Curs VI

Influenta
grupelor
functionale
biocompatibilitatii. Notiuni introductive (V)

asupra

mbuntirea i implementarea de programe universitare de master n domeniul Chimiei Aplicate i tiinei Materialelor ChimMaster
POSDRU/156/1.2/G/135764

Tautomeria Enol-Cetona

The a-Hydrogen Is Acidic

the anion is stabilized

by resonance

A carbon acid is a compound with a relatively acidic

hydrogen bonded to an sp3-hybridized carbon

An Enol Is a Better Nucleophile

Than an Alkene

Carbonyl compounds that form enol undergo substitution

reactions at the a-carbon: an a-substitution reaction

An Acid-Catalyzed
a-Substitution Reaction

A Base-Catalyzed
a-Substitution Reaction

An Enolate Is an Ambident Nucleophile

Reaction at the C or O site depends on the electrophile

and on the reaction condition

Protonation occurs preferentially on the O site

Otherwise, the C site is likely the nucleophile

Conversion of a Methyl Ketone to a

Carboxylic Acid

Reactia de eliminare
Addition and elimination reactions are exactly opposite. A bond is formed in
elimination reactions, whereas a bond is broken in addition reactions.

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Reactia de eliminare

In an elimination reaction, two groups X and Y are removed from a

starting material.
Two bonds are broken, and a bond is formed between
adjacent atoms.
The most common examples of elimination occur when X = H and
Y is a heteroatom more electronegative than carbon.
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Reactia de eliminare

Exercitii propuse:
Determinai pentru urmtoarele structuri, caracterul nucleofil sau electrofil,
pentru atomii marcai:

Exercitii propuse:

Reactiile de oxidare si reducere

Commonly Termed REDOX Reactions

From General Chemistry, we Will Recall

Oxidation: Loss of Electrons
Reduction: Gain of Electrons
Organic Chemists will Typically use Different Definitions
Reduction: Increase Hydrogen Content (Decrease Oxygen)
Oxidation: Decrease Hydrogen Content (Increase Oxygen)
Oxidizing/Reducing Agents: Usually Inorganic Compounds (M+)

Some common reducing agents

Some common oxidizing agents

Reactiile de oxidare si reducere

Oxidation results in an increase in the number of bonds

between C and a more electronegative atom, CZ, (usually
CO) or decrease in the number of CH bonds.
Reduction results in a decrease in the number of CZ bonds
(usually CO) or an increase in the number of
CH bonds.
Figure 12.1 A general scheme for the oxidation and reduction of a carbon compound

Introduction:
Two carbon atoms may be involved in a single oxidation or
reduction reaction.
The conversion of an alkyne to an alkene, or an alkene to an
alkane are examples of this type reduction because each
process adds two new CH bonds to the starting material.

Figure 12.2 Oxidation

and reduction of
hydrocarbons

Reducing Agents:
There are three ways of introducing 2 Hs in a reduction.
1. The first method uses H2 gas. Catalytic hydrogenation requires a metal
catalyst (usually Pt, Pd or Ni) with H2.
2. A second method adds two protons and two electrons to a substrate, and 2H+
+ 2e- = H2
Reductions of this sort use alkali metals as a source of electrons, and liquid
ammonia as a source of protons, Nao in NH3 (liq) or Lio in NH3 (liq).
These are called dissolving metal reductions.

Reducing Agents:
3. The third way is to add hydride (H) and a proton (H+).
The most common hydride reducing agents contain a hydrogen atom
bonded to boron or aluminum. Simple examples include sodium
borohydride (NaBH4) and lithium aluminum hydride (LiAlH4).
NaBH4 and LiAlH4 deliver H to the substrate, and then a proton is added
from H2O or an alcohol.

Reduction of Alkenes: Catalytic Hydrogenation

The addition of H2 occurs only in the presence of a metal catalyst,

and thus it is called catalytic hydrogenation.
The catalyst consists of a metal, usually Pd, Pt, or Ni, adsorbed
onto a finely divided inert solid, such as charcoal.
H2 adds in a syn fashion.

Oxidation and Reduction

Reduction of Alkenes: Catalytic Hydrogenation

Alkyne reduction to a Trans Alkene:

Reduction of Polar CX Bonds:

Alkyl halides can be reduced to alkanes with LiAlH4.
Epoxide rings can be opened with LiAlH4 to form alcohols.

Figure 12.6 Examples

of reduction of C X
bonds with LiAIH4

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Reduction of Polar CX Bonds:

This reaction follows an SN2 mechanism.

Unhindered CH3X and 1 alkyl halides are more easily reduced
than more substituted 2 and 3 halides.
In unsymmetrical epoxides, nucleophilic attack of H (from LiAlH4)
occurs at the less substituted carbon atom.

Oxidizing Agents:

There are two main categories of oxidizing agents:

1. Reagents that contain an oxygen-oxygen bond
2. Reagents that contain metal-oxygen bonds

Oxidizing agents containing an OO bond include O2, O3

(ozone), H2O2 (hydrogen peroxide), (CH3)COOH (tert-butyl
hydroperoxide), and peroxyacids.
Peroxyacids (or peracids) have the general formula
RCO3H.

Figure 12.7
Common
peroxyacids
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Oxidizing Agents:

The most common oxidizing agents with metal-oxygen bonds

contain either chromium +6 (six CrO bonds) or manganese +7
(seven MnO bonds).
Common Cr6+ reagents include CrO3 and sodium or potassium
dichromate (Na2Cr2O7 and K2Cr2O7). Pyridinium chlorochromate
(PCC) is a more selective Cr6+ oxidant.

The most common Mn7+ reagent is KMnO4 (potassium

permanganate).
Other oxidizing agents that contain metals include OsO4 (osmium
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tetroxide) and Ag2O [silver(I) oxide].

Oxidizing Agents:
Figure 12.8 Oxidation reactions of alkenes, alkynes, and alcohols