Isoquinoline N-oxide

In a 50 mL round bottom flask, quinoline 1.29 g, hydrogen peroxide (35percent mass fraction) 1.1 g, 5percent by mass were added in order.Number of perfluorosulfonic acid resin, 10 ml of water as a solvent, and the resulting mixture reacted for 15 minutes in a 30 W/20 KHz ultrasonic reactorbell. The resin catalyst in the reaction system is removed by filtration, the water in the reaction solvent is removed under reduced pressure, and finally recrystallized to obtain the correspondingQuinoline nitrogen oxide 1.39 g, yield 96percent.{Mo132} 100 mg, Isoquinoline 1 mmol, 30percent Hydrogen peroxide 5 mmol, Ethanol 2 ml and water 3 ml were mixed and stirred at room temperature, After the reaction for 24 hours, it was extracted with dichloromethane and then purified by distillation with organic phase dichloromethane to give the isoquinoline pyridine nitroxide in a yield of 90percent.To a stirred solution of isoquinoline (43-1) (2 g, 15.4 mmol) in dichloromethane (50 mL) at 0°C, was added mCPBA (3.77 g, 16.9 mmol) portionwise and the reaction mixture was stirred at RT for 18 h. After consumption of starting material as evident from TLC, the reaction mixture was quenched with a saturated solution of sodium sulphite, the organic layer was separated and washed with a saturated solution of sodium carbonate, brine, dried over anhydrous sodium sulphate, and concentrated under reduced pressure to afford isoquinoline 2-oxide (43-2) (2.00 g, General procedure: Catalyst (0.03 mmol), Hstep one, Tungsten-loaded titanium dioxide is used as a catalyst.50g isoquinoline, 40mL 30percent hydrogen peroxide solution, 5g of the catalyst prepared in step (a) was added to the three-necked flask;Step two, The mixture prepared in step 1 is stirred and reacted at 40° C. for 24 hours.After the reaction liquid is naturally cooled to room temperature, it is filtered, washed and concentrated.After the filtrate is concentrated, the yield of isoquinoline nitrogen oxide product is 86.8percent.The purity by HPLC was 94.8percent.General procedure: To a solution of pyridine derivative 1 or tertiary amine 2(1 mmol) in acetonitrile (5 mL) was added 1, 2-diphenyl-1, 1, 2, 2-tetrahydroperoxyethane (1 g, 3 mmol). The resulting mixture was stirred at room temperature for an appropriate time (Table 2). After completion of the reaction as monitored by TLC, the reaction mixture was diluted with toluene (10 mL) and water (6 mL). The aqueous layer which contained the product was separated from theorganic layer and evaporated under reduced pressure toleave the product. The products were characterized on the basis of their melting points, elemental analysis and IR, 1HNMR and 13C NMR spectral analysis.General procedure: To a stirred solution of amine (1 mmol), trichloroacetonitrile (2 mmol), and NaHCOAdd isoquinoline (500.00 g, 3.75 moles) and ethyl acetate (7.60 L, 77.62 moles) to a 22 L three- necked round-bottom flask in a water bath equipped with overhead stirrer, thermocoupler, nitrogen inlet/outlet, and addition funnel. Stir to dissolve. At room temperature add peracetic acid (1.25 L, 5.94 moles) dropwise over 0.5 ours. Stir at room temperature overnight. Chill the reaction flask in an ice-water bath, then quench the reaction by dropwise addition of dimethyl sulfide (525.00 mL, 7.14 moles) over 45 minutes. Stir overnight while warming to room temperature. Test the reaction mixture for peroxide.Combine two lots of the reaction mixture. Transfer the reaction mixtures to a 50 L separatory funnel and add water (2.00 L, 111.02 moles) and dichloromethane (12.00 L, 187.21 moles). Add sodium carbonate (2.07 kg, 19.53 moles) in portions, then separate layers. Extract the aqueous layer with dichloromethane ( 3 x 4 L), combine the organic layers and dry over sodium sulfate. Filter and remove solvent under reduced pressure to afford a crude dark red oil/liquid.Add ethyl acetate (8.00 L, 81.76 moles) to the crude dark red oil/liquid, then stir under reduced pressure until 6.8 L of ethyl acetate are removed. Filter the precipitated solid, wash with cold ethyl acetate (750.00 mL, 7.66 moles), then heptane (800.00 mL, 5.46 moles) wash. Dry the solid to afford isoquinoline- 2-oxide, 714.20 g (64percent) as a fine sand-like solid.As an alternative work-up, prior to the heptane wash, remove IL of solvent from the filtrate. Allow the filtrate to stand overnight. Filter the solid and wash with cold ethyl acetate (500.00 mL, 5.11 moles), followed by a heptane (500.00 mL, 3.41 moles) wash. The solid was dried to afford isoquinoline-2-oxide, 110.10 g (10percent) as a fine sand-like solid - cropNo.2 (total yield 74percent).General procedure B. To a stirred solution of amine (0.3-0.8 mmol) in methanol (0.5 M) was added at 0 °C UHP (3 mol equiv) and catalyst 1 (2 mol percent). The mixture was stirred at room temperature for the necessary time (see Table 2). The reaction mixture developed a red-orange colour that disappeared at different times depending on the amine type. The reaction mixture, then, remained yellow and in some cases a white precipitate formed. After removal of the solvent under reduced pressure, dichloromethane was added and the slurry formed was filtered through Celite. The solvent was evaporated and the crude residue purified by flash column chromatography.

Molecular Weight:145.16
XLogP3:0.3
Hydrogen Bond Acceptor Count:1
Exact Mass:145.052763847
Monoisotopic Mass:145.052763847
Topological Polar Surface Area:25.5
Heavy Atom Count:11
Complexity:138
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes