Ketone bisulfite

The kinetics and mechanism of the ketone-bisulfite addition were studied by the use of the polarographic technique (Rao Salunke, Reaction Kinetics and Catalysis Letters 26 273, 1984).The specific rate was found to depend on pH. For an equimolar solution of bisulfite and acetone in a deaerated solution of potassium hydrogen phthalate buffer containing potassium iodide as the... 

Gastaldi synthesis. Formation of dicyanopyra-zines by cyclization of two molecules of an amino-cyanomethyl ketone, produced by treatment of an isonitrosomethyl ketone bisulfite compound with potassium cyanide, heating in hydrochloric acid, and oxidation. 

Stelling (1928) found an absorption band in formaldehyde and acetone bisulfite addition compounds at 4992.0 A similar to that in sulfonic acids at 4992.2 and differing from that of metal alkyl (4996.0) and dialkyl sulfites (4997.7). He concluded from this that the sulfonic acid structure must be present. Raman spectral examinations of several aldehyde and ketone bisulfites by Caughlan and Tartar (1941) revealed the presence of a carbon-sulfur bond, possibly a carbon-hydroxyl bond, but no carbon doubly bonded to oxygen. This thus aided in discrediting both the tripartite molecule and the sulfurous acid ester structures. Sundman (1949) believes that formation of a stable monomolecular complex of boric acid and glucose bisulfite would be impossible if Schroeter s tripartite molecular structure were correct. His examinations of this complex led him to believe that its structure could be represented only by ... 

Aldehydes and ketones. Bisulfite method, neutral sulfite method, phenylhy-drazine method, hydroxylamine method. 

For years chemists have been using sodium bisulfite (that is BISULFITE not BISULFATE) to actually crystallize a ketone out of solution in order to separate it. As it so happens, our happy little MD-P2P is a ketone. And when an oil mixture containing it is mixed with a saturated solution of sodium bisulfite (NaHSOs) the MD-P2P crystallizes out as a bisulfite addition product . It can then be easily separated by filtration. Here s how it goes... 

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... 

Many of these reactions are reversible, and for the stronger nucleophiles they usually proceed the fastest. Typical examples are the addition of ammonia, amines, phosphines, and bisulfite. Alkaline conditions permit the addition of mercaptans, sulfides, ketones, nitroalkanes, and alcohols to acrylamide. Good examples of alcohol reactions are those involving polymeric alcohols such as poly(vinyl alcohol), cellulose, and starch. The alkaline conditions employed with these reactions result in partial hydrolysis of the amide, yielding mixed carbamojdethyl and carboxyethyl products. 

Sulfitation and Bisulfitation of Unsaturated Hydrocarbons. Sulfites and bisulfites react with compounds such as olefins, epoxides, aldehydes, ketones, alkynes, a2iridines, and episulftdes to give aHphatic sulfonates or hydroxysulfonates. These compounds can be used as intermediates in the synthesis of a variety of organic compounds. 

The butanals form the conventional aldehyde hydra2one, semicarba2one, and dimedone-type derivatives. In the absence of other aldehydes and ketones, -butyraldehyde can be deterrnined by addition of sodium bisulfite and the excess bisulfite deterrnined with iodine or thiosulfate (34). 

Cyclohexanone shows most of the typical reactions of aUphatic ketones. It reacts with hydroxjiamine, phenyUiydrazine, semicarbazide, Grignard reagents, hydrogen cyanide, sodium bisulfite, etc, to form the usual addition products, and it undergoes the various condensation reactions that are typical of ketones having cx-methylene groups. Reduction converts cyclohexanone to cyclohexanol or cyclohexane, and oxidation with nitric acid converts cyclohexanone almost quantitatively to adipic acid. 

Ketones are more stable to oxidation than aldehydes and can be purified from oxidisable impurities by refluxing with potassium permanganate until the colour persists, followed by shaking with sodium carbonate (to remove acidic impurities) and distilling. Traces of water can be removed with type 4A Linde molecular sieves. Ketones which are solids can be purified by crystallisation from alcohol, toluene, or petroleum ether, and are usually sufficiently volatile for sublimation in vacuum. Ketones can be further purified via their bisulfite, semicarbazone or oxime derivatives (vide supra). The bisulfite addition compounds are formed only by aldehydes and methyl ketones but they are readily hydrolysed in dilute acid or alkali. 

In a 3-I. flask are placed a solution of 184 g. (4.6 moles) of sodium hydroxide in 300-400 cc. of water and sufficient ice to make the total volume about 1500 cc. Chlorine is passed into the solution, keeping the temperature below 0° by means of a salt-ice bath, until the solution is neutral to litmus (Note i). After the addition of a solution of 34 g. of sodium hydroxide in 50 cc. of water, the flask is supported by a clamp and equipped with a thermometer and an efficient stirrer. The solution is warmed to 55°, and 85 g. (0.5 mole) of methyl d-naphthyl ketone (Note 2) is added. The mixture is vigorously stirred and, after the exothermic reaction commences, the temperature is kept at 60-70° (Note 3) by frequent cooling in an ice bath until the temperature no longer tends to rise. This requires thirty to forty minutes. The solution is stirred for thirty minutes longer and then the excess hypochlorite is destroyed by adding a solution of 50 g. of sodium bisulfite in 200 cc. of water (Note 4). After cooling to room temperature, the reaction mixture is transferred to a 4-I. beaker and carefully acidified with 200 cc. 

An alternate method of producing the 21-hydroxy-20-ketone consists in lithium aluminum hydride reduction of the dimethyl acetal, hydrolysis to the 20-hydroxy-21-aldehyde and rearrangement, preferably via the bisulfite addition product... 

The enhanced reactivity of fluoroalkyl ketones is also manifested in the failure to stop the reaction with hydrogen cyanide at the stage of cyanohydrins Instead, oxazohdinones or dioxolanones are formed (equation 11) If, however, the reaction IS conducted under basic conditions with sodium bisulfite and sodium cyanide, the desired cyanohydrin can be prepared [ll ... 

The cyanohydrin of methyl perfluoroheptyl ketone was synthesized by a two-step process addition of sodium bisulfite and subsequent treatment with sodium cyanide. When the ketone was reacted with sodium cyanide, cyclic addition products were obtained, instead of the product of cyanohydrin formation. This result was attributed to the solubility characteristic of a long perfluoroalkyl group, which makes the compound less soluble in water and polar organic solvents [54] (equation 40) (Table 14). 

A solution of 100 g of sodium bisulfite in 200 ml of water is added, and the stirring is continued for 10 hours with exclusion of air. A thick precipitate separates after a few minutes. The bisulfite compound is collected by suction filtration, washed with ether until colorless, and then decomposed in a flask with a lukewarm solution of 125 g of sodium carbonate in 150 ml of water. The ketone layer is separated, and the aqueous layer is extracted four times with 30-ml portions of ether. The combined organic layers are dried over anhydrous magnesium sulfate, the ether is removed at atmospheric pressure, and the residual oil is fractionated under reduced pressure through a short column. The cycloheptanone, bp 64-65°/ 2 mm, is obtained in about 40% yield. 

A mixture of 59.5 g of that oily product, 1.B5 liters of benzene and 1 kg of potassium bisulfite in 200 liters of water is stirred at room temperature for two hours. The precipitated bisulfite addition product of the ketone is isolated by filtration and washed with isopropanol and then with ether. Five hundred grams of the adduct is mixed with 119.5 g of potassium cyanide, 292 ml of B5% hydrazine hydrate and 910 ml of water. The mixture is stirred overnight at room temperature after which the product is isolated by filtration. The product is washed 3 times with 250 ml portions of water and then 3 times with 230 ml portions of ether. It is then air dried and vacuum dried at room temperature. The intermediate so produced has the following formula ... 

Bisulfite addition products are formed from aldehydes, methyl ketones, cyclic ketones (generally seven-membered and smaller rings), a-keto esters, and isocyanates, upon treatment with sodium bisulfite. Most other ketones do not undergo the reaction, probably for steric reasons. The reaction is reversible (by treatment of the addition product with either acid or base ) and is useful for the purification of the starting compounds, since the addition products are soluble in water and many of the impurities are not. ... 

Sodium borohydride Hydroxylamine Sodium bisulfite Ketones, aldehydes. 

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