CN1042938C - Synthesizing method for propyl-bromo-phopshorous of organic phosphorous insecticide - Google Patents
Synthesizing method for propyl-bromo-phopshorous of organic phosphorous insecticide Download PDFInfo
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- CN1042938C CN1042938C CN94108485A CN94108485A CN1042938C CN 1042938 C CN1042938 C CN 1042938C CN 94108485 A CN94108485 A CN 94108485A CN 94108485 A CN94108485 A CN 94108485A CN 1042938 C CN1042938 C CN 1042938C
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Abstract
The present invention relates to a method for preparing profenofos insecticidal agents. Under the existence of catalysts, sodium hydroxide is used as acid-binding agents; 0, 0-diethyl thiophosphoryl chloride reacts with 2-chlorine 4-bromophenol, which generates 0, 0-diethyl 0-(2-chlorine 4-bromine)phenyl thiophosphonate ester. Under the existence of amine, an alkyl-removing reaction is carried out, and 0-ethyl 0-(2-chlorine 4-bromine)phenyl thiophosphonate ammonium salts are obtained; after concentrated, the 0-ethyl 0-(2-chlorine 4-bromine)phenyl thiophosphonate ammonium salts directly react with bromopropane, and the profenofos is obtained. The present invention has the advantages of few reaction steps and simple process, the profenofos insecticidal agents have the advantages of easily acquired raw material, no environmental pollution and high yield and content, and consequently, the present invention is easy to industrialize.
Description
The present invention relates to the preparation method of Profenofos.
Profenofos is 0-ethyl S-propyl group 0-(2-chlorine 4-bromine) phenyl thiophosphatephosphorothioate, is a kind of asymmetric thiophosphatephosphorothioate insecticides that contains the rosickyite base, has broad-spectrum insecticidal activity, and antagonism insect, particularly antagonism bollworm insecticidal effect are outstanding.
Usually, Profenofos 1 has following synthetic method
To need with propylmercaptan or propylmercaptan derivative be that initiator makes (day disclosure special permission communique 80139394) to used intermediate 2 in the method 1, and mercaptan is not only expensive but also have a bad smell.Preparation 2 other method is to use the propoxy-phosphorothioic dichlorides, behind the first isomery again with ethanol synthesis, the not high by product of isomerization reaction productive rate more (U.S.3337658).Method 2 is because preparation high-content high yield 3 very difficult makes the productive rate of final product and content all lower.Method 3 has problems in environment protection owing to produce stench and volatile by product sulfur alcohol.
Synthetic method of the present invention is with 0,0-o,o-diethylthiophosphoryl chloride (hereinafter to be referred as muriate) is as the phosphorated starting raw material, when it and 2-chlorine 4-bromine phenol are acid binding agent when reacting with sodium hydroxide, obtain 0,0-diethyl 0-(2-chlorine 4-bromine) phenyl thiophosphatephosphorothioate 6 in the presence of catalyzer.Usually, the reinforced mol ratio of muriate, 2-chlorine 4-bromine phenol and sodium hydroxide is 1.05: 1: 1.10-1.20, add alkali at twice, and add earlier and the equimolar alkali of 2-chloro-4-bromine phenol, when being warming up to 40-50 ℃, add remaining alkali again.Temperature of reaction is 25～50 ℃, and catalyzer can be with various tertiary amines or tertiary ammonium salt, and consumption is the 0.5-5% of muriate weight.Obtain 6 content 89～92% (in 2-chlorine 4-bromine phenol) like this.
+ HCl (reaction 1)
The committed step of present method is 6 to go alkylation reaction to obtain 0-ethyl-10-(2-chlorine 4-bromine) phenyl thiophosphoric acid amine salt 7 in the presence of amine.Amine commonly used is dialkylamine, alkylamine or ammonia etc.Temperature of reaction can not coexisting between 0-80 ℃ according to used amine.6 with the mol ratio of amine be 1: 1.5～4.0.
67 (reactions 2)
R
1,R
2=H,Me,Et,Pr,Bu
7 without separation, after concentrating, add water directly and bromopropane reaction can obtain the Profenofos 1 of high-content high yield.In this reaction, it is excessive that N-PROPYLE BROMIDE needs, with 7 mol ratio be 1.2～4: 1.Temperature of reaction is 50～75 ℃.Profenofos 1 content that obtains like this is 90-92%, and productive rate is 84～86% (in 2-chlorine 4-bromine phenol, three step overall yields).
The invention has the advantages that: (1), obtains easily and is of high quality (general content＞95%) as phosphorous starting raw material with the muriate of heavy industrialization.(2) adopt amine as the alkali that removes alkylation reaction, do not use sulfohydrate,, avoid generation to have malodorous sulfur alcohol, help environment protection as Sodium sulfhydrate, potassium bisulfide, sulphur hydrogenation ammonium etc.(3) it is all very high respectively to go on foot reaction yield, can obtain high quality, Profenofos cheaply.(4) reactions steps is less, and technological process is simple, is easy to realize industrialization.
Example 1.0,0-diethyl 0-(2-chlorine 4-bromine) phenyl thiophosphatephosphorothioate 6 synthetic
Put into 0.1mol sodium hydroxide, 10ml water and 0.1g trimethylamine hydrochloride in the 100ml there-necked flask, stir adding 0.1mol 2-chlorine 4-bromine phenol down, drip 20g (0.105mol) muriates at 25～35 ℃ then.Slowly be warming up to 40～50 ℃ after adding, add 0.02molNaOH reactant aqueous solution 0.5h, stopped reaction, layering is placed in cold back.Get product 6 35.1g, content 92.55% (GC analytical results), productive rate 90.4% (in 2-chlorine 4-bromine phenol).
Synthesizing of example 2. Profenofos
In the 100ml there-necked flask, put into phosphorothioate triesters 6 and 21.9g (0.3mol) diethylamine and 45ml water,, generate thiophosphoric acid amine salt 7 in 65～70 ℃ of reaction 4h. by example 1 preparation.Reactant concentrates the back and adds 30ml water, 36.9g (0.3mol) N-PROPYLE BROMIDE and 0.1g dimethyl formamide catalyzer, and in 65～70 ℃ of reaction 4h, layering is placed in cold back.N-PROPYLE BROMIDE is reclaimed in the oil reservoir distillation, and excess gets Profenofos 35.5g through decompression dehydration, content 88.93% (GC analytical results), productive rate 84.5% (in 2-chlorine 4-bromine phenol).
Example 3.
Operation is just used diethylamine instead 40% dimethylamine agueous solution with example 2, gets Profenofos 35.1g, content 90.61% (GC analytical results), productive rate 85.2%6 (in 2-chlorine 4-bromine phenol).
Example 4.
Operation is just used diethylamine instead 40% aqueous methylamine solution with example 2, gets Profenofos 34.8g, content 87.68% (GC analytical results), productive rate 81.7% (in 2-chlorine 4-bromine phenol).
Claims (2)
1. method for preparing Profenofos, it is characterized in that it is with 0, the 0-o,o-diethylthiophosphoryl chloride is a raw material, the reaction of water as solvent and 2-chlorine 4-bromine phenol obtains 0 in the presence of catalyzer and acid binding agent, 0-diethyl (2-chlorine 4-bromine) phenyl thiophosphatephosphorothioate, in the presence of amine, go alkylation reaction to obtain 0-ethyl-10-(2-chlorine 4-bromine) phenyl thio-ammonium phosphate then, again with bromopropane reaction get final product product, its step is as follows:
(a) 0,0-dialkyl sulfide substituted phosphorus oxychloride and 2-chlorine 4-bromine phenol with water as solvent, sodium hydroxide as the salt of acid binding agent and Trimethylamine 99 as under the catalyzer condition, reaction is 3 hours under 25～50 ℃ of temperature, and layering is placed in cooling, and the mol ratio of reaction is 1.05: 1, catalyst levels is 0,0.5～5% of 0-dialkyl sulfide substituted phosphorus oxychloride consumption, the mol ratio of sodium hydroxide and 2-chloro-4-bromine phenol is 1.1 0～1.20: 1, and adds alkali at twice;
(b) obtain 0 with above-mentioned, 0-diethyl 0-(2-chlorine 4-bromine) phenyl thiophosphatephosphorothioate removes alkylation reaction in the presence of amine, and temperature of reaction is 0～80 ℃, and the time is 4 hours, and the mol ratio of reactant and amine is 1: 1.5～4.0, and amine is C
1-4Dialkylamine or C
1-4Alkylamine;
(c) concentrate after, add water and add excessive N-PROPYLE BROMIDE, mol ratio is 1: 1.2～4, reaction is 4 hours under 50～75 ℃ of temperature, N-PROPYLE BROMIDE is reclaimed in the oil reservoir distillation, low-boiling-point substance is taken off in the excess decompression, bromine third phosphorus.
2. according to the described method for preparing Profenofos of claim 1, it is characterized in that said amine is dialkylamine or the alkylamine that contains ethyl or methyl.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94108485A CN1042938C (en) | 1994-07-23 | 1994-07-23 | Synthesizing method for propyl-bromo-phopshorous of organic phosphorous insecticide |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94108485A CN1042938C (en) | 1994-07-23 | 1994-07-23 | Synthesizing method for propyl-bromo-phopshorous of organic phosphorous insecticide |
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| Publication Number | Publication Date |
|---|---|
| CN1101646A CN1101646A (en) | 1995-04-19 |
| CN1042938C true CN1042938C (en) | 1999-04-14 |
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| CN94108485A Expired - Fee Related CN1042938C (en) | 1994-07-23 | 1994-07-23 | Synthesizing method for propyl-bromo-phopshorous of organic phosphorous insecticide |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348602C (en) * | 2005-10-26 | 2007-11-14 | 浙江工业大学 | Synthesis method of (R,S)-S-secondary butyl o-ethyl-2-oxo-1,3-thiazolidine-3-thiosulphate |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617636B (en) * | 2012-02-24 | 2015-05-27 | 山东科源化工有限公司 | Preparation method of high-purity profenofos |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3337658A (en) * | 1964-04-27 | 1967-08-22 | Dow Chemical Co | Method for the manufacture of s-substituted phosphoro-dichloridothioates |
| JPS55139394A (en) * | 1979-04-19 | 1980-10-31 | Nippon Tokushu Noyaku Seizo Kk | Novel synthetic method of thiol phosphate ester chloride |
-
1994
- 1994-07-23 CN CN94108485A patent/CN1042938C/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3337658A (en) * | 1964-04-27 | 1967-08-22 | Dow Chemical Co | Method for the manufacture of s-substituted phosphoro-dichloridothioates |
| JPS55139394A (en) * | 1979-04-19 | 1980-10-31 | Nippon Tokushu Noyaku Seizo Kk | Novel synthetic method of thiol phosphate ester chloride |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100348602C (en) * | 2005-10-26 | 2007-11-14 | 浙江工业大学 | Synthesis method of (R,S)-S-secondary butyl o-ethyl-2-oxo-1,3-thiazolidine-3-thiosulphate |
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| CN1101646A (en) | 1995-04-19 |
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