Pyridine → HCID 68498360, Verbindung

HRID 16541

Reaktionsgleichung

Reaktionsgleichung von HRID 16541
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

Komponenten

6

Edukt 4

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

Produkt 1

HCID 68498360HCID 68498360, VerbindungAusbeute 46 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 6344DichloromethaneLösungsmittel2×

Versuchsvorschrift

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+].

Aufarbeitung

  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

Quellen und Nachweise

ORD-Eintrag
ord-9d6bb39db55247be82e16b23b4c1f94d
Quelldatensatz
uspto-grants-2010_06
Patentnummer
US07737164B2

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