Mono- and diiodo-1,2,3-triazoles and their mono nitro derivatives

Article abstract of DOI:10.1039/c6dt01731b

4-Iodo-1H-1,2,3-triazole (2) and 4,5-diiodo-1H-1,2,3-triazole (3) were synthesized using an efficient and viable synthetic route. The N-alkylation of 3 resulted in the formation of two tautomers. The N-alkyl-diiodo-triazoles were nitrated with 100% nitric

Full text of DOI:10.1039/c6dt01731b

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Mono‐ and Diiodo‐1,2,3‐Triazoles and Their Mono Nitro
Derivatives
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
b
c
d
Deepak Chand , Chunlin He , Joseph P. Hooper , Lauren A. Mitchell , Damon A. Parrish , and
*
a
Jean’ne M. Shreeve
DOI: 10.1039/x0xx00000x
4‐Iodo‐1H‐1,2,3‐triazole (2) and 4, 5‐diiodo‐1H‐1,2,3‐triazole (3) were synthesized using an efficient and viable synthetic
www.rsc.org/
route. The N‐alkylation of 3 resulted in the formation of two tautomers. The N‐alkyl‐diiodo‐triazoles were nitrated with
1
00% nitric acid to form monoiodo‐mononitro‐triazoles. The structures of 2‐methyl‐4,5‐diiodo‐1,2,3‐triazole (5), 1‐ethyl‐
,5‐diiodo‐1,2,3‐triazole (6), 1‐methyl‐4‐nitro‐5‐iodo‐1,2,3‐triazole (8) and 1‐ethyl‐4‐nitro‐5‐iodo‐1,2,3‐triazole (10) were
4
confirmed by X‐ray crystal analysis. All of the new triazoles were fully characterized via NMR, and infrared spectra, and
elemental analyses as well as by their thermal and sensitivity properties. Decomposition products calculated using
Cheetah
7
software
show
that
these
iodo‐nitro
triazoles
liberate
iodine.
alkylation reactions were successful. The resulting N-alkyl
triazoles are tautomeric, and can be nitrated using 100% nitric
acid. Gaussian 03 calculations were employed to predict the
heat of formation values which were used as input parameters
for Cheetah 7 calculations to obtain detonation properties and
decomposition products.
Introduction
Iodine has been used as a powerful disinfectant for over 100
years. When in contact with micro-organisms such as bacteria,
viruses, fungi and protozoa, iodine is able to rapidly penetrate
cell walls and oxidise a number of critical components within
the cell. The combined effect of these oxidative reactions is cell
death. In aqueous solution, iodine is found as four principal
Results and discussion
2 3
), hypoiodous acid (HIO), triiodide (I
-) and
forms: iodine (I
iodate (IO -). Both I
3
2
and HIO are strong antibacterial agents. Synthesis
-
-
The I
3
and IO
3
species are only present in very low
Compounds
Iodo-1,2,3-triazole (
1 – 11 were synthesized as shown in Scheme 1. 1-
concentrations and are only significant at pH greater than 8.5.1
The 1,2,3-triazole ring is a moiety present in anti-allergic,
antibacterial, antifungal, anti-virial, and analgesic drugs. Of the
two constitutional triazole isomers, 1,2,3-triazole and 1,2,4-
triazole, the latter has been extensively investigated for
) was synthesized based on the literature.4
1
3
,5-Dimethyl-1,2,4-triazole, an expensive and not readily
available reagent, has been used previously to transform
1
.5 To our delight, we found that this conversion
into
2 and 3
happens by using an inexpensive and readily available reagent,
i.e., aqueous ammonia. When 1-iodo-1,2,3-triazole was heated
in aqueous ammonia in a thick-walled-pressure tube at 100 °C
2
energetic materials applications. Likely because the syntheses
of the precursors are more difficult, there are fewer reports
dealing with similar applications of 1,2,3-triazole.3
In this work an efficient and practical synthesis for 4-iodo-
1H-1,2,3-triazole (2) and 4,5-diiodo-1H-1,2,3-triazole (3) was
for 10 – 15 min, ammonium salts of
2 and 3 were obtained.
An aqueous solution of the resulting salts, when acidified
with concentrated hydrochloric acid, formed a precipitate which
developed. A nitro functionality is helpful in enhancing the
energy content as well as to attain a better oxygen balance.
However, due to the instability of these triazoles in strongly
acidic solutions, direct nitration was not possible. Although, the
iodo triazoles are less acidic than the parent 1,2,3-triazoles, the
was isolated by filtration and identified as 3,5-diiodo-1
triazole ( ). 4-Iodo-1 -1,2,3-triazole ( ) was isolated from the
filtrate by ether extraction. Because of the low stability of and
in acidic solution, direct nitration was not possible. Low
H-1,2,3-
3
H
2
2
3
temperature alkylation of
3 was accomplished by using
potassium carbonate as base and methyl and ethyl iodides as
electrophiles. N1- and N2-alkylated products were isolated in
excellent yields. Column chromatography (ethyl acetate:
hexane) was employed to separate the resulting N-alkyl
a.
Department of Chemistry, University of Idaho, Moscow, Idaho, 83844‐2343 USA.
Department of Physics, Naval Postgraduate School, Monterey, CA 93943 USA.
Department of Chemistry, University of Minnesota, Minneapolis, MN 55455 USA.
Naval Research Laboratory, 4555 Overlook Avenue, Code 6030, Washington, D.C.
b.
c.
d.
compounds. By refluxing in 100% nitric acid, nitration of 4, 5,
2
0375‐5001, USA.
Electronic Supplementary Information (ESI) available: CCDC – 1446302, 1446304,
446331, 1446333. Isodesmic reactions; NMR, DSC and IR spectra. X‐ray diffraction
1
data. See DOI: 10.1039/x0xx00000x
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Table 1: Properties of compounds 2 ̶ 11
a]
[b]
d[c]
[gcm ]
°[d]
D[e]
[ms ]
P[f]
[GPa]
Comp
T [
[
m
T
d
ΔH
[kJ mol ]
f
ΔH
[kJ g ]
f
°
Iodine
[%]
‐
3
‐1
‐1
‐1
°C]
[°C]
2
3
4
5
6
7
8
9
110.8
‐
156.7
189.9
212.7
‐
170.9
‐
‐
235.0
253.7
‐
2.71
3.32
3.11
2.90
2.81
2.73
2.41
2.13
2.17
2.11
430.0
474.4
373.1
358.6
459.1
443.7
683.1
671.1
672.5
658.7
2.2
1.5
1.1
1.1
1.3
1.3
2.7
2.6
2.5
2.5
5112
4090
3985
3639
4066
3926
6028
5512
5710
5602
15.33
11.41
10.07
7.91
9.96
9.07
21.24
16.85
20.03
19.12
65.1
79.1
75.8
75.8
72.7
72.7
50.0
50.0
47.4
47.4
185.7
129.7
127.5
108.1
98.0
156.0
48.3
111.2
1
1
0
1
[
a] melting point; [b] decomposition temperature; [c] density ‐ gas pycnometer 25 °C ; [d] heat of formation ‐ Gaussian 03; [e] detonation
velocity ‐ Cheetah 7; [f] detonation pressure ‐ Cheetah 7.
7
6
and
Compounds
spectral analysis, DSC and elemental analysis. Single crystal
7
was successful in forming the 4-nitro products. 31+G** for first row and second row elements. Single-point
2
– 11 were fully characterized with NMR, and IR energy (SPE) refinement on the optimized geometries were
structures were obtained for 5, 6, 8 and 10.
1
) aq. NH
3
, 100 °C,
I
I
I
NaOEt, EtOH, ICl
10-15 min
2) H+
N
NH
N
N
N
NH
N
NH
N
N
I
N
N
1
2
3
I
I
O
2
N
I
1
00% HNO
3
N
N
R
N
N
N
100 °C, 6 hrs
R
N
R = Me 4
R = Et 6
R = Me
8
I
I
R = Et
10
K
2
CO
3
, DMF,
N
NH MeI or EtI, -20 °C
N
O
2
N
I
I
I
1
00% HNO
3
N
N
Figure 1. The sums of iodine‐containing species in the decomposition products of
compounds 2, 3, 4, 6, 8 and 11 (weight percent).
N
N
100 °C, 6 hrs
N
R
N
R
R = Me 9
R = Et 11
R = Me 5
R = Et 7
‐
1
Table 2. Major decomposition products ‐ Cheetah 7 calculations [wt. % kg kg ]
comp
N
2
[g]
I
2
[g]
HI [g]
C [s]
Scheme 1: Synthesis of compounds 1 ‐11
2
3
4
6
8
11
21.6
12.0
12.6
12.0
22.1
21.0
64.1
78.4
74.8
71.6
49.0
16.4
1.0
1.0
1.0
1.1
1.0
1.1
9.3
6.6
8.1
10.0
5.9
7.9
Properties of compounds
The physical properties of
2
–
11 are summarized in Table 1.
Heats of formation of all compounds were calculated with the
Gaussian 03 program suite using isodesmic reactions6
(
Electronic Supporting Information (ESI) Scheme S1). For
performed with the use of MP2/6-311++G** level.
Corresponding iodine sets were constructed in MP2 method by
using all electron calculations and quasi relativistic energy-
adjusted spin-orbit-averaged seven-valence-electron effective
core potentials (ECPs). All compounds have positive heats of
these iodine-containing compounds, the (15s, 11p, 6d) basis of
Strömberg et al. was augmented with other p shell and the five
valence sp exponents optimized resulting in a [5211111111,
4
11111111, 3111] contraction scheme in conjunction with 6-
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formation. As expected, 8, 9, 10 and 11 with nitro substituents structure analysis. There are two molecules in the unit cell in
have higher positive heats of formation. The calculated values the P-1 space group (Figure 3). Crystal units are packed so as to
for heats of formation and experimental densities were used to separate the bulky N-ethyl groups as seen in Fig. 3 (b).
predict the detonation velocities (
) using the Cheetah 7 program. All of the compounds have
low detonation pressures which range from 7.91 to 21.24 GPa
D) and detonation pressures
(
P
-
1
and a range of detonation velocities from 3639 to 6028 ms .
The decomposition products, I and HI, were predicted
using Cheetah 7. As shown in Figure 1, has the highest iodine
concentration in its decomposition products at ~79%, followed
by at 75%. Each of the isomeric N-alkyl triazole pairs, i.e.,
and as well as and 10 11 give identical calculated
decomposition products.
2
3
4
4,
5
6
,
7
8,
9
,
X‐ray Crystallography
Figure 4. a) Thermal ellipsoid plot (50%) and labeling scheme for 8. b) Packing diagram
of 8 along a axis
Triclinic crystals of
8 were obtained by slow evaporation of
a saturated solution in benzene and diethyl ether at room
temperature. There are two molecules per unit cell in the crystal
which belongs to the P-1 space group. As shown in Figure 4,
there are strong intermolecular hydrogen bonding interactions
between hydrogen atoms of the methyl group and the oxygen
atoms of the nitro group. A nitro group adjacent to a carbon-
bearing iodine atom does not appear to influence the carbon
iodine bond length C(5)-I(6) [2.072(5) Å].
Figure 2: a) Thermal ellipsoid plot (50%) and labeling scheme for 5. b) Packing diagram
of 5 along a axis.
Crystallographic data for
5
,
6,
8
and 10 are summarized in
Table S1 (ESI). Crystals of
5
were obtained by slow
evaporation of a saturated solution of the compound in a
mixture of ethyl acetate and hexane. The crystals belong to
orthorhombic crystal system and are in the Pmn2 space group
1
with two molecules per unit cell. The N2-methyl substituent
does not appear to hinder strong π – π stacking interaction
between the rings as shown in Figure 2 (b). The carbon- iodine
bond length I(1)-C(2) [2.070(5) Å] is comparable to similar
bonds in
6 (Figure 3).
Figure 5. a) Thermal ellipsoid plot (50%) and labeling scheme for 10. b) Packing
diagram of 10 along a axis.
Crystals of 10 suitable for X-ray crystallography were
obtained by using a procedure similar to 8. The triclinic crystals
belong to the P-1 space group. The planarity of the ring is
preserved in spite of the presence of the bulkier ethyl group. As
a result there is strong π–π stacking interaction between the
rings (Figure 5).Additionally, intermolecular van der Waals
forces of attraction exist between the iodine and the oxygen
atoms of the nitro group. The carbon-iodine bond length is
similar to that in the other compounds.
Figure 3. a) Thermal ellipsoid plot (50%) and labeling scheme for 6. b) Packing diagram
of 6 along a axis
Conclusions
4
-Iodo-[1
H]-1,2,3-triazole (2) and 4, 5-diiodo-[1H]-1,2,3-
) were synthesized using an efficient synthetic route.
Slow evaporation of a saturated solution of
ethyl acetate and hexane gave suitable crystals for X-ray crystal
6 in a mixture of
triazole (
3
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N-alkylation of
3
gave N1- and N2-alkylated isomers in each filtered and washed with cold water. The compound was
]-1,2,3-triazole ( ). The filtrate
triazoles with improved oxygen balances. The iodo triazoles was extracted with diethyl ether which was evaporated using a
may increase the utility of 1 -1, 2, 3-triazoles in synthetic rotary evporator and the residue was dried in vacuo. The
case. Nitration of these N-alkylated species resulted in iodo identified as 4,5-diiodo-[1
H
3
H
organic chemistry as well as in medicinal chemistry.
compound was identified as 4-iodo-1,2,3-triazole (
: Yield 33.3%. (3.9 g). T = 110.8 °C, Tdec (onset) = 156. 6 C;
IR (KBr) υ 3429, 3115, 2962, 2916, 1633, 1504, 1445, 1300,
2).
o
2
m
Experimental Section
1
1
224, 1178, 1136, 1074, 927, 864, 817, 636 cm-1 ; 1H NMR δ
General Methods
5.4 (broad, NH), 8.0 (ring – CH) ; 13C NMR δ 135.9, 89.4;
1H and 13C NMR spectra were recorded on a 300 MHz (Bruker elemental analysis: (%) calculated for C
2
2 3
H IN (194.96): C,
Avance 300) nuclear magnetic resonance spectrometer 12.32; H, 1.03; N, 21.55; found C, 12.15; H, 1.03; N, 21.15.
o
operating at 300.13 and 75.48 MHz, respectively, by using
3: Yield 25%. Tdec (onset) = 189. 9 C; IR (KBr) υ 3430, 3121,
[
D6]DMSO as solvent and locking solvent unless otherwise 2943, 2827, 1718, 1629, 1556, 1503, 1444, 1332, 1284, 1179,
stated. A 500 MHz (Bruker AVANCE 500) nuclear magnetic 1091, 1008, 979, 804, 458 cm ; 1H NMR δ 15.6 (broad, NH) ;
resonance spectrometer operating at 50.69 MHz was used to 13C NMR δ 104.2; elemental analysis: (%) calculated for C
H I
(320.86): C, 7.49; H, 0.31; N, 13.10; found C, 7.65; H, 0.24;
S, and nitromethane for 15N. The N, 13.10.
-1
2
2
obtain 15N spectra.The chemical shifts in H and C spectra are
1
13
3
N
reported relative to Me
4
decomposition temperatures (onset) were obtained using a 1-Methyl-4,5-diiodo-1,2,3-triazole (4) and 2-methyl-4,5-
differential scanning calorimeter (DSC) (Model Q 10, TA diiodo-1,2,3-triazole (5).
Instruments Co.) at a scanning rate of 5 °C per minute in closed 4,5-Diiodo-1,2,3-[1H]-triazole (14.6 mmol, 4.7 g) was
aluminum containers with a small hole in the lids. IR spectra dissolved in DMF (5 mL) and potassium carbonate (23.15
were recorded using KBr pellets on a BIORAD model 3000 mmol, 3.2g) was added. The mixture was cooled to -20 °C in an
FTS spectrometer. Densities were determined at room ice-salt bath. Iodomethane (21.8 mmol, 1.36 mL) was added to
temperature employing a Micromeritics AccuPyic 1330 gas the cooled mixture and stirred for two hours. An off-white
pycnometer. Elemental analyses were carried out using an precipitate was formed which was filtered and washed with
Exeter CE-440 elemental analyzer.
X‐ray Crystallography
water. Analysis by TLC indicated the mixture contained two
constituents which were separated using column
Colorless plate crystals of dimensions 0.399 x 0.206 x 0.018 chromatography [eluent - hexane: ethyl acetate (2:8)]. Yield =
3
3
mm for
0
5
, 0.316 x 0.115 x 0.104 mm for
6
, 0.223 x 0.150 x 82% (4.7 g).
3
3
o
.037 mm for 8, and 0.174 x 0.077 x 0.014 mm for 10 were
m
4: Yield 48 %. T = 185.7 °C, Tdec (onset) = 212.7 C; IR (KBr)
-
1 1
mounted on MiteGen MicroMesh using a small amount of υ 2924, 1421, 1383, 1265, 1195, 1084, 1028, 983, 709 cm ; H
Cargille immersion oil. Data were collected on a Bruker three- NMR δ 4.1 (methyl, H), 8.0; 13C NMR δ 102.7, 95.3; 15N NMR
circle platform diffractometer equipped with a SMART APEX δ –0.5, -19.9, -133.7; elemental analysis: (%) calculated for
II CCD detector. The crystals were irradiated using graphite
monochromated MoK
radiation (λ = 0.71073). An Oxford 11.10; H, 0.91; N, 12.31.
3 3 2 3
C H I N (334.88): C, 10.76; H, 0.90; N, 12.55; found C,

Cobra low temperature device was used to keep the crystals at a
constant 150(2) K during data collection.
5
: Yield 52 %, T
m
= 129.7 °C; IR (KBr) υ 2925, 2854, 1638,
-
1 1
1438, 1413, 1365, 1292, 1018, 716, 644, 448 cm ; H NMR δ
Data collection was performed and the unit cell was initially 15.4 (broad, NH), 4.1 ( methyl – H) ; 13C NMR δ 104.3, 42.3;
refined using APEX3 [v2014.3-0].8 Data reduction was 15N NMR δ –39.5, -117.1; elemental analysis: (%) calculated
performed using SAINT [v7.68A]9 and XPREP [v2014/2].10 for C
3 3 2 3
H I N (334.88): C, 10.76; H, 0.90; N, 12.55; found C,
Corrections were applied for Lorentz, polarization, and 10.78; H, 0.88; N, 12.21.
absorption effects using SADABS [v2008/1].11 The structure 1-Ethyl-4,5-diiodo-1,2,3-triazole (6) and 2-ethyl-4,5-diiodo-
was solved and refined with the aid of the programs SHELXL- 1,2,3-triazole (7).
2,
13
2
014/7 within WingX.1
The full-matrix least-squares N-ethylation of 4,5-diiodo-1,2,3-triazole was carried out using
and . Yield 85%. The two isomers
were separated using silica gel column chromatography.
[Eluent – hexane: ethyl acetate (1:9)]
: Yield 47%. T = 127.5 °C, T = 170.9 °C ; IR (KBr) υ 2992,
2975, 2955, 2932, 1631, 1531, 1418, 1438, 1431, 1404, 1376,
-Iodo-1,2,3-triazole 4 (0.06 mol, 11g) was supended in 15 % 1340, 1296, 1238, 1097, 989, 1045, 989, 958, 785, 683 cm-1
aqueous ammonia (10 mL) and heated with occasional shaking 1H NMR δ 4.4 (CH ) ; 13C NMR δ 102.9, 93.9, 15.1;
), 1.4 (CH
at 100 °C in a thick-walled pressure tube. After 10-15 minutes, elemental analysis: (%) calculated for C (348.91): C,
heating was stopped when a clear solution was obtained. After 13.77; H, 1.44; N, 12.04; found C, 13.67; H, 1.42; N, 11.52.
cooling the tube, the aqueous ammonia was evaporated by
: Yield 47%. T = 108.1 °C ; IR (KBr) υ 2981, 2926, 2852,
blowing air over the solution and the residue was taken up in 1443, 1386, 1361, 1330, 1084, 1016, 964, 795, 690, 657, 430
2
refinement on F included atomic coordinates and anisotropic the procedure used for
4
5
6
thermal parameters for all non-H atoms. The H atoms were and
included using a riding model.
-Iodo-[1 ]-1,2,3-triazole (2) and 4,5-diiodo-[1
triazole (3).
7
4
H
H]-1,2,3-
6
m
d
1
;
2
3
4
5 2 3
H I N
7
m
water (100 mL). The solution was acidified with concentrated cm-1 ; H NMR δ 4.4 (CH
HCl to pH 3 to obtain an off-white precipitate which was 50.7, 14.5; 15N NMR δ –1.8, -19.5, -121.9; elemental analysis:
1
), 1.4 (CH
3
) ; 13C NMR δ 104.4,
2
4
| Dalton Trans., 2012, 00, 1‐3
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2
3
a) P. Yin, J. M. Shreeve, Angew. Chem. Int. Ed., 2015, 54
,
(
%) calculated for C
4
H
5
I
2
N
3
(348.91): C, 13.77; H, 1.44; N,
2.04; found C, 13.98; H, 1.44; N, 12.04.
-Methyl-4-nitro-5-iodo-1,2,3-triazole
-Methyl-4,5-diiodo-1,2,3-triazole (1 g, 3 mmol) was added
1
4513 – 14517. b) R. Haiges, G. Belanger-Chabot, S. M.
1
1
1
Kaplan, K. O. Christe, Dalton Trans., 2015, 44, 2978 – 2988.
c) P. Yin, D. A. Parrish, J. M. Shreeve, Angew. Chem. Int.
Ed., 2014, 53, 12889 –12892. d) D. E. Chavez, J. C. Bottaro,
(8).
portion wise to 10 mL of 100% nitric acid and the mixture was
heated at reflux for six hours. After cooling to room
temperature the mixture was poured onto crushed ice to give a
pale yellow precipitate which was filtered, and washed with
cold water (10 mL x 3) to obtain 8.
M. Petrie, D. A. Parrish, Angew. Chem. Int. Ed., 2015, 54
2973 12975. e) A. A. Dippold, T. M. Klapötke, J. Am.
Chem. Soc. 2013, 135, 9931–9938.
a) Y. Zhang, D. A. Parrish, J. M. Shreeve, J. Mater. Chem.
A, 2013, , 585 – 593. b) A. T. Baryshnikov, B. I. Erashko,
,
1
̶
1
N. I. Zubanova, B. I. Ugrak, Bull. Russ. Acad. Sci., Chem.
8
1
m
: Yield 62 %. T = 98.0 °C ; IR (KBr) υ 2924, 2853, 1539,
Ser., 1992, 41, 751–757.
A. C. Tome, Science of Synthesis, 2004, 13, 415 – 601.
R. Miethchen, H. Albrecht, E. Rachow, Z. Chem., 1970, 10,
-
1
4
5
435, 1377, 1300, 1267, 1219, 1097, 1045, 831, 717, 435 cm ;
1H NMR δ 4.1(CH
); 13C NMR δ 155.3, 88.3, 38.6; 15N NMR δ
3
2
20 – 221.
-
11.6, -25.2, -35.0, -128.4; elemental analysis: (%) calculated
for C IN (253.99): C, 14.19; H, 1.19; N, 22.06; found C,
4.49; H, 1.22; N, 21.63.
-Methyl-4-nitro-5-iodo-1,2,3-triazole (9)
6
M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria,
M. A. Robb, J. R. Cheeseman, J. A. Montgomery, Jr., T.
Vreven, K. N. Kudin, J. C. Burant, J. M. Millam, S. S.
Iyengar, J. Tomasi, V. Barone, B. Mennucci, M. Cossi, G.
Scalmani, N. Rega, G. A. Petersson, H. Nakatsuji, M. Hada,
M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T.
Nakajima, Y. Honda, O. Kitao, H. Nakai, M. Klene, X. Li, J.
E. Knox, H. P. Hratchian, J. B. Cross, V. Bakken, C. Adamo,
J. Jaramillo, R.Gomperts, R. E. Stratmann, O. Yazyev, A. J.
Austin, R. Cammi, C. Pomelli, J. W. Ochterski, P. Y. Ayala,
K. Morokuma, G. A. Voth, P. Salvador, J. J. Dannenberg, V.
G. Zakrzewski, S. Dapprich, A. D. Daniels, M. C. Strain, O.
Farkas, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B.
Foresman, J. V. Ortiz, Q. Cui, A. G. Baboul, S. Clifford, J.
Cioslowski, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz,
I. Komaromi, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-
Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M.
W. Gill, B. Johnson, W. Chen, M. W. Wong, C. Gonzalez, J.
A. Pople, Gaussian 03 (Revision D.01), Gaussian, Inc.,
Wallingford CT, 2004.
3
H
3
4 2
O
1
2
.
Compound
for
mmol).
9
was prepared following a procedure similar to that
8
by using 2-methyl-4, 5-diiodo-1,2,3-triazole (1 g, 3
9
m d
: Yield 63.3 %. T = 156.0 °C, T = 235.0 °C; IR (KBr) υ
2
924, 2853, 1633, 1541, 1416, 1362, 1331, 1085, 831, 725, 644
cm-1 ; 1H NMR δ 4.2 (CH
); 13C NMR δ 154.3, 91.4, 38.6; 15
3
N
NMR δ -26.4, -31.5, -49.8, -123.0; elemental analysis: (%)
calculated for C IN (253.99): C, 14.19; H, 1.19; N, 22.06;
found C, 14.63; H, 1.23; N, 20.91.
-Ethyl-4-nitro-5-iodo-1, 2, 3-triazole
Compound 10 was prepared following a procedure similar to
3
H
3
4 2
O
1
(10).
that for
mmol).
8
by using 1-ethyl-4, 5-diiodo-1, 2, 3-triazole (1 g, 2.9
= 111.2 °C, T = °C, T = 235.0 °C; IR
10: Yield 63 %. T
m
d
d
7
8
9
A. Strȍmberg, O. Gropen, U. Wahlgren, J. Comput. Chem.,
1
983, 4, 181 – 186.
(
5
KBr) υ 1537, 1431, 1387, 1325, 1095, 1072, 968, 827, 650,
71, 474, 426 cm-1 ; 1H NMR δ 4.5(CH ); 13C NMR
Bruker (2014). APEX2 v2010.3-0. Bruker AXS Inc.,
), 1.4 (CH
3 2
Madison, Wisconsin, USA.
Bruker (2009). SAINT v7.68A. Bruker AXS Inc., Madison,
Wisconsin, USA.
δ 154.2, 91.4, 51.8, 13.8; elemental analysis: (%) calculated for
I N (268.01): C, 17.93; H, 1.88; N, 20.90; found C,
C
4
H
5
4 2
O
1
2
8.14; H, 1.87; N, 20.66
-Ethyl-4-nitro-5-iodo-1, 2, 3-triazole (11).
10 Bruker (2014). XPREP v2008/2. Bruker AXS Inc., Madison,
Wisconsin, USA.
1
1 Bruker (2008). SADABS v2008/1, Bruker AXS Inc.,
Compound 11 was prepared following a procedure similar to
by using 2-ethyl-4, 5-diiodo-1, 2, 3-triazole (1 g, 2.9 mmol). 11
Yield 64 %. Tm = 111.2 °C, Td = °C; IR (KBr) υ 2992, 2924,
8
:
Madison, Wisconsin, USA.
1
2 Sheldrick, G. M. (2014). SHELXL-2014/7. University of
Göttingen, Germany.
1
1
1
5
635, 1538, 1484, 1440, 1410, 1374, 1295, 1255, 1186, 1105, 13 L. J. Farrugia, J. Appl. Cryst., 2012, 45, 849 – 854.
043, 958, 833, 692 cm-1 ; 1H NMR δ 4.5(CH3), 1.4 (CH2);
3C NMR δ 155.3, 87.0, 47.2, 14.4; 15N NMR δ -26.3, -34.0, -
2.1, -111.5 elemental analysis: (%) calculated for C4H5IN4O2
(
268.01): C, 17.93; H, 1.88; N, 20.90; found C, 17.99; H, 1.84;
N, 20.50
Acknowledgements
Financial support from the Office of Naval Research (N00014-16-1-
2
0
089), and the Defense Threat Reduction Agency (HDTRA 1-15-1-
028) is gratefully acknowledged.
References
1
a) S. L. Chang, J. Am. Pharm. Assoc. 1958, 47, 417–423. b)
W. P. Oziminskia, J. C. Dobrowolskia, A. P. Mazureka, J.
Mol. Struct., 2003, 651, 697–704.
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DOI: 10.1039/C6DT01731B
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An efficient synthetic route to mono and diiodo-1H-1,2,3-triazoles