CN112876394A - Preparation method of DL-hydroxyselenomethionine - Google Patents
Preparation method of DL-hydroxyselenomethionine Download PDFInfo
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- CN112876394A CN112876394A CN202110177941.2A CN202110177941A CN112876394A CN 112876394 A CN112876394 A CN 112876394A CN 202110177941 A CN202110177941 A CN 202110177941A CN 112876394 A CN112876394 A CN 112876394A
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- butyrolactone
- hydroxyselenomethionine
- gamma
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- sodium
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- FWIBCWKHNZBDLS-UHFFFAOYSA-N 3-hydroxyoxolan-2-one Chemical compound OC1CCOC1=O FWIBCWKHNZBDLS-UHFFFAOYSA-N 0.000 claims abstract description 14
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 230000033444 hydroxylation Effects 0.000 claims abstract description 3
- 238000005805 hydroxylation reaction Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- LFJJGHGXHXXDFT-UHFFFAOYSA-N 3-bromooxolan-2-one Chemical compound BrC1CCOC1=O LFJJGHGXHXXDFT-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 3
- PHSPJQZRQAJPPF-UHFFFAOYSA-N N-alpha-Methylhistamine Chemical compound CNCCC1=CN=CN1 PHSPJQZRQAJPPF-UHFFFAOYSA-N 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- -1 methyl Sodium selenoxide Chemical class 0.000 claims description 2
- 230000000269 nucleophilic effect Effects 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 238000007142 ring opening reaction Methods 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- 239000011593 sulfur Substances 0.000 claims description 2
- PPXAQNPNOPCBRG-UHFFFAOYSA-M [Se](=O)(=O)(OC)[O-].[Na+] Chemical compound [Se](=O)(=O)(OC)[O-].[Na+] PPXAQNPNOPCBRG-UHFFFAOYSA-M 0.000 claims 3
- 239000000010 aprotic solvent Substances 0.000 claims 1
- 239000003586 protic polar solvent Substances 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 abstract description 5
- 239000011734 sodium Substances 0.000 abstract description 5
- 229910052708 sodium Inorganic materials 0.000 abstract description 5
- 238000005893 bromination reaction Methods 0.000 abstract description 2
- 150000002894 organic compounds Chemical class 0.000 abstract description 2
- 229940091258 selenium supplement Drugs 0.000 description 17
- 229910052711 selenium Inorganic materials 0.000 description 16
- 239000011669 selenium Substances 0.000 description 16
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 241001465754 Metazoa Species 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 206010039921 Selenium deficiency Diseases 0.000 description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Chemical compound BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- GWEVNJPQPBNPPS-UHFFFAOYSA-N [Li].C[SeH] Chemical compound [Li].C[SeH] GWEVNJPQPBNPPS-UHFFFAOYSA-N 0.000 description 2
- HUGQWUJVICPBEX-UHFFFAOYSA-N [Na].C[SeH] Chemical compound [Na].C[SeH] HUGQWUJVICPBEX-UHFFFAOYSA-N 0.000 description 2
- WFHHBONIRRAXAT-UHFFFAOYSA-N butaneselenal Chemical compound CCCC=[Se] WFHHBONIRRAXAT-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- DVSDBMFJEQPWNO-UHFFFAOYSA-N methyllithium Chemical compound C[Li] DVSDBMFJEQPWNO-UHFFFAOYSA-N 0.000 description 2
- 229960002718 selenomethionine Drugs 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PMYDPQQPEAYXKD-UHFFFAOYSA-N 3-hydroxy-n-naphthalen-2-ylnaphthalene-2-carboxamide Chemical compound C1=CC=CC2=CC(NC(=O)C3=CC4=CC=CC=C4C=C3O)=CC=C21 PMYDPQQPEAYXKD-UHFFFAOYSA-N 0.000 description 1
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 101710088194 Dehydrogenase Proteins 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- 208000036626 Mental retardation Diseases 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 206010028289 Muscle atrophy Diseases 0.000 description 1
- 240000004808 Saccharomyces cerevisiae Species 0.000 description 1
- RJFAYQIBOAGBLC-BYPYZUCNSA-N Selenium-L-methionine Chemical compound C[Se]CC[C@H](N)C(O)=O RJFAYQIBOAGBLC-BYPYZUCNSA-N 0.000 description 1
- RJFAYQIBOAGBLC-UHFFFAOYSA-N Selenomethionine Natural products C[Se]CCC(N)C(O)=O RJFAYQIBOAGBLC-UHFFFAOYSA-N 0.000 description 1
- 206010039966 Senile dementia Diseases 0.000 description 1
- 102000003929 Transaminases Human genes 0.000 description 1
- 108090000340 Transaminases Proteins 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 208000026106 cerebrovascular disease Diseases 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000002526 effect on cardiovascular system Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000037406 food intake Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VRDKYJSLDJDLML-UHFFFAOYSA-N methylselenol Chemical compound [Se]C VRDKYJSLDJDLML-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000020763 muscle atrophy Effects 0.000 description 1
- 201000000585 muscular atrophy Diseases 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- SPVXKVOXSXTJOY-UHFFFAOYSA-N selane Chemical compound [SeH2] SPVXKVOXSXTJOY-UHFFFAOYSA-N 0.000 description 1
- 229910000058 selane Inorganic materials 0.000 description 1
- 125000003748 selenium group Chemical group *[Se]* 0.000 description 1
- 229960001881 sodium selenate Drugs 0.000 description 1
- 239000011655 sodium selenate Substances 0.000 description 1
- 235000018716 sodium selenate Nutrition 0.000 description 1
- 229960001471 sodium selenite Drugs 0.000 description 1
- 239000011781 sodium selenite Substances 0.000 description 1
- 235000015921 sodium selenite Nutrition 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 208000024891 symptom Diseases 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C391/00—Compounds containing selenium
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D307/32—Oxygen atoms
- C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the field of preparation of organic compounds. The invention provides a preparation method of DL-hydroxyselenomethionine. The method is characterized in that gamma-butyrolactone is used as a raw material, alpha-hydroxy-gamma-butyrolactone is synthesized through alpha-bromination and hydroxylation, and then the alpha-hydroxy-gamma-butyrolactone reacts with sodium methylselenolate to obtain DL-hydroxyselenomethionine. The method has the advantages of easily available raw materials, mild reaction conditions and low cost, and is suitable for mass preparation of DL-hydroxyselenomethionine.
Description
Technical Field
The invention belongs to the field of preparation of organic compounds. The invention relates to a method for preparing DL-hydroxyselenomethionine.
Background
Selenium is an indispensable microelement in human bodies and animal bodies, and has obvious effects on preventing and inhibiting cancers, delaying aging and the like. 42 kinds of diseases such as cancer, cardiovascular and cerebrovascular diseases, children's mental retardation, senile dementia and the like of human beings are related to selenium deficiency. Selenium deficiency in animals can lead to increased mortality, muscle atrophy, and other symptoms. Therefore, the world health organization identified selenium as an essential trace element for humans and animals in 1973. Inorganic selenium is a first-generation selenium source, sodium selenite and sodium selenate can be used as a feed additive, and the inorganic selenium is low in price, but is mainly absorbed in a simple diffusion mode, poor in organism absorption and low in effective utilization rate, can generate toxicity to organisms under the condition of high ingestion, can only meet the requirement of preventing selenium deficiency of animals, and is difficult to realize effective selenium supplement to promote the health and the production performance of the animals. Therefore, the addition of inorganic selenium not only can not achieve the ideal selenium supplementing effect, but also can pollute the environment. DL-hydroxyselenomethionine is a new generation of organic selenium source which is newly developed. Is a selenomethionine hydroxyl analogue, and can be completely converted into L-selenomethionine in organisms through the action of dehydrogenase and transaminase. The compound was approved by the european union as organic selenium in 5 months in 2013 to be applicable to all animal feeds, and was introduced by the company edisu france under the tradename Selisseo in 2014. The organic selenium is derived from chemical synthesis, has purity of over 99.5%, and biological utilization rate remarkably higher than that of yeast selenium and inorganic selenium, and is used as organic selenium source, easy for QC detection and management, and good in batch consistency and stability. The original research process route of DL-hydroxyselenomethionine is that methyl lithium and selenium are prepared into methyl selenol lithium in ether, and then the methyl selenol lithium reacts with alpha-hydroxybutyric lactone to prepare the DL-hydroxyselenomethionine, the process not only uses flammable and explosive methyl lithium and ether, but also uses the alpha-hydroxybutyrolactone which is not easy to obtain as raw materials, and the industrial production cost is high (WO2006008190A 2); the other process route is that methyl selenol and acrolein are reacted to prepare 3-methyl seleno-propionaldehyde, and then the 3-methyl seleno-propionaldehyde is added with a virulent reagent sodium cyanide or hydrogen cyanide and then hydrolyzed to obtain the product, wherein the route not only uses cyanide, hydrogen selenide and various toxic reagents of acrolein, but also has longer reaction route of a selenium-bearing intermediate with poor stability, poor quality control in the process and very strict requirements on industrial production conditions (CN 109232342A). Therefore, the development of a new method for preparing DL-hydroxyselenomethionine with simplicity, high efficiency and low cost has important value for the application and popularization of the emerging selenium source.
Disclosure of Invention
The invention aims to develop a method for preparing DL-hydroxyselenomethionine, which is simple, efficient, mild in condition and low in cost.
The invention is characterized in that: using gamma-butyrolactone as raw material, firstly synthesizing alpha-hydroxy-gamma-butyrolactone through alpha-bromination and hydroxylation, then reacting with methyl sodium selenol to obtain DL-hydroxyselenomethionine. The method has the advantages of easily available raw materials, mild reaction conditions and low cost, and is suitable for mass preparation of DL-hydroxyselenomethionine.
The structure of the synthesized DL-hydroxyselenomethionine is characterized in that: represented by the formula
The invention adopts the following technical scheme:
1) the gamma-butyrolactone is used as a raw material and reacts with liquid bromine to obtain the alpha-bromo-gamma-butyrolactone.
2) The alpha-bromine-gamma-butyrolactone is hydrolyzed in potassium carbonate to obtain the alpha-hydroxy-gamma-butyrolactone.
3) Reacting alpha-hydroxy-gamma-butyrolactone with sodium methylselenolate, and acidifying to obtain DL-hydroxyselenomethionine.
Detailed Description
The synthesis of DL-hydroxyselenomethionine adopts gamma-butyrolactone as a raw material, firstly, the gamma-butyrolactone reacts with liquid bromine to obtain alpha-bromo-gamma-butyrolactone, then the alpha-bromo-gamma-butyrolactone is hydrolyzed in potassium carbonate to obtain alpha-hydroxy-gamma-butyrolactone, and finally, the alpha-hydroxy-gamma-butyrolactone reacts with sodium methylselenolate and is acidified to obtain DL-hydroxyselenomethionine.
In the invention, the preparation of the alpha-bromo-gamma-butyrolactone can be completed by selecting no catalyst or using a catalyst, wherein the catalyst used can be phosphorus or sulfur or phosphorus tribromide; in the last nucleophilic ring-opening preparation of DL-hydroxyselenomethionine, dry methyl selenol sodium or methyl selenol sodium solution can be used, and the solvent for reaction can be non-proton solvent such as tetrahydrofuran, methyl tetrahydrofuran, 1, 4-dioxane and the like or proton solvent such as methanol, ethanol and the like.
Example of the implementation
The present invention will be described in detail below with reference to examples. However, the present invention is not limited to the embodiments shown in the embodiments, and the specific embodiments may be variously modified within the scope of the description of the specific embodiments of the present invention.
Preparation of 1 alpha-bromo-gamma-butyrolactone
Adding 2.2ml of phosphorus tribromide into 100g of gamma-butyrolactone, heating to 100 ℃ under the protection of nitrogen, slowly dripping 176.4g of bromine, continuing to keep the temperature and stir for reaction for 4 hours after the dripping is finished, and performing reduced pressure concentration to remove low-boiling-point substances after the reaction to obtain 172.5g of alpha-bromo-gamma-butyrolactone crude product which is directly used for the next reaction.
Preparation of 2 alpha-hydroxy-gamma-butyrolactone
217g of potassium carbonate is dissolved in 1L of deionized water, heated to reflux, 172.5g of the crude product of alpha-bromo-gamma-butyrolactone obtained in example 1 is slowly added dropwise, the mixture is kept at the temperature and stirred for reaction for 2 hours after the addition, the reaction temperature is reduced to room temperature after the reaction is finished, 177mL of concentrated hydrochloric acid is added dropwise, and then the reaction mixture is concentrated to dryness under reduced pressure. Adding 500mL of absolute ethyl alcohol into the residue, stirring and pulping for 30 minutes, filtering to remove insoluble substances, concentrating the filtrate under reduced pressure to remove the solvent to obtain a crude product, and distilling under reduced pressure to obtain 90.1g of alpha-hydroxy-gamma-butyrolactone colorless oily liquid.1H NMR (400MHz,CDCl3)：δ＝4.48(dd,J＝10.1,8.5Hz,1H),4.33(td,J＝9.1,2.1Hz,1H), 4.19-4.13(m,1H),2.56-2.49(m,1H),2.24-2.13(m,1H),1.96(bs,1H)。
Preparation of 3 DL-alpha-hydroxyselenomethionine (1)
Under the protection of nitrogen at room temperature, 10g of alpha-hydroxy-gamma-butyrolactone is dripped into 200mL of methanol solution containing 17g of sodium methylselenolate, and after the dripping is finished, the temperature is raised to reflux and the reaction is continued overnight. Then decompressing and concentrating the reaction liquid to be dry, putting the residue into ice water, dropwise adding concentrated hydrochloric acid to adjust the pH value to be less than or equal to 1, extracting tert-butyl methyl ether, drying anhydrous sodium sulfate, and concentrating to obtain 14.1g of product, namely yellow oily liquid.1H NMR(400MHz,CDCl3)：δ＝ 4.46(dd,J＝8.1,3.8Hz,1H),2.72(m,2H),2.25(m,1H),2.10(m,1H),2.04(s, 3H)。
Preparation of 4 DL-alpha-hydroxyselenomethionine (2)
Under the protection of nitrogen at room temperature, 8g of dry sodium methylselenolate is dispersed into 100mL of anhydrous tetrahydrofuran solution, 5g of alpha-hydroxy-gamma-butyrolactone is slowly dripped, and the temperature is raised to reflux after the dripping is finished, and the reaction is continued overnight. Then, the reaction solution is decompressed and concentrated to be dry, the residue is put into ice water, concentrated hydrochloric acid is dripped to adjust the pH value to be less than or equal to 1, and the anhydrous sodium sulfate is dried after the methyl tetrahydrofuran is extracted, and the product is concentrated to obtain 7.3 g.
Claims (3)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114181177A (en) * | 2021-11-25 | 2022-03-15 | 烟台泽湃新材料科技有限公司 | Production method of novel alpha-bromo-gamma-butyrolactone |
| CN117402128A (en) * | 2023-10-17 | 2024-01-16 | 河北圣泰材料股份有限公司 | Preparation method of 3-fluorodihydrofuran-2 (3H) -ketone |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114181177A (en) * | 2021-11-25 | 2022-03-15 | 烟台泽湃新材料科技有限公司 | Production method of novel alpha-bromo-gamma-butyrolactone |
| CN117402128A (en) * | 2023-10-17 | 2024-01-16 | 河北圣泰材料股份有限公司 | Preparation method of 3-fluorodihydrofuran-2 (3H) -ketone |
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