반응 #1153159

반응 방정식

hexamethylenetetramine

4-(5-trifluoromethyl-tetrazol-1-yl)-phenol

trifluoroacetic acid

hexamethylenetetramine

H2SO4

→

title compound

수율 66.4%

2-Hydroxy-5-(5-trifluoromethyl-tetrazol-1-yl)-benzaldehyde

수율 66.4%

용매

water

반응 조건

후처리

1. 1
   기타To a 2 L nitrogen purged round bottom flask fitted with a condenser
2. 2
   온도The solution was heated
3. 3
   온도to reflux
4. 4
   온도refluxed for 4 h
5. 5
   온도the solution refluxed overnight
6. 6
   온도The reaction was cooled
7. 7
   여과The yellow suspension was filtered
8. 8
   세척the cake washed with water until the filtrate
9. 9
   workup.DISSOLUTIONThe cake was dissolved in methylene chloride
10. 10
    여과filtered through 300 g of Silica Gel 60 (70-230 mesh)
11. 11
    기타flushed with 6 L of methylene chloride
12. 12
    기타The solvent was removed in vacuo
13. 13
    기타the residue flushed with hexanes
14. 14
    여과filtered
15. 15
    기타The white crystalline product that was obtained
16. 16
    기타was dried

실험 절차

To a 2 L nitrogen purged round bottom flask fitted with a condenser was charged 67.7 g (0.29 mol) of 4-(5-trifluoromethyl-tetrazol-1-yl)-phenol, 540 mL trifluoroacetic acid, and 86.3 g (0.62 mol, 2.1 eq) of hexamethylenetetramine. The solution was heated to reflux and refluxed for 4 h. An additional 10 g (0.07 mol, 0.24 equiv) of hexamethylenetetramine was added and the solution refluxed overnight. The reaction was cooled and poured slowly into 3 L of 1N H2SO4. The suspension was diluted with an additional 500 mL of water and aged at room temperature for 30 min and at 0° C. and for additional 30 min. The yellow suspension was filtered and the cake washed with water until the filtrate was neutral. The cake was dissolved in methylene chloride and filtered through 300 g of Silica Gel 60 (70-230 mesh) and flushed with 6 L of methylene chloride. The solvent was removed in vacuo and the residue flushed with hexanes. The resulting slurry was cooled to room temperature and filtered. The white crystalline product that was obtained was dried yielding 50.4 g (66.4% yield) of the title compound. An additional 6.9 g (9.1%, for a combined yield of 57.3 g, 75.5% yield) was obtained by extracting the aqueous filtrate with ether and chromatographing (Silica Gel 60, methylene chloride): 1H NMR (CDCI3) δ 7.23 (d, J=9 Hz, 1H), 7.62 (dd, J=9, 2 Hz, 1H), 7.73 (d, J=2.5 Hz, 1H), 9.96 (s, 1H). MS (EI) m/z 258. Anal. Calcd for C9H5F3N4O2: C, 41.87; H, 1.95; F, 22.08; N, 21.70. Found: C, 41.87; H, 1.98; F, 22.61; N, 21.74.

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