CN102690237A - Method for synthesizing high-purity azoxystrobin - Google Patents
Method for synthesizing high-purity azoxystrobin Download PDFInfo
- Publication number
- CN102690237A CN102690237A CN2012101889894A CN201210188989A CN102690237A CN 102690237 A CN102690237 A CN 102690237A CN 2012101889894 A CN2012101889894 A CN 2012101889894A CN 201210188989 A CN201210188989 A CN 201210188989A CN 102690237 A CN102690237 A CN 102690237A
- Authority
- CN
- China
- Prior art keywords
- icia
- reaction
- pyrimidine
- hours
- synthesis
- 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
- 0 *=*=CCC1C=CCCC1 Chemical compound *=*=CCC1C=CCCC1 0.000 description 2
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Abstract
The invention relates to a method for synthesizing high-purity azoxystrobin. The azoxystrobin is obtained through reaction of pyrimidine chloride and o-cyanobenzyl phenol under the action of alkali. The method comprises the following steps of: in a reaction vessel, adding reaction solvent, dehydrating agent and the o-cyanobenzyl phenol through inert gas shielding; stirring at room temperature, adding the pyrimidine chloride and phase transfer catalyst, and reacting for 3 hours after heating up to 50-110 DEG C; and filtering, decompressing and concentrating the filtrate to recover methylbenzene, adding methyl alcohol to dissolve, cooling to be 4 DEG C for crystallizing, and filtering to obtain the azoxystrobin. The method has the characteristic of high synthesis total recovery, and an easy-to-get and safe chemical reagent is used, so that the synthesizing process is more environmental-friendly and is safe to operate.
Description
Technical field
The present invention relates to a kind of method of synthesis of high purity ICIA 5504.
Background technology
ICIA 5504 (Azoxystrobin) is prompt sharp Kanggong's department's exploitation and first commercial methoxy acrylic bactericide, and the chemical name of ICIA 5504 is (E)-2-(2-(6-(2-cyano-benzene oxygen) pyrimidine-4-oxygen base) phenyl)-3-methoxy-methyl acrylate (I).Efficient and the wide spectrum of this sterilant; Almost can prevent and treat all fungies, Oomycete, Phycomycetes, Ascomycetes and deuteromycetes disease, and on cereal, paddy rice, grape, yam, vegetables, fruit tree, beans and other crop, use through cauline leaf processing, seed treatment.
The method of producing ICIA 5504 at present mainly contains:
(1) be starting raw material from o-hydroxy phenylacetic acid; Through cyclization is benzofuranone; Then introduce the methoxy methene with trimethyl orthoformate or methyl-formiate; Then obtain (2-hydroxy phenyl)-3 with sodium methylate/methyl alcohol open loop addition, 3-dimethoxy methyl propionate is with 4; Obtain (E) 2-(2-(6-chloro-pyrimidine-4-oxygen base) phenyl)-3-methoxy-methyl acrylate (hereinafter to be referred as " pyrimidine muriate ") with the sal enixum separating methanol after the condensation of 6-dichloro pyrimidine, obtain ICIA 5504 with adjacent cyanophenol condensation then.This is to comprise just reaching earlier the widely used compound method with domestic and international most of enterprise.GB2291874，WO1998007707?，Australian?Journal?of?Chemistry,?26(5),1079,1973;?Journal?of?Organic?Chemistry,?40(24),?3474,?1975。
(2) 4; The 6-dichloro pyrimidine obtains 2-(2-(6-(2-cyano-benzene oxygen) pyrimidine-4-oxygen base) phenyl)-methyl acetate with adjacent cyanophenol and the condensation of o-hydroxy phenylacetic acid methyl esters successively; Prepare ICIA 5504 with highly basic alkylations such as butyllithiums again; It is higher that this method prepares general alkylation products yield, but it is lower to prepare the ICIA 5504 yield, and butyllithium is dangerous higher in large-scale production.Like patent WO02100837, US20060229450, US20040242607, US7244737, US7084272, EP1399427, CN02810368.
(3) 2-(2-(6-(2-cyano-benzene oxygen) pyrimidine-4-oxygen base) phenyl)-methyl acetate is with titanium tetrachloride catalysis and trimethyl orthoformate or methyl-formiate formylation; Etherificate is introduced the methoxy thiazolinyl and is obtained ICIA 5504 again, and this is the working method of Beijing Yingtai Jiahe Technology Co., Ltd.Like patent CN200710163386, WO2009052719.
(4) the recent public use triethylene diamine of Syngenta Co.,Ltd is as catalyzer, and the condensation under the alkali effect of pyrimidine muriate and adjacent cyanophenol obtains ICIA 5504.Like patent WO2008/043978.
Method (1) is at present widely used synthetic ICIA 5504 technology, and owing to reasons such as side reaction make synthesis yield not ideal enough, impurity is more during especially final step is produced for production process, and product needed repeatedly purifying just can reach 99% above content.Method (2) is owing to the activity of butyllithium, and very easily combustion explosion generally seldom applies to large-scale commercial prodn.Method (3) will use titanium tetrachloride as catalyzer though on total recovery, improve in the production process.The unstable chemcial property of titanium tetrachloride is met moisture and is emitted white cigarette immediately, uses inconvenience, obtains many insoluble substance titanium oxide in addition in the post-reaction treatment and forms the pasty state colloid, the product separation trouble.Method (4) has used triethylene diamine as catalyzer, can reduce temperature of reaction, improve yield, but the catalyzer price comparison is expensive.The aftertreatment of this method has a large amount of spent process waters to produce, and producing one ton of ICIA 5504 has the higher waste water of 2.6 tons of ammonia-nitrogen contents (catalyzer triethylene diamine and do not steam clean solvent DMF) generation.
Summary of the invention
Its purpose of the present invention just is to provide a kind of method of synthesis of high purity ICIA 5504, has the high characteristics of synthetic total recovery, and has used the safe chemical reagent that is easy to get, and synthesis technique is environmental friendliness and operational safety more.
The technical scheme that realizes above-mentioned purpose and take is that pyrimidine muriate and adjacent cyanophenol exist
The effect of alkali reaction down obtains ICIA 5504, comprises step, in reaction vessel, is the benchmark raw material with the pyrimidine muriate, and logical protection of inert gas adds 2.73 times of reaction solvents, 0.182 times of dewatering agent and 0.375 times of adjacent cyanophenol, stirring at room 2 hours; Add pyrimidine muriate and 0.01 times of phase-transfer catalyst, stirring at room 2 hours is warmed up to 50-110 ℃ of reaction 3 hours; Filter, filtrate decompression concentrates and reclaims toluene, adds 0.78 times of dissolve with methanol, is cooled to 4 ℃ of crystallizations 6 hours, filters and obtains ICIA 5504.
Compared with prior art the present invention has the following advantages.
Have the high characteristics of synthetic total recovery, and used the safe chemical reagent that is easy to get, synthesis technique is environmental friendliness and operational safety more.
Embodiment
Pyrimidine muriate and adjacent cyanophenol react under the effect of alkali and obtain ICIA 5504, comprise step
1) in reaction vessel, be the benchmark raw material with the pyrimidine muriate, logical protection of inert gas adds 2.73 times of reaction solvents, 0.182 times of dewatering agent and 0.375 times of adjacent cyanophenol, stirring at room 2 hours;
2) add pyrimidine muriate and 0.01 times of phase-transfer catalyst, stirring at room 2 hours is warmed up to 50-110 ℃ of reaction 3 hours;
3) filter, filtrate decompression concentrates and reclaims toluene, adds 0.78 times of dissolve with methanol, is cooled to 4 ℃ of crystallizations 6 hours, filters and obtains ICIA 5504.
Said rare gas element comprises nitrogen or argon gas.
Said reaction solvent comprises aromatic hydrocarbon such as toluene, YLENE or chlorobenzene, ether solvents such as isopropyl ether, glycol dimethyl ether or butyl ether, ketones solvents such as acetone, butanone or MIBK, esters solvents such as ETHYLE ACETATE, propyl acetate or butylacetate.
Said dewatering agent comprises the stable neutral siccative of chemical property such as molecular sieve, anhydrous magnesium sulfate, SODIUM SULPHATE ANHYDROUS 99PCT or anhydrous calciumsulphate.
Said phase-transfer catalyst comprises quaternary ammonium salt catalysts such as tetrabutylammonium chloride, Tetrabutyl amonium bromide, benzyltriethylammoinium chloride or palmityl trimethyl ammonium chloride.
Said alkali comprises yellow soda ash, salt of wormwood, sodium hydroxide or Pottasium Hydroxide.
The method synthetic ICIA 5504 product that patent WO2008/043978 provides is analyzed, has been isolated two content, carried out the structure evaluation, and analyzed the principle that impurity produces than higher impurity:
Impurity one:
Impurity two
The major cause of two impurity generations is that all the water that produces in the reaction system causes; DMF hydrolysis under alkaline condition produces n n dimetylaniline and the reaction of pyrimidine muriate obtains impurity one, and the pyrimidine muriate is hydrolyzed to hydroxy pyrimidine and obtains impurity two with the condensation of pyrimidine muriate again.Therefore we added dewatering agent and remove to anhydrate and just can reduce and even avoid the generation of impurity before adding the pyrimidine muriate.
The synthesis technology principle is following:
Type reaction process of the present invention: reactor drum is handled through the vacuum exchange, nitrogen protection, and toluene is as solvent; Add molecular sieve as dewatering agent (siccative); Adjacent cyanophenol and yellow soda ash react certain hour under benzyltriethylammoinium chloride catalysis, add pyrimidine muriate reaction certain hour then, concentrate toluene behind the heat filtering; Obtain the ICIA 5504 product of purity more than 99% with recrystallizing methanol, yield is more than 95%.
The reaction process blanketing with inert gas, for example nitrogen and argon gas etc. are preferably used nitrogen.Reaction kettle is with vacuum and nitrogen interaction process; Reaction process can avoid the phenol negative ion by dioxygen oxidation with nitrogen protection; Influence reaction yield on the one hand, the more important thing is that avoiding the oxidized quinones by product of adjacent cyanophenol to bring into causes product colour darker in the product.
Reaction solvent can be selected aromatic hydrocarbon such as toluene, YLENE and chlorobenzene for use, ether solvents such as isopropyl ether, glycol dimethyl ether and butyl ether, ketones solvents such as acetone, butanone and MIBK; Esters solvents such as ETHYLE ACETATE, propyl acetate and butylacetate; Wherein preferred toluene, wide material sources are stable, low price; The recovery is high, and byproduct of reaction is minimum.
Dewatering agent can select the stable neutral siccative of chemical property such as molecular sieve, anhydrous magnesium sulfate, SODIUM SULPHATE ANHYDROUS 99PCT and anhydrous calciumsulphate; Wherein the preferred molecular sieve effect is best; And easy recovery recycles, and consumption is the 10-50% of substrate pyrimidine muriate weight, and preferred 15-20% is best.
Phase-transfer catalyst can reduce temperature of reaction, reduces the generation of by product.Catalyzer can be selected quaternary ammonium salt catalysts such as tetrabutylammonium chloride, Tetrabutyl amonium bromide, benzyltriethylammoinium chloride and palmityl trimethyl ammonium chloride; Preferred benzyltriethylammoinium chloride; Consumption is the 0.1%-5% of substrate pyrimidine muriate weight, the most handy 0.5%-1%.
Alkali can be selected yellow soda ash, salt of wormwood, sodium hydroxide and Pottasium Hydroxide etc. for use, preferred yellow soda ash, and low price, safe in utilization.
Temperature of reaction can be carried out between 50-110 ℃, and temperature too low reaction is too slow, lacks efficient, and temperature is too high, and energy consumption is big, and side reaction is many, takes all factors into consideration between 80-90 ℃ of the control relatively good.
Reaction finishes after heat and removes by filter inorganic salt sodium-chlor and the molecular sieve that reaction produces, can reclaim after the separation molecular sieve again activation apply mechanically.
This method yield is high, and product purity is high, and the three wastes are few, is an environmentally friendly technology of producing ICIA 5504.
Below in conjunction with embodiment the present invention is further specified, but the present invention applies for the content of protection and the restriction that scope does not receive following embodiment.
Embodiment one
According to the method embodiment one that patent WO2008/043978 provides, use DMF to be solvent, triethylene diamine is a catalyzer, and pyrimidine muriate and adjacent cyanophenol be the synthetic ICIA 5504 that obtains under the salt of wormwood effect, and it is following to obtain impurity through column chromatography for separation:
Impurity one:
1HNMR（CDCl
3）,δ：8.19(1H,s)，7.35(1H,s)，7.22(2H,m),7.13(1H,m)，7.06(1H,m)，5.61(1H,s)，3.63(3H,s)，3.49(3H,s)，2.93(6H,s)
MS（EI
+）m/Z:330(M+1)
Impurity two:
1HNMR（CDCl
3）,δ：8.52(2H,s)，7.47(2H,s)，7.41(2H,m)，7.34(4H,m)，7.20(2H,d)，6.50(2H,s)，3.74(6H,s)，3.60(6H,s)
MS（EI
+）m/Z:587(M+1)
Embodiment two
In there-necked flask, vacuum displacement 3 times adds 100 milliliters of toluene, 5.3 gram soda ash lights and the adjacent cyanophenol of 12 grams, 6 grams, 4 molecular sieves, stirring at room 1 hour; Add 33 gram pyrimidine muriates (content 97%) and 0.3 gram benzyltriethylammoinium chloride, be warmed up to 85 ℃ of reactions 3 hours, filtered while hot, filtrate decompression concentrate and reclaim toluene, add the dissolving of 25 ml methanol, are cooled to 4 ℃ of crystallizations; Filtration obtains 38.8 grams, content 99.9% (HPLC), 99.1% (external standard), yield 95.5%.
Embodiment three
In there-necked flask, vacuum displacement 3 times adds 180 milliliters of toluene, 10.6 gram soda ash lights and the adjacent cyanophenol of 24 grams, 12 grams, 4 molecular sieves, stirring at room 1.5 hours; Add 66 gram pyrimidine muriate (content 97%) and 0.5 benzyltriethylammoinium chlorides, be warmed up to 85 ℃ of reactions 3 hours, filtered while hot, filtrate decompression concentrate and reclaim toluene, add the dissolving of 50 ml methanol, are cooled to 4 ℃ of crystallizations; Filtration obtains 77.2 grams, content 99.9% (HPLC), 99.3% (external standard), yield 95.2%.
Embodiment four
In 2000 liters of enamel reaction stills,, adds 900 kilograms of toluene, 53 kilograms of soda ash lights and 120 kg neighbour cyanophenol, 60 kilogram of 4 molecular sieve, stirring at room 2.5 hours with vacuum displacement 3 times; Add 330 kilograms of pyrimidine muriates (content 97%) and 2.65 kilograms of benzyltriethylammoinium chlorides, be warmed up to 85 ℃ of reactions 5 hours; Heat filtering, filtrating is transferred in 2000 liters of stainless steel cauldrons, and concentrating under reduced pressure reclaims 825 kilograms of toluene, adds 250 kilograms of dissolve with methanol, is cooled to 4 ℃ of crystallizations; Centrifugal, oven dry obtains 386 kilograms of products, content 99.9% (HPLC), 99.5% (external standard), yield 95.4%.
Comparative example one (without nitrogen protection, molecular sieve and phase-transfer catalyst)
In there-necked flask, add 180 milliliters of toluene, 10.6 gram soda ash lights and the adjacent cyanophenol of 24 grams, stirring at room 1.5 hours; Add 66 gram pyrimidine muriates (content 97%), be warmed up to 105 ℃ of reactions 5 hours, filtered while hot, filtrate decompression concentrate and reclaim toluene, add the dissolving of 50 ml methanol, are cooled to 4 ℃ of crystallizations; Filtration obtains 71.6 grams, content 98.1% (HPLC), 95.6% (external standard), yield 85.0%.
Comparative example two (without molecular sieve and phase-transfer catalyst)
In there-necked flask,, add 180 milliliters of toluene, 10.6 gram soda ash lights and the adjacent cyanophenol of 24 grams, stirring at room 1.5 hours with vacuum displacement 3 times; Add 66 gram pyrimidine muriates (content 97%), be warmed up to 105 ℃ of reactions 5 hours, filtered while hot, filtrate decompression concentrate and reclaim toluene, add the dissolving of 50 ml methanol, are cooled to 4 ℃ of crystallizations; Filtration obtains 72.5 grams, content 98.5% (HPLC), 96.6% (external standard), yield 87.0%.
Comparative example three (without phase-transfer catalyst)
In there-necked flask,, add 180 milliliters of toluene, 10.6 gram soda ash lights and the adjacent cyanophenol of 24 grams, 12 grams, 4 molecular sieves, stirring at room 1.5 hours with vacuum displacement 3 times; Add 66 gram pyrimidine muriates (content 97%), be warmed up to 105 ℃ of reactions 5 hours, filtered while hot, filtrate decompression concentrate and reclaim toluene, add the dissolving of 50 ml methanol, are cooled to 4 ℃ of crystallizations; Filtration obtains 74.4 grams, content 99.1% (HPLC), 98.6% (external standard), yield 91.1%.
Claims (6)
1. the method for a synthesis of high purity ICIA 5504, pyrimidine muriate and adjacent cyanophenol react under the effect of alkali and obtain ICIA 5504, it is characterized in that, comprise step
(1) in reaction vessel, be the benchmark raw material with the pyrimidine muriate, logical protection of inert gas adds 2.73 times of reaction solvents, 0.182 times of dewatering agent and 0.375 times of adjacent cyanophenol, stirring at room 2 hours;
(2) add pyrimidine muriate and 0.01 times of phase-transfer catalyst, stirring at room 2 hours is warmed up to 50-110 ℃ of reaction 3 hours;
(3) filter, filtrate decompression concentrates and reclaims toluene, adds 0.78 times of dissolve with methanol, is cooled to 4 ℃ of crystallizations 6 hours, filters and obtains ICIA 5504.
2. the method for a kind of synthesis of high purity ICIA 5504 according to claim 1 is characterized in that, said rare gas element comprises nitrogen or argon gas.
3. the method for a kind of synthesis of high purity ICIA 5504 according to claim 1; It is characterized in that; Said reaction solvent comprises aromatic hydrocarbon such as toluene, YLENE or chlorobenzene; Ether solvents such as isopropyl ether, glycol dimethyl ether or butyl ether, ketones solvents such as acetone, butanone or MIBK, esters solvents such as ETHYLE ACETATE, propyl acetate or butylacetate.
4. the method for a kind of synthesis of high purity ICIA 5504 according to claim 1 is characterized in that, said dewatering agent comprises the stable neutral siccative of chemical property such as molecular sieve, anhydrous magnesium sulfate, SODIUM SULPHATE ANHYDROUS 99PCT or anhydrous calciumsulphate.
5. the method for a kind of synthesis of high purity ICIA 5504 according to claim 1; It is characterized in that said phase-transfer catalyst comprises quaternary ammonium salt catalysts such as tetrabutylammonium chloride, Tetrabutyl amonium bromide, benzyltriethylammoinium chloride or palmityl trimethyl ammonium chloride.
6. the method for a kind of synthesis of high purity ICIA 5504 according to claim 1 is characterized in that, said alkali comprises yellow soda ash, salt of wormwood, sodium hydroxide or Pottasium Hydroxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101889894A CN102690237A (en) | 2012-06-11 | 2012-06-11 | Method for synthesizing high-purity azoxystrobin |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101889894A CN102690237A (en) | 2012-06-11 | 2012-06-11 | Method for synthesizing high-purity azoxystrobin |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102690237A true CN102690237A (en) | 2012-09-26 |
Family
ID=46855989
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012101889894A Pending CN102690237A (en) | 2012-06-11 | 2012-06-11 | Method for synthesizing high-purity azoxystrobin |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102690237A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265496A (en) * | 2013-05-16 | 2013-08-28 | 北京颖泰嘉和生物科技有限公司 | Preparation method of azoxystrobin |
| CN112094238A (en) * | 2020-09-23 | 2020-12-18 | 江苏大学 | Method for post-treatment of azoxystrobin production |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101163682A (en) * | 2005-04-26 | 2008-04-16 | 先正达有限公司 | Chemical process |
| WO2008075341A1 (en) * | 2006-12-17 | 2008-06-26 | Makhteshim Chemical Works Ltd. | Process for the preparation of substituted cynophenoxy-pyrimidinyloxy-phenyl acrylate derivatives |
| CN101522639A (en) * | 2006-10-09 | 2009-09-02 | 先正达有限公司 | Preparation of azoxystrobin |
-
2012
- 2012-06-11 CN CN2012101889894A patent/CN102690237A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101163682A (en) * | 2005-04-26 | 2008-04-16 | 先正达有限公司 | Chemical process |
| CN101522639A (en) * | 2006-10-09 | 2009-09-02 | 先正达有限公司 | Preparation of azoxystrobin |
| WO2008075341A1 (en) * | 2006-12-17 | 2008-06-26 | Makhteshim Chemical Works Ltd. | Process for the preparation of substituted cynophenoxy-pyrimidinyloxy-phenyl acrylate derivatives |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103265496A (en) * | 2013-05-16 | 2013-08-28 | 北京颖泰嘉和生物科技有限公司 | Preparation method of azoxystrobin |
| CN103265496B (en) * | 2013-05-16 | 2015-02-25 | 北京颖泰嘉和生物科技有限公司 | Preparation method of azoxystrobin |
| EP2998299A4 (en) * | 2013-05-16 | 2017-01-04 | Nutrichem Company Limited | Preparation method of azoxystrobin |
| US9611226B2 (en) | 2013-05-16 | 2017-04-04 | Nutrichem Company Limited | Preparation method for azoxystrobin |
| CN112094238A (en) * | 2020-09-23 | 2020-12-18 | 江苏大学 | Method for post-treatment of azoxystrobin production |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102050781B (en) | Industrial preparation method of hydroxychloroquine sulfate | |
| CN103553881A (en) | Biphenol compound preparation method | |
| CN102627573A (en) | Synthesis method for 5-aminolevulinic acid hydrochloride | |
| CN103130657B (en) | Synthetic method of 2-chloro-4-aminophenol | |
| CN110668918B (en) | Chemical synthesis method of 3-chloro-1-propanol | |
| CN102690237A (en) | Method for synthesizing high-purity azoxystrobin | |
| CN103086959A (en) | Novel process for producing 3,5,6-sodium trichloropyrindinol | |
| CN112295608A (en) | Recycling method for regenerating ferric trichloride for aromatizing triazole compounds | |
| CN109503343B (en) | Preparation method of photoinitiator 184 | |
| CN102040486B (en) | Preparation method of trimethylolpropane diallyl ether | |
| CN106432114A (en) | Method for synthesizing 2-(2,4-dihydroxyphenyl)-4,6-diphenyl-1,3,5-sym-triazine | |
| CN103351291B (en) | It is a kind of that natural phlorizin is semi-synthetic prepares Phloretin technique | |
| CN108031476B (en) | Catalyst for preparing β -ionone, preparation method thereof and method for preparing β -ionone by using catalyst | |
| CN110128246B (en) | Preparation method of hydroxytyrosol | |
| CN110734368A (en) | Preparation method of buparvaquone | |
| CN105566223A (en) | Crude iminostilbene product recrystallization method | |
| CN104356103A (en) | Synthetic method of 6, 7-dimethoxyl coumarin | |
| CN110272451B (en) | Preparation method of tetraphenylphenol phosphonium salt | |
| JP5236274B2 (en) | Method for producing 6-hydroxy-2-naphthoic acid regenerated product | |
| CN102285878B (en) | Method for preparing 2-halo-4,5-dimethoxy benzoic acid | |
| CN102746260A (en) | Method for preparing benzofuran-2-(3H)-one | |
| CN102241575B (en) | Method for preparing protocatechuic aldehyde from vanillin | |
| CN114031568B (en) | Novel triazine derivative and synthetic method thereof | |
| CN108069897B (en) | Method for synthesizing nicotinic acid by using carbon dioxide | |
| CN115974727B (en) | Synthesis method of bifenazate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20120926 |