Nitrogen → 5-ethynyl-1-methyl-1H-indole

HRID 1258423

Reaktionsgleichung

Reaktionsgleichung von HRID 1258423
I[C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][CH:10]=1)[N:7]([CH3:11])[CH:6]=[CH:5]2.[Si]([C:16]#[CH:17])(C)(C)C.N#N>C(Cl)Cl.CCN(CC)CC.CCCCCC.Cl[Pd](Cl)([P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)[P](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Cu]I>[C:16]([C:2]1[CH:3]=[C:4]2[C:8](=[CH:9][CH:10]=1)[N:7]([CH3:11])[CH:6]=[CH:5]2)#[CH:17]

Komponenten

9

Edukt 3

HCID 947Nitrogen2×HCID 66111TrimethylsilylacetyleneHCID 113228355-iodo-1-methyl-1H-indole

Produkt 1

HCID 122962615-ethynyl-1-methyl-1H-indole

Reagenzien, Katalysatoren, Lösungsmittel 5

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 178418476HCID 178418476, VerbindungKatalysatorHCID 6344DichloromethaneLösungsmittelHCID 8058HexaneLösungsmittelHCID 8471TriethylamineLösungsmittel

Versuchsvorschrift

5-iodo-1-methyl-1H-indole (1.5 g, 5.84 mmol) were dissolved in mixture of CH2Cl2 (10 ml) and NEt3 (5 ml) and the system was evacuated-back filled by N2 thrice. Pd(PPh3)2Cl2 (122 mg, 3% mol) and TMS-acetylene (0.858 g, 8.7 mmol) were added to it and again flushed N2 into the system. CuI (89 mg, 8% mol) was added and flushed N2 very quickly and reaction was stirred under positive pressure of N2 until reaction completed by TLC (ca. 3 hours). The reaction mixture was diluted with 10 ml of hexane and filtered through celite plug, purified by passing through small column and then suspended in MeOH (20 ml) containing 10 ml of THF. NaOH was added to reaction mixture and stirred at room temp until starting material consumed completely. The reaction mixture was concentrated to 10 ml and extracted with EtOAc from aqueous NH4Cl solution, which was purified by column chromatography; Yield (60%); 1H NMR (300 MHz, CDCl3) δ: 3.03 (s, 1H), 3.73 (s, 3H, NMe), 6.45 (d, J=3.0 Hz, 1H), 7.05 (d, J=3.0 Hz, 1H), 7.23 (d, J=9.0 Hz, 1H), 7.33 (dd, J=9.0, 1.2 Hz, 1H), 7.80 (bs, 1H).

Aufarbeitung

  1. customthe system was evacuated-back
  2. additionfilled by N2 thrice
  3. customflushed N2 very quickly
  4. customreaction
  5. customcompleted by TLC (ca. 3 hours)
  6. filtrationfiltered through celite plug
  7. custompurified
  8. additioncontaining 10 ml of THF
  9. additionNaOH was added to reaction mixture
  10. customconsumed completely
  11. concentrationThe reaction mixture was concentrated to 10 ml
  12. extractionextracted with EtOAc from aqueous NH4Cl solution, which
  13. customwas purified by column chromatography
  14. customYield (60%)

Quellen und Nachweise

ORD-Eintrag
ord-d60b3960279d4fd8aaf5511a0e28b811
Quelldatensatz
uspto-grants-2013_06
Patentnummer
US08466163B2

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