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Hetero cyclic Analogues of Naphthalene with one heteroatom

(1) (2) (3)

N

Quinoline isoquinoline

N N+

Quinolizinium

The most investigated compound of this group contain a nitrogen atom , and theoretically can be drived from naphthalene by the substation of carbon or carbon and hydrogen atoms by a nitrogen atom .The same result can be obtained by fusing a benzene on to that of pyridine and three structure result .Derivative of all three ring system 1 , 2 , 3 occure naturally in the form of alkaloide

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(4) (5) (6)

O

Benzopyrylium

+

2H -Benzopyrylium

O O

4H -Benzopyrylium

These three type of compound are essentially aromatic in character .The oxygen analogues of naphthalene which will be considered here are those

derived from benzopyrylium cation (4) and benzopyranes (5) and (6) derivatives of these systems occure widely in plants and the

anthocyanins. subistituted benzopyrylium salt are responsible for most red and blue flower coloure .very few sulphur analogues are known and at

present they are not of general interest .

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Physical properties and structure

CHO

NH2

+ |CHO

CH3 NaOH

N

H2O2

NHOOC

HOOC

or KMnO4

)1( )2(

O3

N

3

O3

O

|CHO

CHO

NOHC

OHC

+

diozonide glyoxal pyridine 2,3 - dicarbaldehyde

2 - amino benzaldehyde

Quinoline is a colourless liquid its b.p 237cº it's miscible with most organic solvent ,its useful high – boiling solvent for many types of organic compound .The structure for quinoline was first proposed by korner ,and was supported at an early stage by an oxidation to

quinolinic acid (2) and by several syntheses of which Friedlander's is shown .

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ozone attacke quinoline at the 5,6 and 7,8 position the initial product is a diozonide , decomposition of diozonide give pyridine 2,3 – dicarbaldehyde and glyoxal

1

345

6

78

N 2

The resonance energy of quinoline (47.3) kcal/ mol calculated from heat of combustion data the position of quinoline ring are

usually numbered as structure .

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Chemical reaction

1 – basicity Quinoline is a slightly weaker base than pyridine and form many salt which sparingly soluble in water .

N N

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Quinoline is a colourless liquid , it form 1 – oxide with hydrogen peroxide and acetic acid and quaternary

salt with methyl iodide which with alkali give the hydroxide these are in equilibrium with the corresponding bases (3) which can be

tautomerize to an open – chain (4) the oxidation of (3)give (5) .

Addition and ring – opening reactions :

H2O2 / ACOH

N NO

+

-

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N

MeI

N+ I-

Me(1)

Na+ OH-

HIMe

+N

(2)

OH-

(3)(5)

N

H

OHMe

+-[O]

N O

H+ OH-

N

H

OHH

MeOH

(4)

ONHMe

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NMe

2

+ OH-Na/Hg

Emde's

methodsNMe

2

3 - phenyl - N - dimethyl-

Propane amine

N

O H

H

H

H

Me2

-H 2 O

Me2

N

Me

N

+MeOH

O - propene - N - dimethylaniline

160

15 mm

ordinary

pressure

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Reduction :

1,2,3,4-tetrahydroquinoline

N

tin / HCl

NH

H2O

Quinoline is easily reduced to tetrahydroquinoline by tin and hydrochloric acid or by hydrogenation .

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Oxidation :

Oxidation of quinoline opens the ring giving quinolinic acid (1) the 2 – phenyl quinoline (2) and hydroxide (3) the nitrogen – containing ring can be split

N

KMnO4

N

HOOC

HOOC

(1)

(2)

N

COOH

NHCOPh

KMnO4

N Ph

N OH

H

R

KMnO4

N

COOH

NCHOR

(3)

N - alkyl - 2 hydroxy quinoline

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N N=C - Ph

OH

H

OH

KMnO4

N Ph

OH

OHN N - C - Ph

C = O

O

H H

H

H

[O]

COOH

N - C - PhH O

-CO2CH3

N - C - PhH O

[O]COOH

N - C - PhH O

(enol form ) ( keto form )

Mechanism

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Substitution reaction

The nitrogen atom deactivates the pyridine ring and so the subistituent enter the benzene ring .calculation of charge densities show that position 8 will be attack by electrophilic reagent and position -2- by nucleophilic reagents .In practice nitration and sulphonation give a mixture of – 5 and 8 – substituted product . In bromination the heterocyclic rings is subistituted in the 3 – position .

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N..

+

-

+

N....

N-

N..

N..

+

Quinoline resonance hybrid indicate the same result for electrophilic and nucleophilic substituent .

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N

fuming HNO 3

fuming H 2SO4N

NO2

NNO2

+

5 - nitroquinoline 8 - nitroquinoline

N 220 c0

fuming H 2SO4

quinoline - 8-sulphonic acid

quinoline - 5-sulphonic acid

+N

SO3HN

SO3H

Electrophilic subistitution

NAgSO4

Br2 H2SO4

5 - bromo-quinoline

+N

Br N

Br

8 - bromo-quinoline

Br2 CCl4 /pyridine N

Br

3 - bromo-quinoline

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N

NaNH2 lig NH 3 +

N NH2N

NH2

2 - amino-quinoline

KOH 220 c0 4 - hydroxy-

quinoline N

OH

N OH +

Nucleophilic subistitution

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Synthesis of quinoline

1 – Skraup's synthesis

H2SO4 C6H5NO2

NNH2

+

CH2OH|CH - OH|CH2OH

+ C6H5NH2 + H2O

It is the most useful method for preparing quinoline from aniline and glycerol in presence of concentrated sulphuric and nitrobenzene .

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The following steps seem to be involved

CH2 - CH - CH2 | | |OH OH OH

H2SO4 -2H2O

CH2 ||CH |C = O |H

CH2 |CH |C - O - |H

+

1 – Dehydration of glycerol by hot sulphuric yield the unsaturated aldehyde acroline .

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NH

H

+H

C

O

CH ||CH2 N

CH2

H

CH2

C

O

H

β ( phenylamino) propionaldehyde

2 – Nucleophilic addition of aniline to acrolein to yield β – (phenylamino) – propionaldehyde .

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NCH2

H

CH2

C

O

HH+

NCH2

H

H

CH2

C

OHH+

NH

OHHH

-H2O

NH

1,2 - dihydroquinoline

3 – Electrophilic attacke on the aromatic ring by the electron deficient carbonyl carbon of the protonated aldehyde .

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NH

+ C6H5NO2H+

N+ C6H5NH2 + H2O

4 – Oxidation by nitrobenzene resulting in the aromatization of the new formed ring