Potassium methacrylate → 4-(6-Methacryloylhexyl)cyclohexyl 4-allyloxybenzoate

HRID 277622Notes

Reaction equation

HRID 277622 reaction equation
[CH2:1]([O:4][C:5]1[CH:27]=[CH:26][C:8]([C:9]([O:11][C@H:12]2[CH2:17][CH2:16][C@H:15]([C:18](=O)[CH2:19][CH2:20][CH2:21][CH2:22][CH2:23]Br)[CH2:14][CH2:13]2)=[O:10])=[CH:7][CH:6]=1)[CH:2]=[CH2:3].[C:28]([O-])(=[O:32])[C:29]([CH3:31])=[CH2:30].[K+]>CN(C)C=O.C(C1C=C(C)C=C(C(C)(C)C)C=1O)(C)(C)C>[CH2:1]([O:4][C:5]1[CH:27]=[CH:26][C:8]([C:9]([O:11][CH:12]2[CH2:17][CH2:16][CH:15]([CH2:18][CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][C:28](=[O:32])[C:29]([CH3:31])=[CH2:30])[CH2:14][CH2:13]2)=[O:10])=[CH:7][CH:6]=1)[CH:2]=[CH2:3]

Participants

5

Reactant 2

HCID 23667354Potassium methacrylateHCID 178458474HCID 178458474, compound

Product 1

HCID 226254514-(6-Methacryloylhexyl)cyclohexyl 4-allyloxybenzoateYield 97.5%

Reagents, catalysts & solvents 2

HCID 314042,6-Di-tert-butyl-4-methylphenolCatalystHCID 6228DimethylformamideSolvent

Conditions

Temperature
72.5 °C

Procedure

55.2 g (0.2 mol) of trans-4-hydroxycyclohexyl allyloxybenzoate prepared as described in Example 1 were dissolved in 300 ml of dry toluene, and 43 g (0.205 mol) of 6-bromohexanoyl chloride (prepared from the free acid by conventional reaction with thionyl chloride; b.p. 60-62° C. at 0.04 mbar) were added dropwise at 105° C. over the course of 60 minutes with stirring. After the mixture had been stirred at 105° C. for a further 90 minutes, the solvent was stripped off under reduced pressure, and the residue was crystallized out using petroleum benzine/methyl tert-butyl ether (20:1), giving 83 g (92%) of trans-[4-(6-bromo-hexanoyl)cyclohexyl] 4-allyloxybenzoate, melting point 56° C. 79 g (0.174 mol) of this ester, 25 g (0.21 mol) of potassium methacrylate and 0.2 g of 2,6-di-tert-butyl-4-methylphenol (stabilizer) were dissolved in 400 ml of dimethylformamide, and the mixture was heated at 70-75° C. for 3 hours with stirring. The solvent was then distilled off under reduced pressure, the residue was taken up in 400 ml of methyl tert-butyl ether, and the solution was washed with water, 0.05 N NaOH, and again with water, dried and evaporated. The residue was recrystallized from methanol, yielding 70 g (87.5%) of the title compound, which melts at 50° C. and clears at 55° C.

Workup

  1. distillationThe solvent was then distilled off under reduced pressure
  2. washthe solution was washed with water, 0.05 N NaOH
  3. dry with materialagain with water, dried
  4. customevaporated
  5. customThe residue was recrystallized from methanol

Sources & evidence

ORD record
ord-653188ab9fc5475ba35f2966cce13f02
Source dataset
uspto-grants-2002_03
Patent number
US06358574B1

Reaction notes

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