CN114539041B - Preparation method of penconazole intermediate - Google Patents
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- CN114539041B CN114539041B CN202011345578.2A CN202011345578A CN114539041B CN 114539041 B CN114539041 B CN 114539041B CN 202011345578 A CN202011345578 A CN 202011345578A CN 114539041 B CN114539041 B CN 114539041B
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- WKBPZYKAUNRMKP-UHFFFAOYSA-N 1-[2-(2,4-dichlorophenyl)pentyl]1,2,4-triazole Chemical compound C=1C=C(Cl)C=C(Cl)C=1C(CCC)CN1C=NC=N1 WKBPZYKAUNRMKP-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000005813 Penconazole Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000460 chlorine Substances 0.000 claims abstract description 18
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 18
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 18
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 8
- 238000005580 one pot reaction Methods 0.000 claims abstract description 6
- 230000009471 action Effects 0.000 claims abstract description 5
- 238000007664 blowing Methods 0.000 claims abstract description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical group OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 239000002798 polar solvent Substances 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- 229940090668 parachlorophenol Drugs 0.000 claims description 4
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229940076286 cupric acetate Drugs 0.000 claims description 3
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 2
- 229940045803 cuprous chloride Drugs 0.000 claims description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 2
- 229940112669 cuprous oxide Drugs 0.000 claims description 2
- 239000005760 Difenoconazole Substances 0.000 claims 2
- BQYJATMQXGBDHF-UHFFFAOYSA-N difenoconazole Chemical compound O1C(C)COC1(C=1C(=CC(OC=2C=CC(Cl)=CC=2)=CC=1)Cl)CN1N=CN=C1 BQYJATMQXGBDHF-UHFFFAOYSA-N 0.000 claims 2
- 230000005587 bubbling Effects 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 239000002699 waste material Substances 0.000 abstract description 4
- 239000002351 wastewater Substances 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 abstract description 2
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 238000004904 shortening Methods 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004128 high performance liquid chromatography Methods 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 2
- XBBGYSIEJHXPLL-UHFFFAOYSA-N 2-bromo-4-fluoro-1-(trifluoromethyl)benzene Chemical compound FC1=CC=C(C(F)(F)F)C(Br)=C1 XBBGYSIEJHXPLL-UHFFFAOYSA-N 0.000 description 1
- -1 4-chlorophenoxy Chemical group 0.000 description 1
- 208000003643 Callosities Diseases 0.000 description 1
- 235000008534 Capsicum annuum var annuum Nutrition 0.000 description 1
- 240000008384 Capsicum annuum var. annuum Species 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 244000068988 Glycine max Species 0.000 description 1
- 235000010469 Glycine max Nutrition 0.000 description 1
- 238000003747 Grignard reaction Methods 0.000 description 1
- 239000007818 Grignard reagent Substances 0.000 description 1
- 241000257303 Hymenoptera Species 0.000 description 1
- 206010020649 Hyperkeratosis Diseases 0.000 description 1
- 241000124008 Mammalia Species 0.000 description 1
- 208000031888 Mycoses Diseases 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
- 241000219094 Vitaceae 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
- 150000008062 acetophenones Chemical class 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000006735 epoxidation reaction Methods 0.000 description 1
- 230000008029 eradication Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 244000037666 field crops Species 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 235000021021 grapes Nutrition 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/44—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reduction and hydrolysis of nitriles
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention belongs to the technical field of intermediate compound preparation, and particularly relates to a preparation method of a penconazole intermediate. The preparation method of the penconazole intermediate is a one-pot synthesis process, and comprises the following steps: under the action of inorganic base and catalyst, taking the reagent with the formula (II) and chlorine as raw materials, and blowing air to react to obtain the target product. The invention provides a one-pot synthesis line, which utilizes oxygen in air to oxidize cyano in formula (II) while chlorine-containing reagent reacts with R group in formula (II), thus greatly shortening reaction process and improving production efficiency; moreover, the reaction condition is milder, the waste water is less and is easy to treat, the method is more suitable for industrialized mass production, and the problems of harsh conditions, large three wastes, bad production environment and the like of the existing intermediate synthesis line are solved. Meanwhile, the cost of raw materials for synthesizing the intermediate of the penconazole can be greatly reduced, and the method has practical economic benefit.
Description
Technical Field
The invention belongs to the technical field of intermediate compound preparation, and particularly relates to a preparation method of a penconazole intermediate.
Background
The penoxsulam (common name: mefenobuconazole) is a triazole bactericide which is newly developed by Basoff company and has epoch-making significance, and is formally marketed in 2019, and the future market is expected to exceed 10 hundred million dollars per year.
The penconazole has the functions of broad spectrum, high efficiency, systemic, eradication, protection and the like, has outstanding biological activity especially on a plurality of fungal diseases which are difficult to control, can obviously strengthen the control of more than 60 crop diseases, such as field crops like corns, grains, soybeans and the like, economic crops like green peppers, grapes and the like, and can also be used for lawn and seed treatment and the like. It has higher bioactivity, good environmental characteristics, low toxicity to mammals, bees and the like, and high safety.
The 4- (4-chlorophenoxy) -2-trifluoromethyl acetophenone is a key intermediate for synthesizing the penconazole, and the penconazole is prepared through epoxidation and ring-opening substitution reaction, so that the process is simple and the yield is higher. The structure is as follows:
the technology currently used for producing 4- (4-chlorophenoxy) -2-trifluoromethyl acetophenone is mostly referred to the technology disclosed in the prior art CN103649057 a. 2-bromo-4-fluoro-benzotrifluoride is taken as a raw material, grignard reagent is prepared in tetrahydrofuran solution, acetyl chloride is added dropwise, after the reaction is finished, 4-fluoro-2-benzotrifluoride is prepared through processes such as extraction, water washing and the like, and then 4- (4-chlorophenoxy) -2-benzotrifluoride is synthesized by reacting with 4-chlorophenol. The specific reaction route is as follows:
however, the process route needs to use a format reaction, the condition is severe, and a large amount of magnesium-containing wastewater is generated after the reaction, so that the magnesium-containing wastewater is difficult to treat.
In conclusion, the existing method has the defects of large three wastes, high cost, bad production environment and the like when preparing the 4-p-chlorophenoxy acetophenone compounds.
Disclosure of Invention
The invention aims to provide a novel preparation method of a penconazole intermediate (4- (4-chlorophenoxy) -2-trifluoromethyl acetophenone).
The preparation method of the penconazole intermediate adopts a one-pot synthesis process; comprising the following steps: under the action of inorganic base and catalyst, the catalyst is represented by formula (II)The chlorine-containing reagent is used as a raw material, and a target product is obtained through air blowing and reaction;
in the formula (II), R is F, cl, br, I, NO 2 OH; preferably F, NO 2 、OH。
The chlorine-containing reagent is p-chlorophenol or p-dichlorobenzene.
Aiming at the defects of the existing synthesis process of the penconazole intermediate, the invention provides a one-pot synthesis line, and when a chlorine-containing reagent reacts with an R group in a formula (II), the cyano group in the formula (II) is oxidized by oxygen in the air, so that the reaction process can be greatly shortened, and the production efficiency is improved; moreover, the reaction condition is milder, the waste water is less and is easy to treat, the method is more suitable for industrialized mass production, and the problems of harsh conditions, large three wastes, bad production environment and the like of the existing intermediate synthesis line are solved.
Furthermore, screening is carried out according to formula (II)As a raw material, the cost of the raw material for synthesizing the intermediate of the penconazole can be greatly reduced, and the method has practical economic benefit.
The air intake is required to meet the actual production requirement, and can be adjusted by combining experience according to actual conditions by a person skilled in the art.
The process route of the invention is as follows:
as one of the specific embodiments of the present invention, R in the formula (II) is selected to be NO 2 The chlorine-containing reagent is parachlorophenol. Under the combined condition, the reaction is more fully carried out, and the yield is higher.
The inorganic base is any one of sodium hydroxide, potassium carbonate or sodium carbonate, preferably sodium carbonate or potassium carbonate. The inorganic base acts as an acid-fuelling agent. Compared with other inorganic bases, the sodium carbonate or the potassium carbonate is more beneficial to promoting the reaction and improving the yield.
The catalyst is any one of copper ions such as cuprous chloride, cuprous iodide, cuprous oxide, cupric acetate and the like, and preferably cupric acetate. Compared with other catalysts, the copper acetate can promote the reaction to be more fully carried out, and the reaction yield is higher.
As another embodiment of the present invention, the inorganic base is selected to be sodium carbonate or potassium carbonate; the catalyst is copper acetate. The catalytic effect of the copper acetate is better under the alkali system, which is more beneficial to the reaction and improves the yield.
The formula (II) described above relative to 1mol of formula (II): inorganic base: chlorine-containing reagent: the molar ratio of the catalyst to the use amount is 1:0.8-2:0.8-2:0.01-0.1; preferably, the molar ratio of the amount used is 1:0.9 to 1.2:0.9-1.1:0.02-0.05; the preferable dosage mole ratio has the advantages of high reaction yield, low cost and less three wastes.
The temperature of the reaction is 80-150 ℃, preferably 110-130 ℃; the time is 2-8 hours, preferably 3-5 hours.
The reaction is carried out in a polar solvent; the polar solvent is one of acetonitrile, dioxane, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone.
As one of specific embodiments of the invention, the preparation method of the penconazole intermediate comprises the following steps:
under the action of inorganic base and catalyst, the catalyst is represented by formula (II)The chlorine-containing reagent is used as a raw material, and a target product is obtained through air blowing and reaction;
wherein R in the formula (II) is NO 2 ；
The chlorine-containing reagent is parachlorophenol;
the inorganic base is potassium carbonate;
the catalyst is copper acetate;
the polar solvent is DMF;
the formula (II): inorganic base: chlorine-containing reagent: the molar ratio of the catalyst to the use amount is 1:0.9 to 1.2:0.9-1.1:0.02-0.05;
the temperature of the reaction is 120-125 ℃.
The beneficial effects of the invention are as follows:
aiming at the defects of the prior art of the intermediate of the penconazole, the invention provides a new synthetic route. By selecting a specific formula (II) as a raw material, the synthesis of a target product is realized by adopting a one-pot method. The method can omit Grignard reaction and avoid harsh reaction conditions; meanwhile, the production cost is greatly reduced, the yield and purity are improved, and the method has industrial application value.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
The amounts of reactants and products were determined 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%.
Selectivity = actual molar amount of target product/theoretical molar amount of target product x 100%
Unless otherwise specified, all materials used are commercially available products.
Example 1
Preparation of 4- (4-chlorophenoxy) -2-trifluoromethyl acetophenone
Into a four-necked flask equipped with a mechanical stirrer, a thermometer and a condenser, 25.7g (0.1 mol, 95%) of formula (II) and 150 mM LDMF were added, followed by 15.4g (0.12 mol, 99%) of p-chlorophenol, 16.8g (0.12 mol, 99%) of potassium carbonate and 0.4g of copper acetate, and the temperature was raised to 120-125℃and air was blown for stirring reaction for 5 hours;
HPLC detection of the raw materials is complete, toluene is added to the recovered solvent, acid water is added to adjust the pH to be 7, the water phase is separated, toluene is removed from the organic layer, 29.8g of 4- (4-chlorophenoxy) -2-trifluoromethyl acetophenone is obtained, the content is 98%, and the yield is 95%.
Example 2
Unlike example 1, the nitro group of formula (II) was replaced by fluoro group, the other conditions were unchanged, the content was 98%, and the yield was 89%.
Example 3
Unlike example 1, the nitro group of formula (II) was replaced with hydroxy group, p-chlorophenol was replaced with p-dichlorobenzene, the other conditions were unchanged, the content was 97%, and the yield was 85%.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one 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 (8)
1. A preparation method of a penconazole intermediate is characterized in that a one-pot synthesis process is adopted; comprising the following steps: under the action of inorganic base and catalyst, the catalyst is represented by formula (II)The chlorine-containing reagent is used as a raw material, and a target product is obtained through bubbling air for reaction;
in the formula (II), R is F, cl, br, I, NO 2 、OH；
The chlorine-containing reagent is p-chlorophenol or p-dichlorobenzene;
the reaction route is as follows:
the inorganic base is any one of sodium hydroxide, potassium carbonate or sodium carbonate;
the catalyst is any one of cuprous chloride, cuprous iodide, cuprous oxide and cupric acetate;
the reaction is carried out in a polar solvent; the polar solvent is one of acetonitrile, dioxane, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide or N-methylpyrrolidone.
2. The method for preparing a penconazole intermediate according to claim 1, wherein R in formula (II) is NO 2 The chlorine-containing reagent is parachlorophenol.
3. The method for preparing a penconazole intermediate according to claim 1, wherein said inorganic base is sodium carbonate or potassium carbonate; the catalyst is copper acetate.
4. The process for preparing a difenoconazole intermediate according to claim 3, wherein the molar ratio of inorganic base to chlorine-containing agent to catalyst is 1:0.8-2:0.8-2:0.01-0.1 with respect to 1mol of formula (II).
5. The process for preparing a difenoconazole intermediate according to claim 4, wherein the molar ratio of said formula (II) to inorganic base to chlorine-containing agent to catalyst is 1:0.9-1.2:0.9-1.1:0.02-0.05 with respect to 1mol of formula (II).
6. The method for preparing a penconazole intermediate according to claim 5, wherein the temperature of said reaction is 80-150 ℃.
7. The method for preparing a penconazole intermediate according to claim 6, wherein the temperature of said reaction is 110-130 ℃.
8. The method for preparing the intermediate of the penconazole according to any one of claims 1 to 7, wherein said method for preparing the intermediate of the penconazole is as follows:
under the action of inorganic base and catalyst, the catalyst is represented by formula (II)The chlorine-containing reagent is used as a raw material, and a target product is obtained through air blowing and reaction;
wherein R in the formula (II) is NO 2 ；
The chlorine-containing reagent is parachlorophenol;
the inorganic base is potassium carbonate;
the catalyst is copper acetate;
the polar solvent is DMF;
the molar ratio of the inorganic base to the chlorine-containing reagent to the catalyst in the formula (II) is 1:0.9-1.2:0.9-1.1:0.02-0.05;
the temperature of the reaction is 120-125 ℃.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1552696A (en) * | 2003-05-30 | 2004-12-08 | 中国科学院大连化学物理研究所 | Synthesis of p-cyanoacetophenone by direct catalyst selective oxidation |
| CN101786948A (en) * | 2010-01-25 | 2010-07-28 | 江苏省农用激素工程技术研究中心有限公司 | Method for preparing 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone |
| CN102675074A (en) * | 2012-05-25 | 2012-09-19 | 江西华士药业有限公司 | Preparation method of cyproconazole key intermediate 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone |
| CN103044230A (en) * | 2012-12-26 | 2013-04-17 | 湖南化工研究院 | Preparation method of 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone |
| CN103649057A (en) * | 2011-07-13 | 2014-03-19 | 巴斯夫欧洲公司 | Fungicidal substituted 2-[2-halogenalkyl-4-(phenoxy)-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds |
| CN105777508A (en) * | 2014-12-22 | 2016-07-20 | 上海泰禾国际贸易有限公司 | Synthesis method of 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone |
| CN105829274A (en) * | 2013-12-18 | 2016-08-03 | 巴斯夫农业公司 | Process for the Preparation of Substituted Phenoxyphenyl Ketones |
| CN106883147A (en) * | 2017-02-13 | 2017-06-23 | 浙江工业大学 | A kind of preparation method of phenyl-pentafluoride formonitrile HCN |
-
2020
- 2020-11-25 CN CN202011345578.2A patent/CN114539041B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1552696A (en) * | 2003-05-30 | 2004-12-08 | 中国科学院大连化学物理研究所 | Synthesis of p-cyanoacetophenone by direct catalyst selective oxidation |
| CN101786948A (en) * | 2010-01-25 | 2010-07-28 | 江苏省农用激素工程技术研究中心有限公司 | Method for preparing 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone |
| CN103649057A (en) * | 2011-07-13 | 2014-03-19 | 巴斯夫欧洲公司 | Fungicidal substituted 2-[2-halogenalkyl-4-(phenoxy)-phenyl]-1-[1,2,4]triazol-1-yl-ethanol compounds |
| CN102675074A (en) * | 2012-05-25 | 2012-09-19 | 江西华士药业有限公司 | Preparation method of cyproconazole key intermediate 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone |
| CN103044230A (en) * | 2012-12-26 | 2013-04-17 | 湖南化工研究院 | Preparation method of 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone |
| CN105829274A (en) * | 2013-12-18 | 2016-08-03 | 巴斯夫农业公司 | Process for the Preparation of Substituted Phenoxyphenyl Ketones |
| CN105777508A (en) * | 2014-12-22 | 2016-07-20 | 上海泰禾国际贸易有限公司 | Synthesis method of 1-(4-chlorphenyl)-2-cyclopropyl-1-acetone |
| CN106883147A (en) * | 2017-02-13 | 2017-06-23 | 浙江工业大学 | A kind of preparation method of phenyl-pentafluoride formonitrile HCN |
Non-Patent Citations (1)
| Title |
|---|
| I. A. Os’kina等.Kinetics of the Reaction of 1-R-3,5-Dinitrobenzenes with 4-Chlorophenol in DMF in the Presence of Potassium Carbonate.Russian Journal of Organic Chemistry.2010,第第46卷卷(第第12期期),第1817–1821页. * |
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