P-Methoxyphenyl acetone

Dimethoxybenzoic acid Tetramethylene dichloride p-Methoxyphenyl acetone Ethylamine... 

In a sensitive and specific colorimetric method 1,1,1-trichloro-2,2-bis(p-methoxyphenyl)-ethane is extracted from plant or animal tissue, using benzene or petroleum ether as the solvent. The solvent is evaporated at room temperature by a current of air and the residue dehydroha log ena ted with 2% alcoholic potassium hydroxide. By petroleum ether extraction the resulting 1,1-dichloro-2,2-bis(p-methoxyphenyl)-ethylene is removed from the reaction mixture. After the solvent is removed by air evaporation the dehydroha log ena ted methoxychlor is isolated from the nonsaponifiable portion of the fats and waxes by dissolving the residue in hot acetone, chilling, and filtering. After the acetone is removed by air evaporation, the residue is treated with 85% sulfuric acid. This produces a red solution with an absorption maximum at 555 m/z, the intensity of which can be read on a colorimeter and is a function of the methoxychlor concentration. Beer s law is obeyed over the range of 1 to 50 micrograms. 

Reduction of diaryltellurium dichlorides with sodium ascorbate (typical procedure). Bis (p-methoxyphenyl)tellurium dichloride (0.20 g, 0.48 mmol) dissolved in acetone (10 mL) was added to a stirred solution of sodium ascorbate (0.20 g, 1.0 mmol) in water/methanol (2+8 mL). After 24 h, water (50 mL) and CH2CI2 (50 mL) were added and the two phases separated. The organic phase was dried (CaCl2) and the solvent evaporated in vacuo. Flash chromatography yielded 0.14 g (84%) of bis(p-methoxyphenyl) telluride. 

Preparation of various enantiomerically pure sulfoxides by oxidation of sulfides seems feasible in the cases where asymmetric synthesis occurs with ee s in the range of 90% giving crystalline products which can usually be recrystallized up to 100% ee. Aryl methyl sulfides usually give excellent enantioselectivity during oxidation and are good candidates for the present procedure. For example, we have shown on a 10-mmol scale that optically pure (S)-(-)-methyl phenyl sulfoxide [a]p -146 (acetone, o 1) could be obtained in 76% yield after oxidation with cumene hydroperoxide followed by flash chromatographic purification on silica gel and recrystallizations at low temperature in a mixed solvent (ether-pentane). Similarly (S)-(-)-methyl o-methoxyphenyl sulfoxide, [a]p -339 (acetone, o 1.5 100% ee measured by HPLC), was obtained in 80% yield by recrystallizations from hexane. 

Similar studies were conducted with 1-phenylethyl benzoate derivatives labeled with, sO (radioactive) or, 70 (NMR active) carbonyl groups. Substituents in the alkyl groups and in the leaving group affect both the rates and the nature of the carbenium ion intermediates. For example, 1-phenylethyl p-nitrobenzoate undergoes solvolysis [Eq. (19)] at 60° C in 70% aqueous acetone 30,000 times slower than the corresponding l-(p-methoxyphenyl)ethyl derivative [54]. 

Another example of an epoxide isomerization occurring by a similar mechanism is the pH-independent reaction of cts-anethole oxide 121, which yields (n-methoxy-phenyl)acetone 125 along with threo and erythro l-(p-methoxyphenyl)-l,2-pro-panediols 126.107 During the course of the reaction, trans-anethole oxide (124) builds up to a level that is detected by JH NMR (Scheme 35). The mechanism for this reaction involves benzylic C-0 bond breaking, rotation about the Cx-Cp bond via zwitterionic structures 122 and 123, and epoxide ring closure to form trans-anethole... 

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

Propanone, l-(p-methoxyphenyl)-. See1-(p-Methoxyphenyl)-2-propanone 2-Propanone oxime. See Acetone oxime 1-Propanone, 1-phenyl-. See Ethyl phenyl ketone Propiophenone... 

Tricyano-4-(p-methoxyphenyl)-butadiene The reaction mixture in each experiment using initiator gave a red butadiene adduct which was isolated after the precipitation of the polymer, by evaporating the methanol. The product was recrystallized from acetone to give red crystals, m.p. 208-209 C. Selected experiment gave 50% butadiene adduct. Solution experiment gave less yield. IR (KBr) 2230 (C=N), 1590 (C=C), 1265 (CH -0-Ar), 840 (1,4-disubstituted phenyl)cm ... 

Small amount of water (10-50 equiv.) are able to affect the stereoselectivity of the products between 9-tosyl-3,4-dihydro-P-carboline and ketones in the presence of L-proline as a catalyst in DMSO (Scheme 24.5a) [131]. This effect was also observed in CH2CI2 and acetone, although it cannot be fully rationalized. Later, proline gave rise to high stereoselectivities in the catalytic reaction of aqueous tetrahydro-2H-pyran-2,6-diol with N-(p-methoxyphenyl) (PMP) aldimines in DMSO to afford the corresponding tetrahydropyridines via a Mannich-type/ intramolecular cycUzation cascade reaction (Scheme 24.5b) [132]. 

Difunctional target molecules are generally easily disconnected in a re/ro-Michael type transform. As an example we have chosen a simple symmetrical molecule, namely 4-(4-methoxyphenyl)-2,6-heptanedione. Only p-anisaldehyde and two acetone equivalents are needed as starting materials. The antithesis scheme given helow is self-explanatory. The aldol condensation product must be synthesized first and then be reacted under controlled conditions with a second enolate (e.g. a silyl enolate plus TiCl4 or a lithium enolate), enamine (M. Pfau, 1979), or best with acetoacetic ester anion as acetone equivalents. 

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). 

D) 4 -[N-Ethyi-1 "-Methyl-2 -(4" -Methoxyphenyl)Ethylamino]Butyi-3,4-Dimethoxybenzoate Hydrochloride 10.3 g of 4 -iodobutyl-3,4-dimethoxybenzoate and 11.0 g of N-ethyl-p-methoxyphenylisopropylamine (obtained by catalytic reduction of an alcoholic solution of an excess quantity (60%) of p-methoxy-phenyl-acetone, to which was added a 33% (weight-for-weight) aqueous solution of ethylamine, with Pt as a catalyst), were boiled in 200 ml of methyl ethyl ketone for 20 hours, cooled and the iodine ion was determined the reaction was found to be complete. Then the methyl ethyl ketone was evaporated in vacuo and the residue was dissolved in 300 ml of water and 30 ml of ether the layers were separated and the water layer was extracted twice more with 20 ml portions of ether. 

The chloroform layer was dried and evaporated to remove the solvent. The residue was dissolved in acetone, and an ethanol solution containing hydrogen chloride was added thereto producing 1.53 grams of 2-(4-methoxyphenyl)3-acetoxy-5-(p-dimethylaminoethyl)-2,3-dihydro-l,5-benzothiazepin-4(5H)-one hydrochloride having a melting point from 187° to 188°C. 

D) 4 -[N-Ethyl-l"-Methyl-2"-(4" -Methoxyphenyl)Ethylamino]Butyl-3,4-Dimethoxybenzoate Hydrochloride 10.3 g of 4 -iodobutyl-3,4-dimethoxybenzoate and 11.0 g of N-ethyl-p-methoxyphenylisopropylamine (obtained by catalytic reduction of an alcoholic solution of an excess quantity (60%) of p-methoxy-phenyl-acetone, to which was added a 33% (weight-for-... 

Methoxyphenyl 2-Oxo-l-propyl Tellurium Dichloride1 0.34 g (1 mmol) of 4-mcthoxyphcnyl tellurium trichloride is dissolved in 5 ml of acetone in a small flask. The acetone is rapidly evaporated at 20°, another 5 ml of acetone are added to the residue, and the acetone is again evaporated. This procedure is repeated three times. The residue is washed with a small volume of cold methanol and then recrystallized from benzene/petroleum ether (b.p. 50-70°) yield. 0.23 g (65%) m.p. 138°. 

Ugi with imine (Scheme 87) [349] Synthesis of N-(4-methoxyphenyl)-(R,S)-valine methylester iso-Butyraldehyde (0.044 mL, 0.48 mmol) and 60 mg p-anisidine (0.48 mmol) were dissolved in 2 mL dry dichloromethane and 50 mg molecular sieve (0.4 nm) was added. The reaction mixture was stirred at r. t. for 1 h. The molecular sieve was filtered off and 0.195 mL dry CH3OH (4.8 mmol), 0.183 mL boron trifluoride etherate (1.44 mmol), and 400 mg isocyanomethyl polystyrene (0.24 mmol) were added together -with 2 mL dry CH2CI2. The reaction mixture was shaken at r.t. for 2 h. The resin was filtered off and washed twice with dry CH2CI2 and dry acetone. 

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