Doctoral Dissertations

Alternative Title

Michael addition of amines to alpha-beta unsaturated esters


"The rate of Michael addition of primary amines to acrylates under different initial conditions was investigated. An acceptable agreement between different mathematical rate expressions was observed. The maximum rate was obtained in protic and polar solvents. The maximum temperature that equivalent amounts of primary amines and acrylates undergo the Michael addition without excessive formation of amide byproducts was about 50°C. The reaction rate was highly affected by the steric hindrance of the amine. Aromatic amines did not have a significant rate of reaction with simple acrylates. Lewis acid catalysts significantly increased the rate. The highest rate increase due to Lewis acid catalysts was obtained with aromatic and secondary amines. The rate was also affected by the structure of the Michael acceptor. The order of reactivity for amine addition to unsaturated esters was acrylates > maleates > fumarates > methacrylates.

A polar concerted mechanism with six-member cyclic transition state for the nucleophilic attack of amine on the Michael acceptor followed by protic medium assisted enol-keto tautomerization to yield the final product was proposed.

Macrocycles based on the Michael addition of primary amines and multi-functional acrylates were synthesized. These macrocycles were also formed as byproducts during polymer synthesis. Optimization of conditions resulted in the formation of macrocycles in high yield"--Abstract, page iii.


Van-De-Mark, Michael R.

Committee Member(s)

Ercal, Nuran
Leventis, Nicholas
Sotiriou-Leventis, Lia
Gale, Nord L.,



Degree Name

Ph. D. in Chemistry


University of Missouri--Rolla

Publication Date



ix, 188 pages

Note about bibliography

Includes bibliographical references (pages 183-187).


© 2000 Kiarash Alavi Shooshtari, All rights reserved.

Document Type

Dissertation - Restricted Access

File Type




Subject Headings

Aromatic amines
Lewis acids
Compounds, Unsaturated
Macrocyclic compounds

Thesis Number

T 7766

Print OCLC #


Electronic OCLC #


Link to Catalog Record

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