Nitro group substitution in 2,4,6-trinitrotoluene under the action of arenethiols and transformations of the reaction products

Article abstract of DOI:10.1023/A:1015095832081

The reactions of 2,4,6-trinitrotoluene with arenethiols in the presence of inorganic bases in dipolar aprotic solvents led to the replacement exclusively of the ortho-nitro group to form 2-arylthio-4,6-dinitrotoluenes. Substitution, oxidation, and reducti

Full text of DOI:10.1023/A:1015095832081

2406
Russian Chemical Bulletin, International Edition, Vol. 50, No. 12, pp. 2406—2410, December, 2001
Nitro group substitution in 2,4,6-trinitrotoluene under the action
of arenethiols and transformations of the reaction products
O. V. Serushkina, M. D. Dutov, V. N. Solkan, and S. A. Shevelev«
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences,
47 Leninsky prosp., 119991 Moscow, Russian Federation.
Fax: +7 (095) 135 5328. E-mail: shevelev@cacr.ioc.ac.ru
The reactions of 2,4,6-trinitrotoluene with arenethiols in the presence of inorganic bases
in dipolar aprotic solvents led to the replacement exclusively of the ortho-nitro group to form
2-arylthio-4,6-dinitrotoluenes. Substitution, oxidation, and reduction of the latter and their
transformation products provided the basis for the preparation of mono- and di-ortho-S-sub-
stituted nitrotoluenes and aminotoluenes. Factors favoring the regiospecificity of
ortho-substitution in 2,4,6-trinitrotoluene are discussed.
Key words: 2,4,6-trinitrotoluene, arenethiols, nitro group substitution, regiospecificity,
selective oxidation, reduction, sulfides, sulfoxides, sulfones, amines.
As part of our continuing studies on the chemical
reactions in DMSO generally give sulfides 2 in lower
yields). Under the above-mentioned conditions, the re-
actions took place even at 20 °C; however, the reactions
proceeded much more rapidly at 50 °C (see Table 1).
The results of the reactions were independent of whether
they were carried out in an inert atmosphere or in air.
utilization of 2,4,6-trinitrotoluene (TNT),1 we are car-
rying out systematic investigation into nucleophilic sub-
stitution of the nitro groups in TNT and in transforma-
tion products of its methyl group, i.e., in 1-R-2,4,6-tri-
nitrobenzenes.2—9 Previously,10—13 we have reported that
arenethiols can replace the nitro group in 2,4,6-trinitro-
toluene in the presence of inorganic bases, only the
ortho-nitro group being replaced to form the corre-
sponding sulfides. The present study is devoted to de-
tailed analysis of the results obtained, including trans-
formations of the products formed upon the replace-
ment of the nitro group. In addition, the reasons for the
observed high regioselectivity of nucleophilic substitu-
tion are considered.
Scheme 1
Me
Me
O2N
NO2
+ ArSH
O2N
SAr
K2CO3
1
NO2
NO2
Results and Discussion
2a—d
Me
We found that various arenethiols 1 replaced the
ortho-nitro group in TNT in dipolar aprotic solvents
(DMF, N-methylpyrrolidone (N-MP), DMSO, acetoni-
trile, etc.) in the presence of alkalis or alkali carbon-
ates (hydrogencarbonates) to form previously un-
known 2-arylthio-4,6-dinitrotoluenes 2 (Scheme 1), no
para-substitution products were detected even in trace
amounts. The yields of sulfides 2 depend on the reaction
conditions because the major process can be accompa-
nied by the side reaction, viz., by the oxidation of the
arenethiolate anions, including oxidation under the ac-
tion of nitro compounds14 to form the corresponding
disulfides. The highest yields of sulfides 2 were achieved
with the use of alkali carbonates as deprotonating agents,
the use of solid K2CO3 and the equimolar ratio of the
reagents being the most convenient (Table 1). Acetoni-
trile, DMF, or N-MP are the solvents of choice (the
PhS
SPh
PhSH
2a
NO2
3
Ar = Ph (a), 4-MeC6H4 (b), 4-ClC6H4 (c), 2-NH2C6H4 (d)
Using sulfide 2a as an example, it was demonstrated
that the second ortho-nitro group can also be replaced
(under the action of PhSH) to yield bissulfide 3 (see
Scheme 1). In this case, the highest yields were obtained
in hexamethylphosphoramide (HMPA) at 20 °C (see
Table 1).
The possibility of selective oxidation of sulfides 2 was
also demonstrated with sulfide 2a as an example. De-
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2297—2301, December, 2001.
1066-5285/01/5012-2406 $25.00 © 2001 Plenum Publishing Corporation

Nitro group substitution in 2,4,6-trinitrotoluene
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 12, December, 2001 2407
Table 1. Reaction conditions and the properties of diaryl sulfides, sulfoxides, and sulfones
Com-
pound
Reagents
Solvent
T/°C
t/h
Yield
(%)
M.p./°C
(solvent)
2à
TNT, 1a, K2CO3
N-MP
DMF
MeCN
50
50
50
50
50
50
50
20
20
B.p.
80
80
80
50
2
2
1
2
2
3
3
24
144
2
6
2
1.5
2
2
0.5
72
79
77
40
77
54
30
40
68
92
38
56
48
62
87
71
96—97 (MeOH)
Ditto
»
»
»
»
DMSO
2b
2ñ
2d
3
TNT, 1b, Ê2ÑÎ3
TNT, 1c, Ê2ÑÎ3
TNT, 1d, Ê2ÑÎ3
2a, 1a, K2CO3
2a, 35% H2O2
2a, 35% H2O2
4, 1a, K2CO3
5, 1a, K2CO3
5, 1c, K2CO3
5, BuiSH, K2CO3
2a, NH2NH2•H2O, Raney Ni
4, NH2NH2•H2O,
FeCl3/activated C
5, NH2NH2•H2O,
FeCl3/activated C
, NH2NH2•H2O,
FeCl3/activated C
N-MP (DMF)
N-MP (DMF)
N-MP (DMF)
HMPA
96—97 (MeOH)
123—124 (Me2CO)
132—133 (CCl4)
163—164 (MeCOEt)
145—146 (ÑCl4)
169—170
119—120 (MeÑN)
127—128 (MeÑN)
135—136 (MeÑN)
112—113 (EtOH)
113.5—114.5
4
5
ÀñÎÍ
ÀñÎÍ
N-MP
N-MP
N-MP
N-MP
MeOH
MeOH
6
7a
7b
7c
8a
8b
B.p.
B.p.
172—173
8ñ
MeOH
MeOH
B.p.
B.p.
1.5
3.5
41
87
223—224
137—138
97ñ
pending on the conditions, the reaction of this sulfide
with 30—35% H2O2 in AcOH afforded either sulfoxide 4
(an equimolar amount of H2O2, 20 °C) or sulfone 5
(a large excess of H2O2, refluxing of the reaction mix-
ture) (Scheme 2; see Table 1).
It was demonstrated that the nitro groups in sulfox-
ide 4 and sulfone 5 can be replaced under the action of
thiols under the conditions identical with those used for
TNT (see Scheme 2, Table 1). In the reactions of
arenethiols with compounds 4 and 5 at 80 °C, exclu-
sively the ortho-nitro group was replaced to give com-
pounds 6 or 7a,b, respectively (see Scheme 2; Table 1).
However, the reaction of sulfone 5 with an alkanethiol
(BuiSH) resulted in para-substitution (according to the
NMR spectroscopic data, ∼20% of the total amount of
substitution products) along with the prevailing replace-
ment of the ortho-nitro group to form 3-isobutylthio-2-
methyl-5-nitrophenyl phenyl sulfone (7c). Previously,
we have observed a decrease in regioselectivity of
ortho-substitution of the nitro group in the reactions of
TNT with bulky alkanethiols.9
Scheme 2
Me
O2N
SPh
H2O2 AcOH
H2O2 AcOH
NO2
2a
O
O
Me
Me
Sulfide 2a, sulfoxide 4, and sulfone 5 were reduced
with hydrazine hydrate to the corresponding diamines 8
using either FeCl3 in the presence of activated carbon15
or Raney nickel as a catalyst (Scheme 3, see Table 1).
Analogously, compound 7c was reduced to the corre-
sponding toluidine 9 (Scheme 3, see Table 1).
O2N
SPh
O2N
SPh
O
NO2
NO2
4
5
Thus, we have developed procedures for the prepara-
tion of various mono- and di-ortho-substituted arylthio-,
arylsulfinyl-, and arylsulfonylnitrotoluenes as well as of
aminotoluenes based on TNT. The structures of the
resulting compounds were established by 1H NMR spec-
troscopy (Table 2), mass spectrometry (electron impact;
in all cases, the molecular ion peaks [M]+ were observed),
PhSH K2CO3
RSH K2CO3
O
O
Me
Me
PhS
SPh
RS
SPh
O
–1
and IR spectroscopy (νas(NO2), 1550—1580 cm ;
–1
–1
νs(NO2), 1350—1380 cm ; ν(SO), 1070—1030 cm ;
NO2
NO2
–1
–1
νas(SO2), 1300—1340 cm ; νs(SO2), 1120—1160 cm ;
6
7a—c
–1
–1
R = Ph (a), 4-ClC6H4 (b), Bui (c)
ν(NH2), 3390—3305 cm ; δ(NH2), 1620—1640 cm )

2408
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 12, December, 2001
Serushkina et al.
Scheme 3
the ortho-nitro group in TNT, favors the necessary change
in hybridization of the ipso-C atom from sp2 to sp3 upon
formation of the ipso-σ-complex because the rotation of
the nitro group decreases the degree of its conjugation
with the aromatic ring even in the starting compound.
This facilitates the formation of the ipso-σ-complex and,
finally, leads to an acceleration of the nucleophilic sub-
stitution of this nitro group as compared with the nitro
group which is coplanar with the aromatic ring. A similar
explanation for the regioselectivity of the replacement of
the ortho-nitro group in some nitrotoluene derivatives
have been proposed previously.20
Me
Me
O2N
S(O)nPh
H2N
S(O)nPh
N2H4•H2O
NO2
NH2
2a, 4, 5
8a—c
O
O
Me
Me
BuiS
BuiS
SPh
O
SPh
O
With the aim of studying the characteristic features of
the nucleophilic substitution of the aromatic nitro group,
we determined the structure of the model ipso-σ-complex
N2H4•H2O
–
formed by 1,3,5-trinitrobenzene with HS by ab initio
NO2
NH2
quantum-chemical calculations (the Hartree—Fock
method with the 6-31G++ basis set and with full geom-
etry optimization). It appeared that the nitro group at
the tetrahedral C atom is twisted by ∼30° out of the plane
7c
9
n = 0 (2a, 8a), 1 (4, 8b), 2 (5, 8c)
formed by the S, C , and N atoms (more detailed
3
sp
and were confirmed by the data from elemental analyses
(see Table 2).
information will be published elsewhere). It can be as-
sumed that the rotation of the nitro group in the starting
nitro compound facilitates the formation of this confor-
mation of the ipso-σ-complex, which is an additional
argument in favor of the high reactivity of the ortho-nitro
group of TNT in nucleophilic substitution reactions.
Simultaneously with the present study, the param-
eters of the replacement of the ortho- and para-nitro
The regiospecificity of substitution of the ortho-nitro
group in TNT calls for an explanation taking into ac-
count unfavorable, as might appear at first sight, steric
and inductive (donor) effects of the methyl group. It is
known16 that the nitro groups in the TNT molecule are
nonequivalent. Thus the para-nitro group is coplanar
with the benzene ring, whereas two ortho-nitro groups
are rotated about the C—N axis by ∼40° and ∼26° with
respect to the benzene ring* due to the steric effect of
the methyl group.
–
groups in TNT under the action of PhS were investi-
gated (taking into account the solvent effect) within the
framework of the SNAr mechanism by the semiempirical
PM3 quantum-chemical method. The principal results
of the cited investigation have been reported earlier.21
From these data it follows that the rate-limiting stage of
the reaction is the formation of the ipso-σ-complex. The
calculated activation energies of the formation of
the 2-ipso-σ- and 4-ipso-σ-complexes are 21.8 and
It is known that the formation of an ipso-σ-com-
plex17 is generally the rate-limiting stage in the classical
mechanism of aromatic nucleophilic substitution (SNAr),
including the nitro group substitution18,19 (Scheme 4).
Scheme 4
–1
25.2 kcal mol , respectively. This difference between
the activation energies indicates that the rate of the
replacement of the 2-nitro group is two orders of magni-
tude higher than that of the 4-nitro group (in the
temperature range of 20—50 °C). Hence, the regio-
specificity of the replacement of the nitro group in TNT
NO2
Nu NO2
–
–
+ Nu
R´
Slow
–
R
R
R´
under the action of PhS can be explained within the
framework of the SNAr mechanism without resorting to
other possible mechanisms, viz., to ion-radical processes,
the intramolecular rearrangement of the ortho-σ-complex
(from positions 1 and 3) into the ipso-σ-complex, etc.
ipso-σ-Complex
Nu
–
+ NO2
Fast
Experimental
R
R´
The melting points of the compounds were determined on
a Boetius stage (the heating rate was 4 deg min–1). The IR
spectra were recorded on a Specord M-80 spectrometer in KBr
pellets. The mass spectra were measured on a Kratos MS-30
spectrometer. The course of the reactions was monitored by
HPLC on a Liquochrom (Model 2010) instrument (Silasorb 18
as the reversed phase, a 3 : 1 MeCN—H2O mixture as
It is believed that the substantial noncoplanarity of
the nitro group and the aromatic ring, as in the case of
* According to the X-ray diffraction data,16 which were ob-
tained under conditions which exclude intermolecular hydro-
gen bonds involving TNT molecules.

Nitro group substitution in 2,4,6-trinitrotoluene
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 12, December, 2001 2409
1
Table 2. Data from H NMR spectroscopy and elemental analysis for the compounds synthesized
Com-
pound
Found
Molecular
formula
1H NMR spectrum
δ (J/Hz)
(%)
Calculated
Solvent
C
H
N
S
2à
2b
53.91
53.79
3.55
3.47
9.82
9.65
10.96
11.04
C13H10N2O4S
C14H12N2O4S
Acetone-d6
Acetone-d6
2.60 (s, 3 H); 7.56 (m, 5 H);
7.91 (d, 1 H, J = 2.2); 8.43 (d, 1 H, J = 2.2)
55.51
55.25
4.03
3.97
9.43
9.21
10.29
10.54
2.42 (s, 3 H); 2.60 (s, 3 H);
7.40 (d, 2 H, J = 8.1); 7.51 (d, 2 H, J = 8.1);
7.84 (d, 1 H, J = 2.3); 8.42 (d, 2 H, J = 2.3)
2c*
48.21
48.08
2.83
2.79
8.75
8.63
9.63
9.87
C13H9ClN2O4S
C13H11N3O4S
CDCl3
2.62 (s, 3 H); 7.45 (m, 4 Í);
7.92 (d, 1 H, J = 2.3); 8.39 (d, 1 H, J = 2.3)
2d
51.29
51.14
3.79 13.90
3.63 13.76
10.35
10.50
Acetone-d6
2.60 (s, 3 H); 5.32 (br.s, 2 Í);
6.78 (t, 1 H, J = 8.2); 7.00 (d, 1 H, J = 8.1);
7.36 (t, 1 H, J = 8.2); 7.45 (d, 1 H, J = 8.1);
7.62 (d, 1 H, J = 2.3); 8.38 (d, 1 H, J = 2.3)
3
4
5
64.61
64.56
4.34
4.28
4.06
3.96
17.96
18.14
C19H15NO2S2
C13H10N2O5S
C13H10N2O6S
CDCl3
2.58 (s, 3 H); 7.49 (m, 10 H);
7.71 (s, 2 H)
50.66
50.98
3.51
3.29
8.97
9.15
10.21
10.47
Acetone-d6
CDCl3
2.60 (s, 3 H); 7.59 (m, 3 H); 7.82 (m, 2 H);
8.82 (d, 1 H, J = 2.2); 9.10 (d, 1 H, J = 2.2)
48.53
48.45
3.18
3.13
8.42
8.69
9.59
9.95
2.68 (s, 3 H); 7.62 (dd, 2 Í, J = 8.1, 8.1);
7.72 (t, 1 H, J = 8.1); 7.94 (d, 2 H, J = 8.1);
8.74 (d, 1 H, J = 2.3); 9.27 (d, 1 H, J = 2.3)
6
61.93
61.77
4.21
4.09
3.83
3.79
17.22
17.36
C19H15NO3S2
C19H15NO4S2
C19H14ClNO4S2
Acetone-d6
Acetone-d6
Acetone-d6
2.49 (s, 3 H); 7.48 (s, 2 H); 7.57 (m, 2 H);
7.78 (m, 1 Í); 7.87 (d, 1 H, J = 2.3);
8.67 (d, 1 H, J = 2.3)
7à
59.43
59.20
4.02
3.92
3.81
3.63
16.42
16.64
2.59 (s, 3 H); 7.51 (s, 2 H); 7.71 (m, 2 H);
7.97 (d, 1 H, J = 2.3); 8.02 (d, 1 H, J = 8.1);
8.82 (d, 1 H, J = 2.3)
7b**
54.43
54.35
3.42
3.36
3.46
3.34
15.03
15.27
2.59 (s, 3 H); 7.50 (s, 4 H); 7.69 (dd, 2 H,
J = 8.1, 8.1); 7.78 (t, 1 H, J = 8.1);
8.01 (d, 2 H, J = 8.1); 8.05 (d, 1 H, J = 2.3);
8.85 (d, 1 H, J = 2.3)
7c
8a
55.99
55.87
5.38
5.24
3.95
3.83
17.38
17.55
C17H19NO4S2
DMSO-d6
DMSO-d6
1.00 (d, 6 H, J = 9.8); 1.88 (non, 1 H,
J = 10.1); 2.40 (s, 3 H); 3.05 (d, 2 H,
J = 9.8); 7.66 (dd, 2 H, J = 8.1; 8.1);
7.78 (t, 1 H, J = 8.1); 7.94 (d, 2 H, J = 8.1);
8.23 (d, 1 H, J = 2.3); 8.62 (d, 1 H, J = 2.3)
68.05
67.79
6.38 12.13
6.13 12.16
13.62
13.92
C13H14N2S
1.95 (s, 3 H); 4.72 (d, 4 H, J = 8.1);
5.97 (d, 1 H, J = 2.3); 6.03 (d, 1 H, J = 2.3);
7.05 (d, 2 H, J = 8.1); 7.12 (t, 1 H,
J = 8.1); 7.26 (dd, 2 H, J = 8.1, 8.1)
8b
8c
9
63.57
63.39
6.02 11.03
5.73 11.37
12.85
13.02
C13H14N2OS
C13H14N2O2S
C17H21NO2S2
DMSO-d6
DMSO-d6
DMSO-d6
1.95 (s, 3 H); 4.86 (br.s, 2 H);
4.98 (br.s, 2 H); 5.98 (d, 1 H, J = 2.3);
6.33 (d, 1 H, J = 2.3); 7.51 (m, 5 H)
59.62
59.52
5.44 10.47
5.38 10.68
12.01
12.22
1.92 (s, 3 H); 4.88 (br.s, 2 H); 5.08 (br.s,
2 H); 6.18 (d, 1 H, J = 2.3); 6.72 (d, 1 H,
J = 2.3); 7.60 (m, 3 H); 7.75 (m, 2 H)
61.02
60.86
6.43
6.31
4.30
4.18
19.01
19.12
0.97 (d, 6 H, J = 9.8); 1.77 (non, 1 Í,
J = 10.1); 2.12 (s, 3 H); 2.72 (d, 2 H,
J = 9.8); 5.60 (br.s, 2 H); 6.81 (d, 1 H,
J = 2.3); 7.25 (d, 1 H, J = 2.3);
7.62 (m, 3 Í); 7.75 (m, 2 H)
* Found (%): Cl, 10.97. Calculated (%): Cl, 10.92.
** Found (%): Cl, 8.52. Calculated (%): Cl, 8.44.
the eluent). The 1H NMR spectra were recorded on a
Bruker AC-200 spectrometer with Me4Si as the internal
standard.
2-Arylthio-4,6-dinitrotoluenes 2a—d. A solution of TNT
(5.675 g, 0.025 mol) in a dipolar aprotic solvent (10 mL) was
added to a mixture of arenethiol 1a—d (0.025 mol), K2CO3

2410
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 12, December, 2001
Serushkina et al.
(3.45 g, 0.025 mol), and the same solvent (15 mL). The reaction
mixture was stirred under conditions indicated in Table 1. Then
the mixture was poured into cold water (120 mL), and the
residue that formed was filtered off, dried, and recrystallized
from the corresponding solvent (see Table 1). Compounds 2c
and 2d were dissolved in CHCl3 and filtered through a silica gel
layer (∼20 g) prior to recrystallization. After completion of the
reactions performed in MeCN, the mixtures were filtered, the
solvent was evaporated, and the residue was recrystallized.
4-Nitro-2,6-bis(phenylthio)toluene (3). A mixture of com-
pound 2a (5.80 g, 0.02 mol), HMPA (20 mL), PhSH (2.20 g,
0.02 mol), and K2CO3 (2.76 g, 0.02 mol) was stirred at ∼20 °C
for 24 h and then poured into cold water (100 mL). The
precipitate that formed was filtered off, dried, and recrystallized.
2-Methyl-3,5-dinitrophenyl phenyl sulfoxide (4). A mix-
ture of sulfide 2a (0.25 mol), 35% H2O2 (2.25 mL), and glacial
AcOH (45 mL) was stirred at ∼20 °C for 6 days and then
poured into water (225 mL). The precipitate that formed was
filtered off, dried, and recrystallized.
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2-Methyl-3,5-dinitrophenyl phenyl sulfone (5). A mixture
of sulfide 2a (0.03 mol), 35% H2O2 (10.2 mL), and glacial
AcOH (70 mL) was refluxed for 2 h and then cooled. The
precipitate that formed was filtered off and dried.
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3-Arylthio(alkylthio)-2-methyl-5-nitrophenyl phenyl sulfox-
ide (6) and sulfones (7a—c). A solution of compound 4 or 5
(0.025 mol) in N-MP (10 mL) was added to a mixture of
arenethiol or alkanethiol (0.025 mol), K2CO3 (3.45 g,
0.025 mol), and N-MP (15 mL). The reaction mixture was
stirred under conditions indicated in Table 1. Then the mix-
ture was poured into cold water (120 mL), and the precipitate
that formed was filtered off, dried, and recrystallized from the
corresponding solvent (see Table 1). Compounds 6, 7a, and 7b
were dissolved in CHCl3 and filtered through a silica gel layer
(∼20 g) prior to recrystallization.
2,4-Diamino-6-phenylthiotoluene (8a). A suspension of Raney
nickel (0.3 g) in MeOH was added portionwise to a mixture of
compound 2a (2.9 g, 0.01 mol), MeOH (30 mL), and hydrazine
hydrate (3.9 mL, 0.08 mol) at 35—40 °C. The reaction mixture
was refluxed with stirring for 2 h. The catalyst was filtered off
and the solvent was evaporated. The residue was dissolved in
H2SO4, reprecipitated with ammonia, filtered off, and dried.
2,4-Diamino-6-phenylsulfinyl(phenylsulfonyl)toluenes (8b
and 8c). Hydrazine hydrate (3.9 mL, 0.08 mol) was added to a
mixture of compound 4 or 5 (0.01 mol), MeOH (30 mL),
FeCl3•6H2O (0.05 g), and activated carbon (0.63 g) at 30 °C.
The reaction mixture was heated to boiling and refluxed with
stirring as indicated in Table 1. Then the carbon was filtered
off, the solution was cooled, and the precipitate was filtered off
and dried. After completion of the reaction giving rise to
compound 8c, MeOH was evaporated, the residue was stirred
with dilute HCl, the carbon was filtered off, and ammonia was
added to the solution. The precipitate that formed was
reprecipitated with water from DMSO, filtered off, and dried.
5-Amino-3-isobutylthio-2-methylphenyl phenyl sulfone (9).
Hydrazine hydrate (0.78 mL) was added to a mixture of
compound 7c (3.65 g, 0.01 mol), MeOH (50 mL), FeCl3•6H2O
(0.03 g), and activated carbon (0.36 g) at 30 °C. The reaction
mixture was refluxed for 3.5 h. Then the carbon was filtered
off, the solution was cooled, and the precipitate was filtered off
and dried
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This study was financially supported by the Interna-
tional Science and Technology Center (ISTC, Project
No. 419).
Received March 27, 2001;
in revised form June 1, 2001