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. 2018 Mar 13;23(3):648.
doi: 10.3390/molecules23030648.

Vinylation of a Secondary Amine Core with Calcium Carbide for Efficient Post-Modification and Access to Polymeric Materials

Konstantin S Rodygin  1 , Alexander S Bogachenkov  2 , Valentine P Ananikov  3   4
Affiliations

Vinylation of a Secondary Amine Core with Calcium Carbide for Efficient Post-Modification and Access to Polymeric Materials

Konstantin S Rodygin et al. Molecules. .

Abstract

We developed a simple and efficient strategy to access N-vinyl secondary amines of various naturally occurring materials using readily available solid acetylene reagents (calcium carbide, KF, and KOH). Pyrrole, pyrazole, indoles, carbazoles, and diarylamines were successfully vinylated in good yields. Cross-linked and linear polymers were synthesized from N-vinyl carbazoles through free radical and cationic polymerization. Post-modification of olanzapine (an antipsychotic drug substance) was successfully performed.

Keywords: acetylene; calcium carbide; functionalization; olanzapine; vinylation.

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Conflict of interest statement

The authors declare no conflict of interest.

Figures

Scheme 1
Scheme 1
Synthetic procedures to access N-vinyl derivatives.
Scheme 2
Scheme 2
Plausible mechanism of vinylation of secondary amines.
Scheme 3
Scheme 3
Structures of vinylated secondary amine products and yields (in %). Reaction conditions: amine 1 (1 mmol), CaC2 (2 mmol), KOH (1.1 mmol), KF (1 mmol), H2O (4 mmol), DMSO (1 mL). NMR yields are given without parentheses, isolated yields are given in parentheses.
Scheme 4
Scheme 4
N-vinyl-1,2,3,4-tetrahydrocarbazole synthesis and polymerization.
Scheme 5
Scheme 5
Double vinylation followed by the polymerization of bis(N-vinyl-3,3′-carbazole) and the X-ray structure of 2m.
Scheme 6
Scheme 6
Vinylation of olanzapine and X-ray structure of the vinylated olanzapine derivative.
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