Ethanol → HCID 10453397, compound

HRID 976173Notes

Reaction equation

HRID 976173 reaction equation
[CH3:1][CH:2]([CH3:69])[CH2:3][CH:4]1[CH2:18][N:17](S(C2C=CC(C)=CC=2)(=O)=O)[CH2:16][CH2:15][N:14](S(C2C=CC(C)=CC=2)(=O)=O)[CH2:13][CH2:12][N:11](S(C2C=CC(C)=CC=2)(=O)=O)[CH2:10][CH2:9][N:8](S(C2C=CC(C)=CC=2)(=O)=O)[CH2:7][CH2:6][N:5]1S(C1C=CC(C)=CC=1)(=O)=O.OS(O)(=O)=O.C(O)C.C(OCC)C>CC#N>[CH3:1][CH:2]([CH3:69])[CH2:3][CH:4]1[CH2:18][NH:17][CH2:16][CH2:15][NH:14][CH2:13][CH2:12][NH:11][CH2:10][CH2:9][NH:8][CH2:7][CH2:6][NH:5]1

Participants

6

Reactant 4

HCID 702EthanolHCID 1118Sulfuric AcidHCID 3283Diethyl EtherHCID 18705599HCID 18705599, compound

Product 1

HCID 10453397HCID 10453397, compoundYield 20%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of 2-(2-methylpropyl)-1,4,7,10,13-penta(p-toluenesulfonyl)-1,4,7,10,13-pentaazacyclopentadecane prepared as in Example 5C (14.1 g, 0.0135 mole) and concentrated H2SO4 (50 ml) was heated at 100° C. with stirring under a dry argon atmosphere for 69 h. To the resulting brown solution ethanol (70 mL) was added dropwise with stirring at 0° C., followed by ethyl ether (1l). The 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. A small amount of solid was removed by filtration, the pH was adjusted to 10-11 with 10N NaOH and the solvent was removed in vacuo. Ethanol (2×250 ml) was then added and removed in vacuo. The resulting brown oily solid was extracted with hot THF (2×500 ml) and filtered at room temperature. The filtrates were combined, the solvent was removed in vacuo and the residue was dissolved in THF and filtered. The solvent was removed in vacuo to give the crude product as a tan oil which was then dissolved in CH3CN and filtered to remove insoluble impurities. Crystallization occurred upon cooling the filtrate to -20° C. Recrystallization from cold (-20° C.) CH3CN gave 715 mg (20% yield) of the product as a white crystalline solid: mp 70°-6° C.; 1H NMR (CDCl3) δ0.89 (d,J=6.5 Hz, 3 H), 0.90 (d, J=6.6 Hz, 3 H), 1.13 (m, 1 H), 1.39 (m, 1 H), 1.64 (sept, J=6.3 Hz, 1 H), 2.05 (br s, 5 H), 2.34 (m, 1 H), 2.75 (m, 18 H); Exact mass (M+Li)+ : calcd. 278.2896; found, 278.2919 (C14H33N5Li).

Workup

  1. stirringwith stirring at 0° C.
  2. filtrationThe 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. customA small amount of solid was removed by filtration
  7. customthe solvent was removed in vacuo
  8. additionEthanol (2×250 ml) was then added
  9. customremoved in vacuo
  10. extractionThe resulting brown oily solid was extracted with hot THF (2×500 ml)
  11. filtrationfiltered at room temperature
  12. customthe solvent was removed in vacuo
  13. dissolutionthe residue was dissolved in THF
  14. filtrationfiltered
  15. customThe solvent was removed in vacuo
  16. customto give the crude product as a tan oil which
  17. filtrationfiltered
  18. customto remove insoluble impurities
  19. customCrystallization
  20. temperatureupon cooling the filtrate to -20° C
  21. customRecrystallization from cold (-20° C.) CH3CN

Sources & evidence

ORD record
ord-9c9acbc1fdb34c8eafdfa1899ed3a121
Source dataset
uspto-grants-1997_03
Patent number
US05610293

Reaction notes

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