Water → 2-Chloro-3-(hydroxymethylidene)cyclohex-1-ene-1-carbaldehyde

HRID 538944Notes

Reaction equation

HRID 538944 reaction equation
O=P(Cl)(Cl)Cl.CN([CH:9]=[O:10])C.[C:11]1(=[O:17])[CH2:16][CH2:15][CH2:14][CH2:13][CH2:12]1.O.[CH2:19]([Cl:21])Cl>>[Cl:21][C:19]1[C:12](=[CH:11][OH:17])[CH2:13][CH2:14][CH2:15][C:16]=1[CH:9]=[O:10]

Participants

6

Reactant 5

HCID 962WaterHCID 6228DimethylformamideHCID 6344Dichloromethane2×HCID 7967CyclohexanoneHCID 24813Phosphorus oxychloride

Product 1

HCID 713999952-Chloro-3-(hydroxymethylidene)cyclohex-1-ene-1-carbaldehyde

Procedure

S1 was synthesized as reported procedure. Zhang, Z.; Achilefu, S. Org. Lett., 2004, 6, 2067-2070. A solution of POCl3 (37 mL, 397 mmol) in CH2Cl2 (35 mL) was slowly added to an ice-cooled solution of DMF (40 mL, 516 mmol) in CH2Cl2 (40 mL). After the addition was finished, cyclohexanone (10 g, 100 mmol) was added dropwisely. The resulted reaction mixture was refluxed for 2 h. The mixture was then cooled in ice. Water (200 mL) was added slowly while the mixture was stirred. The mixture was stirred for 1 h. The organic layer was collected and the water layer was extracted with additional CH2Cl2 (40 mL×3). The combined organic layers were dried over Na2SO4 and then evaporated. The residue was taken up in a mixture of AcOEt-diethylether (3:1), and the mixture was washed with water (30 mL×5) to remove DMF. The combined organic layers were dried over Na2SO4 and then evaporated. The residue was treated with pentane (200 mL) to give 4.2 g (23%) of S1 as yellow crystalline solid. LRMS (ESI): calculated for [(M+H)+] 173.1. found 173.1.

Workup

  1. customS1 was synthesized
  2. additionAfter the addition
  3. customThe resulted reaction mixture
  4. temperaturewas refluxed for 2 h
  5. temperatureThe mixture was then cooled in ice
  6. stirringThe mixture was stirred for 1 h
  7. customThe organic layer was collected
  8. extractionthe water layer was extracted with additional CH2Cl2 (40 mL×3)
  9. dry with materialThe combined organic layers were dried over Na2SO4
  10. customevaporated
  11. additionThe residue was taken up in a mixture of AcOEt-diethylether (3:1)
  12. washthe mixture was washed with water (30 mL×5)
  13. customto remove DMF
  14. dry with materialThe combined organic layers were dried over Na2SO4
  15. customevaporated
  16. additionThe residue was treated with pentane (200 mL)
  17. customto give 4.2 g (23%) of S1 as yellow crystalline solid

Sources & evidence

ORD record
ord-3b5a2a7017dd453d887a5fc161d7bb10
Source dataset
uspto-grants-2014_10
Patent number
US08865914B2

Reaction notes

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