JPH0322423B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to halotriazinyl-containing compounds, their preparation and use as fiber-reactive dyes. More specifically, the present invention provides an asymmetric compound represented by the following formula. In the above formula, D is the following formula (a), (b), (c), (d), (e), and (f), R ₄ represents hydrogen, C _1-4 alkyl or C _1-4 alkoxy, R ₅ represents hydrogen, C _1-4 alkyl, C _1-4 alkoxy, -NHCOCH ₃ or -
_NHCONH2 , _R7 represents hydrogen or _C1-4 alkyl, _R8 represents hydrogen or _C1-4 alkyl, _R9
represents hydrogen or sulfo, R ₁₁ represents hydrogen, carboxy, sulfo, sulfomethylene or -CONH ₂ , R ₁₂ represents hydrogen or C _1-4 alkyl, R ₁₃ represents hydrogen or sulfo (provided that the group ( e) shall contain at least 2 sulfos), n is 1 or 2, m is 0 or 1 (provided that the sum of m+n is at least 2), and D' is defined in D above. (However, D and D′ are different), and R ₁ is each independently hydrogen or
represents C _1-4 alkyl, R ₂ and R ₃ each independently represent hydrogen, C _1-4 alkyl or 2-, 3- or 4-hydroxy-C _2-4 alkyl, and X is a straight chain or branched Represents a chain C _2-6 alkylene group or a monohydroxy-substituted linear or branched C _3-6 alkylene group, Ha
represents fluorine or chlorine. These compounds may be in free acid form or salt form, or a mixture thereof. X is preferably X′ i.e. straight chain or branched chain
_C2-3 alkylene or monohydroxy-substituted straight or branched _C3-4 alkylene. Ha is preferably chlorine. Any alkyl as R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₇ , R ₈ and R ₁₂ preferably contains 1 or 2 carbon atoms. Any alkyl as R ₄ or R ₅ preferably contains 1 or 2 carbon atoms, especially methoxy. Preferably, R ₁ is each independently R′ ₁ , hydrogen, methyl or ethyl, more preferably R″ ₁ , hydrogen or methyl, and particularly preferably hydrogen. R ₂ and R ₃ are each Preferably R ₂ ′ and R ₃ ′ are independently hydrogen, methyl, ethyl or hydroxyethyl. More preferably R ₂ and R ₃ are R ₂ ″ and
R ₃ ″, i.e. each independently hydrogen or methyl;
Most preferred is hydrogen. R ₄ is preferably R ₄ ', ie hydrogen, methyl or methoxy. _R5 is preferably _R5 ', ie hydrogen, methyl or _-NHCOCH3 or _-NHCONH2 . When _R5 is _-NHCOCH3 or _-NHCONH2 , _R4 is preferably hydrogen, and when _R5 is _C1-4 alkyl, especially methyl, _R4 is preferably hydrogen or methoxy. If R ₅ is hydrogen
Preferably R ₄ is hydrogen, R ₇ is preferably hydrogen. R ₈ is preferably R ₈ ', hydrogen, methyl or ethyl. R ₁₁ is preferably R ₁₁ ′, hydrogen, sulfomethylene or -CONH ₂ . R ₁₂ is preferably R ₁₂ ', ie hydrogen or C _1-2 alkyl, with ethyl being particularly preferred. R ₁₃ is hydrogen when R ₁₁ ' is sulfomethylene, and is sulfo when R ₁₁ ' is hydrogen or -CONH ₂ . In the radical of formula (a), the azo group is bonded in the 1 or 2 position, preferably in the 2 position. In the group of formula (a), an azo group is bonded to the 2-position, and n
is 2 and m is 1, the sulfo group is in the 3,6,8-, 4,6,8-, 1,5,7- or 3,5,7-position, preferably in the 3,6 , 8- or 4,6,8-positions. If the azo group is in the 1-position, the sulfo group is preferably in the 2,5,7- or 3,6,8-position. When n is 1 and m is 1 in the group of formula (a), the azo group is preferably in the 2-position and the sulfo group is preferably in the 1,5-, 6- or 4,8-position. Preferably, when n is 2 and m is 0, these are preferably in the 6,8-position. In the group of formula (d), the azo group is preferably bonded to the 2-position, and the sulfo group is preferably bonded to the 1,5- or 1,6-position. In the groups of formulas (b), (c) and (d), the sulfo group on the hydroxynaphthalene is preferably in the 3-position. In the group of formula (g), preferably the azo group is in the 2-position and the sulfo group is in the 1-position. In the group of formula (c), preferably R ₈ , R ₉ and one of the sulfo groups are in the 2-position, more preferably the sulfo group is in the 2-position. Preferred formula compounds are as follows.
(i) D is a group of formula (a), m is 1 and n is 1 or 2, or m is 0 and n is 2, R ₄ is hydrogen, and R ₅ is -NHCOCH ₃ or -NHCONH ₂ , Ha is chlorine, R ₂ and R ₃ are R ₂ ' and
R ₃ ', D' is a group of formula (a), m is 1 and n is 1 or 2, R ₄ is R ₄ ', R ₅ is hydrogen or methyl, and A compound where is X′. (ii) D is a group of formula (a), m is 1, and n is 2
, R ₂ and R ₃ are R ₂ ′ and R ₃ ′, R ₄ is hydrogen, and R ₅ is −NHCOCH ₃ or −NHCONH ₂
, Ha is chlorine, D' is a group of formula (a), m is 1, n is 1, R ₄ is R ₄ ', R ₅ is R ₅ ', A compound in which X is X'. (iii) D is a group of formula (a), m is 1, and n is 2
, R ₂ and R ₃ are R ₂ ′ and R ₃ ′, and R ₄ is
R ₄ ′, R ₅ is R ₅ ′, Ha is hydrogen,
D′ is a group of formula (b) or (c), R ₇ is hydrogen,
A compound in which R ₈ is R ₈ ' and X is X'. (iv) D is a group of formula (a), m is 1, and n is 1
or 2, or m is 0, n is 2, R ₂ and R ₃ are R ₂ ' and R 3 ', R ₄ is R ₄ ', R ₅ is R _{5 '} , Ha is hydrogen,
D′ is a group of formula (b) or (c), R ₇ is hydrogen,
A compound in which R ₈ is R ₈ ' and X is X'. (v) D is a group of formula (d), and R ₂ and R ₃ are R ₂ ' and
R ₃ ′, D′ is a group of formula (c) or (f), and R ₈ and R ₉
is hydrogen, Ha is chlorine, and X is X'. (vi) D is a group of formula (e), R ₁₁ is R ₁₁ ' and R ₁₂ is
R ₁₂ ′, R ₂ and R ₃ are R ₂ ′ and R ₃ ′, and D′ is the formula
(b) or (c), R ₇ is hydrogen, and R ₈ is
A compound in which R ₈ ', Ha is chlorine, and X is X'. (vii) Compounds (i) to (vi) in which R ₁ , R ₂ and R ₃ are hydrogen. When the compound of formula is in salt form, the cation of the sulfo group can be any of the non-chromogenic cations common to reactive dye chemistry. Examples of suitable cations are sodium, lithium, potassium,
Alkali metal cations and substituted or unsubstituted ammonium, such as ammonium, mono-, di- and tetra-methylammonium, triethylammonium and mono- and triethanolammonium. The present invention further provides a method for preparing a compound of the formula defined above, which method comprises the following formula: [In the above formula, F represents D or D'] The compound represented by the following formula: [In the above formula, when F is D, F ₁ represents D′,
When F is D', F ₁ represents D]. This reaction is carried out according to known methods. The reaction is suitably carried out in a neutral to alkaline medium in the presence of an acid binder. The reaction temperature is 30
Preferably, the temperature is in the range of ~60°C. Compounds of formula and can be produced according to known methods. The compound of formula is preferably
The dye F ₁ -NHR ₁ is 2,4,6-trihalo-
It is prepared by reacting with 1,3,5-triazine and then reacting the product with _HNR2 -X- _NR3H . The second reaction is suitably carried out in the presence of a free acid binding agent in a neutral medium at temperatures between room temperature and 50°C. The compounds of the formula and mixtures thereof are useful as reactive dyes for dyeing or printing hydroxyl and nitrogen containing organic substrates. Preferably the substrate is a fibrous material containing or consisting of natural or synthetic polyamides such as leather and wool, silk and nylon, or natural or regenerated cellulose such as cotton, viscose and spun rayon. When Ha is chlorine, staining can be carried out as well at 80°C as at 100°C. When Ha is fluorine, the dye is a so-called low-temperature dye, ie the dyeing is preferably carried out at a temperature in the range from 20 to 40°C. It can be dyed or carried out according to known methods. Preferably, the dyeing is carried out by the exhaust method. The dyeings obtained have good warm fastnesses, such as washing, water and sweat fastnesses, and these dyes give good color yields and are hardly affected by salt. Furthermore, these dyes have good fastness to chlorine and peracid bleaching. The following examples serve to further illustrate the invention. In the examples, "parts" are expressed in weight, and temperatures are expressed in degrees Celsius. Note that Examples 19 and 30 are reference examples. Example 1 191.5 parts of 2-aminonaphthalene-3,6,8
-Tolsulfonic acid was suspended in 500 parts of water.
30% of 125 parts while cooling to 0-6° by adding ice.
After addition of hydrochloric acid, diazotization was carried out with 125 parts of 4N sodium nitrite solution for 45 minutes. Stirring was continued for 1 hour and excess nitrite was destroyed by aminosulfonic acid. 75.5 parts of 1-amine-3-ureidobenzene
50 parts of 30% hydrochloric acid were added and dissolved in 250 parts of water while lowering the temperature to below 5° with ice. The diazo suspension obtained as described above was slowly added thereto, and at the same time 100 parts of sodium acetate (crystals) was added little by little. The solution was stirred overnight and then a small amount of
Adjust the PH to 4.5 with 20% soda solution, approx. 10
Salting out was performed with mol% sodium chloride. Then I took out the dye. 50 parts of cyanuric chloride are added to a solution of 800 parts of the dye thus obtained in water at about 2°,
The pH of this solution was adjusted to 5-5.5. Stirring was carried out at a temperature of less than 5°. Next, 42 parts of cyanuric chloride were added and the PH was adjusted to about 5.5 by addition of sodium carbonate. After completion of the condensation, the reaction mixture was treated with activated carbon and then filtered to clarify. To the dye solution thus obtained was added 37 parts of 1,3-diaminopropanol-2 in 600 parts of water, this was stirred overnight at room temperature and the mixture was adjusted to PH
7 and the whole was stirred for an additional approximately 6 hours at 30-40°C. The product was salted out with sodium chloride,
Filtered. Meanwhile, 285 parts of the trisodium salt of 8-amino-1-hydroxy-2-(2'-sulfophenylazo)naphthalene-3,6-disulfonic acid in 800 parts of water was heated at 0 to 5° with 92 parts of cyanuric chloride. I reacted. The pH of this solution was adjusted to 4-4.5 by adding an aqueous sodium carbonate solution. The product thus obtained was stirred overnight at room temperature and then at a temperature of 40-50° C. for about 6 hours and the pH was adjusted to 7. , 3-diaminopropanol-2. After salting out with sodium chloride, filtration and drying in vacuo at about 80°C, a dye of the following formula was obtained. This dye dyed natural and regenerated cellulose in a scarlet color. Spectroscopic analysis (with water as solvent) of this dye gave the following maximum absorption wavelengths: λmax(1)=428nm=36′300 λmax(2)=504nm=35′200 Example 2 Diazotized 2-aminonaphthalene-3,6,
6.9 parts of the dichlorotriazine monoazo dye obtained by acidic coupling of 8-trisulfonic acid with m-aminophenyl urea and subsequent condensation with cyanuric chloride are dissolved in 70 parts of water, rendered neutral and 8 parts of It was reacted with a solution consisting of 0.8 parts of 1,2-dianopropane in water and 2 parts of 30% hydrochloric acid. The mixture was reacted for 5 hours at a pH of 7-8 and a temperature of 25-35°C. The pH was maintained by the addition of about 1 part calcined soda dissolved in a small amount of water. After the reaction was completed, the completely produced precipitated amino dye was filtered to separate it from by-products. Stir the press cake in 70 parts of water at room temperature,
It was then combined with about 70 parts by volume of an aqueous solution containing 5 parts of the dye obtained as described below. Diazotized 2-aminonaphthalene-4,8
Disulfonic acid and 2-amino-1-methoxy-4-
4 parts of the dye obtained by the acidic coupling component with methylbenzene are dissolved in 50 parts of water, made neutral and then reacted with 1.8 parts of cyanuric chloride under vigorous stirring and brought to a pH of 20 to 20 by adding an aqueous soda solution.
5 at 25°C. After the reaction was completed, the colorless solid impurity was separated, and the solution was ready for use. The binding of the two monoazo dyes takes place at 20-30° for 5 hours, during which
The pH is reduced to 11 by continuous addition of a solution of sodium hydroxide.
held at ~11.5. After completion of the reaction in a neutral PH medium, the disazo dye was precipitated with sodium chloride, which was then filtered. After drying and grinding, an orange powder was obtained, which dyed the cotton and regenerated cellulose fibers in a bright golden yellow color. The product had the following formula in free acid form. λmax=429nm. Examples 3 to 52 The other dyes shown in the table below could be prepared analogously to those described in Examples 1 and 2. These dyes were obtained in sodium salt form. However, these could be converted into other salt forms according to known methods. In Examples 3-19 _R2 and _R3 are hydrogen. Also, in Examples 20 to 52, Ha is chlorine.

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golden
Ten
Same as above
Same as above Nyero 427


-

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[Table] Application example 1 part of the dyestuff from Example 1 was dissolved in 300 parts of water. 10 parts of cotton were placed in this dyebath and the temperature was raised to 80°C within 10 minutes. 15 parts of Glauber's salt were added and 30 minutes later 3 parts of sodium carbonate were added. Staining continued for 1 hour. The dyed material was then washed in cold water and then in hot water. The dyeing was soaped for 20 minutes at boiling temperature in 500 parts of water and 0.5 parts of sodium alkylsulfonate. After washing with water, good sunlight, moisture,
A scarlet red dyeing having a fastness to chlorine and a color fastness to chlorine was obtained.

Claims (1)

[Scope of Claims] 1. Compounds represented by the following formulas and mixtures thereof in free acid form or salt form. In the above formula, D is the following formula (a), (b), (c), (d), (e), and (f), R ₄ represents hydrogen, C _1-4 alkyl or C _1-4 alkoxy, R ₅ represents hydrogen, C _1-4 alkyl, C _1-4 alkoxy, -NHCOCH ₃ or -
_NHCONH2 , _R7 represents hydrogen or _C1-4 alkyl, _R8 represents hydrogen or _C1-4 alkyl, _R9
represents hydrogen or sulfo, R ₁₁ represents hydrogen, carboxy, sulfo, sulfomethylene or -CONH ₂ , R ₁₂ represents hydrogen or C _1-4 alkyl, R ₁₂ represents hydrogen or sulfo (provided that the group ( e) shall contain at least 2 sulfos), n is 1 or 2, m is 0 or 1 (provided that the sum of m+n is at least 2), and D' is defined in D above. (However, D and D′ are different), and R ₁ is each independently hydrogen or
represents C _1-4 alkyl, R ₂ and R ₃ each independently represent hydrogen, C _1-4 alkyl or 2-, 3- or 4-hydroxy C _2-4 alkyl, and X is a straight or branched chain C _2-6 alkylene group or monohydroxy-substituted linear or branched C _3-6 alkylene group, Ha represents fluorine or chlorine 2 X is X', that is, linear or branched C _3-3 2. The compound according to claim 1, which is an alkylene group or a monohydroxy-substituted linear or branched _C3-4 alkylene group. 3. The compound or salt thereof according to claim 1, which has the following formula. 4. The compound or salt thereof according to claim 1, which has the following formula. 5 The following formula in free acid form or salt form, [In the above formula, D is the following formula (a), (b), (c), (d), (e), and (f), R ₄ represents hydrogen, C _1-4 alkyl or C _1-4 alkoxy, R ₅ represents hydrogen, C _1-4 alkyl, C _1-4 alkoxy, -NHCOCH ₃ or -
_NHCONH2 , _R7 represents hydrogen or _C1-4 alkyl, _R8 represents hydrogen or _C1-4 alkyl, _R9
represents hydrogen or sulfo, R ₁₁ represents hydrogen, carboxy, sulfo, sulfomethylene or -CONH ₂ , R ₁₂ represents hydrogen or C _1-4 alkyl, R ₁₃ represents hydrogen or sulfo (provided that the group ( e) shall contain at least two sulfo groups), n is 1 or 2, m is 0 or 1 (provided that the sum of m+n is at least 2), and D' is the above-mentioned D
(however, D and D' are different), R ₁ each independently represents hydrogen or C _1-4 alkyl, R ₂ and R ₃ each independently represent hydrogen, C _1-4 alkyl or 2-, 3- or 4-
represents hydroxy- _C2-4 alkyl, X represents a straight-chain or branched-chain _C2-6 alkylene group or a monohydroxy-substituted straight-chain or branched _C3-6 alkylene group, Ha
represents fluorine or chlorine] To produce the compound represented by the following formula: [In the above formula, F represents D or D'] The compound represented by the following formula: [In the above formula, when F is D, F ₁ represents D′,
When F is D', F ₁ represents D]. 6 When dyeing or printing a nitrogen-containing or hydroxy-containing organic substrate, the following formula, in free acid form or salt form, is used as a dyeing or printing agent on the substrate: [In the above formula, D is the following formula (a), (b), (c), (d), (e), and (f) R ₄ represents hydrogen, C _1-4 alkyl or C _1-4 alkoxy, R ₅ represents hydrogen, C _1-4 alkyl, C _1-4 alkoxy, -NHCOCH ₃ or -
_NHCONH2 , _R7 represents hydrogen or _C1-4 alkyl, _R8 represents hydrogen or _C1-4 alkyl, _R9
represents hydrogen or sulfo, R ₁₁ represents hydrogen, carboxy, sulfo, sulfomethylene or -CONH ₂ , R ₁₂ represents hydrogen or C _1-4 alkyl, R ₁₃ represents hydrogen or sulfo (provided that the group ( e) shall contain at least two sulfo groups), n is 1 or 2, m is 0 or 1 (provided that the sum of m+n is at least 2), and D' is the above-mentioned D
(however, D and D' are different), R ₁ each independently represents hydrogen or C _1-4 alkyl, R ₂ and R ₃ each independently represent hydrogen, C _1-4 alkyl or 2-, 3- or 4-
represents hydroxy-C _2-4 alkyl, X represents a straight-chain or branched-chain C _2-6 alkylene group or a monohydroxy-substituted straight-chain or branched C _3-6 alkylene group, Ha
represents fluorine or chlorine] or a mixture thereof.