Pirol

Furan
H
S
Tiophen
N
Piridin
Quinolin
N
N
O

CH
2
CH
2
CH
2
CH
2

O C C
O O O
N
N
N
1
1
H
2
4
1,2,4-Triazol
N
N
N
1,2,4-Triazin
1
2
4
N
S
1
H
2
4
1,3-Thiazol
3
O
N
1
2
4
1,2-oxazol
3
S
N
1,4-Thiazin
2
3
4

MT S VN C BN CA HP CHT D VNG
A. nh ngha v cch gi tn
1. nh ngha chung: D vng l nhng cht hu c m phn t ca chng c cu to vng kn
v trong vng c cha mt hay nhiu d t (nguyn t khng phi l cacbon c trong b khung
phn t cht hu c)
V d:





2. Ch : c mt s hp cht tha mn vi nh ngha trn
nhng khng c xp vo loi hp cht d vng.
V d: etylenoxit, anhydrit sucxinicnhng cht ny d b v
vng, khng bn do tc dng cu nhit v han ton khng biu
l tnh thm.


3. Cch gi tn:
a) Tn thng thng: V d Furan ; Pirol ; Piridin ; Thiophen
(Nu d t l S th tip u ng l thio- ; nu d t l oxi th tip v ng l an)
b) Tn h thng:
* Qui tc: Ghp - Mt t c bn ni ln s cnh ca vng
- Mt hay nhiu tip u ng ch s lng v tn cc d t trong vng
- Mt tip v ng ni ln mc bo ha cu vng
+T c bn: - Vng 3 cnh: -ir- ; 4 cnh: -et- ; 5 cnh: -ol- ; 6 cnh: -in ; 7 cnh: -ep-
+Tip u ng: oxa ch oxi; thia ch lu hunh ; aza ch nit (s lng d t l di,
tri)
+Tip v ng: -vng 5 cnh cha nit cha bo ha c ui ol, nhng bo ha c ui
olidin
- vng 5 cnh khng cha nit, cha bo ha c ui ol, nhng bo ha c ui olan
- vng 6 cnh cha nit, cha bo ha c ui in, nhng bo ha c ui an
* Cch nh s:
- nu d vng cha 1 d t th s 1 dnh cho d t v tip tc ngc chiu kim ng h.
- nu d vng cha nhiu d t ging nhau th nh s sao cho cc d t c ch s nh nht(nu
c 2 d t l N c bc khc nhau th bt u t d t bc 2)
- nu d vng cha nhiu d t khc nhau th s 1 u tin cho O S N.
V d:







4. Phn loi: (thng c 2 cch phn loi)
- Phn loi theo s cnh: d vng 5 cnh; d vng 6 cnh
- Phn loi theo d t: d vng cha nit; d vng cha oxi; d vng cha lu hunh
B. Phng php tng hp d vng:
Ni chung c 2 cch iu ch cc d vng: - D vng ha cc hp cht mch khng vng
CH CH
CH CH
2
CH
2
CH CH
CH
2
O
O
OH
HO
P
2
O
5
P
2
S
5
NH
3
O
(furan)
S
( thiofen)
N
( pyrol)
H
CH
2
C C
CH
2
O
O
H
3
C CH
3
P
2
O
5
nung
O
(2,5-dimetylfuran)
CH
3 H
3
C

HC
CH CH
CH
C
C
P
2
S
5
NH
3
O
(furan)
S
( thiofen)
N
( pyrol)
H
CH
2
C C
CH
2
O O
HO OH
OH
OH
HO
HO
O
OH HO
O
t
0
O
COOH
- CO
2
t
0
HC
CH CH
CH
C
C
OH
OH
HO
HO
O
ONH
4
+
H
4
N
+
O
O


CH CH + 2HCHO
2 2
Cu Cl
HO-CH
2
-C C-CH
2
-OH
3
NH ,P

N
H
- Vng ha cc hp cht thm c mch nhnh.
V d:
a) i t 1,4-diandehit hay dixeton:


















b) i t diaxit:















c) Pyrol c th tng hp bng cch:




d) Thiophen thu c bng cch nung n-butan vi lu hunh nhit cao:

CH
3
CH
2
CH
2
CH
3
+ S
560
0
C
S
+ H
2
S

e) Ngng t andehit o, | cha no vi NH
3
:
N
H
KOH
N
K
+
(-)
+H
2
O

N
N
H

N
CH
3
CO
2
NO
2
(CH
3
CO)
2
O, 5
0
C
N
NO
2


2CH
2
=CH - CHO + NH
3
- H
2
O
N
CH
3

f) Ngng t este | - xetoaxit vi andehit v NH
3
:


ROCO CH
2
CH
3
C=O
+
CH
3
CHO
NH
3
+
O=C
CH
2
COOR
CH
3
N
ROCO
CH
3 CH
3
COOR
H
CH
3


N
CH
3
CH
3 CH
3
ROCO COOR
2H
+HNO
3
+HOH
2C
2
H
5
OH, 2CO
2
N
CH
3
CH
3
CH
3


C. Tnh cht ha hc:
1. c tnh ca D vng: l c tnh ca hp cht thm.
- D vng bn vng vi nhit v cc tc nhn oxiha.
- D vng 5,6 cnh c h thng ni i lin hp d phn ng th v kh phn ng cng.
- D t cng tham gia vo h lin hp bng cch gp cp e t do vo h tnh cht ca d t
cng gim i hoc mt hn.
2. Tnh cht ca d t:
* D vng 6 cnh: pyridin ch c 1e ha tr ca nit tham gia vo vic hnh thnh h thng e
kiu benzoit(tnh cht thm gy ra bi s lin hp gia 5e ca 5 cacbon vi 1e ca nit lai ha
sp
2
to thnh h lin hp e t chung cho vng). Cp e t do ca nit vn cn nn pyridin vn
cn nguyn tnh baz.
* D vng 5 cnh c mt d t (nh pyrol) c cp e t do tham gia vo h thng thm nn tnh
ba z ca nit b gim hn v khng cn r rt na. Thiofen thc t khng c tnh baz, hon
ton khng to mui. Ngc li pyrol c tnh axit yu(pK
a
~ 16,5) to mui vi kim loi kim.





- D vng 5 cnh c 2 d t (nh imidazol) 2 nguyn t N tham
gia vo h thng theo 2 cch khc nhau, trong mt d t vn
cn nguyn cp e t do nn imidazol vn cn tnh baz.

3. Tnh cht ca nhn thm:
a) Phn ng th:
* D vng 5 cnh phn ng th electrofin C
2
(C

) v cacbon ny in tch m ln hn v
nng lng ca trng thi chuyn tip thp hn so vi v tr |. Phn ng d hn benzen v
khng i hi phi c xc tc mnh.
V d:
N
Br
2
,300
0
C
N N
Br
V
Br Br

O
N
S
+H
2
+H
2
+H
2
Ni,t
0
O
TetrahidroFuran
+H
2
H
Ni,t
0
N
Pyrolidin
H
Ni,t
0
Ni,t
0
S
Tiolan
N N
Piperidin
H

N
N
N
+
H
X
Y
X
+
Y
H
B-ly proton
Z-ly hidrua
N
N
X
Y
+BH
+
+ZH
S
E
S
N




* D vng 6 cnh phn ng th electrofin C
3
(C

) trong nhng iu kin cao hn khi th vo

benzen, v khi c axit cho proton d vng chuyn thnh cation lm b ng ha vng thm.

V d:



- Ngc li, phn ng th nucleofin li xy ra v tr C
2
(C
o
) v C
4
(C

) do nguyn t N ht e t
ca vng thm lm mt e ca ton vng thm b gim i v gim nhiu hn v tr o v .
Tng qut:








b) Phn ng cng:
* Cc d vng khng no u d phn ng hidro ha c xc tc to ra cc d vng no





























BI 2: MT S BI LUYN TP V HP CHT D VNG
A. Danh php v cu to :
Cu1. Gi tn cc hp cht sau, s dng ch s v tr bng s m v bng ch ci Hi-Lp.
(a)
C
CH
S
HC
HC
CH
3
(b)
C
CH
O
C
HC
CH
3
H
3
C

(c)
CH
C
O
C
HC
H
3
C
CH
3
(d)
C
CH
N
C
HC
Br COOH
C
2
H
5

GII: (a) 2-metylthiophen (2-metylthiol) hoc o-metylthiophen, (b) 2,5-dimetylfuran (2,5-
dimetyloxol) hoc o,o'-dimetylfuran, (c) 2,4-dimetylfuran (2,4-dimetyloxol) hoc o,|'-
dimetylfuran, (d) axit 1-etyl-5-brom-2-pirolcacboxilic (axit N-etyl-5-bromazol-2-cacboxilic)
hoc axit N-etyl-o-brom-o'-pirolcacboxilic.
Cu2. Vit cng thc cu to cho cc hp cht c tn gi :
(a) axit 3-furansunfonic ; (b) 2-benzoylthiophen ; (c) o,|'-diclopirol.
GII:
(a) (b) (c)



Cu 3. Vit cng thc cu to cc hp cht:
a) 2,5-dimetyl furan b) o-brom thiophen
c) o,o'-dimetylpirol d) 2-amino piridin
e) 2-metyl-5-vynyl piridin f) |-piridin sunfoaxit
g) axit 4-indol cacboxylic h) 2-metyl Quinolin
GII:
a) b) c) d)



e) f) g) h)



Cu 4. Gi tn cc hp cht sau:
C
CH
S
HC
HC
C
O
Ph CH
C
O
HC
HC SO
3
H
C
CH
N
HC
C
Cl
H
Cl
O
H
3
C CH
3
S
Br CH
3
H
N
H
3
C
N
NH
2
N
CH
2
=CH
CH
3 N
SO
3
H
N
CH
3
COOH
N
H
a)
O
CH
3
b)
S
C CH
3
O
c)
N
H
COOH
d)
N
OH

e)
N
H
CH
2
-COOH
f)
N
NO
2

GII: (a) 2-metyl furan (b) 2-axetyl thiofen (c) axit 2-pirol cacboxylic
(d) 4-hidroxy piridin (e) axit 2-indol axetic (f) 3-nitro quinolin.
Cu 5: Gi tn cc cht di y :
(a)
N
N
, (b)
S
N
, (c)
N
N
, (d)
O
N
, (e)
N
H
N

(a) 1,3-diazin (pirimidin), (b) 1,3-thiazol, (c) 1,4-diazin (pirazin), (d) 1,2-oxazon, (e)
imidazol
Cu 5. Vit cng thc cu to v gi tn cc ng phn ca metylpiridin.
GII:
C ba ng phn :
N CH
3
2-hoc o-metylpiridin
(opicolin)
1
2 (o)
3 (|)
4 ()
5
6

N
3-hoc |-metylpiridin
(|picolin)
CH
3

N
4-hoc -metylpiridin
(picolin)
CH
3

Cu 6. Vit cng thc cu to v gi tn cc ng phn ca thiofen c cng thc C
6
H
8
S.
GII: C 6 ng phn :

S
C
2
H
5
2-etyl Thiofen

S
3-etyl Thiofen
C
2
H
5

S
2,3-dimetyl Thiofen
CH
3
CH
3

S
2,4-dimetyl Thiofen
CH
3
H
3
C


S
2,5-dimetyl Thiofen
CH
3
H
3
C

S
3,4-dimetyl Thiofen
H
3
C
CH
3

Cu 7. Gii thch cu to thm ca furan, pirol v thiophen, bit cc phn t ny c cu to
phng vi gc lin kt 120
o
.
GII:
Xem hnh 20-1. Bn nguyn t C v d t Z s dng cc ohital lai ha sp
2
hnh thnh
cc lin kt o. Nu Z l O hoc S th mi nguyn t ny s cn mt obitan lai ha sp
2
cha hai
electron. Mi nguyn t C cn mt obitan p thun khit cha electron c thn v d t Z c
mt obitan p thun khit cha cp electron. Nm obitan p ny song song vi nhau v xen ph
c hai pha to lin hp t vi 6 electron. Cc hp cht ny c tnh thm do ph hp vi qui
tc Hckel 4n+2.
Cu 8. Ti sao momen lung cc ca furan bng 0,7D (phn cc v pha vng) cn ca tetra
hidrofuran li bng 1,7D (phn cc v pha O).
GII:
Trong tetrahidrofuran, do nguyn t O c m in ln hn lm cho lin kt C-O phn cc
v pha O. Trong furan, do cp electron t do ca O khng nh x m to lin hp vi vng
lam tng mt in tch m trong vng, phn t phn cc v pha vng. Xem hnh 20-1
( Hnh 20-1)




Cu 9.
(a) Gii thch tnh thm ca piridin, bit piridin c cu to phng vi gc lin kt bng 120
o
.
(b) Piridin c tnh baz khng ? Ti sao ?
(c) Gii thch ti sao piperidin (azaxyclohexan) li c tnh baz mnh hn so vi piridin.
(d) Vit phng trnh phn ng gia piridin v HCl.
GII:
(a) Cu to thm ca piridin (azabenzen) tng t cu to benzen, ba lin kt i ng
gp su electron p to ra h lin hp t ph hp vi qui tc Hckel 4n+2.
(b) C. Khc vi pirol, nguyn t N trong piridin tham gia h lin hp t bng electron p
thun thit v do vy n cn mt cp electron lai ha sp
2
t do c kh nng kt hp proton.
(c) Khi % ca s trong obitan lai ha cha cp electron t do t hn th tnh baz s mnh hn.
N
Piperidin
H
Lai ha sp
3
(% s nh)

N
Piperidin
Lai ha sp
2
(% s l n)

(d) C
5
H
5
N +HCl C
5
H
5
NH
+
Cl
-
Cu 10. a) Pirazol l ng phn izo ca Imidazol cng cng thc phn t C
3
H
4
N
2
. Tng t
Thiazol v izothiazol l ng phn cng cng thc C
3
H
3
NS cn Oxazol v izoxazol l ng
phn cng cng thc C
3
H
3
NO. Hy vit cu to cc cht trn.
b) Pirazol l cht kt tinh, 400 gam dung dch nc cha pirazol nng 6,8% ng c
271K. Bit hng s nghim lnh ca pirazol bng 3,73. Hy xc nh cu to ca pi razol
trong dung dch.
GII: (a)
C C
C
Z
C H
H H
H
CH
2
CH
2
O
H
2
C
H
2
C
O

N
N N
N
H
H

N
N
H
Pirazol

N
N
H
Imidazol

N
S
Thiazol

S
N
IzoThiazol

N
O
Oxazol

O
N
Izoxazol

(b) Trong 400 gam dung dch c 400 . 0,68 = 27,2 gam pirazol v 372,8 gam nc.
Theo nh lut Raoun: t = k. m (trong m l nng molan) m =
2
3,73
=0,536
Phn t khi ca pirazol trong iu kin ny =
27,2 . 1000
0,536 . 372,8
=136
ln gp 2 ln phn t khi ca pirazol = 68 (tnh theo
cng thc C
3
H
4
N
2
) chng t trong dung dch
pirazol tn ti dng dime do c lin kt hidro lin
phn t.


Cu 11. Vit nhng dng lin kt hidro gia cc phn t :
a) Imidazol Imidazol
b) Imidazol Indol
GII: (a)

N N N N N N H
H
H

(b)

N N H H N

Cu 12. Ba pirimidin i y l tham gia cu thnh axit nucleic :
N
N
NH
2
OH
Cytosin

N
N
OH
OH
Uracin

N
N
OH
OH
Thymin
H
3
C

Vit cu trc tautome ca cc pirimidin ny.
GII:

N
H
N
NH
2
O
Cytosin

N
H
NH
O
O
Uracin

N
H
NH
O
O
Thymin
H
3
C

B. Vit cc phng trnh phn ng:
Cu 13. Vit phng trnh biu din cu to cc sn phm theo s sau:

N
a) A
B
C
D
(CH
3
CO)
2
O, 5
0
C
Pyridin, SO
3
, 90
0
C
Br
2
(CH
3
CO)
2
O, 200
0
C
CH
3
CONO
2

b)
N
G
H
O
2
N-C
6
H
4
-N
2
+
KOH
CH
3
MgBr
E
F
HCN+HCl
H
2
O



c)
O
I
K
L
M
(CH
3
CO)
2
O, 10
0
C
Pyridin, SO
3
, 90
0
C
Dioxan, Br
2
(CH
3
CO)
2
O, BF
3
CH
3
CONO
2

d)
S
O
P
Q
(CH
3
CO)
2
O, 0
0
C
H
2
SO
4
Br
2
CH
3
COCl
CH
3
CONO
2
AlCl
3
N



e) X
1
X
2
X
3
Br
2
,300
0
C
HNO
3
, H
2
SO
4
N
300
0
C
H
2
SO
4
, 350
0
C
CH
3
COCl, AlCl
3
X
4

f)
Y
3
Y
4
CH
3
I
HBr
SO
3
Y
1
Y
2
BF
3
N





N
g)
NaOH
NaNH
2
300
0
C
170
0
C
A
1
B
1
A
2
B
2



N
h)
H
2
SO
4
NaNH
2
HNO
3
C
1
D
1
+ C
2



i)
H
2
SO
4
SO
3
HNO
3
E
1
E
2
N
N
H
H
+

N
N
H
H
2
SO
4
HNO
3
F
1
F
3
Br
2
F
2
k)


GII:

N
a)
(CH
3
CO)
2
O, 5
0
C
Pyridin, SO
3
, 90
0
C
Br
2
(CH
3
CO)
2
O, 200
0
C
CH
3
CONO
2
H
N
SO
3
H
H
N
COCH
3
H
N
Br
H
Br
Br
Br
N
NO
2
H

+
b)
N
O
2
N-C
6
H
4
-N
2
+
KOH
CH
3
MgBr
HCN+HCl
H
2
O
H
N
K
-
N
Mg
+
Br
-
N
CHO
H
N
N=N-C
6
H
4
NO
2
H



c)
O
(CH
3
CO)
2
O, 10
0
C
Pyridin, SO
3
Dioxan, Br
2
(CH
3
CO)
2
O
CH
3
CONO
2
BF
3
O
NO
2
O
SO
3
H
O
Br
O
COCH
3

d)
S
H
2
SO
4
A lCl
3
(CH
3
CO)
2
O, 0
0
C
Br
2
(CH
3
CO)
2
O
CH
3
CONO
2
S
NO
2
O
SO
3
H
O
Br
O
COCH
3


e)
Br
2
,300
0
C
HNO
3
, H
2
SO
4
N
300
0
C
H
2
SO
4
, 350
0
C
CH
3
COCl, AlCl
3
N
NO
2
Br
N
N
SO
3
H
khng phn ng

f)
CH
3
I
HBr
SO
3
+
BF
3
N
N
Br
-
H
N
SO
3
+
N
BF
3
-
+
N
CH
3
I
-



N
g)
NaOH
NaNH
2
300
0
C
170
0
C
N
OH
N
NH
2
N
H
O
H
2
N
2-Piridon
N
NH
2
DiaminoPyridin


N
h)
H
2
SO
4
NaNH
2
HNO
3
+
N
NO
2
N
NO
2
N
NH
2



i)
H
2
SO
4
SO
3
HNO
3
N
N
H
H
+
N
N
H
O
2
N
N
N
H
HO
3
S

N
N
H
H
2
SO
4
HNO
3
Br
2
k)
N
N
H
Br
N
N
H
N
N
H
O
2
N
HO
3
S


Cu 14. Hy cho bit sn phm phn ng ca piridin vi :
a) HCl ; b) B(CH
3
)
3
; c) CH
3
I ; d) tert butylclorua.
GII:
a) Piridin l baz Bronstet, cho mui piridini clorua C
5
H
5
NH
+
Cl

.
b) Piridin l tc nhn nucleofin, phn ng vi B(CH
3
)
3
l axit lewis cho C
5
H
5
N B(CH
3
)
3
.
c) Phn ng th S
N
2 to N metyl piridini iodua C5H5N
+
CH
3
I

.
d) Do piridin l baz nn halogenua bc ba d phn ng tch E
2
thay cho phn ng S
N
2. Sn
phm l :




Cu 15. Pirol c kh bng Zn v CH
3
COOH thnh Pirolin C
4
H
7
N.
a) Hy vit 2 cng thc c th ca Pirolin.
b) Chn ng phn ng tha mn: khi ozon phn s c cht A (C
4
H
7
O
4
N), cht A c
tng hp t 2 mol axit monocloaxetic v amoniac.
GII:
N
H
Cl
+
+
CH
2
C
CH
3
CH
3
N
2,5-dihidropirol (A)
N
2,3-dihidropirol (B)
a) Hai cht c th l:




b) ng phn A cho HOOC CH
2
NH CH
2
COOH. (C)
ng phn B cho HOOC NH CH
2
CH
2
COOH. (D)
ch c (C) l c th tng hp c t 2 mol Cl CH
2
COOH v 1mol NH
3
nn Pirolin l
(A)


Cu 16: Vit s phn ng th electrofin vo o,| - dimetylpiridin. ng phn no c to
thnh l ch yu?
GII: Th v tr (5) l ch yu.
Cu 17:
a) Hy cho bit cc bc phn ng trong tng hp Quinolin theo Skarup phng trnh phn
ng sau:

C
6
H
5
NH
2
+C
6
H
5
NO
2
+CH
2
CH CH
2
OH
OH OH
H
2
SO
4
FeSO
4
,t
0
Quinolin
+C
6
H
5
NH
2
+H
2
O

b) Ti sao khng dng CH
2
=CH CHO thay cho Glyxerin ?
GII:
a) Bc 1: Dehidrat ha:

CH
2
CH
2
CH
OH
OH OH
Glyxerin
H
2
SO
4
CH
2
CH CHO
+2 H
2
O
Acrolein

Bc 2: Cng hp Michael:

NH
2
+ CH
2
=CH-CHO
NH -CH
2
-CH
2
-CHO
(C)

Bc 3: S tn cng electrofin:

(C)
N
H
+
H
OH
H
+
H
+
N
H
H
OH
H
+
H
2
O
N
1,2-dihidroquinolin(D)

Bc 4: Oxiha vi C
6
H
5
NO
2
.
(D) + C
6
H
5
NO
2
Quinolin + C
6
H
5
NH
2
.
C
6
H
5
NH
2
c hnh thnh trong giai on oxiha c a tr li vo bc 2. V vy cht b
tiu tn l C
6
H
5
NO
2
v ch cn 1 lng nh anilin bt u cho phn ng. Nu dng cht
oxiha khc nitrobenzen th mi cn 1 ng lng anilin. Xc tc FeSO
4
dng iu chnh
s oxiha mnh lit.
b) Khng dng acrolein, v acrolein s b oxiha thnh axit.
Cu 18: Hy cho bit cng thc cu trc ca cc cht t A C trong dy chuyn ho sau :
o-NH
2
-C
6
H
4
-COOH +Cl-CH
2
-COOH
HCl
A
0
2
( H O)
t

B
2
CO
C C
8
H
7
ON (D)
GII:

NH-CH
2
-COOH
COOH
(A)
N
CH -COOH
C
O
H
(B)



N
C
OH
H
N
C
O
H
(C)
(D)
( C
8
H
7
ON )


Cu 19: Vit cng thc cu trc v gi tn cc hp cht t A n D trong cc phn ng sau:
a) Ure +O=CH CH
2
COO-C
2
H
5

2 5
C H O

A
b) S =C(NH
2
)
2
+CH
3
I
HI
B
3 2 5
+O=CH-CH(CH )-COO-C H
C
dd HBr
D (C
5
H
6
O
2
N
2
)
GII: a)

O =C
NH
2
NH
2
+
O =C
CH
2
O =C
O -C
2
H
5
H
N
N
CH
C
H
O
O
H
N
N
CH
OH
HO
A ( Uraxin )

b)

S =C
NH
2
NH
2
+ CH
3
I
NH
NH
2
CH
3
S C
( B )
N
N
CH
3
S
H
CH
3
O
( C )
N
N
CH
3
HO OH
( D ) Thimin


Cu 20: a) Hy ngh cu trc ca cc cht t A n G trong dy tng hp Papaverin (G):
3,4 dimetoxi cloruabenzyl
KCN
A
2
0
H
Ni, t
B
3
0
H O
t
+
C
5
PCl
D
D
B +
E
2 5
P O
F
0
Pd, t
G (C
20
H
21
O
4
N)
b) Trong Papaverin c cha d vng no?
GII: a)
CH
2
Cl
CH
2
CN
CH
2
CH
2
NH
2
CH
2
COOH
CH
2
COCl
OCH
3
OCH
3
KCN
OCH
3
OCH
3
H
2
d
2 mol
H
3
O
+
OCH
3
OCH
3
OCH
3
OCH
3
PCl
5
OCH
3
OCH
3
(A)
(B)
(C)
(D)


CH
3
O
CH
3
O
NH
O =C
CH
2
OCH
3
OCH
3
(E)


CH
3
O
CH
3
O
CH
2
OCH
3
OCH
3
N
CH
3
O
CH
3
O
CH
2
OCH
3
OCH
3
N
(F) (G)

b) Trong Papaverin (G) cha d vng Isoquinolin
Cu 21: (a) Da trn tnh bn tng i ca trng thi trung gian, hy gii thch ti sao tc
nhn electrophin (E
+
) u tin tn cng vo v tr o ca cc d vng furan, pirol, thiophen hn so
vi v tr |?
(b) Ti sao cc d vng ny c i lc vi tc nhn electrophin cao hn so vi vng benzen?
GII:
(a) Qu trnh tn cng vo v tr o to trng thi trung gian v chuyn tip R
+
l mt cn bng
gia ba cu trc cng hng c nng lng thp, trong khi trng thi trung gian ca qu
trnh tn cng vo v tr | c nng lng cao hn do ch c hai cu to cng hng. Trong s
di y, dng I v II l cc cacbocation alylic bn vng cn V khng c dng alylic.
(b) Dng cng hng III gii thch ti sao cc d vng li c i lc vi tc nhn electrophin cao
hn so vi benzen, dng ny d t Z tch in dng v cc nguyn t trong vng u c lp
v electron t bt t. Cc d vng ny hot ng nh phenol PhOH v anilin PhNH
2
.


Z
Z Z Z Z
Z Z Z
H
E
H
E
H
E
E
H
E
H
E
E
I II III IV V
sn phm chnh
sn phm ph
tn cng o tn cng |

Cu 22: Cho bit loi phn ng, cng thc v tn gi ca sn phm to thnh t phn ng gia :
(a) furfuran v dung dch KOH;
(b) furan vi (i) CH
3
CO-ONO
2
(axetyl nitrat) trong piridin, (ii) (CH
3
CO)
2
O v BF
3
sau
l H
2
O;
(c) pirol v (i) SO
3
trong piridin, (ii) CHCl
3
v KOH, (iii) PhN
2
+
Cl
-
, (iv) Br
2
v C
2
H
5
OH;
(d) thiophen v (i) H
2
SO
4
, (ii) (CH
3
CO)
2
O v CH
3
CO-ONO
2
, (iii) Br
2
trong benzen.
O
CHO
Fufuran (o-Furancacboxandehit)

GII:
(a) Phn ng Canizaro :
O
COOK
kali furoat
v
O
CH
2
OH
ancol fufuryl

(b) (i) Nitro ha :
O
NO
2
2-nitrofuran

(ii) Axetyl ha :
O
COCH
3
2-axetylfuran

(c) (i) Sulfo ha :
N
H
SO
3
H
axit 2-pirolsunfonic

(ii) Fomyl ha Reimer-Tiemann :
N
H
CHO
2-pirolcaboxandehit (2-fomylpirol)

(iii) Kt hp :
N
H
N
2-phenylazopirol
NPh

(iv) Brom ha : 2,3,4,5-tetrabrompirol
(d) (i) Sulfo ha :
S
SO
3
H
axit thiophen-2-sunfonic

(ii) Nitro ha :
S
NO
2
2-nitrothiophen

(iii) Brom ha : 2,5-dibomthiophen (Thiophen hot ng yu hn pirol v furan)
Cu 23: Vit cng thc ca sn phm to thnh khi mononitro ha cc hp cht sau v gii
thch s hnh thnh ca chng :
(a) 3-nitropirol ; (b) 3-metoxithiophen ; (c) 2-axetylthiophen ;
(d) 5-metyl-2-metoxithiophen ; (e) axit 5-metylfuran-2-cacboxilic.
GII:
(a) Nitro ha ti C
5
(i) hnh thnh 2,4-dinitropirol (sau khi nitro ha C
5
thnh C
2
v C
3
thnh
C
4
). Nitro ha ti C
2
(ii) to ra mt trng thi trung gian mang in tch dng trn C
3
, ni c
nhm -NO
2
ht electron.
N
H (i)
NO
2
O
2
N
H

N
H (ii)
NO
2
H
NO
2

(b)
S
NO
2
2-nitro-3-metoxithiophen
(o v ortho i v i OCH
3
)
OCH
3
(c)
S
OCH
3
2-axetyl-5-nitrothiophen
(tn cng vtro )
O
2
N
(d)
S
OCH
3
2-metoxi-3-nitro-5-metylthiophen
(ortho i v i OCH
3
, ho t ha
nhn m nh hn CH
3
)
NO
2
H
3
C

(e)
+
NO
2
tn cng vo v tr C
2
, sau tch CO
2
v H
+
:

O
NO
2
2-metyl-5-nitrofuran
H
3
C
O
NO
2
H
3
C
O
COOH H
3
C
NO
2
C OH
O
-CO
2
-H
+

Cu 24: Gi tn sn phm to thnh khi hidro ha c xc tc (a) furan, (b) pirol.
GII:
a)
O tetrahidrofuran, oxaxyclopentan
, (b)
N
H pirolidin, azaxyclopentan

Cu 25 : Cht no c to thnh trong cc phn ng sau:
a) 2,5 dimetylfuran + anhidrit axetic
3
BF

b) Thiophen + anhidrit axetic
4
SnCl

c) o - metylpirol
0
3
CH MgI , t
A
3
2
1. CH CHO
2. H O

B
GII: a) 2,5 dimetyl 3 axetyl Furan b) o - axetyl Thiophen
c) A : o - (o metyl Pirolyl)magie iodua ; B : metyl - o - (o metyl Pirolyl) cacbinol
Cu26 : Vit phng trnh phn ng xy ra khi cho cc cht di y i qua nhm oxit nung
nng 450
0
C (gi tn h thng cc sn phm to thnh):
a) o - metylfuran vi metylamin.
b) Thiophen vi metylamin.
c) o - metylpirol vi hidrosunfua.
GII: a) N metyl 2 metyl pirol ; b) N etyl pirol ; c) 2 metyl thiofen
Cu 27: Vit cc phng trnh phn ng sau:
a) Pirol trong mi trng axit.
b) Piridin trong mi trng axit. Gii thch.
GII:
a) Xy ra s proton ha v tr o :
N
+H
+
N
H
H
+
H
H

Sau axit lin hp to thnh tn cng phn t pirol v xy ra s polime ha.

N
H
+
N - H
H H
H
+
H
N
N
H
H
+
v.v....

b) To mui.

Cu 28: Vit sn phm ca phn ng Diels-Alder gia furan v anhidrit maleic
GII:
Trong s cc d vng nm cnh th furan c tnh thm yu nht v do vy n c th phn ng
nh mt dien :
O
O
O
O
O
O
O
O

Cu 29: Vit phn ng xy ra khi cho pirol phn ng vi:
(a) I
2
trong dung dch KI; (b) CH
3
CN +HCl, sau thy phn; (c) CH
3
MgI.
GII: (a) 2,3,4,5-tetraiotpirol (b) o-axetylpirol
(c)
CH
CH
N
H
HC
HC
CH
3
MgI
N
CH
4
MgI

Cu 30: Cho bit cc giai on trung gian ca qu trnh m vng khi tin hnh phn ng :
(a) 2,5-dietylfuran vi axit (H
3
O
+
).
(b) pirol vi hidroxylamin Cl
-
H
3
N
+
OH.
GII:
(a)
HC CH
CC
2
H
5
C
2
H
5
C
HC CH
C C
OH OH
CH
2
H
3
O
+
diendiol 3,6-octandion
C
2
H
5
C
2
H
5
o
C
2
H
5
C
CH
2
CC
2
H
5
O
O

(b)
HC CH
CH HC
HC CH
CH CH
OH OH
butandiandioxim
N
H
2
O
H
2
C CH
2
CH CH
O O
H
2
C CH
2
CH CH
NOH HON

Cu 31: Hy gii thch ti sao piridin:
(a) u tin th electrophin ti v tr | ; (b) km hot ng hn benzen ?
GII:
a) Khi tc nhn electrophin tn cng vo v tr o hoc ca piridin th s to cu trc cng
hng (I, IV) trong nguyn t N ch c su electron lp ngoi cng v mang mt in tch
dng. Nguyn t N li c m in ln nn trng thi trung gian ny khng bn.
Khi tc nhn electrophin tn cng vo v tr |, in tch dng ca trng thi trung gian s ch
phn b trn cc nguyn t C. Cu trc su electron ngoi cng v mang in tch dng ca
C li kh bn. Do vy, phn ng th electrophin ca piridin u tin xy ra ti v tr | l v tr
c trng thi trung gian bn vng hn.

N N N
Tn cng vtro
H
E
H
E
H
E
I
II III

N N N
Tn cng vtr
H E H E
H E
IV V VI

N N N
Tn cng vtr|
H
E
H
E
H
E

(b) Piridin km hot ng hn benzen l v nguyn t N trong piridin c m in ln (cng
do nguyn t N ny phn ng vi tc nhn electrophin to cation piridinium) ht electron (-I)
lm mt in tch m trong vng v lm mt n nh trng thi trung gian R
+
.
Cu 32: Xc nh cng thc cu to v gi tn sn phm to thnh khi cho piridin phn ng
vi: (a) Br
2
300
o
C; (b) KNO
3
, H
2
SO
4
300
o
C, sau thm KOH;
(c) H
2
SO
4
350
o
C; (d) CH
3
COCl/AlCl
3
.
GII:
(a)
N
Br
N
Br Br
3-brom v 3,5-dibrompiridin
(b)
N
NO
2
3-nitropiridin

(c)
N
H
SO
3
-
axit 3-piridinsunfonic
(d) Khng phn ng.
Cu 33: D on sn phm to thnh khi oxi ha o-phenylpiridin, bit phn ng oxi ha l
phn ng electrophin.
GII: Do vng piridin km hot ng vi tc nhn electrophin, nn phn ng oxi ha s din
ra vng benzen to sn phm l axit o-piconilic (o-NC
5
H
4
COOH)
Cu 34: D on v gii thch sn phm thu c, cng nh iu kin phn ng khi nitro ha
2-aminopiridin.
GII: Sn phm l 2-amino-5-nitropiridin, do v tr u tin th ca vng piridin (v tr |) cng
ng thi l v tr u tin th i vi nhm -NH
2
(v tr para). iu kin th nh nhng hn so
vi piridin do -NH
2
l nhm hot ha nhn thm.
Cu 35: Gii thch ti sao:
(a) piridin v NaNH
2
to sn phm o-aminopiridin,
(b) 4-clopiridin v NaOMe to sn phm 4-metoxipirridin,
(c) 3-clopiridin v NaOMe khng phn ng ?
GII:
Nguyn t N ht electron lm cho tc nhn nucleophin tn cng thun li vo cc v tr o v
. Trng thi trung gian c bn ha nh s cng hng gia cc lin kt t v nguyn t N
tch in m, cc cacbanion trung gian ny ng thi cng d dng tr li cu trc vng thm
bn vng bng cch tch ion H
-
(nh phn ng a) hoc Cl
-
(nh phn ng b).
(a)
N
Na
+
NH
2
-
un nng
N
NH
2
H
Na
+ N
NH
2
+Na
+
H
-

(b)
N
MeO
-
N N
+Cl
-
Cl
MeO
Cl
OMe

(c) Qu trnh tn cng vo v tr | khng to c trng thi trung gian vi nguyn t N
tch in m.
Cu 36: Xc nh sn phm to thnh khi cho piridin phn ng vi:
(a) BMe
3
, (b) H
2
SO
4
, (c) EtI, (d) t-BuBr, (e) axit peroxibenzoic PhCO-
OOH.
GII: Piridin thuc loi amin bc 3.
(a) C
5
H
5
N
+
-
-
BMe
3
;
(b) (C
5
H
5
N)
2
+
SO
4
2-
(piridinium sunfat);
(c) (C
5
H
5
N
+
-Et)I
-
(N-etylpiridium iodua);
(d) C
5
H
5
N
+
Br
-
+Me
2
C=CHMe (halogen bc 3 d tch hn th S
N
2);
(e) C
5
H
5
N
+
-O
-
(piridin-N-oxit)
Cu 37: Hp cht no to thnh khi cho o-metyl piridin phn ng vi cc cht sau:
a) PhenylLiti ; b) Benzandehit ; c) Natriamidua, t
0
.
GII: a) C
5
H
4
NCH
2
Li ; b) C
5
H
4
N CH =CH C
6
H
5
.
c) 2 metyl 3 aminopiridin v 2 metyl 5 aminopiridin.
Cu 38: Cho bit sn phm to thnh khi -picolin phn ng vi C
6
H
5
Li v sau s l tip
bng: (a) 1. CO
2
, 2. H
3
O
+
; (b) 1. C
6
H
5
CHO, 2. H
3
O
+
.
GII:

N
N N
C
6
H
5
-
Li
+
(a)
CH
3
CH
2
CH
2
C
6
H
6
+
N
CH
2
COOH
N
CH=CHC
6
H
5
(b)
axit 4-piridylaxetic
4-stibazol

Cu 39: Axit cacboxilic no hnh thnh khi oxi ha quinolin (1-azanaphtalen) v 2-
aminoquinolin
GII: - Vng piridin bn hn vng benzen nn sn phm oxi ha phi l axit quinolinic :
- Khi c nhm amino v tr s 2 ca vng piridin th bn ca vng piridin gim i v b
oxiha nn sn phm oxiha l axit phtalic.
Quinolin
N
KMnO
4
N
Axit quinolinic
COOH
COOH
v
N
NH
2
KMnO
4
COOH
COOH
2-aminoQuinolin Axit Phtalic


Cu 40: Vit phng trnh phn ng thy phn vitamin PP (amit ca axit nicotinic). Cc cht
thu c trong mi trng axit, trung tnh v kim c cu trc nh th no?
GII: Cu to ca vitamin PP v phng trnh phn ng thy phn:

N
CONH
2
Vitamin PP
+ H
2
O
N
COOH
+ NH
3

Sn phm trong mi trng axit:
N
COOH
+
H
trong mi trng kim:
N
COO

v trong mi trng trung tnh:
N
COO
H
+

Cu 41: Clo metylat piridin tc dng vi dung dch kim nc ri oxiha nh to ra cht rn A
c cng thc phn t C
6
H
7
NO. Cht A khng cha nhm hidroxyl. Hy cho bit cu trc ca
hp cht A v n c to thnh nh th no? Phn ng tng t c xy ra vi piridin khng?
GII:

N
CH
3
Cl
+
Clo metylat Piridin
OH
H
2
O
N
CH
3
(A) C
6
H
7
NO
+
N
CH
3
S
N
HO
OH [O]
N
CH
3
O
( X )
( Y )

Phn ng tng t khng xy ra vi piridin v mt e trn N thp

CH CH +2HCHO
2 2
Cu C
HOCH
2
C C CH
2
OH
3
NH , p



N
H
CH
HC CH
HC CH
N
t
0


N

CH
3
CH
2
CH
2
O
CH
3
C
C
CH
3
O
O
H
H
3
C
CH
3
N
H
3
C
CH
3
S
H
3
C
P
2
O
5
nung
nung
P
2
S
5
(NH
4
)
2
CO
3
100
0
C

Cu 42: Ngi ta iu ch quinolin bng phn ng Skraup t anilin, glyxerin v nitrobenzen.
ngh mt c ch lin quan n phn ng cng Michael ca anilin vo o,|-andehit cha
no, ng vng, sau dehidrat ha v oxi ha.
GII: Cc bc ca phn ng nh sau :
(1) CH
2
OH-CHOH-CH
2
OH
4 2
SO H
CH
2
=CH-CHO +2H
2
O
(2) Phn ng cng Michael :

N
CH
CH
2
HC
O
H
H
N
H
CH
2
CH
2
HC
O
H
+
N
H
CH
2
CH
2
HC
OH

(3) Khp vng do s tn cng ca C-cacbonyl electrophin vo v tr para ca nhn thm.
Ru bc hai di tc dng ca axit mnh s dehidrat ha to thnh 1,2-dihidroquinolin:
N
H
CH
2
CH
2
HC
OH
N
H
CH
2
CH
2
C
H OH
H
+
H
+
-H
2
O
N
H
CH
CH
2
H
C
PhNO
2
N

(4) PhNO
2
oxi ha 1,2-dihidroquinolin thnh hp cht thm quinolin. PhNO
2
b kh thnh
PhNH
2
quay tr li bc phn ng vi acrolein.

C. iu ch :
Cu 43: Vit phng trnh phn ng iu ch:
a) Hai cht Pyrol, Pyridin t axetylen, fomandehit, axit xianhydric v cc iu kin cn thit.
b) Ba cht 2,5-dimetyl furan; 2,5-dimetyl Pyrol; 2,5-dimetyl thiofen t axetonyl axeton
(hexadion 1,5) v cc tc nhn, iu kin cn thit.
GII:
a) iu ch Pyrol:


iu ch Pyridin:



b)












Cu 44: Hy iu ch cc hp cht sau y bng cch un nng hp cht dicacbonyl 1,4 vi
cc tc nhn v c thch hp:
a) 3,4 dimetylfuran.
b) 2,5 dimetylthiophen.
c) 2,3 dimetylpirol.
GII: a)

CH
3
CH
H C
CH CH
3
C
CH
3
O
P
2
O
5
O
H
CH
3
CH
H C
CH CH
3
C
OH OH
H
O
H
3
C

b)

CH
3
CH
2
C
CH
2
CH
3
C
CH
3
O
P
2
S
5
O
S
H
3
C
axetonylaxeton

c)

CH
3
CH
2
H C
CH CH
3
C
CH
3
O
(NH
4
)
2
CO
3
O
3-metyl-4oxopentanal
N
CH
3



Cu 45: T axit sucxinic hy iu ch pirol.
GII:

CH
2
CH
2
O
C
COOH
CH
2
C
Zn
O
P
2
S
5
,t
0
O
N
OH
COOH
H
2
O
CH
2
O
NH
3
H
2
O
C
N
C =O
H
HO
H
N
H
Kh

Cu 46: iu ch o, o, | , | tetrametylthiophen t etylaxetat v cc cht cn thit.
GII: 2CH
3
-COO-C
2
H
5

2 5
C H ONa
CH
3
-CO-CH
2
-COO-C
2
H
5

2 5 2
C H ONa/ I


CH
3
CH
CH CO CO CH
3
C
2
H
5
-O O-C
2
H
5
C
C
O O
2C
2
H
5
-ONa
2CH
3
I CH
3
CO CO CH
3 C
CH
3
C
CH
3
C
2
H
5
-O
C
O
O-C
2
H
5
C
O


CH
3
CH CH CH
3
C
O
H
3
C CH
3
1) OH
2) H
3
O+
C
O
CH
3
CH
3
P
2
S
5
S
CH
3
H
3
C

Cu 47: T Piridin hoc cc ng phn Picolin hy iu ch:
a) 2 n butylpiridin ; b) 2 n butylpiperidin ; c) 3 aminopiridin ; d) 2 - xianpiridin
e) 2 piridon ; f) 2 clopiridin ; g) 3 xianpiridin (bng 2 cch)
h) 2 PyCH
2
CH
2
NH
2
.
GII: a) b) C th ankyl ha bng s th nucleofin R

(hoc Ar

) ri hidro ha:

N
+CH
3
-CH
2
-CH
2
-CH
2
Li
LiH
N
C
4
H
9
H
2
/ Ni
N
C
4
H
9

c) Nitro ha ri kh hp cht nitro bng Sn /HCl v OH

hoc:

N
CH
3
N N N
KMnO
4
COOH
SOCl
2
COCl
NH
3
N
CONH
2
NaOBr
OH
NH
2

d) 2- aminopiridin khng diazo ha c theo cch thng thng v khng th chuyn thnh
hp cht xian. Nhm xiano c iu ch t amit l tt nht.

N
CH
3
N
COOH
N
COCl
N
CN
N
CONH
2
KMnO
4
SOCl
2
NH
3
P
2
O
5

e) v f) Hydroxyl ha trc tip piridin cho hiu sut thp v OH

khng phi l tc nhn

nucleofin mnh.

N
C
2
H
5
O
O-C
2
H
5
N
H
3
O+
N
O
H
N
Cl
PCl
3

g) 2 cch: iu ch 3-amin piridin v dn xut amit ca n theo cu (c)

N
NH
2
N
CN
N
CONH
2
P
2
O
5
1) HNO
2
,O
0C
2) CuCN

h)

N
Br
NaCH(COOC
2
H
5
)
2
N CH(COOC
2
H
5
)
2
N
1) OH , t
0
2) H
3
O
+
CH
2
-COOH
SOCl
2


N
COCl
N CH
2
CONH
2
N
CH
2
-CH
2
-NH
2
NH
3 LiAlH
4

Cu 48: T 2-metylpiridin v hp cht bo bt k hy iu ch:
a) 2 axetyl piridin (A) ; b) 2 vinyl piridin (B) ; c) 2 fomyl piridin (C)
d) 2 xiclopropyl piridin (D) ; e) 2 Py C(CH
3
) =CH CH
3
(E)
GII: a)

N
CH
3
KMnO
4
N
COOH
1) C
2
H
5
OH /H
2
SO
4
2)NaOH(trung hoa)
N
COOC
2
H
5



CH
3
COO-C
2
H
5
N
COCH
2
COO-C
2
H
5
1) OH ,t
0
2) H
3
O
+
N
COCH
3
C
2
H
5
ONa
(A)

b)

N
COCH
3
NaBH
4
N
CH
N
CH
OH
CH
3
P
2
O
5
CH
2
(B)

c) v d)

N
COCH
3
1 ) O
3
N
CH CH
2
(C)
2 ) Zn / CH
3
COOH
N
CH
CH
2
CH
2
(D)
CH
2
N
2
Tia t ngoi

e) Dng phn ng Vittic:

( cis- v trans- )
N
C(CH
3
)=CH-CH
3
N
COCH
3
(E)
+
C
6
H
5
C
6
H
5
C
6
H
5
CH-CH
3
P



Cu 49: T Fufural hy iu ch:
a) Etyl 5 brom 2 furoat . b) 1,2,5 - tribrompentan
c) Tetrahidropirrol d) N metyl pirol
GII: a)

O
CHO
Ag(NH
3
)
2
+
O
COOH
C
2
H
5
OH
H
+
O O
C O
OC
2
H
5
Br
2
Br C O
OC
2
H
5

b)

O
CHO CH
2
OH
HBr
H
2
Ni,t
0
O
CH
2
Br
Br
Br

c) v d)
O
CHO
Ag(NH
3
)
2
+
O
COOH
Al
2
O
3
,450
0
C
t
0
CO
2
O N
N
NH
3
CH
3
I
CH
3

Cu 50: T Quinolin v cc cht bo cn thit hy iu ch:
a) 8 hidroxiquinolin bng 2 phng php.
b) 2 aminoquinolin
GII: a)

N
H
2
SO
4
HNO
3
N
NO
2
+
H
Sn / HCl
N
NH
2
+
H
N
OH
1) NaNO
2
,0
0
C
2) H
2
O ,t
0
C

hoc:

N
H
2
SO
4
t
0
C
N
SO
3
H
N
OH
1) NaOH
2) H
3
O
+

Ch : Trong c 2 trng hp giai on u u cn loi b ng phn v tr (5)
b) Cng ging nh pyridin, quinolin tip nhn phn ng th nucleofin v tr (2) v (4)

N
1) NaNH
2
, t
0
2) H
2
O
N
NH
2

Cu 51: Hy tng hp 2 metoxifuran t metyl o - furoat v cc tc nhn cn thit.
GII: Furan khng d phn ng th nucleofin. Nhng halogen c th th c nu nhm th
lm bn trng thi trung gian. Nhm hot ha c chn l COOR(H) v d b tch ra.
O
O
C
Br
O
CH
3
O
O
CH
3
O
O
OCH
3
C O
OCH
3
C O
OCH
3
Br
2
CH
3
ONa
CH
3
OH
1) OH
-
2) Cu, quinolin,t
0

Cu 52: Vit y cc phng trnh phn ng theo s sau:

N
CH
3
[O]
A
SOCl
2
B
NH
3
C
D
E
C
2
H
5
OH( H
+
)
NH
3
C
6
H
6
( AlCl
3
)

GII: A l axit isonicotinic B l Cloruaaxit ca A C l amit ca A D l este

N
COOH

N
COCl

N
CONH
2

N
CO-OC
2
H
5

E l 4 Benzoyl pyridin
N
C
O

D. So snh kh nng phn ng v tnh ba z:
Cu 53. a) Nu c ch phn ng th electrofin vo d vng 5 cnh v d vng 6 cnh
b) So snh kh nng phn ng th electrofin gia d vng 5 cnh v d vng 6 cnh vi benzen.
GII:
a) C ch phn ng: Phn ng to thnh trng thi chuyn tip c nng lng thp (v tr C
2

trong d vng 5 cnh v v tr C
3
trong d vng 6 cnh) ti cc v tr c mt e ln hn.
N

(Quinolin)
b)

Z Z
( Z l d t N, O, S)

V c tnh baz nn pyridin kh tham gia phn ng th electrofin , phn ng din ra trong mi
trng axit nn giai on u s to ra ion N
+
lm cho phn ng chm n 10
12
10
18
ln so
vi benzen.
Cu 54. So snh tnh baz ca cc cp cht sau y v gii thch:
a) Metyl amin, Pyridin v Anilin
b) Quinolin v Pyridin
c)

N
N
N N
H
H H

d)


N
N
N



e)

N N
N
H H
H

g)

N
N
N
N N
O
NH

GII: a)

CH
3
NH
2
N
NH
2
Lai ha C
sp
3
Lai ha C
sp
2
(- C)

b)

N N
Hiu ng - C

c) Gii thch bng m in ca Csp
2
>Csp
3

N
N
N
N
H
H H

d)

N N
N
( Ch c - I ca vng,khng c
s lin hp gia N v h thm )

e)

N N
N
H H
H
(-I )
(-I mnh hn ; - C)

g)

N
N
N
N N
O
NH
N
l nguyn t N
c tnh baz


Cu 55. Cho 4 hp cht:

NH
2
(A)
NH
2
N
H
H
N
(B)
(C) (D)

Hy sp xp cng thc cc cht theo trnh t tng dn tnh baz, gii thch.
GII: (C) < (A) < (B) < (D) ;
- N trong (B) l bc 1 c tnh baz yu hn N trong (D) l bc 2.
- (A) c nhm ht e lm gim mt e trn N tnh baz gim
- N trong (C) tham gia vo h lin hp vi vng thm nn hu nh khng cn tnh baz.
Cu 56. Cho cc cht: Piridin, Piperidin, Pirol, Anilin, Xiclohexylamin, p-amino piridin, m-
amino piridin v morpholin. Cho cc pKa tng ng: 5,17 - 11,11 - 0,4 - 4,58 - 10,64 -
9,11 - 6,03 v 8,33. Hy so snh v gii thch tnh baz gia:
a. Piridin v Piperidin.
b. Piridin v Pirol.
c. Anilin v Xiclohecxylamin.
d. p aminopiridin v Piridin.
e. Morpholin v Piperidin.
GII:
a) Pyridin < Piperidin : do i e gy tnh baz ca pyridin thuc obital sp
2
, n b gi cht hn
so vi trng hp piperidin vi obital sp
3
( m in ca obital sp
2
>sp
3
)
b) Piridin > Pyrol : do pyrol ch c th kt hp vi proton khi nh i tnh thm ca vng.
N
O
H
( Morpholin )


(B)

COOH
N
c) Xiclohexylamin > anilin : - do nguyn t N trong anilin lin kt vi nguyn t Csp
2
ca
vng thm, nguyn t C ny c m in mnh hn nguyn t Csp
3
ca xiclohexylamin. Mt
khc, cc e khng lin kt c th c phn tn trn vng thm. Cc cng thc cng hng ch
rng c s gim mt e ti Nit.

NH
2 NH
2
+
NH
2
+
NH
2
+

d) Para amino anilin > Piridin : do hiu ng lin hp p - t gia cp e n ca N vi h e t ca
vng thm nn mt e trong vng tng v mt e N cng tng.
e) Piperidin > Morpholin : Nguyn t oxi trong morpholin c m in ln hn nhm
CH
2
( cng v tr) ca piperidin, v th mt e trn nguyn t N ca morpholin s nh hn so
vi piperidin.
Cu 57.
So snh nhit nng chy ca:

N
N
H
H
( Imidazol )
N
( Indol )
H
N
N N
N
( Purin )

GII:

N N N N N N H
H
H


Indol c lin kt hidro nhng rt yu. Indol (52
0
C) <Imidazol (91
0
C) <Purin (217
0
C)

Cu 58. So snh kh nng phn ng halogen ha ca nhn pirol, thiofen, benzen v piridin.
GII: Pirol > Thiofen > Benzen > Pyridin
- Phn ng halogen ha vo nhn thm theo c ch eletrofin (tc nhn E
+
tn cng ) v
thng xy ra mi trng axit mnh: s tn cng ca mt ion tch in dng vo nhn
thm to ra hp cht trung gian cng l mt ion tch in dng. Do tnh baz, mi trng
ny pyridin l mt ion amoni tch in dng, s c mt ca ion tch in dng nhn thm
s ngn cn s to thnh in tch dng th 2. Do pyridin phn ng kh khn nht.
- Trong cc d vng Furan, pirol, thiofen c s phn b bt i xng in tch, lm cho trn cc
nguyn t cacbon ca vng tch in m ln hn trn nguyn t cacbon ca vng benzen.
l nguyn nhn gy ra tnh nhy cm cao ca d vng i vi s th electrofin.
- Do kh nng to hiu ng lin hp khc nhau v gim dn t O N S nn mt e trn
nguyn t cacbon 3 vng Furan, Pyrol, Thiofen cng gim dn. V d:

S
C
O
O
1) CH
3
COO
-
NO
2
+
,-10
0
C
2) Pyridin
S
C
O
O
NO
2
(51%)

Cu 59.
Hp cht hu c M c khi lng phn t 127. Trong M c 75,6%
C; 13,38% H ; M c kh nng lm xanh qu tm , khng lm mt
mu dung dch Br
2
/CCl
4
hay dung dch KMnO
4
long , khi hidro
ho M thu c cht A (C
8
H
11
N) oxi ho A thu c cht B:
Trong c 2 phn ng trn u khng c s ng hay m vng v
phn t M khng c cac bon bc ba.




CH
2
-CH
2
-CH
3

N



CH
2
-CH
2
-CH
3

N
1- Xc nh cng thc cu to ca M.
2- tch ly M nn dng dung mi no trong cc dung mi sau, gii thch: nc, ru etylic,
dung dch NaOH, dung dch HCl.
GII:
1.-Tm ra CTPT: C
8
H
17
N bt bo ho =1
;
- M khng lm mt mu dd Br
2
..=>M c
vng no.
- T CTCT ca B; CTPT ca A C
8
H
11
N
=>CTCT A: A ch c 1 gc hidrocacbon
M khng c cac bon bc ba nn

CTCT ca M l: v CTCT ca A l:
2- tch M dng dung dch HCl v: C
8
H
17
N + HCl C
8
H
17
N
+
HCl
-
- Nu dng H
2
O , M c gc R ln kh tan trong nc
- Nu dng C
2
H
5
OH, khng c tnh chn lc v C
2
H
5
OH c kh nng ho tan nhiu cht khc.
- Nu dng dd NaOH, M kh tan v M c tnh baz.
Dng dd HCl: C
8
H
17
N
+
HCl
-
+ NaOH C
8
H
17
N (Khng tan) +NaCl + H
2
O
Cu 60.
X l cht c c trong thuc l. Phn tch nguyn t cho thy X cha 74,07% cacbon; 8,64%
hiro v 17,28% nit. Dung dch 0,799 g X trong 100g benzen c nhit ng c l 5,28
0
C.
Xc nh cng thc phn t ca X, bit rng benzen c nhit ng c l 5,53
0
C v hng
s nghim lnh K = 5.07. Khi xi ho X bng dung dch Na
2
Cr
2
O
2
trong mi trng a xt thu
c mt trong cc sn phm l (M). xi ho X trong nhng iu kin thch hp li thu c
mt trong cc sn phm l (N).
1- Vit cng thc cu to ca X.
2- Vit phng trnh phn ng ca X, M, N vi dung dch HCl.
3- Sp xp s tng dn tnh a xt ca M, N, a xt benzonic, gii thch.

N
COOH
( Cht M )
N
H
COOH
( Cht N )

GII:
1- Xc nh cng thc cu to ca X:
Tm c cng thc n gin nht ca X l: C
5
H
2
N
Mx =5,07
100 ). 28 , 5 53 , 5 (
000 . 1 . 799 , 0

=162 . Phn t khi ca X l 162 dvc.

(C
5
H
7
N)
n
=162 n =2 . Cng thc phn t ca X l: C
10
H
14
N
2

Lp lun dn n cng thc cu to ca X l :
2. Phn ng vi HCl:
N
N
CH
3


N
N
CH
3
+ 2HCl
N
N
CH
3
H
+
Cl
+
H
Cl
N
COOH
+ HCl
N
COOH
H
+
Cl
N
CH
3
COOH
+ HCl
N
CH
3
COOH
+
H
Cl

3. Xp s tng dn tnh axit: (N) < Axit benzoic < (M)
Do kh nng ht electron ca cc bc gim theo th t sau:
piridyl > phenyl >1 metyl pirolidyl
Cu 61.
1.Trong thuc l c cht anabazin v mt ng phn cu to ca n l nicotin (rt c). Ngoi ra
ngi ta cn tng hp c cht nicotirin c cu to tng t nicotin:

N
N
N
N
CH
3
H
N
N
CH
3
Anabazin Nicotin
Nicotirin

a)Vit phng trnh phn ng xy ra khi cho mi hp cht trn tc dng vi HCl theo t l mol
1:1. Sp xp chng theo trnh t tng dn kh nng phn ng . Gii thch.
b)Trong s 3 hp cht trn, cht no c nhit si cao nht? Gii thch.
2.Oxi ho nicotin bng K
2
Cr
2
O
7
trong dd H
2
SO
4
thu c axit nicotinic dng iu ch cc
amit ca n l vitamin PP v coiamin (thuc cha bnh tim):

N
C NH
2
O
N
C N(C
2
H
5
)
2
O
( Vitamin PP) ( Codiamin )

a) Vit cng thc cu to ca axit nicotinic v so snh nhit nng chy ca n vi axit
benzoic. Gii thch.
b*) Cho bit trng thi lai ho ca cc nguyn t nit trong phn t vitamin PP. So snh tnh
baz ca cc nguyn t nit : gii thch.
c)Vitamin PP nng chy nhit cao hn coiamin, mc d c phn t khi nh hn. Ti
sao?
GII: 1. a)

N
N
H
Anabazin
+HCl
N
N
H
+
H
Cl

HCl phn ng vo nhm NH do tnh baz ca NH (amin bc hai, N trng thi lai ho sp
3
v
lin kt vi hai nguyn t Csp
3
) ln hn tnh baz ca N trong vng (N trng thi lai ho sp
2

v lin kt vi hai nguyn t Csp
2
).
N ... H N

N
N
H
CH
3
Nicotin
+HCl
N
N
CH
3
Nicotin
+
Cl

Do tnh baz ca nhm CH
3
N (amin bc ba, N trng thi lai ho sp
3
) ln hn tnh baz ca N
trong vng thm.

N
N
CH
3
Nicotirin
+HCl
N
N
CH
3
H
+
Cl

Do tnh baz ca nhm CH
3
N (cp electron ca N tham gia vo h lin hp thm) km tnh
baz ca N trong vng thm
-Trnh t tng dn kh nng phn ng:
Nicotirin < Nicotin < Anabazin
(Tnh baz do (Tnh baz do (Tnh baz do
vng piriin: vng piroliin: vng piperiin:
Nsp
2
ni Csp
2
) N-th: amin bc ba) amin no bc hai)
b) Anabazin c nhit si cao nht, v c lin kt hiro lin phn t:

2. a) Axit nicotinic nng chy nhit cao hn so vi axit benzoic, v c lin kt hiro lin
phn t:

N
COOH COOH
Axit Nicotinic Axit Benzoic


b) Trng thi lai ho: N
(a)
: sp
2
; N
(b)
: sp
3
.
Tnh baz ca N
(a)
>N
(b)

v nhm C =O ht electron lm gim mt electron trn N
(b)
.


c) V vitamin PP c lin kt hiro lin phn t:

GIO N
BUI 1: L THUYT C BN.
1. nh ngha:
2. Cch gi tn d vng 5 cnh v d vng 6 cnh:
* Vng cha N c tn bt u aza; cha O c tn bt u oxa; cha S c tn bt u thio.
* Vng cha bo ha: - 5 cnh (cha hoc khng cha N)c ui ol;
- 6 cnh cha N c ui in .
3. Cch nh s: - bt u t d t v theo chiu ngc chiu kim ng h vi ch s nh nht.
- u tin cho O S N
4. Phng php tng hp: - D vng ha cc hp cht khng vng
- Mt s phn ng iu ch ring
N
C NH
2
O
(a )
( b )

N ... H NH C

5. Tnh cht :
a) Tnh baz: - Pyridin c tnh baz cn d vng 5 cnh hu nh khng c tnh baz
b) Phn ng th:
* D vng 5 cnh ch c phn ng th S
E
. Phn ng xy ra C
2
v d hn benzen
* D vng 6 cnh d c phn ng th S
E
v S
N
. Nhng:
- Phn ng S
E
xy ra kh khn hn benzen v v tr C
3
. c bit khng d p Friedell-Craff.
- Phn ng S
N
xy ra d dng hn v v tr C
2
v C
4
.
c) Phn ng cng: ty tc nhn kh c th bo ha 1 phn hay ton phn cc lin kt t.
BUI 2: LUYN TP.
Cu 1: Ti lp : a, b, e, f. V nh : c, d
Cu 2: Ti lp : a V nh : b
Cu 4: Ti lp : 1a, 1c. V nh : 2, 3.
Cu 7 (ti lp) V nh cu 6