CN107840825B - Hepta-fluoroiso-propyl quinolines and the preparation method and application thereof - Google Patents
Hepta-fluoroiso-propyl quinolines and the preparation method and application thereof Download PDFInfo
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- CN107840825B CN107840825B CN201610838440.3A CN201610838440A CN107840825B CN 107840825 B CN107840825 B CN 107840825B CN 201610838440 A CN201610838440 A CN 201610838440A CN 107840825 B CN107840825 B CN 107840825B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D215/00—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems
- C07D215/02—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom
- C07D215/16—Heterocyclic compounds containing quinoline or hydrogenated quinoline ring systems having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen atoms or carbon atoms directly attached to the ring nitrogen atom 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
- C07D215/20—Oxygen atoms
- C07D215/22—Oxygen atoms attached in position 2 or 4
- C07D215/233—Oxygen atoms attached in position 2 or 4 only one oxygen atom which is attached in position 4
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01G—HORTICULTURE; CULTIVATION OF VEGETABLES, FLOWERS, RICE, FRUIT, VINES, HOPS OR SEAWEED; FORESTRY; WATERING
- A01G13/00—Protecting plants
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- 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
Abstract
The invention discloses hepta-fluoroiso-propyl quinolines shown in formula (I) and the preparation method and application thereof.R in formula1、R2、R3、R4、R5And R6With definition given in specification.Formula (I) compound of the present invention has sterilization and/or kills insects mites bioactivity, especially has very high activity to insect pests such as the diseases such as powdery mildew and aphids.
Description
Technical field
The invention belongs to sterilize, kill insects mites agent field, and in particular to the seven fluorine isopropyls for having sterilization, killing insects mites bioactivity
Base quinolines and preparation method thereof, the sterilization containing the compound are killed insects mites agent composition and are changed with these
Close object control disinfect pathogen, the purposes and method of evil insects mites.
Background technique
Disinfect pathogen, the prevention and treatment of evil insects mites are extremely important during realizing high-efficiency agriculture.Disinfect pathogen, evil simultaneously
The prevention and treatment of insects mites woods, herd, in the fields such as secondary, fishing and public health it is also critically important.It falls ill although having much to have in the market
Bacterium, pest/acarid control medicament, but the continuous expansion due to market, external disinfect pathogen and evil insects mites, disinfect pathogen and evil
The problems such as drug resistances of insects mites, drug service life, Pharmacoeconomic and people need science to the pay attention to day by day of environment
Family constantly research, and then develop the compatible and sterilization with different role mode of new efficient, safety, economy, environment, kill
Insects mites agent new varieties.
CN1193017 discloses quinolines shown in formula (K1) and its purposes as fungicide, wherein formula
(K2) compound represented is developed as fungicide, general entitled Tebufloquin；Based on hepta-fluoroiso-propyl amine,
CN104628639 discloses hepta-fluoroiso-propyl quinolines shown in formula (K3) and its purposes as disinfectant use in agriculture,
Wherein formula (K4) compound represented has preferable bactericidal activity.
There is more efficient and/or more broad-spectrum biological activity novel quinoline class compound to obtain, based on pertinent literature and
The work of our early periods, we design and synthesize have not been reported with having shown in formula (I), sterilization, to kill insects mites active
Quinolines.The compounds of this invention is shown compared with the higher bactericidal activity of Tebufloquin shown in K2, while of the present inventionization
Conjunction object, which also has, kills insects mites activity.
Summary of the invention
The present invention provides the hepta-fluoroiso-propyls shown in formula (I) with bioactivity such as prevention and treatment disinfect pathogen, evil insects mites
Quinolines and its isomers:
Wherein:
I.R1COR, CSR, propargyl or allyl are represented, wherein R represents C4-C5Naphthenic base, C4-C5Cycloalkyl oxy, C4-
C5Cycloalkylsulfanyl, C4-C5Naphthenic base amido, C4-C5Heterocyclylalkyl, C4-C5Heterocyclylalkyl oxygroup, C4-C5Heterocyclylalkyl sulfenyl,
C4-C5Heterocyclylalkyl amido；And R1Middle hydrogen moiety can all be taken by identical or different substituent group in following
Generation: halogen, C1-C6Alkyl, C1-C6Halogenated alkyl, C1-C6Alkoxy, C1-C6Halogenated alkoxy, C1-C6Alkyl sulfenyl, C1-C6Halogen
For alkylthio group, C1-C6Alkyl amine group, C1-C6Halogenated alkyl amido；
II.R2And R3, R4, R5, R6It is same or different, and represents hydrogen, halogen, C1-C12Alkyl, C1-C12Alkoxy,
C1-C12Halogenated alkyl or C1-C12Halogenated alkoxy；
In the definition of compound (I) given above, no matter term used exclusive use is also used in compound word, represent
Following substituent group:
Halogen: refer to fluorine, chlorine, bromine, iodine；
Alkyl: refer to linear or branched alkyl group；
Naphthenic base: refer to saturated or unsaturated naphthenic base；
Heterocyclylalkyl: refer to saturation or unsaturated heterocycle alkyl, at least 1 N, O and/or S in formula；
It is halogenated: to refer to hydrogen moiety therein or all replaced by halogen atom.
Currently preferred compound are as follows: in formula (I):
I.R1COR, CSR, propargyl or allyl are represented, wherein R represents C4-C5Naphthenic base, C4-C5Cycloalkyl oxy, C4-
C5Cycloalkylsulfanyl, C4-C5Naphthenic base amido, C4-C5Heterocyclylalkyl, C4-C5Heterocyclylalkyl oxygroup, C4-C5Heterocyclylalkyl sulfenyl or
C4-C5Heterocyclylalkyl amido；And R1Middle hydrogen moiety can all be taken by identical or different substituent group in following
Generation: halogen, C1-C6Alkyl, C1-C6Halogenated alkyl, C1-C6Alkoxy, C1-C6Halogenated alkoxy, C1-C6Alkylthio group, C1-C6It is halogenated
Alkylthio group, C1-C6Alkylamino radical or C1-C6Halogenated alkylamino radical；
II.R2And R3, R4, R5, R6It is same or different, and represents hydrogen, C1-C12Alkyl or C1-C12Halogenated alkyl.
The further preferred compound of the present invention are as follows: in formula (I):
I.R1COR or CSR is represented, wherein R represents C4-C5Naphthenic base, C4-C5Cycloalkyl oxy, C4-C5Cycloalkylsulfanyl,
C4-C5Naphthenic base amido, C4-C5Heterocyclylalkyl, C4-C5Heterocyclylalkyl oxygroup, C4-C5Heterocyclylalkyl sulfenyl or C4-C5Heterocyclylalkyl
Amido；And R1Middle hydrogen moiety can all be replaced by identical or different substituent group in following: halogen, C1-C6Alkane
Base, C1-C6Halogenated alkyl, C1-C6Alkoxy, C1-C6Halogenated alkoxy, C1-C6Alkyl sulfenyl, C1-C6Halogenated alkylthio, C1-C6
Alkylamino radical or C1-C6Halogenated alkylamino radical；
II.R2And R3, R4, R5, R6It is same or different, and represents hydrogen or C1-C6Alkyl.
Compound specifically preferred according to the invention are as follows: in formula (I):
I.R1COR or CSR is represented, wherein R represents cyclopenta, cyclopentyloxy, tetrahydrofuran -3- base, tetrahydrofuran -2-
Base, tetrahydrofuran -3- base oxygroup, tetrahydrofuran -2- base oxygroup；And R1Middle hydrogen moiety all can be by following
Identical or different substituent group replaces: halogen, C1-C4Alkyl, C1-C4Halogenated alkyl, C1-C4Alkoxy, C1-C4Halogenated alkoxy；
II.R2And R3, R4, R5, R6It is same or different, and represents hydrogen or C1-C6Alkyl.
Formula (I) compound specifically preferred according to the invention is compound as follows:
The compound of the present invention can exist in the form of one or more isomers.Isomers includes enantiomter, non-
Enantiomter, geometric isomer and cis-trans-isomer.Such as formula (I) compound represented of the present invention, due to carbon-carbon therein
Double bond connects different substituent groups and can form geometric isomer (indicating different configurations respectively with Z and E), and the present invention includes
The mixture of Z-type isomers and E-isomer and their any ratios.Formula (I) compound represented of the present invention, due to wherein
A carbon atom on connect four different substituent groups and form stereoisomer (different configurations is indicated with R and S respectively),
The present invention includes the mixture of R type isomers and S type isomers and their any ratios.Chemical combination shown in formula (I) of the present invention
Object forms cis-trans-isomer (respectively with cis due to connecting 2 or more substituent groups on naphthenic base therein or Heterocyclylalkyl
Different configurations is indicated with trans), the present invention includes cis type isomers and trans type isomers and their any ratios
Mixture.
The invention further relates to a kind of formula (I) compound containing biologic effective dose prevented and treated disinfect pathogen, do harm to insects mites and extremely
A kind of few other composition selected from surfactant, solid diluent and liquid diluent.
The invention further relates to a kind of prevention and treatment disinfect pathogen, does harm to formula (I) compound containing biologic effective dose of insects mites and have
The composition of at least one other bioactive compound or preparation of effect amount.
The invention further relates to a kind of prevention and treatment disinfect pathogens, the method for evil insects mites, including changing the formula (I) of biologic effective dose
Close object contact disinfect pathogen, evil insects mites or its environment.Such a disinfect pathogen, pest/acarid control method are also related to,
Disinfect pathogen, formula (I) compound for doing harm to insects mites or its environment biologic effective dose contain formula (I) compound and biologically effective
The mixture of at least one other compound or preparation of amount is contacted to prevent and treat disinfect pathogen, evil insects mites.
Formula (I) compound of the invention has broad spectrum of activity: the compound having can be used for preventing and treating disinfect pathogen, it may also be used for
Pest control/mite；And the compound having has very high bioactivity to certain target pest germs, so that in very low agent
Good effect is obtained under amount.
Currently preferred composition is the composition containing above-mentioned preferred compound.It is preferable that with above-mentioned excellent
The method for selecting compound.
The part formula (I) compound listed below with table 1 is to further illustrate the present invention, but restriction is of the invention.This
Fusing point given in invention is not calibrated, and when formula (I) compound synthesized by the present invention is viscous solid, some viscous solids are put
Non-tacky solids can be cured as by postponing, and when formula (I) compound synthesized by the present invention is viscous liquid, some viscous liquids are placed
After can solidify, all compounds are considerable in LC-MS (APCI, Pos) (Agilent 1100Series LC/MSD) in table 1
Observe its molecular ion peak.Compound in table 11H NMR (Varian INOVA-300spectrometer) with
Tetramethylsilane (TMS) makees internal standard, deuterated chloroform (CDCl3) or deuterated dimethyl sulfoxide (DMSO) make solvent.
Table 1:
Table 2
Formula (I) compound represented of the present invention can be obtained by reaction equation 1 shown below；(II) in reaction equation 1
It can be obtained by reaction equation 2 shown below；(IV) in (III) and reaction equation 2, (V) and (VII) in reaction equation 1 can
To be synthesized by purchase or referring to pertinent literature；L in reaction equation 1 is leaving group, such as chlorine, bromine, iodine, sulphonic acid ester,
Other substituent groups are outer unless specified otherwise to be limited as preceding.
Reaction equation 1:
Reaction equation 2:
The compound of formula (I) can prepare in this way (reaction equation 1): solvent-free or in suitable solvent such as dichloromethane
In alkane, dichloroethanes, toluene, n,N-Dimethylformamide (DMF), tetrahydrofuran or dioxane etc., in -10~60 DEG C, In
In the presence of suitable alkali such as triethylamine, pyridine, sodium hydride, potassium hydroxide, potassium carbonate, sodium hydroxide or sodium carbonate, formula is used
(II) compound reacts to obtain formula (I) compound with the compound of formula (III).
The compound of formula (II) can prepare in this way (reaction equation 2): in water, ether, methyl tertiary butyl ether(MTBE), ethyl alcohol, two
The single solvent of chloromethanes, dichloroethanes, toluene, N,N-dimethylformamide (DMF), tetrahydrofuran or dioxane etc. is appointed
Both meanings in the mixed solvent, phase transfer catalyst such as tetrabutylammonium bromide and suitable alkali for example triethylamine, pyridine, sodium hydride,
In the presence of potassium hydroxide, potassium carbonate, sodium hydroxide or sodium carbonate etc. and sodium hydrosulfite, with compound and formula (V) of formula (IV)
Compound reacts to obtain formula (VI) compound；In suitable solvent such as toluene or dimethylbenzene, deposited in catalyst such as p-methyl benzenesulfonic acid
Under, under the conditions of return stirring divides water, formula (II) chemical combination is reacted to obtain with the compound of formula (VI) with the compound of formula (VII)
Object.
Specific synthetic method has more detailed elaboration in the following embodiments.
Formula (I) compound provided by the invention has broad-spectrum biological living under 15~2250 grams of effective components/hectare dosage
Property, it can be not only used for prevention and treatment disinfect pathogen, it may also be used for prevention and treatment harmful insect and harmful mite.Some compounds, which have to have well, falls ill
Bacterium preventive and therapeutic effect is obtained with good effect under very low dosage.
Formula (I) compound provided by the invention, with bioactivity and the compound that has has good bioactivity special
Be not agricultural, gardening, flowers and hygienic disinfect pathogen, evil insects mites prevention and treatment in terms of show activity.Nocuousness described here
Biology include but are not limited to this:
Harmful pathogen: Phytophthora type, white powder category type, Gibberella type, Venturia type, Sclerotinia kind
Class, Rhizoctonia type, Botrytis type, Pyricularia Sacc. type, Fusarium type, such as rice blast (Pyricularia
oryzae)；Stripe rust of wheat (Puccinia striiformis), leaf rust (Puccinia recondita) and other rust
Disease；Big wheat yellow rust (Puccinia striiformis), leaf rust (Puccinia recondita) and other rust；Barley
With wheat powdery mildew (Erysiphe graminis), powdery mildew of cucumber (Sphaerotheca fuligenea), apple mildew
(Podosphaera leucotrichar) and uncinula necator (Podosphaera leucotrichar)；Wheat sharp eyespot and
Glume blight (Septoria nodorum).The compacted spore of length on cereal, mouth spore is mould, Septoria is sick, caryosphere shell Pseudomonas disease,
Pseudocercosporella herpotrichoides and take-all (Gaeumannomyces graminis).Peanut
Brown spot (Cercospora arachidicola) and the cercospora black spot of peanut (Cercosporidium personata)；Apple wheel
Line germ (Botryosphaeria berengriana f.sp piricola), Valsa mali (Cytospora sp.)；
Its Cercospora disease on beet, soybean and paddy.Tomato, cucumber, grape grey mould (Botrytis cinerea).Vegetables
Hinge spore on (such as cucumber) belongs to disease.Anthracnose on cucumber, scab of apple, cucumber downy mildew, downy mildew of garpe, potato
With the epidemic disease on tomato, list bacterium Thanatephorus cucumeris and other hosts such as wheat and barley on paddy,
Other rhizoctonias on vegetables；Sclerotinia sclerotiorum (Sclerotonia sclerotiorum)；Wheat scab (Gibberella
zeae)；Phytoph-thora capsici leonian (Phytophythora capsici).
Harmful insect: Lepidoptera such as oriental armyworm, prodenia litura, diamondback moth, beet armyworm, cabbage looper, cabbage caterpillar, directly
Wing mesh such as blattaria, Thysanoptera such as cotton thrips, rice thrips, melon thrips, Homoptera such as leafhopper, plant hopper, aphid, Hymenoptera such as sawfly children
Worm, Diptera such as yellow-fever mosquito, culex, fly；Acarina such as Jie-Li enzyme-SQ, cotton spider mites, T.urticae Koch；
It is that effectively, they can also be with to control disinfect pathogen, evil insects mites when formula (I) compound of the present invention is used alone
It is used together with other biological chemical substance, these biochemicals include other insecticides, nematicide, acaricide and kill
Microbial inoculum.
With (I) compound provided by the invention, as the Agrotechnical formulation of effective ingredient, desired any one can be made
Such as dry compressed particle of kind of dosage form, Yi Liudong intermixture, granula, wettable powder, water dispersible granules, emulsifiable concentrate,
Pulvis, powdery concentrate, microemulsion, suspending agent, missible oil, aqueous emulsion, soluble liquid, aqua, dispersible agent, suitable helps
Agent includes carrier (diluent) and other adjuvants such as spreader-sticker, emulsifier, wetting agent, dispersing agent, sticker and distintegrant.This
Contain in a little preparations and is mixed with the compound of the present invention with the acceptable solid of inert, pharmacology or liquid diluent.
Such as dry compressed particle of desired any dosage form, Yi Liudong can also be made in composition example of the invention
Intermixture, granula, wettable powder, water dispersible granules, emulsifiable concentrate, pulvis, powdery concentrate, microemulsion, suspension
Agent, missible oil, aqueous emulsion, soluble liquid, aqua, dispersible agent, suitable auxiliary agent include carrier (diluent) and other auxiliary
Auxiliary agent such as spreader-sticker, emulsifier, wetting agent, dispersing agent, sticker and distintegrant.Containing with inert, pharmacology in these preparations
It learns acceptable solid or liquid diluent is mixed with the compound of the present invention.
The invention will be further described with reference to embodiments, and the yield in embodiment is not optimized, the present invention its
Its compound is referred to following embodiments and prepared by pertinent literature.
Specific embodiment
Embodiment 1 this example demonstrates that in table 1 compound 13 and 14 preparation method
3- methyl -4- hepta-fluoroiso-propyl aniline is under the cooling simultaneously stirring condition of ice-water bath, hepta-fluoroiso-propyl iodine
(0.10mol), m-toluidine (0.11mol), natrium carbonicum calcinatum (0.12mol), tetrabutylammonium bromide (catalytic amount), sodium hydrosulfite
After the mixture reaction 4-6h of (0.06mol), water (100mL) and methyl tertiary butyl ether(MTBE) (90mL), then sodium hydrosulfite is added portionwise
(0.06mol) and give free rein to temperature reaction stay overnight.Reaction mixture is poured into ice water, ethyl acetate extraction is washed organic
Layer, be concentrated under reduced pressure after anhydrous sodium sulfate is dry brown liquid title object 23.5g, be directly used in and react in next step.
The pure and mild 2,3,7- trimethyl -6- hepta-fluoroiso-propyl quinoline -4- of 2,3,5- trimethyl -6- hepta-fluoroiso-propyl quinoline -4-
3- methyl -4- hepta-fluoroiso-propyl aniline (0.03mol) is added in the there-necked flask equipped with magnetic stir bar and water segregator in alcohol, 2- first
Base methyl acetoacetate (0.06mol), p-methyl benzenesulfonic acid (0.03mol) and dimethylbenzene (150mL) divide under the conditions of being stirred at reflux
Cooling after water reacts 6-8h, the khaki solid 8.0g for filtering precipitation (is that 2,3,5- trimethyl -6-, seven fluorine is different through analyses such as MS
The mixture of pure and mild 2,3,7- trimethyl -6- hepta-fluoroiso-propyl quinoline -4- alcohol of propyl quinoline -4-), it is directly used in down without further purification
Single step reaction.
Carbonic acid cyclopenta (2,3,5- trimethyl -6- hepta-fluoroiso-propyl quinolyl-4) diester (13) and carbonic acid cyclopenta (2,
3,7- trimethyl -6- hepta-fluoroiso-propyl quinolyl-4s) diester (14) is under room temperature and stirring condition, to 2,3,5- trimethyl -6-
The mixture (4.0mmol) and hydrogen of the pure and mild 2,3,7- trimethyl -6- hepta-fluoroiso-propyl quinoline -4- alcohol of hepta-fluoroiso-propyl quinoline -4-
Change in n,N-Dimethylformamide (DMF, the 50mL) reaction mixture of sodium (60%, 7.5mmol) and chloroformate cyclopentyl ester is added dropwise
(4.6mmol) continues at room temperature reaction 2-4h after being added dropwise.Referring to 3- methyl -4- hepta-fluoroiso-propyl aniline synthesis example, to anti-
It answers mixture to carry out conventional post-processing, and column chromatographic purifying (V is carried out to crude productPetroleum ether/VEthyl acetate=50:1~20:1), respectively
Yellow liquid title object 13 and 14, total 0.95g are obtained, content is greater than 95.0%.
Embodiment 2 this example demonstrates that in table 1 compound 107 preparation method
Synthesis side of the 2- methyl -4- hepta-fluoroiso-propyl aniline referring to 3- methyl -4- hepta-fluoroiso-propyl aniline in embodiment 1
Method replaces m-toluidine with o-toluidine, can synthesize to obtain 2- methyl -4- hepta-fluoroiso-propyl aniline.
2,3,8- trimethyl -6- hepta-fluoroiso-propyl quinoline -4- alcohol is different referring to 2,3,7- trimethyl seven fluorine of -6- in embodiment 1
The synthetic method of propyl quinoline -4- alcohol replaces 3- methyl -4- hepta-fluoroiso-propyl aniline with 2- methyl -4- hepta-fluoroiso-propyl aniline,
It can synthesize to obtain 2,3,8- trimethyl -6- hepta-fluoroiso-propyl quinoline -4- alcohol.
Carbonic acid (tetrahydrofuran -3- base) (2,3,8- trimethyl -6- hepta-fluoroiso-propyl quinolyl-4) diester in room temperature and stirs
Under the conditions of mixing, to 2,3,8- trimethyl -6- hepta-fluoroiso-propyl quinoline -4- alcohol (8.0mmol) and sodium hydride (60%, 15mmol)
Chloro-carbonic acid tetrahydrofuran -3- base ester (9.0mmol) is added dropwise in n,N-Dimethylformamide (100mL) mixture, after being added dropwise
Continue at room temperature reaction 2-4h.Referring to embodiment 1, conventional post-processing is carried out to reaction mixture, and column layer is carried out to crude product
Analysis purifying (VPetroleum ether/VEthyl acetate=25:1), obtain yellow liquid title object 2.12g, content 95.2%.
Embodiment 3 this example demonstrates that in table 1 compound 110 preparation method
Synthesis of the 2,3- dimethyl -4- hepta-fluoroiso-propyl aniline referring to 3- methyl -4- hepta-fluoroiso-propyl aniline in embodiment 1
Method replaces m-toluidine with 2,3- dimethylaniline, can synthesize to obtain 2,3- dimethyl -4- hepta-fluoroiso-propyl aniline.
2,3,7,8- tetramethyl -6- hepta-fluoroiso-propyl quinoline -4- alcohol is referring to seven fluorine of 2,3,7- trimethyl -6- in embodiment 1
The synthetic method of isopropyl quinoline -4- alcohol replaces seven fluorine isopropyl of 3- methyl -4- with 2,3- dimethyl -4- hepta-fluoroiso-propyl aniline
Base aniline can synthesize to obtain 2,3,7,8- tetramethyl -6- hepta-fluoroiso-propyl quinoline -4- alcohol.
Carbonic acid (tetrahydrofuran -3- base) (2,3,7,8- tetramethyl -6- hepta-fluoroiso-propyl quinolyl-4) diester in room temperature simultaneously
Under stirring condition, to 2,3,7,8- trimethyl -6- hepta-fluoroiso-propyl quinoline -4- alcohol (8.0mmol) and sodium hydride (60%,
Chloro-carbonic acid tetrahydrofuran -3- base ester (9.0mmol) is added dropwise in n,N-Dimethylformamide (100mL) mixture 15mmol), drop
It adds and continues at room temperature reaction 2-4h after finishing.Referring to embodiment 1, conventional post-processing is carried out to reaction mixture, and to crude product
Carry out column chromatographic purifying (VPetroleum ether/VEthyl acetate=30:1~20:1), obtain yellow liquid title object 1.96g, content 95.8%.
Other compounds of the invention are referred to embodiment 1-3 and are synthesized, and when necessary, reference may also be made to coherent reference text
It offers.
4 carbonic acid of embodiment (tetrahydrofuran -3- base) (2,3,8- trimethyl -6- hepta-fluoroiso-propyl quinolyl-4) diester (table
Compound 107 in 1) 10% oil slick preparation
Weigh compound 107 in formula provided by the invention (I) compound such as table 1 of appropriate (by weight percentage 10%),
Suitable cosolvent (such as ethyl acetate or acetone), suitable pesticide auxiliaries and solvent (such as toluene) are put into reaction kettle, first
A certain amount of solvent (such as toluene) is added and defoaming agent stirs 10~30min, adds suitable stabilizer, synergist, penetrate
The components such as agent continue 10~30min of stirring, adjust pH value, then a effective amount of solvent is put into kettle, blowing is after mixing evenly
Obtain 10% missible oil of carbonic acid (tetrahydrofuran -3- base) (2,3,8- trimethyl -6- hepta-fluoroiso-propyl quinolyl-4) diester.
It is raw to survey embodiment
The compounds of this invention sterilize and has killed insects mites activity test, part of test results is as follows.
Bactericidal activity (pot-culture method) of the embodiment 5 to wheat powdery mildew (Erisiphe griminis)
Method is as follows: untested compound is dissolved in suitable solvent such as n,N-Dimethylformamide (DMF), then with containing 0.2%
The sterile water of Tween80 emulsifier is diluted to required concentration；The basin alms bowl of cut-off stem 15cm or so, every alms bowl sow the full stalwartness of wheat
20, seed, wait grow two leaves wholeheartedly afterwards be for experiment；Ready wheat seedling plant is taken to spray through certain density medicament
Mist processing, carries out germ inoculation after one day.3 repetitions of every processing, set the blank without untested compound separately as blank control, quotient
Product fungicide Fluoxastrobin is commercial References；After the onset of moisturizing thermophilic culture to blank control, lesion area is checked, calculate medicament
Preventive effect.Activity in percentage, is divided into A, B, C, D level Four relative to blank control, and 100%≤Fang Xiao≤90% is A grades, and 90%
> Fang Xiao≤70% is B grades, and 70% > Fang Xiao≤50% is C grades, and 50% > Fang Xiao≤0% is D grades.The result shows that of the invention
Compound has control efficiency to wheat powdery mildew, and the compound having still has good effect at very low concentrations.For
Compare the compounds of this invention and K2 (Tebufloquin) compound represented to the activity height of wheat powdery mildew, selection is originally
Invention compound 13,107 etc. is representative, is that control is tested with K2, the results showed that the compounds of this invention 107 etc. are to white wheat
The activity of powder disease is much better than K2 to the activity of wheat powdery mildew.Partial results are as follows:
Under 500mg/L concentration, the compounds of this invention 11,12,13,82,106,107,108,110,177,195,196,
197, compound shown in 207 etc. and K2 (Tebufloquin) has A grades of prevention and treatment activity to wheat powdery mildew；
Under 100mg/L concentration, the compounds of this invention 11,12,13,82,106,107,108,110,177 and 207 etc. is to small
Wheat powdery mildew has A grades of prevention and treatment activity；
Under 25mg/L concentration, the compounds of this invention 13,106,107 and 108 etc. there are A grades of prevention and treatments to live wheat powdery mildew
Property；
Further to compare the compounds of this invention and K2 to the activity height of wheat powdery mildew, the compounds of this invention is selected
13,106,107 and 108 etc. be representative, is that control has carried out deep screening with K2 and commercialization fungicide Flusilazole, the results showed that
The compounds of this invention is much better than K2 to the activity of wheat powdery mildew, is in same level with Flusilazole.Such as the compounds of this invention
107,108 and Flusilazole to the EC of wheat powdery mildew50Value is in 1~2mg/L, 13 and 106 etc. to the EC of wheat powdery mildew50Value <
5mg/L, and EC of the K2 to wheat powdery mildew under similarity condition50Value > 5mg/L.
Insecticidal Activity of the embodiment 6 to aphid (Aphis fabae)
It is evaluation the compounds of this invention to the activity of homoptera pest, selects aphid for object, use infusion process indoors
The compounds of this invention is determined to the activity of aphid.
Infusion process: untested compound is dissolved in suitable solvent such as n,N-Dimethylformamide (DMF), then with containing 0.2%
The clear water of Tween80 emulsifier is diluted to required concentration, if the blank without untested compound is control, 3 repetitions of every processing.
Black bean aphid is connected on just unearthed bean seedlings, every plant connects 20 or more, and bean seedlings are then dipped in the present invention together with test worm and are mentioned
In formula (I) medical fluid of confession, is taken out after 5 seconds, suck extra medical fluid, be inserted into the sponge of water suction, covered with glass-tube, after 24 hours
Check survival and dead borer population, results are averaged.Active (death rate) in percentage with respect to blank control, be divided into A, B, C,
D level Four, 100 >=death rate (%) >=90 are A grades, and 90 > death rate (%) >=70 is B grades, and 70 > death rate (%) >=50 is C grades,
50 > death rate (%) >=0 is D grades.The result shows that the compounds of this invention has activity well to aphid, and the compound having exists
Still there is high activity under lower concentration, partial results are listed below:
Under 500mg/L concentration, the compounds of this invention 11,12,13,107,108,110,114 and 177 etc. has A to aphid
Grade activity；
Under 200mg/L concentration, the compounds of this invention 11,12,13 and 107 etc. has A grades of activity to aphid；
Under 50mg/L concentration, the compounds of this invention 107,110 and 114 etc. is active with A grades to aphid, under similarity condition,
Compound shown in formula K2 (Tebufloquin) is to the active less than 30% of aphid.
Under 12.5mg/L concentration, the compounds of this invention 110 is equal active with 60% or more C grade to aphid.
Embodiment 7 evaluates the acaricidal activity of two-spotted spider mite (Tetranychus urticae)
Method: untested compound is dissolved in suitable solvent such as n,N-Dimethylformamide (DMF), then with containing 0.2%
The water of Tween80 emulsifier is diluted to required concentration, if the blank without untested compound is blank control, 3 weights of every processing
It is multiple；Select the bean seedlings to grow fine inoculation red spider that will cut with mite bean seedlings after red spider colonizes in the prepared present invention
It being impregnated 10 seconds in the medical fluid of formula (I) compound of offer, taking-up sucks extra medical fluid with filter paper, and it inserts in and is filled with water in beaker, in
It is cultivated in observation ward, survival and dead mite number is checked after 48 hours, has 100-200 mite on every plant of bean seedlings.Results are averaged.
Simultaneously using K2 as standard control.Active (death rate) in percentage, is divided into A, B, C, D level Four relative to blank control, 100 >=
The death rate (%) >=90 is A grades, and 90 > death rate (%) >=70 is B grades, and 70 > death rate (%) >=50 is C grades, 50 > death rate
(%) >=0 is D grades.The result shows that the compounds of this invention has preferable activity to red spider.Such as under 500mg/L concentration, this
Invention compound 108 and 114 etc. is active with A grades to red spider, under similarity condition, formula K2 compound represented
It (Tebufloquin) is the C grade activity less than 70% to the activity of red spider.
Biological evaluation of the embodiment 8 to mythimna separata (Mythimna separata)
Potter spray-on process: appropriate the compounds of this invention is weighed, is dissolved with n,N-Dimethylformamide, adds and spits on a small quantity
Warm 80 emulsifiers, stir evenly, and quantitative clear water is added, is configured to required concentration, if clear water is control.Fresh and tender maize leaves are taken to cut
At the almost the same segment of size, it is put into and is lined in the culture dish (Ф 90mm) of filter paper in advance.Then 3 age of mythimna separata is accessed in ware
It larva 10, is put under Potter spray tower and carries out metered dose, spray liquid measure 1ml, 3 repetitions of every concentration.It is disposed, covers
Upper ware lid is placed in culture, routine observation in recovery room, test worm death condition is checked and recorded after 72 hours, calculates the death rate
(%), results are averaged.Activity in percentage, is divided into A, B, C, D level Four, 100 >=death rate relative to blank control
(%) >=90 is A grades, and 90 > death rate (%) >=70 is B grades, and 70 > death rate (%) >=50 is C grades, 50 > death rate (%) >=0
It is D grades.The result shows that the compounds of this invention has preferable activity to mythimna separata.Such as under 500mg/L concentration, the compounds of this invention
110 is equal active with A grades to mythimna separata, and under similarity condition, K2 compound represented (Tebufloquin) is 0 to the activity of mythimna separata.
Claims (7)
1. hepta-fluoroiso-propyl quinolines, it is characterised in that indicated with logical formula (I):
Wherein:
I.R1COR, propargyl or allyl are represented, wherein R represents cyclopentyloxy, tetrahydrofuran -3- base oxygroup or tetrahydro furan
It mutters -2- base oxygroup；And hydrogen moiety or it can all be replaced by identical or different substituent group in following in allyl:
Halogen, C1-C6Alkyl, C1-C6Halogenated alkyl；
II.R2And R3, R4, R5, R6It is same or different, and represents hydrogen or C1-C6Alkyl；
In the definition of compound (I) given above, no matter term used exclusive use is also used in compound word, represent as follows
Substituent group:
Halogen: refer to fluorine, chlorine, bromine, iodine；
Alkyl: refer to linear or branched alkyl group；
It is halogenated: to refer to hydrogen moiety therein or all replaced by halogen atom.
2. hepta-fluoroiso-propyl quinolines according to claim 1, it is characterised in that logical formula (I) compound is:
3. the preparation method of hepta-fluoroiso-propyl quinolines according to claim 1, it is characterised in that shown in formula (I)
Compound be prepared by reaction shown below,
Reaction equation 1:
Reaction equation 2:
In methylene chloride, dichloroethanes, toluene, dimethylbenzene, N,N-dimethylformamide, tetrahydrofuran or dioxane
In, in -10~60 DEG C, in the presence of alkali triethylamine, pyridine, sodium hydride, potassium hydroxide, potassium carbonate, sodium hydroxide or sodium carbonate,
Formula (I) compound is reacted to obtain with the compound of formula (II) with the compound of formula (III)；
In solvent toluene, chlorobenzene or dimethylbenzene, in the presence of catalyst benzene sulfonic acid or p-methyl benzenesulfonic acid, in reflux water-dividing condition
Under, formula (II) compound is reacted to obtain with the compound of formula (IV) with the compound of formula (V)；
R in formula1、R2、R3、R4、R5And R6With defining given in claim 1, L is leaving group chlorine, bromine or iodine.
4. the purposes of hepta-fluoroiso-propyl quinolines according to claim 1 or 2, it is characterised in that 15~5000
There is sterilization and/or desinsection, mite killing bioactivity under gram effective component/hectare dosage.
5. hepta-fluoroiso-propyl quinolines according to claim 1 or 2 be used to prepare with sterilization and/or desinsection,
The purposes of the drug of acaricidal activity.
6. a kind of sterilization or Pesticidal combination, it is characterised in that: containing as the as claimed in claim 1 or 2 of active component
Hepta-fluoroiso-propyl quinolines, the weight percentage of active component is 0.5-99% in composition.
7. a kind of method of anti-pathogen or evil insects mites, it is characterised in that: by a effective amount of as claimed in claim 1 or 2 seven
Fluorine isopropyl quinoline class compound imposes on the germ, evil insects mites or its somatomedin.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034717A (en) * | 1988-01-29 | 1989-08-16 | 伊莱利利公司 | The quinoline and the cinnolines that replace |
| CN1444562A (en) * | 2000-05-30 | 2003-09-24 | 明治制果株式会社 | Rice blast control agents |
| CN104628639A (en) * | 2013-11-13 | 2015-05-20 | 浙江省化工研究院有限公司 | Heptafluoroisopropyl quinoline compounds as well as preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1034717A (en) * | 1988-01-29 | 1989-08-16 | 伊莱利利公司 | The quinoline and the cinnolines that replace |
| CN1444562A (en) * | 2000-05-30 | 2003-09-24 | 明治制果株式会社 | Rice blast control agents |
| CN104628639A (en) * | 2013-11-13 | 2015-05-20 | 浙江省化工研究院有限公司 | Heptafluoroisopropyl quinoline compounds as well as preparation method and application thereof |
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