ancaloit tropan, nh atropin, hyosxiamin hay cocain u l este ca axit thm vi cc tropanol. Khung c bn cu trc ca cc tropanol l tropan, mt amin bixiclo, c tn IUPAC l 8-metyl-8aza-bixiclo[3.2.1]octan:
S ct mch hyosxiamin cho 3-tropanol v axit-(S)-tropic. T s phn tch cu trc ca axit tropic ngi ta thu c cc d liu sau: Axit tropic d b oxy ha bng K2Cr2O7/H2SO4.
- Axit hydrotropic c tng hp t axit tropc theo s :
S phn tch nguyn t ca axit hydrotropic cho kt qa l 72,0 % C; 6,67 % H v phn cn li l O. S oxy ha 3-tropanol cho tropinon, cu trc ca n ln u tin c xc nh bi Robert Robinson nm 1917 theo s di y:
Phn ng ca amin bc ba tropinon vi benzyl bromua cho ra hai mui amoni bc 4 A v B. S oxy ha tropinon bng CrO3 trong axit H2SO4 c nng cho axit tropinic (C8H13O4N). Axit tropinic cho im cn bng trung tnh 94 1, khng phn ng vi Br2 trong CCl4 v vn cha nhm chc amin bc 3. Nu s dng imetyleste ca axit-3-oxopentanoic thay cho propanon trong s tng hp tropinon ca Robinson th nhn c ieste tng ng ca tropinon C nh l mt cht trung gian trong s tng hp khung cu trc cocain. S di y ch ra mt con ng tng hp cocain.
19

a) Hy cho bit cng thc cu to ca axit hirotropic, axit tropic. V cu trc ca axit-(S)tropic v hyosxiamin. b) Xy dng c ch ca phn ng gia andehit sucxinic vi mt mol metylamin sinh ra imin (phn ng xy ra trong iu kin axit yu) v phn ng ca imin vi enol ca propanon (axeton) sinh ra baz Mannich. c) Xc nh cng thc cu to ca A, B, D, E, F, X. d) Cocain thin nhin c cu trc nh sau:
Xc nh cu hnh R-S ca cc tm bt i.
Bi 25
Franois Auguste Victor Grignard (1871 - 1935) tng l gio s ha hc ca i hc Lyon (Php), ng l ngi u tin nghin cu su v ng dng nhng hp cht c magie vo tng hp hu c. Chnh nh nhng ng dng to ln ca loi hp cht phc hp ny m ng c nhn gii thng Nobel ha hc v tn tui ca ng c ghi danh bi vic c dng t tn chung cho nhng hp cht c magie m ng pht hin Grignard reagent (Tc nhn Grignard). Hp cht ny thng c tng hp bng cch cho phoi Mg tc dng vi cc dn xut halogen trong ete.
20

Hp cht Grignard c th phn ng vi cc hp cht carbonyl , khng no to thnh cc sn phm cng 1,2 v 1,4 nh butaien-1,3 vi cc tc nhn electrophile. S cnh tranh gia phn ng cng 1,2 v cng 1,4 chu s chi phi rt mnh ca hiu ng khng gian. Hy xc nh cu trc ca cc cht trong chui phn ng sau:
Trnh by c th cc bc to thnh sn phm.
Bi 26
Patchoulol hay ancol patchouli (C15H26O) l mt terpen c trch ra t patchouli - mt loi tho mc ca h bc h. Loi tho mc ny c tm thy nhiu cc quc gia vng Caribe hoc chu , c bit l Trung Quc, n , Inonesia,... Patchoulol c mi hng rt nng v mnh, n c s dng lm nc hoa t nhiu th k trc cho n tn by gi. Nm 1984, nh khoa hc ngi Nht Bn Yamda K cng cc ng s cng b trn tp ch Tetrahedron cng trnh tng hp patchoulol t cc hp cht hu c n gin. Mt phn trong quy trnh tng hp patchoulol c tm tt trong s sau y (sn phm cui l mt tin cht ca patchoulol).
21

Hy d on cc sn phm trung gian, tc nhn phn ng (cn thiu bc cui cng).
Bi 27
Cc hp cht vng lin hp n gin c s electron tha mn quy tc Hckel th vic gii thch
tnh cht thm khng qu phc tp, tuy nhin vi nhng hp cht ngng t m c s electron khng
tha mn quy tc Hckel nhng vn c tnh thm th vic gii thch tnh cht thm phi theo hng
khc. C th vng ngng t no c t hp t nhng vng n vi s electron tha mn k = 4n +
2, to thnh h vng kn th hp cht l thm, khng ph thuc vo tng s electron trong c hp cht. V d trong trng hp koronen (coronene). Hp cht ny c th c xem nh to nn bi hai h vng 18 electron v 6 electron, u l nhng h vng thm c s electron tha mn quy tc Hckel nn koronen l mt h thm. Koronen c th tng hp t m-xilen qua mt chui phn ng nh sau:
B l sn phm ca phn ng sau:
Xc nh cu trc ca cc cht B, C, D, E, F trong chui phn ng.
22

Bi 28
Cho 2 - cacbetoxixixlopentanon phn ng vi 1,3 - ibrompropan khi c mt NaH trong DMF. Sn phm A nhn c c un nng vi mt ng lng NaH trong hn hp benzen - DMF cho php thu c dn xut bixiclic B C11H16O3. B chu tc dng ca etanithiol khi c mt BF3 v Ni Raney trong metanol hnh thnh sn phm C. X phng ha C bng NaOH sau thy phn ri x l vi thionyl clorua v cui cng bng NaN3 trong axeton. un hi lu hn hp trn khi c mt vt axit H+ s thu c D C8H15N. Bng tc dng ca fomandehit trong axit fomic 100oC D chuyn thnh E. Sau khi x l E bng metyl ioua, sau bng Ag2O trong nc, un sn phm thu c 200oC khi c mt 1,3 iphenylisobenzofuran ngi ta s nhn c hai ng phn C28H26O l (I) v (II) vi hiu sut thp.
Bi 29
Reserpin l mt ankaloit c c lp ln u tin vo nm 1952 t r kh ca mt loi cy cha c nc c ca rn. Reserpin c s dng iu ch cc dc phm cha bnh huyt p cao hay cha bnh trm cm, tuy nhin n cng c s dng ch to cc loi ma ty rt nguy him, bi vy nn trong mt thi gian n b cm Vng quc Anh. Cch y gn mt na th k, nh ha hc ngi M Robert Burns Woodward (1917 - 1979), ngi dnh c gii thng Nobel Ha hc vo nm 1965 thc hin thnh cng tng hp ton phn reserpin. Mt s giai on u ca tng hp ny c trnh by nh s di y.
Hy vit cng thc cu to v xc nh ha lp th ca cc cht A, B, C, D trong chui phn ng trn. Cho bit rng phn ng kh ha A c chn lc lp th v khi un nng B vi Ac2O s to ra
23

lacton vi hiu sut cao. bit thm v qu trnh tng hp reserpin ca Woodward, chng ta c th tm hiu tip mt giai on khc trong qu trnh tng hp ton phn.
NH2 O H H HOOC i) CH 2N 2 OH OCH3 ii) Ac2 O iii) OsO4 E i) HIO4 ii) CH 2N 2 H3 CO F N H G NaBH4 MeOH H
Hy xc nh cu trc ca E, F, G, H (khng cn quan tm n ha lp th).
Bi 30
Ankaloit (alkaloid) l nhng amin hu c cha d vng nit c ngun gc thin nhin. Cc Ankaloit thng c tm thy cc loi thc vt, i khi l c ng vt v nm. Nhiu loi trong s chng c kh nng gy ra nhng tc ng dc l hc ln c th ngi v ng vt, c bit l h thn kinh. Vi mt lng nh c ankaloit l cht c gy cht ngi nhng li c khi n l thn dc tr bnh c hiu. Nhng ankaloit c cha h vng piroliziin c gi vi tn chung l ankaloit piroliziin. Retronexin (retronecine) - mt pheromon ca cn trng l mt trong s khong hn 100 ankaloit piroliziin c pht hin. N c phn lp ln u tin vo nm 1909, nhng phi mt hn mt na th k ngi ta mi tng hp nhn to c retronexin bng con ng ha hc (1962).
EtOOC H N EtOOC COOEt O NaBH4 O N COOEt D i) H 2O/OH- , t o ii) HCl BrCH 2COOEt Na 2CO3 F C 10 H15O 4N KOEt Na COOEt A C 16 H27O 8N NaOEt B C14H 21O7 N i) HCl ii) EtOH/HCl C C 11 H17O 5N
OH COOEt H F N G O
H2 Pt, t o
H C 10 H17O 4N
i) H 2O/OH- , t o ii) HCl
i) EtOH/H
OH CH2 OH H N
C 8H 11O3 N ii) LiAlH 4 iii) H3 O+
24

Hy xc nh cng thc cu to ca cc cht A, B, C, E, F, H, I (khng cn quan tm n ha lp th ca cc sn phm v cc phn ng).
Bi 31
Cloroquyn (chloroquine) thuc nhm p-aminoquinolin c s dng iu ch mt trong nhng dc phm phng chng bnh st rt u tin trn th gii. Tuy nhin do n gy ra nhng phn ng ph nh gy nga, nhc mt, au u,... nn dn dn b thay th bi cc loi thuc hiu qu hn v t gy phn ng ph. N c tng hp t m-cloanilin v etilen oxit theo s sau y:
Hy hon chnh s tng hp trn bng cch ch ra cng thc cu to ca cc cht cha bit.
Bi 32
T c xa, con ngi a thch s dng cc loi du thm tch t thc vt. Hng thm m cng cha, cng nng n cc c thn n u a thch l hng thm ca hoa hng. Cc hp phn chnh to nn mi thm ca tinh du thc vt, ca hoa hng v cc loi hoa khc c phn loi da trn cu trc ha hc l terpen (nu l hirocacbon) hoc l terpenoit (dn xut cha oxi ca terpen). Di y l s tng hp terpenoit fenchone, mt cht lng khng mu c phn lp c t cy th l v cy ngi ng. Fenchone c s dng nhiu lm hng liu thc phm v lm nc hoa.
25

Xc nh cc cht v tc nhn cn thiu trong s tng hp ny (C th c mt hay nhiu tc nhn tham gia vo cng mt giai on chuyn ha, yu cu s tc nhn cng t cng tt).
Bi 33
Thuc nhum hay phm nhum l nhng hp cht hu c c mu, c kh nng nhum mu cc vt liu nh vi, giy, nha, da. Ngoi nhng nhm mang mu (quinon, azo, nitro,... ), phm nhum cn cha cc nhm tr mu nh OH, NH2... c tc dng lm tng mu v tng tnh bm ca phm vo si. Ngi c i chit ly phm nhum t nhin t mt vi loi thc vt hay ng vt bin, nhng gn nh tt c phm nhum mu chm ngy nay u c sn xut bng phng php tng hp. Ngi ta tng hp mt phm nhum thioinigo thng dng nhum mu cho o qun mt s nc chu u theo s sau:
Hy xc nh cng thc cu to ca cc cht A, B, C, K, L. Bit rng phn ng gia iazo vi Na2S2 l ghp mch hai phn t iazo vi cu lu hynh S S chung v gii phng N2.
26

Bi 34
Trong vic kho st ha thc vt ca mt loi cy thuc tr chng mt tr nh Trung Quc th cc nh khoa hc ca quc gia ny phn lp c hot cht chnh th hin tnh cht ny l Huperzine A. Hp cht ny cn c s dng iu tr bnh st hay ri lon ng mu. S di y c cc nh ha hc Trung Quc s dng tng hp hp Huperzine A. Hy xc nh cu to cc cht cha bit trong s .
Bi 35
Axit lysergic c bit nhiu dng axit D-lysergic l mt tin cht ca h ancaloit ergoline, n c tng hp trong cc loi nm ca g v mt s loi thc vt. ietylamit ca axit ny, c bit nhiu di ci tn LSD l mt loi dc phm gy o gic mnh. LSD c tng hp ln u tin bi thin ti ha hc ngi Thy S Albert Hofmann (1906 2008), ng l tc gi ca hn 100 bi bo v cng trnh nghin cu khoa hc ni ting v c xp cng Tim Berners Lee ngi pht minh ra mng internet v tr cao nht trong danh sch 100 thin ti ng i (do 6 chuyn gia trong lnh vc sng to v sng kin, t cng-ty t vn ton cu Creators Synectics cng b vo thng 10/2007). LSD c nh hng rt ln i vi th gii trn nhiu lnh vc. Axit lysergic thng thu c bng cch thy phn LSD nhng cng c th c tng hp trong phng th nghim qua cc chui tng hp ton phn ht sc phc tp.
27

V d nh s tng hp sau:
Hy xc nh cng thc cu to (khng cn quan tm n ha lp th) ca cc cht cn thiu trong s tng hp trn.
28

HHCo

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Trung tm hc liu box Ha hc Olympiavn

Advanced organic chemistry exams

Trung tm hc liu box Ha hc Olympiavn

Mt dn xut c ch khc ca shikonin cng c th tng hp theo s sau:

Trung tm hc liu box Ha hc Olympiavn

Hy xc nh cng thc cu to ca B v Gingerol.

Trung tm hc liu box Ha hc Olympiavn

Xc nh cu trc ca cc hp cht B,C , D, E, G, H, I. Bit I c cha nhm cacbonyl.

(Tt c u l sn phm chnh) Hy xc nh cng thc cu to ca cc cht A, B, C, D, E trong s tng hp trn.

Trung tm hc liu box Ha hc Olympiavn

Trung tm hc liu box Ha hc Olympiavn

Trung tm hc liu box Ha hc Olympiavn

Trung tm hc liu box Ha hc Olympiavn

i) RMgBr ii) HCl

Da trn cc d kin cho, hy xc nh cng thc cu to ca cc cht t A G trong s tng hp cho.

Trung tm hc liu box Ha hc Olympiavn

Trung tm hc liu box Ha hc Olympiavn

i) O 3, CH 2Cl2 ii) Zn, H2O

Trung tm hc liu box Ha hc Olympiavn

Trung tm hc liu box Ha hc Olympiavn

G c tng hp t etilen oxit v imetylamin qua hai giai on:

Cn vic tng hp H c xut pht t cht u l benzen thiol:

SOCl2 H 2O H C 17H 20S2 OH (-CH4 N 2O) S

Da trn cc d kin cho hy xc nh cu trc cc cht t G M, tc nhn phn ng N.

i) NaOH/H2O ii) H+, H 2 O iii) to

i) PCl3 ii) AlCl3

Trung tm hc liu box Ha hc Olympiavn

tng hp hai ng phn E v K ngi ta tng hp theo cch sau:

rn cha natri v anion L. Xc nh xem L c tnh thm hay khng?

Trung tm hc liu box Ha hc Olympiavn

Trung tm hc liu box Ha hc Olympiavn

Trung tm hc liu box Ha hc Olympiavn

Trung tm hc liu box Ha hc Olympiavn

Xc nh cng thc cu to ca cc cht F, G, H, I, K, L, M, N, P v nicotin trong s trn.

Hy xc nh cng thc cu to ca cc cht A, B, C, X, Y trong s tng hp trn.

Trung tm hc liu box Ha hc Olympiavn

Trung tm hc liu box Ha hc Olympiavn

- Axit hydrotropic c tng hp t axit tropc theo s :

Trung tm hc liu box Ha hc Olympiavn

Trung tm hc liu box Ha hc Olympiavn

Trnh by c th cc bc to thnh sn phm.

Trung tm hc liu box Ha hc Olympiavn

Hy d on cc sn phm trung gian, tc nhn phn ng (cn thiu bc cui cng).

B l sn phm ca phn ng sau:

Xc nh cu trc ca cc cht B, C, D, E, F trong chui phn ng.

Trung tm hc liu box Ha hc Olympiavn

Trung tm hc liu box Ha hc Olympiavn

Hy xc nh cu trc ca E, F, G, H (khng cn quan tm n ha lp th).

i) H 2O/OH- , t o ii) HCl

C 8H 11O3 N ii) LiAlH 4 iii) H3 O+

Trung tm hc liu box Ha hc Olympiavn

Hy xc nh cng thc cu to ca cc cht A, B, C, E, F, H, I (khng cn quan tm n ha lp th ca cc sn phm v cc phn ng).

Trung tm hc liu box Ha hc Olympiavn

Trung tm hc liu box Ha hc Olympiavn

Trung tm hc liu box Ha hc Olympiavn

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