CN102617410B

CN102617410B - Method for purifying 3,4,5,6-tetrahalogenated phenolsulfonphthalein

Info

Publication number: CN102617410B
Application number: CN 201210068919
Authority: CN
Inventors: 王立坚; 赵春影
Original assignee: Changchun Wancheng Bioelectronic Engineering Co Ltd
Current assignee: Changchun Wancheng Bioelectronic Engineering Co Ltd
Priority date: 2012-03-15
Filing date: 2012-03-15
Publication date: 2013-11-06
Anticipated expiration: 2032-03-15
Also published as: CN102617410A

Abstract

The invention relates to a method for purifying 3,4,5,6-tetrahalogenated phenolsulfonphthalein, belonging to the technical field of preparation of chemical medicaments. The method comprises the following steps of: reacting 3,4,5,6-tetrahalogenated o-sulfobenzoic anhydride with phenol to obtain crude 3,4,5,6-tetrahalogenated phenolsulfonphthalein; extracting the crude 3,4,5,6-tetrahalogenated phenolsulfonphthalein with a solvent; and recrystallizing, wherein the solvent extraction step comprises the following steps of: proportionally mixing the crude product with acetonitrile or ethyl acetate; heating, stirring and refluxing; filtering; concentrating a filtrate; and drying to obtain an extraction product; and the recrystallizing step comprises the following steps of: proportionally mixing the extraction product with ethyl ether or petroleum ether; heating, stirring and refluxing; cooling to the room temperature; filtering; and drying a filter cake to obtain a final product. The purifying method has the advantages of simple process, low cost, convenience for producing, low toxicity, recyclability of used reagents and low environmental pollution.

Description

A kind of 3,4,5, the purification process of 6-four halogenated phenols sulfonephthalein

Technical field

The present invention relates to the technical field of a kind of chemicals preparation, especially a kind of 3,4,5, the purification process of 6-four halogenated phenols sulfonephthalein.

Background technology

3,4,5,6-, four halogenated phenols sulfonephthalein are derivatives of a kind of phenolsulfonphthalein, are a kind of important acid base indicators, are also simultaneously the starting raw materials of synthetic other multiple indicator, and its structural formula is as follows:

In structural formula A and B, X can be Cl, Br, I.Wherein A represents the general structure formula of this compounds in protonic solvent, said protonic solvent such as water, ethanol etc.; B represent this compound with dry powder form pure or be in aprotic solvent in structural formula, said aprotic solvent such as acetonitrile, ethyl acetate, acetone, ether etc.

When X was Br, this compound was 3,4,5,6 ,-tetrabromophenolsulfonphthalein is a kind of acid base indicator, be also a kind of important protein error indicator, can be synthesized by it and detect a kind of substrate that microalbumin test paper in urine or reagent place use, see US Patent No. 5187104.

3,4,5 of bibliographical information, the synthetic method of 6-four halogenated phenols sulfonephthalein is normally raw material with 3,4,5,6-, four halo o-methyl benzoic acid anhydrides, makes 3,4,5,6-, four halogenated phenols sulfonephthalein with phenol reactant, reaction formula is as follows:

In reaction formula, X can be Cl, Br, I.

In synthetic 3,4,5,6-, four halogenated phenols sulfonephthalein processes, 3,4,5,6-, four halo o-methyl benzoic acid anhydrides at first with a part phenol generation addition reaction, generate the adduct intermediate, and then with the condensation of a part phenol, slough simultaneously a part water, generate the phenolsulfonphthalein product.Usually reaction is complete not due to raw material phenol and adduct, brings in final product, affects the purity of product.

About the purification process of 3,4,5,6-, four halogenated phenols sulfonephthalein, bibliographical information is less, and the method for having reported normally with the inorganic alkali solution of its crude product, adds hydrochloric acid to separate out product, then recrystallization in hot benzene.

Yet in use alkali acid treatment and hot benzene, the purification process of recrystallization, all can not fully remove the major impurities such as phenol and adduct, and use benzene solvent, and serious environment pollution also causes very large murder by poisoning to human body.

In addition, this compounds is at present domestic not to be produced, and the product dependence on import is expensive.And the existing product purity lower (75%～80%) of producing of external producer wherein all contains the impurity such as a certain amount of phenol and adduct, and the existence of these impurity has a strong impact on the quality of product, also can exert an influence to its result of use simultaneously.

Therefore, this just need a kind of technique simple, with low cost, be convenient to produce, lowly poison, oligosaprobic purification process, can fully remove impurity, improve product purity, guarantee its result of use.

Summary of the invention

The invention provides a kind ofly 3,4,5, the purification process of 6-four halogenated phenols sulfonephthalein to solve the deficiency in existing technology of preparing, increases substantially by the method the material purity that makes, thus the satisfying the market requirement.

Concrete technical scheme of the present invention is as follows:

With 3,4,5,6-, four halo o-methyl benzoic acid anhydrides and phenol reactant make 3,4,5, at first 6-four halogenated phenols sulfonephthalein crude products pass through solvent extraction, and then recrystallization, make final product;

Described 3,4,5,6-four halogenated phenols sulfonephthalein are 3,4,5,6-tetra-chloro-phenol sulfonephthalein, 3,4,5,6-tetrabromophenolsulfonphthalein or 3,4,5,6-tetraiodo phenolsulfonphthalein;

Described solvent extraction is that crude product is mixed with acetonitrile 1: 8 in proportion～16 (w/v) or mixes with ethyl acetate 1: 10 in proportion～20 (w/v), and heated and stirred refluxed 1～2 hour, filter, filtrate is concentrated, in 105 ℃ of dryings 2～3 hours, makes extract product;

Described recrystallization is that extract product is mixed with ether 1: 5 in proportion～10 (w/v) or mixes with sherwood oil 1: 10 in proportion～20 (w/v), and heated and stirred refluxed 1～2 hour, cool to room temperature, filter, filter cake makes final product in 105 ℃ of dryings 2～3 hours.

The present invention is a kind of 3,4,5, the purification process of 6-four halogenated phenols sulfonephthalein, and described solvent extraction is completed in aprotic polar solvent; Described recrystallization is completed in aproticapolar solvent.Further, be the four halophenol sulfonephthalein crude products process aprotic polar solvent extractings that at first will make, and then make through recrystallization in aproticapolar solvent.

Show by experimental study of the present invention, phenol, adduct, four halogenated phenols sulfonephthalein all are soluble in protonic solvent, and are difficult to be isolated, and therefore can not use protonic solvent extracting or recrystallization;

When using the aprotic polar solvent extracting, because the partial impurities such as adduct are insoluble to aprotic polar solvent, and four halogenated phenols sulfonephthalein can dissolve fully non-proton polarity molten in, therefore, the product that makes does not contain the partial impurities such as adduct;

When using the aproticapolar solvent recrystallization, because the partial impurities such as phenol can be dissolved in aproticapolar solvent fully, and four halogenated phenols sulfonephthalein are slightly soluble in aproticapolar solvent, crystallization from aproticapolar solvent like this, therefore, contain hardly the partial impurities such as phenol in the product that makes.

Therefore, purification process of the present invention must be crude product is used the aprotic polar solvent extracting after, re-use aproticapolar solvent to its recrystallization, just can obtain outstanding effect, otherwise, do not reach expected effect.

In solvent extraction step of the present invention, said aprotic polar solvent can be acetone, acetonitrile, ethyl acetate, wherein use ethyl acetate, acetonitrile to compare with acetone, the partial impurities such as products therefrom adduct are low, product purity is high, productive rate is high, therefore use ethyl acetate and acetonitrile implementation result better.

In re-crystallization step of the present invention, said aproticapolar solvent can be tetracol phenixin, sherwood oil, ether, wherein, use ether, sherwood oil to compare with tetracol phenixin, the partial impurities such as products therefrom phenol are low, product purity is high, and productive rate is high, production cost is low, poison little, pollute littlely, therefore, use ether and sherwood oil implementation result better.

With existing 3,4,5, the purification process of 6-four halogenated phenols sulfonephthalein is compared, and purification process of the present invention has the following advantages:

1) purification process technique of the present invention simple, with low cost, be convenient to produce, and do not use kind solvents such as benzene and tetracol phenixin, toxic is little, reagent used all can reclaim, environmental pollution is low.

2) purification process of the present invention has successively used two kinds of methods of solvent extraction and recrystallization, and is namely first in the solvent extraction step, uses ethyl acetate or acetonitrile, effectively removed the partial impurities such as adduct; Then in re-crystallization step, use ether or sherwood oil, the partial impurities such as phenol is retained in crystalline mother solution, effectively removed the partial impurities such as phenol.Like this, contain hardly phenol, adduct and other partial impurities in the product that finally makes, thereby significantly improved product purity (more than 95%).

Implement according to the method for the invention, the four halogenated phenols sulfonephthalein impurity that finally make are low, purity is high, yield is high.Therefore, purification process of the present invention can be guaranteed the quality of four halogenated phenols sulfonephthalein.

Purification process of the present invention not only can be used for by 3,4, and 5, the purifying of the four halophenol sulfonephthalein crude products that 6-four halo o-methyl benzoic acid anhydrides are produced, furthermore, also can be used for the purifying of commercially available four halophenol sulfonephthalein raw materials, this purification process can overcome deficiency of the prior art.

Therefore, to develop a kind of purification process of new four halogenated phenols sulfonephthalein be very necessary in the present invention.

Embodiment

Purity described in the present invention, its analytical procedure all adopt the RP-HPLC method to analyze, and calculate with area normalization method, and the method can specifically be used following chromatographic condition and carry out:

Detect wavelength: 254nm; Chromatographic column: C18 post (5 μ m, 4.6 * 250mm); Moving phase: acetonitrile-water (40: the 60) solution that contains 0.1%TFA; 30 ℃ of column temperatures; Flow velocity: 1mL/ minute.

Below in conjunction with embodiment, the purification process of a kind of four halogenated phenols sulfonephthalein of the present invention is described further, but protection scope of the present invention is not limited to embodiment.

Embodiment 1:3,4,5,6-tetra-chloro-phenol sulfonephthalein is synthetic

Phenol 146.2 grams (1.55moL) are added in reactor, in 110 ℃ of temperature control stirrings 1 hour, then add tetrachloro o-methyl benzoic acid anhydride 200 grams (0.62moL), stir until all dissolvings, add 80 milliliters of tin tetrachloride of being fuming, then temperature is raised to 120-130 ℃, temperature control stirring heating 8 hours, monitoring reaction under ultraviolet 254nm, developping agent: methyl alcohol: ethyl acetate=1: 5.React complete after, melts is poured in 10L boiling water, heated and stirred 30 minutes is filtered, filter cake makes approximately 259 grams of crude product in 105 ℃ of oven dry 4 hours.

Embodiment 2:3,4,5,6-tetrabromophenolsulfonphthalein is synthetic

Phenol 105.4 grams (1.12moL) are added in reactor, in 110 ℃ of temperature control stirrings 1 hour, add tetrabromo o-methyl benzoic acid anhydride 200 grams (0.4moL), stir, cool the temperature under 80 ℃, add 95 milliliters of the tin tetrachloride of being fuming, mixed solution is warmed up to 130-140 ℃, temperature control heated and stirred reaction 7 hours, monitoring reaction under ultraviolet 254nm, developping agent: methyl alcohol: ethyl acetate=1: 5.React complete after, product is added in 10L boiling water, heated and stirred 30 minutes is filtered, filter cake makes approximately 235 grams of crude product in 105 ℃ of oven dry 4 hours.

Embodiment 3:3,4,5,6-tetraiodo phenolsulfonphthalein is synthetic

Phenol 82.1 grams (0.87mole) are added in reactor, in 110 ℃ of temperature control stirrings 1 hour, add tetrabromo o-methyl benzoic acid anhydride 200 grams (0.29mole), stir, cool the temperature under 80 ℃, add 105 milliliters of the tin tetrachloride of being fuming, mixed solution is warmed up to 130-140 ℃, temperature control heated and stirred reaction 7 hours, monitoring reaction under ultraviolet 254nm, developping agent: methyl alcohol: ethyl acetate=1: 5.React complete after, product is added in 10L boiling water, heated and stirred 30 minutes is filtered, filter cake makes approximately 212 grams of crude product in 105 ℃ of oven dry 4 hours.

Embodiment 4:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 8 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.0 grams, purity 87.2%.

Get extract product 10 grams, 1: 5 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.2 grams, purity 97.5% in 105 ℃ of dryings 2 hours.

Embodiment 5:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 8 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.2 grams, purity 87.5%.

Get extract product 10 grams, 1: 7.5 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.1 grams, purity 97.8% in 105 ℃ of dryings 2 hours.

Embodiment 6:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 8 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.5 grams, purity 86.8%.

Get extract product 10 grams, 1: 10 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 7.8 grams, purity 97.9% in 105 ℃ of dryings 2 hours.

Embodiment 7:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 8 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 10.8 grams, purity 87.1%.

Get extract product 10 grams, 1: 10 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.1 grams, purity 96.5% in 105 ℃ of dryings 2 hours.

Embodiment 8:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 8 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 10.8 grams, purity 86.9%.

Get extract product 10 grams, 1: 15 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 7.8 grams, purity 96.8% in 105 ℃ of dryings 2 hours.

Embodiment 9:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 8 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 10.9 grams, purity 87.6%.

Get extract product 10 grams, 1: 20 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 7.7 grams, purity 97.2% in 105 ℃ of dryings 2 hours.

Embodiment 10:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 12 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.5 grams, purity 86.3%.

Get extract product 10 grams, 1: 5 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.4 grams, purity 97.1% in 105 ℃ of dryings 2 hours.

Embodiment 11:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 12 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.7 grams, purity 86.2%.

Get extract product 10 grams, 1: 7.5 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 7.9 grams, purity 97.2% in 105 ℃ of dryings 2 hours.

Embodiment 12:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 12 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.3 grams, purity 86.8%.

Get extract product 10 grams, 1: 10 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 7.8 grams, purity 97.2% in 105 ℃ of dryings 2 hours.

Embodiment 13:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 12 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.3 grams, purity 86.9%.

Get extract product 10 grams, 1: 10 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.1 grams, purity 96.3% in 105 ℃ of dryings 2 hours.

Embodiment 14:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get extract product 10 grams, 1: 15 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.1 grams, purity 97.2% in 105 ℃ of dryings 2 hours.

Embodiment 15:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 12 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.0 grams, purity 87.3%.

Get extract product 10 grams, 1: 20 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 7.8 grams, purity 97.1% in 105 ℃ of dryings 2 hours.

Embodiment 16:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 16 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.0 grams, purity 86.9%.

Get extract product 10 grams, 1: 5 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.3 grams, purity 97.1% in 105 ℃ of dryings 2 hours.

Embodiment 17:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 16 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.3 grams, purity 87.3%.

Get extract product 10 grams, 1: 7.5 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.1 grams, purity 96.9% in 105 ℃ of dryings 2 hours.

Embodiment 18:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 16 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.4 grams, purity 86.6%.

Get extract product 10 grams, 1: 10 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 7.9 grams, purity 97.8% in 105 ℃ of dryings 2 hours.

Embodiment 19:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 16 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.4 grams, purity 86.2%.

Get extract product 10 grams, 1: 10 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.4 grams, purity 96.5% in 105 ℃ of dryings 2 hours.

Embodiment 20:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 16 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.5 grams, purity 86.8%.

Get extract product 10 grams, 1: 15 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.2 grams, purity 97.2% in 105 ℃ of dryings 2 hours.

Embodiment 21:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 16 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.6 grams, purity 86.6%.

Get extract product 10 grams, 1: 20 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 7.7 grams, purity 96.9% in 105 ℃ of dryings 2 hours.

Embodiment 22:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 10 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.5 grams, purity 87.5%.

Get extract product 10 grams, 1: 5 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.5 grams, purity 96.5% in 105 ℃ of dryings 2 hours.

Embodiment 23:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 10 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.4 grams, purity 87.2%.

Get extract product 10 grams, 1: 7.5 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.4 grams, purity 97.6% in 105 ℃ of dryings 2 hours.

Embodiment 24:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 10 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.5 grams, purity 87.1%.

Get extract product 10 grams, 1: 10 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 7.9 grams, purity 97.6% in 105 ℃ of dryings 2 hours.

Embodiment 25:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 10 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.6 grams, purity 86.5%.

Get extract product 10 grams, 1: 10 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.3 grams, purity 96.5% in 105 ℃ of dryings 2 hours.

Embodiment 26:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 10 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.5 grams, purity 87.6%.

Get extract product 10 grams, 1: 15 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.4 grams, purity 96.5% in 105 ℃ of dryings 2 hours.

Embodiment 27:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 10 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.2 grams, purity 87.5%.

Get extract product 10 grams, 1: 20 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.1 grams, purity 97.8% in 105 ℃ of dryings 2 hours.

Embodiment 28:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 15 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.5 grams, purity 87.0%.

Get extract product 10 grams, 1: 5 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.6 grams, purity 97.1% in 105 ℃ of dryings 2 hours.

Embodiment 29:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 15 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.6 grams, purity 87.3%.

Embodiment 30:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 15 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.6 grams, purity 87.6%.

Get extract product 10 grams, 1: 10 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.0 grams, purity 97.9% in 105 ℃ of dryings 2 hours.

Embodiment 31:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 15 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.6 grams, purity 87.4%.

Get extract product 10 grams, 1: 10 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.3 grams, purity 97.5% in 105 ℃ of dryings 2 hours.

Embodiment 32:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 15 in proportion (w/v) mixes according to crude product and ethyl acetate acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.4 grams, purity 86.8%.

Get extract product 10 grams, 1: 15 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.3 grams, purity 97.1% in 105 ℃ of dryings 2 hours.

Embodiment 33:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 15 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.4 grams, purity 87.0%.

Get extract product 10 grams, 1: 20 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 7.8 grams, purity 97.3% in 105 ℃ of dryings 2 hours.

Embodiment 34:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 20 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.3 grams, purity 88.7%.

Get extract product 10 grams, 1: 5 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.5 grams, purity 97.1% in 105 ℃ of dryings 2 hours.

Embodiment 35:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 20 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.6 grams, purity 86.4%.

Get extract product 10 grams, 1: 7.5 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.2 grams, purity 97.5% in 105 ℃ of dryings 2 hours.

Embodiment 36:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 20 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.7 grams, purity 86.8%.

Get extract product 10 grams, 1: 10 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 7.9 grams, purity 98.3% in 105 ℃ of dryings 2 hours.

Embodiment 37:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 20 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.4 grams, purity 87.2%.

Get extract product 10 grams, 1: 10 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.3 grams, purity 96.8% in 105 ℃ of dryings 2 hours.

Embodiment 38:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 20 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.6 grams, purity 87.1%.

Get extract product 10 grams, 1: 15 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.4 grams, purity 97.1% in 105 ℃ of dryings 2 hours.

Embodiment 39:3,4,5,6-tetra-chloro-phenol sulfonephthalein purifying

Get according to embodiment 1 method make 3,4,5,6-tetra-chloro-phenol sulfonephthalein crude product 20 grams, 1: 20 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.7 grams, purity 87.1%.

Embodiment 40:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 8 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.1 grams, purity 86.2%.

Get extract product 10 grams, 1: 5 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.3 grams, purity 97.9% in 105 ℃ of dryings 2 hours.

Embodiment 41:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 8 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.3 grams, purity 87.5%.

Get extract product 10 grams, 1: 7.5 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.2 grams, purity 97.9% in 105 ℃ of dryings 2 hours.

Embodiment 42:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 8 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.8 grams, purity 86.7%.

Get extract product 10 grams, 1: 10 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 7.9 grams, purity 98.0% in 105 ℃ of dryings 2 hours.

Embodiment 43:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 8 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 10.8 grams, purity 87.1%.

Get extract product 10 grams, 1: 10 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.2 grams, purity 96.6% in 105 ℃ of dryings 2 hours.

Embodiment 44:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 8 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 10.9 grams, purity 86.8%.

Get extract product 10 grams, 1: 15 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 7.9 grams, purity 96.9% in 105 ℃ of dryings 2 hours.

Embodiment 45:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 8 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 10.9 grams, purity 87.5%.

Embodiment 46:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 12 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.6 grams, purity 86.4%.

Get extract product 10 grams, 1: 5 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.5 grams, purity 97.2% in 105 ℃ of dryings 2 hours.

Embodiment 47:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 12 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.7 grams, purity 86.4%.

Get extract product 10 grams, 1: 7.5 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 7.9 grams, purity 97.6% in 105 ℃ of dryings 2 hours.

Embodiment 48:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 12 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.4 grams, purity 86.9%.

Embodiment 49:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 12 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.3 grams, purity 86.9%.

Get extract product 10 grams, 1: 10 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.1 grams, purity 96.4% in 105 ℃ of dryings 2 hours.

Embodiment 50:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get extract product 10 grams, 1: 15 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.4 grams, purity 97.5% in 105 ℃ of dryings 2 hours.

Embodiment 51:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 12 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.2 grams, purity 87.5%.

Get extract product 10 grams, 1: 20 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 7.9 grams, purity 97.3% in 105 ℃ of dryings 2 hours.

Embodiment 52:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 16 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.1 grams, purity 87.8%.

Get extract product 10 grams, 1: 5 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.4 grams, purity 97.3% in 105 ℃ of dryings 2 hours.

Embodiment 53:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 16 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.3 grams, purity 87.3%.

Embodiment 54:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 16 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.4 grams, purity 86.6%.

Embodiment 55:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 16 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.5 grams, purity 86.2%.

Get extract product 10 grams, 1: 10 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.5 grams, purity 96.6% in 105 ℃ of dryings 2 hours.

Embodiment 56:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 16 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.5 grams, purity 86.8%.

Get extract product 10 grams, 1: 15 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.6 grams, purity 97.6% in 105 ℃ of dryings 2 hours.

Embodiment 57:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 16 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.8 grams, purity 86.7%.

Get extract product 10 grams, 1: 20 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 7.8 grams, purity 97.0% in 105 ℃ of dryings 2 hours.

Embodiment 58:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 10 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.5 grams, purity 87.5%.

Get extract product 10 grams, 1: 5 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.5 grams, purity 96.3% in 105 ℃ of dryings 2 hours.

Embodiment 59:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 10 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.4 grams, purity 87.4%.

Get extract product 10 grams, 1: 7.5 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.4 grams, purity 97.8% in 105 ℃ of dryings 2 hours.

Embodiment 60:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 10 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.6 grams, purity 87.3%.

Embodiment 61:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 10 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.7 grams, purity 86.6%.

Get extract product 10 grams, 1: 10 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.5 grams, purity 96.2% in 105 ℃ of dryings 2 hours.

Embodiment 62:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 10 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.4 grams, purity 87.7%.

Get extract product 10 grams, 1: 15 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.5 grams, purity 96.3% in 105 ℃ of dryings 2 hours.

Embodiment 63:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 10 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.2 grams, purity 87.2%.

Embodiment 64:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 15 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.3 grams, purity 87.6%.

Get extract product 10 grams, 1: 5 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.6 grams, purity 97.3% in 105 ℃ of dryings 2 hours.

Embodiment 65:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 15 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.4 grams, purity 87.5%.

Embodiment 66:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 15 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.6 grams, purity 87.4%.

Embodiment 67:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 15 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.5 grams, purity 87.9%.

Get extract product 10 grams, 1: 10 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.3 grams, purity 97.8% in 105 ℃ of dryings 2 hours.

Embodiment 68:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 15 in proportion (w/v) mixes according to crude product and ethyl acetate acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.4 grams, purity 86.9%.

Embodiment 69:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 15 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.4 grams, purity 87.0%.

Get extract product 10 grams, 1: 20 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 7.6 grams, purity 97.8% in 105 ℃ of dryings 2 hours.

Embodiment 70:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 20 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.3 grams, purity 88.7%.

Embodiment 71:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 20 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.4 grams, purity 86.5%.

Embodiment 72:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 20 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.5 grams, purity 86.9%.

Get extract product 10 grams, 1: 10 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 7.9 grams, purity 98.5% in 105 ℃ of dryings 2 hours.

Embodiment 73:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 20 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.3 grams, purity 88.2%.

Get extract product 10 grams, 1: 10 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.0 grams, purity 96.4% in 105 ℃ of dryings 2 hours.

Embodiment 74:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 20 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.6 grams, purity 87.1%.

Get extract product 10 grams, 1: 15 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.3 grams, purity 97.4% in 105 ℃ of dryings 2 hours.

Embodiment 75:3,4,5,6-tetrabromophenolsulfonphthalein purifying

Get according to embodiment 2 methods make 3,4,5,6-tetrabromophenolsulfonphthalein crude product 20 grams, 1: 20 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.6 grams, purity 87.3%.

Get extract product 10 grams, 1: 20 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.3 grams, purity 97.2% in 105 ℃ of dryings 2 hours.

Embodiment 76:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 8 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.1 grams, purity 87.3%.

Get extract product 10 grams, 1: 5 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.8 grams, purity 97.1% in 105 ℃ of dryings 2 hours.

Embodiment 77:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 8 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.5 grams, purity 87.2%.

Get extract product 10 grams, 1: 7.5 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.0 grams, purity 97.3% in 105 ℃ of dryings 2 hours.

Embodiment 78:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 8 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.5 grams, purity 86.8%.

Embodiment 79:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 8 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 10.7 grams, purity 87.5%.

Get extract product 10 grams, 1: 10 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.3 grams, purity 96.3% in 105 ℃ of dryings 2 hours.

Embodiment 80:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 8 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 10.6 grams, purity 87.0%.

Embodiment 81:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 8 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 10.4 grams, purity 87.6%.

Get extract product 10 grams, 1: 20 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 7.9 grams, purity 97.8% in 105 ℃ of dryings 2 hours.

Embodiment 82:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 12 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.8 grams, purity 86.8%.

Embodiment 83:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 12 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.7 grams, purity 86.2%.

Get extract product 10 grams, 1: 7.5 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 7.9 grams, purity 97.9% in 105 ℃ of dryings 2 hours.

Embodiment 84:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 12 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.7 grams, purity 86.5%.

Embodiment 85:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 12 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.8 grams, purity 86.6%.

Get extract product 10 grams, 1: 10 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.1 grams, purity 97.3% in 105 ℃ of dryings 2 hours.

Embodiment 86:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 12 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.4 grams, purity 86.5%.

Embodiment 87:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 12 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.3 grams, purity 87.6%.

Embodiment 88:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 16 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.5 grams, purity 86.9%.

Get extract product 10 grams, 1: 5 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.8 grams, purity 97.4% in 105 ℃ of dryings 2 hours.

Embodiment 89:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 16 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.6 grams, purity 87.3%.

Get extract product 10 grams, 1: 7.5 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.3 grams, purity 96.5% in 105 ℃ of dryings 2 hours.

Embodiment 90:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 16 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.5 grams, purity 86.8%.

Embodiment 91:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 16 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.6 grams, purity 86.5%.

Get extract product 10 grams, 1: 10 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.6 grams, purity 96.4% in 105 ℃ of dryings 2 hours.

Embodiment 92:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 16 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.8 grams, purity 86.3%.

Get extract product 10 grams, 1: 15 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.3 grams, purity 97.5% in 105 ℃ of dryings 2 hours.

Embodiment 93:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 16 in proportion (w/v) mixes according to crude product and acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.5 grams, purity 86.7%.

Get extract product 10 grams, 1: 20 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 7.8 grams, purity 96.3% in 105 ℃ of dryings 2 hours.

Embodiment 94:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 10 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.3 grams, purity 87.8%.

Get extract product 10 grams, 1: 5 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.4 grams, purity 96.5% in 105 ℃ of dryings 2 hours.

Embodiment 95:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 10 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.5 grams, purity 87.5%.

Get extract product 10 grams, 1: 7.5 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.5 grams, purity 97.8% in 105 ℃ of dryings 2 hours.

Embodiment 96:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 10 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.4 grams, purity 88.1%.

Embodiment 97:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 10 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.7 grams, purity 87.5%.

Embodiment 98:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 10 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.6 grams, purity 87.8%.

Get extract product 10 grams, 1: 15 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.6 grams, purity 96.5% in 105 ℃ of dryings 2 hours.

Embodiment 99:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 10 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.5 grams, purity 87.6%.

Get extract product 10 grams, 1: 20 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.1 grams, purity 97.9% in 105 ℃ of dryings 2 hours.

Embodiment 100:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 15 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.2 grams, purity 87.8%.

Embodiment 101:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 15 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.8 grams, purity 87.8%.

Get extract product 10 grams, 1: 7.5 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.5 grams, purity 97.2% in 105 ℃ of dryings 2 hours.

Embodiment 102:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 15 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.8 grams, purity 87.3%.

Get extract product 10 grams, 1: 10 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.2 grams, purity 97.5% in 105 ℃ of dryings 2 hours.

Embodiment 103:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 15 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.8 grams, purity 87.6%.

Get extract product 10 grams, 1: 10 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.5 grams, purity 97.6% in 105 ℃ of dryings 2 hours.

Embodiment 104:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 15 in proportion (w/v) mixes according to crude product and ethyl acetate acetonitrile, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.3 grams, purity 86.6%.

Embodiment 105:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 15 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.5 grams, purity 87.3%.

Embodiment 106:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 20 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.5 grams, purity 88.8%.

Get extract product 10 grams, 1: 5 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.6 grams, purity 97.7% in 105 ℃ of dryings 2 hours.

Embodiment 107:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 20 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.8 grams, purity 86.1%.

Get extract product 10 grams, 1: 7.5 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.6 grams, purity 97.3% in 105 ℃ of dryings 2 hours.

Embodiment 108:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 20 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.2 grams, purity 86.9%.

Get extract product 10 grams, 1: 10 in proportion (w/v) mixes with ether, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 7.8 grams, purity 98.5% in 105 ℃ of dryings 2 hours.

Embodiment 109:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 20 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.2 grams, purity 87.5%.

Embodiment 110:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 20 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.4 grams, purity 87.2%.

Get extract product 10 grams, 1: 15 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.5 grams, purity 97.3% in 105 ℃ of dryings 2 hours.

Embodiment 111:3,4,5,6-tetraiodo phenolsulfonphthalein purifying

Get according to embodiment 3 methods make 3,4,5,6-tetraiodo phenolsulfonphthalein crude product 20 grams, 1: 20 in proportion (w/v) mixes according to crude product and ethyl acetate, and heated and stirred refluxed 1 hour, filters, and filtrate is concentrated, in 105 ℃ of dryings 2 hours, make extract product 11.9 grams, purity 87.5%.

Get extract product 10 grams, 1: 20 in proportion (w/v) mixes with sherwood oil, and heated and stirred refluxed 1 hour, and cool to room temperature filters, and filter cake makes product 8.3 grams, purity 97.6% in 105 ℃ of dryings 2 hours.

Claims

1. one kind 3,4,5, the purification process of 6-four halogenated phenols sulfonephthalein is characterized in that: with 3,4,5,6-, four halo o-methyl benzoic acid anhydrides and phenol reactant make 3,4,5, at first 6-four halogenated phenols sulfonephthalein crude products pass through solvent extraction, and then recrystallization;

2. according to claim 1 a kind of 3,4,5, the purification process of 6-four halogenated phenols sulfonephthalein is characterized in that: described 3,4,5,6-four halogenated phenols sulfonephthalein are 3,4,5,6-tetra-chloro-phenol sulfonephthalein, 3,4,5,6-tetrabromophenolsulfonphthalein or 3,4,5,6-tetraiodo phenolsulfonphthalein.