Bisulfite, reaction with

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. 

Acetaldehyde can be isolated and identified by the characteristic melting points of the crystalline compounds formed with hydrazines, semicarbazides, etc these derivatives of aldehydes can be separated by paper and column chromatography (104,113). Acetaldehyde has been separated quantitatively from other carbonyl compounds on an ion-exchange resin in the bisulfite form the aldehyde is then eluted from the column with a solution of sodium chloride (114). In larger quantities, acetaldehyde may be isolated by passing the vapor into ether, then saturating with dry ammonia acetaldehyde—ammonia crystallizes from the solution. Reactions with bisulfite, hydrazines, oximes, semicarb azides, and 5,5-dimethyl-1,3-cyclohexanedione [126-81 -8] (dimedone) have also been used to isolate acetaldehyde from various solutions. 

The reaction with sodium sulfite or bisulfite (5,11) to yield sodium-P-sulfopropionamide [19298-89-6] (C3H7N04S-Na) is very useful since it can be used as a scavenger for acrylamide monomer. The reaction proceeds very rapidly even at room temperature, and the product has low toxicity. Reactions with phosphines and phosphine oxides have been studied (12), and the products are potentially useful because of thek fire retardant properties. Reactions with sulfide and dithiocarbamates proceed readily but have no appHcations (5). However, the reaction with mercaptide ions has been used for analytical purposes (13)). Water reacts with the amide group (5) to form hydrolysis products, and other hydroxy compounds, such as alcohols and phenols, react readily to form ether compounds. Primary aUphatic alcohols are the most reactive and the reactions are compHcated by partial hydrolysis of the amide groups by any water present. 

Sodium P-chloroethanesulfonate [15484-44-3] can be obtained by reacting vinyl chloride with sodium bisulfite [7631-90-5] (66). Reaction with nitronium tetrafluoroborate [13826-86-3] yi ds l-chloro-l- uoro-2-nitroethane [461-70-1] (67). 

There are several comprehensive reviews of analytical methods for vitamin K (19,20). Owiag to the preseace of a aaphthoquiaoae aucleus, the majority of analytical methods use this stmctural feature as a basis for analysis. Several identity tests such as its reaction with sodium bisulfite or its uv spectmm exploit this characteristic. Although not specific, titrimetric, polarographic, and potentiometric methods have also been used (20). 

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. 

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 ... 

Reduction by sodium dithionite. A small amount of sodium dithionite, solid or in solution, is added to a luciferase solution made with 50 mM phosphate, pH 7.0, containing 50 pM FMN. The amount of dithionite used should be minimal but sufficient to remove oxygen in the solution and to fully reduce the flavin. The solution made is injected into an air-equilibrated buffer solution containing a long-chain aldehyde and luciferase to initiate the luminescence reaction. With this method, the reaction mixture will be contaminated by bisulfite and bisulfate ions derived from dithionite. 

Further studies by Bode and co-workers have shown that enolate formation from a-chloroaldehydes and subsequent reaction with 4-oxo-enoates or unsaturated a-ketoesters 232 generates dihydropyranones 233 in excellent diastereo- and enantio-selectivities, and with impressively low catalyst loadings [90], This work has been extended to the generation of enolate equivalents from bisulfite adducts of a-haloaldehydes 234 under aqueous conditions (Scheme 12.50) [91]. 

Initially, 50 was converted into the benzoxazinone 51 by reaction with phosgene in the presence of triethylamine and 51 was isolated in 95% yield upon crystallization from methanol. Deprotection of the pMB group from 51 was accomplished with ceric ammonium nitrate (CAN) in aqueous acetonitrile. Efavirenz was isolated in 76% yield after crystallization from EtOAc-heptane (5 95), as shown in Scheme 1.19. There were two issues identified in this route. First, lequiv of ani-saldehyde was generated in this reaction, which could not be cleanly rejected from product 1 by simple crystallization to an acceptable level under the ICH guideline. Anisaldehyde was removed from the organic extract as a bisulfite adduct by washing with aqueous Na2S205 twice, prior to the crystallization of 1. Secondly,... 

Many of the modifications of the pyrazolone antiinflammatory agents are intended to increase the limited hydrophilicity of the parent molecules. Reaction of aminopyrine (157) with formaldehyde and sodium hydrogen sulfite affords dipyrone (158). The first step can be rationalized as an Eschweiler-Clark type N-methylation reaction, with bisulfite acting as the reducing agent. The resulting mono N-methyl analogue of 157 then apparently forms the sulfite adduct of the carbinolamine of formaldehyde. 

DNA and RNA may be modified with hydrazide-reactive probes by reacting their cytosine residues with bisulfite to form reactive sulfone intermediates. These derivatives can undergo transamination reactions with hydrazide- or amine-containing probes to yield covalent bonds (Draper and Gold, 1980) (Chapter 27, Section 2.1). 

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