Cannizzaro reaction for

Phytochemical reduction must be regarded as a special case of oxidation-reduction. Since it is enzymatically conducted it should be distinguished from the analogously formulated Cannizzaro reaction. For this reason Neuberg, Hirsch and Reinfurth suggested the name dismutation for the physiological process, and in the last 25 years... 

Exercise 17-43 Write a mechanism analogous to that for the Cannizzaro reaction for the benzilic acid transformation. What product would you expect to be formed from diphenylethanedione with potassium terf-butoxide in ferf-butyl alcohol Would you expect a benzilic acid-type rearrangement to occur with 2,3-butanedione Give your reasoning. 

Hydrohydrastinine does not arise by ring olosure of the corresponding alcohol during the reaction, since the alcohol is stable to alkali under the conditions of the reaction. Further examples of the Cannizzaro reaction for polysubstituted benzaldehydes are given in Table V. 

Various methods, many with an eye towards industrial application, have been examined to accelerate Cannizzaro reactions. For example copper-silica catalysts,Na2S, Na2S203 or NaaSOs supported on AI2O3, and ultrasound all have been reported to accelerate certain Cannizzaro processes. An extremely promising development is the use of transition metal catalysts, which may be employed under neutral conditions in the absence of strong base. This permits the use of enolizable aldehydes like (28), which under basic conditions would immediately be consumed via aldol reactions. For example, in the presence... 

J. Rebek et al. synthesized novel dibenzoheptalene bislactones via a double intramolecular Cannizzaro reaction for condensation polymerization and remote catalysis studies. These bislactones are chiral, atropisomeric molecules. 

The analogy has been drawn between the chemistry catalyzed by dehydrogenases and the base-catalyzed hydride transfer chemistry of Meerwein-Ponndon-Verley (MPV) reductions or the Cannizzaro reaction (for recent reviews of the chemistry of pyridine nucleotides see Refs. 1,3, and 5). In MPV reductions [reaction (2)] aluminum or lithium salts of the alkoxide activate the C-H bond for transfer of hydrogen to suitable acceptors. Both direct hydride transfer (52) and radical intermediates (55) have been suggested for this reac-... 

The analogous dismutation of furfural is described in Section V,8. For crossed Cannizzaro reaction , see discussion following Section IV,199. 

Sodium hydroxide solution cannot be used at this stage since it may produce benzoic acid by the Cannizzaro reaction (Section IV,123) from any unchanged benzaldehyde. If, however, the reaction mixture is diluted with 3-4 volumes of water, steam distilled to remove the unreacted benzaldehyde, the residue may then be rendered alkaline with sodium hydroxide solution. A few grams of decolourising carbon are added, the mixture boiled for several minutes, and filtered through a fluted filter paper. Upon acidifying carefully with concentrated hydrochloric acid, cinnamic acid is precipitated. This is collected, washed and purified as above. 

Aromatic aldehydes react with the dimedone reagent (Section 111,70,2). All aromatic aldehydes (i) reduce ammoniacal silver nitrate solution and (ii) restore the colour of SchifiF s reagent many react with sodium bisulphite solution. They do not, in general, reduce Fehling s solution or Benedict s solution. Unlike aliphatic aldehydes, they usually undergo the Cannizzaro reaction (see Section IV,123) under the influence of sodium hydroxide solution. For full experimental details of the above tests, see under Ali-phalic Aldehydes, Section 111,70. They are easily oxidised by dilute alkaline permanganate solution at the ordinary temperature after removal of the manganese dioxide by sulphur dioxide or by sodium bisulphite, the acid can be obtained by acidification of the solution. 

By the Cannizzaro reaction. This consists in the action of a concentrated aqueous solution of sodium or potassium hydroxide upon an aldehyde (see detailed discussion before Section IV, 123), for example ... 

Aromatic aldehydes, and also aliphatic aldehydes containing no a-hydrogen atom, undergo the Cannizzaro reaction (see Section IV,123) when treated with aqueous alkali, for example ... 

The adduct can be prepared and decomposed as described for aldehydes. Alternatively, because no Cannizzaro reaction is possible, it can also be decomposed with 0.5N NaOH. 

The applicability of the Cannizzaro reaction may be limited, if the substrate aldehyde can undergo other reactions in the strongly basic medium. For instance an a ,a ,a -trihalo acetaldehyde reacts according to the haloform reaction. 

The Cannizzaro reaction takes place by nucleophilic addition of OH- to an aldehyde to give a tetrahedral intermediate, which expels hydride ion as a leaving group and is thereby oxidized. A second aldehyde molecule accepts the hydride ion in another nucleophilic addition step and is thereby reduced. Benzaldehyde, for instance, yields benzyl alcohol plus benzoic acid when heated with aqueous NaOH. 

Historical. PE was first isolated by Tollens who was examining the effect of heat and reagents on formaldehyde. Apparently the crude formaldehyde he was working with contained a small % of acetaldehyde, which accounts for the PE formed. Although Tollens isolated it in 1882, it was not identified as PE until 1888 (Ref 2). Further details of the prepn and props of PE appeared in 1891 (Ref 3). The prepn is essentially a condensation betw 3 moles of formaldehyde and 1 of acetaldehyde to give an intermediate tris(hydroxymethyl)-acetaldehyde which is not isolated. An Intermolecular oxidn/redn then takes place betw this intermediate, and a 4th mole of formaldehyde, giving PE and formic ac (Ref 13, p 2). This type reaction is discussed under Cannizzaro Reaction in the Encycl (Vol 2, C25)... 

For a microwave assisted crossed Cannizzaro reaction, see Varma, R.S. Naicker, K.P. Liesen, P.J. Tetrahedron Lett 1998, 39, 8437. 

The synthesis is very easy condensation of i-PrCHO with CH2O in base gives a 96% yield of (20), not (21). The reason for this is that f -HgO and base is a reducing system by a Cannizzaro reaction (22). 

The solvent-free Cannizzaro reaction has some advantages. In addition to simplicity and cleanness of the procedure, the solvent-free reaction proceeds much faster than a solution reaction. For example, reaction of 51 in 60% aqueous NaOH takes 24 h to complete [10], although the solvent-free reaction is completed within 5 min [9]. 

The slow, rate-limiting step is almost certainly the migration of phenyl that occurs in the initial eOH adduct (135). This is essentially the analogue for 1,2-diketones of the intramolecular Cannizzaro reaction on the 1,2-dialdehyde glyoxal, OHCCHO (p. 217). In the latter... 

Several cases of spontaneous ignition after exposure to air of fine coke particles removed from filter strainers on a petroleum refinery furfural extraction unit have been noted. This has been associated with the use of sodium hydrogen carbonate (bicarbonate) injected into the plant for pH control, which produced a pH of 10.5 locally. This would tend to resinify the aldehyde, but there is also the possibility of a Cannizzaro reaction causing conversion of the aldehyde to furfuryl alcohol and furoic acid. The latter, together with other acidic products of autoxidation of the aldehyde, would tend to resinily the furfuryl alcohol. Pyrolysis GLC showed the presence of a significant proportion of furfuryl alcohol-derived resins in the coke. The latter is now discarded into drums of water, immediately after discharge from the strainers, to prevent further incidents. 

An interesting decrease in rate was observed for the Cannizzaro reaction upon addition of 18-crown-6 [3] (Gokel et al., 1976). With solid KOH and... 

A different behavior is exhibited by naphthalene-1,8-dicarbocal-dehyde (73). No m-naphthane derivatives are obtained on reaction with nitromethane, nitroethane or other methylene components. The basic medium, required for aldol type additions, causes the dialdehyde to undergo Cannizzaro reaction to the naphthopyranon (74) via an intramolecular 1,5-hydride shift, which is sterically favoured by the peri-position of the two aldehyde functions 28). 

A crossed Cannizzaro reaction is similar to a normal Cannizzaro reaction however, two different aldehydes are reacting. Normally one of the aldehydes is formaldehyde because there are fewer chances for side reactions. (It also has the advantage of being cheap.) The reactions in Figures 11-34 and 11-35 are crossed Cannizzaro reactions using an excess of formaldehyde. The excess of formaldehyde increases the probability of the initial attack by the hydroxide being on the formaldehyde instead of the other aldehyde. Figure 11-35 shows the synthesis of pentaerythritol. 

Polyacetal resins have a repeating unit of -O-CH2-. They are strong, stiff polymers for valves, hoses, and tube connectors. Pentaerythritol finds end-uses in alkyd resins and explosives (pentaerythritol tetranitrate). To appreciate this synthesis, the student should review two condensation reactions, the crossed aldol and the crossed Cannizzaro. Acetaldehyde reacts with 3 mol of formaldehyde in three successive aldol condensations. This product then undergoes a Cannizzaro reaction with formaldehyde. 

Unlike the starting material, the product of this reduction contains an asymmetric carbon atom and it was found to be optically active. Since in the case of ketones a Cannizzaro reaction cannot take place, this mechanism for alcohol formation is out of the question. Consideration of the reduction of ketones thus clearly shows that an actual biohydrogenation is involved. 

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