Hydrochloric Acid → 2,5-Bis[4,10-dicarboxymethyl-1,4,7,10-tetraazacyclododecan-1-yl]hexan-1,6-dioic acid

HRID 618911Notes

Reaction equation

HRID 618911 reaction equation
C([N:3]1[CH2:14][CH2:13][N:12]([CH2:15][C:16]([O:18]C(C)(C)C)=[O:17])[CH2:11][CH2:10][N:9]([CH:23]([CH2:30][CH2:31][CH:32]([N:39]2[CH2:50][CH2:49][N:48]([CH2:51][C:52]([O:54]C(C)(C)C)=[O:53])[CH2:47][CH2:46][N:45](C=O)[CH2:44][CH2:43][N:42]([CH2:61][C:62]([O:64]C(C)(C)C)=[O:63])[CH2:41][CH2:40]2)[C:33]([O:35]C(C)C)=[O:34])[C:24]([O:26]C(C)C)=[O:25])[CH2:8][CH2:7][N:6]([CH2:69][C:70]([O:72]C(C)(C)C)=[O:71])[CH2:5][CH2:4]1)=O.O.[Li+].[OH-].Cl>C(O)C>[C:52]([CH2:51][N:48]1[CH2:47][CH2:46][NH:45][CH2:44][CH2:43][N:42]([CH2:61][C:62]([OH:64])=[O:63])[CH2:41][CH2:40][N:39]([CH:32]([CH2:31][CH2:30][CH:23]([N:9]2[CH2:8][CH2:7][N:6]([CH2:69][C:70]([OH:72])=[O:71])[CH2:5][CH2:4][NH:3][CH2:14][CH2:13][N:12]([CH2:15][C:16]([OH:18])=[O:17])[CH2:11][CH2:10]2)[C:24]([OH:26])=[O:25])[C:33]([OH:35])=[O:34])[CH2:50][CH2:49]1)([OH:54])=[O:53]

Participants

6

Reactant 4

HCID 313Hydrochloric AcidHCID 962WaterHCID 3939Lithium HydroxideHCID 88278247Diisopropyl 2,5-bis[7-formyl-4,10-di-tertbutoxycarbonylmethyl-1,4,7,10-tetraazacyclododecan-1-yl]hexan-1,6-dioate

Product 1

HCID 218448692,5-Bis[4,10-dicarboxymethyl-1,4,7,10-tetraazacyclododecan-1-yl]hexan-1,6-dioic acid

Reagents, catalysts & solvents 1

HCID 702EthanolSolvent

Conditions

Temperature
100 °C

Procedure

In a 250 mL RB flask the ester of Example 4 (1.77 g, 1.63 mmol) was dissolved in ethanol (30 ml) and water was added until the solution turned slightly turbid. The temperature was elevated to 100° C. and 1N LiOH (13 mL) was added. After maintaining the mixture at 100° C. for 7 hours, the reaction was stirred at 50° C. for a further 18 hours. The solution was adjusted to pH 0.5 with 5N HCl (aq), and the mixture was refluxed for 1.5 hours and stirred at ambient temperature for an additional 18 hours. The material was loaded onto a bed of AG5OW-X8 [80 mL, (H+ -form)] strongly acidic cation exchange resin. After rinsing with water (1100 mL), the target material was eluted from the bed using 0.25N NH4OH solution. The fractions containing the title product were combined and evaporated to afford 0.79 g (79%) as a glassy solid. 1H NMR (D2O) δ 3.81 (br, 2H), 3.58-2.78 (br, 40H), 2.135 (br, 2H), 1.85 (br, 2H). 13C NMR (D2O): 22.5, 23.1, 40.6, 46.4, 48.6, 54.5, 62.6, 170.3, 175.7. MS (FAB): m/e 719.4 (MH+).

Workup

  1. customwas elevated to 100° C.
  2. temperaturethe mixture was refluxed for 1.5 hours
  3. stirringstirred at ambient temperature for an additional 18 hours
  4. washAfter rinsing with water (1100 mL)
  5. washthe target material was eluted from the bed
  6. additionThe fractions containing the title product
  7. customevaporated
  8. customto afford 0.79 g (79%) as a glassy solid

Sources & evidence

ORD record
ord-a40985e01f564e2abb5422c0a877549f
Source dataset
uspto-grants-1999_09
Patent number
US05958373

Reaction notes

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