Methacryloyl chloride → HCID 86618070, compound

HRID 1644152Notes

Reaction equation

HRID 1644152 reaction equation
C([Li])CCC.[F:6][C:7]([F:23])([F:22])[C:8]([CH:14]1[CH2:19][CH2:18][CH2:17][CH2:16][C:15]1([CH3:21])[OH:20])([OH:13])[C:9]([F:12])([F:11])[F:10].[C:24](Cl)(=[O:28])[C:25]([CH3:27])=[CH2:26]>O1CCCC1>[C:24]([O:20][C:15]1([CH3:21])[CH2:16][CH2:17][CH2:18][CH2:19][CH:14]1[C:8]([OH:13])([C:9]([F:11])([F:10])[F:12])[C:7]([F:22])([F:23])[F:6])(=[O:28])[C:25]([CH3:27])=[CH2:26]

Participants

5

Reactant 3

HCID 13528Methacryloyl chlorideHCID 59429093HCID 59429093, compoundHCID 178418339Butyllithium

Product 1

HCID 86618070HCID 86618070, compound

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

To a flame-dried, nitrogen-purged 250 mL 3-neck roundbottom flask with 50 mL pressure-equalizing addition funnel and magnetic stirbar was charged 85 mL n-butyl lithium (136 mmol, 2 equiv., 1.6 M in hexanes). A degassed solution of 12-(1,1,1,3,3,3-hexafluoro-2-hydroxypropan2-yl)-1-methylcyclohexanol (X) (.about.68 mmol, 1 eq.) in 50 mL anhydrous tetrahydrofuran was charged to the addition funnel and added to the reaction mixture dropwise at 0° C. over 30 minutes. The reaction mixture was warmed for 15 minutes on a hot water bath to ensure the reaction was complete. The reaction vessel was cooled to 0° C. and 7.46 g methacryloyl chloride (71.4 mmol, 1.05 eq.) was added dropwise and allowed to stir for 15 minutes. The addition funnel was replaced with a reflux condenser and the reaction heated to reflux for 20 hours. After the reaction was complete, it was cooled to 0° C. and quenched with dilute HCl solution until the pH was less than 5.0. The reaction solution was neutralized with saturated aqueous sodium bicarbonate until the pH was greater than 8. The product was extracted into ethyl ether and the organic phase washed sequentially with aqueous sodium bicarbonate, water, and brine and then dried over magnesium sulfate, filtered, concentrated in vacuo, and stored over a small amount of sodium bicarbonate. The crude product mixture was purified via silica gel column chromatography (20:1 hexane:ethyl acetate eluent) to afford 3.08 of 2-(1,1,1,3,3,3-hexafluoro-2-hydroxypropan-2-yl)-1-methylcyclohex-1-yl methacrylate (XII) as a colorless liquid (1 isomer) of only 66% purity. After standing in the refrigerator overnight, 2-(1,1,1,3,3,3-hexafluoro-2-hydroxypropan-2-yl)-1-methylcyclohex-1-yl methacrylate (XII) crystallizes out of the mixture a white crystalline solid.

Workup

  1. customTo a flame-dried, nitrogen-purged 250 mL
  2. additionroundbottom flask with 50 mL pressure-equalizing addition funnel
  3. additionadded to the reaction mixture dropwise at 0° C. over 30 minutes
  4. temperatureThe reaction mixture was warmed for 15 minutes on a hot water bath
  5. customThe addition funnel was replaced with a reflux condenser
  6. temperaturethe reaction heated
  7. temperatureto reflux for 20 hours
  8. temperatureit was cooled to 0° C.
  9. customquenched with dilute HCl solution until the pH was less than 5.0
  10. extractionThe product was extracted into ethyl ether
  11. washthe organic phase washed sequentially with aqueous sodium bicarbonate, water, and brine
  12. dry with materialdried over magnesium sulfate
  13. filtrationfiltered
  14. concentrationconcentrated in vacuo
  15. customThe crude product mixture was purified via silica gel column chromatography (20:1 hexane:ethyl acetate eluent)

Sources & evidence

ORD record
ord-951d3f7028234a88a7fe670697388c5c
Source dataset
uspto-grants-2012_02
Patent number
US08124327B2

Reaction notes

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