DE90212C - - Google Patents

Description

IMPERIAL

PATENT OFFICE ^

in LUDWIGSHAFEN a. Rh.

In the patent specification No. 79570 a method for the preparation of basic dyes described, which are derived from phenanthrophenazine. These contain an alkyl or phenyl etc. on the azine nitrogen. Group and are therefore referred to as "phenanthrophenazines substituted on the azine nitrogen" been.

It was observed that in this class of compounds the presence of an alkyl or phenyl, etc. group is an absolute requirement for the formation of a permanent dye. This also seemed to apply to the derivatives of phenanthronaphtazine, because the sulfonic acids of the only known body of this type, the "Eurhodol" or p-oxyphenanthronaphtazine described by Witt (Ber. XIX. P. 2793), whose hydroxyl group is in a ₂ position located

proved to be quite unstable to soap and alkalis and thus useless as dyes.

Of the other oxyderivatives of phenanthronaphtazine, the one with the hydroxyl group in a ₃ -position respectively showed. its sulfoderivatives still resemble Eurhodol. All the more surprising was the perception that the sulfonic acids of the third of the three possible α-oxyphenanthronaphtazines, namely that with the hydroxyl group in the peri (position of an azine nitrogen

yellow wool dyes are very fast. Can be used to represent the new dyes

man

a) either condense a U ₁ ß _x - diamidonaphtol with phenanthrenequinone to form an oxyphenanthronaphtazine and convert it into soluble form by sulphation, or

b) Condensing sulfonic acids of diamidonaphthols of the type mentioned with phenanthrenequinone and thus get directly to water-soluble dyes.

Example I.

Representation of a dye by condensation of phenanthrenequinone with diamidonaphtol and subsequent

Sulfonation.

_{The Ct 1} ßj-diamido-a ₄ -naphtol necessary for the preparation of the peri-oxyphenanthronapthazine is obtained by reducing sulfanilazo - P ₁ - amido - ct ₄ - naphthol, which is obtained by combining diazosulfanilic acid with β _x - amido-α ₄ -naphtol was produced in acetic acid solution.

37 kg of the sodium salt of the azo dye are reduced in a known manner in about 1 percent neutral or weakly acetic acid solution with zinc dust. The resulting Ct ₁ P ₁ -diamido-Ct ₄ -naphtol is not deposited due to its instability. Rather, the solution thereof filtered from the zinc dust is used directly. The same is applied to a weak acetic heated to 90 ⁰ C. solution of 20 kg phenanthrenequinone 100 kg bisulfite as 40 ° and 1000 1 of water.

When heated to 90 to 95 ^° C., the condensation product separates out. The reaction is ended when nothing more is deposited from a filtered sample on prolonged heating. The peri-oxyphenanthronaphtazine formed is separated from the mother liquor by filtration, washed, dried and boiled with alcohol for purification. It is very sparingly soluble in the common solvents and, in contrast to the Eurhodol by Witt mentioned at the beginning, also almost insoluble in alcoholic sodium hydroxide solution; In concentrated sulfuric acid, peri-oxyphenanthronaphtazine gives a green-blue solution, while Eurhodol dissolves with a pure blue color.

The oxyphenanthronaphtazine is stirred with 5 parts of cold, fuming sulfuric acid from 23 pCt. free anhydride content until a sample dissolves in dilute caustic solution one has a sulphonic acid, which is rather sparingly soluble even in hot water, which is found on wool turns a somewhat cloudy yellow.

With 5 parts of fuming sulfuric acid of 23 pCt. Anhydride content arises at 40 ° C. a sulphonic acid which is already soluble in cold water, its sodium salt, which is also easily soluble is precipitated from the solution by means of common salt; it also turns a cloudy yellow.

Example II.

Representation of a dye by condensation of phenanthrenequinone . with diamidonaphthol sulfonic acids.

The azo dye prepared from diazosulfanilic acid and β-amidoct ₄ -naphthol-β ₃ -sulfonic acid in acidic solution is suspended in twenty times the amount of hot water, mixed with hydrochloric acid and tin chloride until it is discolored. After cooling, the precipitated! Crystallization is separated from the mother liquor and washed out well with dilute hydrochloric acid. The H ₁ P ₁ - diamido - a ₄ - naphthol - P ₃ - sulfonic acid obtained in this way is sparingly soluble in water; Particularly characteristic of these diamidonaphthol sulfonic acids, as for those listed below, is the property of condensing with phenanthrenequinone to form alkaline-fast yellow dyes. The formation of a phenanthronaphtazindenvate also proves the ortho position of the amido groups. The condensation is carried out as follows:

402 kg of a 5 percent phenanthrenequinone paste are mixed with 260 kg of a 10 percent paste of Ct ₁ P ₁ - diamido - a ₄ - naphthol-P ₃ -sulfonic acid and heated to 90 to 95 ° C. after adding 350 liters of water until the phenanthrenequinone has disappeared and a sample of the mixture is soluble in hot water until it is clear with a yellow color. When this point is reached, the condensation product formed is completely precipitated with common salt and separated from the mother liquor by filtration. The yellow dye thus obtained is entirely crystalline, it is very sparingly soluble in water and is expediently used in the form of a paste; The sodium salt is also sparingly soluble in water, and the dye dissolves in concentrated sulfuric acid. green-blue color.

If the diamidonaphthol sulfonic acid mentioned is replaced in this example by the Ct ₁ P ₁ -diamido-Ct ₄ -naphthol-a ₂ -monosulfonic acid or the O ₁ P ₁ -diamido-a ₄ -naphthol-ct ₃ -monosulfonic acid, in Sulphonic acids hardly soluble in cold water; if, however, the corresponding amount of Ct ₁ P ₁ - diamido - a ₄ - naphthol -a ₃ ß ₄ -disulfonic acid or the α _λ P ₁ -diamido -Ct ₄ -naphthol-ß ₂ ß ₈ -disulfonic acid is used in this process, see above more easily soluble sulfonic acids are obtained, which at the same time show a purer yellow tone.

In all cases, these diamidonaphthol sulfonic acids are best prepared by reducing the azo dyes of the corresponding amidonaphthol sulfonic acids. This creates the α j P ₁ - diamido-α ₄ -naphtol-α. ₂ -monosulfonic acid

in the reduction of azo dyes, which are formed by _{combining diazo compounds with Ct 1} ct ₄ - amidonaphthol - a ₂ - monosulfonic acid in acidic solution. The Ct ₁ ßj-diamido-α ₄ -naphtol-α ₃ -monosulfonic acid by reduction of an azo dye prepared in acidic solution from Ct ₁ ct ₄ -amidonaphtol-a ₃ -monosulfonic acid, the Ct ₁ ßj - diamido-a ^ -naphtolßj β ₃ - disulfonic acid by reducing an azo dye prepared in acidic solution from A ₁ a ₄ - amidonaphtol - ß ₂ ß ₃ -disulfonic acid and the Ct ₁ ßj-diamido-Ct ₄ -naphtol-ct ₃ ß ₄ -disulfo-

SO, H

OH

acid by reducing an azo dye of the Ct ₁ Ct ₄ amidonaphthol - Ct ₃ ß ₄ - disulfonic acid. The diamidonaphthol sulfonic acids mentioned are obtained in crystalline form on reduction with hydrochloric acid and tin chloride; the differences which the dyes shown therefrom show are compiled in the table below.

The position of the sulfo groups in these dyes corresponds to the position of the sulfo groups in the starting materials, e.g. B. arises from

SO, H

SO, H

H ₉ N

SO, H

Phenanthrenequinone + "' ^ö

In those resulting from subsequent sulfonation of the peri-oxyphenanthronaphtazine Sulfonic acids (example i) is the position of

Sulfo groups unknown. - The more detailed characteristics of the dyes result from the following Tabel:

dye . In water In diluted
Caustic soda In cone.
sulfur
acid coloring
on
Wool peri-oxyphenanthronaphtazine with rough
cold sulfonated sulfuric acid
according to example I. pretty hard
also soluble in
hot water easily soluble reddish blue cloudy yellow peri-oxyphenanthronaphtazine with rough
chender sulfuric acid at 40 ° sulfo
not according to example I. pretty easy
soluble easily soluble reddish blue cloudy yellow peri - Oxvphenanthronaphtazine mono-
sulfonic acid from α _l β j - Diamido - α ₄ -
naphtol - ß ₃ - monosulfonic acid according to
Example II very poorly soluble;
more easily soluble in
hot water very poorly soluble;
more easily soluble
in hot lye green Blue yellow peri - oxyphenanthronaphtazine mono-
sulfonic acid from Ci ₁ ß ^ Diamido-a ,, -
naphtol - a ₂ - monosulfonic acid according to
Example II poorly soluble;
pretty easy
soluble in heifsem
water poorly soluble;
pretty easy
soluble in hot
Lye blue green yellow reddish peri - oxyphenanthronaphtazine mono-
sulfonic acid from α _τ β j - Diamido - α ₄ -
naphtol - « ₃ - monosulfonic acid after
Example II poorly soluble
also in heifsem
water quite soluble;
in hot lye
easily soluble blue yellow peri - oxyphenanthronaphtazine disulfo-
acid from a _x ßj-Diamido-ct ^ -naph
tol - β 2 β 3 - disulfonic acid according to Bei
game II easily soluble easily soluble green Blue pure yellow peri - oxyphenanthronaphtazine disulfo-
acid from H ₁ ß ^ Diamido-c ^ -naphtol-
Ct ₃ ß ₄ - disulfonic acid according to Example II easily soluble easily soluble violet pure yellow ..

Claims (1)

Patent Claims: Process for the preparation of yellow dyes, consisting in using phenanthrenequinone either a) condensed with peri-oxy-ctj ß _x - diamidonaphthalenes and sulfonated the oxyphenanthronaphtazines obtained by known methods;
. b) or condensed with sulfonic acids of the diamidonaphthols mentioned under a).
The embodiment of the process protected by claim ι using ad a) Ci ₁ ß _x - Diamido-a ₄ -naphtol, ad b) Ci ₁ B ₁ - Diamido - a _i - naphtol a ₂ - monosulfonic acid,
a _x β j - Diamido - a ₄ - naphtol a ₃ - monosulfonic acid,
O ₁ P ₁ - Diamido - a ₄ - naphtol ß ₈ - monosulfonic acid,
CL ₁ β j - Diamido-α ₄ -naphtol- «3 ß ₄ - disulfonic acid
a j ßj-Diamido-α ₄ -naphtol-ß ₂ 'ß ₃ - disulfonic acid.