Bisulfite addition product

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... 

D. Now the ether will be a deep reddish yellow. Distill off the ether...quack...and take the temp up to 170 C to drive off any other volatiles. Should recover 90%+ of the original weight of oil. Now add 500 ml of saturated bisulfite and stir for 1.5 hours...Quack Vacuum Filter, the duck fat crystals Wash with water and ether, yield dull fine ppt in the filter cake...stable bisulfite addition product...can be stored forever...QuackU Yield -50 to 80% depending on a ducks technique ... 

Not-Strike may have seen. But what Dr. Quack did that SWINS did not was use the bisulfite test with positive results. What does that mean It means that some doublebonded oxygen was formed, unless Dr. Quack was fibbing to us, It cannot have been a propiophenone (don t ask) because propiophenones cannot form the bisulfite addition product. Could an aldehyde have formed (don t ask) Maybe. But highly unlikely considering the mechanism of the reaction. 

Isolate. A relatively pure chemical produced from natural raw materials by physical means, eg, distillation, extraction, crystallization, etc, and therefore natural or by chemical means, ie, via hydrolysis, bisulfite addition products, and regeneration, etc, and therefore artificial by 1993 U.S. labeling regulations. 

Unlike simple, unhindered carbonyl compounds, the quinones do not yield bisulfite addition products, but undergo ring addition. Another significant carbonyl reaction is the addition of tertiary phosphites under anhydrous conditions (98). The ester product (99) is easily hydroly2ed, and the overall sequence produces excellent yields of hydroquinone monoethers. 

M-Methylpiperldine (3). To the gluteraldehyde 1 bisulfite addition product (3 08 g, 10 mmol) and 2 HCI (1 3 g, 20 mmol) in MeOH (50 mL) was added NaBHsCN (500 mg, 9 mmol) After 48 h at 25 C it was acidified to pH-2, evaporated and the residue dissolved in water and basified with 6 N KOH Alter extraction with EtjO (8x25 mL), drying (MgS04) and evaporation the residue in EtOH (3 mL) was treated with picric acid (10 mmol) in EtOH to give 1 38 g ol 3 picrate (43%) mp 147 t49°C... 

Mandelic acid is best prepared by the hydrolysis of mandeloni-trile with hydrochloric acid. The mandelonitrile has been prepared from amygdalin, by the action of hydrocyanic acid on benzaldehyde, and by the action of sodium or potassium cyanide on the sodium bisulfite addition product of benzaldehyde. ... 

The method in the procedure differs from any previously described in that the sodium bisulfite addition product of benzal-dehyde is prepared in the presence of sodium cyanide and the nitrile is formed immediately. 

Muconic acid has been obtained in a variety of ways. The procedures that seem most important from a preparative point of view are by treatment of ethyl o ,5-dibromoadipate with alcoholic potassium hydroxide, by condensation of glyoxal (as the sodium bisulfite addition product) with malonic acid, by heating ethyl l-acetoxy-l,4-dihydromuconate (obtained by condensing ethyl oxalate and ethyl crotonate, acetylating, and reducing),and by oxidation of phenol with peracetic acid. ... 

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... 

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 ... 

The crude ester is cooled, an equal volume of benzene is added, then the free acid is neutralized by shaking with about 250 cc. of a 10 per cent solution of sodium carbonate (Note 4). The benzene solution is poured into 1300 cc. of a saturated solution of sodium bisulfite (about 60 g. of technical sodium bisulfite per 100 cc.), contained in a wide-neck bottle equipped with an efficient stirrer, and the mixture stirred for two and a half hours. The mixture soon warms up a little and becomes semi-solid. It is filtered through a 20-cm. Buchner funnel and carefully washed, first with 200 cc. of a saturated solution of sodium bisulfite, finally with two 150-cc. portions of benzene (Notes 5 and 6). The white pearly flakes of the sodium bisulfite addition product are transferred to a 3-I. round-bottom wide-neck flask equipped with a mechanical stirrer and containing 700 cc. of water, 175 cc. of concentrated sulfuric acid, and 500 cc. of benzene. The flask is heated on a steam bath under a hood, the temperature being kept at 55°, and the mixture is stirred for thirty minutes (Note 7). The solution is then poured into a separatory funnel, the benzene separated and the water layer extracted with a 200-cc. portion of benzene. The combined benzene solution is shaken with excess of 10 per cent sodium carbonate solution to remove free acid and sulfur dioxide (Note 8). The benzene is washed with a little water and then dried over anhydrous potassium carbonate (Note 9). The benzene is distilled at ordinary pressure over a free flame from a 500-cc. Claisen flask, the solution being added from a separatory funnel as fast as the benzene distils. It is advisable to distil the ester under reduced pressure although it can be done under ordinary pressure. The fraction distilling around n8°/5mm., 130710 mm., 138715 mm., 148725 mm., 155735 mm., or... 

A mixture of 1.5 1. of water and 624 g. (6.00 moles) of sodium bisulfite in a 5-1. beaker equipped with a mechanical stirrer is stirred until solution is complete. Benzaldehyde (Note 1) (636 g., 6.00 moles) is added and the mixture is stirred for 20 minutes, during which time a slurry of the benzaldehyde-bisulfite addition product is formed. A 25% aqueous solution of dimethylamine (1100 g.) containing 275 g. (6.13 moles) of the amine is run in, and stirring is continued as most of the addition compound dissolves. The beaker is immersed in an ice bath, and 294 g. (6.00 moles) of sodium cyanide (CautionI Toxic) is added over a period of 20-25 minutes. 

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. ... 

Frequently, it is the bisulfite addition product that is treated with CN. This method is especially useful for aromatic aldehydes, since it avoids competition from the benzoin condensation. If desired, it is possible to hydrolyze the cyanohydrin in situ to the corresponding a-hydroxy acid. This reaction is important in the Kiliani-Fischer method of extending the carbon chain of a sugar. 

The pseudoionone bisulfite addition product, unlike that of citral, apparently decomposes rather slowly if the separation is made too soon, some undecomposed bisulfite compound is left in solution. This is later decomposed and, in contact with the alkali, polymerizes to a dark red gum. 

The mixture is extracted with ten 175-ml. portions of benzene or 1 1 benzene-ether mixture (Note 4). The combined extract is washed with 75-ml. portions of water until the washings are neutral to litmus. The organic solvent is removed by distillation on a steam bath. The crude oily residue is converted directly (Note 5) to the /3-tetralone bisulfite addition product. 

B. Bisulfite addition product of /3-tetralone. To a solution of 325 g. (3.12 moles) of sodium bisulfite (commercial purified grade) in 565 ml. of water is added 175 ml. of 95% ethanol. The mixture is allowed to stand overnight, and the precipitated sodium bisulfite is removed by filtration. The filtrate is added to the crude /3-tetralone, and the mixture is shaken vigorously. Within a few minutes the addition product separates as a voluminous precipitate. The mixture is kept cold for several hours, shaken periodically, and then filtered with the aid of suction. The precipitate is washed well, first with 125 ml. of 95% ethanol, then four times with 125-ml. portions of ether (Note 6). The colorless addition product is air-dried (Note 5) and is stored in air-tight containers. The yield is 113-131 g. (60-70% based on /3-naphthyl ethyl ether) (Note 7). 

C. Regeneration of 0-tetralone. Fifty grams (0.20 mole) of /3-tetralone bisulfite addition product is suspended in 250 ml. of water, and 75 g. (0.6 mole) of sodium carbonate monohydrate is added. At this point the pH of the solution is approximately 10. The mixture is extracted with five 100-ml. portions of ether (Note 8). The combined extract is washed with 100 ml. of 10% hydrochloric acid, then with 100-ml. portions of water until the washings are neutral to litmus, and is dried over anhydrous magnesium sulfate. The ether is removed by distillation, and the residue is distilled from a Claisen flask under reduced pressure, preferably in a nitrogen atmosphere. The pure /3-tetralone is obtained as a colorless distillate b.p. 70-71°/0.25 mm. (92-940/1.8 mm., 114-11674.5 mm.) n 1.5594. The yield is 17-21 g. (40-50% based on /3-naphthyl ethyl ether). 

In this step the /3-tetralone is separated from starting material and other neutral substances in the reaction mixture. /3-Tetralone is sensitive to air oxidation therefore it should not be stored in the free state. The bisulfite addition product is stable, and the dry material can be stored indefinitely without deterioration. 

The yield of the bisulfite addition product is subject to variation owing to coprecipitation of sodium bisulfite. 

The ether extract and the water layer may be tested for the presence of /3-tetralone or the bisulfite addition product by the tetralone blue test. 

A solution of 100 g. of sodium bisulfite (Note 5) in 200 ml. of water is added as stirring is continued. After a few minutes a thick precipitate separates. The mixture is stirred or preferably shaken mechanically at room temperature with exclusion of air for 10 hours. The bisulfite addition product is separated by suction filtration, washed with ether until colorless, and decomposed in a flask with a lukewarm solution of 125 g. of sodium carbonate in 150 ml. of water. The ketone layer is separated, the aqueous layer is extracted with four 25-ml. portions of ether, and the combined organic layers are dried over anhydrous sodium sulfate. Most of the ether is removed by distillation at atmospheric pressure, and the residual oil is distilled at reduced pressure (Note 6). 

Formation of Bisulfite Addition Products O-Hydro-C-sulfonato-addition... 

F. Sodium Bisulfite Addition Product Formation The red color of aminochrome solutions is rapidly discharged by the addition of sodium bisulfite with the formation of pale-yellow fluorescent solutions. The reactions of adrenochrome with sulfites and bisulfites have been the subject of several previous reports.12, 102.109.118,119.123,128,148.182.155. 158,173-177 Although it was originally... 

The 7-iodoaminochromes also form addition products with sodium bisulfite, although formation of these adducts usually appears to be accompanied by some deiodination, with the consequent formation of the corresponding deiodinated complexes.155 The 7-iodonor-adrenochrome-sodium bisulfite addition product has been reported to be more stable in this respect (i.e. it shows less tendency to deiodinate) than the corresponding 7-iodoadrenochrome adduct.119 Although it has not proved possible to demonstrate effectively the presence of both the 7-iodoaminochrome complex and the corres-... 

Paper Chromatographic Data on Some Aminochrome-Sodium Bisulfite Addition Products"... 

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