Hydrochloric Acid → 4,5-Dichloro-9-anthraldehyde

HRID 1381739

反応式

HRID 1381739 の反応式
[Cl:1][C:2]1[C:15]2[C:6](=[CH:7][C:8]3[C:13]([CH:14]=2)=[C:12]([Cl:16])[CH:11]=[CH:10][CH:9]=3)[CH:5]=[CH:4][CH:3]=1.N#N.Cl[Sn](Cl)(Cl)Cl.ClC[CH:26]([O:29]C(CCl)CCl)CCl.Cl>O.C(Cl)Cl>[Cl:1][C:2]1[C:15]2[C:6](=[C:7]([CH:26]=[O:29])[C:8]3[C:13]([CH:14]=2)=[C:12]([Cl:16])[CH:11]=[CH:10][CH:9]=3)[CH:5]=[CH:4][CH:3]=1

参加物

8

反応物 5

HCID 313Hydrochloric AcidHCID 947NitrogenHCID 24287Tin tetrachlorideHCID 93323Bis(1,3-dichloroisopropyl ether)HCID 6188901,8-Dichloroanthracene2 回

生成物 1

HCID 6007414,5-Dichloro-9-anthraldehyde収率 21%

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 6344Dichloromethane溶媒

実験手順

1,8-Dichloroanthracene prepared by the method of H. O. House et. al. (J. Org. Chem. 38 1167 (1973)). A 3 L 3-neck flask fitted with overhead mechanical stirrer, thermometer, condenser, and N2 line was charged with 1,8-dichloroanthracene (17.3 g, 70 mmol) and CH2Cl2 (1500 mL). After further cooling with salt-ice bath to 5°, SnCl4 (Aldrich, 98%, 36.5 g, 0.14 mol, 16.4 mL), was added in one portion to the reaction. No temperature change occurred. The pot temperature was kept below 5°, and 1,1-dichloromethylmethylether (Aldrich, 16.09 g, 0.14 mol, 12.60 mL) was added dropwise over 1 h. The resulting suspension was warmed slowly to reflux (37°). Considerable HCl gas evolution occurred during the warming and the early part of the reaction at 37°. The reaction mixture was then cooled to 10° and hydrolysed by careful addition of 1 L of cold H2O. After 4 h the layers were separated and the organic layer filtered, dried with anhydrous Na2SO4 (Mallinckrodt, 100 g) and filtered again and the volume reduced to 100 mL. The clear yellow solution was passed through a 1000 g plug of SiO2 using PhCH3 as the eluting solvent with 500 mL fractions. This chromatography separated unreacted 1,8-dichloroanthracene (11 g, 63%) from the aldehyde and a more polar product. Fractions containing the aldehyde were combined and the PhCH3 removed, to give 5.83 g (21%) of 4,5-dichloro-9-anthracenecarbaldehyde mp 218°-220°, (PhCH3 /CH3OH), (C, H, Cl), (lit. 224°-226°, E. L. Stogryn, J. Med. Chem. 17 563 (1974)).

後処理

  1. customA 3 L 3-neck flask fitted with overhead mechanical stirrer
  2. temperatureAfter further cooling with salt-ice bath to 5°
  3. customwas kept below 5°
  4. temperatureThe resulting suspension was warmed slowly
  5. temperatureto reflux (37°)
  6. customthe early part of the reaction at 37°
  7. customAfter 4 h the layers were separated
  8. filtrationthe organic layer filtered
  9. dry with materialdried with anhydrous Na2SO4 (Mallinckrodt, 100 g)
  10. filtrationfiltered again
  11. customThis chromatography separated unreacted 1,8-dichloroanthracene (11 g, 63%) from the aldehyde
  12. additionFractions containing the aldehyde
  13. customthe PhCH3 removed

出典と根拠

ORDレコード
ord-05508be33ade40b99d0481a3d5c3ae93
出典データセット
uspto-grants-1989_02
特許番号
US04803226

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