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Structure of 51012-64-7
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CAS No. : | 51012-64-7 |
Formula : | C9H9BrO |
M.W : | 213.07 |
SMILES Code : | CC1=CC(C(CBr)=O)=CC=C1 |
MDL No. : | MFCD07364269 |
InChI Key : | BANFRNTVKCHZDE-UHFFFAOYSA-N |
Pubchem ID : | 10036129 |
GHS Pictogram: |
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Signal Word: | Danger |
Hazard Statements: | H302-H314 |
Precautionary Statements: | P260-P264-P270-P280-P301+P330+P331-P303+P361+P353-P304+P340-P305+P351+P338-P310-P363-P405-P501 |
Class: | 8 |
UN#: | 3261 |
Packing Group: | Ⅱ |
* 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 |
---|---|---|
96% | With Oxone; ammonium bromide; In methanol; for 0.666667h;Reflux; | General procedure: Oxone (1.352 g, 2.2 mmol) was added to the well stirred solution of substrate (2 mmol) and NH4Br (0.215 g, 2.2 mmol) in methanol (10 ml) and the reaction mixture was allowed to stir at room temperature (or reflux temperature). After completion of the reaction, as monitored by TLC, the reaction mixture was quenched with aqueous sodium thiosulfate, and extracted with ethyl acetate (3×25 ml). Finally, the combined organic layer was washed with water, dried over anhydrous sodium sulfate, filtered and removal of solvent in vacuo yielded a crude residue, which was further purified by column chromatography over silica gel (finer than 200 mesh) to afford pure products. All the products were identified on the basis of 1H NMR and mass spectral data. |
80% | With bromine; In 1,4-dioxane; diethyl ether; at 20℃; for 5h; | To a solution of 1-m-tolyl-ethanone (6.Og, 44.72mmol) in dioxane (5ml), bromine (7.14g, 44.72mmol) in dioxane (10ml) and ether (15ml) was added and stirred at room temperature for 5 hr. The reaction mixture was poured into ice water and the compound was extracted using ethyl acetate. The organic layer was washed with water and brine, dried over anhydrous sodium sulfate, filtered and then evaporated to give crude 2- bromo- 1-m-tolyl-ethanone, 7.6g (80%). The crude compound obtained was used in the next step without further purification. |
With bromine; In diethyl ether; at 0℃; | Example 21: 4-[2,5-Dioxo-4-hydroxymethyl-3-methyl-4-(3-methylphenyl)imidazolidin-l-yl]-2- trifluoromethyl-benzonitrile (Method A)Step I: 2-bromo- 1 -(3-methylphenyl)ethanone; [00339] To a solution of l-(3-methylphenyl)ethanone (2 g) in ethyl ether (20 mL) is added bromine (726 muL) at 00C. The mixture is treated with an aqueous solution of sodium bicarbonate, extracted with ethyl ether, dried over magnesium sulfate, concentrated and purified on silica gel (ethyl acetate/cyclohexane 0/100) to give the desired compound.TLC: Fr = 0.42 (ethyl acetate/cyclohexane 10/90). delta 1H NMR (CDCl3): 2.47 (s, 3H); 4.49 (s, 2H); 7.40-7.47 (m, 2H); 7.81-7.91 (m, 2H).LCMS: (Rt = 3.42 min): not ionisable. |
With N-Bromosuccinimide; trimethylsilyl trifluoromethanesulfonate; In acetonitrile; at 40℃;Darkness; | General procedure: Ketone (1 eq) and N-bromosuccinimide (NBS) (2 eq) were solved in acetonitrile and trimethylsilyl trifluoromethanesulfonate (TMS-OTf) (1 eq) was added. The reactions were stirred at T = 40 C until completeness, diluted with diethyl ether (2 ml), washed with H2O (3 x 2 ml), dried over Na2SO4 and concentrated under reduced pressure. This procedure provided bromoketones intermediates in 75-90% overall yield, with purities generally >90% as determined by HPLC-MS. The compounds was used without further purification. | |
With hydrogen bromide; bromine; acetic acid; at 0 - 5℃; | General procedure: General procedure to obtainalpha-bromoacetophenonederivatives Acetophenone derivative (10 mmol) was solved in acetic acid(50 mL) and hydrobromic acid (0.5 mL) mixture. Bromine(10 mmol, 0.52 mL) was added dropwise to this mixture at 0-5Ctemperatureandthemixturewasstirredfor6-7h.Afterthisperiod, the mixture was poured into ice-water, collapsed portionwas filtrated and after dryness it was crystallized from ethanol. | |
With N-Bromosuccinimide; toluene-4-sulfonic acid; In acetonitrile; at 50℃; for 24h; | General procedure: Synthesis of alpha-Aminocarbonyl Compounds by a Two-Step Method. First Step Synthesis of alpha-bromoacetophenone: to a solution of the acetophenone derivative (15.0 mmol, 1 equiv) in 8 mL of acetonitrile were added NBS (2.72 g, 15.3 mmol, 1.02 equiv) and p-toluenesulfonic acid (2.85 g, 15.0 mmol, 1 equiv). The reaction mixture was stirred for 24 h at 50 C. After that time, the solvent was evaporated under reduced pressure. A water solution of saturated NaHCO3 (30 mL) was then added, and the solution was extracted with dichloromethane (3 × 30 mL). The organic layers were combined and dried over Na2SO4. The solvent was evaporated, and the residue was purified by silica gel column chromatography (petroleum ether/ethyl acetate = 25:1, V/V) to afford the desired product in 82% yield as a white solid. After that, alpha-bromoacetophenone (5 mmol) and with aniline (5 mmol) and NaHCO3 (5 mmol) were added to a stirred solution of EtOH (20 ml) at room temperature for 12 h. The crude product was filtered under reduced pressure to give a yellow precipitate, which was recrystallized by EtOH and the yellow solid was isolated in 86% yield. | |
With bromine; In chloroform; at 20℃; for 1h;Cooling with ice; | 3-methylacetophenone (1.34 g, 10 mmol) was dissolved in 100 ml of chloroform.Br2 (1.91 g, 12 mmol) was slowly added dropwise under ice bath, and the mixture was stirred at room temperature for 1 h.After completion of the reaction, the reaction was quenched with saturated sodium sulfite, and the organic phase was washed with saturated sodium bicarbonate, and saturated brine.After dried over anhydrous sodium sulfate, the solvent was removed in vacuo to give a crude product 2.13g. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Typical examples of the halomethyl phenyl ketones (2) wherein X is a bromine atom include 2 -bromoacetophenone, 2-bromo-3'-chloroacetophenone, 2-bromo-3'-bromoacetophenone, 2-bromo-3'-fluoroacetophenone, 2-bromo-3'-methylacetophenone, 2-bromo-3'-ethylacetophenone, 2-bromo-3'-propylacetophenone, 2-bromo-3'-butylacetophenone, 2-bromo-3'-methoxyacetophenone, 2-bromo-3'-ethoxyacetophenone, ... | ||
Preparation Example 5 Preparation of 2-bromo-3'-methylacetophenone 31-methylacetophenone was used as a raw material and the target compound was obtained in the same manner as in Preparation Example 1. 1H-NMR (CDCl3, ppm) 2.43 (s, 3 H), 4.45 (s, 2 H), 7.35~7.44 (m, 3 H), 7.80 (s, 1 H) | ||
With bromine; acetic acid; at 20℃; for 3h; | General procedure: 6.02.01.01 2-bromo-1-(4-fluoro-3-methyl-phenyl)-ethanone 0.67 mL bromine was added to 2 g 1-(4-fluoro-3-methyl-phenyl)-ethanone in 10 mL conc. acetic acid. The reaction was stirred for 3 h at RT and added to ice water. The precipitate was filtered, washed with water and dried to give 2.7 g desired product. Rt: 1.10 min (method B), (M+H)+: 231 By using the same synthesis strategy as for 2-bromo-1-(4-fluoro-3-methyl-phenyl)-ethanone the following compound was obtained: |
With bromine; acetic acid; at 20℃; for 3h; | General procedure: 6.02.01.01 2-bromo- 1 -(4-fluoro-3-methyl-phenyl)-ethanone 0.67 mL bromine was added to 2 g l-(4-fluoro-3-methyl-phenyl)-ethanone in 10 mL cone, acetic acid. The reaction was stirred 3h at RT. The mixture was added to ice water. The precipitate was filtered, washed with water and dried to give 2.7 g desired product. Rt: 1.10 min (method A), (M+H)+: 231 | |
With bromine; acetic acid; at 20℃; for 3h; | General procedure: 6.02.01.01 2-bromo- 1 -(4-fluoro-3-methyl-phenyl)-ethanone 0.67 mL bromine was added to 2 g l-(4-fluoro-3-methyl-phenyl)-ethanone in 10 mL cone, acetic acid. The reaction was stirred for 3h at RT and added to ice water. The precipitate was filtered, washed with water and dried to give 2.7 g desired product. Rt: 1.10 min (method B), (M+H)+: 231 | |
With bromine; acetic acid; at 20℃; for 3h; | General procedure: 6.02. Synthesis of Imidazoles [0157] 6.02.01 2-bromo-1-(4-fluoro-3-methyl-phenyl)-ethanone 6.02.01.01 2-bromo-1-(4-fluoro-3-methyl-phenyl)-ethanone [0158] 0.67 mL bromine was added to 2 g 1-(4-fluoro-3-methyl-phenyl)-ethanone in 10 mL conc. acetic acid. The reaction was stirred 3 h at RT. The mixture was added to ice water. The precipitate was filtered, washed with water and dried to give 2.7 g desired product. [0159] Rt: 1.10 min (method A), (M+H)+: 231 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With water; In acetonitrile; at 125℃; for 0.833333h; | Step 2: 2-hydroxy-l-(3-methylphenyl)ethanone; [00340] A solution of 2-bromo- 1 -(3 -methylphenyl)ethanone (1 g) in acetonitrile (2.5 mL) and water (13 mL) is treated under microwave irradiation (125C, 50 min). The same experiment is repeated three times. All the vials are collected, extracted with DCM, dried over magnesium sulfate and concentrated under vacuum to give the desired compound.TLC: Fr = 0.15 (ethyl acetate/cyclohexane : 10/90). delta 1H NMR (CDCl3): 2.47 (s, 3H); 4.90 (s, 2H); 7.41-7.49 (m, 2H); 7.74-7.78 (m, 2H). | |
29 g | With water; sodium hydroxide; In ethanol; for 20h;Reflux; | 50 g of 2-bromo-1-(3-methylphenyl)ethanone was added to 600 ml of ethanol, 100 ml of water and 80 g of sodium hydroxide were added, and the mixture was heated under reflux for 20 hours, cooled, concentrated, and then added with ethyl acetate to separate the liquid. After drying and concentrating, the residue was separated by column to give 29 g of 1-(3-methylphenyl)-2-hydroxyethanone. |
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