CN101418013A - Process for preparing intermediate ethyl methyl propionaldehyde phosphonate - Google Patents
Process for preparing intermediate ethyl methyl propionaldehyde phosphonate Download PDFInfo
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- CN101418013A CN101418013A CNA2008101537456A CN200810153745A CN101418013A CN 101418013 A CN101418013 A CN 101418013A CN A2008101537456 A CNA2008101537456 A CN A2008101537456A CN 200810153745 A CN200810153745 A CN 200810153745A CN 101418013 A CN101418013 A CN 101418013A
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- phosphonate
- methyl
- propionaldehyde
- diethyl
- ethyl methyl
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Abstract
The invention provides a process for preparing methyl oxopropyl ethyl methyl phosphonate intermediate. The process comprises the following steps: diethyl methyldiethoxypropyl phosphonate is prepared by the synthetic reaction of pdiethyl methyl-phoshphonite and 3-bromodiethoxypropane and reduced pressure distillation; the obtained diethyl methyldiethoxypropyl phosphonate is subjected to acidification and hydrolization to give the methyl oxopropyl ethyl methyl phosphonate. The invention has the advantages of simple process, low preparation cost, strong practicality, suitability for industrial production, and significance for large-scale development and utilization of glufosinate-ammonium herbicide.
Description
(1) technical field
The present invention relates to the preparation technology of organic phosphates weedicide grass ammonium phosphine, particularly a kind of preparation technology of ethyl methyl propionaldehyde phosphonate intermediate.
(2) background technology
Grass ammonium phosphine (glufosinate-ammonium or glufosinate) is a kind of efficient, low toxicity, non-selective (property killed) contact killing type organic phosphates weedicide with part systemic action, it is a racemic mixture, developed at first by German Hoechst company, commodity are called Basta.The effective constituent of grass ammonium phosphine is phosphinothricin (being called for short PPT), and chemical formula is C
5H
12NO
4P, soluble in water, be not soluble in organic solvent, stable to light; Facile hydrolysis in the aqueous solution of pH=5～9.Grass ammonium phosphine comprises: DL-type, its fusing point are 229～231 ℃; L type, its fusing point are 214～216 ℃; Wherein have only L-type grass ammonium phosphine to have phytotoxicity, its weeding activity is 2 times of racemic mixture, and the target enzyme is glutamine synthetase (GS).Effective constituent PPT in the grass ammonium phosphine can suppress all known form of GS, and the result of inhibition GS can cause the excess accumulation of nitrogen metabolism disorder in the plant materials, ammonia, chloroplast(id) to disintegrate, thereby makes photosynthesis be subjected to press down, and finally causes plant death.Grass ammonium phosphine toxicity is low, use safer, be easy to degraded in soil, to crop safety, it is little to drift about, herbicidal spectrum is wide, active high, consumption is few, and environmental stress is little, kill grass rapidly, can prevent and kill off or kill fast annual or perennial dicotyledonous broad-leaved or the gramineous weedss more than 100 kinds such as lady's-grass, rye grass.Used water is made base (solvent), and is safe and convenient to use.Grass ammonium phosphine is not transferred to other places because its drug effect is only conducted in cotyledon, can not work by root to the plant of being unearthed, so its poisoning is less, and through the soil that careless ammonium phosphine was handled, sows all kinds of plants subsequently, and its growth can be not influenced yet.This shows, the development and use of careless ammonium phosphine are seemed extremely important.
Development, exploitation and the application of grass ammonium phosphine, closely related with the conclusive evidence of the discovery of bialaphos (bialaphos) and structure thereof.Bialaphos is the natural antibiotics of isolated a kind of tripeptides class from the fermented liquid of soil actinomycete or streptomycete (streptomyces hygroscopicus), it is a kind of analogue of L-glutamic acid, itself does not have weeding activity, but can be the careless ammonium phosphine with weeding activity at the plant materials intracellular metabolite.Take a broad view of the document patent report of relevant careless ammonium phosphine both at home and abroad, except that available two third ammonia phosphorus through microbial fermentation is produced careless ammonium phosphine, also can adopt synthetic method production, its synthetic method is a raw material with phosphorus trichloride or phosphinate usually, phosphonic acid ester is synthesized in after chemical reaction, and then takes place to answer with aminoderivative; Because careless ammonium phosphine itself promptly is a seed amino acid, therefore also can phosphinate with the olefine aldehydr reaction after utilize Strecker to react again, or will utilize synthetic careless ammonium phosphine such as Gaburial reaction behind the derivatives reaction of phosphonic acid ester and diethyl malonate again.At present, the method that adopts synthesis method to prepare careless ammonium phosphine mainly comprises: and the high pressure catalysis synthesis process (US 4,906, and 764; The flat 2-184692 of JPN; EP0,292,918), the directed synthesis method of low temperature (US 4,779,279; EP 0,127, and 429; Ger Offen 4,407,197), (spy opens clear 48-91019 to the synthetic careless ammonium phosphine of bromination; Agricultural chemicals, 2001,40 (4), 15), this special tired Ke Er prepared in reaction grass ammonium phosphine method (WO79/00405; Gauszecka.Ewa, Roxz.Chem.1975,49 (12), 2127-8), close your (MICHAEL) additive process (Eur, Pat.Appl 83/92,448 (From CA 102:P185488); India J.chem.197311 (11), 1205-1206).Prepare in the method for careless ammonium phosphine in above-mentioned employing synthesis method, except that this special tired Ke Er prepared in reaction grass ammonium phosphine method, all there is expensive raw material price in other method, needs the shortcomings such as condition of high pressure, high temperature or extreme low temperature, is unsuitable for suitability for industrialized production.
The tired Ke Er prepared in reaction grass of Si Te ammonium phosphine method is present mature methods, and its synthesis technique can be represented with following reaction formula:
In this synthesis technique, the intermediate ethyl methyl propionaldehyde phosphonate is the key of synthetic careless ammonium phosphine, in view of such weedicide is badly in need of in China, therefore develops the careless ammonium phosphine synthesis technique with independent intellectual property right and has important practical significance.
(3) summary of the invention
The objective of the invention is problem, provide that a kind of technology is simple, preparation cost is low, the preparation technology of practical, the intermediate ethyl methyl propionaldehyde phosphonate that is suitable for suitability for industrialized production at above-mentioned existence.
Technical scheme of the present invention:
A kind of preparation technology of intermediate ethyl methyl propionaldehyde phosphonate comprises two processing steps: 1) utilize the contract building-up reactions of propionic aldehyde of methyl phosphonous acid diethyl ester and 3-bromine diethyl, and make the methyl diethyl propionaldehyde phosphonate ethyl ester that contracts through underpressure distillation; 2) the methyl diethyl that makes is contracted propionaldehyde phosphonate ethyl ester carries out the acidification hydrolization reaction and makes ethyl methyl propionaldehyde phosphonate in solvent.
The processing parameter of described building-up reactions is: temperature of reaction is 50～170 ℃, and the reaction times is 3～10 hours; The contract mol ratio of propionic aldehyde of methyl phosphonous acid diethyl ester and 3-bromine diethyl is 1:0.5～5.
Described solvent is acetone and 6N hydrochloric acid, and the contract mass ratio of propionaldehyde phosphonate ethyl ester, acetone, 6N hydrochloric acid of methyl diethyl is 1:1:1～10.
The temperature of reaction of described acidification hydrolization is 25～100 ℃.
Technological principle of the present invention can be represented by following chemical equation:
Advantage of the present invention is: technology is simple, preparation cost is low, practical, is suitable for suitability for industrialized production, to China's large-scale development with utilize Effictive nuisancelless grass ammonium phosphine weedicide, has important practical significance.
(4) embodiment
Embodiment 1:
1) the methyl diethyl preparation of propionaldehyde phosphonate ethyl ester of contracting
The 3-bromine diethyl propionic aldehyde that contracts is mixed with the methyl-phosphorous acid diethyl ester of 4 times of molar weights, and in 160 ℃ of reactions 8 hours, underpressure distillation made the methyl diethyl propionaldehyde phosphonate ethyl ester that contracts, yield 40%, boiling point 120-124 ℃/8mmHg.Nuclear magnetic data is,
1HNMR (CDCl
3, δ ppm): 1.14 (m, 6H),, 1.26 (t, 3H), 1.39 (d, 3H), 1.65-1.95 (m, 4H), 3.44 (q, 2H), 3.60 (q, 2H), 3.99 (t, 2H), 4.44 (t, 1H);
2) preparation of ethyl methyl propionaldehyde phosphonate
The methyl diethyl that quality such as adds in reaction flask contract propionic aldehyde phosphinic acid ethyl ester, acetone, 6N hydrochloric acid feed nitrogen, and 95 ℃ of reactions were used CH after 2.5 hours
2Cl
2, drying concentrates, and gets the weak yellow liquid ethyl methyl propionaldehyde phosphonate, yield 41%.Nuclear magnetic data is,
1H NMR (CDCl
3, δ ppm): 1.30 (t, 3H),, 1.48 (d, 3H), 2.03 (m, 2H), 2.80 (m, 2H), 4.04 (q, 2H), 9.80 (s, 1H).
Embodiment 2:
1) the methyl diethyl preparation of propionaldehyde phosphonate ethyl ester of contracting
The 3-bromine diethyl propionic aldehyde that contracts is mixed with the methyl-phosphorous acid diethyl ester of equimolar amount, and in 160 ℃ of reactions 8 hours, underpressure distillation made the methyl diethyl propionaldehyde phosphonate ethyl ester that contracts, yield 36%, boiling point 120-124 ℃/8mmHg;
2) preparation of ethyl methyl propionaldehyde phosphonate
The methyl diethyl that quality such as adds in the reaction flask 6N hydrochloric acid of propionic aldehyde phosphinic acid ethyl ester, acetone and 8 times of amounts that contracts feeds nitrogen, and 95 ℃ of reactions were used CH after 2.5 hours
2Cl
2, drying concentrates, and gets the weak yellow liquid ethyl methyl propionaldehyde phosphonate, yield 44%.
Embodiment 3:
1) the methyl diethyl preparation of propionaldehyde phosphonate ethyl ester of contracting
The 3-bromine diethyl propionic aldehyde that contracts is mixed with the methyl-phosphorous acid diethyl ester of equimolar amount, and in 60 ℃ of reactions 4 hours, underpressure distillation made the methyl diethyl propionaldehyde phosphonate ethyl ester that contracts, yield 38%, boiling point 120-124 ℃/8mmHg;
2) preparation of ethyl methyl propionaldehyde phosphonate
The methyl diethyl that quality such as adds in the reaction flask 6N hydrochloric acid of propionic aldehyde phosphinic acid ethyl ester, acetone and 8 times of amounts that contracts feeds nitrogen, and 35 ℃ of reactions were used CH after 2.5 hours
2Cl
2, drying concentrates, and gets the weak yellow liquid ethyl methyl propionaldehyde phosphonate, yield 44%.
Embodiment 4:
1) the methyl diethyl preparation of propionaldehyde phosphonate ethyl ester of contracting
The 3-bromine diethyl propionic aldehyde that contracts is mixed with the methyl-phosphorous acid diethyl ester of equimolar amount, and in 80 ℃ of reactions 6 hours, underpressure distillation made the methyl diethyl propionaldehyde phosphonate ethyl ester that contracts, yield 45%, boiling point 120-124 ℃/8mmHg;
2) preparation of ethyl methyl propionaldehyde phosphonate
The methyl diethyl that quality such as adds in reaction flask contract propionic aldehyde phosphinic acid ethyl ester, acetone, 6N hydrochloric acid feed nitrogen, and 95 ℃ of reactions were used CH after 2.5 hours
2Cl
2, drying concentrates, and gets the weak yellow liquid ethyl methyl propionaldehyde phosphonate, yield 41%.
Claims (4)
1. the preparation technology of an intermediate ethyl methyl propionaldehyde phosphonate is characterized in that: comprise two processing steps:
1) utilizes the contract building-up reactions of propionic aldehyde of methyl phosphonous acid diethyl ester and 3-bromine diethyl, and make the methyl diethyl propionaldehyde phosphonate ethyl ester that contracts through underpressure distillation;
2) the methyl diethyl that makes is contracted propionaldehyde phosphonate ethyl ester carries out the acidification hydrolization reaction and makes ethyl methyl propionaldehyde phosphonate in solvent.
2. the preparation technology of intermediate ethyl methyl propionaldehyde phosphonate according to claim 1 is characterized in that: the processing parameter of described building-up reactions is: temperature of reaction is 50～170 ℃, and the reaction times is 3～10 hours; The contract mol ratio of propionic aldehyde of methyl phosphonous acid diethyl ester and 3-bromine diethyl is 1:0.5～5.
3. the preparation technology of intermediate ethyl methyl propionaldehyde phosphonate according to claim 1 is characterized in that: described solvent is acetone and 6N hydrochloric acid, and the contract mass ratio of propionaldehyde phosphonate ethyl ester, acetone, 6N hydrochloric acid of methyl diethyl is 1:1:1～10.
4. the preparation technology of intermediate ethyl methyl propionaldehyde phosphonate according to claim 1 is characterized in that: the temperature of reaction of described acidification hydrolization is 25～100 ℃.
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| CNA2008101537456A CN101418013A (en) | 2008-12-05 | 2008-12-05 | Process for preparing intermediate ethyl methyl propionaldehyde phosphonate |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497039A (en) * | 2014-12-23 | 2015-04-08 | 利尔化学股份有限公司 | Preparation method of amino-nitrile and intermediate for preparing glufosinate-ammonium |
| CN105044224A (en) * | 2015-05-11 | 2015-11-11 | 石家庄瑞凯化工有限公司 | Detection method of 3-(1-methylethoxylphosphityl)-propanal |
| CN107286191A (en) * | 2017-04-16 | 2017-10-24 | 内蒙古佳瑞米精细化工有限公司 | A kind of preparation method of glufosinate-ammonium intermediate ethyl methyl propionaldehyde phosphonate |
| CN109134534A (en) * | 2018-08-08 | 2019-01-04 | 江苏好收成韦恩农化股份有限公司 | A kind of 3,3- dialkyloxypropyl methyl phosphonate simple preparation method |
| CN109879910A (en) * | 2018-10-22 | 2019-06-14 | 江苏长青农化股份有限公司 | A kind of preparation method of glufosinate-ammonium intermediate |
-
2008
- 2008-12-05 CN CNA2008101537456A patent/CN101418013A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104497039A (en) * | 2014-12-23 | 2015-04-08 | 利尔化学股份有限公司 | Preparation method of amino-nitrile and intermediate for preparing glufosinate-ammonium |
| CN105044224A (en) * | 2015-05-11 | 2015-11-11 | 石家庄瑞凯化工有限公司 | Detection method of 3-(1-methylethoxylphosphityl)-propanal |
| CN105044224B (en) * | 2015-05-11 | 2017-03-15 | 石家庄瑞凯化工有限公司 | A kind of detection method of 3 (1 methyl ethoxy phosphorous acyl group) propionic aldehyde |
| CN107286191A (en) * | 2017-04-16 | 2017-10-24 | 内蒙古佳瑞米精细化工有限公司 | A kind of preparation method of glufosinate-ammonium intermediate ethyl methyl propionaldehyde phosphonate |
| CN109134534A (en) * | 2018-08-08 | 2019-01-04 | 江苏好收成韦恩农化股份有限公司 | A kind of 3,3- dialkyloxypropyl methyl phosphonate simple preparation method |
| WO2019034182A1 (en) * | 2018-08-08 | 2019-02-21 | 江苏好收成韦恩农化股份有限公司 | Simple preparation method for dialkoxypropyl methylphosphonate |
| CN109134534B (en) * | 2018-08-08 | 2020-09-08 | 江苏好收成韦恩农化股份有限公司 | Simple preparation method of 3, 3-dialkoxy propyl methylphosphonate |
| CN109879910A (en) * | 2018-10-22 | 2019-06-14 | 江苏长青农化股份有限公司 | A kind of preparation method of glufosinate-ammonium intermediate |
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Open date: 20090429 |