Acetic Acid → Ethyl(Z)-4-[2-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-2-(trimethylsilyl)vinyl]benzoate

HRID 1071332Notes

Reaction equation

HRID 1071332 reaction equation
[CH3:1][C:2]1[C:3](/[C:16](/[Si:26]([CH3:29])([CH3:28])[CH3:27])=[CH:17]/[C:18]2[CH:25]=[CH:24][C:21]([CH2:22][OH:23])=[CH:20][CH:19]=2)=[CH:4][C:5]2[C:6]([CH3:15])([CH3:14])[CH2:7][CH2:8][C:9]([CH3:13])([CH3:12])[C:10]=2[CH:11]=1.[C-]#N.[Na+].[C:33](O)(=[O:35])[CH3:34]>[O-2].[O-2].[Mn+4].CCCCCC>[CH3:1][C:2]1[C:3](/[C:16](/[Si:26]([CH3:28])([CH3:27])[CH3:29])=[CH:17]/[C:18]2[CH:25]=[CH:24][C:21]([C:22]([O:35][CH2:33][CH3:34])=[O:23])=[CH:20][CH:19]=2)=[CH:4][C:5]2[C:6]([CH3:15])([CH3:14])[CH2:7][CH2:8][C:9]([CH3:12])([CH3:13])[C:10]=2[CH:11]=1

Participants

6

Reactant 3

HCID 176Acetic AcidHCID 8929Sodium CyanideHCID 9866068(Z)-4-[2-(3,5,5,8,8-Pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-2-(trimethylsilyl)vinyl]benzyl Alcohol2×

Product 1

HCID 9955320Ethyl(Z)-4-[2-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-2-(trimethylsilyl)vinyl]benzoate

Reagents, catalysts & solvents 2

HCID 178418406HCID 178418406, compoundCatalyst2×HCID 8058HexaneSolvent

Procedure

Manganese dioxide (265 mg, 2.96 mmol) was added to a solution of (Z)-4-[2-(3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydronaphthalen-2-yl)-2-(trimethylsilyl)vinyl]benzyl alcohol (Compound 3, 60 mg, 0.15 mmol) and 3.65 mL of hexane. The solution was stirred at room temperature for 16 hours, the manganese dioxide filtered off, and the hexane removed in vacuo. The residue was dissolved in 2 mL of ethanol and treated with sodium cyanide (37.5 mg, 0.77 mmol) and acetic acid (13.7 mg, 0.23 mmol). After 15 minutes, the solution was treated with 265 mg (3.0 mmol) of manganese dioxide. The suspension was stirred at room temperature for 6 hours and the manganese dioxide removed by filtration. The solution was poured into a separatory funnel containing water and ether. The layers were separated and the aqueous layer was extracted 3 times with ether. The combined organic layers were washed once with brine, and dried over magnesium sulfate, and the solvents were removed under reduced pressure. The residue was purified by silica gel chromatograhy (97:3, hexane:ethyl acetate) to give the title compound. PNMR (300 MHz, CDCl3)-0.11 (s, 9H), 1.28 (s, 12H), 1.41 (t, 3H, J=7.1 Hz), 1.68 (s, 4H), 2.23 (s, 3H), 4.39 (q, 2H, J=7.1 Hz), 6.86 (s, 1H), 7.08 (s, 1H), 7.17 (s, 1H), 7.41 (d, 2H, J=8.5 Hz), 8.03 (d, 2H, J=8.5 Hz).

Workup

  1. filtrationthe manganese dioxide filtered off
  2. customthe hexane removed in vacuo
  3. dissolutionThe residue was dissolved in 2 mL of ethanol
  4. waitAfter 15 minutes
  5. stirringThe suspension was stirred at room temperature for 6 hours
  6. customthe manganese dioxide removed by filtration
  7. additionThe solution was poured into a separatory funnel
  8. additioncontaining water and ether
  9. customThe layers were separated
  10. extractionthe aqueous layer was extracted 3 times with ether
  11. washThe combined organic layers were washed once with brine
  12. dry with materialdried over magnesium sulfate
  13. customthe solvents were removed under reduced pressure
  14. customThe residue was purified by silica gel chromatograhy (97:3, hexane:ethyl acetate)

Sources & evidence

ORD record
ord-2be333284b554a548772427dbafb692b
Source dataset
uspto-grants-2005_06
Patent number
US06906057B1

Reaction notes

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