Related Experiment Video
Updated: Jun 19, 2026
09:44
Design, Synthesis, and Photochemical Properties of Clickable Caged Compounds
Published on: October 15, 2019
Cage hydrocarbons derived from dibenzosuberenone.
Marcus Pillekamp1, Wasim Alachraf, Iris M Oppel
1Faculty for Chemistry & Biochemistry, Ruhr-University Bochum, D-44780 Bochum, Germany.
The Journal of Organic Chemistry
|October 8, 2009
Summary
Revisiting cage compound 2 synthesis revealed structural errors. The photodimer and intermediate were reassigned as a pyramidalized alkene and a spirocyclic dichloride, respectively.
Area of Science:
- Organic Chemistry
- Photochemistry
- Synthetic Chemistry
Background:
- The synthesis of cage compound 2 has been previously reported.
- The structure of the photodimer and an intermediate were based on prior investigations.
Purpose of the Study:
- To reinvestigate the synthesis of cage compound 2.
- To clarify the structural assignments of the photodimer and intermediate products.
Main Methods:
- Spectroscopic analysis (e.g., NMR, Mass Spectrometry)
- X-ray crystallography
- Re-synthesis and characterization of reaction products
Main Results:
- The structure of the photodimer of compound 2 was incorrectly assigned.
- The isolated intermediate, previously identified as 9, was structurally misidentified.
- The photodimer was reassigned as monomeric pyramidalized alkene 3.
- The intermediate was reassigned as spirocyclic dichloride 10.
Conclusions:
- The reinvestigation led to a correction of the structural elucidation of key products in the synthesis of cage compound 2.
- Accurate structural assignment of alkene 3 and dichloride 10 is crucial for understanding the reaction mechanism and future synthetic endeavors.
Related Concept Videos
01:28Reduction of Benzene to Cyclohexane: Catalytic Hydrogenation
Unlike the easy catalytic hydrogenation of an alkene double bond, hydrogenation of a benzene double bond under similar reaction conditions does not take place easily. For example, in the reduction of stilbene, the benzene ring remains unaffected while the alkene bond gets reduced. Hydrogenation of an alkene double bond is exothermic and a favorable process. In contrast, to hydrogenate the first unsaturated bond of benzene, an energy input is needed; that is, the process is endothermic. This is...
02:28Cycloalkanes
Cycloalkanes are saturated cyclic hydrocarbons with carbon atoms arranged in the form of rings. They have two fewer hydrogen atoms than the corresponding acyclic alkane; therefore, their general formula is CnH2n. The structural formulas of cycloalkanes are simplified using the line-angle representation. The regular polygons are used to represent the cycloalkane rings, with each side representing a carbon-carbon bond.
The IUPAC nomenclature of cycloalkanes follows similar rules that apply to...
The IUPAC nomenclature of cycloalkanes follows similar rules that apply to...
01:28Stability of Conjugated Dienes
Introduction
A comparison of the enthalpies of hydrogenation of dienes reveals that conjugated dienes release less heat on hydrogenation, rendering them more stable than their nonconjugated analogs.
A comparison of the enthalpies of hydrogenation of dienes reveals that conjugated dienes release less heat on hydrogenation, rendering them more stable than their nonconjugated analogs.
01:23Nomenclature of Aromatic Compounds with a Single Substituent
Benzene is the simplest aromatic hydrocarbon or arene. The IUPAC names for simple monosubstituted benzene derivatives are derived by adding the substituent's name as a prefix to the parent benzene. For example, halobenzene, where the halogen could be fluoro (F), chloro (Cl), bromo (Br), and iodo (I).
01:11Nucleophilic Aromatic Substitution: Elimination–Addition
Simple aryl halides do not react with nucleophiles. However, nucleophilic aromatic substitutions can be forced under certain conditions, such as high temperatures or strong bases. The mechanism of substitution under such conditions involves the highly unstable and reactive benzyne intermediate. Benzyne contains equivalent carbon centers at both ends of the triple bond, each of which is equally susceptible to nucleophilic attack. This 50–50 distribution of products is confirmed through isotopic...
01:10Hydrolysis of Chlorobenzene to Phenol: Dow Process
Simple aryl halides do not react with nucleophiles under normal conditions. However, the reaction can proceed under drastic conditions involving high temperatures and high pressure to give the substituted products. For example, chlorobenzene is converted to phenol using aqueous sodium hydroxide at 350 °C under high pressure by the Dow process. The reaction follows an elimination-addition mechanism involving a benzyne intermediate. Here, the chloride ion is eliminated to generate the benzyne...