Methallyl alcohol → Methyl 3-methoxy-4-(2-methylallyloxy)benzoate

HRID 72927

反応式

HRID 72927 の反応式
[OH:1][C:2]1[CH:11]=[CH:10][C:5]([C:6]([O:8][CH3:9])=[O:7])=[CH:4][C:3]=1[O:12][CH3:13].[CH3:14][C:15](=[CH2:18])[CH2:16]O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C1COCC1>[CH3:13][O:12][C:3]1[CH:4]=[C:5]([CH:10]=[CH:11][C:2]=1[O:1][CH2:16][C:15]([CH3:18])=[CH2:14])[C:6]([O:8][CH3:9])=[O:7]

参加物

6

反応物 4

HCID 10557Methallyl alcoholHCID 11776TriphenylphosphineHCID 19844Methyl VanillateHCID 5363146Diisopropyl azodicarboxylate

生成物 1

HCID 51109732Methyl 3-methoxy-4-(2-methylallyloxy)benzoate収率 75%

試薬・触媒・溶媒 1

HCID 8028Tetrahydrofuran溶媒

反応条件

温度
55 °C

実験手順

To a stirred solution of methyl 4-hydroxy-3-methoxy-benzoate (2 g, 10.98 mmol), 2-methylprop-2-en-1-ol (871.0 mg, 1.0 mL, 12.1 mmol) and triphenylphosphine (3.17 g, 2.8 mL, 12.1 mmol) in THF (63.28 mL) at 0° C. was added DIAD (2.44 g, 2.34 mL, 12.1 mmol). The ice bath was removed and the reaction was stirred at 55° C. for 16 hours. The reaction mixture was diluted with EtOAc and washed sequentially with NaHCO3 (2×20 mL) and brine (2×20 mL) solutions. The organic layer was separated, dried over Na2SO4, filtered and the solvent was evaporated under reduced pressure. The crude product was purified with silica gel using (0-30%) ethyl acetate-hexanes to yield methyl 3-methoxy-4-(2-methylallyloxy)benzoate (1.94 g, 75%) as a viscous liquid. ESI-MS m/z calc. 236.1. Found 237.1 (M+1)+. Retention time: 1.63 minutes (3 min run). 1H NMR (400 MHz, DMSO) δ 7.56 (dd, J=8.4, 2.0 Hz, 1H), 7.47 (d, J=1.9 Hz, 1H), 7.06 (d, J=8.5 Hz, 1H), 5.07 (br s, 1H), 4.97 (br s, 1H), 4.55 (s, 2H), 3.83 (s, 3H), 3.82 (s, 3H), 1.78 (s, 3H).

後処理

  1. customThe ice bath was removed
  2. additionThe reaction mixture was diluted with EtOAc
  3. washwashed sequentially with NaHCO3 (2×20 mL) and brine (2×20 mL) solutions
  4. customThe organic layer was separated
  5. dry with materialdried over Na2SO4
  6. filtrationfiltered
  7. customthe solvent was evaporated under reduced pressure
  8. customThe crude product was purified with silica gel using (0-30%) ethyl acetate-hexanes

出典と根拠

ORDレコード
ord-5d033869e9ff42b489a208698f25705b
出典データセット
uspto-grants-2014_09
特許番号
US08828996B2

関連ノート

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