CN112608272A - Preparation method of picloram potassium salt bulk drug - Google Patents
Preparation method of picloram potassium salt bulk drug Download PDFInfo
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- CN112608272A CN112608272A CN202011565245.0A CN202011565245A CN112608272A CN 112608272 A CN112608272 A CN 112608272A CN 202011565245 A CN202011565245 A CN 202011565245A CN 112608272 A CN112608272 A CN 112608272A
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- Prior art keywords
- aminopyralid
- potassium
- raw material
- reaction
- preparing
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- 239000003814 drug Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229940079593 drug Drugs 0.000 title claims abstract description 17
- ZRHANBBTXQZFSP-UHFFFAOYSA-M potassium;4-amino-3,5,6-trichloropyridine-2-carboxylate Chemical compound [K+].NC1=C(Cl)C(Cl)=NC(C([O-])=O)=C1Cl ZRHANBBTXQZFSP-UHFFFAOYSA-M 0.000 title claims abstract description 8
- 239000005468 Aminopyralid Substances 0.000 claims abstract description 44
- NIXXQNOQHKNPEJ-UHFFFAOYSA-N aminopyralid Chemical compound NC1=CC(Cl)=NC(C(O)=O)=C1Cl NIXXQNOQHKNPEJ-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims abstract description 20
- 235000015497 potassium bicarbonate Nutrition 0.000 claims abstract description 20
- 239000011736 potassium bicarbonate Substances 0.000 claims abstract description 20
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims abstract description 20
- 239000000843 powder Substances 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 17
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 14
- 229910052700 potassium Inorganic materials 0.000 claims description 14
- 239000011591 potassium Substances 0.000 claims description 14
- XUYNZTABHAFFAO-UHFFFAOYSA-M potassium;4-amino-3,6-dichloropyridine-2-carboxylate Chemical compound [K+].NC1=CC(Cl)=NC(C([O-])=O)=C1Cl XUYNZTABHAFFAO-UHFFFAOYSA-M 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000004898 kneading Methods 0.000 claims description 2
- 239000008186 active pharmaceutical agent Substances 0.000 claims 4
- 229940088679 drug related substance Drugs 0.000 claims 4
- 239000000463 material Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 239000002699 waste material Substances 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 3
- 230000008025 crystallization Effects 0.000 abstract description 3
- 238000001914 filtration Methods 0.000 abstract description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 abstract description 2
- 238000003756 stirring Methods 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 125000006378 chloropyridyl group Chemical group 0.000 abstract 1
- 238000003912 environmental pollution Methods 0.000 abstract 1
- NQQVFXUMIDALNH-UHFFFAOYSA-N picloram Chemical compound NC1=C(Cl)C(Cl)=NC(C(O)=O)=C1Cl NQQVFXUMIDALNH-UHFFFAOYSA-N 0.000 description 10
- 239000005595 Picloram Substances 0.000 description 9
- 238000013461 design Methods 0.000 description 7
- 241000196324 Embryophyta Species 0.000 description 6
- 238000003860 storage Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000002363 herbicidal effect Effects 0.000 description 3
- 239000004009 herbicide Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 240000001140 Mimosa pudica Species 0.000 description 1
- 235000016462 Mimosa pudica Nutrition 0.000 description 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 1
- 206010043275 Teratogenicity Diseases 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000003688 hormone derivative Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-N picolinic acid Chemical compound OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 231100000211 teratogenicity Toxicity 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
- C07D213/79—Acids; Esters
- C07D213/803—Processes of preparation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a preparation method of a raw material drug of picloram potassium salt, which mainly comprises the following steps: adding aminopyralid raw powder and potassium bicarbonate into a kneader according to the molar ratio of 1:1-1.1, mixing for 15min at 25 ℃, heating and keeping the temperature at 40-80 ℃, then adding water, and continuously mixing, stirring and reacting for 60-120 min. And after the reaction is finished, drying to obtain the raw material medicament of the chloropyridyl acid potassium salt. The advantages are that: the materials are always kept in a solid state in the whole production process, a subsequent crystallization and filtration process is not needed, three wastes are not generated, and the production process is safe, economical, environment-friendly and less in environmental pollution.
Description
Technical Field
The invention relates to a preparation method of a picloram potassium salt raw material medicine, which has the advantages of safe and simple process, high product utilization rate, low cost and environmental friendliness, and belongs to the field of herbicide manufacture.
Background
Aminopyralid, also called amfenadine, chemical name 4-amino-3, 5, 6-trichloropyridine carboxylic acid, is a pyridine carboxylic acid novel herbicide developed by the agricultural department of pottery, and is widely used for weed control in mountainous regions, grasslands, planting lands and uncultivated areas. The aminopyralid belongs to a synthetic hormone type herbicide, can be quickly absorbed by stems, leaves and roots of plants, induces the plants to generate partial sexual reaction in sensitive plants, thereby leading the growth of the plants to be stagnated and the plants to rapidly die, has good systemic property, has the characteristics of low toxicity, high efficiency, no teratogenicity, low toxicity of mutagenicity to human beings and the like, and is researched and developed to be applied to the fields of rape and cereal crops to prevent and kill weeds. The method has the following defects: the aminopyralid needs to be prepared into a preparation for use when in use, the common preparation at present is a water aqua, and the water aqua has low mass concentration, so that the storage and transportation cost is high. Secondly, the conventional method for preparing the raw material drug of the picloram potassium salt is to react the picloram raw material drug with potassium hydroxide in a liquid phase, and then obtain the raw material drug through the working procedures of concentration, cooling, alcohol precipitation, suction filtration, drying and the like. The liquid phase method preparation process has the disadvantages of complex process, use of a large amount of organic solvent, generation of more waste water and the like.
Disclosure of Invention
The design purpose is as follows: the defects in the background technology are avoided, and the preparation method of the raw material drug of the picloram potassium salt is designed, wherein the product does not need concentration, crystallization, filtration and washing, can ensure the required quality concentration, and has the advantages of simple production process, low storage and transportation cost and almost no generation of three wastes.
The design scheme is as follows: in order to achieve the above design objectives. The picloram is prepared into the potassium salt bulk drug, and the picloram bulk drug is soluble in water, so that the picloram bulk drug is prepared into soluble powder or soluble granules, and the storage and transportation cost can be greatly reduced. Secondly, the preparation method adopts solid-solid reaction in the production process, the product does not need concentration, crystallization, filtration and washing, and the three wastes are hardly generated, so that the production process is simpler, the requirement on equipment is low, and the safety is greatly improved.
The technical scheme is as follows: a preparation method of a picloram potassium salt raw material medicine comprises the following steps of (1) putting picloram raw powder and potassium bicarbonate into a kneader according to a molar ratio of 1:1-1.1, mixing for 15-30min at 24.5-25.5 ℃, heating, keeping the temperature at 30-50 ℃, adding water, wherein the water amount is 1-8% of the mass of the picloram raw powder, and kneading for 60-120 min. (2) And after the reaction is finished, drying in a drying device at 65-100 ℃ to obtain the aminopyralid potassium salt raw material medicine.
Compared with the background technology, firstly, the solid-solid reaction is adopted in the production process, the product does not need to be concentrated, crystallized, filtered and washed, the three wastes are hardly generated, the production process is simpler, and the requirement on equipment is low; secondly, the storage and transportation cost is low, the safety is good, the utilization rate is high, and the manufacturing cost is low.
Detailed Description
A preparation method of aminopyralid raw material medicine comprises the following steps:
adding the aminopyralid raw powder and the potassium bicarbonate into a kneader according to the molar ratio of 1:1-1.1, mixing for 15-30min at 25 ℃, heating, keeping the temperature at 30-50 ℃, adding a proper amount of water, wherein the added amount of water is 1-8% of the mass of the aminopyralid raw powder, reacting for 60-120min, and sending into an oven for drying after the reaction is finished to obtain the aminopyralid raw material medicine.
In the reaction step, a kneader plays a role in extruding, stirring and mixing, a proper amount of water is added to initiate reaction, so that reactants are contacted more uniformly and the reaction is more complete, the reaction rate is increased by properly increasing the reaction temperature, and the reaction time is shortened.
The molar ratio of aminopyralid to potassium bicarbonate in the above preparation method is 1:1-1.1, preferably 1: 1.04.
In the preparation method, the solid aminopyralid and the potassium bicarbonate are firstly premixed at the room temperature of 25 ℃ for 15-30min, preferably 20-25min, and then heated to the reaction temperature for reaction.
In the preparation method, the reaction temperature of the aminopyralid raw powder and the potassium bicarbonate is 40-80 ℃, and the preferable temperature is 60-70 ℃.
In the preparation method, the reaction time of the aminopyralid raw powder and the potassium bicarbonate is 60-120min, preferably 90-120 min.
In the preparation method, the drying mode is drying in an oven, the drying temperature is 65-100 ℃, and the preferable temperature is 80 ℃.
Example 1: the preparation method of the potassium aminopyralid comprises the following steps: 1000g of aminopyralid raw powder (with the purity of 95%) and 482g of potassium bicarbonate (with the purity of 99%) are put into a kneader with the capacity of 2L together, premixed for 20min under the conditions of normal temperature and normal pressure, heated to 60 ℃, added with 50g of water at a constant speed, stirred and kneaded continuously, and sampled after 90min to detect the reaction condition of the materials, wherein detection shows that the materials can be completely dissolved in water, no bubble is generated in the dissolving process, and the reaction of the aminopyralid and the potassium bicarbonate is completely finished. The materials are sent into an oven and dried at 80 ℃ to obtain 1168g of the picloram chloride dry product, the content of the picloram chloride is detected to be 95.1%, and the yield is 99.1%.
Example 2: the preparation method of the potassium aminopyralid comprises the following steps: 300Kg of aminopyralid raw powder (with the purity of 95%) and 144.8Kg of potassium bicarbonate (with the purity of 99%) are put into a kneader with the capacity of 500L together, premixed for 20min under the conditions of normal temperature and normal pressure, heated to 60 ℃, added with 3Kg of water at uniform speed, stirred and kneaded continuously, and sampling is carried out after 90min to detect the reaction condition of the materials, and the detection shows that the materials can be completely dissolved in water, and no bubble is generated in the dissolving process, which indicates that the aminopyralid raw powder is completely converted into the potassium aminopyralid. The materials are sent into an oven and dried at 80 ℃ to obtain 351Kg of dry product of the aminopyralid, the content of the aminopyralid is detected to be 95.3 percent, and the yield is 99.2 percent.
Example 3: the preparation method of the potassium aminopyralid comprises the following steps: 1200Kg of aminopyralid raw powder (with the purity of 95 percent) and 579.2Kg of potassium bicarbonate (with the purity of 99 percent) are put into a kneader with the capacity of 2000L together, premixed for 25min under the conditions of normal temperature and normal pressure, heated to 60 ℃, added with 10Kg of water at uniform speed, continuously stirred and mixed, and sampled after 100min to detect the reaction condition of the materials, the detection shows that the materials can be completely dissolved in water, and no bubble is generated in the dissolving process, which indicates that the aminopyralid raw powder is completely converted into the potassium aminopyralid. The materials are sent into an oven and dried at the temperature of 80 ℃ to obtain 1410Kg of a dried product of the aminopyralid potassium salt, the content of the aminopyralid potassium salt is detected to be 95.1 percent, and the yield is 99.4 percent.
The product performance obtained in examples 1 to 3 is tested, namely the test result of the performance of the raw material drug of the picloram chloride potassium salt
It is to be understood that: although the above embodiments have described the design idea of the present invention in more detail, these descriptions are only simple descriptions of the design idea of the present invention, and are not limitations of the design idea of the present invention, and any combination, addition, or modification without departing from the design idea of the present invention falls within the scope of the present invention.
Claims (10)
1. A preparation method of a raw material drug of picloram potassium salt is characterized by comprising the following steps:
(1) putting the aminopyralid raw powder and potassium bicarbonate into a kneader according to a molar ratio of 1:1-1.1, mixing for 15-30min at 24.5-25.5 ℃, heating, keeping the temperature at 30-50 ℃, adding water, wherein the water amount is 1-8% of the mass of the aminopyralid raw powder, and kneading for 60-120 min;
(2) and after the reaction is finished, drying in a drying device at 65-100 ℃ to obtain the aminopyralid potassium salt raw material medicine.
2. The method for preparing the raw material drug of the potassium aminopyralid according to claim 1, which is characterized in that: the mol ratio of the aminopyralid to the potassium bicarbonate is 1:1-1.1, preferably 1: 1.04.
3. The method for preparing a potassium aminopyralid drug substance according to claim 1 or 2, characterized in that: the mol ratio of the aminopyralid to the potassium bicarbonate is 1: 1.04.
4. The method for preparing the raw material drug of the potassium aminopyralid according to claim 1, which is characterized by comprising the following steps: the solid aminopyralid and the potassium bicarbonate are premixed for 15-30min at the room temperature of 25 ℃, and then the temperature is raised to the reaction temperature for solid-solid reaction.
5. The method for preparing a potassium aminopyralid drug substance according to claim 1 or 4, which is characterized by comprising the following steps: the solid aminopyralid and the potassium bicarbonate are premixed for 20-25min at the room temperature of 25 ℃, and then the temperature is raised to the reaction temperature for solid-solid reaction.
6. The method for preparing the raw material drug of the potassium aminopyralid according to claim 1, which is characterized in that: the reaction temperature of the aminopyralid raw powder and the potassium bicarbonate is 40-80 ℃.
7. The method for preparing a potassium aminopyralid drug substance according to claim 1 or 6, characterized in that: the reaction temperature of the aminopyralid raw powder and the potassium bicarbonate is 60-70 ℃.
8. The method for preparing the raw material drug of the potassium aminopyralid according to claim 1, which is characterized in that: the reaction time of the aminopyralid raw powder and the potassium bicarbonate is 60-120min, preferably 90-120 min.
9. The method for preparing a potassium aminopyralid drug substance according to claim 1 or 8, characterized in that: the reaction time of the aminopyralid raw powder and the potassium bicarbonate is 90-120 min.
10. The method for preparing the raw material drug of the potassium aminopyralid according to claim 1, which is characterized in that: the drying mode in the drying device is drying in an oven, and the drying temperature is 65-100 ℃ or 80 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011565245.0A CN112608272A (en) | 2020-12-25 | 2020-12-25 | Preparation method of picloram potassium salt bulk drug |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011565245.0A CN112608272A (en) | 2020-12-25 | 2020-12-25 | Preparation method of picloram potassium salt bulk drug |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112608272A true CN112608272A (en) | 2021-04-06 |
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| CN202011565245.0A Pending CN112608272A (en) | 2020-12-25 | 2020-12-25 | Preparation method of picloram potassium salt bulk drug |
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| Country | Link |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE602006002738D1 (en) * | 2006-06-26 | 2008-10-23 | Chemagis Ltd | Improved process for the preparation of moxonidine |
| CN105820115A (en) * | 2016-06-01 | 2016-08-03 | 山东润博生物科技有限公司 | Preparing method for environment-friendly picloram salt |
| CN106035337A (en) * | 2016-06-01 | 2016-10-26 | 山东润博生物科技有限公司 | Water soluble granules of picloram salt and preparation method thereof |
-
2020
- 2020-12-25 CN CN202011565245.0A patent/CN112608272A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE602006002738D1 (en) * | 2006-06-26 | 2008-10-23 | Chemagis Ltd | Improved process for the preparation of moxonidine |
| CN105820115A (en) * | 2016-06-01 | 2016-08-03 | 山东润博生物科技有限公司 | Preparing method for environment-friendly picloram salt |
| CN106035337A (en) * | 2016-06-01 | 2016-10-26 | 山东润博生物科技有限公司 | Water soluble granules of picloram salt and preparation method thereof |
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