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Structure of 204513-31-5

Chemical Structure| 204513-31-5

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Product Details of [ 204513-31-5 ]

CAS No. :204513-31-5
Formula : C4H4BrNOS
M.W : 194.05
SMILES Code : OCC1=NC(Br)=CS1
MDL No. :MFCD09746337
InChI Key :FLYOCGYCIHPZRF-UHFFFAOYSA-N
Pubchem ID :11041630

Safety of [ 204513-31-5 ]

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H315-H319-H335
Precautionary Statements:P261-P305+P351+P338

Application In Synthesis of [ 204513-31-5 ]

* 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.

  • Downstream synthetic route of [ 204513-31-5 ]

[ 204513-31-5 ] Synthesis Path-Downstream   1~1

  • 1
  • [ 167366-05-4 ]
  • [ 204513-31-5 ]
YieldReaction ConditionsOperation in experiment
99% With methanol; sodium tetrahydroborate; at 20℃; for 0.5h; Sodium borohydride (99 mg, 2.60 mmol) was added to a stirring solution of 5- chlorothiazole-2-carboxaldehyde (500 mg, 2.60 mmol) in MeOH (5.2 mL) at RT. The mixture was stirred for 30 min at RT and then concentrated in vacuo. The residue was taken up in EtOAc (40 mL) and washed sequentially with water (30 mL) and brine (20 mL). The organic layer was then dried over Na2SO4, filtered and concentrated in vacuo to give (4-bromothiazol-2-yl)methanol as a brown oil that was used without further purification (406A, 499 mg, 99%). LC/MS (ESI+) m/z = 194.0 (M+H)+. 1H NMR (400 MHz, chloroform-d) delta 7.23 (s, 1 H), 4.97 (d, J=6.06 Hz, 2H), 2.51 (t, J=5.38 Hz, 1 H).
95.2% With sodium tetrahydroborate; (4-Bromothiazol-2-yl)methanol (2) To a solution of <strong>[167366-05-4]4-bromothiazole-2-carbaldehyde</strong> (10.4 g, 0.0542 mol) in MeOH (150 mL) was added NaBH4 (4.10 g, 0.108 mol) at 0 C. The mixture was stirred at 25 C. for 2 hrs. TLC showed the reaction was completed and one new spot was observed. The mixture was quenched with water (70 mL), stirred for 0.5 hr and concentrated to remove most of MeOH. The aqueous layer was extracted with EtOAc (30 mL*3). The combined organic layers were washed with brine (50 mL), dried over Na2SO4, filtered and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (SiO2, Petroleum ether/Ethyl acetate=10: to 3:1) to give (4-bromothiazol-2-yl)methanol (10.0 g, 0.0515 mol, yield: 95.2%) as white solid. 1H NMR (400 MHz, CDCl3) delta 7.23 (s, 1H), 4.96 (d, J=6.0 Hz, 2H), 2.79 (t, J=6.0 Hz, 1H).
With sodium tetrahydroborate; In methanol; at 20℃; 2,4-Dibromothiazole (4.31 g, 17.7 mmol) are dissolved in anhydrous diethyl ether (170 ml) and the solution is cooled to -78 C. (dry ice-acetone bath). n-Butyllithium (1.6 M in hexanes, 13 ml, 20.8 mmol) is added dropwise to the reaction mixture and the resulting solution is stirred at the same temperature for 30 minutes. Anhydrous DMF (ml, mmol) is then added at -78 C. and, after being stirred at the -78 C. for 30 minutes, the reaction mixture is warmed to room temperature over a period of 2 hours. Hexanes (300 ml), were added and the resulting mixture is passed through a short silica cake eluting with 30% EtOAc-hexanes. The solvents are evaporated to yield the crude aldehyde which is used directly in the next step. To a solution of the above aldehyde in MeOH (80 ml) is added sodium borohydride (g, mmol), and the resulting mixture is stirred room temperature for hours. Hexanes (300 ml) are added and the mixture is passed through a short silica cake eluting with EtOAc. The crude alcohol is further purified by flash chromatography on silica with 20-50% EtOAc-hexanes as an eluant to yield g (mmol, %) of the pure desired product.
With sodium tetrahydroborate; In methanol; at 0 - 25℃;Inert atmosphere; In a flame dried round-bottomed flask equipped with a magnetic stir bar and under inert atmosphere (N2), <strong>[167366-05-4]4-bromo-thiazole-2-carbaldehyde</strong> (1.68 g, 8.75 mmol) was dissolved in MeOH (10 mL). NaBH4 (428 mg, 10.86 mmol) was added portionwise at 0 0C and the reaction mixture stirred at rt for 1 h. Water (10 mL) was added and the mixture extracted with EA (3 x 20 mL). The combined org. extracts were dried over Na2SO4, filtered, and the solvents were removed under reduced pressure. Purification of the residue by FC (6:1 -> 2:1 hept-EA) gave the title compound as a pale yellow solid. TLC: rf (1 :1 hept-EA) = 0.31. LC-MS-conditions 02: tR = 0.62 min [M+H]+ = 194.31.
With sodium tetrahydroborate; In methanol; at 20℃; To an ice-cold solution of <strong>[167366-05-4]4-bromothiazole-2-carbaldehyde</strong> (1.78 g, 9.27 mmol, crude obtained above), in methanol (30 ml) was added NaBH4 (1.76 g, 46.35 mmol) portion wise. The resulting reaction mixture was stirred at room temperature for 2 h. After completion of the reaction (TLC monitoring), the reaction mass was cooled to 0 C., quenched it with 25 ml of water and concentrated under vacuum. Added 50 ml water and extracted with EtOAc (3×100 ml). The combined organics was dried over anhydrous Na2SO4, filtered and concentrated under reduced pressure. The crude residue was purified over silica gel (60-120 M, 10% EtOAc-Hexane) to get the desired product (1.40 g, 78%). MS: 194.01 (M+H)+.
With sodium tetrahydroborate; In methanol; at 0 - 20℃;Inert atmosphere; (4-Bromo-thiazol-2-yl)-methanol:; In a flame dried round-bottomed flask equipped with a magnetic stir bar and under inert atmosphere (N2), <strong>[167366-05-4]4-bromo-thiazole-2-carbaldehyde</strong> (1.68 g, 8.75 mmol) was dissolved in MeOH (10 ml_). NaBH4 (428 mg, 10.86 mmol) was added portionwise at 0 0C and the reaction mixture stirred at rt for 1 h. Water (10 ml.) was added and the mixture extracted with EA (3 x 20 ml_). The combined org. extracts were dried over Na2SO4, filtered, and the solvents were removed under reduced pressure. Purification of the residue by FC (6:1 ->; 2:1 hept-EA) gave the title compound as a pale yellow solid. TLC: rf (1 : 1 hept-EA) = 0.31. LC-MS-conditions 02: tR = 0.62 min [M+H]+ = 194.31.
To a solution (20 mL) of crude <strong>[167366-05-4]4-bromo-1,3-thiazole-2-carbaldehyde</strong> in ethanol was added sodium tetrahydroborate (935 mg, 24.7 mmol), and the mixture was stirred at room temperature for 3 hr. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The obtained organic layer was washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure. The obtained crude product was purified by column chromatography (hexane - hexane/ethyl acetate=75/25) to give the title compound (1.8 g, 44%) as a pale-yellow oil. 1H NMR (300 MHz, CHLOROFORM-d) delta ppm 2.60 (1 H, t, J=6.2 Hz), 4.96 (2 H, d, J=6.2 Hz), 7.22 (1 H, s)
865 mg With methanol; sodium tetrahydroborate; In tetrahydrofuran; at 0 - 35℃; for 1h; A) (4-bromothiazol-2-yl)methanol To a solution of <strong>[167366-05-4]4-bromothiazole-2-carbaldehyde</strong> (1.20 g) in THF (10 mL) were successively added sodium borohydride (236 mg) and methanol (1.0 mL) at 0C, and the mixture was stirred at room temperature for 1 hr. 1N Hydrochloric acid was added, and the reaction mixture was extracted with ethyl acetate. The extract was washed with saturated brine, and dried over anhydrous sodium sulfate. The solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography (NH, ethyl acetate/hexane) to give the title compound (865 mg) as a colorless oil. 1H NMR (300 MHz, DMSO-d6) delta 4.72 (2H, d, J = 6.0 Hz), 6.19 (1H, t, J = 5.9 Hz), 7.75 (1H, s).
3.28 g With sodium tetrahydroborate; In methanol; at 20℃; for 0.333333h; Step 1: (4-Bromo-thiazol-2-yI)-methanol [00308] To a solution of <strong>[167366-05-4]4-bromo-2-formylthiazole</strong> (4.00 g, 20.8 mmol) in methanol (60.0 mL, 1480 mmol) was slowly added sodium tetrahydroborate (0.946 g, 25.0 mmol), and the reaction was stirred at rt for 20 min. The reaction was concentrated in vacuo, diluted with EtOAc, and washed with water 2x and then brine l x. Organic layer was dried over Na2S04, filtered and concentrated in vacuo. The residue was purified via column chromatograpy (40g column, 20% - 50% EtOAc in hexanes over 30min) to give a light yellow oil. Yield = 3.28 g. NMR (400 MHz, Chloroform-d) delta 7.22 (s, 1H), 4.95 (d, J = 6.2 Hz, 2H), 2.76 (t, J = 6.2 Hz, 1H). LCMS (FA): 196.0 m/z (M + 1).

 

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