CN106674194B - A kind of nicotinic insecticide of structure novel and its preparation method and application - Google Patents
A kind of nicotinic insecticide of structure novel and its preparation method and application Download PDFInfo
- Publication number
- CN106674194B CN106674194B CN201611158148.3A CN201611158148A CN106674194B CN 106674194 B CN106674194 B CN 106674194B CN 201611158148 A CN201611158148 A CN 201611158148A CN 106674194 B CN106674194 B CN 106674194B
- Authority
- CN
- China
- Prior art keywords
- hydrogen atom
- trifluoromethyl
- hydrogen
- phenyl
- ring
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
-
- 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
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
- A01N43/42—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings condensed with carbocyclic rings
-
- 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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
- C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
- C07D221/22—Bridged ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Agronomy & Crop Science (AREA)
- Pest Control & Pesticides (AREA)
- Plant Pathology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Dentistry (AREA)
- General Health & Medical Sciences (AREA)
- Wood Science & Technology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Plural Heterocyclic Compounds (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention discloses nicotinic insecticide of a kind of structure novel and its preparation method and application, the general structure I of the insecticide is as follows:(I)；Wherein R1、R2、R3And R4The substituent group of representative can be the same or different, and the substituent group represented may is that the alkyl of hydrogen, the alkyl of C1-4, C1-4, and the hydrogen atom one or more on alkyl is substituted with halogen atoms；Q is phenyl ring, hydrogen atom one or more is replaced by halogen atom or trifluoromethyl on phenyl ring phenyl or pyridine ring etc.；The nicotinic insecticide of structure novel of the invention efficiently solves the resistance problem that existing insecticide generates, and insecticidal effect is significant, can reach good insecticidal effect under lower concentration；The insecticidal activity of the insecticide of structure novel of the invention is high, and insecticidal spectrum is wide, can kill most pests, and cross resistance is not present between traditional pesticide, can replace the higher insecticide of current toxicity.
Description
Technical field
The present invention relates to the nicotinic insecticides and its system of a kind of technical field of insecticide more particularly to a kind of structure novel
Preparation Method and purposes.
Background technique
In the control of insect of agricultural and gardening, nicotinic insecticide is an important kind, pyrrole especially therein
The insecticides such as worm quinoline, Acetamiprid, Diacloden occupy the very big market share in the market, as imidacloprid be current sales volume most
Big nicotinic insecticide.But this current insecticides controlling object is produced during prolonged use it is anti-
Property, so that its using effect declines.
Novel pesticide is put forward new requirements at present, the biocidal activity for not requiring nothing more than such is high, and insecticidal spectrum is wide, right
Mammal and aquatic animal safety, while also to have between good system physical property and environment friendly, with traditional pesticide
There is no cross resistances, could replace current high poison insecticide in this way.
Summary of the invention
In view of the above-mentioned problems, it is an object of that present invention to provide nicotinic insecticides of a kind of structure novel and preparation method thereof
And purposes.
The present invention to achieve the above object, is achieved through the following technical solutions:
A kind of nicotinic insecticide of structure novel, general structure I are as follows:
Wherein R1、R2、R3And R4The substituent group of representative can be the same or different, and the substituent group represented may is that
Hydrogen, the alkyl of C1-4, C1-4 alkyl, the hydrogen atom one or more on alkyl is substituted with halogen atoms, the alkoxy of C1-4,
The alkoxy of C1-4, the hydrogen atom one or more on alkoxy is substituted with halogen atoms, nitro, amido, hydroxyl, fluorine, chlorine,
Bromine, iodine, cyano, phenyl, the phenyl that hydrogen atom one or more is replaced by halogen atom or trifluoromethyl on phenyl ring, phenoxy group,
The phenoxy group that hydrogen atom one or more is replaced by halogen atom or trifluoromethyl on phenyl ring；
Q is one in following group: hydrogen atom one or more is taken by halogen atom or trifluoromethyl on phenyl ring, phenyl ring
The phenyl in generation, pyridine ring, pyridine ring, the thiazole that hydrogen atom one or more is replaced by halogen atom or trifluoromethyl on pyridine ring
The thiazole ring that hydrogen atom one or more is replaced by halogen atom or trifluoromethyl on ring, thiazole ring.
Preferably, Q is
It is further preferred that R1=R2=R3=R4=H.
Preferably, R1=R3=R4=H, R2=CF3, Q=
Preferably, R1=R3=R4=H, R2=
The invention also includes the preparation methods of the nicotinic insecticide of structure novel, comprising the following steps:
It willOr its hydrochloride andIt is added in solvent and dissolves, phase is added and turns
Shifting catalyst and alkali adjust pH to 8~10, are heated to 40~100 DEG C, are stirred to react 2~24 hours, obtain general structure I's
Compound；
Wherein R1、R2、R3And R4The substituent group of representative can be the same or different, and the substituent group represented may is that
Hydrogen, the alkyl of C1-4, C1-4 alkyl, the hydrogen atom one or more on alkyl is substituted with halogen atoms, the alkoxy of C1-4,
The alkoxy of C1-4, the hydrogen atom one or more on alkoxy is substituted with halogen atoms, nitro, amido, hydroxyl, fluorine, chlorine,
Bromine, iodine, cyano, phenyl, the phenyl that hydrogen atom one or more is replaced by halogen atom or trifluoromethyl on phenyl ring, phenoxy group,
The phenoxy group that hydrogen atom one or more is replaced by halogen atom or trifluoromethyl on phenyl ring；
The group that Q is represented may is that phenyl ring, hydrogen atom one or more is replaced by halogen atom or trifluoromethyl on phenyl ring
Phenyl, pyridine ring, pyridine ring, the thiazole that hydrogen atom one or more is replaced by halogen atom or trifluoromethyl on pyridine ring
The thiazole ring that hydrogen atom one or more is replaced by halogen atom or trifluoromethyl on ring, thiazole ring；
WhereinOr its hydrochloride,Molar ratio with phase transfer catalyst is
1:1~3:0.001~0.005；
The solvent is acetone, butanone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or dimethyl sulfoxide；
The phase transfer catalyst is quaternary ammonium salt-type phase transfer catalyst；
The alkali is potassium carbonate, sodium carbonate, saleratus or sodium bicarbonate.
Preferred preparation method, phase transfer catalyst are tetrabutylammonium bromide or benzyltriethylammoinium chloride.
Raw material in preparation method of the present inventionIt can be easy to directly commercially.Raw materialFor agent for stopping smoking tartaric acid varenicline intermediateSubstituent, according toPreparation side
Method (CN1263745C) professional technician is easy to prepare raw material
The invention also includes the application of the nicotinic insecticide of structure novel, for prevent and treat the plant hopper occurred on crops,
The Thysanopteras such as the homoptera pests such as aleyrodid, leafhopper, aphid and thrips.
Preferred application method is that auxiliary agent is configured to agriculture common formulations, in parts by weight, including general structure I0.1~
90 parts and 10~99.9 parts of auxiliary component.
The present invention has the advantage that compared with prior art
The nicotinic insecticide of structure novel of the invention efficiently solves the resistance problem that existing insecticide generates, and kills
Worm significant effect can reach good insecticidal effect under lower concentration；The insecticide of structure novel of the invention kills
Worm activity is high, and insecticidal spectrum is wide, can kill most pests, and cross resistance, Neng Gouqu are not present between traditional pesticide
For the higher insecticide of current toxicity；
The toxicity of the nicotinic insecticide of present invention structure containing benzazepine is lower, and the residual in crops is few, right
The harmfulness of people, animal is small, solves existing insecticide very well and is more toxic, and the more problem of the residual in crop improves
The safety of agricultural production；Antibody will not be generated to insecticide of the invention using pest in a long time, have fine
Insecticidal effect；The present invention also provides the structure method for producing insecticide, and the preparation method step is few, and technique is easy to grasp
Make, can be used for large-scale industrial production.
Specific embodiment
The object of the present invention is to provide nicotinic insecticide of a kind of structure novel and its preparation method and application, by with
Lower technical solution is realized:
A kind of nicotinic insecticide of structure novel, general structure I are as follows:
Wherein R1、R2、R3And R4The substituent group of representative can be the same or different, and the substituent group represented may is that
Hydrogen, the alkyl of C1-4, C1-4 alkyl, the hydrogen atom one or more on alkyl is substituted with halogen atoms, the alkoxy of C1-4,
The alkoxy of C1-4, the hydrogen atom one or more on alkoxy is substituted with halogen atoms, nitro, amido, hydroxyl, fluorine, chlorine,
Bromine, iodine, cyano, phenyl, the phenyl that hydrogen atom one or more is replaced by halogen atom or trifluoromethyl on phenyl ring, phenoxy group,
The phenoxy group that hydrogen atom one or more is replaced by halogen atom or trifluoromethyl on phenyl ring；
Q is one in following group: hydrogen atom one or more is taken by halogen atom or trifluoromethyl on phenyl ring, phenyl ring
The phenyl in generation, pyridine ring, pyridine ring, the thiazole that hydrogen atom one or more is replaced by halogen atom or trifluoromethyl on pyridine ring
The thiazole ring that hydrogen atom one or more is replaced by halogen atom or trifluoromethyl on ring, thiazole ring.
Preferably, Q is
It is further preferred that R1=R2=R3=R4=H.
Preferably, R1=R3=R4=H, R2=CF3, Q=
Preferably, R1=R3=R4=H, R2=
The invention also includes the preparation methods of the nicotinic insecticide of structure novel, comprising the following steps:
It willOr its hydrochloride andIt is added in solvent and dissolves, phase is added and turns
Shifting catalyst and alkali adjust pH to 8~10, are heated to 40~100 DEG C, are stirred to react 2~24 hours, obtain general structure I's
Compound；
Wherein R1、R2、R3And R4The substituent group of representative can be the same or different, and the substituent group represented may is that
Hydrogen, the alkyl of C1-4, C1-4 alkyl, the hydrogen atom one or more on alkyl is substituted with halogen atoms, the alkoxy of C1-4,
The alkoxy of C1-4, the hydrogen atom one or more on alkoxy is substituted with halogen atoms, nitro, amido, hydroxyl, fluorine, chlorine,
Bromine, iodine, cyano, phenyl, the phenyl that hydrogen atom one or more is replaced by halogen atom or trifluoromethyl on phenyl ring, phenoxy group,
The phenoxy group that hydrogen atom one or more is replaced by halogen atom or trifluoromethyl on phenyl ring；
The group that Q is represented may is that phenyl ring, hydrogen atom one or more is replaced by halogen atom or trifluoromethyl on phenyl ring
Phenyl, pyridine ring, pyridine ring, the thiazole that hydrogen atom one or more is replaced by halogen atom or trifluoromethyl on pyridine ring
The thiazole ring that hydrogen atom one or more is replaced by halogen atom or trifluoromethyl on ring, thiazole ring；
WhereinOr its hydrochloride,Molar ratio with phase transfer catalyst is
1:1~3:0.001~0.005；
The solvent is acetone, butanone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or dimethyl sulfoxide；
The phase transfer catalyst is quaternary ammonium salt-type phase transfer catalyst；
The alkali is potassium carbonate, sodium carbonate, saleratus or sodium bicarbonate.
Preferred preparation method, phase transfer catalyst are tetrabutylammonium bromide or benzyltriethylammoinium chloride.
The invention also includes the application of the nicotinic insecticide of structure novel, for prevent and treat the plant hopper occurred on crops,
The Thysanopteras such as the homoptera pests such as aleyrodid, leafhopper, aphid and thrips.
Preferred application method is that auxiliary agent is configured to agriculture common formulations, in parts by weight, including general structure I0.1~
90 parts and 10~99.9 parts of auxiliary component.
The example that the present invention can prevent and treat harmful organism has:
Anoplura: blind pediculus is several, and Linognathusspp is several, and Cuclotogaster is several, and cotten aphid is several and Phylloxera spp is several；
Thysanoptera: Thrips are several, and Hercinothrips spp belongs to several, and Graminothrips are several, pale brown thrips, cotton thrips and African campanulaceae
Thrips；
Heteroptera: Cimex is several, Distantiella theobroma, and red stinkbug belongs to several, and brown scutteleerid belongs to several, and Leptocorisa spp belongs to several,
Bemisia spp is several, and quasi- lace bug belongs to several, red pig stinkbug, Sahlbergella singularis, and black stinkbug belongs to several and pig stinkbug of sucking blood belongs to several.
Homoptera, such as wolly whitefly, wild cabbage aleyrodid, the red a red-spotted lizard of circle belong to several, and Aphidiadae, Aphis is several, and circle a red-spotted lizard belongs to several, sweet potato
Aleyrodid, lecanium belong to several, Chrysomphalus aonidium, and rose takes turns Qi, Coccushesperidum, and Empoasca spp belongs to several, apple aphid, Erythroneura spp category tree species,
Gummy a red-spotted lizard, brown small brown rice planthopper belong to several, and brown ash lecanium, lepidosaphes belongs to several, and pipe Aphis is several, and tumor aphid genus is several, rice green leafhopper category number
Kind, brown back rice plant hopper belongs to several, and tumor woolly aphid belongs to several, and citrus mealy bug belongs to several, and white peach scale belongs to several, and mealybug belongs to several, and Psylla spp is several,
Circle a red-spotted lizard belongs to several, and Rhopalosiphum is several, and grey a red-spotted lizard belongs to several, and leafhopper belongs to several, and y-bend Aphis is several, long tube stinkbug, Trialeurodes vaporariorum Westwood,
African citrus mesh lice and Unaspis citri.
Effective component according to the invention can prevent and treat, that is, contain or destroy above-mentioned harmful organism, especially occur
In plant, the part of useful plant or these plants especially in terms of agricultural, gardening and forest, such as fruit, flower, leaf, master
Stem, stem tuber or root, the new first portion of plant can also be protected causing harm from these harmful organisms in some cases.
Suitable target crops particularly relate to, cereal such as wheat, barley, rye, oat, rice, corn or sorghum；Sweet tea
Vegetables such as sugar beet and fodder beet；Fruit such as the operatic circle, xylocarp and mushy fruit, such as apple, pears, plum, almond, cherry or berries,
Such as strawberry, Rubus corchorifolius or blackberry, blueberry；Leguminous plant, such as semen viciae fabae, lens, pea or soybean；Oil crop, as rape, mustard, opium poppy,
Olive, sunflower, castor-oil plant, coconut, cocoa or peanut；Cucurbit class, such as pumpkin, cucumber or watermelon；Fibre plant class, as cotton,
Flax, hemp or jute；Citrus, such as orange, lemon, grape fruit or red tangerine；Greengrocery, as spinach, lettuce, asparagus, Chinese cabbage,
Cucurbit fore-telling, garlic, tomato, potato or loudspeaker green pepper；Laurel class, such as avocado, camphor platymiscium or camphor；There are also tobacco, dry fruit, coffees
Coffee, eggplant, sugarcane, tea, pepper, vine, hops, Musaceae, latex plant and ornamental plant.
The compounds of this invention can further be diluted with its dosage form or as the preparation prepared by use form make
With, such as ready to use solution agent, suspending agent, seed coat agent, emulsion, pulvis, paste and granule.It may be carried out by conventional means and apply
With, such as pour, be sprayed, atomizing, dust, seed treatment or spreading fertilizer over the fields.
Table 1 is that the compound structure of the nicotinic insecticide (I) of structure novel measures analytical table
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
The compound for preparing serial number 1 in table 1 includes the following steps:
2,3,4,5- tetrahydro -1,5- first bridge -1H-3- benzazepine hydrochloride 19.6g are added into reaction kettle
Carbonic acid is added in (0.1mol), acetone 200ml, tetrabutylammonium bromide 0.32g, 2-vhloro-5-chloromethylpyridine 16.2g (0.1mol)
Potassium 45g adjusts pH to 10, is warming up to back flow reaction 6h, is cooled to room temperature, filters, 30ml acetone washing filter cake, and filtrate negative pressure is de-
Except solvent acetone, kettle is residual plus methanol 50ml recrystallization, filtration drying obtain target compound 22.3g, yield about 78.2%.Purity
98% or more.
Elemental analysis result: C:71.70%；H:6.02%；Cl:12.45%；N:9.84%.
M/z:284.11 (100.0%), 286.11 (33.7%), 285.11 (19.3%), 287.11 (6.0%).
Embodiment 2:
The compound for preparing serial number 8 in table 1 includes the following steps:
7- trifluoromethyl -2,3,4,5- tetrahydro -1,5- first bridge -1H-3- benzazepine 22.7g are added into reaction kettle
(0.1mol), n,N-Dimethylformamide 200ml, benzyltriethylammoinium chloride 1.14g, 2-vhloro-5-chloromethylpyridine 32.4g
(0.2mol) is added potassium carbonate 40g and adjusts pH to 9, be warming up to 80 DEG C of insulation reaction 10h, be cooled to room temperature, filter, 30mlN,
Dinethylformamide washs filter cake, and filtrate negative pressure removes solvent n,N-Dimethylformamide, and kettle is residual plus methanol 80ml is recrystallized,
Filtration drying obtains target compound 26.0g, yield about 73.6%.98% or more purity.
Elemental analysis result: C:61.28%；H:4.57%；Cl:10.05%；F:16.16%；N:7.94%.
M/z:352.10 (100.0%), 354.09 (32.0%), 353.10 (19.7%), 355.10 (6.3%),
354.10 (1.9%).
Embodiment 3:
The compound for preparing serial number 22 in table 1 includes the following steps:
6,7,8,9- tetra- fluoro- 2,3,4,5- tetrahydro -1,5- first bridge -1H-3- benzazepine 23.1g are added into reaction kettle
Carbonic acid is added in (0.1mol), acetone 200ml, tetrabutylammonium bromide 0.95g, 2-vhloro-5-chloromethylpyridine 48.6g (0.3mol)
Potassium 45g adjusts pH to 10, is warming up to back flow reaction 6h, is cooled to room temperature, filters, 30ml acetone washing filter cake, and filtrate negative pressure is de-
Except solvent, kettle is residual plus methanol 50ml recrystallization, filtration drying obtain target compound 25.2g, yield about 70.6%.Purity 98%
More than.
Elemental analysis result: C:57.23%；H:3.67%；Cl:9.94%；F:21.30%；N:7.85%.
M/z:356.07 (100.0%), 358.07 (32.1%), 357.07 (19.1%), 359.07 (5.9%),
358.08 (1.6%).
Embodiment 4:
The compound for preparing serial number 65 in table 1 includes the following steps:
7- cyano -2,3,4,5- tetrahydro -1,5- first bridge -1H-3- benzazepine 18.4g are added into reaction kettle
(0.1mol), n,N-Dimethylformamide 200ml, benzyltriethylammoinium chloride 0.25g, 2,3,4,5,6- five fluorine benzyl chloride 21.7g
(0.1mol) is added sodium carbonate 25g and adjusts pH to 8, be warming up to 60 DEG C of insulation reaction 10h, be cooled to room temperature, filter, 30mlN,
Dinethylformamide washs filter cake, and filtrate negative pressure removes solvent n,N-Dimethylformamide, and kettle is residual plus methanol 80ml is recrystallized,
Filtration drying obtains target compound 27.3g, yield about 75%.98% or more purity.
Elemental analysis result: C:62.64%；H:3.60%；F:26.06%；N:7.70%.
M/z:364.10 (100.0%), 365.10 (21.3%), 366.11 (2.0%).
Embodiment 5:
The compound for preparing serial number 100 in table 1 includes the following steps:
7- (3,5- dichlorophenyl) -2,3,4,5- tetrahydro -1,5- first bridge -1H-3- benzazepine is added into reaction kettle
30.4.4g (0.1mol), the fluoro- 5- trifluoromethyl benzyl chloride of n,N-Dimethylformamide 300ml, tetrabutylammonium bromide 0.65g, 2-
21.3g (0.1mol) is added potassium carbonate 40g and adjusts pH to 9, be warming up to 70 DEG C of insulation reaction 10h, be cooled to room temperature, filters,
50mlN, dinethylformamide wash filter cake, and filtrate negative pressure removes solvent n,N-Dimethylformamide, and kettle is residual to add methanol 100ml
Recrystallization, filtration drying obtain target compound 29.1g, yield about 60.6%.98% or more purity.
Elemental analysis result: C:62.51%；H:3.99%；Cl:14.76%；F:15.82%；N:2.92%.
M/z:479.08 (100.0%), 481.08 (64.0%), 480.09 (27.3%), 482.08 (17.5%),
483.08 (10.3%), 481.09 (3.6%), 484.08 (2.8%), 483.09 (2.3%).
Embodiment 6:
The compound for preparing serial number 114 in table 1 includes the following steps:
7- nitro -2,3,4,5- tetrahydro -1,5- first bridge -1H-3- benzazepine 20.4g are added into reaction kettle
Carbonic acid is added in (0.1mol), butanone 200ml, tetrabutylammonium bromide 0.58g, 2- chloro-5-chloromethyl thiazole 16.8g (0.1mol)
Potassium 40g adjusts pH to 9, is warming up to 40 DEG C of insulation reaction 15h, is cooled to room temperature, filters, and 30ml butanone washs filter cake, and filtrate is negative
Pressure-off removes solvent n,N-Dimethylformamide, and kettle is residual plus ethyl alcohol 80ml recrystallization, filtration drying obtain target compound 23.5g,
Yield about 69.9%.98% or more purity.
Elemental analysis result: C:53.65%；H:4.20%；Cl:10.56%；N:12.51%；O:9.53%；S:
9.55%.
M/z:335.05 (100.0%), 337.05 (37.2%), 336.05 (18.2%), 338.05 (6.3%),
339.04 (1.5%), 337.06 (1.3%).
The dosage form citing of part of compounds composition in table 1.
740% compound of embodiment, 1 wettable powder is made of following raw material: compound 140%, sodium lignin sulfonate
6%, sodium butylnaphthalenesulfonate 4.5%, poly- trisiloxanes 2%, alkyl benzene sulphonate ammonium 2% and white carbon black surplus.
820% compound of embodiment, 22 suspending agent is made of following raw material: compound 2220%, poly- methyl carboxylic acids sodium
1.5%, di-2-ethylhexylphosphine oxide ethyl sodium naphthalene sulfonate 1.2%, sodium metnylene bis-naphthalene sulfonate 1.0%, poly- trisiloxanes 0.4%, propylene glycol
4.5%, xanthan gum 0.2% and water surplus.
920% compound 56 of embodiment can be dispersed oil-suspending agent and be made of following raw material: compound 5620%, dodecyl
Benzene sulfonic acid calcium 1%, lauryl alcohol ether polyoxypropylene ester 8%, organobentonite 2% and methyl oleate surplus.
The compound in table 1 is tested using indoor measurement method:
1. the virulence of antagonism cotten aphid is tested
Test using leaching worm leaf dipping method, in resistance serious farming region acquisition do not contacted any medicament with 50
The cotton seedling of larvae aphid, which is inverted in dilution series medicament, to be soaked 10 seconds, is then put back in the dactylethrae equipped with nutrient solution, after moisture evaporation
It checks original borer population, and is put into Nutrition Dept. and cultivates.Each concentration is repeated 3 times, and clear water processing is control group, temperature in insectary
25 ± 1 DEG C are maintained at, relative humidity 50~60%, light dark period is 14:10 (L:D).For 24 hours, survival borer population, meter are checked after 48h
Calculate the death rate and corrected mortality, record total borer population before medicine, after medicine for 24 hours, 48h record total borer population (death toll).According to following public affairs
Formula calculates the death rate (%) and corrected mortality (%).
The death rate (%)=dead borer population/total borer population × 100；
Corrected mortality (%)=(the processing death rate-control death rate)/(100- compares the death rate) × 100；
The LC of each processing is calculated with statistical analysis system50。
Experimental result is as shown in table 2:
The virulence test result of the antagonism cotten aphid of compound in 2 table 1 of table
The nicotine compound of structure novel of the invention is dense with the semilethal of 48h for 24 hours it can be seen from the result of table 2
Degree is small compared with existing pesticide imidacloprid, and virulence value can have preferable control efficiency compared with imidacloprid height with antagonism cotten aphid.
2. the toxicity test of pair aleyrodid (being acquired from the serious farming region of resistance)
Leaf dipping method is taken in experiment, will not break into the small of diameter 35mm by the fresh chilli leaf that medicament pollutes with punch first
Disk, impregnates naturally dry after 10s in series of concentrations medical fluid, and face of blade is layered on downward in the culture dish that diameter is 35mm
(agar of 14gL-1 is poured into culture dish in advance)；After the puberty of short duration freezing of consistent Bemisia tabaci adults, gently beat in training
It supports on the roundlet blade in ware, 20-30 adult of every culture dish, with the sealing of hole preservative film is pricked, when Bemisia tabaci is extensive from narcosis
After coming again, by culture dish be inverted in (25 ± 1) DEG C, relative humidity 65%, illumination 14:10 (L:D) incubator in.It is each dense
Degree sets 3 repetitions.After 48h, Bemisia tabaci adults death condition is checked, calculate the death rate and corrected mortality.It is with statistical analysis
Statistics calculates the LC of each processing50, experimental result is as shown in table 3.
The virulence test result of the antagonism aleyrodid of compound in 3 table 1 of table
It can be seen from the result of table 3 half lethal concentration of the nicotine compound 48h of structure novel of the invention compared with
Small, virulence value is high compared with imidacloprid, Acetamiprid, can have preferable control efficiency with antagonism aleyrodid.
3. the toxicity test of pair brown paddy plant hopper (being acquired from the serious farming region of resistance)
Test is carried out referring to " farm-chemical indoor determination test rule-insecticide ", measures medicament using rice-stem dipping method
To the virulence of brown paddy plant hopper.The specific method is as follows: extracting with root healthy and strong seeding stage rice strain, rice height is cleaned, 5 in 5cm or so
It one group, dries in the air to surface in shady place without bright water.Medicament is diluted to series of concentrations, then by rice seedling respectively in various concentration
15s is impregnated in medical fluid, is compareed with clear water, and each concentration is repeated 3 times, and after taking-up is dried, encases root with the absorbent cotton soaked
(outside is sealed with preservative film, moisturizing) is put into culture cup, the access consistent 3 age mid-term nymph of standard, and 10 every glass.Stand 1
After~2h, impaired individuals are rejected.Connecing and culture cup is put into temperature after worm is (25 ± 1) DEG C, and the photoperiod is the greenhouse of 16:8 (L:D)
Middle raising.For 24 hours, after 48h, 72h, the stiff person of stimulation is touched as death with writing brush, dead borer population is recorded, it is dead to calculate each processing
Rate and corrected mortality.The LC of each processing is calculated with statistical analysis system50, experimental result is as shown in table 4.
The virulence test result of the antagonism brown paddy plant hopper of compound in 4 table 1 of table
It can be seen from the result of table 4 nicotine compound of structure novel of the invention for 24 hours, half cause of 48h and 72h
Dead concentration is smaller, and virulence value has preferable control efficiency compared with Nitenpyram height, antagonism brown paddy plant hopper.
Claims (9)
1. a kind of nicotinic insecticide, it is characterised in that: general structure I is as follows:
Wherein R1、R2、R3And R4The substituent group of representative can be the same or different；
R1The substituent group of representative is: hydrogen, nitro, hydroxyl, fluorine or iodine；
R2The substituent group of representative is: hydrogen, the alkyl of C1-4, C1-4 alkyl, the hydrogen atom one or more on alkyl is by halogen original
Sub- substitution, the alkoxy of C1-4, C1-4 alkoxy, the hydrogen atom one or more on alkoxy is substituted with halogen atoms, nitre
Base, amido, hydroxyl, fluorine, chlorine, bromine, iodine, cyano, phenyl, on phenyl ring hydrogen atom one or more by halogen atom or trifluoromethyl
Substituted phenyl, phenoxy group, the phenoxy group that hydrogen atom one or more is replaced by halogen atom or trifluoromethyl on phenyl ring；
R3The substituent group of representative is: hydrogen, hydroxyl, nitro, amido, fluorine, chlorine or bromine；
R4The substituent group of representative is: hydrogen or fluorine；
Q is one in following group: hydrogen atom one or more is replaced by halogen atom or trifluoromethyl on phenyl ring phenyl,
Hydrogen atom one or more is replaced by halogen atom or trifluoromethyl on pyridine ring, pyridine ring pyridine ring, thiazole ring, thiazole ring
The thiazole ring that upper hydrogen atom one or more is replaced by halogen atom or trifluoromethyl.
2. nicotinic insecticide according to claim 1, it is characterised in that: Q is
3. nicotinic insecticide according to claim 2, it is characterised in that: R1=R2=R3=R4=H.
4. nicotinic insecticide according to claim 2, it is characterised in that: R1=R3=R4=H, R2=CF3,
5. nicotinic insecticide according to claim 1, it is characterised in that: R1=R3=R4=H,
6. the preparation method of nicotinic insecticide described in claim 1, it is characterised in that: the following steps are included:
It willOr its hydrochloride andIt is added in solvent and dissolves, phase transfer is added and urges
Agent and alkali adjust pH to 8~10, are heated to 40~100 DEG C, are stirred to react 2~24 hours, obtain the chemical combination of general structure I
Object；
Wherein R1、R2、R3And R4The substituent group of representative can be the same or different；
R1The substituent group of representative is: hydrogen, nitro, hydroxyl, fluorine or iodine；
R2The substituent group of representative is: hydrogen, the alkyl of C1-4, C1-4 alkyl, the hydrogen atom one or more on alkyl is by halogen original
Sub- substitution, the alkoxy of C1-4, C1-4 alkoxy, the hydrogen atom one or more on alkoxy is substituted with halogen atoms, nitre
Base, amido, hydroxyl, fluorine, chlorine, bromine, iodine, cyano, phenyl, on phenyl ring hydrogen atom one or more by halogen atom or trifluoromethyl
Substituted phenyl, phenoxy group, the phenoxy group that hydrogen atom one or more is replaced by halogen atom or trifluoromethyl on phenyl ring；
R3The substituent group of representative is: hydrogen, hydroxyl, nitro, amido, fluorine, chlorine or bromine；
R4The substituent group of representative is: hydrogen or fluorine；
Q is one in following group: hydrogen atom one or more is replaced by halogen atom or trifluoromethyl on phenyl ring phenyl,
Hydrogen atom one or more is replaced by halogen atom or trifluoromethyl on pyridine ring, pyridine ring pyridine ring, thiazole ring, thiazole ring
The thiazole ring that upper hydrogen atom one or more is replaced by halogen atom or trifluoromethyl；
WhereinOr its hydrochloride,With the molar ratio of phase transfer catalyst be 1:1~
3:0.001~0.005；
The solvent is acetone, butanone, N,N-dimethylformamide, DMAC N,N' dimethyl acetamide or dimethyl sulfoxide；
The phase transfer catalyst is quaternary ammonium salt-type phase transfer catalyst；
The alkali is potassium carbonate, sodium carbonate, saleratus or sodium bicarbonate.
7. the preparation method of nicotinic insecticide according to claim 6, it is characterised in that: phase transfer catalyst is four fourths
Base ammonium bromide or benzyltriethylammoinium chloride.
8. the application of nicotinic insecticide described in claim 1, it is characterised in that: for prevent and treat occur on crops fly
The Thysanopteras such as the homoptera pests such as lice, aleyrodid, leafhopper, aphid and thrips.
9. the application of nicotinic insecticide according to claim 8, it is characterised in that: be configured to the common agent of agricultural with auxiliary agent
Type includes 0.1~90 part and 10~99.9 parts of auxiliary component of general structure I in parts by weight.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611158148.3A CN106674194B (en) | 2016-12-14 | 2016-12-14 | A kind of nicotinic insecticide of structure novel and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611158148.3A CN106674194B (en) | 2016-12-14 | 2016-12-14 | A kind of nicotinic insecticide of structure novel and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106674194A CN106674194A (en) | 2017-05-17 |
| CN106674194B true CN106674194B (en) | 2019-03-05 |
Family
ID=58869267
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611158148.3A Active CN106674194B (en) | 2016-12-14 | 2016-12-14 | A kind of nicotinic insecticide of structure novel and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106674194B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1715280A (en) * | 1997-12-31 | 2006-01-04 | 辉瑞产品公司 | Aryl fused azapolycyclic compounds |
| WO2006006071A1 (en) * | 2004-07-07 | 2006-01-19 | Pfizer Products Inc. | Resolution of an aryl-fused azapolycyclic compound |
| CN101693712A (en) * | 2009-10-13 | 2010-04-14 | 上海立科化学科技有限公司 | Method for synthesizing Varenicline intermediate 2, 3, 4, 5-tetralin-1, 5-methylene-hydrogen-benzoazepine |
| CN103204804A (en) * | 2013-04-10 | 2013-07-17 | 山东省联合农药工业有限公司 | Nicotine compound containing double benzene and preparation method and use thereof |
| CN103232434A (en) * | 2013-03-11 | 2013-08-07 | 山东省联合农药工业有限公司 | Nicotine compound, preparation method and uses thereof |
-
2016
- 2016-12-14 CN CN201611158148.3A patent/CN106674194B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1715280A (en) * | 1997-12-31 | 2006-01-04 | 辉瑞产品公司 | Aryl fused azapolycyclic compounds |
| WO2006006071A1 (en) * | 2004-07-07 | 2006-01-19 | Pfizer Products Inc. | Resolution of an aryl-fused azapolycyclic compound |
| CN101693712A (en) * | 2009-10-13 | 2010-04-14 | 上海立科化学科技有限公司 | Method for synthesizing Varenicline intermediate 2, 3, 4, 5-tetralin-1, 5-methylene-hydrogen-benzoazepine |
| CN103232434A (en) * | 2013-03-11 | 2013-08-07 | 山东省联合农药工业有限公司 | Nicotine compound, preparation method and uses thereof |
| CN103204804A (en) * | 2013-04-10 | 2013-07-17 | 山东省联合农药工业有限公司 | Nicotine compound containing double benzene and preparation method and use thereof |
Non-Patent Citations (1)
| Title |
|---|
| Synthesis od 2,3,4,5-Tetradysro-1,5-methano-1H-3-benzazepibe via Oxidative Cleavage and Reductive Amination Strayegies;Paige R. Brooks;《Synthesis》;20040507(第11期);化合物8 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106674194A (en) | 2017-05-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR100784746B1 (en) | Pyrazole derivatives and process for producing the same, and pesticides containing the same as the active ingredient | |
| CN109864067B (en) | Weeding composition and application | |
| EA000973B1 (en) | Novel 5-amino-3-cyano-4-ethylsulfinyl-1-phenylpyrazole compounds and their use as pesticides | |
| WO2017173957A1 (en) | Use of tenvermectin in control of harmful insects in agricultural and forest crops | |
| RU2077201C1 (en) | Derivatives of 1-phenylimidazole, method of struggle against agriculture pests and composition for pesticide treatment | |
| CN105211094B (en) | Woods fruit insect prevention liniment, preparation method and application | |
| KR101225103B1 (en) | The use of insecticidal composition comprising extracts of albizzia julibrissin | |
| CN106674194B (en) | A kind of nicotinic insecticide of structure novel and its preparation method and application | |
| CN113367164A (en) | Method for extracting castor-oil plant insecticidal active substance and combined application of castor-oil plant insecticidal active substance and microbial source insecticide | |
| CN105794813B (en) | A kind of Pesticidal combination and its method for controlling agricultural pests | |
| CN109673598A (en) | The control method of state's scholartree olethreutree | |
| PL200927B1 (en) | Synergistic insecticidal compositions | |
| CN106614692B (en) | A kind of dinotefuran fumicants for preventing and treating edible fungus cluster mosquito | |
| CN103918705B (en) | Pesticidal combination containing spiral shell worm ethyl ester and gamma cyhalothrin and application thereof | |
| CN109042753A (en) | A kind of long-acting slow-release plant source compound Herbicidal combinations and preparation method thereof | |
| CN107646899A (en) | A kind of green high-efficient rice seed dressing agent and its preparation method and application | |
| CN106699765B (en) | A kind of novel nicotinamide insecticide and its preparation method and application | |
| CN101553117B (en) | 3-(2, 4, 6-trimethylphenyl)-4-neopentyl carbonyloxy-5, 5-tetramethylene-△3-dihydrofuran-2-one is used for preventing and treating Diptera of gall mosquito family | |
| CN105410075A (en) | Botanical reagent for prevention and treatment of meloidogyne and preparation and use method thereof | |
| CN105794798B (en) | A kind of Pesticidal combination | |
| BR112020013292A2 (en) | methods to control pests of soybean plants, method to control pests of the families pentatomidae, agromyzidae, noctuidae, pyralidae, and / or thripidae and use of one or more compounds of formula i | |
| CN105557709B (en) | Purposes of eight yuan of oxygen bridge heterocyclic compounds as insecticidal synergist | |
| CN104522036B (en) | Insecticidal composition used for preventing and controlling lepidoptera pests and homoptera pests | |
| CN115886007B (en) | Pesticide composition, application thereof and pesticide preparation containing pesticide composition | |
| Roark | A review of information on anabasine |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |