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CAS No. : | 107947-17-1 | MDL No. : | MFCD09751943 |
Formula : | C8H6BrClO2 | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | CLRJXWANIVYEHH-UHFFFAOYSA-N |
M.W : | 249.49 | Pubchem ID : | 22352523 |
Synonyms : |
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Signal Word: | Warning | Class: | |
Precautionary Statements: | P280-P305+P351+P338 | UN#: | |
Hazard Statements: | H302 | 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 |
---|---|---|
With potassium acetate;(1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; In N,N-dimethyl-formamide; at 95℃; for 12h; | A mixture of 3-bromo-4-chloro-benzoic acid methyl ester (3.13 g, 12.6 mmol), bis(pinacolato)diboron (4.79 g, 18.8 mmol), PdCI2(dppf)2 (0.74 g, 1.0 mmol), KOAc (3.69 g, 37.7 mmol) in DMF (50 mL) was sealed and heated at 95 0C for 12 hrs. The mixture was partitioned between ethyl acetate and water. Organic layer was separated, washed with water, brine, dried over MgSO4. After filtration and concentration, purification by silica gel chromatography eluting with ethyl acetate/hexane (1/9) gave 4-chloro-3-(4,4,5,5-tetramethyl-[1 ,3,2]dioxaborolan-2-yl)- benzoic acid methyl ester (3.5 g). NMR (DMSO-d6), δ, 8.19 (1 H, d, J = 2.1 Hz), 7.99( 1 H, dd, J = 2.1 , 8.4 Hz), 7.58(1 H, d, J = 8.4 Hz)1 3.85(3H, s), 1.31(12H, s). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With sulfuric acid; at 80℃; for 17h; | Example 1313.1[0208] Methyl-<strong>[42860-10-6]3-bromo-4-chlorobenzoate</strong> (13.1).; To a round bottom flask containing <strong>[42860-10-6]3-bromo-4-chlorobenzoic acid</strong> (5.0 g, 21.2 mmol) (commercially available from Aldrich, CAS No. 42860-10-6) was added a cold solution of MeOH (60 mL) and sulfuric acid (1.4 mL). The mixture was heated to 80 °C and monitored with TLC. After 17 hours, the reaction was cooled to room <n="87"/>temperature and diluted with water. The aqueous phase was extracted with diethyl ether (3 x 50 mL), and the combined organic layers were dried over anhydrous magnesium sulfate. After filtration, the organic solvent was removed in vacuo to yield white solid 13.1 (5.0 g, 96 percent yield). 1H NMR (400 MHz, CDCl3) delta ppm 8.28 (1 H, d, J=2.0 Hz), 7.93 (1 H, m), 7.52 (1 H, d, J= 8.2 Hz), 3.93 (3 H, s). |
130 mg | With sulfuric acid; at 70℃; | 3-Bromo-4-chlorobenzoic acid (200 mg, 0.849 mmol) was refluxed in the presence of concentrated sulfuric acid (5.49 mg, 0.042 mmol) in methanol (10 mL) at 70 °C for overnight. The reaction was monitored by TLC. After completion of the reaction, the solvent was removed by vacuum, and the compound was purified by column chromatography affording the title compound (130 mg). 1H NMR (400 MHz, CDCI3): delta 8.29 (d, 1 H, J = 2.0 Hz), 7.91 (dd, 1 H, J = 2.0 & 8.4 Hz), 7.52 (d, 1 H, J = 8.4 Hz), 3.92 (s, 3H). ESI-MS: 250.9 [M+H]+. |
With acetyl chloride; at 0 - 20℃; for 12h; | To a suspension of <strong>[42860-10-6]3-bromo-4-chloro-benzoic acid</strong> (10 g, 42.6 mmol) inMeOH (100 ml.) cooled with ice bath, was added acetyl chloride (30.4 mL, 0.43 mol) dropwise. The mixture was then stirred at room temperature for 12 hrs and concentrated to yield <strong>[42860-10-6]3-bromo-4-chloro-benzoic acid</strong> methyl ester as a yellow solid(10.6 g). NMR (CDCI3), delta, 8.28 (1 H, s), 7.91(1 H, brs), 7.52(1 H, brs), 3.92(3H, s). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
57% | In methanol; at 0℃; for 18h; | 4-Chloro-3-bromobenzoic acid 19a (2 g, 8.5 mmol) was dissolved in methanol (400 mL) and cooled to 0 C., next acetyl chloride (2.3 g, 30 mmol) was then added dropwise and stirring was continued for 18 hours, after the reaction was finished, the solvent was removed under reduced pressure, and the residue was purified by silica gel column chromatography (petroleum ether/ethyl acetate=10/1), so as to obtain the title product methyl 4-chloro-3-bromobenzoate 19b (1.2 g, yellow solid), and the yield was 57%. 1H NMR (400 MHz, CDCl3) delta 8.31 (d, J=1.9 Hz, 1H), 7.93 (dd, J=8.3, 1.9 Hz, 1H), 7.55 (d, J=8.3 Hz, 1H), 3.95 (s, 3H). |
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