Methyl 4-hydroxy-3,5-diiodobenzoate

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of phenylboronic acid (4.95 g, 40.57 mmol), Ba(OH)2.H2O (10.48 g, 55.33 mmol), and Pd(OAc)2 (0.414 g, 1.84 mmol) in DME/H2O (110 mL/20 mL) was added 3,5-diiodo-4-hydroxybenzoic acid methyl ester (7.45 g, 18.44 mmol). The mixture was stirred at 85° C. for 3 h and was then cooled and concentrated. The residue was partitioned between ethyl acetate/2N HCl. The organic phase was dried (MgSO4) and concentrated to give a solid which was triturated with diethyl ether/petroleum ether to give 3.51 g (62.5%) of product as a white solid. 1H NMR (DMSO-d6) δ9.27 (s, 1H), 7.27 (s, 2H), 7.25-7.40 (m, 10H), 3.81 (s, 3H). was then cooled concentrated The residue was partitioned between ethyl acetate/2N HCl The organic phase was dried (MgSO4) concentrated to give a solid which was triturated with diethyl ether/petroleum ether

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirring solution of 3,5-diiodo-4-hydroxybenzoic acid (10.00 g, 25.65 mmol) in dry methanol (250 mL) was added TiCl4 (1.41 mL, 12.82 mmol) in one lot. The reaction was stirred at reflux for 6 h and was then stirred at room temperature for 24 h. The mixture was concentrated down and the residue was taken up in diethyl ether and filtered through a plug of silica gel. The filtrate was concentrated down and the residue was recrystallized from hot methanol to give 7.84 g (76%) of the ester as white crystalline needles. 1H NMR (DMSO-d6) δ10.41 (br s, 1H), 8.22 (s, 2H), 3.79 (s, 3H). at reflux for 6 h was then stirred at room temperature for 24 h The mixture was concentrated down filtered through a plug of silica gel The filtrate was concentrated down the residue was recrystallized from hot methanol

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Methyl 4-hydroxy-3,5-diiodobenzoate (D254) was prepared in an analogous manner to Description 25 (D25) from commercially available 4-hydroxy-3,5-diiodobenzoic acid.

反応条件: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of phenylboronic acid (4.95 g, 40.57 mmol), Ba(OH)2.H2O (10.48 g, 55.33 mmol), and Pd(OAc)2 (0.414 g, 1.84 mmol) in DME/H2O (110 mL/20 mL) was added 3,5-diiodo-4-hydroxybenzoic acid methyl ester (7.45 g, 18.44 mmol). The mixture was stirred at 85° C. for 3 h and was then cooled and concentrated. The residue was partitioned between ethyl acetate/2N HCl. The organic phase was dried (MgSO4) and concentrated to give a solid which was triturated with diethyl ether/petroleum ether to give 3.51 g (62.5%) of product as a white solid. 1H NMR (DMSO-d6) δ9.27 (s, 1H), 7.27 (s, 2H), 7.25-7.40 (m, 10H), 3.81 (s, 3H). was then cooled concentrated The residue was partitioned between ethyl acetate/2N HCl The organic phase was dried (MgSO4) concentrated to give a solid which was triturated with diethyl ether/petroleum ether

反応条件: temp:85.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirred solution of phenylboronic acid (4.95 g, 40.57 mmol), Ba(OH)2.H2O (10.48 g, 55.33 mmol), and Pd(OAc)2 (0.414 g, 1.84 mmol) in DME/H2O (110 mL/20 mL) was added 3,5-diiodo-4-hydroxybenzoic acid methyl ester (7.45 g, 18.44 mmol). The mixture was stirred at 85° C. for 3 h and was then cooled and concentrated. The residue was partitioned between ethyl acetate/2N HCl. The organic phase was dried (MgSO4) and concentrated to give a solid which was triturated with diethyl ether/petroleum ether to give 3.51 g (62.5%) of product as a white solid. 1H NMR (DMSO-d6) δ9.27 (s, 1H), 7.27 (s, 2H), 7.25-7.40 (m, 10H), 3.81 (s, 3H). was then cooled concentrated The residue was partitioned between ethyl acetate/2N HCl The organic phase was dried (MgSO4) concentrated to give a solid which was triturated with diethyl ether/petroleum ether

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirring solution of 3,5-diiodo-4-hydroxybenzoic acid (10.00 g, 25.65 mmol) in dry methanol (250 mL) was added TiCl4 (1.41 mL, 12.82 mmol) in one lot. The reaction was stirred at reflux for 6 h and was then stirred at room temperature for 24 h. The mixture was concentrated down and the residue was taken up in diethyl ether and filtered through a plug of silica gel. The filtrate was concentrated down and the residue was recrystallized from hot methanol to give 7.84 g (76%) of the ester as white crystalline needles. 1H NMR (DMSO-d6) δ10.41 (br s, 1H), 8.22 (s, 2H), 3.79 (s, 3H). at reflux for 6 h was then stirred at room temperature for 24 h The mixture was concentrated down filtered through a plug of silica gel The filtrate was concentrated down the residue was recrystallized from hot methanol

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: To a stirring solution of 3,5-diiodo-4-hydroxybenzoic acid (10.00 g, 25.65 mmol) in dry methanol (250 mL) was added TiCl4 (1.41 mL, 12.82 mmol) in one lot. The reaction was stirred at reflux for 6 h and was then stirred at room temperature for 24 h. The mixture was concentrated down and the residue was taken up in diethyl ether and filtered through a plug of silica gel. The filtrate was concentrated down and the residue was recrystallized from hot methanol to give 7.84 g (76%) of the ester as white crystalline needles. 1H NMR (DMSO-d6) δ10.41 (br s, 1H), 8.22 (s, 2H), 3.79 (s, 3H). at reflux for 6 h was then stirred at room temperature for 24 h The mixture was concentrated down filtered through a plug of silica gel The filtrate was concentrated down the residue was recrystallized from hot methanol

反応条件: temp:0.00; pressure:0.00; stir: