CN108479821A - A kind of catalyst and its application for synthesizing prothioconazoles intermediate - Google Patents
A kind of catalyst and its application for synthesizing prothioconazoles intermediate Download PDFInfo
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- CN108479821A CN108479821A CN201810440598.4A CN201810440598A CN108479821A CN 108479821 A CN108479821 A CN 108479821A CN 201810440598 A CN201810440598 A CN 201810440598A CN 108479821 A CN108479821 A CN 108479821A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- 239000000047 product Substances 0.000 claims abstract description 17
- 238000013019 agitation Methods 0.000 claims abstract description 14
- 229910003471 inorganic composite material Inorganic materials 0.000 claims abstract description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 230000004044 response Effects 0.000 claims abstract description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 230000004224 protection Effects 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910021205 NaH2PO2 Inorganic materials 0.000 claims abstract description 4
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical class [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 4
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 4
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 4
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 4
- 210000002268 wool Anatomy 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 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 25
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 claims description 20
- 230000015572 biosynthetic process Effects 0.000 claims description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 16
- 238000003786 synthesis reaction Methods 0.000 claims description 16
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 15
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- 229910052801 chlorine Inorganic materials 0.000 claims description 13
- LVZWSLJZHVFIQJ-UHFFFAOYSA-N Cyclopropane Chemical compound C1CC1 LVZWSLJZHVFIQJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000460 chlorine Substances 0.000 claims description 11
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- 125000001376 1,2,4-triazolyl group Chemical group N1N=C(N=C1)* 0.000 claims description 7
- 239000012043 crude product Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 238000002425 crystallisation Methods 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 238000001556 precipitation Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- SJHPCNCNNSSLPL-CSKARUKUSA-N (4e)-4-(ethoxymethylidene)-2-phenyl-1,3-oxazol-5-one Chemical class O1C(=O)C(=C/OCC)\N=C1C1=CC=CC=C1 SJHPCNCNNSSLPL-CSKARUKUSA-N 0.000 claims description 3
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 claims description 3
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 3
- SEXVNMRDIDKTKW-UHFFFAOYSA-N [N+](=O)(O)[O-].C(C)C(=O)CC Chemical compound [N+](=O)(O)[O-].C(C)C(=O)CC SEXVNMRDIDKTKW-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 238000013517 stratification Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000008569 process Effects 0.000 abstract description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 abstract 4
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 abstract 1
- 239000006227 byproduct Substances 0.000 abstract 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 abstract 1
- 235000011181 potassium carbonates Nutrition 0.000 description 16
- 150000000178 1,2,4-triazoles Chemical class 0.000 description 15
- 235000013495 cobalt Nutrition 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 5
- 201000010099 disease Diseases 0.000 description 5
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- 150000003852 triazoles Chemical class 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000209140 Triticum Species 0.000 description 2
- 235000021307 Triticum Nutrition 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical group COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 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
- 241001530056 Athelia rolfsii Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- DGBIUVCNEOCAAV-UHFFFAOYSA-N CCCCCCCCCCCCCCC[ClH]C1(CC1)Cl Chemical compound CCCCCCCCCCCCCCC[ClH]C1(CC1)Cl DGBIUVCNEOCAAV-UHFFFAOYSA-N 0.000 description 1
- 241000221785 Erysiphales Species 0.000 description 1
- 240000005979 Hordeum vulgare Species 0.000 description 1
- 235000007340 Hordeum vulgare Nutrition 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 206010027146 Melanoderma Diseases 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical group [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- XVVLAOSRANDVDB-UHFFFAOYSA-N formic acid Chemical group OC=O.OC=O XVVLAOSRANDVDB-UHFFFAOYSA-N 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/28—Phosphorising
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
- C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
- C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of catalyst and its applications for synthesizing prothioconazoles intermediate, by nickel acetylacetonate, four water cobalt acetates, polyvinylpyrrolidone, terephthalic acid (TPA) is put into the N of water sum, in N dimethyl formamide mixed solutions, magnetic agitation, it transfers the solution into the dynamic response kettle equipped with polytetrafluoroethyllining lining, dynamic response kettle is sealed, the organic inorganic composite materials of nickel cobalt are obtained by the reaction, wait for that reaction is cooled to room temperature, by product deionized water with N, N dimethyl formamide cross washings, it is dried in baking oven for 24 hours, the yellowish powdered organic inorganic composite materials of nickel cobalt are obtained with NaH2PO2The two in tube furnace is placed on together to separate using silica wool, under Ar protections, the nanoscale nickel cobalt bimetallic catalyst by the product utilization deionized water obtained after phosphatization with being dried to obtain black in absolute ethyl alcohol cross washing baking oven.Nickel cobalt bimetallic catalyst of the present invention increases substantially prothioconazoles intermediate yield, the technological process of production, reduces energy consumption.
Description
Technical field
The present invention relates to a kind of catalyst and its applications for synthesizing prothioconazoles intermediate, belong to catalysis technique neck
Domain.
Background technology
Prothioconazoles are worked by inhibiting the biosynthesis of mycosterol, have very extensive fungicidal spectrum.Rosickyite bacterium
Azoles interior suction is good, has excellent protection, treats and root out activity, the lasting period is long.Prothioconazoles not only have crop good
Safety, and preventing disease theraping effect is good, and volume increase is apparent.Compared with other triazole bactericidal agents, prothioconazoles more wide spectrum.Almost
To all wheat diseases have good control effect, as on wheat and barley powdery mildew, banded sclerotial blight, droop, leaf spot,
Rust, sclerotiniose, net blotch, moire disease etc.;The soil-borne disease of rape and peanut, such as sclerotiniose and main leaf can also be prevented
Face disease, such as gray mold, black spot, brown spot, balck shank, sclerotiniose and rust.But current prothioconazoles are produced
There is also many deficiencies from the point of view of method：Such as production process route complexity, the production cycle is long, causes producing cost excessively high；It prepared
Impurity is introduced in journey, and quality is caused to decline；If carrying out secondary crystallization, and operating cost is caused to increase, yield declines, and cost increases
1- (1- chlorine cyclopropyl) -2-（1,2,4- triazolyl) ethyl ketone be it is a kind of synthesis prothioconazoles important intermediate, improve its yield,
It is of great significance for shortening the prothioconazoles technological process of production, reducing energy consumption, finds a kind of raising 1- (1- chlorine cyclopropyl)-
2-（1,2,4- triazolyls) ethyl ketone synthetic yield catalyst and synthesis condition have very important significance.
Invention content
The purpose of the present invention is to provide a kind of catalyst and its application for synthesizing prothioconazoles intermediate, catalyst
Prothioconazoles intermediate 1,2,4- triazoles can be catalyzed well with optimal conditions and the chloro- 1- chloracetyls cyclopropane of 1- is anti-
It answers, there is higher product yield.
A kind of catalyst for synthesizing prothioconazoles intermediate, the catalyst are nickel cobalt bimetallic catalyst.
The nickel cobalt bimetallic catalyst preparation method is as follows：
Step 1, by 100mg nickel acetylacetonates, tetra- water cobalt acetates of 100mg, 400mg polyvinylpyrrolidones, 50mg terephthaldehydes
Acid is put into 80ml water and the N of 160ml, N dimethyl formamide mixed solution, magnetic agitation 20min, is uniformly mixed；
Above-mentioned solution is transferred in the dynamic response kettle equipped with polytetrafluoroethyllining lining by step 2, and dynamic response kettle is sealed
It is good, 6h is reacted at a temperature of 150 DEG C, obtains the organic inorganic composite materials of nickel cobalt, waits for that reaction is cooled to room temperature, product is spent
Ionized water with N, N dimethyl formamides cross washing 3 times, in 7400r/min centrifugations, 60 DEG C of baking ovens it is dry for 24 hours, obtain micro- Huang
The organic inorganic composite materials of powdered nickel cobalt of color；
Step 3, by the organic inorganic composite materials of the nickel cobalt obtained after drying with NaH2PO2It is placed in tube furnace together, with
The mass ratio of the organic inorganic composite materials of nickel cobalt is 5:1, the two is separated using silica wool, under Ar protections, from 20 DEG C of room temperature
Lower heating, heating rate are 2 DEG C/min, and reacting 3h at 350 DEG C just obtains product；
Step 4 centrifuges the product utilization deionized water obtained after phosphatization with absolute ethyl alcohol cross washing 5 times, 8500r/min
The nanoscale nickel cobalt bimetallic catalyst of black is dried to obtain in 6min, 60 DEG C of baking ovens.
Application of the catalyst in synthesis prothioconazoles intermediate.
The prothioconazoles intermediate is 1- (1- chlorine cyclopropyl) -2-（1,2,4- triazolyls) ethyl ketone.
Specific synthesis application is as follows：
Water, 1,2,4- triazole, Anhydrous potassium carbonate and nickel cobalt bimetallic catalyst, magnetic force is added in step 1 in three-necked flask
Stirring is heated to 65 DEG C, reacts 1h；
Step 2, at such a temperature, the mixed solution of the chloro- 1- chloracetyls cyclopropane of 1- and tetrahydrofuran is slowly dropped into, about
0.5h is added dropwise, and stops after the reaction was continued 4.5h；
Step 3 is down to room temperature after completion of the reaction, and stratification separates oil reservoir, with tetrahydrofuran aqueous layer extracted, merges organic phase,
Anhydrous magnesium sulfate is dried, and filtering is evaporated off solvent, obtains brown oil liquid crude product；
Step 4 puts above-mentioned crude product to carbon tetrachloride in 250mL three-necked flasks, is added, and stirring is added dropwise dense to being completely dissolved
Nitric acid, 30 DEG C of dropping temperature, about 10min is added dropwise, and continues to stir 1h, has white solid precipitation, be cooled to 15 DEG C, will be white
Solid (1-（1- chlorine cyclopropyl）- 2- (1,2,4- triazolyls) ethyl ketone nitrate) filtering；
Above-mentioned oxazolone salt is added in the three-necked flask containing ethyl acetate by step 5, under stiring, 30% sodium hydroxide is added dropwise
Weak solution adjusts pH=7, and the reaction was continued at 30 DEG C half an hour；
Step 6, standing, layering, organic solvent is spin-dried for, and residue is poured out while hot, and rapid crystallization, drying obtain after purification
1-（1- chlorine cyclopropyl）- 2- (1,2,4- triazolyls) ethyl ketone solid.
Advantageous effect：Catalyst can be catalyzed prothioconazoles intermediate 1,2,4- triazoles well with optimal conditions and 1- is chloro-
1- chloracetyl cyclopropane reacts, and has higher product yield.
Its reaction condition is to use normal pressure, nitrogen protection, water and tetrahydrofuran as solvent, with the chloro- 1- chloracetyls of 1-
Cyclopropane and 1,2,4- triazoles are raw material, are obtained among it through N- alkylated reactions under the action of nickel cobalt bimetallic catalyst
Body；It is that 1,2,4- triazoles generate triazole sylvite with carbonic acid nak response to react the first step, which is dissolved in water phase, second
Step is that the chloro- 1- chloracetyls cyclopropane of 1- in the organic phase instilled is reacted with the triazole sylvite in water phase, which is SN2
Reaction mechanism, the primary halocarbon in the chloro- 1- chloracetyls cyclopropane of lone pair electrons attack 1- in triazole sylvite on nitrogen-atoms are former
Son, chlorine atom are left away, and ammonium salt is generated, and potassium atom transfer is left away produces potassium chloride with chlorine atom, obtains product 1-（1- chlorine ring third
Base）- 2- (1,2,4- triazolyls) ethyl ketone.
Specific implementation mode
Embodiment 1
1- (1- chlorine cyclopropyl) -2-（1,2,4- triazolyl) ethyl ketone synthetic method, this approach includes the following steps：
20mL water, 1.104g 1,2,4- triazoles, 7.776g Anhydrous potassium carbonates and 2g nickel cobalts is added in step 1 in three-necked flask
Bimetallic catalyst, magnetic agitation are heated to 65 DEG C, react 1h；
Step 2, at such a temperature, the mixed solution of the chloro- 1- chloracetyls cyclopropane of 7.65g 1- and 20mL tetrahydrofurans is delayed
Slow to instill, about 0.5h is added dropwise, and stops after the reaction was continued 4.5h；
Step 3 is down to room temperature after completion of the reaction, and stratification separates oil reservoir, with tetrahydrofuran aqueous layer extracted, merges organic phase,
Anhydrous magnesium sulfate is dried, and filtering is evaporated off solvent, obtains brown oil liquid crude product；
Step 4 puts above-mentioned crude product to 100mL carbon tetrachloride in 250mL three-necked flasks, is added, and stirring is dripped to being completely dissolved
Add the nitric acid of 6ml concentration 65%, 30 DEG C of dropping temperature, about 10min is added dropwise, and continues to stir 1h, there is white solid precipitation, cold
But to 15 DEG C, by white solid (1-（1- chlorine cyclopropyl）- 2- (1,2,4- triazolyls) ethyl ketone nitrate) filtering；
Above-mentioned oxazolone salt is added in the three-necked flask containing 80mL ethyl acetate by step 5, under stiring, 30% hydrogen-oxygen is added dropwise
Change sodium weak solution and adjust pH=7, the reaction was continued at 30 DEG C half an hour；
Step 6, standing, layering, organic solvent is spin-dried for, and residue is poured out while hot, and rapid crystallization, drying obtain after purification
1-（1- chlorine cyclopropyl）- 2- (1,2,4- triazolyls) ethyl ketone solid.
The nickel cobalt bimetallic catalyst preparation method is as follows：
Step 1, by 100mg nickel acetylacetonates, tetra- water cobalt acetates of 100mg, 400mg polyvinylpyrrolidones, 50mg terephthaldehydes
Acid is put into 80ml water and the N of 160ml, N dimethyl formamide mixed solution, magnetic agitation 20min, is uniformly mixed；
Above-mentioned solution is transferred in the dynamic response kettle equipped with polytetrafluoroethyllining lining by step 2, and dynamic response kettle is sealed
It is good, 6h is reacted at a temperature of 150 DEG C, obtains the organic inorganic composite materials of nickel cobalt, waits for that reaction is cooled to room temperature, product is spent
Ionized water with N, N dimethyl formamides cross washing 3 times, in 7400r/min centrifugations, 60 DEG C of baking ovens it is dry for 24 hours, obtain micro- Huang
The organic inorganic composite materials of powdered nickel cobalt of color；
Step 3, by the organic inorganic composite materials of the nickel cobalt obtained after drying with NaH2PO2It is placed in tube furnace together, with
The mass ratio of the organic inorganic composite materials of nickel cobalt is 5:1, the two is separated using silica wool, under Ar protections, from 20 DEG C of room temperature
Lower heating, heating rate are 2 DEG C/min, and reacting 3h at 350 DEG C just obtains product；
Step 4 centrifuges the product utilization deionized water obtained after phosphatization with absolute ethyl alcohol cross washing 5 times, 8500r/min
The nanoscale nickel cobalt bimetallic catalyst of black is dried to obtain in 6min, 60 DEG C of baking ovens.
Embodiment 2
20mL water, 0.552 g, 1,2,4- triazoles, 7.176g Anhydrous potassium carbonates and 2g nickel is added in step 1 in three-necked flask
Cobalt dual-metal catalyst, magnetic agitation are heated to 65 DEG C, react 1h；Remaining step is the same as embodiment 1.
Embodiment 3
20mL water, 0.276 g, 1,2,4- triazoles, 7.176g Anhydrous potassium carbonates and 2g nickel is added in step 1 in three-necked flask
Cobalt dual-metal catalyst, magnetic agitation are heated to 65 DEG C, react 1h；Remaining step is the same as embodiment 1.
Embodiment 4
20mL water, 2.208 g, 1,2,4- triazoles, 7.176g Anhydrous potassium carbonates and 2g nickel is added in step 1 in three-necked flask
Cobalt dual-metal catalyst, magnetic agitation are heated to 65 DEG C, react 1h；Remaining step is the same as embodiment 1.
Embodiment 5
20mL water, 4.416 g, 1,2,4- triazoles, 7.176g Anhydrous potassium carbonates and 2g nickel is added in step 1 in three-necked flask
Cobalt dual-metal catalyst, magnetic agitation are heated to 65 DEG C, react 1h；Remaining step is the same as embodiment 1.
Embodiment 6
20mL water, 6.624g 1,2,4- triazoles, 7.176g Anhydrous potassium carbonates and 2g nickel cobalts is added in step 1 in three-necked flask
Bimetallic catalyst, magnetic agitation are heated to 65 DEG C, react 1h；Remaining step is the same as embodiment 1.
Embodiment 7
20mL water, 1.104g 1,2,4- triazoles, 3.588 g Anhydrous potassium carbonates and 2g nickel is added in step 1 in three-necked flask
Cobalt dual-metal catalyst, magnetic agitation are heated to 65 DEG C, react 1h；Remaining step is the same as embodiment 1.
Embodiment 8
20mL water, 1.104g 1,2,4- triazoles, 1.196 g Anhydrous potassium carbonates and 2g nickel is added in step 1 in three-necked flask
Cobalt dual-metal catalyst, magnetic agitation are heated to 65 DEG C, react 1h；Remaining step is the same as embodiment 1.
Embodiment 9
20mL water, 1.104g 1,2,4- triazoles, 9.568 g Anhydrous potassium carbonates and 2g nickel is added in step 1 in three-necked flask
Cobalt dual-metal catalyst, magnetic agitation are heated to 65 DEG C, react 1h；Remaining step is the same as embodiment 1.
Embodiment 10
20mL water, 1.104g 1,2,4- triazoles, 15.95 g Anhydrous potassium carbonates and 2g nickel is added in step 1 in three-necked flask
Cobalt dual-metal catalyst, magnetic agitation are heated to 65 DEG C, react 1h；Remaining step is the same as embodiment 1.
Reference examples 1
It is with 1 difference of embodiment：In the synthesis step 1 of intermediate, Anhydrous potassium carbonate, remaining step and implementation be not added
Example 1 is identical.
Reference examples 2
It is with 1 difference of embodiment：In the synthesis step 1 of intermediate, cobalt nickel bimetal catalyst, remaining step are not added
It is identical with embodiment 1.
Reference examples 3
It is with 1 difference of embodiment：In the synthesis step 2 of intermediate, by the chloro- 1- chloracetyls cyclopropane of 3.83g 1- and
The mixed solution of 20mL tetrahydrofurans is slowly dropped into, remaining step is identical with embodiment 1.
Reference examples 4
It is with 1 difference of embodiment：In the synthesis step 2 of intermediate, by the chloro- 1- chloracetyls cyclopropane of 1.91g 1- and
The mixed solution of 20mL tetrahydrofurans is slowly dropped into, remaining step is identical with embodiment 1.
Reference examples 5
It is with 1 difference of embodiment：In the synthesis step 4 of intermediate, concentrated nitric acid is not added, remaining step and embodiment 1
It is identical.
Reference examples 6
It is with 1 difference of embodiment：In the synthesis step 4 of intermediate, replaced with the hydrochloric acid of equivalent, remaining step and embodiment
1 is identical.
Reference examples 7
It is with 1 difference of embodiment：In the synthesis step 5 of intermediate, PH=3.0 are adjusted；Remaining step is complete with embodiment 1
It is identical.
Reference examples 8
It is with 1 difference of embodiment：In the synthesis step 5 of intermediate, PH=10.0 are adjusted；Remaining step is complete with embodiment 1
It is identical.
Reference examples 9
It is with 1 difference of embodiment：In the synthesis step 5 of intermediate, ethyl acetate is not added, remaining step and embodiment
1 is identical.
Reference examples 10
It is with 1 difference of embodiment：It is constant with formic acid formic acid substituted acetic acid ethyl ester dosage in the synthesis step 5 of intermediate,
Remaining step is identical with embodiment 1.
It is as shown in the table for reaction result under embodiment and reference examples different condition
The experimental results showed that catalyst has catalysis 1,2,4- triazoles and the chloro- 1- chloracetyls cyclopropane synthetic reactions of 1-
Good catalytic effect, in one timing of reaction condition, intermediate yield is higher, and catalytic performance is better, otherwise poorer；1,2,4- tri-
Nitrogen azoles, Anhydrous potassium carbonate mass ratio are 1:7 and 1:When 14,（Embodiment 1,2）Other dispensings are fixed, and synthetic effect is best, with reality
Example 1,2 is applied the difference lies in that embodiment 3 changes to embodiment 10 1,2,4- triazole of primary raw material, Anhydrous potassium carbonate respectively
Dosage and proportioning have the yield of synthetic product different influences；Reference examples 1 to reference examples 2 do not add catalyst and anhydrous
Potassium carbonate, other steps are identical, and product yield is caused to be substantially reduced, and illustrate the receipts of catalyst and Anhydrous potassium carbonate to reaction
Rate influences very big；Reference examples 3 to reference examples 4 reduce the chloro- 1- chloracetyls cyclopropane dosages of 1-, and effect is still bad, illustrates 1-
Its dosage is also critically important as reactant for chloro- 1- chloracetyls cyclopropane；Reference examples 5 to the hydrochloric acid of reference examples 6 replaces concentrated nitric acid,
So that product obtains yield reduction, reaction effect is obviously deteriorated, and illustrates the very big on the precipitation of crude product influence of concentrated nitric acid；Reference examples 7
To reference examples 10 adjust pH value and use methyl formate substituted acetic acid ethyl ester, reactant composition and solution environmental changes, reaction
Variation with obvious effects, product yield be not still high；Therefore using the catalyst of the present invention to 1-（1- chlorine cyclopropyl）-2-(1,2,
4- triazolyls) ethyl ketone synthetic reaction have excellent catalytic effect.
Claims (5)
1. a kind of catalyst for synthesizing prothioconazoles intermediate, which is characterized in that the catalyst is nickel cobalt bimetallic catalytic
Agent.
2. a kind of catalyst for synthesizing prothioconazoles intermediate according to claim 1, which is characterized in that
The nickel cobalt bimetallic catalyst preparation method is as follows：
Step 1, by 100mg nickel acetylacetonates, tetra- water cobalt acetates of 100mg, 400mg polyvinylpyrrolidones, 50mg terephthaldehydes
Acid is put into 80ml water and the N of 160ml, N dimethyl formamide mixed solution, magnetic agitation 20min, is uniformly mixed；
Above-mentioned solution is transferred in the dynamic response kettle equipped with polytetrafluoroethyllining lining by step 2, and dynamic response kettle is sealed
It is good, 6h is reacted at a temperature of 150 DEG C, obtains the organic inorganic composite materials of nickel cobalt, waits for that reaction is cooled to room temperature, product is spent
Ionized water with N, N dimethyl formamides cross washing 3 times, in 7400r/min centrifugations, 60 DEG C of baking ovens it is dry for 24 hours, obtain micro- Huang
The organic inorganic composite materials of powdered nickel cobalt of color；
Step 3, by the organic inorganic composite materials of the nickel cobalt obtained after drying with NaH2PO2It is placed in tube furnace together, with nickel
The mass ratio of the organic inorganic composite materials of cobalt is 5:1, the two is separated using silica wool, under Ar protections, at 20 DEG C of room temperature
Heating, heating rate are 2 DEG C/min, and reacting 3h at 350 DEG C just obtains product；
Step 4 centrifuges the product utilization deionized water obtained after phosphatization with absolute ethyl alcohol cross washing 5 times, 8500r/min
The nanoscale nickel cobalt bimetallic catalyst of black is dried to obtain in 6min, 60 DEG C of baking ovens.
3. catalyst as described in claim 1 is in the application of synthesis prothioconazoles intermediate.
4. application according to claim 3, which is characterized in that the prothioconazoles intermediate is 1- (1- chlorine rings third
Base) -2-（1,2,4- triazolyls) ethyl ketone.
5. application according to claim 4, which is characterized in that specific synthesis application is as follows：
Water, 1,2,4- triazole, Anhydrous potassium carbonate and nickel cobalt bimetallic catalyst, magnetic force is added in step 1 in three-necked flask
Stirring is heated to 65 DEG C, reacts 1h；
Step 2, at such a temperature, the mixed solution of the chloro- 1- chloracetyls cyclopropane of 1- and tetrahydrofuran is slowly dropped into, about
0.5h is added dropwise, and stops after the reaction was continued 4.5h；
Step 3 is down to room temperature after completion of the reaction, and stratification separates oil reservoir, with tetrahydrofuran aqueous layer extracted, merges organic phase,
Anhydrous magnesium sulfate is dried, and filtering is evaporated off solvent, obtains brown oil liquid crude product；
Step 4 puts above-mentioned crude product to carbon tetrachloride in 250mL three-necked flasks, is added, and stirring is added dropwise dense to being completely dissolved
Nitric acid, 30 DEG C of dropping temperature, about 10min is added dropwise, and continues to stir 1h, has white solid precipitation, be cooled to 15 DEG C, will be white
Solid (1-（1- chlorine cyclopropyl）- 2- (1,2,4- triazolyls) ethyl ketone nitrate) filtering；
Above-mentioned oxazolone salt is added in the three-necked flask containing ethyl acetate by step 5, under stiring, 30% sodium hydroxide is added dropwise
Weak solution adjusts pH=7, and the reaction was continued at 30 DEG C half an hour；
Step 6, standing, layering, organic solvent is spin-dried for, and residue is poured out while hot, and rapid crystallization, drying obtain after purification
1-（1- chlorine cyclopropyl）- 2- (1,2,4- triazolyls) ethyl ketone solid.
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