Nitrogen → 6-Chrysenecarbaldehyde

HRID 2413547

反応式

HRID 2413547 の反応式
N#N.[CH:3]1[C:20]2[CH:19]=[CH:18][C:17]3[C:8](=[CH:9][CH:10]=[C:11]4[C:16]=3[CH:15]=[CH:14][CH:13]=[CH:12]4)[C:7]=2[CH:6]=[CH:5][CH:4]=1.Cl[Sn](Cl)(Cl)Cl.ClC[CH:28]([O:31]C(CCl)CCl)CCl>O.ClC1C=CC=CC=1Cl>[CH:3]1[C:20]2[CH:19]=[CH:18][C:17]3[C:8](=[CH:9][C:10]([CH:28]=[O:31])=[C:11]4[C:16]=3[CH:15]=[CH:14][CH:13]=[CH:12]4)[C:7]=2[CH:6]=[CH:5][CH:4]=1

参加物

7

反応物 4

HCID 947NitrogenHCID 9171ChryseneHCID 24287Tin tetrachlorideHCID 93323Bis(1,3-dichloroisopropyl ether)

生成物 1

HCID 124387746-Chrysenecarbaldehyde

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 72391,2-Dichlorobenzene溶媒

実験手順

A 5 L 3-neck flask fitted with overhead mechanical stirrer, thermometer, condenser and N2 line was charged with chrysene (Eastman Kodak Co., Rochester, NY, 14650, 100 g, 0.438 mol) and o-dichlorobenzene (2.5 L). The liquid was warmed until all the large chunks of solid dissolved (80°) and then cooled quickly to give finely divided crystals. After further cooling with a salt-ice bath to 5°, SnCl4 (Aldrich Chemical Co., Milwaukee, WI, 53201, 98%, 228.2 g, 0.876 mol, 102.4 mL) was added in one portion. No temperature change occurred. The reaction mixture was kept below 5°, and 1,1-dichloromethylmethylether (Aldrich, 70.48 g, 0.613 mol, 55.45 mL) was added dropwise over 1 h. The resulting suspension was warmed slowly to 40°. 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 Co., St. Louis, MO, 63147, 100 g) and filtered again. The clear yellow solution was split into 2 portions and each passed through a 500 g plug of SiO2 using PhCH3 as the eluting solvent with 500 mL fractions. This chromatography separated unreacted chrysene (3 g) from the aldehyde and a more polar product. Fractions containing the aldehyde were combined and the PhCH3 removed. Crystals formed during this process and were removed periodically by filtration. After drying (at 60°) the yield of 6-chrysenecarbaldehyde was 89.46 g (79.7%) mp 167°-169°, (C,H), (lit. 168°, N. P. Buu Hoi, J.-P. Hoffinger, and P. Jacquignon, Bull. Soc. Chim. Fr. 3808 (1968)).

後処理

  1. customA 5 L 3-neck flask fitted with overhead mechanical stirrer
  2. temperatureThe liquid was warmed until all the large chunks of solid
  3. dissolutiondissolved (80°)
  4. temperaturecooled quickly
  5. customto give finely divided crystals
  6. temperatureAfter further cooling with a salt-ice bath to 5°
  7. customwas kept below 5°
  8. temperatureThe resulting suspension was warmed slowly to 40°
  9. customthe layers were separated
  10. filtrationthe organic layer filtered
  11. dry with materialdried with anhydrous Na2SO4 (Mallinckrodt Co., St. Louis, MO, 63147, 100 g)
  12. filtrationfiltered again
  13. customThe clear yellow solution was split into 2 portions
  14. customThis chromatography separated unreacted chrysene (3 g) from the aldehyde
  15. additionFractions containing the aldehyde
  16. customthe PhCH3 removed
  17. customCrystals formed during this process
  18. customwere removed periodically by filtration
  19. dry with materialAfter drying (at 60°) the yield of 6-chrysenecarbaldehyde
  20. custom89.46 g (79.7%) mp 167°-169°, (C,H), (lit. 168°, N. P. Buu Hoi, J.-P. Hoffinger, and P. Jacquignon, Bull. Soc. Chim. Fr. 3808 (1968))

出典と根拠

ORDレコード
ord-3e9a8a4010004863a4d35d4bd899113e
出典データセット
uspto-grants-1988_01
特許番号
US04719046

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