1.

Xc nh cng thc cu to cc hp cht hu c A, B, C, D, A1, A2, A3, A4 trong cc s phan

ng sau (khng ghi phan ng):
CH OH CH =C(CH )COOCH
H SO a
c, to D
H O
B
C
3
2
4
3
2
3
3

+
+Benzen/H A3 +1)O2, 2)H2SO4
Cra

ckinh
(3)
(2)
A5 (C3H6O)(propan-2-on)
b) CnH2n+2
A2
(1)
A1(kh)
(4)
A4 (5)+O2/xt
+H O/H+

a) A
HCN

2. Hon thnh cc phng trnh phan ng:

to
+KMnO
4
CH2 CH(CH )
a)
3 2

b) Glixerol +Cu(OH)2

o
V O , 350450o C
c) Naphtalen + O2
d) Nitrobenzen + Cl2
Fe, t , 1:1
2 5
A: CH3COCH3
B: (CH3)2C(OH) CN
C : (CH3)2C(OH) COOH
D: CH2=C(CH3)COOH
A1: CH3-CH2-CH2-CH3
A2: CH3- CH=CH2
A3: C6H5-CH(CH3)2 (Cumen)
A4: CH3-CH(OH)-CH3

CH2 CH CH3+ 8 KMnO4

to

1,0

3 C6H5COOK + 3 CH3COCH3 + 5KOH + 8 MnO2 + 2 H2O

CH

3
a)
b) 2C3H5(OH)3 +Cu(OH)2 [C3H5(OH)2O]2Cu + 2H2O
c)

+ 9/2O2
CO

V2O5 , 350450o C

1,0

CO

+ 2CO2+ 2H2O

d)
NO2

NO2

Fe, t , 1:1

+ Cl2

Cl

+ HCl

2. Hon thnh cc phng trnh phan ng theo s sau:

+Mg/ete
Etyl bromua
A
(1)

H2 O
+HCHO
X1
X2
(3)
(2)
+CH3COCH3
H2 O
Y1
Y2
(4)
(5)

+CO2
(6)

Z1

H2 O
(7)

Z2

3. un nng 0,16 mol hn hp E gm hai peptit X (C xHyOzN6) v Y (CnHmO6Nt) cn dng 600 ml

dung dch NaOH 1,5M ch thu c dung dch cha 2 mui ca 2 aminoaxit c dng H2N-R-COOH.
Vit cc phng trnh phan ng v tnh s mol ca X, Y.
4. Hirocacbon C7H12 (A) b oxi ha bng axit cromic to ra axit xiclopentancacboxylic, (A) tc
dng vi H2SO4 c ri thy phn thu c ancol C7H14O, ancol ny cho phan ng ioofom. Vit cu to
ca hirocacbon trn v vit cc phng trnh phan ng giai thch.

Cu 2. (5,0 im)
1. Trnh by phng php ha hc phn bit 4 l ha cht lng mt nhn gm axit fomic, axit
acrilic, ancol etylic v ancol propylic.
2. Bit cng thc ca mt anehit no (A) l (C 2H3O)n. Hy xc nh cng thc cu to ca A.
Chn mt ng phn anehit ca A ri vit phng trnh phan ng xay ra ln lt vi lng d: dung
dch AgNO3/NH3, Br2/H2O; Cu(OH)2/NaOH.
3. A1 l hp cht thm c cng thc phn t C 7H8O2. A1 phan ng ht vi Na d sinh ra H 2 c s
mol bng s mol ca A1. A1 tc dng c vi Na2CO3, nhng khng phan ng vi NaHCO 3. Khi tc dng
vi HCl to hp cht c cng thc C 7H7OCl, cn tc dng vi Br2 to c dn xut tribrom. Lp lun xc
nh cu to, gi tn A1 v vit cc phng trnh phan ng xay ra.
4. a) Trong phng th nghim ngi ta iu ch etilen bng cch un nng etanol vi H 2SO4 c
170o C. Giai thch ti sao cn dn san phm li qua dung dch NaOH long.
b) X, Y, Z, T l cc ng phn c cng thc chung C 4H7Br. un nng X hoc Y vi dung dch
NaOH u thu c anehit butiric, un nng Z hoc T vi dung dch NaOH u thu c etylmetylxeton. X
bn hn Y, Z bn hn T. Vit cng thc cu trc X, Y, Z, T v cc phan ng xay ra.
Cu 3. (5,0 im)
1. Mt hp cht A1 c trong t nhin, ch cha C, H, O v c thnh phn nguyn t cu to gm:
63,16%, 5,26% H, 31,58% O.
a) Xc nh cng thc phn t A1, bit M(A1)=152vC.
b) A1 tc dng c vi dung dch NaOH trong nc, nhng khng tc dng c vi dung dch
NaHCO3 trong nc. A1 c th to c gng bc vi dung dch Ag(NH3)2+ v ch c lin kt hiro lin
phn t mt chiu. Hy vit bn cng thc cu to c th c ca hp cht A1.
2. Cht hu c A2 c cng thc phn t l C9H9Cl. Khi oxi ha A2 bng dung dch KMnO4 trong
H2SO4, un nng th thu c axit benzoic. A2 tc dng c vi dung dch NaOH cho hai san phm X 2,
Y2 u c cng thc phn t l C9H10O. Xc nh cng thc cu to ca A2, X2, Y2.
Vit cc phng trnh phan ng xay ra.
3. Cht hu c X l mt ancol no, hai chc, mch h. Dung dch X 62% trong nc c nhit
ng c l

930 o
C.
19

a) Xc nh cng thc cu to ca X. Bit hng s nghim lnh ca nc l 1,86.

b) Trnh by 3 cch khc nhau iu ch X t etilen.
c) Khi c mt cht xc tc thch hp th cht (X) kh nc to ra cht (A). Trong mi trng kim,
hai phn t (A) kt hp vi nhau to ra cht (B) khng bn. Khi un nng th (B) tch nc to ra cht (D).
T (D) cho tc dng vi HCl to cht (E).
- Thc hin s chuyn ha trn xc nh cng thc cu to ca A, B, D, E.
- Dng c ch phan ng giai thch qu trnh (A) to thnh (B).
- E c ng phn lp th hay khng? Hy xc nh cu trc cc ng phn lp th ca E.
2. Cng thc ca axit cacboxylic A1 mch h, khng nhnh l (CHO)n. Bit rng c 1 mol A1 tc
dng ht vi NaHCO3 giai phng ra 2 mol CO2; dng P2O5 tch nc t mt phn t A1 to ra cht B1 c cu
to mch vng. Vit cng thc cu to ca A1, B1, gi tn A1 v vit phan ng to ra B1.
3. Hp cht hu c X c cng thc C 5H4O2 phan ng vi thuc th Sip v vi phenylhirazin (X
hp cht mch vng c nhm -CHO). Ngi ta thc hi n m t s chuyn ha nh sau:
KMnO

C5H4O3(A)

t0

C4H4O(B)

H O
2
C6H8N2(E)

H2
xt

HCl d
C4H8O(C)

H N(CH2 )6 NH2
C6H10O4 (G)
2

KCN
C4H8Cl2 (D)

nilon 6,6.

Bit A tan c trong dung dch NaHCO3, C tan c trong H2SO4 c , lnh, khng lm mt mu dung
dch KMnO4, C khng c nhm chc - OH. Hy xc nh cu to ca X v cc san phm t A n G.
Cu
Ni dung
im
Cu 1 1 Chiu tng dn linh ng ca nguyn t H trong nhm OH:
0,5
C2H5OH< C6H5-CH2OH < p-CH3-C6H4OH< C6H5OH< CH3COOH< CH2=CHCOOH<HCOOH

Cu

2 Cc phng trnh phan ng :

CH3CH2Br + Mg
ete

im

CH3CH2MgBr

H C
O

CH3 CH2MgBr

Ni dung

CH3 CH2 CH2 OMgBr

CH3 CH2 CH2 OMgBr + H2O

CH3 CH2 CH2 OH + Mg(OH)Br

CH3 CH2MgBr + CH3

CH3
CH3 CH2 C CH3
OMgBr

C
O

CH3

CH3
CH3 CH2 C CH3 + H2O
OMgBr

1,5

CH3
CH3 CH2 C CH3 + Mg(OH)Br
OH

CH3CH2MgBr + CO2 CH3CH2COOMgBr

CH3 CH2 C

CH3 CH2 C

OMgBr + H2O

OH + Mg(OH)Br

VXvYchccutobicc aminoaxit c dng H2N-R-COOH

aminoaxitcha1chcNH2v1chcCOOH
VyXlhexapeptitvYlpentapeptit
GismolcaXvYlnltlx,ytrong0,16molhnhp
Phnng:X+6NaOHMuicaaa+H2O(1)
Y+5NaOHMuicaaa+H2O(2)

1,5

x y 0,16 x 0,1

6x 5y 0,9 y 0,06
Ta thy: (A) c = 2 , c cha vng 5 cnh, vy A c 2 nguyn t C trn nhnh to 1
lin kt i C=C. Vy A l
Tach:

CH=CH2

(vinyl xiclopentan)

Oxi ha

CH=CH2

CH=CH2

H2SO4

CH(SO4H)-CH3

CH(OH)-CH3

Cu 2

COOH

CH(SO4H)-CH3

H2O

3I2+4NaOH

CH(OH)-CH3

COONa +CHI +3NaI+4H O

3
2

- Nhn ra hai axit cacboxylic bng qu tm m, ri phn bit hai axit bng phan ng
trng gng (axit fomic to kt ta Ag).
RCOOH + H2O

RCOO- + H3O+

HCOOH+2AgNO3+ 4NH3 + H2O

1,5

to

(NH4)2CO3 +2Ag + 2NH4NO3

- Dng I2/NaOH phn bit hai ancol (ch etanol to kt ta vng iodofom).

1,0

Cu

Ni dung
CH3CH2OH + 4I2 + 6NaOH HCOONa + CHI3 + 5NaI + 5H2O

im

CTPT anehit: C2nH3nOn <=> C2n-nH3n-n (CHO)n <=> CnH2n (CHO)n

=> n = 2 C4H6O2

iu kin anehit no: Vy: 2n=2n+2-n

C2H4(CHO)2+ 4Ag[(NH3)2]OH

to

C2H4(COONH4)2 + 6NH3 + 4Ag+2H2O

1,0

C2H4(CHO)2 + 2Br2 + 2H2O C2H4(COOH)2 + 4HBr

C2H4(CHO)2 + 4Cu(OH)2 + 2NaOH
3

to

C2H4(COONa)2 + 2Cu2O + 6H2O

C7H8O2 c = 4, nh vy A1 c mt nhn thm.

A1 + Na d sinh ra H2 c s mol bng s mol ca A1 A1 c hai nhm OH
A1 + Na2CO3, nhng khng phan ng vi NaHCO3 A1 c nhm phenol
A1 + HCl cho thy A cha nhm ancol.
A1 + Br2 dn xut tribrom 2 nhm th trn nhn thm v tr meta
Cu to v tn gi :

1,5
Cc phng trnh phan ng :
HOCH2C6H4OH + 2Na NaOC6H4CH2ONa + H2
HOCH2C6H4OH + Na2CO3 HOCH2C6H4ONa + NaHCO3
HOCH2C6H4OH + HCl ClCH2C6H4OH + H2O

4 San phm sinh ra ngoi CH =CH cn CO ,SO (do H SO ) c nng oxi ha cht
2
2
2
2
2
4
hu c) v C2H5OH b cun theo. Dung dch NaOH phan ng vi CO2,SO2
2NaOH + SO2 Na2SO3 + H2O

0,5

2NaOH + CO2 Na2CO3 + H2O

C2H5OH tan mt phn trong dung dch NaOH long
Cng thc cu trc X, Y, Z, T:
0,5

Cc phng trnh phan ng :

CH3-CH2-CH=CHBr + NaOH

to

CH3-CH2-CH2-CH=O + NaBr

0,5

Cu 3

CH3-CH=CBr-CH3 + NaOH t
CH3-CH2-CO-CH3+ NaBr
Cng thc nguyn v phn t: C8H8O3. Bn cu to ng phn:

O2
Ag, to

1,0

Cu

Ni dung

im

C9H9Cl c s lin kt + s vng no l 5

KMnO4/H
A

C6H5COOH Vy A2 c 1 nhnh vng benzen

2
A 2
NaOH X 2,Y2 c ctpt C9H10O A2: C6H5 CH = CH CH2Cl
(c 2 dng cis v trans)
X2, Y2 ln lt l: C6H5 CH = CH CH2OH
(c 2 dng cis v trans)
v C6H5 CH(OH)CH = CH2
5 C6H5CH=CH-CH2Cl+8 KMnO4+12 H2SO4
5 C6H5-COOH+4K2SO4+8MnSO4+5ClCH2-COOH+12 H2O

1,0

0,5

t CTTQ ca X: CnH2n+2-k(OH)k
+ Khi lng X c trong 1000 gam H2O:

1000.62 31000
=
38
19

31000
= 62 (g/ mol)
930

14n + 16k = 60

19
0+

19
Nghim ph hp: k = 2 v n = 2 CT ca X: C2H4(OH)2
MX = k

mX
= 1,86.
Dt

dd KMnO4, lanh

+ CH2 = CH2
+ CH2 = CH2

Cl2, CCl4

+ CH2 = CH2

CH2

CH3CH=CH-CHO (D)

o
ClCH2CH2Cl dd NaOH, t
CHH
CH2
CH2
2 2O

HCl

OH

CH3CHO(A)
OH

HO-CH2CH2OH

OH

CH3CH(OH)CH2CHO(B)
t

0,5

CH3CHClCH2CHO (E)

C ch: CHOH
3 CHO
- - H2O
CH3 CH O

CH2

HO-CH2CH2OH

H2SO4
HO-CH2CH2OH(X)
170
oC

1,0

CHO

E c ng phn lp th do c C*

1,0
CH3 CH
O-

CH2 CHO

H2O

CH3 CH
OH

CH2 CHO

Cu

Ni dung
CH2 - CHO
R

CH2 - CHO

Cl

Cl

CH3

CH3

Trch MT cho tc dng vi H2O, xc tc HgSO4, un nng. Ly san phm thc hin
phan ng trng gng:
-Nu to Ag CH3CHO C2H2
0
Phan ng: C2H2 + H2O HgSO4 ,t
CH3CHO
CH3CHO + 2Ag(NH3)2OH CH3COONH4 + 2Ag + 3NH3 + H2O
-Nu khng phan ng l CH3CO-CH3 CH3C CH
0
CH3C CH + H2O HgSO4 ,t

im

2,0

CH3CO-CH3

V 1 mol A1 tc dng c vi NaHCO3 giai phng 2 mol CO2 A l mt axit 2 nc

CTPT ca A1 phai l C4H4O4 hay C2H2(COOH)2. ng vi mch khng nhnh c 2
ng phn cis-trans l:
HOOC

H
C

COOH

HOOC

COOH

axit trans-butenioic (axit fumaric) axit cis-butenioic (axit maleic)

Ch c ng phn cis mi c kha nng tch nc to anhirit:

1,0

O
C

COOH

H
C

P2O5

+H2O

C
COOH

3
NH2(CH2)6NH(

Cu 4

(CH2)4

Nilon 6,6:

C NH

(CH2)6

) C
n
O

NH

(CH2)4

COOH

CN
(CH2)4

G l:

COOH
COOH

(CH2)4

C6H10O4

(CH2)4

D l

E l:
Cl

C6H8N2
CN

C4H8Cl2

Cl

C l:
B l:

2,0

Theo u bi, X phai l m t hp cht c nhm cacbonyl v phan ng vi thuc th Sip

v vi phenylhirazin. Vi cng thc C5H4O2 c th suy ra X l m t fufurol. Khi oxi
ha fufurol ta se c axit A:
CHO

COOH

KCN

Cl

CN(CH2)4CN

O
H2O
H

(CH2)4

HCl du

H2

Cl

KMnO4

COOH
COOH

xt

NH2(CH2)6NH2

nilon 6,6

1. Cho cc cht: C6H5OH, C2H5OH, CH3COOH, C6H5ONa, C2H5ONa. Vit cc phng trnh phan ng xay
ra (nu c, trong iu kin thch hp) khi trn cc cht vi nhau tng i mt.
2. Hon thnh cc phng trnh phan ng theo s chuyn ho sau:
C11H21 O4N NaOH C5H7O4NNa2 (B) + C3H8O (C)
C5H10O4NCl (D)
C3H6O (E)
C3H9O2N (F)
Bit B l mui ca mt - aminoaxit c mch cacbon khng phn nhnh.
3. Hon thnh cc phng trnh phan ng theo s chuyn ho sau:
Br2

X NaOH

Y
CuO, t

O , xt

CH OH, t o , xt

2
3
Z
T

4. Vit cc phng trnh ho hc trc tip iu ch cc loi t sau: axetat, nilon-6,6, lapsan.

C3H6

1. CH3COOH + C2H5OH

xt,t 0

E (a chc).

CH3COOC2H5 + H2O

CH3COOH + C6H5ONa
CH3COONa + C6H5OH
CH3COOH + C2H5ONa
CH3COONa + C2H5OH
C6H5OH + C2H5ONa
C6H5ONa + C2H5OH
o
t
2. H3C-[CH2]2-OOCCH(NH2)[CH2]2COO-[CH2]2CH3 + 2 NaOH
2CH3-CH2CH2OH + NaOOC-CH(NH2)[CH2]2COONa
NaOOC-CH[CH2]2COONa+3HClHOOC-CH(NH3Cl)[CH2]2COOH+ 2NaCl
o
CH3-CH2CH2OH + CuO
CH3-CH2CHO + Cu + H2O
t
o
t
C2H5CHO+ 2[Ag(NH3)2]OH
C2H5COONH4 + 2Ag + 3NH3 + H2O

3. C3H6 (xiclopropan) + Br2 Br-CH2CH2CH2Br

o
Br-CH2CH2CH2Br + 2NaOH
HO-CH2CH2CH2OH + 2 NaCl
t
o

HO-CH2CH2CH2OH + 2CuO
O=HC-CH2CH=O + 2Cu + 2H2O
t
o
O=HC-CH2CH=O + O2
HOOCCH2COOH
xt,t
H SO ac,t
4. HOOCCH2COOH+CH3OH
2 4

CH3OOCCH2COOCH3+H2O

o
nHOOC-C6H4-COOH + nHO-CH2-CH2-OH xt,t ,p
o
[C6H7O2(OH)3]n + 2n(CH3CO)2O xt,t ,p
o
[C6H7O2(OH)3]n +3 n(CH3CO)2O xt,t ,p

(-CO-C6H4-CO-O-CH2-CH2-O-)n + nH2O

[C6H7O2(OH)(OCOCH3)2]n + 2nCH3COOH
[C6H7O2(OCOCH3)3]n + 3nCH3COOH

o
nHOOC-(CH2)4-COOH + nH2N-(CH2)6-NH2 xt,t ,p

(-OC-[CH2]4-CO-HN-[CH2]6-NH-)n + 2nH2O

Cu 5. (4,0 im)
1. Xc nh cc cht hu c A, B, C, D, E thch hp tha mn s phan ng sau:
H3O
CH3OH,xt,to
H2SO4a
c,to
to,p,xt
HCN
A
B

C
D
E
F
F l poli(metyl metacrylat).
2. Hp cht X c cng thc C8H14O4. T X thc hin cc phan ng (theo ng t l mol):
a) X + 2NaOH X1 + X2 + H2O
b) X1 + H2SO4 X3 + Na2SO4
c) nX3 + nX4 nilon-6,6 + 2nH2O
d) 2X2 + X3 X5 + 2H2O
Hy vit cc phng trnh phan ng xay ra.
1
Cc phan ng xay ra:

1,5

HCOOH + NaOH HCOONa + H2O

CH3COOCH=CH2 + NaOH

CH3COOC6H5 + 2NaOH

HCOOH + 2Ag(NH3)2OH

t0

t0

CH3COONa + CH3CHO
CH3COONa + C6H5ONa + H2O

t0

(NH4)2CO3 + 2Ag +2 NH3 + H2O

HCOOH + Br2 CO2 + 2HBr

CH3COOCH=CH2 + Br2 CH3COOCHBrCH2Br
2

Hon thnh s chuyn ho sau:

0
HCOOCH2CH2COOCH=CH2+2 NaOH
t

HCOONa+HOCH2CH2COONa+ CH3CHO

HCOONa + H2SO4 HCOOH + Na2SO4

1,0

HOCH2CH2COONa + H2SO4 HOCH2CH2COOH +Na2SO4

H SO , 180oC
HOCH2CH2COOH
2 4

CH2=CH-COOH + H2O

1. Mt hc sinh c phn cng tin hnh 2 th nghim sau:

Th nghim 1: Dn kh axetilen i chm qua dung dch nc brom.
Th nghim 2: Nh vi git dung dch AgNO3 vo ng nghim ng dung dch NH3 d, lc nh.
Thm tip dung dch glucoz vo, sau t ng nghim vo cc nc nng.
Nu hin tng, vit cc phng trnh phan ng ho hc xay ra.
2. Vit cc phng trnh phan ng thc hin s chuyn ho sau. Cc cht vit dng cng thc
cu to thu gn.
(1)

C3H6O

(2)

C3H6O2

(3)

C5H10O2

C3H8O
(4)

C5H10O2

(5)

C2H3O2Na

3. Vit cc ng phn cu to mch h, n chc, c cng cng thc phn t C3H6O2. Trnh by
phng php ha hc dng phn bit tng cht . Vit phng trnh phan ng ha hc xay ra
Cu

Ni dung
im
II

1
(1)

+) Th nghim 1:
- Hin tng: Dung dch brom nht mu dn sau b mt mu.
C2H2 + Br2 C2H2Br2
C2H2Br2 + Br2 C2H2Br4
Hoc C2H2 + 2Br2 C2H2Br4
+) Th nghim 2:
- Hin tng:
*) Khi cho dung dch AgNO3 vo dung dch NH3 d c kt ta, lc nh kt ta
tan ra
*) Thm tip dung dch glucoz vo, sau t ng nghim vo cc nc
nng c kt ta trng bm quanh ng nghim

0,25

0,25

AgNO3+3NH3+H2O [Ag(NH3)2]OH + NH4NO3

t0
C5H11O5CHO+2[Ag(NH3)2]OH

C5H11O5COONH4+2Ag+ 3NH3 + H2O

t0
Hoc C5H11O5CHO+2AgNO3+3NH3+H2O

C5H11O5COONH4+2Ag +2NH4NO3

0,25

0,25
2
(1)

t
(1) CH3CH2CH2OH + CuO
CH3CH2CHO + Cu + H2O
0
t , xt
(2) 2CH3CH2CHO + O2
2CH3CH2COOH

0,25

H SO

4
2

CH3CH2COOC2H5 + H2O
(3) CH3CH2COOH + C2H5OH

H SO

4
2

CH3COOCH2CH2CH3 + H2O
(4) CH3CH2CH2OH + CH3COOH

0,25

t
(5) CH3COOCH2CH2CH3 + NaOH
CH3COONa + CH3CH2CH2OH

0,25

0,25
3
(1)

+) C3H6O2 c 3 ng phn cu to, mch h n chc

CH3CH2COOH; HCOOCH2CH3; CH3COOCH3
+) Nhng qu tm ln lt vo 3 mu th ca 3 cht trn
- Qu tm ha l: CH3CH2COOH
- Qu tm khng i mu l: HCOOCH2CH3; CH3COOCH3
+) Cho ln lt 2 cht: HCOOCH2CH3; CH3COOCH3 tc dng vi dung dch
AgNO3 trong NH3, un nng
- C kt ta trng l HCOOCH2CH3
t0
HCOOCH2CH3 + 2AgNO3+3NH3+H2O

NH4OCOOCH2CH3+ 2Ag+ 2NH4NO3

- Khng hin tng l CH3COOCH3

0,5

0,25

0,25

1. A l mt ng ng ca benzen c t khi hi so vi metan bng 5,75. A tham gia chuyn

ha theo s

Hy vit cc phng trnh ha hc theo s trn, cc cht hu c vit dng cng thc cu
to rt gn, cho bit B, C, D, E l cc cht hu c.
2
(4,0)

MA = 16
t cng thc A : CnH2n-6 14n-6 = 92 n =7

2,0

CT :

Phng trnh:
C6H5-CH3 + Cl2

C6H5-CH2Cl + HCl

C6H5-CH3 + 3H2 d
C6H5-CH3 + 3HNO3

C6H11-CH3
H2SO4 C6H2(NO2)3-CH3 + 3H2O

C6H5-CH3 + 2KMnO4

C6H5-COOK + 2MnO2 + KOH + H2O

Bi 7 (1,0 im). Tm cc cht thch hp ng vi cc k hiu A1, A2, A3, A4, A5 trong s sau v hon
thnh cc phng trnh phan ng di dng cng thc cu to?
+Benzen/H+
CnH2n+2
A1(kh)

Bi 7
1,0

Crackinh

(1)

A3

(2)

A2

(4)
+H2O/H+

A4

+O2,xt
(3)

A5 (C3H6O)

(5) +O2/xt

* Cc cht cn tm:
A1: CH3-CH2-CH2-CH3
A2: CH3- CH=CH2
A3: C6H5-CH(CH3)2 (Cumen)
A4: CH3-CH(OH)-CH3
A5: CH3-CO-CH3
* Cc phan ng:
1. CH3-CH2-CH2-CH3

0,25
Crackinh

(A1)

H2SO4

2. CH3-CH=CH2 +

CH(CH3)2
3.

CH3-CH=CH2 + CH4
(A2) CH(CH3)2

(A3)

0,25

OH

1.O2
2.H2SO4(l)

+ CH3-CO-CH3
(A5)

H+

4.

CH3-CH=CH2 + H2O

5.

CH3-CH(OH)-CH3 + 1/2O2

Cu,t0

0,25

CH3-CH(OH)-CH3 (A4)
CH3-CO-CH3
(A5)

+ H2O

Ghi ch:
Khi chm nu hc sinh gii theo cc phng php khc, nu ng vn cho s im.

0,25

Trong mt bi th sinh lm ng n phn no th tnh im n phn theo thang im.

Cu 3 (1,5 im)
1. T qua cy vanilla ngi ta tch c 4-hidroxi-3-metoxibenzandehit (vanilin) c cng thc
phn t C8H8O3, dng lm cht thm cho bnh ko. T qua cy hi, ngi ta tch c
4metoxibenzandehit c cng thc phn t C8H8O2. T qua cy hi hoang, ngi ta tch c
pisopropylbenzandehit c cng thc phn t C10H12O.
a. Hy vit cng thc cu to ca ba cht trn.
b. Trong ba cht , cht no c nhit si cao nht?
2. Mt hidrocacbon mch h A c cng thc phn t C 10H18 (khung cacbon gm hai n v isopren
ni vi nhau theo quy tc u ui). Oxi ha A bng dung dch KMnO 4 trong H2SO4, thu c hn hp
cc cht A1, A2 v A3. Cht A1 (C3H6O) tc dng vi H2 (xc tc Ni) to ancol bc 2. Cht A2 (C2H4O2) phan
ng c vi Na2CO3. Cht A3 (C5H8O3) cha nhm cacbonyl (C=O), phan ng c vi Na2CO3.
a. Vit cng thc cu to ca A1, A2, A3 v A.
b. Vit cng thc cc ng phn hnh hc ca A.
1.a.
HO

H3C

CHO

H3CO

CH

CHO

CHO

H3C

H3CO

4-hiroxi-3-metoxibenzandehit 4-metoxibenzanehit
p-isopropylbenzanehit
----------------------------------------------------------------------------------------------b. Cht 4-hiroxi-3-metoxibenzandehit c nhit si cao nht
2. a. Cng thc cu to:
A1: CH3 CO CH3
A2: CH3 COOH
CH3 - C = CH - CH2 - CH2 - C = CH- CH3
HOOC - CH2 - CH2 - C - CH3
CH3
CH3
O
A3:
A:
----------------------------------------------------------------------------------------------b. Vit ng 2 ng phn hnh hc
H3C

H2C
C

CH2
C

H3C

H3C

CH3

H3C

H2C
C

CH2
C

H3C

H
C

H3C

CH3

1. A, B, C, D l cc cht kh u lm mt mu nc brom. Khi i qua nc brom th A to ra mt cht

1
kh vi s mol bng
s mol A; B to thnh cht lng khng trn ln vi nc; C to ra kt ta mu
2
vng; cn D ch lm mt mu nc brom to thnh dung dch trong sut. Hi A, B, C, D l cc kh g?
2. Vit cc phng trnh ho hc hon thnh s cc phan ng ho hc sau:
Heptan

-A
xt

+B
xt

Y1
Y2

+B

+B

+B

+ C + C'

+D

2,4,6-triamintoluen

1.
+ A l amoniac v:
2NH3 + 3Br2 N2 + 6HBr
+ B l hirocacbon khng no nh etilen; propilen: C2H4 + Br2 C2H4Br2.
+ C l H2S v: H2S + Br2 2HBr + S(nu un nng th: H2S + 4Br2 + 4H2O 8HBr + H2SO4)

1,0

IV
(2,5)

+ D l SO2 v: SO2 + Br2 + 2H2O 2HBr + H2SO4.

2.
A l hiro; X l toluen; B l HNO3; Y1; Y2 l o, p nitrotoluen; Z l 2,4-initrotoluen;
T l 2,4,6-trinitrotoluen; C v C l Fe + HCl; U l CH3-C6H2(NH3Cl)3; D l Kim (NaOH).
Heptan

-A
xt

+B
xt

Y1
Y2

+B

+B

+B

+ C + C'

+D

2,4,6-triamintoluen

1. A l hp cht thm c cng thc phn t C 7H8O2. A phan ng ht vi Na d sinh ra H 2 c s mol bng
s mol ca A. A tc dng c vi Na 2CO3, nhng khng phan ng vi NaHCO 3. Khi tc dng vi
HCl to hp cht c cng thc C7H7OCl, cn tc dng vi Br2 to c dn xut tribrom.
(a) Lp lun xc nh cu to A v gi tn.
(b) Vit cc phng trnh phan ng xay ra.
1. (a) C7H8O2 c = 4, nh vy A c mt nhn thm.
A phan ng ht vi Na d sinh ra H 2 c s mol bng s mol ca A, nh vy A c hai
nhm chc cha H linh ng (hai nhm OH).
A tc dng c vi Na2CO3, nhng khng phan ng vi NaHCO 3, nh vy A c
nhm phenol. A tc dng vi HCl cho thy A cha nhm ancol.
Khi tc dng vi Br2, A to c dn xut tribrom, nh vy hai nhm th trn nhn
thm v tr meta-.
Cu to v tn gi :

Cc phng trnh phan ng :

HOCH2C6H4OH + 2Na NaOC6H4CH2ONa + H2
HOCH2C6H4OH + Na2CO3 HOCH2C6H4ONa + NaHCO3
HOCH2C6H4OH + HCl ClCH2C6H4OH + H2O

1. Hp cht X c cng thc phn t C 9H10O2 phan ng vi dung dch NaHCO3 giai phng kh CO2. X
khng lm mt mu dung dch nc brom. X khng phan ng vi CH 3OH khi c m t H2SO4 c. Khi cho
H2SO4 c vo X sau cho hn hp vo CH3OH c lm lnh th thu c hp cht B c cng thc
phn t C10H12O2. Hy vit cng thc cu to ca A. Giai thch cc tnh cht trn ca A v c ch phan ng
to thnh B.
2. ixian l hp cht c cng thc C2N2. Vit CTCT ca ixian, khi un nng ixian n 500 0C thu
c cht rn A c mu en, cng thc (CN)n. Vit CTCT ca A.
1. A ( C9H10O2):
- Phan ng vi NaHCO3 giai phng CO2 nn A cha nhm COOH
- Khng lm mt mu nc brom nn A cha benzen
- A l axit m khng phan ng este ha vi CH3OH nn A phai c n ng khng gian nhm
COOH ln, do A c cu to l:

1,5

CH3
COOH
CH3
S to thnh B:
CH3
C

O
OH

CH3

CH3
O -- H O
2
C
OH2
CH3

CH3

CH3
C O

CH3OH
-H+

CH3

O
OCH3

CH3

(cng

m t m t phng)
2. Hng dn:
CTCT ca ixian: N C C N
Khi nung nng 5000C A : (CN)n.
CTCT ca A:
C

C
C
C
N
N
N
N
1. Xc nh cng thc cu to cc cht v hon thnh s cc chuyn ha sau:
A

A1
B1

C3H8

A2
B2

CH3COOH

B
B3

A1

2. Ch dng dung dch HBr c th nhn bit c nhng cht no trong s cc cht cho sau y (cht
lng hoc dung dch trong sut): ancol etylic, toluen, anilin, natri hidrocacbonat , natri phenolat. Vit
phng trnh ha hc cc phan ng xay ra.
3. Cho ln lt cc cht: axit acrylic; p-crezol; tristearin; glucoz; tinh bt ln lt tc dng cc cht
nhit thch hp: dung dch HCl; dung dch NaOH; Cu(OH) 2 ( nhit thng). Vit phng trnh phan
ng xay ra (nu c).
1 (1,0 im)
A: C2H4;
A1: CH3CHO;
A2: C2H5OH
B: CH4;
B1: HCHO
B2: CH3OH
B3: C2H2
B4: CH3CHO
0
C3H8 t , xt
C2H4 + CH4
t 0 , xt
2CH2=CH2 + O
2CH3CHO
2
t 0 , Ni
CH3CHO + H
CH3CH2OH
2
men giam
CH3CH2OH + O2
CH3COOH + H2O
0
t , xt
CH4 + O
HCHO + H2O
2
t 0 , Ni
HCHO + H
CH3OH
2
0
CH3OH + CO t , Ni CH3COOH
0

C
san pham1500
2CH4
lam lanh nhanh
0

C2H2 + H2O t , xt
2CH3CHO + O
2

C2H2 + 3H2

CH3CHO
, xt
2 CH3COOH

2 (0,5 im)
C th nhn bit tt ca cc cht v chng gy ra cc hin tng khc nhau khi cho cc cht vo
dung dch HBr:
+Nu to thnh dung dch ng nht => mu l C2H5OH
+ Nu c hin tung phn tch thnh 2 lp => mu l C6H5CH3 (toluen)
+ Nu ban u c hin tng tch lp, sau tan dn to dung dch ng nht => Mu l
C6H5NH2 (anilin)
C6H5NH2 + HBr
C6H5NH3Br
+ Nu c si bt kh khng mu, khng mi => mu l NaHCO3:
NaHCO3 + HBr
NaBr + CO2 + H2O
+ Nu to cht khng tan, vn c mu trng => mu l C6H5ONa (Natri phenolat):
C6H5ONa + HBr
C6H5OH + NaBr
3 (0,5 im)
+ Phan ng ca axit acrylic
CH2=CH-COOH + HCl ClCH2CH2COOH v CH3CHClCOOH
CH2=CH-COOH + NaOH CH2=CH-COONa + H2O
2CH2=CH-COOH + Cu(OH)2 (CH2=CH-COOH)2Cu + 2H2O
+ Phan ng ca p-crezol:
p-HO-C6H4-CH3 + NaOH p-NaO-C6H4-CH3 + H2O
+ Phan ng ca tristearin:
0

HCl , t
(C17H35COO)3C3H5 + 3H2O
3C17H35COOH + C3H5(OH)3
(C17H35COO)3C3H5 + 3NaOH (dd) 3C17H35COONa + C3H5(OH)3
+ Phan ng ca glucoz:
2 C6H12O6 + Cu(OH)2 (C6H11O6)2Cu + 2H2O
+ Phan ng ca tinh bt:
HCl , t 0
(C6H10O5)n + n H2O
n C6H12O6
1. Cho hn hp X gm Glyxin v Alanin tham gia phan ng iu kin thch hp thu c cc san phm
ipeptit. Vit phng trnh phan ng v gi tn san phm to thnh.
2. Cho dy bin ho sau:
Al4C3

polivinylancol

B
G

Cao su Buna

Xc nh cc cht A, B, C, D, E, F, G v vit cc phng trnh phan ng (ghi r iu kin nu c).

2
1
0,25
2CH2-COOH
CH2-CO-NH-CH2-COOH + H2O
(1)
N
NH2
(Gly-Gly)
H2
0,25
2CH3-CH-COOH
CH3-CH-CO-NH-CH+ H2O

NH2

NH2
COOH

(Ala-Ala)

CH3
0,25

CH2-COOH + CH3-CH-COOH
NH2
NH2

CH2-COOH + CH3-CH-COOH
NH2
NH2

CH3-CH-CO-NH-CH2-COOH + H2O
NH2
(Ala-Gly)

CH2-CO-NH-CH-COOH
NH2
CH
3

(Gly-Ala)

+ H2O

0,25

2 Al4C3A: Al4C3 + 12H2O 4Al(OH)3 + 3CH4

(1)

(A)

CH CH + 3H2

AB:

C
1500
2CH4
LLN

BC:

(A)
(B)
CH CH + CH3COOH

xt

CH3COOCH=CH2

(B)

(C)

0,25

t0 , p
xt

nCH3COOCH=CH
2

CD:

0,25

(CH2-CH)n

(C)

(D)

OOC-CH3

Dpolivinylancol:
(CH2-CH)n

+ nNaOH(
CH
t 2-CH)n

OOC-CH3

OH

(D)

BE:

+ nCH3COONa
polivinylancol

CH CH + H2O

H , Hg 2
800 C

(B)
EF:

(E)

CH3CHO + H
2

Ni ,t

C2H5OH

(E)
FG:

2C2H5OH

0,25

CH3CHO

(F)
Al2O3 / ZnO
4500

CH2=CH-CH=CH2 + H2 + 2H2O

(F)
G Cao su Buna:

0,25

(G)
0

t ,p
nCH2=CH-CH=CH
2 ( CH
xt2-CH=CH-CH2)n

(G)
Cao su Buna
1. Cho s chuyn ha gia cc cht hu c nh sau:
A
C

dd KMnO4

B
D

dd H2SO4 c
t0C

CH3CHO
F (Mui amoni)
E

(Cc ch ci A, B, C, D, E, F l k hiu cc cht khc nhau cng c 2 nguyn t Cacbon trong phn t)
Tm cng thc cu to ca cc cht A, B, C, D, E, F v vit cc phng trnh phan ng xay ra theo
s bin ha trn, ghi r iu kin phan ng xay ra (nu c).
1
(1)
Cng thc cu to cc cht:
A. CH2=CH2
B. HOCH2-CH2OH
C. CH3-CH2-Cl
D. CH3-CH2-OH
E. CH3-COOH
F. CH3-COONH4

AB:

3CH2=CH2 + 2KMnO4 + 4H2O 3 HOCH2-CH2OH + 2KOH + 2MnO2

BCH3CHO: HOCH2-CH2OH

dd H2SO4 c
t 0C

CH3-CHO + H2O

A C: CH2=CH2 + HCl

CH3-CH2-Cl

C D: CH3-CH2-Cl + NaOH
D E: CH3-CH2-OH + O2

t 0C
Men gim

CH3-CH2-OH + NaCl
CH3-COOH + H2O

CH3-CHO F:
0

t
CH3-CHO + 2AgNO3 + 3NH3 + H2O

CH3-COONH4 + 2Ag + 2NH4NO3

E F: CH3COOH + NH3 CH3COONH4

Cu 6:
Hp cht A c cng thc phn t C 7H6O2, tan t trong nc nhng tan tt trong dung dch NaOH to
thnh mui B (cng thc C7H5O2Na). B tc dng vi nc brom to ra hp cht D, trong phn t D cha
64% Br v khi lng. Kh 6,1 gam hp cht A bng hidro (xc tc Pt) 20 0C thu c 5,4 gam hp cht
thm G.
a. Tnh hiu sut ca phan ng to ra G.
b. Xc nh cng thc cu to ca cc hp cht A, B, D, G.
Hng dn chm
Cu 6

Ni dung

im

Do s nguyn t C gn bng s nguyn t H v kha nng ha tan km ca A

trong nc, tc dng vi H2 to ra hp cht thm G A l hp cht thm. A tc
dng c vi NaOH => c cha nhm -OH thuc phenol hoc nhm COOH v
u ch cha mt nhm (do to san phm cha 1 nguyn t Na). iu kin
thng B tc dng vi dung dch nc brom nn B l mui ca phenol nhm
th cn li l CHO. Vy cng thc ca A l HO-C6H4-CHO.
Phan ng ca A vi H2 to HO-C6H4-CH2OH (G)
Theo l thuyt, s gam G thu c l 6,1.124/122 = 6,2 gam
Hiu sut to ra G = 5,4/6,2 = 0,871 hay 87,1%
Gi san phm ca B vi nc brom l HO-C6H4-nBrn-COOH ta c
80n/(138+79n) = 0,64 n =3.
Vy cng thc ca D l HO-C6HBr3-COOH
Trong A cc nhm th phai v tr meta vi nhau v ch trng hp ny vng
benzen mi c 3 nguyn t H b thay th bi brom. T cng thc cu to
ca A, B, D, G ln lt l

0,5
im

0,5
im

ONa

ONa

ONa

OH

Br

Br

1,0
im

CHO

CHO

CHO

CH2OH

Br