Cyanohydrins stability

Acetone cyanohydrin (stabilized), 6 Acetone tliiosemicarbazide, 6 Acetonitrile, 6 Acetophenetidin, 7 Acetophenone, 7 Acetyl acetone peroxide, 7 Acetyl bromide, 7 Acetyl chloride, 7... 

Acetone Cyanohydrin, stabilized Acetone Oils 1541 1091 55 26 Alcohol (beverage) Alcohol, denatured 1170 26... 

Although usually handled as an aqueous solution, formaldehyde cyanohydrin can be isolated in the anhydrous form by ether extraction, followed by drying and vacuum distillation (23). Pure formaldehyde cyanohydrin tends to be unstable especially at high pH. Small amounts of phosphoric acid or monochloroacetic acid are usually added as a stabiLher. Monochloroacetic acid is especially suited to this purpose because it codistiHs with formaldehyde cyanohydrin (24). Properly purified formaldehyde cyanohydrin has excellent stability (25). 

The requisite starting cyanohydrin is readily prepared from a 20-keto-pregnane substitution at C-21 has no effect on the success of this step. However, the stability of the cyanohydrin is markedly dependent on other features of the molecule thus a 3-acetate confers greater stability than the free alcohol, and a 3-ketone is so unstable that subsequent dehydration with phosphorus oxychloride gives poor yields of the A -unsaturated nitrile. 

The mechanism of the cyanide- and thioazolium ion-catalyzed conjugate addition reactions is considered to be analogous to the Lapworth mechanism for the cyanide-catalyzed benzoin condensation. Thus the cyano-stabilized carbanion resulting from deprotonation of the cyanohydrin of the aldehyde is presumed to be the actual Michael donor. After conjugate addition to the activated olefin, cyanide is eliminated to form the product and regenerate the catalyst. 

Nucleophilic substitutions of 0-activated 2-hydroxy carboxylic acids and esters, respectively, are well established, but little is known about the analogous reactions of activated cyanohydrins. Chiral 2-sulfonyloxynitriles, accessible from non-racemic cyanohydrins, have a relatively high configurational stability. They react with nucleophiles under very mild conditions under inversion of configuration (Scheme 8). ° ... 

Because of the instability of cyanohydrins, the characterization of cyanohydrins mostly should be hydroxyl protected. In 2001, Gerrits et al. [26] investigated the influence of solvent composition on the stability of unprotected cyanohydrins and then described a method to analyze unprotected cyanohydrins (with regard to enantiomeric purity and conversion) via chiral high-performance liquid chromatography (HPLC). Hernandez et al. [27] and the groups... 

Olefination of the Aldehyde 178 using a stabilized Wittig reagent followed by protecting group chemistry at the lower branch and reduction of the a,p-unsaturated ester afforded the allylic alcohol 179 (Scheme 29). The allylic alcohol 179 was then converted into an allylic chloride and the hydroxyl function at the lower branch was deprotected and subsequently oxidized to provide the corresponding aldehyde 161 [42]. The aldehyde 161 was treated with trimethylsilyl cyanide to afford the cyanohydrin that was transformed into the cyano acetal 180. The decisive intramolecular alkylation was realized by treatment of the cyano acetal 180 with sodium bis(trimethylsi-lyl)amide. Subsequent treatment of the alkylated cyano acetal 182 with acid (to 183) and base afforded the bicyclo[9.3.0]tetradecane 184. 

The Sheldon group [87] prepared aquagels of different HNLs and compared them in the synthesis reaction of different cyanohydrins with the CLEAs and the free enzymes. The activity recovery for the aquagels and CLEAs measured by a photometric assay were quite low. Using the same loadings, the aquagels turned out to be much faster than the free enzyme. This confirms the underestimation of the recovery of activity by fast assays due to diffusion problems, as reported earlier [74, 75]. The stability and the catalytic performance of the immobilized HNLs are strongly influenced by the solvent, the immobilization method, and the enzyme source. 

Not surprisingly, nitriles that liberate cyanide more readily are more toxic. Logically, structural features that are expected to increase a-carbon radical formation and stability are likely to favor hydrogen atom abstraction from the a-carbon. The more quickly hydrogen atom abstraction occurs at the a-carbon, the more quickly cyanohydrin formation occurs and the more quickly cyanide is released and, hence, the more toxic the nitrile is expected to be. 

Since tJtiis reaction is an equilibrium, the amount of cyanohydrin formed from any given carbonyl compound will depend on the relative stabilities of the carbonyl compound itself and the product. There can be many substituents X on a carbonyl compound R.CO.X, such as Cl, Me, NH2, Ph, OEt, H. Some have inductive effects, some conjugate with the carbonyl group. Some stabilise RCOX making it less reactive. Others activate it towards nucleophilic attack. Arrange the compounds RCOX, where X can be the substituents listed above, into an order of reactivity towards a nucleophile. 

Cyanohydrins should be stabilized with acid to pH 3-4 to prevent decomposition 10 hydrogen cyanide and carbonyl compound. When cyanohydrins are shipped, steel drums, carboys, tank cars, and barges are used. In general, cyanohydrins are combustible liquids and many decompose upon heating. They should be stored in a cool, dry place, preferably outside and separated from other storage. Containers should be protected against physical damage. 

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