반응 #2500692

반응 방정식

1,1-dichloromethylmethylether

N2

triphenylene

HCl

SnCl4

→

2-triphenylenecarbaldehyde

용매

H2O

o-dichlorobenzene

반응 조건

후처리

1. 1
   기타A 1 L 3-neck flask fitted with overhead mechanical stirrer
2. 2
   온도The liquid was warmed until all the large chunks of solid
3. 3
   workup.DISSOLUTIONdissolved (80°)
4. 4
   온도cooled quickly
5. 5
   기타to give finely divided crystals
6. 6
   온도After further cooling with a salt-ice bath to 5°
7. 7
   기타was kept below 5°
8. 8
   온도The resulting suspension was warmed slowly to 40° over 2 h
9. 9
   기타the early part of the reaction at 40°
10. 10
    기타After 4 h the layers were separated
11. 11
    여과the organic layer filtered
12. 12
    건조dried with anhydrous Na2SO4 (Mallinckrodt Co., 2nd and Mallinckrodt St., St. Louis, MO, 63147, 100 g)
13. 13
    여과filtered again
14. 14
    기타The solvent was removed
15. 15
    기타to give a crude yellow oil which
16. 16
    기타was purified by preparative HPLC
17. 17
    workup.ADDITIONThe fractions containing the aldehyde
18. 18
    기타the solvent removed
19. 19
    기타to give an oil which
20. 20
    기타This material was used without further purification
21. 21
    기타Recrystallization from CH2Cl2 /CH3OH

실험 절차

A 1 L 3-neck flask fitted with overhead mechanical stirrer, thermometer, condenser, and N2 line was charged with triphenylene (Aldrich Chemical Co., Milwaukee, WI, 53201, 30 g, 0.131 mol) and o-dichlorobenzene (150 mL). 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, 98%, 58 g, 0.223 mol, 26 mL), was added in one portion to the mixture. No temperature change occurred. The pot temperature was kept below 5°, and 1,1-dichloromethylmethylether (Aldrich, 25.6 g, 0.223 mol, 20 mL) was added dropwise over 1 h. The resulting suspension was warmed slowly to 40° over 2 h and further stirred for 16 h. Considerable HCl gas evolution occurred during the warming and the early part of the reaction at 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., 2nd and Mallinckrodt St., St. Louis, MO, 63147, 100 g) and filtered again. The solvent was removed to give a crude yellow oil which was purified by preparative HPLC using PhCH3 as the eluting solvent. The fractions containing the aldehyde were combined and the solvent removed to give an oil which solidified (8.31 g, 25%). This material was used without further purification. Recrystallization from CH2Cl2 /CH3OH gave pure 2-triphenylenecarbaldehyde mp 160°-161.5°, (C,H).

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