Improvements in and relating to the Manufacture and Production of New Materials for the Preparation of Dyestuffs.
Year: 1890

page_text: Date of Application, 7th Aug.. 1890
Complete Specification Left, 4th May, 1891-Accepted. 6th June, 1891
PROVISIONAL SPECIFICATION.
Improvements in and relating to the Manufacture and Production of
New Materials for the Preparation of Dyestuffs.
I, JAMES YATE JOHNSON of 47 Lincoln's Inn 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) to be as follows:-
As is well known, naphthoxy-acetic acids, or as they can also be called naphthyl-
glycolic acids can be prepared by the interaction of monochloracetic acid (mono-
bromacetic acid) and alpha- or betanaphthol (Spica Journal of the Chemical
Society Vol. 52 page 495). Previous to this invention no means of applying these
compounds in the dyestuff industry were known.
This invention is based upon the discovery that these bodies can by suitable
treatment be converted into valuable materials for the manufacture of dyestuffs
also that new sulpho-acids of the naphthoxy-acetic acids can be obtained which are
likewise susceptible of a similar conversion. The new sulpho acids are obtained by
acting on alpha- and beta- naphthol- sulpho acids with monochloracetic acid.
By nitrating these bodies and reducing the nitro-compounds obtained, amido
derivatives are ultimately formed which can be combined with diazo- and tetrazo
compounds, to yield a series of new dyestuffs.
As a convenient means of illustrating and explaining with greater detail the
nature of the invention I give by way of example directions for obtaining :-
(1) alpha-amido-beta-naphthoxy-acetic acid.
:-
(2) beta-naphthoxy-acetic-beta-sulphoacid from Schaeffer's beta-naphthol-mono-
sulpho acid.
(3) alpha-amido-beta-naphthoxy-acetic-beta-sulphoacid.
The invention is not however confined to the production and manufacture of
these bodies and intermediate products in their formation.
By parts throughout this Specification are meant parts by weight.
EXAMPLE 1. PREPARATION OF ALPHA-AMIDO-BETA-NAPHTHOXYACETIC ACID.
Stir about one part of beta-naphthoxy-acetic acid gradually into about four parts
of nitric acid (containing about fifty eight to sixty per cent. real nitric acid HÑO,)
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. Allow the mixture to cool, dilute with water,
filter, wash and press.
In order to convert this anhydride into the acid, mix the
press cakes obtained, and whilst still moist, with about four parts of caustic soda
solution (containing about thirty five per cent. sodium hydrate) diluted with about
three to four parts of water. Boil for a short time. The sodium salt of the alpha-
amido-beta-naphthoxy-acetic-acid is formed and separates out (particularly on

page_text: cooling) as bright crystalline needles of a pale brownish colour. Filter, wash with
a little cold water, press and preserve for use in the moist state, or if preferred, dry
with great care.
The alpha-nitro-beta naphthoxy-acetic acid obtained as an intermediate product
in the above process, when pure, crystallizes in thick pale-yellow needles which
melt at a temperature of about 190 to 192 degrees Centigrade. It is but slightly
soluble in boiling water, more readily soluble in acetic acid glacial acetic acid and
alcohol at their boiling points. Hot soda solution dissolves it easily and on cooling
the sodium salt crystallizes out in long needles of a pale yellow colour.
The second intermediate product above mentioned, the alpha-amido-beta-
naphthoxy-acetic anhydride is an inert body, and does not combine with diazo-
compounds; it appears to have the constitution represented by the following
formula
The sodium salt of the alpha-amido-beta-naphthoxy-acetic acid, obtained as
above described, is rather soluble in cold water but very soluble in hot water. If
a well cooled solution be carefully treated with acetic acid or dilute hydrochloric
acid, a white flocculent precipitate is formed which consists probably of the free
amido-acid, which changes on standing, or immediately on heating, into the above
described anhydride.
EXAMPLE 2. PREPARATION OF BETA-NAPHTHOXY-ACETIC-BETA-SULPHOACID.
Dissolve about one hundred parts of the acid sodium salt of Schäffer's beta-
naphthol-sulpho-acid in about five hundred parts of boiling water made alkaline
with about fifty seven parts of caustic soda solution containing about thirty five per
cent. of sodium hydrate; and add a solution of sodium mono-chloracetate prepared
by neutralizing carefully in the cold about fifty parts monochloracetic acid dissolved
in about fifty parts of water, with about fifty five parts of caustic soda solution
(containing about thirty five per cent. of sodium hydrate). Heat this mixture for
from six to eight hours upon the water bath. The neutral sodium salt of the beta-
naphthoxy-acetic-sulphoacid is formed and begins to separate out. Allow to cool
and filter. To remove any unchanged naphthol sulphoacid, redissolve in about six
hundred parts of boiling water and add from seventy to a hundred parts of caustic
soda solution containing about thirty five per cent. of sodium hydrate. Filter when
cold, and wash with dilute caustic soda until a test portion of the crystals on the
filter after solution in water gives no colour reaction with diazo-compounds.
The sodium salt of the beta-naphthoxy-acetic beta-sulphoacid thus obtained
crystallizes in short bright rhombic plates, which are colourless or slightly tinged
with red. It is but slightly soluble in cold water, more readily in hot water and
scarcely soluble in alcohol. It is probably a neutral salt of the constitution
represented by the formula:
If a hot aqueous solution be treated with an excess of hydrochloric acid, delicate
colourless acicular crystals separate out on cooling. This is probably an acid salt
and by addition of alkali is reconverted into the neutral salt.
EXAMPLE 3. PREPARATION OF THE ALPHA-AMIDO-BETA-NAPHTHOXY-ACETIC-
BETA-SULPHOACID,
The nitration of the naphthoxy-acetic-sulpho-acid can be effected by treating its
above described sodium salt with nitric acid in accordance with the directions given
in Example for the nitration of the naphthoxy-acctic-acid. On pouring the

page_text: nitration product into ice-water, a clear solution is obtained; to this add a large
excess of caustic soda and common salt. The sodium salt of the nitro body
separates out. Filter off and press, and, if desired, purify by redissolving in water
and precipitating with caustic soda.
Next dissolve about two parts of the sodium salt of the nitro acid in about four
parts of boiling water and add about one part of acetic acid (containing about
twenty per cent. real acid) boil and add gradually to the boiling solution about one
part of iron filings. As soon as the solution is no longer yellowish neutralise with
soda and filter hot. In the filtrate on cooling a crystalline precipitate separates
out, it consisting of the anhydride of the beta naphthoxy-beta-sulphoacid in the
form of a sodium salt. Filter, wash with a little cold water and press. To hydrate
this and convert in into the acid, boil about one part with a mixture of seven parts
of caustic soda solution (containing about 35 per cent. of sodium hydrate) and five
parts of water for about fifteen to thirty minutes. A. clear solution is obtained
from which shortly the sodium salt begins to separate out. This can be obtained
by cooling, filtering, and pressing, but it is better to dilute the solution obtained as
above described and to use that directly in the manufacture of dyestuff's.
The sodium salt of the anhydride of the beta-naphthoxy-acetic-beta-sulphoacid
obtained as an intermediate product in the above process has probably the con-
stitution represented by the formula :
it can be obtained in beautiful glittering crystalline scales and is slightly soluble in
cold water, readily soluble in hot water.
The sodium salt of the alpha-amido-beta-naphthoxy-beta-sulphoacid prepared as
above described, is a powder, which has not yet been obtained in a distinctly
crystalline form; it is very soluble in water but only slightly so in caustic soda.
On heating with mineral acids it is converted into the anhydric salt.
Dated this 7th day of August 1890.
J. H. JOHNSON & Co.,
Agents.
COMPLETE SPECIFICATION.
Improvements in and relating to the Manufacture and Production of
New Materials for the Preparation of Dyestuffs.
1, 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
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:-
As is well known, naphthoxy-acetic acids (or as they may also be called naphthyl-
glycolic acids) can be prepared by the interaction of mono-chlor-acetic acid (mono-
brom-acetic acid) and alpha- or beta-naphthol (Spica Journal of the Chemical
Society Volume 52 page 495). Previous to this invention so far as I am aware no
means of applying these compounds in the dyestuff industry were known.
This invention is based upon the discovery that these bodies by suitable treatment
can be converted into valuable materials for the manufacture of dyestuff's, also that
new sulpho-acids, of the naphthoxy-acetic-acids can be obtained, which are likewise
susceptible of a similar conversion. The new sulpho-acids are obtained by acting
on alpha- and beta-naphthol-sulpho-acids with mono-chlor-acetic-acid.
By nitrating these bodies and reducing the nitro-compounds obtained, amido-
derivatives are ultimately formed which can be combined with diazo- and tetrazo-

page_text: compounds, to yield new dyestuffs the production of some of which forms the
subject matter of the application for Letters Patent No. 14,416 of 1890.
As a convenient means of illustrating and explaining with greater detail the
nature of the invention and the manner in which it can be carried into practical
effect, I give by way of example directions for obtaining,
(1) alpha-amido-beta-naphthoxy-acetic acid.
(2) beta-naphthoxy-acetic-beta-sulpho-acid from Schaeffer's beta-naphthol-mono-
sulpho-acid.
(3) alpha-amido-beta-naphthoxy-acetic-beta-sulpho-acid; but as will be easily
understood by chemists, alpha-naphthol can be used instead of beta-naphthol
and other naphthol-sulpho-acids will probably be found to be capable of use instead
of the Schaeffer's acid mentioned.
By parts throughout this Specification are meant parts by weight.
EXAMPLE 1. PREPARATION OF ALPHA-AMIDO-BETA-NAPHTHOXY-ACETIC ACID.
Stir about one part of beta-naphthoxy-acetic acid gradually into about four
parts of nitric acid (containing about fifty eight to sixty per cent. real nitric
acid H.N.O,) 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 crystallization 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 three and a half parts of concentrated hydro-
chloric acid (containing about thirty-eight per cent. of real hydrochloric acid HCI)
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 inter-
mediate product. Allow the mixture to cool, dilute with water, filter, wash and
press. In order to convert this anhydride into the acid, mix the press-cakes
obtained, and whilst still moist, with about four parts of caustic soda solution
(containing about thirty-five per cent. sodium hydrate) diluted with about three to
four parts of water. Boil for a short time. The sodium salt of the alpha-
amido-beta-naphthoxy-acetic acid is formed and separates out (particularly on
cooling). Filter, wash with a little cold water (or better with common salt
solution) press and preserve for use in the moist state, or if preferred dry with
great care.
An improved yield of alpha-nitro-beta-naphthoxy-acetic acid can be obtained by
nitrating the naphthoxy-acetic acid in the form of its ethyl-ether, proceeding as
hereinbefore described and subsequently saponifying the ethylated nitro-body
produced. The ethyl-ether of the naphthoxy-acetic acid, can be obtained by the
usual ethylating process.
The alpha-nitro-beta-naphthoxy-acetic acid obtained as an intermediate product
in the above process, when pure, crystallizes in thick pale-yellow needles which
melt at a temperature of about 190° to 192 degrees Centigrade. It is but slightly
soluble in boiling water but is more readily soluble in acetic acid, glacial acetic acid
and alcohol at their boiling points. Hot soda solution dissolves it easily and on
cooling the sodium salt crystallizes out in long needles of a pale yellow colour.
The second intermediate product above mentioned (the alpha-amido-beta-
naphthoxy-acetic anhydride) is an inert body and does not combine with diazo-
compounds it appears to have the constitution represented by the following
formula,

page_text: The sodium salt of the alpha-amido-beta-naphthoxy-acetic acid, obtained as
above described, is rather soluble in cold water but very soluble in hot water. If
a well cooled solution be carefully treated with acetic acid or with dilute hydro-
chloric acid, a white flocculent precipitate is formed which consists probably of the
free amido-acid, which changes on standing, or immediately on heating, into the
above described anhydride.
EXAMPLE 2. PREPARATION OF BETA-NAPHTHOXY-ACETIC-BETA-SULPHO-ACID.
Dissolve about one hundred parts of the acid sodium salt of Schaeffer's beta-
naphthol-mono-sulpho-acid in about five hundred parts of boiling water made
alkaline with about fifty-seven parts of caustic soda-solution containing about
thirty-five per cent. of sodium hydrate; and add a solution of sodium mono-chlor-
acetate prepared by neutralizing carefully in the cold, about fifty parts mono-
chlor-acetic acid dissolved in about fifty parts of water with about fifty-five parts
of caustic soda-solution (containing about thirty-five per cent. of sodium hydrate).
Heat this mixture for from six to eight hours upon the water bath. The neutral
sodium salt of the beta-naphthoxy-acetic-sulpho-acid is formed and begins to
separate out. Allow to cool and filter. To remove any unchanged aphthol-
sulpho-acid, redissolve in about six hundred parts of boiling water, and add from
seventy to one hundred parts of caustic soda solution containing about thirty-
five per cent. of sodium hydrate. Filter when cold and wash with dilute caustic
soda until a test portion of the crystals on the filter, after solution in water, gives
no colour reaction with diazo-compounds.
The sodium salt of the beta-naphthoxy-acetic-beta-sulpho-acid thus obtained
crystallizes in short bright rhombic plates, which are colourless or slightly tinged
with red. It is but slightly soluble in cold water, more readily in hot water, and
scarcely soluble in alcohol. It is probably a neutral salt of the constitution
represented by the formula,
If a hot aqueous solution be treated with an excess of hydrochloric acid, delicate
colourless acicular crystals separate out on cooling. This is probably an acid salt
and, by addition of alkali, is reconverted into the neutral salt.
EXAMPLE 3. PREPARATION OF THE ALPHA-AMIDO-BETA-NAPHTHOXY-ACETIC-
BETA-SULPHO-ACID.
The nitration of the naphthoxy-acetic-sulpho-acid can be effected by treating its
above described sodium salt with nitric acid in accordance with the directions given
in Example for the nitration of the naphthoxy-acetic-acid. On pouring the
nitration product into ice-water a clear solution is obtained, to this add a large
excess of caustic soda and common salt. The sodium salt of the nitro-body
separates out. Filter off and press, and if desired, purify by redissolving in water
and precipitating with caustic soda.
Next dissolve about two parts of the sodium salt of the nitro-acid in about four
parts of boiling water and add about one part of acetic acid (containing about
twenty per cent. real acid) boil and add gradually to the boiling solution about one
part of iron filings. As soon as the solution loses its yellowish colour neutralize
with soda and filter hot. From the filtrate on cooling a crystalline precipitate
separates out the said precipitate consisting of the anhydride of beta-naphthoxy-
beta-sulpho-acid in the form of a sodium salt. Filter, wash with a little cold water
and press. To hydrate this and convert it into the acid, boil about one part with a
mixture of seven parts of caustic soda solution (containing about 35 per cent. of
sodium hydrate) and five parts of water for about fifteen to thirty minutes.
clear solution is obtained from which the sodium salt soon begins to separate out.
A

page_text: This can be obtained by cooling, filtering, and pressing; but it is better to dilute
the solution obtained as above described and to use that directly in the manufacture
of dyestuffs.
The sodium salt of the anhydride of the beta-naphthoxy-acetic-beta-sulpho-acid
obtained as an intermediate product in the above process has probably the 5
constitution represented by the formula,
it can be obtained in beautiful glittering crystalline scales and is slightly soluble
in cold water but readily soluble in hot water.
The sodium-salt of the alpha-amido-beta-naphthoxy-beta-sulpho-acid prepared
as above described is a powder, which has not yet been obtained in a distinctly
crystalline form, it is very soluble in water but only slightly soluble in caustic soda
solution. On heating with mineral acids it is converted into the anhydride-salt.
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 I
claim is.
First. The manufacture of alpha-amido-beta-naphthoxy-acetic acid by first
preparing alpha-nitro-beta-naphthoxy-acetic-acid, then reducing this body to obtain
an anhydride of the amido-body and finally hydrating this anhydride, all
substantially as hereinbefore described.
Second. The manufacture of beta-naphthoxy-acetic-beta-sulpho-acid by the
action of mono-chlor-acetic-acid on Schaeffer's beta-naphthol-mono-sulpho-acid
substantially as hereinbefore described.
Third. The manufacture of alpha-amido-beta-naphthoxy-acetic-beta-sulpho-acid
by nitrating beta-naphthoxy-acetic-beta-sulpho-acid, then reducing the nitro-
compound to obtain an anhydride of the amido-derivative and finally hydrating
this anhydride all substantially as hereinbefore described.
Fourth. As new products of manufacture the materials for the preparation of
dyestuffs herein before described namely alpha-nitro-beta-naphthoxy-acetic-acid;
alpha-amido-beta-naphthoxy-acetic-anhydride; alpha-amido-beta-naphthoxy-acetic-
beta-naphthoxy-acetic-beta-sulpho-acid; alpha-nitro-beta-naphthoxy-acetic-
beta-sulpho-acid; the anhydride of alpha-amido-beta-naphthoxy-acetic-beta-sulpho-
acid; and alpha-amido-beta-naphthoxy-acetic-beta-sulpho-acid.
acid;
Dated this ith dow of Na 1901
J. H. JOHNSON & Co.,
Agents.