| 98% |
In pyridine for 1.16667h; Cooling with ice; |
|
| 97% |
With montmorillonite K-10 In dichloromethane at 40℃; for 0.5h; |
|
| 96% |
With trifluorormethanesulfonic acid In acetonitrile at 20℃; for 1h; |
4.2. General procedure for O-acylation of phenols in TfOH
General procedure: Phenol (0.28 mmol) and acyl chloride (0.84 mmol, 3 equiv) were dissolved in 1% TfOH/CH3CN (1 ml) at room temperature. The reaction mixture was stirred at same temperature for an hour, then poured into cold water and ethyl acetate. The organic layer was washed with 1 M HCl, saturated NaHCO3, and saturated NaCl, and dried over MgSO4, then filtered. The filtrate was concentrated to afford O-acylated products. All spectral data were identical with the literatures.[27], 27(a), 27(b), 27(c), 27(d), 27(e), 27(f), 27(g) and 27(h) |
| 96% |
With P2W18O62(6-)*6H(1+)*14H2O In neat (no solvent) at 20℃; for 0.15h; Green chemistry; |
Typical benzoylation procedure
General procedure: The procedure was done in a well-ventilated hood. In a 10mL flask, benzoyl chloride(1 mmol, 0.16 ml) was added to the appropriate amine or phenol (1 mmol) and the mixture was stirred at room temperature in the presence of 0.003 g H6P2W18O62*14H2O as catalyst under solvent-free conditions for the appropriate time. During the reaction, the formation of hydrogen chloride gas was observed. After completion of the reaction (as monitored by TLC), diethyl ether (8 mL) was added, and the products were obtained by filtration. The products were then recrystallized from n-hexane/diethyl ether to give the N-Bz and O-Bz derivatives in the yields specified in Table 2. |
| 95% |
With pyridine for 1h; Heating; |
|
| 95% |
With 1,4-diaza-bicyclo[2.2.2]octane for 0.166667h; |
|
| 95% |
With zinc oxide at 20℃; for 0.5h; |
|
| 93% |
at 20 - 60℃; for 12h; |
2
A mixture of 7.0 gm (0.05 mole) of benzoyl chloride and 4.7 gm (0.05 moles) of phenol and 0.1 gm of boron carbide was heated to about 60° C. for 12 hours. The semi-solid material was allowed to cool to room temperature. A solid material was recovered and dissolved in acetone, filtered to remove the boron carbide catalyst. The acetone was removed at reduced pressure and the remaining solid was identified as phenyl benzoate by its infrared spectra. The yield of product was 93%. |
| 92% |
With titanium(IV) dioxide at 25℃; for 0.5h; |
|
| 91% |
Stage #1: phenol With potassium mirror In trihexyltetradecylphosphonium decanoate; toluene at 80℃; for 3h;
Stage #2: benzoyl chloride In trihexyltetradecylphosphonium decanoate; toluene at 80℃; for 2h; |
13
13. Synthesis of a phenoxide in a phosphonium-based ionic liquid and its reactivity; [00065] Phenol (0.2 g, 2.13 mmol) was added to IL 103 (5.0 mL) followed bytoluene (0.5 mL) to reduce viscosity. Potassium metal previously washed with THF (0.12 g, 3.19 mmol) was added to the reaction mixture and it was heated at 80 °C for 3 hours under nitrogen. A white precipitate formed. The excess potassium metal was removed and one equivalent of benzoyl chloride was added and the mixture was heated at 80 °C for 2 hours. No color change was observed. The reaction mixture was then quenched with water and extracted with dichloromethane. The extracts were dried with anhydrous magnesium sulphate and analyzed by GC-MS and the data was consistent with a 91 % yield of phenyl benzoate. |
| 91% |
With dmap; triethylamine In dichloromethane at 0 - 20℃; |
|
| 90% |
With potassium carbonate; sodium chloride at 64℃; for 0.0333333h; Microwave irradiation; Sealed tube; Green chemistry; |
Typical Procedure for Benzoylation of Phenol
Phenol (2.0 mL, 20.0 mmol) was mixed with well ground K2CO3 (1.5 g, 10.0 mmol) and NaCl (1.5 g)mixture and transferred into the quartz reaction vessel. To this reaction mixture, benzoyl chloride (2.3 mL, 20.0 mmol) was added and mixed thoroughly. The reaction vessel was placed into the microwave reactor under sealed conditions with a stirrer and irradiated at the power of 100 W, 70 °C, and 5 bar (maximum pressure) for 2 min. During the reaction, the pressure of the reaction vessel raised to 4.8bar. The completion of the reaction was monitored through TLC. After completion of the reaction, the reactor was allowed to coolalong with the reaction vessel for 10min. The reaction mixture was then poured into ice water. The solid product thus obtained was filtered and washed with cold water. It was then recrystallized from methano/lwater to obtain the desired phenyl benzoate (2a), 3.5 g, 90%yield, mp70 °C. |
| 90% |
Stage #1: phenol With N,N,N-trimethyl-2-hydroxyethyl-ammonium hydroxide In water monomer at 20℃; for 0.25h;
Stage #2: benzoyl chloride In water monomer at 20℃; for 24h; |
the synthesis of O-substituted phenolic derivatives.[13]
General procedure: A typical procedure: A flask was charged with phenol (3.0 mmol) and choline hydroxide (0.66 mL). Then, the mixture was stirred at room temperature in open air for 15 min. Next, benzyl bromide (3.0 mmol) was added into the flask, then the resulting mixture (two phases: top ChOH layer and bottom benzyl bromide layer) allowed to stir at room temperature for 24 h. The reaction mixture (two phases: top product layer and bottom aqueous ChOH layer) was extracted with diethyl ether (3 × 10 mL). The combined organic layers were washed with water, then dried with anhydrous Na2SO4, and evaporated under reduced pressure. The crude mixture was purified by column chromatography on silica gel (hexanes/ethyl acetate). Benzyl phenyl ether (3a); 1H NMR (400 MHz, CDCl3) δ (ppm): 7.48-7.40 (m, 4H), 7.37-7.28 (m, 3H), 7.03-6.97 (m, 3H), 5.10 (s, 2H); 13C NMR (100 MHz, CDCl3) δ (ppm): 158.8, 137.1, 129.5, 128.6, 127.9, 127.5, 120.9, 114.9, 69.9. |
| 90% |
With dmap; triethylamine In dichloromethane at 0 - 20℃; for 12h; Schlenk technique; Inert atmosphere; |
|
| 89% |
With triethylamine In dichloromethane for 0.5h; Reflux; |
|
| 89% |
Stage #1: phenol With manganese(IV) oxide; naphthalene; lithium In tetrahydrofuran at 20℃; for 0.166667h;
Stage #2: benzoyl chloride In tetrahydrofuran at 20℃; for 0.5h; |
Phenyl 3-Chlorobenzoate (1c); Typical Procedure
General procedure: A 25 mL flask was charged with lithium (0.07 g, 9.68 mmol),naphthalene (0.19 g, 1.48 mmol), anhyd MnI2 (1.45 g, 4.71 mmol), and freshly distilled THF (10 mL) under argon pressure,and the mixture was stirred for 1 h at r.t. To the resultingslurry, containing 2.5 mmol of highly active manganese, wasadded PhOH (0.47 g, 5.0 mmol) and the resulting mixture wasstirred at r.t. for 10 min. Neat 3-chlorobenzoyl chloride (0.88 g,5.0 mmol) was then added to the flask, and the mixture wasstirred at r.t. for 30 min. The reaction was then quenched with3 M aq HCl, and the mixture was extracted with Et2O (3 × 10 mL).The organic layers were combined and washed with sat. aqNaHCO3 (3 × 10 mL), sat. aq Na2S2O3 (3 × 10 mL), and brine (3 ×10 mL), then dried (MgSO4). Column chromatography (silica gel,1% EtOAc-hexanes) gave a pale-yellow solid.yield: 0.96 g (83%). |
| 89% |
With pyrographite; sodium hydroxide |
2.2 Synthesis of organic esters
General procedure: 2.35g phenol (0.025mol) for OE1 and 3.61g of 1-naphthol (0.025mol) for OE2 was added to 20ml of 5% NaOH solution in separate flasks. 0.75g decolorizing carbon was added in each flask and was filtered off. Solutions were separately poured into 100ml two necked flasks and 7.0g of benzoyl chloride (2.9ml, 0.025mol)) was added in each flask while stirring vigorously for 10-15min until odor of benzoyl chloride disappeared. Solid products obtained were filtered off using Buckner funnel followed by washing with cold water. The products were then recrystallized from 30ml rectified spirit. White crystals appeared which were removed from mother liquor by filtration and dried in the air (Scheme 1 |
| 88% |
With caesium fluoride In acetonitrile at 82℃; |
|
| 88% |
With caesium fluoride In acetonitrile at 82℃; |
|
| 88% |
With triethylamine In dichloromethane at 0 - 20℃; |
3 2.3. Synthesis of phenyl benzoate (1)
In a round bottom flask, first we dissolved 14 benzoyl chloride (0.83mL, 7.1mmol) in 15mL of 15 dichloromethane and then stirred it well at 0°C. To this solution, 16 triethyl amine (1.98mL, 14.2mmol) was added dropwise followed by mixture of 17 phenol (0.69mL, 7.81mmol) and dichloromethane (5mL), and stirred it overnight at room temperature. After overnight stirring this mixture was poured into ice cold 18 water followed by its extraction with dichloromethane. The organic layer was washed with water and dried over Na2SO4. Then solvent was evaporated and then the reaction mixture was purified by column chromatography to afford 9 phenyl benzoate (1.23g, 88%) as a white solid powder. 1H NMR (200MHz, CDCl3) δ: 7.11-7.25 (m, 3H), 7.31-7.39 (m, 2H), 7.39-7.50 (m, 2H), 7.52-7.62 (m, 1H), 8.10-8.19 (m, 2H). |
| 86% |
With triethylamine In dichloromethane at 0℃; for 5h; |
|
| 85% |
With sodium hydroxide for 0.5h; |
|
| 83% |
With triethylamine at 50℃; for 3h; |
|
| 83% |
With triethylamine In dichloromethane at 20℃; for 0.5h; |
|
| 77% |
With Mg-Al hydrotalcite with Mg/Al molar ratio in 2-3.5 In water monomer at 20℃; for 0.0833333h; |
|
| 76% |
With sodium hydroxide |
|
| 74% |
With pyridine; aluminum(III) oxide at 109 - 111℃; for 0.0666667h; microwave irradiation; |
|
| 70% |
With zinc oxide at 40℃; for 2h; |
|
| 65% |
In dichloromethane at 25℃; for 3h; ultrasound; |
|
| 48.3% |
With pyridine for 6h; |
|
|
With C-200 In tetrahydrofuran for 0.333333h; Heating; var. reagents; |
|
|
With triethylamine In dichloromethane at 0℃; further bases effect; |
|
|
With magnesium; benzene |
|
|
With aluminium chloride anhydrous; benzene |
|
|
With sulfur(IV) oxide |
|
|
With anhydrous tin tetrachloride |
|
|
With sodium hydroxide |
|
|
With zinc powder |
|
|
With potassium carbonate; benzene |
|
|
With 1-methylpyridine-2-thione; sodium hydroxide 1.) H2O, CHCl3; 2.) rt. 1.5 h; Yield given. Multistep reaction; |
|
|
In pyridine |
|
|
With pyridine Heating; |
|
|
In pyridine |
|
|
With triethylamine In dichloromethane |
|
|
With sodium hydroxide for 0.5h; |
|
|
Stage #1: benzoyl chloride; phenol With triethylamine In dichloromethane
Stage #2: With 5-hydroxymethylbicyclo[2.2.1]hept-2-ene In dichloromethane Heating;
Stage #3: With [{1,3-bis(mesyl)imidazolidin-2-yl}RuCl2(PCy3)(=CHPh)] In dichloromethane Heating; Further stages.; |
|
|
With triethylamine In diethyl ether |
|
|
at 60℃; |
|
|
at 60℃; Inert atmosphere; |
|
|
With triethylamine In diethyl ether |
|
| 30 %Chromat. |
With zinc oxide at 20℃; for 0.0833333h; |
|
| 72 %Spectr. |
With 1-n-butyl-3-methylimidazolium chloride; sodium hydroxide In water monomer; toluene at 45.5℃; for 0.75h; |
|
|
In neat (no solvent) at 20℃; for 0.5h; |
4.2 General procedure for Fries rearrangement and catalyst preparation
General procedure: Catalyst (FSG) was purchased from Fluorous Technologies Inc. and used without further purification. Its synthesis procedure is reported by Curran et al. [24]. General procedure for Fries rearrangement was done by adding FSG to aryl ester at the ambient temperatures. Before adding FSG to reaction mixture, aryl esters were obtained by in situ formation through the reaction of acyl chloride derivatives and phenol derivatives. Thus, to a 100ml round bottom flask stirring by a magnetic bar 10mmol of phenols was added and then, 10mmol of acyl chloride derivatives (for catechols 20mmol) was added dropwise and allowed to react at room temperature. After 30min, temperature was raised to remove HCl from reaction mixture. Then 1g of FSG was added to reaction mixture at ambient temperature. After 4h heating at appropriate temperature in oil bath, the reaction mixture was cooled to room temperature and washed with dichloromethane. The catalyst was separated by filtration. The solvent was removed by rotary evaporator and resulting mixture was separated by column chromatography (stationary phase: silica-gel, eluent:hexane:ethyl acetate) and purified by recrystallization. All isolated products successfully gave related spectral data of IR, NMR, and mass spectrometers. |
|
In dichloromethane |
General procedure: Y-Substituted-phenyl benzoates (5a-j) wereprepared by modification of literature procedures by addingthe respective phenol to the solution of benzoyl chloride inmethylene chloride as reported previously.21 The crude productwas purified by column chromatography (silica gel,methylene chloride/n-hexane 50/50). The purity was checkedby their melting points and 1H NMR spectra. |
|
With sodium hydroxide |
4.2.2. Synthesis of substitutedphenyl benzoate (II)
General procedure: Substituted benzoyl chloride (0,1 mol) was reacted with phenol(0.1 mol in 100 mL of 10% sodium hydroxide solution). The crudeproduct was washed with water and recrystallized from ethanol[12,20]. |
|
Stage #1: phenol With bis(η5-cyclopentadienyl) titanium dichloride; manganese powder; diiodomethane In tetrahydrofuran at 20℃; for 2.5h; Inert atmosphere;
Stage #2: benzoyl chloride In tetrahydrofuran at 20℃; for 1.5h; Inert atmosphere; |
|
|
With sodium hydroxide at 0℃; |
|
| 99 %Spectr. |
With 1-methyl-1H-imidazole In toluene at 90℃; Flow reactor; Ionic liquid; Green chemistry; |
|
|
With potassium carbonate In acetone at 20℃; for 3h; |
3.3. General Procedure for Synthesis of Aryl Esters
General procedure: To a stirred solution of phenol derivatives (0.04 mol) and K2CO3 (0.04 mol) in dry acetone (150 mL), benzoyl chloride/acetic anhydride (0.04 mol) was added dropwise. The reactionmixture was stirred at ambient temperature for 3 h. When thereaction was complete (TLC), the solvent was removed byrotary evaporator to afford the pure desired aryl esters thatwashed with water, and air-dried. The structures and purityof the desired aryl esters were confirmed by 1H NMR spectroscopy(see the Supporting Information, Fig. 1S-11S). |
|
Stage #1: phenol With sodium hydroxide
Stage #2: benzoyl chloride |
|
|
at 39.84℃; |
|
|
With sodium hydroxide |
Synthesis of the substituted hydrazide derivatives (iii).
General procedure: Firstly 4-substituted aroyl chloride (10 mmol)was reacted with phenol (10 mmol in 100 mL of 10% sodium hydroxide solution) to form 4-substituted phenyl benzoate. The crude product was washed with water and recrystallized from ethanol. Then the 4-substituted phenyl benzoate (5 mmol) was reacted with hydrazine hydrate (10 mmol) in methanol. The mixture was refluxed and monitored by TLC. The crude product was washed with water and recrystallized from ethanol [54]. |
|
With dmap In tetrahydrofuran for 16h; Reflux; |
|
| 0.97 g |
In chloroform at 0℃; Reflux; |
|
| 208.5 mg |
In acetonitrile at 80℃; for 11h; Schlenk technique; Sealed tube; |
Typical procedure for the preparation of the target molecules:
General procedure: Under air, tert-butyl ester 1 (1.3 or 0.3 mmol), PCl3 (1.0 equiv.), and CH3CN (0.6 mL) were added to a 25-mLsealed Schlenk tube equipped with a magnetic stir bar. Themixture was stirred at 80 °C for 3 h. Next, the correspondingalcohol (5.0 equiv.) or amine (1.0 or 3.0 equiv.) wasadded to the reaction and the mixture was stirred at the indicatedtemperature for the indicated amount of time. Themixture was then quenched with aqueous NaHCO3 solutionand extracted with EtOAc (×3). The combined organiclayer was dried over MgSO4 and filtered. After evaporationof the solvent under reduced pressure, the residue was purifiedby column chromatography on silica gel to give theanalytically pure product 2 or 3. |
|
With sodium hydroxide In water monomer at 20℃; for 15h; |
|
|
With sodium hydroxide at 20℃; for 0.25h; |
2.2.1. Compound A
In a 100 ml flask, 0.01 M of Benzoyl Chloride was added to 0.01 M ofphenol in 10% sodium hydroxide and coalesced for 15 min at roomtemperature. The solid particles obtained, were then filtered usingwhatman filter paper and air dried for 24 h, following which air driedparticles were recrystallized by ethanol for purification by ethanol andagain air dried. |
|
Stage #1: phenol With sodium hydroxide
Stage #2: benzoyl chloride |
Synthesis of substituted phenyl benzoate (4a-m)
General procedure: 0.1 mol of phenol is dissolved in 10% NaOH. 0.1 mol of substituted benzoyl chloride is added to the solution. After solidformation is observed, the reaction is continued to stir for another 1-2 h, and the solid formed is filtered off. The solid iswashed with water and recrystallized from ethanol [27, 28]. |
|
Stage #1: phenol With sodium hydroxide
Stage #2: benzoyl chloride |
Synthesis of substituted phenyl benzoate (4a-m)
General procedure: 0.1 mol of phenol is dissolved in 10% NaOH. 0.1 mol of substituted benzoyl chloride is added to the solution. After solidformation is observed, the reaction is continued to stir for another 1-2 h, and the solid formed is filtered off. The solid iswashed with water and recrystallized from ethanol [27, 28]. |
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