CN116041270A - Preparation process of intermediate chloroisoxazole for synthesizing fenpyr-diethyl - Google Patents
Preparation process of intermediate chloroisoxazole for synthesizing fenpyr-diethyl Download PDFInfo
- Publication number
- CN116041270A CN116041270A CN202310292827.3A CN202310292827A CN116041270A CN 116041270 A CN116041270 A CN 116041270A CN 202310292827 A CN202310292827 A CN 202310292827A CN 116041270 A CN116041270 A CN 116041270A
- Authority
- CN
- China
- Prior art keywords
- chloroisoxazole
- synthesizing
- preparing
- haloxyfop
- acid
- 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.)
- Pending
Links
- AJRGDQWFWJDYDP-UHFFFAOYSA-N 3-chloro-1,2-oxazole Chemical compound ClC=1C=CON=1 AJRGDQWFWJDYDP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims abstract description 23
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000008569 process Effects 0.000 claims abstract description 15
- 239000002994 raw material Substances 0.000 claims abstract description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- MFSWTRQUCLNFOM-UHFFFAOYSA-N methyl 2-(4-{[3-chloro-5-(trifluoromethyl)pyridin-2-yl]oxy}phenoxy)propanoate Chemical group C1=CC(OC(C)C(=O)OC)=CC=C1OC1=NC=C(C(F)(F)F)C=C1Cl MFSWTRQUCLNFOM-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002253 acid Substances 0.000 claims abstract description 10
- 239000011230 binding agent Substances 0.000 claims abstract description 10
- 239000005708 Sodium hypochlorite Substances 0.000 claims abstract description 9
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims abstract description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000007363 ring formation reaction Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 6
- LJHFIVQEAFAURQ-ZPUQHVIOSA-N (NE)-N-[(2E)-2-hydroxyiminoethylidene]hydroxylamine Chemical compound O\N=C\C=N\O LJHFIVQEAFAURQ-ZPUQHVIOSA-N 0.000 claims abstract description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006482 condensation reaction Methods 0.000 claims abstract description 4
- 235000019253 formic acid Nutrition 0.000 claims abstract description 4
- JIRJHEXNDQBKRZ-UHFFFAOYSA-N phosgene oxime Chemical compound ON=C(Cl)Cl JIRJHEXNDQBKRZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000004519 manufacturing process Methods 0.000 claims description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 5
- 150000007529 inorganic bases Chemical group 0.000 claims description 4
- 238000005660 chlorination reaction Methods 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 238000009776 industrial production Methods 0.000 abstract description 6
- 239000000575 pesticide Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 238000010924 continuous production Methods 0.000 abstract 1
- 239000000543 intermediate Substances 0.000 description 22
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 8
- 239000000047 product Substances 0.000 description 5
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- MFSWTRQUCLNFOM-SECBINFHSA-N haloxyfop-P-methyl Chemical group C1=CC(O[C@H](C)C(=O)OC)=CC=C1OC1=NC=C(C(F)(F)F)C=C1Cl MFSWTRQUCLNFOM-SECBINFHSA-N 0.000 description 4
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 4
- 235000017557 sodium bicarbonate Nutrition 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- VTNQPKFIQCLBDU-UHFFFAOYSA-N Acetochlor Chemical compound CCOCN(C(=O)CCl)C1=C(C)C=CC=C1CC VTNQPKFIQCLBDU-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000004009 herbicide Substances 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- GOCUAJYOYBLQRH-UHFFFAOYSA-N 2-(4-{[3-chloro-5-(trifluoromethyl)pyridin-2-yl]oxy}phenoxy)propanoic acid Chemical compound C1=CC(OC(C)C(O)=O)=CC=C1OC1=NC=C(C(F)(F)F)C=C1Cl GOCUAJYOYBLQRH-UHFFFAOYSA-N 0.000 description 1
- WVQBLGZPHOPPFO-UHFFFAOYSA-N 2-chloro-N-(2-ethyl-6-methylphenyl)-N-(1-methoxypropan-2-yl)acetamide Chemical compound CCC1=CC=CC(C)=C1N(C(C)COC)C(=O)CCl WVQBLGZPHOPPFO-UHFFFAOYSA-N 0.000 description 1
- 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 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 244000020551 Helianthus annuus Species 0.000 description 1
- 235000003222 Helianthus annuus Nutrition 0.000 description 1
- 239000005927 Pyriproxyfen Substances 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- KJADKKWYZYXHBB-XBWDGYHZSA-N Topiramic acid Chemical compound C1O[C@@]2(COS(N)(=O)=O)OC(C)(C)O[C@H]2[C@@H]2OC(C)(C)O[C@@H]21 KJADKKWYZYXHBB-XBWDGYHZSA-N 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 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
- 230000009471 action Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- -1 and preferably Chemical compound 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002363 herbicidal effect Effects 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- NHDHVHZZCFYRSB-UHFFFAOYSA-N pyriproxyfen Chemical compound C=1C=CC=NC=1OC(C)COC(C=C1)=CC=C1OC1=CC=CC=C1 NHDHVHZZCFYRSB-UHFFFAOYSA-N 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229960004394 topiramate Drugs 0.000 description 1
- 238000009333 weeding Methods 0.000 description 1
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
-
- 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
Abstract
The invention belongs to the field of pesticide synthesis, and relates to a preparation process of an intermediate chloroisoxazole for synthesizing haloxyfop-methyl and a process for synthesizing haloxyfop-methyl. The preparation process of the intermediate chloroisoxazole comprises the following steps: s1, adding hydroxylamine hydrochloride into raw material glyoxylic acid at room temperature, and performing condensation reaction to generate glyoxime formic acid; s2, chloridizing in concentrated hydrochloric acid and sodium hypochlorite in an acid binding agent and an organic solvent at the temperature of 30-50 ℃ to generate dichloroaldoxime; s3, introducing isobutene gas into the dichloroformaldehyde oxime at the temperature of 30-100 ℃ to carry out cyclization reaction, thus obtaining an intermediate chloroisoxazole. The process is a continuous process, effectively reduces the cost of raw materials, reduces the generation of three wastes, has high product yield, and is suitable for industrial production.
Description
Technical Field
The invention belongs to the field of pesticide synthesis, and relates to a preparation process of an intermediate chloroisoxazole for synthesizing haloxyfop-methyl and a process for synthesizing haloxyfop-methyl.
Background
The pyriproxyfen (Pyroxasulfone) is a broad-spectrum herbicide variety with residual activity, can be used for the pre-emergence soil treatment agent of most crop fields, has the action mechanism similar to that of acetochlor and related herbicides, has wide application crop variety and biological activity far greater than that of acetochlor and metolachlor, can be safely used for a series of crops such as corn, soybean, cotton, peanut, wheat, sunflower, potato and the like, has obvious weeding effect and is safe to the environment.
In the prior art for synthesizing the haloxyfop-methyl and the intermediate thereof, the defects of difficult acquisition of raw materials or the intermediate thereof, overlong reaction time, low conversion efficiency, more byproducts, high production scale, no utilization of industrial production and the like exist. Therefore, it has been a research hotspot and objective in the art to find a process for synthesizing metazopyr and its intermediates which is low in cost, short in synthesis time, mild in conditions, easy to operate and high in product yield.
Disclosure of Invention
Aiming at the defects in the existing process for synthesizing the halofop-butyl and the intermediate thereof, the invention aims to provide a novel preparation process of the intermediate chloroisoxazole for synthesizing the halofop-butyl, which has low cost and low synthesis route severity, and a novel process for synthesizing the halofop-butyl.
In one aspect, the invention provides a preparation process of an intermediate chloroisoxazole for synthesizing metazopyr, which comprises the following steps:
s1, adding hydroxylamine hydrochloride into raw material glyoxylic acid at room temperature to perform condensation reaction to generate glyoxime formic acid;
s2, chloridizing in concentrated hydrochloric acid and sodium hypochlorite in an acid binding agent and an organic solvent at the temperature of 30-50 ℃ to generate dichloroaldoxime;
s3, introducing isobutene gas into the dichloroformaldehyde oxime at the temperature of 30-100 ℃ to carry out cyclization reaction, thus obtaining the intermediate chloroisoxazole.
Further, in the preparation process, glyoxylate: hydroxylamine hydrochloride: the molar ratio of sodium hypochlorite is 1 (1.1-4.0): 2.1-4, preferably 1 (1.1-1.3): 2.1-1.3.
Preferably, the temperature at which the chlorination reaction is carried out in step S2 is 30-40 ℃.
Preferably, the temperature at which the ring closure reaction is carried out in step S3 is 70-85 ℃.
Further, in step S2, the acid-binding agent is an inorganic base, preferably, any one selected from sodium bicarbonate, potassium carbonate and sodium carbonate; more preferably, sodium bicarbonate.
Further, in step S2, the organic solvent is any one selected from the group consisting of dichloroethane, dichloromethane, chloroform, preferably dichloromethane.
Further, in steps S1 and S2, the molar ratio of glyoxylic acid to the acid-binding agent is 1 (1.1-4.0), preferably 1 (1.1-1.3).
Further, in step S3, the molar ratio of the dichloroaldoxime to the isobutylene is 1 (1.1-4.0), preferably 1 (1.1-2.0).
In a second aspect, the present invention provides a process for the synthesis of topiramate comprising the process for the preparation of the intermediate chloroisoxazole described in the first aspect above.
Advantageous effects
Through the technical scheme, the invention at least overcomes some defects in the existing process for synthesizing the haloxyfop-R-methyl, and obtains a novel preparation process of the intermediate chloroisoxazole which is more suitable for industrial production of the haloxyfop-R-methyl.
Compared with the existing preparation process for synthesizing the haloxyfop-R-methyl and the intermediate thereof, the preparation method adopts relatively low-cost starting materials, is easy to obtain and has low cost; the reaction steps S1-S3 are simple to operate, have milder conditions and can be continuously carried out, so that the problems of harsh reaction conditions and high equipment cost in some synthesis processes are solved, and the raw material cost is effectively reduced.
The synthesis route has the advantages of greatly reduced risk, less three-waste discharge, high intermediate yield and high purity, and is more beneficial to large-scale popularization and industrial production.
Detailed Description
The technical solution of the present invention is further explained below with reference to the specific embodiments, but the present invention is not limited in any way, and any modification, alteration or equivalent substitution method that can be implemented by those skilled in the art to which the present invention pertains will fall within the scope of the claims of the present invention without departing from the technical solution of the present invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified. Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
In the present invention, room temperature refers to 20 to 30℃unless otherwise specified.
In the synthetic route of the present invention, the content (purity) of the intermediate and target products was measured by liquid chromatography (Agilent HPLC 1260). The conversion and selectivity of the reaction were calculated by the following formula:
conversion= (molar amount of raw material charged-molar amount of raw material remaining in product)/molar amount of raw material charged x 100%.
Yield = actual molar amount of target product/theoretical molar amount of target product x 100%.
In some embodiments of the present invention, there is provided a process for preparing chloroisoxazole, an intermediate for synthesizing haloxyfop-methyl, comprising:
s1, adding hydroxylamine hydrochloride into raw material glyoxylic acid at room temperature to perform condensation reaction to generate glyoxime formic acid;
s2, chloridizing in concentrated hydrochloric acid and sodium hypochlorite in an acid binding agent and an organic solvent at the temperature of 30-50 ℃ to generate dichloroaldoxime;
s3, introducing isobutene gas into the dichloroformaldehyde oxime at the temperature of 30-100 ℃ to carry out cyclization reaction, thus obtaining the intermediate chloroisoxazole.
In the preparation process, glyoxylate: hydroxylamine hydrochloride: the molar ratio of the sodium hypochlorite to the feed is 1 (1.1-4.0) to 2.1-4. Preferably, the molar ratio is 1 (1.1-1.3): 2.1-1.3.
In some embodiments, it is preferred that the temperature at which the chlorination reaction is carried out in step S2 is 30-40 ℃.
In some embodiments, it is preferred that the temperature at which the ring closure reaction is performed in step S3 is 70-85 ℃.
In some embodiments, in step S2, the acid-binding agent is an inorganic base, preferably any one selected from sodium bicarbonate, potassium carbonate, and sodium carbonate; more preferably, sodium bicarbonate. In step S2, the organic solvent is any one selected from the group consisting of dichloroethane, dichloromethane, and chloroform, and preferably, dichloromethane.
In some embodiments, in steps S1 and S2, the molar ratio of glyoxylic acid to the acid-binding agent is 1 (1.1-4.0), preferably the molar ratio is 1 (1.1-1.3).
In some embodiments, in step S3, the molar ratio of dichloroaldoxime to isobutylene is 1 (1.1-4.0), preferably the molar ratio is 1 (1.1-2.0).
In other embodiments of the present invention, there is provided a process for the synthesis of haloxyfop, which comprises the process for the preparation of the intermediate chloroisoxazole described in the previous embodiments.
Example 1
1.01mol of 50% glyoxylate aqueous solution is added into a flask as an initial raw material, 50ml of water is added, 1.19mol of hydroxylamine hydrochloride is added during stirring, and stirring reaction is carried out for 4 hours at room temperature; then 200g of dichloroethane and 80g of 30% sodium bicarbonate solution are added into the reaction system, then 2.2mol of 30% hydrochloric acid is added into the reaction system, 2.2mol of 10% sodium hypochlorite is dropwise added at the reaction temperature of 40 ℃ and the reaction is continued for 2 hours; separating, transferring the lower organic phase into a 500ml round bottom flask, adding 165g of sodium bicarbonate, heating to 80 ℃, and introducing isobutene gas at a rate of 5g/min for reaction for 5h; filtering and concentrating to obtain the chloro isoxazole.
Calculated by taking the glyoxylic acid as a raw material compound as a reference, the yield of the intermediate chloroisoxazole is 81 percent, and the purity is 94.5 percent.
Example 2
1.01mol of 50% aqueous glyoxylate is added into a flask as an initial raw material, 50ml of water is added, 1.19mol of hydroxylamine hydrochloride is added during stirring, and the mixture is stirred at room temperature for reaction for 4 hours; then 200g of dichloroethane and 70g of 30% sodium bicarbonate solution are added into the reaction system, then 2.2mol of 30% hydrochloric acid is added into the reaction system, 2.2mol of 30% sodium hypochlorite is dropwise added at the reaction temperature of 40 ℃ and the reaction is continued for 2 hours; separating, transferring the lower organic phase into a 500ml round bottom flask, adding 165g of sodium bicarbonate, heating to 60 ℃, and introducing isobutene gas at a rate of 5g/min for reaction for 4 hours; filtering and concentrating to obtain the chloro isoxazole.
Calculated by taking the glyoxylic acid as a raw material compound as a reference, the yield of the intermediate chloroisoxazole is 79 percent, and the purity is 92.5 percent.
From the above examples, it can be seen that in examples 1 and 2, the reaction conditions are mild, the equipment requirement is not high, and the yield of the intermediate is high; the whole production cost is lower, and the solvent can be recycled, so that the method is suitable for industrial production. It can be seen that the preparation process of the invention can obtain the intermediate chloroisoxazole with high purity and high yield. In a specific embodiment, the yield of the chloroisoxazole obtained by the preparation process disclosed by the invention reaches more than 79%, the purity reaches more than 92.5%, and a better choice is provided for the existing synthesis process of the haloxyfop-R-methyl and the intermediate thereof. In addition, the preparation process can be continuously implemented, and is a process suitable for industrial production and environment-friendly.
Claims (10)
1. The preparation process of the intermediate chloroisoxazole for synthesizing the haloxyfop-methyl is characterized by comprising the following steps of:
s1, adding hydroxylamine hydrochloride into raw material glyoxylic acid at room temperature to perform condensation reaction to generate glyoxime formic acid;
s2, chloridizing in concentrated hydrochloric acid and sodium hypochlorite in an acid binding agent and an organic solvent at the temperature of 30-50 ℃ to generate dichloroaldoxime; and
s3, introducing isobutene gas into the dichloroformaldehyde oxime at the temperature of 30-100 ℃ to carry out cyclization reaction, thus obtaining the intermediate chloroisoxazole.
2. The process for preparing chloroisoxazole as an intermediate for synthesizing haloxyfop-methyl according to claim 1, wherein, in the reaction system, glyoxylate: hydroxylamine hydrochloride: the molar ratio of the sodium hypochlorite to the feed is 1 (1.1-4.0) to 2.1-4.
3. The process for preparing chloroisoxazole as an intermediate for synthesizing metazopyr as claimed in claim 2, wherein the molar ratio of the reaction system is 1 (1.1-1.3) (2.1-1.3).
4. The process for preparing chloroisoxazole as an intermediate for synthesizing pyrifos according to claim 1, wherein the temperature at which the chlorination reaction is performed in step S2 is 30-40 ℃.
5. The process for preparing chloroisoxazole as an intermediate for synthesizing pyrifos according to claim 1, wherein the temperature of the ring closure reaction performed in the step S3 is 70-85 ℃.
6. The process for preparing chloroisoxazole as an intermediate for synthesizing haloxyfop-methyl according to claim 1, wherein in step S2, the acid-binding agent is an inorganic base.
7. The process for preparing chloroisoxazole as an intermediate for synthesizing pyrifos according to claim 6, wherein the inorganic base is any one selected from sodium bicarbonate, potassium carbonate and sodium carbonate.
8. The process for preparing chloroisoxazole as an intermediate for synthesizing haloxyfop-methyl according to claim 1, wherein in the steps S1 and S2, the molar ratio of glyoxylic acid to acid-binding agent is 1 (1.1-4.0).
9. The process for preparing chloroisoxazole as an intermediate for synthesizing haloxyfop-methyl according to claim 1, wherein in the step S3, the feeding molar ratio of dichloroaldoxime to isobutene is 1 (1.1-4.0).
10. A process for synthesizing haloxyfop-methyl, comprising the process for preparing the intermediate chloroisoxazole according to any one of claims 1 to 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310292827.3A CN116041270A (en) | 2023-03-24 | 2023-03-24 | Preparation process of intermediate chloroisoxazole for synthesizing fenpyr-diethyl |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310292827.3A CN116041270A (en) | 2023-03-24 | 2023-03-24 | Preparation process of intermediate chloroisoxazole for synthesizing fenpyr-diethyl |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116041270A true CN116041270A (en) | 2023-05-02 |
Family
ID=86114915
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310292827.3A Pending CN116041270A (en) | 2023-03-24 | 2023-03-24 | Preparation process of intermediate chloroisoxazole for synthesizing fenpyr-diethyl |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116041270A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106432069A (en) * | 2016-09-09 | 2017-02-22 | 安徽工业大学 | A method for preparation of 2-amino-5-chloro-pyridine |
| CN110698452A (en) * | 2019-10-27 | 2020-01-17 | 淮安瀚康新材料有限公司 | Preparation method of chlorinated ethylene carbonate by using novel initiator |
| CN113336716A (en) * | 2021-06-10 | 2021-09-03 | 江苏省农用激素工程技术研究中心有限公司 | Preparation method of topramezone intermediate |
| 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 |
| WO2021176456A1 (en) * | 2020-03-05 | 2021-09-10 | Adama Agan Ltd. | Process and intermediates for the preparation of pyroxasulfone |
| CN114957233A (en) * | 2022-07-05 | 2022-08-30 | 淄博新农基作物科学有限公司 | Sulfoxapyrazole and preparation method thereof |
-
2023
- 2023-03-24 CN CN202310292827.3A patent/CN116041270A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106432069A (en) * | 2016-09-09 | 2017-02-22 | 安徽工业大学 | A method for preparation of 2-amino-5-chloro-pyridine |
| CN110698452A (en) * | 2019-10-27 | 2020-01-17 | 淮安瀚康新材料有限公司 | Preparation method of chlorinated ethylene carbonate by using novel initiator |
| WO2021176456A1 (en) * | 2020-03-05 | 2021-09-10 | Adama Agan Ltd. | Process and intermediates for the preparation of pyroxasulfone |
| 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 |
| CN113336716A (en) * | 2021-06-10 | 2021-09-03 | 江苏省农用激素工程技术研究中心有限公司 | Preparation method of topramezone intermediate |
| CN114957233A (en) * | 2022-07-05 | 2022-08-30 | 淄博新农基作物科学有限公司 | Sulfoxapyrazole and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106749072A (en) | The preparation method of clomazone | |
| CN107963993A (en) | A kind of preparation method of high-purity ethiprole | |
| CN111170892B (en) | Synthesis method of N-methyl (2S) -2-N-fluorenylmethoxycarbonylamino-aspartic acid (4-tert-butyl ester) | |
| CN110117256B (en) | Synthesis method of bixafen | |
| CN109467532B (en) | Preparation method of 4-trifluoromethyl nicotinic acid | |
| CN112645833A (en) | Synthesis method of (S) -2, 6-diamino-5-oxohexanoic acid | |
| CN116041270A (en) | Preparation process of intermediate chloroisoxazole for synthesizing fenpyr-diethyl | |
| CN115141147B (en) | Synthesis method of N-methyl-3-substituted methyl-4-pyrazole formamide derivative | |
| CN111170846A (en) | Method for preparing 3, 3-dimethyl-2-oxo-butyric acid | |
| CN102452977A (en) | Method for preparing 2-chloro-5-trichloromethylpyridine | |
| CN114671859A (en) | Preparation method of rosuvastatin calcium and intermediate thereof | |
| CN114717280A (en) | Synthesis method of monopilavir | |
| CN113149899A (en) | Method for preparing 4-trifluoromethyl nicotinic acid | |
| Kim et al. | A Facile Synthetic Method of Herbicidal 2, 3-Dihydro-3-methylene-2-substituted-phenyl-1 H-isoindol-1-one Derivatives | |
| CN114456048B (en) | Preparation method of penconazole intermediate | |
| CN113045424A (en) | Synthetic method of 2- (5-fluoro-2-nitrophenoxy) acetate compound | |
| CA2867936C (en) | Industrial method for manufacturing high-purity methiozolin | |
| CN111732553B (en) | Method for synthesizing herbicide fenoxaprop-p-ethyl | |
| CN115181031B (en) | Preparation method of 2-amino-5-chlorobenzoic acid derivative | |
| CN113717123B (en) | Preparation method of metamifop | |
| CN115784837B (en) | Process for preparing 3-chlorobicyclo [3.2.1] -3-octen-2-ol | |
| CN113979953B (en) | Method for preparing saflufenacil intermediate | |
| CN117024406A (en) | Synthesis method of imazethapyr | |
| CN113754602B (en) | Synthesis method of 5, 5-dimethyl-4, 5-dihydro-isoxazole-3-one | |
| CN115873019A (en) | Preparation method of pinoxaden and intermediate thereof |
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 | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20230502 |