Catalysts and methods for polymer synthesis
A metal complex and unsaturated technology, applied in chemical instruments and methods, physical/chemical process catalysts, organic compounds/hydrides/coordination complex catalysts, etc., can solve problems such as lengthy synthesis processes
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example 1
[0484] A general route to the synthesis of symmetrical cobalt(III)-salen ligands of the invention is shown in Schemes E1 and E2 below:
[0485] Scheme E1
[0486]
[0487] Formylation of disubstituted phenols E1-a, as shown in Scheme E1, affords salicylaldehyde derivatives E1-b. Subsequently, 2 equivalents of this aldehyde are reacted with a diamine, in this case 1,2-diaminocyclohexane, to give the Schiff base E1-c. This compound is then reacted with cobalt(II) acetate to obtain a Co(II)-salen complex (not shown), which is oxidized with air in the presence of trifluoroacetic acid to obtain an active cobalt(III) catalyst. Similar chemical pathways are suitable for the synthesis of the catalysts described above. Those skilled in the art of organic synthesis can adapt this chemistry if necessary to provide the specific catalysts described herein.
example 2
[0489] A typical route to the synthesis of asymmetric cobalt(III)-Saren ligands is shown in Scheme E2:
[0490] Scheme E2
[0491]
[0492] Disubstituted salicylaldehyde derivative E1-b was treated with 1 equivalent of 1,2 cyclohexanediamine monohydrochloride as shown in Scheme E2. The resulting Schiff base E2-a was subsequently neutralized and another, different salicylaldehyde derivative was added. This compound is then reacted with cobalt(II) acetate to obtain a Co(II)-salen complex, which is oxidized with air in the presence of trifluoroacetic acid to obtain an active cobalt(III) catalyst. Similar chemical pathways are suitable for the synthesis of the catalysts described above. Those skilled in the art of organic synthesis can adapt this chemistry if necessary to provide the specific catalysts described herein.
example 3
[0494] Example 3 describes the catalyst The synthetic method of, wherein M is Co(III), is salcy, yes Z is the P-linked phosphorimine moiety and m is 1, where there exist one or two group (see Schemes E4 and E3, respectively).
[0495] Scheme E3
[0496]
[0497] As shown in Scheme E3, protection of trihydric alcohol E3-a in ketal form affords monohydric alcohol E3-b, which is subsequently alkylated with bromide E3-c to afford benzyl ether E3-d. Deprotection and another oxidation of benzyl alcohol affords salicylaldehyde E3-e, which is condensed with cyclohexanediamine as described above to afford ligand E3-f. Subsequent quaternization of the phosphoroimide nitrogen and metal complex formation as previously described affords catalyst E3-h. In another route not shown here, the metal is intercalated first, followed by a quaternization reaction.
[0498] Scheme E3b
[0499]
[0500] Condensation of salicylaldehyde E3-e (described above) with cyclohexanediamine...
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Abstract
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