Ammonium Chloride → Bis(4-tert-butylphenyl)cyclopentadienyl(octamethyloctahydrodibenzofluorenyl)methane

HRID 746980Notes

Reaction equation

HRID 746980 reaction equation
[CH3:1][C:2]1([CH3:29])[CH:7]2[CH:8]3[CH2:22][CH2:21][CH:20]=[CH:19][C:9]3=[C:10]3[C:18]([CH2:17][C:16]4[CH:15]=[CH:14][CH:13]=[CH:12][C:11]3=4)=[C:6]2[C:5](C)([CH3:23])[C:4]([CH3:26])([CH3:25])[C:3]1([CH3:28])[CH3:27].[CH2:30]([Li])CCC.[C:35]([C:39]1[CH:44]=[CH:43][C:42]([C:45]([C:51]2[CH:56]=[CH:55][C:54]([C:57]([CH3:60])([CH3:59])[CH3:58])=[CH:53][CH:52]=2)=[C:46]2[CH:50]=[CH:49][CH:48]=[CH:47]2)=[CH:41][CH:40]=1)([CH3:38])([CH3:37])[CH3:36].[Cl-].[NH4+]>O1CCCC1.C(OCC)C.CCCCCC>[C:57]([C:54]1[CH:55]=[CH:56][C:51]([C:45]([C:42]2[CH:43]=[CH:44][C:39]([C:35]([CH3:38])([CH3:37])[CH3:36])=[CH:40][CH:41]=2)([CH:46]2[CH:50]=[CH:49][CH:48]=[CH:47]2)[C:7]2([CH3:30])[C:6]3[C:5]([CH3:23])([CH:12]4[CH2:13][CH2:14][CH:15]=[CH:16][C:11]4=[C:10]4[C:18]=3[CH2:17][C:19]3[CH:20]=[CH:21][CH:22]=[CH:8][C:9]4=3)[C:4]([CH3:26])([CH3:25])[C:3]([CH3:28])([CH3:27])[C:2]2([CH3:1])[CH3:29])=[CH:52][CH:53]=1)([CH3:60])([CH3:59])[CH3:58]

Participants

8

Reactant 4

HCID 25517Ammonium ChlorideHCID 183685676,6-Bis(4-tert-butylphenyl)fulveneHCID 86606716OctamethyloctahydrodibenzofluoreneHCID 178418339Butyllithium

Product 1

HCID 131726950Bis(4-tert-butylphenyl)cyclopentadienyl(octamethyloctahydrodibenzofluorenyl)methaneYield 70.1%

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Procedure

A 300 ml two-necked flask equipped with a magnetic stirrer, a three-way cock and a dropping funnel, was purged thoroughly with nitrogen. Into the flask, octamethyloctahydrodibenzofluorene 2.01 g (5.21 mmol) and dehydrated tetrahydrofuran 40 ml were introduced. With cooling in an ice bath, 1.56 mol/L n-hexane solution of n-butyllithium, 3.5 ml (5.5 mmol), was dropwise added. The contents were stirred at room temperature in a nitrogen atmosphere for 1 day. With the flask cooled in a dry ice/methanol bath, a solution of 6,6-bis(4-tert-butylphenyl)fulvene 1.78 9 (5.20 mmol) in 20 ml of tetrahydrofuran, was dropwise added to the solution by means of the dropping funnel over a period of 20 minutes. The liquid temperature was then slowly raised to room temperature, and the solution was stirred in a nitrogen atmosphere at the temperature for 3 days. Then, a saturated aqueous solution of ammonium chloride 100 ml and diethyl ether 100 ml were gradually added to the solution in this order. The resulting two-phase solution was poured into a 300 ml separation funnel, and the funnel was shaken several timessothatthewaterphasewasremoved. Theobtainedorganic phase was washed three times with water 100 ml and once with a saturated salt solution 100 ml, and dried over anhydrous magnesium sulfate. The solution was filtered to remove solids, and the solvent of the filtrate was distilled away. The residual solid was washed with n-hexane to give 2.664 g of bis(4-tert-butylphenyl)cyclopentadienyl(octamethyloctahydrodibenzofluorenyl)methane as a white solid (3.65 mmol, 70.1% yield). Identification of the bis(4-tert-butylphenyl)cyclopentadienyl(octamethyloctahydrodibenzofluorenyl)methane was made by 1H NMR and the FD-mass spectrometric analysis, the results being given below:

Workup

  1. customA 300 ml two-necked flask equipped with a magnetic stirrer
  2. customa three-way cock and a dropping funnel, was purged thoroughly with nitrogen
  3. temperatureWith cooling in an ice bath
  4. temperatureWith the flask cooled in a dry ice/methanol bath
  5. temperatureThe liquid temperature was then slowly raised to room temperature
  6. stirringthe solution was stirred in a nitrogen atmosphere at the temperature for 3 days
  7. additionThe resulting two-phase solution was poured into a 300 ml separation funnel
  8. stirringthe funnel was shaken several timessothatthewaterphasewasremoved
  9. washTheobtainedorganic phase was washed three times with water 100 ml
  10. dry with materialonce with a saturated salt solution 100 ml, and dried over anhydrous magnesium sulfate
  11. filtrationThe solution was filtered
  12. customto remove solids
  13. distillationthe solvent of the filtrate was distilled away
  14. washThe residual solid was washed with n-hexane

Sources & evidence

ORD record
ord-bf6f52a40c1846ce94df22cdd527e15d
Source dataset
uspto-grants-2008_07
Patent number
US07393965B2

Reaction notes

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