Diethyl Ether → Chlorodicyclohexyl(2,7-di-tert-butylfluorenyl)silane

HRID 746974Notes

Reaction equation

HRID 746974 reaction equation
[C:1]([C:5]1[CH:17]=[CH:16][C:15]2[C:14]3[C:9](=[CH:10][C:11]([C:18]([CH3:21])([CH3:20])[CH3:19])=[CH:12][CH:13]=3)[CH2:8][C:7]=2[CH:6]=1)([CH3:4])([CH3:3])[CH3:2].C(OCC)C.C([Li])CCC.[Cl:32][Si:33](Cl)([CH:40]1[CH2:45][CH2:44][CH2:43][CH2:42][CH2:41]1)[CH:34]1[CH2:39][CH2:38][CH2:37][CH2:36][CH2:35]1>CCCCCC>[Cl:32][Si:33]([CH:40]1[CH2:41][CH2:42][CH2:43][CH2:44][CH2:45]1)([CH:34]1[CH2:39][CH2:38][CH2:37][CH2:36][CH2:35]1)[C:10]1[C:9]2[CH2:8][C:7]3[C:15](=[CH:16][CH:17]=[C:5]([C:1]([CH3:4])([CH3:3])[CH3:2])[CH:6]=3)[C:14]=2[CH:13]=[CH:12][C:11]=1[C:18]([CH3:21])([CH3:20])[CH3:19]

Participants

6

Reactant 4

HCID 3283Diethyl EtherHCID 40900822,7-Di-tert-butylfluoreneHCID 10869176DichlorodicyclohexylsilaneHCID 178418339Butyllithium

Product 1

HCID 23078773Chlorodicyclohexyl(2,7-di-tert-butylfluorenyl)silaneYield 101.8%

Reagents, catalysts & solvents 1

HCID 8058HexaneSolvent2×

Procedure

A 300 ml two-necked flask equipped with a three-way cock, a dropping funnel and a magnetic stirrer, was thoroughly purged with nitrogen. Into the flask was introduced 2,7-di-tert-butylfluorene 3.01 g (10.81 mmol), and dissolved by addition of dehydrated diethyl ether 60 ml. With cooling in an ice bath, 1.56 mol/L n-hexane solution of n-butyllithium, 6.9 ml (11.0 mmol), was added to the solution, and the mixture was stirred in a nitrogen atmosphere at room temperature for 20 hours. Separately, a 500 ml three-necked flask equipped with a 100 ml dropping funnel, a three-way cock and a magnetic stirrer was thoroughly purged with nitrogen, and dehydrated n-hexane 120 ml and dichlorodicyclohexylsilane 2.6 ml (11.0 mmol) were introduced into the flask. With the flask cooled in a dry ice/methanol bath, the above-prepared solution was dropwise added over a period of 1 hour by means of the dropping funnel. While allowing the liquid temperature to rise gradually to room temperature, the contents were stirred for 3 days in a nitrogen atmosphere. The resulting slurry was filtered to remove solids, and the solvent of the filtrate was distilled away under reduced pressure to obtain 5.5 g of chlorodicyclohexyl(2,7-di-tert-butylfluorenyl)silane as a light yellow solid (11.0 mmol, 100% yield). The 1H NMR spectrum as measured with respect to the chlorodicyclohexyl(2,7-di-tert-butylfluorenyl)silane is given below:

Workup

  1. customA 300 ml two-necked flask equipped with a three-way cock, a dropping funnel and a magnetic stirrer
  2. customwas thoroughly purged with nitrogen
  3. temperatureWith cooling in an ice bath
  4. customSeparately, a 500 ml three-necked flask equipped with a 100 ml
  5. additionwere introduced into the flask
  6. temperatureWith the flask cooled in a dry ice/methanol bath
  7. additionthe above-prepared solution was dropwise added over a period of 1 hour by means of the dropping funnel
  8. customto rise gradually to room temperature
  9. stirringthe contents were stirred for 3 days in a nitrogen atmosphere
  10. filtrationThe resulting slurry was filtered
  11. customto remove solids
  12. distillationthe solvent of the filtrate was distilled away under reduced pressure

Sources & evidence

ORD record
ord-3d7effc12eac4ed4a28f11ff05ba0dd6
Source dataset
uspto-grants-2008_07
Patent number
US07393965B2

Reaction notes

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