Synthesis and crystal structure of N,N-BIS[(4-aminophenoxy)ethyl]benzene sulfonamide

Article abstract of DOI:10.14233/ajchem.2014.15827

The reaction of diethanol amine and benzene sulfonyl chloride produced the benzene sulfonate intermediates, then it was nucleophilicly substituted by 4-nitrophenol and subsequently reduced by hydrazine hydrate in the presence of activated carbon and iron(

Full text of DOI:10.14233/ajchem.2014.15827

Asian Journal of Chemistry; Vol. 26, No. 10 (2014), 2854-2856
ASIAN JOURNAL OF CHEMISTRY
http://dx.doi.org/10.14233/ajchem.2014.15827
Synthesis and Crystal Structure of N,N-Bis[(4-aminophenoxy)ethyl]benzene Sulfonamide
1,*
2
1
GUANG-QI JIANG , YONG-ZHONG LU and JIE CAI
1College of Chemistry and Chemical Engineering, Guizhou University, Guiyang 550025, P.R. China
2College of Pharmaceutical Engineering, Guizhou Institute of Technology, Guiyang 550003, P.R. China
*Corresponding author: Tel: +86 851 8292313; E-mail: gqjiang@163.com
Received: 24 May 2013;
Accepted: 31 July 2013;
Published online: 10 May 2014;
AJC-15133
The reaction of diethanol amine and benzene sulfonyl chloride produced the benzene sulfonate intermediates, then it was nucleophilicly
substituted by 4-nitrophenol and subsequently reduced by hydrazine hydrate in the presence of activated carbon and iron(III) chloride. A
new binary aromatic amine, N,N-bis[(4-aminophenoxy)ethyl]benzene sulfonamide was prepared. The intermediates and the final product
were structurally characterized by the means of IR, 1H NMR and single crystal X-ray diffraction analysis.
Keywords: Benzene sulfonamide, Aromatic amine, Crystal structure.
aminophenoxy)ethyl]benzene sulfonamide is illustrated in
INTRODUCTION
Scheme-I.
The aromatic amines are important intermediates in the
synthesis of organic functional materials such as dyes, pigments
and bioactive compounds1-3. It is well known that the aromatic
amines are prepared mainly depending on the condensation
of amino-containing compounds and the reduction of the nitro
compounds4,5. Since the amino-containing compounds conden-
sation reactions need to be added an amino-protecting group
and their lower yields, so it is generally difficult to synthesize
a specific aromatic amine. Now, the reduction of the nitro
compounds to the corresponding amino compound has become
a commonly used method in the preparation of fine chemical
productions. Among the reduction process, methods of
catalytic hydrogenation, metal reduction, hydration hydrazine
reduction, electrochemical reduction are widely used6-9. In this
paper, low cost and available diethanol amine was adopted as
raw material, a new binary aromatic amine, N,N-bis[(4-amino-
phenoxy)ethyl]benzene sulfonamide, was synthesized. The
final product was structurally characterized by the methods of
IR, 1H NMR and single crystal X-ray diffraction analysis.
O
S
N
O
O
S
Cl
HO
NO2
H
O
S
O
S
O
N
HO
OH
O
O
O
O
DMF 100 °C
1
2
N
O
S
N
O
O
S
N
O
Hydrazine hydrate
C, FeCl3
O
O
O
O
NO2
NO2
NH2
NH2
4
3
Scheme-I: Synthetic route of N,N-bis[(4-aminophenoxy)ethyl]benzene
sulfonamide
Synthesis of the compound (2): Benzene sulfonyl chloride
(80 mL, 630 mmol) was added dropwise to a stirred mixture
of diethanolamine (20.0 mL, 208.5 mmol) and pyridine (105
mL) in a three-necked flask with the temperature lower than
35 ºC. The mixture was stirred for 2.5 h, subsequently stirred
for 1 h in a water bath of 40 ºC. After cooling to room tempe-
rature, concentrated hydrochloric acid (20 mL) was added,
white solid was precipitated, then filtrated and washed three
times with distilled water. The precipitate was further crysta-
llized from ethanol solvent, yielding 74.3 % white solid: m.p.
EXPERIMENTAL
All the reagents and solvents were used as commercial
sources without further purification. The IR spectra were
recorded on a Bio-Rad spectrophotometer using KBr discs
1
in the 4000-400 cm-1 region. The H NMR spectra of the
compound was recorded on a JEOL ECX 500 MHz spec-
trometer. Crystal structure was determinated on a Bruker
Apex 2 diffractometer. The synthesis route of N,N-bis[(4-

Vol. 26, No. 10 (2014)
Synthesis and Crystal Structure of N,N-Bis[(4-aminophenoxy)ethyl]benzene Sulfonamide 2855
116-117 ºC; 1H NMR (500 MHz, CDCl3): δ (ppm) = 3.42 (t,
4H, J = 5.8 Hz, -N-CH2), 4.15 (t, 4H, J = 6.3Hz, -O-CH2),
7.26-7.89 (m, 15H, Ar-H) ; IR (KBr, νmax, cm-1): 3436(s),
3067(w), 2998(w), 2892(w), 1447(s), 1403(m), 1361(s),
757(s).
Synthesis of the compound (3): Compound 2 (5.26 g,
10 mmol) dissolved in DMF (30 mL) was added dropwise to
a solution of anhydrous potassium carbonate (2.76 g, 20 mmol)
and 4-nitrophenol (2.78 g, 20 mmol) in DMF (40 mL) at 60 ºC
for 2 h. The mixture was stirred at 100 ºC for 24 h, after cooling
to room temperature, 1 mol/L NaOH solution (100 mL) was
added, pale yellow solid was precipitated. The precipitate was
filtrated and washed with distilled water, yielding 55.4 % solid
of 3: m.p. 153-154 ºC; IR (KBr, νmax, cm-1): 3436(s), 2928(w),
1594(s), 1511(vs), 1336(vs), 1264(s), 1161(m), 1111(m),
851(w), 580(w).
refined with anisotropic thermal parameters. Hydrogen atoms
were added theoretically and refined with riding model.
RESULTS AND DISCUSSION
The synthesis of benzene sulfonate is sensitive to the
reaction temperature, it should be strictly controlled in an ice
bath blew 35 ºC, when the reaction was performed at ambient
temperature, reaction temperature raised quickly and no white
solid was precipitated out. The nitro compound of 3 exhibits
poor solubility in common organic solvents, only IR spectrum
data can be obtained for it. In the process of reduction, hydrazine
hydrate should be added slowly and tracked by TLC, 24 h is
needed for the reduction reaction.
X-Ray diffraction analysis reveals there are two
crystallographically independent molecules in the asymmetric
unit. The molecular structure of compound 4 (Fig. 1) shows it
crystallized in the monoclinic system, P 21/n space group,
with the crystal cell parameters a = 13.599 (6), b = 16.852 (7),
c = 19.928 (9) Å, β = 109.046 (5)º, V = 4317 (3) Å3, Z = 8, Dc
= 1.316 g/cm3, F(000) = 1808.0, Mr = 427.52, R1 = 0.0503, wR2
= 0.1117. The selected bond lengths and bond angles are listed
in Table-1, the hydrogen bondings parameters are given in
Table-2.
Synthesis of the compound (4): Compound 3 (4.87g, 10
mmol) and actived carbon (0.6 g, 50 mmol) and FeCl3 (3.25
g, 20 mmol) were suspended in ethanol solvent (50 mL), with
continuously stirred and heated to reflux, 80 % hydrazine
hydrate (10 mL) was added dropwise, refluxed for 24 h and
separated by filtration, the filtrate was kept at room temperature
for slow evaporation. Colourless crystals were obtained after
1
a few days in a yield of 43.3 %. m.p. 106-107 ºC; H NMR
(500 MHz, DMSO-d6): δ (ppm) = 3.52 (t, 4H, J = 6.3Hz, -N-
CH2), 3.96 (t, 4H, J = 5.8 Hz, -O-CH2), 4.62 (s, 4H, -NH2),
6.47-6.56 (m, 8H, Ar-H) , 7.60-7.87 (m, 5H, Ar-H); IR (KBr,
νmax, cm-1): 3425(m), 3202(w), 1627(s), 1514(vs), 1443(s),
1295(w), 1283(w), 826(s).
Crystal structure determination: The X-ray data were
collected on a Bruker Apex-II CCD diffractometer using
graphite monochromated MoKα radiation (λ = 0.71073 Å) at
293 (2) K with crystal size 0.11 mm × 0.14 mm × 0.15 mm. A
total of 7757 (Rint = 0.0816) independent reflections were
collected by ö and ù scans technique in the range of 0.909 ≤ θ
≤ 26.04º from which 5198 [I > 2σ(I)] reflection were corrected
for Lorentz and polarization factors. The structure was solved
by direct method and refined using a full-matrix least-squares
procedure on F2 in SHELXS-97.All non-hydrogen atoms were
Fig. 1. Molecular structure of compound 4
TABLE-1
SELECTED BOND DISTANCES (Å) AND ANGLES (º)
S(1)-N(1)
C(1)-N(1)
C(9)-N(1)
S(1)-O(3)
S(1)-O(4)
C(2)-O(1)
1.626(2)
1.483(3)
1.473(3)
1.4344(19)
1.436(2)
1.428(3)
C(10)-O(2)
C(3)-O(1)
C(11)-O(2)
C(6)-N(2)
C(14)-N(3)
C(1)-C(2)
1.434(3)
1.389(3)
1.386(3)
1.400(4)
1.405(4)
1.503(4)
N(1)- S(1)-C(17)
N(1)- S(1)-O(3)
N(1)- S(1)-O(4)
C(2)- O(1)-C(3)
C(10)-O(2)-C(11)
N(1)-C(1)-C(2)
108.19(11)
107.03(11)
107.20(11)
116.79(19)
117.90(19)
112.4(2)
TABLE-2
HYDROGEN BOND DISTANCES (Å) AND ANGLES (º)
Type (D-H···A)
d (D-H)
d (H···A)
d (D···A)
Symmetry codes
∠(DHA)
168.00
172.00
161.00
159.00
102.00
106.00
108.00
121.00
105.00
N(2)-H(2D)···N(3)
N(3)-H(3B)···O(3)
N(5)-H(5B)···N(6)
N(6)-H(6A)···O(8)
C(9)-H(9B)···O(3)
C(18)-H(18)···O(3)
C(23)-H(23A)···O(7)
C(23)-H(23B)···O(6)
C(44)-H(44)···O(8)
0.8600
0.8600
0.8600
0.8600
0.9700
0.9300
0.9700
0.9700
0.9300
2.3900
2.2700
2.3600
2.3400
2.5400
2.4900
2.4500
2.4700
2.5200
3.240(4)
3.124(3)
3.187(4)
3.160(3)
2.905(4)
2.886(4)
2.903(3)
3.086(3)
2.896(3)
x, 1 + y, z
3/2-x, -1/2 + y, 1/2-z
x, 1 + y, z
1/2-x, -1/2 + y, 1/2-z
x, y, z
x, y, z
x, y, z
x, y, z
x, y, z

2856 Jiang et al.
Asian J. Chem.
In compound 4, the three phenyl rings possess different
ACKNOWLEDGEMENTS
orientations, with the bond angles of N(1)-S(1)-C(17), N(1)-
C(1)-C(2), N(1)-C(9)-C(10) are 108.19 (11), 112.4 (2), 115.4
(2)º, respectively. Five intramolecular C-H···O hydrogen
bondings and few intermolecular N-H···N as well as N-H···O
hydrogen bondings are involved in the structure to stabilize
the crystal. Furthermore, intramolecular π-π stacking inter-
actions have been found in the structure, with the distance of
Cg2···Cg3 is 3.956 (3) Å, where Cg is the corresponding phenyl
ring defined by C(11)-C(16) and C(17)-C(22) atoms.
The authors gratefully acknowledged the financial support
from the Foundation of Guizhou Province China (No. [2012]
2153).
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Conclusion
A new binary aromatic amine, N,N-bis[(4-aminophenoxy)-
ethyl]benzene sulfonamide, has been prepared by the method
of hydration hydrazine reduction and characterized by the
1
means of IR, H NMR and single crystal X-ray diffraction
analysis. Intramolecular and intermolecular hydrogen bondings
as well as π-π stacking interactions are involved in the structure
to stabilize the crystal. The new compound not only enriches
the family members of aromatic amines, but also has promising
applications in chemical industries.
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Supplementary material
Crystallographic data for the structure reported in this
paper have been deposited with the Cambridge Crystallo-
graphic Data Center as supplementary publication No. CCDC
936538.