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CAS No. : | 2835-95-2 | MDL No. : | MFCD00043922 |
Formula : | C7H9NO | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | DBFYESDCPWWCHN-UHFFFAOYSA-N |
M.W : | 123.15 | Pubchem ID : | 17818 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P264-P280-P302+P352-P312-P337+P313-P305+P351+P338-P362+P364-P332+P313 | UN#: | |
Hazard Statements: | H315-H319-H303 | 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 |
---|---|---|
26% | To a solution of 5-AMINO-2-METHYLPHENOL (10 G, 81.2 MMOL) in hydrobromic acid (40 mL, 48 % solution) and water (50 mL) at 0 C was added a solution of sodium nitrite (5.6 g, 81.2 MMOL) in water (15 mL) and the mixture stirred at this temperature for 30 minutes. To this was added copper (I) bromide (11.6 G, 81. 2 MMOL) in hydrobromic acid (15 mL, 48% solution) and the reaction was subsequently heated at reflux for 2 hours. Upon cooling to room temperature the resulting mixture was extracted with ethyl acetate (2 x 200 mL) and the combined organic extracts were washed with aqueous potassium hydroxide solution (-1 M, 200 mL), dried (magnesium sulphate) and concentrated under reduced pressure. The crude product was purified by column chromatography [SI02 ; light petroleum to 4: 1 light petroleum-ethyl acetate] to give the title compound as a COLOURLESS OIL, WHICH CRYSTALLISED to give fine colourless needles upon standing overnight (4 G, 26 %). Rf = 0.26 [4: 1 light petroleum-ethyl acetate]. 1H NMR 5 2.21 (3 H, s), 4.89-4. 95 (1 H, br, s), 6.96-6. 97 (1 H, br, m), 6.99-7. 00 (2 H, m). | |
24% | To a solution of 5-amino-2-methylphenol (50 g, 0.41 mol) in hydrobromic acid (200 mL, 48 % solution) and water (200 ml) in a brine ice bath was added sodium nitrite (30.5 g, 0.45 mol, 1.1 equiv.) portion-wise at such a rate that the temperature remained below +10 C, and the mixture was stirred for a EPO <DP n="68"/>further 15 minutes. To this solution was added copper(l) bromide (64 g, 0.44 mol, 1.1 equiv.) and the reaction was subsequently heated to 80 0C. Effervescence was observed at 60-65 C indicating that the reaction had occurred. The mixture was heated at 80 C for a further 30 minutes and then allowed to cool to room temperature. The resulting black tarry mixture was extracted with petroleum ether 40-60 0C (4 x 400 ml) and the combined organic extracts were dried (MgSO4) and concentrated under reduced pressure. [Note that a large tarry component does not dissolve in either petrol or the aqueous layer and sometimes the petrol layer was simply decanted from this once all the aqueous layer had been run out from the separating funnel]. The resulting orange-white solid was recrystallised from petrol to give the product as a white solid (13 g 17 %). The mother liquors were further purified by dry flash column chromatography (particle size 3-35 A), eluting with 0-20% diethyl ether in petroleum ether 40-60 0C to give a yellow-white crystalline solid which was re-crystallised from petroleum ether 40-60 C to give a further 5 g and an overall yield of 18 g (24 %); Rf = 0.26 (4:1 petrol- ethyl acetate), m.p. 77-78 C (from petrol). 1H NMR deltaH 2.21 (3 H, s), 4.89- 4.95 (1 H, br, s), 6.96-6.97 (1 H, br, m) and 6.99-7.00 (2 H, m). | |
20% | Example 60; Synthesis of 4-(4-methyl-3-(5-(trifluoromethyl)pyridin-2-yloxy)benzylidene)-N-(pyridin-3-yl)piperidine-1-carboxamide; Step 1; 5-Bromo-2-methylphenol; 5-Amino-2-methylphenol (5 g, 0.04 mol) was dissolved in HBr (20 mL) and H2O (20 mL) was added dropwise maintaining a temperature below 0 C. The resulting mixture was stirred for 5 min and a solution of NaNO2 (2.76 g, 0.04 mol) in H2O (7.5 mL) was added dropwise. The mixture was stirred for 30 min below 0 C. Then a solution of cuprous bromide (5.73 g, 0.04 mol) in HBr (7.5 mL) cooled to 0 C. was added dropwise. The resulting mixture was warmed to RT and then refluxed for 2 h. The reaction was cooled and filtered through celite. The filtrate was diluted with water and extracted with EtOAc. The organic extract was dried over Na2SO4, and concentrated under reduced pressure. The residue was purified by column chromatography (2.5% EtOAc-97.5% Hexane) to give the pure title compound (1.57 g, 20%). 1H NMR (500 MHz, CDCl3): delta 6.97 (s, 3H), 4.89 (s, 1H), 2.19 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With pyridine hydrochloride; In 2-ethoxy-ethanol; | EXAMPLE 276 4-(3-Hydroxy-4-methyl-phenylamino)-8-methoxy-quinoline-3-carbonitrile Using an analogous procedure to that described in Example 274. A reaction mixture of 328.0 mg (1.5 mmol) of 4-chloro-8-methoxy -3-quinolinecarbonitrile, 173.3 mg (1.5 mmol) of pyridine hydrochloride and 203.2 mg (1.7 mmol) of 3-hydroxy-4-methyl-aniline in 15 mL of 2-ethoxyethanol was heated at 100 C. for 1.5 hr. After the work up, 407.7 mg (89.4%) of the product was obtained as a yellow solid, m.p. 148-150 C., mass spectrum (electrospray, m/e): M+H 306.9. | |
With pyridine hydrochloride; In 2-ethoxy-ethanol; | EXAMPLE 276 4-(3-Hydroxy-4-methyl-phenylamino)-8-methoxy-quinoline-3-carbonitrile Using an analogous procedure to that described in Example 274. A reaction mixture of 328.0 mg (1.5 mmol) of 4-chloro-8-methoxy -3-quinolinecarbonitrile, 173.3 mg (1.5 mmol) of pyridine hydrochloride and 203.2 mg (1.7 mmol) of 3-hydroxy-4-methylaniline in 15 mL of 2-ethoxyethanol was heated at 100 C. for 1.5 hr. After the work up, 407.7 mg (89.4%) of the product was obtained as a yellow solid, m.p. 148-150 C., mass spectrum (electrospray, m/e): M+H 306.9. | |
With pyridine hydrochloride; In 2-ethoxy-ethanol; | Example 276 4-(3-Hydroxy-4-methyl-phenylamino)-8-methoxy-quinoline-3-carbonitrile Using an analogous procedure to that described in Example 274. A reaction mixture of 328.0 mg (1.5 mmol) of 4-chloro-8-methoxy -3-quinolinecarbonitrile, 173.3 mg (1.5 mmol) of pyridine hydrochloride and 203.2 mg (1.7 mmol) of 3-hydroxy-4-methylaniline in 15 mL of 2-ethoxyethanol was heated at 100 C for 1.5 hr. After the work up, 407.7 mg (89.4%) of the product was obtained as a yellow solid, m.p. 148-150C, mass spectrum (electrospray, m/e): M+H 306.9. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
18% | With triethylamine; In tetrahydrofuran; at 0 - 20℃; for 15h; | Reference Example 32; tert-butyl (3-hydroxy-4-methylphenyl) carbamate; To a solution of 5-amino-2-methylphenol (10.0 g, 81.2 mmol) and triethylamine (16.9 rtiL, 122 mmol) in tetrahydrofuran (75 mL) was added dropwise with stirring under ice-cooling a solution of di-tert-butyl-dicarbonate (19.5 g, 89.3 mmol) in tetrahydrofuran(25 mL) , and the mixture was stirred at room temperature for 15 hr. The reaction mixture was diluted with water and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous magnesium sulfate and filtrated. The filtrate was concentrated under reduced pressure, and the residue was purified by column chromatography (silica gel, hexane/ethyl acetate =95/5->50/50) to give the title compound (3.25 g, 18%) as a colorless oil.1H-NMR (DMSOd6, 300 MHz) delta 1.46 (9H, s) , 2.02 (3H, s) , 6.71 (IH, dd, J = 8.2, 1.8 Hz), 6.87 (IH, d, J = 8.2 Hz), 7.07 (IH, d, J = 1.8 Hz), 9.09 (IH, s) , 9.16 (IH, s) . |