Ethanol → HCID 15301550, compound

HRID 976170Notes

Reaction equation

HRID 976170 reaction equation
[CH3:1][C@H:2]1[CH2:16][N:15](S(C2C=CC(C)=CC=2)(=O)=O)[CH2:14][CH2:13][N:12](S(C2C=CC(C)=CC=2)(=O)=O)[CH2:11][CH2:10][N:9](S(C2C=CC(C)=CC=2)(=O)=O)[CH2:8][CH2:7][N:6](S(C2C=CC(C)=CC=2)(=O)=O)[CH2:5][CH2:4][N:3]1S(C1C=CC(C)=CC=1)(=O)=O.OS(O)(=O)=O.C(O)C>C(OCC)C>[CH3:1][C@H:2]1[CH2:16][NH:15][CH2:14][CH2:13][NH:12][CH2:11][CH2:10][NH:9][CH2:8][CH2:7][NH:6][CH2:5][CH2:4][NH:3]1

Participants

5

Reactant 3

HCID 702EthanolHCID 1118Sulfuric AcidHCID 53890187HCID 53890187, compound

Product 1

HCID 15301550HCID 15301550, compoundYield 12%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of (S)-2-methyl-1,4,7,10,13-penta(p-toluenesulfonyl)-1,4,7,10,13-pentaazacyclopentadecane prepared as in Example 3C (22.9 g, 0.0229-mole) and concentrated H2SO4 (85 ml) was heated at 100° C. with stirring under a dry argon atmosphere for 71 h. To the resulting brown solution, ethanol (100 ml) was added dropwise with stirring at 0° C. followed by ethyl ether 1l). The dark brown solid was filtered and washed thoroughly with ethyl ether. The solid was then dissolved in H2O (100 ml) and the resulting solution washed with ethyl ether. The pH of the solution was adjusted to 11 with 10 N NaOH and the solvent was removed in vacuo. Ethanol (2×500 ml) was then added and removed in vacuo. The resulting brown oily solid was extracted with hot THF (2×500 ml) and filtered. The filtrates were combined and the solvent was removed in vacuo. The residue was dissolved in hot THF (500 ml) and was filtered. The solvent was removed in vacuo and the residue was dissolved in CHCl3. After filtering to remove cloudiness, the solvent was removed in vacuo and the crude product was purified by fractional distillation in vacuo to give a pale yellow oil which crystallized on standing. The material was further purified by recrystallization from cold (-20° C.) CH3CN to give 641 mg (12% yield) of the product as a white crystalline solid: mp 87°-9° C.; [α]d20 =+37.2° (C=0.01,C6H6); 1H NMR (CDCl3) δ1.02 (d, J=6.3 Hz, 3 H), 1.81 (br s, 5 H), 2.37 (m, 1 H), 2.75 (m, 18 H); Exact mass (M+Li)+ : calcd., 236.2426; found, 236.2425 (C11H27N5Li).

Workup

  1. stirringwith stirring at 0° C.
  2. filtrationThe dark brown solid was filtered
  3. washwashed thoroughly with ethyl ether
  4. dissolutionThe solid was then dissolved in H2O (100 ml)
  5. washthe resulting solution washed with ethyl ether
  6. customthe solvent was removed in vacuo
  7. additionEthanol (2×500 ml) was then added
  8. customremoved in vacuo
  9. extractionThe resulting brown oily solid was extracted with hot THF (2×500 ml)
  10. filtrationfiltered
  11. customthe solvent was removed in vacuo
  12. dissolutionThe residue was dissolved in hot THF (500 ml)
  13. filtrationwas filtered
  14. customThe solvent was removed in vacuo
  15. dissolutionthe residue was dissolved in CHCl3
  16. filtrationAfter filtering
  17. customto remove cloudiness
  18. customthe solvent was removed in vacuo
  19. distillationthe crude product was purified by fractional distillation in vacuo
  20. customto give a pale yellow oil which
  21. customcrystallized
  22. customThe material was further purified by recrystallization from cold (-20° C.) CH3CN

Sources & evidence

ORD record
ord-d59a67212ae84000bb654ec71c5f31ef
Source dataset
uspto-grants-1997_03
Patent number
US05610293

Reaction notes

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