Structure of 5471-82-9
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CAS No. : | 5471-82-9 |
Formula : | C9H9NO4 |
M.W : | 195.17 |
SMILES Code : | C1=C(C(=C(C=C1)C)[N+]([O-])=O)C(OC)=O |
MDL No. : | MFCD01003947 |
InChI Key : | NJHDBIXFFZVJGZ-UHFFFAOYSA-N |
Pubchem ID : | 79621 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H302-H315-H319-H332-H335 |
Precautionary Statements: | P261-P280-P305+P351+P338 |
* 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 |
---|---|---|
41% | With N-Bromosuccinimide; Perbenzoic acid; In tetrachloromethane; for 12.0h;Heating / reflux; | Step B; Methyl 3-Bromomethyl-2-nitrobenzoate; Heat a mixture of methyl 3-methyl-2-nitrobenzoate (12.34 g, 63.23 mmol), benzoyl peroxide (0.920 g, 3.80 mmol) and N-bromosuccinimide (11.25 g, 63.21 mmol) in carbon tetrachloride (330 mL) at reflux under nitrogen for 12 h. Dilute the cooled mixture with methylene chloride (150 mL), treat with silica gel (30 g) and remove the solvents under reduced pressure. Purify the residue by flash column chromatography on silica gel, eluting with ethyl acetate/hexanes (15: 85), to provide methyl 3-bromomethyl-2- nitrobenzoate (1B) as a pale yellow solid (7.15 g, 41%) :'H NMR (CDC13) 8 3.91 (s, 3H), 4.46 (s, 2H), 7.58 (t, 1H), 7.74 (dd, 1H), 7.96 (dd, 1H). |
35% | With N-Bromosuccinimide; dibenzoyl peroxide; In tetrachloromethane; for 12.0h;Reflux; Inert atmosphere; | Weigh compound 1 (2.34g, 12mmol), dissolve it with 0.2M carbon tetrachloride solution, add benzoyl peroxide (0.17g, 0.72mmol), NBS (2.18g, 14.16mmol), and reflux under nitrogen. 12 hours.After the mixture was cooled to room temperature, the filtrate was concentrated under reduced pressure, 30 mL of water was added, and extracted with EA three times. The organic phase was washed with brine, dried over anhydrous sodium sulfate, filtered, and distilled under reduced pressure to obtain a yellow mixture, which was subjected to column chromatography (eluent was Petroleum ether: ethyl acetate = 90: 1) to give Compound 2 (1.15 g, 35%) as a white flocculent solid. |
30% | With N-Bromosuccinimide; dibenzoyl peroxide; In tetrachloromethane; for 20.0h;Inert atmosphere; | A mixture of Compound E (5.13 g, 26.3 mmol), benzoyl peroxide (511 mg, 2.11 mmol), and N- bromosuccinamide (14.1 g, 78.8 mmol) in CCU (120 mL) was heated under a nitrogen atmosphere for 20 h. The mixture was cooled to ambient temperature, diluted with dichloromethane and concentrated under reduced pressure. The residue was purified by flash column chromatography on silica gel using 10% EtOAc/hexanes (10:90) to yield Compound F (2.14 g, 7.80 mmol) in 30% yield as an off-white solid. NMR (400 MHz, CDCh) delta 7.93 (d, J= 7.7 Hz, 1H), 7.72 (d, J= 7.7 Hz, 1H), 7.57 (t, J = 7.7 Hz, 1H), 4.43 (s, 2H), 3.88 (s, 3H). MS (ES+) m/z: C9H8BrN04 requires 273/275, found 242/244 (M - MeO) 227/229 (M - N02). Physical state: Off-white solid; R/= 0.7 (mobile phase: EtOAc/hexanes, 20:80). |
Part B. Methyl 3-(bromomethyl)-2-nitrobenzoate This product was prepared by following the procedure of Example 6, but substituting methyl 3-methyl-2-nitrobenzoate for 8-methylquinoline. The product was purified by chromatography on silica gel and was crystallized from ethyl acetate:hexane; mp 91-95 C. | ||
With N-Bromosuccinimide; dibenzoyl peroxide; In tetrachloromethane; for 12.0h;Reflux; | Step 2: Methyl 3-(bromomethyI)-2-nitrobenzoate (A2); A mixture of (Al) (1.0 eq.), (BzO)2 (0.06 eq.) and NBS (1.18 eq.) in CCl4 (0.2 M, with respect to Al) was heated at reflux under N2 atmosphere for 12 hr. The mixture was cooled to RT, diluted with DCM, concentrated under reduced pressure whilst dry loading onto SiO2. The residue was purified by flash column chromatography on SiO2 using 10:90 EtO Ac/Petroleum ether to yield the desired (A2) as a white solid. 1H NMR (400MHz, CDCl3, 300K) delta 7.93 (1 H, d, J = 7.7 Hz), 7.72 (IH, d, J = 7.7 Hz), 7.57 (IH, t, J = 7.7 Hz), 4.43 (2H, s), 3.88 (3H, s). MS (ES) C9H8BrNO4 requires: 273:275, found: 242:244 (M-MeO)+, 227:229 (M-NO2) +. | |
With N-Bromosuccinimide; dibenzoyl peroxide; In benzene; at 90.0℃; | Process 2 Bromination Benzoyl peroxide was added to the mixture of methyl 2-nitro-3-methylbenzoate (1.6 g), N-bromosucciimide (2.0g) and benzene (15 mL) and stirred at 90 C. overnight. After removing the solvent, the residue was diluted with ethyl acetate and washed with sodium thiosulfate aqueous solution, 1M sodium hydrate aqueous solution, water and saturated aqueous solution of sodium chloride respectively. Then the obtained substance was concentrated and dried, and the obtained crude material was purified with silica gel column chromatography to obtain methyl 3-bromomethyl-2-nitrobenzoate. | |
With N-Bromosuccinimide; dibenzoyl peroxide; In tetrachloromethane; for 12.0h;Heating / reflux; | Step 2: Methyl 3-(bromomethyl)-2-nitrobenzoate (A2); A mixture of (Al) (1.0 eq.), (BzO)2 (0.06 eq.) and NBS (1.18 eq.) in CCl4 (0.2 M) was heated at reflux under N2 atmosphere for 12 hr. The mixture was cooled to RT, diluted with DCM, concentrated under reduced pressure whilst dry loading onto SiO2. The residue was purified by flash column chromatography on SiO2 using 10:90 EtO Ac/Petroleum ether to yield the desired (A2) as a white solid. 1H NMR (400MHz, CDCl3, 300K) delta 7.93 (IH, d, J = 7.7 Hz), 7.72 (IH, d, J = 7.7 Hz), 7.57 (IH, t, J = 7.7 Hz), 4.43 (2H, s), 3.88 (3H, s). MS (ES) C9H8BrNO4 requires: 273:275, found: 242:244 (M-MeO)+, 227:229 (M-NO2) +. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In tetrachloromethane; | Step 2: Synthesis of Methyl 2-nitro-3-bromomethylbenzoate: Methyl 2-nitro-3-methylbenzoate (15.3 gm) was suspended in carbon tetrachloride (45 mL) along with N-bromosuccinimide (15 3 gm) and heated to reflux. 2,2'-Azobis(2-methylpropionitrile) (AIBN) (0.4 gm) was added to the refluxing solution in four equal portions over 48 hours. The reaction was cooled to room temperature, filtered, and concentrated. The residue consisted of a mixture of starting material, desired product, and dibrominated material which were difficult to separate and so were used in the next step without purification. |
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