Table Of ContentS-TRIAZINES AND DERIVATIVES
TbiJ is the thirternth uohme published in the JeriPr
THE CHEMISTRY OF HETEROCYCLIC COMPOUNDS
THE CHEMISTRY OF HETEROCYCLIC COMPOUNDS
A MONOGRAPHS
SERIES OF
A RN 0 LD WE I BERG ER, Consulting Editor
S S
S-TRI A 2 I N E S
and
D E R I V ATIVE S
Edwin M. Smolin and Lorence Rapoport
Central Research Divkion, American Cyanamid Company,
Stamf wd, Connecticut
1959
INTERSCIENCE PUBLISHERS INC., NEW YORK
IN TE I C L I LT D., L 0 D 0
R S C E N E PUB S HER S N N
Library of Congress Catalog Card Number 59-8840
INTERSCIENCE PUBLISHERS, INC., 250 Fifth Avenue, New York 1, N.Y.
For Great Britain and Northern Ireland:
Interscience Publishers Ltd., 88/90 Chancery Lane, London, W.C. 2
The Chemistry of Heterocyclic Compounds
The chemistry of heterocyclic compounds is one of the most complex
branches of organic chemistry. It is equally interesting for its theoretical
implications, for the diversity of its synthetic procedures, and for the physio-
logical 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 com-
prehensive 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 ac-
commodate the specific interests of the authors.
Research Laboratories ARNOLDW EISSBERGER
Eastma% Kodak Comfmfiy
Rochester, New York
V
Preface
The subject matter contained in this book was originally intended to be
part of a single volume covering the entire field of Triazines and Tetrazines.
It became apparent from a preliminary consideration of the literature that
this area encompassed too large an amount of published work to be covered
in a single volume of reasonable size. Accordingly, the 1,2,P, and 1,2,3-
triazines and the tetrazines have been covered by Drs. Erickson, Wiley, and
Wystrach leaving the 1,3,5- or s-triazines and the borazoles for the present
volume.
We have made an effort to consider the s-triazines from the point of
view of an organic chemist who, entering the field to do research, wants
information about the literature. An attempt has been made to give physical
properties, especially melting or boiling point and solubility, but without
taking the space to do more than mention other readily accessible seldom
used data. Modern electronic concepts of organic chemistry have been called
upon where possible although mechanistic and kinetic data are largely
lacking in this field. Frequently the classical “balloon” equations were re-
tained to indicate a possible course for certain complex reactions. They are,
of course, in no way intended to represent actual reaction steps. Emphasis
is laid on monomeric finite compounds and on their preparation and reactions
rather than on their applications. The voluminous fields of melamine,
guanamine, and ammeline resins have been by-passed with only a few
introductory paragraphs.
The chemistry of the borazoles is taken up because of their admittedly
superficial structural relationship to the s-triazines, because of the recent
interest in this branch of boron chemistry, and because the borazoles are not
covered in any of the other volumes of this series. Hexamethylenetetramine
chemistry is treated only in so far it is of interest for s-triazines. The field
as
has been covered in the readily available literature and duplicating appeared
unwarranted.
s-Triazine, the fundamental member of the series of compounds treated
in this volume, was unknown at the time of completion of the manuscript,
and has been characterized only recently. Its discussion has been included as
part of the Introduction rather than as an Appendix because the authors feel
that it ought to be discussed in the most easily accessable locationpossible.
An effort has been made to cover the literature from 1860 through 1953
VII
VIII Preface
comprehensively except for historical purposes. From January 1, 1954 to
April 1, 1955, all literature references that were for any reason considered
important were incorporated into the text. was especially necessary for
This
the example of s-triazine discussed in the preceding paragraph.
We wish to express our deep gratitude to the following without whose
help this work would have been immeasurablym ore difficult if not impossible :
Dr. D. W. Kaiser and Dr. F. C. Schaeffer for making available to us their
authoritative opinions and wide experience in the entire field of s-triazine
chemistry: Dr. R. S. Long for his suggested revisions in the section on
s-triazine dye chemistry; Dr. J. H. Fletcher for his suggestions on nomen-
clature; Dr. R. C. Hirt for ultraviolet spectra interpretation; Dr. V. P.
Wystrach who, with Dr. J. G. Erickson, first interested us in participating
in this project; and the American Cyanamid Company for contributing the
use of library and secretarial facilities, kindly authorized by Dr. J. H. Paden
and generously continued by Mr. D. W. Jape.
We also thank Dr. A. L. Peiker and Dr. E. R. Northey for reviewing
Chapter I and suggesting appropriate changes.
E. SMOLIN
M.
RAPOPORT
L.
February, 1959
Contents
Introduction .................................................... 1
1.General ............................................... 1
1I.s-Triazine ............................................ 6
1.Genera.I ............................................ 6
2 . Synthesis .......................................... 9
3.Reactions .......................................... 11
A . Formation .................................. 11
Salt
B. Hydrolysis ...................................... 11
C. Reaction with Hydrogen Chloride .................. 12
D . Reaction with Amines ............................ 13
E . Reaction with Halogens ............................ 13
F. Reaction with Sodamide .......................... 14
G . Hydrogenation .................................. 14
.
H Friedel-Crafts Reaction of s-Triazine and Its Hydro- 14
..............................
chloride Derivatives
I. Grignard Reaction ................................ 15
.
I Cyanuric Acid and Derivatives .............................. 17
.
I Introduction ........................................... 17
I1. Cyanunc Acid ........................................ 20
1. Historical .......................................... 20
2 . Physical Properties .................................. 20
A . General ........................................ 20
B. Density .......................................... 21
C. Thermal Properties ................................ 21
.
D Heat of Neutralization ............................ 22
E . Dissociation Constant .............................. 22
F . Percentage Dissociated at 35" ...................... 22
G . Conductivity .................................... 22
H . Viscosity and Density of Solutions .................. 22
I . Specific Heat .................................... 23
J . Magnetic Susceptibility ............................ 23
K . Raman, Infrared, and Ultraviolet Spectra ............ 23
L. Polarographic Behavior .......................... 23
M . Crystallography and Miscellaneous Properties ........ 23
3 . Synthesis and Occurrence ............................ 24
A . Natural Occurrence ................................ 24
B . From Cyanuric Halides ............................ 24
IX
Contents
X
C. Polymerization of Cyanic Acid ...................... 25
D . From Urea and Urea Derivatives .................. 26
E . From Uric Acid ..................................
29
F. From Allophanates and Carbamyl Chlorides .......... 30
G . From Carbonyl Diurethane and Carbethoxybiuret ....
H . From Formamide Electrolytically .................. 3311
I . From Acetoxamide ................................ 32
J . From Carbaminothioglycolic Acid Anilide ............ 32
.
K Miscellaneous Preparations ........................ 32
4 . Structure ............ .......................... 33
5 . Salts of Cyanuric Acid ................................ 36
6 . Reactions of Cyanuric Acid .......................... 44
A . Hydrolysis ...................................... 44
B. Reaction with Active Halogen Compounds .......... 44
C. Thermal Action .................................. 45
D . Reaction with Ammonia .......................... 45
E . Esterification .................................... 45
F . Acetylation ...................................... 46
G . Reaction with Fatty Acids ........................ 46
H . Reaction with a-Haloacids ........................ 47
I . Rearrangement ................................. 47
7. Applications of Cyanuric Acid ........................ 47
A . Physiological and Technical Significance. ............. 47
B . Melamine Formation .............................. 47
C. Rubber Manufacture .............................. 48
D . Resins ..........................................
I11 . Cyanuric Halides ...................................... 48
1. Cyanuric Chloride .................................... 4488
A . History ..........................................
. 48
B Physical ..............................
C. SyntheticPMroeptehrotidess ................................ 4590
(1) From Cyanogen Chloride ........................
50
(2) From Hydrocyanic Acid ........................ 51
(3) From Cyanuric Acid .......................... 52
(4) Miscellaneous Methods .......................... 52
D . Structure ........................................ 52
E . Reactions ........................................ 53
(1) Hydrolysis and Alcoholysis .................... 53
(2) Reaction with Hydroxy Compounds ............ 54
(3) Reaction with Amino Compounds .............. 55
(4) Reaction with Sulfhydryl Compounds ............ 58
(5) Reaction with Salts of Hydrazoic Acid ..........
58
(6) Reaction with Silver Nitrate ....................
58
(7) Grignard Reaction ............................ 58
Wurtz-Fittig Reaction ........................
(8) 59
(9) Friedel-Crafts Reaction ........................
59
........
(10) Reaction with Carboxylic Acids and Salts
59
Contents
XI
(1 1) Reaction with Malonic Ester .................... 60
(12) Reaction with Hydriodic Acid .................. 60
(13) Reduction .................................. 60
(14) Reaction with Benzamide ...................... 61
F. Physiological Properties ............................ 62
2 . Cyanuric Bromide .................................... 62
A . Synthesis ........................................ 62
(1) Polymerization of Cyanogen Bromide ............ 62
(2) From Bromine and Potassium Ferrocyanide ...... 63
B . Reactions and Structure .......................... 63
(1) Hydrolysis .................................... 63
(2) Reaction with Amines .......................... 63
(3) With Acetic Acid .............................. 64
(4) Reaction with Urea ............................ 64
3 . Cyanuric Iodide .................................... 65
4. CyanuricFluorida .................................... 66
5. 2-Bromo-4,6-dichloros-- triazine ........................ 66
.......................... 67
IV . 6C.y2a-nChulriocr oA-c4i,d6 -Edsitieords o-.s.-.t.r.i.a.z.i.n.e. ....................... 67
1. Alkyl Esters ........................................ 67
A . MethylEsters .................................... 68
(1) Trimethyl Ester ................................ 68
(2) Diethyl Ester ................................ 71
(3) Halomethoxy-s-triazines ........................ 71
(4) Mixed Methyl Esters .......................... 73
.
B EthylEsters .................................... 75
(1) Triethyl Ester ................................ 75
(2) Dimethyl Ester ................................ 79
(3) Monoethyl Ester .............................. 79
(4) Haloethoxy-s-triazines .......................... 79
C. Triallyl Cyanurate ................................ 80
(1) Physical Properties ............................ 80
(2) Synthesis .................................... 81
(3) Reactions .................................... 81
(4) Commercial Applications ........................ 82
(5) Physiological Properties ........................ 83
D . Other Alkyl Esters ................................ 84
2 . Aryl and Arylalkyl Esters ............................ 85
A. TriphenylEster .................................. 85
(1) History ...................................... 85
(2) Physical Properties ............................ 85
(3) Synthetic Methods ............................ 86
(4) Reactions .................................... 87
B.TrixylylEster .................................... 87
C. Tris(P-diisobutylphenyl) Ester ...................... 88
D . Tris(P-chlorophenyl)E ster .......................... 88
.
E 9-Nitrophenyl Esters .............................. 88
