CN1267422C - Preparation method of pyriproxyfen - Google Patents
Preparation method of pyriproxyfen Download PDFInfo
- Publication number
- CN1267422C CN1267422C CN 200510023399 CN200510023399A CN1267422C CN 1267422 C CN1267422 C CN 1267422C CN 200510023399 CN200510023399 CN 200510023399 CN 200510023399 A CN200510023399 A CN 200510023399A CN 1267422 C CN1267422 C CN 1267422C
- Authority
- CN
- China
- Prior art keywords
- reaction
- pyriproxyfen
- phenoxy group
- solvent
- phenoxy
- 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.)
- Expired - Fee Related
Links
Landscapes
- Pyridine Compounds (AREA)
Abstract
The present invention discloses a preparation method for pyriproxyfen. The method comprises the following steps: step a, water is used as a solvent for making phenoxyphenol react with propylene oxide under the catalysis of an alkali catalyst, and 1-(4-phenoxy phenoxy)-2-propanol is obtained; step b, ether or N-methyl pyrrolidone is used as a solvent for making the 1-(4-phenoxy phenoxy)-2-propanol react with 2-chloropyridine under the catalysis of an alkali catalyst, and after the reaction is finished, the filtration is carried out. The solvent is removed through steaming, and a pyriproxyfen crude product is obtained. In the present invention, the pyriproxyfen is prepared with a two step method, a phase transfer catalyst does not exist in step a, the cost is low, and the ether or the N-methyl pyrrolidone is used as the reaction solvent in step b.Compared with the existing patent technologies, the pyriproxyfen of the present invention has the advantages of less side reaction, easy product purification and high reaction yield. The reaction yield is larger than or is equal to 85%.
Description
Technical field
The present invention relates to a kind of preparation method who contains the insect growth regulator(IGR) of phenyl ether structure, relate to a kind of preparation method of pyriproxyfen in particular.
Background technology
Pyriproxyfen (pyriproxyfen), chemical name are 4-phenoxy group phenoxy group-(RS)-2-(2-pyridyloxy) propyl ether, molecular formula C
20H
19NO
3, molecular weight 321.38, chemical structural formula is as follows:
Pyriproxyfen is a kind of insect growth regulator(IGR) with juvenile hormone activity, can be used for preventing and treating Homoptera, Thysanoptera, Diptera, lepidopterous Agricultural pests, remove whitefly in bt cotton, greenhouse whitefly has outside the high activity, to pear psyllid, scale insects such as Red Garden a red-spotted lizard, black peach aphid, prodenia litura, Agricultural pests such as colorado potato bug all have good prevention effect, its action principle is the etap (as the larva end length of time and pupa time) of selecting insect under normal circumstances not secrete or seldom secrete neotonin to use this insect growth regulator(IGR) to cast off a skin with the metamorphosis that suppresses insect, influence reproduction and the growth of insect, even cause the death of insect.Generally, synthesizing in two steps of pyriproxyfen: the first step is raw material with the p-phenoxyphenol, with propylene oxide reaction, obtains 1-(4-phenoxy group phenoxy group)-2-propyl alcohol under alkaline condition; Second step with 1-(4-phenoxy group phenoxy group)-2-propyl alcohol and the reaction of 2-chloropyridine, obtained pyriproxyfen in inert solvent, chemical equation is as follows:
The first step
Second step
Chinese invention patent publication number CN 1347864, Japanese kokai publication sho 60-36403 had once reported the preparation method of 1-(4-phenoxy group phenoxy group)-2-propyl alcohol, under phase-transfer catalyst catalysis, with p-phenoxyphenol and the synthetic 1-(4-phenoxy group phenoxy group) of propylene oxide reaction-2-propyl alcohol, reaction yield is 83.8%.Its shortcoming is that phase-transfer catalyst costs an arm and a leg, the running cost height.Chinese invention patent publication number CN 03112989.7 with the p-phenoxyphenol be raw material in alcohol solvent with propylene oxide reaction, synthetic 1-(4-phenoxy group phenoxy group)-2-propyl alcohol, then in toluene with 2-chloropyridine prepared in reaction pyriproxyfen.The shortcoming of this method is that reaction yield is low, and total recovery only is about 40%.Japanese kokai publication sho 58-73400, U.S. Pat P 4751225, USP 4879292, USP 4970222 propose at inert solvent (as N, dinethylformamide, tetrahydrofuran (THF), methyl-sulphoxide, toluene, glycol dimethyl ether) in be catalyzer with the sodium hydride, make 1-(4-phenoxy group phenoxy group)-2-propyl alcohol and 2-chloropyridine prepared in reaction pyriproxyfen.But can explode because sodium hydride is met water, above-mentioned reaction is dangerous, and the post-reaction treatment complexity, and product needs to separate with silica gel chromatographic column, and yield is about 79%.
Summary of the invention
Technical problem to be solved by this invention is the disadvantages associated that overcomes existing pyriproxyfen preparation method, and a kind of simple, efficient, pyriproxyfen preparation method that yield is high is provided.
Technical scheme of the present invention: a kind of preparation method of pyriproxyfen comprises the following steps:
A. with water solvent, under potassium hydroxide, sodium hydroxide or potassium alkaline catalyst, make p-phenoxyphenol and propylene oxide reaction, the mol ratio of phenoxy phenyl and basic catalyst and propylene oxide is 1: 0.1~2: 2~5, the temperature of reaction of phenoxy phenyl and propylene oxide is controlled at 20~60 ℃, reaction times was controlled at 1~6 hour, obtained 1-(4-phenoxy group phenoxy group)-2-propyl alcohol;
B. be solvent with dioxane or ethylene glycol diethyl ether or N-Methyl pyrrolidone, under above-mentioned basic catalyst catalysis, making the above-mentioned 1-that obtains (4-phenoxy group phenoxy group)-2-propyl alcohol and basic catalyst and 2-chloropyridine is 1: 2~5: 1~1.6 in mol ratio, temperature of reaction is controlled at 60~160 ℃, reaction times was controlled under 1~12 hour reacts, finish after-filtration in reaction, steaming desolventizes, and promptly gets the pyriproxyfen crude product.
The invention has the beneficial effects as follows: the present invention prepares pyriproxyfen by two-step approach, and the yield of step a is more than 90%, and no phase-transfer catalyst, and cost is low.Pyriproxyfen elaboration purity 〉=98.5% that the pyriproxyfen crude product that step b obtains obtains through recrystallization.The present invention adopts ether or N-Methyl pyrrolidone as reaction solvent, compares with existing patented technology, and side reaction is few, and product is easy to purifying, reaction yield height (yield 〉=85%).
Embodiment
Below in conjunction with embodiment the present invention is described in further detail: a kind of preparation method of pyriproxyfen: (a) be solvent with water, under the catalysis of potassium hydroxide, sodium hydroxide or salt of wormwood, with p-phenoxyphenol and propylene oxide reaction, the mol ratio of phenoxy phenyl and basic catalyst and propylene oxide is 1: 0.1~2: 2~5, temperature of reaction is controlled at 20~60 ℃, reaction times is 1~6 hour, after reaction finishes, filter step product 1-(4-phenoxy group the phenoxy group)-2-propyl alcohol of promptly winning, yield can be more than 90%; (b) adopting ether solvent (as dioxane, ethylene glycol diethyl ether etc.) or N-Methyl pyrrolidone is solvent, with above-mentioned the first step product 1-(4-phenoxy group phenoxy group)-2-propyl alcohol and basic catalyst (potassium hydroxide, sodium hydroxide), react with the 2-chloropyridine, mol ratio is 1: 2~5: 1~1.6, temperature of reaction is controlled at 60~160 ℃, reaction times is 1~12 hour, reaction finishes after-filtration, steaming desolventizes, promptly get the pyriproxyfen crude product, crude product promptly gets the pyriproxyfen elaboration through recrystallization, purity 〉=98.5%.
Embodiment 1
The first step: in 250 milliliter of four neck reaction flask that thermometer, reflux condensing tube, agitator are housed, add 30.0 gram (0.16 mole) p-phenoxyphenols, 2.7 gram (0.048 mole) potassium hydroxide and 100 ml waters, stir and drip 22.5 gram (0.39 mole) propylene oxide down, at room temperature continue after dripping off to stir 3 hours.Reaction mixture filters, and oven dry can be won and be gone on foot product 1-(4-phenoxy group phenoxy group)-2-propyl alcohol 37 grams, yield 94.0%.
Second step: in 250 milliliter of four neck reaction flask that thermometer, reflux condensing tube, agitator are housed, add above-mentioned the first step product 1-(4-phenoxy group phenoxy group)-2-propyl alcohol, 25.2 gram (0.45 mole) potassium hydroxide and 100 milliliters of N-Methyl pyrrolidone, be heated to 150 ℃, slowly drip 25 gram (0.22 mole) 2-chloropyridines, insulation reaction is 5 hours then, cooling is filtered.Promptly get the pyriproxyfen crude product behind the pressure reducing and steaming solvent, after recrystallization, drying, get pyriproxyfen finished product 38.0 grams, two step total recoverys 73.4%, product fusing point: 47.2~47.8 ℃.
Embodiment 2
The first step: in 250 milliliter of four neck reaction flask that thermometer, reflux condensing tube, agitator are housed, add 30.0 gram (0.16 mole) p-phenoxyphenols, 27.6 gram (0.2 mole) salt of wormwood and 100 ml waters, stir and drip 27.8 gram (0.48 mole) propylene oxide down, at room temperature continue after dripping off to stir 3 hours.Reaction mixture filters, and oven dry can be won and be gone on foot product 1-(4-phenoxy group phenoxy group)-2-propyl alcohol.
Second step: in 250 milliliter of four neck reaction flask that thermometer, reflux condensing tube, agitator are housed, add above-mentioned the first step product 1-(4-phenoxy group phenoxy group)-2-propyl alcohol, 25.2 gram (0.45 mole) potassium hydroxide and 100 milliliters of ethylene glycol diethyl ethers, be heated to 120 ℃, slowly drip 25 gram (0.22 mole) 2-chloropyridines, insulation reaction is 3 hours then, cooling is filtered.Promptly get the pyriproxyfen crude product behind the pressure reducing and steaming solvent, after recrystallization, drying, get pyriproxyfen finished product 37.5 grams, two step total recoverys 72.4%, product fusing point: 48.1~48.7 ℃.
Embodiment 3
In 250 milliliter of four neck reaction flask that thermometer, reflux condensing tube, agitator are housed, add 1-(4-phenoxy group phenoxy group)-2-propyl alcohol 25 grams (0.10 mole), potassium hydroxide 19.6 gram (0.35 mole), 50 milliliters of ethylene glycol diethyl ethers, be heated to 124 ℃, slowly drip 17 gram (0.15 mole) 2-chloropyridines, insulation reaction is 3 hours then, cooling is filtered.Promptly get the pyriproxyfen crude product behind the pressure reducing and steaming solvent, after recrystallization, drying, get pyriproxyfen finished product 28 grams, yield 87.1%, fusing point: 48.3~49.0 ℃.
Reference examples 1
With reference to embodiment one, other conditions are constant, and the first step is solvent with ethanol, and 84%, the second step of yield, other conditions were constant, were solvent with toluene, and 110 ℃ of temperature of reaction get pyriproxyfen 24 grams, and yield is 46.5%.
Reference examples 2
With reference to embodiment three, other conditions are constant, and with N, dinethylformamide is a solvent, and 150 ℃ of temperature of reaction get pyriproxyfen 16.8 grams, and yield is 52.4%.
Above said content only is the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.
Claims (1)
1. the preparation method of a pyriproxyfen is characterized in that the following step:
A. with water solvent, under potassium hydroxide, sodium hydroxide or potassium alkaline catalyst, make p-phenoxyphenol and propylene oxide reaction, the mol ratio of phenoxy phenyl and basic catalyst and propylene oxide is 1: 0.1~2: 2~5, the temperature of reaction of phenoxy phenyl and propylene oxide is controlled at 20~60 ℃, reaction times was controlled at 1~6 hour, obtained 1-(4-phenoxy group phenoxy group)-2-propyl alcohol;
B. be solvent with dioxane or ethylene glycol diethyl ether or N-Methyl pyrrolidone, under above-mentioned basic catalyst catalysis, making the above-mentioned 1-that obtains (4-phenoxy group phenoxy group)-2-propyl alcohol and basic catalyst and 2-chloropyridine is 1: 2~5: 1~1.6 in its mol ratio, temperature of reaction is controlled at 60~160 ℃, reaction times was controlled under 1~12 hour reacts, finish after-filtration in reaction, steaming desolventizes, and promptly gets the pyriproxyfen crude product.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 200510023399 CN1267422C (en) | 2005-01-18 | 2005-01-18 | Preparation method of pyriproxyfen |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN 200510023399 CN1267422C (en) | 2005-01-18 | 2005-01-18 | Preparation method of pyriproxyfen |
Publications (2)
Publication Number | Publication Date |
---|---|
CN1650709A CN1650709A (en) | 2005-08-10 |
CN1267422C true CN1267422C (en) | 2006-08-02 |
Family
ID=34875852
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN 200510023399 Expired - Fee Related CN1267422C (en) | 2005-01-18 | 2005-01-18 | Preparation method of pyriproxyfen |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN1267422C (en) |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105601564A (en) * | 2015-12-21 | 2016-05-25 | 江西安利达化工有限公司 | Preparation method of pyriproxyfen compound |
CN107474012A (en) * | 2017-09-05 | 2017-12-15 | 南通派斯第农药化工股份有限公司 | A kind of preparation method of Nylar |
CN107827716A (en) * | 2017-09-28 | 2018-03-23 | 大连天源基化学有限公司 | The residual processing method of kettle in the production of 1 (4 phenoxy phenoxy base) 2 propyl alcohol |
CN112724075A (en) * | 2020-12-31 | 2021-04-30 | 上海科利生物医药有限公司 | Preparation method of pyriproxyfen |
-
2005
- 2005-01-18 CN CN 200510023399 patent/CN1267422C/en not_active Expired - Fee Related
Also Published As
Publication number | Publication date |
---|---|
CN1650709A (en) | 2005-08-10 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
AU745789B2 (en) | A method for producing para-menthane-3,8-diol | |
CN1267422C (en) | Preparation method of pyriproxyfen | |
CN110845447B (en) | Synthesis method of sex pheromone component of fall webworm | |
CN105294624B (en) | A kind of preparation method of Dapagliflozin | |
CN101531640A (en) | Preparation method of quizalofop-p-ethyl with high optical content | |
US20110092578A1 (en) | Broad Spectrum Gram-Positive Antimicrobials and Anthelmintics with Efficacy Against Drug-Resistant Strains and Mycobacterium Species | |
CN103570601A (en) | Preparation method of optical active medicine intermediate | |
CN114478353A (en) | Synthesis method of melatonin | |
US20070292545A1 (en) | Anti-infective agents and methods of use | |
CN1286814C (en) | Separation and purification method of pyriproxyfen | |
CN108250156B (en) | Cinnamylate oxadiazine derivative and preparation method and application thereof | |
CN115974640A (en) | Synthetic method of psylla chinensis sex pheromone | |
CN114478667A (en) | 4', 23-oxygen ether group substituted avermectin B2a/B2B derivative and preparation method and application thereof | |
WO2004032629A1 (en) | Mixed compositions for controlling parasitic insects | |
DE2947775C2 (en) | ||
CN101967097B (en) | Fluorine-containing pyrethrin compound, preparation method and applications thereof | |
CN101273720A (en) | Method for preparing raw medicament of stable fenpyroximate | |
CN109699646B (en) | Preparation method of rice stem borer pheromone component | |
CN114258913B (en) | Temperature-sensitive controlled-release nano pesticide vesicle and preparation method and application thereof | |
JP2942408B2 (en) | Pest repellent | |
CN1259308C (en) | New technology of synthesizing fenoxycarb | |
CN115710180A (en) | Method for asymmetrically synthesizing sex pheromone of mealybugs of hibiscus syriacus | |
CN103450128B (en) | Preparation method of prostaglandin analogue midbody Corey aldehyde for treating glaucoma | |
CN111909081B (en) | Method for purifying pyriproxyfen technical, product obtained by method and application of pyriproxyfen technical | |
CN115466208B (en) | Method for purifying spirotetramat cis-intermediate |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
C06 | Publication | ||
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
C14 | Grant of patent or utility model | ||
GR01 | Patent grant | ||
C19 | Lapse of patent right due to non-payment of the annual fee | ||
CF01 | Termination of patent right due to non-payment of annual fee |