Sodium Hydroxide → HCID 69516187, Verbindung

HRID 1297213Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1297213
[C:1]([N:20]1[N:24]=[N:23][C:22]([CH2:25][C:26]#[N:27])=[N:21]1)([C:14]1[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=1)([C:8]1[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.C1(C=O)CCCCC1.[OH-].[Na+].[I-].C[S+](C)(C)=O.[H-].[Na+].[CH:46]1([CH:52]=[C:53](C2N=NN(C(C3C=CC=CC=3)(C3C=CC=CC=3)C3C=CC=CC=3)N=2)C#N)[CH2:51][CH2:50][CH2:49][CH2:48][CH2:47]1>C1C=CC=CC=1.[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.CN(C=O)C.CCOC(C)=O>[CH:46]1([CH:52]2[CH2:53][C:25]2([C:22]2[N:23]=[N:24][N:20]([C:1]([C:2]3[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=3)([C:8]3[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=3)[C:14]3[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=3)[N:21]=2)[C:26]#[N:27])[CH2:51][CH2:50][CH2:49][CH2:48][CH2:47]1

Komponenten

11

Edukt 6

HCID 14798Sodium HydroxideHCID 16275CyclohexanecarboxaldehydeHCID 24758Sodium hydrideHCID 74498Sulfoxonium, trimethyl-, iodide (1:1)HCID 58914637HCID 58914637, VerbindungHCID 69516184HCID 69516184, Verbindung

Produkt 1

HCID 69516187HCID 69516187, VerbindungAusbeute 89,4 %

Reagenzien, Katalysatoren, Lösungsmittel 4

HCID 74236Tetrabutylammonium BromideKatalysatorHCID 241BenzeneLösungsmittelHCID 6228DimethylformamideLösungsmittel2×HCID 8857Ethyl AcetateLösungsmittel

Versuchsvorschrift

To a solution of (2-trityl-2H-tetrazol-5-yl)-acetonitrile (1.0 g, 2.85 mmol) in 15 mL benzene was added cyclohexanecarboxaldehyde (0.38 mL, 3.13 mmol), 10 mL 10% NaOH (aq), and tetrabutylammonium bromide (50 mg). The mixture was stirred for 1 h, then poured into EtOAc. The phases were separated, and the organic phase dried (MgSO4) and concentrated. Meanwhile, to trimethylsulfoxonium iodide (0.75 g, 3.42 mmol) in 7.0 mL DMF was added sodium hydride (60% dispersion in mineral oil, 0.14 g, 3.42 mmol). The mixture was stirred for 30 min at which time a solution of crude 3-cyclohexyl-2-(2-trityl-2H-tetrazol-5-yl)-acrylonitrile 2 (ca. 2.8 mmol) in 5.0 mL DMF was added quickly dropwise. The orange solution was stirred overnight, partitioned between EtOAc and H2O, and the phases separated. The organic phase was washed with brine, dried (MgSO4) and concentrated. Flash chromatography of the residue (15→20% EtOAc/hexanes) provided 1.15 g (88%, two steps) of 2-cyclohexyl-1-(2-trityl-2H-tetrazol-5-yl)-cyclopropanecarbonitrile as a colorless foam. 1H NMR (CDCl3) δ 7.33 (m, 9H), 7.07 (m, 6H), 1.88 (dd, J=4.9, 8.8 Hz, 1H, cyclopropyl —CHH), 1.66-1.84 (m, 4H), 1.57 (dd, J=4.9, 7.7 Hz, 1H, cyclopropyl —CHH), 1.25 (m, 8H).

Aufarbeitung

  1. customThe phases were separated
  2. dry with materialthe organic phase dried (MgSO4)
  3. concentrationconcentrated
  4. additionwas added quickly dropwise
  5. stirringThe orange solution was stirred overnight
  6. custompartitioned between EtOAc and H2O
  7. customthe phases separated
  8. washThe organic phase was washed with brine
  9. dry with materialdried (MgSO4)
  10. concentrationconcentrated

Quellen und Nachweise

ORD-Eintrag
ord-f213cf0fa26f4df28c2bcb771a2f51ee
Quelldatensatz
uspto-grants-2007_07
Patentnummer
US07250433B2

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