Ethanol → HCID 14942567, compound

HRID 363392Notes

Reaction equation

HRID 363392 reaction equation
C1(C)C=CC(S([N:10]2[CH2:30][CH2:29][N:28](S(C3C=CC(C)=CC=3)(=O)=O)[CH2:27][CH2:26][N:25](S(C3C=CC(C)=CC=3)(=O)=O)[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>[NH:10]1[CH2:30][CH2:29][NH:28][CH2:27][CH2:26][NH:25][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

5

Reactant 3

HCID 702EthanolHCID 1118Sulfuric AcidHCID 18705616HCID 18705616, compound

Product 1

HCID 14942567HCID 14942567, compoundYield 8.2%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of 1,4,7,10,13,16,19-hepta(p-toluenesulfonyl)-1,4,7,10,13,16,19-heptaazacycloheneicosane (28.3 g, 0.0205 mole) and concentrated H2SO4 (85 ml) was heated at 100° C. with stirring under a dry argon atmosphere for 4 days. To the resulting solution, ethanol (170 mL) was added dropwise with stirring at 0° C., followed by ethyl ether (430 ml). The solid was filtered and dried in vacuo over P2O5. The solid was then dissolved in H2O (75 ml) and the pH of the solution was adjusted to 10 with 10N NaOH. Insoluble impurities were removed by filtration and the solution was extracted with 6×CHCl3. The extracts were combined, dried (Na2SO4) and the solvent removed in vacuo to give a yellow oil which crystallized on standing. The aqueous layer was taken to dryness in vacuo and the resulting brown oily solid was extracted with hot THF (2×500 ml). The THF extracts were filtered and combined with the yellow solid obtained above. Insoluble impurities were removed by filtration and the solvent was removed in vacuo to give a yellow crystalline solid. The crude solid was crystallized from CHCl3 -acetonitrile to give 505 mg (8% yield) of the product as colorless needles: mp 163°-5° C.; 1H NMR (CDCl3) δ 2.99 (s, 28 H), 4.00 (br s, 7 H); Exact mass (M+H)+ : calcd., 302.3032; Found: 302.3097 (C14H36N7).

Workup

  1. stirringwith stirring at 0° C.
  2. filtrationThe solid was filtered
  3. dry with materialdried in vacuo over P2O5
  4. dissolutionThe solid was then dissolved in H2O (75 ml)
  5. customInsoluble impurities were removed by filtration
  6. extractionthe solution was extracted with 6×CHCl3
  7. dry with materialdried (Na2SO4)
  8. customthe solvent removed in vacuo
  9. customto give a yellow oil which
  10. customcrystallized
  11. extractionthe resulting brown oily solid was extracted with hot THF (2×500 ml)
  12. filtrationThe THF extracts were filtered
  13. customobtained above
  14. customInsoluble impurities were removed by filtration
  15. customthe solvent was removed in vacuo
  16. customto give a yellow crystalline solid
  17. customThe crude solid was crystallized from CHCl3 -acetonitrile

Sources & evidence

ORD record
ord-152e29675d6f4c598ebb651afbeebf24
Source dataset
uspto-grants-1999_02
Patent number
US05874421

Reaction notes

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