DE168299C - - Google Patents

Description

IMPERIAL

PATENT OFFICE.

Through patents 68303 and 128619 it has become known that certain derivatives of o-p · diamidophenol, namely the o-p · diamidophenol-o-carboxylic acid respectively. -osulfonic acid

(OH:

COOH

= 1: 2: 4: 6;

Let tetrazotize smoothly. This contrasts with the behavior of o-p · diamidophenol itself compared to nitrous acid nothing has been known so far. But considering that this m-diamidophenol has quite an analogous constitution, such as e.g. B. m-tolylenediamine

(C i / ₃ : NH ₂ : NH ₂ = 1: 2: 4;
or chloro-m-phenylenediamine

(Cl: NH ₂ : NH ₂ = 1: 2: 4),

which bodies, as is well known, cannot be tetrazotized smoothly by being intermediately forming m-tetrazo compound in statu nascendi, even in the presence of free Mineral acid, would immediately couple with unaltered m-diamine that is still present would have been expected that o-p · diamidophenol

(OH: NH ₂ : NH ₂ = 1: 2: 4)

to nitrous acid would behave analogously to the m-diamines mentioned.

As has now been found, however, this is not the case; on the contrary, the o-p · diamidophenol in the presence of a sufficient excess of mineral acid, can be converted smoothly into the tetrazo compound without this Formation of colorants similar to Bismarck brown occurs. This behavior of the o-p · diamidophenol but could from the already known tetrazotizability of the above ο - ρ · diamidophenol - ο - carboxylic acid or -o-sulfonic acid by no means by analogy can be derived by the tetrazotizability of these bodies by the in o-position carboxyl respectively. Sulfo group which has a protective influence on the neighboring 5-position, where the entry of the diazo group takes place in the Bismarck brown formation, so that the ability of the o-p · diamidophenol-o-carboxylic acid to combine. -o-sulfonic acid in acidic solution is so reduced that the complete tetrazotization occurs sooner than Dye formation can occur. As can be easily seen, with o-p · diamidophenol such a steric hindrance does not exist. Therefore, when o-p · diamidophenol nevertheless not like m-toluylenediamine or chlorophenylenediamine with an analogous structure behaves, but like the op · diamidophenol-o-carboxylic acid respectively. -o-sulfonic acid can be tetrazotized smoothly, this behavior must be quite surprising are designated.

The tetrazotization of o-p'-diamidophenol

is best done at temperatures below o ° C. and in the presence of an abundant Excess mineral acid. This gives a reddish yellow colored tetrazo solution, which is very reactive and z. B. with naphthol sulfonic acid ι: 4 or 1: 5 already combine in acetic acid solution to form a poorly soluble, burgundy intermediate product lets, which then in soda or.

Caustic solution with another molecule of the same or different Azo component can be coupled. The nuances of the dyes obtained in this way vary from burgundy to violet and change into violet-black to green-black by post-treating the dyed fiber with chromium salts etc. The chromed dyes are characterized by excellent flex, light and decade fastness.

The presentation of the new dyes can be seen from the following examples.

Example I.

10 kg diamidophenol chlorohydrate
(OH: NH ₂ : NH ₂ = 1: 2: 4;

are dissolved in a little water and cooled to -5 ^{0 using ice and table salt.} After adding 25 kg of hydrochloric acid (tech.), A 10% nitrite solution containing 7 kg of sodium nitrite is allowed to flow in slowly with thorough stirring. The tetrazo solution thus obtained has a reddish color and is well-preserved, even at ordinary temperature

one in the presence of an excess of sodium acetate with 12.3 kg of naphtolsulfosaurem Soda 1: 4. After a short time, the formation of the red intermediate product is complete, which you can do directly or, if necessary, to remove the brine, afterwards Filtration with 10 kg of ß-naphtol sodium in the presence of excess soda solution expediently combined with gradual heating of the mixture to 40 ° C. In the end If you warm up to 70 to 80 °, the separation of the partially precipitated completes Dye by adding sodium chloride, filtered, pressed and dried. The dye dissolves in hot water violet color that turns red when acids are added, produced on wool in acidic bath clear bordeaux tones, which are extremely washable and washable when chromium plating deliver water-resistant, violet-tinged black.

A dye with very similar properties is obtained by replacing 1: 4-naphthol sulfonic acid by the 1 ^ -naphthol sulfonic acid, 2: 6-Naphtholsulfonic acid sheep r, as well as when replacing ß-naphthol with dioxynaphthalene, e.g. 2: 7-dioxynaphthalene.

Example II.

10 kg of hydrochloric acid diamidophenol, as previously tetrazotized, are mixed with a dissolution of 13 kg of ι: 5-naphthol sulfonic acid in 100 l of water; the red, sparingly soluble intermediate is formed on addition of 30 kg of sodium acetate. After the lapse of one hour ι outputs the same to a means of ice on 5 to io ° accommodated solution of 10 kg Dioxynaphtalin 1: ⁽⁰ 30 Be.) 5 in 1001 of water and 50 kg of sodium hydroxide. The formation of the dye begins immediately and ends after 12 hours. Warming up to 30 to 40 ° speeds it up. The excess alkali is neutralized with hydrochloric acid and the dye is isolated as usual. It creates violet tones on wool, which turn into black when chrome-plated.

The table below shows the characteristics compiled a number of dyes represented by means of tetrazophenol.

Combination of 1 mole. Tetraz. 2: 4 diamido
45 phenol and II. Component Solution in conc.
sulfur
acid Coloring on wool after-
chromed I. component 2: 7-dioxynaphthalene water blue angry deep black 50 ι: 4-naphthol sulfonic acid the same violet-
black black blue Brown violet
black 1: 5-naphthol sulfonic acid • m-amidophenol the same bluish
black bordeaux deep brown
black 55 the same. β - naphtol red-brown blue red-brown black 1: 8- dioxynaphthalene-
3: 6-disulfonic acid ι: 8-amidonaphtol-
4 - sulfonic acid blue blue black , purple the same ⁶⁰ 1: 5-naphthol sulfonic acid blue black the same

Combination of ι mol. Tetraz. 2: 4 diamido
phenol and II. Component Solution in conc.
sulfur
acid Coloring on wool after-
chromed 5 I. component β - naphtol water blue angry black 1: 5-naphthol sulfonic acid the same violet
black blue black red-brown violet
black ¹⁰ 2: 6-naphthol sulfonic acid the same blue black blue bordeaux the same ι 14-naphthol sulfonic acid α-naphtol violet
black blue black violet Brown
black ¹ ^ 1: 5-naphthol sulfonic acid 2: 6-naphthol sulfonic acid purple brown violet
black purple brown black
Brown β - oxynaphtoic acid
FP 216 ° 2: 7-dioxynaphthalene. Brown
black blue Brown black ²⁰ ι: 8-dioxynaphthalene
3: 6-disulfonic acid Resorcinol blue red-brown violet
black Brown
black m - toluenediaminesulfo-
acid ι: 6-dioxynaphthalene yellow-brown violet
black orange brown purple brown 1: 5-naphthol sulfonic acid ι: 2-naphthol sulfonic acid purple brown blue red-brown yellow-brown a - naphtol 2: 7-dioxynaphthalene the same violet the same Brown
black 30th
1: 4- naphthylamine sulfo-
acid Resorcinol red-brown red-brown violet red-brown. the same
35 yellow-brown Red orange

Claims (1)

Pate nt-An SPRU ch:
Process for the preparation of disazo dyes for wool, consisting in that the tetrazo compound of diamidophenol (OH: NH ₂ : NH ₂ = 1: 2: 4) first with 1 molecule of an azo component to a so-called intermediate 80 products are combined and this is then combined with a second molecule of the same or different azo component.