CN1569829A - Method for preparing 2-amino-4-methylthio-(s-oxo-s-imino)-butyric acid phosphate or succinate - Google Patents
Method for preparing 2-amino-4-methylthio-(s-oxo-s-imino)-butyric acid phosphate or succinate Download PDFInfo
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- CN1569829A CN1569829A CN 200410029882 CN200410029882A CN1569829A CN 1569829 A CN1569829 A CN 1569829A CN 200410029882 CN200410029882 CN 200410029882 CN 200410029882 A CN200410029882 A CN 200410029882A CN 1569829 A CN1569829 A CN 1569829A
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- butyric acid
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Abstract
The invention relates to a method for preparing 2-amino-4-methylthio-(S-oxo-S-imino)-butyric acid phosphate or succinate that are used in agriculture as a fodder supplement for agricultural animals and poultry for elevating their productivity. 2-amino-4-methylthio-(S-oxo-S-imino)-butyric acid sulfate is subjected for interaction with calcium phosphates taken in the equimolar ratio of components to prepare 2-amino-4-methylthio-(S-oxo-S-imino)-butyric acid phosphate. Or by interaction with calcium hydroxide, 2-amino-4-methylthio-(S-oxo-S-imino)-butyric acid sulfate is transformed to 2-amino-4-methylthio-(S-oxo-S-imino), and the latter reacts with orthophosphate. 2-amino-4-methylthio-(S-oxo-S-imino)-butyric acid sulfate is subjected for interaction with calcium succinate taken in the equimolar ratio of components to prepare 2-amino-4-methylthio-(S-oxo-S-imino)-butyric acid succinate .
Description
Technical field:
The invention belongs to the organic chemistry category, specifically, promptly the 2-of butyric acid amino-4-methylthio group-(S-oxygen-S-imino-) [2-amino-4-(methyl sulphonyl imido acid fat)-butane acid-(JUPAC)] phosphoric acid salt or succinate is synthetic.They are used for agricultural, as the fodder additives of farming animals and poultry, are intended to improve its ratio defective product.Its effect (mechanism) is based on the metabolism of activator matter, thereby the immunizing power of enhancing (animal) body is accelerated its speed of growth, puts on weight, and improves its immunity, and feed is absorbed by farming animals and poultry more fully.
Background technology:
The preparation method of 2-amino-4-methylthio group-(S-oxygen-S-imino-) inorganic salt, organic salt, amide, an alkali metal salt and the alkaline earth metal salt of existing known butyric acid.These salts are produced with the interaction of corresponding acids or metal hydroxides by 2-amino-4-methylthio group-(S-oxygen-S-imino-) aqueous solution of butyric acid.
The phosphatic example of producing: concentration is 50 milliliters of 10% phosphoric acid, inserts 2-amino-4-methylthio group-(the S-oxygen-S-imino-) of the butyric acid of 9 grams.Under vacuum, 35 ℃, make solution concentration, up to obtaining throw out.Throw out is cooled to 5 ℃, makes its crystallization, products therefrom is filtered quiet.(No. 3295949 patent 71-2.7 class of the U.S. 1967).
The weak point of this method is that the finished product rate is low.When the 2-of butyric acid amino-4-methylthio group-(S-oxygen-S-imino-) aqueous solution and concentration are 10% phosphoric acid when interacting, hydrolytic action can appear, its as a result methylsulfonyl imino-family separate, product damages.In addition, when dewatering with distillation method, portioned product can take place damage phenomenon, thereby reduce the yield rate of special product.
The preparation method of 2-amino-4-methylthio group-(the S-oxygen-S-imino-) of existing known butyric acid: being under 60-65 ℃ the condition in temperature, in the water medium, is that 30% hydrogen peroxide makes the methionine(Met) oxidation with excessive, concentration.Gained methionine sulphoxide and sodiumazide are under 25-50 ℃ the condition in temperature in the oleum medium of 98% sulfuric acid and 20%, produce to interact, and can obtain 2-amino-4-methylthio group-(S-oxygen-S-imino-) vitriol of butyric acid thus; Reaction mixture is placed on ice,, the aqueous solution is passed contain the adsorption tower (post) of polyethylene Phenylsulfonic acid type ion exchange resin with the dilution of 4 liters water.Use 12 liters water rinse resin afterwards, to pH value be 6-7, again with 2 normal oxyammonia standardized solution flushings, so that from adsorbent, extract special product.The major portion of product folds from 800 milliliters elutant when pH value ≈ 7.By distillation and under vacuum and 50-60 ℃ of temperature, it is dried subsequently, can get yield rate and be 87.6% product.When pH value is 8.5-11, from 240 milliliters of elutants subsequently, fold the rest part of product, yield rate is 7.1%.Total yield rate of the 2-amino-4-methylthio group of butyric acid-(S-oxygen-S-imino-) is 94.7%.(No. 3607928 patent C07C101/00 of the U.S. 1971).
Although the yield rate that special product folds is enough high, this method of folding can run into a series of substantive obstacles in technical scale, that is:
1. must use the solution of utmost point dilution; Owing to fluming water solution causes extra energy expenditure;
2. form the waste water that needs purification in a large number;
3. for making yield rate reach 94.7%, folding of product need be divided into 2 steps;
4. ion exchange resin is short work-ing life;
5. the regeneration frequency height of adsorption tower (post);
6. need several adsorption towers (post) in the full scale plant.
According to Patent data, from methionine(Met), the phosphatic synthetic following chemical step that comprises of the 2-of butyric acid amino-4-methylthio group-(S-oxygen-S-imino-):
1, by in water medium, using the method for hydrogen peroxide oxidation methionine(Met), produces methionine sulphoxide.
2,2-amino-4-methylthio group-(S-oxygen-S-imino-) vitriol of butyric acid is produced in the interaction of methionine sulphoxide and sodiumazide in the sulfuric acid of high density and oleum medium.
3, produce 2-amino-4-methylthio group-(the S-oxygen-S-imino-) of butyric acid by the interaction of vitriol and alkali (alkali).
4,2-amino-4-methylthio group-(S-oxygen-S-imino-) phosphoric acid salt of butyric acid is produced in the interaction of the 2-of butyric acid amino-4-methylthio group-(S-oxygen-S-imino-) and phosphoric acid.
Summary of the invention:
The objective of the invention is to develop yield rate high, better 2-amino-4-methylthio group-(S-oxygen-S-imino-) phosphoric acid salt of butyric acid or the preparation method of succinate.
The present invention is achieved by adopting following technical proposals:
Use the hydrogen peroxide oxidation methionine(Met), formed methionine sulphoxide and sodiumazide produce in the sulfuric acid of high density and oleum medium subsequently and interact, and can get 2-amino-4-methylthio group-(S-oxygen-S-imino-) vitriol of butyric acid thus; In waiting mol ratio to add calcium phosphate or succinate calcium, its result forms 2-amino-4-methylthio group-(S-oxygen-S-imino-) phosphoric acid salt or succinate finished product calibration amount, that be easy to the butyric acid that folds with aqueous solution form to the 2-of butyric acid amino-4-methylthio group-(S-oxygen-S-imino-) vitriol aqueous suspensions.In fact calcium sulfate be insoluble to reaction medium, can be used as the raw material of material of construction after it is filtered.
2-amino-4-methylthio group-(S-oxygen-S-imino-) in order to produce butyric acid adds calcium hydroxide in its vitriol aqueous suspensions, be 7-7.5 up to PH; Stir aqueous suspensions,,, throw out is dried the filtrate evaporate to dryness with its filtration.Available in case of necessity alcohol or Virahol cleaning products.The simulator of employing standard is dried product as vacuum-rake formula or spraying type moisture eliminator.
2-amino-4-the methylthio group of the butyric acid of according to said method producing-(S-oxygen-S-imino-) can be used alone as special product, also can be used as and further produces its esters, comprises work in-process such as sodium salt, sylvite, calcium salt.
Produce phosphatic inventor's suggestion from 2-amino-4-methylthio group-(the S-oxygen-S-imino-) of butyric acid, the interaction of acids should be carried out with solid or paste form; 2-amino-4-methylthio group-(the S-oxygen-S-imino-) of crystalline butyric acid is stirred with just anhydrous-phosphoric acid,, can get the product of quantitative yield rate up to forming the shot powder.
The high density of the 2-amino-4-methylthio group of crystalline butyric acid-(S-oxygen-S-imino-) and 60-100% just-phosphoric acid produces and interacts, and forms the paste reactant; Stir the paste reactant, in temperature be under 65-70 ℃ the condition with its oven dry, grind afterwards.The finished product rate is 98%.
Embodiment:
The present invention is further illustrated below in conjunction with embodiment.
Producing of the 2-amino-4-methylthio group of butyric acid-(S-oxygen-S-imino-) vitriol.
To be heated to 50 ℃ by the suspension that the methionine(Met) and 92 milliliters the water of 150 grams are formed, and in stirring, allocate 85 ml concns into and be 36% superoxol, action is very fast, and the temperature of mixture must not be above 55 ℃; Allocate into finish after, make reaction mixture be in this temperature 1 hour, make it be cooled to 20-25 ℃ afterwards; Be the formed paste of oven dry under 75-80 ℃ the condition in temperature, can get the methionine sulphoxides of 165 grams.
By 432 gram concentration is that 97% sulfuric acid and 432 gram concentration are the mixture that 20% oleum is formed, is under 40-45 ℃ the condition in temperature, it carried out part stir on one side, insert 165 methionine sulphoxides that restrain on one side; Reaction vessel washes with nitrogen, under 40 ℃ of temperature, allocates the sodiumazide of 67.5 grams within 3 hours into.Joined after the sodiumazide, reaction mixture was placed 40-45 ℃ of temperature following 1 hour, be cooled to 20-25 ℃ afterwards, poured out 350 milliliters water, do not made temperature surpass 50 ℃ while stir; The gained mixture is cooled to 10-15 ℃, inserts 1 liter ethanol again to it; The suspension that will form under 10-15 ℃ of temperature was placed several hours, filtered afterwards.Throw out on the strainer can get the moist throw out of 365 grams with cold water (2 * 50 milliliters) flushing, includes 2-amino-4-methylthio group-(S-oxygen-S-imino-) vitriol of 245 gram butyric acid; Make products therefrom in 500 milliliters water, become suspensoid, be no more than in temperature under 35-40 ℃ the condition, while stir the calcium hydroxides that add 70 grams, to pH value be 7.0-7.5; Suspension was stirred 1 hour, filter afterwards, water flushing calcium sulfate concentrates filtrate under vacuum, with the throw out oven dry, can get 2-amino-4-methylthio group-(the S-oxygen-S-imino-) of the butyric acid of 149.5 grams, and the content of its essential substance is about 94%.Calculate with original methionine(Met) in theory, its yield rate is 71.5%.
2-amino-4-the methylthio group of butyric acid-(S-oxygen-S-imino-) phosphatic producing.
Be used to stir and grind 2-amino-4-methylthio group-(the S-oxygen-S-imino-) of putting into the crystalline butyric acid of 96 grams in the agitator of drying composite, stir on one side and insert the 49 just anhydrous-phosphoric acid that restrain.Be to stir the mixture under 40-45 ℃ the condition in temperature,, can obtain 2-amino-4-methylthio group-(S-oxygen-S-imino-) phosphoric acid salt of 145 gram butyric acid up to forming the shot powder.2-amino-4-methylthio group-(S-oxygen-S-imino-) with butyric acid calculates, and the yield rate of product is 100% (being quantitative).
2-amino-4-the methylthio group of example 2. butyric acid-(S-oxygen-S-imino-) phosphatic producing.
Put into 2-amino-4-methylthio group-(the S-oxygen-S-imino-) of crystalline butyric acid of 96 grams in the agitator, stir on one side insert 49 restrain concentration be 60% just-phosphate aqueous solution; Formed paste was stirred 10-15 minute, under 65-70 ℃ temperature, dry, its grinding.Can obtain 2-amino-4-methylthio group-(S-oxygen-S-imino-) phosphoric acid salt of 142.5 gram butyric acid.2-amino-4-methylthio group-(S-oxygen-S-imino-) with the primary butyric acid calculates in theory, and yield rate is 98%.
2-amino-4-the methylthio group of butyric acid-(S-oxygen-S-imino-) phosphatic producing.
While stirring, the vitriol aqueous suspensions inserts the 13.4 hydrogenation raw calcium phosphate hydrates (hydration tricalcium orthophosphate) that restrain to 2-amino-4-methylthio group-(the S-oxygen-S-imino-) that contains 27.3 gram butyric acid; Mixture was placed under the 45-50 ℃ of temperature 30-60 minute, filter afterwards quiet, concentrate and oven dry, can get 2-amino-4-methylthio group-(S-oxygen-S imino-) phosphoric acid salt of the butyric acid of 26 grams.2-amino-4-methylthio group-(S-oxygen-S-imino-) vitriol with butyric acid calculates in theory, and the yield rate of product is 95%.
Producing of the 2-amino-4-methylthio group of example 4. butyric acid-(S-oxygen-S-imino-) succinate.
2-amino-4-methylthio group-(S-oxygen-S-imino-) to the butyric acid that contains 7.1 grams inserts the 4 succinate calcium that restrain while the vitriol aqueous suspensions stirs; Mixture was placed under the 40-45 ℃ of temperature 30-60 minute, filter afterwards, dewater, dry, can get 2-amino-4-methylthio group-(S-oxygen-S-imino-) succinate of the butyric acid of 7.7 grams.2-amino-4-methylthio group-(S-oxygen-S-imino-) vitriol with butyric acid calculates, and the yield rate of product is 100% (quantitative).
Producing of the 2-amino-4-methylthio group of example 5. butyric acid-(S-oxygen-S-imino-) succinate.
2-amino-4-methylthio group-(the S-oxygen-S-imino-) of 45 butyric acid that restrain is dissolved in 85 milliliters water; Solution is removed by filter impurity, while stir the Succinic Acid that inserts 30 grams to gained filtrate; With mixture heating up till the Succinic Acid dissolving; It is concentrated, under 60-65 ℃ temperature, make afterwards to concentrate back residuum drying, can get 2-amino-4-methylthio group-(S-oxygen-S-imino-) succinate of the butyric acid of 72 grams.2-amino-4-methylthio group-(S-oxygen-S-imino-) with butyric acid calculates in theory, and the finished product rate is 97%.
The advantage of the preparation method of the 2-amino-4-methylthio group of butyric acid of the present invention-(S-oxygen-S-imino-) phosphoric acid salt or succinate is:
For industrial purposes, this is that 2-amino-4-methylthio group-(the S-oxygen-S-imino-) of a feasible butyric acid folds method, can remove the purification work of a large amount of waste water from.
2. the calcium sulfate that processing waste can be used for industrial purposes is as the raw material of making material of construction.
3. can reduce the chemical step that salt is produced in the process to be adopted.Replace (original) four chemical steps, the process of producing of this method only needs three chemical steps: the step of producing that folds step and its class of the 2-amino-4-methylthio group of butyric acid-(S-oxygen-S-imino-) unites two into one.
Claims (2)
1, a kind of 2-of butyric acid amino-4-methylthio group-(S-oxygen-S-imino-) phosphoric acid salt or succinate preparation method, it is characterized in that: the 2-amino-4-methylthio group of butyric acid-(S-oxygen-S-imino-) vitriol produces in equimolar ratio and calcium phosphate and interacts, to produce phosphoric acid salt; Or in equimolar ratio and the interaction of succinate calcium, to produce succinate.
2, the 2-of butyric acid according to claim 1 amino-4-methylthio group-(S-oxygen-S-imino-) phosphoric acid salt or succinate preparation method is characterized in that: the high density of using the 2-amino-4-methylthio group (S-oxygen-S-imino-) of crystalline butyric acid and 60-100% just-phosphoric acid.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RU2003109462 | 2003-04-04 | ||
| RU2003109462/04A RU2232752C1 (en) | 2003-04-04 | 2003-04-04 | Method for preparing 2-amino-4-methylthio-(s-oxo-s-imino)-butyric acid phosphate or succinate |
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| Publication Number | Publication Date |
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| CN1569829A true CN1569829A (en) | 2005-01-26 |
| CN100534980C CN100534980C (en) | 2009-09-02 |
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| CNB2004100298820A Expired - Fee Related CN100534980C (en) | 2003-04-04 | 2004-03-31 | Method for preparing 2-amino-4-methylthio-(s-oxo-s-imino)-butyric acid phosphate or succinate |
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| RU (1) | RU2232752C1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| BRPI1014528A2 (en) * | 2009-03-18 | 2016-04-05 | Olatec Ind Llc | compounds for treating inflammation and pain |
| RU2730533C1 (en) * | 2019-10-23 | 2020-08-24 | Федеральное казенное предприятие "Государственный научно-исследовательский институт химических продуктов" (ФКП "ГосНИИХП") | Method of producing methionine sulphoximine or phosphoric acid salt thereof |
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- 2003-04-04 RU RU2003109462/04A patent/RU2232752C1/en not_active IP Right Cessation
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- 2004-03-31 CN CNB2004100298820A patent/CN100534980C/en not_active Expired - Fee Related
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| CN100534980C (en) | 2009-09-02 |
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Granted publication date: 20090902 Termination date: 20100331 |