CN102617636A - Preparation method of high-purity profenofos - Google Patents
Preparation method of high-purity profenofos Download PDFInfo
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- CN102617636A CN102617636A CN2012100442332A CN201210044233A CN102617636A CN 102617636 A CN102617636 A CN 102617636A CN 2012100442332 A CN2012100442332 A CN 2012100442332A CN 201210044233 A CN201210044233 A CN 201210044233A CN 102617636 A CN102617636 A CN 102617636A
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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 Tambo.
Background technology
Tambo, promptly O-(4-bromo-2-chloro-phenyl-)-O-ethyl-S-n-propyl thiophosphatephosphorothioate is a kind of thiophosphatephosphorothioate insecticides that contains the rosickyite base, has the characteristics of high-efficiency broad spectrum, has intensive to tag and stomach poison function, can desinsection, can kill ovum again.Insects such as the bollworm of cotton, fruit tree, water paddy and wheat class, soybean, seeding corn and other crops, pink bollworm, cotten aphid, cigarette beetle, tetranychid, aleyrodid had good control effect.Because its mechanism of action is unique, the antagonism insect shows high reactivity, and the control effect of antagonism bollworm is particularly evident.Its structural formula is following:
But it is the Tambo about 90 quality % that existing Tambo production technology can only be produced purity; Its reason is to produce in the raw material 2-chloro-4-bromophenol of Tambo and contains 2-chloro-6-bromophenol and many bromos sub product, and the sub product in these raw materials can make the purity drop of Tambo.
Summary of the invention
The invention provides a kind of preparation method of high purity Tambo, this method has improved the purity of 2-chloro-4-bromophenol through recrystallization repeatedly, uses the Tambo purity of this method preparation can reach 96 quality %.
The preparation method of high purity Tambo of the present invention may further comprise the steps:
1) ortho chloro phenol and Br
2Reaction obtains brominated product; Wherein brominated product comprises 2-chloro-4-bromophenol and the by product 2-chloro-6-bromophenol of 3-4 quality % and the many bromos by product of 2-3 quality % of 94-95 quality %;
2) recrystallization: the brominated product that slow heating steps 1) obtains; Bromizating product heats up with 0.8-1 ℃/hour speed; Reach 48-50 ℃ to the brominated product temperature and stop heating; Naturally be cooled to the brominated product temperature then and reach 42-43 ℃, the process of lowering the temperature naturally again after the above-mentioned slow intensification is called recrystallization process, the repeated recrystallization process is 2-4 time again; Repeatedly recrystallization 3-5 time can be from brominated product cutting out partial 2-chloro-6-bromophenol and many bromos by product, the purity of 2-chloro-4-bromophenol in the brominated product is increased to 97 quality %;
3) O, O-o,o-diethylthiophosphoryl chloride and step 2) brominated product that obtains is that acid binding agent reacts and obtains O, O-diethylammonium-O-(2-chloro-4-bromophenyl)-thiophosphatephosphorothioate with sodium hydroxide; Gained O wherein, the purity of O-diethylammonium-O-(2-chloro-4-bromophenyl)-thiophosphatephosphorothioate (abbreviating three esters as) is 98 quality %;
4) in the presence of Trimethylamine 99; O, O-diethylammonium-O-(2-chloro-4-bromophenyl)-thiophosphatephosphorothioate reflux and go alkylation reaction to obtain O-ethyl-O-(2-chloro-4-bromophenyl) tri o cresyl thiophosphate ammonium carbamate, and rotary evaporation is sloughed water; The decompression rotary evaporation is sloughed Trimethylamine 99, obtains the amine salt midbody;
5) in the step 4) products therefrom, add N-PROPYLE BROMIDE,, react the generation Tambo under the condition that dinethylformamide (being abbreviated as DMF) exists at catalyst n;
6) with step 5) products therefrom standing demix, remove the water on upper strata, products therefrom is the Tambo bullion, and the washing of Tambo bullion, distillation are removed and desolvate, and promptly gets the Tambo product.
The preparation method of high purity Tambo of the present invention, wherein ortho chloro phenol and Br in the step 1)
2Mol ratio be 1: 1, temperature of reaction is 30-50 ℃, the reaction times is 20-25 hour.
The preparation method of high purity Tambo of the present invention, wherein in the step 3), 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 ℃, the reaction times is 20-25 hour.
The preparation method of high purity Tambo of the present invention, O in the step 4) wherein, the mol ratio of O-diethylammonium-O-(2-chloro-4-bromophenyl)-thiophosphatephosphorothioate and Trimethylamine 99 is 1: (1-4), reflux temperature is 50-80 ℃, reaction 6-10h.
The preparation method of high purity Tambo of the present invention, wherein in the step 5), the mol ratio of ammonium salt intermediate, N-PROPYLE BROMIDE and DMF is 1 in the step 4) products therefrom: (2-5): 0.005, temperature of reaction is 50-100 ℃, reaction 4-8h.
Preparing method's difference from prior art of high purity Tambo of the present invention is through recrystallization repeatedly the purity of raw material 2-chloro-4-bromophenol to be increased to 97% by 94%, thereby makes product Tambo purity can reach 96 quality % (employing gas chromatographic analysis).
Embodiment
Embodiment 1
1) mol ratio is 1: 1 ortho chloro phenol and Br
2Reaction, temperature of reaction is 30 ℃, and the reaction times is 25 hours, obtains brominated product, and wherein brominated product comprises 2-chloro-4-bromophenol and the by product 2-chloro-6-bromophenol of 3-4 quality % and the many bromos by product of 2-3 quality % of 94-95 quality %;
2) recrystallization: the brominated product that slow heating steps 1) obtains; Bromizating product heats up with 0.8 ℃/hour speed; Reach 48 ℃ to the brominated product temperature and stop heating; Naturally be cooled to the brominated product temperature then and reach 42 ℃, the process of lowering the temperature naturally again after the above-mentioned slow intensification is called recrystallization process, the repeated recrystallization process is 2 times again; Repeatedly recrystallization 3 times can be from brominated product cutting out partial 2-chloro-6-bromophenol and many bromos by product, the purity of 2-chloro-4-bromophenol in the brominated product is increased to 97%;
3) O, O-o,o-diethylthiophosphoryl chloride and step 2) brominated product that obtains is that acid binding agent reacts and obtains O, O-diethylammonium-O-(2-chloro-4-bromophenyl)-thiophosphatephosphorothioate with sodium hydroxide; Step 2 wherein) brominated product that obtains: sodium hydroxide: O; The mol ratio of O-o,o-diethylthiophosphoryl chloride is 1: 2: 2, and temperature of reaction is 60 ℃, and the reaction times is 20 hours; Gained O, the purity of O-diethylammonium-O-(2-chloro-4-bromophenyl)-thiophosphatephosphorothioate is 98 quality %;
4) in the presence of Trimethylamine 99, O, O-diethylammonium-O-(2-chloro-4-bromophenyl)-thiophosphatephosphorothioate reflux and go alkylation reaction to obtain O-ethyl-O-(2-chloro-4-bromophenyl) tri o cresyl thiophosphate ammonium carbamate; Rotary evaporation is sloughed water, and the decompression rotary evaporation is sloughed Trimethylamine 99, obtains the amine salt midbody; O wherein; The mol ratio of O-diethylammonium-O-(2-chloro-4-bromophenyl)-thiophosphatephosphorothioate and Trimethylamine 99 is 1: 1, and reflux temperature is 80 ℃, reaction 6h;
5) in the step 4) products therefrom, add N-PROPYLE BROMIDE and catalyst n, dinethylformamide (being abbreviated as DMF) reacts; The preparation method of high purity Tambo of the present invention, wherein the mol ratio of ammonium salt intermediate, N-PROPYLE BROMIDE and DMF is 1: 2: 0.005, temperature of reaction is 100 ℃, reaction 4h;
6) with step 5) products therefrom standing demix, remove the water on upper strata, products therefrom is the Tambo bullion, and the washing of Tambo bullion, distillation are removed and desolvate, and promptly gets the Tambo product, and this Tambo product purity is 96.1 quality %, and total recovery is 90.0%.
Embodiment 2
1) mol ratio is 1: 1 ortho chloro phenol and Br
2Reaction, temperature of reaction is 50 ℃, and the reaction times is 20 hours, obtains brominated product, and wherein brominated product comprises 2-chloro-4-bromophenol and the by product 2-chloro-6-bromophenol of 3-4 quality % and the many bromos by product of 2-3 quality % of 94-95 quality %;
2) recrystallization: the brominated product that slow heating steps 1) obtains; Bromizating product heats up with 1.0 ℃/hour speed; Reach 50 ℃ to the brominated product temperature and stop heating; Naturally be cooled to the brominated product temperature then and reach 43 ℃, the process of lowering the temperature naturally again after the above-mentioned slow intensification is called recrystallization process, the repeated recrystallization process is 4 times again; Repeatedly recrystallization 5 times can be from brominated product cutting out partial 2-chloro-6-bromophenol and many bromos by product, the purity of 2-chloro-4-bromophenol in the brominated product is increased to 97%;
3) O, O-o,o-diethylthiophosphoryl chloride and step 2) brominated product that obtains is that acid binding agent reacts and obtains O, O-diethylammonium-O-(2-chloro-4-bromophenyl)-thiophosphatephosphorothioate with sodium hydroxide; Step 2 wherein) brominated product that obtains: sodium hydroxide: O; The mol ratio of O-o,o-diethylthiophosphoryl chloride is 1: 1: 1, and temperature of reaction is 30 ℃, and the reaction times is 25 hours; Gained O, the purity of O-diethylammonium-O-(2-chloro-4-bromophenyl)-thiophosphatephosphorothioate is 98 quality %;
4) in the presence of Trimethylamine 99, O, O-diethylammonium-O-(2-chloro-4-bromophenyl)-thiophosphatephosphorothioate reflux and go alkylation reaction to obtain O-ethyl-O-(2-chloro-4-bromophenyl) tri o cresyl thiophosphate ammonium carbamate; Rotary evaporation is sloughed water, and the decompression rotary evaporation is sloughed Trimethylamine 99, obtains the amine salt midbody; O wherein; The mol ratio of O-diethylammonium-O-(2-chloro-4-bromophenyl)-thiophosphatephosphorothioate and Trimethylamine 99 is 1: 4, and reflux temperature is 50 ℃, reaction 10h;
5) in the step 4) products therefrom, add N-PROPYLE BROMIDE and catalyst n, dinethylformamide (being abbreviated as DMF) reacts; The preparation method of high purity Tambo of the present invention, wherein the mol ratio of ammonium salt intermediate, N-PROPYLE BROMIDE and DMF is 1: 5: 0.005, temperature of reaction is 50 ℃, reaction 8h;
6) with step 5) products therefrom standing demix, remove the water on upper strata, products therefrom is the Tambo bullion, and the washing of Tambo bullion, distillation are removed and desolvate, and promptly gets the Tambo product, and this Tambo product purity is 96.5 quality %, and total recovery is 90.5%.
Above-described embodiment describes preferred implementation of the present invention; Be not that scope of the present invention is limited; Design under the prerequisite of spirit not breaking away from the present invention; Various distortion and improvement that those of ordinary skills make technical scheme of the present invention all should fall in the definite protection domain of claims of the present invention.
Claims (5)
1. the preparation method of a high purity Tambo is characterized in that: may further comprise the steps:
1) ortho chloro phenol and Br2 reaction obtains brominated product;
2) recrystallization: the brominated product that slow heating steps 1) obtains; Bromizating product heats up with 0.8-1 ℃/hour speed; Reach 48-50 ℃ to the brominated product temperature and stop heating; Naturally be cooled to the brominated product temperature then and reach 42-43 ℃, the process of lowering the temperature naturally again after the above-mentioned slow intensification is called recrystallization process, the repeated recrystallization process is 2-4 time again;
3) O, O-o,o-diethylthiophosphoryl chloride and step 2) brominated product that obtains is that acid binding agent reacts and obtains O, O-diethylammonium-O-(2-chloro-4-bromophenyl)-thiophosphatephosphorothioate with sodium hydroxide;
4) in the presence of Trimethylamine 99; O, O-diethylammonium-O-(2-chloro-4-bromophenyl)-thiophosphatephosphorothioate reflux and go alkylation reaction to obtain O-ethyl-O-(2-chloro-4-bromophenyl) tri o cresyl thiophosphate ammonium carbamate, and rotary evaporation is sloughed water; The decompression rotary evaporation is sloughed Trimethylamine 99, obtains the amine salt midbody;
5) in the step 4) products therefrom, add N-PROPYLE BROMIDE,, react the generation Tambo under the condition that dinethylformamide exists at catalyst n;
6) with step 5) products therefrom standing demix, remove the water on upper strata, products therefrom is the Tambo bullion, and the washing of Tambo bullion, distillation are removed and desolvate, and promptly gets the Tambo product.
2. the preparation method of high purity Tambo according to claim 1 is characterized in that: in the step 1), the mol ratio of ortho chloro phenol and Br2 is 1: 1, and temperature of reaction is 30-50 ℃, and the reaction times is 20-25 hour.
3. the preparation method of high purity Tambo according to claim 2; It is characterized in that: in the step 3); 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 ℃, and the reaction times is 20-25 hour.
4. the preparation method of high purity Tambo according to claim 3; It is characterized in that: in the step 4), O, the mol ratio of O-diethylammonium-O-(2-chloro-4-bromophenyl)-thiophosphatephosphorothioate and Trimethylamine 99 is 1: (1-4); Reflux temperature is 50-80 ℃, reaction 6-10h.
5. the preparation method of high purity Tambo according to claim 4 is characterized in that: in the step 5), the mol ratio of ammonium salt intermediate, N-PROPYLE BROMIDE and DMF is 1 in the step 4) products therefrom: (2-5): 0.005, and temperature of reaction is 50-100 ℃, reaction 4-8h.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103143244A (en) * | 2013-03-08 | 2013-06-12 | 山东科源化工有限公司 | Treatment method for exhaust gases in production of profenofos |
| CN103387484A (en) * | 2013-07-23 | 2013-11-13 | 山东科源化工有限公司 | Preparation method of 2-chloro-4-bromophonel with high purity |
| CN103588811A (en) * | 2013-11-19 | 2014-02-19 | 山东科源化工有限公司 | Preparation method of profenofos intermediate triester |
| 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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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103143244A (en) * | 2013-03-08 | 2013-06-12 | 山东科源化工有限公司 | Treatment method for exhaust gases in production of profenofos |
| 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 |
| CN103387484A (en) * | 2013-07-23 | 2013-11-13 | 山东科源化工有限公司 | Preparation method of 2-chloro-4-bromophonel with high purity |
| 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 |
| CN103588811A (en) * | 2013-11-19 | 2014-02-19 | 山东科源化工有限公司 | Preparation method of profenofos intermediate triester |
| 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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