CN113651708A - Preparation and post-treatment method of 5-aminolevulinic acid ester - Google Patents
Preparation and post-treatment method of 5-aminolevulinic acid ester Download PDFInfo
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- CN113651708A CN113651708A CN202110945142.5A CN202110945142A CN113651708A CN 113651708 A CN113651708 A CN 113651708A CN 202110945142 A CN202110945142 A CN 202110945142A CN 113651708 A CN113651708 A CN 113651708A
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- aminolevulinic acid
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- acid ester
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- 229960002749 aminolevulinic acid Drugs 0.000 title claims abstract description 30
- -1 5-aminolevulinic acid ester Chemical class 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 21
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 13
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000012046 mixed solvent Substances 0.000 claims abstract description 10
- ZGXJTSGNIOSYLO-UHFFFAOYSA-N 88755TAZ87 Chemical compound NCC(=O)CCC(O)=O ZGXJTSGNIOSYLO-UHFFFAOYSA-N 0.000 claims abstract description 9
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 7
- 150000002314 glycerols Chemical class 0.000 claims abstract description 7
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 7
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 5
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000007864 aqueous solution Substances 0.000 claims abstract description 4
- 238000010992 reflux Methods 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 229940070710 valerate Drugs 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229940126062 Compound A Drugs 0.000 abstract description 9
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 abstract description 9
- 238000002425 crystallisation Methods 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- 230000008025 crystallization Effects 0.000 abstract description 3
- 239000007983 Tris buffer Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 239000003814 drug Substances 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 229940079593 drug Drugs 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000000575 pesticide Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- XHFLOLLMZOTPSM-UHFFFAOYSA-M sodium;hydrogen carbonate;hydrate Chemical compound [OH-].[Na+].OC(O)=O XHFLOLLMZOTPSM-UHFFFAOYSA-M 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 2
- RKOGJKGQMPZCGG-UHFFFAOYSA-N 2-methoxypropane-1,3-diol Chemical compound COC(CO)CO RKOGJKGQMPZCGG-UHFFFAOYSA-N 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229930002875 chlorophyll Natural products 0.000 description 1
- 235000019804 chlorophyll Nutrition 0.000 description 1
- ATNHDLDRLWWWCB-AENOIHSZSA-M chlorophyll a Chemical compound C1([C@@H](C(=O)OC)C(=O)C2=C3C)=C2N2C3=CC(C(CC)=C3C)=[N+]4C3=CC3=C(C=C)C(C)=C5N3[Mg-2]42[N+]2=C1[C@@H](CCC(=O)OC\C=C(/C)CCC[C@H](C)CCC[C@H](C)CCCC(C)C)[C@H](C)C2=C5 ATNHDLDRLWWWCB-AENOIHSZSA-M 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000004494 ethyl ester group Chemical group 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
- C07C227/42—Crystallisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a preparation and post-treatment method of 5-aminolevulinic acid ester, adding a mixed solvent of liquid saturated chain hydrocarbon and dimethylformamide into a reaction container under low temperature, stirring and cooling, adding 5-aminolevulinic acid and a corresponding glycerol derivative, stirring and dissolving, adding 4-dimethylaminopyridine, dropwise adding dicyclohexylcarbodiimide, reacting after keeping the temperature at normal temperature, dissolving the hydrochloride of the 5-aminolevulinic acid ester obtained by the preparation by using the solvent, stirring and refluxing, dropwise adding a sodium bicarbonate aqueous solution when the temperature of the mixed solution is 35-45 ℃, stirring and crystallizing, drying and crushing to obtain the compound A, wherein the compound A obtained by crystallization is small in particle and easy to crush, and related substances can be effectively removed, and the problems in the prior art are well solved.
Description
Technical Field
The invention relates to the technical field of drug synthesis, in particular to a preparation and post-treatment method of a 5-aminolevulinic acid ester.
Background
5-aminolevulinic acid is a biological endogenous substance, is a precursor substance for biosynthesis of animal hemoglobin and plant chlorophyll, is widely applied to the field of medicines, can be used as a photosensitizer for treating various cancers, and can also be used for preparing pesticides, herbicides and the like. Due to the unstable structure and limited permeability of 5-aminolevulinic acid, various esterified medicaments such as methyl ester, ethyl ester and the like are continuously on the market in the past 90 s.
In the prior art, a 5-aminolevulinic acid ester compound A for application in the fields of medicines and pesticides is disclosed, and the compound is formed by esterifying 5-aminolevulinic acid and glycerol derivatives, has good stability and permeability, and can be applied in the fields of medicines and pesticides.
The synthetic route is as follows, and is prepared by esterifying 5-aminolevulinic acid and glycerol derivatives, and mainly adopting concentrated sulfuric acid condensation, or esterifying reagents such as thionyl chloride and the like by adopting a conventional mode.
The reaction temperature is high, the reaction regulation is severe, and the above synthesis mode has the problems of more impurities, difficulty in purification, low compound yield and the like. After the compound is formed into hydrochloride, the compound is crystallized by a conventional method, and has the problems of large particles and difficult pulverization.
Disclosure of Invention
Aiming at the defects and problems in the prior art, the invention provides a preparation and post-treatment method of a 5-aminolevulinic acid ester, which can obtain a compound A with high yield and low impurity content and solves the problems that the compound A has large particles and is difficult to crush after being converted into hydrochloride.
In order to achieve the purpose, the invention provides the following technical scheme:
a preparation method of 5-aminolevulinic acid ester comprises the following steps:
adding a mixed solvent of liquid saturated chain hydrocarbon and dimethylformamide into a reaction container under a low-temperature condition, stirring and cooling, adding 5-aminolevulinic acid and a corresponding glycerol derivative, stirring and dissolving, adding 4-dimethylaminopyridine, dropwise adding dicyclohexylcarbodiimide, and reacting after keeping the temperature at normal temperature to obtain the product;
the liquid saturated chain hydrocarbon comprises one or more mixed solutions of ethane, propane, hexane and heptane;
in the mixed solvent, the weight ratio of the liquid saturated chain hydrocarbon is 20-80%;
the low temperature is in the range of-10 to 5 ℃;
the glycerol derivative has a formula structure as follows:
wherein R1 is methyl, ethyl or propyl group capable of increasing liposolubility.
In the technical scheme, the mixed solvent can be replaced by dichloromethane or dimethylformamide, but the yield of the mixed solvent is improved by about 20 percent compared with that of the conventional dichloromethane or dimethylformamide, the product purity is also improved, and the yield of the post-treatment is not reduced by selecting the mixed solvent.
A preparation post-treatment method of 5-aminolevulinic acid ester comprises the following steps:
dissolving compound A hydrochloride in solvent, stirring and refluxing, dripping sodium bicarbonate water solution when the temperature of the mixed solution is 35-45 ℃, stirring and crystallizing, drying and crushing to obtain the compound A hydrochloride;
the solvent is alcohol compound, including methanol and ethanol.
In the above technical solution, the concentration of the aqueous solution of sodium bicarbonate is 0.5-10% (m/m), preferably 4-5%;
in the technical scheme, the drying temperature is 30-60 ℃.
The invention adopts an unconventional crystallization method of dripping the sodium bicarbonate aqueous solution, can obtain the compound A with high yield and low impurity, and the compound A obtained by crystallization by the method has small particles and is easy to crush, can effectively remove related substances, and better solves the problems in the prior art.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
An example of the synthesis of a 5-aminolevulinic acid ester as shown in the example is as follows:
1. synthesis of 2-methylpropane-1, 2, 3-tris (5-aminolevulinic acid ester)
1,1,1- (trihydroxymethyl) -ethane
5-aminolevulinic acid
2-methylpropane-1, 2, 3-tris (5-aminolevulinic acid ester) hydrochloride
Adding 2000g of 40% ethane and 60% dimethylformamide mixed solvent into a reaction container, cooling to-5 ℃, adding 50g of 2-methyl glycerol, 78g of 5-aminolevulinic acid and 10g of 4-dimethylaminopyridine under stirring, slowly dropwise adding 60g of dicyclohexylcarbodiimide after uniformly stirring, reacting for 0.5 hour under stirring, heating to 20 ℃, reacting for 8 hours under heat preservation, filtering to remove impurities, concentrating to a small volume, adding 500ml of ethyl acetate to dissolve, concentrating to a small volume, and crystallizing to obtain 81g of 2-methylpropane-1, 2, 3-tris (5-aminolevulinic acid ester).
2. Synthesis of 2-methylpropane-1, 2, 3-tris (5-aminolevulinic acid ester) hydrochloride
Adding 800ml of dichloromethane into a reaction vessel, adding 80g of 2-methylpropane-1, 2, 3-tris (5-aminolevulinic acid ester) into the reaction vessel, stirring and dissolving the mixture, slowly dropwise adding 50ml of concentrated hydrochloric acid, and stirring the mixture for 2 hours at the temperature of 30 ℃. Adjusting pH value to be neutral by NaOH, concentrating to be oily, adding 600ml of methanol, stirring for dissolving, concentrating to be small in volume, stirring for crystallization, and obtaining 76g of 2-methylpropane-1, 2, 3-tris (5-aminolevulinic acid ester) hydrochloride.
3. Working up of 2-methylpropane-1, 2, 3-tris (5-aminolevulinic acid ester) hydrochloride
Dissolving 100g of 2-methylpropane-1, 2, 3-tris (5-aminoketone valerate) hydrochloride by 900ml of ethanol, stirring, heating, refluxing, cooling to 40 ℃, dropwise adding 200ml of 1% sodium bicarbonate water solution, stirring, crystallizing, drying under reduced pressure at 40 ℃, and crushing to obtain the compound.
4. Effect of solvent in 2-methylpropane-1, 2, 3-tris (5-aminolevulinic acid ester)
The above description is only for the specific embodiments of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art can easily conceive of the changes or substitutions within the technical scope of the present invention, and all the changes or substitutions should be covered within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.
Claims (5)
1. A preparation method of 5-aminolevulinic acid ester is characterized by comprising the following steps: comprises the following steps:
adding a mixed solvent of liquid saturated chain hydrocarbon and dimethylformamide into a reaction container under a low-temperature condition, stirring and cooling, adding 5-aminolevulinic acid and a corresponding glycerol derivative, stirring and dissolving, adding 4-dimethylaminopyridine, dropwise adding dicyclohexylcarbodiimide, and reacting after keeping the temperature at normal temperature to obtain the product;
the liquid saturated chain hydrocarbon comprises one or more mixed solutions of ethane, propane, hexane and heptane;
in the mixed solvent, the weight ratio of the liquid saturated chain hydrocarbon is 20-80%;
the low temperature is in the range of-10 to 5 ℃;
the glycerol derivative has a formula structure as follows:
wherein R1 is methyl, ethyl or propyl group capable of increasing liposolubility.
2. The method for producing a 5-aminolevulinic acid ester according to claim 1, wherein: and replacing the mixed solvent with dichloromethane or dimethylformamide.
3. A preparation post-treatment method of 5-aminolevulinic acid ester is characterized by comprising the following steps: dissolving hydrochloride of 5-aminoketone valerate prepared in claims 1-2 in a solvent, stirring and refluxing, dripping sodium bicarbonate aqueous solution when the temperature of the mixed solution is 35-45 ℃, stirring and crystallizing, drying and crushing;
the solvent is alcohol compound, including methanol and ethanol.
4. The method of claim 3, wherein the method comprises the following steps: the concentration of the aqueous sodium bicarbonate solution is 0.5 to 10% (m/m), preferably 4 to 5%.
5. The method of claim 3, wherein the method comprises the following steps: the drying temperature is 30-60 ℃.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110945142.5A CN113651708A (en) | 2021-08-17 | 2021-08-17 | Preparation and post-treatment method of 5-aminolevulinic acid ester |
| PCT/CN2021/139309 WO2023019839A1 (en) | 2021-08-17 | 2021-12-17 | Preparation and post-treatment method for 5-aminolevulinate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110945142.5A CN113651708A (en) | 2021-08-17 | 2021-08-17 | Preparation and post-treatment method of 5-aminolevulinic acid ester |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113651708A true CN113651708A (en) | 2021-11-16 |
Family
ID=78480715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110945142.5A Pending CN113651708A (en) | 2021-08-17 | 2021-08-17 | Preparation and post-treatment method of 5-aminolevulinic acid ester |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN113651708A (en) |
| WO (1) | WO2023019839A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023019838A1 (en) * | 2021-08-17 | 2023-02-23 | 湖南复瑞生物医药技术有限责任公司 | 5-aminolevulinic acid ester, use and pesticide composition |
| WO2023019839A1 (en) * | 2021-08-17 | 2023-02-23 | 湖南复瑞生物医药技术有限责任公司 | Preparation and post-treatment method for 5-aminolevulinate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1178521A (en) * | 1995-03-10 | 1998-04-08 | 光治疗公司 | Esters of 5-aminolevulinic acid as photosensitizing agents in photochemotherapy |
| US20100273725A1 (en) * | 2007-12-14 | 2010-10-28 | Thomas Glanzmann | Novel compounds useful in therapeutic and cosmetic methods |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113651708A (en) * | 2021-08-17 | 2021-11-16 | 湖南复瑞生物医药技术有限责任公司 | Preparation and post-treatment method of 5-aminolevulinic acid ester |
-
2021
- 2021-08-17 CN CN202110945142.5A patent/CN113651708A/en active Pending
- 2021-12-17 WO PCT/CN2021/139309 patent/WO2023019839A1/en not_active Ceased
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1178521A (en) * | 1995-03-10 | 1998-04-08 | 光治疗公司 | Esters of 5-aminolevulinic acid as photosensitizing agents in photochemotherapy |
| US20100273725A1 (en) * | 2007-12-14 | 2010-10-28 | Thomas Glanzmann | Novel compounds useful in therapeutic and cosmetic methods |
Non-Patent Citations (1)
| Title |
|---|
| SINAN H. BATTAH等: "Synthesis and Biological Studies of 5-Aminolevulinic Acid-Containing Dendrimers for Photodynamic Therapy", BIOCONJUGATE CHEM., vol. 12, no. 6, 11 March 2001 (2001-03-11), pages 980 - 988, XP001092540, DOI: 10.1021/bc010027n * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023019838A1 (en) * | 2021-08-17 | 2023-02-23 | 湖南复瑞生物医药技术有限责任公司 | 5-aminolevulinic acid ester, use and pesticide composition |
| WO2023019839A1 (en) * | 2021-08-17 | 2023-02-23 | 湖南复瑞生物医药技术有限责任公司 | Preparation and post-treatment method for 5-aminolevulinate |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2023019839A1 (en) | 2023-02-23 |
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