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CAS No. : | 138229-59-1 | MDL No. : | MFCD14706049 |
Formula : | C9H7NO5 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | NSLOBVGASZUPDO-UHFFFAOYSA-N |
M.W : | 209.16 | Pubchem ID : | 44549250 |
Synonyms : |
|
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P273-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319-H335-H412 | 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 |
---|---|---|
78% | With 4-methylmorpholine N-oxide; In acetonitrile; at 20.0℃; for 2.0h;Molecular sieve; Inert atmosphere; | Compound 2 (2.74 g, 10 mmol) was weighed into a 150 mL single-necked flask, and a mixture (0.2 M) of molecular sieve in acetonitrile was added to dissolve it. Under the protection of nitrogen, N-methylmorpholine-N-oxide (2.34) was added. g, 20 mmol), reacted at room temperature for 2 hours, concentrated and poured into water, extracted three times with EA, the organic phase was washed with 1N HCl, brine, dried, filtered, concentrated, and subjected to column chromatography (eluent is petroleum ether : Ethyl acetate = 80: 1) to give Compound 3 (1.63 g, 78%) as a pale yellow solid. |
74% | With 4-methylmorpholine N-oxide; In acetonitrile; at 20.0℃; for 1.5h; | Step C; Methyl 3-Formyl-2-nitrobenzoate; Add N-methylmorpholine oxide (NMO, 6.10 g, 52.07 mmol) to a mixture of <strong>[132874-06-7]methyl 3-bromomethyl-2-nitrobenzoate</strong> (7.13 g, 26.023 mmol) and 4 A molecular sieves (35.32 g) in acetonitrile (150 mL) = at room temperature under nitrogen and stir for 1.5 h. Dilute the mixture with ethyl acetate (600 mL), filter the mixture by vacuum filtration and wash the filtrate with water (100 mL), 1 N HC1 (100 mL) and brine (150 mL) and dry over Na2S04. Remove the solvents under reduced pressure and purify the residue by flash column chromatography on silica gel, eluting with ethyl acetate/hexanes (1: 3), to provide methyl 3-formyl-2-nitrobenzoate as an off-white solid (4.04 g, 74%) : 1H NMR (CDC13) 8 3.95 (s, 3H), 7.77 (t, 1H), 8. 18 (dd, 1H), 8.28 (dd, 1H), 9. 98 (s, 1H). |
54% | With 4-methylmorpholine N-oxide; In acetonitrile; at 20.0℃; for 12.0h; | To a mixture of Compound F (1.97 g, 7.18 mmol) in MeCN (20 mL) was added N- methylmorpholine N-oxide (2.15 g, 17.9 mmol) at ambient temperature, and the reaction mixture was stirred for 12 h. The reaction mixture was diluted with EtOAc, washed with water, 1 M HCl and brine. The organic extracts were dried over Na2S04, filtered and evaporated under reduced pressure. The residue was purified by flash column chromatography on silica gel using 5% EtO Ac/petroleum ether to provide Compound G (824 mg, 3.93 mmol) in 54% yield. MR (400 MHz, CDCb) delta 9.96 (s, 1H), 8.26 (d, J= 7.9 Hz, 1H), 8.18 (d, J = 7.9 Hz, 1H), 7.77 (t, J= 7.9 Hz, 1H), 3.93 (s, 3H). MS (ES -) m/z: C9H7NO5 requires 209, found 208 (M - H)". Physical state: Off- white solid; R = 0.6 (mobile phase: EtOAc/hexanes, 1 :9). |
With 4-methylmorpholine N-oxide; In acetonitrile; at 20.0℃;Molecular sieve; | Step 3: Methyl 3-formyI-2-nitrobenzoate (A3); To a mixture of (A2) (1.0 eq.) and 4A mol. sieves in MeCN (0.2M) at RT was addedNMMO (2.0 eq.) and the reaction mixture was stirred for 1.5 hr under N2 atmosphere. Then, the mixture was diluted with EtOAc, filtered and the filtrate was washed with H2O, IN HCl, brine <n="37"/>and dried (Na2SO4). Evaporation of the solvent gave (A3) as a white solid which was used in the next step without further purification. 1H NMR (400MHz, CDCl3, 300K) delta 9.96 (IH, s), 8.26 (IH, d, J= 7.9 Hz), 8.18 (IH, d, J = 7.9 Hz), 7.77 (IH, t, J = 7.9 Hz), 3.93 (3H, s). MS (ES) C9H7NO5 requires: 209, found: 208 (M-H)'. | |
With 4-methylmorpholine N-oxide; In acetonitrile; at 20.0℃; for 1.5h;Molecular sieve; | Step 3: Methyl 3-formyl-2-nitrobenzoate (A3); To a mixture of (A2) and 4A mol. sieves (15 g) in MeCN (0.2M) at RT was added NMMO (2.0 eq.) and the reaction mixture was stirred for 1.5 hr under N2 atmosphere. Then, the mixture was diluted with EtOAc, filtered and the filtrate was washed with H2O, IN HCl, brine and dried (Na2SO4). Evaporation of the solvent gave (A3) as a white solid which was used in the next step without further purification. 1H NMR (400MHz, CDC13, 3OOK) delta 9.96 (IH, s), 8.26 (IH, d, J= 7.9 Hz), 8.18 (IH, d, J = 7.9 Hz), 7.77 (IH, t, J = 7.9 Hz), 3.93 (3H, s). MS (ES) C9H7NO5 requires: 209, found: 208 (M-H)". |
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