CN105131031A - Method for synthesizing N-alkylthiophosphoryl triamide through continuous reaction - Google Patents
Method for synthesizing N-alkylthiophosphoryl triamide through continuous reaction Download PDFInfo
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- CN105131031A CN105131031A CN201510395880.1A CN201510395880A CN105131031A CN 105131031 A CN105131031 A CN 105131031A CN 201510395880 A CN201510395880 A CN 201510395880A CN 105131031 A CN105131031 A CN 105131031A
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- hydrocarbylthio
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Abstract
The invention discloses a method for synthesizing N-alkylthiophosphoryl triamide through a continuous reaction. The method comprises the following steps: 1, mixing thiophosphoryl chloride with an organic solvent, pre-cooling the obtained mixture in a heat exchanger to -5-0DEG C, mixing the material with an aminated compound pre-cooled to -5-0DEG C, and reacting the obtained mixture in a micro-reactor to obtain N-alkylthiophosphoryl dichloride at the outlet of the reactor; and 2, allowing N-alkylthiophosphoryl dichloride to directly enter an ammoniation reactor, carrying out an ammoniation reaction on N-alkylthiophosphoryl dichloride and ammonia gas, and post-processing after the ammoniation reaction is completed to obtain N-alkylthiophosphoryl triamide. N-alkylthiophosphoryl triamide is synthesized through a micro-reaction technology with high mass transfer and heat transfer efficiency, so conversion of intermittence to continuity is realized, the operating step is simplified, and the reaction yield is improved.
Description
Technical field
The invention belongs to chemosynthesis technical field, relate to the method for successive reaction synthesis N-hydrocarbylthio phosphoryl triamide.
Background technology
N-propyl thiophosphoryl triamide, normal-butyl thiophosphoryl triamine are all effective soil urease inhibitor.They with urea with the activity of certain proportion mixing suppression soil urokinase, significantly can reduce the degradation speed of urea, improve the utilization ratio of nitrogen, provide the elements such as S, P simultaneously, have good soil improvement action.
The current synthetic method of N-hydrocarbylthio phosphoryl triamide is substantially all carry out in a kettle., comprise following two class methods: (1) two-step approach, patent US4530714, US5883297 and CN101337976A discloses " two-step approach " prepares the method for N-alkyl base thiophosphoryl triamide, namely under acid binding agent existent condition or without under the condition of acid binding agent, by phosphorus thiochloride solution and the direct hybrid reaction of alkylamine solution, or adopt the mode dripping alkylamine solution to obtain N-alkylthio phosphinylidyne two chloromethylated intermediate, another reactor is proceeded to by after this intermediate separation and purification, logical ammonia, N-alkyl thiophosphoryl triamide is separated to obtain through process after reaction for some time.This complex process, relates to low-temp reaction and long reaction time, and energy consumption is large, and yield low cost is high; (2) one kettle way, CN101412733A discloses, and " one kettle way " prepares the method for N-hydrocarbylthio phosphoryl triamide, namely under the condition of acid binding agent, phosphorus thiochloride and alkyl uncle generate intermediate N hydrocarbylthio phosphinylidyne dichloro and acid binding agent hydrochloride by reacting, then at same reaction system and ammonia gas react, target product N-hydrocarbylthio phosphoryl triamide, acid binding agent and ammonium chloride is generated.Although this technique saves step but must use acid binding agent, be again that one kettle way adds post-processing difficulty, complex operation step.
In addition, two-step reaction involved in this building-up reactions is thermopositive reaction, reaction process is comparatively violent, and above technique is carried out all in a kettle., weak heat-dissipating and be difficult to avoid back-mixing between reaction raw materials and product, therefore the by product such as di-n-butyl thiophosphoryl triamide and three normal-butyl thiophosphoryl triamine is more.Therefore there is production equipment on producing huge, the problems such as aftertreatment difficulty, environmental protection pressure increase.
Summary of the invention
The invention provides the method for a kind of successive reaction synthesis N-hydrocarbylthio phosphoryl triamide, the method increase the yield of reaction, operation is more simple, and production efficiency is improved.
A method for successive reaction synthesis N-hydrocarbylthio phosphoryl triamide, comprises the steps:
(1) in interchanger ,-5 ~ 0 DEG C is chilled to by after phosphorus thiochloride and organic solvent mixing in advance, and then mix with the aminated compounds being chilled to-5 ~ 0 DEG C in advance, the mixture obtained reacts in microreactor, obtains N-hydrocarbylthio phosphinylidyne dichloro from reactor outlet;
Described microreactor is microchannel reactor, and the internal diameter of described microchannel reactor is 10 ~ 500 μm;
The structural formula of described aminated compounds is RNH
2;
The structure of described N-hydrocarbylthio phosphinylidyne dichloro is as shown in formula II:
(2) the N-hydrocarbylthio phosphinylidyne dichloro that step (1) obtains directly enters in ammoniation reactor and carries out aminating reaction with ammonia, obtains described N-hydrocarbylthio phosphoryl triamide after aminating reaction is complete through process later;
The structure of described N-hydrocarbylthio phosphoryl triamide is as shown in formula I:
Wherein, R is selected from C
1~ C
8alkyl, C
1~ C
8cycloalkyl or benzyl.
The microchannel reactor that present invention employs particular inside diameters carrys out continuous synthesis N-hydrocarbylthio phosphinylidyne dichloro, this microchannel reactor has higher mass transfer and heat transfer efficiency, simultaneously, in advance precooling is carried out to reaction raw materials at the initial period of reaction, effectively improve the yield of reaction, directly can enter ammoniation reactor without separation from the reaction solution of microreactor outlet and generate N-hydrocarbylthio phosphoryl triamide with ammonia gas react, production efficiency and the security of whole continuous reaction process are higher.
In step (1), the kind of organic solvent can produce larger impact to the yield of reaction, and described organic solvent is at least one in ethyl acetate, toluene, chlorobenzene, methylene dichloride, tetrahydrofuran (THF) and 2-methyltetrahydrofuran.As preferably, described organic solvent is methylene dichloride or tetrahydrofuran (THF).
In step (1), controlling suitable throughput ratio is the key that each raw material can fully react completely, the volume flow ratio of described phosphorus thiochloride, organic solvent, alkyl primary amine is 1:0.5 ~ 15:1.0 ~ 2.0, is preferably 1:5 ~ 8:1.5 ~ 1.8.
As preferably, described R is n-propyl, normal-butyl or isobutyl-.
In step (1), reactor cooling bath temperature is-20 ~ 0 DEG C, is preferably-10 DEG C;
Stable reactor inlet temperatures is less than 35 DEG C, and the reaction solution residence time is 1 ~ 8min, is preferably 2 ~ 4min.
Described microreactor is the microchannel reactor of multi-stage series, and volume is 30ml ~ 120ml.The reactor of every section of series connection, all with outlet, according to reacting the degree of carrying out, can derive reaction solution from different outlets.
As further preferred, the internal diameter of described microchannel reactor is 150 ~ 200 μm, and volume is 60 ~ 90ml, and the flow velocity of described phosphorus thiochloride is 2.5 ~ 3.5ml/min, the flow velocity of described organic solvent is 14 ~ 21ml, and the flow velocity of described amine chemical combination is 3.6 ~ 5.5ml/min.Now, the efficiency of reaction improves greatly, and side reaction obviously reduces.
Compared with the existing technology, beneficial effect of the present invention is embodied in:
(1) the micro-reacting tcchnology synthesis N-hydrocarbylthio phosphoryl triamide with higher mass transfer and heat transfer efficiency is adopted.The method can realize the conversion from interval to continuous print, and operating process is simple, and reaction yield is high.Production efficiency and security will be largely increased;
(2) although the temperature sensor reading of Reactor inlet about 30 DEG C, and reactor outlet temperature is all the time below 5 DEG C, and proved response device exchange capability of heat is enough, and thermal diffusivity is good;
(3) reactor can meet the service requirements under high temperature, high pressure operating mode.And it is good to have handiness based on the microreactor that modular designs, reliability is high and be easy to advantages such as safeguarding.
Embodiment
Below in conjunction with technical scheme and example in detail the specific embodiment of the present invention, but the content of invention can not be limited.
The preparation of embodiment 1N-n-propyl phosphorothioic dichlorides
Phosphorus thiochloride (SPCl
3), organic solvent (tetrahydrofuran THF or methylene dichloride CH
2cl
2) and Tri N-Propyl Amine (n-C
3h
9n) microreactor system is injected respectively by ram pump, phosphorus thiochloride and organic solvent are first via precooling in micro-interchanger (-5 ~ 0 DEG C) after a mixing tank mixing, and then mix at a stacked mixing tank with the Tri N-Propyl Amine (-5 ~ 0 DEG C) through precooling, the microchannel reactor that the mixture obtained enters multi-stage series carries out time delay reaction, the internal diameter of every section of microchannel reactor is 200 μm, volume is 30mL, and every section of microchannel reactor is provided with and independently exports.Control reactor cooling bath temperature and reaction time, collect and obtain intermediate reaction liquid, contained N-n-propyl phosphorothioic dichlorides adopts HPLC area normalization method to carry out characterizing (the results are shown in Table 1).
The reaction conditions of table 1 embodiment 1 and result
The preparation of embodiment 2N-normal-butyl phosphorothioic dichlorides
(1) phosphorus thiochloride (SPCl
3), organic solvent (tetrahydrofuran THF or methylene dichloride CH
2cl
2) and n-Butyl Amine 99 (n-C
4h
11n) microreactor system is injected respectively by ram pump, phosphorus thiochloride and organic solvent are first via precooling in micro-interchanger (-5 ~ 0 DEG C) after a mixing tank mixing, and then mix at a stacked mixing tank with the Tri N-Propyl Amine (-5 ~ 0 DEG C) through precooling, the microchannel reactor that the mixture obtained enters multi-stage series carries out time delay reaction, the internal diameter of every section of microchannel reactor is 150 μm, volume is 30mL, and every section of microchannel reactor is provided with and independently exports.Control reactor cooling bath temperature and reaction time, collect and obtain intermediate reaction liquid, contained N-normal-butyl phosphorothioic dichlorides adopts HPLC area normalization method to carry out characterizing (the results are shown in Table 2).
(2) the intermediate reaction liquid that step (1) obtains directly passes into and is equipped with in the ammoniation reactor of methylene dichloride, react with ammonia under 25 DEG C of normal pressures, after reacting completely, add water stirring 1 hour, stratification, after organic solvent vacuum distillation recovered solvent, resistates adds mixed solvent (methylene dichloride: sherwood oil=1:1) and is cooled to-5 ~ 0 DEG C of crystallization and obtains normal-butyl thiophosphoryl triamine sterling, for white crystal, yield and purity are in table 2.
The reaction conditions of table 2 embodiment 2 and result
The preparation of embodiment 3N-isobutylthio phosphinylidyne dichloro
Phosphorus thiochloride (SPCl
3), organic solvent (tetrahydrofuran THF or methylene dichloride CH
2cl
2) and isobutylamine (i-C
4h
11n) microreactor system is injected respectively by ram pump, phosphorus thiochloride and organic solvent are first via precooling in micro-interchanger (-5 ~ 0 DEG C) after a mixing tank mixing, and then mix at a stacked mixing tank with the Tri N-Propyl Amine (-5 ~ 0 DEG C) through precooling, the microchannel reactor that the mixture obtained enters multi-stage series carries out time delay reaction, the internal diameter of every section of microchannel reactor is 150 μm, volume is 30mL, and every section of microchannel reactor is provided with and independently exports.Control reactor cooling bath temperature and reaction time, collect and obtain intermediate reaction liquid, contained N-isobutylthio phosphinylidyne dichloro adopts HPLC area normalization method to carry out characterizing (the results are shown in Table 3).
The reaction conditions of table 3 embodiment 3 and result
Comparative example 1
(1) phosphorus thiochloride (SPCl
3), organic solvent (tetrahydrofuran THF or methylene dichloride CH
2cl
2) and n-Butyl Amine 99 (n-C
4h
11n) microreactor system is injected respectively by ram pump, phosphorus thiochloride and organic solvent first mix via under a mixing tank room temperature, and then mix at a stacked mixing tank under room temperature with Tri N-Propyl Amine, the microchannel reactor that the mixture obtained enters multi-stage series carries out time delay reaction, the internal diameter of every section of microchannel reactor is 150 μm, volume is 30mL, and every section of microchannel reactor is provided with and independently exports.Control reactor cooling bath temperature and reaction time, collect and obtain intermediate reaction liquid, contained N-normal-butyl phosphorothioic dichlorides adopts HPLC area normalization method to carry out characterizing (the results are shown in Table 4).
(2) the intermediate reaction liquid that step (1) obtains directly passes into and is equipped with in the ammoniation reactor of methylene dichloride, react with ammonia under 25 DEG C of normal pressures, after reacting completely, add water stirring 1 hour, stratification, after organic solvent vacuum distillation recovered solvent, resistates adds mixed solvent (methylene dichloride: sherwood oil=1:1) and is cooled to-5 ~ 0 DEG C of crystallization and obtains normal-butyl thiophosphoryl triamine sterling, for white crystal, yield and purity are in table 4.
Comparative example 2
(1) phosphorus thiochloride (SPCl
3), organic solvent (tetrahydrofuran THF or methylene dichloride CH
2cl
2) and n-Butyl Amine 99 (n-C
4h
11n) microreactor system is injected respectively by ram pump, phosphorus thiochloride and organic solvent are first via precooling in micro-interchanger (-5 ~ 0 DEG C) after a mixing tank mixing, and then mix at a stacked mixing tank with the Tri N-Propyl Amine (-5 ~ 0 DEG C) through precooling, the microchannel reactor that the mixture obtained enters multi-stage series carries out time delay reaction, the internal diameter of every section of microchannel reactor is 600 μm, volume is 30mL, and every section of microchannel reactor is provided with and independently exports.Control reactor cooling bath temperature and reaction time, collect and obtain intermediate reaction liquid, contained N-normal-butyl phosphorothioic dichlorides adopts HPLC area normalization method to carry out characterizing (the results are shown in Table 4).
(2) the intermediate reaction liquid that step (1) obtains directly passes into and is equipped with in the ammoniation reactor of methylene dichloride, react with ammonia under 25 DEG C of normal pressures, after reacting completely, add water stirring 1 hour, stratification, after organic solvent vacuum distillation recovered solvent, resistates adds mixed solvent (methylene dichloride: sherwood oil=1:1) and is cooled to-5 ~ 0 DEG C of crystallization and obtains normal-butyl thiophosphoryl triamine sterling, for white crystal, yield and purity are in table 4.
The reaction conditions of table 4 comparative example 1 and comparative example 2 and result
From the result of comparative example 1, if without precooling step, the reaction efficiency of step (1) significantly reduces; The result of comparative example 2 illustrates, when the internal diameter of pipeline is larger, reaction effect also obviously reduces.
Claims (10)
1. a method for successive reaction synthesis N-hydrocarbylthio phosphoryl triamide, is characterized in that, comprise the steps:
(1) in interchanger ,-5 ~ 0 DEG C is chilled to by after phosphorus thiochloride and organic solvent mixing in advance, and then mix with the aminated compounds being chilled to-5 ~ 0 DEG C in advance, the mixture obtained reacts in microreactor, obtains N-hydrocarbylthio phosphinylidyne dichloro from reactor outlet;
Described microreactor is microchannel reactor, and the internal diameter of described microchannel reactor is 10 ~ 500 μm;
The structural formula of described aminated compounds is RNH
2;
The structure of described N-hydrocarbylthio phosphinylidyne dichloro is as shown in formula II:
(2) the N-hydrocarbylthio phosphinylidyne dichloro that step (1) obtains directly enters in ammoniation reactor and carries out aminating reaction with ammonia, obtains described N-hydrocarbylthio phosphoryl triamide after aminating reaction is complete through process later;
The structure of described N-hydrocarbylthio phosphoryl triamide is as shown in formula I:
Wherein, R is selected from C
1~ C
8alkyl, C
1~ C
8cycloalkyl or benzyl.
2. the method for successive reaction synthesis N-hydrocarbylthio phosphoryl triamide according to claim 1, it is characterized in that, in step (1), described organic solvent is at least one in ethyl acetate, toluene, chlorobenzene, methylene dichloride, tetrahydrofuran (THF) and 2-methyltetrahydrofuran.
3. the method for successive reaction synthesis N-hydrocarbylthio phosphoryl triamide according to claim 2, it is characterized in that, described organic solvent is methylene dichloride or tetrahydrofuran (THF).
4. the method for successive reaction synthesis N-hydrocarbylthio phosphoryl triamide according to claim 1, it is characterized in that, in step (1), the volume flow ratio of described phosphorus thiochloride, organic solvent, alkyl primary amine is 1:0.5 ~ 15:1.0 ~ 2.0.
5. the method for successive reaction synthesis N-hydrocarbylthio phosphoryl triamide according to claim 4, it is characterized in that, the volume flow ratio of described phosphorus thiochloride, organic solvent, alkyl primary amine is 1:5 ~ 8:1.5 ~ 1.8.
6. the method for successive reaction synthesis N-hydrocarbylthio phosphoryl triamide according to claim 1, it is characterized in that, in step (1), described R is n-propyl, normal-butyl or isobutyl-.
7. the method for successive reaction synthesis N-hydrocarbylthio phosphoryl triamide according to claim 1, it is characterized in that, in step (1), reactor cooling bath temperature is-20 ~ 0 DEG C;
Stable reactor inlet temperatures is less than 35 DEG C, and the reaction solution residence time is 1 ~ 8min.
8. the method for successive reaction synthesis N-hydrocarbylthio phosphoryl triamide according to claim 7, it is characterized in that, reactor cooling bath temperature is-10 DEG C, and the reaction solution residence time is 2 ~ 4min.
9. the method for successive reaction synthesis N-hydrocarbylthio phosphoryl triamide according to claim 1, it is characterized in that, in step (1), described microreactor is the microchannel reactor of multi-stage series, and cumulative volume is 30ml ~ 120ml.
10. the method for successive reaction synthesis N-hydrocarbylthio phosphoryl triamide according to claim 9, it is characterized in that, the cumulative volume of described microreactor is 60 ~ 90ml.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110950904A (en) * | 2019-11-12 | 2020-04-03 | 武威金仓生物科技有限公司 | Continuous preparation method and device of N-N-butyl thiophosphoryl triamide |
| CN111808132A (en) * | 2019-04-11 | 2020-10-23 | 西南科技大学 | Method for continuously and rapidly preparing N-phenyl thiophosphoryl dichloride by using microreactor |
Citations (3)
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|---|---|---|---|---|
| CN101525348A (en) * | 2009-04-07 | 2009-09-09 | 林文斌 | Method for industrialized production of N-alkyl substituted phosphoric triamide |
| WO2010045895A2 (en) * | 2008-10-20 | 2010-04-29 | Agra Group, A.S. | A process for preparing n-(hydrocarbyl) phosphoric or thiophosphoric triamides |
| CN104370957A (en) * | 2014-10-28 | 2015-02-25 | 浙江奥复托化工有限公司 | Microchannel synthesis technology for N-(n-Butyl)thiophosphoric triamide |
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2015
- 2015-07-03 CN CN201510395880.1A patent/CN105131031B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010045895A2 (en) * | 2008-10-20 | 2010-04-29 | Agra Group, A.S. | A process for preparing n-(hydrocarbyl) phosphoric or thiophosphoric triamides |
| CN101525348A (en) * | 2009-04-07 | 2009-09-09 | 林文斌 | Method for industrialized production of N-alkyl substituted phosphoric triamide |
| CN104370957A (en) * | 2014-10-28 | 2015-02-25 | 浙江奥复托化工有限公司 | Microchannel synthesis technology for N-(n-Butyl)thiophosphoric triamide |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111808132A (en) * | 2019-04-11 | 2020-10-23 | 西南科技大学 | Method for continuously and rapidly preparing N-phenyl thiophosphoryl dichloride by using microreactor |
| CN110950904A (en) * | 2019-11-12 | 2020-04-03 | 武威金仓生物科技有限公司 | Continuous preparation method and device of N-N-butyl thiophosphoryl triamide |
| CN110950904B (en) * | 2019-11-12 | 2023-05-05 | 武威金仓生物科技有限公司 | Continuous preparation method and preparation device for N-N-butyl thiophosphoric triamide |
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