Tetrahydrofuran → 8,9-Dihydrocyclopenta[def]phenanthrene

HRID 1172021ノート

反応式

HRID 1172021 の反応式
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

参加物

9

反応物 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

生成物 1

HCID 6057498,9-Dihydrocyclopenta[def]phenanthrene

試薬・触媒・溶媒 4

HCID 74236Tetrabutylammonium Bromide触媒HCID 178418397HCID 178418397、化合物触媒HCID 962Water溶媒HCID 1140Toluene溶媒

反応条件

温度
100 °C

実験手順

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).

後処理

  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

出典と根拠

ORDレコード
ord-fccf89fd1d3e403780096be215d2b6fc
出典データセット
uspto-grants-2010_11
特許番号
US07833635B2

反応ノート

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