CN111777567A - Method for refining cyromazine technical product - Google Patents
Method for refining cyromazine technical product Download PDFInfo
- Publication number
- CN111777567A CN111777567A CN202010734619.0A CN202010734619A CN111777567A CN 111777567 A CN111777567 A CN 111777567A CN 202010734619 A CN202010734619 A CN 202010734619A CN 111777567 A CN111777567 A CN 111777567A
- Authority
- CN
- China
- Prior art keywords
- cyromazine
- refining
- steps
- following
- triazine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- LVQDKIWDGQRHTE-UHFFFAOYSA-N cyromazine Chemical compound NC1=NC(N)=NC(NC2CC2)=N1 LVQDKIWDGQRHTE-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 239000005891 Cyromazine Substances 0.000 title claims abstract description 55
- 229950000775 cyromazine Drugs 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 16
- 238000007670 refining Methods 0.000 title claims abstract description 9
- 239000003814 drug Substances 0.000 claims abstract description 26
- 229940079593 drug Drugs 0.000 claims abstract description 25
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- RHYYBHZFUCSINS-UHFFFAOYSA-N 2,4-dichloro-6-cyclopropyl-1,3,5-triazine Chemical compound ClC1=NC(Cl)=NC(C2CC2)=N1 RHYYBHZFUCSINS-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 11
- 239000012452 mother liquor Substances 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- 241001517923 Douglasiidae Species 0.000 description 5
- 238000000746 purification Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 244000295724 Allium chinense Species 0.000 description 2
- 235000018645 Allium odorum Nutrition 0.000 description 2
- 240000008654 Allium ramosum Species 0.000 description 2
- 235000005338 Allium tuberosum Nutrition 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000238631 Hexapoda Species 0.000 description 2
- 244000046052 Phaseolus vulgaris Species 0.000 description 2
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 235000016790 Allium chinense Nutrition 0.000 description 1
- 240000002234 Allium sativum Species 0.000 description 1
- 244000241257 Cucumis melo Species 0.000 description 1
- 235000015510 Cucumis melo subsp melo Nutrition 0.000 description 1
- 241000594034 Liriomyza huidobrensis Species 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 235000012055 fruits and vegetables Nutrition 0.000 description 1
- 235000004611 garlic Nutrition 0.000 description 1
- 235000021384 green leafy vegetables Nutrition 0.000 description 1
- 239000003630 growth substance Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 230000005923 long-lasting effect Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- SNICXCGAKADSCV-UHFFFAOYSA-N nicotine Chemical compound CN1CCCC1C1=CC=CN=C1 SNICXCGAKADSCV-UHFFFAOYSA-N 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D251/00—Heterocyclic compounds containing 1,3,5-triazine rings
- C07D251/02—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings
- C07D251/12—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
- C07D251/26—Heterocyclic compounds containing 1,3,5-triazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members with only hetero atoms directly attached to ring carbon atoms
- C07D251/40—Nitrogen atoms
- C07D251/54—Three nitrogen atoms
- C07D251/70—Other substituted melamines
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/66—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms
- A01N43/68—1,3,5-Triazines, not hydrogenated and not substituted at the ring nitrogen atoms with two or three nitrogen atoms directly attached to ring carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a method for refining cyromazine technical, which comprises the following steps: s1: adding a cyromazine crude drug prepared by taking 2-N cyclopropyl-4, 6 dichloro-s-triazine as a raw material into an alkaline water system; s2: then heating to 30-100 ℃, stirring for 2-6 hours at the temperature, and then cooling to 0-20 ℃; s3: filtering and drying to obtain the refined cyromazine original drug. The invention utilizes the characteristic that cyromazine is easy to dissolve in water solution, the cyromazine is dissolved at high temperature, after insoluble impurities are removed by filtration, the cyromazine is cooled and crystallized, and the refined cyromazine is obtained, the yield is 95 percent, and the content is 99 percent.
Description
Technical Field
The invention relates to the technical field of cyromazine technical, in particular to a refining method of cyromazine technical.
Background
N-cyclopropyl-1, 3, 5-triazine-2, 4, 6-triamine (cyromazine technical) is a low-toxicity insecticide of insect growth regulator type developed by Ciha-Gergy of Switzerland, which was introduced in the sixty and seventy years of the 20 th century, has very strong selectivity and is mainly active against dipteran insects. At present, the fruit and vegetable production is mainly used for prevention and treatment: various leaf miners such as Meizhou leaf miners, south American leaf miners, bean stem black leaf miners, scallion leaf miners and clover leaf miners for various melons, solanaceous fruits, beans and various leaf vegetables, root maggots of Chinese chives, scallion and garlic (the root maggots of the slow eye mushrooms (x wen) of the Chinese chives), and the like. The medicine has effects of contact killing and stomach poisoning, and has strong systemic conductivity, long lasting period, but slow action speed. The cyromazine has no toxic and side effects on human and livestock, and is safe to environment.
The cyromazine original drug is mainly synthesized by taking 2-N cyclopropyl-4, 6 dichloro-s-triazine as a raw material and ammoniating the raw material with liquid ammonia, and is a commonly adopted process route at home and abroad at present. The purification method of cyromazine has been reported in the research on synthesis and purification of cyromazine in the known documents "research on synthesis and application of cyromazine" (Chen Silo, 0258-. The prior art related to the purification method of cyromazine is mainly an ethanol recrystallization method, which has long purification period, high cost and large safety risk, thus being not suitable for industrial production.
Disclosure of Invention
The invention aims to provide a method for refining cyromazine technical product, which comprises the following steps:
s1: adding a cyromazine crude drug prepared by taking 2-N cyclopropyl-4, 6 dichloro-s-triazine as a raw material into an alkaline water system;
s2: then heating to 30-100 ℃, stirring for 2-6 hours at the temperature, and then cooling to 0-20 ℃;
s3: filtering and drying to obtain the refined cyromazine original drug.
Preferably, the alkaline water is one or more of sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate and potassium carbonate aqueous solution with the pH value of 10-14.
Preferably, the mass ratio of the alkaline water to the cyromazine crude product is as follows: 1-13: 1.
preferably, the preparation method of the cyromazine crude product prepared by taking 2-N cyclopropyl-4, 6 dichloro-s-triazine as a raw material comprises the following steps: adding 2-N cyclopropyl-4, 6 dichloro-s-triazine into the autoclave, then introducing ammonia at the temperature of 110-plus-130 ℃ for reaction for 4-8h, cooling and filtering to obtain the crude cyromazine.
Compared with the prior art, the invention has the beneficial effects that: the invention utilizes the characteristic that cyromazine is easy to dissolve in water solution, the cyromazine is dissolved at high temperature, after insoluble impurities are removed by filtration, the cyromazine is cooled and crystallized, and the refined cyromazine is obtained, the yield is 95 percent, and the content is 99 percent.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the embodiment, the cyromazine original drug is prepared by taking 2-N cyclopropyl-4, 6 dichloro-s-triazine as a raw material, the percentage content of the cyromazine original drug is determined by liquid chromatogram, and the chromatogram condition is as follows: mobile phase: methanol: water 50:50, column C18.
Example 1
Adding 1kg of cyromazine crude drug into a dry 10L reaction kettle, adding 5kg of sodium hydroxide solution with pH of 12 into the reaction kettle, heating to 98 ℃, stirring for 2h, carrying out suction filtration while hot, slowly cooling mother liquor to 8 ℃, filtering and drying to obtain 945g of cyromazine crude drug with the purity of 99.5%, wherein the yield is 94.5%.
Example 2
Adding 1kg of cyromazine crude drug into a dry 10L reaction kettle, adding 5kg of sodium hydroxide solution with pH of 12 into the reaction kettle, heating to 98 ℃, stirring for 2h, carrying out suction filtration while hot, slowly cooling mother liquor to 8 ℃, filtering and drying to obtain 936g of cyromazine crude drug with the purity of 99.7%, wherein the yield is 93.6%.
Example 3
Adding 1kg of cyromazine crude drug into a dry 10L reaction kettle, adding 5kg of sodium hydroxide solution with pH of 12 into the reaction kettle, heating to 98 ℃, stirring for 2h, carrying out suction filtration while hot, slowly cooling mother liquor to 8 ℃, filtering and drying to obtain 952g of cyromazine crude drug with purity of 98.5%, wherein the yield is 95.2%.
Example 4
Adding 1kg of cyromazine crude drug into a dry 10L reaction kettle, adding 5kg of sodium hydroxide solution with pH of 12 into the reaction kettle, heating to 96 ℃, stirring for 2h, carrying out suction filtration while hot, slowly cooling mother liquor to 8 ℃, filtering and drying to obtain 954g of cyromazine crude drug with purity of 98.9%, wherein the yield is 95.4%.
Example 5
Adding 1kg of cyromazine crude drug into a dry 10L reaction kettle, adding 5kg of sodium hydroxide solution with pH of 12 into the reaction kettle, heating to 96 ℃, stirring for 2h, carrying out suction filtration while hot, slowly cooling mother liquor to 8 ℃, filtering and drying to obtain 939g of cyromazine crude drug with the purity of 99.1%, wherein the yield is 93.9%.
Example 6
Adding 1kg of cyromazine crude drug into a dry 10L reaction kettle, adding 5kg of sodium hydroxide solution with pH of 12 into the reaction kettle, heating to 97 ℃, stirring for 2h, carrying out suction filtration while hot, slowly cooling mother liquor to 8 ℃, filtering and drying to obtain 948g of cyromazine crude drug with the purity of 99.4%, wherein the yield is 94.8%.
Example 7
Adding 1kg of cyromazine crude drug into a dry 10L reaction kettle, adding 5kg of sodium hydroxide solution with pH of 12 into the reaction kettle, heating to 97 ℃, stirring for 2h, carrying out suction filtration while hot, slowly cooling mother liquor to 8 ℃, filtering and drying to obtain 938g of cyromazine crude drug with the purity of 99.7%, wherein the yield is 93.8%.
Example 8
Adding 1kg of cyromazine crude drug into a dry 10L reaction kettle, adding 5kg of sodium hydroxide solution with pH of 12 into the reaction kettle, heating to 97 ℃, stirring for 2h, carrying out suction filtration while hot, slowly cooling mother liquor to 8 ℃, filtering and drying to obtain 947g of cyromazine crude drug with the purity of 99.6%, wherein the yield is 94.7%.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (4)
1. A method for refining cyromazine technical is characterized by comprising the following steps:
s1: adding a cyromazine crude drug prepared by taking 2-N cyclopropyl-4, 6 dichloro-s-triazine as a raw material into an alkaline water system;
s2: then heating to 30-100 ℃, stirring for 2-6 hours at the temperature, and then cooling to 0-20 ℃;
s3: filtering and drying to obtain the refined cyromazine original drug.
2. The method for refining cyromazine according to claim 1, wherein the method comprises the following steps: the alkaline water is one or more of aqueous solution of sodium hydroxide, potassium hydroxide, sodium bicarbonate, sodium carbonate and potassium carbonate with pH value of 10-14.
3. The method for refining cyromazine according to claim 1, wherein the method comprises the following steps: the mass ratio of the alkaline water to the cyromazine crude product is as follows: 1-13: 1.
4. the method for refining cyromazine according to claim 1, wherein the method comprises the following steps: the preparation method of the cyromazine crude product prepared by taking 2-N cyclopropyl-4, 6 dichloro-s-triazine as a raw material comprises the following steps: adding 2-N cyclopropyl-4, 6 dichloro-s-triazine into the autoclave, then introducing ammonia at the temperature of 110-plus-130 ℃ for reaction for 4-8h, cooling and filtering to obtain the crude cyromazine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010734619.0A CN111777567A (en) | 2020-07-27 | 2020-07-27 | Method for refining cyromazine technical product |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010734619.0A CN111777567A (en) | 2020-07-27 | 2020-07-27 | Method for refining cyromazine technical product |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111777567A true CN111777567A (en) | 2020-10-16 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010734619.0A Pending CN111777567A (en) | 2020-07-27 | 2020-07-27 | Method for refining cyromazine technical product |
Country Status (1)
| Country | Link |
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| CN (1) | CN111777567A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116041269A (en) * | 2022-03-31 | 2023-05-02 | 瑞普（天津）生物药业有限公司 | Novel cyromazine crystal form and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1202487A (en) * | 1997-06-18 | 1998-12-23 | 吉林化学工业公司江南设计研究院 | Two-step process for synthesizing anabasine |
| CN1356039A (en) * | 2001-11-09 | 2002-07-03 | 复旦大学 | Process for preparing insecticide 'Huanbingmazhen' |
| CN108084102A (en) * | 2017-11-27 | 2018-05-29 | 河南后羿制药有限公司 | A kind of preparation method of cyromazine |
| CN111620831A (en) * | 2020-07-06 | 2020-09-04 | 山东国邦药业有限公司 | Preparation method of cyromazine |
-
2020
- 2020-07-27 CN CN202010734619.0A patent/CN111777567A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1202487A (en) * | 1997-06-18 | 1998-12-23 | 吉林化学工业公司江南设计研究院 | Two-step process for synthesizing anabasine |
| CN1356039A (en) * | 2001-11-09 | 2002-07-03 | 复旦大学 | Process for preparing insecticide 'Huanbingmazhen' |
| CN108084102A (en) * | 2017-11-27 | 2018-05-29 | 河南后羿制药有限公司 | A kind of preparation method of cyromazine |
| CN111620831A (en) * | 2020-07-06 | 2020-09-04 | 山东国邦药业有限公司 | Preparation method of cyromazine |
Non-Patent Citations (1)
| Title |
|---|
| 邱家军，等: "环丙氨嗪合成工艺研究", 《精细化工中间体》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116041269A (en) * | 2022-03-31 | 2023-05-02 | 瑞普（天津）生物药业有限公司 | Novel cyromazine crystal form and preparation method and application thereof |
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Application publication date: 20201016 |
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