Methyl iodide → 1,3-Bis(ethoxymethoxy)-4-isopropoxy-2-methylbenzene

HRID 1511217노트

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HRID 1511217 반응식
[CH2:1]([O:3][CH2:4][O:5][C:6]1[CH:11]=[C:10]([O:12][CH2:13][O:14][CH2:15][CH3:16])[CH:9]=[CH:8][C:7]=1[O:17][CH:18]([CH3:20])[CH3:19])[CH3:2].[Li][CH2:22]CCC.CI>C1COCC1>[CH2:15]([O:14][CH2:13][O:12][C:10]1[CH:9]=[CH:8][C:7]([O:17][CH:18]([CH3:20])[CH3:19])=[C:6]([O:5][CH2:4][O:3][CH2:1][CH3:2])[C:11]=1[CH3:22])[CH3:16]

참가 물질

5

반응물 3

HCID 6328Methyl iodideHCID 251409942,4-Bis(ethoxymethoxy)-1-isopropoxybenzeneHCID 178418339Butyllithium

생성물 1

HCID 251402561,3-Bis(ethoxymethoxy)-4-isopropoxy-2-methylbenzene수율 79%

시약·촉매·용매 1

HCID 8028Tetrahydrofuran용매2회

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온도
-78 °C

실험 절차

A solution of 4c (190 mg, 0.67 mmol) in anhydrous THF (530 μL) was added dropwise to a solution of nBuLi (2.5 M in hexanes, 410 μL, 1.00 mmol) in anhydrous THF (440 μL) at room temperature. After 1 hour, the solution was cooled to −78° C. and methyl iodide (170 μL, 2.67 mmol) was added. The resulting solution was warmed to room temperature over 12 hours, and the reaction was quenched by the addition of saturated aqueous NH4Cl. Water (5 mL) was added and the solution was extracted with CH2Cl2 (3×10 mL). Combined organic fractions were dried (Na2SO4), filtered, and concentrated. The residue was purified via column chromatography (SiO2, 6:1 Hexane:EtOAc) to afford 5c as a yellow oil (157 mg, 79%): 1H NMR (CDCl3, 500 MHz) 6.70 (d, J=9.0 Hz, 1H), 6.61 (d, J=9.0 Hz, 1H), 5.10 (s, 2H), 5.08 (s, 2H), 4.34 (quintet, J=6.1 Hz, 1H), 3.78 (q, J=7.1 Hz, 2H), 3.67 (q, J=7.1 Hz, 2H), 2.13 (s, 3H), 1.23 (d, J=6.1 Hz, 6H), 1.24-1.15 (m, 6H); 13C NMR (CDCl3, 125 MHz) δ 150.3, 146.6, 145.3, 122.7, 113.7, 110.1, 97.3, 94.0, 71.5, 65.4, 64.2, 29.4, 22.2, 15.2, 15.2, 9.9; IR (film) νmax 2924, 2853, 2359, 2339, 1591, 1483, 1113, 1057, 974 cm−1; HRMS (ESI+) m/z: [M+H]+ calcd for C16H26O5, 299.1858. found, 299.1909.

후처리

  1. temperatureThe resulting solution was warmed to room temperature over 12 hours
  2. customthe reaction was quenched by the addition of saturated aqueous NH4Cl
  3. additionWater (5 mL) was added
  4. extractionthe solution was extracted with CH2Cl2 (3×10 mL)
  5. dry with materialCombined organic fractions were dried (Na2SO4)
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customThe residue was purified via column chromatography (SiO2, 6:1 Hexane:EtOAc)

출처 및 근거

ORD 기록
ord-ba422ca97921477a956e97e1df3e7fab
출처 데이터셋
uspto-grants-2012_07
특허 번호
US08212011B2

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