Pyridine → 3'-Methoxy-4'-tetrahydropyranylacetophenone

HRID 1918401

反応式

HRID 1918401 の反応式
O.C1(C)C=CC(S(O)(=O)=O)=CC=1.N1C=CC=CC=1.[CH3:19][C:20]([C:22]1[CH:30]=[CH:29][C:27](O)=[C:24]([O:25][CH3:26])[CH:23]=1)=[O:21].[O:31]1[CH:36]=[CH:35][CH2:34][CH2:33][CH2:32]1>C(Cl)Cl>[CH3:26][O:25][C:24]1[CH:23]=[C:22]([C:20](=[O:21])[CH3:19])[CH:30]=[CH:29][C:27]=1[CH:32]1[CH2:33][CH2:34][CH2:35][CH2:36][O:31]1

参加物

6

反応物 4

HCID 1049PyridineHCID 2214Acetovanillone2 回HCID 80803,4-dihydro-2H-pyranHCID 521998p-Toluenesulfonic acid monohydrate

生成物 1

HCID 684983603'-Methoxy-4'-tetrahydropyranylacetophenone収率 46%

試薬・触媒・溶媒 1

HCID 6344Dichloromethane溶媒2 回

実験手順

In an oven-dried, 500 mL round bottom flask equipped with a stir bar and an addition funnel, p-toluenesulfonic acid monohydrate (156 mg, 0.82 mmol), pyridine (66 μL, 0.82 mmol), acetovanillone (6.10 g, 36.7 mmol), and CH2Cl2 (170 mL) were combined and rapidly stirred. Dihydropyran (10 mL, 110 mmol) was diluted with 40 mL of CH2Cl2, poured into the addition funnel, and added drop wise to the acetovanillone solution over a period of 2 h. The reaction was stirred for an additional 12 h at room temperature, after which it was washed with 200 mL of 1.0 N NaOH (2×). The organic phase was dried over Na2SO4, filtered, and concentrated to a clear oil under reduced pressure. The oil crystallized upon standing to afford 4.2 g of THP-C as a white solid (46% yield). The solid was used without further purification. TLC: Rf=0.19 (hexane/EtOAc 4:1); Melting point: 67-69° C.; 1H NMR: (300 MHz, CDCl3) δ 7.52 (s, 1H), 7.50 (d, J=10 Hz, 1H), 7.13 (d, J=8 Hz, 1H), 5.50 (t, J=3 Hz, 1H), 3.90 (s, 3H), 3.89 (m, 1H), 3.59 (m, 1H), 2.54 (s, 3H), 1.95 (m, 3H), 1.63 (m, 1H); 13C NMR: (75 MHz, CDCl3) δ 197.08, 150.92, 150.12, 131.60, 123.18, 115.65, 111.29, 97.14, 62.31, 56.32, 30.33, 26.45, 25.31, 18.79; IR (ATR): 2966, 2936, 2880, 1672, 1585, 1510, 1462, 1442, 1413, 1390, 1352, 1290, 1272, 1243, 1221, 1201, 1172, 1153, 1120, 1110, 1051, 1032, 1020, 959 1046 cm−1; ESI-MS: expected, 250.1; observed, m/z 251.1 [M+H+].

後処理

  1. customIn an oven-dried, 500 mL round bottom flask equipped with a stir bar and an addition funnel
  2. additionpoured into the addition funnel
  3. stirringThe reaction was stirred for an additional 12 h at room temperature
  4. washafter which it was washed with 200 mL of 1.0 N NaOH (2×)
  5. dry with materialThe organic phase was dried over Na2SO4
  6. filtrationfiltered
  7. concentrationconcentrated to a clear oil under reduced pressure
  8. customThe oil crystallized

出典と根拠

ORDレコード
ord-8383e157675241819a1a6673fc377da5
出典データセット
uspto-grants-2013_12
特許番号
US08618327B2

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