CN103641782A - Pyrazol acylhydrazone compounds and application thereof - Google Patents
Pyrazol acylhydrazone compounds and application thereof Download PDFInfo
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- CN103641782A CN103641782A CN201310731345.XA CN201310731345A CN103641782A CN 103641782 A CN103641782 A CN 103641782A CN 201310731345 A CN201310731345 A CN 201310731345A CN 103641782 A CN103641782 A CN 103641782A
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- acylhydrazone
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 32
- WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 title abstract 2
- 241000607479 Yersinia pestis Species 0.000 claims abstract description 8
- 150000003217 pyrazoles Chemical class 0.000 claims description 7
- 241000238631 Hexapoda Species 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 239000004480 active ingredient Substances 0.000 claims description 3
- 230000000749 insecticidal effect Effects 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000002917 insecticide Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 241000500437 Plutella xylostella Species 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- MOTPCOWWOZSEHC-UHFFFAOYSA-N 5-chloro-1h-pyrazole-3-carboxylic acid Chemical compound OC(=O)C=1C=C(Cl)NN=1 MOTPCOWWOZSEHC-UHFFFAOYSA-N 0.000 description 5
- 238000009835 boiling Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- -1 Pyrazole acyl chloride Chemical class 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000000975 bioactive effect Effects 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- JCOHRMJIHAFFBC-UHFFFAOYSA-N ethyl 5-tert-butyl-2-methylpyrazole-3-carboxylate Chemical compound CCOC(=O)C1=CC(C(C)(C)C)=NN1C JCOHRMJIHAFFBC-UHFFFAOYSA-N 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 3
- 239000005457 ice water Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- WPALTCMYPARVNV-UHFFFAOYSA-N tolfenpyrad Chemical compound CCC1=NN(C)C(C(=O)NCC=2C=CC(OC=3C=CC(C)=CC=3)=CC=2)=C1Cl WPALTCMYPARVNV-UHFFFAOYSA-N 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- FKLJPTJMIBLJAV-UHFFFAOYSA-N Compound IV Chemical compound O1N=C(C)C=C1CCCCCCCOC1=CC=C(C=2OCCN=2)C=C1 FKLJPTJMIBLJAV-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- WYACBZDAHNBPPB-UHFFFAOYSA-N diethyl oxalate Chemical compound CCOC(=O)C(=O)OCC WYACBZDAHNBPPB-UHFFFAOYSA-N 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- NLFBCYMMUAKCPC-KQQUZDAGSA-N ethyl (e)-3-[3-amino-2-cyano-1-[(e)-3-ethoxy-3-oxoprop-1-enyl]sulfanyl-3-oxoprop-1-enyl]sulfanylprop-2-enoate Chemical compound CCOC(=O)\C=C\SC(=C(C#N)C(N)=O)S\C=C\C(=O)OCC NLFBCYMMUAKCPC-KQQUZDAGSA-N 0.000 description 2
- RCXMILPYEKVQLB-UHFFFAOYSA-N ethyl 5-tert-butyl-1h-pyrazole-3-carboxylate Chemical compound CCOC(=O)C=1C=C(C(C)(C)C)NN=1 RCXMILPYEKVQLB-UHFFFAOYSA-N 0.000 description 2
- GFAUNYMRSKVDJL-UHFFFAOYSA-N formyl chloride Chemical compound ClC=O GFAUNYMRSKVDJL-UHFFFAOYSA-N 0.000 description 2
- 150000007857 hydrazones Chemical class 0.000 description 2
- 230000010534 mechanism of action Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 description 2
- 0 CC(C)(C)c1n[n](*)c(*)c1 Chemical compound CC(C)(C)c1n[n](*)c(*)c1 0.000 description 1
- UZWLNLVFIVHIID-UHFFFAOYSA-N CC(C)(C)c1n[n](C)c(C(Cl)=O)c1Cl Chemical compound CC(C)(C)c1n[n](C)c(C(Cl)=O)c1Cl UZWLNLVFIVHIID-UHFFFAOYSA-N 0.000 description 1
- PWNMMQXAXFGQSW-UHFFFAOYSA-N CC(C)(C)c1n[n](C)c(C(O)=O)c1Cl Chemical compound CC(C)(C)c1n[n](C)c(C(O)=O)c1Cl PWNMMQXAXFGQSW-UHFFFAOYSA-N 0.000 description 1
- 241001414720 Cicadellidae Species 0.000 description 1
- 239000005760 Difenoconazole Substances 0.000 description 1
- 240000007817 Olea europaea Species 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 244000269722 Thea sinensis Species 0.000 description 1
- 241001414989 Thysanoptera Species 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 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 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- JZMJDSHXVKJFKW-UHFFFAOYSA-M methyl sulfate(1-) Chemical compound COS([O-])(=O)=O JZMJDSHXVKJFKW-UHFFFAOYSA-M 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- PJGSXYOJTGTZAV-UHFFFAOYSA-N pinacolone Chemical compound CC(=O)C(C)(C)C PJGSXYOJTGTZAV-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000011272 standard treatment Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000375 suspending agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D231/16—Halogen atoms or nitro radicals
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Dentistry (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Plant Pathology (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
Abstract
The invention discloses pyrazol acylhydrazone compounds with structural formulas shown in a formula I which is shown in the specification. The compounds have insecticidal action and can be used for preventing and treating common agricultural pests.
Description
Technical field the invention belongs to agricultural insecticide field, is specifically related to a kind of pyrazoles acylhydrazone and as the purposes of agricultural insecticide.
Background technology harmful insect harms the crops and causes crop failure and quality to reduce, no matter biotic pesticide or chemical insecticide, and a large amount of frequent uses all easily cause the resistance of insect; Developing new insecticide variety and especially develop the insecticide variety of new mechanism of action, is the effective way of administering pest resistance to insecticide.CN101774951P has reported that formula II compound and control thereof control the purposes of insect pest, and its mechanism of action is different from existing sterilant, can be used for preventing and treating resistanc pest, but this compound is as sterilant not yet commercialization at home; US0053248421A discloses formula III compound, and these compound commodity are called " Tolfenpyrad ", for thrips and tea lesser leafhopper etc., have good prevention effect.But this compou nd synthesis need be used catalysis high-pressure hydrogenation, production security and cost factor cause it to hold at high price, and are difficult to generally promote.In the prior art, as pyrazoles acylhydrazone of the present invention (formula I) and insecticidal activity thereof are not reported.
Summary of the invention the object of this invention is to provide a kind of novel structure, good disinsection effect, pyrazoles acylhydrazone class agricultural insecticide that cost accounting is low.
Technical scheme of the present invention is as follows:
A pyrazoles acylhydrazone, structure is suc as formula shown in I:
Formula I compound of the present invention can be prepared by following reaction:
The chloro-4-(4-chlorophenoxy of 2-) methyl phenyl ketone and hydrazine hydrate back flow reaction in ethanol make compounds Ⅳ; Pyrazole acyl chloride (compound V) be take triethylamine or pyridine and is made the compounds of this invention (formula I) as acid binding agent and compounds Ⅳ at room temperature react 2h.
The compounds of this invention structurally has certain similarity with formula II, formula III compound, but as bioactive molecule, structural nuance all can affect the dredging property of compound in organism and the suitability of being combined with target action site, thereby causes bioactive varying.In the prior art, the transporting of bioactive molecules in harmful organisms and the suitability of being combined with action site are unpredictable, need a large amount of creative works just can know.Evidence, the compounds of this invention has beyond thought insecticidal effect to insect, as to the activity of small cabbage moth far above commercial sterilant " Tolfenpyrad " (formula III compound), therefore, the present invention also comprises that formula I compound is for the purposes of pest control.
Advantage of the present invention and positively effect: hydrazone insecticides commercialization kind is very few at present, and its insecticidal mechanism is different from existing other type sterilant, thereby the compounds of this invention has good application potential and value to control resistanc pest.The compounds of this invention is prepared the chloro-4-(4-chlorophenoxy of raw materials used 2-) methyl phenyl ketone belongs to the intermediate of production " difenoconazole ", and domestic have a plurality of manufacturer production; Pyrazole acyl chloride preparation method is similar to " Tolfenpyrad " (formula III compound) part intermediate, does not have technical problem.Thereby compound of the present invention is formulated new variety as agricultural chemicals, there is the advantages such as low resistance, low cost and technique are simple, also made up the problem of current hydrazone insecticides shortage simultaneously, China's resistant insect is administered and had very positive meaning.
The present invention also comprises that formula I compound is as the insect-killing composition of active ingredient, also comprises the upper acceptable carrier of agricultural in said composition.
The compounds of this invention, when pest control, can be used alone, and also can be used in combination with other active compound, is beneficial to improve the integrated control function of product.
Composition of the present invention can preparation form use, formula I compound is dissolved in or is scattered in carrier or solvent as active ingredient, adds suitable surfactant and makes missible oil, microemulsion, aqueous emulsion or suspension agent etc.
Should be clear and definite, in claim of the present invention institute limited range, can carry out various conversion and change.
Embodiment:
Following synthetic example and the raw result of surveying can be used to further illustrate the present invention, but do not mean that restriction the present invention.
Synthetic example
The preparation of example 1, formula 1 compound
(1) 1,1,1-pivalyl Pyruvic Acid Ethyl ester synthetic
Step: add 150mL dehydrated alcohol in 500mL four-hole boiling flask; nitrogen protection; add in three batches 14.64g(0.64mol) sodium Metal 99.5; in question response liquid, after sodium Metal 99.5 disappearance, ice-water bath cooling continues to stir 20min; to slowly dripping 40.00g(0.46mol in reaction flask) pinacolone and 66.38g(0.46mol) mixed solution of oxalic acid diethyl ester; 1h drips off, and drips off rear continuation reaction 2h, and TLC detects oxalic acid diethyl ester and disappears.Adding 37% concentrated hydrochloric acid adjust pH is 5 left and right, solvent is steamed, and resistates washing suction filtration, filter cake is product 1,1, and 1-pivalyl Pyruvic Acid Ethyl ester obtains 80.63g white solid after oven dry, and productive rate is 88.6%.
(2) the 3-tertiary butyl-5-pyrazole carboxylic acid ethyl ester is synthetic
Step: add 37.47g(0.19mol in 250mL four-hole boiling flask) 1,1,1-pivalyl Pyruvic Acid Ethyl ester, 120mL Glacial acetic acid, ice-water bath temperature control 20-30 ℃, slowly drips the hydrazine hydrate (0.23mol) of 14.05g80%, drips and is warming up to back flow reaction 1h, it is complete that TLC detects raw material reaction, cooling, revolves and steams solvent, and resistates washes with water, suction filtration, obtaining white powder solid 35.19g productive rate is 96.0%.
(3) the 1-methyl-3-tertiary butyl-5-pyrazole carboxylic acid ethyl ester is synthetic
Step: add 26.00g(0.13mol in 250mL four-hole boiling flask) the 3-tertiary butyl-5-pyrazole carboxylic acid ethyl ester, 120mL1,2-ethylene dichloride, under mechanical stirring, slowly splash into 18.39g(0.15mol) methyl-sulfate, in 0.5h, drip off, drip off rear temperature rising reflux reaction 2h, it is complete that TLC detects raw material reaction of disappearance, is down to room temperature.Adding saturated aqueous sodium carbonate adjust pH is 7, reaction solution is placed in separating funnel, branch vibration layer, 30mL saturated common salt water washing for organic layer, separate organic layer and add anhydrous sodium sulfate drying, suction filtration, filtrate evaporate to dryness, obtain the product 1-methyl-3-tertiary butyl-5-pyrazole carboxylic acid ethyl ester 24.24g, productive rate is 87.1%.
(4) the chloro-5-pyrazole carboxylic acid of the 1-methyl-3-tertiary butyl-4-ethyl ester is synthetic
Step: add 27.86g(0.13mol in 250mL four-hole boiling flask) the 1-methyl-3-tertiary butyl-5-pyrazole carboxylic acid ethyl ester, 120mL1,2-ethylene dichloride, slowly drip 37.90g(0.28mol) SULPHURYL CHLORIDE, drip and be warming up to back flow reaction 1h, TLC detects to raw material and disappears, cooling, reaction solution is revolved and steamed except desolventizing and excessive SULPHURYL CHLORIDE, obtain the chloro-5-pyrazole carboxylic acid of the oily product 1-methyl-3-tertiary butyl-4-ethyl ester 30.24g, productive rate is 93.0%.
(5) the chloro-5-pyrazole carboxylic acid of the 1-methyl-3-tertiary butyl-4-is synthetic
Step: add 32.52g(0.13mol in 250mL four-hole bottle) the chloro-5-pyrazole carboxylic acid of the 1-methyl-3-tertiary butyl-4-ethyl ester, 100mL methyl alcohol, adds 14.99g(0.38mol under stirring) 40% aqueous solution that is made into of sodium hydroxide, add and be warming up to 40 ℃, stirring reaction 4h, TLC detects raw material and disappears, and methyl alcohol is revolved to evaporate to dryness, after resistates cooling, add 50mL water, with 37% hydrochloric acid adjust pH, be 3, suction filtration, filter cake 20mL water washing, dry to obtain 23.73g white solid, productive rate is 81.4%.
(6) the chloro-5-pyrazol formyl chloride of the 1-methyl-3-tertiary butyl-4-is synthetic
Step: add dry 37.07g(0.17mol in 500mL four-hole boiling flask) the chloro-5-pyrazole carboxylic acid of the 1-methyl-3-tertiary butyl-4-, 150mL toluene and 5 DMF, under stirring at normal temperature, drip 78.20g(0.66mol) sulfur oxychloride, temperature rising reflux 5h, in reaction process, solution becomes clarification, TLC detects raw material and disappears, and cooling is revolved to steam and removed toluene and excess chlorination sulfoxide, obtain light yellow oily liquid 39.21g, productive rate 97.8%.
(7) intermediate compound IV is synthetic
In the rear flask of step: 250mL tetra-, add 42.16g(0.15mol) ether ketone and 100mL dehydrated alcohol, stir the lower hydrazine hydrate (0.60mol) of 37.47g80% that slowly drips, temperature rising reflux 4h, TLC detects raw material and disappears, cooling, revolves and steams solvent, and resistates adds 50ml water after dropping to room temperature, suction filtration obtains white powder solid 41.25g, and productive rate is 93.2%.
(8) Compound I is synthetic
Step: add 2.95g(10.00mmol in 100mL there-necked flask) intermediate compound IV, 40mL acetonitrile and 2.22g(22.00mmol) triethylamine, ice-water bath cooling continues to stir 10min, drip 5.64g50%(12.00mmol) the chloro-5-pyrazol formyl chloride of the 1-methyl-3-tertiary butyl-4-, add stirring at normal temperature reaction 2h, TLC detection reaction is complete.Add the saturated NaHCO of 10mL
3the aqueous solution, suction filtration, 10mL for filter cake * 2 distilled water wash, dries to obtain white solid 4.69g, and productive rate is 95.1%, fusing point: 141-144 ℃.
Formula I compound proton magnetic data is as follows:
1H?NMR（500MHzDMSO）：δ/ppm1.21（s,3H）,1.35（s,9H）,3.82（s,3H）,6.78-7.56（m,8H）
The raw example of surveying
Example 2, kill small cabbage moth determination of activity
Adopt leaf dipping method.The leaf dipping method that adopts the international resistance council (IRAC) to propose.With the liquid to be measured preparing, with straight peen ophthalmology tweezers dipping olive blade, time 3-5 second, get rid of remaining liquid, each 1,3, each sample, is successively placed in treatment paper by sample flag sequence.After liquid is dry, put into the long straight barrel type pipe of the markd 10cm of tool, 30 of access diamondback moth larvaes in 2 age, build the mouth of pipe with gauze.Sample tubes is placed in standard treatment chamber, and check result after 48h, touches polypide with pulling needle, and motionless person is dead.Calculate mortality ratio (3 repetitions are done in experiment, average).
According to above method, the compounds of this invention I and known compound III are killed to the active parallel comparison (mortality ratio %) of small cabbage moth, the results are shown in Table 1:
Table 1 kills small cabbage moth determination of activity table
Table 1 insecticidal test result shows, compares with compound III, and the compounds of this invention I has more excellent insecticidal effect to small cabbage moth.
Claims (3)
1. a pyrazoles acylhydrazone, structure is suc as formula shown in I:
2. a kind of pyrazoles acylhydrazone according to claim 1 is controlled the purposes of insect pest.
3. an insect-killing composition, containing formula I compound claimed in claim 1 is the upper acceptable carrier of active ingredient and agricultural.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310731345.XA CN103641782B (en) | 2013-12-26 | 2013-12-26 | Pyrazol acylhydrazone compounds and application thereof |
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| CN201310731345.XA CN103641782B (en) | 2013-12-26 | 2013-12-26 | Pyrazol acylhydrazone compounds and application thereof |
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| Publication Number | Publication Date |
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| CN103641782A true CN103641782A (en) | 2014-03-19 |
| CN103641782B CN103641782B (en) | 2015-01-28 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105968092A (en) * | 2016-06-01 | 2016-09-28 | 西安近代化学研究所 | N1-(3-substituted pyrazol-5-formyl)-substituted oxygen alkyl benzene N-hydrazide derivative and application thereof |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105968092A (en) * | 2016-06-01 | 2016-09-28 | 西安近代化学研究所 | N1-(3-substituted pyrazol-5-formyl)-substituted oxygen alkyl benzene N-hydrazide derivative and application thereof |
| CN106083838A (en) * | 2016-06-01 | 2016-11-09 | 西安近代化学研究所 | A kind of 2,5 2 replacement 1,3,4 oxadiazole derivative and application thereof |
| CN106083838B (en) * | 2016-06-01 | 2018-10-12 | 西安近代化学研究所 | A kind of bis- substitution -1,3,4- oxadiazole derivatives of 2,5- and its application |
| CN109422690A (en) * | 2017-08-31 | 2019-03-05 | 浙江省化工研究院有限公司 | A method of preparing 1- alkyl -3- alkyl pyrazole -5- formic acid esters |
| CN111635399A (en) * | 2020-07-01 | 2020-09-08 | 南通大学 | Pyrazole derivative containing thiadiazole heterocyclic unit and preparation method and application thereof |
| WO2022002193A1 (en) * | 2020-07-01 | 2022-01-06 | 南通大学 | Preparation method for and application of pyrazole acylhydrazone containing trifluoromethyl thiadiazole unit |
| CN111635399B (en) * | 2020-07-01 | 2022-05-03 | 南通大学 | Pyrazole derivative containing thiadiazole heterocyclic unit and preparation method and application thereof |
| GB2610789A (en) * | 2020-07-01 | 2023-03-15 | Univ Nantong | Preparation method for and application of pyrazole acylhydrazone containing trifluoromethyl thiadiazole unit |
| GB2610789B (en) * | 2020-07-01 | 2024-09-18 | Univ Nantong | Preparation method for and application of pyrazole acylhydrazone containing trifluoromethyl thiadiazole unit |
| CN113717035A (en) * | 2021-09-13 | 2021-11-30 | 江苏禾本生化有限公司 | Recycling method of difenoconazole waste intermediate |
| CN113717035B (en) * | 2021-09-13 | 2024-03-26 | 江苏禾本生化有限公司 | Recycling method of difenoconazole waste intermediate |
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