Coumarin vanillin

Since several related compounds give the same colour reactions as vanillin and coumarin the above methods are not specific and a method has been developed in which coumarin, vanillin and ethyl vanillin are separated from each other by partition chromatography and subsequently determined spectrophotometrically. 

In some cases, especially when the family is directed more toward Oriental fragrances, the use of vanillin can be up to 5%. These types of perfumes include Spanish fougnre, sweet or fmity chypres, woody Oriental, or spicy Oriental notes. AH the perfumes based on the sweet, warm, and powdery impressions brought by vanillin belong to the great family of the Oriental notes and of the amber notes. Vanillin, when used together with coumarin and nitro-musks, can have a concentration of up to 10%. 

In detergent perfumes, the stabiUty of vanillin is not always certain. It depends on the association made with other raw materials, eg, with patchouli, frankincense, cloves, most of the animal notes, and such chemicals as amyl saUcylate, methyl ionones, heflotropin, gamma undecalactone, linalool, methyl anthrarulate, benzyl acetate, phenyl ethyl alcohol, cedar wood derivatives, oak mosses, coumarin, benzoin. Pern balsam, and cistus derivatives. In some cases, these mixtures can cause discoloration effects. 

Essence of Vanilla.—The substance sold under this name is, properly, a spirituous extract of the vanilla bean. Many samples, however, are little more than alcoholic solutions of artificial vanillin, coloured with caramel. Some samples, which cannot be described as adulterated, contain a little coumarin or other odorous substance, added to varj- the characteristic vanillin odour and flavour somewhat. 

Tests for Caramel.—Valuable indications of the nature of an extract are obtained in the process of determination of vanillin and coumarin. Pure extracts of vanilla beans give, with lead acetate, a bulky, more or less glutinous, brown-grey precipitate, and a yellow or straw-coloured filtrate, whereas purely artificial extracts coloured with caramel give a slight dark brown precipitate and a dark brown filtrate. If both vanilla bean extract and caramel are present the precipitate is more or less bulky and dark coloured, and the filtrate is more or less brown. The soluticm remaining after extraction of the vanillin and coumarin with ether, if dark coloured, should be tested for caramel. 

Winton and Bailey determine vanillin, coumarin, and acetanilide (which is sometimes found as an adulterant of artificial vanillin, and therefore indicates its presence) in the following manner, which is a modification of the method devised by Hess and Prescott — ... 

Heliotropin melts at 37°, but its perfume is injured by exposure to a temperature several degrees below this, and it should always be stored in cool dark places. In very hot weather the stock may with advantage be kept dissolved in alcohol, ready for use. Its perfume is a powerful heliotrope odour, and is improved by blending it with a little coumarin or vanillin, or with bergamot, lemon, or neroli oil. Attention should be drawn to the fact that the fancy perfumes whose names resemble heliotrope are usually mixtures of heliotropin—the cheaper ones being chiefly acetanilide, the more expensive ones containing vanillin or coumarin. 

The vanillin ethers 36 and 39 exhibited the IR band of the lactone carbonyl group at 1710-1720 cm whereas the aldehydic carbonyl stretching was observed in the range of 1680-1690 cm In the NMR spectra all the protons resonated at expected fields. The aldehydic proton appeared downfield around 9-10 aromatic protons in the range of 7-8 and the C3 - H of coumarin around 6.5. The methylene, methoxy, and methyl protons resonated around 5, 3.8, and 2.2, S respectively. 

The chemical synthesis of natural flavours started some time ago with the synthesis of coumarin in 1868 and vanillin in 1874 [7]. The development of the petrochemical industry and the availability of cheap oil has meant that most of the plant-derived products are now synthesised from crude oil. In addition, flavours can now be produced using microbial cultures. Thus, to achieve sustainable development plants will have to provide many of the products currently produced from petrochemicals, including flavours. In this chapter the possible use of plant tissue culture techniques and processes in the sustainable production of flavours is outlined and discussed. 

Coumarin is widely distributed in the plant kingdom, but for commercial use has been mostly produced synthetically for many years. In addition to its use in the perfumery, cosmetic and related industries, coumarin has several other industrial applications. Formerly, large quantities of coumarin were used in the food industry, mostly associated with vanillin, for flavouring chocolates, baked goods, and in cream soda-flavoured beverages (Perone, 1972), but since 1954 its use as a direct food additive has been suspended in the United States (Boisde Meuly, 1993 Lake, 1999). 

Keywords Meldrum s acid, o-vanillin, Knoevenagel condensation, 3-carboxy-coumarin... 

Aging in oak cooperage encourages the extraction of a series of benzoic and cinnamic phenolics (including vanillin and syringic acid), gallic acid, and coumarins. It also induces modifications in their physical and chemical parameters (Del Alamo Sanza et al., 2004). 

Hydroxy Coumarine a Versatile Reagent for the Synthesis of Heterocyclic and Vanillin Ether Coumarins with Biological Activities... 

Ghate M, Kulkarni MV, Shobha R, Kattimani SY (2003) Synthesis of vanillin ethers from 4-(bromomethyl) coumarins as anti-inflammatory agents. Eur J Med Chem 38 297... 

In chapter nine Hamdi et al. describes the synthesis and biological activities of the heterocyclic and vanillin ether coumarins. 

One of the earliest perfumery materials to be produced industrially was benzaldehyde, prepared from toluene in 1866. In 1868 coumarin was first synthesized, soon to be followed by heliotropin, ionone, and vanillin. The first nitro musks appeared in 1888, and amyl salicylate in 1898. Since then, for the last hundred years, the history of perfumery has been dominated by the creation of new aromatic chemicals. 

Initially, at the beginning of the present century, the traditional structure of the earlier perfumes was for the most part retained. "Fresh" natural materials such as bergamot and lemon, in combination with other essential oils, formed a large proportion of the composition, supported by animal and balsamic fixatives. To these were added the newly discovered synthetic and derived materials such as vanillin, coumarin, hydroxycitronellal, vetiveryl acetate, and methyl ionone, to-... 

In Arpege (Lanvin 1927) the floral aspect of the fragrance was further developed by the use of compounded floral bases. Greater emphasis was also placed on the woody notes, including vetiveryl acetate, and on the animalic character, with a corresponding reduction in the vanillin and coumarin. 

The woody part of the perfume is again based on vetiveryl acetate with vetiver (6%) and sandalwood. The oakmoss is backed up by a small amount of Evemyl, a synthetic material created as a result of the study of natural oakmoss, and one that has come to play an increasingly important role in modern perfumery. Coumarin is again present with a trace of vanillin, and cyclopentadecanolide backs up the musk ketone. 

Another perfume that may be included in the sweet floral family, and that has enjoyed great success in the United States, is Vanderbilt, created in 1981. Built around a combination of fresh citrus top notes, orange blossom, and tuberose, Hedione, methyl ionone, heliotropin, vanillin, and musk ketone, with iso E super coming in as the woody note, it lacks much of the heavy floral sweetness of the other perfumes in the group, lacking most of the eugenol with little or no ylang or coumarin. 

At the time when Shalimar was made it was customary to use a high proportion of the alcoholic tinctures made from natural products, rather than the concentrated absolutes and resins. These would have included such products as vanilla, benzoin, and tonka to give naturalness to the ethyl vanillin and coumarin, as well as tinctures of civet, castoreum, ambergris, and musk. Such products retain more of the most volatile components of the starting material, giving a wonderful quality and life to the finished product. 

Otherwise, in general construction the perfume follows closely that of a classical oriental, with citrus oils (making up some 25%), lavender, sandalwood, patchouli, vanillin, coumarin, castoreum, and rose. The general sweetness of the perfume is further enhanced by the choice of musk materials, Galaxolide (5%), Tonalid, ethylene brassylate, and musk ketone, as well as by the use of Cashmeran, an intensely sweet fruity musk material associated with the synthesis of Galaxolide. 

Waliszewski et al. (2007b) described a simple and rapid HPLC technique for vanillin determination in alcohol vanilla extract, and the method has been applied successfully for the determination of vanillin in some commercial extracts for routine analysis. de Jager et al. (2007) developed a LC-MS method for the determination of vanillin, coumarin and ethyl vanillin in vanilla products using LC-electrospray ionization in the positive ionization mode. The limits of detection for the method ranged from 0.051 to 0.073 pg/ml. 

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