1,3-Propanediol → Ethyl 9-[N-(2-chloro-4-fluorophenyl)sulfamoyl]-1,5-dioxaspiro[5.5]undec-7-ene-8-carboxylate

HRID 546338Notes

Reaction equation

HRID 546338 reaction equation
[Cl:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[NH:9][S:10]([CH:13]1[C:18]([C:19]([O:21][CH2:22][CH3:23])=[O:20])=[CH:17][C:16](=[O:24])[CH2:15][CH2:14]1)(=[O:12])=[O:11].[CH2:25](O)[CH2:26][CH2:27][OH:28].C1(C)C=CC(S([O-])(=O)=O)=CC=1.[NH+]1C=CC=CC=1.C(=O)([O-])O.[Na+]>C1(C)C=CC=CC=1>[Cl:1][C:2]1[CH:7]=[C:6]([F:8])[CH:5]=[CH:4][C:3]=1[NH:9][S:10]([CH:13]1[CH2:14][CH2:15][C:16]2([O:28][CH2:27][CH2:26][CH2:25][O:24]2)[CH:17]=[C:18]1[C:19]([O:21][CH2:22][CH3:23])=[O:20])(=[O:12])=[O:11]

Participants

6

Reactant 4

HCID 104421,3-PropanediolHCID 466102Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1)HCID 516892Sodium BicarbonateHCID 57870910Ethyl 6-(N-(2-chloro-4-fluorophenyl)sulfamoyl)-3-oxocyclohex-1-ene-1-carboxylate

Product 1

HCID 57871040Ethyl 9-[N-(2-chloro-4-fluorophenyl)sulfamoyl]-1,5-dioxaspiro[5.5]undec-7-ene-8-carboxylateYield 51.2%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

100 mg (0.27 mmol) of ethyl 6-[N-(2-chloro-4-fluorophenyl)sulfamoyl]-3-oxo-1-cyclohexene-1-carboxylate obtained in Example 7 was dissolved in 2 ml of toluene, and 0.04 ml (0.54 mmol) of propane-1,3-diol and 68 mg (0.27 mmol) of pyridinium p-toluenesulfonate were added thereto, followed by heating under reflux for 1 hour. After the reaction solution was cooled to room temperature, a saturated aqueous sodium hydrogencarbonate solution was added and extracted with ethyl acetate. The organic layer was washed with water and dried over anhydrous magnesium sulfate, followed by concentration under reduced pressure. The residue was subjected to silica gel column chromatography (solvent; hexane:ethyl acetate=2:1), and the resulting solid was further washed with hexane to give 60 mg of the title compound as a white powder (yield: 51%).

Workup

  1. temperatureby heating
  2. temperatureunder reflux for 1 hour
  3. extractionextracted with ethyl acetate
  4. washThe organic layer was washed with water
  5. dry with materialdried over anhydrous magnesium sulfate
  6. concentrationfollowed by concentration under reduced pressure
  7. washthe resulting solid was further washed with hexane

Sources & evidence

ORD record
ord-55ffefd6aa704bc3b99883cdc5c89a40
Source dataset
uspto-grants-2011_05
Patent number
US07935835B2

Reaction notes

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