Saturated aqueous solution of sodium hydrogen carbonate

Saturated aqueous solution of sodium hydrogen carbonate... 

A solution of 4-[(2 )-(2-acetoxypropyl)]-5-amino-l,2-dimethoxy-3-methylbenzene (1.96 g, 7.33 mmol) and tricarbonyl(ri -cyclohexadienylium)iron tetrafluoroborate (1.12 g, 3.66 mmol) in acetonitrile (30 mL) was stirred at room temperature for 9 days in air. A saturated aqueous solution of sodium hydrogen carbonate (20 mL) was added to the reaction mixture and the aqueous layer was extracted with ethyl acetate (3 x 20 mL). The combined organic layers were washed with water (2 x 20 mL) and dried with sodium sulfate. After removal of the solvent, the residue was subjected to flash chromatography (hexane/ethyl acetate/triethylamine, 8 2 1) on silica gel to afford the tricarbonyl(il -4a,9a-dihydrocarbazole)iron complex as a bright yellow viscous liquid [a]n = -13.0 (c = 0.5, CHCI3) 1.67g(94%). ... 

The residue was subjected to azeotropic operation with toluene two times, and ether was added to the residue. The precipitate derived from trioxane was removed by filtration and washed with ether, and the combined ethereal solutions were concentrated under reduced pressure. The residue was dissolved in ethyl acetate, and the solution was washed with water and aqueous saturated solution of sodium chloride, was dried, and was concentrated to give 4 g of an oily material. The oily material was dissolved in 20 ml of methanol and to the solution was added 20 ml of aqueous 1 N solution of sodium hydroxide, and the mixture was stirred for 14 hours at room temperature. After removal of methanol under reduced pressure, water was added to the mixture, and this solution was acidified to pH 3 with aqueous 2 N hydrochloric acid. The mixture was extracted five times with ethyl acetate, and the ethyl acetate extract was dried and concentrated to give 3.5 g of crude crystals. After addition of ethanol to the crude crystals, the crude crystals were filtered. The filtrate was concentrated, and to the residue was added ethanol and ethyl acetate, and precipitate was collected by filtration. The combined amount of the crude crystals was 1.6 g. After the combined crude crystals were methylated with diazomethane, the reaction product was dissolved in 20 ml of ethyl acetate. To this solution was added 1.5 g of sodium acetate and 300 mg of 10% palladium-carbon, and the mixture was stirred for 2 hours under hydrogen. Then, the reaction product was filtered, and after addition of aqueous saturated solution of sodium hydrogen carbonate to the filtrate, the mixture was extracted two times with ethyl acetate. The extract was washed with an aqueous saturated solution of sodium chloride, dried, and concentrated to give 1.3 g of crude crystals. The crude crystals were recrystallized from ethyl acetate to yield 765 mg of the title compound (melting point 134-135°C, yield 43%). 

To a solution of 1.14 g of 3-methyl-trans-4a-cisoid-4a,5a-cis-5a-l,4a,5,5a,10b,10c-hexahydro-7-dioxino[5,4-a]cyclopenta[b]benzofuranyl-methanol in 10 ml of dimethoxyethane cooled in an ice bath was added 0.43 ml of anhydrous pyridine and 0.38 ml ofthionyl chloride, and the mixture was stirred for 3 hours at room temperature. After addition of ether to the reaction mixture, the precipitate was filtered, and water was added to the filtrate and the mixture was extracted three times with ether. The extract was washed with aqueous saturated solution of copper sulfate, water, aqueous saturated solution of sodium hydrogen carbonate and aqueous saturated solution of sodium chloride, dried, and concentrated to give 1.2 g of crude crystals. The crude crystals were recrystallized from ethyl acetate-hexane to yield 1 g of the pure titled chloride (m.p. 94-95°C, yield 83%). 

To a stirred solution of 122 mg of ll,15-dideoxy-ll-acetoxy-16-methyl-15-oxo-18,19-tetradehydro-5,6,7-trinor- 4,8-inter-m-phenylene PGI2 in 10 ml of methanol was added 150 mg of cerium chloride heptahydrate, and then the solution was cooled in an ice bath, and 15 mg of sodium borohydride was added to the solution. After 10 min, to the mixture was added 2 ml of aqueous saturated solution of sodium hydrogen carbonate, and the mixture was further stirred for 10 min. 

Dissolve 5.3 g (0.05 mol) of benzaldehyde (previously shaken with sodium hydrogen carbonate solution) and 0.25 g (0.67 mmol) of tetrabutylammonium iodide in 50 ml of dichloromethane. Place this solution in a 250-ml, three-necked round-bottomed flask equipped with an efficient sealed stirrer unit, a reflux condenser and a thermometer sited in a screw-capped adapter, and supported in an oil bath mounted on an electric hot plate. Introduce 50 ml of a 50 per cent (w/v) aqueous solution of sodium hydroxide, and then 10.2 g (0.05 mol) of finely powdered trimethylsulphonium iodide. Adjust the electric hot plate so that the oil bath is maintained at a constant temperature of 55 °C for 60 hours and during this period stir the reaction mixture rapidly (1). Pour the reaction mixture on to ice, separate the organic phase and extract the aqueous solution with one 20 ml portion of dichloromethane. Wash the combined organic phases successively with four 20 ml portions of water, two 10 ml portions of a saturated solution of sodium metabisulphite and finally two 20 ml portions of water. Dry the organic phase over anhydrous calcium sulphate, remove the dichloromethane on a rotary evaporator and distil the residue. Collect the phenyloxirane as a fraction having b.p. 191— 192 °C the yield is 4.7 g (78%). 

A solution of Sml2 (0.1m in THF, 0.4 mL) was added dropwise to a solution of 43 (R = Ph) (112.0 mg, 0.4 mmol) and freshly distilled benzaldehyde (1.6 mmol) in dry toluene (4 mL) at room temperature under an argon atmosphere. The reaction mixture was stirred for 4 h at 80 °C, after which TLC analysis showed the starting material had disappeared completely. Then a saturated solution (3 mL) of sodium hydrogen carbonate was added. The organic layer was separated, and the aqueous phase was extracted with ethyl acetate (3 x 10 mL). The combined extracts were dried over anhydrous Na2S04. Evaporation of the solvent and column chromatography of the crude product on silica gel (petroleum ether/ethyl acetate 30 1 to 15 1) afforded 44 (R = Ph) (147.0 mg, 0.38 mmol, 95%). 

The hexane solvent was removed from a solution of DIB AL (22 mmol, 1 Min hexane) at reduced pressure and at ambient temperature, and ether (10 ml) was introduced. l-Cyclohexyl-2-trimethylsilylethyne (20 mmol) was added at such a rate as to maintain ambient temperature within the reaction, and. after 15 min, the reaction flask was placed in a preheated (40 °C) bath for I h. The resulting clear solution was transferred by means of a double-ended syringe to a vigorously stirred cold solution of HC1 (50 ml, 10%). The flask was rinsed with ether (20 ml), and the mixture was stirred until the resulting phases were almost clear. The layers were separated, and the aqueous layer was extracted with ether (40 ml). The combined organic extracts were washed successively with dilute HC1 (20%), saturated sodium hydrogen carbonate solution and brine, and dried. 

A solution of ( )-l,2-bis(trimethylsilyl)oct-l-ene (12mmol) in glacial AcOH (31 ml) and H20 (1.6 ml) was heated with stirring at 110°C for 29 h. The mixture was then cooled to0°C, aqueous NaOH (60 ml, 9 m) added, and the total was extracted with ether (50 ml). The ethereal extract was washed with saturated sodium hydrogen carbonate solution and brine, and dried. Concentration and distillation gave 2-trimethylsilyloct-l-ene (U.5mmol, 96%), b.p. 106 °C/1 mmHg. 

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