CN102796136A - Synthesis method of dimethylheptyl methylphosphonate - Google Patents
Synthesis method of dimethylheptyl methylphosphonate Download PDFInfo
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- CN102796136A CN102796136A CN2012102420766A CN201210242076A CN102796136A CN 102796136 A CN102796136 A CN 102796136A CN 2012102420766 A CN2012102420766 A CN 2012102420766A CN 201210242076 A CN201210242076 A CN 201210242076A CN 102796136 A CN102796136 A CN 102796136A
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- methyl
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- aromatic heterocycle
- phosphorous acid
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Abstract
The invention relates to a synthesis method of dimethylheptyl methylphosphonate, and aims to solve the difficulty in raw material measurement and the safety problem caused by the use of the high-pressure reaction kettle in the existing technique, thereby lowering the production cost. The invention has the advantages of simple operating procedure, high output and high yield, and is suitable for industrial production. The method comprises the following steps: adding an acyl-chlorination reagent into a reaction vessel, wherein the acyl-chlorination reagent is thionyl chloride, phosphorous pentachloride or triphosgene; dropwisely adding dimethyl methyl phosphonate (DMMP) into the acyl-chlorination reagent at room temperature and adding catalytic amount of catalyst, wherein the consumption of the acyl-chlorination reagent is 2-5 times of the DMMP (0.6-1.5 times for triphosgene) on mol basis, and the catalyst is N,N-di-substituted-formamide or N-containing aromatic heterocyclic ring or N-substituted N-containing aromatic heterocyclic ring or tertiary amine; and uniformly stirring at room temperature.
Description
Technical field
The invention belongs to the organo phosphorous compounds preparation field, relate in particular to a kind of compound method of methyl-phosphorous acid diformazan heptyl ester.
Background technology
Methyl-phosphorous acid diformazan heptyl ester (trade(brand)name: be present widely used efficient neutral organophosphorus extraction agent P350), be used for the extracting and separating of rare earth, uranium-thorium, cobalt-nickel and scandium, its structural formula is as follows:
At present, the general compound method of methyl-phosphorous acid diformazan heptyl ester is, generates the methyl mixture by methyl chloride, phosphorus trichloride, aluminum chloride at the autoclave internal reaction, by secondary octanol mixture carried out alcoholysis then and obtains, and this synthetic route is as follows.
CH
3Cl+PCl
3+AlCl
3→[CH
3PCl
3]
+[AlCl
4]
-
[CH
3PCl
3]
+[AlCl
4]
-+3ROH→CH
3P(O)(OR)
2
R＝C
6H
13CH(CH
3)-
The key of this route is the synthetic of midbody methyl mixture, because the raw material methyl chloride is gas at normal temperatures and pressures, and this is reflected under the comparatively high temps and carries out, and maximum can reach 50kg pressure in the reaction kettle.The metering of methyl chloride simultaneously is also not too accurate, therefore, in large-scale production process, has potential safety hazard, present domestic this product of manufacturer production that almost do not have.
Summary of the invention
For solving the problems of the technologies described above; The present invention provides a kind of raw material metering difficult problem and autoclave that can solve in the current technology to use the safety-problems of bringing; Thereby reduce production costs; And operating procedure is simple, output, yield height, the compound method of the methyl-phosphorous acid diformazan heptyl ester that suitability for industrialized is produced.
The compound method of methyl-phosphorous acid diformazan heptyl ester of the present invention, it comprises the steps:
A, chloride reagent is joined in the reaction vessel, chloride reagent is a kind of in sulfur oxychloride, phosphorus pentachloride, the TRIPHOSGENE 99.5, and (DMMP) at room temperature is added drop-wise in the chloride reagent with dimethyl methyl phosphonate; With mol is measure unit, and the consumption of chloride reagent is 2-5 times of dimethyl methyl phosphonate (DMMP), and adds the catalyzer of catalytic amount; Catalyzer is N, and N-two substituted formamides or contain the N aromatic heterocycle or N-replaces and to contain N aromatic heterocycle or tertiary amine stir under the room temperature; Then the material in the reaction vessel is warming up to 60-150 ℃, insulation reaction 1.5-2.5h, underpressure distillation again; Collect the cut of 56-57 ℃/14torr of boiling point, get the methyl phosphonyl dichloride;
B, under agitation condition; Excessive secondary octanol is added drop-wise in the methyl phosphonyl dichloride, is measure unit with mol, and the consumption of secondary octanol is 2-10 a times of methyl phosphonyl dichloride;-10 ℃-40 ℃ are reacted 30-60min earlier; Respectively react 30-60min at 50 ℃-80 ℃ and 80 ℃-150 ℃ respectively then, in this process, vacuumize the HCl that generates except that dereaction;
C, be chilled to room temperature, washing is to neutral, and underpressure distillation is collected 140-145 ℃/2mmHg cut and got product methyl-phosphorous acid diformazan heptyl ester.
The compound method of methyl-phosphorous acid diformazan heptyl ester of the present invention wherein is measure unit with mol, said N, N-two substituted formamides or contain the N aromatic heterocycle or N-to replace the consumption contain N aromatic heterocycle or tertiary amine be the 0.1%-10% of dimethyl methyl phosphonate.
Compared with prior art, beneficial effect of the present invention is:
The present invention adopts chloride reagent and DMMP under the effect of catalyzer, to generate active intermediate-methyl phosphonyl dichloride, further carries out esterification with secondary octanol, thereby makes methyl-phosphorous acid diformazan heptyl ester.This technology has been avoided the use of methyl chloride gas, is reflected under the normal pressure to carry out, and the metering difficult problem and the autoclave that have solved the raw material in the current technology use the safety-problems of bringing.Because be reflected under the normal pressure and carry out, all raw materials are liquid, avoided the metering difficult problem of the raw material in the current technology and autoclave to use the safety-problems of bringing.Chloride reagent and DMMP be at N, and N-two substituted formamides contain the N aromatic heterocycle, N-replaces and contains under the effect of catalyzer such as N aromatic heterocycle, tertiary amine, can quantitative reaction generate active intermediate-methyl phosphonyl dichloride.Methyl phosphonyl dichloride and secondary octanol carry out esterification, make methyl-phosphorous acid diformazan heptyl ester, and this reaction divides three temperature ranges, both can save energy, and can reduce the generation of multiple side reaction again.Therefore, the present invention not only productive rate is high, and wastage of material is few, also can reduce cost significantly, reduces facility investment.In a word, the compound method of methyl-phosphorous acid diformazan heptyl ester of the present invention is easy and simple to handle, output, yield height, and production cost is low, and facility investment is few, and more existing method is applicable to suitability for industrialized production more.Therefore, the compound method of methyl-phosphorous acid diformazan heptyl ester of the present invention has outstanding substantive distinguishing features and obvious improvement, and is promptly creative.
Embodiment
Following specific embodiments of the invention describes in further detail.
Following examples are used to explain the present invention, but are not used for limiting scope of the present invention.
The compound that the present invention relates to (I) composition principle is as follows:
At N, N-two substituted formamides contain N aromatic heterocycle, N-and replace and contain under the effect of catalyzer such as N aromatic heterocycle, tertiary amine, and quantitative reaction generation methyl phosphonyl dichloride almost can take place for DMMP and acylating reagent.The methyl phosphonyl dichloride further generates title product with secondary octanol reaction.This technology has been avoided the use of methyl chloride gas, is reflected under the normal pressure to carry out, and the metering difficult problem and the autoclave that have solved the raw material in the current technology use the safety-problems of bringing.
Embodiment 1
The compound method of methyl-phosphorous acid diformazan heptyl ester of the present invention comprises the steps:
A, chloride reagent is joined in the reaction vessel, chloride reagent is a kind of in sulfur oxychloride, phosphorus pentachloride, the TRIPHOSGENE 99.5, and (DMMP) at room temperature is added drop-wise in the chloride reagent with dimethyl methyl phosphonate; With mol is measure unit, and the consumption of chloride reagent is 2 times or 2.5 times or 3 times or 3.5 times or 4 times or 4.5 times or 5 times of dimethyl methyl phosphonate (DMMP), and adds the catalyzer of catalytic amount; Catalyzer is N; N-two substituted formamides or contain the N aromatic heterocycle or N-replaces and to contain N aromatic heterocycle or tertiary amine stir under the room temperature, then the material in the reaction vessel are warming up to 60 ℃ or 150 ℃; Insulation reaction 1.5h or 2.5h or 2.5h; Underpressure distillation again, the cut of 56-57 ℃/14torr of collection boiling point gets the methyl phosphonyl dichloride;
B, under agitation condition; Excessive secondary octanol is added drop-wise in the methyl phosphonyl dichloride; With mol is measure unit; The consumption of secondary octanol is 2 times or 2.5 times or 3 times or 3.5 times or 4 times or 4.5 times or 5 times or 5.5 times or 6 times or 6.5 times or 7 times or 7.5 times or 8 times or 8.5 times or 9 times or 10 times of methyl phosphonyl dichloride; Earlier-10 ℃ or 0 ℃ or 10 ℃ or 20 ℃ or 25 ℃ or 30 ℃ or 40 ℃ of reaction 30min or 40min or 50min or 55min or 60min, then respectively at 50 ℃ or 55 ℃ or 60 ℃ or 65 ℃ or 70 ℃ or 75 ℃ or 80 ℃, and 80 ℃ or 85 ℃ or or 90 ℃ or 95 ℃ or 100 ℃ or 105 ℃ or 120 ℃ or 130 ℃ or 135 ℃ or 140 ℃ or 150 ℃ respectively react 30-60min; In this process, vacuumize the HCl that generates except that dereaction;
C, be chilled to room temperature, washing is to neutral, and underpressure distillation is collected 140-145 ℃/2mmHg cut and got product methyl-phosphorous acid diformazan heptyl ester.
With mol is measure unit, above-mentioned N, N-two substituted formamides or contain the N aromatic heterocycle or N-to replace the consumption contain N aromatic heterocycle or tertiary amine be the 0.1%-10% of dimethyl methyl phosphonate, yield 96%.
Embodiment 2
The compound method of methyl-phosphorous acid diformazan heptyl ester of the present invention comprises the steps:
(1) acyl chloride reaction: the mixed solution of dimethyl methyl phosphonate 124.08g (1mol) and 0.8g pyridine (0.01mol) is added drop-wise to 520.6gPCl under 20 ℃
5(2.5mol), keep stirring at room 1h, be warming up to 80 ℃, insulation reaction 2h, the material that 56-57 ℃/14mmHg of boiling point is collected in underpressure distillation gets the methyl phosphonyl dichloride, yield 94.2%, purity 98.1%.
(2) esterification: under agitation, 14.9g methyl phosphonyl dichloride (0.1mol) is slowly joined in the secondary octanol of 65.1g (0.5mol), the HCl gas of generation absorbs with alkali lye, and the methyl chloride that generates is collected.Elder generation's room temperature (about 30 ℃) reaction 45min, 55 ℃ are reacted 1.5h then, last 85 ℃ of reaction 2h.
(3) aftertreatment: reaction solution is chilled to room temperature, and washing is carried out drying to neutral with SODIUM SULPHATE ANHYDROUS 99PCT, and underpressure distillation is collected 140-145 ℃/2mmHg cut and got product, productive rate 92%.
The analytical data of product methyl-phosphorous acid diformazan heptyl ester of the present invention is following:
1H?NMR(CDCl
3，300Hz)δ(ppm)：0.85(s，3H，P-CH
3)，0.98(t，6H，2CH
3)，1.15(d，6H，2CH
3)，1.20-1.35(m，16H，8CH
2)，1.60-1.65(m，4H，2CH
2)，4.47-4.51(m，2H，2CH)，
31P?NMR(CDCl
3，300Hz)δ(ppm)：29.23(s，P)；ESI-MS?m/z：321.03[M+H]
+。
Embodiment 3
The compound method of methyl-phosphorous acid diformazan heptyl ester of the present invention comprises the steps:
(1) acyl chloride reaction: the mixed solution of 124.08g dimethyl methyl phosphonate (1mol) and 0.73gDMF (0.01mol) is slowly dropped in the 297.5g sulfur oxychloride (2.5mol); Be heated to backflow; Be incubated 4 hours, after the reaction solution cooling, the material that 56-57 ℃/14mmHg of boiling point is collected in underpressure distillation gets the methyl phosphonyl dichloride; Yield 96.4%, purity 98.5%.
(2) esterification: under agitation, 14.9g methyl phosphonyl dichloride (0.1mol) is slowly joined in the secondary octanol of 78.1g (0.6mol), the HCl gas of generation absorbs with alkali lye, and the methyl chloride that generates is collected.Elder generation's room temperature (about 30 ℃) reaction 45min, 55 ℃ are reacted 1.5h then, last 85 ℃ of reaction 2h.
(3) aftertreatment: reaction solution is chilled to room temperature, and washing is carried out drying to neutral with SODIUM SULPHATE ANHYDROUS 99PCT, and underpressure distillation is collected 140-145 ℃/2mmHg cut and got product, productive rate 93%.
The analytical data of product methyl-phosphorous acid diformazan heptyl ester of the present invention is following:
1H?NMR(CDCl
3，300Hz)δ(ppm)：0.85(s，3H，P-CH
3)，0.98(t，6H，2CH
3)，1.15(d，6H，2CH
3)，1.20-1.35(m，16H，8CH
2)，1.60-1.65(m，4H，2CH
2)，4.47-4.51(m，2H，2CH)，
31P?NMR(CDCl
3，300Hz)δ(ppm)：29.23(s，P)；ESI-MS?m/z：321.03[M+H]
+。
The above only is a preferred implementation of the present invention; Should be pointed out that for those skilled in the art, under the prerequisite that does not break away from know-why of the present invention; Can also make some improvement and modification, these improve and modification also should be regarded as protection scope of the present invention.
Claims (2)
1. the compound method of methyl-phosphorous acid diformazan heptyl ester is characterized in that comprising the steps:
A, chloride reagent is joined in the reaction vessel, chloride reagent is a kind of in sulfur oxychloride, phosphorus pentachloride, the TRIPHOSGENE 99.5, and (DMMP) at room temperature is added drop-wise in the chloride reagent with dimethyl methyl phosphonate; With mol is measure unit, and the consumption of chloride reagent is 2-5 times of dimethyl methyl phosphonate (DMMP), and adds the catalyzer of catalytic amount; Catalyzer is N, and N-two substituted formamides or contain the N aromatic heterocycle or N-replaces and to contain N aromatic heterocycle or tertiary amine stir under the room temperature; Then the material in the reaction vessel is warming up to 60-150 ℃, insulation reaction 1.5-2.5h, underpressure distillation again; Collect the cut of 56-57 ℃/14torr of boiling point, get the methyl phosphonyl dichloride;
B, under agitation condition; Excessive secondary octanol is added drop-wise in the methyl phosphonyl dichloride, is measure unit with mol, and the consumption of secondary octanol is 2-10 a times of methyl phosphonyl dichloride;-10 ℃-40 ℃ are reacted 30-60min earlier; Respectively react 30-60min at 50 ℃-80 ℃ and 80 ℃-150 ℃ respectively then, in this process, vacuumize the HCl that generates except that dereaction;
C, be chilled to room temperature, washing is to neutral, and underpressure distillation is collected 140-145 ℃/2mmHg cut and got product methyl-phosphorous acid diformazan heptyl ester.
2. the compound method of methyl-phosphorous acid diformazan heptyl ester according to claim 2; It is characterized in that: be measure unit with mol; Said N, N-two substituted formamides contain the N aromatic heterocycle or N-to replace the consumption contain N aromatic heterocycle or tertiary amine be the 0.1%-10% of dimethyl methyl phosphonate.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106749397A (en) * | 2016-12-09 | 2017-05-31 | 西安元创化工科技股份有限公司 | A kind of preparation method of extraction |
| CN107383091A (en) * | 2017-07-14 | 2017-11-24 | 吉林大学 | A kind of new method for synthesizing substitution phosphinate |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1514029A (en) * | 2002-12-10 | 2004-07-21 | 中国科学院长春应用化学研究所 | Method of extracting rare earth from apatite |
| WO2005030779A2 (en) * | 2003-09-23 | 2005-04-07 | Eisai Co. Ltd. | Laulimalide analogs with anti-cancer activitity |
-
2012
- 2012-07-13 CN CN201210242076.6A patent/CN102796136B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1514029A (en) * | 2002-12-10 | 2004-07-21 | 中国科学院长春应用化学研究所 | Method of extracting rare earth from apatite |
| WO2005030779A2 (en) * | 2003-09-23 | 2005-04-07 | Eisai Co. Ltd. | Laulimalide analogs with anti-cancer activitity |
Non-Patent Citations (1)
| Title |
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| P. K. GUTCH, ET AL.: "N,N-Dichloro Poly(styrene-co-divinyl benzene) Sulfonamide Polymeric Beads: An Efficient and Recyclable Decontaminating Reagent for O,S-Diethyl Methyl Phosphonothiolate, a Simulant of VX", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106749397A (en) * | 2016-12-09 | 2017-05-31 | 西安元创化工科技股份有限公司 | A kind of preparation method of extraction |
| CN106749397B (en) * | 2016-12-09 | 2019-01-18 | 西安元创化工科技股份有限公司 | A kind of preparation method of extraction |
| CN107383091A (en) * | 2017-07-14 | 2017-11-24 | 吉林大学 | A kind of new method for synthesizing substitution phosphinate |
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| CN102796136B (en) | 2017-01-25 |
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