Document Type

Thesis - University Access Only

Award Date


Degree Name

Master of Science (MS)

Department / School

Chemistry and Biochemistry


The first synthesis of amphipathic Lucifer yellow dyes from the anhydride rather than by derivatization of Lucifer Yellow CH or VS has been carried out. The results of the first systematic study of the synthesis of 4-alkylaminoN-alkyl-1,8-naphthalimides from 4-c hloro-1,8-naphthalic anhydride which also defines the structural limitations on the amine used are reported. The synthesis of the symmetrical 4-alkylamino-N-alkyl-1,8-naphthalimides by refluxing 4-chloro- 1,8-napthalic anhydride in straight chain amines proceeds smoothly, but displacement of the chlorine in this reaction is prevented by a-branching in the amine; substitution of the chlorine atom by sec-butylamine does not occur. The first study of the bromination of 4-alkylamino-N-alkyl-1, 8-naphthalimides and structural limitations on this reaction has been carried out. It shows that the bromination of the symmetrical monomeric 4-alkylamino-Nalkyl- 1,8-naphthalimides occurs regiospecifically at the 3- position. Oxidative dealkylation of 4-alkylamino-N-alkyl-3-bromo-1,8-naphthalimides has been found to be the only reaction of these compounds with excess bromine. These results have been confined by single crystal X-ray structure analyses of the brorninated and dealkylated products. No bromination occurs at the 6- position of the naphthalirnide. The first systematic study of the alkylation of the amino group of 4-aminoN- alkyl-1,8-naphthalimides has been carried out. It is shown that alkylation of the unsubstituted amino group of 4-amino-N-alkyl-1,8-naphthalimides can be effected by heating the amine and the alkyl halide in an aprotic dipolar solvent, either with or without sodium hydride as a base. The introduction of factors that increase the steric interaction in the product or lower the reactivity of the alkylating agent prevent the reaction from occurring. The first synthesis of bis-naphthalimides based on 4-alkylamino-N-alkyl-3- bromo-1,8-naphthalimide monomers is reported, and limitations on the synthesis of such species are specified. In particular, the presence of an amino group at the 􀥸 position of the 4-alkylamino group results in failure of the bromination, thus limiting bromination to steps of the synthetic sequence occurring after acylation of the an amino group in this position.

Library of Congress Subject Headings

Organic compounds -- Synthesis

Dyes and Dyeing -- Chemistry



Number of Pages



South Dakota State University