CN102146061A - Red reactive dye compound, preparation method of red reactive dye compound and dye containing red reactive dye compound - Google Patents
Red reactive dye compound, preparation method of red reactive dye compound and dye containing red reactive dye compound Download PDFInfo
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- CN102146061A CN102146061A CN2010101082354A CN201010108235A CN102146061A CN 102146061 A CN102146061 A CN 102146061A CN 2010101082354 A CN2010101082354 A CN 2010101082354A CN 201010108235 A CN201010108235 A CN 201010108235A CN 102146061 A CN102146061 A CN 102146061A
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000000985 reactive dye Substances 0.000 title claims abstract description 21
- 239000000975 dye Substances 0.000 title abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 28
- 239000012467 final product Substances 0.000 claims description 18
- JYGXADMDTFJGBT-VWUMJDOOSA-N hydrocortisone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 JYGXADMDTFJGBT-VWUMJDOOSA-N 0.000 claims description 16
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 12
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 12
- OMFXVFTZEKFJBZ-HJTSIMOOSA-N corticosterone Chemical compound O=C1CC[C@]2(C)[C@H]3[C@@H](O)C[C@](C)([C@H](CC4)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 OMFXVFTZEKFJBZ-HJTSIMOOSA-N 0.000 claims description 11
- 238000005859 coupling reaction Methods 0.000 claims description 11
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 10
- 238000001514 detection method Methods 0.000 claims description 8
- 229960000890 hydrocortisone Drugs 0.000 claims description 8
- 235000010288 sodium nitrite Nutrition 0.000 claims description 8
- 238000006193 diazotization reaction Methods 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 159000000000 sodium salts Chemical class 0.000 claims description 4
- 229940126062 Compound A Drugs 0.000 claims description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 238000004065 wastewater treatment Methods 0.000 abstract description 5
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 22
- 238000006482 condensation reaction Methods 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000010298 pulverizing process Methods 0.000 description 6
- 238000004043 dyeing Methods 0.000 description 5
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 description 4
- ZAJAQTYSTDTMCU-UHFFFAOYSA-N 3-aminobenzenesulfonic acid Chemical compound NC1=CC=CC(S(O)(=O)=O)=C1 ZAJAQTYSTDTMCU-UHFFFAOYSA-N 0.000 description 4
- 125000006414 CCl Chemical group ClC* 0.000 description 4
- 238000004566 IR spectroscopy Methods 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000010009 beating Methods 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 239000012954 diazonium Substances 0.000 description 4
- 150000001989 diazonium salts Chemical class 0.000 description 4
- -1 ethyl sulfonyl sulfate Chemical compound 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- QPILZZVXGUNELN-UHFFFAOYSA-M sodium;4-amino-5-hydroxynaphthalene-2,7-disulfonate;hydron Chemical compound [Na+].OS(=O)(=O)C1=CC(O)=C2C(N)=CC(S([O-])(=O)=O)=CC2=C1 QPILZZVXGUNELN-UHFFFAOYSA-M 0.000 description 4
- 229920000742 Cotton Polymers 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 235000017550 sodium carbonate Nutrition 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- JGIGXKSJLSQJGQ-UHFFFAOYSA-K trisodium 5-[[4-chloro-6-(N-methylanilino)-1,3,5-triazin-2-yl]amino]-4-hydroxy-3-[(2-sulfonatophenyl)diazenyl]naphthalene-2,7-disulfonate Chemical compound [Na+].[Na+].[Na+].CN(c1ccccc1)c1nc(Cl)nc(Nc2cc(cc3cc(c(N=Nc4ccccc4S([O-])(=O)=O)c(O)c23)S([O-])(=O)=O)S([O-])(=O)=O)n1 JGIGXKSJLSQJGQ-UHFFFAOYSA-K 0.000 description 3
- 0 *c1nc(Nc2c3c(O)c(C=C=Nc4cccc(S(O)(=O)=O)c4)c(S(O)(=O)=O)cc3cc(S(O)(=O)=O)c2)nc(Cl)n1 Chemical compound *c1nc(Nc2c3c(O)c(C=C=Nc4cccc(S(O)(=O)=O)c4)c(S(O)(=O)=O)cc3cc(S(O)(=O)=O)c2)nc(Cl)n1 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical group [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- HTSVYUUXJSMGQC-UHFFFAOYSA-N 2-chloro-1,3,5-triazine Chemical compound ClC1=NC=NC=N1 HTSVYUUXJSMGQC-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000005183 environmental health Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000001044 red dye Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Landscapes
- Coloring (AREA)
Abstract
The invention discloses a red reactive dye compound shown as a formula A, a preparation method of the red reactive dye compound and a dye containing the red reactive dye compound, wherein R1 represents H, CH or CH2CH3; R2 is unequal to R3; R2 and R3 independently represent H, -SO3Na or -SO2CH2CH2OSO3Na; and at least one of R2 and R3 is -SO2CH2CH2OSO3Na. The dye compound can be used for fixing color in the environment of low temperature of 40 DEG C and has higher color fixing rate, lower energy consumption and lower wastewater treatment pressure.
Description
Technical field
The present invention is specifically related to a kind of red reactive dyes compound, its preparation method and contains its dyestuff.
Background technology
Reactive dyestuffs are the important synthetic dyestuff of a class, its group by having reactive behavior in the chemical structure and cellulosic fibre generation chemical reaction and therefore set is called chemically-reactive dyes (ReactiveDyes) again.Along with the day by day raising of people to sense comfortable and easy to wear and environmental health requirement, textile product is concentrated to cotton and cotton type fabric more and more, and the demand of reactive dyestuffs is also increased sharply year by year, becomes one of present most widely used synthetic dyestuff.
Conventional variety in the reactive dyestuffs is used more at present, as following two kinds of active red dyes, according to general technology, need finish fixation under 60 ℃ of conditions, and energy consumption is very high, and degree of fixation is on the low side, wastewater treatment after dyeing is finished.
CI reactive red 24
CI reactive red 24:1
Therefore develop a kind of can be under 40 ℃ of environment of low temperature fixation, and the higher relatively reactive dyestuffs of degree of fixation are problems that market in urgent need solves.
Summary of the invention
Technical problem to be solved by this invention is that the color fixing temperature height, the energy consumption that exist in the prior art are higher, degree of fixation is not high in order to overcome, the problem that wastewater treatment pressure is bigger, provide a kind of can be under 40 ℃ of environment of low temperature fixation, degree of fixation is higher, energy consumption is lower and wastewater treatment pressure is less red reactive dyes compound and preparation method thereof and contain its dyestuff.
The deficiency that the inventor exists at existing double-active radical dye, find by lot of experiments: on the basis of existing dye molecule, molecular structure is improved, promptly change the connection base between a chloro-s-triazine active group and the beta-sulfuric ester ethyl sulfonyl active group, can make the active group of dyestuff have more activity, itself and cellulosic molecule is easier reacts under lower temperature.
Therefore the present invention relates to a kind of suc as formula the red reactive dyes compound shown in the A;
Wherein,
R
1=H, CH
3Or CH
2CH
3, R
2=H or-SO
3Na, R
3And R
4Independently be H or-SO
2CH
2CH
2OSO
3Na, and R
3And R
4In have at least one to be-SO
2CH
2CH
2OSO
3Na, but R
3≠ R
4
The invention further relates to the preparation method of above-claimed cpd A, it comprises the following step: with compd A ' and alkaline sodium salt reaction, get final product;
Wherein,
R
1=H, CH
3Or CH
2CH
3, R
2=H or-SO
3H, R
3And R
4Independently be H or-SO
2CH
2CH
2OSO
3H, and R
3And R
4In have at least one to be-SO
2CH
2CH
2OSO
3H, but R
3≠ R
4
Wherein, ordinary method when the preparation method of described compd A prepares dye composition for this area, what described alkaline sodium salt was preferable is yellow soda ash, preferred step and condition are as follows: at the preparation compd A ' reaction finish after, the refined salt that adds reaction solution volume 5～25%, saltout under stirring, at last after filtration, oven dry, pulverizing, stdn, promptly make compd A.What wherein, described refined salt was preferable is sodium-chlor, Repone K or sodium sulfate etc.Wherein, the process that promptly comprises alkaline sodium salt and A ' reaction in the stdn.
Among the present invention, described compd A ' can make by following method: compd B and C are carried out nucleophilic substitution reaction, get final product;
Wherein, R
1=H, CH
3Or CH
2CH
3, R
2=H or-SO
3H, R
3And R
4Independently be H or-SO
2CH
2CH
2OSO
3H, and R
3And R
4In have at least one to be-SO
2CH
2CH
2OSO
3H, but R
3≠ R
4
Wherein, the method of described nucleophilic substitution reaction and condition all can be the ordinary method and the condition of this type of reaction of this area, and preferred especially following method of the present invention and condition: in the solvent, pH is controlled at 6.5～7.0, compd B and C are carried out nucleophilic substitution reaction, get final product; Wherein, described preferred solvents is water; What the mol ratio of described compd B and C was preferable is 1: 1～1: 1.05, and better is 1: 1.02; What the temperature of described reaction was preferable is 30～50 ℃, preferred 40～45 ℃; The time of described reaction preferable with detection reaction fully till, be generally 3 hours.
Among the present invention, described compd B can be made by following method: compd E and D are carried out coupled reaction, get final product;
Wherein, the method for described coupled reaction and condition all can be the ordinary method and the condition of this type of coupled reaction of this area, preferred especially following method of the present invention and condition: in the solvent, control pH is 6.0～7.0, and compd E and D are carried out coupled reaction, gets final product.Wherein, described preferred solvents is water; What the mol ratio of described compd E and D was preferable is 1: 1～1: 1.05, and better is 1: 1.02; Described pH preferred 7.0; What the temperature of described reaction was preferable is 0～20 ℃, preferred 0 ℃～5 ℃; The time of described reaction preferable with detection reaction fully till, be generally 3.0～3.5 hours.
Among the present invention, described compd E can be made by following method: compound F 17-hydroxy-corticosterone is carried out diazotization reaction, get final product.
Wherein, the method for described diazotization reaction and condition all can be the ordinary method and the condition of this type of reaction of this area, preferred especially following method of the present invention and condition: in the dilute acid solution, diazotization reaction is carried out in compound F 17-hydroxy-corticosterone and acid and Sodium Nitrite, get final product.That wherein, described dilute acid solution is preferable is rare HCl and/or rare H
2SO
4The aqueous solution; What the massfraction of dilute acid solution was preferable is 30～40%; What the mol ratio of described compound F 17-hydroxy-corticosterone and Sodium Nitrite was preferable is 1: 1.02～1: 1.08, and better is 1: 1.05; What the mol ratio of described compound F 17-hydroxy-corticosterone and acid was preferable is 1: 2～1: 5, and better is 1: 3; What the temperature of described reaction was preferable is-5～15 ℃, preferred 0～5 ℃; The time of described reaction preferable with detection reaction fully till, be generally 0.5～1 hour.
Among the present invention, described Compound D can be made by following method: compound G and cyanuric chloride are carried out nucleophilic substitution reaction, get final product;
Wherein, the method of described nucleophilic substitution reaction and condition all can be the ordinary method and the condition of this type of reaction of this area, preferred especially following method of the present invention and condition: in the solvent, under the effect of acid, compound G and cyanuric chloride are carried out nucleophilic substitution reaction, get final product; Wherein, described preferred solvents is water; What the mol ratio of described compound G and cyanuric chloride was preferable is 1: 1～1: 1.05, and better is 1: 1.03; What the temperature of described reaction was preferable is 0～15 ℃, preferred 5～10 ℃; The time of described reaction preferable with detection reaction fully till, be generally 4 hours.
Among the present invention, each step among the above-mentioned preparation method can be carried out continuously, promptly carries out simple aftertreatment according to this area ordinary method, the product of each step is not purified, and directly carries out next step.In such cases, the usage ratio of each reactant that each step relates to is 100% to calculate according to the productive rate of the product of a last reactions steps all, as prepare in the step of compd A, if the product compd B in the last reaction does not have to purify and directly carries out the preparation of compd A, then prepare in the step of compd A, the usage ratio of compd B and C is 100% to calculate according to the productive rate of compd B in the last reaction.
Among the present invention, but each the optimum condition arbitrary combination among the above-mentioned preparation method promptly gets each preferred embodiment of the present invention.
The invention still further relates to a kind of midbody compound A ' for preparing the red reactive dyes compd A;
Wherein,
R
1=H, CH
3Or CH
2CH
3, R
2=H or-SO
3H, R
3And R
4Independently be H or-SO
2CH
2CH
2OSO
3H, and R
3And R
4In have at least one to be-SO
2CH
2CH
2OSO
3H, but R
3≠ R
4
The invention still further relates to a kind of red reactive dyes that comprises above-mentioned red reactive dyes compd A.Described red reactive dyes can be prepared by the conventional preparation method of this type of dyestuff of this area, the preferred following preparation method of the present invention: after the reaction of above-mentioned preparation compd A finishes, the refined salt that adds reaction solution volume 5～25%, saltout under stirring, at last after filtration, oven dry, pulverizing, stdn, promptly obtain commercial red reactive dyes.What wherein, described refined salt was preferable is sodium-chlor, Repone K or sodium sulfate etc.
Raw material that the present invention is used or reagent except that specifying, all commercially available getting.
Positive progressive effect of the present invention is: dye composition of the present invention can be under 40 ℃ of environment of low temperature fixation, degree of fixation is higher, energy consumption is lower and wastewater treatment pressure is less.
Embodiment
Further specify the present invention with embodiment below, but the present invention is not limited.
Embodiment 1
Preparation is synthetic as shown in the formula the compound shown in the I:
In the 500mL there-necked flask, add 100mL water, and adding 18.8g cyanuric chloride under stirring (184.41,102mmol), mix making beating; (319.30,100mmol) solution reacts 4h down at 5 ℃, and it is stand-by to obtain condensation reaction solution in the slowly H acid of adding 212.7g 15%.
(173.19,97mmol) solution adds in the 500mL there-necked flask, adds Sodium Nitrite (103mmol) solution of 23.7g 30% again, stirs with the m-sulfanilic acid of 113.1g 15%; Add 43.5mL water, the hydrochloric acid of 59.6g 30% (497mmol), temperature of reaction is controlled at about 0 ℃, reaction times 1h.The diazonium salt solution that makes thus adds in the 1000mL there-necked flask, stirs down to add above-mentioned condensation reaction solution, and controlled temperature is 15 ℃, time 3.0h, pH=7.0.
(309.35,110mmol) in the adding coupled reaction liquid, heating is carried out the secondary condensation reaction, 45 ℃ of temperature of reaction, reaction times 3h, pH=6.5～7.0 under stirring with 34.1g 3-(β-ethyl sulfonyl sulfate)-N-ethylaniline.
After reaction finishes, add the salt of products therefrom volume 25%, saltout under stirring, at last after filtration, oven dry, pulverizing, stdn get finished product.Through high-efficient liquid phase chromatogram HPLC its content is analyzed, recording degree of purity of production is 84.38%.
After the refining purification of compound (I), carry out Infrared spectroscopy, the wave number data of each functional group are :～3430cm
-1(NH) ,～2970cm
-1(CH
3) ,～2930cm
-1(CH
2) ,～1570cm
-1With～1530cm
-1(aromatic ring and triazine ring) ,～1200cm
-1With～1050cm
-1(sulfonic group) ,～1140cm
-1(ethyl sulfonyl sulfate) ,～650cm
-1(C-Cl).
Embodiment 2
Preparation is synthetic as shown in the formula the compound shown in the I:
In the 500mL there-necked flask, add 100mL water, stir adding 18.8g cyanuric chloride (184.41) down, mix making beating; H acid (319.30) solution that slowly adds 212.7g 15% reacts 4h down at 10 ℃, and it is stand-by to obtain condensation reaction solution.
M-sulfanilic acid (173.19) solution of 113.1g 15% is added in the 500mL there-necked flask, add the sodium nitrite solution of 23.7g 30% again, stir; Add 43.5mL water, the hydrochloric acid of 59.6g 30%, temperature of reaction is controlled at about 5 ℃, reaction times 1h.The diazonium salt solution that makes thus adds in the 1000mL there-necked flask, stirs down to add above-mentioned condensation reaction solution, and controlled temperature is 10 ℃, time 3.0h, pH=7.0.
34.1g 3-(β-ethyl sulfonyl sulfate)-N-ethylaniline (309.35) is added in the coupled reaction liquid, stir heating down and carry out the secondary condensation reaction, 40 ℃ of temperature of reaction, reaction times 3h, pH=6.5～7.0.
After reaction finishes, add the salt of products therefrom volume 15%, saltout under stirring, at last after filtration, oven dry, pulverizing, stdn get finished product.Through high-efficient liquid phase chromatogram HPLC its content is analyzed, recording degree of purity of production is 82.60%.
After the refining purification of compound (I), carry out Infrared spectroscopy, the wave number data of each functional group are :～3430cm
-1(NH) ,～2970cm
-1(CH
3) ,～2930cm
-1(CH
2) ,～1570cm
-1With～1530cm
-1(aromatic ring and triazine ring) ,～1200cm
-1With～1050cm
-1(sulfonic group) ,～1140cm
-1(ethyl sulfonyl sulfate) ,～650cm
-1(C-Cl).
Embodiment 3
Preparation is synthetic as shown in the formula the compound shown in the II:
In the 500mL there-necked flask, add 100mL water, stir adding 18.4g cyanuric chloride (184.41) down, mix making beating; H acid (319.30) solution that slowly adds 155g 20% reacts 4h down at 5 ℃, and it is stand-by to obtain condensation reaction solution.
M-sulfanilic acid (173.19) solution of 115.3g 15% is added in the 500mL there-necked flask, add the sodium nitrite solution of 23.7g 30% again, stir; Add 45mL water, the hydrochloric acid of 60.0g 30%, temperature of reaction is controlled at about 5 ℃, reaction times 1.5h.The diazonium salt solution that makes thus adds in the 1000mL there-necked flask, stirs down to add above-mentioned condensation reaction solution, and controlled temperature is 10 ℃, time 3.5h, pH=7.0.
38.6g 5-(β-ethyl sulfonyl sulfate)-methylphenylamine-2-sulfonic acid (375.38) is added in the coupled reaction liquid, stir heating down and carry out the secondary condensation reaction, 45 ℃ of temperature of reaction, reaction times 3h, pH=6.5～7.0.
After reaction finishes, add the salt of products therefrom volume 20%, saltout under stirring, at last after filtration, oven dry, pulverizing, stdn get finished product.Through high-efficient liquid phase chromatogram HPLC its content is analyzed, recording degree of purity of production is 87.43%.
After the refining purification of compound (II), carry out Infrared spectroscopy, the wave number data of each functional group are :～3430cm
-1(NH) ,～2970cm
-1(CH
3) ,～2930cm
-1(CH
2) ,～1570cm
-1With～1530cm
-1(aromatic ring and triazine ring) ,～1200cm
-1With～1050cm
-1(sulfonic group) ,～1140cm
-1(ethyl sulfonyl sulfate) ,～650cm
-1(C-Cl).
Embodiment 4
Preparation is synthetic as shown in the formula the compound shown in the II:
In the 500mL there-necked flask, add 100mL water, stir adding 18.4g cyanuric chloride (184.41) down, mix making beating; H acid (319.30) solution that slowly adds 155g 20% reacts 3.5h down at 10 ℃, and it is stand-by to obtain condensation reaction solution.
M-sulfanilic acid (173.19) solution of 115.3g 15% is added in the 500mL there-necked flask, add the sodium nitrite solution of 23.7g 30% again, stir; Add 45mL water, the hydrochloric acid of 60.0g 30%, temperature of reaction is controlled at about 0 ℃, reaction times 1.5h.The diazonium salt solution that makes thus adds in the 1000mL there-necked flask, stirs down to add above-mentioned condensation reaction solution, and controlled temperature is 12 ℃, time 3.5h, pH=7.0.
37.5g 5-(β-ethyl sulfonyl sulfate)-methylphenylamine-2-sulfonic acid (375.38) is added in the coupled reaction liquid, stir heating down and carry out the secondary condensation reaction, 40 ℃ of temperature of reaction, reaction times 3h, pH=6.5～7.0.
After reaction finishes, add the salt of products therefrom volume 15%, saltout under stirring, at last after filtration, oven dry, pulverizing, stdn get finished product.Through high-efficient liquid phase chromatogram HPLC its content is analyzed, recording degree of purity of production is 81.77%.
After the refining purification of compound (II), carry out Infrared spectroscopy, the wave number data of each functional group are :～3430cm
-1(NH) ,～2970cm
-1(CH
3) ,～2930cm
-1(CH
2) ,～1570cm
-1With～1530cm
-1(aromatic ring and triazine ring) ,～1200cm
-1With～1050cm
-1(sulfonic group) ,～1140cm
-1(ethyl sulfonyl sulfate) ,～650cm
-1(C-Cl).
Effect embodiment
Dye composition I, II among the embodiment 1～4 that the present invention relates to are dyeed according to 40 ℃ of technologies, and wherein the alkaline agent consumption is: soda ash 5g/L, caustic soda 1g/L; Dyeing time: 90min.
60 ℃ of dyeing down, the alkaline agent consumption is Reactive Brilliant Red K-2BP (CI reactive red 24): soda ash 20g/L according to common process; Dyeing time: 60min,
Above-mentioned dyeing course all uses pure cotton knitted fabric to carry out.
Use HunterLab ColorQuest XE computer color measurement instrument that the tinctorial pattern that obtains is carried out strength test, under identical dye level, the weighed intensities that dyestuff I of the present invention, II obtain tinctorial pattern obtains the weighed intensities high 4.30% and 5.14% of tinctorial pattern respectively than K-2BP, all the raising to the utilization ratio of dyestuff has very big contribution.Carry out the mensuration of degree of fixation according to the standard of GB/T 2391-2006, the degree of fixation of dyestuff I, II that the present invention obtains is respectively 86% and 84%.
Claims (12)
1. one kind suc as formula the red reactive dyes compound shown in the A;
Wherein,
R
1=H, CH
3Or CH
2CH
3, R
2=H or-SO
3Na, R
3And R
4Independently be H or-SO
2CH
2CH
2OSO
3Na, and R
3And R
4In have at least one to be-SO
2CH
2CH
2OSO
3Na, but R
3≠ R
4
2. the preparation method of compd A as claimed in claim 1 is characterized in that comprising the following step: with compd A ' and alkaline sodium salt reaction, get final product;
Wherein,
R
1=H, CH
3Or CH
2CH
3, R
2=H or-SO
3H, R
3And R
4Independently be H or-SO
2CH
2CH
2OSO
3H, and R
3And R
4In have at least one to be-SO
2CH
2CH
2OSO
3H, but R
3≠ R
4
3. the preparation method of compd A as claimed in claim 2 is characterized in that: described compd A ' make by following method: compd B and C are carried out nucleophilic substitution reaction, get final product;
Wherein, R
1=H, CH
3Or CH
2CH
3, R
2=H or-SO
3H, R
3And R
4Independently be H or-SO
2CH
2CH
2OSO
3H, and R
3And R
4In have at least one to be-SO
2CH
2CH
2OSO
3H, but R
3≠ R
4
4. preparation method as claimed in claim 3 is characterized in that: the method and the condition of described nucleophilic substitution reaction are as follows: in the solvent, pH is controlled at 6.5～7.0, and compd B and C are carried out nucleophilic substitution reaction, gets final product; Wherein, described solvent is a water; The mol ratio of described compd B and C is 1: 1～1: 1.05; The temperature of described reaction is 30～50 ℃; The time of described reaction with detection reaction fully till.
5. preparation method as claimed in claim 3 is characterized in that: described compd B is made by following method: compd E and D are carried out coupled reaction, get final product;
6. preparation method as claimed in claim 5 is characterized in that: the method and the condition of described coupled reaction are as follows: in the solvent, control pH is 6.0～7.0, and compd E and D are carried out coupled reaction, gets final product; Wherein, described solvent is a water; The mol ratio of described compd E and D is 1: 1～1: 1.05; The temperature of described reaction is 0～20 ℃; The time of described reaction with detection reaction fully till.
7. preparation method as claimed in claim 5 is characterized in that: described compd E is made by following method: compound F 17-hydroxy-corticosterone is carried out diazotization reaction, get final product;
8. preparation method as claimed in claim 7 is characterized in that: the method and the condition of described diazotization reaction are as follows: in the dilute acid solution, diazotization reaction is carried out in compound F 17-hydroxy-corticosterone and acid and Sodium Nitrite, get final product; Wherein, described dilute acid solution is rare HCl and/or rare H
2S0
4The aqueous solution; The massfraction of dilute acid solution is 30～40%; The mol ratio of described compound F 17-hydroxy-corticosterone and Sodium Nitrite is 1: 1.02～1: 1.08; The mol ratio of described compound F 17-hydroxy-corticosterone and acid is 1: 2～1: 5; The temperature of described reaction is-5～15 ℃; The time of described reaction with detection reaction fully till.
9. preparation method as claimed in claim 5 is characterized in that: described Compound D is made by following method: compound G and cyanuric chloride are carried out nucleophilic substitution reaction, get final product;
10. preparation method as claimed in claim 9 is characterized in that: the method and the condition of described nucleophilic substitution reaction are as follows: in the solvent, under the effect of acid, compound G and cyanuric chloride are carried out nucleophilic substitution reaction, get final product; Wherein, described solvent is a water; The mol ratio of described compound G and cyanuric chloride is 1: 1～1: 1.05; The temperature of described reaction is 0～15 ℃; The time of described reaction with detection reaction fully till.
11. midbody compound A ' who prepares the red reactive dyes compd A;
Wherein,
R
1=H, CH
3Or CH
2CH
3, R
2=H or-SO
3H, R
3And R
4Independently be H or-SO
2CH
2CH
2OSO
3H, and R
3And R
4In have at least one to be-SO
2CH
2CH
2OSO
3H, but R
3≠ R
4
12. red reactive dyes that comprises red reactive dyes compd A as claimed in claim 1.
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| CN 201010108235 CN102146061B (en) | 2010-02-09 | 2010-02-09 | Red reactive dye compound, preparation method of red reactive dye compound and dye containing red reactive dye compound |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010108235 CN102146061B (en) | 2010-02-09 | 2010-02-09 | Red reactive dye compound, preparation method of red reactive dye compound and dye containing red reactive dye compound |
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| Publication Number | Publication Date |
|---|---|
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| CN102146061B CN102146061B (en) | 2013-04-03 |
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ID=44420553
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| CN 201010108235 Active CN102146061B (en) | 2010-02-09 | 2010-02-09 | Red reactive dye compound, preparation method of red reactive dye compound and dye containing red reactive dye compound |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584786A (en) * | 2011-12-28 | 2012-07-18 | 泰兴锦云染料有限公司 | Activity-brilliant-red LA and preparation method thereof |
| CN104194395A (en) * | 2014-08-06 | 2014-12-10 | 浙江瑞华化工有限公司 | Reactive red dye composition, reactive red dye as well as preparation method and application of active red dye |
| CN105038312A (en) * | 2015-05-29 | 2015-11-11 | 浙江龙盛集团股份有限公司 | Red reactive dye compound as well as preparation method and application thereof |
| CN111925666A (en) * | 2020-08-20 | 2020-11-13 | 浙江亿得新材料股份有限公司 | High-solarization red reactive dye and preparation method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000069974A1 (en) * | 1999-05-19 | 2000-11-23 | The Procter & Gamble Company | Reactive dye compounds |
| KR20070086016A (en) * | 2004-11-12 | 2007-08-27 | 훈츠만 어드밴스트 머티리얼스(스위처랜드) 게엠베하 | Reactive dyes, a process for their preparation and their use |
| CN100434484C (en) * | 2006-06-19 | 2008-11-19 | 湖北华丽染料工业有限公司 | Ozo dye mixture |
| CN100567403C (en) * | 2007-05-10 | 2009-12-09 | 佛山市焱基化工染料有限公司 | A kind of composite active black dye |
-
2010
- 2010-02-09 CN CN 201010108235 patent/CN102146061B/en active Active
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584786A (en) * | 2011-12-28 | 2012-07-18 | 泰兴锦云染料有限公司 | Activity-brilliant-red LA and preparation method thereof |
| CN104194395A (en) * | 2014-08-06 | 2014-12-10 | 浙江瑞华化工有限公司 | Reactive red dye composition, reactive red dye as well as preparation method and application of active red dye |
| CN105038312A (en) * | 2015-05-29 | 2015-11-11 | 浙江龙盛集团股份有限公司 | Red reactive dye compound as well as preparation method and application thereof |
| CN105038312B (en) * | 2015-05-29 | 2017-10-20 | 浙江龙盛集团股份有限公司 | A kind of red reactive dyes compound and its preparation and application |
| CN111925666A (en) * | 2020-08-20 | 2020-11-13 | 浙江亿得新材料股份有限公司 | High-solarization red reactive dye and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN102146061B (en) | 2013-04-03 |
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