Methanol → 1-Carbomethoxy-6-chloro-3,4-dihydronaphthalene

HRID 6395Notes

Reaction equation

HRID 6395 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]2[C:9](=[CH:10][CH:11]=1)[C:8]([C:12]#N)=[CH:7][CH2:6][CH2:5]2.[OH2:14].[CH3:15][OH:16]>S(=O)(=O)(O)O>[C:12]([C:8]1[C:9]2[C:4](=[CH:3][C:2]([Cl:1])=[CH:11][CH:10]=2)[CH2:5][CH2:6][CH:7]=1)([O:16][CH3:15])=[O:14]

Participants

5

Reactant 3

HCID 887MethanolHCID 962WaterHCID 197932786-Chloro-3,4-dihydronaphthalene-1-carbonitrile

Product 1

HCID 197931711-Carbomethoxy-6-chloro-3,4-dihydronaphthaleneYield 26%

Reagents, catalysts & solvents 1

HCID 1118Sulfuric AcidSolvent

Procedure

6-Chloro-1-cyano-3,4-dihydronaphthalene (5 g, 263 mmol), lit ref, was dissolved in 77% sulfuric acid in methanol and the resulting solution was heated at 95°-100° C. for 2.5 h. The reaction mixture was allowed to cool to ambient temperature and 45 mL was added, followed by 5 mL of water. The reaction mixture was stirred at ambient temperature for 2 days and then concentrated under reduced pressure. The residue was partitioned between ethyl acetate and water. The organic layer was concentrated in vacuo. The residue was purified by chromatography on silica gel eluted with 20% ethyl acetate in hexane to give 1.53 g (26% yield) of the title compound; MS DCl--NH3M/Z: 240 (M+H)+ ; 1H NMR (CDCl3) δ2.37-2.45 (2H, m), 2.75 (2H, t, J=7.5 Hz), 3.85 (3H, s), 7.15 (1H, d, J=1.5 Hz), 7.15 (1H, d, 9 Hz), 7.2 (1H, d, J=7.5 Hz), 7.77 (1H, d, J=7.5).

Workup

  1. temperaturethe resulting solution was heated at 95°-100° C. for 2.5 h
  2. addition45 mL was added
  3. concentrationconcentrated under reduced pressure
  4. customThe residue was partitioned between ethyl acetate and water
  5. concentrationThe organic layer was concentrated in vacuo
  6. customThe residue was purified by chromatography on silica gel
  7. washeluted with 20% ethyl acetate in hexane

Sources & evidence

ORD record
ord-0e9e6791f66b44a5853ffa9b8e1fcd15
Source dataset
uspto-grants-1993_09
Patent number
US05248677

Reaction notes

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