The Manufacture and Production of New Amido Azo Compounds and Azo-dyes therefrom.
Year: 1890

page_text: Date of Application, 12th Sept., 1890
Complete Specification Left, 4th May, 1891-Accepted, 6th June, 1891
PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Amido Azo Compounds
and Azo-dyes therefrom.
I JAMES YATE JOHNSON of 47 Lincolns Inn Fields in the County of
Middlesex Gentleman do hereby declare the nature of this invention which has
been communicated to me from abroad by Badische Anilin & Soda Fabrik of
Ludwigshafen-on-Rhine in the Empire of Germany to be as follows:-
--
In the Specification to the application for Letters Patent No. 12386 of the
7th August 1890 I have described the manufacture of new amido-compounds
namely amido-naphthoxy-acetic acid and its sulpho acids.
The present invention relates to the manufacture of azo-dyes from the said new
amido-compounds.
°
By the combination of these substances with diazo- or tetrazo compounds, amido-
azo- bodies are formed which are themselves colouring-matters, but which derive
their principal value from the fact, that they can be again diazotised and the new
diazo compounds so obtained can then be combined with amido- or phenolic-bodies
or sulpho- or carboxylic acids thereof to yield a class of dyestuffs of which several
possess very valuable properties.
The following is an example to illustrate the nature of this invention using
amido-naphthoxy-acetic acid, and for the sake of convenience I first give directions
for the manufacture of the said amido- acid. By parts throughout this Specification
are meant parts by weight.
Stir about one part of beta-naphthoxy-acetic acid (see Journal of the Chemical
Society Vol. 52 page 495) gradually into about four parts of nitric acid (containing
about fifty eight to sixty per cent. real nitric acid HNO³) at a temperature of about
fifteen to twenty degrees Centigrade and continue to stir the mixture for say
about twelve hours at about the same temperature. Next pour the whole into
about six parts of ice water. The nitro acid separates out. Filter, wash with
water, press and dry. It may if desired be purified by recrystallization from, say,
boiling alcohol.
Take about one part of this product, the alpha-nitro-beta-naphthoxy-acetic acid;
and add it gradually in the form of a fine powder, to a boiling solution of about
three parts of stannous chloride in about three and a half parts of concentrated
hydrochloric acid (containing about thirty eight per cent. of real hydrochloric
acid HCl) and continue boiling for a short time. The nitro body is reduced but
the compound which separates out, is not the desired amido compound, but its
anhydride, an intermediate product. Filter, wash with water then with dilute
warm soda solution, then again with water, press and dry.
This anhydride is then to be converted into the amido-acid by treatment with
caustic alkalies.
In carrying out this invention it is advantageous to perform this operation
immediately before using the said amido-acid in the new manufacture. For this
purpose take about twenty parts of the anhydride obtained as above described and
mix well with about one hundred parts of water and about one hundred parts of
caustic soda-lye containing about thirty five per cent. of sodium hydrate, and boil
until the whole turns semi-solid forming a thick paste owing to the formation of the
sodium salt of the amido-acid. To prepare a new amido-azo body in accordance
with this invention introduce the mass into about a thousand parts of cold water
und cool it further by the addition of about five hundred parts of ice and quickly
add about one hundred and twenty parts of hydrochloric acid containing about
hirty eight per cent. real hydrochloric acid (HCI) diluted with about an equal
quantity of water. To this solution add immediately a solution of the diazo
compound of the so-called Freund's naphthylamine disulpho-acid (see British
[Price Bd273

page_text: Patent, No. 1069 of 1883) obtained from about thirty two and a half parts of the
acid sodium salt of the said acid. The new amido azo body soon forms and partly
separates out (unless too much acid has been used in the preparation of the above
solutions, in which case the requisite quantity of sodium acetate must be added as
will be readily understood by chemists). The new compound may either be
practically completely precipitated by the addition of common salt and filtered off,
pressed and then brought again into suspension in about fifteen hundred parts of
water and diazotised or the mixture obtained as above described can at once be
diazotised. In either case this operation is effected as follows:-
To the solution or mixture in water add about forty five parts of hydrochloric
acid containing about thirty eight per cent. of real hydrochloric acid (HCl) and a
strong aqueous solution of sodium nitrite containing, about seven to eight parts of
pure nitrite and stir, till the liquid is of a bright brownish-yellow colour. This
point being reached, the production of a new diazo- compound is complete. Next,
pour the whole into a solution of about thirty five parts of beta-naphthol-disulpho
acid (R salt) and about two hundred parts of calcined soda in about fifteen hundred
parts of water. Stir for a short time, precipitate the colouring matter still in
solution with common salt, filter and press and purify if necessary by redissolving
and reprecipitating.
The amido-naphthoxy-acetic-sulpho-acids of the Specification No. 12386 are
produced as follows:-
A sulpho acid of naphthol such as for instance Schaeffer's beta-naphthol-beta-
sulpho-acid is treated with mono-chloracetic acid to produce in this case beta-
naphthoxy-acetic-beta sulpho-acid; and then this compound is nitrated and reduced
for the production of the anhydride of the amido acid in the manner hereinbefore
described. The sulphonated anhydride so obtained can be converted into the
corresponding amido acid and used instead of the unsulphonated amido acid in the
manner given in the above example.
Instead of the Freund's naphthylamine disulpho acid equivalent quantities of
other amido compounds can be used and instead of the R-salt equivalent quantities
of other amido- or phenolic bodies can be used so that a large number of bodies can
be prepared according to this invention;-to illustrate this I give the following table
shewing some typical combinations:-

page_text: The dyestuffs Nos. 1 to 6 dye wool directly from an acid bath. The compound
No. 6 of which the preparation is described in the example yields a green-black
colour which is fast to soap. The dyes 7 to 12 are dyed upon wool which has
received a chrome-mordant, and give shades which are fast to milling.
Dated this 12th day of September 1890.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.
COMPLETE SPECIFICATION.
The Manufacture and Production of New Amido-azo Compounds
and Azo-dyes therefrom.
I, JAMES YATE JOHNSON of 47 Lincolns Inn Fields in the County of
Middlesex Gentleman do hereby declare the nature of this invention which has
been communicated to me from abroad by the Badische Anilin- and Soda Fabrik of
Ludwigshafen-on-Rhine in the Empire of Germany and in what manner the same
is to be performed to be particularly described and ascertained in and by the
following statement :-
In the Specification of the application for Letters Patent No. 12386 of the
7th August 1890 there is described the manufacture of new amido-compounds, namely
amido-naphthoxy-acetic acid and its sulpho-acids. The present invention relates
to the manufacture of azo-dyes from the said new amido-compounds which takes
place in two steps or stages. First, by the combination of the said amido-
compounds with diazo- or tetrazo-compounds such as are used by manufacturers in
the preparation of azo dyes, new amido-azo-bodies are formed which, are them-
selves colouring matters but which derive their principal value from the fact that
in the second stage they can be themselves diazotized and the new diazo- or tetrazo-
compounds so obtained, can then be combined with amido- or phenolic bodies or
sulpho- or carboxylic-acids thereof. In this way the new azo-dyes are obtained of
which several possess very valuable properties.
The following is an example to illustrate the nature of this invention and the
manner in which it can be carried into practical effect. By parts throughout this
Specification are meant parts by weight.
In carrying out this invention it is advantageous to start from the anhydride of
the amido-acid used and to convert it into the free amido-acid immediately before
using it in the new manufacture. For this purpose take about twenty parts of the
anhydride of alpha-amido-beta-naphthoxy-acetic acid obtained as described in the
Specification of the application for Letters Patent No. 12386 of 1890 and mix
well with about one hundred parts of water and about one hundred parts of caustic
soda lye containing about thirty-five per cent. of sodium hydrate, and boil. Towards
the end of the reaction the whole becomes semi-solid, forming a thick paste and the
boiling is continued until a sample dissolved in cold water gives no precipitate with
acetic acid.
To prepare a new amido-azo body in accordance with this invention introduce the
mass into about one thousand parts of cold water and cool it further by the addition
of about five hundred parts of ice, and quickly add about one hundred and twenty
parts of hydrochloric acid containing about thirty eight per cent. real hydrochloric
acid (HCI) diluted with about an equal quantity of water.
To this solution add
immediately a solution of the diazo-compound of the so-called Freund's naphthyl-
amine disulpho-acid (see British Patent No. 1069 of 1883) obtained from about
thirty-two and a half parts of the acid sodium salt of the said acid. The new
amido-azo-body soon forms and partly separates out (unless too much acid has
been used in the preparation of the above solutions in which case the requisite
quantity of sodium acetate must be added as will be readily understood by chemists).
To obtain a new azo-dye from the new amido-azo compound thus obtained, this new

page_text: compound may either be practically completely precipitated by the addition of
common salt and filtered off, pressed and then brought again into suspension in
about fifteen hundred parts of water and diazotised; or the mixture obtained as
above described can at once be diazotised. In either case this operation is effected
as follows:-
To this solution or mixture in water add about forty-five parts of hydrochloric
acid containing about thirty-eight per cent. of real hydrochloric acid (HCl) and a
strong aqueous solution of sodium nitrite containing about seven to eight parts of
pure nitrite, and stir till the liquid is of a bright brownish-yellow colour. This
point being reached, the production of a new diazo-compound is complete. Next
pour the whole into a solution of about thirty-five parts of beta-naphthol-disulpho-
acid (R-salt) and about two hundred parts of calcined soda in about fifteen
hundred parts of water. Stir for a short time, precipitate the colouring matter
still in solution with common salt, filter and press and purify if necessary by
redissolving and reprecipitating.
Instead of the alpha-amido-beta-naphthoxy-acetic acid used in the above example
the alpha-amido-beta-naphthoxy-acetic-beta-sulpho acid described in the Speci-
fication of the aforesaid application for Letters Patent No. 12386 of 1890 can be
used and instead of the Freund's naphthylamine-di-sulpho acid equivalent quantities
of other amido- compounds and instead of the R-salt equivalent quantities
of other amido- or phenolic bodies (such as are in ordinary use by manufacturers
for combination with diazo- or tetrazo-compounds in the preparation of azo-dyes);
so that a large number of bodies can be prepared according to this invention; to
illustrate this, I give the following table shewing some typical combinations:-

page_text: this way a green-black colour which is fast to soap. The dyes Nos. 7 to 12 are
dyed upon wool which has received a chrome-mordant and give shades which are
fast to milling.
Having now particularly described and ascertained the nature of the said
invention and in what manner the same is to be performed I declare that what I
claim is :-
(1) The manufacture of amido-azo-compounds by combining diazo- or tetrazo-
compounds with alpha-amido-beta-naphthoxy-acetic-acid or with alpha amido-beta-
naphthoxy-acetic-beta-sulpho-acid.
(2) The manufacture of azo-dyes by combining alpha-amido-beta-naphthoxy-
acetic acid or alpha-amido-beta-naphthoxy-acetic-beta-sulpho acid with a diazo- or
tetrazo compound to form an amido-azo-body, then diazotizing this body and
combining the resulting diazo- or tetrazo-compound with amido- or phenolic bodies
all substantially as hereinbefore explained.
(3) The manufacture of azo-dyes by combining alpha-amido-beta-naphthoxy-
acetic acid or alpha amido-beta-naphthoxy-acetic-beta-sulpho-acid with a diazo-
compound herein before mentioned to form an amido-azo-compound then diazotizing
this amido-azo-compound and combining the resulting diazo-compound with the
amido or phenolic bodies herein before mentioned all substantially as hereinbefore
described.
(4) As new articles of manufacture the new dyestuffs such as are produced as
hereinbefore described and claimed.
Deted this 4th day of May 1891
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.