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With sulfuric acid;nitric acid; at -5 - 0℃; for 3.5h; |
Example 122A5-Chloro-2-methyl-3-nitrobenzoic acid[00751] To a cone. H2S04 (90 mL) was added portionwise 5-chloro-2-methylbenzoic acid (13.2 g, 77.6 mmol) at -5-0 C. Then a mixture of cone. HN03 (10.5 g, 1744 mmol) in cone. H2S04 (15 mL) was added dropwise at -5-0 C over a period of about 1.5 hr. After the addition, the mixture was stirred at this temperature for 2 hr. The mixture was poured into crashed ice with vigorous stirring and the precipitate was collected by filtration. The precipitate was dissolved in EtOAc, washed with brine, dried over anhydrous Na2S04, and concentrated to give a crude title compound (13.2 g), which was used in the next step without further purification. |
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With nitric acid; In sulfuric acid; at -15℃; for 2h; |
To H2S04 (250 ml, 4690 mmol) with stirring at -15 oc (NaCl ice bath) was addedportionwise 5-chloro-2-methylbenzoic acid (25 g, 147 mmol) (slowly went into solution).Next a cooled mixture of fuming nitric acid (12.5 ml, 280 mmol) in H2S04 (62 mL) wasadded dropwise. After stirring at -15 oc for 2 hr a cloudy suspension began to form. Thereaction was poured onto ice (~500 mL) and stirred for 30 minutes. The suspension was filtered, washed with water, and dried under vacuum to give the product 5-chloro-2-methyl-3-nitrobenzoic acid (30.58 g, 142 mmol, 97% yield) as an off-white solid. 81%pure by LCMS did not show a mass ion. Only ~73% pure byNMR. Used as is in the nextreaction. 1H NMR (400MHz, DMSO-d6) 8 = 13.89 (br. s., 1 H), 8.22 (d, J= 2.0 Hz, 1 H),8.03 (d, J = 2.0 Hz, 1 H), 2.47 (s, 3 H). |
| 39 g |
With sulfuric acid; nitric acid; at 0℃; for 6h; |
To a solution of 5-chloro-2-methylbenzoic acid (50 g) in conc. H2SO4(300 mL) at 0 was added a mixture of nitric acid (65 1.92 g) and conc. sulfuric acid (50 mL) portionwise. The mixture was stirred for 6 hours and then poured into ice (1 kg) . The resulting mixture was diluted with water (100 mL) . After filtration the solid was collected and redissolved in EA (300 mL) . The solution was washed with brine dried over Na2SO4 filtered and concentrated in vacuo. The residue was washed with EA and PE (21 50 mL) twice to afford the title compound (39 g) as a yellow solid. MS (ESI) C8H6ClNO4requires 215 found 216 [M+H]+. |
| 39 g |
With sulfuric acid; nitric acid; at 0℃; for 6h; |
To a solution of 5-chloro-2-methylbenzoic acid (50 g) in cone. H2S04 (300 mL) at 0C was added a mixture of nitric acid (65%, 1.92 g) and conc. sulfuric acid (50 mL) portionwise. The mixture was stirred for 6 hours, and then poured into ice (1 kg). The resulting mixture was diluted with water (100 mL). After filtration, the solid was collected and redissolved in EA (300 mL). The solutionwas washed with brine, dried over Na2SO4, filtered and concentrated in vacuo. The residue waswashed with EA and PE (2:1, 50 mL) twice to afford the title compound (39 g) as yellow solid. MS(ESI): C8H6C1NO4 requires 215; found 216 [M+H]. |
| 10.7 g |
With sulfuric acid; nitric acid; at 0 - 20℃; for 5h; |
Description 1365-Chloro-2-methyl-3-nitrobenzoic acid (D136)To a solution of 5-chloro-2-methylbenzoic acid (8.5 g) in con. sulfuric acid (98%, 150 mL), nitric acid (65%, 17.1 mL) was added dropwise at 0C and the mixture was warmed gradually to RT and stirred at RT for 5 hours. The mixture was poured into ice (500 g), the resulting solid was collected and washed with water three times, dried to afford title compound (10.7 g), with its regioisomer. ?H NMR (400 MHz, DMSO-d6): 8.19 (d, J 2.3 Hz, 1H), 8.02 (d, J= 2.3 Hz, lH), 2.47 (s,4H). MS (ESI): C8H6C1NO4 requires 215; found 238 [M+Na]. |
| 39 g |
With sulfuric acid; nitric acid; at 0℃; for 6h; |
At 0 c, In a medium containing 5-chloro-2-methylbenzoic acid (50 g) Concentrated H2SO4 solution (300 mL) was added in portions with nitric acid (65%, 1.92 g) with concentrated sulfuric acid (50 mL) of the mixture. After stirring the mixture for 6 hours, Down to the ice The resulting mixture was diluted with water (100 mL). After filtration,The solid was collected and dissolved again in EpsilonAlpha (300 mL).The solution was washed with brine, dehydrated by Na2SO4, filtered, and concentrated in vacuo. The residue was washed twice with EA and PE (2: 1, 50 mL) to give the title compound (39 g) as a yellow solid. |
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With sulfuric acid; nitric acid; at 0℃; for 0.5h; |
5-Chloro-2-methylbenzoic acid (75.0 g, 439 mmol) was added portion-wise to cone.sulphuric acid (525 ml, 7 vol) at 0C. After complete addition a solution of cone. nitricacid ( 41.1 g, 978 mmol, 67%) in cone. sulphuric acid (82.5 ml) was added drop-wisemaintaining internal temperature at 0C. On complete addition the reaction mixture was stirred for an additional 30 mins at 0C. The mixture was poured onto ice/water and theprecipitate was filtered, washed with water, dried and filtered to afford title compound asan off-white solid. (80.0 g, 84.4 %, as a mixture of isomers)1H NMR (400MHz, CDCI 3) o = 8.18 (d, J = 2.4 Hz, 1H), 7.90 (d, J = 2.4 Hz, 1H), 2.66 (s,3H). Peaks at 7.55 (d, J = 8.3 Hz, 1H), 7.39 (d, J = 8.3 Hz, 1H), 2.57 (s, 3H) relate to regioisomer. LCMS Method 1: m/z 214.03 [M-H+]; RT = 2.49 min. |
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