Natural vanillin

Recently, a two-step enzymatic conversion of ferulic acid (3) leading to natural vanillin was disclosed, with a price indication of about 700 kg-1. 

To produce natural vanillin at a lower price, various biotechnological approaches have been explored, such as plant cell cultures and bioconversion of natural compounds by means of microorganisms or isolated enzymes. 

Single natural aroma compounds like natural vanillin are obtained through physical separation techniques from edible materials or through natural fermentative processes. 

Vanillylamine [(4-hydroxy-3-methoxy-phenyl)methylamine] is the substrate of choice for the formation of vanillin with the help of amine oxidase. It can be obtained by cleavage of capsaicin (N-[(4-hydroxy-3-methoxy-phenyl)methyl]-8-methyl-6-nonenamide) isolated from pepper and capsicum [83]. As natural vanillin extracted from beans of Vanilla planifolia is rare and extremely expensive, this pathway for the production of natural vanillin is regarded to have a great potential. The vanillin obtained by the process can be labelled as natural if the cleavage of capsaicin is performed enzymatically. 

Scheme 23.6 Microbial strategies for the production of natural vanillin...

Synthetic vanillin formulations dominate global use of vanillin. As noted, approximately 50 tons of natural vanillin is used annually global use of synthetic vanillin is approximately... 

C/12C ratio in natural vanillin is smaller than that observed in synthetic vanillin. The same effect applies to glucose, whose isotopic carbon distribution varies depending on the biological cycle of the plant. 

The isotopic factor 6 of carbon, measured from the carbon dioxide resulting from the combustion of a natural vanillin, is fj = —20. A value arising from a synthetic vanillin is t> = —30. Calculate the percentage of these two species within a sample of mixed vanillin, knowing that a previously measured value S = —23.5 has been obtained. 

Although more than 12,0001 of vanillin is produced each year, less than 1% of this is natural vanillin from Vanilla-, the remainder is synthesized much more cheaply via chemical processes. 

Lopez-Malo, A., Alzamora, S.M. and Argaiz, A. (1 995) Effect of natural vanillin on germination time and radial growth of moulds in fruit-based agar systems. Food Microbiology 12, 21 3-219. 

Westcott, R.J., Cheetham, P.S.J. and Barraclough, A.J. (1 993) Use of organized viable vanilla plant aerial roots for the production of natural vanillin. Phytochemistry 35(1), 135-138. 

Enzymatic syntheses of CPS have also been reported, using various lipase-catalyzed transacylations [69]. Interestingly, a biotechnological process to obtain natural vanillin from CPS has been developed, capitalizing on the enzymatic hydrolysis of CPS and the oxidation of vanillamine with a flavoprotein vanillyl alcohol oxidase [70]. 

Comments Vanilla and natural vanillin only. About 30/lb. I was quoted. A lot lower than I thought Also sell fatty acid oils like coconut and palm for all you do-it-yourself soap makers. 

D.A. Krueger, H.W. Krueger (1983) Carbon isotopes in vanillin and the detection of falsified natural vanillin. J. Agric. Food Chem. 3J., 1265-1268... 

Asther, M., et al. (1997). Fungal biotransformation of European agricultural by-products to natural vanillin A two-step process. Food Ingredients Porte de Versailles, Paris, France, 12-14 November 1996 pp. 123-125. 

In India, there is no source of natural vanillin. It is either imported from China and Mexico or partly made from sulflte liquor wastes. The technology for synthesis from p-cresol has been developed by one or two companies, such as Zora Pharma, Ahmedabad. Indian market is estimated to the tune of 100 tpa. 

The popular misconceptions about natural and synthetic products, widely disseminated by the press, have led to a desire to be able to distinguish between the two. This has not yet had much impact on the total synthesis of monoterpenoids most analysts consider that the optical activity is sufficient measure to determine a natural. Nevertheless, a team under G.J. Martin in France has been studying the very small differences in site-specific isotope ratios of natural products, and claim to be able to distinguish not only the differences between, say, synthetic and natural vanillin, but, by using the different isotope... 

Isotope fractionation occurs during processes like evaporation or condensation and during chemical reactions. In the living world, isotopes of the same element can be differentiated by the biosynthetic pathways they follow. Furthermore, the rate at which a molecule crosses cellular membranes will depend of the molecule s isotopic distribution. For example, the isotopic ratio of natural vanillin is... 

The vanillin market is in fact shared by two products the natural vanillin contained in vanilla beans, an extremely highly priced ( 4000 /kg) and scarce product, and the synthetic (from phenols) or hemisynthetic (from lignin) vanillins which are produced in large quantities and are relatively cheap (40 /kg). 

Unfortunately, the natural product is heavier than its synthetic counterpart and it is relatively easy and not prohibitively expensive to add a small quantity of C enriched vanillin to the synthetic product. From this point of view, vanillin exlignin is preferred to vanillin ex-guaiacol since the quantity of labelled material required is lower. Applying isotopic dilution equations, it is apparent that less than one hundred milligrams of 99% 13C-labelled vanillin are required to transform 1kg vanillin ex-lignin into 1kg natural vanillin ... 

One simple test is to measure the level of radioactivity from the sample. Synthetic vanillin is not radioactive. However, natural vanilla, like all natural products, is. This is, of course, because atmospheric carbon dioxide contains some radioactive 14C formed by exposure to cosmic radiation in the upper atmosphere. Plants then incorporate this into their photosynthetic pathway and produce metabolites, which exhibit a low level of radioactivity. Synthetic vanillin is prepared from coal tar, which is not radioactive since the 14C has long since decayed. However, unscrupulous dealers know this and can synthesise radiolabelled or hot vanillin and dose it into synthetic material so that the level of radioactivity matches that of a natural sample. Another method of checking for naturalness must therefore be found. When plant enzymes synthesise molecules, they, like all catalysts, are susceptible to isotope effects. The vanilla plant is no exception and examination of the distribution of hydrogen and carbon isotopes in the vanillin molecule reveals that the heavier deuterium and 13C isotopes accumulate at certain specific sites. A suitable NMR spectrometer can determine the isotopic distribution in a sample and the cost of using 2H, 13C and 14C labelled synthetic materials to replicate the NMR spectra and radioactivity of natural vanillin in a synthetic sample would not be financially attractive. Furthermore, the 2H and 13C labelling patterns in the vanilla bean are different from those of other natural shikimate sources and so the NMR technique can also distinguish between vanillin from vanilla and vanillin produced by... 

The Remier-Tiemann reaction is also used to produce another form of vanillin called ethyl vanillin. Ethyl vanillin is the ethyl ether of 4-hydroxybenzoic acid, 4-hydroxy-3-ethoxybenzaldehyde ((CH3CH20)(0H)C6H3CH0). It is a close chemical relative of natural vanillin in which the methyl ( CH3) group of natural vanillin is replaced by an ethyl ( CH2CH3) group. Ethyl vanillin is also known as artificial vanilla or synthetic vanilla. Its flavor is about three times as strong as that of methyl vanillin and is used to fortify or replace natural vanillin and lignin vanillin. 

Natural vanilla flavor and natural vanillin are in high demand and alternative production routes such as using PTC or microbial systems are being sought [60]. De novo synthesis of vanillin and vanilla plant cells and plant callus tissue are important commercial products biosynthesized by PTC. Alternatively, hair roots of vanilla plant have been used as a biocatalyst to convert the precursor ferulic acid into vanillin [104]. 

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