Sodium Hydroxide → HCID 85692231, compound

HRID 1109713Notes

Reaction equation

HRID 1109713 reaction equation
[C:1]1([C:25]([CH2:27][CH2:28][C:29]([OH:31])=[O:30])=O)[C:18]2[C:19]3[C:24]4[C:3](=[CH:4][CH:5]=[C:6]5[C:23]=4[C:22]4[C:9](=[CH:10][CH:11]=[C:12]6[C:21]=4[C:20]=3[C:15](=[CH:16][CH:17]=2)[CH:14]=[CH:13]6)[CH:8]=[CH:7]5)[CH:2]=1.[OH-].[Na+]>C(O)COCCO>[C:1]1([CH2:25][CH2:27][CH2:28][C:29]([OH:31])=[O:30])[C:18]2[C:19]3[C:24]4[C:3](=[CH:4][CH:5]=[C:6]5[C:23]=4[C:22]4[C:9](=[CH:10][CH:11]=[C:12]6[C:21]=4[C:20]=3[C:15](=[CH:16][CH:17]=2)[CH:14]=[CH:13]6)[CH:8]=[CH:7]5)[CH:2]=1

Participants

4

Reactant 2

HCID 14798Sodium HydroxideHCID 54489600HCID 54489600, compound

Product 1

HCID 85692231HCID 85692231, compoundYield 86%

Reagents, catalysts & solvents 1

HCID 8117Diethylene GlycolSolvent

Conditions

Temperature
180 °C

Procedure

The Huang-Minlon method was used essentially as described in Clar and Zanders (1958), with modifications to increase the overall yield of the acid: 3-coronenoyl propionic acid (100mg), 80% hydrated hydrazine (74.8 μl), NaOH (60mg), and diethylene glycol (249μl) were combined in a 5ml round-bottomed flask. The mixture was refluxed for 90 minutes at 180° C, then water and excess hydrazine hydrate were distilled off until the temperature rose to 200° C. The mixture was refluxed for an additional 3.5 hours at 195° C., cooled to room temperature and diluted with water and 2M HCl. The resulting solid was collected by vacuum filtration and washed with cold water and 2M HCl. The product was recrystallized from xylene, dried under vacuum for 48 hours. 50mg of crystalline product was further purified by flash chromatography on a silica gel G column (100cm×2.5cm; 40 micron particle size) with a nitrogen pressure of 5-10 p.s.i. using ethyl acetate/xylene (2:1; v/v) as the running solvent. The eluant was tested using TLC (silica gel G plates) and THF/xylene (1:1; v/v) as the running solvent. The pure 4-coronenyl butyric acid (FIG. 1, compound III) exhibited a single spot (Rf=0.65) under these conditions. Fractions containing pure product were pooled and dried by rotary evaporation. A yield of 86% was obtained (66.4 mg) with a melting point of 273° C. IR and NMR analysis showed spectra consistent with the expected product. Compound III in THF had an absorption band ε294 =23,644±97 80M-1 cm-1.

Workup

  1. temperatureto increase the overall yield of the acid
  2. distillationwater and excess hydrazine hydrate were distilled off until the temperature
  3. customrose to 200° C
  4. temperatureThe mixture was refluxed for an additional 3.5 hours at 195° C.
  5. temperaturecooled to room temperature
  6. additiondiluted with water and 2M HCl
  7. filtrationThe resulting solid was collected by vacuum filtration
  8. washwashed with cold water and 2M HCl
  9. customThe product was recrystallized from xylene
  10. customdried under vacuum for 48 hours
  11. custom50mg of crystalline product was further purified by flash chromatography on a silica gel G column (100cm×2.5cm; 40 micron particle size) with a nitrogen pressure of 5-10 p.s.i
  12. additionFractions containing pure product
  13. customdried by rotary evaporation
  14. customA yield of 86% was obtained (66.4 mg) with a melting point of 273° C

Sources & evidence

ORD record
ord-8ab430fe835843aab24614f7c5a09974
Source dataset
uspto-grants-1994_06
Patent number
US05322794

Reaction notes

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