18-Crown-6 → (E)-2-iodo-1-methyl-4-(2-(2,6,6-trimethylcyclohex-1-enyl)vinyl)benzene

HRID 628626

Reaktionsgleichung

Reaktionsgleichung von HRID 628626
[Br-].C1([P+](C2C=CC=CC=2)(C2C=CC=CC=2)[CH2:9][C:10]2[C:15]([CH3:17])([CH3:16])[CH2:14][CH2:13][CH2:12][C:11]=2[CH3:18])C=CC=CC=1.C1OCCOCCOCCOCCOCCOC1.CC(C)([O-])C.[K+].[I:55][C:56]1[CH:57]=[C:58]([CH:61]=[CH:62][C:63]=1[CH3:64])[CH:59]=O.[PH4+]>C(Cl)Cl>[I:55][C:56]1[CH:57]=[C:58](/[CH:59]=[CH:9]/[C:10]2[C:15]([CH3:16])([CH3:17])[CH2:14][CH2:13][CH2:12][C:11]=2[CH3:18])[CH:61]=[CH:62][C:63]=1[CH3:64]

Komponenten

7

Edukt 5

HCID 2855718-Crown-6HCID 5460504PhosphoniumHCID 10950920Agn-PC-0nddf92×HCID 123302543-Iodo-4-methylbenzaldehyde2×HCID 23665647Potassium tert-butoxide2×

Produkt 1

HCID 68947343(E)-2-iodo-1-methyl-4-(2-(2,6,6-trimethylcyclohex-1-enyl)vinyl)benzene

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel2×

Reaktionsbedingungen

Temperatur
-78 °C

Versuchsvorschrift

To a −78° C. solution of triphenyl((2,6,6-trimethylcyclohex-1-enyl)methyl)phosphonium bromide (24) (0.3787 g, 0.79 mmol) and 18-crown-6 (0.0246 g, 0.093 mmol) in CH2Cl2 (7 mL) was added potassium tert-butoxide (0.0991 g, 0.88 mmol). The mixture was sonicated at room temperature under argon for 2 min, resulting in a deep red solution. The mixture was cooled to −78° C. then a solution of 3-iodo-4-methylbenzaldehyde (0.1742 g, 0.71 mmol) in CH2Cl2 (3 mL+2 mL) was added and stirred for 5 min. The reaction mixture was allowed to warm to room temperature. Additional phosphonium salt 24 (0.3725 g, 1.6 mmol), 3-iodo-4-methylbenzaldehyde (0.2538 g, 1.7 mmol) and potassium tert-butoxide (0.1548 g, 1.38 mmol) were then added and the reaction was stirred at room temperature for 4.3 h. The reaction was partitioned between EtOAc and water then the combined organics were washed with brine, dried over MgSO4 and concentrated under reduced pressure. Purification by flash chromatography (6 to 50% EtOAc-hexanes gradient) gave (E)-2-iodo-1-methyl-4-(2-(2,6,6-trimethylcyclohex-1-enyl)vinyl)benzene as a white solid. Yield (0.26 g, 45%): NMR (400 MHz, DMSO-d6) δ 7.91 (d, J=1.6 Hz, 1H), 7.44 (dd, J=7.6, 1.2 Hz, 1H), 7.29 (d, J=7.2 Hz, 1H), 6.71 (d, J=16.4 Hz, 1H), 6.28 (6, J=16.8 Hz, 1H), 2.35 (s, 3H), 2.01 (t, J=6.4 Hz, 2H), 1.72 (s, 3H), 1.57-1.64 (m, 2H), 1.43-1.47 (m, 2H), 1.04 (s, 6H).

Aufarbeitung

  1. customThe mixture was sonicated at room temperature under argon for 2 min
  2. customresulting in a deep red solution
  3. temperatureto warm to room temperature
  4. stirringthe reaction was stirred at room temperature for 4.3 h
  5. customThe reaction was partitioned between EtOAc and water
  6. washthe combined organics were washed with brine
  7. dry with materialdried over MgSO4
  8. concentrationconcentrated under reduced pressure
  9. customPurification by flash chromatography (6 to 50% EtOAc-hexanes gradient)

Quellen und Nachweise

ORD-Eintrag
ord-1f81ea17ae2a46e39306a46045232d6d
Quelldatensatz
uspto-grants-2016_04
Patentnummer
US09314467B2

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