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Aldehydes and Ketones II. Oxidation and Reduction: Synthesis

This document is from a chemistry class and covers various methods for reducing carbonyl groups in aldehydes and ketones, including: - Lithium aluminum hydride and sodium borohydride reduction, which convert carbonyl groups to alcohols. Specific examples and reaction mechanisms are provided. - Catalytic hydrogenation over nickel, which reduces carbonyl groups to alcohols. - The Clemmensen and Wolff-Kishner reductions, which reduce carbonyl groups to methylene groups using zinc-mercury amalgam or hydrazine respectively. Examples are given. - Desulfurization using Raney nickel catalyst, which removes thiol groups from carbonyl

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Matthew M. Seabaugh
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60 views34 pages

Aldehydes and Ketones II. Oxidation and Reduction: Synthesis

This document is from a chemistry class and covers various methods for reducing carbonyl groups in aldehydes and ketones, including: - Lithium aluminum hydride and sodium borohydride reduction, which convert carbonyl groups to alcohols. Specific examples and reaction mechanisms are provided. - Catalytic hydrogenation over nickel, which reduces carbonyl groups to alcohols. - The Clemmensen and Wolff-Kishner reductions, which reduce carbonyl groups to methylene groups using zinc-mercury amalgam or hydrazine respectively. Examples are given. - Desulfurization using Raney nickel catalyst, which removes thiol groups from carbonyl

Uploaded by

Matthew M. Seabaugh
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPT, PDF, TXT or read online on Scribd
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Chapter 17

Aldehydes and Ketones II. Oxidation and Reduction: Synthesis

WWU -- Chemistry

Assignment for Chapter 17


Sections 17.0 through 17.2 Section 17.3 -- SKIP Sections 17.4 through 17.12 Section 17.13 through 17.15 -SKIP Sections 17.16 through 17.20 Problems
WWU -- Chemistry

Problem Assignment
In-Text Problems
17-1 through 17-11 17-15 through 17-18

End-of-Chapter Problems
1 through 4 (all parts)

WWU -- Chemistry

Reduction of a Carbonyl Group to an Alcohol

WWU -- Chemistry

What If We Had the Worlds Simplest Nucleophile?


:O : R _ H: C R R _ .. : O: C H R H2O R OH C H R

WWU -- Chemistry

If we could make this work, we would have means of reducing the carbonyl group.
Go back and re-read the Special Topics box at the beginning of Chapter 14.

WWU -- Chemistry

Lithium Aluminum Hydride


H H Al H
Lithium aluminum hydride, LiAlH4, is a very powerful hydride donor, and thus it is an excellent reducing agent.
WWU -- Chemistry

Li

Outline
O C R Al H H R R C R O

WWU -- Chemistry

Lithium Aluminum Hydride Reduction of Aldehydes and Ketones


O LiAlH4 + 4 R C R H R C R 4 O Al Li
+

R H C R 4 O Al Li
+

O + 4 H2O 4 R C H

H R + Al(OH)3

LiOH

These reactions typically go in very high yield.


WWU -- Chemistry

Learn it this way:

O LiAlH4 C R R R

O H2O C H R R

OH C H R

WWU -- Chemistry

Aluminum is required to coordinate with the oxygen of the carbonyl group. For example, in the absence of aluminum (using sodium hydride, NaH as the reducing agent), there is no reduction.

WWU -- Chemistry

You Must Be Careful!

LiAlH4 + 4 H 2O

LiOH + Al(OH) + 4 H2 3

WWU -- Chemistry

A similar, but less reactive, reducing agent is sodium borohydride, NaBH4.


H H B H H Na

WWU -- Chemistry

Sodium Borohydride Reduction of Aldehydes and Ketones

O C R R NaBH4 R

O Na C H

O H H2O R C H R

WWU -- Chemistry

Example
H O NaBH4 or LiAlH4 H2O OH

In general, the reduction should proceed equally easily from either side, yielding two mirror-image products.

WWU -- Chemistry

Sodium Borohydride Reduction of Camphor


H3C CH3 H3C 1) NaBH4 2) H2O H3C O Camphor H3C OH Borneol (15%) (endo) H H3C H Isoborneol (85%) CH3 H3C CH3

+ OH

(exo)

In this case, approach by borohydride from the upper side is sterically hindered by the bridge methyl group. The result is a predominance of exo alcohol.
WWU -- Chemistry

Sodium Borohydride Reduction of Norcamphor


1) NaBH4 2) H2O O Bicyclo[2.2.1}heptan-2-one (Norcamphor) OH endo alcohol (86%) H H exo alcohol (14%) + OH

Here, it is the underside of the molecule that is more sterically hindered, so the favored alcohol is the endo alcohol. Similar results are obtained with lithium aluminum hydride.
WWU -- Chemistry

Another example:

O C H LiAlH4 or NaBH4 CH2 OH

WWU -- Chemistry

Contrast these two reactions


O C CH3 CH2 CH2 C O O C CH3 CH2 CH2 C O O CH2 CH3 1) NaBH4 2) H2O CH3 OH CH CH2 CH2 C O O CH2 CH3 O CH2 CH3 1) LiAlH4 2) H2O CH3 OH CH CH2 CH2 CH2 OH

Note that sodium borohydride is more selective.


WWU -- Chemistry

Catalytic Hydrogenation of Aldehydes and Ketones


O C R R + H2 (1000 psi) Ni 50 H R O C H R

WWU -- Chemistry

Reduction of a Carbonyl Group to a Methylene Group

WWU -- Chemistry

We are trying to accomplish...


O C CH2

WWU -- Chemistry

Clemmensen Reduction
O Zn(Hg) R C R HCl (conc.) H R C R H

Zn(Hg) is a zinc amalgam


WWU -- Chemistry

The mechanism of the Clemmensen reduction involves the formation of some sort of zincketone complex. This reaction is a good method for the reduction of acid-stable carbonyl compounds (Note that the reaction takes place in the presence of concentrated HCl).

WWU -- Chemistry

Example of a Clemmensen Reduction


O C O CH 2 CH 2 C OH Zn(Hg) conc. HCl heat 90% yield O CH 2 CH 2 CH 2 C OH

Notice that the reduction does not affect the carboxyl group
WWU -- Chemistry

Wolff-Kishner Reduction
O KOH R C R + H2N NH2
H O CH 2 CH 2 OH

H R 190 - 200 C + C H N2 + H2O R

WWU -- Chemistry

The mechanism involves the formation of a hydrazine adduct, which loses water to form a hydrazone. The hydrazone then rearranges to lose a molecule of nitrogen gas, leaving behind a carbanion. The carbanion picks up a proton from the solvent to form the product.

WWU -- Chemistry

This will never show up on any of my exams!


O H 2N C R R acid NH NH2 NH2 NH2 R C R N OH - H2O R C R

rearrange

H H H2O R C H N R R C + N R H R C N N R

WWU -- Chemistry

The Wolff-Kishner reduction is useful for the reduction of carbonyl compounds that are stable in strong base. (Note that the reaction takes place in the presence of concentrated KOH or other base)

WWU -- Chemistry

Example
O H2N O N H Isatin NaOCH2CH3 CH3CH2OH N H NH2 O N NH2

O N H 75% yield

WWU -- Chemistry

Desulfurization
O C R R + CH2 CH2

HS CH2 CH2 SH

BF3 diethyl ether

S C R

S R

H2 O

CH2 CH2 S C R R S +

H2

Raney Ni

H C R +

H + R 2 NiS CH3 CH3

WWU -- Chemistry

Advantages: High yields Mild and nearly neutral reaction conditions

Disadvantages: Stinky! Raney Nickel is tricky to prepare

WWU -- Chemistry

Example of a Raney Nickel Desulfurization


CH2 HS CH2 S O BF3 ether S H2 Raney Ni SH

WWU -- Chemistry

WWU -- Chemistry

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