CN107628974B - A kind of dimercaptosuccinic acid and its salt and preparation method - Google Patents
A kind of dimercaptosuccinic acid and its salt and preparation method Download PDFInfo
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Abstract
The present invention relates to technical field of organic synthesis, in particular to a kind of dimercaptosuccinic acid and its salt and preparation method.The method of the present invention is reacted ethyl xanthate and 2, bis- bromosuccinic acid of 3-, obtains 2,3- auligen ester-Isosorbide-5-Nitrae succinic acid；2,3- Dimercaptosuccinate solution will be obtained after the hydrolysis of -1,4 succinic acid of gained 2,3- auligen ester；It is acidified gained 2,3- Dimercaptosuccinate solution to obtain 2,3- dimercaptosuccinic acid.The method of the present invention simple process does not need liquid thioacetic acid strong using stink and unstable quality, does not need using unsafe addition reaction, short preparation period, high income are at low cost, it is promoted suitable for industrialized production, Dimercaptosuccinate product can further be prepared.Dimercaptosuccinic acid product and Dimercaptosuccinate product purity of the present invention is high, at low cost.
Description
Technical field
The present invention relates to technical field of organic synthesis, in particular to a kind of dimercaptosuccinic acid and its salt and preparation
Method.
Background technique
Dimercaptosuccinic acid (Dimercaptosuccinic acid, DMSA) is a kind of excellent heavy metal detoxification agent,
Structure is as follows:
With deepening continuously for application study, its application field has been extended to many aspects of industry and daily life.
Therefore, seem particularly necessary to the further investigation of its synthesis technology and improvement.
Current country DMSA mainstream industry route of synthesis is with 2,3- dibromosuccinic acid for starting material, is occurred with caustic alkali
Elimination reaction generates intermediate acetylenedicarboxylic acid disodium.Addition reaction occurs with thioacetic acid under strong acidic condition in it, generates 2,
3- diacetyl sulfenyl succinic acid.This object does not need to be separated, and DMSA crude product is obtained after direct acid hydrolysis, then obtain through an one-step refining
DMSA.Synthetic route is as follows:
The advantages of above method is that synthesis step is brief, and defect is that malodorous agent is used in addition process --- it is thio
Acetic acid, production environment are more severe；In addition, using addition reaction because extreme heat emission can be such that temperature steeply rises, therefore there is safety
Hidden danger.
Another preparation method disclosed in the related technology, synthetic route are as follows:
This method replaces thioacetic acid as addition reagent using acetylenedicarboxylic acid as starting material, using sodium thiosulfate, and
Low temperature addition reaction 20 hours or more in the presence of strong acid, 2,3- bisthiosulfate butyl, two acid sodium-salt crude product is obtained by dehydration.
The crude product heats hydrolysis in the strongly acidic aqueous solution of methanol or dioxane, cooling that inorganic salts are precipitated, the mother after filtering desalination
Liquid obtains paste or resin-like object crude product after being evaporated in vacuo.This crude product is primary through being recrystallized with methanol-acetone mixed solvent
Or repeatedly after obtain 2,3- dimercaptosuccinic acid raceme.But product purity and yield are not disclosed.
The advantages of this method is that addition reagent sodium thiosulfate and its five water objects are odorless, less toxic and inexpensive.But addition reaction
Period is long, and actual recovery is low, and needs to be removed water with freeze-drying after reaction, thus energy consumption is high, and production capacity is low, lacks industry
Change productive value.
2,3- dimercapto butyrates (such as 2,3- dimercapto butyric acid disodium) can be prepared into liquid drugs injection, in acute heavy metal
Viral disease people, in the related technology there is not yet about 2, the open periodical of 3- dimercapto butyric acid salt production process is reported.It is actually to adopt
2,3- dimercapto butyrate is prepared with 2,3- dimercapto butyric acid, because 2,3- dimercapto butyric acid is difficult to be fully converted into disodium salt, meeting
There are the impurity such as a small amount of dimercaptosuccinic acid crystal and alkali, it is difficult to obtain 2, the 3- dimercapto butyric acid product salt of high-purity.
In view of this, the present invention is specifically proposed.
Summary of the invention
The first object of the present invention is to provide a kind of preparation method of dimercaptosuccinic acid, this method simple process, no
Liquid thioacetic acid strong using stink and unstable quality is needed, is not needed using unsafe addition reaction, preparation week
Phase is short, high income, at low cost, is suitable for industrialized production and promotes.
The second object of the present invention is to provide a kind of preparation method using above-mentioned dimercaptosuccinic acid and is prepared
Dimercaptosuccinic acid product, the described dimercaptosuccinic acid product purity is high, at low cost.
The third object of the present invention is to provide a kind of preparation method of Dimercaptosuccinate, this method simple process,
It is at low cost, it is suitable for industrialized production and promotes.
The fourth object of the present invention is to provide a kind of preparation method using above-mentioned Dimercaptosuccinate and is prepared into
The Dimercaptosuccinate product arrived, the Dimercaptosuccinate product purity is high, at low cost.
In order to realize above-mentioned purpose of the invention, the following technical scheme is adopted:
A kind of preparation method of dimercaptosuccinic acid, by ethyl xanthate and 2, bis- bromosuccinic acid of 3- is reacted,
Obtain -1,4 succinic acid of 2,3- auligen ester；It will be obtained after the hydrolysis of -1,4 succinic acid of gained 2,3- auligen ester
2,3- Dimercaptosuccinate solution；It is acidified gained 2,3- Dimercaptosuccinate solution to obtain 2,3- dimercaptosuccinic acid.
The preparation method simple process of dimercaptosuccinic acid of the present invention, it is unstable not need and quality strong using stink
Liquid thioacetic acid is not needed using unsafe addition reaction, and short preparation period, high income is at low cost, is suitable for industrial metaplasia
It produces and promotes.
Optionally, the ethyl xanthate includes one of ethoxy-dithioformic acid metal salt or a variety of, preferably includes second
One of base xanthan acid alkali metal salt is a variety of, further preferably includes ethoxy-dithioformic acid sodium salt and/or ehtyl potassium xanthate
Salt.
Optionally, the molar ratio of 2, the 3- dibromosuccinic acid and ethyl xanthate is 1:2-4, preferably 1:2.4-3.
Optionally, described by ethyl xanthate and 2, bis- bromosuccinic acid of 3- carry out the solvent that uses of reaction be acetone with
The mixed solution of water.
Optionally, in the mixed solution of the acetone and water the volume ratio of acetone and water be 1:0.1-2.3, preferably 1:
0.4-1.4。
Optionally, described by ethyl xanthate and 2, the temperature that bis- bromosuccinic acid of 3- is reacted is 45-55 DEG C, excellent
It is selected as 50-55 DEG C.
Optionally, described by ethyl xanthate and 2, the time that bis- bromosuccinic acid of 3- is reacted is 2-6h, preferably
For 3-3.5h.
Optionally, gained 2,3- auligen ester-Isosorbide-5-Nitrae succinic acid and aqueous slkali or acid solution are hydrolyzed instead
It answers, obtains 2,3-dimercaptosuccinic acid salting liquid.
Optionally, the aqueous slkali includes one of inorganic base aqueous solution or a variety of, preferably in alkali metal aqueous solution
One or more, further preferably sodium hydrate aqueous solution.
Optionally, the acid solution includes one of inorganic acid aqueous solution or a variety of, preferably inorganic acid aqueous solution
One of or a variety of, further preferably aqueous hydrochloric acid solution and/or aqueous sulfuric acid.
Optionally, the hydrolysis carries out under a shielding gas.
Optionally, the protective gas includes one of nitrogen and inert gas or a variety of, preferably nitrogen.
Optionally, the mass fraction of the aqueous slkali is 10%-25%, preferably 15%-20%.
Optionally, the mass fraction of the acid solution is 10%-35%, preferably 15%-30%.
Optionally, 2, the 3- bis- replaces the molar ratio of xanthate -1, 4- succinic acid and alkali to be 1:2-6.
Optionally, 2, the 3- bis- replaces the molar ratio of xanthate -1, 4- succinic acid and acid to be 1:2-10.
Optionally, the temperature of the hydrolysis is 75-95 DEG C, preferably 85-90 DEG C.
Optionally, the time of the hydrolysis is 2-6h, preferably 3-3.5h.
Optionally, described to be acidified gained 2,3-dimercaptosuccinic acid salting liquid to obtain 2,3-dimercaptosuccinic acid, made
Acidulant includes one of inorganic acid or a variety of, preferably one of inorganic acid or a variety of, further preferably
Hydrochloric acid and/or sulfuric acid.
Optionally, the temperature of the acidification is 0-30 DEG C, preferably 10-20 DEG C.
Optionally, gained 2,3-dimercaptosuccinic acid is recrystallized.
Optionally, the solvent that the recrystallization uses includes one of alcoholic solvent or a variety of, preferably includes methanol, ethyl alcohol
With one of isopropanol or a variety of, further preferably ethyl alcohol.
Optionally, it is decolourized in the recrystallization process using decolorising agent.
Optionally, the decolorising agent includes active carbon.
The dimercaptosuccinic acid product being prepared using a kind of preparation method of above-mentioned dimercaptosuccinic acid.
Dimercaptosuccinic acid product purity of the present invention is high, at low cost.
A kind of preparation method of above-mentioned dimercaptosuccinic acid is prepared by a kind of preparation method of Dimercaptosuccinate
It after the dimercaptosuccinic acid solution arrived, is neutralized using aqueous slkali, crystallization obtains Dimercaptosuccinate.
The preparation method simple process and low cost of Dimercaptosuccinate of the present invention is suitable for industrialized production and promotes.
Optionally, the solvent that the dimercaptosuccinic acid solution uses is alcoholic solution, preferably methanol and/or ethyl alcohol.
Optionally, the mass ratio of the dimercaptosuccinic acid and methanol is 1:15-22.
Optionally, the mass ratio of the dimercaptosuccinic acid and ethyl alcohol is 1:16-24.
Optionally, dimercaptosuccinic acid is dissolved by heating in a solvent.
Optionally, the heating temperature is reflux temperature.
Optionally, the aqueous slkali includes one of inorganic alkali solution and organic alkali solution or a variety of, it is preferred to use nothing
One of machine aqueous slkali is a variety of, further preferably uses one of carbonate solution or bicarbonate solution or a variety of,
More preferably use sodium carbonate liquor and/or solution of potassium carbonate.
Optionally, the mass fraction of the aqueous slkali is 2.0%-20.0%, preferably 3.0%-8.0%.
Optionally, the temperature of the neutralization is 0 DEG C or more, preferably -50 DEG C of room temperature.
Optionally, the terminal pH of the neutralization is 6.5-8, preferably 6.5-7.5.
Optionally, the neutralization carries out under a shielding gas.
Optionally, the protective gas includes one of nitrogen and inert gas or a variety of.
Optionally, it is aged after the crystallization.
Optionally, the temperature of the ageing is -5.0 to 5.0 DEG C, preferably 0-5 DEG C.
Optionally, the time of the ageing is 4-15h, preferably 8-10h.
Optionally, it after the ageing, is filtered, washed, is dried to obtain Dimercaptosuccinate product.
The Dimercaptosuccinate product being prepared using a kind of preparation method of above-mentioned Dimercaptosuccinate.
Dimercaptosuccinate product purity of the present invention is high, at low cost.
Optionally, the Dimercaptosuccinate includes sodium dimercaptosuccinate salt and/or dimercaptosuccinic acid sylvite, excellent
Choosing includes dimercaptosuccinic acid disodium salt and/or dimercaptosuccinic acid di-potassium.
Compared with prior art, the invention has the benefit that
The preparation method simple process of dimercaptosuccinic acid of the present invention, it is unstable not need and quality strong using stink
Liquid thioacetic acid is not needed using unsafe addition reaction, and short preparation period, high income is at low cost, is suitable for industrial metaplasia
It produces and promotes.Dimercaptosuccinic acid of the present invention can further be prepared Dimercaptosuccinate product, preparation method simple process,
It is at low cost, it is suitable for industrialized production and promotes.Dimercaptosuccinic acid product and Dimercaptosuccinate product purity of the present invention is high, at
This is low.
Specific embodiment
Technical solution of the present invention is clearly and completely described below in conjunction with specific embodiment, but ability
Field technique personnel will be understood that following described embodiments are some of the embodiments of the present invention, instead of all the embodiments,
It is merely to illustrate the present invention, and is not construed as limiting the scope of the invention.Based on the embodiments of the present invention, the common skill in this field
Art personnel every other embodiment obtained without making creative work belongs to the model that the present invention protects
It encloses.The person that is not specified actual conditions in embodiment, carries out according to conventional conditions or manufacturer's recommended conditions.Agents useful for same or instrument
Production firm person is not specified, is the conventional products that can be obtained by commercially available purchase.
A kind of preparation method of dimercaptosuccinic acid is provided in the specific embodiment of the invention, by ethyl xanthate with
2,3- bis- bromosuccinic acids are reacted, and 2,3- auligen ester-Isosorbide-5-Nitrae succinic acid is obtained；Gained 2,3- diethyl is yellow
2,3- Dimercaptosuccinate solution is obtained after the hydrolysis of -1,4 succinic acid of ortho esters；By gained 2,3- Dimercaptosuccinate solution
Acidification obtains 2,3- dimercaptosuccinic acid.
Present invention ehtyl potassium xanthate (or sodium) makees nucleophilic displacement of fluorine reagent, is allowed in aqueous acetone solvent and 2,3- bis-
Nucleophilic substitution occurs for bromosuccinic acid, and generates xanthate, and then hydrolysis obtains dimercapto fourth two in alcohol aqueous slkali
Acid sodium-salt, acidified rear 2,3-dimercaptosuccinic acid are precipitated from water phase, filter 2,3-dimercaptosuccinic acid sediment, filter cake warp
2,3-dimercaptosuccinic acid crude product is obtained after being washed to no acid group detection, then obtains 2,3-, bis- mercapto with ethyl alcohol recrystallization after drying
Base succinic acid.
A kind of synthetic route of the 2,3- dimercaptosuccinic acid of specific embodiment of the present invention is as follows:
The preparation method simple process of dimercaptosuccinic acid of the present invention, the solid-state ethyl slight and inexpensive using a kind of stink
Xanthates (sodium salt or sylvite) the substitution liquid thioacetic acid that stink is strong and quality is unstable, and omitted than prior art
One step elimination reaction especially thoroughly eliminates unsafe addition reaction operation, and be highly advantageous to following industrialized production,
Short preparation period, high income is at low cost, is suitable for industrialized production and promotes.
In a kind of preferred embodiment of the present invention, the ethyl xanthate includes in ethoxy-dithioformic acid metal salt
It is one or more, preferably include one of ethoxy-dithioformic acid alkali metal salt or a variety of, further preferably include ethyl xanthan
Acid sodium-salt and/or ethoxy-dithioformic acid sylvite.
In a kind of preferred embodiment of the present invention, mole of 2, the 3- dibromosuccinic acid and ethyl xanthate
Than for 1:2-4, preferably 1:2.4-3.
Using the molar ratio of specific 2,3- dibromosuccinic acid and ethyl xanthate, 2,3- dibromosuccinic acid is helped to improve
To the conversion ratio and product purity of target product.
It is described by ethyl xanthate and 2 in a kind of preferred embodiment of the present invention, bis- bromosuccinic acid of 3- into
The solvent that row reaction uses is the mixed solution of acetone and water.
In a kind of preferred embodiment of the present invention, the volume of acetone and water in the mixed solution of the acetone and water
Than for 1:0.1-2.3, preferably 1:0.4-1.4.
It is described by ethyl xanthate and 2 in a kind of preferred embodiment of the present invention, bis- bromosuccinic acid of 3- into
The temperature of row reaction is 45-55 DEG C, preferably 50-55 DEG C.
It is described by ethyl xanthate and 2 in a kind of preferred embodiment of the present invention, bis- bromosuccinic acid of 3- into
The time of row reaction is 2-6h, preferably 3-3.5h.
Facilitate the abundant progress of substitution reaction using specific reaction temperature and reaction time, improves 2,3- diethyl xanthan
The yield and purity of -1,4 succinic acid of acid esters.
In a kind of preferred embodiment of the present invention, by gained 2,3- auligen ester-Isosorbide-5-Nitrae succinic acid and alkali
Reaction is hydrolyzed in solution or acid solution, obtains 2,3-dimercaptosuccinic acid salting liquid.
In a kind of preferred embodiment of the present invention, the aqueous slkali includes one of inorganic base aqueous solution or more
Kind, preferably one of alkali metal aqueous solution or a variety of, further preferably sodium hydrate aqueous solution.
In a kind of preferred embodiment of the present invention, the acid solution includes one of inorganic acid aqueous solution or more
Kind, preferably one of inorganic acid aqueous solution or a variety of, further preferably aqueous hydrochloric acid solution and/or aqueous sulfuric acid.
In a kind of preferred embodiment of the present invention, the hydrolysis carries out under a shielding gas.
In a kind of preferred embodiment of the present invention, the protective gas includes one of nitrogen and inert gas
Or a variety of, preferably nitrogen.
In a kind of preferred embodiment of the present invention, the mass fraction of the aqueous slkali is 10%-25%, preferably
15%-20%.
In a kind of preferred embodiment of the present invention, the mass fraction of the acid solution is 10%-35%, preferably
15%-30%.
In a kind of preferred embodiment of the present invention, 2, the 3- bis- replaces xanthate -1, 4- succinic acid and alkali
Molar ratio be 1:2-6.
In a kind of preferred embodiment of the present invention, 2, the 3- bis- replaces xanthate -1, 4- succinic acid and acid
Molar ratio be 1:2-10.
In a kind of preferred embodiment of the present invention, the temperature of the hydrolysis is 75-95 DEG C, preferably 85-
90℃。
In a kind of preferred embodiment of the present invention, the time of the hydrolysis is 2-6h, preferably 3-3.5h.
Using specific hydrolysis temperature and time, facilitate the abundant progress of hydrolysis, improves 2,3-dimercaptosuccinic acid
The yield of salt.
It is described to be acidified gained 2,3-dimercaptosuccinic acid salting liquid in a kind of preferred embodiment of the present invention
To 2,3-dimercaptosuccinic acid, used acidulant includes one of inorganic acid or a variety of, preferably in inorganic acid
It is one or more, further preferably hydrochloric acid and/or sulfuric acid.
In a kind of preferred embodiment of the present invention, the temperature of the acidification is 0-30 DEG C, preferably 10-20 DEG C.
In a kind of preferred embodiment of the present invention, gained 2,3-dimercaptosuccinic acid is recrystallized.
In a kind of preferred embodiment of the present invention, the solvent that the recrystallization uses includes one of alcoholic solvent
Or it is a variety of, preferably include one of methanol, ethyl alcohol and isopropanol or a variety of, further preferably ethyl alcohol.)
In a kind of preferred embodiment of the present invention, decolourized in the recrystallization process using decolorising agent.
In a kind of preferred embodiment of the present invention, the decolorising agent includes active carbon.
The dimercaptosuccinic acid product being prepared using a kind of preparation method of above-mentioned dimercaptosuccinic acid.
Dimercaptosuccinic acid product purity of the present invention is high, at low cost.
A kind of preparation method of above-mentioned dimercaptosuccinic acid is prepared by a kind of preparation method of Dimercaptosuccinate
It after the dimercaptosuccinic acid solution arrived, is neutralized using aqueous slkali, crystallization obtains Dimercaptosuccinate.
The preparation method simple process and low cost of Dimercaptosuccinate of the present invention is suitable for industrialized production and promotes.
A kind of synthetic route of the 2,3- Dimercaptosuccinate of specific embodiment of the present invention is as follows:
In a kind of preferred embodiment of the present invention, the solvent that the dimercaptosuccinic acid solution uses is molten for alcohol
Liquid, preferably methanol and/or ethyl alcohol.
In a kind of preferred embodiment of the present invention, the mass ratio of the dimercaptosuccinic acid and methanol is 1:15-
22。
In a kind of preferred embodiment of the present invention, the mass ratio of the dimercaptosuccinic acid and ethyl alcohol is 1:16-
24。
Using specific solvent, facilitate dimercaptosuccinic acid and sufficiently dissolve, improve and neutralize conversion ratio, improves gained dimercapto
The purity of succinate.
In a kind of preferred embodiment of the present invention, dimercaptosuccinic acid is dissolved by heating in a solvent.
In a kind of preferred embodiment of the present invention, the heating temperature is reflux temperature.
Using the mode of heating for dissolving, facilitates dimercaptosuccinic acid and quickly, sufficiently dissolves,
In a kind of preferred embodiment of the present invention, the aqueous slkali includes in inorganic alkali solution and organic alkali solution
It is one or more, it is preferred to use one of inorganic alkali solution is a variety of, further preferably use carbonate solution or carbonic acid
One of hydrogen salt solution is a variety of, more preferably uses sodium carbonate liquor and/or solution of potassium carbonate.
In a kind of preferred embodiment of the present invention, the mass fraction of the aqueous slkali is 2.0%-20.0%, excellent
It is selected as 3.0%-8.0%.
Using the aqueous slkali of extra fine quality score, can be avoided in not up to and before terminal pH, alkali is precipitated from solution,
Influence the purity of gained Dimercaptosuccinate product.
In a kind of preferred embodiment of the present invention, the temperature of the neutralization is 0 DEG C or more, preferably room temperature -50
℃。
In a kind of preferred embodiment of the present invention, the terminal pH of the neutralization is 6.5-8, preferably 6.5-7.5.
In a kind of preferred embodiment of the present invention, the neutralization carries out under a shielding gas.
In a kind of preferred embodiment of the present invention, the protective gas includes one of nitrogen and inert gas
Or it is a variety of.
In a kind of preferred embodiment of the present invention, it is aged after the crystallization.
In a kind of preferred embodiment of the present invention, the temperature of the ageing is -5.0 to 5.0 DEG C, preferably 0-5
℃。
In a kind of preferred embodiment of the present invention, the time of the ageing is 4-15h, preferably 8-10h.
In a kind of preferred embodiment of the present invention, after the ageing, it is filtered, washed, is dried to obtain dimercapto
Succinate product.
Optionally, after filtering out mother liquor, filter wash cake first is stirred with the Diluted Alcohol of certain moisture content, so as to the carbonic acid that will do not acted on
Sodium is washed out from crystallized product and (is no longer changed with pH value as washing terminal).
Optionally, it is flowed back and is washed with dehydrated alcohol, sufficiently to remove the 2,3-dimercaptosuccinic acid not being neutralized.
Optionally, the drying includes vacuum drying.
Optionally, the temperature of the drying is 60 DEG C or less.
It dries to rewinding after no longer loss of weight, and drying product is sealed rapidly, obtained product is without the crystallization water
2,3- Dimercaptosuccinate.
The Dimercaptosuccinate product being prepared using a kind of preparation method of above-mentioned Dimercaptosuccinate.
Dimercaptosuccinate product purity of the present invention is high, at low cost.
In a kind of preferred embodiment of the present invention, the Dimercaptosuccinate includes sodium dimercaptosuccinate salt
And/or dimercaptosuccinic acid sylvite, preferably include dimercaptosuccinic acid disodium salt and/or dimercaptosuccinic acid di-potassium.
Embodiment 1
A kind of preparation method of dimercaptosuccinic acid, includes the following steps:
1. substitution reaction:
600mL acetone-water mixed solvent (wherein acetone and water are successively put into drying, clean 1000mL reaction flask
Volume ratio be 1:0.8) and 153.1g (content 95.0%, 1.2moL) ehtyl potassium xanthate, stirring and with warming-in-water to 40-
45 DEG C, until it is complete it is molten after be slowly added into bis- bromosuccinic acid of 141g (0.5moL) 2,3-.It finishes, is slowly ramped to 55 DEG C, and continue
3.0h is reacted, and terminal is determined with HPLC method.Reaction solution is slowly cooled to 15 DEG C hereinafter, and standing 2 hours after reaction
Potassium bromide precipitating is precipitated sufficiently, refilters removing.Closed container is placed in when filter vacuum to be concentrated into the 1/3 of original volume then
In it is spare.
2. hydrolysis:
Mass fraction is put into 1000mL reaction flask for 15.0% sodium hydrate aqueous solution 500mL, after stirring and dissolving
45 DEG C -50 DEG C are warming up to, then drops evenly above-mentioned concentration filtrate into bottle under nitrogen protection.It finishes, rises in boiling water bath
Temperature determines reaction end with HPLC method to 85 DEG C of sustained response 3.5h.After reaction, reaction flask is taken out from heating bath, it is cold
It stands overnight to room temperature and naturally.
3. acidification:
The hydrolysis liquid stood overnight is placed in cool bath, temperature is maintained at 15 DEG C, and is slowly added dropwise with stirring
6.0mol/L hydrochloric acid is carefully acidified to pH 1.2-1.5, generates 2,3-dimercaptosuccinic acid crude product precipitating immediately, continues to stir
React 1h.In 10-15 DEG C and vacuum filter after 2h is aged after acidification.Filter cake washed repeatedly with purified water up to no chlorine from
Son detection, being finally cooled to the ethanol washing that 10 DEG C of volume fraction is 95% with 100mL, 2 times (each dosage respectively is
60mL, 40mL), and sufficiently drain.Wet filter cake is placed in a vacuum drying oven and is dried under reduced pressure in 55 DEG C or less to doing, is obtained white
The powdered 2,3-dimercaptosuccinic acid crude product of color.Net weight 57.05g, purity 98.33% (normalization method), yield: 62.26%.
4. purification:
55g crude product is put into round-bottomed bottle, the ethyl alcohol 1200mL that volume fraction is 95% is added, uses warming-in-water under stirring
Make to dissolve.Then 0.25g active carbon, and the 20min that decolourizes that flows back is added, filters while hot, filtrate is slowly cooled to room temperature with stirring,
And overnight.Next day filtering, ethanol washing 3 times that filter cake is 95% with volume fraction (each solvent usage respectively be 40mL,
30mL, 20mL), it is dried under vacuum to after sufficiently draining in 55 DEG C or less dry.It is glossy and with foul smell 2,3- to obtain 48.4 whites
Dimercaptosuccinic acid crystalline powder fusing point: 191.5 DEG C -192.8 DEG C, purity 99.56% (HPLC method).
Elemental analysis result:
5. the concentration and recovery target product from crystalline mother solution:
The refinement mother liquor for taking full batch is placed in water-bath and is concentrated in vacuo to feed liquid and taking-up when muddiness just occurred, is added appropriate
Identical solvent simultaneously is heated to filtering after 0.02g active carbon reflux decoloration 15min is added after clarifying.By filtrate in accordance with the law crystallisation by cooling,
1.4g 2,3-dimercaptosuccinic acid product (two analysis objects) is obtained after filtering, 50-55 DEG C of vacuum drying.Content 99.48%.It is molten
Point: 191.1-192.7 DEG C.Total output 49.8g, with 2,3-, bis- bromosuccinic acid meter, total recovery: 55.27%.
Embodiment 2
Under the technique of embodiment 1, the volume ratio of acetone-water in the mixed solvent acetone and water is 1:0.1；Bis- bromo of 2,3-
The dosage of succinic acid is 169.2g (0.6mol)；Substitution reaction is warming up to 45 DEG C, reacts 6h；With mass fraction be 10.0% it is dilute
The sodium hydrate aqueous solution that mass fraction is 15.0% in hydrochloric acid alternative embodiment 1 makees hydrolysis (nitrogen protection) reagent, water
Solution reaction is warming up to 75 DEG C, reacts 6h；Souring temperature is maintained at 0 DEG C；Other processes and condition are completely the same in embodiment 1.Most
After obtain 2,3-dimercaptosuccinic acid one analyse produce product 57.7g, fusing point: 191.5 DEG C -192.9 DEG C, content 99.60% (HPLC).
Elemental analysis result:
It is concentrated from primary purification mother liquor, decolourizes, obtains two analysis object 1.98g after crystallization, fusing point: 191.1 DEG C -192.7 DEG C,
Content 99.50% (HPLC).One analysis object, two analysis object total output 59.68g, with 2,3-, bis- bromosuccinic acid meter, total recovery:
55.19%.
Embodiment 3
Under the technique of embodiment 1, the volume ratio of acetone-water in the mixed solvent acetone and water is 1:2.3；Bis- bromo of 2,3-
The dosage of succinic acid is 84.6g (0.3mol)；Substitution reaction is warming up to 55 DEG C, reacts 2h；The hydrogen for being 25.0% with mass fraction
The sodium hydrate aqueous solution that mass fraction is 15.0% in aqueous solution of sodium oxide alternative embodiment 1 makees hydrolysis (nitrogen protection)
Reagent, hydrolysis are warming up to 95 DEG C, react 2h；Souring temperature is maintained at 30 DEG C；Other processes and condition are complete in embodiment 1
Unanimously.It finally obtains 2,3-dimercaptosuccinic acid one and analyses produce product 28.86g, fusing point: 191.5 DEG C -192.9 DEG C, content
99.64% (HPLC).
Elemental analysis result:
It is concentrated from primary purification mother liquor, decolourizes, obtains two analysis object 1.05g fusing points after crystallization: 191.1 DEG C -192.7 DEG C,
Content 99.52% (HPLC).One analysis object, two analysis object total output 29.91g, with 2,3-, bis- bromosuccinic acid meter, total recovery:
55.32%.
Embodiment 4
Under the technique of embodiment 1, the volume ratio of acetone-water in the mixed solvent acetone and water is 1:0.4；Bis- bromo of 2,3-
The dosage of succinic acid is 112.8g (0.4mol)；Substitution reaction is warming up to 50 DEG C, reacts 3.5h；It is 35.0% with mass fraction
The sodium hydrate aqueous solution that mass fraction is 15.0% in dilute hydrochloric acid alternative embodiment 1 makees hydrolysis (nitrogen protection) reagent,
Hydrolysis is warming up to 85 DEG C, reacts 3.5h；Souring temperature is maintained at 10 DEG C；Other processes and condition are in embodiment 1 complete one
It causes.It finally obtains 2,3-dimercaptosuccinic acid one and analyses produce product 38.48g, fusing point: 191.5 DEG C -192.8 DEG C, content 99.69%
(HPLC)。
Elemental analysis result:
It is concentrated from primary purification mother liquor, decolourizes, obtains two analysis object 1.43g after crystallization, fusing point: 191.1 DEG C -192.7 DEG C,
Content 99.55% (HPLC).One analysis object, two analysis object total output 39.91g, with 2,3-, bis- bromosuccinic acid meter, total recovery:
55.37%.
Embodiment 5
Under the technique of embodiment 1, the volume ratio of acetone-water in the mixed solvent acetone and water is 1:1.4；With mass fraction
The sodium hydrate aqueous solution for being 15.0% for mass fraction in 20.0% sodium hydrate aqueous solution alternative embodiment 1 makees hydrolysis instead
(nitrogen protection) reagent is answered, hydrolysis is warming up to 90 DEG C, reacts 3h；Souring temperature is maintained at 20 DEG C；Other processes and condition
It is completely the same in embodiment 1.It finally obtains 2,3-dimercaptosuccinic acid one and analyses produce product 48.31g, fusing point: 191.5 DEG C -192.8
DEG C, content 99.72% (HPLC).
Elemental analysis result:
It is concentrated from primary purification mother liquor, decolourizes, obtains two analysis object 1.64g after crystallization, fusing point: 191.1 DEG C -192.7 DEG C,
Content 99.57% (HPLC).One analysis object, two analysis object total output 49.95g, with 2,3-, bis- bromosuccinic acid meter, total recovery:
55.43%.
Comparative example 1
A kind of preparation method of dimercaptosuccinic acid, includes the following steps:
1. the preparation of acetylenedicarboxylic acid disodium:
480mL purified water and 91.6g (2.2mol) sodium hydroxide are first put into reaction flask, are cooled to after stirring to fully dissolved
Room temperature is hereinafter, it is 140.9g (0.5mol) 2,3- dibromosuccinic acid that total amount is added by several times.It finishes, is warming up to 40 DEG C, to feed liquid base
A small amount of insoluble matter is filtered to remove after this clarification.Filtrate is cooled to 10 DEG C or less after 40 DEG C of insulation reaction 3h and is aged 2h then
Filtering, washs filter cake with cold water, until again with methanol washing after pH value is constant, until in cleaning solution without bromide detection.
Then it is dried under vacuum in 60 DEG C or less dry, obtains white crystalline acetylenedicarboxylic acid disodium product (one analysis object) 85.16g, content:
98.04%, yield 72.6%.
Separately the acetylenedicarboxylic acid disodium two of 10% or more recycling analyses object from an analysis object mother liquor.Therefore, total recovery: 79.5-
82.5%
The preparation of 2.2,3- dimercaptosuccinic acid:
Dilute sulfuric acid 114.2g and 85g (0.36mol) acetylenedicarboxylic acid two that mass fraction is 30% is sequentially added in reaction flask
Sodium hydrate finishes, after stir about 15min in it is closed it is good under the conditions of 60.9g (0.78mol) thioacetic acid is slowly added dropwise,
It finishes, is warming up to 58-60 DEG C, and insulation reaction 1.5h adds 228g, the dilute sulfuric acid that mass fraction is 30%, after mixing in proper order
Stirring heating, and 4hr is stirred to react in 90-95 DEG C.Vacuum filter after reactant is cooled to 10-13 DEG C after reaction, and
Filter cake is sufficiently washed with large-scale purification water, until primary with ethanol washing again after sulfate radical-free detection.Wet cake is true in 55-60 DEG C
Sky is dry to doing, and obtains white powder 2,3-dimercaptosuccinic acid crude product 38.9g. content 98.45%.Addition, hydrolytic process
Total recovery: 51.71%
3. recrystallization:
33.5g. crude product is put into the ethyl alcohol that 700mL volume fraction is 95%, stir lower water-bath be heated to it is complete it is molten after,
0.15g active carbon and the flowing back 10min that decolourizes is added to filter while hot.Filtrate is filtered after being cooled to room temperature hereinafter, being aged 2h again.Filter cake
It is dried under vacuum to then at 60 DEG C or less dry after cold ethanol washing through being 95% with volume fraction is light to filter liquor, obtains
The powdered 2,3- dimercaptosuccinic acid product of 27.09g white group.Content: 99.22%, fusing point: 191.1 DEG C -192.7 DEG C.
Elemental analysis result:
Theoretical value: C.26.37% H.3.32% O.35.12%
Measured value: C.26.35% H.3.31% O.35.14%
Crystallisation by cooling, filtration drying recycle 2,3- dimercaptosuccinic acid crude product to primary purification mother liquor again after being concentrated in vacuo
This crude product of 5.41g. is re-refined once according to the above method, obtains qualified finished product 2.85g. purification yield: 89.37%.With 2,3- bis-
Dibromo-succinic acid meter, three step total recoverys: 52.47%
Comparative example 2
A kind of preparation method of dimercaptosuccinic acid (imitative 4,550,193 embodiment 1 of US and 5 method of example), including walk as follows
It is rapid:
In the reaction flask for being equipped with condenser, magnetic stirring apparatus and PH meter, 140ml. distilled water and 11.4g are successively put into
(0.1mol) acetylenedicarboxylic acid, 5 DEG C of are cooled to after stirring and dissolving and that reaction solution is adjusted to pH=3 with soda lye is latter
Secondary addition 31.6g (0.2mol.) sodium thiosulfate, is stirred to react 20hr under equality of temperature, therebetween, by the way that the dilute salt of 1mol/L is added dropwise
Acid is to maintain the pH value of reaction solution between 2.8-3.3.When reaction reaches terminal, the concentration of thiosulfate anion is connect in reaction solution
It is bordering on zero (iodimetry instruction).A large amount of water is removed with freeze-drying after reaction solution is adjusted to pH=7 with lye, is obtained
The tetrasodium salt of bis- sulfosuccinate of 2,3- and the mixture 48.7g of sodium chloride.
The mixture of above-mentioned tetrasodium salt is added in the mixed liquor that 200mL methanol and 50mL concentration are 6mol/L hydrochloric acid,
In being heated to 70 DEG C in water-bath and be cooled to room temperature hereinafter, being filtered to remove inorganic salts after reacting 2h.Filtrate after being concentrated in vacuo again
Cooling, filtering and vacuum drying, obtain the flaxen paste of 6.7g --- 2,3-dimercaptosuccinic acid crude product, content:
85.65%.Pure yield: 31.8%.
By above-mentioned crude product through obtaining 4.56g white powder object with recrystallizing methanol 2 times --- 2,3- dimercapto fourths
Diacid.Fusing point: 190.8 DEG C -192.6 DEG C, content: 98.75%.In terms of acetylenedicarboxylic acid, total recovery: 24.99%.
The comparison of each embodiment and comparative example is, it can be seen that use the preparation of dimercaptosuccinic acid of the present invention through the invention
Method prepares dimercaptosuccinic acid product, products obtained therefrom purity and yield obviously higher than comparative example method is used, and furthermore can also
Elimination reaction process is saved, with the addition reaction operation that mild substitution reaction substitution is fierce and dangerous, and with ethoxy-dithioformic acid
Salt substitutes thioacetic acid as sulfhydrylization reagent, so that production environment is greatly improved.
Embodiment 6
The resulting 2,3-dimercaptosuccinic acid of 1 method of Example refines sample 45.3g (0.25mol) in reaction flask,
Dehydrated alcohol 1150mL is added, stirs lower heating water bath and adds boiling, and is observed after the 10min that flows back, static 15min whether there is or not molten object,
If any because being filtered to remove.Then water-bath is removed, and is cooled to 50 DEG C, in nitrogen strength protection and continues to drop evenly under stirring
Mass fraction is 3% sodium carbonate liquor, and being carefully neutralized to pH is 7.5, continues to stir 10min, and repetition measurement 3 times, until pH
Until 7.4.It neutralizes and finishes, continue to stir evenly speed being cooled to 5 DEG C, make to crystallize abundant precipitation, be subsequently placed in refrigerating chamber standing
Overnight.Next day vacuum suction filter, and mother liquor is sufficiently drained, first 3 (40mL+ of filter cake are washed with the 70% alcohol 95 mL for being cooled to 5 DEG C in advance
30mL+25mL), until eluate pH value is constant.Filter cake is poured into reaction flask after draining, 200mL dehydrated alcohol is added,
It is extremely boiled, and the 10min that flows back, is filtered after being cooled to room temperature, filter cake washes one through being stirred with 50ml dehydrated alcohol with heating water bath under stirring
It is secondary, in being placed with P after draining2O5It is dried under vacuum to dry for 60 DEG C or less in the drier of desiccant, obtains pure white color 2,3- dimercapto fourth
Diacid Disodium salt crystal product 45.4g, liquid phase purity 99.63%, yield: 80.71%.
Elemental analysis:
C4H4Na2O4S2Calculated value: O.28.30 S.28.35 C.21.24 H.1.78 Na.20.33
C4H4Na2O4S2Assay value: O.28.32 S.28.34 C.21.23 H.1.78 Na.20.32
Remarks: will be the anhydride after sufficiently drying for the test sample of elemental analysis, same as below.
From concentration and recovery in sodium salt crystal mother liquor and purified salt:
Taking-up when being concentrated in vacuo to the 1/3 of original volume in 80 DEG C of water-baths after the filtrated stock of full batch is merged, and in
Dehydrated alcohol is dropped evenly under stirring, is precipitated until crystallization is obvious, then be cooled to 3-5 DEG C and be aged vacuum filter after 4h.Filter cake
Through being washed several times with the cold ethyl alcohol of 75% under equality of temperature, until pH value is constant.Wet crystallization and 50 DEG C or less vacuum drying
To doing, pure white color sodium salt product 4.40g. mono- analysis object, the two analysis object total output 49.8g of purity 99.57% are obtained, with 2,3-, bis- mercapto
Base succinic acid meter, total recovery: 88.40%.
Embodiment 7
1150mL dehydrated alcohol in embodiment 6 is replaced with into 1025mL methanol, neutralization temperature is room temperature, and neutralization terminal is pH
It is 7.0, crystallisation by cooling temperature is 0 DEG C, and digestion time 8h, subsequent filter, washing and drying condition are constant, and it is clean to obtain 44.9g
White 2,3- dimercaptosuccinic acid Disodium salt crystal product.Liquid phase purity 99.61%, yield: 79.85%.
Crystalline mother solution is handled by 6 method of embodiment, obtains 4.32g, obtains purity 99.60% (two analysis objects).One analysis object, two
Object total output 49.22g. is analysed in terms of 2,3-dimercaptosuccinic acid, total recovery: 86.90%.
Elemental analysis:
C4H4Na2O4S2Calculated value: O.28.30 S.28.35 C.21.24 H.1.78 Na.20.33
C4H4Na2O4S2Assay value: O.28.31 S.28.33 C.21.23 H.1.78 Na.20.32
Embodiment 8
Sodium carbonate in embodiment 6 is replaced with into potassium carbonate (mass fraction 8%), neutralization temperature is room temperature, is neutralized eventually
It is 6.5 that point, which is pH, and crystallisation by cooling temperature is -5 DEG C, digestion time 10h, other preparation conditions are constant, obtain white dimercapto
Potassium succinate crystalline solid 52.0g, liquid phase purity: 99.70%, yield: 80.94%.
Elemental analysis:
C4H4K2O4S2Calculated value: C.18.59 H.1.56 O.24.77 S.24.81 K.30.26
C4H4K2O4S2Assay value: C.18.57 H.1.56 O.24.75 S.24.83 K.30.29
Crystalline mother solution is handled by 6 method of embodiment, obtains 4.74g, purity 99.61%. mono- is obtained and analyses object, two analysis object total yields
49.64g. is measured in terms of 2,3-dimercaptosuccinic acid, total recovery: 88.26%.
Although illustrate and describing the present invention with specific embodiment, it will be appreciated that the above various embodiments is only used
To illustrate technical solution of the present invention, rather than its limitations；Those skilled in the art should understand that: without departing substantially from this hair
It in the case where bright spirit and scope, is possible to modify the technical solutions described in the foregoing embodiments, or to wherein
Some or all of technical characteristic is equivalently replaced；And these are modified or replaceed, and do not make the essence of corresponding technical solution
It departs from the scope of the technical solutions of the embodiments of the present invention；It is, therefore, intended that in the following claims including belonging to the present invention
All these substitutions and modifications in range.
Claims (61)
1. a kind of preparation method of dimercaptosuccinic acid, which is characterized in that by ethyl xanthate and 2, bis- bromosuccinic acid of 3-
It is reacted, obtains 2,3- auligen ester -1, 4- succinic acid；By gained 2,3- auligen ester -1,4- fourth two
2,3- Dimercaptosuccinate solution is obtained after sour water solution；It is acidified gained 2,3- Dimercaptosuccinate solution to obtain 2,3- bis-
Dimercaptosuccinic acid.
2. a kind of preparation method of dimercaptosuccinic acid according to claim 1, which is characterized in that the ethoxy-dithioformic acid
Salt includes one of ethoxy-dithioformic acid metal salt or a variety of.
3. a kind of preparation method of dimercaptosuccinic acid according to claim 2, which is characterized in that the ethoxy-dithioformic acid
Salt includes one of ethoxy-dithioformic acid alkali metal salt or a variety of.
4. a kind of preparation method of dimercaptosuccinic acid according to claim 3, which is characterized in that the ethoxy-dithioformic acid
Salt includes ethoxy-dithioformic acid sodium salt and/or ethoxy-dithioformic acid sylvite.
5. a kind of preparation method of dimercaptosuccinic acid according to claim 1, which is characterized in that 2,3-, bis- bromo
The molar ratio of succinic acid and ethyl xanthate is 1:2-4.
6. a kind of preparation method of dimercaptosuccinic acid according to claim 5, which is characterized in that 2,3-, bis- bromo
The molar ratio of succinic acid and ethyl xanthate is 1:2.4-3.
7. a kind of preparation method of dimercaptosuccinic acid according to claim 1, which is characterized in that described by ethyl xanthan
Hydrochlorate react the solvent used with bis- bromosuccinic acid of 2,3- as the mixed solution of acetone and water.
8. a kind of preparation method of dimercaptosuccinic acid according to claim 7, which is characterized in that the acetone and water
The volume ratio of acetone and water is 1:0.1-2.3 in mixed solution.
9. a kind of preparation method of dimercaptosuccinic acid according to claim 8, which is characterized in that the acetone and water
The volume ratio of acetone and water is 1:0.4-1.4 in mixed solution.
10. a kind of preparation method of dimercaptosuccinic acid according to claim 7, which is characterized in that described by ethyl Huang
The temperature that ortho acid salt is reacted with bis- bromosuccinic acid of 2,3- is 45-55 DEG C.
11. a kind of preparation method of dimercaptosuccinic acid according to claim 10, which is characterized in that described by ethyl Huang
The temperature that ortho acid salt is reacted with bis- bromosuccinic acid of 2,3- is 50-55 DEG C.
12. a kind of preparation method of dimercaptosuccinic acid according to claim 7, which is characterized in that described by ethyl Huang
The time that ortho acid salt is reacted with bis- bromosuccinic acid of 2,3- is 2-6h.
13. a kind of preparation method of dimercaptosuccinic acid according to claim 12, which is characterized in that described by ethyl Huang
The time that ortho acid salt is reacted with bis- bromosuccinic acid of 2,3- is 3-3.5h.
14. a kind of preparation method of dimercaptosuccinic acid according to claim 1, which is characterized in that by gained 2,3- bis-
Ethoxy-dithioformic acid ester -1, 4- succinic acid is hydrolyzed with aqueous slkali and reacts, and obtains 2,3-dimercaptosuccinic acid salting liquid.
15. a kind of preparation method of dimercaptosuccinic acid according to claim 14, which is characterized in that the aqueous slkali packet
Include one of inorganic base aqueous solution or a variety of.
16. a kind of preparation method of dimercaptosuccinic acid according to claim 15, which is characterized in that the aqueous slkali is
Sodium hydrate aqueous solution.
17. a kind of preparation method of dimercaptosuccinic acid according to claim 14, which is characterized in that the hydrolysis
It carries out under a shielding gas.
18. a kind of preparation method of dimercaptosuccinic acid according to claim 17, which is characterized in that the protective gas
For nitrogen.
19. a kind of preparation method of dimercaptosuccinic acid according to claim 14, which is characterized in that the aqueous slkali
Mass fraction is 10%-25%.
20. a kind of preparation method of dimercaptosuccinic acid according to claim 19, which is characterized in that the aqueous slkali
Mass fraction is 15%-20%.
21. a kind of preparation method of dimercaptosuccinic acid according to claim 14, which is characterized in that 2, the 3- diethyl
The molar ratio of base xanthate -1,4- succinic acid and alkali is 1:2-6.
22. a kind of preparation method of dimercaptosuccinic acid according to claim 14, which is characterized in that the hydrolysis
Temperature be 75-95 DEG C.
23. a kind of preparation method of dimercaptosuccinic acid according to claim 22, which is characterized in that the hydrolysis
Temperature be 85-90 DEG C.
24. a kind of preparation method of dimercaptosuccinic acid according to claim 14, which is characterized in that the hydrolysis
Time be 2-6h.
25. a kind of preparation method of dimercaptosuccinic acid according to claim 24, which is characterized in that the hydrolysis
Time be 3-3.5h.
26. a kind of preparation method of dimercaptosuccinic acid according to claim 1, which is characterized in that it is described by gained 2,
3- Dimercaptosuccinate solution is acidified to obtain 2,3-dimercaptosuccinic acid, and used acidulant includes one of inorganic acid
Or it is a variety of.
27. a kind of preparation method of dimercaptosuccinic acid according to claim 26, which is characterized in that used acidification
Agent is one of inorganic acid or a variety of.
28. a kind of preparation method of dimercaptosuccinic acid according to claim 27, which is characterized in that used acidification
Agent is hydrochloric acid and/or sulfuric acid.
29. a kind of preparation method of dimercaptosuccinic acid according to claim 26, which is characterized in that the temperature of the acidification
Degree is 0-30 DEG C.
30. a kind of preparation method of dimercaptosuccinic acid according to claim 29, which is characterized in that the temperature of the acidification
Degree is 10-20 DEG C.
31. a kind of preparation method of dimercaptosuccinic acid according to claim 1, which is characterized in that by gained 2,3- bis-
Dimercaptosuccinic acid is recrystallized.
32. a kind of preparation method of dimercaptosuccinic acid according to claim 31, which is characterized in that the recrystallization is adopted
Solvent includes one of alcoholic solvent or a variety of.
33. a kind of preparation method of dimercaptosuccinic acid according to claim 32, which is characterized in that the recrystallization is adopted
Solvent includes one of methanol, ethyl alcohol and isopropanol or a variety of.
34. a kind of preparation method of dimercaptosuccinic acid according to claim 33, which is characterized in that the recrystallization is adopted
Solvent is ethyl alcohol.
35. a kind of preparation method of dimercaptosuccinic acid according to claim 31, which is characterized in that described to recrystallize
It is decolourized in journey using decolorising agent.
36. a kind of preparation method of dimercaptosuccinic acid according to claim 35, which is characterized in that the decolorising agent packet
Include active carbon.
37. a kind of preparation method of Dimercaptosuccinate, which is characterized in that by any described one kind two of claim 1-36
It after dimercaptosuccinic acid solution is prepared in the preparation method of dimercaptosuccinic acid, is neutralized using aqueous slkali, crystallization obtains dimercapto
Succinate.
38. a kind of preparation method of Dimercaptosuccinate according to claim 37, which is characterized in that the dimercapto
The solvent that succinic acid solution uses is alcoholic solution.
39. a kind of preparation method of Dimercaptosuccinate according to claim 38, which is characterized in that the dimercapto
The solvent that succinic acid solution uses is methanol and/or ethyl alcohol.
40. a kind of preparation method of Dimercaptosuccinate according to claim 39, which is characterized in that the dimercapto
The mass ratio of succinic acid and methanol is 1:15-22.
41. a kind of preparation method of Dimercaptosuccinate according to claim 39, which is characterized in that the dimercapto
The mass ratio of succinic acid and ethyl alcohol is 1:16-24.
42. a kind of preparation method of Dimercaptosuccinate according to claim 37, which is characterized in that by dimercapto fourth
Diacid dissolves by heating in a solvent.
43. a kind of preparation method of Dimercaptosuccinate according to claim 42, which is characterized in that the heating temperature
Degree is reflux temperature.
44. a kind of preparation method of Dimercaptosuccinate according to claim 37, which is characterized in that the aqueous slkali
Including one of inorganic alkali solution and organic alkali solution or a variety of.
45. a kind of preparation method of Dimercaptosuccinate according to claim 44, which is characterized in that the aqueous slkali
Including one of inorganic alkali solution or a variety of.
46. a kind of preparation method of Dimercaptosuccinate according to claim 45, which is characterized in that the aqueous slkali
Including one of carbonate solution or bicarbonate solution or a variety of.
47. a kind of preparation method of Dimercaptosuccinate according to claim 46, which is characterized in that the aqueous slkali
For sodium carbonate liquor and/or solution of potassium carbonate.
48. a kind of preparation method of Dimercaptosuccinate according to claim 47, which is characterized in that the sodium carbonate
Mass fraction be 2.0%-20.0%.
49. a kind of preparation method of Dimercaptosuccinate according to claim 48, which is characterized in that the sodium carbonate
Mass fraction be 3.0%-8.0%.
50. a kind of preparation method of Dimercaptosuccinate according to claim 37, which is characterized in that the neutralization
Temperature is 0 DEG C or more.
51. a kind of preparation method of Dimercaptosuccinate according to claim 50, which is characterized in that the neutralization
Temperature is -50 DEG C of room temperature.
52. a kind of preparation method of Dimercaptosuccinate according to claim 37, which is characterized in that the neutralization
Terminal pH is 6.5-8.
53. a kind of preparation method of Dimercaptosuccinate according to claim 52, which is characterized in that the neutralization
Terminal pH is 6.5-7.5.
54. a kind of preparation method of Dimercaptosuccinate according to claim 37, which is characterized in that in described and
It is carried out under protective gas.
55. a kind of preparation method of Dimercaptosuccinate according to claim 54, which is characterized in that the protection gas
Body includes nitrogen.
56. a kind of preparation method of Dimercaptosuccinate according to claim 37, which is characterized in that after the crystallization
It is aged.
57. a kind of preparation method of Dimercaptosuccinate according to claim 56, which is characterized in that the ageing
Temperature is -5.0 to 5.0 DEG C.
58. a kind of preparation method of Dimercaptosuccinate according to claim 57, which is characterized in that the ageing
Temperature is 0-5 DEG C.
59. a kind of preparation method of Dimercaptosuccinate according to claim 56, which is characterized in that the ageing
Time is 4-15h.
60. a kind of preparation method of Dimercaptosuccinate according to claim 59, which is characterized in that the ageing
Time is 8-10h.
61. a kind of preparation method of Dimercaptosuccinate according to claim 56, which is characterized in that the ageing
Afterwards, it is filtered, washed, is dried to obtain Dimercaptosuccinate product.
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| US4208398A (en) * | 1973-04-23 | 1980-06-17 | Hoffman-La Roche Inc. | Technetium-labeled complexes, production and use thereof |
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| US4208398A (en) * | 1973-04-23 | 1980-06-17 | Hoffman-La Roche Inc. | Technetium-labeled complexes, production and use thereof |
| CN102716719A (en) * | 2012-07-04 | 2012-10-10 | 汪志友 | Heavy metal adsorbent for extracorporeal perfusion method and preparation method of heavy metal absorbent |
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