Methanol → 2-(4-Nitrobenzyl)-1,4,7,10,13,16-hexaazacyclooctadecane

HRID 719665Notes

Reaction equation

HRID 719665 reaction equation
[N+:1]([C:4]1[CH:30]=[CH:29][C:7]([CH2:8][CH:9]2[NH:26][CH2:25][C:24](=O)[NH:23][CH2:22][CH2:21][NH:20][CH2:19][CH2:18][NH:17][CH2:16][CH2:15][NH:14][CH2:13][CH2:12][NH:11][C:10]2=O)=[CH:6][CH:5]=1)([O-:3])=[O:2].CO>C1COCC1.O>[N+:1]([C:4]1[CH:30]=[CH:29][C:7]([CH2:8][CH:9]2[CH2:10][NH:11][CH2:12][CH2:13][NH:14][CH2:15][CH2:16][NH:17][CH2:18][CH2:19][NH:20][CH2:21][CH2:22][NH:23][CH2:24][CH2:25][NH:26]2)=[CH:6][CH:5]=1)([O-:3])=[O:2]

Participants

5

Reactant 2

HCID 887MethanolHCID 158906023-(4-Nitrobenzyl)-2,6-dioxo-1,4,7,10,13,16-hexaazacyclooctadecane

Product 1

HCID 158906032-(4-Nitrobenzyl)-1,4,7,10,13,16-hexaazacyclooctadecaneYield 55%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

A solution of BH3 in THF (100 mmol) was added dropwise to a stirred suspension of 3-(4-nitrobenzyl)-2,6-dioxo-1,4,7,10,13,16-hexaazacyclooctadecane (4) (10 mmol) in THF (50 ml) at 0° C. under nitrogen atmosphere. The solution was heated at reflux for 36 hours. Methanol was added slowly to the solution at 0° C. after which the solvent was removed and the residue was dissolved in methanol (50 ml); the resulting mixture was cooled at 0° C. and gaseous HCl was bubbled through the solution and then the mixture was refluxed for 12 hours. The resulting precipitate was collected washed with ether to give a white powder. The solid was dissolved in water and was loaded on a column of DOWEX 1X-8 anion-exchange resin (OH− form). The column was eluted with water; alkaline fractions were collected, and the water was removed under vacuum to give pale yellow oil. The yield was 55%.

Workup

  1. temperatureThe solution was heated
  2. temperatureat reflux for 36 hours
  3. customwas removed
  4. dissolutionthe residue was dissolved in methanol (50 ml)
  5. customgaseous HCl was bubbled through the solution
  6. temperaturethe mixture was refluxed for 12 hours
  7. customThe resulting precipitate was collected
  8. washwashed with ether
  9. customto give a white powder
  10. washThe column was eluted with water
  11. customalkaline fractions were collected
  12. customthe water was removed under vacuum
  13. customto give pale yellow oil

Sources & evidence

ORD record
ord-bc29a12cb048463e89f1fc5759d52d43
Source dataset
uspto-grants-2006_11
Patent number
US07132513B2

Reaction notes

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