反应详情

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 nore 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)).

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))