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Exercises · 9.20

Q.How would you convert the following compounds into benzene?

(i) Ethyne
(ii) Ethene
(iii) Hexane
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The key idea is to use cyclic trimerisation reactions — three molecules of a suitable precursor cyclise to form the six‑membered aromatic ring. Ethyne trimerises directly over a hot metal catalyst; ethene must first be dehydrogenated to ethyne; hexane must be aromatised via catalytic reforming (dehydrocyclisation). The final product in each case is benzene, CX6HX6\ce{C6H6}.


The Concept: Building an Aromatic Ring from Small Molecules

Benzene is a flat, hexagonal ring of six carbons with alternating single and double bonds (delocalised electrons). To make it from smaller compounds, we need to join three two‑carbon units (or rearrange a six‑carbon chain) and then create the conjugated π\pi‑system. The reactions that do this are all examples of cyclisation — but the starting material determines the exact path.

Let’s take each compound in turn.


1. From Ethyne (HC≡CH\ce{HC#CH})

Ethyne is the simplest alkyne. Three molecules of ethyne can be passed through a red‑hot iron tube (or over a catalyst like Ni(CO)X2\ce{Ni(CO)2} or Pd/C\ce{Pd/C}) at about 300 ∘C300\,^\circ\mathrm{C}. The triple bonds break and the six carbons join head‑to‑tail to form a ring. The driving force is the enormous stability of the aromatic ring compared to three isolated triple bonds.

The reaction is called cyclic trimerisation of alkynes:

3 HC≡CH→heatFe tubeCX6HX63\,\ce{HC#CH} \xrightarrow[\text{heat}]{\text{Fe tube}} \ce{C6H6}

Tip

This is the most direct route — no extra steps, no by‑products (except sometimes a little hydrogen). It works because each ethyne molecule contributes two π\pi‑bonds that can overlap to form the delocalised ring.


2. From Ethene (CHX2=CHX2\ce{CH2=CH2})

Ethene is an alkene — it has a double bond, not a triple bond. It cannot trimerise directly to benzene because the π\pi‑bonds are not reactive enough to cyclise without first being converted to a more unsaturated form.

The standard industrial route is:

  1. Dehydrogenate ethene to ethyne by passing it over a hot catalyst (e.g., CrX2OX3/AlX2OX3\ce{Cr2O3/Al2O3} at 600 ∘C600\,^\circ\mathrm{C}):

CHX2=CHX2→−HX2HC≡CH\ce{CH2=CH2 ->[-\ce{H2}] HC#CH}

  1. Then trimerise the ethyne as in step 1.

Alternatively, ethene can be passed over a platinum‑alumina catalyst at high temperature — this simultaneously dehydrogenates and cyclises, but the net reaction is the same:

3 CHX2=CHX2→heatPt/Al2O3CX6HX6+3 HX23\,\ce{CH2=CH2} \xrightarrow[\text{heat}]{\text{Pt/Al2O3}} \ce{C6H6} + 3\,\ce{H2}

Watch out

A common mistake is to think ethene trimerises like ethyne. It does not — the double bond is too strong and too localised. You must first make a triple bond (or use a catalyst that strips hydrogen in situ).


3. From Hexane (CHX3CHX2CHX2CHX2CHX2CHX3\ce{CH3CH2CH2CH2CH2CH3})

Hexane is a straight‑chain alkane — no multiple bonds at all. To get benzene, we need to dehydrogenate (remove hydrogen) and cyclise (form a ring) in one step. This is called catalytic reforming or dehydrocyclisation. …

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