Fatty aldehyde

Aldehydes fiad the most widespread use as chemical iatermediates. The production of acetaldehyde, propionaldehyde, and butyraldehyde as precursors of the corresponding alcohols and acids are examples. The aldehydes of low molecular weight are also condensed in an aldol reaction to form derivatives which are important intermediates for the plasticizer industry (see Plasticizers). As mentioned earlier, 2-ethylhexanol, produced from butyraldehyde, is used in the manufacture of di(2-ethylhexyl) phthalate [117-87-7]. Aldehydes are also used as intermediates for the manufacture of solvents (alcohols and ethers), resins, and dyes. Isobutyraldehyde is used as an intermediate for production of primary solvents and mbber antioxidants (see Antioxidaisits). Fatty aldehydes Cg—used in nearly all perfume types and aromas (see Perfumes). Polymers and copolymers of aldehydes exist and are of commercial significance. 

Malachite green (0.0...2.0) uracil derivatives, triazine herbicides [163] polar lipids [246, 247] phospholipids [248, 249] fatty acids, fatty aldehydes, phospholipids and glycolipids [250] microbiocidal isothiazolones [251]... 

J iivj.lrric. -lid/i/ii/de.—Traces ol Ibis fatty aldehyde fhH CHO have been isolated, and recognised bv its thiosomiearbazQne. melllQ at 49° to oJ -. 

The following are the general methods by which the higher fatty aldehydes may be produced. 

Schimmel Co. have prepared a number of fatty aldehydes bj a modification of this reaction. They distilled mixtures of barium formate with the barium salt of the corresponding acid, in a vacuum, as it was well known that this increases the yield when working with the higher aldehydes, which volatilise with difficulty. 

Table 2.2 Amounts of Saturated Fatty Aldehyde Extracted from 40 g of Luminous Bacteria (Shimomura et al., 1974a)...

Fig. 2.1 Mechanism of the bacterial bioluminescence reaction. The molecule of FMNH2 is deprotonated at N1 when bound to a luciferase molecule, which is then readily peroxidized at C4a to form Intermediate A. Intermediate A reacts with a fatty aldehyde (such as dodecanal and tetradecanal) to form Intermediate B. Intermediate B decomposes and yields the excited state of 4a-hydroxyflavin (Intermediate C) and a fatty acid. Light (Amax 490 nm) is emitted when the excited state of C falls to the ground state. The ground state C decomposes into FMN plus H2O. All the intermediates (A, B, and C) are luciferase-bound forms. The FMN formed can be reduced to FMNH2 in the presence of FMN reductase and NADH.

In the presence of a long-chain fatty aldehyde, intermediate A (Fig. 2.1) is converted into intermediate B that contains a perox-yhemiacetal of flavin (Macheroux et al., 1993). The apparent Km value of the intermediate B produced with an aldehyde of 10-13 carbon atoms is approximately 200 pM when P. phosphoreum luciferase is used (Watanabe and Nakamura, 1972), and 1-10 pM when P. fischeri luciferase is used (Spudich and Hastings, 1963 Hastings and Nealson, 1977). The decomposition of intermediate B,... 

Strehler, B. L., and Cormier, M. J. (1954). Isolation, identification, and function of long chain fatty aldehydes affecting the bacterial luciferin-luciferase reaction. J. Biol. Chem. 211 213-225. 

The chapters in this book are arranged roughly in the chronological order of bioluminescence systems discovered, based on the date of the major breakthrough made in each bioluminescence system, such as the discovery of ATP in the firefly system (McElroy, 1947) and the identification of fatty aldehyde as the luciferin in luminous bacteria (Cormier and Strehler, 1953). This differs from Harvey s 1952 book, which is arranged in the order of taxonomic classification. 

Precursor and derived lipids These include fatty acids, glycerol, steroids, other alcohols, fatty aldehydes, and ketone bodies (Chapter 22), hydrocarbons, hpid-soluble vitamins, and hormones. 

The use of the fire fly light-emitting system. Light generation depends on the oxidation of a substance known as luciferin. This is a fatty aldehyde such as dodecanal. An enzyme called luciferase, extracted from fire flies, catalyses the oxidation. The reaction also requires ATP. Thus, light emission measures ATP. 

Aliphatic aldehydes are among the most important components used in perfumery. Although the lower fatty aldehydes C2-C7 occur widely in nature, they are - with the exception of hexanal - seldom used in fragrance compositions. The lower... 

Fatty aldehydes are generally produced by dehydrogenation of alcohols in the presence of suitable catalysts. The alcohols are often cheap and available in good purity. Aldehyde synthesis via the oxo process is less suitable since the resultant products are often not pure enough for flavor and perfume purposes. Specific syntheses for the branched-chain and unsaturated aldehydes that are important in perfumery and flavoring techniques are described under the individual compounds. 

In comparison with other fatty aldehydes, 2-methylundecanal is used in perfumery in rather large amounts to impart conifer notes, particularly fir impressions, but frequently also in phantasy compositions. 

The main component of coriander oil is (+)-linalool (60-80%) [452-460c]. Mono- and polyunsaturated fatty aldehydes, although minor components, contribute to the characteristic aroma of the oil because of their powerful odor. In contrast to the seed oil, coriander leaf oil contains these aldehydes as main constituents, e.g. 2-decenal and 2-dodecenal. 

Fatty aldehyde dehydrogenase (FALDH) and Fatty alcohohNAD oxidoreductase (FAO) Sjogren Larsson syndrome... 

FALDH Fatty aldehyde dehydrogenase and fatty alcohol NAD-oxidoreducease phosphate oxidoreductase... 

Triacylglycerols and the ether lipids described in the previous section are classified as neutral lipids. Other neutral lipids are alcohols, waxes, aldehydes, and hydrocarbons derived from fatty acids. These sometimes have specific biological functions. For example, fatty aldehydes are important in the bioluminescence of bacteria (Eq. 23-47). 

In plants a-dioxygenases (Chapter 18) convert free fatty acids into 2(R)-hydroperoxy derivatives (Eq. 7-3, step d).32a These may be decarboxylated to fatty aldehydes (step e, see also Eq. 15-36) but may also give rise to a variety of other products. Compounds arising from linoleic and linolenic acids are numerous and include epoxides, epoxy alcohols, dihydroxy acids, short-chain aldehydes, divinyl ethers, and jasmonic acid (Eq. 21-18).32a... 

The simplest class of lipids are FAs. This group includes various types of fatty acids, eicosanoids, fatty alcohols, fatty aldehydes, fatty esters, fatty amides, fatty nitriles, fatty ethers, and hydrocarbons. Many FAs, especially the eicosanoids derived from n-6 and n-3 polyunsaturated fatty acids, have... 

Fatty acyls FA Fatty acids and conjugates Octadecanoids Eicosanoids Docosanoids Fatty alcohols Fatty aldehydes Fatty esters 0 Fatty acid palmitic acid... 

Cheesbrough T. M. and Kolattukudy P. E. (1988) Microsomal preparations from animal tissue catalyzes release of carbon monoxide from a fatty aldehyde to generate an alkane. J. Biol. Chem. 263, 2738-2743. 

Dennis M. W. and Kolattukudy P. E. (1992) A cobalt-porphyrin enzyme converts a fatty aldehyde to a hydrocarbon and CO. Proc. Natl. Acad. Sci. USA 89, 5306-5310. 

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