CN115073441A - Synthetic method of topramezone intermediate - Google Patents
Synthetic method of topramezone intermediate Download PDFInfo
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- CN115073441A CN115073441A CN202110267253.5A CN202110267253A CN115073441A CN 115073441 A CN115073441 A CN 115073441A CN 202110267253 A CN202110267253 A CN 202110267253A CN 115073441 A CN115073441 A CN 115073441A
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- 238000010189 synthetic method Methods 0.000 title claims description 5
- IYMLUHWAJFXAQP-UHFFFAOYSA-N topramezone Chemical compound CC1=C(C(=O)C2=C(N(C)N=C2)O)C=CC(S(C)(=O)=O)=C1C1=NOCC1 IYMLUHWAJFXAQP-UHFFFAOYSA-N 0.000 title description 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 40
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 27
- QWXYZCJEXYQNEI-OSZHWHEXSA-N intermediate I Chemical compound COC(=O)[C@@]1(C=O)[C@H]2CC=[N+](C\C2=C\C)CCc2c1[nH]c1ccccc21 QWXYZCJEXYQNEI-OSZHWHEXSA-N 0.000 claims abstract description 16
- 239000002904 solvent Substances 0.000 claims abstract description 16
- 239000002585 base Substances 0.000 claims abstract description 14
- 229940126062 Compound A Drugs 0.000 claims abstract description 12
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001308 synthesis method Methods 0.000 claims abstract description 11
- 230000009471 action Effects 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- -1 sulfuryl pyraflufen Chemical compound 0.000 claims abstract description 4
- 238000007149 pericyclic reaction Methods 0.000 claims abstract 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 6
- 235000015497 potassium bicarbonate Nutrition 0.000 claims description 6
- 239000011736 potassium bicarbonate Substances 0.000 claims description 6
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims description 6
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 5
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 5
- 125000003158 alcohol group Chemical group 0.000 claims description 3
- 150000002923 oximes Chemical class 0.000 claims description 2
- 230000008569 process Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000036632 reaction speed Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000001514 detection method Methods 0.000 description 11
- 238000004128 high performance liquid chromatography Methods 0.000 description 10
- CASLETQIYIQFTQ-UHFFFAOYSA-N 3-[[5-(difluoromethoxy)-1-methyl-3-(trifluoromethyl)pyrazol-4-yl]methylsulfonyl]-5,5-dimethyl-4h-1,2-oxazole Chemical compound CN1N=C(C(F)(F)F)C(CS(=O)(=O)C=2CC(C)(C)ON=2)=C1OC(F)F CASLETQIYIQFTQ-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 238000007792 addition Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- 241000196324 Embryophyta Species 0.000 description 2
- 239000005605 Pyraflufen-ethyl Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- DIYSFZUJSGOINT-UHFFFAOYSA-N 5,5-dimethyl-4h-1,2-oxazole Chemical compound CC1(C)CC=NO1 DIYSFZUJSGOINT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- ASWVTGNCAZCNNR-UHFFFAOYSA-N sulfamethazine Chemical compound CC1=CC(C)=NC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1 ASWVTGNCAZCNNR-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Plural Heterocyclic Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of a sulfuryl pyraflufen intermediate, which comprises the following reaction steps: a. reacting the compound A with dibromoformyloxime in a first solvent under the action of first alkali to generate an intermediate I; b. the intermediate I and isobutene undergo a pericyclic reaction under the action of a second base to generate a sulfonepyrazoxazole intermediate II. The synthesis method has the advantages of high reaction speed, high product purity and yield, mild reaction conditions, extensive synthesis process, optimized reaction conditions, reduced reaction equipment cost, easy separation of the obtained product and simplified production process.
Description
Technical Field
The invention relates to a sulfonylpyrafluzole intermediate, in particular to a synthetic method of 3- [ [5- (difluoromethoxy) -1-methyl-3- (trifluoromethyl) pyrazol-4-yl ] methylsulfonyl ] -5, 5-dimethyl-4H-1, 2-oxazole, belonging to the technical field of organic synthesis.
Background
Sulfoxaden is developed by Nippon combinatorial chemical having the structure shown below:
it can be used as a pre-emergence soil treatment for most crop fields. The applied sulpyrazone is absorbed by young roots and young buds of weeds, inhibits the early growth of seedlings, destroys meristems and coleoptiles, and is a serious potential inhibitor in the biosynthesis of VLCFA (very long side chain fatty acid) (C20-C30) in plants.
3- [ [5- (difluoromethoxy) -1-methyl-3- (trifluoromethyl) pyrazol-4-yl ] methylsulfonyl ] -5, 5-dimethyl-4H-1, 2-oxazole as a key intermediate in the synthesis of sulfonepyrazoxazole, which is disclosed in the prior art, for example, CN102666503, can be synthesized using the following pathway:
the method specifically comprises the following steps: under the alkaline condition, 1-methyl-3- (trifluoromethyl) -1H-pyrazole-5-alcohol, formaldehyde aqueous solution and 5, 5-dimethyl-4, 5-dihydro isoxazole sulfamidine hydrochloride are subjected to condensation reaction in water and then alkylated with freon to obtain the key intermediate of the sulfuryl pyrafluzole
However, the synthesis method has the defects of low product yield, difficult treatment of sulfur-containing wastewater, three wastes and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a synthesis method of a sulfuryl pyraflufen intermediate, which has the advantages of mild reaction conditions, high product yield, less three wastes generated in the reaction process and the like.
In order to achieve the purpose, the invention adopts the following technical scheme:
a synthetic method of a sulfuryl pyraflufen intermediate comprises the following reaction steps:
a. the compound A and dibromoformyl oxime react in a first solvent under the action of a first base to generate an intermediate I:
b. the intermediate I and isobutene undergo a cyclotomic reaction under the action of a second base to generate the intermediate II of the sulfonepyrazoxazole:
further: the step a comprises the following steps: dissolving a compound A in a first solvent, and adding a first base for reaction; followed by the addition of dibromoformyloxime.
Further: in the step a, the reaction temperature is 0-60 ℃.
Further: the first alkali is sodium bicarbonate and/or potassium bicarbonate; and the reaction molar ratio n of compound a to the first base (compound a): n (first base) is 1:1.05 to 1: 1.3.
Further: the first solvent is an alcohol.
Further: the first solvent is methanol or ethanol.
Further: in the step b, the reaction temperature is-20 ℃ to 50 ℃.
Further: the second alkali is sodium hydroxide and/or potassium hydroxide; and the reaction molar ratio of the intermediate I to isobutylene is n (intermediate I): n (isobutylene) is 1:1.1 to 1: 1.5.
The invention provides a novel method for synthesizing a key intermediate of sulfone pyraflufen-ethyl, which comprises the steps of reacting a compound A with dibromoformyloxime to generate an intermediate I, and then carrying out a cyclization reaction on the intermediate I and isobutene under an alkaline condition to finally obtain the intermediate of the sulfone pyraflufen-ethyl
Compared with the existing synthesis method, the synthesis method has the following characteristics: (1) the reaction condition is mild, high temperature and high pressure are not needed, and the requirement on equipment is low; (2) the reaction selectivity is high, the reaction yield is high, and the yield is over 80 percent; (3) the post-treatment is simple and extensive, and is suitable for large-scale production; (4) no catalyst is needed; (5) the three wastes generated in the synthesis process are less and easy to treat.
Detailed Description
The invention provides a novel method for synthesizing a key intermediate 3- [ [5- (difluoromethoxy) -1-methyl-3- (trifluoromethyl) pyrazol-4-yl ] methylsulfonyl ] -5, 5-dimethyl-4H-1, 2-oxazole of sulfonepyrafluzole, which adopts the following synthesis mechanism:
specifically, the synthesis step of the intermediate 3- [ [5- (difluoromethoxy) -1-methyl-3- (trifluoromethyl) pyrazol-4-yl ] methylsulfonyl ] -5, 5-dimethyl-4H-1, 2-oxazole comprises the following steps: a. reacting the compound A with dibromoformyloxime in a first solvent under the action of first alkali to generate an intermediate I; and b, the intermediate I and isobutene have a cycloreaction under the action of a second base to generate the 3- [ [5- (difluoromethoxy) -1-methyl-3- (trifluoromethyl) pyrazol-4-yl ] methylsulfonyl ] -5, 5-dimethyl-4H-1, 2-oxazole (intermediate II) disclosed by the application.
Wherein, in the step a, the reaction temperature is 0-60 ℃; the first alkali can adopt sodium bicarbonate and/or potassium bicarbonate; and the reaction molar ratio n of compound a to the first base (compound a): n (first base) is 1:1.05 to 1: 1.3; and the first solvent is an alcohol, preferably methanol or ethanol.
In the step b, the reaction temperature is-20 ℃ to 50 ℃; the second alkali is sodium hydroxide and/or potassium hydroxide; and the reaction molar ratio of the intermediate I to the isobutene is n (intermediate I): n (isobutylene) is 1:1.1 to 1: 1.5.
The technical solution of the present invention is further described below with reference to specific examples, but the present invention is not limited to the following examples. The raw materials used in the present invention are commercially available if not otherwise specified.
Example 1
Adding 13.1g of compound A into 100ml of ethanol at room temperature and stirring until the mixture is clear; then adding 4.2g of sodium bicarbonate to react for 1 hour; then adding 10.1g of dibromoformyloxime, continuously reacting for 4hr at room temperature, and cooling to-10 ℃ after HPLC detection reaction; adding 2.5g of sodium hydroxide, introducing 3.1g of isobutene, detecting the reaction by HPLC after 2 hours, and spin-drying the solvent to obtain 16.19g of oil, wherein the purity is 92.1% and the total yield in two steps is 83%.
Example 2:
adding 13.1g of the compound A into 100ml of ethanol at room temperature and stirring until the mixture is clear; then 5.5g of potassium bicarbonate is added for reaction for 1 hour; then adding 10.1g of dibromoformyloxime, continuously reacting for 4 hours at room temperature, and cooling to-10 ℃ after the HPLC detection reaction is finished; adding 3.63g of potassium hydroxide, introducing 3.1g of isobutene, after 2 hours, detecting by HPLC to finish the reaction, and spin-drying the solvent to obtain 16.4g of oily substance with the purity of 93.3% and the total yield of the two steps of 85.2%.
Example 3:
13.1g of Compound A are added to 100ml of methanol and stirred at 15 ℃ until clear; then 5.5g of potassium bicarbonate is added to react for 1 hour at the temperature of 15 ℃; then adding 10.1g of dibromoformyloxime, continuing the heat preservation reaction at the temperature for 4 hours, reducing the temperature to-20 ℃ after the HPLC detection reaction is finished, adding 3.63g of potassium hydroxide, introducing 3.1g of isobutene, completing the HPLC detection reaction after 4 hours, and spin-drying the solvent to obtain 16.55g of oily matter, wherein the purity is 91.7 percent through detection, and the total yield of the two steps is 84.5 percent.
Example 4:
13.1g of Compound A are added to 100ml of methanol and stirred at 30 ℃ until clear; then 6g of potassium bicarbonate is added to react for 1 hour at the temperature of 30 ℃; then adding 10.1g of dibromoformyloxime, continuing to carry out heat preservation reaction at the temperature for 4 hours, supplementing 3.95g of potassium hydroxide after the HPLC detection reaction is finished, introducing 3.65g of isobutene to continue the reaction at the temperature, finishing the HPLC detection reaction after 4 hours, and drying the solvent by spinning to obtain 16.07g of oily matter, wherein the purity is 90.2 percent by detection, and the total yield of the two steps is 80.7 percent.
Example 5:
adding 13.1g of the compound A into 100ml of ethanol at room temperature and stirring until the mixture is clear; then 4.2g of sodium bicarbonate is added to react for 1 hour at room temperature; and then adding 10.1g of dibromoformyloxime, continuing to react for 4 hours at room temperature, cooling to 0 ℃ after the HPLC detection reaction is finished, supplementing 2.71g of sodium hydroxide and introducing 3.65g of isobutene, completing the HPLC detection reaction after 2 hours, and spin-drying the solvent to obtain 16.14g of oily matter, wherein the purity is 92.6 percent through detection, and the total yield of the two steps is 83.2 percent.
The present invention has been described in detail with reference to the preferred embodiments. However, variations and additions to the embodiments will become apparent to those of ordinary skill in the art upon a reading of the foregoing description. It is the intention of the applicants that all such variations and additions fall within the scope of the claims. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Any modification and improvement of this product, and the substitution and use of the same or similar substances within the scope or range of patents, shall fall within the scope of protection of this invention.
Claims (8)
1. A synthetic method of a sulfuryl pyraflufen intermediate is characterized by comprising the following steps: the method comprises the following reaction steps:
a. the compound A and dibromoformyl oxime react in a first solvent under the action of a first base to generate an intermediate I:
b. the intermediate I and isobutene undergo a pericyclic reaction under the action of a second base to generate a sulfonepyrazoxazole intermediate II:
2. the method of synthesis according to claim 1, characterized in that: the step a comprises the following steps: dissolving a compound A in a first solvent, and adding a first base for reaction; followed by the addition of dibromoformyloxime.
3. The synthesis method according to claim 1 or 2, characterized in that: in the step a, the reaction temperature is 0-60 ℃.
4. The synthesis method according to claim 1 or 2, characterized in that: the first alkali is sodium bicarbonate and/or potassium bicarbonate; and the reaction molar ratio n of compound a to the first base (compound a): n (first base) is 1:1.05 to 1: 1.3.
5. The synthesis method according to claim 1 or 2, characterized in that: the first solvent is an alcohol.
6. The method of synthesis according to claim 5, characterized in that: the first solvent is methanol or ethanol.
7. The synthesis method according to claim 1 or 2, characterized in that: in the step b, the reaction temperature is-20 ℃ to 50 ℃.
8. The synthesis method according to claim 1 or 2, characterized in that: the second alkali is sodium hydroxide and/or potassium hydroxide; and the reaction molar ratio of the intermediate I to isobutylene is n (intermediate I): n (isobutylene) is 1:1.1 to 1: 1.5.
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Cited By (1)
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| WO2020240392A1 (en) * | 2019-05-24 | 2020-12-03 | Pi Industries Limited | Process for preparation of pyroxasulfone |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020240392A1 (en) * | 2019-05-24 | 2020-12-03 | Pi Industries Limited | Process for preparation of pyroxasulfone |
| 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 |
Cited By (1)
| 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 |
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