Natural vanilla

Vanilla flavoring in bakery goods, confectionery, and many fro2en desserts need not be natural vanilla. The artificial and synthetic vanilla flavors that are used include vanillin [121-33-5] from lignin (wood pulp), ethyl vanillin [121 -32-4] and vanitrope [94-86-0], the latter two are synthetics. Over 90% of the U.S. market for vanilla flavor contains vanillin. These synthetics continue to dominate the market because of availabiUty, quahty, and relatively low and stable prices. 

Flavors, emulsifiers, or cocoa butter are often added during conching. The flavoring materials most commonly added in the United States are vanillin, a vanillalike artificial flavor, and natural vanilla (25) (see Flavors AND SPiCEs). Cocoa butter is added to adjust viscosity for subsequent processing. 

M. T. Belay and C. E. Poole, Determination of vanillin and related flavor compounds in natural vanilla exti acts and vanilla-flavored foods by thin layer chromatography and automated multiple development , Chromatographia 37 365-373(1993). 

Because it does not have quite the same taste as the much more complex mixture of compounds found in natural vanilla extract, it is most often used with stronger flavors and scents such as chocolate, cloves, nutmeg, or cinnamon. 

Benzoic aldehydes mainly cover syringaldehyde and vanillin. Natural vanilla is prepared from the seeds (beans) of Vanilla planifolia, which may contain about 21 mg/ 100 g FW total phenols, including the major components vanillin (19.4 mg/100 g FW), 4-hydroxybenzaldehyde (1 mg/100 g FW), and vanillic acid (0.4 mg/100 g FW) (Clifford 2000b). In mango, vanillin has been found as free as well as vanillyl glu-coside (Sakho and others 1997). It has also been found in lychees (Ong and Acree 1998) and wines (Moreno and others 2007). For analysis of both brandy and wine aged in oak barrels, the limits of detection were found to be 27.5, 14.25, 14.75, and... 

Natural vanilla beans are expensive and the vanillin content is just 1.5-2 wt.%. Harvests of the beans fluctuate, as do the prices. The world production of vanilla beans in 2005 [10] was 1275 t (of which 700 t alone was by Madagascar/ Malagasy). In 2004 the production was 1975 t. Halfway through 2004 the price... 

Whereas natural vanilla flavor from beans (recognized by the black dots ), is used in premium ice creams, soft drinks are flavored with synthetic vanillin. Natural vanilla contains other flavoring agents as well. Thus, F F is the only segment of the chemical industry where impurities add to the quality—and the price—of a product ... 

Brownell R (2005) The commercial survival of natural vanilla. In Vanilla The first international congress. Allured, Carol Stream, pp 1-3... 

Remaud GS, Martin YK, Giles G, Martin GJ (1997) Detection of natural vanilla flavors and extracts Application of the SNIF-NMR to vanillin and p-hydroxybenzaldehyde. J Agric Food Chem 45 859-866... 

Many aldehydes are particularly fragrant. A number of flowers, for example, owe their pleasant odor to the presence of simple aldehydes. The smells of lemons, cinnamon, and almonds are due to the aldehydes citral, cinnamalde-hyde, and benzaldehyde, respectively. The structures of these three aldehydes are shown in Figure 12.21. The aldehyde vanillin, introduced at the beginning of this chapter, is the key flavoring molecule derived from the vanilla orchid. You may have noticed that vanilla seed pods and vanilla extract are fairly expensive. Imitation vanilla flavoring is less expensive because it is merely a solution of the compound vanillin, which is economically synthesized from the waste chemicals of the wood pulp industry. Imitation vanilla does not taste the same as natural vanilla extract, however, because in addition to vanillin many other flavorful molecules contribute to the complex taste of natural vanilla. Many books made in the days before acid-free paper smell of vanilla because of the vanillin formed and released as the paper ages, a process that is accelerated by the acids the paper contains. 

VANILLIN. Vanillin, [CAS 121-35-5]. CgHgCL, a natural product, can be found as a glucoside (ghicovanillin) in vanilla beans, at concentrations of about 2%. It can be extracted with water, alcohol, or other organic solvents. Approximately 250 by-products have been identified m natural vanilla, out of which 26 are present at levels in excess of 1 ppm. The balance of all these products contributes to the subtle taste of vanilla beans, The vanilla bean contains about 2% vanillin, but the 10% extract prepared from beans has several times lire strength of a solution of 2% vanillin. The best known natural source of vanillin is the vanilla plant, Vanilla planifolia A., which belongs to the orchid family. It is cultivated mainly in Mexico, Madagascar, Reunion, Java, and Tahiti. 

Although natural flower absolutes are less important than in Chanel No. 5 and Arpege in establishing the essential character of the fragrance, rose, jasmin, and tuberose may be added, together with tonka, to back up the coumarin (1.5%), and a trace of natural vanilla. A trace also of ambrette seed can give a wonderful smoothness to the composition, working particularly well as part of the rose accord. 

Vanilla essence comes in two forms the actual extract of the seedpods and the far cheaper synthetic essence, basically consisting of a solution of synthetic vanillin in ethanol. Natural vanilla is an extremely complicated mixture of several hundred different compounds, versus synthetic vanillin which is derived from phenol and is of high purity. Many commercial vanilla extracts are now actually blends of natural and synthetic vanillin. The occurrence of several non-vanillin aroma and flavour components in minor or trace amounts in beans is the reason for their organoleptic superiority over synthetic vanilla and blends. Natural vanilla has a delicate, rich and mellow aroma and aftertaste, while the synthetic material is quite heavy, grassy and less pleasant. 

There are three main commercial forms of natural vanilla ... 

Boyce, M.C., Haddad, P.R. and Sostaric, T. (2003) Determination of flavour components in natural vanilla extracts and synthetic flavourings by mixed micellar electrokinetic capillary chromatography. Analytica Chimica Acta 485(2), 1 79-1 86. 

Remaud, C.S., Martin, Y.-L., Martin, C.C. and Martin, C.J. (1997) Detection of sophisticated adulterations of natural vanilla flavors and extracts application of the SNIF-NMR method to vanillin and p-hydroxyben-zaldehyde. Journal of Agricultural and Food Chemistry 45, 859-866. 

Sometimes chemists analyze a compound that is found in nature to learn how to produce it more cheaply in a laboratory. For example, consider the flavour used in vanilla ice cream, which may come from natural or artificial vanilla extract. Natural vanilla extract is made from vanilla seed pods, shown on the left. The seed pods must be harvested and processed before being sold as vanilla extract. The scent and flavour of synthetic vanilla come from a compound called vanillin, which can be produced chemically in bulk. Therefore its production is much cheaper. Similarly, many medicinal chemicals that are found in nature can be produced more cheaply and efficiently in a laboratory. 

Vanilla extract is used to flavor a wide variety of foods and 1s very expensive. Herrman and StockH (48) developed an HPLC method to determine the major components of vanilla extracts. This method can be used to help differentiate natural vanilla extracts from cheaper substitutes. Shown in Figure 2a 1s a separation of standards of the major components 1n vanilla. Shown in Figure 2b is the chromatogram from a typical vanilla extract. It should be noted in Figure 2b that natural vanilla extracts apparently lack ethyl vanillin, a commonly used flavor substitute. 

Vanillin is widely used as a flavor in pharmaceuticals, foods, beverages, and confectionery products, to which it imparts a characteristic taste and odor of natural vanilla. It is also used in perfumes, as an analytical reagent and as an intermediate in the synthesis of a number of pharmaceuticals, particularly methyl-dopa. Additionally, it has been investigated as a potential therapeutic agent in sickle cell anemia and is claimed to have some antifungal properties. 

The vanillin in the mixture is not a natural product. Natural vanilla extract is a mixture of hundreds of compounds in addition to vanillin. 

PCT WO 93/25088 Method for Obtaining a Natural Vanilla Aroma by Treatment of Vanilla Beans, and Aroma thus Obtained, v. Mane FUs S.A. 1992... 

CIC Vanillin, the main component in vanilla flavour is the basic key ingredient for the creamy, sweet character. All other volatile flavouring compounds have been identified only in small traces. Among them 2-methoxy phenol and 2-methoxy-4-vinyl phenol are responsible for the phenolic, smoky odour. 4-Methoxy benzalde-hyde, 3,4-methylene-dioxy-benzaldehyde, methyl benzoate and methyl ciimamate impart the warm, powdery, aromatic floral character. Vitispirane adds a fruity, floral topnote. Natural vanilla extract blends very well with other flavourings and it has been modified in different directions ethyl vanillin is used to increase the sweet, creamy vanillin aspect. Tonka beans and coumarin add a full, dried hay, slightly caramel-like custard aspect, supported by the butter notes of diacetyl and 4-hydroxy-decanolide. 

In the USA a standard of identity exists for ice-cream vanilla flavours. This standard of identity contains three categories. Category 1 vanilla-flavoured ice-cream can contain only all natural vanilla flavour. Category 2 can contain a blend of natural vanilla flavour plus an equal fold of artificial vanillin per gallon. A fold of vanillin is equal to 1 oz of vanillin per gallon of natural vanilla flavour. Category 3 is the general realm of artificial vanilla flavours. 

These detectors are commonly used in HPLC analysis. The absorption of the substances in the eluate by a specific wavelength normally between 190 and 700 nm is proportional to their concentration. This technique is widely used for quality control of flavourings, e.g. for the quantification of the vanillin/p-hydroxybenzaldehyde ratio for natural vanilla products, for the determination of caffeine in extracts and drinks, or for the detection and quantification of restricted ingredients such as quassine, coumarin or p-asarone in natural extracts [11-12[. 

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 synthesize radio-labelled 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 synthesize molecules, they, like all catalysts, are suscep-... 

Many aldehydes and ketones are produced industrially as food and fragrance chemicals, medicinals, and agricultural chemicals. They are particularly important to the food industry, in which they are used as artificial and/or natural additives to food. Vanillin, a principal component of natural vanilla, is shown in Figure 14.3. Artificial vanilla flavoring is a dilute solution of synthetic vanillin dissolved in ethanol. Figure 14.3 also shows other examples of important aldehydes and ketones. 

Some people prefer a vanilla product that contains no, or almost no, alcohol. If alcohol is removed, almost pure vanilla is left behind, leaving a product known as natural vanilla flavoring. 

Natural vanilla flavours have a much more aromatic and delicate character than pure vanillin because more than 250 components contribute to the flavour. However, because of high demand, vanillin is manufactured by biosynthesis, using micro-organisms to imitate the formation of vanillin during the curing process. Vanillin can also be... 

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