CN1650709A - Preparation method of pyriproxyfen - Google Patents
Preparation method of pyriproxyfen Download PDFInfo
- Publication number
- CN1650709A CN1650709A CN 200510023399 CN200510023399A CN1650709A CN 1650709 A CN1650709 A CN 1650709A CN 200510023399 CN200510023399 CN 200510023399 CN 200510023399 A CN200510023399 A CN 200510023399A CN 1650709 A CN1650709 A CN 1650709A
- Authority
- CN
- China
- Prior art keywords
- pyriproxyfen
- reaction
- phenoxy group
- preparation
- base catalyst
- 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.)
- Granted
Links
Landscapes
- Pyridine Compounds (AREA)
Abstract
A process for preparing pyriproxyfen includes reaction between p-phenoxyphenol and epoxy propane in water under catalysis of alkaline catayst to obtain 1-(4-phenoxyphenoxy)-2-propanol, reacting on 2-chloropyridine in ether or N-methyl pyrrolidone under catalysis of alkaline catalyst, filtering, and evaporating solvent.
Description
Technical field
The present invention relates to a kind of preparation method who contains the insect growth regulator, IGR of diphenyl 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-pyridine oxygen base) 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, thrips, diptera, lepidopterous pest, 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, pest such as colorado potato beetle all have good control efficiency, its action principle is the developmental stage (as the larva end length of time and pupa time) of selecting insect under normal circumstances not secrete or seldom secrete juvenile hormone 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 alkali condition; Second step with 1-(4-phenoxy group phenoxy group)-2-propyl alcohol and the reaction of 2-chloropyridine, obtained pyriproxyfen in atent solvent, chemical equation is as follows:
The first step
Second step
Chinese invention patent publication number CN1347864, 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 CN03112989.7 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 P4751225, USP4879292, USP4970222 propose at atent solvent (as N, dinethylformamide, oxolane, methyl-sulfoxide, 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. be solvent with water, under base catalyst catalysis, make p-phenoxyphenol and propylene oxide reaction, obtain 1-(4-phenoxy group phenoxy group)-2-propyl alcohol;
B. be solvent with ethers or N-Methyl pyrrolidone, under base catalyst catalysis, make the reaction of above-mentioned 1-(4-phenoxy group phenoxy group)-2-propyl alcohol and 2-chloropyridine, finish the back in reaction and filter, steaming desolventizes, and promptly gets the pyriproxyfen crude product.
Described base catalyst is selected from potassium hydroxide, sodium hydroxide or potash.
The mol ratio of phenoxy phenyl and base catalyst and expoxy propane is 1: 0.1～2: 2～5 among the step a, and the reaction temperature of phenoxy phenyl and expoxy propane is controlled at 20～60 ℃, and the reaction time was controlled at 1～6 hour.
Ether solvent described in the step b is selected from dioxane or ethylene glycol diethyl ether.
The mol ratio of 1-among the step b (4-phenoxy group phenoxy group)-2-propyl alcohol and base catalyst and the reaction of 2-chloropyridine is 1: 2～5: 1～1.6, and reaction temperature is controlled at 60～160 ℃, and the reaction time was controlled at 1～12 hour.
The invention has the beneficial effects as follows: the present invention prepares pyriproxyfen by two-step method, 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 dissolvent, 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 potash, with p-phenoxyphenol and propylene oxide reaction, the mol ratio of phenoxy phenyl and base catalyst and expoxy propane is 1: 0.1～2: 2～5, reaction temperature is controlled at 20～60 ℃, reaction time 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 first step product 1-(4-phenoxy group phenoxy group)-2-propyl alcohol and base catalyst (potassium hydroxide, sodium hydroxide), react with the 2-chloropyridine, mol ratio is 1: 2～5: 1～1.6, reaction temperature is controlled at 60～160 ℃, reaction time is 1～12 hour, reaction finishes the back and filters, steaming desolventizes, promptly get the pyriproxyfen crude product, crude product promptly gets pyriproxyfen elaboration, purity 〉=98.5% through recrystallization.
Embodiment 1
The first step: in 250 milliliter of four neck reaction bulb 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) expoxy propane down, at room temperature continue after dripping off to stir 3 hours.Reactant 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 bulb that thermometer, reflux condensing tube, agitator are housed, add above-mentioned 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 bulb that thermometer, reflux condensing tube, agitator are housed, add 30.0 gram (0.16 mole) p-phenoxyphenols, 27.6 gram (0.2 mole) potash and 100 ml waters, stir and drip 27.8 gram (0.48 mole) expoxy propane down, at room temperature continue after dripping off to stir 3 hours.Reactant 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 bulb that thermometer, reflux condensing tube, agitator are housed, add above-mentioned 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 bulb 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 reaction temperatures 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 reaction temperatures 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 (5)
1. the preparation method of a pyriproxyfen is characterized in that the following step:
A. be solvent with water, under base catalyst catalysis, make p-phenoxyphenol and propylene oxide reaction, obtain 1-(4-phenoxy group phenoxy group)-2-propyl alcohol;
B. be solvent with ethers or N-Methyl pyrrolidone, under base catalyst catalysis, make the reaction of above-mentioned 1-(4-phenoxy group phenoxy group)-2-propyl alcohol and 2-chloropyridine, finish the back in reaction and filter, steaming desolventizes, and promptly gets the pyriproxyfen crude product.
2. the preparation method of pyriproxyfen according to claim 1, it is characterized in that: described base catalyst is selected from potassium hydroxide, sodium hydroxide or potash.
3. the preparation method of pyriproxyfen according to claim 1, it is characterized in that: the mol ratio of phenoxy phenyl and base catalyst and expoxy propane is 1: 0.1～2: 2～5 among the step a, the reaction temperature of phenoxy phenyl and expoxy propane is controlled at 20～60 ℃, and the reaction time was controlled at 1～6 hour.
4. the preparation method of pyriproxyfen according to claim 1, it is characterized in that: the ether solvent described in the step b is selected from dioxane or ethylene glycol diethyl ether.
5. according to the preparation method of claim 1,2 or 4 described pyriproxyfens, it is characterized in that: the mol ratio of 1-among the step b (4-phenoxy group phenoxy group)-2-propyl alcohol and base catalyst and the reaction of 2-chloropyridine is 1: 2～5: 1～1.6, reaction temperature is controlled at 60～160 ℃, and the reaction time was controlled at 1～12 hour.
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 true CN1650709A (en) | 2005-08-10 |
| CN1267422C 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) |
Cited By (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 compounds |
| 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
Cited By (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 compounds |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1267422C (en) | 2006-08-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3450680B2 (en) | Method for producing para-menthane-3,8-diol | |
| CN1650709A (en) | Preparation method of pyriproxyfen | |
| CN102391184A (en) | Synthesis method of celecoxib | |
| CN105294624A (en) | Preparation method for dapagliflozin | |
| CN107474021B (en) | Oxadiazine derivatives, preparation method and application thereof | |
| CN114478353A (en) | Synthesis method of melatonin | |
| CN1663384A (en) | Pesticide and its preparing method | |
| TWI343254B (en) | A method of purifying moxidectin through crystallization | |
| 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 | |
| CN1487932A (en) | New process for the preparation of the anti-migraine drug | |
| CN110305156A (en) | A kind of alkynes derivative and its preparation method and application containing nitrogen-oxygen bond | |
| CN101273720A (en) | Method for preparing raw medicament of stable fenpyroximate | |
| CN101209968B (en) | Improved synthesis method for tea caterpillar sex pheromone | |
| CN109699646B (en) | Preparation method of rice stem borer pheromone component | |
| CN111909081B (en) | Method for purifying pyriproxyfen technical, product obtained by method and application of pyriproxyfen technical | |
| KR100928656B1 (en) | Method for producing 1,2,4-butanetriol | |
| CN1259308C (en) | New technology of synthesizing fenoxycarb | |
| CN114258913B (en) | Temperature-sensitive controlled-release nano pesticide vesicle and preparation method and application thereof | |
| CN115466208B (en) | Method for purifying spirotetramat cis-intermediate | |
| CN110105311B (en) | Synthetic method of sex pheromone intermediate of fall webworm | |
| JP4397990B2 (en) | Purification method of 3-alkylflavanonol derivatives | |
| CN101891569A (en) | Preparation method of alpha-aromatic ketone compound | |
| CN1329387C (en) | Alpha-vitamine E cyclopropane carboxylate, vitamine E derivs. and preparing method thereof |
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 |