Chain branching aldehydes

Phospholipids contribute specific aroma to heated milk, meat and other cooked foods through lipid oxidation derived volatile compounds and interaction with Maillard reaction products. Most of the aroma significant volatiles from soybean lecithin are derived from lipid decomposition and Maillard reaction products including short-chain fatty acids, 2-heptanone, hexanal, and short-chain branched aldehydes formed by Strecker degradation (reactions of a-dicarbonyl compounds with amino acids). The most odor-active volatiles identified from aqueous dispersions of phosphatidylcholine and phos-phatidylethanolamine include fra 5 -4,5-epoxy-c/5-2-decenal, fran5,fran5-2,4-decadienal, hexanal, fra 5, d5, d5 -2,4,7-tridecatrienal (Table 11.9). Upon heating, these phospholipids produced cis- and franj-2-decenal and fra 5-2-undecenal. Besides fatty acid composition, other unknown factors apparently affect the formation of carbonyl compounds from heated phospholipids. 

Branched-Chain Carboxylic Acids. Branched-chain acids such as 2-methylbutyric, 3-methylbutyric, isooctanoic, and isononanoic acids are produced by the oxo reaction, giving first the corresponding aldehyde, which is then oxidized to the acid. 2-EthyIhexanoic acid is produced by the aldol route from butyaldehyde in three steps aldol condensation hydrogenation of the carbon—carbon double bond and oxidation of the branched-chain saturated aldehyde to 2-ethyIhexanoic acid (see Carboxylic Acids, branched-chain acids). 

Cyanohydrin Synthesis. Another synthetically useful enzyme that catalyzes carbon—carbon bond formation is oxynitnlase (EC 4.1.2.10). This enzyme catalyzes the addition of cyanides to various aldehydes that may come either in the form of hydrogen cyanide or acetone cyanohydrin (152—158) (Fig. 7). The reaction constitutes a convenient route for the preparation of a-hydroxy acids and P-amino alcohols. Acetone cyanohydrin [75-86-5] can also be used as the cyanide carrier, and is considered to be superior since it does not involve hazardous gaseous HCN and also virtually eliminates the spontaneous nonenzymatic reaction. (R)-oxynitrilase accepts aromatic (97a,b), straight- (97c,e), and branched-chain aUphatic aldehydes, converting them to (R)-cyanohydrins in very good yields and high enantiomeric purity (Table 10). 

Eleven aromatic and aliphatic aldehydes have been alkylated with Et2Zn in the presence of homoannularyl bridged hydroxyamino ferrocene (—>123. The resulting carbinols have ee values varying from 66% to 97%. This new ferro-cenyl catalyst has been used successfully to alkylate aromatic and linear or branched chain aliphatic aldehydes to secondary alcohols with up to 97% ee. This ligand is effective even for -branched aliphatic substrate. 

A typical feature of hydroformylation is the fact that both sides of the double bond are in principle reactive, so only ethene yields propanal as a single product. From propene, two isomers are formed linear or normal butanal and 2-methylpropanal (branched or iso product). With longer chain 1-alkenes, the isomerization of the double bond to the thermodynamically more favored internal positions is possible, yielding the respective branched aldehydes (Fig. 1). Frequently, terminal hydroformylation is targeted because of the better biodegradability of the products. Thus, not only stability, activity, and chemoselectivity of the catalysts are important. A key parameter is also the regioselectivity, expressed by the n/i ratio or the linearity n/(n+i). 

At first, the question of the relative importance of ROOH versus aldehydes as intermediates was much debated however, recent work indicates that the hydroperoxide step dominates. Aldehydes are quite important as fuels in the cool-flame region, but they do not lead to the important degenerate chain branching step as readily. The RO compounds form ROH species, which play no role with respect to the branching of concern. 

Dondoni pioneered the use of 2-(trimethylsilyl)thiazole (71) as a formyl anion equivalent for the homologation of aldehydes. Extension of this reaction to ketones would be very useful, but has thus far been restricted to tritluoromethyl cases. However, it has now been widened to include several a, a -alkoxy ketones, as demonstrated in a new route to branched-chain monosaccharides. Aldehydes catalyse the reaction, although the scope is still limited electrophilic aldehydes, such as 2-fluorobenzaldehyde, promote the addition of (71) to electrophilic ketones. 

Our investigation (27, 28) of the decomposition of peracrylic acid by various homogeneous metal catalysts helped to verify the above steps as the initiation reaction. But Step 1" plays no fundamental role since it occurs very slowly. The metal catalysts also accelerate the decomposition of the peracid-aldehyde complex which forms the radicals of chain branching. Step 1, and the steps just mentioned, become comprehensible in view of the initiation of the catalyzed oxidation as described above. 

In addition to the straight-chain saturated aldehydes, a number of branched-chain and unsaturated aliphatic aldehydes are important as fragrance and flavoring materials. The double unsaturated 2-trviolet leaf aldehyde (the dominant component of cucumber aroma), is one of the most potent fragrance and flavoring substances it is, therefore, only used in very small amounts. 2-frfatty odor character is indispensible in chicken meat flavor compositions. 

Simple straight-chain aliphatic aldehydes (C2 to Cj2 tested) and mono a-branched aldehydes. ... 

The effect of aldehyde chain branching was examined using cyclohex-anecarboxaldehyde 244 (Scheme 75). The results are shown in Table 15. 

Once the aldehyde concentration builds up to a critical level (and even in the oxidation of secondary alcohols, small quantities of aldehydes are produced by side-reactions), then autocatalysis is observed. It is suggested that the aldehydes bring about chain-branching by reacting directly with oxygen... 

The results can again be explained [26] by the propagation of a linear chain by HOj radicals which produce hydrogen peroxide and iso-butyraldehyde when sufficient aldehyde has accumulated chain-branching can begin and the reaction accelerates. 

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