| 96% |
With gallium(III) trichloride; silver hexafluoroantimonate In 1,2-dichloro-ethane for 7h; Heating; |
|
| 96% |
With bismuth(III) chloride at 110℃; for 6h; |
|
| 95% |
With zinc(II) oxide at 20℃; for 0.0833333h; |
|
| 95% |
With iron(III) oxide at 20℃; for 0.166667h; regioselective reaction; |
|
| 95% |
With Silica gel supported aluminium trichloride at 20℃; for 0.8h; neat (no solvent); regioselective reaction; |
|
| 95% |
With zinc oxide nanoparticles supported on polyaniline at 20℃; for 0.166667h; Neat (no solvent); |
|
| 95% |
With iron oxide In neat (no solvent) at 20℃; for 0.0833333h; Green chemistry; |
|
| 95% |
With VNU-1 In nitrobenzene at 120℃; for 0.0833333h; Microwave irradiation; |
|
| 94% |
With bismuth(lll) trifluoromethanesulfonate; 1-(n-butyl)-3-methylimidazolium triflate at 120℃; for 0.5h; Microwave irradiation; Green chemistry; |
Typical procedure for the benzoylation reaction in ionic liquids:
General procedure: a glass tube was filled with Bi(OTf)3 (0.0328 g, 0.05 mmol), [BMIM]OTf (0.1 g), anisole (0.108 g, 1 mmol), and benzoyl chloride (0.281 g, 2 mmol) and reacted at 120 °C for 30 min under microwave activation. After cooling, the mixture was extracted with Et2O (3 × 20 mL). The organic layer was decanted, washed with water (10 mL), aqueous NaHCO3 (2 × 20mL), brine (10 mL), and dried over MgSO4. The solvent was removed using a rotary evaporator. Conversion was determined by GC analysis using n-hexadecane as the internal standard. The isolated yield was determined after purification by flash chromatography (n-hexane, then 10 % EtOAc in n-hexane) to give 4-methoxybenzophenone (0.1993 g, 94 % yield). The purity and authenticity of the product were confirmed by GC-MS and 1H NMR spectroscopy. The same procedure was carried out under conventional heating method. |
| 94% |
With bismuth(lll) trifluoromethanesulfonate In neat (no solvent) at 100℃; for 0.166667h; Sealed tube; Microwave irradiation; |
EXPERIMENTAL
General procedure: A 10-mL pressurized glass tube with Teflon-coated septum equipped with amagnetic stirrer was charged with substrate (1 mmol), benzoyl chloride (1 mmol),and metal triflate (0.1 equiv). The tube was sealed and placed into a CEM microwaveat the temperature for the appropriate time. The reaction mixture was allowed tocool to the room temperature in the MW oven. After cooling, water (15 mL) wasadded to the mixture and the product was extracted by ethyl acetate or dichloromethane,which gave similar results (315mL). The organic layer was decanted;washed with water, aqueous NaHCO3, and brine; and dried with MgSO4. Thesolvent was then removed on a rotary evaporator and subjected to flash chromatographyon silica gel (mixture of hexane and ethyl acetate solvent to elute theproduct). The fractions containing product were concentrated and dried undervacuum to yield pure product. All products are known compounds; the purity and identityof all products were confirmed by GC-MS and 1H and 13C NMR spectroscopy. |
| 94.1% |
With 0.1 zirconium doped porous magadiite heterostructure at 140℃; for 3h; |
|
| 94.8% |
With o-tetrachloroquinone; (η5,η5-(C5H4)2SiMe2)Mo2(CO)6 In 1,2-dichloro-ethane at 80℃; for 24h; Inert atmosphere; Schlenk technique; |
4.6. Catalytic tests
General procedure: Under an argon atmosphere, the monobridged bis(cyclopentadienyl)molybdenum carbonyl complex (0.1 mmol) and o-chloranil (0.098 g, 0.4 mmol) were mixed with 1,2-dichloroethane (3.5 mL)in a 25 mL round-bottom flask at room temperature with magneticstirring. The solution was immediately darkened. After the mixturehad been stirred for 40 min at room temperature, aromatic compoundsand acylation reagents were added by syringe. The reactionmixture was heated at 80 °C in an oil bath for 24 h. After cooling toroom temperature, the solvent was removed by rotary evaporation,and the residue was purified by Al2O3 column chromatography,eluting with petroleum ether developed colorless liquid thatafforded the corresponding white solid product. The catalyst wasrecovered and washed with petroleum ether, then reused forfurther cycles. The course of the reaction was monitored using anAgilent 6820 gas chromatograph. |
| 89% |
In chlorobenzene at 120℃; for 2h; |
|
| 89% |
With copper(II) ferrite In neat (no solvent) at 35 - 38℃; for 18h; |
General procedure: The FC acylation of various benzenes with acid chlorides was carried out in the presence of magnetic nano CuFe2O4 (particle size = 50 nm) by using one of the reaction condition (A-D) given below. Condition A: Anisole/arene (1 mmol), acid chloride (1.2 mmol), nano CuFe2O4 (20 mol %), 1,2-DCE (2 mL), 80 C and 24 h. Condition B: Anisole/arene (1 mmol), acid chloride (1.2 mmol), nano CuFe2O4 (20 mol %), 1,2-DCE (2 mL), rt (35-38 C) and 18 h. Condition C: Neat reaction, anisole/arene (3.3 mmol), acid chloride (1.2 mmol), nano CuFe2O4 (20 mol %), rt (35-38 C) and 18 h. Condition D: Neat reaction, arene/anisole (3.3 mmol), acid chloride (1.2 mmol), nano CuFe2O4 (20 mol %), 80 C and 18 h. |
| 86% |
With iron(III) sulfate In hexane at 20℃; for 0.583333h; Sonication; |
|
| 84% |
With water In 1,2-dichloro-ethane at 80℃; for 3h; |
|
| 83% |
With indium at 100℃; for 2h; |
|
| 80% |
In dichloromethane for 24h; Ambient temperature; |
|
| 80% |
With silver nitrate In ethanol at 20℃; |
|
| 80% |
With choline chloride * 2ZnCl2 In neat (no solvent) at 70℃; for 0.75h; Green chemistry; |
General procedure for aromatic ketone compounds synthesis
General procedure: A mixture of electron-rich arenes a (2.0 mmol), acylation reagent b ((2.0 mmol)and catalytic solvent DES [ChCl][ZnCl 2 ] 2 (2.0 mmol) were added and stirred in a25 mL round-bottomed ask at 70 C for the desired time. The reaction procedurewas monitored by TLC and recorded the experimental phenomena. Aftercompletion of the reaction, 10 mL of water and 10 mL of ethyl acetate wereadded to the mixture and then cooled to room temperature, collecting the productand solvent from the organic phase and water, respectively. The organic phase waswashed with saturated sodium hydrogen carbonate solution and saturated brinesuccessively, then evaporated under high vacuum to give the target compound. PureDES was obtained by drying sufciently in a vacuum, and it could be reused foranother cycle. |
| 78% |
With Envirocat EPZG for 25h; Heating; |
|
| 78% |
With Cl4Fe(1-)*C9H7N3O2*H(1+) In neat (no solvent) at 100℃; for 2h; Inert atmosphere; |
(4-Methoxyphenyl)-phenylmethanone (4a).
To a solution of aryl alkane 2a (217 L, 2 mmol), acyl chloride3a (116 L, 1 mmol), and ionic liquid 1d (349 mg, 0.9 mmol) were stirred at 100 C for two hours. Aftercooling, the reaction mixture was washed by diethyl ether (2 40 mL). The diethyl ether layer wasdecanted, extracted with water, aqueous NaHCO3, and brine, and dried over MgSO4. After filtration,the organic solvent was then removed on a rotary evaporator. The residue was purified by flashchromatography to give the desired product 4a (165 mg, 78%) as a light yellow oil. Rf 0.37 (EtOAc/Hex= 1/6). IR (NaCl) v 3060, 3006, 2840, 1651, 1597, 1508, 1171 cm1; 1H NMR (Supplementary Materials)(400 MHz, CDCl3) 7.82 (d, J = 8.8 Hz, 2H), 7.74 (d, J = 6.8 Hz, 2H), 7.55 (t, J = 7.4 Hz, 1H), 7.45 (t, J =7.6 Hz, 2H), 6.95 (d, J = 9.2 Hz, 2H), 3.86 (s, 3H); 13C NMR (101 MHz, CDCl3) 195.4, 163.1, 138.2, 132.4,131.8, 130.0, 129.6, 128.1, 113.4, 55.4; HRMS (EI,M+) calculated for C14H12O2 212.0837, found 212.0834. |
| 76% |
With Si-MCM-41 supported gallium oxide In 1,2-dichloro-ethane at 80℃; for 3h; |
|
| 75% |
at 25℃; for 0.75h; |
|
| 72.4% |
at 60℃; for 3h; |
4.a
Benzoylation of anisole 373 mg benzoyl chloride were reacted with 12 ml anisole and 200 mg of the above prepared catalyst at 60° C. for 3 hours. 50 mg dodecane were added to the reaction mixture as internal standard for quantitative GC analysis. The conversion was 100%, the yield of methoxybenzophenone was 72.4%. |
| 71% |
With zinc at 120 - 121℃; for 0.00277778h; microwave irradiation; |
|
| 65% |
at 120℃; for 5h; |
|
| 61% |
With samarium (III) iodide In acetonitrile at 45℃; for 4h; |
|
| 56.2% |
With C19H13O4Re In 1,2-dichloro-ethane at 84℃; for 24h; Inert atmosphere; Schlenk technique; Green chemistry; regioselective reaction; |
2.10. Catalytic tests
General procedure: The catalytic reactions were carried out under an argon atmosphere with magnetic stirring;the required complexes (0.02 mmol) were mixed with 1,2-dichloroethane (3.5 mL) in a 25 mLround-bottom flask at room temperature. Aromatic compounds and alkylation/acylationreagents were added by syringe. The reaction mixture was heated in an oil bath at 84 °C for15 and 24 h. After cooling to room temperature, the solid catalyst was separated from thereaction mixture by filtration, solvent was removed through rotary evaporation, and theresidue was purified by Al2O3 column chromatography, eluting with petroleum ether to givethe corresponding products. The progress of the reaction was monitored using an Agilent6820 gas chromatograph. |
| 50% |
With aluminium trichloride for 12h; Ambient temperature; |
|
| 50% |
In 1,2-dichloro-ethane Heating; |
|
| 48.2% |
In benzene at 20℃; for 12h; Heating / reflux; |
4
A mixture of 5.4 gm (0.05 moles) of anisole and 7.0 gm (0.05) moles of benzoyl chloride and 0.5 gm of boron carbide was placed in 50 ml of benzene. This mixture was allowed to react as described in Example 3. A yield of 48.2% of p-methoxy benzophenone was obtained, and 0.5 gm of the boron carbide catalysts was recovered. |
| 47% |
at 60℃; Heating / reflux; |
11
370 mg of benzoylchloride were reacted with 12 ml anisole to give the benzoylated product 4-methoxybenzophenone in 47% yield. The catalyst used is a HS-AlF3 metal fluoride on a Al2O3 support prepared according to the present invention, which is used in an amount of 300 mg. The reaction is carried out in a discontinuous batch process at 60° C. under reflux with stirring. When using a conventionally prepared AlF3 catalyst no reaction occured, GC yield 0%. Products and yields were estimated by GC. Internal standard is tridecane. |
| 34% |
With 1,1,1,3',3',3'-hexafluoro-propanol at 20℃; for 5h; Inert atmosphere; |
|
|
With diethyl ether; zinc |
|
|
With zinc(II) chloride zuletzt bei Siedetemperatur; |
|
|
With phosphoric acid at 100 - 105℃; |
|
|
With Fuller's Earth at 90 - 120℃; |
|
|
With iodine auf Siedetemperatur; |
|
|
With carbon disulfide; aluminium trichloride |
|
| 85 % Chromat. |
With pyrographite In chlorobenzene at 120℃; for 8h; |
|
| 79 % Chromat. |
With scandium tris(trifluoromethanesulfonate) In nitromethane at 50℃; for 18h; |
|
|
Stage #1: benzoyl chloride With aluminium trichloride In nitrobenzene at 0 - 8℃; for 0.166667h;
Stage #2: methoxybenzene In nitrobenzene at 6 - 20℃; |
|
|
at 70℃; for 2h; |
|
| 0% |
at 60℃; Heating / reflux; |
11
370 mg of benzoylchloride were reacted with 12 ml anisole to give the benzoylated product 4-methoxybenzophenone in 47% yield. The catalyst used is a HS-AlF3 metal fluoride on a Al2O3 support prepared according to the present invention, which is used in an amount of 300 mg. The reaction is carried out in a discontinuous batch process at 60° C. under reflux with stirring. When using a conventionally prepared AlF3 catalyst no reaction occured, GC yield 0%. Products and yields were estimated by GC. Internal standard is tridecane. |
|
at 80℃; for 8h; Inert atmosphere; |
36
In a glovebox under argon, 1 mmol of the copper salt Cu.(BFST)2 obtained according to the process of example 16 and 20 ml of BMIm.BFST, prepared according to the process of example 18, were introduced into a round-bottomed flask, and then the medium was brought to 80° C. for 10 min in order to make it homogeneous. After cooling, 10 mmol of benzoyl chloride (Aldrich) and 50 mmol of anisole were introduced. The reaction medium was then brought to 80° C. for 8 hours, and then extracted several times with ether after cooling. The organic phase was washed with water, with aqueous NaHCO3 and with a saturated aqueous solution of salt. After evaporation of the solvent, the product was purified by flash chromatography separation (eluant: 10/1 petroleum ether/ethyl acetate). The product below, mainly substituted in the para position, was thus obtained: |
|
With aluminum (III) chloride In 1,2-dichloro-ethane at 0 - 20℃; |
|
|
With macroreticular p-(ω-sulfonic-perfluoroalkylated) polystyrene (FPS) resin for 8h; Inert atmosphere; Reflux; Green chemistry; |
|
|
With Hierarchical-Beta zeolite In neat (no solvent) at 119.84℃; for 4.5h; |
2.3.2. Benzoylation reaction
General procedure: In a typical benzoylation reaction, substrate, benzoylating agent(benzoic acid or benzoyl chloride) and catalyst (activated at 473 K)were mixed in a 25 mL round bottom flask. Reactions were con-ducted at a desired temperature for a stipulated time period insolvent/neat condition. The reaction mixture was analyzed usingGC. Reactant conversion and product selectivity were obtainedusing GC. Products were confirmed using GC-MS. In most of thecases, products were also confirmed by the authentic samplesobtained from Aldrich (based on the retention time of the authenticsample in the GC analysis). |
|
With phosphotungstic heteropoly acid (26.5 percentwt) encapsulated into zeolite imidazolate framework (ZIF-67) at 120℃; for 6h; |
2.4. Catalytic performance testing
The Friedel-Crafts acylation of anisole with benzoyl chloride using PTAZIF-67(ec) catalyst was carried out in the magnetically stirred round-bottom flask. In a typical reaction, a mixture of an-isole and benzoyl chloride with molar ratio1:2, n-Dodecane as an internal standard was charged into a 50mL flask containing the PTAZIF-67(ec) catalyst. The reaction mixture was then heated to 120 °C with continuously stirring for 6h. After 6h, the reaction mixture was quenched with anaqueous NaOH solution (1%,0.15mL). The organic components were extracted using diethylether (2mL), dried over anhydrous Na2SO4 and the product was analyzed by GC. The structure of the product was defined by GC-MS. For the investigating the reusability of the catalyst, the PTAZIF-67(ec) catalyst was separated by simple centrifugation from the reaction mixture, was hed with abundant amounts of dichloromethane(DCM), dried under vacuum at room temperature for 6h and reused in reaction. |
|
With C21H28BiF20O11P2(1+)*C4F10O2P(1-) at 140℃; for 1.5h; Schlenk technique; Inert atmosphere; |
|
| 20.1 %Chromat. |
With o-tetrachloroquinone; [(η2-2-C5H4N)CH=N(C6H4-Cl)]Mo(CO)4 In 1,2-dichloro-ethane at 80℃; for 24h; Inert atmosphere; Schlenk technique; regioselective reaction; |
General procedure for catalytic tests
General procedure: The catalytic reactions were carried out under an argon atmosphere with magnetic stirring. The required Mo complex (0.4 mmol) and o-chloranil (0.57 g, 2.4 mmol) was mixed with 1,2-dichloroethane (4.5 mL) in a 25-mL round bottomflask at room temperature. Aromatic compounds (2 mmol) and acylation reagents (2 mmol) were added by syringe. The reaction mixture was heated at 80 °C for 24 h. After cooling to room temperature, the solid catalyst was separated from the reaction mixture by filtration. The solvent was removed by rotary evaporation, and the residue was purified by Al2O3 column chromatography, eluting with petroleum ether and dichloromethane to give the corresponding products. The progress of the reaction was monitored using an Agilent 6820 gas chromatograph. |
|
With o-tetrachloroquinone; [(η5-(tetramethylcyclopentadienyl)Ph)Mo(CO)3]2 In 1,2-dichloro-ethane at 80℃; for 24h; Inert atmosphere; Schlenk technique; regioselective reaction; |
General procedure for catalytic tests
General procedure: Under an argon atmosphere, the required molybdenumcarbonyl complex (0.2 mmol) and o-chloranil (0.8 mmol) were mixed with 1,2-dichloroethane (3.5 mL) in a 25 mL round-bottom flask at room temperature. The solution was immediately darkened. After stirring for 40 min at room temperature, the aromatic compound (2 mmol) and acylating reagent (6 mmol) were added by syringe. The reaction mixture was then heated on an oil bath at 80 °Cfor 24 h. After cooling to room temperature, the solvent was removed through rotary evaporation. The residue was purified by Al2O3 column chromatography. Elution with petroleum ether/ethyl acetate (4:1, V/V) developed a colorless liquid that afforded the corresponding product. The course of the reaction was monitored using an Agilent 6820 gas chromatograph. |
|
With Bi[(C2F5)2PO2]3 at 140℃; for 1.5h; Schlenk technique; Inert atmosphere; |
C.5.6 Example 6. Friedel-Crafts Acylation with Bi[(C2F5)2PO2]3 as Catalyst
149 mg (0.134 mmol) of 47 Bi[(C2F5)2PO2]3 and 441 mg (3.137 mmol) of 43 benzoyl chloride are initially introduced in a 25 ml Schlenk tube in a counterstream of 8 nitrogen. 293 mg (2.710 mmol) of 44 anisole are added, and the mixture is stirred at 140° C. for 1.5 hours. The solution rapidly becomes yellow, later dark red. The conversion to 45 4-methoxybenzophenone detected by 1H- and 13C-NMR spectroscopy is 90%. The reaction product is obtained by extraction of the reaction mixture with diethyl ether. The extract is washed twice with water and concentrated NaHCO3 solution. The organic phase is dried over magnesium sulfate, and the solvent is distilled off under reduced pressure. The residue is crystallised from n-hexane/diethyl ether (2:1). |
|
With sulfonated & fluorinated polymerized 2,2',4,4',6,6'-hexafluoro-3,3'-divinyl-1,1'-biphenyl at 100℃; for 10h; |
|
|
With aluminum (III) chloride In dichloromethane at 0℃; for 2h; Sealed tube; Inert atmosphere; |
Typical Procedure for Transformation of Arenes 1 into 5-Alkyl-1-aryltetrazoles 3:
General procedure: To a solution ofcumene 1A (1.0 mmol, 120.0 mg) in CH2Cl2 (2.0 mL) in a 30 mL sealed tube was added acetyl chloride(1.2 mmol, 85.4 μL) at 0 °C. After flash with argon gas, the mixture was stirred for a few minutes.Anhydrous AlCl3 (1.2 mmol, 161.0 mg) was added and the obtained mixture was stirred for 2 h at 0 °C.Then, the reaction mixture was quenched with cooled water (1.0 mL) and stirred for 0.5 h. Afterremoval of the solvent under reduced pressure, MeOH (3.0 mL), NH2OHHCl (1.5 mmol, 107.0 mg), andK2CO3 (1.5 mmol, 207.0 mg) were added. After flash with argon gas, the obtained mixture was stirredfor 16 h at rt. After removal of the solvent under reduced pressure, toluene (3.0 mL), DPPA (2.5 mmol,0.54 mL), and DBU (3.5 mmol, 0.53 mL) were added to the residue. After flash with argon gas, themixture was warmed at 120 °C for 16 h. The mixture was cooled to rt and then, sat. NaHCO3 aq. (15.0mL) was added. The mixture was filtered through Celite, and the filtrate was extracted with AcOEt(20.0 mL ×3). The organic layer was dried over Na2SO4. After removal of the solvent under reducedpressure, the residue was purified by short column chromatography on silica gel (n-hexane/AcOEt,3:1-1:3) to afford 1-(4’-isopropylphenyl)-5-methyl-1H-tetrazole 3Aa in 60% yield (121.1 mg). |
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