Tetrahydrofuran → 2-Bromo-cyclopenta[def]phenanthren-4-one

HRID 254131Notes

Reaction equation

HRID 254131 reaction equation
[Br:1][C:2]1[CH:15]=[C:14]2[CH2:16][C:11]3[C:12]4[C:13]2=[C:4]([CH2:5][CH2:6][C:7]=4[CH:8]=[CH:9][CH:10]=3)[CH:3]=1.CC1(C)C(C)(C)OB(C2C3C(C(C4C=CC=CC=4)=C4C=2C=CC=C4)=CC=CC=3)[O:19]1.C([O-])([O-])=O.[K+].[K+].C1COCC1>[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.O.C1(C)C=CC=CC=1>[Br:1][C:2]1[CH:15]=[C:14]2[C:16](=[O:19])[C:11]3[C:12]4=[C:13]2[C:4](=[CH:5][CH:6]=[C:7]4[CH:8]=[CH:9][CH:10]=3)[CH:3]=1

Participants

9

Reactant 4

HCID 8028TetrahydrofuranHCID 11430Potassium CarbonateHCID 125243632-bromo-8,9-dihydro-4H-cyclopenta[def]phenanthreneHCID 592076184,4,5,5-Tetramethyl-2-(10-phenylanthracen-9-yl)-1,3,2-dioxaborolane

Product 1

HCID 125243702-Bromo-cyclopenta[def]phenanthren-4-one

Reagents, catalysts & solvents 4

HCID 74236Tetrabutylammonium BromideCatalystHCID 178418397HCID 178418397, compoundCatalystHCID 962WaterSolventHCID 1140TolueneSolvent

Conditions

Temperature
100 °C

Procedure

The compound 2 (1.0 g, 1 eq., 2.02 mmol), 4,4,5,5-tetramethyl-2-(10-phenyl-anthracene-9-yl)-[1,3,2]dioxaborolane (0.77 g, 1 eq., 2.02 mmol), tetrakis(triphenylphosphine)palladium(0) (0.23 g, 0.1 eq., 0.2 mmol), 2M K2CO3 (1 ml, 1 eq., 2.02 mmol), and tetrabutylammoniumbromide (0.65 g, 1 eq., 2.02 mmol) were put into a 100 ml round bottom flask under an argon gas atmosphere, and THF (50 ml) and toluene (20 ml) were added thereto. The reaction mixture was refluxed at 100° C. for 16 hours. When the reaction solution turned dark brown, water was added, and the resultant solution was extracted with ethylacetate. The extracted organic phase was dried over anhydrous magnesium sulfate and filtered to remove a solvent. The residue was dissolved in a trace amount of toluene and purified on a silica gel column. The resultant solid was recrystallized from toluene and methanol to give a material 1 represented by Formula 18 (0.71 g, 52%). 1H NMR (300 MHz, CDCl3, δ): 8.11 (s, 2H), 7.98 (s, 3H), 7.81 (s, 2H), 7.75-7.10 (m, 13H), 1.93 (m, 4H), 1.21 (m, 20H), 0.87 (m, 6H), 0.65 (broad s, 4H).

Workup

  1. extractionthe resultant solution was extracted with ethylacetate
  2. dry with materialThe extracted organic phase was dried over anhydrous magnesium sulfate
  3. filtrationfiltered
  4. customto remove a solvent
  5. dissolutionThe residue was dissolved in a trace amount of toluene
  6. custompurified on a silica gel column
  7. customThe resultant solid was recrystallized from toluene and methanol

Sources & evidence

ORD record
ord-c7693fbbabb24202b4000e05f77b4fe3
Source dataset
uspto-grants-2011_01
Patent number
US07875367B2

Reaction notes

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