530145-16-5|Methyl 5-(hydroxymethyl)thiophene-2-carboxylate| Ambeed

Yield	Reaction Conditions	Operation in experiment
95%	With 1H-imidazole; bromine; triphenylphosphine; In dichloromethane; at 20℃; for 0.166667h;	Bromine (0.47 mL, 9.12 mmol) was added to a solution of imidazole (617 mg, 9.06 mmol) and triphenylphosphine (2.40 g, 9.15 mmol) in CH2Cl2 (30 mL) at room temperature. A solution of methyl 5-hydroxymethyl-thiophene-2-carboxylate (prepared according to the procedures described in WO2004/037808; 1.30 g, 7.59 mmol) in CH2Cl2 (10 mL) was then added. After 10 min at room temperature, the reaction mixture was concentrated in vacuo. Purification of the crude residue by flash column chromatography on 80 g of silica gel (hexane?EtOAc, gradient) afforded 1.70 g (95%) of the title compound (B).
95%	With 1H-imidazole; bromine; triphenylphosphine; In dichloromethane; at 20℃; for 0.166667h;	Preparation 1; Methyl 5-bromomethyl-thiophene-2-carboxylate (B); Bromine (0.47 mL, 9.12 mmol) was added to a solution of imidazole (617 mg, 9.06 mmol) and triphenylphosphine (2.40 g, 9.15 mmol) in CH2Cl2 (30 mL) at room temperature. A solution of methyl 5-hydroxymethyl-thiophene-2-carboxylate (prepared according to the procedures described in WO2004/037808; 1.30 g, 7.59 mmol) in CH2Cl2 (10 mL) was then added. After 10 min at room temperature, the reaction mixture was concentrated in vacuo. Purification of the crude residue by flash column chromatography on 80 g of silica gel (hexane ?EtOAc, gradient) afforded 1.70 g (95%) of the title compound (B).
84%	With 1H-imidazole; bromine; triphenylphosphine; In dichloromethane; at 20℃; for 4h;	To a flask charged with dry dichloromethane (50 mL) was added in order triphenyl phosphine (228 mg, 0.87 mmol), imidazole (59.3 mg, 0.87 mmol) and bromine (44.6muL, 0.87 mmol). The reaction mixture was then treated with a solution of 1 (100 mg, 0.58 mmol, in <n="38"/>dichloromethane (5 niL)), dropwise and stirred at room temperature under nitrogen for 4 h. When the reaction was deemed complete the mixture was concentrated to dryness under reduced pressure and subjected to flash chromatography (20%ethyl acetate/petrol) to afford the desired 5-bromomethyl-thiophene-2-carboxylic acid methyl ester (m) as colourless crystals, (115 mg, 84%).1H NMR (300 MHz, CDCl3) delta 3.89 (3H, s, CH3), 4.67 (2H, s, CH2), 7.10 (IH, m, thienylH), 7.64 (IH, d, /=3.6Hz, thienylH).HPLCmethod2 92%/1.14 min.

Yield	Reaction Conditions	Operation in experiment
92%	With methanol; sodium tetrahydroborate; at 0℃;	Methyl 5-formylthiophene-2-carboxylate (1.0 g, 5.87 mmol, 1.0 eq.) was dissolved in 50 mL MeOH cooled to 0 °C in an ice bath. To this solution was added NaBH4 (0.445 g, 11.75 mmol, 2.0 eq.) slowly in portions and the reaction was monitored by TLC (Si02, 9:1 n- hexanes:EtOAc). Upon full conversion of the aldehyde, the reaction was quenched by slow addition of ice cooled water (10 mL). The mixture was then transferred into a separation funnel, diluted with 50 mL H20 end extracted with diethyl ether (3 times 100 mL). The combined organics were washed with brine (50 mL), dried over Na2S04, filtered and concentrated under reduced pressure. The product was obtained pure (0.935 g, 5.4 mmol, 92percent) and used for the next step without further purification. NMR (300 MHz, CDC13) delta 7.67 (d, J= 3.8 Hz, 1H), 6.98 (dt, J= 3.8, 0.8 Hz, 1H), 4.85 (d, J= 0.7 Hz, 2H), 3.87 (s, 3H), 1.95 (s (br), 1H).
		Preparation 24 A solution of <strong>[67808-64-4]methyl 5-formylthiophene-2-carboxylate</strong> (486 mg) in MeOH (20 mL) was cooled to 0°C, and was added sodium borohydride (108 mg) slowly. The reaction mixture was stirred at 0°C for 30 minutes. To the reaction mixture was added saturated NH4Cl aqueous solution (20 mL) and stirred. The mixture was concentrated to approximately 25 mL under reduced pressure and extracted with EtOAc. The organic layer was washed with water and brine, dried over anhydrous MgSO4 and filtered. The filtrate was evaporated in vacuo to afford methyl 5-(hydroxymethyl)thiophene-2-carboxylate (472 mg) as a colorless oil.
303 mg	With sodium tetrahydroborate; ammonium chloride; In methanol; water; for 2.16667h;Cooling with ice;	Methyl 5-formylthiophene-2-carboxylate (311 mg,1.82 mmol) was dissolved in MeOH (4 mE), cooled in an ice bath and NaI3H4 (68 mg, 1.82 mmol) added portion wise over ten minutes. The reaction was stirred for 2 h after which time sat. aq. ammonium chloride (10 mE) was added. The aqueous phase was extracted with DCM (2x1 5 mE), passed through a phase separator and concentrated in vacuo to yield the sub-title compound (303 mg) as a colourless oil.1H NMR (400 MHz, CDC13) oe 7.61 (d. 1H), 6.92 (dt, 1H), 4.86-4.69 (m, 2H), 3.81 (s, 3H).

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Methyl 5-(hydroxymethyl)thiophene-2-carboxylate

CAS No.: 530145-16-5

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Product Details of [ 530145-16-5 ]

Safety of [ 530145-16-5 ]

Application In Synthesis of [ 530145-16-5 ]

[ 530145-16-5 ] Synthesis Path-Downstream 1~3

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H226	Flammable liquid and vapour
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H230	May react explosively even in the absence of air
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