Methyl iodide → 1-(3-Bromophenyl)-1-methylhydrazine

To a solution of 3-bromophenylhydrazine hydrochloride (15 g, 67 mmol) in anhydrous THF (360 mL) was added LiHMDS (1.0 M solution in THF, 127 mL, 127 mmol) dropwise over a period of 1 h at 0° C. The reaction mixture was stirred for 30 min while warming to room temperature. The flask was recooled to −78° C., and MeI (4.1 mL, 67 mmol) was added. The reaction mixture was stirred for 2 h at 0° C. and then was quenched with water (600 mL). The aqueous layer was extracted with methylene chloride (3×200 mL), and the combined organic layers were dried over sodium sulfate, filtered, and concentrated under reduced pressure. Purification by flash column chromatography (silica gel, hexanes/EtOAc, 60:40) gave the title compound (10.2 g, 76%) as yellow oil: 1H NMR (300 MHz, CDCl3) δ 7.18 (t, J=3.5 Hz, 1H), 7.08 (t, J=13.5 Hz, 1H), 6.91-6.86 (m, 2H), 3.69 (br s, 2H), 3.11 (s, 3H).

1. customwas recooled to −78° C.
2. stirringThe reaction mixture was stirred for 2 h at 0° C.
3. customwas quenched with water (600 mL)
4. extractionThe aqueous layer was extracted with methylene chloride (3×200 mL)
5. dry with materialthe combined organic layers were dried over sodium sulfate
6. filtrationfiltered
7. concentrationconcentrated under reduced pressure
8. customPurification by flash column chromatography (silica gel, hexanes/EtOAc, 60:40)

ORD record

ord-8169869bd53243db86f23821d31cc6b3

Source dataset

uspto-grants-2015_07

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09073925B2