Article pubs.acs.org/joc
Cite This: J. Org. Chem. XXXX, XXX, XXX−XXX
Synthesis of Nitroolefins and Nitroarenes under Mild Conditions Mahmoud Zarei,† Ehsan Noroozizadeh,† Ahmad R. Moosavi-Zare,*,‡ and Mohammad A. Zolfigol*,† †
Department of Organic Chemistry, Faculty of Chemistry, Bu-Ali Sina University, Hamedan, 6517838683, Iran Sayyed Jamaleddin Asadabadi University, Asadabad, 6541861841, Iran
‡
S Supporting Information *
ABSTRACT: 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.
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INTRODUCTION Nitro aromatic compounds are valuable materials because of their applications in 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 reactions, the Diels−Alder reaction, and the Michael reaction to prepare various organic intermediates and also can be reduced to 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 been successfully used as catalysts and reagents for the synthesis of some important organic compounds such as bis(indolyl)methanes,5,6 N-sulfonyl imines,7 nitro phenolic compounds,8 1-amidoalkyl-2-naphthols,9 benzimidazoles,10 xanthene derivatives,11 1,2,4,5-tetrasubstituted imidazoles,12 and amido-alkyl-phenols.13 Herein we have synthesized 1,3-disulfonic acid imidazolium nitrate {[Dsim]NO3} and fully characterized by IR, 1H and 13C NMR, TG, DTG, and mass spectra (Scheme 1). [Dsim]NO3
was successfully used as a novel ionic liquid and nitrating agent for the ipso-nitration reaction of arylboronic acids to give nitroarenes (Scheme 2) and nitro-Hunsdiecker reactions by the Scheme 2. Synthesis of Nitroarenes by Ipso-Nitration Reaction of Arylboronic Acids Using [Dsim]NO3
decarboxylative nitration of various α,β-unsaturated acids and benzoic acid derivatives to give various (E)-nitroolefins and nitroarenes, respectively, under mild and solvent-free conditions without using any cocatalysts. All products were synthesized fast in high yields and in very short reaction times (Schemes 2 and 3). Scheme 3. Synthesis of (E)-Nitroolefins and Nitroarenes by the Nitro-Hunsdiecker Reaction Using [Dsim]NO3
Scheme 1. Synthesis of 1,3-Disulfonic Acid Imidazolium Nitrate [Dsim]NO3
Received: December 29, 2017 Published: March 5, 2018 © XXXX American Chemical Society
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DOI: 10.1021/acs.joc.7b03289 J. Org. Chem. XXXX, XXX, XXX−XXX
Article
The Journal of Organic Chemistry
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RESULTS AND DISCUSSION
Scheme 4. Synthesis of Nitro Aromatic Compounds by IpsoNitration of Various Arylboronic Acids Using [Dsim]NO3
At first, by the reaction of imidazole (1 mmol) and chlorosulfonic acid (2 mmol) in CH2Cl2 as a solvent, 1,3disulfonic 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 1,3-disulfonic acid imidazolium nitrate {[Dsim]NO3} as a novel ionic liquid and nitrating agent by the release of HCl (1 mmol) (Scheme 1). The structure of [Dsim]NO3 was studied and identified by IR, 1H and 13C NMR, TG, DTG, and mass spectra (Figures S1−S5). The thermal gravimetric (TG) and differential thermal gravimetric (DTG) analyses of [Dsim]NO3 were studied, and the main weight loss occurred after 200 °C which was related to molecular decomposition of [Dsim]NO3 (Figure S5). Also, the weight loss of the reagent during the increase in temperature from 75 °C to 200 °C could be related to the release of NO2. To show the efficiency of [Dsim]NO3 on the preparation of nitro aromatic compounds, we have tested it on the ipsonitration reaction of various arylboronic acids. This reaction was previously reported in the presence of some various nitrating agents, cocatalysts, and solvents such as Bi(NO3)5H2O/K2S2O8/toluene under nitrogen atmosphere,1 tert-butyl nitrile/dioxane,14 NH4NO3/(CF3CO)2O/CH3CN,15 [bis(trifluoroacetoxy)]iodobenzene/N-bromosuccinimide (NBS)/sodium nitrite/CH3CN,16 HNO3/TMS-Cl/CH2Cl2,17 tert-butyl nitrite/MeCN,18 and Bi(NO3)3·5H2O/toluene or benzene under nitrogen atmosphere.19 Using cocatalysts and solvents, high temperature, long reaction times, and low yields are some disadvantages of previous reported works. In the present work, the reaction of 3-nitrophenyl 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 solvent-free conditions. The best result was obtained at room temperature in the absence of solvent (Table 1).
According to previous studies,2,20 to show that NO2 in equilibrium with N2O4 could be derived from [Dsim]NO3, the released gas was conducted to a round-bottomed flask containing copper powder and ethyl acetate. By the reaction of NO2 with copper powder, Cu(NO3)2 was prepared with blue color. The black sediment was collected in the round-bottomed flask as a result of the reaction of excess copper powder with O2 produced from [Dsim]NO2 (Figure 1).
Table 1. Effect of Various Temperatures and Solvents on the Reaction of 3-Nitrophenyl Boronic Acid (1 mmol) with [DSim]NO3 (1 mmol)
a
entry
solvent
temp (°C)
time (min)
yielda (%)
1 2 3 4 5 6 7 8 9
− − − CH2Cl2 CHCl3 H2O EtOH Acetone EtOAc
rt 50 70 rt rt rt rt rt rt
1 1 1 8 60 60 60 60 60
92 92 92 59 38 18 21 31 32
Figure 1. Synthesis of copper nitrate by the reaction of nitrogen oxide with copper powder.
In the proposed mechanism, the released nitrogen dioxide from [Dsim]NO3 was 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 to III. Then, by the intramolecular rearrangement of III, nitrobenzene 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). 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
Isolated yield.
After the optimization of the reaction condition, various arylboronic acids containing electron-releasing substituents, electron-withdrawing 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 in high yields and in very short reaction times (Scheme 4). Many of the compounds as shown in Scheme 4 are hardly produced by previous methods. B
DOI: 10.1021/acs.joc.7b03289 J. Org. Chem. XXXX, XXX, XXX−XXX
Article
The Journal of Organic Chemistry Scheme 5. Proposed Mechanism for the Ipso-Nitration Reaction of Arylboronic Acid Using [DSim]NO3
Table 3. Effect of Various Temperatures and Solvents on the Reaction of (E)-3-(3,4,5-Trimethoxyphenyl)acrylic Acid (1 mmol) with [Dsim]NO3 (1 mmol) under Nitrogen Atmosphere
a
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.
I2 (mmol)
time (min)
yield (%)
BHT (mmol)
time (min)
yield (%)
1 2 3 4 5 6
0 0.2 0.4 0.6 0.8 1
1 240 240 240 240 240
92 55 48 36 28 15
0 0.2 0.4 0.6 0.8 1
1 240 240 240 240 240
92 54 46 35 27 2
a
solvent
temp (°C)
time (min)
yielda (%)
1 2 3 4 5 6 7 8 9
− − − CH2Cl2 CHCl3 H2O EtOH acetone EtOAc
rt 50 70 reflux 50 50 50 reflux 50
45 10 10 15 60 60 60 60 60
trace 80 80 53 15 − 12 25 35
Isolated yield.
Scheme 6. Preparation of (E)-Nitroolefins and Nitroarenes by the Nitro-Hunsdiecker Reaction of Various α,βUnsaturated Acids and Benzoic Acid Derivatives with [Dsim]NO3 under Nitrogen Atmosphere and Solvent-Free Conditions
Table 2. Effect of Iodine and BHT as Radical Scavengers on the Synthesis of 1,3-Dinitrobenzene Using [DSim]NO3 entry
entry
Isolated yield.
The synthesis of nitroolefin derivatives in the presence of various nitrating agents, cocatalysts, and solvents such as tBuONO/TEMPO/CH3CN,4 Fe(NO3)3/pyridine/toluene,21 Cu(NO3)2/CH3CN,22 HNO3/AIBN/CH3CN,23 and AgNO2/ TEMPO/dichloroethane was previously reported.24 However, some of these methods have disadvantages such as low yields, long reaction times, harsh reaction conditions, and usage of solvents and cocatalysts. In the next step, to show the ability of [Dsim]NO3 as a nitrating agent, we tested it on the nitro-Hunsdiecker reaction to give nitroolefins and nitroarenes by in situ generation of NO2 without using any cocatalysts under nitrogen atmosphere. For this purpose, the reaction of (E)-3-(3,4,5-trimethoxyphenyl)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 shown in Table 3, the best result was achieved at 50 °C. The yield of product was 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). Table 3 shows 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. After the optimization of the reaction condition, the reaction of various α,β-unsaturated acids and benzoic acid derivatives with [Dsim]NO3 was investigated to prepare of various (E)nitroolefins and nitroarenes under nitrogen atmosphere and solvent-free conditions (Scheme 6).
In the proposed mechanism according to reported literature,3,21−23 decarboxylative nitration of α,β-unsaturated acids could have occurred through three pathways (Scheme 7). In path 1, decarboxylation was carried out and then the NO2 group was added to the substrate. But in the other pathways, after addition of NO2 group to the substrate, decarboxylation occurred and nitroolefin compound was prepared. In the proposed mechanism for the nitrodecarboxylation of aryl carboxylic acid,3,23 it is suggested that benzoic acid could be reacted with nitrogen dioxide, which is derived 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). To confirm the effect of nitrogen dioxide, as a radical species, on the progression of the reaction, nitro-decarboxylation of (E)-3-(3,4,5-trimethoxyphenyl)acrylic acid using [DSim]NO3 was tested in the presence of iodine or butylated C
DOI: 10.1021/acs.joc.7b03289 J. Org. Chem. XXXX, XXX, XXX−XXX
Article
The Journal of Organic Chemistry Scheme 7. Proposed Mechanism for the Nitro-Hunsdiecker Reaction of α,β-Unsaturated Acids Using [DSim]NO3
Table 5. Comparison of the Results for the Nitrodecarboxylation of (E)-3-(3,4,5-Trimethoxyphenyl)acrylic Acid Using Different Reagents and Conditions entry
reaction condition
time (min)
yield (%)
ref
1 2 3 4
t-BuONO/TEMPO/CH3CN, 50 °C Cu(NO3)2/CH3CN HNO3/AIBN/CH3CN, 50 °C [DSim]NO3, 50 °C
180 480 120 10
80 93 80 82
4 22 23 −a
a
nitration reaction of arylboronic acids to give nitroarenes at room temperature under solvent-free conditions. Also, it was used for the nitro-Hunsdiecker reaction by the decarboxylative nitration of different α,β-unsaturated acids and benzoic acid derivatives to prepare of various (E)-nitroolefins and nitroarenes, respectively, without using any cocatalysts at 50 °C under solvent-free conditions and nitrogen atmosphere. All products were synthesized fast in high yields and in very short reaction times.
Scheme 8. Proposed Mechanism for the Nitrodecarboxylation of Aryl Carboxylic Acids Using [DSim]NO3
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Table 4. Effect of Iodine and BHT as Radical Scavengers on Nitro-decarboxylation of (E)-3-(3,4,5Trimethoxyphenyl)acrylic Acid Using [DSim]NO3 I2 (mmol)
time (min)
yielda(%)
BHT (mmol)
time (min)
yielda(%)
1 2 3 4 5 6
0 0.2 0.4 0.6 0.8 1
10 240 240 240 240 240
82 42 35 32 22 10
0 0.2 0.4 0.6 0.8 1
10 240 240 240 240 240
82 55 45 38 30 15
a
EXPERIMENTAL SECTION
General Methods. All chemicals were purchased from Merck, Sigma-Aldrich, or Fluka chemical companies. The known products were identified by comparison of their physical and spectral data (IR, 1 H NMR, 13C NMR, and mass) with those previously reported in the literature. Progress of the reaction was monitored by TLC. Procedure for the Synthesis of 1,3-Disulfonic Acid Imidazolium Nitrate [Dsim]NO3. To a round-bottomed 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) dropwise over a period of 20 min at room temperature. After the addition was completed, the reaction mixture was stirred for 12 h under a continuous flow of nitrogen (to remove the produced HCl) and allowed to stand for 5 min, and the CH2Cl2 was decanted. The residue was washed with dry CH2Cl2 (3 × 50 mL) and dried under vacuum to make viscous, pale yellow [Dsim]Cl.9 Then nitric acid 100% (0.315 g, 5 mmol) was added dropwise to [Dsim]Cl (0.993 g, 5 mmol) over a period of 5 min at room temperature under a continuous flow of nitrogen to remove the HCl gas that is produced. The resulting mixture was stirred for 10 min under this condition to give [Dsim]NO3 as a viscous yellow-red oil. Spectral Data of [Dsim]NO3. Pale yellow-red oil; IR (KBr): 576, 1068, 1175, 1286, 1585, 3100−3500 cm−1; 1H NMR (300 MHz, DMSO-d6): δ (ppm) 7.51 (s, 2H), 8.88 (s, 1H), 12.83 (s, 2H); 13C NMR (75 MHz, DMSO-d6): δ (ppm) 119.7, 134.6; M.S (M+): 291. Procedure for the Preparation of Nitroarenes by IpsoNitration Reaction of Boric Acid Using [Dsim]NO3. To a roundbottomed flask (10 mL) containing of [Dsim]NO3 (0.291 g, 1 mmol) was added arylboronic acid (1 mmol), 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 min, and then the desired product was easily extracted, dried over MgSO4, and filtered. Finally, the product was purified by plate chromatography (EtOAc/n-hexane: 1/4). Procedure for the Preparation of (E)-Nitroolefins and Nitroarenes by Nitro-Hunsdiecker Reaction of Various α,βUnsaturated Acids and Benzoic Acid Derivatives Using [DSim]NO3. To a round-bottomed flask (10 mL) containing of [Dsim]NO3 (0.291 g, 1 mmol), α,β-unsaturated acid (1 mmol) or benzoic acid derivative (1 mmol) was added and the mixture was stirred at 50 °C for the 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 min, dried over MgSO4, and filtered. Finally, the product was purified by plate chromatography (EtOAc/n-hexane: 1/4).
hydroxytoluene (BHT) as a radical scavenger (Table 4). With the increase of iodine or BHT, the yield of product decreased
entry
Our method.
Isolated yield.
even after a long time. This observation clearly showed that nitrogen dioxide with radical properties is effective in this reaction. To demonstrate the suitability of this method in comparison with some previous reported works, the results for nitrodecarboxylation of (E)-3-(3,4,5-trimethoxyphenyl)acrylic acid using some different reagents and conditions were studied and summarized in Table 5. As shown in Table 5, the presented method is superior to other mentioned methods. Long reaction time, high temperature, and use of cocatalyst and solvent are some disadvantages for the previous methods.
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CONCLUSION We have prepared 1,3-disulfonic acid imidazolium nitrate [Dsim]NO3 as a new ionic liquid and fully characterized by IR, 1 H and 13C NMR, TG, DTG, and mass spectra. [Dsim]NO3 was successfully applied as a nitrating agent for the ipsoD
DOI: 10.1021/acs.joc.7b03289 J. Org. Chem. XXXX, XXX, XXX−XXX
Article
The Journal of Organic Chemistry
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. (E)-1,2,3-Trimethoxy-5-(2-nitrovinyl)benzene (1b). Yellow solid; mp 118−120 °C (lit.,4 mp 121 °C); isolated yield 82% (0.196 g); IR (KBr, cm−1): 3116, 2924, 1518, 1467, 1383, 1264, 1122, 826, 650; 1H NMR (400 MHz, DMSO-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, DMSO-d6): 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)-(2-Nitrovinyl)benzene (2b). Yellow solid; mp 60−64 °C (lit.,22 mp 55−58 °C); isolated yield 77% (0.114 g); IR (KBr, cm−1): 3112,3045, 2967, 2921, 2851, 1519, 1344, 767; 1H NMR (400 MHz, DMSO-d6): δ (ppm) 7.44−7.57 (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); 13C NMR (100 MHz, DMSO-d6): δ (ppm) = 27.6, 71.6, 120.8, 122.8, 127.3, 129.1, 130.3, 132.0, 132.1, 137.3. (E)-1-Methoxy-4-(2-nitrovinyl)benzene (3b). Yellow solid; mp 88− 90 °C (lit.,4 mp 89−92 °C); isolated yield 85% (0.152 g); IR (KBr, cm−1): 3317,3119, 2921, 1544, 1529, 1421, 1397, 1322, 824; 1H NMR (400 MHz, CDCl3): δ (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), 7.88 (d, J = 13.6 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ (ppm) 55.5, 114.9, 122.5, 131.2, 135.0, 139.0, 162.9; M.S (M+): 179. (E)-5-(2-Nitrovinyl)benzo[d][1,3]dioxole (4b). Orange yellow solid; mp 142−145 °C (lit.,4 mp 139 °C); isolated yield 75% (0.144 g); isolated yield 85% (0.152 g); IR (KBr, cm−1): 3436, 3113, 2924, 1507, 1334, 1271, 1031; 1H NMR (400 MHz, DMSO-d6): δ (ppm) 6.44 (s, 2H), 7.69 (s, 2H), 7.91 (s, 1H), 8.23 (d, J = 12 Hz, 1H), 8.47 (d, J = 12 Hz, 1H); 13C NMR (100 MHz, DMSO-d6): 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 95−98 °C (lit.,24 mp 97−100 °C); isolated yield 70% (0.051 g); IR (Nujol, cm−1): 3430, 3117, 1522, 1421, 1286, 1233, 1081, 665; 1H NMR (300 MHz, acetone-d6): δ (ppm) 6.9 (s, 1H), 7 (s, 1H), 7.4 (s, 1H); 13C NMR (75 MHz, acetone-d6): δ (ppm) 120.2, 137.9. 1-Chloro-4-nitrobenzene (6b). Yellow solid; mp 78−80 °C (lit.,2 mp 82−84 °C); isolated yield 75% (0.118 g); IR (KBr, cm−1): 3317, 3119, 2921, 1544, 1529, 1486,1397, 1322, 1293, 824; 1H NMR (400 MHz, CDCl3): δ (ppm) 7.3 (d, J = 0.8 Hz, 1H), 7.7 (d, J = 1.2 Hz, 1H); 13C NMR (100 MHz, CDCl3): δ (ppm) 120.2, 128.7, 130.9, 136.6; M.S (M+): 157. 1, 2, 3-Trimethoxy-5-nitrobenzene (7b). Yellow solid; mp 100− 103 °C (lit.,26 mp 98 °C); isolated yield 78% (0.166 g); IR (KBr, cm−1): 3436, 3111, 2979, 2949, 1523, 1498,1338, 1318; 1H 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. 1-Methyl-4-nitrobenzene (8b). Yellow solid; mp 51−53 °C (lit.,2 mp 52−54 °C); isolated yield 76% (0.104 g); IR (KBr, cm−1): 3436,3117, 2925, 1521, 1384, 1232, 1081, 665; 1H NMR (300 MHz, DMSO-d6): δ (ppm) 2.4 (s, 3H), 7.46 (d, J = 8.4 Hz, 2H), 8.11 (d, J = 8.4 Hz, 2H); 13C NMR (75 MHz, DMSO-d6): δ (ppm) 21.0, 123.2, 130.7, 145.5, 146.3. 1-Methoxy-4-nitrobenzene (9b). Yellow solid; mp 50−53 °C (lit.,2 mp 52−54 °C); isolated yield 74% (0.113 g); IR (KBr, cm−1): 3121,3045, 2946, 1591, 1508, 1342, 1267, 848; 1H NMR (300 MHz, DMSO-d6): δ (ppm) 3.9 (s, 3H), 7.1 (d, J = 9.3 Hz, 2H), 8.2 (d, J = 9.3 Hz, 2H); 13C NMR (75 MHz, DMSO-d6): δ (ppm) 56.6, 115.0, 126.3, 141.2, 165.0. Nitrobenzene (10b). Yellow liquid; mp 208−210 °C (lit.,24 mp 213-215 °C); isolated yield 74% (0.091 g); IR (Nujol, cm−1): 3111,2955, 1520, 1358, 1288, 1233, 1080, 664; 1H NMR (300 MHz, DMSO-d6): 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, DMSO-d6): δ (ppm) 123.4, 129.3, 134.6, 148.1; M.S (M+): 123. 1-Bromo-4-nitrobenzene (11b). Yellow solid; mp 123−125 °C(lit.17); isolated yield 77% (0.155 g); isolated yield 77% (0.154 g); 1H NMR (400 MHz, DMSO-d6) δ (ppm) 7.86 (dd, J = 7.2, 2 Hz, 2H), 8.14 (dd, J = 7.2, 2 Hz, 2H); 13C NMR (100 MHz, DMSO-d6) δ (ppm) 125.2, 129.2, 132.6, 146.1.
Spectral Data of Compounds. 1-Fluoro-4-nitrobenzene (1a). Yellow solid; mp 109−112 °C (lit.17); isolated yield 84% (0.118 g); 1H NMR (400 MHz, acetone-d6) δ (ppm) 7.53 (dd, J = 6, 3.2 Hz, 2H), 7.64 (dd, J = 6, 3.2 Hz, 2H); 13C NMR (100 MHz, acetone-d6) δ (ppm) 125.2, 127.4, 127.9, 171.7; M.S (M+): 141. 1-Fluoro-3-nitrobenzene (2a). Yellow solid; mp 42−45 °C (lit.28); isolated yield 78% (0.110 g); IR (KBr) 747, 1303, 1563, 2939 cm−1; 1 H NMR (400 MHz, acetone-d6) δ (ppm) 7.68−7.72 (m, 2H), 8.57 (s, br, 2H); 13C NMR (100 MHz, acetone-d6) δ (ppm) 112.4, 112.6, 121.1; M.S (M+): 141. 1-Nitrobenzene (3a). Yellow oil; mp 215−217 °C (lit.24 mp 213− 215 °C); isolated yield 74% (0.091 g); 1H 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 = 8.1 Hz, 2H); 13C NMR (100 MHz, DMSO-d6) δ (ppm) 123.4, 129.3, 134.6, 148.1; M.S (M+): 123. 1-Methoxy-4-nitrobenzene (4a). Yellow solid; mp 53−55 °C (lit.,2 mp 52−54 °C); isolated yield 90% (0.137 g); IR (KBr) 751, 1344, 1591, 3081 cm−1; 1H NMR (300 MHz, DMSO-d6) δ (ppm) 3.90 (s, 3H), 7.15 (d, J = 9.3 Hz, 2H), 8.22 (d, J = 9.3 Hz, 2H), 13C NMR (100 MHz, DMSO-d6) δ (ppm) 56.67, 115.06, 126.3, 141.2, 165.0; M.S (M+ + 1): 154. 1-tert-Butyl-4-nitrobenzene (5a). Yellow solid; mp 99−102 °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), 8.09 (d, J = 8.4 Hz, 2H), 13C NMR (100 MHz, CDCl3) δ (ppm) 31.2, 35.1, 124.9, 127.3, 135.6, 155.9; M.S (M+): 179. 4-Nitrobenzaldehyde (6a). Yellow solid; mp 103−106 °C (lit.,29 mp 105−107 °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 Hz, 2H), 8.39 (d, J = 8.4 Hz, 2H), 10.17 (s, 1H), 13C NMR (100 MHz, CDCl3) δ (ppm) 124.3, 130.5, 140.0, 151.0, 190.4; M.S (M+): 151. 1-Methyl-4-nitrobenzene (7a). Yellow solid; mp 50−52 °C (lit.,2 mp 52−54 °C); isolated yield 85% (0.116 g); IR (KBr) 737, 1345, 1597, 3084 cm−1; 1H NMR (400 MHz, DMSO-d6) δ (ppm) 2.43 (s, 3H), 7.45 (d, J = 8.4 Hz, 2H), 8.11 (d, J = 8.4 Hz, 2H), 8.57 (s, 2H); 13 C NMR (100 MHz, DMSO-d6) δ (ppm) 21.0, 123.2, 130.1, 145.5, 146.3; M.S (M+): 137. 1-Bromo-4-nitrobenzene (8a). Yellow solid; mp 123−125 °C (lit.17); isolated yield 77% (0.155 g); IR (KBr) 701, 1344, 1520, 2917, 3110; 1H NMR (400 MHz, DMSO-d6) δ (ppm) 7.86 (dd, J = 4.8, 2 Hz, 2H), 8.13 (dd, J = 4.8, 2 Hz, 2H), 13C NMR (100 MHz, DMSOd6) δ (ppm) 125.2, 129.3, 132.7, 146.7; M.S (M+ + 1): 203. 1,3-Dinitrobenzene (9a). Yellow solid; mp 83−85 °C (lit.27 mp 89−90 °C); isolated yield 92% (0.154 g); IR (KBr) 712, 1347, 1541, 3108 cm−1; 1H NMR (400 MHz, CDCl3) δ (ppm) 8.05 (t, J = 8.4 Hz, 1H), 8.73 (dd, J = 8, 2.4 Hz, 2H), 8.91 (t, J = 2 Hz, 1H), 13C NMR (100 MHz, CDCl3) δ (ppm) 118.4, 129.3, 131.5, 147.9; M.S (M+): 168. 1-(4-Nitrophenyl)ethanone (10a). Yellow solid; mp 75−77 °C (lit.,28 mp 76−78 °C); isolated yield 78% (0.128 g); IR (KBr) 764, 1344, 1527, 1693, 3108 cm−1; 1H NMR (400 MHz, DMSO-d6) δ (ppm) 2.6 (s, 3H), 8.28 (d, J = 8.8 Hz, 2H), 8.44 (d, J = 8.8 Hz, 2H), 11.07 (s, 1H), 13C NMR (100 MHz, DMSO-d6) δ (ppm) 27.2, 123.8, 129.5, 141.2, 149.8, 197.1; M.S (M+): 165. 4-Nitrophenol (11a). Yellow solid; mp 42−45 °C (lit.,2 mp 43−47 °C); isolated yield 78% (0.108 g); IR (KBr) 753, 1337, 1594, 3078, 3372 cm−1; 1H NMR (400 MHz, DMSO-d6) δ (ppm) 6.92 (d, J = 8.8 Hz, 2H), 8.11 (d, J = 8.8 Hz, 2H), 11.07 (s, 1H), 13C NMR (100 MHz, DMSO-d6) δ (ppm) 115.7, 126.1, 139.4, 163.9; M.S (M+): 139. 2-Methoxy-5-nitrobenzaldehyde (12a). Yellow solid; mp 80−82 °C (lit.,29 mp 75−79 °C); isolated yield 82% (0.148 g); IR (KBr) 1342, 1544, 1669, 3072 cm−1; 1H NMR (400 MHz, DMSO-d6) δ (ppm) 4.13 (s, 3H), 7.45 (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), 13C NMR (100 MHz, DMSO-d6) δ (ppm) 57.4, 114.0, 123.5, 125.2, 129.1, 130.9, 165.4, 187.9; M.S (M+): 181. 1,4-Dinitrobenzene (13a). Yellow solid; mp 167−169 °C (lit.,27 mp 165−166 °C); isolated yield 75% (0.126 g); IR (KBr) 799, 1360, 1588, E
DOI: 10.1021/acs.joc.7b03289 J. Org. Chem. XXXX, XXX, XXX−XXX
Article
The Journal of Organic Chemistry
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(b) Ghaderi, H.; Zolfigol, M. A.; Bayat, Y.; Zarei, M.; Noroozizadeh, E. Synlett 2016, 27, 2246. (c) Shiri, M.; Zolfigol, M. A.; Kruger, H. G.; Tanbakouchian, Z. Tetrahedron 2010, 66, 9077. (21) Yang, Z.; Li, J.; Hua, J.; Yang, T.; Yi, J.; Zhou, C. Synlett 2017, 28, 1079. (22) Luo, Z.-G.; Xu, F.; Fang, Y.-Y.; Liu, P.; Xu, X.-M.; Feng, C.-T.; Li, Z.; He, J. Res. Chem. Intermed. 2016, 42, 6079. (23) Das, J. P.; Sinha, P.; Roy, S. Org. Lett. 2002, 4, 3055. (24) Maity, S.; Manna, S.; Rana, S.; Naveen, T.; Mallick, A.; Maiti, D. J. Am. Chem. Soc. 2013, 135, 3355. (25) Hanson, J. R.; Hitchcock, P. B.; Toche, F. J. Chem. Res. 2008, 476. (26) Patil, V. V.; Shankarling, G. S. J. Org. Chem. 2015, 80, 7876. (27) Maggini, M.; Passudetti, M.; Gonzales-Trueba, G.; Prato, M.; Quintily, U.; Scorrano, G. J. Org. Chem. 1991, 56, 6406. (28) Laali, K. K.; Koser, G. F.; Subramanyam, S.; Forsyth, D. A. J. Org. Chem. 1993, 58, 1385. (29) Holan, M.; Jahn, U. Org. Lett. 2014, 16, 58.
ASSOCIATED CONTENT
S Supporting Information *
The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.joc.7b03289. Experimental procedures and compound characterization data (PDF)
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AUTHOR INFORMATION
Corresponding Authors
*E-mail:
[email protected]. *E-mail: zolfi@basu.ac.ir; mzolfi
[email protected]. ORCID
Ahmad R. Moosavi-Zare: 0000-0003-0321-9326 Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS We thank Bu-Ali 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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REFERENCES
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DOI: 10.1021/acs.joc.7b03289 J. Org. Chem. XXXX, XXX, XXX−XXX
