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

HRID 628626

反応式

HRID 628626 の反応式
[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]

参加物

7

反応物 5

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

生成物 1

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

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒2 回

反応条件

温度
-78 °C

実験手順

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).

後処理

  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)

出典と根拠

ORDレコード
ord-1f81ea17ae2a46e39306a46045232d6d
出典データセット
uspto-grants-2016_04
特許番号
US09314467B2

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