Nitromethane → HCID 11446856, Verbindung

HRID 1297221Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1297221
[CH3:1][O:2][C:3](=[O:13])[C:4]([C:11]#[N:12])=[C:5]1[CH2:10][CH2:9][CH2:8][CH2:7][CH2:6]1.[N+]([CH3:17])([O-])=O.C1CCN2C(=NCCC2)CC1>C(#N)C.CCOCC>[CH3:1][O:2][C:3]([C:4]1([C:11]#[N:12])[C:5]2([CH2:6][CH2:7][CH2:8][CH2:9][CH2:10]2)[CH2:17]1)=[O:13]

Komponenten

6

Edukt 3

HCID 6375NitromethaneHCID 811841,8-Diazabicyclo(5.4.0)undec-7-eneHCID 11229121CYANO-CYCLOHEXYLIDENE-ACETIC ACID METHYL ESTER

Produkt 1

HCID 11446856HCID 11446856, VerbindungAusbeute 86 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 3283Diethyl EtherLösungsmittelHCID 6342AcetonitrileLösungsmittel

Versuchsvorschrift

To a solution of cyano-cyclohexylidene-acetic acid methyl ester (20.0 g, 112 mmol) in acetonitrile (400 mL) was added nitromethane (30 mL, 558 mmol) followed by dropwise addition of DBU (16.9 mL, 113 mmol) over five minutes. The solution went from clear to orange and was stirred at room temperature for 5.5 hours. The solution was diluted with ether (1 L), washed with 1N HCl (2×250 mL) and then brine (2×250 mL). The organic layer was dried over sodium sulfate, filtered and evaporated. The residue was chromatographed on a wet-packed silica gel column (6.5×40 cm) eluting with 95:5 hexanes/ethyl acetate. The appropriate fractions were combined and evaporated to give 18.6 g (86%) of 1-cyano-spiro[2.5]octane-1-carboxylic acid methyl ester as a clear oil: 1H NMR (300 MHz, CDCl3) δ 1.35 (m, 1H), 1.49 (d, J=5.0 Hz, 1H), 1.5-1.75 (m, 9H), 1.82 (d, J=5.0 Hz, 1H), 3.83 (s, 3H).

Aufarbeitung

  1. washwashed with 1N HCl (2×250 mL)
  2. dry with materialThe organic layer was dried over sodium sulfate
  3. filtrationfiltered
  4. customevaporated
  5. customThe residue was chromatographed on a wet-packed silica gel column (6.5×40 cm)
  6. washeluting with 95:5 hexanes/ethyl acetate
  7. customevaporated

Quellen und Nachweise

ORD-Eintrag
ord-94133b73468843fb9204de4ca8c17d13
Quelldatensatz
uspto-grants-2007_07
Patentnummer
US07250433B2

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