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CAS No. : | 89976-27-2 | MDL No. : | MFCD08064223 |
Formula : | C8H6INO4 | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | SCMBIQRYVKITCY-UHFFFAOYSA-N |
M.W : | 307.04 | Pubchem ID : | 297884 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | |
Hazard Statements: | H315-H319-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 |
---|---|---|
85% | With sulfuric acid; at 0 - 0.7℃; for 8h; | Example 1 Preparation of 4-iodo-3-nitrobenzoic Acid Methyl Ester Using Methanol/Sulfuric Acid To a solution of <strong>[35674-27-2]4-iodo-3-nitrobenzoic acid</strong> (3 g, 10 mmol) in methanol (30 ml) cooled to 0 C., sulfuric acid (3.4 g, 34.6 mmol) is added slowly. The reaction mixture is warmed to room temperature and then refluxed (?70 C.) for 8 hours. After cooling, the reaction mixture is neutralized with solid NaHCO3 and the salts are filtered. The filtrate is evaporated under reduced pressure. To the residue obtained, water (30 ml) is added and the mixture extracted with MTBE (30 ml*2). The combined organic phase is washed with brine, dried using anhydrous sodium sulfate and filtered. After evaporating the solvent under reduced pressure, <strong>[35674-27-2]4-iodo-3-nitro-benzoic acid</strong> methyl ester is obtained as a yellow solid (2.67 g, 85% yield, 98% HPLC). |
83% | With sulfuric acid; at 0 - 20℃; for 16h;Inert atmosphere; | [00095] To a stirred solution of <strong>[35674-27-2]4-iodo-3-nitrobenzoic acid</strong> 46 (15 g, 51.36 mmol) in MeOH (150 mL) under inert atmosphere was added concentrated sulphuric acid (15 mL) dropwise for 10 min at 0 C; warmed to RT at stirred for 16 h. The reaction was monitored by TLC; after completion of the reaction, the volatiles were removed in vacuo. The residue was diluted with ice-cold water (500 mL) and extracted with EtOAc (3 x 100 mL). The combined organic extracts were washed saturated sodium bicarbonate solution (2 x 100 mL) dried over sodium sulfate, filtered and concentrated in vacuo to afford compound 47 (13 g, 83%) as an off-white solid. TLC: 30% EtOAc/ hexanes (R/. 0.8); 1H NMR (CDC13, 500 MHz) delta 8.45 (s, 1H), 8.15 (d, J = 8.4 Hz, 1H), 7.88 (dd, J = 8.2, 1.9 Hz, 1H), 3.97 (s, 3H). |
77% | With sulfuric acid; for 6h;Heating / reflux; | b) 4-Iodo-3-nitro-benzoic acid methyl ester A methanolic solution of <strong>[35674-27-2]4-iodo-3-nitro-benzoic acid</strong> (10.0 g, 34.13 mmol, 1 eq. ) was treated with concentrated sulfuric acid (7 mL) and the reaction heated to reflux. After 6 hours, the acid was neutralized with solid sodium bicarbonate and the methanol removed in vacuo. The residual oil was diluted with water and extracted with diethyl ether. Combined the organics, washed with brine, dried, filtered, and removed the solvent in vacuo leaving an orange oil which was purified via normal phase chromatography to leave <strong>[35674-27-2]4-iodo-3-nitro-benzoic acid</strong> methyl ester (8.08 g, 77% yield) as a yellow solid. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With hydrogen;5% sulfided platinum on carbon; In ethyl acetate; | c) 3-Amino-4-iodo-benzoic acid methyl ester An ethyl acetate solution of 4-iodo-3-nitro-benzoic acid methyl ester (17.6 g, 57.32 mmol, 1 eq. ) was hydrogenated over 5% sulfided platinum on carbon to give 3- amino-4-iodo-benzoic acid methyl ester (14.3 g, 90% yield). |
88% | With iron; acetic acid; In ethanol; at 80℃; for 1h; | A solution of 4-iodobenzoic acid methyl ester (5.24 g, 20.0 mmol) in sulfuric acid was treated with 1.43 mL of concentrated nitric acid in a dropwise fashion at 0 C. After 5 hours at room temperature, the reaction mixture was heated to 40 C for 1 hour. The resulting orange solution was added to 100 g of ice, treated with 200 mL of ethyl acetate, shaken for 30 minutes, and filtered. The phases were separated and the aqueous layer was extracted with 200 mL of ethyl acetate. The combined organic layers were washed with saturated sodium bicarbonate solution and brine, dried over magnesium sulfate, filtered, and concentrated in vacuo. The residue was passed through a column of silica gel (100% ethyl acetate) to give 2.0 g of 4-iodo-3- nitrobenzoic acid methyl ester as a yellow solid (33% yield). A solution of 4-iodo-3-nitrobenzoic acid methyl ester (2.0 g, 6.50 mmol) in 25 mL of absolute alcohol and 15 mL of glacial acetic acid was treated with iron powder (3.6 g, 65.0 mmol) and the mixture was heated at 80 C. After 1 hour, the reaction mixture was filtered through a pad of silica, washed with ethanol, and concentrated in vacuo. The residue was diluted with a solution of potassium carbonate and extracted with ethyl acetate. The combined organic layers were washed with brine, dried over sodium sulfate, filtered, and concentrated in vacuo to give 1.6 g of 3-amino-4-iodobenzoic acid methyl ester as a white solid (88% yield). A solution of 3-amino-4-iodobenzoic acid methyl ester (1.59 g, 5.74 mmols) in 40 ML of dichloromethane was reacted with trifluoroacetic anhydride (3 mL, 21 mmol) at room temperature. After 30 minutes, the reaction mixture was concentrated in vacuo and the residue was taken up in cold water, filtered, and dried to give 2.1 g of the title product as an off-white solid (quantitative yield). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | at 0.11℃; for 15h; | Example 2 Preparation of 4-iodo-3-nitrobenzoic Acid Methyl Ester Using Trimethyl Orthoacetate A solution of <strong>[35674-27-2]4-iodo-3-nitrobenzoic acid</strong> (3 g, 10 mmol) in trimethyl orthoacetate (30 ml) is refluxed (?110 C.) for 15 hours and then solvent is evaporated under reduced pressure. The <strong>[35674-27-2]4-iodo-3-nitrobenzoic acid</strong> methyl ester is obtained as a yellow solid (3.11 g, 99% yield, 97.5% HPLC). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71.5% | With potassium carbonate; triethylamine; In acetonitrile; Petroleum ether; at 0 - 40℃; for 8h; | Example 2 Preparation of methyl 4-iodo-3-nitrobenzoate (Compound IV) 55 g (0.19 mol) <strong>[35674-27-2]4-Iodo-3-nitrobenzoic acid</strong> (Compound V), 16.5 g (0.12 mol) potassium carbonate and 550 ml acetonitrile were added into a reaction flask, and started to stir. The mixture was cooled to 0 to 5 C., and 52.9 ml (0.38 mol) triethylamine was added. The temperature was controlled below 10 C., and 71 ml (1.12 mol) iodomethane was added. The mixture was heated to about 40 C. for 8 hours, and concentrated under reduced pressure after completing the reaction until most of the acetonitrile was evaporated. The mixture was then extracted with 500 ml ethyl acetate, washed with water for three times, and the organic layer was dried over anhydrous sodium sulfate, filtered, and the filtrate was concentrated to the least amount, and then 300 ml petroleum ether was added, stirred for 30 min, and then filtered. The filter cake was washed with petroleum ether, and dried to obtain methyl 4-iodo-3-nitrobenzoate (Compound IV), about 41.2 g (0.13 mol), yield 71.5%. 1HNMR (400 MHz, DMSO-d6): delta 3.91 (s, 3H), 7.87 (dd, 1H, J1=8.08 Hz, J2=1.88 Hz), 8.26 (d, 1H, J=8.12 Hz), 8.34 (d, 1H, J=9.12 Hz); MS (m/z): 308 [M+H]. |
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