Ethyl Vanillin Methylation

After a nitrogen atmosphere has been established, 332.4 g of ethyl vanillin are loaded into a 2000 mL. 3-necked round-bottomed flask heated by an electric heating mantle, stirred mechanically, and equipped with two dropping funnels, a condenser, devices for measuring the temperature and the pH, and a nitrogen inlet. 

360 g of aqueous 30.5% sodium hydroxide solution (pH=9) are added, followed by 350 g of dimethyl sulphate, over 2 hours. 

The reaction medium is left stirring for 1 hour at 90° C. and is then cooled to 70° C. and allowed to separate by settling. 

The upper organic layer is washed and is then distilled at 120° C. under a reduced pressure of 10 mm of mercury (1330 Pa), to give 3-ethoxy-4-methoxybenzaldehyde. 

The results obtained, after assaying by high performance liquid chromatography, are as follows  

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Methyl vanillin is used in flavorings, fragrances, pharmaceuticals, and perfumes. It is closely related to ethyl vanillin, a slightly larger molecule. 

SYNTHESIS A solution of 83 g bourbonal (also called ethyl vanillin, or vanillal, or simply 3-ethoxy-4-hydroxybenzaldehyde) in 500 mL MeOH was treated with a solution of 31.5 g KOH pellets (85% material) dissolved in 250 mL H,0. There was then added 71 g methyl iodide, and the mixture was held under reflux conditions for 3 h. All was added to 3 volumes of H20, and this was made basic with the addition... 

CIC The main components, responsible for the repulsive odour are 1-propanethiol, ethanthiol and methanethiol, and the corresponding sulfides. Ethyl butyrate and ethyl-2-methyl butyrate impart the fruity, fresh strawberry character. Components like vanillin, 2,5-dimethyl-4-hydroxy-furan-3(2H)-one, 3-methyl-cyclopent-2-en-2-ol-l-one, gamma-decalactone (all not yet identified in Durian) may support the creamy nutty character. 

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. 

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. 

Cherry Benzaldehyde, Tolyl aldehyde (para) Chocolate 5-Methyl-2-phenyl-2-hexenal. Isoamyl butyrate, vanillin, ethyl vanillirt, methyl methoxypyrazine... 

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. 

Methamidophos, see Acephate Methane, see Acetaldehyde, Benzoic acid, 7 Bromobenzoic acid. 3-Bromobenzoic acid. 4-Bromobenzoic acid. Bromoform, Carbatyl, Catechol, 2-Chlorobenzoic acid. 3-Chlorobenzoic acid. Chloroform, Dibromochloromethane, 2,5-Dichlorobenzoic acid. 1,2-Dichloroethane, Ethylamine, Ethyl bromide. Ethylene dibromide, Ethylenimine, Formic acid, Hydroqninone, 4 Hvdroxvbenzoic acid. Indole, 2-Iodobenzoic acid. 3 lodobenzoic acid. Methyl bromide, 4-Iodobenzoic acid. 2-Methylphenol, 4-Methylphenol, Phenol, Prorocatechuic acid. Svringic acid. Svringaldehvde. TCDD, Tetrachloroethylene, Toluene, Trichloroethylene, Vanillin. Vanillic acid. Vinyl chloride... 

The impact of MOX upon reductive odors was included in the study of McCord (2003) for MOX at 5-10 mL/L/month over 5 months on a Cabernet Sauvignon wine in commercial scale tanks. Lower concentrations of methyl mercaptan and ethyl mercaptan were observed in the oxygenated wines, but no impact was seen upon disulfides, in spite of the suggestion that concentrations of the disulfides could increase due to direct oxidation of sulfides. Dimethyl sulfide concentrations were not affected, except that lower concentrations were seen in wines with added toasted oak staves or segments, with or without MOX. The concentrations of various oak extracted compounds were also measured in this study, with similar levels seen with and without MOX alongside appreciable increases due to the presence of the oak staves or segments in some cases (e.g., lactones and vanillin), oxygenation appeared to enhance aroma extraction. 

In one, S-adenosyl-L-methionine was the methyl donor, norepinephrine was the substrate, while products of the reaction, normeranephrine and norparanephrine, were converted to the more stable and more easily obtained compounds vanillin and isovanillin, respectively, by periodate oxidation. The oxidation also allowed for the extraction of the incubation mixture with organic solvents such as ethyl acetate, affording a more complete deproteinization. 

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