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CAS No. : | 1023-17-2 | MDL No. : | MFCD00017177 |
Formula : | C15H14O2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | PLALKSRAHVYFOH-UHFFFAOYSA-N |
M.W : | 226.27 | Pubchem ID : | 231093 |
Synonyms : |
|
Num. heavy atoms : | 17 |
Num. arom. heavy atoms : | 12 |
Fraction Csp3 : | 0.13 |
Num. rotatable bonds : | 4 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 67.62 |
TPSA : | 26.3 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | Yes |
CYP2C19 inhibitor : | Yes |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | Yes |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -5.44 cm/s |
Log Po/w (iLOGP) : | 2.55 |
Log Po/w (XLOGP3) : | 3.15 |
Log Po/w (WLOGP) : | 3.12 |
Log Po/w (MLOGP) : | 2.86 |
Log Po/w (SILICOS-IT) : | 3.78 |
Consensus Log Po/w : | 3.09 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 0.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -3.49 |
Solubility : | 0.0739 mg/ml ; 0.000327 mol/l |
Class : | Soluble |
Log S (Ali) : | -3.37 |
Solubility : | 0.096 mg/ml ; 0.000424 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -5.4 |
Solubility : | 0.000895 mg/ml ; 0.00000395 mol/l |
Class : | Moderately soluble |
PAINS : | 0.0 alert |
Brenk : | 0.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.55 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P280-P305+P351+P338 | UN#: | N/A |
Hazard Statements: | H302 | 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 |
---|---|---|
86% | With copper(ll) bromide In dichloromethane; ethyl acetate for 18h; Reflux; Inert atmosphere; | 4.2. A representative synthetic procedure of skeletons 3 and 6 is as follows General procedure: Copper(II) bromide (CuBr2, 268 mg, 1.2 mmol) was added to a solution of skeleton 5 (1.0 mmol) in the co-solvent of EtOAc and CH2Cl2 (1:1, 20 mL), at 25 °C. The reaction mixture was stirred at reflux for 18 h. The reaction mixture was cooled to 25 °C. Saturated NaHCO3 (5 mL) was added to the reaction mixture and the solvent was concentrated. The residue was diluted with water (10 mL) and the mixture was extracted with EtOAc (3 x 20 mL). The combined organic layers were washed with brine, dried, filtered and evaporated to afford crude product. Purification on silica gel (hexanes/EtOAc = 10/1-6/1) afforded skeletons 3 and 6. |
60% | With N-Bromosuccinimide In neat (no solvent) at 27℃; for 24h; Irradiation; regioselective reaction; | General procedure for photo-induced reactions with NBS under SFRC General procedure: To a ketone (0.3 mmol), NBS (0.33 or 0.66 mmol, 20 or 39 mg) was added and the resulted reaction mixture was stirred under illumination with an 8-W energy-saving light bulb for 19-29 h. At the end of the reaction, conversions and the product distribution were determined by 1H NMR spectroscopy of the crude reaction mixture. Pure products were obtained after separation by either CC or preparative TLC and were analyzed by 1H NMR, 13C NMR, IR, HRMS and melting point when solid. Spectroscopic data of the known compounds are available in Supporting Information and are in accordance with the literature data. |
With tetrachloromethane; bromine unter Bestrahlung mit Gluehlampenlicht; |
With aluminium trichloride; diethyl ether; bromine | ||
With diethyl ether; bromine | ||
With bromine In tetrachloromethane Irradiation; | ||
With bromine In chloroform | ||
With bromine In chloroform | ||
With bromine In 1,4-dioxane at 20℃; | 78.2 A suspension of 74 (5.0 g, 0.022 mol) in dioxane (50 mL) was cooled down in an icebath, then treated with bromine (1.1 mL, 0.021 mol) in 3 portions during a period of 30 min.The reaction was left to stir at rt overnight, then poured into water, extracted with EtOAc, andpurified by silica gel column chromatography to obtain a mixture of 2-bromo-l-(4-hydroxy-phenyl)-2-phenyl-ethanone 75 (MS: 305.1, 307.1, M+l) and some dibromo product (6.4 g).This mixture was directly used for the next step. | |
With bromine In chloroform at 50℃; for 0.5h; | ||
With copper(ll) bromide In chloroform; ethyl acetate for 2h; Reflux; | ||
With bromine In acetic acid at 20℃; | ||
With bromine; acetic acid at 25℃; for 2h; | ||
With copper(ll) bromide In chloroform; ethyl acetate for 3h; Reflux; | 1 1.10 g of cinnamamide and 1.20 g of trichloroaldehyde hydrate were added to 30 ml of toluene and refluxed at 110° C. for 8 h, cooled to room temperature to precipitate a large amount of yellow lamellar crystal of (2E)-3-(2-thienyl)-N-(1-hydroxy-2,2,2-trichloroethyl)acrylamide (1.20 g). It was dissolved in 20 ml of anhydrous THF, DMF was added as catalyst, and 1.2 ml of SOCl2 was added dropwise at room temperature, heated to 60° C. and reacted for 2 h. The solvent was evaporated to give a yellow solid of (2E)-3-(2-thienyl)-N-(1,2,2,2-tetrachloroethyl)acrylamide, which was washed with cool petroleum ether to neutral, and dried in vacuum for use. 1.44 g of phenylacetic acid was dissolved in 20 ml of THF, and 2.50 g of SOCl2 was added dropwise at room temperature, refluxed for 2 h, rotary evaporated to remove the solvent to obtain a yellow oil. The yellow oil was dissolved in 10 ml of anhydrous chloroform, and slowly added dropwise under ice-bath to a solution of 1.06 g of methyl phenyl ether and 2.66 g of aluminum trichloride in 20 ml of chloroform, and reacted at room temperature for 2 h after the addition. The reaction solution turned from orange to dark brown. 20 ml of water was slowly added dropwise, the reaction solution was layered. The lower layer was washed with saturated brine for 3 times, 20 ml per time. The organic layer was rotary evaporated to obtain 4′-methoxy-2-phenyl-phenylethylketone. It was refluxed with 4.40 g of CuBr2 in a mixture solvent of 10 ml of ethyl acetate and 10 ml of chloroform for 3 h, the black solid turned white, and the solution turned from clear to dark green. The solid was removed by filtration after the reaction The reaction solution was rotary evaporated and dissolved in 15 ml isopropanol, added with 0.76 g of thiourea, refluxed for 1.5 h, and a large amount of faint yellow solid was precipitated as 4-(4-methoxyphenyl)-5-phenyl-2-aminothiazole. It was added to 20 ml of DMF together with the above mentioned (2E)-3-(2-thienyl)-N-(1,2,2,2-tetrachloroethyl)acrylamide, and stirred at room temperature for 24 h. The reaction solution was poured into 40 ml of water, extracted with ethyl acetate for 3 times, 20 ml each, the organic phases were combined and washed with saturated brine for 3 times, 50 ml each. The organic phase was directly added with 4 g of crude silica gel and stirred, eluted with petroleum ether:ethyl acetate=4:1, to obtain 0.30 g of white solid. [0064] 1H-NMR (400 MHz, DMSO-d6) δ3.74 (s, 3H); 56.84-6.86 (dd, 2H); 6.94-6.98 (m, 1H); δ7.26-7.46 (m, 6H); 57.55-7.61 (t, 1H); δ8.71-8.73 (d, 1H); 69.03-9.05 (d, 1H). MS (TOF) 559.5 (M+). | |
With bromine In chloroform for 2h; Reflux; | ||
With bromine In diethyl ether at 20℃; for 2h; Inert atmosphere; | Synthesis of intermediate 3a-3w. General procedure: The intermediate 2a-2w (8mmol) was added into Et2O (30mL) under the atomsphere of argon at room temperature for 2h. Then, the solvent was concentrated in vacuo to afford the crude product 3a-3w which was directly for next reaction without further purification. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With sodium tetrahydroborate In ethanol | |
Reduktion nach Meerwein-Ponndorf; | ||
With sodium tetrahydroborate In isopropyl alcohol |
With sodium tetrahydroborate In tetrahydrofuran; water at 20℃; | ||
With sodium tetrahydroborate In methanol at 0 - 20℃; | Synthesis of alcohol substrates General procedure: Alcohols (2-3a, 14-15a, 19-22a, 24-25a) were synthesized by reduction ofcorresponding ketones with NaBH4 in MeOH according to the previous report.1Typically, ketone (15 mmol) was dissolved in 100 mL MeOH. Then the solution wascooled to 0 °C in ice bath, followed by slow addition of NaBH4 (5 mmol). The reactionwas kept stirring at 0 °C for 10 min and warmed to room temperature for 1 h to 12 huntil ketone was fully consumed. Then the reaction mixture was concentrated in vacuobefore adding 100 mL saturated aqueous NH4Cl. The aqueous phase was extracted withethyl acetate for three times (3×100 mL). The organic phase was washed with brine,dried with anhydrous Na2SO4, and finally concentrated in vacuo to produce thecorresponding alcohols. Further purification was conducted using gel columnchromatography if necessary. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With selenium(IV) oxide In dimethyl sulfoxide at 170℃; for 0.0166667h; Microwave irradiation; | 4.2.2. Experimental Procedure for Ethanediones 12 [36] General procedure: Selenium dioxide (1.5 mmol) was added into a solutionof ethanone derivatives 11 (1 mmol) in DMSO (1.5 mL) andirradiated in the microwave oven for 1 min at 170C. The hotmixture was filtered to remove the selenium metal and thefiltrate was purified by column chromatography in silica gelusing EtOAc/hexanes 7:3 as eluent. |
96% | With potassium hydrogencarbonate; dimethyl sulfoxide at 80℃; | |
93% | With N-Bromosuccinimide; dimethyl sulfoxide for 72h; Ambient temperature; |
90% | With oxygen; copper(II) acetate monohydrate; potassium carbonate In N,N-dimethyl-formamide at 50℃; for 3h; | |
85% | With selenium(IV) oxide In dimethyl sulfoxide for 0.00972222h; microwave irradiation; | |
85% | With selenium(IV) oxide In dimethyl sulfoxide for 0.00972222h; microwave irradiation; | |
77% | With C42H42CeN6Ni3O6(3+)*3C2H3O2(1-) In acetonitrile at 20℃; for 18h; Irradiation; | |
64% | With 1,4-diaza-bicyclo[2.2.2]octane; tetra-(n-butyl)ammonium iodide In acetonitrile at 20℃; for 6h; Electrochemical reaction; | |
62% | With copper diacetate; triphenylphosphine at 100℃; for 0.75h; | |
With 1,4-dioxane; selenium(IV) oxide | ||
With pyridine; selenium(IV) oxide | ||
With selenium(IV) oxide In 1,4-dioxane; water for 8h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydroxylamine | ||
With pyridine; hydroxylamine In ethanol | ||
With hydroxylamine hydrochloride; sodium acetate In ethanol; water at 20℃; for 49h; | 46.A; 100.A.B To a solution consisting of 1-(4-methoxy-phenyl)-2-phenyl-ethanone (commercially available, 1011 g, 4468 mmoles) in absolute ethanol (2 gallons) is added hydroxylamine hydrochloride (373 g, 5362 mmoles) and sodium acetate (440 g, 5362 mmoles.) The reaction mixture is stirred at room temperature for two days. The mixture is diluted with water (8 L) and the resultant mixture is stirred at room temperature for one hour. The mixture is subsequently filtered to give a solid, which is rinsed with water (3×4 L.) The product is dried to afford the synthetic intermediate 1-(4-methoxy-phenyl)-2-phenyl-ethanone oxime (948 g.); To a solution of the product of Step A, 1-(4-methoxy-phenyl)-2-phenyl-ethanone, (1011 g, 4468 mmoles) in absolute ethanol (2 gallons) is added hydroxylamine hydrochloride (373 g, 5362 mmoles) and sodium acetate (440 g, 5362 mmoles.) The reaction mixture is stirred at room temperature for two days. The mixture is diluted with water (8 L) and the resultant mixture is stirred at room temperature for one hour. The mixture is subsequently filtered to give a solid, which is rinsed with water (3×4 L.) The product is dried to afford the synthetic intermediate 1-(4-methoxy-phenyl)-2-phenyl-ethanone oxime (948 g.) |
With hydroxylamine hydrochloride; sodium acetate In ethanol at 20℃; for 24h; | 137 A one-neck 250 mL round-bottomed flask is charged with 1-(4-methoxy-phenyl)-2-phenyl-ethanone, which may be produced by any of the methods described Example 133 (limiting reagent, 9.5 g) and absolute ethanol (80 mL). To the slurry is added hydroxylamine hydrochloride (3.47 g) followed by sodium acetate (4.1 g). The reaction is stirred for 24 h at room temperature. Water (150 mL) is added to the slurry. After stirring for 15 minutes, the solids are isolated by filtration and washed with a 10% citric acid solution (100 mL), water (100 mL), and acetonitrile (50 mL). The solids are placed in a vacuum oven for 2 hours, providing the title compound (8.9 g) as a mixture of geometric isomers. | |
With pyridine; hydroxylamine hydrochloride In ethanol at 20℃; | 62 Example 62 [ 4- (4-PHENYL-5-TRIFLUOROMETHYL-ISOXAZOL-3-VL)-PHENOL] [1- (4-METHOXY-PHENYI)-2-PHENYI-ETHANONE] oxime To a solution of deoxy-4-methoxybenzoin (2. 00g, 8.88 [MMOL)] in EtOH [(50MOI)] and pyridine [(30MI)] was added hydroxylamine hydrochloride (3.08g, 44.4 [MMOL).] The reaction was stirred at room temperature overnight. The reaction mixture was concentrated in vacuo and diluted with Et2O [(50MOI).] The mixture was washed with 10% HCI (2x50ml) and brine [(1X50ML).] The organic layer was dried [(NA2SO4),] filtered and concentrated in vacuo to give [1- (4-METHOXY-PHENYL)-2-PHENYL-ETHANONE] oxime (1.4g, 5.82 [MMOL).] | |
With hydroxylamine hydrochloride; sodium acetate In methanol; water at 20℃; | ||
With hydroxylamine hydrochloride; sodium acetate In methanol; water at 20℃; | General procedure: General procedure: A mixture solvent of MeOH/H2O(20:1, V:V) was added to a mixture of 2-phenylacetophenones (1.0 mmol, 1.0 eq), NH2OH·HCl (1.5eq) and sodium acetate (2.0 eq) in a round bottom flask. Theresulting solution was stirred at room temperature and monitored by TLC. Afterreaction completed, the solvent was removed in vacuo and added CH2Cl2. Then, the mixture wassequentially washed with sat. NaHCO3and brine. The Organic layer was dried over Na2SO4.Concentration afforded the oximes, which was used directly for the next step.To a solution of the crude oximes (1.0 eq) in dry THF was added triethylamine(1.5 eq) and methanesulfonyl chloride (1.5 eq) sequentially at 0°C. The resulting mixture was stirred for 30 min,and DBU (1.5 eq) was then added over 1 min. After stirred for additional 30min, the reaction mixture was filtered by sand core funnel with silica gel,washed with Et2O.The eluent was concentrated in vacuoand the residue was purified by column chromatography on silica gel(eluted with PE/EA = 30 : 1) to give the 2H-azirines(2a-d). | |
With ammonium hydroxide hydrochloride; sodium acetate In methanol; water at 20℃; | ||
With hydroxylamine hydrochloride; sodium acetate In methanol; water at 20℃; Schlenk technique; Inert atmosphere; | ||
With hydroxylamine hydrochloride; sodium acetate In methanol; water at 20℃; Inert atmosphere; | ||
With hydroxylamine hydrochloride; sodium acetate In methanol; water at 25℃; | ||
With hydroxylamine hydrochloride; sodium acetate In methanol; water at 20℃; | ||
With hydroxylamine hydrochloride; sodium acetate In methanol; water at 20℃; | ||
With hydroxylamine hydrochloride; sodium acetate In methanol at 120℃; | ||
With hydroxylamine hydrochloride; sodium acetate In ethanol; water at 100℃; for 6h; | ||
With hydroxylamine hydrochloride; sodium acetate In methanol; water at 20℃; for 5h; | ||
With pyridine; hydroxylamine hydrochloride In ethanol at 60℃; for 1h; | ||
With hydroxylamine hydrochloride; sodium acetate In methanol; water at 20℃; | ||
With hydroxylamine hydrochloride; sodium hydroxide In methanol at 20℃; for 2h; | 2,3-Diphenyl-2H-azirine (1a); Typical Procedure for the Synthesis of 2H-Azirines 1 General procedure: 1,2-Diphenylethan-1-one (1.0 equiv) was added dropwise to a mixture of NH2OH·HCl (1.1 equiv) and NaOH (1.1 equiv) in MeOH (20 mL) at room temperature. After stirring for 2 h, the solvent was removed under reduced pressure. Then, CH2Cl2(20 mL) was added and the mixture was washed with H2O (2 × 15 mL). The organic layer was dried over anhydrous Na2SO4, and the solvent was evaporated to give crude 1,2-diphenylethan-1-one oxime which was used for the next step without purification. The crude ketoxime was dissolved in THF (30 mL), and then Et3N (1.0 equiv) and methanesulfonyl chloride (1.1 equiv) were added at 25 °C. After stirring for 1 h, DBU (1.0 equiv) was added, and the reaction mixture was stirred for 4 h at 25 °C; after completion of the reaction, the solvent was removed in vacuo. The crude material was purified by flash chromatography on silica gel (EtOAc/n-hexane, 1:10) to yield 2,3-diphenyl-2H-azirine (1a, 70 %). | |
With hydroxylamine hydrochloride; sodium acetate In methanol; water at 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With pyridine; hydroxylamine hydrochloride In ethanol | 62 1-(4-Methoxy-phenyl)-2-phenyl-ethanone oxime 1-(4-Methoxy-phenyl)-2-phenyl-ethanone oxime To a solution of deoxy-4-methoxybenzoin (2.00 g, 8.88 mmol) in EtOH (50 ml) and pyridine (30 ml) was added hydroxylamine hydrochloride (3.08 g, 44.4 mmol). The reaction was stirred at room temperature overnight. The reaction mixture was concentrated in vacuo and diluted with Et2O (50 ml). The mixture was washed with 10% HCl (2*50 ml) and brine (1*50 ml). The organic layer was dried (Na2SO4), filtered and concentrated in vacuo to give 1-(4-methoxy-phenyl)-2-phenyl-ethanone oxime (1.4 g, 5.82 mmol). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With trifluoromethylsulfonic anhydride In dichloromethane Cooling with ice; | 4.1.1. 1-(2,4-Dimethoxyphenyl)-2-p-tolylethanone (7a) General procedure: Into a 100mL round bottom flask equipped with magnetic stirring was placed 4-tolylacetic acid (0.524g, 3.61mmol) along with 15mL of dry dichloromethane (DCM). To this mixture with ice bath cooling was added 1,3-dimethoxybenzene (0.542g, 3.61mmol) and 4.33mL (4.33mmol) of a 1.00M solution of triflic anhydride in anhydrous DCM. The resulting mixture was stirred overnight, diluted with 20mL of saturated aqueous bicarbonate and extracted with DCM (3×20mL). The DCM solution was dried over anhydrous sodium sulfate, filtered through a fritted glass funnel and the filtrate was then passed through a short plug of silica gel and the plug was then washed with 50mL of ethyl acetate. The combined filtrates were concentrated in vacuo to yield a dark grey solid (0.918g, 94% yield). |
94% | With aluminium dodecatungsten phosphate; trifluoroacetic anhydride at 20℃; for 2h; | |
92% | With pyrographite; toluene-4-sulfonic acid at 90℃; for 3.5h; |
86% | With PPA | |
80% | With phosphoric acid; trifluoroacetic anhydride In water at 25℃; for 0.0166667h; | |
80% | With polyphosphoric acid at 100℃; | |
76% | With methanesulfonic acid; phosphorus pentoxide at 50 - 60℃; for 1.5h; | |
75% | Stage #1: phenylacetic acid; methoxybenzene With tetraphosphoric acid In acetonitrile at 20℃; for 0.166667h; Stage #2: With trifluoroacetic anhydride In acetonitrile at 20℃; for 8h; | 4.2. A representative synthetic procedure of skeleton 3 is as follows General procedure: PPA (H6P4O13, polyphosphoric acid, 1.7 g, 5.0 mmol) was added to a solution of substituted arenes (3.3 mmol) and phenylacetic acids (3.0 mmol) in MeCN (10 mL) at rt. The reaction mixture was stirred at rt for 10 min. TFAA (trifluoroacetic anhydride, 850 mg, 4.0 mmol) was added to the reaction mixture at rt. The reaction mixture was stirred at rt for 8 h. The solvent was concentrated. The residue was diluted with water (10 mL) and the mixture was extracted with CH2Cl2 (320 mL). The combined organic layers were washed with brine, dried, filtered and evaporated to afford crude product under reduced pressure. Purification on silica gel (hexanes/EtOAc=8/1-4/1) afforded 3. |
73% | With PPA; Polyphosphoric acid (PPA) at 95℃; for 0.5h; | |
With Chloroacetic anhydride at 180℃; | ||
With PPA | ||
With PPA for 0.5h; Heating; | ||
With eatons reagnt | 133.B A 100 mL round-bottomed flask containing a stir bar is purged with nitrogen and charged with 10.27 g of phenylacetic acid and 50 mL of Eaton's reagent. The mixture is stirred and 8.2 mL of anisole is added. The solution is stirred overnight and then poured into a mixture of 100 mL of toluene and 100 mL of water. The mixture is stirred 30 min and then the layers are separated. The organic layer is washed with 100 mL of water, 100 mL of 5% potassium carbonate and 100 mL of water. The organic layer is dried over magnesium sulfate, filtered and concentrated at the Rotavap. The oil is triturated with 100 mL of heptane. The slurry is stirred for one hour and then filtered. The solids are washed with petroleum ether and then air dried overnight giving 13.26 g. | |
With phosphoric acid; trifluoroacetic anhydride at 25℃; for 0.0166667h; | ||
With polyphosphoric acid at 100℃; | ||
With phosphoric acid; trifluoroacetic anhydride at 25℃; | ||
With phosphoric acid; acetic anhydride at 25℃; for 0.0166667h; | ||
Stage #1: phenylacetic acid With thionyl chloride In tetrahydrofuran for 2h; Reflux; Stage #2: methoxybenzene With aluminum (III) chloride In chloroform at 20℃; for 2h; Cooling with ice; | 1 1.10 g of cinnamamide and 1.20 g of trichloroaldehyde hydrate were added to 30 ml of toluene and refluxed at 110° C. for 8 h, cooled to room temperature to precipitate a large amount of yellow lamellar crystal of (2E)-3-(2-thienyl)-N-(1-hydroxy-2,2,2-trichloroethyl)acrylamide (1.20 g). It was dissolved in 20 ml of anhydrous THF, DMF was added as catalyst, and 1.2 ml of SOCl2 was added dropwise at room temperature, heated to 60° C. and reacted for 2 h. The solvent was evaporated to give a yellow solid of (2E)-3-(2-thienyl)-N-(1,2,2,2-tetrachloroethyl)acrylamide, which was washed with cool petroleum ether to neutral, and dried in vacuum for use. 1.44 g of phenylacetic acid was dissolved in 20 ml of THF, and 2.50 g of SOCl2 was added dropwise at room temperature, refluxed for 2 h, rotary evaporated to remove the solvent to obtain a yellow oil. The yellow oil was dissolved in 10 ml of anhydrous chloroform, and slowly added dropwise under ice-bath to a solution of 1.06 g of methyl phenyl ether and 2.66 g of aluminum trichloride in 20 ml of chloroform, and reacted at room temperature for 2 h after the addition. The reaction solution turned from orange to dark brown. 20 ml of water was slowly added dropwise, the reaction solution was layered. The lower layer was washed with saturated brine for 3 times, 20 ml per time. The organic layer was rotary evaporated to obtain 4′-methoxy-2-phenyl-phenylethylketone. It was refluxed with 4.40 g of CuBr2 in a mixture solvent of 10 ml of ethyl acetate and 10 ml of chloroform for 3 h, the black solid turned white, and the solution turned from clear to dark green. The solid was removed by filtration after the reaction The reaction solution was rotary evaporated and dissolved in 15 ml isopropanol, added with 0.76 g of thiourea, refluxed for 1.5 h, and a large amount of faint yellow solid was precipitated as 4-(4-methoxyphenyl)-5-phenyl-2-aminothiazole. It was added to 20 ml of DMF together with the above mentioned (2E)-3-(2-thienyl)-N-(1,2,2,2-tetrachloroethyl)acrylamide, and stirred at room temperature for 24 h. The reaction solution was poured into 40 ml of water, extracted with ethyl acetate for 3 times, 20 ml each, the organic phases were combined and washed with saturated brine for 3 times, 50 ml each. The organic phase was directly added with 4 g of crude silica gel and stirred, eluted with petroleum ether:ethyl acetate=4:1, to obtain 0.30 g of white solid. [0064] 1H-NMR (400 MHz, DMSO-d6) δ3.74 (s, 3H); 56.84-6.86 (dd, 2H); 6.94-6.98 (m, 1H); δ7.26-7.46 (m, 6H); 57.55-7.61 (t, 1H); δ8.71-8.73 (d, 1H); 69.03-9.05 (d, 1H). MS (TOF) 559.5 (M+). | |
With phosphoric acid; trifluoroacetic anhydride at 20℃; for 0.0833333h; | General procedure for the preparation of compounds 5a-d General procedure: To a stirred solution of phenylacetic acid derivative (1mmol), anisole (1.2 mmol) and phosphoric acid (1.2 mmol)was added trifluoroacetic acid anhydride (4 mmol) andstirred for 5 min at room temperature. Then crushed ice wasadded to the reaction mixture while stirring and the precipitatewas filtered and washed with water and then petroleumether respectively. The crude product was used inthe next step without further purification. | |
With polyphosphoric acid at 100℃; | ||
With phosphoric acid; trifluoroacetic anhydride at 20℃; for 0.166667h; | Synthesis of 1,2-Diarylethanones (1a-j) General procedure: To a mixture of arylacetic acid derivatives (1 eq), anisole or thioanisole (1.2 eq) and phosphoric acid (1.2 eq), was added trifluoroacetic anhydride (4 eq) and the resulting mixture was stirred at room temperature for 10 min. Crushed ice was added to the mixture to precipitate the product and then it was filtered and washed with water and petroleum ether. It was used in the next step without further purification. Compounds characterization was previously reported by us in our recent publication (Kucukkilinc et al. 2017; Valipour et al. 2019). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With zinc(II) oxide at 20℃; for 0.0833333h; | |
96% | With zinc oxide nanoparticles supported on polyaniline at 20℃; for 0.166667h; Neat (no solvent); | |
91% | With iron(III) oxide at 20℃; for 0.166667h; regioselective reaction; |
89% | With aluminium trichloride In dichloromethane at -10℃; for 16h; | |
84% | With aluminum (III) chloride In dichloromethane at 0 - 20℃; | |
81% | With aluminum (III) chloride In chloroform at 0℃; for 1h; | 4.3 General procedure for preparing 2-phenylacetophenone (4,5 & 6) General procedure: Benzyl phenyl ketone was prepared by Friedel Craft reaction. To a solution of phenyl acetic acid (0.01 mol) in chloroform (25 mL), thionyl chloride 97.3 mL, (0.01 mol) was added. This was refluxed on a water bath for 30 min. Finely powdered anhydrous aluminium chloride, (0.01 mol) was added in small portions to a mixture of acid chloride and electron rich arenes (0.01 mol) at 0 °C. The mixture was stirred for 1 h at 0 °C and poured over chopped ice. It was extracted with chloroform and dried over anhydrous sodium sulphate. Removal of solvent by distillation gave the desired product in 75-81% yield. |
78% | With aluminum (III) chloride In dichloromethane at 0 - 20℃; | |
76.8% | With aluminium trichloride In 1,2-dichloro-ethane for 2h; Heating; | |
75% | With copper(II) ferrite In 1,2-dichloro-ethane 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. |
75% | With aluminum (III) chloride at 0 - 20℃; for 1.33333h; Inert atmosphere; | |
75% | Stage #1: methoxybenzene; phenylacetyl chloride With aluminum (III) chloride In dichloromethane at 0℃; for 0.5h; Stage #2: With hydrogenchloride | |
74% | In 1,2-dichloro-ethane at 80℃; for 3h; | |
73% | With aluminum (III) chloride at 0 - 20℃; for 1h; Inert atmosphere; | |
65% | With aluminum (III) chloride at 25℃; for 0.75h; Cooling; | 4.2.1. Experimental Procedure for Ethanones 11 [36] General procedure: The acyl chloride 9 (1 mmol) was cooled and addeddropwise into the cooled mixture of AlCl3 (1.5 mmol) andsubstituted aromatic compounds 10 (1 mmol). The reactionmixture was stirred for 45 min at room temperature. Themixture was then quenched with cold 1M HCl aqueous solution(3 mL), and extracted with chloroform (3 x 1 mL). Thecombined organic extracts were washed with sodium bicarbonatesolution (3 mL), water (3 mL) and dried over anhydroussodium sulfate. After solvent removal, the ethanonederivatives 11 were obtained by recrystallization frommethanol. |
63% | With Si-MCM-41 supported gallium oxide; water In 1,2-dichloro-ethane at 80℃; for 3h; | |
61% | With aluminium trichloride In 1,2-dichloro-ethane for 2h; Heating; | |
51.3% | With aluminum (III) chloride In 1,2-dichloro-ethane at 0 - 20℃; for 2h; | |
49.6% | 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. |
46.4% | With C18H11O3Re 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. |
With tin(IV) chloride; benzene | ||
With mercury dichloride at 100℃; | ||
With carbon disulfide; aluminium trichloride | ||
With aluminium trichloride | ||
With aluminium trichloride 0 to 25 deg C, 1-2 h; | ||
Friedel-Crafts conditions; | ||
61 % Chromat. | With pyrographite In 1,2-dichloro-ethane for 8h; Heating; | |
With aluminium trichloride In carbon disulfide Ambient temperature; | ||
With Nafion resin NR50 at 59.85℃; for 2h; | ||
With aluminium trichloride In dichloromethane at 0 - 20℃; | ||
With aluminium trichloride In dichloromethane at 0 - 20℃; | ||
With aluminium trichloride In dichloromethane | ||
With aluminium trichloride at 20℃; for 0.75h; | ||
With hydrogenchloride In dichloromethane | 1.a a) a) 1-(4'-Methoxyphenyl)-2-phenylethan-1-one To 10.8 g (0.10 mole) methoxybenzene and 13.9 g. (0.09 mole) phenylacetyl chloride in 1.0 1. methylene chloride there are added, by small amounts, 13.3 g. (0.10 mole) aluminium chloride at room temperature and with strong agitation. The reaction mixture is agitated for a further 2 hours and then is poured onto ice and 50 ml. hydrochloric acid are added. After separation of the organic phase, the aqueous solution is shaken out twice with 500 ml. methylene chloride each time, the combined organic phases are washed with water and the solvent is removed in vacuo. The smeary residue is freed of the volatile components by steam distillation and the remaining solid is crystallized from ethanol after filtration and washing with water. Obtained are colorless crystals having a melting point of 75° C.; Rf 0.7 [CHCl3 /CH3 OH (9/1)]; yield: 18.3 g. (90%). | |
With aluminium trichloride at 20℃; for 0.75h; | ||
With aluminum (III) chloride at 0 - 20℃; Inert atmosphere; | ||
Stage #1: methoxybenzene; phenylacetyl chloride With aluminum (III) chloride In 1,2-dichloro-ethane at 0 - 20℃; Stage #2: With hydrogenchloride In water; 1,2-dichloro-ethane Cooling with ice; | 3A Example 3A1-(4-Methoxyphenyl)-2-phenylethanone At 0° C., 10.0 g (64.7 mmol) of phenylacetyl chloride were added dropwise to a suspension of 9.86 g (73.9 mmol) of aluminum trichloride in 200 ml of 1,2-dichloroethane. The mixture was stirred at 0° C. for 5 min, and 6.66 g (61.6 mmol) of anisole were then added dropwise (internal temperature 5-8° C.). After the addition had ended, cooling was removed and the mixture was stirred at RT for 2.5 h. With vigorous stirring, the mixture was then added to ice-water. After addition of conc. hydrochloric acid, the mixture was extracted with 1,2-dichloroethane. The organic phase was washed successively with water, 1 N aqueous sodium hydroxide solution and sat. sodium chloride solution, dried over sodium sulfate and concentrated under reduced pressure. The residue was dried under high vacuum. This gave 16.24 g of the target product, which was used without further purification for the subsequent reaction.LC-MS (Method 1): Rt=2.50 min; m/z=227 (M+H)+ 1H-NMR (400 MHz, DMSO-d6): δ=8.04 (d, 2H), 7.35-7.20 (m, 5H), 7.05 (d, 2H), 4.32 (s, 2H), 3.86 (s, 3H). | |
With aluminum (III) chloride In chloroform at 20℃; for 3h; | ||
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 aluminum (III) chloride In dichloromethane at 0 - 20℃; for 0.5h; | ||
With aluminum (III) chloride In dichloromethane at 0 - 20℃; for 1h; | 2. General procedure for the preparation of substrates General procedure: A 50 mL round bottom flask was charged with 15 mL dichloromethane, a phenylacetyl chloride (30 mmol) and an aromatic hydrocarbon (36 mmol). Aluminum trichloride (4.4 g, 33 mmol) was slowly added with stirring at 0 °C. After 1 hour, the reaction mixture was allowed to warm toroom temperature and stirred overnight. After the reaction was completed (monitored by TLC), the reaction mixture was quenched with ice water and extracted with ethyl acetate (320 mL). The organic layers were combined, dried over anhydrous Na2SO4, concentrated, and washed with n-hexane to obtain the target compound 1. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63.7% | With hydrogenchloride In dichloromethane; methoxybenzene | 14.A A. A. 1-(4-Methoxyphenyl)-2-phenylethanone (11) Phenylacetyl chloride (30.9 g, 0.2 mol) in CH2 Cl2 (100 ml) was added dropwise to a solution of AlCl3 (32 g, 0.24 mol) and anisole (21.6 g, 0.2 mol) in CH2 Cl2 (400 ml) at room temperature. The reaction was complete (by TLC) after 4 hours and was poured over an ice; 10% HCl slurry. The organic layer was washed with H2 O and brine, dried over MgSO4, and the solvent was removed under reduced pressure. The crude solid was chromatographed SiO2 (1500 g), eluding with toluene to afford 11 (20.2 g, 63.7%, para isomer), m.p. 74°-75.5° C. |
With nitromethane; silver perchlorate | ||
Stage #1: methoxybenzene With aluminum (III) chloride at -8.6 - 2.4℃; for 0.416667h; Stage #2: phenylacetyl chloride In water; toluene at -5 - 50℃; for 2.25h; Stage #3: With potassium carbonate In water at 50℃; | 100.A.A A five-liter four-neck reaction flask with a mechanical stirrer, constant addition funnel, nitrogen line, cooling bath and temperature probe is assembled. The flask is purged with nitrogen and charged with anisole (1050 mL.) The liquid is stirred and cooled to -8.6° C. using a dry-ice/acetone bath. Aluminum trichloride (474.0 g) is added in portions over 25 minutes while the internal temperature is maintained below +2.4° C. The mixture is stirred and cooled to -5.0° C. and phenylacetyl chloride (433 mL) is subsequently added over 75 minutes using a constant addition funnel while the temperature is maintained below +4.5° C. The reaction mixture continued stirring cold. A ten-liter rotary evaporator flask with a mechanical stirrer and digital thermometer is assembled. The flask is charged with toluene (2.25 L), water (3.5 L) and ice (840 g) and with stirring the reaction mixture is slowly added over 30 minutes while maintaining the temperature below +50° C. The reaction flask is rinsed with a mixture of toluene (1.0 L) and water (0.5 L) and the rinsate is transferred to the rotary evaporator flask. The biphasic mixture is stirred for 30 minutes and is subsequently allowed to stand. The aqueous layer is removed by vacuum and the organic layer is washed with a fresh portion of water (1.5 L), 5% aqueous potassium carbonate (1.5 L), and another portion of water (1.5 L.) The organic layer is concentrated under reduced pressure (50 Torr) on the rotary evaporator with a bath temperature of 50° C. About 1 L of toluene is removed and the mixture is allowed to stand for the evening. The mixture is concentrated further on the rotary evaporator until pressure is reduced to 34 Torr and very little solvent is distilling over. The total amount of solvent removed is about 3 L. The flask is removed from the rotary evaporator and equipped with a mechanical stirrer. Heptane (2.0 L) is added with stirring. A precipitate formed and the suspension thickened with time. The suspension is diluted further with heptane (3.0 L.) The resulting suspension is stirred for 30 minutes and subsequently filtered. The solids are washed with heptane (2×1 L) and dried in a vacuum oven at 45° C. for 19 hours, 45 minutes to afford the synthetic intermediate 1-(4-methoxy-phenyl)-2-phenyl-ethanone (561.67 g.) |
Stage #1: methoxybenzene With aluminum (III) chloride at 0 - 10℃; Stage #2: phenylacetyl chloride at 20℃; | 133.A Alternatively, A two liter, three neck round bottom flask fitted with a thermocouple is charged with anisole (985 mL, Sigma-Aldrich Chemical, catalog No.12,322-6, lot No.05107AV.) The reaction vessel is cooled to near 0° C. and aluminum trichloride (477 gram, Sigma-Aldrich Chemical, catalog No.195352, lot No.17019MO) is added in 50 gram shots while keeping the temperature below 5° C. While maintaining the temperature between 5° C. and 10° C., phenylacetyl chloride (503 grams, Sigma-Aldrich Chemical, catalog No.P16753, lot No.03618HA) is added. The addition is done over a two and one half hour period. During the addition, the mixture went from a dilute pale yellow slurry to a very deep red colored solution. The reaction is left to warm to room temperature. After stirring overnight, the reaction is quenched by slowly pumping (via syringe pump, J-KEM) to 2.25 liters of cold (-5° C.) water. The temperature is maintained between 5° C. and 10° C. during the addition. The addition is done over a ten-hour period due to the slow output of the pump. After the addition is complete, toluene (1 liter) is added. The mixture is stirred for one hour. The stirrer is stopped and the phases are left to separate overnight. The material is transferred to a six liter separatory and toluene is added until all the solids went into solution (1.25 liters). The phases are separated and the aqueous is washed with toluene (500 mL). The aqueous phase is sampled and checked for product via HPLC. None found. The organics are combined and concentrated via vacuum (40 mm Hg) roto-evaporation (bath at 50° C.) The valve to the receiver is closed and heptane (two liters) is added by way of the feed line. The heptane started to reflux as it is being added and this cooled the liquid in the flask. After cooling to room temperature, the solids are filtered, washed with heptane (2×300 mL) and left to air dry to afford the dry solid title compound (662.6 g.) | |
Stage #1: methoxybenzene With aluminum (III) chloride at -5 - 1.2℃; for 0.416667h; Stage #2: phenylacetyl chloride In water; toluene at 0 - 25.5℃; for 21.6667h; Stage #3: With potassium carbonate In water at 75℃; | 133.A An oven-dried 1 L three-neck flask equipped with mechanical stirrer, constant addition funnel, and digital thermometer probe is purged with nitrogen and is charged with anisole (190 mL.) The liquid is stirred and cooled to -5.0° C. with a methanol-ice bath. A total of 102 g of aluminum trichloride is added in four portions over 25 minutes keeping the internal mixture temperature at or below +1.2° C. A yellow slurry is formed, and the internal mixture is cooled to -4.1° C. The phenylacetyl chloride (92 mL) is added dropwise from the addition funnel over 85 minutes keeping the internal temperature below +6.8° C. The reaction mixture is allowed to warm slowly to room temperature as it is stirred for 20 hours. A 2 L three-neck flask equipped with mechanical stirrer, constant addition funnel, and digital thermometer probe is charged with toluene (500 mL) and ice-cooled water (800 mL.) The flask is submerged into an ice-water bath for additional cooling. The biphasic mixture is stirred vigorously, and the dark red reaction mixture that had been transferred to the additional funnel is added slowly over 15 minutes keeping the internal temperature below +25.5° C. The reaction flask is rinsed with toluene and the rinse is likewise added to the stirring biphasic mixture. The phases (both layers are cloudy tan oily suspensions) are separated using a 2 L separatory funnel and the organic phase is washed with 20% aqueous potassium carbonate (500 mL) and a portion of fresh water (500 mL), is dried over anhydrous potassium carbonate, and is concentrated in vacuo (water bath temperature=75° C., 200 mbar vacuum), until no further toluene is removed, to a clear yellow oil. With the oil still warm, hexanes are added with swirling to form an oily suspension that is allowed to stand open at room temperature in the fume hood for several hours as a white crystalline solid precipitates. The crystals are collected by vacuum filtration. After rinsing with hexanes, the product is suction dried to afford the white crystalline solid title compound (114.65 g); 1H-NMR (400 MHz, CDCl3) δ 8.00 (m, 2H), 7.34-7.22 (m, 5H), 6.92 (m, 2H), 4.23 (s, 2H), 3.85 (s, 3H); 13C-NMR (100 MHz, CDCl3) 196.4, 163.7, 135.2, 131.2, 129.9, 129.6, 128.9, 127.0, 114.0, 55.7, 45.5; MS (APCI+) 227 (MH+.) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With scandium tris(trifluoromethanesulfonate) In toluene at -78℃; for 0.166667h; Inert atmosphere; | |
55% | In dichloromethane at 20℃; for 12.5h; | |
90 % Spectr. | With lithium bromide In diethyl ether at -5 - 0℃; protected from light; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88.3% | With 4-acetamidobenzenesulfonyl azide; 1,8-diazabicyclo[5.4.0]undec-7-ene In toluene for 7h; | 12 Mix 30g (0.133mol) of the compound of formula (I-12) with 24.2g (0.159mol) DBU, add 300mL of toluene, stir and mix well, control the temperature of the ice-water bath to be 0-5°C, and add 38.2g (0.159mol) in batches 4-acetylaminobenzenesulfonyl azide was stirred and reacted for 3h. The amount added each time was 10% of the total amount of 4-acetamidobenzenesulfonyl azide. After 60min was added, it was naturally returned to room temperature (25°C), and the stirring was continued. The reaction was carried out for 3 h, extracted twice with 100 mL of ethyl acetate, left to stand for stratification, the organic phases were combined, the temperature of the water bath was controlled to be 35°C, and spun dry to obtain 35.6 g of crude product with a purity of 92.8%;35.6 g of crude product was slurried using 100 mL of a solvent with a volume ratio of petroleum ether:ethyl acetate=8:1, filtered and dried to obtain 30 g of benzyldiazo acetophenone compounds , purity 95.9%, yield 88.3% . |
79% | With 4-acetamidobenzenesulfonyl azide; 1,8-diazabicyclo[5.4.0]undec-7-ene In acetonitrile at 0 - 20℃; for 1h; Inert atmosphere; | |
36% | With 4-acetamidobenzenesulfonyl azide; 1,8-diazabicyclo[5.4.0]undec-7-ene In acetonitrile at 0 - 20℃; for 5h; Inert atmosphere; |
With 4-toluenesulfonyl azide; potassium ethanolate In diethyl ether; ethanol | ||
With 4-acetamidobenzenesulfonyl azide; 1,8-diazabicyclo[5.4.0]undec-7-ene In acetonitrile at 0 - 25℃; for 2h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With phosphorus pentachloride In benzene | 14 Preparation of p-Methoxy-α-chlorostilbene (Compound 33) EXAMPLE 14 Preparation of p-Methoxy-α-chlorostilbene (Compound 33) The procedure of Nagano (NAGANO. T. (1955), "Triphenylethylene derivatives", Journal of the American Chemical Society, 77, 1691), was followed wherein p-methoxydeoxybenzoin (Compound 32) is treated with PCl5 in refluxing benzene. A reddish oil, obtained upon evaporation of the solvent in vacuo and solidified immediately, was recrystallized from EtOH to give colorless plates (80%), mp 70°-71° C. (lit (Nagano, 1955) 72°-72° C.). 1 H NMR (CDCL3) δ 3.83 (s, 3H, (OCH3), 6.86-7.86 (m, 10H, ArH and C=CH). |
75% | With silica gel; acetyl chloride; zinc(II) chloride In 1,2-dichloro-ethane at 30℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | Stage #1: 4-methoxyphenyl benzyl ketone With potassium hexamethylsilazane In tetrahydrofuran; toluene at -78℃; for 1h; Stage #2: 2-bromo-1-(4-methoxyphenyl)butan-1-one In tetrahydrofuran; toluene at -78 - 20℃; Further stages.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | Stage #1: 4-methoxyphenyl benzyl ketone With sodium hydride In tetrahydrofuran; mineral oil at 0 - 20℃; Stage #2: ethyl bromide With potassium iodide In tetrahydrofuran; mineral oil at 20℃; for 12h; | |
With potassium <i>tert</i>-butylate In diethyl ether Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89.9% | In toluene at 50 - 80℃; | 4A Example 4A3-(Dimethylamino)-1-(4-methoxyphenyl)-2-phenylprop-2-en-1-one 21.7 g (95.9 mmol) of 1-(4-methoxyphenyl)-2-phenylethanone were dissolved in 110 ml of toluene and warmed to 50° C., and 19.1 ml (143.9 mmol) of N,N-dimethylformamide dimethyl acetal were added. The reaction mixture was stirred at 80° C. overnight and then, after cooling, concentrated under reduced pressure. The residue was repeatedly taken up in toluene and in each case concentrated to dryness under reduced pressure again. The solid obtained was triturated with petroleum ether, filtered off and dried under high vacuum. This gave 24.26 g of the target product (89.9% of theory).1H-NMR (400 MHz, DMSO-d6): δ=7.37 (d, 2H), 7.31-7.18 (m, 4H), 7.10 (d, 2H), 6.87 (d, 2H), 3.28 (s, 3H), 2.68 (s, 6H). |
85% | In N,N-dimethyl-formamide at 100℃; for 2h; Microwave irradiation; | 4.1.10. 4-Dimethylamino-3-(4-methoxyphenyl)-but-3-en-2-one (8a) General procedure: Into a 20mL microwave vial equipped with a magnetic stir bar and crimping cap was added 4-methoxyphenylacetone (0.545g, 3.32mmol), N,N-dimethylformamide dimethyl acetal (3.18g, 26.6mmol), and dimethylformamide (5mL). The reaction mixture was heated in a microwave reactor for 2h at 100°C. The solvent was removed in vacuo, the crude mixture was diluted with water (30mL), and the aqueous solution was extracted with ethyl acetate (3×15mL). The combined organic phases were washed with aqueous lithium chloride (20mL), dried over anhydrous sodium sulfate, and concentrated in vacuo to yield an orange solid (0.721g, 99% yield) |
57% | In 5,5-dimethyl-1,3-cyclohexadiene for 2h; Reflux; | 5.1.7. 3-(dimethylamino)-1-(4-methoxyphenyl)-2-phenyl-2-propen-1-one (16b) Dimethylformamide dimethylacetal (10 mmol) was added to a suspension of 15b (10 mmol) in xylene (30 mmol) and the mixture was refluxed for 2 h. After solvent evaporation, the residue was chromatographed on silica gel eluting with cyclohexane/AcOEt 7:3 and, then, AcOEt. The first eluate gave the starting product, the second eluate gave 16b as a yellow solid, crystallized from diethyl ether, mp 92-94 °C. Yield 57%. 1H NMR (200 MHz, CDCl3): δ 2.90 [6H, s, N(CH3)2],3.98 (3H, s, OCH3), 6.92 (2H, d, J = 8.8, Ar), 7.29-7.50 (5H, m, Ar + =CH), 7.55-7.61 (3H, m, Ar). Anal. calcd. for C18H19NO2: C, 76.84; H, 6.81; N, 4.98; found: C, 76.86; H, 6.84; N, 4.95. |
for 12h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 4-methoxyphenyl benzyl ketone With chlorosulfonic acid In dichloromethane at 20℃; Stage #2: With ammonia In water at 20℃; | ||
28 EXAMPLE 28: EXAMPLE 28: Preparation of 2-(4-aminosulfonylphenyl)-1-(4-methoxyphenyl)ethanone (intermediate 7, R4= R5= H, R6= OCH3) The title compound was obtained from 2-phenyl-1-(4-methoxyphenyl)ethanone as a pale yellow powdered solid, using the method of Example 23. | ||
With chlorosulfonic acid; ammonium hydroxide In (2S)-N-methyl-1-phenylpropan-2-amine hydrate; water; ethyl acetate; acetone | 45.2 4-[5-Difluoromethyl-3-(4-methoxyphenyl)isoxazol-4-yl]benzenesulfonamide Step 2. Preparation of 1-(4-methoxyphenyl)-2-(4-aminosulfonylphenyl)-ethan-1-one. Chlorosulfonic acid (30 mL) was cooled to -78° C. and treated with 1-(4-methoxyphenyl)-2-phenyl-ethan-1-one from Step 1 (4.0 g, 18 mmol). The mixture was warmed to 0° C. and stirred for 2 hours, then added dropwise to ice water (500 mL). Ammonium hydroxide (100 mL) and ethyl acetate (100 mL) were added and the solution was stirred for 16 hours. A sticky white solid, isolated by filtration, was dissolved in boiling acetone/water, and allowed to stand overnight. A white solid was isolated by filtration (2.4 g, 44%): mp 253.7°-257.7° C. 1 H NMR (DMSO-d6 /300 MHz) 8.0 (d, J=8.1 Hz, 2H), 7.7 (d, J=7.5 Hz, 2H), 7.4 (d, J=7.8 Hz, 2H), 7.2 (bs, 2H), 7.0 (d, J=7.8 Hz, 2H), 4.4 (s, 2H), 3.8 (s, 3H). Anal. Calc'd. for C16 H13 BrN2 O3 S: C, 48.87; H, 3.33; N, 7.12. Found: C, 48.77; H, 3.21; N, 6.99. |
Multi-step reaction with 2 steps 1: chlorosulfonic acid / 2 h / -78 - 0 °C 2: ammonia / water; ethyl acetate |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With toluene-4-sulfonic acid In ethanol at 120℃; for 0.5h; microwave irradiation; | |
80% | With toluene-4-sulfonic acid In ethanol at 78℃; for 72h; | |
74% | With silver hexafluoroantimonate; 1,3-bis(2,6-di-isopropylphenyl)imidazole-2-ylidenegold(I) chloride In 1,4-dioxane; water monomer at 80℃; for 16h; |
65% | With water monomer; trifluoromethane sulfonic acid silver salt In chlorobenzene at 100℃; for 44h; Sealed tube; Inert atmosphere; | 2.3; 3 A magnetic stirring bar, 1-p-tolylhexane-1-yne (1.45 g, 7 mmol), and AgOTf (89.9 mg, 0.35 mmol) were added to the sealed tube, and the system was protected by argon. Water (8.4 mmol) was dissolved in 10 mL of PhCl, and the seal tube was quickly added with a 20 mL syringe, after which the seal tube was sealed. The sealed tube was placed in an oil bath pot on a magnetic stirrer with heating function, and the reaction was stirred at a constant temperature of 100 °C for 46 hours, and the reaction was monitored by thin-layer chromatography. After being cooled to room temperature, concentrated under reduced pressure and separated by column chromatography to obtain the product 1-(4-methoxyphenyl)-2-phenylethan-1-one (1 g, 63% yield), |
22% | With 1,10-Phenanthroline; copper(II) dichloride dihydrate; trifluoromethane sulfonic acid silver salt; aniline; 1,2-(diphenylphosphino)ethane; palladium (II) chloride In 1,4-dioxane; water monomer at 100℃; for 24h; | General procedure: To a tube equipped with a condenser was added aniline (1, 0.2 mmol), diphenylacetylene (2, 0.4 mmol), PdCl2 (3.5 mg,0.02 mmol), CuCl2·2H2O (6.8 mg, 0.04 mmol), DPPE (7.9 mg,0.02 mmol), 1,10-phenanthroline monohydrate (15.9 mg, 0.08 mmol), AgOTf (10.3mg, 0.04 mmol), H2O (18 mg, 18 μL, 1 mmol), dioxane (0.25 mL). Themixture was stirred and heated at 100 °C for 24 h until the substratedisappeared as monitored by TLC. The reaction mixture was cooled down to room temperature,dried under vacuum and purified by column chromatography on silica gel toobtain the desired products 3 (petroleumether:ethyl acetate = 20:1). |
With hydrogenchloride; water monomer; N-hexadecyl-N,N,N-trimethylammonium bromide In isopropanol at 140℃; for 10h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With [2,2]bipyridinyl; palladium diacetate; trifluoroacetic acid In tetrahydrofuran; water at 80℃; for 36h; Inert atmosphere; Schlenk technique; | |
92% | With ammonium chloride In water at 100℃; for 24h; | |
87% | In nitromethane for 24h; Heating; |
86% | With bathophenanthroline; water; copper diacetate; manganese(III) triacetate dihydrate In 1,4-dioxane at 90℃; | General procedure for the synthesis of arylketones General procedure: In a 25mL round bottom flask (oven-dried overnight) was added the phenyl boronic acid (1a, 1.0 mmol) followed by the addition of 1,4-dioxane (6mL). To this solution, manganese (III) acetate. dihydrate (5mol%), Bphen (3e, 10mol%), Cu(OAc)2 (5mol%), nitrile (0.5mmol) and water (0.5mmol) were added sequentially. The reaction was then stirred at room temperature for 10min and slowly brought to 90°C under air. The reaction was allowed to run for overnight at the same temperature. After the completion, the reaction mixture was quenched and extracted with ethyl acetate and water. The organic layer was collected, and the aqueous layer was again extracted with ethyl acetate for three more times. The combined organic layer was further washed with sodium bicarbonate and brine solution. The organic layer was then dried over sodium sulfate, filtered and evaporated using rotavap. The crude compound obtained was further purified using column chromatography (EA:hexane 10:90). |
80% | With 1,2-bis(diphenylphosphino)ethane nickel(II) chloride; water; zinc(II) chloride In 1,4-dioxane at 80℃; for 8h; Inert atmosphere; | |
40% | With palladium diacetate; 2-(3,5-dimethyl-1H-pyrazol-1-yl)pyridine In trifluorormethanesulfonic acid; water at 60℃; for 3.5h; | General procedure I for the synthesis of deoxybenzoin analogues (15B-G, I-O) General procedure: To a solution of phenylacetonitrile (14) (1 mmol,1.00 equiv.) and boronic acid (13) (1.20 equiv.), in water and triflic acid (3:1, 12 mL), was added 2-(3,5-dimethyl-1H-pyrazol-1-yl)pyridine (0.05 equiv.) and Pd(OAc)2 (0.05 equiv.). This reaction mixture was stirred at 60C for 3.5 h. The mixture was cooled to room temperature, neutralised with sat. aq. NaHCO3 and extracted with diethyl ether (3 30 mL). The organic extracts were combined, washed with brine (100 mL), dried over MgSO4 and concentrated in vacuo. The residue was then purified by column chromatography to yield the product. |
With 1,2-bis(diphenylphosphino)ethane nickel(II) chloride; zinc(II) chloride In 1,4-dioxane; water at 80℃; for 8h; Inert atmosphere; | ||
With {NiJ2-1.2-Bis-diphenylphosphino-aethan}; water; zinc(II) chloride In 1,4-dioxane at 80℃; for 24h; Sealed tube; Inert atmosphere; | ||
With [2,2]bipyridinyl; palladium diacetate; trifluoroacetic acid In tetrahydrofuran; water at 80℃; for 36h; Inert atmosphere; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | Stage #1: 1-bromo-4-methoxy-benzene; 1-(2-methoxyvinyl)benzene With sodium hydrogencarbonate In N,N-dimethyl-formamide at 150℃; for 20h; Stage #2: With hydrogenchloride In tetrahydrofuran at 25℃; Further stages.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With 1,3-dimethyl-3,4,5,6-tetrahydro-2(1H)-pyrimidinone; sodium hexamethyldisilazane In tetrahydrofuran at -78 - 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 4 steps 1: 97 percent / Zn; I2 / benzene / 1 h / Heating 2: 90 percent / Et3SiH; TFA; BF3*Et2O / CH2Cl2 / 8 h / Heating 3: 92 percent / aq. KOH / 8 h / Heating 4: 85 percent / polyphosphoric acid / 1 h / 80 °C | ||
Multi-step reaction with 4 steps 1: zinc; iodine / diethyl ether; benzene / 20 °C / Inert atmosphere 2: hydrogen; palladium 10% on activated carbon / ethyl acetate; methanol / 24 h / 20 °C / Inert atmosphere 3: sodium hydroxide / methanol; water / Reflux 4: polyphosphoric acid / 100 °C | ||
Multi-step reaction with 4 steps 1: zinc; iodine / diethyl ether; benzene / 20 °C / Inert atmosphere 2: hydrogen; palladium 10% on activated carbon / ethyl acetate; methanol / 24 h / 20 °C / Inert atmosphere 3: sodium hydroxide / methanol; water / Reflux 4: polyphosphoric acid / 100 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 51 percent 2: 65 percent / H2SO4, NaNO2 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With hydrogenchloride; sodium nitrite In water at 23℃; for 3h; Sealed tube; | |
Multi-step reaction with 2 steps 1: S2O8(2-), HClO4 / Cu(ClO4)2 / acetonitrile; H2O / 0.42 h / 83 °C / other reaction conditions, other substrate 2: pyridine-chlorochromate | ||
Multi-step reaction with 3 steps 1: S2O8(2-), HClO4 / Cu(ClO4)2 / acetonitrile; H2O / 0.42 h / 83 °C / other reaction conditions, other substrate 3: pyridine-chlorochromate |
With ketoreductase-P1-B12; oxygen; NADPH; 9-(2-mesityl)-10-methylacridinium perchlorate In water; acetonitrile at 23℃; for 24h; Irradiation; Enzymatic reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With chloro(1,5-cyclooctadiene)rhodium(I) dimer; sodium 2,2,2-trifluoroacetate; diphenyl(methyl)phosphine; bis(pinacol)diborane In tetrahydrofuran at 70℃; for 10h; Glovebox; Sealed tube; Inert atmosphere; stereoselective reaction; | |
Multi-step reaction with 2 steps 1: Reduktion nach Meerwein-Ponndorf 2: acetic acid; H2SO4 | ||
Multi-step reaction with 2 steps 1: sodium-amalgam 2: acetic acid; concentrated aqueous HCl |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
40.3% | With hydrogenchloride; paraformaldehyde; In nitromethane; ethanol; water; toluene; | EXAMPLE 8 A mixture of 125 ml of nitromethane, 20 ml of ethanol, 35 ml of toluene and2 ml of concentrated hydrochloric acid was added with 22.6 g of p-methoxyphenyl benzyl ketone, 18.2 g of <strong>[6091-44-7]<strong>[6091-44-7]piperidine</strong> hydrochloride</strong> and 6.9 g of paraformaldehyde. The mixture was heated under reflux for 1.5 hrs. while distilling off water generated through the reaction. After cooling, the solvent was removed from the reaction mixture under reduced pressure. The residue was dissolved in water, and the solution was extracted with ether, then with benzene, and the extract was dried over anhydrous sodium sulfate. Recrystallization of the product from methanol-acetone after removal of the solvent gave 14.5 g of white crystals of 4'-methoxy-2-phenyl-3-piperidinopropiophenone hydrochloride. (yield 40.3%), m.p. 148-149 C. Elementary analysis (C21 H25 NO2.HCl) |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: (diethylamino)(4-methoxyphenyl)acetonitrile With sodium hydride In DMF (N,N-dimethyl-formamide) at 20℃; for 1h; Stage #2: benzyl chloride In DMF (N,N-dimethyl-formamide) at 20℃; Stage #3: With hydrogenchloride; methanol; water more than 3 stages; | 5 Reference Example 5; (4-METHOXYPHENYL)-(BENZYL)-KETONE Sodium hydride (50% dispersion in oil, 960mg, [20MMOL)] was washed with petrol and suspended in anhydrous DMF [(LOML)] under nitrogen. N, [N-DIETHYL-N-(A-CYANO-4-] methoxybenzyl) amino (Method 4: 3.27g, 15mmol) was placed in anhydrous DMF (20ml) and added to the reaction which was stirred at room temperature for 1 hour. Benzyl chloride (1.89g, 1. 73ml, [15MMOL)] in anhydrous DMF [(LOML)] was added dropwise over 1 hour at room temperature (slight exotherm) and the reaction was stirred overnight at room temperature. Methanol [(5ML)] was added and the solvent removed in vacuo at [90°C] followed by high vacuum for 2 hours, to give a yellow oil. This was stirred in hydrochloric acid (6M; 40ml) for 16 hours, and then extracted into chloroform (3 x 30ml), washed with water, dried [(MGS04)] and evaporated to dryness to give a yellow oil. This was purified by column chromatography with ether: hexane (2: 1). The product was then recrystallized from [40-60°C] petrol to give a colourless solid 410mg. Mp [68-69°C] ; m/z 226. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With pyrrolidine; 1,3-bis-(diphenylphosphino)propane; bis(dibenzylideneacetone)-palladium(0) In N,N-dimethyl-formamide at 115℃; for 6h; Molecular sieve; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
55% | With potassium phosphate; palladium diacetate; tricyclohexylphosphine In water at 80℃; for 20h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With triethylamine In tetrahydrofuran; acetonitrile at 20℃; for 2h; | Typical procedure for the synthesis of amide 3 by the reaction of benzyl carbonyl compounds 2 and ADMP 1. General procedure: To a solution of 2-azido-1,3-dimethylimidazolinium hexafluorophosphate (ADMP, 1) (258 mg, 0.90 mmol) in MeCN (0.7 mL), deoxybenzoin 2a (118 mg, 0.60 mmol), and Et3N (1.2 mmol) in THF (2.7 mL) were added at 0 °C and the reaction mixture was stirred for 10 min. The reaction was quenched with H2O (5 mL), and the organic materials were extracted with EtOAc (3 × 10 mL). The combined extracts were washed with H2O (3 × 30 mL), and brine (20 mL), and then dried over anhydrous Na2SO4. The solvent was removed in vacuo to afford crude compounds, which were purified by flash column chromatography (silica gel: chloroform-methanol) to give the pure migratory amidated compound 3a in 89% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With palladium diacetate; 1,4-di(diphenylphosphino)-butane; zinc In 1,4-dioxane at 100℃; for 16h; Inert atmosphere; Autoclave; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
7.5% | With hydrogenchloride; In ethanol; water; for 48.0h;Reflux; | 165] To a mixture of l-(4-methoxyphenyl)-2-phenylethanone (200 mg, 0.88 mmol),<strong>[178686-24-3]3-ethoxy-4-hydroxy-5-nitrobenzaldehyde</strong> (187 mg, 0.89 mmol), and urea (159 mg, 2.65 mmol) in anhydrous EtOH (20 mL) was added concentrated HC1 solution (0.1 mL). The reaction mixture was refluxed for two days. When TLC (EtOAc:MeOH=10: l) showed that about 30% of the starting materials were consumed, the reaction mixture was concentrated. The residue was purified by column chromatography (EtOAc:MeOH=40: l) and preparative HPLC to afford Compound 20 as a yellow solid (30 mg, yield: 7.5%). 1H NMR (DMSO- 6 300 MHz): delta 10.30 (s, 1H), 8.65 (s, 1H), 7.52 (s, 1H), 7.45 (s, 1H), 7.20 (s, 1H), 7.09-7.15 (m, 2H), 6.96-7.08 (m, 3H), 6.75-6.82 (m, 4H), 5.12(s, 1H), 4.00-4.10 (m, 2H), 3.70 (s, 3H), 1.34(t, J = 6.9 Hz, 3H); MS (ESI): m/z 462.0 [M+l]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With piperidine; acetic acid In benzene for 30h; Reflux; | 1-(4-Methoxyphenyl)-2-phenyl-3-(4-hydroxyphenyl)-3-propen-1-one (16): To a solution of 4-methoxydeoxybenzoin 15 (22.6 g, 0.1mol) and 4-hydroxybenzaldehyde (12.2 g, 0.1mol) in dry benzene (100 mL) was added piperidine (1 ml) and CH3COOH (0.5 mL). The reaction mixture was refluxed for 30 h,removing water azeotropically. The reaction mixture was then cooled and washed with water. The organic layer was separated, dried over anhydrous sodium sulphate and concentrated. The residue was chromatographed over a column of silica gel, eluting with the ethyl acetate-hexane to afford compound 16. Yield: 80 %, m.p.131-133°C. FABMS: 331; IR (cm-1): 3445, 1650, 1501; 1H NMR(δ): 3.08 (s, 3H, OCH3), 6.63 (d, J = 8.60 Hz, 2H, ArH), 6.83 (d, J = 8.90 Hz, 2H, ArH), 7.08 (s, 1H, CH), 7.23 (m, 5H, ArH), 7.40 (d, J = 7.00 Hz, 2H, ArH), 7.97(d, J = 8.90 Hz, 2H, ArH). Anal. Calcd. for C22H18O3; C, 80.00; H, 5.45. Found: C, 80.21; H, 5.63. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With caesium carbonate In 1,2-dimethoxyethane at 20℃; for 5h; Inert atmosphere; | A representative synthetic procedure of skeleton 4 or 6 is as follows: General procedure: Cs2CO3 (652 mg, 2.0 mmol) was added to a solution of skeleton 2 or 5 (1.0 mmol) in dimethoxyethane (DME, 10 mL) at rt. Then triflic anhydride (Tf2O, 290 mg, 1.03 mmol) was slowly added to the reaction mixture. The reaction mixture was stirred at rt for 5 h. The reaction was traced by TLC until skeleton 2 or 5 was consumed. Next, Pd(OAc)2 (34 mg, 0.15 mmol) and racemic BINAP (100 mg, 0.16 mmol) were added to the stirred solution at rt for 10 min. Then NaNO2 (280 mg, 5.0 mmol) and TBAB (322 mg, 1.0 mmol) were added to the reaction mixture. The reaction mixture was stirred at reflux for 5 h. The reaction mixture was cooled to rt. NH4Cl (aq) (1 N, 5 mL) was added to the reaction mixture and the solvent was concentrated. The residue was diluted with water (10 mL) and the mixture wasextracted with EtOAc (3 x 20 mL). The combined organic layers were washed with brine, dried, filtered and evaporated to afford crude product. Purification on silica gel (hexanes/EtOAc = 20/1~6/1) afforded skeleton 4 or 6. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With palladium diacetate; 1,4-di(diphenylphosphino)-butane In tetrahydrofuran at 90℃; for 1h; Sealed tube; Microwave irradiation; chemoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide In ethanol at 20℃; Green chemistry; | General procedure for preparing 1,2,3,5-tetraphenylpentan-1,5-diones (9-23) General procedure: A mixture of 2-phenylacetophenone (4/5/6) (0.01 mol), acetophenones (7) (0.01 mol), bezaldehydes (8) (0.01 mol) and sodium hydroxide solution (10 mL, 10%) in ethanol (50 mL) was stirred for 60 min at room temperature. The solid that separated was filtered and was recrystallized from ethanol. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With sodium hydroxide In ethanol at 20℃; Green chemistry; | General procedure for preparing 1,2,3,5-tetraphenylpentan-1,5-diones (9-23) General procedure: A mixture of 2-phenylacetophenone (4/5/6) (0.01 mol), acetophenones (7) (0.01 mol), bezaldehydes (8) (0.01 mol) and sodium hydroxide solution (10 mL, 10%) in ethanol (50 mL) was stirred for 60 min at room temperature. The solid that separated was filtered and was recrystallized from ethanol. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With C16H14N6O4Pd; potassium <i>tert</i>-butylate In acetonitrile at 82℃; for 2h; Schlenk technique; Reflux; | Synthetic procedure for ketone a-arylations reaction General procedure: An oven-dried, resealable Schlenk tube containing a stirbar was charged with aryl halide (1.0 mmol), ketone(1.1 mmol), potassium tert-butoxide (1.5 mmol), and1.0 mol % catalyst. Acetonitrile (10 mL) was sequentiallyadded and the tube was backfilled with nitrogen, and themixture was stirred in an oil bath at reflux temperature forthe time specified. After the reaction was completed, thesolvent was removed on a rotary evaporator and the mixturewas purified by chromatography on silica gel. The pure product was obtained, and the yield was calculated basedon ArX. |
71% | With tris-(dibenzylideneacetone)dipalladium(0); bis[2-(diphenylphosphino)phenyl] ether; sodium t-butanolate In tetrahydrofuran at 70℃; for 3h; Schlenk technique; Inert atmosphere; | |
54% | With bis[2-(diphenylphosphino)phenyl] ether; sodium t-butanolate In tetrahydrofuran at 70℃; for 3h; Inert atmosphere; |
92 %Chromat. | With potassium <i>tert</i>-butylate In acetonitrile at 81℃; for 2h; Inert atmosphere; Schlenk technique; | 2.7. Catalysis and recycling General procedure: The catalytic experiments were carried out using potassium tertbutoxide(1.5 mmol) as a base, functionalized silica materials (approx.Pd content 1.0 mol%) as catalyst, and ketone (1.0 mmol), and aryl halide(1.2 mmol) as reagents in acetonitrile (10 mL) at reflux temperature.After cooling the reaction mixture, the reaction vessel was centrifugedto settle the silica and the catalyst was separated from theliquid product by decanting the supernatant carefully and then filtration.The filtrate was analyzed by gas chromatography to determine theyield of the product. The recovered catalyst was washed twice withCH2Cl2 and dried in vacuo. It was then used for the next run. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
63% | In toluene at 120℃; Inert atmosphere; | Typical procedure for the cross-coupling betweenthe ion pair in sulfonium tetraphenylborates General procedure: To atwo-neck flask equipped with a condenser which is connected to a nitrogenballoon, thiolanium tetraphenylborate 2a(210.6 mg, 0.4 mmol) and toluene (8 mL) which was degassed by purgingnitrogen was added by syringe. The reaction mixture was heated in an oil bath(bath temperature, 120 °C). The reaction was monitored by TLC. After reaction, the reactionmixture was cooled down to room temperature, evaporated to remove solvent, andthen separated by preparative TLC (silica gel). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
71% | Stage #1: 4-methoxyphenyl benzyl ketone With silver fluoride In 5,5-dimethyl-1,3-cyclohexadiene at 140℃; for 10h; Stage #2: With toluene-4-sulfonic acid In 5,5-dimethyl-1,3-cyclohexadiene for 3h; | |
64% | With oxygen; copper(II) acetate monohydrate; trifluoroacetic acid; silver(l) oxide In 5,5-dimethyl-1,3-cyclohexadiene at 140℃; for 8h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With copper(l) cyanide; lithium chloride In tetrahydrofuran at 0℃; for 2h; Inert atmosphere; | Copper-Catalyzed Cross-Coupling Reaction General procedure: Into a 25 mL round-bottomed flask were placed CuCN (0.02 g,10 mol%) and LiCl (0.02 g, 20 mol%). Benzylic zinc mesylate (I,5.0 mL, 0.5 M in THF, 2.5 mmol) was added into the flask underan argon atmosphere. Next, 4-bromobenzoyl chloride (0.44 g,2.0 mmol) was slowly added via a syringe while being stirred at0 °C. The resulting mixture was at 0 °C for 2 h, quenched with3.0 M HCl solution, then extracted with Et2O (3 × 10 mL),washed with sat. NaHCO3, Na2S2O3 solution and brine, and thendried over anhydrous MgSO4. Purification by column chromatographyon silica gel (EtOAc-heptane, 2:98) afforded 0.38 g of 1-(4-bromophenyl)-2-phenylethanone (1b) in 70% isolatedyield as a white solid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | Stage #1: 4-methoxyphenyl benzyl ketone With sodium hydride In tetrahydrofuran at 20℃; for 0.166667h; Inert atmosphere; Stage #2: propargyl bromide In tetrahydrofuran for 8h; Reflux; Inert atmosphere; | |
76% | Stage #1: 4-methoxyphenyl benzyl ketone With sodium hydride In tetrahydrofuran; mineral oil at 20℃; for 0.166667h; Stage #2: propargyl bromide In tetrahydrofuran for 8h; Reflux; | 4.3. A representative synthetic procedure of skeleton 4 is as follows General procedure: NaH (120 mg, 60 % in oil, 3.0 mmol) was added to a solution of 3 (1.0 mmol) in THF (10 mL) at rt. The reaction mixture was stirred at rt for 10 min. Propargyl bromide (140 mg, 1.2 mmol) was added to the reaction mixture at rt. The reaction mixture was stirred at reflux for 8 h. The reaction mixture was cooled to rt and the solvent was concentrated. The residue was diluted with water (10 mL) and the mixture was extracted with CH2Cl2 (320 mL). The combined organic layers were washed with brine, dried, filtered and evaporated to afford crude product under reduced pressure. Purification on silica gel (hexanes/EtOAc = 8/1-4/1) afforded 4. |
With potassium carbonate In acetone |
With potassium carbonate |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | Stage #1: 4-methoxyphenyl benzyl ketone With sodium hydride In tetrahydrofuran; mineral oil at 25℃; for 0.166667h; Inert atmosphere; Stage #2: prenyl bromide In tetrahydrofuran for 8h; Reflux; Inert atmosphere; | |
65% | Stage #1: 4-methoxyphenyl benzyl ketone With sodium hydride In tetrahydrofuran; mineral oil for 0.25h; Inert atmosphere; Stage #2: prenyl bromide In tetrahydrofuran; mineral oil for 24h; Inert atmosphere; Reflux; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With potassium tert-butylate; In dimethyl sulfoxide; at 120℃; for 12.0h;Inert atmosphere; | In the reaction flask, 0.25 mmol of o-fluorophenylacetylene was added,0.25 mmol of 1-(4-methoxyphenyl)-2-phenylethanone, 0.25 mmol of potassium tert-butoxide and 1 ml of dimethylsulfoxide were added and stirred under a nitrogen gas atmosphere at 120C for 12 hours. The heating and stirring were stopped, and the mixture was cooled to room temperature. The crude product was distilled under reduced pressure and purified by column chromatography to obtain the desired product. The eluant used in the column chromatography was pure hexane, and the yield was 72%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
73% | With bis(1,5-cyclooctadiene)nickel (0); 1,3-bis(2,6-diisopropylphenyl)dihydroimidazol-2-ylidene In tetrahydrofuran at 23℃; for 24h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 40% 2: 48% | With iodine; dimethyl sulfoxide; sodium sulfate at 120℃; for 12h; | |
With nitric acid In dimethyl sulfoxide at 100℃; for 12h; Sealed tube; | 2 Example 2 Put 0.1mmol oxidized lignin model substrate 1 in a 10mL pressure tube, add 0.01mmol HNO3, 1mL DMSO and 0.2mmol o-phenylenediamine 2,After tightening the cap, heat the resulting reaction solution (the concentration of oxidized lignin in the reaction solution is 0.1 mmol/mL) in an oil bath at 100°C for 12 hours,The decomposition reaction is carried out. After the reaction is completed, the obtained product is taken out and the solvent is drained and separated by a column to obtain two nitrogen-containing heterocyclic products. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: copper(ll) bromide / ethyl acetate; dichloromethane / 18 h / Reflux; Inert atmosphere 2: 1,4-dioxane; water / 18 h / Reflux; Inert atmosphere 3: boron trifluoride diethyl etherate / dichloromethane / 2 h / 20 °C / Inert atmosphere |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | With tert.-butylhydroperoxide; bis[dichloro(pentamethylcyclopentadienyl)iridium(III)]; calcium oxide In nonane at 140℃; for 48h; Inert atmosphere; Schlenk technique; Sealed tube; | 3. Experimental Procedures General procedure: Under nitrogen, a 20 mL Schlenk tube equipped with a stir bar was charged with 1 (0.1 mmol), [Cp*IrCl2] (0.005 mmol), tert-butyl hydroperoxide (TBHP, 5.5 M in nonane, 4.0 equiv), CaO (0.2 mmol, 2.0 equiv), 3-aminopropanol (0.25 mL). The tube was sealed with a Teflon lined cap. The reaction mixture was stirred at 140 °C for 48 h in oil bath (Because of the TBHP was heated to 140oC, be careful with the amplification reaction). After the completion of the reaction, the solvent was concentrated in vacuum and the residue was purified by flash column chromatography on silica gel with petroleum ether-EtOAc as the eluent to give the desired product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Stage #1: 4-methoxyphenyl benzyl ketone With sodium In methanol for 0.0833333h; Stage #2: With n-Butyl nitrite In methanol at 20℃; for 0.5h; | General procedure for the preparation of compounds 6a-d General procedure: To a stirred solution of 1-(4-methoxyphenyl)-2-arylethanone5a-d (1 mmol) in methanol was added a preparedsolution of sodium (1.5 mmol) in methanol and the resultingmixture was stirred for 5 min. Then butyl nitrite (1 mmol)was added and stirring was continued for 30 min. Reactionmixture was monitored by TLC. After completion of thereaction, it was concentrated under vacuum, diluted withwater and pH was adjusted to neutral by adding HCl 10%.Aqueous phase was extracted three times with ethyl acetate,dried and evaporated. The residue was recrystalized frommethanol to give pure compounds 6a-d.2-(Hydroxyimino)-1-(4-methoxyphenyl)-2-phenylethanone(6a) Yield 67%; mp: 107-109 °C; IR (KBr, cm-1) υmax:1638 (C=O). 1H-NMR (400 MHz, DMSO-d6) δ (ppm):3.84 (s, 3H, OCH3), 7.11 (d, J = 9 Hz, 2H, Ar-H),7.40-7.49 (m, 5H, Ar-H), 7.81 (d, J = 8.92 Hz, 2H, Ar-H),11.69 (s, 1H, NOH). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
37% | With copper(l) iodide; trifluoroacetic acid; silver(l) oxide In 1,2-dichloro-benzene at 120℃; for 7h; Sonication; Sealed tube; | |
With copper(l) iodide; silver(l) oxide In 1,2-dichloro-benzene; trifluoroacetic acid at 120 - 130℃; Sonication; | 3 Example 3 Preparation of [60]fullerene dihydrofuran derivatives 2c Fullerene C60 (54.0 mg, 0.075 mmol) was first added to the dried reaction tube and Cul (2.9 mg, 0.015 mmol), Ag2O (35.0 mg, 0.15 mmol) and (0.15 mmol or 0.30 mmol were added Add to the reaction tube, add the mixed solvent of trifluoroacetic acid and anhydrous ortho-dichlorobenzene and ultrasonically dissolve, and then plug the plug into the oil bath at 120 °C or 130 °C to stir the reaction, and the TLC test is complete. The reaction mixture was filtered through a short column of silica gel to remove any insoluble material. The solvent was evaporated in vacuo. The remaining solid was dissolved in CS2 and loaded onto the column. The unreacted fullerene C60 was first collected using CS2 as eluent. Elution with a mixed solution of CS2 and DCM as eluent gave the target product 2c. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With acetic acid; 1,1,1,3,3,3-hexamethyl-disilazane Reflux; | 299.A Step A General procedure: Hexamethyldisilazane (1.5 eq) was added dropwise to HOAc (7 mL). The resulting mixture was added to a suspension of malononitrile 52 (2.0 eq) and compound 59 (1.0 eq) in HOAc (5 mL). The reaction mixture was stirred with reflux overnight then, allowed to cool down to RT and diluted with toluene (30 mL) and water (20 mL). The organic layer was separated, washed with water (3*2 mL), dried over Na2SO4 and concentrated under reduced pressure affording compound 60. The scale was calculated based on a theoretical yield of 2 g of product. |
22% | With ammonium acetate; acetic acid In toluene at 120℃; Dean-Stark; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | Stage #1: 4-methoxyphenyl benzyl ketone; 1-(1-methyl-1H-indol-2-yl)-3-phenyl-prop-2-yn-1-one With caesium carbonate In dimethyl sulfoxide at 80℃; for 2h; Inert atmosphere; Stage #2: With hydrogenchloride; iron(III) chloride; dipotassium peroxodisulfate In water; dimethyl sulfoxide at 60℃; for 4h; Inert atmosphere; | 7 Example 1: Synthesis of IG The decyne ketone compound, the α-carbonyl compound, the promoter, the solvent, the catalyst, and the oxidizing agent are respectively selected from phenylethynyl-2-one, p-methoxyphenyl-2-phenylethanone, Cs2CO3, and dimethyl sulfoxide. , ferric chloride, potassium persulfate, the amount of raw materials are 0.3 mmol of phenylacetylene fluoren-2-one, 0.33 mmol of p-methoxyphenyl-2-phenylethanone, 0.15 mmol of Cs2CO3, solvent dimethyl sulfoxide 3 ml, reacted at 80 ° C for 2 hours, then cooled to room temperature, adding 6 mmol of hydrochloric acid 0.9 mmol, ferric chloride 0.015 mmol, potassium persulfate 0.9 mmol, and reacting at 60 ° C for 4 hours to obtain the target product formula (IG), yellow Solid, isolated yield 79%. Mp 255-257 ° C. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 1h; Inert atmosphere; Stage #2: 4-methoxyphenyl benzyl ketone In tetrahydrofuran at 50℃; for 1h; Inert atmosphere; | |
88% | Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 20℃; for 1h; Inert atmosphere; Stage #2: 4-methoxyphenyl benzyl ketone In tetrahydrofuran at 20℃; Inert atmosphere; | General Procedure for the Synthesis of olefins 5 or 8 [1]. General procedure: To a suspension of tBuOK (1.2 equiv.) in anhydrous THF (2 mL/mmol) was added MePPh3Br (1.2 equiv.) under argon atmosphere. The resulting yellow suspension was stirred at room temperature for 1 h, and then a solution of ketone (1.0 equiv.) was added. The resulting mixture was further stirred at room temperature overnight. The mixture was filtered through a short pad of silica gel, which was subsequently washed with Petroleum. After the filtrate was concentrated in vacuo, the crude products were purified by flash chromatography on silica gel (Petroleum) to afford the desired olefins 5 or 8. |
Stage #1: Methyltriphenylphosphonium bromide With potassium <i>tert</i>-butylate In tetrahydrofuran at 0℃; for 0.75h; Stage #2: 4-methoxyphenyl benzyl ketone In tetrahydrofuran at 20℃; for 16h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | In a round bottom flask, compound 16 (5.0 g, 22.12 mmol) was dissolved in dry THF (50 mL) over an ice bath and sodium hydride (NaH, 1.25 g, 52.08 mmol) was added to the solution. After 20 min. stirring, <strong>[7425-53-8]ethyl 4-iodobutyrate</strong> (10.74 g, 44.24 mmol) was added to the reaction mixture. The solution was kept over ice-bath for 15 min., and then transferred to room temperature. The progress of reaction was monitored by TLC. After completion of reaction, the reaction mixture was quenched with saturated solution of NH4Cl and worked up with ethyl-acetate and washed with water. The organic layer was separated, dried over anhydrous sodium sulphate (Na2SO4) and concentrated. The crude product was then chromatographed over a column of silicagel (100-200 mesh) eluting with the ethyl acetate-hexane (2:98) to afford compound 21a as white solid. Yield: 70%; mp: 50-51C; Rf: 0.60 (30% Ethyl acetate-Hexane); IR (KBr, numax/cm-1): 2957, 1729, 1673, 1599, 1261, 1026, 830, 741; 1H NMR (CDCl3, 500 MHz, delta ppm): 1.21 (t, J = 7.0 Hz, 3H, CH3), 1.25-1.65 (m, 2H, CH2), 1.83 (d, J = 5.0 Hz, 1H, CH2), 2.16 (t, J = 5.5 Hz, 1H, CH2), 2.27-2.32 (m, 2H, CH2), 3.81 (s, 3H. OCH3). 4.08 (q, J = 7.0 Hz, 2H, OCH2), 4.49 (t, J = 7.0 Hz, 1H, CH), 6.84-6.87 (m, 2H, ArH), 7.17-7.20 (m, 1H, ArH), 7.26-7.30 (m, 4H, ArH), 7.93-7.96 (m, 2H, ArH); 13C NMR (CDCl3, 125 MHz, delta ppm): 14.2, 23.1, 33.4, 34.2, 53.1, 55.4, 60.2, 113.7 (2xC), 127.0, 128.1 (2xC), 128.9 (2xC), 129.7, 130.9 (2xC), 139.7, 163.3, 173.4, 198.0; EIMS (C21H24O4): m/z = 341.2 [M+H]+. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | Stage #1: 4-methoxyphenyl benzyl ketone With sodium hydride In tetrahydrofuran at 20℃; for 0.333333h; Stage #2: ethyl 6-iodohexanoate In tetrahydrofuran for 0.25h; | Synthesis of ethyl 6-(4-methoxyphenyl)-6-oxo-5-phenylhexanoate (21a): General procedure: In a round bottom flask, compound 16 (5.0 g, 22.12 mmol) was dissolved in dry THF (50 mL) over an ice bath and sodium hydride (NaH, 1.25 g, 52.08 mmol) was added to the solution. After 20 min. stirring, ethyl 4-iodobutyrate (10.74 g, 44.24 mmol) was added to the reaction mixture. The solution was kept over ice-bath for 15 min., and then transferred to room temperature. The progress of reaction was monitored by TLC. After completion of reaction, the reaction mixture was quenched with saturated solution of NH4Cl and worked up with ethyl-acetate and washed with water. The organic layer was separated, dried over anhydrous sodium sulphate (Na2SO4) and concentrated. The crude product was then chromatographed over a column of silicagel (100-200 mesh) eluting with the ethyl acetate-hexane (2:98) to afford compound 21a as white solid. Yield: 70%; mp: 50-51C; Rf: 0.60 (30% Ethyl acetate-Hexane); |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
57% | With hydrogenchloride In water; isopropyl alcohol for 24h; Reflux; | Synthesis of (E)-1,2-Diarylethylidenecarboximidamides (2a-j) General procedure: To a suspension of 1,2-diarylethanones (1a-j) (1 eq) in 2-propanol, was added aminoguanidine (1.5 eq) and catalytic amounts of hydrochloric acid (37%) and the mixture was refluxed for 24 h to complete the reaction monitored by TLC. After completion of reaction, it was cooled to room temperature to precipitate the product, then filtered off and washed by water. If necessary, recrystallization was performed in 2-propanol to give the pure product. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With lithium diisopropyl amide In tetrahydrofuran at 60℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
42% | With copper diacetate In 1,2-dichloro-ethane at 70℃; for 0.5h; Inert atmosphere; | 6. General Procedure C for the copper catalyzed a-arylation of aromatic ketones General procedure: In a flamed-dried 4 ml screw vial backfilled with argon closed by a septum cap was added diaryliodonium triflate (0.25 mmol) and 0.5 mL of a solution of 5 mol% of Copper (II) acetate (0.00125 mmol) in 5 ml of DCE. Then, silyl enol ether (0.375 to 0.625 mmol) was added with a syringe and the cap was changed by an impervious cap under an argon flow. The mixture was stirred at 70 °C during 0.5 h and was after quenched by a saturated solution of NH4Cl. The product was extracted with Et2O, dried over MgSO4, filtrated and concentrated under vacuum. The product was purified on silica column with the corresponding eluent to give the α-arylated aromatic ketone. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With sulfuric acid In ethanol at 90℃; | Typical Procedure B General procedure: A mixture of 2-phenyl-1-(p-tolyl)ethan-1-one (3b; 210.0 mg, 1.0mmol, 1.0 equiv) and phenylhydrazine (108.0 mg, 1.0 mmol, 1.0equiv) was dissolved in EtOH (15 mL). Then, concentrated sulfuric acid (196.0 mg, 2.0 mmol, 2.0 equiv) was slowly added to the reaction mixture and the resulting solution was refluxed at 90 °C. After the reactionwas completed (detected by TLC), the resulting mixture was poured into water and extracted with DCM (3 × 20 mL). The combinedorganic layers were dried over Mg2SO4 and concentrated in vacuo. Theresidue was purified by column chromatography on silica gel (EA/PE,1:30 to 1:10) to give 3-phenyl-2-(p-tolyl)-1H-indole (1b; 198.1 mg,70%) as a yellow oil. Similarly, compounds 1c-1q and 1u were obtainedusing this method. |
Tags: 1023-17-2 synthesis path| 1023-17-2 SDS| 1023-17-2 COA| 1023-17-2 purity| 1023-17-2 application| 1023-17-2 NMR| 1023-17-2 COA| 1023-17-2 structure
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