CN102617636B - Preparation method of high-purity profenofos - Google Patents
Preparation method of high-purity profenofos Download PDFInfo
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- CN102617636B CN102617636B CN201210044233.2A CN201210044233A CN102617636B CN 102617636 B CN102617636 B CN 102617636B CN 201210044233 A CN201210044233 A CN 201210044233A CN 102617636 B CN102617636 B CN 102617636B
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Abstract
The invention relates to a preparation method of high-purity profenofos. The preparation method improves purity of 2-chloro-4-bromophenol by repeated recrystallization, and the purity of profenofos prepared by the method can reach 96 mass%. The preparation method comprises the following steps: (1) brominating; (2) recrystalizing for 3-5 times; (3) enabling O,O-diethyl sulfo phosphoryl chloride to react with a recrystalized bromination product to obtain O,O-diethyl-O-(2-chloro-4-bromophenyl)-phosphorothioate; (4) in the presence of trimethylamine, obtaining O-ethyl-O-(2-chloro-4-bromophenyl) thiophosphoric acid trimethylamine by backflow of O,O-diethyl-O-(2-chloro-4-bromophenyl)-phosphorothioate, and obtaining amine salt intermediates by dehydration and trimethylamine removal; (5) adding bromopropane and catalyst dimethyl formamide into the product obtained in the step (4) to react so that profenofos is formed; and (6) carrying out layering, washing and solvent removal to the product obtained in the step (5), and obtaining a profenofos product.
Description
Technical field
The present invention relates to a kind of preparation method of Profenofos.
Background technology
Profenofos, i.e. O-(the bromo-2-chloro-phenyl-of 4-)-O-ethyl-S-n-propyl thiophosphatephosphorothioate, be a kind of thiophosphatephosphorothioate insecticides containing rosickyite base, have the feature of high-efficiency broad spectrum, have strong tagging and stomach poison function, can desinsection, again can ovicidal.To the insect such as bollworm, pink bollworm, cotten aphid, cigarette beetle, tetranychid, aleyrodid of cotton, fruit tree, water paddy and wheat class, soybean, seeding corn and other crops, there is good prevention effect.Because its mechanism of action is unique, antagonism insect shows high reactivity, and the prevention effect of antagonism bollworm is particularly evident.Its structural formula is as follows:
But existing Profenofos production technology can only produce the Profenofos that purity is about 90 quality %, its reason is that the byproduct in these raw materials can make the purity drop of Profenofos containing the chloro-6-bromophenol of 2-and many bromos byproduct in the raw material 2-chloro-4-bromophenol of production Profenofos.
Summary of the invention
The invention provides a kind of preparation method of high purity Profenofos, the method improves the purity of the chloro-4-bromophenol of 2-by recrystallization repeatedly, and the Profenofos purity using the method to prepare can reach 96 quality %.
The preparation method of Profenofos of the present invention, comprises the following steps:
1) ortho chloro phenol and Br
2reaction, obtains brominated product; Wherein brominated product comprises many bromos by product of the 2-chloro-4-bromophenol of 94-95 quality % and the chloro-6-bromophenol of by product 2-of 3-4 quality % and 2-3 quality %;
2) recrystallization: slowly heating steps 1) brominated product that obtains, bromizate product to heat up with the speed of 0.8-1 DEG C/h, reach 48-50 DEG C to brominated product temperature and stop heating, then Temperature fall reaches 42-43 DEG C to brominated product temperature, by after above-mentioned slow intensification again the process of Temperature fall be called recrystallization process, then repeated recrystallization process 2-4 time; Repeatedly recrystallization 3-5 time can from brominated product the chloro-6-bromophenol of cutting out partial 2-and many bromos by product, the purity of chloro-for 2-in brominated product 4-bromophenol is increased to 97 quality %;
3) O, O-o,o-diethylthiophosphoryl chloride and step 2) brominated product that obtains is that acid binding agent carries out being obtained by reacting O with sodium hydroxide, O-diethyl-O-(the chloro-4-bromophenyl of 2-)-thiophosphatephosphorothioate; Wherein the purity of gained O, O-diethyl-O-(the chloro-4-bromophenyl of 2-)-thiophosphatephosphorothioate (referred to as three esters) is 98 quality %;
4) under Trimethylamine 99 exists, O, the backflow of O-diethyl-O-(2-chloro-4-bromophenyl)-thiophosphatephosphorothioate goes alkylation reaction to obtain O-ethyl-O-(the chloro-4-bromophenyl of 2-) tri o cresyl thiophosphate ammonium carbamate, rotary evaporation sloughs water, decompression rotary evaporation sloughs Trimethylamine 99, obtains amine salt intermediate;
The structural formula of wherein said amine salt intermediate is:
5) in step 4) add N-PROPYLE BROMIDE in products therefrom, at catalyst n, carry out reaction under dinethylformamide (being abbreviated as DMF) existent condition and generate Profenofos;
6) by step 5) products therefrom stratification, the water on removing upper strata, products therefrom and Profenofos crude product, wash Profenofos crude product, distill except desolventizing, obtain Profenofos product.
The preparation method of Profenofos of the present invention, wherein step 1) in ortho chloro phenol and Br
2mol ratio be 1:1, temperature of reaction is 30-50 DEG C, and the reaction times is 20-25 hour.
The preparation method of Profenofos of the present invention, wherein step 3) in, step 2) brominated product that obtains: sodium hydroxide: the mol ratio of O, O-o,o-diethylthiophosphoryl chloride is 1:(1-2): (1-2), temperature of reaction is 30-60 DEG C, and the reaction times is 20-25 hour.
The preparation method of Profenofos of the present invention, wherein step 4) in the mol ratio of O, O-diethyl-O-(the chloro-4-bromophenyl of 2-)-thiophosphatephosphorothioate and Trimethylamine 99 be 1:(1-4), reflux temperature is 50-80 DEG C, reacts 6-10h.
The preparation method of Profenofos of the present invention, wherein step 5) in, step 4) in products therefrom the mol ratio of ammonium salt intermediate, N-PROPYLE BROMIDE and DMF be 1:(2-5): 0.005, temperature of reaction is 50-100 DEG C, reaction 4-8h.
Preparation method's difference from prior art of Profenofos of the present invention is, by recrystallization repeatedly, the purity of chloro-for raw material 2-4-bromophenol is increased to 97% by 94%, thus makes product Profenofos purity can reach 96 quality % (employing gas chromatographic analysis).
Embodiment
Embodiment 1
1) mol ratio is ortho chloro phenol and the Br of 1:1
2reaction, temperature of reaction is 30 DEG C, and the reaction times is 25 hours, obtains brominated product, and wherein brominated product comprises many bromos by product of the 2-chloro-4-bromophenol of 94-95 quality % and the chloro-6-bromophenol of by product 2-of 3-4 quality % and 2-3 quality %;
2) recrystallization: slowly heating steps 1) brominated product that obtains, bromizate product to heat up with the speed of 0.8 DEG C/h, reach 48 DEG C to brominated product temperature and stop heating, then Temperature fall reaches 42 DEG C to brominated product temperature, by after above-mentioned slow intensification again the process of Temperature fall be called recrystallization process, then repeated recrystallization process 2 times; Repeatedly recrystallization 3 times can from brominated product the chloro-6-bromophenol of cutting out partial 2-and many bromos by product, the purity of chloro-for 2-in brominated product 4-bromophenol is increased to 97%;
3) O, O-o,o-diethylthiophosphoryl chloride and step 2) brominated product that obtains is that acid binding agent carries out being obtained by reacting O with sodium hydroxide, O-diethyl-O-(the chloro-4-bromophenyl of 2-)-thiophosphatephosphorothioate, wherein step 2) brominated product that obtains: sodium hydroxide: O, the mol ratio of O-o,o-diethylthiophosphoryl chloride is 1:2:2, temperature of reaction is 60 DEG C, reaction times is 20 hours, the purity of gained O, O-diethyl-O-(the chloro-4-bromophenyl of 2-)-thiophosphatephosphorothioate is 98 quality %;
4) under Trimethylamine 99 exists, O, the backflow of O-diethyl-O-(2-chloro-4-bromophenyl)-thiophosphatephosphorothioate goes alkylation reaction to obtain O-ethyl-O-(the chloro-4-bromophenyl of 2-) tri o cresyl thiophosphate ammonium carbamate, rotary evaporation sloughs water, and decompression rotary evaporation sloughs Trimethylamine 99, obtains amine salt intermediate, wherein O, the mol ratio of O-diethyl-O-(the chloro-4-bromophenyl of 2-)-thiophosphatephosphorothioate and Trimethylamine 99 is 1:1, and reflux temperature is 80 DEG C, reaction 6h;
5) in step 4) add N-PROPYLE BROMIDE and catalyst n in products therefrom, dinethylformamide (being abbreviated as DMF) reacts; The preparation method of high purity Profenofos of the present invention, wherein the mol ratio of ammonium salt intermediate, N-PROPYLE BROMIDE and DMF is 1:2:0.005, and temperature of reaction is 100 DEG C, reaction 4h;
6) by step 5) products therefrom stratification, the water on removing upper strata, products therefrom and Profenofos crude product, Profenofos crude product is washed, distills except desolventizing, obtain Profenofos product, this Profenofos product purity is 96.1 quality %, and total recovery is 90.0%.
Embodiment 2
1) mol ratio is ortho chloro phenol and the Br of 1:1
2reaction, temperature of reaction is 50 DEG C, and the reaction times is 20 hours, obtains brominated product, and wherein brominated product comprises many bromos by product of the 2-chloro-4-bromophenol of 94-95 quality % and the chloro-6-bromophenol of by product 2-of 3-4 quality % and 2-3 quality %;
2) recrystallization: slowly heating steps 1) brominated product that obtains, bromizate product to heat up with the speed of 1.0 DEG C/h, reach 50 DEG C to brominated product temperature and stop heating, then Temperature fall reaches 43 DEG C to brominated product temperature, by after above-mentioned slow intensification again the process of Temperature fall be called recrystallization process, then repeated recrystallization process 4 times; Repeatedly recrystallization 5 times can from brominated product the chloro-6-bromophenol of cutting out partial 2-and many bromos by product, the purity of chloro-for 2-in brominated product 4-bromophenol is increased to 97%;
3) O, O-o,o-diethylthiophosphoryl chloride and step 2) brominated product that obtains is that acid binding agent carries out being obtained by reacting O with sodium hydroxide, O-diethyl-O-(the chloro-4-bromophenyl of 2-)-thiophosphatephosphorothioate, wherein step 2) brominated product that obtains: sodium hydroxide: O, the mol ratio of O-o,o-diethylthiophosphoryl chloride is 1:1:1, temperature of reaction is 30 DEG C, reaction times is 25 hours, the purity of gained O, O-diethyl-O-(the chloro-4-bromophenyl of 2-)-thiophosphatephosphorothioate is 98 quality %;
4) under Trimethylamine 99 exists, O, the backflow of O-diethyl-O-(2-chloro-4-bromophenyl)-thiophosphatephosphorothioate goes alkylation reaction to obtain O-ethyl-O-(the chloro-4-bromophenyl of 2-) tri o cresyl thiophosphate ammonium carbamate, rotary evaporation sloughs water, and decompression rotary evaporation sloughs Trimethylamine 99, obtains amine salt intermediate, wherein O, the mol ratio of O-diethyl-O-(the chloro-4-bromophenyl of 2-)-thiophosphatephosphorothioate and Trimethylamine 99 is 1:4, and reflux temperature is 50 DEG C, reaction 10h;
5) in step 4) add N-PROPYLE BROMIDE and catalyst n in products therefrom, dinethylformamide (being abbreviated as DMF) reacts; The preparation method of high purity Profenofos of the present invention, wherein the mol ratio of ammonium salt intermediate, N-PROPYLE BROMIDE and DMF is 1:5:0.005, and temperature of reaction is 50 DEG C, reaction 8h;
6) by step 5) products therefrom stratification, the water on removing upper strata, products therefrom and Profenofos crude product, Profenofos crude product is washed, distills except desolventizing, obtain Profenofos product, this Profenofos product purity is 96.5 quality %, and total recovery is 90.5%.
Above-described embodiment is only be described the preferred embodiment of the present invention; not scope of the present invention is limited; under not departing from the present invention and designing the prerequisite of spirit; the various distortion that those of ordinary skill in the art make technical scheme of the present invention and improvement, all should fall in protection domain that claims of the present invention determines.
Claims (5)
1. a preparation method for 96 quality % Profenofos, is characterized in that: comprise the following steps:
1) ortho chloro phenol and Br
2reaction, obtains brominated product;
2) recrystallization: slowly heating steps 1) brominated product that obtains, bromizate product to heat up with the speed of 0.8-1 DEG C/h, reach 48-50 DEG C to brominated product temperature and stop heating, then Temperature fall reaches 42-43 DEG C to brominated product temperature, by after above-mentioned slow intensification again the process of Temperature fall be called recrystallization process, then repeated recrystallization process 2-4 time;
3) O, O-o,o-diethylthiophosphoryl chloride and step 2) brominated product that obtains is that acid binding agent carries out being obtained by reacting O with sodium hydroxide, O-diethyl-O-(the chloro-4-bromophenyl of 2-)-thiophosphatephosphorothioate;
4) under Trimethylamine 99 exists, O, the backflow of O-diethyl-O-(2-chloro-4-bromophenyl)-thiophosphatephosphorothioate goes alkylation reaction to obtain O-ethyl-O-(the chloro-4-bromophenyl of 2-) tri o cresyl thiophosphate ammonium carbamate, rotary evaporation sloughs water, decompression rotary evaporation sloughs Trimethylamine 99, obtains ammonium salt intermediate; The structural formula of described ammonium salt intermediate is as follows:
5) in step 4) add N-PROPYLE BROMIDE in products therefrom, at catalyst n, carry out reaction under dinethylformamide existent condition and generate Profenofos;
6) by step 5) products therefrom stratification, the water on removing upper strata, products therefrom and Profenofos crude product, wash Profenofos crude product, distill except desolventizing, obtain Profenofos product.
2. the preparation method of 96 quality % Profenofos according to claim 1, is characterized in that: step 1) in, ortho chloro phenol and Br
2mol ratio be 1:1, temperature of reaction is 30-50 DEG C, and the reaction times is 20-25 hour.
3. the preparation method of 96 quality % Profenofos according to claim 2, it is characterized in that: step 3) in, step 2) brominated product that obtains: sodium hydroxide: O, the mol ratio of O-o,o-diethylthiophosphoryl chloride is 1:(1-2): (1-2), temperature of reaction is 30-60 DEG C, and the reaction times is 20-25 hour.
4. the preparation method of 96 quality % Profenofos according to claim 3, it is characterized in that: step 4) in, O, the mol ratio of O-diethyl-O-(the chloro-4-bromophenyl of 2-)-thiophosphatephosphorothioate and Trimethylamine 99 is 1:(1-4), reflux temperature is 50-80 DEG C, reaction 6-10h.
5. the preparation method of 96 quality % Profenofos according to claim 4, it is characterized in that: step 5) in, step 4) in products therefrom the mol ratio of ammonium salt intermediate, N-PROPYLE BROMIDE and DMF be 1:(2-5): 0.005, temperature of reaction is 50-100 DEG C, reaction 4-8h.
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| CN103143244B (en) * | 2013-03-08 | 2014-11-05 | 山东科源化工有限公司 | Treatment method for exhaust gases in production of profenofos |
| CN103387484B (en) * | 2013-07-23 | 2015-03-25 | 山东科源化工有限公司 | Preparation method of 2-chloro-4-bromophonel with high purity |
| CN103588811B (en) * | 2013-11-19 | 2016-03-30 | 山东科源化工有限公司 | A kind of preparation method of Profenofos intermediate three ester |
| CN109836454A (en) * | 2019-04-02 | 2019-06-04 | 山东科源化工有限公司 | A kind of no catalyst Profenofos raw medicine synthetic method |
| CN110922425A (en) * | 2019-11-07 | 2020-03-27 | 山东亿盛实业股份有限公司 | Continuous countercurrent extraction synthesis method of profenofos intermediate triester |
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| CN1101646A (en) * | 1994-07-23 | 1995-04-19 | 南开大学 | Synthesizing method for propyl-bromo-phopshorous of organic phosphorous insecticide |
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