Methacryloyl chloride → 6-Methacryloxymethyl-2-naphthol

HRID 720805Notes

Reaction equation

HRID 720805 reaction equation
[OH:1][CH2:2][C:3]1[CH:4]=[C:5]2[C:10](=[CH:11][CH:12]=1)[CH:9]=[C:8]([OH:13])[CH:7]=[CH:6]2.C([Li])CCC.[C:19](Cl)(=[O:23])[C:20]([CH3:22])=[CH2:21].[Cl-].[NH4+]>C1COCC1>[C:19]([O:1][CH2:2][C:3]1[CH:4]=[C:5]2[C:10](=[CH:11][CH:12]=1)[CH:9]=[C:8]([OH:13])[CH:7]=[CH:6]2)(=[O:23])[C:20]([CH3:22])=[CH2:21]

Participants

6

Reactant 4

HCID 13528Methacryloyl chlorideHCID 25517Ammonium ChlorideHCID 113327606-(Hydroxymethyl)naphthalen-2-olHCID 178418339Butyllithium2×

Product 1

HCID 218953606-Methacryloxymethyl-2-naphtholYield 56%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
5 °C

Procedure

To a 3-necked, 500-mL round bottomed flask equipped with an overhead stirrer, a digital thermometer and a 250-mL constant-pressure addition funnel with a nitrogen inlet was added 25 g (0.14 mol) of 6-hydroxymethyl-2-naphthol and 100 mL of anhydrous THF. The addition funnel was charged with 190 mL (0.3 mol) of n-butyllithium (1.6 M in hexane). The flask was cooled to 5° C. and the butyllithium was added slowly while maintaining a temperature of less than 15° C. The resulting suspension was stirred for 1 h at which time a solution of 14.9 g (0.15 mol) of methacryloyl chloride in 100 mL of anhydrous THF was slowly added while maintaining a temperature of less than 10° C. Stirring was continued with cooling for 6 h at which time the reaction mixture was poured into 300 mL of saturated ammonium chloride with vigorous stirring. The organic layer was separated and the aqueous layer extracted with ethyl acetate. The combined organic phases were washed with water and brine, dried and evaporated. The resulting residue was chromatographed on silica gel with 35% ethyl acetate in hexane. The fractions containing the pure product were combined and evaporated to yield 19 g (56%) of the title compound as an off-white solid.

Workup

  1. customTo a 3-necked, 500-mL round bottomed flask equipped with an overhead stirrer
  2. additiona digital thermometer and a 250-mL constant-pressure addition funnel with a nitrogen inlet
  3. temperaturewhile maintaining a temperature of less than 15° C
  4. additionwas slowly added
  5. temperaturewhile maintaining a temperature of less than 10° C
  6. temperaturewith cooling for 6 h at which time the reaction mixture
  7. customThe organic layer was separated
  8. extractionthe aqueous layer extracted with ethyl acetate
  9. washThe combined organic phases were washed with water and brine
  10. customdried
  11. customevaporated
  12. customThe resulting residue was chromatographed on silica gel with 35% ethyl acetate in hexane
  13. additionThe fractions containing the pure product
  14. customevaporated

Sources & evidence

ORD record
ord-992c2e01941f480eb5877d2b22cfb0fb
Source dataset
uspto-grants-2006_11
Patent number
US07135595B2

Reaction notes

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