Reaction #1885007

Reaction equation

tin chloride

4-n-butylaniline

Sodium nitrite

→

solid

Yield 66.0%

p-Butylphenylhydrazine

Yield 66.0%

Solvents

hydrochloric acid

hydrochloric acid

water

Conditions

Workup

1. 1
   Temperaturecooled
2. 2
   workup.ADDITIONwas added slowly
3. 3
   workup.STIRRINGthe resulting suspension was stirred at 0° C. for 3 h
4. 4
   FiltrationThe solid was filtered
5. 5
   workup.DISSOLUTIONdissolved in a mixture of 40% potassium hydroxide solution (200 mL) and ethyl acetate (200 mL)
6. 6
   OtherThe organic layer was separated
7. 7
   Extractionthe aqueous layer was further extracted with ethyl acetate
8. 8
   WashThe combined organic extracts were washed with 10% hydrochloric acid (120 mL)
9. 9
   Filtrationthe solid was filtered
10. 10
    OtherThe organic layer was separated
11. 11
    Dryingdried over Na2SO4
12. 12
    Otherthe solvent was evaporated
13. 13
    OtherThe resulting solid was recrystallized from ethanol

Procedure

Sodium nitrite (11.74 g, 0.17 mol) in water (50 mL) was added over 30 min to an ice-cooled and stirred suspension of 4-n-butylaniline (24.30 g, 0.16 mol) in 6 N hydrochloric acid (190 mL). After an additional 15 min, a suspension of tin chloride dehydrate (108.3 g, 0.4 mol) in 6 N hydrochloric acid (190 mL) was added slowly, and the resulting suspension was stirred at 0° C. for 3 h. The solid was filtered and dissolved in a mixture of 40% potassium hydroxide solution (200 mL) and ethyl acetate (200 mL). The organic layer was separated and the aqueous layer was further extracted with ethyl acetate. The combined organic extracts were washed with 10% hydrochloric acid (120 mL), a solid started to develop in the organic layer. After cooled it to 0° C., the solid was filtered. The organic layer was separated, dried over Na2SO4, and the solvent was evaporated. The resulting solid was recrystallized from ethanol to afford a white solid (17.35 g, 54%). 1H NMR (300 MHz, DMSO-d6): δ 10.18 (s, 3H), 7.10 (d, 2H, J=8.4 Hz), 6.92 (d, 2H, J=8.7 Hz), 2.51 (t, 2H, J=7.5 Hz), 1.50 (pentet, 2H, J=7.5 Hz), 1.27 (sextet, 2H, J=7.8 Hz), 0.88 (t, 3H, J=7.5 Hz).

Source