Hydrochloric Acid → HCID 68500262, compound

HRID 2241054Notes

Reaction equation

HRID 2241054 reaction equation
[CH3:1][C:2]1([CH3:11])[CH2:7][C:6]([CH3:9])([CH3:8])[CH2:5][C:4](=O)[CH2:3]1.[OH:12][C:13]1[CH:14]=[C:15]([C:20]([C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)=O)[CH:16]=[CH:17][C:18]=1[CH3:19].Cl.[CH2:29]1COCC1>CCOC(C)=O.[Zn].Cl[Ti](Cl)(Cl)Cl>[CH2:19]([C:18]1[CH:17]=[CH:16][C:15]([C:20]([C:22]2[CH:27]=[CH:26][CH:25]=[CH:24][CH:23]=2)=[C:4]2[CH2:3][C:2]([CH3:11])([CH3:1])[CH2:7][C:6]([CH3:9])([CH3:8])[CH2:5]2)=[CH:14][C:13]=1[OH:12])[CH3:29]

Participants

8

Reactant 4

HCID 313Hydrochloric AcidHCID 8028Tetrahydrofuran2×HCID 843993,3,5,5-TetramethylcyclohexanoneHCID 68504327HCID 68504327, compound

Product 1

HCID 68500262HCID 68500262, compound

Reagents, catalysts & solvents 3

HCID 23994ZincCatalystHCID 24193Titanium TetrachlorideCatalystHCID 8857Ethyl AcetateSolvent

Procedure

To a stirred suspension of Zn powder (2.0 g, 36.0 mmol) and THF (50 mL) under N2 was added TiCl4 (6.0 g, 18.0 mmol). The resulting yellow suspension was refluxed for 1 h. A solution of 3,3,5,5-tetramethylcyclohexanone (1.6 g, 10.7 mmol) and compound 40 (1.00 g, 3.6 mmol) in THF (50 mL) was added dropwise to the refluxing reaction over 15 min. After 2 h, the reaction was cooled to RT and then poured into 150 mL 50% aqueous HCl and stirred for 30 min. The mixture was then diluted with EtOAc (150 mL) and the phase separated. The aqueous phase was washed with 2×100 mL EtOAc and the combined organics washed with brine (150 mL). The organics were then dried over MgSO4, filtered, and the solvents removed in vacuuo. The crude material was purified by column chromatography on silica gel (150 g) with 20% EtOAc to give a the desired product contaminated with 3% of 3,3,5,5-tetramethylcyclohexanone. The desired product was recrystallized from hexanes to give 1.8 g (48%) of 41 as a colorless solid. 1H NMR (400 MHz, CDCl3): δ 0.89 (s, 6H), 0.93 (s, 6H), 1.25 (s, 2H), 1.75 (s, 2H), 1.90 (s, 2H), 2.13 (s, 3H), 6.57-6.89 (m, 3H), 7.01-7.30 (m, 5H), 9.15 (s, 1H).

Workup

  1. temperatureThe resulting yellow suspension was refluxed for 1 h
  2. customthe phase separated
  3. washThe aqueous phase was washed with 2×100 mL EtOAc
  4. washthe combined organics washed with brine (150 mL)
  5. dry with materialThe organics were then dried over MgSO4
  6. filtrationfiltered
  7. customthe solvents removed in vacuuo
  8. customThe crude material was purified by column chromatography on silica gel (150 g) with 20% EtOAc

Sources & evidence

ORD record
ord-1e95f41758564e0ab88a8b8544cceead
Source dataset
uspto-grants-2010_05
Patent number
US07723393B2

Reaction notes

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