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Search for reports by entering the product batch number.
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Search for reports by entering the product batch number.
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CAS No. : | 13031-43-1 |
Formula : | C10H10O3 |
M.W : | 178.18 |
SMILES Code : | CC(=O)OC1=CC=C(C=C1)C(C)=O |
MDL No. : | MFCD00017229 |
Boiling Point : | No data available |
InChI Key : | SMIOEQSLJNNKQF-UHFFFAOYSA-N |
Pubchem ID : | 83063 |
GHS Pictogram: |
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Signal Word: | Warning |
Hazard Statements: | H315-H319-H335 |
Precautionary Statements: | P261-P305+P351+P338 |
* 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 |
---|---|---|
72% | With tert.-butylnitrite; N-hydroxyphthalimide; In acetonitrile; at 80℃; for 24h;Schlenk technique; | into a 25mL Schlenk reaction tube added NHPI 1.0equivalent, dried in vacuum for 15 minutes, put on an oxygen sphere, under the oxygen atmosphere followed by adding acetonitrile 1mL, tert-butyl nitrite 2.0 equiv., P-acetoxyethyl benzene 0.5mmol, on the reaction tube add Poly tetra-fluoroethylene plug into the oil bath after the pot, and carry on reaction at 80 C for 24 h. After completion of the reaction, the solvent acetonitrile has been removed by concentration under reduced pressure, column chromatography, the eluent is petroleum ether / ethyl acetate (nu: nu = 10: 1), and then obtained 4-acetoxyacetophenone. Yield 72%, white solid; |
69% | With pyridine; dipotassium peroxodisulfate; oxygen; In acetonitrile; at 80℃; under 760.051 Torr; for 16h;Green chemistry; | General procedure: Ethylbenzene (3a) (0.0531 g, 0.5 mmol), K2S2O8 (0.2703 g, 1.0 mmol), pyridine (0.0158 g, 0.2 mmol) and CH3CN (1.0 mL) were added to an oven-dried pressure vessel with a magnetic stir bar. Then the pressure vessel was filled with dioxygen and the reaction mixture was stirred at 80 C for 16 hours (oil bath). After the completion of the reaction, the solvent was evaporated and the reaction mixture was purified with column chromatography (eluenet: ethyl acetate/PE = 1/10) to give acetophenone (4a) (0.0535 g yield 89%). |
10% | With (2,2?-bipyridine)Zn(CF3)2; zinc diacetate; copper(l) cyanide; zinc trifluoromethanesulfonate; N-fluorobis(benzenesulfon)imide; at 20℃; for 24h;Sealed tube; Glovebox; Inert atmosphere; | To a dried sealed tube (10 mL) equipped with a Teflon septum and a magneticstirring bar in a glove box were added successively CuCN (1.8 mg, 0.02 mmol), NFSI(189 mg, 0.60 mmol), (bpy)Zn(CF3)2 (144 mg, 0.40 mmol), Zn(OTf)2 (36 mg, 0.1 mmol)and Zn(OAc)2 (18 mg, 0.1 mmol). The solution of 4-ethylphenyl acetate (3a, 33mg,0.20 mmol) in PhCF3 (4.0 mL) was added into the tube. The reaction mixture wasstirred at room temperature for 24 h under air. The resulting mixture was filtered through celite, and the filtrate was concentrated under reduced pressure. The residuewas purified by column chromatography on silica gel with a gradient eluent ofpetroleum ether and ethyl acetate to give 4a-O (3.6 mg, 10%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With bromine; triethyl phosphite; In chloroform; nitrogen; acetic acid; isopropyl alcohol; | (a) alpha-Brom-4-acetoxyacetophenone There was added to a solution of 17.8 kg of p-acetoxy acetophenone in 90 liters of dry chloroform a solution of 9.2 kg of bromine in 20 liters of chloroform with stirring in a nitrogen stream within 3 hours. After the HBr formed was completely driven out by nitrogen, there were added 0.37 kg of glacial acetic acid and 1 kg of triethyl phosphite and stirring continued for 1 hour at 20 C. and for another 1/2 hour at reflux temperature. Then it was evaporated in a vacuum and the residue dissolved in isopropanol. After 8 hours the mixture was filtered with suction and dried at 40 C. in a vacuum. Yield: 20.8 kg=81% of Theory; M.P. 68 C.; DC (solvent:chloroform): 1 HF, no side spots. | |
With bromine; In dichloromethane; at 0 - 20℃; | Preparation of Compound I To a solution of 4-acetoxyacetophenone (1.0 eq) in dichloromethane on an ice bath was added bromine (1.05 eq). The bromine was added slowly at 0 C. The ice bath was removed and stirring continued at the ambient temperature until the reaction was complete (monitored by HPLC). The reaction mixture was concentrated in vacuum to provide 4-acetoxy-alpha-bromoacetophenone that was used without further purification. | |
With pyridinium hydrobromide perbromide; In 1,4-dioxane; for 5h; | Pyridinium bromide perbromide (33.6g, 0.105 mole) was added to a solution of 4- acetylphenyl acetate (17.8 g, 0.1 mole) in dioxane (100 mL). The heterogeneous mixture was stirred for 5 hours. During the course of the reaction the intensity of the red color decreased and a white solid was formed. The reaction mixture was diluted with ether (200 mL) and washed with water (3X100 mL), brine (75 mL), dried (MgS04) and removed in vacuo to give the desired product as an oil, which solidified upon standing at room temperature (26.0 g). This product was used in the next transformation without further purification. |
With bromine; In ethyl acetate; at 50℃; for 0.0216667h;Sealed tube; | 1, the preparation of raw materials:100 mL of a 4-acetoxyacetophenone ethyl acetate solution having a mass concentration of 16.6%Into the container, stirring to mix evenly sealed.Then, 200 mL of a bromine ethyl acetate solution having a mass concentration of 11.6%Placed in another container, sealed.2. With the apparatus of the present invention, Fig. 2,Follow the steps below:(1) The ethyl acetate solution containing 4-acetoxyacetophenone in the raw material tank 1 was passed through a metering pump 3Corning Microchannel Reactor 7,The ethyl acetate solution of the bromine in the raw material tank 2 is passed through the metering pump 4 into the Corning microchannel reactor 7;(2) Setting the flow rates of the ethyl acetate solution of the metering pump 3 and the metering pump 4 controlling the 4-acetoxyacetophenone:15 mL / min,The flow rate of the bromine-controlled ethyl acetate solution was 28.8 mL / min,The molar ratio of 4-acetoxyacetophenone to bromine was 1: 1.5,Set the heat exchanger temperature of 50 ;(3) the reaction channelThrough the stop valves 5 and 6 to prevent the back flow of materials;(4) After the mixing reaction in the Corning microchannel reactor 7, the reaction time is 1.3 min,The brominated product is continuously withdrawn and collected in a collection tank 8, The product was analyzed by LC.3. The purity of organic bromide in the reaction product was 80.5%Yield 72%. | |
With bromine; In chloroform; for 3h; | General procedure: The suitable aceticacid acetylphenylester derivative and bromine were separately dissolved in chloroform and the reaction was carried out by dropping bromine for 3 h. When the reaction conclude, solvent was evaporated and viscous liquid substance was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
> 99%Chromat. | With borane-ammonia complex; In methanol; water; at 20℃; for 0.0833333h; | General procedure: mpg-C3N4/Pd (4 mg) and the ketone or aldehyde (0.35 mmol)were suspended in methanol/water mixture (2 mL, 1:1) in apressure tube. Subsequently, AB (0.75 mmol) was addedand the solution was magnetically stirred for 2 (for aldehydes)or 5 min (for ketones) at room temperature. Aftercompletion of the reaction, the catalyst was filtered andwashed with methanol for further use. The solvent wasremoved under the reduced pressure. The yield of each alcoholwas determined by gas chromatography-mass spectrometry(GC-MS). |
1440 g | With 5%-palladium/activated carbon; hydrogen; In toluene; at 15 - 20℃; under 6000.6 Torr;Large scale; | Put 2880g of toluene, 1440g of p-acetoxyacetophenone (obtained in Example 1), and 72g of Pd / C (50% water content, 5% Pd on dry basis) into a 5L pressure reactor, followed by nitrogen, hydrogen After the replacement, the internal temperature was controlled at 15 to 20 C, and the reaction was stirred under a hydrogen pressure of 8 bar.After the reaction, Pd / C was recovered by filtration, the solvent was recovered by distillation of the filtrate, and the concentrate was further distilled under reduced pressure to obtain 1440 g of 1- (4-acetoxyphenyl) ethanol. The HPLC purity was 99.0%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With graphite oxide; In dichloromethane; at 30℃; for 1h;Green chemistry; | General procedure: To a solution of alcohols or phenols (3 mmol) and Ac2O (4.5 mmol; 9 mmol for dihydroxybenzenes) in CH3CN or CH2Cl2(2 mL) in a round-bottom flask was added GO (5 wt% of alcohols orphenols). The mixture was stirred at 20 C and the progress of the reaction was monitored by thin layer chromatography (TLC) analysis. After the completion of the reaction, the catalyst was filtered and washed with ethyl acetate (20 mL x 2). The filtrate was combined and washed with 15 mL of saturated sodium carbonate. The organic phase was dried over Na2SO4 and evaporated in vacuo to obtain the desired products. To determine the catalytic activity of Mn and K, we added MnO2, MnSO4 or KCl in the reaction between2-phenylethanol with Ac2O instead of GO and the yields of the corresponding ester (determined by 1H NMR) were listed in Table S1. |
With sulfuric acid; for 3h;Reflux; | General procedure: The suitable hydroxyacetophenone and acetic anhydride were refluxed with 2 drops concentrated sulfuric acid for 3 h.The reaction was checked using TLC. The reaction mixturewas poured into ice-water. The crystalline raw product was filtered and recrystallized from ethanol. | |
With potassium carbonate; In dichloromethane; at 20℃; for 24h; | General procedure: Ac2O (0.6 mL, 6 mmol) was added to a mixture of phenol (0.47 g, 5mmol), and K2CO3 (1.35 g, 10 mmol) in CH2Cl2 (25 mL). The mixture was stirred for 24 h at r.t. The resulting mixture was washed several times with H2O. The organic phase was dried (anhyd Na2SO4) and then evaporated under reduced pressure. Pure phenyl acetate was obtained in 95% yield (120 mg) after column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
12.25 g (94%) | With N-ethyl-N,N-diisopropylamine; In dichloromethane; | EXAMPLE 1 2-(4-Hydroxyphenyl)-6-(4-morpholinyl)-4H-pyran-4-one (Compound 1) 4'-Hydroxyacetophenone (10 g, 73.4 mmole) was suspended in 200 ml dichloromethane in a 500 ml one neck round bottom flask under nitrogen at 0 C. The suspension was treated with diisopropylethylamine (14.7 ml, 84.5 mmole) followed by acetyl chloride (6.0 ml, 84.5 mmole) in 1*50 ml dichloromethane slowly dropwise. The reaction mixture was stirred 30 minutes at 0 C. and then for 1 hour at room temperature. The mixture was washed with 1*100 ml 10% hydrochloric acid and the organics were dried over magnesium sulfate. The dried organics were concentrated in vacuo to a yellow oil. The oil was distilled via kugelrohr (high vacuum, 165 C.) to give 12.25 g (94%) of 4'-acetoxy-acetophenone as a white solid. |
Clean and dry 250-ml two neck RB flask was takenand fitted with condenser and addition funnel. About.5 mol of 4-hydroxyacetophenone was taken and 200 mlof chloroform was added to it with stirring. The reactionmixture was cooled at 5-10C and .5 mol of acetyl chloridewas added dropwise to the reaction mixture. Stirringwas continued for another 15 min and .5 mol of potassiumcarbonate was slowly added. Reaction was continuedfor another 4 h and monitored using TLC. Thereaction mass was transferred into 1-l beaker and washedtwice with water (2 × 250 ml). The chloroform layer wasseparated and washed with 10% NaOH solution (2 ×250 ml). The chloroform layer formed was separated and dried with anhydrous sodium sulphate. The chloroformlayer was filtered and concentrated under reduced pressureusing rotary vacuum, cooled and hexane was addedto it. Solid was precipitated which is filtered and the productwas air dried (Figure 2(a)). | ||
1660 g | With sodium carbonate; In ethyl acetate; at 20 - 30℃; for 8h;Large scale; | In a 10L reaction flask, 4080 g of ethyl acetate, 1360 g of p-hydroxyacetophenone, and 1272 g of sodium carbonate were sequentially added, and stirring was started, and 1335 g of acetyl chloride was added dropwise at a controlled temperature of 20-30 C.After the dropwise addition was completed, the mixture was kept under stirring for 8 hours, and then filtered. The filtrate was washed and separated with 3022 g of an 8% aqueous sodium hydrogen carbonate solution. The organic layer was recovered by distillation, and 1380 g of hexane was added to the concentrated residue. After the cake was dried, 1660 g of acetoxyacetophenone was obtained, and the HPLC purity was> 99.9%. |
Tags: p-Acetylphenyl acetate | Aryls | Ketones | Esters | Organic Building Blocks | 13031-43-1
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