Document Type
Thesis
Date of Award
5-31-1987
Degree Name
Master of Science in Engineering Science- (M.S.)
Department
Chemical Engineering, Chemistry and Environmental Science
First Advisor
Arthur Greenberg
Second Advisor
Carol A. Venanzi
Third Advisor
Tamara M. Gund
Abstract
The work undertaken in this thesis is in two parts. In the first, the structure and heat of formation of substituted cyclobutanes were studied via the computer program MMII using an IBM PCXT personal computer with a math co-processor chip. Structurally, a trend was seen to be followed in which bulkier substituents were pushed away from any steric interaction with the ring. This was accomplished by having the latter alter its puckering angle, C2C1C4 angle, HCX angle, and to a smaller extent, the bond lengths immediately adjacent to the substituted carbon atom. This results demonstrated that the ring was very flexible, however a Taft simulated reaction contradicted this finding. The heat of formation for these molecules is shown to be more exothermic when the substituent is in the equatorial position. Generally, homodesmotic equations using our calculated heats of formation and other cyclic homologues, favored the substituents to be placed on the cyclobutyl ring. However, homodesmotic equations run with the cyclopropyl ring did not follow this behavior.
The second part attempts the synthesis of 1,3-diphenyl 2,2,4,4-tetrafluorobicyclo[1.1.0]butane by trying to react PhHgCF3 with diphenylacetylene in a 1:3 mole ratio in the presence of 18-crown-6 and (n-but)4 N+I- as catalysts. All attempts at this reaction were unsuccessful. However, under the same reacting conditions, cyclooctene gave a yield of 9,9-difluorobicyclo(6.1.0)nonane of 51.70%.
Recommended Citation
Reyesgavilan, Jose Luis, "Geometric and enthalpic calculational study of monosubstituted cyclobutanes ; Attempted synthesis of 1,3-diphenyl-2,2,4,4-tetrafluorobicyclo [1.1.0] butane" (1987). Theses. 3306.
https://digitalcommons.njit.edu/theses/3306
