The oxidation of secondary alcohols by dipotassium tetraoxoferrate (VI) In concentrated and dilute potassium hydroxide solutions

<p>Potassium ferrate of known purity was used to oxidize three alcohols (propanol-2, 1,1,1-trifluoropropanol-2, and 1,1,1,3,3,3- hexafluoropropanol-2) in 8 ~ potassium hydroxide, and a series of substituted phenyltrifluoromethyl carbinols (m-nitrophenyl-, m-bromophenyl-, p-methylphenyl-, and unsubstituted) in 0.5 ~potassium hydroxide and 3.5 ~potassium fluoride. The reactions were found to obey pseudofirst order kinetics and shown to be first order in ferrate ion and first order in alkoxy i on (ionized carbinol or alcohol); acetone production I from the oxidation of propanol-2 al so followed first order kinetics; oxygen evolution was 3/2 order· in some reactive intermediate, other than iron-VI. Deuterium isotope effects show that the breaking of the C-1! bond on the alpha-carbon is the rate determining step for the oxidation. The isotope effects also indicate, by applying the Swain Criteria, that a hydride mechanism is likely. The salt effect, isokinetic relationship, and Hammett plot all give confirmation of the suggested hydride mechanism.</p>

Name thesis:degree_name

Master of Arts (MA)

Level thesis:degree_level

Thesis

Discipline thesis:degree_discipline

Chemistry

Year

1965

Author dc:creator

• Lewis, William C.

Contributors dc:contributor

• C. M. Hull
• B. E. Norcross

Repository record dc:identifier

https://orb.binghamton.edu/dissertation_and_theses/113

OAI identifier oai:identifier

oai:orb.binghamton.edu:dissertation_and_theses-1114