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Cyanohydrins elimination with bases

Cyanohydrins can be reconverted to carbonyl compounds by treatment with base. This process is just the reverse of the addition of HCN deprotonation followed by elimination of CN. [Pg.791]

Three additional approaches to the synthesis of CNT are shown in Fig. 9. The first [77, 78] involves transformation of 3 -ketonucleoside 44 into cyanohydrin 45, followed by deoxygenation at 3 and then at 2 to afford 47, which is easily epimerized to 31 by treatment with base (pH = 9). Treatment of 2 -0-acyl derivatives of 46 with bases produced elimination to give the 2, 3 -unsaturated nucleoside 48. An important factor in the chemistry of these cyanonucleosides is the acidity of the H-3 hydrogen atom in a-position to the nitrile group. This acidity is responsible for the facile epimerization 47 31 and for the elimination... [Pg.331]

Cyanohydrins eliminate HCN under basic conditions, giving the corresponding planar aldehyde or ketone. When combined with an asymmetric reaction, the equilibrium can be used for an efficient in situ racemization of cyanohydrins, leading to a DKR process. For example, chiral secondary cyanohydrins can be acylated by isopropenyl acetate in the presence of lipase and solid base such as anion-exchange resin (OH" form) [8a,b] or silica-supported ammonium hydroxide [8c] (Scheme 5.31). A range of aromatic cyanohydrin acetates can be obtained in high chemical and optical yields, although the efficiency is lower for aliphatic precursors [8a]. The success of DKR is ascribable not only to the stereochemical... [Pg.187]

Cyanohydrin derivatives have also been widely used as acyl anion synthons. They are prepared from carbonyl compounds by addition of hydrogen cyanide. A very useful variant is to use trimethylsilyl cyanide with an aldehyde to produce a trimethylsilyloxy cyanide. The cyano group acidifies the a position (pKA 25) and the a proton can be removed by a strong base. Alkylation of the anion and unmasking of the hydroxy group cause elimination of cyanide and re-formation of the carbonyl group. [Pg.304]

Purification this step features the second innovation of the process which, to eliminate the by-product acrolein, favors the formation of cyanohydrin by means of the hydrogen cyanide which is also present This operation takes place at low temperature (20 Q in agitated reactors, either continuously in the presence of a copper-based catalyst, or semi-continuously with a reaction phase in basic medium (caustic soda addition), followed by a neutralization period (sulfuric acid addition). The cyanohydrin obtained is then removed by vacuum distillation. The withdrawal may be sent to a thin layer evaporator to recover entrained acrylonitrile. These treatments must be conducted in the presence of a polymerization inhibitor and at a temperature below 55 C to prevent the rede-composition of cyanohydrin.... .. ... [Pg.228]


See other pages where Cyanohydrins elimination with bases is mentioned: [Pg.294]    [Pg.9]    [Pg.196]    [Pg.398]    [Pg.135]    [Pg.120]    [Pg.235]    [Pg.80]    [Pg.197]    [Pg.742]    [Pg.439]   
See also in sourсe #XX -- [ Pg.224 ]




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