CN104326947B

CN104326947B - The preparation method of reactive brilliant bule K-GR intermediate

Info

Publication number: CN104326947B
Application number: CN201410521270.7A
Authority: CN
Inventors: 吕荣文; 高崑玉
Original assignee: Dalian University of Technology
Current assignee: Dalian University of Technology
Priority date: 2013-10-14
Filing date: 2014-09-30
Publication date: 2016-08-24
Anticipated expiration: 2034-09-30
Also published as: CN104326947A

Abstract

The present invention provides the preparation method of a kind of reactive brilliant bule K GR intermediate, comprise the following steps: use and include the copper complex formazan catalyst system of monovalence, catalysis bromamine acid and 2,4 diamino benzene sulfonic acids or 2,4 diamino benzene sulfonic acid sodium mediated condensated reactions, obtain reactive brilliant bule K GR intermediate (1 amino 4 ((4 amino 3 sulfonic group phenyl) amino) anthraquinone 2 sodium sulfonate).The preparation method of reactive brilliant bule K GR intermediate of the present invention can effectively reduce the usage amount of Cu-lyt. and copper powder, reduces the content of heavy metal in dye product, reduces the content of beary metal in waste water, reduces environmental pollution and reduces production cost；Also avoid the generation of bromamine acid hydrolysising by-product (purple secondary), greatly reduce the generation of debrominate by-product, hence it is evident that reduce the generation of double contracting thing, improve condensation reaction and dyestuff yield, reduce containing acid and the discharge capacity of the deep waste water of colourity.

Description

The preparation method of reactive brilliant bule K-GR intermediate

Technical field

The present invention relates to reactive dye technology, particularly relate to the preparation method of a kind of reactive brilliant bule K-GR intermediate.

Background technology

Reactive brilliant bule K-GR intermediate (1-amino-4-((4-amino-3-sulfonic group phenyl) amino)-anthraquinone-2-sulfonic acid Sodium) it is acid stain, also it is important dyestuff intermediate (blue base) simultaneously, mainly for the production of reactive dye, as gorgeous in activity Blue K-GR (C.I. reactive blue 2), C.I. reactive blue 4, C.I. reactive blue 5 etc., these reactive dye alkaline resistance properties are excellent, have excellence Sun-proof and fastness to soaping, and have good dissolubility.

Reactive brilliant bule K-GR intermediate is for having compounds of formula I:

It is commercially used for the condensation of bromamine acid and the 2,4-diamino benzene sulfonic acid preparing reactive brilliant bule K-GR intermediate at present Course of reaction is as follows:

In said process, bromamine acid and 2, the condensation reaction of 4-diamino benzene sulfonic acid is at substantial amounts of Cu-lyt .-copper powder In the presence of carry out, this reaction exists bromamine acid hydrolysis (purple secondary), debrominate side reaction, and bromamine acid convert not exclusively.Reaction In product mixtures, condensation substance content is 55.74%, containing double contracting things 5%, bromamine acid 2.66% and purple pair 6.19% etc., causes useless Colority of water and COD value are high, and content of beary metal is up to 45mg/L.

This reaction is the aryl amination reaction of bromamine acid, in addition to using Cu-lyt .-copper powder catalyst system and catalyzing, the most once has document report Road uses CuSO₄、CuSO₄-FeSO₄And CuSO₄-SnCl₂For catalyst system and catalyzing, wherein CuSO₄、CuSO₄-FeSO₄Urging of catalyst system and catalyzing Change effect is not as good as Cu-lyt. catalyst system and catalyzing, and CuSO₄-SnCl₂Although the catalytic effect of catalyst system and catalyzing is better than Cu-lyt. catalysis System, but the separation of tin-oxide is difficult, and add heavy metal pollution.

Summary of the invention

It is an object of the invention to, the preparation method bromamine acid for existing reactive brilliant bule K-GR intermediate cannot convert completely Entirely, by-product is many and problem high for COD in waste water, proposes the preparation method of a kind of reactive brilliant bule K-GR intermediate, to realize bromine Propylhomoserin nearly 100% converts, without bromamine acid hydrolysis (purple secondary) and debrominate by-product, the generation significantly reducing pair contracting thing, make condensation produce Thing yield significantly improves, and reduces containing acid and the discharge capacity of the deep waste water of colourity；The most also can reduce the usage amount of catalyst, not use Copper powder, reduces the content of heavy metal in condensed products, reduces the content of beary metal in waste water, reduce environmental pollution, reduce and produce Cost.

For achieving the above object, the technical solution used in the present invention is: the preparation side of a kind of reactive brilliant bule K-GR intermediate Method, described reactive brilliant bule K-GR intermediate is for having compounds of formula I:

Wherein M is H, NH₄Or alkali metal, described alkali metal is Li, Na or K, the system of described reactive brilliant bule K-GR intermediate Preparation Method comprises the following steps: uses and includes the copper complex formazan catalyst system of monovalence, in a solvent catalysis bromamine acid and 2, 4-diamino benzene sulfonic acid or 2,4-diamino benzene sulfonic acid sodium mediated condensated reaction, reaction terminates the gorgeous blue K-GR of rear isolated Product Activity Intermediate.

Bromamine acid therein is the compound with formula II, and wherein M is H, NH₄Or alkali metal, described alkali metal be Li, Na or K:

Described 2,4-diamino benzene sulfonic acid is the compound with general formula III, and wherein M is H, NH₄Or alkali metal, described alkali Metal is Li, Na or K:

Further, described monovalence copper complex is:

With water soluble bivalent nantokite for copper source, the method for reducing agent reduction or electrochemical reduction is used to be reduced to by cupric Monovalence copper, wherein said reducing agent is water miscible organic or inorganic reducing agent；Add part and monovalence copper complexation formation Monovalence copper complex；

Or with water soluble bivalent nantokite for copper source, under conditions of part exists, cupric is reduced to monovalence copper, formed Cupprous complex；

Or with monovalence copper for copper source, directly monovalence copper is acted in the solution with organic ligand, form monovalence copper complex.

Further, described cupric salt is: CuBr₂、CuCl₂、Cu(NO₃)₂、CuSO₄With Cu (CH₃COO)₂In one Or multiple, described cuprous salt is one or more in CuCl, CuBr and CuI.

Further, described part is:

In one or more.

The title of above-mentioned part is respectively as follows: 4-((pyridine-2-base) methyl-imino) 2 pentanone, 1,4,7,10-tetra-nitrogen ten Dioxane-1,3-diene, 1,2,3,4,5,6,7,8,9,10-octahydro phendioxin, 4,7,10-teteaazacyclododecane, 3,4,5,6,7, 8,9,10-octahydro benzo-2,5,8,11-tetraazacyclododecane tetradecene, 2,3,4,5,6,7,8,9-octahydro phendioxin, 10,4,7-bis- Sulfur diazacyclo dodecane, 3,4,5,6,7,8-hexahydro benzo-1,4,7,10-teteaazacyclododecane-2,9-diketone, 5,6,8, 10-tetrahydro benzo-4,7,1,10-disulfide dinitrogen triazacyclododecane-2,9-diketone, 2,3-diphenyl-1,4,7,10-four nitrogen ten Two-1,3-diene, 2,2'-(ethane-1,2-two replacement is double (amino subunit) double (methylene)) diphenol, N, N-dimethyl second two Amine, 2-(propyl group-2-methylene) thiosemicarbazides, 2-isopropylamino thiourea, 2-pyridine aldoxime, N-(2-picolyl) hydroxyl Amine, 2-(((2-pyridylmethyl) imino group) methyl) phenol, 2-(((2-pyridylmethyl) amino) methyl) phenol, 4-hydroxyl Base-3-(((2-picolyl) imino group) methyl) benzenesulfonic acid, 4-hydroxyl-3-(((2-picolyl) amino) methyl) benzene sulphur Acid, 2-(2-phenol methylene) thiosemicarbazides, 2-(2-hydroxybenzyl) thiosemicarbazides, 2-((2-(6-picoline)) methylene Base) thiosemicarbazides, 2-((2-(6-picoline)) methyl) thiosemicarbazides, 2-((2-pyridine) methylene) thiosemicarbazides, 2-(pyrrole Pyridine-2-methylene) thiosemicarbazides, 2-benzylideneamino thiourea, 2-benzylamino thiourea, 2-hydroxyl-3-(((2-pyridine radicals first Base) imino group) methyl) benzoic acid, 2-hydroxyl-3-(((2-pyridylmethyl) amino) methyl) benzoic acid, 3-((2-amino sulfur Acute pyogenic infection of nails acyl hydrazono-) methyl)-2 hydroxybenzoic acid, 3-((2-aminothio formohydrazide group) methyl)-2 hydroxybenzoic acid, 4-(((2-pyridylmethyl) imino group) methyl) 1,3-Benzodiazepines, 4-(((2-pyridylmethyl) amino) methyl) 1,3-benzene two Phenol, 2-(2,4-dihydroxy benzenes methylene) thiosemicarbazides, 2-(2,4-dihydroxy benzyl) thiosemicarbazides, 2-(((2-(dimethylamino Base) ethyl) imino group) methyl) phenol, 2-(((2-(dimethylamino) ethyl) amino) methyl) phenol, five ethylene triamines, 2- (((2-mercapto ethyl) imino group) methyl) phenol, 2-(((2-mercapto ethyl) amino) methyl) phenol, 2-(((2-ethoxy) imido Base) methyl) phenol, 2-(((2-ethoxy) amino) methyl) phenol.

Further, the copper ion in copper source is 1:1 to 1:2 with the mol ratio of part.

Further, described reducing agent is: ascorbic acid (Vc), azanol, FeCl₂、SnCl₂、FeSO₄、Na₂SO₃、 Na₂S₂O₃、NO、NaHSO₃, one or more in arabo-ascorbic acid and oxalic acid.Described reducing agent is 1:1 with the mol ratio in copper source To 1:1.2.

Further, described solvent is: one or more in water, ethanol, DMF and DMSO.

Further, the consumption of solvent in the present invention, bromamine acid conversion ratio, hydrolysising by-product (purple secondary) content are had important Impact.When solvent is water, when the consumption of water converts completely with bromamine acid in system 2,4-diamino benzene sulfonic acid or 2,4-diamino The molar concentration of base benzene sulfonic acid sodium salt is that 0.1-0.8M is advisable, and preferred consumption is 0.2-0.8M, under the conditions of preferred water consumption, Generate without hydrolysising by-product；The kind of alkali (acid binding agent) and consumption affect reacting liquid pH value, and the content of debrominate by-product.

Further, described condensation reaction is carried out in the presence of acid binding agent, and described acid binding agent can neutralize condensation reaction and generate HBr, described acid binding agent can the most once add or be dividedly in some parts；Described acid binding agent is: NaHCO₃、KHCO₃、 NH₄HCO₃、Na₂HPO_4、Na₂CO₃、KOH、NaOH、MgO、NaOAc、K₃PO₄、CsCO₃And K₂CO₃In one or more.Keep anti- The pH answering system is 7.2-8.5, when the ph is lower, and the activity of amine (2,4-diamino benzene sulfonic acids or 2,4-diamino benzene sulfonic acid sodium) Reduce；When pH is higher, bromamine acid easily hydrolyzes.

Further, the mole dosage of described acid binding agent is 2-6 times of bromamine acid.

Further, the copper complex formazan mole of described monovalence is the 0.5% to 20% of bromamine acid, preferably 3% to 10%. Described cupprous complex is prepared in situ before being typically reaction.

Further, described monovalence copper complex is supported on carrier, such as pottery or polymer.

Further, described bromamine acid and 2,4-diamino benzene sulfonic acid or 2,4-diamino benzene sulfonic acid sodium mediated condensated reaction anti- The temperature is answered to be: 65 DEG C-100 DEG C, preferably 80 DEG C-90 DEG C.Response time is 10 minutes to 5 hours.The addition sequence of each material is such as Under: bromamine acid, 2,4-diamino benzene sulfonic acid or 2,4-diamino benzene sulfonic acid sodium, acid binding agent disposably add, and catalyst in increments adds Enter；Also can 2,4-diamino benzene sulfonic acid or 2,4-diamino benzene sulfonic acid sodium, acid binding agent once add, and bromamine acid divides with catalyst Criticize, be alternately added.

Further, described bromamine acid and 2,4 diamino benzene sulfonic acids or 2, the molar ratio of 4-diamino benzene sulfonic acid sodium is 1:1.2 to 1:3.

The preparation method of reactive brilliant bule K-GR intermediate of the present invention achieves bromamine acid nearly 100% and converts, without bromamine acid water Solving the content of double contracting things in (purple secondary) and the generation of debrominate by-product, product, less than 3%, makes condensation product yield substantially carry Height, reduces containing acid and the discharge capacity of the deep waste water of colourity；The most also can reduce the usage amount of catalyst, not use copper powder, reduce contracting Close the content of heavy metal in product, reduce the content of beary metal in waste water, reduce environmental pollution, reduce production cost.

The method of the present invention is applicable not only to laboratory preparation on a small scale, and the industrialization being also suitably for chemical plant is given birth on a large scale Produce.Concrete response parameter when industrialization large-scale production can be determined by normal experiment by those skilled in the art.

Accompanying drawing explanation

Fig. 1 is the mass spectrum of reactive brilliant bule K-GR intermediate (I), m/z (-)=488.0 it is [M-H]^-Molecular ion peak, F_W=489.

Detailed description of the invention

Embodiment 1

Weigh 2,8.4 grams of 4-diamino benzene sulfonic acid sodium, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, In the container of condenser and thermometer, under stirring, it is heated to 80 DEG C.Weighing bromamine acid 8.08 grams respectively, 15%mol is (with bromamine acid On the basis of) monovalence copper and Cyclen-1,3-diene (C₈H₁₈N₄) complex solution.By solid Bromamine acid and monovalence copper complex were alternately added in container in 1 hour, kept reaction temperature 80-82 DEG C, the pH of reaction system 9, stirring reaction 3 hours；Liter high reaction temperature is to 85-90 DEG C, and stirring is reacted, and thin layer chromatography and liquid-phase chromatographic analysis are done in sampling, It is reaction end without bromamine acid.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, trace debrominate is had to produce Thing.

Above-mentioned material is cooled to 40 DEG C, slowly regulates pH 2.8-3.0 with hydrochloric acid, stir 30 minutes, filter, reclaim 2, 4-diamino benzene sulfonic acid (filter cake).Filtrate is warmed up to 60 DEG C, adjusts pH < 1,15%-20% by volume to add sodium chloride, stirs, After filter paper point sample clear spot, being cooled to room temperature, filter, filter cake is reactive brilliant bule K-GR intermediate, its mass spectrum such as Fig. 1 institute Show.

Embodiment 2

Weigh 2,4-diamino benzene sulfonic acid 21 grams, sodium carbonate 26.5 grams, 50 milliliters of water, join equipped with agitator, condensation Device, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 20.2 grams respectively, 10%mol is (with bromamine acid as base Accurate) monovalence copper and Cyclen-1,3-diene (C₈H₁₈N₄) complex solution.By solid bromine ammonia Acid and monovalence copper complex were alternately added in container in 2.5 hours, kept reaction temperature 78-82 DEG C, the pH 8-of reaction system 9, stirring reaction 3-5 hour；Keeping reaction temperature 80-90 DEG C, stirring reaction, thin layer chromatography and liquid-phase chromatographic analysis are done in sampling, It is reaction end without bromamine acid.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, trace debrominate is had to produce Thing.

Above-mentioned material cools to 40 DEG C, slowly regulates pH 2.8-3.0 with hydrochloric acid, stirs 30 minutes, filters, and reclaims 2,4- Diamino benzene sulfonic acid.Filtrate is warmed up to 60 DEG C, adjusts pH < 1,15%-20% by volume to add sodium chloride, stirring, filter paper point sample After clear spot, being cooled to room temperature, filter, filter cake is reactive brilliant bule K-GR intermediate.

Embodiment 3

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and Cyclen-1,3-diene (C₈H₁₈N₄) ethanol solution of complex.Will be solid Body bromamine acid and monovalence copper complex were alternately added in container in 1 hour, kept reaction temperature 75-80 DEG C, reaction system PH 8, stirring reaction 3-4 hour；Keeping reaction temperature 85-90 DEG C, stirring reaction, thin layer chromatography is done in sampling and liquid chromatograph is divided Analysis, is reaction end without bromamine acid.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, there is trace debrominate Product.

Embodiment 4

Weigh 2,4-diamino benzene sulfonic acid 21 grams, sodium carbonate 26.5 grams, 50 milliliters of water, join equipped with agitator, condensation Device, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 20.2 grams respectively, 15%mol is (with bromamine acid as base Accurate) monovalence copper and Cyclen-1,3-diene (C₈H₁₈N₄) ethanol solution of complex.By solid Bromamine acid and monovalence copper complex were alternately added in container in 2.5 hours, kept reaction temperature 70-75 DEG C, reaction system PH 7.5-9, stirring reaction 3-5 hour；Keeping reaction temperature 85-90 DEG C, stirring reaction, thin layer chromatography and liquid phase color are done in sampling Analysis of spectrum, is reaction end without bromamine acid.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, there is trace Debrominate product.

Embodiment 5

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 2,3-diphenyl-Cyclen-1,3-diene (C₂₀H₂₄N₄) second of complex Alcoholic solution.Solid bromamine acid and monovalence copper complex are alternately added in container in 1 hour, keep reaction temperature 70-80 DEG C, The pH 7-9 of reaction system, stirring reaction 3-6 hour；Keeping reaction temperature 80-90 DEG C, stirring reaction, thin layer chromatography is done in sampling And liquid-phase chromatographic analysis, it is reaction end without bromamine acid.Without bromamine acid hydrolyzate (purple secondary) and double contracting in reactant liquor mixture Thing, has trace debrominate product.

Embodiment 6

Weigh 2,4-diamino benzene sulfonic acid 21 grams, sodium carbonate 26.5 grams, 50 milliliters of water, join equipped with agitator, condensation Device, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 20.2 grams respectively, 10%mol is (with bromamine acid as base Accurate) monovalence copper and 2,3-diphenyl-Cyclen-1,3-diene (C₂₀H₂₄N₄) ethanol of complex Solution.Solid bromamine acid and monovalence copper complex are alternately added in container in 2.5 hours, keep reaction temperature 75-80 DEG C, The pH 7-8 of reaction system, stirring reaction 3-4 hour；Keeping reaction temperature 80-90 DEG C, stirring reaction, thin layer chromatography is done in sampling And liquid-phase chromatographic analysis, it is reaction end without bromamine acid.Without bromamine acid hydrolyzate (purple secondary) and double contracting in reactant liquor mixture Thing, has trace debrominate product.

Embodiment 7

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 1,10-phenanthroline (C₁₂H₈N₂) ethanol solution of complex.By solid bromamine acid and monovalence copper complex Being alternately added in container in 1 hour, keep reaction temperature 75-80 DEG C, the pH 7.5-8 of reaction system, reaction 3-5 is little in stirring Time；Keeping reaction temperature 80-90 DEG C, stirring reaction, sampling does thin layer chromatography and liquid-phase chromatographic analysis, without bromamine acid for reaction eventually Point.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, there is trace debrominate product.

Embodiment 8

Weigh 2,4-diamino benzene sulfonic acid 21 grams, sodium carbonate 26.5 grams, 50 milliliters of water, join equipped with agitator, condensation Device, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 20.2 grams respectively, 15%mol is (with bromamine acid as base Accurate) monovalence copper and 1,10-phenanthroline (C₁₂H₈N₂) ethanol solution of complex.By solid bromamine acid and monovalence copper complex 1 It is alternately added in hour in container, keeps reaction temperature 75-80 DEG C, the pH 7.5 of reaction system, stirring reaction 3-4 hour； Keeping reaction temperature 85-90 DEG C, stirring reaction, sampling is done thin layer chromatography and liquid-phase chromatographic analysis, is reaction end without bromamine acid. Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, there is trace debrominate product.

Embodiment 9

Weigh 2,4-diamino benzene sulfonic acid 21 grams, sodium carbonate 26.5 grams, 50 milliliters of water, join equipped with agitator, condensation Device, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 20.2 grams respectively, 10%mol is (with bromamine acid as base Accurate) monovalence copper and salicylidene-PA (C₁₃H₁₂N₂O) ethanol solution of complex.By solid bromamine acid and monovalence Copper complex was alternately added in container in 2.5 hours, keeps reaction temperature 75 DEG C, the pH 7.5 of reaction system, stirs reaction 4 Hour；Keeping reaction temperature 80-90 DEG C, stirring reaction, thin layer chromatography and liquid-phase chromatographic analysis are done in sampling, are reaction without bromamine acid Terminal.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, there is trace debrominate product.

Embodiment 10

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 5-sulfonic group salicylidene-PA (C₁₃H₁₂N₂O₄S) complex solution.By solid bromine ammonia Acid and monovalence copper complex were alternately added in container in 1 hour, kept reaction temperature 75 DEG C, the pH 7.5 of reaction system, stirred Mix reaction 5 hours；Keeping reaction temperature 85-90 DEG C, stirring reaction, sampling does thin layer chromatography and liquid-phase chromatographic analysis, without bromine ammonia Acid is reaction end.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, there is trace debrominate product.

Embodiment 11

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and triethanolamine (C₆H₁₅NO₃) complex solution.By solid bromamine acid and monovalence copper complex 1 hour Inside it is alternately added in container, keeps reaction temperature 75 DEG C, the pH 7.5 of reaction system, stirring reaction 4 hours；Keep reaction temperature Spending 80-90 DEG C, stirring reaction, sampling is done thin layer chromatography and liquid-phase chromatographic analysis, is reaction end without bromamine acid.Reactant liquor mixes Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in thing, there is trace debrominate product.

Embodiment 12

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and tetrahydroxyethyl-ethylene diamine (C₁₀H₂₄N₂O₄) complex solution.By solid bromamine acid and monovalence copper complexation Thing was alternately added in container in 1 hour, kept reaction temperature 75 DEG C, the pH 9 of reaction system, stirring reaction 5 hours；Keep Reaction temperature 85-90 DEG C, stirring reaction, sampling is done thin layer chromatography and liquid-phase chromatographic analysis, is reaction end without bromamine acid.Reaction Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in liquid mixture, there is trace debrominate product.

Embodiment 13

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and glyoxime (C₂H₄N₂O₂) ethanol solution of complex.By little to solid bromamine acid and monovalence copper complex 1 Time interior be alternately added in container, keep reaction temperature 80-85 DEG C, the pH 7.5 of reaction system, stirring reaction 3 hours；Keep Reaction temperature 85-90 DEG C, stirring reaction, sampling is done thin layer chromatography and liquid-phase chromatographic analysis, is reaction end without bromamine acid.Reaction Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in liquid mixture, there is trace debrominate product.

Embodiment 14

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and Biformyl (C₂H₂O₂) complex solution.Hand in solid bromamine acid and monovalence copper complex 1 hour For joining in container, keep reaction temperature 80-82 DEG C, the pH 7.5 of reaction system, stirring reaction 5 hours；Keep reaction temperature Spending 85-90 DEG C, stirring reaction, sampling is done thin layer chromatography and liquid-phase chromatographic analysis, is reaction end without bromamine acid.Reactant liquor mixes Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in thing, there is trace debrominate product.

Embodiment 15

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 15%mol (with bromamine acid is Benchmark) monovalence copper and the sub-ethylenediamine (C of N, N'-double (salicylidene)₁₆H₁₆N₂O₂) complex ethanol solution.By solid bromamine acid And monovalence copper complex was alternately added in container in 1 hour, keep reaction temperature 75 DEG C, the pH 7.5 of reaction system, stirring React 5 hours；Keeping reaction temperature 85-90 DEG C, stirring reaction, sampling does thin layer chromatography and liquid-phase chromatographic analysis, without bromamine acid For reaction end.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, there is trace debrominate product.

Embodiment 16

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and mercaptoethanol (C₂H₆The aqueous solution of the complex OS) formed.By solid bromamine acid and monovalence copper complex It is alternately added in container in 1 hour, keeps reaction temperature 80-82 DEG C, the pH 9 of reaction system, stirring reaction 5 hours；Keep Reaction temperature 85-90 DEG C, stirring reaction, sampling is done thin layer chromatography and liquid-phase chromatographic analysis, is reaction end without bromamine acid.Reaction Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in liquid mixture, there is trace debrominate product.

Embodiment 17

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 3,4,5,6,7,8,9,10-octahydro benzo-2,5,8,11-tetraazacyclododecane tetradecene (C₁₄H₂₀N₄) formed The ethanol solution of complex.Solid bromamine acid and monovalence copper complex are alternately added in container in 1 hour, keep reaction Temperature 80-85 DEG C, the pH 7.5 of reaction system, stirring reaction 3 hours；Keep reaction temperature 85-90 DEG C, stirring reaction, sampling Do thin layer chromatography and liquid-phase chromatographic analysis, be reaction end without bromamine acid.Without bromamine acid hydrolyzate (purple in reactant liquor mixture Secondary) and double contracting thing, there is trace debrominate product.

Embodiment 18

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 2,3,4,5,6,7,8,9-octahydro phendioxin, 10,4,7-disulfide dinitrogen triazacyclododecane (C₁₂H₁₈N₂S₂) The ethanol solution of the complex formed.Solid bromamine acid and monovalence copper complex are alternately added in container in 1 hour, keep Reaction temperature 80-85 DEG C, the pH 7.5 of reaction system, stirring reaction 3-4 hour；Keeping reaction temperature 80-90 DEG C, stirring is anti- Should, thin layer chromatography and liquid-phase chromatographic analysis are done in sampling, are reaction end without bromamine acid.Reactant liquor mixture hydrolyzes without bromamine acid Product (purple secondary) and double contracting thing, have trace debrominate product.

Embodiment 19

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 12%mol (with bromamine acid is Benchmark) monovalence copper and 1,2,3,4,5,6,7,8,9,10-octahydro phendioxin, 4,7,10-teteaazacyclododecane (C₁₂H₂₀N₄) shape The ethanol solution of the complex become.Solid bromamine acid and monovalence copper complex are alternately added in container in 1 hour, keep anti- Answer temperature 80-85 DEG C, the pH 8.5 of reaction system, stirring reaction 3-4 hour；Reaction temperature 80-90 DEG C, stirring is kept to react, Thin layer chromatography and liquid-phase chromatographic analysis are done in sampling, are reaction end without bromamine acid.Reactant liquor mixture produces without bromamine acid hydrolysis Thing (purple secondary) and double contracting thing, have trace debrominate product.

Embodiment 20

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 5,6,8,10-tetrahydro benzo-4,7,1,10-disulfide dinitrogen triazacyclododecane-2,9-diketone (C₁₂H₁₄N₄O₂S₂) aqueous solution of complex that formed.Solid bromamine acid and monovalence copper complex are alternately added in 1 hour In container, keep reaction temperature 80-85 DEG C, the pH 8.5 of reaction system, stirring reaction 3 hours；Keep reaction temperature 85-90 DEG C, stirring reaction, sampling is done thin layer chromatography and liquid-phase chromatographic analysis, is reaction end without bromamine acid.Nothing in reactant liquor mixture Bromamine acid hydrolyzate (purple secondary) and double contracting thing, have trace debrominate product.

Embodiment 21

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and N, N-dimethyl-ethylenediamine (C₂H₁₂N₂) ethanol solution of complex that formed.By solid bromamine acid and Monovalence copper complex was alternately added in container in 1 hour, holding reaction temperature 75-80 DEG C, the pH 7.5-8.5 of reaction system, Stirring reaction 3-5 hour；Keeping reaction temperature 80-90 DEG C, stirring reaction, thin layer chromatography and liquid-phase chromatographic analysis, nothing are done in sampling Bromamine acid is reaction end.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, there is trace debrominate product.

Embodiment 22

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 3,4,5,6,7,8-hexahydro benzo-1,4,7,10-teteaazacyclododecane-2,9-diketone (C₁₂H₁₆N₄O₂) Complex ethanol solution.Solid bromamine acid and monovalence copper complex are alternately added in container in 1 hour, keep reaction temperature 80-82 DEG C, the pH 9 of reaction system, stirring reaction 3 hours；Keeping reaction temperature 85-90 DEG C, stirring reaction, thin layer is done in sampling Chromatograph and liquid-phase chromatographic analysis, be reaction end without bromamine acid.In reactant liquor mixture without bromamine acid hydrolyzate (purple secondary) and Double contracting things, have trace debrominate product.

Embodiment 21

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 2-(propyl group-2-methylene) thiosemicarbazides (C₄H₉N₃S) complex ethanol solution.By solid bromamine acid and Monovalence copper complex was alternately added in container in 1 hour, kept reaction temperature 75-80 DEG C, the pH 8-9 of reaction system, stirring React 3-5 hour；Keeping reaction temperature 80-90 DEG C, stirring reaction, sampling does thin layer chromatography and liquid-phase chromatographic analysis, without bromine ammonia Acid is reaction end.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, there is trace debrominate product.

Embodiment 24

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 2-isopropylamino thiourea (C₄H₁₁N₃S) complex ethanol solution.By solid bromamine acid and monovalence copper network Compound was alternately added in container in 1 hour, kept reaction temperature 70-75 DEG C, the pH 7.5-9 of reaction system, stirring reaction 3- 5 hours；Keeping reaction temperature 85-90 DEG C, stirring reaction, sampling is done thin layer chromatography and liquid-phase chromatographic analysis, is anti-without bromamine acid Answer terminal.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, there is trace debrominate product.

Embodiment 25

2,4-diamino benzene sulfonic acids 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, condenser, In the container of thermometer, under stirring, it is heated to 80 DEG C.Weigh bromamine acid 8.08 grams, 10%mol (on the basis of bromamine acid) respectively Monovalence copper and 2-pyridine aldoxime (C₆H₆N₂O) complex ethanol solution.By in solid bromamine acid and monovalence copper complex 1 hour It is alternately added in container, keeps reaction temperature 70-80 DEG C, the pH 7.5-8.5 of reaction system, stirring reaction 3-6 hour；Protect Holding reaction temperature 80-90 DEG C, stirring reaction, sampling is done thin layer chromatography and liquid-phase chromatographic analysis, is reaction end without bromamine acid.Instead Answer in liquid mixture without bromamine acid hydrolyzate (purple secondary) and double contracting thing, have trace debrominate product.

Embodiment 26

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and N-(2-picolyl) hydroxylamine (C₆H₈N₂O) complex ethanol solution.By solid bromamine acid and monovalence Copper complex was alternately added in container in 1 hour, kept reaction temperature 75-80 DEG C, the pH 7-8 of reaction system, stirring reaction 3-6 hour；Keeping reaction temperature 80-90 DEG C, stirring reaction, sampling is done thin layer chromatography and liquid-phase chromatographic analysis, without bromamine acid is Reaction end.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, there is trace debrominate product.

Embodiment 27

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and triethanolamine (C₆H₁₅NO₃) complex solution.By solid bromamine acid and monovalence copper complex 1 hour Inside it is alternately added in container, keeps reaction temperature 75-80 DEG C, the pH 7.5-8 of reaction system, stirring reaction 3-6 hour；Protect Holding reaction temperature 85-90 DEG C, stirring reaction, sampling is done thin layer chromatography and liquid-phase chromatographic analysis, is reaction end without bromamine acid.Instead Answer in liquid mixture without bromamine acid hydrolyzate (purple secondary) and double contracting thing, have trace debrominate product.

Embodiment 28

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 2-(((2-pyridylmethyl) amino) methyl) phenol (C₁₃H₁₄N₂O) complex solution.By solid bromine Propylhomoserin and monovalence copper complex were alternately added in container in 1 hour, kept reaction temperature 75-80 DEG C, the pH of reaction system 7.5, stirring reaction 4 hours；Keeping reaction temperature 80-90 DEG C, stirring reaction, thin layer chromatography and liquid-phase chromatographic analysis are done in sampling, It is reaction end without bromamine acid.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, trace debrominate is had to produce Thing.

Embodiment 29

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 4-hydroxyl-3-(((2-picolyl) amino) methyl) benzenesulfonic acid (C₁₃H₁₄N₂O₄S) complex ethanol is molten Liquid.Solid bromamine acid and monovalence copper complex are alternately added in container in 1 hour, keep reaction temperature 75 DEG C, reactant The pH 7.5 of system, stirring reaction 4 hours；Keeping reaction temperature 85-90 DEG C, stirring reaction, thin layer chromatography and liquid phase color are done in sampling Analysis of spectrum, is reaction end without bromamine acid.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, there is trace Debrominate product.

Embodiment 30

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 2-(2-phenol methylene) thiosemicarbazides (C₈H₈N₃OS) complex DMSO solution.By solid bromamine acid And monovalence copper complex was alternately added in container in 1 hour, keep reaction temperature 75 DEG C, the pH 7.5 of reaction system, stirring React 5 hours；Keeping reaction temperature 80-90 DEG C, stirring reaction, sampling does thin layer chromatography and liquid-phase chromatographic analysis, without bromamine acid For reaction end.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, there is trace debrominate product.

Embodiment 31

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 2-(2-hydroxybenzyl) thiosemicarbazides (C₈H₁₀N₃OS) complex DMSO solution.By solid bromamine acid and Monovalence copper complex was alternately added in container in 1 hour, kept reaction temperature 75 DEG C, the pH 7.5 of reaction system, and stirring is anti- Answer 4 hours；Keeping reaction temperature 85-90 DEG C, stirring reaction, sampling is done thin layer chromatography and liquid-phase chromatographic analysis, without bromamine acid is Reaction end.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, there is trace debrominate product.

Embodiment 32

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 2-((2-(6-picoline)) methylene) thiosemicarbazides (C₈H₁₀N₄S) complex DMSO solution.Will be solid Body bromamine acid and monovalence copper complex were alternately added in container in 1 hour, kept reaction temperature 80 DEG C, the pH of reaction system 9, stirring reaction 3 hours；Keeping reaction temperature 85-90 DEG C, stirring reaction, thin layer chromatography and liquid-phase chromatographic analysis, nothing are done in sampling Bromamine acid is reaction end.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, there is trace debrominate product.

Embodiment 33

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 2-((2-(6-picoline)) methyl) thiosemicarbazides (C₈H₁₂N₄S) complex DMSO solution.By solid Bromamine acid and monovalence copper complex were alternately added in container in 1 hour, kept reaction temperature 80-85 DEG C, reaction system PH7.5, stirring reaction 3 hours；Keeping reaction temperature 85-90 DEG C, stirring reaction, thin layer chromatography is done in sampling and liquid chromatograph is divided Analysis, is reaction end without bromamine acid.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, there is trace debrominate Product.

Embodiment 34

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 2-((2-pyridine) methylene) thiosemicarbazides (C₇H₈N₄S) complex DMSO solution.By solid bromamine acid And monovalence copper complex was alternately added in container in 1 hour, keeps reaction temperature 80-82 DEG C, the pH 7.5 of reaction system, stir Mix reaction 5 hours；Keeping reaction temperature 85-90 DEG C, stirring reaction, sampling does thin layer chromatography and liquid-phase chromatographic analysis, without bromine ammonia Acid is reaction end.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, there is trace debrominate product.

Embodiment 35

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 50 milliliters of water, join equipped with silver reference electricity Pole, platinum to electrode, platinum working electrode, condenser flask in, be heated to 80 DEG C under stirring.Weigh bromamine acid 8.08 grams respectively, The monovalence copper of 10%mol (on the basis of bromamine acid) and 2-(((2-pyridylmethyl) amino) methyl) phenol (C₁₃H₁₄N₂O) network Compound aqueous solution.Solid bromamine acid and monovalence copper complex are joined in container.Energising, 0.56 and 0.88V, 60- 200mV.Keep reaction temperature 80-82 DEG C, the pH 9 of reaction system, stirring reaction 3 hours；Keep reaction temperature 85-90 DEG C, stir Mixing reaction, sampling is done thin layer chromatography and liquid-phase chromatographic analysis, is reaction end without bromamine acid.Without bromamine acid in reactant liquor mixture Hydrolyzate (purple secondary) and double contracting thing, have trace debrominate product.

Embodiment 36

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 50 milliliters of water, join equipped with silver reference electricity Pole, platinum to electrode, platinum working electrode, condenser flask in, be heated to 80 DEG C under stirring.Weigh bromamine acid 8.08 grams respectively, The monovalence copper of 10%mol (on the basis of bromamine acid) and pentamethyl-diethylenetriamine (C₉H₂₃N₃) complex solution.By solid Bromamine acid and monovalence copper complex join in container.Energising, 0.56 and 0.88V, 60-200mV.Keep reaction temperature 80-82 DEG C, the pH 9 of reaction system, stirring reaction 3 hours；Keeping reaction temperature 85-90 DEG C, stirring reaction, thin layer is done in sampling Chromatograph and liquid-phase chromatographic analysis, be reaction end without bromamine acid.In reactant liquor mixture without bromamine acid hydrolyzate (purple secondary) and Double contracting things, have trace debrominate product.

Embodiment 37

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and pentamethyl-diethylenetriamine (C₉H₂₃N₃) complex ethanol solution.By solid bromamine acid and monovalence copper network Compound was alternately added in container in 1 hour, kept reaction temperature 80-85 DEG C, the pH 7.5 of reaction system, and stirring reaction 3 is little Time；Keeping reaction temperature 85-90 DEG C, stirring reaction, sampling does thin layer chromatography and liquid-phase chromatographic analysis, without bromamine acid for reaction eventually Point.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, there is trace debrominate product.

Embodiment 38

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 2-(((2-pyridylmethyl) amino) methyl) phenol (C₁₃H₁₄N₂O) complex solution.By solid bromine Propylhomoserin and monovalence copper complex were alternately added in container in 1 hour, kept reaction temperature 80-85 DEG C, the pH of reaction system 7.5, stirring reaction 3-4 hour；Keeping reaction temperature 80-90 DEG C, stirring reaction, thin layer chromatography is done in sampling and liquid chromatograph is divided Analysis, is reaction end without bromamine acid.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, there is trace debrominate Product.

Embodiment 39

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 2-((2-pyridine) methyl) thiosemicarbazides (C₇H₁₀N₄S) complex DMSO solution.By solid bromamine acid and Monovalence copper complex was alternately added in container in 1 hour, kept reaction temperature 80 DEG C, the pH 8.5 of reaction system, and stirring is anti- Answer 3-4 hour；Keeping reaction temperature 80-90 DEG C, stirring reaction, sampling does thin layer chromatography and liquid-phase chromatographic analysis, without bromamine acid For reaction end.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, there is trace debrominate product.

Embodiment 40

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 2-benzylideneamino thiourea (C₈H₉N₃S) complex DMSO solution.By solid bromamine acid and monovalence copper Complex was alternately added in container in 1 hour, keeps reaction temperature 80-85 DEG C, the pH 8.5 of reaction system, stirs reaction 3 Hour；Keeping reaction temperature 85-90 DEG C, stirring reaction, thin layer chromatography and liquid-phase chromatographic analysis are done in sampling, are reaction without bromamine acid Terminal.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, there is trace debrominate product.

Embodiment 41

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 2-benzylamino thiourea (C₈H₁₁N₃S) complex DMSO solution.By solid bromamine acid and monovalence copper complexation Thing was alternately added in container in 1 hour, kept reaction temperature 75-80 DEG C, the pH 7.5-8.5 of reaction system, stirring reaction 3- 5 hours；Keeping reaction temperature 80-90 DEG C, stirring reaction, sampling is done thin layer chromatography and liquid-phase chromatographic analysis, is anti-without bromamine acid Answer terminal.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, there is trace debrominate product.

Embodiment 42

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 2-hydroxyl-3-(((2-pyridylmethyl) imino group) methyl) benzoic acid (C₁₄H₁₂N₂O₃) complex second Alcoholic solution.Solid bromamine acid and monovalence copper complex are alternately added in container in 1 hour, keep reaction temperature 75-80 DEG C, The pH 7.5 of reaction system, stirring reaction 3-5 hour；Keeping reaction temperature 85-90 DEG C, stirring reaction, thin layer chromatography is done in sampling And liquid-phase chromatographic analysis, it is reaction end without bromamine acid.Without bromamine acid hydrolyzate (purple secondary) and double contracting in reactant liquor mixture Thing, has trace debrominate product.

Embodiment 43

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 2-hydroxyl-3-(((2-pyridylmethyl) amino) methyl) benzoic acid (C₁₄H₁₄N₂O₃) complex ethanol Solution.Solid bromamine acid and monovalence copper complex are alternately added in container in 1 hour, keep reaction temperature 80-85 DEG C, instead Answer the pH 7-7.5 of system, stirring reaction 3-6 hour；Keeping reaction temperature 85-90 DEG C, stirring reaction, thin layer chromatography is done in sampling And liquid-phase chromatographic analysis, it is reaction end without bromamine acid.Without bromamine acid hydrolyzate (purple secondary) and double contracting in reactant liquor mixture Thing, has trace debrominate product.

Embodiment 44

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 3-((2-aminothio formyl hydrazono-) methyl)-2 hydroxybenzoic acid (C₉H₉N₃O₃S) complex DMSO solution.Solid bromamine acid and monovalence copper complex are alternately added in container in 1 hour, keep reaction temperature 80 DEG C, The pH 7.5 of reaction system, stirring reaction 3-5 hour；Keeping reaction temperature 85-90 DEG C, stirring reaction, thin layer chromatography is done in sampling And liquid-phase chromatographic analysis, it is reaction end without bromamine acid.Without bromamine acid hydrolyzate (purple secondary) and double contracting in reactant liquor mixture Thing, has trace debrominate product.

Embodiment 45

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 3-((2-aminothio formohydrazide group) methyl)-2 hydroxybenzoic acid (C₉H₁₁N₃O₃S) complex DMSO Solution.Solid bromamine acid and monovalence copper complex are alternately added in container in 1 hour, keep reaction temperature 80-82 DEG C, instead Answer the pH 9 of system, stirring reaction 3 hours；Keeping reaction temperature 85-90 DEG C, stirring reaction, thin layer chromatography and liquid phase are done in sampling Chromatography, is reaction end without bromamine acid.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, have micro- Amount debrominate product.

Embodiment 46

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 4-(((2-pyridylmethyl) imino group) methyl) 1,3-Benzodiazepines (C₁₃H₁₂N₂O₂) complex ethanol is molten Liquid.Solid bromamine acid and monovalence copper complex are alternately added in container in 1 hour, keep reaction temperature 75-80 DEG C, reaction The pH 7-8 of system, stirring reaction 3-4 hour；Keeping reaction temperature 80-90 DEG C, stirring reaction, thin layer chromatography and liquid are done in sampling Analysis of hplc, is reaction end without bromamine acid.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, have Trace debrominate product.

Embodiment 47

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 4-(((2-pyridylmethyl) amino) methyl) 1,3-Benzodiazepines (C₁₃H₁₄N₂O₂) complex ethanol is molten Liquid.Solid bromamine acid and monovalence copper complex are alternately added in container in 1 hour, keep reaction temperature 75 DEG C, reactant The pH7.5 of system, stirring reaction 5 hours；Keeping reaction temperature 85-90 DEG C, stirring reaction, thin layer chromatography and liquid chromatograph are done in sampling Analyze, be reaction end without bromamine acid.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, trace is had to take off Bromine product.

Above-mentioned material cools to 40 DEG C, slowly regulates pH 2.8-3.0 with hydrochloric acid, stirs 30 minutes, filters, and reclaims 2,4- Diamino benzene sulfonic acid.Filtrate is warmed up to 60 DEG C, adjusts pH < 1,15-20% by volume to add sodium chloride, stirring, filter paper point sample speckle After point is clear, being cooled to room temperature, filter, filter cake is reactive brilliant bule K-GR intermediate.

Embodiment 48

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 2-(2,4-dihydroxy benzenes methylene) thiosemicarbazides (C₈H₉N₃O₂S) complex DMSO solution.By solid Bromamine acid and monovalence copper complex were alternately added in container in 1 hour, kept reaction temperature 80-82 DEG C, the pH of reaction system 9, stirring reaction 3 hours；Keeping reaction temperature 85-90 DEG C, stirring reaction, thin layer chromatography and liquid-phase chromatographic analysis, nothing are done in sampling Bromamine acid is reaction end.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, there is trace debrominate product.

Embodiment 49

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 2-(2,4-dihydroxy benzyl) thiosemicarbazides (C₈H₁₁N₃O₂S) complex DMSO solution.By solid bromine ammonia Acid and monovalence copper complex were alternately added in container in 1 hour, kept reaction temperature 75-80 DEG C, the pH 8 of reaction system, stirred Mix reaction 5 hours；Keeping reaction temperature 85-90 DEG C, stirring reaction, sampling does thin layer chromatography and liquid-phase chromatographic analysis, without bromine ammonia Acid is reaction end.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, there is trace debrominate product.

Embodiment 50

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 4-((pyridine-2-base) methyl-imino) 2 pentanone (C₁₁H₁₄N₂O) complex ethanol solution.By solid Bromamine acid and monovalence copper complex were alternately added in container in 1 hour, kept reaction temperature 80-85 DEG C, the pH of reaction system 7.5, stirring reaction 3 hours；Keeping reaction temperature 85-90 DEG C, stirring reaction, thin layer chromatography and liquid-phase chromatographic analysis are done in sampling, It is reaction end without bromamine acid.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, trace debrominate is had to produce Thing.

Embodiment 51

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 2-(((2-(dimethylamino) ethyl) imino group) methyl) phenol (C₁₁H₁₆N₂O) complex ethanol is molten Liquid.Solid bromamine acid and monovalence copper complex are alternately added in container in 1 hour, keep reaction temperature 75 DEG C, reactant The pH 7.5 of system, stirring reaction 5 hours；Keeping reaction temperature 85-90 DEG C, stirring reaction, thin layer chromatography and liquid phase color are done in sampling Analysis of spectrum, is reaction end without bromamine acid.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, there is trace Debrominate product.

Embodiment 52

Weigh 2,4-diamino benzene sulfonic acid 8.4 grams, sodium bicarbonate 8.4 grams, 20 milliliters of water, join equipped with agitator, cold Condenser, thermometer container in, be heated to 80 DEG C under stirring.Weighing bromamine acid 8.08 grams respectively, 10%mol (with bromamine acid is Benchmark) monovalence copper and 2-(((2-(dimethylamino) ethyl) amino) methyl) phenol (C₁₁H₁₈N₂O) complex solution.Will Solid bromamine acid and monovalence copper complex were alternately added in container in 1 hour, kept reaction temperature 75-80-DEG C, reaction system PH 7.5, stirring reaction 3 hours；Keeping reaction temperature 85-90 DEG C, stirring reaction, thin layer chromatography and liquid chromatograph are done in sampling Analyze, be reaction end without bromamine acid.Without bromamine acid hydrolyzate (purple secondary) and double contracting thing in reactant liquor mixture, trace is had to take off Bromine product.

The present invention is not limited to the preparation method of reactive brilliant bule K-GR intermediate, wherein catalyst one described in embodiment 1-52 Valency copper complex kind or the change of consumption, the change of solvent species, acid binding agent kind or the change of consumption, bromamine acid and 2,4- The change of diamino benzene sulfonic acid consumption and reaction temperature is all within protection scope of the present invention.

Last it is noted that various embodiments above is only in order to illustrate technical scheme, it is not intended to limit；To the greatest extent The present invention has been described in detail by pipe with reference to foregoing embodiments, it will be understood by those within the art that: it depends on So the technical scheme described in foregoing embodiments can be modified, or the most some or all of technical characteristic is entered Row equivalent；And these amendments or replacement, do not make the essence of appropriate technical solution depart from various embodiments of the present invention technology The scope of scheme.

Claims

1. a preparation method for reactive brilliant bule K-GR intermediate, described reactive brilliant bule K-GR intermediate is the change with formula I Compound:

Wherein M is H, NH₄Or alkali metal, described alkali metal is Li, Na or K, it is characterised in that: in the middle of described reactive brilliant bule K-GR The preparation method of body comprises the following steps: uses and includes the copper complex formazan catalyst system of monovalence, in a solvent catalysis bromine ammonia Acid and 2,4-diamino benzene sulfonic acid or 2,4-diamino benzene sulfonic acid sodium mediated condensated reaction, described solvent is water；

Described monovalence copper complex is:

With water soluble bivalent nantokite for copper source, use the method for reducing agent reduction or electrochemical reduction that cupric is reduced to monovalence Copper, wherein said reducing agent is water miscible organic or inorganic reducing agent；Add the monovalence that part is formed with monovalence copper complexation Copper complex；

Or with water soluble bivalent nantokite for copper source, under conditions of part exists, cupric is reduced to monovalence copper, forms monovalence Copper complex；

Or with monovalence copper for copper source, directly monovalence copper is acted in the solution with organic ligand, form monovalence copper complex；

Described part is:

In one or more.

The preparation method of reactive brilliant bule K-GR intermediate the most according to claim 1, it is characterised in that: described cupric salt For: CuBr₂、CuCl₂、Cu(NO₃)₂、CuSO₄With Cu (CH₃COO)₂In one or more, described cuprous salt be CuCl, One or more in CuBr and CuI.

The preparation method of reactive brilliant bule K-GR intermediate the most according to claim 1, it is characterised in that: described reducing agent is； Ascorbic acid (Vc), azanol, FeCl₂、SnCl₂、FeSO₄、Na₂SO₃、Na₂S₂O₃、NO、NaHSO₃, in arabo-ascorbic acid and oxalic acid One or more.

The preparation method of reactive brilliant bule K-GR intermediate the most according to claim 1, it is characterised in that: described solvent is: water, One or more in ethanol, DMF and DMSO；When solvent is water, when the consumption of water can make bromamine acid convert completely in system The molar concentration of 2,4-diamino benzene sulfonic acid or 2,4-diamino benzene sulfonic acid sodium is 0.1-0.8M.

The preparation method of reactive brilliant bule K-GR intermediate the most according to claim 1, it is characterised in that: described condensation reaction exists Carrying out in the presence of acid binding agent, described acid binding agent the most once adds or is dividedly in some parts；The acid binding agent used is NaHCO₃、 KHCO₃、NH₄HCO₃、Na₂HPO₄、Na₂CO₃、KOH、NaOH、MgO、NaOAc、K₃PO₄、CsCO₃And K₂CO₃In one or more, The pH of reaction system is 7.2-8.5；The mole dosage of described acid binding agent is 2-6 times of bromamine acid.

The preparation method of reactive brilliant bule K-GR intermediate the most according to claim 1, it is characterised in that: described monovalence copper complexation Mole is bromamine acid the 0.5% to 20% of thing.

The preparation method of reactive brilliant bule K-GR intermediate the most according to claim 1, it is characterised in that: described monovalence copper complexation Thing is supported on carrier.

8. according to the preparation method of reactive brilliant bule K-GR intermediate described in any one in claim 1-7, it is characterised in that: institute The mol ratio stating bromamine acid and 2,4-diamino benzene sulfonic acid or 2,4-diamino benzene sulfonic acid sodium is 1:1.2 to 1:3.