CN107236001A - A kind of synthetic method of phosphine aldehyde - Google Patents
A kind of synthetic method of phosphine aldehyde Download PDFInfo
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- CN107236001A CN107236001A CN201610208423.1A CN201610208423A CN107236001A CN 107236001 A CN107236001 A CN 107236001A CN 201610208423 A CN201610208423 A CN 201610208423A CN 107236001 A CN107236001 A CN 107236001A
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- ethyl alcohol
- absolute ethyl
- synthetic method
- methacrylaldehyde
- phosphine aldehyde
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- -1 phosphine aldehyde Chemical class 0.000 title claims abstract description 63
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 42
- 238000010189 synthetic method Methods 0.000 title claims abstract description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 68
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 59
- STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 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 abstract description 36
- 229960000583 acetic acid Drugs 0.000 claims abstract description 34
- 239000012362 glacial acetic acid Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000002904 solvent Substances 0.000 claims abstract description 9
- 238000006243 chemical reaction Methods 0.000 claims description 27
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000011259 mixed solution Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 7
- 230000006378 damage Effects 0.000 abstract description 4
- 238000004821 distillation Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract 1
- IAJOBQBIJHVGMQ-UHFFFAOYSA-N 2-amino-4-[hydroxy(methyl)phosphoryl]butanoic acid Chemical compound CP(O)(=O)CCC(N)C(O)=O IAJOBQBIJHVGMQ-UHFFFAOYSA-N 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000003786 synthesis reaction Methods 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 5
- 238000009790 rate-determining step (RDS) Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 4
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- 239000005561 Glufosinate Substances 0.000 description 3
- 230000002363 herbicidal effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 150000001469 hydantoins Chemical class 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- HTSGKJQDMSTCGS-UHFFFAOYSA-N 1,4-bis(4-chlorophenyl)-2-(4-methylphenyl)sulfonylbutane-1,4-dione Chemical compound C1=CC(C)=CC=C1S(=O)(=O)C(C(=O)C=1C=CC(Cl)=CC=1)CC(=O)C1=CC=C(Cl)C=C1 HTSGKJQDMSTCGS-UHFFFAOYSA-N 0.000 description 1
- SVRWFDBCXSSJRD-UHFFFAOYSA-N 3-ethylidenepentane-2,4-dione Chemical group CC=C(C(C)=O)C(C)=O SVRWFDBCXSSJRD-UHFFFAOYSA-N 0.000 description 1
- 238000006150 Bucherer-Bergs reaction Methods 0.000 description 1
- JPFLNQBVZQXYRD-UHFFFAOYSA-N C(C)(=O)OC(C)=O.CC(C=O)=C Chemical compound C(C)(=O)OC(C)=O.CC(C=O)=C JPFLNQBVZQXYRD-UHFFFAOYSA-N 0.000 description 1
- AVXBTEZHGRNURI-UHFFFAOYSA-N CN=C(N)S.CN=C(N)S.COP(O)O Chemical compound CN=C(N)S.CN=C(N)S.COP(O)O AVXBTEZHGRNURI-UHFFFAOYSA-N 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- CDPKWOKGVUHZFR-UHFFFAOYSA-N dichloro(methyl)phosphane Chemical compound CP(Cl)Cl CDPKWOKGVUHZFR-UHFFFAOYSA-N 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HOCOIDRZLNGZMV-UHFFFAOYSA-N ethoxy(oxido)phosphanium Chemical compound CCO[PH2]=O HOCOIDRZLNGZMV-UHFFFAOYSA-N 0.000 description 1
- 244000037671 genetically modified crops Species 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002903 organophosphorus compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 230000009261 transgenic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/30—Phosphinic acids [R2P(=O)(OH)]; Thiophosphinic acids ; [R2P(=X1)(X2H) (X1, X2 are each independently O, S or Se)]
- C07F9/32—Esters thereof
- C07F9/3205—Esters thereof the acid moiety containing a substituent or a structure which is considered as characteristic
- C07F9/3211—Esters of acyclic saturated acids which can have further substituents on alkyl
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of synthetic method of phosphine aldehyde, using absolute ethyl alcohol as solvent, using glacial acetic acid, methacrylaldehyde and methylisothiouronium methylphosphite diethylester as raw material, phosphine aldehyde is made after blended, heating, distillation.The more Japanese Mingzhi Fruit patent yields of this method are significantly improved, up to 93.3%, close to the product yield of Hoechst patents, while turn avoid safety and the employment injuries that generation ether is brought, meet clean manufacturing requirement, with preferable practicality.
Description
Technical field
The present invention is a kind of synthetic method of phosphine aldehyde, and in particular to glufosinate-ammonium intermediate methyl-（3- oxo-propylls）Phosphinicacid ethyl ester（Referred to as " phosphine aldehyde "）Synthetic method, belong to organic phosphine chemosynthesis technical field.
Background technology
Phosphine aldehyde is a kind of intermediate for synthesizing organic phosphorus compound, is also herbicide glufosinate-ammonium (glufosinate) important intermediate.Glufosinate-ammonium is the preferable herbicide of transgenic resistance crop, with efficient, low toxicity and the characteristics of wide herbicidal spectrum.With the fast development of genetically modified crops, such as transgenosis glufosinate-resistant paddy rice, transgenosis glufosinate-resistant soybean, the market demand of glufosinate-ammonium also increases sharply.The chemical property of phosphine aldehyde is active, easily with the water and oxygen reaction in air, easy spontaneous combustion, and hardly possible storage, in the market can not be directly commercially available.Therefore, as the phosphine aldehyde of synthesis glufosinate-ammonium key intermediate, it, which is researched and developed, has wide market prospects.
There are the preparation method of more document report phosphine aldehyde in foreign countries, for example：First phosphine aldehyde is made with the reaction of methylisothiouronium methylphosphite diethylester again with ethanol generation acetal in Mingzhi's Fruit patents methacrylaldehyde, but yield is low；Hoechst patents are using aceticanhydride methacrylaldehyde and methylisothiouronium methylphosphite diethylester as raw material; aceticanhydride first reacts generation diacetyl propylene with methacrylaldehyde; again with methylisothiouronium methylphosphite diethylester addition; acetyl group is removed again obtains phosphine aldehyde; there is higher recovery rate, but there are problems that product has ether to bring safety and employment injuries.
Domestic literature is also disclosed the preparation method of phosphine aldehyde, for example：Patent document CN103396440A（A kind of preparation method of glufosinate-ammonium, 2013.11.20）A kind of new preparation process of the glufosinate-ammonium proposed, methyl acid phosphate lipoid substance IV is made with methyl dichloro phosphorus and alcohol reaction, methyl propionaldehyde phosphate compounds II are made with acrolein reaction again in methyl acid phosphate lipoid substance IV, the hydantoin derivative shown in formula III is made by Bucherer-Bergs ring-closure reactions for methyl propionaldehyde phosphonate ester type compound II, hydantoin derivative again by hydrolysis be made formula I shown in glufosinate-ammonium compound, with mild condition, easily detection, raw material is easy to get, cost is low, product yield high, high purity the features such as.
The content of the invention
It is an object of the invention to provide a kind of synthetic method of phosphine aldehyde, the more Japanese Mingzhi Fruit patent yields of this method are significantly improved, up to 93.3%, close to the product yield of Hoechst patents, safety and employment injuries that generation ether is brought are turn avoid simultaneously, meet clean manufacturing requirement, with preferable practicality
The present invention is achieved through the following technical solutions：A kind of synthetic method of phosphine aldehyde, using absolute ethyl alcohol as solvent, using glacial acetic acid, methacrylaldehyde and methylisothiouronium methylphosphite diethylester as raw material, is made phosphine aldehyde after blended, back flow reaction.
The invention provides one kind in high yield, the synthetic method of the high phosphine aldehyde of production safety coefficient, making solvent using absolute ethyl alcohol can be such that reaction balances to positive reaction, reaction rate be improved, while saving the reaction time.
The phosphine aldehyde of acquisition can be directly used for glufosinate-ammonium synthesis procedure or be re-fed into glufosinate-ammonium synthesis procedure after the phosphine aldehyde of acquisition to be removed to the ethanol and ethyl acetate in course of reaction through distillation.
The mixing includes：
A：Absolute ethyl alcohol and glacial acetic acid are added in a reservoir, add methylisothiouronium methylphosphite diethylester, mixed solution is obtained after stirring, it is standby；
B：Absolute ethyl alcohol and methacrylaldehyde are added in another container, is stirred, and the mixed solution made from dropwise addition step A in whipping process.
Control in the step A, the mixing temperature of absolute ethyl alcohol, glacial acetic acid and methylisothiouronium methylphosphite diethylester is -10~15 DEG C.
Absolute ethyl alcohol is added in the step B, in another container and the mol ratio of methacrylaldehyde is（5~15）：1, preferably（10~15）：1.
Control temperature≤40 DEG C of the step B.
The back flow reaction includes：It is to be mixed finish after, persistently stir 15~30min, be to slowly warm up to backflow, keep 70~75 DEG C at a temperature of flow back 30~90 min.
Methylisothiouronium methylphosphite diethylester ethanol, ethanol acetate liquid and methacrylaldehyde ethanol are prepared respectively, and methylisothiouronium methylphosphite diethylester ethanol and ethanol acetate liquid are added dropwise into methacrylaldehyde ethanol simultaneously.
In the raw material, the mol ratio of glacial acetic acid, absolute ethyl alcohol and methylisothiouronium methylphosphite diethylester is（1~1.5）：（3~40）：1.
The present invention compared with prior art, with advantages below and beneficial effect：
（1）The present invention controls the mixing temperature of absolute ethyl alcohol, glacial acetic acid and methylisothiouronium methylphosphite diethylester at -10~15 DEG C, can suppress the generation of side reaction, improves reaction efficiency.
（2）The present invention exists the mol ratio control of glacial acetic acid, absolute ethyl alcohol and methylisothiouronium methylphosphite diethylester（1~1.5）：（3~40）：1, be conducive to improving phosphine aldehyde yield.
（3）The present invention is using absolute ethyl alcohol, glacial acetic acid, methacrylaldehyde and methylisothiouronium methylphosphite diethylester as reaction raw materials, nothing brings safety and the hidden danger of employment injuries in product, the phosphine aldehyde of acquisition can be directly used for glufosinate-ammonium synthesis procedure or be re-fed into glufosinate-ammonium synthesis procedure after the phosphine aldehyde of acquisition to be removed to the ethanol and ethyl acetate in course of reaction through distillation, and operating process is simple and easy to control.
Embodiment
The present invention is described in further detail with reference to embodiment, but the implementation of the present invention is not limited to this.
Embodiment 1：
A kind of synthetic method of phosphine aldehyde, using absolute ethyl alcohol as solvent, using glacial acetic acid, methacrylaldehyde and methylisothiouronium methylphosphite diethylester as raw material, is made phosphine aldehyde after blended, back flow reaction.
The phosphine aldehyde obtained by this method can be directly used for glufosinate-ammonium synthesis procedure or be re-fed into glufosinate-ammonium synthesis procedure after the phosphine aldehyde of acquisition to be removed to the ethanol and ethyl acetate in course of reaction through distillation.
Embodiment 2：
The present embodiment is that mixed process in embodiment 1 is further described, and the concrete operations of mixing can be：Using absolute ethyl alcohol as solvent, methylisothiouronium methylphosphite diethylester ethanol, ethanol acetate liquid and methacrylaldehyde ethanol are made respectively, methylisothiouronium methylphosphite diethylester ethanol, ethanol acetate liquid are added dropwise into methacrylaldehyde ethanol simultaneously.
In mixed process, the mol ratio of glacial acetic acid, absolute ethyl alcohol and methylisothiouronium methylphosphite diethylester is controlled 1： 40：1.
Embodiment 3：
The present embodiment and the difference of embodiment 2 are that the concrete operations of mixing are different, and in the present embodiment, blend step includes：
A：Absolute ethyl alcohol and glacial acetic acid are added in a reservoir, add methylisothiouronium methylphosphite diethylester, mixed solution is obtained after stirring, it is standby；
B：Absolute ethyl alcohol and methacrylaldehyde are added in another container, is stirred, and the mixed solution made from dropwise addition step A in whipping process.
In mixed process, the mol ratio of glacial acetic acid, absolute ethyl alcohol and methylisothiouronium methylphosphite diethylester is controlled 1.5： 3：1.
Embodiment 4：
The present embodiment is proposed on the basis of embodiment 3, in the step A that the present embodiment is related to, and the mixing temperature of absolute ethyl alcohol, glacial acetic acid and methylisothiouronium methylphosphite diethylester is controlled at -10 DEG C.
Embodiment 5：
The present embodiment is proposed on the basis of embodiment 3, in the step B that the present embodiment is related to, and the mol ratio that absolute ethyl alcohol and methacrylaldehyde are added in another container is 5：1.
Embodiment 6：
The present embodiment is proposed on the basis of embodiment 3, and rate-determining steps B temperature is 40 DEG C.
Embodiment 7：
The present embodiment is that mixed process in embodiment 1 is further described, and back flow reaction includes：It is to be mixed finish after, persistently stir 15min, be to slowly warm up to backflow, keep flowing back 30 min at a temperature of 70 DEG C.
Embodiment 8：
The present embodiment is related to a kind of synthetic method of phosphine aldehyde, using absolute ethyl alcohol as solvent, using glacial acetic acid, methacrylaldehyde and methylisothiouronium methylphosphite diethylester as raw material, methylisothiouronium methylphosphite diethylester ethanol, ethanol acetate liquid and methacrylaldehyde ethanol are made respectively, methylisothiouronium methylphosphite diethylester ethanol, ethanol acetate liquid are added dropwise into methacrylaldehyde ethanol simultaneously, after above-mentioned raw materials are mixed, phosphine aldehyde is made after back flow reaction.
In mixed process, the mol ratio of glacial acetic acid, absolute ethyl alcohol and methylisothiouronium methylphosphite diethylester is controlled 1.5：20：1.
In back flow reaction, after completion of dropping to be mixed, 30min is persistently stirred, backflow is to slowly warm up to, the 80min that flowed back at a temperature of 75 DEG C is kept.
Embodiment 8：
The present embodiment is related to a kind of synthetic method of phosphine aldehyde, using absolute ethyl alcohol as solvent, using glacial acetic acid, methacrylaldehyde and methylisothiouronium methylphosphite diethylester as raw material, methylisothiouronium methylphosphite diethylester ethanol, ethanol acetate liquid and methacrylaldehyde ethanol are made respectively, methylisothiouronium methylphosphite diethylester ethanol, ethanol acetate liquid are added dropwise into methacrylaldehyde ethanol simultaneously, after above-mentioned raw materials are mixed, phosphine aldehyde is made after back flow reaction.
In mixed process, the mol ratio of glacial acetic acid, absolute ethyl alcohol and methylisothiouronium methylphosphite diethylester is controlled 1.2：18：1.
In back flow reaction, after completion of dropping to be mixed, 28min is persistently stirred, backflow is to slowly warm up to, the 85min that flowed back at a temperature of 72 DEG C is kept.
Embodiment 9：
A kind of synthetic method of phosphine aldehyde, using absolute ethyl alcohol as solvent, using glacial acetic acid, methacrylaldehyde and methylisothiouronium methylphosphite diethylester as raw material, is made phosphine aldehyde after blended, back flow reaction.
Blend step includes：
A：Absolute ethyl alcohol and glacial acetic acid are added in a reservoir, add methylisothiouronium methylphosphite diethylester, mixed solution is obtained after stirring, it is standby, wherein, the mixing temperature of absolute ethyl alcohol, glacial acetic acid and methylisothiouronium methylphosphite diethylester is controlled at 15 DEG C；
B：It is 15 that mol ratio is added in another container：1 absolute ethyl alcohol and methacrylaldehyde, stirs, and mixed solution made from step A is added dropwise in whipping process, and rate-determining steps B temperature is 36 DEG C.
In mixed process, the mol ratio of glacial acetic acid, absolute ethyl alcohol and methylisothiouronium methylphosphite diethylester is controlled 1.4：16：1.
In back flow reaction, after completion of dropping to be mixed, 28min is persistently stirred, backflow is to slowly warm up to, 65 min that flowed back at a temperature of 70 DEG C are kept.
Embodiment 10：
A：Absolute ethyl alcohol and glacial acetic acid are added in a reservoir, add methylisothiouronium methylphosphite diethylester, mixed solution is obtained after stirring, it is standby, wherein, the mixing temperature of absolute ethyl alcohol, glacial acetic acid and methylisothiouronium methylphosphite diethylester is controlled at -5 DEG C；
B：It is 10 that mol ratio is added in another container：1 absolute ethyl alcohol and methacrylaldehyde, stirs, and mixed solution made from step A is added dropwise in whipping process, and rate-determining steps B temperature is 40 DEG C.
In mixed process, the mol ratio of glacial acetic acid, absolute ethyl alcohol and methylisothiouronium methylphosphite diethylester is controlled 1：35：1.
In back flow reaction, after completion of dropping to be mixed, 20min is persistently stirred, backflow is to slowly warm up to, 70 min that flowed back at a temperature of 75 DEG C are kept.
Embodiment 11：
A：Absolute ethyl alcohol and glacial acetic acid are added in a reservoir, add methylisothiouronium methylphosphite diethylester, mixed solution is obtained after stirring, it is standby, wherein, the mixing temperature of absolute ethyl alcohol, glacial acetic acid and methylisothiouronium methylphosphite diethylester is controlled at 5 DEG C；
B：It is 12 that mol ratio is added in another container：1 absolute ethyl alcohol and methacrylaldehyde, stirs, and mixed solution made from step A is added dropwise in whipping process, and rate-determining steps B temperature is 35 DEG C.
In mixed process, the mol ratio of glacial acetic acid, absolute ethyl alcohol and methylisothiouronium methylphosphite diethylester is controlled 1.5：25：1.
In back flow reaction, after completion of dropping to be mixed, 28min is persistently stirred, backflow is to slowly warm up to, 90 min that flowed back at a temperature of 75 DEG C are kept.
Embodiment 12：
A：Absolute ethyl alcohol and glacial acetic acid are added in a reservoir, add methylisothiouronium methylphosphite diethylester, mixed solution is obtained after stirring, it is standby, wherein, the mixing temperature of absolute ethyl alcohol, glacial acetic acid and methylisothiouronium methylphosphite diethylester is controlled at 15 DEG C；
B：It is 14 that mol ratio is added in another container：1 absolute ethyl alcohol and methacrylaldehyde, stirs, and mixed solution made from step A is added dropwise in whipping process, and rate-determining steps B temperature is 40 DEG C.
In mixed process, the mol ratio of glacial acetic acid, absolute ethyl alcohol and methylisothiouronium methylphosphite diethylester is controlled 1.3：22：1.
In back flow reaction, after completion of dropping to be mixed, 24min is persistently stirred, backflow is to slowly warm up to, 50 min that flowed back at a temperature of 70 DEG C are kept.
It is described above, only it is presently preferred embodiments of the present invention, any formal limitation is not done to the present invention, every any simple modification made according to technical spirit of the invention to above example, equivalent variations are each fallen within protection scope of the present invention.
Claims (8)
1. a kind of synthetic method of phosphine aldehyde, it is characterised in that：Using absolute ethyl alcohol as solvent, using glacial acetic acid, methacrylaldehyde and methylisothiouronium methylphosphite diethylester as raw material, phosphine aldehyde is made after blended, back flow reaction.
2. a kind of synthetic method of phosphine aldehyde according to claim 1, it is characterised in that：The mixing includes：
A：Absolute ethyl alcohol and glacial acetic acid are added in a reservoir, add methylisothiouronium methylphosphite diethylester, mixed solution is obtained after stirring, it is standby；
B：Absolute ethyl alcohol and methacrylaldehyde are added in another container, is stirred, and the mixed solution made from dropwise addition step A in whipping process.
3. a kind of synthetic method of phosphine aldehyde according to claim 2, it is characterised in that：Control in the step A, the mixing temperature of absolute ethyl alcohol, glacial acetic acid and methylisothiouronium methylphosphite diethylester is -10~15 DEG C.
4. a kind of synthetic method of phosphine aldehyde according to claim 2, it is characterised in that：Absolute ethyl alcohol is added in the step B, in another container and the mol ratio of methacrylaldehyde is（5~15）：1.
5. a kind of synthetic method of phosphine aldehyde according to claim 2, it is characterised in that：Control temperature≤40 DEG C of the step B.
6. a kind of synthetic method of phosphine aldehyde according to claim 1, it is characterised in that：Described mixing includes：The back flow reaction includes：It is to be mixed finish after, persistently stir 15~30min, be to slowly warm up to backflow, keep 70~75 DEG C at a temperature of flow back 30~90
min。
7. a kind of synthetic method of phosphine aldehyde according to claim 1, it is characterised in that：Described mixing includes：Methylisothiouronium methylphosphite diethylester ethanol, ethanol acetate liquid and methacrylaldehyde ethanol are prepared respectively, and methylisothiouronium methylphosphite diethylester ethanol and ethanol acetate liquid are added dropwise into methacrylaldehyde ethanol simultaneously.
8. according to a kind of any one of claim 1 or 7 synthetic method of phosphine aldehyde, it is characterised in that：In the raw material, the mol ratio of glacial acetic acid, absolute ethyl alcohol and methylisothiouronium methylphosphite diethylester is（1~1.5）：（3~40）：1.
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|---|---|---|---|---|
| US4264532A (en) * | 1977-12-19 | 1981-04-28 | Takashi Tsuruoka | Process for preparing D,L-2-amino-4-methylphosphinobutyric acid |
| CN1261442C (en) * | 1997-08-20 | 2006-06-28 | 赫彻斯特-舍林农业发展有限公司 | Method and intermediate for preparing glufosinate |
| CN1858054A (en) * | 2005-10-17 | 2006-11-08 | 浙江大学 | Process for preparing phosphine oxamate and its derivatives |
| CN103396440A (en) * | 2013-08-23 | 2013-11-20 | 重庆紫光化工股份有限公司 | Preparation method of glufosinate-ammonium |
| CN105001259A (en) * | 2015-07-28 | 2015-10-28 | 河北威远生化农药有限公司 | Technology and equipment for continuously producing 3-(methyl hydroxyl phosphonyl) propionaldehyde |
-
2016
- 2016-04-06 CN CN201610208423.1A patent/CN107236001A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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