Tetrahydrofuran → 8,9-Dihydrocyclopenta[def]phenanthrene

HRID 1172021Notes

Reaction equation

HRID 1172021 reaction equation
Br[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]=[C:9](Br)[CH:10]=3)[CH:3]=1.CC1(C)C(C)(C)OB(C2C=CC3N(C4C=CC(C)=CC=4)C4C(OC=3C=2)=CC=CC=4)O1.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>[CH:3]1[C:4]2[CH2:5][CH2:6][C:7]3[CH:8]=[CH:9][CH:10]=[C:11]4[CH2:16][C:14]([C:13]=2[C:12]=34)=[CH:15][CH:2]=1

Participants

9

Reactant 4

HCID 8028TetrahydrofuranHCID 11430Potassium CarbonateHCID 125243672,6-dibromo-8,9-dihydro-4H-cyclopenta[def]phenanthreneHCID 686569163-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolane-2-yl)-10-p-tolyl-10H-phenoxazine

Product 1

HCID 6057498,9-Dihydrocyclopenta[def]phenanthrene

Reagents, catalysts & solvents 4

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

Conditions

Temperature
100 °C

Procedure

1.14 g (1 eq, 2.0 mmol) of the compound 2, 0.8 g (1 eq, 2.0 mmol) of 3-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolane-2-yl)-10-p-tolyl-10H-phenoxazine, 0.23 g (0.1 eq, 0.2 mmol) of tetrakis(triphenylphosphine)palladium(0), 1 ml (1 eq, 2.0 mmol) of 2M K2CO3, and 0.65 g (1 eq, 2.0 mmol) of tetrabutylammoniumbromide 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 10 (0.95 g, 50%). 1H NMR (300 MHz, CDCl3, δ): 8.11(s, 2H), 7.98(s, 2H), 7.81(s, 2H), 7.25-5.87(m, 22H), 2.51(s, 3H), 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-fccf89fd1d3e403780096be215d2b6fc
Source dataset
uspto-grants-2010_11
Patent number
US07833635B2

Reaction notes

Loading…