Camphor can be made on an industrial scale from \(\alpha\) -pinene (turpentine) by the following reactions, some of which involve carbonium-ion rearrangements of a type particularly prevalent in the bicyclic terpenes and the scourge of the earlier workers in the field trying to determine terpene structures.

Short Answer

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The conversion of α-pinene to camphor involves a series of chemical reactions: 1. Isomerization of α-pinene to camphene: \[ \text{α-pinene} \rightarrow \text{camphene} \] 2. Hydration of camphene to isoborneol, catalyzed by H₂SO₄: \[ \text{camphene} + \text{H₂O} \xrightarrow[\text{H₂SO₄}]{\text{catalyst}} \text{isoborneol} \] 3. Carbonium-ion rearrangement, converting isoborneol to borneol: \[ \text{isoborneol} \rightarrow \text{borneol} \] 4. Oxidation of borneol to camphor using Jones reagent: \[ \text{borneol} + \text{CrO₃} \xrightarrow[\text{H₂SO₄}]{\text{catalyst}} \text{camphor} + \text{Cr(III) salt} \] During this process, the structural formulas of reactants and products should be shown to emphasize the changes in the molecules.

Step by step solution

01

Isomerization of α-pinene to camphene

To start the conversion of α-pinene to camphor, we first need to isomerize α-pinene into camphene. In this reaction, the carbon-carbon double bond in α-pinene rearranges to form camphene as shown below: \[ \text{α-pinene} \rightarrow \text{camphene} \]
02

Hydration of camphene to isoborneol

Next, we will hydrate the double bond in camphene to form an alcohol. This reaction is catalyzed by a strong acid such as sulfuric acid (H₂SO₄). The alcohol is called isoborneol: \[ \text{camphene} + \text{H₂O} \xrightarrow[\text{H₂SO₄}]{\text{catalyst}} \text{isoborneol} \]
03

Carbonium-ion rearrangement

In this step, the carbonium-ion formed as an intermediate in the above reaction undergoes a 1,2-hydride shift, leading to the formation of borneol: \[ \text{isoborneol} \rightarrow \text{borneol} \]
04

Oxidation of borneol to camphor

To complete the conversion of α-pinene to camphor, we need to oxidize borneol. Jones reagent (CrO₃ in H₂SO₄) is commonly used for this oxidation. In this reaction, borneol is converted to camphor: \[ \text{borneol} + \text{CrO₃} \xrightarrow[\text{H₂SO₄}]{\text{catalyst}} \text{camphor} + \text{Cr(III) salt} \] At this point, we have successfully converted α-pinene to camphor using a series of chemical reactions, including a carbonium-ion rearrangement. The structural formulas of reactants and products in each step of the reaction should be shown to highlight the changes in the molecules during the process.

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Most popular questions from this chapter

(a) Write out all of the possible carbon skeletons for acyclic terpene and sesquiterpene hydrocarbons that follow the isoprene rule. Do not consider double-bond position isomers. (b) Do the same for monocyclic terpenes with a six-membered ring.

(a) Account for the aromatic properties of the imidazole ring. (b) Arrange the nitrogen atoms of histamine (the substance responsible for many allergenic reactions) in order of their expected basicity, and account for your answer.

A synthesis of the alkaloid morphine was completed by Gates and Tschudi in 1952 by way of the following key intermediates starting from naphthalene. Show the reagents, conditions, and important reaction intermediates that you expect would be successful in achieving each of the indicated transformations, noting that more than one synthetic step may be required between each key compound and considering carefully the order in which the operations should be carried out. Indicate those reactions which might be expected to give mixture of stereo- or position-isomers.

The blood of lobsters contains a blue copper porphyrin complex. As a model for the lobster blood pigment, draw the structure of the \(\mathrm{Cu}^{2+}\) pigment of octamethylporphin. What charge, if any, does this complex have?

Citral, \(\mathrm{C}_{10} \mathrm{H}_{16} \mathrm{O}\), is a terpene that is the major constituent of lemongrass oil. It reacts with hydroxylamine to yield a compound of formula \(\mathrm{C}_{10} \mathrm{H}_{17} \mathrm{ON}\), and with Tollens' reagent to give a silver mirror and a compound of formula \(\mathrm{C}_{10} \mathrm{H}_{16} \mathrm{O}_{2}\). Upon vigorous oxidation citral yields acetone, oxalic acid \((\mathrm{HOOC}-\mathrm{COOH})\), and levulinic acid \(\left(\mathrm{CH}_{3} \mathrm{COCH}_{2} \mathrm{CH}_{2} \mathrm{COOH}\right)\). (a) Propose a structure for citral that is consistent with these facts and with the isoprene rule. (b) Citral has two isomers, geranial and neral, which yield the same oxidation products. What is the most likely structural difference between these two isomers? (c) Geranial is obtained by mild oxidation of geraniol; neral is obtained in a similar way from nerol. On this basis assign structures to geranial and neral.

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