Diethyl Ether → Silane, bis(4-butylphenyl)dichloro-

HRID 1441771Notes

Reaction equation

HRID 1441771 reaction equation
[Mg].Br[C:3]1[CH:8]=[CH:7][C:6]([CH2:9][CH2:10][CH2:11][CH3:12])=[CH:5][CH:4]=1.C(O[CH2:16][CH3:17])C.[Cl:18][Si:19]([Cl:22])([Cl:21])[Cl:20]>C1(C)C=CC=CC=1>[CH2:9]([C:6]1[CH:7]=[CH:8][C:3]([Si:19]([Cl:21])([Cl:20])[Cl:18])=[CH:4][CH:5]=1)[CH2:10][CH2:11][CH3:12].[CH2:9]([C:6]1[CH:7]=[CH:8][C:3]([Si:19]([C:3]2[CH:8]=[CH:7][C:6]([CH2:9][CH2:10][CH2:16][CH3:17])=[CH:5][CH:4]=2)([Cl:22])[Cl:18])=[CH:4][CH:5]=1)[CH2:10][CH2:11][CH3:12]

Participants

7

Reactant 4

HCID 3283Diethyl Ether3×HCID 24816Silicon tetrachlorideHCID 5210591-Bromo-4-butylbenzene2×HCID 5462224Magnesium

Product 2

HCID 4193591Silane, bis(4-butylphenyl)dichloro-HCID 68542293(4-Butylphenyl)(trichloro)silane

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent2×

Procedure

A 3 L-volume four-necked flask equipped with a Dimroth condenser, a dropping funnel and a stirrer was charged with magnesium (15.7 g, 0.645 moles, in a flaky state), and the inside of the flask was purged with nitrogen. Diethyl ether (200 mL) was poured while keeping the inside of the flask at a positive pressure, and one piece of iodine was added while stirring. Furthermore, 1-bromo-4-butylbenzene (141.6 g, 0.665 moles) and diethyl ether (500 mL) were charged into the dropping funnel while keeping the inside of the flask at a positive pressure. When the diethyl ether was heated, and refluxing started, the diethyl ether solution of 1-bromo-4-butylbenzene was dropped from the dropping funnel under mild refluxing over about 4.5 hours, and the mixture was stirred for one hour as it was. After finishing stirring under heating, the reaction solution was cooled to room temperature and diluted with 300 mL of toluene. Tetrachlorosilane (44.6 g, 0.263 moles) and toluene (200 mL) were charged into the dropping funnel while keeping the inside of the flask at a positive pressure and dropped at room temperature over about 30 minutes. After completion of the dropping, stirring of the reaction solution was continued at room temperature overnight. A formed crystal of magnesium bromide was filtered, the obtained filtrate was concentrated, and the concentrated liquid was distilled in vacuo. 4-Butylphenyl trichlorosilane as an initial distillate and 48.5 g of pale yellow bis(4-butylphenyl)dichlorosilane (153 to 155° C./4 to 5 Torr) as a major distillate were obtained. This compound was confirmed to be the desired silane compound (aromatic monomer (B1)) from chemical shift, branching and integration values of signals obtained by the 1HNMR measurement (using chloroform as a heavy solvent at 400 MHz) (see FIG. 2). In the following polymerization reaction, a purified material obtained by vacuum distillation of this major distillate just before that was provided. Also, all of the solvents to be used were dried by a molecular sieve and then used.

Workup

  1. customA 3 L-volume four-necked flask equipped with a Dimroth condenser, a dropping funnel and a stirrer
  2. customin a flaky state), and the inside of the flask was purged with nitrogen
  3. additionDiethyl ether (200 mL) was poured
  4. additionwas added
  5. temperaturerefluxing
  6. temperatureunder mild refluxing over about 4.5 hours
  7. stirringthe mixture was stirred for one hour as it
  8. stirringAfter finishing stirring
  9. temperatureunder heating
  10. additiondropped at room temperature over about 30 minutes
  11. stirringAfter completion of the dropping, stirring of the reaction solution
  12. filtrationA formed crystal of magnesium bromide was filtered
  13. concentrationthe obtained filtrate was concentrated
  14. distillationthe concentrated liquid was distilled in vacuo

Sources & evidence

ORD record
ord-b92cce0f5d9c4d9c82754d3f50574b45
Source dataset
uspto-grants-2010_02
Patent number
US07655745B2

Reaction notes

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