CN111087294A - A kind of preparation method of high-purity prohexadione calcium - Google Patents
A kind of preparation method of high-purity prohexadione calcium Download PDFInfo
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- CN111087294A CN111087294A CN201911311025.2A CN201911311025A CN111087294A CN 111087294 A CN111087294 A CN 111087294A CN 201911311025 A CN201911311025 A CN 201911311025A CN 111087294 A CN111087294 A CN 111087294A
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- NLKUPINTOLSSLD-UHFFFAOYSA-L calcium;4-(1-oxidopropylidene)-3,5-dioxocyclohexane-1-carboxylate Chemical compound [Ca+2].CCC([O-])=C1C(=O)CC(C([O-])=O)CC1=O NLKUPINTOLSSLD-UHFFFAOYSA-L 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000047 product Substances 0.000 claims abstract description 87
- 230000008707 rearrangement Effects 0.000 claims abstract description 80
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 49
- 239000007788 liquid Substances 0.000 claims abstract description 40
- 239000012043 crude product Substances 0.000 claims abstract description 35
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000012312 sodium hydride Substances 0.000 claims abstract description 26
- 229910000104 sodium hydride Inorganic materials 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 22
- MJHQRRSBNKKDKV-UHFFFAOYSA-N ethyl 3,5-dioxo-4-propanoylcyclohexane-1-carboxylate Chemical compound CCOC(=O)C1CC(=O)C(C(=O)CC)C(=O)C1 MJHQRRSBNKKDKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000967 suction filtration Methods 0.000 claims abstract description 15
- 239000003960 organic solvent Substances 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 239000005986 Prohexadione Substances 0.000 claims abstract description 7
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 7
- BUCOQPHDYUOJSI-UHFFFAOYSA-N prohexadione Chemical compound CCC(=O)C1C(=O)CC(C(O)=O)CC1=O BUCOQPHDYUOJSI-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 239000002253 acid Substances 0.000 claims description 29
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 23
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000007858 starting material Substances 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 239000011976 maleic acid Substances 0.000 claims description 8
- -1 maleic acid diester Chemical class 0.000 claims description 8
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 8
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- 230000007062 hydrolysis Effects 0.000 claims description 6
- 239000012670 alkaline solution Substances 0.000 claims description 4
- 238000003512 Claisen condensation reaction Methods 0.000 claims description 3
- 238000005917 acylation reaction Methods 0.000 claims description 3
- 238000007792 addition Methods 0.000 claims description 3
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 238000006462 rearrangement reaction Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 238000012805 post-processing Methods 0.000 claims 1
- 150000003839 salts Chemical class 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract description 22
- 230000001376 precipitating effect Effects 0.000 abstract description 9
- 238000001914 filtration Methods 0.000 abstract description 8
- 238000000034 method Methods 0.000 abstract description 5
- 238000004440 column chromatography Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000002244 precipitate Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 150000005690 diesters Chemical class 0.000 description 6
- 239000012265 solid product Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- NIQQIJXGUZVEBB-UHFFFAOYSA-N methanol;propan-2-one Chemical compound OC.CC(C)=O NIQQIJXGUZVEBB-UHFFFAOYSA-N 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 239000002689 soil Substances 0.000 description 3
- HLVQZEMFVYGIGH-UHFFFAOYSA-L 4-(1-oxidopropylidene)-3,5-dioxocyclohexane-1-carboxylate Chemical compound CCC([O-])=C1C(=O)CC(C([O-])=O)CC1=O HLVQZEMFVYGIGH-UHFFFAOYSA-L 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 239000005648 plant growth regulator Substances 0.000 description 2
- 239000003375 plant hormone Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- VWUWYWZCDPICJM-UHFFFAOYSA-N 2-propanoylcyclohex-4-ene-1,3-dione Chemical compound CCC(=O)C1C(=O)CC=CC1=O VWUWYWZCDPICJM-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- 208000035240 Disease Resistance Diseases 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 244000038559 crop plants Species 0.000 description 1
- FWFSEYBSWVRWGL-UHFFFAOYSA-N cyclohex-2-enone Chemical compound O=C1CCCC=C1 FWFSEYBSWVRWGL-UHFFFAOYSA-N 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 239000007954 growth retardant Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 230000008121 plant development Effects 0.000 description 1
- 230000008635 plant growth Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/09—Preparation of carboxylic acids or their salts, halides or anhydrides from carboxylic acid esters or lactones
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of high-purity prohexadione calcium, which comprises the following steps: sodium hydride is dissolved in an organic solvent A to prepare a liquid B. Adding a crude product of the rearrangement product of the 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester into the organic solvent A, stirring and dissolving for 0.5-2h, standing and precipitating, filtering to remove insoluble impurities, dropwise and slowly dropping the prepared liquid B into the formed solution for reaction, carrying out suction filtration after dropping, and obtaining a solid which is a purified rearrangement product of the sodium salt by suction filtration; hydrolyzing the obtained rearrangement product sodium salt under an alkaline condition, and acidifying to obtain a prohexadione; finally, the prohexadione reacts with calcium salt to prepare the target product prohexadione-calcium. The method has the advantages of simple reaction condition, convenient operation, no need of column chromatography separation, stable yield, low requirement on equipment, environmental friendliness and good industrialization prospect.
Description
Technical Field
The invention relates to the technical field of organic pesticide synthesis, in particular to a preparation method of high-purity prohexadione calcium.
Background
A plant growth regulator is a kind of agricultural chemicals for regulating plant growth and development, including artificially synthesized compound with similar action of natural plant hormone and natural plant hormone extracted from living beings. Prohexadione Calcium is a novel cyclohexenone plant growth regulator firstly developed by Nippon combinatorial chemistry industry company in 1983, belongs to 2-acyl-1, 3-cyclohexanedione compounds, has a chemical name of 3, 5-dioxo-4-propionyl cyclohexene carboxylate Calcium, is called Calcium 3, 5-dioxo-4-propionocyclohexenone carboxylic acid in English, and has a structural formula shown as formula 1:
the prohexadione calcium is mainly used for controlling the growth of cereal crops, can shorten the length of crop stems, can enhance the disease resistance, cold resistance and stress resistance of plants, and has obvious lodging resistance. Compared with the triazole retardant which is widely applied at present, Prohexadione-Ca has no residual toxicity to crop plants and no pollution to the environment, and is degraded into carbon dioxide very quickly under the conditions of flooding soil and mountain land soil, so that the Prohexadione-Ca can replace the triazole growth retardant and has wide market prospect.
The degradation reaction process of the prohexadione calcium in the soil is as follows:
in recent years, a great deal of research is carried out on the synthetic route of prohexadione calcium at home and abroad, for example, CN 104140368A introduces a route with industrial prospect. In the document, diethyl maleate is used as a starting material, and the prohexadione calcium is prepared through six steps of reactions such as Michale addition, Claisen condensation, acylation reaction, rearrangement, hydrolysis, salification and the like. Therefore, how to obtain prohexadione calcium with higher purity and improve the purity thereof is a technical problem to be solved urgently.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a preparation method for purifying prohexadione calcium, which has the advantages of simple preparation method, convenient operation and low requirement on equipment.
The preparation method of the high-purity prohexadione calcium is characterized by comprising the following steps:
1) dissolving sodium hydride in an organic solvent A to prepare a liquid B with the mass percent concentration of the sodium hydride of 1.5-5%;
2) adding a crude product of the rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester into an organic solvent A, stirring and dissolving for 0.5-2h, standing and precipitating, filtering to remove insoluble impurities, dropwise and slowly dropping the filtered solution into the liquid B obtained in the step 1) for reaction, carrying out suction filtration after the dropping of the liquid B is finished, wherein the solid obtained by suction filtration is the purified rearrangement product sodium salt, and the molecular structure of the rearrangement product sodium salt is shown as the formula (I);
3) stirring and hydrolyzing the rearrangement product sodium salt obtained in the step 2) in an alkaline solution, hydrolyzing the rearrangement product sodium salt to generate a cycloregulated acid sodium salt shown in a formula (II), adding an acid to regulate the pH value of the reaction solution to 7.5-8.5, acidifying the cycloregulated acid sodium salt shown in the formula (II) to generate cycloregulated acid, then adding a calcium salt to react at the temperature of 50-70 ℃ for 1-3h, and after the reaction is finished, carrying out post-treatment on the reaction solution to obtain the cycloregulated calcium salt product;
the preparation method of the high-purity prohexadione calcium is characterized in that the crude product of the rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylate is prepared by taking maleic acid diester and acetone as starting raw materials and sequentially carrying out Michale addition, Claisen condensation, acylation reaction and rearrangement reaction.
The preparation method of the high-purity prohexadione calcium is characterized in that the organic solvent A is one or two mixed solvents of methanol and acetone.
The preparation method of the high-purity prohexadione-calcium is characterized in that in the step 2), the standing and precipitating time is 2-2.5 h.
The preparation method of the high-purity prohexadione calcium is characterized in that in the step 2), the feeding molar ratio of the rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester to the sodium hydride is 1.0: 1.0-1.2, preferably 1: 1.1; the temperature at which the liquid B was added dropwise to carry out the reaction was room temperature.
The preparation method of the high-purity prohexadione calcium is characterized in that in the step 3), the alkaline solution is a NaoH aqueous solution with the mass concentration of 10-20%, the stirring hydrolysis temperature is 50-70 ℃, and the stirring hydrolysis time is 1-3 h.
The preparation method of the high-purity prohexadione calcium is characterized in that in the step 3), the feeding molar ratio of the rearrangement product sodium salt to the calcium salt is 1: 1-1.5, and preferably 1: 1.2.
The preparation method of the high-purity prohexadione-calcium is characterized in that in the step 3), the step of post-treating the reaction liquid is as follows: and (4) carrying out suction filtration on the reaction solution, washing filter residues with deionized water, and drying.
Compared with the prior art, the invention has the beneficial effects that:
firstly, a crude product of rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester reacts with sodium hydride in organic solvents such as methanol, acetone and the like, and the reaction formula is as follows:
the rearrangement product sodium salt which is insoluble in organic solvents such as methanol, acetone and the like is generated through the reaction, then the suction filtration is carried out, and the solid obtained through the suction filtration is the rearrangement product sodium salt after purification, and the good purification effect can be achieved through the operation process. Then stirring and hydrolyzing the purified rearrangement product sodium salt in NaOH aqueous solution, wherein the reaction formula of stirring and hydrolyzing is as follows:
sodium salt of prohexadione is generated after stirring and hydrolysis reaction, and then prohexadione is generated after acidification, and then the prohexadione reacts with calcium salt to obtain the prohexadione calcium product. In the process of preparing the high-purity prohexadione calcium, the invention has the advantages of simple operation steps, simple reaction conditions, low requirement on equipment and environmental protection, does not need column chromatography separation in the whole operation process, has stable yield of the target prohexadione calcium and has good industrialization prospect.
Detailed Description
The present invention is further illustrated by the following examples, which should not be construed as limiting the scope of the invention.
Example 1
According to the route provided in example 1 of Chinese patent CN 104140368A, the crude product of rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester is prepared by using maleic acid diester as starting material and is marked as rearrangement product crude product.
The high-purity prohexadione calcium is prepared by taking the rearrangement product crude product as an initial raw material, and the steps are as follows:
1) dissolving sodium hydride by using methanol, preparing a liquid B with the mass percent concentration of the sodium hydride of 2.53 percent, and transferring the liquid B into a dropping funnel;
2) weighing 20g of the rearrangement product crude product, adding the rearrangement product crude product into 400ml of methanol, stirring and dissolving for 1h, standing and precipitating for 2h, filtering to remove insoluble impurities, and obtaining a clear rearrangement product methanol solution marked as liquid C;
3) slowly dropwise adding the liquid B (the feeding molar ratio of the rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester to the sodium hydride is 1.0:1.1) into the liquid C obtained in the step 2) at room temperature, and performing suction filtration after the dropwise adding is finished to obtain 16.4g of beige precipitate, wherein the beige precipitate is the rearrangement product sodium salt;
4) stirring and hydrolyzing the rearrangement product sodium salt obtained in the step 3) in a NaOH aqueous solution with the mass concentration of 15 percent, and performing hydrolysis at the temperature of 60 DEG CHydrolyzing for 1.5h (hydrolyzing rearrangement product sodium salt to generate cycloregulated acid sodium salt), adding acid to adjust the pH of the reaction solution to about 8.0 (acidifying the cycloregulated acid sodium salt to generate cycloregulated acid), and adding CaCl with the mass concentration of 10%288.8g of aqueous solution is reacted for 2 hours at the temperature of 60 ℃, then is filtered, and filter residue is washed by deionized water and then is dried, finally obtaining a light yellow solid product prohexadione calcium with the purity of 95.1 percent and the yield of 42.5 percent (calculated by the initial raw material maleic diester).
Example 2
According to the route provided in example 1 of Chinese patent CN 104140368A, the crude product of rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester is prepared by using maleic acid diester as starting material and is marked as rearrangement product crude product.
The high-purity prohexadione calcium is prepared by taking the rearrangement product crude product as an initial raw material, and the steps are as follows:
1) dissolving sodium hydride by using acetone, preparing a liquid B with the mass percent concentration of the sodium hydride of 2.53 percent, and transferring the liquid B into a dropping funnel;
2) weighing 20g of the rearrangement product crude product, adding the rearrangement product crude product into 400ml of acetone, stirring and dissolving for 1h, standing and precipitating for 2.3h, filtering to remove insoluble impurities, and obtaining a clear acetone solution of the rearrangement product, wherein the acetone solution is marked as liquid C;
3) slowly dropwise adding the liquid B (the feeding molar ratio of the rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester to the sodium hydride is 1.0:1.1) into the liquid C obtained in the step 2) at room temperature, and performing suction filtration after the dropwise adding is finished to obtain 16.2g of beige precipitate, wherein the beige precipitate is the rearrangement product sodium salt;
4) stirring and hydrolyzing the rearrangement product sodium salt obtained in the step 3) in a NaOH aqueous solution with the mass concentration of 15%, hydrolyzing for 1.5h at the temperature of 60 ℃ (hydrolyzing the rearrangement product sodium salt to generate a cycloregulated acid sodium salt), then adding acid to adjust the pH of the reaction solution to about 8.0 (acidifying the cycloregulated acid sodium salt to generate cycloregulated acid), and then adding CaCl with the mass concentration of 10%288.8g of aqueous solution is reacted for 2 hours at the temperature of 60 ℃, then is filtered, filter residue is washed by deionized water and is dried, finally, a light yellow solid product prohexadione calcium is obtained,purity 95.0% and yield 42.1% (based on the starting material, maleic diester).
Example 3
According to the route provided in example 1 of Chinese patent CN 104140368A, the crude product of rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester is prepared by using maleic acid diester as starting material and is marked as rearrangement product crude product.
The high-purity prohexadione calcium is prepared by taking the rearrangement product crude product as an initial raw material, and the steps are as follows:
1) dissolving sodium hydride by using methanol, preparing a liquid B with the mass percent concentration of the sodium hydride of 2.53 percent, and transferring the liquid B into a dropping funnel;
2) weighing 20g of the rearrangement product crude product, adding the rearrangement product crude product into 200ml of methanol, stirring and dissolving for 1h, standing and precipitating for 2h, filtering to remove insoluble impurities, and obtaining a clear rearrangement product methanol solution marked as liquid C;
3) slowly dropwise adding the liquid B (the feeding molar ratio of the rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester to the sodium hydride is 1.0:1.1) into the liquid C obtained in the step 2) at room temperature, and performing suction filtration after the dropwise adding is finished to obtain 16.1g of beige precipitate, wherein the beige precipitate is the rearrangement product sodium salt;
4) stirring and hydrolyzing the rearrangement product sodium salt obtained in the step 3) in a NaOH aqueous solution with the mass concentration of 15%, hydrolyzing for 1.5h at the temperature of 60 ℃ (hydrolyzing the rearrangement product sodium salt to generate a cycloregulated acid sodium salt), then adding acid to adjust the pH of the reaction solution to about 8.0 (acidifying the cycloregulated acid sodium salt to generate cycloregulated acid), and then adding CaCl with the mass concentration of 10%288.8g of aqueous solution is reacted for 2 hours at the temperature of 60 ℃, then is filtered, and filter residue is washed by deionized water and then is dried, finally obtaining a light yellow solid product prohexadione calcium with the purity of 94.1 percent and the yield of 42.4 percent (calculated by the initial raw material maleic diester).
Example 4
According to the route provided in example 1 of Chinese patent CN 104140368A, the crude product of rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester is prepared by using maleic acid diester as starting material and is marked as rearrangement product crude product.
The high-purity prohexadione calcium is prepared by taking the rearrangement product crude product as an initial raw material, and the steps are as follows:
1) dissolving sodium hydride by using acetone, preparing a liquid B with the mass percent concentration of the sodium hydride of 2.53 percent, and transferring the liquid B into a dropping funnel;
2) weighing 20g of the rearrangement product crude product, adding the rearrangement product crude product into 200ml of acetone, stirring and dissolving for 1h, standing and precipitating for 2.3h, filtering to remove insoluble impurities, and obtaining a clear acetone solution of the rearrangement product, wherein the acetone solution is marked as liquid C;
3) slowly dropwise adding the liquid B (the feeding molar ratio of the rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester to the sodium hydride is 1.0:1.1) into the liquid C obtained in the step 2) at room temperature, and performing suction filtration after the dropwise adding is finished to obtain 16.0g of beige precipitate, wherein the beige precipitate is the rearrangement product sodium salt;
4) stirring and hydrolyzing the rearrangement product sodium salt obtained in the step 3) in a NaOH aqueous solution with the mass concentration of 15%, hydrolyzing for 1.5h at the temperature of 60 ℃ (hydrolyzing the rearrangement product sodium salt to generate a cycloregulated acid sodium salt), then adding acid to adjust the pH of the reaction solution to about 8.0 (acidifying the cycloregulated acid sodium salt to generate cycloregulated acid), and then adding CaCl with the mass concentration of 10%288.8g of aqueous solution is reacted for 2 hours at the temperature of 60 ℃, then is filtered, and filter residue is washed by deionized water and then is dried, finally obtaining a light yellow solid product prohexadione calcium with the purity of 93.7 percent and the yield of 42.2 percent (calculated by the initial raw material maleic diester).
Example 5
According to the route provided in example 1 of Chinese patent CN 104140368A, the crude product of rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester is prepared by using maleic acid diester as starting material and is marked as rearrangement product crude product.
The high-purity prohexadione calcium is prepared by taking the rearrangement product crude product as an initial raw material, and the steps are as follows:
1) dissolving sodium hydride by using a methanol-acetone mixed solution with the volume ratio of 1:1, preparing to obtain a liquid B with the mass percent concentration of the sodium hydride of 2.53%, and transferring the liquid B into a dropping funnel;
2) weighing 20g of the rearrangement product crude product, adding the rearrangement product crude product into 400ml of methanol-acetone mixed solution with the volume ratio of 1:1, stirring and dissolving for 1h, standing and precipitating for 2.3h, filtering to remove insoluble impurities, and obtaining a clear solution marked as liquid C;
3) slowly dropwise adding the liquid B (the feeding molar ratio of the rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester to the sodium hydride is 1.0:1.1) into the liquid C obtained in the step 2) at room temperature, and performing suction filtration after the dropwise adding is finished to obtain 16.1g of beige precipitate, wherein the beige precipitate is the rearrangement product sodium salt;
4) stirring and hydrolyzing the rearrangement product sodium salt obtained in the step 3) in a NaOH aqueous solution with the mass concentration of 15%, hydrolyzing for 1.5h at the temperature of 60 ℃ (hydrolyzing the rearrangement product sodium salt to generate a cycloregulated acid sodium salt), then adding acid to adjust the pH of the reaction solution to about 8.0 (acidifying the cycloregulated acid sodium salt to generate cycloregulated acid), and then adding CaCl with the mass concentration of 10%288.8g of aqueous solution is reacted for 2 hours at the temperature of 60 ℃, then is filtered, and filter residue is washed by deionized water and then is dried, finally obtaining a light yellow solid product prohexadione calcium with the purity of 94.1 percent and the yield of 42.0 percent (calculated by the initial raw material maleic diester).
Example 6
According to the route provided in example 1 of Chinese patent CN 104140368A, the crude product of rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester is prepared by using maleic acid diester as starting material and is marked as rearrangement product crude product.
The high-purity prohexadione calcium is prepared by taking the rearrangement product crude product as an initial raw material, and the steps are as follows:
1) dissolving sodium hydride by using a methanol-acetone mixed solution with the volume ratio of 1:1, preparing to obtain a liquid B with the mass percent concentration of the sodium hydride of 2.53%, and transferring the liquid B into a dropping funnel;
2) weighing 20g of the rearrangement product crude product, adding the rearrangement product crude product into 200ml of methanol-acetone mixed solution with the volume ratio of 1:1, stirring and dissolving for 1h, standing and precipitating for 2.3h, filtering to remove insoluble impurities, and obtaining a clear solution marked as liquid C;
3) slowly dropwise adding the liquid B (the feeding molar ratio of the rearrangement product 3, 5-dioxo-4-propionyl cyclohexanecarboxylic acid ethyl ester to the sodium hydride is 1.0:1.1) into the liquid C obtained in the step 2) at room temperature, and performing suction filtration after the dropwise adding is finished to obtain 16.1g of beige precipitate, wherein the beige precipitate is the rearrangement product sodium salt;
4) stirring and hydrolyzing the rearrangement product sodium salt obtained in the step 3) in a NaOH aqueous solution with the mass concentration of 15%, hydrolyzing for 1.5h at the temperature of 60 ℃ (hydrolyzing the rearrangement product sodium salt to generate a cycloregulated acid sodium salt), then adding acid to adjust the pH of the reaction solution to about 8.0 (acidifying the cycloregulated acid sodium salt to generate cycloregulated acid), and then adding CaCl with the mass concentration of 10%288.8g of aqueous solution is reacted for 2 hours at the temperature of 60 ℃, then is filtered, and filter residue is washed by deionized water and then is dried, finally obtaining a light yellow solid product prohexadione calcium with the purity of 93.5 percent and the yield of 42.1 percent (calculated by the initial raw material maleic diester).
The purity of the prepared prohexadione-calcium product is detected by adopting a high performance liquid chromatography, a mixed solution of acetonitrile, water and phosphoric acid with the volume ratio of 70:30:0.1 is used as a mobile phase, and a chromatographic column uses C18The stainless steel column as filler was quantified by external standard method.
The statements in this specification merely set forth a list of implementations of the inventive concept and the scope of the present invention should not be construed as limited to the particular forms set forth in the examples.
Claims (8)
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| CN111972411A (en) * | 2020-09-07 | 2020-11-24 | 安徽省四达农药化工有限公司 | Preparation and application of prohexadione calcium suspending agent |
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