13.12: Dehydration Reactions of Alcohols

Dehydration of Alcohols to Yield Alkenes

One way to synthesize alkenes is by dehydration of alcohols, a process in which alcohols undergo E1 or E2 mechanisms to lose water and form a double bond. The dehydration reaction of alcohols to generate alkene proceeds by heating the alcohols in the presence of a strong acid, such as sulfuric or phosphoric acid, at high temperatures.

The required range of reaction temperature decreases with increasing substitution of the hydroxy-containing carbon:

• 1° alcohols: 170° - 180°C
• 2° alcohols: 100°– 140 °C
• 3° alcohols: 25°– 80°C

If the reaction is not sufficiently heated, the alcohols do not dehydrate to form alkenes, but react with one another to form ethers (e.g., the Williamson Ether Synthesis).

Alcohols are amphoteric; they can act both as acid or base. The lone pair of electrons on oxygen atom makes the –OH group weakly basic. Oxygen can donate two electrons to an electron-deficient proton. Thus, in the presence of a strong acid, R—OH acts as a base and protonates into the very acidic alkyloxonium ion ⁺OH₂ (The pKa value of a tertiary protonated alcohol can go as low as -3.8). This basic characteristic of alcohol is essential for its dehydration reaction with an acid to form alkenes.

Mechanism for the Dehydration of Alcohol into Alkene

Different types of alcohols may dehydrate through a slightly different mechanism pathway. However, the general idea behind each dehydration reaction is that the –OH group in the alcohol donates two electrons to H⁺ from the acid reagent, forming an alkyloxonium ion. This ion acts as a very good leaving group which leaves to form a carbocation. The deprotonated acid (the nucleophile) then attacks the hydrogen adjacent to the carbocation and form a double bond.

Primary alcohols undergo bimolecular elimination (E2 mechanism) while secondary and tertiary alcohols undergo unimolecular elimination (E1 mechanism). The relative reactivity of alcohols in dehydration reaction is ranked as the following

Methanol < primary < secondary < tertiary

Primary alcohol dehydrates through the E2 mechanism. Oxygen donates two electrons to a proton from sulfuric acid H₂SO₄, forming an alkyloxonium ion. Then the nucleophile HSO₄^– back-side attacks one adjacent hydrogen and the alkyloxonium ion leaves in a concerted process, making a double bond.

Secondary and tertiary alcohols dehydrate through the E1 mechanism. Similarly to the reaction above, secondary and tertiary –OH protonate to form alkyloxonium ions. However, in this case the ion leaves first and forms a carbocation as the reaction intermediate. The water molecule (which is a stronger base than the HSO_4^- ion) then abstracts a proton from an adjacent carbon, forming a double bond. Notice in the mechanism below that the aleke formed depends on which proton is abstracted: the red arrows show formation of the more substituted 2-butene, while the blue arrows show formation of the less substituted 1-butene. Recall the general rule that more substituted alkenes are more stable than less substituted alkenes, and trans alkenes are more stable than cis alkenes. Thereore, the trans diastereomer of the 2-butene product is most abundant.

Dehydration reaction of secondary alcohol

The dehydration mechanism for a tertiary alcohol is analogous to that shown above for a secondary alcohol.

The E2 elimination of 3º-alcohols under relatively non-acidic conditions may be accomplished by treatment with phosphorous oxychloride (POCl₃) in pyridine. This procedure is also effective with hindered 2º-alcohols, but for unhindered and 1º-alcohols an S_N2 chloride ion substitution of the chlorophosphate intermediate competes with elimination. Examples of these and related reactions are given in the following figure. The first equation shows the dehydration of a 3º-alcohol. The predominance of the non-Zaitsev product (less substituted double bond) is presumed due to steric hindrance of the methylene group hydrogen atoms, which interferes with the approach of base at that site. The second example shows two elimination procedures applied to the same 2º-alcohol. The first uses the single step POCl₃ method, which works well in this case because S_N2 substitution is retarded by steric hindrance. The second method is another example in which an intermediate sulfonate ester confers halogen-like reactivity on an alcohol. In every case the anionic leaving group is the conjugate base of a strong acid.

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Contributors

• Jeffrey Ma