CN102604414B - Azo compound containing phenylindole, preparation method and application thereof - Google Patents
Azo compound containing phenylindole, preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the technical field of azo dyes, which provides an azo compound containing phenylindole, a preparation method and application of the azo compound to solve the problem that the light fastness of disperse azo dyes with good tinctorial strength is not desired. The preparation method comprises the steps of firstly preparing a diazo salt, and then preparing the azo compound containing phenylindole through a coupling reaction. Azo dyes prepared by using the azo compound containing phenylindole provided by the invention are suitable for dyeing hydrophobic fiber materials, such as terylene, acetate fibers, acrylon, polyester, mixture yarn and the like, are satisfactory in fastness to washing and crockfastness, excellent in light fastness, and further solve the problem that conventional high sun exposure products can not have both the satisfactory fastness to washing and crockfastness and the excellent light fastness.
Description
Technical field
The present invention relates to the azoic dyestuff technical field, relate in particular to a kind of azo-compound containing Phenylindole and preparation method thereof and application.
Background technology
In recent years, filamentary material has more application on cloth textile, along with the expansion in tint applications field and the differentiation of product, the range of application of filamentary material enlarges rapidly, and one of them is exactly that Polyester Fibers is developed and is applied on automotive trim and house decorative material.Automobile is because using region, the difference in season, and vehicle interior temperature easily raises, and photostabilization, the thermotolerance of interior trim DYED FABRICS just had to higher requirement.The photostabilization of trevira, thermotolerance are all better, and feel is also fine, therefore are widely used in upholstery, and the dyestuff of simultaneously selecting has also required fastness preferably, and the light fastness under comparatively high temps.But in dispersed dye, what light fastness was taught is anthraquinone dyes, but their tinting strength is really poor, and the good general light fastness of azo dispersion dyes of tinting strength is undesirable.Contain at present the research of azo-compound aspect dyestuff of Phenylindole also in the starting stage.
Summary of the invention
The present invention is in order to solve the undesirable problem of azo dispersion dyes light fastness that tinting strength is good, a kind of azo-compound containing Phenylindole and preparation method thereof and application have been proposed, the dyestuff that uses the present invention to make containing the azo-compound of Phenylindole is applicable to terylene, the vinegar fibre, acrylic fibers, the dyeing of the hydrophobic fiber material such as polyester and blending, not only possesses gratifying washable, crock fastness, and there is remarkable light fastness, also solved the two problem that can not take into account of conventional high Exposure to Sunlight kind.
The present invention is achieved by the following technical solutions, a kind of azo-compound containing Phenylindole, and general formula is as shown in formula I:
(Ⅰ)，
In logical formula I: R is selected from alkyl or the propenyl of C1 ~ C4, and D is selected from the group shown in following formula II or formula III,
In formula II, formula III: X
1Be selected from hydrogen, chlorine, bromine a kind of, X
2Be selected from hydrogen or sulfydryl.
A kind of preparation method of the azo-compound containing Phenylindole carries out as follows:
(1) will lead to the compound shown in formula IV or general formula (V) and carry out diazotization reaction with diazo reagent under acidic conditions, obtain diazonium salt, then be diluted with frozen water, standby.Diazo reagent is selected from nitrosyl sulfuric acid solution, the mixing solutions of the mixing solutions of hydrochloric acid and Sodium Nitrite or sulfuric acid and Sodium Nitrite,
In above-mentioned general formula, X1 is selected from hydrogen, chlorine or bromine a kind ofly, and X2 is selected from hydrogen or sulfydryl;
Wherein, the consumption of hydrochloric acid is to be 2.25 ~ 3.0:1 with the molar mass ratio that leads to the compound shown in formula IV or general formula (V); The consumption of sulfuric acid is to be 1.05 ~ 6:1 with the molar mass ratio that leads to the compound shown in formula IV or general formula (V); The molar mass ratio of the compound shown in the consumption of Sodium Nitrite or nitrosyl sulfuric acid and logical formula IV or general formula (V) is 1.05 ~ 1.1:1; The sodium nitrite solution mass concentration is 20% ~ 40%; Nitrosyl sulfuric acid is industrial goods, and mass concentration is 40%; H 2 so 4 concentration is 50% ~ 98%, and hydrochloric acid is selected from industrial concentrated hydrochloric acid, and mass concentration is 30%; The frozen water amount of dilution diazonium salt and the mass ratio of diazonium salt are 2 ~ 10:1.
(2) in container, by the compound shown in logical formula VI, first use sulfuric acid dissolution, solvent temperature is 0 ~ 50 ℃, the solution of compound shown in the logical formula VI dissolved is added dropwise in the diluent of the diazonium salt that step (1) obtains, first add emulsifying agent before dropping, then carry out coupled reaction, at-5 ~ 20 ℃, keep 1 ~ 10 hour, then be warming up to 60 ~ 75 ℃, after keeping 1 ~ 5 hour, filtered, filter cake, through washing, obtains target product and shown in logical formula I, contains the azo dyestuff cpds of Phenylindole.
As preferably, emulsifying agent is selected from 8#OP, 10#OP, tween-80, Tween-60, A-20, and shown in the consumption of emulsifying agent and logical formula VI, the mass ratio of compound is 0.001 ~ 0.05:1.
Wherein the mass ratio of the consumption of sulfuric acid and logical formula VI consumption is 1 ~ 10:1, and h 2 so 4 concentration is 50% ~ 98%, and diazonium salt is 1:0.8 ~ 1.2 with the compound molar mass ratio shown in logical formula VI.
In general formula, R is selected from alkyl or the propenyl of C1 ~ C4,
A kind of preparation method's concrete steps of the azo-compound containing Phenylindole are:
Be selected from shown in logical formula IV when in compound, X1 is chlorine or bromine, use nitrosyl sulfuric acid diazotization; Being selected from shown in logical formula IV X1 in compound is hydrogen, or while being selected from compound shown in general formula (V), the sodium nitrite solution diazotization of use.
While using nitrosyl sulfuric acid diazotization, preparation method's step (1) is: the nitrosyl sulfuric acid of inciting somebody to action slowly joins in sulfuric acid, then by compound shown in the logical formula IV of general formula, wherein X1 is chlorine or bromine, slowly joins in above-mentioned solution, control temperature at 15 ~ 35 ℃, react 1 ~ 5 hour, to the solution clarification, obtain diazonium salt, with frozen water, diluted, standby.The consumption of nitrosyl sulfuric acid is 1.05 ~ 1.1:1 with the molar mass ratio of compound shown in logical formula IV; Nitrosyl sulfuric acid is industrial goods, and mass concentration is 40%; H 2 so 4 concentration is 50% ~ 98%, and the consumption of sulfuric acid is to be 1.05 ~ 6:1 with the molar mass ratio that leads to compound shown in formula IV; (2) add emulsifying agent in the diazonium salt diluent in step (1); (3) in another container, by the compound shown in logical formula VI, first use sulfuric acid dissolution, solvent temperature is 0 ~ 50 ℃, the solution of compound shown in the logical formula VI dissolved is added dropwise in the diluent of the diazonium salt that has added emulsifying agent in step (2) and carries out coupled reaction, at-5 ~ 20 ℃, keep 1 ~ 10 hour, then be warming up to 60 ~ 75 ℃, keep after 1 ~ 5 hour, filtered, filter cake, through washing, obtains the i.e. azo dyestuff cpds containing Phenylindole shown in logical formula I of target product.
Selecting shown in logical formula IV X1 in compound is hydrogen, while perhaps being selected from compound shown in general formula (V), preparation method's step (1) is: first will lead to compound shown in compound shown in formula IV (X1 is hydrogen) or general formula (V) and be added in hydrochloric acid or sulfuric acid, 0 ~ 10 ℃ of making beating, to abundant, mix, then with ice bath, reaction solution is cooled to 0 ~ 5 ℃, by sodium nitrite solution, join in above-mentioned solution, stir 0.5 ~ 2 hour, clarify to solution, obtain diazonium salt, then diluted with frozen water, standby.The consumption of hydrochloric acid is to be 2.25 ~ 3.0:1 with the molar mass ratio that leads to the compound shown in formula IV or general formula (V); The consumption of sulfuric acid is to be 1.05 ~ 6:1 with the molar mass ratio that leads to the compound shown in formula IV or general formula (V); The molar mass ratio of the compound shown in the consumption of Sodium Nitrite and logical formula IV or general formula (V) is 1.05 ~ 1.1:1; The sodium nitrite solution mass concentration is 20% ~ 40%; H 2 so 4 concentration is 50% ~ 98%, and hydrochloric acid is selected from industrial concentrated hydrochloric acid, and mass concentration is 30%; (2) add emulsifying agent in the diazonium salt diluent in step (1); (3) in another container, by the compound shown in logical formula VI, first use sulfuric acid dissolution, solvent temperature is 0 ~ 50 ℃, the solution of compound shown in the logical formula VI dissolved is added dropwise in the diluent of the diazonium salt that has added emulsifying agent in step (2) and carries out coupled reaction, at-5 ~ 20 ℃, keep 1 ~ 10 hour, then be warming up to 60 ~ 75 ℃, keep after 1 ~ 5 hour, filtered, filter cake, through washing, obtains the i.e. azo dyestuff cpds containing Phenylindole shown in logical formula I of target product.
Preparation containing the azo-compound of Phenylindole, be applicable to hydrophobic fibre is dyeed as fiber-like such as trevira, diacetate fiber, triacetate fiber, polyacrylonitrile fibres.
As preferably, a kind of azo-compound containing Phenylindole is selected from following structural:
With technology arranged compare, the invention has the beneficial effects as follows: the dyestuff that the present invention makes containing the azo-compound of Phenylindole is applicable to terylene, the vinegar fibre, acrylic fibers, the dyeing of the hydrophobic fiber material such as polyester and blending, not only possess gratifying washable, crock fastness, and there is remarkable light fastness, also solved the two problem that can not take into account of conventional high Exposure to Sunlight kind.
The accompanying drawing explanation
The nucleus magnetic hydrogen spectrum figure that Fig. 1 is embodiment 1;
The partial enlarged drawing that Fig. 2 is embodiment 1 nucleus magnetic hydrogen spectrum figure;
The mass spectrum that Fig. 3 is embodiment 1;
The nucleus magnetic hydrogen spectrum figure that Fig. 4 is embodiment 3;
The partial enlarged drawing that Fig. 5 is embodiment 3 nucleus magnetic hydrogen spectrum figure;
The mass spectrum that Fig. 6 is embodiment 3.
Embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but protection scope of the present invention is not only for therewith.Raw material used in embodiment is commercially available prod.
(1) add 98% sulfuric acid 120g in flask, 40% nitrosyl sulfuric acid 68g, stir 1 hour, control 25 ℃ of temperature, under agitation add 41.4g(0.2mol) 2, the 6-Dichloro-4-nitroaniline, about insulation reaction 5 hours, diazotization completes, and adds the 400g frozen water, under stirring, above-mentioned diazonium salt is added and is diluted;
(2) add 1.2g 10#OP in the diazonium salt diluent in step (1);
(3) the another flask adds 98% sulfuric acid 330g, controls 25 ℃ of temperature, adds N-methyl-2-phenylindone 41.4g altogether under stirring, and insulation keeps 2 hours CLs, treats coupling.
Added in step (2) and be added dropwise to slowly the above-mentioned N-of dissolving methyl-2-phenylindone in the diazonium salt diluent of emulsifying agent under 4 ℃ and carry out coupled reaction, adding rear insulation 5 hours to coupled reaction finishes, then be warming up to 70 ℃, keep after 2 hours, filtered, filter cake, through washing, can make the orange azo-compound containing Phenylindole of following formula (I-1).As depicted in figs. 1 and 2, mass spectrum as shown in Figure 3 for nucleus magnetic hydrogen spectrum figure.
Embodiment 2
(1) add 98% sulfuric acid 90g in flask, 40% nitrosyl sulfuric acid 173g, stir 0.5 hour, control 35 ℃ of temperature, under agitation add 148g(0.5mol) 2, the bromo-4-N-methyl-p-nitroaniline of 6-bis-, about insulation reaction 2 hours, diazotization completes, and then adds the 1200g frozen water, under stirring, above-mentioned diazonium salt is added and is diluted;
(2) add 1g 8#OP in the diazonium salt diluent in step (1);
(3) to add mass concentration be 75% sulfuric acid 860g to the another flask, controls 15 ℃ of temperature, adds N-ethyl-2-phenylindone 121.5g altogether under stirring, and insulation keeps 5 hours CLs, treats coupling.
Added in step (2) and be added dropwise to slowly the above-mentioned N-of dissolving ethyl-2-phenylindone in the diazonium salt diluent of emulsifying agent under 0 ℃ and carry out coupled reaction, adding rear insulation 5 hours to coupled reaction finishes, then be warming up to 60 ℃, keep after 5 hours, filtered, filter cake, through washing, can make the orange azo-compound containing Phenylindole of following formula (I-4).
(Ⅰ-4)
Embodiment 3
(1) add 60% sulphuric acid soln 140g altogether in reaction vessel, under stirring, add 3-amino-1,2,4-triazole 16.8g(0.2mol), 10 ℃ of making beating 3.0 hours.Be cooled to 5 ℃, at this temperature, add the sodium nitrite solution that concentration is 32% to be total to 46g, at 5 ℃, keep stirring within 1 hour, to make diazonium salt, then add frozen water 520g to be diluted, standby.
(2) add 0.8g 10#OP in the diazonium salt diluent in step (1);
(3) add 98% sulfuric acid 305g at flask, control 20 ℃ of temperature, add 2-phenylindone 38.6g altogether under stirring, insulation keeps 2 hours CLs, treats coupling.
By above-mentioned dissolving, the sulphuric acid soln of good 2-phenylindone adds in the diazonium salt diluent that adds emulsifying agent of preparation in step (2) slowly, control 5 ℃ of temperature, keep reaction 5 hours to coupled reaction to finish, coupled reaction is warming up to 75 ℃ and keeps being turned in 1 hour brilliant after finishing, then filtered, washed, can be made following formula (I-2) containing the Phenylindole azo-compound.As shown in Figure 4 and Figure 5, mass spectrum as shown in Figure 6 for nucleus magnetic hydrogen spectrum figure.
(1) add industrial concentrated hydrochloric acid 82.1g in reaction vessel, add 4-nitro-aniline 41.4g(0.3mol under stirring), normal temperature making beating 1 hour.Add trash ice 90g, be cooled to 2.5 ℃, at this temperature, add the sodium nitrite solution that concentration is 20% to be total to 111.8g, at 2.5 ℃, keep stirring within 1 hour, to make diazonium salt, then add frozen water 1250g to be diluted, standby.
(2) add 1.8g emulsifying agent A-20 in the diazonium salt diluent in step (1);
(3) add 85% sulfuric acid 525g at flask, control temperature 50 C, add N-methyl 2-phenylindone 74.5g altogether under stirring, insulation keeps 1 hour CL, treats coupling.
By above-mentioned dissolving, the sulphuric acid soln of good N-methyl-2-phenylindone adds in the diazonium salt diluent that adds emulsifying agent of preparation in step (2) slowly, control 20 ℃ of temperature, keep reaction 1 hour to coupled reaction to finish, coupled reaction is warming up to 60 ℃ and keeps being turned in 5 hours brilliant after finishing, then filtered, washed, can be made following formula (I-5) containing the Phenylindole azo-compound.
Embodiment 5
(1) add 98% sulfuric acid 52.5g in flask, 40% nitrosyl sulfuric acid 168.3g, stir 1 hour, control 30 ℃ of temperature, under agitation add 103.5g(0.5mol) 2, the 6-Dichloro-4-nitroaniline, about insulation reaction 1 hour, diazotization completes, and then adds the 1620g frozen water, under stirring, above-mentioned diazonium salt is added and is diluted;
(2) add 1g emulsifier tween-60 in the diazonium salt diluent in step (1);
(3) add 50% sulfuric acid 93 2g at flask, control 30 ℃ of temperature, add N-propenyl-2-phenylindone 93.2g altogether under stirring, insulation keeps 1 hour CL, treats coupling.
By above-mentioned dissolving, the sulphuric acid soln of good N-methyl-2-phenylindone adds in the diazonium salt diluent that adds emulsifying agent of preparation in step (2) slowly, control 10 ℃ of temperature, keep reaction 1 hour to coupled reaction to finish, coupled reaction is warming up to 65 ℃ and keeps being turned in 4 hours brilliant after finishing, then filtered, washed, can be made following formula (I-3) containing the Phenylindole azo-compound.
Embodiment 6
(1) add industrial concentrated hydrochloric acid 109.5g in reaction vessel, add 5-sulfydryl-3-amino-1,2 under stirring, 4-triazole 34.8g(0.3mol), normal temperature making beating 3.0 hours.Be cooled to 5 ℃, at this temperature, add the sodium nitrite solution that concentration is 40% to be total to 54.3g, at 0 ~ 5 ℃, keep stirring within 2 hours, to make diazonium salt, then add frozen water 3600g to be diluted, standby.
(2) add 2g emulsifier tween-80 in the diazonium salt diluent in step (1);
(3) add 98% sulfuric acid 62.1g at flask, control 40 ℃ of temperature, add N-methyl-2-phenylindone 62.1g altogether under stirring, insulation keeps 2 hours CLs, treats coupling.
By above-mentioned dissolving, the sulphuric acid soln of good 2-phenylindone adds in the diazonium salt diluent that adds emulsifying agent of preparation in step (2) slowly, control 5 ℃ of temperature, keep reaction 4 hours to coupled reaction to finish, coupled reaction is warming up to 75 ℃ and keeps being turned in 2 hours brilliant after finishing, then filtered, washed, can be made following formula (I-6) containing the Phenylindole azo-compound.
Embodiment 7 ~ 16
According to the described method of above embodiment 1 ~ 6, logical formula IV or general formula (V), logical formula VI carries out the equimolar amount replacement by the component shown in table 1, can make the azo-compound containing Phenylindole of the present invention.
| Embodiment | Logical formula IV or general formula (V) | Logical formula VI | The azo-compound containing Phenylindole made |
| 7 | 2,6-Dichloro-4-nitroaniline | 2-phenylindone |
 |
| 8 | 2,6-Dichloro-4-nitroaniline | N-ethyl-2-phenylindone | |
| 9 | The bromo-4-N-methyl-p-nitroaniline of 2,6-bis- | N-methyl-2- |
 |
| 10 | The bromo-4-N-methyl-p-nitroaniline of 2,6-bis- | N-propenyl-2- |
 |
| 11 | 3-amino-1,2, the 4-triazole | N-methyl-2- |
 |
| 12 | The 4-N-methyl-p-nitroaniline | N-ethyl-2- |
 |
| 13 | The 4-N-methyl-p-nitroaniline | N-propenyl-2- |
 |
| 14 | 3-amino-1,2, the 4-triazole | N-ethyl-2- |
 |
| 15 | 3-amino-1,2, the 4-triazole | N-propenyl-2-phenylindone |
 |
| 16 | 5-sulfydryl-3-amino-1,2, the 4-triazole | N-ethyl-2-phenylindone |  |
Embodiment 17
Get respectively each 10 grams of the azo-compound containing Phenylindole of embodiment 1 ~ 16 preparation, even with 60 gram pure water sand milling together with 15 gram dispersing agent MFs in sand mill, then drying and dehydrating obtains corresponding commercial dye.
Apply this commercial dye, utilize High Temperature High Pressure to dye model machine, under pH value 4 ~ 4.5 conditions, in 130 ℃ of dyeing 60 minutes, hyperfine polyester fiber is dyeed, and carry out reduction clearing.
Adopt that GB GB/T3921-1997, GB/T3920-1997, GB/T8427-1998, GB/T5718-1997 test that it is water-fastness, rub resistance, sunlight fastness, fastness to sublimation.Test result is as shown in table 2.
Table 2
| Embodiment | Water-fastness | Rub resistance | Sun-resistant | Anti-distillation | Degree of fixation | Maximum absorption wavelength |
| Embodiment | ||||||
| 1 | 5 | 5 | 7 | 4~5 | 99.1% | 400nm |
| Embodiment 2 | 5 | 5 | 7 | 3~4 | 98.9% | 393 nm |
| Embodiment 3 | 5 | 4~5 | 6~7 | 4 | 100.2% | 402 |
| Embodiment | ||||||
| 4 | 4~5 | 4~5 | 7 | 4 | 100.1% | 395 nm |
| Embodiment 5 | 4~5 | 4~5 | 7 | 3~4 | 99.3% | 390 nm |
| Embodiment 6 | 4~5 | 4~5 | 7 | 3~4 | 99.5% | 385 nm |
| Embodiment 7 | 4~5 | 5 | 6~7 | 3 | 96.2% | 388 nm |
| Embodiment 8 | 4~5 | 5 | 7 | 4~5 | 99.9% | 396 nm |
| Embodiment 9 | 5 | 4~5 | 7 | 4 | 98.5% | 408 |
| Embodiment | ||||||
| 10 | 4~5 | 5 | 6~7 | 3 | 98.6% | 410 |
| Embodiment | ||||||
| 11 | 4~5 | 5 | 6~7 | 3~4 | 98.9% | 405 |
| Embodiment | ||||||
| 12 | 5 | 4~5 | 7 | 3 | 99.7% | 402 |
| Embodiment | ||||||
| 13 | 5 | 4~5 | 6~7 | 4 | 99.1% | 405 |
| Embodiment | ||||||
| 14 | 4~5 | 5 | 6~7 | 3~4 | 97.9% | 412 |
| Embodiment | ||||||
| 15 | 5 | 4~5 | 6~7 | 4 | 98.2% | 398 nm |
| Embodiment 16 | 4~5 | 4~5 | 6~7 | 4 | 100.3% | 392 nm |
Annotate: maximum absorption wavelength is measured in acetone.
As shown in table 2, azo-compound of the present invention is applied in terylene, the vinegar fibre, and acrylic fibers, the dyeing of the hydrophobic fiber materials such as polyester and blending, not only have remarkable light fastness, also possesses gratifying washable, crock fastness.
Claims (4)
1. the preparation method containing the azo-compound of Phenylindole, is characterized in that, the described azo-compound general formula containing Phenylindole is as shown in formula I:
In logical formula I: R is selected from alkyl or the propenyl of C1～C4, and D is selected from the group shown in following formula II or formula III,
In formula II, formula III: X
1Be selected from hydrogen, chlorine, bromine a kind of, X
2Be selected from hydrogen or sulfydryl,
The preparation method of the above-mentioned azo-compound containing Phenylindole carries out as follows:
(1) will lead to the compound shown in formula IV or general formula (V) and carry out diazotization reaction with diazo reagent under acidic conditions, obtain diazonium salt, then with frozen water, carry out diluted for use,
X in above-mentioned general formula
1Be selected from hydrogen, chlorine or bromine a kind of, X
2Be selected from hydrogen or sulfydryl;
Diazo reagent is selected from nitrosyl sulfuric acid solution, the mixing solutions of the mixing solutions of hydrochloric acid and Sodium Nitrite or sulfuric acid and Sodium Nitrite;
(2) add emulsifying agent in the diazonium salt diluent in step (1), shown in the consumption of emulsifying agent and logical formula VI, the mass ratio of compound is 0.001～0.05:1;
(3) in another container, by the compound shown in logical formula VI, first use sulfuric acid dissolution, solvent temperature is 0～50 ℃, the solution of compound shown in the logical formula VI dissolved is added dropwise in the diluent of the diazonium salt that has added emulsifying agent in step (2) and carries out coupled reaction, at-5～20 ℃, keep 1～10 hour, then be warming up to 60～75 ℃, keep after 1～5 hour, filtered, filter cake, through washing, obtains the i.e. azo dyestuff cpds containing Phenylindole shown in logical formula I of target product
（Ⅵ）
In general formula, R is selected from alkyl or the propenyl of C1～C4,
Described diazonium salt is 1:0.8～1.2 with the compound molar mass ratio shown in logical formula VI,
The mass ratio of the consumption of described sulfuric acid and logical formula VI compound amount is 1～10:1, and h 2 so 4 concentration is 50%～98%.
2. the preparation method of a kind of azo-compound containing Phenylindole according to claim 1, is characterized in that, in step (1) in compound shown in logical formula IV X
1While being selected from chlorine or bromine, use nitrosyl sulfuric acid diazotization, concrete steps are; Nitrosyl sulfuric acid is slowly joined in sulfuric acid, then will lead to compound shown in formula IV, wherein X
1For chlorine or bromine, slowly join in above-mentioned solution, control temperature at 15～35 ℃, react 1～5 hour, to the solution clarification, obtain diazonium salt, with frozen water, diluted, standby,
Wherein, the consumption of nitrosyl sulfuric acid is 1.05～1.1:1 with the molar mass ratio of the compound shown in logical formula IV, and the consumption of sulfuric acid is to be 1.05～6:1 with the molar mass ratio that leads to compound shown in formula IV or general formula (V); The frozen water amount of dilution diazonium salt and the mass ratio of diazonium salt are 2～10:1.
3. the preparation method of a kind of azo-compound containing Phenylindole according to claim 1, is characterized in that, in step (1) in compound shown in logical formula IV X
1For hydrogen, or while being selected from compound shown in general formula (V), use the mixed solution diazotization of sodium nitrite solution and hydrochloric acid or sulfuric acid, concrete steps are: first will lead to X in formula IV
1For compound shown in compound shown in hydrogen or general formula (V) is added in hydrochloric acid or sulfuric acid, 0～10 ℃ of making beating, to abundant, mix, then with ice bath, reaction solution is cooled to 0～5 ℃, by the sodium nitrite solution of mass concentration 20%～40%, joins in above-mentioned solution, stir 0.5～2 hour, to the solution clarification, obtain diazonium salt, then with frozen water, diluted, standby
Wherein, while using hydrochloric acid, the consumption of hydrochloric acid is to be 2.25～3.0:1 with the molar mass ratio that leads to compound shown in formula IV or general formula (V); While using sulfuric acid, the consumption of sulfuric acid is to be 1.05～6:1 with the molar mass ratio that leads to compound shown in formula IV or general formula (V); The consumption of Sodium Nitrite is 1.05～1.1:1 with the molar mass ratio of the compound shown in logical formula IV, and the frozen water amount of dilution diazonium salt and the mass ratio of diazonium salt are 2～10:1.
4. according to the preparation method of claim 1 or 2 or 3 described a kind of azo-compounds containing Phenylindole, it is characterized in that, the mass concentration of nitrosyl sulfuric acid is 40%, and h 2 so 4 concentration is 50%～98%, and hydrochloric acid is selected from industrial concentrated hydrochloric acid, and mass concentration is 30%.
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| DE1644071A1 (en) * | 1967-09-29 | 1971-03-25 | Basf Ag | Monoazo dyes free of sulfonic acid groups |
| US3829411A (en) * | 1972-03-29 | 1974-08-13 | Eastman Kodak Co | Thiadiazolyl-azo-indole compounds |
| DE2527712A1 (en) * | 1975-06-21 | 1976-12-30 | Bayer Ag | AZO DYES |
| DE2715135A1 (en) * | 1977-04-05 | 1978-10-19 | Bayer Ag | AZO DYES |
| DE2916861A1 (en) * | 1979-04-26 | 1980-11-06 | Bayer Ag | METHOD FOR DYEING AND PRINTING CELLULOSE FIBERS |
| JPH068387B2 (en) * | 1986-11-26 | 1994-02-02 | 日本化薬株式会社 | Monoazo compound and dyeing method for hydrophobic fiber using the same |
| JP2872387B2 (en) * | 1990-11-07 | 1999-03-17 | 日本化薬株式会社 | Disperse dye composition and method for dyeing hydrophobic fiber |
| JP2006008871A (en) * | 2004-06-25 | 2006-01-12 | Dystar Japan Ltd | Disperse dye for polylactic acid fiber |
| JP5610610B2 (en) * | 2010-01-15 | 2014-10-22 | 日本化薬株式会社 | Azo dye |
-
2012
- 2012-02-14 CN CN2012100317987A patent/CN102604414B/en active Active
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| Publication number | Publication date |
|---|---|
| CN102604414A (en) | 2012-07-25 |
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