Ch.11 - Reactions of Alcohols

Wade9th EditionOrganic ChemistryISBN: 9780135213728Not the one you use?Change textbook

Wade 9th Edition

Ch.11 - Reactions of Alcohols

Problem 4c(3,4)

Chapter 11, Problem 4c(3,4)

Give the structure of the principal product(s) when each of the following alcohols reacts with (3) DMP, and (4) 1 equiv NaOCl-TEMPO.
c. 4-hydroxydecanal

Verified step by step guidance

Step 1: Understand the reagents involved in the reaction. (3) DMP refers to Dess-Martin periodinane, which is a mild oxidizing agent used to convert primary alcohols to aldehydes and secondary alcohols to ketones. (4) NaOCl-TEMPO is another oxidizing system that selectively oxidizes primary alcohols to aldehydes and secondary alcohols to ketones.

Step 2: Analyze the structure of the given compound, 4-hydroxydecanal. It contains both a primary alcohol (-OH group) at the 4th position and an aldehyde (-CHO group) at the terminal position. Consider how each reagent will interact with these functional groups.

Step 3: Reaction with DMP: Dess-Martin periodinane will oxidize the primary alcohol (-OH group) at the 4th position to a ketone (-C=O group). The aldehyde group (-CHO) at the terminal position will remain unaffected because DMP does not oxidize aldehydes further.

Step 4: Reaction with NaOCl-TEMPO: This reagent will also oxidize the primary alcohol (-OH group) at the 4th position to a ketone (-C=O group). Similar to DMP, the aldehyde group (-CHO) at the terminal position will remain unchanged.

Step 5: Summarize the principal product(s): In both cases, the primary alcohol at the 4th position is oxidized to a ketone, while the aldehyde group remains intact. The resulting structure will have a ketone at the 4th position and an aldehyde at the terminal position.

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Key Concepts

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

Oxidation of Alcohols

Alcohols can undergo oxidation to form carbonyl compounds, such as aldehydes or ketones. The choice of oxidizing agent influences the reaction outcome; for instance, DMP (Dess-Martin periodinane) is a mild oxidant that selectively converts primary alcohols to aldehydes without over-oxidizing them to carboxylic acids.

Mechanism of DMP Oxidation

The mechanism of DMP oxidation involves the formation of a cyclic intermediate that facilitates the transfer of oxygen to the alcohol. This process is highly efficient and allows for the selective oxidation of alcohols, making it a valuable method in organic synthesis, particularly for sensitive substrates.

NaOCl-TEMPO Oxidation

The combination of sodium hypochlorite (NaOCl) and TEMPO (2,2,6,6-tetramethylpiperidin-1-oxyl) serves as a mild and selective oxidation system for alcohols. This method typically converts primary alcohols to aldehydes and secondary alcohols to ketones, while minimizing side reactions, making it useful for functionalized substrates.

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Related Practice

Textbook Question

We have covered several oxidants that use a multi-valent atom (Cr, Cl, S, or I) as their active species, going from a higher oxidation state before the oxidation to a lower oxidation state after oxidizing the alcohol. Draw the Lewis structures of the following atoms, before and after the oxidation of an alcohol to a ketone or aldehyde. How many bonds to oxygen does each atom have before and after the oxidation?

a. the Cr in chromic acid

b. the Cl in sodium hypochlorite

c. the S in the Swern oxidation

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Textbook Question

Give the structure of the principal product(s) when each of the following alcohols reacts with (1) Na₂Cr₂O₇/H₂SO₄, (2) PCC

d. 1-methylcyclohexan-1,4-diol

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Textbook Question

Predict the products you expect when the following starting material undergoes oxidation with an excess of each of the reagents shown below.

a. chromic acid

b. PCC (pyridinium chlorochromate)

c. sodium hypochlorite/acetic acid

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Textbook Question

Give the structure of the principal product(s) when each of the following alcohols reacts with (1) Na₂Cr₂O₇/H₂SO₄, (2) PCC

c. 4-hydroxydecanal

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Textbook Question

Give the structure of the principal product(s) when each of the following alcohols reacts with (1) Na₂Cr₂O₇/H₂SO₄, (2) PCC, (3) DMP, and (4) 1 equiv NaOCl-TEMPO.

a. octan-1-ol

b. octan-3-ol

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Textbook Question

Predict the products of the reactions of the following compounds with:

1. chromic acid or excess sodium hypochlorite with acetic acid.

2. PCC or NaOCl (1 equivalent) with TEMPO.

g. hexan-1-ol

h. acetaldehyde, CH₃CHO

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