prepare 2-mythe propene by dehydration of alcohol
Answers
Acetone can be converted to 2 methyl propene by first converting it into propanol using Grignard reagent and then dehydration leads to 2-methyl propene.
Answer:
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.
general rxn complete.png
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).
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Alcohols are amphoteric; they can act as both 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.
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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 base) then reacts with 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 reactions is ranked as follows:
Methanol < primary < secondary < tertiary
Primary alcohols dehydrate through the E2 mechanism. The hydroxyl oxygen donates two electrons to a proton from sulfuric acid (H2SO4), forming an alkyloxonium ion. Then the conjugate base, HSO4–, reacts with one of the adjacent (beta) hydrogen atoms while the alkyloxonium ion leaves in a concerted process, forming a double bond.
primary rxn complete.png
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 HSO4- ion) then abstracts a proton from an adjacent carbon to form a double bond. Notice in the mechanism below that the alkene 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 that according to Zaitsev's Rule, the more substituted alkenes are formed preferentially because they are more stable than less substituted alkenes. Additinally, trans alkenes are more stable than cis alkenes and are also the major product formed. For the example below, the trans diastereomer of the 2-butene product is most abundant.