Nitro-vanillin

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%. 

Eupe also found that one osmophore can be replaced by another without greatly altering the type of the odour, thus vanilline, p-nitro-guaiacol, and p-cyanoguaiacol all have similar odours but varying in strength. 

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. 

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. 

Vanillic acid, 30, 101, 103 Vanillin, 30, 102, 104 33, 17 Veratraldehyde, 31, 58 33, 65 Veratraldehyde, 6-nitro-, 33, 65 Vinyl acetate, 30, 106 Vinyl caprate, 30,108 Vinyl caproate, 30, 108 Vinyl caprylate, 30,108 Vinyl 10-hendecenoate, 30, 108 Vinyl laurate, 30, 106 Vinyl myristate, 30, 108 Vinyl oleate, 30, 108 Vinyl palmitate, 30, 108 Vinyl pelargonate, 30, 108 Vinyl stearate, 30, 108 Vinyl undecylenate, 30, 108... 

Nitro- and 6-nitroveratric acids, prepared from vanillin by the method of R. Pschorr and C. Sumuleanu (29), were separately subjected to the Bischoff synthesis (27), their chlorides being condensed with diethyl malonate, and the products reduced, cyclized and decarboxylated by treatment with tin and aqueous-alcoholic hydrochloric acid. 

Vanillin is a flavoring agent used in syrups, ice cream, and other edible products. Xuebao Fine Chemicals Co. Ltd. (China) used to manufacture vanillin from o-nitro chlorobenzene. The process produced toxic chemicals, three to five different tars, high CODs, high VOCs, high health and safety risks, and unacceptable standards for a flavoring product. The plant dumped untreated effluents into a nearby river, and toxic tars were stockpiled in unmonitored landfills. Rhodia Chemicals purchased Xuebao in 2000. The process was modified so that it is now based on the catechol route (see Fig. 9.29). This process does not produce any waste and uses several heterogeneous catalysts. 

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