Aldehydes, aromatic decarbonylation

Aldehydes, both aliphatic and aromatic, can be decarbonylated by heating with chlorotris(triphenylphosphine)rhodium or other catalysts such as palladium. The compound RhCl(Ph3P)3 is often called Wilkinson s catalyst.In an older reaction, aliphatic (but not aromatic) aldehydes are decarbonylated by heating with di-tert-peroxide or other peroxides, usually in a solution containing a hydrogen donor, such as a thiol. The reaction has also been initiated with light, and thermally (without an initiator) by heating at 500°C. 

In addition, concentrated sulfuric acid catalyzes the decarbonylation of aldehydes, aromatic acids, and aliphatic carboxylic acids, such as formic acid ... 

Decarbonylation of aldehydes. Some aromatic aldehydes are decarbonylated when heated with 5% palladium on charcoal, for example "... 

Decarbonytation. Aromatic aldehydes undergo decarbonylation on refluxing with Sc(OTf)j in methanol (forming HCOOMe as a by-product). The presence of electron-releasing substituents facilitates the reaction. 

A number of derivatives of compound A were prepared that included acetates, ethers, olefin reduction products, aldehyde and ketone reduction products, aromatic decarbonylated derivatives, and derivatives where the aldehyde was converted to a methyl ester [122]. 

Because of the correlation of the rate of aromatic decarbonylations vdth the acidity function H , Hammett (1940) suggested that the mechanism involved an unimolecular decomposition of a conjugate acid of the aldehyde (17). 

Aldehydes are decarbonylated catalytically using solutions of bis(triphenylphosphine)(tetraphenylphorphyrinato)ruthenium(ii) at, or slightly above, room temperature. Decarbonylation of aromatic aldehydes takes place... 

Decarbonylation of aromatic aldehydes proceeds smoothly[71], Terephthalic acid (86), commercially produced by the oxidation of p-.xylene (85), contains p-formylbenzoic acid (87) as an impurity, which is removed as benzoic acid (88) by Pd-catalyzed decarbonylation at a high temperature. The benzoic acid produced by the decarbonylation can be separated from terephthalic acid (86) based on the solubility difference in water[72]. 

At elevated temperatures, methylene carbons cleave from aromatic rings to form radicals (Fig. 7.44). Further fragmentation decomposes xylenol to cresols and methane (Fig. 7.44a). Alternatively, auto-oxidation occurs (Fig. 1.44b ). Aldehydes and ketones are intermediates before decarboxylation or decarbonylation takes place to generate cresols and carbon dioxide. These oxidative reactions are possible even in inert atmospheres due to the presence of hydroxyl radicals and water.5... 

The decarbonylation of aromatic aldehydes with sulfuric acid" is the reverse of the Gatterman-Koch reaction (11-16). It has been carried out with trialkyl- and trialkoxybenzaldehydes. The reaction takes place by the ordinary arenium ion mechanism the attacking species is H and the leaving group is HCO, which can lose a proton to give CO or combine with OH from the water solvent to give formic acid." Aromatic aldehydes have also been decarbonylated with basic catalysts." When basic catalysts are used, the mechanism is probably similar to the SeI process of 11-38. See also 14-39. 

The decarboxylation of carboxylic acid in the presence of a nucleophile is a classical reaction known as the Hunsdiecker reaction. Such reactions can be carried out sometimes in aqueous conditions. Man-ganese(II) acetate catalyzed the reaction of a, 3-unsaturated aromatic carboxylic acids with NBS (1 and 2 equiv) in MeCN/water to afford haloalkenes and a-(dibromomethyl)benzenemethanols, respectively (Eq. 9.15).32 Decarboxylation of free carboxylic acids catalyzed by Pd/C under hydrothermal water (250° C/4 MPa) gave the corresponding hydrocarbons (Eq. 9.16).33 Under the hydrothermal conditions of deuterium oxide, decarbonylative deuteration was observed to give fully deuterated hydrocarbons from carboxylic acids or aldehydes. 

The decarbonylations, which do not appear to be affected by light, are reasonably selective with aromatic aldehydes, yielding the expected product however, significant amounts of other products are obtained with non-aromatic substrates (e.g. cyclohexane-aldehyde gives methylcyclopentane and small amounts of n-hexane, as well as the expected cyclohexane and cyclohexen-4-al gives both cyclohexene and cyclohexane). Indeed, the unexpected products perhaps provided a major clue to an understanding of the reaction mechanism(s) involved. 

A 5% palladium on charcoal when heated with some aromatic aldehydes brings about its decarbonylation. 

The acyl radicals obtained by hydrogen abstraction from aldehydes easily attack protonated heteroaromatic bases. With secondary and tertiary acyl radicals decarbonylation competes with the aromatic acylation [Eq. (12)]. 

Oxidations of [ F]Fluorobenzaldehydes to [ F]Fluorophenols. . 228 Decarbonylation of F-Aromatic Aldehydes and AppHcations. . 229... 

Due to its strong activating effect in nucleophilic aromatic substitutions and to the possibility of its removal by decarbonylation, the aldehyde function has been used for the preparation of [ F]fluoroarenes not bearing electron-withdrawing substituents. Decarbonylations, possible in the presence of Pd/C [ 161 ], are more efficient in terms of time (15 min vs 1 h) and yields (80%) when using Wilkin-... 

Decarbonylation of Aromatic Aldehydes Hydro-de-formylation or Deformylation... 

Decarbonylation of aromatic aldehydes or deacylation of aromatic ketones... 

Many carboxylic acids lose carbon dioxide on either direct or sensitized irradiation, and in some cases (4.10 the evidence points to the operation of an initial electron-transfer mechanism rather than primary a-deavage. Cleavage occurs readily with acyl halides, and this can [ead to overall decarbonylation (4.11). Aldehydes also cleave readily, since the (0=)C—H bond is more prone to homolysis than the (0= C-C bond. This offers a convenient method for replacing the aldehydic hydrogen by deuterium in aromatic aldehydes (4.12. and a similar initial reaction step accounts for the production of chain-Iengtheped amides when formamide is irradiated in the presence of a terminal alkene (4.13). 

Rhodium(II) acetate catalyzes C—H insertion, olefin addition, heteroatom-H insertion, and ylide formation of a-diazocarbonyls via a rhodium carbenoid species (144—147). Intramolecular cyclopentane formation via C—H insertion occurs with retention of stereochemistry (143). Chiral rhodium (TT) carboxamides catalyze enantioselective cyclopropanation and intramolecular C—N insertions of CC-diazoketones (148). Other reactions catalyzed by rhodium complexes include double-bond migration (140), hydrogenation of aromatic aldehydes and ketones to hydrocarbons (150), homologation of esters (151), carbonylation of formaldehyde (152) and amines (140), reductive carbonylation of dimethyl ether or methyl acetate to 1,1-diacetoxy ethane (153), decarbonylation of aldehydes (140), water gas shift reaction (69,154), C—C skeletal rearrangements (132,140), oxidation of olefins to ketones (155) and aldehydes (156), and oxidation of substituted anthracenes to anthraquinones (157). Rhodium-catalyzed hydrosilation of olefins, alkynes, carbonyls, alcohols, and imines is facile and may also be accomplished enantioselectively (140). Rhodium complexes are moderately active alkene and alkyne polymerization catalysts (140). In some cases polymer-supported versions of homogeneous rhodium catalysts have improved activity, compared to their homogenous counterparts. This is the case for the conversion of alkenes direcdy to alcohols under oxo conditions by rhodium—amine polymer catalysts... 

Alcohol and aldehyde decarbonylation on Rh(l 11), activation of C-H, C-C, and C-0 bonds, 345-353 Alkane dehydroeyelization with Pt-Sn-alumina catalysts aromatic formation, 120 preparation condition effect, 119... 

These compounds have been obtained130 by nucleophilic substitution (equation 60) with [18F]F" on the corresponding activated aromatic nitro aldehyde precursors, followed by decarbonylation (equation 60a) proceeding usually in 84 5% yields131-134. 

The production of hydrocarbons from aromatic alcohols is most readily explained by the hydrogenolysis of the alcohol, but an alternate possibility should be considered. The formation of an aldehyde and its subsequent decarbonylation under reaction conditions could lead to the hydrocarbon. Both toluene and 2-phenylethanol, the mixture of products secured from benzyl alcohol, may be regarded as derived from phenylacetaldehyde as an intermediate ... 

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