Water → (2E)-4,4-dimethyl-2-(((triisopropylsilyl)oxy)methylene)cyclohexanone

HRID 1920484Notes

Reaction equation

HRID 1920484 reaction equation
[CH3:1][CH:2]1[CH2:6][CH2:5][CH2:4][O:3]1.[CH2:7](N(CC)CC)C.[CH:14]([Si:17](Cl)([CH:21]([CH3:23])[CH3:22])[CH:18]([CH3:20])[CH3:19])([CH3:16])[CH3:15].[CH3:25][CH2:26][CH2:27]CCCC.[OH2:32]>C1(C)C=CC=CC=1>[CH3:1][C:2]1([CH3:7])[CH2:27][CH2:26][C:25](=[O:32])/[C:5](=[CH:4]/[O:3][Si:17]([CH:21]([CH3:23])[CH3:22])([CH:18]([CH3:20])[CH3:19])[CH:14]([CH3:16])[CH3:15])/[CH2:6]1

Participants

7

Reactant 5

HCID 962WaterHCID 73012-MethyltetrahydrofuranHCID 8471TriethylamineHCID 8900HeptaneHCID 139400Triisopropylsilyl chloride

Product 1

HCID 44594328(2E)-4,4-dimethyl-2-(((triisopropylsilyl)oxy)methylene)cyclohexanone

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Conditions

Temperature
2.5 °C

Procedure

EXAMPLE 1 (21 g as an 18% solution in toluene) was charged to a 1 L flask followed by 2-methyltetrahydrofuran (300 mL). The reaction mixture was cooled to between 0-5° C., and triethylamine (20.67 g, 1.5 equiv) was charged maintaining a reaction temperature between 0-5° C. Triisopropylsilylchloride (TIPSCl) (28.9 g, 1.1 equiv) was slowly charged, maintaining a reaction temperature between 0-5° C. The reaction mixture was mixed at a temperature range between 0-5° C. and monitored by GC for completion. Heptane (430 mL) was added, and temperature was adjusted to 10° C. Water (300 mL) was added, maintaining an internal temperature below 15° C. The reaction mixture was mixed thoroughly, and the layers were separated. The organic layer was washed with water (2×200 mL), 20% aqueous NaCl (200 mL) and 20% aqueous NaCl (360 mL). The organic layer was distilled to approximately 100 mL and chased with toluene (280 mL). The title compound was stored as a toluene solution in the refrigerator. 1H NMR (400 MHz, CDCl3) δ 1.03 (s, 6 H) 1.07 (d, J=5.76 Hz, 14 H) 1.10 (s, 10 H) (with overlapping residual solvent resonances) 1.23 (dd, J=14.55, 6.59 Hz, 3 H) 1.26-1.29 (m, 2 H) (residual solvent) 1.64 (t, J=7.00 Hz, 2 H) 2.06 (s, 1 H), 2.26-2.28 (m, 2 H) 2.38 (t, J=7.00 Hz, 2 H) 7.55 (t, J=1.92 Hz, 1 H) ppm. Mass spec: DCI/NH3 M+1=311 amu; M+NH3=328 amu.

Workup

  1. additionwas charged
  2. temperaturemaintaining a reaction temperature between 0-5° C
  3. additionThe reaction mixture was mixed at a temperature range between 0-5° C.
  4. customwas adjusted to 10° C
  5. temperaturemaintaining an internal temperature below 15° C
  6. additionThe reaction mixture was mixed thoroughly
  7. customthe layers were separated
  8. washThe organic layer was washed with water (2×200 mL), 20% aqueous NaCl (200 mL) and 20% aqueous NaCl (360 mL)
  9. distillationThe organic layer was distilled to approximately 100 mL and chased with toluene (280 mL)

Sources & evidence

ORD record
ord-4d768d04b55e4b6fa9da1374395a70eb
Source dataset
uspto-grants-2012_05
Patent number
US08168784B2

Reaction notes

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