Manufacture of Naphthasetoldisulphonic Aoids and of New Colouring Matters Derived therefrom.
Year: 1898

page_text: Manufacture of Naphthasetoldisulphonic Aoids and of New
Colouring Matters Derived therefrom.
I, OLIVER IMRAY, of Birkbeck Bank Chambers, Southampton Buildings, in the
County of London, Chartered Patent Agent, do hereby declare the nature of this
invention, (which has been communicated to me from abroad by the Society of
Chemical Industry in Basle, Basle, Switzerland, Chemical Manufacturers), and in what
manner the same is to be performed, to be particularly described and ascertained
in and by the following statement :-
My foreign correspondents have found that by acetylising certain amidonaphtholdı-
sulphonic acids by appropriate means an acetyl group can he introduced into the
amido-group whereby the acids lose the properties which characterise them as
derivatives of amidonaphthols and assume entirely the characteristics of naphthol
sulphonic acids. If, as has been proposed by O. N. Witt and Dedichen in the Berichte
der deutschen chemischen Gesellschaft, Vol. xxix, page 2947, the amidonaphthol
acetylised in the amido-group be distinguished by the name "naphthacetol," the
acids described below must be considered as naphthacetoldisulphonic acids, and
consequently the colouring matters derived froin them and containing the acetyl
group are naphthacetol derivatives and may be briefly desiguated "acetylene colouring
matters."
So far as 18 at present known, by the researches of my correspondents, the
naphthacetoldisulphonic acids which especially possess peculiar technical interest are
the 1. 8 3 6-, 18: 2 4,1 8. 4. 6-, and 1. 5. 3 7-acids, while
the 2. 8. 6-naphthacetolsulphonic acid and 2 8 3. 6-naphthacetoldisulphonic
acid, which contain the acetamido-group in the ẞ-position are only of secondary
interest.
The following example illustrates the method for preparing these substances
5 parts of the 1: 8. 3. 6- amidonaphtholdisulphonate of sodium-well dried
and finely powdered, are mixed with 15 parts of anhydrous sodium acetate, 2.5 parts
of acetic anhydride and 2 parts of glacial acetic acid; the mixture is boiled gently
man oil bath, the vessel being provided with a reflux condenser, until a sample
withdrawn from the mixture and dissolved in water no longer gives a colour when
treated with a little acid and sodium nitrite and on addition of a solution of sodium
carbonate.
The product of the reaction obtained in this way consists principally of a mixture
of the sodium salts of the required 1:8:3 6-naphthacetoldisulphonic acid and of a
diacetamidonaphtholdisulphonic acid, and sometimes even of this last acid alone if
the acetylisation has occurred very energetically
Unlike the naphthacetoldisulphonic acid which combines easily with diazo-,
compounds yielding extremely beautiful azo-colouring matters, this diacetamido-
•

page_text: naphtholdisulphonic acid 18 indifferent towards diazo-compounds and is consequently
valueless for the preparation of azo-colouring matters.
The diacetylised acid can be at once easily and quantitatively transformed into
naphthacetoldisulphonic acid by heating it, either by itself or mixed with the
naphthacetoldisulphonic acid, with some alkali or dilute acid or even by mere
prolonged boiling with water
To this end the mixture from the reaction, after the acetic acid has been distilled
away, is dissolved in water and heated for a short time at a temperature of from 80°
to 90° C. with a 5 per cent. solution of sodium carbonate On account of its great
solubility naphthacetoldisulphonic acid can only be isolated with great difficulty and
with considerable loss of material; it is therefore most advantageously kept in
solution for its diverse uses.
If, in the foregoing example, for the 1: 8:3: 6-amidonaphtholdisulphonic acid
there be substituted 1:8:4: 6-, 1:8:2: 4-, or 1:5: 8: 7-amidonaphthol-
disulphonic acid there will be obtained in an analogous manner 1:8:4:6-,
1:824, or 1 5:3: 7-naphthacetoldisulphonic acid. The proportions, and the
duration and temperature of heating may be varied within sufficiently wide limits,
and my foreign correspondents consequently are not limited strictly to the numbers
given in the example For the acetic anhydride may be substituted acetyl chloride
or substances which will act like acetic anhydride under the conditions of the
reaction.
The naphthacetoldisulphonic acids are characteristically distinct from the
amidonaphthol sulphonic acids from which they are derived and therefore yield
colouring matters different from those furnished by the last mentioned acids.
While the amidonaphthol sulphonic acids are relatively difficultly soluble in water,
the naphthacetol sulphonic acids are very soluble and are precipitated by acids only
from concentrated solutions of their salts and not, therefore, under conditions under
which the amidonaphtholdirulphonic acids are precipitated This difference of
solubility may therefore be used for separating the naphthacetoldisulphonic acids
from admixed amidonaphthol-disulphonic acids.
The naphthacetoldisulphonic acids and the azo-colouring matters derived from
them are not attacked by nitrous acid. With diazo-compounds they yield both in
alkaline and feebly acid solution one and the same series of colouring matters, while
the amidonaphtholdisulphonic acids yield under these conditions two distinct series
of colouring matters Thus, the naphthacetoldisulphonic acids react only with one
molecular proportion of a diago-compound.
As to the colouring matters derived from naphthacet oldisulphonic acids, the
monazo-colouring matters furnish on wool blue-red to violet tints and the disazo-
colouring matters furnish on unmordanted cotton violet to blue tints of a more
brilliant and pure shade than the analogous colouring matters derived from the
amidonaphtholdisulphonic acids. They are resistant to acids and are not altered by
dilute solutions of nitrous acid.
The colouring matters derived from naphthacetoldisulphonic acids are at once of a
much more blaish and more beautiful shade than those derived from the correspon-
ding naphtholdisulphonic acids which do not contain the acetamido-group.
For these reasons the application of the naphthacetoldisulphonic acids leads to
technical effects which it was impossible to obtain heretofore, either by the use of
the amidonaphtholdisulphonic acids or of the corresponding naphtholdisulphonic acids.
The following examples illustrate the preparation of the monazo-colouring matters,
the intermediate products and the disazo-colouring matters :—

page_text: The colouring matter thus formed 18 precipitated by addition of common salt; it
dyes wool, in an acid bath, a very pure and uniform bluish-red. There are obtained
with diazobenzene sulphonic acid a red of a little yellowish shade, with diazotoluene
and diazoxylene reds which are still more blue than that just mentioned, with
paradiazoacetanilide a brilliant red violet, with diazonaphthalenesulphonic acids
violet reds, with 1: 4-diazoacetnaphthalide a violet blue and a similar product, fast
alkalies and dyeing very uniformly on wool, by reducing, by means of sodium sulphide,
the colouring matter derived from one molecule of paranitrodiazobenzene and one
molecole of naphthacetoldisulphonic acid.
1.84 parts of benzidine, or 2.12 parts of tolidine, or 2.44 parts of dianisidine or
an equivalent quantity of diamidostilbene, are diazotised in the usual manner by
means of 5.5 parts of hydrochloric acid and 4-6 parts of a 30 per cent solution of
sodium nitrite; the solution of the tetrazo-compound thus obtained 18 introduced
into a cold aqueous solution of 3.6 parts of naphthacetoldisulphonic acid containing
an excess of sodium carbonate or sodium acetate. The intermediate product at once
separates in the form of a dark masa, except when diamidodiphenolether (dianisidine)
is used when the larger part remains in solution
As soon as the free tetrazo-compound has disappeared there is introduced into the
mass one molecular proportion of one of the substances hereinafter specified and
the formation of the colouring matter is effected by agitating the mixture for some
hours and then heating to the boiling point; the colouring matter is precipitated by
common salt, filtered, pressed and dried. Among the compounds which may be
added to the non-diazotisable intermediate products for producing colouring matters,
the following are particularly advantageous, namely.
(a) a-naphthol (1·5 parts), 8-naphthol, 2 : 6- and 2·7- dioxynaphthalenes and the
like. The colouring matters produced dye unmordanted cotton very pure tints
passing from violet to blue-green, benzidine yielding particularly the redder and
dianisidine the blue tints, while tolidine and diamidostilbene yield intermediate
tints; none of these colouring matters is modified by nitrous acid either in solution
or on the fibre.
(b) 14, 15-, or 2 6-naphtholsulphonic acid 2.5 parts naphtholcarboxylic acid
or the like; these yield reddish to greenish blues of great purity and not altered by
nitrous acid.
(o) amidonaphtholdisulphonic acids (3.3 parts), and particularly the 1: 8:3: 6-,
18.4:6, 18:2: 4-, and 1:53: 7- acids, with which the intermediate pro-
ducts form, in alkaline solution, colouring matters which vary from blue to blue-green
and are of great purity. These colouring matters contain only one diazotisable
amido-group, and consequently absorb only one molecular proportion of nitrous
acid; by diazotisation on the fibre and development with B-naphthol or
metaphenylenediamine, they yield trisazo-colouring matters with a variation in tint,
not towards black, as is the case with the so called diamine colouring matters, but
towards deep blue.
(d) a-naphthylamine (1 parts), paraxylidine and paracresidine which, when
combined in an acetic acid solution with the intermediate products, yield intense
tints varying from mauve to violet and passing by diazotisation on the fibre and
development with 8-naphthol to fast shades varying from violet to blue. Instead of
a-naphthylamine, paraxylidine or paracresidine, amidonaphthols and diamines may be
used in which case, also new colouring matters will be obtained
(e) 2
8: 6- amidonaphtholsulphonic acid (2.3 parts) which combines with the
intermediate products yielding violets when the combination occurs in an acetic acid
solution, and blues when it occurs in an alkaline solution; these blues, by diazotisation
on the fibre and development with 8-naphthol or metaphenylenediamine, pass to a
dark blue, while the analogous diamine colouring matter, that is diamine-black B.H.,
is developed, under the same conditions, to a black.

page_text: The production of colouring matters occurs in a similar manner, if, instead of
simple tetrazo-compounds, azoteraz -compounds are used, or the naphthacetol-
disulphonic acids are combined with the known intermediate products used for the
preparation of disazo colouring matters and produced by the combination of one
molecular proportion of a tetrazo-compound and one molecular proportion of another
suitable compound But as the naphtbacetoldisulphonic acids combine, generally
speaking, a little slowly, and react a little less smoothly, with these known inter-
mediate products than with the new intermediate products derived from one
molecular proportion of a naphthacetoldisulphonic acid and one molecular proportion
of a tetrazo-compound, it 18 most frequently preferable to use these new intermediate
products.
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 :-
1. Manufacture of naphthacetoldisulphonic acids or their salts by heating amido-
naphtholdisulphonates with acetylising agents, preferably with acetic anhydride and
glacial acetic acid (until a sample taken from the mixture and treated with nitrona
acid no longer shews by its reactions the formation of a diazo-compound), and by
converting the diacetamidonaphtholdisulphonic acids, which are formed at the same
time, into naphthacetoldisulphonic acids (monoacetamidonaphtholdisulphonic acids)
by heating with alkalies or acids in dilute aqueous solutions.
.
•
2. Manufacture of 1:8 3 6-, 1 : 8 : 4 6-, 1:8: 2:4-and 1:5 3: 7-naphth-
acet oldisulphonic acids by acetylising the corresponding 1: 8: 8 6-, 184: 6-,
1:8:24- and 1: 5:3: 7-amidonaphtholsulphonates in the manner referred to in
Claim 1.
3. Manufacture of colouring matters for wool, dyeing from blueish-red to violet, by
combining the naphthacetoldisulphonic acids referred to in Claims 1 and 2, in an
alkaline or feebly acid solution, with the diazo-derivatives of aromatic primary
amido-compounds
4. Manufacture of new non-diazotisable intermediate products by combining one
molecular proportion of the naphthacetoldisulphonic acids referred to in Claims 1
and 2 with one molecular proportion of a tetrazo-compound, in alkaline or acetic acid
solution, and the transformation of these intermediate products into colouring matters
dyeing unmordanted cotton, by combining one molecular proportion of the inter-
mediate products with one molecular proportion of an aromatic monamine, or
diamine, of a phenol, of an amidophenol, of a dioxynaphthalene, or of the sulphonio
acid or carboxylic acid derivatives of these compounds, or with one molecular pro-
portion of a naphthacetol sulphonic acid.
5. Manufacture of intermediate products from one molecular proportion of tetrazo.
diphenyl, tetrazoditolyl, tetrazodiphenol ether, or tetrazo-stilbene, and one molecular
proportion of 1:8:3:0, 1:8:4:6, 1:8.2: 4-, 1:6:3: 7-naphthacetoldi-
sulphonic acids, and the transforination of these intermediate products into violet
and blue colouring matters, dyeing unmordanted cotton, by combining one mole-
cular proportion of these intermediate products with one molecular proportion of
a-naphthol, 8-naphthol, a-naphthylamine, 8-naphthylamine, paraxylidine, para-
cresidine, 1: 4-, 1:5-, 2:8- etc. naphtholsulphonic acids, 1: 8:4- or 2.8: 8- amido-
naphtholmonosulphonic acid (in alkaline or acetic acid solution), 1:8: 8: 6-,
1: 8 4 6-, 1: 8:2: 4-, and 1:5: 8: 7-amidonaphtholdisulphonic acid, 1:8:4
dioxynaphthalenemonosulphonic acid and 1:8:2:4- dioxynaphthalene-disulphonic
acid, in alkaline solution.
6. Manufacture of colouring matters from the naphthacetoldisulphonic acids
referred to in Claims 1 and 2, by combining the said acids with intermediate pro-
ducts still capable of coupling and formed in the known manner from one molecular
proportion of a tetrazo-compound and one molecular proportion of a compound
applicable for the formation of azo-colouring matters.

page_text: 7. As new raw materials for the manufacture of colouring matters, the naphth-
acetoldisulphonic acids referred to in Claims 1 and 2.
8. As new industrial products the inonazo- disazo- and polyazo-colouring matters
capable of being prepared according to the processes referred to in Claims 3, 4, 5
and 6.
ABEL & IMRAY,
Agents for the Applicant.