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Stage #1: With isopropylmagnesium chloride In tetrahydrofuran for 1 h; Cooling with ice; Inert atmosphere Stage #2: With zinc(II) chloride-TMEDA In tetrahydrofuran at 20℃; for 1 h; Cooling with ice; Inert atmosphere Stage #3: With tetrakis(triphenylphosphine) palladium(0) In tetrahydrofuran for 1.5 h; Reflux; Inert atmosphere
A flask which in 2-bromothiazole (16.4 g) and 50 ml of THF solution were put was cooled in an iced bath, and then 55 ml of a THF solution of 2 M isopropylmagnesium chloride was added dropwise there to under in a in nitrogen atmosphere while stirring the solution. After dropewise addition the rection mixture was stirred for 1 hour, and then a zinc chloride-tetramethylethylenediamine complex (30.3 g) was added. the resuting mixture was stirring for 1 hour at room temperature, and then 1-bromo-4-iodobenzene (28.3 g) and Pd(PPh3)4 (3.5 g) were added and then heated and stirred for 1.5 hours at reflux temperature. After cooling the reaction solution to room temperature, to remove the metal ions of the catalyst, a solution prepared by dissolving the compound ethylenediamine Inc. acid, use the sodium salt dihydrate equivalent to approximately 2-fold molar with respect to the objective to the appropriate amount of water (after and it stirred to fall abbreviated) EDTA · 4Na in an aqueous solution. Then, after removing also separated by adding toluene, and the solvent was distilled off under reduced pressure to the solution, and purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 50/1 (volume ratio)) to give 2-(4-bromophenyl)thiazole (18.3g).
Reference:
[1] Patent: KR2015/138163, 2015, A, . Location in patent: Paragraph 0333; 0334
2
[ 96159-83-0 ]
[ 27149-27-5 ]
Reference:
[1] Chemistry - An Asian Journal, 2013, vol. 8, # 7, p. 1408 - 1411
3
[ 589-87-7 ]
[ 121359-48-6 ]
[ 27149-27-5 ]
Reference:
[1] Journal of the American Chemical Society, 2017, vol. 139, # 24, p. 8267 - 8276
[2] Tetrahedron Letters, 2006, vol. 47, # 4, p. 599 - 603
4
[ 623-00-7 ]
[ 27149-27-5 ]
Reference:
[1] Chemistry - An Asian Journal, 2013, vol. 8, # 7, p. 1408 - 1411
With copper(l) iodide; potassium carbonate; N,N`-dimethylethylenediamine; In acetonitrile; for 18h;Heating / reflux;
EXAMPLE 16; (R)-5-(((5-oxo-1-(4-(thiazol-2-yl)phenyl)pyrrolidin-2-yl)methoxy)methyl)thiophene-2-carboxylic acid (58); Step 1. Arylation of 1 to Give 56; Potassium carbonate (800 mg, 5.79 mmol), copper(I) iodide (55 mg, 0.29 mmol) and N,N'-dimethylethylene diamine (62 muL, 0.58 mmol) were added sequentially to a solution of amide 1 (400 mg, 3.47 mmol) and <strong>[27149-27-5]2-(4-bromophenyl)thiazole</strong> (for representative preparation, see Chemica Scripta 1985, 25(4), 295-299; 694 mg, 2.89 mmol) in MeCN (6.6 mL). The reaction flask was fitted with a reflux condenser, the mixture was degassed with nitrogen by evac/fill (5×) and then heated at reflux. After 18 hours, the mixture was cooled, diluted with EtOAc and filtered through celite, washing with excess EtOAc. The filtrate was concentrated in vacuo. The crude residue was purified on 40 g silica (CH2Cl2?15% MeOH/CH2Cl2, gradient) to afford 530 mg (67%) of 56.
With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; potassium acetate; for 3h;Reflux; Inert atmosphere;
A flask in which 2-(4-bromophenyl) thiazole (9.0 g), bis(pinacolato)diboron (11.4 g), Pd(dppf)Cl2·CH2Cl2 (0.9 g), potassium acetate (7.4 g) and cyclopentyl methyl ether (50 ml) into a flask under a nitrogen atmosphere for 3 hours heating at reflux It was stirred. After completion of the heating, the reaction solution was cooled to room temperature, collected by suction filtration, to remove the insoluble matter. A sense of solvent Was distilled off under pressure, short column of activated carbon, then was purified by NH silica gel short column formula, 2- (4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)phenyl)thiazole was obtained (7.7 g). The obtained 2-(4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl)phenyl)thiazole was used to synthesis a Compound (1-25) descriped below.
A flask which in 2-bromothiazole (16.4 g) and 50 ml of THF solution were put was cooled in an iced bath, and then 55 ml of a THF solution of 2 M isopropylmagnesium chloride was added dropwise there to under in a in nitrogen atmosphere while stirring the solution. After dropewise addition the rection mixture was stirred for 1 hour, and then a zinc chloride-tetramethylethylenediamine complex (30.3 g) was added. the resuting mixture was stirring for 1 hour at room temperature, and then 1-bromo-4-iodobenzene (28.3 g) and Pd(PPh3)4 (3.5 g) were added and then heated and stirred for 1.5 hours at reflux temperature. After cooling the reaction solution to room temperature, to remove the metal ions of the catalyst, a solution prepared by dissolving the compound ethylenediamine Inc. acid, use the sodium salt dihydrate equivalent to approximately 2-fold molar with respect to the objective to the appropriate amount of water (after and it stirred to fall abbreviated) EDTA · 4Na in an aqueous solution. Then, after removing also separated by adding toluene, and the solvent was distilled off under reduced pressure to the solution, and purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 50/1 (volume ratio)) to give 2-(4-bromophenyl)thiazole (18.3g).
2,2 '-((2-phenylanthracene-9,10-diyl)bis(4,1-phenylene))dithiazole[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
1.9 g
With potassium phosphate; tetrakis(triphenylphosphine) palladium(0); In water; for 7.5h;Reflux;
A flask in which 2,2 '-(2-phenylanthracene-9,10-diyl)bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolane)(3.5 g) See the sythesis method described in Japanese Patent Publication No. 2008-247895, 2- (4-bromophenyl)thiazole (3.7 g), tripotassium phosphate (5.9 g), Pd(PPh3)4 (0.2g), 1,2,4-trimethylbenzene (20 ml) flask and water (2 ml) was stirred into the heated 7.5 hours at reflux temperature. The reaction mixture was cooled to room temperature and was separated by adding water and toluene. The solvent was distilled off under reduced pressure, purified by silica gel column chromatography (eluent: toluene / ethyl acetate = 50/1 (volume ratio)) was purified by. Recrystallization of the solid obtained by distilling off the solvent under reduced pressure from chlorobenzene, compound (1-3): 2,2 '-((2-phenylanthracene-9,10-diyl)bis(4,1-phenylene))dithiazole (1.9 g).