A kind of rare earth lanthanum complex and its synthesis method
A synthesis method and complex technology, applied in the field of rare earth lanthanum complexes and their synthesis, to achieve the effects of simple synthesis method, mild reaction conditions, and high purity
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[0040] The preparation method of the above-mentioned rare earth lanthanum complex may include:
[0041]1) Synthesis of 4,7,13,16-tetracarboxymethyl-1,10-dioxo-4,7,13,16-tetraazacycloctadecane, referred to as L, the synthesis route is as follows:
[0042]
[0043] The synthesis method is: dissolving 1,10-dioxo-4,7,13,16-tetraaza-18-crown-6 in CH 2 Cl 2 Finally, add anhydrous potassium carbonate, heat to reflux for 0.5-3h, add ethyl bromoacetate and then heat to reflux for 18-24 hours, filter and evaporate to obtain an oily substance; among them, ethyl bromoacetate and 1,10-dioxo- The molar ratio of 4,7,13,16-tetraza-18-crown-6 is preferably 4-7; CH 2 Cl 2 The ratio of volume to 1,10-dioxo-4,7,13,16-tetraza-18-crown-6 moles is preferably 10L / mol-20L / mol; anhydrous potassium carbonate and 1,10-di The molar ratio of oxygen-4,7,13,16-tetraaza-18-crown-6 is preferably 4-8.
[0044] Mix the above oil with hydrochloric acid aqueous solution to obtain a mixed solution, heat the...
Embodiment 1
[0070] Weigh 0.52g (2mmol) of 1,10-dioxo-4,7,13,16-tetraza-18-crown-6 in a 50mL round bottom flask,
[0071] Add 20mL CH 2 Cl 2 As a solvent, add 1.2g (8.8mmol) of anhydrous potassium carbonate, reflux for 3h, then add 0.92mL (8.4mmol) of ethyl bromoacetate, reflux for 24h under normal pressure, filter, and rotate the filtrate to obtain 1.0 g of oil.
[0072] by HCl:H 2 The volume ratio of O=1.5:1 prepares hydrochloric acid aqueous solution, the obtained oil is mixed with hydrochloric acid aqueous solution (20mL) to obtain a mixed solution, which is refluxed at normal pressure for 24 hours and then filtered to obtain a filtrate. The filtrate was evaporated to about 10ml, and the hydrochloride crystals of Ligand L precipitated out. The crystals were collected by filtration and dried at room temperature to obtain 0.9gL, whose M.p.>300°C.
[0073] Weigh 0.128g (0.2mmol) of Ligand L into a 50mL beaker, add 20mL of absolute ethanol, and stir to form a suspension of Ligand L. W...
Embodiment 2
[0075] Weigh 0.78g (3mmol) of 1,10-dioxo-4,7,13,16-tetraza-18-crown-6 in a 50mL round bottom flask,
[0076] Add 45mLCH 2 Cl 2 As a solvent, add 2.5g (18mmol) of anhydrous potassium carbonate, reflux for 1.5h, then add 1.96mL (18mmol) of ethyl bromoacetate, reflux for 20h, filter, and rotate the filtrate to obtain 1.4g of oil .
[0077] by HCl:H 2 Aqueous hydrochloric acid was prepared at a volume ratio of O=2:1, and the resulting oil was mixed with aqueous hydrochloric acid (25mL) to obtain a mixed solution, which was refluxed at normal pressure for 18 hours and then filtered to obtain a filtrate, which was evaporated To about 12ml, the hydrochloride crystals of Ligand L were precipitated, and the crystals were collected by filtration and dried in air at room temperature to obtain 1.4gL, whose M.p.>300°C.
[0078] Weigh 0.192g (0.3mmol) of Ligand L into a 50mL beaker, add 25mL of absolute ethanol, and stir to form a suspension of Ligand L. Weigh 0.096g (2.4mmol) of NaOH,...
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