Hetero cyclic Analogues of Naphthalene with one heteroatom
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
N
Quinoline
N isoquinoline
N
+
Quinolizinium
(1) (2) (3) lec
9 1

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 .
+
O O O
Benzopyrylium 2H -Benzopyrylium
4H -Benzopyrylium
(4) (5) (6) lec
9 2

Quinoline is a colourless liquid its b.p 237 cº 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 .
CHO
NH
2
+
|
CH
3
CHO
- amino benzaldehyde 2
NaOH
O
3
) 1 (
N
O 3
H 2 O 2 or KMnO 4
HOOC
HOOC
) 2 (
N
N
O
3 diozonide
OHC
CHO
|
CHO
+
OHC
N pyridine 2,3
- dicarbaldehyde glyoxal lec
9 3

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
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 .
6
7
5
8
4
3
N 2
1 lec
9 4

Quinoline is a slightly weaker base than pyridine and form many salt which sparingly soluble in water .
N
N lec
9 5

Addition and ring – opening reactions :
Quinoline is a colourless liquid , it form 1 – oxide with hydrogen peroxide and acetic acid and quaternary
H2O2 / ACOH
N
+
N
O
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) .
lec
9 6

N
MeI
(1)
+
N
Me
I
-
Na+ OH-
HI
+
N
Me
(2)
OH
-
[O]
NH
Me
(4)
O
N
(5)
O
H+ OH-
H
N
OH
H
Me
OH
(3)
-
N
Me
H
+
OH lec
9 7

Na/Hg
+
N
Me
2
OH
-
Emde's methods
160
15 mm ordinary pressure
N
Me
2
3 - phenyl - N - dimethyl-
Propane amine
H
N
Me
2
O H
H
H
-H 2 O
N
Me
2
O - propene - N - dimethylaniline
N
Me
+ MeOH lec
9 8

Quinoline is easily reduced to tetrahydroquinoline by tin and hydrochloric acid or by hydrogenation .
N tin / HCl
H2O
N
H
1,2,3,4-tetrahydroquinoline lec
9 9

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
HOOC
HOOC
N
(1)
COOH
N
KMnO4
Ph N
NHCOPh
(2)
COOH
H
OH
KMnO4
N
R
(3)
N
N - alkyl - 2 hydroxy quinoline lec
9
NCHO
R
10

OH
KMnO4
N
Ph
OH
COOH
N - C - Ph
H O
-CO2
OH
N
H
N=C - Ph
OH
(enol form )
CH
3
N - C - Ph
H O
[O]
H H
N
C = O
H
N - C - Ph
H O
( keto form )
[O]
COOH
N - C - Ph
H O lec
9 11

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 .
lec
9 12

Quinoline resonance hybrid indicate the same result for electrophilic and nucleophilic substituent .
..
N
..
N
..
N
-
+
+
..
N
+
..
N
lec
9 13

NO
2 fuming HNO3 fuming H2SO4 N
N
N
+
NO
2
N fuming H2SO4
5 - nitroquinoline 8 - nitroquinoline
SO
3
H
+
220 c0 N
SO
3
H
N quinoline - 5sulphonic acid
Br quinoline - 8sulphonic acid
N
Br2
H2SO4
AgSO4
N
5 - bromoquinoline
+
N
Br
8 - bromoquinoline
Br2
CCl4 / pyridine
N
3 - bromoquinoline
Br
14

N
NaNH2
lig NH3
KOH
220 c
0
NH
2
N
+
N OH
+
N NH
2
2 - aminoquinoline
OH
N
4 - hydroxyquinoline lec
9 15

1 – Skraup's synthesis
It is the most useful method for preparing quinoline from aniline and glycerol in presence of concentrated sulphuric and nitrobenzene .
NH
2
+
|
CH2OH
|
CH - OH
CH2OH
H2SO4
C6H5NO2
N
+ C6H5NH2 + H2O lec
9 16

The following steps seem to be involved
1 – Dehydration of glycerol by hot sulphuric yield the unsaturated aldehyde acroline .
CH2 - CH - CH2
| | |
OH OH OH
H2SO4
-2H2O
CH2
||
CH
|
|
C = O
H
+
|
CH2
|
CH
C - O -
|
H lec
9 17

2 – Nucleophilic addition of aniline to acrolein to yield β –
(phenylamino) – propionaldehyde .
NH
+
O
H
C
CH
||
CH
2
H
O
H
C
CH
2
CH
2
N
H
β ( phenylamino) propionaldehyde lec
9 18

3 – Electrophilic attacke on the aromatic ring by the electron deficient carbonyl carbon of the protonated aldehyde .
H
O
C
CH
2
CH
2
N
H
H OH
H
N
H
H+
H
+
C
H
OH
CH
2
CH
2
N
H
-H2O
N
H
1,2 - dihydroquinoline lec
9 19

4 – Oxidation by nitrobenzene resulting in the aromatization of the new formed ring
N
H
+ C6H5NO2
H+
N
+ C6H5NH2 + H2O lec
9 20