Chloranil → HCID 86689403, Verbindung

HRID 926662

Reaktionsgleichung

Reaktionsgleichung von HRID 926662
BrC1C=CC(C(O)C(O)=O)=CC=1.C(C1C=C(O)C(CCCCCCCC)=CC=1O)CCCCCCC.[Br:37][C:38]1[CH:43]=[CH:42][C:41]([CH:44]2[C:48](=[O:49])[O:47][C:46]3=[C:50]([CH2:73][CH2:74][CH2:75][CH2:76][CH2:77][CH2:78][CH2:79][CH3:80])[C:51]4[CH:55]([C:56]5[CH:61]=[CH:60][C:59]([Br:62])=[CH:58][CH:57]=5)[C:54](=[O:63])[O:53][C:52]=4[C:64]([CH2:65][CH2:66][CH2:67][CH2:68][CH2:69][CH2:70][CH2:71][CH3:72])=[C:45]23)=[CH:40][CH:39]=1.C1(Cl)C(=O)C(Cl)=C(Cl)C(=O)C=1Cl>ClC1C=CC=C(Cl)C=1Cl.C(O)(=O)C>[Br:62][C:59]1[CH:58]=[CH:57][C:56]([C:55]2[C:54](=[O:63])[O:53][C:52]3=[C:64]([CH2:65][CH2:66][CH2:67][CH2:68][CH2:69][CH2:70][CH2:71][CH3:72])[C:45]4[C:46](=[C:50]([CH2:73][CH2:74][CH2:75][CH2:76][CH2:77][CH2:78][CH2:79][CH3:80])[C:51]=23)[O:47][C:48](=[O:49])[C:44]=4[C:41]2[CH:42]=[CH:43][C:38]([Br:37])=[CH:39][CH:40]=2)=[CH:61][CH:60]=1

Komponenten

7

Edukt 4

HCID 8371ChloranilHCID 827231,4-Benzenediol, 2,5-dioctyl-HCID 97930p-Bromomandelic acidHCID 66654027HCID 66654027, Verbindung

Produkt 1

HCID 86689403HCID 86689403, VerbindungAusbeute 9 %

Reagenzien, Katalysatoren, Lösungsmittel 2

HCID 176Acetic AcidLösungsmittelHCID 68951,2,3-TrichlorobenzeneLösungsmittel

Reaktionsbedingungen

Temperatur
200 °C

Versuchsvorschrift

In a 100 cm3 flask fitted with a condenser and a reverse Dean-Stark apparatus, (4-bromo-phenyl)-hydroxy-acetic acid (6.043 g, 26.16 mmol) and 2,5-dioctyl-benzene-1,4-diol (Bao, Z.; Chan, W. K.; Yu, L. J. Am. Chem. Soc. 1995, 117, 12426-12435.) (3.500 g, 10.46 mmol) are dissolved in 1,2-dichlorochlorobenzene (35 cm3). The reaction mixture is heated to 200° C. and the generated water is distilled off the using a reverse Dean-Stark apparatus. After 2 hours stirring, the reaction mixture is cooled down and the solvent was removed in vacuo. (9.501 g, Crude yield: 125%). The crude 3,7-bis-(4-bromo-phenyl)-4,8-dioctyl-3,7-dihydro-benzo[1,2-b;4,5-b′]difuran-2,6-dione (7.500 g, 10.35 mmol) is dissolved into acetic acid (125 cm3) at 50° C. before adding chloranil (5.090 g, 20.70 mmol). After 16 hours stirring, the reaction mixture is cooled down and the resulting precipitate is filtered. The recovered solid is purified by column chromatography (95:5, petroleum ether (40-60):Ethyl acetate as eluant) to obtain a crystalline orange solid (0.642 g, Yield: 9%). NMR (1H, 300 MHz, CDCl3): δ 7.63 (d, J=8.5 Hz, 4H); 7.30 (d, J=8.5 Hz, 4H); 2.46 (m, 4H); 1.19 (m, 16H); 0.98 (m, 8H); 0.88 (t, J=7.1 Hz, 6H)

Aufarbeitung

  1. customIn a 100 cm3 flask fitted with a condenser
  2. distillationthe generated water is distilled off the using a reverse Dean-Stark apparatus
  3. temperaturethe reaction mixture is cooled down
  4. customthe solvent was removed in vacuo
  5. stirringAfter 16 hours stirring
  6. temperaturethe reaction mixture is cooled down
  7. filtrationthe resulting precipitate is filtered
  8. customThe recovered solid is purified by column chromatography (95:5, petroleum ether (40-60):Ethyl acetate as eluant)

Quellen und Nachweise

ORD-Eintrag
ord-bf8b9990784941b4812abade30b76aa5
Quelldatensatz
uspto-grants-2016_03
Patentnummer
US09287504B2

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