CN103304596A - Waste residue-free preparation method of O,O-dialkyl thiophosphoryl chloride - Google Patents
Waste residue-free preparation method of O,O-dialkyl thiophosphoryl chloride Download PDFInfo
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- CN103304596A CN103304596A CN201310186901XA CN201310186901A CN103304596A CN 103304596 A CN103304596 A CN 103304596A CN 201310186901X A CN201310186901X A CN 201310186901XA CN 201310186901 A CN201310186901 A CN 201310186901A CN 103304596 A CN103304596 A CN 103304596A
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- dialkyl
- phosphorus oxychloride
- substituted phosphorus
- waste residue
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Abstract
The invention discloses a waste residue-free preparation method of O,O-dialkyl thiophosphoryl chloride, which is characterized by comprising the following steps: by taking dialkyl chlorophosphite as an intermediate, performing chlorination with O,O-dialkyl phosphorodithioate under the effect of strong Lewis acid metal chloride to prepare O,O-dialkyl thiophosphoryl chloride with the structural general formula shown in the specification, wherein the chemical equation is shown in the specification. The method for preparing high-content O,O-dialkyl thiophosphoryl chloride, disclosed by the invention, has the advantages of simple process route, mild reaction conditions, simple after-treatment and low production cost, and is convenient for industrial transformation; and the method avoids or reduces pollution, strictly controls the process, saves after-treatment and prevents the generation of viscose waste sulfur residues.
Description
Technical field
The present invention relates to O, the O-dialkyl sulfide substituted phosphorus oxychloride does not have the waste residue preparation method.
Background technology
O, O-dialkyl sulfide substituted phosphorus oxychloride are the important intermediate of producing organophosphorus pesticide and cephalosporin antimicrobial drug.
There is wretched insufficiency in the thiophosphoric anhydride method that generally adopts both at home and abroad at transformation efficiency and content at present, produces a large amount of reluctant viscosity sulfur sludges, and seriously polluted, and difficulty of governance is big (referring to US5278331; CN101130554); The thiophosphoryl chloride method of Beyer Co., Ltd's research and development is in a large amount of excessive reactions down of alkyl alcohol, and the exothermic heat of reaction amount is big, must maintain reaction about 0 ℃, and energy consumption is big, product content is low (referring to US5948930).
Summary of the invention
The objective of the invention is to for overcoming O in the past, the defective of O-dialkyl sulfide substituted phosphorus oxychloride synthetic method, a kind of O is provided, the O-dialkyl sulfide substituted phosphorus oxychloride does not have the waste residue preparation method, not only stop the generation of viscosity sulphur but also improved yield and quality, this method is convenient to aftertreatment, pollutes less, easily handles, and has improved the content of product.
For solving the problems of the technologies described above, the present invention adopts following technical scheme to realize,
A kind of O, the O-dialkyl sulfide substituted phosphorus oxychloride does not have the waste residue preparation method, be included in the existing thiophosphoric anhydride technology chlorination process that to increase torak acid dialkyl be intermediate, the O of synthetic following general structure under the muriatic effect of strong lewis acid metal (M), the O-dialkyl sulfide substituted phosphorus oxychloride:
Under the prerequisite that does not influence reaction, the substituted alkyl R in the general structure
1=R
2Also can R
1≠ R
2, R wherein
1, R
2For methyl alcohol, ethanol, Virahol reach ether and the aldehyde that derives thus.
Used metal chloride comprises the muriate of iron, aluminium, lead, copper, tin, zinc, nickel, silicon, manganese, and the optimal chlorination thing is aluminum chloride and zinc chloride class.
Chemical equation is as follows:
O, the mole proportioning of O-dialkyl dithiophosphate and torak acid dialkyl is 1.25～1.00:1, best proportioning is 1.10～1.02:1.
Chlorine and O, the mole proportioning of O-dialkyl dithiophosphate is 1.5～1.0:1, best proportioning is 1.15～1.0:1.
The mole proportioning of metal chloride and torak acid dialkyl ester is 0.16～0.002:1, and best proportioning is 0.02～0.01:1.
Reaction need not solvent one step and finishes, and technology is simple, the yield height.
Reaction temperature and, temperature of reaction is controlled at 30～95 ℃, optimum temps is 50～70 ℃.
The control of reaction soaking time was at 3～12 hours, and best soaking time is 4～8 hours.
With existing O, O-dialkyl sulfide substituted phosphorus oxychloride synthesis technique relatively the invention has the advantages that:
1, operational path is simple, the reaction conditions gentleness;
2, low production cost is convenient to the industrialization transformation;
3, aftertreatment is simple, one-step synthesis high-content O, O-dialkyl sulfide substituted phosphorus oxychloride;
4, stop or reduce pollution, strict control technology is saved aftertreatment, has stopped the generation of waste water, waste residue.
?
Embodiment
Below by the specific embodiment mode the present invention is elaborated.
Embodiment 1
In having the 1000ml four-hole boiling flask of airway, refrigerating unit, thermometer, drop into the torak diethyl phthalate 310g that accurately measures, O, O-diethyl phosphorothioate 372g, aluminum chloride 2g successively; Slowly be warming up to 35 ℃, in 4 hours, feed chlorine 164g, be incubated 4 hours, drive excessive chlorine and hydrogen chloride gas away with nitrogen; Discontinuity stirs, fast cooling to 25 ℃; Under 25 ℃, filter O, O-o,o-diethylthiophosphoryl chloride 735g, content are 98%; Be 96% with torak diethyl phthalate calculated yield.
Embodiment 2
In having the 1000ml four-hole boiling flask of airway, refrigerating unit, thermometer, drop into the torak diethyl phthalate 310g that accurately measures, O, O-diethyl phosphorothioate 372g, aluminum chloride 2g successively; Slowly be warming up to 35 ℃, in 4 hours, feed chlorine 164g, be incubated 4 hours, drive excessive chlorine and hydrogen chloride gas away with nitrogen; Be cooled to 25 ℃; Filter down at 25 ℃, filtrate through washing, separate O, O-o,o-diethylthiophosphoryl chloride 715g, content are 99.5%; Be 95% with torak diethyl phthalate calculated yield.
Embodiment 3
In having the 1000ml four-hole boiling flask of airway, refrigerating unit, thermometer, drop into the torak diethyl phthalate 310g accurately measure successively, O, O-diethyl phosphorothioate 372g, aluminum chloride 0.5g and last crowd filter residue 2.5g; Slowly be warming up to 35 ℃, in 4 hours, feed chlorine 164g, be incubated 4 hours, drive excessive chlorine and hydrogen chloride gas away with nitrogen; Discontinuity stirs, fast cooling to 25 ℃; Under 25 ℃, filter O, O-o,o-diethylthiophosphoryl chloride 735g, content are 98%; Be 96% with torak diethyl phthalate calculated yield.
Above-described embodiment is only in order to technical scheme of the present invention to be described but not design of the present invention and protection domain are limited; those of ordinary skill of the present invention is made amendment to technical scheme of the present invention or is equal to replacement; and not breaking away from aim and the scope of technical scheme, it all should be encompassed in the claim scope of the present invention.
Claims (15)
1. O, the O-dialkyl sulfide substituted phosphorus oxychloride does not have the waste residue preparation method, it is characterized in that: comprise that with torak acid dialkyl be intermediate, under the effect of strong lewis acid metal chloride with O, the O-dialkyl dithiophosphate is prepared as follows the O of general structure, O-dialkyl sulfide substituted phosphorus oxychloride through chlorination:
Wherein, substituted alkyl R
1=R
2Also can R
1≠ R
2, R
1, R
2Be methyl alcohol, ethanol, isopropyl alcohols, and the ether that derives thus and aldehyde.
2. a kind of O according to claim 1, the O-dialkyl sulfide substituted phosphorus oxychloride does not have the waste residue preparation method, it is characterized in that: under the effect of strong lewis acid metal chloride, be intermediate and O with torak acid dialkyl, O-dialkyl dithiophosphate reaction temperature and preparation.
3. a kind of O according to claim 1 and 2, the O-dialkyl sulfide substituted phosphorus oxychloride does not have the waste residue preparation method, it is characterized in that: used strong lewis acid metal chloride comprises the muriate of iron, aluminium, lead, copper, tin, zinc, nickel, silicon, manganese.
4. a kind of O according to claim 3, the O-dialkyl sulfide substituted phosphorus oxychloride does not have the waste residue preparation method, it is characterized in that: preferred muriate is aluminum chloride and zinc chloride class.
5. a kind of O according to claim 1 and 2, the O-dialkyl sulfide substituted phosphorus oxychloride does not have the waste residue preparation method, it is characterized in that: preparation O, the O of O-dialkyl sulfide substituted phosphorus oxychloride, the mole proportioning of O-dialkyl dithiophosphate and torak acid dialkyl is 1.25～1.00:1.
6. a kind of O according to claim 5, the O-dialkyl sulfide substituted phosphorus oxychloride does not have the waste residue preparation method, it is characterized in that: preparation O, the O of O-dialkyl sulfide substituted phosphorus oxychloride, O-dialkyl group two
The mole proportioning of thiophosphatephosphorothioate and torak acid dialkyl is 1.10～1.02:1.
7. a kind of O according to claim 1 and 2, the O-dialkyl sulfide substituted phosphorus oxychloride does not have the waste residue preparation method, it is characterized in that: preparation O, the mole proportioning of the chlorine of O-dialkyl sulfide substituted phosphorus oxychloride and torak acid dialkyl ester is 1.5～1.0:1.
8. a kind of O according to claim 7, the O-dialkyl sulfide substituted phosphorus oxychloride does not have the waste residue preparation method, it is characterized in that: preparation O, the mole proportioning of the chlorine of O-dialkyl sulfide substituted phosphorus oxychloride and torak acid dialkyl ester is 1.15～1.0:1.
9. a kind of O according to claim 1 and 2, the O-dialkyl sulfide substituted phosphorus oxychloride does not have the waste residue preparation method, it is characterized in that: preparation O, the mole proportioning of the metal chloride of O-dialkyl sulfide substituted phosphorus oxychloride and torak acid dialkyl ester is 0.08～0.001:1.
10. a kind of O according to claim 9, the O-dialkyl sulfide substituted phosphorus oxychloride does not have the waste residue preparation method, it is characterized in that: preparation O, the mole proportioning of the metal chloride of O-dialkyl sulfide substituted phosphorus oxychloride and torak acid dialkyl ester is 0.01～0.005:1.
11. a kind of O according to claim 1 and 2, the O-dialkyl sulfide substituted phosphorus oxychloride does not have the waste residue preparation method, it is characterized in that: reaction temperature and, temperature of reaction is 30～95 ℃.
12. a kind of O according to claim 11, the O-dialkyl sulfide substituted phosphorus oxychloride does not have the waste residue preparation method, it is characterized in that: temperature of reaction is 50～70 ℃.
13. a kind of O according to claim 1 and 2, the O-dialkyl sulfide substituted phosphorus oxychloride does not have the waste residue preparation method, it is characterized in that: the reaction soaking time is 3～12 hours.
14. a kind of O according to claim 13, the O-dialkyl sulfide substituted phosphorus oxychloride does not have the waste residue preparation method, it is characterized in that: the reaction soaking time is 4～8 hours.
15. a kind of O according to claim 1 and 2, the O-dialkyl sulfide substituted phosphorus oxychloride does not have
The waste residue preparation method is characterized in that: after insulation reaction finished, discontinuity stirred, fast cooling to 25 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310186901.XA CN103304596B (en) | 2013-05-20 | 2013-05-20 | O, O-dialkyl sulfide substituted phosphorus oxychloride is without waste residue preparation method |
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|---|---|---|---|
| CN201310186901.XA CN103304596B (en) | 2013-05-20 | 2013-05-20 | O, O-dialkyl sulfide substituted phosphorus oxychloride is without waste residue preparation method |
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|---|---|
| CN103304596A true CN103304596A (en) | 2013-09-18 |
| CN103304596B CN103304596B (en) | 2016-03-09 |
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|---|---|---|---|
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104072536A (en) * | 2014-07-11 | 2014-10-01 | 武汉理工大学 | Method for desulfurizing in ethyl chloride production |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4287136A (en) * | 1980-06-16 | 1981-09-01 | Ciba-Geigy Corporation | Process for the preparation of O,O-dialkylthionophosphoric acid chlorides |
-
2013
- 2013-05-20 CN CN201310186901.XA patent/CN103304596B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4287136A (en) * | 1980-06-16 | 1981-09-01 | Ciba-Geigy Corporation | Process for the preparation of O,O-dialkylthionophosphoric acid chlorides |
Non-Patent Citations (1)
| Title |
|---|
| 汤崇铭 等: "O,O-二乙基硫代磷酰氯及O,O-二甲基硫代磷酰氯新合成工艺的研究", 《云南师范大学学报》, vol. 13, no. 4, 31 December 1993 (1993-12-31), pages 55 - 58 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104072536A (en) * | 2014-07-11 | 2014-10-01 | 武汉理工大学 | Method for desulfurizing in ethyl chloride production |
| CN104072536B (en) * | 2014-07-11 | 2016-05-11 | 武汉理工大学 | The method of diethylaluminum monochloride production desulfurization |
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| CN103304596B (en) | 2016-03-09 |
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