CN1104645A - Synthesis of O,S-dialkyl-dithiophosphoryl chloride - Google Patents
Synthesis of O,S-dialkyl-dithiophosphoryl chloride Download PDFInfo
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- CN1104645A CN1104645A CN 94106602 CN94106602A CN1104645A CN 1104645 A CN1104645 A CN 1104645A CN 94106602 CN94106602 CN 94106602 CN 94106602 A CN94106602 A CN 94106602A CN 1104645 A CN1104645 A CN 1104645A
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- phosphorodithioic acid
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- alkyl ester
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Abstract
The process for preparing O,S-dialkyl dithiophosphoryl chloride by removing alkyl and chloridization features less reaction steps, high yield rate, high purity of product and the by-products sodium bromide and tertiary amine, which can be reclaimed.
Description
The present invention relates to O, the preparation method of S-dialkyl dithio phosphoryl chloride.
O, S-dialkyl dithio phosphoryl chloride are the important pesticide intermediates of the asymmetric phosphorodithioate sterilant of preparation high-efficiency low-toxicity, and it can be represented with following general formula:
R wherein, R ' is for C1-C4 straight chain identical or inequality or have the alkyl of side chain.
According to reported in literature, this intermediate synthetic mainly contains two routes, and the one: Eur.Pat.219770(1987); Jpn. Kokai Tokkyo Koho, 206393(1984); The Swiss1097631 report generates S-alkyl sulfhydryl for phosphinylidyne dichloro for the phosphinylidyne dichloro through isomerization with O-alkyl thioketones, obtains S-alkyl dithio phosphinylidyne dichloro with the thiophosphoric anhydride effect again, obtains general formula compound with the alcohol reaction then:
Wherein, the S-alkyl sulfhydryl is for the phosphinylidyne dichloro, Ger. Offen., and 3716003(1988) also available alkane sulphur chlorine of report and phosphorus trichloride react in the presence of organic acid anhydride and produce:
Another route, Ger. Offen 2532396(1977); U.S.3879500(1975) report adopts the reaction of alkanethiol and phosphorus thiochloride, again with the alcohol effect:
Article one, route technology more complicated, the used mercaptan price of second route height, and cacosmia bring many inconvenience to production.
The purpose of this invention is to provide a kind of new preparation O, the method for S-dialkyl dithio phosphoryl chloride, this processing step is few, and is easy to operate, the product yield height, purity is good.
The present invention is raw material and the synthetic phosphorodithioic acid alkyl ester of haloalkane reaction with the phosphorodithioate of cheapness, after take off alkyl and chlorination reaction obtains final product.
X＝Br、Cl B＝（CH
3）
2NH，（C
2H
5）
2NH
The available known method of phosphorodithioic acid alkyl ester (II) (J. Am. Chem. Soc., 1952,74,161.) is prepared.The present invention has done some improvement, is reflected in the aqueous solution to carry out, and temperature of reaction 20-60 ℃, reaction times 1-6 hour, yield was more than 85%.
The reaction of phosphorodithioic acid alkyl ester (II) and secondary amine obtains corresponding ammonium salt (III), and temperature of reaction 40-70 ℃, reaction times 4-8 hour, the yield of both mol ratios 1: 1.5～4. was more than 95%.Ammonium salt (III) obtains final product (I) with the phosphorus pentachloride reaction, and temperature of reaction 0-30 ℃, reaction times 1-3 hour, both mol ratios 1: 1～1.1.
Table 1 is several O, the physical constant of S-dialkyl sulfide substituted phosphorus oxychloride.
Synthetic method provided by the present invention has following characteristics:
1. reactions steps is few, and is easy to operate; 2. all to be that useful industrial chemicals is recyclable use Sodium Bromide, the tertiary amine that generates in the reaction again; 3. reaction yield height, good product purity.
Example 1.0,0-diethyl, S-n-propyl phosphorodithioate
0,0-diethyl phosphorothioate (content 91%, 0.1mol) under cooling, mix with 20% aqueous sodium hydroxide solution (0.1mol), stirred 10 minutes, under 20 ℃, the 0.5mol n-propyl bromide is slowly added, after adding, temperature rises to 60 ℃ of reactions 2 hours, cooling Petroleum ether extraction organic layer.Drying steams solvent, and underpressure distillation is collected b.p.78-80 ℃/1mmHg, yield 85%.
Example 2 0-ethyl-S-n-propyl phosphorodithioic acid diformazan ethyl amine salt
With the O that example 1 makes, O-diethyl-S-n-propyl phosphorodithioate 0.1mol and 0.4mol 30% dimethylamine agueous solution are heated to 60 ℃, react 6 hours, and decompression steams water, obtains faint yellow transparent thick liquid, yield 95%.
Example 3 O-ethyl-S-n-propyl dithio phosphoryl chloride
The 0.1mol phosphorus pentachloride is suspended in the 25ml phosphorus oxychloride, at 0-15 ℃, example 2 gained ammonium salts are splashed into, maintain 20 ℃ of reactions 2 hours, decompression steams phosphorus oxychloride, in the resistates impouring frozen water, and use Petroleum ether extraction, steam solvent, underpressure distillation, collect b.p.78-82 ℃/1mmHg, yield 80%.
Example 4 O-ethyl-S-n-propyl phosphorodithioic acid triethyl ammonium salt
O, O-diethyl-S-n-propyl phosphorodithioate 0.1mol is dissolved in the 50ml dehydrated alcohol, with 0.2mol diethylamine back flow reaction 8 hours, steams ethanol and excessive diethylamine, thick liquid, yield 80%.
Several O of table 1, S-dialkyl dithio phosphoryl chloride phosphorus oxychloride physical constant
Claims (1)
1, a kind of preparation O, the method for S-dialkyl dithio phosphoryl chloride (I),
R ' wherein, R is C identical or inequality
1-C
4Straight chain or have the alkyl of side chain, it is characterized in that it is is the synthetic phosphorodithioic acid alkyl ester of raw material and haloalkane reaction with the phosphorodithioate, and then through taking off alkyl and chlorination reaction, operation steps is as follows:
(a) phosphorodithioate and haloalkane react in the aqueous solution, and mol ratio is 1: 1～1.1, makes acid binding agent with sodium hydroxide, react 1～6 hour under 20～60 ℃ of temperature, and extraction steams solvent, obtains the phosphorodithioic acid alkyl ester;
(b) phosphorodithioic acid alkyl ester and secondary amine reaction, mol ratio is 1: 1.5～4, reacts 4～8 hours under 40～70 ℃ of temperature, underpressure distillation obtains the phosphorodithioic acid ammonium salt;
(c) phosphorodithioic acid ammonium salt and phosphorus pentachloride carry out chlorination reaction, and mol ratio 1: 1～1.1 was reacted 1～3 hour under 0～30 ℃ of temperature, and decompression steams phosphorus oxychloride, and Petroleum ether extraction steams solvent, and underpressure distillation promptly gets product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94106602A CN1042426C (en) | 1994-06-15 | 1994-06-15 | Synthesis of O,S-dialkyl-dithiophosphoryl chloride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94106602A CN1042426C (en) | 1994-06-15 | 1994-06-15 | Synthesis of O,S-dialkyl-dithiophosphoryl chloride |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1104645A true CN1104645A (en) | 1995-07-05 |
| CN1042426C CN1042426C (en) | 1999-03-10 |
Family
ID=5032603
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94106602A Expired - Fee Related CN1042426C (en) | 1994-06-15 | 1994-06-15 | Synthesis of O,S-dialkyl-dithiophosphoryl chloride |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1042426C (en) |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3879500A (en) * | 1973-10-15 | 1975-04-22 | Stauffer Chemical Co | Process for Preparing mono- and di-alkylmercaptophosphorothionochloridates |
| US4736050A (en) * | 1985-10-17 | 1988-04-05 | Ishihara Sangyo Kaisha Ltd. | Process for preparing a S-substituted phosphoro-chloridothiolate |
| US4727178A (en) * | 1986-07-14 | 1988-02-23 | Stauffer Chemical Co. | Process for preparing phosphorodichloridothiolate |
-
1994
- 1994-06-15 CN CN94106602A patent/CN1042426C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1042426C (en) | 1999-03-10 |
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| C14 | Grant of patent or utility model | ||
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| CF01 | Termination of patent right due to non-payment of annual fee |