CN102584758A - Indeno oxa-carboxylic acid derivative with bioactivities and method for preparing same - Google Patents
Indeno oxa-carboxylic acid derivative with bioactivities and method for preparing same Download PDFInfo
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- CN102584758A CN102584758A CN201110005453XA CN201110005453A CN102584758A CN 102584758 A CN102584758 A CN 102584758A CN 201110005453X A CN201110005453X A CN 201110005453XA CN 201110005453 A CN201110005453 A CN 201110005453A CN 102584758 A CN102584758 A CN 102584758A
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- 0 *OC(C(Cc1ccccc11)(C1=O)O)=O Chemical compound *OC(C(Cc1ccccc11)(C1=O)O)=O 0.000 description 5
- HGFCZPZUFUWSOZ-UHFFFAOYSA-N CC(C1)C=CC(C(C(O)OC2(CN)C3)=C2c2c3cccc2)=C1Cl Chemical compound CC(C1)C=CC(C(C(O)OC2(CN)C3)=C2c2c3cccc2)=C1Cl HGFCZPZUFUWSOZ-UHFFFAOYSA-N 0.000 description 1
- BUXHJZQEBAEHRI-UHFFFAOYSA-N CCC(CN)(C(C)C1C(CC2)=CC=C2I)OC1=O Chemical compound CCC(CN)(C(C)C1C(CC2)=CC=C2I)OC1=O BUXHJZQEBAEHRI-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses an indeno oxa-carboxylic acid derivative with insecticidal, acaricidal and/or bactericidal bioactivities in a formula (I), a method for preparing same and an application thereof, wherein R is C1-C3 alkyl; R1 is H or halogen; and R2 is halogen and phenyl, and the phenyl is substituted by at most 5 same or different substituent groups which are selected from the following list: H, halogen, C1-C3 alkyl, C1-C3 halogenated alkyls, C1-C3 alkoxy and C1-C3 halogenated alkoxy. The indeno oxa-carboxylic acid derivative has bioactivities, and has the acaricidal, insecticidal and bactericidal bioactivities under the usage of 2.5-5000mg/L.
Description
Technical field
The present invention relates to sterilization, desinsection, kill the bioactive indeno oxa-of mite carboxylic acid derivative and preparation method thereof.
Background technology
The control of insect, evil mite, germ is extremely important in the process that realizes high-efficiency agriculture.The control of insect, evil mite, germ simultaneously woods, herd, also very important in secondary, fishing and the public health.Though existing a lot of insects, evil mite, bacteria-treating agent on the market; But because problem such as the continuous expansion in market and insect, evil mite, the resistance of germ, the work-ing life of medicine and the economy of medicine and people are to the environment pay attention to day by day; Need scientists constantly to study, and then make new advances safe, efficient, economical of exploitation and have the desinsection of different effects mode, mite, sterilant kind extremely.
The compound that be to obtain to have new role mechanism and have broad-spectrum biological activity, the inventor has designed and synthesized to have desinsection, kills mite, the bioactive indeno oxa-of sterilization carboxylic acid derivative.Do not see as yet at present about indeno oxa-carboxylic acid derivative as sterilization, desinsection, kill the pertinent literature report of mite bioactive compounds.
Summary of the invention
The invention provides having desinsection, kill mite and/or the bioactive indeno oxa-of sterilization carboxylic acid derivative shown in the formula (I):
Wherein:
R is C
1～C
3Alkyl;
R
1Be H or halogen;
R
2Be halogen, phenyl, phenyl is selected from 5 identical or different substituting groups of following middle as many as and is replaced: hydrogen, halogen, C
1～C
3Alkyl, C
1～C
3Haloalkyl, C
1～C
3Alkyl oxy, C
1～C
3Haloalkyl oxygen base;
In the definition of the compound that provides above (I), no matter following substituting group is represented in the separately use or be used in the compound word of used term:
Halogen: refer to fluorine, chlorine, bromine, iodine;
Alkyl: refer to the straight or branched alkyl;
Haloalkyl: refer to the straight or branched alkyl, the Wasserstoffatoms on these alkyl is partly or entirely replaced by halogen atom;
Alkyl oxy: refer to have the straight or branched alkyl oxy of 1-3 carbon atom, be connected on the structure through the Sauerstoffatom key;
Haloalkyl oxygen base: refer to have the straight or branched alkyl oxy of 1-3 carbon atom, the Wasserstoffatoms on these alkyl oxies can partly or entirely be replaced by halogen atom.
Compound of the present invention can one or more steric isomers form exist.Various isomer comprise enantiomorph, diastereomer, geometrical isomer.
The invention still further relates to the formula that contains biologic effective dose (I) compound and at least a other compsn that is selected from tensio-active agent, solid diluent and liquid diluent of a kind of pest control, evil mite, germ.
The invention still further relates to the method for a kind of pest control, evil mite, germ, comprise formula (I) compound contact insect, evil mite, germ or its environment biologic effective dose.Also relate to simultaneously a kind of like this insect, evil mite, bacteria-treating method, insect, evil mite, germ or its environment are with formula (I) compound of biologic effective dose or contain at least a additional compounds of formula (I) compound and biologic effective dose or the mixture of preparation contacts pest control.
Formula of the present invention (I) compound has broad spectrum of activity: the compound that has can be used for preventing and treating on the various crops the various mite classes such as cotton spider mites, tangerine Panonychus citri; The compound that has can be used for preventing and treating on the various crops such as various harmful insects such as mythimna separata, small cabbage moth, prodenia litura, beet armyworm, leafhopper, aphids; The compound that has can be used for preventing and treating on various crops by multiple fungus-caused diseases such as Haplomycetes, Phycomycetes, Oomycete, Ascomycetes and deuteromycetes.
In view of the economy and the biological activity of compound, the preferred formula of the present invention (I) compound is:
The present invention lists segment bounds (I) compound that comprises above-mentioned preferred compound with table 1 and further specifies the present invention, but does not limit the present invention.Among the present invention the fusing point of giving all not calibrated, (APCI, Pos) (EI, 70eV all can be observed its molecular ion peak in m/z) to all compounds for (Agilent 1100Series LC/MSD) and GC-Mass at LC-MS in the table 1.Compound in the table 1
1Mark in H NMR (Varian INOVA-300spectrometer) does with tetramethylsilane (TMS).
Table 1:
Compound shown in the formula of the present invention (I) obtains through the reaction formula 1 shown in following, and (II) in the reaction formula 1 obtains through the reaction formula 2 shown in following, and (III) in the reaction formula 2 obtains through reaction formula 3.Substituting group wherein except that specializing all like preceding qualification.
Reaction formula 1:
Reaction formula 2:
Reaction formula 3:
The preparation (reaction formula 1) of formula (I) compound: at solvent N; In dinethylformamide (DMF) or methyl-sulphoxide (DMSO), THF (THF), terepthaloyl moietie diether or the dioxane; In 45～65 ℃, handle the compound shown in the formula (II) with Diisopropylamine, tetramethyleneimine, pyridine, triethylamine and promptly get formula (I) compound.
The preparation (reaction formula 2) of formula (II) compound: in toluene or benzene, methylene dichloride, ethylene dichloride, trichloromethane solvent; Under the solvent refluxing temperature; Add triethylamine or pyridine acid binding agent, promptly get formula (II) compound with compound shown in the formula (III) and corresponding acyl chloride reaction.
The preparation (reaction formula 3) of formula (III) compound: in 50～80 ℃, in the presence of lewis acid catalyst aluminum chloride, handle benzene or halogeno-benzene (VII), get phenyl-β-chloro alkyl ketone (VI) with the 3-chlorpromazine chloride; At 80～120 ℃, in the solvent octane, get 2 with the above-mentioned phenyl-β of vitriolization-chloro alkyl ketone (VI), 3-indone (V); At 25～50 ℃, in the presence of the alkali sodium hydride, at solvent N, in the dinethylformamide, handle with methylcarbonate or diethyl carbonate, dipropyl carbonate, carbonic acid diisopropyl ester above-mentioned 2,3-indone (V), 2,3-indone-2-carboxylicesters (IV); At 15～35 ℃, in methylene chloride or ethylene dichloride, trichloromethane, to handle above-mentionedly 2 with the oxygenant metachloroperbenzoic acid, 3-indone-2-carboxylicesters (IV) promptly gets the compound of formula (III), like reaction formula 3,
Among the concrete compound method embodiment below more detailed elaboration is arranged.
Formula provided by the invention (I) compound, biologically active and the compound that has have good biological activity. particularly aspect the preventing and treating of agricultural, gardening, flowers and sanitary insect pest, evil mite, germ, show activity.Harmful organism described here include but not limited to this:
Harmful insect: Orthoptera such as blattaria; Thysanoptera such as cotton thrips, rice thrips, melon thrips; Homoptera such as leafhopper, plant hopper, aphid, lepidopteran such as oriental armyworm, prodenia litura, small cabbage moth, beet armyworm, trichoplusia ni, cabbage caterpillar; Hymenoptera such as sawfly larva, Diptera such as yellow-fever mosquito, culex, fly;
Pest mite class: acarina such as tangerine Panonychus citri, cotton spider mites, T.urticae Koch;
Harmful pathogenic bacteria: the phytophthora kind, white powder belongs to kind, the Gibberella kind, the Venturia kind, species of Monilinia fructicola, the Rhizoctonia kind, the Staphlosporonites kind, the Pyricularia Sacc. kind, the fusarium kind is like rice blast (Pyricularia oryzae); Stripe rust of wheat (Puccinia striiformis), leaf rust (Puccinia recondita) and other rust; Big wheat yellow rust (Puccinia striiformis), leaf rust (Puccinia recondita) and other rust; Barley and wheat powdery mildew (Erysiphegraminis), powdery mildew of cucumber (Sphaerotheca fuligenea), apple mildew (Podosphaera leucotrichar) and uncinula necator (Podosphaera leucotrichar); Wheat hypochnus and glume blight (Septoria nodorum).Length on the cereal wriggle spore, the mouth spore is mould, Septoria is sick, caryosphere shell Pseudomonas is sick, Pseudocercosporella herpotrichoides and take-all (Gaeumannomyces graminis).The cercospora brown spot of peanut (Cercospora arachidicola) and the cercospora black spot of peanut (Cercosporidium personata); The mould genus of its tail spore on beet, soybean and the paddy is sick.Tomato, cucumber, grape grey mould (Botrytis cinerea).Hinge spore on the vegetables (like cucumber) belongs to sick.Anthrax on the cucumber, scab of apple, cucumber downy mildew, downy mildew of garpe, the eqpidemic disease on yam and the tomato, other rhizoctonia on the list bacterium Thanatephorus cucumeris on the paddy and other hosts such as wheat and barley, the vegetables; Sclerotinia rot of colza (Sclerotonia sclerotiorum); Wheat scab (Gibberella zeae); Phytophthora capsici sick (Phytophythora capsici).
Formula provided by the invention (I) compound is effective for Pest Control, evil mite and germ.Usually use formula (I) compound of 5-5000ppm, it is dispersed in water or other the aqueous carrier, impose in the soil of plant, crop or plant growth, can prevent effectively that crop from suffering the infringement of insect, evil mite, germ.
Below in conjunction with embodiment the present invention is described further, the yield among the embodiment is all without optimization.
Embodiment
Embodiment 1
The preparation of compound 01 among the present embodiment instruction card l.
In the reaction flask (1000mL) that has whisking appliance, TM and tail gas reception, add chlorobenzene (VII-01646.0g) and aluminum chloride (193g), in 10～25 ℃; Drip 3-chlorpromazine chloride (170g); Drip and finish extremely fully, reactant is slowly added in the solution of concentrated hydrochloric acid (80.0g) and trash ice (2000g) composition the solid crude product that suction filtration is separated out in 50～60 ℃ of insulation reaction; Alcoholic solvent such as ethyl alcohol recrystallization get (VI-01) 276.6g, content 99.0% (GC).
In 90～110 ℃, in the mixing solutions of the vitriol oil (100mL) and octane (50mL), slowly drip octane (200mL) solution of (VI-01) (12.6) g, drip and finish; Be cooled to room temperature, inclining the octane layer, stirs down on the slow impouring trash ice of reaction solution (1000g); Filter and collect the solid of separating out; Washing, drying gets (V-01) 7.65g.
With sodium hydride (60%, 24g) be suspended among the DMF (200mL), in below 35 ℃, stir drip down (V-01) (63.6g) with the solution of DMF (150mL), stir 30min after, drip methylcarbonate (38mL), drip finish after, behind stirring 1.5h under the room temperature, placement is spent the night.In the mixture with careful impouring concentrated hydrochloric acid of reaction mixture (100mL) and 100 trash ices (100g), the extracted with diethyl ether secondary merges organic layer, wash anhydrous magnesium sulfate drying, concentrated brown oil (IV-01) 69.5g three times.
At 15～25 ℃, with metachloroperbenzoic acid (50%～60%, 50g) add in (IV-01) methylene dichloride (300mL) solution (25.0g) in batches; After finishing, continue stirring reaction 0.5～2.5h, be cooled to-5～5 ℃; Stir and slowly drip saturated aqueous sodium carbonate (500mL) down, tell organic layer, saturated sodium sulfite anhy 96 washing once; The water washing secondary, dried over mgso gets yellow solid (III-01) 20.5g after concentrating.
(III-01) (2.4g) is dissolved in the toluene (100mL), adds triethylamine (2.5g), stir down, slowly drip toluylic acid acyl chlorides (3.0g) in room temperature, drip finish after, be warming up to back flow reaction 3h.After being cooled to room temperature reaction solution is poured in the 250mL frozen water, told organic layer, wash three times, anhydrous sodium sulfate drying concentrates and obtains red-brown oily liquids (II-01) 2.5g, content 91.4%.
The preparation of (01) compound in the table 1: (II-01) (91.4%, 1.80g), DMF (20ml), Diisopropylamine (1.0g) is in 45～65 ℃ of reaction 4～6h; Cooling is poured in the frozen water, ethyl acetate extraction, washing organic layer; Drying, ETHYLE ACETATE+sherwood oil column chromatography or recrystallization purifying, must table 1 in (01); Pink solid 1.22g, content 95.0%, yield 71.7%.Fusing point: 145.6～147.5 ℃.
1H NMR (CDCl
3) 3.113 (d, J=15Hz, 1H, CH
2), 3.732 (s, 3H, OCH
3), 3.907 (d, J=15Hz, 1H, CH
2), 7.260-7.764 (m, 8H, Ph-H) .LC-MS (Pos M
+) m/z) calc:341, found:341.
Embodiment 2
The preparation method of compound 12 in the present embodiment instruction card 1.
In the 1000mL reaction flask that has whisking appliance, TM and tail gas reception, add benzene (VII-12448.0g) and aluminum chloride (192.9g), in 10～25 ℃; Drip 3-chlorpromazine chloride (168g); Drip and finish in 50～60 ℃ of insulation reaction extremely fully, reactant is slowly added in the solution of 80.0g concentrated hydrochloric acid and 2000g frozen water composition, cooling, suction filtration get bullion; Alcoholic solvent such as ethyl alcohol recrystallization get (VI-12) 228.4g, content 97.2%.
In 90～110 ℃, in the mixing solutions of the vitriol oil (100mL) and octane (50mL), slowly drip (VI-12) octane (200mL) solution (10.1g), drip and finish; Be cooled to room temperature, inclining the octane layer, stirs down on the slow impouring trash ice of reaction solution (1000g); Solid collected by filtration, washing, drying; Get (V-12) 6.05g, 94.6～95.7 ℃ of fusing points.
With sodium hydride (60%, 24g) be suspended among the DMF (200mL), in below 35 ℃, stir and to drip (V-12) (50.1g down; 0.3mol) and the solution of 150mL DMF, stir 30min after, drip methylcarbonate (38mL, 0.45mol); After drip finishing, under room temperature, stir 1.5h, place then and spend the night.In the mixture with reaction mixture careful impouring 100mL concentrated hydrochloric acid and 100mL ice, the extracted with diethyl ether secondary merges organic layer, wash anhydrous magnesium sulfate drying, concentrated brown oil (IV-12) 59.9g three times.
At 15～25 ℃, (50%～60%, 50g) add (IV-12) (25.0g is in methylene dichloride 0.11mol) (300mL) solution in batches with metachloroperbenzoic acid; After finishing, continue stirring reaction 0.5～2.5h, be cooled to-5～5 ℃, stir and slowly drip saturated aqueous sodium carbonate (500mL) down; Tell organic layer, saturated sodium sulfite anhy 96 washs once, the water washing secondary; Dried over mgso gets yellow solid (III-12) 20.5g, 139.4～141.1 ℃ of fusing points after concentrating.
(III-12) (2.4g) is dissolved in the toluene (100mL), adds triethylamine (2.5g), stir down, slowly drip toluylic acid chlorine (3.0g) in room temperature, drip finish after, be warming up to back flow reaction 3h.After being cooled to room temperature reaction solution is poured in the 250mL frozen water, told organic layer, wash three times, anhydrous sodium sulfate drying concentrates and obtains henna oily liquids (II-12) 2.5g, content 90.4%.
The preparation of (12) compound in the table 1: (II-12) (90.4%, 2.0g), DMF (20m1), Diisopropylamine (1.2g) is under the nitrogen protection; In 45～65 ℃ of reaction 4h, ethyl acetate extraction is poured in the frozen water in cooling into; The washing organic layer, drying concentrates ETHYLE ACETATE+sherwood oil column chromatography (1: 15); In must table 1 (12), faint yellow solid 0.52g, content 96.1%, yield 30.6%.Fusing point: 171.7～173.1 ℃.
1H NMR (CDCl
3) 3.154 (d, J=15Hz, 1H, CH
2), 3.723 (s, 3H, OCH
3), 3.912 (d, J=15Hz, 1H, CH
2), 7.262-7.827 (m, 9H, Ph-H) .LC-MS (Pos M
+) m/z) calc:307, found:307.
Reference implementation example 1 and embodiment 2, No.02～No.11 and No.13～No.20. in the synthetic table 1
Embodiment 3
The preparation suspension agent: the wetting dispersing agent with 2-6% is diluted in the frostproofer of 4-10% earlier; And in this solution, slowly add a certain amount of water; Then under the high speed shear cutter stirs; Formula provided by the invention (I) active compound that adds 5-80% successively, 0.01-0.05% sanitas, 0.01-0.05% skimmer and thickening material etc.Mill in the last impouring sand mill, add solvent again to volume.Be diluted with water to required any concentration during use.
Embodiment 4
The preparation emulsifiable concentrates: water, tensio-active agent, antifreezing agent, skimmer, thickening material and the sanitas with certain proportioning mixes composition homogeneous water earlier, formula provided by the invention (I) compound, suitable solvent and emulsifying agent, co-emulsifier mixed making it become even oil phase then.At last under high-speed stirring with the even oil phase emulsifiable concentrates that promptly can be made into mixed with water.Be diluted with water to required any concentration during use.
Institute's synthetic compound has been carried out desinsection, killed mite, and part of test results is listed in sterilization and weeding activity test at present.
The evaluated biological activity of 5 pairs of mythimna separatas of embodiment (Mythimna separata)
The Potter spray method: take by weighing an amount of formula provided by the invention (I) compound, with suitable solvent such as N, dinethylformamide or acetone solution add a small amount of tween 80 emulsifying agent again, stir, and add quantitative clear water, are mixed with desired concn, establish clear water and are contrast.Get fresh and tender leaf of Semen Maydis and be cut into the fragment of big or small basically identical, put into the petridish (Φ 90mm) that is lined with filter paper in advance.In ware, insert 10 of mythimna separata 3 instar larvaes then, be put under the Potter spray tower and quantitatively spray, spraying liquid amount 1ml, every concentration repeats for 3 times.Dispose, cover the ware lid, place the recovery indoor cultivation, routine observation, record of search examination worm death condition is calculated mortality ratio (%), results averaged after 72 hours.Last active with respect to blank in per-cent.Under the 1000mg/L condition, active (mortality ratio) is more than 85% like 04 grade for part of compounds.
The acaricidal activity evaluation of 6 pairs of two-spotted spider mites of embodiment (Tetranychus urticae)
Method is following: medicament is prepared with embodiment 5, selects the bean seedlings inoculation red spider grow fine, treat that red spider grows surely after; Flooded 10 seconds being with the mite bean seedlings to cut in formula provided by the invention (I) soup for preparing; Taking-up is inhaled with filter paper and is removed unnecessary soup, inserts in the beaker that is filled with water, in observing indoor cultivation; Inspection survival and dead mite number have 100-200 mite after 48 hours on every strain bean seedlings.Experiment repetition 3 times.Results averaged.Active with respect to blank in per-cent.Under the 500mg/L condition, active (mortality ratio) is about 50% like 12 grades for part of compounds.
Embodiment 7
Insecticidal activity evaluation to bean aphid (Aphis fabae)
Method is following: medicament is prepared with embodiment 5, and bean aphid is connected on the bean seedlings that just have been unearthed, and every strain connects more than 20; Then bean seedlings are dipped in formula provided by the invention (I) the soup soup together with the examination worm; Take out after 5 seconds, inhale and remove unnecessary soup, insert in the sponge of suction; Cover inspection survival and dead borer population after 24 hours with glass-tube.Repeat results averaged 3 times.Active blank relatively is in per-cent.Under the 500mg/L condition, part of compounds is as 08 etc., and active (mortality ratio) reaches 95%; Part of compounds like 14,15,19 isoreactivities (mortality ratio) 50～70%; Part of compounds like 03,04,09 etc. activity (mortality ratio) 40～50%.
The fungicidal activity of 8 pairs of Sclerotinia sclerotiorums of embodiment (Sclerotonia sclerotiorum)
Method is (toxic medium therapy) as follows: (1) Sclerotinia sclerotiorum (Sclerotonia sclerotiorum) bacterial classification is kept in the refrigerator (4-8 ℃), is inoculated in the petridish from the test tube slant in 2-3 days before the test, under optimal temperature, cultivates to be for experiment.(2) the medicament preparation is with embodiment 5.Taking liquid 2mL adds in the potato agar substratum (PDA) of the 38mL that is cooled to 45 ℃, and being mixed with concentration is the pastille culture medium flat plate of 25mg/L.(3) get 6.5mm diameter mycelia piece from cultured test germ colony edge, move on the pastille substratum, every processing repeats for 4 times.Dispose, place 28 ℃ the biochemical incubator of constant temperature to cultivate, measure colony diameter after 4-6 days, calculate growth inhibition ratio.(4) under 25mg/L concentration; Part of compounds shows the obvious sterilization activity; Like compound 01,13,14 etc. the growth inhibition ratio of Sclerotinia sclerotiorum is reached 90～100%, compound 02,03,05,07 etc. reach 50～70% to the growth inhibition ratio of Sclerotinia sclerotiorum.Wherein 01 compound such as grade still shows very high activity (seeing table 2) under lower concentration.
Table 2 part of compounds is to the biological activity (%) of Sclerotinia sclerotiorum
The fungicidal activity of 9 pairs of wheat powdery mildews of embodiment (Blumeria graminis)
Method is (pot-culture method) as follows: (1) wheat powdery mildew (Blumeria graminis) is preserved spore with stem and leaf of Wheat and is for experiment.(2) the medicament preparation is with embodiment 5.(3) select for use seedling to grow to the susceptible variety stem and leaf of Wheat of 2 leaves～3 leaf phases; With spray method with 500mg/L compound medicine liquid spray on stem and leaf of Wheat, dry naturally, evenly shake off to be inoculated on the stem and leaf of Wheat the fresh spore of white powder germ that produced in last 24 hour of morbidity wheat leaf blade; Every processing is no less than 3 basins; Every basin 10 strains, the protectiveness test is inoculation in 24 hours after chemicals treatment, puts then under the suitable condition and cultivates.According to blank incidence classification investigation, calculate control effect.(4) under 500mg/L concentration, part of compounds shows the obvious sterilization activity, reaches 90～100% like the preventive effect of 01 pair of wheat powdery mildew of compound, and the preventive effect of 07 pair of wheat powdery mildew of compound reaches 70～90%.
The fungicidal activity of 10 pairs of rice blast fungus of embodiment (Pyricularia oryzae)
Method is following: medicament is prepared with embodiment 5.Get 1 milliliter of soup in 50 milliliters of PDA substratum that dissolve with transfer pipet, after fully shaking up, pour into respectively in 3 petridish and repeat as 3 times, cooling back use inoculating needle picking diameter is that 5 millimeters bacterium cake places petridish central authorities, establishes thinner simultaneously and is contrast.Active with respect to blank in per-cent.Part of compounds shows the obvious sterilization activity; Under 25mg/L concentration; The activity of 01,07 pair of rice blast fungus of compound reaches 90～100%, and the activity of 04 pair of rice blast fungus of compound reaches 70～90%, and the activity of 05,06 pair of rice blast fungus of compound reaches 50～70%.
The fungicidal activity of 11 pairs of Rhizoctonia solani Kuhns of embodiment (Rhizoctonia solani)
Method is (broad bean blade method) as follows: (1) Rhizoctonia solani Kuhn (Rhizoctonia solani) bacterial classification is kept in the refrigerator (4-8 ℃), is inoculated in the petridish from the test tube slant in 2-3 days before the test, under optimal temperature, cultivates to be for experiment.(2) the medicament preparation is with embodiment 5.(3) blade of clip broad bean susceptible variety; Put in the petridish, with atomizer 500mg/L compound soup is squirted vacuum side of blade, behind the natural air drying; Use inoculator to have the one side of mycelia to be inoculated in as 6.5mm bacterium cake diameter and handle blade central authorities; The protectiveness test is inoculation in 24 hours after chemicals treatment, and inoculation is placed in the growth cabinet, under the condition of 26～28 ℃ of temperature, relative humidity 80%～90%, cultivates.Look the blank incidence, calculate control effect.(4) part of compounds shows the obvious sterilization activity, and under 500mg/L concentration, compound 01 grade reaches 70～90% to the control effect of Rhizoctonia solani Kuhn, and compound 09 grade reaches 50～70% to the control effect of Rhizoctonia solani Kuhn.
The fungicidal activity of 12 pairs of gibberellic hyphas of embodiment, phytophthora root rot bacterium, ash arrhizus bacteria
Method with reference to embodiment 7～embodiment 11; Studied the sterilization biological activity of the right gibberellic hypha of compound shown in the formula (I), phytophthora root rot bacterium, ash arrhizus bacteria etc.; The result shows that part of compounds shows obvious activity to one or more of above-mentioned germ; To the activity of gibberellic hypha, phytophthora root rot bacterium, ash arrhizus bacteria all 50～70%, the activity of 04 pair of gibberellic hypha of compound, ash arrhizus bacteria all reaches 50～70% etc. like compound 07 grade.
Claims (5)
1. the indeno oxa-carboxylic acid derivative of biologically active is characterized in that representing with general formula (I):
Wherein:
R is C
1～C
3Alkyl;
R
1Be H or halogen;
R
2Be halogen, phenyl, phenyl is selected from 5 identical or different substituting groups of following middle as many as and is replaced: hydrogen, halogen, C
1～C
3Alkyl, C
1～C
3Haloalkyl, C
1～C
3Alkyl oxy, C
1～C
3Haloalkyl oxygen base;
In the definition of the compound that provides above (I), no matter following substituting group is represented in the separately use or be used in the compound word of used term:
Halogen: refer to fluorine, chlorine, bromine, iodine;
Alkyl: refer to the straight or branched alkyl;
Haloalkyl: refer to the straight or branched alkyl, the Wasserstoffatoms on these alkyl is partly or entirely replaced by halogen atom;
Alkyl oxy: refer to have the straight or branched alkyl oxy of 1-3 carbon atom, be connected on the structure through the Sauerstoffatom key;
Haloalkyl oxygen base: refer to have the straight or branched alkyl oxy of 1-3 carbon atom, the Wasserstoffatoms on these alkyl oxies can partly or entirely be replaced by halogen atom.
2. the indeno oxa-carboxylic acid derivative of biologically active according to claim 1 is characterized in that preferred general formula (I) compound and chemical structural formula are following:
3. the indeno oxa-carboxylic acid derivative of biologically active according to claim 1 and 2 is characterized in that general formula (I) compound is that form with one or more isomer exists, and comprises enantiomorph or diastereomer, geometrical isomer.
4. the preparation method of the indeno oxa-carboxylic acid derivative of biologically active according to claim 1 and 2; It is characterized in that at solvent N; In dinethylformamide (DMF) or methyl-sulphoxide (DMSO), THF (THF), terepthaloyl moietie diether, the dioxane; In 45～65 ℃, handle the compound shown in the formula (II) with alkali Diisopropylamine, tetramethyleneimine, pyridine or triethylamine and promptly get formula (I) compound, like reaction formula 1;
Reaction formula 1:
In solvent toluene or benzene, methylene dichloride, ethylene dichloride, trichloromethane, under the solvent refluxing temperature, add acid binding agent triethylamine or pyridine, promptly get formula (II) compound with compound shown in the formula (III) and corresponding acyl chloride reaction, like reaction formula 2;
Reaction formula 2:
In 50～80 ℃, in the presence of lewis acid catalyst aluminum chloride, handle benzene or halogeno-benzene (VII) with the 3-chlorpromazine chloride, get phenyl-β-chloro alkyl ketone (VI); At 80～120 ℃, in the solvent octane, get 2 with the above-mentioned phenyl-β of vitriolization-chloro alkyl ketone (VI), 3-indone (V); At 25～50 ℃, in the presence of the alkali sodium hydride, at solvent N, in the dinethylformamide, handle with methylcarbonate or diethyl carbonate, dipropyl carbonate, carbonic acid diisopropyl ester above-mentioned 2,3-indone (V), 2,3-indone-2-carboxylicesters (IV); At 15～35 ℃, in methylene chloride or ethylene dichloride, trichloromethane, to handle above-mentionedly 2 with the oxygenant metachloroperbenzoic acid, 3-indone-2-carboxylicesters (IV) promptly gets the compound of formula (III), like reaction formula 3,
Reaction formula 3:
R in reaction formula 1～reaction formula 3
1, R
2Have with R and to give definition in the claim 1.
5. the purposes of indeno oxa-carboxylic acid derivative according to claim 1 and 2 is characterized in that biologically active, under 2.5～5000mg/L consumption, has mite, desinsection, sterilization biological activity extremely.
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| CN101928272A (en) * | 2010-06-12 | 2010-12-29 | 湖南化工研究院 | 3-o-methylphenyl-2-oxo-1-oxaspiro[4,5]-decyl-3-alkene-4-ol derivative |
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