Sodium hydride → HCID 89452004, compound

HRID 1497555Notes

Reaction equation

HRID 1497555 reaction equation
[H-].[Na+].COP([CH:9]([CH3:20])[C:10]([O:12][CH2:13][C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)=[O:11])(OC)=O.[Si]([O:28][C:29]1[CH:36]=[CH:35][C:32]([CH:33]=O)=[C:31]([Cl:37])[CH:30]=1)(C(C)(C)C)(C)C.[Cl-].[NH4+]>O1CCCC1.C(OCC)(=O)C.O>[Cl:37][C:31]1[CH:30]=[C:29]([OH:28])[CH:36]=[CH:35][C:32]=1/[CH:33]=[C:9](\[CH3:20])/[C:10]([O:12][CH2:13][C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=1)=[O:11]

Participants

8

Reactant 4

HCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 589074694-[(Tert-butyldimethylsilyl)oxy]-2-chlorobenzaldehydeHCID 89451919HCID 89451919, compound

Product 1

HCID 89452004HCID 89452004, compoundYield 72.9%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

To a solution of 55% sodium hydride (128 mg) in tetrahydrofuran (15.0 mL) was added benzyl 2-(dimethoxyphosphoryl)propanoate (796 mg) under ice-cooling, followed by stirring for 30 minutes under ice-cooling. Subsequently, a solution of 4-{[tert-butyl(dimethyl)silyl]oxy}-2-chlorobenzaldehyde (720 mg) in tetrahydrofuran (3.00 mL) was added thereto, followed by stirring at room temperature for 4 hours. To the reaction mixture were added a saturated aqueous ammonium chloride solution, water, and ethyl acetate, and the organic layer was extracted. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. To a solution of the residue in tetrahydrofuran (10.0 mL) was added a 1 M solution of tetra-n-butylammonium fluoride in tetrahydrofuran (2.70 mL) under ice-cooling, followed by stirring for 30 minutes under ice-cooling. After completion, to the reaction mixture were added a saturated aqueous ammonium chloride solution, water, and ethyl acetate, and the organic layer was extracted. The organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane-ethyl acetate) to obtain benzyl (2E)-3-(2-chloro-4-hydroxyphenyl)-2-methylacrylate (587 mg).

Workup

  1. temperaturecooling
  2. temperaturecooling
  3. stirringby stirring at room temperature for 4 hours
  4. extractionthe organic layer was extracted
  5. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  6. concentrationconcentrated under reduced pressure
  7. additionTo a solution of the residue in tetrahydrofuran (10.0 mL) was added a 1 M solution of tetra-n-butylammonium fluoride in tetrahydrofuran (2.70 mL) under ice-
  8. temperaturecooling
  9. stirringby stirring for 30 minutes under ice-
  10. temperaturecooling
  11. additionAfter completion, to the reaction mixture were added a saturated aqueous ammonium chloride solution, water, and ethyl acetate
  12. extractionthe organic layer was extracted
  13. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  14. concentrationconcentrated under reduced pressure
  15. customThe residue was purified by silica gel column chromatography (hexane-ethyl acetate)

Sources & evidence

ORD record
ord-936e8b02945b48149528722d14fc5a75
Source dataset
uspto-grants-2015_12
Patent number
US09199927B2

Reaction notes

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