CN105669748A - Synthesis method of methyl phosphorus dichloride - Google Patents
Synthesis method of methyl phosphorus dichloride Download PDFInfo
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- CN105669748A CN105669748A CN201610095303.5A CN201610095303A CN105669748A CN 105669748 A CN105669748 A CN 105669748A CN 201610095303 A CN201610095303 A CN 201610095303A CN 105669748 A CN105669748 A CN 105669748A
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- petroleum ether
- methyl dichloro
- synthetic method
- chloride
- dichloro phosphorus
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- CDPKWOKGVUHZFR-UHFFFAOYSA-N dichloro(methyl)phosphane Chemical compound CP(Cl)Cl CDPKWOKGVUHZFR-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000001308 synthesis method Methods 0.000 title abstract 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 84
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 71
- 239000003208 petroleum Substances 0.000 claims abstract description 42
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000004821 distillation Methods 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 230000000694 effects Effects 0.000 claims abstract description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 40
- FLKPEMZONWLCSK-UHFFFAOYSA-N diethyl phthalate Chemical compound CCOC(=O)C1=CC=CC=C1C(=O)OCC FLKPEMZONWLCSK-UHFFFAOYSA-N 0.000 claims description 30
- 238000010189 synthetic method Methods 0.000 claims description 28
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims description 23
- 239000011780 sodium chloride Substances 0.000 claims description 20
- 229910052782 aluminium Inorganic materials 0.000 claims description 19
- 239000000843 powder Substances 0.000 claims description 19
- 239000004411 aluminium Substances 0.000 claims description 18
- 238000011084 recovery Methods 0.000 claims description 16
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 15
- 239000011777 magnesium Substances 0.000 claims description 15
- 229910052749 magnesium Inorganic materials 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 8
- 230000006837 decompression Effects 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000012546 transfer Methods 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 10
- 238000003786 synthesis reaction Methods 0.000 abstract description 10
- 239000007789 gas Substances 0.000 abstract description 7
- 238000005516 engineering process Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 3
- 239000003446 ligand Substances 0.000 abstract description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 abstract 1
- SWRNIYAQKATHDJ-UHFFFAOYSA-N dichloro(dichlorophosphanyl)phosphane Chemical compound ClP(Cl)P(Cl)Cl SWRNIYAQKATHDJ-UHFFFAOYSA-N 0.000 abstract 1
- 239000010815 organic waste Substances 0.000 abstract 1
- IAJOBQBIJHVGMQ-UHFFFAOYSA-N 2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid Chemical compound CP(O)(=O)CCC(N)C(O)=O IAJOBQBIJHVGMQ-UHFFFAOYSA-N 0.000 description 7
- 238000006722 reduction reaction Methods 0.000 description 6
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 4
- KGOSUPNCDMJKPH-UHFFFAOYSA-N C[P](C)(Cl)Cl Chemical compound C[P](C)(Cl)Cl KGOSUPNCDMJKPH-UHFFFAOYSA-N 0.000 description 4
- 239000005561 Glufosinate Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000002363 herbicidal effect Effects 0.000 description 3
- 230000009261 transgenic effect Effects 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000006276 transfer reaction Methods 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 244000037671 genetically modified crops Species 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 210000000582 semen Anatomy 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/52—Halophosphines
-
- 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
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/505—Preparation; Separation; Purification; Stabilisation
- C07F9/509—Preparation; Separation; Purification; Stabilisation by reduction of pentavalent phosphorus derivatives, e.g. -P=X with X = O, S, Se or -P-Hal2
Landscapes
- 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)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a synthesis method of methyl phosphorus dichloride. According to the synthesis method, methyl chloride, aluminum trichloride and phosphorus trichloride serve as raw materials, petroleum ether serves as a solvent, ligands CH3PCl4.AlCl3 are generated through reaction, after petroleum ether is recycled through distillation, aluminum powder and petroleum ether are added, and the methyl phosphorus dichloride is obtained through reduction under the action of a catalyst. The synthesis method of methyl phosphorus dichloride can replace an existing technology to solve the problem of emission of organic waste gas in the preparation process, and the method is a complete synthesis technology process according with the clean production principle better. Besides, compared with the prior art, the synthesis method has a better production effect, and in other words, the yield of the methyl phosphorus dichloride can reach 91% (denoted by phosphorus dichloride).
Description
Technical field
The present invention is the synthetic method of a kind of methyl dichloro phosphorus, is specifically related to the synthetic method of a kind of important organophosphor intermediate methyl dichloro phosphorus, belongs to organophosphorus chemistry synthesis technical field.
Background technology
Methyl dichloro phosphorus is a kind of intermediate synthesizing organic phosphorus compound, is also the important intermediate of herbicide glufosinate-ammonium (glufosinate). Glufosinate-ammonium is the desirable herbicide of transgenic resistance crop, has efficiently, low toxicity and the wide feature of herbicidal spectrum. Along with the fast development of genetically modified crops, such as transgenic glufosinate-resistant Oryza sativa L., transgenic glufosinate-resistant Semen sojae atricolor etc., the market demand of glufosinate-ammonium also increases sharply. The chemical property of methyl dichloro phosphorus is active, very easily with the water in air and oxygen reaction, and easy spontaneous combustion, difficult storage, market cannot directly be commercially available. Accordingly, as the methyl dichloro phosphorus of synthesis glufosinate-ammonium important intermediate, its research and development have wide market prospect.
The preparation method abroad having more bibliographical information methyl dichloro phosphorus, wherein " synthesis of methyl dichloro phosphorus " with pesticide magazine in February, 2011 (the 50th volume second phase) is comparatively complete, the synthesis of methyl dichloro phosphorus is proposed preferably method, the method is with chloromethanes, aluminum chloride and Phosphorous chloride. for raw material, with the higher sym-tetrachloroethane of boiling point for solvent, the coordination compound that is obtained by reacting is dried, after heating and melting, with aluminum reduction, slough aluminum chloride through sodium chloride and obtain the methyl dichloro phosphorus of higher degree. Being reported by the document, it is known that the product methyl dichloro phosphorus that this synthetic method obtains, purity 98.0%, total recovery reaches 76.2%(in aluminum chloride). But have in industrialization and be difficult to solve the technical problem that, part needs prepared by the method proceed to reduction and resolve prepared methyl dichloro phosphorus after filtering, solid-liquid separation process is difficult to avoid that the uncontrollable discharge of organic exhaust gas, the sym-tetrachloroethane that particularly boiling point is higher, poisonous and there is the zest of chloroform, it is easy to cause employment injuries problem.
Summary of the invention
In preparing for methyl dichloro phosphorus, the emission problem of organic exhaust gas, the invention provides the synthetic method of a kind of methyl dichloro phosphorus, calculates with Phosphorous chloride., and the yield of this synthetic method can reach 91%, and purity is up to 99.5%.
The present invention is achieved through the following technical solutions: the synthetic method of a kind of methyl dichloro phosphorus, and with chloromethanes, aluminum chloride and Phosphorous chloride. for raw material, with petroleum ether for solvent, reaction generates part CH3PCl4·AlCl3, after Distillation recovery petroleum ether, add aluminium powder and sodium chloride, under the effect of catalyst, reduction parsing obtains product methyl dichloro phosphorus.
The present invention adopts the petroleum ether being easily recycled as solvent, in building-up process, after condensation reaction terminates, do not need to filter and transfer reaction still, either directly through distillating recovering solvent petroleum ether, obtain coordination compound solid to continue in former reactor, carry out reduction reaction, discharge without organic exhaust gas, meet cleaning and produce principle.
For convenience of operation, add described petroleum ether and Phosphorous chloride. in a kettle., after stirring, add aluminum chloride and chloromethanes, after stirring, generate part CH3PCl4·AlCl3. When actual production, chloromethanes should be slowly introducing bottom reactor, is conducive to increasing gas liquid contacting efficiency.
Described reactor meets:
Before reinforced, evacuation reaches pressure, and < 10Pa, after eliminating air, fills with nitrogen;
After reinforced, reaction temperature controls to be room temperature, and reaction pressure controls at 0.02～0.2MPa.
Above-mentioned technology controlling and process, has safety, risk little, it is ensured that the feature that reaction is smoothed out.
The mass ratio of described petroleum ether and Phosphorous chloride. is (2～15): 1.
Complex for ensureing reaction gained has and better obtained mobility, it is easy to the recovery of petroleum ether and subsequent reactions, and the mol ratio of described Phosphorous chloride. and aluminum chloride is 1:(1.5～2.1).
The mol ratio of described chloromethanes and Phosphorous chloride. is (0.9～1.2): 1. The purpose selecting this ratio is to improve the utilization rate of Phosphorous chloride., reduces offal treatment difficulty.
After Distillation recovery petroleum ether, the mol ratio adding described aluminium powder and sodium chloride is 1:(2～3.1), adding sodium chloride is the fine powder less than 150 orders, is 1:(1.0～2.0 with the mol ratio of Phosphorous chloride .).
Described catalyst includes mass ratio for (0.2～1): the diethyl phthalate of (0.5～1.5) and magnesium. In the present invention, the use of catalyst can improve the yield of dimethyl phosphorus dichloride.
Described still-process is to transfer decompression distillation to when vapo(u)rizing temperature rises to 80 DEG C, it is ensured that petroleum ether is removed completely, after Distillation recovery petroleum ether, it is cooled to 55～70 DEG C, it is initially charged diethyl phthalate and magnesium, after adding aluminium powder and sodium chloride, adds thermal distillation.
Collecting the fraction of 82～84 DEG C in described heating still-process, namely obtain product methyl dichloro phosphorus, calculate with Phosphorous chloride., the yield of this synthetic method can reach 91%, and purity is up to 99.5%.
The present invention compared with prior art, has the following advantages and beneficial effect:
(1) methyl dichloro phosphorus synthetic method of the present invention is that one can substitute prior art, solve the emission problem of organic exhaust gas in preparation process, more meet the synthesis technique flow process that cleaning produces the complete set of principle, in addition, this synthetic method also makes prior art have better production effect, that is, the yield of product methyl dichloro phosphorus can reach 91%(in Phosphorous chloride .).
(2) synthetic method of the present invention is with petroleum ether for solvent, when with mol ratio for (0.9～1.2): 1:(1.5～2.1) chloromethanes, aluminum chloride and Phosphorous chloride. synthetic ligands CH when being raw material3PCl4·AlCl3, after reaction terminates, do not need to filter and transfer reaction still, either directly through distillating recovering solvent petroleum ether, coordination compound solid can be obtained and continue in former reactor, carry out reduction reaction, discharge without organic exhaust gas poisonous, irritating, meeting cleaning and produce principle, security risk is little.
(3) present invention selects mass ratio to be (0.2～1): the diethyl phthalate of (0.5～1.5) and magnesium composition catalyst, when selecting properly material proportion (mol ratio of aluminium powder and sodium chloride is 1:(2～3.1)), improving the yield of product dimethyl phosphorus dichloride, the yield of product dimethyl phosphorus dichloride can reach more than 91%.
(4) present invention is (0.9～1.2) in the mol ratio of selecting properly chloromethanes, aluminum chloride and Phosphorous chloride.: 1:(1.5～2.1), synthesis technique effect can also be improved in material fluidity, raw material availability etc., to ensure that this synthetic method obtains best technological effect, lay the foundation for improving product dimethyl phosphorus dichloride yield and purity.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1:
The present embodiment proposes the synthetic method of a kind of methyl dichloro phosphorus, and with chloromethanes, aluminum chloride and Phosphorous chloride. for raw material, with petroleum ether for solvent, reaction generates part CH3PCl4·AlCl3, after Distillation recovery petroleum ether, add aluminium powder and sodium chloride, under the effect of catalyst, reduction obtains product methyl dichloro phosphorus.
Embodiment 2:
The present embodiment, on the basis of embodiment 1, further defines, and adds petroleum ether and Phosphorous chloride. in a kettle., after stirring, adds aluminum chloride and chloromethanes, generates part CH after stirring3PCl4·AlCl3。
Embodiment 3:
The present embodiment, on the basis of embodiment 2, defines reactor and meets:
Before reinforced, evacuation reaches pressure, and < 10Pa, after eliminating air, fills with nitrogen;
After reinforced, reaction temperature controls to be room temperature, and reaction pressure controls at 0.02MPa.
Embodiment 4:
The present embodiment is on the basis of embodiment 1, the data such as consumption that make of the proportioning of raw material each in synthetic method, solvent is defined, including herein below:
The mass ratio of petroleum ether and Phosphorous chloride. meets 2:1;
The mol ratio of Phosphorous chloride. and aluminum chloride meets 1:1.5;
The mol ratio of chloromethanes and Phosphorous chloride. meets 0.9:1.
Embodiment 5:
Raw material composition in synthetic method, solvent, on the basis of embodiment 3, are made consumption etc. be defined, including herein below by the present embodiment:
The mass ratio of petroleum ether and Phosphorous chloride. meets 15:1;
The mol ratio of Phosphorous chloride. and aluminum chloride meets 1:2.1;
The mol ratio of chloromethanes and Phosphorous chloride. meets 1.2:1.
Embodiment 6:
The present embodiment and embodiment 4 are distinctive in that: after Distillation recovery petroleum ether, the mol ratio adding described aluminium powder and sodium chloride is 1:2; Catalyst includes diethyl phthalate and the magnesium that mass ratio is 0.2:1.5.
Embodiment 7:
The present embodiment and embodiment 5 are distinctive in that: after Distillation recovery petroleum ether, the mol ratio adding described aluminium powder and sodium chloride is 1:3.1; Catalyst includes diethyl phthalate and the magnesium that mass ratio is 1:0.5.
Embodiment 8:
The present embodiment and embodiment 6 are distinctive in that: still-process is to transfer decompression distillation to when vapo(u)rizing temperature rises to 80 DEG C, after Distillation recovery petroleum ether, it is cooled to 55 DEG C, it is initially charged diethyl phthalate and magnesium, after adding aluminium powder and sodium chloride, add thermal distillation, collect the fraction of 82 DEG C in described heating still-process, namely obtain product methyl dichloro phosphorus.
Embodiment 9:
The present embodiment and embodiment 7 are distinctive in that: still-process is to transfer decompression distillation to when vapo(u)rizing temperature rises to 80 DEG C, after Distillation recovery petroleum ether, it is cooled to 70 DEG C, it is initially charged diethyl phthalate and magnesium, after adding aluminium powder and sodium chloride, add thermal distillation, collect the fraction of 84 DEG C in described heating still-process, namely obtain product methyl dichloro phosphorus.
Embodiment 10:
The synthetic method of a kind of methyl dichloro phosphorus, with chloromethanes, aluminum chloride and Phosphorous chloride. for raw material, with petroleum ether for solvent, during synthesis, add petroleum ether and Phosphorous chloride. first in a kettle., after stirring, add aluminum chloride and chloromethanes, after stirring, generate part CH3PCl4·AlCl3;Decompression distillation is transferred to when vapo(u)rizing temperature rises to 80 DEG C, after Distillation recovery petroleum ether, it is cooled to 60 DEG C, it is initially charged catalyst (diethyl phthalate and magnesium), after adding aluminium powder and sodium chloride, add thermal distillation, collect the fraction of 83 DEG C in described heating still-process, namely obtain product methyl dichloro phosphorus.
In above-mentioned building-up process, reactor meets:
Before reinforced, evacuation reaches pressure 9.5Pa, after eliminating air, fills with nitrogen;
After reinforced, reaction temperature controls to be room temperature, and reaction pressure controls at 0.15MPa.
In addition, the present embodiment also meets the following conditions:
Mass ratio=the 8:1 of petroleum ether and Phosphorous chloride.,
Mol ratio=the 1:1.8 of Phosphorous chloride. and aluminum chloride,
Mol ratio=the 1.0:1 of chloromethanes and Phosphorous chloride.,
Mol ratio=the 1:2.2 of aluminium powder and sodium chloride,
Catalyst includes the magnesium of diethyl phthalate that mass percent is 0.8% and 1.3%.
Embodiment 11:
The synthetic method of a kind of methyl dichloro phosphorus, with chloromethanes, aluminum chloride and Phosphorous chloride. for raw material, with petroleum ether for solvent, during synthesis, add petroleum ether and Phosphorous chloride. first in a kettle., after stirring, add aluminum chloride and chloromethanes, after stirring, generate part CH3PCl4·AlCl3; Decompression distillation is transferred to when vapo(u)rizing temperature rises to 80 DEG C, after Distillation recovery petroleum ether, it is cooled to 66 DEG C, it is initially charged catalyst (diethyl phthalate and magnesium), after adding aluminium powder and sodium chloride, add thermal distillation, collect the fraction of 82 DEG C in described heating still-process, namely obtain product methyl dichloro phosphorus.
In above-mentioned building-up process, reactor meets:
Before reinforced, evacuation reaches pressure 9Pa, after eliminating air, fills with nitrogen;
After reinforced, reaction temperature controls to be room temperature, and reaction pressure controls at 0.08MPa.
In addition, the present embodiment also meets the following conditions:
Mass ratio=the 11:1 of petroleum ether and Phosphorous chloride.,
Mol ratio=the 1:2 of Phosphorous chloride. and aluminum chloride,
Mol ratio=the 0.9:1 of chloromethanes and Phosphorous chloride.,
Mol ratio=the 1:2.8 of aluminium powder and sodium chloride,
Catalyst includes the magnesium of diethyl phthalate that mass percent is 0.9% and 1.0%.
Embodiment 12:
The synthetic method of a kind of methyl dichloro phosphorus, with chloromethanes, aluminum chloride and Phosphorous chloride. for raw material, with petroleum ether for solvent, during synthesis, add petroleum ether and Phosphorous chloride. first in a kettle., after stirring, add aluminum chloride and chloromethanes, after stirring, generate part CH3PCl4·AlCl3; Decompression distillation is transferred to when vapo(u)rizing temperature rises to 80 DEG C, after Distillation recovery petroleum ether, it is cooled to 62 DEG C, it is initially charged catalyst (diethyl phthalate and magnesium), after adding aluminium powder and sodium chloride, add thermal distillation, collect the fraction of 83 DEG C in described heating still-process, namely obtain product methyl dichloro phosphorus.
In above-mentioned building-up process, reactor meets:
Before reinforced, evacuation reaches pressure 9.6Pa, after eliminating air, fills with nitrogen;
After reinforced, reaction temperature controls to be room temperature, and reaction pressure controls at 0.13MPa.
In addition, the present embodiment also meets the following conditions:
Mass ratio=the 10:1 of petroleum ether and Phosphorous chloride.,
Mol ratio=the 1:1.8 of Phosphorous chloride. and aluminum chloride,
Mol ratio=the 1.2:1 of chloromethanes and Phosphorous chloride.,
Mol ratio=the 1:3.0 of aluminium powder and sodium chloride,
Catalyst includes the magnesium of diethyl phthalate that mass percent is 0.6% and 1.1%.
The above, be only presently preferred embodiments of the present invention, and the present invention not does any pro forma restriction, every above example is made according to the technical spirit of the present invention any simple modification, equivalent variations, each fall within protection scope of the present invention.
Claims (10)
1. the synthetic method of a methyl dichloro phosphorus, it is characterised in that: with chloromethanes, aluminum chloride and Phosphorous chloride. for raw material, with petroleum ether for solvent, reaction generates part CH3PCl4·AlCl3, after Distillation recovery petroleum ether, add aluminium powder and sodium chloride, under the effect of catalyst, reduction obtains product methyl dichloro phosphorus.
2. the synthetic method of a kind of methyl dichloro phosphorus according to claim 1, it is characterised in that: add described petroleum ether and Phosphorous chloride. in a kettle., after stirring, add aluminum chloride and chloromethanes, after stirring, generate part CH3PCl4·AlCl3。
3. the synthetic method of a kind of methyl dichloro phosphorus according to claim 2, it is characterised in that: described reactor meets:
Before reinforced, evacuation reaches pressure, and < 10Pa, after eliminating air, fills with nitrogen;
After reinforced, reaction temperature controls to be room temperature, and reaction pressure controls at 0.02～0.2MPa.
4. the synthetic method of a kind of methyl dichloro phosphorus according to claim 1, it is characterised in that: the mass ratio of described petroleum ether and Phosphorous chloride. is (2～15): 1.
5. the synthetic method of a kind of methyl dichloro phosphorus according to claim 1, it is characterised in that: the mol ratio of described Phosphorous chloride. and aluminum chloride is 1:(1.5～2.1).
6. the synthetic method of a kind of methyl dichloro phosphorus according to claim 1, it is characterised in that: the mol ratio of described chloromethanes and Phosphorous chloride. is (0.9～1.2): 1.
7. the synthetic method of a kind of methyl dichloro phosphorus according to claim 1, it is characterised in that: after Distillation recovery petroleum ether, the mol ratio adding described aluminium powder and sodium chloride is 1:(2～3.1).
8. the synthetic method of a kind of methyl dichloro phosphorus according to claim 1, it is characterised in that: described catalyst includes mass ratio for (0.2～1): the diethyl phthalate of (0.5～1.5) and magnesium.
9. the synthetic method of a kind of methyl dichloro phosphorus according to claim 8, it is characterized in that: described still-process is to transfer decompression distillation to when vapo(u)rizing temperature rises to 80 DEG C, after Distillation recovery petroleum ether, it is cooled to 55～70 DEG C, it is initially charged diethyl phthalate and magnesium, after adding aluminium powder and sodium chloride, add thermal distillation.
10. the synthetic method of a kind of methyl dichloro phosphorus according to claim 9, it is characterised in that: collect the fraction of 82～84 DEG C in described heating still-process, namely obtain product methyl dichloro phosphorus.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106046052A (en) * | 2016-06-27 | 2016-10-26 | 安徽国星生物化学有限公司 | Synthesis method of glufosinate-ammonium intermediate methylphosphorus dichloride |
| CN106565779A (en) * | 2016-11-10 | 2017-04-19 | 安徽国星生物化学有限公司 | Novel synthesis process of methyl phosphorus dichloride |
| CN106967118A (en) * | 2017-03-27 | 2017-07-21 | 南京奥格美化学研究所有限公司 | A kind of method for preparing the alkylphosphines of dichloro one |
| CN107602608A (en) * | 2017-09-26 | 2018-01-19 | 安徽国星生物化学有限公司 | A kind of preparation method of diethyl methyl-phosphonite |
| CN108558943A (en) * | 2018-05-10 | 2018-09-21 | 四川福思达生物技术开发有限责任公司 | A method of dissociation dichloromethylphosphine and aluminum chloride complex |
| CN108864190A (en) * | 2018-08-01 | 2018-11-23 | 河北威远生物化工有限公司 | A method of producing alkyl phosphorus dichloride |
| CN110283205A (en) * | 2018-03-19 | 2019-09-27 | 浙江新安化工集团股份有限公司 | A kind of system and method preparing methylisothiouronium methylphosphite ester |
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| CN110283204A (en) * | 2018-03-19 | 2019-09-27 | 浙江新安化工集团股份有限公司 | It is a kind of using methyl chloride aluminum for the system and preparation method of methylisothiouronium methylphosphite ester |
| CN110283203A (en) * | 2018-03-19 | 2019-09-27 | 浙江新安化工集团股份有限公司 | It is a kind of using methyl chloride aluminum for the system and preparation method of methylisothiouronium methylphosphite ester |
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| CN106046052A (en) * | 2016-06-27 | 2016-10-26 | 安徽国星生物化学有限公司 | Synthesis method of glufosinate-ammonium intermediate methylphosphorus dichloride |
| CN106565779A (en) * | 2016-11-10 | 2017-04-19 | 安徽国星生物化学有限公司 | Novel synthesis process of methyl phosphorus dichloride |
| CN106565779B (en) * | 2016-11-10 | 2018-06-19 | 安徽国星生物化学有限公司 | A kind of methyl dichloro phosphorus new technique for synthesizing |
| CN106967118A (en) * | 2017-03-27 | 2017-07-21 | 南京奥格美化学研究所有限公司 | A kind of method for preparing the alkylphosphines of dichloro one |
| CN107602608A (en) * | 2017-09-26 | 2018-01-19 | 安徽国星生物化学有限公司 | A kind of preparation method of diethyl methyl-phosphonite |
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| CN110283205A (en) * | 2018-03-19 | 2019-09-27 | 浙江新安化工集团股份有限公司 | A kind of system and method preparing methylisothiouronium methylphosphite ester |
| CN110283204A (en) * | 2018-03-19 | 2019-09-27 | 浙江新安化工集团股份有限公司 | It is a kind of using methyl chloride aluminum for the system and preparation method of methylisothiouronium methylphosphite ester |
| CN110283203A (en) * | 2018-03-19 | 2019-09-27 | 浙江新安化工集团股份有限公司 | It is a kind of using methyl chloride aluminum for the system and preparation method of methylisothiouronium methylphosphite ester |
| CN110283202B (en) * | 2018-03-19 | 2021-03-23 | 浙江新安化工集团股份有限公司 | System and method for preparing methylphosphonite from aluminum methylchloride |
| CN110283205B (en) * | 2018-03-19 | 2021-03-23 | 浙江新安化工集团股份有限公司 | System and method for preparing methylphosphonite |
| CN110283204B (en) * | 2018-03-19 | 2022-02-22 | 浙江新安化工集团股份有限公司 | System and method for preparing methyl phosphite ester by adopting aluminum methyl chloride |
| CN108558943A (en) * | 2018-05-10 | 2018-09-21 | 四川福思达生物技术开发有限责任公司 | A method of dissociation dichloromethylphosphine and aluminum chloride complex |
| CN108558943B (en) * | 2018-05-10 | 2020-06-19 | 四川福思达生物技术开发有限责任公司 | Method for dissociating methyl phosphine dichloride and aluminum trichloride complex |
| CN108864190A (en) * | 2018-08-01 | 2018-11-23 | 河北威远生物化工有限公司 | A method of producing alkyl phosphorus dichloride |
| CN108864190B (en) * | 2018-08-01 | 2020-08-07 | 河北威远生物化工有限公司 | Method for producing alkyl phosphorus dichloride |
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