2,3-Dichloro-5,6-dicyano-1,4-benzoquinone → HCID 21923182, Verbindung

HRID 1244848Notizen

Reaktionsgleichung

Reaktionsgleichung von HRID 1244848
[C:1]1([C:6]2[N:7]([Si:11]([CH:18]([CH3:20])[CH3:19])([CH:15]([CH3:17])[CH3:16])[CH:12]([CH3:14])[CH3:13])[CH:8]=[CH:9][CH:10]=2)[CH2:5][CH2:4][CH2:3][CH:2]=1.C1(C2C=CN([Si](C(C)C)(C(C)C)C(C)C)C=2)CCCC=1.[C:41]([O:50][CH2:51][CH3:52])(=[O:49])/[CH:42]=[CH:43]/[C:44]([O:46][CH2:47][CH3:48])=[O:45].C(C1C(=O)C(Cl)=C(Cl)C(=O)C=1C#N)#N>C1C=CC=CC=1>[CH:12]([Si:11]([CH:15]([CH3:17])[CH3:16])([CH:18]([CH3:20])[CH3:19])[N:7]1[C:6]2[C:10](=[C:42]([C:41]([O:50][CH2:51][CH3:52])=[O:49])[C:43]([C:44]([O:46][CH2:47][CH3:48])=[O:45])=[C:2]3[CH2:3][CH2:4][CH2:5][C:1]3=2)[CH:9]=[CH:8]1)([CH3:13])[CH3:14]

Komponenten

6

Edukt 4

HCID 67752,3-Dichloro-5,6-dicyano-1,4-benzoquinoneHCID 638144Diethyl fumarateHCID 13291167HCID 13291167, VerbindungHCID 21923206HCID 21923206, Verbindung

Produkt 1

HCID 21923182HCID 21923182, VerbindungAusbeute 21 %

Reagenzien, Katalysatoren, Lösungsmittel 1

HCID 241BenzeneLösungsmittel

Reaktionsbedingungen

Temperatur
150 °C

Versuchsvorschrift

A 2:1 mixture of 2-(cyclopenten-1-yl)-1-(triisopropylsilyl)pyrrole and 3-(cyclopenten-1-yl)-1-(triisopropylsilyl)pyrrole (1.16 g, 4.01 mmol) and diethyl fumarate (0.75 g, 4.36 mmol) was heated under nitrogen to 150° C. for 64 h, affording the crude Diels-Alder adduct as an amber oil. The pure Diels-Alder adduct could be isolated by chromatography on silica gel (hexanes-ether 90:10). NMR (CDCl3) δ 6.68 (d, 1H), 6.16 (d, 1H), 4.20 (m, 4H), 3.95 (d, 1H), 2.91 (t, 2H), 2.49 (m, 1H), 2.09 (m, 1H), 1.73 (m, 2H), 1.48 (septet, 3H), 1.30 (2t, 6H), 1.27 (d, 9H), 1.07 (d, 9H). MS m/e 462 (M+H)+. DDQ (2.2 g, 9.7 mmol) was added in three portions to a benzene solution (16 mL) of the crude Diels-Alder adduct at 50° C. until no starting material remained (TLC and NMR). After 8 h, the mixture was filtered through Celite®. The precipitate was rinsed with benzene, and the filtrate was evaporated to give 1.52 g of a black solid. This was chromatographed on silica gel (hexanes-ether 15:85 to 20:80) to give the product (380 mg, 21% yield, 35% yield from 2-isomer) as a colorless oil. NMR (CDCl3) δ 7.42 (d, 1H), 7.05 (d, 1H), 4.40 (2q, 4H), 3.20 (t, 2H), 3.12 (t, 2H), 2.17 (quintet, 2H), 1.67 (septet, 3H), 1.39 (t, 3H), 1.36 (t, 3H), 1.20 (d, 18H). MS m/e 458 (M+H)+.

Aufarbeitung

  1. customaffording the crude Diels-Alder adduct as an amber oil
  2. customThe pure Diels-Alder adduct could be isolated by chromatography on silica gel (hexanes-ether 90:10)
  3. filtrationthe mixture was filtered through Celite®
  4. washThe precipitate was rinsed with benzene
  5. customthe filtrate was evaporated

Quellen und Nachweise

ORD-Eintrag
ord-2e077240aa544520bde0c127fbb6bd8e
Quelldatensatz
uspto-grants-2006_10
Patentnummer
US07122679B2

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