Arenediazonium o-Benzenedisulfonimides
FULL PAPER
described in the appropriate section. ε and λmax values are as fol-
lows:
[1]
H. Zollinger, Acc. Chem. Res. 1973, 6, 335Ϫ341. H. Zollinger
in The Chemistry of Functional groups. The Chemistry of amino,
nitroso, nitro and related groups, Supplement F2s. (Ed.: S. Patai),
Part 2, John Wiley & Sons, New York, 1996, chapter 13.
M. Barbero, I. Degani, R. Fochi, P. Perracino (National Re-
search Council of Italy) PCT/EP98/01145, 1998; Chem. Abstr.
Compound 8: methanol/water (2:1), λmax ϭ 509 nm (log ε ϭ 4.16)
Compound 8: acetic acid/sodium acetate buffer, λmax ϭ 509 nm (log
ε ϭ 4.26)
[
2]
Compound 12: acetonitrile, λmax ϭ 480 nm (log ε ϭ 4.46)
Compound 12: methanol, λmax ϭ 480 nm (log ε ϭ 4.45)
Compound 13: methanol/water (2:1), λmax ϭ 420 nm (log ε ϭ 4.13)
Compound 13: methanol, λmax ϭ 420 nm (log ε ϭ 4.23)
Compound 13: acetonitrile, λmax ϭ 420 nm (log ε ϭ 4.22)
1
998, 129, 244942; M. Barbero, M. Crisma, I. Degani, R.
Fochi, P. Perracino, Synthesis 1998, 1171Ϫ1175.
C. Colas, M. Goeldner, Eur. Org. Chem. 1999, 1357Ϫ1366.
M. Barbero, I. Degani, N. Diulgheroff, S. Dughera, R. Fochi,
Synthesis 2001, 585.
[3]
[4]
[
[
[
5]
6]
7]
M. Barbero, I. Degani, N. Diulgheroff, S. Dughera, R. Fochi,
M. Migliaccio, J. Org. Chem. 2001, 65, 5600Ϫ5608.
M. Barbero, I. Degani, N. Diulgheroff, S. Dughera, R. Fochi,
Synthesis 2001, 2180Ϫ2190.
H. Zollinger, Color Chemistry, VCH Verlagsgesellschaft,
Weinheim, 1991.
ϱ
Usually, the experimental A values, obtained from reaction mix-
tures after addition of appropriate amount of base (DABCO,
NaOH), at the end of the reaction are very near to the ‘theoretical’
A
ϱ
values obtained from ε values. In a few cases, though, the ex-
perimental A values were lower than the theoretical A values. In
these cases, kinetic runs were not considered.
[8]
[9]
H. Zollinger, Diazo Chemistry I, VCH Verlagsgesellschaft,
Weinheim, 1994.
ϱ
ϱ
R. Schank, in The Chemistry of Functional groups. The Chem-
istry of Diazonium and Diazo groups. (Ed.: S. Patai) Part 2,
John Wiley & Sons, New York, 1978, chapter 14.
A. F. Hegarty, Kinetics and Mechanisms of Reactions Involving
Diazonium and Diazo groups. In The Chemistry of Diazonium
and Diazo Compounds, (Ed.: S. Patai) John Wiley & Sons, New
York, 1978, chapter 12.
H. Kropacova, J. Panchartek, V. Sterba, K. Valter, Coll. Czech.
Chem. Commun. 1970, 35, 3287Ϫ3295.
S. Koller, H. Zollinger, Helv. Chim. Acta 1970, 53, 78Ϫ89.
L. Forlani, J. Phys. Org. Chem. 1999, 12, 417Ϫ424.
Y. Hashida, H. Ishida, S. Sekiguchi, K. Matsui, Bull. Chem.
Soc. Japan 1974, 47, 1224Ϫ1227.
In particular, the reactions between p-methoxybenzenediazonium
o-benzenedisulfonimide (1) or the related tetrafluoroborate 3 and
sodium 1-naphthol-4-sulfonate (6) were performed in a buffered
aqueous solution obtained by adding sodium acetate (4.10 g) to
acetic acid (2.85 mL) in 100 mL of water and the pH value was
checked by a pH meter with a glass electrode.
[10]
[
[
11]
12]
Under these experimental conditions, the formation of azo dye 8
[
10,11]
takes place from the naphtholate ion.
The rate for the naph-
[13]
[14]
7
9
tholate ion is usually about 10 Ϫ10 times higher than the rate for
the undissociated naphthol.
[
[
15]
16]
Ϫ
ϩ
M. S. Newman, J. Blum, J. Am. Chem. Soc. 1964, 86, 503Ϫ507.
K. Kalfus, V. Sterba, Coll. Czech. Chem. Commun. 1969, 34,
The equation k
second order rate constant, K
of the considered naphthol (K
0
ϭ kobsd. [H ]/K
a
, where kobsd. is the experimental
a
is the apparent dissociation constant
ϭ 6.3 ϫ 10 ), [H ] is the con-
3
183Ϫ3186.
Ϫ9 [11]
ϩ
a
C. Reichardt, Solvent Effects in Organic Chemistry, Verlag
Chemie, Weinheim, 1979.
H. Zollinger, Helv. Chim. Acta 1955, 38, 1597Ϫ1616, and
1617Ϫ1622.
Ϫ
centration of the proton (pH ϭ 4.66), allows to calculate k
0
values.
[17]
obsd. ϭ 53.3 (sϪ1 molϪ1dm ) mean of 4 determinations; [sodium
3
k
[
[
18]
19]
Ϫ4
Ϫ3
H. Zollinger, Helv. Chim. Acta 1955, 38, 1623Ϫ1631.
G. Dauphin, A. Kergomard, Bull. Soc. Chim. France 1961,
1
-naphthol-4-sulfonate]
0
from 6.6 ϫ 10 to 2.0 ϫ 10 [1] ϭ 1.13
Ϫ4
Ϫ3
ϫ 10 mol dm
.
4
86Ϫ492.
Ϫ1
3
k
obsd. ϭ 50.3 (s molϪ1dm ) mean of 4 determinations; [sodium
[20]
[21]
J. T. Hewitt, H. V. Mitchell, J. Chem. Soc. 1906, 89,
167Ϫ1173.
P. B. Fisher, H. Zollinger, Helv. Chim. Acta 1972, 55,
139Ϫ2146.
Ϫ4
Ϫ3
1
0
-naphthol-4-sulfonate] from 6.6 ϫ 10 to 2.2 ϫ 10 [3] ϭ 1.15
1
Ϫ4
Ϫ3
ϫ 10 mol dm
.
2
The pKa of 5 in CH
literature method.
3
15]
2
OH/H O (2:1 by vol.) was determined by the
[22]
[
M. Bosco, L. Forlani, P. E. Todesco, Gazz. Chim. Ital. 1967,
7, 1594Ϫ1603. M. Bosco, V. Cal o` , F. Ciminale, L. Forlani,
L. Lopez, E. Nonnis, P. E. Todesco, Gazz. Chim. Ital. 1971,
01, 685Ϫ693.
9
1
[
[
23]
24]
Acknowledgments
This work was supported by the Ministero dell’Universit a` e della
Ricerca Scientifica e Tecnologica (MURST), National Project
J. R. Penton, H. Zollinger, Helv. Chim. Acta 1971, 543,
5
573Ϫ5779.
L. Forlani, Gazz. Chim. Ital. 1982, 112, 205Ϫ211.
R. Foster, Organic Charge Transfer Complexes, Academic
Press, New York, 1962.
S. D. Ross, I. Kuntz, J. Am. Chem. Soc. 1954, 76, 3000Ϫ3005.
Received May 17, 2002
[25]
"
Dry-state arenediazonium o-benzenedisulfonimides: synthesis, re-
activity and applications", by the National Research Council of
Italy (CNR), and by the University of Bologna (funds for selected
research topics A. A. 1999Ϫ2001).
[26]
[O92259]
Eur. J. Org. Chem. 2002, 3837Ϫ3843
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