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CAS No. : | 7463-51-6 | MDL No. : | MFCD00002315 |
Formula : | C8H9BrO | Boiling Point : | No data available |
Linear Structure Formula : | - | InChI Key : | WMUWDPLTTLJNPE-UHFFFAOYSA-N |
M.W : | 201.06 | Pubchem ID : | 81970 |
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 |
---|---|---|
With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate;palladium diacetate; In water; toluene; at 60℃; for 14.5h; | Production Example 9 In an atmosphere of nitrogen, a mixture of methyl 2-methyl-3-(4,4,5,5-tetrarnethyl-1,3,2-dioxaborolan-2-yl)benzoate, 4-bromo-3,5-dimethylphenol, palladium acetate, dicyclohexyl(2',6'-dimethoxybiphenyl-2-yl)phosphine, tripotassium phosphate, toluene and water was stirred for 14.5 hours with heating at 60C to obtain ethyl 4'-hydroxy-2,2',6'-trimethylbiphenyl-3-carboxylate. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With potassium carbonate; In N,N-dimethyl-formamide; at 90℃; for 24h;Inert atmosphere; | To a solution of 4-bromo-3,5-dimethylphenol (2.01g, lOmmol) and 3 -(methyl sulfonyl)propyl 4-methylbenzenesulfonate (3.5 lg, 12.0mmol) in N,N-dimethylformamide (20mL) was added potassium carbonate (1.80g, 13.0mmol), and the mixture was stirred at 90 C for 24 hr under nitrogen atmosphere. Water was added to the reaction mixture, and the mixture was extracted with ethyl acetate. The extract was washed successively with 1M aqueous sodium hydroxide solution and saturated brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The residue was purified by column chromatography (ethyl acetate : hexane=40:60-80:20), and the obtained crystals were recrystallized from heptane-ethyl acetate to give a colorless crystals product 25 (2.73g, yield 85%). |
67% | With potassium carbonate; In N,N-dimethyl-formamide; at 90℃; for 24h; | Weighing 4-bromo-3,5(dimethyl)phenol (2.0g, 10mmol), YZ-1 (2.92g, 10mmol), potassium carbonate (2.76g, 20mmol), dissolved in 20ml N,N-dimethyl formamide, in the reaction system 90 C stirring in oil bath 24 hours. In the reaction system by adding 150 ml ethyl acetate dilution, water sequentially, saturated salt water washing, anhydrous sulfuric acid nano dry, filtered, concentrated to obtain crude products, rapid column chromatography purification (petroleum ether: ethyl acetate: dichloromethane = 1:1:1), to obtain the product 12e (2.15g), yield 67%. |
With potassium carbonate; In N,N-dimethyl-formamide; at 70℃; for 46h;Product distribution / selectivity; | Example 9Synthesis of 2-bromo-l, 3-dimethyl-5- [3- (methylsulfonyl) propoxy] benzene; [0420][0421]4-Bromo-3, 5-dimethylphenol (40.00 g) , 3- (methylsulfonyl) propyl 4-methylbenzenesulfonate (72.71 g) and potassium carbonate (35.75 g) were added toN, N-dimethylformamide (400 mL) , and the mixture was stirred. The mixture was heated to 70C, stirred for 46 hr, and cooled to 5C. Water (200 mL) was added dropwise at 10C or below, seed crystal (60 mg) was added, and water (400 mL) was continuously added. After stirring for 2 hr, the precipitated crystals were collected by filtration, washed with water (400 mL) and dried to give the title compound (63.08 g) .XH NMR (300 MHz, CDC13) : delta 2.28-2.36 (m, 2H) , 2.38 (s, 6H) , 2.93-2.97 (m, 3H) , 3.20-3.26 (m, 2H) , 4.07 (t, J=5.8 Hz, 2H) , 6.63 (s, 2H) , 7.26 (s, 1H) . |
With potassium carbonate; In N,N-dimethyl-formamide; at 100℃; for 18h; | Step C: 2-bromo- 1,3 -dimethyl-5 -(3 -(methylsulfonyl)propoxy)benzene (34-3)To a solution of compound 34-2 (32.1 g, 110 mmol) in DMF (300 mL) was added 4-bromo-3,5- dimethylphenol (20.1 g, 100 mmol), and K2C03 (16.5 g, 120 mmol). The resulting mixture was stirred at 100 C for 18 hours. Then water was added and the mixture was extracted with ethyl acetate (150 mL x 3). The combined organic layers were washed with brine, dried and concentrated to give a residue. The residue was purified by chromatography on silica gel(petroleum ether:ethyl acetate = 3/1) to give compound 34-3. MS (ESI) m1z(M+H):32 1.0/323.0. | |
With potassium carbonate; In N,N-dimethyl-formamide; at 100℃; for 18h; | To a solution of compound 34-2 (32.1 g, 110 mmol) in DMF (300 mL) was added 4-bromo-3,5-dimethylphenol (20.1 g, 100 mmol), and K2C03 (16.5 g, 120 mmol). The resulting mixture wasstirred at 100 C for 18 hours. Then water was added and the mixture was extracted with ethylacetate (150 mL x 3). The combined organic layers were washed with brine, dried andconcentrated to give a residue. The residue was purified by chromatography on silica gel15 (petroleum ether:ethyl acetate= 3/1) to give compound 34-3. MS (ESI) m/z(M+Hf:321.0/323.0. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
3.5 g | With potassium carbonate; In N,N-dimethyl-formamide; at 20℃; for 12h; | Step 1: 3-((4-Bromo-3,5-dimethylphenoxy)methyl)-3-methyloxetane To a solution of 4-bromo-3,5-dimethylphenol (3.0 g) and K2CO3 (5.5 g) in N,N-dimethylformamide (10 mL) is added <strong>[78385-26-9]3-(bromomethyl)-3-methyloxetane</strong> (2.95 g). The mixture is stirred for 12 hours at room temperature and then partitioned between saturated aqueous NaHCO3 solution and ethyl acetate. The aqueous phase is extracted with ethyl acetate and the combined organic phases are dried (MgSO4). The solvent is evaporated and the residue is chromatographed on silica gel (cyclohexane/ethyl acetate 100:0?70:30) to give the title compound. Yield: 3.5 g; LC (method 4): tR=1.81 min; Mass spectrum (ESI+): m/z=285 [M+H]+. |
3.5 g | With potassium carbonate; In N,N-dimethyl-formamide; at 20℃; for 12h; | To a solution of 4-bromo-3,5-dimethylphenol (3.0 g) and K2CO3 (5.5 g) in N,N- dimethylformamide (10 mL) is added <strong>[78385-26-9]3-(bromomethyl)-3-methyloxetane</strong> (2.95 g). The mixture is stirred for 12 hours at room temperature and then partitioned between saturated aqueous NaHCO3 solution and ethyl acetate. The aqueous phase is extracted with ethyl acetate and the combined organic phases are dried (MgSO4). The solvent is evaporated and the residue is chromatographed on silica gel (cyclohexane/ethyl acetate 100:0?70:30) to give the title compound. Yield: 3.5 g; LC (method 4): tR = 1 .81 min; Mass spectrum (ESI+): m/z = 285 [M+H]+. |
3.5 g | With potassium carbonate; In N,N-dimethyl-formamide; at 20℃; for 12h; | To a solution of 4-bromo-3,5-dimethylphenol (3.0 g) and K2CO3 (5.5 g) in N,N- dimethylformamide (10 mL) is added <strong>[78385-26-9]3-(bromomethyl)-3-methyloxetane</strong> (2.95 g). The mixture is stirred for 12 hours at room temperature and then partitioned between saturated aqueous NaHCO3 solution and ethyl acetate. The aqueous phase is extracted with ethyl acetate and the combined organic phases are dried (MgSO4). The solvent is evaporated and the residue is chromatographed on sil ica gel (cyclohexane/ethyl acetate 100:0?70:30) to give the title compound. Yield: 3.5 g; LC (method 4): tR = 1 .81 min; Mass spectrum (ESI+): m/z = 285 [M+H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
251 mg | With caesium carbonate; In N,N-dimethyl-formamide; at 100℃; for 12.0h; | Step 2: 3-(4-Bromo-3,5-dimethylphenoxy)-2,2-dimethylpropan-1-ol To a mixture of 4-bromo-3,5-dimethylphenol (625 mg) and Cs2CO3 (5 g) in N,N-dimethylformamide (10 mL) is added 5,5-dimethyl-[1,3,2]dioxathiane-2-oxide (467 mg). The mixture is stirred for 12 hours at 100 C. and then partitioned between water and ethyl acetate. The organic phase is washed with brine and dried (MgSO4). The solvent is evaporated and the residue is purified by HPLC on reversed phase to give the title compound. Yield: 251 mg; LC (method 7): tR=1.16 min; Mass spectrum (ESI+): m/z=287 [M+H]+. |
372 mg | With caesium carbonate; In N,N-dimethyl-formamide; at 120℃; for 12.0h;Microwave irradiation; Sealed tube; | I n a m icrowave vial CS2CO3 (5.4 g) is added to a soltuion of 5,5-dimethyl- [1 ,3,2]dioxathiane 2-oxide (500 mg) and 4-bromo-3,5-dimethylphenol (670 mg) in Ν,Ν-dimethylformamide (5 mL). The vial is sealed and the mixture is heated to 120C for 12 hours. The mixture is partitioned between ethyl acetate and water. The organic phase is washed three times with 2 M aqueous NaOH and with brine. After drying (MgSO4) and concentration the residue is chromatographed on silica gel (cyclohexane/ethyl acetate 99:1→50:50) to give the title compound. Yield: 372 mg; LC (method 7): tR = 1 .17 min; Mass spectrum (ESI+): m/z = 287 [M+H]+. |
372 mg | With caesium carbonate; In N,N-dimethyl-formamide; at 120℃; for 12.0h;Microwave irradiation; Sealed tube; | I n a m icrowave vial CS2CO3 (5.4 g) is added to a soltuion of 5,5-dimethyl- [1 ,3,2]dioxathiane 2-oxide (500 mg) and 4-bromo-3,5-dimethylphenol (670 mg) in N,N-dimethylformamide (5 mL). The vial is sealed and the mixture is heated to 120C for 12 hours. The mixture is partitioned between ethyl acetate and water. The organic phase is washed three times with 2 M aqueous NaOH and with brine. After drying (MgSO4) and concentration the residue is chromatographed on silica gel (cyclohexane/ethyl acetate 99:1→50:50) to give the title compound. Yield: 372 mg; LC (method 7): tR = 1 .17 min; Mass spectrum (ESI+): m/z = 287 [M+H]+. |
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