2-phenoxyaniline

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 2-Phenoxyaniline (5.57 g) and triethylamine (4.2 mL) were dissolved in 100 mL of 1,2-dichloroethane. Triphosgene (Cl3COC(=O)OCCl3, 2.97 g) was added and a precipitate formed. The mixture was heated to reflux and the solid redissolved. After 5.5 h, the solution was cooled and 1.6 mL of methyl hydrazine was added and a new precipitate formed. The mixture was stirred at room temperature overnight. The solvent was removed and the residue was partitioned between ethyl acetate and 1N aqueous HCl solution. The organic phases were dried (MgSO4), filtered, and concentrated under reduced pressure. The residue was purified by flash chromatography (1:1 hexane:ethyl acetate as eluant). The second-least polar component was collected, the eluant was removed under reduced pressure, and the residue was triturated with hexane to afford 3.86 g (50%) of the title compound of Step A, m.p. 117-119° C. a precipitate formed The mixture was heated to reflux the solid redissolved the solution was cooled a new precipitate formed The solvent was removed the residue was partitioned between ethyl acetate and 1N aqueous HCl solution The organic phases were dried (MgSO4) filtered concentrated under reduced pressure The residue was purified by flash chromatography (1:1 hexane:ethyl acetate as eluant) The second-least polar component was collected the eluant was removed under reduced pressure the residue was triturated with hexane

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 1.96 g (0.011 mol) of thiocarbonyl diimidazole were added to a solution of 1.85 g (0.01 mol) of 2-phenoxyaniline in 50 ml of THF and the mixture was stirred at room temperature for 4 hours, giving, after removal of the solvent by distillation, the compound as a brown amorphous product. giving after removal of the solvent by distillation

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-Dimethylamino-3-phenoxybenzenediazonium hexafluoroarsenate was also prepared by the following route: o-phenoxyaniline was methylated with dimethyl sulfate to N,N-dimethyl-o-phenoxyaniline, m. 34°-5°, which was coupled with 2,5-dichlorobenzenediazonium chloride to give 4-(2,5-dichlorophenylazo)-N,N-dimethyl-2-phenoxyaniline, m. 93°-4°. This was then reduced catalytically to N1,N1 -dimethyl-2-phenoxy-p-phenylenediamine, m. 76°-6°, which was diazotized as above. 34°-5°, which

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: 4-Dimethylamino-3-phenoxybenzenediazonium hexafluoroarsenate was also prepared by the following route: o-phenoxyaniline was methylated with dimethyl sulfate to N,N-dimethyl-o-phenoxyaniline, m. 34°-5°, which was coupled with 2,5-dichlorobenzenediazonium chloride to give 4-(2,5-dichlorophenylazo)-N,N-dimethyl-2-phenoxyaniline, m. 93°-4°. This was then reduced catalytically to N1,N1 -dimethyl-2-phenoxy-p-phenylenediamine, m. 76°-6°, which was diazotized as above. 34°-5°, which

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: o-Nitrophenyl phenyl ether was reduced catalytically to o-phenoxyaniline, m. 43°-5°, which was acetylated to 2'-phenoxyacetanilide, m. 82°-4°. Yields from both reactions were essentially quantitative. The 2'-phenoxy-acetanilide was dissolved in acetic acid and treated at 60°-80° with red fuming nitric acid to produce a 60-70% yield of 4'-nitro-2'-phenoxy-acetanilide, m. 176°-183°. This was deacetylated by refluxing with methanolic hydrochloric acid to 4-nitro-2-phenoxyaniline, m. 116°-8°. The yield was 99% of theoretical. 43°-5°, which 82°-4° Yields from both reactions