CN102898365A - High-yield high-quality one-pot method for synthesizing pyrithione urea - Google Patents
High-yield high-quality one-pot method for synthesizing pyrithione urea Download PDFInfo
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- CN102898365A CN102898365A CN2012103110875A CN201210311087A CN102898365A CN 102898365 A CN102898365 A CN 102898365A CN 2012103110875 A CN2012103110875 A CN 2012103110875A CN 201210311087 A CN201210311087 A CN 201210311087A CN 102898365 A CN102898365 A CN 102898365A
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Abstract
The invention relates to a high-yield high-quality one-pot method for synthesizing pyrithione urea. The method relates to an organic synthesizing method of pyrithione urea. The synthesizing method comprises the steps that: 1, halopyridine and an oxidant are heated to a temperature of 40-100 DEG C according to a molar ratio of 1:1-2 under the existence of 1-10% of a catalyst; the reaction is carried out for 3-24h, and an intermediate halopyridine-N-oxidant is prepared; 2, without purification, halopyridine-N-oxidant is directly concentrated to a certain concentration, a proper amount of a solvent is added for diluting, and the material is preserved for later use; 3, according to the molar weight of halopyridine-N-oxidant, thiourea with a molar weight of 1-3 times is added, and the temperature is heated to 20-50 DEG C; and a reaction is carried out for 1-3h, such that the pyrithione urea PM is prepared. According to the invention, original reaction steps are simplified, highly dangerous reaction processes are removed, intermediate purification is not needed, the steps are simple, the reaction is mild and controllable, target product yield is high, the quality of the finished product is stable, and three-waste discharging is reduced.
Description
Technical field:
The present invention relates to the methodology of organic synthesis of pyrithione urea, a kind of high yield particularly, the method for high-quality one kettle way pyridine synthesis thioketones urea.
Background technology:
Pyrithione urea (PM) is a kind of good antimildew and antibacterial agent, and structural formula is as follows.Have efficient, low toxicity, wide spectrum, water-soluble, stable, the excellent characteristics of valency.Use safety, be widely used in the career fields such as daily chemical products, coating, paper, seed treatment, fruit tree, fruit antisepsis, leatherware, industrial circulating cooling water, tackiness agent, papermaking, medicine, agricultural chemicals, heritage archive preservation.Especially in shampoo, use and have extremely strong anti-dandruff and itching-relieving effect.
The building-up process of pyrithione urea mainly divided for three steps carried out both at home and abroad at present, the first step is that haloperidid carries out the nitrogen oxidation in the presence of oxygenant, second step is extraction and the purification of haloperidid-N-oxide compound, and the 3rd step was the haloperidid of purifying-N-oxide compound and the condensation reaction of thiocarbamide in solvent.Because be subjected to the impact of the first step catalyzed oxidation yield and second step extraction yield, the ultimate yield of pyrithione urea is often on the low side, does not possess the industrial production condition.
R.A1an Jones and A.R.Katritzky are at Journal of the Chemical Society, taken the lead in delivering the 3rd step synthetic method of pyrithione urea on the 2937-42, one-step reaction yield at that time only has 60% and do not report first and second step reaction method and yield.Edrissi.0. and So1eymani, M in 2011 at Chemical Engineering ﹠amp; Technology, 34 (6), 991-996; The 3rd step synthetic method yield of also having delivered the pyrithione urea derivatives on 2011 is not quite clear.
The domestic people of having uses PA to make first the 2-chloropyridine through diazotization, chlorination reaction, carry out the first step reaction with Peracetic Acid again, with chloroform extraction 2-bromopyridine-N-oxide compound, obtain the second step product through ethyl alcohol recrystallization, carry out three-step reaction with thiocarbamide in solvent more at last and make finished product, total recovery is lower than 60%.This method production cycle is long, and total reaction needs more than 24 hours usually; Use Peracetic Acid as oxygenant, operational hazards, very easily blast; Intermediate 2-chloropyridine-N-oxide compound needs a large amount of solvent of purification by liquid extraction consumption, takies many complete equipments, produces a large amount of sewage; Ultimate yield is not high, is worth without industrial production.
Summary of the invention:
The method that the purpose of this invention is to provide a kind of high yield, high-quality one kettle way pyridine synthesis thioketones urea, it simplifies original reactions steps, remove high-risk reaction process, the intermediate of need not purifying, step is simple, reaction temperature and controlled, and the target product yield is high, final product quality is stable, and reduces three waste discharge.
In order to solve the existing problem of background technology, the present invention is by the following technical solutions: its synthetic method is: 1, haloperidid and oxygenant are heated up 40～100 ℃ according to mol ratio 1: 1～2 under the condition that 1%～10% catalyzer exists, react 3～24 hours preparation intermediate haloperidid-N-oxide compounds; 2, after haloperidid-N-oxide compound directly was concentrated into finite concentration without purifying, it was for subsequent use to add an amount of solvent cut; 3, according to the molar weight of haloperidid-N-oxide compound, the thiocarbamide that adds 1～3 times of molar weight heats up 20～50 ℃, reacts to make pyrithione urea PM in 1～3 hour.
Described haloperidid is 2-chloropyridine, 2-bromopyridine, 2-fluorine pyridine or 2-iodine pyridine.
Described oxygenant is hydrogen peroxide, Peracetic Acid, the mixture of one or more in the Glacial acetic acid.
Described catalyzer is one or more mixture in wolframic acid, sodium wolframate, three oxidations, two tungsten, MALEIC ANHYDRIDE, the Tetra hydro Phthalic anhydride.
The thickening temperature of described second step haloperidid-N-oxide compound is 50～100 ℃.
Described solvent is: ethyl acetate, acetone, 2-methyl chloride, 3-methyl chloride, 1, the mixture of one or more in the 2-ethylene dichloride.
Described three-step reaction halo adjoins the mol ratio 1: 1～3 of pyridine-N-oxide compound and thiocarbamide.
Described intermediate haloperidid-N-oxide compound does not need solvent extraction to purify, and participates in the next step directly.
The present invention has following beneficial effect: 1, oxidization time only has 50% of traditional technology, and oxidation operation safety is without explosion hazard; 2, intermediate haloperidid-N-oxide compound need not extract directly and concentrate, and saves the solvent expense, reduces three waste discharge; 3, pyrithione urea yield height 〉=90%, steady quality content 〉=98%.
Embodiment:
This embodiment is by the following technical solutions: its synthetic method is: 1, haloperidid and oxygenant are heated up 40～100 ℃ according to mol ratio 1: 1～2 under the condition that 1%～10% catalyzer exists, react and prepared intermediate haloperidid-N-oxide compound in 3～24 hours; 2, after haloperidid-N-oxide compound directly was concentrated into finite concentration without purifying, it was for subsequent use to add an amount of solvent cut; 3, according to the molar weight of haloperidid-N-oxide compound, the thiocarbamide that adds 1～3 times of molar weight heats up 20～50 ℃, reacts to make pyrithione urea PM in 1～3 hour.
Embodiment 1:
Add 2-chloropyridine 500g in the 5000ml four-hole boiling flask, add the 20g sodium wolframate, add 35% hydrogen peroxide 700g, temperature rises to 80 ℃ of stirring reactions 8 hours.Oxidizing reaction finishes, and does not lower the temperature, and about 60 ℃, directly concentrated material stops the concentrated 1000g1 of adding, 2-ethylene dichloride, cooling down till crystallization arranged.Add the 440g thiocarbamide, stirring reaction 2 hours below the cooling 2-chloropyridine-N-oxide compound 1,2-dichloroethane solution to 50 ℃.Filter to get product pyrithione urea solid 820g, total recovery 90.6%, content 99.1%.
Embodiment 2:
Add 2-bromopyridine 700g in the 5000ml four-hole boiling flask, add the 100g MALEIC ANHYDRIDE, add 35% hydrogen peroxide 970g, temperature rises to 85 ℃ of stirring reactions 12 hours.Oxidizing reaction finishes, and does not lower the temperature, and about 60 ℃, directly concentrated material stops the concentrated 1000g of adding trichloromethane, cooling down till crystallization arranged.Add the 440g thiocarbamide, stirring reaction 2 hours below cooling 2-bromopyridine-N-oxide compound chloroformic solution to 50 ℃.Filter to get product pyrithione urea solid 1012g, total recovery 91.4%, content 98.5%.
Claims (8)
1. the method for a high yield, high-quality one kettle way pyridine synthesis thioketones urea, the synthetic method that it is characterized in that it is: 1, haloperidid and oxygenant are heated up 40～100 ℃ according to mol ratio 1: 1～2 under the condition that 1%～10% catalyzer exists, react 3～24 hours preparation intermediate haloperidid-N-oxide compounds; 2, after haloperidid-N-oxide compound directly was concentrated into finite concentration without purifying, it was for subsequent use to add an amount of solvent cut; 3, according to the molar weight of haloperidid-N-oxide compound, the thiocarbamide that adds 1～3 times of molar weight heats up 20～50 ℃, reacts to make pyrithione urea PM in 1～3 hour.
2. the method for a kind of high yield according to claim 1, high-quality one kettle way pyridine synthesis thioketones urea is characterized in that described haloperidid is 2-chloropyridine, 2-bromopyridine, 2-fluorine pyridine, 2-iodine pyridine.
3. the method for a kind of high yield according to claim 1, high-quality one kettle way pyridine synthesis thioketones urea is characterized in that described oxygenant is hydrogen peroxide, Peracetic Acid, the mixture of one or more in the Glacial acetic acid.
4. the method for a kind of high yield according to claim 1, high-quality one kettle way pyridine synthesis thioketones urea is characterized in that described catalyzer is one or more mixture in wolframic acid, sodium wolframate, three oxidations, two tungsten, MALEIC ANHYDRIDE, the Tetra hydro Phthalic anhydride.
5. the method for a kind of high yield according to claim 1, high-quality one kettle way pyridine synthesis thioketones urea is characterized in that the thickening temperature of described second step haloperidid-N-oxide compound is 50～100 ℃.
6. the method for a kind of high yield according to claim 1, high-quality one kettle way pyridine synthesis thioketones urea, it is characterized in that described solvent is: ethyl acetate, acetone, 2-methyl chloride, 3-methyl chloride, 1, the mixture of one or more in the 2-ethylene dichloride.
7. the method for a kind of high yield according to claim 1, high-quality one kettle way pyridine synthesis thioketones urea is characterized in that the mol ratio 1: 1～3 of described three-step reaction haloperidid-N-oxide compound and thiocarbamide.
8. the method for a kind of high yield according to claim 1, high-quality one kettle way pyridine synthesis thioketones urea is characterized in that described intermediate haloperidid-N-oxide compound does not need solvent extraction to purify, and participates in the next step directly.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262247A (en) * | 2014-09-18 | 2015-01-07 | 西安近代化学研究所 | Method for synthesizing 2,6-diamino-3,5-dinitropyridine-1-oxide |
| CN106619487A (en) * | 2016-11-24 | 2017-05-10 | 浙江三禾纳米科技有限公司 | Antibacterial gel for skin and preparation method of antibacterial gel |
| CN106973931A (en) * | 2017-05-19 | 2017-07-25 | 乔丽丽 | Home-use sterilization bacteriostatic agent and its application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3047579A (en) * | 1958-07-18 | 1962-07-31 | Shell Oil Co | Process for preparing n-oxides |
| US4504667A (en) * | 1983-06-24 | 1985-03-12 | Olin Corporation | Process for oxidizing halopyridines to halopyridine-N-oxides |
-
2012
- 2012-08-29 CN CN2012103110875A patent/CN102898365A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3047579A (en) * | 1958-07-18 | 1962-07-31 | Shell Oil Co | Process for preparing n-oxides |
| US4504667A (en) * | 1983-06-24 | 1985-03-12 | Olin Corporation | Process for oxidizing halopyridines to halopyridine-N-oxides |
Non-Patent Citations (2)
| Title |
|---|
| 《Chemical Engineering &Technology》 20111231 Mohammad Edrissi et al. Synthesis of Nano-gamma-Ferric Oxide by Thermolysis of the 2-Mercapto-5-Methylpyridine-N-Oxide-Iron(III) Complex via Factorial Design 991-996 1-8 第34卷, 第6期 * |
| MOHAMMAD EDRISSI ET AL.: "Synthesis of Nano-γ-Ferric Oxide by Thermolysis of the 2-Mercapto-5-Methylpyridine-N-Oxide-Iron(III) Complex via Factorial Design", 《CHEMICAL ENGINEERING &TECHNOLOGY》, vol. 34, no. 6, 31 December 2011 (2011-12-31), pages 991 - 996 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262247A (en) * | 2014-09-18 | 2015-01-07 | 西安近代化学研究所 | Method for synthesizing 2,6-diamino-3,5-dinitropyridine-1-oxide |
| CN106619487A (en) * | 2016-11-24 | 2017-05-10 | 浙江三禾纳米科技有限公司 | Antibacterial gel for skin and preparation method of antibacterial gel |
| CN106973931A (en) * | 2017-05-19 | 2017-07-25 | 乔丽丽 | Home-use sterilization bacteriostatic agent and its application |
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