Methanol → HCID 131715221, compound

HRID 1789089Notes

Reaction equation

HRID 1789089 reaction equation
CC(C[AlH]CC(C)C)C.[CH3:10][C:11]([SiH2:14][O:15][CH:16]1[CH2:21][C:20]2([CH2:26][CH2:25][CH2:24][CH2:23][O:22]2)[O:19][CH:18]([CH2:27]/[CH:28]=[C:29](\[CH3:35])/[C:30](OCC)=[O:31])[CH2:17]1)([CH3:13])[CH3:12].CO.C(OCC)(=O)C.CCCCCC>C(Cl)Cl>[CH3:13][C:11]([SiH2:14][O:15][CH:16]1[CH2:21][C:20]2([CH2:26][CH2:25][CH2:24][CH2:23][O:22]2)[O:19][CH:18]([CH2:27][CH2:28]/[C:29](/[CH3:35])=[CH:30]/[OH:31])[CH2:17]1)([CH3:10])[CH3:12]

Participants

6

Reactant 4

HCID 887MethanolHCID 14487Diisobutylaluminum hydrideHCID 21226206Ethyl acetate hexaneHCID 131715222HCID 131715222, compound

Product 1

HCID 131715221HCID 131715221, compound

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of 1M DIBAL (155 ml; 155 mmoles) is added dropwise to a solution of ethyl 4-[4-[(1,1-dimethylethyl)silyl]oxy-1,7-dioxaspiro[5.5]undec-2-yl]-2-methyl-2E-butenoate, (29.0 g; 70.3 mmoles) in methylene chloride (350 ml) with stirring under nitrogen at -78°. Upon completion of the addition, the reaction mixture is allowed to warm to 2° and stirred for two hours. The reaction mixture is cooled to 0° and treated dropwise (slight foaming) with methanol (45 ml). After 15 minutes the reaction mixture is partitioned between methylene chloride (500 ml) and a mixture of 6.67N sulfuric acid (150 ml) and crushed ice (300 g). The mixture is intermittently shaken over a ten minute period. The layers are separated and the aqueous phase extracted with methylene chloride (500 ml). The combined organic phases are dried over anhydrous sodium sulfate, filtered through celite, and concentrated in vacuo to give an oil. Chromatography (15-40% ethyl acetate/hexane) yields the title compound, 4-[4-[(1,1-dimethylethyl)silyl]oxy-1,7-dioxaspiro[5.5]undec-2-yl]-2-methyl-2E-butenol; (21.8 g; 83.8%) as an oil.

Workup

  1. additionUpon completion of the addition
  2. temperatureto warm to 2°
  3. stirringstirred for two hours
  4. temperatureThe reaction mixture is cooled to 0°
  5. customAfter 15 minutes the reaction mixture is partitioned between methylene chloride (500 ml)
  6. additiona mixture of 6.67N sulfuric acid (150 ml)
  7. customcrushed ice (300 g)
  8. stirringThe mixture is intermittently shaken over a ten minute period
  9. customThe layers are separated
  10. extractionthe aqueous phase extracted with methylene chloride (500 ml)
  11. dry with materialThe combined organic phases are dried over anhydrous sodium sulfate
  12. filtrationfiltered through celite
  13. concentrationconcentrated in vacuo
  14. customto give an oil

Sources & evidence

ORD record
ord-b1c8ce92ad7041c4bfcaac9c619c0317
Source dataset
uspto-grants-1987_08
Patent number
US04686297

Reaction notes

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