Anisyl Acetone

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... 

Synonyms Anisyl acetone 2-Butanone, 4-(p-methoxyphenyl)- 4-Methoxybenzylacetone p-Methoxyphenylbutanone Raspberry ketone methyl ether... 

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. 

This with potassium hydroxide in methanol forms de-OiV-dimethylarmepavine, m.p. 86-7°, (B. HCl, m.p. 229-30°) of which the methiodide, m.p. 233-4°, on treatment with alkali decomposes into trimetHylamine and a -p-anisyl-/3-(3 4-dimethoxy- 6 - vinylphenyl) -ethylene, m.p. 79°. The latter is oxidised by permanganate in acetone to anisic and m-hemipinic acids. With ethyl sulphate and alkali, armepavine gives 0-ethylarmepavine, an oil, which permanganate oxidises to p-ethoxybenzoic acid. Armepavine is similarly oxidised to p-hydroxybenzoic acid and l-keto-6 7-dimethoxy-2-methyl-1 2 3 4-tetiahydrowoquinoline and is therefore 6 7-dimethoxy-l-p-hydroxybenzyI-2-methyI-l 2 3 4-tetrahydrowoquinoline, i.e., it is laudanosine (p. 187) with MeO. at C replaced by H and MeO at C changed to HO. ... 

When the ditelluride is refluxed with methyl iodide it yields p-anisyl dimeihyltelluri-iodide,2 CH3O.C6H4.Te(CH3)2I, as a microcrystalline salmon-coloured precipitate, M.pt. 170° to 172° C., almost insoluble in acetone, benzene and other organic solvents, but hydrolysed by boiling alcohol. 

A mixture of 6.6 parts of y-chloro-p-fluoro-butyrophenone and 12.5 parts of 1-(o-anisyl)piperazine is heated for 10 hours at a temperature of 110°C. The reaction mixture is treated with 800 parts of ether and filtered. The ether layer is washed with water, dried over anhydrous potassium carbonate and filtered, whereupon hydrogen chloride gas is introduced into the solution. The precipitate is collected on a filter and dissolved in a mixture of 240 parts of 2-propanol and 80 parts of acetone to yield l-[y-(p-fluorobenzoyl)propyl]-4-(o-... 

The remarkable reactivity of trianisyl derivatives is certainly due to the a-anisyl group and not to the j8-groups. The rate of compound 138 relative to 139 in buffered acetone-water 7 3 at 120° is 830 whereas... 

The approach we adopted was to examine the exo endo rate ratios of highly stabilized tertiary 2-norbomyl derivatives. There is general agreement that such highly stabilized tertiary 2-norbomyl derivatives cannot involve a-bridging29, 30. Yet the solvolyses of the 2-p-anisyl-2-norbornylp-nitrobenzoate (26, 27) in 80% acetone at 25 °C reveal an exo endo rate ratio (RR) of 28431 ... 

A solution of 2.5 g (7.72 mmol) of ( )-2,5-di(p-anisyl)-2,5-dimethyl-3-hexene in 1 L of acetone was irradiated through Pyrex in an 450 W Hanovia apparatus for 20 h and concentrated under vacuum. The residual oil was separated by chromatography on a 148 x 27 cm silica gel column with hexane elution 100 mL fractions were collected. Fraction... 

Fig. 1. Free energy diagram for a the acetolysis of exo- and endo-norbornyl tosylate b the solvolysis of 2-p-anisyl-2-norbomyl p-nitrobenzoates in 80% aqueous acetone at 25 °C...

Anisole p-AnIsyl acetate p-Anisyl alcohol Anisyl formate Benzoic acid Benzyl alcohol Benzyl formate Benzylidene acetone Boronia (Boronia meqastiqma) flowers 2-Butanol... 

Solvolysis of the p-nitrobenzoate of (196) is ten times faster than that of (197) at 100 °C in aqueous acetone. Both give the same wide range of products, suggesting that a common ion is involved, but this intermediate must differ from the one involved in acetolysis of (198), which gives different products. Solvolyses of exo- and eni/o-dinitrobenzoates (199) (R = H, Me, Ph, or p-anisyl) have been compared. Although methyl substitution increased the rate of the less reactive exo-ester by 5 x 10 but of the endo-isomers by only 20, it has little effect on the type of product formed. The aryl substituents, unlike H and Me, led to considerable amounts of products with unrearranged skeletons. It is concluded that cyclobutyl cations will only be stable... 

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