Sodium Hydroxide → HCID 21272039, compound

Temperature

-10 °C

A mixture of 3-chloro-2-(2,2,2-trifluoroethoxy)aniline hydrochloride (20 g, 77 mmol), concentrated HCl (50 mL), and H2O (30 mL) was cooled to -10° C. Sodium nitrite (10.7 g, 155 mmol) dissolved in H2O (30 mL) was added dropwise at a rate to maintain the temperature below -5° C. The solution was stirred for an additional 30 minutes. At the end of this time SnCl2.2H2O (65 g, 289 mmol) in 125 mL of 6N HCl was added dropwise over 1 hour at 0° C. When addition was complete the mixture was allowed to warm to room temperature and stirred an additional 18 hours. The reaction was cooled to -5° C. and 50% NaOH solution was added slowly to pH=13. This alkaline solution was extracted with EtOAc (3×500 mL), and the combined organic layers were washed with brine (2×500 mL), dried (MgSO4), and concentrated to yield an orange oil. This residue was dissolved in 100 mL Et2O and saturated with HCl gas, which resulted in a turbid solution. After the addition of hexane (~10 volumes) and cooling, the 3-chloro-2-(2,2,2-trifluoroethoxy)phenylhydrazine hydrochloride 17.1 g (86%) was collected by filtration as a tan solid, m.p. 158°-165° C.

1. additionwas added dropwise at a rate
2. temperatureto maintain the temperature below -5° C
3. additionWhen addition
4. temperatureto warm to room temperature
5. stirringstirred an additional 18 hours
6. temperatureThe reaction was cooled to -5° C.
7. extractionThis alkaline solution was extracted with EtOAc (3×500 mL)
8. washthe combined organic layers were washed with brine (2×500 mL)
9. dry with materialdried (MgSO4)
10. concentrationconcentrated
11. customto yield an orange oil
12. customresulted in a turbid solution
13. temperaturecooling
14. filtrationthe 3-chloro-2-(2,2,2-trifluoroethoxy)phenylhydrazine hydrochloride 17.1 g (86%) was collected by filtration as a tan solid, m.p. 158°-165° C.

ORD record

ord-1d7a86fd9ebf4414a6949f2f0bcb652a

Source dataset

uspto-grants-1989_03

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US04810699