Professional Documents
Culture Documents
vn copyright 2009
08 2009
i ni u
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:
(1) SR
(2) SO2R
(3) SOR
b. Hiu ng C ca:
(1) R2NCO
(2) R2NC(=NR)
(3) (R)2NC(=+NR2)
c. Hiu ng +C ca:
(1) RCON(R)
(3) RCH2N(R)
Bi 2: Da vo hin tng cng hng, vit cng thc gii hn (nu c) ca cc cht sau y:
a. CH2=CHCH2Cl.
c. C6H5CN.
b. p-NO2C6H4NH2.
d. C6H5CH3.
Bi 3: Gii thch ti sao nhng v tr o- hay p- ca hp cht C6H5CH2Cl tng i giu in t trong khi
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)
(2)
(3)
(4)
(5)
(1)
(2)
(3)
(4)
(5)
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.
c. Vinyl Bromide.
b. Buta1,3diene.
d. Acrolein.
CH3OH
C2H5OH
C3H7OH
C4H9OH
65
78,5
97,2
138
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
Nicotine
Vindoline
************************************************
Part: 1
HNG DN GII
Bi 3: Gii thch:
-
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
CH3CH2CH2CH2Cl + H2O c vn tc phn ng l v2
(2) CH3CH2CH2CH2OH + HCl
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:
-
Cl gy hiu ng I, +C
N+(CH3)3 gy hiu ng I
C(CH3)3 gy hiu ng +I
b. Buta1,3diene:
c. Vinyl Bromide:
d. Acrolein:
CH2CH=CHCH2
CH2CH=Br+
CH2CH=CHO
Bi 12: Xt bng:
acid
H2O
C6H5NH3(+)
C2H5OH
H3O(+)
base lin hp
OH
C6H5NH2
C2H5O
H2O
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
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.
HOOC
H
COOH
F Axit fumaric
- H+
H
F
OH ...O
COO-
- H+
M Axit maleic
O
H
OOC
- H+
COO-
H
F
-
.... O
- H+
,,
COO-
OOC
....
OH
H
OH ... O
H
M,
M,,
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
-
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).
************************************************
Part 2
NG PHN
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c.
C6H14.
b.
C5H11OH.
d.
C4H9Cl.
(CH3)2CHCH=CH2
f.
b.
CH3CH=CHCH3
g.
Nha Guttapercha
c.
CH3CH=CHF
h.
CH3CH=C=C=C=CHCH3
d.
C2H5C(CH3)=CHCH3
i.
1,2dimethylcyclopropane
e.
CH3CH=C=CHCH3
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.
FHC=CHF
A = 0 D
B = 2,42 D
b.
CH3CH=CHBr
A = 1,57 D
B = 1,69 D
c.
pNO2C6H4CH=CHC6H4
A = 3,11 D
B = 4,52 D
1phenylethanol.
b.
2chlorobut2ene.
c.
1,2dibromopentane.
d.
Alanine.
(a)
(b)
(c)
(CH3)2CHCH2CH3.
b.
CH3CH=CH2.
c.
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.
CH3COCH2CH3.
b.
CH3COCH2COCH3.
c.
C6H5NHCONHC6H5.
Serine
Adrenaline (Corticoid)
Menthone
Bi 10: Vit cng thc dng h bin v cho bit loi h bin trong hai trng hp sau:
a.
b.
Cyclohexanone.
(CH3)2CHN=O.
HH
HH
A
[ ]D = +33o
Cl
Xc nh cu trc ca (E) v (F) v cho bit phn ng (2) thuc loi phn ng g.
b.
Cho bit phn ng thy phn cc ester loi nh (F) trong mi trng kim vi s hin din ca
OH
RCOO18H + ROH
9
8
HO
O
2
mycrene
Bi 20: C ba hp cht: A, B v C
a.
b.
c.
Part 2
HNG DN GII
5 2 + 2 10
= 1 , theo C5H10 c cha mt vng ( = 1 ) nn l cycloalkane.
2
b. C5H11OH c bt bo ha =
5 2 + 2 12
= 0 nn l alcohol no n chc. C 8 ng phn.
2
c. C6H14 c = 0 , c 5 ng phn.
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
-
Bi 3: Xt bng
10
Cu
ng phn
Cis
trans
Bi 4:
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)
(b)
(c)
11
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
12
A l cisdecalin
B l transdecalin
(A)
(B)
Bi 12:
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*.
-
Cu trc ca (E) l:
Phn ng (2) l phn ng SN2 => sn phm alcohol ca phn ng (3) c cu hnh nghch vi
Cu trc ca (F) l:
Co
Cis
Co
Cl
Trans
Cl
Cl
Co
Co
Cl
Bi 16:
-
Tn: 8hydroxy7phenyl2,6dioxabicyclo[3.3.1]nonane3one
4
3
2
H5C 6
HO
4
3
5
O
8
C6H5
OH
H5C 6
HO
O
1
O
5
O
1
C6H5
OH
13
Bi 19: Ta c 4 ng phn lp th
(I)
(II)
(III)
(IV)
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.
14
Part 3
C CH PHN NG
(- )
OEt
HN
OEt
OEt
N
N
N
N
N
-H
N CH3
+H
+ CO2 + HN
O2 S
O2 S
N CH3
O2 S N
N CH3
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
H
g. 2C2H5OH
b. CH3CH2Cl + KCN
h. Pyridine + C2H5I
c. CH3Cl + H2NCH3
i. C6H5OH + HCHO
OH
d. CH3CH2Cl + H2O
e. C6H5ONa + CH3I
OH
j. C6H5CHO + CH3CHO
o
k. CH3CH2CH(OSO3H)CH3 + H2O
f. C6H5OH + CH3OH
l. CH3COOC2H5 + OH
600 C
a. CH3CH=CH2 + Cl2
1:1
CCl4
b. CH2=CH2 + Br2
1:1
CCl4
c. H2C=CHCH=CH2 + Br2
1:1
o
t C
d. C6H5CH3 + Cl2
1:1,Fe,xt
15
(II)
(I)
HO
HO
1.
C 6H 5MgBr
H
(A)
2 . H 2O
HBr a
c
B
C 3H 7
H 3C C C CH3
(1)
(2)
(3)
(1)
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
LiAlH 4
H2
A (1) ; But 2 ine
A (2) . Trong
Bi 13: Cho cc phn ng sau: But 2 ine
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:
18
Part 3
HNG DN GII
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Bi 1:
AN
(CH3)2C(C2H5)OMgCl
a. CH3MgCl + C2H5COCH3
2
SN
CH3CH2CN + Cl
b. CH3CH2Cl + KCN
2
SN
CH3HNCH3 + HCl
c. CH3Cl + H2NCH3
2
SN
CH3CH2OH + HCl
d. CH3CH2Cl + H2O
2
SN
e. C6H5ONa + CH3I
+ NaI
SE
CH3C6H4OH (o-, p-) + H2O
f. C6H5OH + CH3OH
2
SN
C2H5OC2H5 + H2O
g. 2C2H5OH
2
SN
[pyridine(N+) C2H5]I
h. Pyridine + C2H5I
SE
(o-, p-) CH2OHC6H4OH
i. C6H5OH + HCHO
AN
C6H5CH=CHCHO + H2O
j. C6H5CHO + CH3CHO
1
SN
CH3CH2CH(OH)CH3 +
k. CH3CH2CH(OSO3H)CH3 + H2O
2
SN
l. CH3COOC2H5 + OH
CH3COO + C2H5OH
Bi 2:
19
Bi 3:
600o C
a. CH3CH=CH2 + Cl2
Cl CH 2 CH = CH 2 + HCl
SR
CCl4
BrCH2CH2Br
b. CH2=CH2 + Br2
AE
CCl 4
(1) + (2) ;
c. H2C=CHCH=CH2 + Br2
AE
t C,1:1,Fe,xt
p CH3C6 H 4Cl + HCl
d. C6H5CH3 + Cl2
SE
Bi 4:
a. (2) > (1)
Bi 5:
.
R
H
H2C
as
HO
HO
to
R
HO
HO
Cudng
d ngbn
bn: S-trans
Cu
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)
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:
(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:
b. Phn ng theo SN1 , m giai on (1) l giai on chm quyt nh tc phn ng v biu thc
21
Bi 10:
a. Sn phm phn ng
CH3
CH2
H 3C
CH3
t p
H 3C
CH3
CH3
2-Metylpropan (Y)
2-Metylpropen (X)
CH3 H
CH3
H
(A)
CH3
o,
CH3
CH3
H3C
CH3
2 H3C
CH3 H
H+
CH2
CH2
CH3 H
H3C
2,4,4-trimetyl pent-1-en
CH3 H
CH3
CH3
2,4,4-trimetyl pent-2-en
CH3
Bc th hai hydro ho Q v Z
H3C
CH3 H
CH3
CH2
H2
CH3 H
H3C
CH3
CH3 H
Ni , t
CH3 H
CH3
CH3 H
CH3
H3C
CH3
H2
CH3
b. C ch phn ng
(0,75 m).
R1
O
CH2
O3
R1
C CH2
R1
Zn/H3O
R1
CH3
CH3
CH3
CH2
O + O
CH2
CH3
Z
O
O
O
O
R2
C
H
CH3
CH3
O3
R2
CH3
R2
CH3
CH3
CH3
Zn/H3O
Q
R2HC
O + CH3COCH3
22
Bi 11:
a. Phn ng sau khng dng tng hp tert-butyl propyl ether.
tert-butyl bromide
c. Phng php tng hp hiu qu l dng phn t phn ng SN2 c nhm alkyl t cn tr hn v
Bi 12:
O
O
O
Cl CH3O
Cl
OCH3
CH3O
CH3OH
OCH3
OCH3
H2O
OH
Bi 13:
a. Gii thch cu hnh A, B
b. C ch chuyn ha A
23
ng phn ha v tr
(B)
(A)
Bi 15: C ch phn ng
a. Phn ng xy ra qua 4 bc
Bc 1: To carbocation
H 2O
(CH3 )3C O + H 2
(CH 3 )3C+
(CH3 )3C OH + H +
24
Bc 2: To isobutene v isobutane
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
25
Part 4
ALKANE, CYCLOALKANE
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
93,60
(CH3)3CF
110,64
HF
135,84
F2
37,20
(CH3)3CCl
81,36
HCl
103,68
Cl2
58,32
(CH3)3CBr
67,44
HBr
87,60
Br2
46,32
(CH3)3CI
52,32
HI
71,29
I2
36,14
a. CH3CH2CH2CH2CH3 + O2
( red )
d. CH3CH2I + HI
b. CH3CH2CH2CH2CH3 + HNO3
Zn / HCl
e. CH3CH2C(=O)CH3
c. (CH3)2CHCl + Na
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:
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
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
b. CH3CH=CH2 + CH2I2
26
sn phm .
c. Trnh by c ch phn ng Cl ha trn.
Bi 18: Cho s sau:
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)
d. (CH3)3CH + I2 (CH3)3CI + HI
H = 6,24 (Kcal/mol)
t
CH 3 + I
Bi 3: C ch tng giai on v hiu ng nhit phn ng: CH3 I
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)
I2 + CH4 ; H = 12,71 (Kcal / mol)
Cng (1) v (2) ta c phn ng: CH3I + HI
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
28
2 Me3CO
(Me3CO)2
+ CCl 4
Me3CCl + CCl3
CCl3
+ Me3CH CHCl3
+ Me3C
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
1chloro2methylbutane (C)
2chloro3methylbutane (E)
2chloro2methylbutane (D)
1chloro3methylbutane (F)
Phn trm
(C)
6 1=6
6
100% 28%
21, 6
(D)
1 5=5
5
100% 23%
21, 6
(E)
2 3,8 = 7,6
7, 6
100% 35%
21, 6
(F)
3 1=3
3
100% 14%
21, 6
Cht
Bi 9: p s: 40,9 g
Bi 10: iu ch:
29
(a)
(b)
(c)
(d)
(e)
(f)
Bi 12:
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:
Bi 14:
a.
(A)
(B)
30
b.
(C)
(D)
Bi 15:
a. Phng trnh phn ng:
askt
185 72, 72
= 134,532g ; m Y = 185 134,532 = 50, 468g
100
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
31
Bi 17:
a. Do cu trc ca spiropentane l i xng, cc nguyn t H trn nhm methylene u nh nhau,
t
(1) C4H10
CH3CH=CH2 + CH4
o
Ni / t
CH3CH2CH3
(2) CH3CH=CH2 + H2
askt
CH3CHBrCH3 + HBr
(3) CH3CH2CH3 + Br2
Ether khan
(CH3)2CHMgBr
(4) CH3CHBrCH3 + Mg
xt,t
CH2=CCH3CH=CH2 + 2H2
(6) (CH3)2CHCH2CH3
o
xt,t
(7) n CH2=CCH3CH=CH2
(CH2CCH3=CHCH2)n
o
1500 C
(8) 2CH 4
HC CH + 3H 2
lanh nhanh
o
Ni / t
CH3 CH3
(9) HC CH + 2H 2
askt
CH3CH2Br + HBr
(10) CH3CH3 + Br2
o
Carbon ,600 C
C6H6
(11) 3HC CH
H 2SO 4
C6H5CH(CH3)2
(12) C6H6 + CH2=CHCH3
o
Fe,t
p-BrC6H4CH(CH3)2 + HBr
(13) C6H5CH(CH3)2 + Br2
askt
(14) p-BrC6H4CH(CH3)2 + Br2
p-BrC6H4CBr(CH3)2 + HBr
H 2SO 4
p-O2NC6H4CH(CH3)2 + H2O
(15) C6H5CH(CH3)2 + HNO3
b. B4 l n-butane
32
Bi 19:
Cht
Cng thc cu to
Cht
Cng thc cu to
CH2=CH2
B1
CH2=CHCH2Cl
C2H5OH
C1
ClCH2CHOHCH2Cl
CH3CHO
D1
HOCH2CHOHCH2OH
CH3COOH
B2
CH3CHClCH3
CH2=CHCH=CH2
C2
(CH3)2CHMgCl
A1
CH3CH=CH2
D2
(CH3)2CHCH2CH2OH
Ngoi ra:
-
Nu C l CH3COOH th D l (CH3COO)2Ca
Nu A l CH4 th B l HC CH , C l CH3CHO
Bi 20:
a.
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
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
************************************************
Part 5
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
33
b. transbut2ene + Br2
(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).
f. 1. O3 ; 2. (CH3)2S.
c. Br2/H2O.
g. 1. B2H6 ; 2. H2O2/OH.
c. Cyclohexanone.
b. Cyclopentanal.
d. CH3 CH CH2
34
Bi 10: Khi cho isobutene vo dung dch c ha tan HBr, NaCl, CH3OH c th to ra nhng cht g, gii
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
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
(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
O
H3C
CH3
Hydro ha (A) vi xc tc kim loi to ra hn hp sn phm (X) gm cc ng phn c cng thc phn
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
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.
2.
b.
Dng cng thc cu trc, vit phng trnh phn ng v trnh by c ch y ca phn ng
tng hp A.
3.
36
4.
5.
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.
Anethole lm mt mu nc bromine.
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:
o
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
Cho bit: X l:
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)
tnc (oC)
%C
%H
68,6
-141
85,63
14,34
67,9
-133
85,63
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:
1.NaNH 2
2.Na/NH
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
F
G(C12 H 20O 2 ).
H 2 (1mol)
Pd/CaCO3
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.
+
H
HOCH 2 CH 2 OH
2
D(C11H18O 2 )
2O B(C19 H13O) p-CH
C(C11H18O 2 )
3CH 3COCH 3 NaNH
A -2H
3C6 H 4SO3 H
3SO 2 Cl
4
4
D KMnO
OH
[E](C11H 20 O 4 ) KMnO
OH
F(C11H18O 4 ) CH
G(C11H15O3 )
pyridine
L
Methyl - 3 - methylpent - 2(Z) - ene - 4 - inoate LDA
DMF
+
4
3 ONa,H 2 O
L NH
M 1.CH
Part 5
HNG DN GII
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
38
Bi 2: Hn hp racemic
Bi 3:
a.
CH3CHO + HCHO.
b.
OHCCHCH3CHO + 2HCHO.
c.
OHCCH2COCH3 + OHCCH2CHO
Bi 4:
HCl
Mg
a. CH3CH = CH 2
CH 3 CHCl CH3
CH3 CH(MgCl) CH3
1.BH3
CrO3
CH 3CH 2 CH 2 OH
CH 3CH 2CHO
CH3CH = CH 2
2.H O ,OH
2
(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.
tert-butyliodide.
b.
Tert-butyliodide.
c.
1bromo2methylpropanol.
d.
e.
2methylpropan1,2diol.
f.
Acetone v formaldehyde.
g.
Isobutanol.
Bi 8:
a.
CH3 CH 2 C C CH 3 .
b.
Sn phm l
c.
Sn phm l
d.
CH3 CHOH CH 2 C C CH 3
Bi 9:
A l HC CMgBr ; B l
; C l
; D l
40
NaCl Na+ Cl
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
41
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.
(C) l: CH3CH=CHCH=CHCH3.
(B) l: CH3CH2CHBrCHBrCH2CH3.
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 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.
CH3
O
H3C
CH3
O
CH3
CH3
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
OH
(+)
OH
OH
OH OH
OH
(+)
Cis-B
(+)
OH
OH
OH
OH
OH
OH
(+)
Trans-B
2 H2O
OH
4.
HO
Cl
H2O
HCl
D
H+
Cl-
(+)
(+)
chuyn v
vi nhau.
Bi 22:
44
(E)-1-methoxy-4-(1-propenyl)benzene
(Z)-1-methoxy-4-(1-propenyl)benzene
45
A l hp cht mch h nn c 2 ni i
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
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
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.NaNH 2
2.Na/NH 3(l)
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
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
Ph 3P
NaI
Bi 30:
a. Cng thc cu to cc cht:
47
************************************************
Part 6
48
alkylhalogenide.
Bi 2: Ba hp cht trimethylbenzene sau, cht no c kh nng hot ha mnh nht trong phn ng th
H 2 O,t
a. Br(CH2)3pC6H4CH2Br
1.KCN,DMSO
b. C6H5CH2Cl
2.H + ,H O,t o
2
1.SO3 .H 2SO 4
c. C6H5CH3
2.HNO3 /H 2SO 4
3.NaOH,t o
d.
1.CH3 (CH 2 )3 Li
2.C6 H 5CHO
3.H 3O + ,t o
e.
Na 2 Cr2 O 7 / H 2SO 4
f.
1.MnO 2
2.KOH,H O,t o
2
c. C6H5COpC6H4COOCH3.
b. p-ClC6H4CONH2.
d. Acid 2,6dibromobenzoic.
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
49
H 3O
SO 2 Cl
KCN
(A)
(B)
(C).
a. CH3CHOHCH 3
CH 2 = CH 2
KCN / alcohol
b. I(CH 2 ) 4 I
(A)
(B).
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.
c. KOH/C2H5OH.
h. CH3COONa.
+
d. 1. KCN ; 2. H3O .
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
(1 mol)
HNO3 1:1
2[ H ]
C
D
Fe / HCl
E
F
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
phn ng ny:
o
+Me2 CHBr/AlCl3
HNO3
+Br2 /Fe
HNO2
H 2O
6[H]
t
Mg
A
B
C
D
E
F
G
H
I
HBF4
Bi 22: Xut pht t Bromobenzene cha C14 v tr 1 v cc cht v c cn thit khng cha C14, hy
c. Acid benzoic.
b. Iodobenzene.
50
Bi 23: Ephedrine (G) l mt hot cht dng lm thuc cha bnh v h hp c chit t cy ma hong.
H 2 / Ni
CH CH NO , OH
AlCl3
3 Br
F CH
G
Ephedrine c tng hp nh sau: C6H6 CO
, HCl
/
D 3 22 E
ephedrine.
Bi 24: Vit cng thc cu to sn phm cui (nu c) ca cc phn ng sau:
************************************************
Part 6
HNG DN GII
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52
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
Bi 4:
a. Br(CH2)3pC6H4CH2OH.
b. C6H5CH2OH.
Bi 5:
a. C6H6
1.CH3CH 2 Cl / AlCl3
2.Br2 ,t o
3.(CH3 )3 COOK
4.HBr,ROOR
5.HC CLi
C6H5CH2CH2C CH.
1.Cl2 / FeCl3
2.Na 2 Cr2 O7
3.SOCl2
4.NH 3
b. C6H5CH3
p-ClC6H4CONH2.
1.KMnO 4 / OH
2.SOCl2
3.C6 H5 CH 3 /AlCl3
4.Na 2 Cr2 O7
5.CH 3OH/H 2SO 4
c. C6H5CH3
C6H5COpC6H4COOCH3.
1.SO3 ,H 2SO 4
2.Br2 ,FeBr3
3.H 2 O,t o
4.Na 2 Cr2 O7 / H 2SO 4
CH 3 CHBr CH 2 CH 2 CH 2 Br
Metylthiophene .
53
Bi 8:
H 3O
SO 2 Cl
KCN
CH3CHClCH 3
CH 3CHCNCH3
CH3CHCOOHCH 3 .
a. CH3CHOHCH 3
CH 2 = CH 2
KCN / alcohol
CH 2 = CH CH = CH 2
cyclohexene.
b. I(CH 2 )4 I
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:
t
A + 8KMnO4
p-KOOCC6H4COOK (B) + 2K2CO3 + 8MnO2 + 2KOH + 4H20.
+ Br2 (Fe)
C+D
A
HBr
f. CH3CHCH3CH2CH2CHCH3CH3.
b. CH3CHCH3CH2OH.
g. CH3CHCH3CH2MgCl.
c. CH3CHCH3=CH2.
h. CH3CHCH3CH2OCOCH3.
d. CH3CHCH3CH2COOH.
i. CH3CHCH3CH2SH.
e. CH3CHCH3CH2NH2.
Bi 16: Ha tan hn hp trong ether v thm mt lng Mg va , khi iodobezene chuyn thnh
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.
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Vy cng thc cu to ca A l:
A l chlorobezene.
D l hydroquinone.
B l phenol.
E l p-nitrophenol.
C l p-benzoquinone.
F l p-aminophenol.
CH3
C
C
CH3
B
O
C
C
O +
C OC2H5
C OC2H5
C2H5OH
O
C
C
C
C
+ NH3 (kh, d- )
C NH2 160OC
C OH
C
C
N H
ftalimit F
N H
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
C2 H5 OH
CH3C+CH3CH(CH3)2
CH2=C(CH3)CH(CH3)2 (C).
A l benzene.
E l p-bromo-m-aminocumene.
B l cumene.
F l p-Br-m-+N2BF4C6H3CH(CH3)2.
C l p-bromocumene.
G l p-bromo-m-fluorcumene.
D l p-bromo-m-nitrocumene.
m-fluor-p-magnesiumbromocumene.
Bi 22: S tng hp
a. Aniline:
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:
57
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58
Part 7
ALCOHOL PHENOL
ALDEHYDE CETONE
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
(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
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
Cyclohexanol
HBr
1. Li
2. CuI
A
3.
CH2
CH2
NBr
O
N H /O
B (NBS) C 2 4 2
Br
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:
o
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
KMnO (c nng)
H Pt
/
Methyl cyclopentane
C10H16 (G)
1. CH MgCl
3
2. H3O+
C 5 H 9 Br( E )
C10H18O (F)
2.Cyclopentanone
3.H 3 O
C6 H 5COOOH
C5H8O (C)
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
59
Bi 7: T nha thng, ngi ta tch c cht hu c (X) v chuyn ha (X) theo s sau:
H 2 ,xt
P,t ,xt
A
B
2HCHO
Trng ngng
+ CuO, t
D (poliether)
Ca (OH )
O2 ,xt
2(d )
E
F (acid a chc)
G
Bi 10: Khi cho cis v trans-3,3-imethyl-2-bromocyclohexanol phn ng nhanh vi base mnh s thu
OEt
ph vng
HOEt
OEt
khp vng
OEt
H
OEt
X
A
D
G
B
C
E
F
Y
Trong X, Y ln lt l:
(X)
Copyright 2009 volcmttl@yahoo.com.vn
(Y)
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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:
C phn ng
HNO3/H2SO4
C phn ng
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
khng cn H2SO4
61
Bi 20: T cc cht ban u c s nguyn t carbon 3, vit cc phng trnh phn ng (ghi r iu kin
Part 7
HNG DN GII
-------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------------
Bi 1: Phn ng gia cc alcohol cho vi HBr l phn ng th theo c ch SN. Giai on trung gian
HCHO
OH
HO
DMF
HO
CH2CN
NaCN
CH2CONH2
H2O
HO
HO
OH
OH
Cl
H2NCOCH2
O
H2NCOCH2
Cl
H2NCOCH2
D1
D2
Sn phm ph:
OH
C19H22O5N2
CH2CONH2
H2NCOCH2
CHO
H
CHO
OH
CH2OH
CH2OH
D-Glyxeraldehit
D-Glyceraldehyde
H
eO
CH2OH
C
MeO
O
CH2OH
O
MeOH
CH2
O
CH2
CH2OH
D
62
63
Bi 7:
a. Cng thc cu to sn phm:
C3 c 2 ng phn quang hc
C2 c 4 ng phn quang hc
D c ng phn E, Z.
Bi 8:
79, 59 12, 25 8,16
=
=
= 13 : 24 :1 => A c cng thc phn t l C13H24O
12
1
16
Tn ca A: 3-Ethyl-7-methyldeca-2,6-diene-1-ol
Copyright 2009 volcmttl@yahoo.com.vn
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:
o
p,t ,xt
HOCH 2 CHO ( A).
2HCHO
xt
HOCH 2 CH 2 OH (B).
HOCH 2 CHO + H 2
(CH3COO)2 C2 H 4 (C).
2CH 3COOH + C2 H 4 (OH)2
trng ngung
(OCH 2 CH 2 )n (D) + nH 2 O.
HOCH 2 CH 2 OH
o
t
OHC CHO (E) + 2H 2O+2Cu.
HOCH 2 CH 2 OH + 2CuO
xt
HOOC COOH (F).
OHC CHO + O 2
Bi 10:
Bi 11:
A l PhCOOH.
E l PhCOPh.
B l PhCOCl.
F l Ph2C=NOH
C l PhCONH2.
G l PhCONHPh.
D l PhNH2 (+CO2).
(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
Bi 13:
OH
Trong mi trng base: C6 H 5CHO + CH3COCH 2 CH 3
C6 H5CH = CHCOCH 2 CH 3 + H 2O .
to
H
Trong mi trng acid: C6 H 5CHO + CH3COCH 2CH 3
C6 H 5CH = C(CH3 ) COCH 3 + H 2O.
to
C l acetone CH3COCH3.
A l CH3CHOHCH2COOH.
B l CH3CH=CHCOOH (cis/trans).
Bi 15:
Vy A l cycloheptadex9enone.
Copyright 2009 volcmttl@yahoo.com.vn
61
A(transv cis)
cis A
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
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:
-
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.
62
Bi 19: Ozone phn A thu c ethadial chng t trong A c nhm =CHCH= . Thu phn B thu c
************************************************
63
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.
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************************************************
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
65