Stannous Chloride → 4-Chloro-3-(pyrid-3-yl)aniline

HRID 586304Notes

Reaction equation

HRID 586304 reaction equation
[Sn](Cl)Cl.[Cl:4][C:5]1[CH:10]=[CH:9][C:8]([N+:11]([O-])=O)=[CH:7][C:6]=1[C:14]1[CH:15]=[N:16][CH:17]=[CH:18][CH:19]=1>C(O)C.O1CCOCC1>[Cl:4][C:5]1[CH:10]=[CH:9][C:8]([NH2:11])=[CH:7][C:6]=1[C:14]1[CH:15]=[N:16][CH:17]=[CH:18][CH:19]=1

Participants

5

Reactant 2

HCID 24479Stannous ChlorideHCID 223295393-(2-Chloro-5-nitrophenyl)pyridine

Product 1

HCID 121019664-Chloro-3-(pyrid-3-yl)anilineYield 87%

Reagents, catalysts & solvents 2

HCID 702EthanolSolventHCID 312751,4-DioxaneSolvent

Procedure

Tin(II) chloride (11.87 g, 62.6 mmol) was added portionwise over 5 min to a stirred mixture of 3-(2-chloro-5-nitrophenyl)pyridine (3.53 g, 15.1 mmol) in ethanol (100 ml) and 1,4-dioxane (100 ml) at 0° C. The mixture was then stirred overnight, gradually warming to room temperature, and then concentrated under reduced pressure. 20% Aqueous ammonia solution (200 ml) and ethanol (300 ml) were added and again the mixture concentrated under reduced pressure. Ethyl acetate (300 ml) was added and the mixture heated to reflux, the solids were filtered off and the process repeated twice more. The combined organic filtrates were concentrated under reduced pressure to yield the title compound (2.69 g, 87%): 1H NMR (360 MHz, CDCl3) δ 6.65-6.70 (2H, m), 7.26 (1H, dt, J 8.5, 1.1 Hz), 7.33 (1H, dd, J 7.8, 4.8 Hz), 7.77 (1H, dt, J 7.8, 1.9 Hz), 8.59 (1H, dd, J 4.8, 1.6 Hz), 8.66 (1H, d, J 1.8 Hz); MS (ES+) m/z 205, 207 (3:1) [M+H]+.

Workup

  1. concentrationconcentrated under reduced pressure
  2. addition20% Aqueous ammonia solution (200 ml) and ethanol (300 ml) were added
  3. concentrationagain the mixture concentrated under reduced pressure
  4. additionEthyl acetate (300 ml) was added
  5. temperaturethe mixture heated
  6. temperatureto reflux
  7. filtrationthe solids were filtered off
  8. concentrationThe combined organic filtrates were concentrated under reduced pressure

Sources & evidence

ORD record
ord-ccd9223cdb8145238cbd0f14d5b0d6d7
Source dataset
uspto-grants-2005_08
Patent number
US06936608B2

Reaction notes

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