Methyl nitrite → HCID 57325265, compound

Temperature

2.5 °C

In general analogy to the process described under 3.1, 59 g (0.48 mol) of thiophene-3-acetonitril are placed in a sulfonation flask and are charged with 19.2 g (0.48 mol) of sodium hydroxide, dissolved in 200 ml of methanol. 0.48 mol of gaseous methyl nitrite is introduced, with stirring, into this solution at 0-5° C. over 4.5 hours. The ice bath is then removed and the brown solution is stirred overnight at room temperature. The methanol is distilled off on a rotary evaporator and the resulting orange residue is charged with water and ethyl acetate. The aqueous phase is separated, washed twice with ethyl acetate and acidified with conc. HCl. The aqueous phase is extracted twice with ethyl acetate, the extracts are washed with water and dried over magnesium sulfate. After fitration, the solvent is distilled off and a brown solid is obtained which is then recrystallised from toluene, giving 28.6 g (39% of theory) of α-hydroxyiminothiophene-3-acetonitrile as a beige solid having a melting point of 96-106° C. The 1H-NMR spectrum is consistent with the proposed structure.

1. customare placed in a sulfonation flask
2. customThe ice bath is then removed
3. stirringthe brown solution is stirred overnight at room temperature
4. distillationThe methanol is distilled off on a rotary evaporator
5. additionthe resulting orange residue is charged with water and ethyl acetate
6. customThe aqueous phase is separated
7. washwashed twice with ethyl acetate
8. extractionThe aqueous phase is extracted twice with ethyl acetate
9. washthe extracts are washed with water
10. dry with materialdried over magnesium sulfate
11. distillationAfter fitration, the solvent is distilled off
12. customa brown solid is obtained which
13. customis then recrystallised from toluene

ORD record

ord-747aeb734a714d87b1aad6b5795353cd

Source dataset

uspto-grants-2004_08

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06770420B2