CN106046051A - Synthesis method of glufosinate intermediate of methyl diethyl phosphite - Google Patents
Synthesis method of glufosinate intermediate of methyl diethyl phosphite Download PDFInfo
- Publication number
- CN106046051A CN106046051A CN201610460721.XA CN201610460721A CN106046051A CN 106046051 A CN106046051 A CN 106046051A CN 201610460721 A CN201610460721 A CN 201610460721A CN 106046051 A CN106046051 A CN 106046051A
- Authority
- CN
- China
- Prior art keywords
- methylisothiouronium methylphosphite
- glufosinate
- reaction
- methylphosphite diethylester
- diethylester
- 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
- 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 title claims abstract description 20
- 238000001308 synthesis method Methods 0.000 title abstract 3
- 239000005561 Glufosinate Substances 0.000 title abstract 2
- UTZAXPKCGJZGLB-UHFFFAOYSA-N diethyl methyl phosphite Chemical compound CCOP(OC)OCC UTZAXPKCGJZGLB-UHFFFAOYSA-N 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000007789 gas Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000006227 byproduct Substances 0.000 claims abstract description 4
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 4
- NSWQJASYEPJGJA-UHFFFAOYSA-N CCOP(C)(O)OCC.CNC(S)=N Chemical compound CCOP(C)(O)OCC.CNC(S)=N NSWQJASYEPJGJA-UHFFFAOYSA-N 0.000 claims description 29
- 238000010189 synthetic method Methods 0.000 claims description 15
- 239000006004 Quartz sand Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000945 filler Substances 0.000 claims description 5
- 238000010521 absorption reaction Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 230000001154 acute effect Effects 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- UAEWCWCMYQAIDR-UHFFFAOYSA-N diethyl methyl phosphate Chemical compound CCOP(=O)(OC)OCC UAEWCWCMYQAIDR-UHFFFAOYSA-N 0.000 abstract 2
- 235000019441 ethanol Nutrition 0.000 abstract 1
- 238000011112 process operation Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- NSSMTQDEWVTEKN-UHFFFAOYSA-N diethoxy(methyl)phosphane Chemical compound CCOP(C)OCC NSSMTQDEWVTEKN-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- NYYLZXREFNYPKB-UHFFFAOYSA-N 1-[ethoxy(methyl)phosphoryl]oxyethane Chemical compound CCOP(C)(=O)OCC NYYLZXREFNYPKB-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- LXCYSACZTOKNNS-UHFFFAOYSA-N diethoxy(oxo)phosphanium Chemical compound CCO[P+](=O)OCC LXCYSACZTOKNNS-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 125000004494 ethyl ester group Chemical group 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004176 ammonification Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- UCQFCFPECQILOL-UHFFFAOYSA-N diethyl hydrogen phosphate Chemical compound CCOP(O)(=O)OCC UCQFCFPECQILOL-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 244000037671 genetically modified crops Species 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- -1 phosphine diethyl methyl-phosphonite Chemical compound 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 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 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
- C07F9/48—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof
- C07F9/4866—Phosphonous acids [RP(OH)2] including [RHP(=O)(OH)]; Thiophosphonous acids including [RP(SH)2], [RHP(=S)(SH)]; Derivatives thereof the ester moiety containing a substituent or structure which is considered as characteristic
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 synthesis method of glufosinate intermediate of methyl diethyl phosphate. According to the synthesis method, MDP is used as raw materials to take a reaction with an ethyl alcohol gas phase in a tubular reactor to generate methyl diethyl phosphate. The process operation process is simplified; the connection is ordered; the labor cost is greatly reduced; the production cost is reduced. The tubular reactor is used; the reaction equipment using a reaction kettle in the prior art is changed; the tubular reactor can realize the fast separation of a byproduct of hydrogen chloride from the product; the product yield is improved; meanwhile, the continuous operation is also realized; the danger in the industrialization process is avoided; the potential safety hazards are eliminated.
Description
Technical field
The present invention relates to the synthetic method of a kind of organic phosphorus compound, be specifically related to a kind of herbicide glufosinate-ammonium intermediate first
The synthetic method of base diethyl phosphite.
Background technology
Glufosinate-ammonium is phosphorus acid herbicides, is current large-tonnage pesticide species and second-biggest-in-the-world genetically modified crops the most in the world
Herbicide-tolerant, and in the important synthesis that methylisothiouronium methylphosphite diethylester is as synthesis glufosinate-ammonium (glufosinate-ammonium)
Mesosome, therefore the synthesis of methylisothiouronium methylphosphite diethylester is most important.
The existing document of route using the synthesis glufosinate-ammonium with methylisothiouronium methylphosphite diethylester as intermediate at present is reported:
Hans-Joachim Zeiss in J.Org.Chem.1991,56,1783-1788 once report with methylisothiouronium methylphosphite diethylester and
Ethyl acrylate catalytic reaction in the basic conditions, can prepare the methylisothiouronium methylphosphite diethylester of 81% yield, afterwards with oxalic acid two
Ethyl ester is catalyzing and condensing under highly basic, and decarboxylation prepares glufosinate-ammonium intermediate 2-ketoacid, and hydrogenation ammonification obtains glufosinate-ammonium.Hoechst
Within 2000, reporting Michael phosphine diethyl methyl-phosphonite, acrylic aldehyde and acetic anhydride in patent US6359162, phosphineization is produced
Thing directly can enter Strecker and glufosinate-ammonium is synthesized；Total recovery is up to 99%.
The synthesis of domestic methylisothiouronium methylphosphite diethylester all rests on lab scale stage, such as Chinese invention patent
(ZL201310299754.7) disclose the synthetic method of a kind of diethyl methyl-phosphonite, comprise the following steps: phosphorous acid two
Ethyl ester and methyl chloride gas carry out reaction in the presence of acid binding agent and prepare methylphosphonic acid diethylester, filter, the first of generation after reaction
Base diethyl phosphonate is present in filtrate；The organic solvent solution dissolved with reducing agent is dripped, by methylphosphonic acid diethyl in filtrate
Ester is reduced to diethyl methyl-phosphonite, has reacted rear distillation reaction liquid, has obtained diethyl methyl-phosphonite, and this synthetic method uses
Reactor, the processes such as reaction requires height, and needs to carry out under solvent condition, follow-up needs distillation, energy consumption is big, is unfavorable for energy-conservation
Reduce discharging；Reactor is used to drip MDP in ethanol in addition with report, with triethylamine or pyridine or ammonia as acid binding agent, due to
The restriction of reactor structure, this reaction needs to carry out under solvent condition, additionally due to MDP is unstable, easily with the alkalescence added
Material reacts under appropriate conditions, and on the one hand material loss is big, and cost of material sharply increases, on the other hand the receipts of product
Rate is low, affects the production of product, and then affects the normal production of company.
Summary of the invention
In order to overcome the defect of prior art, the invention provides a kind of glufosinate-ammonium intermediate methylisothiouronium methylphosphite diethylester
Synthetic method, uses tubular reactor to carry out additive reaction, and reaction raw materials can be not required to the charging of solvent direct seriality and prepare product
Methylisothiouronium methylphosphite diethylester, simplifies operating process, reduces production cost, beneficially energy-saving and emission-reduction.
The above-mentioned purpose of the present invention is achieved through the following technical solutions:
The synthetic method of a kind of glufosinate-ammonium intermediate methylisothiouronium methylphosphite diethylester, with MDP as raw material, in tubular reactor
It is summed into reaction with ethanol gas and obtains methylisothiouronium methylphosphite diethylester.
Further, described tubular reactor internal diameter is 32mm, and it is built with quartz sand filler, the MDP of gas phase and second
Alcohol contact in reactor after vigorous reaction generate liquid phase methylisothiouronium methylphosphite diethylester, after slow outflow reactor collect, gas
Tail gas absorption after phase ethanol and by-product hydrogen chloride outflow system.
Further, in described method, the pressure of methylisothiouronium methylphosphite diethylester synthetic reaction is 0.1-0.5MPa, passes through
Regulation gas evaporation amount and counterbalance valve control expellant gas amount and carry out regulation system pressure to improve selectivity of product.
Further, in described method, the temperature of methylisothiouronium methylphosphite diethylester synthetic reaction is 85-120 DEG C, and temperature is led to
The external heat set crossing tubular reactor controls.
Further, in described method, the liquid air speed of methylisothiouronium methylphosphite diethylester synthetic reaction is 0.6-12g h-1,
Reaction velocity is controlled by the inlet amount of regulation raw material.
Further, in described method, MDP and the ethanol raw materials components mole ratio of methylisothiouronium methylphosphite diethylester synthetic reaction are
1:(2-4)。
Compared with prior art, the beneficial effect comprise that:
1) synthetic method of the present invention, with MDP as raw material, generates methyl with ethanol gas phase reaction sub-in tubular reactor
Diethyl phosphate, simplifies operational process of craft, and linking is in order, greatly reduces cost of labor, has saved production cost；
2) present invention uses tubular reactor, changes the consersion unit using reactor in prior art, tubular reactor
It is possible not only to realize being rapidly separated of by-product hydrogen chloride and product, improves product yield, also achieve continuous operation simultaneously,
Avoid the danger in course of industrialization, eliminate potential safety hazard；
3) present invention is without solvent, decreases the processes such as follow-up distillation, reduces energy consumption, saved resource, reacted
Few refuse that journey produces, it is convenient to process, environmentally friendly.
Accompanying drawing explanation
The present invention is further described below in conjunction with the accompanying drawings.
Fig. 1 is the structural representation that synthetic method of the present invention uses tubular reactor.
Detailed description of the invention
Below in conjunction with three groups of comparative examples, the present invention is described in detail, in order to is better understood from the interior of the present invention
Hold, specific as follows:
As it is shown in figure 1, the synthetic effect of glufosinate-ammonium intermediate methylisothiouronium methylphosphite diethylester is adopted in embodiment of the present invention method
Being evaluated with tubular reactor, raw material and product use gas chromatogram to be analyzed, and are had by following three groups of embodiments
Body illustrates, numbered A, B and C.
First group:
Using internal diameter in the lab is the tubular reactor of 32mm, and loading quartz sand is filler, uses liquid phase to enter continuously
Material additive reaction, reaction pressure 0.2MPa, MDP and ethanol mol ratio 1:5, concrete data see table 1:
Second group:
Using internal diameter in the lab is the tubular reactor of 32mm, and loading quartz sand is filler, uses liquid phase to enter continuously
Material additive reaction, reaction pressure 0.3MPa, MDP and ethanol mol ratio 1:5, concrete data see table 2:
3rd group:
Using internal diameter in the lab is the tubular reactor of 32mm, and loading quartz sand is filler, uses liquid phase to enter continuously
Material additive reaction, reaction pressure 0.3MPa, MDP and ethanol mol ratio 1:10, concrete data see table 3:
Claims (6)
1. the synthetic method of a glufosinate-ammonium intermediate methylisothiouronium methylphosphite diethylester, it is characterised in that with MDP as raw material, at pipe
Formula reactor is summed into reaction obtains methylisothiouronium methylphosphite diethylester with ethanol gas.
The synthetic method of glufosinate-ammonium intermediate methylisothiouronium methylphosphite diethylester the most according to claim 1, it is characterised in that institute
The tubular reactor internal diameter stated is 32mm, and it is built with quartz sand filler, and the MDP of gas phase is acute after contacting in reactor with ethanol
The methylisothiouronium methylphosphite diethylester of strong reaction solution phase, collects after slow outflow reactor, gaseous ethanol and by-product hydrogen chloride stream
Go out tail gas absorption after system.
The synthetic method of glufosinate-ammonium intermediate methylisothiouronium methylphosphite diethylester the most according to claim 1, it is characterised in that institute
In the method stated, the pressure of methylisothiouronium methylphosphite diethylester synthetic reaction is 0.1-0.5MPa.
The synthetic method of glufosinate-ammonium intermediate methylisothiouronium methylphosphite diethylester the most according to claim 1, it is characterised in that institute
In the method stated, the temperature of methylisothiouronium methylphosphite diethylester synthetic reaction is 85-120 DEG C.
The synthetic method of glufosinate-ammonium intermediate methylisothiouronium methylphosphite diethylester the most according to claim 1, it is characterised in that institute
In the method stated, the liquid air speed of methylisothiouronium methylphosphite diethylester synthetic reaction is 0.6-12g h-1。
The synthetic method of glufosinate-ammonium intermediate methylisothiouronium methylphosphite diethylester the most according to claim 1, it is characterised in that institute
In the method stated, MDP and the ethanol raw materials components mole ratio of methylisothiouronium methylphosphite diethylester synthetic reaction are 1:(2-4).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610460721.XA CN106046051A (en) | 2016-06-21 | 2016-06-21 | Synthesis method of glufosinate intermediate of methyl diethyl phosphite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610460721.XA CN106046051A (en) | 2016-06-21 | 2016-06-21 | Synthesis method of glufosinate intermediate of methyl diethyl phosphite |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106046051A true CN106046051A (en) | 2016-10-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610460721.XA Pending CN106046051A (en) | 2016-06-21 | 2016-06-21 | Synthesis method of glufosinate intermediate of methyl diethyl phosphite |
Country Status (1)
| Country | Link |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111004281A (en) * | 2019-10-10 | 2020-04-14 | 利尔化学股份有限公司 | Continuous flow preparation method of diethyl methylphosphite |
| CN111004280A (en) * | 2019-10-10 | 2020-04-14 | 利尔化学股份有限公司 | Continuous flow preparation method of diethyl methylphosphite |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2903475A (en) * | 1956-04-16 | 1959-09-08 | Virginia Carolina Chem Corp | Production of esters of phosphonous and phosphinous acids |
| US4549995A (en) * | 1982-12-08 | 1985-10-29 | Hoechst Aktiengesellschaft | Process for making alkanephosphonous acid esters |
-
2016
- 2016-06-21 CN CN201610460721.XA patent/CN106046051A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2903475A (en) * | 1956-04-16 | 1959-09-08 | Virginia Carolina Chem Corp | Production of esters of phosphonous and phosphinous acids |
| US4549995A (en) * | 1982-12-08 | 1985-10-29 | Hoechst Aktiengesellschaft | Process for making alkanephosphonous acid esters |
Non-Patent Citations (2)
| Title |
|---|
| 尹志刚主编: "《有机磷化合物》", 31 March 2011 * |
| 庄建元 等: ""草铵膦国外工业化路线的探讨和启迪"", 《农药》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111004281A (en) * | 2019-10-10 | 2020-04-14 | 利尔化学股份有限公司 | Continuous flow preparation method of diethyl methylphosphite |
| CN111004280A (en) * | 2019-10-10 | 2020-04-14 | 利尔化学股份有限公司 | Continuous flow preparation method of diethyl methylphosphite |
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