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

HRID 2413616

반응식

HRID 2413616 반응식
[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

참가 물질

8

반응물 5

HCID 313Hydrochloric AcidHCID 947NitrogenHCID 24287Tin tetrachlorideHCID 93323Bis(1,3-dichloroisopropyl ether)HCID 6188901,8-Dichloroanthracene2회

생성물 1

HCID 6007414,5-Dichloro-9-anthraldehyde수율 21%

시약·촉매·용매 2

HCID 962Water용매HCID 6344Dichloromethane용매

실험 절차

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 a 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)).

후처리

  1. customA 3 L 3-neck flask fitted with overhead mechanical stirrer
  2. temperatureAfter further cooling with a 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

출처 및 근거

ORD 기록
ord-3dae78d223f945128f5d36091d10a65c
출처 데이터셋
uspto-grants-1988_01
특허 번호
US04719047

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