CN105622422B - A kind of bromo hexahydro indanone compounds and its production and use - Google Patents
A kind of bromo hexahydro indanone compounds and its production and use Download PDFInfo
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- C07C67/307—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
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Abstract
The invention provides a kind of halo hexahydro indanone compounds and its production and use, and the present invention relates to bromo hexahydro indanone compounds, and they have the chemical structure of general formula as shown in I.
Description
Technical field
Technical scheme is related to the hexahydro indanone compounds of halogen atom-containing, and in particular to bromo hexahydro indone
Class compound.
Background technology
Halogen has unique physicochemical property, therefore, brings halogen-containing compound to have unique bioactivity, different
Due to its atomic radius and the difference of electronegativity between halogen atom, different halide also have different physicochemical properties and
Bioactivity.In pesticide species, chloro thing and bromo-derivative and iodo thing are respectively provided with different bioactivity, for example, by alkene
Two isomers of flumorph after Cl atoms in morpholide are substituted with F atom are respectively provided with good bactericidal activity, and alkene acyl
Morpholine then only has an isomers to have bactericidal activity.This seminar is by the 4- methyl isophthalic acids with inducing anti-disease activity, 2,3- thiophenes
4- bromomethyls -1,2 that methyl H in diazole -5- Ethyl formates is generated after being substituted with Br atoms, 3- thiadiazoles -5- Ethyl formates
Then there is good bactericidal activity.
Indanone compounds are the important intermediates of organic synthesis, such as 2- acetoxyl groups indenone can be used for organic conjunction
Into, and the structure of indone is widely present and in the bioactive molecule such as natural products and medicine and agricultural chemicals, it is in organic light emission
With in photochromic and fuel and important construction unit.
Halogen atom is introduced into hexahydro indone guide structure using the principle of pesticide molecule design and is designed synthesis by the present invention
A kind of halo hexahydro indanone compounds, and the bioactivity screening of system has been carried out, to being provided for the initiative of novel pesticide
More efficient candidate compounds.
The content of the invention
The technical problems to be solved by the invention are：The synthetic method of new bromo hexahydro indanone compounds is provided, carried
For this kind of compound modulates agricultural, gardening and health and the bioactivity and its measure of forestry plant insect and the phytopathy original
Method, while middle application of these compounds in agriculture field, horticultural field, field of forestry and health field is provided.
Technical scheme is used by the present invention solves the technical problem：With agriculture field, horticultural field, forestry and
Health field insecticidal activity, bactericidal activity, the general structure of bromo hexahydro indanone compounds of anti-phytoviral activity are I：
Wherein, R1Selected from phenyl, 2- aminomethyl phenyls, 3- aminomethyl phenyls, 4- aminomethyl phenyls, 2- methoxyphenyls, 3- methoxies
Base phenyl, 4- methoxyphenyls, 2- chlorphenyls, 3- chlorphenyls, 4- chlorphenyls, 2- fluorophenyls, 3- fluorophenyls, 4- fluorophenyls, 2-
Trifluoromethyl, 3- trifluoromethyls, 4- trifluoromethyls, 2- nitrobenzophenones, 3- nitrobenzophenones, 4- nitrobenzophenones,
4- ethylphenyls, 4- methyl isophthalic acids, 2,3- thiadiazolyl groups, 2- furyls, 2- methyl -2- (4- chlorphenyls) -1- propyl group, three chloromethanes
Base, chrysanthemum acyl group, dichloro chrysanthemum acyl group, 4- fluorobenzene ethyl, 2,6- dichlorophenyls, methyl, propyl group, heptyl, 3,5- dichlorophenyls, 3,5-
Dimethyl, 3- (2- chlorphenyls) -5- methyl-isoxazole -4- bases, 2,4- dimethyl -1- phenyl give a tongue-lashing azoles -3- bases, cyclohexyl, 2- fluorine
Phenethyl, 3,6- dichloros give a tongue-lashing pyridine -2- bases, 5- ethyl -1- methylpyrazole -3- bases, the group of 2- fluorobenzene ethyls, 4- methyl isophthalic acids, and 2,
3- thiadiazoles -5- bases, 5- methyl isophthalic acids, 2,3- thiadiazoles -4- bases, the chloroisothiazole -5- bases of 3,4- bis-；X is selected from F, Cl, Br, I；X1
Selected from F, Cl, Br, I；X2Selected from F, Cl, Br, I；NXS is selected from N- bromo-succinimides, N- chlorosuccinimides.
The bromo hexahydro indanone compounds I of present invention synthetic method is as follows：
Wherein, R1Selected from phenyl, 2- aminomethyl phenyls, 3- aminomethyl phenyls, 4- aminomethyl phenyls, 2- methoxyphenyls, 3- methoxies
Base phenyl, 4- methoxyphenyls, 2- chlorphenyls, 3- chlorphenyls, 4- chlorphenyls, 2- fluorophenyls, 3- fluorophenyls, 4- fluorophenyls, 2-
Trifluoromethyl, 3- trifluoromethyls, 4- trifluoromethyls, 2- nitrobenzophenones, 3- nitrobenzophenones, 4- nitrobenzophenones,
4- ethylphenyls, 4- methyl isophthalic acids, 2,3- thiadiazolyl groups, 2- furyls, 2- methyl -2- (4- chlorphenyls) -1- propyl group, three chloromethanes
Base, chrysanthemum acyl group, dichloro chrysanthemum acyl group, 4- fluorobenzene ethyl, 2,6- dichlorophenyls, methyl, propyl group, heptyl, 3,5- dichlorophenyls, 3,5-
Dimethyl, 3- (2- chlorphenyls) -5- methyl-isoxazole -4- bases, 2,4- dimethyl -1- phenyl give a tongue-lashing azoles -3- bases, cyclohexyl, 2- fluorine
Phenethyl, 3,6- dichloropyridine -2- bases, 5- ethyl -1- methylpyrazole -3- bases, the group of 2- fluorobenzene ethyls, 4- methyl isophthalic acids, 2,
3- thiadiazoles -5- bases, 5- methyl isophthalic acids, 2,3- thiadiazoles -4- bases, the chloroisothiazole -5- bases of 3,4- bis-；X is selected from F, Cl, Br, I；X1
Selected from F, Cl, Br, I；X2Selected from F, Cl, Br, I；NXS is selected from N- bromo-succinimides, N- chlorosuccinimides.
It is specifically divided into following steps：
A. compound III preparation：
3.2 mMs of compound II is added in 100 milliliters of two-mouth bottles, vacuumized, injection nitrogen protection, is then added
25 milliliters of dry tetrahydrofuran solutions, 3.5 mMs of vinyl magnesium bromides are slowly added dropwise into reaction bulb under ice salt bath, are added dropwise
After, ice salt bath stirs 20 minutes, removes ice bath, is stirred at room temperature 2 hours, and after reaction completely, reaction solution adds 20 milliliters and satisfied
Be quenched with sodium bicarbonate solution, ethyl acetate extraction, isolate ethyl acetate layer, ethyl acetate phase again with saturated sodium bicarbonate and
Saturated sodium-chloride is respectively dried after washing one time through anhydrous magnesium sulfate, is filtered, concentration, removal of solvent under reduced pressure, residue through 200~
300 mesh silica gel column chromatographies purify to obtain compound III, and eluant, eluent is that volume ratio is ethyl acetate: the stone of 60~90 degrees Celsius of cuts
Oily ether=6: 1 mixed liquor；With gained sterling calculated yield, yield 70%；Amount and the body of reaction vessel prepared by compound III
Product is expanded or shunk by corresponding proportion.
B. compound IV preparation：
0.76 mM of compound III is dissolved in 20 milliliters of dry tetrahydrofuran solutions, then adds 2.27 mmoles
Your sodium borohydride, the tetrahydrofuran solution of 3.04 mMs of BFEEs, after being added dropwise, ice bath are slowly added dropwise under ice bath
Stirring removes ice bath in 15 minutes again, is then stirred at room temperature 2 hours, is slowly added dropwise after stopping reaction under ice bath into reaction bulb
4.6 mMs of Jones reagents, continue stirring 2 hours in room temperature after being added dropwise, after reaction completely, add 20 milliliters of water, use
Ethyl acetate extracts, and isolates ethyl acetate layer, ethyl acetate phase is again with the respectively washing one of saturated sodium bicarbonate and saturated sodium-chloride
Time, ethyl acetate phase is dried through anhydrous magnesium sulfate, is filtered, concentration, and after removal of solvent under reduced pressure, residue is through 200~300 mesh silica gel
Column chromatography purifies to obtain compound IV, and eluant, eluent volume ratio is ethyl acetate: petroleum ether=4 of 60~90 degrees Celsius of cuts: 1 it is mixed
Close liquid；With gained sterling calculated yield, yield 45%；Amount and the volume of reaction vessel prepared by compound IV is expanded by corresponding proportion
Big or diminution.
C. compound V preparation：
1.9 mMs of compound IV are dissolved in the mixed solution that 15 milliliters of volume ratios are tetrahydrofuran and water is 10: 1,
2 mMs of sodium borohydrides are added portionwise under ice bath into reaction solution, after addition, remove ice bath, are stirred at room temperature 1 hour, instead
15 milliliters of saturated sodium bicarbonates should be added afterwards completely to be quenched, be extracted with ethyl acetate, isolate ethyl acetate layer, ethyl acetate phase
Again with respectively washing one time of saturated sodium bicarbonate and saturated sodium-chloride, ethyl acetate phase is dried through anhydrous magnesium sulfate, is filtered, concentration,
After removal of solvent under reduced pressure, residue purifies to obtain compound V through 200~300 mesh silica gel column chromatographies, and eluant, eluent is that volume ratio is acetic acid
Ethyl ester: petroleum ether=3 of 60~90 degrees Celsius of cuts: 1 mixed liquor；With gained sterling calculated yield, yield 68%；Compound
Amount and the volume of reaction vessel prepared by V is expanded or shunk by corresponding proportion.
D. compound VI preparation：
By 3.5 mMs of compound V be dissolved in 25 milliliters again steam after dichloromethane in, vacuumize, injection nitrogen protection, ice
14 mMs of triethylamine is added under bath into reaction bulb, acyl chlorides R is then slowly added dropwise1COCl, after being added dropwise, remove ice
Bath, is stirred overnight at room temperature, and 20 milliliters of saturated sodium bicarbonate solution extractions are added after reacting completely, separate dichloromethane layer, dichloro
Methane mutually again with respectively washing one time of saturated sodium bicarbonate and saturated sodium-chloride, mutually through anhydrous magnesium sulfate dry, and filters by dichloromethane,
Concentrate, after removal of solvent under reduced pressure, residue purifies to obtain compound VI through 200~300 mesh silica gel column chromatographies, and eluant, eluent is volume ratio
It is ethyl acetate: petroleum ether=8 of 60~90 degrees Celsius of cuts: 1 mixed liquor；With gained sterling calculated yield, yield 90%；
Amount and the volume of reaction vessel prepared by compound VI is expanded or shunk by corresponding proportion.
E. compound VII preparation：
0.7 mM of compound VI is dissolved in 6 milliliters of methanesulfonic acids, then add 0.01 mM of phosphorus pentoxide with
35-40 degrees Centigrades react 6 hours, add 20 milliliters of water after reacting completely, are extracted with ethyl acetate, isolate ethyl acetate
Layer, ethyl acetate phase again with respectively washing one time of saturated sodium bicarbonate and saturated sodium-chloride, through anhydrous magnesium sulfate do by ethyl acetate phase
It is dry, filter, concentration, after removal of solvent under reduced pressure, residue purifies to obtain compound VII through 200~300 mesh silica gel column chromatographies, elution
Agent is that volume ratio is ethyl acetate: petroleum ether=8 of 60~90 degrees Celsius of cuts: 1 mixed liquor；Calculated and received with gained sterling
Rate, yield 60%；Amount and the volume of reaction vessel prepared by compound VII is expanded or shunk by corresponding proportion.
F. compound I preparation：
Work as R1For Ph, X1For Br, X2For H when, compound I preparation method is as follows：
7 mMs of compound VII are dissolved in dry carbon tetrachloride, then sequentially add 7.7 mMs of N- bromo fourths
Imidodicarbonic diamide, 0.07 mM of azodiisobutyronitrile, in the reaction of 50 degrees Centigrades overnight, after reaction completely, filter, concentration,
Removal of solvent under reduced pressure, residue purify to obtain compound I through 200~300 mesh silica gel column chromatographies, and eluant, eluent is that volume ratio is acetic acid second
Ester: petroleum ether=10 of 60~90 degrees Celsius of cuts: 1 mixed liquor；With gained sterling calculated yield, yield 50%；With N- chlorine
Corresponding chloro thing can be prepared by substituting N- bromo-succinimides for succimide；Amount and reaction prepared by compound I is held
The volume of device is expanded or shunk by corresponding proportion.
Work as R1For Ph, X1For H, X2For Br when, compound I preparation method is as follows：
0.4 mM of compound VII is dissolved in 15 milliliters of dry acetonitriles, then sequentially adds 0.44 mM of N- bromine
For succimide, 0.02 mmoles Trimethylsilyl trifluoromethanesulfonate, after addition, it is stirred overnight at room temperature, after reaction completely
20 milliliters of saturated sodium bicarbonate solution extractions are added, is extracted with ethyl acetate, isolates ethyl acetate layer, ethyl acetate phase is used again
Saturated sodium bicarbonate and saturated sodium-chloride respectively washing one time, ethyl acetate phase is dried through anhydrous magnesium sulfate, is filtered, and is concentrated, decompression
After removing solvent, residue purifies to obtain compound I through 200~300 mesh silica gel column chromatographies, and eluant, eluent is that volume ratio is ethyl acetate
: petroleum ether=10 of 60~90 degrees Celsius of cuts: 1 mixed liquor；With gained sterling calculated yield, yield 46%；With N- chloros
Succimide, which substitutes N- bromo-succinimides, can prepare corresponding chloro thing；Amount and reaction vessel prepared by compound I
Volume expanded or shunk by corresponding proportion.
G. bromo hexahydro indanone compounds I of the invention bactericidal activity measure：
The bromo hexahydro indanone compounds I of present invention sterilization or bacteriostatic activity use thalli growth rate determination method, have
Body step is：Take 1.8 milligrams of samples to be dissolved in 2 drop DMFs, be i.e. in DMF, then told with containing a certain amount of
The aqueous solution of warm 20 emulsifying agents is diluted to the medicament of 500 mcg/mls, and reagent agent is aseptically respectively drawn into 1 milliliter
In in culture dish, then 9 milliliters of PDA culture mediums are separately added into, 50 mcg/ml drug containing flat boards are made after shaking up, with 1 milliliter of addition
The flat board of aqua sterilisa does blank control, cuts bacterium disk along mycelia outer rim with 4 millimeters of card punch of diameter, moves on drug containing flat board,
Put in equilateral triangle, often processing is repeated 3 times, and culture dish is placed in 24 ± 1 degrees Celsius of constant incubators and cultivated, waits to compare
Colony diameter investigates each processing bacterium disk extension diameter after expanding to 2-3 centimetres, average, calculated compared with blank control relative
Bacteriostasis rate, for the kind that examination strain is most of typical plant pathogen that field actually occurs in China's agricultural production, its generation
Number and title it is as follows：AS：Tomato early blight bacterium, its Latin are entitled：Alternaria solani、BC：Botrytis cinerea pers, its
Latin is entitled：Botrytis cinerea、CA：Peanut Cercospora bacteria, its Latin are entitled：Cercospora arachidicola、
GZ：Fusarium graminearum, its Latin are entitled：Gibberella zeae、PI：Phytophthora infestans, its Latin are entitled：
Phytophthora infestans(Mont.)de Bary、PP：Botryosphaeria berengeriana f. sp, its Latin are entitled：Physalospora
piricola、PS：Rhizoctonia solani Kuhn, its Latin are entitled：Pellicularia sasakii、RC：Rhizoctonia cerealis, its Latin
It is entitled：Rhizoctonia cerealis、SS：Sclerotinia sclerotiorum, its Latin are entitled：Sclerotinia
sclerotiorum。
H. the measure of bromo hexahydro indanone compounds I of the invention to aphid cytotoxicity：
The bromo hexahydro indanone compounds I of the present invention uses infusion process to the measure of aphid cytotoxicity, and black bean aphid is
The normal population of indoor feeding, the entitled Aphis laburni Kaltenbach (ALK) of Latin；Weigh the milli of test compound 2.5
Gram in beaker, 1 drop DMF is added dropwise, be i.e. DMF, adds 5 milliliters of acetone vibration dissolving samples, has added tween
80 water is made into the solution to be measured of 200 mcg/mls；The bean plant that supplies to try with least 30 black bean aphids is cut from basin
Under, impregnated 5 seconds in each decoction to be measured, unnecessary decoction is gently got rid of in taking-up, is inserted in and is protected on water saturated sponge
It is wet, escaped, cultivated to prevent aphid with cloche cover, the opening of cloche upper end is sealed with gauze after decoction natural air drying
Indoor feeding checks aphid death state after 72 hours, standard is：It can be creeped or can stood or six legs can be transported acutely with test worm
It is dynamic to be considered as worm living；Corrected mortality is calculated by control of clear water.
I. bromo hexahydro indanone compounds I of the invention inducing anti-disease activity measure：
The screening technique of the bromo hexahydro indanone compounds I evoking tobacco activity of resisting tobacco mosaic virus of the present invention is such as
Under, tobacco mosaic virus (TMV) is abbreviated as TMV：
(1) positive controls activating plants agent：It is positive control to select tiadinil of the quality purity purity more than 99.5%
Activating plants agent；S- methyl benzo [1,2,3] thiadiazoles -7- carbothioic acid esters are abbreviated as BTH；
(2) screening technique of the anti-TMV activity of bromos hexahydro indanone compounds I evoking tobacco：It is in vitro directly antiviral
The measure of activity is carried out using half leaf method；Live body induction is that 3 basins are one group, before inoculation by the consistent common cigarette of seedling age
The tobacco seedlings of 7d pre-treatments, processing mode include：Spray test compounds solution 2 to 3 times, 10 milliliters every time, or soil treatment,
10 milliliters every time, measure concentration is 50 mcg/mls, in frictional inoculation TMV on the tobacco leaf newly grown, tobacco seedlings is placed within the 7th day
After being cultivated 3 days under its growth preference temperature and illumination, incidence is checked, comprehensive scab number is calculated as follows out for examination chemical combination
Induction antiviral effect of the thing to TMV, each processing set 3 repetitions, blank control and standard agent control select respectively water and
BTH：
Wherein, R be test compound TMV anti-to tobacco inducing effect, unit：%；CK is that clear water compares the flat of blade
Equal withered spot number, unit：It is individual；I is that the average withered spot number for handling rear blade is induced through test compound, unit：It is individual；
In addition to carrying out the measure of above-mentioned induced activity, while carry out target compound I anti-TMV therapeutic activities, passivation
The measure of activity and protection activity.
The beneficial effects of the invention are as follows：Guide's optimization has been carried out to bromo hexahydro indanone compounds I, and to the new of synthesis
Compound carries out the screening of insecticidal activity, bacteriostatic activity, antiviral activity.
The present invention passes through specific preparation and the more specific explanation bromo hexahydro indone class chemical combination of biological activity determination embodiment
Thing I synthesis and bioactivity and application, the embodiment, which is only used for illustrating the present invention, to be not intended to limit the present invention, especially
Bioactivity is merely illustrative of, and unrestricted this patent, embodiment are as follows：
Embodiment 1
Compound III preparation：
3.2 mMs of compound II is added in 100 milliliters of two-mouth bottles, vacuumized, injection nitrogen protection, is then added
25 milliliters of dry tetrahydrofuran solutions, 3.5 mMs of vinyl magnesium bromides are slowly added dropwise into reaction bulb under ice salt bath, are added dropwise
After, ice salt bath stirs 20 minutes, removes ice bath, is stirred at room temperature 2 hours, and after reaction completely, reaction solution adds 20 milliliters and satisfied
Be quenched with sodium bicarbonate solution, ethyl acetate extraction, isolate ethyl acetate layer, ethyl acetate phase again with saturated sodium bicarbonate and
Saturated sodium-chloride is respectively dried after washing one time through anhydrous magnesium sulfate, is filtered, concentration, removal of solvent under reduced pressure, residue through 200~
300 mesh silica gel column chromatographies purify to obtain compound III, and eluant, eluent is that volume ratio is ethyl acetate: the stone of 60~90 degrees Celsius of cuts
Oily ether=6: 1 mixed liquor；With gained sterling calculated yield, yield 70%；Compound III physical and chemical parameter and structural parameters is shown in
Table 1；Amount and the volume of reaction vessel prepared by compound III is expanded or shunk by corresponding proportion.
Embodiment 2
Compound IV preparation：
0.76 mM of compound III is dissolved in 20 milliliters of dry tetrahydrofuran solutions, then adds 2.27 mmoles
Your sodium borohydride, the tetrahydrofuran solution of 3.04 mMs of BFEEs, after being added dropwise, ice bath are slowly added dropwise under ice bath
Stirring removes ice bath in 15 minutes again, is then stirred at room temperature 2 hours, is slowly added dropwise after stopping reaction under ice bath into reaction bulb
4.6 mMs of Jones reagents, continue stirring 2 hours in room temperature after being added dropwise, after reaction completely, add 20 milliliters of water, use
Ethyl acetate extracts, and isolates ethyl acetate layer, ethyl acetate phase is again with the respectively washing one of saturated sodium bicarbonate and saturated sodium-chloride
Time, ethyl acetate phase is dried through anhydrous magnesium sulfate, is filtered, concentration, and after removal of solvent under reduced pressure, residue is through 200~300 mesh silica gel
Column chromatography purifies to obtain compound IV, and eluant, eluent volume ratio is ethyl acetate: petroleum ether=4 of 60~90 degrees Celsius of cuts: 1 it is mixed
Close liquid；With gained sterling calculated yield, yield 45%；Compound IV physical and chemical parameter and structural parameters is shown in Table 1；Compound IV systems
Standby amount and the volume of reaction vessel are expanded or shunk by corresponding proportion.
Embodiment 3
Compound V preparation：
1.9 mMs of compound IV are dissolved in the mixed solution that 15 milliliters of volume ratios are tetrahydrofuran and water is 10: 1,
2 mMs of sodium borohydrides are added portionwise under ice bath into reaction solution, after addition, remove ice bath, are stirred at room temperature 1 hour, instead
15 milliliters of saturated sodium bicarbonates should be added afterwards completely to be quenched, be extracted with ethyl acetate, isolate ethyl acetate layer, ethyl acetate phase
Again with respectively washing one time of saturated sodium bicarbonate and saturated sodium-chloride, ethyl acetate phase is dried through anhydrous magnesium sulfate, is filtered, concentration,
After removal of solvent under reduced pressure, residue purifies to obtain compound V through 200~300 mesh silica gel column chromatographies, and eluant, eluent is that volume ratio is acetic acid
Ethyl ester: petroleum ether=3 of 60~90 degrees Celsius of cuts: 1 mixed liquor；With gained sterling calculated yield, yield 68%；Compound
V physical and chemical parameter and structural parameters is shown in Table 1；Amount and the volume of reaction vessel prepared by compound V is expanded or contracted by corresponding proportion
It is small.
Embodiment 4
Compound VI preparation：
By 3.5 mMs of compound V be dissolved in 25 milliliters again steam after dichloromethane in, vacuumize, injection nitrogen protection, ice
14 mMs of triethylamine is added under bath into reaction bulb, acyl chlorides R is then slowly added dropwise1COCl, after being added dropwise, remove ice
Bath, is stirred overnight at room temperature, and 20 milliliters of saturated sodium bicarbonate solution extractions are added after reacting completely, separate dichloromethane layer, dichloro
Methane mutually again with respectively washing one time of saturated sodium bicarbonate and saturated sodium-chloride, mutually through anhydrous magnesium sulfate dry, and filters by dichloromethane,
Concentrate, after removal of solvent under reduced pressure, residue purifies to obtain compound VI through 200~300 mesh silica gel column chromatographies, and eluant, eluent is volume ratio
It is ethyl acetate: petroleum ether=8 of 60~90 degrees Celsius of cuts: 1 mixed liquor；With gained sterling calculated yield, yield 90%；
Compound VI physical and chemical parameter and structural parameters is shown in Table 1；Amount and the volume of reaction vessel prepared by compound VI presses corresponding proportion
Expand or shrink.
Embodiment 5
Compound VII preparation：
0.7 mM of compound VI is dissolved in 6 milliliters of methanesulfonic acids, then add 0.01 mM of phosphorus pentoxide with
35-40 degrees Centigrades react 6 hours, add 20 milliliters of water after reacting completely, are extracted with ethyl acetate, isolate ethyl acetate
Layer, ethyl acetate phase again with respectively washing one time of saturated sodium bicarbonate and saturated sodium-chloride, through anhydrous magnesium sulfate do by ethyl acetate phase
It is dry, filter, concentration, after removal of solvent under reduced pressure, residue purifies to obtain compound VII through 200~300 mesh silica gel column chromatographies, elution
Agent is that volume ratio is ethyl acetate: petroleum ether=8 of 60~90 degrees Celsius of cuts: 1 mixed liquor；Calculated and received with gained sterling
Rate, yield 60%；Compound VII physical and chemical parameter and structural parameters is shown in Table 1；Amount and reaction vessel prepared by compound VII
Volume is expanded or shunk by corresponding proportion.
Embodiment 6
Compound I preparation：
Work as R1For Ph, X1For Br, X2For H when, compound I preparation method is as follows：
7 mMs of compound VII are dissolved in dry carbon tetrachloride, then sequentially add 7.7 mMs of N- bromo fourths
Imidodicarbonic diamide, 0.07 mM of azodiisobutyronitrile, in the reaction of 50 degrees Centigrades overnight, after reaction completely, filter, concentration,
Removal of solvent under reduced pressure, residue purify to obtain compound I through 200~300 mesh silica gel column chromatographies, and eluant, eluent is that volume ratio is acetic acid second
Ester: petroleum ether=10 of 60~90 degrees Celsius of cuts: 1 mixed liquor；With gained sterling calculated yield, yield 50%；With N- chlorine
Corresponding chloro thing can be prepared by substituting N- bromo-succinimides for succimide；Compound I physical and chemical parameter and structure
Parameter is shown in Table 1；Amount and the volume of reaction vessel prepared by compound I is expanded or shunk by corresponding proportion.
Work as R1For Ph, X1For H, X2For Br when, compound I preparation method is as follows：
0.4 mM of compound VII is dissolved in 15 milliliters of dry acetonitriles, then sequentially adds 0.44 mM of N- bromine
For succimide, 0.02 mmoles Trimethylsilyl trifluoromethanesulfonate, after addition, it is stirred overnight at room temperature, after reaction completely
20 milliliters of saturated sodium bicarbonate solution extractions are added, is extracted with ethyl acetate, isolates ethyl acetate layer, ethyl acetate phase is used again
Saturated sodium bicarbonate and saturated sodium-chloride respectively washing one time, ethyl acetate phase is dried through anhydrous magnesium sulfate, is filtered, and is concentrated, decompression
After removing solvent, residue purifies to obtain compound I through 200~300 mesh silica gel column chromatographies, and eluant, eluent is that volume ratio is ethyl acetate
: petroleum ether=10 of 60~90 degrees Celsius of cuts: 1 mixed liquor；With gained sterling calculated yield, yield 46%；With N- chloros
Succimide, which substitutes N- bromo-succinimides, can prepare corresponding chloro thing；Compound I physical and chemical parameter and structure ginseng
Number is shown in Table 1；Amount and the volume of reaction vessel prepared by compound I is expanded or shunk by corresponding proportion.
Embodiment 7
The bromo hexahydro indanone compounds I of present invention Antibacterial Activity result：
The code name and title for the frequently seen plants disease fungus that the present invention tests are as follows：AS：Tomato early blight bacterium, its latin name
For：Alternaria solani、BC：Botrytis cinerea pers, its Latin are entitled：Botrytis cinerea、CA：Peanut foxiness
Germ, its Latin are entitled：Cercospora arachidicola、GZ：Fusarium graminearum, its Latin are entitled：Gibberella
zeae、PI：Phytophthora infestans, its Latin are entitled：Phytophthora infestans(Mont.)de Bary、PP：Apple
Fruit Target spot pathogen, its Latin are entitled：Physalospora piricola、PS：Rhizoctonia solani Kuhn, its Latin are entitled：
Pellicularia sasakii、RC：Rhizoctonia cerealis, its Latin are entitled：Rhizoctonia cerealis、SS：Sclerotina Sclerotiorum in Winter Rape
Core germ, its Latin are entitled：Sclerotinia sclerotiorum, these strains have representativeness well, can represented
The kind for most of pathogen that field occurs in agricultural production.
Thalli growth rate method measurement result is shown in Table 2, and table 2 shows, in 50 mcg/ml, all bromines of the invention synthesized
There are different degrees of bactericidal activity, most of bromo hexahydro indanone compounds I of the invention for hexahydro indanone compounds I
With preferable bactericidal activity；For tomato early blight bacterium, the bacteriostatic activities of all compounds of the invention 35% with
On, wherein compound zyj05-186 bacteriostatic activity highest, it is 28.00%.For botrytis cinerea pers, institute of the invention
There is the bacteriostatic activity of compound more than 28%, wherein compound zyj05-172 bacteriostatic activity highest, be 61.85%.It is right
For peanut Cercospora bacteria, the bacteriostatic activity of all compounds of the invention is more than 30%, wherein compound zyj05-186
Bacteriostatic activity highest, be 46.67%.For fusarium graminearum, the bacteriostatic activity of all compounds of the invention exists
More than 30%, wherein compound zyj05-154 bacteriostatic activity highest, it is 58.49%.For Phytophthora infestans, this
The bacteriostatic activity of all compounds of invention is more than 20%, and wherein compound zyj05-171 bacteriostatic activity highest is
39.18.00%.For Botryosphaeria berengeriana f. sp, compound zyj05-154, zyj05-155 of the invention, zyj05-157,
Zyj05-171, zyj05-172 bacteriostatic activity are more than 28%, wherein compound zyj05-157 bacteriostatic activity highest,
For 39.15%.For Rhizoctonia solani Kuhn, the bacteriostatic activity of all compounds of the invention is more than 27%, wherein changing
Compound zyj05-172 bacteriostatic activity highest, it is 40.29%.For Rhizoctonia cerealis, the suppression of all compounds of the invention
Bacterium activity is more than 20%, wherein compound zyj05-186 bacteriostatic activity highest, is 42.31%.To Sclerotinia sclerotiorum
For, the bacteriostatic activity of all compounds of the invention is more than 60%, and wherein compound zyj05-186 bacteriostatic activity is most
Height, it is 86.96%.
Embodiment 8
The bromo hexahydro indanone compounds I insecticidal activities of the present invention：
Bromo hexahydro indanone compounds I insecticidal activity assay the results are shown in Table 3, and table 3 is visible：The bromo hexahydro of the present invention
Indanone compounds I has preferable insecticidal activity, and when reagent agent concentration is 100 mg/litre, observation acts on 72 hours
Afterwards, bromo hexahydro indanone compounds I of the invention has preferable toxic action to aphid, and all compounds of the invention are killed
Worm activity is more than 25%；Wherein compound zyj05-176 insecticidal activity highest, it is 46.4%.
The chloro isothiazole anabasine compound I of the present invention is also to Orthoptera, Isoptera, Semiptera, Homoptera, tassel wing
Mesh, coleoptera, Lepidoptera, Neuroptera, Diptera, Hymenoptera and the agricultural of Acarina and forestry and gardening plant insect evil mite
With good insecticidal activity.
Embodiment 9
The bromo hexahydro indanone compounds I of the present invention anti-TMV activity：
The measurement result of the anti-TMV activity of bromo hexahydro indanone compounds I is shown in Table 4, and table 4 shows, bromo six of the invention
Hydrogen indanone compounds I has preferably anti-TMV activity.For protecting assivation property, the passivation of all compounds of the invention is lived
Property be above 30%, wherein compound zyj05-171 passivation activity highest, be 49.90%.For induced activity, this hair
The passivation activity of bright all compounds is above 20%, wherein compound zyj05-186 passivation activity highest, is
59.99%.
The present invention all bromo hexahydro indanone compounds I also to rice dwarf virus disease, BYDV, stripe virus disease, kind
Eggplant ferm-leaf viral disease, pepper mosaic virus disease viral disease, tobacco veinal necrosis virus disease, maize dwarf mosaic, cauliflower mosaic virus, citrus
Virosis, cymbidium mosaic virus disease, the agricultural of cybidium ring spot virus and forestry and gardening plant virus disease have good
Antiviral activity.
Embodiment 10
The bromo hexahydro indanone compounds I of the present invention is with insecticide composition in preventing and treating agricultural and forestry and gardening plant
Application in insect pest：
All bromo hexahydro indanone compounds I of the present invention combine shape with any one in commodity insecticide or two kinds
It is used to prevent and treat agricultural and forestry and gardening plant insect pest into Pesticidal combination, the commodity insecticide is selected from：Chlopyrifos, it is sub-
Nong, Acetamiprid, emamectin benzoate, milbemectin, AVM, pleocidin, fenvalerate, esfenvalerate, chlorine
Cyano chrysanthemate, effective cypermethrin, Cyhalothrin, decis, Fenpropathrin, Beta- cyfloxylates, Lambda- tri-
Cyfloxylate, Permanone, permethrin, allethrin, Biphenthrin, Permethrin, ethofenprox, flumethrin,
Fluvalinate, imidacloprid, Nitenpyram, fluorine thiophene quinoline, thiacloprid, Diacloden, clothianidin, MTI-446, clothianadin, Da Te
South, diflubenzuron, d ichlorbenzuron, Teflubenzuron, deinsectization are grand, HEXAFLUMURON, flufenoxuron, pyridine worm are grand, lufenuron, poisonous insect urea, penfluron,
Noviflumuron is noviflumuron, its No. CAS be 121451-02-3, flucycloxuron, Novaluron be Rimon, chlorfluazuron,
Bay sir 6874 are that { 1- [(3.5- bis- chloro- 4) 4-nitrophenoxy phenyl 3-3- (2- chlorobenzenes)-urea }, Bay SIR-8514 are
[1- (4- Trifluoromethoxyphen-ls) -3- (2- chlorobenzenes)-urea], piperazine worm urea, Bistrifluron are bistrifluron, furans worm acyl
Hydrazine, tebufenozide, chlorine tebufenozide, methoxyfenozide, ring tebufenozide, Rogor, flolimat, DDVP, orthene, triazole
Phosphorus, quinalphos, pyridaphethione, isazofos, isoprocarb, sevin, Aphox, MTMC, Mobucin, cartap, Bassa, leaf
Disperse, carbaryl, Benfuracard micro, carbosulfan, cartap, fenisobromolate, Hexythiazox, fenpyroximate, pyridaben, clofentezine,
Propargite, diafenthiuron, pymetrozine, Envidor, spiral shell worm ester, spiral shell worm ethyl ester, butene-fipronil, azacyclotin, Buprofezin, phonamiphos,
Ethiprole, Cupric sulfate, dimehypo, chlorantraniliprole, Flubendiamide, fluorine cyanogen insect amide, cyanogen insect amide, Tolfenpyrad, chlorfenapyr, pyrrole
Piperazine ketone, etoxazole, tebufenpyrad, rattle away young ketone, Nylar, emaricin；The bromo hexahydro indanone compounds I of the present invention is described
Weight/mass percentage composition in Pesticidal combination is 1%-90%, bromo hexahydro indanone compounds I of the invention and foregoing commodity
The ratio of insecticide is mass percent 1%: 99% to 99%: 1%；The formulation of the Pesticidal combination processing is selected from：Seed
Handle emulsion, aqueous emulsion, microemulsion, suspension emulsion, capsule suspension, water-soluble granule, granula subtilis, soluble thick agent, poison grain, block
Shape poison bait, granular poison bait, sheet poison bait, dense poison bait, sustained-release block, electrostatic spray agent, oil in water emulsion, smoke candle, smoke candle, cigarette
Mist cylinder, smog rod, smog piece, smog ball, foaming agent, ointment, thermal fog, harl agent, aerosol, solid-liquid mixing dress agent, liquid/
Solid liquid mixing dress agent, solid/mixing dress agent, medicine paint, fine granule, tracking pulvis, oil suspending agent, oil-dispersing property pulvis, dense jelly, bold and vigorous pour
Agent, seed coat agent, liniment, film forming finish, ultra low volume liquids, steam releasing agent；The plant worm of the Pesticidal combination preventing and treating
Evil is selected from：Red spider, Asiatic migrotory locust, reading room management, Chinese rice grasshopper, Patanga japonica (l.Bol.), single thorn mole cricket, Oriental burmeister, rice thripses,
Onion thrips, greenhouse thrips, haplothrips aculeatus, Mai Jian pipes thrips, Trialeurodes vaporariorum Westwood, Bemisia tabaci, rice green leafhopper, green leaf hopper, cotton leaf
Cicada, spot clothing plant hopper, brown paddy plant hopper, white backed planthopper, small brown rice planthopper, the flat angle plant hopper of sugarcane, cotten aphid, green bugs, grain aphid, black peach aphid,
Kaoliang aphid, radish aphid, icerya purchasi, Pseudaulacaspis pentagona, unaspis shield kuwana, san jose scale, wax insect, ceroplastes rubens, Didesmococcus koreanus Borchs, pear lace bug, perfume (or spice)
Any of several broadleaf plants lace bug, thin corner piece stinkbug, Orius minutus, slender rice bug, paddy fly, niphe elongata, scotinophora lurida, green rice bug, green plant bug, clover are blind
Stinkbug, black striped plant bug, chrysopa septempunctata, beautiful Chrysopa, Chinese green lacewing, rain moth, casemaking clothes moth, oriental moth, brown slug moth, thosea siensis, gelechiid, the red bell of cotton
Worm, brachmia triannuella, diamondback moth, small heart-eating peach worm, eating-core bean worm, small heart-eating peach worm, apple Spilonota lechriaspis, brown belt length leaf roll
Moth, Adoxophyes cyrtosema, striped rice borer, bean-pod borer, corn borer, yellow rice borer, Oeobia undalis, rice leaf roller, bar snout moth's larva, Notarchaderogata,
Dichocrocis punctiferalis, armyworm, prodenia litura, rice green caterpillar, anomis flava, beet armyworm, pink rice borer, bollworm, ancient cooking vessel point spark, small ground are old
Brave, big cutworm, yellow cutworm, steal poison moth, gypsymoth, palaearctic sweet potato, greenish brown hawk moth, straight burr rice hesperiidae, pelopidas mathias, citrus
Swallowtail butterfly, Common Mormon, cabbage butterfly, pyrameis indica, a ramie Huang a kind of butterfly harmful to crop plants, beans blister beetle, Venus ground beetle, wrinkle sheath ground beetle, wheat head ground beetle,
It is the small buprestid beetle of pleonomus canaliculatus, Agriotes subrittatus Motschulsky, khapra beetle, attagenus piceus, citrus, golden edge buprestid beetle, yellow meal worm, dark mealworm, red
Intend ostomatid, confused flour beetle, verdigris different beetle, H. parallela, holotrichia oblita, mulberry borer, longicorn beetle, nadezhdiella cantori,
Pink neck longicorn, big daikon leaf beetle, daicon leaf beetle, aulacophora femoralis, phyllotreta striolata, Callosobruchus chinensis, pea weevil, broad bean weevil, sitophilus zea-mais, rice
As, dolerus tritici, pear fruit sawfly, yellowish leukorrhea ichneumon wasp, armyworm white star ichneumon wasp, corn earworm hang cocoon ichneumon wasp, Campoletis chlorideae, snout moth's larva stain wart
Ichneumon wasp, mosquito, fly, horsefly, wheat midge, contarinia tritici, pachydiplosis oryzae, citrus fruit fly, melonfly, the latent fly of wheat leaf ash, America
Liriomyza bryoniae, Soybean stem borer, frit fly, Hylemyia Platura Meigen, onion fly, radish fly, full skirt Exorista civilis, corn borer are strict to post fly, armyworm；It is described to kill
The plant of worm composition for preventing and controlling is selected from：Paddy, wheat, barley, oat, corn, sorghum, sweet potato, potato, cassava, soybean, lotus
Lan Dou, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, sunflower, beet, sugarcane, coffee, cocoa,
Ginseng, fritillaria, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, oil
Dish, green onion, garlic, watermelon, muskmelon, "Hami" melon, pawpaw, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper,
Banana, papaya, orchid, potted landscape.
Embodiment 11
The bromo hexahydro indanone compounds I of the present invention is with antimicrobial combination in preventing and treating agricultural and forestry and gardening plant
Application in disease：
All bromo hexahydro indanone compounds I of the present invention combine shape with any one in commodity bactericide or two kinds
It is used to prevent and treat agricultural and forestry and gardening plant disease into bactericidal composition, the commodity bactericide is selected from：Diazosulfide,
Tiadinil, it is abbreviated as TDL, tisocromide, first thiophene and lures amine, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- formic acid, 4- methyl isophthalic acids, 2,3- thiophenes
Diazole -5- sodium formates, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- Ethyl formates, DL- beta-aminobutyric acids, isotianil, its English are logical
With entitled：Isotianil, the chloroisothiazole -5- formic acid of 3,4- bis-, the chloroisothiazole -5- sodium formates of 3,4- bis-, the different thiophene of 3,4- dichloros
Azoles -5- Ethyl formates, virazole, antofine, Ningnanmycin or salicylic acid, cymoxanil, thiram, ziram, Mancozeb, second
Phosphorus aluminium, thiophanate-methyl, Bravo, enemy can pine, procymidone, fenpropidin, thiophanate methyl, thiophanate, Metalaxyl-M, fluorine
Quinoline, dimethomorph, mefenoxam, benalaxyl-M, double chlorine zarilamid, flusulfamide, first flusulfamide, thiophene fluorine bacterium amine, flutolanil,
Tecloftalam, ring propionyl bacterium amine, cyflufenamid, fenhexamid, zarilamid, Silthiopham, furametpyr, pyrrole metsulfovax, double alkynes acyls
Bacterium amine, zoxamide, fenfuram, carboxin, chlozolinate, iprodione, Fluoxastrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, benzene
Oxygen bacterium amine, orysastrobin, ZEN 90160, pyraclostrobin, trifloxystrobin, Enestroburin, alkene oxime amine, oxygen ring azoles, bromuconazole, ring third
Azoles alcohol, Difenoconazole, olefin conversion, efficient olefin conversion, epoxiconazole, RH-7592, Fluquinconazole, Flusilazole, Flutriafol, hexaconazole,
Glyoxalin, kind bacterium azoles, metconazole, nitrile bacterium azoles, penconazole, propiconazole, prothioconazoles, simeconazoles, Tebuconazole, tetraconazole, three
Azoles alcohol, triticonazole, bitertanol, probenazole, furidazol, imazalil, efficient imazalil, Prochloraz, fluorine bacterium azoles, cyazofamid,
The white spirit of Fenamidone, Evil imidazoles, pefurazoate, famoxadones, SYP-Z048, hymexazo, Evil, Guardian, Grandox fumigant, pungent thiophene
Ketone, benthiozole, dodemorph, butadiene morpholine, tridemorph, fenpiclonil, fludioxonil, fluazinam, pyrifenox, ring pyridine bacterium
Amine, Boscalid, fluopicolide, pyridine bacterium amine, cyprodinil, fluorine mepanipyrim, ferimzone, mepanipyrim, pyrimethanil, chlorobenzene pyrimidine
Alcohol, nuarimol, chinomethionat, dithianon, ethoxyquin, oxyquinoline, the third oxygen quinoline, quinoxyfen, diethofencarb, isopropyl
Bacterium amine, benzene metsulfovax, Propamocarb, methasulfocarb, edifenphos, different rice blast net, pyrazophos, tolelofos-methyl, blasticidin-S, spring thunder are mould
Element, polyoxin, Polyoxin, valida, jinggangmeisu, streptomysin, metalaxyl, furalaxyl, M 9834, ofurace, go out
Rust amine, carbendazim, benomyl, thiophanate-methyl, triazolone, bupirimate, dimethirimol, ethirimol, difoltan, gram bacterium
Pellet, folpet, vinclozolin, fluoromide, dimethachlon, Bravo, Isoprothiolane, kitazine, Yekuzuo, pentachloro- nitro
Benzene, Propineb, phosethyl-Al, sulphur, Bordeaux mixture, copper sulphate, copper oxychloride, cuprous oxide, Kocide SD, metrafenone,
Pencycuron, diclomezin, Rabcide, pyroquilon, volution bacterium amine, tricyclazole, triforine, more fruit pyridines, the pungent salt of biguanides, biguanides are pungent
Amine, botran, benzene flusulfamide, toluene flusulfamide, K-281, fenaminosulf, oxolinic acide, probenazole, bronopol, iodomethane,
Metham-sodium, enemy's line ester, dazomet, nemamort, lythidathion, cadusafos, fensulfothion, thionazin, fenamiphos, phonamiphos, except line
The different thiophene of phosphorus, isazofos, fosthietan, oxamyl, Aldicarb, carbofuran, vikane, dichloropropylene, dichloro-isonicotinic acid, allyl
Azoles；Total weight/mass percentage compositions of the bromo hexahydro indanone compounds I of the present invention in the bactericidal composition is 1%-
The ratio of 90%, bromo hexahydro indanone compounds I of the invention and foregoing commodity bactericide is mass percent 1%: 99%
To 99%: 1%；The formulation of the bactericidal composition processing is selected from：Seed treatment emulsion, aqueous emulsion, microemulsion, suspension emulsion, glue
Capsule suspending agent, water-soluble granule, granula subtilis, soluble thick agent, poison grain, block poison bait, granular poison bait, sheet poison bait, dense poison bait,
Sustained-release block, electrostatic spray agent, oil in water emulsion, smoke candle, smoke candle, smoke cartridge, smog rod, smog piece, smog ball, get angry
Solid agent, ointment, thermal fog, harl agent, aerosol, the agent of solid-liquid mixing dress, the agent of liquid liquid mixing dress, solid/mixing fill agent, medicine paint,
Fine granule, tracking pulvis, oil suspending agent, oil-dispersing property pulvis, dense jelly, sprinkle and pour agent, seed coat agent, liniment, film forming finish, ultralow
Volume liquids, steam releasing agent；The plant disease of the bactericidal composition preventing and treating is selected from：Seedling blight of rice, tomato root rot, horse
Bell potato late blight, tobacco black shank, millet powdery mildew, downy mildew of garpe, downy mildew of lettuce, cucumber downy mildew, cucumber anthracnose；
The applicable plant of the bactericidal composition is selected from：Paddy, wheat, barley, oat, corn, sorghum, sweet potato, Ma Lingzhu, cassava,
Soybean, garden pea, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, sunflower, beet, sugarcane, coffee
Coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube,
Beet, rape, green onion, garlic, watermelon, muskmelon, "Hami" melon, pawpaw, apple, citrus and peach, tea, wild vegetables, bamboo shoots, beer
Flower, pepper, banana, papaya, orchid, potted landscape.
Embodiment 12
The bromo hexahydro indanone compounds I of the present invention is combined with anti-plant virus agent in preventing and treating agricultural and forestry and garden
Application in skill viral diseases of plants：
All bromo hexahydro indanone compounds I of the present invention and any one in commodity antiviral agent or two kinds of groups
Conjunction forms antiviral composition and is used to prevent and treat agricultural and forestry and gardening plant virus disease, the commodity antiviral agent choosing
From：Diazosulfide, tiadinil, TDL, isotianil are abbreviated as, its English is general entitled：Isotianil, 4- methyl isophthalic acid,
2,3- thiadiazoles -5- formic acid, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- sodium formates, 4- methyl isophthalic acids, 2,3- thiadiazoles -5- formic acid second
Ester, the chloroisothiazole -5- formic acid of 3,4- bis-, the chloroisothiazole -5- sodium formates of 3,4- bis-, the chloroisothiazole -5- Ethyl formates of 3,4- bis-,
DL- beta-aminobutyric acids, virazole, antofine, Ningnanmycin, tisocromide, first thiophene lure amine or salicylic acid, cytosintetidemycin, dichloro different
Nicotinic acid, allyl isothiazole, well ridge azanol, jinggangmeisu；The bromo hexahydro indanone compounds I of the present invention is at described antiviral group
Total weight/mass percentage composition in compound is 1%-90%, and bromo hexahydro indanone compounds I of the invention resists with foregoing commodity
The ratio of plant virus agent is mass percent 1%: 99% to 99%: 1%；The formulation choosing of the antiviral composition processing
From：Seed treatment emulsion, aqueous emulsion, microemulsion, suspension emulsion, capsule suspension, water-soluble granule, granula subtilis, soluble thick agent,
Poison grain, block poison bait, granular poison bait, sheet poison bait, dense poison bait, sustained-release block, electrostatic spray agent, oil in water emulsion, smoke candle, cigarette
Mist candle, smoke cartridge, smog rod, smog piece, smog ball, foaming agent, ointment, thermal fog, harl agent, aerosol, solid-liquid mixing dress
Gu agent, the agent of liquid liquid mixing dress, solid/mixing dress agent, medicine paint, fine granule, tracking pulvis, oil suspending agent, oil-dispersing property pulvis, dense glue
Agent, sprinkle and pour agent, seed coat agent, liniment, film forming finish, ultra low volume liquids, steam releasing agent；The antiviral composition preventing and treating
Virus disease be selected from：Rice dwarf virus disease, BYDV, stripe virus disease, fern leaf of tomato viral disease, pepper mosaic virus disease viral disease, cigarette
Careless veinal necrosis virus disease, maize dwarf mosaic, cauliflower mosaic virus, citrus virosis, cymbidium mosaic virus, sword-leaved cymbidium ring spot
Poison；The plant that the antiviral composition is used to prevent and treat is selected from：Paddy, wheat, barley, oat, corn, sorghum, sweet potato, Ma Ling
Potato, cassava, soybean, garden pea, broad bean, pea, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, sunflower, beet,
Sugarcane, coffee, cocoa, ginseng, fritillaria, rubber, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery
Dish, hot pickled mustard tube, beet, rape, green onion, garlic, watermelon, muskmelon, "Hami" melon, pawpaw, apple, citrus and peach, tea, wild vegetables, bamboo
Bamboo shoot, hops, pepper, banana, papaya, orchid, potted landscape.
Embodiment 13：The bromo hexahydro indanone compounds I of the present invention combine with acaricide prevent and treat agriculture and forestry with
And the application in gardening plant mite evil：
All bromo hexahydro indanone compounds I of the present invention combine shape with any one in commodity acaricide or two kinds
It is used to prevent and treat agricultural and forestry into miticide composition and gardening plant mite does harm to, the commodity acaricide is selected from：Azacyclotin, three rings
Tin, fenbutatin oxide, three phosphor tins, chlorfenviphos, dimethylvinphos, crotoxyphos, DDVP, heptenophos, Menite, Azodrin, 2-dichloroethylk dimethyl phosphate,
Chlopyrifos, Diothyl, imino-formyl chloride sulphur phosphorus, omethoate, dioxathion, Ethodan, malathion, methacrifos, Phosalone, pungent sulphur
Phosphorus, methylpyrimidine sulphur phosphorus, quinalphos, sulfotep, Hostathion, Kilval, isocarbophos, acephatemet, propetamphos, chlorimide sulphur
Phosphorus, phosmet, acrinathrin, Biphenthrin, lambda-cyhalothrin, smart gamma cyhalothrin, Fenpropathrin, the chrysanthemum of fluorine cyanogen penta
It is ester, flumethrin, taufluvalinate, brofluthrinate, Bifenazate, fenothiocarb, Aldicarb, butocarboxim, oxamyl, pest-resistant
Prestige, thiofanox, benomyl, sok, carbofuran, carbosulfan, MTMC, promacyl, Carzol, single carbonamidine, mite killing
Amidine, Amitraz, Spanon, Ergol, fenisobromolate, cyflumetofen, acequinocyl, Nissol, flufenoxuron, macro tetrolide, worm
Mite mycin, thuringiensin, tetranactin, macro tetrolide, AVM, doractin, eprinomectin, ivermectin, Sai La
Rhzomorph, moxidectin, pyrethrin, nicotine, matrine, nimbin, rotenone, tebufenpyrad, pyridaben, fenpyroximate, clofentezine,
Propargite, Hexythiazox, Envidor, fluacrypyrim, chlorfenizon, propargite, pyridaben；The bromo hexahydro indanone compounds of the present invention
Total weight/mass percentage compositions of the I in the miticide composition is 1%-90%, bromo hexahydro indanone compounds I of the invention
It is mass percent 1%: 99% to 99%: 1% with the acaricidal ratio of the commodity；The formulation of the miticide composition processing
It is selected from：Seed treatment emulsion, aqueous emulsion, microemulsion, suspension emulsion, capsule suspension, water-soluble granule, granula subtilis, soluble thick
Agent, poison grain, block poison bait, granular poison bait, sheet poison bait, dense poison bait, sustained-release block, electrostatic spray agent, oil in water emulsion, smog
Tank, smoke candle, smoke cartridge, smog rod, smog piece, smog ball, foaming agent, ointment, thermal fog, harl agent, aerosol, solid-liquid
Gu the agent of mixing dress, the agent of liquid liquid mixing dress, solid/mixing dress agent, medicine paint, fine granule, tracking pulvis, oil suspending agent, oil-dispersing property powder
Agent, dense jelly, sprinkle and pour agent, seed coat agent, liniment, film forming finish, ultra low volume liquids, steam releasing agent；The mite killing combination
The mite evil of thing preventing and treating is selected from：Mite evil is selected from Tetranychidae, Tenuipalpidae, furan line mite, Eriophyidae, tetranychus telarius category, the evil mite of Eriophyidae,
These evil mites are worldwide Agricultural Mites, forestry harmful mites, gardening evil mite and hygienic evil mite；The miticide composition is used for what is prevented and treated
Plant is selected from：Paddy, wheat, barley, oat, corn, sorghum, sweet potato, potato, cassava, soybean, garden pea, broad bean, pea
Beans, mung bean, red bean, cotton, silkworm and mulberry, peanut, rape, sesame, sunflower, beet, sugarcane, coffee, cocoa, ginseng, fritillaria, rubber
Glue, coconut, oil palm, sisal hemp, tobacco, tomato, capsicum, radish, cucumber, Chinese cabbage, celery, hot pickled mustard tube, beet, rape, green onion, garlic, west
Melon, muskmelon, "Hami" melon, pawpaw, apple, citrus and peach, tea, wild vegetables, bamboo shoots, hops, pepper, banana, papaya, orchid
Flower, potted landscape.
The bromo hexahydro indanone compounds I of the present invention of table 1 chemical constitution and physical and chemical parameter
The bromo hexahydro indanone compounds I of the present invention of table 2 bacteriostatic activity (suppression/% of 50 mcg/mls)
| Sequence number | Numbering | AS | BC | CA | GZ | PI | PP | PS | RC | SS |
| 1 | zyj05-154 | 35.72 | 47.38 | 36.87 | 58.49 | 35.46 | 29.00 | 36.08 | 28.95 | 77.43 |
| 2 | zyj05-155 | 36.29 | 45.76 | 40.50 | 48.02 | 32.72 | 36.88 | 27.52 | 29.33 | 68.18 |
| 3 | zyj05-157 | 42.52 | 61.46 | 45.00 | 49.50 | 30.56 | 39.15 | 29.67 | 38.17 | 75.29 |
| 4 | zyj05-171 | 45.53 | 28.28 | 35.67 | 34.88 | 39.18 | 28.00 | 27.05 | 31.76 | 70.09 |
| 5 | zyj05-172 | 44.56 | 61.85 | 35.99 | 51.05 | 34.72 | 30.00 | 40.29 | 25.45 | 78.99 |
| 6 | zyj05-176 | 42.31 | 50.00 | 33.33 | 40.00 | 22.22 | 4.00 | 31.03 | 23.08 | 73.91 |
| 7 | zyj05-186 | 50.00 | 41.67 | 46.67 | 44.00 | 29.63 | 8.00 | 37.93 | 42.31 | 86.96 |
| 8 | Isotianil | 0 | 34.50 | 13.30 | 8.30 | 22.70 | 32.00 | 13.30 | 34.80 | 87.50 |
The bromo hexahydro indanone compounds I's of the present invention of table 3 kills aphid activity (death rate, %, 100 mg/mls)
| Sequence number | Numbering | The death rate/% |
| 1 | zyj05-154 | 25.0 |
| 2 | zyj05-155 | 32.6 |
| 3 | zyj05-157 | 28.3 |
| 4 | zyj05-171 | 45.9 |
| 5 | zyj05-172 | 39.7 |
| 6 | zyj05-176 | 46.4 |
| 7 | zyj05-186 | 40.9 |
| 8 | Thiacloprid | 51.48 |
The bromo hexahydro indanone compounds I of the present invention of the table 4 activity of resisting tobacco mosaic virus (suppression of 100 mcg/mls
Rate/% processed)
| Sequence number | Numbering | Passivation pattern | Induction pattern |
| 1 | zyj05-154 | 45.15±4.35 | 28.38±5.12 |
| 2 | zyj05-155 | 47.37±6.28 | 49.89±3.55 |
| 3 | zyj05-157 | 38.56±7.00 | 56.66±5.00 |
| 4 | zyj05-171 | 49.90±3.55 | 35.55±4.44 |
| 5 | zyj05-172 | 42.58±5.38 | 37.90±5.68 |
| 6 | zyj05-176 | 37.99±4.81 | 57.62±6.99 |
| 7 | zyj05-186 | 39.50±4.19 | 59.99±4.27 |
| 9 | Virazole | 38.05±3.50 | - |
| 33 | Tiadinil | 24.99±4.58 | 46.58±6.12 |
Claims (6)
1. a kind of bromo hexahydro indanone compounds, it is characterised in that there is following test code number and chemical constitution：
Bz in above-mentioned chemical constitution is benzoyl.
2. the synthetic method of the bromo hexahydro indanone compounds described in claim 1, specific synthetic route are as follows：
The synthetic method of bromo hexahydro indanone compounds described in claim 1 is divided into following steps：
A. compound III preparation：
3.2 mMs of compound II is added in 100 milliliters of two-mouth bottles, vacuumized, injection nitrogen protection, then adds 25 millis
Dry tetrahydrofuran solution is risen, 3.5 mMs of vinyl magnesium bromides are slowly added dropwise into reaction bulb under ice salt bath, are added dropwise
Afterwards, ice salt bath stirs 20 minutes, removes ice bath, is stirred at room temperature 2 hours, and after reaction completely, reaction solution adds 20 milliliters of saturated carbons
Sour hydrogen sodium solution is quenched, and ethyl acetate extraction, isolates ethyl acetate layer, ethyl acetate phase uses saturated sodium bicarbonate and saturation again
Sodium chloride is dried after respectively washing one time through anhydrous magnesium sulfate, is filtered, and concentration, removal of solvent under reduced pressure, residue is through 200~300 mesh
Silica gel column chromatography purifies to obtain compound III, and eluant, eluent is that volume ratio is ethyl acetate: the petroleum ether of 60~90 degrees Celsius of cuts=
6: 1 mixed liquor；With gained sterling calculated yield, yield 70%；Amount and the volume of reaction vessel prepared by compound III presses phase
Ratio is answered to expand or shrink；
B. compound IV preparation：
0.76 mM of compound III is dissolved in 20 milliliters of dry tetrahydrofuran solutions, then adds 2.27 mMs of boron
Sodium hydride, the tetrahydrofuran solution of 3.04 mMs of BFEEs is slowly added dropwise under ice bath, after being added dropwise, ice bath stirring
Ice bath being removed again within 15 minutes, being then stirred at room temperature 2 hours, 4.6 millis are slowly added dropwise into reaction bulb under ice bath after stopping reaction
Mole Jones reagents, after being added dropwise room temperature continue stirring 2 hours, reaction completely after, add 20 milliliters of water, use acetic acid
Ethyl ester extracts, and isolates ethyl acetate layer, ethyl acetate phase is again with respectively washing one time of saturated sodium bicarbonate and saturated sodium-chloride, second
Acetoacetic ester is mutually dried through anhydrous magnesium sulfate, is filtered, concentration, and after removal of solvent under reduced pressure, residue is through 200~300 mesh silica gel column layers
Analysis purifies to obtain compound IV, and eluant, eluent volume ratio is ethyl acetate: petroleum ether=4 of 60~90 degrees Celsius of cuts: 1 mixing
Liquid；With gained sterling calculated yield, yield 45%；Amount and the volume of reaction vessel prepared by compound IV is expanded by corresponding proportion
Or reduce；
C. compound V preparation：
It is ice bath in the mixed solution that tetrahydrofuran is 10: 1 with water that 1.9 mMs of compound IV are dissolved in into 15 milliliters of volume ratios
It is lower that 2 mMs of sodium borohydrides are added portionwise into reaction solution, after addition, ice bath is removed, is stirred at room temperature 1 hour, has reacted
15 milliliters of saturated sodium bicarbonates are added after complete to be quenched, and are extracted with ethyl acetate, are isolated ethyl acetate layer, ethyl acetate phase is used again
Saturated sodium bicarbonate and saturated sodium-chloride respectively washing one time, ethyl acetate phase is dried through anhydrous magnesium sulfate, is filtered, and is concentrated, decompression
After removing solvent, residue purifies to obtain compound V through 200~300 mesh silica gel column chromatographies, and eluant, eluent is that volume ratio is ethyl acetate
: petroleum ether=3 of 60~90 degrees Celsius of cuts: 1 mixed liquor；With gained sterling calculated yield, yield 68%；Compound V systems
Standby amount and the volume of reaction vessel are expanded or shunk by corresponding proportion；
D. compound VI preparation：
By 3.5 mMs of compound V be dissolved in 25 milliliters steam again after dichloromethane in, vacuumize, injection nitrogen protection, under ice bath
14 mMs of triethylamine is added into reaction bulb, acyl chlorides PhCOCl is then slowly added dropwise, after being added dropwise, removes ice bath, room
Temperature is stirred overnight, and 20 milliliters of saturated sodium bicarbonate solution extractions are added after reacting completely, separate dichloromethane layer, dichloromethane phase
Again with respectively washing one time of saturated sodium bicarbonate and saturated sodium-chloride, dichloromethane is mutually dried through anhydrous magnesium sulfate, is filtered, concentration,
After removal of solvent under reduced pressure, residue purifies to obtain compound VI through 200~300 mesh silica gel column chromatographies, and eluant, eluent is that volume ratio is second
Acetoacetic ester: petroleum ether=8 of 60~90 degrees Celsius of cuts: 1 mixed liquor；With gained sterling calculated yield, yield 90%；Chemical combination
Amount and the volume of reaction vessel prepared by thing VI is expanded or shunk by corresponding proportion；
E. compound VII preparation：
0.7 mM of compound VI is dissolved in 6 milliliters of methanesulfonic acids, then adds 0.01 mM of phosphorus pentoxide and 35-40
Degrees Centigrade reacts 6 hours, adds 20 milliliters of water after reacting completely, is extracted with ethyl acetate, isolates ethyl acetate layer, second
Acetoacetic ester mutually again with respectively washing one time of saturated sodium bicarbonate and saturated sodium-chloride, through anhydrous magnesium sulfate dry, and takes out by ethyl acetate phase
Filter, concentrate, after removal of solvent under reduced pressure, residue purifies to obtain compound VII through 200~300 mesh silica gel column chromatographies, and eluant, eluent is body
Product ratio is ethyl acetate: petroleum ether=8 of 60~90 degrees Celsius of cuts: 1 mixed liquor；With gained sterling calculated yield, yield
60%；Amount and the volume of reaction vessel prepared by compound VII is expanded or shunk by corresponding proportion；
F. the preparation of the bromo hexahydro indanone compounds described in claim 1：
7 mMs of compound VII are dissolved in dry carbon tetrachloride, then sequentially add 7.7 mMs of N- bromo succinyl
Imines, 0.07 mM of azodiisobutyronitrile, in the reaction of 50 degrees Centigrades overnight, after reaction completely, filter, concentrate, decompression
Remove solvent, residue purifies to obtain bromo hexahydro indone class chemical combination described in claim 1 through 200~300 mesh silica gel column chromatographies
Thing, eluant, eluent are that volume ratio is ethyl acetate: petroleum ether=10 of 60~90 degrees Celsius of cuts: 1 mixed liquor；With gained sterling
Calculated yield, yield 50%；Amount and the volume of reaction vessel prepared by the bromo hexahydro indanone compounds described in claim 1
Expanded or shunk by corresponding proportion；
0.4 mM of compound VII is dissolved in 15 milliliters of dry acetonitriles, then sequentially adds 0.44 mM of N- bromo fourth
Imidodicarbonic diamide, 0.02 mmoles Trimethylsilyl trifluoromethanesulfonate, after addition, is stirred overnight at room temperature, and is added after reacting completely
20 milliliters of saturated sodium bicarbonate solution extractions, are extracted with ethyl acetate, isolate ethyl acetate layer, ethyl acetate phase uses saturation again
Sodium acid carbonate and saturated sodium-chloride respectively washing one time, ethyl acetate phase is dried through anhydrous magnesium sulfate, is filtered, and concentration, is removed under reduced pressure
After solvent, residue purifies to obtain bromo hexahydro indanone compounds described in claim 1 through 200~300 mesh silica gel column chromatographies,
Eluant, eluent is that volume ratio is ethyl acetate: petroleum ether=10 of 60~90 degrees Celsius of cuts: 1 mixed liquor；With gained sterling meter
Calculate yield, yield 46%；Amount and the volume of reaction vessel prepared by the bromo hexahydro indanone compounds described in claim 1 is pressed
Corresponding proportion is expanded or shunk.
3. the bromo hexahydro indanone compounds described in claim 1 are with agriculturally acceptable auxiliary agent in fungicide is prepared
Purposes.
4. the bromo hexahydro indanone compounds described in claim 1 are with agriculturally acceptable auxiliary agent in aphicide is prepared
Purposes.
5. the bromo hexahydro indanone compounds described in claim 1 are preparing anti-Tobacco mosaic with agriculturally acceptable auxiliary agent
Purposes in viral agent.
6. the bromo hexahydro indanone compounds described in claim 1 are preparing activating plants agent with agriculturally acceptable auxiliary agent
For preventing and treating the purposes in virus disease caused by tobacco mosaic virus (TMV).
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| PCT/CN2017/072489 WO2017129113A1 (en) | 2016-01-29 | 2017-01-24 | Bromohexahydroindanone compounds, preparation method for same, and uses thereof |
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| CN108675974B (en) * | 2018-05-07 | 2020-04-07 | 南开大学 | Strigolactone derivatives and preparation method and application thereof |
| CN108558796B (en) * | 2018-05-07 | 2020-04-07 | 南开大学 | Hydroxy methylene hydrindone derivatives, preparation method and application thereof |
| CN108892604B (en) * | 2018-08-15 | 2022-05-31 | 江西师范大学 | Method for preparing halogenated benzo [ b ] fluorenone series compounds |
| CN111704569A (en) * | 2020-07-27 | 2020-09-25 | 江西禾益化工股份有限公司 | Method for synthesizing dimethachlon |
| CN114057691B (en) * | 2021-12-07 | 2022-10-04 | 浙江工业大学 | Bisamide 1-indanone compound and preparation method and application thereof |
| CN115216194B (en) * | 2022-08-24 | 2022-12-27 | 中国科学院兰州化学物理研究所 | Self-polishing antifouling coating for embedding crushed Chinese prickly ash and preparation method and application thereof |
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| JPS61103850A (en) * | 1984-10-29 | 1986-05-22 | Ono Pharmaceut Co Ltd | 3-(indan-5-yloxy(or thio))cyclopentanecarboxylic acid derivative, its production, and remedy containing same as active ingredient |
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| JP5767831B2 (en) * | 2011-03-04 | 2015-08-19 | 花王株式会社 | Raw dry odor control agent |
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