Unless otherwise stated, all images in this file have been reproduced from:
Blackman, Bottle, Schmid, Mocerino and Wille,
Chemistry, 2012 (John Wiley & Sons)
ISBN: 9 78047081 0866
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Aldehydes and ketones
Lecture 10 Lecture 11 Lecture 12
Acid-base properties Grignard reagents More oxidation &
Addition reduction
Elimination Nucleophilic acyl
substitution
Oxidation & reduction
Recap: How do carbonyls react?
The carbon in a carbonyl group is a good electrophile
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Recap: Hydride addition to C=O
Hydride (H-) adds to the electrophilic carbon atom of the C=O group. The charged
oxygen in the intermediate product, the alkoxide, picks up something in the reaction
to give a neutral product. Most often this is a proton from water, when we “work-up”
the reaction to isolate the organic product.
H H
H
This means we have performed an addition (of H-H) across the C=O.
The thing that reacted with the carbonyl group was a nucleophile, so this is a
Nucleophilic Addition 4
More useful: addition of carbon-based nucleophiles
Imagine instead of hydride, H–, we could add
nucleophiles based on carbon
We could build up complex molecules by making the
carbon framework of molecules bigger
Worksheet – Q1 5
Taming the beast: Grignard reagents
Carbanions can be handled in the lab if the electron-rich carbon can
bond a little to an electropositive atom, like a metal.
One that works well is magnesium (which is itself bonded to a
halogen, like bromine)
These are known as Grignard Reagents
Worksheet – Q2, Q3 6
Making Grignard reagents
One of the most useful features of Grignard reagents is that they may
be made from organohalides and magnesium metal
“isopropylmagnesium bromide”
“cyclopentylmagnesium iodide”
“phenylmagnesium chloride”
We won’t ask you to name Grignard reagents, but there are rules and they are logical
Notice that the bond from carbon in the Grignard reagent is always
to the metal, not the halogen atom. You don’t need to know the
mechanism of Grignard reagent formation.
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Worksheet – Q4, Q5, Q6
A little history while you work
Nobel Prize in 1912 …for metal-catalysed
Shared with: hydrogenation (see
Addition lecture)
Victor Grignard Paul Sabatier
1871–1935 1854–1941
Grignard reagents are one part of organometallic chemistry. It’s
possible to make carbon nucleophilic with other metals, too, such as
zinc, copper or lithium (next year…)
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A note about what’s coming next
Aldehydes and ketones will react in a
certain way
That will be different to carboxylic acids
And different to esters
And different to amides
(that’s why we call these functional groups
different things! See video for more.) 9
Learning outcomes
After this lecture you should be able to:
• Describe how to synthesise Grignard reagents
• Draw mechanisms for the nucleophilic addition of Grignard reagents to
carbonyl-containing molecules
• Appreciate the usefulness of carbon-based nucleophiles in the synthesis of
complex molecules
Further reading: Blackman 21.1-21.5
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