Synthesis of 1,2,3-triazoles from heterocyclic α-nitro azides

Article abstract of DOI:10.1007/s11172-012-0296-y

Noncatalytic and Cu(I)-catalyzed dipolar cycloadditions of heterocyclic a-nitro azides to substituted alkynes were studied. Catalytic cyclization gave 1,4-disubstituted triazoles only. The effect of the substituents in alkynes and that of the nature of th

Full text of DOI:10.1007/s11172-012-0296-y

Russian Chemical Bulletin, International Edition, Vol. 61, No. 11, pp. 2114—2123, November, 2012
2114
Synthesis of 1,2,3ꢀtriazoles from heterocyclic ꢀnitro azides
D. V. Katorov, G. F. Rudakov, I. N. Katorova, A. V. Yakushkov, D. P. Simonov, and V. F. Zhilin
D. I. Mendeleyev University of Chemical Technology of Russia,
9 Miusskaya pl., 125047 Moscow, Russian Federation.
Fax: +7 (495) 496 6027. Eꢀmail: KatorovDV@gmail.com
Noncatalytic and Cu(I)ꢀcatalyzed dipolar cycloadditions of heterocyclic ꢀnitro azides to
substituted alkynes were studied. Catalytic cyclization gave 1,4ꢀdisubstituted triazoles only.
The effect of the substituents in alkynes and that of the nature of the starting heterocycles on the
isomer ratio of triazoles were examined. New representatives of 1,2,3ꢀtriazoles were obtained;
their physicochemical properties were studied. A comparative analysis of the spectral characꢀ
teristics of the resulting regioisomeric triazole derivatives was performed.
Key words: geminal nitro azides, 1,3ꢀdipolar cycloaddition, 1,2,3ꢀtriazoles.
Having unique properties, 1,2,3ꢀtriazole derivatives ocꢀ
diol (1) by oxidative azidation of sodium salts of secondꢀ
cupy an important place in organic chemistry. They find
applications as intermediates in organic synthesis, exhibit
a wide spectrum of biological activity,1—4 and can be used
as optical bleaching agents5 and components of chemiluꢀ
minescent formulations.6
ary nitroalkanes21 (Scheme 1).
Scheme 1
The 1,2,3ꢀtriazole ring contributes 168 kJ mol–1 to the
enthalpy of formation of the compound;7 along with high
chemical and thermal stability, this makes the compounds
of this class attractive as components of highꢀenergy forꢀ
mulations.8—11
Substituted 1,2,3ꢀtriazoles are most commonly obꢀ
tained by 1,3ꢀdipolar cycloaddition of azides to alkynes.
Elevated temperature is usually required for the reaction
to occur. Nonsymmetric alkynes yield mixtures of 1,4ꢀ
and 1,5ꢀdisubstituted isomers. The reaction is regiospecifꢀ
ic when silylꢀsubstituted alkynes,12 ynamines,13 and Grigꢀ
nard reagents14,15 are used as dipolarophiles. In the last few
years, selective synthesis of 1,4ꢀdisubstituted 1,2,3ꢀtriꢀ
azoles has been implemented most often by means of
catalysis with CuI ions,16 while 1,5ꢀdisubstituted derivaꢀ
tives have been selectively obtained in the presence of ruꢀ
thenium complex salts.17
Despite much research dealing with the mechanism of
[3+2] cycloaddition, it still remains not fully understood
how the reaction pathway depends on the structure of the
starting azides. Very scarce and contradictory data on the
reactivity of geminal nitro azides18—20 preclude any preꢀ
dictions of the effect of the ꢀnitro group on the 1,3ꢀdiꢀ
polar addition to alkynes.
R = NO2 (a), But (b)
We studied both thermal and CuIꢀcatalyzed cycloꢀ
additions of heterocyclic ꢀnitro azides to butꢀ2ꢀyneꢀ1,4ꢀ
diol (6), phenylacetylene (7), propargyl alcohol (8), and
trimethylsilylacetylene (9), which are most commonly
used for this purpose.
Thermal cyclization of 3ꢀazidoꢀ1,3ꢀdinitroazetidine
(2a) and 5ꢀazidoꢀ2,2ꢀdimethylꢀ5ꢀnitroꢀ1,3ꢀdioxane (3)
with internal alkyne 6 gave 1,4,5ꢀtrisubstituted triazoles
10 and 11 (Scheme 2, Table 1). The reactions were carried
out in boiling solvents (toluene, benzene) and melted butꢀ
2ꢀyneꢀ1,4ꢀdiol. When the temperature of the cyclization
of azide 2a with alkyne 6 was lowered from 110 to 80 C
To find out how the structure of a nitroheterocycle
influences the cycloaddition regioselectivity, here we emꢀ
ployed heterocyclic ꢀnitro azides 2—5 prepared from
easily accessible 2ꢀ(hydroxymethyl)ꢀ2ꢀnitropropaneꢀ1,3ꢀ
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2098—2107, November, 2012.
1066ꢀ5285/12/6111ꢀ2114 © 2012 Springer Science+Business Media, Inc.

1,2,3ꢀTriazoles from heterocyclic ꢀnitro azides
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 11, November, 2012 2115
donating (tertꢀbutyl) substituents are less stable,21 the cyꢀ
clizations of nitro azides 2b, 4b, and 5 were studied at
room temperature.
Table 1. Outcomes of the cyclization reactions of nitro azides 2a
and 3 with butꢀ2ꢀyneꢀ1,4ꢀdiol (6)
Comꢀ
pound
T/C
t/h
Yields (%) of
triazoles 10 and 11
M.p./C
The ratio of the reaction products was determined by
1
analyzing the chemical shifts of the H NMR signals for
the proton of the triazole ring. The proton in position 5 of
the triazole ring of 1,4ꢀdisubstituted isomers is less shieldꢀ
ed (and, accordingly, is always manifested as a lowerꢀfield
signal in the 1H NMR spectrum) than the proton in posiꢀ
tion 4 of 1,5ꢀdisubstituted isomers.22,23
We found that the nature of the terminal acetylene is
decisive for the cyclization reaction. With trimethylsilylꢀ
acetylene (9), the cyclizations selectively give 1,4ꢀdisubꢀ
stituted triazoles, regardless of the structure of heteroꢀ
cyclic ꢀnitro azide.
2a
3
110
80
80
5
62
85
35
52
185—190
135—137
24
48
24
70*
* In the presence of excess alkynediol 6.
(replacement of toluene by benzene), the yield of 4,5ꢀbisꢀ
(hydroxymethyl)ꢀ1,2,3ꢀtriazole (10) was increased to 85%,
though the reaction time was extended as well.
Cycloaddition of phenylacetylene (7) is usually not regioꢀ
specific, yielding 1,4ꢀ and 1,5ꢀisomers in equal amounts.19
With sterically hindered azides, 4ꢀphenyltriazole is a preꢀ
dominant cycloadduct,24 with few exceptions of a preꢀ
dominant 1,5ꢀisomer.25 Apparently, the exceptions include
ꢀnitro azides as well. Cyclization reactions of azides 2a,
3, and 4a with phenylacetylene produce 1,5ꢀdisubstituted
isomer (b) as a major product. This is confirmed by the
literature data19 on the preferential formation of 5ꢀpheꢀ
nyltriazole (73%) from 1ꢀazidoꢀ1ꢀnitroethane (ꢀnitro
azide) and phenylacetylene and on the formation of
a mixture of isomers from 1ꢀazidoꢀ2ꢀnitroethane and
phenylacetylene, the 1,4ꢀdisubstituted isomer being preꢀ
dominant.
Scheme 2
R =
(2a, 10),
(3, 11)
Nitro azide 3 is less reactive toward butꢀ2ꢀyneꢀ1,4ꢀ
Except for azide 2a, the reactions with propargyl alcoꢀ
hol (8) mainly give the 1,4ꢀisomer (a). Cycloadditions of
nitro azides 2a,b, 3, 4b, and 5 in excess propargyl alcohol
as well as cycloadditions at elevated temperatures are all
nonselective (see Table 2). The ratio of regioisomeric
cycloadducts is virtually independent of the reaction conꢀ
ditions. Little changes were noticed only for compounds
2a and 3. A decrease in the temperature augments the
fraction of the 1,4ꢀdisubstituted isomer.
5ꢀAzidoꢀ3ꢀtertꢀbutylꢀ5ꢀnitrotetrahydroꢀ1,3ꢀoxazine (4b)
and 5ꢀazidoꢀ1,3ꢀdiꢀtertꢀbutylꢀ5ꢀnitrohexahydropyrimidꢀ
ine (5) decompose under the reaction conditions in 10 h.
The substituent in position 1 of the azetidine ring also
has some influence on the outcome of the reaction. Cycloꢀ
addition of nitro azide 2a containing the Nꢀnitro group to
propargyl alcohol mainly yields the 1,5ꢀdisubstituted isoꢀ
mer. In contrast, the 1,4ꢀdisubstituted isomer is slightly
dominant in the products obtained from Nꢀtertꢀbutylꢀsubꢀ
stituted nitro azide 2b.
diol (6). In benzene (80 C), the slow formation of triazole 11
is accompanied by decomposition of the starting azide 3.
A solventꢀfree reaction in the presence of excess alkynediol
6 allows higher yields of the target product in a shorter
cyclization time.
As expected, thermal cyclization of ꢀnitro azides with
terminal alkynes 7 and 8 proceeds slowly to give mixtures
of regioisomers a (1,4ꢀdisubstituted) and b (1,5ꢀdisubstiꢀ
tuted) (Scheme 3, Table 2). The reactions were carried out
in toluene or with no solvent added, in an excess of the
substituted alkyne. Since nitro azides containing electronꢀ
Scheme 3
N–
i
R2
N+
N
+
7—9
R1
Cyclizations of ꢀnitro azides with alkyne 9 proceed
slowly, and a tenfold excess of the alkyne is required. With
a lower ratio of the reactants, the reaction does not reach
completion even upon prolonged heating. The synthesis at
elevated temperatures allows substantial reduction in the
reaction time. As expected, the 1,4ꢀdisubstituted isomer is
the only product in all cases.
2—5
N
N
R1
R1
N
N
N
N
+
R2
R2
12b—23b
12a—23a

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Katorov et al.
Table 2. Outcomes of the thermal cyclizations of azides 2a,b, 3, 4a,b, and 5
Starting compounds and substituents
T/C
t/h Yields (%) of
the products
(%)
Ratio of
the isomers
(1,4 : 1,5)
R1N3
R1
HCCR2
R2
2a
7
Ph
110
15
65
19 : 81 (12a : 12b)
8
9
CH2OH
Me3Si
110
18а
55
11
110
7
85
90
78
28 : 72 (13a : 13b)
36 : 64 (13a : 13b)
100 (14a)
2b
8
CH2OH
18а
240
78
53 : 47 (15a : 15b)
60а
18а
7
360
91
62
54 : 46 (15a : 15b)
100 (16a)
9
7
Me3Si
Ph
3
110
11
74
37 : 63 (17a : 17b)
8
9
CH2OH
Me3Si
110
20а
55
13
160
13
72
76
76
64 : 36 (18a : 18b)
74 : 26 (18a : 18b)
100 (19a)
4a
7
8
Ph
110
110
12
10
48
47
34 : 66 (20a : 20b)
64 : 36 (21a : 21b)
CH2OH
4b
5
9
Me3Si
Me3Si
18а
840
960
58
70
100 (22a)
100 (23a)
9
18а
a In the presence of excess alkyne.
Because the reactions of nitro azides with terminal
alkynes (except for alkyne 9) give both isomers, selective
methods of 1,3ꢀdipolar cycloaddition are wanted.
Selective synthesis of 1,4ꢀdisubstituted triazoles was
implemented by CuIꢀcatalyzed cycloaddition of a nitro
azide to a terminal alkyne in the system ascorbic acid—
cupric sulfate.26 In all the reactions studied, the yields
were increased to 70—96%, the 1,4ꢀdisubstituted isoꢀ
mer being the only reaction product (Scheme 4, Table 3).
Another benefit is a much higher rate of the reaction
completed within 3 h against 10—15 h for thermal cyꢀ
clization.

1,2,3ꢀTriazoles from heterocyclic ꢀnitro azides
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 11, November, 2012 2117
Table 3. Outcomes of the copper(I)ꢀcatalyzed cyclizations of
azides 2a,b, 3, 4a,b, and 5
When the "Sharpless catalyst" was replaced by cuprous
chloride, the same products were obtained in lower yields,
although the amount of cuprous chloride used was twice
as high as that of the copper component of the Sharpless
catalyst (see Table 3).
Starting compounds
and substituents
t/h
Yields (%)
of the products
(%)
M.p./C
R1N3
HCCR2
1,5ꢀDisubstituted azetidinyltriazoles 12b and 13b
differ substantially in physicochemical properties
2a
7
8
7
8
9
7
2
2
2
2
72
1.5
4
2
1
3.5
3
0.5
0.5
71 (12a)
96 (13a)
66 (24)
163—168
115—117
131—133
115—117
88—86
from their 1,4ꢀregioisomers 12a and 13a and can easily
be isolated in the individual state simply by recrystallizaꢀ
tion.
Structures 12b and 13b were examined by 1H, 13C, and
{1H—15N}HMBC NMR spectroscopy (Table 4, Figs 1
and 2).
The signals for the carbon atoms in 1,5ꢀdisubstituted
triazoles (b) are more closely located than the signals for
the same atoms in 1,4ꢀdisubstituted triazoles. The signals
for the C(4) and C(5) atoms in 1,4ꢀdisubstituted triazoles
are shifted downfield and upfield, respectively. A similar
spectral pattern has been observed for 1ꢀethylꢀ4(5)ꢀnitroꢀ
1,2,3ꢀtriazoles.27
2b
3
62 (15a)
20 (16a)
86 (17a)
44 (17a)a
86 (18a)
89 (20a)
54 (20a)a
83 (21a)
60 (25)
53—56
8
7
165—167
154—156
4a
8
7
8
—
4b
5
150—153
150—152
84 (26)
a In the presence of Cu2Cl2 (0.3 equiv.).
The {1H—15N}HMBC NMR spectra of triazoles b reꢀ
veal couplings of the proton of the triazole ring with all
three N atoms of the triazole ring (in 1,4ꢀdisubstituted
triazoles, the ring proton couples only with the N(1) and
N(3) atoms). Also, the CH2 protons of the hydroxymethyl
group couple with the N(1) atom and weakly couple
with the N(3) atom. The absence of the coupling with
the N(1) atom in 1,4ꢀdisubstituted triazoles provides
evidence for the correct location of the hydroxymethyl
group in position 4 of the triazole ring. In phenyltriazoles,
no couplings were revealed between the N atoms and
the phenyl protons in both regioisomers. These comꢀ
pounds can be distinguished only by the couplings beꢀ
tween the N atoms and the proton of the triazole ring,
Scheme 4
We found that the use of trimethylsilylacetylene in catꢀ
alytic cycloaddition results in appreciably lower yields and
longer reaction times.
Table 4. Comparative table of the 1H, 13C, and 15N NMR signals for triazoles 12a,b and 13a,b
Atom

12a
12b
13a
13b
N—NO2
N—NO2
–224
–19
–222
–20
–223
–20
–223
–19
C—NO2
–2
1
–1
1
C—CH2—N—NO2
5.50 (s, 4 H)
5.15 (d, 2 H,
J = 11.2 Hz);
5.21 (d, 2 H,
J = 11.2 Hz)
5.43 (s, 4 H)
5.40 (d, 2 H,
J = 11.8 Hz);
5.59 (d, 2 H,
J = 11.8 Hz)
Atoms of the triazole fragment
N(1)
N(2)
–138
—
–142
–16
–140
—
–142
–15
N(3)
–28
–21
–22
–23
C(4)
C(5)
С(4)—Н
С(5)—Н
147.09
128.66
—
133.61
139.19
8.11
149.15
124.08
—
132.30
138.79
7.80
9.02
—
8.53
—

2118
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 11, November, 2012
Katorov et al.
a

1
250
200
150
100
50
0
9.2
8.8
8.4
8.0
7.6
7.2
6.8
6.4
6.0
5.6

2
b

1
200
150
100
50
0
8.1
7.8 7.5
7.2
6.9 6.6
6.3
6.0
5.7
5.4

2
Fig. 1. {1H—15N}HMBC NMR spectra of compounds 12a (a) and 12b (b).
which are similar with those in hydroxymethyl analogs
(see Figs 1 and 2).
tives, which are of interest as intermediates in the syntheꢀ
sis of various classes of chemical (specifically, highꢀenerꢀ
gy) compounds.
It should be noted that the protons of the Nꢀnitroazetiꢀ
dine ring are manifested as different signals (a singlet for
1,4ꢀdisubstituted triazoles and two doublets for 1,5ꢀdisubꢀ
stituted triazoles, see Table 4), which can be due to the
different rates of the conformational changes of the azetiꢀ
dine ring (in 1,5ꢀdisubstituted triazoles, the rate is lower).
To sum up, we were the first to study 1,3ꢀdipolar cycloꢀ
addition of heterocyclic ꢀnitro azides to substituted
alkynes, both with and without copper(I) salts as catalysts.
We examined the properties of new 1,2,3ꢀtriazole derivaꢀ
Experimental
1
H and 13C NMR spectra were recorded on Bruker AC200
(200 MHz), Bruker AM300 (300 MHz), and Bruker AMX 400
instruments (400 MHz) in CDCl3 and DMSOꢀd6. {1H—15N}ꢀ
HMBC NMR spectra were recorded on a Bruker AV600 instruꢀ
ment (600 MHz) in DMSOꢀd6 with nitromethane as a standard.
IR spectra were recorded on a Thermo Nicolet 360 FTIR

1,2,3ꢀTriazoles from heterocyclic ꢀnitro azides
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 11, November, 2012 2119
a

1
250
200
150
100
50
0
–50
8.6 8.2
7.8
7.4
7.0
6.6
6.2 5.8
5.4
5.0
4.6

2
b

1
240
220
200
180
160
140
120
100
80
60
40
20
0
–20
8.0
7.5
7.0
6.5
6.0
5.5
5.0

2
Fig. 2. {1H—15N}HMBC NMR spectra of compounds 13a (a) and 13b (b).
spectrometer (KBr pellets, 7 mm in diameter). Melting points
were determined on a Boetius hot stage (heating rate 2 deg•min–1).
The course of the reactions was monitored by TLC on Sorbfil
plates.
The starting nitro azides were prepared as described earliꢀ
er.21 Butꢀ2ꢀyneꢀ1,4ꢀdiol (6), phenylacetylene (7), propargyl alꢀ
cohol (8) were purchased from Aldrich. Trimethylsilylacetylene
(9) was synthesized as described earlier.28
methyl)ꢀ1Hꢀ1,2,3ꢀtriazole (10). A mixture of 3ꢀazidoꢀ1,3ꢀdiꢀ
nitroazetidine (2a) (2.42 g, 12.9 mmol) and butꢀ2ꢀyneꢀ1,4ꢀdiol
(6) (1.11 g, 12.9 mmol) in benzene (50 mL) was heated to boiling
with vigorous stirring and left for 24 h. On cooling, the precipiꢀ
tate that formed was filtered off and washed with benzene. Yield
3 g (85%), m.p. 185—190 C (decomp.). IR, /cm–1: 3498, 3280
(OH); 3052, 3037, 2987, 2929 (CH), 1579, 1538, 1341, 1272
(NO2). 1H NMR (200 MHz, DMSOꢀd6), : 4.55 (s, 2 H,
C(4)—CH2—OH); 4.71 (s, 2 H, C(5)—CH2—OH); 5.37 (d, 3 H,
N—CH2—O, OH, J = 11.8 Hz); 5.59 (d, 2 H, N—CH2—C,
J = 11.8 Hz); 5.81 (s, 1 H, OH). 13C NMR (50 MHz, DMSOꢀd6),
: 52.33 (C(5)—CH2—OH); 54.02 (C(4)—CH2—OH); 64.72
(N—CH2—C); 87.70 (C—NO2); 135.71 (N—C(5)(CH2)=C);
144.65 (C=C(4)(CH2)—N). Found (%): C, 30.60; H, 3.61;
Cycloaddition of ꢀnitro azides to substituted alkynes
Cycloaddition of ꢀnitro azides to internal alkyne 6 (butꢀ2ꢀ
yneꢀ1,4ꢀdiol). 1ꢀ(1,3ꢀDinitroazetidinꢀ3ꢀyl)ꢀ4,5ꢀbis(hydroxyꢀ

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Russ.Chem.Bull., Int.Ed., Vol. 61, No. 11, November, 2012
Katorov et al.
N, 30.75. C7H10N6O6. Calculated (%): C, 30.66; H, 3.68;
N, 30.65.
(a mixture of regioisomers, 15a : 15b = 53 : 47). 1,4ꢀIsomer.
1H NMR (300 MHz, DMSOꢀd6), : 4.09 (d, N—CH2—C,
J = 10.3 Hz); 4.23—4.33 (m, N—CH2—C); 4.60 (s, CH2—OH);
8.52 (s, CH). 1,5ꢀIsomer. 1H NMR (300 MHz, DMSOꢀd6),
: 4.23—4.33 (m, N—CH2—C); 4.62 (s, CH2—OH); 7.78 (s, CH).
Method B. Yield 91% (a mixture of regioisomers, 15a : 15b =
= 54 : 46). 1,4ꢀIsomer. 1H NMR (300 MHz, DMSOꢀd6), : 4.09
(d, N—CH2—C, J = 10.0 Hz); 4.24—4.32 (m, N—CH2—C);
4.60—4.62 (m, CH2—OH); 5.27 (t, OH, J = 5.1 Hz); 8.51 (s, CH).
1,5ꢀIsomer. 1H NMR (300 MHz, DMSOꢀd6), : 4.24—4.32
(m, N—CH2—C); 4.60—4.62 (m, CH2—OH); 5.55 (t, OH,
J = 5.1 Hz); 7.77 (s, CH).
1ꢀ(2,2ꢀDimethylꢀ5ꢀnitroꢀ1,3ꢀdioxanꢀ5ꢀyl)ꢀ4ꢀphenylꢀ1Hꢀ1,2,3ꢀ
triazole (17a) and 1ꢀ(2,2ꢀdimethylꢀ5ꢀnitroꢀ1,3ꢀdioxanꢀ5ꢀyl)ꢀ5ꢀ
phenylꢀ1Hꢀ1,2,3ꢀtriazole (17b). A reaction of 5ꢀazidoꢀ2,2ꢀdiꢀ
methylꢀ5ꢀnitroꢀ1,3ꢀdioxane with phenylacetylene was carried
out according to method B. Yield 74% (a mixture of regioisoꢀ
mers, 17a : 17b = 37 : 63). 1,4ꢀIsomer. 1H NMR (300 MHz,
DMSOꢀd6), : 1.34 (s, Me); 4.86 (d, O—CH2—C, J = 12.8 Hz);
5.12 (d, O—CH2—C, J = 12.5 Hz); 7.37—7.61 (m, Ph); 7.90
(d, Ph, J = 7.3 Hz); 9.25 (s, CH). 1,5ꢀIsomer. 1H NMR (300 MHz,
DMSOꢀd6), : 1.34 (s, Me); 4.54 (d, O—CH2—C, J = 12.5 Hz);
4.65 (d, O—CH2—C, J = 13.2 Hz); 7.33 (d, Ph, J = 6.6 Hz);
7.37—7.61 (m, Ph); 7.95 (s, CH).
1ꢀ(2,2ꢀDimethylꢀ5ꢀnitroꢀ1,3ꢀdioxanꢀ5ꢀyl)ꢀ4,5ꢀbis(hydroxyꢀ
methyl)ꢀ1Hꢀ1,2,3ꢀtriazole (11). A mixture of 5ꢀazidoꢀ2,2ꢀdiꢀ
methylꢀ5ꢀnitroꢀ1,3ꢀdioxane (3) (10 g, 49.5 mmol) and butꢀ2ꢀ
yneꢀ1,4ꢀdiol (6) (12 g, 140 mmol) was heated to 70 C. The
resulting melt was stirred for 24 h, cooled, and washed with 15%
NaCl (50 mL). The precipitate that formed was filtered off,
washed with ice water, and dried in air. Yield 7.5 g (52%), m.p.
135—137 C. IR, /cm–1: 3345 (OH); 3000, 2960, 2892 (CH),
1568, 1343 (NO2). 1H NMR (300 MHz, DMSOꢀd6), : 1.40 (s, 6 H,
Me); 4.53 (d, 2 H, CH2OH, J = 5.4 Hz); 4.64 (d, 2 H, CH2OH,
J = 4.8 Hz); 4.88 (d, 2 H, O—CH2—C, J = 12.9 Hz); 4.97 (d, 2 H,
O—CH2—C, J = 12.9 Hz); 5.27 (t, 1 H, OH, J = 5.1 Hz); 5.70
(t, 1 H, OH, J = 4.3 Hz). 13C NMR (75 MHz, DMSOꢀd6),
: 21.41 (Me); 24.92 (Me); 51.00 (C(5)—CH2—OH); 53.84
(C(4)—CH2—OH); 62.65 (O—CH2—C); 95.11 (C—NO2); 100.07
(O—C(Me)2—O); 135.26 (N—C(CH2)=C(CH2)); 146.08
(C(CH2)=C(CH2)—N). Found (%): C, 41.73; H, 5.65; N, 19.34.
C10H16N4O6. Calculated (%): C, 41.67; H, 5.59; N, 19.44.
Cyclization of ꢀnitro azides with terminal alkynes. Method A.
A mixture of a nitro azide and propargyl alcohol in a molar ratio
of 1 : 15 was kept at room temperature for 7—10 days until the
starting azide was consumed completely (monitoring by TLC).
The excess propargyl alcohol was removed in vacuo and the
residue was examined by 1H NMR spectroscopy.
[1ꢀ(2,2ꢀDimethylꢀ5ꢀnitroꢀ1,3ꢀdioxanꢀ5ꢀyl)ꢀ1Hꢀ1,2,3ꢀtriꢀ
azolꢀ4ꢀyl]methanol (18a) and [1ꢀ(2,2ꢀdimethylꢀ5ꢀnitroꢀ1,3ꢀdiꢀ
oxanꢀ5ꢀyl)ꢀ1Hꢀ1,2,3ꢀtriazolꢀ5ꢀyl]methanol (18b). A reaction of
5ꢀazidoꢀ2,2ꢀdimethylꢀ5ꢀnitroꢀ1,3ꢀdioxane with propargyl alcoꢀ
hol was carried out according to methods A and B. Method A.
Yield 76% (a mixture of regioisomers, 18a : 18b = 74 : 26).
Method B. A terminal alkyne (1.2 mol) was added to a mixꢀ
ture of the starting azide (1 mol) and toluene. The reaction mixꢀ
ture was refluxed until the starting azide was consumed comꢀ
pletely (monitoring by TLC). The solvent and the excess alkyne
1
1
were removed in vacuo. The residue was examined by H NMR
1,4ꢀIsomer. H NMR (300 MHz, DMSOꢀd6), : 1.41 (s, Me);
spectroscopy.
4.58 (s, CH2—OH); 4.79 (d, O—CH2—C, J = 13.2 Hz); 5.07 (d,
O—CH2—C, J = 13.2 Hz); 8.59 (s, CH). 1,5ꢀIsomer. H NMR
1
1ꢀ(1,3ꢀDinitroazetidinꢀ3ꢀyl)ꢀ4ꢀphenylꢀ1Hꢀ1,2,3ꢀtriazole (12a)
and 1ꢀ(1,3ꢀdinitroazetidinꢀ3ꢀyl)ꢀ5ꢀphenylꢀ1Hꢀ1,2,3ꢀtriazole (12b).
A reaction of 3ꢀazidoꢀ1,3ꢀdinitroazetidine with phenylacetylene
was carried out according to method B. Yield 65% (a mixture of
regioisomers, 12a : 12b = 19 : 81). 1,4ꢀIsomer. 1H NMR (300 MHz,
DMSOꢀd6), : 5.50 (s, N—CH2—C); 7.29—7.58 (m, Ph); 9.0
(300 MHz, DMSOꢀd6), : 1.41 (s, Me); 4.63 (s, CH2—OH);
4.86 (d, O—CH2—C, J = 13.2 Hz); 4.98 (d, O—CH2—C,
J = 13.2 Hz); 7.80 (s, CH). Method B. Yield 72% (a mixture
of regioisomers, 18a : 18b = 64 : 36). 1,4ꢀIsomer. 1H NMR
(300 MHz, DMSOꢀd6), : 1.41 (s, Me); 4.58 (s, CH2—OH);
4.79 (d, O—CH2—C, J = 12.5 Hz); 5.07 (d, O—CH2—C,
J = 13.2 Hz); 8.59 (s, CH). 1,5ꢀIsomer. 1H NMR (300 MHz,
DMSOꢀd6), : 1.41 (s, Me); 4.64 (s, CH2—OH); 4.86 (d,
O—CH2—C, J = 12.5 Hz); 4.98 (d, O—CH2—C, J = 13.2 Hz);
7.80 (s, CH).
1
(s, CH). 1,5ꢀIsomer. H NMR (300 MHz, DMSOꢀd6), : 5.15
(d, N—CH2—C, J = 10.3 Hz); 5.21 (d, N—CH2—C, J = 10.3 Hz);
7.29—7.58 (m, Ph); 7.88 (d, Ph, J = 8.1 Hz); 8.11 (s, CH).
[1ꢀ(1,3ꢀDinitroazetidinꢀ3ꢀyl)ꢀ1Hꢀ1,2,3ꢀtriazolꢀ4ꢀyl]methanꢀ
ol (13a) and [1ꢀ(1,3ꢀdinitroazetidinꢀ3ꢀyl)ꢀ1Hꢀ1,2,3ꢀtriazolꢀ5ꢀyl]ꢀ
methanol (13b). A reaction of 3ꢀazidoꢀ1,3ꢀdinitroazetidine with
propargyl alcohol was carried out according to methods A and B.
Method A. Yield 90% (a mixture of regioisomers, 13a : 13b =
= 36 : 64). 1,4ꢀIsomer. 1H NMR (400 MHz, DMSOꢀd6), : 4.61
(s, CH2); 5.39—5.47 (m, N—CH2—C); 8.45 (s, CH). 1,5ꢀIsomer.
1H NMR (400 MHz, DMSOꢀd6), : 4.65 (s, CH2); 5.39—5.47
(m, N—CH2—C); 5.59 (d, N—CH2—C, J = 11.2 Hz); 5.77
(s, OH); 7.78 (s, CH). Method B. Yield 85% (a mixture of regioꢀ
isomers, 13a : 13b = 28 : 72). 1,4ꢀIsomer. 1H NMR (200 MHz,
DMSOꢀd6), : 4.62—4.67 (m, CH2—OH); 5.37—5.62 (m,
N—CH2—C, OH); 8.45 (s, CH). 1,5ꢀIsomer. 1H NMR
(200 MHz, DMSOꢀd6), : 4.62—4.67 (m, CH2—OH); 5.37—5.62
(m, N—CH2—C); 5.85 (s, OH); 7.80 (s, CH).
3,5ꢀDinitroꢀ5ꢀ(4ꢀphenylꢀ1Hꢀ1,2,3ꢀtriazolꢀ1ꢀyl)tetrahydroꢀ
1,3ꢀoxazine (20a) and 3,5ꢀdinitroꢀ5ꢀ(5ꢀphenylꢀ1Hꢀ1,2,3ꢀtriazolꢀ
1ꢀyl)tetrahydroꢀ1,3ꢀoxazine (20b). A reaction of 5ꢀazidoꢀ3,5ꢀ
dinitrotetrahydroꢀ1,3ꢀoxazine (4a) with phenylacetylene was
carried out according to method B. Yield 48% (a mixture of
regioisomers, 20a : 20b = 34 : 66). 1,4ꢀIsomer. 1H NMR
1
(400 MHz, DMSOꢀd6), : 9.27 (s, CH). 1,5ꢀIsomer. H NMR
(400 MHz, DMSOꢀd6), : 7.96 (s, CH).
[1ꢀ(3,5ꢀDinitrotetrahydroꢀ1,3ꢀoxazinꢀ5ꢀyl)ꢀ1Hꢀ1,2,3ꢀtriꢀ
azolꢀ4ꢀyl]methanol (21a) and [1ꢀ(3,5ꢀdinitrotetrahydroꢀ1,3ꢀoxꢀ
azinꢀ5ꢀyl)ꢀ1Hꢀ1,2,3ꢀtriazolꢀ5ꢀyl]methanol (21b). A reaction of
5ꢀazidoꢀ3,5ꢀdinitrotetrahydroꢀ1,3ꢀoxazine with propargyl alcoꢀ
hol was carried out according to method B. Yield 47% (a mixture
of regioisomers, 21a : 21b = 64 : 36). 1,4ꢀIsomer. 1H NMR
[1ꢀ(1ꢀtertꢀButylꢀ3ꢀnitroazetidinꢀ3ꢀyl)ꢀ1Hꢀ1,2,3ꢀtriazolꢀ4ꢀ
yl]methanol (15a) and [1ꢀ(1ꢀtertꢀbutylꢀ3ꢀnitroazetidinꢀ3ꢀyl)ꢀ1Hꢀ
1,2,3ꢀtriazolꢀ5ꢀyl]methanol (15b). A reaction of 3ꢀazidoꢀ1ꢀtertꢀ
butylꢀ3ꢀnitroazetidine (2b) with propargyl alcohol was carried
out according to methods A and B. Method A. Yield 78%
1
(400 MHz, DMSOꢀd6), : 8.66 (s, CH). 1,5ꢀIsomer. H NMR
(400 MHz, DMSOꢀd6), : 8.32 (s, CH).
1ꢀ(1,3ꢀDinitroazetidinꢀ3ꢀyl)ꢀ5ꢀphenylꢀ1Hꢀ1,2,3ꢀtriazole (12b).
Phenylacetylene (7) (0.14 g, 1.35 mmol) was added to 3ꢀazidoꢀ

1,2,3ꢀTriazoles from heterocyclic ꢀnitro azides
Russ.Chem.Bull., Int.Ed., Vol. 61, No. 11, November, 2012 2121
1,3ꢀdinitroazetidine (2a) (0.20 g, 1.06 mmol) in toluene (30 mL).
The reaction mixture was refluxed for 6 h. On cooling, the preꢀ
cipitate that formed was filtered off and washed with toluene.
Yield 0.13 g (41%), light creamꢀcolored crystals, m.p. 193.5—195 C.
IR, /cm–1: 3151 (CHtr), 3065, 3028 (CHPh), 2968 (CH), 1591,
1553, 1353, 1299 (NO2). 1H NMR (300 MHz, DMSOꢀd6),
: 5.15 (d, 2 H, CH2, J = 11.2 Hz); 5.21 (d, 2 H, CH2, J =
= 11.2 Hz); 7.29 (d, 2 H, Ph, J = 6.4 Hz); 7.59 (m, 3 H, Ph);
8.11 (s, 1 H, CH). 13C NMR (50 MHz, DMSOꢀd6), : 64.50
(CH2); 87.20 (C—NO2); 124.59 (pꢀCPh); 128.46 (oꢀCPh);
129.50 (mꢀCPh); 130.64 (ipsoꢀCPh); 133.61 (C=CH—N); 139.19
(N—C(Ph)=CH). Found (%): C, 45.47; H, 3.36; N, 28.99.
C11H10N6O4. Calculated (%): C, 45.52; H, 3.47; N, 28.96.
[1ꢀ(1,3ꢀDinitroazetidinꢀ3ꢀyl)ꢀ1Hꢀ1,2,3ꢀtriazolꢀ5ꢀyl]methanꢀ
ol (13b). A solution of 3ꢀazidoꢀ1,3ꢀdinitroazetidine (2a) (0.65 g,
3.46 mmol) and propargyl alcohol (0.30 g, 5.36 mmol) in toluꢀ
ene (30 mL) was refluxed for 11 h. On cooling, the precipitate
that formed was filtered off. The crude product was purified by
preparative TLC followed by recrystallization from ethyl aceꢀ
tate. Yield 0.40 g (47%), m.p. 188—190 C. IR, /cm–1: 3250
(OH), 3163 (CHtr), 3052, 2994 (CH), 1579, 1532, 1340 (NO2).
1H NMR (200 MHz, DMSOꢀd6), : 4.66 (d, 2 H, CH2—OH,
J = 3.8 Hz); 5.40 (d, 2 H, N—CH2—C, J = 11.8 Hz); 5.59 (d, 2 H,
N—CH2—C, J = 11.8 Hz); 5.84 (s, 1 H, OH); 7.80 (s, 1 H, CH).
13C NMR (50 MHz, DMSOꢀd6), : 52.46 (CH2—OH); 64.46
(N—CH2—C); 87.24 (C—NO2); 132.30 (C=CH—N); 138.79
(N—C(CH2)=CH). Found (%): C, 29.45; H, 3.38; N, 34.50.
C6H8N6O5. Calculated (%): C, 29.51; H, 3.30; N, 34.42.
Found (%): C, 48.47; H, 7.81; N, 23.49. C12H23N5O2Si. Calcuꢀ
lated (%): C, 48.46; H, 7.79; N, 23.55.
1ꢀ(2,2ꢀDimethylꢀ5ꢀnitroꢀ1,3ꢀdioxanꢀ5ꢀyl)ꢀ4ꢀtrimethylsilylꢀ
1Hꢀ1,2,3ꢀtriazole (19a) was obtained according to method B.
Yield 76%, m.p. 126—127 C. IR, /cm–1: 3094, 2999, 2959,
2900 (CH), 1563, 1377 (NO2), 1254, 840 (TMS). 1H NMR
(300 MHz, DMSOꢀd6), : 0.28 (s, 9 H, Si—Me); 1.39 (s, 3 H,
Me); 1.44 (s, 3 H, Me); 4.77 (d, 2 H, CH2, J = 12.8 Hz); 5.11
(d, 2 H, CH2, J = 12.8 Hz); 8.76 (s, 1 H, CH). 13C NMR (75 MHz,
DMSOꢀd6), : –1.27 (Si—Me); 20.79 (Me); 25.58 (Me);
61.94 (CH2); 91.29 (C—NO2); 99.54 (O—C(Me)2—O); 129.85
(N—CH=C); 145.98 (CH=C(TMS)—N). Found (%): C, 44.00;
H, 6.79; N, 18.52. C11H20N4O4Si. Calculated (%): C, 43.98;
H, 6.71; N, 18.65.
3ꢀtertꢀButylꢀ5ꢀnitroꢀ5ꢀ(4ꢀtrimethylsilylꢀ1Hꢀ1,2,3ꢀtriazolꢀ1ꢀ
yl)tetrahydroꢀ1,3ꢀoxazine (22a) was obtained according to methꢀ
od A. Yield 58%, m.p. 121—124.5 C. IR, /cm–1: 3141 (CHtr),
2973 (CH), 1565, 1345 (NO2), 1251, 846 (TMS). 1H NMR
(300 MHz, DMSOꢀd6), : 0.30 (s, 9 H, Si—Me); 1.08 (s, 9 H,
C—Me); 3.51 (d, 1 H N—CH2—C, J = 12.5 Hz); 4.13 (d, 1 H,
N—CH2—O, J = 8.1 Hz); 4.31 (d, 1 H, O—CH2—C, J = 12.5 Hz);
4.46 (d, 1 H, N—CH2—C, J = 12.5 Hz); 4.61 (d, 1 H, N—CH2—O,
J = 8.1 Hz); 5.15 (d, 1 H, O—CH2—C, J = 12.5 Hz); 8.79 (s, 1 H,
CH). 13C NMR (75 MHz, DMSOꢀd6), : –1.24 (Si—Me);
26.37 (C—Me); 50.40 (N—CH2—C); 52.96 (C—Me); 67.97
(C—CH2—O); 80.21 (N—CH2—O); 93.19 (C—NO2); 129.65
(N—CH=C); 145.81 (CH=C(TMS)—N). Found (%): C, 47.66
H, 7.59; N, 21.42 C13H25N5O3Si. Calculated (%): C, 47.68;
H, 7.70; N, 21.39.
1,3ꢀDiꢀtertꢀbutylꢀ5ꢀnitroꢀ5ꢀ(4ꢀtrimethylsilylꢀ1Hꢀ1,2,3ꢀtriꢀ
azolꢀ1ꢀyl)hexahydropyrimidine (23a) was obtained according to
method A. Yield 70%, m.p. 138—141.5 C. IR, /cm–1: 3122
(CHtr), 2983, 2966 (CH), 1566, 1555, 1363 (NO2), 1252, 845,
832 (TMS). 1H NMR (300 MHz, CDCl3), : 0.31 (s, 9 H, Si—Me);
1.12 (s, 18 H, C—Me); 3.21 (d, 1 H, N—CH—N, J = 8.8 Hz);
3.28 (d, 2 H, N—CH2—C, J = 12.1 Hz); 3.83 (d, 1 H, N—CH—N,
J = 8.8 Hz); 4.18 (d, 2 H, N—CH2—C, J = 12.1 Hz); 7.79 (s, 1 H,
CH). 13C NMR (75 MHz, DMSOꢀd6), : –1.24 (Si—Me); 26.05
(C—Me); 50.96 (N—CH2—C); 53.40 (C—Me); 63.01
(N—CH2N); 95.20 (C—NO2); 129.35 (N—CH=C); 145.51
(CH=C(TMS)—N). Found (%): C, 53.42; H, 9.03; N, 21.87.
C17H34N6O2Si. Calculated (%): C, 53.37; H, 8.96; N, 21.97.
Synthesis of 1,2,3ꢀtriazoles
Synthesis of trimethylsilylꢀ1,2,3ꢀtriazoles. Method A. A mixꢀ
ture of a nitro azide and trimethylsilylacetylene (9) in a molar
ratio of 1 : 10 was kept at room temperature for 20—30 days until
the starting azide was consumed completely (monitoring by
TLC). The excess trimethylsilylacetylene (9) was removed. When
needed, the product was recrystallized from chloroform—hexane.
Method B. A mixture of a nitro azide and trimethylsilylacetylꢀ
ene (9) in a molar ratio of 1 : 10 was kept in CH2Cl2 at 55 C for
7—13 h. The reaction mixture was cooled to room temperature
and concentrated in vacuo. When needed, the product was puriꢀ
fied by preparative TLC.
1ꢀ(1,3ꢀDinitroazetidinꢀ3ꢀyl)ꢀ4ꢀtrimethylsilylꢀ1Hꢀ1,2,3ꢀtriꢀ
azole (14a) was obtained according to method B. Yield 78%,
m.p. 132—135 C. IR, /cm–1: 3123 (CHtr), 3037, 2967 (CH),
1588, 1538, 1343, 1288 (NO2), 1247, 843 (TMS). 1H NMR
(200 MHz, DMSOꢀd6), : 0.3 (s, 9 H, Si—Me); 5.4 (s, 4 H, CH2);
8.6 (s, 1 H, CH). 13C NMR (50 MHz, DMSOꢀd6), : –1.17
(Si—Me); 65.16 (CH2); 86.46 (C—NO2); 132.01 (N—CH=C);
146.15 (CH=C(TMS)—N). Found (%): C, 33.60; H, 4.82; N, 29.48.
C8H14N6O4Si. Calculated (%): C, 33.56; H, 4.93; N, 29.35.
1ꢀ(1ꢀtertꢀButylꢀ3ꢀnitroazetidinꢀ3ꢀyl)ꢀ4ꢀtrimethylsilylꢀ1Hꢀ
1,2,3ꢀtriazole (16a) was obtained according to method A. Yield
62%, m.p. 86—88 C. IR, /cm–1: 3113 (CHtr), 2967 (CH),
1560, 1365, 1352 (NO2), 1249, 854, 840 (TMS). 1H NMR
(300 MHz, DMSOꢀd6), : 0.31 (s, 9 H, Si—Me); 0.97 (s, 9 H,
C—Me); 4.10 (d, 2 H, CH2, J = 9.1 Hz); 4.33 (d, 2 H, CH2,
J = 9.1 Hz); 8.72 (s, 1 H, CH). 13C NMR (50 MHz, DMSOꢀd6),
: –1.23 (Si—Me); 23.64 (C—Me); 52.05 (C—Me); 55.84 (CH2);
89.46 (C—NO2); 131.75 (N—CH=C); 146.02 (CH=C(TMS)—N).
Copper(I)ꢀcatalyzed synthesis of 1,2,3ꢀtriazoles
Freshly prepared aqueous solutions of ascorbic acid and
CuSO4•5H2O were added to a solution of an azide and an alkyne
in THF; the molar ratio of azide : alkyne : ascorbic acid : CuSO4
was 1 : 1.2 : 0.5 : 0.15. The reaction mixture was stirred at room
temperature for 1—3 h and diluted with water. The product was
extracted with ethyl acetate. The extract was dried with Na2SO4
and concentrated in vacuo. When needed, the product was puriꢀ
fied by preparative TLC with ethyl acetate—hexane as an eluent
(see Table 3).
1ꢀ(1,3ꢀDinitroazetidinꢀ3ꢀyl)ꢀ4ꢀphenylꢀ1Hꢀ1,2,3ꢀtriazole (12a).
IR, /cm–1: 3130 (CHtr), 3104 (CHPh), 3032, 2979 (CH), 1558,
1343, 1289 (NO2). 1H NMR (300 MHz, DMSOꢀd6), : 5.50 (s, 4 H,
CH2); 7.40 (m, 1 H, Ph); 7.51 (t, 2 H, Ph, J = 7.6 Hz); 7.88
(d, 2 H, Ph, J = 8.1 Hz); 9.02 (s, 1 H, CH). 13C NMR (75 MHz,
DMSOꢀd6), : 64.96 (CH2); 86.81 (C—NO2); 122.69 (pꢀCPh);

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Russ.Chem.Bull., Int.Ed., Vol. 61, No. 11, November, 2012
Katorov et al.
125.44 (oꢀCPh); 128.66 (N—CH=C); 129.16 (mꢀCPh); 129.48
(ipsoꢀCPh); 147.09 (CH=C(Ph)—N). Found (%): C, 45.56;
H, 3.39; N, 29.05. C11H10N6O4. Calculated (%): C, 45.52;
H, 3.47; N, 28.96.
[1ꢀ(1,3ꢀDinitroazetidinꢀ3ꢀyl)ꢀ1Hꢀ1,2,3ꢀtriazolꢀ4ꢀyl]methꢀ
anol (13a). IR, /cm–1: 3341 (OH), 3154 (CHtr), 2970 (CH),
1584, 1559, 1355, 1338, 1281 (NO2). 1H NMR (300 MHz,
DMSOꢀd6), : 4.61 (s, 2 H, CH2—OH); 5.39 (s, 1 H, OH); 5.43
(s, 4 H, N—CH2—C); 8.44 (s, 1 H, CH). 13C NMR (75 MHz,
DMSOꢀd6), : 54.82 (CH2—OH); 65.04 (N—CH2—C); 86.75
(C—NO2); 124.08 (N—CH=C); 149.15 (CH=C(CH2)—N).
Found (%): C, 29.54; H, 3.25; N, 34.49. C6H8N6O5. Calculatꢀ
ed (%): C, 29.51; H, 3.30; N, 34.42.
[1ꢀ(3,5ꢀDinitrotetrahydroꢀ1,3ꢀoxazinꢀ5ꢀyl)ꢀ1Hꢀ1,2,3ꢀtriꢀ
azolꢀ4ꢀyl]methanol (21a). IR, /cm–1: 3386 (OH), 3155 (CHtr),
3039, 2941, 2887 (CH), 1576, 1339, 1290 (NO2), 1083, 1022
(C—O). 1H NMR (300 MHz, DMSOꢀd6), : 4.60 (d, 2 H,
CH2—OH, J = 5.1 Hz); 4.89 (d, 1 H, O—CH2—C, J = 12.5 Hz);
5.10 (d, 1 H, O—CH2—C, J = 12.5 Hz); 5.19 (d, 1 H, N—CH2—C,
J = 15.4 Hz); 5.28 (d, 1 H, O—CH2—N, J = 11.7 Hz); 5.43 (m, 1 H,
OH); 5.86 (m, 2 H, O—CH2—C, N—CH2—C); 8.67 (s, 1 H,
CH). 13C NMR (50 MHz, DMSOꢀd6), : 49.57 (N—CH2—C);
54.82 (CH2—OH); 68.99 (C—CH2—O); 76.64 (N—CH2—O);
90.84 (C—NO2); 123.11 (N—CH=C); 149.23 (CH=C(CH2)—N).
Found (%): C, 30.68; H, 3.77; N, 30.69. C7H10N6O6. Calculatꢀ
ed (%): C, 30.66; H, 3.68; N, 30.65.
[1ꢀ(1ꢀtertꢀButylꢀ3ꢀnitroazetidinꢀ3ꢀyl)ꢀ1Hꢀ1,2,3ꢀtriazolꢀ4ꢀ
yl]methanol (15a). IR, /cm–1: 3199 (OH), 3143 (CHtr), 2978
(CH), 1566, 1370, 1353 (NO2). 1H NMR (300 MHz, DMSOꢀd6),
: 0.96 (s, 9 H, Me); 4.09 (d, 2 H, N—CH2—C, J = 9.5 Hz); 4.31
(d, 2 H, N—CH2—C, J = 9.5 Hz); 4.60 (d, 2 H, CH2—OH,
J = 5.1 Hz); 5.34 (t, 1 H, OH, J = 5.1 Hz); 8.53 (s, 1 H, CH).
13C NMR (75 MHz, DMSOꢀd6), : 23.63 (Me); 52.06 (C—Me);
54.88 (CH2—OH); 55.81 (N—CH2—C); 89.75 (C—NO2); 123.98
(N—CH=C); 149.03 (CH=C(CH2)—N). Found (%): C, 47.12;
H, 6.68; N, 27.36. C10H17N5O3. Calculated (%): C, 47.05;
H, 6.71; N, 27.43.
1ꢀ(1ꢀtertꢀButylꢀ3ꢀnitroazetidinꢀ3ꢀyl)ꢀ4ꢀphenylꢀ1Hꢀ1,2,3ꢀtriꢀ
azole (24). IR, /cm–1: 3128 (CHtr), 3085, 3066 (CHPh), 3034,
2969 (CH), 1565, 1353 (NO2). 1H NMR (300 MHz, DMSOꢀd6),
: 0.99 (s, 9 H, Me); 4.17 (d, 2 H, CH2, J = 8.8 Hz); 4.37 (d, 2 H,
CH2, J = 9.5 Hz); 7.40 (m, 1 H, Ph); 7.50 (t, 2 H, Ph, J = 7.0 Hz);
7.91 (d, 2 H, Ph, J = 7.3 Hz); 9.14 (s, 1 H, CH). 13C NMR
(75 MHz, DMSOꢀd6), : 23.63 (Me); 52.08 (C—Me); 55.66
(CH2); 89.91 (C—NO2); 122.57 (pꢀCPh); 125.44 (oꢀCPh); 128.53
(N—CH=C); 129.03 (mꢀCPh); 129.65 (ipsoꢀCPh); 147.12
(CH=C(Ph)—N). Found (%): C, 59.75; H, 6.40; N, 23.21.
C15H19N5O2. Calculated (%): C, 59.79; H, 6.36; N, 23.24.
3ꢀtertꢀButylꢀ5ꢀnitroꢀ5ꢀ(4ꢀphenylꢀ1Hꢀ1,2,3ꢀtriazolꢀ1ꢀyl)ꢀ
tetrahydroꢀ1,3ꢀoxazine (25). IR, /cm–1: 3122 (CHtr), 3092
(CHPh), 3027, 3006, 2970 (CH), 1563, 1367 (NO2). 1H NMR
(300 MHz, DMSOꢀd6), : 1.09 (s, 9 H, Me); 3.64 (d, 1 H,
N—CH2—C, J = 11.7 Hz); 4.18 (d, 1 H, N—CH2—O, J = 7.3 Hz);
4.43 (d, 2 H, N—CH2—C, O—CH2—C, J = 11.0 Hz); 4.60
(d, 1 H, N—CH2—O, J = 7.3 Hz); 5.12 (d, 1 H, O—CH2—C,
J = 11.7 Hz); 7.44 (m, 3 H, Ph); 7.90 (d, 2 H, Ph, J = 7.3 Hz);
9.28 (s, 1 H, CH). 13C NMR (75 MHz, DMSOꢀd6), : 26.41
(Me); 50.34 (N—CH2—C); 53.05 (C—Me); 67.87 (C—CH2—O);
80.33 (N—CH2—O); 93.47 (C—NO2); 120.84 (pꢀCPh); 125.39
(oꢀCPh); 128.62 (N—CH=C); 129.05 (mꢀCPh); 129.54 (ipsoꢀCPh);
146.94 (CH=C(Ph)—N). Found (%): C, 58.08; H, 6.44;
N, 21.08. C16H21N5O3. Calculated (%): C, 57.99; H, 6.39;
N, 21.13.
[1ꢀ(1,3ꢀDiꢀtertꢀbutylꢀ5ꢀnitrohexahydropyrimidinꢀ5ꢀyl)ꢀ1Hꢀ
1,2,3ꢀtriazolꢀ4ꢀyl]methanol (26). IR, /cm–1: 3278 (OH), 3176
(CHtr), 2974 (CH), 1559, 1367, 1346 (NO2). 1H NMR
(300 MHz, CDCl3), : 1.12 (s, 18 H, Me); 3.46 (m, 3 H,
N—CH—N, N—CH2—C); 3.62 (d, 1 H, N—CH—N, J = 8.8 Hz);
3.93 (d, 2 H, N—CH2—C, J = 11.7 Hz); 4.80 (s, 2 H, CH2—OH);
7.89 (s, 1 H, CH). 13C NMR (75 MHz, DMSOꢀd6), : 26.07
(Me); 50.93 (N—CH2—C); 53.51(C—Me); 54.82 (CH2—OH);
63.13 (N—CH2—N); 95.48 (C—NO2); 122.12 (N—CH=C);
148.46 (CH=C(CH2)—N). Found (%): C, 52.82; H, 8.36;
N, 24.68. C15H28N6O3. Calculated (%): C, 52.92; H, 8.29;
N, 24.69.
1ꢀ(2,2ꢀDimethylꢀ5ꢀnitroꢀ1,3ꢀdioxanꢀ5ꢀyl)ꢀ4ꢀphenylꢀ1Hꢀ1,2,3ꢀ
triazole (17a). IR, /cm–1: 3128 (CHtr), 3103 (CHPh), 3092,
2999 (CH), 1572, 1380 (NO2). 1H NMR (300 MHz, DMSOꢀd6),
: 1.43 (s, 3 H, Me); 1.44 (s, 3 H, Me); 4.85 (d, 2 H, CH2,
J = 13.2 Hz); 5.11 (d, 2 H, CH2, J = 12.5 Hz); 7.39 (t, 1 H, Ph,
J = 7.3 Hz); 7.50 (t, 2 H, Ph, J = 7.3 Hz); 7.89 (d, 2 H, Ph,
J = 8.1 Hz), 9.25 (s, 1 H, CH). 13C NMR (75 MHz, DMSOꢀd6),
: 21.38 (Me); 24.95 (Me); 61.89 (CH2); 91.51 (C—NO2); 99.69
(O—C(Me)2—O); 121.08 (pꢀCPh); 125.40 (oꢀCPh); 128.63
(N—CH=C); 129.06 (mꢀCPh); 129.44 (ipsoꢀCPh); 147.07
(CH=C(Ph)—N). Found (%): C, 55.30; H, 5.27; N, 18.47.
C14H16N4O4. Calculated (%): C, 55.26; H, 5.30; N, 18.41.
[1ꢀ(2,2ꢀDimethylꢀ5ꢀnitroꢀ1,3ꢀdioxanꢀ5ꢀyl)ꢀ1Hꢀ1,2,3ꢀtriꢀ
azolꢀ4ꢀyl]methanol (18a). IR, /cm–1: 3298 (OH), 3145 (CHtr),
3009, 2935 (CH), 1575, 1360 (NO2). 1H NMR (300 MHz,
DMSOꢀd6), : 1.41 (s, 6 H, Me); 4.58 (d, 2 H, CH2—OH,
J = 4.4 Hz); 4.79 (d, 2 H, O—CH2—C, J = 12.5 Hz); 5.07 (d, 2 H,
O—CH2—C, J = 12.5 Hz); 5.38 (t, 1 H, OH, J = 5.1 Hz); 8.60
(s, 1 H, CH). 13C NMR (75 MHz, DMSOꢀd6), : 21.58 (Me);
24.78 (Me); 54.82 (CH2—OH); 61.93 (O—CH2—C); 91.52
(C—NO2); 99.64 (O—C(Me)2—O); 122.50 (N—CH=C); 148.94
(CH=C(CH2)—N). Found (%): C, 41.90; H, 5.38; N, 21.64.
C9H14N4O5. Calculated (%): C, 41.86; H, 5.46; N, 21.70.
3,5ꢀDinitroꢀ5ꢀ(4ꢀphenylꢀ1Hꢀ1,2,3ꢀtriazolꢀ1ꢀyl)tetrahydroꢀ
1,3ꢀoxazine (20a). IR, /cm–1: 3140 (CHtr), 3109 (CHPh), 3046,
3030 (CH), 1579—1570, 1293 (NO2), 1011 (COC). 1H NMR
(300 MHz, DMSOꢀd6), : 4.97 (d, 1 H, O—CH2—C, J = 12.4 Hz);
5.17 (d, 1 H, O—CH2—C, J = 12.4 Hz); 5.30 (m, 2 H,
O—CH2—C, N—CH2—C); 5.92 (m,
2 H, O—CH2—C,
References
N—CH2—C); 7.41 (m, 1 H, Ph); 7.52 (t, 2 H, Ph, J = 8.0 Hz);
7.90 (d, 2 H, Ph, J = 7.1 Hz); 9.30 (s, 1 H, CH). 13C NMR
(75 MHz, DMSOꢀd6), : 49.43 (N—CH2—C); 68.86 (C—CH2—O);
76.51 (N—CH2—O); 90.73 (C—NO2); 121.59 (pꢀCPh); 125.37
(oꢀCPh); 128.71 (N—CH=C); 129.06 (mꢀCPh); 129.22 (ipsoꢀCPh);
147.18 (CH=C(Ph)—N). Found (%): C, 45.04; H, 3.80;
N, 26.23. C12H12N6O5. Calculated (%): C, 45.00; H, 3.78;
N, 26.24.
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Received February 17, 2012;
in revised form October 2, 2012