* 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] Revue Roumaine de Chimie, 2014, vol. 59, # 11-12, p. 1021 - 1027
2
[ 541-73-1 ]
[ 611-06-3 ]
[ 618-62-2 ]
[ 601-88-7 ]
Reference：
[1] Synthesis, 1994, # 8, p. 841 - 845
[2] Synthesis, 1994, # 8, p. 841 - 845
3
[ 7697-37-2 ]
[ 541-73-1 ]
[ 611-06-3 ]
[ 601-88-7 ]
Reference：
[1] Recueil des Travaux Chimiques des Pays-Bas, 1904, vol. 23, p. 359
4
[ 601-88-7 ]
[ 17802-02-7 ]
Reference：
[1] Patent: US2010/94000, 2010, A1,
5
[ 608-31-1 ]
[ 601-88-7 ]
Yield
Reaction Conditions
Operation in experiment
92%
Stage #1: With sodium tungstate (VI) dihydrate; sulfuric acid In methanol at 40℃; Stage #2: With dihydrogen peroxide In methanol; water at 40℃; for 9 h; Stage #3: With potassium hydroxide In methanol; water at 20 - 40℃; for 2 h;
1.32 g (4.0 mmol) of sodium tungstate dihydrate and 4.0 g (40 mmol) of concentrated sulfuric acid were added to a solution of 16.2 g (100 mmol) of 2,6-dichloroaniline in 120 ml of methanol, and the mixture was heated to 40° C. 30 ml (291 mmol) of a 30percent hydrogen peroxide solution was added dropwise over 10 hours. The pH value at this time was 0.5. After the completion of the dropwise addition, the mixture was stirred at 40° C. for 9 hours. After the disappearance of the 2,6-dichloroaniline was confirmed by gas chromatography (area percentage method), a solution of 9.8 g (150 mmol) of 86percent potassium hydroxide in 24.3 ml of methanol was added dropwise while the temperature of the reaction liquid was adjusted to 40° C. or less. After the completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, and the reaction was completed. After the completion of the reaction, 95 ml of toluene and 32 ml of water were added, and the mixture was stirred for a while, and filtered. The filtrate was separated. The obtained organic phase was washed with 8 ml of water, and then heated to reflux, and dehydrated. Thus, 2,6-dichloronitrobenzene was obtained as a toluene solution. This solution was analyzed by gas chromatography by the absolute calibration method, and as a result, the yield was 92percent.
75%
With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0 - 20℃; for 2 h;
2.1.5. 1,3-Dichloro-2-nitrobenzene [4] A solution of 2,6-dichloroaniline (8.10 g, 50.0 mmol) in dichloromethane (200 mL) was cooledto 0 °C before a solution of 3-chloroperbenzoic acid (24.6 g, 100 mmol) in dichloromethane(250 mL) was added dropwise to the reaction mixture over a period of 1.5 h at 0 °C.Thereafter the solution was stirred for 2 h at room temperature before it was diluted withdichloromethane (250 mL). The reaction mixture was washed two times with an aqueoussodium thiosulfate solution (2 wt percent, 2 × 100 mL), with an aqueous sodium bicarbonatesolution (4 × 50 mL), and finally with deionized water (200 mL). The organic layer was driedwith magnesium sulfate and the solvent was removed in vacuo. The residue was suspendedin 40 mL n-hexane and irradiated by ultrasound for 5 min, filtered off, washed with n-hexane(2 × 20 mL) to give 1,3-dichloro-2-nitrobenzene (6.63 g, 37.7 mmol, 75percent) as a beige solid
Reference：
[1] Patent: US2014/163256, 2014, A1, . Location in patent: Paragraph 0161-0162
[2] Tetrahedron Letters, 1983, vol. 24, # 14, p. 1505 - 1508
[3] Tetrahedron, 1987, vol. 43, # 8, p. 1753 - 1758
[4] Beilstein Journal of Organic Chemistry, 2017, vol. 13, p. 768 - 778
[5] Journal of Medicinal Chemistry, 1968, vol. 11, # 4, p. 814 - 819
[6] Tetrahedron, 2000, vol. 56, # 2, p. 165 - 173
6
[ 5942-05-2 ]
[ 601-88-7 ]
Reference：
[1] Journal of the American Chemical Society, 1939, vol. 61, p. 2658,2660
7
[ 15307-79-6 ]
[ 59-48-3 ]
[ 87-65-0 ]
[ 15362-40-0 ]
[ 69220-40-2 ]
[ 601-88-7 ]
[ 15307-93-4 ]
[ 10113-35-6 ]
[ 6697-95-6 ]
[ 39920-37-1 ]
[ 13603-93-5 ]
[ 608-31-1 ]
Reference：
[1] Revue Roumaine de Chimie, 2014, vol. 59, # 11-12, p. 1021 - 1027
8
[ 541-73-1 ]
[ 611-06-3 ]
[ 618-62-2 ]
[ 601-88-7 ]
Reference：
[1] Synthesis, 1994, # 8, p. 841 - 845
[2] Synthesis, 1994, # 8, p. 841 - 845
9
[ 19230-28-5 ]
[ 601-88-7 ]
Reference：
[1] Angewandte Chemie - International Edition, 2016, vol. 55, # 31, p. 8928 - 8932[2] Angew. Chem., 2016, vol. 128, # 31, p. 9074 - 9078,5
10
[ 31592-84-4 ]
[ 601-88-7 ]
Reference：
[1] Justus Liebigs Annalen der Chemie, 1879, vol. 196, p. 225,226[2] Zhurnal Russkago Fiziko-Khimicheskago Obshchestva, 1879, vol. 11, p. 334,335
[3] Justus Liebigs Annalen der Chemie, 1879, vol. 196, p. 225,226[4] Zhurnal Russkago Fiziko-Khimicheskago Obshchestva, 1879, vol. 11, p. 334,335
11
[ 1194-66-7 ]
[ 601-88-7 ]
Reference：
[1] Journal of the Chemical Society [Section] B: Physical Organic, 1966, p. 1004 - 1011
12
[ 99-09-2 ]
[ 601-88-7 ]
Reference：
[1] Atti della Accademia Nazionale dei Lincei, Classe di Scienze Fisiche, Matematiche e Naturali, Rendiconti, 1909, vol. <5> 18 I, p. 100
13
[ 59992-52-8 ]
[ 601-88-7 ]
Reference：
[1] Recueil des Travaux Chimiques des Pays-Bas, 1904, vol. 23, p. 359
[2] Justus Liebigs Annalen der Chemie, 1879, vol. 196, p. 225,226[3] Zhurnal Russkago Fiziko-Khimicheskago Obshchestva, 1879, vol. 11, p. 334,335
14
[ 129825-24-7 ]
[ 601-88-7 ]
Reference：
[1] Atti della Accademia Nazionale dei Lincei, Classe di Scienze Fisiche, Matematiche e Naturali, Rendiconti, 1909, vol. <5> 18 I, p. 100
15
[ 7697-37-2 ]
[ 541-73-1 ]
[ 611-06-3 ]
[ 601-88-7 ]
Reference：
[1] Recueil des Travaux Chimiques des Pays-Bas, 1904, vol. 23, p. 359
16
[ 15307-79-6 ]
[ 59-48-3 ]
[ 87-65-0 ]
[ 15362-40-0 ]
[ 69220-40-2 ]
[ 601-88-7 ]
[ 15307-93-4 ]
[ 10113-35-6 ]
[ 6697-95-6 ]
[ 39920-37-1 ]
[ 13603-93-5 ]
[ 608-31-1 ]
Reference：
[1] Revue Roumaine de Chimie, 2014, vol. 59, # 11-12, p. 1021 - 1027
17
[ 601-88-7 ]
[ 59483-54-4 ]
Reference：
[1] Heterocycles, 1980, vol. 14, # 10, p. 1497 - 1516
[2] Recueil des Travaux Chimiques des Pays-Bas, 1949, vol. 68, p. 88,89
[3] Journal of Chemical Research, Miniprint, 1982, # 4, p. 1218 - 1225
18
[ 601-88-7 ]
[ 59483-54-4 ]
Reference：
[1] Recueil des Travaux Chimiques des Pays-Bas, 1949, vol. 68, p. 88,89
A mixture of <strong>[601-88-7]1,3-dichloro-2-nitrobenzene</strong> (10 g) and sodium methoxide (28percent in methanol, 12.06 g) was refluxed for 18 h. The mixture was diluted with ethyl acetate, and washed with 1N hydrochloric acid, and saturated brine. The organic layer was separated, dried over anhydrous magnesium sulfate and concentrated. To a solution of the residue in dichloromethane (50 ml) was added tribromoborane (1M in dichloromethane, 104.2 ml) at -20° C. Then, the reaction mixture was warmed to room temperature, and stirred for 1 h at the temperature. The mixture was poured into ice-water, and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate and concentrated to give the title compound (9.56 g).1H-NMR (300 MHz, DMSO-d6) delta: 7.06-7.14 (2H, m), 7.41 (1H, t, J=8.3 Hz), 11.53 (1H, s).
1.32 g (4.0 mmol) of sodium tungstate dihydrate and 4.0 g (40 mmol) of concentrated sulfuric acid were added to a solution of 16.2 g (100 mmol) of 2,6-dichloroaniline in 120 ml of methanol, and the mixture was heated to 40° C. 30 ml (291 mmol) of a 30percent hydrogen peroxide solution was added dropwise over 10 hours. The pH value at this time was 0.5. After the completion of the dropwise addition, the mixture was stirred at 40° C. for 9 hours. After the disappearance of the 2,6-dichloroaniline was confirmed by gas chromatography (area percentage method), a solution of 9.8 g (150 mmol) of 86percent potassium hydroxide in 24.3 ml of methanol was added dropwise while the temperature of the reaction liquid was adjusted to 40° C. or less. After the completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, and the reaction was completed. After the completion of the reaction, 95 ml of toluene and 32 ml of water were added, and the mixture was stirred for a while, and filtered. The filtrate was separated. The obtained organic phase was washed with 8 ml of water, and then heated to reflux, and dehydrated. Thus, 2,6-dichloronitrobenzene was obtained as a toluene solution. This solution was analyzed by gas chromatography by the absolute calibration method, and as a result, the yield was 92percent.
75%
With 3-chloro-benzenecarboperoxoic acid; In dichloromethane; at 0 - 20℃; for 2h;
2.1.5. 1,3-Dichloro-2-nitrobenzene [4] A solution of 2,6-dichloroaniline (8.10 g, 50.0 mmol) in dichloromethane (200 mL) was cooledto 0 °C before a solution of 3-chloroperbenzoic acid (24.6 g, 100 mmol) in dichloromethane(250 mL) was added dropwise to the reaction mixture over a period of 1.5 h at 0 °C.Thereafter the solution was stirred for 2 h at room temperature before it was diluted withdichloromethane (250 mL). The reaction mixture was washed two times with an aqueoussodium thiosulfate solution (2 wt percent, 2 × 100 mL), with an aqueous sodium bicarbonatesolution (4 × 50 mL), and finally with deionized water (200 mL). The organic layer was driedwith magnesium sulfate and the solvent was removed in vacuo. The residue was suspendedin 40 mL n-hexane and irradiated by ultrasound for 5 min, filtered off, washed with n-hexane(2 × 20 mL) to give 1,3-dichloro-2-nitrobenzene (6.63 g, 37.7 mmol, 75percent) as a beige solid
2-[4-(3-chloro-2-nitroanilino)phenyl]ethanol[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
72%
With sodium acetate; at 160℃; for 3h;in a sealed tube;
A mixture of <strong>[601-88-7]2,6-dichloronitrobenzene</strong> (Norman, M. H.; Chen, N.; et al. PCT Int. Appl., WO 9940091 (1999)., Spada, A. P.; Fink, C. A.; Myers, M. R. PCT Int. Appl., WO 9205177 (1992)., 6.3 g, 32.8 mmol), 4-aminophenylethyl alcohol (4.9 g, 36 mmol) and sodium acetate (3.2 g, 39.3 mmol) was placed in a sealed tube and heated at 160° C. for 3 h. After cooling, the mixture was poured into water (100 mL) and extracted with ethyl acetate (300 mL). The organic layer was washed with 2N aqueous NaOH (100 mL) and brine (100 mL), then dried (Na2SO4), and concentrated. Purification by flash column chromatography on silica gel eluting with hexane/ethyl acetate (1:1) to afford 4.57 g (72percent) of the title compound as a red oil: 1H-NMR (CDCl3) delta 7.09-7.28 (6H, m), 6.91 (1H, dd, J=2.0, 7.1 Hz), 3.87 (2H,t, J=6.6 Hz), 2.86 (2H, t J=6.6 Hz).
EXAMPLE 7 Preparation of 2-(beta,gamma-dihydroxypropyl)amino-6-chloronitrobenzene STR15 0.2 mole (38.4 g) of <strong>[601-88-7]2,6-dichloronitrobenzene</strong> and 0.6 mole (54.6 g) of 3-aminopropane-1,2-diol in 200 ml of 1-methyl-2-pyrrolidone are heated to 80° C. The reaction mixture is diluted with ice. The product expected precipitates. After recrystallizing from isopropanol, it melts at 126° C. Analysis of the product obtained gives the following results:
EXAMPLE 6 Preparation of 2-(beta-hydroxyethyl)amino-6-chloronitrobenzene (compound known by the formula III) STR14 0.04 mole (7.7 g) of <strong>[601-88-7]2,6-dichloronitrobenzene</strong> in 30 ml of ethanolamine is heated for 8 hours at 70° C. The reaction mixture is poured onto ice, and then extracted with ethyl acetate. After washing and drying, the ethyl acetate phase is evaporated to dryness under vacuum. The dry extract is recrystallized from ethanol. The product obtained melts at 78° C. (literature value 78.5° C.).
EXAMPLE 8 Preparation of 3-Chloro-2-nitro-benzenethiol (32). To a solution of <strong>[601-88-7]2,6-dichloronitrobenzene</strong> (31, 5.0 g, 26 mmol) in DMSO (30 mL) was added sodium sulfide nonahydrate (6.15 g, 26 mmol). The mixture was stirred at room temperature overnight. The small amount of precipitation was filtered off and water (210 mL) was added to the filtrate. The solution was then concentrated under reduced pressure to about 40 mL. Concentrated HCl was used to adjust the pH to 3-4 and the desired product was precipitated out as a yellow solid.
N-{2,4-dichloro-3-[N'-6-amino-3-(trans-4-trifluoromethyl-cyclohexylcarbamoyl)-2-(2,2-difluoro-ethoxy)-pyridin-5-ylthioureido]benzyl}-2,2-dimethyl-propionamide[ No CAS ]
N-{2,4-dichloro-3-[6-(trans-4-trifluoromethyl-cyclohexylcarbamoyl)-5-(2,2-difluoro-ethoxy)-1H-imidazo[4,5-b]pyridin-2-ylamino]benzyl}-2,2-dimethyl-propionamide[ No CAS ]
N-{2,4-dichloro-3-[6-(trans-4-trifluoromethyl-cyclohexylcarbamoyl)-5-(2,2-difluoro-ethoxy)-1H-imidazo[4,5-b]pyridin-2-ylamino]benzyl}-2,2-dimethyl-propionamide[ No CAS ]
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