1-Heptanethiol → 2,7-Dibromo-9-(bis-heptylsulfanyl-methylene)fluorene

HRID 393126

反応式

HRID 393126 の反応式
[H-].[Na+].[CH2:3]([SH:10])[CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH3:9].[Br:11][C:12]1[CH:24]=[CH:23][C:22]2[C:21]3[C:16](=[CH:17][C:18]([Br:25])=[CH:19][CH:20]=3)[C:15](=[C:26](Br)Br)[C:14]=2[CH:13]=1>C(COC)OC.[Ni](Cl)Cl.N1C=CC=CC=1C1C=CC=CN=1.C1(C)C=CC=CC=1>[Br:25][C:18]1[CH:19]=[CH:20][C:21]2[C:22]3[C:14](=[CH:13][C:12]([Br:11])=[CH:24][CH:23]=3)[C:15](=[C:26]([S:10][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH3:9])[S:10][CH2:3][CH2:4][CH2:5][CH2:6][CH2:7][CH2:8][CH3:9])[C:16]=2[CH:17]=1

参加物

7

反応物 3

HCID 154221-HeptanethiolHCID 24758Sodium hydrideHCID 226485382,7-Dibromo-9-(dibromomethylidene)-9H-fluorene

生成物 1

HCID 226485432,7-Dibromo-9-(bis-heptylsulfanyl-methylene)fluorene収率 75%

試薬・触媒・溶媒 3

HCID 14742,2'-Bipyridine触媒HCID 15773433Dichloronickel;1,2-dimethoxyethane触媒HCID 1140Toluene溶媒

実験手順

A 60% dispersion of sodium hydride in mineral oil (3.45 g, 86.25 mmol) was added under a heavy flow of nitrogen to anhydrous toluene (1 L). 1-Heptanethiol (14.65 g, 17.0 mL, 110.7 mmol) was added via syringe. Once effervescence stopped, 2,7-dibromo-9-dibromomethylene-fluorene (2) (18.50 g, 37.46 mmol) was added followed by 2,2′-bipyridyl (0.29 g, 1.87 mmol) and nickel(II) chloride dimethoxyethane adduct (0.41 g, 1.87 mmol). The reaction was stirred overnight at reflux. After cooling to room temperature, the reaction mixture was washed with 2M aqueous sodium hydroxide (2×100 mL), 5% aqueous hydrochloric acid (2×100 mL), water (200 mL), and brine (200 ml) before being dried over sodium sulphate and evaporated to dryness. Excess 1-heptanethiol was removed via Kugelrohr distillation. The crude product was purified by flash chromatography (eluent: petrol 40-60) followed by recrystallisation from iso-hexane to afford 2,7-dibromo-9-(bis-heptylsulfanyl-methylene)-fluorene (3) (16.76 g, 75%) as a bright yellow solid, purity 100% (GC): υmax (KBr, cm−1) 3068, 2949, 2920, 2851, 1588, 1559, 1513, 1443, 1396, 1330; δH(CDCl3, 300 MHz) 9.09 (2H, s), 7.53 (2H, d, 3JHH=6.0 Hz), 7.43 (2H, d, 3JHH=6.0 Hz), 3.04 (4H, t, 3JHH=7.5 Hz) 1.70 (4H, m), 1.43 (4H, m), 1.26 (12H, m), 0.86 (6H, m); δc(CDCl3, 75 MHz) 145.5, 139.7, 137.6, 136.1, 130.3, 129.5, 121.1, 120.3, 36.4, 31.7, 30.1, 28.9, 22.6, 14.1; M+=596 (t).

後処理

  1. temperatureat reflux
  2. washthe reaction mixture was washed with 2M aqueous sodium hydroxide (2×100 mL), 5% aqueous hydrochloric acid (2×100 mL), water (200 mL), and brine (200 ml)
  3. dry with materialbefore being dried over sodium sulphate
  4. customevaporated to dryness
  5. customExcess 1-heptanethiol was removed via Kugelrohr distillation
  6. customThe crude product was purified by flash chromatography (eluent: petrol 40-60)
  7. customfollowed by recrystallisation from iso-hexane

出典と根拠

ORDレコード
ord-5ce32c9e0d404cd6986424775c9d44c7
出典データセット
uspto-grants-2004_10
特許番号
US06805922B2

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