Sodium hydride → 3,4-dihydro-2H-1,5-benzodioxepin-3-spiro-2'-oxirane

HRID 267772Notes

Reaction equation

HRID 267772 reaction equation
[O:1]=[C:2]1[CH2:8][O:7][C:6]2[CH:9]=[CH:10][CH:11]=[CH:12][C:5]=2[O:4][CH2:3]1.[CH3:13]S(C)(=O)=C.[H-].[Na+].[I-].C[S+](C)(C)=O>CS(C)=O>[O:1]1[CH2:13][C:2]21[CH2:3][O:4][C:5]1[CH:12]=[CH:11][CH:10]=[CH:9][C:6]=1[O:7][CH2:8]2

Participants

6

Reactant 4

HCID 24758Sodium hydrideHCID 74498Sulfoxonium, trimethyl-, iodide (1:1)HCID 6396768Dimethylsulfoxonium methylideHCID 113097002H-1,5-Benzodioxepin-3(4H)-one

Product 1

HCID 155573103,4-dihydro-2H-1,5-benzodioxepin-3-spiro-2'-oxirane

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Procedure

3-Oxo-3,4-dihydro-2H-1,5-benzodioxepin (1.64 g.; 10 millimoles) from Example 1, Step C, is added slowly with stirring during 15 minutes at ambient temperature to a solution of dimethyloxosulfonium methylide prepared under nitrogen from 15 millimoles of sodium hydride, 15 millimoles of trimethyloxosulfonium iodide, and 30 mls. of dimethyl sulfoxide. The mixture is stirred for 24 hours at ambient temperature and then 2 hours at 45°-50° C. The mixture is cooled and poured onto 50 g. of ice and repeatedly extracted with diethyl ether. The ethereal extract is washed with water, dried over anhydrous magnesium sulfate and evaporated. The crude product is crystallized from methanol to afford the 3,4-dihydro-2H-1,5-benzodioxepin-3-spiro-2'-oxirane identical with the product prepared from 3-hydroxy-3-aminomethyl-3,4-dihydro-2H-1,5-benzodioxepin as described in Example 57, Step A.

Workup

  1. custom2 hours
  2. customat 45°-50° C
  3. temperatureThe mixture is cooled
  4. additionpoured onto 50 g
  5. extractionof ice and repeatedly extracted with diethyl ether
  6. extractionThe ethereal extract
  7. washis washed with water
  8. dry with materialdried over anhydrous magnesium sulfate
  9. customevaporated
  10. customThe crude product is crystallized from methanol

Sources & evidence

ORD record
ord-4b09d94c95654783901e301ef1576681
Source dataset
uspto-grants-1976_03
Patent number
US03944560

Reaction notes

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