Ammonium Chloride → Cyclopentadienyl(octamethyloctahydrodibenzofluorenyl)di-p-tolylmethane

HRID 746979Notes

Reaction equation

HRID 746979 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]1([CH3:54])[CH:40]=[CH:39][C:38]([C:41]([C:47]2[CH:52]=[CH:51][C:50]([CH3:53])=[CH:49][CH:48]=2)=[C:42]2[CH:46]=[CH:45][CH:44]=[CH:43]2)=[CH:37][CH:36]=1.[Cl-].[NH4+]>O1CCCC1.O.C(OCC)C.CCCCCC>[CH:42]1([C:41]([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])([C:38]2[CH:37]=[CH:36][C:35]([CH3:54])=[CH:40][CH:39]=2)[C:47]2[CH:48]=[CH:49][C:50]([CH3:53])=[CH:51][CH:52]=2)[CH:43]=[CH:44][CH:45]=[CH:46]1

Participants

9

Reactant 4

HCID 25517Ammonium ChlorideHCID 124276304,4'-(Cyclopenta-2,4-dien-1-ylidenemethylene)bis(methylbenzene)HCID 86606716OctamethyloctahydrodibenzofluoreneHCID 178418339Butyllithium

Product 1

HCID 131726949Cyclopentadienyl(octamethyloctahydrodibenzofluorenyl)di-p-tolylmethaneYield 71.3%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 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 2.98 g (7.71 mmol) was introduced, and dehydrated tetrahydrofuran 60 ml was further added. With cooling in an ice bath, 1.56 mol/L n-hexane solution of n-butyllithium, 5.2 ml (8.1 mmol), was dropwise added. The contents were stirred at room temperature in a nitrogen atmosphere for 7 hours. With the flask cooled in a dry ice/methanol bath, a solution of 6,6-di-p-tolyl fulvene 2.40 g (9.27 mmol) in 30 ml of dehydrated tetrahydrofuran, was dropwise added to the flask over a period of 20 minutes by means of the dropping funnel. The liquid temperature was gradually raised to room temperature, and the solution was stirred in a nitrogen atmosphere at the temperature for 21 hours. A saturated aqueous solution of ammonium chloride 100 ml and diethyl ether 100 ml were gradually added in this order. The resulting two-phase solution was poured into a 300 ml separation funnel, and the funnel was shaken several times so that the water phase was removed. The obtained organic phase was washed twice 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 3.55 g of cyclopentadienyl(octamethyloctahydrodibenzofluorenyl)di-p-tolyl methane as a white solid (5.50 mmol, 71.3% yield). Identification of the cyclopentadienyl(octamethyloctahydrodibenzofluorenyl)di-p-tolyl 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 gradually raised to room temperature
  6. stirringthe solution was stirred in a nitrogen atmosphere at the temperature for 21 hours
  7. additionThe resulting two-phase solution was poured into a 300 ml separation funnel
  8. customwas removed
  9. washThe obtained organic phase was washed twice with water 100 ml and once with a saturated salt solution 100 ml
  10. dry with materialdried 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-3f684b9b2a1e4881a44011a00cf355a5
Source dataset
uspto-grants-2008_07
Patent number
US07393965B2

Reaction notes

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