Acetic Acid → 1-[(1,1-Dioxidoisothiazolidin-2-yl)methyl]tricyclo[3.3.1.03,7]nonane-3-carboxylicacid

HRID 1015539Notes

Reaction equation

HRID 1015539 reaction equation
[OH-].[Na+].BrBr.Br[O-].[O:7]=[S:8]1(=[O:26])[CH2:12][CH2:11][CH2:10][N:9]1[CH2:13][C:14]12[CH2:22][CH:18]3[CH2:19][CH:20]([CH2:21]1)[C:16]([C:23](=[O:25])C)([CH2:17]3)[CH2:15]2.CC(O)=[O:29]>O1CCOCC1.O>[O:26]=[S:8]1(=[O:7])[CH2:12][CH2:11][CH2:10][N:9]1[CH2:13][C:14]12[CH2:22][CH:18]3[CH2:19][CH:20]([CH2:21]1)[C:16]([C:23]([OH:25])=[O:29])([CH2:17]3)[CH2:15]2

Participants

8

Reactant 5

HCID 176Acetic AcidHCID 14798Sodium HydroxideHCID 24408BromineHCID 5460626HypobromiteHCID 670178461-{1-[(1,1-Dioxido isothiazolidin-2-yl)methyl]tricyclo[3.3.1.03,7]non-3-yl}ethanone

Product 1

HCID 673003471-[(1,1-Dioxidoisothiazolidin-2-yl)methyl]tricyclo[3.3.1.03,7]nonane-3-carboxylicacidYield 70.4%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 312751,4-DioxaneSolvent2×

Procedure

To a stirred mixture of NaOH (1.2 g, 27.8 mmol), H2O (8 mL), and 1,4 dioxane (1 mL) at ice bath temperature was added Br2 (0.56 mL, 10.4 mmol) and the mixture was stirred for 15 minutes. The resulting hypobromite solution was added drop-wise to a stirred solution of the compound obtained in step II (0.55 g, 1.85 mmol) in 1,4-dioxane (3 mL) at ice bath temperature. The reaction mixture was gradually warmed to room temperature and after stirring for 1 h; it was cooled to ice bath temperature and quenched by adding AcOH (1.7 mL, 27.8 mmol). The reaction mixture was diluted with water and extracted with EtOAc. 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)methyl]tricyclo[3.3.1.03,7]nonane-3-carboxylicacid (0.39 g) in 70% yield. m/z (M−1) 298; 1H NMR (CDCl3) 300 MHz δ 3.32 (t, J=6.8 Hz, 2H), 3.10 (t, J=7.4 Hz, 2H), 2.95 (s, 2H), 2.80-2.73 (m, 1H), 2.43-2.41 (m, 1H), 2.40-2.29 (m, 2H), 2.10-2.0 (m, 2H), 1.82-1.72 (m, 3H), 1.67-1.54 (m, 4H), 1.46 (dd, J=3.2, 11.0 Hz, 1H).

Workup

  1. stirringafter stirring for 1 h
  2. temperatureit was cooled to ice bath temperature
  3. customquenched
  4. extractionextracted with EtOAc
  5. washThe combined organic layer was washed with brine
  6. dry with materialdried over Na2SO4
  7. customthe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-7356293eab98487fb94e5a7b43936d3f
Source dataset
uspto-grants-2011_07
Patent number
US07985759B2

Reaction notes

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