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CAS No. : | 50671-05-1 | MDL No. : | MFCD03424813 |
Formula : | C11H11BrO3 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | IFSMFGOJDWUHEW-UHFFFAOYSA-N |
M.W : | 271.11 | Pubchem ID : | 2757148 |
Synonyms : |
|
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302-H315-H319 | Packing Group: | N/A |
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 |
---|---|---|
92% | With triethylamine; magnesium chloride; In acetonitrile; at 20℃; | Experimental operation: Take malonate potassium salt 1.00g (about 5.47mmol) and anhydrous magnesium chloride was added 0.65g (about 6.84mmol) in 25mL round bottom flask, 0.55g triethylamine was dropped after 6mL dissolved in acetonitrile, stirred at room temperature for 30min. Then dropped by 2mL acetonitrile dissolved 0.48g (2.5mmol) of o-bromobenzoyl chloride 1e, supplemented triethylamine 0.06mL, stirred at room temperature overnight. Post-treatment: 30mL of water was added to dilute the reaction solution, and then were added 30,20,20mL ethyl acetate and the ethyl acetate layer was collected. After washing with saturated brine 30mL ethyl acetate layer was dried over anhydrous sodium sulfate, and spin dry column chromatography (PE: EA = 15: 1) 2e of product obtained is isolated, a yield of 92% |
92% | Experimental operation: Take malonate potassium salt 1.00 g (about5.47 mmol) of anhydrous magnesium chloride and 0.65 g (about 6.84mmol) in 25 mLround bottom flask, was added dropwise 0.55 g of triethylamine was added after6 mL of acetonitrile was dissolved, followed by stirring at room temperature for30 min.Then dropped by 2 mL of acetonitrile was dissolved 0.48 g (2.5 mmol) o-bromobenzoyl chloride 1e, supplemented with triethylamine 0.06 mL, stirred atroom temperature overnight. After treatment: 30 mL of water was added to dilutethe reaction solution, and then were added 30,20,20 mL ethyl acetate, and theethyl acetate layer was collected. After, 30 mL with saturated brine ethylacetate layer was dried over anhydrous sodium sulfate, and spin dry columnchromatography (PE: EA = 15: 1) to give the product isolated 2e, in 92% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | With copper(l) iodide; potassium carbonate; propionic acid; In isopropyl alcohol; at 100℃; for 24h;Sealed tube; Inert atmosphere; Molecular sieve; | General procedure: 4.3.1. General procedure II for the CuI-catalyzed synthesis of 2 a-n. An oven-dried 10 mL vial equipped with a magnetic stir barwas charged with CuI (0.05 mmol, 10 mg) and K2CO3 (1 mmol,138 mg). The sealed tube was evacuated and backfilled with argon (two times). Then, them<strong>[50671-05-1]ethyl 3-(2-bromophenyl)-3-oxopropanoate</strong> 1 (1 mmol), propionic acid (22 mg, 0.3 mmol) and freshly distilled isopropanol (2 mL) were added and the reaction mixturewas stirredat 100 C for 24 h. After cooling to room temperature, the reaction mixture was diluted with water (15 mL) and extracted with EtOAc(320 mL). The combined organic layers were dried over anhydrous MgSO4, filtered and the solvents were evaporated in vacuo. The crude product was purified by flash column chromatography on silica gel to afford the 1-naphthol 2 in analytically pure form. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | General procedure: Method A:16,17 A two-necked round-bottomed flask equipped with a reflux condenser and a magnetic stir bar was charged with the 2-bromobenzoic acid (20mmol) and freshly distilled methanol (25mL). The solution was heated in a hot water bath, conc. H2SO4 (8mmol) was added slowly and the reaction mixture was refluxed for 24h. After cooling to room temperature around half of the amount of the solvent was removed in vacuo and the residue was partitioned between water (50mL) and diethyl ether (70mL). The organic layer was separated and washed with saturated NaHCO3 (2×50mL), water (50mL) and brine (50mL), dried over anhydrous MgSO4 and the volatiles were removed under reduced pressure. The crude product thus obtained was purified by flash chromatography on silica gel to afford the alkyl-2-halobenzoate. (0023) In a two-necked round-bottomed flask equipped with a reflux condenser and a magnetic stir bar the alkyl 2-halobenzoate (22.5mmol) was dissolved in freshly distilled dry THF (30mL) under argon. The solution was cooled to 0C using an ice bath and NaH (60% in mineral oil, 15mmol) was added portionwise. After stirring for 15min a solution of the alkyl acetate (15mmol) in dry THF (30mL) was added dropwise to the reaction mixture at 0C. The mixture was warmed up, stirred at room temperature for 2h and heated under reflux for 24h. After cooling to room temperature around half of the amount of the solvent was removed in vacuo and the reaction mixture was diluted with toluene (50mL). The resulting mixture was washed with 2N HCl (50mL), saturated NH4Cl (50mL), dried over anhydrous MgSO4 and the volatiles were removed under reduced pressure. The crude product was purified by flash column chromatography on silica gel to afford the alkyl 3-(2?-halophenyl)-3-oxo-propanoate 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | Experiment operation: Take 0.452g (2mmol) 2e in 25mL round bottom flask was added 0.16g of sodium ethoxide was dissolved with 10mL ethanol, stirred for fifteen minutes at room temperature, followed by taking 0.162mL (2mmol) -propenone in the flask, stirred at room temperature 2h . Post-treatment: 5% hydrochloric acid was added to dilute the reaction solution, and then were extracted with ethyl 30,20,20mL aqueous phase was washed with saturated brine and good oil layer, spin dried over anhydrous sodium sulfate, column chromatography (the PE: EA = 10: 1) to give the product isolated 3e, yield 85% | |
85% | Experiment operation: take 0.452 g (2 mmol) 2e in 25 mL roundbottom flask, 0.16 g of sodium ethoxide was added after 10 ml ethanol solutionwas added and stirred for 15 minutes at room temperature, followed by taking0.162 mL (2 mmol) in propenone flask, stirred at room temperature 2 h.Post-treatment: 5% hydrochloric acid 30,20,20 mL was added to dilute thereaction solution, and then were extracted with ethyl acetate and the aqueousphase was washed with saturated brine and dried over anhydrous sodium sulfateand purified by spin column chromatography (PE: EA = 10: 1) to give the isolatedproduct 3e, a yield of 85%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With copper(l) chloride; dibenzoyl peroxide; In N,N-dimethyl-formamide; at 110℃; | In the reaction flask by adding 3 - (2-bromophenyl) - 3- oxo ethyl propionate (0.269g, 1 . 0mmol), triethyl phosphite (1.162g, 7 . 0mmol), cuprous chloride (0.010g, 0 . 1mmol), benzoyl peroxide (1.694g, 7 . 0mmol) and dimethyl formamide (5 ml), 110 C reaction;TLC until the complete end tracking of the reaction;After the reaction the crude product by column chromatography (petroleum ether: ethyl acetate = 4:1), to obtain the target product (yield 79%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydride; In toluene; at 70℃; for 0.333333h;Inert atmosphere; | 97.1 o-bromoacetophenone as starting material,2.5 eq of NaH and 2.0 eq of diethyl carbonate were added to the toluene.Heated at 70 C under nitrogen for 20 min.After the reaction,Add cold water to room temperature,Add glacial acetic acid to the system neutral,Extracted with ethyl acetate (50 mL×3).Divide the organic layer,Washed with 10 ml of saturated saline solution,Dry over anhydrous sodium sulfate,The solvent was distilled off under reduced pressure.Crude column chromatography(petroleum ether: ethyl acetate = 40:1)Compound 97-1,O-bromobenzoylacetate; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
39% | With zinc(II) iodide; In dichloromethane; at 110℃; for 0.5h;Sealed tube; | General procedure: 1,4-naphthoquinone (1.5equiv.) ZnI2 (0.7equiv.) and b-keto esters5 a-n (1.0 equiv.) were dissolved in dry CH2Cl2(6 mL) in a 10mLreaction glass vial containing a tiny stirring magnet The vial wassealed tightly with an aluminium-Teflon crimp top and themixture was irradiated for 30 min at a pre-selected temperature of110 C, with an irradiation power of 60W. After the reaction, thevial was cooled to 50 C by gas jet cooling. The crude mixture wasportioned between CH2Cl2 and saturated solution of sodium chloride(6 mL) and the aqueous layer was extracted with methylenchloride (3 6 mL). The combined organic layer were dried onSodium sulfate anhydrous, filtered and the solvent was removedunder reduce pressure. Then, final crude compounds were purifiedby flash chromatography over silica gel. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With ammonium acetate; acetic acid; In toluene; at 140℃; for 0.333333h;Molecular sieve; Sealed tube; | General procedure: b-keto esters 5 a-n (1.0 equiv.), Ammonium acetate (3.0 equiv.)and Acetic acid (drops) were dissolved in dry Toluol (6 mL) in a10 mL reaction glass vial containing a tiny stirring magnet andmolecular sieves. The vial was sealed tightly with an aluminium-Teflon crimp top and the mixture was irradiated for 20 min at apre-selected temperature of 140 C, with an irradiation power of60W. After the reaction, the vial was cooled to 50 C by gas jetcooling. The crude mixture was portioned between ethyl acetateand saturated solution of Sodium bicarbonate (15 mL of each) andthe aqueous layer was extracted with ethyl acetate (3 15 mL). Thecombined organic layer were dried on Sodium sulfate anhydrous,filtered and the solvent was removed under reduce pressure. Then,final crude compounds were purified by flash chromatography oversilica gel. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With zinc(II) iodide; In dichloromethane; at 110℃; for 0.5h;Sealed tube; Microwave irradiation; | General procedure: 1,4-naphthoquinone (1.5equiv.) ZnI2 (0.7equiv.) and b-keto esters5 a-n (1.0 equiv.) were dissolved in dry CH2Cl2(6 mL) in a 10mLreaction glass vial containing a tiny stirring magnet The vial wassealed tightly with an aluminium-Teflon crimp top and themixture was irradiated for 30 min at a pre-selected temperature of110 C, with an irradiation power of 60W. After the reaction, thevial was cooled to 50 C by gas jet cooling. The crude mixture wasportioned between CH2Cl2 and saturated solution of sodium chloride(6 mL) and the aqueous layer was extracted with methylenchloride (3 6 mL). The combined organic layer were dried onSodium sulfate anhydrous, filtered and the solvent was removedunder reduce pressure. Then, final crude compounds were purifiedby flash chromatography over silica gel. | |
With copper(II) bis(trifluoromethanesulfonate); for 10h;Inert atmosphere; Reflux; | 97.2 ethyl o-bromobenzoylacetate,Dissolved in 5% with copper 5% triflate,0.6 eq of 1,4 benzoquinone was slowly added dropwise under nitrogen protection.Heated back to reflux for 10 h,Cool to room temperature.NH4Cl is quenched,Extracted with ethyl acetate (50 mL×3).Divide the organic layer,Washed with 10 ml of saturated saline solution,Dry over anhydrous sodium sulfate,The crude product obtained by evaporation of ethyl acetate was purified by silica gel column chromatography.(Petroleum ether: ethyl acetate = 20:1) Compound 97-2 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Ethyl potassium malonate (1 .39 g, 8.2 mmol) was suspended in dry MeCN (22 mL) under a flow of nitrogen, and the mixture was cooled to 10C. Et3N (1.2 mL, 8.6 mmol) and MgCI2 (935 mg, 9.84 mmol) were added and the reaction was stirred at rt for 2 h 30 min. The reaction was once again cooled to 10C and 2-bromobenzoyl chloride (900 mg, 4.1 mmol) followed by further Et3N (1 14 muIota, 0.82 mmol) were added. The mixture was stirred at rt overnight. The reaction was quenched with a saturated NH4CI solution and extracted with EtOAc. The combined organic layers were dried over MgS04, filtered and evaporated in vacuo. The crude product was purified by flash chromatography on silica gel using a gradient of EtOAc in cHex to yield the desired product 2A (379 mg, 34%) as a mixture of tautomers, which was used in the following step without further purification. 1H NMR (400MHz, CDCI3) delta 7.63-7.58 (m, 1 H), 7.39-7.21 (m, 2H), 4.16 (q, 2H), 3.99 (s, 2H), 1 .22 (t, 3H) - tautomer 1 , ethyl 3-(2-bromophenyl)-3-oxopropanoate 1H NMR (400MHz, CDCI3) delta 12.40 (s, 1 H), 7.52-7.45 (m, 1 H), 7.39-7.21 (m, 2H), 5.43 (s, 1 H), 4.25 (q, 2H), 3.99 (s, 1 H), 1.31 (t, 3H) - tautomer 2, (Z)-ethyl 3-(2-bromophenyl)-3- hydroxyacrylate MS (ES) C11H11BrO3 requires: 270/272, found: 271/273(M+H), -100% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: ammonium formate / ethanol / 20 h / Reflux; Schlenk technique; Inert atmosphere 2: sulfur; caesium carbonate / acetonitrile / 48 h / 90 °C / Inert atmosphere; Schlenk technique |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: ammonium formate / ethanol / 20 h / Reflux; Schlenk technique; Inert atmosphere 2: sulfur; caesium carbonate / acetonitrile / 48 h / 90 °C / Inert atmosphere; Schlenk technique |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: ammonium formate / ethanol / 20 h / Reflux; Schlenk technique; Inert atmosphere 2: sulfur; 1,10-Phenanthroline; copper; sodium phosphate / acetonitrile / 20 h / 90 °C / Inert atmosphere; Schlenk technique |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine In toluene at 120℃; for 48h; Dean-Stark; Overall yield = 74 percent; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With Candida antarctica lipase B; Selectfluor In aq. phosphate buffer at 50℃; for 12h; Enzymatic reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: Selectfluor; Candida antarctica lipase B / aq. phosphate buffer / 12 h / 50 °C / pH 7.4 / Enzymatic reaction 2: D-glucose / aq. phosphate buffer / 30 °C / pH 6.5 / Microbiological reaction |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1.4 g | In toluene at 100℃; for 2h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: toluene / 2 h / 100 °C 2: bis(η3-allyl-μ-chloropalladium(II)); tBu-RuPhos; potassium carbonate / tetrahydrofuran / 36 h / 35 °C / Inert atmosphere; Schlenk technique |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: ammonium acetate / methanol / Reflux 2: [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I); 1,10-Phenanthroline / acetonitrile / 50 °C |
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