Sodium Cyanide → 6-Oxo-3,4,5,6-tetrahydro-1H-azepino[5,4,3-cd]indole-2-carbonitrile

HRID 33319

Reaktionsgleichung

Reaktionsgleichung von HRID 33319
I[C:2]1[NH:3][C:4]2[CH:5]=[CH:6][CH:7]=[C:8]3[C:14](=[O:15])[NH:13][CH2:12][CH2:11][C:10]=1[C:9]=23.[C-:16]#[N:17].[Na+]>C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[Pd].[Cu]I>[O:15]=[C:14]1[C:8]2[C:9]3[C:10](=[C:2]([C:16]#[N:17])[NH:3][C:4]=3[CH:5]=[CH:6][CH:7]=2)[CH2:11][CH2:12][NH:13]1

Komponenten

5

Edukt 2

HCID 8929Sodium CyanideHCID 98832232-Iodo-1,3,4,5-tetrahydro-azepino[5,4,3-cd]indol-6-one

Produkt 1

HCID 111383936-Oxo-3,4,5,6-tetrahydro-1H-azepino[5,4,3-cd]indole-2-carbonitrile

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)KatalysatorHCID 11979704Tetrakis(triphenylphosphine)palladiumKatalysator

Reaktionsbedingungen

Temperatur
80 °C

Versuchsvorschrift

Following a procedure from JOC 1998, p. 8224, 2-iodo-1,3,4,5-tetrahydro-azepino[5,4,3-cd]indol-6-one (100 mg, 0.32 mmol), sodium cyanide (31 mg, 0.64 mmol), palladium tetrakis(triphenylphosphine) (19 mg, 0.05 mmol), and copper(I) iodide were combined in a schlenk tube. The vessel was evacuated and refilled with argon gas three times. Degassed propionitrile (2 mL) was added, and the reaction was stirred at 80° C. under an argon atmosphere for 15 h. The reaction mixture was partitioned between water and 25% iPrOH/CHCl3. The layers were separated and the aqueous layer extracted thrice with 25% iPrOH/CHCl3. The combined organic layers were dried (MgSO4) and concentrated in vacuo. The yellow solid was recrystallized from CH2Cl2/MeOH/hexanes to yield 6-oxo-3,4,5,6-tetrahydro-1H-azepino[5,4,3-cd]indole-2-carbonitrile, 38 mg (56%) as a pale yellow solid: m.p. 315° C. (dec); 1H NMR (300 MHz, d6-DMSO) δ 3.04 (m, 2H), 3.47 (m, 2H), 7.46 (t, J=7.5 Hz, 1H), 7.64 (dd, J=8.1, 0.9 Hz, 1H), 7.81 (dd, J=7.2, 0.9 Hz, 1H), 8.24 (br t, 1H), 12.44 (br s, 1H). MS (electrospray, [M+Na]+): 234. Anal. (C12H9N3O) C, H, N.

Aufarbeitung

  1. customThe vessel was evacuated
  2. additionrefilled with argon gas three times
  3. additionDegassed propionitrile (2 mL) was added
  4. customThe reaction mixture was partitioned between water and 25% iPrOH/CHCl3
  5. customThe layers were separated
  6. extractionthe aqueous layer extracted thrice with 25% iPrOH/CHCl3
  7. dry with materialThe combined organic layers were dried (MgSO4)
  8. concentrationconcentrated in vacuo
  9. customThe yellow solid was recrystallized from CH2Cl2/MeOH/hexanes

Quellen und Nachweise

ORD-Eintrag
ord-36b5e29ead064e4ba2e1b30288fc20df
Quelldatensatz
uspto-grants-2008_09
Patentnummer
US07429578B2

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