CN111808132A - Method for continuously and rapidly preparing N-phenyl thiophosphoryl dichloride by using microreactor - Google Patents
Method for continuously and rapidly preparing N-phenyl thiophosphoryl dichloride by using microreactor Download PDFInfo
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- CN111808132A CN111808132A CN201910288322.3A CN201910288322A CN111808132A CN 111808132 A CN111808132 A CN 111808132A CN 201910288322 A CN201910288322 A CN 201910288322A CN 111808132 A CN111808132 A CN 111808132A
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- 238000000034 method Methods 0.000 title claims abstract description 21
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 238000005935 nucleophilic addition reaction Methods 0.000 claims abstract description 17
- SXIWNIQDOJKDGB-UHFFFAOYSA-N dichloro-phenyl-sulfanylidene-$l^{5}-phosphane Chemical compound ClP(Cl)(=S)C1=CC=CC=C1 SXIWNIQDOJKDGB-UHFFFAOYSA-N 0.000 claims abstract description 13
- BMDVPRGEZHHGLJ-UHFFFAOYSA-N [S](Cl)(Cl)Cl.[P] Chemical compound [S](Cl)(Cl)Cl.[P] BMDVPRGEZHHGLJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 11
- 239000012043 crude product Substances 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- 238000007670 refining Methods 0.000 claims description 8
- 238000000746 purification Methods 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- FNGLQNMQHOAIJQ-UHFFFAOYSA-N Cl[S](Cl)Cl Chemical compound Cl[S](Cl)Cl FNGLQNMQHOAIJQ-UHFFFAOYSA-N 0.000 claims description 2
- LTYMSROWYAPPGB-UHFFFAOYSA-N diphenyl sulfide Chemical compound C=1C=CC=CC=1SC1=CC=CC=C1 LTYMSROWYAPPGB-UHFFFAOYSA-N 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 claims 1
- 238000005086 pumping Methods 0.000 claims 1
- 239000007858 starting material Substances 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 16
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000002347 injection Methods 0.000 description 7
- 239000007924 injection Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 108091034117 Oligonucleotide Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- -1 biology Substances 0.000 description 1
- 229960000074 biopharmaceutical Drugs 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical class OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000007344 nucleophilic reaction Methods 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000012047 saturated solution Substances 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 description 1
- 229910000342 sodium bisulfate Inorganic materials 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- WQYSXVGEZYESBR-UHFFFAOYSA-N thiophosphoryl chloride Chemical group ClP(Cl)(Cl)=S WQYSXVGEZYESBR-UHFFFAOYSA-N 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/26—Amides of acids of phosphorus containing P-halide groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
The invention discloses a continuous and rapid preparation method by utilizing a microreactorN-phenylthiophosphoryl dichloride. In a micro-structure reactor, taking trichloro-sulfur phosphorus and aniline as raw materials, and carrying out nucleophilic addition reaction under the continuous flow condition; the crude product is separated and purified to obtain the high-qualityN-phenylthiophosphoryl dichloride. The invention has the advantages of rapid and continuous preparationNThe method has the characteristics of phenyl thiophosphoryl dichloride, simple operation, continuous and controllable process, mild condition, good product selectivity and capability of realizing industrial production.
Description
Technical Field
The invention relates to a rapid, continuous and high-selectivity synthesis in a microreactorN-phenylthiophosphoryl dichloride.
Background
NPhenylthiophosphoryl dichlorides are of particular interest as intermediates for the synthesis of pharmaceuticals, biologicals and fine chemicals, in particular for the preparation of oligonucleotide phosphorodithioates.
Pitto et al (m.e. pitto, j.n. Granger, y. Cho, n. Farschtschi, d. g. gorenstein.Tetrahedron1991, 47, 2449-24611) uses trichloro sulfur phosphorus, aniline, benzene, 20% sodium hydroxide aqueous solution as raw material, and the raw material is processed at low temperature (-5)oC) Reacted to obtain a catalyst containingN-a suspension of phenylthiophosphoryl dichloride, which is diluted with benzene, washed with a saturated solution of NaCl containing 1% sodium bisulfate and subjected to a series of subsequent treatmentsIs processed to obtainNPhenyl thiophosphoryl dichloride in a yield of 72.0%. The reaction process has the defects of long reaction period, complex post-treatment, high solvent toxicity and the like. However, in connection with the synthesisNThe patent of phenylthiophosphoryl dichloride has not been reported.
A microreactor is a three-dimensional structural element which can be used for carrying out chemical reactions and which is manufactured in a solid matrix by means of special microfabrication techniques. The micro-reactor has the characteristics of small channel size, large specific surface area and the like, so that the micro-reactor has the advantages of high heat transfer and mass transfer efficiency, easiness in operation, accurate control, safety, reliability, no amplification effect and the like (B.P. Mason, K.E.price, J.L. Steinbacher, A.R. Bogdan, D.T. McQuade.Chem. Rev,.2007, 107, 2300-2318.), which is widely applied to the fields of nano materials, fine chemicals, biology, medicine and the like (X.C. Solvas, A. deMello).Chem. Commun., 2011, 47, 1936-1942; M. A. M. Gijs, F. Lacharme,U. Lehmann.Chem. Rev.2010, 110, 1518-1563; J. Yoshida, A. Nagaki, T.Yamada.Chem. Eur. J., 2008, 14, 7450-7459.). In a micro-reactor, taking trichloro-sulfur-phosphor and aniline as raw materials to synthesizeNThe process for the preparation of phenylthiophosphoryl dichloride has not yet been reported. The micro-structure reactor is adopted, the process is safe and reliable, continuous flow operation is realized in the whole process, and the product selectivity is good.
Disclosure of Invention
The invention aims to provide a simple, quick and efficient synthesisN-phenylthiophosphoryl dichloride.
Preparation of the inventionNThe process for the preparation of phenylthiophosphoryl dichloride is: respectively preparing trichloro-sulfur phosphorus and aniline into a certain concentration, making nucleophilic addition reaction in a continuous flow microreactor to obtain crude product, separating, purifying and refining to obtain the invented productN-phenylthiophosphoryl dichloride.
The solvent used in the nucleophilic addition reaction is one or a mixture of more of dichloromethane, benzene, tetrahydrofuran and 1, 4-dioxane.
The micro-reactor used in the invention comprises a micro-mixer and a micro-channel reactor, and the micro-mixer and the micro-channel reactor are connected together. The inner diameter of the micro-mixer channel is 1-10 mm, and the inner diameter of the micro-channel reactor is 1-10 mm. Its advantages are large specific surface area of reactor, large contact area of reaction liquid, and high heat and mass transfer speed. The micro-structure reactor has small internal volume, small liquid holdup, safe and reliable process and can realize continuous operation.
The temperature of the microstructure reactor during nucleophilic addition is-20 to 40 DEG CoC, the raw materials have the molar ratio: trichloro sulfur and phosphorus: aniline =1: 0.8-1: 2, raw material concentration is 0.1-1.5 mol/L of trichloro sulfur phosphorus, aniline is 0.2-2 mol/L, and residence time is 0.5-60 min (reaction time of a micro mixer is not counted).
The invention overcomes the defects of the traditional method and has the following advantages: (1) the reaction condition is mild, and the process is continuous, rapid, safe and controllable; (2) product ofNThe-phenyl thiophosphoryl dichloride has the characteristics of high selectivity and high yield; (3) various number levels of production can be achieved without amplification effects.
The innovation point of the invention is to provide a method for preparing the catalyst by utilizing a micro-structure reactor, which realizes the preparation with the advantages of mild conditions, continuous and controllable process and high selectivityN-phenylthiophosphoryl dichloride. The invention utilizes the advantages of small liquid holdup, strong mass transfer and heat transfer capacities and the like of the micro-structure reactor, avoids the requirement of ultralow temperature environment required by the traditional reaction, and simplifies the preparationNA step of phenylthiophosphoryl dichloride and a continuous operation is achieved.
Drawings
FIG. 1 is a microstructure reactor fabricationNA schematic diagram of the apparatus scheme for the reaction of phenylthiophosphoryl dichloride; a1 and A2 are high-pressure injection pumps, B1 is a micro mixer, C1 is a micro-channel reactor, D1 is a low-temperature tank or a constant-temperature water bath, E is a product collecting bottle, and F is an HCl gas absorption bottle.
Detailed Description
The following examples are helpful in understanding the present invention, but are not limited to the summary of the invention. The simple replacement or improvement of the present invention by those skilled in the art is within the technical scheme of the present invention.
Example 1
As shown in the figure, a tetrahydrofuran solution of trichlorosulfur phosphorus R1 (0.1 mol/L) and aniline R2 (0.2 mol/L) is respectively injected into a micro mixer B1 (T-shaped tee joint, inner diameter: 1 mm) by a high-pressure injection pump A1 and A2 according to the molar ratio of 1:0.8 to be mixed, and then enters a micro-channel reactor C1 (inner diameter: 1 mm) to continue to be in a low-temperature tank D1 (-20 mm)oC) The nucleophilic addition reaction is carried out for 60 min, a sample is collected by a product collecting bottle E, and HCl is treated by a gas absorbing bottle F and then is emptied. The crude product is prepared by separation, purification and refiningN-phenylthiophosphoryl dichloride. The product GC analysis yield is 67%, and the selectivity is 90%.
Example 2
As shown in the figure, 1, 4-dioxane solution of trichlorosulfur phosphorus R1 (0.5 mol/L) and aniline R2 (1.0 mol/L) is respectively injected into a micro mixer B1 (Y-type micro mixer, inner diameter: 3 mm) by high-pressure injection pumps A1 and A2 according to the molar ratio of 1:1 to be mixed, and then enters a micro-channel reactor C1 (inner diameter: 3 mm) to continue to be in a low-temperature tank D1 (-10 mm)oC) And (4) performing nucleophilic addition and reacting for 30 min, collecting the sample by using a product collecting bottle E, treating HCl by using a gas absorption bottle F, and then emptying. The crude product is prepared by separation, purification and refiningN-phenylthiophosphoryl dichloride. The product GC analysis yield is 80%, and the selectivity is 91%.
Example 3
As shown in the figure, benzene solutions of trichlorosulfur phosphorus R1 (0.5 mol/L) and aniline R2 (1.5 mol/L) are respectively injected into a micro mixer B1 (J-type micro mixer, inner diameter: 6 mm) by high-pressure injection pumps A1 and A2 according to the molar ratio of 1:1.2 to be mixed, and then enter a micro-channel reactor C1 (inner diameter: 3 mm) to continue to be in a low-temperature tank D1 (0.5 mol/L)oC) The nucleophilic addition reaction is carried out for 40 min, a sample is collected by a product collecting bottle E, and HCl is treated by a gas absorbing bottle F and then is emptied. The crude product is prepared by separation, purification and refiningN-phenylthiophosphoryl dichloride. The product GC analysis yield is 84%, and the selectivity is 94%.
Example 4
As shown in the figure, a dichloromethane solution of trichlorosulfur phosphorus R1 (1.5 mol/L) and aniline R2 (1.5 mol/L) was injected into a micromixer B1 (Y-type micromixer, inner diameter: 6 mm) from a high-pressure injection pump A1 and A2, respectively, at a molar ratio of 1:1.4After mixing, the mixture enters a microchannel reactor C1 (inner diameter: 10 mm) and continues in a low-temperature tank D1 (10)oC) The nucleophilic addition reaction is carried out for 20 min, a sample is collected by a product collecting bottle E, and HCl is treated by a gas absorbing bottle F and then is emptied. The crude product is prepared by separation, purification and refiningN-phenylthiophosphoryl dichloride. The product GC analysis yield is 86%, and the selectivity is 95%.
Example 5
As shown in the figure, a tetrahydrofuran solution of trichlorosulfur phosphorus R1 (1.5 mol/L) and aniline R2 (2 mol/L) is respectively injected into a micro mixer B1 (T-shaped tee joint, inner diameter: 1 mm) by high-pressure injection pumps A1 and A2 according to the molar ratio of 1:1.6 to be mixed, and then enters a micro-channel reactor C1 (inner diameter: 6 mm) to continue to be in a low-temperature tank D1 (20: 6 mm)oC) And (4) carrying out nucleophilic addition and reaction for 5 min, collecting a sample by using a product collecting bottle E, treating HCl by using a gas absorption bottle F, and then emptying. The crude product is prepared by separation, purification and refiningN-phenylthiophosphoryl dichloride. Irreversible clogging of the microchannel occurs.
Example 6
As shown in the figure, mixed solution of trichlorothiophosphoryl R1 (1.5 mol/L) and aniline R2 (2.0 mol/L) of dichloromethane and tetrahydrofuran (the volume ratio of dichloromethane to tetrahydrofuran is 1: 1) is respectively injected into a micro mixer B1 (T-type micro mixer, inner diameter: 10 mm) by high-pressure injection pumps A1 and A2 according to the molar ratio of 1:2 to be mixed, and then enters a micro-channel reactor C1 (inner diameter: 6 mm) to continue to be in a low-temperature tank D1 (40: 6 mm)oC) The nucleophilic addition reaction is carried out for 0.5 min, a sample is collected by a product collecting bottle E, and HCl is discharged after being treated by a gas absorption bottle F. The crude product is prepared by separation, purification and refiningN-phenylthiophosphoryl dichloride. The product GC analysis yield is 82%, and the selectivity is 90%.
In the description of the embodiments of the present invention, it should be understood that the terms "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "center", "top", "bottom", "top", "root", "inner", "outer", "peripheral", "inner", "outer", and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, only for the purpose of describing the present invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be construed as limiting the present invention. Where "inside" refers to an interior or enclosed area or space. "periphery" refers to an area around a particular component or a particular area.
In the description of the embodiments of the present invention, the terms "first", "second", "third", and "fourth" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, features defined as "first", "second", "third", "fourth" may explicitly or implicitly include one or more of the features. In the description of the present invention, "a plurality" means two or more unless otherwise specified.
In the description of the embodiments of the present invention, it should be noted that, unless otherwise explicitly specified or limited, the terms "mounted," "connected," and "assembled" are to be construed broadly and may, for example, be fixedly connected, detachably connected, or integrally connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
In the description of the embodiments of the invention, the particular features, structures, materials, or characteristics may be combined in any suitable manner in any one or more embodiments or examples.
In the description of the embodiments of the present invention, it is to be understood that "-" and "-" denote ranges of two numerical values, and the ranges include endpoints. For example, "A-B" means a range greater than or equal to A and less than or equal to B. "A to B" represents a range of A or more and B or less.
In the description of the embodiments of the present invention, the term "and/or" herein is only one kind of association relationship describing an associated object, and means that there may be three kinds of relationships, for example, a and/or B, and may mean: a exists alone, A and B exist simultaneously, and B exists alone. In addition, the character "/" herein generally indicates that the former and latter related objects are in an "or" relationship.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (8)
1. Preparation by using microreactorN-phenylthiophosphoryl dichloride process comprising the main steps of:
(1) nucleophilic addition: pumping the trichloro-sulfur phosphorus and aniline with certain concentration into a micro-reactor respectively to carry out nucleophilic addition reaction to obtain a crude product;
(2) the crude product is prepared by separation, purification and refiningN-phenylthiophosphoryl dichloride.
2. Preparation according to claim 1NThe method of phenyl thiophosphoryl dichloride is characterized in that the solvent used in the nucleophilic addition reaction in the step (1) is one or a mixture of more of dichloromethane, benzene, tetrahydrofuran and 1, 4-dioxane.
3. Preparation according to claim 1N-phenylthiophosphoryl dichloride process, characterized in that a microreactor is used which comprises a micromixer and a microchannel reactor, the micromixer and the microchannel reactor being connected together.
4. Preparation according to claim 1NThe method of phenyl thiophosphoryl dichloride is characterized in that the inner diameter of a channel of a micro mixer is 1-10 mm, and the inner diameter of a micro channel reactor is 1-10 mm.
5. As claimed in claim 1The preparation ofNThe method of-phenyl thiophosphoryl dichloride is characterized in that the temperature of a microstructure reactor during nucleophilic addition is-20 to 40oC。
6. Preparation according to claim 1N-phenylthiophosphoryl dichloride process, characterized in that the nucleophilic addition reaction of step (1) is carried out with a molar ratio of starting materials: trichloro sulfur and phenyl sulfide =1: 0.8-1: 2.
7. Preparation according to claim 1NThe method for preparing the phenyl thiophosphoryl dichloride is characterized in that the concentration of raw materials for nucleophilic addition reaction in the step (1) is 0.1-1.5 mol/L of trichloro-sulfur phosphorus and 0.2-2 mol/L of aniline.
8. Preparation according to claim 1NThe method of the phenyl thiophosphoryl dichloride is characterized in that the retention time of the nucleophilic addition reaction in the step (1) is 0.5-60 min.
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Citations (4)
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|---|---|---|---|---|
| US5770771A (en) * | 1997-01-21 | 1998-06-23 | Albemarle Corporation | Preparation of N-hydrocarbylthiophosphoric triamides |
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| 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 |
| CN105131031A (en) * | 2015-07-03 | 2015-12-09 | 上虞盛晖化工股份有限公司 | Method for synthesizing N-alkylthiophosphoryl triamide through continuous reaction |
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2019
- 2019-04-11 CN CN201910288322.3A patent/CN111808132A/en active Pending
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| 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 |
| CN105131031A (en) * | 2015-07-03 | 2015-12-09 | 上虞盛晖化工股份有限公司 | Method for synthesizing N-alkylthiophosphoryl triamide through continuous reaction |
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