Ethanol → 1,4,7,10,13-Pentaazacyclopentadecane

HRID 363374Notes

Reaction equation

HRID 363374 reaction equation
C1(C)C=CC(S([N:10]2[CH2:24][CH2:23][N:22](S(C3C=CC(C)=CC=3)(=O)=O)[CH2:21][CH2:20][N:19](S(C3C=CC(C)=CC=3)(=O)=O)[CH2:18][CH2:17][N:16](S(C3C=CC(C)=CC=3)(=O)=O)[CH2:15][CH2:14][N:13](S(C3C=CC(C)=CC=3)(=O)=O)[CH2:12][CH2:11]2)(=O)=O)=CC=1.OS(O)(=O)=O.C(O)C.C(OCC)C>CC#N>[NH:10]1[CH2:24][CH2:23][NH:22][CH2:21][CH2:20][NH:19][CH2:18][CH2:17][NH:16][CH2:15][CH2:14][NH:13][CH2:12][CH2:11]1

Participants

6

Reactant 4

HCID 702EthanolHCID 1118Sulfuric AcidHCID 3283Diethyl EtherHCID 3661486HCID 3661486, compound

Product 1

HCID 1201961,4,7,10,13-PentaazacyclopentadecaneYield 31%

Reagents, catalysts & solvents 1

HCID 6342AcetonitrileSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of 1,4,7,10,13-penta(p-toluenesulfonyl)-1,4,7,10,13-pentaazacyclopentadecane prepared as in Example 1D (168 g, 0.170 mole) and concentrated H2SO4 (500 ml) was heated at 100° C. with stirring under a dry argon atmosphere for 70 h. To the resulting dark brown solution ethanol (500 ml) was added dropwise with stirring at 0° C. followed by ethyl ether (3 l). The white solid was filtered and washed with ethyl ether. The solid was then dissolved in H2O (500 ml) and the resulting solution washed with ethyl ether. Upon reducing the volume of the solution in vacuo to 200 ml, the pH was adjusted to 10-11 with 10N NaOH and the solvent was removed in vacuo. Ethanol (500 ml) was then added and removed in vacuo to dryness. The resulting tan oily solid was extracted with hot THF (2×500 ml) and filtered at room temperature. The filtrates were combined and the solvent removed in vacuo to give the crude product as a yellow crystalline solid which was then redissolved in CH3CN and filtered to remove insoluble impurities. Recrystallization from cold (-20° C.) CH3CN gave 11.3 g (31% yield) of the product as colorless needles: mp 108°-9° C.; 1H NMR (CDCl3) δ 1.74 (br s, 5 H), 2.73 (s, 20 H); Exact mass (M+Li)+ : calcd, 222.2270; Found, 222.2269 (C10H25N5Li).

Workup

  1. stirringwith stirring at 0° C.
  2. filtrationThe white solid was filtered
  3. washwashed with ethyl ether
  4. dissolutionThe solid was then dissolved in H2O (500 ml)
  5. washthe resulting solution washed with ethyl ether
  6. customthe solvent was removed in vacuo
  7. additionEthanol (500 ml) was then added
  8. customremoved in vacuo to dryness
  9. extractionThe resulting tan oily solid was extracted with hot THF (2×500 ml)
  10. filtrationfiltered at room temperature
  11. customthe solvent removed in vacuo
  12. customto give the crude product as a yellow crystalline solid which
  13. filtrationfiltered
  14. customto remove insoluble impurities
  15. customRecrystallization from cold (-20° C.) CH3CN

Sources & evidence

ORD record
ord-01d127c3887b43e0b6022dc10e8a1bee
Source dataset
uspto-grants-1999_02
Patent number
US05874421

Reaction notes

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