Tetrahydrofuran → HCID 12058650, compound

HRID 1287968Notes

Reaction equation

HRID 1287968 reaction equation
[Li].[C:2]1([P:8]([C:15]2[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=2)[C:9]2[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=2)[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C(Cl)(C)(C)C.ClC1C=CC([Si:33]([O:40][CH2:41][CH3:42])([O:37][CH2:38][CH3:39])[O:34][CH2:35][CH3:36])=CC=1.[O:43]1CCCC1>>[C:15]1([P:8]([C:2]2[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=2)([C:9]2[CH:14]=[CH:13][C:12]([Si:33]([O:40][CH2:41][CH3:42])([O:37][CH2:38][CH3:39])[O:34][CH2:35][CH3:36])=[CH:11][CH:10]=2)=[O:43])[CH:16]=[CH:17][CH:18]=[CH:19][CH:20]=1

Participants

6

Reactant 5

HCID 8028Tetrahydrofuran3×HCID 10486tert-BUTYL CHLORIDEHCID 11776TriphenylphosphineHCID 89018(4-Chlorophenyl)triethoxysilaneHCID 3028194Lithium2×

Product 1

HCID 12058650HCID 12058650, compoundYield 15%

Procedure

To a suspension of lithium (2.1 g, 0.3 g atom) in 150 ml of anhydrous tetrahydrofuran held under nitrogen, a solution of triphenylphosphine (26.2 g, 0.1 ml) in 150 ml dry tetrahydrofuran is added in a period of 1/2 hour. The temperature rises from 25° C to 55° C. The solution turns blood-red and nearly all of the lithium dissolves in 3 hours. To this solution t-butyl chloride (9.3 g, 0.1 mol) is added to destroy the phenyl lithium. The solution is filtered, and to it 4-chlorophenyl triethoxysilane (27.5 g, 0.1 mol) dissolved in 50 ml of dry tetrahydrofuran is added and the solution refluxed 4 hours. The red color is not fully discharged in this time due to the sluggish nature of the nucleophilic displacement of the aryl chloride. The excess lithium diphenylphosphide is destroyed by addition of 25 ml of ethanol and finally, water. The solvents are removed in vacuum. The liquid is taken up in toluene and filtered to remove precipitated lithium chloride. Gas-liquid chromatographic analysis of this solution shows the presence of recovered chlorophenyl silane, triphenylphosphine, and only a small amount (estimated 15 percent yield) of 4-(diphenylphosphinyl)phenyl triethoxysilane.

Workup

  1. customrises from 25° C to 55° C
  2. customto destroy the phenyl lithium
  3. filtrationThe solution is filtered
  4. additionis added
  5. temperaturethe solution refluxed 4 hours
  6. customThe excess lithium diphenylphosphide is destroyed by addition of 25 ml of ethanol
  7. customThe solvents are removed in vacuum
  8. filtrationfiltered
  9. customto remove
  10. customprecipitated lithium chloride

Sources & evidence

ORD record
ord-78cc579ed5e14581b2a61ffe1404ce28
Source dataset
uspto-grants-1976_10
Patent number
US03987009

Reaction notes

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