The Synthesis of Sulfo Derivatives of Calix[4]arenes Yury Yu. Morzherin Ekaterinburg Department of...
-
Upload
ruby-banks -
Category
Documents
-
view
229 -
download
0
description
Transcript of The Synthesis of Sulfo Derivatives of Calix[4]arenes Yury Yu. Morzherin Ekaterinburg Department of...
The Synthesis of Sulfo Derivatives
of Calix[4]arenes
Yury Yu. Morzherin
Ekaterinburg
Department of Technology for Organic Synthesis
The Urals State Technical University – UPI
Sulfo Derivatives of Calix[4]arenes
OO O O
S S S S
R R R R
O O O OO
OOO
OHOHOHOH
OO O OR R R R
H2SO4
80%
OO O OR R R R
AlCl3
Shinkai S.; Mori S.; Sone T.; Manade O. Tetrahedron Lett. 1984, 25, 5315
H2SO4
Scharff J.; Mahjoubi M. J.New.Chem. 1991, 15, 883
Water-soluble Receptors
OO O O
S S S S
OOOO
OHOH
OHOH
O O O OO
OOO
OHOHOHOH
S.Shinkai, K.Araki, M. Kubota, T. Arimura, T.Matsuda, J.Org.Chem. 1991, 56, 295
for Cu2+, Zn2+, Ni2+, UO22+
G.Arena, A.Contino, F.Gulino, A.Margi, D.Sciotto, R.Ungaro, Tetrahedron Lett. 2000, 41,
9327
OO O O
S S S S
H H H H
O O O OO
OOO
OHOHOHOH
for acetonitrile, acetone
Chlorosulfonylated of Calix[4]arene
Morzherin, Yu.; Rudkevich, D.M.; Verboom, W.; Reinhoudt, D.N. J.Org.Chem. 1993, 58, 7602
OO O OR R R R OO O O
S S S S
R R R R
O O O OO
OO
OClCl Cl Cl
HSO3Cl
r.t.
50-95%
OO O O
S S S S
H H H H
O O O OO
OO
OClCl Cl Cl
20-35%
for R = Me, Et, Pr
OO O O
OOOO
EtOEtO
OEtOEt
OO O O
S S S S
OOOO
EtOEtO
OEtOEt
O O O OO
OOO
ClClClCl
HSO3Cl
r.t.
OO O O
OOOO
NN
NN
OO O O
S S
OOOO
NN
NN
O OO O
ClCl
HSO3Cl
r.t.
OO O O
OO O OCH3
CH3 CH3CH3
1 OO O O
S S S S
OO O OCH3
CH3 CH3CH3
O O O OO
OO
OClCl Cl Cl
HSO3Cl
r.t.
75%
2
OO O O
S S S S
OO O OCH3
CH3 CH3CH3
O O O OO
OO
ONH NH NH NH
AlkAlk AlkAlk
AlkNH2
3OO O O
S S S S
OO O OCH3
CH3 CH3CH3
O O O OO
OO
ONH NH
NH NH
NH NHNH
NH
O CH3CH3
OCH3
OCH3
O
NH2NH
O
CH3
80-90%
4
The Synthesis of Anion Receptors
Anion Receptors
A- Cl- HSO4- HNO3
- ClO4-
Kass= 1250 103400 513 <1
OO O O
S S S S
OO O OCH3
CH3 CH3CH3
O O O OO
OO
ONH NH
NH NH
NH NHNH
NH
O CH3CH3
OCH3
OCH3
O
4
Morzherin, Yu.; Rudkevich, D.M.; Verboom, W.; Reinhoudt, D.N. J.Org.Chem. 1993, 58, 7602
A-
OO O O
S S S S
OO O OCH3
CH3 CH3CH3
O O O OO
OO
ONH NH
NH NH
3
A-
A- Cl- HSO4- HNO3
- ClO4-
Kass= 360 970 240 <1
OO O O
S S S S
R R R R
O O O OO
OOO
OHOHOHOH
OO O OR R R R
H2SO4
Na+
OO O O
S S S S
R R R R
O O O OO
OOO
OHOHOHOH
Synthesis of p-sulfonatocalix[4]arenes
OO O O
S S S S
OOOO
EtOEtO
OEtOEt
O O O OO
OOO
OHOHOHOH
OO O O
OOOO
EtOEtO
OEtOEt
SO3 (30-40%)
H2SO4
Sodium free
OO O O
OOOO
NN
NN
OO O O
S S S S
OOOO
NN
NN
O O O OO
OOO
OHOHOHOH
H2SO4
SO3 (30-40%)
Sodium free
OO O O
OOOO
NN
NN
HH
H
HH
H HH
OO O O
S S S S
OOOO
NN
NN
O O O OO
OOO
OHOHOHOH
HHH
HH
HHH
H2SO4
SO3 (30-40%)
SO
OOH
O
H+
Synthesis of ditopic receptors
OO O O
S S S S
OOOO
NN
NN
O O O OO
OOO
OHOHOHOH
5
OO O O
S S S S
OOOO
NN
NN
O O O OO
OOO
ClClClCl
SOCl2
6
R1NH2
OO O O
S S S S
OOOO
NN
NN
O O O OO
OOO
NHNHNH
NH R1
R1R1R1
7
Met+
A-
The NMR Determination of Kass
OO O O
S S S SO O O O
OO
OONH NH NH NH
R1 R1 R1 R1
O O OO
Met+
A-
OO O O
S S S S
OOOO
NN
NN
O O O OO
OOO
NHNHNHNH
R1R1R1R1
OO O O
S S S S
OOOO
NN
NN
O O O OO
OOO
NHNHNHNH
R1R1R1R1
Shift from 6.6 to 7.5 ppmShift from 6.6 to 5.8 ppm
Kass, M-1 in CH3CN-H2O
A-
OO O O
S S S SO O O O
OO
OONH NH NH NH
R1 R1 R1 R1
O O OO
3
A-
R1 = i-Pr
t-Bu
Cl- HSO4-
180 650
72 134
Fe2+
A-
OO O O
S S S S
OOOO
NN
NN
O O O OO
OOO
NHNHNHNH
R1R1R1R1
7
A-
R1 = i-Pr
t-Bu
Cl- HSO4-
1270 8020
970 4000
Acknowledgment • Prof. David Reinhoudt• Dr. Wim Verboom• Dr. Dmitry Rudkevich
The authors also thank the Russian Foundation for Basic Research (Grant 01-03-96431a)
Research team• A.I. Matern, PhD
• T.V. Glukhareva, PhD • M.F. Kosterina, PhD-student