CN109776605B - Synthesis method of glufosinate-ammonium - Google Patents
Synthesis method of glufosinate-ammonium Download PDFInfo
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- CN109776605B CN109776605B CN201910042722.6A CN201910042722A CN109776605B CN 109776605 B CN109776605 B CN 109776605B CN 201910042722 A CN201910042722 A CN 201910042722A CN 109776605 B CN109776605 B CN 109776605B
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- glufosinate
- ammonium
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- isonitrile
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- 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 33
- 238000001308 synthesis method Methods 0.000 title claims abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 62
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 32
- -1 3-methyl n-butoxy phosphono propionaldehyde Chemical compound 0.000 claims abstract description 22
- 239000002904 solvent Substances 0.000 claims abstract description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 14
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 8
- 150000002527 isonitriles Chemical class 0.000 claims abstract description 8
- 230000007062 hydrolysis Effects 0.000 claims abstract description 4
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 27
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 11
- 239000005561 Glufosinate Substances 0.000 claims description 4
- YFTRHHTUIXPTLJ-UHFFFAOYSA-N 1-isocyano-2,4-dimethylbenzene Chemical compound CC1=CC=C([N+]#[C-])C(C)=C1 YFTRHHTUIXPTLJ-UHFFFAOYSA-N 0.000 claims description 3
- DNJLFZHMJDSJFN-UHFFFAOYSA-N 2-isocyano-1,3-dimethylbenzene Chemical compound CC1=CC=CC(C)=C1[N+]#[C-] DNJLFZHMJDSJFN-UHFFFAOYSA-N 0.000 claims description 3
- BHXFKXOIODIUJO-UHFFFAOYSA-N benzene-1,4-dicarbonitrile Chemical compound N#CC1=CC=C(C#N)C=C1 BHXFKXOIODIUJO-UHFFFAOYSA-N 0.000 claims description 3
- RCIBIGQXGCBBCT-UHFFFAOYSA-N phenyl isocyanide Chemical group [C-]#[N+]C1=CC=CC=C1 RCIBIGQXGCBBCT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 7
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 abstract description 6
- 231100000167 toxic agent Toxicity 0.000 abstract description 3
- 239000003440 toxic substance Substances 0.000 abstract description 3
- 239000012467 final product Substances 0.000 description 8
- 238000003760 magnetic stirring Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 238000010189 synthetic method Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 239000005562 Glyphosate Substances 0.000 description 2
- XDDAORKBJWWYJS-UHFFFAOYSA-N glyphosate Chemical compound OC(=O)CNCP(O)(O)=O XDDAORKBJWWYJS-UHFFFAOYSA-N 0.000 description 2
- 229940097068 glyphosate Drugs 0.000 description 2
- WJRBRSLFGCUECM-UHFFFAOYSA-N hydantoin Chemical compound O=C1CNC(=O)N1 WJRBRSLFGCUECM-UHFFFAOYSA-N 0.000 description 2
- 150000004715 keto acids Chemical group 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- UYQVCLAMCWIBKC-UHFFFAOYSA-N OOP(=O)(OC)CCC(N)C(=O)O Chemical compound OOP(=O)(OC)CCC(N)C(=O)O UYQVCLAMCWIBKC-UHFFFAOYSA-N 0.000 description 1
- 206010034133 Pathogen resistance Diseases 0.000 description 1
- 238000006058 Ugi-reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001370 alpha-amino acid derivatives Chemical class 0.000 description 1
- 235000008206 alpha-amino acids Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 239000004009 herbicide Substances 0.000 description 1
- 229940091173 hydantoin Drugs 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000009261 transgenic effect Effects 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
Abstract
A synthesis method of glufosinate-ammonium comprises the following steps: step (1), 3-methyl n-butoxy phosphono propionaldehyde, acetic acid, isonitrile and ammonia water are used as raw materials and fully reacted in a solvent; step (2), distilling the reaction liquid obtained in the step (1) to remove the solvent; and (3) adding a hydrochloric acid aqueous solution into the product obtained in the step (2) for hydrolysis to obtain glufosinate-ammonium. The invention provides a synthesis method of glufosinate-ammonium, which is environment-friendly and low in cost, and the yield of the obtained glufosinate-ammonium is high; the invention avoids the use of the highly toxic substance sodium cyanide in the previous synthetic route, and has the advantages of mild reaction conditions, high yield and good industrialization prospect.
Description
Technical Field
The invention belongs to the technical field of pesticides, and relates to a synthesis method of glufosinate-ammonium.
Background
Glufosinate-ammonium, chemical name 4- [ hydroxy (methyl) phosphono ] -DL-homoalanine. Glufosinate-ammonium is a non-selective contact herbicide with low toxicity and high efficiency. Compared with glyphosate, glufosinate-ammonium has the advantages of non-descending conductivity, high weeding speed, wide action range, small influence on plant regeneration, good multiple resistance and cross resistance and the like, is more and more widely used in industries such as forestry, agriculture, animal husbandry and the like at present, becomes herbicide-tolerant for the second major transgenic crops in the world, and has continuously increased market value along with the continuous emergence of glyphosate-resistant weeds. The structural formula of glufosinate-ammonium is as follows:
at present, three methods are mainly used in the synthetic route of glufosinate-ammonium reported at home and abroad. The first is the Strecker route, which was reported in 1979 by Takashi in patent US 4264532A, and which reacts mildly, but with low overall yields of only 29%; in 1983, Finke et al in patent US4521348 improved this route, increasing the safety of the operation; in 1998, Willms et al improved this route in patent US6359162B1, as follows:
the route shortens the reaction steps and improves the yield, and has been widely used industrially at home and abroad. However, in the Strecker route, a highly toxic substance sodium cyanide is used as a raw material, and at present, relevant departments in China have made strict limitations on the raw material, and simultaneously, a large amount of ammonium chloride needs to be added, and the ammonium chloride and the glufosinate-ammonium are difficult to separate, and the problems of high operation risk factor, slightly high cost, low product purity and the like exist.
The second is the hydantoin route, plum by name et al reported a number of methods for preparing glufosinate by hydrolysis of the hydantoin ring to give the alpha-amino acid, the latest process route is as follows:
the reaction conditions of the route are mild, three wastes are less, but the route is long, and a highly toxic substance sodium cyanide is used as a raw material to generate a large amount of ammonium chloride inorganic salt.
The third is a ketoacid route, which is reported in all domestic and foreign patents, such as SU1583424A1, CN103665032A and CN103539815A, and the latest domestic report of the ketoacid route for preparing glufosinate-ammonium is that proposed by Xulinjie in patent CN105837624A, and the specific route is as follows:
the route avoids the use of sodium cyanide, and has higher yield, but the route has high cost, complex process and great difficulty in experimental operation.
Disclosure of Invention
In order to overcome the defects of long synthesis period, high cost, use of raw material sodium cyanide, more three wastes and the like in the existing synthetic route of glufosinate-ammonium, the invention provides a synthetic method of glufosinate-ammonium, which is green, environment-friendly and low in cost, and the yield of the obtained glufosinate-ammonium is high.
In order to solve the technical problems, the invention adopts the technical scheme that:
a synthesis method of glufosinate-ammonium comprises the following steps:
step (1), 3-methyl n-butoxy phosphono propionaldehyde, acetic acid, isonitrile and ammonia water are used as raw materials and fully reacted in a solvent; the reaction process has the following reaction formula:
step (2), distilling the reaction liquid obtained in the step (1) to remove the solvent;
and (3) adding a hydrochloric acid aqueous solution into the product obtained in the step (2) for hydrolysis to obtain glufosinate-ammonium, wherein the equation of the hydrolysis reaction is as follows:
further, in the step (1), the isonitrile is phenyl isonitrile, 2, 6-dimethylphenyl isonitrile, 2, 4-dimethylphenyl isonitrile, terephthalonitrile and p-toluenesulfonyl phenyl isonitrile.
Preferably, in the step (1), the solvent is one of methanol, ethanol and acetonitrile, or a mixture thereof.
Further preferably, the solvent is methanol.
Further, in the step (1), the reaction temperature is 10-30 ℃, and the reaction time is 18-24 hours.
Still further, in the step (1), the feeding molar ratio of the raw materials 3-methyl n-butoxy phosphono propionaldehyde, acetic acid, isonitrile and ammonia water is 1: (1-2) 1 (1-5).
Preferably, in the step (3), the mass fraction of the hydrochloric acid is 10% to 37%.
Preferably, in the step (3), the temperature of the hydrolysis reaction is 100-120 ℃, and the reaction time is 4-6 h.
Preferably, in the step (3), the molar ratio of the hydrochloric acid to the 3-methyl n-butoxy phosphonopropionaldehyde is (4-6): 1.
the invention has the following beneficial effects: the method adopts an Ugi reaction route, takes 3-methyl n-butoxy phosphono propionaldehyde, acetic acid, isonitrile and ammonia water as raw materials, avoids the use of sodium cyanide, adopts alcohols as solvents, accords with the principle of green chemistry, has mild reaction conditions, high yield, high atom economy and high safety, only generates a molecular water byproduct in the total reaction, is simple and convenient to operate, can be used for reaction by boiling in one pot, and has very good industrial prospect.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments. It will be understood by those skilled in the art that these embodiments are provided to illustrate the basic principles, essential features and advantages of the present invention, and the present invention is not limited by the following embodiments. The implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments. Not indicated, "%" is mass percent, and the ratio is mass ratio.
Example 1
20mL of methanol, 1.2370g (5.0mmol) of 3-methyl n-butoxy phosphonopropionaldehyde, 0.3018g (5.0mmol) of acetic acid, 1.0064g (5.0mmol) of p-toluenesulfonylphenylisonitrile and 0.3400g (5.0mmol) of ammonia water are sequentially added into a 50mL single-neck flask, the temperature is controlled to be 10 ℃, and the reaction is carried out under magnetic stirring for 24 hours. The reaction solution was then distilled until the solvent was removed. Then, 10% by mass of hydrochloric acid aqueous solution (2.0000g of 37% hydrochloric acid +5.5000g of water, the molar weight of the hydrochloric acid is 20.0mmol) is added, the reaction temperature is 100 ℃, and the reaction time is 4 hours. The final product yield was 75%.
Example 2
20mL of ethanol, 1.2370g (5.0mmol) of 3-methyl n-butoxy phosphonopropionaldehyde, 0.3603g (6.0mmol) of acetic acid, 1.0064g (5.0mmol) of p-toluenesulfonylphenylisonitrile and 0.6800g (10.0mmol) of ammonia water are sequentially added into a 50mL single-neck flask, the temperature is controlled to be 20 ℃, and the reaction is carried out under magnetic stirring for 22 hours. The reaction solution was then distilled until the solvent was removed. Then 20% hydrochloric acid aqueous solution (2.5000g of 37% hydrochloric acid +2.1875g of water, the molar weight of hydrochloric acid is 25.0mmol) is added by mass fraction, the reaction temperature is 110 ℃, and the reaction time is 5 h. The final product yield was 70%.
Example 3
20mL of acetonitrile, 1.2370g (5.0mmol) of 3-methyl n-butoxy phosphonopropionaldehyde, 0.4504g (7.5mmol) of acetic acid, 1.0064g (5.0mmol) of p-toluenesulfonylphenylisonitrile and 1.0200g (15.0mmol) of ammonia water are sequentially added into a 50mL single-neck flask, the temperature is controlled at 30 ℃, and the reaction is carried out under magnetic stirring for 20 hours. The reaction solution was then distilled until the solvent was removed. Then, 10% by mass of hydrochloric acid aqueous solution (3.0000g of 37% hydrochloric acid +8.2500g of water, the molar weight of the hydrochloric acid is 30.0mmol) is added, the reaction temperature is 120 ℃, and the reaction time is 6 hours. The final product yield was 63%.
Example 4
A synthetic method of glufosinate-ammonium comprises the steps of sequentially adding a mixed solution of 10mL of methanol and 10mL of ethanol, 1.2370g (5.0mmol) of 3-methyl n-butoxy phosphonopropionaldehyde, 0.5405g (9.0mmol) of acetic acid, 0.5156g (5.0mmol) of phenylisonitrile and 1.3600g (20.0mmol) of ammonia water into a 50mL single-neck flask, controlling the temperature to be 10 ℃, and carrying out magnetic stirring reaction for 20 hours. The reaction solution was then distilled until the solvent was removed. Then, 30% by mass of hydrochloric acid aqueous solution (2.0000g of 37% hydrochloric acid +0.5000g of water, the molar weight of the hydrochloric acid is 20.0mmol) is added, the reaction temperature is 110 ℃, and the reaction time is 4 hours. The final product yield was 85%.
Example 5
A synthetic method of glufosinate-ammonium comprises the steps of sequentially adding a mixed solution of 10mL of methanol and 10mL of acetonitrile, 1.2370g (5.0mmol) of 3-methyl n-butoxy phosphonopropionaldehyde, 0.6005g (10.0mmol) of acetic acid, 0.6559g (5.0mmol) of 2, 6-dimethyl phenyl isonitrile and 1.7000g (25.0mmol) of ammonia water into a 50mL single-neck flask, controlling the temperature to be 20 ℃, and reacting by magnetic stirring for 20 hours. The reaction solution was then distilled until the solvent was removed. Then 20% hydrochloric acid aqueous solution (3.0000g hydrochloric acid with concentration of 37% +2.6250g water, molar weight of hydrochloric acid 30.0mmol) was added at 120 ℃ for 5 h. The final product yield was 83%.
Example 6
A synthetic method of glufosinate-ammonium comprises the steps of sequentially adding a mixed solution of 10mL of ethanol and 10mL of acetonitrile, 1.2370g (5.0mmol) of 3-methyl n-butoxy phosphonopropionaldehyde, 0.4504g (7.5mmol) of acetic acid, 0.6559g (5.0mmol) of 2, 4-dimethylphenyl isonitrile and 0.6120g (15.0mmol) of ammonia water into a 50mL single-neck flask, controlling the temperature to be 30 ℃, and reacting for 18 hours under magnetic stirring. The reaction solution was then distilled until the solvent was removed. Then, 10% by mass of hydrochloric acid aqueous solution (2.0000g of 37% hydrochloric acid +5.5000g of water, the molar weight of the hydrochloric acid is 20.0mmol) is added, the reaction temperature is 100 ℃, and the reaction time is 4 hours. The final product yield was 83%.
Example 7
20mL of methanol, 1.2370g (5.0mmol) of 3-methyl n-butoxy phosphonopropionaldehyde, 0.4504g (7.5mmol) of acetic acid, 0.6407g (5.0mmol) of terephthalonitrile and 0.6120g (15.0mmol) of ammonia water are sequentially added into a 50mL single-neck flask, the temperature is controlled to be 10 ℃, and the reaction is carried out by magnetic stirring for 24 hours. The reaction solution was then distilled until the solvent was removed. Then, 10% by mass of hydrochloric acid aqueous solution (2.0000g of 37% hydrochloric acid +5.5000g of water, the molar weight of the hydrochloric acid is 20.0mmol) is added, the reaction temperature is 100 ℃, and the reaction time is 4 hours. The final product yield was 80%.
Example 8
A synthetic method of glufosinate-ammonium comprises the steps of sequentially adding a mixed solution of 8mL of methanol, 6mL of ethanol and 6mL of acetonitrile, 1.2370g (5.0mmol) of 3-methyl n-butoxy phosphonopropionaldehyde, 0.3018g (5.0mmol) of acetic acid, 1.0064g (5.0mmol) of p-toluenesulfonyl phenyl isonitrile and 0.3400g (5.0mmol) of ammonia water into a 50mL single-neck flask, controlling the temperature to be 30 ℃, and reacting for 24 hours under magnetic stirring. The reaction solution was then distilled until the solvent was removed. Then, 37% by mass of hydrochloric acid aqueous solution (2.0000g of 37% hydrochloric acid, the molar weight of the hydrochloric acid is 20.0mmol) is added, the reaction temperature is 120 ℃, and the reaction time is 6 hours. The final product yield was 87%.
The above embodiments are merely illustrative of the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the content of the present invention and implement the invention, and not to limit the scope of the invention, and all equivalent changes or modifications made according to the spirit of the present invention should be covered by the scope of the present invention.
Claims (8)
1. A synthesis method of glufosinate-ammonium, characterized by comprising the following steps:
step (1), 3-methyl n-butoxy phosphono propionaldehyde, acetic acid, isonitrile and ammonia water are used as raw materials and fully reacted in a solvent; the reaction process has the following reaction formula:
step (2), distilling the reaction liquid obtained in the step (1) to remove the solvent;
and (3) adding a hydrochloric acid aqueous solution into the product obtained in the step (2) for hydrolysis to obtain glufosinate-ammonium, wherein the equation of the hydrolysis reaction is as follows:
in the step (1), the isonitrile is phenyl isonitrile, 2, 6-dimethylphenyl isonitrile, 2, 4-dimethylphenyl isonitrile, terephthalonitrile and p-toluenesulfonyl phenyl isonitrile.
2. The method for synthesizing glufosinate according to claim 1, wherein in the step (1), the solvent is one of methanol, ethanol and acetonitrile or a mixture thereof.
3. The method for synthesizing glufosinate-ammonium according to claim 2, wherein the solvent is methanol.
4. The method for synthesizing glufosinate-ammonium according to claim 1, wherein in the step (1), the reaction temperature is 10-30 ℃ and the reaction time is 18-24 h.
5. The method for synthesizing glufosinate according to claim 1, wherein in the step (1), the feeding molar ratio of the raw materials 3-methyl n-butoxy phosphono propionaldehyde, acetic acid, isonitrile and ammonia water is 1: (1-2) 1 (1-5).
6. The method for synthesizing glufosinate according to claim 1, wherein in the step (3), the mass fraction of the hydrochloric acid is 10% to 37%.
7. The method for synthesizing glufosinate-ammonium according to claim 1, wherein in the step (3), the temperature of the hydrolysis reaction is 100-120 ℃, and the reaction time is 4-6 h.
8. The method for synthesizing glufosinate-ammonium according to claim 1, wherein in the step (3), the molar ratio of the hydrochloric acid to the 3-methyl-n-butoxy phosphonopropionaldehyde is (4-6): 1.
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| CN112574118B (en) * | 2019-09-29 | 2023-10-31 | 利尔化学股份有限公司 | Process for preparing glufosinate-hydantoin intermediates and analogues |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102584893A (en) * | 2012-02-07 | 2012-07-18 | 浙江工业大学 | Preparation method for glufosinate |
| CN103374030A (en) * | 2012-04-13 | 2013-10-30 | 浙江新安化工集团股份有限公司 | Method for preparing glufosinate-ammonium and preparation method for intermediate thereof |
| 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 |
| WO2018108794A1 (en) * | 2016-12-15 | 2018-06-21 | Bayer Cropscience Aktiengesellschaft | Method for producing d-glufosinate or salts thereof using ephedrine |
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| CN102584893A (en) * | 2012-02-07 | 2012-07-18 | 浙江工业大学 | Preparation method for glufosinate |
| CN103374030A (en) * | 2012-04-13 | 2013-10-30 | 浙江新安化工集团股份有限公司 | Method for preparing glufosinate-ammonium and preparation method for intermediate thereof |
| 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 |
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| 钯催化的酰胺羰基化反应合成草铵膦;詹意等;《农药》;20180330;第406-408页 * |
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