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CAS No. : | 2835-98-5 | MDL No. : | MFCD00007693 |
Formula : | C7H9NO | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | HCPJEHJGFKWRFM-UHFFFAOYSA-N |
M.W : | 123.15 | Pubchem ID : | 76082 |
Synonyms : |
|
Chemical Name : | 2-Amino-5-methylphenol |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H315-H319-H335 | Packing Group: | N/A |
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 |
---|---|---|
20% | With hydrogen bromide; sodium nitrite;copper(I) bromide; In water; ethyl acetate; | A. 2-Bromo-5-methylphenol A solution of sodium nitrite (2.8 g, 41 mmol) in 5 ml water was added rapidly with stirring to an ice-cooled mixture of 6-amino-m-cresol (5.0 g, 41 mmol) and 48% hydrobromic acid (17 ml, 100 mmol). The temperature was kept below 10 C. by addition of ice chips. The diazonium salt solution was then added in portions over a period of 30 min to a boiling mixture of copper(I) bromide (6.4 g, 22 mmol) and 48% hydrobromic acid (5 ml). The resulting mixture was refluxed for an additional 30 min, then was cooled and extracted with ether (2*100 ml). The combined organic extracts were washed with water, dried over magnesium sulfate, and evaporated. The residue was chromatographed on silica gel using 98:2 hexanes/ethyl acetate to afford 233A (1.6 g, 20%) as an oil. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | In acetonitrile; at 23 - 70℃; | To a solution of 2-amino-5-methylphenol (777 mg, 6.32 mmol) in acetonitrile (27 mL) at 23 C. was added 1,1'-carbonyldiimidazole (3.07 g, 18.9 mmol) and the reaction mixture was heated to 70 C., and stirred overnight. The reaction mixture was cooled to room temperature and partitioned between ethyl acetate (150 mL) and H2O (100 mL). The organic layer was separated and washed with brine (100 mL), dried (MgSO4) and concentrated to yield the crude product which was purified by silica gel column chromatography (20-50% EtOAc in hexanes) to yield 6-methyl-3H-benzooxazol-2-one (853 mg, 90%). |
In dichloromethane; at 20℃; for 24h;Inert atmosphere; | General procedure: To a solution of the corresponding 2-amino phenol (1 equiv.) in dry dichloromethane was added 1,1’,-dicarbonyldiimidazole (1.1 equiv) and stirred at ambient temperature under a nitrogen atmosphere for 24 h. The reaction mixture was quenched with water and extracted with ethyl acetate (3x). The organic layer was washed with brine, dried over sodium sulfate, filtered and concentrated in vacuo. The benzoxazolone residue was purified by silica gel chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With triethylamine; In tetrahydrofuran; at 0 - 20℃; | A solution of triphosgene (1.93g, 6.5mmol) in anhydrous THF (40mL) was added to a solution of 2-amino-5-methylphenol (10g, 8.1mmol) and Et3N (2.3mL) in anhydrous THF (40mL) at 0C. The resulting solution was stirred at room temperature (RT) for overnight and was diluted with water (10mL). After 30min, the reaction mixture was concentrated in vacuo and the residue was extracted with ethyl acetate (50mL×3). The combined organic layer was washed by saturated sodium chloride solution for three times, dried over anhydrous Na2SO4 and concentrated under reduced pressure to afford 6-methylbenzo[d]oxazol-2(3H)-one as an off-white solid. Yield 83% (1.93g). MS (ESI): 150.1 [M+H]+ |
With N-ethyl-N,N-diisopropylamine; In dichloromethane; at 0℃;Inert atmosphere; | Synthesis of 3-benzyl-6-methyl-3H-benzooxazol-2-one (2)A solution of 2-amino-5-methyl-phenol (1.0 gm, 8.1 mmol) in CH2Cl2 (30 ml) was cooled to 0 0C. Triphosgene (721 mg, 2.43 mmol) was added followed by diisopropylethylamine (7.0 ml, 17.6 mmol) and the reaction mixture was stirred under nitrogen atmosphere for 2 h. The reaction mixture was washed with water and brine. The organic phase was dried over anhydrous MgSO4 and evaporated under vacuum. The crude product 6- methylbenzo[d]oxazol-2(3H)-one was used for the next step without any purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | A mixture of <strong>[155601-65-3]2,6-difluoronicotinaldehyde</strong> (2 g, 13.9 mmol), 2-amino-5-methylphenol (1.7 g, 13.8 mmol) and 2,3-butanedione monoxime (1.065 g, 10.5 mnol) in acetic acid (120 mL) was heated at 120 C for 1.5 hours. After cooling down to room temperature, zinc powder (2 g) was added and the mixture heated one hour at 120 C and left overnight at room temperature. The suspension is then filtered and filtrate is reduced to about 20 mL. Water was added (about 100 mL) and aqueous KOH was added up to pH ~ 8. The mixture was extracted with dichloromethane and the crude obtained purified by column chromatography using CH2Cl2/Et2O as eluent. The ligand was obtained as a beige solid (2.14 g, yield 68 %) 1H NMR (CDCl3, 400 MHz): delta 8.28 (t, J= 8.0 Hz, 1H); 7.25 (d, J= 1.6 Hz, 1H); 7.09 (d, J= 8.4 Hz, 1H); 6.99 (ddd, J= 8.0, 2.0, 0.8 Hz, 1H); 6.79 (dd, J= 8.4, 2.8 Hz, 1H); 2.27 (s, 3H); 2.24 (d, J= 0.8 Hz, 3H); 2.19 (d, J= 0.8 Hz, 3H). | |
68% | <strong>[155601-65-3]2,6-difluoronicotinaldehyde</strong> was obtained as described in M. Schlosser and T. Rausis, Eur. J. Org. Chem. 2004, 1018.A mixture of <strong>[155601-65-3]2,6-difluoronicotinaldehyde</strong> (2 g, 13.9 mmol), 2-amino-5- methylphenol (1.7 g, 13.8 mmol) and 2,3-butanedione monoxime (1.065 g, 10.5 mmol) in acetic acid (120 mL) was heated at 120C for 1.5 hours. After cooling down to room temperature, zinc powder (2 g) was added and the mixture heated one hour at 120C and left overnight at room temperature. The suspension is then filtered and filtrate is reduced to about 20 mL. Water was added (about 100 mL) and aqueous KOH was added up to pH ~ 8. The mixture was extracted with dichloromethane and the crude obtained purified by column chromatography using CH2Cl2/Et20 as eluent. The ligand was obtained as a beige solid (2.14 g, yield 68 %).1H MR (CDC13, 400 MHz) : delta 8.28 (t, J= 8.0 Hz, IH) ; 7.25 (d, J= 1.6 Hz, IH) ; 7.09 (d, J= 8.4 Hz, IH) ; 6.99 (ddd, J= 8.0, 2.0, 0.8 Hz, IH) ; 6.79 (dd, J= 8.4, 2.8 Hz, IH) ; 2.27 (s, 3H) ; 2.24 (d, J= 0.8 Hz, 3H) ; 2.19 (d, J= 0.8 Hz, 3H). |