CN105439896A - Diaminoazobenzene compound - Google Patents
Diaminoazobenzene compound Download PDFInfo
- Publication number
- CN105439896A CN105439896A CN201410509993.5A CN201410509993A CN105439896A CN 105439896 A CN105439896 A CN 105439896A CN 201410509993 A CN201410509993 A CN 201410509993A CN 105439896 A CN105439896 A CN 105439896A
- Authority
- CN
- China
- Prior art keywords
- compound
- reaction
- preferred
- acid
- condition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention discloses a diaminoazobenzene compound 1. The diaminoazobenzene compound 1 has satisfactory washing fastness and excellent sublimation fastness, has a novel structure and is suitable for dyeing and printing of a polyester fiber textile material and a blend fiber product.
Description
Technical field
The present invention relates to a kind of compound of nitrogen benzide amine.
Background technology
Dispersed dye are that a class formation is simple, water-soluble low, mainly with the non-ionic dye that molecule is dispersion state existence in dye bath, be mainly used in dyeing and the stamp of trevira and BLENDED FABRIC thereof, also can be used for dyeing and the stamp of the hydrophobic textile material such as cellulose acetate fibre and tynex.In recent years, along with the continuous growth of trevira output and consumption, dispersed dye occupy an important position in the world and domestic Dyestuff Market always.
Now, green environment and healthy living have become the topic of people's growing interest, and the security of taking textiles also becomes important concern content thereupon, and this just proposes more and more higher application requiring to textiles dyestuff used.Dyefastness is one of important indicator characterizing application performance, and the content that dyefastness relates to is more, wherein comparatively common are washing fastness and sublimation fastness.
The Conventional dye kind widely applied in the market still has the space of lifting in sublimation fastness and washing fastness.
Summary of the invention
Technical problem to be solved by this invention is defect in order to overcome existing dye sublimation fastness and washing fastness difference and provides a kind of compound of nitrogen benzide amine.The compound of nitrogen benzide amine of the present invention not only has gratifying washing fastness and remarkable fastness to sublimation, and novel structure, is applicable to dyeing and the stamp of polyester woven material and mixed fibre goods thereof.
The invention provides a kind of compound 1 of nitrogen benzide amine:
Wherein, R
1for
or hydrogen atom; R
2for C
1-C
4alkyl (such as methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or the tertiary butyl); R
3for
or
r
4for C
1-C
3alkyl (such as methyl, ethyl, propyl group or sec.-propyl) or hydrogen atom.
R
1preferred hydrogen atom; R
2preferable methyl or ethyl; R
4preferable methyl.
Present invention also offers the preparation method of compound 1, it comprises the following steps: in water, under sour existent condition, compound 2 and compound 3 is carried out coupled reaction, obtains compound 1;
Wherein, R
1, R
2and R
3definition all same as above,
for Cl
-, CH
2cOO
-, H
2pO
4 -, HSO
4 -or NO
3 -.
Described coupled reaction can be carried out according to the ordinary method of such reaction in this area, particularly preferably following reaction method and condition:
In coupled reaction, the Molar of described water and described compound 2 than preferred 1.6L/mol ~ 4.7L/mol, preferred 2.3L/mol ~ 3.5L/mol further, more preferred 2.7L/mol ~ 3.0L/mol further.
In coupled reaction, one or more in the preferred hydrochloric acid of described acid, acetic acid, phosphoric acid, nitric acid and sulfuric acid, one or more further preferably in hydrochloric acid, acetic acid and sulfuric acid, then preferably sulfuric acid and/or hydrochloric acid further; Described acid can participate in reaction with the form of aqueous acid, the massfraction of described aqueous acid preferably 3% ~ 98%, and further preferably 5% ~ 80%.
In coupled reaction, the volume ratio of described acid and described water preferably 0.01 ~ 0.06, further preferably 0.015 ~ 0.04, further preferably 0.033.
In coupled reaction, described compound 2 and the preferred 1.5:1 ~ 1:1 of mol ratio of compound 3, further preferred 1.2:1 ~ 1:1, further preferred 1.1:1.
In coupled reaction, the temperature of described coupled reaction preferably-10 DEG C ~ 30 DEG C, preferred-10 DEG C ~ 10 DEG C further, more preferred-5 DEG C ~ 5 DEG C further.
In coupled reaction, the process of described coupled reaction can be monitored by traditional test methods in this area (as filter paper oozes circle method), and ooze circle with compound 2 and do not develop the color for reaction end, the preferred reaction time is 1h ~ 3h, further preferred 2h.
The preparation method of compound 1 can also comprise the following steps: work as R
3for
or
time, under solvent-free existent condition, under vitriol oil existent condition, nitrosyl sulfuric acid and compound 8 are carried out diazotization reaction, obtains compound 3; Work as R
3for
time, under sour existent condition, by nitrite or nitrosyl sulfuric acid, carry out diazotization reaction with compound 8, obtain compound 3;
Wherein,
definition all same as above.
Described diazotization reaction can be carried out according to the ordinary method of such reaction in this area, particularly preferably following reaction method and condition:
In diazotization reaction, described is under solvent-free existent condition under the condition of anhydrous condition and/or organic solvent-free.
In diazotization reaction, described vitriol oil preferred mass mark is the vitriol oil of 98%.
In diazotization reaction, work as R
3for
time, preferably carry out in presence of water; The Molar of described water and compound 8 than preferred 0.13L/mol ~ 1.33L/mol, preferred 0.27L/mol ~ 0.67L/mol further.
In diazotization reaction, work as R
3for
time, can carry out under solvent-free existent condition.
In diazotization reaction, work as R
3for
time, one or more in the preferred hydrochloric acid of described acid, acetic acid and sulfuric acid, further preferably sulfuric acid and/or hydrochloric acid; Described acid can participate in reaction with the form of aqueous acid, the massfraction of described aqueous acid preferably 5% ~ 99%, and further preferably 10% ~ 80%.
In diazotization reaction, described compound 8 and the preferred 1:2 ~ 1:5 of mol ratio of described acid, further preferred 1:2.5 ~ 1:4, further preferred 1:2.8.
In diazotization reaction, the preferred Sodium Nitrite of described nitrite.
In diazotization reaction, described compound 8 and the preferred 1:1 ~ 1:1.2 of mol ratio of described nitrite or described nitrosyl sulfuric acid, further preferred 1:1 ~ 1:1.1, further preferred 1:1.05.
In diazotization reaction, the temperature of described reaction preferably-10 DEG C ~ 30 DEG C, preferred-10 ~ 20 DEG C further.
In diazotization reaction, the process of described diazotization reaction can by traditional test methods (as TLC) monitoring in this area, for reaction end when no longer reacting with described compound 8, the preferred reaction time is 1h ~ 5h, further preferred 2h ~ 3h.
The preparation method of compound 1 can also comprise the following steps: under the existence of catalyzer and alkali, compound 4 and compound 5 is carried out condensation reaction, obtains compound 2; Described catalyzer is alkali metal halide;
Wherein, R
1and R
2definition all same as above.
Described condensation reaction can be carried out according to the ordinary method of such reaction in this area, particularly preferably following reaction method and condition:
In the condensation reaction, described reaction is preferably carried out under solvent-free existent condition.
In the condensation reaction, one or more in the preferred potassiumiodide of described alkali metal halide, sodium iodide, Potassium Bromide and Sodium Bromide, further preferred Sodium Bromide.
In the condensation reaction, the preferred 0.01:1 ~ 1:1 of mol ratio of described catalyzer and described compound 4, further preferred 0.2:1 ~ 0.4:1, further preferably 0.24:1.
In the condensation reaction, the preferred mineral alkali of described alkali, one or more in the preferred sodium hydroxide of described mineral alkali, potassium hydroxide, salt of wormwood, sodium bicarbonate, saleratus and anhydrous sodium carbonate, further preferred anhydrous sodium carbonate.
In the condensation reaction, the preferred 1.0:1 ~ 5:1 of mol ratio of described alkali and described compound 4, further preferred 1.0:1 ~ 1.5:1, further preferably 1.2:1.
In the condensation reaction, described compound 4 and the preferred 1:2 ~ 1:2.5 of mol ratio of described compound 5, further preferred 1:2 ~ 1:2.2.
In the condensation reaction, the temperature of described condensation reaction preferably 50 DEG C ~ 150 DEG C, preferably 70 DEG C ~ 120 DEG C further, more preferably 100 DEG C further.
In the condensation reaction, the process of described condensation reaction can be monitored by testing method (as HPLC) conventional in this area, and for reaction end when no longer reacting with compound 4, the preferred reaction time is 2h ~ 10h, further preferred 4h ~ 8h.
The preparation method of compound 1 can also comprise the following steps: compound 6 and Mono Chloro Acetic Acid are carried out esterification, obtains compound 5;
Wherein, R
2definition same as above.
Described esterification can be carried out according to the ordinary method of such reaction in this area, particularly preferably following reaction method and condition:
In the esterification reaction, described reaction is preferably carried out in the absence of a solvent.
In the esterification reaction, described reaction is preferably carried out under the katalysis of catalyzer; Described catalyzer can be strong acid, preferably sulfuric acid and/or tosic acid, further preferred tosic acid; Preferred 0.01:1 ~ the 1:1 of mol ratio of described catalyzer and described compound 6, further preferred 0.03:1 ~ 0.1:1, further preferred 0.05:1.
In the esterification reaction, the preferred 1:1 ~ 1:1.2 of mol ratio of described Mono Chloro Acetic Acid and described compound 6, further preferred 1:1 ~ 1:1.1.
In the esterification reaction, the temperature of described esterification preferably 70 DEG C ~ 150 DEG C, preferably 100 DEG C ~ 130 DEG C further, more preferably 120 DEG C further.
In the esterification reaction, the process of described esterification can be monitored by testing method (as TLC) conventional in this area, and be reaction end when no longer reacting with Mono Chloro Acetic Acid, the preferred reaction time is 2h ~ 6h, further preferred 3h ~ 5h.
Present invention also offers a kind of midbody compound that can be used for preparing compound 1, it is
wherein, R
1and R
2definition as described in any one of claims 1 to 3.
Present invention also offers the application of above-claimed cpd 1 as dispersed dye.Compound 1 of the present invention can process according to the conventional treatment method (as sand milling) in this area, obtains commercialization dispersed dye.
The commercialization dispersed dye that compound of the present invention is obtained, can be applied to dyeing and the stamp of trevira and mixed fibre goods thereof according to the common staining method of this type disperse dye in this area.Described trevira and pet fiber and mixed fibre goods thereof, if polyester/cotton, polyester/wool are trevira conventional in this area and mixed fibre goods thereof.Described mixed fibre goods can be the conventional existence form of this area, as fiber, yarn, woven fabrics, knitted fabrics or non-woven fabric.
On the basis meeting this area general knowledge, above-mentioned each optimum condition, can arbitrary combination, obtains the preferred embodiments of the invention.
Room temperature in the present invention is 10 DEG C ~ 30 DEG C.
Agents useful for same of the present invention and raw material are all commercially.
Positive progressive effect of the present invention is: the compound of nitrogen benzide amine not only has gratifying washing fastness and remarkable fastness to sublimation, and novel structure, is applicable to dyeing and the stamp of polyester woven material and mixed fibre goods thereof.
Embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, conventionally and condition, or selects according to catalogue.
LC-MS data described in the present invention are by WatersUPLC-SQD LC-MS instrument (moving phase is acetonitrile/water system, 60%-90% acetonitrile V/V, column temperature 40 DEG C) test gained.
The preparation of embodiment 1 compound 5-1
CICH
2COOCH
2CH
2OCv
35-1
Under room temperature condition, in the 100ml there-necked flask of a drying, add 17.08g ethylene glycol monomethyl ether, in stirring, then add about 18.9g Mono Chloro Acetic Acid and 2g tosic acid, stir.Slowly be warming up to 120 DEG C of insulation backflows after stirring, after about reacting 3h, raw material reaction is complete.Be cooled to room temperature, underpressure distillation to 80 DEG C excessive ethylene glycol monomethyl ether of removing and water, continue to heat up, collect 100 DEG C of-140 DEG C of cuts.Again underpressure distillation removing moisture is carried out to cut, obtain compound 5-125.1g, yield 82.25%, purity 96.3%.
The preparation of embodiment 2 compound 2-3
Under room temperature condition, in the 100ml there-necked flask of a drying, add about 23.5g compound 5-1, in stirring, then add 10.51g 3-acetylaminoaniline, 8.92g anhydrous sodium carbonate and 1.75g Sodium Bromide, stir.Then 100 DEG C of insulation reaction are slowly warming up to.HPLC monitoring reaction is until 3-acetylaminoaniline reacts completely.Add about 20ml water and make dissolution of solid, regulate PH to neutral, pour separating funnel stratification into.Add water after branch vibration layer again and be about 20ml, fully stratification after concussion, collects organic phase, and underpressure distillation removing moisture, obtain compound 2-325.4g, yield 94.89%, the result that purity 96.5%, LC-MS measures compound 2-3 is [M+H]
+383.52, [M+Na]
+405.5.
Prepare compound 2-1 ~ 2-4 according to the method for embodiment 1 ~ 2, its relevant experimental data and Structural Identification data are in table 1.
The experimental data of table 1 compound 2-1 ~ 2-4 and Structural Identification data
The preparation of embodiment 3 compound 1-3
Under room temperature condition, in the 100ml there-necked flask of a drying, add the sulphuric acid soln of the sulfuric acid of 11.2g98%, the nitrosyl sulfuric acid of 13.34g40%, after stirring, ice bath is cooled to 10 DEG C-15 DEG C, slowly add about 7.32g2,4-dinitraniline, about adds 1h, is incubated 3h and obtains transparent diazo liquid after adding under 10 DEG C of-15 DEG C of conditions.Then in a 2000ml beaker, add liquid at the bottom of 120ml water, 4ml vitriol oil preparation coupling, on the rocksly be cooled to 0-5 DEG C, then in 1h, drip 16.64g compound 2-3 and above-mentioned diazo liquid carries out coupled reaction simultaneously, in dropping process, ensure that compound 2-3 is micro-excessive to ooze circle measuring.Drip rear control temperature on the rocks 0 DEG C-5 DEG C, insulation 2h completes coupling, is then naturally stirred to room temperature, filters, and washing is dried, obtained the dyestuff filter-cakes 21.3g of compound 1-3.Yield 92.37%.HPLC purity 94.5%.The result that LC-MS measures compound 1-3 is [M+H]
+577.6, [M+Na]
+599.5.
The preparation of embodiment 4 compound 1-5
Under room temperature condition, in a 100ml there-necked flask, add the hydrochloric acid of 20ml water, 12.17g36%, then under agitation add 4.14g p-Nitroaniline, 70 DEG C are warming up to after stirring, insulation 2h makes p-Nitroaniline fully dissolve, then Temperature fall to 50 DEG C, then is cooled to 0-5 DEG C with ice bath.Then control temperature is at 0-5 DEG C, slowly drips 9.12g25% sodium nitrite in aqueous solution, about drips 20min, adds rear 0-5 DEG C of insulation 1h and obtains diazo liquid.Then in a 1000ml beaker, add liquid at the bottom of 90ml water, 3ml vitriol oil preparation coupling, on the rocksly be cooled to 0-5 DEG C, then in 1h, drip 10.55g compound 2-1 and above-mentioned diazo liquid carries out coupled reaction simultaneously, in dropping process, ensure that compound 2-1 is micro-excessive to ooze circle measuring.Drip rear control temperature on the rocks 0 DEG C-5 DEG C, insulation 2h completes coupling, is then naturally stirred to room temperature, filters, and washing is dried, obtained the dyestuff filter-cakes 13.4g of compound 1-5.Yield 94.2%.HPLC purity 95.3%.The result that LC-MS measures compound 1-5 is [M+H]
+475.4, [M+Na]
+497.5.
Compound 1-1 ~ 1-12 is prepared according to the method for embodiment 1 ~ 4.Relevant experimental data and Structural Identification data are in table 2.
The experimental data of table 2 compound 1-1 ~ 1-12 and Structural Identification data
Effect example 1
The compound 1-3 getting 5 grams of embodiments 3 obtained is dispersed in 500 ml waters, draw 20 milliliters to mix with the water of 80 milliliters, dye bath pH is adjusted to be 4 ~ 5 with acetic acid, be warming up to 70 DEG C to put into 5 grams of polyester fiber cloths simultaneously and dye, 130 DEG C are warming up to by 70 DEG C in 30 minutes, be incubated 50 minutes, be cooled to less than 90 DEG C draining cleanings.The 100 milliliters of reduction clearing liquid put into by cloth specimen again containing 1 grams per liter caustic soda and 3 grams per liter vat powders clean in 80 DEG C, and the time is 20 minutes.
The dispersed dye prepared compound 1-1 ~ 1-12 according to the method for effect example 1 and control compounds I ~ III dye, and adopt GB GB/T3921-2008, GB/T5718-1997 tests its washing fastness and sublimation fastness, its test result is in table 3.
The Color data of dispersed dye prepared by table 3 compound 1-1 ~ 1-12
The data presentation of table 3: dye composition I ~ III that is conventional and structural similitude of the present invention on contrast market, dispersed dye of the present invention, not only have higher washing fastness, and have excellent sublimation fastness.
Claims (4)
1. the compound 1 of a nitrogen benzide amine,
Wherein, R
1for
or hydrogen atom, R
2for C
1-C
4alkyl, R
3for
or
r
4for C
1-C
3alkyl or hydrogen atom.
2. compound 1 as claimed in claim 1, is characterized in that, described C
1-C
4alkyl be methyl, ethyl, propyl group, sec.-propyl, butyl, isobutyl-or the tertiary butyl;
And/or, described C
1-C
3alkyl be methyl, ethyl, propyl group or sec.-propyl.
3. compound 1 as claimed in claim 2, is characterized in that, described R
1for hydrogen atom;
And/or, described R
2for methyl or ethyl;
And/or, described R
4for methyl.
4. compound 1 as claimed in claim 1, it is characterized in that, described compound 1 is following arbitrary compound:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410509993.5A CN105439896A (en) | 2014-09-28 | 2014-09-28 | Diaminoazobenzene compound |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410509993.5A CN105439896A (en) | 2014-09-28 | 2014-09-28 | Diaminoazobenzene compound |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105439896A true CN105439896A (en) | 2016-03-30 |
Family
ID=55550598
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410509993.5A Pending CN105439896A (en) | 2014-09-28 | 2014-09-28 | Diaminoazobenzene compound |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105439896A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107474582A (en) * | 2017-05-19 | 2017-12-15 | 杭州福莱蒽特精细化工有限公司 | A kind of carbuncle azo dyes and its preparation method and application |
| CN107501989A (en) * | 2017-05-19 | 2017-12-22 | 杭州福莱蒽特精细化工有限公司 | A kind of blue azo dyes and its preparation method and application |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5070673A (en) * | 1973-10-30 | 1975-06-12 | ||
| US4119624A (en) * | 1972-06-08 | 1978-10-10 | Imperial Chemical Industries Limited | Disperse monoazo dyestuffs |
| JPS55116754A (en) * | 1979-03-05 | 1980-09-08 | Mitsui Toatsu Chem Inc | Monoazo compound, its preparation, and dyeing of synthetic fiber |
| JPS6141382A (en) * | 1984-07-27 | 1986-02-27 | 三菱化学株式会社 | Alkali resist style composition for polyester fiber |
| EP0684287A1 (en) * | 1994-05-20 | 1995-11-29 | Hoechst Mitsubishi Kasei Co., Ltd. | Water insoluble red monoazo dyes, their preparation and the use thereof |
| CN1059456C (en) * | 1993-05-06 | 2000-12-13 | 希巴特殊化学控股公司 | Azo dyes |
-
2014
- 2014-09-28 CN CN201410509993.5A patent/CN105439896A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4119624A (en) * | 1972-06-08 | 1978-10-10 | Imperial Chemical Industries Limited | Disperse monoazo dyestuffs |
| JPS5070673A (en) * | 1973-10-30 | 1975-06-12 | ||
| JPS55116754A (en) * | 1979-03-05 | 1980-09-08 | Mitsui Toatsu Chem Inc | Monoazo compound, its preparation, and dyeing of synthetic fiber |
| JPS6141382A (en) * | 1984-07-27 | 1986-02-27 | 三菱化学株式会社 | Alkali resist style composition for polyester fiber |
| CN1059456C (en) * | 1993-05-06 | 2000-12-13 | 希巴特殊化学控股公司 | Azo dyes |
| EP0684287A1 (en) * | 1994-05-20 | 1995-11-29 | Hoechst Mitsubishi Kasei Co., Ltd. | Water insoluble red monoazo dyes, their preparation and the use thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107474582A (en) * | 2017-05-19 | 2017-12-15 | 杭州福莱蒽特精细化工有限公司 | A kind of carbuncle azo dyes and its preparation method and application |
| CN107501989A (en) * | 2017-05-19 | 2017-12-22 | 杭州福莱蒽特精细化工有限公司 | A kind of blue azo dyes and its preparation method and application |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102603572B (en) | Monoazo compound as well as preparation method and application thereof | |
| CN104059000B (en) | A kind of reactive dyestuffs and its production and use | |
| CN101117446A (en) | Process for synthesizing azo dispersion dyes monomer compound | |
| CN105439896A (en) | Diaminoazobenzene compound | |
| CN102453348B (en) | Reactive yellow compound and application thereof | |
| CN113583468A (en) | Dispersed brown and preparation method thereof | |
| CN103214877B (en) | A kind of active red dye composition | |
| CN105524483A (en) | Application of azoaniline compound as disperse dye | |
| CN105523959A (en) | Method for preparing azoaniline compound | |
| EP0038296B1 (en) | Bisazo compounds | |
| CN102504596A (en) | Bi-component monoazo disperse blue dye composition | |
| CN105439891A (en) | Azoaniline compound | |
| CN105254517A (en) | Naphthalene ring compound and preparation method thereof | |
| CN103233370B (en) | Disperse dye application | |
| KR20070015584A (en) | Monoazo dyes | |
| CN105218396A (en) | A kind of preparation method of azo-compound | |
| CN105111775A (en) | Application of azo compound | |
| CN105152964A (en) | Azo-compound | |
| CN106892874A (en) | The preparation method of monoazos | |
| CN105778563B (en) | A kind of Black reactive dye composition and its production and use | |
| CN105238094B (en) | A kind of feux rouges blueness azo dispersion dyes with intensity of colour occurred frequently and preparation method thereof | |
| CN116445004B (en) | Red disperse dye and preparation method thereof | |
| CN104497625A (en) | Yellow active dye compound, and preparation method and application thereof | |
| CN105295425A (en) | Environment-friendly weak acid red dye and preparation method thereof | |
| CN107141265A (en) | A kind of azo compound, its preparation method, intermediate and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160330 |
|
| WD01 | Invention patent application deemed withdrawn after publication |