IMPROVEMENTS IN THE PRO- DUCTION OF BASES FOR COLOURING MATTERS
Year: 1883

page_text: LETTERS PATENT to Edward Griffith Brewer of 33 Chancery Lane in the
County of Middlesex for an Invention of "IMPROVEMENTS IN THE PRO-
DUCTION OF BASES FOR COLOURING MATTERS" communicated to him from
abroad by The Chemische Fabrik auf Actien (vormals E. Schering) of Berlin
Germany
PROVISIONAL SPECIFICATION left by the said Edward Griffith Brewer
at the Office of the Commissioners of Patents on the 21st February 1883.
EDWARD GRIFFITH BREWER of 33 Chancery Lane in the County of Middlesex
"IMPROVEMENTS IN THE PRODUCTION OF BASES FOR COLOURING MATTERS
(A Com-
munication to me from abroad by The Chemische Fabrik auf Action (vormals
E Schering) of Berlin Germany)
"
This invention refers to the production of bases which are closely allied in their.
composition and in their properties to the Chinoline bases; the same is produced
by the reaction of acetic aldehyde and of certain other aldehydes upon the salts
of primary aromatic amines and the same may be denominated "Chinaldine
Bases"
These chinaldine bases are applicable for the production of colouring matters.
For the purpose of identifying the process of producing the said bases, I will
hereinafter describe the method of preparing the base arising from Aniline and
acetic aldehyde which is the simplest and the typical representative of the whole
group of Chinaldine bases.
Preparation of Chinaldine (C₁, H, N) Aniline (1 part by weight) Paraldehyde
(1% parts by weight) fuming raw hydrochloric acid (2 parts by weight) and about
1-50%. Chloride of Aluminium are kept boiling for three hours the product is
poured into water, the new base is separated by Natron lye and purified by
fractionnation. The base thus produced, the Chinaldine has the following com-
position vis C, H, N and boils at 240°. Its formation takes place according to
the following equation vis: C, H,N + 2 C, H₂O = C₁₂N + 2 H₂O + H.
The above indicated proportions for the production of the Chinaldine which test
has shown to be the most suitable may be varied in various directions. Instead
CT

page_text: of the hydrochloric acid other acids may be used, for instance hydrobromic acid
concentrated sulphuric acid, phosphoric acid.
The chloride of Aluminium may be replaced by other metallic salts for instance
Chloride of zinc, Chloride of tin or even by metals themselves. The addition of
these bodies has for its object only to start the reaction and to further the progress
thereof,, the reaction will however take place though with a less satisfactory result
even without the same.
The transformation of the Aniline into Chinaldine is effected not only by the
paraldehyde but also with a smaller yield by common aldehyde, Adol-Acetal,
croton-aldehyde and also by lactic acid.
The process which serves for preparing the Chinaldine from Aniline will also be
used without essential alteration for preparing the corresponding bases from other
primary amines of the aromatic series. From the homologues and derivatives of
the Aniline are produced under similar treatment with aldehyde in acid solution,
the corresponding homologues and derivatives of the Chinaldine. Thus the
Toludines (C. H.H) furnish methyl-chinaldine [(C H₂) C, H, N] the Amydo-
phenols (C. H.H*) give oxychinaldines [(OH) C₂ H¸ N] and so forth.
N
NH,
The Invention specially refers to the application of the described process to the
following aminos.
1) Amiline and its homologues Toludine, Xylidine, Cumidine.
2) Amydophenols and their homologues as well as Amydophenol ether
(C, H. 3) as for instance Anisidine (C, H. NHL) and their homologues.
NH
O [R).
The Chinaldine bases produced according to this process are transformed into
hydric or hydrated and Alkyl hydrobases in the following manner.
Chinaldine is together with tin and concentrated hydrochloric acid heated for
several hours, on cooling the double tin salt of the tetra-hydrochinaldine
separates.
This is deprived of the tin, the tetra hydrobase is eliminated by natron lye.
The latter has the following composition C₁, H₁, N and forms an oleaginous liquid
having a pleasant odour and boiling at 246-248°. Instead of tin and hydrochloric
acid other reducing agents may be used for instance zinc and sulphuric acid.
By heating the tetra hydrochinaldine with chloralkylene Bromalkylene or
Iodalkylene it is transformed into Alkyle hydrochinaldine (C₁ H₁₂ (R¹) N) which
acts as tertiary bases and from these, colouring matters may also be produced.
By the same method the remaining above mentioned Chinaldine bases are also
transformed into hydrobases and Alkylehydrobases.
The sulpho acids are produced from Chinaldine and its homologues and
derivatives by heating the same for some considerable time together with concen-
trated sulphuric acid to a higher temperature (not below 120°) and then
transforming the sulpho acids thus produced into the natron salt or the calcium
salt. Instead of the concentrated sulphuric acid monochlorhydrine may also
be used.
By melting the sulpho acids with caustic alkali the above mentioned oxychinal-
dines can be produced.
Bases of the chinoline serves analogous to the chinaldine bases can also be
obtained from the salts of the above named Amines by treatment with certain
other aldehydes.
If for instance Aniline raw hydrochloric acid and Cinnamon aldehyde are heated
for a short time with some Chloride of Aluminium then a base is obtained which
crystallizes in needles and whose composition is C₁, H₁ N and which is separated
from the product of the reaction by natron lye and likewise belongs to the
Chinoline series. It is formed according to the following equation vis :

page_text: Cinnamon aldhyde will act in a similar manner upon the homologues of aniline
and upon Amydophenol and Amydophenol ether.
Similar bases are obtained from the salts of the above named Amines by
heating with Benzylidenacetone C, H, C, H, CO. OH, according to the same
method.
Another essential feature in the Invention is the application of the described
process upon the following Aldehydes.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed
by the said Edward Griffith Brewer in the Great Seal Patent Office on the
21st August 1883.
:
"
EDWARD. GRIFFITH BREWER of 33 Chancery Lane in the County of Middlesex
"IMPROVEMENTS IN THE PRODUCTION OF BASES FOR COLOURING MATTERS (A com-
munication to me from abroad by The "Chemische Fabrik auf Actien (vormals
E. Schering)" of Berlin Germany)
By heating acetic aldehydes with the salts of primary aromatic amine, bases are
produced which may be called chinaldine bases and which in their composition and
their properties are closely allied to the chinoline bases. They may be rendered
into hydro-derivates as well as oxy-derivates, which are applicable for the
production of colouring matter and also as antiseptic and antipyretic means.
The simplest representative of these bases, the chinaldine C₁, H, N, produced
from aniline and aldehyde, is formed by the reaction expressed by the following:
equation:-
C, H, N + 2C, H¸O = C₁ H, N + 2 H₂O + H₂
The process for producing the oxy-hydro-chinaldines and their methylic and
ethylic derivates falls into three consecutive stages of the reaction viz.
1. Production of the chinaldines.
2. Rendering of the chinaldines into oxy-chinaldines and their methyl and
ethyl-ethers.
3. Rendering of the oxychiṇaldines, and their methyl-and ethyl-ether into
hydrocompounds.
I Production of the chinaldines. A mixture of 100 parts (by weight) of aniline
(or 115 parts Toluidine and 130 parts xylidine), 150 parts par-aldehyde, 200 parts
of crude hydrochloric acid, and 2 to 5 parts chloride of aluminium is kept boiling
for three to six hours; the product is poured into water, and the filtered solution
over saturated with soda lye. The base thus separated is distilled with steam and
purified by fractionation. The proportions here given have been found specially
suitable, but may be varied. Thus instead of the paraldehyde may, though not so
suitably, be substituted ordinary aldehyde, acetal, croton-aldehyde, aldol or lactic
acid. Instead of hydrochloric acid other acids may be used such as hydrobromic
acid, concentrated sulphuric acid or phosphoric acid. The reaction will also take
place without chloride of aluminium but will be expedited by the addition of this
body. Other metallic salts such as chloride of zinc or chloride of tin, or even
metals act similarly to the chloride of aluminium. The reaction will also though
imperfectly and slowly take place at a lower temperature, and heat is therefore
preferable in most cases
The bases thus produced will distil without separating and behave as regards
chemical reagents analogous to the chinoline bases. The following give the
characteristics of some of them.
Chinaldine C, H, N (from aniline) forms a liquid that smells similarly to
chinoline and boils at 240° C (464° F).
Ortho-methyl-chinaldine. (CH) C₁, H₂ N, is a liquid which boils at 249–251° C
(480-484° F)
Para-Methyl-chinaldine (CH) C, H, N, which is isomeric with the last named,
is solid and forms colourless crystals which melt at 59-60° C (138–140° F)
As according to the latest researches chinaldine C H¸¨N is found quite ‍formed

page_text: the derivates from chinaldine to be described below may also be produced from this
naturally existing chinaldine.
'
II. The production of the oxy-methoxy- and ethoxy-chinaldines.
The hydroxyl-methoxyl-and-ethoxyl-derivates from the chinaldines produced as
in section I are obtained according to the following two methods.
a. Chinaldine or the methylated chinaldines are put into a surplus quantity of
smoking sulphuric acid (H, SO.+ X SO₂) or sulphuric acid chlorhydrine, and the
solution is heated for some time to 120° C (248° F) or more. The sulpho-acid
thereby formed is transformed into the salt of lime, and this latter by treatinent
with soda into the salt of soda. The salt of soda is melted up with about four
times the quantity of caustic soda, dissolved in water, well neutralized with
sulphuric acid, and the separated oxychinaldine purified by distillation.
This process of producing the oxychinaldine takes place according to the
following formula :—
(H SO₂) C, H, N + 2 Na O H = (О H) C₁ HÅ¨N + SO, Na₂ + H₂ O.
The oxychinaldine so obtained is transformed into methoxy- or ethoxy-
chinaldine by treatment with methyl- and ethyliodide, or the chlorides of these
alkyles.
b. By the same process as the chinaldine from aniline are obtained oxychinaldine,
ப
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page_text: the halogenous combinations of methyl-ethyl and amyl be transformed into methyl,
ethyl and amyl-compounds which also form pleasantly smelling liquids.
The oxy-hydro-chinaldines and their methyl and ethyl-derivates made according
to this part of the invention will in combination with diazo-benzol salt yield
reddish brown dyes and in combination with tri-chlorides of benzole green dyes.
The intermediate products mentioned in the first and second part of this
invention in connection with the production of the oxy-bydro-chinaldines yield
similar dyes.
Having now described the nature of the said invention and in what manner the
same is to be performed I declare that I claim as the invention communicated
to me:
First: The production or manufacture of chinaldines by the action of aldehyde
on the salts of aniline, toluidine and xylidine, as set forth
Second-The production or manufacture of oxy-methoxy and ethoxy-chinaldine
either by treating the chinaldine with sulphuric acid, melting the sulpho acid
hereby formed with caustic soda and ethylizing and methylizing the hydroxy
compounds so produced by the halogenous compounds of the ethyl and the methyl,
or by the action of aldehyde on the salts of amido-phenoles and amido-phenol-
methyl-and ethyl-ethers as set forth.
Third: The production or manufacture of oxy-hydro chinaldines and their
ethyl and methyl derivates by treating the oxy-methoxy and ethoxy-chinaldines
produced according to the method secondly claimed with reducing agents as set
forth.
In witness whereof I the said Edward Griffith Brewer have hereunto set my
hand and seal this Twentyfirst day of August in the year of our Lord One
thousand eight hundred and eighty three.
EG BREWER (L.S.)