Methylenecyclohexane → HCID 67515548, Verbindung

HRID 1754336Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1754336
[Br:1][C:2]1[CH:3]=[C:4]([C:9]2[CH2:13][C:12]3([CH2:18][CH2:17][CH2:16][CH2:15][CH2:14]3)[O:11][N:10]=2)[CH:5]=[CH:6][C:7]=1[CH3:8].CC1C=C(C=CC=1C)C=NO.C=C1CCCCC1.C1C(=O)N([Br:44])C(=O)C1>C(Cl)(Cl)Cl.CC(N=NC(C#N)(C)C)(C#N)C>[Br:44][CH:13]1[C:12]2([CH2:14][CH2:15][CH2:16][CH2:17][CH2:18]2)[O:11][N:10]=[C:9]1[C:4]1[CH:5]=[CH:6][C:7]([CH3:8])=[C:2]([Br:1])[CH:3]=1

Komponenten

7

Edukt 4

HCID 14502MethylenecyclohexaneHCID 67184N-bromobutanimideHCID 53395410N-[(3,4-Dimethylphenyl)methylidene]hydroxylamineHCID 67515835HCID 67515835, Verbindung

Produkt 1

HCID 67515548HCID 67515548, VerbindungAusbeute 23,9 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 6547AzobisisobutyronitrileKatalysatorHCID 6212ChloroformLösungsmittel2×

Versuchsvorschrift

To a solution of 3-(3-bromo-4-methylphenyl)-1-oxa-2-azaspiro[4.5]dec-2-ene (2.0 g, 6.49 mmol, 1.0 eq) (prepared by following the procedure described for step-2 of the intermediate 27 by the reaction of 3-methyl-4-methylbenzaldehyde oxime with methylenecyclohexane) in chloroform (20 mL) was added NBS (1.15 g, 6.49 mmol, 1.0 eq) followed by catalytic amount of AIBN (21 mg, 0.13 mmol, 0.02 eq). The resulting mixture was stirred at room temperature overnight. The reaction was diluted with chloroform (50 mL) and washed with water (50 mL) and brine (50 mL). The organic layer was dried (Na2SO4) and filtered. The filtrate was concentrated under vacuum. The crude product was purified by flash column chromatography (silica gel, ethyl acetate and hexane) to afford 600 mg of the title product as a white solid. 1HNMR (400 MHz, CDCl3) δ 7.97 (d, J=2.0 Hz, 1H), 7.65 (dd, J=8.0, 2.0 Hz, 1H), 7.29 (d, J=8.0 Hz, 1H), 5.14 (s, 1H), 2.43 (s, 3H), 2.13-2.10 (m, 1H), 2.01-1.99 (m, 1H), 1.82-1.76 (m, 4H), 1.65-1.62 (m, 1H), 1.52-1.45 (m, 3H); ESI-MS (m/z) 386, 388, 390 [(MH)+ Br79,81].

Aufarbeitung

  1. washwashed with water (50 mL) and brine (50 mL)
  2. dry with materialThe organic layer was dried (Na2SO4)
  3. filtrationfiltered
  4. concentrationThe filtrate was concentrated under vacuum
  5. customThe crude product was purified by flash column chromatography (silica gel, ethyl acetate and hexane)

Quellen und Nachweise

ORD-Eintrag
ord-3e8ddc976ece4129adfe4225724b923a
Quelldatensatz
uspto-grants-2015_10
Patentnummer
US09169242B2

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