BOC-3-AMINOBENZOIC ACID

Brown powder

General procedure: To a stirred solution of 4-aminobenzoic acid 6a (5.00 g, 36.5 mmol) and sodium hydroxide (1.56 g, 39.3 mmol) in 1:1 water/dioxane (60 mL) at 0 °C was added di-tert-butyl dicarbonate (14.3 g, 65.4 mmol). The resulting mixture was stirred for 3 h, then warmed to room temperature and stirred overnight. The aqueous mixture was then washed with ethyl acetate (60 mL) before further ethyl acetate (60 mL) was added and the resulting mixture neutralised with 1 M aqueous KHSOTo a solution of 3-aminobenzoic acid (6 g, 0.043 mmol), Triethyl amine (12.1 mL, 87.6 mmol), water (50 mL) in 1-4 Dioxane (100 mL) was added Boc anhydride (15 mL, 65.7 mmol) at room temperature. Reaction mixture was allowed to stir for 16 h at room temperature. TLC showed absence of starting material (RGeneral procedure: To a solution of 12a (2.0 g, 14.6 mmol) in 67percent 1.4-dioxane/water(48 mL) was added triethylamine (4.07 mL, 29.2 mmol) at room temperature and allowed to stir for 5 min. Di-tert-butyl decarbonate(6.37 mL, 29.2 mmol) was then added to the solution. After beingstirred for 26 h, the reaction mixture was concentrated and acidified with 2M hydrochronic acid to yield a white precipitate. The slurry wasthen filtered, washed with water and dried over in vacuo to afford 13a(2.94 g, 86percent) as a white solid.:[0145]The mixture of 3-aminobenzoic acid (500 mg, 3.65 mmol) and triethylamine (1.11 g, 10.97 mmol) in methanol (6 mL) was allowed to cool to 0 before di-tert-butyl dicarbonate (880 mg, 4.03mmol) was added. Then, the resulting mixture was stirred at room temperature for 10 h before quenched with water. The solvent was removed under reduced pressure. The residue was purified by column chromatography (silica gel, dichloromethane/methanol 100: 1 to 10: 1) to give 3- ( (tert-butoxycarbonyl) amino) benzoic acid (1) as a white solid (800 mg, yield 92.5) . Mass spectrum (ESI) m/z calc. for CCommercially available 3-amino benzoic acid (5 g, 36 mmol) was dissolved in 1 M sodium hydroxide solution (40 mL, 40 mmol) and 1, 4-dioxane (30 mL). After the addition of di-tert-butyl dicarbonate (7.85 g, 36 mmol), the mixture was stirred at room temperature over the weekend. The dioxane was removed in vacuo and the residue was diluted with water (100 mL). Then concentrated hydrochloric acid (37percent) was added until pH3. The precipitate was collected by filtration, washed with water (100 mL) and air-dried to afford the title compound as a white solid (7.3 g, 84percent).3-aminobenzoic acid (4.4 g, 32.1 mmol) and di-tert-butyl dicarbonate (10.5 g, 48.2 mmol) were dissolved in anhydrous THF (60 mL) . Then N-ethyl-N-isopropylpropan-2-amine (8.3 g, 64.2 mmol) was added. The reaction mixture was stirred at room temperature. After the completion of the reaction, it was concentrated in vacco and the residue was extracted with ethyl acetate. The organic layer was concentrated and the residue was purified by column chromatograph to provide the desired product (6.2 g, 82) MS [MH] -calcd for C12H14NO4 236.10, found 236.10.To a stirred solution of 3-aminobenzoic acid (5 g, 36.5 mmol) in water (40.0 ml) was added aq. solution of sodium hydroxide (2.187 g, 54.7 mmol) followed by (BOC)20 (10.16 ml, 43.8 mmol) in dioxane (20.0 ml) under ice cooling. The mixture was stirred under ice cooling for 30 min and further at room temperature for 12 hrs. To the reaction mixture ethyl acetate (50.0 ml) was added and the aq. layer was separated. The aq. layer was acidified up to pH 4 using 2N HC1 and precipitated crystals were collected by filtration (7.2 gm). Step a: The ester prepared in preparation 25 (750 mg, 2.83 mmol), lithium hydroxide (415 mg, 9.89 mmol), methanol (15 mL), water (15 mL), and tetrahydrofuran (45 mL), were combined in a 250 mL round bottomed flask, fitted with a stirbar, and under a nitrogen atmosphere. The mixture was stirred vigorously at room temperature for 16 hours, then was concentrated under vacuum, dissolved in 1N HCl, and extracted with methylene chloride (100 mL*3). Organic layer was dried (MgSO4), filtered, and concentrated under vacuum, yielding 600 mg of white solid. This material was purified by recrystallization in hexanes:ethyl acetate, yielding the title compound as 580 mg (86percent) white solid.[0184] Electrospray-MS 238.0 (M*+1).Step A:; Di-tert-Butyl carbonate (1.28 g, 58.4 mmol) was added to solution of m-aminobenzoic acid (0.5 g, 36.5 mmol), sodium hydroxide (0.21 g, 51.4 mmol), DMF (10 mL) and water (10 mL) at 0° C. The reaction mixture was allowed to reach ambient temperature while stirring for 16 h. A 6 mL of 1 N HCl was added to the solution to bring it to pH 6. The precipitate was collected to yield the tBoc protected aminobenzoic acid (0.5 6 g, 23.6 mmol, 65percent) as a white solid.

Molecular Weight:237.25
XLogP3:2.7
Hydrogen Bond Donor Count:2
Hydrogen Bond Acceptor Count:4
Rotatable Bond Count:4
Exact Mass:237.10010796
Monoisotopic Mass:237.10010796
Topological Polar Surface Area:75.6
Heavy Atom Count:17
Complexity:295
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes