Proton sponge → HCID 131718234, compound

HRID 1656884Notes

Reaction equation

HRID 1656884 reaction equation
[OH2:1].[OH2:2].O.O.[C:5]([O-:8])(=[O:7])[CH3:6].[Gd+3].[C:10]([O-:13])(=[O:12])[CH3:11].[C:14]([O-])(=[O:16])C.CN(C1C2C(N(C)C)=CC=CC=2C=CC=1)C>C(Cl)(Cl)Cl.CO>[CH3:5][OH:7].[C:11]([OH:2])(=[O:1])[C:10]([OH:13])=[O:12].[OH:16][CH2:14][CH:6]([CH2:5][OH:8])[OH:12]

Participants

4

Reactant 2

HCID 88675Proton spongeHCID 23371183Gadolinium acetate--water (1/3/4)

Product 1

HCID 131718234HCID 131718234, compound

Reagents, catalysts & solvents 1

HCID 21584188Chloroform methanolSolvent

Procedure

The sp3 form of ligand 11 (42 mg, 0.08 mmol) was stirred with gadolinium acetate tetrahydrate (122 mg, 0.3 mmol) and proton sponge (54 mg, 0.25 mmol) in chloroform/methanol (150 ml, v/v 1/2) for one day. The dark green reaction mixture was concentrated under reduced pressure and chromatographed through silica gel (25 cm.×1.5 cm.) which was pretreated with chloroform/triethylamine (50 ml, v/v 25/1). Chloroform/triethylamine (25/1) and chloroform/methanol/triethylamine 25/2.5/1 v/v) was used as eluents. A dark red band was first collected followed by two green bands. The last green band, which showed a clear aromatic pattern by UV/VlS, was concentrated and recrystallized from chloroform/n-hexane to give 14 mg (22%) of the Gd complex 7BFor 7BFAB MS (methanol/oxalic acid/glycerol matrix): m/e (relative intensity) 671 (155G, 58), 672 (156Gd, 78), 673 (157Gd, 94), 674 (158Gd, 100), 676 (160Gd, 64); HRMS, M+ 674 2366 (calcd. for C34H38N5158Gd 674.2368): UV/VIS (CHCl3) λmax nm (ε) 339.5 (14,850), 450.5 (36,350), 694.5 (6,757), 758.0 (23,767); IR (KBr) ν2990, 2960, 2900, 2830, 2765, 2700, 2620, 2515, 1710, 1550, 1440, 1410, 1395, 1365, 1265, 1220, 1180, 1150, 1105, 1090, 1060, 1040, 1095, 1045, 1015, 680 cm-1 ; Anal. calc. for C34H38N5Gd.(OH)2.2H2O: C, 54.89; H, 5.96; N, 9.41. Found: C, 54.49; H, 5.95; N, 8.97.

Workup

  1. concentrationThe dark green reaction mixture was concentrated under reduced pressure
  2. customchromatographed through silica gel (25 cm.×1.5 cm.) which
  3. customA dark red band was first collected
  4. concentrationwas concentrated
  5. customrecrystallized from chloroform/n-hexane

Sources & evidence

ORD record
ord-0665b471c38443bba2ad054cbda21718
Source dataset
uspto-grants-1993_10
Patent number
US05256399

Reaction notes

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