One-step synthesis of 6-acetamido-3-(N-(2-(dimethylamino) ethyl) sulfamoyl) naphthalene-1-yl 7-acetamido-4-hydroxynaphthalene-2-sulfonate and its characterization with 1D and 2D NMR techniques

Article abstract of DOI:10.1002/mrc.3955

A one-step method was reported for the synthesis of 6-acetamido-3-(N-(2- (dimethylamino) ethyl) sulfamoyl) naphthalene-1-yl 7-acetamido-4- hydroxynaphthalene-2-sulfonate by treating 7-acetamido-4-hydroxy-2- naphthalenesulfonyl chloride with equal moles of N, N-dimethylethylenediamine in acetonitrile in the presence of K₂CO₃. The chemical structure of the obtained compounds was characterized by MS, FTIR, ¹H NMR, ¹³C NMR, gCOSY, TOCSY, gHSQC, and gHMBC. The chemical shift differences of ¹H and ¹³C being δ 0.04 and 0.2, respectively, were unambiguously differentiated. Copyright 2013 John Wiley & Sons, Ltd. 6-Acetamido-3-(N-(2-(dimethylamino) ethyl) sulfamoyl) naphthalene-1-yl 7-acetamido-4-hydroxynaphthalene-2-sulfonate was prepared by a one-step method. The structure of the compound was elucidated by 1D and 2D NMR. The chemical shift differences of ¹H and ¹³C being δ 0.04 and 0.2, respectively, were unambiguously differentiated. Copyright

Full text of DOI:10.1002/mrc.3955

MRC Letters
Received: 24 February 2013
Revised: 21 March 2013
Accepted: 22 March 2013
Published online in Wiley Online Library: 29 April 2013
(wileyonlinelibrary.com) DOI 10.1002/mrc.3955
One-step synthesis of 6-acetamido-3-(N-(2-
dimethylamino) ethyl) sulfamoyl) naphthalene-
-yl 7-acetamido-4-hydroxynaphthalene-2-
(
1
sulfonate and its characterization with 1D
and 2D NMR techniques
Wei Zhang*
A one-step method was reported for the synthesis of 6-acetamido-3-(N-(2-(dimethylamino) ethyl) sulfamoyl) naphthalene-1-yl 7-
acetamido-4-hydroxynaphthalene-2-sulfonate by treating 7-acetamido-4-hydroxy-2-naphthalenesulfonyl chloride with equal
moles of N, N-dimethylethylenediamine in acetonitrile in the presence of K
2
CO
3
. The chemical structure of the obtained com-
1
13
pounds was characterized by MS, FTIR, H NMR, C NMR, gCOSY, TOCSY, gHSQC, and gHMBC. The chemical shift differences of
1
13
H and C being d 0.04 and 0.2, respectively, were unambiguously differentiated. Copyright © 2013 John Wiley & Sons, Ltd.
1
13
Keywords: NMR; H NMR; C NMR; 2D NMR; synthesis
Introduction
Experimental
Owing to the distinct features of fabric and dyestuff, for any given
Materials and apparatus
[
1]
fabric, only limited types of dyestuffs are applicable. If one dye
can be used to color all types of fabrics, both the dyeing process
and effluent treatment can be simplified. As the residual dye bath
may be reused, the amount of dyeing effluent can be reduced as
well. Apparently, all of these will lower the dyeing costs and pro-
vide environmental advantages. However, the proof of concept
of universal dye is in its infancy, and the development of novel
All chemical reagents were the commercial products of analytical
grade. The mass spectra were obtained on an HP 1100 System of
HPLC/MSD or HP6890 Series GC System/5973 Mass Select Detec-
tor (Hewlett Packard Ltd. Co., Palo Alto, CA, USA). The IR spectra
(the sample was made into KBr wafer) were recorded with an FTIR
430 infrared spectrophotometer (JASCO Ltd. Co., Tokyo, Japan).
Varian INOVA 400 MHz NMR spectrometer (Varian, Palo Alto, CA,
USA) was used for the characterization of sulfonate III in deuter-
[
2–5]
universal dyes is high desirable.
Herein, we design a new uni-
versal dye precursor, 6-acetamido-3-(N-(2-(dimethylamino) ethyl)
sulfamoyl) naphthalene-1-yl 7-acetamido-4-hydroxynaphthalene-
ated dimethyl sulfoxide (~0.1 mol in concentration). The TMS
1
(
d 0.00) was used as chemical shift reference. H NMR spectrum
2
-sulfonate (III) (Scheme 1); the structure of which has several
was operated at 399.715 MHz with 10 000 Hz spectral width,
characteristics. (i) A naphthalene sulfonamide moiety is included,
ꢀ
ꢀ
flip angle 30 , and recycle time 7 s, and determined at 40 C.
which is thought to be beneficial for the improvement of
13
ꢀ
C NMR spectrum was performed at 100.518 MHz and 40 C with
Waltz proton decoupling, flip angle 30 , spectral width 22 000 Hz,
[
6]
sublimation fastness of dye on fabrics. (ii) Two naphthalene
rings are presented, which may increase the substantivity of
ꢀ
recycle time 6.2 s, and accumulation 1600 times. The gCOSY and
TOCSY experiments were run at 5911Hz spectral width, zero filling
to 4096 Â 4096 data matrix, relaxation delay 1 s, and acquisition
time 0.167 s. The gHSQC and gHMBC were recorded at spectral
[7]
dye to fibers. (iii) A tertiary amine group is incorporated, which
means this structure has the potential to be used as the precursor
[8]
for cationic dyes.
Conventionally, III can be synthesized by two steps: the
1
13
widths of 4650 Hz for H and 21894 Hz for C, zero filling to
condensation of 7-acetamido-4-hydroxy-2-naphthalenesulfonyl
2
048 Â 4096 data matrix, relaxation delay 1 s, and 32 repetitions.
[
9]
chloride (II) with N,N-dimethylethylene-diamine and followed
by the esterfication of hydroxyl group using excessive sulfonyl
chloride (II) in high boiling point solvents such as N,N-
dimethylformamide, N,N-dimethylacetamide, and 1-methyl-2-
pyrrolidone in the presence of a base, for instance, triethylamine
A sinbell window function was used prior to Fourier transformation.
* Correspondence to: Wei Zhang, State Key Laboratory of Structural Analysis for
Industrial Equipment, Faculty of Vehicle Engineering and Mechanics, Dalian
University of Technology, Dalian 116024, China. E-mail: wei.zhang@dlut.edu.cn
[
10–12]
and pyridine.
applied to synthesize III by the condensation of sulfonyl chloride
II) with equal moles of N,N-dimethylethylenediamine in acetoni-
trile in the presence of K CO , and the structure of III was
In this study, a one-step approach was
(
State Key Laboratory of Structural Analysis for Industrial Equipment, Faculty of
Vehicle Engineering and Mechanics, Dalian University of Technology, Dalian
116024, China
2
3
1
13
unambiguously confirmed by H and C NMR.
Magn. Reson. Chem. 2013, 51, 431–434
Copyright © 2013 John Wiley & Sons, Ltd.

W. Zhang
Scheme 1. Synthesis route for 6-acetamido-3-(N-(2-(dimethylamino) ethyl) sulfamoyl) naphthalene-1-yl 7-acetamido-4-hydroxynaphthalene-2-
sulfonate (III).
Synthesis of III
atom and the naphthalene ring. As a hydroxyl group is present
in the ortho-position of H2, its chemical shift should appear in a
higher field (d 7.09), whereas as a strong electron-withdrawing
Scheme 1 illustrates the synthesis route for III.
Synthesis of N,N-dimethylethylenediamine
2
group sulphonyl (–SO –) is present in the ortho-position of H15,
its chemical shift should appear in a lower field (d 7.44).
The gCOSY spectrum indicates the coupling interactions
between H2 and H4 and between H15 and H17; consequently,
chemical shifts d 7.90 and 8.20 are assigned to H4 and H17,
respectively. The gCOSY spectrum also suggests the coupling
interactions among H5, H7, and H8 and among H18, H20, and
H21, although it is not possible to assign the accurate chemical
shift to individual H.
N,N-Dimethylethylenediamine was synthesized using ethanol
[13]
amine in accordance with references, as illustrated in Scheme 2.
ꢀ
Boiling point: 97–102 C. GS/MS: m/z (relative intensity) 58 (100%),
+
42(25%), 30(23%), 88(M , 6%); relative purity: 89. 2%.
Synthesis of sulfonyl chloride (II)
To the mixture of 5.4 g I, 6.6 ml N,N-dimethylacetamide, and 28 ml
acetonitrile, 4.9ml phosphorus oxychloride was added. The
resulting mixture was stirred at 55–60 C for 4 h and poured into
The TOCSY spectrum demonstrates a weak connectivity
between H4 and H5 and between H17 and H18; consequently,
the chemical shifts d 8.32 and 8.45 are assigned to H5 and H18,
respectively. Then, in reference to gCOSY, chemical shifts d 7.73
and 8.11 are assigned to H7 and H8, respectively; chemical shifts
d 7.67 and 7.88 are assigned to H20 and H21, respectively.
The assignment of H NMR signals of III was further completed
with gHMBC and gHSQC. It is worth noting that the difference in
chemical shifts between H11 and H29 is fairly marginal, only d 0.04
ꢀ
cold water. II was collected by filtration with a yield of 92%. TLC:
Rf = 0.86 (EtOAc/HOAc/EtOH, 4 : 1 : 3). The structure of II was
confirmed by the comparison of its IR spectrum with standard IR
spectrum of I. The main absorption bands of I appear at
À1
À1
À1
1
3
480 cm (–SO
2
–OH), 3387 cm (–NH–), and 1672 cm (–CO).
À1
À1
The main absorption peaks of II (cm ) are present at 3383 cm
–NH–), 1677 cm (–CO), 1358 cm (–SO), and 1167 cm (–SO).
À1
À1
À1
(
(
d 12.30, 12.26), which suggests the complexity in assigning the
Synthesis of III
NMR resonance signals. GHMBC indicates the connectivity among
H11 and C5, C6, C7, C12; thus, the chemical shift d 10.26 is assigned
to H11. As H29 and C18, C19, C20, C30 are also coupling related in
gHMBC, the chemical shift d 10.30 is assigned to H29. Concurrently,
the assignment of C NMR signals could be completed, and this in
turn supports the assignment of H NMR signals. Strikingly, d 169.1
A suspension of 2.0 g II in 40 ml acetonitrile was added dropwise
into 0.6 g N,N-dimethylethylenediamine, 1.0 g K CO , and 30 ml
2
ꢀ
3
acetonitrile. This mixture was stirred at 35–40 C for 4 h and
refluxed for further 2 h. After extraction with ethyl acetate and re-
crystallization from acetonitrile, III was obtained in white color
with a yield of 36.2%. Mass spectral analysis (Atmospheric Pres-
sure Ionization-Electrospray Ionization positive): m/z 615.1
13
1
and 168.9 are assigned unambiguously to C12 and C30, respectively;
the difference in chemical shifts is only d 0.2.
+
+
1
13
(
[M + H] , 66.9%), 637.1 ([M + Na] , 100%).
In essence, the H and C NMR signals of III were assigned,
1
1
and the H– H coupling constants are listed in Table 1.
Results and Discussion
Conclusions
Because of the analogy of the substituted groups and their posi-
tions on the two naphthalene rings, it is impossible to elucidate
the structure of III solely by its MS, 1D H NMR, and 1D
NMR spectra. The assignments of the resonances to individual
protons and carbons are based on 2D NMR spectra including
gCOSY, TOCSY, gHSQC, and gHMBC.
Compared with other aromatic hydrogens, the resonance
signals of H2 and H15 should appear in a higher field because
of the p–p conjugation interactions between the ortho-oxygen
A convenient approach was developed to prepare 6-acetamido-3-
(N-(2-(dimethylamino) ethyl) sulfamoyl) naphthalene-1-yl 7-
acetamido-4-hydroxynaphthalene-2-sulfonate, through which the
condensation of sulfonyl chloride with N,N-dimethylethylenediamine
and the condensation of naphtholic hydrogen with sulfonyl chloride
take place concurrently. The H and C NMR spectra were
interpreted unambiguously, and the H– H coupling constants and
the chemical shifts of H and C were reported for the first time.
1
13
C
1
13
1
1
1
13
Scheme 2. Synthesis route for N,N-dimethylethylenediamine.
wileyonlinelibrary.com/journal/mrc
Copyright © 2013 John Wiley & Sons, Ltd.
Magn. Reson. Chem. 2013, 51, 431–434

1
D and 2D NMR techniques, m-naphtholic sulfonyloxy-naphthalene sulfonamide derivative
Table 1. NMR data of 6-acetamido-3-(N-(2-(dimethylamino) ethyl) sulfamoyl) naphthalene-1-yl 7-acetamido-4-hydroxynaphthalene-2-sulfonate (III)
1
1
1
No.
d
H
d
C
H– H coupling
TOCSY
gCOSY
gHSQC J(C,H)
gHMBC
constants (Hz)
cross signal
cross signal
2
1
/
154.9
/
/
/
/
2[ J(C,H)]
3
8
[ J(C,H)]
4
3
2
3
7.09
/
102.4
131.9
J(H
2
,H
/
4
):1.4
2,4,5,7,8
/
2,4
/
+
/
4[ J(C,H)]
2
2[ J(C,H)]
2
4
[ J(C,H)]
4
4
3
4
5
7.90
8.32
120.0
115.9
J(H
J(H
2
,H
,H
4
7
):1.4
):1.5
2,4,5,7,8
2,4,5,7,8
2,4
5,7
+
+
2[ J(C,H)]
3
5
4[ J(C,H)]
3
7
[ J(C,H)]
3
1
1[ J(C,H)]
2
6
7
/
139.1
122.3
/
/
/
/
5[ J(C,H)]
3
8
[ J(C,H)]
2
1
1[ J(C,H)]
a
4
3
7.73
J(H
5
,H
7
):1.5
2,4,5,7,8
5,7 7,8
+
5[ J(C,H)]
3
3
J(H
J(H
7
,H
,H
/
8
8
): 9.1
): 9.1
11[ J(C,H)]
3
2
8
9
8.11
/
123.2
123.4
7
2,4,5,7,8
/
7,8
/
+
/
7[ J(C,H)]
3
2[ J(C,H)]
3
4
5
7
[ J(C,H)]
3
[ J(C,H)]
3
[ J(C,H)]
3
1
1
1
0
1
2
/
133.6
/
/
/
/
/
/
/
/
/
/
/
/
/
8[ J(C,H)]
10.26
/
/
2
168.9
11[ J(C,H)]
2
1
3[ J(C,H)]
a
1
3
4
2.09
/
24.1
/
/
/
/
/
/
+
/
/
2
1
145.4
15[ J(C,H)]
4
1
2
7[ J(C,H)]
3
1[ J(C,H)]
4
3
1
1
5
6
7.44
/
112.9
138.0
J(H15,H17):1.3
15,17,18,20,21
/
15,17
/
+
/
17[ J(C,H)]
2
/
15[ J(C,H)]
2
1
7[ J(C,H)]
4
4
3
1
1
7
8
8.20
8.45
125.6
115.6
J(H15,H17):1.3
J(H18,H20):1.4
15,17,18,20,21
15,17,18,20,21
15,17
+
+
15[ J(C,H)]
3
1
8[ J(C,H)]
3
17,18,20
17[ J(C,H)]
3
2
2
0[ J(C,H)]
3
9[ J(C,H)]
2
1
2
9
0
/
139.1
123.0
/
/
/
/
18[ J(C,H)]
3
2
2
1[ J(C,H)]
2
9[ J(C,H)]
4
3
3
3
7.67
J(H18,H20):1.4
J(H20,H21):9.1
J(H20,H21):9.1
/
15,17,18,20,21
18,20 20,21
+
18[ J(C,H)]
3
29[ J(C,H)]
a
2
2
2
1
2
7.88
/
122.2
123.9
15,17,18,20,21
/
20,21
/
+
/
20[ J(C,H)]
3
15[ J(C,H)]
3
1
1
2
7[ J(C,H)]
3
8[ J(C,H)]
3
0[ J(C,H)]
2
2
3
/
133.9
/
/
/
/
17[ J(C,H)]
3
2
1[ J(C,H)]
3
3
2
2
2
5
6
2.69
2.16
40.5
57.9
J(H25,H26):6.6
J(H25,H26):6.6
26
25
25,26
26,25
+
+
26[ J(C,H)]
2
25[ J(C,H)]
3
2
2
7[ J(C,H)]
3
8[ J(C,H)]
3
2
2
2
7
8
9
2.01
2.01
44.8
44.8
/
/
/
/
/
/
/
/
/
/
+
+
/
26[ J(C,H)]
3
2
7[ J(C,H)]
3
26[ J(C,H)]
3
2
7[ J(C,H)]
10.30
/
(Continues)
Magn. Reson. Chem. 2013, 51, 431–434
Copyright © 2013 John Wiley & Sons, Ltd.
wileyonlinelibrary.com/journal/mrc

W. Zhang
Table 1. (Continued)
No.
1
1
1
d
H
d
C
H– H coupling
TOCSY
gCOSY
gHSQC J(C,H)
gHMBC
constants (Hz)
cross signal
cross signal
2
3
0
/
169.1
24.1
/
/
/
/
/
/
29[ J(C,H)]
2
3
1[ J(C,H)]
a
3
1
2.10
/
+
/
a
These peaks are assigned tentatively.
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Acknowledgements
1
The National Natural Science Foundation of China (51105051)
and the Fundamental Research Funds for the Central Universities
of China (DUT11RC(3)79) were acknowledged for the financial
support.
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Copyright © 2013 John Wiley & Sons, Ltd.
Magn. Reson. Chem. 2013, 51, 431–434