The Manufacture of Dyestuffs from Oxyethers of Alpha Naphtylamine and their Sulphoacids.
Year: 1889

page_text: Date of Application, 27th Apr., 1889
Complete Specification Left, 23rd Jan., 1890-Accepted, 1st Mar., 1890
The Manufacture of Dyestuffs from Oxyethers of Alpha
Naphtylamine and their Sulphoacids.
I, SYDNEY PITT of Sutton in the County of Surrey Gentleman (a communication
to me from abroad by Leopold Cassella & Co. of Frankfort-on-Main in the Empire of
Germany Manufacturing Chemists) do hereby declare the nature of this Invention to
be as follows:-"
Oxyether groups, can be introduced. into a naphtylamine and dyestuffs of great value
and of special properties may be obtained from these substituted bases or their
sulfoacids.
I.
The simplest way is to depart from the naphtolethers transforming the same into
their nitro-derivatives and treating these with reducing agents. Likewise the mono-
nitronaphtols can be transformed into ethers and then reduced.
Example: 172 kilo. of naphtolethylether I introduce into 30 kilo. of nitric acid
of 40° Bé. taking care that the temperature does not exceed 40° C. The nitro product
is washed with water and reduced by means of 20 kilo. of iron in presence of hydro-
chloric acid or acetic acid. I dissolve the reduced product in diluted hot hydrochloric
acid and precipitate from the solution the chlorhydrate by excess of muriatic acid or
the sulphate by the addition of Glauber's salt. The salts can be purified by
crystallisation.
In an analogous manner I obtain the methyl amyle or benzyl ethers.
The bases are difficultly soluble in water easily soluble in alcohol and ethers, these
solutions have a violet fluorescence. The chlorhydrates are pretty easily soluble in
hot water less soluble in cold water, the sulphates are difficultly soluble.
II.
In order to obtain sulphoacids, the thus obtained bases can be treated with fuming
sulphuric acid at not too high temperatures, or the nitrouaphtol ethers
can be
sulphonated and reduced. It is however more advantageous to depart from the ethers
of naphtolsulphonic acids (which are obtained by sulfonating the naphtol ethers, or
by transforming the naphtol sulfoacids into ethers) to nitrate and then to reduce.
Example: 24'6 kilo. of F. naphtolsulphonate of sodium, I dissolve with 4 kilo.
hydrate of sodium in 200 litres of 50% alcohol. I then add 11 kilo. of bromethyl
and heat several hours to 60. 80° C. When cooling down the sulphonaphtolethylether
crystallises in silvery large crystals. I then filter and put the dry ether into cooled
nitric acid of 40° Bé., in which it dissolves with a dark yellow colour. I then pour the
solution in water and by means of common salt the nitro sulphonaphtolethylether will
be precipitated in yellowish shining crystals. By reducing agents as for instance
Zn and HCl I obtain immediately the pure oxethylnaphtylaminesulphonic acid in
form of colourless needles, which are very difficultly soluble in water.
In a similar manner I obtain other ethers as methyle amyle, benzyle. The other
naphtolmono and disulphonic acids react in an analogous manner.
III.
Diazo and tetrazo compounds react upon the new bases and sulphoacids forming
new dyestuffs.
Example:-30 kilo of nanhtelamins disulabonia anid
1 1
°

page_text: together with a solution of 21 kilo. methoxy a naphtylamine chlorhydrate; the dyestuff
will be immediately formed and precipitated.
Or 184 kilo. benzidine are diazotized and brought together with a neutral solution
of 50 kilo.
amidosulphonaphtolethylether, after allowing to stand a short time a
a
reddish violet dyestuff will be formed.
Thus a large number of new dyestuff's can be produced, which are partly valuable
by themselves and partly obtain a special value by the property that their free amido
groups can be diazotized again, and that these tetrazo compounds produce dyestuffs of
a greenish blue shade when combined with phenols and their sulphonic acids with
amines.
IV.
In order to carry into effect the last mentioned reaction I proceed as follows:-
Example: I dissolve in soda the violet body formed by 186 kilo. toluidinemono-
sulphonic acid and the equivalent quantity of amidonaphtolether I add 7 kilo nitrite
of soda and acidulate with hydrochloric acid. The tetrazo compound separates in
form of a yellow crystalline precipitate which I filter and introduce into a solution of
36 kilo. naphtol
disulphonic acid. The dyestuff dyes wool and silk a dark
blue shade.
a
Or I combine 30 kilo naphtylamin disulphonic acid-as mentioned under IV with
amidonaphtolether and then diazotize. The tetrazo compound dissolves in water with
a brown colour. I combine the same with one equivalent of ẞ naphtoldisulphonic
acid. The dyestuff dyes wool and silk a blueish green shade.
Or I combine in an analogous manner 34 kilo. of benzidinedisulphonic acid with
amidonaphtolether and then diazotize. The difficultly soluble tetrazo compound, I
combine with 50 kilo. a naphtol a sulphonic acid. The dyestuff dyes wool, silk and
cotton a dark blue shade.
The colouring matters of shades varying from red to violet deriving from diazo
compounds and the above described sulphonaphtolethers are likewise converted by
nitrous acid into yellow to brown tetrazo compounds, which in combination with
phenols or amines produce valuable dyestuffs of dark greenish blue shades.
Dated this 27th day of April 1889
CARPMAEL & Co.,
Agents.
The Manufacture of Dyestuffs from Oxyethers of Alpha
Naphtylamine and their Sulphoacids.
I, SYDNEY PITT, of Sutton in the County of Surrey, Gentleman, (a communication
to me from abroad by Leopold Cassella & Co. of Frankfort-on-Main in the Empire of
Germany Manufacturing Chemists) do hereby declare the nature of this Invention and
in what manner the same is to be performed to be particularly described and
ascertained in and by the following statement:-
My correspondents have found that dyestuffs of great value and of special
properties may be obtained from the oxyethers of a naphtylamine and their sulpho-
acids.
I.
I first describe the bodies herein termed oxyethers of naphtylamine, and how to
obtain the same.
The simplest way is to start from the naphtolethers transforming the same into
their nitroderivatives, and treating these with reducing agents. Likewise the mono-
nitronaphtols can be transformed into ethers and then reduced.
Example 172 kilos. of naphtolethylether are introduced into 30 kilos. of nitric acid
of 40° Bé. taking care that the temperature does not exceed 40° C.
The nitro

page_text: product is washed with water and reduced by means of 20 kilos. of iron in presence
of hydrochloric acid or acetic acid. The reduced product is dissolved in diluted
hot hydrochloric acid and from the solution the chlorhydrate is precipitated by
excess of muriatic acid or the sulphate by the addition of Glauber's salt. The salts
can be purified by crystallisation.
In an analogous manner, the methyl amyle- or benzyl-ethers are obtained.
The bases are difficultly soluble in water easily soluble in alcohol and ether, these
solutions have a violet fluoresence. The chlorhydrates are prettly easily soluble in hot
water, less soluble in cold water, the sulphates are difficultly soluble.
In order to produce sulphoacids the bases thus obtained can be treated with
fuming sulphuric acid, at not too high temperatures or the nitronaphtolethers can
be sulphonated and reduced. It is however more advantageous to start from the
ethers of naphtolsulphonic acids (which are obtained by sulphonating the naphtol-
ethers, or by transforming the naphtolsulphoacids into ethers) to nitrate first and then
to reduce.
Example: 24'6 kilos. of F. naphtolsulphonate of sodium is dissolved with 4 kilos.
hydrate of sodium in 200 litres of 50%, alcohol. 11 kilos. of bromethyl is then added
and the mixture heated for several hours to 60-80° C. When cooling down the
sulphonaphtolethylether crystallises in silvery large crystals. Then filter and put the
dry ether into cooled nitric acid of 40° Bé. in which it dissolves with a dark yellow
color, then pour the solution into water and by means of common salt precipitate the
nitro-sulphonaphtolethylether; it appears in yellowish shining crystals. By the use
of reducing agents, as for instance zinc and muriatic acid the pure oxethylnaphtyl-
aminesulphonic acid is immediately obtained in the form of colorless needles, which are
very difficulty soluble in water.
In a similar manner other ethers are obtained as methyle, benzyle. Other
naphtol sulphoacids, for instance the so called Schäffer acid, react in an analogous
In order to bring about the last mentioned reaction proceed as follows:-
Example: Dissolve in soda the violet body formed by 186 kilos. toluidinemono-
sulphonic acid and the equivalent quantity of amidonaphtolether; add 7 kilos. nitrite
of soda and acidulate with hydrochloric acid. The tetrazo-compound separates in
form of a yellow crystalline precipitate, which filter out and introduce into a solution
of 36 kilos. ẞ naphtol a disulphonic acid. The dyestuff dyes wool and silk a dark blue
shade.

page_text: Or combine 30 kilos. naphtylaminedisulphonic acid, as mentioned under III with
amidonaphtolether and then diazotize. The tetrazo-compound dissolves in water
with a brown color. Combine the same with one equivalent of ẞ naphtoldisulphonic
acid. This dyestuff dyes wool and silk a blueish green shade.
Or combine in an analogous manner 34 kilos. of benzidinedisulphonic acid with
amidonaphtolether and then diazotize. The difficultly soluble tetrazo-compound
combine with 50 kilos. a naphtol a sulphonic acid. This dyestuff dyes wool silk and
cotton a dark blue shade.
The coloring matters of shades varying from red to violet deriving from diazo
compounds, and the above described sulphonaphtolethers are likewise converted by
nitrous acid into yellow te brown tetrazo compounds, which in combination with
phenols or amines produce valuable dyestuffs of dark greenish blue shades.
Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed 1 declare that what I
claim is:
1. The process of producing coloring matters by the action of diazo compounds, such
as the diazo-derivatives of aniline, toluidine, xylidine a and ẞ naphtylamine, benzidine,
tolidine or their mono- di and trisulpho acids upon the herein described oxyethers of
naphtylamine or their sulpho acids.
a
2. The transformation of the compounds obtained according to first claim into
diazo-azo-compounds by treating them with nitrous acid.
3. The process of preparing coloring matters by acting with the diazo-azo-compounds
obtained according to claim 2 upon phenols or phenolsulpho acids, such as a or
ẞ naphtol or dioxynaphtalines and the mono- di- or trisulphonic acids therefrom.
4. As new articles of manufacture the new dyestuffs obtained as herein described.
Dated this 17th day of January 1890.
CARPMAEL & Co.,
Agents for the Applicant.