CN101928272B - 3-o-methylphenyl-2-oxo-1-oxaspiro[4,5]-decyl-3-alkene-4-ol derivative - Google Patents

3-o-methylphenyl-2-oxo-1-oxaspiro[4,5]-decyl-3-alkene-4-ol derivative Download PDF

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CN101928272B
CN101928272B CN 201010199257 CN201010199257A CN101928272B CN 101928272 B CN101928272 B CN 101928272B CN 201010199257 CN201010199257 CN 201010199257 CN 201010199257 A CN201010199257 A CN 201010199257A CN 101928272 B CN101928272 B CN 101928272B
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compound
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oxaspiro
alkene
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CN101928272A (en
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王晓光
柳爱平
裴晖
祝小星
刘兴平
喻快
胡礼
刘卫东
刘民华
毛冠群
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Hunan Research Institute of Chemical Industry
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/94—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom spiro-condensed with carbocyclic rings or ring systems, e.g. griseofulvins
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/12—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings condensed with a carbocyclic ring
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • A01N47/06—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom containing —O—CO—O— groups; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof

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Abstract

The invention discloses a 3-o-methylphenyl-2-oxo-1-oxaspiro[4,5]-decyl-3-alkene-4-ol derivative with insecticidal, acaricidal and antifungal biological activities and a preparation method thereof, wherein R is a substituent shown as the description.

Description

3-o-methyl-phenyl--2-oxo-1-oxaspiro [4,5]-last of the ten Heavenly stems-3-alkene-4-alcohol derivate
Technical field
The present invention relates to have desinsection, kill mite, the 3-of antifungal bioactivity o-methyl-phenyl--2-oxo-1-oxaspiro [4,5]-last of the ten Heavenly stems-3-alkene-4-alcohol derivate and their preparation method.
Background technology
The control of insect, evil mite, germ is extremely important in realizing the process of high-efficiency agriculture.The simultaneously control of insect, evil mite, germ woods, herd, also very important in secondary, fishing and public health.Although existing a lot of insects, evil mite, bacteria-treating agent on market, but due to the problem such as the continuous expansion in market and insect, evil mite, sick resistance, the work-ing life of medicine and the economy of medicine and people to the environment pay attention to day by day, need scientists constantly to study, and then efficient, safety, the economy and the desinsection with different modes of action that make new advances of exploitation, kill mite, sterilant kind.
Beyer Co., Ltd discloses the spirocyclic tetronic acid compounds with desinsection, acaricidal activity shown in formula (P) in DE 19901943 and EP 0528156, in formula (P), and X, Y, Z are alkyl, halogen, alkoxyl group.By the further research to this compounds, Beyer Co., Ltd has developed the spiral shell mite ester shown in formula (P-i) in succession, spiral shell worm ethyl ester shown in Spiromesifen shown in formula (P-ii) and formula (P-iii), spiral shell mite ester shown in formula (P-i), spiral shell worm ethyl ester shown in Spiromesifen shown in formula (P-ii) and formula (P-iii) are also present only three the commercialization pesticide species of such active compound.
Figure DEST_PATH_GSB00000325473900011
Have better for designing and synthesizing, broad-spectrum biological activity more, more economical new spiral shell ester compound again simultaneously, we are that the 2-methylphenyl acetic acid replaces the disubstituted benzene acetic acid in spiral shell worm ethyl ester, spiral shell mite ester, Spiromesifen with mono-substituted toluylic acid, simultaneously the carboxylic acid derivative of sulphur, oxygen or halogen is introduced in the spirocyclic tetronic acid structure, design and synthesize have no bibliographical information have the 3-o-methyl-phenyl-with desinsection, acaricidal activity shown in formula (I)-2-oxo-1-oxaspiro [4,4]-ninth of the ten Heavenly Stems-3-alkene-4-alcohol and derivative thereof.Wherein part of compounds (as 02 etc.) demonstrate than spiral shell mite ester, Spiromesifen more preferably economy and Geng Gao desinsection, kill mite or antifungal bioactivity.
Summary of the invention
The invention provides having desinsection, kill mite shown in formula (I), the 3-of antifungal bioactivity o-methyl-phenyl--2-oxo-1-oxaspiro [4,5]-last of the ten Heavenly stems-3-alkene-4-alcohol derivate and isomer thereof:
Wherein: R is substituting group as follows:
Figure BSA00000141001100021
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 composition that is selected from tensio-active agent, solid diluent and liquid diluent of a kind of pest control, evil mite.
The invention still further relates to a kind of method of pest control, evil mite, comprise formula (I) compound contact insect or its environment with biologic effective dose.Also relate to simultaneously a kind of like this insect, control of pest mite method, insect, evil mite or its environment are with formula (I) compound of biologic effective dose or contain at least a other compound 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 various crops the various mite classes such as cotton spider mites, tangerine Panonychus citri; Some compounds can be used for preventing and treating on various crops the various harmful insects such as mythimna separata, small cabbage moth, prodenia litura, beet armyworm, leafhopper, aphid, and the compound that has has very high biological activity to some target pest, evil mite and makes under very low dosage and just can obtain good effect.
In view of economy and the biological activity of compound, the preferred formula of the present invention (I) compound is:
Figure BSA00000141001100022
The preferred composition of the present invention is the composition that contains above-mentioned preferred compound.Preferred method is to use the method for above-mentioned preferred compound.
The present invention lists above-mentioned preferred formula (I) compound (01)～(13) with table 1 and further illustrates the present invention, but does not limit the present invention.In the present invention the fusing point of giving all not calibrated, in table 1, all compounds all can be observed its molecular ion peak in LC-MS (APCI, Pos) (Agilent 1100Series LC/MSD) and GC-Mass (EI, 70eV, m/z).Compound in table 1 1Mark in H NMR (Varian INOVA-300spectrometer) does with tetramethylsilane (TMS).
Table 1:
Figure BSA00000141001100041
Compound shown in formula of the present invention (I) can obtain by the reaction formula 1 shown in following, and (II) in reaction formula 1 can obtain by the reaction formula 2 shown in following, and (IV) in reaction formula 2 can obtain by reaction formula 3.Substituting group wherein except specializing all as front restriction.
Reaction formula 1:
Reaction formula 2:
Figure BSA00000141001100043
Reaction formula 3:
Figure BSA00000141001100044
The compound of formula (I) can prepare (reaction formula 1) like this: in suitable solvent such as methylene dichloride or toluene, in-5～55 ℃, under suitable alkali such as triethylamine, pyridine exist, acyl chloride reaction with shown in the compound shown in formula (II) and corresponding formula (III) adds suitable catalyzer such as 4-dimethylamino pyridine (DMAP) can add fast response or improves reaction yield.
The compound of formula (II) can prepare (reaction formula 2) like this: in solvent-free or suitable solvent such as toluene, sulfur oxychloride and o-Tolylacetic acid (II-a), react under the system reflux temperature, slough solvent and get o-methyl-benzene Acetyl Chloride 98Min. (II-b); As in toluene, benzene, add suitable catalyzer such as 4-dimethylamino pyridine in suitable solvent, react to get formula (II-c) with the o-methyl-benzene Acetyl Chloride 98Min. (II-b) of above-mentioned gained and the compound shown in formula (IV) under the system reflux conditions; In suitable solvent such as pyridine, in 15～30 ℃ of formula (II-c) compounds with suitable alkali such as potassium hydroxide, the above-mentioned gained of sodium-hydroxide treatment, more namely get formula (II) compound with 5%～20% salt acid treatment.
The compound of formula (IV) can make by reaction formula 3 by reference [US 6861391B1].
Concrete synthetic method has more detailed elaboration in the following embodiments.
Formula provided by the invention (I) compound has biological activity and the compound that has has good biological activity. particularly show high reactivity aspect the preventing and treating of agricultural, gardening, flowers and sanitary insect pest, evil mite.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, cabbage looper, 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;
Formula provided by the invention (I) compound is effective for Control pests and mite.Usually use formula (I) compound of 5-5000ppm, it is dispersed in water or other aqueous carrier, impose in the soil of plant, crop or plant growth, can prevent effectively that crop from suffering the infringement of worm and/or mite.
When using formula of the present invention (I) compound separately, be that effectively they also can use together with the other biological chemical substance to controlling worm and/or mite, these biochemicals comprise other sterilants, nematocides and miticide.
With (I) provided by the invention compound, Agrotechnical formulation as effective ingredient, can make desirable any formulation as the compressing grains done, easily flow mixture, granula, wettable powder, water dispersible granules, emulsifiable concentrate, pulvis, powdery enriched material, microemulsion, suspension agent, missible oil, aqueous emulsion, soluble liquid, aqua, dispersible agent, suitable auxiliary agent comprises carrier (thinner) and other auxiliary such as spreader-sticker, emulsifying agent, wetting agent, dispersion agent, tackiness agent and decomposition agent.Contain in these preparations with inertia, compound of the present invention that the acceptable solid of pharmacology or liquid diluent have mixed.
For example: wettable powder of the present invention, pulvis and powder enriched material, can be by with the about formula of 5-30% (I) compound of weight, with weight approximately the solid anion surfactant of 5-30% mill together and prepare.The dioctyl ester that a kind of suitable anion surfactant is sodium sulfosuccinate.The also inert solid diluent of operating weight 40%-90% in these preparations is as talcum, kaolin, diatomite, Wingdale, silicate etc.
The preparation of compressing grains be with about equivalent as 5-30 part formula (I) compound and solid surfactant and approximately the gypsum of 40-90 part mill together, then the mixture recompression is approximately 10-100 order (1.676-0.152mm) size or larger particle.
The solid surfactant that uses in the present invention's formula not only has the dioctyl phenyl ester of the sodium sulfosuccinate of negatively charged ion, also has the block polymer of non-ionic type oxyethane and propylene oxide.
Easily flowing agent can be used together with the aqueous solution on the spot.
Formula (I) solid preparation can be combined with other sterilant, can be used as multicomponent mixture and uses, and perhaps sequentially uses.
In like manner, the liquid preparation of formula (I) also can be combined with other sterilant, can mix in container or use successively respectively in the liquid spray mode.Effective formula (I) compound that should contain the 50-5000ppm that has an appointment in spray liquid agent prescription of the present invention.
The example of composition of the present invention can be also wettable powder, pulvis, granule and liquor, emulsible enriching agent, emulsion, suspension enriching agent, aerosol and smoke substance.Wettable powder contains 15,25,50 weight activeconstituentss usually, and usually except solid inert carrier, also contains 3-10% weight fraction powder, can add in case of necessity 0-10% weight stablizer and/or other additive such as permeate agent and tackiness agent.Pulvis may be molded to the pulvis enriching agent that has the composition similar to wettable powder but there is no dispersion agent usually.Granula is made usually has 10-100 order (1.676-0.152mm) size, and available agglomerating or implantttion technique preparation.Usually, granula contains the activeconstituents of 0.5-50% weight and 0-10% weight additive such as stablizer, tensio-active agent, slowly-releasing modifying agent.Outside but emulsion concentrate desolventizes, can contain cosolvent in case of necessity, the 1-50%W/V activeconstituents, other additive of 2-20%W/V emulsifying agent and 0-20%W/V such as stablizer, permeate agent and corrosion inhibitor, suspension enriching agent contain the activeconstituents of 10-75% weight, the dispersion agent of 0.5-15% weight, other additive such as defoamer, corrosion inhibitor, stablizer, permeate agent and the tackiness agent of 0.1-10% weight usually.
Water dispersant and emulsion, for example by dilute with water according to the composition that wettable powder of the present invention or enriched material obtain, also list scope of the present invention in.Indication emulsion comprises two kinds of water-in-oil and oil-in-waters.
The invention will be further described below in conjunction with embodiment, and the yield in embodiment is all without optimization.
Embodiment
Embodiment 1
The preparation method of compound 01 in the present embodiment instruction card 1.
Figure BSA00000141001100061
The preparation of 2-methylthio group propionyl chloride
The preparation of 2-methylthio group propionic acid
Under stirring at room, 2-chloropropionic acid (4.63g) is added drop-wise to 6% NaHCO 3(60ML) in the aqueous solution, react to the solution without Bubble formation, remove most of water on Rotary Evaporators, get the aqueous solution of 2-chloropropionic acid sodium, then add wherein sodium methyl mercaptide (20ML) aqueous solution of dimethyl formamide (DMF, 20mL) and 20%, be warming up to 80 ℃, stirring reaction 10-20 hour, be cooled to after room temperature slowly in impouring water (20-50ML), the 2N hcl acidifying is to PH=3-4, ethyl acetate extraction, the washing organic phase, anhydrous Na SO 4Drying, concentrated on Rotary Evaporators, get 2-methylthio group propionic acid liquid 3.96g, yield 76%.
The preparation of 2-methylthio group propionyl chloride adds 2-methylthio group propionic acid (5.0g in the single neck flask of 100mL, 41.6mmol), methylene dichloride (30mL), dimethyl formamide (5), drip oxalyl chloride (6.50g under ice bath, 51.18mmol), 30min dropwises, and naturally is warming up to room temperature, and stirring reaction spends the night, desolvation and excessive oxalyl chloride on Rotary Evaporators get 2-methylthio group propionyl chloride 5.25g.
3-(2-aminomethyl phenyl)-2-oxo-1-oxaspiro [4,5]-last of the ten Heavenly stems-preparation (II) of 3-alkene-4-alcohol
The preparation of 2-methylbenzene Acetyl Chloride 98Min. (II-b) adds 2-methylphenyl acetic acid (15.1g), sulfur oxychloride (29.8g) and toluene (120ML) in being furnished with the 250mL there-necked flask of magnetic stirring apparatus, thermometer and prolong, fully after dissolving, be heated to reflux temperature reaction 3-6 hour, underpressure distillation removes toluene and superfluous thionyl chloride, get 2-methylbenzene Acetyl Chloride 98Min. sorrel oily transparent liquid 13.5g, content 97.0%, yield 77.2%.
The preparation of 1-(2-(2-aminomethyl phenyl)-acetoxyl group)-cyclohexyl ethyl formate adds 1-hydroxy-cyclohexyl ethyl formate (13.2g), toluene (100ML), 4-dimethylamino pyridine (1.0g) in the there-necked flask of the 250mL that is furnished with magnetic stirring apparatus, thermometer, prolong and constant pressure funnel, drip 2-methylbenzene Acetyl Chloride 98Min. (29.3g) under stirring at room, dripped complete heating reflux reaction 12 hours.Cooling, suction filtration, underpressure distillation are sloughed toluene and are got 1-(2-(2-aminomethyl phenyl)-acetoxyl group)-greyish white solid of cyclohexyl ethyl formate (22.8g), content 93.0%, yield 91.0%.
3-(2-aminomethyl phenyl)-2-oxo-1-oxaspiro [4, 5]-last of the ten Heavenly stems-preparation (II) of 3-alkene-4-alcohol adds 1-(2-(2-aminomethyl phenyl)-acetoxyl group)-cyclohexyl ethyl formate (22.8g) in the there-necked flask of 250mL, potassium hydroxide (8.28g) and pyridine (80ML), stirring at room reaction 2～4 hours, in cold hydrochloric acid (500ML) with reactant impouring 10%, under stirring at room, separate out pale yellow solid, filter, washing, sherwood oil is washed, dry 3-(2-the aminomethyl phenyl)-2-oxo-1-oxaspiro [4 that gets, 5]-last of the ten Heavenly stems-3-alkene-4-alcohol 14.7g, content 93.0%, yield 70.6%.
3-(2-aminomethyl phenyl)-2-oxo-1-oxaspiro [4,5]-last of the ten Heavenly stems-3-alkene-4-base-2-methylthio group propionic acid ester synthesis (No.01 in table 1)
is being furnished with magnetic stirring apparatus, add 3-(2-aminomethyl phenyl)-2-oxo-1-oxaspiro [4 in the there-necked flask of the 100mL of thermometer and prolong, 5]-last of the ten Heavenly stems-3-alkene-4-alcohol (1.50g), methylene dichloride (40ml) and pyridine (0.6g), abundant stirring and dissolving, drip the 2-methylthio group propionyl chloride (1.21g) that is dissolved in methylene dichloride (10ML) under condition of ice bath, drip and finish, after room temperature reaction 3～5 hours, the reactant frozen water is washed, the saturated common salt washing, anhydrous magnesium sulfate drying, concentrated, purification by silica gel column chromatography (sherwood oil: ethyl acetate 10: 1) get title compound 0.83g, content 95.5%, yield 38.0%.The white solid fusing point of class: 98.8～100.4 ℃. 1H NMR (CDCl 3) 1.342-1.366 (d, 3H, CH 3), 1.703 (s, 3H, SCH 3), 1.789-1.797 (m, 10H, hexanaphthene), 2.294 (s, 3H, Ph-CH 3), 3.296-3.368 (q, 1H, CH), 7.130-7.262 (m, 4H, Ph-H) .LC-MS (Pos M +) m/z) calc:361, found:361.
Embodiment 2
The preparation method of compound 02 in the present embodiment instruction card 1.
3-(2-aminomethyl phenyl)-2-oxo-1-oxaspiro [4,5]-last of the ten Heavenly stems-3-alkene-4-base-chloro trimethylacetic acid ester synthesis (No.02 in table 1)
is being furnished with magnetic stirring apparatus, add 3-(2-aminomethyl phenyl)-2-oxo-1-oxaspiro [4 in the there-necked flask of the 100mL of thermometer and prolong, 5]-last of the ten Heavenly stems-3-alkene-4-alcohol (0.50g), methylene dichloride (40ml) and triethylamine (0.3g), fully dissolving is stirred, drip the Chloropivaloyl chloride (0.42g) that is dissolved in methylene dichloride (10ML) under condition of ice bath, drip and finish, room temperature reaction 3-5 hour, reactant is washed, the saturated common salt washing, anhydrous magnesium sulfate drying, concentrated, purification by silica gel column chromatography (sherwood oil: ethyl acetate 10: 1) get title compound 0.32g, content 94.5%, yield 41.4%.The white solid fusing point of class: 97.1～98.8 ℃. 1HNMR (CDCl 3) 1.161 (s, 6H, 2CH 3), 1.791 (m, 10H, hexanaphthenes), 2.281 (s, 3H, Ph-CH 3), 3.543 (s, 2H, CH 2), 7.039-7.246 (m, 4H, Ph-H) .LC-MS (Pos M +) m/z) calc:377, found:377.
Embodiment 3
The preparation method of compound 03 in the present embodiment instruction card 1.
Figure BSA00000141001100072
Figure BSA00000141001100081
The preparation of 2-methylthio group-2 methyl-prop acyl chlorides
The preparation of 2-methylthio group-2 methylpropanoic acid adds 20% the sodium methyl mercaptide aqueous solution (41.2g) in the 100mL three-necked flask that thermometer, prolong, constant pressure funnel are housed, under ice-water bath, after 2 bromo 2 methyl propionic acid (6.68g) is dissolved in 20mL water, be added drop-wise in mentioned solution, 25min dropwises, after 10～15 ℃ of reaction 3h, under room temperature, reaction is spent the night, react complete after, slowly drip the 20Ml concentrated hydrochloric acid, transfer to Ph=3～4, reaction mixture 20mL extracted with diethyl ether three times, 20mL chloroform extraction secondary merges organic layer, anhydrous Na SO 4Drying, concentrated on Rotary Evaporators, get lurid liquid 4.01g, yield 75.0%.
With reference to the correlation method of embodiment 1, prepare 2-methylthio group-2 methyl-prop acyl chlorides by 2-methylthio group-2 methylpropanoic acid.
3-(2-aminomethyl phenyl)-2-oxo-1-oxaspiro [4,5]-last of the ten Heavenly stems-3-alkene-4-base-2-methylthio group-2 Methylpropionic acid ester synthesis (No.03 in table 1)
is being furnished with magnetic stirring apparatus, add 3-(2-aminomethyl phenyl)-2-oxo-1-oxaspiro [4 in the there-necked flask of the 100mL of thermometer and prolong, 5]-last of the ten Heavenly stems-3-alkene-4-alcohol (0.52g), methylene dichloride (40ml) and pyridine (0.5g), fully dissolving is stirred, drip the 2-methylthio group isobutyryl chloride (0.38g) that is dissolved in methylene dichloride (10ML) under condition of ice bath, drip and finish, room temperature reaction 3-6 hour, reactant is washed, the saturated common salt washing, anhydrous magnesium sulfate drying, concentrated, purification by silica gel column chromatography (sherwood oil: ethyl acetate 15: 1) get title compound 0.30g, content 93.8%, yield 37.5%.The white solid fusing point of class: 104.4～105.5 ℃. 1H NMR (CDCl 3) 1.430 (s, 6H, 2CH 3), 1.591 (s, 3H, CH 3), 1.794 (br, 10H, hexanaphthenes), 2.303 (s, 3H, Ph-CH 3), 7.132-7.247 (m, 4H, Ph-H) .LC-MS (Pos M +) m/z) calc:375, found:375.
Embodiment 4
The preparation method of compound 04 in this example instruction card 1.
Figure BSA00000141001100082
3-(2-aminomethyl phenyl)-2-oxo-1-oxaspiro [4,5]-last of the ten Heavenly stems 3-alkene-4-base-ethylene-acetic acid ester synthesis (No.04 in table 1)
is being furnished with magnetic stirring apparatus, add 3-(2-aminomethyl phenyl)-2-oxo-1-oxaspiro [4 in the there-necked flask of the 100mL of thermometer and prolong, 5]-last of the ten Heavenly stems-3-alkene-4-alcohol (0.52g), methylene dichloride (40ml) and triethylamine (0.60g), fully dissolving is stirred, drip the cyclopropyl formyl chloride (0.36g) that is dissolved in methylene dichloride (10ML) under condition of ice bath, drip and finish, room temperature reaction 4-5 hour, reactant is washed, the saturated common salt washing, anhydrous magnesium sulfate drying, concentrated, purification by silica gel column chromatography (sherwood oil: ethyl acetate 15: 1) get title compound 0.28g, content 96.1%, yield 41.0%.The white solid fusing point of class: 115.6.1～116.5 ℃. 1HNMR (CDCl 3) 0.864-0.950 (m, 4H, CH 2CH 2), 1.261-1.285 (m, 1H, CH), 1.704-1.835 (m, 10H, hexanaphthene), 2.258 (s, 3H, CH 3), 7.104-7.207 (m, 4H, Ph H); GC-MS (M +) m/z) calc:326, found:326
Embodiment 5
Reference example 1～embodiment 4, No.05～No.13. in synthetic table 1
Embodiment 6
Reference example 1～embodiment 4 and relevant references, other compound in synthetic the present invention.
Embodiment 7
The preparation suspension agent: first the wetting dispersing agent with 2-6% is diluted in the frostproofer of 4-10%, and slowly add a certain amount of water in this solution, then under the high speed shear cutter stirs, formula provided by the invention (I) active compound that adds successively 5-80%, the 0.01-0.05% sanitas, 0.01-0.05% defoamer and thickening material etc.Mill in last impouring sand mill, then add solvent to volume.Be diluted with water to required any concentration during use.
Embodiment 8
The preparation emulsifiable concentrates: first water, tensio-active agent, antifreezing agent, defoamer, thickening material and the sanitas with certain proportioning mixes composition homogeneous water, then formula provided by the invention (I) compound, suitable solvent and emulsifying agent, co-emulsifier mixed making it become even oil phase.At last under high-speed stirring with the even oil phase emulsifiable concentrates that namely can be made into mixed with water.Be diluted with water to required any concentration during use.
Embodiment 9
3-(2-aminomethyl phenyl)-2-oxo-1-oxaspiro [4,5]-last of the ten Heavenly stems-preparation of 3-alkene-4-base-2-methylthio group propionic ester (No.01 in table 1) 10% suspension agent
first with 5 parts of suitable tensio-active agents such as naphthalenesulfonic acid-formaldehyde condensate, the sodium dibutyl naphthalene sulfonate formaldehyde condensation products is diluted in 5 parts of suitable frostproofers such as ethylene glycol, in glycerol, and slowly add entry in this solution, add successively 10 parts of active compound 3-provided by the invention (2-aminomethyl phenyl)-2-oxo-1-oxaspiro [4 under rapid stirring, 5]-last of the ten Heavenly stems-3-alkene-4-base-2-methylthio group propionic ester (No.01 in table 1) and other suitable auxiliary agent such as sanitas (phenylformic acid or formaldehyde etc.), defoamer (organic silicone) and thickening material (xanthan gum or carboxymethyl cellulose etc.), mill, add at last residual solvent to volume.
Institute's synthetic compound has been carried out desinsection, killed mite, and part of test results is now listed in sterilization and weeding activity test.
The evaluated biological activity of 10 pairs of mythimna separatas of embodiment (Mythimna separata)
The Potter spray method: take appropriate 3-provided by the invention (2-aminomethyl phenyl)-2-oxo-1-oxaspiro [4,5]-last of the ten Heavenly stems-3-alkene-4-alcohol derivate, with N, the dinethylformamide dissolving, then add a small amount of tween 80 emulsifying agent, stir, add quantitative clear water, be mixed with desired concn, establish clear water and be contrast.Get fresh and tender leaf of Semen Maydis and be cut into the basically identical fragment of size, put into the culture dish (Φ 90mm) that is lined with in advance filter paper.Then access 10 of mythimna separata 3 instar larvaes in ware, be put under the Potter spray tower and quantitatively spray, spraying liquid amount 1ml, every concentration repeats for 3 times.Be disposed, cover the ware lid, be placed in the recovery indoor cultivation, routine observation, record of search examination worm death condition, calculate mortality ratio (%), results averaged after 72 hours.Activity in per-cent, is divided into A, B, C, D level Four with respect to blank, and mortality ratio 100%-90% is the A level, and mortality ratio 90%-70% is the B level, and mortality ratio 70%-50% is the C level, and mortality ratio 0%-50% is the D level.Take Spiromesifen shown in spiral shell mite ester shown in formula (P-i) and/or formula (P-ii) as standard control, partial results sees Table 2～table 4 simultaneously.
Table 2 part of compounds when test concentrations is 1000mg/L to the activity of mythimna separata
Figure BSA00000141001100101
Table 3 part of compounds when test concentrations is 400mg/L to the activity of mythimna separata
Figure BSA00000141001100102
Table 4 part of compounds is in the activity of 25～100mg/L to mythimna separata
Figure BSA00000141001100103
The acaricidal activity evaluation of 11 pairs of two-spotted spider mites of embodiment (Tetranychus urticae)
Method is as follows: medicament is prepared with embodiment 10, the bean seedlings inoculation red spider that selection is grown fine, after red spider grows surely, with cut with the mite bean seedlings in the 3-provided by the invention for preparing (2-aminomethyl phenyl)-2-oxo-1-oxaspiro [4,5]-last of the ten Heavenly stems-3-alkene-4-alcohol or derivatives thereof liquid in dipping 10 seconds, take out and suck unnecessary liquid with filter paper, insert in the beaker that is filled with water, in observing indoor cultivation, checking after 48 hours survival and dead mite number has 100-200 mite on every strain bean seedlings.Experiment repeats 3 times.Results averaged.Activity in per-cent, is divided into A, B, C, D level Four with respect to blank, and grade scale is with embodiment 10, and simultaneously take Spiromesifen shown in spiral shell mite ester shown in formula (P-i) and/or formula (P-ii) as standard control, partial results sees Table 5～table 7.
Table 5 part of compounds when test concentrations is 500mg/L to the activity of two-spotted spider mite
Figure BSA00000141001100104
Table 6 part of compounds when test concentrations is 100mg/L to the activity of two-spotted spider mite
Figure BSA00000141001100105
Table 7 part of compounds when test concentrations is 10mg/L and 1mg/L to the activity of two-spotted spider mite
The potted plant test of pesticide effectiveness of embodiment 12 control two-spotted spider mites (Tetranychus urticae)
Method is as follows: transplant broad bean seedling of uniform size in the polypots of bore 30cm, when treating that seedling grows up to, the two-spotted spider mite of indoor feeding is connected on the broad bean seedling, allow it take food.Every 1 basin seedling is a residential quarter, and every concentration repeats 3 times, random alignment, and establishing clear water is blank, totally 36 residential quarters.Dispenser is label on porcelain alms bowl interpolation before, investigates and record two-spotted spider mite number on every young plant.Investigate and completely at once with electronic throat spray, 3 pot seedlings are sprayed simultaneously, the atomizer operating pressure is 0.1Mpa, injection diameter 1mm, and each processes spray amount 4ml.Investigated remaining insect population on the 1st, 3,7,14,21 day after dispenser, calculate prevention effect according to following formula, partial results sees Table 8.
Figure BSA00000141001100112
Table 8 part of compounds control two-spotted spider mite results from pot experiment test (preventive effect %)
Figure BSA00000141001100113
Embodiment 13
Insecticidal Activity to bean aphid (Aphis fabae)
Method is as follows: medicament is prepared with embodiment 10, bean aphid is connected on the bean seedlings that just have been unearthed, every strain connects more than 20, then with bean seedlings together with the examination worm be dipped in 3-provided by the invention (2-aminomethyl phenyl)-2-oxo-1-oxaspiro [4,5]-last of the ten Heavenly stems-3-alkene-4-alcohol or derivatives thereof liquid liquid in, take out after 5 seconds, suck unnecessary liquid, insert in the sponge of suction, cover with glass-tube, check survival and dead borer population after 24 hours.Repeat results averaged 3 times.Active blank relatively in per-cent, is divided into A, B, C, D level Four, and grade scale is with embodiment 10, and simultaneously take Spiromesifen shown in spiral shell mite ester shown in formula (P-i) and/or formula (P-ii) as standard control, partial results sees Table 9 and table 10.
Table 9 part of compounds when test concentrations is 500mg/l to the activity of bean aphid (Aphis fabae)
Figure BSA00000141001100121
Table 10 part of compounds when test concentrations is 100mg/l to the activity of bean aphid (Aphis fabae)
Figure BSA00000141001100122
The fungicidal activity of 14 pairs of Sclerotinia sclerotiorums of embodiment (Sclerotonia sclerotiorum)
Method following (toxic medium therapy): (1) Sclerotinia sclerotiorum (Sclerotonia sclerotiorum) bacterial classification is kept in refrigerator (4-8 ℃), test was inoculated in culture dish from the test tube slant in front 2-3 days, cultivated to be for experiment under optimal temperature.(2) take appropriate 3-provided by the invention (2-aminomethyl phenyl)-2-oxo-1-oxaspiro [4,5]-last of the ten Heavenly stems-3-alkene-4-alcohol derivate, with DMF dissolving, then be diluted with water to desired concn 500mg/L.Get 500mg/L liquid 2mL, add in the potato agar substratum (PDA) of the 38mL that is cooled to 45 ℃, 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.Be disposed, the constant temperature biochemical cultivation case that is placed in 28 ℃ is cultivated, and measures colony diameter after 4 days, calculates growth inhibition ratio.(4) part of compounds shows obvious fungicidal activity, the growth inhibition ratio to Sclerotinia sclerotiorum under 25mg/L concentration all reaches more than 90% as compound 06 and compound 11, and the growth inhibition ratio to Sclerotinia sclerotiorum under 25mg/L concentration of Spiromesifen shown in spiral shell mite ester shown in formula (P-i) and formula (P-ii) is all 0%.
The fungicidal activity of 15 pairs of Rhizoctonia solani Kuhns of embodiment (Rhizoctonia solani)
Method following (Broad Bean Leaves method): (1) Rhizoctonia solani Kuhn (Rhizoctonia solani) bacterial classification is kept in refrigerator (4-8 ℃), test was inoculated in culture dish from the test tube slant in front 2-3 days, cultivated to be for experiment under optimal temperature.(2) take appropriate 3-provided by the invention (2-aminomethyl phenyl)-2-oxo-1-oxaspiro [4,5]-last of the ten Heavenly stems-3-alkene-4-alcohol derivate, with DMF dissolving, then be diluted with water to desired concn 500mg/L.(3) blade of clip broad bean susceptible variety; put in culture dish; with atomizer with the 500mg/L compound liquid medicine jet wet leaves sheet back side; after natural air drying; be that 6.5mm bacterium cake has the one side of mycelia to be inoculated in to process blade central authorities with inoculator with diameter; the protectiveness test is inoculation in 24 hours after chemicals treatment, and inoculation is placed in growth cabinet, cultivates under the condition of 26～28 ℃ of temperature, relative humidity 80%～90%.Depending on the blank incidence, calculate prevention effect.(4) part of compounds shows obvious fungicidal activity, reach more than 90% as compound 06 prevention effect to Rhizoctonia solani Kuhn under 500mg/L concentration, and the prevention effect to Rhizoctonia solani Kuhn under 500mg/L concentration of Spiromesifen shown in spiral shell mite ester shown in formula (P-i) and formula (P-ii) is all 0%.
The fungicidal activity of 16 pairs of wheat powdery mildews of embodiment (Blumeria graminis)
Method following (pot-culture method): (1) wheat powdery mildew (Blumeria graminis) is preserved spore with stem and leaf of Wheat and is for experiment.(2) take appropriate 3-provided by the invention (2-aminomethyl phenyl)-2-oxo-1-oxaspiro [4,5]-last of the ten Heavenly stems-3-alkene-4-alcohol derivate, with DMF dissolving, then be diluted with water to desired concn 500mg/L.(3) select 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; naturally dry; evenly shake off to be inoculated on stem and leaf of Wheat the fresh spore of Powdery Mildew that the morbidity wheat leaf blade produced in upper 24 hour; every processing is no less than 3 basins; every basin 10 strains, the protectiveness test is inoculation in 24 hours after chemicals treatment, then puts under suitable condition and cultivates.According to blank incidence classification investigation, calculate prevention effect.(4) part of compounds shows obvious fungicidal activity, the preventive effect to wheat powdery mildew under 500mg/L concentration reaches more than 60% as compound 06 and compound 11, and the prevention effect to wheat powdery mildew under 500mg/L concentration of spiral shell mite ester shown in formula (P-i) is 0%, and the prevention effect to wheat powdery mildew under 500mg/L concentration of Spiromesifen shown in formula (P-ii) is 60%.
The further screening of embodiment 17 pairs of Sclerotinia sclerotiorums, Pyricularia oryzae, Rhizoctonia solani Kuhn and wheat powdery mildews
With reference to the method for embodiment 14～embodiment 16, further studied the sterilization biological activity of part of compounds, table 11～table 12 has been listed the partial results of compound 06.
The activity (toxic medium therapy) of 06 pair of Sclerotinia sclerotiorum of table 11 compound and Pyricularia oryzae
Figure BSA00000141001100131
The prevention effect (pot-culture method) of 06 pair of Rhizoctonia solani Kuhn of table 12 compound and wheat powdery mildew
Figure BSA00000141001100132

Claims (3)

1. has bioactive 3-o-methyl-phenyl--2-oxo-1-oxaspiro [4,5]-last of the ten Heavenly stems-3-alkene-4-alcohol derivate, it is characterized in that the compound with general formula (I) expression is (01), (02), (04), (05), (06), (10), (11), their structural formula is as follows:
2. 3-o-methyl-phenyl-according to claim 1-2-oxo-1-oxaspiro [4,5]-last of the ten Heavenly stems-preparation method of 3-alkene-4-alcohol derivate, it is characterized in that in suitable methylene chloride or toluene, in-5～55 ℃, under suitable alkali triethylamine or pyridine existence, add suitable catalyzer 4-dimethylamino pyridine to add fast response or improve reaction yield, use formula, (II) compound shown in and corresponding formula, (III) acyl chloride reaction shown in, namely get general formula, (I) compound, as reaction formula 1
Reaction formula 1:
Figure FDA00002766823100012
In solvent-free or solvent toluene, sulfur oxychloride and o-Tolylacetic acid (II-a) react under the system reflux temperature, slough solvent and get o-methyl-benzene Acetyl Chloride 98Min. (II-b); (II-b) in suitable solvent toluene or benzene, add catalyzer 4-dimethylamino pyridine, react to get formula (II-c) with the compound shown in formula (IV) under the system reflux conditions; In the solvent pyridine, with alkali potassium hydroxide or sodium-hydroxide treatment formula (II-c) compound, more namely get the compound of formula (II) with 5%～20% salt acid treatment in 15～30 ℃, as reaction formula 2,
Reaction formula 2:
Figure FDA00002766823100013
The compound of formula (IV) is pressed reaction formula 3, and popular response obtains,
Reaction formula 3:
Figure FDA00002766823100021
In reaction formula 1 R have in claim 1 to definition.
3-o-methyl-phenyl-according to claim 1-2-oxo-1-oxaspiro [4,5]-last of the ten Heavenly stems-purposes of 3-alkene-4-alcohol derivate, it is characterized in that having the mite of killing, desinsection, antifungal bioactivity under 15～375 gram effective constituent/hectare consumptions.
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