CN113024600A - Process for preparing chloromethyl phosphonic acid - Google Patents
Process for preparing chloromethyl phosphonic acid Download PDFInfo
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- CN113024600A CN113024600A CN202110272990.4A CN202110272990A CN113024600A CN 113024600 A CN113024600 A CN 113024600A CN 202110272990 A CN202110272990 A CN 202110272990A CN 113024600 A CN113024600 A CN 113024600A
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- acid
- reaction
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- hydrochloric acid
- chloromethylphosphonic
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- MOFCYHDQWIZKMY-UHFFFAOYSA-N chloromethylphosphonic acid Chemical compound OP(O)(=O)CCl MOFCYHDQWIZKMY-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 53
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 8
- -1 hydroxymethyl phosphonate diester Chemical class 0.000 claims abstract description 5
- 238000001816 cooling Methods 0.000 claims abstract description 4
- 238000001704 evaporation Methods 0.000 claims abstract description 4
- 238000004108 freeze drying Methods 0.000 claims abstract description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 12
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- GTTBQSNGUYHPNK-UHFFFAOYSA-N hydroxymethylphosphonic acid Chemical compound OCP(O)(O)=O GTTBQSNGUYHPNK-UHFFFAOYSA-N 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 150000005690 diesters Chemical class 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- UAXIBJPHBMEGSP-UHFFFAOYSA-N di(propan-2-yloxy)phosphorylmethanol Chemical compound CC(C)OP(=O)(CO)OC(C)C UAXIBJPHBMEGSP-UHFFFAOYSA-N 0.000 claims description 4
- RWIGWWBLTJLKMK-UHFFFAOYSA-N diethoxyphosphorylmethanol Chemical compound CCOP(=O)(CO)OCC RWIGWWBLTJLKMK-UHFFFAOYSA-N 0.000 claims description 4
- OIERWUPLBOKSRB-UHFFFAOYSA-N dimethoxyphosphorylmethanol Chemical compound COP(=O)(CO)OC OIERWUPLBOKSRB-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 abstract description 17
- 239000002699 waste material Substances 0.000 abstract description 5
- 239000000047 product Substances 0.000 description 18
- 238000001228 spectrum Methods 0.000 description 5
- 238000004128 high performance liquid chromatography Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- 229930040373 Paraformaldehyde Natural products 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920002866 paraformaldehyde Polymers 0.000 description 2
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 239000005562 Glyphosate Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000219000 Populus Species 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 1
- 229940097068 glyphosate Drugs 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
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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
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3808—Acyclic saturated acids which can have further substituents on alkyl
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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)
Abstract
The invention discloses a process method for preparing chloromethyl phosphonic acid, which comprises the following steps: s1: adding a solvent and hydrochloric acid into a reaction vessel in sequence, and stirring uniformly; s2: adding hydroxymethyl phosphonate diester, and stirring to obtain a reaction solution; s3: and cooling the reaction solution, decompressing, evaporating the reaction solution to dryness, adding hydrochloric acid into the obtained residue, standing and freeze-drying to obtain chloromethyl phosphonic acid. The raw materials are safe and easy to obtain, the process safety is high, the waste is less, and the product purity is high.
Description
Technical Field
The invention relates to the field of intermediate preparation, in particular to a process method for preparing chloromethyl phosphonic acid.
Background
Chloromethylphosphonic acid (CAS: 2565-58-4), an important chelating agent, is commonly used in the production of water-based lubricants and cellulosic ion exchangers; meanwhile, the compound is also an important pesticide intermediate, and can be reacted with glycine under alkaline conditions to prepare the herbicide, namely the glyphosate.
Chloromethyl phosphonic acid has only 1 of the currently reported synthetic routes with practical value, namely, poplar and bin are equivalent to the following reported in 2005 at university of southwest university (nature science edition):
the route adopts a 2-step synthesis method, phosphorus trichloride and paraformaldehyde are taken as initial raw materials, and chloromethyl phosphonic acid is prepared by aluminum trichloride catalysis and hydrolysis.
When the method is used for hectogram amplification, 4 serious problems exist: firstly, the main material phosphorus trichloride is a dangerous material, is very difficult to purchase and transport, has very large potential safety risk to operators, and belongs to raw materials which need to be avoided as much as possible in chemical reaction; secondly, the reaction conditions in the first step are harsh, the reaction is carried out by heating to 180 ℃ and the operation is difficult, the operation has high safety risk, the operation is not friendly to operators, and the principle of green production is not met; thirdly, the waste materials in the reaction process are numerous, paraformaldehyde can be carbonized and polymerized into a large amount of black residues at high temperature, a large amount of colloidal aluminum hydroxide precipitates can be generated in the post-treatment process of aluminum trichloride, and the principle of green production is not met; fourthly, the product contains various impurities such as aluminum salt, hydroxymethylphosphonic acid and the like, the purity of the product is low and can not reach 95 percent, and the requirement of the industry on the product with the purity of more than 98 percent can not be met.
These 4 problems severely limit the further application of the process and also make the hectogram and kilogram scale up of the product very difficult.
In order to solve the problems of high initial raw material risk, poor process safety, more waste materials, low product purity, unfriendliness to operators and the like of the conventional process route of chloromethylphosphonic acid, the method for synthesizing chloromethylphosphonic acid has the advantages of reasonable route design, safe and easily obtained raw materials, high process safety, less waste materials, high product purity and great significance for the friendliness of operators.
Disclosure of Invention
In order to overcome the defects in the prior art, the embodiment of the invention provides a process method for preparing chloromethylphosphonic acid, which has the advantages of safe and easily obtained raw materials, high process safety, less waste and high product purity.
In order to achieve the above object, the embodiments of the present application disclose a process for preparing chloromethylphosphonic acid, which comprises the following steps:
s1: adding a solvent and hydrochloric acid into a reaction vessel in sequence, and stirring uniformly;
s2: adding hydroxymethyl phosphonate diester, stirring uniformly, heating to 80-120 ℃ for reaction, and keeping the temperature for reaction until the raw materials completely disappear to obtain a reaction solution;
s3: and cooling the reaction solution to 20-50 ℃, decompressing, evaporating the reaction solution to dryness, adding hydrochloric acid into the obtained residue, standing for 6-24 h, and freeze-drying to obtain chloromethyl phosphonic acid.
Preferably, the diester of hydroxymethylphosphonic acid is one or more of dimethyl hydroxymethylphosphonate, diethyl hydroxymethylphosphonate and diisopropyl hydroxymethylphosphonate.
Preferably, the reaction of the diester of hydroxymethylphosphonic acid with hydrochloric acid is carried out in a solvent which is one or more of water, toluene, ethyl acetate, tetrahydrofuran, tert-butyl methyl ether, dioxane, n-hexane, n-heptane, petroleum ether, methanol, ethanol, isopropanol, tert-butanol, acetonitrile.
Preferably, the S1 is performed under stirring at room temperature.
Preferably, the amount of the hydrochloric acid in the S1 is 1-3 times of the molar equivalent.
Preferably, the amount of the hydrochloric acid in the S3 is 0.05-0.4 times of the molar equivalent.
The invention has the following beneficial effects:
the key raw materials in the synthetic route of the invention are cheap and easy to obtain; the reaction condition is mild, the operation is convenient and fast, and the process safety is high; the reaction yield is high, the product purity is high, the production cost is greatly reduced, and the requirement of large-scale industrial production of the product can be fully met.
In order to make the aforementioned and other objects, features and advantages of the invention comprehensible, preferred embodiments accompanied with figures are described in detail below.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a nuclear magnetic hydrogen spectrum diagram of a process for preparing chloromethylphosphonic acid according to an embodiment of the present invention;
FIG. 2 is a nuclear magnetic carbon spectrum of a process for preparing chloromethylphosphonic acid according to an embodiment of the present invention;
FIG. 3 is an HPLC inspection chart of a process for preparing chloromethylphosphonic acid in an example of the present invention;
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In order to achieve the above object, the present invention provides a process for preparing chloromethylphosphonic acid, which comprises the following steps:
s1: adding a solvent and hydrochloric acid into a reaction vessel in sequence, and stirring uniformly;
s2: adding hydroxymethyl phosphonate diester, stirring uniformly, heating to 80-120 ℃ for reaction, and keeping the temperature for reaction until the raw materials completely disappear to obtain a reaction solution;
s3: and cooling the reaction solution to 20-50 ℃, decompressing, evaporating the reaction solution to dryness, adding hydrochloric acid into the obtained residue, standing for 6-24 h, and freeze-drying to obtain chloromethyl phosphonic acid.
Further, the diester of hydroxymethylphosphonic acid is one or more of dimethyl hydroxymethylphosphonate, diethyl hydroxymethylphosphonate and diisopropyl hydroxymethylphosphonate.
Further, the reaction of the hydroxymethyl phosphonic acid diester and hydrochloric acid is carried out in a solvent, wherein the solvent is one or more of water, toluene, ethyl acetate, tetrahydrofuran, tert-butyl methyl ether, dioxane, n-hexane, n-heptane, petroleum ether, methanol, ethanol, isopropanol, tert-butanol and acetonitrile.
Further, the S1 was performed under stirring at room temperature.
Further, the amount of the hydrochloric acid in the S1 is 1-3 times of the molar equivalent.
Further, the amount of the hydrochloric acid used in the S3 is 0.05-0.4 times of the molar equivalent.
Further, the temperature rise range in the S2 is 95-115 ℃.
Further, the reaction solution in the S3 is cooled to 25-45 ℃.
Example 1
Stirring at room temperature, sequentially adding 5L of water and 10kg of hydrochloric acid into a 50L reaction kettle, and uniformly stirring; then 10kg of diethyl hydroxymethylphosphonate is added into the mixture and stirred evenly; after the addition is finished, heating the reaction solution to 100 ℃ for reaction, and keeping the temperature for reaction until the raw materials completely disappear; the reaction solution was cooled to 40 ℃, the reaction solution was evaporated to dryness under reduced pressure, 2kg of hydrochloric acid was added to the obtained residue, and the mixture was allowed to stand for 12 hours and lyophilized to obtain 7.61kg of a white solid, powdery chloromethylphosphonic acid product with a yield of 98.07%.
HPLC purity of the product: 99.12 percent.
Nuclear magnetic data: 1H NMR (400MHz, D2O): δ 3.31(d, 2H); 13C NMR (100MHz, D2O): δ 35.59, 34.11.
Please refer to fig. 1 or fig. 2 for nuclear magnetic spectrum.
It is understood that the reaction yield is high and the product purity is high.
Example 2
Under stirring at room temperature, sequentially adding 1L of toluene and 0.8kg of hydrochloric acid into a 5L reaction bottle, and uniformly stirring; then 1.1kg dimethyl hydroxymethyl phosphonate is added into the mixture and stirred evenly; after the addition, heating the reaction solution to 110 ℃ for reaction, and keeping the temperature for reaction until the raw materials completely disappear; the reaction solution was cooled to 30 ℃, the reaction solution was evaporated to dryness under reduced pressure, and 0.1kg of hydrochloric acid was added to the obtained residue, which was allowed to stand for 8 hours and lyophilized to obtain 0.99kg of a white solid powdery chloromethylphosphonic acid product with a yield of 96.63%.
HPLC purity of the product: 98.53 percent.
Nuclear magnetic data: 1H NMR (400MHz, D2O): δ 3.31(d, 2H); 13C NMR (100MHz, D2O): δ 35.59, 34.11.
Please refer to fig. 1 and 2 for nuclear magnetic spectrum.
It can be understood that the reaction yield is high and the product purity is high.
Example 3
Stirring at room temperature, sequentially adding 1.5L of n-heptane and 0.7kg of hydrochloric acid into a 5L reaction bottle, and uniformly stirring; then 1.2kg of diisopropyl hydroxymethylphosphonate is added into the mixture and stirred evenly; after the addition is finished, heating the reaction solution to 100 ℃ for reaction, and keeping the temperature for reaction until the raw materials completely disappear;
the reaction solution was cooled to 30 ℃, the reaction solution was evaporated to dryness under reduced pressure, and 0.1kg of hydrochloric acid was added to the obtained residue, which was allowed to stand for 6 hours and lyophilized to obtain 0.78kg of a white solid powdery chloromethylphosphonic acid product with a yield of 97.74%.
Referring to fig. 3, the product HPLC purity: 99.27 percent.
Nuclear magnetic data: 1H NMR (400MHz, D2O): δ 3.31(d, 2H); 13C NMR (100MHz, D2O): δ 35.59, 34.11.
Please refer to fig. 1 and 2 for nuclear magnetic spectrum.
It is understood that the reaction yield is high and the product purity is high.
The principle and the implementation mode of the invention are explained by applying specific embodiments in the invention, and the description of the embodiments is only used for helping to understand the method and the core idea of the invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present invention.
Claims (6)
1. A process for preparing chloromethylphosphonic acid, which comprises:
s1: adding a solvent and hydrochloric acid into a reaction vessel in sequence, and stirring uniformly;
s2: adding hydroxymethyl phosphonate diester, stirring uniformly, heating to 80-120 ℃ for reaction, and keeping the temperature for reaction until the raw materials completely disappear to obtain a reaction solution;
s3: and cooling the reaction solution to 20-50 ℃, decompressing, evaporating the reaction solution to dryness, adding hydrochloric acid into the obtained residue, standing for 6-24 h, and freeze-drying to obtain chloromethyl phosphonic acid.
2. A process for preparing chloromethylphosphonic acid as claimed in claim 1, wherein said diester of hydroxymethylphosphonic acid is one or more of dimethyl hydroxymethylphosphonate, diethyl hydroxymethylphosphonate and diisopropyl hydroxymethylphosphonate.
3. A process for preparing chloromethylphosphonic acid as claimed in claim 1, wherein the reaction of the diester of hydroxymethylphosphonic acid with hydrochloric acid is carried out in a solvent selected from one or more of water, toluene, ethyl acetate, tetrahydrofuran, tert-butyl methyl ether, dioxane, n-hexane, n-heptane, petroleum ether, methanol, ethanol, isopropanol, tert-butanol and acetonitrile.
4. The process for preparing chloromethylphosphonic acid as claimed in claim 1, wherein S1 is carried out under stirring at room temperature.
5. A process for preparing chloromethylphosphonic acid as claimed in claim 1, wherein the amount of hydrochloric acid used in S1 is 0.5-10 times the molar equivalent.
6. A process for preparing chloromethylphosphonic acid as claimed in claim 1, wherein the amount of hydrochloric acid used in S3 is 0.01 to 1 times the molar equivalent.
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| CN202110272990.4A CN113024600A (en) | 2021-03-14 | 2021-03-14 | Process for preparing chloromethyl phosphonic acid |
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| CN202110272990.4A CN113024600A (en) | 2021-03-14 | 2021-03-14 | Process for preparing chloromethyl phosphonic acid |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1634941A (en) * | 2004-10-20 | 2005-07-06 | 西南师范大学 | Process for one-pot preparation of chloromethyl monosodium phosphonate |
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2021
- 2021-03-14 CN CN202110272990.4A patent/CN113024600A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1634941A (en) * | 2004-10-20 | 2005-07-06 | 西南师范大学 | Process for one-pot preparation of chloromethyl monosodium phosphonate |
Non-Patent Citations (2)
| Title |
|---|
| IVAN ROSENBERG ET AL.: "PHOSPHONYLMETHYL ANALOGUES OF RIBONUCLEOSIDE 2\',3\'-CYCLIC PHOSPHATES AND 2\'(3\')-NUCLEOTIDE METHYL ESTERS: SYNTHESIS AND PROPERTIES", 《COLLECTION CZECHOSLOVAK CHEM. COMMUN.》, vol. 50, no. 7, pages 1507 - 1513 * |
| ZASUKHA, S. V.ET AL.: "(Aryl)(α-fluoro)- and (aryl)(α-chloro)methylenebisphosphonic acids and their chloranhydrides", 《UKRAINSKII KHIMICHESKII ZHURNAL》, vol. 80, no. 1, pages 38 - 43 * |
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