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CAS No. : | 284030-58-6 | MDL No. : | MFCD06201870 |
Formula : | C8H6F2N2O4 | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | HOJFIOHGPQOQBF-UHFFFAOYSA-N |
M.W : | 232.14 | Pubchem ID : | 2759749 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P264-P270-P301+P312-P330 | UN#: | |
Hazard Statements: | H302-H315-H320-H335 | Packing Group: | |
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 |
---|---|---|
92% | With methanol; In tetrahydrofuran; at 0 - 20℃; for 0.5h; | Step C: 4-Amino-2,3-difluoro-5-nitro-benzoic acid methyl ester 4. A 2 M solution of TMS diazomethane in hexanes (6.88 mL, 13.75 mmol) is added to a suspension of <strong>[284030-57-5]4-amino-2,3-difluoro-5-nitro-benzoic acid</strong> 3 (2.00 g, 9.17 mmol) in 25 mL of 4:1 THF:MeOH at 0 C. under nitrogen atmosphere. Upon completion of addition, reaction mixture is warmed to room temperature. After 0.5 hours, excess TMS diazomethane is destroyed by the careful addition of acetic acid. The reaction is then concentrated under reduced pressure and dried in vacuo to give 1.95 g (92%) of pure desired product: MS APCI (-) m/z 231 (M-1) detected. |
92% | A 2 M solution of TMS diazomethane in hexanes (6.88 ml, 13.75 mmol) is added to a suspension of <strong>[284030-57-5]4-amino-2,3-difluoro-5-nitro-benzoic acid</strong> 3 (2.00 g, 9.17 mmol) in 25 ml of 4:1 THF:MeOH at 0 C. under nitrogen atmosphere. Upon completion of addition, reaction mixture is warmed to room temperature. After 0.5 h, excess TMS diazomethane is destroyed by the careful addition of acetic acid. The reaction is then concentrated under reduced pressure and dried in vacuo to give 1.95 g (92%) of pure desired product: MS APCI (-) m/z 231 (M-1) detected. | |
92% | In tetrahydrofuran; methanol; hexane; at 0 - 20℃; for 0.5h;Inert atmosphere; | 4-Amino-2, 3-difluoro-5-nitro-benzoic acid methyl ester 4A 2 M solution of TMS diazomethane in hexanes (6.88 ml, 13.75 mmol) is added to a suspension of <strong>[284030-57-5]4-amino-2,3-difluoro-5-nitro-benzoic acid</strong> 3 (2.00 g, 9.17 mmol) in 25 ml of 4:1 THF:MeOH at 0 C under nitrogen atmosphere. Upon completion of addition, reaction mixture is warmed to room temperature. After 0.5 h, excess TMS diazomethane is destroyed by the careful addition of acetic acid. The reaction is then concentrated under reduced pressure anddried in vacuo to give 1.95 g (92%) of pure desired product: MS APCI (-) m/z 231 (M-1) detected. |
84% | In methanol; at 0℃; for 1h; | Trimethylsilylated diazomethane (1.26 g, 11.02 mmol) was slowly added dropwise to a solution of compound 3 (2.0 g, 9.17 mmol) in methanol at 0 C, and the reaction was continued for 1 h. The reaction was quenched by the addition of a few drops of acetic acid, and then the mixture was evaporated. EtOAc (EtOAc) Methanol (10 ml) was beaten to obtain a pure product of 1.8 g in a yield of 84%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1.95 g (92%) | With acetic acid; In tetrahydrofuran; methanol; | Step C 4-Amino-2,3-difluoro-5-nitro-benzoic acid methyl ester A 2 M solution of TMS diazomethane in hexanes (6.88 ml, 13.75 mmol) is added to a suspension of <strong>[284030-57-5]4-amino-2,3-difluoro-5-nitro-benzoic acid</strong> (2.00 g, 9.17 mmol) in 25 ml of 4:1 THF:MeOH at 0 C. under nitrogen atmosphere. Upon completion of addition, reaction mixture is warmed to room temperature. After 0.5 h, excess TMS diazomethane is destroyed by the careful addition of acetic acid. The reaction is then concentrated under reduced pressure and dried in vacuo to give 1.95 g (92%) of pure desired product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With diazomethyl-trimethyl-silane; In tetrahydrofuran; methanol; hexane; at 0 - 20℃; for 0.5h; | A 2 M solution of tetramethylsilane (TMS) diazomethane in hexanes (6.88 ml, 13.75 mmol) was added to a suspension of <strong>[284030-57-5]4-amino-2,3-difluoro-5-nitrobenzoic acid</strong> (2.00 g, 9.17 mmol) in 25 ml of 4: 1 Tetrahydrofuran (THF):MeOH at 0 0C under nitrogen atmosphere. Upon completion of addition, reaction mixture was warmed to room temperature. After 0.5 hours, excess TMS diazomethane was destroyed by the careful addition of acetic acid. The reaction was then concentrated under reduced pressure and dried in vacuo 1.95 g (92%) of pure desired product: MS APCI (-) m/z 231 (M-I) detected. |
70% | With hydrogenchloride; In methanol; | Step c Preparation of methyl 4-amino-2,3-difluoro-5-nitrobenzoate Hydrogen chloride gas was dissolved in anhydrous methanol (30 ml) until the solution was warm. The solid <strong>[284030-57-5]4-amino-2,3-difluoro-5-nitrobenzoic acid</strong> (0.47 g; 0.00215 mol) was dissolved in this solution and the reaction mixture was brought to reflux with vigorous stirring for 23 hours under a nitrogen atmosphere. The reaction mixture was allowed to cool slowly on the bench. A yellow precipitate formed and was collected by vacuum filtration and dried with suction to afford 0.35 g of yellow microfilaments; 70% yield; m.p. 183.5-184 C.; 1H-NMR (400 MHz; DMSO) delta8.36 (dd, 1H, J=7.3, 1.7 Hz), 8.06 (s, 2H), 3.78 (s, 3H); 19F-NMR (376 MHz; DMSO) delta-128.85 to -128.92 (m), -153.29 (d); MS (APCl-) 231 (M-1, 100); IR (KBr) 3433, 3322, 1700, 1650, 1549, 1343, 1285 cm-1; Anal. calcd/found for: C8H6F2N2O4 C, 41.39/41.40; H, 2.61/2.50; N, 12.07/11.98; F, 16.37/16.58. |
70% | With hydrogenchloride; In methanol; for 23h;Heating / reflux; | Hydrogen chloride gas was dissolved in anhydrous methanol (30 ml) until the solution was warm. The solid <strong>[284030-57-5]4-amino-2,3-difluoro-5-nitrobenzoic acid</strong> (0.47 g; 0.00215 mol) was dissolved in this solution and the reaction mixture was brought to reflux with vigorous stirring for 23 hours under a nitrogen atmosphere. The reaction mixture was allowed to cool slowly on the bench. A yellow precipitate formed and was collected by vacuum filtration and dried with suction to afford 0.35 g of yellow microfilaments; 70% yield; m.p. 183.5-184 C.; 1H-NMR (400 MHz; DMSO) delta 8.36 (dd, 1H, J=7.3, 1.7 Hz), 8.06 (s, 2H), 3.78 (s, 3H); 19F-NMR (376 MHz; DMSO) delta -128.85 to -128.92 (m), -153.29 (d); MS (APCl-) 231 (M-1, 100); IR (KBr) 3433, 3322, 1700, 1650, 1549, 1343, 1285 cm-1; Anal. calcd/found for: C8H6F2N2O4 C, 41.39/41.40; H, 2.61/2.50; N, 12.07/11.98; F, 16.37/16.58. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With chloro-trimethyl-silane; for 15.0833h;Heating / reflux; | Step C; 4-Amino-2,3-difluoro-5-nitrobenzoic acid methyl ester; TMSCl (132 g, 1.21 mol, 2.0 equiv) was added over 5 minutes to a slurry of 4-amino-2,3- difluoro-5-nitrobenzoic acid (132.3 g, 0.607 mol, 1 equiv.) in 325 mL of MeOH. The mixture was heated at reflux for 15 hours. When the reaction was complete as determined by HPLC, the mixture was cooled in an ice-water bath for 45 minutes. The reaction mixture was then filtered and the cake was washed with 65 mL of MeOH. The wet cake was dried overnight at 55 0C under high vacuum to give 128.8 g (92%) of 4-amino-2,3-difluoro-5- nitrobenzoic acid methyl ester. HPLC was 97.9 a% (220 n?i) and 99.2 a % (254 nm). 1H NMR (400 MHz, DMSO-d6) delta 3.84 (3H, s, OMe), 8.1 (2H, br s, NH2), 8.43 (IH, apparent dd, J 1.9, 7.2, Ar-H). 19F NMR (376 MHz, D6 DMSO) delta -153.6, -129.2. 13C NMR (100 MHz, DMSO-d6) delta 52 (CH3O), 105 (C, d, J 10), 125 (CH, t, J 2.7,), 128 (CH, d, J 5), 140 (C-F, dd, J 244, 15,), 141 (C, dd, J 14, 5), 152 (C-F, dd, J263, 11), 162 (COO, t, J3). IR vmjcm l 3433, 3322, 1699, 1637, 1548, 1342, 1234. MS APCI (-) m/z 231 (M-I) detected. |
92% | With chloro-trimethyl-silane; for 15h;Heating / reflux; | TMSCl (132 g,1.21 mol, 2.0 equiv) was added over 5 minutes to a slurry of 4-amino-2,3-difluoro-5- nitrobenzoic acid (3) (132.3 g, 0.607 mol, 1 equiv) in 325 mL of MeOH. The mixture was heated at reflux for 15 hours. Once the reaction was complete by HPLC, the reaction mixture was cooled in an ice- water bath for 45 minutes. Then the reaction mixture was filtered and the cake was washed with 65 mL of MeOH. The wet cake was dried overnight at 55 C under high vacuum to provide 128.8 g (92%) of <strong>[284030-57-5]4-amino-2,3-difluoro-5-nitrobenzoic acid</strong> methyl ester (4). HPLC was 97.9 a% (220 nm) and 99.2 a % (254 nm). 1H NMR (400 MHz, d6 DMSO) delta 3.84 (3H, s, OMe)5 8.1 (2H, br s, NH2), 8.43 (IH, apparent dd, J 1.9, 7.2, Ar-H). 19F NMR (376 MHz, d6 DMSO) delta -153.6, -129.2. 13C NMR (100 MHz, d6 DMSO) delta 52 (CH3O), 105 (C, d, J 10), 125 (CH, t, J2.7,), 128 (CH5 d, J 5), 140 (C-F5 dd, J244, 15,), 141 EPO <DP n="66"/>(C, dd, J 14, 5), 152 (C-F, dd, J263, 11), 162 (COO, t, J 3). IR vmax/cm'' 3433, 3322, 1699, 1637, 1548, 1342, 1234. MS APCI (-) m/z 23.1 (M-I) detected.; TMSCl (132 g,1.21 mol, 2.0 equiv) was added over 5 minutes to a slurry of 4-amino-2,3-difluoro-5- nitrobenzoic acid (3) (132.3 g, 0.607 mol, 1 equiv) in 325 mL of MeOH. The mixture was EPO <DP n="78"/>heated at reflux for 15 hours. Once the reaction was complete by HPLC, the reaction mixture was cooled in an ice-water bath for 45 minutes. Then the reaction mixture was filtered and the cake was washed with 65 mL of MeOH. The wet cake was dried overnight at 55 C under high vacuum to provide 128.8 g (92%) of <strong>[284030-57-5]4-amino-2,3-difluoro-5-nitrobenzoic acid</strong> methyl ester (4). HPLC was 97.9 a% (220 nm) and 99.2 a % (254 nm). 1H NMR (400 MHz, d6 DMSO) delta 3.84 (3H, s, OMe), 8.1 (2H, br s, NH2), 8.43 (IH, apparent dd, J 1.9, 7.2, Ar-H). 19F NMR (376 MHz, d6 DMSO) delta -153.6, -129.2. 13C NMR (100 MHz, d6 DMSO) delta 52 (CH3O), 105 (C, d, J 10), 125 (CH, t, J2.7,), 128 (CH, d, J5), 140 (C-F, dd, J244, 15,), 141 (C, dd, J 14, 5), 152 (C-F, dd, J263, 11), 162 (COO, t, J 3). IR vmjcra l 3433, 3322, 1699, 1637, 1548, 1342, 1234. MS APCI (-) m/z 231 (M-I) detected. |