1,1',1''-(Chlorosilylidyne)tris(benzene) → HCID 59469955, compound

HRID 2364925Notes

Reaction equation

HRID 2364925 reaction equation
Br[C:2]1[CH:3]=[CH:4][C:5]2[NH:6][C:7]3[C:12]([C:13]=2[CH:14]=1)=[CH:11][C:10](Br)=[CH:9][CH:8]=3.[H-].[Na+].Cl[Si:19]([CH2:24][CH3:25])([CH2:22][CH3:23])[CH2:20][CH3:21].[CH2:26]([Li])[CH2:27][CH2:28][CH3:29].Cl[Si:32]([C:45]1[CH:50]=[CH:49][CH:48]=[CH:47][CH:46]=1)([C:39]1[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=1)[C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=1.[Cl-].[NH4+]>C1COCC1>[C:20]1([Si:19]([C:24]2[CH:25]=[CH:9][CH:8]=[CH:7][CH:12]=2)([C:22]2[CH:13]=[CH:14][CH:2]=[CH:3][CH:23]=2)[C:2]2[CH:3]=[CH:4][C:5]3[NH:6][C:7]4[C:12]([C:13]=3[CH:14]=2)=[CH:11][C:10]([Si:32]([C:45]2[CH:50]=[CH:49][CH:48]=[CH:47][CH:46]=2)([C:39]2[CH:44]=[CH:43][CH:42]=[CH:41][CH:40]=2)[C:33]2[CH:38]=[CH:37][CH:36]=[CH:35][CH:34]=2)=[CH:9][CH:8]=4)[CH:29]=[CH:28][CH:27]=[CH:26][CH:21]=1

Participants

8

Reactant 6

HCID 64581,1',1''-(Chlorosilylidyne)tris(benzene)HCID 13819ChlorotriethylsilaneHCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 2748743,6-DibromocarbazoleHCID 178418339Butyllithium2×

Product 1

HCID 59469955HCID 59469955, compoundYield 66%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent3×

Conditions

Temperature
0 °C

Procedure

A solution of 3,6-dibromocarbazole (9.1 g, 1 eq) in dry THF (400 ml) at 0° C. under argon is admixed slowly with NaH (60% in mineral oil, 1.3 g, 1.2 eq) and stirred at 0° C. for 2 h. After adding a solution of chlorotriethylsilane (5.1 g, 1.2 eq) in dry THF (80 ml), the solution is stirred at RT (room temperature) for 1 h. The solution is cooled to −78° C. and admixed with n-butyllithium (1.6 M in hexane, 43.8 ml, 2.5 eq) and stirred at −78° C. for 1 h. After adding a solution of chlorotriphenylsilane (29.8 g, 3.5 eq) in dry THF (100 ml) at −78° C., the mixture is warmed to room temperature overnight with stirring. Excess butyllithium is hydrolyzed with saturated ammonium chloride solution. The precipitated product is filtered off and washed thoroughly with methylene chloride. The combined methylene chloride filtrates are extracted by shaking with water and dried over sodium sulfate. The organic phase is admixed with tetra-n-butylammonium fluoride (TBAF, 1 M in THF, 2 ml) and stirred at RT for 4 h. The mixture is concentrated down to 100 ml. The resulting precipitate is filtered and washed with n-hexane. Yield 66%.

Workup

  1. customat 0° C.
  2. stirringthe solution is stirred at RT (room temperature) for 1 h
  3. temperatureThe solution is cooled to −78° C.
  4. stirringstirred at −78° C. for 1 h
  5. temperaturethe mixture is warmed to room temperature overnight
  6. stirringwith stirring
  7. filtrationThe precipitated product is filtered off
  8. washwashed thoroughly with methylene chloride
  9. extractionThe combined methylene chloride filtrates are extracted
  10. stirringby shaking with water
  11. dry with materialdried over sodium sulfate
  12. stirringstirred at RT for 4 h
  13. concentrationThe mixture is concentrated down to 100 ml
  14. filtrationThe resulting precipitate is filtered
  15. washwashed with n-hexane

Sources & evidence

ORD record
ord-f71db7a5f70c4737b0674cdd3991713f
Source dataset
uspto-grants-2014_04
Patent number
US08697255B2

Reaction notes

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