CN112142781A - Preparation method of methyl hypophosphorous acid - Google Patents
Preparation method of methyl hypophosphorous acid Download PDFInfo
- Publication number
- CN112142781A CN112142781A CN201910570556.7A CN201910570556A CN112142781A CN 112142781 A CN112142781 A CN 112142781A CN 201910570556 A CN201910570556 A CN 201910570556A CN 112142781 A CN112142781 A CN 112142781A
- Authority
- CN
- China
- Prior art keywords
- phosphine
- methyl
- preparation
- reaction
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- -1 methyl hypophosphorous acid Chemical compound 0.000 title claims abstract description 23
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 38
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 26
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 claims abstract description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 20
- SAWKFRBJGLMMES-UHFFFAOYSA-N methylphosphine Chemical compound PC SAWKFRBJGLMMES-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- BCDIWLCKOCHCIH-UHFFFAOYSA-N methylphosphinic acid Chemical compound CP(O)=O BCDIWLCKOCHCIH-UHFFFAOYSA-N 0.000 claims abstract description 14
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 239000002585 base Substances 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 230000035484 reaction time Effects 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 5
- 150000007530 organic bases Chemical class 0.000 claims description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000000197 pyrolysis Methods 0.000 abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000003063 flame retardant Substances 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- ZBMRKNMTMPPMMK-UHFFFAOYSA-N 2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid;azane Chemical compound [NH4+].CP(O)(=O)CCC(N)C([O-])=O ZBMRKNMTMPPMMK-UHFFFAOYSA-N 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- CDPKWOKGVUHZFR-UHFFFAOYSA-N dichloro(methyl)phosphane Chemical compound CP(Cl)Cl CDPKWOKGVUHZFR-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-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
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
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)
Abstract
The invention discloses a preparation method of methyl hypophosphorous acid, which comprises the following steps: adding phosphorous acid into a reaction kettle, adding a catalyst, and pyrolyzing at 170-190 ℃ to generate phosphine; introducing the obtained phosphine and chloromethane into a strong alkali solution, adding organic alkali, heating and pressurizing, and reacting for 0.5-2 h to obtain methyl phosphine; adding the obtained methyl phosphine into a solvent, adding hydrogen peroxide under the stirring condition, and reacting to obtain the methylphosphinic acid. According to the preparation method of the methyl hypophosphorous acid, the methyl hypophosphorous acid is prepared by adopting a three-step process, the preparation method is simple, and the reaction conditions are mild; firstly, phosphine is prepared by phosphorous acid pyrolysis, and the obtained phosphine has high purity; then, the phosphine, the chloromethane and the strong base react to obtain the methyl phosphine, and the reaction time is short and the reaction rate is high; and finally, the methyl phosphine reacts with hydrogen peroxide, so that the raw materials in the whole process are easy to obtain, the preparation cost is low, and the method is suitable for industrial production.
Description
Technical Field
The invention relates to a preparation method of methyl hypophosphorous acid, belonging to the technical field of organic compound preparation.
Background
The methylphosphinic acid is a good flame retardant, has good flame retardant performance and plasticizing performance in plastics and rubber, is a best substitute for hypophosphorous acid and salts thereof, has better flame retardant performance than hypophosphite, is less in addition amount, and has little influence on the mechanical performance of added products.
The methyl hypophosphorous acid is also an important intermediate of herbicide glufosinate-ammonium, the synthesis is difficult, Bayer companies adopt a Grignard reagent method laboratory for synthesizing the methyl hypophosphorous acid at the earliest time, and the industrial value is lost due to the strict requirement on equipment, too large investment, long period of the produced product, low yield, low purity and large difficulty in purifying the intermediate.
Chinese patent with patent publication No. CN108456226A discloses a synthetic preparation method of methylphosphinic acid and methylphosphinic acid salt, which comprises the following steps: step one, preparing raw materials; step two, adding raw materials; step three, vacuum replacement; step four, reaction; step five, distilling out the methyl phosphorus dichloride and step six, distilling out acid water. Under the action of methane or chloromethane, metallic tin, metallic aluminum, metallic sodium, metallic lithium and alloy thereof, the methyl hypophosphorous acid is synthesized with yellow phosphorus or phosphorus trichloride, water and organic solvent, the production period is short, the yield is high, the disadvantages of flammability and explosiveness of an intermediate in the original synthesis method are avoided, but reversible reaction exists in the reaction, the reaction condition is not easy to control, and the reaction yield is influenced.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art and provide a preparation method of methyl hypophosphorous acid, which is simple and has high reaction yield.
The technical purpose of the invention is realized by the following technical scheme:
a preparation method of methyl hypophosphorous acid comprises the following steps:
(1) adding phosphorous acid into a reaction kettle, adding a catalyst, and pyrolyzing at 170-190 ℃ to generate phosphine;
(2) introducing the obtained phosphine and chloromethane into a strong alkali solution, adding organic alkali, heating and pressurizing, and reacting for 0.5-2 h to obtain methyl phosphine;
(3) adding the obtained methyl phosphine into a solvent, adding hydrogen peroxide under the stirring condition, and reacting to obtain the methylphosphinic acid.
By adopting the technical scheme, the methyl hypophosphorous acid is prepared by adopting a three-step process, the preparation method is simple, and the reaction conditions are mild.
Preferably, the catalyst in step (1) is a platinum carbon catalyst or a palladium carbon catalyst.
By adopting the technical scheme, the platinum-carbon catalyst or the palladium-carbon catalyst is used as the catalyst in the process of preparing the phosphine, so that the reaction rate can be improved, the prepared phosphine can be directly subjected to the next reaction, the reaction time is saved, and the reaction efficiency is improved.
Preferably, the weight of the catalyst in the step (1) is 0.001-0.01 of the weight of phosphorous acid.
By adopting the technical scheme, the reaction rate can be improved and the reaction cost can be saved in a certain range by adopting a certain amount of catalyst.
Preferably, the strong base in step (2) is one of sodium hydroxide or potassium hydroxide.
By adopting the technical scheme, sodium hydroxide or potassium hydroxide can rapidly react with phosphine and chloromethane, so that the reaction efficiency is improved.
Preferably, the reaction temperature in the step (2) is 60-100 ℃, and the reaction pressure is 1-5 MPa.
By adopting the technical scheme, the reaction temperature and the reaction pressure in the range are adopted, so that the reaction rate of the gas and the liquid is accelerated.
Preferably, the organic base in step (2) is triethylamine.
Preferably, the addition amount of the organic base in the step (2) is 5-10% of the mass of the strong base.
By adopting the technical scheme, the organic base with proper dosage can activate reactants, promote reaction and simultaneously do not influence the purity of products.
Preferably, the solvent in the step (3) is one of toluene, chloroform, benzene or cyclohexane.
By adopting the technical scheme, the proper solvent is adopted to promote the dissolution of reactants, thereby being beneficial to the reaction.
Preferably, the reaction temperature in the step (3) is 80-100 ℃, and the reaction time is 4-10 h.
In conclusion, the invention has the following beneficial effects:
(1) according to the preparation method of the methyl hypophosphorous acid, the methyl hypophosphorous acid is prepared by adopting a three-step process, the preparation method is simple, and the reaction conditions are mild;
(2) according to the preparation method of the methyl hypophosphorous acid, phosphine is prepared by phosphorous acid pyrolysis, and the obtained phosphine is high in purity; then, the phosphine, the chloromethane and the strong base react to obtain the methyl phosphine, and the reaction time is short and the reaction rate is high; and finally, the methyl phosphine reacts with hydrogen peroxide, so that the raw materials in the whole process are easy to obtain, the preparation cost is low, and the method is suitable for industrial production.
Detailed Description
The invention is further described below. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
A preparation method of methyl hypophosphorous acid comprises the following steps:
(1) adding phosphorous acid into a reaction kettle, adding a catalyst, and pyrolyzing at 170-190 ℃ to generate phosphine;
(2) introducing the obtained phosphine and chloromethane into a strong alkali solution, adding organic alkali, heating and pressurizing, and reacting for 0.5-2 h to obtain methyl phosphine;
(3) adding the obtained methyl phosphine into a solvent, adding hydrogen peroxide under the stirring condition, and reacting to obtain the methylphosphinic acid.
The reaction process is as follows:
example 1
A preparation method of methyl hypophosphorous acid comprises the following steps:
(1) 1kg of phosphorous acid is added into a reaction kettle, 1g of platinum carbon catalyst is added, and the mixture is pyrolyzed at 170 ℃ to generate phosphine;
(2) introducing the obtained phosphine and chloromethane into 100mL of 5mol/L sodium hydroxide solution, adding 1g of triethylamine, heating and pressurizing, and reacting at 60 ℃ and 5MPa for 0.5h to obtain methyl phosphine;
(3) adding the obtained methyl phosphine into 100mL of toluene, adding 200mL of hydrogen peroxide under the stirring condition, reacting at 100 ℃ for 4 hours to obtain the methylphosphinic acid, washing with water, and drying to obtain the final product with the total yield of 75.5% and the purity of gas chromatography of 87.2%.
Example 2
A preparation method of methyl hypophosphorous acid comprises the following steps:
(1) adding 1kg of phosphorous acid into a reaction kettle, adding 5g of palladium carbon catalyst, and pyrolyzing at 180 ℃ to generate phosphine;
(2) introducing the obtained phosphine and chloromethane into 100mL of 5mol/L sodium hydroxide solution, adding 1.5g of triethylamine, heating and pressurizing, and reacting for 1h at 80 ℃ and 3MPa to obtain methyl phosphine;
(3) adding the obtained methyl phosphine into 100mL of benzene, adding 150mL of hydrogen peroxide under the stirring condition, reacting at 80 ℃ for 7 hours to obtain the methyl phosphinic acid, washing with water, and drying to obtain the final product with the total yield of 76.4% and the purity of gas chromatography of 88.4%.
Example 3
A preparation method of methyl hypophosphorous acid comprises the following steps:
(1) adding 1kg of phosphorous acid into a reaction kettle, adding 10g of palladium carbon catalyst, and pyrolyzing at 190 ℃ to generate phosphine;
(2) introducing the obtained phosphine and chloromethane into 100mL of 5mol/L sodium hydroxide solution, adding 2g of triethylamine, heating and pressurizing, and reacting for 2h at 100 ℃ and 1MPa to obtain methyl phosphine;
(3) adding the obtained methyl phosphine into 100mL of cyclohexane, adding 150mL of hydrogen peroxide under the stirring condition, reacting at 80 ℃ for 10h to obtain the methylphosphinic acid, washing with water, and drying to obtain the final product with the total yield of 78.2% and the purity of gas chromatography of 87.4%.
According to the preparation method of the methyl hypophosphorous acid, the methyl hypophosphorous acid is prepared by adopting a three-step process, the preparation method is simple, and the reaction conditions are mild; according to the preparation method of the methyl hypophosphorous acid, phosphine is prepared by phosphorous acid pyrolysis, and the obtained phosphine is high in purity; then, the phosphine, the chloromethane and the strong base react to obtain the methyl phosphine, and the reaction time is short and the reaction rate is high; and finally, the methyl phosphine reacts with hydrogen peroxide, so that the raw materials in the whole process are easy to obtain, the preparation cost is low, and the method is suitable for industrial production.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments, and all technical solutions belonging to the idea of the present invention belong to the protection scope of the present invention. It should be noted that modifications and embellishments within the scope of the invention may occur to those skilled in the art without departing from the principle of the invention, and are considered to be within the scope of the invention.
Claims (9)
1. The preparation method of the methyl hypophosphorous acid is characterized by comprising the following steps:
(1) adding phosphorous acid into a reaction kettle, adding a catalyst, and pyrolyzing at 170-190 ℃ to generate phosphine;
(2) introducing the obtained phosphine and chloromethane into a strong alkali solution, adding organic alkali, heating and pressurizing, and reacting for 0.5-2 h to obtain methyl phosphine;
(3) adding the obtained methyl phosphine into a solvent, adding hydrogen peroxide under the stirring condition, and reacting to obtain the methylphosphinic acid.
2. The method according to claim 1, wherein the catalyst in step (1) is a platinum-carbon catalyst or a palladium-carbon catalyst.
3. The method according to claim 1 or 2, wherein the weight of the catalyst in step (1) is 0.001 to 0.01 weight percent of the weight of the phosphorous acid.
4. The method for preparing methylphosphinic acid according to claim 1, wherein the strong base in step (2) is one of sodium hydroxide and potassium hydroxide.
5. The process according to claim 1, wherein the reaction temperature in step (2) is 60 to 100 ℃ and the reaction pressure is 1 to 5 MPa.
6. The method according to claim 1, wherein the organic base used in step (2) is triethylamine.
7. The method for preparing methylphosphinic acid according to claim 1 or 6, wherein the amount of organic base added in step (2) is 5-10% by mass of the strong base.
8. The method for preparing methylphosphinic acid according to claim 1, wherein the solvent used in step (3) is one of toluene, chloroform, benzene or cyclohexane.
9. The method for preparing methylphosphinic acid according to claim 1, wherein the reaction temperature in step (3) is 80-100 ℃ and the reaction time is 4-10 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910570556.7A CN112142781A (en) | 2019-06-27 | 2019-06-27 | Preparation method of methyl hypophosphorous acid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910570556.7A CN112142781A (en) | 2019-06-27 | 2019-06-27 | Preparation method of methyl hypophosphorous acid |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112142781A true CN112142781A (en) | 2020-12-29 |
Family
ID=73868881
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910570556.7A Pending CN112142781A (en) | 2019-06-27 | 2019-06-27 | Preparation method of methyl hypophosphorous acid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112142781A (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4839105A (en) * | 1984-01-21 | 1989-06-13 | Hoechst Aktiengesellschaft | Process for the preparation of alkanephosphonous acids |
| CN103318860A (en) * | 2013-07-10 | 2013-09-25 | 常州宏福高端膦技术研发中心有限公司 | Method for producing hydrogen phosphide by utilizing phosphorous acid pyrolysis |
| CN107118232A (en) * | 2017-06-29 | 2017-09-01 | 南京宏福高端膦技术研发中心有限公司 | The method for preparing monoalkyl hypophosphorous acid |
-
2019
- 2019-06-27 CN CN201910570556.7A patent/CN112142781A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4839105A (en) * | 1984-01-21 | 1989-06-13 | Hoechst Aktiengesellschaft | Process for the preparation of alkanephosphonous acids |
| CN103318860A (en) * | 2013-07-10 | 2013-09-25 | 常州宏福高端膦技术研发中心有限公司 | Method for producing hydrogen phosphide by utilizing phosphorous acid pyrolysis |
| CN107118232A (en) * | 2017-06-29 | 2017-09-01 | 南京宏福高端膦技术研发中心有限公司 | The method for preparing monoalkyl hypophosphorous acid |
Non-Patent Citations (1)
| Title |
|---|
| LANGHANS, KLAUS P. ET AL: "Synthesis of primary and secondary phosphines by selective alkylation of PH3 under phase transfer conditions", 《ZEITSCHRIFT FUER NATURFORSCHUNG, B: CHEMICAL SCIENCES》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104892670A (en) | Preparation method of glufosinate and analogue of glufosinate | |
| CN103665032A (en) | Preparation method of glufosinate | |
| CN101638224B (en) | Method for purifying phosphine by-product and application method of phosphine by-product | |
| CN112979498A (en) | Preparation method of 3-fluoro-4-trifluoromethyl benzonitrile | |
| CN106543026B (en) | A kind of preparation method of methyl hydrazine | |
| CN103374033A (en) | Functionalized quaternary phosphonium salt ionic liquid of organic phosphine and preparation method thereof | |
| CN102093253A (en) | Preparation method of benzoxylamine hydrochloride compounds | |
| CN105017525B (en) | A kind of branched modification agent and corresponding fire-retardant nylon resin | |
| CN102285937B (en) | Method for synthesizing febuxostat | |
| CN112142781A (en) | Preparation method of methyl hypophosphorous acid | |
| CN105732708A (en) | Method for producing dichlorophenylphosphine | |
| CN110229184B (en) | Preparation method of methyl ethyl phosphinic acid and aluminum salt thereof | |
| CN108530301B (en) | Synthetic method of 2,4, 6-trifluorobenzylamine | |
| WO2010066088A1 (en) | Method for synthesizing o-diphenylphosphino benzoic acid | |
| CN102161678A (en) | Glycine and application of acid salt thereof in preparation of glyphosate | |
| CN107001250B (en) | A method of Ao Dangka is prepared for intermediate | |
| CN103554186A (en) | Preparation method of phosphonitrilic chloride trimer | |
| CN102295623A (en) | Method for preparing N-acetylmorpholine by using ketene | |
| CN112142783A (en) | Preparation method of methylphosphinic acid ester | |
| CN103739624B (en) | The synthetic method of aluminum diethylphosphinate | |
| CN109111371B (en) | Preparation method of hydrazino ethyl acetate hydrochloride | |
| CN114369031B (en) | Synthesis method of 4,4' -diaminoterphenyl | |
| CN113493401B (en) | Preparation method of p-methylsulfonylbenzoic acid | |
| CN115364896B (en) | Catalyst for synthesizing dialkyl alkylphosphonate, and preparation method and application thereof | |
| CN114249768B (en) | Amino acid-based phosphorus flame retardant, and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20201229 |
|
| WD01 | Invention patent application deemed withdrawn after publication |