* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Reference：
[1] Journal of the American Chemical Society, 1948, vol. 70, p. 3787
2
[ 89-58-7 ]
[ 610-29-7 ]
Reference：
[1] American Chemical Journal, 1888, vol. 10, p. 474,483
3
[ 106-42-3 ]
[ 89-58-7 ]
Yield
Reaction Conditions
Operation in experiment
86.4%
With nitric acid In acetic anhydride at 20℃; for 10 h;
General procedure: Quantities are recorded in the footnotes to the appropriate tables. All reactions were carried out in a 50 mL two-necked round bottomed flask equipped with a water condenser and a magnetic stirrer. In a typical experiment, a mixture of zeolite HBEA-25 (Si/Al = 25, 0.11g), o-xylene (0.60 mL, 5 mmol ), nitric acid ( 65percent, 0.68 mL, 10 mmol ) in acetic anhydride (5.0 mL) at room temperature for 10 h. When the reaction was over, the zeolite was removed by filtration and the filter liquor was washed with NaHCO3 (3 × 10 mL) and water (3× 10 mL). The organic phase separated was dried with anhydrous sodium sulfate, and filtrated to give a straw yellow liquid residue. The isomer distribution and yields of products were estimated from the peak areas based on the internal standard technique using gas chromatography. The straw yellow products with further purification by column chromatography, and were identified by comparison of their analytical data with those of authentic samples.
86%
With oxygen; nitronium ion In acetic anhydride at 35℃; for 12 h; Green chemistry
General procedure: The reactions were carried out in a batch reactor. In a typical run: 5 mmol o-xylene ( 0.53 g ) and freshly activated zeolite ( 0.11 g Zeolites were calcined at 550 °C for 2 h in air prior to use) were taken in a 100 mL three necked flask along with 5 mL of acetic anhydride, and a balloon filled with oxygen was connected to reactor. The reaction was carried out with stir at room temperature. The mixture samples were drawn at regular intervals and analyzed with gas chromatography. On completion of the reaction, excess nitrogen dioxide was removed by blowing air into the solution, and collected in a cold trap for reuse. The mixture was filtered through a sintered glass funnel, and filtrate was diluted with water and organic phase was extracted with dichloromethane. The concentrated mixture was separated by column chromatography. The nitro isomer distribution and yield were analyzed from the peak areas based on the internal standard technique using gas chromatography (GC-2041C, WONDACAP-1 df=1.5μm 0.53mm I.D×30m). Nitro-o-xylene products were identified by comparison of their analytical data with those of authentic samples.
86.2%
With nitric acid; acetic anhydride In dichloromethane at 0 - 20℃; for 24 h;
General procedure: A typical nitration of m-xylene over zeolite with nitric acid and acetic anhydride was carried out as follows. Zeolite (0.1 g,calcinated at 550 °C for 2 h before use), m-xylene (5 mL), and acetic anhydride (0.613 g, 6 mmol) were mixed under stirring at 0 °C. Then nitric acid (0.199 g, 95 percent, 3 mmol) was added dropwise. The mixture was stirred for 30 min and then allowed to warm to room temperature and allowed to stand for 24 h. The catalyst was removed by filtration and washed with dichloromethane (10 mL). The organic layers were washed with water (10 mL x 2), NaHCO3 solution (10 percent, 10 mL), and water (10 mL x 2), and dried with MgSO4. A known amount of p-nitrotoluene was added as internal standard. Then the solution was analysed by gas chromatography to get the total yield and ratio of 2,4-dimethylnitrobenzene to 2,6-dimethylnitrobenzene
100 %Chromat.
for 1.5 h; Schlenk technique; Ionic liquid; Inert atmosphere; Heating
General procedure: The ionic liquid (3.5–4.0 mL) was charged into an oven-dried Schlenk tube under a nitrogen atmosphere and Bi(NO3)3·5H2O (1.5 mmol) was added. The respective aromatic compound (1 mmol) was then introduced into the Schlenk tube under a nitrogen atmosphere. The reaction mixture was magnetically stirred, initially at rt for about 10 min followed by stirring in a pre-heated oil bath at 80–85 °C, until completion (as monitored by GC–MS). Once the reaction was over, the contents were cooled to rt and extracted with EtOAc–Hexane (2:3 vol/vol), until the final extraction did not show a spot corresponding to the starting material or to the product. The combined organic extracts were washed with 10percent NaHCO3 solution, dried with MgSO4, and concentrated to give the crude product. Isomer distributions were determined by GC–MS, and/or by 1H NMR.
Reference：
[1] Russian Journal of Organic Chemistry, 1993, vol. 29, # 3.2, p. 457 - 466[2] Zhurnal Organicheskoi Khimii, 1993, vol. 29, # 3, p. 546 - 558
[3] Tetrahedron Letters, 1996, vol. 37, # 4, p. 513 - 516
[4] Journal of Fluorine Chemistry, 2008, vol. 129, # 6, p. 524 - 528
[5] Organic Letters, 2018, vol. 20, # 11, p. 3197 - 3201
[6] Green Chemistry, 2015, vol. 17, # 6, p. 3446 - 3451
[7] Journal of Fluorine Chemistry, 1990, vol. 46, # 3, p. 507 - 513
[8] Synthetic Communications, 2005, vol. 35, # 17, p. 2237 - 2241
[9] Journal of Organic Chemistry, 2006, vol. 71, # 10, p. 3952 - 3958
[10] Journal of Organic Chemistry, 1981, vol. 46, # 17, p. 3533 - 3537
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[19] Journal of Organic Chemistry, 1981, vol. 46, # 17, p. 3533 - 3537
[20] Journal of the American Chemical Society, 1992, vol. 114, # 5, p. 1756 - 1770
[21] Journal of the American Chemical Society, 1948, vol. 70, p. 3787
[22] Journal fuer Praktische Chemie (Leipzig), 1935, vol. <2> 142, p. 153,166
[23] Justus Liebigs Annalen der Chemie, 1875, vol. 176, p. 55
[24] Journal of the American Chemical Society, 1953, vol. 75, p. 4307,4310
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[29] Journal of Organic Chemistry, 1961, vol. 26, p. 919 - 923
[30] Magnetic Resonance in Chemistry, 1985, vol. 23, # 7, p. 597 - 604
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[38] Catalysis Communications, 2014, vol. 49, p. 82 - 86
4
[ 95-72-7 ]
[ 89-58-7 ]
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[1] Journal of the American Chemical Society, 2009, vol. 131, # 36, p. 12898 - 12899
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[1] Journal of the Chemical Society, Perkin Transactions 2: Physical Organic Chemistry (1972-1999), 1982, p. 965 - 970
19
[ 106-42-3 ]
[ 95-87-4 ]
[ 589-18-4 ]
[ 89-58-7 ]
[ 104-87-0 ]
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[1] Journal of Physical Chemistry, 1981, vol. 85, # 19, p. 2740 - 2746
20
[ 67-56-1 ]
[ 54874-33-8 ]
[ 89-58-7 ]
[ 104824-12-6 ]
[ 104824-13-7 ]
[ 74894-53-4 ]
[ 74894-52-3 ]
[ 105-67-9 ]
Reference：
[1] Canadian Journal of Chemistry, 1986, vol. 64, p. 1093 - 1101
21
[ 54874-31-6 ]
[ 29559-27-1 ]
[ 712-32-3 ]
[ 89-58-7 ]
[ 133205-71-7 ]
[ 133205-72-8 ]
[ 133205-72-8 ]
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[1] Australian Journal of Chemistry, 1991, vol. 44, p. 43 - 51
22
[ 106-42-3 ]
[ 7697-37-2 ]
[ 89-58-7 ]
Reference：
[1] Justus Liebigs Annalen der Chemie, 1875, vol. 176, p. 55
23
[ 89-58-7 ]
[ 696-01-5 ]
Reference：
[1] Journal of Fluorine Chemistry, 1990, vol. 46, # 3, p. 507 - 513
24
[ 89-58-7 ]
[ 27329-27-7 ]
Yield
Reaction Conditions
Operation in experiment
75%
With oxygen; sodium hydroxide In ethanol; water at 65℃; for 24 h; Autoclave
1,4-dimethyl-2-nitrobenzene (907 mg, 6 mmol, 1.0 eq)Sodium hydroxide (1.8 g, 45.0 mmol, 7.5 eq)Was added to a 100 ml autoclave,10 ml of 80percent (v / v) ethanol (8 ml of ethanol, 2 ml of water)After charging oxygen three times,Passing oxygen gas (pressure 1.8MPa),In the oil bath temperature control 65 for 24 hoursAfter the reaction was diluted with methanol,Neutral and PH = 2-3,The solvent was removed under reduced pressure,After adding ethyl acetate, the mixture was dried and filtered.Separated by chromatography,1,4-dimethyl-2-nitrobenzene recovered 129mg (0.85mmol),The conversion of 1,4-dimethyl-2-nitrobenzene was 86percent4-methyl-2-nitrobenzoic acid was obtained811 mg (4.48 mmol) in 75percent yield
Reference：
[1] Patent: CN106995374, 2017, A, . Location in patent: Paragraph 0031; 0032; 0033; 0034; 0035; 0036; 0037-0042
[2] Journal of Organic Chemistry, 2018, vol. 83, # 15, p. 8092 - 8103
25
[ 89-58-7 ]
[ 3096-71-7 ]
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[1] Chemische Berichte, 1894, vol. 27, p. 1930
[2] Bulletin de la Societe Chimique de France, 1966, p. 1848 - 1858
With N-ethyl-N,N-diisopropylamine; In tetrahydrofuran; at 0 - 20℃;
[0057] Synthesis of S3: 4-methyl-3-nitroaniline (2.0 g, 13.1 mmol) was added to an oven- dried flask. Tetrahydrofuran (66 mL) was added. The reaction mixture was then cooled to 0 C using an ice bath. 3-trifluoromethylbenzoyl chloride (2.742 g, 13.1 mmol) was then added, followed by diisopropylethylamine (2.039 g, 15.77 mmol). The reaction mixture was then allowed to warm to room temperature and stirred overnight. Tetrahydrofuran was then removed via rotary vaporization. The crude mixture was then suspended in water, filtered, and then rinsed with water twice. After drying, 4.1 g of S3 as a light yellow solid was obtained (96 % yield). Spectral data: 1H NMR (400 MHz, DMSO-d6) δ 10.77 (s, 1H), 8.50 (d, J = 2.3 Hz, 1H), 8.31 - 8.22 (m, 2H), 7.97 (t, J = 9.4 Hz, 2H), 7.77 (t, J = 7.8 Hz, 1H), 7.47 (d, J = 8.4 Hz, 1H), 1.23 (s, 3 H) ; 19F NMR (376 MHz, dmso) δ -61.14.; HRMS-ESI (m/z): [M + H]+ calcd for C15H11F3N2O3, 325.0795; found 325.0794.
With oxygen; sodium hydroxide; In ethanol; water; at 65℃; under 13501.4 Torr; for 24h;Autoclave;
1,4-dimethyl-2-nitrobenzene (907 mg, 6 mmol, 1.0 eq)Sodium hydroxide (1.8 g, 45.0 mmol, 7.5 eq)Was added to a 100 ml autoclave,10 ml of 80% (v / v) ethanol (8 ml of ethanol, 2 ml of water)After charging oxygen three times,Passing oxygen gas (pressure 1.8MPa),In the oil bath temperature control 65 for 24 hoursAfter the reaction was diluted with methanol,Neutral and PH = 2-3,The solvent was removed under reduced pressure,After adding ethyl acetate, the mixture was dried and filtered.Separated by chromatography,1,4-dimethyl-2-nitrobenzene recovered 129mg (0.85mmol),The conversion of 1,4-dimethyl-2-nitrobenzene was 86%4-methyl-2-nitrobenzoic acid was obtained811 mg (4.48 mmol) in 75% yield
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