Improvements in the Manufacture and Production of New Diphenyl Derivatives and a New Base for use in the Preparation of Dyestuffs.
Year: 1890

page_text: Date of Application, 11th Aug., 1890
Complete Specification Left, 11th May, 1891-Accepted, 20th June, 1891
Improvements in the Manufacture and Production of New Diphenyl
Derivatives and a New Base for use in the Preparation of
Dyestuffs.
I, JAMES YATE JOHNSON of 47 Lincoln's 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,
Ludwigshafen on Rhine, in the Empire of Germany) to be as follows :-
Although the action of reducing agents on ortho-nitro-phenoxy-acetic acid has
been studied by independent investigators, still up to the present time no one
has succeeded in obtaining a diphenyl derivative from it. (See Fritzsche, Journal
für Practische Chemie N.F. 20, 283; Journal of the Chemical Society 38, 319;
Thate, Journ. f. Pract. Chemie 29, 145 et seq; Journ. Chem. Soc. 46, 1170.)
The present invention relates to the production of such diphenyl-derivatives and
ultimately of para-di-amido-di-ortho-phenoxy-acetic acid, which has probably the
constitution represented by the formula:
Improvements in the Manufacture and Production of New Diphenyl
Derivatives and a New Base for use in the Preparation of
Dyestuffs.
I, JAMES YATE JOHNSON of 47 Lincoln's 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,
Ludwigshafen on Rhine, in the Empire of Germany) to be as follows :-
Although the action of reducing agents on ortho-nitro-phenoxy-acetic acid has
been studied by independent investigators, still up to the present time no one
has succeeded in obtaining a diphenyl derivative from it. (See Fritzsche, Journal
für Practische Chemie N.F. 20, 283; Journal of the Chemical Society 38, 319;
Thate, Journ. f. Pract. Chemie 29, 145 et seq: Journ. Chem. Soc. 46, 1170.)
The present invention relates to the production of such diphenyl-derivatives and
ultimately of para-di-amido-di-ortho-phenoxy-acetic acid, which has probably the
constitution represented by the formula:
NH₂
CH,
OCH, . COOH
OCH,. COOH
C₂H₂
NH,
By treatment with nitrous acid this can be converted into a tetrazo-compound,
which combines with amido and phenolic bodies to yield a series of new dyestuffs.
Neither the action of mineral acids on the hydrazo-derivative from ortho-nitro-
phenoxy-acetic acid, nor the acid reduction of the corresponding azo or azoxy-
compounds yield the new amido-acid directly, as far as has been at present observed;
but in all the processes according to this invention an internal anhydride is first
obtained, which is subsequently hydrated (by the action of alkalies) to the amido-
acid itself.
This anhydride probably has the constitution represented by the formula:

page_text: EXAMPLE 1.-PREPARATION OF THE ANHYDRIDE FROM HYDRAZO-PHENOXY-
ACETIC ACID.
It is preferred in preparing the anhydride in this way to carry on the production
of the hydrazo-compound and its conversion into the anhydride in one continuous
series of operations without separating and isolating the hydrazo-compound. It is
therefore convenient to describe also, at this place the production of the hydrazo-
compound from the nitro-compound, although it is not new. Dissolve about twenty
parts of ortho-nitro-phenoxy-acetic acid in about one hundred parts of water and
add about forty-one parts of caustic soda solution (containing about thirty-five per
cent. of sodium hydrate). Boil and to the boiling solution add alternately zinc
dust and further quantities of caustic soda until the solution is practically colourless.
This will require about thirty-two parts of zinc dust and about sixty-two parts of
caustic soda solution (containing about thirty-five per cent. of sodium hydrate).
Exclude the air as far as possible during this operation. When the solution is
colourless, the formation of the hydrazo-phenoxy-acetic acid is complete. To
convert it into the anhydride in accordance with this invention, pour the whole
mass (still excluding the air as far as possible) into a large excess of strong
hydrochloric acid, stir well and continue heating until the last portions of zinc dust
are dissolved. By this time some of the anhydride will have separated out as a
white precipitate. Cool filter, wash well with water, press and keep for further
use without drying.
EXAMPLE 2-PREPARATION OF THE ANHYDRIDE FROM AZO-PHENOXY-
ACETIC ACID AND FROM AZOXY-PHENOXY-ACETIC ACID.
Make a hot solution of about three parts crystallized stannous chloride in about
eleven parts of concentrated hydrochloric acid (containing about thirty eight per
cent. of real hydrochloric acid HCI) and add gradually whilst well stirring, about two
parts of azo-phenoxy-acetic acid (or the equivalent quantity of the azoxy-compound)
and heat the mixture on the water bath for several hours, or until the red colour of
the precipitate in suspension has disappeared, or nearly so, and on heating a
filtered portion of the liquid, no more white precipitate forms. This point being
reached, dilute with about half its volume of cold water, filter off the anhydride
formed, wash well and press.
The anhydride obtained according to either of the above processes is when
dried a white heavy crystalline powder almost completely insoluble in the
ordinary neutral solvents, and practically insoluble in dilute mineral acids and
in glacial acetic acid. It cannot be diazotized by nitrous acid. It is soluble in
strong sulphuric acid and is precipitated unchanged from the solution by water.
Similarly hot strong caustic soda solution dissolves it; and it crystallizes out
unchanged on cooling, provided that the heating is not continued too long.
When subjected to continued heating it is hydrated to form the sodium salt of
the diamido-diphenoxy-acetic acid.
EXAMPLE 3. CONVERSION OF THE ANHYDRIDE
DIPHENOXY-ACETIC ACID.
INTO THE DIAMIDO-
Dissolve the moist anhydride as obtained by either of the above processes in a
hot solution of caustic soda, taking about seven parts of caustic soda solution
(containing about thirty five per cent. of sodium hydrate) and about five parts of
water for the amount of anhydride obtained by either process from two parts of
nitro-phenoxy-acetic acid, or from the equivalent quantity of azo or azoxy-
compound. Boil until the addition of dilute hydrochloric acid to a filtered cold
test portion, gives no precipitate of the anhydride. Cool and add common salt.

page_text: mass.
The common salt of the desired compound separates out, usually as a light grey
Filter and press and, if desired, recrystallize from a little water adding
common salt solution and caustic soda to assist the separation.
The sodium salt of diamido-diphenoxy-acetic acid is a white powder, which has
not yet been obtained in a distinctly crystalline form. It is practically insoluble in
absolute alcohol, very soluble even in cold water, and can be precipitated from
its concentrated solutions by caustic soda.
Dilute mineral acids produce at first no precipitate in cold aqueous solutions;
but on heating, or on standing with concentrated mineral acids the anhydride is
formed again and separates out. Nitrous acid in acid solution converts it into the
tetrazo-compound as above mentioned.
Dated this 11th day of August 1890.
J. H. JOHNSON & Co..
Agents.
Improvements in the Manufacture and Production of New Diphenyl
Derivatives and a New Base for use in the Preparation of
Dyestuffs.
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 com-
municated 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 :-
Although the action of reducing agents on ortho-nitro-phenoxy-acetic acid has
been studied by independent investigators, still up to the present time no one has
succeeded in obtaining a diphenyl-derivative from it (see Fritzsche, Journal fur
Practische Chemie N.F. 20, 283; Journal of the Chemical Society 38, 319; Thate,
Journal f. Pract. Chemie 29, 145 et seq, Journal Chemical Society 46, 1170).
The present invention relates to the production of such diphenyl-derivatives and
ultimately of para-di-amido-di-ortho-phenoxy-acetic acid, which has probably the
constitution represented by the formula.
Improvements in the Manufacture and Production of New Diphenyl
Derivatives and a New Base for use in the Preparation of
Dyestuffs.
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 com-
municated 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 :-
Although the action of reducing agents on ortho-nitro-phenoxy-acetic acid has
been studied by independent investigators, still up to the present time no one has
succeeded in obtaining a diphenyl-derivative from it (see Fritzsche, Journal fur
Practische Chemie N.F. 20, 283; Journal of the Chemical Society 38, 319; Thate,
Journal f. Pract. Chemie 29, 145 et seq, Journal Chemical Society 46, 1176).
The present invention relates to the production of such diphenyl-derivatives and
ultimately of para-di-amido-di-ortho-phenoxy-acetic acid, which has probably the
constitution represented by the formula.
NH,
C₁₂H3
O.H, COOH
O. CH, COOH
C.H,
NH,
By treatment with nitrous acid this can be converted into a tetrazo-compound,
which combines with amido and phenolic bodies to yield a series of new dyestuffs.
Neither the action of mineral acids on the hydrazo derivative from ortho-nitro-
phenoxy-acetic acid, nor the acid reduction of the corresponding azo or azoxy-
compounds yields the new amido acid directly as far as has been at present observed:
but in all the processes according to this invention an internal anhydride is first
obtained, which is subsequently hydrated (by the action of alkalies) to the amido-
acid itself. This anhydride probably has the constitution represented by the
formula.

page_text: The following examples illustrate the nature of the invention and the manner in
which it may be carried into practical effect.
Throughout the Specification by parts are meant parts by weight.
EXAMPLE 1-PREPARATION OF THE ANHYDRIDE FROM HYDRAZO-PHENOXY-
ACETIC ACID.
It is preferred in preparing the anhydride in this way to carry on the production
of the hydrazo-compound and its conversion into the anhydride in one continuous
series or chain of operations without separating and isolating the hydrazo-compound.
It is therefore convenient to describe also, at this place the production of the
hydrazo-compound from the nitro compound, although it is not new.
Dissolve
about twenty parts of ortho-nitro-phenoxy-acetic-acid in about one hundred parts
of water and add about forty-one parts of caustic soda solution (containing about
thirty-five per cent. of sodium hydrate). Boil, and to the boiling solution add
alternately zinc dust and further quantities of caustic soda until the solution is
practically colourless. This will require about thirty two parts of zinc-dust and
about sixty two parts of caustic soda-solution (containing about thirty-five per cent.
of sodium hydrate).
Exclude the air as far as possible during this operation. When the solution is
colourless, the formation of the hydrazo-phenoxy-acetic-acid is complete. To
convert it into the anhydride in accordance with this invention, pour the whole
mass (still excluding the air as far as possible) into a large excess of strong hydro-
chloric acid, stir well and continue heating until the last portions of zinc-dust are
dissolved. By this time most of the anhydride will have separated out as a white
precipitate. Cool, filter, wash well with water, press and keep for further use
without drying.
EXAMPLE 2.--PREPARATION
ANHYDR
OF THE ANHYDRIDE FROM AZO-PHENOXY-
ACETIC ACID AND FROM AZOXY-PHENOXY-ACETIC ACID.
Make a hot solution of about three parts of crystallised stannous chloride in
about eleven parts of concentrated hydrochloric acid (containing about thirty eight
per cent. of real hydrochloric acid HCI) and add gradually whilst well stirring,
about two parts of azo-phenoxy acetic acid (or the equivalent quantity of the azoxy
compound) and heat the mixture on the water bath for several hours or until the
red colour of the precipitate in suspension has disappeared or nearly so and on
heating a filtered portion of the liquid, no more white precipitate forms. This
point being reached, dilute with about half its volume of cold water, filter off the
anhydride formed, wash well and press.
The anhydride obtained according to either of the above processes is when dried a
white heavy crystalline powder almost completely insoluble in the ordinary neutral
solvents and practically insoluble in dilute mineral acids and in glacial acetic acid.
It cannot be diazotized by nitrous acid. It is soluble in strong sulphuric acid and

page_text: is precipitated unchanged from the solution by water. Hot strong caustic soda
solution dissolves it; and it crystallizes out unchanged on cooling, provided that
the heating is not continued too long. When subjected to continued heating it is
hydrated to form the sodium salt of the di-amido-diphenoxy-acetic-acid.
EXAMPLE 3.-CONVERSION
ANHYDRIDE
OF THE
DIPHENOXY-ACETIC ACID.
INTO THE DIAMIDO-
Dissolve the moist anhydride as obtained by either of the above processes in a
hot solution of caustic soda, taking about seven parts of caustic soda solution,
(containing about thirty five per cent. of sodium hydrate) and about five parts of
water for the amount of anhydride obtained by either process from two parts of
nitro-phenoxy-acetic acid, or from the equivalent quantity of azo or azoxy compound.
Boil until the addition of dilute hydrochloric acid to a filtered cold test portion,
gives no precipitate of the anhydride, which usually requires about one hour.
Cool and add common salt.
The desired base or amido-acid separates out in the form of its sodium salt,
usually as a light grey mass. Filter and press and, if desired, recrystallize
from a little water adding common salt solution and caustic soda to assist the
separation.
The sodium salt of di-amido-diphenoxy-acetic acid is a white powder, which has
not yet been obtained in a distinctly crystalline form. It is practically insoluble in
absolute alcohol, very soluble even in cold water, and can be precipitated from its
concentrated solution by caustic soda. Dilute mineral acids produce at first no
precipitate in cold aqueous solutions; but on heating, or on standing with concen-
trated mineral acids, the anhydride is formed again and separates out. Nitrous
acid in acid solution converts it into the tetrazo-compound as above mentioned.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed I declare that what
claim is,
First. The manufacture of a new diphenyl derivative, being the anhydride of the
amido-acid, or base, di amido di-phenoxy-acetic-acid, by first preparing the hydrazo-
derivative of ortho-nitro-phenoxy-acetic acid and then treating this with concen-
trated hydrochloric acid, all substantially as hereinbefore described.
Second. The manufacture of the same anhydride by treating the azo or azoxy
derivatives of ortho-nitro-phenoxy-acetic acid with stannous chloride in hydro-
chloric acid solution, all substantially as herein before described.
Third. The manufacture of the new base or amido-acid-di-amido-di-phenoxy-
acetic acid by first preparing the anhydride thereof by either of the processes
hereinbefore claimed and then hydrating this by the action of an alkali; all sub-
stantially as hereinbefore described.
Fourth. In the manufacture of di-amido-di-phenoxy-acetic acid the conversion of
the anhydride thereof into the amido-acid or base by treatment with an alkali,
substantially as herein before described.
Fifth. As new articles of manufacture, the diamido-di-phenoxy-acetic acid and
the anhydride thereof hereinbefore described.
Dated the 11th day of May 1891
J. H. JOHNSON & Co.,
Agents.