Tributyltin azide → HCID 15725753, compound

HRID 982083Notes

Reaction equation

HRID 982083 reaction equation
[C:1]1([C:7]2[C:11]([C:12]3[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=3)=[C:10]([C:18]3[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=3)[N:9]([CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][C:32]#[N:33])[N:8]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C([Sn]([N:47]=[N+:48]=[N-:49])(CCCC)CCCC)CCC>C(OCC)(=O)C>[C:1]1([C:7]2[C:11]([C:12]3[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=3)=[C:10]([C:18]3[CH:19]=[CH:20][CH:21]=[CH:22][CH:23]=3)[N:9]([CH2:24][CH2:25][CH2:26][CH2:27][CH2:28][CH2:29][CH2:30][CH2:31][C:32]3[N:47]=[N:48][NH:49][N:33]=3)[N:8]=2)[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=1

Participants

4

Reactant 2

HCID 4984872Tributyltin azideHCID 15725752HCID 15725752, compound

Product 1

HCID 15725753HCID 15725753, compoundYield 73%

Reagents, catalysts & solvents 1

HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
140 °C

Procedure

A mixture of 3,4,5-triphenyl-lH-pyrazole-1-nonanenitrile (1.25 g, 2.9 mmol) and tri-n-butyltin azide (1.15 g, 3.5 mmol) was heated with stirring at 140° C. under an atmosphere of nitrogen. After 2.5 hours, the mixture was cooled to room temperature, diluted with ethyl acetate and washed with 0.5 N HCl (3 x) and saturated sodium chloride solution before being dried and concentrated in vacuo. The residual oil was chromatographed on a column of silica gel using first a mixture of ethyl acetate and hexane (1:1) and subsequently methanol/chloroform (1:9) as eluent. The recovered oil was dissolved in CH2Cl2 and stirred with a concentrated aqueous solution of potassium floride. After 24 hours, the layers were separated and the aqueous layer extracted with dichloromethane. The organic extracts were dried over sodium sulfate and concentrated in vacuo to give an oil that solidified. Recrystallization from a mixture of hexane and dichloromethane (2:1) afforded the title compound (1.00 g, 73%); m.p.=158°-160° C. MS(CI): m/e =477 (MH+).

Workup

  1. temperaturewas heated
  2. temperaturethe mixture was cooled to room temperature
  3. washwashed with 0.5 N HCl (3 x) and saturated sodium chloride solution
  4. custombefore being dried
  5. concentrationconcentrated in vacuo
  6. customThe residual oil was chromatographed on a column of silica gel using first
  7. additiona mixture of ethyl acetate and hexane (1:1) and subsequently methanol/chloroform (1:9) as eluent
  8. dissolutionThe recovered oil was dissolved in CH2Cl2
  9. stirringstirred with a concentrated aqueous solution of potassium floride
  10. waitAfter 24 hours
  11. customthe layers were separated
  12. extractionthe aqueous layer extracted with dichloromethane
  13. dry with materialThe organic extracts were dried over sodium sulfate
  14. concentrationconcentrated in vacuo
  15. customto give an oil that solidified
  16. customRecrystallization
  17. additionfrom a mixture of hexane and dichloromethane (2:1)

Sources & evidence

ORD record
ord-fb8a4c47a9744c868c578db1d302b069
Source dataset
uspto-grants-1991_02
Patent number
US04994482

Reaction notes

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