POCl3 (4.73 mL, 50.79 mmol) was slowly added to a solution of DMF (6.56 mL, 84.75 mmol) while the temperature was maintained below 40 °C. Then, benzofuran 1 (2.00 g,16.93 mol) was added dropwise to this reaction mixture below 40 °C, over a period of 15 min. The mixture was heated at 80 °C for 24 h. The reaction mixture was then poured into ice-water and carefully quenched with a solution of sodium hydroxide. The organic material was separated, and the aqueous layer was extracted with ethyl acetate. It was washed with brine and dried over anhydrous magnesium sulfate. The filtrate was concentrated, and was purified on silica gel column (petroleum ether: EtOAc = 10:1) to give product 2 (2.27 g, 90percent) as brown oil. 1H NMR (400 MHz,CDCl3): δ 9.83 (1H, s, COH), 7.75-7.70 (1H, m, H-4), 7.56-7.54 (2H, m, H-6,7), 7.46 (1H, s, H-3), 7.32-7.28 (1H, m, H-5). 13C NMR (100 MHz, CDCl3): δ 179.63 (COH), 156.03 (C-7a), 152.52 (C-2), 129.07 (C-3a), 126.51 (C-6), 124.05 (C-5), 123.58 (C-4), 117.93 (C-3), 112.44 (C-7).
80%
Stage #1: With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1 h; Stage #2: at 20℃;
1. To a solution of benzofuran (1.5 g, 12.69 mmol) in 60 mL of THF, was added 5.08 mL(12.69 mmol) of n-BuLi solution in hexanes (2.5 M) at -78 °C. After 1 hr at -78 °C, the reaction mixture was added DMF (3.43 mL). After overnight at RT, the reaction was quenched with saturated ammonium chloride, and extracted with EtOAc (x3). The combined organic extracts were dried (MgS04), filtered, and concentrated. Flash chromatography (10 percentEtOAc/Hexanes) gave benzofuran-2-carbaldehyde (1.48 g, 80percent). *H NMR (400 MHz, CDC13) δ ppm: 9.88 (s, IH), 7.76 (d, J=8.4 Hz, IH), 7.62 (d, J=8.4 Hz, IH), 7.57 (s, IH), 7.52 (td, J=7.2, 1.2 Hz IH), 7.35 (td, J=7.2, 1.2 Hz, IH).
61%
Stage #1: With n-butyllithium; ammonium chloride In tetrahydrofuran; hexane at -78℃; for 0.5 h; Inert atmosphere Stage #2: at -78℃; for 1 h;
Step 1: benzofuran-2-carbaldehyde To a solution of benzofuran (10 g, 84.7 mmol) in dry THF was added n-BuLi (2.5 M solution in hexane, 33.9 mL, 84.7 mmol) dropwise at -78° C. under nitrogen, the mixture was stirred at -78° C. for 0.5 h, and then added DMF (19.6 mL, 254 mmol). The resulted mixture was kept at -78° C. and stirred for 1 h. The reaction was quenched by addition of saturated NH4Cl aqueous solution (20 mL), and then added ethyl acetate (300 mL) and H2O (100 mL), the aqueous layer was extracted with ethyl acetate (50 mL). The combined organic layer was washed with water and brine, dried over sodium sulfate and concentrated under vacuum, the residue was purified by column chromatography on silica gel (ethyl acetate:petroleum ether=10:1) to afford benzofuran-2-carbaldehyde (7.5 g, yield: 61percent) as yellow oil. 1H NMR (400 MHz, CDCl3): δ 9.90 (s, 1H), 7.78 (d, J=8.8 Hz, 1H), 7.63 (d, J=8.2 Hz, 1H), 7.59 (s, 1H), 7.53-7.57 (m, 1H), 7.35-7.39 (m, 1H).
40%
at 80℃;
Preparation of 2,3-Benzofuran-5-carboxaldehyde 39[0201] To a DMF (0.580 mL) solution of 2,3-benzofuran 38 (0.331 mL, 3.0 mmol) was added phosphorous oxychloride (0.302 mL, 3.3 mmol). The reaction mixture was stirred overnight at 80 °C, then the excess solvent was removed in vacuo. The residue was diluted with ethyl acetate (100 mL), then washed with water (2 X 20 mL). The organic layer was dried with brine and MgSC>4, then concentrated in vacuo. Flash column chromatography on silica gel (n-hexanes : ethyl acetate = 50:1) of the residue afforded the desired product 39 in 40percent yield (172 mg, yellow oil). LH NMR (400 MHz, CDC13): 9.88 (s, 1H), 7.76 (d, J= 7.2 Hz, 2H), 7.62 (dd, J= 8.4, 0.8 Hz, 1H), 7.54 (d, J= 0.8 Hz, 1H), 7.53 (td, J= 12, 1.2 Hz, 1H), 7.35 (td, J= 7.2, 0.8 Hz, 1H).
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[ 271-89-6 ]
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With 2,2,6,6-Tetramethyl-1-piperidinyloxy free radical; sodium perchlorate; acetic acid; lithium hexamethyldisilazane; In acetonitrile; for 15h;Electrochemical reaction;
General procedure: Preparative electrolysis experiments were performed using 263 APotentiostat/Galvanostat (Princeton Applied Research, USA). 0.1 MNaClO4-CH3CN solution (10 mL) containing aldehydes (1 mmol),TEMPO (0.1 mmol), HMDS (2.5mmol) and AcOH (2.5mmol) was electrolyzedwith stirring in an undivided cell (30 mL) equipped with twoplatinum sheets as anode (1.5 cm2) and cathode (3.0 cm2) respectivelyat a constant potential of 1.5 V vs Ag/Ag+ (0.1MAgNO3 in acetonitrile).The electrode separation was 1 cm. When the reaction was finished,10mL of saturatedNa2SO3 solution was added into the reactionmixtureand stirred for 15 min. Then the mixture was extracted with CH2Cl2(20 mL × 3). The organic layer was dried with anhydrous Na2SO4 andconcentrated in a rotary evaporator. The productswere obtained via purificationof column chromatography and their structures were confirmedby 1H NMR, 13C NMR and MS. NMR was performed on a BrukerAvance III spectrometer. GC-MS was performed on the Thermo TraceISQ instrument with TG 5MS capillary column.
77%
With trifluorormethanesulfonic acid; trimethylsilylazide; In acetonitrile; at 20℃; for 0.333333h;Sealed tube; Inert atmosphere;
General procedure: To a solution of an aromatic aldehyde 1 (0.500 mmol, 1.0 equiv) and TMSN3 (115 mg, 1.00 mmol,2.0 equiv) in a premixed HFIP/ACN mixture (2.0 mL, 1:1) in a nitrogen-flushed two dram vial wasadded triflic acid (TfOH; 17.7 L, 0.200 mmol, 0.40 equiv) (exotherm and brisk effervescence due tonitrogen gas evolution was immediately observed). The vial was capped and the reaction mixture wasallowed to stir at rt for 20-75 min. The reaction mixture was concentrated under nitrogen. The residueobtained was suspended in CH2Cl2/hexanes mixture and loaded on a silica gel in a 5 g samplecartridge. Purification using a normal phase silica flash column on a CombiFlash purification systemafforded a corresponding aromatic nitrile 2 upon concentration of appropriate fractions.
72%
With tert.-butylhydroperoxide; ammonium acetate; iodine; sodium carbonate; In ethanol; at 50℃; for 5h;
In a 25 mL two-necked round bottom flask equipped with a thermometer and a magnetic stirrer4 mmolofBenzofuran-2-carbaldehyde (1-19), 6 mmol of NH4OAc, 4 mmol of Na2CO3, 4.4 mmol of TBHP, 0.1 mmol of I2, 5 mL of absolute ethanol Solvent, followed by placing the reaction flask in an oil bath preheated to 50 C and opening the magnetic stirrer for 5 h. The reaction solution By adding sodium thiosulfate solution, stirring, and then extracting with ether, separating the organic layer, and removing the solvent under reduced pressure, The eluate was collected with the mixture of ethyl acetate / petroleum ether in a volume ratio of 1: 100 as the eluent, and the eluate containing the target compound was collected. The solvent was distilled off to give benzofuran-2-carbonitrile with an isolated yield of 72%.
With sodium acetate; In acetic acid; at 135℃; for 12h;
General procedure: To a solution of the <strong>[556-90-1]pseudothiohydantoin</strong> 6a (139 mg, 1.2 mmol), and sodium acetate (328 mg, 4.0 mmol) in acetic acid (5 ml) was added 5-phenyl-2-furaldehyde 5a (172 mg,1.0 mmol) at 25C. The solution was refluxed at 135C for 12 h. The precipitate was filtered and washed with water and diethyl ether. The filter cake was dried under high vacuum to afford 230 mg (85%) of compound 7a as an orange solid.
2'(tert-butylamino)-5'-hydroxy-6'-undecyl[2,3'-bibenzofuran]-4',7'-dione[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
59%
With ethylenediaminediacetic acid; In 1,2-dichloro-ethane; at 180℃; for 0.25h;Irradiation;
General procedure: To a mixture of 0.1 mmol of the corresponding isocyanide,0.1 mmol of the corresponding aldehyde, and 10 mol % of EDDA in2 mL of DCE, were added 30 mg of <strong>[550-24-3]embelin</strong> (0.1 mmol). The reactionmixture was stirred and irradiated for 15 min at 180 C. The solvent wasremoved under vacuum, and the crude product was purified by preparative-TLC to yield the corresponding furan derivative.
2'-(cyclohexylamino)-5'-hydroxy-6'-undecyl-[2,3'-bibenzofuran]-4',7'-dione[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
64%
With ethylenediaminediacetic acid; In 1,2-dichloro-ethane; at 180℃; for 0.25h;Irradiation;
General procedure: To a mixture of 0.1 mmol of the corresponding isocyanide,0.1 mmol of the corresponding aldehyde, and 10 mol % of EDDA in2 mL of DCE, were added 30 mg of <strong>[550-24-3]embelin</strong> (0.1 mmol). The reactionmixture was stirred and irradiated for 15 min at 180 C. The solvent wasremoved under vacuum, and the crude product was purified by preparative-TLC to yield the corresponding furan derivative.
2'-(benzylamino)-5'-hydroxy-6'-undecyl[2,3'-bibenzofuran]-4',7'-dione[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
63%
With ethylenediaminediacetic acid; In 1,2-dichloro-ethane; at 180℃; for 0.25h;Irradiation;
General procedure: To a mixture of 0.1 mmol of the corresponding isocyanide,0.1 mmol of the corresponding aldehyde, and 10 mol % of EDDA in2 mL of DCE, were added 30 mg of <strong>[550-24-3]embelin</strong> (0.1 mmol). The reactionmixture was stirred and irradiated for 15 min at 180 C. The solvent wasremoved under vacuum, and the crude product was purified by preparative-TLC to yield the corresponding furan derivative.
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