Water → HCID 19705246, compound

HRID 727163Notes

Reaction equation

HRID 727163 reaction equation
[H-].[Na+].[Cl-].[Cl:4][C:5]1[CH:6]=[C:7]([CH2:12][P+](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[CH:8]=[C:9]([Cl:11])[CH:10]=1.[CH2:32]1[O:42][C:35]2([CH2:40][CH2:39][C:38](=O)[CH2:37][CH2:36]2)[O:34][CH2:33]1.O>CS(C)=O>[Cl:11][C:9]1[CH:8]=[C:7]([CH:12]=[C:38]2[CH2:39][CH2:40][C:35]3([O:42][CH2:32][CH2:33][O:34]3)[CH2:36][CH2:37]2)[CH:6]=[C:5]([Cl:4])[CH:10]=1

Participants

6

Reactant 4

HCID 962WaterHCID 24758Sodium hydrideHCID 5674151,4-Dioxaspiro[4.5]decan-8-oneHCID 19705252HCID 19705252, compound

Product 1

HCID 19705246HCID 19705246, compoundYield 32.4%

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
90 °C

Procedure

Under a nitrogen atmosphere, a stirred mixture of 4.2 grams (0.11 mole) of sodium hydride (60% in mineral oil) in 200 mL of anhydrous dimethyl sulfoxide was heated to about 90° C. where it was maintained for 10 minutes. After this time the reaction mixture was cooled to 25° C., and 46.0 grams (0.10 mole) of 3,5-dichlorophenylmethyltriphenylphosphonium chloride was added, followed by 14.0 grams (0.10 mole) of 1,4-cyclohexanedione mono-ethylene ketal. Upon completion of addition the reaction mixture was again warmed to 90° C., then it was allowed to cool to ambient temperature. After this time the reaction mixture was poured into 400 mL of water, and the mixture was extracted with two 250 mL portions of diethyl ether. The combined extracts were then washed with two 100 mL portions of water. The organic layer was concentrated under reduced pressure to an oily solid residue. The oily solid was taken up in a solution of 90 mL of petroleum ether and 10 mL of diethyl ether, and filtered. The filtrate was concentrated under reduced pressure to a residue. The residue was subjected to column chromatography using silica gel. Elution was accomplished using 10% diethyl ether in petroleum ether. The product-containing fractions were combined and concentrated under reduced pressure, yielding 9.7 grams of 8-(3,5-dichlorophenylmethylene)-1,4-dioxaspiro[4.5]decane, mp about 66° C. The NMR spectrum was consistent with the proposed structure.

Workup

  1. temperaturewas maintained for 10 minutes
  2. temperatureAfter this time the reaction mixture was cooled to 25° C.
  3. additionUpon completion of addition the reaction mixture
  4. temperaturewas again warmed to 90° C.
  5. temperatureto cool to ambient temperature
  6. extractionthe mixture was extracted with two 250 mL portions of diethyl ether
  7. washThe combined extracts were then washed with two 100 mL portions of water
  8. concentrationThe organic layer was concentrated under reduced pressure to an oily solid residue
  9. filtrationfiltered
  10. concentrationThe filtrate was concentrated under reduced pressure to a residue
  11. washElution
  12. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-b985015810c2414692427d8eb46db7d1
Source dataset
uspto-grants-1998_01
Patent number
US05712281

Reaction notes

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