Sulfuric Acid → 1-(1,1-Dioxidoisothiazolidin-2-yl)tricyclo[3.3.1.03,7]nonan-3-amine

HRID 1015527Notes

Reaction equation

HRID 1015527 reaction equation
[O:1]=[S:2]1(=[O:19])[CH2:6][CH2:5][CH2:4][N:3]1[C:7]12[CH2:15][CH:11]3[CH2:12][CH:13]([CH2:14]1)[C:9](C(O)=O)([CH2:10]3)[CH2:8]2.OS(O)(=O)=O.[N-:25]=[N+]=[N-].[Na+]>C(Cl)(Cl)Cl.O>[O:1]=[S:2]1(=[O:19])[CH2:6][CH2:5][CH2:4][N:3]1[C:7]12[CH2:15][CH:11]3[CH2:12][CH:13]([CH2:14]1)[C:9]([NH2:25])([CH2:10]3)[CH2:8]2

Participants

6

Reactant 3

HCID 1118Sulfuric AcidHCID 33557Sodium AzideHCID 866427391-(1,1-Dioxido iso thiazolidin-2-yl)tricyclo[3.3.1.03,7]nonane-3-carboxylic acid

Product 1

HCID 593749741-(1,1-Dioxidoisothiazolidin-2-yl)tricyclo[3.3.1.03,7]nonan-3-amineYield 66.3%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6212ChloroformSolvent

Conditions

Temperature
45 °C

Procedure

To a stirred solution of the acid obtained in step II (0.29 g, 1.0 mmol) in CHCl3 (5 mL) at room temperature was added conc. H2SO4 (0.53 mL, 10 mmol) followed by the addition NaN3 (0.2 g, 3.0 mmol) in portions over a period of 30 min; while maintaining the temperature below 40° C. The reaction mixture was warmed to 45° C. and stirred for 2 h. The reaction mixture was cooled to ice bath temperature, diluted with water and extracted with EtOAc. The aqueous layer was basified by adding a 50% NaOH solution and extracted with CHCl3. The combined organic layer was washed with brine, dried over Na2SO4 and the solvent was removed under reduced pressure to obtain 1-(1,1-dioxidoisothiazolidin-2-yl)tricyclo[3.3.1.03,7]nonan-3-amine as a viscous liquid (0.17 g) in 66% yield. m/z (M+1) 257; 1H NMR (CDCl3) 300 MHz δ 3.36 (t, J=6.6 Hz, 2H), 3.15 (t, J=7.5 Hz, 2H), 2.40-2.24 (m, 4H), 2.18 (dd, J=3.0, 10.4 Hz, 1H), 2.13-1.83 (m, 6H), 1.76 (dd, (J=2.4, 10.8 Hz, 1H), 1.65-1.58 (m, 1H), 1.48 (dd, J=2.4, 10.8 Hz, 1H).

Workup

  1. temperaturewhile maintaining the temperature below 40° C
  2. temperatureThe reaction mixture was cooled to ice bath temperature
  3. extractionextracted with EtOAc
  4. additionby adding a 50% NaOH solution
  5. extractionextracted 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-aad493a8acbd4d7e8649d8495fe32469
Source dataset
uspto-grants-2011_07
Patent number
US07985759B2

Reaction notes

Loading…