CN107501987A - A kind of preparation method of the para-totuidine base anthraquinone of 1 hydroxyl 4 - Google Patents
A kind of preparation method of the para-totuidine base anthraquinone of 1 hydroxyl 4 Download PDFInfo
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- CN107501987A CN107501987A CN201710745426.3A CN201710745426A CN107501987A CN 107501987 A CN107501987 A CN 107501987A CN 201710745426 A CN201710745426 A CN 201710745426A CN 107501987 A CN107501987 A CN 107501987A
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- anthraquinones
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Classifications
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- 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
- C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
- C09B1/50—Amino-hydroxy-anthraquinones; Ethers and esters thereof
- C09B1/51—N-substituted amino-hydroxy anthraquinone
- C09B1/514—N-aryl derivatives
- C09B1/5145—N-aryl derivatives only amino and hydroxy groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/30—Complexes comprising metals of Group III (IIIA or IIIB) as the central metal
- B01J2531/38—Lanthanides other than lanthanum
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The invention provides a kind of preparation method of the para-totuidine base anthraquinone of 1 hydroxyl 4, by Isosorbide-5-Nitrae dihydroxy anthraquinone, para-totuidine, ether solvent, condensation catalyst is put into reactor, and system gradually reacted by heating, after reaction terminates, product is filtered, filter cake is scrubbed, drying, then obtains the para-totuidine base anthraquinone finished product of 1 hydroxyl 4 through process for refining.
Description
Technical field
The present invention relates to the preparation method of dyestuff, especially a kind of preparation method of 1- hydroxyls -4- para-totuidine base anthraquinones.
Background technology
Chinese:1- hydroxyls -4- (para-totuidine base)-anthraquinone, Chinese nickname:Borane reagent;Transparent violet B;Oil Violet 13;
Oil Violet B；English name:1-hydroxy-4- (p-toluidino) anthraquinone, the clever enzymatic reagent as measure boron
It is mainly used in the dope dyeing of polyester fiber, it can also be used to prepare terylene Masterbatch.
CN104341790B is related to a kind of new method for preparing 1- hydroxyl -4- aryl amine anthraquinones, quinizarin and its leuco compound
Mixture, micro- excessive arylamine carry out condensation reaction in containing a kind of water of anion surfactant, react without using boric acid
Or other condensing agents, condensation product obtain the 1- hydroxyl -4- aryl amines that purity is higher than 97.0% through DMF aqueous solution refinement treatments
Anthraquinone, two condensation product contents are less than 2.0% in product, and Isosorbide-5-Nitrae-dihydroxy anthraquinone residual is less than 1.0%.The present invention is by strict
Condensation reaction condition controls, such as the selection of micro- excessive arylamine, anion surfactant so that condensation reaction rests on a contracting
Conjunction stage, two condensation reactions are effectively suppressed, and reduce the generation of double condensation products, improve the purity of product, so that reduce
Later stage refined difficulty.Arylamine is strict controlled in micro- excess, that is, meets reaction, and without recovery；Anion surfactant
Use effectively promote the progress of condensation reaction, reduce cost and reaction difficulty.
The method that CN1407024A provides the 1- amino-4-hydroxy anthraquinos for preparing logical formula (I), wherein, R is fat-based
Or aryl, it is characterised in that in the presence of METHYLPYRROLIDONE, Isosorbide-5-Nitrae-dihydroxy anthraquinone and fatty amine or fragrance
Amine reacts.In an especially preferred embodiment, method of the invention is carried out in the presence of boric acid.Boric acid it is preferred
Dosage is the 0.025-1 molar equivalents of anthraquinone (quinizarin and procrypsis quinizarin total amount), especially 0.025-0.4 molar equivalents.
Of the prior art to make condensation catalyst using boric acid in the prior art, product purity is low, without using boric acid
Or other condensing agents, condensation reaction condition is harsh, and anion surfactant is difficult to remove in the DLF aqueous solution, can bring dirt
The added burden of water process.
The content of the invention
Present invention aims at solve above-mentioned technical problem present in prior art, there is provided a kind of 1- hydroxyl -4- are to first
The preparation method of anilino- anthraquinone.
In order to solve the above-mentioned technical problem, the present invention adopts the following technical scheme that, first be made condensation catalyst, by Isosorbide-5-Nitrae-
Dihydroxy anthraquinone, para-totuidine, dibutyl ethylene glycol ether, condensation catalyst are put into reactor, and system gradually heats up progress
Reaction, through separation, purification, obtain 1- hydroxyl -4- para-totuidine base anthraquinone products.
A kind of preparation method of 1- hydroxyls -4- para-totuidine base anthraquinones, preparation process include：
（1）The preparation of condensation catalyst：By weight, 100 parts of thiourea resins are swollen in 500-1000 part boric acid and soaks 1-
5h, filtering, PH=7 are washed till using deionized water, add the 2-hydroxy-5-sulfobenzoic acid of 1-10 parts, the vinegar of 0.01-0.1 parts
Sour neodymium;5, the 6- diaminostilbenes of 0.01-0.1 parts, 10- Phens, the 2- fluorine isonicotinic acid of 1-5 parts are anti-in 20-50 DEG C of stirring
5-10h is answered, reaction terminates, and filters, and drying, obtains condensation catalyst；
（2）The preparation of 1- hydroxyl -4- para-totuidine base anthraquinones：
By weight, by 100 parts of Isosorbide-5-Nitrae-dihydroxy anthraquinones, 80-150 part para-totuidine, 300-800 part ether solvents, 30-100
Part condensation catalyst is put into reactor, and system gradually is reacted by heating, and after reaction terminates, product is filtered, filter cake warp
Washing, drying, then obtain 1- hydroxyl -4- para-totuidine base anthraquinone finished products through process for refining.
It is one or more of in the preferred tetraethylene glycol dimethyl ether of described ether solvent, diphenyl ether, dibutyl ethylene glycol ether
Combination.
100-150 DEG C of the reaction temperature.
The reaction time 10-20h.
The scrubbed process of filter cake is：Filter cake washs through methanol, then through hot wash.
The process for refining includes rectifying and vacuum distillation.
Described thiourea resin, boric acid, 2-hydroxy-5-sulfobenzoic acid, acetic acid neodymium, 5,6- diaminostilbenes, 10- are adjacent luxuriant and rich with fragrance
Sieve quinoline, 2- fluorine isonicotinic acid, Isosorbide-5-Nitrae-dihydroxy anthraquinone, para-totuidine is commercially available prod.
The present invention is by adopting the above-described technical solution, have the advantages that：
1st, using the condensation catalyst of macromolecular scaffold structure, solid catalyst makes reaction more stable, is not likely to produce temperature runaway, can
To avoid side reaction, the yield of 1- hydroxyl -4- para-totuidine base anthraquinones is improved.
2nd, using solid catalyst, 2-hydroxy-5-sulfobenzoic acid, acetic acid neodymium;5,6- diaminostilbenes, 10- Phens
, the complicated complex compound of 2- fluorine isonicotinic acid generation, make the active group of solid catalyst more firm, while avoid liquid catalyst
Agent enters in product the shortcomings that being not readily separated, and reduces the quantum of output of the three wastes.
Embodiment
Following instance is only to further illustrate the present invention, is not limitation the scope of protection of the invention.
Embodiment 1：
A kind of preparation method of 1- hydroxyls -4- para-totuidine base anthraquinones, it is characterised in that preparation process includes：
（1）The preparation of condensation catalyst：By weight, 100 parts of thiourea resins are swollen in 700 parts of boric acid and soak 3h, filtered,
PH=7 are washed till using deionized water, add 3 parts of 2-hydroxy-5-sulfobenzoic acid, 0.04 part of acetic acid neodymium, the 5 of 0.03 part,
6- diaminostilbenes, 10- Phens, 2 parts of 2- fluorine isonicotinic acid, in 30 DEG C of stirring reaction 7h, reaction terminates, and filters, drying,
Obtain condensation catalyst；
（2）The preparation of 1- hydroxyl -4- para-totuidine base anthraquinones：
By weight, by 100 parts of Isosorbide-5-Nitrae-dihydroxy anthraquinones, 90 parts of para-totuidine, 500 parts of dibutyl ethylene glycol ethers, 70 parts of condensations
Catalyst is put into reactor, and system gradually reacted by heating, 110 DEG C of the reaction temperature, the reaction time 14h,
After reaction terminates, product is filtered, and filter cake is scrubbed, drying, then obtains 1- hydroxyl -4- para-totuidine base anthraquinones through process for refining
Finished product, products obtained therefrom numbering is L-1.
Embodiment 2：
A kind of preparation method of 1- hydroxyls -4- para-totuidine base anthraquinones, it is characterised in that preparation process includes：
（1）The preparation of condensation catalyst：By weight, 100 parts of thiourea resins are swollen in 500 parts of boric acid and soak 1h, filtered,
PH=7 are washed till using deionized water, add 1 part of 2-hydroxy-5-sulfobenzoic acid, 0.01 part of acetic acid neodymium;The 5 of 0.01 part,
6- diaminostilbenes, 10- Phens, 1 part of 2- fluorine isonicotinic acid, in 20 DEG C of stirring reaction 10h, reaction terminates, and filters, drying,
Obtain condensation catalyst；
（2）The preparation of 1- hydroxyl -4- para-totuidine base anthraquinones：
By weight, by 100 parts of Isosorbide-5-Nitrae-dihydroxy anthraquinones, 80 parts of para-totuidine, 300 parts of tetraethylene glycol dimethyl ethers, the contracting of 30-100 parts
Close catalyst to put into reactor, system gradually reacted by heating, 100 DEG C of reaction temperature, reaction time 20h.Reaction knot
Shu Hou, product is filtered, and filter cake is scrubbed, drying, then obtains 1- hydroxyl -4- para-totuidine base anthraquinone finished products through process for refining,
Products obtained therefrom numbering is L-2.
Embodiment 3：
A kind of preparation method of 1- hydroxyls -4- para-totuidine base anthraquinones, it is characterised in that preparation process includes：
（1）The preparation of condensation catalyst：By weight, 100 parts of thiourea resins are swollen in 1000 parts of boric acid and soaks 5h, mistake
Filter, PH=7 are washed till using deionized water, add 10 parts of 2-hydroxy-5-sulfobenzoic acid, 0.1 part of acetic acid neodymium;0.1 part
5,6- diaminostilbenes, 10- Phens, 5 parts of 2- fluorine isonicotinic acid, in 50 DEG C of stirring reaction 5h, reaction terminates, and filters, and dries
It is dry, obtain condensation catalyst；
（2）The preparation of 1- hydroxyl -4- para-totuidine base anthraquinones：
By weight, by 100 parts of Isosorbide-5-Nitrae-dihydroxy anthraquinones, 150 parts of para-totuidine, 800 parts of diphenyl ether, 100 parts of condensation catalysts
Put into reactor, system gradually reacted by heating, 150 DEG C of the reaction temperature, the reaction time 10h, reaction knot
Shu Hou, product is filtered, and filter cake is scrubbed, drying, then obtains 1- hydroxyl -4- para-totuidine base anthraquinone finished products through process for refining,
Products obtained therefrom numbering is L-3.
Comparative example 1：2-hydroxy-5-sulfobenzoic acid is added without, the other the same as in Example 1.Products obtained therefrom numbering is L-4.
Comparative example 2：Acetic acid neodymium is added without, the other the same as in Example 1.Products obtained therefrom numbering is L-5.
Comparative example 3：5,6- diaminostilbenes, 10- Phens are added without, the other the same as in Example 1.Products obtained therefrom numbering is L-
6。
Comparative example 4：2- fluorine isonicotinic acid is added without, the other the same as in Example 1.Products obtained therefrom numbering is L-7.
Comparative example 5：Step 1 is cancelled, and condensation catalyst uses boric acid, the other the same as in Example 1.Products obtained therefrom numbering is L-8.
Embodiment 4
Product L-1~the L-3 and comparative example L-4~L-8 that the embodiment of the present invention obtains, through gas chromatographic detection finished product content,
The conversion ratio of Isosorbide-5-Nitrae-dihydroxy anthraquinone is obtained, as shown in table 1：
The comparison for the test specimen that the different process of table 1 is made
The specific embodiment of the present invention is these are only, but the technical characteristic of the present invention is not limited thereto.
Claims (8)
1. a kind of preparation method of 1- hydroxyls -4- para-totuidine base anthraquinones, it is characterised in that preparation process includes：
By weight, by 100 parts of Isosorbide-5-Nitrae-dihydroxy anthraquinones, 80-150 part para-totuidine, 300-800 part ether solvents, 30-100
Part condensation catalyst is put into reactor, and system gradually is reacted by heating, and after reaction terminates, product is filtered, filter cake warp
Washing, drying, then obtain 1- hydroxyl -4- para-totuidine base anthraquinone finished products through process for refining.
A kind of 2. preparation method of 1- hydroxyls -4- para-totuidine base anthraquinones according to claim 1, it is characterised in that：Institute
The preparation method for stating condensation catalyst comprises the following steps：
By weight, 100 parts of thiourea resins are swollen in 500-1000 part boric acid and soaks 1-5h, filtered, use deionized water
PH=7 are washed till, add the 2-hydroxy-5-sulfobenzoic acid of 1-10 parts, the acetic acid neodymium of 0.01-0.1 parts;The 5,6- of 0.01-0.1 parts
Diaminostilbene, 10- Phens, the 2- fluorine isonicotinic acid of 1-5 parts, in 20-50 DEG C of stirring reaction 5-10h, reaction terminates, filtering,
Drying, obtains condensation catalyst.
A kind of 3. preparation method of 1- hydroxyls -4- para-totuidine base anthraquinones according to claim 1, it is characterised in that：Institute
The ether solvent stated includes one or more of combinations in tetraethylene glycol dimethyl ether, diphenyl ether, dibutyl ethylene glycol ether.
A kind of 4. preparation method of 1- hydroxyls -4- para-totuidine base anthraquinones according to claim 1, it is characterised in that：Institute
State 100-150 DEG C of reaction temperature.
A kind of 5. preparation method of 1- hydroxyls -4- para-totuidine base anthraquinones according to claim 1, it is characterised in that：Institute
State reaction time 10-20h.
A kind of 6. preparation method of 1- hydroxyls -4- para-totuidine base anthraquinones according to claim 1, it is characterised in that：Institute
Stating the scrubbed process of filter cake is：Filter cake washs through methanol, then through hot wash.
A kind of 7. preparation method of 1- hydroxyls -4- para-totuidine base anthraquinones according to claim 1, it is characterised in that：Institute
Stating process for refining includes rectifying and vacuum distillation.
A kind of 8. preparation method of 1- hydroxyls -4- para-totuidine base anthraquinones according to claim 1, it is characterised in that：Contracting
Conjunction catalyst is boric acid.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108017935A (en) * | 2017-12-26 | 2018-05-11 | 江苏道博化工有限公司 | Blue mixed dye and preparation method thereof |
| CN110713732A (en) * | 2019-10-18 | 2020-01-21 | 湖北彩德新材料科技有限公司 | Solvent pigment 5B green and preparation method thereof |
| CN112322067A (en) * | 2020-11-04 | 2021-02-05 | 罗子木 | Plastic colorant purple B and preparation method thereof |
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|---|---|---|---|---|
| GB2013701A (en) * | 1978-02-03 | 1979-08-15 | Ici Ltd | An Improved Process for the Preparation of Arylamino Derivatives of Anthraquinone |
| CN1407024A (en) * | 2001-08-16 | 2003-04-02 | 拜尔公司 | Preparation of 1-amino-4-hydroxy anthraquino |
| CN101195581A (en) * | 2006-12-07 | 2008-06-11 | 朗盛德国有限责任公司 | Preparation of substituted aminoanthraquinones |
| CN101786017A (en) * | 2010-02-05 | 2010-07-28 | 绍兴文理学院 | Preparation method of solid-acid catalyst |
-
2017
- 2017-08-26 CN CN201710745426.3A patent/CN107501987A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2013701A (en) * | 1978-02-03 | 1979-08-15 | Ici Ltd | An Improved Process for the Preparation of Arylamino Derivatives of Anthraquinone |
| CN1407024A (en) * | 2001-08-16 | 2003-04-02 | 拜尔公司 | Preparation of 1-amino-4-hydroxy anthraquino |
| CN101195581A (en) * | 2006-12-07 | 2008-06-11 | 朗盛德国有限责任公司 | Preparation of substituted aminoanthraquinones |
| CN101786017A (en) * | 2010-02-05 | 2010-07-28 | 绍兴文理学院 | Preparation method of solid-acid catalyst |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108017935A (en) * | 2017-12-26 | 2018-05-11 | 江苏道博化工有限公司 | Blue mixed dye and preparation method thereof |
| CN108017935B (en) * | 2017-12-26 | 2019-04-05 | 江苏道博化工有限公司 | Blue mixed dye and preparation method thereof |
| CN110713732A (en) * | 2019-10-18 | 2020-01-21 | 湖北彩德新材料科技有限公司 | Solvent pigment 5B green and preparation method thereof |
| CN112322067A (en) * | 2020-11-04 | 2021-02-05 | 罗子木 | Plastic colorant purple B and preparation method thereof |
| CN112322067B (en) * | 2020-11-04 | 2022-06-10 | 罗子木 | Plastic colorant purple B and preparation method thereof |
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Inventor after: Yang Weitong Inventor after: Wang Yonghua Inventor before: Guo Zhiyi Inventor before: Yang Weitong Inventor before: Tu Renhua Inventor before: Yan Fuchi Inventor before: Zhao Hanan Inventor before: Gu Canbo |
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Inventor after: Yang Weitong Inventor after: Wang Yonghua Inventor before: Guo Zhiyi Inventor before: Yang Weitong Inventor before: Tu Renhua Inventor before: Yan Fuchi Inventor before: Zhao Hanan Inventor before: Gu Canbo |
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Application publication date: 20171222 |