Chloranil → HCID 86689403、化合物

HRID 926662

反応式

HRID 926662 の反応式
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

参加物

7

反応物 4

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

生成物 1

HCID 86689403HCID 86689403、化合物収率 9%

試薬・触媒・溶媒 2

HCID 176Acetic Acid溶媒HCID 68951,2,3-Trichlorobenzene溶媒

反応条件

温度
200 °C

実験手順

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)

後処理

  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)

出典と根拠

ORDレコード
ord-bf8b9990784941b4812abade30b76aa5
出典データセット
uspto-grants-2016_03
特許番号
US09287504B2

関連ノート

読み込み中…