Hydrochloric Acid → Di-2-naphthyl(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)methane

HRID 1050672Notes

Reaction equation

HRID 1050672 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.CCCCCC.[CH:41]1[C:50]2[C:45](=[CH:46][CH:47]=[CH:48][CH:49]=2)[CH:44]=[CH:43][C:42]=1[C:51]([C:57]1[CH:66]=[CH:65][C:64]2[C:59](=[CH:60][CH:61]=[CH:62][CH:63]=2)[CH:58]=1)=[C:52]1[CH:56]=[CH:55][CH:54]=[CH:53]1.Cl>O1CCCC1.C(OCC)C>[CH:58]1[C:59]2[C:64](=[CH:63][CH:62]=[CH:61][CH:60]=2)[CH:65]=[CH:66][C:57]=1[C:51]([C:42]1[CH:43]=[CH:44][C:45]2[C:50](=[CH:49][CH:48]=[CH:47][CH:46]=2)[CH:41]=1)([CH:52]1[CH:56]=[CH:55][CH:54]=[CH:53]1)[C:7]1([CH3:30])[C:6]2[C:5]([CH3:23])([CH:12]3[CH2:13][CH2:14][CH:15]=[CH:16][C:11]3=[C:10]3[C:18]=2[CH2:17][C:19]2[CH:20]=[CH:21][CH:22]=[CH:8][C:9]3=2)[C:4]([CH3:26])([CH3:25])[C:3]([CH3:28])([CH3:27])[C:2]1([CH3:1])[CH3:29]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 86606716OctamethyloctahydrodibenzofluoreneHCID 866231976,6-Di-2-naphthylfulveneHCID 178418244HCID 178418244, compound

Product 1

HCID 131736085Di-2-naphthyl(cyclopentadienyl)(octamethyloctahydrodibenzofluorenyl)methane

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

A 200-ml two-necked flask equipped with a magnetic stirrer, a three-way cock and a 100-ml dropping funnel was thoroughly purged with nitrogen, and sequentially charged with 1.35 g (3.48 mmol) of octamethyloctahydrodibenzofluorene and 40 mL of tetrahydrofuran. Then, 2.30 ml (3.60 mmol) of a 1.58 mol/l n-butyllithium/hexane solution was gradually added while cooling the mixture in an ice water bath, and then the mixture was stirred at room temperature for 20 hours under a nitrogen atmosphere. Subsequently, 1.18 g (3.57 mmol) of 6,6-di-2-naphthylfulvene dissolved in 30 ml of tetrahydrofuran in advance was gradually added over 30 minutes while cooling the mixture in a methanol/dry ice bath. The mixture was gradually warmed to room temperature, and stirred for 20 hours at room temperature under a nitrogen atmosphere. Then, 100 ml of 1 N hydrochloric acid was gradually added, and subsequently 100 ml of diethyl ether was added. The two-layered solution thus obtained was transferred to a 300-ml separatory funnel and the funnel was shaken several times. The aqueous layer was then removed. Subsequently, the organic layer obtained was washed 2 times with 100 ml of water and once with 100 ml of saturated brine, and dried over anhydrous magnesium sulfate for 3 hours. The solids were separated by filtration, and the solvent was distilled off. The residue was purified by separation using silica gel chromatography to obtain a target product (yield 1.28 g (51%)). The target product was identified by 1H-NMR and FD-MS spectroscopy.

Workup

  1. customA 200-ml two-necked flask equipped with a magnetic stirrer
  2. customwas thoroughly purged with nitrogen
  3. temperaturewhile cooling the mixture in an ice water bath
  4. additionwas gradually added over 30 minutes
  5. temperaturewhile cooling the mixture in a methanol/dry ice bath
  6. temperatureThe mixture was gradually warmed to room temperature
  7. stirringstirred for 20 hours at room temperature under a nitrogen atmosphere
  8. customThe two-layered solution thus obtained
  9. customwas transferred to a 300-ml separatory funnel
  10. stirringthe funnel was shaken several times
  11. customThe aqueous layer was then removed
  12. customSubsequently, the organic layer obtained
  13. washwas washed 2 times with 100 ml of water
  14. dry with materialonce with 100 ml of saturated brine, and dried over anhydrous magnesium sulfate for 3 hours
  15. customThe solids were separated by filtration
  16. distillationthe solvent was distilled off
  17. customThe residue was purified by separation
  18. customto obtain a target product (yield 1.28 g (51%))

Sources & evidence

ORD record
ord-e00956fb26c449958f60f9564ca18648
Source dataset
uspto-grants-2016_07
Patent number
US09382356B2

Reaction notes

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