2,4,6-Trimethylaniline → HCID 12606994, compound

To a stirred ice-cold solution of 2,4,6-trimethylaniline (13.5 g, 100 mmol) in dioxane (50 mL) under argon was added 1.2 equivalents of 1.6 M n-BuLi in hexane drop-wise. The brown mixture was allowed to warm up to room temperature during 1 h. At the end 50 mL (approx. 5 equiv.) of 1,3-dibromopropane was added in one lot and stirred for 42 h. Precipitated LiBr was filtered and the volatiles were removed in vacuo. The residue was partitioned between ethyl acetate (300 mL) and water (3×100 mL). The organic layer was dried (Na2SO4) and evaporated to give the crude product whose purity by LC-MS analysis was 61%. Silica gel chromatography of the crude product with acetone/hexane (1:9) as eluent gave pure bromopropyl aniline (3.3 g) and an impure fraction which upon crystallization from ethyl acetate hexane gave an additional 2.4 g. (22% yield). LC/MS: tR=1.2 min; [M+H]=256, 258 (bromine pattern), 1H NMR (CD3OD) δ 7.07 (2 H, s), 3.59 (2 H, t, Jvic=6.4 Hz), 3.51 (2 H, t, Jvic=8.1 Hz), 2.46 (6 H, s), 2.45–2.38 (2 H, m), 2.30 (3 H, s).

1. filtrationPrecipitated LiBr was filtered
2. customthe volatiles were removed in vacuo
3. customThe residue was partitioned between ethyl acetate (300 mL) and water (3×100 mL)
4. dry with materialThe organic layer was dried (Na2SO4)
5. customevaporated
6. customto give the crude product whose purity by LC-MS analysis

ORD record

ord-977fc55b95834d3b8bd0de911a063b3e

Source dataset

uspto-grants-2007_05

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07211669B2