Stannous Chloride → 4-(Methylthio)benzene-1,2-diamine

5-(Methylthio)-2-nitroaniline (12.9 g, 70.1 mmol) was dissolved In 475 mL of EtOH with stirring. Tin (II) Chloride (74.0 g, 392 mmol) was added and the reaction was refluxed for 20 h. The reaction was cooled to rt and concentrated in vacuo to a volume of 150 mL. The pH of the solution was adjusted to approximately 10 using concentrated aqueous 3N NaOH. EtOAc (1.5 L) was added and the reaction was filtered through Celite, washing with water and EtOAc. The aqueous layer was separated, then extracted with EtOAc (2×). The combined organic layers were washed with brine, dried over MgSO4, filtered, and concentrated in vacuo to give 10.7 g (99%) of the crude 4-(methylthio)benzene-1,2-diamine as a dark oil. 1H NMR (400 MHz, DMSO-d6) δ 6.52 (m, 1H), 6.44 (m, 1H), 6.37 (m, 1H), 4.49 (br s, 4H), 2.29 (s, 3H).

1. temperaturethe reaction was refluxed for 20 h
2. concentrationconcentrated in vacuo to a volume of 150 mL
3. additionEtOAc (1.5 L) was added
4. filtrationthe reaction was filtered through Celite
5. washwashing with water and EtOAc
6. customThe aqueous layer was separated
7. extractionextracted with EtOAc (2×)
8. washThe combined organic layers were washed with brine
9. dry with materialdried over MgSO4
10. filtrationfiltered
11. concentrationconcentrated in vacuo

ORD record

ord-7430e71f16a4481386f9093788c68647

Source dataset

uspto-grants-2009_11

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US07615643B2