A New Practical One-Pot Conversion of Phenols to Anilines

Abstract

A novel one-pot synthesis of anilines from phenols was developed. Using this methodology, anilines are produced in good yield (86%) by a reaction of phenols with 2-bromo-2-methylpropionamide and NaOH in DMA via Smiles rearrangement. Phenols, which are substituted electron-withdrawing groups, are more reactive for Smiles rearrangement. Thiophenols are also converted to anilines. The process is a convenient, safe, and inexpensive method for large-scale preparation of anilines. [reaction: see text]

The Application of the Schmidt Reaction and Beckmann Rearrangement to the Synthesis of Bicyclic Lactams: Some Mechanistic Considerations

“…[77] 6-Amino-1-tetralone 60 can be accessed in many ways and the use of commercially available 6-hydroxy-1-tetralone 61 in the one-pot Smiles rearrangement has been recently reported (Scheme 2). [78,79] Addition of 2-bromo-2-methylpropanamide to a mixture of 60 and sodium hydroxide in N,N-dimethylacetamide resulted in the formation of the intermediate 62. Further addition of excess sodium hydroxide resulted in the formation of the amide 63 through the Smiles rearrangement of 62.…”

Keto‐benzo[h]‐Coumarin‐Based Near‐Infrared Dyes with Large Stokes Shifts for Bioimaging Applications

“…Compound 1 was preparedi ng ood yield from the reaction of 6-hydroxy-3,4-dihydro-1(2 H)-naphthalenone with 2-bromo-2-methylpropionamide and NaOH in N,N-dimethylacetamide (DMA) through aS miles rearrangement. [15] The dimethylation of compound 1 with MeI and K 2 CO 3 in DMF at 45 8Cp roduced compound 2. [16] An aldehyde group was introduced onto the skeleton of compound 2 and subsequentoxidation with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ)a fforded compound 3.C ondensation of compound 3 with ethyl acetoacetate in the presence of morpholine in anhydrous EtOH produced k-BC as ar ed-browns olid in 76 %y ield.…”

“…Compound 1 was synthesized according to am odified literature procedure. [15] NaOH (720 mg, 18 mmol) was added to as olution of 6-hydroxy-3,4-dihydro-1(2 H)naphthalenone (974 mg, 6mmol) in DMA (10 mL), which was stirred at RT for 1h.2 -Bromo-2-methylpropanamide (2.98 g, 18 mmol) was added and the solution was stirred at RT for 5h.T hen, NaOH (2.16 g, 54 mmol) was added and the solution was stirred at 50 8Cf or 1h.N ext, water (10 mL) was added, the solution was heated at reflux for 1h,a nd as econd batch of water (10 mL) was added. After cooling to RT,t he resulting precipitate was collected and washed with plenty of water.T he sample was dried and purified by column chromatography on silica gel (petroleum ether/EtOAc, 6:1v /v) to give compound 1 as an off-white powder (534 mg, 55 %y ield).…”

Reactivity of 2,1‐Benzisoxazole in Palladium‐Catalyzed Direct Arylation with Aryl Bromides

“…(2-Aminophenyl)(phenyl)methanone (28) [17] (2-Aminophenyl)(naphthalen-2-yl)methanone( 29) [18] From 3-(naphthalen-2-yl)benzo [ (2-Aminophenyl)(naphthalen-1-yl)methanone( 30) [19] From 3-(naphthalen- (2-Aminophenyl)(2-(trifluoromethyl)phenyl)methanone (32) [20] …”