CN105646574A - Synthesizing method of 3-(alkoxy methyl phosphoryl) propionic ester, analogue and phosphinothricin - Google Patents
Synthesizing method of 3-(alkoxy methyl phosphoryl) propionic ester, analogue and phosphinothricin Download PDFInfo
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- CN105646574A CN105646574A CN201610125377.9A CN201610125377A CN105646574A CN 105646574 A CN105646574 A CN 105646574A CN 201610125377 A CN201610125377 A CN 201610125377A CN 105646574 A CN105646574 A CN 105646574A
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- Prior art keywords
- phosphoryl
- synthetic method
- propionic ester
- alkoxy methyl
- methyl
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- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 title claims abstract description 12
- IAJOBQBIJHVGMQ-UHFFFAOYSA-N Phosphinothricin Natural products CP(O)(=O)CCC(N)C(O)=O IAJOBQBIJHVGMQ-UHFFFAOYSA-N 0.000 title abstract 3
- IAJOBQBIJHVGMQ-BYPYZUCNSA-N glufosinate-P Chemical compound CP(O)(=O)CC[C@H](N)C(O)=O IAJOBQBIJHVGMQ-BYPYZUCNSA-N 0.000 title abstract 3
- 230000002194 synthesizing effect Effects 0.000 title abstract 3
- 239000002904 solvent Substances 0.000 claims abstract description 13
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical class [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002253 acid Substances 0.000 claims abstract description 9
- 239000011230 binding agent Substances 0.000 claims abstract description 7
- 238000006467 substitution reaction Methods 0.000 claims abstract description 6
- 239000000047 product Substances 0.000 claims abstract description 4
- 239000006227 byproduct Substances 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 36
- 238000010189 synthetic method Methods 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- WTEJQBARPJSNLZ-UHFFFAOYSA-N C(C(=O)N)(=O)O.P Chemical compound C(C(=O)N)(=O)O.P WTEJQBARPJSNLZ-UHFFFAOYSA-N 0.000 claims description 12
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 5
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- CMEWLCATCRTSGF-UHFFFAOYSA-N N,N-dimethyl-4-nitrosoaniline Chemical compound CN(C)C1=CC=C(N=O)C=C1 CMEWLCATCRTSGF-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 125000001501 propionyl group Chemical group O=C([*])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- -1 propionyl halide Chemical class 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000006114 decarboxylation reaction Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000005494 condensation Effects 0.000 abstract 1
- 238000009833 condensation Methods 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 238000009835 boiling Methods 0.000 description 7
- 239000000706 filtrate Substances 0.000 description 6
- 238000011534 incubation Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000004448 titration Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 4
- RZWZRACFZGVKFM-UHFFFAOYSA-N propanoyl chloride Chemical compound CCC(Cl)=O RZWZRACFZGVKFM-UHFFFAOYSA-N 0.000 description 4
- 229910019142 PO4 Inorganic materials 0.000 description 3
- NEHMKBQYUWJMIP-UHFFFAOYSA-N anhydrous methyl chloride Natural products ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 3
- CDPKWOKGVUHZFR-UHFFFAOYSA-N dichloro(methyl)phosphane Chemical compound CP(Cl)Cl CDPKWOKGVUHZFR-UHFFFAOYSA-N 0.000 description 3
- 229940102396 methyl bromide Drugs 0.000 description 3
- GZUXJHMPEANEGY-UHFFFAOYSA-N methyl bromide Substances BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 3
- 229940050176 methyl chloride Drugs 0.000 description 3
- 239000010452 phosphate Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000006482 condensation reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- RIBFXMJCUYXJDZ-UHFFFAOYSA-N propanoyl bromide Chemical compound CCC(Br)=O RIBFXMJCUYXJDZ-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance 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
- XVMSFILGAMDHEY-UHFFFAOYSA-N 6-(4-aminophenyl)sulfonylpyridin-3-amine Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=N1 XVMSFILGAMDHEY-UHFFFAOYSA-N 0.000 description 1
- FKCLZDBBWQTVIS-UHFFFAOYSA-N C(=O)=C(C(=O)O)CC=P(=O)CO Chemical compound C(=O)=C(C(=O)O)CC=P(=O)CO FKCLZDBBWQTVIS-UHFFFAOYSA-N 0.000 description 1
- NSWQJASYEPJGJA-UHFFFAOYSA-N CCOP(C)(O)OCC.CNC(S)=N Chemical compound CCOP(C)(O)OCC.CNC(S)=N NSWQJASYEPJGJA-UHFFFAOYSA-N 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 238000005654 Michaelis-Arbuzov synthesis reaction Methods 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000007059 Strecker synthesis reaction Methods 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- OAEDQDDHNNHCFI-UHFFFAOYSA-N [NH4+].C(C(=O)N)(=O)[O-].P Chemical compound [NH4+].C(C(=O)N)(=O)[O-].P OAEDQDDHNNHCFI-UHFFFAOYSA-N 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- SOWBFZRMHSNYGE-UHFFFAOYSA-N oxamic acid Chemical compound NC(=O)C(O)=O SOWBFZRMHSNYGE-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 125000001476 phosphono group Chemical group [H]OP(*)(=O)O[H] 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002699 waste material Substances 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
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3264—Esters with hydroxyalkyl compounds
-
- 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)]
- C07F9/301—Acyclic saturated acids which can have further substituents on alkyl
-
- 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)]
- C07F9/32—Esters thereof
- C07F9/3258—Esters thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3282—Esters with hydroxyaryl compounds
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 synthesizing method of 3-(alkoxy methyl phosphoryl) propionic ester, analogue and phosphinothricin. The method is characterized in that 3-(methyl halogenated phosphoryl) propionyl halide is used as raw material, the 3-(methyl halogenated phosphoryl) propionyl halide has substitution reaction with ROH in solvent under a low-temperature condition to obtain the product, and the byproduct HX is neutralized through acid-binding agent. The 3-(alkoxy methyl phosphoryl) propionic ester and analogue synthesized by the method is subjected to direct condensation and decarboxylation to obtain phosphinothricin key intermediate 2-carbonyl-4-(alkoxy methyl phosphoryl)-butyric acid. The synthesizing method is simple to operate, low in production cost, safe, environmental friendly, and capable of avoiding the risks in the industrialization process.
Description
Technical field
The invention belongs to chemosynthesis technical field, particularly relate to the synthetic method of a kind of 3-(alkoxy methyl phosphoryl) propionic ester and the like and phosphine oxamate.
Background technology
Phosphine oxamate (glufosinate-ammonium) by Hoechest company in the eighties of last century Development and Production eighties; chemical name 4-[hydroxyl (methyl) phosphono]-DL-high lactamine; also known as phosphine oxamate ammonium salt, for phosphorus acid herbicides.
In the phosphine oxamate synthesis main flow route of current bibliographical information, methyl dichloro phosphorus and methylisothiouronium methylphosphite ester are its two important intermediate products. Meiji Seika Kaisba company proposes in US4510102, US4101573 and JP Publication 80-60298 and initiates formatted reaction with tris phosphite and finally give methylisothiouronium methylphosphite diethylester, and first, the feature of grignard reaction is: 1) alkyl halide magnesium avoids water; 2) needing ether or oxolane polar solvent, waste is big; 3) reaction need to operate at low temperatures, and energy consumption is big; 4) yield is not high, and large-scale production difficulty is big; Secondly, intermediate can react by automatic Arbuzov when normal pressure nearly its boiling point (122 DEG C), and the purity of this ester is more high more is susceptible to; Arbuzov reaction meeting very exothermic, stores and transport aspect is also required to expend very big goods and materials.
The industrializing synthesis route being intermediate with methyl dichloro phosphorus, intermediate synthesis can be divided into the synthesis of ternary complexes method and methane high temperature method to synthesize two kinds; Phosphine oxamate route is removable is divided into two kinds: 1 in later stage synthesis) methyl dichloro phosphorus and the unstable methylisothiouronium methylphosphite ester type compound of alcohol substitution reaction synthesis, the Strecker reaction that then Michael addition is gone further traditional; This route needs also exist for the methylisothiouronium methylphosphite ester type compound that experience is unstable, and Strecker route need to use the Cyanogran. of severe toxicity; 2) the methyl dichloro phosphorus-bis-acyl chlorides-cycli phosphate acid anhydride-one acid-phosphine oxamate route of Beyer Co., Ltd's exploitation; This route total recovery is up to 80%, and without using severe poisonous chemicals; But the condensation reaction of cycli phosphate acid anhydride needs to use highly basic, it is easy under high temperature destroy cyclic acid anhydride, affects product yield.
But forefathers cannot walk around unstable methylisothiouronium methylphosphite ester type compound intermediate and cycli phosphate acid anhydride instability ester condensation reaction to produce phosphine oxamate; the present invention adopts intermediate 3-(alkoxy methyl phosphoryl) propionic ester synthesis phosphine oxamate, at present not yet open relevant synthesis technique.
Summary of the invention
In order to overcome the problems referred to above, it is an object of the invention to provide the synthetic method of a kind of 3-(alkoxy methyl phosphoryl) propionic ester and the like and phosphine oxamate, to reduce production cost, simplify operating process, avoid the danger in course of industrialization simultaneously.
The above-mentioned purpose of the present invention is achieved through the following technical solutions: the synthetic method of a kind of 3-(alkoxy methyl phosphoryl) propionic ester and the like formula (I); with 3-(methyl halogenated phosphoryl) propionyl halogenide formula (II) for raw material; under cryogenic conditions; substitution reaction is carried out in a solvent with Formula (III); obtain product; by-product HX adopts acid binding agent to neutralize
Wherein, described X is halogen atom, and described R is the alkyl or phenyl of hydrogen or C1��C6.
Optimizing further, described acid binding agent is NH3, ethylenediamine, triethylamine, N, accelerine, pyridine or Na2CO3��K2CO3, one or more in NaOH, KOH.
Optimizing further, described solvent is one or more in benzene,toluene,xylene.
Optimizing further, described cryogenic conditions is temperature is-50��0 DEG C, it is desirable to for-50��-30 DEG C.
Optimizing further, the mass ratio of described Formula (II), Formula (III), acid binding agent and solvent is 1:2.2��4.0:2.2��4.0:5.0��20.0.
Optimizing further, the compound (III) of described substitution reaction adopts the mode of dropping to carry out.
It is a further object of the present invention to provide the synthetic method of a kind of phosphine oxamate, its intermediate is above-mentioned 3-(alkoxy methyl phosphoryl) propionic ester and the like.
Compared with prior art, 3-(alkoxy methyl phosphoryl) propionic ester that the method having the technical effect that the present invention that the present invention produces synthesizes and the like direct polycondensation, decarboxylation prepare phosphine oxamate key intermediate 2-carbonyl-4-(hydroxymethyl phosphoryl)-butanoic acid; The present invention is easy and simple to handle, and production cost is low, safety and environmental protection, avoids the danger in course of industrialization simultaneously.
Detailed description of the invention
Illustrated embodiment is to better present disclosure be illustrated, but is not that present disclosure is only limitted to illustrated embodiment.
Embodiment 1
0.25mol3-(methyl chloride is for phosphoryl) propionyl chloride and 2.0mol toluene is added in 500ml four-hole boiling flask; normal pressure constant voltage titration funnel adds 0.60mol methanol; it is down to-30 DEG C when temperature and starts to drip methanol, 4��5 per second, and metering passes into 0.6molNH in system3, after dropwising, it being incubated 2h, rise to incubation at room temperature 12h, add toluene and filter out insoluble salt, filtrate adopts Rotary Evaporators to steam solvent, obtains white solid 0.218mol, content 95.6%.
Embodiment 2
Adding 0.25mol3-(methyl bromide is for phosphoryl) propionyl bromide and 2.0mol benzene in 500ml four-hole boiling flask, normal pressure constant voltage titration funnel adds 0.60mol methanol, is down to-20 DEG C when temperature and starts to drip methanol; 4��5 per second; and metering passes into 0.6molN in system, accelerine, after dropwising; insulation 2h; rising to incubation at room temperature 12h, add benzene and filter out insoluble salt, filtrate adopts Rotary Evaporators to steam solvent; obtain white solid 0.206mol, content 94.3%.
Embodiment 3
0.25mol3-(methyl bromide is for phosphoryl) propionyl chloride and 2.0mol toluene is added in 500ml four-hole boiling flask; normal pressure constant voltage titration funnel adds 0.60mol ethanol; it is down to-50 DEG C when temperature and starts to drip ethanol, 4��5 per second, and in system, add 0.4mol ethylenediamine and 0.2molK2CO3, after dropwising, it being incubated 2h, rise to incubation at room temperature 12h, add toluene and filter out insoluble salt, filtrate adopts Rotary Evaporators to steam solvent, obtains white solid 0.231mol, content 97.5%.
Embodiment 4
0.25mol3-(methyl chloride is for phosphoryl) propionyl chloride and 2.0mol toluene is added in 500ml four-hole boiling flask; normal pressure constant voltage titration funnel adds 0.60mol isopropanol, is down to-30 DEG C when temperature and starts to drip isopropanol, 4��5 per second; and metering passes into 0.8mol pyridine in system; after dropwising, it is incubated 2h, rises to incubation at room temperature 12h; add toluene and filter out insoluble salt; filtrate adopts Rotary Evaporators to steam solvent, obtains white solid 0.237mol, content 97.2%.
Embodiment 5
0.25mol3-(methyl bromide is for phosphoryl) propionyl bromide and 2.0mol toluene is added in 500ml four-hole boiling flask; normal pressure constant voltage titration funnel adds 0.60mol phenol; it is down to-40 DEG C when temperature and starts to drip phenol, 4��5 per second, and metering passes into 0.4molNH in system3And 0.2molNaOH, after dropwising, it being incubated 2h, rise to incubation at room temperature 12h, add toluene and filter out insoluble salt, filtrate adopts Rotary Evaporators to steam solvent, obtains white solid 0.245mol, content 98.1%.
Embodiment 6
0.25mol3-(methyl chloride is for phosphoryl) propionyl chloride and 2.0mol toluene is added in 500ml four-hole boiling flask; normal pressure constant voltage titration funnel adds 0.60mol methanol, is down to-10 DEG C when temperature and starts to drip methanol, 4��5 per second; and metering adds 0.6mol triethylamine in system; after dropwising, it is incubated 2h, rises to incubation at room temperature 12h; add toluene and filter out insoluble salt; filtrate adopts Rotary Evaporators to steam solvent, obtains white solid 0.189mol, content 90.2%.
Claims (8)
1. the synthetic method of 3-(alkoxy methyl phosphoryl) propionic ester and the like and phosphine oxamate; it is characterized in that; with 3-(methyl halogenated phosphoryl) propionyl halogenide formula (II) for raw material; under cryogenic conditions; substitution reaction is carried out in a solvent with Formula (III); obtaining product, by-product HX adopts acid binding agent to neutralize
Wherein, described X is halogen atom, and described R is the alkyl or phenyl of hydrogen or C1��C6.
2. synthetic method according to claim 1, it is characterised in that described acid binding agent is NH3, ethylenediamine, triethylamine, N, accelerine, pyridine, Na2CO3��K2CO3, one or more in NaOH, KOH.
3. synthetic method according to claim 1, it is characterised in that described solvent is one or more in benzene,toluene,xylene.
4. synthetic method according to claim 1, it is characterised in that described cryogenic conditions is temperature is-50��0 DEG C.
5. synthetic method according to claim 1, it is characterised in that described cryogenic conditions is temperature is-50��-30 DEG C.
6. synthetic method according to claim 1, it is characterised in that the mass ratio of described Formula (II), Formula (III), acid binding agent and solvent is 1:2.2��4.0:2.2��4.0:5.0��20.0.
7. synthetic method according to claim 1, it is characterised in that the compound (III) of described substitution reaction adopts the mode of dropping to add.
8. the synthetic method of a phosphine oxamate; its intermediate is 3-(alkoxy methyl phosphoryl) propionic ester and the like; it is characterized in that, described 3-(alkoxy methyl phosphoryl) propionic ester and the like is prepared by the method for claim 1-7.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565778A (en) * | 2016-11-10 | 2017-04-19 | 安徽国星生物化学有限公司 | Novel synthesis method for 3-(alkoxy methyl phosphoryl)propionate |
| CN106957334A (en) * | 2017-03-24 | 2017-07-18 | 马鞍山中创环保科技有限公司 | A kind of ion-exchange fibre as acid binding agent nitration mixture ester preparation method |
| CN113717224A (en) * | 2021-07-28 | 2021-11-30 | 南通江山农药化工股份有限公司 | MPP microchannel reaction preparation process and MPP |
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| US5153345A (en) * | 1989-10-20 | 1992-10-06 | Hoechst Aktiengesellschaft | Process for the preparation of alkyl methyl-3-carbalkoxyethylphosphinates |
| CN103539815A (en) * | 2013-10-14 | 2014-01-29 | 苏州联合伟业科技有限公司 | Preparation method of 4-(hydroxy-(methyl)phosphinyl)-2-oxobutyric acid |
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| US5153345A (en) * | 1989-10-20 | 1992-10-06 | Hoechst Aktiengesellschaft | Process for the preparation of alkyl methyl-3-carbalkoxyethylphosphinates |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106565778A (en) * | 2016-11-10 | 2017-04-19 | 安徽国星生物化学有限公司 | Novel synthesis method for 3-(alkoxy methyl phosphoryl)propionate |
| CN106565778B (en) * | 2016-11-10 | 2018-09-28 | 安徽国星生物化学有限公司 | A kind of 3- (alkoxy methyl phosphoryl) propionic ester synthetic method |
| CN106957334A (en) * | 2017-03-24 | 2017-07-18 | 马鞍山中创环保科技有限公司 | A kind of ion-exchange fibre as acid binding agent nitration mixture ester preparation method |
| CN113717224A (en) * | 2021-07-28 | 2021-11-30 | 南通江山农药化工股份有限公司 | MPP microchannel reaction preparation process and MPP |
| CN113717224B (en) * | 2021-07-28 | 2023-08-01 | 南通江山农药化工股份有限公司 | MPP microchannel reaction preparation process and MPP |
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