Carbonyl cyanide, with alcohols

Carbon tetrachloride-organo-phosphine, chlorides from alcohols with, 54, 63 CARBONYL CYANIDE, 51, 70 Carbonyl cyanide, with alcohols, 51, 72... 

Hydroboration of a,C0-dienes with monoalkylboranes gives reactive organoboron polymers which can be transformed into polymeric alcohols or polyketones by carbonylation, cyanidation, or the DOME reaction followed by oxidation (446—448). 

Another procedure replaces the above combination of ammonium chloride and alkali cyanide with ammonium cyanide. This reagent and the carbonyl compound in alcoholic solution are allowed to react at room temperature for several days. Aliphatic and alkyl aryl ketones, but not diaryl ketones, give products in 20% to 90% yield. 

Cyanide addition to the lactamic carbonyl group has been described in a reaction in which the cyanide ion acts as a catalyst (Fig. 14).The intermediate acyl cyanide can be attacked by an added nucleophile (allylic, propargylic, benzylic alcohols, aniline, benzylmercaptan). Comparative experiments were carried out using more classical procedures, such as under catalysis by potassium cyanide with stirring at room temperature, and with sodium alkoxides at -78 C. This last method provides the highest yields, up to 95% in most of the cases tested, but the sonochemical method proceeds under less basic conditions. Both methods preserve the integrity of the asymmetric center. 

The arylation of sodium cyanide can be achieved in moderate yields with electron-withdrawing iodonium salts [87]. The synthesis of esters was achieved by palladium-catalyzed carbonylative reaction of alcohols with diaiyliodonium salts under a CO atmosphere [262]. More recently, a base-mediated arylation of qui-nones with electron-donating iodonium salts in refluxing DCE was reported in moderate to good yields [263]. Quinoline anilides could be arylated at the P-carbon by a Pd- or Ni-catalyzed reaction proceeding via activation of sp C-H bonds (Scheme 22a) [264, 265]. Vinyl isocyanides were arylated at room temperature in a photoredox-catalyzed system with an iridium catalyst and visible light, followed by cyclizatimi to give isoquinoline derivatives [266]. 

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. 

Reactions of the Side Chain. Benzyl chloride is hydrolyzed slowly by boiling water and more rapidly at elevated temperature and pressure in the presence of alkaHes (11). Reaction with aqueous sodium cyanide, preferably in the presence of a quaternary ammonium chloride, produces phenylacetonitrile [140-29-4] in high yield (12). The presence of a lower molecular-weight alcohol gives faster rates and higher yields. In the presence of suitable catalysts benzyl chloride reacts with carbon monoxide to produce phenylacetic acid [103-82-2] (13—15). With different catalyst systems in the presence of calcium hydroxide, double carbonylation to phenylpymvic acid [156-06-9] occurs (16). Benzyl esters are formed by heating benzyl chloride with the sodium salts of acids benzyl ethers by reaction with sodium alkoxides. The ease of ether formation is improved by the use of phase-transfer catalysts (17) (see Catalysis, phase-thansfer). 

Palladium complexes also catalyze the carbonylation of halides. Aryl (see 13-13), vinylic, benzylic, and allylic halides (especially iodides) can be converted to carboxylic esters with CO, an alcohol or alkoxide, and a palladium complex. Similar reactivity was reported with vinyl triflates. Use of an amine instead of the alcohol or alkoxide leads to an amide. Reaction with an amine, AJBN, CO, and a tetraalkyltin catalyst also leads to an amide. Similar reaction with an alcohol, under Xe irradiation, leads to the ester. Benzylic and allylic halides were converted to carboxylic acids electrocatalytically, with CO and a cobalt imine complex. Vinylic halides were similarly converted with CO and nickel cyanide, under phase-transfer conditions. ... 

Addition of alcohols to lactones results in the formation of orthoacid or orthoester derivatives. Thus, reaction of lactone 95a with potassium cyanide in ethanol led to displacement of the tosyl group by cyanide and addition of ethanol to the lactone carbonyl group, to give the orthoacid derivative 95b, which was isolated as its acetate 95c. Mild deacylation of 95c led back to 95b, but under more vigorous reaction conditions the open-chain methyl aldon-ate was obtained (90). 

The first product of the oxidation of alcohol is acetaldehyde and an important end-product is fulminic add, which latter can, however, only be isolated if silver or mercury ions are present. With these ions it forms salts—fulminates—which are stable towards nitric add in them, it must be presumed, the linkage with the metal is homopolar and non-ionogenic, as in mercuric cyanide. The formation of fulminic acid takes place because the carbonyl group of the aldehyde confers reactivity on the adjacent methyl group which then forms a point of attack for the nitrous acid. The various stages in the process are indicated by the following formulae ... 

Related to the epoxy ether preparations is another reaction, involving the same precursors and an essentially identical mechanism. When certain a-haloketones are treated -with potassium cyanide in aqueous alcoholic media, there are obtained, among other products, glycidonitriles. In this instance the carbonyl function suffers attack by a CN ion, rather than a methoxide, and the intermediate an kin collapses quickly to a glytddonitrile by ejecting a halide ion as shown in Eq. (228). 

---