Hydrochloric Acid → (1,1,3,6,8,8-hexamethyl-1H,8H-dicyclopenta[b,h]fluorenyl)(cyclopentadienyl)di-p-tolylmethane

HRID 1174076Notes

Reaction equation

HRID 1174076 reaction equation
[CH3:1][C:2]1([CH3:25])[C:17]2[CH:16]=[C:15]3[C:7]([C:8]4[CH:9]=[C:10]5[C:20]([CH3:21])=[CH:19][C:18]([CH3:23])([CH3:22])[C:11]5=[CH:12][C:13]=4[CH2:14]3)=[CH:6][C:5]=2[C:4]([CH3:24])=[CH:3]1.C([Li])CCC.CCCCCC.[C:37]1([CH3:56])[CH:42]=[CH:41][C:40]([C:43]([C:49]2[CH:54]=[CH:53][C:52]([CH3:55])=[CH:51][CH:50]=2)=[C:44]2[CH:48]=[CH:47][CH:46]=[CH:45]2)=[CH:39][CH:38]=1.Cl>O1CCCC1.C(OCC)C>[CH3:1][C:2]1([CH3:25])[C:17]2[CH:16]=[C:15]3[C:7]([C:8]4[CH:9]=[C:10]5[C:20]([CH3:21])=[CH:19][C:18]([CH3:23])([CH3:22])[C:11]5=[CH:12][C:13]=4[CH2:14]3)=[CH:6][C:5]=2[C:4]([CH3:24])=[C:3]1[C:43]([CH:44]1[CH:45]=[CH:46][CH:47]=[CH:48]1)([C:40]1[CH:39]=[CH:38][C:37]([CH3:56])=[CH:42][CH:41]=1)[C:49]1[CH:50]=[CH:51][C:52]([CH3:55])=[CH:53][CH:54]=1

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 124276304,4'-(Cyclopenta-2,4-dien-1-ylidenemethylene)bis(methylbenzene)HCID 586524371,1,3,6,8,8-hexamethyl-1H,8H-dicyclopenta[b,h]fluoreneHCID 178418244HCID 178418244, compound

Product 1

HCID 131728536(1,1,3,6,8,8-hexamethyl-1H,8H-dicyclopenta[b,h]fluorenyl)(cyclopentadienyl)di-p-tolylmethaneYield 29.6%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

To a 200-ml two-neck flask equipped with a magnetic stirrer, a three-way cock and a 50 ml dropping funnel, 749 mg (2.29 mmol) of 1,1,3,6,8,8-hexamethyl-1H,8H-dicyclopenta[b,h]fluorene and 30 ml of tetrahydrofuran were charged under nitrogen atmosphere. 1.56 ml (2.43 mmol) of 1.56 mol/l n-butyllithium/hexane solution was gradually added thereto, while cooling it in an ice water bath, and the mixture was stirred at room temperature for 6.5 hours. 718 mg (2.78 mmol) of 6,6-di-p-tolylfulvene dissolved in 30 ml of tetrahydrofuran in advance was gradually added thereto over 20 minutes using the dropping funnel, while cooling it in a methanol/dry ice bath. The temperature of the reaction solution was gradually elevated back to room temperature, and the solution was stirred at room temperature for 20 hours. 50 ml of 1 N hydrochloric acid was gradually added thereto, and 50 ml of diethyl ether was further added to the mixture. The organic layer was separated, washed twice with 50 ml of water, once with 50 ml of saturated solution of salt. After the solution was dried over magnesium sulfate, the solvent was distilled off, and the obtained product was purified by column chromatography. The production quantity was 397 mg (0.679 mmol), and the yield was 29.6%. Identification was performed by 1H-NMR spectrum and FD-MS spectrum. The measurement results are shown as follows.

Workup

  1. customTo a 200-ml two-neck flask equipped with a magnetic stirrer
  2. temperaturewhile cooling it in an ice water bath
  3. additionwas gradually added
  4. waitover 20 minutes using
  5. temperaturethe dropping funnel, while cooling it in a methanol/dry ice bath
  6. customwas gradually elevated back to room temperature
  7. stirringthe solution was stirred at room temperature for 20 hours
  8. customThe organic layer was separated
  9. washwashed twice with 50 ml of water, once with 50 ml of saturated solution of salt
  10. dry with materialAfter the solution was dried over magnesium sulfate
  11. distillationthe solvent was distilled off
  12. customthe obtained product was purified by column chromatography
  13. customThe measurement results

Sources & evidence

ORD record
ord-e9cd1d122ee447a6a0592b7ea054e0d3
Source dataset
uspto-grants-2010_11
Patent number
US07834204B2

Reaction notes

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