HCID 23356090, compound → HCID 23356091, compound

HRID 233619Notes

Reaction equation

HRID 233619 reaction equation
[CH2:1]([O:3][C:4]([CH:6]1[CH2:15][C:14]2[C:9](=[C:10]([O:19]C)[C:11]([Cl:18])=[CH:12][C:13]=2[O:16]C)[CH2:8][O:7]1)=[O:5])[CH3:2]>C(#N)C.O.C(Cl)Cl>[CH2:1]([O:3][C:4]([CH:6]1[CH2:15][C:14]2[C:13](=[O:16])[CH:12]=[C:11]([Cl:18])[C:10](=[O:19])[C:9]=2[CH2:8][O:7]1)=[O:5])[CH3:2]

Participants

5

Reactant 1

HCID 23356090HCID 23356090, compound

Product 1

HCID 23356091HCID 23356091, compoundYield 55%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6342AcetonitrileSolventHCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of 1.0 g (3.7 mmol) of the chloroiso-chroman from step 6 in 20 ml of acetonitrile was added dropwise a solution containing 6.25 g (11.4 mmol) of ceric ammonium nitrate in 20 ml of water. The mixture was stirred overnight and then diluted with 50 ml of CH2Cl2. The organic layer was separated and the aqueous phase was extracted twice with 25 ml CH2Cl2. The combined organic layer was washed once with 50 ml H2O, 50 ml brine and then dried over Na2SO4. After evaporation of solvents, flash chromatography of the residue with a solvent gradient of 5 to 20% ethyl acetate in toluene yielded 495 mg (55%) of the titled compound. (MP: 83.5° C.) 1H NMR (200 MHz, CDCl3) δ: 1.27 (t, 3H, J=7.1 Hz, CH3), 2.58 (ddt, 1H, J=19.0, 8.8, 3.2 Hz, HCHaCHC=O), 2.83 (d multiplets, 1H, HCHeCHC=O), 4.17 (dd, 1H, J=8.7, 3.3 Hz, OCHC=O), 4.20 (q, 2H, J=7.0 Hz, OCH2), 4.44 (dt, 1H, J=18.8, 3.4 Hz, HCHaO), 4.78 (d multipier, 1H, J=18.8, 2.6, 1.7 Hz, HCHeO), 6.95 (s, 1H, C=CH).

Workup

  1. customThe organic layer was separated
  2. extractionthe aqueous phase was extracted twice with 25 ml CH2Cl2
  3. washThe combined organic layer was washed once with 50 ml H2O, 50 ml brine
  4. dry with materialdried over Na2SO4
  5. customAfter evaporation of solvents, flash chromatography of the residue with a solvent gradient of 5 to 20% ethyl acetate in toluene

Sources & evidence

ORD record
ord-dd975d56bb264309a573d4ad795a614b
Source dataset
uspto-grants-1997_01
Patent number
US05593970

Reaction notes

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