Vanillylamide

Peusch et al. (330) developed a method for the determination of C, DHC, and NC by RP-HPLC and fluorimetric detection at 320 nm (Aex = 280 nm), using as external standard C or nonanoic acid vanillylamide. The method was applied to low-pungency paprika and oleoresins. 

Other capsaicinoids are available. Pelargonic acid vanillylamide (PAVA or nonivamide), shown in Figure 12.10, is a synthetic form of capsaicin. Nonivamide was first synthesized by Nelson (1919). Nonivamide was originally found to be a minor component in Capsicum annum peppers (Constant and Cordell, 1996) however, the majority of PAVA is derived from synthesis rather than extraction from natural plant sources. As a result, the composition and concentration of PAVA can remain consistent (Haber et al, 2007). 

Capsaicin and capsaicinoids undergo Phase I metabolic bioconversion to catechol metabolites via hydroxylation of the vanillyl ring moiety (Lee and Kumar, 1980 Miller et al, 1983). Metabohsm involves oxidative, in addition to non-oxidative, mechanisms. An example of oxidative conversion involves the liver mixed-function oxidase system to convert capsaicin to an electrophilic epoxide, a reactive metabolite (Olajos, 2004). Surh and Lee (1995) have also demonstrated the formation of a phenoxy radical and quinine product the quinine pathway leads to formation of a highly reactive methyl radical (Reilly et al, 2003). The alkyl side chain of capsaicin also undergoes rapid oxidative deamination (Wehmeyer et al, 1990) or hydroxylation (Surh et al, 1995 Reilly et al, 2003) to hydroxycapsaicin as a detoxification pathway. An example of nonoxidative metabolism of capsaicin is hydrolysis of the acid-amide bond to yield vanillylamide and fatty acyl groups (Kawada et al, 1984 Oi et al, 1992). 

Haber, L., Nance, P., Maier, A., Price, P., Olajos, E., Bickford, L., McConnell, M., Klauenberg, B.J. (2007). Human effectiveness and risk characterization of oleoresin capsicum (OC) and pelargonic acid vanillylamide (PAVA or nonivamide) handheld devices. Air Force Research Laboratory, DTIC Technical Report No. ADA476262, May 1. 

Constituent of wormwood absinthe, a popular emerald liquor, 4-methyl-l-(l methylethyl) bicycle [3.1.0] hexan-3-one Riot control agent (pelargonic acid vanillylamide)... 

An exception to this is capsaicin (III), which is oxidized with a kinetic constant similar to phenolics (Table 1), but this compound, which is considered as the main alkaloid present in Capsicum fioiits, is oxidized at the level of the / hydroxy substituent of the vanillylamide moiety [51] (Scheme II). 

OC is a reddish-brown oily liquid obtained by extracting dried, ripe fruit of chili peppers, usually Capsicum annuum or Capsicum fruitescenes. The oleoresin is a mixture of many compounds. Its composition is variable and depends on factors such as maturity of the fruit and the environment in which the plants are grown, as well as the conditions of the extraction. More than 100 compounds have been identified in oleoresin capsicum. Among the branched-and straight-chain alkyl vanillylamides isolated from oleoresin capsicum, capsaicin is the major pungent component in many peppers, and it is particularly noted for its irritant properties. Depending on the variety of chili pepper, the oleoresin contains from 0.01% to 1.0% capsaicinoids on a dry mass basis. Other components of the oleoresin such as phenolic compounds, acids, and esters may also possess irritant properties. 

Hydroxy-4-methoxybenzophenone-5-sodium sulfonate. See Benzophenone-5 2-Hydroxy-4-methoxybenzophenone-5-sulfonic acid. See Benzophenone-4 N-(4-Hydroxy-3-methoxybenzyl) nonanamide. See Pelargonyl vanillylamide Nonanoyl 4-hydroxy-3-methoxybenzylamide 4-Hydroxy-3-methoxycinnamic acid. See Ferulic acid... 

Nonanoic acid, 1-methyl-1,2-ethanediyl ester. See Propylene glycol dipelargonate Nonanoic acid vanillylamide. See Nonanoyl 4-hydroxy-3-methoxybenzylamide Nonanoic aldehyde. See Nonanal Nonanol. See 3,5,5-Trimethylhexan-1-ol Nonan-1-ol 1-Nonanol. See Nonyl alcohol 2-Nonanol CAS 628-99-9 FEMA 3315... 

Synonyms Capsaicin synthetic analog N-(4-Hydroxy-3-methoxybenzyl) nonanamide Nonanoic acid vanillylamide Nonivamide Nonylvanylamide Pelargonic acid vanillylamide ... 

See Pelarqonyl vanillylamide Nonanoyl peroxide. See Pelargonyl peroxide N-Nonanoyl vanillylamide. See Pelargonyl vanillylamide... 

Octyl octanoate Octyl phenylacetate Octyl propionate Palmitic acid Paraldehyde PEG-10 sorbitan laurate PEG-3 sorbitan oleate PEG-3 sorbitan stearate Pelargonyl vanillylamide Pentadecalactone Pentane-2,3-dione 4-Pentenoic acid 1-Penten-3-ol Pentyl 2-furyl ketone Perillaldehyde Perillyl acetate Perillyl alcohol a-Phellandrene Phenethyl alcohol Phenethyl anthranilate... 

Nonyl alcohol Nonyl isovalerate Nonyl octanoate y-Octalactone n-Octanal Octanal dimethyl acetal 2-Octanol 3-Octanol 3-Octanone 3-Octanon-1-ol 1-Octen-3-ol cis-3-Octen-1-ol 1-Octen-3-yl acetate 1-Octen-3-yl butyrate Octyl acetate 3-Octyl acetate Octyl butyrate Octyl formate Octyl isobutyrate Octyl isovalerate Octyl octanoate Octyl phenylacetate Octyl propionate Pelarqonyl vanillylamide Pentadecalactone... 

N-Butyl-N-acetolyl-benzamid 9, 211. PelaTgonsftiiie>[44)xy.3.methoxy.beiizyl amid], Felargonstare-vanillylamid lSI322,n l. 

Related amides are vanillylamides, such as capsaicin and dihydrocapsaicin, which are derived from vanillylamine and fatty acids. Vanillylamides are the main hot substances of peppers. A similar compound in peppers is capsaicinol, which does not create a burning sensation, but is effective as an antioxidant (see Section 10.3.2.1.7). 

Capsaicinoids (vanillylamides) Leu, Phe, Val, malonyl-CoA Chili pepper Capsaicine, nordihydrocapsaicine, homodihydrocapsalcine... 

Capsaicinoids (10-29) are vanillylamides (AT-vaniUylacylamides) derived from Cg to Cj j branched and straight chain traws-monoenic and saturated fatty acids. The main components causing a burning sensation when in contact with mucous membranes are capsaicin (E)-8-methyl-N-vanillylnon-6-enamide and dihydrocapsaicin (8-methyl-N-vanillylnonanamide), which constitute about 90% of total capsaicinoids. These capsaicinoids are accompanied by... 

Capsaicin is the vanillylamide of / o-decenoic acid (8-methyl-iV-vanil-lylnon-6-enamide) synthetic compounds that have a close chemical similarity to capsaicin also have pungent properties and are used in place of, or in addition to, naturally occurring material. The method given above will not differentiate between capsaicin and a synthetic compound such as iV-vanillylnonanamide. A method has been suggested by Datta and Susi for the quantitative differentiation between natural capsaicin and the synthetic material, based on infra-red measurements at 970 cm the peak at this wavelength is due to a trans double bond present in the fatty acid moiety of the natural compound, and appears to be unique for capsaicin. Datta and Susi only applied their method to mixtures of pure materials but it is possible that a quantitative determination of capsaicin in capsicum could be worked out which would detect adulteration with synthetic capsaicin-like material. 

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