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CAS No. : | 80866-75-7 | MDL No. : | MFCD00007171 |
Formula : | C8H9NO3 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | KOVQGYQQVNCUBR-UHFFFAOYSA-N |
M.W : | 167.16 | Pubchem ID : | 591360 |
Synonyms : |
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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 |
---|---|---|
89.9% | With borane-THF; In tetrahydrofuran; at 0 - 20℃; for 3h;Inert atmosphere; | To a solution of 3-methyl-4-nitro-benzoic acid (2 g, 11.04 mmol, 1 eq) in anhydrous THF (20 mL) was added BH3-THF (1 M, 27.60 mL, 2.5 eq) at 0-5 C. under N2 atmosphere. The mixture was stirred at 20 C. for 3 h. The reaction mixture was quenched by addition of MeOH (30 mL) at 20 C. then stirred at 20 C. for 0.5 h. The mixture was concentrated to afford the crude product (3-methyl-4-nitro-phenyl)methanol (1.66 g, 9.93 mmol, 89.9% yield, 100% purity) as an off-white solid which was used in the next step without further purification. 1H NMR (400 MHz, CD3OD) δ ppm 7.97 (d, J=8.3 Hz, 1H), 7.46-7.35 (m, 2H), 4.90 (s, 2H), 2.59 (s, 3H); ES-LCMS m/z 168.2 [M+H]+. |
67 g | With Trimethyl borate; dimethylsulfide borane complex; In tetrahydrofuran; methanol; dichloromethane; at 65℃; for 6h;Inert atmosphere; | A flask purged with nitrogen was charged with 3-methyl-4-nitro-benzoic acid (72.5 g, 0.400 mol), trimethyl borate (166.2 g, 1.600 mol) and dry tetrahydrofuran (1449 mL). A solution of borane dimethyl sulfide complex (63.8 g, 79.8 mL, 0.840 mol) was added drop-wise to the stirred batch at 20-35 C. over at least 30 min. An exotherm and effervescence were observed during the addition. The mixture was stirred at 65 C. for at least 6 h or until in-process HPLC analysis showed that conversion was greater than 97%. Reaction was quenched at 20-40 C. with cooling by drop-wise addition of methanol (46 mL) followed by aq 5 N hydrochloric acid (144 mL) over at least 30 min. Exotherm and effervescence were observed during the quench. After stirring the batch at 50 C. for at least 1 h, it was concentrated under reduced pressure to a volume of 360 mL. The concentrated batch was washed with water (453 mL) and the solids were collected on a filter. The wet filter cake was dissolved in CH2Cl2 (2170 mL) at and the resulting solution dried over anhydrous magnesium sulfate (36 g). The dried filtrate solution containing the title compound (67 g, 100% yield) was used directly in the preparation of 3-methyl-4-nitro-benzaldehyde. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | palladium-carbon; In ethanol; | Example 79 Preparation of 4-(hydroxymethyl)-2-methylaniline (105) (Literature reference for making this compound see: Sun, J.-H.; Teleha, C. A.; Yan, J.-S.; Rodgers, J. D.; Nugiel, D. A. J. Org. Chem. 1997, 62, 5627-5629). A solution of <strong>[80866-75-7]3-methyl-4-nitrobenzyl alcohol</strong> (compound 104, 8.5 g, 50.9 mmol) in ethanol (100 mL) was stirred at room temperature, while 10% Pd/C (1.0 g) was added in one portion. The resulting suspension was hydrogenated (10 psi) in a Parr apparatus at room temperature for 1.5 hours. The catalyst was removed by filtration, and solvent was evaporated under vacuum to give the title compound (105, 6.9 g, 99%). MS (electrospray) 138 (M+1); 1H N MR (CDCl3) δ 2.16 (s, 3H), 2.72 (br s, 3H), 4.52 (s, 2H), 6.64 (d, 1H, J=8.0 Hz), 7.02 (d, 1H, J=8.0 Hz), 7.05 (s, 1H). Use of high pressure (30 Psi) of hydrogen and a long reaction time (8 hours) resulted a hydrogenolysis product. The same starting material (104) (21.05 g, 126 mmol) yielded 2,4-dimethylaniline (15.20 g, 100%) under such conditions. MS (electrospray) 122 (M+1); 1H N MR (CDCl3) δ 2.14 (s, 3H), 2.23 (s, 3H), 3.72 (br s, 1H), 6.58 (d, 1H, J=8.0 Hz), 6.84 (d, 1H, J=8.0 Hz), 6.87 (s, 1H). |
99% | palladium-carbon; In ethanol; | Example 68 Preparation of 4-(hydroxymethyl)-2-methylaniline (90) (Literature reference for making this compound see: Sun, J.-H.; Teleha, C. A.; Yan, J.-S.; Rodgers, J. D.; Nugiel, D. A. J. Org. Chem. 1997, 62, 5627-5629). A solution of <strong>[80866-75-7]3-methyl-4-nitrobenzyl alcohol</strong> (compound 89, 8.5 g, 50.9 mmol) in ethanol (100 mL) was stirred at room temperature, while 10% Pd/C (1.0 g) was added in one portion. The resulting suspension was hydrogenated (10 psi) in a Parr apparatus at room temperature for 1.5 hours. The catalyst was removed by filtration, and solvent was evaporated under vacuum to give the title compound (90, 6.9 g, 99%). MS (electrospray) 138 (M+1); 1H N MR (CDCl3) δ2.16 (s, 3H), 2.72 (br s, 3H), 4.52 (s, 2H), 6.64 (d, 1H, J=8.0 Hz), 7.02 (d, 1H, J=8.0 Hz), 7.05 (s, 1H). Use of high pressure (30 Psi) of hydrogen and a long reaction time (8 hours) resulted a hydrogenolysis product. The same starting material (89) (21.05 g, 126 mmol) yielded 2,4-dimethylaniline (15.20 g, 100%) under such conditions. MS (electrospray) 122 (M+1); 1H N MR (CDCl3) δ2.14 (s, 3H), 2.23 (s, 3H), 3.72 (br s, 1H), 6.58 (d, 1H, J=8.0 Hz), 6.84 (d, 1H, J=8.0 Hz), 6.87 (s, 1H). |
97% | With hydrogen;palladium 10% on activated carbon; In ethanol; at 20℃; | Example 4F1-(Tetrahydro-pyran-2-yl-1 H-indazo-5-yl}-methylamine: synthesized as described in the reference. JOC, 62, 5627(1997).268 269 270Part A:A mixture of 3-methyl -4-nitro benzyl alcohol 264 (2.10 g, 12.6 mmol) and 10% Palladium on carbon (0.2 g) in 25 mL of EtOH was hydrogenated at room temperature. After completion of the reaction, the catalyst was removed by filtration. <n="143"/>The solvent was evaporated and residue dried in a vacuum to give title compound as yellow solid 1.7 g, 97% ), 1H NMR (CDCI3), δ 7.06(s,1 H),7.03(d, J=8.0 Hz, 1 H), 6.66 (d, J=7.7 Hz, 1 H), 4.53 (s, 1 H), 3.62(br, 2H), 2.17 (s, 3H); mass calculated for compound 265 is 137.17, observed LCMS m/z 138.2 (M+H). |
91.4% | With hydrogen;palladium 10% on activated carbon; In methanol; at 25℃; | A solution of <strong>[80866-75-7]3-methyl-4-nitrobenzyl alcohol</strong> (Aldrich; 2.000 g; 12.0 mmol) in MeOH (90 ml) is passed through the H-Cube flow hydrogenator fitted with a 10 mol% Pd/C catalyst cartridge (30 x 4 mm) heated to 25 0C with the full hydrogen option enabled. The flow rate is set at 1 mL/min. Solvent was removed to give the title compound (1.50 g, 91.4 %) without further purification. MS (ESI+): 138.1. HPLC (Condition A): Rt 1.41 min (HPLC purity 53.8 %). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With pyridinium chlorochromate; In dichloromethane; at 20℃; for 3h; | Step 1: 3-methyl-4-nitrobenzaldehyde: To a solution of (3-methyl-4- nitrophenyl)methanol (1.0 equiv.) in dichoromethane, pyridinium chlorochromate (1.1 equiv.) was added and the reaction mixture was stirred at room temperature for 3 hours. The reaction mixture was filtered through celite and the filtrate was evaporated. The residue was adsorbed on silica (100-200 mesh) and purified by flash chromatography on silica gel, eluting with 5% ethyl acetate in petroleum ether (60-80), to provide the title compound in the form of creamish crystals (93%); 1H NMR (300 MHz, CDCl3) δ: 2.66 (s, 3H), 7.84-7.87 (m, 2H), 8.04-8.07 (d, J = 8.7 Hz, IH), 10.12 (s, IH); IR (KBr) 3104, 3079, 2981, 2857, 2743, 1702, 1607, 1518, 1383, 1361, 1308, 1226, 1153, 1008, 832, 735 cm"1. |
With manganese(IV) oxide; In dichloromethane; at 20℃; for 48h; | Intermediates 25 & 26 To a stirred solution of Intermediate 23 or 24 (60 mmol) in methylene chloride (200 mL) was added manganese oxide (52 g, 600 mmol). The reaction mixture was stirred at room temperature for 2 days and filtered through diatomaceous. The filter cake was washed with methylene chloride (500 mL) and the filtrate was concentrated under reduced pressure to afford the crude aldehyde. To a solution of the aldehyde (8.7 g, 54 mmol) at -78 0C in tetrahydrofuran (180 mL) was added MeLi (2 M in THF, 80 mmol, 40 mL) dropwise via addition funnel. The resulting solution was stirred under nitrogen, at -78 0C, for 4 hours. The reaction mixture was quenched slowly with saturated ammonium chloride solution at -78 0C and warmed to 0 C. The mixture was partitioned between ethyl acetate (500 mL) and water (300 mL). The organic layer was separated, dried over sodium sulfate and concentrated under reduced pressure. The crude oil was purified by chromatography (silica gel, 2:1 hexanes/ethyl acetate) to afford the alcohol intermediate. To a stirred solution of EPO <DP n="65"/>the alcohol (4.0 g, 22 mmol) in methylene chloride (75 ml_) was added manganese oxide (26 g, 300 mmol). The reaction mixture was stirred at room temperature for 2 days and then filtered through diatomaceous. The filter cake was washed with methylene chloride (500 ml_) and the filtrate was concentrated under reduced pressure and the resulting solid was purified by chromatography (silica gel, 4:1 hexanes/ethyl acetate).Intermediate 25 (4.3 g, 35% for 3 steps): 1H NMR (500 MHz, CDCI3) .58.01-7.99 (m, 1 H), 7.91 (s, 1 H), 7.89-7.82 (m, 1H), 2.65-2.64 (m, 6H); HPLC >99%, tR = 8.05 min;Intermediate 26 (1.6 g, 24% for 3 steps): 1H NMR (500 MHz, CDCI3) 67.90-7.88 (m, 1 H), 7.68 (s, 1 H), 7.53-7.55 (m, 1 H), 4.01 (s, 3H), 2.65 (s, 3H). | |
58 g | With manganese(IV) oxide; In dichloromethane; at 40℃; for 2h; | A flask was charged with <strong>[80866-75-7](3-methyl-4-nitro-phenyl)-methanol</strong> (66.9 g, 0.400 mol), manganese(IV) oxide (85%, 5 μm powder, 409.1 g, 4.00 mol), and CH2Cl2 (1337 mL). The mixture was stirred at 40 C. for at least 2 h or until HPLC analysis showed that the reaction had proceeded to greater the 97% completion. The cooled batch was diluted with CH2Cl2 (1 L) and filtered through a Celite pad (34 g), and the filter cake was rinsed with more CH2Cl2 (1 L). The filtrate and washes were concentrated under in vacuo to dryness to give the title compound as a yellow solid (58 g, 87% yield). |
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