CN1101646A

CN1101646A - Synthesizing method for propyl-bromo-phopshorous of organic phosphorous insecticide

Info

Publication number: CN1101646A
Application number: CN 94108485
Authority: CN
Inventors: 唐除痴; 刘纶祖; 吴桂萍; 李�真; 朱昌寿
Original assignee: Nankai University
Current assignee: Nankai University
Priority date: 1994-07-23
Filing date: 1994-07-23
Publication date: 1995-04-19
Anticipated expiration: 2014-07-23
Also published as: CN1042938C

Abstract

The process can obtain 0,0-diethyl 0-(2chloro 4-bromo) phenyl thiophosphonate ester from 0,0-diethyl thiophosphoryl chloride and 2-chloro-4-bromophenol through reactions with catalyst and sodium hydroxide as acid binder and then with amine presence, to obtain 0-ethyl 0-(2-chloro-4bromo) ammonium phenyl thiophosphate and to obtain the insecticide phosphorus propyl bromide in direct reaction with bromopropane after concentration. The invention has many advantages for industrial production.

Description

Synthesizing method for propyl-bromo-phopshorous of organic phosphorous insecticide

The present invention relates to the preparation method of Profenofos.

Profenofos is an O-ethyl S-propyl group O-(2-chlorine 4-bromine) the phenyl thiophosphatephosphorothioate, be a kind of asymmetric thiophosphatephosphorothioate insecticides that contains the rosickyite base, have broad-spectrum insecticidal activity, 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 80 139394) 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 in the presence of catalyzer are that acid binding agent is when reacting with sodium hydroxide, obtain 0,0-diethyl 0-(2-chlorine 4-bromine) phenyl thiophosphatephosphorothioate 6.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 content 89～92%(of 6 like this in 2-chlorine 4-bromine phenol).

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.

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%, productive rate be 84～86%(in 2-chlorine 4-bromine phenol, three the 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 is 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 at 25～35 ℃ then) muriate.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%(is 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 by example 1 preparation) diethylamine and 45ml water, in 65～70 ℃ of reaction 4h, generate thiophosphoric acid amine salt 7.Reactant concentrates the back and adds 30ml water, 36.9g(0.3mol) N-PROPYLE BROMIDE and 0.1g dimethyl formamide catalyzer, 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%(is 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%(is 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%(is in 2-chlorine 4-bromine phenol).

Claims

1, a kind of 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 tertiary amine or tertiary amine 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 1.10～1.20: 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, temperature of reaction is 0～80 ℃, and the time is 4 hours, the mol ratio of reactant and amine is 1: 1.5～4.0, and amine is dialkylamine, alkylamine or ammonia;

(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,, it is characterized in that said amine is dialkylamine or the alkylamine that contains ethyl or methyl according to the described method for preparing Profenofos of claim 1.