Sulfuric Acid → 1-(1H-1,2,4-triazol-1-ylmethyl)tricyclo[3.3.1.03,7]nonan-3-amine

HRID 1015533Notes

Reaction equation

HRID 1015533 reaction equation
[N:1]1([CH2:6][C:7]23[CH2:15][CH:11]4[CH2:12][CH:13]([CH2:14]2)[C:9](C(O)=O)([CH2:10]4)[CH2:8]3)[CH:5]=[N:4][CH:3]=[N:2]1.OS(O)(=O)=O.[N-:24]=[N+]=[N-].[Na+]>C(Cl)(Cl)Cl.O>[N:1]1([CH2:6][C:7]23[CH2:15][CH:11]4[CH2:12][CH:13]([CH2:14]2)[C:9]([NH2:24])([CH2:10]4)[CH2:8]3)[CH:5]=[N:4][CH:3]=[N:2]1

Participants

6

Reactant 3

HCID 1118Sulfuric AcidHCID 33557Sodium AzideHCID 673003701-(1H-1,2,4-triazol-1-ylmethyl)tricyclo[3.3.1.03,7]nonane-3-carboxylic acid

Product 1

HCID 670178971-(1H-1,2,4-triazol-1-ylmethyl)tricyclo[3.3.1.03,7]nonan-3-amineYield 70.5%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6212ChloroformSolvent

Procedure

To a stirred suspension of 1-(1H-1,2,4-triazol-1-ylmethyl)tricyclo[3.3.1.03,7]nonane-3-carboxylic acid (0.13 g, 0.52 mmol) obtained in step III, in CHCl3 (2.6 mL) was added conc. H2SO4 (0.25 mL, 5.2 mmol). To this homogenous solution NaN3 (0.1 g, 1.56 mmol) was added in portions over a period of 30 minutes, while keeping the temperature of the reaction below 40° C. After stirring the reaction mixture for 2 h at r.t., the reaction mixture was cooled to ice bath temperature, diluted with water and extracted with EtOAc. The aqueous layer was basified by adding 50% aq. NaOH solution and extraction with CHCl3. The combined organic layer was washed with brine, dried over Na2SO4 and the solvent was removed under reduced pressure to obtain 1-(1H-1,2,4-triazol-1-ylmethyl)tricyclo[3.3.1.03,7]nonan-3-amine (0.08 g) as a viscous liquid in 70% yield. m/z (M+1) 219; 1H NMR (CDCl3) 300 MHz δ 7.98 (s, 1H), 7.93 (s, 1H), 4.07 (s, 2H), 2.38-2.30 (m, 1H), 2.06-1.98 (m, 1H), 1.96-1.80 (m, 2H), 1.72-1.57 (m, 4H), 1.55-1.36 (m, 4H).

Workup

  1. customthe temperature of the reaction below 40° C
  2. temperaturethe reaction mixture was cooled to ice bath temperature
  3. extractionextracted with EtOAc
  4. additionby adding
  5. extraction50% aq. NaOH solution and extraction with CHCl3
  6. washThe combined organic layer was washed with brine
  7. dry with materialdried over Na2SO4
  8. customthe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-b20a61ff27854a3b880e4cd157c3dd03
Source dataset
uspto-grants-2011_07
Patent number
US07985759B2

Reaction notes

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