Acetic 4-methoxy-2-methylphenyl

When Cl and MeO substituents are attached to the phenolic ring, the PFR may result in displacement of those substituents by the acyl moiety. An example of chlorine displacement has been given in Section I, whereas Scheme 10 shows the case of 2-methoxy-4-methylphenyl benzoate (26), where the reaction mixture contains 2-hydroxy-5-methylbenzophenone (27), a product of methoxy substim-tion [37]. Hageman also reported the substitution of MeO by acetyl in the photolysis of 4-methoxyphenyl acetate and related esters [32]. 

An autoclave was charged with palladium acetate (0.0140 g), l,3-bis[bis(2-methoxy-5-methylphenyl)phosphino]propane (0.0398 g), trifluoroacetic acid (0.0499 g), benzothiazole (0.4225 g), and 100 ml of acetone. The solution was then treated with 2497.5 ml of methanol and water (1000 ppm) and then sealed and stirred at 800 rpm. The mixture was heated to 70°C and carbon monoxide and ethylene having a molar ratio of 1 1.8, respectively, added until the internal pressure of the autoclave was 100 bar. The mixture was then stirred for 2 hours while the internal temperature and the internal pressure were maintained at 100 bar and 70°C. After cooling the contents were removed, degassed, filtered, washed with methanol several times, and 51.5 g of product isolated. 

SYNTHESIS A solution of 0.4 g 1 -(2,5-dimethoxy-4-methylphenyl)-1 -methoxy-2-nitroethane (see preparation in the recipe for BOD) in 3.0 mL acetic acid was heated to 100 °C on a steam bath. There was added 1.0 g powdered zinc, followed by additional acetic acid as needed to maintain smooth stirring. After0.5 h there was... 

To a solution of 11.35 g 5-ethoxy-2-methoxy-4-methylbenzaldehyde in 48 mL glacial acetic acid containing 4 g anhydrous ammonium acetate there was added 10 mL nitroethane, and the mixture heated on the steam bath for 2 h. Standing at room temperature overnight allowed a heavy crop of hrilliant crystals to deposit. These were removed by filtration, washed cautiously with acetic acid, and air dried to give 8.6 g l-(5-ethoxy-2-methoxy-4-methylphenyl)-2-nitropropene with a mp of 118-120 °C. Rccrystallization of all from 200 mL boiling MeOH gave 8.3 g of lustrous crystals with a mp of 121-122 °C. 

ARIADNE itself, reduced not with LAH or AH (which would give the primary amine), but rather with sodium borohydride and borane dimethylsulfide. The product, 1-(2,5-dimethoxy-4-methylphenyl)-N-hydroxy-2-aminobutane hydrochloride, was a white crystalline material. The TOM analogue got as far as the nitrostyrene. This was made from 2-methoxy-4-methyl-5-(methylthio)benzaldehyde (see under the 5-TOM recipe for its preparation) and nitropropane in acetic acid, and gave bright yellow crystals. The true pseudo-analogue is the 2,4,6-trimethoxy material based on TMA-6, which is the "real" pseudo-TMA-2. The nitrostyrene from 2,4,6-trimethoxybenzaldehyde and nitropropane crystallized from MeOH/CH3CN as fine yellow crystals, and this was reduced with AH in cold THF to 1-(2,4,6-trimethoxyphenyl)-2-aminobutane which was a bright, white powder. 

Synonyms 2-Chloro-6 -ethyl-N-(2-methoxy-1 -methylethyl) acet-o-toluidide a-Chloro-2 -ethyl-6 -methyl-N-(1-methyl-2-methoxyethyl)-acetanilide 2-Chloro-N-(2-ethyl-6-methylphenyl)-N-(2-methoxy-1-methylethyl) acetamide 2-Chloro-N-(6-ethyl-o-tolyl)-N-(2-methoxy-1 -methylethylj-acetamide 2-Ethyl-6-methyl-1 -N-(2-methoxy-1 -methylethyl) chloroacetanilide Classification Chloracetanilide Empirical C1SH22CINO2... 

Synonyms Bicep CGA 24705 2-Chloro-A-(2-ethyl-6-methylphenyl)-A-(2-methoxy-l-methylethyl)acetamide 2-Chloro-6 -ethyl-A-(2-methoxy-1 -methylethyl)acet-(9-toluid-ide a-Chloro-2 -ethyl-6 -methyl-7V-(l-methyl-2-methoxyethyl)acetanilide 2-Chloro-A-(2-ethyl-6-methylphenyl)-A-(2-methoxy-l-methylethyl)acetamide Codal Cotoran multi Dual Dual 8E Dual 25G 2-Ethyl-6-methyl-l-A-(2-methoxy-l-methylethyl)chloroaceta-nilide Metelilachlor Milocep Ontrack 8E Pennant Pennant 5G Primagram Primextra. 

Also obtained (poor yield) by photo-Fries rearrangement of 2-methoxy-4-meth-ylphenyl benzoate (creosol baizoate) in benzene or ethanol for 4 h (6-7%) [620]. As an historical curiosity, this compound has also been obtained by Fries rearrangement of p-tolyl benzoate with aluminium chloride in the presence of another aromatic compounds, at 150° for 15 min [580] mesitol (83%) 2,6-dimethylphenyl acetate (53%) 2-chloro-4-methylphenyl acetate (20-34%) mesityl acetate (18%). 

Preparation by oxidation of 5-methoxy-2,3-diphenylbenzofuran with chromium trioxide in boiling acetic acid for 30 0 min, followed by saponification of the keto ester formed, the 2-(benzoyloxy)-5-methoxybenzophenone with sodium hydroxide in refluxing ethanol for 1 h [44,682], The same result was obtained by using 5-methoxy-2-(4-methoxyphenyl)-3-phenylbenzofuran or 5-methoxy-2-(4-methylphenyl)-3-phenylbenzofuran [46],... 

Also obtained by oxidation of 6-methoxy-3-(4-methylphenyl)-2-phenylbenzo-furan with chromium trioxide in boiling acetic acid for 30-40 min, followed by saponification of the keto ester so formed [44,46]. 

Also obtained by adding aluminium chloride to a stirred suspension of (4-hydroxy-3-methoxy-5-nitrophenyl) (4-methylphenyl)methanone in ethyl acetate at r.t. under nitrogen, followed by pyridine. The red solution obtained was refluxed for... 

Preparation by UV light irradiation (photo-Fries rearrangement) of 2-methoxy-4-methylphenyl acetate (creosol acetate) in ethanol (68%), in benzene or in hexane (56-55%) [2198]. 

Also obtained by photo-Fries rearrangement of 4-methoxy-3-methylphenyl acetate in ethanol under nitrogen (19%) [3024],... 

Preparation by demethylation of 2-hydroxy-4-methoxy-3-methylphenyl benzyl ketone with hydriodic acid in refluxing acetic anhydride (125-135°) for 2 h (64%) [5319]. 

Preparation by treatment of l-(4-hydroxy-3-methoxy-5-nittophenyl)-2-(4-methylphenyl) ethanone with aluminium chloride in refluxing ethyl acetate/pyridine mixture for 2 h (90-96%) [5193]. 

Obtained by hydrogenolysis of 4,6-bis(benzyloxy)-2-methoxy-3-methylphenyl 4-methoxybenzyl ketone (m.p. 106°) in the presence of Pd/C in acetic acid for 10 min (quantitative yield) [5549],... 

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