CN103242183A - Preparation method of green feed additive gamma-aminobutyric acid - Google Patents
Preparation method of green feed additive gamma-aminobutyric acid Download PDFInfo
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- CN103242183A CN103242183A CN2013101719440A CN201310171944A CN103242183A CN 103242183 A CN103242183 A CN 103242183A CN 2013101719440 A CN2013101719440 A CN 2013101719440A CN 201310171944 A CN201310171944 A CN 201310171944A CN 103242183 A CN103242183 A CN 103242183A
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Abstract
The invention aims at providing a preparation method of green feed additive gamma-aminobutyric acid. The preparation method has obvious advantages that reaction time is short, yield is high, cost is low, raw materials are easily available and operations are simple and safe and hereby is favorable for industrialized production. The preparation method mainly comprises the following steps of: preparing phthalimide potassium (3); preparing methyl-4-chlorobutyrate; preparing phthaloyl imino acid methyl butyrate (4); and preparing the gamma-aminobutyric acid. The gamma-aminobutyric acid prepared through the method has good effects of promoting animal ingestion, regulating incretion, improving immune performance and enhancing the anti-stress level of livestock and poultry and meets the requirement for resource-saving environmental-friendly sustainable stockbreeding development. Thus, the gamma-aminobutyric acid which can be used as a green feed additive has good application prospect in feed industry.
Description
Technical field
The present invention relates to a kind of amino acid whose preparation method, the preparation method of a kind of green feed additive γ-An Jidingsuan of saying so more specifically.
Background technology
γ-An Jidingsuan γ-aminobutyric acid (GABA), chemical name: the 4-aminobutyric acid is a kind of natural non-protein amino acid in the organism, it is a kind of active skull cap components, be distributed widely in the animal and plant body, participate in multiple Metabolic activity, have very high physiologically active.The γ-An Jidingsuan molecular formula is C
4H
9NO
2, molecular weight: 103.1, chemical structural formula is:
On September 27th, 2009, Ministry of Health of the People's Republic of China's approval γ-An Jidingsuan is new resource food.Along with growth in the living standard, people are also more and more higher for the requirement of animal product, and not only requirement quantitatively more requires qualitative qualifiedly, and this just requires product that the feed industry provides not only to want efficient, more will accomplish safety and environmental protection.As fodder additives, γ-An Jidingsuan both can improve breeding performonce fo animals, met in the world the requirement for the requirement of food safety and feed safety and livestock-raising, fodder additives development again.
γ-An Jidingsuan is inhibitory nerve mediator important in the mammalian central nervous system, and is useful to growth of animal, modulation of appetite and anti-stress aspect.Animal searches for food not only to vital movement and the production performance of keeping animal provides the sufficient nutrient material, and is the visualize of its healthy state of reflection, and is closely related with production performance.Studies show that in a large number γ-An Jidingsuan is alleviating the basal metabolism of animal, the utilization ratio aspect of improving production performance and raising feed nutrient has good result.When adding γ-An Jidingsuan 10mg/kg and 20mg/kg in daily ration, pig feed intake significantly improves; The Gabanergic that adds 10mg/kg in producing the fattening pig daily ration improves day weight gain and dressing percentage; The promotes growth effect of in the weanling pig daily ration, adding γ-An Jidingsuan 50mg/kg amount best (Liu Zhenjun etc., γ-An Jidingsuan to the influence of early-weaned piglets growth performance and physiochemical indice, Sichuan Agricultural University's academic dissertation).In recent years, studies show that, add γ-An Jidingsuan in the livestock and poultry diet and can promote that animal searches for food that endocrine regulation improves immune performance and improves livestock and poultry anti-stress level.
Therefore, γ-An Jidingsuan will have a good application prospect in fodder industry as a kind of green feed additive.
Summary of the invention
The purpose of this invention is to provide a kind of green feed additive---the preparation method of γ-An Jidingsuan.Adopt preparation method of the present invention, the reaction times is short, the yield height, and cost is low, and raw material is easy to get, and is simple to operate, and safety is convenient to suitability for industrialized production.
Reaction equation of the present invention:
A kind of preparation method of green feed additive γ-An Jidingsuan, concrete steps are as follows:
A. potassium phthalimide preparation 3.
1. 100-140 gram Tetra hydro Phthalic anhydride drops into rapidly in the reactor of preheating with 40-60 gram urea mixing, the stirring heating melting reaction adds water the 400-450 gram rapidly after 15-20 minute, from water, separate out crystal, obtain phthalic imidine 2., after the drying, be dissolved in the ethanol, be adjusted to alkalescence with potassium hydroxide, generate potassium phthalimide 3..
B.4-the preparation of chloro-butyric acid methyl esters
In the 1000mL there-necked flask, add 86-215 gram (1-2.5mol) gamma-butyrolactone, add 178-595 gram (1.5-5.0mol) sulfur oxychloride under the room temperature and stir dropping 48-120 gram anhydrous methanol down, water-soluble be warming up to 50 ℃ the reaction 2-4 hour, be warming up to 60 ℃ of reactions 2-4 hour then, reaction finishes, and is cooled to 25 ℃, and the agitation and dropping saturated sodium bicarbonate solution is to PH=7, leave standstill and make it layering, oil phase washes with water to neutral (about four times).The oil phase anhydrous sodium sulfate drying obtains 4-chloro-butyric acid methyl esters.
C. phthaloyl imino acid methyl-butyrate preparation 4.
3. potassium phthalimide is dissolved in the dimethyl formamide, add in the solution of generation 0.1-1.5mol/L and be equivalent to 3. 0.2-3.0mol/L4-chloro-butyric acid methyl esters, be heated to 160-180 ℃, with reaction mixture refluxed, react after 1.5-3 hour, 4. crystallisation by cooling obtains phthaloyl imino acid methyl-butyrate.
D. the preparation of γ-An Jidingsuan
4. be dissolved in cold phthaloyl imino acid methyl-butyrate in the ethanol, make the solution of 0.2-1.5mol/L, add and be equivalent to the 4. hydrochloric acid of 1-2mol/L, be adjusted to PH=2,50-70 ℃ of reaction 3-5 hour, the sodium hydroxide of 1-2mol/L is adjusted to PH=7.2 with being equivalent to 4., is cooled to 0 ℃, filters to obtain γ-An Jidingsuan sodium, be neutralized to PH=4 with hydrochloric acid, be evaporated to pasty state, add 95% ethanol, dissolving refluxes, the filtering precipitation, filtrate decompression concentrates, cooling, and crystallization obtains γ-An Jidingsuan.
In existing industrial practice, γ-An Jidingsuan preparation method pyrrolidone is starting raw material, needs high-temperature high-voltage reaction 20 hours, the production cost height, and investment is big.Compared with the existing, it is that raw material is made the reaction of 4-chloro-butyric acid methyl esters and potassium phthalimide that γ-An Jidingsuan preparation method provided by the present invention adopts gamma-butyrolactone, has that route is short, product yield is high, low cost and other advantages.
Embodiment:
According to above Production Flow Chart, below provide several embodiments:
Embodiment 1:
A kind of preparation method of green feed additive γ-An Jidingsuan, concrete steps are as follows:
A. potassium phthalimide preparation 3.
1. 100 gram Tetra hydro Phthalic anhydrides restrain the urea mixings with 40, drop into the reactor of preheating rapidly, stirring heating is melted, react after 15 minutes, add 400 gram water rapidly, from water, separate out crystallization, obtain phthalic imidine 2., be dissolved in after the drying in the ethanol, be adjusted to alkalescence with sodium hydroxide, generate potassium phthalimide 3..
B.4-the preparation of chloro-butyric acid methyl esters
In the 1000mL there-necked flask, add 86 gram (1mol) gamma-butyrolactones, add 178 gram (1.5mol) sulfur oxychlorides under the room temperature and stir the 48 gram anhydrous methanols of dropping down, water-soluble be warming up to 50 ℃ the reaction 2 hours, be warming up to 60 ℃ of reactions 2 hours then, reaction finishes, and is cooled to 25 ℃, and the agitation and dropping saturated sodium bicarbonate solution is to PH=7, leave standstill and make it layering, oil phase washes with water to neutral (about four times).The oil phase anhydrous sodium sulfate drying obtains 4-chloro-butyric acid methyl esters.
C. phthaloyl imino acid methyl-butyrate preparation 4.
3. potassium phthalimide is dissolved in the dimethyl formamide, adds in the solution of generation 0.1mol/L and be equivalent to 3. 0.2mol/L4-chloro-butyric acid methyl esters, be heated to 160 ℃, with reaction mixture refluxed, react after 1.5 hours, 4. crystallisation by cooling obtains phthaloyl imino acid methyl-butyrate.
D. the preparation of γ-An Jidingsuan
4. cold phthaloyl imino acid methyl-butyrate is dissolved in the ethanol, makes the solution of 0.2mol/L, add and be equivalent to the 4. hydrochloric acid of 1mol/L, be adjusted to PH=2,50 ℃ of reactions 3 hours, the sodium hydroxide of 1mol/L was adjusted to PH=7.2 with being equivalent to 4., be cooled to 0 ℃, filter and obtain γ-An Jidingsuan sodium, be neutralized to PH=4 with hydrochloric acid, be evaporated to pasty state, add 95% ethanol, dissolving refluxes, the filtering precipitation, filtrate decompression concentrates, cooling, and crystallization obtains γ-An Jidingsuan.
Embodiment 2:
A kind of preparation method of green feed additive γ-An Jidingsuan, concrete steps are as follows:
A. potassium phthalimide preparation 3.
1. 110 gram Tetra hydro Phthalic anhydrides restrain the urea mixings with 50, drop into the reactor of preheating rapidly, stirring heating is melted, react after 16 minutes, add 410 gram water rapidly, from water, separate out crystallization, obtain phthalic imidine 2., be dissolved in after the drying in the ethanol, be adjusted to alkalescence with sodium hydroxide, generate potassium phthalimide 3..
B.4-the preparation of chloro-butyric acid methyl esters
In the 1000mL there-necked flask, add 129 gram (1.5mol) gamma-butyrolactones, add 178 gram (1.5mol) sulfur oxychlorides under the room temperature and stir the 238 gram anhydrous methanols of dropping down, water-soluble be warming up to 50 ℃ the reaction 2.5 hours, be warming up to 60 ℃ of reactions 2 hours then, reaction finishes, and is cooled to 25 ℃, and the agitation and dropping saturated sodium bicarbonate solution is to PH=7, leave standstill and make it layering, oil phase washes with water to neutral (about four times).The oil phase anhydrous sodium sulfate drying obtains 4-chloro-butyric acid methyl esters.
C. phthaloyl imino acid methyl-butyrate preparation 4.
3. potassium phthalimide is dissolved in the dimethyl formamide, adds in the solution of generation 0.3mol/L and be equivalent to 3. 0.6mol/L4-chloro-butyric acid methyl esters, be heated to 170 ℃, with reaction mixture refluxed, react after 1.5 hours, 4. crystallisation by cooling obtains phthaloyl imino acid methyl-butyrate.
D. the preparation of γ-An Jidingsuan
4. cold phthaloyl imino acid methyl-butyrate is dissolved in the ethanol, makes the solution of 0.4mol/L, add and be equivalent to the 4. hydrochloric acid of 1.4mol/L, be adjusted to PH=2,60 ℃ of reactions 3.5 hours, the sodium hydroxide of 1.5mol/L was adjusted to PH=7.2 with being equivalent to 4., be cooled to 0 ℃, filter and obtain γ-An Jidingsuan sodium, be neutralized to PH=4 with hydrochloric acid, be evaporated to pasty state, add 95% ethanol, dissolving refluxes, the filtering precipitation, filtrate decompression concentrates, cooling, and crystallization obtains γ-An Jidingsuan.
Embodiment 3:
A kind of preparation method of green feed additive γ-An Jidingsuan, concrete steps are as follows:
A. potassium phthalimide preparation 3.
1. 140 gram Tetra hydro Phthalic anhydrides restrain the urea mixings with 60, drop into the reactor of preheating rapidly, stirring heating is melted, react after 20 minutes, add 450 gram water rapidly, from water, separate out crystallization, obtain phthalic imidine 2., be dissolved in after the drying in the ethanol, be adjusted to alkalescence with sodium hydroxide, generate potassium phthalimide 3..
B.4-the preparation of chloro-butyric acid methyl esters
In the 1000mL there-necked flask, add 215 gram (2.5mol) gamma-butyrolactones, add 595 gram (1.5mol) sulfur oxychlorides under the room temperature and stir the 120 gram anhydrous methanols of dropping down, water-soluble be warming up to 50 ℃ the reaction 2.5 hours, be warming up to 60 ℃ of reactions 2 hours then, reaction finishes, and is cooled to 25 ℃, and the agitation and dropping saturated sodium bicarbonate solution is to PH=7, leave standstill and make it layering, oil phase washes with water to neutral (about four times).The oil phase anhydrous sodium sulfate drying obtains 4-chloro-butyric acid methyl esters.
C. phthaloyl imino acid methyl-butyrate preparation 4.
3. potassium phthalimide is dissolved in the dimethyl formamide, adds in the solution of generation 1.5mol/L and be equivalent to 3. 3.0mol/L4-chloro-butyric acid methyl esters, be heated to 180 ℃, with reaction mixture refluxed, react after 3.0 hours, 4. crystallisation by cooling obtains phthaloyl imino acid methyl-butyrate.
D. the preparation of γ-An Jidingsuan
4. cold phthaloyl imino acid methyl-butyrate is dissolved in the ethanol, makes the solution of 1.5mol/L, add and be equivalent to the 4. hydrochloric acid of 2.0mol/L, be adjusted to PH=2,60 ℃ of reactions 3.5 hours, the sodium hydroxide of 1.5mol/L was adjusted to PH=7.2 with being equivalent to 4., be cooled to 0 ℃, filter and obtain γ-An Jidingsuan sodium, be neutralized to PH=4 with hydrochloric acid, be evaporated to pasty state, add 95% ethanol, dissolving refluxes, the filtering precipitation, filtrate decompression concentrates, cooling, and crystallization obtains γ-An Jidingsuan.
Claims (4)
1. the preparation method of a green feed additive γ-An Jidingsuan, step comprises:
(1) potassium phthalimide preparation 3.
1. the Tetra hydro Phthalic anhydride of getting the 100-140 gram drops into rapidly in the reactor of preheating with the urea mixing, the stirring heating melting reaction adds water the 400-450 gram rapidly after 15-20 minute, from water, separate out crystal, obtain phthalic imidine 2., after the drying, be dissolved in the ethanol, be adjusted to alkalescence with potassium hydroxide, generate potassium phthalimide 3..
(2) preparation of 4-chloro-butyric acid methyl esters
In the 1000mL there-necked flask, add 86-215 gram (1-2.5mol) gamma-butyrolactone, add 178-595 gram (1.5-5.0mol) sulfur oxychloride under the room temperature and stir dropping 48-120 gram anhydrous methanol down, water-soluble be warming up to 50 ℃ the reaction 2-4 hour, be warming up to 60 ℃ of reactions 2-4 hour then, reaction finishes, and is cooled to 25 ℃, and the agitation and dropping saturated sodium bicarbonate solution is to PH=7, leave standstill and make it layering, oil phase washes with water to neutral (about four times).The oil phase anhydrous sodium sulfate drying obtains 4-chloro-butyric acid methyl esters.
(3) phthaloyl imino acid methyl-butyrate preparation 4.
3. potassium phthalimide is dissolved in the dimethyl formamide, add in the solution of generation 0.1-1.5mol/L and be equivalent to 3. 0.2-3.0mol/L4-chloro-butyric acid methyl esters, be heated to 160-180 ℃, with reaction mixture refluxed, react after 1.5-3 hour, 4. crystallisation by cooling obtains phthaloyl imino acid methyl-butyrate.
(4) preparation of γ-An Jidingsuan
4. be dissolved in the cold phthaloyl imino acid methyl-butyrate of 100-140 gram in the ethanol, make 0.2-1.5mol/L solution, add and be equivalent to the 4. hydrochloric acid of 1-2mol/L, be adjusted to PH to acid, 50-70 ℃ of reaction 3-5 hour, the sodium hydroxide of 1-2mol/L is adjusted to PH to weakly alkaline with being equivalent to 4., is cooled to 0 ℃, filters to obtain γ-An Jidingsuan sodium, be neutralized to PH to slightly acidic with hydrochloric acid, be evaporated to pasty state, add 95% ethanol, dissolving refluxes, the filtering precipitation, filtrate decompression concentrates, cooling, and crystallization obtains γ-An Jidingsuan.
2. the process of claim 1 wherein that step (4) will reach pH=2, pH=7.2 and pH=4 respectively through 3 pH values adjustment.
3. the process of claim 1 wherein in the step (4) the preferred 55-65 of temperature of reaction ℃, preferred 3.5-4 of reaction times hour.
4. the method for claim (4), wherein said step comprises:
2) preparation of 4-chloro-butyric acid methyl esters
(4) preparation of γ-An Jidingsuan
4. be dissolved in cold phthaloyl imino acid methyl-butyrate in the ethanol, make 0.2-1.5mol/L solution, add and be equivalent to the 4. hydrochloric acid of 1-2mol/L, be adjusted to PH=2,55-65 ℃ of reaction 3.5-4 hour, the sodium hydroxide of 1-2mol/L is adjusted to PH=7.2 with being equivalent to 4., is cooled to 0 ℃, filters to obtain γ-An Jidingsuan sodium, be neutralized to PH=4 with hydrochloric acid, be evaporated to pasty state, add 95% ethanol, dissolving refluxes, the filtering precipitation, filtrate decompression concentrates, cooling, and crystallization obtains γ-An Jidingsuan.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112028923A (en) * | 2020-08-21 | 2020-12-04 | 齐齐哈尔大学 | Siloxane 3-phthalimidopropyltriethoxysilane and preparation method thereof |
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| US4029700A (en) * | 1975-12-24 | 1977-06-14 | Rakhil Khatskelevna Freidlina | Process for the production of even series ω-amino acids |
| CN101830842A (en) * | 2010-05-30 | 2010-09-15 | 中国科学院亚热带农业生态研究所 | Preparation method of functional amino proline |
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2013
- 2013-04-28 CN CN2013101719440A patent/CN103242183A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4029700A (en) * | 1975-12-24 | 1977-06-14 | Rakhil Khatskelevna Freidlina | Process for the production of even series ω-amino acids |
| CN101830842A (en) * | 2010-05-30 | 2010-09-15 | 中国科学院亚热带农业生态研究所 | Preparation method of functional amino proline |
Non-Patent Citations (4)
| Title |
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| RUJEE K. DUKE等: "Synthesis and resolution of 2-methyl analogues of GABA", 《TETRAHEDRON: ASYMMETRY》 * |
| 张聪等: "《饲料添加剂γ-氨基丁酸的合成新方法》", 《饲料与畜牧》 * |
| 林亲录等: "γ-氨基丁酸的研究进展", 《现代食品科技》 * |
| 赵炳超等: "新型饲料添加剂—γ-氨基丁酸的制备", 《中国畜牧兽医》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112028923A (en) * | 2020-08-21 | 2020-12-04 | 齐齐哈尔大学 | Siloxane 3-phthalimidopropyltriethoxysilane and preparation method thereof |
| CN112028923B (en) * | 2020-08-21 | 2023-08-22 | 齐齐哈尔大学 | Siloxane 3-phthalimide propyl triethoxysilane and preparation method thereof |
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Application publication date: 20130814 |