Vanillin crystallization

The use of high concentrations of vanillin in soap perfumery can cause discoloring effects over time, dark or black spots appear on the soap and foaming power is reduced. In some cases, however, the use of Rhodiarome ethylvanillin is possible, because ethylvanillin [121 -32-4] does not cause the same discoloration problems and, being at least three times more powerful than vanillin, can be used alone. Some surprising cases show that with oak or tree mosses and large amounts of methyl ionones, the soap perfume may look fine and have a low discoloration, and yet over time vanillin crystals can appear on the soap itself. 

Sometimes there are problems in using CO2 extracts in the usual formulation because of the high concentration of vanillin. The concentration is up to 100 times higher than in alcohol extracts, where it is only 0.2%. Under certain conditions, crystalline vanillin is separated from the water phase of the extract. After drying this crystalline phase, a product with more than 90% vanillin can be produced. By mixing these vanillin crystals back with the oil-phase any desired vanillin concentration can be obtained, which makes the product very useful for the food industry. 

According to Gildemeister and Hoffmann (1899), vanillin crystallizes from hot water in the form of colourless needles at 81-82°C. It possesses the strong and intensely sweet... 

Vanillin crystallizes in needles which melt at 81°. It gives a blue coloration with an aqueous solution of ferric chloride, reduces an ammoniacal solution of silver nitrate, and decomposes carbonates. It is oxidized by moist air to vanillic acid, which is formed as the result of the conversion of the aldehyde group into a carboxyl group. 

CgHeOa. White crystals m.p. 37°C, b.p. 263°C. Occurs associated with vanillin. Obtained on oxidation of various natural products such as piperine. Used extensively in soap perfumery. 

Preparation from Waste Sulfite Liquors. The starting material for vanillin production can also be the lignin (qv) present in sulfite wastes from the ceUulose industry. The concentrated mother Hquors are treated with alkaH at elevated temperature and pressure in the presence of oxidants. The vanillin formed is separated from the by-products, particularly acetovanillone, 4-hydroxy-3-methoxyacetophenone, by extraction, distillation, and crystallization. 

Particle-Size Distribution. Particle size, crystal shape, and distribution of vanillin ate important and gready affect parameters such as taste. 

Fig. 2. Particle size distribution of crystallized Rhovanil Extra Pure vanillin.

It is easy to smell a difference in the quaUty of vanillins from different origins, but it is normally difficult to taste the same difference, provided the various samples are of good quaUty. Vanillin is sensitive to contamination with other crystalline odor chemicals. Adherent or absorbed odor on the crystals perceptibly affects the odor of vanillin from a ftber-dmm or other large containers. 

Available Grades. Rhovanil Extra Pure is the trade name of the food-grade vanillin of Rhc ne-Poulenc, worldwide leader in the diphenols area. The following grades are commercially available Rhovanil Extra Pure crystallized, Rhovanil Pine Mesh, Rhovanil Pree Plow, and Rhovanil Liquid. 

Perfumes and Cosmetics. Vanillin, a crystal, is the main constituent of the vanilla bean. Its importance can be illustrated by the fact that human preferences in fragrances and in flavors, as determined by various studies, comprise three main smells or tastes rose, vanilla, and strawberry. 

Valence, 286 Valence electrons, 269 and ionization energies, 269 Vanadium atomic radius, 399 eleciron configuration, 389 oxidation numbers, 391 pentoxide catalyst, 227 properties, 400, 401 van der Waals forces, 301 elements that form molecular crystals using, 301 and molecular shape, 307 and molecular size, 307 and molecular substances, 306 and number of electrons, 306 van der Waals radius, 354 halogens, 354 Vanillin, 345... 

Rhombic prism lattice, 8 114t Rhombohedral structure, of ferroelectric crystals, 11 95, 96 Rhombohedron lattice, 8 114t Rhomboidal symmetry, 8 114t Rhone-Poulenc process, 24 482, 485 Rhovanil extra pure vanillin, 25 548t, 549-550... 

Keywords Black liquor, crystallization process, oil palm empty fmit bunches, soda lignin, vanillin... 

In this study the percentage of vanilhn present in the soda lignin sample will be determined. Next, the vanillin compound will be separated from soda lignin via crystallization technique. 

Separation process via crystallization technique was used to separate vanillin from other components present in the hgnin. The precipitate obtained from this process... 

Fig. 9.2 IR spectrum of the precipitate sample (believe to be vanillin) from the crystallization...

The H-FT-NMR spectra were obtained from a Bruker Avance 300 operating in the FT mode at 400 MHz under total proton decoupled conditions. The spectra were recorded at 40°C from 200 mg sample vanillin dissolved in 1 mL CDClj after 3,000 scans. A 90° pulse flipping angle, a 26.6 ps pulse width and a 1.74 s acqnisi-tion time were employed. There was no significant difference in the stractnre of vanillin precipitated from crystallization process and standard vanillin based on H-NMR analysis (Fig. 9.5). Incomplete dissolntion of the sample may becanse of the rmexpected high signaPnoise ratio. The peaks show that the chemical shifts for both of vanillins are very similar. 

In conclusion, the HPLC, FT-IR and H-FT-NMR analyses confirmed that the precipitate obtained via the crystallization process was vanillin. 

Fig. 9.4 The HPLC chromatograms of precipitate from the crystallization process and the standard vanillin (1 ppm)...

Fig. 9.5 IH-NMR spectrums for standard vanillin and sample vanillin percipitate from crystallization process...

Hydroxy-3-methoxy-B-nitrostyrene. A mixture of methylamine hydrochloride (7 g, see precursor section for synthesis) and 10 g of sodium carbonate in 100 ml of methanol is stirred well, filtered, and added to a solution of 219 g of vanillin and 85 ml of nitromethane in 600 ml of ethanol. Keep this solution in the dark at room temp for 71 hours to make the nitrostyrene crystallize out. Filter and wash with cold methanol. Yield 225 grams, nip 166-168°. This and the other two nitriles are reduced by the method listed in the reduction section, JACS, 72, 2781. This reduction can be used to reduce many of the nitro type compounds. 

Particle-Size Distribution. Particle size, crystal shape, and distribution of vanillin are important and greatly affect parameters such as taste, flavor, solubility, case of dispersion in solvent, flowability of the powder, caking effect, and production of dust. 

SYNTHESIS To an ice cold and well stirred solution of 15 g vanillin and 20 g sodium thiocyanate in 150 mL acetic acid there was added, dropwise over the course of 15 min, a solution of 16 g elemental bromine in 40 mL acetic acid. This was followed by the addition of 30 mL of 5% HC1 and 300 mL EtOH, and stirring was continued for an additional 30 min. The mixture was heated to its boiling point, and filtered while hot. The mother liquor was diluted with an equal volume of H20, which initiated the crystallization of crude 5-form yl-7-methoxy-2-oxo-l,3-benzoxathiole as a flocculant yellow solid. On filtration and airdrying, this weighed 12.5 g. After recrystallization from EtOH, the product was white and had a mp of 164 °C sharp. 

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