Tetrahydrofuran → 8,9-Dihydrocyclopenta[def]phenanthrene

HRID 1172021노트

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HRID 1172021 반응식
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

참가 물질

9

반응물 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

생성물 1

HCID 6057498,9-Dihydrocyclopenta[def]phenanthrene

시약·촉매·용매 4

HCID 74236Tetrabutylammonium Bromide촉매HCID 178418397HCID 178418397, 화합물촉매HCID 962Water용매HCID 1140Toluene용매

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온도
100 °C

실험 절차

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).

후처리

  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

출처 및 근거

ORD 기록
ord-fccf89fd1d3e403780096be215d2b6fc
출처 데이터셋
uspto-grants-2010_11
특허 번호
US07833635B2

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