3-Chlorocyclopent-1-ene → 3-(5-[(1,1-Dimethylethyl)dimethylsiloxy]pent-1-yl)cyclopentene

HRID 1789543Notes

Reaction equation

HRID 1789543 reaction equation
Cl[CH2:2][CH2:3][CH2:4][CH2:5][CH2:6]O[Si](CC(C)C)(C)C.Cl[CH2:16][CH2:17][CH2:18][CH2:19][CH2:20][O:21][Si:22]([C:25]([CH3:28])([CH3:27])[CH3:26])([CH3:24])[CH3:23].[Mg].ClC1CCC=C1>O1CCCC1.O>[CH3:26][C:25]([Si:22]([CH3:24])([CH3:23])[O:21][CH2:20][CH2:19][CH2:18][CH2:17][CH2:16][CH:5]1[CH2:4][CH2:3][CH:2]=[CH:6]1)([CH3:28])[CH3:27]

Participants

7

Reactant 4

HCID 72973-Chlorocyclopent-1-eneHCID 5462224MagnesiumHCID 13249888Tert-butyl[(5-chloropentyl)oxy]dimethylsilaneHCID 20028701(5-Chloro-1-pentyloxy)(2,2-dimethylethyl)dimethylsilane

Product 1

HCID 139240733-(5-[(1,1-Dimethylethyl)dimethylsiloxy]pent-1-yl)cyclopentene

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

All reactions are carried out under an inert atmosphere. The starting material, (5-chloro-1-pentyloxy)(2,2-dimethylethyl) dimethylsilane {[(5-chloropentyl)oxy](1,1-dimethylethyl)dimethylsilane} (534 g, 2.26 moles), diluted in tetrahydrofuran (500 ml), is added portionwise to a refluxing solution of tetrahydrofuran and granular magnesium (75 g). After the addition is complete the reaction is refluxed an additional 2 hours and the resultant Grignard salt is cooled to room temperature, cannulated into a three liter flask, and cooled to -20° C. A solution of Li2CuCl4 (6.4 mmoles) is added, followed by the dropwise addition of 3-chlorocyclopentene (219 g, 2.1 moles) cooled in a -20° C. dry ice/ethanol bath. After the addition is complete the mixture is warmed to room temperature. Water (500 ml) is added. The reaction mixture is extracted with hexane (3×400 ml). The organic layers are combined, washed with brine (2×500 ml) and dried over anhydrous sodium sulfate. The remaining solvent is removed under vacuum leaving a clear yellow oil. The crude product is fractionally distilled under reduced pressure leaving a clear, colorless oil (478 g, 1.78 moles), BP 96° C./0.3 mm.

Workup

  1. additionAfter the addition
  2. temperatureis refluxed an additional 2 hours
  3. customcannulated into a three liter flask
  4. temperaturecooled to -20° C
  5. temperaturecooled in a -20° C. dry ice/ethanol bath
  6. additionAfter the addition
  7. temperatureis warmed to room temperature
  8. extractionThe reaction mixture is extracted with hexane (3×400 ml)
  9. washwashed with brine (2×500 ml)
  10. dry with materialdried over anhydrous sodium sulfate
  11. customThe remaining solvent is removed under vacuum
  12. customleaving a clear yellow oil
  13. distillationThe crude product is fractionally distilled under reduced pressure

Sources & evidence

ORD record
ord-44a89d079e1d4521b5a9c6a109d06cd9
Source dataset
uspto-grants-1987_08
Patent number
US04689345

Reaction notes

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