Structure of 20951-14-8
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CAS No. : | 20951-14-8 |
Formula : | C8H9FO3S |
M.W : | 204.22 |
SMILES Code : | O=S(C1=CC=C(OC)C(F)=C1)(C)=O |
MDL No. : | MFCD21090339 |
Boiling Point : | No data available |
InChI Key : | RJKIPWHQSXCLHA-UHFFFAOYSA-N |
Pubchem ID : | 56971745 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302-H315-H319-H335 |
Precautionary Statements: | P261-P305+P351+P338 |
* 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 |
---|---|---|
With 3-chloro-benzenecarboperoxoic acid; In dichloromethane; at 20℃; for 2.0h; | To a stirred solution of the product from Step B (557 mg, 3.24 mmol) in dichloromethane ( 15 mL) was added m-chloroperbenzoic acid (2.19 g, 12.7 mmol). After stirring at room temperature for 2 h, the reaction was diluted with ethyl acetate. The organic phase was washed sequentially with 1 N aqueous sodium hydroxide solution and brine, and concentrated in vacuo. Purification by flash chromatography (silica gel, 75:25 hexanes/ethyl acetate) afforded the desired compound. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With water; hydrogen bromide; acetic acid; for 24.0h;Heating / reflux; | 3. Preparation of 2-Fruoro-(4-methylsulfonvDphenol 2020463; Carried out over two equal batches. A mixture of 2-fluoro-l-methoxy-4- (methylsulfonyl)benzene 2009330 (2.00 kg, 9.82 mol) in 48% aqueous hydrogen bromide (6 L) and 33% hydrogen bromide in acetic acid (3 L) was heated at reflux for 24 h in a 20 L flange pot equipped with an overhead stirrer, condenser, and scrubber. The reaction <n="13"/>mixture was then allowed to cool to room temperature and was concentrated under reduced pressure to give a dark oil, which solidified upon standing. The resultant off- white solid was taken up in toluene (7 L) and the mixture was heated at reflux to azeotrope off water. Once collection of water had ceased, the mixture was cooled to 6O0C and an oil was decanted from the toluene. This oil was then stirred with toluene (1 L) until a precipitate formed. The resultant solid was collected by filtration, washed with toluene and hexane, dried under reduced pressure, and then allowed to form a slurry with hexane (3.5 L). The solid was once again collected by filtration, washed with hexane (1 L) and dried under reduced pressure to give 2-fiuoro-(4-methylsulfonyl)phenol 2020463 (1.76 kg, 94%) as an off-white solid, mp 91-95C. 1H NMR (300 MHz, J6-DMSO) δ 3.14 (s, 3H), 7.15 (app t, IH), 7.55 (dd, IH), 7.67 (dd, IH), 11.09 (br s, IH). |
86% | With water; hydrogen bromide; acetic acid; for 29.0h;Reflux; | Step 3: 2-Fluoro-4-methanesulfonyl-phenol; A solution of <strong>[20951-14-8]2-fluoro-4-methanesulfonyl-1-methoxy-benzene</strong> (1.00 g, 4.9 mmol) in a mixture of 48% aqueous HBr (3 mL) and 33% HBr in acetic acid (1.5 mL) was heated at reflux for 20 h. The reaction mixture was cooled to room temperature and extracted with ethyl acetate. The organic layer was dried (sodium sulfate), filtered, evaporated and chromatographed, eluting with 30% ethyl acetate/hexanes, to give 2-fluoro-4-methanesulfonyl-phenol (800 mg, 86%) as a white solid. Mass spectrum (APCI) m/z M-H=189. |
With boron tribromide; In dichloromethane; at -78 - 20℃; for 12.0h; | To a stirred solution of the product from Step B (480 mg, 2.35 mmol) in dichloromethane (10 mL) was added boron tribromide (12.0 mL, 1.0 M in dichloromethane, 12.0 mmol) at-78 C. The reaction was then allowed to warm to room temperature slowly. After stirring at room temperature for 12 h, the reaction was concentrated under reduced pressure and the residue was purified by flash chromatography (silica gel, 50:50 hexanes/ethyl acetate) to give the desired compound. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
94% | With potassium hydroxide; In water; for 3.0h;Heating / reflux; | 2. Preparation of 2-Fluoro- 1 -methoxy-4-(methylsulfonyl)benzene 2009330; Carried out over two equal batches. A solution of 85% potassium hydroxide (824 g, 12.51 mol) in methanol (5 L) was added in 500 niL portions over a period of 2 h to a refluxing solution of l,2-difluoro-4-(methylsulfonyl)benzene 2008101 (2.00 kg, 10.4 mol) in methanol (5 L). Upon complete addition, the reaction mixture was heated at reflux for a further 1 h before being allowed to cool to room temperature. The mixture was then concentrated under reduced pressure and water (10 L) was added to the residue. The resultant precipitate was collected by filtration, washed with water (5 L) and dried to give 2-fluoro-l-methoxy-4-(methylsulfonyl)benzene 2009330 (2.0 kg, 94%) as a white solid, mp 98-1010C. 1H NMR (300 MHz, CDCl3) δ 3.05 (s, 3H), 3.96 (s, 3H), 7.09 (app t, IH), 7.63 (dd, IH), 7.70 (dd, IH). |
85% | With potassium hydroxide; for 1.33333h;Reflux; | Step 2: 2-Fluoro-4-methanesulfonyl-1-methoxy-benzene; A solution of potassium hydroxide (85%; 824 mg, 12.5 mmol) in methanol (5 mL) was added to a refluxing solution of 1,2-difluoro-4-methanesulfonyl-benzene (2.00 g, 10.4 mmol) in methanol (10 mL) over 20 min. The resulting mixture was heated at reflux for 1 h and then cooled to room temperature. The solvent was evaporated, water was added, and the resulting precipitate was filtered off, washed with water, and dried in vacuo to give 2-fluoro-4-methanesulfonyl-1-methoxy-benzene (1.8 g, 85%) as a white solid which was used directly in the next step without purification. |
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