Glycidol → 2,5-Bis[7-(2,3-dihydroxypropyl)-4,10-di-carboxymethyl-1,4,7,10-tetraazacyclododecan-1-yl]hexan-1,6-dioic acid

HRID 618912Notes

Reaction equation

HRID 618912 reaction equation
[C:1]([CH2:4][N:5]1[CH2:16][CH2:15][NH:14][CH2:13][CH2:12][N:11]([CH2:17][C:18]([OH:20])=[O:19])[CH2:10][CH2:9][N:8]([CH:21]([CH2:25][CH2:26][CH:27]([N:31]2[CH2:42][CH2:41][N:40]([CH2:43][C:44]([OH:46])=[O:45])[CH2:39][CH2:38][NH:37][CH2:36][CH2:35][N:34]([CH2:47][C:48]([OH:50])=[O:49])[CH2:33][CH2:32]2)[C:28]([OH:30])=[O:29])[C:22]([OH:24])=[O:23])[CH2:7][CH2:6]1)([OH:3])=[O:2].[OH-:51].[K+].[CH2:53]1[O:55][CH:54]1[CH2:56][OH:57]>O>[OH:55][CH:54]([CH2:56][OH:57])[CH2:53][N:37]1[CH2:36][CH2:35][N:34]([CH2:47][C:48]([OH:50])=[O:49])[CH2:33][CH2:32][N:31]([CH:27]([CH2:26][CH2:25][CH:21]([N:8]2[CH2:7][CH2:6][N:5]([CH2:4][C:1]([OH:3])=[O:2])[CH2:16][CH2:15][N:14]([CH2:53][CH:54]([OH:55])[CH2:56][OH:51])[CH2:13][CH2:12][N:11]([CH2:17][C:18]([OH:20])=[O:19])[CH2:10][CH2:9]2)[C:22]([OH:24])=[O:23])[C:28]([OH:30])=[O:29])[CH2:42][CH2:41][N:40]([CH2:43][C:44]([OH:46])=[O:45])[CH2:39][CH2:38]1

Participants

5

Reactant 3

HCID 11164GlycidolHCID 14797Potassium HydroxideHCID 218448692,5-Bis[4,10-dicarboxymethyl-1,4,7,10-tetraazacyclododecan-1-yl]hexan-1,6-dioic acid

Product 1

HCID 218448712,5-Bis[7-(2,3-dihydroxypropyl)-4,10-di-carboxymethyl-1,4,7,10-tetraazacyclododecan-1-yl]hexan-1,6-dioic acidYield 75%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

The amine of Example 5 (1.0 g; 1.4 mmol) was dissolved in water (5 ml) and the pH adjusted to 11.5 using 1N KOH solution. Glycidol was added in five aliquots of 140 μL each over a five day period. Throughout, the system was maintained at ambient temperature under nitrogen with continuous stirring. After five days, the reaction mixture was adjusted to pH 12 and loaded on to a bed of AG1-X8 ion exchange resin (80 mL, OAc-form). After rinsing with water (1.9 L), the target compound was eluted from the column using 0.5N acetic acid solution. After repeated concentration from water to remove the acetic acid, the material was lyophilized to yield 0.9 g (75%) of material. This was then further purified by preparative HPLC to yield the title compound as a white solid. 1H NMR (D2O) δ 3.51 (br), 3.25 (br), 3.11 (br), 2.89 (br), 2.67 (br), 1.66 (br, 4H). 13C NMR (D2O, 365° K): 178.16, 177.99, 177.93, 177.83, 175.34, 175.10, 174.99, 72.44, 72.28, 72.19, 71.81, 67.94, 67.84, 67.48, 67.34, 66.91, 66.81, 60.01, 59.87, 59.57, 59.36, 54.57, 54.39, 54.29, 53.50, 50.36, 50.24, 29.31, 29.09, 28.71. MS (FAB): m/E 867.7 (MH+). Anal. Calcd for C36H60N8O16 8H2O: C, 43.02; H, 8.62; N, 11.18. Found C, 43.15; H, 8.15; N, 11.18.

Workup

  1. washAfter rinsing with water (1.9 L)
  2. washthe target compound was eluted from the column
  3. concentrationconcentration from water
  4. customto remove the acetic acid

Sources & evidence

ORD record
ord-c735c4d1347d499f86bdaeff5bea6a57
Source dataset
uspto-grants-1999_09
Patent number
US05958373

Reaction notes

Loading…