4-Anisyl alcohol

Uses Mostly as an intermediate in pharmaceutical, flavor, and fragrance. 

Manufacturing process m-Anisic aldehyde can be directly reduced to the alcohol by hydrogenation using Raney-Nickel catalyst around 90-100°C and 6-7 atm pressure. Other processes also exist but they are not commercially viable. BASF, H R, Givaudan are also some pharmaceutical majors manufacturing some quantities captively. 

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In a 1-1. flask fitted with a paddle-blade stirrer are placed 138 g. (1 mole) of anisyl alcohol (Note 1) and 248 ml. of concentrated hydrochloric acid. After stirring vigorously for 15 minutes the contents of the flask are transferred to a separatory funnel. The... 

In a 2-1. three-necked round-bottomed flask, fitted with an efficient sealed stirrer and a reflux condenser capped by a drying tube, are placed the dried anisyl chloride (Notes 2 and 3), 73.6 g. (1.5 moles) of finely powdered sodium cyanide, 10 g. of sodium iodide, and 500 ml. of dry acetone (Note 4). The heterogeneous reaction mixture is heated under reflux with -sngorous stirring for 16-20 hours, then cooled and filtered with suction. The solid on the filter is washed with 200 ml. of acetone and discarded (Note 5). The combined filtrates are distilled to remove the acetone. The residual oil is taken up in 300 ml. of benzene and washed with three 100-ml. portions of hot water. The benzene solution is dried over anhydrous sodium sulfate for about 15 minutes, and the solvent is removed by distillation at the reduced pressure of the water aspirator (Note 6). The residual -methoxyphenyl-acetonitrile is purified by distillation under reduced pressure through an 8-in. Vigreux column b.p. 94—97°/0.3 mm. 1.5285-1.5291. The yield is 109-119 g., or 74-81% based on anisyl alcohol (Notes 7 and 8). 

This method is particularly applicable to the more reactive benzyl halides which are easily hydrolyzed in the aqueous media usually employed for the metathetical reaction with alkali cyanides. For example, anisyl chloride treated with sodium cyanide in aqueous dioxane gives, as a by-product, 5-10% of anisyl alcohol as determined by infrared analysis. The use of anhydrous acetone not only prevents hydrolysis to the alcohol but also decreases the formation of isonitriles. This method was also applied successfully by the submitters to the preparation of -chlo-rophenylacetonitrile in 74% yield. 

Verhagen FJM, HJ Swarts, JBPA Wijnberg, JA Field (1998) Biotransformation of the major fungal metabolite 3,5-dichloro-p-anisyl alcohol under anaerobic conditions and its role in formation of bis(3,5-dichloro-4-hydroxyphenyl)methane. Appl Environ Microbiol 64 3225-3231. 

Anisamide, m54 Anisic acids, m57, m58, m59 Anidisines, m48, m49, m50 Anisole, m55 p-Anisoyl chloride, m60 p-Anisyl alcohol, m61 Anthranilamide, all2 Anthranilic acid, all8 Araboascorbic acid, i61 APDC, p282 Arsanilic acids, all3... 

This is a rapid, convenient procedure. If trimethoxybenzyl alcohol is used in place of p-anisyl alcohol, mescaline will result. Shake 100 g p-anisyl alcohol (or 0.72 moles analog) with 500 ml concentrated HCI for 2 minutes. Wash the organic phase with water, 5% NaHC03 and water, and then add over 40 minutes to a stirred slurry of 49 g NaCN in 400 ml dimethylsulfoxide with ice water cooling to keep temperature at 35-40°. After completing addition, remove cooling bath, stir for 90 minutes and then add to 300 ml water. Separate the small upper layer and extract the aqueous-DMSO layer... 

I. 4-methoxyacetophenone (30 //moles) was added as an internal standard. The reaction was stopped after 2 hours by partitioning the mixture between methylene chloride and saturated sodium bicarbonate solution. The aqueous layer was twice extracted with methylene chloride and the extracts combined. The products were analyzed by GC after acetylation with excess 1 1 acetic anhydride/pyridine for 24 hours at room temperature. The oxidations of anisyl alcohol, in the presence of veratryl alcohol or 1,4-dimethoxybenzene, were performed as indicated in Table III and IV in 6 ml of phosphate buffer (pH 3.0). Other conditions were the same as for the oxidation of veratryl alcohol described above. TDCSPPFeCl remaining after the reaction was estimated from its Soret band absorption before and after the reaction. For the decolorization of Poly B-411 (IV) by TDCSPPFeCl and mCPBA, 25 //moles of mCPBA were added to 25 ml 0.05% Poly B-411 containing 0.01 //moles TDCSPPFeCl, 25 //moles of manganese sulfate and 1.5 mmoles of lactic acid buffered at pH 4.5. The decolorization of Poly B-411 was followed by the decrease in absorption at 596 nm. For the electrochemical decolorization of Poly B-411 in the presence of veratryl alcohol, a two-compartment cell was used. A glassy carbon plate was used as the anode, a platinum plate as the auxiliary electrode, and a silver wire as the reference electrode. The potential was controlled at 0.900 V. Poly B-411 (50 ml, 0.005%) in pH 3 buffer was added to the anode compartment and pH 3 buffer was added to the cathode compartment to the same level. The decolorization of Poly B-411 was followed by the change in absorbance at 596 nm and the simultaneous oxidation of veratryl alcohol was followed at 310 nm. The same electrochemical apparatus was used for the decolorization of Poly B-411 adsorbed onto filter paper. Tetrabutylammonium perchlorate (TBAP) was used as supporting electrolyte when methylene chloride was the solvent. 

Table III. Oxidation of anisyl alcohol by TDCSPPFeCl in aqueous solution in the presence of veratryl alcohol (pH 3)...

Anisyl Alcohol (/imoles) Veratryl Alcohol (/imoles) % yield of Anisaldehyde % TDCSPPFeCl Left After Reaction... 

Table IV. Oxidation of Anisyl Alcohol by TDCSPPFeCl and mCPBA in Aqueous Solution in the Presence of 1,4-dimethoxybenzene (pH 3)...

Anisalcohol or Anisic Alcohol. Same as Anisyl Alcohol... 

Anisyl Alcohol or Metboxybenzyl Alcohol, HjCO-CtHi-CHaOH. All three isomers o-, m- and p- are described in Beil 6, 893, 896, 897, (439,440) (878, 881 883)... 

Anisyl Alcohol, Azido—, CgH NjOj and Diaziod—, QH0NsO3 Derivatives were not found in Beil or CA through 1956 Anisyl Alcohol, Nitrates, HjCO QH+ CHa -0N03. Aii three isomers o-, m- and p- were prepd by J.W.Baker T.G.Heggs, Chemistry A. Industry 1954 464 from Ag nitrate and the corresponding chlorides. The p-isomer was too unstable to distil... 

Anisyl alcohol and derivs 1 A456-A457 anisyl alcohol, nitrates 1 A456 dinitroanisylalcohols 1 A456-A457 mononitroanisylalcohols 1 A456... 

Flowery Anisyl alcohol Benzyl acetate, phenylaceiate Cinnamic acid Cinnamyl acetate Citronellyl formate Crcsyl acetate Decanal Dimethyl benzyl carbinol Dimethyl benzyl carbinyl acetate Ethyl anthranilate Geranyl acetate Hydroxycitronellal dimethyl acetate Linalool Linalyl acetate Methyl benzoate Pcnethyl acetate 2-Phcnylpropionaldehyde 3-Phenylpropionaldehvde. 

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 ... 

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