CN113527255B - Method for synthesizing chlorantraniliprole intermediate - Google Patents
Method for synthesizing chlorantraniliprole intermediate Download PDFInfo
- Publication number
- CN113527255B CN113527255B CN202110821154.7A CN202110821154A CN113527255B CN 113527255 B CN113527255 B CN 113527255B CN 202110821154 A CN202110821154 A CN 202110821154A CN 113527255 B CN113527255 B CN 113527255B
- Authority
- CN
- China
- Prior art keywords
- compound
- chlorantraniliprole
- reaction
- synthesizing
- tribromooxyphosphorus
- 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.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention relates to the technical field of chemical synthesis, and particularly discloses a synthesis method of a chlorantraniliprole intermediate. The synthesis method comprises the following steps: under the condition of organic solvent, taking a compound I and tribromooxyphosphorus as raw materialsAnd carrying out bromination oxidation one-step reaction to obtain a compound II. According to the invention, under the condition of a specific solvent, the compound I and the tribromooxyphosphorus are used as raw materials in a specific proportion, the compound II is prepared by one-step reaction, the reaction product can be obtained into a product with the purity of more than 98.5% only by simple post-treatment, the yield can reach more than 92%, the raw materials are few in variety, the production cost is low, the three wastes generated in the reaction process are few, the process is green and environment-friendly, and the method is suitable for large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of chemical synthesis, in particular to a synthesis method of a chlorantraniliprole intermediate.
Background
Chlorantraniliprole is an efficient, broad-spectrum and low-toxicity o-formamido benzamide pesticide developed by DuPont company in 2000, has a chemical name of 3-bromo-N- [ 4-chloro-2-methyl-6- (methylcarbamoyl) benzene ] -1- (3-chloropyridin-2-yl) -1H-pyrazole-5-formamide, and has a structural formula shown in a formula III.
3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-ethyl formate is an important intermediate of chlorantraniliprole, and the structural formula is shown as a formula II. The 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxylic acid ethyl ester is hydrolyzed to generate 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxylic acid, and then the 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxylic acid ethyl ester reacts with 2-amino-5-chloro-N, 3-dimethylformamide to generate chlorantraniliprole. Currently, the main synthesis method of ethyl 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxylate is: 2- (3-chloropyridin-2-yl) -5-oxo-pyrazolidine-3-ethyl formate is used as a raw material, brominated by a bromination reagent to obtain 3-bromo-1- (3-chloropyridin-2-yl) -4, 5-dihydro-1H-pyrazole-5-ethyl formate, then oxidized by sulfate to obtain 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-ethyl formate with the total yield of 85 percent, step-by-step reaction is needed, the production efficiency is low, a large amount of mixed acid wastewater containing hydrobromic acid and phosphoric acid is generated in a bromination reaction part, a large amount of sulfate wastewater and an organic solvent containing water are generated in an oxidation reaction part, the three wastes are more in variety and more in treatment difficulty. Therefore, the development of the high-efficiency synthesis method of the chlorantraniliprole intermediate which is environment-friendly and has higher yield and purity has very important significance.
Disclosure of Invention
Aiming at the problems of more reaction steps, lower yield and purity and large difficulty in treating generated three wastes in the synthesis method of the chlorantraniliprole intermediate in the prior art, the invention provides the synthesis method of the chlorantraniliprole intermediate.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a method for synthesizing a chlorantraniliprole intermediate comprises the following steps:
under the condition of an organic solvent, taking a compound I and tribromooxyphosphorus as raw materials, and preparing a compound II through one-step reaction of bromination and oxidation;
wherein the organic solvent is valeronitrile, dichlorobutane, phenylacetonitrile or diethylene glycol dimethyl ether; the molar ratio of the compound I to the tribromooxyphosphorus is 1: 2-5.
Compared with the prior art, the synthesis method of the chlorantraniliprole intermediate provided by the invention has the advantages that under the condition of a specific solvent, the compound I and the tribromooxyphosphorus are used as raw materials in a specific proportion, the bromination and the oxidation reaction are simultaneously carried out, the existing reaction for preparing the compound II by a two-step method is simplified into a one-step method, the reaction steps are simplified, the production efficiency is obviously improved, meanwhile, the yield and the purity of the compound II are obviously improved, the yield can reach more than 92 percent, the purity can reach more than 98.5 percent, in addition, the generation of a large amount of sulfate and an aqueous organic solvent is avoided, the three-waste variety is simplified, the environmental protection treatment difficulty is reduced, the requirements of a green production process are better met, the large-scale industrial production is favorably realized, and the synthesis method has very important significance for the development of chlorantraniliprole pesticide.
Preferably, the synthesis method of the chlorantraniliprole intermediate specifically comprises the following steps:
step a, adding tribromooxyphosphorus into an organic solvent, uniformly mixing, adding a compound I, and reacting at 100-130 ℃ for 5-10 h to obtain a reaction solution containing a compound II;
and b, removing part of the solvent of the reaction solution containing the compound II, cooling to 0-30 ℃, adding water, stirring, carrying out suction filtration, and drying to obtain the compound II. The reaction equation is as follows:
the synthesis method of the chlorantraniliprole intermediate simplifies the step of oxidation reaction by adopting persulfate after bromination, simplifies the reaction steps, reduces the types of raw materials, avoids the generation of a large amount of sulfate waste, has mild reaction conditions and simple post-treatment, obtains the product with the yield of more than 92% and the purity of more than 98.5% only by washing and drying, obviously reduces the reaction cost and energy consumption, is green and environment-friendly, improves the feasibility of industrialization, and has wide application prospect.
Preferably, the organic solvent is valeronitrile.
Preferably, the molar ratio of the compound I to the tribromooxyphosphorus is 1: 2-3.
Preferably, the mass ratio of the organic solvent to the compound I is 3-5: 1.
The preferable reaction conditions can avoid side reactions while ensuring the full reaction of the reaction raw materials, thereby improving the yield and purity of the target product.
Preferably, in the step a, the reaction temperature is 125-130 ℃, and the reaction time is 5-6 h.
The optimal reaction temperature and reaction time can improve the reaction efficiency and ensure the yield and quality of the target product on the premise of reducing side reactions to the maximum extent.
Preferably, in the step b, the removal amount of the solvent is 90-98% of the total mass of the added organic solvent.
The removed fractions mainly comprise organic solvent and excessive tribromooxyphosphorus can be recycled to the reaction step a, so that the reaction cost is saved, and the generation amount of hazardous waste is reduced.
Preferably, in step b, the amount of water added is 3 to 5 times the mass of compound I.
Preferably, in the step b, the temperature is reduced to 0-30 ℃ after removing part of the solvent.
The optimized solvent removal amount, the water addition amount and the cooling temperature are favorable for fully separating out the compound II, reducing the separation of impurities and improving the yield and the purity of a target product.
Preferably, in step b, the recovered solvent is recycled back to step a for use as a reaction solvent and starting material.
And (b) when the solvent is recovered, unreacted tribromooxyphosphorus is recovered together, so that the recovered solvent is applied to the step a to serve as the reaction solvent and the raw material, the three-waste treatment amount is reduced, the energy consumption for three-waste treatment is reduced, the consumption of tribromooxyphosphorus in the application batch is reduced, the raw material cost is reduced, and the economic benefit and the environmental benefit are higher.
Further preferably, when the recovered solvent is recycled to step a, the molar ratio of the compound I to the tribromooxyphosphorus is controlled to be 1: 2-3.
Because the recovered solvent contains part of unreacted tribromooxyphosphorus, in order to ensure that the molar ratio of the compound I to tribromooxyphosphorus in the reaction system is within the range of 1:2-5, when the recovered solvent is used, the molar ratio of the compound I to tribromooxyphosphorus in the step a needs to be controlled to be 1:2-3 so as to prevent the excessive tribromooxyphosphorus from generating side reaction, thereby reducing the yield and the purity of the compound II.
According to the invention, under the condition of a specific solvent, the compound I and the tribromooxyphosphorus are used as raw materials in a specific proportion, the compound II is prepared by one-step reaction, the reaction product can be obtained into a product with the purity of more than 98.5% only by simple post-treatment, the yield can reach more than 92%, the raw materials are few in variety, the production cost is low, the three wastes generated in the reaction process are few, the process is green and environment-friendly, and the method is suitable for large-scale industrial production.
Drawings
FIG. 1 is a high performance liquid chromatogram of a reaction liquid obtained after the reaction of 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxylic acid ethyl ester prepared in example 1 of the present invention;
FIG. 2 is a high performance liquid chromatogram of the reaction solution after the reaction of comparative example 1 according to the present invention.
FIG. 3 is a high performance liquid chromatogram of the reaction liquid after the reaction of ethyl 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxylate prepared in comparative example 2 of the present invention is completed.
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 order to better illustrate the invention, the following examples are given by way of further illustration.
Example 1
A method for synthesizing a chlorantraniliprole intermediate comprises the following steps:
86.88g of tribromooxyphosphorus (0.3mol, the content is 99%) and 137.60g of valeronitrile are added into a dry four-mouth bottle and stirred for 10min, 27.52g of ethyl 2- (3-chloro-pyridin-2-yl) -5-oxo-pyrazolidine-3-carboxylate (0.10mol, the content is 98%) are added, the temperature is slowly raised to 125-. The liquid phase detection spectrum of the reaction feed liquid after the reaction is finished is shown in figure 1.
1 HNMR (DMSO,43MHz) δ 8.59-7.74(2H, m),7.74-6.87(2H, m),3.89(2H, q, J ═ 7.1Hz),3.04(1H, s),2.25(1H, q, J ═ 1.9Hz),0.81(3H, t, J ═ 7.1 Hz). Melting point: 117.0-117.5 ℃.
Example 2
A method for synthesizing a chlorantraniliprole intermediate comprises the following steps:
289.3g of tribromooxyphosphorus (1mol, the content of which is 99%) and 413.00g of dichlorobutane are added into a dry four-mouth bottle, stirred for 10min, 137.60g of ethyl 2- (3-chloro-pyridin-2-yl) -5-oxo-pyrazolidine-3-carboxylate (0.50mol, the content of which is 98%) are added, the temperature is slowly raised to 125 ℃ and 130 ℃, the heat preservation reaction is carried out for 5H, then 98 wt% of dichlorobutane is removed under reduced pressure, the temperature is reduced to 5-10 ℃, 412.80g of water is added, the stirring and the suction filtration are carried out, and after a filter cake is dried, 157.44g of ethyl 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxylate is obtained, the white powder is similar to white, the yield is 94.30%, and the purity of a liquid chromatography is 99.00%.
1 HNMR (DMSO,43MHz) δ 8.59-7.74(2H, m),7.74-6.87(2H, m),3.89(2H, q, J ═ 7.1Hz),3.04(1H, s),2.25(1H, q, J ═ 1.9Hz),0.81(3H, t, J ═ 7.1 Hz). Melting point: 117.2-117.6 ℃.
Example 3
A method for synthesizing a chlorantraniliprole intermediate comprises the following steps:
144.80g of tribromooxyphosphorus (0.50mol, the content of which is 99%) and 139.00g of phenylacetonitrile are added into a dry four-mouth bottle, the mixture is stirred for 10min, 27.80g of 2- (3-chloropyridine-2-yl) -5-oxo-pyrazolidine-3-ethyl formate (0.10mol, the content of which is 98%) is added, the temperature is slowly raised to 105 ℃ for heat preservation reaction for 8H, then 90 wt% of phenylacetonitrile is removed under reduced pressure, the temperature is reduced to 10-15 ℃, 139.29g of water is added, the mixture is filtered, and after a filter cake is dried, 31.28g of 3-bromo-1- (3-chloropyridine-2-yl) -1H-pyrazole-5-ethyl formate is obtained, the yield is 93.65%, and the purity of a liquid chromatogram is 98.97%.
1 HNMR (DMSO,43MHz) δ 8.59-7.74(2H, m),7.74-6.87(2H, m),3.89(2H, q, J ═ 7.1Hz),3.04(1H, s),2.25(1H, q, J ═ 1.9Hz),0.81(3H, t, J ═ 7.1 Hz). Melting point: 117.0-117.4 deg.C。
Example 4
A method for synthesizing a chlorantraniliprole intermediate comprises the following steps:
58.02g of tribromooxyphosphorus (0.2mol, content 99%) and 160g of the recovered solvent obtained in example 1 are added into a dry four-mouth bottle, stirred for 10min, 27.80g of 2- (3-chloropyridin-2-yl) -5-oxo-pyrazolidine-3-ethyl formate (0.10mol, content 98%) are added, the temperature is slowly raised to 125 ℃ and 130 ℃, the reaction is kept for 7H, 98 wt% of valeronitrile is removed under reduced pressure, the temperature is reduced to 15-20 ℃, 139.00g of water is added, stirring and suction filtration are carried out, and after a filter cake is dried, 31.55g of 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-ethyl formate is obtained, the yield is 94.37%, and the purity of liquid chromatography is 98.88%.
1 HNMR (DMSO,43MHz) δ 8.59-7.74(2H, m),7.74-6.87(2H, m),3.89(2H, q, J ═ 7.1Hz),3.04(1H, s),2.25(1H, q, J ═ 1.9Hz),0.81(3H, t, J ═ 7.1 Hz). Melting point: 117.2-117.6 ℃.
Example 5
A method for synthesizing a chlorantraniliprole intermediate comprises the following steps:
95.60g of tribromooxyphosphorus (0.33mol, content 99%) and 125.5g of valeronitrile are added into a dry four-mouth bottle, stirred for 10min, 30.20g of ethyl 2- (3-chloropyridin-2-yl) -5-oxo-pyrazolidine-3-carboxylate (0.11mol, content 98%) are added, the temperature is slowly raised to 115 ℃ for heat preservation reaction for 8H, then 95 wt% of valeronitrile is removed under reduced pressure, the temperature is reduced to 0-5 ℃, 151.10g of water is added, stirred, filtered, and filter cakes are dried to obtain 34.21g of ethyl 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxylate which is white powder with yield of 92.84% and liquid chromatography purity of 98.68%.
1 HNMR (DMSO,43MHz) δ 8.59-7.74(2H, m),7.74-6.87(2H, m),3.89(2H, q, J ═ 7.1Hz),3.04(1H, s),2.25(1H, q, J ═ 1.9Hz),0.81(3H, t, J ═ 7.1 Hz). Melting point: 117.1-117.6 ℃.
Example 6
A method for synthesizing a chlorantraniliprole intermediate comprises the following steps:
86.88g of tribromooxyphosphorus (0.3mol, content 99%) and 83.60g of diethylene glycol dimethyl ether are added into a dry four-mouth bottle, stirred for 10min, 27.84g of 2- (3-chloropyridine-2-yl) -5-oxo-pyrazolidine-3-ethyl formate (0.10mol, content 98%) are added, the temperature is slowly raised to 125-130 ℃, the temperature is kept for reaction for 10H, then 96 wt% of ethylene glycol dimethyl ether is removed under reduced pressure, the temperature is reduced to 20-30 ℃, 139.20g of water is added, stirring and suction filtration are carried out, and after a filter cake is dried, 30.91g of 3-bromo-1- (3-chloropyridine-2-yl) -1H-pyrazole-5-ethyl formate is obtained, white powder is similar to the ethyl powder, the yield is 92.10%, and the purity of liquid chromatography is 98.50%.
1 HNMR (DMSO,43MHz) δ 8.59-7.74(2H, m),7.74-6.87(2H, m),3.89(2H, q, J ═ 7.1Hz),3.04(1H, s),2.25(1H, q, J ═ 1.9Hz),0.81(3H, t, J ═ 7.1 Hz). Melting point: 117.0-117.4 ℃.
Comparative example 1
A method for synthesizing a chlorantraniliprole intermediate comprises the following steps:
400mL of acetonitrile, 50.0g of ethyl 2- (3-chloropyridin-2-yl) -5-oxo-pyrazolidine-3-carboxylate (0.185mol, content 98%) and 267.86g of tribromooxyphosphorus (0.925mol, content 99%) were added to a dry four-necked flask, mixed well, and nitrogen was introduced to the mixture to conduct reflux reaction for 10 hours, and no ethyl 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxylate was formed as detected by liquid phase.
The liquid phase detection spectrum of the reaction feed liquid after the reaction is finished is shown in figure 2.
Comparative example 2
A method for synthesizing a chlorantraniliprole intermediate comprises the following steps:
172.0g of tribromooxyphosphorus (0.6mol, content 99%) and 137.60g of valeronitrile are added into a dry four-mouth bottle, stirred for 20min, 27.52g of ethyl 2- (3-chloropyridin-2-yl) -5-oxo-pyrazolidine-3-carboxylate (0.10mol, content 98%) are added, the temperature is slowly raised to 125 ℃ and 130 ℃, the reaction is kept for 5H, 98 wt% of valeronitrile is removed under reduced pressure, the temperature is reduced to 5-10 ℃, 137.60g of water is added, stirred, filtered, and dried to obtain 27.61g of ethyl 3-bromo-1- (3-chloropyridin-2-yl) -1H-pyrazole-5-carboxylate, white powder is obtained, the yield is 80.63%, and the purity of liquid chromatography is 96.54%.
The liquid phase detection spectrum of the reaction solution after the reaction is finished is shown in FIG. 3.
1 HNMR(DMSO,43MHz)δ:8.59-7.74(2H,m),7.74-6.87(2H,m),3.89(2H,q,J＝7.1Hz),3.04(1H,s),2.25(1H,q,J＝1.9Hz),0.81(3H,t,J＝7.1Hz)。
In the above examples and comparative examples, the liquid chromatography is used to detect the purity of the reaction solution and the final product after the end of the detection, and the specific test conditions are as follows:
and (3) chromatographic column: inertsil ODS-4(4.6 x 250mm, 5 μm); detection wavelength: 215 nm; mobile phase: acetonitrile/water (pH 2.5, 0.02M ammonium dihydrogen phosphate) 6: 4; sample injection amount: 20 mu L of the solution; flow rate: 1 mL/min; column temperature: at 30 ℃.
The above description is intended to be illustrative of the preferred embodiment of the present invention and should not be taken as limiting the invention, but rather, the invention is intended to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the invention.
Claims (9)
1. A synthetic method of a chlorantraniliprole intermediate is characterized by comprising the following steps:
step a, adding tribromooxyphosphorus into an organic solvent, uniformly mixing, adding a compound I, and reacting at 100-130 ℃ for 5-10 h to obtain a reaction solution containing a compound II;
b, removing and recovering part of the solvent of the reaction solution containing the compound II, cooling to 0-30 ℃, adding water, stirring, filtering, and drying to obtain a compound II;
wherein the organic solvent is valeronitrile, dichlorobutane, phenylacetonitrile or diethylene glycol dimethyl ether; the molar ratio of the compound I to the tribromooxyphosphorus is 1: 2-5.
2. The method for synthesizing the chlorantraniliprole intermediate as claimed in claim 1, wherein the organic solvent is valeronitrile.
3. The method for synthesizing the chlorantraniliprole intermediate as claimed in claim 1, wherein the molar ratio of the compound I to the tribromooxyphosphorus is 1: 2-3.
4. The method for synthesizing the chlorantraniliprole intermediate according to claim 1, wherein the mass ratio of the organic solvent to the compound I is 3-5: 1.
5. The method for synthesizing chlorantraniliprole intermediate as claimed in claim 1, wherein in the step a, the reaction temperature is 125-130 ℃ and the reaction time is 5-6 h.
6. The method for synthesizing chlorantraniliprole intermediate as claimed in claim 1, wherein in the step b, the solvent removal amount is 90-98% of the total mass of the added organic solvent.
7. The method for synthesizing chlorantraniliprole intermediate as claimed in claim 1, wherein in the step b, the amount of the added water is 3-5 times of the mass of the compound I.
8. The method for synthesizing chlorantraniliprole intermediates as claimed in claim 1, wherein in the step b, the recovered solvent is recycled to the step a to be used as a reaction solvent and a raw material.
9. The method for synthesizing chlorantraniliprole intermediates as claimed in claim 8, wherein when the recovered solvent is back-packed, the molar ratio of the compound I to the tribromooxyphosphorus in the step a is controlled to be 1: 2-3.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110821154.7A CN113527255B (en) | 2021-07-20 | 2021-07-20 | Method for synthesizing chlorantraniliprole intermediate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110821154.7A CN113527255B (en) | 2021-07-20 | 2021-07-20 | Method for synthesizing chlorantraniliprole intermediate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113527255A CN113527255A (en) | 2021-10-22 |
| CN113527255B true CN113527255B (en) | 2022-09-30 |
Family
ID=78129030
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110821154.7A Active CN113527255B (en) | 2021-07-20 | 2021-07-20 | Method for synthesizing chlorantraniliprole intermediate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113527255B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114217000A (en) * | 2021-12-15 | 2022-03-22 | 重庆华歌生物化学有限公司 | High performance liquid chromatography detection method for chlorantraniliprole in solution |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103058993B (en) * | 2013-01-08 | 2014-06-04 | 河南师范大学 | Chlorantraniliprole preparation method |
| CN111072630A (en) * | 2019-12-13 | 2020-04-28 | 东南大学 | Preparation method and application of bromopyrazole compound intermediate |
| CN111440144A (en) * | 2020-03-06 | 2020-07-24 | 山东华科化工有限公司 | Method for industrially producing bromopyrazolic acid through micro-channel |
-
2021
- 2021-07-20 CN CN202110821154.7A patent/CN113527255B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113527255A (en) | 2021-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US9783506B2 (en) | Process for the large scale production of 1H-[1,2,3]triazole and its intermediate 1-benzyl-1H-[1,2,3]triazole | |
| CN104177272B (en) | A kind of preparation method of Bromfenac sodium | |
| CN113999142B (en) | Preparation method of chiral N-Boc-trans-1, 2-cyclohexanediamine | |
| CN113527255B (en) | Method for synthesizing chlorantraniliprole intermediate | |
| CN105348172A (en) | Preparation of (S)-1-(4-methoxy-3-ethoxy)phenyl-2-methylsulfonyl ethylamine and preparation method of apremilast | |
| CN103288743B (en) | Method for synthesizing benzimidazole compounds | |
| CN116178338A (en) | Preparation method of chlorantraniliprole compound | |
| Ou et al. | Retracted article: An efficient and practical synthesis of chiral imidazolium ionic liquids and their application in an enantioselective Michael reaction | |
| CN104529935B (en) | Method for synthesizing ethyl 2-(3-aldehyde-4-isobutyloxyphenyl)-4-methylthiazole-5-formate | |
| CN101628909A (en) | Method for synthesizing 1,4-dioxane-2-ketone by ethylene glycol | |
| CN111454216A (en) | Process for the preparation of HMG-CoA reductase inhibitors and intermediates thereof | |
| CN1166608C (en) | Three-phase phase-transfer catalytic synthesis process of 9,9-dimethoxyl methyl) fluorene | |
| CN114315609A (en) | Process for preparing cis-2-aminocyclohexanol | |
| CN114349686B (en) | 1, 4-dihydropyridine chiral hybrid hydrogenation reagent, preparation method and application thereof | |
| CN111269149B (en) | Production process of 5- (3,3-dimethylguanidino) -2-oxopentanoic acid | |
| CN108911972B (en) | Racemization recovery method for by-product in resolution mother liquor of sitafloxacin intermediate | |
| CN1196665C (en) | Process for the preparation of 5-[4-chlorophenyl)-methyl]-2, 2-dimethylcyclopentanone | |
| CN110511182B (en) | Method for synthesizing 7-nitro-1,2,3,4-tetrahydroquinoline by continuous flow reaction | |
| CN108203385B (en) | Method for preparing 3- (4-fluoro-2-nitrophenyl) acetone | |
| CN109836374B (en) | Environment-friendly preparation method of vitamin B6 | |
| KR101894091B1 (en) | New method for preparation of chromanone derivatives | |
| CN112645866A (en) | Synthesis and application of 1-benzyl-4-methyl-5-alkoxy-1, 2,3, 6-tetrahydropyridine derivative | |
| JP5660784B2 (en) | Method for producing N- (2-aminoethyl) azole compound | |
| CN105330550A (en) | Optical activity 1-cyclohexyl ethylamine preparation method | |
| CN110003083A (en) | A kind of process using Ir catalyst preparation S- indoline-2-carboxylic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |