The aza crown, sym-1,2-benzo-aza-17-crown-5, was synthesized from 6-aza-3,9-dioxa-1,11-undecanediol, and , -dibromo-o-xylene in the presence of potassium tert-butoxide. This new crown ether was reacted with 4-bromobenzyl bromide and chloroacetyl chloride to form the N-substituted 4-bromobenzyl and chloroacetyl derivatives, respectively. The aza crown and its derivatives were identified with spectroscopic data. The bidentate phosphine amine, Ph2P(CH2)3NH2, was prepared via reduction of 3-(diphenylphosphino)propionitrile by lithium tetrahydroaluminate. Schiff-base reactions between the amine group in Ph2P(CH2)3NH2 and the aldehyde group in benzaldehyde and 4-formyl-benzo-15-crown-5 provided the respective phosphine derivatives. These products were identified with spectroscopic and analytical data. Finally, palladium derivatives of these phosphine-Shiff base ligands (Ph2P(CH2)3NCHR; R = Ph, benzo-15-crown-5) were synthesized from the reactions between (Ph2CN)2PdCl2 and the ligands.

This study has resulted in a phosphine funetionalized crown ether. synrdiQ-methoxy-5-diphenylphosphino-1.3-cplyl l-24-crown-6, obtained tkmt a live step synthesis. 4-13romophenol was treated in turn with formaldehyde. di methyl sulfate, and phosphorous trihromide. producing 4-bromo-2.6-his(bromomethyl )anisole. The key intermediate. spm-di(2-methoz}-5-bromo-I.3-z( I).l )-24-crown-6. was obtained from treating 4-hromo-3.6-bis(bromomethyl )anisole with diethylenc glycol and potassium thutoyide. The potassium ion apparently provided a template to assist the formation of the product. SLm-di(2-methosp-5-diphenylphosphino- I.3-x lyl )-24-crown-6 was obtained from treating sm-di(2-methos5-5-hromo-I.3-x'kI -24-crown-6 in sequence with n-BuLi and methyldiphern I phosphinite. The nP NMR of the phosphine crown ether showed a single signal at 6 -5.35 ppm. consistent with the formation of a single product.The'1I NMR of the phosphine crown ether in chloroform-d showed signals at6354-3.56 (crown CIF). 3.61 I OCI I;I. 4.44 (benzylic Cl I.6 and 7.25-7.29 (aromatic Ii) ppm.The integrated areas were consistent with the formula. The `C NNIR of the phosphine crown ether in chloroform-d displaced signals at 6 63.1, 68.5. 70.0. 70.1. 128.5 and 128.6 (d). 128.7. 131.8 and 131.9 (d), 132.0. 133.6 and 133.7 (d). 136.1 and 136.4 (d). 137.4 and 137.5 (dl, and 158.4 ppm. The "C signals were consistent with the formula and structure. The br)minated crown ether was characterized with 'I I and ''C NMR. as well as X-ray crystallography and elemental analysis. / Department of Chemistry

No description available.

Thesis (M.S.)--University of Missouri-Columbia, 2007. / The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file (viewed Nov. 1, 2007). Vita. Includes bibliographical references.

Thesis (M.S.)--Villanova University, 2008. / Chemistry Dept. Includes bibliographical references.

Thesis (Ph. D.) -- California Institute of Technology, 2010. / Title from home page (viewed 03/22/2010). Advisor and committee chair names found in the thesis' metadata record in the digital repository. Includes bibliographical references.

University, Diss., 2006--Wüzburg.

Universiẗat, Diss., 2003--Kiel.

Th. 3e cycle--Chim. struct.--Toulouse 3, 1977. N°: 1980.

No description available.