4-Methyl-2-methylene valeric acid → HCID 67982622, compound

HRID 1525466Notes

Reaction equation

HRID 1525466 reaction equation
[C:1]([C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][C:6]=1[O:11][CH3:12])([CH3:4])([CH3:3])[CH3:2].[CH2:13]([C:17](=[CH2:21])[C:18](O)=[O:19])[CH:14]([CH3:16])[CH3:15]>O>[C:1]([C:5]1[CH:10]=[C:9]2[C:8]([CH2:21][CH:17]([CH2:13][CH:14]([CH3:16])[CH3:15])[C:18]2=[O:19])=[CH:7][C:6]=1[O:11][CH3:12])([CH3:4])([CH3:2])[CH3:3]

Participants

4

Reactant 2

HCID 1686594-Methyl-2-methylene valeric acidHCID 270626tert-Butylanisole

Product 1

HCID 67982622HCID 67982622, compound

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
60 °C

Procedure

To Iton reagent (obtained from 110 g of P4O10 and 560 ml of methanesulfonic acid at 110° C.) a mixture of 59.4 g (0.362 mol) of 1-tert-butyl-2-methoxybenzene and 51.5 g (0.402 mol) of 2-isobutylacrylic acid was added dropwise at vigorous stirring in such a rate to maintain temperature at 60±1° C. (for ca. 40 min). The resulting mixture was stirred for 40 min at 65° C., cooled to room temperature, and then poured on 1000 cm3 of ice with 1000 cm3 of water. The product was extracted by 3×500 ml of dichloromethane. The combined organic extract was washed by aqueous K2CO3, dried over Na2SO4 and then evaporated to dryness. Fractional rectification of the residue gave dark red oil, b.p. 165-174° C./5 mm Hg. This oil was recrystallized from 100 ml of hexanes. White crystals precipitated at 5° C. were collected, washed by 20 ml of cold hexanes, and dried in vacuum. Yield 24.9 g (25%) of the title product.

Workup

  1. additionwas added dropwise
  2. stirringThe resulting mixture was stirred for 40 min at 65° C.
  3. temperaturecooled to room temperature
  4. extractionThe product was extracted by 3×500 ml of dichloromethane
  5. extractionThe combined organic extract
  6. washwas washed by aqueous K2CO3
  7. dry with materialdried over Na2SO4
  8. customevaporated to dryness
  9. customFractional rectification of the residue gave dark red oil, b.p. 165-174° C./5 mm Hg
  10. customThis oil was recrystallized from 100 ml of hexanes
  11. customWhite crystals precipitated at 5° C.
  12. customwere collected
  13. washwashed by 20 ml of cold hexanes
  14. customdried in vacuum

Sources & evidence

ORD record
ord-7f2c91caaa2a4332960a05bef5c196d2
Source dataset
uspto-grants-2015_07
Patent number
US09079985B2

Reaction notes

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