DE83572C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

contains sulfonic acid in the middle position.

Patent specification No. 58306 shows that the naphthol black series of dyes the a-naphthyl-

N Ά

amine can be replaced by the following two sulfonic acids

5O ₃ H

and

It has now been shown that the applicability of these acids for the intended purpose depends on the position of the sulpho groups, and that the nonethoxylated acids, the O _{1, 3} - and α-β ^ -naphthylamine sulphonic acid, can also be used in the middle position. The representation of dyes of this type is protected in patent no.73901, namely the combinations of diazosulfonic acids (naphthoic acid) with the O ₁ ß ₄ - acid and further coupling with amines (a-naphthylamine, phenyl - α - naphthylamine etc.). Other valuable combinations are obtained by combining unsulfated or sulfated diazo bodies with the O ₁ ß ₃ -acid and then further combined with phenols such as ß-naphthol, its sulfonic acids, and amidonaphthol sulfonic acids; or by adding diazocarboxylic acids with the CL ₁ ß ₃ - acid

/ OC ₂ H,

combines and then further combined with phenols or amines.

I. Dyes from unsulfurized diazo compounds.

Example: 14.3 kg of 0. - naphthylamine are diazotized and the diazo compound is added to the solution of 25 kg of the sodium _{salt of Ct 1} ß ₃ -naphthylamine sulfonic acid. To terminate the reaction, the free mineral acid is truncated with sodium acetate. The precipitated amidoazosulfonic acid is dissolved in dilute sodium hydroxide solution, 7 kg of nitrite are added to the solution and acidified with hydrochloric acid. The diazo-azo compound is sparingly soluble. It is filtered off and added to the alkaline solution of 36 kg of β-naptol disulfonic acid R.

The dye separates out. He dyes wool blue-black.

In an analogous manner, dyes are obtained from the diazo compounds of aniline and its homologues or from other naphthol derivatives. the Nuances of such combinations are the following:

combined with
^α ι ßs ~ naphtylamine sulfo-
acid Diazo compound of: aniline ρ-toluidine α-naphthylamine ß-naphtylamiri dyes wool in an acid bath purple black
grey black purple black
grey black blue black
black (reddish)
deep black black
black (reddish)
deep black. and with ß-naphthol disulphonic acid R ..
Ci ₁ a ₂ -naphthol sulfonic acid ...
γ- amidonaphthol sulfonic acid

II. Dyestuffs from sulfated diazo

links.

Example: 24.5 kg of naphthoic acid sodium are dissolved in 300 liters of water and diazotized; the neutral solution of 24.5 kg of the sodium _{salt of Ci 1} ß ₃ -naphthylamine sulfonic acid is then run in, and an excess of acetic acid sodium is added. The amidoazodisulfonic acid formed remains dissolved with a brown color. If you now add hydrochloric acid and 7 kg of nitrite, the poorly soluble diazoazodisulfonic acid is formed. The latter is added to the alkaline solution of 25 kg Ci ₁ α with soda., - Naphthol sulfonic acid. The dye is precipitated with table salt. He dyes wool blue-black.

The naphthylamine sulfonic acid can also be replaced by other monosulfonic acids the naphthol sulfonic acid by other naphthol derivatives. The nuances of some embodiments result from the following compilation :

combined with Sulfanilic acid Diazo compound of: Naphthoic acid Ci ₁ ß ₃ - naphthylamine sulfonic acid
and with ß-naphthol disulphonic acid R
Ct ₁ a. ₂ - naphthol sulfonic acid
y-amidonaphthol sulfonic acid purple black
grey black 0 -Toluidine sulfonic acid blue black
deep black dyes wool in an acid bath purple (blackish)
grey black

or: 34.7 kg of Ct ₁ -naphthylamine-β ₂ β ^ -disulphonic acid are diazotized and added to the solution of 24.5 kg of the sodium _{salt of C 1} β ₃ -naphthylamine sulphonic acid. The amidoazo body forms immediately. It is transformed by diazotization into the brown colored diazoazotrisulfonic acid which can be precipitated by common salt. If this is added to an alkaline solution of 36 kg of ß-naphtholedisulphonic acid R, a very easily soluble dye is formed, which is deposited by salting out. He dyes wool blue-black.

Instead of α - naphtylamine disulfonic acid, ß-naphtylamine disulfonic acid, a different naphthol derivative can be used instead of R-salt.

Valuable combinations are the following:

combined with Diazo compound of: ß, -naphthylamine- (3 ₃ ß ₄ -disulfonic acid purple black
blue black. Ct ₁ ß ₃ - naphthylamine sulfonic acid
and with a ₁ -naphthylamine-ß ₂ ß ₄ -disulfonic acid dyes wool in an acid bath ß-naphtol
ßi ßä - naphthol sulfonic acid
ß-naphthol disulphonic acid R purple black
blue black

Claims (1)

III. Dyes from carboxylated diazo compounds. Example: 20 kg of p-amidosalicylic acid are diazotized and the diazo compound is added to a solution of 24.5 kg of the sodium _salt of α ß ₃ -naphthylamine sulfonic acid. The amidoazosulfocarboxylic acid formed after about 24 hours is dissolved in alkalis and diazotized with the aid of 7 kg of nitrite. The sparingly soluble, brown colored diazoazo-sulphocarboxylic acid formed is introduced into the dilute solution of 17 kg of monoethyl-a-naphthylamine in 12 kg of hydrochloric acid. The dye formation is complete after a few hours. It is then made alkaline with soda, and the precipitated dye is filtered off. He dyes chrome-stained wool, as well as wool in an acid bath, blue-black. If the ethyl-a-naphthylamine is replaced by other components, one also obtains Dyes, which wool both directly and with the use of ghromite stains to dye. Valuable results
End components: give the following Amidosalicylic acid ß-naphtol combined with Ci ₁ ßg-Naphtylaminsulfosäure and with £ 1
rt in
Ci CD
, Λ B
ί ^ Λ Ο
CCL PLtI
-es ρ
ag 0 a-naphthyl
amine Ethyl-a-
naphtylamine y-amido
naphthol sulfo-
acid blue
black XS.
.2 "«
I Gh
approx II
Gj (Sl
«$
a blue
black black-
blue violet
black blue
black black
green. colors
chrome-stained wool blue
black
(reddish). blue
black Pateντ claims:
Process for the preparation of secondary disazo dyes which _{contain O 1} βg-naphthylamine sulfonic acid in the middle position, consisting in that diazo bodies are combined with that acid, the resulting amidoazosulfonic acids are further diazotized and combined with phenols or amines. The particular embodiments of the method protected by claim 1, consisting in that the diazo compounds of aniline, p-toluidine, a- or ß-naphthylamine, sulfanilic acid, ο -toluidinsulfonic acid, naphthionic acid combined with O ₁ ß ₃ -naphthylamine sulfonic acid and the diazo compounds of the resulting amidoazomonobesw. disulfonic acids are combined with ß-naphthol disulfonic acid R, OL ₁ α, -naphthol sulfonic acid, y-amidonaphthol sulfonic acid, the diazo compounds of a _x ß, ß ₄ - or U ₁ ß ₃ a ₄ -naphthylamine disulfonic acid with a. _x ßg-naphthylamine sulfonic acid combined and the diazo compounds of the amidoazotrisulfonic acids formed are combined with ß-naphthol, ßj ß ₃ -naphthol sulfonic acid, ß-naphthol disulfonic acid R, the diazo compound of p-amidosalicylic acid combined with Ci ₁ ß ₃ -naphthylamine sulfonic acid and the diazo compound of the resulting diazoazosulfocarboxylic acid is combined with ß-naphthol, ß ₁ ß ₄ -dioxynaphthalene, Ct ₁ a. _2- naphthol sulfonic acid, U ₁ ß ₂ -naphthol sulfonic acid, C ₁ ß ₂ ß ₄ -naphthol disulfonic acid, α-naphthylamine, ethyl-α-naphthylamine, γ-amidonaphthol sulfonic acid. Confirmed by decision of the Imperial Patent Office of January 26, 1899 by decision of the Reichsgericht dated January 3, 1900, the patent 83572 is through Deletion of claim 1 has been partially declared null and void.