반응 #329904

ord-5f33ccf406034e1dbb379159b510b051

반응 방정식

[PH4+]
phosphonium
CC1=C(C[P+](c2ccccc2)(c2ccccc2)c2ccccc2)C(C)(C)CCC1.[Br-]
24
CC1=C(C[P+](c2ccccc2)(c2ccccc2)c2ccccc2)C(C)(C)CCC1.[Br-]
triphenyl((2,6,6-trimethylcyclohex-1-enyl)methyl)phosphonium bromide
Cc1ccc(C=O)cc1I
3-iodo-4-methylbenzaldehyde
CC(C)(C)[O-].[K+]
potassium tert-butoxide
CC1=C(C[P+](c2ccccc2)(c2ccccc2)c2ccccc2)C(C)(C)CCC1.[Br-]
triphenyl((2,6,6-trimethylcyclohex-1-enyl)methyl)phosphonium bromide
C1COCCOCCOCCOCCOCCO1
18-crown-6
CC(C)(C)[O-].[K+]
potassium tert-butoxide
Cc1ccc(C=O)cc1I
3-iodo-4-methylbenzaldehyde
CC1=C(/C=C/c2ccc(C)c(I)c2)C(C)(C)CCC1
(E)-2-iodo-1-methyl-4-(2-(2,6,6-trimethylcyclohex-1-enyl)vinyl)benzene

반응 조건

온도
-78°CELSIUS
상세 조건
See reaction.notes.procedure_details.

후처리

  1. 1
    기타The mixture was sonicated at room temperature under argon for 2 min
  2. 2
    기타resulting in a deep red solution
  3. 3
    온도to warm to room temperature
  4. 4
    workup.STIRRINGthe reaction was stirred at room temperature for 4.3 h
  5. 5
    기타The reaction was partitioned between EtOAc and water
  6. 6
    세척the combined organics were washed with brine
  7. 7
    건조dried over MgSO4
  8. 8
    농축concentrated under reduced pressure
  9. 9
    기타Purification by flash chromatography (6 to 50% EtOAc-hexanes gradient)

실험 절차

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%): 1H 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).

출처

DOI: 10.6084/m9.figshare.5104873.v1특허: US08653142B2uspto-grants-2014_02