BASIC ORGANIC CHEMISTRY SKO 3013 Dr.

SARIPAH SALBIAH SYED ABDUL AZIZ

MOHD AIDIL UBAIDILLAH B RAZILAN D20091035132 MOHAMAD ARIF BIN NASARUDDIN D20091035123

Nucleophilic Addition

Hemiacetal and Acetal Formation

Baeyer-Villiger oxidation

Ketones Reaction

The Reduction of a Ketone

Formation of Cyanohydrin

Formation of Imine

R C R O + H

Nu

Nu

C
R

OH

Nucleophilic Addition to the Carbon- Oxygen Double bond

C R

:Nu

C
R

The arrangement of group around the carbonyl carbon atom is relatively open to attack from above and below the plane of carbonyl group. The positive charge on the carbonyl group mean susceptible to attack by nucleophilic The negative charge on the carbonyl oxygen mean that nucleophilic addition is susceptible to acid catalysis. Nucleophilic addition to the carbon-oxygen doube bond occurs, therefore, in either of two generals ways.

Nu
+ _

O:

First Way

 When the reagent is strong nucleophile (Nu:- ), addition usually takes place in the following way, converting the trigonal planar ketone into tetrahedral product * Important aspect of this step is the

C R

O + :Nu

In this type of addition the nucleophile uses its electron pair to form a bond to the carbonyl carbon atom As this happen the electron pair of the carbon oxygen bond shift out to electronegative carbonyl oxygen atom and the hybridization change from sp2 to sp3 In the second step the oxygen atom accepts a proton. This happen because the oxygen atom is now much more basic; it carries a full negative charge as an alkoxide anion

R C R

: O: :

Nu
+ -

ability of the carbonyl oxygen atom to accommodate the electron pair of the carbon- oxygen double bond

H
Nu : R C R O

Nu
-

H + :Nu

Second Way

A second general mechanism that operate in nucleophilic addition to carbon- oxygen double bond is an by acid- catalyzed mechanism

STEP 1

R R

O + H

In this step an electron pair of the carbonyl oxygen accept a proton from an acid, producing an oxonium cation. The carbon of the oxonium cation is more susceptible to nucleophilic attack than the carbonyl of the starting ketone

R R

OH +

..

R R

C +

.. OH ..

+ A:-

STEP 2
+

H Nu R C R A::Nu : R C R O
..

C
R

OH +

:Nu

: O
: A

In the first of those two step, the oxonium cation accepts the electron pair of the nucleophile. In the second step, a base removes a proton from positively charged atom, regenerating the acid.

H + H

NOTE!!!
This mechanism operate when carbonyl compound are treated with strong acid in the presence of weak nucleophiles. In the first step the acid donates a proton to an electron pair of the carbonyl oxygen atom. The resulting protonated carbonyl compound an oxonium cation, is highly reactive toward nucleophilic attack at the carbonyl carbon atom because the carbonyl carbon atom carries more positive charge than it does in the unprotonated compound.

Hemiacetal Formation and Acetal Formation

R2C=O + R'OH
R2C=O + 2 R'OH

R'O(R2)COH (a hemiacetal)
R2C(OR')2 + H2O (an acetal)

Formation of Imines

R2C=O

R'NH2

R2C=NR' + H2O

Cyanohydrin Formation
RCH=O + HCN RCH(OH)CN

Organometallic Addition Reaction

Halogenation of Ketones

In the presence of a base, ketones with hydrogens react to form haloketones.

Iodoform Test

When methyl ketones react with iodine in the presence of a base, complete halogenation occurs.

The generation of sodium hypoiodate in solution from the reaction of iodine with sodium hydroxide leads to the formation of iodoform and sodium benzoate

The Reduction of a Ketone

or

Reduction of a ketone leads to a secondary alcohol

Using lithium tetrahydridoaluminate (lithium aluminium hydride)

In the first stage, a salt is formed containing a complex aluminium ion.

The product is then treated with a dilute acid (such as dilute sulphuric acid or dilute hydrochloric acid) to release the alcohol from the complex ion.

Using sodium tetrahydridoborate (sodium borohydride)

Solid sodium tetrahydridoborate is added to a solution of the aldehyde or ketone in an alcohol such as methanol, ethanol or propan-2-ol.

In the second stage of the reaction, water is added and the mixture is boiled to release the alcohol from the complex.

Baeyer-Villiger Oxidation

It is Ketone oxidation, and it requires the extremely strong oxidizing agent peroxybenzoic acid. For example, peroxybenzoic acid oxidizes phenyl methyl ketone to phenyl acetate (an ester).