Dichloromethane → HCID 66716977, compound

Add 14.31 g (44.0 mmol) of 3.6-dibromo carbazole (A-1), 25.01 g (176.1 mmol) of 5-methyl-2-thiophen boronic acid, and 1.30 g of tetrakis(triphenylphosphine) palladium to a solvent mixture of 180 ml of toluene and 60 ml of ethanol; add an aqueous solution in which 37.3 g of sodium carbonate is dissolved in 90 ml of distilled water to the liquid mixture; reflux the mixture for 15 hours while heating in nitrogen atmosphere; next, filter the resultant with celite with heat to remove insoluble matters; separate the organic layer; distill away the solvent under a reduced pressure; subsequent to water-washing of the residual matter, dry the resultant to obtain a yellow brown solid; refine the resultant with silica gel column chromatography using a solvent mixture of methylene chloride and hexane as an eluting solution to obtain 12.25 g of 3,6-bis(5-methylthiophene-2-yl)carbazole (A-2); mix 8.07 g (22.4 mmol) of the thus obtained 3,6-bis(5-methylthiophene-2-yl)carbazole, 21.00 g (89.7 mmol) of 4-iodine anisole, 0.71 g of copper powder, and 12.40 g of potassium carbonate; reflux the mixture for six hours while heating in nitrogen atmosphere followed by cooling-down to 100° C.; next, add 80 ml of toluene to the resultant; filter the resultant with celite with heat to remove insoluble matters; distill away the solvent under a reduced pressure; dissolve the residual in methylene chloride followed by water-washing; dry the resultant to obtain brown liquid; next, refine the resultant with silica gel column chromatography using a solvent mixture of methylene chloride and hexane as an eluting solution to obtain 4.39 g of 3,6-bis(5-methylthiophene-2-yl)-9-(4-methoxyphenyl)carbazole (B-2); dissolve 3.73 g (8.0 mmol) of the thus obtained 3,6-bis(5-methylthiophene-2-yl)-9-(4-methoxyphenyl)carbazole in 30 ml of methylene chloride; drip 8 ml of a methylene chloride solution of 1M boron tribromide to the resultant solution at −10° C. followed by stirring at room temperature; subsequent to water-washing, dry the resultant and thereafter remove the solvent to obtain a gray solid; furthermore, refine the resultant with silica gel column chromatography using a solvent mixture of methylene chloride and hexane as an eluting solution to obtain 3.47 g of 3,6-bis(5-methylthiophene-2-yl)-9-(4-hydroxyphenyl)carbazole (B-3); dissolve 1.81 g (4.0 mmol) of the thus obtained 3,6-bis(5-methylthiophene-2-yl)-9-(4-hydroxyphenyl)carbazole and 4.35 g (16.0 mmol) of 1,8-dibromooctane in 20 ml of methylethyl ketone; add 0.83 g of potassium carbonate to the solution; reflux the solution for seven hours while heating; next, filter the resultant to remove insoluble matters; distill away the solvent under a reduced pressure; dissolve the residual in methylene chloride followed by water-washing; dry the resultant and thereafter remove the solvent to obtain pale yellow liquid; next, refine the resultant with silica gel column chromatography using a solvent mixture of methylene chloride and hexane as an eluting solution to obtain 1.83 g of 3,6-bis(5-methylthiophene-2-yl)-9-[4-(8-bromooctyloxy)phenyl]carbazole; dissolve 1.50 g (2.3 mmol) of the thus obtained 3,6-bis(5-methylthiophene-2-yl)-9-[4-(8-bromooctyloxy)phenyl]carbazole in a solvent mixture of 20 ml of tetrahydrofuran (THF) and 20 ml of ethanol; add 0.40 g (3.5 mmol) of potassium thioacetate to the solution in nitrogen atmosphere; reflux the solution for five hours while heating followed by cooling down to room temperature; pour water to the solution followed by extraction with methylene chloride; subsequent to water-washing, dry the resultant and thereafter remove the solvent to obtain a pale yellow white solid; furthermore, refine the resultant with silica gel column chromatography using a solvent mixture of methylene chloride and hexane as an eluting solution to obtain 1.22 g of 8-{4-[3,6-bis(5-methylthiophene-2-yl)-9-yl]phenoxy}octylester (C-3); dissolve 1.02 g (1.6 mmol) of the thus obtained 8-{4-[3,6-bis(5-methylthiophene-2-yl)-9-yl]phenoxy}octylester in a solvent mixture of 30 ml of tetrahydrofuran (THF) and 10 ml of ethanol in nitrogen atmosphere; add 0.5 ml of NaOH aqueous solution having 50% by weight to the solution followed by stirring at room temperature for one hour; pour water to the solution followed by extraction with chloroform; subsequent to water-washing, dry the resultant and thereafter distill away the solvent to obtain a coarse product; next, refine the resultant with silica gel column chromatography using a solvent mixture of chloroform and hexane as an eluting solution to obtain 0.86 g of 8-{4-[3,6-bis(5-methylthiophene-2-yl)carbazole-9-yl]phenoxy}octane-1-thiol (C-4) (hereinafter referred to as carbazole derivative 1) represented by the following chemical structure 7.

1. temperaturereflux the solution for seven hours
2. temperaturewhile heating
3. filtrationnext, filter the resultant
4. customto remove insoluble matters
5. distillationdistill away the solvent under a reduced pressure
6. dissolutiondissolve the residual in methylene chloride
7. washwashing
8. customdry the resultant
9. customremove the solvent
10. customto obtain pale yellow liquid

ORD record

ord-d1e02f4e12b040aabc7aa2516012bba9

Source dataset

uspto-grants-2016_02

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09263682B2