Ethanol → 1,5,9,13-Tetraazacyclohexadecane

HRID 363387Notes

Reaction equation

HRID 363387 reaction equation
C1(C)C=CC(S([N:10]2[CH2:25][CH2:24][CH2:23][N:22](S(C3C=CC(C)=CC=3)(=O)=O)[CH2:21][CH2:20][CH2:19][N:18](S(C3C=CC(C)=CC=3)(=O)=O)[CH2:17][CH2:16][CH2:15][N:14](S(C3C=CC(C)=CC=3)(=O)=O)[CH2:13][CH2:12][CH2:11]2)(=O)=O)=CC=1.OS(O)(=O)=O.C(O)C>C(OCC)C>[NH:10]1[CH2:11][CH2:12][CH2:13][NH:14][CH2:15][CH2:16][CH2:17][NH:18][CH2:19][CH2:20][CH2:21][NH:22][CH2:23][CH2:24][CH2:25]1

Participants

5

Reactant 3

HCID 702EthanolHCID 1118Sulfuric AcidHCID 10919958HCID 10919958, compound

Product 1

HCID 63980531,5,9,13-TetraazacyclohexadecaneYield 47%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of 1,5,9,13-tetra(p-toluenesulfonyl)-1,5,9,13-tetraazacyclohexadecane prepared as in Example 10E (33.7 g, 0.0399 mole) and concentrated H2SO4 (100 ml) was heated at 100° C. with stirring under a dry argon atmosphere for 72 h. To the resulting brown solution, ethanol (200 mL) was added dropwise with stirring at 0° C., followed by ethyl ether (500 ml). The tan solid was filtered and washed thoroughly with ethyl ether. The solid was then dissolved in H2O (50 ml), the pH was adjusted to 11 with solid NaOH, and the solvent was removed in vacuo. The resulting brown oily solid was extracted with hot THF (4×100 ml) and the extracts were filtered. The filtrates were combined and filtered to remove cloudiness. The solvent was removed in vacuo and the crude product was purified by recrystallization from CHCl3 -ethyl ether to give 4.29 g (47% yield) of the product as colorless prisms: mp 84°-6° C.; 1H NMR (CDCl3) δ 1.54 (br s, 4 H), 1.70 (quint, J=6.0 Hz,8 H), 2.72 (t, J=6.1 Hz, 16 H); Exact mass (M+H)+ : calcd., 229.2391; Found, 229.2417 (C12H29N4).

Workup

  1. stirringwith stirring at 0° C.
  2. filtrationThe tan solid was filtered
  3. washwashed thoroughly with ethyl ether
  4. dissolutionThe solid was then dissolved in H2O (50 ml)
  5. customthe solvent was removed in vacuo
  6. extractionThe resulting brown oily solid was extracted with hot THF (4×100 ml)
  7. filtrationthe extracts were filtered
  8. filtrationfiltered
  9. customto remove cloudiness
  10. customThe solvent was removed in vacuo
  11. customthe crude product was purified by recrystallization from CHCl3 -ethyl ether

Sources & evidence

ORD record
ord-4de0494edfef4527bffeb7412bf708f0
Source dataset
uspto-grants-1999_02
Patent number
US05874421

Reaction notes

Loading…