CN107118169B - Synthesis method of 4-amino-6-tert-butyl-3-methylthio-1, 2, 4-triazine-5 (4H) -ketone - Google Patents
Synthesis method of 4-amino-6-tert-butyl-3-methylthio-1, 2, 4-triazine-5 (4H) -ketone Download PDFInfo
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- CN107118169B CN107118169B CN201710310571.9A CN201710310571A CN107118169B CN 107118169 B CN107118169 B CN 107118169B CN 201710310571 A CN201710310571 A CN 201710310571A CN 107118169 B CN107118169 B CN 107118169B
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- 238000001308 synthesis method Methods 0.000 title description 2
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims abstract description 60
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 42
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- 229940102396 methyl bromide Drugs 0.000 claims abstract description 28
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- FOXFZRUHNHCZPX-UHFFFAOYSA-N metribuzin Chemical compound CSC1=NN=C(C(C)(C)C)C(=O)N1N FOXFZRUHNHCZPX-UHFFFAOYSA-N 0.000 claims abstract description 25
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 11
- 238000007036 catalytic synthesis reaction Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- 229940123973 Oxygen scavenger Drugs 0.000 claims description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 2
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 2
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 24
- 238000004519 manufacturing process Methods 0.000 abstract description 15
- 239000005583 Metribuzin Substances 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004880 explosion Methods 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- 231100000331 toxic Toxicity 0.000 abstract description 2
- 230000002588 toxic effect Effects 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 24
- QMNWYGTWTXOQTP-UHFFFAOYSA-N 1h-triazin-6-one Chemical compound O=C1C=CN=NN1 QMNWYGTWTXOQTP-UHFFFAOYSA-N 0.000 description 10
- 150000001875 compounds Chemical class 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- OFKAVNQBCRJBJE-UHFFFAOYSA-N 4-amino-6-tert-butyl-3-sulfanylidene-2h-1,2,4-triazin-5-one Chemical compound CC(C)(C)C1=NNC(=S)N(N)C1=O OFKAVNQBCRJBJE-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 2
- 229920002556 Polyethylene Glycol 300 Polymers 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 150000002923 oximes Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009885 systemic effect Effects 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
- FZENGILVLUJGJX-NSCUHMNNSA-N (E)-acetaldehyde oxime Chemical compound C\C=N\O FZENGILVLUJGJX-NSCUHMNNSA-N 0.000 description 1
- WHIVNJATOVLWBW-PLNGDYQASA-N (nz)-n-butan-2-ylidenehydroxylamine Chemical compound CC\C(C)=N/O WHIVNJATOVLWBW-PLNGDYQASA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 208000003643 Callosities Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 206010020649 Hyperkeratosis Diseases 0.000 description 1
- 235000007688 Lycopersicon esculentum Nutrition 0.000 description 1
- 240000004658 Medicago sativa Species 0.000 description 1
- 235000017587 Medicago sativa ssp. sativa Nutrition 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 240000003768 Solanum lycopersicum Species 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 125000002816 methylsulfanyl group Chemical group [H]C([H])([H])S[*] 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical compound [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 description 1
- 235000019252 potassium sulphite Nutrition 0.000 description 1
- 235000012015 potatoes Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D253/00—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00
- C07D253/02—Heterocyclic compounds containing six-membered rings having three nitrogen atoms as the only ring hetero atoms, not provided for by group C07D251/00 not condensed with other rings
- C07D253/06—1,2,4-Triazines
- C07D253/065—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members
- C07D253/07—1,2,4-Triazines having three double bonds between ring members or between ring members and non-ring members 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
- C07D253/075—Two hetero atoms, in positions 3 and 5
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a catalytic synthesis method of 4-amino-6-tert-butyl-3-methylthio-1, 2, 4-triazine-5 (4H) -ketone, which comprises the following steps: sequentially adding process water, caustic soda flakes, triazone and a catalyst into a dissolving kettle, and stirring until the process water, the caustic soda flakes, the triazone and the catalyst are completely dissolved; transferring the materials into a synthesis kettle, introducing methyl bromide into the synthesis kettle under the stirring condition to prepare metribuzin, and preserving the temperature of the system for 0.5-1 h after the reaction is finished; introducing nitrogen into the reaction kettle to blow off redundant methyl bromide, raising the temperature in the synthesis kettle to 48-55 ℃, and preserving the temperature for 0.5-1.5 h; and cooling, washing and suction-filtering the material to obtain metribuzin. The method provided by the invention has the advantages that the addition amount of the catalyst is small, no toxic or side effect exists, and on one hand, the raw material input cost and the post-treatment process cost of product solvent recovery are reduced; on the other hand, the catalyst has less consumption, avoids the danger of easy explosion compared with methanol, and improves the safety factor of the production process.
Description
Technical Field
The invention belongs to the technical field of fine chemical engineering, and particularly relates to a catalytic synthesis method of systemic herbicide 4-amino-6-tert-butyl-3-methylthio-1, 2, 4-triazine-5 (4H) -ketone.
Background
The 4-amino-6-tert-butyl-3-methylthio-1, 2, 4-triazine-5 (4H) -ketone is also called metribuzin, is a systemic selective herbicide, is mainly absorbed by roots of crops, is widely used for preventing and killing various weeds on crops such as tomatoes, soybeans, potatoes, corns, alfalfa, sugarcanes and the like, and is widely researched by scientific researchers due to the characteristics of high efficiency and low toxicity.
Currently, metribuzin is prepared by taking methanol as a catalyst and taking 4-amino-6-tert-butyl-3-mercapto-1, 2, 4-triazine-5 (4H) -one (triazone) and methyl bromide as raw materials under the alkaline condition. However, in the preparation process, a large amount of methanol is required, so that on one hand, the recovery cost of raw materials and a solvent is increased; on the other hand, methanol is volatile and has a low boiling point, so that the danger of explosion exists in the production process, namely the danger coefficient of the production process is increased by using methanol as a catalyst; in addition, because methyl bromide is not easy to dissolve in water, the reaction is slow, so that the conversion rate of the raw material triazone is not high; and because oxygen in a reaction system can not be removed, bromine is dissociated in the synthesis, the color of the product is further influenced, and a series of problems that the product quality is not over-critical, the post-treatment operation is increased, the production cost is increased and the like are caused.
Research shows that impurities contained in the finished metribuzin product produced by the prior art have the following structures:
the presence of the above impurities seriously affects the quality and efficacy of metribuzin, and therefore it is desirable to minimize the content of these impurities.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a catalytic synthesis method of 4-amino-6-tert-butyl-3-methylthio-1, 2, 4-triazine-5 (4H) -ketone, which aims at overcoming the defects of the prior art, reduces side reactions, improves the conversion rate of raw materials, improves the yield and quality of products, is simple and convenient to operate and has high safety coefficient.
The technical scheme is as follows: the invention relates to a catalytic synthesis method of 4-amino-6-tert-butyl-3-methylthio-1, 2, 4-triazine-5 (4H) -ketone (II), which is characterized by comprising the following steps:
(1) sequentially adding process water, caustic soda flakes, 4-amino-6-tert-butyl-3-mercapto-1, 2, 4-triazine-5 (4H) -ketone (I) and a catalyst into a dissolving kettle, and stirring until the catalyst is completely dissolved, wherein the catalyst is one or more of polyethylene glycol (PEG), nonylphenol polyoxyethylene ether or ethylene glycol dimethyl ether;
(2) transferring the material in the step (1) into a synthesis kettle, controlling the temperature in the synthesis kettle to be 20-28 ℃, introducing bromomethane into the synthesis kettle under the stirring condition, and controlling the first half-process speed of introducing the bromomethane to be 10-1.5 kg/min; the feeding speed of the second half is 0.5-0.8 kg/min, and the pH value of the system is controlled to be 8.5-9 in the feeding process of the methyl bromide; in the process, 4-amino-6-tert-butyl-3-mercapto-1, 2, 4-triazine-5 (4H) -ketone (I) and methyl bromide react under the condition of a catalyst to prepare 4-amino-6-tert-butyl-3-methylthio-1, 2, 4-triazine-5 (4H) -ketone (II), and after the reaction is finished, the system is kept warm for 0.5-1H;
(3) introducing nitrogen into the reaction kettle to blow off redundant methyl bromide, raising the temperature in the synthesis kettle to 48-55 ℃, and preserving the temperature for 0.5-1.5 h;
(4) and (4) cooling, washing and filtering the materials in the step (3) to obtain 4-amino-6-tert-butyl-3-methylthio-1, 2, 4-triazine-5 (4H) -ketone (II).
Further, in order to further improve the quality of the product, control the color of the product and reduce the cost of the post-treatment process, the oxygen scavenger is also added in the step (1).
Further, the oxygen scavenger is one or more of sulfite, oxime or hydrazine hydrate.
Further, the sulfite is sodium sulfite or potassium sulfite; the oxime is dimethyl ketoxime or butanone oxime or acetaldoxime.
Further, the oxygen scavenger is one or a mixture of sodium sulfite and dimethyl ketoxime.
Furthermore, in order to improve the activity of the catalyst relative to a reaction system, the molecular weight of the catalyst in the step (1) is 200-1000 g/mol.
Further, the caustic soda flakes in the step (1) are sodium hydroxide.
Further, the feeding mass ratio of the process water, the flake caustic soda and the 4-amino-6-tert-butyl-3-mercapto-1, 2, 4-triazine-5 (4H) -ketone in the step (1) is as follows: 3-4: 0.1-0.3: 1.
Further, the adding amount of the catalyst in the step (1) is 3-5% of the mass of 4-amino-6-tert-butyl-3-mercapto-1, 2, 4-triazine-5 (4H) -ketone; the addition amount of the deoxidant is 0.08-0.15% of the mass of the process water.
Further, the mass ratio of the introduction amount of the methyl bromide in the step (2) to the 4-amino-6-tert-butyl-3-mercapto-1, 2, 4-triazin-5 (4H) -one (I) is 1: 1.6-1: 1.7.
has the advantages that: (1) the method provided by the invention adopts a catalyst more suitable for the reaction system, the addition amount of the catalyst is small, no toxic or side effect is caused, and compared with the existing production process in which methanol is added as the catalyst, the method reduces the raw material input cost and the post-treatment process cost of product solvent recovery; on the other hand, the catalyst is less in dosage, and compared with methanol, the danger of easy explosion is avoided, and the safety coefficient of the production process is improved;
(2) the catalyst used in the invention is beneficial to dissolving insoluble substances in the third substance and transferring specific ions to an organic phase, so that the reaction of the ions and organic matters is increased, and the problems of slow reaction and low raw material conversion rate caused by the fact that methyl bromide is insoluble in water in the original production process are avoided;
(3) the catalyst used in the invention can effectively reduce the generation of byproducts (III), (IV) and (V), particularly can reduce the generation of the byproduct (V) to zero, and improves the overall quality of the product;
(4) the invention selects the deoxidant which is proper to the catalyst, has the effect of controlling the color of the product, improves the appearance quality of the product on the one hand, avoids the post-treatment process which is carried out because the product is deepened by oxidation color in the original process on the other hand, and saves the production cost.
Drawings
FIG. 1 is a NMR chart of 4-amino-6-tert-butyl-3-methylsulfanyl-1, 2, 4-triazin-5 (4H) -one obtained in example 2.
Detailed Description
The technical solution of the present invention is described in detail by the following examples, but the scope of the present invention is not limited to the examples.
Example 1: existing production process
367g of process water is put into a 500ml four-mouth bottle, 22g of sodium hydroxide is added, stirring is started, and the process water is completely dissolved; adding 100g of triazinone into a reaction bottle until the triazinone is completely dissolved; then 10g of methanol was added to the reaction flask; the reaction temperature was adjusted to 25 ℃ and 61.22g of methyl bromide was initially introduced at the rate: the first half is 1.2 kg/min; the second half is 0.7 kg/min; after the introduction of the methyl bromide is finished, adjusting the pH value of the system to 8.5-9 by using a 10% NaOH solution, and stirring for 0.5 h; then raising the temperature to 50 ℃, simultaneously introducing nitrogen to remove the residual methyl bromide in the reaction bottle, and keeping the temperature for 1 h; and cooling, washing, suction-filtering and drying the materials in the reaction bottle to obtain 91 g of metribuzin product, wherein the product is light red in appearance, has the purity of 94%, the yield of 85% and the content of the compound (V) of 0.5%, and is shown in the data in the table 1.
Example 2: the production process of the invention
367g of process water is put into a 500ml four-mouth bottle, 22g of sodium hydroxide is added, stirring is started, and the process water is completely dissolved; adding 100g of triazinone into a reaction bottle until the triazinone is completely dissolved; then 4g PEG-200, 0.37g Na was added to the reaction flask2SO3(ii) a The reaction temperature was adjusted to 25 ℃ and 61.22g of methyl bromide was initially introduced at the rate: the first half is 1.2 kg/min; the second half is 0.7 kg/min; after the introduction of the methyl bromide is finished, adjusting the pH value of the system to 8.5-9 by using a 10% NaOH solution, and stirring for 0.5 h; then raising the temperature to 50 ℃, simultaneously introducing nitrogen to remove the residual methyl bromide in the reaction bottle, and keeping the temperature for 1 h; and cooling, washing, filtering and drying the materials in the reaction bottle to obtain 100g of metribuzin product, wherein the product is white in appearance, the purity is 97.8%, the yield is 93.5%, and the content of the compound (V) is 0%, as shown in the data in the table 1.
FIG. 1 is a nuclear magnetic resonance image of 4-amino-6-tert-butyl-3-methylsulfanyl-1, 2, 4-triazin-5 (4H) -one obtained in this example, as determined by the dissolution in DMSO, at δ -5.932 (ppm) (s,2H, -NH)2),δ＝2.459(ppm)(s,3H,-SCH3),δ＝1.364(ppm)(s,9H,-CH3) All appear the characteristic peak of 4-amino-6-tert-butyl-3-methylthio-1, 2, 4-triazine-5 (4H) -ketone, and prove that the method successfully synthesizes the 4-amino-6-tert-butyl-3-methylthio-1, 2, 4-triazine-5 (4H) -ketone.
Example 3: the production process of the invention
Adding 300g of process water into a 500ml four-mouth bottle, adding 10.5g of sodium hydroxide, stirring, and dissolving completely; adding 100g of triazinone into a reaction bottle until the triazinone is completely dissolved; adding 3g of PEG-200 into the reaction bottle; the reaction temperature was adjusted to 20 ℃ and 62.5g of methyl bromide was initially introduced at the rate: the first half is 1 kg/min; the second half is 0.5 kg/min; after the introduction of the methyl bromide is finished, adjusting the pH value of the system to 8.5-9 by using a 10% NaOH solution, and stirring for 0.5 h; then raising the temperature to 48 ℃, simultaneously introducing nitrogen to remove the residual methyl bromide in the reaction bottle, and keeping the temperature for 1 h; and cooling, washing, filtering and drying the materials in the reaction bottle to obtain 98.5 g of metribuzin product, wherein the product is off-white in color, the purity is 97%, the yield is 92%, and the content of the compound (V) is 0%, as shown in the data in Table 1.
Example 4: the production process of the invention
Adding 400g of process water into a 500ml four-mouth bottle, adding 30g of potassium hydroxide, stirring, and completely dissolving; adding 100g of triazinone into a reaction bottle until the triazinone is completely dissolved; then 5g of PEG-300 is added into the reaction bottle; adjusting the reaction temperature to 28 ℃, and starting to introduce 58.8g of methyl bromide at the speed of 1.5kg/min in the first half; the second half is 0.8 kg/min; after the introduction of the methyl bromide is finished, adjusting the pH value of the system to 8.5-9 by using a 10% NaOH solution, and stirring for 0.5 h; then raising the temperature to 55 ℃, simultaneously introducing nitrogen to remove the residual methyl bromide in the reaction bottle, and keeping the temperature for 1 h; and cooling, washing, filtering and drying the materials in the reaction bottle to obtain 99.5 g of metribuzin product, wherein the product is off-white in color, the purity is 97.5%, the yield is 93%, and the content of the compound (V) is 0%, as shown in the data in Table 1.
Example 5: the production process of the invention
367g of process water is put into a 500ml four-mouth bottle, 22g of sodium hydroxide is added, stirring is started, and the process water is completely dissolved; adding 100g of triazinone into a reaction bottle until the triazinone is completely dissolved; 4g of PEG-300 and 0.37g of Dimethylketoxime (DMKO) were added to the reaction flask; the reaction temperature was adjusted to 25 ℃ and 61.22g of methyl bromide was initially introduced at the rate: the first half is 1.2 kg/min; the second half is 0.7 kg/min; after the introduction of the methyl bromide is finished, adjusting the pH value of the system to 8.5-9 by using a 10% NaOH solution, and stirring for 0.5 h; then raising the temperature to 50 ℃, simultaneously introducing nitrogen to remove the residual methyl bromide in the reaction bottle, and keeping the temperature for 1 h; and then cooling, washing, suction-filtering and drying the materials in the reaction bottle to obtain 99.5 g of metribuzin product, wherein the product is white in color, the purity is 97.6%, the yield is 93%, and the content of the compound (V) is 0%, as shown in the data in Table 1.
TABLE 1 EXAMPLES 1-5 product inspection data
As can be seen from the comparison of the data in Table 1, the product synthesized by the prior art has low yield and purity and high impurity content, while the product prepared by the method provided by the invention has high yield and purity, white color and low content of by-products, especially 0 content of by-product (V). This demonstrates the significant advantage of the production process over existing production processes.
As noted above, while the present invention has been shown and described with reference to certain preferred embodiments, it is not to be construed as limited thereto. Various changes in form and detail may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (6)
1. A catalytic synthesis method of 4-amino-6-tert-butyl-3-methylthio-1, 2, 4-triazine-5 (4H) -ketone (II) is characterized by comprising the following steps:
(1) sequentially adding process water, caustic soda flakes, 4-amino-6-tert-butyl-3-mercapto-1, 2, 4-triazine-5 (4H) -ketone (I) and a catalyst into a dissolving kettle, and stirring until the catalyst is completely dissolved, wherein the catalyst is one or more of polyethylene glycol (PEG), nonylphenol polyoxyethylene ether or ethylene glycol dimethyl ether;
(2) transferring the material in the step (1) into a synthesis kettle, controlling the temperature in the synthesis kettle to be 20-28 ℃, introducing bromomethane into the synthesis kettle under the stirring condition, and controlling the first half-process speed of introducing the bromomethane to be 10-1.5 kg/min; the feeding speed of the second half is 0.5-0.8 kg/min, and the pH value of the system is controlled to be 8.5-9 in the feeding process of the methyl bromide; in the process, 4-amino-6-tert-butyl-3-mercapto-1, 2, 4-triazine-5 (4H) -ketone (I) and methyl bromide react under the condition of a catalyst to prepare 4-amino-6-tert-butyl-3-methylthio-1, 2, 4-triazine-5 (4H) -ketone (II), and after the reaction is finished, the system is kept warm for 0.5-1H;
(3) introducing nitrogen into the reaction kettle to blow off redundant methyl bromide, raising the temperature in the synthesis kettle to 48-55 ℃, and preserving the temperature for 0.5-1.5 h;
(4) cooling, washing and filtering the materials in the step (3) to obtain 4-amino-6-tert-butyl-3-methylthio-1, 2, 4-triazine-5 (4H) -ketone (II);
adding an oxygen scavenger in the step (1);
the oxygen scavenger is one or a mixture of sodium sulfite and dimethyl ketoxime.
2. The process for the catalytic synthesis of 4-amino-6-tert-butyl-3-methylsulfanyl-1, 2, 4-triazin-5 (4H) -one (II) according to claim 1, characterized in that: the molecular weight of the catalyst in the step (1) is 200-1000 g/mol.
3. The process for the catalytic synthesis of 4-amino-6-tert-butyl-3-methylsulfanyl-1, 2, 4-triazin-5 (4H) -one (II) according to claim 1, characterized in that: the flake caustic soda in the step (1) is sodium hydroxide.
4. The process for the catalytic synthesis of 4-amino-6-tert-butyl-3-methylsulfanyl-1, 2, 4-triazin-5 (4H) -one (II) according to claim 1, characterized in that: the feeding mass ratio of the process water, the caustic soda flakes and the 4-amino-6-tert-butyl-3-mercapto-1, 2, 4-triazine-5 (4H) -ketone in the step (1) is as follows: 3-4: 0.1-0.3: 1.
5. The process for the catalytic synthesis of 4-amino-6-tert-butyl-3-methylsulfanyl-1, 2, 4-triazin-5 (4H) -one (II) according to claim 1, characterized in that: the adding amount of the catalyst in the step (1) is 3-5% of the mass of 4-amino-6-tert-butyl-3-mercapto-1, 2, 4-triazine-5 (4H) -ketone; the addition amount of the deoxidant is 0.08-0.15% of the mass of the process water.
6. The process for the catalytic synthesis of 4-amino-6-tert-butyl-3-methylsulfanyl-1, 2, 4-triazin-5 (4H) -one (II) according to claim 1, characterized in that: the mass ratio of the introduction amount of the methyl bromide to the 4-amino-6-tert-butyl-3-mercapto-1, 2, 4-triazine-5 (4H) -ketone (I) in the step (2) is 1: 1.6-1: 1.7.
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| CN103333129A (en) * | 2013-07-03 | 2013-10-02 | 苏州诚和医药化学有限公司 | Method for preparing 4-amino-6-tertiary butyl-3-methylmercapto-1,2,4-triazine-5(4H)-ketone |
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| CN103333129A (en) * | 2013-07-03 | 2013-10-02 | 苏州诚和医药化学有限公司 | Method for preparing 4-amino-6-tertiary butyl-3-methylmercapto-1,2,4-triazine-5(4H)-ketone |
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