* 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.
With 2-Picolinic acid; potassium phosphate; copper(l) iodide In dimethyl sulfoxide at 80℃; for 15 h;
3-Aminophenol (6.0 g, 54.8 mmol), 3-iodoaniline (10.0 g, 45.7 mmol), picolinic acid (0.56 g, 4.6 mmol), copper(I) iodide and potassium phosphate (19.4 g, 91 mmol) were added to DMSO (100 mL) and the reaction mixture degassed by bubbling nitrogen into the mixture for 1 hour. The reaction flask was then placed into a preheated 80° C. oil bath and stirred for 15 hours before cooling to room temperature. The reaction mixture was then poured into 150 mL of water and extracted with 3×50 mL EtOAc. The combined organics were washed with 50 mL water, 50 mL brine, dried and evaporated. The crude oil was chromatographed on silica with 80/20 hexane/EtOAc (v/v) followed by 50/50 hexane/EtOAc (v/v) to give 7.2 g (79percent) of 3,3′-oxydianiline as a white solid. The product was confirmed by GC/MS and NMR.
Reference:
[1] Angewandte Chemie - International Edition, 2013, vol. 52, # 2, p. 650 - 654[2] Angew. Chem., 2013, vol. 125, # 2, p. 678 - 682,5
[3] Patent: US9461254, 2016, B2, . Location in patent: Page/Page column 195-196
[4] Journal of the American Chemical Society, 2009, vol. 131, # 47, p. 17423 - 17429
2
[ 38490-83-4 ]
[ 15268-07-2 ]
Reference:
[1] Journal of Physical Organic Chemistry, 1994, vol. 7, p. 495 - 502
[2] Yakugaku Zasshi, 1955, vol. 75, p. 1077,1079[3] Chem.Abstr., 1956, p. 5618
[4] Bulletin de la Societe Chimique de France, 1974, p. 641 - 648
[5] Russian Journal of Applied Chemistry, 1998, vol. 71, # 12, p. 2171 - 2176
[6] Organic Letters, 2007, vol. 9, # 14, p. 2629 - 2632
[7] J.Fac.Sci.Hokkaido Univ., 1951, vol. <III>4, p. 70,88
3
[ 585-79-5 ]
[ 15268-07-2 ]
Reference:
[1] Organic Letters, 2007, vol. 9, # 14, p. 2629 - 2632
[2] Yakugaku Zasshi, 1955, vol. 75, p. 1077,1079[3] Chem.Abstr., 1956, p. 5618
Examples of the diamine are aromatic diamines, and the specific examples are: ... 4,4'-(m-phenylenediisopropylidene)dianiline, 2,2-bis[4-(p-aminophenoxy)phenyl]hexafluoropropane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, ...
With 2-Picolinic acid; potassium phosphate; copper(l) iodide; In dimethyl sulfoxide; at 80℃; for 15h;
3-Aminophenol (6.0 g, 54.8 mmol), 3-iodoaniline (10.0 g, 45.7 mmol), picolinic acid (0.56 g, 4.6 mmol), copper(I) iodide and potassium phosphate (19.4 g, 91 mmol) were added to DMSO (100 mL) and the reaction mixture degassed by bubbling nitrogen into the mixture for 1 hour. The reaction flask was then placed into a preheated 80 C. oil bath and stirred for 15 hours before cooling to room temperature. The reaction mixture was then poured into 150 mL of water and extracted with 3×50 mL EtOAc. The combined organics were washed with 50 mL water, 50 mL brine, dried and evaporated. The crude oil was chromatographed on silica with 80/20 hexane/EtOAc (v/v) followed by 50/50 hexane/EtOAc (v/v) to give 7.2 g (79%) of 3,3?-oxydianiline as a white solid. The product was confirmed by GC/MS and NMR.
79%
With 2-Picolinic acid; potassium phosphate; copper(l) iodide; In dimethyl sulfoxide; at 80℃; for 16h;Inert atmosphere;
Synthesis of 3,3'-oxydianiline: 3-Aminophenol (6.0 g, 54.8 mmol), 3-iodoaniline (10.0 g, 45.7 mmol), picolinic acid (0.56 g, 46 mmol), copper(I) iodide and potassium phosphate (19.4 g, 91 mmol) were added to DMSO (100 mL) and the reaction mixture degassed by bubbling nitrogen into the mixture for 1 hour. The reaction flask was then placed into a preheated 80 C. oil bath and stirred for 15 hours before cooling to room temperature. The reaction mixture was then poured into 150 mL of water and extracted with 3*50 mL EtOAc. The combined organics were washed with 50 mL water, 50 mL brine, dried and evaporated. The crude oil was chromatographed on silica with 80/20 hexane/EtOAc (v/v) followed by 50/50 hexane/EtOAc (v/v) to give 7.2 g (79%) of3,3'-oxydianiline as a white solid. The product was confirmed by GC/MS and NMR.
With toluene-4-sulfonic acid; potassium iodide; sodium nitrite; In water; tert-butyl alcohol; at 10 - 20℃; for 4h;
To a suspension of p-toluenesulfonic acid hydrate (30.8 g, 162 mmol) in tert-butylalcohol (110 mL) and water (5 mL) was added 3,3?-oxydianiline (3.6 g, 17.9 mmol) and the reaction mixture cooled to 10 C. in an ice/water bath. A solution of sodium nitrite (7.4 g, 108 mmol) and potassium iodide (22.4 g, 135 mmol) in water (30 mL) was added dropwise over 1 hour, keeping the temperature below 15 C. The cold bath was removed and the reaction mixture allowed to warm to room temperature and stirred for another 3 hours. To the reaction mixture was added 15 g NaHCO3 to pH 8 followed by 35 g Na2S2O3 and the mixture stirred for 30 minutes before being poured into 300 mL of water. The mixture was extracted 2×100 mL with ether and 3×100 mL DCM. The combined extracts were washed with 2×100 mL water, dried over sodium sulfate and evaporated leaving 4.5 g of a dark liquid. The crude oil was chromatographed on silica with hexane to give 4.8 g (79%) of 3,3?-oxybis(iodobenzene) as a white solid. The product was confirmed by GC/MS and NMR.
79%
With toluene-4-sulfonic acid; potassium iodide; sodium nitrite; In water; tert-butyl alcohol; at 10 - 20℃; for 4h;
To a suspension of p-toluenesulfonic acid hydrate (30.8 g, 162 mmol) in tert-butylalcohol (110 mL) and water (5 mL) was added 3,3?-oxydianiline (3.6 g, 17.9 mmol) and the reaction mixture cooled to 10 C. in an ice/water bath. A solution of sodium nitrite (7.4 g, 108 mmol) and potassium iodide (22.4 g, 135 mmol) in water (30 mL) was added dropwise over 1 hour, keeping the temperature below 15 C. The cold bath was removed and the reaction mixture allowed to warm to room temperature and stirred for another 3 hours. To the reaction mixture was added 15 g NaHC03 to pH -8 followed by 35 g Na2S20 3 and the mixture stirred for 30 minutes before being poured into 300 mL of water. The mixturewas extracted 2×100 mL with ether and 3×100 mL DCM. The combined extracts were washed with 2×100 mL water, dried over sodium sulfate and evaporated leaving 4.5 g of a dark liquid. The crude oil was chromatographed on silica with hexane to give 4.8 g (79%) of 3,3?-oxybis(iodobenzene) as a white solid. The product was confirmed by GC/MS and NMR
72%
In a 250 mL round bottomed flask, <strong>[15268-07-2]3,3'-oxydianiline</strong> (4 g, 20.0 mmol) was dissolved in 100 mL of acetone. To the flask 21 mL of concentrated HCl in 30 mL of water was added dropwise. The solution was cooled to 0 C. and sodium nitrite (8.4 g, 121.8 mmol) in 50 mL of water was added slowly. The solution was stirred at 0 C. for another hour before potassium iodide (25 g, 150.6 mmol) in 50 mL water was added dropwise. The solution was stirred at 0 C. for 2 h, then at 60 C. for 4 h. Upon cooling, sodium bisulfite was added until all iodine in the solution was consumed. The mixture was then concentrated under reduced pressure. The product was dissolved in dichloromethane and washed sequentially with water and brine. The organic layer was dried over MgSO4, filtered and the solvent was removed under reduced pressure. The solid was then purified using flash chromatography through silica using hexane as eluent to give 6.09 g 3,3'-oxybis(iodobenzene) as white powder (72% yield). 1H NMR (300 MHz, CHLOROFORM-d) delta=7.55-7.42 (m, 2H), 7.41-7.30 (m, 2H), 7.15-7.03 (m, 2H), 7.03-6.90 (m, 2H).