CN114644602B - Preparation method of dihydro isoxazole compound - Google Patents
Preparation method of dihydro isoxazole compound Download PDFInfo
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- CN114644602B CN114644602B CN202011497632.5A CN202011497632A CN114644602B CN 114644602 B CN114644602 B CN 114644602B CN 202011497632 A CN202011497632 A CN 202011497632A CN 114644602 B CN114644602 B CN 114644602B
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- -1 dihydro isoxazole compound Chemical class 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 18
- 239000002994 raw material Substances 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000005658 halogenation reaction Methods 0.000 claims abstract description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 8
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 6
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical group [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 4
- ZKQDCIXGCQPQNV-UHFFFAOYSA-N Calcium hypochlorite Chemical compound [Ca+2].Cl[O-].Cl[O-] ZKQDCIXGCQPQNV-UHFFFAOYSA-N 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- TXXJGCVOHDSYBC-UHFFFAOYSA-N n-methylaniline;2,2,2-trifluoroacetic acid Chemical compound [O-]C(=O)C(F)(F)F.C[NH2+]C1=CC=CC=C1 TXXJGCVOHDSYBC-UHFFFAOYSA-N 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 230000026030 halogenation Effects 0.000 claims 1
- 150000007522 mineralic acids Chemical class 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 125000005048 dihydroisoxazolyl group Chemical class O1N(CC=C1)* 0.000 abstract 1
- VEEFADFWCHSFIU-UHFFFAOYSA-N 3-methylbut-3-enal Chemical compound CC(=C)CC=O VEEFADFWCHSFIU-UHFFFAOYSA-N 0.000 description 7
- SEPQTYODOKLVSB-UHFFFAOYSA-N 3-methylbut-2-enal Chemical compound CC(C)=CC=O SEPQTYODOKLVSB-UHFFFAOYSA-N 0.000 description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 5
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 5
- 229910052794 bromium Inorganic materials 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- DIYSFZUJSGOINT-UHFFFAOYSA-N 5,5-dimethyl-4h-1,2-oxazole Chemical class CC1(C)CC=NO1 DIYSFZUJSGOINT-UHFFFAOYSA-N 0.000 description 4
- PXAJQJMDEXJWFB-UHFFFAOYSA-N acetone oxime Chemical compound CC(C)=NO PXAJQJMDEXJWFB-UHFFFAOYSA-N 0.000 description 4
- 208000012839 conversion disease Diseases 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- ACWQBUSCFPJUPN-UHFFFAOYSA-N Tiglaldehyde Natural products CC=C(C)C=O ACWQBUSCFPJUPN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004009 herbicide Substances 0.000 description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 2
- ASMQGLCHMVWBQR-UHFFFAOYSA-N Diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-N 0.000 description 2
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical compound Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 description 2
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- AFBPFSWMIHJQDM-UHFFFAOYSA-N N-methylaniline Chemical compound CNC1=CC=CC=C1 AFBPFSWMIHJQDM-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 description 2
- 230000002363 herbicidal effect Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- ITMCEJHCFYSIIV-UHFFFAOYSA-N triflic acid Chemical compound OS(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-N 0.000 description 2
- FJRPOHLDJUJARI-UHFFFAOYSA-N 2,3-dihydro-1,2-oxazole Chemical class C1NOC=C1 FJRPOHLDJUJARI-UHFFFAOYSA-N 0.000 description 1
- 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
- VTNQPKFIQCLBDU-UHFFFAOYSA-N Acetochlor Chemical compound CCOCN(C(=O)CCl)C1=C(C)C=CC=C1CC VTNQPKFIQCLBDU-UHFFFAOYSA-N 0.000 description 1
- WTEVQBCEXWBHNA-UHFFFAOYSA-N Citral Natural products CC(C)=CCCC(C)=CC=O WTEVQBCEXWBHNA-UHFFFAOYSA-N 0.000 description 1
- 239000005592 Penoxsulam Substances 0.000 description 1
- SYJGKVOENHZYMQ-UHFFFAOYSA-N Penoxsulam Chemical compound N1=C2C(OC)=CN=C(OC)N2N=C1NS(=O)(=O)C1=C(OCC(F)F)C=CC=C1C(F)(F)F SYJGKVOENHZYMQ-UHFFFAOYSA-N 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229940043350 citral Drugs 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- DMKOEAUNIVCIPW-UHFFFAOYSA-N diphenyl hydrogen phosphate;n-methylaniline Chemical compound CNC1=CC=CC=C1.C=1C=CC=CC=1OP(=O)(O)OC1=CC=CC=C1 DMKOEAUNIVCIPW-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- WTEVQBCEXWBHNA-JXMROGBWSA-N geranial Chemical compound CC(C)=CCC\C(C)=C\C=O WTEVQBCEXWBHNA-JXMROGBWSA-N 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000003756 stirring Methods 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
Abstract
The invention relates to the technical field of organic synthesis, in particular to a preparation method of dihydro isoxazole compounds. A process for producing a 3-chloro-5, 5-dimethyl-4, 5-dihydroisoxazole compound represented by the formula (I), comprising: taking a compound shown in a formula (II), hypochlorite and inorganic acid as raw materials to carry out halogenation reaction; a process for producing a 5, 5-dimethyl-4, 5-dihydroisoxazole compound represented by the formula (II), comprising: the method is characterized in that a compound shown in a formula (III) and a hydroxylamine compound are used as raw materials to react under the action of a catalyst. The preparation method provided by the invention has the advantages of high conversion rate, high selectivity, high product yield and low cost.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of dihydro isoxazole compounds.
Background
The weeding activity of the penoxsulam herbicide is 8-12 times that of acetochlor and metolachlor, and the herbicide has quite considerable market prospect; and 3-halogenated 5, 5-dimethyl-4, 5-dihydro-isoxazole compounds are important intermediates for preparing haloxyfop herbicides. Numerous literature reports the preparation of 3-halogenated 5, 5-dimethyl-4, 5-dihydroisoxazole compounds as follows: glyoxylic acid is used as a raw material, firstly reacts with hydroxylamine hydrochloride to prepare oxime, then reacts with bromine to replace decarboxylation to prepare dibromoaldoxime, more than 2eq of expensive bromine is needed, and the bromine utilization rate is only 25%, so that the cost of the method is high.
WO2011063842 discloses a preparation method, wherein 3-methyl-2-butenal and acetoxime are subjected to cyclization in the presence of an acid-base catalyst to prepare 5, 5-dimethyl-4, 5-dihydro-isoxazole, and then chlorine is used for chloro to prepare a 3-chloro 5, 5-dimethyl-4, 5-dihydro-isoxazole compound; TW201945347A discloses a process for preparing 5, 5-dimethyl-4, 5-dihydroisoxazole compounds from aqueous solutions of 3-methyl-2-butenal and hydroxylamine in the presence of acid-base catalysts. 3-methyl-2-butenal is a raw material for preparing citral, which is prepared by high-temperature isomerization of 3-methyl-3-butenal catalyst, and thus, the above preparation method is also high in cost.
In view of this, the present invention has been made.
Disclosure of Invention
The invention aims to provide a preparation method of a 3-chloro-5, 5-dimethyl-4, 5-dihydro-isoxazole compound, which avoids the use of dangerous chlorine or bromine, is safer, and the obtained 3-chloro-5, 5-dimethyl-4, 5-dihydro-isoxazole compound has high yield and high purity; the invention also aims to provide a preparation method of the 5, 5-dimethyl-4, 5-dihydro-isoxazole compound, which adopts 3-methyl-3-butenal and hydroxylamine compounds as raw materials, greatly reduces the cost, and has high yield and high purity of the obtained 5, 5-dimethyl-4, 5-dihydro-isoxazole compound.
Specifically, the invention provides the following technical scheme:
A process for producing a 3-chloro-5, 5-dimethyl-4, 5-dihydroisoxazole compound represented by the formula (I), which comprises: taking a compound shown in a formula (II), hypochlorite and inorganic acid as raw materials to carry out halogenation reaction;
The invention discovers that the 3-chloro-5, 5-dimethyl-4, 5-dihydro-isoxazole compound obtained by taking the compound shown in the formula (II), hypochlorite and inorganic acid as raw materials for carrying out halogenation reaction has high purity and high yield.
Preferably, the hypochlorite is sodium hypochlorite or calcium hypochlorite;
Preferably, the inorganic acid is hydrochloric acid or hydrobromic acid.
Aiming at the halogenated reaction system, sodium hypochlorite or calcium hypochlorite is adopted as hypochlorite, hydrochloric acid or hydrobromic acid is adopted as inorganic acid, and the reaction conversion rate is improved.
Preferably, the halogenation reaction is carried out in a solvent which is an alcoholic nitrile or an aromatic hydrocarbon;
preferably, the halogenation reaction is carried out at a temperature of-10 to 100 ℃; preferably, the halogenation reaction is carried out at 0 to 10 ℃.
Preferably, the compound represented by formula (II): hypochlorite: mineral acid = 1:1 to 3:1 to 5.
The invention also provides the 3-chloro-5, 5-dimethyl-4, 5-dihydro-isoxazole compound prepared by the method.
The invention also provides a preparation method of the 5, 5-dimethyl-4, 5-dihydro-isoxazole compound shown in the formula (II), wherein the 5, 5-dimethyl-4, 5-dihydro-isoxazole compound shown in the formula (II) is the same as the above.
Specifically, the preparation method comprises the following steps: taking a compound shown in a formula (III) as a raw material, and reacting under the action of a catalyst;
Preferably, the hydroxylamine compound is acetoxime or hydroxylamine aqueous solution.
Preferably, the hydroxylamine compound is used in an amount of 1 to 3mol based on 1mol of the compound represented by the formula (III); preferably 1.1 to 1.5mol.
Aiming at the reaction system, the aqueous solution of acetoxime or hydroxylamine is adopted as hydroxylamine compound, which is beneficial to improving the reaction conversion rate; and when the amount of the compound represented by the formula (III) to be used is in the above range, the reaction conversion is higher.
Preferably, the catalyst is an acid-base composite catalyst;
Wherein the acid is organic acid or inorganic acid (organic acid such as alkyl sulfonic acid, aryl sulfonic acid, alkyl phosphate, aryl phosphate, halogenated alkyl carboxylic acid, etc., inorganic acid such as hydrochloric acid, sulfuric acid, phosphoric acid, etc.), preferably one or more of methanesulfonic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, citric acid, diphenyl phosphoric acid;
the base is an organic base, preferably a secondary amine (e.g., N-alkylaniline, substituted N-alkylaniline, tetrahydropyrrole, 2, 3-indoline, substituted 2, 3-indoline, etc.);
more preferably, the catalyst is one of diphenyl phosphoric acid and N-methylaniline, trifluoroacetic acid and 2, 3-indoline, trifluoromethanesulfonic acid and 2, 3-indoline.
For the above reaction system, the effect is best when the catalyst is trifluoroacetic acid and 2, 3-indoline.
Preferably, the catalyst is used in an amount of 1 to 5mol% relative to 1mol of the compound represented by the formula (III); preferably 1mol%.
Preferably, the reaction is carried out at 0 to 30 ℃.
The invention also provides the 5, 5-dimethyl-4, 5-dihydro-isoxazole compound prepared by the method.
The invention has the excellent effects that:
(1) The hypochlorite is adopted as the chloro reagent, so that dangerous chlorine or bromine is avoided, and the process is safer; and by selecting specific raw materials to react with hypochlorite, the method has high conversion rate, high selectivity, high product yield and low cost.
(2) The invention adopts 3-methyl-3-butenal and hydroxylamine compound as raw materials to react under the action of the catalyst, and has high reaction conversion rate, high selectivity, high product yield and low cost.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
In the examples below, the amounts of reactants and products were measured by liquid chromatography (AGILENT HPLC 1260).
In the following examples, the conversion and selectivity of the reaction were calculated by the following formulas:
conversion= (molar amount of raw material charged-molar amount of raw material remaining in product)/molar amount of raw material charged x 100%;
Selectivity = actual molar amount of target product/theoretical molar amount of target product x 100%.
Example 1 preparation of 5, 5-dimethyl-4, 5-dihydroisoxazole Compound
100G (1.37 mol) of acetoxime and 110g of 3-methyl-3-butenal (1.3 mol) are added into a four-port bottle provided with a mechanical stirrer, a thermometer and a condenser, the mixture is stirred and cooled to 10 ℃ to be fully mixed, 2g N-methylaniline diphenyl phosphate is added at one time, the mixture is stirred for one hour at 10 ℃, the temperature is restored to room temperature, stirring is carried out for 5 hours, the 3-methyl-3-butenal is detected to react completely in a gas phase, and 110g (75-77 ℃/50 Torr) of a target product is obtained through direct rectification, and the conversion rate of the reaction is 99 percent and the yield is 85 percent.
Example 2 preparation of 5, 5-dimethyl-4, 5-dihydroisoxazole Compound
110G of 3-methyl-3-butenal (1.3 mol), 92.4g of hydroxylamine aqueous solution are added into a four-necked flask equipped with a mechanical stirrer, a thermometer and a condenser, the mixture is stirred and cooled to 10 ℃ to be fully mixed, 2g N-methylaniline trifluoroacetate is added at one time, the mixture is stirred for one hour at 10 ℃, the temperature is restored to be stirred for 5 hours, the reaction of 3-methyl-3-butenal is detected to be complete in a gas phase, 115g of target product is obtained through direct rectification, and the conversion rate of the reaction is 99% and the yield is 89%.
EXAMPLE 33 preparation of chloro-5, 5-dimethyl-4, 5-dihydroisoxazole Compound
100G (1 mol) of 5, 5-dimethyl-4, 5-dihydroisoxazole compound (prepared in example 1) and 200mL of tertiary butanol are added into a four-port bottle provided with a mechanical stirrer, a thermometer and a condenser tube, the mixture is stirred and fully mixed, the temperature is reduced to 10 ℃, 150g (1.5 mol) of hydrochloric acid aqueous solution is added, 1.1kg of sodium hypochlorite aqueous solution is slowly added dropwise for 2 hours, the thermal insulation reaction is continuously carried out for 1 hour after the dropwise addition, the reaction of the raw materials is detected to be complete, the tertiary butanol is removed under negative pressure, and the toluene is extracted to obtain the target product, the conversion rate is 98 percent, and the quantitative yield is 90 percent.
While the invention has been described in detail in the foregoing general description, embodiments and experiments, it will be apparent to those skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (6)
1. A process for producing a 5, 5-dimethyl-4, 5-dihydroisoxazole compound represented by the formula (II), which comprises: taking a compound shown in a formula (III) and hydroxylamine aqueous solution as raw materials, and reacting under the action of a catalyst N-methylaniline trifluoroacetate;
The compound of formula (II), Formula (III)
The dosage of the hydroxylamine aqueous solution is 1.1 to 1.5mol relative to the dosage of the compound shown in the formula (III) of 1 mol; the catalyst is used in an amount of 1 to 5mol% relative to 1mol of the compound represented by the formula (III);
The reaction is carried out at 0-30 ℃.
2. The preparation method according to claim 1, wherein the catalyst is used in an amount of 1mol% relative to 1mol of the compound represented by the formula (III).
3. A process for producing a 3-chloro-5, 5-dimethyl-4, 5-dihydroisoxazole compound represented by the formula (I), which comprises: taking a compound shown in a formula (II), hypochlorite and hydrochloric acid as raw materials to carry out halogenation reaction;
The compound of formula (I), Formula (II);
further comprising the step of preparing a compound of formula (II) according to the method of claim 1 or 2.
4. A method of preparation according to claim 3, wherein the hypochlorite is sodium hypochlorite or calcium hypochlorite.
5. The process according to claim 3 or 4, wherein the halogenation is carried out in a solvent which is an alcohol, nitrile or aromatic hydrocarbon;
and/or the halogenation reaction is carried out at the temperature of-10-100 ℃.
6. The process according to claim 3 or 4, wherein the compound represented by the formula (II): hypochlorite: hydrochloric acid = 1: 1-3: 1-5.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4192820A (en) * | 1977-04-05 | 1980-03-11 | Basf Aktiengesellschaft | Preparation of 3-methyl-2-buten-1-al |
| CN102666502A (en) * | 2009-11-26 | 2012-09-12 | 巴斯夫欧洲公司 | Method for producing 5,5-disubstituted 4,5-dihydroisoxazol-3-thiocarboxamidine salts |
| CN110878058A (en) * | 2018-09-06 | 2020-03-13 | 东莞市东阳光农药研发有限公司 | Isoxazoline derivatives and their use in agriculture |
| CN112004805A (en) * | 2018-04-27 | 2020-11-27 | 组合化学工业株式会社 | Process for producing 5, 5-disubstituted-4, 5-dihydroisoxazoles |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10975041B2 (en) * | 2017-12-15 | 2021-04-13 | Kumiai Chemical Industry Co., Ltd. | Method for producing 5, 5-disubstituted-4, 5-dihydroisoxazole |
| WO2019131715A1 (en) * | 2017-12-27 | 2019-07-04 | クミアイ化学工業株式会社 | Method for producing thiocarboxamidine salt compound |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4192820A (en) * | 1977-04-05 | 1980-03-11 | Basf Aktiengesellschaft | Preparation of 3-methyl-2-buten-1-al |
| CN102666502A (en) * | 2009-11-26 | 2012-09-12 | 巴斯夫欧洲公司 | Method for producing 5,5-disubstituted 4,5-dihydroisoxazol-3-thiocarboxamidine salts |
| CN112004805A (en) * | 2018-04-27 | 2020-11-27 | 组合化学工业株式会社 | Process for producing 5, 5-disubstituted-4, 5-dihydroisoxazoles |
| CN110878058A (en) * | 2018-09-06 | 2020-03-13 | 东莞市东阳光农药研发有限公司 | Isoxazoline derivatives and their use in agriculture |
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