Organic Chemistry : Redox Chemistry

Study concepts, example questions & explanations for Organic Chemistry

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Example Questions

Example Question #1 : Using Pcc

What is the product of the reaction shown?

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Possible Answers:

Correct answer:

Explanation:

PCC can be used to oxidize primary alcohols into aldehydes, or secondary alcohols into ketones. The starting material shown is a secondary alcohol, so the product will be a ketone (a carbonyl () group where the carbonyl carbon is also attached to two other carbons).

Example Question #1 : Using Dichromate Compounds

A chemist adds the orange oxidizing agent, Na2Cr2O7, to the following substrates and dissolves the mixture in an aqueous solution of sulfuric acid. Oxidation is indicated by the disappearance of the orange color. Which of the substrate-oxidant solutions will remain orange?

               Q10

Possible Answers:

II

III

IV

I

All of the solutions will lose their orange color, indicating oxidation

Correct answer:

II

Explanation:

The following reaction schemes show the oxidation of all substrates, indicating that substrate II is in the highest oxidation state possible, and that an oxidation of this compound will not proceed.

Remember that in sulfuric acid and water, Na2Cr2O7 will be converted to CrO3, the active oxidant species. Furthermore, the oxidation mechanism involving this species includes the key step in which a hydrogen bonded to the carbon in question is eliminated, and simutaneously, a double bond from that carbon to an oxygen is installed. Thus, all substrates that feature at least one hydrogen bonded to the carbon to be oxidized can and will be oxidized in the precense of chromium trioxide.

Lastly, remember that these reactions are taking place in the prescence of water. While substrates such as compound III do not appear to be oxidizable, attack of water at the aldehyde carbon will give a dialcohol tetrathedral intermediate that can be immediately oxidized by chromium trioxide to the corresponding carboxylic acid. A similar mechanism occurs for substrate I, wherein, after the ketone oxidation state is achieved, an attack of water furnishes the same dialcohol intermediate that is oxidized to the carboxylic acid. Remember that the highest oxidation state available for organic compounds containing more than one carbon is the carboxylic acid oxidation state. Chromium trioxide will oxidize all organics to this oxidation state, unless directly-bonded hydrogens are not present in lower oxidation states, such as shown with substrate IV. 

                             A10

Example Question #2 : Using Dichromate Compounds

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Which of the following reagents would satisfy the given reaction?

Possible Answers:

Correct answer:

Explanation:

In order to drive the reactant, we must first convert the alcohol group on the ethanol into a carboxylic acid. We do so by using the oxidizing agent, , a very strong oxidizing agent that is well known to oxidize primary alcohols into carboxylic acids (among other functions). Once we have our carboxylic acid, we can simply use  to convert our carboxylic acid into an acid halide to attain our desired final product.

Example Question #1 : Using Dichromate Compounds

Which of the following substrates will be oxidized into a ketone when reacting with ?

Possible Answers:

A carboxylic acid

An aldehyde

A secondary alcohol

A primary alcohol

Correct answer:

A secondary alcohol

Explanation:

 is a strong oxidizing agent.

Not only can  reduce secondary alcohols into ketones, but it can reduce primary alcohols and aldehydes into carboxylic acids.

Example Question #1 : Using Dichromate Compounds

Screen shot 2015 12 29 at 7.16.04 am

What would be the product of the given reaction?

Possible Answers:

Screen shot 2015 12 29 at 7.16.21 am

Screen shot 2015 12 29 at 7.24.09 am

Screen shot 2015 12 29 at 7.16.25 am

Screen shot 2015 12 29 at 7.16.11 am

Correct answer:

Screen shot 2015 12 29 at 7.16.11 am

Explanation:

The reaction given would give a ketone. This type of reaction is called an oxidation reaction. Oxidation of a secondary alcohol as in the reaction given by  (sodium dichromate) in an aqueous solution of  (acetic acid) solvent yields a ketone. However, if we performed the same reaction with a primary alcohol, a carboxylic acid would have formed.

Example Question #1 : Using Other Organic Oxidizing Agents

Which of the following reagents can turn primary alcohols into a carboxylic acid?

Possible Answers:

Tollen's test

Jones Reagent (chromic acid in acetone)

PCC

Correct answer:

Jones Reagent (chromic acid in acetone)

Explanation:

The Jones reagent can convert primary alcohol to acids and secondary alcohols to ketones. The Tollen's test only converts aldehydes to carboxylic acids. PCC can only convert primary and secondary alcohol to aldehydes and ketones, respectively.  and  are reducing agents. 

Example Question #1 : Using Other Organic Oxidizing Agents

What is an appropriate reagent to convert a primary alcohol to an aldehyde? 

Possible Answers:

Correct answer:

Explanation:

To form the aldehyde, the alcohol must be oxidized. However, potassium permanganate and chromic acid are too strong and would yield a carboxylic acid. Ozonolysis works with alkenes and oxygen over platinum would not react. PCC is correct because it will oxidize the alcohol to form an aldehyde but is too weak to continue on to form the carboxylic acid.

Example Question #1 : Using Sodium Borohydride

As a reducing agent,  donates a(n) __________ to a ketone or aldehyde.

Possible Answers:

proton

hydrogen atom

hydrogen molecule

hydride ion

electron

Correct answer:

hydride ion

Explanation:

Sodium borohydride donates a hydride ion to a ketone or aldehyde. In order to form a ketone or aldehyde, a nucleophile must attack the carbonyl group. This is because the ketone or aldehyde has an electrophilic carbon—a nucleophile must attack it in order for any reaction to occur. A hydride ion is the only answer choice that plays the role of a nucleophile.

Example Question #2 : Using Sodium Borohydride

Which of the following reaction conditions will selectively reduce the ketone in the following compound, retaining the alkene functionality?

                                          Q8

Possible Answers:

LiAlH4 in THF

CeCl3 and NaBH4 in MeOH

NaBH4 in MeOH

Pd and H2 in hexanes

Pd, BaSO4, and H2 in hexanes

Correct answer:

CeCl3 and NaBH4 in MeOH

Explanation:

The correct choice, CeCl3 and NaBH4 in MeOH, shows reagents know as "Luche conditions," which are able to modify the reactivity of sodium borohydride to reduce the carbonyl to an alcohol without affecting alkene groups. This occurs as the cerium ion coordinates strongly to the carbonyl oxygen, which subsequently greatly enhances the electrophilicity at the carbonyl carbon. Nucleophilic attack of the hydride readily occurs, simultaneously destroying the electropilicty of the beta carbon of the alkene, such that it will not be reduced by the hydride reagent.

 

The incorrect answer choices would give various undesired products as detailed below:

NaBH4 in MeOH

Use of unmodified sodium borohydride would result in a 1,4 conjugate addition reaction, saturating the alkene, with a subsequent reduction of the ketone to an alcohol.

LiAlH4 in THF

Use of lithium aluminum hydride would give the same product as use of unmodified sodium borohydride, following the same reduction mechanism.

Pd and H2 in hexanes

This reagent will give reduction of the alkene only.

Pd, BaSO4, and H2 in hexanes

This reagent combination, known as Lindlar's catalyst, will also reduce the alkene only. This reagent is typically used to selectively reduce an alkyne to an alkene.

 

 

Example Question #2 : Using Sodium Borohydride

Which of these can be reduced by sodium borohydride?

Possible Answers:

2-butene

3-pentanone

2-butanol

Propanoic acid

None of these

Correct answer:

3-pentanone

Explanation:

Sodium borohydride is a reducing agent with formula . It is a reducing agent, but it is not extremely strong. It reduces ketones to alcohols, but it does not affect carboxylic acids. 3-pentanone is the only ketone of the given choices. It would be reduced to 3-pentanol.

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