CN1493623A - Monoazo reactive red dyestuff - Google Patents
Monoazo reactive red dyestuff Download PDFInfo
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- CN1493623A CN1493623A CNA021503184A CN02150318A CN1493623A CN 1493623 A CN1493623 A CN 1493623A CN A021503184 A CNA021503184 A CN A021503184A CN 02150318 A CN02150318 A CN 02150318A CN 1493623 A CN1493623 A CN 1493623A
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Abstract
A reactive red monoazo dye for cotton, artificial cotton, bast fibre, wool, silk and artificial fibres is disclosed. Its advantages are high washing off properties, dyeing uniformity and fastness.
Description
Technical field
Technical field of the present invention relates to fibre-reactive dyes, particularly relevant for the reactive orchil of a kind of monoazo of novelty.
Background technology
When dyeing with fibre-reactive dyes, the high-quality journey of dying of dying thing and economy is highly expected.Therefore, it is desired by industry with its quality of Continual Improvement to need novel fibre-reactive dyes.Especially can dye red high fastness characteristic and dye the chemically-reactive dyes of thing.In English Patent the 836th, No. 248, United States Patent (USP) the 2nd, 979, No. 498, and European patent discloses in the 0 No. 070806, once expose several red fibre-reactive dyes, but be to use the getable thing fastness characteristic of dying of these dyestuffs, especially daylight fastness and sweat daylight fastness all to need to improve again.
In addition, United States Patent (USP) the 5th, 227, once the fibre-reactive dyes that disclosed as shown in the formula (II) for No. 475, the dyeing quality and the lifting of dying method efficient are benefited to some extent, it has general dyestuff to outstanding characteristic of dying of fiber and fastness characteristic, but the daylight fastness of red fibre-reactive dyes and sweat daylight fastness still must be improved.
Summary of the invention
The object of the present invention is to provide the reactive orchil of a kind of monoazo, it can dye the thing that dyes of red high fastness characteristic; Especially daylight fastness and sweat daylight fastness all meet the needs of industry.
Novel azo-compound provided by the present invention has improved the characteristic of this respect, and this azo-compound is suc as formula shown in (I):
Wherein
X is-NHCN ,-OH ,-SCH
2COOH ,-NHSO
2CH
3, 3-carboxyl pyridine (3-carboxypyridinium),
Or halogen; Preferable, X is-NHCN, 3-carboxyl pyridine or halogen, and wherein halogen preferably is fluorine atom or chlorine atom;
D is for having 0 to 3 substituent phenyl ring or naphthalene nucleus, and this substituting group is to be selected from respectively to comprise: halogen, C
1-4Alkyl, C
1-4Alkoxyl group, nitro, amido, hydroxyl, carboxyl, phosphate and sulfonic group person; Preferable, D is for having 0 to 3 substituent phenyl ring;
Z is-SO
2-CH=CH
2Or-SO
2-CH
2-CH
2-U; U is-OSO
3H, Cl, Br ,-OPO
3H
2,-SSO
3H or
Preferable, Z is-SO
2-CH-CH
2Or-SO
2-CH
2-CH
2-OSO
3H;
R
2Be sulfonic group, carboxyl, halogen or C
1-4Alkoxyl group; Preferable, R
2Be to be sulfonic group or carboxyl;
N is 0 or 1, and is preferable, and n is 1.
When X is halogen atom, R then
1Be to be hydrogen atom and R
3Be to be C
1-4Alkyl or have at least 1 substituent C
1-4Alkyl; Preferable when X be fluorine atom or chlorine atomic time, R
1Be to be hydrogen atom and R
3Be to be C
1-4Alkyl;
When X be-NHCN ,-OH ,-SCH
2COOH ,-NHSO
2CH
3, 3-carboxyl pyridine (3-carboxypyridinium) or
The time, R then
1And R
3Independent mutually being selected from respectively comprises hydrogen atom, C
1-4Alkyl, phenyl,
Or have one or more substituent C
1-4Alkyl, this substituting group are to be selected from respectively to comprise: the many bases of hydroxyl (hydroxyl), carboxyl (carboxyl), sulfonic group (sulfo), amine formyl (carbamoyl) or methoxy (methoxy carbonyl) person; Preferable, when X be-NHCN ,-OH ,-SCH
2COOH ,-NHSO
2CH
3, the 3-carboxyl pyridine or
The time, R
1And R
3Be to be hydrogen atom or C
1-4Alkyl.
Formula of the present invention (I) monoazo chemically-reactive dyes, preferable, be to be monoazo chemically-reactive dyes as shown in the formula (Ia).
Wherein
X is-NHCN ,-OH ,-SCH
2COOH ,-NHSO
2CH
3, 3-carboxyl pyridine (3-carboxypyridinium),
Or halogen; Preferable, X is-NHCN, 3-carboxyl pyridine, fluorine atom or chlorine atom;
D is for having 0 to 3 substituent phenyl ring or naphthalene nucleus, and this substituting group is to be selected from respectively to comprise: halogen, C
1-4Alkyl, C
1-4Alkoxyl group, nitro, amido, hydroxyl, carboxyl, phosphate and sulfonic group person; Preferable, D is for having 0 to 3 substituent phenyl ring;
Z is-SO
2-CH=CH
2Or-SO
2-CH
2-CH
2-U; U is-OSO
3H, Cl or Br ,-OPOH
2,-SSO
3H or
Preferable, Z is-SO
2CH=CH, or-SO
2-CH
2-CH
2-OSO
3H;
N is 0 or 1, and is preferable, and n is 1;
When X is halogen atom, R then
1Be to be hydrogen atom and R
3Be to be C
1-4Alkyl or have at least 1 substituent C
1-4Alkyl; Preferable, when X is fluorine atom or chlorine atomic time, R
1Be to be hydrogen atom and R
3Be to be C
1-4Alkyl;
When X be-NHCN ,-OH ,-SCH
2COOH ,-NHSO
2CH
3, 3-carboxyl pyridine (3-carboxypyridinium) or
The time, R then
1And R
3Independent mutually being selected from respectively comprises hydrogen atom, C
1-4Alkyl, phenyl,
Or have one or more substituent C
1-4The alkyl person, this substituting group is to be selected from respectively to comprise: hydroxyl (hydroxyl), carboxyl (carboxyl), sulfonic group (sulfo), amine formyl (carbamoyl) or methoxycarbonyl (methoxy carbonyl) person; Preferable, when X be-NHCN ,-OH ,-SCH
2COOH, NHSO
2CH
3, the 3-carboxyl pyridine or
The time, R
1And R
3Be to be hydrogen atom or C
1-4Alkyl.
Formula of the present invention (I) monoazo chemically-reactive dyes, especially good, be to be monoazo chemically-reactive dyes as shown in the formula (Ib).
Wherein
X is-NHCN ,-OH ,-SCH
2COOH, NHSO
2CH
3, 3-carboxyl pyridine (3-carboxypyridinium),
Or halogen; Good especially, X is-NHCN, 3-carboxyl pyridine, chlorine atom or fluorine atom;
Z is-SO
2=CH=CH
2Or-SO
2-CH
2-CH
2-U; U is-OSO
3H, Cl or Br; Good especially, Z is-SO
2-CH
2-CH
2-OSO
3H;
N is 0 or 1, and is preferable, and n is 1;
When X is chlorine atom or fluorine atom, R then
1Be to be hydrogen atom and R
3Be to be C
1-4Alkyl; Preferable, when X is chlorine atom or fluorine atom, R
1Be to be hydrogen atom and R
3Be to be methyl or ethyl;
When X be-NHCN ,-OH ,-SCH
2COOH ,-NHSO
2CH
3, 3-carboxyl pyridine (3-carboxypyridinium) or
The time, R then
1And R
3Independent mutually being selected from respectively comprises hydrogen atom, C
1-4Alkyl or have one or more substituent C
1-4The alkyl person, this substituting group is to be selected from respectively to comprise: hydroxyl (hydroxyl), carboxyl (carboxyl), sulfonic group (sulfo), amine formyl (carbamoyl) or methoxycarbonyl (methoxy carbonyl) person; Preferable, when X be-NHCN ,-OH ,-SCH
2COOH, NHSO
2CH
3, 3-carboxyl-pyridine or
The reactive orchil of the monoazo of formula of the present invention (Ib) preferably is the chemically-reactive dyes as shown in the formula (I-1):
The reactive orchil of the monoazo of formula of the present invention (Ib) preferably is the chemically-reactive dyes as shown in the formula (I-2):
The reactive orchil of the monoazo of formula of the present invention (Ib) preferably is the chemically-reactive dyes as shown in the formula (I-3):
The reactive orchil of the monoazo of formula of the present invention (Ib) preferably is the chemically-reactive dyes as shown in the formula (I-4):
The reactive orchil of the monoazo of formula of the present invention (Ib) preferably is the chemically-reactive dyes as shown in the formula (I-5):
The reactive orchil of the monoazo of formula of the present invention (Ib) preferably is the chemically-reactive dyes as shown in the formula (I-6):
This type of dyestuff is applicable to cellulosic fibres such as cotton, artificial cotton, fiber crops and artificial fiber crops, and the dyeing of tynex such as wool, silk and nylon and trevira.Also applicable to cellulosic fibre or the blending of tynex and trevira, polyacrylonitrile and other fibers or the dyeing of intertexture, can obtain various dyeing properties good dye thing, excellent performance is especially more arranged on daylight fastness.
Embodiment
The preparation of formula of the present invention (I) compound can utilize known method to be synthesized, be exemplified below state step (a) to step (c) but synthetic method preparation formula (I) monoazo chemically-reactive dyes.
Step (a), at first with the azoic dyestuff look of following (III) female with as shown in the formula three halogen Mitsuis (trihalogen triazine) compound of (IV) at pH-value 3-7
Under temperature 0-30 ℃, preferable temperature is reaction below 20 ℃, can obtain the formula V compound, and wherein Hal is halogen, for example fluorine, chlorine or bromine atom.
Step (b), when X is non-when being halogen, then again with the formula V compound with as shown in the formula (VI) compound at pH-value 4 to 12, preferable, pH-value 6 to 10 and temperature 20-80 ℃, preferable, temperature 40-60 is reaction down,
Can obtain the compound of formula (VII), wherein X can be-NHCN ,-OH ,-SCH
2COOH ,-HSO
2CH
3, 3-carboxyl pyrrole forms sediment,
R
1, R
2, R
3Reach n and state as defined above shown in formula (I) reactive azo dyes, Hal is halogen, for example fluorine, chlorine or bromine atom.
Step (c), at last again with formula (VII) compound and as shown in the formula (VIII) compound, or when X is halogen, then directly with the formula V compound and as shown in the formula (VIII) compound,
At pH-value pH=3-11, preferable, pH-value pH=3-7, and under temperature 30-100 ℃, preferable, temperature 55-85 ℃ of following condensation reaction can obtain the reactive azo dyes of formula of the present invention (I).
Aforementioned processing procedure of giving an example, its mutual reaction sequence can arbitrarily change, and (I) reactive azo dyes that similarly obtains formula.
The synthetic method of formula (III) compound can be with reference to United States Patent (USP) the 4th, 837, and is disclosed in No. 310.
The synthesis step of formula (III) compound, be exemplified below, will as shown in the formula the nitro-compound of (X) in temperature-10 after 20 ℃ of following diazotization, again with as shown in the formula the naphthol compound of (XI) in temperature-10 to 50 ℃, preferable, under 0 to 30 ℃, the control pH-value is 1 to 7, and is preferable, at 1 to 5 time, carry out coupled reaction and promptly can be made into the compound as shown in the formula (XII), now carries out the compound that nitro-reduction reaction can make formula (III) for 40 to 100 ℃ in temperature under sodium sulphite exists again.
Above-mentioned formula (X) compound can be listed below example: 2-methoxyl group-4-N-methyl-p-nitroaniline (2-methoxy-4-nitroaniline), 2-oxyethyl group-4-N-methyl-p-nitroaniline (2-ethoxy-4-nitroaniline), 2-propoxy--4-N-methyl-p-nitroaniline (2-propoxy-4-nitroaniline), 2-butoxy-4-N-methyl-p-nitroaniline (2-butoxy-4-nitroaniline), 4-N-methyl-p-nitroaniline-2-sulfonic acid (4-nitroaniline-2-sulfonic acid), 2-carboxyl-4-N-methyl-p-nitroaniline (2-carboxy-4-nitroaniline), 2-fluoro-4-N-methyl-p-nitroaniline (2-fluoro-4-nitroaniline), 2-chloro-4-N-methyl-p-nitroaniline (2-chloro-4-nitroaniline), 2-bromo-4-N-methyl-p-nitroaniline (2-bromo-4-nitroaniline) etc.
Above-mentioned formula (XI) compound can be listed below example:
The aromatic amine of above-mentioned formula (VIII) is to obtain via the capable alkylated reaction of aromatic amine of following formula (XIII); Employed alkylating agent can be alkyl halide (alkylhalide), dialkylsulfates (dialkylsulfate), single displacement ethene (monosubstituted ethylene), or oxide compound (oxide).
H
2N-D-Z
(XIII) alkyl halide can be methyl chloride (methylchloride), ethyl chloride (ethylchloride), normal propyl chloride (n-propylchloride), isopropyl chloride (isopropylchloride), n-butyl chloride (n-buihylchloride), isobutyl chloride (isobuthylchloride), second Butyryl Chloride (sec-buihylchloride), monobromomethane (methylbromide), monobromoethane (eihylbromide), positive propyl bromo (n-propylbromide), isopropyl bromide (isopropylbromide), n-butyl bromide (n-buthylbromide), isobutyl bromide (isobuihylbromide), or second butyl bromide (sec-buthylbromide) etc.
Dialkylsulfates can be dimethyl sulphide acid esters (dimethylsulfate), diethyl sulfide acid esters (diethylsulfate), dipropyl sulfuric acid ketone (dipropylsulfate) etc.; Single displacement ethene has propylene moon green grass or young crops (acrylonitrile), vinylformic acid (acrylic acid), methyl acrylate (methylacrylate), ethyl propenoate (ethylacrylate), acrylamide (acrylamide), vinyl sulfonic acid (vinylsulfonicacid) etc.
Oxide compound has ethylene oxide (ethyleneoxide), propylene oxide (propyleneoxide), ethylene glycol (glycol), oxidation trimethylene (trimethyleneoxide), oxidation of beta-butylene (β-buihyloxide), oxidation 2-methyl-alpha-butylene (2-methyl-α-buthyleneoxide), oxidation 2-ethyl-3-ethylene methacrylic (2-eihyl-3-methyleneoxide), oxidation methoxy-ethylene (methoxyethyleneoxide), or oxidation n-butoxy ethene (n-buthoxyleneoxide) etc.
Above-mentioned formula (XIII) compound can be listed below example: and 1-amido benzene-3-β-sulfate radical network second sulphonyl (1-aminobenzene-3-β-sulfatoethylsulfone); 1-amido benzene-2-β-sulfate radical network second sulphonyl (1-aminobenzene-2-β-sulfatoethylsulfone); 1-amido benzene-3-phosphate radical network ethylbenzene (1-aminobenzene-3-phosphatoethylbenzene); 1-amido-4-methylbenzene-3-β-sulfate radical network second sulphonyl (1-amino-4-methylbenzene-3-β-sulfatoethylsulfone); 1-amido benzene-3-β-chlorination second sulphonyl (1-aminobenzene-3-β-chloroethylsulfone); 1-amido-4-anisole-3-β-sulfate radical network second sulphonyl (1-amino-4-methoxybenzene-3-β-sulfatoethylsulfone); 1-amido-2; 5-dimethyl benzene-4-β-sulfate radical network second sulphonyl (1-amino-2; 5-dimethylbenzene-4-β-sulfatoethylsulfone); 1-amido-2-anisole-4-β-sulfate radical network second sulphonyl (1-amin-2-methoxybenzene-4-β-sulfatoethylsulfone); 1-amido-2-chlorobenzene-4-β-sulfate radical network second sulphonyl (1-amino-2-chlorobenzene-4-β-sulfatoethylsulfone); 1-amido-4-anisole-5-β-sulfate radical network second sulphonyl (1-amino-4-methoxybebzene-5-β-sulfatoethylsulfone); 2-amido naphthalene-8-β-sulfate radical network second sulphonyl-6-sulfonic acid (2-aminonaphthalene-8-β-sulfatoethylsulfone-6-sulfonic acid); 2-amido naphthalene-8-β-sulfate radical network second sulphonyl (2-aminonaphthalene-8-β-sulfatoethylsulfone); 1-amido-2; the 5-dimethoxy benzene-(1-amino 2 for 4-ethene sulphonyl; 5-dimethoxybenzene-4-vinylsulfone); 1-amido-2-methoxyl group-5-methylbenzene-4-β-sulfate radical network second sulphonyl (1-amino-2-methoxy-5-methylbenzene-4-β-sulfatoethylsulfone); 2-amido naphthalene-4; 5; 6-β-sulfate radical network second sulphonyl (2-aminonaphthalene-4; 5; 6-β-sulfatoethylsulfone); 2-amido naphthalene-4; 5; 7-β-sulfate radical network second sulphonyl (2-aminonaphthalene-4; 5; 7-β-sulfatoethylsulfone); 1-amido-2-bromobenzene-4-ethene sulphonyl (1-amino-2-bromobenzene-4-vinylsulfone); 2-amido-8-sulfonic group naphthalene-6-β-sulfate radical network second sulphonyl (2-amino-8-sulfonaphthalene-6-β-sulfatoethylsulfone); 2-amido naphthalene-8-β-phosphate radical network second sulphonyl-6-sulfonic acid (2-aminonaphthalene-8-β-phhosphatoethylsulfone-6-sulfonic acid); 2-amido naphthalene-8-ethene sulphonyl-6-sulfonic acid (2-aminonaphthalene-8-vinylsulfone-6-sulfonic acid); 1-amido-2-methoxyl group-5-methylbenzene-4-β-gasification second sulphonyl (1-amino-2-methoxy-5-methylbenzene-4-chloroethylsulfone); 1-amido benzene-2; 3-ethene sulphonyl (1-aminobenzene-2; 3-vinylsulfone); 1-amido benzene-2; 4-ethene sulphonyl (1-aminobenzene-2,4-vinylsulfone); 1-amido-2-methoxyl group-5-chlorobenzene-4-β-gasification second sulphonyl (1-amin-2-methoxy-5-chlorobenzene-4-β-chloroethylsulfone); 1-amido-2-methoxyl group-5-chlorobenzene-4-ethene sulphonyl (1-amino-2-methoxy-5-chlorobenzene-4-vinylsulfone); 1-amido-2-oxyethyl group-5-chlorobenzene-4-β-gasification second sulphonyl (1-amino-2-ethoxy-5-chlorobenzene-4-β-chloroethylsulfone); 1-amido-2-oxyethyl group-5-chlorobenzene-4-ethene sulphonyl (1-amino-2-ethoxy-5-chlorobenzene-4-vinylsulfone); 2-amido naphthalene-8-β-sulfate radical network second sulphonyl-1-sulfonic acid (2-aminonaphthalene-8-β-sulfatoethylsulfone-1-sulfonic acid); 5-chloroaniline-2-β-sulfate radical network second sulphonyl (5-chloroaniline-2-β-sulfatoethylsulfone); 5-sulfo aniline-2-β-sulfate radical network second sulphonyl (5-sulfoaniline-2-β-sulfatoethylsulfone); aniline-2-β-phosphate radical network second sulphonyl (aniline-2-β phosphatoethylsulfone); 5-chloroaniline-2-β-phosphate radical network second sulphonyl (5-chloroaniline-2-β-phosphatoethylsulfone); 5-chloroaniline-2-ethene sulphonyl (5-chloroanilined-2-vinylsulfone); 5-sulfo aniline-2-ethene sulphonyl (5-sulfoaniline-2-vinylsulfone); aniline-2-β-chlorination second sulphonyl (aniline-2-β-chloroethylsulfone); 5-chloroaniline-2-β-chlorination second sulphonyl (5-chloroaniline-2-β-chloroethylsulfone); 5-sulfo aniline-2-β-chlorination second sulphonyl (5-sulfoaniline-2-β-chloroethylsulfone); aniline-2-β-thiosulfate anion network second sulphonyl (aniline-2-β-thiosulfatoethylsulfone); 5-chloroaniline-2-β-thiosulfate anion network second sulphonyl (5-chloroaniline-2-β-thiosulfatoethylsulfone); 5-moraine acidic group aniline-2-β-thiosulfate anion network second sulphonyl (5-sulfoaniline-2-β-thiosulfatoethylsulfone); 3-amido-2 '-(2-sulfate radical network ethylsulfonyl) ethylbenzene acid amides (3-Amino-2 '-(2-sulfatoethylsulfonyl) ethylbenzamide); 4-amido-2 '-(2-sulfate radical network ethylsulfonyl) ethylbenzene acid amides (4-Amino-2 '-(2-sulfatoethylsulfonyl) ethylbenzamide) etc.
Dyestuff of the present invention can be via the aforesaid method manufacturing, and reaction conditions is clear narration in above-mentioned explanation.Dyestuff of the present invention can obtain with spray method, settling process or filter press technique, and the kenel of dyestuff has powder, fine powder, particle or liquid state and auxiliary agent to add for example retarding agent, dye leveller, dyeing accelerant, interfacial agent or dispersion agent etc.
Dyestuff of the present invention contains an anion-radicals, for example sulfonic group at least.Represent with the sour form of freedom in specification sheets that for convenience of description dyestuff of the present invention kenel with water soluble salt when a large amount of manufacturing exists, particularly for example sodium salt, lithium salts, sylvite or ammonium salt of an alkali metal salt is preferable with sodium salt.
Formula (I) dyestuff meets the present invention to have fiber reactivity and is used in dye transfer and comprise the hydroxide radical group and comprise aminocompound group material.
Formula of the present invention (I) dyestuff is suitable for the various differing materials of dye transfer.Filamentary material such as silk, skin, hair, tynex and polyureas alkane, especially all cellulose.The example of this fiber material is a native cellulose fibre, such as cotton, flax and hemp, and Mierocrystalline cellulose and regenerated cellulose.The dyestuff of formula (I) also is suitable for the dye transfer hydroxyl and is contained in the fiber of the thing of blending, for example the mixture of cotton and trevira or tynex.
Dyestuff of the present invention can be in every way, and especially aqueous dye solutions stamp paste form is applied to fiber and fixation in fiber.It is suitable for the dyeing of dip method and pad dyeing method, if contain the salt that matches, then the dye transfer article are contaminated and painted in aqueous dye solutions, if under suitable heat effect, dyestuff in fixation after the alkaline purification or in the presence of the alkali on the dye transfer article.The dyestuff of invention is specially adapted to the so-called cold rolling method of dying, and wherein dyestuff imposes on the pad fix machine with alkali, and now at room temperature stores a few hours and fixation.After the fixation,,, necessity removed not outstanding admittedly part if then adding dispersion agent with cold water and hot water rinsing dye transfer thing.
The present invention is the purposes and the relevant method of utilizing method dyeing (comprising printing and dyeing) dye transfer material of practising of dyeing (comprising printing and dyeing) the dye transfer material of relevant this formula (I) compound also, its Chinese style (I) is a colorant, its with formula (I) compound put on material mat heat in the aqueous medium or alkali or the two with its fixation in the dye transfer material.
The characteristic of the dyestuff of formula (I) is a hyperergy, good fixation ability and splendid depth.Also have outstanding color depth, equalization and detergency, and have high dissolubility, height and exhaust when high solid work ratio.Therefore it can be used for the dip-dye method and need only lack the steam treatment time at pad steaming process at low dyeing temperature.The non-outstanding admittedly part of the high and easy eccysis of degree of fixation, dye uptake and degree of fixation differences are minimum, and the loss of promptly soaping is extremely low.Formula (I) dyestuff also is suitable for printing and dyeing especially, and is especially cotton, also is suitable for the nitrogen-containing fiber of printing and dyeing in the same manner, for example hair or silk or contain hair or the BLENDED FABRIC of silk.
Have high chroma and high fiber with dyestuff of the present invention for the dyeing and the printing and dyeing of cellulosic fibre material, dyestuff is in conjunction with stability, in acid and alkali scope all in this way, other has good anti-daylight fastness, sweat proof daylight fastness and splendid moisture-proof fastness characteristic, such as water-fastly wash, water-fast, sea water resistance, anti-cross dyeing and perspiration resistance fastness, and the good pleat of anti-crape fastness, anti-flatiron fastness and fastness to rubbing.
The detailed description of preferred embodiment
Therefore following example is in explanation the present invention, and claim of the present invention can't be and restricted.Compound shown in the general formula is to be the acid type attitude of dissociating; Usually they are to isolate and be used for dyeing with its esters kenel with the kenel of its an alkali metal salt.The acid type attitude initial compounds of mentioning in following example that dissociates similarly can be used for synthetic immediately or be used for synthetic with its esters kenel (being preferably alkaline metal salt, for example sodium salt or sylvite).
Following example is in explanation the present invention, if there is not special proof, then umber and per-cent are by weight.The relation of parts by weight and volume parts is just as the relation of kilogram with litre.
Optical density maximum value (λ in the visible-range of The compounds of this invention
Max) be to measure by means of its an alkali metal salt in the aqueous solution.
Embodiment 1
With 21.8 parts 4-N-methyl-p-nitroaniline-2-sulfonic acid and 21.7 part 35% sodium nitrite solution, dissolving is scattered in 150 parts of water, and now comprises its adding in the ice sour water of 300 portions of frozen water and 35.5 parts of concentrated hydrochloric acids, continues stirring until then and finishes diazotization.
Then, add 31.9 parts of 2-amino-8-hydroxyl naphthalene-3, the 6-disulfonic acid is in wherein, and at room temperature stirs this mixture to finishing coupled reaction.Then, this reaction mixture pH-value is adjusted to 8 to 10, mix again, with this mixture heating up to 60 ℃ and keep temperature to finishing reductive action with 10.7 parts of sodium sulphite.
In reaction mixture, add 40 parts of sodium-chlor then, filter then and wash it.The above-mentioned thing that leaches is scattered in 400 portions of frozen water, adds 16.7 parts of tricyanogen chlorides again, stir this mixture down, keep pH-value in 4 to 5 scopes with aqueous sodium carbonate simultaneously, can obtain containing the mixture (A) of formula (I) compound at 0 to 10 ℃ in wherein
Embodiment 2
In mixture (A), add 1-N-ethyl amido benzene-3-β-sulfate radical network second sulphonyl of 27.8 parts, and be heated to 55 ℃ and maintenance pH-value 4 to 5, finish after the filtration of saltouing can obtain formula (2) compound, (λ to reacting
Max=525nm),
Embodiment 3 to 33
Repeat the step of embodiment 2, react but replace 1-N-ethyl amido benzene-3-β-sulfate radical network second sulphonyl with the alternative compounds shown in following respectively; Can obtain at 525 ± 2nm blue light red monoazo-dyes.
| The embodiment numbering | Alternative compounds |
| Embodiment 3 | 1-N-ethyl amido benzene-4-β-sulfate radical network second sulphonyl |
| Embodiment 4 | 1-N-ethyl amido benzene-2-β-sulfate radical network second sulphonyl |
| Embodiment 5 | 1-N-ethylamine-4-anisole-3-β-sulfate radical network second sulphonyl |
| Embodiment 6 | 1-N-methyl amido benzene-3-β-sulfate radical network second sulphonyl |
| Embodiment 7 | 1-N-methyl amido benzene-4-β-sulfate radical network second sulphonyl |
| Embodiment 8 | 1-N-methyl amido benzene-2-β-sulfate radical network second sulphonyl |
| Embodiment 9 | 1-N-methylamine-4-anisole-3-β-sulfate radical network second sulphonyl |
| Embodiment 10 | 1-N-β-amine formyl ethyl amido benzene-3-β-sulfate radical network second sulphonyl |
| Embodiment 11 | 1-N-β-amine formyl ethyl amido benzene-4-β-sulfate radical network second sulphonyl |
| Embodiment 12 | 1-N-β-amine formyl ethyl amido benzene-2-β-sulfate radical network second sulphonyl |
| Embodiment 13 | 1-N-β-amine formyl ethyl amido-4-anisole-3-β-sulfate radical network second sulphonyl |
| Embodiment 14 | 1-N-n-propyl amido benzene-3-β-sulfate radical network second sulphonyl |
| Embodiment 15 | 1-N-n-propyl amido benzene-4-β-sulfate radical network second sulphonyl |
| Embodiment 16 | 1-N-n-propyl amido benzene-2-β-sulfate radical network second sulphonyl |
| Embodiment 17 | 1-N-n-propyl amine-4-anisole-3-β-sulfate radical network second sulphonyl |
| Embodiment 18 | 1-N-β-cyanoethyl amido benzene-3-β-sulfate radical network second sulphonyl |
| Embodiment 19 | 1-N-β-cyanoethyl amido benzene-4-β-sulfate radical network second sulphonyl |
| Embodiment 20 | 1-N-β-cyanoethyl amido benzene-2-β-sulfate radical network second sulphonyl |
| Embodiment 21 | 1-N-β-cyanoethyl amine-4-anisole-3-β-sulfate radical network second sulphonyl |
| Embodiment 22 | 1-N-beta-hydroxyethyl amido benzene-3-β-sulfate radical network second sulphonyl |
| Embodiment 23 | 1-N-beta-hydroxyethyl amido benzene-4-β-sulfate radical network second sulphonyl |
| Embodiment 24 | 1-N-beta-hydroxyethyl amido benzene-2-β-sulfate radical network second sulphonyl |
| Embodiment 25 | 1-N-beta-hydroxyethyl amine-4-anisole-3-β-sulfate radical network second sulphonyl |
| Embodiment 26 | 1-N-β-sulfonic acid ethyl amido benzene-3-β-sulfate radical network second sulphonyl |
| Embodiment 27 | 1-N-beta-methoxy-carbonyl ethyl amido benzene-3-β-sulfate radical network second sulphonyl |
| Embodiment 28 | 1-N-ethylamine-2-anisole-5-β-sulfate radical network second sulphonyl |
| Embodiment 29 | 1-N-ethylamine-2,4-dimethyl benzene-5-β-sulfate radical network second sulphonyl |
| Embodiment 30 | 1-N-ethylamine-2-methylbenzene-5-methylbenzene-3-β-sulfate radical network second sulphonyl |
| Embodiment 31 | 1-N-ethyl amido naphthalene-6-β-sulfate radical network second sulphonyl |
| Embodiment 32 | 1-N-ethylamine-8-sulfonic acid naphthalene-6-β-sulfate radical network second sulphonyl |
| Embodiment 33 | 1-N-methyl amido naphthalene-8-β-sulfate radical network second sulphonyl |
Embodiment 34
In mixture (A), add 3.78 parts of atmosphere amine aqueous solutions that are dissolved in 100 parts of water, and be heated to 40 to 60 ℃, simultaneously with aqueous sodium carbonate control pH-value in 8 to 10 scopes, to reaction finish mixture (B), filter three mouthfuls of hydrazinium compounds of monochloro that can obtain formula (34) again through saltouing.
Embodiment 35
In mixture (B), add 1-amido benzene-3-β-sulfate radical network second sulphonyl of 25.3 parts, and be heated to 55 ℃ and keep pH-value 4 to 6 to reaction to finish after saltout to filter and to obtain formula (35) compound, (λ
Max=525nm),
Embodiment 36 to 76
Repeat the step of embodiment 35, react but replace 1-amido benzene-3-β-sulfate radical network second sulphonyl with the alternative compounds shown in following respectively; Can obtain at 525 ± 2nm blue light red monoazo-dyes.
| The embodiment numbering | Alternative compounds |
| Embodiment 36 | 1-N-ethyl amido benzene-4-β-sulfate radical network second sulphonyl |
| Embodiment 37 | 1-N-ethyl amido benzene-2-β-sulfate radical network second sulphonyl |
| Embodiment 38 | 1-N-ethylamine-4-anisole-3-β-sulfate radical network second sulphonyl |
| Embodiment 39 | 1-N-methyl amido benzene-3-β-sulfate radical network second sulphonyl |
| Embodiment 40 | 1-N-methyl amido benzene-4-β-sulfate radical network second sulphonyl |
| Embodiment 41 | 1-N-methyl amido benzene-2-β-sulfate radical network second sulphonyl |
| Embodiment 42 | 1-N-methylamine-4-anisole-3-β-sulfate radical network second sulphonyl |
| Embodiment 43 | 1-N-β-amine formyl ethyl amido benzene-3-β-sulfate radical network second sulphonyl |
| Embodiment 44 | 1-N-β-amine formyl ethyl amido benzene-4-β-sulfate radical network second sulphonyl |
| Embodiment 45 | 1-N-β-amine formyl ethyl amido benzene-2-β-sulfate radical network second sulphonyl |
| Embodiment 46 | 1-N-β-amine formyl ethyl amido-4-anisole-3-β-sulfate radical network second sulphonyl |
| Embodiment 47 | 1-N-n-propyl amido benzene-3-β-sulfate radical network second sulphonyl |
| Embodiment 48 | 1-N-n-propyl amido benzene-4-β-sulfate radical network second sulphonyl |
| Embodiment 49 | 1-N-n-propyl amido benzene-2-β-sulfate radical network second sulphonyl |
| Embodiment 50 | 1-N-n-propyl amine-4-anisole-3-β-sulfate radical network second sulphonyl |
| Embodiment 51 | 1-N-β-cyanoethyl amido benzene-3-β-sulfate radical network second sulphonyl |
| Embodiment 52 | 1-N-β-cyanoethyl amido benzene-4-β-sulfate radical network second sulphonyl |
| Embodiment 53 | 1-N-β-cyanoethyl amido benzene-2-β-sulfate radical network second sulphonyl |
| Embodiment 54 | 1-N-β-cyanoethyl amine-4-anisole-3-β-sulfate radical network second sulphonyl |
| Embodiment 55 | 1-N-beta-hydroxyethyl amido benzene-3-β-sulfate radical network second sulphonyl |
| Embodiment 56 | 1-N-beta-hydroxyethyl amido benzene-4-β-sulfate radical network second sulphonyl |
| Embodiment 57 | 1-N-beta-hydroxyethyl amido benzene-2-β-sulfate radical network second sulphonyl |
| Embodiment 58 | 1-N-beta-hydroxyethyl amine-4-anisole-3-β-sulfate radical network second sulphonyl |
| Embodiment 59 | 1-N-β-sulfonic acid ethyl amido benzene-3-β-sulfate radical network second sulphonyl |
| Embodiment 60 | 1-N-beta-methoxy-carbonyl ethyl amido benzene-3-β-sulfate radical network second sulphonyl |
| Embodiment 61 | 1-N-ethylamine-2-anisole-5-β-sulfate radical network second sulphonyl |
| Embodiment 62 | 1-N-ethylamine-2,4-dimethyl benzene-5-β-sulfate radical network second sulphonyl |
| Embodiment 63 | 1-N-ethylamine-2-methylbenzene-5-methylbenzene-3-β-sulfate radical network second sulphonyl |
| Embodiment 64 | 1-N-ethyl amido naphthalene-6-β-sulfate radical network second sulphonyl |
| Embodiment 65 | 1-N-ethylamine-8-sulfonic acid naphthalene-6-β-sulfate radical network second sulphonyl |
| Embodiment 66 | 1-N-methyl amido naphthalene-8-β-sulfate radical network second sulphonyl |
| Embodiment 67 | 1-N-amido benzene-4-β-sulfate radical network second sulphonyl |
| Embodiment 68 | 1-N-amido benzene-2-β-sulfate radical network second sulphonyl |
| Embodiment 69 | 1-N-ethyl amido benzene-3-β-sulfate radical network second sulphonyl |
| Embodiment 70 | 1-amido-4-anisole-3-β-sulfate radical network second sulphonyl |
| Embodiment 71 | 1-amido-2-anisole-5-β-sulfate radical network second sulphonyl |
| Embodiment 72 | 1-amido-2-methoxyl group-5-methylbenzene-4-β-sulfate radical network second sulphonyl |
| Embodiment 73 | 1-amido-2,4-dimethyl benzene-5-β-sulfate radical network second sulphonyl |
| Embodiment 74 | 1-amido naphthalene-6-β-sulfate radical network second sulphonyl |
| Embodiment 75 | 1-amido-8-sulfonic acid naphthalene-6-β-sulfate radical network second sulphonyl |
| Embodiment 76 | 1-amido naphthalene-8-β-sulfate radical network second sulphonyl |
Embodiment 77
The 1-amido benzene-3-β-sulfate radical network second sulphonyl that in mixture (A), adds 25.3 parts, and be heated to 55 ℃ and keep pH-value 4 to 5, after extremely reaction is finished, add 18.5 parts 3-carboxyl pyridine again and be heated to 85 to 90 ℃ and maintenance pH-value 4 to 5, finish after the filtration of saltouing can obtain formula (77) compound (λ to reacting
Max=528nm),
Embodiment 78 to 118
Repeat the step of embodiment 77,1-amido benzene-3-β-sulfate radical network second sulphonyl reacts among the embodiment 77 but replace with the alternative compounds shown in following respectively; Can obtain at 528 ± 2nm basket light red monoazo-dyes.
| The embodiment numbering | Alternative compounds |
| Embodiment 78 | 1-N-ethyl amido benzene-4-β-sulfate radical network second sulphonyl |
| Embodiment 79 | 1-N-ethyl amido benzene-2-β-sulfate radical network second sulphonyl |
| Embodiment 80 | 1-N-ethylamine-4-anisole-3-β-sulfate radical network second sulphonyl |
| Embodiment 81 | 1-N-methyl amido benzene-3-β-sulfate radical network second sulphonyl |
| Embodiment 82 | 1-N-methyl amido benzene-4-β-sulfate radical network second sulphonyl |
| Embodiment 83 | 1-N-methyl amido benzene-2-β-sulfate radical network second sulphonyl |
| Embodiment 84 | 1-N-methylamine-4-anisole-3-β-sulfate radical network second sulphonyl |
| Embodiment 85 | 1-N-β-amine formyl ethyl amido benzene-3-β-sulfate radical network second sulphonyl |
| Embodiment 86 | 1-N-β-amine formyl ethyl amido benzene-4-β-sulfate radical network second sulphonyl |
| Embodiment 87 | 1-N-β-amine formyl ethyl amido benzene-2-β-sulfate radical network second sulphonyl |
| Embodiment 88 | 1-N-β-amine formyl ethyl amido-4-anisole-3-β-sulfate radical network second sulphonyl |
| Embodiment 89 | 1-N-n-propyl amido benzene-3-β-sulfate radical network second sulphonyl |
| Embodiment 90 | 1-N-n-propyl amido benzene-4-β-sulfate radical network second sulphonyl |
| Embodiment 91 | 1-N-n-propyl amido benzene-2-β-sulfate radical network second sulphonyl |
| Embodiment 92 | 1-N-n-propyl amine-4-anisole-3-β-sulfate radical network second sulphonyl |
| Embodiment 93 | 1-N-β-cyanoethyl amido benzene-3-β-sulfate radical network second sulphonyl |
| Embodiment 94 | 1-N-β-cyanoethyl amido benzene-4-β-sulfate radical network second sulphonyl |
| Embodiment 95 | 1-N-β-cyanoethyl amido benzene-2-β-sulfate radical network second sulphonyl |
| Embodiment 96 | 1-N-β-cyanoethyl amine-4-anisole-3-β-sulfate radical network second sulphonyl |
| Embodiment 97 | 1-N-beta-hydroxyethyl amido benzene-3-β-sulfate radical network second sulphonyl |
| Embodiment 98 | 1-N-beta-hydroxyethyl amido benzene-4-β-sulfate radical network second sulphonyl |
| Embodiment 99 | 1-N-beta-hydroxyethyl amido benzene-2-β-sulfate radical network second sulphonyl |
| Embodiment 100 | 1-N-beta-hydroxyethyl amine-4-anisole-3-β-sulfate radical network second sulphonyl |
| Embodiment 101 | 1-N-β-sulfonic acid ethyl amido benzene-3-β-sulfate radical network second sulphonyl |
| Embodiment 102 | 1-N-beta-methoxy-carbonyl ethyl amido benzene-3-β-sulfate radical network second sulphonyl |
| Embodiment 103 | 1-N-ethylamine-2-anisole-5-β-sulfate radical network second sulphonyl |
| Embodiment 104 | 1-N-ethylamine-2,4-dimethyl benzene-5-β-sulfate radical network second sulphonyl |
| Embodiment 105 | 1-N-ethylamine-2-methylbenzene-5-methylbenzene-3-β-sulfate radical network second sulphonyl |
| Embodiment 106 | 1-N-ethyl amido naphthalene-6-β-sulfate radical network second sulphonyl |
| Embodiment 107 | 1-N-ethylamine-8-sulfonic acid naphthalene-6-β-sulfate radical network second sulphonyl |
| Embodiment 108 | 1-N-methyl amido naphthalene-8-β-sulfate radical network second sulphonyl |
| Embodiment 109 | 1-N-amido benzene-4-β-sulfate radical network second sulphonyl |
| Embodiment 110 | 1-N-amido benzene-2-β-sulfate radical network second sulphonyl |
| Embodiment 111 | 1-N-ethyl amido benzene-3-β-sulfate radical network second sulphonyl |
| Embodiment 112 | 1-amido-4-anisole-3-β-sulfate radical network second sulphonyl |
| Embodiment 113 | 1-amido-2-anisole-5-β-sulfate radical network second sulphonyl |
| Embodiment 114 | 1-amido-2-methoxyl group-5-methylbenzene-4-β-sulfate radical network second sulphonyl |
| Embodiment 115 | 1-amido-2,4-dimethyl benzene-5-β-sulfate radical network second sulphonyl |
| Embodiment 116 | 1-amido naphthalene-6-β-sulfate radical network second sulphonyl |
| Embodiment 117 | 1-amido-8-sulfonic acid naphthalene-6-β-sulfate radical network second sulphonyl |
| Embodiment 118 | 1-amido naphthalene-8-β-sulfate radical network second sulphonyl |
Embodiment 119
With 21.8 parts 4-N-methyl-p-nitroaniline-2-sulfonic acid and 21.7 part 35% sodium nitrite solution, dissolving is scattered in 150 parts of water, and now comprises its adding in the ice sour water of 300 portions of frozen water and 35.5 parts of concentrated hydrochloric acids, continues stirring until then and finishes diazotization.
Now adds 33.3 parts of 2-N-methylaminos-8-hydroxyl naphthalene-3, and the 6-disulfonic acid is in wherein, and at room temperature stirs this mixture to finishing coupled reaction.Then, this reaction mixture pH-value is adjusted to 8 to 10, mix again, with this mixture heating up to 60 ℃ and keep temperature to finishing reductive action with 10.7 parts of sodium sulphite.
In reaction mixture, add 40 parts of sodium-chlor then, filter then and wash it.The above-mentioned thing that leaches is scattered in 400 portions of frozen water, adds 16.7 parts of tricyanogen chlorides again, under 0 to 10 ℃, stir this mixture, keep pH-value in 4 to 5 scopes, to finish with aqueous sodium carbonate simultaneously, can finish first condensation reaction to reacting in wherein.Add 3.78 parts of cyanamides and be dissolved in 100 parts of aqueous solution in the water and go in this reaction mixture, this mixture heating up to 40 to 60 ℃, is finished to reaction in 8 to 10 scopes with aqueous sodium carbonate control pH-value simultaneously, can finish second condensation reaction.
In addition, add 25.3 parts of 1-amido benzene-3-β-sulfate radical network second sulphonyl to the above-mentioned reaction mixture, with this mixture heating up to 55 ℃ and protect the pH-value 4 to 6 of fighting, finish after saltout to filter and to obtain formula (119) compound, (λ to reaction
Max=530nm),
Embodiment 120 to 193
Repeat embodiment 119, formula (XI) naphthol compound with second hurdle that is listed in the table below replaces 2-N-methylamino-8-hydroxyl naphthalene-3,-6-disulfonic acid, formula (X) compound of listing in third column replaces 4-N-methyl-p-nitroaniline-2-sulfonic acid, list in the cyanamide on the 4th hurdle, and formula (VIII) the aromatic amines compound replacement 1-amido benzene-3-β-sulfate radical network second sulphonyl of listing in the 5th hurdle, can obtain each desired Monoazo compound.
Real
Execute the form and aspect of molecular formula (X) the cyanamide molecular formula (VIII) of molecular formula (XI)
The compound compound of example compound
Compile
Number
Embodiment 194
With 21.8 parts 4-N-methyl-p-nitroaniline-2-sulfonic acid and 21.7 part 35% sodium nitrite solution, dissolving is scattered in 150 parts of water, and now comprises its adding in the ice sour water of 300 portions of frozen water and 35.5 parts of concentrated hydrochloric acids, continues stirring until then and finishes diazotization.
Now adds 33.3 parts of 2-N-methylaminos-8-hydroxyl naphthalene-3, and the 6-disulfonic acid is in wherein, and at room temperature stirs this mixture to finishing coupled reaction.Then, this reaction mixture pH-value is adjusted to 8 to 10, mix again, with this mixture heating up to 60 ℃ and keep temperature to finishing reductive action with 10.7 parts of sodium sulphite.
In reaction mixture, add 40 parts of sodium vapors then, filter then and wash it.The above-mentioned thing that leaches is scattered in 400 portions of frozen water, adds 16.7 parts of tricyanogen chlorides again, under 0 to 10 ℃, stir this mixture, keep pH-value in 4 to 5 scopes, to finish with aqueous sodium carbonate simultaneously, can finish first condensation reaction to reacting in wherein.Add 25.3 parts of 1-amido benzene-3-β-sulfate radical network second sulphonyl and go in this reaction mixture, with this mixture heating up to 55 ℃ and keep in the pH-value 4 to 6 finishing, can finish second condensation reaction to reaction.
In addition, add 18.5 parts of 3-carboxyl pyridines to above-mentioned reaction mixture, this mixture heating up to 85 to 90 ℃ and maintenance pH-value 4 to 5, is finished after the filtration of saltouing can obtain formula (194) compound (λ to reacting
Max=535nm).
Embodiment 195 to 268
Repeat embodiment 194, formula (XI) naphthol compound with second hurdle that is listed in the table below replaces 2-N-methylamino-8-hydroxyl naphthalene-3, the 6-disulfonic acid, formula (X) compound of listing in third column replaces 4-N-methyl-p-nitroaniline-2-sulfonic acid, list in the 3-carboxyl pyridine on the 4th hurdle, and formula (VIII) the aromatic amines compound replacement 1-amido benzene-3-β-sulfate radical network second sulphonyl of listing in the 5th hurdle, can obtain each desired Monoazo compound.
Real
Execute the form and aspect of molecular formula (X) the 3-carboxyl molecular formula (VIII) of molecular formula (XI)
The compound pyridine compounds of example compound
Compile
Number
Embodiment 269
With 21.8 parts 4-N-methyl-p-nitroaniline-2-sulfonic acid and 21.7 part 35% sodium nitrite solution, dissolving is scattered in 150 parts of water, and now comprises its adding in the ice sour water of 300 portions of frozen water and 35.5 parts of concentrated hydrochloric acids, continues then to whisk to finishing diazotization.
Then, add 23.8 parts of 2-amino-8-hydroxyl naphthalene-6-sulfonic acid in wherein, and at room temperature stir this mixture to finishing coupled reaction.Then, this reaction mixture pH-value is adjusted to 8 to 10, mix again, with this mixture heating up to 60 ℃ and keep temperature to finishing reductive action with 10.7 parts of sodium sulphite.
In reaction mixture, add 40 parts of sodium vapors then, filter then and wash it.The above-mentioned thing that leaches is scattered in 400 portions of frozen water, adds 16.7 parts of trimerization chlorination helium again, under 0 to 10 ℃, stir this mixture, keep pH-value in 4 to 5 scopes, to finish with the sodium carbonate aqueous solution simultaneously, can finish first condensation reaction to reacting in wherein.The 1-N-ethyl amido benzene-3-β-sulfate radical network second sulphonyl that adds 27.8 parts and is heated to 55 ℃ and keep pH-value 4 to 5 to the above-mentioned reaction mixture, finishes after saltout to filter and can obtain formula (269) compound, (λ to reaction
Max=518nm).
Embodiment 270 to 295
Repeat embodiment 269, formula (XI) naphthol compound with second hurdle that is listed in the table below replaces 2-amino-8-hydroxyl naphthalene-6-sulfonic acid, formula (X) compound of listing in third column replaces 4-N-methyl-p-nitroaniline-2-sulfonic acid, list in the tricyanogen chloride or the trimerization fluoro-cyanogen on the 4th hurdle and then represent tricyanogen chloride and trimerization fluoro-cyanogen with Cl and F individually, and formula (VIII) the aromatic amines compound replacement 1-N-ethyl amido benzene-3-β-sulfate radical network second sulphonyl of listing in the 5th hurdle, can obtain each desired Monoazo compound.
Real
Execute the form and aspect of molecular formula (X) the trimerization chlorination molecular formula (VIII) of molecular formula (XI)
The compound cyanogen or the trimerizing compound of example compound
Compile fluoro-cyanogen
Number
Embodiment 296
Earlier 100 parts in urea, reduction are prevented 10 parts of agent, 20 parts in sodium bicarbonate, 55 parts of sodium alginates, and 815 parts in warm water adds up to 1000 parts can get auxiliary agent and stick with paste through stirring; Get 3 parts of embodiment, 2 prepared formula (2) dyestuffs and spill in above-mentioned 100 parts auxiliary agent is stuck with paste, and stir fast.45 degree twill version stamp half tones with 100mesh cover on the mercerized cotton drills of a suitable size, and the look paste was being scraped, and the cloth of scraping is put into oven dry in 5 minutes in 65 ℃ of baking ovens; The cloth that oven dry is good is put into steam box with normal pressure saturated vapo(u)r 102-105 ℃ steaming place 10 minutes.Afterwards, resultant blueness is dyed thing earlier through cold wash, through boiling hot water wash 10 minutes, soaps 10 minutes through the ebullient nonionic detergent, wash down once with cold water again, drying.The thing that dyes that can obtain the blue light redness possesses excellent characteristic.
Embodiment 297
Get 3 parts of embodiment, 2 prepared formula (2) dyestuffs and be dissolved in 100 ml waters, be mixed with 30 parts/dye liquor boosts; Get alkaline agent (30 parts/liter in 15 milliliters/liter of 38 ° of Be ' of use caustic soda and saltcake) and be incorporated in (the alkaline agent consumption is 1/4th of the pressure dye liquor) even stirring in the pressure dye liquor, the gained mixed solution is poured roller (Roller) pressure into and is dyed in the device, after then cotton fabric being dyed through the roller pressure, be rolled into a shape again.This form cotton fabric at room temperature stores 4 hours.Afterwards, resultant blueness is dyed thing earlier through cold wash, through boiling hot water wash 10 minutes, soaps 10 minutes through the ebullient nonionic detergent, wash down once with cold water again, drying.The thing that dyes that can obtain basket light redness possesses excellent characteristic.
Embodiment 298
Get 0.25 part of embodiment, 2 prepared formula (2) dyestuffs and be dissolved in 250 ml waters, be called mother liquor (0.1%), get 40 milliliters in 0.1% mother liquor in staining bottle, put into 2 parts of cotton fabrics, put into 2.4 parts of saltcake again, put into 2.5 milliliters of 32% soda ash solutions again; To dye bottle and put into 60 ℃ level concussion dyeing machinery, be incubated 60 minutes.Afterwards, resultant blueness is dyed thing earlier through cold wash, through boiling hot water wash 10 minutes, soaps 10 minutes through the ebullient nonionic detergent, wash down once with cold water again, drying.Prepared basket light redness is dyed thing and is possessed excellent characteristic.
Embodiment 299
Get 0.25 part of embodiment, 35 prepared formula (35) dyestuffs and be dissolved in 250 ml waters, be called mother liquor (0.1%), get 40 milliliters in 0.1% mother liquor in staining bottle, put into 2 parts of cotton fabrics, put into 2.4 parts of saltcake again, put into 2.5 milliliters of 32% soda ash solutions again; To dye bottle and put into 60 ℃ level concussion dyeing machinery, be incubated 60 minutes.Afterwards, resultant blueness is dyed thing earlier through cold wash, through boiling hot water wash 10 minutes, soaps 10 minutes through the ebullient nonionic detergent, wash down once with cold water again, drying.Prepared blue light redness is dyed thing and is possessed excellent characteristic.
Embodiment 300
Get 0.25 part of prepared formula (77) dyestuff of embodiment 77=and be dissolved in 250 ml waters, be called mother liquor (0.1%), get 40 milliliters in 0.1% mother liquor in staining bottle, put into 2 parts of cotton fabrics, put into 2.4 parts of saltcake again, put into 2.5 milliliters of 32% soda ash solutions again; To dye bottle and put into 60 ℃ level concussion dyeing machinery, be incubated 60 minutes.Afterwards, resultant blueness is dyed thing earlier through cold wash, through boiling hot water wash 10 minutes, soaps 10 minutes through the ebullient nonionic detergent, wash down once with cold water again, drying.Prepared basket light redness is dyed thing and is possessed excellent characteristic.
Embodiment 301
Get 0.25 part of embodiment, 119 prepared formula (119) dyestuffs and be dissolved in 250 ml waters, be called mother liquor (0.1%), get 40 milliliters in 0.1% mother liquor in staining bottle, put into 2 parts of cotton fabrics, put into 2.4 parts of saltcake again, put into 2.5 milliliters of 32% soda ash solutions again; To dye bottle and put into 60 ℃ level concussion dyeing machinery, be incubated 60 minutes.Afterwards, resultant blueness is dyed thing earlier through cold wash, through boiling hot water wash 10 minutes, soaps 10 minutes through the ebullient nonionic detergent, wash down once with cold water again, drying.Prepared basket light redness is dyed thing and is possessed excellent characteristic.
Embodiment 302
Get 0.25 part of embodiment, 194 prepared formula (194) dyestuffs and be dissolved in 250 ml waters, be called mother liquor (0.1%), get 40 milliliters in 0.1% mother liquor in staining bottle, put into 2 parts of cotton fabrics, put into 2.4 parts of saltcake again, put into 2.5 milliliters of 32% soda ash solutions again; To dye bottle and put into 60 ℃ level concussion dyeing machinery, be incubated 60 minutes.Afterwards, resultant blueness is dyed thing earlier through cold wash, through boiling hot water wash 10 minutes, soaps 10 minutes through the ebullient nonionic detergent, wash down once with cold water again, drying.Prepared blue light redness is dyed thing and is possessed excellent characteristic.
Embodiment 303
Get 0.25 part of embodiment, 269 prepared formula (269) dyestuffs and be dissolved in 250 ml waters, be called mother liquor (0.1%), get 40 milliliters in 0.1% mother liquor in staining bottle, put into 2 parts of cotton fabrics, put into 2.4 parts of saltcake again, put into 2.5 milliliters of 32% soda ash solutions again; To dye bottle and put into 60 ℃ level concussion dyeing machinery, be incubated 60 minutes.Afterwards, resultant blueness is dyed thing earlier through cold wash, through boiling hot water wash 10 minutes, soaps 10 minutes through the ebullient nonionic detergent, wash down once with cold water again, drying.Prepared basket light redness is dyed thing and is possessed excellent characteristic.
Be noted that above-mentioned is embodiment only, but not is limited to embodiment.Do not break away from basic framework of the present invention such as this, all should be the interest field that this patent is advocated, and should be as the criterion with patent claim.
Claims (29)
1. the reactive orchil of the monoazo as shown in the formula (I) is characterized in that,
Wherein
X is-NHCN ,-OH ,-SCH
2COOH ,-NHSO
2CH
3, the 3-carboxyl pyridine,
D is for having 0 to 3 substituent phenyl ring or naphthalene nucleus, and this substituting group is to be selected from respectively to comprise: halogen, C
1-4Alkyl, C
1-4Alkoxyl group, nitro, amido, hydroxyl, carboxyl, phosphate and sulfonic group;
Z is-SO
2-CH=CH
2Or-SO
2-CH
2-CH
2-U; U is-OSO
3H, Cl, Br ,-OPO
3H
2,-SSO
3H or
R
2Be sulfonic group, carboxyl, halogen or C
1-4Alkoxyl group;
N is 0 or 1;
When X is halogen atom, R then
1Be to be hydrogen atom and R
3Be to be C
1-4Alkyl or have at least 1 substituent C
1-4Alkyl;
When X be-NHCN ,-OH ,-SCH
2COOH ,-NHSO
2CH
3, the 3-carboxyl pyridine or
Or have one or more substituent C
1-4The alkyl person, this substituting group is to be selected from respectively to comprise: the many bases of hydroxyl, carboxyl, sulfonic group, amine formyl or methoxy.
2. the reactive orchil of monoazo as claimed in claim 1 is characterized in that, wherein X is-NHCN, 3-carboxyl pyridine, chlorine atom or fluorine atom.
2. the reactive orchil of monoazo as claimed in claim 1 is characterized in that wherein D is for having 0 to 3 substituent phenyl ring.
4. the reactive orchil of monoazo as claimed in claim 1 is characterized in that, wherein Z is-SO
2=CH=CH
2Or-SO
2-CH
2-CH
2-OSO
3H.
5. the reactive orchil of monoazo as claimed in claim 1 is characterized in that, wherein R
2Be to be sulfonic group or carboxyl.
6. the reactive orchil of monoazo as claimed in claim 1 is characterized in that wherein n is 1.
7. the reactive orchil of monoazo as claimed in claim 1 is characterized in that, wherein when X is chlorine atom or fluorine atom, and R then
1Be to be hydrogen atom and R
3Be to be C
1-4Alkyl.
8. the reactive orchil of monoazo as claimed in claim 1 is characterized in that, wherein work as X to be-NHCN ,-OH ,-SCH
2COOH ,-NHSO
2CH
3, the 3-carboxyl pyridine or
The time, R then
1And R
3Independent mutually hydrogen atom or the C of being selected from respectively
1-4Alkyl.
9. the reactive orchil of monoazo as claimed in claim 1 is characterized in that its Chinese style (I) is to be the chemically-reactive dyes as shown in the formula (Ia),
Wherein
X is-NHCN ,-OH ,-SCH
2COOH ,-NHSO
2CH
3, the 3-carboxyl pyridine,
D is for having 0 to 3 substituent phenyl ring or naphthalene nucleus, and this substituting group is to be selected from respectively to comprise: halogen, C
1-4Alkyl, C
1-4Alkoxyl group, nitro, amido, hydroxyl, carboxyl, phosphate and sulfonic group;
Z is-SO
2-CH=CH
2Or-SO
2-CH
2-CH
2-U; U is-OSO
3H, Cl or Br ,-OPOH
2,-SSO
3H or
N is 0 or 1;
When X is halogen atom, R then
1Be to be hydrogen atom and R
3Be to be C
1-4Alkyl or have at least 1 substituent C
1-4Alkyl;
When X be-NHCN ,-OH ,-SCH
2COOH ,-NHSO
2CH
3, the 3-carboxyl pyridine or
The time, R then
1And R
3Independent mutually being selected from respectively comprises hydrogen atom, C
1-4Alkyl, phenyl,
Or have one or more substituent C
1-4The alkyl person, this substituting group is to be selected from respectively to comprise: hydroxyl, carboxyl, sulfonic group, amine formyl or methoxycarbonyl.
10. the reactive orchil of monoazo as claimed in claim 9 is characterized in that, wherein X is-NHCN, 3-carboxyl pyridine, chlorine atom or fluorine atom.
11. the reactive orchil of monoazo as claimed in claim 9 is characterized in that wherein D is for having 0 to 3 substituent phenyl ring.
12. the reactive orchil of monoazo as claimed in claim 9 is characterized in that, wherein Z is-SO
2=CH=CH
2Or-SO
2-CH
2-CH
2-OSO
3H.
13. the reactive orchil of monoazo as claimed in claim 9 is characterized in that wherein n is 1.
14. the reactive orchil of monoazo as claimed in claim 9 is characterized in that, wherein when X is chlorine atom or fluorine atom, and R then
1Be to be hydrogen atom and R
3Be to be C
1-4Alkyl.
15. the reactive orchil of monoazo as claimed in claim 9 is characterized in that, wherein work as X to be-NHCN ,-OH ,-SCH
2COOH ,-NHSO
2CH
3, the 3-carboxyl pyridine or
16. the reactive orchil of monoazo as claimed in claim 1 is characterized in that its Chinese style (I) is to be the chemically-reactive dyes as shown in the formula (Ib),
Wherein
X is-NHCN ,-OH ,-SCH
2COOH, NHSO
2CH
3 -, the 3-carboxyl pyridine,
Z is-SO
2=CH=CH
2Or-SO
2-CH
2-CH
2-U; U is-OSO
3H, Cl or Br;
N is 0 or 1;
When X is chlorine atom or fluorine atom, R then
1Be to be hydrogen atom and R
3Be to be C
1-4Alkyl;
When X be-NHCN ,-OH ,-SCH
2COOH ,-NHSO
2CH
3, the 3-carboxyl pyridine or
The time, R then
1And R
3Independent mutually being selected from respectively comprises hydrogen atom, C
1-4Alkyl or have one or more substituent C
1-4The alkyl person, this substituting group is to be selected from respectively to comprise: hydroxyl, carboxyl, sulfonic group, amine formyl or methoxycarbonyl.
17. the reactive orchil of monoazo as claimed in claim 16 is characterized in that, wherein X is-NHCN, 3-carboxyl pyridine, chlorine atom or fluorine atom.
18. the reactive orchil of monoazo as claimed in claim 16 is characterized in that, wherein Z is-SO
2=CH=CH
2Or-SO
2-CH
2-CH
2-OSO
3H.
19. the reactive orchil of monoazo as claimed in claim 16 is characterized in that wherein n is 1.
20. the reactive orchil of monoazo as claimed in claim 16 is characterized in that, wherein when X is chlorine atom or fluorine atom, and R then
1Be to be hydrogen atom and R
3Be to be methyl or ethyl.
21. the reactive orchil of monoazo as claimed in claim 16 is characterized in that, wherein work as X to be-NHCN ,-OH ,-SCH
2COOH ,-NHSO
2CH
3, the 3-carboxyl pyridine or
The time, R then
1And R
3Independent mutually hydrogen atom, methyl or the ethyl of being selected from respectively.
22. the reactive orchil of monoazo as claimed in claim 16 is characterized in that its Chinese style (Ib) is to be the chemically-reactive dyes as shown in the formula (I-1).
23. the reactive orchil of monoazo as claimed in claim 16 is characterized in that its Chinese style (Ib) is to be the chemically-reactive dyes as shown in the formula (I-2),
24. the reactive orchil of monoazo as claimed in claim 16 is characterized in that its Chinese style (Ib) is to be the chemically-reactive dyes as shown in the formula (I-3),
25. the reactive orchil of monoazo as claimed in claim 16 is characterized in that its Chinese style (Ib) is to be the chemically-reactive dyes as shown in the formula (I-4),
26. the reactive orchil of monoazo as claimed in claim 16 is characterized in that its Chinese style (Ib) is to be the chemically-reactive dyes as shown in the formula (I-5),
27. the reactive orchil of monoazo as claimed in claim 16 is characterized in that its Chinese style (Ib) is to be the chemically-reactive dyes as shown in the formula (I-6),
28. one kind is filamentary material dyeing or the method for printing that contains hydroxy or aminocompound group, it is characterized in that, it comprises the reactive orchil aqueous solution processing of use monoazo as claimed in claim 1 filamentary material.
29. method as claimed in claim 28 is characterized in that, wherein filamentary material is to be cotton.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02150318 CN1257233C (en) | 2002-11-01 | 2002-11-01 | Monoazo reactive red dyestuff |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02150318 CN1257233C (en) | 2002-11-01 | 2002-11-01 | Monoazo reactive red dyestuff |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1493623A true CN1493623A (en) | 2004-05-05 |
| CN1257233C CN1257233C (en) | 2006-05-24 |
Family
ID=34233929
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 02150318 Expired - Fee Related CN1257233C (en) | 2002-11-01 | 2002-11-01 | Monoazo reactive red dyestuff |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1257233C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100413930C (en) * | 2005-08-31 | 2008-08-27 | 明德国际仓储贸易(上海)有限公司 | Reactivity dye composition and application thereof |
| CN102911528A (en) * | 2012-10-31 | 2013-02-06 | 无锡润新染料有限公司 | Sunlight-resistant chlorine-leaching-resistant composite reactive brilliant red dye |
| CN101624478B (en) * | 2008-07-09 | 2013-03-27 | 上海雅运纺织化工股份有限公司 | Red reactive dye composition and application thereof |
| CN103509371A (en) * | 2012-06-26 | 2014-01-15 | 台湾永光化学工业股份有限公司 | Reactive dye |
-
2002
- 2002-11-01 CN CN 02150318 patent/CN1257233C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100413930C (en) * | 2005-08-31 | 2008-08-27 | 明德国际仓储贸易(上海)有限公司 | Reactivity dye composition and application thereof |
| CN101624478B (en) * | 2008-07-09 | 2013-03-27 | 上海雅运纺织化工股份有限公司 | Red reactive dye composition and application thereof |
| CN103509371A (en) * | 2012-06-26 | 2014-01-15 | 台湾永光化学工业股份有限公司 | Reactive dye |
| CN102911528A (en) * | 2012-10-31 | 2013-02-06 | 无锡润新染料有限公司 | Sunlight-resistant chlorine-leaching-resistant composite reactive brilliant red dye |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1257233C (en) | 2006-05-24 |
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