Uncommon Four-Membered Building Blocks - Cyclobutenes, Azetines and Thietes

Heterocyclic aromatic compounds are cyclic compounds that are aromatic and have one or more heteroatoms—atoms other than carbon, in the ring. Depending upon the number of atoms present in the ring, they can be either five or six-membered. Examples of five-membered heterocyclic aromatic compounds include pyrrole, furan, thiophene, and imidazole. Pyrrole consists of one nitrogen atom having one lone pair of electrons. Furan and thiophene have one oxygen and one sulfur heteroatom,...

Alkynes are unsaturated hydrocarbons characterized by the presence of carbon-carbon triple bonds and have a general formula CnH2n-2. The nomenclature of alkynes follows a set of rules similar to alkanes and alkenes; however, alkynes bear the suffix "-yne" instead of "-ane" or "-ene." There are two approaches to naming alkynes:

Like benzene, cyclobutadiene and cyclooctatetraene are cyclic compounds with alternate single and double bonds. However, their chemical behavior differs from benzene, as they are unstable and not aromatic. So, what are the structural characteristics of unsaturated compounds categorized as aromatic?  
For the first time, Eric Hückel, a German chemical physicist, derived a set of structural features for a compound to be classified as aromatic. This is now known as Hückel’s rule or the 4n +...

The simplest aromatic amine is phenylamine, which contains an –NH2 functionality directly attached to an aromatic ring. The name aniline is designated for this skeleton. As shown in Figure 1, the common names of the functionalized anilines involve prefixes ortho-, meta-, and para- to indicate the substitution position. Different functionalized aniline derivatives also have notable trivial names.

Cycloheptatriene is a neutral monocyclic unsaturated hydrocarbon that consists of an odd number of carbon atoms and an intervening sp3 carbon in the ring. The three double bonds in the ring correspond to 6 π electrons, which is a Huckel number, and therefore satisfies the criteria of 4n + 2 π electrons. However, the intervening sp3 carbon disrupts the continuous overlap of p orbitals. As a result, cycloheptatriene is not aromatic.
Removing one hydrogen from the intervening CH2 group...

Cyclic ethers are heterocyclic compounds with an oxygen atom in the ring along with carbon atoms. They are named depending on the number of carbon atoms present in their ring system. Cyclic ethers with a three-membered ring system are called “oxirane”, four-membered ring systems as “oxetane”, five-membered ring systems as “oxolane”, and six-membered ring systems as “oxane”. The cyclic structure of these rings imposes angle strain, and this strain...