Tributyltin azide → HCID 178477998, compound

HRID 639412Notes

Reaction equation

HRID 639412 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:12]([C:13]3[CH:18]=[CH:17][N:16]=[C:15]([NH:19][C:20]4[CH:27]=[CH:26][C:23]([C:24]#[N:25])=[CH:22][CH:21]=4)[N:14]=3)=[CH:11][NH:10][N:9]=2)=[CH:4][CH:3]=1.[N:28]([Sn](CCCC)(CCCC)CCCC)=[N+:29]=[N-:30]>CC1C=CC=CC=1C>[Cl:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]2[C:12]([C:13]3[CH:18]=[CH:17][N:16]=[C:15]([NH:19][C:20]4[CH:27]=[CH:26][C:23]([C:24]5[NH:30][N:29]=[N:28][N:25]=5)=[CH:22][CH:21]=4)[N:14]=3)=[CH:11][NH:10][N:9]=2)=[CH:6][CH:7]=1

Participants

4

Reactant 2

HCID 4984872Tributyltin azide2×HCID 178510035HCID 178510035, compound2×

Product 1

HCID 178477998HCID 178477998, compound

Reagents, catalysts & solvents 1

HCID 7237O-XyleneSolvent

Conditions

Temperature
160 °C

Procedure

The title compound is prepared starting from 4-{4-[3-(4-chloro-phenyl)-1H-pyrazol-4-yl]-pyrimidin-2-ylamino}-benzonitrile. 4-{4-[3-(4-chloro-phenyl)-1H-pyrazol-4-yl]-pyrimidin-2-ylamino}-benzonitrile (0.932 g; 2.5 mMol) is suspended in o-xylene (10 mL) and treated at rt with azidotributyltin (1.66 g; 1.37 mL; 5 mMol). After stirring the yellow suspension at 160° C. for 117 h the reaction mixture is filtered off without cooling and the crystals are washed with o-xylene. Since the reaction is still incomplete, the crude product is resuspended in o-xylene (20 mL) and treated at rt with azidotributyltin (1.37 mL; 5 mMol). After stirring the yellow suspension at 160° C. for 117 h the reaction mixture is filtered off without cooling and the crystals are washed with o-xylene. The crude product is suspended in methanol (1.00 mL), refluxed and filtered without cooling. The crude product is acidified with 4N HCL/methanol and extracted with ethyl acetate. The aqueous layer is basified with 4N NaOH (ca. pH 12) and extracted with ethyl acetate. Upon this treatment, the product precipitates from the aqueous layer and is filtered off to obtain the title compound.

Workup

  1. customThe title compound is prepared
  2. filtrationis filtered off
  3. temperaturewithout cooling
  4. washthe crystals are washed with o-xylene
  5. stirringAfter stirring the yellow suspension at 160° C. for 117 h the reaction mixture
  6. filtrationis filtered off
  7. temperaturewithout cooling
  8. washthe crystals are washed with o-xylene
  9. temperaturerefluxed
  10. filtrationfiltered
  11. temperaturewithout cooling
  12. extractionextracted with ethyl acetate
  13. extractionextracted with ethyl acetate
  14. customUpon this treatment, the product precipitates from the aqueous layer
  15. filtrationis filtered off

Sources & evidence

ORD record
ord-5ccc78d57a684abda84c133218a52e85
Source dataset
uspto-grants-2010_04
Patent number
US07691855B2

Reaction notes

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