Aniline → 6-bromo-N-phenylnaphthalen-2-amine

HRID 1871157Notes

Reaction equation

[Br:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[CH:8]=[C:7](O)[CH:6]=[CH:5]2.[NH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1.O.C1(C)C=CC(S(O)(=O)=O)=CC=1.C([O-])(=O)C.[Na+]>C(O)C.C1(C)C(C)=CC=CC=1>[C:14]1([NH:13][C:7]2[CH:6]=[CH:5][C:4]3[C:9](=[CH:10][CH:11]=[C:2]([Br:1])[CH:3]=3)[CH:8]=2)[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1

Participants

Conditions

Temperature: 85 °C

Procedure

Xylene was distilled from a mixture of 6-bromo-2-naphthol (16.4 g., 0.0735 mol.), aniline (25 ml, 0.274 mol.), xylene (25 ml), and p-toluene sulfonic acid monohydrate (2.7 g., 0.014 mol.) until the reaction temperature reached 190° C. The mixture was held at this temperature for 5 hours, and then cooled to 85° C. Sodium acetate (3.7 g.) and ethanol (100 ml) were added and the mixture was heated to reflux. The solution was cooled to 5° C. and the resulting slurry was filtered. The solids were washed with cold ethanol (50 ml). The air-dried solids (19.5 g.) were reslurried in hot water (150 ml) and filtered to give a gray solid, 19.3 g, 88% yield, m.p. 126.2-128.3° C. Two successive recrystalizations from heptane-ethyl acetate (19:1) gave a sample for analysis, m.p. 131-133° C. Mass Spec: m/z 297, 299 (M+). Analysis: Calculated for C16H12NBr: C, 64.45; H, 4.06; N, 4.70, Br, 26.80. Found: C, 64.36; H, 4.02; N, 4.67; Br, 27.04.

Workup

customreached 190° C
temperaturethe mixture was heated to reflux
temperatureThe solution was cooled to 5° C.
filtrationthe resulting slurry was filtered
washThe solids were washed with cold ethanol (50 ml)
filtrationfiltered
customto give a gray solid, 19.3 g, 88% yield, m.p. 126.2-128.3° C
customTwo successive recrystalizations from heptane-ethyl acetate (19:1)
customgave a sample for analysis, m.p. 131-133° C

Sources & evidence

ORD record: ord-5c37a5dc0c3942278fde2b4aeba32a46
Source dataset: uspto-grants-2000_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US06100405

Reaction notes

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