CN106432010A - Dye intermediate namely (3-beta-hydroxyethylsulfonyl)aniline-4-aminobenzenesulfonic acid and preparation method thereof - Google Patents
Dye intermediate namely (3-beta-hydroxyethylsulfonyl)aniline-4-aminobenzenesulfonic acid and preparation method thereof Download PDFInfo
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- CN106432010A CN106432010A CN201610715988.9A CN201610715988A CN106432010A CN 106432010 A CN106432010 A CN 106432010A CN 201610715988 A CN201610715988 A CN 201610715988A CN 106432010 A CN106432010 A CN 106432010A
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- hydroxyethylation
- added
- chlorosulfonation
- dyestuff
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Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C317/00—Sulfones; Sulfoxides
- C07C317/26—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
- C07C317/32—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
- C07C317/34—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring
- C07C317/36—Sulfones; Sulfoxides having sulfone or sulfoxide groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton with sulfone or sulfoxide groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having sulfone or sulfoxide groups and amino groups bound to carbon atoms of six-membered aromatic rings being part of the same non-condensed ring or of a condensed ring system containing that ring with the nitrogen atoms of the amino groups bound to hydrogen atoms or to carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
- C07C303/02—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of sulfonic acids or halides thereof
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/04—Preparation of sulfones; Preparation of sulfoxides by reactions not involving the formation of sulfone or sulfoxide groups
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B62/00—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves
- C09B62/44—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring
- C09B62/503—Reactive dyes, i.e. dyes which form covalent bonds with the substrates or which polymerise with themselves with the reactive group not directly attached to a heterocyclic ring the reactive group being an esterified or non-esterified hydroxyalkyl sulfonyl or mercaptoalkyl sulfonyl group, a quaternised or non-quaternised aminoalkyl sulfonyl group, a heterylmercapto alkyl sulfonyl group, a vinyl sulfonyl or a substituted vinyl sulfonyl group, or a thiophene-dioxide group
- C09B62/5033—Dioxazine dyes
Abstract
The invention relates to a dye intermediate namely (3-beta-hydroxyethylsulfonyl)aniline-4-aminobenzenesulfonic acid and a preparation method thereof. The intermediate is (3-beta-hydroxyethylsulfonyl)aniline-4-aminobenzenesulfonic acid which has a structural formula as shown in a formula (I) in the specification. According to the invention, the dye intermediate is prepared through a series of preparation processes like chlorosulfonation of 2-chloro-5-nitrobenzenesulfonic acid, reduction with sodium sulfite, hydroxyethylation, a condensation reaction of the hydroxyethylated product and p-aminobenzenesulfonic acid, nitro hydrogenation reduction, etc. Compared with a common dye intermediate, the novel dye intermediate prepared by using the method provided by the invention can well improve water solubility of a prepared dye, and reduce production cost and environmental pollution.
Description
Technical field
The present invention relates to dyestuff intermediate field, more particularly to a kind of dyestuff intermediate (3- β-hydroxyethyl sulfone) aniline-
4- p-aminobenzene sulfonic acid and preparation method thereof.
Background technology
Dyestuff intermediate refers to the various arene derivatives for producing dyestuff and organic pigment, mainly with from Coal Chemical Industry
And the aromatic hydrocarbons such as the benzene of petrochemical industry, toluene, naphthalene, anthracene is base stock, to be obtained by a series of organic synthesis.
The purpose of the present invention is to prepare a kind of important dyestuff intermediate (3- β-hydroxyethyl sulfone) aniline -4- p-aminophenyl sulphur
Acid, can have extensive market application foreground as the coupling component of azo dye in the preparation field of reactive dye.
Content of the invention
The technical problem to be solved in the present invention is to provide a kind of dyestuff intermediate and preparation method thereof.
The technical solution used in the present invention is：
A kind of dyestuff intermediate, the intermediate is (3- β-hydroxyethyl sulfone) aniline -4- p-aminobenzene sulfonic acid, structural formula such as formula
(I) shown in：
Present invention also offers the preparation method of above-mentioned dyestuff intermediate, the method comprises the steps：
1), chlorosulfonation：Chloro- for 2- 5- nitrobenzene-sulfonic acid and chlorosulfonic acid are carried out chlorosulfonation, prepared chlorosulfonation product；
2), reduce：Chlorosulfonation product and sodium sulfite are carried out reduction reaction, prepared reduzate in the basic conditions；
3), hydroxyethylation：By reduzate and reacting ethylene oxide, prepared hydroxyethylation product；
4), it is condensed：Hydroxyethylation product and p-aminobenzene sulfonic acid are condensed, are obtained condensation substance；
5), hydrogenating reduction：Condensation substance is carried out hydrogenating reduction, that is, dyestuff intermediate is obtained.
Specifically, the preparation method of above-mentioned dyestuff intermediate, comprises the steps：
1), chlorosulfonation：To in dry four-hole bottle, addition chlorosulfonic acid, 15～20 DEG C of water bath heat preservation, are slowly added to the chloro- 5- of 2-
Nitrobenzene-sulfonic acid；120～135 DEG C of reactions are to slowly warm up to, after being reacted with liquid chromatogram measuring completely, reactant liquor are slowly dripped
Ice analysis in the beaker equipped with mixture of ice and water is added to, temperature remains at -5～0 DEG C；It is filtrated to get filter cake；
2), reduce：Sodium sulfite is added to the water dissolving, pH=7.5～8.0 ice-water bath is adjusted with NaOH (30%) and is kept
15～20 DEG C of temperature, by step 1) products therefrom is slowly added in system, keeps system pH=7～8.0 with NaOH (30%)；
Add, continuously stirred 1h, keep pH=7.5～8.0,20～25 DEG C of temperature；NaCl is added to saltout, product is filtrated to get after separating out
Filter cake；
3), hydroxyethylation：By step 2) products therefrom water beating, 55～60 DEG C are warmed up to, are allowed to be completely dissolved；Maintain
Temperature is 60 DEG C, is passed through ethylene oxide gas, while using H in system2SO4(25-30%) pH=6.8～7.2 are adjusted, continues
18～20h is passed through, system solution gradually has solid particle to separate out, as generates product；After liquid chromatogram measuring reaction completely,
Cool to 40 DEG C；Filter, washing obtains product for hydroxyethylation product；Then product is put in 80 DEG C of baking boxs and dries, obtain hydroxyl
Ethylation products dry product；
4), it is condensed：By step 3) product is added in isopropanol and is heated to boiling point, and stop heating, be subsequently adding to amino
Benzenesulfonic acid, then returns and evaporates until reacting complete；
5), hydrogenating reduction：By step 4) products therefrom put in autoclave, adds catalyst Raney's nickel, seals high pressure
Kettle is passed through nitrogen thereto, displaces the air of the inside, is then passed through hydrogen again, is heated to 100 DEG C, keeps being passed through Hydrogen Vapor Pressure
1.2MPa, cooling discharge after reaction completely, refined salt is added, analysis of material is filtrated to get final product (3- β-hydroxyethyl sulfone) aniline -4-
P-aminobenzene sulfonic acid.
The reaction that above-mentioned steps of the present invention are related to is as follows：
Present invention also offers application of the above-mentioned dyestuff intermediate in dyestuff is prepared.
Present invention also offers a kind of utilize dyestuff obtained in above-mentioned dyestuff intermediate, the dyestuff has the knot of following (II)
Structure：
The present invention is had the advantage that：
The present invention is by the chlorosulfonation of the chloro- 5- nitrobenzene-sulfonic acid of 2-, sodium sulfite reduction, hydroxyethylation and p-aminophenyl
Sulfonic acid condensation reacts, a series of preparation process such as nitro hydrogenation reduction has been obtained the dyestuff intermediate, present invention exploitation
New dyestuff intermediate, compared to conventional dyestuff intermediate, can improve the water solublity of the dyestuff of preparation well, reduce life
Produce cost and reduce environmental pollution.
Specific embodiment
Below by example, the present invention is described in detail, these embodiments are only intended to explain the technical side of the present invention
Case, is not to form any restriction to the present invention.
Embodiment 1：
The preparation method of (3- β-hydroxyethyl sulfone) aniline -4- p-aminobenzene sulfonic acid, comprises the steps：
1), chlorosulfonation：To in dry four-hole bottle, addition 240g chlorosulfonic acid, 15～20 DEG C of water bath heat preservation, are slowly added to do
The chloro- 5- nitrobenzene-sulfonic acid of product raw material 47.52g (100%) 2-；120～135 DEG C of reaction 4h are to slowly warm up to, are surveyed with liquid chromatograph
After fixed reaction completely, reactant liquor is slowly dropped to ice analysis in the beaker equipped with mixture of ice and water, temperature remains at -5
Less than～0 DEG C；It is filtrated to get filter cake；
2), reduce：50g sodium sulfite is added to the water dissolving, pH=7.5～8.0 ice-water bath is adjusted with NaOH (30%)
At 15～20 DEG C of keeping temperature, by step 1) products therefrom is slowly added in system, keeps system pH=7 with NaOH (30%)
～8.0；Add, continuously stirred 1h, keep pH=7.5～8.0,20～25 DEG C of temperature；NaCl is added to saltout, mistake after product precipitation
Filter obtains filter cake；
3), hydroxyethylation：By step 2) products therefrom 250mL water beating, 55～60 DEG C are warmed up to, are allowed to completely molten
Solution；Into reaction vessel, inflated with nitrogen excludes air；Slow heating solution is to 60 DEG C, then is passed through ethylene oxide gas in system,
While using H2SO4(25-30%) pH=6.8～7.2 are adjusted, 18～20h is continually fed into, system solution gradually has solid particle to analyse
Go out, as generate product；It is when the chloro- 5- nitro benzenesulfinic acid of raw material 2- cannot be detected with liquid chromatographic detection and reacts
Completely, then 40 DEG C are cooled to；Filter, washing obtains product for hydroxyethylation product；Then product is put in 80 DEG C of baking boxs
Dry, obtain hydroxyethylation product dry product；
4), it is condensed：93g hydroxyethylation product dry product is added in 84mL isopropanol boiling point is heated to, stop heating, use
15min adds 189.26g p-aminobenzene sulfonic acid, then returns and evaporates 1h until reacting complete；
5), hydrogenating reduction：35g (3- β-hydroxyethyl sulfone) Nitrobenzol -4- p-aminobenzene sulfonic acid is added in pressure reaction still, plus
After entering 2g Raney's nickel catalyst, sealing autoclave is passed through nitrogen thereto, displaces the air of the inside, then passes to hydrogen,
Catalytic hydrogenation under the pressure of 1.2MPa, maintains temperature for 100 DEG C until reacting 5h, till not consuming hydrogen, after reaction completely
Cooling discharge, adds refined salt to saltout, and analysis of material is filtrated to get (3- β-hydroxyethyl sulfone) aniline -4- p-aminobenzene sulfonic acid.
Embodiment 2
A kind of blue active dye, the compound with formula II structure：
The preparation method of the blue active dye, comprises the steps：
A () is condensed
500mL bottom water is added in 1000mL beaker, add 100% amount
80.59g, is warmed up to 60 DEG C, is gradually added into 100%
The tetrachloroquinone 26.93g of amount, uses NaHCO3PH=6～7 are adjusted, joining day general control is in 1h, and temperature control is 55～65
DEG C, holding 2h is finished, reaction is cooled to less than 30 DEG C after terminating, and adds the NaCl of volume ratio 20% to saltout, filters, and filter cake is used full
With brine It 2 times, in 60～80 DEG C of dryings, condensation substance dry product is obtained, dry product is standby after crushing.
(b) esterification, closed loop
The oleum 432.6g of 20% concentration in 500mL four-hole bottle, is added, is slowly added into above-mentioned condensation substance dry product
72.1g, is lowered the temperature with cool brine, charge temperature≤30 DEG C, finishes holding 2h；Then 54g potassium peroxydisulfate is slowly added into again
(K2S2O8), control charge temperature≤30 DEG C, feed time 4h, holding 2h is finished, to be diluted.
(c) dilution, neutralization
Above-mentioned reactant liquor is diluted in mixture of ice and water, controls temperature≤5 DEG C, addition volume ratio 20% is finished in dilution
NaCl saltouts, and saltout time 2h, filters, and gained acidic filter cake is beaten with 400mL frozen water, then uses NaHCO3Regulation pH=5～
6, the spray-dried blue active dye for obtaining shown in formula II.
The performance of blue active dye prepared by the embodiment of the present invention 2 is as follows：
The method of the present invention is described by specific embodiment.Those skilled in the art can use for reference this
The links such as the appropriate feed change of bright content, process conditions realizing other purposes corresponding, its correlation change all without departing from
Present disclosure, all similar replacements and change are it will become apparent to those skilled in the art that be considered as
It is included within the scope of the present invention.
Claims (4)
1. a kind of dyestuff intermediate, it is characterised in that：The intermediate is (3- β-hydroxyethyl sulfone) aniline -4- p-aminobenzene sulfonic acid,
Shown in structural formula such as formula (I)：
2. the preparation method of dyestuff intermediate described in claim 1, it is characterised in that：The method comprises the steps：
1), chlorosulfonation：Chloro- for 2- 5- nitrobenzene-sulfonic acid and chlorosulfonic acid are carried out chlorosulfonation, prepared chlorosulfonation product；
2), reduce：Chlorosulfonation product and sodium sulfite are carried out reduction reaction, prepared reduzate in the basic conditions；
3), hydroxyethylation：By reduzate and reacting ethylene oxide, prepared hydroxyethylation product；
4), it is condensed：Hydroxyethylation product and p-aminobenzene sulfonic acid are condensed, are obtained condensation substance；
5), hydrogenating reduction：Condensation substance is carried out hydrogenating reduction, that is, dyestuff intermediate is obtained.
3. the preparation method of dyestuff intermediate according to claim 1, it is characterised in that：The method comprises the steps：
1), chlorosulfonation：To in dry four-hole bottle, addition chlorosulfonic acid, 15～20 DEG C of water bath heat preservation, are slowly added to the chloro- 5- nitro of 2-
Benzenesulfonic acid；120～135 DEG C of reactions are to slowly warm up to, after being reacted with liquid chromatogram measuring completely, reactant liquor are slowly dropped to
Ice analysis in beaker equipped with mixture of ice and water, temperature remains at -5～0 DEG C；It is filtrated to get filter cake；
2), reduce：Sodium sulfite is added to the water dissolving, pH=7.5～8.0 ice-water bath keeping temperature is adjusted with NaOH (30%)
15～20 DEG C, by step 1) products therefrom is slowly added in system, keeps system pH=7～8.0 with NaOH (30%)；Plus
Complete, continuously stirred 1h, keep pH=7.5～8.0,20～25 DEG C of temperature；NaCl is added to saltout, product is filtrated to get filter after separating out
Cake；
3), hydroxyethylation：By step 2) products therefrom water beating, 55～60 DEG C are warmed up to, are allowed to be completely dissolved；Maintain temperature
For 60 DEG C, in system, ethylene oxide gas are passed through, while using H2SO4(25-30%) pH=6.8～7.2 are adjusted, is continually fed into
18～20h, system solution gradually has solid particle to separate out, and as generates product；After liquid chromatogram measuring reaction completely, cooling
To 40 DEG C；Filter, washing obtains product for hydroxyethylation product；Then product is put in 80 DEG C of baking boxs and dries, obtain ethoxy
Change product dry product；
4), it is condensed：By step 3) product is added in isopropanol and is heated to boiling point, and stop heating, be subsequently adding p-aminophenyl sulphur
Acid, then returns and evaporates until reacting complete；
5), hydrogenating reduction：By step 4) products therefrom put in autoclave, adds catalyst Raney's nickel, sealing autoclave to
Nitrogen is wherein passed through, the air of the inside is displaced, is then passed through hydrogen again, 100 DEG C are heated to, keep being passed through Hydrogen Vapor Pressure
1.2MPa, cooling discharge after reaction completely, refined salt is added, analysis of material is filtrated to get final product (3- β-hydroxyethyl sulfone) aniline -4-
P-aminobenzene sulfonic acid.
4. a kind of using dyestuff obtained in dyestuff intermediate described in claim 1, it is characterised in that：The dyestuff has following (II)
Structure：
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| CN201610715988.9A CN106432010A (en) | 2016-08-24 | 2016-08-24 | Dye intermediate namely (3-beta-hydroxyethylsulfonyl)aniline-4-aminobenzenesulfonic acid and preparation method thereof |
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| CN201610715988.9A CN106432010A (en) | 2016-08-24 | 2016-08-24 | Dye intermediate namely (3-beta-hydroxyethylsulfonyl)aniline-4-aminobenzenesulfonic acid and preparation method thereof |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4629788A (en) * | 1983-10-11 | 1986-12-16 | Bayer Aktiengesellschaft | Triphendioxazine reactive dyestuffs |
| EP0234778A2 (en) * | 1986-02-17 | 1987-09-02 | Sumitomo Chemical Company, Limited | Dioxazine compound having vinylsulfone type fiber reactive group |
| JP2001192581A (en) * | 2000-01-05 | 2001-07-17 | Sumitomo Chem Co Ltd | Unsymmetrical dioxazine compound or its salt, and their application |
| CN102504580A (en) * | 2011-09-29 | 2012-06-20 | 天津德凯化工股份有限公司 | Azo-series red reactive dye and preparation method thereof |
| CN104387302A (en) * | 2014-09-26 | 2015-03-04 | 天津德凯化工股份有限公司 | Dye intermediate and preparation method thereof |
| CN104387794A (en) * | 2014-09-26 | 2015-03-04 | 天津德凯化工股份有限公司 | Blue reactive dye and preparation method thereof |
-
2016
- 2016-08-24 CN CN201610715988.9A patent/CN106432010A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4629788A (en) * | 1983-10-11 | 1986-12-16 | Bayer Aktiengesellschaft | Triphendioxazine reactive dyestuffs |
| EP0234778A2 (en) * | 1986-02-17 | 1987-09-02 | Sumitomo Chemical Company, Limited | Dioxazine compound having vinylsulfone type fiber reactive group |
| JP2001192581A (en) * | 2000-01-05 | 2001-07-17 | Sumitomo Chem Co Ltd | Unsymmetrical dioxazine compound or its salt, and their application |
| CN102504580A (en) * | 2011-09-29 | 2012-06-20 | 天津德凯化工股份有限公司 | Azo-series red reactive dye and preparation method thereof |
| CN104387302A (en) * | 2014-09-26 | 2015-03-04 | 天津德凯化工股份有限公司 | Dye intermediate and preparation method thereof |
| CN104387794A (en) * | 2014-09-26 | 2015-03-04 | 天津德凯化工股份有限公司 | Blue reactive dye and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 赵德丰 等: "活性艳蓝KN-FB的研制", 《精细与专用化学品》 * |
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Application publication date: 20170222 |