Thermochemical studies of carbonyl reactions. 4. Enthalpies of hydrolysis of norbornyl ketals

Journal Article · Thu Jan 18 23:00:00 EST 1990 · Journal of Organic Chemistry; (United States)

DOI:https://doi.org/10.1021/jo00289a051· OSTI ID:5955632

Wiberg, K B; Cunningham, Jr, W C ^[1]

---

1. Yale Univ., New Haven, CT (United States)

The dimethyl ketals of norbornanone and of eight methyl-substituted norbornanones were prepared, and the enthalpies of hydrolysis were determined. The compounds were chosen to provide a variety of steric interactions between the methyl substituents and the ketal group, much of which would be relieved on going to the ketone. The enthalpies of reaction varied by over 4 kcal/mol. The experimental data were modeled by molecular mechanics (MM2), and although a good correlation was found for the less substituted compounds, the ketal of camphor fell off the slope = 1 correlation line. The free energy changes were determined, and were found not to be well correlated with the enthalpy changes.

• OSTI ID: 5955632
• Journal Information: Journal of Organic Chemistry; (United States), Journal Name: Journal of Organic Chemistry; (United States) Vol. 55:2; ISSN 0022-3263; ISSN JOCEA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ACETALS
ACTIVATION ENERGY
ALDEHYDES
ALKENES
CARBONYLS
CHEMICAL REACTIONS
CYCLOALKENES
DECOMPOSITION
ENERGY
ENTHALPY
ENTROPY
ESTERS
ETHERS
FREE ENERGY
HYDROCARBONS
HYDROLYSIS
KETONES
LYSIS
ORGANIC COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
PHYSICAL PROPERTIES
SOLVOLYSIS
THERMODYNAMIC PROPERTIES