Synthesis of nitroolefins and nitroarenes under mild conditions

Article abstract of DOI:10.1021/acs.joc.7b03289

1,3-Disulfonic acid imidazolium nitrate {[Dsim]NO₃} was prepared and characterized as a new ionic liquid and nitrating agent for the ipso-nitration of various arylboronic acids and nitro-Hunsdiecker reaction of different α,β-unsaturated acids and benzoic acid derivatives, by in situ generation of NO₂ to give various nitroarenes and nitroolefins without using any cocatalysts and solvents under mild conditions.

Full text of DOI:10.1021/acs.joc.7b03289

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Synthesis of Nitroolefins and Nitroarenes under mild conditions
Mahmoud Zarei, Ehsan Noroozizadeh, Ahmad Reza Moosavi-Zare, and Mohammad Ali Zolfigol
J. Org. Chem., Just Accepted Manuscript • DOI: 10.1021/acs.joc.7b03289 • Publication Date (Web): 05 Mar 2018
Downloaded from http://pubs.acs.org on March 5, 2018
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Synthesis of Nitroolefins and Nitroarenes under mild
conditions
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Mahmoud Zarei,a,* Ehsan Noroozizadeh,a Ahmad R. MoosaviꢀZare, b,* and Mohammad A.
Zolfigola,*
aDepartment of Organic Chemistry, Faculty of Chemistry, BuꢀAli Sina University, Hamedan,
6541861841, Iran
bSayyed Jamaleddin Asadabadi University, Asadabad, 6541861841, Iran
Eꢀmail address: moosavizare@yahoo.com, mzolfigol@yahoo.com
Solvent-free, 50 oC
NO2
70-85% yields
R
COOH
R
COOH
R
NO2
R
[Dsim]NO3
B(OH)2
NO2
R
R
Solvent-free, r.t.
75-92% yields
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ABSTRACT
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1,3ꢀdisulfonic acid imidazolium nitrate {[Dsim]NO3} was prepared and characterized as a new
ionic liquid and nitrating agent, for the ipsoꢀnitration of various arylboronic acids and nitroꢀ
Hunsdiecker reaction of different α,βꢀunsaturated acids and benzoic acid derivatives, by in situ
generation of NO2, to give various nitroarenes and nitroolefins without using any coꢀcatalysts
and solvents under mild conditions.
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KEYWORDS
1,3ꢀdisulfonic acid imidazolium nitrate, Ipsoꢀnitration, NitroꢀHunsdiecker reaction, Nitroolefin,
Nitroarene.
INTRODUCTION
Nitro aromatic compounds are valuable materials because of their applications on the
preparation of chemical intermediates for the synthesis of dyes, plastics, perfumes, energetic
materials and pharmaceuticals.1, 2 They have been used as significant intermediates in various
functional group transformations.3 Nitroolefins, as another group of nitro compounds, are widely
used in cycloaddition reaction, Diels–Alder reaction and Michael reaction to prepare various
organic intermediates and also with reduction process of them it can produce nitroalkanes.4
Recently, sulfonic acid functionalized imidazolium salts have been designed as an efficient
and important group of acidic ionic liquids and solid salts. They have successfully used as
catalysts and reagents for the synthesis of some important organic compounds such as
bis(indolyl)methans,5,6 Nꢀsulfonyl imines,7 nitro phenolic compounds,8 1ꢀamidoalkylꢀ2ꢀ
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naphthols,9 benzimidazoles,10 xanthene derivatives,11 1,2,4,5ꢀtetrasubstituted imidazoles,12 and
amidoꢀalkylꢀphenols.13
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Herein, we have synthesized 1,3ꢀdisulfonic acid imidazolium nitrate {[Dsim]NO3} and
fully characterized by IR, 1H NMR and 13C NMR, TG, DTG as well as mass spectra (Scheme 1).
[Dsim]NO3 was successfully used as a novel ionic liquid and nitrating agent for the ipsoꢀnitration
reaction of arylboronic acids to give nitroarenes (Scheme 2) and nitroꢀHunsdiecker reactions by
the decarboxylative nitration of various α,βꢀunsaturated acids and benzoic acid derivatives to
give various (E)ꢀnitroolefins and nitroarenes, respectively, under mild and solventꢀfree
conditions without using any coꢀcatalysts. All products were synthesized fast with high yields
and in very short reaction times (Schemes 2 & 3).
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Scheme 1. The synthesis of 1,3ꢀdisulfonic acid imidazolium nitrate [Dsim]NO3.
B(OH)2
NO2
[DSim]NO3
r.t.
R
R
Scheme 2. The synthesis of nitroarenes by ipso nitration reaction of arylboronic acids using [Dsim]NO3.
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Scheme 3. The synthesis of (E)ꢀnitroolefins and nitroarenes by the nitroꢀHunsdiecker reaction using [Dsim]NO3.
RESULTS AND DISCUSSION
At first, by the reaction of imidazole (1 mmol) and chlorosulfonic acid (2 mmol) in CH2Cl2
as a solvent, 1,3ꢀdisulfonic acid imidazolium chloride {[Dsim]Cl} was prepared.8, 9 In the next
step, HNO3 (1 mmol) was reacted with [Dsim]Cl (1 mmol) to give 1,3ꢀdisulfonic acid
imidazolium nitrate {[Dsim]NO3} as a novel ionic liquid and nitrating agent by the release of
1
HCl (1 mmol) (Scheme 1). The structure of [Dsim]NO3 was studied and identified by IR, H
NMR, 13C NMR, TG, DTG as well as mass spectra (Figures S1ꢀS5).
The thermal gravimetric (TG) and differential thermal gravimetric (DTG) analysis of
[Dsim]NO3 were studied and the main weight loss occurred after 200 ºC which was related to
molecular decomposition of [Dsim]NO3 (Figure S5). Also, the weight loss of the reagent during
the range of 75 ºC to 200 ºC could be related to release of NO2.
To show the efficiency of [Dsim]NO3 on the preparation of nitro aromatic compounds, we
have tested it on the ipsoꢀnitration reaction of various arylboronic acids. This reaction was
previously reported in the presence of some various nitrating agents, coꢀcatalysts and solvents
such as Bi(NO3)5H2O/K2S2O8/ toluene under nitrogen atmosphere,1 tertꢀbutyl nitrile/dioxane,14
NH4NO3/(CF3CO)2O/CH3CN,15
[bisꢀ(trifluoroacetoxy)]iodobenzene/Nꢀbromosuccinimide
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(NBS)/sodium nitrite/ CH3CN,16 HNO3/TMSꢀCl/CH2Cl2,17 tertꢀbutyl nitrite/MeCN18 and
Bi(NO3)3. 5H2O/Toluene or Benzene under nitrogen atmosphere.19 Using coꢀcatalysts and
solvents, high temperature, long reaction times and low yields are some disadvantages of
previous reported works. In the present work, the reaction of 3ꢀnitrophenyl boronic acid (1
mmol) with [DSim]NO3 (1 mmol) was selected as a model reaction and tested at different
temperatures in various solvents such as CH2Cl2, CHCl3, H2O, EtOH, Acetone and EtOAc in
comparison with solventꢀfree conditions. The best result was obtained at room temperature in the
absence of solvent (Table 1).
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Table 1. The effect of various temperatures and solvents on the reaction of 3ꢀnitrophenyl boronic acid (1 mmol) with
[DSim]NO3 (1 mmol).
Entry
Solvent
ꢀ
Temp. (˚C)
Time (min)
Yield [a] (%)
1
2
3
4
5
6
7
8
9
r.t.
50
70
r.t.
r.t.
r.t.
r.t.
r.t.
r.t.
1
1
1
92
92
92
59
38
18
21
31
32
ꢀ
ꢀ
CH2Cl2
CHCl3
H2O
EtOH
Acetone
EtOAc
8
60
60
60
60
60
[a] Isolated yield.
After the optimization of the reaction condition, various arylboronic acids containing
electronꢀreleasing substituents, electronꢀwithdrawing substituents and halogens on the aromatic
ring of boronic acids were reacted with [Dsim]NO3 to give the desired nitro aromatic
compounds. All products were prepared with high yields in very short reaction times (Scheme 4).
Many of the compounds which is shown in Scheme 4 are hardly produced by previously
methods.
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Scheme 4. The synthesis of nitro aromatic compounds by ipsoꢀnitration of various arylboronic acids using
[Dsim]NO3
According to previous studies,2, 20 to show that NO2 in equilibrium with N2O4 could be
exposed from [Dsim]NO3, the released gas was conducted to a roundꢀbottomed flask containing
copper powder and ethyl acetate. By the reaction of NO2 with copper powder, Cu(NO3)2 was
prepared with blue colour. The black sediment was collected in the roundꢀbottomed flask as a
result of the reaction of excess copper powder with O2 produced from [Dsim]NO2 (Figure 1).
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Figure 1. The synthesis of copper nitrate by the reaction of nitrogen oxide with copper powder.
In the proposed mechanism, the released nitrogen dioxide from [Dsim]NO3 could be
reacted with phenylboronic acid to give I and nitrous acid. In the next step, by the reaction of I,
as a radical intermediate compound, with nitrogen dioxide, II was prepared which could be
easily converted in III. Then, by the intramolecular rearrangement of III, nitro benzene and
oxoborinic acid were obtained. Finally, by the reaction of oxoborinic acid with one molecule of
H2O, boric acid was prepared at the end of reaction (Scheme 5).
N
N
4
N
N
+
4NO2 + O2 + 2H2O
SO3
NO3
4 HO3S
SO3H
HO3S
•
NO2
•
O
NO2
•
OH
O
B
N
O
B
- HNO2
O
B
OH
I
OH
II
OH
NO2
O
N
B
O
HO
O
O
B
III
OH
HO
OH
B
B
H2O
HO
O
OH
Scheme 5. The proposed mechanism for the ipso nitration reaction of arylboronic acid using
[DSim]NO3.
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To illustrate the effect of nitrogen dioxide, as a radical species, on the progression of the
reaction, the model reaction was studied in the presence of different amounts of iodine or
butylated hydroxytoluene (BHT) as a radical scavenger. According to Table 2, as the amount of
iodine or BHT increased, the reaction yield was decreased. This observation clearly confirmed
the radical pathway of the reaction mechanism.
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Table 2. The effect of iodine and BHT as radical scavengers on the synthesis of
1,3ꢀdinitrobenzene using [DSim]NO3.
Entry
I2 (mmol)
Time
(min)
1
240
240
240
240
240
Yield (%)
BHT
(mmol)
0
Time
(min)
1
240
240
240
240
240
Yield (%)
1
2
3
4
5
6
0
92
55
48
36
28
15
92
54
46
35
27
2
0.2
0.4
0.6
0.8
1
0.2
0.4
0.6
0.8
1
aIsolated yield.
The synthesis of nitroolefin derivatives previously was reported in the presence of some
various nitrating agents, coꢀcatalysts and solvents such as tꢀBuONO / TEMPO/ CH3CN,4
Fe(NO3)3/ pyridine/ toluene,21 Cu(NO3)2/ CH3CN,22 HNO3/AIBN/CH3CN23 and
AgNO2/TEMPO/dichloroethane.24 However, some of these methods have some disadvantages
such as low yields, long reaction times, hard reaction conditions, usage of solvents and coꢀ
catalysts.
In the next step, to show the ability of [Dsim]NO3 as a nitrating agent, we tested it on the
nitroꢀHunsdiecker reaction to give nitroolefins and nitroarenes by in situ generation of NO2
without using any coꢀcatalysts under nitrogen atmosphere. For this purpose, the reaction of (E)ꢀ
3ꢀ(3,4,5ꢀtrimethoxyphenyl)acrylic acid with [Dsim]NO3 was considered as a model reaction and
tested at different temperatures to demonstrate the best reaction condition (Table 3). As it is
shown in Table 3, indicates that, the best result was achieved at 50 °C. The yield of product was
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not improved by increasing the temperature and reaction time. The model reaction was also
tested in the presence of various solvents such as CHCl3, H2O, EtOH and EtOAc at 50 ˚C and in
CH2Cl2 and acetone under reflux conditions (Table 3). As results from Table 3, indicates that the
best result was obtained in the absence of solvent. The model reaction was also tested under
oxygen atmosphere but the result was not satisfactory.
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Table 3. The effect of various temperatures and solvents on the reaction of (E)ꢀ3ꢀ(3,4,5ꢀtrimethoxyphenyl)acrylic
acid (1 mmol) with [Dsim]NO3 (1 mmol) under nitrogen atmosphere.
Entry
Solvent
Temp.(ºC)
Time (min)
Yield [a] (%)
1
2
3
4
ꢀ
ꢀ
ꢀ
r.t.
50
70
45
10
10
15
Trace
80
80
CH2Cl2
reflux
53
5
CHCl3
50
60
15
6
7
8
9
H2O
EtOH
Acetone
EtOAc
50
50
reflux
50
60
60
60
60
ꢀ
12
25
35
[a] Isolated yield.
After the optimization of the reaction condition, the reaction of various α,βꢀunsaturated
acids and benzoic acid derivatives with [Dsim]NO3 was investigated to prepare of various (E)ꢀ
nitroolefins and nitroarenes under nitrogen atmosphere and solventꢀfree conditions (Scheme 6).
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Scheme 6. The preparation of (E)ꢀnitroolefins and nitroarenes by the nitroꢀHunsdiecker reaction of various α,βꢀ
unsaturated acids and benzoic acid derivatives with [Dsim]NO3 under nitrogen atmosphere and solventꢀfree
conditions.
In the proposed mechanism according to reported literature,3, 21ꢀ23 decarboxylative nitration
of α,βꢀunsaturated acids could be occurred through three pathways (Scheme 7). In path 1,
decarboxylation was carried out and then NO2 group was added to substrate. But in the other
pathways, after addition of NO2 group to substrate, decarboxylation occurred and nitroolefin
compound was prepared.
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Scheme 7. The proposed mechanism for the nitroꢀHunsdiecker reaction of α,βꢀunsaturated acids using [DSim]NO3.
3, 23
In the proposed mechanism for the nitrodecarboxylation of aryl carboxylic acid,
suggested that benzoic acid could be reacted with nitrogen dioxide, which was exposed from
[DSim]NO3, to give benzoic nitric anhydride and nitrous acid. Then, benzoic nitric anhydride
was decomposed to benzoate radical and nitrogen dioxide and finally by the reaction of these
compounds together, nitrobenzene was prepared (Scheme 8).
it is
Scheme 8. The proposed mechanism for the nitro decarboxylation of aryl carboxylic acids using [DSim]NO3.
To confirm the effect of nitrogen dioxide, as a radical species, on the progression of the
reaction, nitro decarboxylation of (E)ꢀ3ꢀ(3,4,5ꢀtrimethoxyphenyl)acrylic acid using [DSim]NO3
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was tested in the presence of iodine or butylated hydroxytoluene (BHT) as a radical scavenger
(Table 4). With the increase of iodine or BHT, the yield of product decreased even after a long
time. This observation clearly showed that nitrogen dioxide with radical properties is effective in
this reaction.
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Table 4. The effect of iodine and BHT as radical scavengers on nitrodecarboxylation of (E)ꢀ3ꢀ(3,4,5ꢀ
trimethoxyphenyl)acrylic acid using [DSim]NO3
Entry
I2 (mmol)
Time
(min)
10
240
240
240
240
240
Yield a(%)
BHT
(mmol)
0
Time
(min)
10
240
240
240
240
240
Yield a(%)
1
2
3
4
5
6
0
82
42
35
32
22
10
82
55
45
38
30
15
0.2
0.4
0.6
0.8
1
0.2
0.4
0.6
0.8
1
[a]Isolated yield.
To demonstrate the suitability of this method in comparison with some previous reported
works, the results for nitro decarboxylation of (E)ꢀ3ꢀ(3,4,5ꢀtrimethoxyphenyl)acrylic acid using
some different reagents and conditions were studied and summarized in Table 5. As it is shown
in Table 5, indicates that the presented method is superior to other mentioned methods. Long
reaction time, high temperature and using of coꢀcatalyst and solvent are some disadvantages for
the previous methods.
Table 5. Comparison of the results for the nitro decarboxylation of (E)ꢀ3ꢀ(3,4,5ꢀtrimethoxyphenyl) acrylic acid
using different reagents and conditions.
Time
(min)
Yield
(%)
Entry
Reaction Condition
Ref.
1
tꢀBuONO / TEMPO/ CH3CN/ 50 °C
180
80
4
2
3
4
Cu(NO3)2/ CH3CN
HNO3/AIBN/ CH3CN/ 50 °C
[DSim]NO3 / 50 °C
480
120
10
93
80
82
22
23
ꢀa
aOur method.
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Conclusion
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In conclusion, we have prepared 1,3ꢀdisulfonic acid imidazolium nitrate [Dsim]NO3 as a
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new ionic liquid and fully characterized by IR, H NMR and C NMR, TG, DTG as well as
mass spectra. [Dsim]NO3 was successfully applied as a nitrating agent for the ipsoꢀnitration
reaction of arylboronic acids to give nitroarenes at room temperature under solventꢀfree
conditions. Also, it was used for the nitroꢀHunsdiecker reaction by the decarboxylative nitration
of different α,βꢀunsaturated acids, and benzoic acid derivatives to prepare of various (E)ꢀ
nitroolefins and nitroarenes respectively without using any coꢀcatalysts at 50 °C under solventꢀ
free conditions and nitrogen atmosphere. All products were synthesized fast with high yields and
in very short reaction times.
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EXPERIMENTAL SECTION
General Methods.
All chemicals were purchased from Merck, SigmaꢀAldrich or Fluka Chemical Companies. The
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known products were identified by comparison of their physical and spectral data (IR, H NMR,
13C NMR, and mass) with previous reported in the literature. Progress of the reaction was
monitored by TLC.
Procedure for the synthesis of 1,3ꢀdisulfonic acid imidazolium nitrate [Dsim]NO3
To a roundꢀbottomed flask (100 mL) containing imidazole (0.340 g, 5 mmol) in dry
CH2Cl2 (50 mL), was added chlorosulfonic acid (1.1885 g, 10.2 mmol) drop wise over a period
of 20 minutes at room temperature. After the addition was completed, the reaction mixture was
stirred for 12 hours under a continuous flow of nitrogen (to remove the produced HCl), standing
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for 5 minutes, and the CH2Cl2 was decanted. The residue was washed with dry CH2Cl2 (3×50
mL) and dried under vacuum to make [Dsim]Cl viscous pale yellow.9 Then, nitric acid 100 %
(0.315 g, 5 mmol) was added drop wise to [Dsim]Cl (0.993 g, 5 mmol) over a period of 5
minutes at room temperature under a continuous flow of nitrogen to remove the HCl gas that is
produced. The resulting mixture was stirred for 10 minutes under this condition to give
[Dsim]NO3 as a viscous yellow red oil.
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Spectral data of [Dsim]NO3
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Pale yellow red oil; IR (KBr): 576, 1068, 1175, 1286, 1585, 3100ꢀ3500 cm–1; H NMR
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(300 MHz, DMSOꢀd6): δ (ppm) 7.51 (s, 2H), 8.88 (s, 1H), 12.83 (s, 2H); C NMR (75 MHz,
DMSOꢀd6): δ (ppm) 119.7, 134.6; M.S (M+): 291.
Procedure for the preparation of nitroarenes by ipso nitration reaction of boric acid using
[Dsim]NO3
To a roundꢀbottomed flask (10 mL) containing of [Dsim]NO3 (0.291 g, 1 mmol),
arylboronic acid (1 mmol) was added and the mixture was stirred at room temperature. After the
reaction was completed as monitored by TLC, dichloromethane (5 mL) was added to the reaction
mixture and stirred for 2 minutes, and then the desired product was easily extracted, dried over
MgSO4 and filtered. Finally, the product was purified by plate chromatography (EtOAc/nꢀ
hexane: 1/4).
Procedure for the preparation of (E)ꢀnitroolefins and nitroarenes by nitroꢀHunsdiecker
reaction of various α,βꢀunsaturated acids and benzoic acid derivatives using [DSim]NO3.
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To a roundꢀbottomed flask (10 mL) containing of [Dsim]NO3 (0.291 g, 1 mmol),
α,βꢀunsaturated acid (1 mmol) or benzoic acid derivative (1 mmol) was added and the mixture
was stirred at 50 °C for appropriate time under nitrogen atmosphere. After the reaction was
completed as monitored by TLC, dichloromethane (5 mL) was added to the reaction mixture and
stirred for 2 minutes, dried over MgSO4 and filtered. Finally, the product was purified by plate
chromatography (EtOAc/nꢀhexane: 1/4).
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Spectral data of compounds:
1ꢀFluoroꢀ4ꢀnitrobenzene (1a)
Yellow solid; mp 109ꢀ112 °C (lit. [17]); isolated yield 84% (0.118 g); 1H NMR (400 MHz,
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Acetoneꢀd6) δ (ppm) 7.53 (dd, J= 6, 3.2 Hz, 2H), 7.64 (dd, J= 6, 3.2 Hz, 2H); C NMR (100
MHz, Acetoneꢀd6) δ (ppm) 125.2, 127.4, 127.9, 171.7; M.S (M+): 141.
1ꢀFluoroꢀ3ꢀnitrobenzene (2a)
Yellow solid; mp 42ꢀ45 °C (lit. [28]); isolated yield 78% (0.110 g); IR (KBr) 747, 1303,
1563, 2939 cm−1; 1H NMR (400 MHz, Acetoneꢀd6) δ (ppm) 7.68ꢀ7.72 (m, 2H), 8.57 (s, br, 2H);
13C NMR (100 MHz, Acetoneꢀd6) δ (ppm) 112.4, 112.6, 121.1; M.S (M+): 141.
1ꢀNitrobenzene (3a)
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Yellow Oil; mp 215ꢀ217 °C (lit. [24] mp 213ꢀ215 °C); isolated yield 74% (0.091 g); H
NMR (300 MHz, CDCl3) δ (ppm) 7.55 (t, J = 8.1 Hz, 2H), 7.71 (t, J = 4.5 Hz, 1H), 8.30 (d, J =
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8.1 Hz, 2H); C NMR (100 MHz, DMSOꢀd6) δ (ppm) 123.4, 129.3, 134.6, 148.1; M.S (M+):
123.
1ꢀMethoxyꢀ4ꢀnitrobenzene (4a)
Yellow solid; mp 53ꢀ55 °C (lit. [2] mp 52ꢀ54 °C); isolated yield 90% (0.137 g); IR (KBr)
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751, 1344, 1591, 3081 cm−1; H NMR (300 MHz, DMSOꢀd6) δ (ppm) 3.90 (s, 3H), 7.15 (d,
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J=9.3 Hz, 2H), 8.22 (d, J= 9.3 Hz, 2H), 13C NMR (100 MHz, DMSOꢀd6) δ (ppm) 56.67, 115.06,
126.3, 141.2, 165.0; M.S (M+ + 1): 154.
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1ꢀTertꢀbutylꢀ4ꢀnitrobenzene (5a)
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Yellow solid; mp 99ꢀ102 °C (lit. [1]); isolated yield 89% (0.159 g); IR (KBr) 697, 1348,
1555, 2967 cm−1; 1H NMR (400 MHz, CDCl3) δ (ppm) 1.31 (s, 9H), 7.46 (d, J = 8.4 Hz, 2H),
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8.09 (d, J = 8.4 Hz, 2H), C NMR (100 MHz, CDCl3) δ (ppm) 31.2, 35.1, 124.9, 127.3, 135.6,
155.9; M.S (M+): 179.
4ꢀNitrobenzaldehyde (6a)
Yellow solid; mp 103ꢀ106 °C (lit. [30] mp 105ꢀ107 °C); isolated yield 88% (0.132 g); IR
(KBr) 739, 1346, 1541, 1708, 3106 cm−1; 1H NMR (400 MHz, CDCl3) δ (ppm) 8.091 (d, J = 8.4
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Hz, 2H), 8.39 (d, J = 8.4 Hz, 2H), 10.17 (s, 1H), C NMR (100 MHz, CDCl3) δ (ppm) 124.3,
130.5, 140.0, 151.0, 190.4; M.S (M+): 151.
1ꢀMethylꢀ4ꢀnitrobenzene (7a)
Yellow solid; mp 50ꢀ52 °C (lit. [2] mp 52ꢀ54 °C); isolated yield 85% (0.116 g); IR (KBr)
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737, 1345, 1597, 3084 cm−1; H NMR (400 MHz, DMSOꢀd6) δ (ppm) 2.43 (s, 3H), 7.45 (d, J=
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8.4 Hz, 2H), 8.11 (d, J= 8.4 Hz, 2H), 8.57 (s, 2H); C NMR (100 MHz, DMSOꢀd6) δ (ppm)
21.0, 123.2, 130.1, 145.5, 146.3; M.S (M+): 137.
1ꢀBromoꢀ4ꢀnitrobenzene (8a)
Yellow solid; mp 123ꢀ125 °C (lit. [17]); isolated yield 77% (0.155 g); IR (KBr) 701, 1344,
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1520, 2917, 3110; H NMR (400 MHz, DMSOꢀd6) δ (ppm) 7.86 (dd, J = 4.8, 2 Hz, 2H), 8.13
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(dd, J = 4.8, 2 Hz, 2H), C NMR (100 MHz, DMSOꢀd6) δ (ppm) 125.2, 129.3, 132.7, 146.7;
M.S (M+ + 1): 203.
1,3ꢀDinitrobenzene (9a)
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Yellow solid; mp 83ꢀ85 °C (lit. [27] mp 89ꢀ90 °C); isolated yield 92% (0.154 g); IR (KBr)
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712, 1347, 1541, 3108 cm−1; 1H NMR (400 MHz, CDCl3) δ (ppm) 8.05 (t, J = 8.4 Hz, 1H), 8.73
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(dd, J = 8, 2.4 Hz, 2H), 8.91 (t, J = 2 Hz, 1H), C NMR (100 MHz, CDCl3) δ (ppm) 118.4,
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129.3, 131.5, 147.9; M.S (M+): 168.
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1ꢀ(4ꢀNitrophenyl)ethanone (10a)
Yellow solid; mp 75ꢀ77 °C (lit. [28] mp 76ꢀ78 °C); isolated yield 78% (0.128 g); IR (KBr)
764, 1344, 1527, 1693, 3108 cm−1; 1H NMR (400 MHz, DMSOꢀd6) δ (ppm) 2.6 (s, 3H), 8.28 (d,
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J = 8.8 Hz, 2H), 8.44 (d, J = 8.8 Hz, 2H), 11.07 (s, 1H), C NMR (100 MHz, DMSOꢀd6) δ
(ppm) 27.2, 123.8, 129.5, 141.2, 149.8, 197.1; M.S (M+): 165.
4ꢀNitrophenol (11a)
Yellow solid; mp 42ꢀ45 °C (lit. [2a] mp 43ꢀ47 °C); isolated yield 78% (0.108 g); IR (KBr)
753, 1337, 1594, 3078, 3372 cm−1; 1H NMR (400 MHz, DMSOꢀd6) δ (ppm) 6.92 (d, J = 8.8 Hz,
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2H), 8.11 (d, J= 8.8 Hz, 2H), 11.07 (s, 1H), C NMR (100 MHz, DMSOꢀd6) δ (ppm) 115.7,
126.1, 139.4, 163.9; M.S (M+): 139.
2ꢀMethoxyꢀ5ꢀnitrobenzaldehyde (12a)
Yellow solid; mp 80ꢀ82 °C (lit. [29] mp 75ꢀ79 °C); isolated yield 82% (0.148 g); IR
(KBr) 1342, 1544, 1669, 3072 cm−1; 1H NMR (400 MHz, DMSOꢀd6) δ (ppm) 4.13 (s, 3H), 7.45
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(d, J= 8.0 Hz, 1H), 8.48 (d, J= 4.0 Hz, 1H), 8.58 (dd, J= 9.2, 3.2 Hz, 1H), 10.38 (s, 1H), C
NMR (100 MHz, DMSOꢀd6) δ (ppm) 57.4, 114.0, 123.5, 125.2, 129.1, 130.9, 165.4, 187.9; M.S
(M+): 181.
1,4ꢀDinitrobenzene (13a)
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Yellow solid; mp 167ꢀ169 °C (lit. [27] mp 165ꢀ166 °C); isolated yield 75% (0.126 g); IR
(KBr) 799, 1360, 1588, 3270 cm−1; 1H NMR (300 MHz, CDCl3) δ (ppm) 8.44 (s, 4H); 13C NMR
(100 MHz, CDCl3) δ (ppm) 124.9, 131.6; M.S (M+ + 1): 169.
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(E)ꢀ1, 2, 3ꢀtrimethoxyꢀ5ꢀ(2ꢀnitrovinyl) benzene (1b)
Yellow solid; mp 118ꢀ120 ˚C mp (lit. [4] mp 121 °C); isolated yield 82% (0.196 g); IR
(KBr, cmꢀ1): 3116, 2924, 1518, 1467, 1383, 1264, 1122, 826, 650; H NMR (400 MHz, DMSOꢀ
1
d6): δ (ppm) 3.726 (s, 3H), 3.89 (s, 6H), 6.75 (d, J = 15.9 Hz, 1H), 7.16 (s, 2H), 7.68 (d, J = 15.9
Hz, 1H); 13C NMR (100 MHz, DMSOꢀd6): δ (ppm) 51.3, 55.9, 60.0, 105.9, 117.0, 129.5, 144.7,
153.0, 166.7; M.S (M+): 239.
(E)ꢀ (2ꢀnitrovinyl) benzene (2b)
Yellow solid; mp 60ꢀ64 ˚C (lit. [22] mp 55ꢀ58 °C); isolated yield 77% (0.114 g); IR (KBr,
cmꢀ1): 3112,3045, 2967, 2921, 2851, 1519, 1344, 767; H NMR (400 MHz, DMSOꢀd6): δ (ppm)
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7.44ꢀ7.57 (m, 3H), 7.87 (d, J= 8.4 Hz, 2H), 8.14 (d, J= 13.6 Hz, 1H), 8.25 (d, J= 13.6 Hz); C
NMR (100 MHz, DMSOꢀd6): δ (ppm) = 27.6, 71.6, 120.8, 122.8, 127.3, 129.1, 130.3, 132.0,
132.1, 137.3.
(E)ꢀ1ꢀmethoxyꢀ4ꢀ(2ꢀnitrovinyl) benzene (3b)
Yellow solid; mp 88ꢀ90 ˚C (lit. [4] mp 89ꢀ92 °C); isolated yield 85% (0.152 g); IR (KBr,
cmꢀ1): 3317,3119, 2921, 1544, 1529, 1421, 1397, 1322, 824; H NMR (400 MHz, CDCl3): δ
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(ppm) 3.78 (s, 3H), 6.86 (d, J = 6.0 Hz, 1H), 7.41 (d, J = 8.8 Hz, 2H), 7.43 (d, J = 13.6 Hz, 1H),
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7.88 (d, J = 13.6 Hz, 1H); C NMR (100MHz, CDCl3): δ (ppm) 55.5, 114.9, 122.5, 131.2,
135.0, 139.0, 162.9; M.S (M+): 179.
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(E)ꢀ5ꢀ(2ꢀnitrovinyl) benzo[d][1,3]dioxole (4b)
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Orange yellow solid; mp142ꢀ145 ˚C (lit. [4] mp 139 °C); isolated yield 75% (0.144 g);
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isolated yield 85% (0.152 g); IR (KBr, cmꢀ1): 3436, 3113, 2924, 1507, 1334, 1271, 1031; H
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NMR (400 MHz, DMSOꢀd6): δ (ppm) 6.44 (s, 2H), 7.69 (s, 2H), 7.91 (s, 1H), 8.23 (d, J = 12 Hz,
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1H), 8.47 (d, J = 12 Hz, 1H); C NMR (100 MHz, DMSOꢀd6): δ (ppm) 104.2, 105.8, 107.9,
121.5, 135.1, 139.9, 144.1, 150.1, 151.8; M.S (M+): 193.
Nitroethene (5b)
Yellow solid; mp 95ꢀ98 ˚C (lit. [24] mp 97ꢀ100 °C); isolated yield 70% (0.051 g); IR
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(Nujol, cmꢀ1): 3430, 3117, 1522, 1421, 1286, 1233, 1081, 665; H NMR (300 MHz, Acetoneꢀd6):
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δ (ppm) 6.9 (s, 1H), 7 (s, 1H), 7.4 (s, 1H); C NMR (75 MHz, Acetoneꢀd6): δ (ppm) 120.2,
137.9.
1ꢀChloroꢀ4ꢀnitrobenzene (6b)
Yellow solid; mp 78ꢀ80 ˚C (lit. [2] mp 82ꢀ84 °C); isolated yield 75% (0.118 g); IR (KBr,
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cmꢀ1): 3317, 3119, 2921, 1544, 1529, 1486,1397, 1322, 1293, 824; H NMR (400 MHz, CDCl3):
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δ (ppm) 7.3 (d, J= 0.8 Hz, 1H), 7.7 (d, J= 1.2 Hz, 1H); C NMR (100 MHz, CDCl3): δ (ppm)
120.2, 128.7, 130.9, 136.6; M.S (M+): 157.
1, 2, 3ꢀTrimethoxyꢀ5ꢀnitrobenzene (7b)
Yellow solid; mp 100ꢀ103 ˚C (lit. [26] mp 98 °C); isolated yield 78% (0.166 g); IR (KBr,
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cmꢀ1): 3436, 3111, 2979, 2949, 1523, 1498,1338, 1318; H NMR (400 MHz, CDCl3): δ (ppm)
3.95 (s, 9H), 7.53 (s, 2H); 13C NMR (100 MHz, CDCl3): δ (ppm) 56.4, 61.1, 101.2, 143.4, 143.7,
152.8; M.S (M+): 213.
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1ꢀMethylꢀ4ꢀnitrobenzene (8b)
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o
Yellow solid; mp 51ꢀ53 C (lit. [2] mp 52ꢀ54 °C); isolated yield 76% (0.104 g); IR (KBr,
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cmꢀ1): 3436,3117, 2925, 1521, 1384, 1232, 1081, 665; H NMR (300 MHz, DMSOꢀd6): δ (ppm)
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2.4 (s, 3H), 7.46 (d, J = 8.4 Hz, 2H), 8.11 (d, J = 8.4 Hz, 2H); 13C NMR (75 MHz, DMSOꢀd6): δ
(ppm) 21.0, 123.2, 130.7, 145.5, 146.3.
1ꢀMethoxyꢀ4ꢀnitrobenzene (9b)
o
Yellow solid; mp 50ꢀ53 C (lit. [2] mp 52ꢀ54 °C); isolated yield 74% (0.113 g); IR (KBr,
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cmꢀ1): 3121,3045, 2946, 1591, 1508, 1342, 1267, 848; H NMR (300 MHz, DMSOꢀd6): δ (ppm)
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3.9 (s, 3H), 7.1 (d, J = 9.3 Hz, 2H), 8.2 (d, J = 9.3 Hz, 2H); C NMR (75 MHz, DMSOꢀd6): δ
(ppm) 56.6, 115.0, 126.3, 141.2, 165.0.
Nitrobenzene (10b)
Yellow liquid; mp 208ꢀ210 ˚C (lit. [24] mp 213ꢀ215 °C); isolated yield 74% (0.091 g); IR
(Nujol, cmꢀ1): 3111,2955, 1520, 1358, 1288, 1233, 1080, 664; 1H NMR (300 MHz, DMSOꢀd6): δ
(ppm) 7.55 (t, J = 8.1 Hz, 2H), 7.71 (t, J = 7.5 Hz, 1H), 8.22 (d, J = 8.1 Hz, 2H ); 13C NMR (75
MHz, DMSOꢀd6): δ (ppm) 123.4, 129.3, 134.6, 148.1; M.S (M+): 123.
1ꢀBromoꢀ4ꢀnitrobenzene (11b)
Yellow solid; mp123ꢀ125 ˚C(lit. [17]); isolated yield 77% (0.155 g); isolated yield 77%
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(0.154 g); H NMR (400 MHz, DMSOꢀd6) δ (ppm) 7.86 (dd, J = 7.2, 2 Hz, 2H), 8.14 (dd, J =
7.2, 2 Hz, 2H); 13C NMR (100 MHz, DMSOꢀd6) δ (ppm) 125.2, 129.2, 132.6, 146.1.
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Supporting Information
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Experimental procedures and compound characterization data.
This material is available free of charge via the Internet at http://pubs.acs.org.
ACKNOWLEDGMENT
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We thank BuꢀAli Sina University, Sayyed Jamaleddin Asadabadi University and Iran National
Science Foundation (INSF) (Grant Number: 940124) for financial support to our research group.
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