JPS604850B2 - Pure asymmetric 1:2 cobalt complex dye and its production method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a dye consisting of at least one pure asymmetric 1:2 cobalt salt and a process for its preparation.

More specifically, the present invention provides a dye comprising at least one pure asymmetric 1:2 cobalt salt represented by the following general formula 1.

In the above formula, X represents hydrogen or nitro, and for R and R2, R represents hydrogen, chlorine, nitro, (C, ~4) alkyl, or (C, ~4) alkoxy, and R2 represents hydrogen, chlorine or nitro, or R represents hydrogen or chlorine, and R2
represents -Sf2NR3R4, and the groups R, and R2
occupies the 4- and 5-positions; for R3 and R4, R3 represents hydrogen or (C,~4)alkyl;
and R4 is hydrogen, (C, ~4) alkyl, or hydroxy or (C, ~4) alkoxy substituted (C,
~4) Represents alkyl or phenyl, or R
3 and R4 form a morpholine ring together with the nitrogen atom to which they are bonded, and B has the following formula {a-, {
ke, 'c} or [d}: [In the above formula, Y is hydrogen, (C, ~
2) represents a divalent group of alkyl or (C, ~2) alkoxy], and D represents the following formula {e}: [Regarding R5 and Y2 in the above formula, R5 is (C, ~4)
Alkyl or the following formula tf} or g): (In the above formula, one of R6 and R7 represents hydrogen, and the other represents hydrogen, chlorine, or (
C, ~2) represents alkyl, R8 represents hydrogen or methyl, R9 represents methyl), and Y2 represents hydrogen, or Rs
-S02 where represents hydrogen and Y2 is the 5-1 or 6-1 position
NHR,.

represents a group (wherein R and o represent hydroxy(C2-4)alkyl)], and M represents hydrogen or a non-chromophoric cation equivalent thereto, provided that the molecule of formula 1 above (l) contains one sulfo group (however, the sulfo group is in the form of a salt), and (ii) at most one sulfonamide group (provided that this sulfonamide group is present in group D). or in the radical R2), but (iii) shall not contain the radical.

When R, in formula 1 is alkyl, such alkyl is preferably methyl or ethyl, particularly preferably methyl.

When R, is alkoxy, it is preferred that such alkoxy is methoxy or ethoxy.

When R3 and/or R4 are unsubstituted alkyl groups, such alkyl groups are preferably straight or branched and contain 1 to 3 carbon atoms, and are methyl, ethyl and isopropyl. is particularly preferred.

Any substituted alkyl group as R4 is preferably monosubstituted.

The term "halogen" means chlorine, bromine or fluorine, with chlorine and bromine being preferred.

R3 is preferably R'3, ie hydrogen, or (C,~3)alkyl.

Most preferably R3 is hydrogen. R4 is preferably R'4 ie hydrogen: (C,~3)alkyl; 8- if <y-hydroxy(C2-3)alkyl; R, . ○−
(CH2)n- (where R, . represents methyl or ethyl, n represents 2, 3 or 4, preferably 2 or 3) or phenyl, more preferably R'4, ie methyl, ethyl, Isopropyl, 2-hydroxyethyl, 1CH21CH(OH)-C, 1(CH2)3-OC or phenyl, even more preferably R, methyl, 1(C)31OCH3 Or phenyl.

R is preferably R', ie hydrogen, methyl, chlorine or nitro, and more preferably R', ie hydrogen, chlorine or nihero. R2 is preferably R'2, ie chlorine,
Nitro, or -S02NHR...4, preferably -S0
2NHR...4.

However, R'2 is -S02NHR''4 or -S02NHR
In the case of river 4, R is hydrogen. R, and R2 are
More preferably each independently is chlorine or nitro.

When one of R and R2 is hydrogen and the other is other than hydrogen, this substituent is preferably in the 4 or 5 position. When R and R2 are both other than hydrogen, these substituents are preferably in the 4 and 6 positions. However, when R2 is -S02NR3R4, the substituents R and R2 are at the 4- and 5-positions. In the formula {b) representing group B, Y, preferably represents Y', ie hydrogen, methyl or methoxy.

More preferably, B is B', i.e. a group of formula {a-, 'c) or {d}, or a group of formula {b'' in which Y is Y',
is a group.

In the group of formula {e-, when R5 is alkyl, it is preferred that it is methyl or ethyl.

When R5 is a group of formula [f-, preferably one of R6 and R7 is hydrogen and the other is hydrogen, chlorine or methyl.

R5 is preferably R'5, i.e. hydrogen (when Y2 is other than hydrogen), phenyl, 2-, 3- or 4-chlorophenyl, 2- or 4-methylphenyl or 2.6- Dimethylphenyl, more preferably R5 is R''5, ie hydrogen (provided that Y2 is other than hydrogen), or phenyl, with phenyl being particularly preferred.

Y2 is preferably hydrogen (when R5 is other than hydrogen), or -S0 is HR',o (when R5 is hydrogen).

D is preferably a group of formula [e}, in which case R5 is R'5 and Y2 is hydrogen or -S02NHR'.

It is preferable that The most preferable group D is the following formula (
It is a group of el'. Preferably, M is an alkali metal cation, an unsubstituted or substituted ammonium ion, or a quaternary amine.

Examples of alkali metal cations include sodium, lithium and potassium, with sodium being preferred. A suitable substituted ammonium ion is (C, ~3)
Alkylammonium and hydroxy (C2-4)
Alkylammoniums such as triethylammonium, mono- and tri-isopropanol ammonium and mono-, di- and tri-isopropanol ammonium. Suitable quaternary amines include cyclic amines such as N-ethyl-N-hexylamine, cyclohexylamine, N·N-dicyclohexylamine, or quaternary morpholine. When M is a quaternary amine, 1:2
The water solubility of the salts is reduced to the extent that they are either slightly soluble or only soluble in the presence of organic solvents. The 1:2 complex salts when M is hydrogen are in some cases slightly soluble in water.

The salt form of the sulfo group may correspond to any of the cations for M above.

The salt cation may be the same as M or may be different. The present invention also provides a method for producing a dye comprising at least one complex salt of formula 1. This method uses at least one species of the free acid form represented by the following formula 0: [In the above formula, L and L2 represent monodentate ligands, and × and B represent the same as defined above]. The method comprises reacting a compound of the formula m with at least one compound represented by the following formula m: [in the above formula, R, R2 and D represent the same as defined above], and A sulfo group may be modified into its salt form.

The reaction is suitably carried out using stoichiometric amounts of the reactants.

Suitable monodentate ligands are colorless inorganic or organic molecules, especially water molecules, containing oxygen or nitrogen groups with electron-donating properties. The reaction is carried out in an aqueous, aqueous/organic or organic medium. Examples of organic solvents include low molecular weight carboxylic acid amides or alkylated derivatives thereof such as formamide or glycols or their ether derivatives such as ethylene glycol, di- or triethylene glycol. The reaction is carried out in a neutral or alkaline medium, with 1
It is appropriate to terminate the reaction after all of the :1 rust salt has been reacted. The product obtained is isolated in the usual manner, for example by salting out or weakly acidified, and after washing with concentrated salt solution is recovered and dried. The resulting asymmetric rust salt is a pure asymmetric rust salt, ie a complex salt containing less than 10% of the symmetric rust salt.

The 1:1 cobalt salt starting material of formula B above is prepared by reacting a compound of formula W below with a cobalt donor compound in the form of a cobalt(0) salt in the presence of an inorganic nitrite salt.

Suitably, the compound of formula W is reacted with the cobalt donor compound in a 1:1 molar ratio.

Preferably, 2 to 6 moles of nitrite are used per gram atom of cobalt. Metallization is carried out in the usual manner. Depending on the reaction and isolation conditions (e.g. the addition of a base to obtain an alkaline pH or the salt used to salt out the product), M is preferably an alkali metal cation such as lithium, sodium or potassium or an ammonium ion. The tsuba salt of formula 1, in which the salt cation of the sulfo group is the same as or different from M, is obtained. When using a weak acid, M
is hydrogen and the sulfo group is in the form of a salt to obtain a suzu salt. Hydrogen ions can be replaced by alkali metal cations or quaternary ammonium ions by addition of alkali metal hydroxides or organic amines. It should be understood that at this time, the cation of the sulfo group can also be replaced at the same time. Compounds of formulas 2, m and W are known or can be prepared from known starting materials in a conventional manner. Materials comprising at least one collar salt of formula 1 are useful as dyes for dyeing and printing nitrogen-containing organic substrates.

Examples of suitable substrates are those consisting of or containing natural or synthetic polyamides, such as wool, silk or nylon, or polyurethane or leather. The dyeings obtained exhibit outstanding light and wet fastness properties.

The dyeings also exhibit remarkable rubfastness and resistance to charring, ironing, wool chlorination and the action of acids and alkalis. These dyes dye polyamide fibers from a neutral medium and the build-up is in a constant tone due to their purely asymmetrical nature.

These dyes also stain wool and nylon equally well when dyeing both. These dyes are suitable for use in combination with other 1:2 metal salts. These rust salts can be formed into suitable printing pastes and dye all types of polyamides well. A chain salt of formula 1 which is well soluble in water, i.e. M is hydrogen or a cyclic group such as N-ethyl-N-hexylamine, cyclohexylamine, N.N dicyclohexylamine or quaternary form of morpholine. Complex salts of formula 1 that are other than amine, such as amine, are
It is also useful for dyeing metals, especially anodized aluminum. Compounds of formula 1 in which M is a quaternary amine as defined above can also be used for the production of print lacquers and ballpoint inks.

The dyes according to the invention can be used as such or in the form of liquid or solid formulations.

Water-soluble organic solvents, optionally mixed with water, are preferably used for liquid formulations in the form of stable concentrated stock solutions, and conventional additives such as solubilizers (e.g. urea or alkali-reactive organic or inorganic substances) are preferably used. ) may be added.

Stock solutions can be diluted with water. Such formulations can be manufactured, for example, according to the procedures described in German Patent No. 1,619,470 or German Patent Application No. 2,033,989. It is also possible to use concentrated, stable aqueous formulations containing conventional additives. It is also possible to use solid formulations in powder or particulate form with an average particle size of at least 20 French, and such formulations may also contain customary additives such as standardizing agents. Solid formulations such as can be manufactured, for example, according to the procedure described in British Patent No. 1,370,845. The solid formulation is highly soluble in water and therefore allows the exact amount of dye formulation required to be added to the liangge. The following examples serve to further explain the invention.

In the examples, "parts" are expressed by weight. Example 1 Diazotized 2-amino-1-hydroxy-4.6-
45 parts of dye obtained by acidic coupling of dinitrobenzene with 2-(3'-chlorophenyl)aminonaphthalene and 1-amino-2-hydroxy-6-nit.

A paste of 1:1 cobalt salt obtained from 44 parts of naphthalene-4-sulfonic acid → 2-hydroxynaphthalene monoazo dye was stirred in 60 parts of water and 30 parts of ethanol, and a sodium hydroxide solution was added. to adjust the pH to 1
Adjust to 1.0 to 11.5. The reaction mixture is heated to 30qC and incubated at this temperature for 24 hours. After this time, if any starting material remains, lower the temperature to 80q.
o and continue stirring until both starting materials have disappeared. The pH is maintained between 11 and 11.5 during the entire reaction time.
The chromatograph of the resulting asymmetric 1:2 cobalt anchor salt should show no or only minimal traces of metal-free dye;
1. It shall not show any trace of cobalt salt. The dyestuff is salted by adding sodium chloride, filtered out, washed with 5% sodium chloride solution and dried. This dye corresponds to the formula: and has a very high degree of purity (up to 5% in total)
symmetrical complex salt).

This dye is highly soluble in water and dyes natural and synthetic polyamide fibers such as wool and nylon gray or black;
Absorbed from the neutral character in the usual way. The dyeing is good,
It has all-round wet fastness and outstanding sunlight fastness as well as outstanding rub fastness. 1 used as starting material
:1 cobalt complex salt can be produced as follows. 28 parts of cobalt(0) sulfate heptahydrate and 28 parts of sodium nitrite are dissolved in 50 parts of water in a beaker.

Next, 44 parts of the monoazo dye, 1-amino-2-hydroxy-6-nitronaphthalene-4-sulfonic acid→2-hydroxynaphthalene, are added with careful stirring. During and after the addition of this monoazo dye, the pH is adjusted to 5.5-6.
．． 0 and held in this range for approximately 20 hours until the original dye is completely converted to a 1:1 cobalt rust salt. During metallization the temperature must be maintained between 20 and 30 degrees Celsius. The 1:1 cobalt key salt is precipitated by salting out with sodium chloride solution.

The obtained 1:1 cobalt rust salt can be directly used in the reaction for producing an asymmetric 1:2 cobalt rust salt. Examples 2-3
6 Table 1 below shows the structures of other dyes of the present invention.

These dyes are obtained analogously to Example 1. The dyes in the table give dyeings on polyamides with properties similar to those of Example 1. The hue of the dye obtained in each case is indicated by the symbols a to h shown in column 1. Symbols a to h have the following meanings. a: black, b: reddish black, c: greeny black, d: bluish black,
e: brown f: reddish brown, g: Bordeaux, h: Rubin. 1st
The maximum absorption wavelengths of Examples 1 to 36 above are shown in Table 2 below.

However, the measurement was performed using the dye dimethylformamide-water (8:
2) A solution in a mixed solution (with a small amount of phosphoric acid added) was tested. Table 2 Application example A: Dissolve 0.03 μl (to obtain a gray color) or 0.15 μl (to obtain a black color) of the dye obtained in Example 1 in 300 μl of water, and add 0.2 μl of ammonium sulfate. Added.

Next, warm the ingredients (5 tbsp wool gabardine or 5 tbsp wool gabardine)
Place the nylon satin in the bath and heat to boiling temperature for 30 minutes. The water evaporated during the 30 minutes of boiling is replenished and the dyeing is completed for a further 30 minutes at boiling temperature and then washed with water.

After drying, a gray or black dyeing with outstanding wet and light fastness is obtained. Dyeing can be carried out using the dyes of Examples 2 to 36 in the same manner as above. Application example B: Printing polyamide with a printing paste containing the following.

Dye of Example 3 5. Ikari Tourea
5-side solubilizing agent (e.g. thiojetyl glycol) Part 5 K Water 30 anchor parts Suitable thickening agent (e.g. one based on locust bean gum)
50 anchorage acid acceptor (e.g. ammonium bottletrate) 6 base thiourea
The imprinted material is steamed (saturated steam) at 10 or 0 for 40 minutes, then washed in cold water, washed with regular detergent at 60 or 0 for 5 minutes, and washed again with water.

A black print is obtained with good wet and light fastness properties. Printing pastes can be produced and printed using the dyes of Examples 1-2 and 4-36 in the same manner as described above.

Claims (1)

[Claims] 1. At least one pure asymmetric type 1 represented by general formula I:
A dye consisting of 2 cobalt complex salts. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the above formula, X represents hydrogen or nitro, and for R_1 and R_2, R_1 is hydrogen, chlorine,
Nitro, (C_1_~_4)alkyl, or (C_1_
~_4) represents alkoxy, and R_2 represents hydrogen, chlorine, or nitro, or R_1 represents hydrogen or chlorine, and R_2 represents -SO_2NR_3R_4
and the groups R_1 and R_2 occupy the 4- and 5-positions, and for R_3 and R_4, R_3 represents hydrogen or (C_1_-_4)alkyl, and
R_4 represents hydrogen, (C_1_-_4) alkyl, (C_1_-_4) alkyl substituted with hydroxy or (C_1_-_4) alkoxy, or phenyl, or R_3 and R_4 are It forms a morpholine ring with the nitrogen atom, and B
is the following formula (a), (b), (c) or (d): ▲ Formula,
There are chemical formulas, tables, etc. ▼ [In the above formula, Y_1 is hydrogen, (C
_1_-_2) represents alkyl or (C_1_-_2) alkoxy]; D represents the following formula (e): ▲There are numerical formulas, chemical formulas, tables, etc.▼ [R_5 and Y_2 in the above formula , R_5 is (C_
1_～_4) Alkyl or the following formula (f) or (g): ▲
There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, one of R_6 and R_7 represents hydrogen, the others represent hydrogen, chlorine, or (C_1_-_2), and R_8
represents hydrogen or methyl, R_9 represents methyl), and Y_2 represents hydrogen, or R
_5 represents hydrogen, and Y_2 is - at the 5- or 6-position
represents a SO_2NHR_1_0 group (wherein R_1_0 represents hydroxy(C_2_-_4)alkyl)] and M represents hydrogen or an equivalent non-chromophoric cation, provided that the molecule of formula I above is (i) one sulfo group in the form of a salt; and (ii) at most one sulfonamide group, provided that this sulfonamide group is present in group D or in group R_2. ), but (iii) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ shall not include groups. 2. The dye according to claim 1, wherein the 1:2 cobalt complex salt is represented by the following formula Ia. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the above formula, R'_1 represents hydrogen, methyl, chlorine, or nitro, and R'_2 represents chlorine, nitro, or -SO_2NHR''
_4, where R'_2 is -SO_2NHR''_4 or -SO_2NHR''' when R'_1 is hydrogen.
_4 only, and B' is the formula (a), (b), (
c) or (d), and when B' is a group of formula (b), Y_1 shall be hydrogen, methyl or methoxy. 3. The dye according to claim 1, wherein the 1:2 cobalt complex salt is represented by the following formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the above formula, M is the same as the above rule. 4. The dye according to claim 1, wherein the 1:2 cobalt complex salt is represented by the following formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the above formula, M is the same as the above rule. 5. The dye according to claim 1, wherein the 1:2 cobalt complex salt is represented by the following formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the above formula, M is the same as the above regulation. 6. The dye according to claim 1, wherein the 1:2 cobalt complex salt is represented by the following formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the above formula, M is the same as the above regulation. 7. The dye according to claim 1, wherein the 1:2 cobalt complex salt is represented by the following formula. ▲There are mathematical formulas, chemical formulas, tables, etc.▼ In the above formula, M is the same as the above regulation. 8 General formula I below: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [However, in the above formula, X represents hydrogen or nitro, and for R_1 and R_2, R_1 is hydrogen, chlorine, nitro,
(C_1_~_4) alkyl, or (C_1_~_4)
represents alkoxy and R_2 represents hydrogen, chlorine or nitro, or R_1 represents hydrogen or chlorine and R_2 represents -SO_2NR_3R_4, and the groups R_1 and R_2 are in the 4- and 5-positions. occupies R_3 and R_4, R_3 represents hydrogen or (C_1_-_4)alkyl, and R_4
is substituted with hydrogen, (C_1_~_4) alkyl, or hydroxy or (C_1_~_4) alkoxy
_1_-_4) represents alkyl or phenyl, or R_3 and R_4 form a morpholine ring together with the nitrogen atom to which they are bonded, and B represents the following formula (a), (b), ( c) or (d): ▲There are mathematical formulas, chemical formulas, tables, etc.▼▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the above formula, Y_1 represents hydrogen, (C_1_~_2) alkyl or (C_1_~_2) alkoxy] ], D represents the following formula (e): ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the above formula, R_5 and Y_2, R_5 is (C_
1_~_4) Alkyl or the following formula (f) or (g):
▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the above formula, one of R_6 and R_7 represents hydrogen, the other represents hydrogen, chlorine, or (C_1_-_2) alkyl, R_8 represents hydrogen or methyl, R_9 represents methyl), and Y_2 represents hydrogen, or R
_5 represents hydrogen, and Y_2 is - at the 5- or 6-position
SO_2NHR_1_0 group (wherein R_1_0 represents hydroxy(C_2_-_4)alkyl)], and M represents hydrogen or an equivalent non-chromophoric cation, provided that the molecule of the above formula I is , (i) contains one sulfo group in the form of a salt, and (ii) at most one sulfonamide group, provided that this sulfonamide group is in the group D or in the group R_2 ), but (iii) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ shall not include groups. ] When producing a dye consisting of at least one pure asymmetric 1:2 cobalt complex salt, the free acid form of the following formula II: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [In the above formula, L_1 and L_2 are represents a monodentate ligand,
and B represent the same thing as defined above] at least one compound represented by the following formula III: ▲ mathematical formula, chemical formula,
There are tables etc. ▼ Pure asymmetric type 1, which comprises reacting with at least one compound represented by [in the above formula, R_1, R_2 and D represent the same thing as defined above]:
2. Method for producing cobalt complex dye.