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CAS No. : | 192642-85-6 | MDL No. : | MFCD09999983 |
Formula : | C7H6BrNO2 | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | ATKULCGQSLCGEK-UHFFFAOYSA-N |
M.W : | 216.03 | Pubchem ID : | 46238459 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P280-P305+P351+P338 | UN#: | |
Hazard Statements: | H302+H312+H332-H315-H319-H335 | Packing Group: | |
GHS Pictogram: |
* 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.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | [Example 60]tert-Butyl 4-[2-[2-(4-methanesulfonylphenoxyethyl)pyridine-5-yl]piperidine-1-carboxylate (1) 2-(5-Bromopyridin-2-yl)ethanol To a solution of (5-bromopyridin-2-yl)acetic acid (60.0 mg, 0.278 mmol) in dry tetrahydrofuran (1.4 mL) was added dropwise borane- tetrahydrofuran complex (1.06M in tetrahydrofuran, 0.34 mL, 0.361 mmol) under N2. The mixture was stirred at room temperature for 19 hours and water(5 mL)-acetic acid (5 mL) was added slowly. The mixture was concentrated under reduced pressure, the residue was poured into saturated aqueous sodium hydrogen carbonate solution and extracted with ethyl acetate. The organic layer was washed with saturated aqueous sodium hydrogen carbonate solution, dried over anhydrous sodium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane/ethyl acetate=7/1→ethyl acetate) to give the title compound as a yellow oil (45 mg, yield 80%).1H NMR(CDCl3,400 MHz): δ= 2.98(2H, t, J=5 Hz), 3.68(1H, brs), 4.01(2H, t, J=5 Hz), 7.09(1H, d, J=8 Hz), 7.75(1H, dd, J=2 Hz, 8 Hz), 8.57(1H, d, J=2 Hz). | |
79% | With diborane; In tetrahydrofuran; at -78 - 20℃; for 16h;Inert atmosphere; | [00543] To a solution of Example 105a (2.16 g, 10.0 mmol) in dry THF (80 mL) was added slowly added BH3/THF (1.0 M, 30 mL) at -78C under nitrogen atmosphere. After addition, the mixture was allowed to stir from -78C to r.t. for 16 h. The reaction was quenched by saturated aqueous K2C03, extracted by EtOAc (50 mL*2), dried over Na2S04, filtered and concentrated. The residue was purified by silica gel chromatography (Petroleum Ether/EtOAc = 30/70) to give the desired product Example 105b (1.6 g, yield 79%) as colorless oil. LCMS [M+l]+ =202.0/204.0 |
51% | With borane-THF; In tetrahydrofuran; at 20℃; for 4h;Inert atmosphere; | To a stirred solution of 2-(5-bromopyridin-2-yl)acetic acid (2 g, 9.25 mmol) in THF (50 mL) was added BH3.THF (12 mL, 12.03 mmol, 1M in THF) drop wise at room temperature under nitrogen and stirred at same temperature for 24 h. The mixture was cooled to 0 C, quenched with water: acetic acid (10 mL, 1:1) and stirred at room temperature for 30 minutes. The reaction mixture was evaporated and resulting residue was diluted with EtOAc (50 mL). The organic layer was washed with saturated aqueous sodium bicarbonate solution and water, dried, filtered and evaporated. The crude compound was chromatographed on silica eluting with 40% EtOAc in petroleum ether affording a yellow liquid (950 mg, 51%). M/z = 202.0 (M+H)+. |
Preparation of 6:2-(5-Bromopyridin-2-yl)ethanolUnder N2, a solution of 2-(5-bromopyridin-2-yl)acetic acid (5, 29.75 g) in THF (450 mL) was cooled to 0C. Borane THF complex (1 M in THF, 413.2 mL, 413.2 mmol) was added dropwise, keeping the reaction temperature below 5C. The mixture was allowed to warm to room temperature and stir for 4h. The mixture was cooled to 0C and saturated aqueous K2C03 solution (500 mL) and H20 (500 mL) were added slowly. The mixture was extracted with EtOAc (3x 500 mL). The combined organic layers were washed with brine (500 mL), dried over Na2S04 and filtered. The solvent was removed in vacuo and the residue was purified by column chromatography (silica,Heptane/EtOAc 3:7) yielding compound 6 (10.9 g, 53.9 mmol, 40% over 2 steps). 1 H- NMR (CDCI3, 300 MHz): δ 3.00 (t, 2H, CH2), 3.64 (bs, 1 H, OH), 4.03 (t, 2H, CH2), 7.10 (d, 1 H, ArH), 7.76 (dd, 1 H, ArH), 8.59 (d, 1 H, ArH). | ||
1.09 g | With borane-THF; In tetrahydrofuran; at 5 - 20℃; | Commercially available 2-(5-bromopyridin-2-yl)acetic acid (1.00 g, 4.6 mmol) in tetrahydrofuran (10 mL) is cooled to 5 C. and treated dropwise over 10 minutes with borane-tetrahydrofuran complex (13.9 mL, 13.9 mmol). After stirring at room temperature for 4 hours, the reaction mixture is quenched with saturated aqueous potassium carbonate (20 mL), extracted with ethyl acetate (50 mL), dried over MgSO4, filtered, the solvent removed under reduced pressure, and the crude material purified by column chromatography on silica gel eluting with a gradient of neat heptane to neat ethyl acetate to afford the title compound (1.09 g): m/z (CI) 203 [M+H]. |
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