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Ch. 23 - Carbohydrates and Nucleic Acids
Wade - Organic Chemistry 9th Edition
Wade9th EditionOrganic ChemistryISBN: 9780135213728Not the one you use?Change textbook
Chapter 23, Problem 33

The Wohl degradation, an alternative to the Ruff degradation, is nearly the reverse of the Kiliani–Fischer synthesis. The aldose carbonyl group is converted to the oxime, which is dehydrated by acetic anhydride to the nitrile (a cyanohydrin). Cyanohydrin formation is reversible, and a basic hydrolysis allows the cyanohydrin to lose HCN. Using the following sequence of reagents, give equations for the individual reactions in the Wohl degradation of D-arabinose to D-erythrose. Mechanisms are not required.
a. hydroxylamine hydrochloride
b. acetic anhydride
c. OH, H2O

Verified step by step guidance
1
Step 1: Start with d-arabinose, which is an aldose sugar. The first reagent, hydroxylamine hydrochloride, reacts with the carbonyl group (aldehyde) of d-arabinose to form an oxime. This reaction involves the nucleophilic attack of hydroxylamine (NH2OH) on the carbonyl carbon, followed by the elimination of water.
Step 2: Treat the oxime formed in Step 1 with acetic anhydride. Acetic anhydride acts as a dehydrating agent, converting the oxime into a nitrile group (-C≡N). This step results in the formation of a cyanohydrin derivative of d-arabinose.
Step 3: The cyanohydrin derivative undergoes basic hydrolysis in the presence of hydroxide ions (-OH) and water (H2O). The nitrile group (-C≡N) is hydrolyzed to a carboxylic acid intermediate, and the molecule loses a molecule of hydrogen cyanide (HCN).
Step 4: The loss of HCN results in the shortening of the carbon chain by one carbon atom, converting d-arabinose (a 5-carbon sugar) into d-erythrose (a 4-carbon sugar). This step completes the Wohl degradation process.
Step 5: Write the chemical equations for each step to represent the transformations. For example, the first equation would show the conversion of d-arabinose to its oxime, the second equation would show the formation of the nitrile, and the third equation would show the hydrolysis and chain shortening to d-erythrose.

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Key Concepts

Here are the essential concepts you must grasp in order to answer the question correctly.

Wohl Degradation

The Wohl degradation is a chemical reaction that transforms aldoses into their corresponding ketoses through a series of steps involving the conversion of the carbonyl group to an oxime, followed by dehydration to form a nitrile. This process is significant in carbohydrate chemistry as it allows for the manipulation of sugar structures, facilitating the synthesis of different sugars.
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Cyanohydrin Formation

Cyanohydrins are formed when a carbonyl compound reacts with hydrogen cyanide (HCN) or a cyanide source, resulting in a compound that contains both a hydroxyl group and a nitrile group. This reaction is reversible, meaning that under certain conditions, cyanohydrins can revert to their original carbonyl forms, which is crucial in the Wohl degradation as it allows for further transformations in the reaction sequence.
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Reagents in Organic Reactions

The reagents used in organic reactions play a critical role in determining the course and outcome of the reaction. In the Wohl degradation, hydroxylamine hydrochloride is used to convert the aldose carbonyl to an oxime, acetic anhydride facilitates the dehydration to a nitrile, and a basic hydrolysis step allows for the removal of HCN from the cyanohydrin. Understanding the function of each reagent is essential for predicting the products of the reaction.
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Related Practice
Textbook Question

In 1891, Emil Fischer determined the structures of glucose and the seven other D-aldohexoses using only simple chemical reactions and clever reasoning about stereochemistry and symmetry. He received the Nobel Prize for this work in 1902. Fischer had determined that D-glucose is an aldohexose, and he used Ruff degradations to degrade it to (+)-glyceraldehyde. Therefore, the eight D-aldohexose structures shown in Figure 23-3 are the possible structures for glucose.

Pretend that no names are shown in Figure 23-3 except for glyceraldehyde, and use the following results to prove which of these structures represent glucose, mannose, arabinose, and erythrose.

(a) Upon Ruff degradation, glucose and mannose give the same aldopentose: arabinose. Nitric acid oxidation of arabinose gives an optically active aldaric acid. What are the two possible structures of arabinose?

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Textbook Question

Draw the structures of the individual mutarotating α and β anomers of maltose.

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Textbook Question

Ruff degradation of D-arabinose gives D-erythrose. The Kiliani–Fischer synthesis converts D-erythrose to a mixture of D-arabinose and D-ribose. Draw out these reactions, and give the structure of D-ribose.

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Textbook Question

D-Altrose is an aldohexose. Ruff degradation of D-altrose gives the same aldopentose as does degradation of D-allose, the C3 epimer of glucose. Give the structure of D-altrose.

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Textbook Question

In 1891, Emil Fischer determined the structures of glucose and the seven other D-aldohexoses using only simple chemical reactions and clever reasoning about stereochemistry and symmetry. He received the Nobel Prize for this work in 1902. Fischer had determined that D-glucose is an aldohexose, and he used Ruff degradations to degrade it to (+)-glyceraldehyde. Therefore, the eight D-aldohexose structures shown in Figure 23-3 are the possible structures for glucose.

Pretend that no names are shown in Figure 23-3 except for glyceraldehyde, and use the following results to prove which of these structures represent glucose, mannose, arabinose, and erythrose.

(b) Upon Ruff degradation, arabinose gives the aldotetrose erythrose. Nitric acid oxidation of erythrose gives an optically inactive aldaric acid, meso-tartaric acid. What is the structure of erythrose?

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Textbook Question

D-Lyxose is formed by Ruff degradation of galactose. Give the structure of D-lyxose. Ruff degradation of D-lyxose gives D-threose. Give the structure of D-threose.

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