1

CHT LNG ION C NHIM

GVHD: GS.TS. L NGC THCH
SVTH: TRNG PHC LC
MSSV: 0914125
I HC QUC GIA THNH PH H CH MINH
TRNG I HC KHOA HC T NHIN
KHOA HA HC
B MN HA HC HU C
CHT LNG ION PROTON
NHM ACID SULFONIC
1
M U
NI DUNG
KT LUN
2

Thay th dung mi c hi
Xc tc phn ng
D thu hi v ti ch
3
M U

1. CHT LNG ION
2. CHT LNG ION C NHIM
3. CHT LNG ION PROTON NHM ACID
SULFONI C

4
NI DUNG
NH NGHA

Cht lng ion:
Cht lng ion nhit phng (Room-
temperature ionic liquid).
Cht lng ion khng cha nc
(Nonaqueous ionic liquid).
Mui hu c lng (Liquid organic salt)
Jason P. Hallett, Tom Welton, Room-temperature ionic liquids: solvents for synthesis and
catalysis. 2, Chem. Rev. 111(5), 3508-3576, 2011.

5
Cht lng ion (Ionic liquid, IL)
IL
C CU

Cation
Amonium
Sulfonium
Phosphonium
Anion
V c
Hu c
L. Greaves Tamar, J. Drummond Calum, Protic ionic liquids: properties and applications, Chem.
Rev. 108(1), 206-237, 2008.

NO
3
-
, PF
6
-
, BF
4
-
,.
CH
3
COO
-
,
6
Danh php

Tn IL = tn anion + tn cation.



Clorur 1-butil-3-metilimidazolium
N N
H
3
C
Cl
Jason P. Hallett, Tom Welton, Room-temperature ionic liquids: solvents for synthesis and
catalysis. 2, Chem. Rev. 111(5), 3508-3576, 2011.

7
IL
Danh php
Mi nhm th dy alkil thay bng mt mu t.
Mi trung tm mang in tch c k hiu khc
nhau, Imidazolium thay bng im.
[bmim]
+
, [BMIM]
+
cation 1-butil-3-
metilimidazolium.


[pmim]
+
thay th :
cation 1-propil-3-metilimidazolium
cation 1-pentil-3-metilimidazolium?


Jason P. Hallett, Tom Welton, Room-temperature ionic liquids: solvents for synthesis and
catalysis. 2, Chem. Rev. 111(5), 3508-3576, 2011.

8
IL
Danh php
H thng ci tin s dng mu t cho trung tm
mang in tch, dy alkil thay bng mu t C s
carbon tng ng:
Cation 1-butil-3-metilimidazolium vit
thnh [C
4
C
1
im]
+
.
i vi dy alkil phn nhnh:
Cation 1-tert-butil-3-metilimidazolium vit
thnh [
t
C
4
C
1
im]
+
.


Jason P. Hallett, Tom Welton, Room-temperature ionic liquids: solvents for synthesis and
catalysis. 2, Chem. Rev. 111(5), 3508-3576, 2011.

9
IL
Danh php
Nu dy mang nhm chc:
[(OH)
4
C
4
C
1
im]
+
cho bit nhm OH cui
dy carbon ca chui butil.
Trong dy c d nguyn t:
[(C
1
OC
2
)C
1
im]
+
, hin th oxigen gia
carbon th hai v cui mch.

IL
Jason P. Hallett, Tom Welton, Room-temperature ionic liquids: solvents for synthesis and
catalysis. 2, Chem. Rev. 111(5), 3508-3576, 2011.

10
Danh php
i vi cation [C
4
C
1
C
1
2
im]
+
:

Thay th cho 1-butil-2,3-dimetilimidazolium
C
1
2
cho bit v tr metil ha trn vng d nguyn t v
tr s 2.
i vi anion:
Gi tn bnh thng theo tn nhm chc,
[C
4
OSO
3
]
-
thay cho sulfat butil.
Jason P. Hallett, Tom Welton, Room-temperature ionic liquids: solvents for synthesis and
catalysis. 2, Chem. Rev. 111(5), 3508-3576, 2011.

11
IL
IL
12
Mt s cation thng gp
Jason P. Hallett, Tom Welton, Room-temperature ionic liquids: solvents for synthesis and
catalysis. 2, Chem. Rev. 111(5), 3508-3576, 2011.

1-Alkil-3-metilimidazolium 1-Alkilpiridinium 1-Alkil-1-metilpirrolidinium
Tetraalkilamonium Tetraalkilphosphonium Trialkilsulfonium
N N
R CH
3
N
R
N
R CH
3
[C
n
C
1
im]
+
[C
n
pyr]
+
[C
n
C
1
pyrr]
+
R
4
N R
4
P R
3
S
[C
4
N] [C
4
P] [C
3
S]
Mt s anion thng gp
Jason P. Hallett, Tom Welton, Room-temperature ionic liquids: solvents for synthesis and
catalysis. 2, Chem. Rev. 111(5), 3508-3576, 2011.

13
IL
Bis(trifluorometilsufonil)imidur Trifluorometansulfonat Sulfat alkil
NTf
2 OTf C
n
OSO
3
triflat
Dicianamidur Hexafluorophosphat Tetrafluoroborat
[N(CN)
2
] [PF
6
] [BF
4
]
F
3
C S
O
O
S
O
O
CF
3
F
3
C S
O
NC
N
CN
F
P
F
F F
F F
F
B
F
F
F
ROSO
3
N
O
O
Lch s pht trin
Ba th h cht lng ion:

IL
N N
N N N N
AlCl
4
BF
4
PF
6
COOH
Th h th nht
Anion nhy vi
hi m
Th h th hai
Cht lng ion bn
vi khng kh v
hi m
Th h th ba
Cht lng ion
gn nhm chc
14
Tnh cht
Bay hi km nhit thng
bn nhit cao
p sut hi rt km
Trng thi lng khong nhit rng
dn ion kh cao
phn cc cao, ph thuc vo thnh phn v c
cu ca cation v anion
Ha tan trong rt nhiu dung mi hu c phn cc.
Ananda S. Amarasekara, Onome S. Owereh, Thermal properties of sulfonic acid group functionalized Br nsted
acidic ionic liquids, J. Therm. Anal. Calorim. 103(3), 1027-1030, 2011.

15
IL
- NH
2
- OH, OR
- SH
- PPh
2
- Si(OR)
3
-Ure, Tioure
- v..v
N N R
FG
X
Rajkumar Kore, Rajendra Srivastava, Synthesis and applications of novel imidazole and benzimidazole
based sulfonic acid group functionalized Brnsted acidic ionic liquid catalysts, Journal of Molecular
Catalysis A: Chemical 345(1-2), 117- 126, 2011.
Sang-gi Lee, Functionalized imidazolium salts for task-specific ionic liquids and their applications, Chem.
Commun., 1049-1063, 2006.


16
Cht lng ion c nhim (Task-
specific ionic liquid, TSIL)
-Xc tc
- Mi trng phn ng
- Dung mi ly trch
Phn loi
TSIL

IL baz
IL gn kim loi
IL th tnh

IL guanidinium
IL acid
IL gn nhm -OH
Caibo Yue, Dong Fang, Lin Liu, Ting-Feng Yi, Synthesis and application of task-specific ionic liquids used as
catalysts and/or solvents in organic unit reactions, Journal of Molecular Liquids 163(3), 99-121, 2011.
17
TSIL
IL acid
IL acid Lewis
IL acid Lewis thng thng.
IL acid Lewis hp ph trn cht mang rn.
IL acid Bronsted
IL nhm acid gn anion.
IL nhm acid gn cation anion.
IL nhm acid gn cation.
IL acid Bronsted Lewis kt hp

Caibo Yue, Dong Fang, Lin Liu, Ting-Feng Yi, Synthesis and application of task-specific ionic liquids used as
catalysts and/or solvents in organic unit reactions, Journal of Molecular Liquids 163(3), 99-121, 2011.
18
TSIL

iu ch
IL nhm acid gn cation






N N
H
3
C
+
O
S
O O
N N
H
3
C
S
O
O
O
N N
H
3
C
S
O
O
OH
X
HX
X = CF
3
SO
3
James H. Davis Jr., Task specific ionic liquids, Chemistry Letters 33(9), 1072 1077, 2004.
Jason P. Hallett, Tom Welton, Room-temperature ionic liquids: solvents for synthesis and catalysis. 2, Chem.
Rev. 111(5), 3508-3576, 2011.


19
Cht lng ion proton (Protic ionic
liquid, PIL) acid sulfonic
iu ch
IL nhm acid gn anion:
PIL acid sulfonic
20
N N
H
3
C
+
H
2
C CH
2
Cl
R
N N
H
3
C R
Cl
N N
H
3
C R
HSO
4
H
2
SO
4
- HCl
James H. Davis Jr., Task specific ionic liquids, Chemistry Letters 33(9), 1072 1077, 2004.
Jason P. Hallett, Tom Welton, Room-temperature ionic liquids: solvents for synthesis and catalysis. 2, Chem.
Rev. 111(5), 3508-3576, 2011.


iu ch
IL nhm acid gn cation anion:









N NH
CH
2
Cl
2
12h
ClSO
3
H
HCl
k
N N
HO
3
S SO
3
H
Cl
12 h
60
o
C
H
2
SO
4
(99.9 %)
HCl
k
N N
HO
3
S SO
3
H
HSO
4
M.A. Zolfigol,V. Khakyzadeh, A.R. Moosavi-Zare, G. Chehardoli, F. Derakhshan-Panah, A. Zare, O. Khaledian,
Novel ionic liquid 1,3-disulfonic acid imidazolium hydrogen sulfate {[Dsim]HSO
4
} efficiently catalyzed N-boc
protection of amines, Scientia Iranica C 19(6), 1584-1590, 2012.

21
PIL acid sulfonic
Tnh cht ha l
im chy
bn nhit
T trng
Ch s khc x
Sc cng b mt
nht
dn ion
phn cc
Tnh acid
Gi tr pK
a
ca PIL c xc nh thng qua vic chun
bng KOH.
L. Greaves Tamar, J. Drummond Calum, Protic ionic liquids: properties and applications, Chem. Rev. 108(1), 206-
237, 2008.
22
PIL acid sulfonic
Ester ha





Xc tc H
2
SO
4
m c, hiu sut 62%.
L Ngc Thch, Ha Hc Hu C, NXB HQG Tp.HCM, 293-294, 2002.
Jason P. Hallett, Tom Welton, Room-temperature ionic liquids: solvents for synthesis and catalysis. 2, Chem. Rev.
111(5), 3508-3576, 2011.
Yue Qin Cai, Guo Qiang Yu, Chuan Duo Liu, Yuan Yuan Xu, Wei Wang, Imidazolium ionic liquid-supported
sulfonic acids: efficient and recyclable catalysts for esterification of benzoic acid, Chinese Chemical Letters 23(1),
1-4, 2012.

23
PIL acid sulfonic
COOH
CH
3
CH
2
OH +
COOC
2
H
5
N N SO
3
H
HSO
4
100
o
C
3 h
98 %
Phn ng chuyn v Beckmann



Xc tc: H
2
SO
4
, PCl
5
, HCl trong hn hp CH
3
COOH
v O(COCH
3
)
2
.
Nhit phn ng cao (khong 130
o
C)
Acid d.
D n mn dng c, nhiu sn phm ph.
Sang-gi Lee, Functionalized imidazolium salts for task-specific ionic liquids and their applications, Chem. Commun.,
1049-1063, 2006.
Jianzhou Gui, Youquan Deng, Zhide Hu, Zhaolin Sun, A novel task-specific ionic liquid for Beckmann
rearrangement: a simple and effective way for product separation, Tetrahedron Letters 45(12), 2681-2683, 2004.
24
PIL acid sulfonic
N
OH
HN
O
31 47 %
Phn ng chuyn v Beckmann

PIL acid sulfonic
25
N N SO
2
Cl
Cl
N N SO
2
Cl
PF
6
NH
4
PF
6
H
2
O, 293 K
9b
N
OH
HN
O
9b
80
o
C
2 h
Sang-gi Lee, Functionalized imidazolium salts for task-specific ionic liquids and their applications, Chem. Commun.,
1049-1063, 2006.
Jianzhou Gui, Youquan Deng, Zhide Hu, Zhaolin Sun, A novel task-specific ionic liquid for Beckmann
rearrangement: a simple and effective way for product separation, Tetrahedron Letters 45(12), 2681-2683, 2004.
98.3 %
Phn ng sc hp indol











Thun li: thao tc n gin, hiu sut tt, phn
ng nhanh, kh nng ti s dng ca cht xc tc v
trnh to thnh dung mi v tc nhn c hi.
Sougata Santra, Adinath Majee, Alakananda Hajra, Task-specific ionic liquid-catalyzed efficient couplings of indoles
with 1,3-dicarbonyl compounds: an efficient synthesis of 3-alkenylated indoles, Tetrahedron Letters 52(29), 3825-
3827, 2011.
26
PIL acid sulfonic
N
H
R
O O
+
N
H
R
O
PIL 10% mol
1.5 h
84 %
Cu hnh E
N N
SO
3
H
OTf
PIL:
Tng hp 1-amidoalkil-2-naptol




Xc tc: acid p-toluensulfonic, Fe(HSO
4
)
3
, acid
sulfamic HSO
3
.NH
2
/ siu m, HClO
4
/ SiO
2
, clorur tritil,
P
2
O
5
,
Hiu sut thp, thi gian phn ng di, lng xc tc
tc s dng nhiu, phng php khng hiu qu khi dng
amid hng phng hoc ure trong phn ng ny, cht xc
tc c v t tin.
Mohammad Ali Zolfigola, Ardeshir Khazaei, Ahmad Reza Moosavi-Zare, Abdolkarim Zare, Vahid Khakyzadeh,
Rapid synthesis of 1-amidoalkyl-2-naphthols over sulfonic acid functionalized imidazolium salts, Applied Catalysis
A: General 400(1-2), 70-81, 2011.
27
PIL acid sulfonic
OH
R H
O
R' NH
2
O
OH
R NH
R' O
+
+
120
o
C

81 96 %
[(HO
3
S)C
1
im]]Cl
(10 % mol)
Bo v amin




Xc tc: 4-(N,N-dimetilamino)piridin (DMAP), AcOH / 1,4-dioxan.
Thi gian phn ng di, c tnh cao (DMAP).

O O O
O O
M.A. Zolfigol,V. Khakyzadeh, A.R. Moosavi-Zare, G. Chehardoli, F. Derakhshan-Panah, A. Zare, O. Khaledian,
Novel ionic liquid 1,3-disulfonic acid imidazolium hydrogen sulfate {[Dsim]HSO
4
} efficiently catalyzed N-boc
protection of amines, Scientia Iranica C 19(6), 1584-1590, 2012.
Cheraiet Zinelaabidine, Ouarna Souad, Jamel Zoubir, Berredjem Malika, Aouf Nour-Eddine, A simple and efficient
green method for the deprotection of N-boc in various structurally diverse amines under water-mediated catalyst-free
conditions, International Journal of Chemistry 4(3), 2012.

28
PIL acid sulfonic
Dicarbonat di-tert-butil (Diboc)
NH
2
O
H
3
C
NH
O
H
3
C
O O
[(HO
3
S)(HO
3
S)im]HSO
4
(0.01 mmol)
Diboc (1 mmol) / EtOH
2 h
88 %
57 %
Thu hi v ti ch











N N
SO
3
H
Cl
N N
ClSO
3
H
i
ii
Mohammad Ali Zolfigola, Ardeshir Khazaei, Ahmad Reza Moosavi-Zare, Abdolkarim Zare, Vahid Khakyzadeh,
Rapid synthesis of 1-amidoalkyl-2-naphthols over sulfonic acid functionalized imidazolium salts, Applied Catalysis
A: General 400(1-2), 70-81, 2011.

29
PIL acid sulfonic
i) Ti ch
ii) Thu hi
PIL acid sulfonic ngy cng c s dng rng ri nh vo
tnh nng khng bay hi nhit phng, lm dung mi v
xc tc thay cho cc dung mi hu c v xc tc khc vn
c hi v gy nhim mi trng.
PIL acid sulfonic iu ch d dng, c hot tnh cao, d kim
sot phn ng, to thnh sn phm nh mong i.
ng vai tr l cht xc tc, dung mi trong nhiu phn ng
tng hp hu c, lng s dng t, rt ngn thi gian phn
ng, cho sn phm hiu sut cao.
D dng thu hi bng cc thao tc n gin, hot tnh PIL
acid sulfonic sau nhiu ln ti ch vn khng b mt i hoc
hot tnh ch gim nh.
30
KT LUN

CM N THY C V
CC BN LNG
NGHE
31
C ch tng hp 1-amidoalkil-2-naptol
Bo v amin