Iodine → (E)-4-((2-Iodovinyl)oxy)-1,1'-biphenyl

HRID 1053503

Reaktionsgleichung

Reaktionsgleichung von HRID 1053503
C([BH-](CC)CC)C.[Li+].[C:9]([O:11][C:12]1[CH:17]=[CH:16][C:15]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)=[CH:14][CH:13]=1)#[CH:10].[I:24]I>C1COCC1>[I:24]/[CH:10]=[CH:9]/[O:11][C:12]1[CH:17]=[CH:16][C:15]([C:18]2[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=2)=[CH:14][CH:13]=1

Komponenten

5

Edukt 3

HCID 807IodineHCID 23664628LithiumtriethylborohydrideHCID 698274994-(Ethynyloxy)-1,1'-biphenyl

Produkt 1

HCID 89873752(E)-4-((2-Iodovinyl)oxy)-1,1'-biphenylAusbeute 55 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 8028TetrahydrofuranLösungsmittel2×

Versuchsvorschrift

To an oven dried, two-necked flask (250 mL) under nitrogen and protected from light was added Cp2ZrCl2 (5.2 g, 20.3 mmol, 2 eq), dry THF (30 mL), and 1M lithium triethylborohydride (Super Hydride) in THF (20 mL, 20 mmol, 1.9 eq). The mixture was stirred for 1 h where the alkyne 3 (1.97 g, 10.2 mmol, 1 eq) was added. After 30 min, iodine (2.57 g, 20.3 mmol, 2 eq) was added and the reaction mixture was stirred for 30-40 min while protected from light. The reaction was quenched by diluting with ethyl acetate/hexane (1:1, 50 mL). The diluted mixture was then washed twice with saturated solution of sodium bicarbonate (150 mL) and the combined aqueous layers were extracted with ethyl acetate/hexane mixture (1:1). 10% aqueous sodium thiosulphate (100 mL) was used to wash the combined organic phases followed by brine (100 mL), dried over sodium sulfate, filtered, concentrated to yellowish slurry which was purified by silica gel column chromatography using 100% hexane as eluent (silica gel was pretreated with 2.5% v/v triethylamine) to afford 4 as white amorphous crystals (1.80 g, 55%): mp 64-660° C. 1H NMR (300 MHz, CDCl3): 7.64-7.52 (m, 4H, HAr), 7.49-7.41 (m, 2H), 7.38-7.32 (m, 1H, HAr), 7.13-7.01 (m, 3H, HAr), 5.74 (s, 1H, CH═CH, J=12.2 Hz) ppm; 13C NMR (75 MHz, CDCl3): 155.5, 150.3, 140.3, 137.0, 128.9, 128.4, 127.2, 126.9, 117.5, 57.9 ppm; IR (cm−1): 3316, 3077, 3034, 2960, 2924, 2874, 2174, 1643, 1623, 1601, 1515, 1485, 1330, 1307, 1226, 1186, 1173, 1093, 1008, 919, 854, 837, 697, 579, 549.

Aufarbeitung

  1. customTo an oven dried
  2. customtwo-necked flask (250 mL) under nitrogen and protected from light
  3. additionwas added
  4. customThe reaction was quenched
  5. additionby diluting with ethyl acetate/hexane (1:1, 50 mL)
  6. washThe diluted mixture was then washed twice with saturated solution of sodium bicarbonate (150 mL)
  7. extractionthe combined aqueous layers were extracted with ethyl acetate/hexane mixture (1:1)
  8. washto wash the combined organic phases
  9. dry with materialdried over sodium sulfate
  10. filtrationfiltered
  11. concentrationconcentrated to yellowish slurry which
  12. customwas purified by silica gel column chromatography

Quellen und Nachweise

ORD-Eintrag
ord-04addc85c8ac4194b0b7ae070a442f1c
Quelldatensatz
uspto-grants-2016_07
Patentnummer
US09393306B2

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