Anisyl aldehyde

This method was introduced by Polonski and Chimiak 192,193) in 1974 (Scheme 47). It is based on the oxidation of Schiff bases (239) to appropriate oxaziridines (240) in ether using monoperphtalic acid (MPP). Bases (239) are obtained from esters of amino acids and anisyl aldehyde (238) and are oxidised without isolation. Oxaziridines (240) are next hydrolyzed with hydrochloric acid to N-hydroxyamino acids (1) or give p-toluenesulfonates of (76, 213), which crystallize readily, by splitting with hydroxylamine j7-toluenesulfonates in alcohol. Use of benzaldehyde is unfavourable and leads to nitrones. Use of mono-perphthalic acid permits one to follow the progress of the reaction due to precipitation of phthalic acid. This method is general. Because bases (239) racemize only very slowly it is possible to obtain 193) optically active compounds (1,76, 213). 

It not tertiary, the product yield is lowered by transfer of the carbinol hydride ion to the aldehyde to produce a new alkoxide and an enolate ion. Thus, propylene oxide, after reductive cleavage with LDBB and trapping with isobutyraldehyde or p-anisaldehyde, provided 5-methyl-2,4-hexanediol in 40-50% yield or 1-p-anisyl-1,3-butanediol in 44% yield, respectively (in both cases about equal mixtures of diastereoisomers were obtained). The cyclohexene oxide-derived dianion, when trapped with isobutyraldehyde, gave 2-(1-hydroxy-2-methylpropyl)cyclohexanol in 71% yield as a mixture of only partially separable isomers in the ratio 15 11 39 35. 

Lund 12°) was first in applying cpe in the oxidation of a primary alcohol to an aldehyde (which under constant current conditions would be partly or completely oxidized to the corresponding carboxylic acid) 121 Anisyl alcohol displays two anodic waves in acetonitrile-sodium perchlorate withiTj /2 of 1.22 and 1.64 V vs. Ag/0.1 M Ag Cpe at the plateau of the first wave (1.35 V) in the same medium consumed only 5 % of the theoretically calculated amount of electricity and no carbonyl compound was formed. Addition of a three-fold excess of pyridine (to act as a proton acceptor) gave a 72 % of anisaldehyde ... 

Anisyl Alcohol 653 Butyl Phenylacetate 668 Cuminic Aldehyde... 

Anisic Alcohol, 456 Anisic Aldehyde, 524 Anisole, 456, 606 Anisyl Acetate, 456, 568, 606 Anisyl Acetone, 524 Anisyl Alcohol, 456, 606 Anisyl Formate, 456, 607 Annatto Extracts, 31 Anthrone TS, (Sl)114 Antimony Trichloride TS, 850, 851 APDC Extraction Method, 766 APM, 35, (S 1)4 APM-Ace, (S3)5 APO, 32 Apocarotenal, 32 p-Apo-8 -Carotenal, 32 Apparatus for Tests and Assays, 4, 727 D-Araboascorbic Acid, 134 L-Arginine, 32, (S3)5 l-Arginine Monohydrochloride, 33 Arsenic Specification, Requirements for Keeping, xv... 

The substituted benzyl alcohols listed below are prepared in a similar manner from the corresponding aldehydes in the yield indicated vanillyl alcohol, m.p. 113-114°, recrystallized from benzene, 95% anisyl alcohol, b.p. 127-130°/8 mm., 92% piperonyl alcohol, m.p. 52-53°, recrystallized from a mixture of ether and petroleum ether, 91% p-chlorobenzyl alcohol, m.p. 71-72.5°, recrystallized from ben-zene-ligroin mixture, 92% o-chlorobenzyl alcohol, m.p. 64 -65°, 96% p-bromobenzyl alcohol, m.p. 76-76.5°, 96%. 

Worldwide p-anisyl alcohol from p-anisic aldehyde is estimated at 1200 tpa. Major producers are ... 

Manufacturing process Several methods exist for reduction of o-anisic aldehyde to o-anisic alcohol, however, direct reduction by hydrogen using Raney-Nickel catalyst system at 90-100° C and 5-7 atm pressure has been commercially most attractive. Most of the key players of p-anisic alcohol such as BASF, Givaudan, Koffoeks, etc. also produce some quantities of o-anisyl alcohol. Application areas include flavor and fragrance, pharmaceuticals, etc. Global demand has been estimated at 300-350 tpa. 

Manufactured from p-cresol via p-anisic aldehyde via p-anisyl alcohol. 

Irradiation of 4-methyl-5-/7-anisyl substituted A-alkoxythiazolethiones brings about N-O bond homolysis with the formation of alkoxy radicals. This technique has been applied to the synthesis the compound (36). The aldehyde (37) undergoes addition to dimesitylsilene when it is irradiated at -57°C in hexane. The product, obtained in 76% yield, was identified as (38). 

Anisic alcohol. See p-Anisyl alcohol Anisic aldehyde. See p-Anisaldehyde o-Anisic aldehyde. Seeo-Methoxybenzaldehyde p-Anisic aldehyde. See p-Anisaldehyde Anisic ketone. See 1-(p-Methoxyphenyl)-2-propanone... 

Benzalkonium chloride Sodium hypochlorite Anisyl alcohol, balsam of Peru, benzyl alcohol, cinnamic alcohol, cinnamic aldehyde, citronellol, coumarin, eugenol Common food dyes are used, e.g.. Food Yellow 4 (C.I. No. 19140)... 

Fragrances (some may also induce immunologic contact urticaria reactions) - cinnamic alcohol, cinnamic aldehyde, geraniol, eugenol, balsam of Peru, anisyl alcohol, benzyml alcohol, coumarin Sorbic acid... 

C, anhydrous DMSO (0.5 mL, 7.06 mmol) was added dropwise with stirring. After 5 min, 2- p-anisyl)ethanol (0.403 g, 2.63 mmol) in dry dichloromethane (10 mL) was added dropwise. The mixture was stirred at —78 °C for an additional 15 min, then triethylamine (2.0 mL, 14.28 mmol) was added, and the reaction mixture was allowed to warm to room temperature ( 10 min). It was quenched with water (50 mL) and the organic phase was washed sequentially with 5% aq. HCl (50 mL), 5% aq. NaHCOa (50 mL), saturated Nad solution, and water. The final organic layer was dried over Na2S04, subjected to flash chromatography (15 g of silica gel), and the solvent was removed under reduced pressure to give the aldehyde 1889 in 79% yield. 

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