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[ CAS No. 2486-70-6 ]

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CAS No. :2486-70-6 MDL No. :MFCD00007736
Formula : C8H9NO2 Boiling Point : 339.5°C at 760 mmHg
Linear Structure Formula :- InChI Key :N/A
M.W :151.16 g/mol Pubchem ID :75598
Synonyms :

Safety of [ 2486-70-6 ]

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:

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  • Upstream synthesis route of [ 2486-70-6 ]
  • Downstream synthetic route of [ 2486-70-6 ]

[ 2486-70-6 ] Synthesis Path-Upstream   1~20

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Reference: [1] Patent: US2012/277224, 2012, A1,
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Reference: [1] Justus Liebigs Annalen der Chemie, 1867, vol. 144, p. 182
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YieldReaction ConditionsOperation in experiment
90%
Stage #1: With hydrogen bromide In water at 25℃; for 1 h;
Stage #2: With sodium nitrate In water at -2 - -1℃; for 1.75 h;
Stage #3: With hydrogen bromide; copper(I) bromide In water at -2 - 70℃; for 2 h;
Example 1 b:4-Bromo-3-methyl-benzoic acidA suspension of compound of Example 1a (73 g, 0.483 mol) in water (411 mL) and 47percent HBr (486 mL) was stirred at 250C for 1 h and then the reaction mixture was cooled to -20C. A solution of sodium nitrate (32 g, 0.463 mol) in water (10OmL) was added to the reaction mixture over a period of 15 min, maintaining the temperature at -1 0C to -2°C. The reaction mixture was stirred at -1 0C to -20C for 1.5h. The reaction mixture was added slowly to a suspension of copper(l)bromide (73 g, 0.508 mol) in water (73 mL) and aqueous HBr (73 mL). The reaction mixture was stirred at 250C for 1 h and then digested at 70 °C for 1 h. The solid was filtered, washed with water till the pH of the filtrate was 7 and dried to obtain the title compound. Yield: 94 g (90percent); 1H NMR (DMSOd6, 300 MHz): δ 2.37 (s, 3H1 CH3), 7.64 (m, 2H1 Ar)1 7.87 (s, 1 H, Ar); MS: m/e (ES-) 214 (M-1).
Reference: [1] Patent: WO2006/51477, 2006, A2, . Location in patent: Page/Page column 54
[2] American Chemical Journal, 1881, vol. 3, p. 431
[3] Patent: US5409928, 1995, A,
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YieldReaction ConditionsOperation in experiment
96% With palladium on activated charcoal; hydrogen In methanol at 20℃; for 24 h; To a solution of 3-methyl-4-nitrobenzoic acid (100 g, 552.04 mmol) in methanol (2000 mL) was added Palladium carbon (5.0 g) at room temperature under an atmosphere of hydrogen. After stirring for 24 h at room temperature, the solids were filtered out. The filtrate was concentrated under vacuum to afford 4-amino-3- methylbenzoic acid as a light yellow solid (80 g, 96percent).
90.1% With hydrogenchloride; tetrabutylammomium bromide; iron; ammonium chloride In water at 110℃; for 2 h; In a reaction flask equipped with a reflux condenser, a thermometer and a stirrer, 3-methyl-4-nitrobenzoic acid is added36.0 g (0.2 mol) of tetrabutylammonium bromide 0.9 g (0.0028 mol) and 300 ml of water are stirred well, then 16.8 g (0.3 mol) of reduced iron powder, 3.0 g (0.056 mol) of ammonium chloride, and concentrated hydrochloric acid are added. 2 ml, heated to 110°C with stirring, refluxThe reaction was carried out for 2 hours until the reaction of 3-methyl-4-nitrobenzoic acid was complete;Cool down to 35 °C, add sodium carbonate and activated carbon to decolorize for 0.5 hours, add sodium carbonate and activated carbonThe mass of 3-methyl-4-nitrobenzoic acid is 1.5percent and the pH is alkaline. Filtrate iron mud, wash twice with 5percent sodium carbonate solution, mixCombined filter mother liquor and cleaning solution, light yellow solution;Add the above pale yellow solution to sulfuric acid, adjust the pH to slightly acidic, precipitate a white precipitate, filter and wash the filter cake.Two times, the filter cake was vacuum dried in a vacuum oven at 70°C to obtain 27.3 g of 3-methyl-4-aminobenzoic acid.The product obtained in Example 2 was analyzed by liquid chromatography. The purity of the product was 99.5percent. The melting point analyzer was used to analyze the product.The melting range was 169-172°C, and the molar yield of the product was calculated to be 90.1percent based on the raw material 3-methyl-4-nitrobenzoic acid.
90.3%
Stage #1: With sodium hydroxide In water for 0.5 h; Autoclave; Inert atmosphere
Stage #2: With ammonia; hydrogen In water at 140℃; for 5 h; Autoclave
In a 1000 ml beaker, 36.2 g (0.2 mol) of 3-methyl-4-nitrobenzoic acid and 300 ml of water were added, and the pH was adjusted with 25percent sodium hydroxide under stirring until the reaction liquid was basic;Then, the above solution was poured into a 1L autoclave, and 3.0 g of Raney nickel catalyst was added. The autoclave was capped with a locking bolt, stirring was started, nitrogen was injected into the autoclave to a pressure of 2.0 MPa, and the nitrogen inlet valve was closed. After 30 minutes, the inside pressure of the autoclave does not decrease, which proves that the autoclave is sealed intact, and each is replaced with nitrogen and hydrogen three times respectively, and the ammonia gas is charged for 2 minutes, and then pressurized with hydrogen to 3.50 MPa, at a pressure of 3.50-2.50 MPa, and a temperature of 140°C. The reaction was performed for about 5 hours until the hydrogen pressure did not decrease any more as the end point of the reaction and the reaction solution was obtained.After the reaction was completed, the temperature was lowered to room temperature, and the catalyst was filtered off. The filtrate was decolored by adding sodium carbonate and activated carbon for 0.5 hour. The amounts of sodium carbonate and activated carbon were respectively 1.5percent of the mass of 3-methyl-4-nitrobenzoic acid, and the activated carbon was filtered out. Sulfuric acid was added to the solution, the pH was adjusted to slightly acidic, a white precipitate was precipitated, and the filter cake was washed with water twice. The filter cake was vacuum dried at 70°C in a vacuum oven to obtain 27.4 g of 3-methyl-4-aminobenzoic acid.FIG. 1 is a nuclear magnetic hydrogen spectrum of 3-methyl-4-aminobenzoic acid prepared in Example 1 of the present invention.As can be seen from FIG. 1 , 3-methyl-4-aminobenzoic acid was successfully prepared by the present invention.The product obtained in Example 1 was subjected to liquid chromatography and sample analysis. The purity of the product was 99.5percent. The melting point was analyzed and the melting range of the product was 169-172°C. The molar content was calculated based on the raw material 3-methyl-4-nitrobenzoic acid. The yield was 90.3percent.
84% With hydrogen In N,N-dimethyl-formamide at 25℃; for 6 h; Example 1a: 4-Amino-3-methyl-benzoic acid EPO <DP n="56"/>To a solution of 3-methyl-4-nitro-benzoic acid (100 g, 0.55 mol) in DMF (500 ml_), suspension of activated Raney Ni (50 g) in DMF (50 mL) was added and was subjected to hydrogenation (200 psi pressure and 250C) for 6 h. The reaction mixture was filtered through celite bed and was concentrated to one third of the total volume. The reaction mixture was poured into water (1300 mL) with stirring. The solid was filtered, washed with water and dried to obtain the title compound. Yield: 70 g (84percent); 1H NMR (DMSOd6, 300 MHz): δ 2.03 (s, 3H, CH3), 5.60 (s, 2H, NH2), 6.56 (d, 1 H, Ar), 7.46 (d, 1 H, Ar), 7.49 (s, 1 H, Ar); MS: m/e (ES-) 150 (M-1).

Reference: [1] Advanced Synthesis and Catalysis, 2010, vol. 352, # 9, p. 1451 - 1454
[2] Patent: WO2014/66795, 2014, A1, . Location in patent: Paragraph 0175
[3] Journal of Organic Chemistry, 2008, vol. 73, # 21, p. 8631 - 8634
[4] Patent: CN106831460, 2017, A, . Location in patent: Paragraph 0029-0059
[5] Patent: CN107501106, 2017, A, . Location in patent: Paragraph 0025-0047
[6] Patent: WO2006/51477, 2006, A2, . Location in patent: Page/Page column 53-54
[7] Organometallics, 2010, vol. 29, # 18, p. 4135 - 4138
[8] Chemische Berichte, 1909, vol. 42, p. 433
[9] Justus Liebigs Annalen der Chemie, 1867, vol. 144, p. 182
[10] Chinese Chemical Letters, 2016, vol. 27, # 1, p. 109 - 113
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Reference: [1] Chemische Berichte, 1909, vol. 42, p. 433
[2] Chemische Berichte, 1909, vol. 42, p. 433
[3] Chemische Berichte, 1909, vol. 42, p. 433
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Reference: [1] Chemische Berichte, 1925, vol. 58, p. 65
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YieldReaction ConditionsOperation in experiment
95% With thionyl chloride In dichloromethane at 80℃; for 3 h; Step 1.
Methyl 4-amino-3-methylbenzoate
A solution of 4-amino-3-methylbenzoic acid (60 g, 396.92 mmol) and SOCl2 (141.9 g, 1.19 mol) in methanol (700 mL) was stirred 3 hours at 80° C.
The resulting solution was concentrated in vacuo to afford a residue, which was dissolved in dichloromethane (500 mL) and washed with saturated aqueous sodium bicarbonate, dried over anhydrous magnesium sulfate and concentrated in vacuo to afford methyl 4-amino-3-methylbenzoate (62 g, 95percent) as a pink solid.
LC/MS (ES, m/z): [M+H]+ 152.1
1H-NMR (300 MHz, CDCl3) δ 7.78 (d, J=0.6 Hz, 1H), 7.74 (d, J=2.1 Hz, 1H), 6.65 (d, J=8.1 Hz, 1H), 4.11 (s, 2H), 3.87 (s, 3H), 2.20 (s, 3H)
95% at 20℃; for 12 h; 4-Amino-3-methylbenzoic acid (20 mmol) and 30 ml MeOH were placed in a flask, and SOCl2 (24 mmol) were added dropwise at -5 °C.
The reaction kept for 12 h at room temperature.
The solvent was evaporated and the residue was basified with NaHCO3 to PH 7 or 8, extracted with ethyl acetate (EA).
The dried organic phase was concentrated to get the compound 4. White solid, yield 95percent, mp 119-120 °C; 1H NMR (400 Hz, CDCl3) δ (ppm): 2.07 (s, 3H, Ar-CH3), 3.73 (s, 3H, OCH3), 5.74 (s, 2H, NH2), 6.60 (d, 1H, JH = 8.0 Hz, Ar-H), 7.52 (dd, 1H, J12 = 2.0 Hz, J13 = 8.4 Hz, J34 = 2.0 Hz, Ar-H), 7.55 (s, 1H, Ar-H).
92% at 90℃; for 10 h; To a solution of 4-amino-3-methylbenzoic acid (80 g, 529.23 mmol) in methanol (1000 mL) was added thionyl chloride (250 g) with stirring for 10 h at 90°C. The resulting mixture was concentrated under vacuum. The resulting mixture was diluted with H20 (200 mL), extracted with dichloromethane (3 x 150 mL) and the organic layers combined and dried over anhydrous sodium sulfate. The solids were filtered out to give the filtered, which was concentrated under vacuum to afford methyl 4-amino-3-methylbenzoate as a light yellow solid (80 g, 92percent). LCMS (ES, m/z): [M+H]+ 166.0 *H NMR (300 MHz, DMSO) δ 8.25 (brs, 2H), 7.60 (s, 1H), 7.59 (s, 1H), 6.86 (d, J = 8.40Hz, 1H), 3.76 (s, 3H), 2.16 (s, 2H)
Reference: [1] Advanced Synthesis and Catalysis, 2010, vol. 352, # 9, p. 1451 - 1454
[2] Patent: US2012/277224, 2012, A1, . Location in patent: Page/Page column 39
[3] Bioorganic and Medicinal Chemistry, 2014, vol. 22, # 22, p. 6366 - 6379
[4] Patent: WO2014/66795, 2014, A1, . Location in patent: Paragraph 0175
[5] Journal of Organic Chemistry, 1996, vol. 61, # 17, p. 5804 - 5812
[6] Patent: EP1568688, 2005, A1, . Location in patent: Page/Page column 30
[7] Patent: US2004/132779, 2004, A1, . Location in patent: Page/Page column 17
[8] Journal of Photochemistry and Photobiology A: Chemistry, 2010, vol. 213, # 2-3, p. 164 - 170
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Reference: [1] Journal of Medicinal Chemistry, 2001, vol. 44, # 25, p. 4416 - 4430
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YieldReaction ConditionsOperation in experiment
93%
Stage #1: With triethylamine In dichloromethane for 0.5 h;
Stage #2: at 20℃; for 72 h;
Et3N (25.09 mL, 180 mmol)was added dropwise to 4-amino-3-methylbenzoic acid I (9 g, 60 mmol) dissolved in CH2Cl2 (100 mL) in a 250 mL flask. After 0.5 h, Ac2O was injected slowly. The reaction mixture was vigorously stirred at room temperature for 3 days. The mixture was evaporated to remove the solvent, and the residues were redissolved in 1 M hydrochloric acid (50mL) and water (100 mL). Overnight, light-pink long crystals grew and were filtered off (10.7 mg, 93percent); m.p. 237–239 (lit.11 114–116 °C);IR (KBr cm-1): 3270, 1662, 1522, 1422, 1279; 1H NMR (DMSO-d6): δ12.79 (s, 1H), 9.40 (s, 1H), 7.78 (s, 1H), 7.73 (s, 2H), 2.27 (s, 3H), 2.11(s, 3H); ESI: m/z = 386.7 [M+H]+ (double).
Reference: [1] Journal of Chemical Research, 2015, vol. 39, # 7, p. 407 - 409
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YieldReaction ConditionsOperation in experiment
56% With acetic anhydride; triethylamine In dichloromethane 4-Acetamido-3-methylbenzoic acid
To a suspension of 4-amino-3-methylbenzoic acid (60 g, 0.40 mol) in methylene chloride (800 mL) was added triethylamine (121 g, 1.19 mol).
The solution became clear.
Then, acetic anhydride (81 g, 0.79 mol) was added and the reaction mixture was stirred for 60 h at room temperature.
The solvent was evaporated.
The residue was diluted with water (400 mL) and extracted with ethyl acetate (3*600 mL).
The combined organic extracts were dried over magnesium sulfate, filtered and evaporated to give the title compound as a tan solid (43 g, 56percent yield).
1H-NMR (d6-DMSO, 300 MHz) δ 9.36 (s, 1H), 7.77 (s, 1H), 7.10 (s, 2H), 2.27 (s, 3H), 2.10 (s, 3H). LC/MS: tR=1.22 min, 194 (MH)+.
Reference: [1] Patent: US2004/204397, 2004, A1,
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Reference: [1] Bioorganic and Medicinal Chemistry, 2014, vol. 22, # 22, p. 6366 - 6379
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Reference: [1] Patent: CN103755641, 2017, B,
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Reference: [1] Journal of Organic Chemistry, 1996, vol. 61, # 17, p. 5804 - 5812
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Reference: [1] Bioorganic and Medicinal Chemistry, 1999, vol. 7, # 12, p. 3011 - 3024
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Reference: [1] Patent: US5965539, 1999, A,
[2] Patent: US5834434, 1998, A,
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Reference: [1] Patent: US2013/79306, 2013, A1,
[2] Patent: US2013/79306, 2013, A1,
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Reference: [1] Patent: US2012/277224, 2012, A1,
[2] Patent: WO2014/66795, 2014, A1,
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Reference: [1] Bioorganic and Medicinal Chemistry Letters, 2014, vol. 24, # 4, p. 1098 - 1103
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YieldReaction ConditionsOperation in experiment
92% With benzotriazol-1-ol; 1-ethyl-(3-(3-dimethylamino)propyl)-carbodiimide hydrochloride; N-ethyl-N,N-diisopropylamine In tetrahydrofuran at 20℃; Step 1.
Synthesis of 4-Amino-N,N,3-trimethylbenzamide
To a solution of 4-amino-3-methylbenzoic acid (1.00 g, 6.60 mmol), EDCI · HCl (1.89 g, 9.90 mmol), HOBt (1.34 g, 9.90 mmol), and dimethylamine hydrochloride (0.650 g, 7.90 mmol) in THF (12 mL) was treated DIPEA (4.00 mL, 2.89 g, 23.1 mmol) in one portion.
The reaction mixture was stirred at r.t. overnight then partitioned between ethyl acetate (60 mL) and 5N NaOH (10 mL).
The organic layer was washed with brine (10 mL) dried over MgSO4 and concentrated to give a crude product which was purified by flash chromatography to give the desired product as a brown viscous liquid (1.08 g, 92percent).
1H NMR (CDCl3, 300 MHz) δ 7.19 (s, 1H), 7.14 (d, 1H), 6.63 (d, 1H), 3.77 (br s, 2H), 3.05 (s, 6H), 2.16 (s, 3H).
Reference: [1] Patent: US2017/253569, 2017, A1, . Location in patent: Paragraph 0725-0726
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Reference: [1] Patent: WO2014/66795, 2014, A1,
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