Structure of 64465-53-8
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CAS No. : | 64465-53-8 |
Formula : | C7H8FNO |
M.W : | 141.14 |
SMILES Code : | C1=C(C(=CC=C1N)F)OC |
MDL No. : | MFCD00665789 |
InChI Key : | XAACOEWSHBIFGJ-UHFFFAOYSA-N |
Pubchem ID : | 2774533 |
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 |
---|---|---|
70% | Aqueous hydrobromic acid (48%, 2.41 mL) was added to 4-fluoro-3-methoxyaniline (1.0 g, 7.1 mmol) in water (10 mL) and the resulting mixture was cooled to 0 C in an ice bath. A solution of sodium nitrite (538 mg, 7.8 mmol) in water (5 mL) was added dropwise during 15 min while maintaining the temperature between 0-5 0C. The resulting diazoniumsalt solution was added to a suspension of copper(I) bromide (1.12 g, 7.8 mmol) in water (5 mL) which had been pre-heated to 75 C. The mixture was shaken thoroughly, aqueous hydrobromic acid (48%, 12.07 mL) was added and the solution was stirred at ambient temperature for 16 h. Excess water was added and the product was extracted with diethyl ether and the combined organic extracts were washed with aqueous saturated sodium chloride, dried over magnesium sulfate, filtered and the solvent was evaporated in vacuo to give 1.02 g (70% yield) of the title compound.: 1H-NMR (DMSO-J6): delta 7.36 (dd, J= 7.78, 2.26 Hz, 1 H), 7.23-7.17 (m, 1 H), 7.14-7.09 (m, 1 H), 3.86 (s, 3 H); MS (EI) (m/z, %) 204,206 (100), 189,191 (23), 161,163 (45) | |
With hydrogen bromide; copper(I) bromide; sodium nitrite; In water; | PREPARATION 13 1-Bromo-4-fluoro-3-methoxybenzene To a stirred suspension of 20.8 g (0.147 mole) of 4-fluoro-3-methoxyaniline (Mulvey et al., Tetrahedron Letters, 16, 1419 [1978]) in 200 ml of water was added 50.2 ml of 48% hydrobromic acid. The resulting mixture was cooled to 0 C., and a solution of 11.2 g (0.162 mole) of sodium nitrite in 100 ml of water was added dropwise during 1 hour, with stirring, maintaining the temperature between 0 and 5 C. The solution of the diazonium salt thus obtained was then added to a suspension of 23.2 g (0.162 mole) of cuprous bromide in 100 ml of water which had been preheated to 75 C. The mixture was shaken thoroughly and then 251 ml of 48% hydrobromic acid was added. The resulting mixture was stirred overnight at room temperature and then it was diluted with an excess of water. The product was extracted into diethyl ether, and the extract was washed with saturated sodium chloride solution and dried (MgSO4). Evaporation of the dried ethereal solution in vacuo afforded a black liquid, which was distilled under reduced pressure. This afforded 23 g of the title compound as a yellow liquid, b.p. 82-85 C. (8 mm of Hg). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With palladium 10% on activated carbon; hydrogen; In methanol; at 20℃; | To a solution of <strong>[454-16-0]1-fluoro-2-methoxy-4-nitrobenzene</strong> (101) (5.0 g, 29.0 mmol) in methanol (25 mL) was added 10 percent Pd/C (500 mg) at room temperature under H2 atmosphere. After reaction completion (monitored by TLC), the mixture was filtered and the filtrate was evaporated under vacuo to afford title compound 202 (4.0 g, 97 percent yield). ?H NIVIR (400 1VIHz, DMSO-d6): 3.72 (s, 3H), 4.93 (s, 2H), 6.02-6.05 (m, 1H), 6.33 (dd, J7.6, 2.4 Hz, 1H),6.81 (dd,J 11.6, 8.8 Hz, 1H). |
93% | N-(4-fluoro-3-methoxyphenyl)pivalamide Step 1 : 4-fluoro-3-methoxyanilineNitro compound Il (6.5 g, 0.038 mol) and iron powder (10.6 g, 0.19 mol) were suspended in ethanol (90 ml) at O0C. HCI cone. (120 ml) was added drop wise to the reaction mixture. The reaction mixture was stirred at 2O0C for 18hr. The reaction mixture was then filtered through celite and washed repeatedly with ethanol. Then ethanol was concentrated and the residue was basified with solid Na2CO3. Then it was extracted with ethyl acetate and washed with water and brine. The organic layer was dried over Na2SO4 and concentrated in vacuum to get the product (5 g, Y= 93percent). HPLC-MS: Purity 97percent, M+1 = 142.1 | |
palladium-carbon; In 1,4-dioxane; | C. 4-Fluoro-3-methoxyaniline A suspension of 10 grams of <strong>[454-16-0]2-fluoro-5-nitroanisole</strong> and 100 ml. of dioxane is reduced catalytically under 40 p.s.i. of hydrogen and 1.0 gram of 5percent Pd/C. After the uptake of hydrogen ceases, the catalyst is filtered, and the filtrate is concentrated in vacuo to yield 4-fluoro-3-methoxyaniline. Alternatively, the compound may be prepared as follows: |
With hydrogenchloride; In methanol; | B. 4-Fluoro-3-methoxyaniline A solution of 5.4 grams <strong>[454-16-0]2-fluoro-5-nitroanisole</strong> in 125 ml. methanol is reduced by hydrogen at room temperature and 40 p.s.i. pressure using 100 mg. platinum oxide catalyst. After the required uptake of hydrogen, the mixture is filtered, 50 ml. 2.5 N hydrochloric acid added and the resulting solution is evaporated in vacuo. After washing the residue with ether, it is dissolved in methanol, filtered and diluted with excess ether. The precipitate is filtered, washed with ether and dried in vacuo at room temperature. The 4-fluoro-3-methoxyaniline hydrochloride darkens at 250° C. and melts 260° - 265° C. Calculated for C7 H8 FNO.HC1: C, 47.33; H, 5.11; N, 7.89; F, 10.70; Cl, 19.96. Found: C, 47.35; H, 5.14; N, 7.66; F, 10.9; Cl, 20.05. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78.9% | With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; N-ethyl-N,N-diisopropylamine; In 1,4-dioxane; at 20 - 50℃; | General procedure: The synthesis was carried out by using the synthetic method a. To a solution of 2-picolinic acid (0.871 g,7.08 mmol), N-hydroxybenzotriazolehydrate (HOBt.H2O,1.084 g, 7.08 mmol), diisopropylethylamine(DIPEA, 1.83 g, 14.17mmol) and N-(3-methylaminopropyl)-N?-ethylcarbodiimidehydrochloride (EDCHCl, 2.036 g, 10.63mmol) in anhydrous 1,4-dioxane (60 mL) was added 3-fluoro-3-methoxyanilline (1.00 g, 7.08 mmol) at room temperature. The mixture was heated to 50 oC and stirred overnight. To the reaction mixture was added 300 mL of dichloromethane, and sequentially washed with water (3 x100 mL). After the organic layer was separated and concentrated, the reaction mixture was purified by silica-gel chromatography (hexane/ethyl acetate) to give the product as a pale-yellow solid (1.559 g, 6.33mmol, 89.4percent yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
46.7% | With sulfuric acid; sodium nitrite; at 0 - 100℃; for 0.5h; | To a suspension of compound 202 (4.0 g, 28.0 mmol) in 30 percent sulfuric acid (15mL) was added sodium nitrite (2.15 g, 31.0 mmol) at 0 °C. The reaction was stirred at 0 °Cfor 20 minutes, and then was added to 60percent sulfuric acid (15 mL) at 100 °C and stirred for 30mm. The reaction mixture was neutralized with anhydrous NaHCO3 and extracted with ethylacetate. The organic layer was washed with water and brine, dried over anhydrous sodiumsulfate and evaporated in vacuo. The crude product was purified by column chromatography(hexanes/dichloromethane: 3/1) to afford the title compound 203 (1.84 g, 46.7 percent yield) as acolorless oil. ?HNIVIR(400 1VIHz, DMSO-d6): 3.76 (s, 3H), 6.24-6.27 (m, 1H), 6.51 (dd, J 6.8, 2.8 Hz, 1H), 6.96 (dd, J 11.2, 8.4 Hz, 1H), 9.36 (s, 1H). |
Tags: 64465-53-8 synthesis path| 64465-53-8 SDS| 64465-53-8 COA| 64465-53-8 purity| 64465-53-8 application| 64465-53-8 NMR| 64465-53-8 COA| 64465-53-8 structure
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