CN113336716A - Preparation method of topramezone intermediate - Google Patents
Preparation method of topramezone intermediate Download PDFInfo
- Publication number
- CN113336716A CN113336716A CN202110647048.1A CN202110647048A CN113336716A CN 113336716 A CN113336716 A CN 113336716A CN 202110647048 A CN202110647048 A CN 202110647048A CN 113336716 A CN113336716 A CN 113336716A
- Authority
- CN
- China
- Prior art keywords
- reaction
- glyoxylic acid
- molar ratio
- preparation
- sodium
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D261/00—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings
- C07D261/02—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings
- C07D261/04—Heterocyclic compounds containing 1,2-oxazole or hydrogenated 1,2-oxazole rings not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of a sulfuryl pyraflufen-ethyl intermediate, which takes glyoxylic acid as a starting material and firstly carries out condensation reaction with hydroxylamine to generate 2- (hydroxyimino) acetic acid; then carrying out bromination reaction in the presence of sodium bromate and sodium bisulfite to generate dibromoformaldoxime; finally, carrying out cyclization reaction with isobutene to generate the 3-bromo-5, 5-dimethyl-4, 5-dihydroisoxazole as the intermediate of the sulfonepyrazoxazole; wherein the bromination reaction temperature is 10-60 ℃, and the molar ratio of the glyoxylic acid to the sodium bromate to the sodium bisulfite is 1: 2-1: 4. According to the method, the sodium bromate and the sodium bisulfite react to slowly release bromine, the reaction is mild, the reaction is easy to control, byproducts are not easy to generate, products generated by introducing the isobutene do not need to be rectified to remove impurities, and the yield is high.
Description
Technical Field
The invention belongs to the technical field of herbicide intermediate preparation, and particularly relates to a preparation method of a sulfonylpyraflufen intermediate 3-bromo-5, 5-dimethyl-4, 5-dihydroisoxazole.
Background
The Pyroxasulfone is an isoxazole herbicide with the chemical name of 3- [5- (difluoromethoxy) -1-methyl-3- (trifluoromethyl) pyrazol-4-yl methylsulfonyl ] -4, 5-dihydro-5, 5-dimethyl-1, 2-isoxazole and the molecular formula of C12H14F5N3O4S, molecular weight 391.32, CAS registry number 447399-55-5. The pyriftalid is mainly used as a pre-emergence sealing treatment agent, and is used for sealing and killing gramineae which is mainly used as broadleaf grass, so that the pyriftalid has a plurality of advantages: the fertilizer has wide applicable crop range and can be used for crops such as wheat, corn, peanut, rice, soybean, cotton and the like; is safe to the environment, and is safe to the current crop and the next crop; the lasting period can reach about 28 days.
3-bromo-5, 5-dimethyl-4, 5-dihydroisoxazole is an important intermediate for synthesizing the sulfonepyrazoxazole.
At present, the main methods for preparing 3-bromo-5, 5-dimethyl-4, 5-dihydroisoxazole are as follows: glyoxylic acid is used as an initial raw material, firstly, the glyoxylic acid reacts with hydroxylamine to generate 2- (hydroxyimino) acetic acid, then, liquid bromine is used for bromination to obtain dibromoformaldehyde oxime, and finally, the dibromoformaldehyde oxime reacts with isobutene to obtain 3-bromo-5, 5-dimethyl-4, 5-dihydroisoxazole.
The reaction formula is as follows:
the method has the following disadvantages: (1) in the bromination reaction, sodium bicarbonate is needed to adjust the pH value while liquid bromine is dripped, and impurities are generated when the pH value is higher or lower, so that the bromination reaction is difficult to control, and the purity and the reaction yield of the product are not ideal; (2) carbon dioxide is also generated in the process of adding sodium bicarbonate, and the carbon dioxide is easy to bring out a large amount of liquid bromine, so that the method is not environment-friendly, has poor safety and is not suitable for industrial production; (3) the final product has more impurities, and the impurities need to be removed through rectification, so that the yield is low.
Disclosure of Invention
The invention aims to solve the problems and provides a preparation method of 3-bromo-5, 5-dimethyl-4, 5-dihydroisoxazole, which is simple and convenient to operate in bromination reaction, more environment-friendly, higher in reaction yield and product purity and suitable for industrial production.
The technical scheme for realizing the purpose of the invention is as follows: a preparation method of a sulfuryl pyraflufen-ethyl intermediate takes glyoxylic acid as a starting material, and firstly carries out condensation reaction with hydroxylamine to generate 2- (hydroxyimino) acetic acid; then carrying out bromination reaction in the presence of sodium bromate and sodium bisulfite to generate dibromoformaldoxime; finally, carrying out cyclization reaction with isobutene to generate the 3-bromo-5, 5-dimethyl-4, 5-dihydroisoxazole as the intermediate of the sulfonepyrazoxazole.
The reaction formula is as follows:
and after the condensation reaction and before the bromination reaction, the pH of the reaction system is adjusted to be neutral by using sodium hydroxide.
The hydroxylamine is hydroxylamine hydrochloride or hydroxylamine sulfate, preferably hydroxylamine sulfate.
The molar ratio of the glyoxylic acid to the hydroxylamine hydrochloride is 1: 1-1: 2, and preferably 1: 1-1: 1.2.
The molar ratio of the glyoxylic acid to the hydroxylamine sulfate is 1: 0.5-1: 1, and preferably 1: 0.5-1: 0.6.
The molar ratio of the glyoxylic acid to the sodium bromate is 1: 2-1: 4, and preferably 1: 2-1: 2.5.
The molar ratio of the glyoxylic acid to the sodium bisulfite is 1: 2-1: 4, and preferably 1: 2-1: 2.5.
The cyclization reaction is carried out in the presence of a basic catalyst; the alkaline catalyst is one of sodium carbonate and potassium carbonate.
The molar ratio of the glyoxylic acid to the basic catalyst is 1: 1-1: 3, and preferably 1: 1.5.
The molar ratio of the glyoxylic acid to the isobutene is 1: 1-1: 3, and preferably 1: 1.5.
The condensation reaction is carried out in water.
The bromination reaction and the cyclization reaction are carried out in an organic solvent; the organic solvent is one of dichloroethane, dichloromethane and chloroform, and preferably dichloroethane.
The condensation reaction temperature is room temperature (15-25 ℃, the same applies below).
The bromination reaction temperature (i.e., the addition temperature of sodium bisulfite) is 10-60 ℃, and preferably 30-35 ℃.
The cyclization reaction temperature (namely the adding temperature of isobutene) is 20-60 ℃, and preferably 40-45 ℃.
The invention has the following positive effects: according to the method, the sodium bromate and the sodium bisulfite react to slowly release bromine, the reaction is mild, the reaction is easy to control, byproducts are not easy to generate, products generated by introducing the isobutene do not need to be rectified to remove impurities, and the yield is high.
Detailed Description
(example 1)
The preparation method of the intermediate of the sulfone pyraclonil in the embodiment is as follows:
100g of a 50wt% aqueous solution of glyoxylic acid (0.67 mol) was placed in a 1-liter four-necked flask, followed by addition of 100g of water and 60g of hydroxylamine sulfate (0.366 mol, 0.54 eq) and condensation reaction was carried out at room temperature with stirring for 1 hour.
After the reaction is finished, 170g of 30wt% sodium hydroxide aqueous solution is dropwise added into the reaction system at room temperature, 200g of dichloroethane is added after dropwise addition is finished, 224g of sodium bromate (1.48 mol, 2.2 eq) is added at room temperature, then the temperature is increased to 30-35 ℃, the sodium bisulfite aqueous solution [ 154g of sodium bisulfite (1.48 mol, 2.2 eq) is dropwise added at controlled temperature and dissolved in 350g of water ], and after dropwise addition, the temperature is kept at (30-35 ℃) for bromination reaction for 2 hours.
After the reaction is finished, layering, transferring the dichloroethane layer at the lower layer into another 500mL four-port bottle, adding 107.4g of sodium carbonate (1.01 mol, 1.5 eq), controlling the temperature to be 40-45 ℃, introducing 56.7g of isobutene (1.01 mol, 1.5 eq) for cyclization, performing suction filtration, and evaporating the mother liquor to dryness to obtain 95.0g of 3-bromo-5, 5-dimethyl-4, 5-dihydroisoxazole with the purity of 96% and the yield of 79.0%.
(examples 2 to 5)
The preparation method of each example is basically the same as that of example 1 except for the differences shown in Table 1.
TABLE 1
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | |
| Amount of sodium bromate | 224g（2.2eq） | 204g（2.0eq） | 255g（2.5eq） | 224g（2.2eq） | 224g（2.2eq） |
| The amount of sodium bisulfite to be used | 154g of water (2.2 eq) dissolved in 350g of water | 140g of water (2.0 eq) dissolved in 320g of water | 175g of this was dissolved in 400g of water (2.5 eq) | 154g of water (2.2 eq) dissolved in 350g of water | 154g of water (2.2 eq) dissolved in 350g of water |
| Dropping sodium bisulfite and bromination reaction temperature and time | 30～35℃，2h | 30～35℃，2h | 30～35℃，2h | 10～15℃，4h | 55～60℃，1.5h |
| Product of | 95.0g | 89.0g | 91.4g | 60.0g | 81.8g |
| Purity of | 96.0% | 95.0% | 94.0% | 80.0% | 85.0% |
| Yield of | 79.0% | 74.0% | 76.0% | 49.9% | 68.0% |
Claims (10)
1. A preparation method of a sulfuryl pyraflufen-ethyl intermediate takes glyoxylic acid as a starting material, and firstly carries out condensation reaction with hydroxylamine to generate 2- (hydroxyimino) acetic acid; then carrying out bromination reaction to generate dibromoformaldehyde oxime; finally, carrying out cyclization reaction with isobutene to generate the 3-bromo-5, 5-dimethyl-4, 5-dihydroisoxazole as the intermediate of the sulfonepyrazoxazole; the method is characterized in that: the bromination reaction is carried out in the presence of sodium bromate and sodium bisulfite.
2. The method for producing a sulfone pyraflufen-ethyl intermediate as claimed in claim 1, characterized in that: the bromination reaction temperature is 10-60 ℃.
3. The method for producing a sulfone pyraflufen-ethyl intermediate as claimed in claim 2, characterized in that: the bromination reaction temperature is 30-35 ℃.
4. The process for the preparation of the intermediate of sulfonepyrazoxazole as claimed in one of claims 1 to 3, characterized in that: the molar ratio of the glyoxylic acid to the sodium bromate is 1: 2-1: 4; the molar ratio of the glyoxylic acid to the sodium bisulfite is 1: 2-1: 4.
5. The process for producing a sulfone pyraflufen-ethyl intermediate as claimed in claim 4, characterized in that: the molar ratio of the glyoxylic acid to the sodium bromate is 1: 2-1: 2.5; the molar ratio of the glyoxylic acid to the sodium bisulfite is 1: 2-1: 2.5.
6. The process for the preparation of the intermediate of sulfonepyrazoxazole as claimed in one of claims 1 to 3, characterized in that: and after the condensation reaction and before the bromination reaction, the pH of the reaction system is adjusted to be neutral by using sodium hydroxide.
7. The process for the preparation of the intermediate of sulfonepyrazoxazole as claimed in one of claims 1 to 3, characterized in that: the hydroxylamine is hydroxylamine hydrochloride or hydroxylamine sulfate; the molar ratio of the glyoxylic acid to the hydroxylamine hydrochloride is 1: 1-1: 2; the molar ratio of the glyoxylic acid to the hydroxylamine sulfate is 1: 0.5-1: 1.
8. The process for producing a sulfone pyraflufen-ethyl intermediate as claimed in claim 7, characterized in that: the hydroxylamine is hydroxylamine sulfate; the molar ratio of the glyoxylic acid to the hydroxylamine sulfate is 1: 0.5-1: 0.6.
9. The process for the preparation of the intermediate of sulfonepyrazoxazole as claimed in one of claims 1 to 3, characterized in that: the cyclization reaction is carried out in the presence of a basic catalyst; the alkaline catalyst is sodium carbonate or potassium carbonate; the molar ratio of the glyoxylic acid to the basic catalyst is 1: 1-1: 3.
10. The process for the preparation of the intermediate of sulfonepyrazoxazole as claimed in one of claims 1 to 3, characterized in that: the molar ratio of the glyoxylic acid to the isobutene is 1: 1-1: 3, and the cyclization reaction temperature is 20-60 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110647048.1A CN113336716B (en) | 2021-06-10 | 2021-06-10 | Preparation method of topramezone intermediate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110647048.1A CN113336716B (en) | 2021-06-10 | 2021-06-10 | Preparation method of topramezone intermediate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113336716A true CN113336716A (en) | 2021-09-03 |
| CN113336716B CN113336716B (en) | 2022-04-08 |
Family
ID=77475656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110647048.1A Active CN113336716B (en) | 2021-06-10 | 2021-06-10 | Preparation method of topramezone intermediate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113336716B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113372288A (en) * | 2021-06-02 | 2021-09-10 | 安徽久易农业股份有限公司 | Synthetic method of topramezone pesticide intermediate |
| CN113735791A (en) * | 2021-10-14 | 2021-12-03 | 杭州欧晨科技有限公司 | Synthetic method of 3-bromo-5, 5-dimethyl-4, 5-dihydroisoxazole |
| CN116023295A (en) * | 2022-12-19 | 2023-04-28 | 青岛润农化工有限公司 | Synthesis method of 1, 1-dihalogen aldoxime |
| CN116041270A (en) * | 2023-03-24 | 2023-05-02 | 启农生物科技(北京)有限公司 | Preparation process of intermediate chloroisoxazole for synthesizing fenpyr-diethyl |
| CN116102510A (en) * | 2021-11-10 | 2023-05-12 | 江西仰立新材料有限公司 | Preparation method of 3-bromo-5, 5-dimethyl-4, 5-dihydro-isoxazole |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111393427A (en) * | 2020-04-30 | 2020-07-10 | 安徽久易农业股份有限公司 | Synthetic method of sulfuryl pyraflufen |
| CN111574511A (en) * | 2020-06-28 | 2020-08-25 | 安徽久易农业股份有限公司 | Synthesis method and application of sulfuryl pyraflufen |
| CN112645894A (en) * | 2020-11-30 | 2021-04-13 | 江苏中旗科技股份有限公司 | Method for preparing sulpirazole intermediate 5, 5-dimethyl-4, 5-dihydroisoxazole-3-thiocarboxamidine hydrochloride |
-
2021
- 2021-06-10 CN CN202110647048.1A patent/CN113336716B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111393427A (en) * | 2020-04-30 | 2020-07-10 | 安徽久易农业股份有限公司 | Synthetic method of sulfuryl pyraflufen |
| CN111574511A (en) * | 2020-06-28 | 2020-08-25 | 安徽久易农业股份有限公司 | Synthesis method and application of sulfuryl pyraflufen |
| CN112645894A (en) * | 2020-11-30 | 2021-04-13 | 江苏中旗科技股份有限公司 | Method for preparing sulpirazole intermediate 5, 5-dimethyl-4, 5-dihydroisoxazole-3-thiocarboxamidine hydrochloride |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113372288A (en) * | 2021-06-02 | 2021-09-10 | 安徽久易农业股份有限公司 | Synthetic method of topramezone pesticide intermediate |
| CN113735791A (en) * | 2021-10-14 | 2021-12-03 | 杭州欧晨科技有限公司 | Synthetic method of 3-bromo-5, 5-dimethyl-4, 5-dihydroisoxazole |
| CN116102510A (en) * | 2021-11-10 | 2023-05-12 | 江西仰立新材料有限公司 | Preparation method of 3-bromo-5, 5-dimethyl-4, 5-dihydro-isoxazole |
| CN116023295A (en) * | 2022-12-19 | 2023-04-28 | 青岛润农化工有限公司 | Synthesis method of 1, 1-dihalogen aldoxime |
| CN116041270A (en) * | 2023-03-24 | 2023-05-02 | 启农生物科技(北京)有限公司 | Preparation process of intermediate chloroisoxazole for synthesizing fenpyr-diethyl |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113336716B (en) | 2022-04-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113336716B (en) | Preparation method of topramezone intermediate | |
| CN111393427B (en) | Synthetic method of sulfuryl pyraflufen | |
| CN110028399B (en) | Preparation method of 2-methyl-4-chlorophenoxyacetic acid | |
| CN110922367A (en) | Intermediate of topramezone and preparation method of topramezone | |
| CN113135867B (en) | S- (5, 5-dimethyl-4, 5-dihydroisoxazol-3-yl) ethyl acetate and synthetic method and application thereof | |
| WO2019041462A1 (en) | Method for preparing 1,1'-ethylene-2,2'-bipyridyl dichloride salt | |
| CN107963993A (en) | A kind of preparation method of high-purity ethiprole | |
| CN113754647A (en) | Synthesis method of sulfuryl pyraflufen-ethyl and intermediate thereof | |
| CN112707809B (en) | Method for preparing oxazoline insecticide fluorine Lei Lana intermediate | |
| CN112645894B (en) | Method for preparing sulpirazole intermediate 5, 5-dimethyl-4, 5-dihydroisoxazole-3-thiocarboxamidine hydrochloride | |
| CN110483429B (en) | Preparation method of 3, 5-disubstituted-4, 5-dihydroisoxazole | |
| CN117327016A (en) | Preparation method of fenpyrad intermediate | |
| CN112409287A (en) | Oxazolecarboxamide intermediate and preparation method of oxazolecarboxamide | |
| CN114957233A (en) | Sulfoxapyrazole and preparation method thereof | |
| CN107629015A (en) | One kind synthesis 1（2,4 dichlorophenyls）The method of the ketone of 3 methyl, 4 difluoromethyl, 1,2,4 triazole 5 | |
| CN108947870B (en) | Preparation method of bromosartanbiphenyl | |
| CN104529924B (en) | The preparation method of 5-cyclopropyl-4-[2-methylthio group-4-(trifluoromethyl) benzoyl] isoxzzole | |
| CN106565556A (en) | Synthetic process of mesotrione | |
| CN101274889A (en) | Preparation for 3-(2-Chloro-alpha,alpha,alpha-trifluoro-p-tolyoxy) benzoic acid | |
| CN106565560A (en) | Synthesis process of mesotrione | |
| CN106986762A (en) | A kind of technique for preparing DL mandelic acids | |
| CN112745272A (en) | Preparation method of nifuratel related substance A | |
| CN109293591A (en) | A kind of preparation method of triazinone | |
| CN106565561A (en) | 2-nitro-4-methylsulfonylbenzoylchloride synthesizing process | |
| CN117603151A (en) | Synthesis method of topiramate intermediate |
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 |