Aldehydes cyanides

Monocarbaboranes are accessible from boranes and acetylides [Eq. (3.3)], aldehydes, cyanides, or isonitriles (Scheme 3.2)." ... 

Beginning in about 1850, Adolph Strecker (Chapter 9, Scheme 9.68) undertook experiments on the reaction between aldehydes, cyanide anion [CN ] (or hydrogen cyanide [HCN] itself) and ammonia [NH3] (commonly in the form of ammonium salts such as ammonium chloride [NH4CI]). The reaction that bears his name, the Strecker reaction, has been used for the preparation of a wide variety of racemic amino acids, and Scheme 12.32 shows how it can be used in the synthesis of alanine... 

Strecker synthesis (Section 23.2) A synthesis of amino acids using an aldehyde, cyanide, and ammonia, followed by hydrolysis. Structural isomers (Section 2.7) Molecules of the same formula... 

This type of reaction can be carried out as a multicomponent reaction by applying carboxylate, aldehyde, cyanide and a sulfonyl chloride [779]. 

By (he direct addition of hydrogen cyanide to aldehydes and ketones, giving cyanhydrins ... 

Many aromatic aldehydes (having the -CHO group joined directly to the benzene ring) undergo polymerisation when heated with a solution of potassium cyanide in aqueous ethanol. Thus benzaldehyde gives benzoin, a compound of double function, since it contains both a secondary alcoholic and a ketonic... 

Noth. The above method can be successfully applied only to dilute solutions of formaldehyde which are free in particular from other alfphatic aldehydes, since the latter, if present, would undergo a similar oxidation. Formaldehyde, if mixed with other aldehydes, should be estimated by quantitative addition of potassium cyanide for details, see advanced text-books of quantitative organic analysis. 

The only important precaution in this preparation is to ensure an excess of zinc chloride over sodium cyanide. If the latter is in excess, the zinc cyanide generally precipitates as a sticky mass, which is difficult to filter and unsatisfactory for the preparation of hydroxy-aldehydes. 

Benzoin condensation. Aromatic aldehydes when treated with an alkali cyanide, usually in aqueous solution, undergo condensation to the -hydroxyketone or benzoin. The best known example is the conversion of benzaldehyde to benzoin ... 

A more elaborate variation gives a generell amino acid synthesis. If the reaction between an aldehyde and cyanide is done in the presence of ammonia, the product is an a-amino-nitrile ... 

The conversion of primary alcohols and aldehydes into carboxylic acids is generally possible with all strong oxidants. Silver(II) oxide in THF/water is particularly useful as a neutral oxidant (E.J. Corey, 1968 A). The direct conversion of primary alcohols into carboxylic esters is achieved with MnOj in the presence of hydrogen cyanide and alcohols (E.J. Corey, 1968 A,D). The remarkably smooth oxidation of ethers to esters by ruthenium tetroxide has been employed quite often (D.G. Lee, 1973). Dibutyl ether affords butyl butanoate, and tetra-hydrofuran yields butyrolactone almost quantitatively. More complex educts also give acceptable yields (M.E. Wolff, 1963). 

With this as background let us now examine how the principles of nucleophilic addition apply to the characteristic reactions of aldehydes and ketones We 11 begin with the addition of hydrogen cyanide... 

The product of addition of hydrogen cyanide to an aldehyde or a ketone contains both a hydroxyl group and a cyano group bonded to the same carbon Compounds of this type are called cyanohydrins... 

Nitriles contain the —C=N functional group We have already discussed the two mam procedures by which they are prepared namely the nucleophilic substitution of alkyl halides by cyanide and the conversion of aldehydes and ketones to cyanohydrins Table 20 6 reviews aspects of these reactions Neither of the reactions m Table 20 6 is suitable for aryl nitriles (ArC=N) these compounds are readily prepared by a reaction to be dis cussed m Chapter 22... 

Section 20 18 Nitnles are prepared by nucleophilic substitution (8 2) of alkyl halides with cyanide ion by converting aldehydes or ketones to cyanohydrins (Table 20 6) or by dehydration of amides... 

The presence of an aldehyde function m their open chain forms makes aldoses reactive toward nucleophilic addition of hydrogen cyanide Addition yields a mixture of diastereo meric cyanohydrins... 

In the Strecker synthesis an aldehyde is converted to an a ammo acid with one more carbon atom by a two stage procedure m which an a ammo nitrile is an mterme diate The a ammo nitrile is formed by reaction of the aldehyde with ammonia or an ammonium salt and a source of cyanide ion Hydrolysis of the nitrile group to a car boxylic acid function completes the synthesis... 

Aldehydes by reaction with ammonia and cyanide ion (the Strecker synthesis)... 

Strecker synthesis (Section 27 4) Method for prepanng amino acids in which the first step is reaction of an aldehyde with ammonia and hydrogen cyanide to give an amino nitnle which IS then hydrolyzed... 

Historically these compounds have been made in two-step processes. Eor smaller volumes, reaction of an appropriate ketone or aldehyde with a cyanide salt followed by treatment with an ammonium salt proves satisfactory (Strecker synthesis). Eor larger volumes, treatment of the ketone or aldehyde with HCN to produce a cyanohydrin, followed by treatment with ammonia has been practiced. However, in 1990, DuPont began practicing a new one-step... 

Analogously, aldehydes react with ammonia [7664-41-7] or primary amines to form Schiff bases. Subsequent reduction produces a new amine. The addition of hydrogen cyanide [74-90-8] sodium bisulfite [7631-90-5] amines, alcohols, or thiols to the carbonyl group usually requires the presence of a catalyst to assist in reaching the desired equilibrium product. 

Synthesis from Aldehydes and Ketones. Treatment of aldehydes and ketones with potassium cyanide and ammonium carbonate gives hydantoias ia a oae-pot procedure (Bucherer-Bergs reactioa) that proceeds through a complex mechanism (69). Some derivatives, like oximes, semicarbazones, thiosemicarbazones, and others, are also suitable startiag materials. The Bucherer-Bergs and Read hydantoia syntheses give epimeric products when appHed to cycloalkanones, which is of importance ia the stereoselective syathesis of amino acids (69,70). 

Synthesis from Thiohydantoins. A modification (71) of the Bucherer-Bergs reaction consisting of treatment of an aldehyde or ketone with carbon disulfide, ammonium chloride, and sodium cyanide affords 2,4-dithiohydantoias (19). 4-Thiohydantoias (20) are available from reaction of amino nitriles with carbon disulfide (72). Compounds (19) and (20) can be transformed iato hydantoias. 

Both -hydroxybenzaldehyde and its methyl ether, -methoxybenzaldehyde [123-11-5] (p-anisaldehyde) have found extensive use in electroplating. The most widespread appHcation has been in alkaline bright zinc plating, both in non-cyanide (77) and in cyanide-containing (78) baths. The aldehydes act as both brightening and leveling agents. 

Peroxomonosulfuric acid oxidi2es cyanide to cyanate, chloride to chlorine, and sulfide to sulfate (60). It readily oxidi2es carboxyflc acids, alcohols, alkenes, ketones, aromatic aldehydes, phenols, and hydroquiaone (61). Peroxomonosulfuric acid hydroly2es rapidly at pH <2 to hydrogen peroxide and sulfuric acid. It is usually made and used ia the form of Caro s acid. 

With secondary alkanolamines, aldehydes in the presence of K CO yield di-tertiary amines, which, on distillation, break down into a,P unsaturated amines and secondary amines. With a mono- or dialkanolamine, an alkaU metal cyanide, and an aldehyde or ketone, aminoacetonitriles are formed. 

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