DE1049996B - Process for the production of basic dyes of the phthalocyanine series - Google Patents

Description

BUISDIiSREPUBL (K iJKUTSCHLANI)

GERMAN

PATENT OFFICE

Class 22e 7/02

INTERNAT. KL. C 09 b ₍

lh C '

EXPLAINING PAPER 1049 996

B 43925 IVb / 22 e

A NMELDE T AG: MARCH 16, 957

BEKAMVTMACtIUJNG THE AHM (LDDNG
LIiNU AUSGAUIi THE
EDITORIAL; FEBRUARY 5, 1959

It has been found that new basic dyes of the phthalocyanine series are obtained if one uses plithalocyanine sulphocene noride with compounds of the general formula

H ₄ N -R-

NH-R '

converts, in which R is an alkylene or cycloalkyl group and R 'is a branched aliphatic or a cycloaliphatic Rest means.

Suitable phthalocyanine sulfochlorides are, for. B. the Ice, tris or tetrakis sulfochlorides of copper, Nickel, cobalt, iron or aluminum phthalocyanine or metal-free phthalocyanine, the sulfochlorides can also differ from substituted. Phthalocyanines]! derive such as B. of mono-, di-, tri- or tetrachloro or Tetra-phthalocyanine or mono- or diaza-phthalocyanine or naphthalocyanine.

As compounds of the general type

H ₂ NR-NHR ',

where R and R 'have the meaning given above, may be mentioned, for example: N-isopropyl-, N-isobutyl-, N-isoamyl- or N-cyclohexyl-propylenediamine- (1,3), N-isopropyl- or N-isoamyl-ethylenediamine (available z. B. by the method of German patent specification 446 547), N - isopropylbutylenediamine - (1,4) (available by reducing ω-isopropylaminobutyronitrile), N-isopropyl-pentylcndiamine- (t, S) (obtainable by reducing ω-isopropylaminovalcronitrile) or 1-isopropylamino-2-aminocyclohexane (obtainable from 1,2-dinitrocyclohexane by catalytic hydrogenation in the presence of isopropylamine).

The implementation can be done in the for the production of sulfonamides !! usual way done by z. B. the two components in an inert organic agent, if necessary in the presence of acid-binding agents Accessories, matches. However, it is more advantageous to work in water using an excess a base of the formula given above.

It is already known from British Patent 520 199 and U.S. Patent 2,459,771 Phthalocvaninsulfonsäurechloride with cyclohexylamine, Implement monoisoalkylamines or heterocyclic amines. This creates dyes that are in organic Solvents, especially in low-boiling alcohols or ketones, such as alcohol or acetone, very easily are soluble.

In some cases this also gives water-soluble dyes or dyes which are insoluble both in water and in organic solvents. For some application purposes, such properties are more or less desirable. Such dyes are suitable because of their good solubility in low-boiling alcohols or ketones z. B. as paint dyes. However, the aforementioned dyes are methods of making more basic
Phthalocyanine series dyes

Applicant:

Aniline & Soda Factory in Baden

Corporation,
ίο Ludwigshafen / Rhine

Dr. Arnold Tartter, Lambsheim (Palatinate),
has been named as the inventor

unsuitable if you have higher demands on the

Solvent resistance of dyes provides, as with dyes, both in water and in the Most common, especially low-boiling solvents can be very sparingly soluble or insoluble should, however, with the help of suitable higher boiling

organic solvent should be allowed to dissolve well. These requirements are met by the invention produced dyes largely met. The new dyes stand out before those from the British U.S. Patent 520 199 and U.S. Patent

2,459,771 known dyes due to their better resistance compared to low-boiling solvents.

It is also known (see. French Patent 1,117,562) that one in higher-boiling organic

Means well soluble basic sulfonamides can be produced if you phthalocyanine sulfochloride with such aliphatic Reacts diamines which have a tertiary amino group in addition to a primary or secondary. the compounds obtainable in this way are also available in diluted organic

niche acids easily soluble. This is desirable in some cases, but is annoying when dealing with such Dyes acidic and acidic dyeings wants to produce on textiles. The according to the crfmdungsgemcn Process produced new dyes

sit compared to the known a lower solubility in acids and therefore show the above-mentioned disadvantage to a far lesser extent.

Let phthalocyanine and high chlorides be substituted with us Alkylenediamines react, so one obtains

Reaction products that z. B. are not or only very slightly soluble in benzyl alcohol. Presumably arise in this reaction by crosslinking higher molecular compounds, which cause the lower solubility. Similar poorly soluble products are obtained from

Claims (10)

Reaction of Phthalocyaninsulfochloridcn with aliphatic Diamines that have a straight lower alkyl radical, such as. ß. a methyl or Ethyl group. It was therefore surprising that the reaction products with amines of the above general formula are almost completely insoluble in most organic solvents, themselves in But benzyl alcohol dissolves excellently. The parts mentioned in the examples are parts by weight. example 1 250 parts of copper phthalocyanine are used in 2000 parts Chlorosulfonic acid heated to 120 ° C for 2.5 hours. Then the cooled solution is poured onto ice, the precipitated Siphoned off sulfochloricrte copper phthalocyanine and washed neutral with ice water. The suction material will pasted with 1000 parts of ice water and in a mixture of 500 parts of N-cyclohexyl-propylenediamine- (l, 3), Stir in 500 parts of water and 500 parts of ice. After stirring for about 15 hours at ordinary temperature it is diluted with 4000 parts of water, heated to about 60 ° C. for a short time and filtered off with suction. After drying and grinding gives about 525 parts of a dye powder which is practically insoluble in acetone and alcohol but it dissolves easily in benzyl alcohol with a blue color. In a similar manner one can obtain from nickel or iron phthalocyanine Dyes of a greenish blue shade, from tetraphenyl copper phthalocvanine a green dye. Example 2 A solution of 20 parts of monochloro copper phthalocyanine in 160 parts of chlorosulfonic acid is ^{heated to 115 °} C. for about 3 hours and, after cooling, poured into ice water. The suction filtered and washed sulfochloride is made into a paste with 100 parts of ice and a little water and, after addition of 30 parts of N-isopropylpropylenediamine- (1.3), stirred for about 10 hours, the mixture being allowed to warm up gradually to the usual temperature. After dilution with 300 parts of water, it is filtered off with suction, dried and ground. A blue dye which is readily soluble in benzyl alcohol is thus obtained in good yield. Is used in place of Monochlorkupferpbthalocyanin the corresponding amount of a Azakupferphthalocyanins obtained by Harnstoffscnmelze of 3 parts of phthalic acid and 2 parts of quinolinic acid in the presence of copper salts, the solution was heated in chlorosulfonic acid for 3 hours at 13O ⁰ C and then sets as described above with N-Isopropylpropylendiamin - (1.3) µm, this gives a dye which is soluble in benzyl alcohol with a reddish blue shade. Example 3 10 parts of a mixture of copper phthalocyaninesulfonic acids obtained by melting urea of 3 mols of sulfoplithalic acid ammonium and 1% of phthalic anhydride are poured into the sulfochlorides with 100 parts of chlorosulfonic acid in the manner described in the preceding examples. The filtered off and washed product is made into a paste with ice and 12 parts of 1-ammo-3- (2-methylpropy]) aminopröpan and stirred for 20 hours at ordinary temperature. Then, the reaction mixture is diluted by stirring in 200 parts of 6O ⁰ C warm water and suction filtered. The dried and ground dye easily dissolves in benzyl alcohol with a pure blue color. Similar dyes are obtained by reacting the sulfochlorination product with N-isopropylethylenediamine or with 1-isopropylamino-2-aminocyclohexane. P A T E N T Λ N S P R U C H: Process for the production of basic dyes egg phthalocyanine series, characterized that you phthalocyaninesulfochloride with compounds of the general formula H ₂ NR-NH-R ' in which R is an alkylene or Cycloalkylcngruppc and R 'a branched aliphatic or a cycloaliphatic]! Rest means. Considered publications:
British Patent No. 520 199;
U.S. Patent No. 2,459,771;
French patent specification No. 1 117 562. When the application was announced, two staining tables were displayed. © 809 74S / 408 1.59