Sulfamic Acid → HCID 178436115, compound

HRID 2395023Notes

Reaction equation

HRID 2395023 reaction equation
[CH2:1]([O:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=1[CH:15]=[CH:16][C:17]1[CH:24]=[CH:23][C:20]([C:21]#[N:22])=[CH:19][CH:18]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C([Sn]([N:38]=[N+:39]=[N-:40])(CCCC)CCCC)CCC.N([O-])=O.[Na+].S(=O)(=O)(O)N>C1(C)C=CC=CC=1>[CH2:1]([O:8][C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][C:10]=1[CH:15]=[CH:16][C:17]1[CH:18]=[CH:19][C:20]([C:21]2[NH:40][N:39]=[N:38][N:22]=2)=[CH:23][CH:24]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 4

HCID 5987Sulfamic AcidHCID 4984872Tributyltin azideHCID 23668193Sodium NitriteHCID 53959650HCID 53959650, compound

Product 1

HCID 178436115HCID 178436115, compound

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A mixture of 4-[2-(2-benzyloxyphenyl)ethenyl]-benzonitrile as a mixture of isomers (7.88 g) and tri-n-butyltin azide (20.03 ml, 2.53M solution in toluene) in toluene 100 ml was heated at reflux for 66 hours. The mixture was cooled (ice bath) and added dropwise to excess sodium nitrite and stirred for 30 minutes. Sulphamic acid (9 g) was added and the mixture left to stand at 5° C. for 18 hours. The resulting yellow precipitate (9.7 g) was filtered off, dried and mixed with potassium carbonate (7.56 g) in DMF (20 ml) and stirred for 10 minutes. Pivaloyloxymethyl chloride (4.78 ml) was added to the mixture and it was stirred for 18 hours, diluted with ethyl acetate (200 ml), and washed with 1M HCl (100 ml), sodium bicarbonate (100 ml) and brine (100 ml), dried (magnesium sulphate), filtered and evaporated. The residue was purified by subjecting to chromatography on silica gel using methanol : dichloromethane (0:100 to 30:70 gradient) as eluant. There was thus obtained N-2-(pivaloyloxymethyl)-5-{-4-[2-(2-benzyloxyphenyl)ethenyl]-phenyl}tetrazole (7.64 g) and N-1-(pivaloyloxymethyl)-5-{-4-[2-(2-benzyloxyphenyl)ethenyl]-phenyl}tetrazole (1.67 g).

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 66 hours
  3. temperatureThe mixture was cooled (ice bath)
  4. waitthe mixture left
  5. waitto stand at 5° C. for 18 hours
  6. filtrationThe resulting yellow precipitate (9.7 g) was filtered off
  7. customdried
  8. additionmixed with potassium carbonate (7.56 g) in DMF (20 ml)
  9. stirringstirred for 10 minutes
  10. additionPivaloyloxymethyl chloride (4.78 ml) was added to the mixture and it
  11. stirringwas stirred for 18 hours
  12. additiondiluted with ethyl acetate (200 ml)
  13. washwashed with 1M HCl (100 ml), sodium bicarbonate (100 ml) and brine (100 ml)
  14. dry with materialdried (magnesium sulphate)
  15. filtrationfiltered
  16. customevaporated
  17. customThe residue was purified

Sources & evidence

ORD record
ord-53b15b17535447928c97e78bd2b904b6
Source dataset
uspto-grants-1998_09
Patent number
US05811459

Reaction notes

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