The synthesis of 1-methyl-promazine, 4-hydroxymethyl-iminodibenzyl, and 4-bromo-5-trimethylsilyl-iminodibenzyl via dilithiation and ¹H-NMR's are described. Molecular modeling was done for the latter compound. The heat of dissociation was 30.6 kcal/mole for the lowest energy conformer. Rotational energies were examined for three bonds. The IC₅₀ values for inhibition of neurotransmitter uptake by rat brain synaptosomes were determined for a series of 1-substituted promazines, and 4-substituted imipramines. 1-Substituted promazines were fair inhibitors of serotonin uptake with an average IC₅₀ of 2000 nm. Their potency for inhibiting norepinephrine uptake was difficult to assess due to poor assay reproducibility, and the average IC₅₀ was estimated at 200 to 1700 nm. Serotonin, but not norepinephrine, uptake inhibition was increased with additional ring substitution at C(2) with a trifluoromethyl group. The 4-substituted imipramines were equal or slightly decreased in potency to unsubstituted imipramine for uptake inhibition of both neurotransmitters. IC₅₀'s were also reported for imipramine and desipramine.

This study has resulted in a crown ether functionalized with both phosphine and phenol groups, 5-diphenylphosphino-1,3-xylyl-18-crown-5. The target molecule was obtained from a six step synthesis. 4-Bromophenol was treated in sequence with formaldehyde, dimethylsulfate, and phosphorus tribromide producing 4-bromo-2,6-bis(bromomethyl)anisole. The main intermediate, 5-diphenylphosphino-1,3-xylyl-18-crown-5, was obtained by treating 4-bromo-2,6-bis(bromomethyl)anisole in sequence with tetraethylene glycol, lithium iodide, and methyldiphenyl phosphonite. The lithium iodide cleaved the anisole-to-methyl group bond, and the methyldiphenyl phosphonite provided the phosphine group for the crown ether following a lithium bromine exchange reaction. The 31P NMR of the phosphine crown ether showed a single signal at 6 -5.9, showing consistency of a single product. The IH NMR of the phosphine crown ether in deuterated chloroform showed signals at 6 3.55-3.7 (crown CH2), 6 4.6 (benzylic CH2), 6 7.1 (d, J = 7.o Hz, crown aromatic CH2), and 6 7.2-7.4 (noncrown aromatic CH2). / Department of Chemistry

Thesis (Ph. D.)--University of Hawaii at Manoa, 1991. / Includes bibliographical references (leaves 41-43, 244-250) / Microfiche. / xiii, 374 leaves, bound ill. 29 cm

Thesis (Ph. D.)--University of Wisconsin--Madison, 1976. / Typescript. Vita. eContent provider-neutral record in process. Description based on print version record. Includes bibliographical references (leaves 281-286).

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

published_or_final_version / Chemistry / Master / Master of Philosophy

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

The literature on preparation and oxidation of carbanions is reviewed. Attempted preparation of many new carbanions, using Lochmann's base (potassium t-butoxide/n-butyllithium), is described; dianions 59, 76, and 85 were prepared for the first time. Preparation of 85, calculated to have the least delocalization energy of all six-carbon acyclic carbanions, completes the series of six-carbon acyclic dianions. Reaction of these and three other dicarbanions (o-48, m-58, and p-58) with dihalides and oxidizing agents were investigated. The shortest routes to certain {n}- and {n,n}-cyclophanes resulted. Good yields were obtained of {9}- and -metacyclophane. Several {n}-2,6-pyridinophanes were synthesized from dianion 59. {6,6}- and {7,7}-metacyclophane and {5,5}-, {7,7}-, and {9,9}- orthocyclophane were synthesized for the first time.

No description available.