Water → Ethyl 4,5,6,7-tetrahydro-1H-4,7-methanoindole-2-carboxylate

HRID 1919145Notes

Reaction equation

HRID 1919145 reaction equation
Cl[C:2]1[CH:7]2[CH2:8][CH:4]([CH2:5][CH2:6]2)[C:3]=1/[CH:9]=[CH:10]/[C:11]([O:13][CH2:14][CH3:15])=[O:12].[N-:16]=[N+]=[N-].[Na+].O>CS(C)=O>[CH:7]12[CH2:8][CH:4]([CH2:5][CH2:6]1)[C:3]1[CH:9]=[C:10]([C:11]([O:13][CH2:14][CH3:15])=[O:12])[NH:16][C:2]2=1

Participants

5

Reactant 3

HCID 962WaterHCID 33557Sodium AzideHCID 58043644(E)-Ethyl 3-(3-Chlorobicyclo[2.2.1]hept-2-en-2-yl)acrylate

Product 1

HCID 67016236Ethyl 4,5,6,7-tetrahydro-1H-4,7-methanoindole-2-carboxylateYield 60%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
105 °C

Procedure

To a solution of 334b (5.0 g, 22 mmol) in DMSO (30 mL) was added NaN3 (2.2 g, 33 mmol) and the mixture was heated at 105° C. for 6 hours. Water (13 mL) was added to reaction the mixture after cooling down to room temperature, and resulting mixture was extracted with methylene chloride (50 mL×3). The organic phase was dried (Na2SO4) and evaporated to dryness. The residue was purified by column chromatography eluting with 20:1 methylene chloride/methanol to give 334c as a brown solid (2.7 g, 60%). MS: [M+H]+ 206. 1H NMR (500 MHz, CDCl3) δ 11.51 (s, 1H), 6.45 (dd, 1H), 4.14-4.19 (m, 2H,), 3.25 (d, 2H,), 1.79-1.82 (m, 2H), 1.73 (d, 1H), 1.22-1.25 (t, J=6.5, 3H), 0.89-0.91 (m, 2H).

Workup

  1. temperatureafter cooling down to room temperature
  2. customresulting mixture
  3. extractionwas extracted with methylene chloride (50 mL×3)
  4. dry with materialThe organic phase was dried (Na2SO4)
  5. customevaporated to dryness
  6. customThe residue was purified by column chromatography
  7. washeluting with 20:1 methylene chloride/methanol

Sources & evidence

ORD record
ord-bfcbd2496ef0463791d010865ea69651
Source dataset
uspto-grants-2013_12
Patent number
US08618107B2

Reaction notes

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