Dichlorodimethylsilane → HCID 59741523, compound

HRID 1675644Notes

Reaction equation

HRID 1675644 reaction equation
[Li]CCCC.CCCCCC.[CH3:12][C:13]1([CH3:28])[C:24]2[C:16](=[CH:17][C:18]3[CH2:19][C:20]([CH3:25])=[CH:21][C:22]=3[CH:23]=2)[C:15]([CH3:27])([CH3:26])[CH2:14]1.[Si:29]([CH3:33])([CH3:32])(Cl)[Cl:30]>CCOCC>[Cl:30][Si:29]([CH:21]1[C:20]([CH3:25])=[CH:19][C:18]2[CH:17]=[C:16]3[C:24]([C:13]([CH3:28])([CH3:12])[CH2:14][C:15]3([CH3:27])[CH3:26])=[CH:23][C:22]1=2)([CH3:33])[CH3:32]

Participants

6

Reactant 4

HCID 6398DichlorodimethylsilaneHCID 8058HexaneHCID 59741527HCID 59741527, compoundHCID 178418339Butyllithium

Product 1

HCID 59741523HCID 59741523, compoundYield 97.9%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

A 2.5 M n-BuLi solution in hexane (3.8 mL, 9.50 mmol, n-BuLi:indacene=1:1) was added dropwise at 0° C. to a solution of 2.16 g of 1,1,3,3,6-pentamethyl-1,2,3,5-tetrahydro-s-indacene (9.54 mmol) in 40 mL of Et2O. At the end of the addition, the resulting light yellow solution was allowed to warm up to room temperature and stirred for 1 h with final formation of a white suspension. An aliquot of this suspension was quenched with CD3OD and dried: the related 1H NMR analysis in CDCl3 showed complete conversion of the starting indacene to the corresponding lithium salt. The latter was then cooled again to 0° C. and added to a solution of Me2SiCl2 (98%, 1.27 g, d=1.064, 9.64 mmol) in 10 mL of Et2O, previously cooled to 0° C. too. The reaction mixture was allowed to warm up to room temperature and stirred for 16 h with final formation of a white suspension. After 40 min stirring at r.t. the conversion was ca. 80% by 1H NMR analysis. The solvents were removed in vacuo and the residue extracted with 70 mL of toluene to remove the LiCl. The filtrate was brought to dryness in vacuo at 40° C. to give a thick yellow oil as product (3.03 g), which tended to crystallize by standing at room temperature. Isolated yield=97.9% (purity 97.9% wt. by 1 H NMR analysis). Starting indacene was still present in 2.1% wt.

Workup

  1. additionAt the end of the addition
  2. customAn aliquot of this suspension was quenched with CD3OD
  3. customdried
  4. temperatureThe latter was then cooled again to 0° C.
  5. temperaturepreviously cooled to 0° C. too
  6. temperatureto warm up to room temperature
  7. stirringstirred for 16 h with final formation of a white suspension
  8. stirringAfter 40 min stirring at r.t. the conversion
  9. customThe solvents were removed in vacuo
  10. extractionthe residue extracted with 70 mL of toluene
  11. customto remove the LiCl
  12. customwas brought to dryness in vacuo at 40° C.
  13. customto give a thick yellow oil as product (3.03 g), which
  14. customto crystallize
  15. customby standing at room temperature
  16. customIsolated yield=97.9% (purity 97.9% wt. by 1 H NMR analysis)

Sources & evidence

ORD record
ord-7d7565ed42e549a091c99e5d3b79de2e
Source dataset
uspto-grants-2011_08
Patent number
US08003743B2

Reaction notes

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