CN1702073A - Process for synthesizing O,O'-alkyl thiophosphoric acid - Google Patents
Process for synthesizing O,O'-alkyl thiophosphoric acid Download PDFInfo
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- CN1702073A CN1702073A CN 200410042569 CN200410042569A CN1702073A CN 1702073 A CN1702073 A CN 1702073A CN 200410042569 CN200410042569 CN 200410042569 CN 200410042569 A CN200410042569 A CN 200410042569A CN 1702073 A CN1702073 A CN 1702073A
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- thiophosphoric acid
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Abstract
The invention discloses a method for synthesizing O, O'-dialkyl phosphorothioic acid, which takes phosphorothioic acid and low-carbon alcohol as materials to synthesize O, O'-dialkyl phosphorothioic acid with the existing of catalyst and organic solvent. The invention chooses organic amine and tervalence organo-phosphines compound as catalyst and choose non-polar organics such as aromatics, alkyl halide and esters as organic solvent. The invention has the advantages of little side reaction, simple removal of reaction heat, low likelihood of accident and high yield.
Description
Technical field:
The present invention relates to a kind of O, the synthetic method of O '-alkylthio phosphoric acid belongs to the thiophosphoric acid class.
Background technology:
Existing O, the synthetic method of O '-alkoxyl group thiophosphoric acid adopts usually under the condition that has thiophosphoric acid to exist, and low-carbon alcohol joined reaction obtains in the thiophosphoric anhydride.For example, Deutsches Reichs-Patent 2500452 had been reported O in 1975, synthesizing of O '-dimethyl thiophosphoric acid, its method is: thiophosphoric anhydride is mixed with the neutral oil (byproduct of reaction) of 15-18%, drip excessive slightly methyl alcohol down at 55 ℃, be warmed up to 60 ℃ again, and reacted 1 hour, product is neutralized into sodium salt and uses for next step, yield 75-80%.Its weak point is: 1. because the thiophosphoric anhydride activity is higher, reaction heat can promote other side reactions of reaction itself and thiophosphoric anhydride to quicken; 2. control badly, be prone to accidents, great hidden danger is arranged in the operation; 3. yield is lower, and by product is more, and is big for environment pollution.
Summary of the invention:
The objective of the invention is to propose a kind of under the condition of catalyzer and solvent existence, low temperature drips low-carbon alcohol to thiophosphoric anhydride, improve the reaction yield of thiophosphoric acid, and reduce the O of the danger of reaction itself, the synthetic method of O '-dialkyl group thiophosphoric acid in thiophosphoric anhydride.
The object of the present invention is achieved like this: with thiophosphoric anhydride and low-carbon alcohol is raw material, synthetic O, and O '-dialkyl group thiophosphoric acid, in the presence of catalyzer and solvent, 0～40 ℃ of control reaction temperature drips low-carbon alcohol, and the reaction times is 80～160 minutes.Described low-carbon alcohol is meant that total carbon atom number is less than eight alcohol compound, as methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol.Described catalyzer is an organic amine, and as Monomethylamine, dimethylamine, Trimethylamine 99, triethylamine, tri-n-butyl amine, trolamine, tervalent organic phosphine compound is as trimethyl phosphite, triethyl-phosphite, triphenyl phosphorus.Described solvent is an aromatic hydrocarbon, as benzene,toluene,xylene, mixed toluene, and haloalkane,, two power methane imitative as power, the immiscible nonpolar organic matter of ester and water is as vinyl acetic monomer, N-BUTYL ACETATE.
Advantage of the present invention is: owing to adopt than low reaction temperatures, side reaction is less, and reaction heat is removed easily, has reduced the possibility that accident takes place.Because adopt catalyzer that reaction is carried out at low temperatures, the side reaction that thiophosphoric anhydride is too much caused is less, and is convenient to control reaction process.Owing to adopt the way of organic solvent, help removing partial reaction heat, side reaction is inhibited, the possibility that accident takes place is greatly reduced, reaction yield is higher.
Embodiment:
This O, the alkyl in O '-alkylthio phosphoric acid comprises methyl, ethyl, propyl group, sec.-propyl, normal-butyl etc.Each alkyl correspondence be the corresponding low-carbon alcohol that participates in reaction, as methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol.
The low-carbon alcohol such as the methyl alcohol that in reactor, add 0～4mol, ethanol, propyl alcohol, Virahol, propyl carbinol, 0～350ml non-polar solvent is an aromatic hydrocarbon, as benzene, toluene, dimethylbenzene, mixed toluene, haloalkane, imitative as power, two power methane, the immiscible nonpolar organic matter of ester and water, as vinyl acetic monomer, N-BUTYL ACETATE, 0～0.10mol catalyzer is an organic amine, as Monomethylamine, dimethylamine, Trimethylamine 99, triethylamine, tri-n-butyl amine, trolamine, tervalent organic phosphine compound, as trimethyl phosphite, triethyl-phosphite, triphenyl phosphorus slowly drops into the thiophosphoric anhydride of 1mol, and controlled temperature is at 0～40 ℃, in 0.5～2 hour, drip 3.8～0mol low-carbon alcohol, maintain 0～70 ℃ again, continue insulation 0～2 hour, obtain O, O '-alkylthio phosphoric acid.
Embodiment 1, O, the preparation of O '-dimethyl thiophosphoric acid: the methyl alcohol that adds 13 grams in reactor, 350 milliliters of benzene, 5 gram triethylamines, under agitation, controlled temperature is between 10～15 ℃, drop into about 222 gram thiophosphoric anhydrides, maintain again and drip 121 gram methyl alcohol between 10～15 ℃ in 30 to 60 minutes, continued insulated and stirred 0～2 hour, obtain O, O '-dimethyl thiophosphoric acid, yield about 98%.
Embodiment 2, and with embodiment 1, controlled temperature obtains O between 20～25 ℃, O '-dimethyl thiophosphoric acid, yield about 98%.
Embodiment 3, and with embodiment 1, controlled temperature obtains O between 35～40 ℃, O '-dimethyl thiophosphoric acid, yield about 98%.
Embodiment 4, O, the preparation of O '-diethyl thiophosphoric acid: the ethanol that adds 18 grams in reactor, 350 milliliters of benzene, 5 gram triethylamines, under agitation, controlled temperature is between 10～15 ℃, drop into about 222 gram thiophosphoric anhydrides, maintain again between 10～15 ℃, drip 174 gram ethanol in 30 to 60 minutes, continued insulated and stirred 0～2 hour, obtain O, O '-diethyl thiophosphoric acid, yield about 97%.
Embodiment 5, and with embodiment 4, controlled temperature obtains O between 20～25 ℃, O '-diethyl thiophosphoric acid, yield about 97%.
Embodiment 6, and with embodiment 4, controlled temperature obtains O between 35～40 ℃, O '-diethyl thiophosphoric acid, yield about 97%.
Embodiment 7, O, the preparation of O '-dipropyl thiophosphoric acid: the propyl alcohol that adds 25 grams in reactor, 350 milliliters of benzene, 5 gram triethylamines, under agitation, controlled temperature is between 10～15 ℃, drop into about 222 gram thiophosphoric anhydrides, maintain again between 10～15 ℃, drip 227 gram propyl alcohol in 30～60 minutes, continued insulated and stirred 0～2 hour, obtain O, O '-dipropyl thiophosphoric acid, yield about 99%.
Embodiment 8, and with embodiment 7, controlled temperature obtains O between 20～25 ℃, O '-dipropyl thiophosphoric acid, yield about 99%.
Embodiment 9, and with embodiment 7, controlled temperature obtains O between 35～40 ℃, O '-dipropyl thiophosphoric acid, yield about 99%.
Embodiment 10, O, the preparation of O '-di-isopropyl thiophosphoric acid: the Virahol that adds 25 grams in reactor, 350 milliliters of benzene, 5 gram triethylamines, under agitation, between 10～15 ℃ of the controlled temperature, drop into about 222 gram thiophosphoric anhydrides, maintain again and drip 227 gram Virahols between 10～15 ℃ in 30～60 minutes, continued insulated and stirred 0～2 hour, obtain O, O '-di-isopropyl thiophosphoric acid, yield about 98%.
Embodiment 11, and with embodiment 10, controlled temperature obtains O between 20～25 ℃, O '-di-isopropyl thiophosphoric acid, yield about 98%.
Embodiment 12, and with embodiment 10, controlled temperature obtains O between 35～40 ℃, O '-di-isopropyl thiophosphoric acid, yield about 98%.
Embodiment 13:O, the preparation of O '-dibutyl thiophosphoric acid: in reactor, add the butanols of 30 grams, 350 milliliters of benzene, 5 gram triethylamines, under agitation, controlled temperature drops into about 222 gram thiophosphoric anhydrides between 10～15 ℃, maintain again between 10～15 ℃, drip 280 gram butanols in 30～60 minutes, continued insulated and stirred 0～2 hour, obtain O, O '-dibutyl thiophosphoric acid, yield about 97%.
Embodiment 14, and with embodiment 13, controlled temperature obtains O between 20～25 ℃, O '-dibutyl thiophosphoric acid, yield about 97%.
Embodiment 15, and with embodiment 13, controlled temperature obtains O between 35～40 ℃, O '-dibutyl thiophosphoric acid, yield about 97%.
Claims (4)
1. O, the synthetic method of O '-dialkyl group thiophosphoric acid, it is a raw material with thiophosphoric anhydride and low-carbon alcohol, synthetic O, O '-dialkyl group thiophosphoric acid is characterized by: in the presence of catalyzer and non-polar solvent, and 0～40 ℃ of control reaction temperature, drip low-carbon alcohol, the reaction times is 80～160 minutes.
2. according to the described O of claim 1, the synthetic method of O '-dialkyl group thiophosphoric acid is characterized by: described low-carbon alcohol is meant that total carbon atom number is less than eight alcohol compound, as methyl alcohol, ethanol, propyl alcohol, Virahol, propyl carbinol.
3. according to the described O of claim 1, the synthetic method of O '-dialkyl group thiophosphoric acid, it is characterized by: described catalyzer is an organic amine, as Monomethylamine, dimethylamine, Trimethylamine 99, triethylamine, tri-n-butyl amine, trolamine, tervalent organic phosphine compound is as trimethyl phosphite, triethyl-phosphite, triphenyl phosphorus.
4. according to the described O of claim 1, the synthetic method of O '-dialkyl group thiophosphoric acid, it is characterized by: described non-polar solvent is an aromatic hydrocarbon, as benzene,toluene,xylene, mixed toluene, haloalkane,, two power methane imitative as power, the immiscible nonpolar organic matter of ester and water is as vinyl acetic monomer, N-BUTYL ACETATE.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410042569 CN1702073A (en) | 2004-05-24 | 2004-05-24 | Process for synthesizing O,O'-alkyl thiophosphoric acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410042569 CN1702073A (en) | 2004-05-24 | 2004-05-24 | Process for synthesizing O,O'-alkyl thiophosphoric acid |
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| CN1702073A true CN1702073A (en) | 2005-11-30 |
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| CN 200410042569 Pending CN1702073A (en) | 2004-05-24 | 2004-05-24 | Process for synthesizing O,O'-alkyl thiophosphoric acid |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017310A (en) * | 2015-07-01 | 2015-11-04 | 辽宁石油化工大学 | Method for catalytic preparation of solvent-free thio-phosphoric acid |
| CN108864181A (en) * | 2018-07-26 | 2018-11-23 | 德州绿霸精细化工有限公司 | A kind of method of synthesis O, O- dimethyl disulfide substituted phosphate |
-
2004
- 2004-05-24 CN CN 200410042569 patent/CN1702073A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105017310A (en) * | 2015-07-01 | 2015-11-04 | 辽宁石油化工大学 | Method for catalytic preparation of solvent-free thio-phosphoric acid |
| CN108864181A (en) * | 2018-07-26 | 2018-11-23 | 德州绿霸精细化工有限公司 | A kind of method of synthesis O, O- dimethyl disulfide substituted phosphate |
| CN108864181B (en) * | 2018-07-26 | 2021-04-13 | 德州绿霸精细化工有限公司 | Method for synthesizing O, O-dimethyl phosphorodithioate |
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