BT Hoa Huu Co Tap1

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vn copyright 2009
Ti liu dnh cho:
Hc sinh chuyn Ha. Sinh vin cc trng i hc. Gio vin Ha hc.
08
2009
i ni u
Ha hc hu c l mt trong nhng b mn rt quan trng trong lnh vc Ha hc ni ring v phm tr Khoa hc t nhin ni chung. Tuy nhin hin nay, cc ti liu tham kho v bi tp ha hc hu c l khng nhiu. V vy vic tng hp cc t liu c mt ti liu tham kho b ch v d tip thu hn l vic rt cn thit. Bi tp Ha hc hu c l mt ti liu c bin son da trn vic tng hp li t nhiu ngun t liu khc nhau theo tng chuyn hc sinh, sinh vin d nm bt. Ti liu gm hai phn: Phn bi tp theo tng chuyn v phn hng dn gii. Cc bi tp trong tng chuyn c tuyn chn k lng nhm mc ch m bo cho cc dng bi tp khng trng lp v hc sinh, sinh vin c th tip cn nhiu hng ra khc nhau t cng mt d liu kin thc. Bi tp Ha hc hu c bao gm hai tp: - Tp 1: Gm by chuyn tng ng vi ni dung thuc phn i cng ha hc hu c v phn kin thc ha hu c t bi alkane n cetone (theo chng trnh ha hc ph thng). - Tp 2: Gm cc phn t acid carboxylic n cc hp cht d vng. Ngoi ra cn minh ha thm mt s bi tp nng cao tng hp cc chuyn . V l ti liu tng hp li cc bi tp nm trong cc gio trnh, sch tham kho bi tp hu c, cc thi hc sinh gii nn p n cho tng bi khng thay i theo p n ca tng ti liu tham kho. V vy Bi tp Ha hc hu c khng phi l mt ti liu do mt nhm tc gi bin son m ch l ti liu tng hp c chn la t cc ngun t liu sn c. (Tng hp t ngun Internet copyright volcmttl@yahoo.com.vn).
Bi tp Ha Hu C Ti liu dnh cho sinh vin cc trng i hc
Part: 1
HIU NG HA HC
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Bi 1: Sp xp cc nhm nguyn t sau theo chiu tng dn hiu ng tng ng, bit trong cu a th R ni trc tip vi S. a. Hiu ng I ca: b. Hiu ng C ca: c. Hiu ng +C ca: a. CH2=CHCH2Cl. b. p-NO2C6H4NH2. ti cc v tr o- hay p- ca C6H5CCl3 th thiu in t. Bi 4: Da vo hiu ng in t, hy so snh tnh acid ca cc cht sau y: a. C6H5OH (1), p-CH3OC6H4OH (2), p-NO2C6H4OH (3), p-CH3COC6H4OH (4), p-CH3C6H4OH (5). b. CH3CH2COOH (1), ClCH2COOH (2), ClC2H4COOH (3), IC2H4COOH (4), ICH2COOH (5). Bi 5: Sp xp cc cht sau theo th t gim dn tnh base: (1) SR (1) R2NCO (1) RCON(R) (2) SO2R (2) R2NC(=NR) (2) RC(=NR) N(R) c. C6H5CN. d. C6H5CH3. (3) SOR (3) (R)2NC(=+NR2) (3) RCH2N(R)
Bi 2: Da vo hin tng cng hng, vit cng thc gii hn (nu c) ca cc cht sau y:
Bi 3: Gii thch ti sao nhng v tr o- hay p- ca hp cht C6H5CH2Cl tng i giu in t trong khi
(1)
(2)
(3)
(4)
(5)
Bi 6: So snh tnh acid ca cc hp cht sau: (1) (CH3)3CCOOH ; (2) CH3CH=CHCH2COOH ; (3) CH3CH2CH=CHCOOH ; (4) (CH3)2CHCOOH ; (5) CH2=CHCH2CH2COOH. Bi 7: So snh tnh base ca cc hp cht sau:
(1)
(2)
(3)
(4)
(5)
Copyright 2009 volcmttl@yahoo.com.vn
Bi 8: Ngi ta nhn thy rng alcohol tertbutylic tc dng ngay lp tc vi acid HCl m c to thnh tertbutylchloride bn vng trong khi alcohol nbutylic trong cng iu kin phn ng rt chm. Bi 9: Xc nh hiu ng ca cc nhm th sau khi lin kt vi gc phenyl: Cl, C(CH3)3, CHO, NO2, CN, CH2CH3, N+(CH3)3. Bi 10: Da vo hin tng cng hng, vit cng thc gii hn (nu c) ca cc cht sau y: a. Aniline. b. Buta1,3diene. Bi 11: So snh bn ca cc ion sau: a. (1) CH2CH3, (2) CH(CH3)2, (3) C(CH3)3. b. (1) CH2CH3, (2) CH2OCH3, (3) CH2NHCH3. c. (1) C(CH3)3, (2) CH2C6H5, (3) CH(C6H5)2. Bi 12: Xc nh base lin hp ca cc acid sau theo quan im ca Brnsted: H2O, C6H5NH3(+), C2H5OH, H3O(+). Bi 13: So snh di lin kt CCl trong CH3CH2Cl v CH2=CHCl. Gii thch. Bi 14: Gii thch s tng dn nhit si ca cc alcohol sau: Alcohol Nhit si (oC) CH3OH 65 C2H5OH 78,5 C3H7OH 97,2 C4H9OH 138 c. Vinyl Bromide. d. Acrolein.
Bi 15: Cho ba gi tr nhit si: 240oC, 273oC, 285oC. Gn ba gi tr trn vo ba ng phn o-, m-, pca benzenediol cho ph hp. Gii thch ngn gn. Bi 16: Gii thch s khc nhau v nhit si trong dy cc cht sau: (1) (2) (3) (4)
115oC
117oC
256oC
187oC
Bi 17: So snh kh nng tan trong nc ca cc cht sau a. (1) HO(CH2)4OH, (2) HO(CH2)3CHO, (3) C3H7CHO. b. (1) C6H5NH3Cl, (2) C6H5NH2, (3) C2H5NH2. Bi 18: Acid fumaric v acid maleic c cc hng s phn li nc 1 (k1), nc 2 (k2). Hy so snh cc cp hng s phn li tng ng ca hai acid ny v gii thch. Bi 19: So snh nhit nng chy v tr s pKa ca 2 acid sau:
(1) acid iso-Crotonic Copyright 2009 volcmttl@yahoo.com.vn
(2) acid Crotonic 2
Bi 20: Xc nh tm base mnh nht trong cc alkaloid sau:
Nicotine *** *** *** *** *** *** *** *** *** ***
Vindoline *** *** *** *** *** ***
Part: 1
HNG DN GII
Bi 1: Sp xp theo chiu tng dn hiu ng in t: a. (1) < (3) < (2). b. (2) < (3) < (1). c. (1) < (2) < (3). Bi 2: Vit cng thc gii hn: a. Cht (a) khng c cng thc gii hn. b. Cng thc gii hn ca (b)
c. Cng thc gii hn ca (c)
d. Cng thc gii hn ca (d)
Bi 3: Gii thch: hp cht C6H5CH2Cl c hiu ng siu lin hp dng +H ca nhm CH2Cl vi vng benzene lm cho nhng v tr o- hay p- ca vng tr nn giu in t. Trong khi nhm CCl3 ht in t mnh (hiu ng siu lin hp m H) nn nhng v tr ohay p- ca C6H5CCl3 th thiu in t. Bi 4: So snh: a. (3) > (4) > (1) > (5) > (2). Bi 5: Chiu gim dn tnh base: (3) > (1) > (4) > (5) > (2). Bi 6: Chiu tng dn tnh acid: (1) < (4) < (3) < (5) < (2). Bi 7: Chiu gim dn tnh base: (3) > (4) > (5) > (1) > (2). Bi 8: Xt 2 phn ng sau:
H (1) (CH3)3COH + HCl (CH3)3CCl + H2O c vn tc phn ng l v1 H (2) CH3CH2CH2CH2OH + HCl CH3CH2CH2CH2Cl + H2O c vn tc phn ng l v2
+ +
b. (2) > (5) > (3) > (4) > (1).
C ch phn ng d l SN1 hay SN2 u tri qua giai on to carbocation. Carbocation cng bn th phn ng xy ra cng u tin. S d v1 >> v2 l do carbocation (CH3)3C bn hn CH3CH2CH2CH2 nhiu. iu ny gii thch da vo +I ca (CH3)3C ln hn nhiu so vi +I ca CH3CH2CH2CH2. Bi 9: Khi lin kt vi gc phenyl th: CHO, NO2, CN gy hiu ng I, C Cl gy hiu ng I, +C N+(CH3)3 gy hiu ng I C(CH3)3 gy hiu ng +I CH2CH3 gy hiu ng +I, +H
Bi 10: Cng thc gii hn: a. Aniline
b. Buta1,3diene: c. Vinyl Bromide: d. Acrolein: Bi 11: So snh bn: a. (3) > (2) > (1). b. (3) > (2) > (1). c. (3) > (2) > (1).
CH2CH=CHCH2
CH2CH=Br+ CH2CH=CHO
Bi 12: Xt bng: acid base lin hp H2O OH C6H5NH3(+) C6H5NH2 C2H5OH C2H5O H3O(+) H2O
Bi 13: di lin kt CCl trong CH2=CHCl ngn hn trong CH3CH2Cl v: CH3CH2Cl c hiu ng I. Ngoi hiu ng I cn c thm hiu ng +C lm gim di lin kt CCl (lm di lin kt CCl ngn hn lin kt CCl bnh thng ng thi lm lin kt C=C di hn di lin kt C=C bnh thng). Bi 14: Do c 4 alcohol u to c th to c lin kt hydro lin phn t nhng do khi lng phn t ca cc alcohol tng dn nn nhit si cng tng dn. Bi 15: Ta c ba ng phn o-, m-, p- ca benzenediol
(1) 240oC
(2) 273oC
(3) 285oC
(1) c lin kt hydro ni phn t nn nhit si l b nht. (2), (3) u c lin kt hydro lin phn t nhng lin kt hydro ca (3) bn hn ca (2) do t b cn tr v mt khng gian. Bi 16: Ta c nhit si ca (1) < (2) l do hai cht ny khng to c lin kt hydro nn nhit si ph thuc vo khi lng phn t. Li c, nhit si ca (4) < (3) l do mc d c hai cht u c lin kt hydro lin phn t nhng lin kt hydro ca (3) dng polymer cn ca (4) dng dimer. Bi 17: Kh nng tan trong nc ca: a. (1) > (2) > (3). Bi 18: Xt cc chuyn ha:
HOOC H - H+ HOOC H F
,
b. (1) > (3) > (2).
H COO- H+
OOC H F
,,
H COO-
H COOH F Axit fumaric
OH ...O O H H OH - H+ O H
OH ... O
.... O
OOC H M,,
COOH
....
- H+
H M,
M Axit maleic
k1(M) > k1(F) l do M c kh nng to lin kt hydro ni phn t, lin kt OH ca M trong qu trnh phn li th nht phn cc hn so vi F v base lin hp M' cng bn hn F'. k2(M) < k2(F) l do lin kt hydro ni phn t lm cho M' bn, kh nhng protone hn so vi F'. Ngoi ra, base lin hp M'' li km bn hn (do nng lng tng tc gia cc nhm COO ln hn) base lin hp F''.
Bi 19: So snh Nhit nng chy ca (2) > (1). Tnh acid ca (1) > (2).
Bi 20: Xc nh tm base mnh nht
Nicotine -
Vindoline
Alkaloid l cc base t nhin, tnh base tp trung ti d t N cho nn nguyn t N cng giu electron th tnh base cng mnh.
Vi Vindoline th N(b) trong nhn indole c tham gia qu trnh cng hng nn ngho electron hn N(a) nn tm base mnh nht ca vindoline l N(a).
Vi Nicotine th tnh base ca N(a) v N(b) gn bng nhau tuy nhin N(a) tham gia vo qu trnh cng hng cho nn tm base mnh nht ca Nicotine l N(b).
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Part 2
NG PHN
6
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Bi 1: Vit cc ng phn cu to ca cc cht sau: a. b. C5H10 (cha mt vng). C5H11OH. c. d. C6H14. C4H9Cl.
Bi 2: Cht no sau y c ng phn hnh hc, gi tn cc ng phn theo danh php Z, E. a. b. c. d. e. (CH3)2CHCH=CH2 CH3CH=CHCH3 CH3CH=CHF C2H5C(CH3)=CHCH3 CH3CH=C=CHCH3 f. g. h. i. Cao su thin nhin Nha Guttapercha CH3CH=C=C=C=CHCH3 1,2dimethylcyclopropane
Bi 3: Da theo gi tr momen lng cc ca cc ng phn hnh hc, hy cho bit trong cc cht A, B sau y ng phn no l cis, ng phn no l trans a. b. c. a. b. c. d. FHC=CHF CH3CH=CHBr pNO2C6H4CH=CHC6H4 A = 0 D A = 1,57 D A = 3,11 D B = 2,42 D B = 1,69 D B = 4,52 D
Bi 4: Nhng cht sau y c th tn ti bao nhiu ng phn lp th. 1phenylethanol. 2chlorobut2ene. 1,2dibromopentane. Alanine.
Bi 5: Trnh by cng thc chiu Fischer v xc nh cu hnh tuyt i ca cc ng phn c cu to sau
(a)
(b)
(c)
Bi 6: Vit cng thc chiu Newman dng bn ca: a. (CH3)2CHCH2CH3. 7
b. c.
CH3CH=CH2. CH3CHO.
Bi 7: Cht A l mt acid hu c c ni i C=C v khng quang hot. Tuy nhin A c ng phn hnh hc v c cng thc phn t l C5H8O2. Khi hydro ha A thu c sn phm B c tnh quang hot. Xc nh hai cht A, B v vit phng trnh phn ng xy ra. Bi 8: Vit cc cng thc h bin ca: a. b. c. CH3COCH2CH3. CH3COCH2COCH3. C6H5NHCONHC6H5.
Bi 9: Hy ghi du * vo bn cnh nguyn t carbon bt i v xc nh cu hnh tuyt i ca Serine, Adrenaline, Menthone.
Serine a.
Adrenaline (Corticoid) b.
Menthone
Bi 10: Vit cng thc dng h bin v cho bit loi h bin trong hai trng hp sau: Cyclohexanone. (CH3)2CHN=O. Bi 11: Xc nh cu hnh ca A, B (dng cis, trans) v vit cu dng gh tng ng H H
H H A Bi 12: Cho cc phn ng sau:
H H B
pyridine (1) C6H5CH2CH(CH3)OH + ClSO2C6H4CH3-p (E) +
[ ]D = +33o (2) (E) + CH3COOK TsOK + (F) (3) (F) + KOH CH3COOK + C6H5CH2CH(CH3)OH [ ]D = 32,2o a. b.
Cl
(Ts l k hiu vit tt ca SO4C6H4CH3-p)
Xc nh cu trc ca (E) v (F) v cho bit phn ng (2) thuc loi phn ng g. Cho bit phn ng thy phn cc ester loi nh (F) trong mi trng kim vi s hin din ca
OH 18 RCOO H + ROH
H2O18 nh sau: RCOOR + H2O18
Da vo cc kt qu trn, hy gii thch s thay i du nng sut quay cc [ ]D ca alcohol ban u v sn phm. Bi 13: Vit tt c cc ng phn ca phc cht [Co(bipy)2Cl2]+ vi bipy l:
Bi 14: Quang ph hp th in t ca formaldehyde c ba cc i 295 nm, 185 nm v 155 nm. Nu cho formaldehyde tc dng vi H2 c xc tc Pt th ba cc i ny cn khng. Gii thch. Bi 15: Vit cng thc cu to cc ng phn mch h c cng thc phn t C3H4BrCl, c ng phn quang hc v ch c mt carbon phi i xng trong phn t. Bi 16: Styryllactone c phn lp t thc vt. Vit cng thc cu dng cc cp ng phn i quang v gi tn styryllactone theo danh php IUPAC.
6 7 8
5 9 1
4 3 2
HO
Bi 17: Khung carbon ca cc hp cht terpene c to thnh t cc phn t isoprene kt ni vi nhau theo quy tc u ui. V d, nu tm quy c: (u) CH2=C(CH3)CH=CH2 (ui) th phn t mycrene c kt hp t 2 n v isoprene. Da vo quy tc trn hy cho bit trong cc cht sau
mycrene
y, cht no l terpene v ch ra n v isoprene trong khung terpene .
Bi 18: Vit cng thc Fischer ca cc cht C v D trong dy chuyn ha sau:
Bi 19: Vit cng thc chiu Fischer cc ng phn lp th ca acid 2bromo3methylsuccinic v ch ra cc cp ng phn i quang v cc cp ng phn khng i quang trong cc ng phn lp th . Copyright 2009 volcmttl@yahoo.com.vn
9
Bi 20: C ba hp cht: A, B v C
a. b. c.
Hy so snh tnh acid ca A v B. Hy so snh nhit si v tan trong dung mi khng phn cc ca B v C. Cho bit s ng phn lp th c th c ca A, B v C.
Part 2
HNG DN GII
5 2 + 2 10 = 1 , theo C5H10 c cha mt vng ( = 1 ) nn l cycloalkane. 2
Bi 1: Vit cc ng phn cu to: a. bt bo ha =
C5H10 (c 1 vng) c 5 ng phn cu to ph hp:
b. C5H11OH c bt bo ha = c. C6H14 c = 0 , c 5 ng phn.
5 2 + 2 12 = 0 nn l alcohol no n chc. C 8 ng phn. 2
d. C4H9Cl c = 0 , c 4 ng phn. Bi 2: Cc cht c ng phn hnh hc l b, c, d, f , g, h, i Vi b, c, d ch c 2 ng phn hnh hc. f (cispolyisoprene) c ng phn l g (transpolyisoprene) v ngc li. h c ng phn hnh hc v c s l lin kt C=C lin nhau nh mt h c nh.
i c hai ng phn hnh hc do vng cyclopropane phng (mt c nh).
Bi 3: Xt bng
10
Cu ng phn Cis trans Bi 4:
a B A
b A B
c B A
a. (A) c 1 C* nn c 21 = 2 ng phn quang hc, (A) khng c ng phn hnh hc. Vy (A) c 2 ng phn lp th. b. (B) c 2 ng phn lp th l 2 ng phn hnh hc. c. (C) c 2 ng phn lp th l 2 ng phn quang hc. d. (D) c 2 ng phn lp th l 2 ng phn quang hc. Bi 5: Cu hnh tuyt i (a) (2S)(3S)dichlorobutane. (b) Acid (2R)(3R)2,3dihydroxy2,3dimethylbutane4al1oic. (c) (2R)(3S)2bromo3chlorobutane.
(a) Bi 6: Vit cng thc chiu Newman a. (A) c 2 dng bn:
(b)
(c)
b. (B) c 1 dng bn:
c. (C) c 1 dng bn:
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Bi 7: A l CH3CH=C(CH3)COOH. B l CH3CH2CH(CH3)COOH. Bi 8: Cng thc h bin a. H bin cetoenol ca dng ceto CH3COCH2CH3 l cc dng enol CH3C(OH)=CHCH3 ; CH2=C(OH)C2H5 b. H bin cetoenol ca dng ceto CH3COCH2COCH3 l cc dng enol CH3C(OH)=CHC(=O)CH3 ; CH2=C(OH)CH2C(=O)CH3 c. H bin cetoenol ca dng ceto C6H5NHCONHC6H5 l dng enol C6H5N=C(OH)NHC6H5 Bi 9: Ghi du * vo bn cnh nguyn t carbon bt i v xc nh cu hnh tuyt i:
* *
R Bi 10: Cng thc dng h bin a. Cyclohexanone. H bin cetoenol
b. (CH3)2CHN=O. H bin nitro-axi
Bi 11: Xc nh cu hnh ca A, B (dng cis, trans) v vit cu dng gh tng ng Copyright 2009 volcmttl@yahoo.com.vn
12
A l cisdecalin Cu dng gh ca (A), (B)
B l transdecalin
(A) Bi 12:
(B)
a. Gi s alcohol ban u c [ ]D = +33o cu hnh R => (E) cng c cu hnh R v phn ng khng xy ra ti C* m ti O, trong khi (F) c cu hnh S ti phn ng xy ra ti C*. Gi s cu trc ban u ca alcohol l:
Cu trc ca (E) l:
Cu trc ca (F) l:
Phn ng (2) l phn ng SN2 => sn phm alcohol ca phn ng (3) c cu hnh nghch vi cu hnh alcohol ban u.
b. Phn ng (1) v (3) khng lm nghch cu hnh, ngc li phn ng (2) c s nghch o cu hnh do phn ng xy ra theo c ch SN2 Bi 13: Quy c biu din bipy bng mt cung li. a. ng phn cis, trans:
Cl Cl Co Cis Cl Co Cl Trans
b. ng phn quang hc:

Cl Co Cl Cl Cl Co
Bi 14: Ba cc i hp th 295 nm, 185 nm v 155 nm tng ng vi s chuyn di in t mc nng lng: n * , n * , * . Khi tc dng vi H2/Pt to ra nhm OH nn lin kt khng cn, do vy ba cc i khng cn. Bi 15: ng phn quang hc:
Bi 16: Tn: 8hydroxy7phenyl2,6dioxabicyclo[3.3.1]nonane3one Cng thc cu dng:

4 3 2
O O
3
O O
2 3 6 2
O
2 3
H5C 6
O O
8 1 6
O
8
O
5 5
O
1
HO
C6H5 OH
H5C 6
O
8 1 9 9 1
O
8
HO
C6H5 OH
Bi 17: Acoron v acid abietic l terpene
Bi 18: Cng thc Fischer ca cc hp cht C, D
13
Bi 19: Ta c 4 ng phn lp th
(I)
(II)
(III)
(IV)
Bi 20: So snh, gii thch a. Tnh acid c nh gi bi s d dng phn li protone ca nhm OH. Kh nng ny thun li
khi c cc hiu ng ko electron (I hoc C) nm k nhm OH. A va c hiu ng lin hp (C) v hiu ng cm ng (I) ; B ch c hiu ng (I). Tnh acid ca (A) > (B). b. Lin kt hydro lm tng im si. Cht C c lin kt hydro ni phn t, B c lin kt hydro lin
phn t nn nhit si ca (C) b hn nhit si ca (B). (C) c tan trong dung mi khng phn cc ln hn (B). c. (A), (B) u c 2 tm bt i, hai nhm th c th nm 2 pha khc nhau ca vng
cyclohexene v chng c th tn ti 4 ng phn lp th. (C) c 4 tm bt i c 16 ng phn.
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Part 3
OEt O C O N O N HN
O2 S
C CH PHN NG
OEt N
-H
+
(- )
O OEt O N N N N
+H
+
C N
O2 S
O N
+ CO2 + HN
N CH3
N CH3
O2 S N
N CH3
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Bi 1: Cho bit cc phn ng sau xy ra theo c ch g. Vit c ch phn ng. a. CH3MgCl + C2H5COCH3 b. CH3CH2Cl + KCN c. CH3Cl + H2NCH3
OH d. CH3CH2Cl + H2O
H g. 2C2H5OH
h. Pyridine + C2H5I
H i. C6H5OH + HCHO OH j. C6H5CHO + CH3CHO t k. CH3CH2CH(OSO3H)CH3 + H2O
o +
e. C6H5ONa + CH3I f. C6H5OH + CH3OH
l. CH3COOC2H5 + OH
Bi 2: Xc nh cc cht cn li trong cc s sau v nu c ch to ra chng a. Hon thnh s sau:
b. Hon thnh s sau:
c. Hon thnh s sau:
Bi 3: Cho bit sn phm to thnh trong cc phn ng sau, nu c ch phn ng

600 C a. CH3CH=CH2 + Cl2 1:1
o
CCl4 b. CH2=CH2 + Br2 1:1 CCl4 c. H2C=CHCH=CH2 + Br2 1:1

t C d. C6H5CH3 + Cl2 1:1,Fe,xt
o
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Bi 4: So snh kh nng phn ng ca cc cp cht sau: a. Theo SN1: CH3CH2CH2Cl (1) ; CH2=CH2CH2Cl (2). b. Theo SN2: CH2=CHCl (1) ; CH3CH2Cl (2). c. Theo SN1: p-NO2C6H4CH2Cl (1) ; p-CH3OC6H4CH2Cl (2) ; CH3CH2CH2Cl (3). Bi 5: Dng mi tn cong ch r c ch chuyn 7-dehydrocholesterole (I) thnh vitamine D3 (II) v cho bit cu dng bn ca n. Bit trong cng thc di y: R l: -CH(CH3)-(CH2)3-CH(CH3)2
R
R
(I)
(II)
HO
HO
Bi 6: Cho s phn ng:

CH 3C=O C 2H 5
1.
C 6H 5MgBr
2 . H 2O
H (A) C 3H 7
HBr a c B
a. Vit c ch phn ng v cng thc cu to cc sn phm. b. Gi tn cu hnh ca B, C theo danh php R, S. Bi 7: Hy gii thch s to thnh nhanh chng 2,4,6-Br3C6H2NH2 (D) khi cho p-H2N-C6H4-SO3H (A) hoc p-H2N-C6H4-COOH (B) tng tc vi dung dch nc Br2. Bi 8: Hy ch ra c ch phn ng v sn phm cui ca phn ng cng Br2 (1:1) vi nhng cht sau: a. Acid maleic (1). b. Acid fumaric (2). c. But-2-ine (3).
H 3C C C CH3 (1) (2) (3)
Bi 9: Xt phn ng th: RCl + OH ROH + Cl c biu thc tc phn ng l: v = k[RCl] hoc v = k[RCl][OH ] a. Cho mt v d c th v RCl trong mi trng hp, gii thch. b. S dung mi gii ca tertButyl bromide trong acid acetic xy ra theo c ch nh sau:
(CH 3 )3 CBr (CH 3 )3 C + + Br

+
(1)
(CH 3 )3 C + CH 3COO (CH 3 )3 COCOCH 3 (2) Hy gii thch ti sao, khi tng hm lng Sodiumacetate (CH3COONa) th khng lm tng tc phn ng.
Copyright 2009 volcmttl@yahoo.com.vn 17
Bi 10: Hp cht 2,2,4-trimethylpentane (A) c sn xut vi quy m ln bng phng php tng hp
xc tc t C4H8 (X) vi C4H10 (Y). A cng c th c iu ch t X theo hai bc: th nht, khi c xc tc acid v c, X to thnh Z v Q ; th hai, hydro ho Q v Z.
a. Vit cc phng trnh phn ng minh ha v tn cc hp cht X, Y, Z, Q theo danh php IUPAC. b. Ozone phn Z v Q s to thnh 4 hp cht, trong c acetone v formaldehyde, trnh by c ch. Bi 11: Gii thch: a. Ti sao phn ng sau khng dng tng hp tert-butyl propyl ether.
CH3CH2CH2ONa +
(CH3)3CBr
(CH3)3COCH2CH2CH3
b. Sn phm chnh ca phn ng ny l g. c. Hy ngh phng php tng hp tert-butyl propyl ether tt hn. Bi 12: X l - halogen cetone vi base mnh to thnh cc sn phm chuyn v. S chuyn v ny gi
l phn ng Favorski: - chlorocyclohexanone s chuyn v thnh methylcyclopentanecacbocylate khi c mt CH3ONa trong ether. Hy xc nh c ch ca phn ng ny.
LiAlH 4 H2 Bi 13: Cho cc phn ng sau: But 2 ine A (1) ; But 2 ine A (2) . Trong Pd / CaCO3
A, B l 2 ng phn lp th. Khi ch ha ring bit A v B bng acid mnh th chng u chu s chuyn ha sau: ng phn ha v tr, ng phn ha khng gian.
a. Xc nh A, B v cc sn phm chuyn ha nu trn. b. Vit c ch cho qu trnh chuyn ha trn. Bi 14: Khi un nng 2methylcyclohexane1,3dione vi but3ene2one trong dung dch kim
ngi ta thu c mt hp cht hu c (sn phm chnh) c cng thc C11H14O2. Hy vit cng thc cu to ca sn phm ny v gii thch qu trnh to ra n.
Bi 15: C mt phn ng chuyn ha theo phng trnh sau:
a. Gii thch c ch. b. Nu thay cht ban u l pxylene th sn phm no to thnh.
18
Part 3
HNG DN GII
2
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Bi 1: AN a. CH3MgCl + C2H5COCH3 (CH3)2C(C2H5)OMgCl

SN b. CH3CH2Cl + KCN CH3CH2CN + Cl SN c. CH3Cl + H2NCH3 CH3HNCH3 + HCl SN d. CH3CH2Cl + H2O CH3CH2OH + HCl SN e. C6H5ONa + CH3I + NaI SE f. C6H5OH + CH3OH CH3C6H4OH (o-, p-) + H2O SN g. 2C2H5OH C2H5OC2H5 + H2O SN h. Pyridine + C2H5I [pyridine(N+) C2H5]I SE i. C6H5OH + HCHO (o-, p-) CH2OHC6H4OH AN j. C6H5CHO + CH3CHO C6H5CH=CHCHO + H2O SN k. CH3CH2CH(OSO3H)CH3 + H2O CH3CH2CH(OH)CH3 + SN l. CH3COOC2H5 + OH CH3COO + C2H5OH
2 1 2 2 2 2 2
Bi 2:
19
Bi 3: 600o C a. CH3CH=CH2 + Cl2 Cl CH 2 CH = CH 2 + HCl SR

CCl4 b. CH2=CH2 + Br2 BrCH2CH2Br AE CCl 4 c. H2C=CHCH=CH2 + Br2 (1) + (2) ; AE
(1) ClCH2CH(Cl)CH=CH2 ; (2) ClCH2CH=CHCH2Cl

t C,1:1,Fe,xt d. C6H5CH3 + Cl2 p CH3C6 H 4Cl + HCl SE
o
Bi 4: a. (2) > (1) Bi 5:

.
R
b. (2) > (1)
c. (2) > (3) > (1)
H H2C
as
HO HO
to
R
HO HO
Cdng b n: Cu u d ngbn S-trans
Bi 6: a. C ch AN. Cng thc ca B v C
b. B: (2R)(3S)2phenyl3ethylhexane2ol, C: (2R)(3S)2phenyl2bromo3ethylhexane Bi 7: Trong nc (A), (B) tn ti dng ion lng cc:
p-H2N-C6H4-SO3H (A) p-H2N-C6H4-COOH (B)
p-+H3N-C6H4-SO3 (A) p-+H3N-C6H4-COO (B)
Mt nhm SO3 trong A hoc COO trong B l do: Br2 Br+ + Br
20
Sau tc nhn electronphile (Br+) s tn cng vo nguyn t carbon ca nhn thm th nhm SO3 trong A hoc COO trong B. Sau xy ra qu trnh tch H+ to thnh nhm NH2. Nhm NH2 vi hiu ng C s nh hng nhm th tip theo vo v tr ortho- theo s sau:
Bi 8: C ch cng Bromine vo ni i C=C xy ra theo c ch cng hp electronphile AE, gm 2 bc:
Trng hp a, b xy ra theo c ch AE nu trn.

a. Phn ng to thnh hn hp raxemic gm 2 acid: acid (2R)(3R)2,3dibromobutanedioic v acid
(2S)(3S)2,3dibromobutanedioic
b. C 4 cch tn cng u cho 1 sn phm duy nht l acid (2R)(3S)2,3dibromobutanedioic c. Cng tng t c ch AE nhng sn phm l: (E)2,3dibromobut2ene. Bi 9: a. Ta c:
v = k[RCl] phn ng th n phn t SN1, trng hp thun li l halogenide bc III nh (CH3)3CCl. v = k[RCl][OH] phn ng th lng phn t SN2, trng hp thun li l halogenide bc I nh CH3CH2CH2Cl
b. Phn ng theo SN1 , m giai on (1) l giai on chm quyt nh tc phn ng v biu thc
tc phn ng khng ph thuc [CH3COO] nn tng nng CH3COONa khng lm thay i tc phn ng.
21
Bi 10: a. Sn phm phn ng

CH3 H 3C C CH2 + H CH3 C CH3 CH3 H t p
o,
CH3 C CH3 CH3
H 3C
C H
C H (A)
2-Metylpropen (X)
CH3 2-Metylpropan (Y)
Phn ng qua 2 bc: Bc th nht gm tng tc gia hai phn t trong mi trng acid:
CH3 H CH3 2 H3C C CH2 H+ H3C C C CH3 C CH2 2,4,4-trimetyl pent-1-en CH3 C CH3 2,4,4-trimetyl pent-2-en
CH3 H CH3 H H3C C CH3 C
Bc th hai hydro ho Q v Z
CH3 H H3C C C CH3 C CH2 + H2
Ni , t
o
CH3 H CH3 H H3C C CH3 C CH3 C CH3 + H2
CH3 H H3C C C
CH3 C H CH3
CH3 H
b. C ch phn ng
(0,75 m).
O R1 C CH3 Z O O R2 C H Q R2HC C CH3 CH3
O3
O O R1 O C CH2
O3
O CH2 O
Zn/H3O
+
R1
C CH2 CH3
R1
C CH3
O + O
CH2
CH3 O O C CH3 CH3 H R2 O C H C O
R2
CH3 CH3
Zn/H3O
O + CH3COCH3
22
Bi 11: a. Phn ng sau khng dng tng hp tert-butyl propyl ether.
CH3CH2CH2ONa + (CH3)3CBr (CH3)3COCH2CH2CH3

Natri propoxide tert-butyl bromide tert-butyl propyl ether. Do phn ng th SN2 khng thc hin vi alkyl halogenide bc ba
b. Ion Alcoholate l mt base mnh, l tc nhn nucleophile nn phn ng tch chim u th nn
sn phm chnh ca phn ng ny l sn phm tch E2
c. Phng php tng hp hiu qu l dng phn t phn ng SN2 c nhm alkyl t cn tr hn v
alcoholate cn tr nhiu hn:
Bi 12:
O Cl CH3O CH3OH O Cl O O CH3O OCH3
OCH3 H2O OH
OCH3
Bi 13: a. Gii thch cu hnh A, B
Do phn ng cng LiAlH4 l phn ng cng trans nn A l transBut2ene. Do phn ng cng H2 xc tc Pd/CaCO3 l phn ng cng cis nn B l cisBut2ene. B
b. C ch chuyn ha A
23
ng phn ha v tr
ng phn ha khng gian Hai cation trung gian hnh thnh khi protone ha A v B l ng nht nn c th chuyn ha A thnh B v ngc li.
(B)
cation trung gian
(A)
Bi 14: Khi un nng 2methylcyclohexane1,3dione vi but3ene2one trong dung dch kim
ngi ta thu c mt hp cht hu c (sn phm chnh) c cng thc C11H14O2.
Bi 15: C ch phn ng a. Phn ng xy ra qua 4 bc
Bc 1: To carbocation
H 2O (CH3 )3C OH + H + (CH3 )3C O + H 2 (CH 3 )3C+
24
Bc 2: To isobutene v isobutane
Bc 3: To carbocation trung gian
Bc 4: To sn phm
b. Nu thay bng p-xylene th phn ng theo c ch SE thng thng v s ly ion hydride t nhm
methyl l khng th c. Sn phm l:
25
Part 4
ALKANE, CYCLOALKANE
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Bi 1: Tnh nhit phn ng H cho cc phn ng sau y: a. (CH3)3CH + F2 (CH3)3CF + HF. b. (CH3)3CH + Cl2 (CH3)3CCl + HCl. c. (CH3)3CH + Br2 (CH3)3CBr + HBr. d. (CH3)3CH + I2 (CH3)3CI + HI.
Cho bit cc gi tr nng lng phn ly lin kt (Kcal/mol): (CH3)3CH = F2 Cl2 Br2 I2 = = = = 93,60 37,20 58,32 46,32 36,14 (CH3)3CF (CH3)3CCl (CH3)3CBr (CH3)3CI = = = = 110,64 81,36 67,44 52,32 HF HCl HBr HI = = = = 135,84 103,68 87,60 71,29
Bi 2: Hon thnh cc phng trnh phn ng sau y:

t a. CH3CH2CH2CH2CH3 + O2
o
( red ) d. CH3CH2I + HI
b. CH3CH2CH2CH2CH3 + HNO3 c. (CH3)2CHCl + Na
Zn / HCl e. CH3CH2C(=O)CH3 h f. CH3CH2CH(CH3)2 + Br2
Bi 3: Cho bit sn phm to thnh khi un nng hn hp kh CH3I v HI. Trnh by c ch v tnh ton
gi tr H cho tng giai on. Bit cc gi tr phn ly lin kt (Kcal/mol): II = 36,24 ; CH3H = 105,26 ; HI = 71,29 ; CH3I = 57,17.
Bi 4: Vit qu trnh phn ng Br ha cc cht sau vi s c mt ca benzoylperoxide a. Isopropylbenzene. b. pchlorotoluene. Bi 5: Cho isopentane tc dng vi Cl2 (nh sng h ) thu c 4 sn phm vi thnh phn t l nh sau:
1chloro2methylbutane (30%), 1chloro3methylbutane (15%), 2chloro3methylbutane (33%) v 2chloro2methylbutane (22%).

a. Cho bit sn phm no d hnh thnh hn, gii thch. b. Tnh kh nng phn ng tng i ca cc nguyn t hydro gn vi carbon bc I, II, III. Bi 6: Vit c ch phn ng ca 2methylpropane v CCl4 c thc hin 130 140o C vi s c mt
ca tert-butylperoxide.
26
Bi 7: T cyclopropane, hy iu ch 2,3dimethylbutane. Bi 8: Kh nng phn ng tng i ca cc hydro bc I, II, III i vi phn ng chloridize (phn ng Cl
ha) l 1: 3,8 : 5 tng ng.

a. Tnh lng tng i ca monochlorobutane nhn c khi Cl ha nbutane b. Tnh phn trm ca cc sn phm khc nhau. c. Tnh phn trm cc sn phm monochlorated (c Cl ha mt ln) khi Cl ha 2methylbutane. Bi 9: Ngi ta chuyn ha 100 g CH4 thnh CH3Cl vi hiu sut l 40%. Sau cho ton b lng
CH3Cl va to thnh tc dng vi Na thu ethane (Hiu sut 50%). Sau ngi ta Br ha ethane, sau khi phn ng kt thc thy thu c 60% bromoethane. Tnh lng bromoethane sau phn ng Br ha.
Bi 10: T isoamyl chloride, hy vit s iu ch 2,3,4,5tetramethylhexane. Bi 11: Vit cng thc cu to ca cc hp cht sau: a. 2,6dimethylspiro[4,5]decane. b. 1,4dimethylspiro[2,2]pentane. c. Spiro[4,4]nonane. d. Spiro[3,4]oct1ene. e. Bicyclo[3.2.1]octane. f. 2,3dimethyl9isopropylbicyclo[5.3.0]decane. Bi 12: T hp cht c 3 nguyn t Carbon, vit phng trnh tng hp bicyclo[4.1.0]heptane. Bi 13: Hon thnh cc phng trnh phn ng sau v cho bit trong mi phn ng, cht no l cht
trung gian hot ng. Gi tn loi phn ng:

a. CH2=CH2 + CH2N2
Cu Zn b. CH3CH=CH2 + CH2I2
Bi 14: Vit cng thc cu trc cc sn phm ca cc phn ng sau:

(CH 3 )3 COK a. 2methylcyclopent1ene + CHCl3 A + B. (CH 3 )3 COK b. 1 methylcyclopent1ene + CHClBr2 C + D.
Bi 15: Cho nbutane phn ng vi Cl2 theo t l 1 : 1 c chiu sng thu c hn hp A v hn hp kh
B. hp th ht kh HCl trong B cn va 1,6 l dung dch NaOH 1,25M.

a. Vit phng trnh phn ng th ca nbutane vi Cl2 (1 : 1) v nu c ch phn ng. b. Tnh khi lng hn hp A. c. Sn phm chnh trong phn ng th trn chim 72,72% khi lng hn hp A. Tnh khi lng
ca sn phm chnh v ph.

d. Hy cho bit nguyn t H nguyn t carbon bc II tham gia phn ng th vi Cl2 d hn nguyn
t H nguyn t carbon bc I bao nhiu ln.

Bi 16: Hai cycloalkane A v B u c t khi hi so vi methane bng 5,25. Khi Cl ha (1 : 1, askt) th
A cho 4 cht cn B ch cho 1 cht. Xc nh A, B v vit cu dng bn nht sn phm Cl ha t B. Copyright 2009 volcmttl@yahoo.com.vn
26
Bi 17: Phn ng gia spiropentane vi Cl2 c chiu sng l mt phng php iu ch
Chlorospiropentane (mt sn phm monochlorated):
a. Gii thch ti sao phn ng trn thng c s dng iu ch chlorospiropentane. b. Nu c sn phm dichlorated (sn phm Cl ha 2 ln) to thnh. Hy nu phng php tch hai
sn phm .
c. Trnh by c ch phn ng Cl ha trn. Bi 18: Cho s sau:
a. Vit cc phng trnh phn ng theo s chuyn ha trn. b. giai on chuyn B2 thnh B3, trong iu kin c rt t Br2, ngoi B3 ngi ta cn thu c mt
lng nh alkane B4 khc. Hy xc nh B4 v gii thch s to thnh B4.

Bi 19: Hon thnh s phn ng sau:
Trong s trn: Cc cht A, A1, B, B1, B2D2 u l cc hp cht hu c.

Bi 20: T cyclopropane v cc cht v c thch hp, vit cc phng trnh phn ng iu ch cc
cht sau:
a. Diphenyl. b. Teflon (CF2CF2)n.
*** *** *** *** *** *** *** ***
*** *** *** *** *** *** *** ***
27
Part 4
HNG DN GII
H = 115 (Kcal/mol) H = 33 (Kcal/mol) H = 15,12 (Kcal/mol) H = 6,24 (Kcal/mol)
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Bi 1: Tnh nhit phn ng H (Kcal/mol): a. (CH3)3CH + F2 (CH3)3CF + HF b. (CH3)3CH + Cl2 (CH3)3CCl + HCl c. (CH3)3CH + Br2 (CH3)3CBr + HBr d. (CH3)3CH + I2 (CH3)3CI + HI Bi 2: Hon thnh cc phng trnh phn ng: a. CO2 + H2O. b. CH3CH2CH(CH3)NO2, CH3CH2CH2CH2NO2, CH3CH2CH2NO2, CH3CH2NO2, CH3NO2. c. (CH3)2CHCH(CH3)2. d. CH3CH3. e. CH3CH2CH2CH3. f. CH3CH2[(Br)C(CH3)]CH3.
t Bi 3: C ch tng giai on v hiu ng nhit phn ng: CH3 I CH 3 + I
o
1. CH 3 + HI CH 4 + I ; H = 71, 29 105, 0 = 33, 71 (Kcal / mol) 2. I + CH3 I I2 + CH3 ; H = 57, 00 36, 00 = 21, 00 (Kcal / mol) Cng (1) v (2) ta c phn ng: CH3I + HI I2 + CH4 ; H = 12,71 (Kcal / mol)

Bi 4: a. Ta c cc qu trnh
(C6 H 5 COO)2 C6 H 5CH(CH 3 ) 2 C6 H 5 C(CH3 ) 2 + C6 H 5COOH SR
C6 H 5 C(CH3 ) 2 + Br2 C6 H 5CBr(CH 3 ) 2 + Br C6 H 5CH(CH 3 ) 2 + Br C6 H 5 C(CH 3 ) 2

+ HBr
C6 H 5 C(CH3 ) 2 + Br2 C6 H 5CBr(CH 3 ) 2 + Br...
b. C ch tng t cu a. Bi 5: a. 2chloro2methylbutane d to thnh nht v trong phn ng th gc SR, gc t do cng bn th
sn phm cng u tin, m gc (CH 3 ) 2 C CH 2CH 3 c electron t do nm trn carbon bc III nn

bn nht. V vy s kt hp ca gc Cl vi gc (CH 3 ) 2 C CH 2CH 3 l d xy ra nht.

b. Kh nng phn ng tng i ca cc nguyn t hydro gn vi carbon bc I : bc II : bc III
tng ng t l: 1 : 3,3 : 4,4. Copyright 2009 volcmttl@yahoo.com.vn

28
Bi 6: Phn ng c thc hin theo c ch gc t do:
(Me3CO)2 Me3C CCl3
2 Me3CO Me3CCl + CCl3 + Me3C
Me3CO + Me3CH Me3COH + Me3C
+ CCl 4
+ Me3CH CHCl3
Qu trnh pht trin dy chuyn cho n khi cc gc t do gp nhau => xy ra s ngt mch.
Bi 7: iu ch
HBr Ca / NaOH HBr Na Cyclopropane CH 3CH3CH 2 Br CH 3CH = CH 2 CH 3CHBrCH 3 sn phm.
Bi 8: a. C 6 nguyn t H hnh thnh 1chlorobutane (A) v 4 H hnh thnh 2chlorobutane (B). T
l nguyn t ca H (I) : H (II) l 3 : 2. Lng tng i ca sn phm l: (A) = 3 1 = 3 v (B) = 2 3,8 = 7,6
b. Phn trm (A) v (B) l:
3 100% 28% 10,6 7,6 100% 72% %B= 10,6 %A=
c. C 4 sn phm monochlorated khc nhau:
1chloro2methylbutane (C) 2chloro2methylbutane (D) Ta c lng tng i v % cc sn phm l:

Cht (C) (D) (E) (F) Bi 9: p s: 40,9 g Bi 10: iu ch: Lng tng i
2chloro3methylbutane (E) 1chloro3methylbutane (F)

Phn trm
6 1=6 1 5=5 2 3,8 = 7,6 3 1=3
6 100% 28% 21, 6 5 100% 23% 21, 6 7, 6 100% 35% 21, 6 3 100% 14% 21, 6
29
Bi 11: Vit cng thc cu to:
(a)
(b)
(c)
(d)
Bi 12:
(e)
(f)
LiAlH 4 1.KCN HBr Br(CH 2 )3 Br HOOC(CH 2 )3 COOH HO(CH 2 )5 OH Br(CH 2 )5 Br 2.H O +

3
C2 H5 OH C2 H5O HOOC(CH 2 )5 COOH C 2 H 5OOC(CH 2 )5 COOC2 H 5 Claisen Condensation H+ 1.KCN 2.H3O+
Bi 13:
(a) cyclopropane ; (b) methylcyclopropane. Cht trung gian hot ng ca phn ng: (a) l carbene :CH2. (b) l carbenoid ICH2ZnI (tin cht ca carbene :CH2).
Bi 14: a.
Loi phn ng ny l: Phn ng cng hp ng vng.
:CCl2 cng hp cis vo C = C, nhng kt qu l vng ba cnh c th v tr cis hoc trans vi
nhm CH3 to (A) hoc (B):
(A)
(B)
30
b.
Anion ClBr2C: c to thnh s mt Br cho carbene ClBrC: ; carbene ny cng vo C = C v Cl hoc Br s v tr cis so vi nhm CH3 c (C) hoc (D):
(C)
Bi 15: a. Phng trnh phn ng:
(D)
CH3CH2CH(Cl)CH3 (X) + HCl CH3CH2CH2CH3 + Cl2

askt
CH3CH2CH2CH2Cl (Y) + HCl C ch phn ng l c ch th gc t do SR: sn phm chnh l (X), sn phm ph l (Y).
b. m A = 1,6 1,25 92,5=185 c. Khi lng mi sn phm:
mX = 185 72, 72 = 134,532g ; m Y = 185 134,532 = 50, 468g 100
d. Gi kh nng phn ng th bi Cl2 ca mt nguyn t H lin kt vi nguyn t carbon bc II l a,
bc I l b ta c:
4a a 100 = 72, 72 109,12a = 436,32b = 3, 998 4 4a + 6b b
Bi 16: a. MA = MB = 16.5,25 = 84 g/mol A v B l ng phn ca nhau (v u l cycloalkane). Gi
CTPT ca A, B l CxHy ( x 3 ; 6 y 2x ) 12x + y = 84 CTPT ca A, B l C6H12. Khi mono-Cl ha B thu c mt hp cht duy nht B l cyclohexane. Khi mono-Cl ha A thu c 4 hp cht V vy A c th l methylcyclopentane hoc A l iso-propylcyclopropane.
b. Cu dng (gh) bn nht ca sn phm mono-Cl ha t B l echlorocyclohexane.
31
Bi 17: a. Do cu trc ca spiropentane l i xng, cc nguyn t H trn nhm methylene u nh nhau,
do phn ng mono-Cl ha c th xy ra trn bt c nhm methylene no.

b. Tch bng phng php chng ct phn on v sn phm mono-Cl ha c nhit si thp hn
sn phm di-Cl ha.

c. Phn ng xy ra theo c ch th gc t do SR. Bi 18: a. Hon thnh s phn ng:
t (1) C4H10 CH3CH=CH2 + CH4 Ni / t (2) CH3CH=CH2 + H2 CH3CH2CH3 askt (3) CH3CH2CH3 + Br2 CH3CHBrCH3 + HBr Ether khan (4) CH3CHBrCH3 + Mg (CH3)2CHMgBr
o o
(5) (CH3)2CHMgBr + C2H5Br (CH3)2CHCH2CH3 + MgBr2

xt,t (6) (CH3)2CHCH2CH3 CH2=CCH3CH=CH2 + 2H2 xt,t (7) n CH2=CCH3CH=CH2 (CH2CCH3=CHCH2)n 1500 C (8) 2CH 4 HC CH + 3H 2 lanh nhanh Ni / t (9) HC CH + 2H 2 CH3 CH3 askt (10) CH3CH3 + Br2 CH3CH2Br + HBr Carbon ,600 C (11) 3HC CH C6H6 H 2SO 4 (12) C6H6 + CH2=CHCH3 C6H5CH(CH3)2 Fe,t (13) C6H5CH(CH3)2 + Br2 p-BrC6H4CH(CH3)2 + HBr askt (14) p-BrC6H4CH(CH3)2 + Br2 p-BrC6H4CBr(CH3)2 + HBr H 2SO 4 (15) C6H5CH(CH3)2 + HNO3 p-O2NC6H4CH(CH3)2 + H2O
o o o o o o
b. B4 l n-butane
To thnh B4 l do phn ng th gc t do SR ca C2H6 vi Br2 nh sau:

askt (1) Br Br 2Br
(2) CH 3 CH 3 + Br CH 3 CH + HBr 2 CH3 CH + Br2 CH3CH 2 Br + Br 2 CH3 CH3 + Br CH3 CH + HBr... 2 (3) CH 3 CH + Br CH 3CH 2 Br 2 Br + Br Br2 CH3 CH + CH 2 CH 3 CH 3CH 2 CH3CH 2 2 Copyright 2009 volcmttl@yahoo.com.vn
32
Bi 19: Cht Cng thc cu to Cht Cng thc cu to
A B C D G A1 Ngoi ra: Bi 20: a.
CH2=CH2 C2H5OH CH3CHO CH3COOH CH2=CHCH=CH2 CH3CH=CH2
B1 C1 D1 B2 C2 D2
CH2=CHCH2Cl ClCH2CHOHCH2Cl HOCH2CHOHCH2OH CH3CHClCH3 (CH3)2CHMgCl (CH3)2CHCH2CH2OH
Nu C l CH3COOH th D l (CH3COO)2Ca Nu A l CH4 th B l HC CH , C l CH3CHO
H2 Cl2 ,askt t 1500 C C C3 H8 CH 4 C 2 H 2 C6 H 6 cyclohexane methylcyclohexane 1:1 600o C xt,t o
+ C6 H 6 xt,t phenylcyclohexane diphenyl AlCl ,t o

3
b.
H2 Cl2 HF Zn xt,t ,p HC CH C 2 H 6 C 2Cl6 CClF2 CClF2 CF2 = CF2 teflon Ni,t o to SbCl ,t o ,p
5
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Part 5
ALKENE, ALKINE, DIENE, TERPENE

33
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Bi 1: Hon thnh cc phng trnh phn ng di y v biu din ng phn lp th ca cc sn phm
to thnh bng cng thc chiu Fischer.

a. cisbut2ene + Br2 b. transbut2ene + Br2
PtO 2 trans3,4dimethylhex3ene + H2 sn phm.
c. Acid fumaric + Br2 d. Acid maleic + Br2
Bi 2: Phn ng sau cho sn phm l hp cht mesomeric hay bin th racemic:
Bi 3: Cho bit sn phm to thnh khi ozone ha cc hp cht sau y: a. CH3CH=CH2. b. CH2CHCH(CH3)CH=CH2. c. 1methylcyclohexa1,4diene. Bi 4: Vit cc qu trnh iu ch: a. CH3CH2COCH(CH3)2 t propene, HCl, Mg, BH3, H2O2, NaOH, CrO3. b. Cyclopentanone t cyclobutene, O3, Zn/CH3COOH, LiAlH4, PBr3, Mg, HCOOCH3, CrO3. Bi 5: em dn xut halogen C6H13I un nng vi dung dch KOH/alcohol thu c sn phm (A). Cho
(A) tc dng vi O3 thy to thnh hp cht ozonide (B). Thy phn (B) cho CH3CHO v aldehyde isobutyric. Xc nh cng thc cu to ca C6H13I, (A) v (B).
Bi 6: Vit phn ng DielsAlder ca Buta1,3diene vi cc hp cht sau y: a. Anhydride maleic. b. Methylvinylcetone. c. Acid maleic. d. Acid fumaric. e. H2C=CHCH=CH2. f. C6H5CH=CHNO2. Bi 7: Cho bit sn phm to thnh khi cho isobutene tc dng vi cc cht sau: a. HI. b. HI (Peroxide). c. Br2/H2O. d. Br2 + NaCl (H2O). Bi 8: Cho bit sn phm chnh to thnh khi cho CH3 C CLi tc dng vi cc hp cht sau y: a. CH3CH2Br. b. Cyclopentanal. c. Cyclohexanone. d. CH3 CH CH2 e. KMnO4 long (lnh). f. 1. O3 ; 2. (CH3)2S. g. 1. B2H6 ; 2. H2O2/OH.
Bi 9: Hon thnh chui phn ng sau y:

1.CH 3COCH3 C2 H5 MgBr 1.CO 2 HC CH BrMgC CMgBr A B C D 2.H O + 2.H O +
3 3
34
Bi 10: Khi cho isobutene vo dung dch c ha tan HBr, NaCl, CH3OH c th to ra nhng cht g, gii
thch v vit c ch phn ng.

Bi 11: Cho dn xut halogen CH3CH=CHCH2Cl (A) a. Cho (A) tc dng vi dung dch Cl2 trong bng ti. Vit cng thc cu to ca sn phm. b. Nu un nng (A) vi dung dch kim long thu c monoalcohol tng ng. Cho thm kim
vo, tc phn ng khng thay i. Hy cho bit c ch phn ng v so snh kh nng phn ng ca (A) vi n-CH3CH2CH2CH2Cl v CH2=CHCH2Cl trong cng iu kin phn ng, gii thch.
Bi 12: Hydrocarbon (X) c trong tinh du tho mc. Khi cho (X) tc dng vi lng d acid HCl thu
c sn phm duy nht c cha 2 nguyn t chlorine trong phn t. Ozone phn (X) thu c hn hp (CH3)2CHCOCH2CHO v CH3COCH2.
a. Xc nh cng thc cu to ca (X). Vit cc phng trnh phn ng xy ra. b. Hydrocarbon (Y) cng c cng cng thc phn t vi (X). Khi ozone phn (Y) thu c (Z) c
cng thc phn t C10H16O2. Cho bit (Z) c cu to i xng v c mch carbon khng phn nhnh. Xc nh cng thc cu to ca (Y) v (Z).
Bi 13: Khi un nng hn hp Buta1,3diene v ethene thy xy ra phn ng ng vng DielsAlder
to thnh cyclohexene. Phn ng ny tr nn d dng hn nu thay H trong ethene bng nhm ht electron nh COOH, COOR, CHO, v thay H trong buta1,3diene bng nhm y electron nh CH3, C2H5,
a. Vit phng trnh phn ng xy ra khi cho Buta1,3diene tc dng vi ethene, cho bit cu trc
ca Buta1,3diene trc phn ng (scis hay strans).

b. un nng transpenta1,3diene vi acid acrylic CH2=CHCOOH, vit cu to sn phm chnh. c. So snh tc phn ng ca mi diene sau vi acid acrylic.
2methylbuta1,3diene v 2chlorobuta1,3diene. Cispenta1,3diene v transpenta1,3diene.
Bi 14: Khi trng hp Buta1,3diene to cao su Buna thng to ra sn phm ph l vng 6 cnh
cha no (phn ng DielsAlder), khi phn ng vi H2 d xc tc Ni th to ra ethylcyclohexane. Vit cc phng trnh phn ng v cho bit iu kin phn ng ng vng DielsAlder xy ra d dng.
Bi 15: C 2 hydrocarbon (A), (B) u c cng thc phn t l C7H14. Bit rng:
Oxygen ha (A) bng dung dch KMnO4/H2SO4 to ra 2 cht CH3CH2COCH3 v CH3CH2COOH. (B) c cu to mch thng v khi oxygen ha bng dung dch K2Cr2O7/HCl to ra CO2.
Xc nh cng thc cu to ca (A), (B) v hon thnh cc phng trnh phn ng.
Bi 16: Mt alkene sau khi ozone phn to ra sn phm hu c duy nht l CH3CHO. Khi cng hp vi
Br2 trong bnh lm bng vt liu phn cc th ch to ra mt sn phm l mt ng phn khng quang hot. Hy cho bit cng thc phn t ca alkene v vit cng thc cu to ca sn phm theo Fischer, Newman ri gi tn sn phm.
35
Bi 17: Alkene (A) c cng thc phn t l C6H12 c ng phn hnh hc, tc dng vi dung dch Br2 cho
hp cht dibromine (B). Cho (B) tc dng vi KOH trong alcohol un nng thu c alkadiene (C) v mt alkine (D). Khi (C) b oxygen ha (oxygenize) bi dung dch KMnO4/H2SO4 v un nng thu c acid acetic v CO2. Xc nh (A), (B), (C), (D) v vit cc phng trnh phn ng xy ra.
Bi 18: Khi cyclotrimer ha buta1,3diene vi s c mt ca cht xc tc c kim, ngi ta iu ch
c (Z, E, E)cyclodeca1,5,9triene. y l mt phng php n gin iu ch hydrocarbon vng ln. Khi dng cc cht xc tc thch hp l cc phc allyn ca kim loi chuyn tip, ngi ta iu ch c (E, E, E)cyclodeca1,5,9triene v (Z, Z, E)cyclodeca1,5,9triene. Vit cng thc cu to ca cc hp cht trn.
Bi 19: Ozone phn mt terpene (A) C10H16 thu c mt cht (B) c cu to nh sau:
CH3 C CH2 CH CH CH2 CH = O O H3C t C10H20.

a. Xc nh cng thc cu to ca (A). b. Vit cng thc cc ng phn cu to trong hn hp (X). Bi 20: T mt loi tinh du ngi ta tch c cht (A) v (B) l ng phn hnh hc ca nhau. Kt qu
C CH3
Hydro ha (A) vi xc tc kim loi to ra hn hp sn phm (X) gm cc ng phn c cng thc phn
phn tch cho thy (A) ch cha 78,95% C v 10,52% H v khi lng, cn li l O. T khi hi ca A so vi H2 l 76. (A) phn ng c vi dung dch AgNO3/NH3 cho kt ta Ag v mui ca acid hu c. Khi b oxygen ha (oxygenize) mnh, (A) cho mt hn hp sn phm gm acetone, acid oxalic v acid levulinic CH3COCH2CH2COOH. Khi cho Br2/CCl4 phn ng vi (A) theo t l mol 1 : 1 thu c ba dn xut dibromine. Phn t (A) bn hn (B). Xc nh cng thc cu to ca (A), (B).
Bi 21: 1.
Hp cht A (C10H18O) c phn lp t mt loi tinh du Vit Nam. A khng lm mt mu nc bromine v dung dch thuc tm long, cng khng tc dng vi hydro c xc tc Ni, nhng li tc dng vi HCl m c sinh ra 1chloro4(1chloro1methylethyl)1methylcyclohexane. Hy xut cu trc ca A.
2.
Hp cht B (C10H20O2 ) c trong mt loi tinh du Nam M. T B c th tng hp c A bng cch un nng vi acid.
a. b.
Vit cng thc cu to v gi tn B. Dng cng thc cu trc, vit phng trnh phn ng v trnh by c ch y ca phn ng tng hp A.
3.
Hp cht B thng c iu ch t C (2,6,6trimethylbicyclo[3.1.1]hept2ene) c trong du thng. Dng cng thc cu to, vit phng trnh phn ng v ch r cc lin kt ca C b t ra.
36
4. 5.
Trong cy long no c hp cht D tn l 1,7,7trimethylbicyclo[2.2.1]heptan2one. Vit s cc phn ng tng hp D t C v cho bit c ch ca giai on u. V cu to ha hc, cc hp cht A, B, C v D trn c c im g chung nht. Minh ha vn tt c im trn cc cng thc cu to ca chng.
Bi 22: Anethole c phn t khi l 148,2 v hm lng cc nguyn t: 81,04% C, 8,16% H, 10,8% O.
(Bit H = 1,008 ; C = 12,000 ; O = 15,999). Hy:

a. Xc nh cng thc phn t ca anethole. b. Vit cng thc cu trc ca anethole da vo cc thng tin sau: -
Anethole lm mt mu nc bromine. Anethole c hai ng phn hnh hc. S oxygen ha anethole to ra acid methoxybenzoic (M) v s nitro ha M ch cho duy nht acid methoxynitrobenzoic.
c. Vit phng trnh ca cc phn ng: (1) anethole vi bromine trong nc ; (2) oxygen ha
anethole thnh acid methoxybenzoic ; (3) nitro ha M thnh acid methoxynitrobenzoic. Vit tn ca anethole v tt c cc sn phm hu c nu trn theo danh php IUPAC.
d. V cu trc hai ng phn hnh hc ca anethole. Bi 23: Tin hnh phn ng gia 3,5,5trimethycyclohex2enone v n-butylmagnesiumiodide. Sau ,
thy phn hn hp bng dung dch HCl 4M thu c hp cht B. B b chuyn thnh nm ng phn, k hiu t D1 n D5 c cng thc phn t C13H22. Vit cng thc cu to ca cc ng phn D1, D2, D3, D4, D5 v gii thch s hnh thnh chng.
Bi 24: Mt monoterpenoid mch h A c cng thc phn t C10H18O (khung carbon gm hai n v
isoprene ni vi nhau theo qui tc uui). Oxygen ho A thu c hn hp cc cht A1, A2 v A3. Cht A1 (C3H6O) cho phn ng iodoform v khng lm mt mu nc bromine. Cht A2 (C2H2O4) phn ng c vi Na2CO3 v vi CaCl2 cho kt ta trng khng tan trong acid acetic ; A2 lm mt mu dung dch KMnO4 long. Cht A3 (C5H8O3) cho phn ng iodoform v phn ng c vi Na2CO3.
a. Vit cng thc cu to ca A1, A2 v A3. b. V cng thc cc ng phn hnh hc ca A v gi tn theo danh php IUPAC. Bi 25: T benzene v cc hp cht hu c c s C 3, vit s tng hp cis-1-phenylhex-2-ene. Bi 26: Hon thnh s phn ng sau, xc nh cc hp cht t A n I:
PCl5 CH3 MgI 1.LiNH 2 H2 Ac2 O 1.Mg,ether khan t X A B C D E F I(C19 H 38O 2 ) 2. CH 2 =C(CH 3 )-CHO 2.C6 H13 Br Pd/C ether khan
o
Cho bit: X l:
A c 1H ethylenic, B c 5H ethylenic, D c 1H ethylenic. Copyright 2009 volcmttl@yahoo.com.vn

37
Bi 27: A, B l hai hydrocarbon c tch t du m c cc tnh cht vt l v d kin phn tch nh sau: ts (oC) A B tnc (oC) %C %H
68,6 67,9
-141 -133
85,63 85,63
14,34 14,34
A cng nh B lm mt mu nhanh chng dung dch KMnO4 v nc bromine, khi ozone phn cho sn phm ging nhau. Xc nh cu trc ca A, B.
Bi 28: Hon thnh s phn ng sau:
NaNH 2 1.CH 3MgBr HC CNa NaI HC CNa 3(l) CH3CH 2 CH 2 I A B C D E(C11H18 ) F Br-(CH 2 )4 -Cl S 2 3.H 2 O 2.CO 2
N
1.NaNH 2 2.Na/NH
F G(C12 H 20O 2 ).
H 2 (1mol) Pd/CaCO3
Bi 29: Pheromol (H) c Bestmann iu ch nm 1982 nh sau:

Me(CH 2 )8 Br 2H 2 1.EtMgBr 1.EtMgBr bromine ha HC CLi A B C D E ( C16 H 29 Br ) 2.HC C-CH 2 -OTs 2.Epoxide Pd,Lindlar CBr4 +PPh 3 Ph 3 P NaI 1.Base E F G H . acetone 2.CH 2 =CH-CHO
Xc nh cng thc cu to cc cht t A n G. Bit H l:

Bi 30: Acid Abscisic (ABA) thuc loi sesquiterpenoid c nhiu trong gii thc vt c tc dng iu
chnh gic ng ng ca cy ci v cho php cy tn ti trong mi trng bt li. C nhiu phng php tng hp ABA. y dn ra phng php i t acetone.
HOCH H 3C H 4 2OHH 3 3CH 3COCH 3 NaNH 2 A -2H 2O B(C19 H13O) p-CH26CHSO C(C11H18O 2 ) D(C11H18O 2 )
+
D KMnO4 [E](C11H 20 O 4 ) KMnO4 F(C11H18O 4 ) CH3SO2Cl G(C11H15O3 ) pyridine OH OHTip theo s ni mch to thnh acid nh sau:
4 Methyl - 3 - methylpent - 2(Z) - ene - 4 - inoate LDA H (Li + C7 H 7 O 2 ) G I(C18 H 22 O5 Li) H 2O K CrSO L DMF
4 L NHO M 1.CH+3 2O acid Abscisic (ABA). ONa,H H2 2.H +
a. Vit CTCT cc cht t A n M bit rng hn hp methanesunfonyl chloride/pyridine dng
tch nc alcohol bc ba.

b. Acid Abscisis c tnh quang hot hay khng, n c cu hnh nh th no.
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Part 5
HNG DN GII
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Bi 1: Biu din cu hnh sn phm bng cng thc chiu Fischer:
38
Bi 2: Hn hp racemic
Bi 3: a. b. c. Bi 4:
HCl Mg a. CH3CH = CH 2 CH 3 CHCl CH3 CH3 CH(MgCl) CH3 1.BH3 CrO3 CH3CH = CH 2 CH 3CH 2 CH 2 OH CH 3CH 2CHO 2.H O ,OH
2 2 +
CH3CHO + HCHO. OHCCHCH3CHO + 2HCHO. OHCCH2COCH3 + OHCCH2CHO
(1) (2)
CrO3 H 3O (1) + (2) CH3CH 2 CHOH CH(CH 3 ) 2 CH3CH 2 CO CH(CH 3 ) 2 .

1.O3 LiAlH 4 1.PBr3 b. cyclobutene OHCCH 2CH 2CHO HO(CH 2 ) 4 OH BrMg(CH 2 )4 MgBr 2.Zn/CH 3COOH 2.2Mg CrO3 1.HCHO cyclopent an ol cyclopen tan one. 2.H O +
3
Bi 5: C6H13I l
Bi 6:
39
Bi 7: a. b. c. d. e. f. g. Bi 8: a. b.
tert-butyliodide. Tert-butyliodide. 1bromo2methylpropanol. 1-bromo-2-chloro-2-methylpropane, 1,2-dibromo-2-methylpropane, 1-bromo-2-methylpropanol. 2methylpropan1,2diol. Acetone v formaldehyde. Isobutanol. CH3 CH 2 C C CH 3 . Sn phm l
c.
Sn phm l
d. Bi 9:
CH3 CHOH CH 2 C C CH 3
A l HC CMgBr ; B l
Bi 10: Sn phm phn ng l hn hp gm:
; C l
; D l
40
(CH3)3CBr ; (CH3)3COH ; CH3[(HO-)C(-Cl)]CH3 ; (CH3)3COCH3 Gii thch da vo c ch phn ng:

-
Trong dung dch c cc qu trnh phn ly: HBr H+ + Br NaCl Na+ Cl Do trong dung dch c 4 tc nhn l Br, Cl, H2O v CH3OH c kh nng kt hp vi carbocation. Phn ng theo c ch cng electrophile (AE). u tin, H+ tn cng vo C to carbocation (CH3)3C (giai on chm.) Sau 4 tc nhn trong dung dch s kt hp carbocation to sn phm (giai on nhanh).
Bi 11: a. CH3CHClCHClCH2Cl. C ch AE. b. C ch SN1: CH3CH=CHCH2Cl > CH2=CHCH2Cl > CH3CH2CH2CH2Cl. Bi 12: a. Cng thc ca X l:
b. Cng thc ca Y v Z ln lt l:
Bi 13: a. Buta1,3dien dng s-cis. Phn ng:
b. Phn t penta1,3diene c nhm CH3 y electron cn acid acrylic c nhm COOH ht electron
nn c s phn cc cc lin kt theo chiu mi tn cong. Sn phm chnh to thnh do cc nguyn t C mang in tch tri du kt hp vi nhau.
c. So snh kh nng phn ng:
41
2methylbuta1,3diene > 2chlorobuta1,3diene. Cispenta1,3diene < transpenta1,3diene.
Bi 14: a. Phng trnh phn ng:
to, xt + ;
+ 2H2
to, xt
b. iu kin: Hp cht diene (A) phi c cu hnh s-cis. Phn ng ny tr nn d dng hn nu thay
H trong dienophile bng nhm ht electron nh COOH, COOR, CHO, v thay H trong diene bng nhm y electron nh: CH3, C2H5,
Bi 15:
A l 3methylhex3ene. B l Hept1ene.
Bi 16:
Alkene l But2ene Phn ng cng Br2 vo But2ene l cng trans nn to ng phn khng quang hot th alkene But2ene phi dng trans.Cng thc Fischer, Newman ln lt l:
Bi 17:
(A) l: CH3CH2CH=CHCH2CH3. (B) l: CH3CH2CHBrCHBrCH2CH3.

Bi 18: Cng thc cu to:
(C) l: CH3CH=CHCH=CHCH3. (D) l: CH3CH 2 C = CCH 2 CH3 .
Z, E, E
E, E, E
Z, Z, E
Bi 19:
42
a. Cng thc cu to ca A:
b. Hn hp X:
Bi 20:
(A) l trans- (CH3)2C=CHCH=C(CH3)CH2CH2CHO. (B) l cis- (CH3)2C=CHCH=C(CH3)CH2CH2CHO.

Bi 21: 1. Xc nh cng tc cu trc ca A(C10H18O). A c = 2 .
A khng lm mt mu dung dch nc bromine v dung dch thuc tm long chng t trong A khng c ni i hay ni ba.
A khng tc dng vi hydro trn cht xc tc Ni chng t trong A khng c nhm chc carbonyl. A tc dng vi acid HCl c c 1chloro4(1chloro1mehylethyl)1methylcyclohexane nn trong A c vng no v c lin kt ether.
Suy ra cng thc cu trc ca A

CH3
O O
CH3 O
H3C
CH3 O CH3
CH3
2.a. Vit cng thc cu to, gi tn B
B l mt diol c b khung carbon nh A Gi tn B: 1-hydroxy-4-(-1-hydroxy-1-methylethyl)-1-methylcyclohexane.
OH
H H2O
+
OH B
2. b. Dng cng thc cu trc, vit phng trnh phn ng v trnh by c ch y ca phn ng.
43
C 2 dng trans v cis ca B u cu dng gh bn vng, tuy vy cu dng gh khng th tham gia ng vng m phi i qua dng thuyn km bn. Dng thuyn s tham gia phn ng SN1 ni phn t.
(+)
OH
+
OH
OH
OH OH
H
+
O OH
(+)
Cis-B
(+)
OH OH OH Trans-B OH OH
H
+
O OH
(+)
3. Lin kt ca C b t cc ng chm chm:

OH +
2 H2O H
+
OH
4.
HCl
Cl
H2O
HO
O
C
H+ Cl-
(+)
(+)
chuy v n
5. c im chung nht v cu to ho hc: mi phn t gm 2 n v isoprene (hoc isopentane) ni
vi nhau.
Bi 22:
44
a. Xc nh cng thc phn t:
C = (81,04/12,00) = 6,75 ; H = (8,16/1,01) = 8,08 ; O = (10,8/16,0 = 0,675 C = 6,75/0,675 = 10 ; H = (8,08/0,675 ) = 12 ; O = 1 => C10H12O
b. Vit cng thc cu trc ca anethole:
Anethole lm mt mu nc bromine nn c lin kt i ; v tn ti dng hai ng phn hnh hc (lin kt i, ) v khi oxygen ha cho acid nn c lin kt i mch nhnh ; v ch cho 1 sn phm sau khi nitro ha nn nhm methoxy v tr 4 (COOH- nhm th loi 2, methoxy nhm th loi 1. l acid 4-methoxy-3- nitrobenzoic. Vy anethole l:
c. Cc phng trnh phn ng:
(1) anethole vi Br2/H2O
(2) oxygen ha anethole thnh acid methoxybenzoic:
(3) nitro ha M thnh acid methoxynitrobenzoic:
Tn ca anethole v tt c cc sn phm hu c nu trn theo danh php IUPAC: (2) 2-Bromo-1-(4-methoxiyphenyl) propan-1-ol. (3) Acid 4-methoxybenzoic ; (4) Acid 4-methoxy-3-nitrobenzoic.
d. Hai ng phn hnh hc ca anetol:
(E)-1-methoxy-4-(1-propenyl)benzene
(Z)-1-methoxy-4-(1-propenyl)benzene
45
hoc (E)-1-(4-methoxyphenyl) prop-1-ene
hoc (Z)-1-(4-methoxyphenyl) prop-1-ene
Bi 23: Cng thc cu to ca 5 ng phn, k hiu t D1, D2, D3, D4 n D5
Bi 24: a. Xc nh A1, A2, A3 -
A l hp cht mch h nn c 2 ni i A1 tham gia phn ng iodofom nn A1 l hp cht metyl xeton CH3COCH3 + I2 /KOH CHI3 + CH3COONa
A2 phn ng vi nn y l mt acid, da vo cng thc phn t y l mt diacid HOOC-COOH + Na2CO3 NaOOCCOONa + H2O + CO2
A3, C5H8O3, cho phn ng iodoform, phn ng c vi Na2CO3. A3 va c nhm chc methyl cetone va c nhm chc acid. Vy A1: CH3COCH3, A2: HOOCCOOH, A3: CH3COCH2CH2COOH
b. A l monoterpene mch h nn c b khung carbon l:
Da vo cu to ca A1, A2, A3 nn xc nh c v tr cc lin kt i trong mch carbon (hnh trn): V c s hnh thnh acid oxalic nn A c th l: (E) hoc (Z)3,7dimethylocta2,6dienol
Bi 25: S tng hp:
1.NaNH 2 1.NaNH 2 H2 HC CH CH 3CH 2CH 2C C H CH3CH 2CH 2C CCH 2C6 H5 2.CH 3CH 2 CH 2 Br 2.C6 H5 CH 2 Br xc tc Lindlar CH 3 Br Br2 ,as C cis-1-phenylhex-2-ene. Trong : HC CH C6 H 6 C6 H 5CH3 C6 H5CH 2 Br. AlBr3 600o C
Bi 26:
46
Bi 27: Da vo kt qu phn tch nguyn t, A v B c cng thc C6H12. c th l ng phn
cis/trans ca hex2ene hoc hex3ene. Do ozone ha cho sn phm ging nhau nn l ng phn ca hex3ene. A l ng phn cis v c nhit nng chy thp hn vo nhit si cao hn => B l trans.
Bi 28:
NaNH 2 HC CNa NaI CH3CH 2 CH 2 I C3 H 7 C CH n - PrC C(CH 2 )3 CH 3 n - PrC C(CH 2 )3 CH 2 I Br-(CH 2 )4 -Cl S 2
N
1.CH3 MgBr HC CNa n - PrC C(CH 2 ) 4 C CH Trans - n - PrCH = CH(CH 2 )4 C CH 3.H 2 O 2.CO 2 H 2 (1mol) Trans - n - PrCH = CH(CH 2 ) 4 C C - COOH Acid dodeca - 2Z,8E - dienoic (C12 H 20 O2 ). Pd/CaCO3
1.NaNH 2 2.Na/NH 3(l)
Bi 29:
t R l CH3(CH2)8:
RBr 1.EtMgBr 1.EtMgBr HC CLi HC CR(A) HC CCH 2 C CR(B) RC CCH 2 C CCH 2 CH 2 OH(C) 2.HC C-CH 2 -OTs 2.Epoxide 2H 2 bromine ha (Z, Z)RCH = CHCH 2 CH = CHCH 2 CH 2 OH(D) (Z, Z)RCH = CHCH 2 CH = CH(CH 2 ) 2 Br(E) Pd,Lindlar CBr4 +PPh 3 Ph 3P NaI (Z, Z)RCH = CHCH 2 CH = CH(CH 2 ) 2 I(F) (Z, Z)RCH = CHCH 2CH = CH(CH 2 ) 2 P Ph 3 I (G) acetone +
Bi 30: a. Cng thc cu to cc cht:
47
b. ABA l hn hp racemic khng c tnh quang hot, c cu hnh Z, E, Z.
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Part 6
HYDROCARBON THM, DN XUT

48
HALOGEN, HP CHT C KIM.

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Bi 1: Gii thch cc d kin sau: a. Kh nng phn ng ca chlorobenzene km benzene trong phn ng th i in t, d rng nh
hng vn u tin o-, p-.

b. Ion phenolate tham gia phn ng th i in t cc v tr o-, p-. c. Phn ng th i in t ca acid benzoic u tin cho sn phm m-. d. Phenol d b Br ha hn benzene. e. Cc dn xut halogen ca hydrocarbon thm kh tham gia phn ng th i nhn hn dn xut
alkylhalogenide.
Bi 2: Ba hp cht trimethylbenzene sau, cht no c kh nng hot ha mnh nht trong phn ng th
in t SE: (1) 1,2,3trimethylbenzene ; (2) 1,2,4trimethylbenzene ; (3) 1,3,5trimethylbezene.

Bi 3: Vit cc sn phm to thnh ca cc phn ng sau y: a. Phn ng sulfonic ha p-methylcumene. Bi 4: Hon thnh cc phn ng chuyn ha sau:
H 2 O,t a. Br(CH2)3pC6H4CH2Br 1.KCN,DMSO b. C6H5CH2Cl 2.H + ,H O,t o
2 o
b. Phn ng sulfonic ha p-acetyltoluene.
1.SO3 .H 2SO 4 c. C6H5CH3 2.HNO3 /H 2SO 4 3.NaOH,t o
d. e.
1.CH3 (CH 2 )3 Li 2.C6 H 5CHO 3.H 3O + ,t o
Na 2 Cr2 O 7 / H 2SO 4
f.
1.MnO 2 2.KOH,H O,t o

2
Bi 5: T benzene hoc methylbenzene, hy vit phng trnh iu ch: a. C6H5CH2CH2C CH. b. p-ClC6H4CONH2. c. C6H5COpC6H4COOCH3. d. Acid 2,6dibromobenzoic.
Bi 6: Cht A c cng thc C8H6 v lm mt mu nc Br2, phn ng vi AgNO3/NH3 cho kt ta,
oxygen ha thu c acid benzoic. Xc nh cng thc cu to ca cht A.

Bi 7: Khi un nng 1,4dibromobutane vi Na2S s to thnh thiophene C4H4S. Bng phng php trn,
hy iu ch methylthiophene.
Bi 8: Trong phn ng Cl ha nh cht xc tc FeCl3, kh nng phn ng tng i ti cc v tr khc
nhau trong cc phn t biphenyl v benzene nh sau:
49
a. Trnh by c ch phn ng Cl ha biphenyl theo hng u tin nht. b. Tc mono-Cl ha biphenyl v benzene hn km nhau bao nhiu ln. c. Trong mt phn ng mono-Cl ha biphenyl thu c 10 grams 2chlorobiphenyl th s thu c
bao nhiu grams 4chlorobiphenyl.

Bi 9: Hon thnh cc chui phn ng sau:
H 3O SO 2 Cl KCN a. CH3CHOHCH 3 (A) (B) (C). CH 2 = CH 2 KCN / alcohol b. I(CH 2 ) 4 I (A) (B).
+
Bi 10: Vit phng trnh phn ng ca ethylmagnesiumbromide vi cc cht sau: a. CH3CH2CN. b. CH3COCl. c. C2H5CHCH3C CH. d. CH3COOC2H5. e. C2H5COCH3. Bi 11: Cho bit sn phm ca cc phn ng sau:
Bi 12: Indene C9H8 c tch t nha than , c phn ng vi KMnO4 v lm mt mu Br2/CCl4. Tin
hnh hydro ha xc tc trong iu kin m du s nhn c indan C9H10 v trong iu kin mnh hn th Azulene c C9H16. Khi oxygen ha indene c acid phthalic.
a. Xc nh indene, indan, C9H16 v vit cc phng trnh phn ng xy ra. b. T indene, hy iu ch azulene C16H26O. Bi 13: Cho cumene tc dng vi CH3Cl/AlCl3 thu c cc sn phm monomethyl ha trong c A.
Khi cho A tc dng vi KMnO4 un nng thu c cht B c cng thc C8H4O4K2. Cho A tc dng vi Br2 (xc tc bt Fe) thu c hai sn phm mono-Br C v D. Vit cng thc cu to, gi tn A, B, C, D v hon thnh cc phng trnh phn ng minh ha.
50
Bi 14: Cho cetone (I) C5H10O tc dng vi ethylmagnesiumbromide ri tch nc hp cht carbonyl to
thnh thu c alkene (II), cht ny ozone ha ri thy phn cho diethycetone v acetaldehyde. Vit cu trc ca cc hp cht (I), (II).
Bi 15: Vit phng trnh phn ng ca isobutylchloride vi: a. AgOH. b. H2O (khi un si). c. KOH/C2H5OH. d. 1. KCN ; 2. H3O . e. NH3 (un trong ng hn kn). Bi 16: Methyl ether ca p-cresol (A) c cha O18 l mt hp cht qu khng may b trn ln vi
+
f. Na kim loi trong hexane. g. Mg trong ether khan. h. CH3COONa. i. KHS.
iodobenzene. Hy dng phng php thun tin nht c th tch ring hai cht trn. Bit nhit si ca hai cht gn bng nhau v lng cht qu t nn khng th dng phng php sc k iu ch.
Bi 17: Cht A c cng thc phn t l C9H14. Khi oxygen ha bng K2Cr2O7/H2SO4 ta thu c
cetodiacid X mch thng (c t hn A mt carbon), A cng hp H2 to ra n-propylcyclohexane. A phn ng vi KMnO4 long thu c Y (190 g/mol) c cng s carbon vi A. Y phn ng vi CH3COOH xc tc H2SO4 ch to cht Z (C15H24O7). Vit phng trnh phn ng, xc nh A.
Bi 18: Tm cc cht A, B, C, D, E, F v vit cc phng trnh phn ng xy ra theo s sau:
Na2Cr2O4
Cl2 ,1mol H 2O Benzen A B FeCl 3 t o ,P
2[ H ] C D Fe / HCl E F
(1 mol)
HNO3 1:1
Bi 19: Oxygen ho hydrocarbon thm A (C8H10) bng oxygen c xc tc cobalt acetate cho sn phm B.
Cht B c th tham gia phn ng: vi dung dch NaHCO3 gii phng kh CO2 ; vi ethanol (d) to thnh D ; un nng B vi dung dch NH3 to thnh E. Thy phn E to thnh G, un nng G nhit khong 160oC to thnh F. Mt khc, khi cho B phn ng vi kh NH3 (d) cng to thnh F. Hy vit cc cng thc cu to ca A, B, D, G, E v F.
Bi 20: 3iodo2,2dimethylbutane khi phn ng vi AgNO3 trong C2H5OH s cho 3 sn phm. Vit
cng thc cu to ca 3 sn phm y v cho bit sn phm no chim t l ln nht.

Bi 21: m-Fluorisopropylbenzene (I) c tng hp theo 8 bc i t benzene (A). Hy hon thin s
phn ng ny:
+Me2 CHBr/AlCl3 HNO3 +Br2 /Fe HNO2 H 2O 6[H] t Mg A B C D E F G H I HBF4
o
Bi 22: Xut pht t Bromobenzene cha C14 v tr 1 v cc cht v c cn thit khng cha C14, hy
iu ch cc hp cht thm cha C14 v tr 3.

a. Aniline. b. Iodobenzene. c. Acid benzoic.
50
Bi 23: Ephedrine (G) l mt hot cht dng lm thuc cha bnh v h hp c chit t cy ma hong.
3 NO , OH Ni Br Ephedrine c tng hp nh sau: C6H6 CO , HCl / D CH 3CH 22 E H 2 / F CH G AlCl3
a. Vit cng thc cu to ca D, E, F v G trong s trn. b. Vit c ch phn ng ca cc giai on to thnh D v E. c. i t benzene, acid propanoic v cc tc nhn cn thit khc, hy a ra mt s tng hp
ephedrine.
Bi 24: Vit cng thc cu to sn phm cui (nu c) ca cc phn ng sau:
Bi 25: Vit cc phn ng tng hp sn phm t cc cht ban u cho di y:
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Part 6
HNG DN GII
52
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Bi 1: a. Do nguyn t Cl c hiu ng +C. b. Do nh hng y in t ca O, cng hng lm cho cc v tr o-, p- c th mang in tch m
(cng thc gii hn).

c. Do nh hng ht in t ca nhm CHO lm cho v tr o-, p- c th mang in tch dng (cng
thc gii hn).

d. Do hiu ng +C ca nhm OH. e. Do nguyn t Cl c hiu ng +C. Bi 2: (3) > (2) > (1). Bi 3: Vit cc sn phm to thnh:
Bi 4: a. Br(CH2)3pC6H4CH2OH. b. C6H5CH2OH.
Bi 5: a. C6H6
C6H5CH2CH2C CH.
1.Cl2 / FeCl3 2.Na 2 Cr2 O7 3.SOCl2 4.NH 3
1.CH3CH 2 Cl / AlCl3 2.Br2 ,t o 3.(CH3 )3 COOK 4.HBr,ROOR 5.HC CLi
b. C6H5CH3
1.KMnO 4 / OH 2.SOCl2 3.C6 H5 CH 3 /AlCl3 4.Na 2 Cr2 O7 5.CH 3OH/H 2SO 4
p-ClC6H4CONH2.
c. C6H5CH3 C6H5COpC6H4COOCH3.
d. C6H5CH3 Acid 2,6dibromobenzoic. Bi 6: Cng thc cu to ca A l: C6H5 C CH .

Na 2S HBr Bi 7: CH 2 = CHCH 2 CH 2OH CH 3 CHBr CH 2 CH 2 CH 2 Br Metylthiophene .
1.SO3 ,H 2SO 4 2.Br2 ,FeBr3 3.H 2 O,t o 4.Na 2 Cr2 O7 / H 2SO 4
53
Bi 8:
Bi 9: Hon thnh cc chui phn ng:

H 3O SO 2 Cl KCN a. CH3CHOHCH 3 CH3CHClCH 3 CH 3CHCNCH3 CH3CHCOOHCH 3 . CH 2 = CH 2 KCN / alcohol b. I(CH 2 )4 I CH 2 = CH CH = CH 2 cyclohexene.
+
Bi 10: a. CH3CH2COCH2CH3. b. CH3COCH2CH3. c. C2H5CHCH3C CMgBr + C2H6 d. CH3COOC2H5. e. (C2H5)2C(OH)CH3. Bi 11: Cho bit san phm ca cc phn ng:
Bi 12: a. Cng thc cu to:
54
b. iu ch:
Bi 13: A l p-methylcumene. Cc phn ng:

t A + 8KMnO4 p-KOOCC6H4COOK (B) + 2K2CO3 + 8MnO2 + 2KOH + 4H20.
o
+ Br2 (Fe) A C + D HBr
Trong : C l o-Bromo-p-methylcumene. D l m-Bromo-p-methylcumene.

Bi 14: Cng thc cu to cc cht: (I) l diethylcetone. (II) l 3ethylpent2ene. Bi 15: a. CH3CHCH3CH2OH. b. CH3CHCH3CH2OH. c. CH3CHCH3=CH2. d. CH3CHCH3CH2COOH. e. CH3CHCH3CH2NH2. Bi 16: Ha tan hn hp trong ether v thm mt lng Mg va , khi iodobezene chuyn thnh f. CH3CHCH3CH2CH2CHCH3CH3. g. CH3CHCH3CH2MgCl. h. CH3CHCH3CH2OCOCH3. i. CH3CHCH3CH2SH.
phenylmagnesiumiodide. Thm nc vo hn hp sau phn ng, khi phenylmagnesiumiodide c th chuyn thnh benzene trong khi methyl ether ca p-cresol khng thay i. Hn hp lc ny gm c
o o Benzene ( t s = 80o C ) v methyl ether ca p-cresol ( t s = 175o C ) c th phn tch d dng bng phng
php chng ct.

Bi 17: -
T d kin A cng hp H2 n-propylcyclohexane v oxygen ha bng K2Cr2O7/H2SO4 ta thu c cetodiacid X mch thng (t hn A mt carbon) => A c t nht mt lin kt i u mch. V X l cetodiacid => A c 2 lin kt i hoc 1 ni i trong vng v phi c nhm: C C = CH C C
A phn ng vi KMnO4 long thu c Y (190 g/mol) c cng s carbon vi A => s nhm OH trong Y l (MY MA)/17 = 4 => CTPT ca Y l C9H14(OH)4. Y phn ng vi CH3COOH xc tc H2SO4 ch to cht Z (C15H24O7) => Z c 3 nhm ester ca acid acetic v trong phn t cn 1 nhm OH khng to ester. Nhm OH lin kt vi C (III).
54
Vy cng thc cu to ca A l:
Vit cc phng trnh phn ng da vo A l hp cht va tm c trn.
Bi 18: Hon thnh s phn ng:
A l chlorobezene. B l phenol. C l p-benzoquinone.

Bi 19: Cng thc cu to ca cc cht:
CH3 CH3 A B O C C O O
D l hydroquinone. E l p-nitrophenol. F l p-aminophenol.
O C C O
O C C O
O C NH2 160OC C OH G O F O C C O N H
O O + C2H5OH D
O O + NH3 (kh d- ) , C C O N H ftalimit F
C OC2H5 C OC2H5 O
Bi 20: (CH3)3CCHICH3 + Ag+ (CH3)3CC+HCH3 + AgI. C2 H5 OH (CH3)3CC+HCH3 (CH3)3CCH=CH2 (A). C2 H5 OH (CH3)3CC+HCH3 (chuyn v CH3) CH3C+CH3CH(CH3)2 (CH3)2CH=CH(CH3)2
Sn phm (B) l chnh.

C2 H5 OH CH3C+CH3CH(CH3)2 CH2=C(CH3)CH(CH3)2 (C).
Bi 21: Hon thnh s phn ng:
A l benzene. B l cumene. C l p-bromocumene. D l p-bromo-m-nitrocumene.

Bi 22: S tng hp a. Aniline:
E l p-bromo-m-aminocumene. F l p-Br-m-+N2BF4C6H3CH(CH3)2. G l p-bromo-m-fluorcumene. H l m-fluor-p-magnesiumbromocumene.
55
b. Iodobenzene:
c. Acid benzoic:
Bi 23: a. Tng hp ephedrine:
b. C ch phn ng: C ch phn ng to thnh D: phn ng th electrophile vo nhn thm, SE:
C ch phn ng to thnh E: phn ng cng nucleophile vo nhm carbonyl, AN:
c. S tng hp khc i t acid propanoic v cc tc nhn cn thit khc:
57
Bi 24: Vit cng thc cu to sn phm cui (nu c) ca cc phn ng:
Bi 25: Vit cc phn ng tng hp:
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58
Part 7
ALCOHOL PHENOL ALDEHYDE CETONE
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Bi 1: Cho cc alcohol: (1) p-CH3-C6H4-CH2OH , (2) p-CH3O-C6H4-CH2OH, (3) p-CN-C6H4-CH2OH v
(4) p-Cl-C6H4-CH2OH. So snh kh nng phn ng ca cc alcohol trn vi HBr v gii thch.
Bi 2: Cho s cc phn ng sau:
OH
HCHO OH -
A NaCN
DMF
H2O
Cl
D1 + D2 + E (sn ph ph) m
Hy vit cng thc cu to ca A, B, C, D1, D2 v E. Bit E c cng thc phn t C19H22O5N2.

Bi 3: Hp cht A (C4H6O3) quang hot, khng tham gia phn ng trng bc, tc dng vi anhydride
acetic to ra dn xut monoacetate. Khi un nng vi methanol, A chuyn thnh cht B (C5H10O4). Di tc dng ca acid v c long, B cho methanol v C (C4H8O4). C tc dng vi anhydride acetic to ra dn xut triacetate, tc dng vi NaBH4 to ra D (C4H10O4) khng quang hot. C tham gia phn ng trng bc to thnh acid carboxylic E (C4H8O5). X l amide ca E bng dung dch long sodium hypochlorite to ra D-(+)-glyceraldehyde (C3H6O3) v ammonia.
Bi 4: Vit cng thc cu to cc sn phm hu c A, B, C v D trong s sau:
O CH2 C NBr C
Cyclohexanol
HBr
A
3.
1. Li 2. CuI Br
CH2
O N H /O B (NBS) C 2 4 2
D KOH
C2H5OH
Bi 5: Xc nh cc cht t A n G v hon thnh cc phng trnh phn ng trong chui bin ha sau:
1.CH3 MgCl H 2SO 4 ,t H 2SO4 ,t C6 H12 O( A) C6 H10 (B) C6 H12 O(D) 2.H O +
3 o o
KMnO (c nng)
4
C10H16 (G)
H2SO4 (un nng)
/ Methyl cyclopentane
2
H Pt
1. CH MgCl
3
2. H3O+
1.Mg ,ether HBr C10H18O (F) C 5 H 9 Br( E ) 2.Cyclopentanone 3.H 3 O

+
C6 H 5COOOH C5H8O (C)
Bi 6: Thc hin dy chuyn ha sau:
PhCHO 1.BuLi HS (CH 2 )3 SH A B 2.Ethyl trans But 2 enoate H+ H 2SO4 Ni,Raney H ,t C D E H2 H2 O

+ o
59
Bi 7: T nha thng, ngi ta tch c cht hu c (X) v chuyn ha (X) theo s sau:
Bit A c cng thc phn t l C9H14O.

a. Vit cng thc cu to cc sn phm hu c A, B, C1, C2, C3, D, E. b. Sn phm no c to thnh ng phn v ch r s lng ng phn ca mi sn phm. Bi 8: Hp cht hu c A cha 79,59 % C ; 12,25 % H ; cn li l O ch chim mt nguyn t trong phn
t. Ozone phn A thu c HOCH2CH=O ; CH3[CH2]2COCH3 v CH3CH2CO[CH2]2CH=O. Nu cho A tc dng vi Br2 theo t l mol 1:1 ri mi ozone phn sn phm chnh sinh ra th ch thu c hai sn phm hu c, trong c mt cetone. un nng A vi dung dch acid d dng thu c sn phm B c cng cng thc phn t nh A, song khi ozone phn B ch cho mt sn phm hu c duy nht.
a. Xc nh cng thc cu to v gi tn A. b. Tm cng thc cu to ca B v vit c ch chuyn A thnh B. Bi 9: Vit cc phng trnh phn ng theo s sau:
+X
H 2 ,xt P,t ,xt 2HCHO A B
o
C (ethylene glycol diacetate) D (poliether)

O2 ,xt 2(d ) E F (acid a chc) G
Trng ngng + CuO, t

o
Ca (OH )
Bi 10: Khi cho cis v trans-3,3-imethyl-2-bromocyclohexanol phn ng nhanh vi base mnh s thu
c 2 sn phm ring bit. Sn phm to thnh t cis-bromoalcohol c vn hp th 1710 cm-1, cn sn phm kia khng c vn hp th ny v cng khng c vn hp th 3350 cm-1. Xc nh cng thc cu to ca cc sn phm trn.
Bi 11: Hp cht A phn ng vi PCl3 cho ra B, kh ha B bng H2/Pd nhn c benzaldehyde. Mt
khc cho B tc dng vi NH3 c C, x l C vi Br2 trong mi trng kim c D. T B c th nhn c E bng cch cho phn ng vi benzene xc tc AlCl3. E chuyn thnh F khi x l vi hydroxylamine, trong mi trng acid F chuyn thnh G. Vit cng thc cu trc cc hp cht trn.
Bi 12: Vit cng thc cu trc ca cc sn phm trung gian v dng mi tn ch r s tng tc ca
nhn vi trung tm phn ng:

OEt ph vng HOEt OEt khp vng OEt H OEt X A B C D E F G Y
+
Trong X, Y ln lt l:
(X) Copyright 2009 volcmttl@yahoo.com.vn
(Y)
60
Bi 13: Tin hnh ngng t gia benzaldehyde v ethyl methyl cetone ln lt trong mi trng acid v
mi trng base ngi ta thu c 2 sn phm khc nhau. Vit CTCT cc sn phm to thnh, gii thch.
Bi 14: Hp cht A C4H8O3 quang hot, tan tt trong nc to thnh dung dch phn ng acid vi giy
qu. un mnh dung dch, A chuyn thnh cht B C4H6O2 khng quang hot tan va phi trong nc v cng cho phn ng acid vi giy qu. B phn ng vi KMnO4 mnh lin hn A. Oxygen ha A bng dung dch H2CrO4 long s thnh cht lng bay hi C C3H6O. C khng phn ng vi KMnO4 nhng cho phn ng vi I2 trong dung dch kim. Vit CTCT cc cht v phng trnh phn ng xy ra. Cc d kin trn iu kin xc nh cu trc ca A cha, gii thch.
Bi 15: Hp cht hu c A c cng thc C17H30O b oxygen ha nh cho 2 acid l: acid octandioic v
acid nonandioic. Hy gi tn A theo danh php IUPAC v chuyn hn hp ng phn ca n thnh cis-A.
Bi 16: Hp cht X C6H9OBr phn ng vi methanol trong mi trng acid sinh ra Y C8H15O2Br. Cho Y
phn ng vi Mg trong ether khan, sau cho phn ng tip vi aldehyde formic c cht E. Thy phn
E trong mi trng acid c F, dehydrate ha F thu c 2-vinylcyclopentanone a. Xc nh CTCT ca X b. Nu mun iu ch F t X c nht thit phi qua cc giai on nh trn khng, v sao. Bi 17: C 5 l khng nhn c k hiu t A n E cha ring l 5 hp cht thm sau:
C6H5COCH2CH3, C6H5COOH, C6H5COCH3, C6H5CH(OH)CH3 v C6H5CHO. Da vo cc kt qu th nghim sau y nhn bit ha cht c trong mi l: Cho vo mi l 1 git dung dch K2Cr2O7/H2SO4 ri lc u. Sau vi pht thy l A v C bin i dung dch mu da cam thnh xanh lc. Cho vo mi cht mt t dung dch NaOH long th ch ring l B tan c. Khi cho tc dng vi I2 trong dung dch kim th l A v E cho kt ta vng. L C, D v E u tc dng vi 2,4-dinitrophenylhydrazine cho kt ta , da cam.
Bi 18: C 4 hp cht thm: C6H5OH ; C6H6 ; C6H5CH3 ; C6H5NO2. Xt bng sau: Cht phn ng A Khng phn ng Nc Br2 Br2/Fe HNO3/H2SO4 B C phn ng Phn ng 0o C v khng cn xc tc Fe Phn ng vi c dung dch HNO3 long C Khng phn ng Ch phn ng khi un nng Ch phn ng khi un nng D Khng phn ng
C phn ng C phn ng
C phn ng C phn ng khng cn H2SO4
a. Xc nh k hiu A, B, C, D cho mi cht. b. Hy sp xp cc cht theo th t tng dn v kh nng tham gia phn ng th vng benzene.
Gii thch s nh hng ca cc nhm th n kh nng .

Bi 19: T ht tiu ngi ta tch c hp cht A (C17H19NO3) l cht trung tnh. Ozone phn A thu
c cc hp cht: ethadial, B, D. Thu phn B thu c OHC-COOH v hp cht d vng 6 cnh piperidine (C5H11N). Cho D tc dng vi dung dch HI c thu c 3,4-dihydroxybenzaldehyde. Hy xc nh cng thc cu to ca A, B, D v cho bit c bao nhiu ng phn lp th ca A. Copyright 2009 volcmttl@yahoo.com.vn
61
Bi 20: T cc cht ban u c s nguyn t carbon 3, vit cc phng trnh phn ng (ghi r iu kin
nu c) iu ch: Acid cyclobutanecarboxylic v Cyclopentanone. *** *** *** *** *** *** *** *** *** *** *** *** *** *** *** ***
Part 7
HNG DN GII
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Bi 1: Phn ng gia cc alcohol cho vi HBr l phn ng th theo c ch SN. Giai on trung gian
to carbocation benzylic. Nhm OCH3 y electron (+C) lm bn ho carbocation ny nn kh nng phn ng tng. Nhm CH3 c (+I) nn cng lm bn ha carbocation ny nhng km hn nhm OCH3 v (+C) > (+I) . Cc nhm Cl (-I > +C) v CN (-C) ht electron lm carbocation tr nn km bn do vy kh nng phn ng gim, nhm CN ht electron mnh hn nhm Cl. Vy sp xp theo trt t tng dn kh nng phn ng vi HBr l:
p-CN-C6H4-CH2OH < p-Cl-C6H4-CH2OH < p-CH3-C6H4-CH2OH < p-CH3O-C6H4-CH2OH. Bi 2: S iu ch p-hydroxyphenylacetamide
HCHO
CH2OH HO A
NaCN DMF
CH2CN HO B
H2O
CH2CONH2 HO C
HO
OH
OH
O Cl
OH O O H2NCOCH2 D1 + H2NCOCH2 D2 O Cl
H2NCOCH2 C
Sn phm ph:
O C19H22O5N2 H2NCOCH2 CH2CONH2 OH O
Bi 3: S chuyn ha gia cc cht:

CHO H OH CH2OH D-Glyxeraldehit D-Glyceraldehyde MeO O O CH2 A
MeOH
COOH
CHO
CH2OH E
M
H eO
CH2OH C
CH2OH O CH2 B CH2OH D

62
Bi 4: Cng thc cu to cc sn phm:
Bi 5: Cng thc cu to cc cht trong s :
Bi 6: Cng thc cu to cc cht trong s :
63
Bi 7: a. Cng thc cu to sn phm:
b. Cc sn phm to thnh c ng phn:
Bi 8:
C3 c 2 ng phn quang hc C2 c 4 ng phn quang hc D c ng phn E, Z.
79, 59 12, 25 8,16 = = = 13 : 24 :1 => A c cng thc phn t l C13H24O 12 1 16
T sn phm ozone phn, tm ra 2 cng thc cu to c th ph hp:
T sn phm Br ha ri ozone phn => A1 ph hp v:
Tn ca A: 3-Ethyl-7-methyldeca-2,6-diene-1-ol
64
b.
B phi l hp cht mch vng cha mt ni i trong vng, B sinh ra t A do phn ng ng vng
Bi 9:
p,t ,xt 2HCHO HOCH 2 CHO ( A). xt HOCH 2 CHO + H 2 HOCH 2 CH 2 OH (B).
o
2CH 3COOH + C2 H 4 (OH)2 (CH3COO)2 C2 H 4 (C).

trng ngung HOCH 2 CH 2 OH (OCH 2 CH 2 )n (D) + nH 2 O. t HOCH 2 CH 2 OH + 2CuO OHC CHO (E) + 2H 2O+2Cu. xt OHC CHO + O 2 HOOC COOH (F).
o
HOOC COOH + Ca(OH) 2 CaC2 O 4 (G ) + 2H 2O.
Bi 10:
trans-3,3-imethyl-2-bromocyclohexanol khng b tch HBr m c th phn ng SN2 ni phn t
cis-3,3-imethyl-2-bromocyclohexanol tch HBr to enol khng bn chuyn thnh cetone (h bin ceto-enol) c vn hp th 1710cm1.
Bi 11:
A l PhCOOH. B l PhCOCl. C l PhCONH2. D l PhNH2 (+CO2).
E l PhCOPh. F l Ph2C=NOH G l PhCONHPh.
(F G chuyn v Beckman)
65
Bi 12: Vit cng thc cu trc ca cc sn phm trung gian v dng mi tn ch r s tng tc ca
nhn vi trung tm phn ng:
Bi 13:
OH Trong mi trng base: C6 H 5CHO + CH3COCH 2 CH 3 C6 H5CH = CHCOCH 2 CH 3 + H 2O . to
H ca CH3 c tnh acid mnh hn H ca CH2. H Trong mi trng acid: C6 H 5CHO + CH3COCH 2CH 3 C6 H 5CH = C(CH3 ) COCH 3 + H 2O. to
+
Khi c xc tc acid, cetone s b enol ha m CH3=C(OH)CHCH3 bn hn.

Bi 14:
C l acetone CH3COCH3. A l CH3CHOHCH2COOH. B l CH3CH=CHCOOH (cis/trans).
iu kin xc nh A v ch c cetoacid th nhm COOH mi d b decarboxyl ha v vy A ch c th l acid 3hydroxybutanoic thay v acid 2hyroxybutanoic.
Bi 15:
Vy A l cycloheptadex9enone. Copyright 2009 volcmttl@yahoo.com.vn

61
Chuyn hn hp cc ng phn v cis:

A(transv cis) cis A
1.Br2 / 20o C 2.C2 H 4 (OH)2 / H + 3.KOH / C2 H5 OH 4.H 2 ,Ni / C 2 H5 OH 5.H 3 O +
Bi 16: a. Cht Y cha nhiu hn X 2 nguyn t carbon, 6 nguyn t hydro v 1 nguyn t oxygen, suy ra X
phn ng vi 2 CH3OH v tch loi 1 phn t H2O dn n s hnh thnh acetal methylic t X. Cht F sau khi dehydrate ha to ra 2vinylcyclopentanone. Vy F phi c cng thc cu to l:
b. Khi iu ch nht thit phi qua cc giai on trn v nu khng qua giai on to Y th hp cht
c magnesium s phn ng vi nhm C=O. Nu a 1 C qua phn ng vi KCN th nhm C=O cng c th phn ng vi KCN.
Bi 17: A l C6H5CHOHCH3 B l C6H5COOH C l C6H5CHO D l C6H5COC2H5 E l C6H5COCH3
Bi 18: a. A l C6H6 ; B l C6H5OH ; C l C6H5NO2 ; D l C6H5CH3 b. Kh nang phn ng th vng benzene tng dn theo th t: C < A < D < B
Gii thich: Phn ng th H vng benzene theo c ch SE. Tc nhn electrophile tn cng vo electron ca nhn thm. Do o nguyn t hay nhm nguyn t no lm tng mt electron ca nhn benzene (nht l v tr ortho-, para-) phn ng cng d dng. Ly C6H6 lm mc so snh, ta thy nhm CH3 c hiu ng +I v nhm OH c nhm +C y electron mnh hn nhm CH3. Hai nhm ny lm tng mt electron ca nhn thm ti cc v tr ortho-, para-. V vy ta c phn ng th ca B > D > A. Nhm NO2 c hiu ng I, C ht electron mnh v lm gim mt electron ca nhn thm, lm gim kh nng phn ng th H vng benzene so vi C6H6 => C < A. Copyright 2009 volcmttl@yahoo.com.vn
62
Bi 19: Ozone phn A thu c ethadial chng t trong A c nhm =CHCH= . Thu phn B thu c
OHC-COOH v piperidine, suy ra B c lin kt O=CN v N nm trong vng 6 cnh. D phn ng vi HI thu c 3,4-dihydroxybenzaldehyde. Vy c cc cng thc cu to:
Trong A c 2 lin kt i, s ng phn hnh hc l 4: ZZ , EE , ZE , EZ.

Bi 20: S iu ch:
*** *** *** *** *** *** *** ***
*** *** *** *** *** *** *** ***
63
TI LIU THAM KHO:

1. Bi tp L thuyt v Thc nghim, tp 2: Ha Hc Hu C Cao C Gic NXB Gio Dc 2006. 2. Bi tp Ha Hu C Trn Th Vit Hoa, Trn Vn Thnh NXB i Hc Quc Gia TP H Ch
Minh 2003.
3. B thi HSG Quc gia lp 12 THPT. 4. B thi Olympic 30/4 cc tnh pha nam. 5. Bi tp Ha Hu C, tp 1 Ng Th Thun NXB i hc Quc Gia H Ni 1999. 6. Bi tp Ha Hu C, tp 2 Ng Th Thun NXB Khoa hc v K thut 2008. 7. Bi tp Ha Hu C i Hc Y Dc TP H Ch Minh 2001. 8. Tng hp Hu C Nguyn Minh Tho. NXB i hc Quc Gia H Ni 2001. 9. Mt s cu hi v bi tp Ho hu c - o Vn ch, Triu Qu Hng - NXB i Hc Quc Gia
H Ni.
64
*** *** *** *** *** *** *** ***

LI M U Phn 1: HIU NG HA HC
*** *** *** *** *** *** *** ***
BI TP ......................................................................................................................................Trang 1 P N .......................................................................................................................................Trang 3 Phn 2: NG PHN BI TP ......................................................................................................................................Trang 7 P N .......................................................................................................................................Trang 10 Phn 3: C CH PHN NG BI TP ......................................................................................................................................Trang 15 P N .......................................................................................................................................Trang 19 Phn 4: ALKANE CYCLOALKANE BI TP ......................................................................................................................................Trang 26 P N .......................................................................................................................................Trang 28 Phn 5: ALKENE ALKINE DIENE TERPENE BI TP ......................................................................................................................................Trang 34 P N .......................................................................................................................................Trang 39 Phn 6: HYDROCARBON THM DN XUT HALOGEN HP CHT C KIM BI TP ......................................................................................................................................Trang 49 P N .......................................................................................................................................Trang 53 Phn 7: ALCOHOL PHENOL ALDEHYDE CETONE BI TP ......................................................................................................................................Trang 58 P N .......................................................................................................................................Trang 61
TI LIU THAM KHO ......................................................................................................Trang 64 MC LC ...................................................................................................................................Trang 65
- - - - - - - - - - Ht tp 1 - - - - - - - - - Copyright 2009 volcmttl@yahoo.com.vn

65

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Ti liu dnh cho:

Bi tp Ha Hu C Ti liu dnh cho sinh vin cc trng i hc

Copyright 2009 volcmttl@yahoo.com.vn

Bi tp Ha Hu C Ti liu dnh cho sinh vin cc trng i hc

(1) acid iso-Crotonic Copyright 2009 volcmttl@yahoo.com.vn

(2) acid Crotonic 2

Bi tp Ha Hu C Ti liu dnh cho sinh vin cc trng i hc

Bi 20: Xc nh tm base mnh nht trong cc alkaloid sau:

Vindoline *** *** *** *** *** ***

c. Cng thc gii hn ca (c)

d. Cng thc gii hn ca (d)

Copyright 2009 volcmttl@yahoo.com.vn

Bi tp Ha Hu C Ti liu dnh cho sinh vin cc trng i hc

b. (2) > (5) > (3) > (4) > (1).

Bi 10: Cng thc gii hn: a. Aniline

Copyright 2009 volcmttl@yahoo.com.vn

Bi tp Ha Hu C Ti liu dnh cho sinh vin cc trng i hc

b. (1) > (3) > (2).

H COOH F Axit fumaric

Copyright 2009 volcmttl@yahoo.com.vn

Bi tp Ha Hu C Ti liu dnh cho sinh vin cc trng i hc

Bi 20: Xc nh tm base mnh nht

*** *** ***

*** *** ***

*** *** ***

*** *** ***

Copyright 2009 volcmttl@yahoo.com.vn

Bi tp Ha Hu C Ti liu dnh cho sinh vin cc trng i hc

Bi 5: Trnh by cng thc chiu Fischer v xc nh cu hnh tuyt i ca cc ng phn c cu to sau

Bi 6: Vit cng thc chiu Newman dng bn ca: a. (CH3)2CHCH2CH3. 7

Copyright 2009 volcmttl@yahoo.com.vn

Bi tp Ha Hu C Ti liu dnh cho sinh vin cc trng i hc

Bi 9: Hy ghi du * vo bn cnh nguyn t carbon bt i v xc nh cu hnh tuyt i ca Serine, Adrenaline, Menthone.

H H A Bi 12: Cho cc phn ng sau:

pyridine (1) C6H5CH2CH(CH3)OH + ClSO2C6H4CH3-p (E) +

(Ts l k hiu vit tt ca SO4C6H4CH3-p)

H2O18 nh sau: RCOOR + H2O18

Copyright 2009 volcmttl@yahoo.com.vn

Bi tp Ha Hu C Ti liu dnh cho sinh vin cc trng i hc

y, cht no l terpene v ch ra n v isoprene trong khung terpene .

Bi 18: Vit cng thc Fischer ca cc cht C v D trong dy chuyn ha sau:

Bi tp Ha Hu C Ti liu dnh cho sinh vin cc trng i hc

Bi 1: Vit cc ng phn cu to: a. bt bo ha =

C5H10 (c 1 vng) c 5 ng phn cu to ph hp:

b. C5H11OH c bt bo ha = c. C6H14 c = 0 , c 5 ng phn.

5 2 + 2 12 = 0 nn l alcohol no n chc. C 8 ng phn. 2

i c hai ng phn hnh hc do vng cyclopropane phng (mt c nh).

Copyright 2009 volcmttl@yahoo.com.vn

Bi tp Ha Hu C Ti liu dnh cho sinh vin cc trng i hc

Cu ng phn Cis trans Bi 4:

(a) Bi 6: Vit cng thc chiu Newman a. (A) c 2 dng bn:

b. (B) c 1 dng bn:

c. (C) c 1 dng bn:

Copyright 2009 volcmttl@yahoo.com.vn

Bi tp Ha Hu C Ti liu dnh cho sinh vin cc trng i hc

R Bi 10: Cng thc dng h bin a. Cyclohexanone. H bin cetoenol

b. (CH3)2CHN=O. H bin nitro-axi

Bi tp Ha Hu C Ti liu dnh cho sinh vin cc trng i hc

A l cisdecalin Cu dng gh ca (A), (B)

b. ng phn quang hc:

Copyright 2009 volcmttl@yahoo.com.vn

Bi tp Ha Hu C Ti liu dnh cho sinh vin cc trng i hc

Vindoline * * * * * *

* * ***

* * ***

* * ***

* * ***