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

HRID 242722

반응식

HRID 242722 반응식
[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]

참가 물질

7

반응물 5

HCID 2855718-Crown-6HCID 5460504PhosphoniumHCID 10950920Agn-PC-0nddf92회HCID 123302543-Iodo-4-methylbenzaldehyde2회HCID 23665647Potassium tert-butoxide2회

생성물 1

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

시약·촉매·용매 1

HCID 6344Dichloromethane용매2회

반응 조건

온도
-78 °C

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).

후처리

  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)

출처 및 근거

ORD 기록
ord-5f33ccf406034e1dbb379159b510b051
출처 데이터셋
uspto-grants-2014_02
특허 번호
US08653142B2

연결된 노트

불러오는 중…