CN118146200A - Coumarin-based imine hydrazide derivative and preparation method and application thereof - Google Patents
Coumarin-based imine hydrazide derivative and preparation method and application thereof Download PDFInfo
- Publication number
- CN118146200A CN118146200A CN202410087052.0A CN202410087052A CN118146200A CN 118146200 A CN118146200 A CN 118146200A CN 202410087052 A CN202410087052 A CN 202410087052A CN 118146200 A CN118146200 A CN 118146200A
- Authority
- CN
- China
- Prior art keywords
- formula
- coumarin
- compound shown
- hydrazide derivative
- compound
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 229960000956 coumarin Drugs 0.000 title claims abstract description 18
- 235000001671 coumarin Nutrition 0.000 title claims abstract description 18
- 150000002466 imines Chemical class 0.000 title claims description 12
- 238000002360 preparation method Methods 0.000 title claims description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 3
- 238000003786 synthesis reaction Methods 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
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000003973 paint Substances 0.000 abstract description 21
- -1 coumarin imide Chemical class 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 5
- HSHNITRMYYLLCV-UHFFFAOYSA-N 4-methylumbelliferone Chemical class C1=C(O)C=CC2=C1OC(=O)C=C2C HSHNITRMYYLLCV-UHFFFAOYSA-N 0.000 abstract description 4
- 239000012752 auxiliary agent Substances 0.000 abstract description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002262 Schiff base Substances 0.000 abstract description 2
- 150000004753 Schiff bases Chemical class 0.000 abstract description 2
- 238000006482 condensation reaction Methods 0.000 abstract description 2
- XZBIXDPGRMLSTC-UHFFFAOYSA-N formohydrazide Chemical compound NNC=O XZBIXDPGRMLSTC-UHFFFAOYSA-N 0.000 abstract description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 230000000996 additive effect Effects 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 4
- 239000000976 ink Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- 238000005201 scrubbing Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- CFNMUZCFSDMZPQ-GHXNOFRVSA-N 7-[(z)-3-methyl-4-(4-methyl-5-oxo-2h-furan-2-yl)but-2-enoxy]chromen-2-one Chemical compound C=1C=C2C=CC(=O)OC2=CC=1OC/C=C(/C)CC1OC(=O)C(C)=C1 CFNMUZCFSDMZPQ-GHXNOFRVSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- YENIOYBTCIZCBJ-UHFFFAOYSA-N acetic acid;1-methoxypropan-2-ol Chemical compound CC(O)=O.COCC(C)O YENIOYBTCIZCBJ-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- QRXWMOHMRWLFEY-UHFFFAOYSA-N isoniazide Chemical compound NNC(=O)C1=CC=NC=C1 QRXWMOHMRWLFEY-UHFFFAOYSA-N 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011414 polymer cement Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002966 varnish Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses a coumarin imide hydrazide derivative, which has the following structure:
Description
Technical Field
The invention belongs to the technical field of paint, and particularly relates to a coumarin-based imine hydrazide derivative, and a preparation method and application thereof.
Background
The film forming additive can gradually form an additive for assisting in a paint film stage, so that the glass transition temperature of solids in the paint can be reduced. To be a good film forming process additive, the most basic condition is solubility. The solid in the emulsion can be well dissolved, so that the film forming additive molecules can be attached to the surface of the solid, and the solid molecules have certain fluidity by the means, so that a series of activities such as stretching can be performed.
The film-forming auxiliary additive has good solubility in emulsion paint, can promote film formation during film formation, and can be smoothly evaporated after film formation is finished. During the final evaporation, no changes in the properties of the paint film are caused. Film forming aids are high boiling point materials added to the paint or ink to aid in film formation, which can enable polymers with higher glass transition temperatures to form films at lower temperatures, thereby achieving better film forming effects. At present, film-forming aids such as alcohol ester 12 and the like applied to water-based paints or inks, which have advantages and disadvantages, respectively, require further improvement.
Therefore, it is desirable to provide a novel film forming aid that has superior properties to existing film forming aids, and coumarin has excellent film forming properties after structural modification, and is low in toxicity, easy to prepare and modify, and stable.
Disclosure of Invention
The invention aims to provide a coumarin-based imine hydrazide derivative.
Another object of the invention is to provide a process for the preparation of said coumarin imide hydrazide derivatives.
It is a further object of the present invention to provide the use of said coumarin-based imine hydrazide derivatives in the preparation of coating film forming aids.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
in a first aspect of the invention, there is provided a coumarin-based imine hydrazide derivative having the structure shown below:
in a second aspect of the invention, there is provided a method for preparing the coumarin imide hydrazide derivative, comprising the steps of:
First, synthesis of a compound represented by formula (II):
Dissolving a compound shown in a formula (III) and urotropine in a molar ratio of 1:1.5-3 (preferably 1:2.1) with acetic acid, carrying out reflux reaction for 1-12 h (preferably 6 h) at a temperature of 80-100 ℃ (preferably 90 ℃), adding a catalyst, and continuing the reaction for 30-90 min (preferably 1 h), wherein the molar ratio of the catalyst to the compound shown in the formula (III) is 0.01-1:1, so as to obtain a compound shown in a formula (II);
Second, synthesizing the compound shown in the formula (I):
dissolving a compound shown in a formula (II) and a compound shown in a formula (IV) in a molar ratio of 1:1-3 (preferably 1:2) in tetrahydrofuran, dropwise adding catalytic amount of acetic acid, and carrying out reflux reaction for 1-12 h (preferably 4 h) at a temperature of 55-80 ℃ (preferably 65 ℃), thereby obtaining the compound shown in the formula (I).
The catalyst in the first step is 20% hydrochloric acid solution.
In a third aspect of the invention, the application of the coumarin-based imine hydrazide derivative in preparing a coating film-forming additive is provided.
By adopting the technical scheme, the invention has the following advantages and beneficial effects:
The coumarin imide hydrazide derivative is prepared by carrying out Schiff base condensation reaction on the 4-methyl-7-hydroxycoumarin derivative and the 4-pyridine formylhydrazine, and the reaction is easy to prepare and simple in post-treatment. The compound of the invention has good effect when being used as a film forming auxiliary agent of paint.
The auxiliary agent synthesized by the invention has good effects on film forming state, film forming time, state in a container, storage stability, water resistance, alkali resistance, scrubbing resistance, lower viscosity, pulverization (grade) and color uniformity.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
Example 1
The synthesis method of coumarin derivative molecules shown in the formula (I) is as follows:
First, synthesis of a compound represented by formula (II):
7-hydroxy-4-methylcoumarin (5 g,28 mmol) of formula (III) and urotropine hexamine (8.7 g,60 mmol) were dissolved in acetic acid (45 mL), and the mixture was refluxed at 90℃for 6 hours, and then a 20% hydrochloric acid solution (1 mL) was added to continue the reaction for 1 hour. The molar ratio of hydrochloric acid to the compound of formula (III) was 0.1:1, and after the reaction was completed, it was cooled to room temperature. Ice water was added and extraction was performed three times with 150mL of ethyl acetate. The organic phase was dried over anhydrous sodium sulfate, filtered and the solvent was removed. The crude product was further purified by column chromatography on silica gel eluting with ethyl acetate/petroleum ether (v: v, 1:5) to give the compound of formula (II) (0.84 g, yield: 14%). Nuclear magnetic spectrum data ：1H NMR(600MHz,DMSO)δ(ppm)11.89(s,1H),10.42(s,1H),7.92(d,1H),6.95(d,1H),6.29(d,1H),2.40(d,3H).13C NMR(151MHz,DMSO)δ(ppm)δ191.31,163.65,158.85,155.10,153.65,133.33,113.51,111.84,111.09,108.99,18.29.
Second, synthesizing the compound shown in the formula (I):
the compound represented by the formula (II) (102.1 mg,0.5 mmol) and 4-pyridine carboxylic acid hydrazide represented by the formula (IV) (137.1 mg,1 mmol) were dissolved in 15mL of tetrahydrofuran, two drops of acetic acid were added dropwise, and the mixture was refluxed at 65℃for 4 hours. A yellow precipitate was precipitated during the reaction, and after completion of the reaction, cooled to room temperature, filtered and dried to give a compound represented by the formula (I) (0.143 g, yield: 88%). Nuclear magnetic pattern data ：1H NMR(400MHz,DMSO)δ(ppm)12.62(s,1H),12.56(s,1H),9.07(s,1H),8.81(d,2H),7.85(d,2H),7.67(d,1H),6.92(d,1H),6.21(s,1H),2.36(s,3H).13C NMR(151MHz,DMSO)δ(ppm)161.02,159.13,153.83,152.54,150.50,144.74,139.08,128.44,121.39,113.35,111.83,110.75,105.31,18.35. mass spectrum data: MS [ ESI ] M/z calculated for [ M+H ] + 324.0984; found 324.0983.
Example 2
Preparation of the solution
The compound (0.0324 g,0.1 mmol) of the formula (I) was dissolved in propylene glycol methyl ether acetic acid (PGMEA) (5 g,38 mmol) to form a solution for use.
Film formation and film Performance test
The compound shown in the formula (I) and the conventional commercial film-forming auxiliary agent-alcohol ester 12 (serving as a control) are respectively applied to oil paint (provided by industrial grade, libang paint (China) Co., ltd.) to respectively obtain paint a (paint a prepared from the compound (I)) and control paint (control paint prepared from the alcohol ester 12).
The formulations of the coating a and the control coating are shown in Table 1:
TABLE 1
The color-changing dye is free of ground color * and titanium dioxide is purchased from Shanghai Gan Tian optical materials limited company.
The film forming time, film forming state, water resistance, alkali resistance and other properties of the test paint a and the control paint are tested according to the GB/T23445-2009 standard of the polymer cement waterproof paint, the film forming time is tested according to the HG/T2454-2006 standard of the solvent polyurethane paint (two components), the water resistance is tested according to the HG/T3668-2009 standard, or the water resistance is tested according to the HG/T2593-1994 standard of the acrylic varnish, the alkali resistance is tested according to the GB/T9756-2001 standard of the latex paint for building indoor use, the scrub resistance is tested according to the JG/T3049-1998 standard of the inner wall putty, or the scrub resistance is tested according to the GB/T19250-2003 standard of the polyurethane waterproof paint.
The test results are shown in Table 2:
TABLE 2
As can be seen from Table 2, the film forming performance (such as film forming grade and film forming time) and the scrubbing resistance, chalking and color uniformity of the aqueous coating or ink using the coumarin-based imine hydrazide derivative of the present invention as a coating film forming aid are superior to those of the aqueous coating or ink using the conventional film forming aid alcohol ester 12.
The film forming state of the compound shown in the formula (I) is better than that of the alcohol ester 12, and the film forming time of the compound shown in the formula (I) is shorter than that of the alcohol ester 12. The compound of formula (I) is in a container in which the alcohol ester 12 is present. The storage stability of the compound of formula (I) is equivalent to that of alcohol ester 12. The water resistance of the compound represented by formula (I) is equivalent to that of alcohol ester 12. Alkali resistant equivalent alcohol ester 12 of the compound of formula (I). The scrub resistance of the compounds of formula (I) is (sub) better than that of the alcohol ester 12. The compound of formula (I) has a lower viscosity than the alcohol ester 12. The powdering (stage) of the compound of formula (I) is better than that of the alcohol ester 12. The compound of formula (I) has better color uniformity (grade) than alcohol ester 12.
The foregoing description is only illustrative of the preferred embodiment of the present invention, and is not to be construed as limiting the invention, but is to be construed as limiting the invention to any and all simple modifications, equivalent variations and adaptations of the embodiments described above, which are within the scope of the invention, may be made by those skilled in the art without departing from the scope of the invention.
Claims (4)
1. A coumarin-based imine hydrazide derivative characterized by the following structure:
2. A process for the preparation of coumarin-based imine hydrazide derivatives according to claim 1, characterized by comprising the steps of:
First, synthesis of a compound represented by formula (II):
Dissolving a compound shown in a formula (III) and urotropine in a molar ratio of 1:1.5-3 by using acetic acid, carrying out reflux reaction for 1-12 h at a temperature of 80-100 ℃, adding a catalyst, and continuing to react for 30-90 min, wherein the molar ratio of the catalyst to the compound shown in the formula (III) is 0.01-1:1, so as to obtain a compound shown in a formula (II);
Second, synthesizing the compound shown in the formula (I):
Dissolving a compound shown in a formula (II) and a compound shown in a formula (IV) in a molar ratio of 1:1-3 in tetrahydrofuran, dropwise adding catalytic amount of acetic acid, and carrying out reflux reaction for 1-12 h at a temperature of 55-80 ℃ to obtain the compound shown in the formula (I).
3. The process for preparing a coumarin-based imine hydrazide derivative according to claim 2, wherein the catalyst in the first step is 20% hydrochloric acid solution.
4. Use of a coumarin-based imine hydrazide derivative according to claim 1 in the preparation of a coating film forming aid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410087052.0A CN118146200A (en) | 2024-01-22 | 2024-01-22 | Coumarin-based imine hydrazide derivative and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202410087052.0A CN118146200A (en) | 2024-01-22 | 2024-01-22 | Coumarin-based imine hydrazide derivative and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118146200A true CN118146200A (en) | 2024-06-07 |
Family
ID=91284228
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202410087052.0A Pending CN118146200A (en) | 2024-01-22 | 2024-01-22 | Coumarin-based imine hydrazide derivative and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN118146200A (en) |
-
2024
- 2024-01-22 CN CN202410087052.0A patent/CN118146200A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5922914A (en) | Process to prepare tolterodine | |
| WO2006135425A2 (en) | Preparation of 4,5-dihydro-pyrazolo[3,4-c]pyrid-2-ones | |
| CN108250094B (en) | Preparation method of piperazine diketone compound | |
| CN114105984A (en) | Preparation method of indolizine corrosion inhibitor | |
| JP2002544207A (en) | 2,2-Dimethyl-1,3-dioxane intermediate salt and method for producing the same | |
| CN118146200A (en) | Coumarin-based imine hydrazide derivative and preparation method and application thereof | |
| JPS6046104B2 (en) | Method for producing butene derivatives | |
| CN110862372A (en) | Synthesis of clopidogrel intermediate (S) -2- (2-thiophene ethylamino) - (2-chlorphenyl) -methyl acetate | |
| CN110551123A (en) | Preparation method of 5- (tert-butyloxycarbonyl) -2-methyl-4, 5,6, 7-tetrahydro-2H-pyrazolo [4,3-C ] pyridine-7-carboxylic acid | |
| TWI796701B (en) | Stereoselective synthesis of intermediate for preparation of heterocyclic compound | |
| JP4994772B2 (en) | Method for producing piperidin-4-one derivative using bisaminol ether compound | |
| US6861525B2 (en) | Process for the preparation imidazo[1,2-A]pyridine-3-acetamides | |
| JPWO2019230848A1 (en) | Method for producing polymerizable compound | |
| CN114805168B (en) | Pyrrolinones and synthesis method thereof | |
| JP4118645B2 (en) | Method for producing calix [4] arene derivative mixture | |
| HU192136B (en) | Process for producing a 2-thiophfene-acetic acid derivative | |
| CN112062739B (en) | Preparation method for reducing lactone into hemiacetal | |
| US11155516B2 (en) | Synthesis of 2-(2-aminoethoxy) ethanol | |
| CN111233864B (en) | Method for industrially producing doxofylline | |
| CN107383010A (en) | A kind of compound and preparation method thereof | |
| JP4355839B2 (en) | Organic sulfonate of tetramethylpiperidine derivative and process for producing the same | |
| EP1631571B1 (en) | Novel intermediate for the preparation of therapeutically active imidazopyridines | |
| JPS6323872A (en) | Manufacture of 6-amino-1,2-dihydro-1-hydroxy- 2-imino-4-piperidinopyrimidine | |
| JPH02127475A (en) | Production of benzoindolenine cyanine dyestuff | |
| CN111333666A (en) | Three-branch benzothiophene acid ester compound and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |