* 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 tetrabutylammonium dichlorobromate; zinc dibromide In nitromethane at 20℃; for 44 h;
Into an eggplant type flask having a capacity of 200 milliliter, m-xylene in an amount of 7.5 mmol (0.795 g), zinc bromide in an amount of 33.6 mmol (7.56 g) and nitromethane in an amount of 60 milliliter were placed, and the resultant solution was stirred at room temperature, followed by adding 15.8 mmol (6.19 g) of tetra n-butylammonium dichlorobromate little by little while dividing into several times. After stirring the resultant solution at room temperature for 44 hours, sodium sulfite aqueous solution was added and the solution was extracted with the use of ether. An organic layer was removed through pressure reduction and as a result, a yellow solid was obtained. After pouring hexane on the yellow solid, the resultant mixture was heated up to the temperature of about 85 °C, and the resultant solution was filtered. The filtrate was removed through pressure reduction and as a result, 0.945 g of white solid as the aimed substance dbb was obtained (yield: 48 percent).
43.7%
With bromine In tetrachloromethane at 0 - 20℃; for 2 h;
1,3-dimethyl-benzene (30.0g, 282.6mmol) and FeCl3 (2.3g, 14.1mmol) is dissolved in CCl4, Br2 to this at 0°C (32.0mL, 621.7mmol) is slowly It was added. After stirring for 2 hours at room temperature, the reaction solution was neutralized with aqueous KOH. Extraction with MC, dried in the subsequent MgSO4, Compound A by distillation, and column separation under reduced pressure (32.5g, 123.12mmol, 43.7percent) was obtained.
Reference：
[1] Tetrahedron, 2016, vol. 72, # 41, p. 6363 - 6367
[2] Chemistry - A European Journal, 2013, vol. 19, # 32, p. 10672 - 10689
[3] Journal of Organic Chemistry, 2005, vol. 70, # 21, p. 8522 - 8526
[4] Patent: EP1816134, 2007, A1, . Location in patent: Page/Page column 32; 33
[5] Patent: JP2016/47836, 2016, A, . Location in patent: Paragraph 0051-0052
[6] Angewandte Chemie - International Edition, 2015, vol. 54, # 35, p. 10317 - 10323[7] Angew. Chem., 2015, vol. 127, p. 10457 - 10461,5
[8] Journal of the Chemical Society. Perkin Transactions 2, 1997, # 2, p. 147 - 156
[9] Journal of the American Chemical Society, 1921, vol. 43, p. 311
[10] Chemische Berichte, 1886, vol. 19, p. 2138
[11] Justus Liebigs Annalen der Chemie, 1870, vol. 156, p. 235
[12] Justus Liebigs Annalen der Chemie, 1868, vol. 147, p. 29
[13] Chemische Berichte, 1899, vol. 32, p. 3317
[14] Journal of the American Chemical Society, 1916, vol. 38, p. 2548
[15] Bulletin de la Societe Chimique de France, 1960, p. 1798 - 1807
[16] Inorganic Chemistry, 2012, vol. 51, # 6, p. 3813 - 3826
[17] ACS Catalysis, 2014, vol. 4, # 6, p. 1953 - 1963
[18] Chemistry - A European Journal, 2015, vol. 21, # 45, p. 16083 - 16090
[19] Patent: CN105399602, 2016, A, . Location in patent: Paragraph 0014; 0021
A 100-mL round bottomed flask wrapped in aluminum foil is charged with m-xylene (40.0 mL, 328 mmol) and iodine (0.48 g, 1.90 mmol). The mixture is stirred for about an hour while cooling in an ice bath. Bromine (34 mL, 656 mmol) is added via dropping funnel over a period of one hour. After overnight reaction, potassium hydroxide (KOH) (20percent aq, 150 mL) is added and the resulting mixture is heated gently using a heating mantle. The solid is melted and the biphasic mixture is stirred for about one hour as the yellow color slowly fades. After cooling, the liquid is decanted and the white solid is collected by filtration and washed with additional water (3*100 mL), then recrystallized from ethanol (250 mL). Yield=42.0 g (48.6percent)
Reference：
[1] Patent: US8592615, 2013, B2, . Location in patent: Sheet 27
[2] Chemische Berichte, 1899, vol. 32, p. 3317
[3] Justus Liebigs Annalen der Chemie, 1870, vol. 156, p. 235
[4] Justus Liebigs Annalen der Chemie, 1868, vol. 147, p. 29
2,2’-(4,6-dimethyl-1,3-phenylene)dipyridine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
33%
With lithium chloride;bis-triphenylphosphine-palladium(II) chloride; In toluene; for 72h;Heating / reflux;
Into an eggplant type flask having a capacity of 200 milliliter, dbb in an amount of 5.11 mmol (1.35 g), (2-pyridyl)trimethyl tin in an amount of 15.3 mmol (3.71 g), Pd (PPh3)2Cl2 in an amount of 0.408 mmol (0.286 g), lithium chloride in an amount of 51.1 mmol (2.17 g) and toluene as a solvent in an amount of 20 milliliter were placed and the resultant solution was refluxed for 3 days. After the resultant solution was cooled by leaving it standing, saturated potassium fluoride aqueous solution was added and the resultant solution was stirred for 30 minutes. After filtering the resultant solution, dichloromethane and 5 % sodium hydrogen carbonate aqueous solution were added to the filtrate and the resultant solution was extracted. Adding sodium sulfate into an organic layer and dehydrating the resultant mixture, the organic layer was removed through pressure reduction, and the remained substance was refined by means of silica gel column chromatography (hexane : ether= 4:1). After re-crystallizing the resultant substance with the use of heated hexane, white crystals of dpyx in an amount of 0.31 g was obtained (yield: 33 %). m.p.: 89 to 90 C
[5-(Bis-{5-[bis-(4-tert-butyl-phenyl)-methoxy-methyl]-2,4-dimethyl-phenyl}-methoxy-methyl)-2,4-dimethyl-phenyl]-bis-(4-tert-butyl-phenyl)-methanol[ No CAS ]
Trifluoro-acetic acid {5-[bis-(4-tert-butyl-phenyl)-(2,2,2-trifluoro-acetoxy)-methyl]-2,4-dimethyl-phenyl}-bis-(4-tert-butyl-phenyl)-methyl ester[ No CAS ]
5-Bromo-2,4-dimethylphenol. In a glovebox, <strong>[615-87-2]1,5-dibromo-2,4-dimethylbenzene</strong> (10.000 g, 37.9 mmol) is dissolved in dry THF (140 mL) in a one-neck round bottomed flask with a thermometer well. The flask is capped with a septum, and removed from the glovebox. Nitrogen purge is provided via a needle through the septum, and the solution is cooled to -70 C. using a dry ice/acetone bath. Butyllithium (BuLi) (1.6M in hexanes, 26 mL, 42 mmol) is added slowly, maintaining the temperature below -65 C. After stirring for 80 minutes at -70 C., trimethylborate (B(OMe)3) (4.2 mL, 37.9 mmol) is added slowly, maintaining the temperature below -62 C., and then the reaction is allowed to slowly warm to room temperature overnight. Solvents are removed on a rotovap, leaving a very pale yellow oily solid, which is dissolved in tetrahydrofuran (THF) (100 mL) and treated with hydrogen peroxide (H2O2) (30% aq, 13 mL) and sodium hydroxide (NaOH) (1M, 25 mL) for two hours. The reaction is then quenched with ammonium chloride (NH4Cl) (aq) and extracted into ether (2*100 mL). The organic fractions are combined, dried over sodium sulfate, filtered and dried in vacuo. Yield=6.60 g (86.7%) of pale yellow waxy solid.
2,2’-(4,6-dimethyl-1,3-phenylene)dipyridine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
69%
With trans-bis(triphenylphosphine)palladium dichloride; lithium chloride; In toluene; at 116℃; for 24h;Inert atmosphere;
A mixture of 2-tri-n-butylstannylpyridine (18.4 g, 0.05 mol), <strong>[615-87-2]1,5-dibromo-2,4-dimethyl-benzene</strong> (5.3 g, 0.02 mol), bis(triphenylphosphine) palladium(II) chloride (0.28 g, 0.4 mmol) and lithium chloride (6.4 g, 0.15 mol) in dry toluene (50 mL) was heated at 116 C under N2 for 24 h. After the reaction mixture cooled to room temperature, saturated KF solution (50 mL) was added and the solution stirred for 30 min. The precipitated solid was removed by filtration and washed with water (50 mL). NaHCO3 solution (10%, 150 mL) was then added to the combined filtrates, extracted with dichloromethane (3×200 mL), and dried over MgSO4. Removal of solvent under reduced pressure and purification of the residue by column chromatography (silica, hexane/dichloromethane=8:1; V/V) gave the desired product as a pale yellow solid (3.62 g, 69%).
Chemistry
Pharmaceutical Intermediates
Inhibitors/Agonists
Material Science
For Research Only
110K+ Compounds
Competitive Price
1-2 Day Shipping
