Heterocyclic Chemistry (Compounds)

Prof.Dr.Tareq Al-Hakeem,
Dr>. Alaa Alnoori Lec.1
These compounds contain at least one atom apart of the ring
other than carbon.

Furan Thiophene Pyrrole Pyridine

Oxazole Trimethyl oxide (Oxetane)

Benzene is homocyclic, all six carbons are

the same. Aroma c heterocyclic compounds apply the rule
4n+2 = π electrons, and behave similar to benzene in their
proper es. They include almost all the drugs and
pharmaceu cals, vitamins B1, B2, B6, Vit. C, nucleic acids, some
amino acids and hemoglobin.

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 Penicillin

Histamine Nico ne amide

Vit. B6 Vit. C
The ring maybe a 3 atom ring, 4, 5 or 6 atom ring,…, maybe
saturated or unsaturated.
Saturated 3 Atom Ring

Azidrine Oxirane Thiirane

(Azidirine)

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 Unsaturated

Azirine Oxirene Thiirene

4 Atoms

Aze dine Oxetane Thietane

Azete Oxete Thiete

Three Membered Ring

Oxiranes (epoxides) are the most common.

They are easily prepared by reac on of alkenes with peracids.

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 Benzoic acids , O benzoic acid, m-chloro per benzoic acid
(MCPBA)

Examples

+ MCPBA
+

Ethylene Oxirane

+ Cl-C6H5COOOH
Cyclopentene

Cyclopentene oxide

Problem: Prepare propylene oxide

CH3CH=CH2 +

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 CH3-CH CH2 +
O

Mechanism of reac on (Peroxida on)

+ +

The rate of peroxida on of alkenes increasing with increasing

electron density of π- electrons. I.e. with increasing electron
dona ng groups.
Compound Rate
CH2=CH2 1
R-CH=CH2 24
R-CH=CH-R 500
*R is electron-dona ng group.
Epoxide Opening
1. Symmetrical Epoxides
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The two carbons are symmetrical, i.e. they are equivalent.

The nucleophilic a ack occurs randomly:

- + H+ 2 1

C2H5OH + H2O
CH2 CH2
C2H5O OH

H2O 2 1

HBr + CH2 CH2

Br OH

H+
CH2 CH2
H2O
OH OH
2. Unsymmetrical Epoxides
The two carbons are not iden cal, such as branched
epoxides:

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 A. In acidic medium, a ack takes place at the most
subs tuted carbon due to charge e ect and called C2
a ack.
CH3 _ +
2 3

CH3 C CH2 + CH3OH

O
1

H2O

CH3
2 1

CH3 C CH2
OCH3 OH

B. In basic medium, the nucleophilic a ack takes place at

the less hindered carbon atom and called C3 a ack due
to steric e ect or space e ect :
CH3 3
_ +
2

CH3 C CH2 + CH3OH

O
1

CH3O- is the nucleophilic group

H2O OH-

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 CH3
3

CH3 C CH2 OCH3

OH

Problem 1- Prepare epoxides from alipha c and cyclic alcohols.

-H2O

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 a. CH3CH2CH2CH-CH3 CH3CH2CH2CH=CH2
Dehydra on
OH
2-Pentanol (Alipha c) 1-pentene

O
pentyl epoxide CH3-CH2CH2CH-CH2 +

Br

-H2O

b.

cyclohexanol cyclohexene
(cyclic)

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 +
cyclohexane epoxide

Problem 2- How you can convert epoxide to diol?

H+
H2O CH2-CH2
OH OH
epoxide diol
i.e. Ring opening
Problem 3- How unsymmetrical epoxides undergo C2- a ack?
In acidic medium and due to charge e ect.

Regards
Prof.Dr. Tareq Al-Hakeem
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