Bisulfite solution

Anyway, one has the P2P/crap oil, right Right. Next one makes a saturated sodium bisulfite solution by dissolving as much sodium bisulfite as will dissolve in a given amount of water (say, lOOOmL). Now one adds the MD-P2P oil into some of the saturated solution and stirs for 30 minutes. The temperature of the reaction will rise and a big old mass of P2P crystals will form. People often say that the crystals look like chicken fat. Those crystals formed because the bisulfite from the sodium bisulfite latched onto the ketone of the P2P to form a precipitate. And since the P2P is probably the only oil component with a ketone, it is gonna be the only thing of any consequence that crystallizes. 

Strike sees a point to this in Vogel s text Practical Organic Chemistry (3 ed.)[37]. In it, Vogel crystallizes his ketones using a saturated sodium bisulfite solution that a/so contains a little solvent. This is in contrast to the straight up aqueous (only water) solution that Strike described above. Here is A/hat Vogel said on page 342 ... 

Either pure aqueous or aqueous/solvent solutions work. It is entirely up to the preference of the chemist as to which one they use. Just to make one feel more secure, there is a little test one can do with the bisulfite solution to see if they got it right. Just put a little of that ketone known as acetone into the saturated solution and watch the crystals grow. Isn t it nice how chemistry works ... 

Now then, there are some chemists that rely on bisulfite as a tool to physically separate all of their ketone from an oil mix. But some chemists, using some methods, are rightfully sure enough that their ketones were produced in such high yields, and so cleanly, that separation isn t necessary at all. But even they, like anyone else, would still like to know for sure that what they made was P2P. This bisulfite procedure works in this regard as well. If one wants to know if what they made is P2P all one has to do is just drop a mL or so into the saturated bisulfite solution and see what happens. If crystals form, one has ketone. If not, one has fucked up. 

So now we have this solvent containing ketone, dried with MgS04... Not being able to vac-distill today, took about 50 mis of solvent/ketone and placed in beaker on stir plate and boiled off the solvent. The resulting oil was a nice reddish-orange color. Had a very unique smell too. Took about 2 grams worth of this ail, added to a test tube containing a saturated solution of sodium bisulfite... In less than 60 seconds the oil precipitated into a whitish yellow mass (very similar to what acetone would do if added to a bisulfite solution). Never had this quick of a crystallization. Not... 

Sodium Bisulfite. Sodium bisulfite, NaHSO, exists in solution but is not a stable compound in the soHd state. The anhydrous sodium bisulfite of commerce consists of sodium metabisulfite, Na2S20. Aqueous sodium bisulfite solution, having specific gravity 1.36 and containing the equivalent of 26—27 wt % SO2, is a commercial product. 

Chemical Properties. The chemistry of sodium metabisulfite is essentially that of the sulfite—bisulfite—metabisulfite—sulfurous acid system. The relative proportions of each species depend on the pH. The pH of a sodium bisulfite solution obtained by dissolving 10 wt % sodium metabisulfite in water at 20°C is 4.9 at 30 wt %, the pH is 4.4. 

Bisulfite Reaction. Coumarin combines readily with sodium bisulfite solutions to form soluble sodium 3- or 4-hydrosulfonates (23). Coumarin can be regenerated by acidification and this method has been used for its purification. 

Golorfastness to Bleaching. In fastness to hypochlorite bleachiag, ISO 10S-N01, the specimen is agitated ia a solution of sodium, calcium, or lithium hypochlorite containing 2 g/L available chlorine buffered to pH 11.0 with sodium carbonate for 1 h at 20°C and 50 1 Hquor-to-goods ratio. The specimen is tinsed ia water, hydrogen peroxide, or sodium bisulfite solution to remove free chlorine, dried, and assessed. 

A mixture of 10 ml of saturated sodium bisulfite and 50 mL of water is used. One or more washings with sodium bisulfite solution are necessary if iodine is present. 

To the acid chloride, mechanically stirred and heated on the steam bath, is added 2.5 kg. (805 ml. 15.6 moles) of dry bromine as rapidly as it will react (Note 5). The addition requires about 12 hours. The contents of the flask are stirred and heated an additional 2 hours, transferred to a dropping funnel (Note 6), and added in a thin stream to 5 1. of absolute ethyl alcohol, which has previously been placed in a 12-1. flask provided with a stopper carrying an effleient reflux condenser, a separatory funnel, and a mechanical stirrer. The resulting vigorous reaction is controlled by external cooling. After the dibromoacid chloride has been added, the reaction mixture is allowed to stand at room temperature overnight and is then poured into 5 1. of cold water. The top alcoholic aqueous layer is decanted and extracted once with 8 1. of ether. The oily bottom layer is dissolved in the ether extract, washed first with 1 1. of a 2% sodium bisulfite solution, then with two 1-1. portions of 3% sodium carbonate solution, and finally with several portions of water. The ether solution is dried over 175 g. of potassium carbonate the solvent is distilled on the steam bath. The yield of residual ester (Note 7) amounts to 2260-2400 g. (91-97% of the theoretical amount). 

The material is triturated with saturated sodium bisulfite solution (2 cc. per gram), and after about three hours the pasty mixture is filtered with suction. The addition product is washed with absolute alcohol and then with ether and transferred to a flask fitted for steam distillation. Excess sodium carbonate solution is added and the aldehyde is distilled in a current of steam. 

A solution of 4.36 g of sodium iodide in 100 ml of ethanol is added to a boiling mixture of 10 g of the tetrabromide in 1.5 liters of ethanol, and the mixture is refluxed for 1 hr. Water is added and the mixture is extracted with ether, the extract washed with dilute sodium bisulfite solution and water, and the ether evaporated. The residue is taken up in 1000 ml. of methanol and refluxed for 1 hr after the addition of a solution of 50 g. of potassium hydroxide in 50 ml. of water. Water is added and the mixture is extracted with ether, the extract washed with water and the ether evaporated. The alkaline layer is acidified and extracted with ether. The extracts are washed... 

The enol lactone (12.7 g) is added to 157 ml of 0.5 M perbenzoic acid in benzene and allowed to stand at 25° for 140 hr. The solution is cooled to 15° and 15% sodium bisulfite solution is added to neutralize the excess peracid. The organic layer is separated and washed with saturated sodium bicarbonate solution and water. The benzene solution is dried over anhydrous sodium sulfate, filtered and concentrated to 30 ml. The product is crystallized by adding 80 ml of petroleum ether, filtered and washed with petroleum ether to yield 12.8 g (98%) of 3a,20,23-trihydroxy-16a-methyl-17(20)-oxido-ll-oxo-21-norchol-22-enoic acid-24(20)-lactone 3,23-diacetate mp 225-227°. 

A mixture of a-naphthol 41 (15.0 g, 0.1 mol), phenylhydrazine 42 (11.0 g, 0.1 mol) and sodium bisulfite solution (36 %, 250 g) was heated at reflux for 15 h. A further 4 g of phenylhydrazine was added and heating continued for 15 h, after which time the majority of the a-naphthol was consumed. After cooling, the mixture was extracted with ether. The oily, ether and aqueous insoluble residue was warmed with cone. HCl until a dark crystalline mass developed. After cooling, the mixture was extracted with ether. The organic extract was dried and concentrated to afford a crystalline residue which was purified by recrystallisation from ethanol to afford the product 43 as a white crystalline solid, mp 225 °C. A reaction yield is not given. 

A 100-ml flask is charged with 25 ml of bromine and 10 g of adamantane and heated under reflux for 3 hours. The cooled mixture is dissolved in 100 ml of carbon tetrachloride, and the carbon tetrachloride solution is washed with 100-ml portions of saturated bisulfite solution until the color of bromine is discharged. The solution is then washed twice with water and dried (magnesium sulfate). The solvent is removed (rotary evaporator) and the product is recrystallized from methanol. (For best recovery of the recrystallized material, the methanol solution should be cooled in a Dry Ice cooling bath.) The product has mp 108°. 

These extracts are then combined with the organic solvent layer and the combined organic phase is extracted four times with 100 ml portions of water. It Is then stirred for an hour with 230 ml of 10% sodium bisulfite solution. The organic solvent phase is then separated, washed seven times with 100 ml portions of water and dried over magnesium sulfate. Evaporation of the solvent gives 1-(4-hydroxy-3-methoxyphenyl)-2-propanone in the form of an oil. 

A solution of 11.2 g of potassium permanganate in 100 ml of warm water was added drop-wise to a well stirred solution of 10 g of 2-(4-chlorophenyl)-3-methyl-4-metathiazanone in 50 ml of glacial acetic acid. The temperature was kept below 30°C with external cooling. An aqueous sodium bisulfite solution was then added to remove the manganese dioxide. The thick whitish oil which separated was taken up in chloroform and the extract was washed with water. Removal of the chloroform by distillation in vacuo yielded an oily residue which solidified. The solid was recrystallized from isopropyl alcohol to give 5 g of the product, 2-(4-chlorophenyl)-3-methyl-4-metathiazanone-1,1-dioxide, MP 116.2° to 118.6°C (corr.). 

When the chlorination is complete, the reaction mixture is poured into 1,000 parts of water and treated with a dilute sodium bisulfite solution, until no more reaction may be observed with starch-potassium iodide paper. Thereby the 5,7-dichloro-8-hydroxy-quinaidine separates out in form of a weakly yellowish colored precipitate. The same is filtered off and thoroughly washed with water. 

A mixture of 1.38 grams of the above compound and 15 cc of dioxane was treated with 1.9 cc of a 0.5 N aqueous solution of perchloric acid and 600 mg of N-bromoacetamide, adding the latter in the dark, in three portions, in the course of half an hour and under continuous stirring. It was then stirred for a further 1% hours in the dark, then the excess of reagent was decomposed by the addition of aqueous sodium bisulfite solution and ice water was added the product was extracted with methylene chloride, washed with water, dried over anhydrous sodium sulfate and the solvent was evaporated under reduced pressure, thus giving a yellow oil consisting of the 16,21-diacetate of 6a-fluoro-9a-bromo-16o-hydroxy-hydrocortisone which was used for the next step without further purification. 

The catalyst was removed by filtration. The filtrate was diluted to about 18 liters, and was acidified with 15 ml concentrated hydrochloric acid. With vigorous stirring, 1,152 ml N KICI2 solution were run into the diluted filtrate over a period of about 20 to 30 minutes. A solid precipitate was formed, and was filtered off after about six hours. The sol id material was washed with water, with sodium bisulfite solution, and again with water. It was dissolved in aqueous ammonium hydroxide solution, the solution was filtered, and the filtrate was acidified with concentrated hydrochloric acid containing a small amount of sodium bisulfite. After a short time, the precipitate formed was filtered with suction, washed with water, and dried. 

A solution of 192 g 3-acetylamino-2,4,6-triiodophenol, sodium (0.35 mol) in 350 ml di-methylacetamide, was mixed with 107.5 g 3-(2-iodoethoxy)-2-ethylpropionic acid ethyl ester (0.35 mol) at 90°C with stirring over a period of about 20 to 30 minutes. Stirring was continued while the mixture was held at 95°C to 100°C for 16 hours. The solvent was then removed by distillation in a vacuum, and the residue was poured into 4,000 ml water. The solid precipitate formed was recovered and washed with water, dilute sodium carbonate solution, dilute sodium bisulfite solution, and again with much water. The ethyl ester was obtained in a yield of 220 g (90%). When recrystallized from 75% aqueous ethanol, it melted at 80°C to 86°C. 

The aqueous portion of the mixture is now siphoned off from the supernatant layer of oily phenyinitropropanol and replaced with a fresh solution of 11.0 kg of sodium bisulfite in 50.0 liters of water. The mixture of phenyinitropropanol and bisulfite solution Is now vigorously agitated for 15 minutes in order to remove and recover small amounts of unreacted benzaldehyde, and is then again allowed to stratify. This time, the phenyinitropropanol is siphoned off and filtered to remove a small amount of resinous material. The aqueous solution of sodium bisulfite remaining behind is reacted with benzaldehyde, as described above, thus making the process continuous. 

The reaction rate increases when heated to temperatures up to 40°C. The amino derivatives can then be quaternized if desired. The N-methylol derivatives of polyacrylamide can be made cationic by heating with amines, or they can be made anionic by heating with aqueous bisulfite solution under basic conditions. 

If the stirring is not very efficient the benzene layer should be stirred with the bisulfite solution a second time. 

Where larger, semibulk quantities of sulfite-based oxygen scavengers are required, a 20 to 25% bisulfite solution is recommended. It is sufficiently concentrated to provide reasonable freeze protection. The overall oxygen scavenging reaction is ... 

When the bisulfite solution is added, the solution acquires a deep brown color and iodine fumes develop. 

Note 5). The layers are separated (Note 6) the aqueous layer is returned to the separatory funnel and covered with 200 cc. of ether. After 100 cc. of 10 per cent sodium hydroxide has been added, the mixture is vigorously shaken, and then the aqueous layer is removed and extracted with another 200-cc. portion of ether. The two ether extractions, one with addition of sodium hydroxide and one without, are repeated. The second half of the bisulfite solution is subjected to the same treatment as the first half, and all the ether extracts are combined (Note 7) and dried over anhydrous sodium sulfate. The ether is removed on the water bath, and the residual yellow-green oil is distilled under reduced pressure, yielding 120-130 g. (45-49 per cent of the theoretical amount, based upon 210 g. of pure citral) of pale yellow pseudoionone, boiling at 114-116°/2 mm. (124-126°/4 mm.). 

A method for the determination of formaldehyde in the presence of acetaldehyde was developed by Nicolet and Shinn.88,100 103 After the excess periodate had been destroyed, these workers swept the acetaldehyde (from the neutral reaction mixture) into a sodium bisulfite solution by means of a stream of carbon dioxide. The acetaldehyde was measured by conventional, bisulfite methods, and the residual formaldehyde was precipitated with Dimedon. This procedure was applied to protein hydroly-zates and to terminal deoxy structures of carbohydrates.88,280 ... 

A mixture of 4.5 g. of 1-hydroxy-2-propanone, 80 ml. of ethyl acetoacetate, 60 ml of 96% ethyl alcohol, and 4 g. of anhydrous zinc chloride is heated under reflux on a steam bath for half an hour. After cooling, it is poured into water and extracted with benzene. The extract is washed successively with a bisulfite solution (twice), dilute aqueous sodium hydroxide, and dilute hydrochloric acid, and is dried over anhydrous sodium sulfate. The benzene is evaporated, giving 4 g. of an almost colorless oil which is saponified by heating with 5 g. of sodium hydroxide in 20 ml. of 96% alcohol for half an hour on a steam bath. Part of the alcohol is evaporated, water is added, and the solution is extracted twice with ether. The aqueous layer is acidified (to Congo Red) with hydrochloric acid (1 1). The resulting solid is removed by filtration and recrystallized from 180 ml. of water yield, about 3 g. It may be purified by steam distillation, affording colorless crystals m. p., 120-122°. 

For handling acrolein, gloves, vapor-proof goggles or a full face mask, and other protective clothing are mandatory (Albin 1962 Beauchamp et al. 1985 NIOSH 1990). Acrolein spills should be neutralized with 10% sodium bisulfite solutions (Albin 1962). Air packs or fresh-air breathing masks, safety showers, and eye baths should be available wherever acrolein is handled (Beauchamp... 

SOXAL A flue-gas desulfurization process, basically similar to the Wellman-Lord process but regenerating the bisulfite solution in a membrane electrochemical cell. Developed by Allied Signal Group and piloted at the Florida Power Light Company, Miami, FL, in 1991. A larger demonstration plant was planned for Dunkirk, New York. 

The ethyl acetate layer is washed with water, sodium bisulfite solution, saturated calcium chloride solution, and again with water. It is further purified as in Note 6, giving 316-400 g. of recovered ester. The amount of recovered ester depends somewhat upon the length of time the two layers are allowed to remain in contact before separating. 

At this point crude phenylthio-1,2-dibromoethane can be isolated by separation of the organic phase, extraction of the aqueous layer with dichloromethane, washing of the combined extracts with saturated sodium bisulfite solution, drying (MgSC>4), and concentration (95% crude yield) 1 H NMR (270 MHz, CDCI3) 5 3.75... 

Sodium bisulfite Solution s Vinyl chloride Unknown 1... 

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