CN105503731B - 1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- methylenes amino-pyrazol type compound and its micro-wave digestion synthetic method and application - Google Patents
1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- methylenes amino-pyrazol type compound and its micro-wave digestion synthetic method and application Download PDFInfo
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- CN105503731B CN105503731B CN201610015077.5A CN201610015077A CN105503731B CN 105503731 B CN105503731 B CN 105503731B CN 201610015077 A CN201610015077 A CN 201610015077A CN 105503731 B CN105503731 B CN 105503731B
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- 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
- C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
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- 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
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- 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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
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- 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
- C07D231/38—Nitrogen atoms
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- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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Abstract
The invention discloses a kind of 1 (2,6 dichloro-4,4 trifluoromethyl) 3 cyano group of phenyl, 5 methylene amino-pyrazol type compound and its micro-wave digestion synthetic method and application.The present invention prepares object using micro-wave digestion synthetic method, and the reaction time is short, and solvent is not volatile in enclosed system, and recoverable, effectively reduces production cost, has the advantages that energy conservation and environmental protection, and easy to operate, and yield is higher.1 (2 be prepared, 6 dichloro-4,4 trifluoromethyls) 3 cyano group of phenyl 5 methylene amino-pyrazol type compound (II) there is good bioactivity, particularly high activity is shown in terms of the prevention of agricultural, gardening, flowers and sanitary insect pest, can be from degraded under sunlight irradiation, it is that a kind of green low-residual has the compound of insecticidal activity, therefore there are very big development and application values.
Description
Technical field
The present invention relates to technical field of organic synthesis, more particularly to a kind of 1- (2,6- dichlor-4-trifluoromethyl) phenyl -3-
Cyano group -5- methylenes amino-pyrazol type compound and its micro-wave digestion synthetic method, further relate to the application of such compound.
Background technology
In recent ten years, heterocyclic compound causes the concern of pesticide circle personage due to its efficient bioactivity, becomes
The hot spot of current pesticide research exploitation.In various heterocycle compounds, there is arylpyrazoles compound extensive biology to live
Property, it is one of primary structure in recent years with insecticidal active compound research.Shown due to arylpyrazoles compound
Efficiently, the diversity of low toxicity and structure, thus there is boundless research and development prospect.Arylpyrazoles pesticide is one
The chloride channel that class is adjusted by γ-aminobutyric acid disturbs the path of chlorion, destroys the activity of pest normal central nervous system,
And cause being overexcited for insect nerves and muscles in the case of sufficient dosage, cause insect to be fainted from fear, dead new type disinsection
Agent.
1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- amino-pyrazols of glycosyl conjugates modification are with plant
Source activity material such as glucose, galactolipin, xylose etc., as homing device, make glycosyl be coupled with pesticide after by homing device
Transfer protein effect conjugates are loaded into plant, and transport to pest and cause harm position through plant phloem, embody
Very strong guidance quality.1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- amino-pyrazols of butylene modification are China's tools
There is the new product of independent intellectual property right, being set to high-toxic pesticide by USDA National agricultural technology center substitutes and promote product.
Due to the introducing of ethylene linkage, molecule can preferably interact with plant metabolites, significantly reduce the toxicity of the product, its is right
Fish low toxicity, production cost is relatively low, this feature opens broader space for it in production application.
Micro-wave digestion is typically referred to using the digestion solution in microwave heating closed vessel and sample so as in high temperature pressurised bar
Make various samples rapidly-soluble wet digesting under part.Closed container reacts and microwave heats the two features, determines that its is complete
Entirely, quickly, the advantages of low latitude is white.1- (the chloro- 4- tri- of 2,6- bis- that the present invention is prepared using micro-wave digestion and catalyst collective effect
Methyl fluoride) phenyl -3- cyano group -5- methylene amino-pyrazol type compounds (II), synthesis material cost is relatively low, and the reaction time is short, molten
Agent is not volatile in enclosed system, and recoverable, significantly reduces production cost, has the advantages that energy conservation and environmental protection, and
And it is easy to operate, yield is higher.1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- methylene amino pyrroles being prepared
Azoles type compound (II) has good bioactivity, the table particularly in terms of the prevention of agricultural, gardening, flowers and sanitary insect pest
Reveal high activity, therefore there are very big development and application values.
The content of the invention
Based on considerations above, applicant's design has synthesized a series of 1- (2,6- dichlor-4-trifluoromethyl) phenyl -3- cyanogen
Base -5- methylenes amino-pyrazol type compound (II) type insecticide.By a variety of imido for introducing the modifications such as alkyl, aryl, heterocycle
Base key, makes metabolite of the molecule preferably with plant interact, drops low molecular toxicity, extend this insecticides and partly decline
Phase；By introducing imino group key, play the guiding role as glycosyl, make imino group and pesticide be coupled after by being oriented to base
Conjugates are loaded into plant by the transfer protein effect of group, and are transported to pest and caused harm position through plant phloem, are allowed to
As the insecticide of the environment-friendly high-efficiency with guide function.Since the compound (II) of carbon-to-nitrogen double bon modification can be irradiated in sunlight
Under can slowly voluntarily photodissociation so that 1- (2,6- dichlor-4-trifluoromethyl) phenyl -3- cyano group -5- methylene amino-pyrazol types
Compound (II) type insecticide spraying for a period of time after can the slow photodissociation under natural environment, catabolite environmental sound, is one
The insecticide of the green low-residual of kind.1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- methylene amino-pyrazol type chemical combination
Thing insecticide has in prevention Orthoptera, Thysanoptera, Homoptera, Heteroptera, Lepidoptera, coleoptera, Hymenoptera, Diptera class pest
Application well, has very big development and application values in agricultural, gardening, flowers and health etc..
Based on considerations above, of the invention three goals of the invention are：
First, a kind of 1- (2,6- dichlor-4-trifluoromethyl) phenyl -3- cyano group -5- methylene amino-pyrazol type compounds, the change
Shown in the structural formula of compound such as general formula (II)：
In general formula (II), R1Any one in following group：- H ,-X (X represents Cl, Br or I),Wherein n=0,1,2 or 3；
Preferably, the R1For-H ,-Br,
Optimal, the R1For
The compoundAny one in following a few class compounds：Chain aldoketones, aromatic aldehyde
Ketone, aldoketones containing heterocycle；
Specifically, the compoundAny one in following compound：
FormaldehydeAcetaldehydePropionic aldehydeN-butanalIsobutylaldehydeThird
Ketone2- butanone2 pentanonePropioneBenzaldehydeP-methoxybenzal-dehydeParanitrobenzaldehydeSalicylaldhyde4-Fluorobenzaldehyde2,3 dichloro benzaldehydeThe fluoro- 4- bromobenzaldehydes of 2-2,5- difluorobenzaldehydes2,6- dimethylbenzaldehydesThe bromo- 4- hydroxy benzaldehydes of 3-3,5- dimethylbenzaldehydes2,4,6- trifluro benzaldehydes3,5- dibromine-4-hydroxy benzaldehydesTri- hydroxyls of 2,3,4-
Benzaldehyde2- hydroxyl -3,5- dichlorobenzaldehydes2,4,5- trimethoxybenzaldehyde1- naphthaldehydes2- hydroxyl-1-naphthalene Formaldehydes1- methoxy-2-naphthaldehydes9- anthraldehydes9- formaldehydesAcetophenone2- bromobenzene second
Ketone3- methoxyacetophenones3,4- dichloroacetophenonesThe fluoro- 1- naphthalenes second of 4-
Ketone2 furan carboxyaldehyde5- methyl -2 furan carboxyaldehyde2- pyrrole aldehydes3- pyrrole aldehydes2 thiophene carboxaldehydeThe bromo- thiophenecarboxaldehydes of 5-
2- pyridine carboxaldehydesThe bromo- 3- pyridine carboxaldehydes of 2-The chloro- 3- pyridine carboxaldehydes of 2,6- bis-
3- quinoline aldehydes3- indolecarboxaldehydes3- benzofuranones
Preferably, the compoundAny one in following compound：
Acetaldehyde2- butanoneBenzaldehydeP-methoxybenzal-dehydeO-hydroxy
Formaldehyde4-FluorobenzaldehydeAcetophenone2- bromoacetophenones
2 furan carboxyaldehyde3- benzofuranones
2nd, second object of the present invention is that providing one kind is easy to efficient preparation, energy conservation and environmental protection, production cost relatively
Low 1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- methylene amino-pyrazol types compound (general formula (II) shownization
Compound) synthetic method.
A kind of synthetic method of structural formula compound as shown in general formula (II)：By 1- (2,6- dichlor-4-trifluoromethyls) benzene
Base -3- cyano group -5- amino-pyrazol type compounds and compoundIn organic solvent through micro-wave digestion and catalyst
Compound shown in general formula (II) is prepared in synergistic effect；
The general structure of 1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- amino-pyrazol type compounds is such as
Shown in formula (I)：
Synthetic route is as follows：
Wherein, R1, compoundDefinition see above the description of mutual-through type (II)；
The organic solvent is toluene, dimethylbenzene, mesitylene, chlorobenzene, bromobenzene, N,N-dimethylformamide or diformazan are sub-
Sulfone.
Preferably, the organic solvent is toluene.
The catalyst is molecular sieve and acid, wherein molecular sieve model 3A types, 4A types, 5A types, and acid is p-methyl benzenesulfonic acid.
Preferably, the catalyst is p-methyl benzenesulfonic acid and 4A type molecular sieves.
Preferably, 1- (2, the 6- dichlor-4-trifluoromethyl) phenyl -3- cyano group -5- amino-pyrazol types compound,The molar ratio of p-methyl benzenesulfonic acid is respectively 1.2：1：0.001,1- (2, the 6- bis- chloro- 4- fluoroforms per 12mmol
Base) phenyl -3- cyano group -5- amino-pyrazol types compound addition 2g4A type molecular sieves.
Preferably, the microwave power is 75~225W, and microwave digestion time is 45~60min.
Preferably, the preparation carries out under agitation.
3rd, third object of the present invention be to provide above-mentioned 1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -
Application of the 5- methylenes amino-pyrazol type compound in the medicine for preparing prevention harmful insect.
To realize third object of the present invention, the present invention by 1- (2,6- dichlor-4-trifluoromethyl) phenyl -3- cyano group -
5- methylene amino-pyrazol type compounds are prepared into the formulations of pesticide, for preventing Orthoptera, Thysanoptera, Homoptera, Heteroptera, squama wing
Mesh, coleoptera, Hymenoptera and Diptera class pest, obtain preferable prevention effect.
Preferably, the pest includes, but are not limited to this：
Orthoptera such as blattaria, Thysanoptera such as cotton thrips, rice thrips, melon thrips, Homoptera such as leafhopper, Fei Wind, aphid, different wing
Mesh such as harlequin bug, Lepidoptera such as oriental armyworm, prodenia litura, diamondback moth, beet armyworm, mosquito powder exigua, cabbage caterpillar, sheath
Wing mesh such as rice flatworm, Hymenoptera such as sawfly larva, Diptera such as yellow-fever mosquito, culex.
Compared with prior art, the advantages of the present invention are as follows：
1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- that the present invention is prepared using micro-wave digestion synthetic method is sub-
Methylamino pyrazoles type compound (II), synthesis material cost is relatively low, and the reaction time is short, and solvent is not volatile in enclosed system,
Recoverable, significantly reduces production cost, has the advantages that energy conservation and environmental protection, and easy to operate, and yield is higher.
1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- methylene amino-pyrazol type compounds being prepared
(II) there is good bioactivity, high work is particularly shown in terms of the prevention of agricultural, gardening, flowers and sanitary insect pest
Property, therefore there are very big development and application values.
The present invention is by the 1- being prepared (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- methylene amino-pyrazol types
Compound achieves preferable photolytic efficiency by (xenon lamp) progress light degradation under simulated solar irradiation.
Embodiment
With reference to specific embodiment, the present invention is described in further detail, but these specific embodiments are not with any
Mode limits the scope of the invention.
Raw material used is known compound in following embodiment, is commercially available, or can be with this area
The method synthesis known, molecular sieve are needed with muffle furnace when 300 DEG C of activation 3 are small before use.
Embodiment 1,1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- phenyl methylidene amino -4- trifluoromethyls
The synthesis of sulfinyl pyrazoles ((II) 1)
4.5g1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -4- trifluoromethyls Asia sulphur is added in microwave reactor
Acyl group -5- amino-pyrazols, 1.05g benzaldehydes, 0.2g p-methyl benzenesulfonic acid, the 4A type molecular sieves of 2g, 45mL toluene simultaneously add magneton,
Microwave reactor is opened after good seal and is adjusted to certain power, closes microwave reactor after reacting 1h, after somewhat cooling down while hot
Filtering, collects filtrate, column chromatography for separation (ethyl acetate：Petroleum ether=1：10) 4.4g (II) 1 is obtained.Yield：84%.mp:
160.4-161.6 DEG C, IR (KBr, ν/cm-1):3083(CH2- H), 2258 (- CN), 1624 (pyrazole ring skeletal vibrations), 1575
With 1497 (phenyl ring skeletal vibrations), 1312 (C-F), 818 (aromatic ring C-H)；1H NMR(δ):8.9 (s, 1H, N=C-H),
7.45-7.83(m,7H,Ar—H)；
Embodiment 2,1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- (furans -2- bases) methylene amino -4-
The synthesis of trifluoromethyl sulfinyl pyrazole ((II) 2)
4.5g1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -4- trifluoromethyls Asia sulphur is added in microwave reactor
Acyl group -5- amino-pyrazols, 0.96g2- furturals, 0.2g p-methyl benzenesulfonic acid, the 3A type molecular sieves of 2g, 45mL diformazan benzos add
Enter magneton, microwave reactor is opened after good seal and is adjusted to certain power, microwave reactor is closed after reacting 1h, somewhat cools down
Filter while hot afterwards, collect filtrate, column chromatography for separation (ethyl acetate：Petroleum ether=1：15) 4.21g (II) 2 is obtained.Yield：82%.
mp:140.4-141.4℃.IR(KBr,ν/cm-1):3083(CH2- H), 2251 (- CN), 1618 (pyrazole ring skeletal vibrations),
1567,1499 and 1456 (phenyl ring skeletal vibrations), 1311 (C-F), 818 (aromatic ring C-H)；1H NMR(δ):8.71(s,1H,N
=C-H), 7.70-7.74 (s, 2H, Ar-H), 7.81 (s, 1H, COC-H), 7.22 (s, 1H, OC-CH), 6.62 (s, 1H, OCH-
CH)；
Embodiment 3,1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- (4- methoxyphenyls) methylene amino -
The synthesis of 4- trifluoromethyl sulfinyl pyrazoles ((II) 3)
4.5g1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -4- trifluoromethyls Asia sulphur is added in microwave reactor
Acyl group -5- amino-pyrazols, 1.36g P-methoxybenzal-dehyde, 0.2g p-methyl benzenesulfonic acid, the 5A type molecular sieves of 2g, the equal front threes of 45mL
Benzo adds magneton, and microwave reactor is opened after good seal and is adjusted to certain power, closes microwave reactor after reacting 1h, slightly
It is chilly but after filter while hot, collect filtrate, column chromatography for separation (ethyl acetate：Petroleum ether=1：15) 4.32g (II) 3 is obtained.Yield：
78%.mp:106.6-109.4℃.IR(KBr,ν/cm-1):3080(CH2- H), 2246 (- CN), 1594,1517 and 1477
(phenyl ring skeletal vibration), 1311 (C-F), 822 (aromatic ring C-H)；1H NMR(δ):(8.77 s, 1H, N=C-H), 6.94-7.82
(m,6H,Ar—H),3.88(s,3H,ArOCH3)；
Embodiment 4,1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- (2- hydroxy phenyls) methylene amino -4-
The synthesis of trifluoromethyl sulfinyl pyrazole ((II) 4)
4.5g1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -4- trifluoromethyls Asia sulphur is added in microwave reactor
Acyl group -5- amino-pyrazols, 1.22g salicylaldhydes, 0.2g p-methyl benzenesulfonic acid, the 4A type molecular sieves of 2g, 45mL toluene simultaneously add
Enter magneton, microwave reactor is opened after good seal and is adjusted to certain power, microwave reactor is closed after reacting 1h, somewhat cools down
Filter while hot afterwards, collect filtrate, column chromatography for separation (ethyl acetate：Dichloromethane：Petroleum ether=5：1：7) 4.37g (II) 4 is obtained.
Yield：81%.mp:138.6-139.4℃.IR(KBr,ν/cm-1):3078(CH2- H), 2254 (- CN), 1606 (pyrazole rings
Skeletal vibration), 1565,1506 and 1472 (phenyl ring skeletal vibrations), 1311 (C-F), 818 (aromatic ring C-H)；1H NMR(δ):
10.77 (s, 1H, O-H), 9.18 (s, 1H, N=C-H), 6.91-7.87 (m, 6H, Ar-H)；
Embodiment 5,1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- (4- fluorophenyls) methylene amino -4- three
The synthesis of methyl fluoride sulfinyl pyrazoles ((II) 5)
4.5g1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -4- trifluoromethyls Asia sulphur is added in microwave reactor
Acyl group -5- amino-pyrazols, 1.24g 4-Fluorobenzaldehydes, 0.2g p-methyl benzenesulfonic acid, the 3A type molecular sieves of 2g, 45mL chlorobenzenes simultaneously add
Magneton, microwave reactor is opened after good seal and is adjusted to certain power, microwave reactor is closed after reacting 1h, after somewhat cooling down
Filter while hot, collect filtrate, column chromatography for separation (ethyl acetate：Petroleum ether=1：15) 3.96g (II) 5 is obtained.Yield：73%.mp:
165.2-165.9℃.IR(KBr,ν/cm-1):3086(CH2- H), 2257 (- CN), 1625 (pyrazole ring skeletal vibrations), 1576
With 1495 (phenyl ring skeletal vibrations), 1313 (C-F), 816 (aromatic ring C-H)；1H-NMR(δ):8.92 (s, 1H, N=C-H),
7.13-7.83(m,6H,Ar—H)。
Embodiment 6,1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- methyl methylenes amino-pyrazols ((II) 6)
Synthesis
4.2g1- (2,6- dichlor-4-trifluoromethyl) phenyl -3- cyano group -5- amino-pyrazols are added in microwave reactor,
0.44g acetaldehyde, 0.2g p-methyl benzenesulfonic acid, the 5A type molecular sieves of 2g, 45mL bromobenzenes simultaneously add magneton, and it is anti-that microwave is opened after good seal
Answer device and adjust to certain power, close microwave reactor after reacting 1h, filtered while hot after somewhat cooling down, collect filtrate, column layer
Analysis separation (ethyl acetate：Petroleum ether=1：15) 2.46g (II) 6 is obtained.Yield：71%.Product is tested through fusing point, infrared, nuclear-magnetism H spectrums
Demonstrate,prove as 1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- methyl methylenes amino-pyrazol (II) 6.
Embodiment 7,1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- (2- butyl) imino group -4- bromine pyrazoles
The synthesis of ((II) 7)
The bromo- 5- amino pyrroles of 4.3g1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -4- are added in microwave reactor
Azoles, 0.44g2- butanone, 0.2g p-methyl benzenesulfonic acid, the 4A type molecular sieves of 2g, 45mLN, dinethylformamide simultaneously add magneton,
Microwave reactor is opened after good seal and is adjusted to certain power, closes microwave reactor after reacting 1h, after somewhat cooling down while hot
Filtering, collects filtrate, column chromatography for separation (ethyl acetate：Petroleum ether=1：15) 3.44g (II) 7 is obtained.Yield：76%.Product passes through
Fusing point, infrared, nuclear-magnetism H spectrums are verified as 1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- (2- butyl) imino group -4-
Bromine pyrazoles (II) 7.
Embodiment 8,1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- (1- phenylethyls) imino group -4- first
The synthesis of sulfenyl pyrazoles ((II) 8)
4.5g1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -4- methyl mercapto -5- ammonia is added in microwave reactor
Base pyrazoles, 1.2g acetophenones, 0.2g p-methyl benzenesulfonic acid, the 3A type molecular sieves of 2g, 45mL dimethyl sulfoxides simultaneously add magneton, good seal
Microwave reactor is opened afterwards and is adjusted to certain power, is closed microwave reactor after reacting 1h, is filtered while hot after somewhat cooling down, is received
Collect filtrate, column chromatography for separation (ethyl acetate：Petroleum ether=1：15) 3.7g (II) 8 is obtained.Yield：79%.Product is through fusing point, red
Outside, nuclear-magnetism H spectrums are verified as 1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- (1- phenylethyls) imino group -4- first
Sulfenyl pyrazoles (II) 8.
Embodiment 9,1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- (1- o-bromophenyls ethyl) methylene ammonia
The synthesis of base -4- cyano group sulfinyls pyrazoles ((II) 9)
4.5g1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -4- cyano group sulfenyls are added in microwave reactor
Base -5- amino-pyrazols, 2.01g2- bromoacetophenones, 0.2g p-methyl benzenesulfonic acid, the 5A type molecular sieves of 2g, 45mL toluene simultaneously add
Magneton, microwave reactor is opened after good seal and is adjusted to certain power, microwave reactor is closed after reacting 1h, after somewhat cooling down
Filter while hot, collect filtrate, column chromatography for separation (ethyl acetate：Petroleum ether=1：15) 3.95g (II) 9 is obtained.Yield：69%.Production
Thing is verified as 1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- (1- o-bromophenyl second through fusing point, infrared, nuclear-magnetism H spectrums
Base) imino group -4- cyano group sulfinyls pyrazoles (II) 9.
Embodiment 10,1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- (3- benzofuranyls) imino group -
The synthesis of 4- ethylsulfinyls pyrazoles ((II) 10)
4.5g1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -4- ethyl sulfenyls are added in microwave reactor
Base -5- amino-pyrazols, 1.34g3- benzofuranones, 0.2g p-methyl benzenesulfonic acid, the 4A type molecular sieves of 2g, 45mL toluene simultaneously add
Magneton, microwave reactor is opened after good seal and is adjusted to certain power, microwave reactor is closed after reacting 1h, after somewhat cooling down
Filter while hot, collect filtrate, column chromatography for separation (ethyl acetate：Petroleum ether=1：15) 3.64g (II) 10 is obtained.Yield：71%.Production
Thing is verified as 1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- (3- benzofurans through fusing point, infrared, nuclear-magnetism H spectrums
Base) imino group -4- ethylsulfinyls pyrazoles (II) 10.
Comparative example, 1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- phenyl methylidene amino -4- trifluoromethyls are sub-
The synthesis of sulfonyl pyrazole ((II) 1)
Separately or concurrently change 1 catalyst of embodiment, reaction time and mode of heating, other are same as Example 1, prepare
1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- phenyl methylidene amino -4- trifluoromethyl sulfinyl pyrazoles ((II)
1) result for, preparing result and embodiment 1 is listed in the table below in 1 at the same time：
(II) 1 synthesis and its yield under 1. different condition of table
From comparative example 1~4 as can be seen that in the case where common oil bath is heated to reflux, adds cation exchange resin and react 5 days,
Yield still is below 10%, adds acetic acid, sulfuric acid and sieve peg-raking catalyst, under microwave heating condition, reacts also base
This does not occur, and when selecting p-methyl benzenesulfonic acid and sieve peg-raking catalyst, yield is increased dramatically.It is aided with microwave heating again
In the case of, not only yield is further lifted, but also the reaction time can be greatly reduced (it is small that the reaction time by 24h is reduced to 1
When, 84%) yield is brought up to by 40%.
Other experiments of inventor show, the p-methyl benzenesulfonic acid in p-methyl benzenesulfonic acid and molecular sieve is changed and makees other acid such as salt
Acid, acetic acid, sulfuric acid or without using molecular sieve, the compound of embodiment 2~5 and other by the present invention formula (I) formula
(II) reaction, yield can all be greatly reduced, and microwave is changed and makees the mode of heatings such as oil bath, and yield can be reduced further.Illustrate this
Not only there is synergistic effect, but also p-methyl benzenesulfonic acid and molecular sieve catalyst between p-methyl benzenesulfonic acid and molecular sieve catalyst in invention
There is also synergistic effect between being reacted with micro-wave digestion.
Embodiment 11,1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- methylene amino-pyrazol type compounds
(II) preparation of suspending agent
The formulations of pesticide prepared by the present embodiment are suspending agent, and alleged below " gross mass " refers to " prepared suspending agent
Gross mass ".
The 10 parts of surfactant for accounting for gross mass 5% naphthalenesulfonic acid-formaldehyde condensates are first diluted in 10 parts respectively and account for total matter
Measure in 5% suitable antifreeze glycol, and be slowly added into the water for accounting for gross mass 25% into the solution respectively, quickly stirring
It is lower to sequentially add the compound (II) 1~10 and account for total for accounting for prepared by the embodiment 1-10 of gross mass 25% into 10 groups of solution respectively
The suitable auxiliaries (preservative benzoic acid, defoamer organosilicon and thickener xanthans) of quality 5%, grind it after adding
Mill, is eventually adding the water for accounting for gross mass 35%.The suspending agent being prepared is added water into dilution and prepares compound (II) respectively
1-10 concentration is the dilute suspension agent of 40,80,100,160 and 500mg/L.That is 10 compound groups, every group of 5 concentration gradients.
Prepared dilute suspension agent is ready for use on following embodiment.
Embodiment 12, the biological evaluation to rice green leafhopper
The dilute suspension agent of the 100mg/L concentration of each compound prepared using embodiment 11, is chosen two core rice seedlings and immersed
Take out and dry in liquid, after 5 seconds, be placed in Boiling tube, often 20 plants of pipe, then often pipe introduces 20 rice green leafhopper 1 age nymphs, pipe
The wrapping of mouth white yarn cloth is placed under room temperature, 24 it is small when after check survival and dead borer population.Experiment is repeated 3 times, as a result
It is averaged.Activity in percentage, is divided into A, B, C, D level Four relative to blank control, and the death rate 100%~90% is A grades,
The death rate 90%~70% is B grades, and the death rate 70%~50% is C grades, and the death rate 0%~50% is D grades.Test result is shown in Table
2。
Table 2 (II) 1~(II) 10 is when test concentrations are 100mg/L to the activity of rice green leafhopper
Embodiment 13, the biological evaluation to mythimna separata
The dilute suspension agent of the 100mg/L concentration of each compound prepared using embodiment 11, every group of selection 10 first 2 age are glued
Worm and 5 one cun of long maize leafs are put in culture dish, and the 100mL that each compound is added dropwise in every group of culture dish respectively is above-mentioned outstanding
Floating agent, moves into greenhouse after drying and normally raises, 24 as a child statistics survivals and death toll.Experiment is repeated 3 times, and is as a result averaged
Value.Activity in percentage, is divided into A, B, C, D level Four relative to blank control, and the death rate 100%~90% is A grades, the death rate
90%~70% is B grades, and the death rate 70%~50% is C grades, and the death rate 0%~50% is D grades.Test result is shown in Table 3.
Table 3 (II) 1~(II) 10 is when test concentrations are 100mg/L to the activity of aphid
Embodiment 14, phloem transport measure
Castor-oil plant seedling to cultivate 6d is used as material to be tested.Castor-oil plant seedling is carefully peelled off into endosperm, is sure not to fold or staves
Cotyledon.10 groups of buffer solutions that its leaf is soaked in compound (II) 1~(II) 10 (contain 100 μm of ol/L to be measuredization in each buffer solution
Compound, 20mmol/L fatty acid methyl ester sulfonate, 0.25mmol/L MgCl2And 0.5mmol/L CaCl2) in, with identical dense
The ethiprole buffer solution of degree is control., will be careful at seedling cotyledon to hypocotyl crotch 1cm after cultivating 2h in each group buffer solution
Cut-out, collects the bast liquid of incision exudation in 3h, 0.22 μm of organic phase miillpore filter is crossed after centrifugation, filtrate is with pure
Water is to be measured after diluting 2 times.Experiment is repeated 5 times, and is averaged.Use chemical combination in high effective liquid chromatography for measuring bast diffusate
(II) 1~(II) 10 content of thing.Test result is shown in Table 4.As known from Table 4, ethiprole does not pass to bast, and (II) 1~
(II) 10 has preferable dredging property of bast.Therefore 1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group of the present invention -
5- methylene amino-pyrazol types compound (II) 1~(II) 10 is respectively provided with guide function.
The content in castor-oil plant seedling bast diffusate of table 4 (II) 1~(II) 10
Embodiment 15, the biological evaluation to coccinella septempunctata
The dilute suspension agent of 40mg/L, 80mg/L concentration of each compound prepared using embodiment 11, in order to verify it
Whether the security of coccinella septempunctata is improved, using the coccinella septempunctata for cultivating 10d as test worm, each compound is determined using spray-on process
To the comprehensive toxicity (contact toxicity and Oral toxicity) of coccinella septempunctata, correlated results is shown in Table 5.
48h Toxicity test results of 5 compound of table (II) 1-10 to coccinella septempunctata
As can be known from Table 5：Ethiprole is higher to coccinella septempunctata toxicity, and there is 4% poisoning rate in when 40mg/L, and
Rate of being poisoned to death during 80mg/L reaches 46% close to half；It is mainly shown as the weak and limp landing of body or death.Compound (II)
1~10 comprehensive toxicity to coccinella septempunctata is relatively low, without poisoning manifestations during 40mg/L processing, when 80mg/L handle also
There is 1 coccinella septempunctata in one group to show the symptom (compound (II) 4) being slightly poisoned.If defining poisoning rate is not higher than 3%
Processing mass concentration is safe quality concentration, then the safe quality concentration of (II) 1~(II) 10 pair of coccinella septempunctata of compound is at least
For 80mg/L, than ethiprole (<40mg/L) at least improve 1 times.
Embodiment 16, evaluate (II) 1, (II) 2, (II) 5, (II) 8, (II) 9 light degradation property of compound
With xenon lamp (350W) for simulated solar radiant, respectively with compound (II) 1, (II) 2, (II) 5, (II) 8, (II)
9 be light degradation substrate, and concentration is 1 × 10-4mol/L.In view of compound (II) 1, (II) 2, (II) 5, (II) 8, (II) 9 is pure
Solubility is relatively low in water, and addition acetonitrile makees cosolvent.Using high performance liquid chromatography measure compound (II) 1, (II) 2, (II) 5,
(II) 8, (II) 9 concentration after degrading at different moments.Chromatographic condition is as follows：Chromatographic column is phenomenex C18 chromatographic columns
(250nm×4.6mm,5μm)；Mobile phase is acetonitrile：Water=62：38；Flow velocity is 1.0mL/min；Detection wavelength is 250nm；Into
20 μ L of sample amount.Experiment is repeated 3 times, and results are averaged.Degradation rate is calculated, probes into compound (II) 1, (II) 2, (II) 5, (II)
8th, (II) 9 light degradation property.The results are shown in Table 6.
Photodegradation rate of 6 compound (II) 1, (II) 2, (II) 5, (II) 8, (II) 9 of table in different time
Claims (4)
- A kind of 1. synthesis side of 1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- methylene amino-pyrazol type compounds Method, shown in the structural formula such as general formula (II) of the compound：It is characterized in that：The compound is by 1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- amino-pyrazol type chemical combination Thing and compoundIt is prepared in organic solvent through micro-wave digestion and catalyst synergistic effect；The structural formula such as general formula of 1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- amino-pyrazol type compounds (I) shown in：The compoundAny one in following compound：In the general formula (I), (II), R1Any one in following group：—H、—X、Wherein, X represents Cl, Br or I；N is represented 0th, 1,2 or 3；R in the general formula (II)2And R3ByWith 1- (2,6- dichlor-4-trifluoromethyls) phenyl -3- cyano group -5- Substituted into after the reaction of amino-pyrazol type compound；The catalyst is molecular sieve and acid, wherein molecular sieve model 3A types, 4A types, 5A types, and acid is p-methyl benzenesulfonic acid；The organic solvent is toluene, dimethylbenzene, mesitylene, chlorobenzene, bromobenzene, N,N-dimethylformamide or dimethyl sulfoxide.
- 2. synthetic method according to claim 1, it is characterised in that：The organic solvent is toluene.
- 3. synthetic method according to claim 1 or 2, it is characterised in that：The catalyst is p-methyl benzenesulfonic acid and 4A types Molecular sieve.
- 4. synthetic method according to claim 1 or 2, it is characterised in that：The microwave power is 75~225W, and microwave disappears The solution time is 45~60min.
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Non-Patent Citations (5)
| Title |
|---|
| Synthesis and evaluation of some substituted pyrazole derivatives of biological interest;S.R. Pattan，等;《Bulgarian Chemical Communications》;20141231;第46卷(第1期);全文，尤其127页 * |
| Synthesis and Insecticidal Activity of Fipronil-5-Amine Derivatives with Aromatic Aldehyde Group;DELIANG LI,等;《J.Chem.Soc.Pak.》;20121231;第34卷(第1期);全文，尤其scheme2 * |
| 氟虫腈偶联磷酸酯及氨基甲酸酯类化合物的合成及生物活性;马远，等;《农药学学报》;20111231;第13卷(第5期);全文，化合物a * |
| 氟虫腈衍生物-糖基偶合物的合成及其在蓖麻韧皮部的输导性研究;李德亮，等;《农药学学报》;20111231;第11卷(第5期);全文，化合物F1 * |
| 离子液体中N-芳基吡唑衍生物Schiff 碱的合成及晶体结构表征;郭圣荣，等;《有机化学》;20061231;第26卷(第9期);全文 * |
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