CN108440428A - A kind of 1- (1- chlorine cyclopropyl) -2-（1,2,4- triazolyls) ethyl ketone synthetic method - Google Patents
A kind of 1- (1- chlorine cyclopropyl) -2-（1,2,4- triazolyls) ethyl ketone synthetic method Download PDFInfo
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- CN108440428A CN108440428A CN201810440579.1A CN201810440579A CN108440428A CN 108440428 A CN108440428 A CN 108440428A CN 201810440579 A CN201810440579 A CN 201810440579A CN 108440428 A CN108440428 A CN 108440428A
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- ethyl ketone
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- 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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Abstract
The invention discloses a kind of 1 (1 chlorine cyclopropyl) 2（1,2,4 triazolyls) ethyl ketone synthetic method,1,2,4 triazoles,Anhydrous potassium carbonate,1 chlorine, 1 chloracetyl cyclopropane,Tetrahydrofuran,Anhydrous magnesium sulfate,Sodium hydroxide,Ethyl acetate and carbon tetrachloride are primary raw material,Using normal pressure,Nitrogen protection,Water and tetrahydrofuran are as solvent,With 1 chlorine, 1 chloracetyl cyclopropane and 1,2,4 triazoles are raw material,Under the action of nickel cobalt bimetallic catalyst wherein mesosome is obtained through N alkylated reactions,The present invention uses normal pressure,Nitrogen protection,Water and tetrahydrofuran are as solvent,With 1 chlorine, 1 chloracetyl cyclopropane and 1,2,4 triazoles are raw material,Wherein mesosome is obtained through N alkylated reactions improve its yield under the action of nickel cobalt bimetallic catalyst,Shorten the prothioconazoles technological process of production,Reduce energy consumption.
Description
Technical field
The present invention relates to a kind of 1- (1- chlorine cyclopropyl) -2-（1,2,4- triazolyls) ethyl ketone synthetic method, belong to catalysis
Technical field.
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, how to improve 1- (1- chlorine cyclopropyl) -2-
（1,2,4- triazolyls) ethyl ketone synthetic yield tool have very important significance.
Invention content
The purpose of the present invention is to provide a kind of 1- (1- chlorine cyclopropyl) -2-（1,2,4- triazolyl) ethyl ketone, this method exists
It can be catalyzed 1,2,4- triazoles and the chloro- 1- chloracetyls cyclopropane reactions of 1- under optimal conditions, there is higher product yield.
A kind of 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, 7.176g 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；
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 6g（0.06mol) concentrated nitric acid (content about 65%), 30 DEG C of dropping temperature, about 10min is added dropwise, and continues to stir 1h, have white
Color solid is precipitated, and 15 DEG C is cooled to, by white solid (1-（1- chlorine cyclopropyl）-2-(1,2,4-
Triazolyl) 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.
Advantageous effect：The present invention provides 1- (1- chlorine cyclopropyl) -2-（1,2,4- triazolyl) ethyl ketone synthetic method, using normal
Pressure, nitrogen protection, water and tetrahydrofuran are as solvent, and with the chloro- 1- chloracetyls cyclopropane of 1- and 1,2,4- triazoles are raw material,
Under the action of nickel cobalt bimetallic catalyst wherein mesosome is obtained through N- alkylated reactions；The reaction first step is 1,2,4- triazoles
Triazole sylvite is generated with carbonic acid nak response, which is dissolved in water phase, and second step is the chloro- 1- of 1- in the organic phase instilled
Chloracetyl cyclopropane is reacted with the triazole sylvite in water phase, which is SN2Reaction mechanism, nitrogen-atoms in triazole sylvite
On the chloro- 1- chloracetyls cyclopropane of lone pair electrons attack 1- in primary halocarbon atom, chlorine atom leaves away, and generates ammonium salt, and potassium is former
Son transfer is left away produces potassium chloride with chlorine atom, obtains product 1-（1- chlorine cyclopropyl）- 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 (2)
1. a kind of 1- (1- chlorine cyclopropyl) -2-（1,2,4- triazolyl) ethyl ketone synthetic method, it is characterised in that this method includes
Following steps：
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.
2. a kind of 1- (1- chlorine cyclopropyl) -2- according to claim 1（1,2,4- triazolyl) ethyl ketone synthetic method, it is special
Sign is,
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.
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Cited By (1)
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| CN109759099A (en) * | 2019-03-04 | 2019-05-17 | 河南城建学院 | A kind of photochemical catalyst and preparation method thereof, application |
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