Acetic Acid → 1-(1H-1,2,4-triazol-1-ylmethyl)tricyclo[3.3.1.03,7]nonane-3-carboxylic acid

HRID 1015532Notes

Reaction equation

HRID 1015532 reaction equation
[OH-].[Na+].BrBr.Br[O-].[N:7]1([CH2:12][C:13]23[CH2:21][CH:17]4[CH2:18][CH:19]([CH2:20]2)[C:15]([C:22](=[O:24])C)([CH2:16]4)[CH2:14]3)[CH:11]=[N:10][CH:9]=[N:8]1.CC(O)=[O:27]>O1CCOCC1.O>[N:7]1([CH2:12][C:13]23[CH2:21][CH:17]4[CH2:18][CH:19]([CH2:20]2)[C:15]([C:22]([OH:24])=[O:27])([CH2:16]4)[CH2:14]3)[CH:11]=[N:10][CH:9]=[N:8]1

Participants

8

Reactant 5

HCID 176Acetic AcidHCID 14798Sodium HydroxideHCID 24408BromineHCID 5460626HypobromiteHCID 670178781-[1-(1H-1,2,4-triazol-1-ylmethyl) tricyclo[3.3.1.03,7]non-3-yl]ethanone

Product 1

HCID 673003701-(1H-1,2,4-triazol-1-ylmethyl)tricyclo[3.3.1.03,7]nonane-3-carboxylic acidYield 75%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 312751,4-DioxaneSolvent2×

Procedure

To a stirred solution of NaOH (1.75 g, 43.8 mmol), H2O (14.6 mL) and 1,4 dioxane (2 mL) at ice bath temperature was added Br2 (0.8 mL, 16.4 mmol) and the mixture was stirred for 5 minutes. The resulting hypobromite solution was added drop-wise to a stirred solution of 1-[1-(1H-1,2,4-triazol-1-ylmethyl)tricyclo[3.3.1.03,7]non-3-yl]ethanone (0.7 g, 2.92 mmol) in 1,4-dioxane (4 mL) at ice bath temperature. The reaction mixture was gradually warmed to room temperature and stirred for 1 h. Then it was cooled to ice bath temperature and quenched by adding AcOH (3.9 mL, 65.7 mmol). The crude 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-(1H-1,2,4-triazol-1-ylmethyl)tricyclo[3.3.1.03,7]nonane-3-carboxylic acid (0.54 g) in 75% yield as an off-white solid. M.R: 230-235° C. m/z (M+1) 248. IR cm−1 3436, 3102, 2924, 2511, 1937, 1689, 1523, 1308, 1137, 979, 732. 1H NMR (CD3OD) 300 MHz δ 8.43 (s, 1H), 7.9 (s, 1H), 4.17 (s, 2H), 2.70-2.62 (m, 1H), 2.40-2.33 (m, 1H), 2.06-1.95 (m, 2H), 1.84-1.1.43 (m, 8H).

Workup

  1. stirringstirred for 1 h
  2. temperatureThen it was cooled to ice bath temperature
  3. customquenched
  4. customThe crude reaction mixture
  5. extractionextracted with EtOAc
  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-d68c1c91f1fc4f84ae80d4e49d07d3af
Source dataset
uspto-grants-2011_07
Patent number
US07985759B2

Reaction notes

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