[go: up one dir, main page]
Scribd
Upload
66 views9 pages

Lecture 12 (Heteroatom Addition) : Reactivity of Carbonyl Compounds

The document summarizes reactivity and addition reactions of carbonyl compounds. It discusses 1,2-addition of nucleophiles to the carbonyl carbon. Specifically, it covers addition of O-, S-, and N-nucleophiles and the mechanisms and products of these reactions like hydrates, hemiacetals, acetals, bisulfite adducts, imines, and enamines. Steric effects and the role of acids or bases in catalyzing the reactions is also addressed.

Uploaded by

Allalann
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as DOCX, PDF, TXT or read online on Scribd
66 views9 pages

Lecture 12 (Heteroatom Addition) : Reactivity of Carbonyl Compounds

The document summarizes reactivity and addition reactions of carbonyl compounds. It discusses 1,2-addition of nucleophiles to the carbonyl carbon. Specifically, it covers addition of O-, S-, and N-nucleophiles and the mechanisms and products of these reactions like hydrates, hemiacetals, acetals, bisulfite adducts, imines, and enamines. Steric effects and the role of acids or bases in catalyzing the reactions is also addressed.

Uploaded by

Allalann
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as DOCX, PDF, TXT or read online on Scribd
You are on page 1/ 9

Lecture 12 (Heteroatom addition)

Reactivity of Carbonyl Compounds


Properties
Sp2 hybridized Binding angle at the C-atom
is 120
Oxygen is strongly electronegative
Polarization
C-atom is positively polarized
O-atom react as nucleophile C atom react
as electrophile

Reactivity

Enols / enolates chapter 16

1,2-addition - Nucleophile attacks C-atom and form negative charge O-


atom

Negative charge atoms are then attacked by electrophile

Rule

1) assign polarities

2) - React with + ( Nuc- react with E+ )

3) Look at product if it can further react? (yes) intermediate > further reaction

Lecture 12 ( Heteroatom addition ) 1


Addition and Acyl Substitution reaction

Steric Effect

With increase in hindrance the rate of reaction decreases

Because of enhance in electrophilicity of carbonyl group thus more


reactive

Lecture 12 ( Heteroatom addition ) 2


1,2 Addition Mechanism

Activated nucleophile by deprotonation or activation of electrophile by


addition of acids

Addition of O-Nucleophiles to carbonyl group ( Weak Nucleophiles ) A)


Hydrazination ( H2O Addition )

Hydrate are not stable upon


isolation

Lecture 12 ( Heteroatom addition ) 3


B) Hemi acetal Formation ( Alcohol-Addition )

Acid catalyzed Favor carbonyl as hemiacetals are not stable upon isolation

Erlenmeyer Rule
Compound with two or more electron negative group
at the same carbon atom are not stable thus

Intra-Molecule elimination

Two OH bond side by side will be


least favoured thus turns into an O double bond

Exception of case are I/M effect and Cyclic


compounds (resonance stabilized )

C) Acetal Formation (2 x Alcohol- Addition)

Lecture 12 ( Heteroatom addition ) 4


Full working

Removal of H20 pushes the equilibrium to product(acetal) Acetal are stabile


Hemi acetal are not stabilize
EXAMPLE
Formation of Cyclic

Formation of protecting Group

Lecture 12 ( Heteroatom addition ) 5


D) Alternative Formation (Catalyst and 1 x Alcohol- Addition )

No H2O is required here

Addition of S-Nucleophiles to carbonyl group ( Weak


Nucleophiles )
Formation of Bisulfite Adducts ( 1,2 addition )
Sulfur is more nucleophilic than
sulfur

EXAMPLE Cyclic dithioacetals

Addition of N-Nucleophiles to carbonyl group (


Weak Nucleophiles)
1,2 Addition of S-Nucleophiles

Lecture 12 ( Heteroatom addition ) 6


Full Working

Special Imines from N Hetero amines

All follow same reaction of Acetal

Example Hydroxy / amine

Lecture 12 ( Heteroatom addition ) 7


Example Hydrazine

Secondary Amines and Carbonyl ( GENRATION OF ENAMINE )

Lecture 12 ( Heteroatom addition ) 8


Example

Thermodynamic reaction control: Most Stable

Lecture 12 ( Heteroatom addition ) 9

You might also like