The synthesis and crystal structure of 5-(4-bromophenylamino)-2- methylsulfanylmethyl-2H-1,2,3-triazol-4-carboxylic acid ethyl ester

Article abstract of DOI:10.1007/s10870-008-9425-8

The 5-(4-bromophenylamino)-2-methylsulfanylmethyl-2H-1,2,3-triazol-4- carboxylic acid ethyl ester 6 was synthesized from p-bromoaniline. The yielded product 6 was investigated with X-ray crystallographic, NMR, MS, and IR techniques. Compound 6, C₁₃

Full text of DOI:10.1007/s10870-008-9425-8

J Chem Crystallogr (2009) 39:95–98
DOI 10.1007/s10870-008-9425-8
ORIGINAL PAPER
The Synthesis and Crystal Structure of 5-(4-Bromophenylamino)-
2-methylsulfanylmethyl-2H-1,2,3-triazol-4-carboxylic Acid Ethyl
Ester
Bin Wang Æ Heng-Shan Dong
Received: 21 July 2006 / Accepted: 4 June 2008 / Published online: 21 June 2008
Ó Springer Science+Business Media, LLC 2008
Abstract The 5-(4-bromophenylamino)-2-methylsulfanyl-
methyl-2H-1,2,3-triazol-4-carboxylic acid ethyl ester 6 was
synthesized from p-bromoaniline. The yielded product 6
was investigated with X-ray crystallographic, NMR, MS,
and IR techniques. Compound 6, C13H15BrN4O2S, Mr =
371.26, crystallizes in the monoclinic space group P21/n
1,2,3-triazole derivatives had been synthesized which
inhibit tumor proliferation, invasion and metastasis [5], and
anti-HIV [6, 7] properties. The 1,2,3-triazole compounds
containing sulfur have been found to possess to a moderate
degree fungicidal activity and better pesticidal activities
[8]. The synthetic route for the intriguing reaction between
1,2,3-triazole and dimethylsulfoxide (DMSO) is shown in
Scheme 1.
with unit cell parameters a = 5.5220(1), b = 26.996(5),
3
˚
˚
c = 10.596(2) A, b = 103.83(3). V = 1533.8(5) A , Z = 4,
Dx = 1.608 mg m-3. The final R1 was 0.0844; wR2 was
0.1560. H-bond is discussed.
Experimental Section
Keywords Crystal structure ꢀ DMSO ꢀ Synthesis ꢀ
2H-1,2,3-triazole ꢀ H-bond ꢀ Dimroth rearrangements ꢀ
2-Methylsulfanylmethyl-2H-1,2,3-triazol-4-carboxylic
acid ethyl ester
All melting points were uncorrected and determined on an
XT4-100x microscopic melting point apparatus. IR spectra
were obtained in KBr disks on a Nicolet NEXUS 670 FT-IR
spectrometer. MS were performed on a HP-5988A spec-
trometer (EI at 70 eV). 1H-NMR spectroscopy (CDCl3) was
recorded on Varian Mercury plus-300 instrument with TMS
as an internal standard. Elemental analyses were carried out
on a Yanaco CHN Corder MT-3 analyzer.
Introduction
In recent years, the thio-function group compounds of
1,2,3-triazole derivatives have been attracting the attention
of chemists and pharmacologists. Certain compounds
having the 1,2,3-triazole nucleus have been reported as
having antibacterial [1], antifungal [2], antiviral [3], anti-
inflammatory, and analgesic [4] properties. Recently, some
2.1 5-Amino-1-(4-bromophenyl)-1,2,3-triazol-4-carbox-
ylic acid ethyl ester 4 was prepared following methods in
the literature [1, 8], m.p. 168–169 °C.
2.2 Procedure of preparation of 5-(4-bromophenylami-
no)-2-methylsulfanylmethyl-2H-1,2,3-triazol-4-carboxylic
acid ethyl ester 6.
A mixture of 5-amino-1-(4-bromophenyl)-1,2,3-triazol-
4-caroxylic acid ethyl ester 4 (0.5 g) and dimethyl sulfoxide
(DMSO) 6.0 mL was heated under 140–150 °C for 10 hwith
stirring. The cooled reaction mixture was poured into 60 mL
water and the thick and cloudy liquor was extracted with
ethyl ether (20 9 5 mL) and then the resulting solution was
dried with anhydrous sodium sulfate for 4 h. The sodium
sulfate was removed by filtration. The extraction solution
was concentrated. The solid was purified by chromatography
B. Wang ꢀ H.-S. Dong (&)
State Key Laboratory of Applied Organic Chemistry, Institute of
Organic Chemistry, College of Chemistry and Chemical
Engineering, Lanzhou University, Lanzhou, Gansu 730000,
People’s Republic of China
e-mail: donghengshan@lzu.edu.cn
B. Wang
College of Science and Engineering, Gansu Association
University, Lanzhou, Gansu 730000, China
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J Chem Crystallogr (2009) 39:95–98
N2+Cl-
Table 1 Crystal data and structure refinement details
NH2
N3
NaN3
0-5°C
Empirical formula
CCDC deposit number
Formula weight
C13H15BrN4O2S
286960
NaNO2,HCl
0-5°C
371.26
Temperature, K
293(2)
Br
1
Br
2
Br
3
˚
Wavelength, A
0.71073
Reflections for cell determination
2h range for above
Crystal system
25
COOC2H5
NH2
10–20°
Monoclinic
N
N
CNCH2COOC2H5
NaOEt, HOEt
Space group
P21/n
N
DMSO
Cell dimensions
a = 5.5220(1)
b = 26.996(5)
140-150°C
˚
c = 10.596(2) A
Br
4
b = 103.83(3)
1533.8(5)
4
3
˚
Volume, A
O
COOC2H5
S
H3C
Z
N
N
H2C
Density (calculated), mg m-3
Absorption coefficient, mm-1
Diffractometer/scan
1.608
N
N
OCH2CH3
N
NH
N
H
2.826
+
HN
Enraf-Nonius
CAD-4 x/2h
752.0
Br
Br
5
F(000)
6
h range for data collection, degree
0.98–24.98
0 B h B 6;
0 B k B 32;
-12 B l B 12
2,664
Scheme 1 The synthesis route of compound 6
Index ranges
on a column of silica gel, was eluted successively with 1:8
ethyl acetate–petroleum ether to give white blocks of com-
pound 5, yield 30.5%, m.p. 164–165 °C. 1H-NMR: 7.932(s,
1H,–NH–), 7.508–7.533(d, 2H, J = 7.5HZ, Ar-3,5), 7.320–
7.345(d, 2H, J = 7.5HZ, Ar-2,6), 7.007(s, 1H, triazole ring-
Reflections collected
Independent reflection
Data/restrains/parameters
Extinction coefficient
Goodness-of-fit on F2
Final R indices [I [ 2r(I)]
1,890
2,664/0/191
0.0000(2)
1.084
H), 4.471–4.533(q, 2H, J = 6.9HZ, OCH2–), 1.444–1.477(t,
ꢀ
3H, J = 6.9HZ, –OCH2CH3). MS m/z: 312(M , 56), 282(3),
þ
R1 = 0.0488,
wR2 = 0.1275
R1 = 0.0844,
wR2 = 0.1560
266(7), 238(2), 209(4), 198(3), 185(100), 171(4), 157(27),
149(13), 130(55), 117(3), 102(21), 91(7), 83(12), 76(23),
69(10), 63(8), 57(10), 50(14), 44(29). IR: 3378, 3164, 3070,
2996, 2929, 1699, 1610, 1571, 1490, 1464, 1400, 1346, 1315,
1274, 1216, 1176, 1113, 1076, 1015, 987, 909, 882, 844, 812,
783, 669, 552, 495. White needles of compound 6, yield
R indices
-3
˚
0.747 and -0.636 eA
Largest different peak and hole
1
62.5%, m.p. 102–103 °C. H-NMR: 8.084(s, 1H, –NH–),
7.476–7.492(d, 2H, J = 4.8HZ, Ar-3,5), 7.318–7.334(d, 2H,
Single crystals were selected and mounted on the tip of a
glass fiber. Preliminary examination and data collection
J = 4.8HZ, Ar-2,6), 5.441(s, 2H, –CH2S–), 4.500–4.571(q,
2H, J = 7.2 Hz, –OCH2–), 2.391(s, 3H, –SCH3), 1.481–
ꢀ
1.529(t, 3H, J = 7.2 Hz, –OCH2CH3). MS m/z: 372(M ,
˚
were performed with MoKa radiation (k = 0.71073 A) on
þ
an Enraf-Nonius CAD4 computer controlled kappa axis
diffractometer operating in the x/2h scanning mode. The
structure was determined by direct methods (SHELXS-86)
and refined by full covariance matrix methods (SHELXL-
97). The crystal data and the refinement details are given in
Table 1.
25), 340(53), 325(14), 297(11), 267(1), 251(17), 223(11),
213(100), 196(26), 182(16), 172(46), 157(33), 145(18),
130(26), 117(8), 102(21), 90(13), 76(23), 61(50), 50(8),
43(6). IR: 3358, 3192, 3087, 2999, 2938, 2914, 1691, 1603,
1566, 1523, 1471, 1407, 1371, 1349, 1304, 1259, 1144, 1114,
1075, 1024, 998, 964, 908, 811, 783, 745, 693, 668, 646, 588,
502.
The structure of the title compound is shown in
Fig. 1. The selected bond lengths are given in Table 2,
selected bond angles are given in Table 3. The geo-
metric calculations were performed using the program
SHELX-97.
The purified product was dissolved in ethyl acetate and
petroleum ether solvent. The crystal was obtained after
7 days by evaporation of the solvent.
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J Chem Crystallogr (2009) 39:95–98
97
C6
C12
C13
O2
C7
Br1
C11
C5
C8
N4
C3
O1
C4
C10
C9
N3
N1
N2
C2
C1
S1
Fig. 1 ORTEP drawing of the title compound 6 showing the atom
numbering scheme (Ellipsoids: 50% probability)
Fig. 2 The H-bond structure of the compound 6 (PWT drawing for
the Platon)
˚
Table 2 All non-hydrogen bond lengths (A)
Results and Discussion
Atoms
Length
Atoms
Length
The structure of the title compound is shown in Fig. 1. In
recent years, the synthesis and characteristics of s-triazol-
o[3,4-b]-1,3,4-thiadiazoles have been investigated [9].
These heterocyclic compounds contain 1,2,3-triazole, 1,2,
4-triazole, and 1,3,4-thiadiazole rings condensed through a
C–N bond. In a continuation of our earlier studies [10], we
now report the crystal structure of 5-(4-bromophenylami-
no)-2-methylsulfanylmethyl-2H-1,2,3-triazol-4-carboxylic
acid ethyl ester 6.
S1–C1
S1–C2
O1–C5
O1–C6
O2–C5
N1–C3
N1–N2
N2–N3
N2–C2
N3–C4
N4–C3
1.788(6)
1.798(6)
1.321(6)
1.450(6)
1.216(6)
1.330(6)
1.354(5)
1.304(6)
1.443(6)
1.343(6)
1.367(6)
N4–C8
1.377(6)
1.894(5)
1.409(7)
1.453(7)
1.480(8)
1.390(6)
1.396(6)
1.370(7)
1.374(7)
1.376(7)
1.374(7)
Br1–C11
C3–C4
C4–C5
C6–C7
C8–C13
C8–C9
C9–C10
C10–C11
C11–C12
C12–C13
Compound 5 is obtained by Dimroth rearrangements.
5-Amino-1-(4-bromophenyl)-1,2,3-triazol-4-caroxylic acid
ethyl ester 4 rearrange into ethyl 5-(4-bromophenylamino)-
1H-1,2,3-triazole-4-carboxyate 5 when heated in DMSO.
Then the reaction of compound 5 with DMSO gives title
compound 6.
Table 3 All non-hydrogen bond angles (8)
Atoms
Angle
Atoms
Angle
The 2H-1,2,3-triazole ring system is planar. The bond
˚
lengths N1–N2 1.354(5), N2–N3 1.304(6) A are in agree-
˚
ment with values reported for triazole, N–N 1.352 A by
C1–S1–C2
C5–O1–C6
C3–N1–N2
N3–N2–N1
N3–N2–C2
N1–N2–C2
N2–N3–C4
C3–N4–C8
N2–C2–S1
N1–C3–N4
N1–C3–C4
N4–C3–C4
N3–C4–C3
N3–C4–C5
C3–C4–C5
100.1(3)
115.4(4)
102.9(4)
116.0(4)
123.4(4)
120.5(4)
104.2(4)
130.0(4)
113.4(4)
125.7(4)
109.0(4)
125.4(4)
107.9(4)
124.8(4)
126.9(4)
O2–C5–O1
124.7(5)
121.2(4)
114.1(4)
108.1(5)
117.5(4)
124.4(4)
118.0(4)
120.2(4)
120.8(5)
120.1(4)
120.0(4)
119.9(4)
119.4(4)
121.5(4)
O2–C5–C4
earlier studies [11]. The bond lengths for C3–N1 and C4–
˚
O1–C5–C4
˚
N3, 1.330(6) A and 1.343(6) A, respectively, are between
those expected for C=N and C–N.
O1–C6–C7
N4–C8–C13
N4–C8–C9
In the crystal structure, there is an intramolecular N4–
H(4)_O2 hydrogen bond involving the C=O O2 atom and
the 5 position N–H. The molecular conformation and
packing are stabilized by intramolecular N4–H(4)_O2
interactions. The bond length of Donor-H_Acceptor is
C13–C8–C9
C10–C9–C8
C9–C10–C11
C10–C11–C12
C10–C11–Br1
C12–C11–Br1
C13–C12–C11
C12–C13–C8
˚
˚
2.88A (N–H 0.90; H_O2 2.22A), the bond angle is 130°.
The H-bond structure of the compound 6 is shown in
Fig. 2.
Acknowledgments The authors wish to acknowledge this project is
supported by Lanzhou University SKLAOC.
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J Chem Crystallogr (2009) 39:95–98
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