Chemistry of Heterocyclic Compounds. Volume 32. Quinolines. Part I

905 Pages·1935·49.81 MB·english

by  Jones G.

QUINOLINES
Part I
This is the thirty-second volume in the series
THE CHEMISTRY OF HETEROCYCLIC COMPOUNDS
THE CHEMISTRY OF HETEROCYCLIC COMPOUNDS
A SERIES OF MONOGRAPHS
ARNOLD WEISSBERGER and EDWARD C. TAYLOR
Editors
Q U I N O L I N E S
Part
I
Edited by
Gurnos Jones
DEPARTMENT OF CHEMISTRY
UNIVERSITY OF KEELE
STAFFORDSHIRE
AN INTERSCIENCE@ PUBLICATION
JOHN WILEY & SONS
LONDON NEW YORK SYDNEY TORONTO
An Interscience@ Publication
Copyright @ 1977, by John Wiley & Sons, Inc.
All rights reserved.
No part of this book may be reproduced by any means, nor
transmitted, nor translated into a machine language without
the written permission of the publisher.
Library of Congress Cataloging in Publication Data:
Main entry under title:
Quinolines.
(The Chemistry of heterocyclic compounds; V. 32)
‘An Interscience publication.’
Includes index.
1. Quinoline. I. Jones, Gurnos.
QD401.Q56 547’.596 76-26941
ISBN 0 471 99437 5
The Chemistry of Heterocyclic Compounds
The chemistry of heterocyclic compounds is one of the most complexes branches
of organic chemistry. It is equally interesting for its theoretical implications, for
the diversity of its synthetic procedures, and for the physiological and industrial
significance of heterocyclic compounds.
A field of such importance and intrinsic difficulty should be made as readily
accessible as possible, and the lack of a modern detailed and comprehensive
presentation of heterocyclic chemistry is therefore keenly felt. It is the intention of
the present series to fill this gap by expert presentations of the various branches of
heterocyclic chemistry. The subdivisions have been designed to cover the field in
its entirety by monographs which reflect the importance and the interrelations of
the various compounds, and accommodate the specific interests of the authors.
In order to continue to make heterocyclic chemistry as readily accessible as
possible new editions are planned for those areas where the respective volumes in
the first edition have become obsolete by overwhelming progress. If, however, the
changes are not too great so that the first editions can be brought up-to-date by
supplementary volumes, supplements to the respective volumes will be published
in the first edition.
ARNOLDW EISSBERGER
Research Laboratories
Eastman Kodak Company
Rochester, New York
EDWARDC. TAYLOR
Princeton University
Princeton, New Jersey
V
Preface
In the first Part of the volume dealing with the chemistry of quinolines we have
tried to cover, in as comprehensive a manner as is possible, the properties of
quinoline itself and of the haloquinolines, and to survey the ways in which the
quinoline ring system can be formed. With a limited topic, such as is dealt with in
Chapter 1 and Chapter 3, a very comprehensive coverage is possible. In the former,
the only deliberate omissions are the metal complexes in which quinoline is a ligand,
and the reactions in which quinoline functions purely as a base (and where any other
high boiling base would have done as well). The same degree of comprehensive
coverage has not been possible with Chapter 2-the ring syntheses. Here the object
has been to condense as many ring syntheses as possible into a readable article.
No attempt at complete tabulation has been made; illustrative tables for some
major syntheses are given. In all three chapters the abstracts are covered to early
1976, and one or two later items will be found. Compounds mentioned in the text
or tabulated in the text will be found in the subject index; compounds tabulated at
the ends of chapters are not entered in the subject index.
I must thank Dr. Smalley for his efforts on a truly enormous task, and our
respective wives for accepting our apparently endless writing. They had even the
fortitude to prepare jointly the author index.
GURNOJSO NES
University of Keele
Stafordsh ire
vii
Contents
.
1 The Physical and Chemical Properties of Quinoline 1
GURNOS JONES
2 Synthesis of the Quinoline Ring System . . 93
GURNOS JONES
. .
3 Haloquinolines 319
ROBERT K. SMALLEY
. .
Author Index 787
.
Subject Index 853
ix
Chemistry of Heterocyclic Compounds, Volume 32
Edited by Gumos Jones
Copyright 0 1977 by John Wiley & Sons, Ltd.
CHAPTER 1
The Physical and Chemical Properties
of Quinoline
GURNOS JONES
. . . . . . . . . .
I. Introduction 2
. . . . . . . .
11. Theoretical Chemistry 3
. . . . . . . .
111. Physical Properties 5
. . . . . . . . . .
1. Electronic Spectra 5
. . . .
2. Infrared and Raman Spectra 10
3. Nuclear Magnetic Resonance Spectra . . .. I. . . . 11
. . . . . . . .
4. Electron Spin Resonance 15
. . . . . . .
5. Mass Spectrum 16
. . .
6. Photoelectron Spectroscopy and Ele.ctron. Spec.trosco.py , . . . 16
7. X-ray Diffraction , . . . . 16
8. Separation, Identification, and Purification 16
9. Freezing Point, Boiling Point, and Azeotropic Data . 18
10. Density, Surface Tension, Viscosity, and Related Properties 19
.
11. Optical and Magnetic Properties; Dipole Moment 21
1 . .
12. Diffraction Constant, Titrations, and Electrical Properties 22
. . . .
13. Thermochemical Data and Heats of Neutralization 25
. . . . . . . . .
IV. Chemical Properties . . . . . . . 25
1. Addition Reactions; Reduction . . . . . 25
2. Nucleophilic Substitution Reactions , 37
. . . .
43.. EHloemctorolypthiicl iSc uSbusbtisttuittiuotnio .nR eRaecaticotniosn s.. ., .. ., .. *.. ... 4523
5. Oxidation Reactions 61
. . .
6. Formation of Biquinolines 63
.
7. Complexes and N-Substituted Quinolines 64
I. ..
8. Reactions involving Pyrolysis, Degradation, or Irradiation 67
. . . . . . . . . . .
V. References 68
2 The Physical and Chemical Properties of Quinoline
List of Tables
.
TABLE 1. Charge-transfer Complexes of Quinoline 9
.
TABLE 2. lH-Nmr Data for Quinoline 12
.
TABLE 3. W-Nmr Shifts of Quinoline Carbon Atoms 13
.
TABLE 4. l3C--l5NC oupling Constants of Quinoline (in Hz). 13
TABLE 5. Lanthanide Shifts for IH and Signals in Quinoline . 14
.
TABLE 6. Hyperfine Splitting Constants for the Quinoline Radical Anion 15
.
TABLE 7. Vapour Pressure of Quinoline 19
TABLE 8. Boiling Point of Quinoline from 1 to 30 atm . 19
.
TABLE 9. Azeotropes of Quinoline 19
.
TABLE 10. Density (d) of Quinoline from 0 "C to 220 "C 20
TABLE 11. Viscosity (y) of Quinoline from 1 "C to 209 "C . 20
.
TABLE 12. Solubility of Quinoline in Water from 10 "C to 73 "C 20
TABLE 13. Refractive Indices of Quinoline at 15 "c . 21
.
TABLE 14. Effect of Mixed Solvents on the PKA of Quinoline at 25 "C 22
.
TABLE 15. Non-aqueous Titrations Involving Quinoline 22
TABLE 16. Dielectric Constants and Dielectric Losses in Pure Liquid Quinoline from
-30 "C to +60 "C , 24
TABLE 17. Percentage Composition of the Mixtures from Phenylating Quinoline and
.
Quinolinium Salts 54
TABLE 18. Yields of 2-Benzylquinoline and 4-Benzylquinoline after Homolytic
.
Benzylation 54
TABLE 19. Percentage Yields of Monomethyiquinoiinesf rom Homoiytic Methyiations 55
TABLE 20. Salts and Molecular Complexes of Quinoline with Inorganic Compounds 67
TABLE 21. Salts and Molecular Complexes of Quinoline with Organic Compounds . 67
I. Introduction
Quinoline was discovered in coal tar distillate by Rungel in 1834 and named
"Leukol" (from AWKU- and oleum). The base was also obtained by GerhardP in
1842 by alkaline distillation of quinine, cinchonine, or strychnine, and was named
by him "Chinolein" or "Chinolin". Not until 1882 was the identity of leukol and
chinolin firmly established, when Hoogewerff and Van Dorp3 showed that the
samples from coal tar and from alkaloid distillation had the same boiling point,
formed the same hydrate (3H,O), platinichloride, bichromate, and argentonitrate.
Both specimens were also converted by oxidation into quinolinic acid, which was
decarboxylated to nicotinic acid. Korner was cited as the first to propose the
structural formula for quinoline (in Die Chemie von Pyridins und Seiner Devioate by
A. Calm) but Dewar4 in 1871 suggested that quinoline bore the same relationship to
pyridine that naphthalene bore to benzene. The structure (1) was confirmed by the
syntheses in which allylaniline was passed over glowing lead oxide,5 or from o-
nitrocinnamaldehyde as shown in reaction (1).6
aFHO*m
a
NI O -3 -s (1)
H
1
Zn/HCI. POCI,/PCI,. HI, AcOH, 240 "C.
Theoretical Chemistry 3
The molecular dimensions of quinoline have not been accurately determined, but
an X-ray structure determination of a nickel complex containing quinoline' gives
the dimensions shown in Fig. 1. Crystal structures of some other quinoline complexes
have been reported;8-10i n one of themlo the bond lengths and angles reported for the
quinolinium ion show appreciable differences from those shown in Fig. 1.
Fig. Dimensions of quinoline in Ni[S,-
1.
PEt,]. C,H,N (bond lengths in A, angles in
degrees, central bond 1.43 A)
II. Theoretical Chemistry
Quinoline has proved a popular subject for theoretical chemists since Coulson and
Longuet-Higgins first attempted to produce n-electron densities for nitrogen
heterocycles in 1947.11 The major difficulties attending such calculations are
exemplified in their treatment which followed an earlier calculation on pyrrole and
pyridine by Wheland and Pauling.12 The resonance integral was taken as equal to
p, the resonance integral for the C-C bond in benzene, or to zero, according as
atoms r and s were or were not joined by a bond; and ar was taken as a++,&
a+ @,* or a, according as r was a nitrogen atom, a carbon atom bonded to nitrogen,
or any other carbon atom respectively, and a was the Coulomb integral for a
carbon atom in benzene. The implications (which have not subsequently been
accepted) were that there is no interaction between non-bonded atoms, and that the
values given for a~ can be used for any nitrogen heterocycle. The calculations showed
very low nelectron densities at position 2 and position 4 in quinoline, in accord with
the known preference for nucleophilic attack at these positions. The figures given for
n-electron density can less confidently be used for discussion of electrophilic attack
because the nitration quoted as proceeding at the 5-position and the 8-position was
performed under protonating conditions.
Since 1947, many other calculations based on the simple HMO treatment have
been published; a review of the literature to 1954 was given by Zahradnik and
Parkanyi.13 The electron-density figures for quinoline and for its protonated form are
m1
0 9885 0 S319 l o ~ 8 ~
10031 10217
+
0 0842 0 8962 0 950 OGDI5
Ooq5
10129 12161 1033 16609
('4)
(B)
Fig. 2. Electron-density figures for (A) quinoline and (B)
protonated quinoline
shown in Fig. 2 and are typical of those obtained by the HMO treatment (in the
protonated quinoline a~ = a,+2/3; in the unprotonated quinoline a~ = ac+O.5P).
* Wheland and Pauling used a+ +/3 for this integral.