Organic dichloromethane

There are also some other features worth mentioning about this protocol. The authors dried the MIP between the aqueous and organic (dichloromethane) washes. This step was thought necessary because the two solvents are immiscible. However,... 

Elfamycins aie slightly acidic because of the 4-hychoxy-2-pyiidone oi the caiboxyhc acid moiety. They are soluble in most polar organic solvents and the alkah and ammonium salts ate water-soluble. The extractabihty of the free acids from aqueous solution into solvents such as dichloromethane and ethyl... 

The preparations are much simplified if a stoichiometric amount of hydrogen halide is added using an indicator to determine the end point. We have found that 1,9-diphenylnona-1,3,6,8-tetraen-5-one (dicinnamalacetone) is of appropriate basicity to detect excess anhydrous hydrogen halides in organic solvents including chloroform, dichloromethane, benzene, toluene, acetic acid, and acetone (but not in alcohols). The reaction between the... 

To a solution of m-ethyl cinnamate (44, 352 mg, 85% pure, 1.70 mmol) and 4-phenylpyridine-A-oxide (85.5 mg, 29 mol%) in 1,2-dichloromethane (4.0 mL) was added catalyst 12 (38.0 mg, 3.5 mol%). The resulting brown solution was cooled to 4°C and then combined with 4.0 mL (8.9 mmol) of pre-cooled bleach solution. The two-phase mixture was stirred for 12 h at 4°C. The reaction mixture was diluted with methyl-t-butyl ether (40 mL) and the organic phase separated, washed with water (2 x 40 mL), brine (40 mL), and then dried over Na2S04. The drying agent was removed by filtration the mother liquors concentrated under reduce pressure. The resulting residue was purified by flash chromatography (silica gel, pet ether/ether = 87 13 v/v) to afford a fraction enriched in cis-epoxide (45, cis/trans . 96 4, 215 mg) and a fraction enriched in trans-epoxide cis/trans 13 87, 54 mg). The combined yield of pure epoxides was 83%. ee of the cis-epoxide was determined to be 92% and the trans-epoxide to be 65%. 

To a solution of nitroolefin 4 (200 mg) and isocyanide 16 (169 mg) in a 1 1 mixture of THF and isopropanol (5 mL) was added the guanidine base A -t-BuTMG (180 mg). The resulting solution was heated to 50°C for 3 h, poured into water, and extracted with dichloromethane. The organic layer was dried over sodium sulfate and filtered through a short column of silica gel (eluent dichloromethane). Evaporation under vacuum of the solvent gave the desired pyrrole as a pale crystalline solid (272 mg, 90%) mp... 

A mixture of 22 parts of 1 -ethyl-1,4-dihydro-5H-tetrazol-5-one,45 parts of 1 -bromo-2-chloro-ethane,26 parts of sodium carbonate,0.3 part of potassium iodide and 240 partsof 4-methyl-2 pentanone is stirred and refluxed overnight with water-separator. The reaction mixture is cooled, water is added and the layers are separated. The aqueous phase is extracted three times with dichloromethane. The combined organic phases are dried, filtered and evaporated. The residue is purified by column-chromatography over silica gel using trichloromethane as eluent. The pure fractions are collected and the eluent is evaporated, yielding 28.4 parts (80%) of 1-(2-chloroethyi)-4-ethyl-1,4-dihydro-5H-tetrazol-5-one as a residue. 

The next step yields 1-(3-acetylthio-2-methylpropanoyl)-L-proline tert-butyl ester. L-proline tert-butyl ester (5.1 g) is dissolved in dichloromethane (40 ml) and the solution stirred and chilled in an ice bath. Dicyclohexylcarbodiimide (15 ml) is added followed immediately by a solution of 3-acetylthio-2-methylpropanoic acid (4.9 g) in dichloromethane (5 ml). After 15 minutes stirring in the ice bath and 16 hours at room temperature, the precipitate is filtered off and the filtrate is concentrated to dryness in vacuo. The residue is dissolved in ethyl acetate and washed neutral. The organic phase is dried over magnesium suifateand concentrated to dryness in vacuo. The residue 1-(3-acetylthio-2-methylpropanoyl)-L-proline tert-butyl ester is purified by column chromatography (silica gel-chloroform), yield 7.9 g. 

Bonhote and co-workers [10] reported that ILs containing triflate, perfluorocar-boxylate, and bistrifylimide anions were miscible with liquids of medium to high dielectric constant (e), including short-chain alcohols, ketones, dichloromethane, and THF, while being immiscible with low dielectric constant materials such as alkanes, dioxane, toluene, and diethyl ether. It was noted that ethyl acetate (e = 6.04) is miscible with the less-polar bistrifylimide and triflate ILs, and only partially miscible with more polar ILs containing carboxylate anions. Brennecke [15] has described miscibility measurements for a series of organic solvents with ILs with complementary results based on bulk properties. 

The cooling bath is then replaced by a steam bath, and the reaction mixture is refluxed for 16 hours. It is then cooled, transferred to a one-necked, 1-1., round-bottomed flask, and concentrated to dryness on a rotary evaporator. The dark residue is dissolved in a mixture of 200 ml. of water, 200 ml. of dichloromethane, and 20 ml. of triethylamine, and the aqueous phase is separated and washed with two 200-ml. portions of dichloromethane. The organic phases are combined and washed with 300 ml. of saturated aqueous sodium chloride, dried over anhydrous magnesium sulfate, and filtered. Removal of the solvent on a rotary evaporator gives a red oil, which solidifies on storage at 0-5° (Note 5). Recrystallization of this solid from 40 ml. of absolute ethanol gives 7.6-8.4 g. (34-37%) of ethyl 4-amino-3-(methylthiomethyl)-benzoate, m.p. 83-85°. A second crop of l.l-2.5g. of crystalline material, m.p. 78-83°, may be obtained by concentration of the mother liquors (Note 6). 

A solution of mcpba (11.5 mmol) in dichloromethane (30 ml) was added to a stirred solution of the vinylsilane (10 mmol) in dichloromethane (50 ml) at 0°C. After stirring for 1 h, the mixture was washed with aqueous sodium hydrogen sulphite (50 ml), saturated sodium hydrogen carbonate solution and brine. The organic solution was then dried and concentrated, prior to purification by distillation or chromatography. 

Cyclohexanone (5.7 mmol) was added to a solution of the reagent (6.2 mmol) at -78 to -50°C. After 0.5 h at this temperature, it was allowed to warm to ambient temperature over 3 h. The mixture was poured into dilute HC1 (25ml, 0.5m), extracted with dichloromethane (3 x 30ml), and the organic extracts dried and concentrated, to give the epoxysilane (4.7mmol, 83%). 

Boron trifluoride etherate (1 mmol) was added dropwise to a stirred solution of the epoxysilane (1 mmol) in dichloromethane (5 ml) at -78 °C, and the mixture was stirred for 5min. The reaction mixture was quenched with saturated sodium hydrogen carbonate solution (1 ml), and allowed to warm gradually to ambient temperature. The organic phase was washed with brine (3 x 5 ml), dried and concentrated. The (Z)-epoxysilane gave the (Z)-silyl enol ether (68%, 96 4(Z) (E)), and the (E)-isomer gave the (E)-silyl enol ether (69%, 95 5 ( ) (Z)). 

A mixture of senecioyl chloride (0.1 mol) and A1C13 (0.1 mol) in dichloromethane (50 ml) was added dropwise over 45 min with stirring to a solution of dimethylallyltrimethylsilane (O.llmol) in dichloromethane (KK)ml), previously cooled to — 60 °C. The reaction mixture was maintained at this temperature for 10 min after the final addition, and then poured slowly onto a mixture of crushed ice and ammonium chloride. After washing of the organic layer with brine and drying, artemisia ketone (0.09 mol, 90%). b.p. 87°C/200mmHg, was obtained. 

To a stirred solution of TMSOTf (0.1 mmol) in dichloromethane (1ml). cooled to -78°C, were added successively methoxytrimethylsilane (20 mmol) and benzaldehyde (10 mmol). The mixture was stirred at — 78 °C for 3h, and then quenched by the addition of pyridine (0.2ml) at — 78°C. The mixture was poured on to saturated sodium hydrogen carbonate solution (15 ml), and extracted with ether (3x15 ml). The combined organic extracts were dried over sodium carbonate/sodium sulphate (1 1), filtered, concentrated and distilled, to give benzaldehyde dimethyl acetal (9.4mmol, 94%), b.p. 125-135°C/51 ramHg. 

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