Additives silica gel

Lyophilized, pulverized leaves (5.35 kg) of S. divinorum were extracted with ether. The nonpolar components were removed from the concentrated extract through partition between hexanes and 90% aqueous methanol. The dried methanolic fraction was crudely purified by silica gel flash column chromatography (hexanes-ethyl acetate 2/1). Further purification of the biologically active fractions by additional silica gel flash column chromatography (methylene chloride-methanol 20/1) followed by repeated recrystallization yielded pure divinorin A (1) (1.2 g) and B (3) 50mg. 

Then 6 mL of 1,5-cyclooctadiene is added to the warm solution and the mixture swirled gently, cooled to room temperature, and diluted with 50 mL of water. The black suspension is stored for one hour at room temperature, and the crude product is collected on a Buchner funnel, washed with SO mL of water, and finally 100 mL of diethyl ether. T e crude product is suspended in 400 mL of dichloromethane and the mixture heated to the boiling point and kept at this temperature for 5 min. The solution is cooled, mixed with 5.0 g of chromatographic-grade silica gel, and allowed to settle. The supernatant liquid should be colorless if not, add additional silica gel in 1-g portions until the solution is clear. The mixture is filtered and the residue washed with two 50-mL portions of dichloromethane. The dichloromethane solution, approximately 500 mL, is evaporated until the product commences to crystallize, about 75 mL. The hot solution is poured into 200 mL of petroleum ether (bp 60-70°), yielding a finely divided white product. The precipitate is washed with 50 mL of petroleum ether and dried. Yield is 2.55 g (80%). 

Unlike halogenated additives silica gel /K2CO3 does not significantly affect the specific heat of combustion when added to PP [227]. Furthermore, since the CO yield and the soot (mean specific extinction area) are not significantly increased by these additives, the use of this system may represent an improvement over halogenated and some phosphorus based additives, which commonly tend to increase CO yield and soot [227]. These data indicate that these additives most likely act primarily in the condensed phase not in the gas phase. The cone calorimeter results for PP are summarized in Table 5.5 along with data for the other polymers examined [227]. 

A solution of 6-bromoindole (O.lOmol) in toluene (200 ml) was treated with Pd(PPh3)4 (5mol%) and stirred for 30 min. A solution of 4-fluorophenyl-boronic acid (0.25 M, 0.15 mol) in abs. EtOH was added, followed immediately by sal aq. NaHCOj (10 eq.). The biphasic mixture was refluxed for several hours and then cooled to room temperature. The reaction mixture was poured into sat. aq. NaCl (200 ml) and the layers separated. The aq. layer was extracted with additional EtOAc (200 ml) and the combined organic layers dried (Na2S04), filtered and concentrated in vacuo. The solution was filtered through silica gel using hexane-CHjCl -hexanc for elution and evaporated. Final purification by recrystallization gave the product (19 g, 90%). 

To a stirred ice-cold solution of ethyl 3,6-dihydro-5-hydroxy-8-methyl-6-(phenylsulfonyl)benzo[l,2-b 4,3-b ]dipyrrole-l-carboxylate (368 mg, 0.85 mmol) in TEA (3ml) was added EtjSiH (1.5 ml), After 15 min the solution was allowed to come to room temperature and stirred for an additional 2h. The solution was evaporated in vacuo and the residue dissolved in CH2CI2 (10 ml), washed.with aq. NaHCOj and dried over MgS04. The solution was mixed with AcjO (1ml) and CH2C12 (1ml) and kept at room temperature for 2 h. The reaction mixture was evaporated and the residue purified by chromatography on silica gel using CHjClj-EtOAc (3 1) for elution. The product (271 mg) was obtained in 71 % yield. 

The reseai ch has been carried out by the liquid chromatograph Perkin-Elmer (Series 200), which has tandem detectors the diode array (X=210 nm) and the refractometer. The temperature of a column was 30 C, speed of a mobile phase is 1.5 ml/ min. As a mobile phase, mixtures of solvents methanol - water and acetonitrile - water with addition of sodium perchlorate. The columns with the modified silica gel C8 and Cl8 (4.6x220 mm, 5 pm) were used for sepai ation of the AIST and FAS components. In order to make the identification of AIST and FAS components more reliable the ratio of the values of the above-mentioned detectors signals of each substance analyzed. 

R,5S,6R)-4-(t-Butoxycarbonyl)-5,6-dlphenyl-3>[(sthoxycarbonyt)methyl]-2,3,5,6-tetrahydro-4H-oxazln-2-one (6) To a stirred solution of erode 4 (226 mg 0 48 mmoQ m CH2CI2 (11 mL) was added ketene acetal 5 (450 mg, 2 42 mmol) followed by addition of 2nCl2 (575 mL, 0 44 mmol, 0 76M m THF) Alter 4 min ( was quenched with water Radial chromatography (silica gel EtOAc hexane 1 4) afforded 179 mg of 6 (78%)... 

Silica gel, per se, is not so frequently used in LC as the reversed phases or the bonded phases, because silica separates substances largely by polar interactions with the silanol groups on the silica surface. In contrast, the reversed and bonded phases separate material largely by interactions with the dispersive components of the solute. As the dispersive character of substances, in general, vary more subtly than does their polar character, the reversed and bonded phases are usually preferred. In addition, silica has a significant solubility in many solvents, particularly aqueous solvents and, thus, silica columns can be less stable than those packed with bonded phases. The analytical procedure can be a little more complex and costly with silica gel columns as, in general, a wider variety of more expensive solvents are required. Reversed and bonded phases utilize blended solvents such as hexane/ethanol, methanol/water or acetonitrile/water mixtures as the mobile phase and, consequently, are considerably more economical. Nevertheless, silica gel has certain areas of application for which it is particularly useful and is very effective for separating polarizable substances such as the polynuclear aromatic hydrocarbons and substances... 

Scott and Kucera [4] carried out some experiments that were designed to confirm that the two types of solute/stationary phase interaction, sorption and displacement, did, in fact, occur in chromatographic systems. They dispersed about 10 g of silica gel in a solvent mixture made up of 0.35 %w/v of ethyl acetate in n-heptane. It is seen from the adsorption isotherms shown in Figure 8 that at an ethyl acetate concentration of 0.35%w/v more than 95% of the first layer of ethyl acetate has been formed on the silica gel. In addition, at this solvent composition, very little of the second layer was formed. Consequently, this concentration was chosen to ensure that if significant amounts of ethyl acetate were displaced by the solute, it would be derived from the first layer on the silica and not the less strongly held second layer. 

Hydrophilic liquids can also cause stabilization and amplification of fluorescence Thus, Dunphy et al employed water or ethanol vapor to intensify the emissions of their chromatograms after treatment with 2, 7 dichlorofluorescein [260] Some groups of workers have pointed out that the layer matenal itself can affect the yield of fluorescent energy [261 —263] Thus, polyamide and cellulose layers were employed m addition to silica gel ones [245] The fluorescence yield was generally increased by a factor of 5 to 10 [264], but the increase can reach 100-fold [234, 265]... 

Note The reagent can be employed on silica gel and cellulose layers and the dipping solution can also be employed as a spray solution. The addition of collidine... 

A mixture of 3.18 g (10 mmoles) of 17 -hydroxy-2-hydroxymethylene-5a-androstan-3-one, 20 ml dry dimethyl formamide and 0.3 g (13 mmoles) of sodium hydride is stirred for 0.5 hr at room temperature under nitrogen. A total of 1.51 g (12.5 mmoles) of redistilled allyl bromide is added and the mixture is stirred for 1 hr on the steam bath. Aqueous potassium hydroxide (2 g in 5 ml of water) is added and stirring is continued for 1 hr on the steam bath. The reaction mixture is diluted with 50 ml of methylene dichloride followed by careful addition of 300 ml of water. The organic phase is separated and the aqueous phase is again extracted with 50 ml of methylene dichloride. The combined extracts are washed with water, dried over sodium sulfate, filtered and chromatographed on 200 g of silica gel. Elution with pentane-ether (4 1) provides 2a-allyl-17j -hydroxy-5a-androstan-3-one 0.85 g (26%) mp 118-119° [aj 14° (CHCI3), after crystallization from ether-hexane. 

After an additional 10 min, a 1 % solution of hydrochloric acid (100 ml) is slowly added to the stirred reaction mixture and the resultant mixture is transferred to a separatory funnel. The ether layer is separated and washed sequentially with water, 5 % sodium bicarbonate solution, water and saturated salt solution. The washed ether solution is dried over anhydrous sodium sulfate, filtered, and evaporated to give an oily residue (0.45 g). Chromatography of the crude product on silica gel (50 g) followed by crystallization of the solid thus obtained (0.18 g) from ethanol gives 3 -hydroxy-B-homo-cholest-5-en-7a-one acetate (67 0.14 g) mp 90-91° [a]o 99° (CHCI3). 

The only recorded example using this method in the sugar series is the chlorination of l,2 3,4-di-0-isopropylidene-D-galactopyranose (73) which affords in addition to the expected 6-chloro-6-deoxy derivative 74a, a 5,6-unsaturated derivative 75 as well. These products were separated by silica gel column chromatography no yields were given. 

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