Dimethyl Sulfoxide → Ethyl 4-(1-oxaspiro[2.5]oct-6-yl)benzoate

HRID 1035706Notes

Reaction equation

HRID 1035706 reaction equation
[H-].[Na+].[I-].C[S+](C)(C)=O.[CH3:9]S(C)=O.[O:13]=[C:14]1[CH2:19][CH2:18][CH:17]([C:20]2[CH:30]=[CH:29][C:23]([C:24]([O:26][CH2:27][CH3:28])=[O:25])=[CH:22][CH:21]=2)[CH2:16][CH2:15]1>CS(C)=O.C1COCC1.O>[O:13]1[C:14]2([CH2:19][CH2:18][CH:17]([C:20]3[CH:21]=[CH:22][C:23]([C:24]([O:26][CH2:27][CH3:28])=[O:25])=[CH:29][CH:30]=3)[CH2:16][CH2:15]2)[CH2:9]1

Participants

7

Reactant 4

HCID 679Dimethyl SulfoxideHCID 24758Sodium hydrideHCID 74498Sulfoxonium, trimethyl-, iodide (1:1)HCID 22633634Ethyl 4-(4-oxocyclohexyl)benzoate

Product 1

HCID 86662113Ethyl 4-(1-oxaspiro[2.5]oct-6-yl)benzoate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 21830753dimethylsulfoxide THFSolvent2×

Conditions

Temperature
10 °C

Procedure

0.246 g of sodium hydride (9.74 mmol, 2 eq.) is placed in 25 mL of a 1/1.5 mixture of THF/DMSO with stirring at 10° C. 2.14 g of trimethylsulfoxonium iodide (9.74 mmol, 1.2 eq.) are added. After 5 minutes, 10 mL of DMSO are added dropwise. After the evolution of gas has ceased, 2 g of ethyl 4-(4-oxocyclohexyl)benzoate (8.12 mmol, 1 eq.) dissolved in a minimum amount of a 2/1 mixture of DMSO/THF are rapidly added at room temperature. After stirring for 1 hour at room temperature and for 1 hour at 50° C., the reaction medium is diluted with 75 mL of water and extracted with ethyl acetate. The organic phases are successively washed twice with water and with brine, dried over sodium sulfate and evaporated. The residue is chromatographed on silica gel with a gradient of methanol in dichloromethane ranging from 1% to 2%. 1.8 g of ethyl 4-(1-oxaspiro[2.5]oct-6-yl)benzoate are obtained.

Workup

  1. additionare rapidly added at room temperature
  2. stirringAfter stirring for 1 hour at room temperature and for 1 hour at 50° C.
  3. extractionextracted with ethyl acetate
  4. washThe organic phases are successively washed twice with water and with brine
  5. dry with materialdried over sodium sulfate
  6. customevaporated
  7. customThe residue is chromatographed on silica gel with a gradient of methanol in dichloromethane ranging from 1% to 2%

Sources & evidence

ORD record
ord-19d5df5b42d64e3c974ec66b1111d556
Source dataset
uspto-grants-2013_10
Patent number
US08546391B2

Reaction notes

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