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