* 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] Scientific Papers of the Institute of Physical and Chemical Research (Japan), 1939, vol. 35, p. 365,369[2] Chem. Zentralbl., 1939, vol. 110, # I, p. 4188
[3] Journal of the American Chemical Society, 1933, vol. 55, p. 4225,4227
[4] Chemische Berichte, 1907, vol. 40, p. 4006
[5] Justus Liebigs Annalen der Chemie, 1910, vol. 372, p. 139
2
[ 6665-97-0 ]
[ 107-06-2 ]
[ 601-89-8 ]
Reference:
[1] Journal of Organic Chemistry, 1951, vol. 16, p. 586,606
3
[ 6665-97-0 ]
[ 2734-70-5 ]
Yield
Reaction Conditions
Operation in experiment
98%
With iron; acetic acid In ethanol; water at 90℃;
To a solution of 78 (170 mg, 0.93 mmol) in AcOH (5 mL), EtOH (5 mL) and H2O (2.5 mL) was added iron powder (311 mg, 325 mesh, 5.57 mmol) portion wise. The mixture was then heated at 90° C. under N2 overnight. After cooling to room temperature, the mixture was poured onto ice, basified using solid Na2CO3 and extracted with EtOAc (3.x.). The combined organic layers were washed with brine, dried over Na2SO4 and concentrated in vacuo to yield 79 as a pale yellow solid (139 mg, 98percent). MS (APCD): m/z 154 (100percent, [M+H]+) which was used in the next step without further purification.
80%
With palladium 10% on activated carbon; hydrogen In ethanol at 20 - 30℃; Autoclave
In a 150-ml autoclave, 2,6-dimethoxynitrobenzene (10 g, 55 mmol) was added in that order,30ml absolute ethanol,0.2 g of 10percent Pd / C catalyst,Into high purity hydrogen to 1.0MPa,Reaction at room temperature.When the hydrogen pressure gauge is not falling as the end of the reaction.Filtration, the filtrate spin dry,A white solid 6.7g, 80percent yield.
60%
With hydrogenchloride; tin(II) chloride dihdyrate In diethyl ether at 20℃; for 30 h;
To conc. hydrochloric acid (15 mL) was added dihydrated tin chloride (69.6 g, 308 mmol) at rt. In another flask, compound 50 (5.6 g, 30.6 mmol) was solubilized in ethyl ether (60 mL). The resulting mixture was added by small portions to dissolved tin chloride in hydrochloric acid. The reaction was run to completion over 12 hours at rt. The mixture was then poured into cold water and basified to pH = 9 with aqueous sodium hydroxide and stirred at rt for 3 hours. The final suspension was filtered on Celite.(R).. After dilution of the filtrate with ethyl acetate and washing with water, the organic layer was dried over MgSO4 and concentrated under reduced pressure. The off-white solid obtained 51 (2.81 g, 60percent) presented the same physico-chemical properties as the commercial product. TLC Rf (EtOAc) = 0.83; 1H NMR (CDCl3, 400 MHz) δ (ppm) 3.81 (s, 2H, NH2), 3.86 (s, 6H, 2OCH3), 6.53 (d, J = 8.2 Hz, 2H, ArH), 6.69 (t, J = 8.2 Hz, 1H, ArH).
Reference:
[1] Patent: US2007/179164, 2007, A1, . Location in patent: Page/Page column 56
[2] Organic Letters, 2011, vol. 13, # 16, p. 4320 - 4323
[3] Chemistry - A European Journal, 2018, vol. 24, # 56, p. 14933 - 14937
[4] Bioorganic and Medicinal Chemistry Letters, 1999, vol. 9, # 20, p. 2929 - 2934
[5] Patent: CN107286036, 2017, A, . Location in patent: Paragraph 0088; 0089
[6] Bioorganic and Medicinal Chemistry, 2011, vol. 19, # 20, p. 6042 - 6054
[7] Journal of the American Chemical Society, 1933, vol. 55, p. 4225,4227
[8] Scientific Papers of the Institute of Physical and Chemical Research (Japan), 1939, vol. 35, p. 365,369[9] Chem. Zentralbl., 1939, vol. 110, # I, p. 4188
[10] Journal of the American Chemical Society, 1953, vol. 75, p. 5280,5282
[11] Acta Chemica Scandinavica (1947-1973), 1952, vol. 6, p. 1016,1017
[12] Justus Liebigs Annalen der Chemie, 1910, vol. 372, p. 139
[13] Journal of the Chemical Society, 1915, vol. 107, p. 472
[14] Chemische Berichte, 1907, vol. 40, p. 4006
[15] Patent: US9486455, 2016, B2, . Location in patent: Page/Page column 155
A mixture of 78 (87 mg, 0.57 mmol) and 6 (93 mg, 0.58 mmol) in AcOH (20 mL) was reflux under N2 overnight. The crude material was then concentrated in vacuo to yield 80 as a brown solid (170 mg, 100%). MS (APCI): m/z 297 (100%, [M+H]+) which was used in the next step without further purification.
With potassium nitrite; copper(II) bis(trifluoromethanesulfonate); In dimethyl sulfoxide; at 135℃; for 60h;Inert atmosphere; Sealed tube;
General procedure: An oven dried pressure tube was charged with haloarenes (0.5 mmol), copper(II) triflate (45 mg, 0.125 mmol), KNO2 (128 mg, 1.5 mmol) and anhydrous DMSO (0.6 mL) under nitrogen atmosphere. The tube was sealed with a teflon screw cap having mininert valve and nitrogen is purged through it for 5 min. It is stirred at room temperature for 10 min and then the temperature was gradually increased to 130 oC and is maintained at the same for 48 h. The reaction mixture was then cooled to room temperature, washed with excess ice cold water and extracted with ethyl acetate (3 x 10 mL). The combined organic extracts were dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure to give the crude product which was purified by column chromatography using silica gel (Table 2, entries 1-18) or basic alumina (Table 2, entries 19-23) and a mixture of ethyl acetate and hexane as the eluent to afford the desired products in good yields.